 
data_MLII-99-2
 
_audit_creation_method            'SHELXL-2014/7'
_shelx_SHELXL_version_number      '2014/7'
_chemical_name_systematic         ?
_chemical_name_common             ?
_chemical_melting_point           ?
_chemical_formula_moiety          ?
_chemical_formula_sum
 'C18 H15 Br F2 N4 O2' 
_chemical_formula_weight          437.25

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'
 'Br'  'Br'  -0.2901   2.4595
 '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'
 'O'  'O'   0.0106   0.0060
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 
_space_group_crystal_system       monoclinic
_space_group_IT_number            4
_space_group_name_H-M_alt         'P 21'
_space_group_name_Hall            'P 2yb'
 
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
 
loop_
 _space_group_symop_operation_xyz
 'x, y, z'
 '-x, y+1/2, -z'
 
_cell_length_a                    12.6771(15)
_cell_length_b                    5.6603(7)
_cell_length_c                    13.2825(15)
_cell_angle_alpha                 90
_cell_angle_beta                  112.3222(18)
_cell_angle_gamma                 90
_cell_volume                      881.68(18)
_cell_formula_units_Z             2
_cell_measurement_temperature     100(2)
_cell_measurement_reflns_used     3964
_cell_measurement_theta_min       3.12
_cell_measurement_theta_max       27.0
 
_exptl_crystal_description        block
_exptl_crystal_colour             colorless
_exptl_crystal_density_meas       ?
_exptl_crystal_density_method     ?
_exptl_crystal_density_diffrn     1.647          
_exptl_crystal_F_000              440
_exptl_transmission_factor_min    ?
_exptl_transmission_factor_max    ?
_exptl_crystal_size_max           0.100
_exptl_crystal_size_mid           0.040
_exptl_crystal_size_min           0.020
_exptl_absorpt_coefficient_mu     2.373
_shelx_estimated_absorpt_T_min    0.797
_shelx_estimated_absorpt_T_max    0.954
_exptl_absorpt_correction_T_min   0.5647                 
_exptl_absorpt_correction_T_max   0.7455     
_exptl_absorpt_process_details    sadabs
_exptl_absorpt_special_details    ?
_diffrn_ambient_temperature       100(2)  
_diffrn_radiation_wavelength      0.71073
_diffrn_radiation_type            MoK\a
_diffrn_radiation_source          'I\mS microfocus tube' 
_diffrn_radiation_monochromator   graphite 
_diffrn_measurement_device_type   
;
Bruker D8 goniometer with CCD area detector  
; 
_diffrn_measurement_method        'omega and phi scans'
_diffrn_detector_area_resol_mean  ?
_diffrn_reflns_number             5582
_diffrn_reflns_av_unetI/netI      0.0652
_diffrn_reflns_av_R_equivalents   0.0299
_diffrn_reflns_limit_h_min        -13
_diffrn_reflns_limit_h_max        16
_diffrn_reflns_limit_k_min        -7
_diffrn_reflns_limit_k_max        7
_diffrn_reflns_limit_l_min        -16
_diffrn_reflns_limit_l_max        16
_diffrn_reflns_theta_min          1.657
_diffrn_reflns_theta_max          27.108
_diffrn_reflns_theta_full         25.242
_diffrn_measured_fraction_theta_max   0.992
_diffrn_measured_fraction_theta_full  0.995
_diffrn_reflns_Laue_measured_fraction_max    0.992
_diffrn_reflns_Laue_measured_fraction_full   0.995
_diffrn_reflns_point_group_measured_fraction_max   0.935
_diffrn_reflns_point_group_measured_fraction_full  0.956
_reflns_number_total              3654
_reflns_number_gt                 2999
_reflns_threshold_expression      'I > 2σ(I)'
_reflns_Friedel_coverage          0.708
_reflns_Friedel_fraction_max      0.864
_reflns_Friedel_fraction_full     0.907
 
