data_2
_audit_creation_date               2019-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2016/6'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
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. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety          
 'C18 H3.4 Br3.4 Cl2.6 N3.4 O8.6 Zn2, 2(C8 H20 N1)'
_chemical_formula_sum              'C34 H43.40 Br3.40 Cl2.60 N5.40 O8.60 Zn2'
_chemical_formula_weight           1159.99
_chemical_melting_point            ?
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'
 'Cl' 'Cl' 0.1484 0.1585 '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'
 'Zn' 'Zn' 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system        'trigonal'
_space_group_IT_number             162
_space_group_name_H-M_alt          'P -3 1 m'
_space_group_name_Hall             '-P 3 2'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-y, x-y, z'
 '-x+y, -x, z'
 '-y, -x, -z'
 '-x+y, y, -z'
 'x, x-y, -z'
 '-x, -y, -z'
 'y, -x+y, -z'
 'x-y, x, -z'
 'y, x, z'
 'x-y, -y, z'
 '-x, -x+y, z'

_cell_length_a                     13.9416(16)
_cell_length_b                     13.9416(16)
_cell_length_c                     10.2616(12)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  120
_cell_volume                       1727.3(4)
_cell_formula_units_Z              0.99996
_cell_measurement_reflns_used      2772
_cell_measurement_temperature      100(2)
_cell_measurement_theta_max        20.60
_cell_measurement_theta_min        2.60
_shelx_estimated_absorpt_T_max     0.970
_shelx_estimated_absorpt_T_min     0.785
_exptl_absorpt_coefficient_mu      2.795
_exptl_absorpt_correction_T_max    0.7457
_exptl_absorpt_correction_T_min    0.5447
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0945 before and 0.0732 after correction. The Ratio of minimum to maximum transmission is 0.7305. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              red
_exptl_crystal_colour_primary      red
_exptl_crystal_density_diffrn      1.115
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         hexagonal
_exptl_crystal_F_000               577
_exptl_crystal_size_max            0.091
_exptl_crystal_size_mid            0.085
_exptl_crystal_size_min            0.011
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.1199
_diffrn_reflns_av_unetI/netI       0.0481
_diffrn_reflns_Laue_measured_fraction_full  0.997
_diffrn_reflns_Laue_measured_fraction_max  0.997
_diffrn_reflns_limit_h_max         13
_diffrn_reflns_limit_h_min         -13
_diffrn_reflns_limit_k_max         13
_diffrn_reflns_limit_k_min         -13
_diffrn_reflns_limit_l_max         10
_diffrn_reflns_limit_l_min         -10
_diffrn_reflns_number              10580
_diffrn_reflns_point_group_measured_fraction_full  0.997
_diffrn_reflns_point_group_measured_fraction_max  0.997
_diffrn_reflns_theta_full          20.803
_diffrn_reflns_theta_max           20.803
_diffrn_reflns_theta_min           2.605
_diffrn_ambient_temperature        99.99
_diffrn_detector_area_resol_mean   ?
_diffrn_measured_fraction_theta_full  0.997
_diffrn_measured_fraction_theta_max  0.997
_diffrn_measurement_device_type    'Bruker APEX-II CCD'
_diffrn_measurement_method         'φ and ω scans'
_diffrn_radiation_type             MoK\a
_diffrn_radiation_wavelength       0.71073
_diffrn_source                     ?
_diffrn_standards_number           0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  446
_reflns_number_total               668
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT V8.38A (?, 2016)'
_computing_data_collection         ?
_computing_data_reduction          'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics      'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement    'XL (Sheldrick, 2008)'
