#==============================================================================
data_New_Global_Publ_Block
_publ_section_related_literature
;
For related structurally characterized NHC-B adducts see: Arduengo et
al., 2000; Kuhn et al., 1997; Nielsen et al., 2003 (analysis
of the Cambridge Structural Database; CSD; Version 5.27, release May 2009;
Allen, 2002; 4 entries, 5 fragments). For a description of the Cambridge
Structural database, see: Allen, 2002.
;
# Added by publCIF - use a unique identifier for each data block
#==============================================================================
# SUBMISSION DETAILS
_publ_contact_author_name
'Maxim V. Borzov' # Name of author for correspondence
_publ_contact_author_address # Address of author for correspondence
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
_publ_contact_author_email 'maxborzov@mail.ru'
_publ_contact_author_fax '+86(29)88303947'
_publ_contact_author_phone '+86(29)88303947'
_publ_contact_letter
;
Please consider this CIF for publication. I certify that this contibution is the
original work of those listed as authors; that it has not been published
before (in any language or medium) and is not being considered for publication
elsewhere; that all authors concur with and are aware of the submission; that
all workers involved in the study are listed as authors or given proper credit
in the acknowledgements; that I have obtained permission for and acknowledged
the source of any excerpts from other copyright works; and that to the best of
my knowledge the paper contains no statements which are libellous, unlawful or
in any way actionable. All coauthors have made significant scientific
contributions to the work reported, including the ideas and their execution,
and share responsibility and accountability for the results.
;
_publ_requested_journal 'Organometallics'
_publ_requested_category FM
#==============================================================================
# TITLE AND AUTHOR LIST
_publ_section_title
;
High-Yield Thermolytic Conversion of Imidazolium Salts into Arduengo Carbene
Adducts with BF~3~ and PF~5~
;
_publ_section_title_footnote # remove if not required
.
# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary.
# NB if using publCIF, the Author database tool might prove useful
# (see the Tools menu in publCIF)
loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
_publ_author_email
'Tian, Chong'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
tianchong30@163.com
;
'Nie, Wanli'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
niewl126@126.com
;
'Borzov, Maxim V.'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
maxborzov@mail.ru
;
'Su, Pengfei'
;
Xi'an Modern Chemistry Research Institute, East Zhangba road 168, Xi'an 71065,
Shaanxi prov., P. R. China
;
.
;
spf1978_2000@163.com
;
#==============================================================================
# TEXT
_publ_section_synopsis
.
_publ_section_abstract
;
Thermolysis of 1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate
(1) and 1,3-dimethyl-1H-imidazolium hexa苯luo訃o計hosphate
(3) under reduced pressure affords Arduengo carbene adducts with BF~3~
and PF~5~ (2 and 4) and HF in a high-yield, what presents the
first example of a direct [C--H] + E--F \\rightarrow [C--E] + H--F bond
rearrangement (E = B or P). Intuitively expected alkylfluorides and imidazole
N-adducts with BF~3~ and/or PF~5~ are not detected at all. DFT computational
study suggests a single step mechanism for the 1 \\rightarrow 2
+ HF conversion. Lower-yield thermolysis of 1,2,3-trimethyl- analogue of
4 into
(1,3-dimethyl-1H-imidazolium-2-yl)methylpenta苯luo訃o計hos計hate
(12) points to a rather general character of this reaction.
;
_publ_section_comment
;\
The title compound, C~5~H~8~F~3~N~2~B, 2, presents a formal adduct of a
N-heterocyclic carbene (NHC),
1-ethyl-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene, and boron
trifluoride. Compound 2 was prepared by a thermolytic decomposition of
1,3-dimethyl-1H-imidazolium tetrafluoroborate at 300-400 \%C under
reduced pressure (1.0--1.5\\times10^--3^ Torr; 1 Torr = 133 Pa). It presents a
thermally stable (sublimes under the preparation conditions) air and protic
solvent resistant compound (can be recrystallized from hot water or ethanol in
presence of air).
The imidazole ring of 2 is planar within 0.003 \%A with the C1 and N1
atoms deviating the most from the PL1 plane (PL1 denotes C1/N1/C2/C3/N2 r.m.s.
plane). Atoms B1, C4, and C6 all lay inside this plane [deviations from PL1
are 0.010 (4), --0.003 (4), and 0.059 (4) \%A, respectively]. The fluorine
atom F3 is oriented towards the C6 methylene group atom [N1/C1/B1/F3 torsion
angle --10.8(3)\%]. The H-atoms at the NCH~3~ group are disordered between two
positions [sof-s 0.72 (3) and 0.28 (3)]. The C5/C4/N1 plane is nearly
perpendicular to the PL1 [interplane angle equals to 88.6(2)\%].
Analysis of the Cambridge Structural Database [CSD, version 5.27, release May
2009 (Allen, 2002)] reveals 19 structurally characterized imidazole-type
NHC--borane adducts (24 fragments). Among them there are only four NHC--BF~3~
type compounds (Arduengo et al., 2000; Kuhn et al., 1997;
Nielsen et al., 2003) (5 fragments), with
{\m-2,2'-oxy-bi[(3-methyl-2,3-dihydro-1H-imidazol-2-ylidene-1-yl-\
\kC^2^)ethane]}bis[trifluoroborane] (Nielsen et al., 2003)
being the closest analogue of I. Of interest, the latter literature compound
(Nielsen et al., 2003), actually, presents two moieties of I linked
together at theend ethyl group carbons with an --O-- bridge, with all related
distances, angles, and even torsion angles being quite similar to those
observed in 2. Statistical analysis of the structural parameters of the
known NHC--BF~3~ type compounds (Arduengo et al., 2000; Kuhn et
al., 1997; Nielsen et al., 2003) reveals that all distances
B1--F1(2,3),C1--B1, C1--N1(2), C2(3)--N1(2), C2--C3 and angles N1(2)--C1--B1,
C1--N1(2)--C2(3), N1(2)--C2(3)--C3(2), N1--C1--N2 in 2 (similar bonds
and angles are grouped) are close to the median values observed earlier
(1.383, 1.644, 1.351, 1.385, 1.343\%A and 126.98, 110.29, 106.97, 105.60\%,
respectively) and are all within the observed intervals of the values.
;
_publ_section_acknowledgements # remove if not required
;
Financial support from the National Natural Science Foundation of China
(projects Nos. 20702041 & 21072157) and Shaanxi province Administration of
Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully
acknowledged.
;
_publ_section_references
;
Allen, F. H. (2002). Acta Cryst. B58, 380--388.
Arduengo, A. J. III, Davidson, F., Krafczyk, R., Marshalll, W. J. & Schmutzler,
R. (2000). Monatschafte f\"ur Chemie, 131, 251-265.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339--341.
Kuhn, N., Fawzi, R., Kotowski, H. & Steimann, M. (1997). Z. Krystallogr.
259-260.
Nielsen, D. J., Kavell, K. J., Skelton, B. W. & White, A. H. (2003). Inorg.
Chim. Acta, 352, 143-150.
Sheldrick, G. M. (1996). SADABS. University of G\"ottingen, Germany.
Sheldrick, G. M. (2008). SHELXS97 and SHELXL97. Acta
Cryst. A64, 112-122.
;
_publ_section_figure_captions
;
Fig. 1. Unsymmetrical unit of I with labeling. Thermal ellipsoids are shown at
the 50% level of probability.
;
_publ_section_exptl_prep
;
Single crystal of I suitable for the X-ray diffraction analysis was prepared by
recrystallization from toluene (evacuated all-sealed glass vessel).
;
_publ_section_exptl_refinement
;
Non-H atoms were refined anisotropically. H atoms except of the disordered ones
at C6 were found from the difference Fourier synthesis and refined
isotropically. The disordered H-atoms at C6 were treated as riding atoms with
distances C---H = 0.96 \%A (CH~3~) and U~iso~(H) = 1.5 U~eq~(C).
The H-atoms at the C6 methyl group carbon atom are disordered between two
positions with sof-s 0.72 (3) and 0.28 (3).
;
#==============================================================================
_publ_manuscript_text
# Used for convenience to store draft or replaced versions
# of the abstract, comment etc.
# Its contents will not be output
?
#==============================================================================
# Formatted by publCIF
data_I
_iucr_refine_instructions_details
;
TITL Z in P2(1)/c
CELL 0.71073 7.2873 7.7101 15.1225 90 101.933 90
ZERR 4 0.0008 0.0008 0.0016 0 0.002 0
LATT 1
SYMM -X,0.5+Y,0.5-Z
SFAC C H B F N
UNIT 24 40 4 12 8
L.S. 10
PLAN 20
SIZE 0.27 0.28 0.36
TEMP 23
BOND $H
CONF
MORE -1
fmap 2
acta
OMIT 0 51
REM C:/frames/guest/110331_MBF/work/A.hkl
WGHT 0.040300 0.196300
FVAR 0.77988 0.72182
B1 3 0.753255 0.767024 0.632300 11.00000 0.04403 0.07903 =
0.04361 -0.00056 0.01177 -0.00647
F1 4 0.622192 0.895414 0.602163 11.00000 0.05340 0.12857 =
0.08366 0.01954 0.02444 0.02366
F2 4 0.666009 0.607421 0.623934 11.00000 0.11176 0.10665 =
0.10056 -0.01372 0.05835 -0.05101
F3 4 0.834565 0.795614 0.721266 11.00000 0.06980 0.13939 =
0.04259 -0.00632 0.01698 0.00128
N1 5 1.091572 0.817555 0.588237 11.00000 0.03954 0.06239 =
0.04449 0.00102 0.00686 -0.00218
N2 5 0.876800 0.721549 0.481399 11.00000 0.04593 0.06635 =
0.03704 0.00136 0.00630 -0.00220
C1 1 0.910834 0.768950 0.568639 11.00000 0.03895 0.05329 =
0.03771 0.00251 0.00519 -0.00268
C2 1 1.035705 0.738823 0.446928 11.00000 0.05962 0.09295 =
0.04189 0.00520 0.01959 0.00713
H2 2 1.037052 0.711292 0.384946 11.00000 0.08679
C3 1 1.169116 0.798350 0.513088 11.00000 0.04488 0.09102 =
0.05953 0.01019 0.02126 0.00326
H3 2 1.296559 0.822999 0.514352 11.00000 0.08687
C4 1 1.196128 0.880521 0.676484 11.00000 0.04958 0.08004 =
0.05983 -0.00791 0.00098 -0.01366
H4A 2 1.291415 0.958217 0.663713 11.00000 0.08482
H4B 2 1.106098 0.947646 0.705943 11.00000 0.07299
C5 1 1.283100 0.736437 0.736531 11.00000 0.05901 0.11170 =
0.05252 -0.00382 -0.00410 0.00961
H5A 2 1.340956 0.785474 0.799715 11.00000 0.09447
H5B 2 1.179482 0.649367 0.744294 11.00000 0.10193
H5C 2 1.377472 0.673018 0.714626 11.00000 0.09521
C6 1 0.694736 0.665650 0.428496 11.00000 0.06603 0.10374 =
0.04558 -0.00743 -0.00519 -0.01762
PART 1
AFIX 33
H6AA 2 0.653392 0.564467 0.455820 21.00000 -1.50000
H6AB 2 0.706753 0.638737 0.367972 21.00000 -1.50000
H6AC 2 0.604785 0.757124 0.427037 21.00000 -1.50000
PART 0
PART 2
H6BD 2 0.701416 0.546040 0.411856 -21.00000 -1.50000
H6BE 2 0.679096 0.730910 0.373386 -21.00000 -1.50000
H6BF 2 0.593426 0.668360 0.460206 -21.00000 -1.50000
HKLF 4
REM Z in P2(1)/c
REM R1 = 0.0391 for 1038 Fo > 4sig(Fo) and 0.0685 for all 1547 data
REM 138 parameters refined using 0 restraints
END
WGHT 0.0403 0.1963
REM Highest difference peak 0.166, deepest hole -0.166, 1-sigma level 0.032
Q1 1 0.6026 0.6924 0.5754 11.00000 0.05 0.17
Q2 1 0.8319 0.7714 0.6016 11.00000 0.05 0.15
Q3 1 0.8740 0.9028 0.7004 11.00000 0.05 0.13
Q4 1 0.7855 0.6377 0.6735 11.00000 0.05 0.13
Q5 1 1.1237 1.0296 0.6812 11.00000 0.05 0.11
Q6 1 0.6204 0.8276 0.5460 11.00000 0.05 0.11
Q7 1 1.2968 0.9201 0.5210 11.00000 0.05 0.11
Q8 1 0.7410 0.9624 0.6422 11.00000 0.05 0.10
Q9 1 0.7252 0.4771 0.6245 11.00000 0.05 0.10
Q10 1 1.1239 1.0088 0.6016 11.00000 0.05 0.09
Q11 1 0.6294 0.5581 0.6436 11.00000 0.05 0.09
Q12 1 0.6791 0.5085 0.4228 11.00000 0.05 0.09
Q13 1 0.8368 0.6698 0.7004 11.00000 0.05 0.08
Q14 1 1.3088 0.5978 0.7117 11.00000 0.05 0.08
Q15 1 1.0780 0.5467 0.6971 11.00000 0.05 0.08
Q16 1 1.3560 0.9102 0.6425 11.00000 0.05 0.08
Q17 1 1.4025 0.8410 0.7803 11.00000 0.05 0.08
Q18 1 1.3946 0.9008 0.6048 11.00000 0.05 0.08
Q19 1 1.1301 0.7305 0.5840 11.00000 0.05 0.08
Q20 1 0.9958 0.8123 0.5829 11.00000 0.05 0.08
;
_audit_creation_method SHELXL-97
_chemical_name_systematic
;\
(1,3-Dimethyl-2,3-dihydro-1H-imidazol-2-ylidene-\kC^2^)\
trifluoroboron
;
_chemical_name_common ?