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
 
_computing_cell_refinement        'SAINT 8.37A (Bruker-AXS, 2015)' 
_computing_data_reduction         'SAINT 8.37A (Bruker-AXS, 2015)' 
_computing_structure_solution     'SHELXT-2014 (Sheldrick, 2015)'
_computing_structure_refinement   'SHELXL-2014 (Sheldrick, 2015)'
_computing_molecular_graphics     'Bruker SHELXTL (Sheldrick, 2015)' 
_computing_publication_material   'Bruker SHELXTL (Sheldrick, 2015)' 
 
_refine_special_details
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. All non-H atoms were located 
 in difference-Fourier maps, and then refined anisotropically. 
;
_refine_ls_structure_factor_coef  Fsqd
_refine_ls_matrix_type            full
_refine_ls_weighting_scheme       calc
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.0656P)²+0.0622P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary      ?
_atom_sites_solution_secondary    ?
_atom_sites_solution_hydrogens    geom
_refine_ls_hydrogen_treatment     constr
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        .
_refine_ls_abs_structure_details
;
 Flack x determined using 1028 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack    -0.004(13)
_chemical_absolute_configuration  ad
_refine_ls_number_reflns          3654
_refine_ls_number_parameters      245
_refine_ls_number_restraints      1
_refine_ls_R_factor_all           0.0683
_refine_ls_R_factor_gt            0.0505
_refine_ls_wR_factor_ref          0.1193
_refine_ls_wR_factor_gt           0.1106
_refine_ls_goodness_of_fit_ref    1.026
_refine_ls_restrained_S_all       1.026
_refine_ls_shift/su_max           0.001
_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_site_symmetry_order  
 _atom_site_calc_flag
 _atom_site_refinement_flags_posn
 _atom_site_refinement_flags_adp
 _atom_site_refinement_flags_occupancy
 _atom_site_disorder_assembly
 _atom_site_disorder_group
Br1 Br 0.02969(6) 0.67683(14) 0.81272(5) 0.0293(2) Uani 1 1 d . . . . .
F1 F 0.5043(3) 0.1961(11) 0.3682(3) 0.0326(10) Uani 1 1 d . . . . .
F2 F 0.4960(4) 0.5667(8) 0.4084(3) 0.0327(11) Uani 1 1 d . . . . .
O1 O 0.7017(5) 0.5123(10) -0.0264(5) 0.0324(13) Uani 1 1 d . . . . .
O2 O 0.7271(5) 0.8668(10) 0.0409(5) 0.0381(15) Uani 1 1 d . . . . .
N1 N 0.2181(4) 0.1459(12) 0.4368(4) 0.0188(13) Uani 1 1 d . . . . .
N2 N 0.2633(5) 0.1363(10) 0.3622(4) 0.0184(14) Uani 1 1 d . . . . .
N3 N 0.2861(5) 0.3619(10) 0.3428(5) 0.0178(12) Uani 1 1 d . . . . .
N4 N 0.6953(4) 0.6660(17) 0.0389(4) 0.0238(12) Uani 1 1 d . . . . .
C1 C 0.5329(6) 0.3180(12) 0.1716(6) 0.0199(15) Uani 1 1 d . . . . .
H1 H 0.4966 0.1690 0.1657 0.024 Uiso 1 1 calc R U . . .
C2 C 0.5878(6) 0.3759(13) 0.1009(5) 0.0201(15) Uani 1 1 d . . . . .
H2 H 0.5886 0.2695 0.0459 0.024 Uiso 1 1 calc R U . . .
C3 C 0.6404(6) 0.5933(12) 0.1144(6) 0.0195(14) Uani 1 1 d . . . . .
C4 C 0.6439(6) 0.7516(13) 0.1948(6) 0.0233(16) Uani 1 1 d . . . . .
H4 H 0.6836 0.8971 0.2027 0.028 Uiso 1 1 calc R U . . .
C5 C 0.5888(5) 0.6952(18) 0.2634(5) 0.0195(13) Uani 1 1 d . . . . .
H5 H 0.5895 0.8019 0.3188 0.023 Uiso 1 1 calc R U . . .
C6 C 0.5318(6) 0.4779(13) 0.2501(6) 0.0195(15) Uani 1 1 d . . . . .
C7 C 0.4673(6) 0.4125(13) 0.3224(6) 0.0235(16) Uani 1 1 d . . . . .
C8 C 0.3387(6) 0.4091(13) 0.2631(6) 0.0210(15) Uani 1 1 d . . . . .
H8 H 0.3190 0.2750 0.2101 0.025 Uiso 1 1 calc R U . . .
C9 C 0.2909(6) 0.6357(13) 0.1994(6) 0.0226(18) Uani 1 1 d . . . . .
H9A H 0.3099 0.7702 0.2509 0.027 Uiso 1 1 calc R U . . .
H9B H 0.3289 0.6634 0.1477 0.027 Uiso 1 1 calc R U . . .
C10 C 0.1640(6) 0.6308(15) 0.1371(6) 0.030(2) Uani 1 1 d . . . . .
H10A H 0.1406 0.7730 0.0920 0.045 Uiso 1 1 calc R U . . .
H10B H 0.1251 0.6259 0.1883 0.045 Uiso 1 1 calc R U . . .
H10C H 0.1435 0.4904 0.0905 0.045 Uiso 1 1 calc R U . . .
C11 C 0.2576(5) 0.5164(11) 0.4054(5) 0.0164(14) Uani 1 1 d . . . . .
H11 H 0.2662 0.6833 0.4081 0.020 Uiso 1 1 calc R U . . .
C12 C 0.2130(5) 0.3761(12) 0.4649(5) 0.0147(13) Uani 1 1 d . . . . .
C13 C 0.1668(6) 0.4482(12) 0.5467(5) 0.0171(14) Uani 1 1 d . . . . .
C14 C 0.1934(5) 0.6682(17) 0.5970(5) 0.0189(12) Uani 1 1 d . . . . .
H14 H 0.2403 0.7742 0.5771 0.023 Uiso 1 1 calc R U . . .
C15 C 0.1524(6) 0.7343(11) 0.6757(5) 0.0193(16) Uani 1 1 d . . . . .
H15 H 0.1715 0.8838 0.7103 0.023 Uiso 1 1 calc R U . . .
C16 C 0.0837(6) 0.5806(12) 0.7031(6) 0.0202(15) Uani 1 1 d . . . . .
C17 C 0.0542(6) 0.3644(12) 0.6539(6) 0.0205(15) Uani 1 1 d . . . . .
H17 H 0.0062 0.2612 0.6736 0.025 Uiso 1 1 calc R U . . .
C18 C 0.0953(5) 0.2977(12) 0.5750(5) 0.0164(14) Uani 1 1 d . . . . .
H18 H 0.0746 0.1487 0.5401 0.020 Uiso 1 1 calc R U . . .
 