_computing_structure_solution      'XT (Sheldrick, 2015)'
_refine_diff_density_max           0.654
_refine_diff_density_min           -0.408
_refine_diff_density_rms           0.089
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     1.065
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       71
_refine_ls_number_reflns           668
_refine_ls_number_restraints       28
_refine_ls_R_factor_all            0.0917
_refine_ls_R_factor_gt             0.0632
_refine_ls_restrained_S_all        1.045
_refine_ls_shift/su_max            0.000
_refine_ls_shift/su_mean           0.000
_refine_ls_structure_factor_coef   Fsqd
_refine_ls_weighting_details      
 'w=1/[σ²(Fo²)+(0.1153P)²+5.3149P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.1768
_refine_ls_wR_factor_ref           0.1966
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Cl1, Br1}
{N1, O1}
3. Restrained distances
 N2-C3
 1.56 with sigma of 0.01
 C4-C3
 1.54 with sigma of 0.01
 N2-C4
 2.56 with sigma of 0.01
 N2-C3 \\sim N2-C5
 with sigma of 0.01
 C4-C3 \\sim C6-C5
 with sigma of 0.01
 N2-C4 \\sim N2-C6
 with sigma of 0.01
4. Restrained planarity
 N2, C3, C5, C4, C6
 with sigma of 0.01
5. Rigid bond restraints
 N2, C3, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, C5
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
6. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C6: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C5 \\sim C6: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
C3 \\sim C4: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Cl1) = Uanis(Br1)
Uanis(N1) = Uanis(O1)
7. Others
 Fixed Sof: N1(0.28333) H1(0.28333) O1(0.71667) Cl1(0.21667) Br1(0.28333)
 C4(0.33333) H4A(0.33333) H4B(0.33333) H4C(0.33333) C5(0.33333) H5A(0.33333)
 H5B(0.33333) C3(0.33333) H3A(0.33333) H3B(0.33333) C6(0.33333) H6A(0.33333)
 H6B(0.33333) H6C(0.33333)
8.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C3(H3A,H3B)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
8.c Aromatic/amide H refined with riding coordinates:
 N1(H1)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
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
 Zn1 Zn 0.333333 0.666667 0.000000 0.0538(11) Uani 1 6 d S T P . .
 N1 N 0.4530(5) 0.6494(5) 0.1059(6) 0.053(2) Uani 0.2833 1 d . . . A 1
 H1 H 0.483268 0.687525 0.177359 0.064 Uiso 0.2833 1 calc R . . A 1
 O1 O 0.4530(5) 0.6494(5) 0.1059(6) 0.053(2) Uani 0.7167 1 d . . . A 2
 N2 N 0.333333 0.666667 0.500000 0.090(5) Uani 1 6 d DS TU P . .
 C1 C 0.4790(8) 0.5801(7) 0.0601(8) 0.044(2) Uani 1 1 d . . . . .
 C2 C 0.5543(10) 0.5543(10) 0.1170(14) 0.058(4) Uani 1 2 d S T P A .
 Cl1 Cl 0.63381(16) 0.63381(16) 0.2635(2) 0.0681(10) Uani 0.4333 2 d S T P A 1
 Br1 Br 0.63381(16) 0.63381(16) 0.2635(2) 0.0681(10) Uani 0.5667 2 d S T P A 2
 C4 C 0.1763(19) 0.491(2) 0.602(3) 0.096(6) Uani 0.3333 1 d D U . B -1
 H4A H 0.132665 0.460279 0.681625 0.143 Uiso 0.3333 1 calc R . . B -1
 H4B H 0.126980 0.482792 0.529670 0.143 Uiso 0.3333 1 calc R . . B -1
 H4C H 0.215015 0.449929 0.581460 0.143 Uiso 0.3333 1 calc R . . B -1
 C5 C 0.421(2) 0.7904(13) 0.511(3) 0.108(11) Uani 0.3333 1 d D U . C -1
 H5A H 0.384450 0.833361 0.531475 0.129 Uiso 0.3333 1 calc R . . C -1
 H5B H 0.472493 0.800520 0.583315 0.129 Uiso 0.3333 1 calc R . . C -1
 C3 C 0.2615(19) 0.614(2) 0.6223(16) 0.094(6) Uani 0.3333 1 d D U . B -1
 H3A H 0.310219 0.621274 0.696543 0.113 Uiso 0.3333 1 calc R . . B -1
 H3B H 0.222163 0.654144 0.644741 0.113 Uiso 0.3333 1 calc R . . B -1
 C6 C 0.4887(18) 0.836(3) 0.385(3) 0.106(11) Uani 0.3333 1 d D U . C -1
 H6A H 0.543427 0.914212 0.396021 0.159 Uiso 0.3333 1 calc R . . C -1
 H6B H 0.526739 0.794357 0.364665 0.159 Uiso 0.3333 1 calc R . . C -1
 H6C H 0.438699 0.827196 0.312827 0.159 Uiso 0.3333 1 calc R . . C -1