_chemical_melting_point ?
_chemical_formula_moiety 'C6 H10 B F3 N2'
_chemical_formula_sum
'C6 H10 B F3 N2'
_chemical_formula_weight 177.97
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'B' 'B' 0.0013 0.0007
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting monoclinic
_symmetry_space_group_name_H-M 'P 21/c'
_symmetry_space_group_name_Hall '-P 2ybc'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
_cell_length_a 7.2873(8)
_cell_length_b 7.7101(8)
_cell_length_c 15.1225(16)
_cell_angle_alpha 90.00
_cell_angle_beta 101.933(2)
_cell_angle_gamma 90.00
_cell_volume 831.31(15)
_cell_formula_units_Z 4
_cell_measurement_temperature 296(2)
_cell_measurement_reflns_used 2223
_cell_measurement_theta_min 2.64
_cell_measurement_theta_max 28.17
_exptl_crystal_description block
_exptl_crystal_colour colourless
_exptl_crystal_size_max 0.36
_exptl_crystal_size_mid 0.28
_exptl_crystal_size_min 0.27
_exptl_crystal_density_meas ?
_exptl_crystal_density_diffrn 1.422
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 368
_exptl_absorpt_coefficient_mu 0.133
_exptl_absorpt_correction_type multi-scan
_exptl_absorpt_correction_T_min 0.9538
_exptl_absorpt_correction_T_max 0.9651
_exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)'
_exptl_special_details
;
Single crystal of I suitable for the X-ray diffraction analysis was prepared by
recrystallization from toluene (evacuated all-sealed glass vessel). Non-H
atoms were refined anisotropically. H atoms except of the disordered ones at
C6 were found from the difference Fourier synthesis and refined isotropically.
The disordered H-atoms at C6 were treated as riding atoms with distances C---H
= 0.96 \%A (CH~3~) and U~iso~(H) = 1.5 U~eq~(C). The H-atoms at
the C6 methyl group carbon atom are disordered between two positions with
sof-s 0.72 (3) and 0.28 (3).
;
_diffrn_ambient_temperature 296(2)
_diffrn_radiation_wavelength 0.71073
_diffrn_radiation_type MoK\a
_diffrn_radiation_source 'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type 'BRUKER SMART APEXII'
_diffrn_measurement_method 'phi and omega scans'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number 0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time .
_diffrn_standards_decay_% ?
_diffrn_reflns_number 4144
_diffrn_reflns_av_R_equivalents 0.0235
_diffrn_reflns_av_sigmaI/netI 0.0292
_diffrn_reflns_limit_h_min -8
_diffrn_reflns_limit_h_max 8
_diffrn_reflns_limit_k_min -9
_diffrn_reflns_limit_k_max 7
_diffrn_reflns_limit_l_min -17
_diffrn_reflns_limit_l_max 18
_diffrn_reflns_theta_min 2.75
_diffrn_reflns_theta_max 25.50
_reflns_number_total 1547
_reflns_number_gt 1038
_reflns_threshold_expression >2sigma(I)
_computing_data_collection 'BRUKER AXS APEX-2 V1.0-8 (Bruker, 2007)'
_computing_cell_refinement 'SAINT v7.34A (Bruker, 2007)'
_computing_data_reduction 'SAINT v7.34A (Bruker, 2007)'
_computing_structure_solution 'SHELXS97 (Sheldrick, 2008)'
_computing_structure_refinement 'SHELXL97 (Sheldrick, 2008)'
_computing_molecular_graphics
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_computing_publication_material
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type full
_refine_ls_weighting_scheme calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0403P)^2^+0.1963P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment mixed
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_reflns 1547
_refine_ls_number_parameters 138
_refine_ls_number_restraints 0
_refine_ls_R_factor_all 0.0685
_refine_ls_R_factor_gt 0.0391
_refine_ls_wR_factor_ref 0.1046
_refine_ls_wR_factor_gt 0.0957
_refine_ls_goodness_of_fit_ref 1.065
_refine_ls_restrained_S_all 1.065
_refine_ls_shift/su_max 0.000
_refine_ls_shift/su_mean 0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
B1 B 0.7533(3) 0.7670(4) 0.63230(15) 0.0552(6) Uani 1 1 d . . .
F1 F 0.62219(17) 0.8954(2) 0.60216(9) 0.0871(5) Uani 1 1 d . . .
F2 F 0.6660(2) 0.6074(2) 0.62393(11) 0.1011(6) Uani 1 1 d . . .
F3 F 0.83456(19) 0.7956(2) 0.72127(8) 0.0832(5) Uani 1 1 d . . .
N1 N 1.0916(2) 0.8176(2) 0.58824(10) 0.0491(4) Uani 1 1 d . . .
N2 N 0.8768(2) 0.7215(2) 0.48140(10) 0.0501(4) Uani 1 1 d . . .
C1 C 0.9108(2) 0.7690(2) 0.56864(12) 0.0437(5) Uani 1 1 d . . .
C2 C 1.1691(3) 0.7983(3) 0.51309(15) 0.0636(6) Uani 1 1 d . . .
H2 H 1.297(4) 0.823(3) 0.5144(17) 0.087(8) Uiso 1 1 d . . .
C3 C 1.0357(3) 0.7388(3) 0.44693(15) 0.0635(6) Uani 1 1 d . . .
H3 H 1.037(3) 0.711(3) 0.3849(19) 0.087(8) Uiso 1 1 d . . .
C4 C 1.1961(3) 0.8805(3) 0.67648(16) 0.0646(6) Uani 1 1 d . . .
H4A H 1.291(3) 0.958(3) 0.6637(15) 0.085(8) Uiso 1 1 d . . .
H4B H 1.106(3) 0.948(3) 0.7059(15) 0.073(7) Uiso 1 1 d . . .
C5 C 1.2831(4) 0.7364(4) 0.73653(17) 0.0767(8) Uani 1 1 d . . .
H5A H 1.341(4) 0.785(3) 0.7997(19) 0.094(8) Uiso 1 1 d . . .
H5B H 1.179(4) 0.649(4) 0.7443(18) 0.102(9) Uiso 1 1 d . . .
H5C H 1.377(4) 0.673(3) 0.7146(18) 0.095(9) Uiso 1 1 d . . .
C6 C 0.6947(3) 0.6657(3) 0.42850(14) 0.0742(7) Uani 1 1 d . . .
H6AA H 0.6534 0.5645 0.4558 0.111 Uiso 0.72(3) 1 calc PR A 1
H6AB H 0.7068 0.6387 0.3680 0.111 Uiso 0.72(3) 1 calc PR A 1
H6AC H 0.6048 0.7571 0.4270 0.111 Uiso 0.72(3) 1 calc PR A 1
H6BD H 0.7014 0.5460 0.4119 0.111 Uiso 0.28(3) 1 d PR A 2
H6BE H 0.6791 0.7309 0.3734 0.111 Uiso 0.28(3) 1 d PR A 2
H6BF H 0.5934 0.6684 0.4602 0.111 Uiso 0.28(3) 1 d PR A 2
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
B1 0.0440(13) 0.0790(17) 0.0436(13) -0.0006(12) 0.0118(10) -0.0065(12)
F1 0.0534(7) 0.1286(13) 0.0837(10) 0.0195(9) 0.0244(7) 0.0237(8)
F2 0.1118(12) 0.1066(12) 0.1006(11) -0.0137(9) 0.0583(10) -0.0510(10)
F3 0.0698(8) 0.1394(13) 0.0426(7) -0.0063(7) 0.0170(6) 0.0013(8)
N1 0.0395(9) 0.0624(10) 0.0445(9) 0.0010(8) 0.0069(7) -0.0022(7)
N2 0.0459(9) 0.0663(11) 0.0370(8) 0.0014(7) 0.0063(7) -0.0022(8)
C1 0.0390(10) 0.0533(11) 0.0377(10) 0.0025(8) 0.0052(8) -0.0027(8)
C2 0.0449(12) 0.0910(17) 0.0595(14) 0.0102(12) 0.0213(11) 0.0033(11)
C3 0.0596(14) 0.0929(17) 0.0419(12) 0.0052(12) 0.0196(10) 0.0071(12)
C4 0.0496(13) 0.0800(17) 0.0598(14) -0.0079(12) 0.0010(11) -0.0137(13)
C5 0.0590(16) 0.112(2) 0.0525(14) -0.0038(15) -0.0041(12) 0.0096(16)
C6 0.0660(14) 0.1037(19) 0.0456(12) -0.0074(12) -0.0052(11) -0.0176(13)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
B1 F3 1.371(3) . ?
B1 F2 1.379(3) . ?
B1 F1 1.386(3) . ?
B1 C1 1.644(3) . ?
N1 C1 1.342(2) . ?
N1 C2 1.378(3) . ?
N1 C4 1.475(3) . ?
N2 C1 1.342(2) . ?
N2 C3 1.371(3) . ?
N2 C6 1.465(3) . ?
C2 C3 1.325(3) . ?
C2 H2 0.94(3) . ?
C3 H3 0.96(3) . ?
C4 C5 1.491(4) . ?
C4 H4A 0.97(3) . ?
C4 H4B 1.01(2) . ?
C5 H5A 1.03(3) . ?
C5 H5B 1.04(3) . ?
C5 H5C 0.96(3) . ?
C6 H6AA 0.9600 . ?
C6 H6AB 0.9600 . ?
C6 H6AC 0.9600 . ?
C6 H6BD 0.9598 . ?
C6 H6BE 0.9599 . ?
C6 H6BF 0.9601 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
F3 B1 F2 109.33(19) . . ?
F3 B1 F1 109.67(19) . . ?
F2 B1 F1 109.51(18) . . ?
F3 B1 C1 111.14(16) . . ?
F2 B1 C1 108.60(18) . . ?
F1 B1 C1 108.56(17) . . ?
C1 N1 C2 109.81(17) . . ?
C1 N1 C4 126.25(17) . . ?
C2 N1 C4 123.94(18) . . ?
C1 N2 C3 110.39(17) . . ?
C1 N2 C6 125.41(17) . . ?
C3 N2 C6 124.16(17) . . ?
N2 C1 N1 105.46(15) . . ?
N2 C1 B1 124.32(16) . . ?
N1 C1 B1 130.21(16) . . ?
C3 C2 N1 107.34(19) . . ?
C3 C2 H2 130.6(16) . . ?
N1 C2 H2 122.1(16) . . ?
C2 C3 N2 106.99(19) . . ?
C2 C3 H3 131.1(15) . . ?
N2 C3 H3 121.9(15) . . ?
N1 C4 C5 112.4(2) . . ?
N1 C4 H4A 106.3(14) . . ?
C5 C4 H4A 110.6(14) . . ?
N1 C4 H4B 107.9(12) . . ?
C5 C4 H4B 110.3(13) . . ?
H4A C4 H4B 109.3(19) . . ?
C4 C5 H5A 109.4(14) . . ?
C4 C5 H5B 108.9(15) . . ?
H5A C5 H5B 107(2) . . ?
C4 C5 H5C 114.5(16) . . ?
H5A C5 H5C 109(2) . . ?
H5B C5 H5C 108(2) . . ?
N2 C6 H6AA 109.5 . . ?
N2 C6 H6AB 109.5 . . ?
H6AA C6 H6AB 109.5 . . ?
N2 C6 H6AC 109.5 . . ?
H6AA C6 H6AC 109.5 . . ?
H6AB C6 H6AC 109.5 . . ?
N2 C6 H6BD 109.7 . . ?
H6AA C6 H6BD 50.9 . . ?
H6AB C6 H6BD 61.5 . . ?
H6AC C6 H6BD 140.5 . . ?
N2 C6 H6BE 104.6 . . ?
H6AA C6 H6BE 143.9 . . ?
H6AB C6 H6BE 45.8 . . ?
H6AC C6 H6BE 68.7 . . ?
H6BD C6 H6BE 106.2 . . ?
N2 C6 H6BF 115.1 . . ?
H6AA C6 H6BF 57.4 . . ?
H6AB C6 H6BF 135.4 . . ?
H6AC C6 H6BF 53.4 . . ?
H6BD C6 H6BF 103.8 . . ?
H6BE C6 H6BF 117.2 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N2 C1 N1 0.6(2) . . . . ?
C6 N2 C1 N1 -177.14(19) . . . . ?
C3 N2 C1 B1 179.5(2) . . . . ?
C6 N2 C1 B1 1.8(3) . . . . ?
C2 N1 C1 N2 -0.6(2) . . . . ?