 
_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
Br1 C16 1.908(7) . ?
F1 C7 1.369(9) . ?
F2 C7 1.373(8) . ?
O1 N4 1.253(9) . ?
O2 N4 1.203(10) . ?
N1 N2 1.320(7) . ?
N1 C12 1.364(9) . ?
N2 N3 1.355(8) . ?
N3 C11 1.347(8) . ?
N3 C8 1.475(8) . ?
N4 C3 1.480(8) . ?
C1 C6 1.384(10) . ?
C1 C2 1.403(9) . ?
C1 H1 0.9500 . ?
C2 C3 1.379(10) . ?
C2 H2 0.9500 . ?
C3 C4 1.381(9) . ?
C4 C5 1.379(9) . ?
C4 H4 0.9500 . ?
C5 C6 1.403(12) . ?
C5 H5 0.9500 . ?
C6 C7 1.524(10) . ?
C7 C8 1.518(10) . ?
C8 C9 1.529(10) . ?
C8 H8 1.0000 . ?
C9 C10 1.505(10) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 C12 1.384(9) . ?
C11 H11 0.9500 . ?
C12 C13 1.473(9) . ?
C13 C14 1.393(12) . ?
C13 C18 1.396(9) . ?
C14 C15 1.384(9) . ?
C14 H14 0.9500 . ?
C15 C16 1.374(10) . ?
C15 H15 0.9500 . ?
C16 C17 1.371(10) . ?
C17 C18 1.387(9) . ?
C17 H17 0.9500 . ?
C18 H18 0.9500 . ?
 