C4 N1 C1 N2 -179.87(19) . . . . ?
C2 N1 C1 B1 -179.4(2) . . . . ?
C4 N1 C1 B1 1.3(3) . . . . ?
F3 B1 C1 N2 170.50(18) . . . . ?
F2 B1 C1 N2 50.2(3) . . . . ?
F1 B1 C1 N2 -68.8(3) . . . . ?
F3 B1 C1 N1 -10.8(3) . . . . ?
F2 B1 C1 N1 -131.2(2) . . . . ?
F1 B1 C1 N1 109.9(2) . . . . ?
C1 N1 C2 C3 0.4(3) . . . . ?
C4 N1 C2 C3 179.7(2) . . . . ?
N1 C2 C3 N2 0.0(3) . . . . ?
C1 N2 C3 C2 -0.4(3) . . . . ?
C6 N2 C3 C2 177.4(2) . . . . ?
C1 N1 C4 C5 88.1(3) . . . . ?
C2 N1 C4 C5 -91.1(3) . . . . ?
_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full 25.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max 0.166
_refine_diff_density_min -0.166
_refine_diff_density_rms 0.032
#===END
#==============================================================================
data_New_Global_Publ_Block
_publ_section_related_literature
;
For related structurally characterized NHC-B adducts see: Arduengo et
al., 2000; Kuhn et al., 1997; Nielsen et al., 2003 (analysis
of the Cambridge Structural Database; CSD; Version 5.27, release May 2009;
Allen, 2002; 4 entries, 5 fragments). For a description of the Cambridge
Structural database, see: Allen, 2002.
;
# Added by publCIF - use a unique identifier for each data block
#==============================================================================
# SUBMISSION DETAILS
_publ_contact_author_name
'Maxim V. Borzov' # Name of author for correspondence
_publ_contact_author_address # Address of author for correspondence
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
_publ_contact_author_email 'maxborzov@mail.ru'
_publ_contact_author_fax '+86(29)88303947'
_publ_contact_author_phone '+86(29)88303947'
_publ_contact_letter
;
Please consider this CIF for publication. I certify that this contibution is the
original work of those listed as authors; that it has not been published
before (in any language or medium) and is not being considered for publication
elsewhere; that all authors concur with and are aware of the submission; that
all workers involved in the study are listed as authors or given proper credit
in the acknowledgements; that I have obtained permission for and acknowledged
the source of any excerpts from other copyright works; and that to the best of
my knowledge the paper contains no statements which are libellous, unlawful or
in any way actionable. All coauthors have made significant scientific
contributions to the work reported, including the ideas and their execution,
and share responsibility and accountability for the results.
;
_publ_requested_journal 'Organometallics'
_publ_requested_category FM
#==============================================================================
# TITLE AND AUTHOR LIST
_publ_section_title
;
High-Yield Thermolytic Conversion of Imidazolium Salts into Arduengo Carbene
Adducts with BF~3~ and PF~5~
;
_publ_section_title_footnote # remove if not required
.
# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary.
# NB if using publCIF, the Author database tool might prove useful
# (see the Tools menu in publCIF)
loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
_publ_author_email
'Tian, Chong'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
tianchong30@163.com
;
'Nie, Wanli'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
niewl126@126.com
;
'Borzov, Maxim V.'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
maxborzov@mail.ru
;
'Su, Pengfei'
;
Xi'an Modern Chemistry Research Institute, East Zhangba road 168, Xi'an 71065,
Shaanxi prov., P. R. China
;
.
;
spf1978_2000@163.com
;
#==============================================================================
# TEXT
_publ_section_synopsis
.
_publ_section_abstract
;\
Thermolysis of 1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate
(1) and 1,3-dimethyl-1H-imidazolium
hexafluorophosphate (3) under reduced pressure affords
Arduengo carbene adducts with BF~3~ and PF~5~ (2 and 4) and HF
in a high-yield, what presents the first example of a direct [C--H] + E--F
\\rightarrow [C--E] + H--F bond rearrangement (E = B or P). Intuitively
expected alkylfluorides and imidazole N-adducts with BF~3~ and/or PF~5~ are
not detected at all. DFT computational study suggests a single step mechanism
for the 1 \\rightarrow 2 + HF conversion. Lower-yield
thermolysis of 1,2,3-trimethyl- analogue of 4 into
(1,3-dimethyl-1H-imidazolium-2-yl)methylpentafluoro\
phosphate (12) points to a rather general character of this
reaction.
;
_publ_section_comment
;\
The title compound, C~5~H~8~F~3~N~2~B, 2, presents a formal adduct of a
N-heterocyclic carbene (NHC),
1-ethyl-3-methyl-2,3-dihydro-1H-imidazol-2-ylidene, and boron
trifluoride. Compound 2 was prepared by a thermolytic decomposition of
1,3-dimethyl-1H-imidazolium tetrafluoroborate at 300-400 \%C under
reduced pressure (1.0--1.5\\times10^--3^ Torr; 1 Torr = 133 Pa). It presents a
thermally stable (sublimes under the preparation conditions) air and protic
solvent resistant compound (can be recrystallized from hot water or ethanol in
presence of air).
The imidazole ring of 2 is planar within 0.004 \%A with the C1 atom
deviating the most from the PL1 plane (PL1 denotes C1/N1/C2/C3/N2 r.m.s.
plane). Atoms B1, C4, and C6 all lay inside this plane [deviations from PL1
are 0.011 (4), --0.003 (4), and 0.054 (4) \%A, respectively]. The fluorine
atom F3 is oriented towards the C6 methylene group atom [N1/C1/B1/F3 torsion
angle --10.9(3)\%]. The H-atoms at the NCH~3~ group are disordered between two
positions (sof-s 0.77 and 0.23). The C5/C4/N1 plane is nearly
perpendicular to the PL1 [interplane angle equals to 88.00(19)\%].
Analysis of the Cambridge Structural Database [CSD, version 5.27, release May
2009 (Allen, 2002)] reveals 19 structurally characterized imidazole-type
NHC--borane adducts (24 fragments). Among them there are only four NHC--BF~3~
type compounds (Arduengo et al., 2000; Kuhn et al., 1997;
Nielsen et al., 2003) (5 fragments), with
{\m-2,2'-oxy-bi[(3-methyl-2,3-dihydro-1H-imidazol-2-ylidene-1-yl-\
\kC^2^)ethane]}bis[trifluoroborane] (Nielsen et al., 2003)
being the closest analogue of 2. Of interest, the latter literature
compound (Nielsen et al., 2003), actually, presents two moieties of
2 linked together at theend ethyl group carbons with an --O-- bridge,
with all related distances, angles, and even torsion angles being quite
similar to those observed in 2. Statistical analysis of the structural
parameters of the known NHC--BF~3~ type compounds (Arduengo et al.,
2000; Kuhn et al., 1997; Nielsen et al., 2003) reveals that all
distances B1--F1(2,3),C1--B1, C1--N1(2), C2(3)--N1(2), C2--C3 and angles
N1(2)--C1--B1, C1--N1(2)--C2(3), N1(2)--C2(3)--C3(2), N1--C1--N2 in 2
(similar bonds and angles are grouped) are close to the median values observed
earlier (1.383, 1.644, 1.351, 1.385, 1.343\%A and 126.98, 110.29, 106.97,
105.60\%, respectively) and are all within the observed intervals of the
values.
;
_publ_section_acknowledgements # remove if not required
;
Financial support from the National Natural Science Foundation of China
(projects Nos. 20702041 & 21072157) and Shaanxi province Administration of
Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully
acknowledged.
;
_publ_section_references
;
Allen, F. H. (2002). Acta Cryst. B58, 380--388.
Arduengo, A. J. III, Davidson, F., Krafczyk, R., Marshalll, W. J. & Schmutzler,
R. (2000). Monatschafte f\"ur Chemie, 131, 251-265.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339--341.
Kuhn, N., Fawzi, R., Kotowski, H. & Steimann, M. (1997). Z. Krystallogr.
259-260.
Nielsen, D. J., Kavell, K. J., Skelton, B. W. & White, A. H. (2003). Inorg.
Chim. Acta, 352, 143-150.
Sheldrick, G. M. (1996). SADABS. University of G\"ottingen, Germany.
Sheldrick, G. M. (2008). SHELXS97 and SHELXL97. Acta
Cryst. A64, 112-122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7--13.
;
_publ_section_figure_captions
;
Fig. 1. Unsymmetrical unit of 2 with labeling. Thermal ellipsoids are
shown at the 50% level of probability.
;
_publ_section_exptl_prep
;
Single crystal of 2 suitable for the X-ray diffraction analysis was
prepared by recrystallization from boiling water (100 \%C, in air).
;
_publ_section_exptl_refinement
;
Non-H atoms were refined anisotropically. H atoms were treated as riding atoms
with distances C---H = 0.96 (CH~3~), 0.97 (CH~2~), 0.93? \%A (C~ArH~), and
U~iso~(H) = 1.5 U~eq~(C), 1.2 U~eq~(C), and 1.2
U~eq~(C), respectively. The H-atoms at the C6 methyl group carbon atom
were treated as disordered between two positions with sof-s 0.77 and
0.23. Presence of any solvent molecules was excluded by a special check
[SQUEEZE routine of the PLATON program package (Spek, 2003)].
;
#==============================================================================
_publ_manuscript_text
# Used for convenience to store draft or replaced versions
# of the abstract, comment etc.
# Its contents will not be output
?
#==============================================================================
# Formatted by publCIF
data_I
_iucr_refine_instructions_details
;
TITL 110105_TC1_1_0m in P21/c #14
CELL 0.71073 7.2918 7.7091 15.126 90 101.9347 90
ZERR 4 0.0015 0.0015 0.0029 0 0.0033 0
LATT 1
SYMM -X,0.5+Y,0.5-Z
SFAC C H B F N
UNIT 24 40 4 12 8
L.S. 10 0 0 511
PLAN 20
SIZE 0.3 0.26 0.16
TEMP 22.7
REM reset to P21/c #14
BOND $H
MORE -1
CONF
fmap 2
acta
OMIT 0 50.2
OMIT 3 1 2
REM D:/STRUCT/Tianchong/110105_TC1_1/work/110105_TC1_1_0m.hkl
WGHT 0.048100 0.139900
FVAR 0.78075 0.76916
F1 4 0.122475 0.895502 0.102091 11.00000 0.05313 0.12568 =
0.08196 0.01868 0.02396 0.02266
F2 4 0.166177 0.607447 0.123909 11.00000 0.11034 0.10345 =
0.09879 -0.01253 0.05693 -0.04985
F3 4 0.334691 0.795906 0.221394 11.00000 0.06837 0.13576 =
0.04134 -0.00681 0.01637 0.00139
N1 5 0.591209 0.817454 0.088143 11.00000 0.03786 0.06085 =
0.04405 0.00149 0.00614 -0.00194
N2 5 0.376625 0.721440 -0.018639 11.00000 0.04636 0.06535 =
0.03595 0.00200 0.00530 -0.00261
C1 1 0.411168 0.768990 0.068755 11.00000 0.04020 0.05060 =
0.03594 0.00268 0.00434 -0.00285
C2 1 0.668903 0.798523 0.013374 11.00000 0.04199 0.09280 =
0.05757 0.01080 0.01987 0.00406
AFIX 43
H2 2 0.792090 0.823145 0.009939 11.00000 -1.20000
AFIX 0
C3 1 0.535857 0.738634 -0.053066 11.00000 0.05926 0.09293 =
0.04180 0.00527 0.02027 0.00712
AFIX 43
H3 2 0.548074 0.713194 -0.111672 11.00000 -1.20000
AFIX 0
C4 1 0.696509 0.880557 0.176017 11.00000 0.05091 0.07419 =
0.05736 -0.00882 -0.00129 -0.01242
AFIX 23
H4A 2 0.612665 0.945799 0.205644 11.00000 -1.20000
H4B 2 0.794615 0.958537 0.166002 11.00000 -1.20000
AFIX 0
C5 1 0.782660 0.736151 0.236685 11.00000 0.05733 0.10898 =
0.05318 -0.00236 -0.00460 0.00912
AFIX 137
H5B 2 0.874892 0.678167 0.210350 11.00000 -1.50000
H5A 2 0.687062 0.655073 0.244110 11.00000 -1.50000
H5C 2 0.841316 0.782539 0.294530 11.00000 -1.50000
AFIX 0
C6 1 0.194836 0.664764 -0.071319 11.00000 0.06266 0.10125 =
0.04588 -0.00668 -0.00614 -0.01639
PART 1
AFIX 137
H6AB 2 0.205519 0.642300 -0.132476 21.00000 -1.50000
H6AC 2 0.103357 0.754082 -0.070730 21.00000 -1.50000
H6AA 2 0.156504 0.560770 -0.045274 21.00000 -1.50000
PART 0
PART 2
H6BE 2 0.104842 0.662498 -0.033131 -21.00000 -1.50000
H6BD 2 0.206812 0.550658 -0.094923 -21.00000 -1.50000
H6BF 2 0.153653 0.743976 -0.120384 -21.00000 -1.50000
AFIX 0
PART 0
B1 3 0.252796 0.767005 0.132195 11.00000 0.04209 0.07539 =
0.04301 0.00100 0.01028 -0.00516
HKLF 4
REM 110105_TC1_1_0m in P21/c #14
REM R1 = 0.0417 for 1007 Fo > 4sig(Fo) and 0.0677 for all 1479 data
REM 112 parameters refined using 0 restraints
END
WGHT 0.0481 0.1399
REM Highest difference peak 0.164, deepest hole -0.156, 1-sigma level 0.032
Q1 1 0.3377 0.7573 0.1022 11.00000 0.05 0.16
Q2 1 0.0999 0.7005 0.0804 11.00000 0.05 0.14
Q3 1 0.0981 0.6188 -0.0360 11.00000 0.05 0.12
Q4 1 0.3936 0.9003 0.2067 11.00000 0.05 0.12
Q5 1 0.2795 0.6460 0.1616 11.00000 0.05 0.11
Q6 1 0.6121 1.0302 0.1802 11.00000 0.05 0.10
Q7 1 0.8312 0.9161 0.1405 11.00000 0.05 0.10
Q8 1 0.8555 0.6433 0.2156 11.00000 0.05 0.09
Q9 1 0.6207 0.6629 -0.0054 11.00000 0.05 0.09
Q10 1 0.7216 1.0179 0.1635 11.00000 0.05 0.09
Q11 1 0.8156 0.8632 0.0424 11.00000 0.05 0.09
Q12 1 0.0058 0.9353 0.1398 11.00000 0.05 0.09
Q13 1 0.0549 0.4774 0.1796 11.00000 0.05 0.09
Q14 1 0.0743 0.5993 0.1825 11.00000 0.05 0.08
Q15 1 0.5968 0.8206 -0.0197 11.00000 0.05 0.08
Q16 1 0.4803 0.8350 0.0789 11.00000 0.05 0.08
Q17 1 0.2535 0.9568 0.1631 11.00000 0.05 0.08
Q18 1 0.5758 0.6086 -0.1002 11.00000 0.05 0.08
Q19 1 0.1333 0.8583 0.0402 11.00000 0.05 0.08
Q20 1 0.4562 0.6598 -0.1272 11.00000 0.05 0.08
;
_audit_update_record
;
2011-01-09 # Formatted by publCIF
;
_audit_creation_method SHELXL-97
_chemical_name_systematic
;\
(1-Ethyl-3-methyl-2,3-dihydro-1H-imidazol-2-yl-idene-\kC^2^)\
trifluoroboron
;
_chemical_name_common ?