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 N1 C12 108.9(6) . . ?
N1 N2 N3 106.8(6) . . ?
C11 N3 N2 111.6(5) . . ?
C11 N3 C8 128.7(6) . . ?
N2 N3 C8 119.6(5) . . ?
O2 N4 O1 124.2(6) . . ?
O2 N4 C3 119.2(7) . . ?
O1 N4 C3 116.6(8) . . ?
C6 C1 C2 120.0(6) . . ?
C6 C1 H1 120.0 . . ?
C2 C1 H1 120.0 . . ?
C3 C2 C1 117.4(6) . . ?
C3 C2 H2 121.3 . . ?
C1 C2 H2 121.3 . . ?
C2 C3 C4 123.5(7) . . ?
C2 C3 N4 119.2(7) . . ?
C4 C3 N4 117.3(6) . . ?
C5 C4 C3 119.0(7) . . ?
C5 C4 H4 120.5 . . ?
C3 C4 H4 120.5 . . ?
C4 C5 C6 119.1(7) . . ?
C4 C5 H5 120.5 . . ?
C6 C5 H5 120.5 . . ?
C1 C6 C5 121.0(6) . . ?
C1 C6 C7 118.5(6) . . ?
C5 C6 C7 120.5(6) . . ?
F1 C7 F2 105.1(5) . . ?
F1 C7 C8 109.8(6) . . ?
F2 C7 C8 109.4(5) . . ?
F1 C7 C6 108.8(5) . . ?
F2 C7 C6 109.5(6) . . ?
C8 C7 C6 113.8(6) . . ?
N3 C8 C7 108.6(6) . . ?
N3 C8 C9 110.9(5) . . ?
C7 C8 C9 113.5(6) . . ?
N3 C8 H8 107.9 . . ?
C7 C8 H8 107.9 . . ?
C9 C8 H8 107.9 . . ?
C10 C9 C8 113.9(6) . . ?
C10 C9 H9A 108.8 . . ?
C8 C9 H9A 108.8 . . ?
C10 C9 H9B 108.8 . . ?
C8 C9 H9B 108.8 . . ?
H9A C9 H9B 107.7 . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
N3 C11 C12 104.1(6) . . ?
N3 C11 H11 127.9 . . ?
C12 C11 H11 127.9 . . ?
N1 C12 C11 108.6(6) . . ?
N1 C12 C13 122.7(6) . . ?
C11 C12 C13 128.7(6) . . ?
C14 C13 C18 118.7(6) . . ?
C14 C13 C12 120.7(6) . . ?
C18 C13 C12 120.7(6) . . ?
C15 C14 C13 120.8(7) . . ?
C15 C14 H14 119.6 . . ?
C13 C14 H14 119.6 . . ?
C16 C15 C14 119.1(7) . . ?
C16 C15 H15 120.4 . . ?
C14 C15 H15 120.4 . . ?
C17 C16 C15 121.6(6) . . ?
C17 C16 Br1 120.5(6) . . ?
C15 C16 Br1 118.0(5) . . ?
C16 C17 C18 119.4(7) . . ?
C16 C17 H17 120.3 . . ?
C18 C17 H17 120.3 . . ?
C17 C18 C13 120.4(6) . . ?
C17 C18 H18 119.8 . . ?
C13 C18 H18 119.8 . . ?
 