_chemical_melting_point ?
_chemical_formula_moiety 'C6 H10 B F3 N2'
_chemical_formula_sum
'C6 H10 B F3 N2'
_chemical_formula_weight 177.97
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'B' 'B' 0.0013 0.0007
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting monoclinic
_symmetry_space_group_name_H-M 'P 21/c'
_symmetry_space_group_name_Hall '-P 2ybc'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'
_cell_length_a 7.2918(15)
_cell_length_b 7.7091(15)
_cell_length_c 15.126(3)
_cell_angle_alpha 90.00
_cell_angle_beta 101.935(3)
_cell_angle_gamma 90.00
_cell_volume 831.9(3)
_cell_formula_units_Z 4
_cell_measurement_temperature 296(2)
_cell_measurement_reflns_used 1105
_cell_measurement_theta_min 2.86
_cell_measurement_theta_max 24.36
_exptl_crystal_description block
_exptl_crystal_colour colourless
_exptl_crystal_size_max 0.30
_exptl_crystal_size_mid 0.26
_exptl_crystal_size_min 0.16
_exptl_crystal_density_meas ?
_exptl_crystal_density_diffrn 1.421
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 368
_exptl_absorpt_coefficient_mu 0.132
_exptl_absorpt_correction_type multi-scan
_exptl_absorpt_correction_T_min 0.9613
_exptl_absorpt_correction_T_max 0.9791
_exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)'
_exptl_special_details
;
Single crystal of 2 suitable for the X-ray diffraction analysis was prepared by
recrystallization from boiling water (100 \%C, in air). Non-H atoms were
refined anisotropically. H atoms were treated as riding atoms with distances
C---H = 0.96 (CH~3~), 0.97 (CH~2~), 0.93? \%A (C~ArH~), and U~iso~(H)
= 1.5 U~eq~(C), 1.2 U~eq~(C), and 1.2 U~eq~(C),
respectively. The H-atoms at the C6 methyl group carbon atom were treated as
disordered between two positions with sof-s 0.77 and 0.23. Presence of
any solvent molecules was excluded by a special check [SQUEEZE routine of the
PLATON program package (Spek, 2003)].
;
_diffrn_ambient_temperature 296(2)
_diffrn_radiation_wavelength 0.71073
_diffrn_radiation_type MoK\a
_diffrn_radiation_source 'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type 'BRUKER SMART APEXII'
_diffrn_measurement_method 'phi and omega scans'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number 0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time .
_diffrn_standards_decay_% ?
_diffrn_reflns_number 4022
_diffrn_reflns_av_R_equivalents 0.0231
_diffrn_reflns_av_sigmaI/netI 0.0319
_diffrn_reflns_limit_h_min -7
_diffrn_reflns_limit_h_max 8
_diffrn_reflns_limit_k_min -8
_diffrn_reflns_limit_k_max 9
_diffrn_reflns_limit_l_min -18
_diffrn_reflns_limit_l_max 16
_diffrn_reflns_theta_min 2.86
_diffrn_reflns_theta_max 25.10
_reflns_number_total 1479
_reflns_number_gt 1007
_reflns_threshold_expression >2sigma(I)
_computing_data_collection 'BRUKER AXS APEX-2 V1.0-8 (Bruker, 2007)'
_computing_cell_refinement 'SAINT v7.34A (Bruker, 2007)'
_computing_data_reduction 'SAINT v7.34A (Bruker, 2007)'
_computing_structure_solution 'SHELXS97 (Sheldrick, 2008)'
_computing_structure_refinement 'SHELXL97 (Sheldrick, 2008)'
_computing_molecular_graphics
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_computing_publication_material
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type full
_refine_ls_weighting_scheme calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0479P)^2^+0.1425P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_reflns 1479
_refine_ls_number_parameters 111
_refine_ls_number_restraints 0
_refine_ls_R_factor_all 0.0677
_refine_ls_R_factor_gt 0.0417
_refine_ls_wR_factor_ref 0.1100
_refine_ls_wR_factor_gt 0.1027
_refine_ls_goodness_of_fit_ref 1.054
_refine_ls_restrained_S_all 1.054
_refine_ls_shift/su_max 0.000
_refine_ls_shift/su_mean 0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
F1 F 0.12247(18) 0.8955(2) 0.10209(9) 0.0855(5) Uani 1 1 d . . .
F2 F 0.1662(2) 0.6075(2) 0.12391(11) 0.0992(6) Uani 1 1 d . . .
F3 F 0.33469(19) 0.7959(2) 0.22139(8) 0.0811(5) Uani 1 1 d . . .
N1 N 0.5912(2) 0.8174(2) 0.08814(11) 0.0479(4) Uani 1 1 d . . .
N2 N 0.3766(2) 0.7214(2) -0.01864(10) 0.0497(4) Uani 1 1 d . . .
C1 C 0.4112(2) 0.7690(2) 0.06875(12) 0.0428(5) Uani 1 1 d . . .
C2 C 0.6689(3) 0.7985(3) 0.01338(15) 0.0627(6) Uani 1 1 d . . .
H2 H 0.7921 0.8231 0.0099 0.075 Uiso 1 1 calc R . .
C3 C 0.5359(3) 0.7386(3) -0.05307(15) 0.0633(6) Uani 1 1 d . . .
H3 H 0.5481 0.7132 -0.1117 0.076 Uiso 1 1 calc R . .
C4 C 0.6965(3) 0.8806(3) 0.17602(15) 0.0626(6) Uani 1 1 d . . .
H4A H 0.6127 0.9458 0.2056 0.075 Uiso 1 1 calc R . .
H4B H 0.7946 0.9586 0.1660 0.075 Uiso 1 1 calc R . .
C5 C 0.7827(3) 0.7362(4) 0.23669(16) 0.0755(8) Uani 1 1 d . . .
H5B H 0.8749 0.6782 0.2104 0.113 Uiso 1 1 calc R . .
H5A H 0.6871 0.6551 0.2441 0.113 Uiso 1 1 calc R . .
H5C H 0.8413 0.7826 0.2945 0.113 Uiso 1 1 calc R . .
C6 C 0.1948(3) 0.6648(4) -0.07131(15) 0.0724(7) Uani 1 1 d . . .
H6AB H 0.2066 0.6381 -0.1319 0.109 Uiso 0.77(3) 1 calc PR A 1
H6AC H 0.1045 0.7558 -0.0726 0.109 Uiso 0.77(3) 1 calc PR A 1
H6AA H 0.1542 0.5633 -0.0439 0.109 Uiso 0.77(3) 1 calc PR A 1
H6BE H 0.1037 0.6668 -0.0337 0.109 Uiso 0.23(3) 1 d PR A 2
H6BD H 0.2057 0.5490 -0.0930 0.109 Uiso 0.23(3) 1 d PR A 2
H6BF H 0.1559 0.7415 -0.1217 0.109 Uiso 0.23(3) 1 d PR A 2
B1 B 0.2528(3) 0.7670(4) 0.13219(16) 0.0533(6) Uani 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
F1 0.0531(8) 0.1257(12) 0.0820(10) 0.0187(9) 0.0240(7) 0.0226(8)
F2 0.1104(12) 0.1035(12) 0.0988(11) -0.0126(9) 0.0569(10) -0.0499(10)
F3 0.0684(8) 0.1358(13) 0.0414(7) -0.0068(8) 0.0164(6) 0.0014(8)
N1 0.0379(9) 0.0609(10) 0.0440(9) 0.0015(8) 0.0062(7) -0.0019(8)
N2 0.0463(9) 0.0654(11) 0.0360(9) 0.0020(8) 0.0053(7) -0.0026(8)
C1 0.0402(10) 0.0506(11) 0.0359(10) 0.0027(9) 0.0043(8) -0.0029(9)
C2 0.0420(11) 0.0928(17) 0.0576(14) 0.0108(12) 0.0199(10) 0.0041(11)
C3 0.0593(13) 0.0929(17) 0.0418(12) 0.0053(12) 0.0203(10) 0.0071(12)
C4 0.0509(12) 0.0742(15) 0.0574(13) -0.0088(12) -0.0013(10) -0.0124(12)
C5 0.0573(14) 0.109(2) 0.0532(14) -0.0023(14) -0.0046(11) 0.0091(14)
C6 0.0627(14) 0.1013(19) 0.0458(13) -0.0067(13) -0.0061(10) -0.0164(13)
B1 0.0421(13) 0.0753(17) 0.0430(13) 0.0010(12) 0.0103(10) -0.0051(12)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
F1 B1 1.383(3) . ?
F2 B1 1.377(3) . ?
F3 B1 1.376(3) . ?
N1 C1 1.338(2) . ?
N1 C2 1.373(3) . ?
N1 C4 1.474(3) . ?
N2 C1 1.344(2) . ?
N2 C3 1.374(3) . ?
N2 C6 1.465(3) . ?
C1 B1 1.647(3) . ?
C2 C3 1.327(3) . ?
C2 H2 0.9300 . ?
C3 H3 0.9300 . ?
C4 C5 1.496(3) . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C5 H5B 0.9600 . ?
C5 H5A 0.9600 . ?
C5 H5C 0.9600 . ?
C6 H6AB 0.9600 . ?
C6 H6AC 0.9600 . ?
C6 H6AA 0.9600 . ?
C6 H6BE 0.9600 . ?
C6 H6BD 0.9600 . ?
C6 H6BF 0.9600 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N1 C2 110.06(16) . . ?
C1 N1 C4 126.49(17) . . ?
C2 N1 C4 123.45(17) . . ?
C1 N2 C3 110.20(17) . . ?
C1 N2 C6 125.48(17) . . ?
C3 N2 C6 124.29(18) . . ?
N1 C1 N2 105.52(16) . . ?
N1 C1 B1 130.49(17) . . ?
N2 C1 B1 123.98(16) . . ?
C3 C2 N1 107.40(18) . . ?
C3 C2 H2 126.3 . . ?
N1 C2 H2 126.3 . . ?
C2 C3 N2 106.81(19) . . ?
C2 C3 H3 126.6 . . ?
N2 C3 H3 126.6 . . ?
N1 C4 C5 112.46(19) . . ?
N1 C4 H4A 109.1 . . ?
C5 C4 H4A 109.1 . . ?
N1 C4 H4B 109.1 . . ?
C5 C4 H4B 109.1 . . ?
H4A C4 H4B 107.8 . . ?
C4 C5 H5B 109.5 . . ?
C4 C5 H5A 109.5 . . ?
H5B C5 H5A 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
N2 C6 H6AB 109.5 . . ?
N2 C6 H6AC 109.5 . . ?
H6AB C6 H6AC 109.5 . . ?
N2 C6 H6AA 109.5 . . ?
H6AB C6 H6AA 109.5 . . ?
H6AC C6 H6AA 109.5 . . ?
N2 C6 H6BE 109.4 . . ?
H6AB C6 H6BE 141.1 . . ?
H6AC C6 H6BE 56.3 . . ?
H6AA C6 H6BE 56.3 . . ?
N2 C6 H6BD 109.5 . . ?
H6AB C6 H6BD 56.3 . . ?
H6AC C6 H6BD 141.0 . . ?
H6AA C6 H6BD 56.2 . . ?
H6BE C6 H6BD 109.5 . . ?
N2 C6 H6BF 109.5 . . ?
H6AB C6 H6BF 56.3 . . ?
H6AC C6 H6BF 56.2 . . ?
H6AA C6 H6BF 141.0 . . ?
H6BE C6 H6BF 109.5 . . ?
H6BD C6 H6BF 109.5 . . ?
F3 B1 F2 109.38(19) . . ?
F3 B1 F1 109.6(2) . . ?
F2 B1 F1 109.81(18) . . ?
F3 B1 C1 110.81(17) . . ?
F2 B1 C1 108.61(18) . . ?
F1 B1 C1 108.57(18) . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 N1 C1 N2 -0.6(2) . . . . ?
C4 N1 C1 N2 -179.93(18) . . . . ?
C2 N1 C1 B1 -179.3(2) . . . . ?
C4 N1 C1 B1 1.3(3) . . . . ?
C3 N2 C1 N1 0.7(2) . . . . ?
C6 N2 C1 N1 -177.42(19) . . . . ?
C3 N2 C1 B1 179.5(2) . . . . ?
C6 N2 C1 B1 1.4(3) . . . . ?
C1 N1 C2 C3 0.3(3) . . . . ?
C4 N1 C2 C3 179.7(2) . . . . ?
N1 C2 C3 N2 0.1(3) . . . . ?
C1 N2 C3 C2 -0.5(3) . . . . ?
C6 N2 C3 C2 177.6(2) . . . . ?
C1 N1 C4 C5 87.5(3) . . . . ?
C2 N1 C4 C5 -91.7(3) . . . . ?
N1 C1 B1 F3 -10.9(3) . . . . ?
N2 C1 B1 F3 170.61(18) . . . . ?
N1 C1 B1 F2 -131.0(2) . . . . ?
N2 C1 B1 F2 50.4(3) . . . . ?
N1 C1 B1 F1 109.6(2) . . . . ?
N2 C1 B1 F1 -68.9(3) . . . . ?
_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full 25.10
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max 0.163
_refine_diff_density_min -0.156
_refine_diff_density_rms 0.032
#===END
#==============================================================================
data_New_Global_Publ_Block
_audit_update_record
;
2011-03-24 # Formatted by publCIF
;
_publ_section_related_literature
;
For related structurally characterized NHC-P^V^ adducts see: Arduengo et
al., 2000; Arduengo et al., 1997; Kuhn et al., 2003
(analysis of the Cambridge Structural Database; CSD; Version 5.27, release May
2009; Allen, 2002; 3 entries, 5 fragments).
;
#Added by publCIF
# Added by publCIF - use a unique identifier for each data block
#==============================================================================
# SUBMISSION DETAILS
_publ_contact_author_name
'Maxim V. Borzov' # Name of author for correspondence
_publ_contact_author_address # Address of author for correspondence
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
_publ_contact_author_email 'maxborzov@mail.ru'
_publ_contact_author_fax '+86(29)88303947'
_publ_contact_author_phone '+86(29)88303947'
_publ_contact_letter
;
Please consider this CIF for publication. I certify that this contibution is the
original work of those listed as authors; that it has not been published
before (in any language or medium) and is not being considered for publication
elsewhere; that all authors concur with and are aware of the submission; that
all workers involved in the study are listed as authors or given proper credit
in the acknowledgements; that I have obtained permission for and acknowledged
the source of any excerpts from other copyright works; and that to the best of
my knowledge the paper contains no statements which are libellous, unlawful or
in any way actionable. All coauthors have made significant scientific
contributions to the work reported, including the ideas and their execution,
and share responsibility and accountability for the results.
;
_publ_requested_journal 'Organometallics'
_publ_requested_category FM
#==============================================================================
# TITLE AND AUTHOR LIST
_publ_section_title
;
High-Yield Thermolytic Conversion of Imidazolium Salts into Arduengo Carbene
Adducts with BF~3~ and PF~5~
;
_publ_section_title_footnote # remove if not required
.
# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary.
# NB if using publCIF, the Author database tool might prove useful
# (see the Tools menu in publCIF)
loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
_publ_author_email
'Tian, Chong'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
?
;
tianchong30@163.com
;
'Nie, Wanli'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
niewl126@126.com
;
'Borzov, Maxim V.'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
maxborzov@mail.ru
;
'Su, Pengfei'
;
Xi'an Modern Chemistry Research Institute, East Zhangba road 168, Xi'an 71065,
Shaanxi prov., P. R. China
;
.
;
spf1978_2000@163.com
;
#==============================================================================
# TEXT
_publ_section_synopsis
.
_publ_section_abstract
;
Thermolysis of 1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate
(1) and 1,3-dimethyl-1H-imidazolium hexa苯luo訃o計hosphate
(3) under reduced pressure affords Arduengo carbene adducts with BF~3~
and PF~5~ (2 and 4) and HF in a high-yield, what presents the
first example of a direct [C--H] + E--F \\rightarrow [C--E] + H--F bond
rearrangement (E = B or P). Intuitively expected alkylfluorides and imidazole
N-adducts with BF~3~ and/or PF~5~ are not detected at all. DFT computational
study suggests a single step mechanism for the 1 \\rightarrow 2
+ HF conversion. Lower-yield thermolysis of 1,2,3-trimethyl- analogue of
4 into
(1,3-dimethyl-1H-imidazolium-2-yl)methylpenta苯luo訃o計hos計hate
(12) points to a rather general character of this reaction.
;
_publ_section_comment
;\
The sample crystal of 4 presented a non-merohedral twin with the
contaminant contribution of 22.4 (4)% what was taken into consideration during
refinement (see Refinement details). An unsymmetric unit of 4 nearly
adopts the C~2~~v~ point group symmetry. The P-atom in 4
is an octahedral coordination environment with all cis-angles being
90\% within 0.43\%. All P---F bond lengths are nearly identical [range from
1.5916 (18) through 1.5988 (18) \%A] and match the range reported for
[1,3-bis(2,4,6-trimethylphenyl)-1H-imidazol-2-ylidene]\
pentafluorophosphorous (Arduengo et al., 2000). P---C bond length in
4 [1.874 (2) \%A] is also close to observed for the
1,3-bis(2,4,6-trimethylphenyl)-1H-imidazol-2-ylidene adducts with PF~5~
(1.898 \%A; Arduengo et al., 2000), PF~4~Ph (1.909 and 1.910 \%A;
Arduengo et al., 1997), and for
4,5-dimethyl-1,3-bis(1-methylethyl)-1H-imidazol-2-ylidene adduct with
PO~2~Cl (1.844 \%A; Kuhn et al., 2003). The imidazole ring in 4
is planar within 0.003 \%A. The P-atom and methyl group atoms deviate from
this r. m. s. plane by 0.003 (4), 0.012 (5), and 0.013 (5) \%A, respectively.
C/P/F~(trans)~ angle is nearly linear [179.4 (1) \%]. C---F bond to this plane
angles are 45.52 (11), 44.05 (11), 46.32 (11), and 44.0 (1)\% (all close to
45\%). This feature was also observed earlier for the analogues with
octahedral P-centres (Arduengo et al., 1997; Arduengo et al.,
2000).
;
_publ_section_acknowledgements # remove if not required
;
Financial support from the National Natural Science Foundation of China
(projects Nos. 20702041 & 21072157) and Shaanxi province Administration of
Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully
acknowledged.
;
_publ_section_references
;
Allen, F. H. (2002). Acta Cryst. B58, 380--388.
Arduengo, A. J. III, Davidson, F., Krafczyk, R., Marshall, W. J. & Schmutzler,
R. (2000). Monatsh. Chem. 131, 251--265.
Arduengo, A. J. III, Krafczyk, R., Marshall, W. J. & Schmutzler, R. (1997).
J. Am. Chem. Soc. 119, 3381--3382.
Armarego, W. L. F. & Perrin, D. D. (1997). Purification of Laboratory
Chemicals, Fourth Edition. Oxford, UK: Pergamon.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339--341.
Kuhn, N., Stroebele, M. & Walker, M. (2003). Z. Anorg. Allg. Chem.
629, 180--181.
Sheldrick, G. M. (1996). TWINABS. University of G\"ottingen, Germany.
Sheldrick, G. M. (2008). SHELXS97 and SHELXL97. Acta
Cryst. A64, 112-122.
;
_publ_section_figure_captions
;
Fig. 1. Unsymmetrical unit of 4 with labeling. Thermal ellipsoids are
shown at the 50% level of probability.
;
_publ_section_exptl_prep
;
Single crystal of 4 suitable for the X-ray diffraction analysis was
prepared by recrystallization from hot ethanol.
;
_publ_section_exptl_refinement
;
The sample crystal of 4 contained a minor non-merohedral twin
contaminant [dominant to minor component transform twin law (matrix row by
row): 0.99982 --0.00013 0.00019 --0.00062 --0.99972 --0.00111 --0.08020
0.00030 --0.99954]. On the data reduction, the generated *_m.mul file was
processed with TWINABS program (version 2008/2). The contribution of
the minor component was estimated to be 23.15%. The structure was then solved
with the detwinned HKLF 4 data file and finally refined with the HKLF 5 format
data file with reflections from only the main component included and merged
accordingly to the point group 2/m [the BASF parameter converges to 0.224
(4)]. Non-H atoms were refined anisotropically. H atoms were treated as riding
atoms with distances C---H = 0.96 (CH~3~), 0.93 \%A (C~Ar~H) and
U~iso~(H) = 1.5 U~eq~(C), 1.2 U~eq~(C), respectively.
;
#==============================================================================
data_I
_iucr_refine_instructions_details
;
TITL Z in P2(1)/n
CELL 0.71073 7.1365 15.0684 7.7793 90 92.141 90
ZERR 4 0.0008 0.0016 0.0009 0 0.002 0
LATT 1
SYMM 0.5-X,0.5+Y,0.5-Z
SFAC C H N F P
UNIT 20 32 8 20 4
L.S. 10
PLAN 20
SIZE 0.3 0.21 0.12
TEMP 23
BOND $H
CONF
MORE -1
fmap 2
acta
OMIT 0 52
REM C:/frames/guest/110310_PF5/work/B.hkl
WGHT 0.076800 0.114800
BASF 0.22365
FVAR 0.74512
P1 5 0.247757 0.357325 0.815484 11.00000 0.06440 0.03263 =
0.03596 0.00284 0.00045 -0.00237
F1 4 0.423970 0.307013 0.740892 11.00000 0.07303 0.05530 =
0.07450 0.01205 0.00164 0.02470
F2 4 0.108714 0.294898 0.705889 11.00000 0.08367 0.04649 =
0.06414 0.00588 -0.00637 -0.02556
F3 4 0.071377 0.408241 0.889246 11.00000 0.09672 0.06758 =
0.06290 0.00966 0.04205 0.01079
F4 4 0.384929 0.420706 0.926639 11.00000 0.11448 0.05693 =
0.05197 0.00107 -0.03185 -0.01950
F5 4 0.243975 0.288394 0.971072 11.00000 0.13336 0.05461 =
0.05018 0.02052 -0.00155 -0.00799
N1 3 0.267795 0.415896 0.464540 11.00000 0.04470 0.05249 =
0.03596 0.00052 0.00309 -0.00045
N2 3 0.237125 0.525663 0.637129 11.00000 0.04714 0.03239 =
0.05044 0.00634 0.00441 0.00006
C1 1 0.251420 0.437307 0.631212 11.00000 0.03323 0.03254 =
0.03759 0.00102 0.00257 -0.00028
C2 1 0.264906 0.492582 0.367820 11.00000 0.05534 0.07805 =
0.04235 0.02191 0.00161 -0.00288
AFIX 43
H2 2 0.275031 0.496345 0.249203 11.00000 -1.20000
AFIX 0
C3 1 0.244954 0.560217 0.475577 11.00000 0.05578 0.05042 =
0.06625 0.02685 0.00060 -0.00046
AFIX 43
H3 2 0.237695 0.619971 0.446154 11.00000 -1.20000
AFIX 0
C4 1 0.286479 0.327047 0.386824 11.00000 0.09492 0.06865 =
0.04608 -0.01987 0.00488 0.00843
AFIX 137
H4A 2 0.384196 0.294742 0.447517 11.00000 -1.50000
H4B 2 0.317190 0.333169 0.268313 11.00000 -1.50000
H4C 2 0.170195 0.295486 0.394131 11.00000 -1.50000
AFIX 0
C5 1 0.217433 0.582521 0.789727 11.00000 0.09309 0.03208 =
0.07477 -0.01085 0.00968 0.00395
AFIX 137
H5A 2 0.119830 0.559514 0.858748 11.00000 -1.50000
H5B 2 0.186082 0.641787 0.753665 11.00000 -1.50000
H5C 2 0.333569 0.583269 0.856090 11.00000 -1.50000
HKLF 5
REM Z in P2(1)/n
REM R1 = 0.0394 for 1356 Fo > 4sig(Fo) and 0.0508 for all 1651 data
REM 121 parameters refined using 0 restraints
END
WGHT 0.0768 0.1148
REM Highest difference peak 0.314, deepest hole -0.358, 1-sigma level 0.084
Q1 1 0.4642 0.4993 0.5302 11.00000 0.05 0.31
Q2 1 0.0548 0.3514 0.7728 11.00000 0.05 0.28
Q3 1 0.1564 0.4932 0.6436 11.00000 0.05 0.28
Q4 1 0.2285 0.3995 0.7187 11.00000 0.05 0.25
Q5 1 0.4735 0.5595 0.5459 11.00000 0.05 0.25
Q6 1 0.0853 0.5853 0.7746 11.00000 0.05 0.24
Q7 1 0.0747 0.4766 0.6787 11.00000 0.05 0.23
Q8 1 0.2993 0.4451 0.1518 11.00000 0.05 0.23
Q9 1 0.0442 0.5470 0.6857 11.00000 0.05 0.23
Q10 1 0.4951 0.3560 0.4266 11.00000 0.05 0.21
Q11 1 0.2835 0.4977 1.0061 11.00000 0.05 0.21
Q12 1 0.5027 0.3945 0.5190 11.00000 0.05 0.21
Q13 1 0.2048 0.5491 0.7058 11.00000 0.05 0.21
Q14 1 0.0517 0.6374 0.5945 11.00000 0.05 0.21
Q15 1 0.3307 0.5346 0.1241 11.00000 0.05 0.20
Q16 1 0.2821 0.4616 0.2121 11.00000 0.05 0.20
Q17 1 0.0779 0.4616 0.8364 11.00000 0.05 0.20
Q18 1 0.3024 0.6041 0.1138 11.00000 0.05 0.20
Q19 1 -0.0073 0.5072 0.7282 11.00000 0.05 0.19
Q20 1 0.3535 0.2995 1.0196 11.00000 0.05 0.19
;
_audit_creation_method SHELXL-97
_chemical_name_systematic
;\
(1,3-Dimethyl-2,3-dihydro-1H-imidazol-2-ylidene-\kC^2^)\
pentafluorophosphorous
;
_chemical_name_common ?