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
C12 N1 N2 N3 -0.3(7) . . . . ?
N1 N2 N3 C11 0.9(7) . . . . ?
N1 N2 N3 C8 179.4(5) . . . . ?
C6 C1 C2 C3 0.9(10) . . . . ?
C1 C2 C3 C4 1.6(10) . . . . ?
C1 C2 C3 N4 -177.5(6) . . . . ?
O2 N4 C3 C2 169.8(7) . . . . ?
O1 N4 C3 C2 -7.8(9) . . . . ?
O2 N4 C3 C4 -9.4(9) . . . . ?
O1 N4 C3 C4 172.9(6) . . . . ?
C2 C3 C4 C5 -2.4(10) . . . . ?
N4 C3 C4 C5 176.8(6) . . . . ?
C3 C4 C5 C6 0.6(10) . . . . ?
C2 C1 C6 C5 -2.6(10) . . . . ?
C2 C1 C6 C7 177.6(6) . . . . ?
C4 C5 C6 C1 1.9(10) . . . . ?
C4 C5 C6 C7 -178.3(6) . . . . ?
C1 C6 C7 F1 52.7(8) . . . . ?
C5 C6 C7 F1 -127.0(7) . . . . ?
C1 C6 C7 F2 167.2(6) . . . . ?
C5 C6 C7 F2 -12.6(9) . . . . ?
C1 C6 C7 C8 -70.0(8) . . . . ?
C5 C6 C7 C8 110.2(7) . . . . ?
C11 N3 C8 C7 86.8(8) . . . . ?
N2 N3 C8 C7 -91.4(7) . . . . ?
C11 N3 C8 C9 -38.6(10) . . . . ?
N2 N3 C8 C9 143.3(6) . . . . ?
F1 C7 C8 N3 62.1(7) . . . . ?
F2 C7 C8 N3 -52.8(7) . . . . ?
C6 C7 C8 N3 -175.7(6) . . . . ?
F1 C7 C8 C9 -174.1(5) . . . . ?
F2 C7 C8 C9 71.0(7) . . . . ?
C6 C7 C8 C9 -51.9(8) . . . . ?
N3 C8 C9 C10 -59.4(8) . . . . ?
C7 C8 C9 C10 177.9(6) . . . . ?
N2 N3 C11 C12 -1.1(7) . . . . ?
C8 N3 C11 C12 -179.4(6) . . . . ?
N2 N1 C12 C11 -0.3(7) . . . . ?
N2 N1 C12 C13 -179.9(6) . . . . ?
N3 C11 C12 N1 0.9(7) . . . . ?
N3 C11 C12 C13 -179.6(6) . . . . ?
N1 C12 C13 C14 160.4(6) . . . . ?
C11 C12 C13 C14 -19.1(10) . . . . ?
N1 C12 C13 C18 -19.8(10) . . . . ?
C11 C12 C13 C18 160.7(7) . . . . ?
C18 C13 C14 C15 1.7(9) . . . . ?
C12 C13 C14 C15 -178.5(6) . . . . ?
C13 C14 C15 C16 -0.7(10) . . . . ?
C14 C15 C16 C17 -0.4(10) . . . . ?
C14 C15 C16 Br1 179.5(5) . . . . ?
C15 C16 C17 C18 0.5(10) . . . . ?
Br1 C16 C17 C18 -179.5(5) . . . . ?
C16 C17 C18 C13 0.6(10) . . . . ?
C14 C13 C18 C17 -1.7(9) . . . . ?
C12 C13 C18 C17 178.5(6) . . . . ?
 
_refine_diff_density_max    1.127
_refine_diff_density_min   -0.381
_refine_diff_density_rms    0.100