_chemical_melting_point ?
_chemical_formula_moiety 'C5 H8 F5 N2 P'
_chemical_formula_sum
'C5 H8 F5 N2 P'
_chemical_formula_weight 222.10
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'P' 'P' 0.1023 0.0942
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting monoclinic
_symmetry_space_group_name_H-M 'P 21/n'
_symmetry_space_group_name_Hall '-P 2yn'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
_cell_length_a 7.1365(8)
_cell_length_b 15.0684(16)
_cell_length_c 7.7793(9)
_cell_angle_alpha 90.00
_cell_angle_beta 92.141(2)
_cell_angle_gamma 90.00
_cell_volume 835.97(16)
_cell_formula_units_Z 4
_cell_measurement_temperature 296(2)
_cell_measurement_reflns_used 3824
_cell_measurement_theta_min 2.86
_cell_measurement_theta_max 28.30
_exptl_crystal_description block
_exptl_crystal_colour colourless
_exptl_crystal_size_max 0.30
_exptl_crystal_size_mid 0.21
_exptl_crystal_size_min 0.12
_exptl_crystal_density_meas ?
_exptl_crystal_density_diffrn 1.765
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 448
_exptl_absorpt_coefficient_mu 0.368
_exptl_absorpt_correction_type multi-scan
_exptl_absorpt_correction_T_min 0.8976
_exptl_absorpt_correction_T_max 0.9572
_exptl_absorpt_process_details 'TWINABS (Sheldrick, 1996)'
_exptl_special_details
;
The sample crystal of 4 contained a minor non-merohedral twin
contaminant [dominant to minor component transform twin law (matrix row by
row): 0.99982 --0.00013 0.00019 --0.00062 --0.99972 --0.00111 --0.08020
0.00030 --0.99954].
;
_diffrn_ambient_temperature 296(2)
_diffrn_radiation_wavelength 0.71073
_diffrn_radiation_type MoK\a
_diffrn_radiation_source 'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type 'BRUKER SMART APEXII'
_diffrn_measurement_method 'phi and omega scans'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number 0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time .
_diffrn_standards_decay_% ?
_diffrn_reflns_number 1651
_diffrn_reflns_av_R_equivalents 0.0000
_diffrn_reflns_av_sigmaI/netI 0.0233
_diffrn_reflns_limit_h_min -8
_diffrn_reflns_limit_h_max 8
_diffrn_reflns_limit_k_min 0
_diffrn_reflns_limit_k_max 18
_diffrn_reflns_limit_l_min 0
_diffrn_reflns_limit_l_max 9
_diffrn_reflns_theta_min 2.70
_diffrn_reflns_theta_max 26.00
_reflns_number_total 1651
_reflns_number_gt 1356
_reflns_threshold_expression >2sigma(I)
_computing_data_collection 'BRUKER AXS APEX-2 v2009.5-1 (Bruker, 2007)'
_computing_cell_refinement 'SAINT v7.34A (Bruker, 2007)'
_computing_data_reduction 'SAINT v7.34A (Bruker, 2007)'
_computing_structure_solution 'SHELXS97 (Sheldrick, 2008)'
_computing_structure_refinement 'SHELXL97 (Sheldrick, 2008)'
_computing_molecular_graphics
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_computing_publication_material
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type full
_refine_ls_weighting_scheme calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0768P)^2^+0.1148P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_reflns 1651
_refine_ls_number_parameters 121
_refine_ls_number_restraints 0
_refine_ls_R_factor_all 0.0508
_refine_ls_R_factor_gt 0.0394
_refine_ls_wR_factor_ref 0.1310
_refine_ls_wR_factor_gt 0.1239
_refine_ls_goodness_of_fit_ref 1.142
_refine_ls_restrained_S_all 1.142
_refine_ls_shift/su_max 0.000
_refine_ls_shift/su_mean 0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
P1 P 0.24776(10) 0.35733(4) 0.81548(8) 0.0444(3) Uani 1 1 d . . .
F1 F 0.4240(2) 0.30701(12) 0.7409(3) 0.0676(6) Uani 1 1 d . . .
F2 F 0.1087(3) 0.29490(11) 0.7059(3) 0.0650(5) Uani 1 1 d . . .
F3 F 0.0714(3) 0.40824(13) 0.8892(2) 0.0748(6) Uani 1 1 d . . .
F4 F 0.3849(3) 0.42071(13) 0.9266(2) 0.0753(6) Uani 1 1 d . . .
F5 F 0.2440(3) 0.28839(12) 0.9711(2) 0.0795(6) Uani 1 1 d . . .
N1 N 0.2678(3) 0.41590(15) 0.4645(3) 0.0443(5) Uani 1 1 d . . .
N2 N 0.2371(3) 0.52566(13) 0.6371(3) 0.0433(5) Uani 1 1 d . . .
C1 C 0.2514(3) 0.43731(15) 0.6312(3) 0.0344(5) Uani 1 1 d . . .
C2 C 0.2649(4) 0.4926(2) 0.3678(4) 0.0586(8) Uani 1 1 d . . .
H2 H 0.2750 0.4963 0.2492 0.070 Uiso 1 1 calc R . .
C3 C 0.2450(4) 0.5602(2) 0.4756(4) 0.0575(7) Uani 1 1 d . . .
H3 H 0.2377 0.6200 0.4462 0.069 Uiso 1 1 calc R . .
C4 C 0.2865(5) 0.3270(2) 0.3868(4) 0.0698(9) Uani 1 1 d . . .
H4A H 0.3842 0.2947 0.4475 0.105 Uiso 1 1 calc R . .
H4B H 0.3172 0.3332 0.2683 0.105 Uiso 1 1 calc R . .
H4C H 0.1702 0.2955 0.3941 0.105 Uiso 1 1 calc R . .
C5 C 0.2174(5) 0.58252(19) 0.7897(4) 0.0665(8) Uani 1 1 d . . .
H5A H 0.1198 0.5595 0.8587 0.100 Uiso 1 1 calc R . .
H5B H 0.1861 0.6418 0.7537 0.100 Uiso 1 1 calc R . .
H5C H 0.3336 0.5833 0.8561 0.100 Uiso 1 1 calc R . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
P1 0.0644(5) 0.0326(4) 0.0360(4) 0.0028(2) 0.0005(3) -0.0024(3)
F1 0.0730(11) 0.0553(11) 0.0745(13) 0.0121(9) 0.0016(9) 0.0247(8)
F2 0.0837(12) 0.0465(10) 0.0641(12) 0.0059(9) -0.0064(9) -0.0256(8)
F3 0.0967(14) 0.0676(13) 0.0629(11) 0.0097(10) 0.0420(10) 0.0108(10)
F4 0.1145(16) 0.0569(12) 0.0520(11) 0.0011(9) -0.0319(10) -0.0195(10)
F5 0.1334(18) 0.0546(11) 0.0502(10) 0.0205(8) -0.0016(11) -0.0080(11)
N1 0.0447(11) 0.0525(13) 0.0360(11) 0.0005(9) 0.0031(8) -0.0005(10)
N2 0.0471(11) 0.0324(10) 0.0504(12) 0.0063(9) 0.0044(9) 0.0001(9)
C1 0.0332(10) 0.0325(11) 0.0376(11) 0.0010(9) 0.0026(8) -0.0003(9)
C2 0.0553(16) 0.078(2) 0.0424(14) 0.0219(15) 0.0016(12) -0.0029(15)
C3 0.0558(15) 0.0504(16) 0.0662(18) 0.0269(15) 0.0006(13) -0.0005(13)
C4 0.095(2) 0.069(2) 0.0461(16) -0.0199(15) 0.0049(16) 0.0084(19)
C5 0.093(2) 0.0321(14) 0.075(2) -0.0108(13) 0.0097(17) 0.0039(15)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
P1 F2 1.5916(18) . ?
P1 F5 1.5959(17) . ?
P1 F1 1.5961(18) . ?
P1 F4 1.5984(18) . ?
P1 F3 1.5988(18) . ?
P1 C1 1.874(2) . ?
N1 C1 1.345(3) . ?
N1 C2 1.379(4) . ?
N1 C4 1.477(4) . ?
N2 C1 1.336(3) . ?
N2 C3 1.363(3) . ?
N2 C5 1.475(4) . ?
C2 C3 1.331(5) . ?
C2 H2 0.9300 . ?
C3 H3 0.9300 . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
F2 P1 F5 89.64(11) . . ?
F2 P1 F1 90.48(11) . . ?
F5 P1 F1 90.14(11) . . ?
F2 P1 F4 179.20(12) . . ?
F5 P1 F4 90.34(10) . . ?
F1 P1 F4 90.32(11) . . ?
F2 P1 F3 89.57(11) . . ?
F5 P1 F3 90.24(11) . . ?
F1 P1 F3 179.61(10) . . ?
F4 P1 F3 89.63(12) . . ?
F2 P1 C1 89.80(10) . . ?
F5 P1 C1 179.40(11) . . ?
F1 P1 C1 89.64(10) . . ?
F4 P1 C1 90.22(10) . . ?
F3 P1 C1 89.98(9) . . ?
C1 N1 C2 109.0(2) . . ?
C1 N1 C4 128.6(2) . . ?
C2 N1 C4 122.4(2) . . ?
C1 N2 C3 110.1(2) . . ?
C1 N2 C5 128.0(2) . . ?
C3 N2 C5 121.9(2) . . ?
N2 C1 N1 106.4(2) . . ?
N2 C1 P1 127.68(18) . . ?
N1 C1 P1 125.96(18) . . ?
C3 C2 N1 107.3(2) . . ?
C3 C2 H2 126.3 . . ?
N1 C2 H2 126.3 . . ?
C2 C3 N2 107.3(2) . . ?
C2 C3 H3 126.4 . . ?
N2 C3 H3 126.4 . . ?
N1 C4 H4A 109.5 . . ?
N1 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
N1 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
N2 C5 H5A 109.5 . . ?
N2 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N2 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N2 C1 N1 -0.2(3) . . . . ?
C5 N2 C1 N1 -179.6(2) . . . . ?
C3 N2 C1 P1 -179.71(17) . . . . ?
C5 N2 C1 P1 0.9(4) . . . . ?
C2 N1 C1 N2 0.5(3) . . . . ?
C4 N1 C1 N2 -179.5(3) . . . . ?
C2 N1 C1 P1 -179.99(18) . . . . ?
C4 N1 C1 P1 0.0(4) . . . . ?
F2 P1 C1 N2 135.3(2) . . . . ?
F1 P1 C1 N2 -134.2(2) . . . . ?
F4 P1 C1 N2 -43.9(2) . . . . ?
F3 P1 C1 N2 45.7(2) . . . . ?
F2 P1 C1 N1 -44.1(2) . . . . ?
F1 P1 C1 N1 46.4(2) . . . . ?
F4 P1 C1 N1 136.7(2) . . . . ?
F3 P1 C1 N1 -133.7(2) . . . . ?
C1 N1 C2 C3 -0.6(3) . . . . ?
C4 N1 C2 C3 179.4(3) . . . . ?
N1 C2 C3 N2 0.5(3) . . . . ?
C1 N2 C3 C2 -0.2(3) . . . . ?
C5 N2 C3 C2 179.3(3) . . . . ?
_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full 26.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max 0.314
_refine_diff_density_min -0.358
_refine_diff_density_rms 0.084
#===END
#==============================================================================
data_New_Global_Publ_Block
_audit_update_record
;
2011-03-24 # Formatted by publCIF
;
_publ_section_related_literature
;
For the structure of 1,2,3-trimethyl-1H-imidazolium triflate, see:
Stenzel et al., 2002. For the description of the Cambridge Structural
Database, see Allen, 2002; 3 entries, 5 fragments).
;
#Added by publCIF
# Added by publCIF - use a unique identifier for each data block
#==============================================================================
# SUBMISSION DETAILS
_publ_contact_author_name
'Maxim V. Borzov' # Name of author for correspondence
_publ_contact_author_address # Address of author for correspondence
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
_publ_contact_author_email 'maxborzov@mail.ru'
_publ_contact_author_fax '+86(29)88303947'
_publ_contact_author_phone '+86(29)88303947'
_publ_contact_letter
;
Please consider this CIF for publication. I certify that this contibution is the
original work of those listed as authors; that it has not been published
before (in any language or medium) and is not being considered for publication
elsewhere; that all authors concur with and are aware of the submission; that
all workers involved in the study are listed as authors or given proper credit
in the acknowledgements; that I have obtained permission for and acknowledged
the source of any excerpts from other copyright works; and that to the best of
my knowledge the paper contains no statements which are libellous, unlawful or
in any way actionable. All coauthors have made significant scientific
contributions to the work reported, including the ideas and their execution,
and share responsibility and accountability for the results.
;
_publ_requested_journal 'Organometallics'
_publ_requested_category FM
#==============================================================================
# TITLE AND AUTHOR LIST
_publ_section_title
;
High-Yield Thermolytic Conversion of Imidazolium Salts into Arduengo Carbene
Adducts with BF~3~ and PF~5~
;
_publ_section_title_footnote # remove if not required
.
# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary.
# NB if using publCIF, the Author database tool might prove useful
# (see the Tools menu in publCIF)
loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
_publ_author_email
'Tian, Chong'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
?
;
tianchong30@163.com
;
'Nie, Wanli'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
niewl126@126.com
;
'Borzov, Maxim V.'
;
Key Laboratory of Synthetic and Natural Chemistry of the Ministry of Education,
College of Chemistry and Material Science, the North-West University of Xi'an,
Taibai Bei avenue 229, Xi'an 710069, Shaanxi prov., P. R. China
;
.
;
maxborzov@mail.ru
;
'Su, Pengfei'
;
Xi'an Modern Chemistry Research Institute, East Zhangba road 168, Xi'an 71065,
Shaanxi prov., P. R. China
;
.
;
spf1978_2000@163.com
;
#==============================================================================
# TEXT
_publ_section_synopsis
.
_publ_section_abstract
;\
Thermolysis of 1-ethyl-3-methyl-1H-imidazolium tetrafluoroborate
(1) and 1,3-dimethyl-1H-imidazolium
hexafluorophosphate (3) under reduced pressure affords
Arduengo carbene adducts with BF~3~ and PF~5~ (2 and 4) and HF
in a high-yield, what presents the first example of a direct [C--H] + E--F
\\rightarrow [C--E] + H--F bond rearrangement (E = B or P). Intuitively
expected alkylfluorides and imidazole N-adducts with BF~3~ and/or PF~5~ are
not detected at all. DFT computational study suggests a single step mechanism
for the 1 \\rightarrow 2 + HF conversion. Lower-yield
thermolysis of 1,2,3-trimethyl- analogue of 4 into
(1,3-dimethyl-1H-imidazolium-2-yl)methylpentafluoro\
phosphate (12) points to a rather general character of this
reaction.
;
_publ_section_comment
;
Zwitterionic
(1,3-dimethyl-1H-imidazolium-2-yl)methylpentafluorophosphate,
C~6~H~10~F~5~N~2~P, 12, presents a combination of a planar imidazolium
and pseudo-octahedral phosphate moieties linked with a methylene group.
Analysis of the Cambridge Structural Database; CSD; Version 5.27, release May
2009; Allen, 2002 reveals no close structurally characterized analogues of
12. Moreover, it is the first structurally characterized compound where
PF~5~-group is linked to a tetrahedral C-atom. C--CH~2~--PF~5~-fragment adopts
a conformation in which PF~5~ is the most remote from the imidazolium ring.
Geometrical parameters for the imidazolium moiety are very close to the ones
reported for 1,2,3-trimethyl-1H-imidazolium cation (Stenzel et
al., 2002).
;
_publ_section_acknowledgements # remove if not required
;
Financial support from the National Natural Science Foundation of China
(projects Nos. 20702041 & 21072157) and Shaanxi province Administration of
Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully
acknowledged.
;
_publ_section_references
;
Allen, F. H. (2002). Acta Cryst. B58, 380--388.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339--341.
Sheldrick, G. M. (1996). TWINABS. University of G\"ottingen, Germany.
Sheldrick, G. M. (2008). SHELXS97 and SHELXL97. Acta
Cryst. A64, 112-122
Stenzel, O., Raubenheimer, H. G. & Esterhuysen, C. (2002). J. Chem. Soc.,
Dalton Trans., 1132-1138.
;
_publ_section_figure_captions
;
Fig. 1. Unsymmetrical unit of I with labeling. Thermal ellipsoids are shown at
the 50% level of probability.
;
_publ_section_exptl_prep
;
Single crystal of 12 suitable for the X-ray diffraction analysis was
prepared by recrystallization from hot methanol.
;
_publ_section_exptl_refinement
;
The sample crystal of I contained a minor non-merohedral twin contaminant
[dominant to minor component transform twin law (matrix row by row): 0.48595
-0.00002 0.51433 -0.00013 -0.99983 0.00002 1.48466 -0.00030 -0.48572]. On the
data reduction, the generated *_m.mul file was processed with TWINABS
program (version 2008/2). The contribution of the minor component was
estimated to be 45.49%. The structure was then solved with the detwinned HKLF
4 data file and finally refined with the HKLF 5 format data file with
reflections from only the main component included [the BASF parameter
converges to 0.472 (3)]. Non-H atoms were refined anisotropically. H atoms
were treated as riding atoms with distances C---H = 0.96 (CH~3~), C---H = 0.97
(CH~2~), 0.93 \%A (C~Ar~H) and U~iso~(H) = 1.5 U~eq~(C), 1.2
U~eq~(C), 1.2 U~eq~(C), respectively.
;
#==============================================================================
data_z
_iucr_refine_instructions_details
;
TITL Z in P2(1)/n
CELL 0.71073 8.3723 7.5087 14.9139 90 94.799 90
ZERR 4 0.0012 0.001 0.0021 0 0.004 0
LATT 1
SYMM 0.5-X,0.5+Y,0.5-Z
SFAC C H N F P
UNIT 24 40 8 20 4
L.S. 10
PLAN 20
SIZE 0.06 0.3 0.38
TEMP 23
BOND $H
MORE -1
CONF
fmap 2
acta
OMIT 0 50.2
OMIT -3 1 11
OMIT -2 1 8
OMIT -1 -1 8
OMIT -2 -1 11
OMIT -6 -4 12
OMIT -1 1 8
OMIT -2 1 11
OMIT 0 -1 8
OMIT 0 1 8
OMIT 1 -1 8
OMIT 1 1 8
REM C:/frames/guest/110822_TC/work/Z.hkl
WGHT 0.091500 0.100800
BASF 0.47180
FVAR 0.75509
C1 1 0.861777 0.308212 0.446735 11.00000 0.03585 0.02889 =
0.03826 0.00049 -0.00198 -0.00543
C2 1 1.030595 0.220909 0.559417 11.00000 0.05179 0.04826 =
0.05381 0.00624 -0.02388 -0.01066
AFIX 43
H2 2 1.072560 0.193000 0.617423 11.00000 -1.20000
AFIX 0
C3 1 1.105555 0.201511 0.484932 11.00000 0.03208 0.04282 =
0.06172 0.00968 -0.01220 0.00133
AFIX 43
H3 2 1.209442 0.160200 0.480948 11.00000 -1.20000
AFIX 0
C4 1 0.758600 0.321076 0.598241 11.00000 0.06543 0.08287 =
0.03437 -0.00510 -0.00022 0.00529
AFIX 137
H4A 2 0.698813 0.425806 0.579795 11.00000 -1.50000
H4B 2 0.808545 0.338036 0.657944 11.00000 -1.50000
H4C 2 0.687571 0.220643 0.597708 11.00000 -1.50000
AFIX 0
C5 1 1.030883 0.247490 0.319244 11.00000 0.05058 0.07446 =
0.06073 0.00140 0.01567 0.00177
AFIX 137
H5A 2 0.975848 0.147572 0.290873 11.00000 -1.50000
H5B 2 1.144151 0.234389 0.315343 11.00000 -1.50000
H5C 2 0.994700 0.355248 0.289432 11.00000 -1.50000
AFIX 0
C6 1 0.718656 0.375813 0.393724 11.00000 0.03774 0.03515 =
0.03982 0.00227 -0.00163 0.00453
AFIX 23
H6A 2 0.753051 0.432243 0.340087 11.00000 -1.20000
H6B 2 0.671024 0.467608 0.428693 11.00000 -1.20000
AFIX 0
N1 3 0.881519 0.288764 0.536340 11.00000 0.04030 0.04346 =
0.04252 -0.00411 -0.00573 -0.00598
N2 3 0.997284 0.255505 0.413842 11.00000 0.02852 0.03779 =
0.04609 0.00242 0.00061 -0.00300
F1 4 0.417165 0.074856 0.325739 11.00000 0.04338 0.05930 =
0.07389 -0.00454 -0.01333 -0.01264
F2 4 0.460956 0.263628 0.441833 11.00000 0.05415 0.12775 =
0.08657 -0.03618 0.03827 -0.03518
F3 4 0.645778 0.054963 0.414276 11.00000 0.06850 0.05060 =
0.14234 0.03766 -0.05477 -0.01553
F4 4 0.649536 0.154954 0.271604 11.00000 0.07583 0.11094 =
0.08595 -0.05477 0.03422 -0.02142
F5 4 0.463766 0.364134 0.300151 11.00000 0.06550 0.06243 =
0.10312 0.02128 -0.04254 0.00336
P1 5 0.559324 0.210574 0.358027 11.00000 0.03073 0.04087 =
0.04145 0.00018 -0.00287 0.00142
HKLF 5
REM Z in P2(1)/n
REM R1 = 0.0574 for 2948 Fo > 4sig(Fo) and 0.0924 for all 4233 data
REM 130 parameters refined using 0 restraints
END
WGHT 0.0915 0.1008
REM Highest difference peak 0.473, deepest hole -0.385, 1-sigma level 0.116
Q1 1 0.7183 0.0606 0.3429 11.00000 0.05 0.47
Q2 1 0.5340 0.1392 0.4387 11.00000 0.05 0.43
Q3 1 0.4313 0.3297 0.3655 11.00000 0.05 0.35
Q4 1 0.6690 0.0220 0.4362 11.00000 0.05 0.34
Q5 1 0.6221 0.0215 0.4233 11.00000 0.05 0.30
Q6 1 0.4639 -0.0207 0.3591 11.00000 0.05 0.30
Q7 1 1.0935 0.4716 0.2557 11.00000 0.05 0.27
Q8 1 1.1151 -0.0103 0.3000 11.00000 0.05 0.27
Q9 1 0.7591 0.4178 0.2787 11.00000 0.05 0.26
Q10 1 0.5364 0.0900 0.2996 11.00000 0.05 0.25
Q11 1 0.3656 0.0556 0.2809 11.00000 0.05 0.25
Q12 1 1.1841 0.0294 0.4558 11.00000 0.05 0.25
Q13 1 0.4056 -0.0587 0.3200 11.00000 0.05 0.25
Q14 1 0.7094 -0.0537 0.2942 11.00000 0.05 0.24
Q15 1 0.6665 0.1261 0.2558 11.00000 0.05 0.24
Q16 1 0.5430 0.4780 0.3101 11.00000 0.05 0.24
Q17 1 0.7470 0.5880 0.4688 11.00000 0.05 0.24
Q18 1 0.6558 0.1268 0.4854 11.00000 0.05 0.23
Q19 1 0.4701 -0.0044 0.2784 11.00000 0.05 0.23
Q20 1 0.7054 0.4466 0.7173 11.00000 0.05 0.23
;
_vrf_PLAT021_z
;
PROBLEM: PLAT021_ALERT_1_B Ratio Unique / Expected Reflections too High ... 2.559
RESPONSE: Sample crystal is a non-merohedral twin. HKLF 5 file is used
(reflections are not merged: MERG 0 enforced by HKLF 5).
;
_vrf_REFLT01_z
;
PROBLEM: REFLT01_ALERT_1_B The number of symmetry-independent reflections cannot
exceed the total number of reflections measured
Number of symmetry-independent reflections = 4233 Total number of reflections =
4232
RESPONSE: We cannot exactly define the origin of the problem and the ways how
to fix it. Most likely, it arises from the simultaneous use of a HKLF 5 file
(twinned crystal, MERG 0 is enforced) on one hand, and OMIT h k l
instructions on the other. This B-alert vanishes only when all OMIT
instructions are absent, however, their application is nesessary to eliminate
some "bad" reflections with abs(Fobs-Fcacl)/sigma > 10. Other attempts to
eliminate this problem failed.
;
_audit_creation_method SHELXL-97
_chemical_name_systematic
;
(1,3-Dimethyl-1H-imidazolium-2-yl)methylpentafluorophosphate
;
_chemical_name_common ?
_chemical_melting_point ?
_chemical_formula_moiety 'C6 H10 F5 N2 P'
_chemical_formula_sum
'C6 H10 F5 N2 P'
_chemical_formula_weight 236.13
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
'C' 'C' 0.0033 0.0016
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'H' 'H' 0.0000 0.0000
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'N' 'N' 0.0061 0.0033
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'F' 'F' 0.0171 0.0103
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
'P' 'P' 0.1023 0.0942
'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_symmetry_cell_setting monoclinic
_symmetry_space_group_name_H-M 'P 21/n'
_symmetry_space_group_name_Hall '-P 2yn'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
_cell_length_a 8.3723(12)
_cell_length_b 7.5087(10)
_cell_length_c 14.914(2)
_cell_angle_alpha 90.00
_cell_angle_beta 94.799(4)
_cell_angle_gamma 90.00
_cell_volume 934.3(2)
_cell_formula_units_Z 4
_cell_measurement_temperature 296(2)
_cell_measurement_reflns_used 3396
_cell_measurement_theta_min 2.44
_cell_measurement_theta_max 28.27
_exptl_crystal_description block
_exptl_crystal_colour colourless
_exptl_crystal_size_max 0.38
_exptl_crystal_size_mid 0.30
_exptl_crystal_size_min 0.06
_exptl_crystal_density_meas ?
_exptl_crystal_density_diffrn 1.679
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 480
_exptl_absorpt_coefficient_mu 0.335
_exptl_absorpt_correction_type multi-scan
_exptl_absorpt_correction_T_min 0.8833
_exptl_absorpt_correction_T_max 0.9802
_exptl_absorpt_process_details 'TWINABS (Sheldrick, 1996)'
_exptl_special_details
;The sample crystal of I contained a minor non-merohedral twin contaminant
[dominant to minor component transform twin law (matrix row by row): 0.48595
-0.00002 0.51433 -0.00013 -0.99983 0.00002 1.48466 -0.00030 -0.48572].
;
_diffrn_ambient_temperature 296(2)
_diffrn_radiation_wavelength 0.71073
_diffrn_radiation_type MoK\a
_diffrn_radiation_source 'fine-focus sealed tube'
_diffrn_radiation_monochromator graphite
_diffrn_measurement_device_type 'BRUKER SMART APEXII'
_diffrn_measurement_method 'phi and omega scans'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number 0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time .
_diffrn_standards_decay_% ?
_diffrn_reflns_number 4232
_diffrn_reflns_av_R_equivalents 0.0000
_diffrn_reflns_av_sigmaI/netI 0.0534
_diffrn_reflns_limit_h_min -9
_diffrn_reflns_limit_h_max 9
_diffrn_reflns_limit_k_min -8
_diffrn_reflns_limit_k_max 8
_diffrn_reflns_limit_l_min -17
_diffrn_reflns_limit_l_max 17
_diffrn_reflns_theta_min 2.70
_diffrn_reflns_theta_max 25.10
_reflns_number_total 4233
_reflns_number_gt 2948
_reflns_threshold_expression >2sigma(I)
_computing_data_collection 'BRUKER AXS APEX-2 v2009.5-1 (Bruker, 2007)'
_computing_cell_refinement 'SAINT v7.34A (Bruker, 2007)'
_computing_data_reduction 'SAINT v7.34A (Bruker, 2007)'
_computing_structure_solution 'SHELXS97 (Sheldrick, 2008)'
_computing_structure_refinement 'SHELXL97 (Sheldrick, 2008)'
_computing_molecular_graphics
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_computing_publication_material
;
SHELXTL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009)
;
_refine_special_details
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type full
_refine_ls_weighting_scheme calc
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0915P)^2^+0.1008P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary direct
_atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens geom
_refine_ls_hydrogen_treatment constr
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_reflns 4233
_refine_ls_number_parameters 130
_refine_ls_number_restraints 0
_refine_ls_R_factor_all 0.0924
_refine_ls_R_factor_gt 0.0574
_refine_ls_wR_factor_ref 0.1659
_refine_ls_wR_factor_gt 0.1501
_refine_ls_goodness_of_fit_ref 1.063
_refine_ls_restrained_S_all 1.063
_refine_ls_shift/su_max 0.000
_refine_ls_shift/su_mean 0.000
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.8618(3) 0.3082(3) 0.4467(2) 0.0346(7) Uani 1 1 d . . .
C2 C 1.0306(5) 0.2209(4) 0.5594(3) 0.0529(11) Uani 1 1 d . . .
H2 H 1.0726 0.1930 0.6174 0.063 Uiso 1 1 calc R . .
C3 C 1.1056(4) 0.2015(4) 0.4849(3) 0.0464(9) Uani 1 1 d . . .
H3 H 1.2094 0.1602 0.4809 0.056 Uiso 1 1 calc R . .
C4 C 0.7586(5) 0.3211(5) 0.5982(2) 0.0611(10) Uani 1 1 d . . .
H4A H 0.6988 0.4258 0.5798 0.092 Uiso 1 1 calc R . .
H4B H 0.8085 0.3380 0.6579 0.092 Uiso 1 1 calc R . .
H4C H 0.6876 0.2206 0.5977 0.092 Uiso 1 1 calc R . .
C5 C 1.0309(6) 0.2475(4) 0.3192(3) 0.0613(11) Uani 1 1 d . . .
H5A H 0.9758 0.1476 0.2909 0.092 Uiso 1 1 calc R . .
H5B H 1.1442 0.2344 0.3153 0.092 Uiso 1 1 calc R . .
H5C H 0.9947 0.3552 0.2894 0.092 Uiso 1 1 calc R . .
C6 C 0.7187(3) 0.3758(3) 0.3937(2) 0.0378(7) Uani 1 1 d . . .
H6A H 0.7531 0.4322 0.3401 0.045 Uiso 1 1 calc R . .
H6B H 0.6710 0.4676 0.4287 0.045 Uiso 1 1 calc R . .
N1 N 0.8815(4) 0.2888(3) 0.5363(2) 0.0426(7) Uani 1 1 d . . .
N2 N 0.9973(3) 0.2555(3) 0.4138(2) 0.0376(7) Uani 1 1 d . . .
F1 F 0.4172(2) 0.0749(2) 0.32574(13) 0.0599(6) Uani 1 1 d . . .
F2 F 0.4610(3) 0.2636(3) 0.44183(19) 0.0877(9) Uani 1 1 d . . .
F3 F 0.6458(3) 0.0550(2) 0.41428(16) 0.0907(9) Uani 1 1 d . . .
F4 F 0.6495(3) 0.1550(3) 0.27160(16) 0.0894(8) Uani 1 1 d . . .
F5 F 0.4638(3) 0.3641(3) 0.30015(16) 0.0798(8) Uani 1 1 d . . .
P1 P 0.55932(9) 0.21057(10) 0.35803(6) 0.0380(3) Uani 1 1 d . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0358(18) 0.0289(14) 0.038(2) 0.0005(14) -0.0020(13) -0.0054(12)
C2 0.052(2) 0.0483(19) 0.054(3) 0.0062(17) -0.024(2) -0.0107(16)
C3 0.032(2) 0.0428(18) 0.062(3) 0.0097(18) -0.0122(18) 0.0013(14)
C4 0.065(3) 0.083(2) 0.034(2) -0.0051(18) -0.0002(18) 0.005(2)
C5 0.051(3) 0.074(3) 0.061(3) 0.0014(17) 0.016(2) 0.0018(16)
C6 0.0377(17) 0.0352(15) 0.0398(18) 0.0023(13) -0.0016(13) 0.0045(13)
N1 0.0403(17) 0.0435(14) 0.0425(18) -0.0041(13) -0.0057(14) -0.0060(12)
N2 0.0285(17) 0.0378(14) 0.046(2) 0.0024(10) 0.0006(14) -0.0030(10)
F1 0.0434(11) 0.0593(11) 0.0739(15) -0.0045(10) -0.0133(10) -0.0126(9)
F2 0.0542(16) 0.1278(19) 0.087(2) -0.0362(13) 0.0383(13) -0.0352(12)
F3 0.0685(16) 0.0506(11) 0.142(2) 0.0377(12) -0.0548(14) -0.0155(10)
F4 0.0758(17) 0.1109(17) 0.0859(19) -0.0548(15) 0.0342(13) -0.0214(15)
F5 0.0655(15) 0.0624(12) 0.1031(19) 0.0213(12) -0.0425(13) 0.0034(11)
P1 0.0307(5) 0.0409(4) 0.0415(6) 0.0002(4) -0.0029(3) 0.0014(3)
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N2 1.333(4) . ?
C1 N1 1.341(4) . ?
C1 C6 1.470(3) . ?
C2 C3 1.329(5) . ?
C2 N1 1.365(5) . ?
C2 H2 0.9300 . ?
C3 N2 1.396(4) . ?
C3 H3 0.9300 . ?
C4 N1 1.459(5) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C5 N2 1.463(5) . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C6 P1 1.866(3) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
F1 P1 1.6097(17) . ?
F2 P1 1.604(3) . ?
F3 P1 1.5784(18) . ?
F4 P1 1.603(2) . ?
F5 P1 1.6122(18) . ?
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 C1 N1 107.3(2) . . ?
N2 C1 C6 125.8(3) . . ?
N1 C1 C6 126.9(3) . . ?
C3 C2 N1 108.4(4) . . ?
C3 C2 H2 125.8 . . ?
N1 C2 H2 125.8 . . ?
C2 C3 N2 106.3(3) . . ?
C2 C3 H3 126.8 . . ?
N2 C3 H3 126.8 . . ?
N1 C4 H4A 109.5 . . ?
N1 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
N1 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
N2 C5 H5A 109.5 . . ?
N2 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N2 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C1 C6 P1 117.06(18) . . ?
C1 C6 H6A 108.0 . . ?
P1 C6 H6A 108.0 . . ?
C1 C6 H6B 108.0 . . ?
P1 C6 H6B 108.0 . . ?
H6A C6 H6B 107.3 . . ?
C1 N1 C2 109.0(3) . . ?
C1 N1 C4 125.3(3) . . ?
C2 N1 C4 125.5(3) . . ?
C1 N2 C3 109.0(3) . . ?
C1 N2 C5 127.3(3) . . ?
C3 N2 C5 123.7(3) . . ?
F3 P1 F4 90.49(15) . . ?
F3 P1 F2 90.70(15) . . ?
F4 P1 F2 177.21(12) . . ?
F3 P1 F1 89.14(9) . . ?
F4 P1 F1 88.90(12) . . ?
F2 P1 F1 88.59(13) . . ?
F3 P1 F5 177.41(11) . . ?
F4 P1 F5 90.11(15) . . ?
F2 P1 F5 88.59(15) . . ?
F1 P1 F5 88.35(10) . . ?
F3 P1 C6 93.18(11) . . ?
F4 P1 C6 91.66(14) . . ?
F2 P1 C6 90.80(13) . . ?
F1 P1 C6 177.60(10) . . ?
F5 P1 C6 89.32(11) . . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C2 C3 N2 -1.4(4) . . . . ?
N2 C1 C6 P1 93.3(3) . . . . ?
N1 C1 C6 P1 -87.1(3) . . . . ?
N2 C1 N1 C2 -0.8(3) . . . . ?
C6 C1 N1 C2 179.6(3) . . . . ?
N2 C1 N1 C4 -176.1(3) . . . . ?
C6 C1 N1 C4 4.2(4) . . . . ?
C3 C2 N1 C1 1.4(4) . . . . ?
C3 C2 N1 C4 176.7(3) . . . . ?
N1 C1 N2 C3 -0.1(3) . . . . ?
C6 C1 N2 C3 179.6(3) . . . . ?
N1 C1 N2 C5 178.0(2) . . . . ?
C6 C1 N2 C5 -2.3(4) . . . . ?
C2 C3 N2 C1 0.9(3) . . . . ?
C2 C3 N2 C5 -177.3(3) . . . . ?
C1 C6 P1 F3 6.3(3) . . . . ?
C1 C6 P1 F4 -84.3(3) . . . . ?
C1 C6 P1 F2 97.0(3) . . . . ?
C1 C6 P1 F5 -174.4(3) . . . . ?
_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full 25.10
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max 0.473
_refine_diff_density_min -0.385
_refine_diff_density_rms 0.116
#===END