_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
 Zn1 N1 2.103(7) 5 ?
 Zn1 N1 2.103(7) 6_565 ?
 Zn1 N1 2.103(7) 3_565 ?
 Zn1 N1 2.103(7) . ?
 Zn1 N1 2.103(7) 4_665 ?
 Zn1 N1 2.103(7) 2_665 ?
 Zn1 O1 2.103(7) . ?
 N1 C1 1.279(10) . ?
 O1 C1 1.279(10) . ?
 N2 C5 1.542(13) . ?
 N2 C3 1.544(10) . ?
 C1 C1 1.483(17) 4_665 ?
 C1 C2 1.397(11) . ?
 C2 Cl1 1.869(14) . ?
 C2 Br1 1.869(14) . ?
 C4 C3 1.539(10) . ?
 C5 C6 1.536(15) . ?

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
 N1 Zn1 N1 93.2(3) 5 2_665 ?
 N1 Zn1 N1 95.7(2) 6_565 4_665 ?
 N1 Zn1 N1 93.2(3) 6_565 . ?
 N1 Zn1 N1 93.2(3) 3_565 4_665 ?
 N1 Zn1 N1 95.7(2) 2_665 . ?
 N1 Zn1 N1 95.7(2) 3_565 . ?
 N1 Zn1 N1 95.7(2) 5 6_565 ?
 N1 Zn1 N1 76.4(4) 5 3_565 ?
 N1 Zn1 N1 76.4(4) 2_665 6_565 ?
 N1 Zn1 N1 168.6(4) 5 . ?
 N1 Zn1 N1 168.6(4) 3_565 6_565 ?
 N1 Zn1 N1 95.7(2) 2_665 3_565 ?
 N1 Zn1 N1 95.7(2) 5 4_665 ?
 N1 Zn1 N1 168.6(4) 2_665 4_665 ?
 N1 Zn1 N1 76.4(4) 4_665 . ?
 C1 N1 Zn1 115.9(6) . . ?
 C1 O1 Zn1 115.9(6) . . ?
 C5 N2 C3 116.1(16) . . ?
 N1 C1 C1 115.9(5) . 4_665 ?
 N1 C1 C2 125.1(9) . . ?
 O1 C1 C1 115.9(5) . 4_665 ?
 O1 C1 C2 125.1(9) . . ?
 C2 C1 C1 119.0(6) . 4_665 ?
 C1 C2 C1 121.9(13) 10 . ?
 C1 C2 Cl1 118.9(6) 10 . ?
 C1 C2 Cl1 118.9(6) . . ?
 C1 C2 Br1 118.9(6) 10 . ?
 C1 C2 Br1 118.9(6) . . ?
 C6 C5 N2 112.4(14) . . ?
 C4 C3 N2 112.1(10) . . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.000 0.000 -0.057 726.1 132.2 ?

_olex2_submission_special_instructions  'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_2
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The crystal diffracted to a resolution of 1.0 A
;
_vrf_PLAT341_2
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0155 Ang.  
RESPONSE: The crystal diffracted to a resolution of 1.0 A
;
# end Validation Reply Form

data_3
_audit_creation_date               2019-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2016/6'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
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. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety           'C18 H3.8 Cl6 N3.8 O8.2 Zn2, 2(C8 H20 N1)'
_chemical_formula_sum              'C34 H43.80 Cl6 N5.80 O8.20 Zn2'
_chemical_formula_weight           1008.43
_chemical_melting_point            ?
loop_
  _atom_type_symbol
  _atom_type_description
  _atom_type_scat_dispersion_real
  _atom_type_scat_dispersion_imag
  _atom_type_scat_source
 'C' 'C' 0.0181 0.0091 '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'
 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Zn' 'Zn' -1.5491 0.6778
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system        'trigonal'
_space_group_IT_number             162
_space_group_name_H-M_alt          'P -3 1 m'
_space_group_name_Hall             '-P 3 2'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-y, x-y, z'
 '-x+y, -x, z'
 '-y, -x, -z'
 '-x+y, y, -z'
 'x, x-y, -z'
 '-x, -y, -z'
 'y, -x+y, -z'
 'x-y, x, -z'
 'y, x, z'
 'x-y, -y, z'
 '-x, -x+y, z'

_cell_length_a                     13.9533(10)
_cell_length_b                     13.9533(10)
_cell_length_c                     10.1333(11)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  120
_cell_volume                       1708.6(3)
_cell_formula_units_Z              0.99996
_cell_measurement_reflns_used      2715
_cell_measurement_temperature      100(2)
_cell_measurement_theta_max        52.35
_cell_measurement_theta_min        3.66
_shelx_estimated_absorpt_T_max     0.801
_shelx_estimated_absorpt_T_min     0.563
_exptl_absorpt_coefficient_mu      3.313
_exptl_absorpt_correction_T_max    0.7505
_exptl_absorpt_correction_T_min    0.4955
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1678 before and 0.0824 after correction. The Ratio of minimum to maximum transmission is 0.6602. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              red
_exptl_crystal_colour_primary      red
_exptl_crystal_density_diffrn      0.980
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         hexagonal
_exptl_crystal_F_000               516
_exptl_crystal_size_max            0.196
_exptl_crystal_size_mid            0.136
_exptl_crystal_size_min            0.07
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.1159
_diffrn_reflns_av_unetI/netI       0.0439
_diffrn_reflns_Laue_measured_fraction_full  0.997
_diffrn_reflns_Laue_measured_fraction_max  0.997
_diffrn_reflns_limit_h_max         13
_diffrn_reflns_limit_h_min         -13
_diffrn_reflns_limit_k_max         11
_diffrn_reflns_limit_k_min         -12
_diffrn_reflns_limit_l_max         9
_diffrn_reflns_limit_l_min         -9
_diffrn_reflns_number              7875
_diffrn_reflns_point_group_measured_fraction_full  0.997
_diffrn_reflns_point_group_measured_fraction_max  0.997
_diffrn_reflns_theta_full          47.179
_diffrn_reflns_theta_max           47.179
_diffrn_reflns_theta_min           5.698
_diffrn_ambient_temperature        99.99
_diffrn_detector_area_resol_mean   ?
_diffrn_measured_fraction_theta_full  0.997
_diffrn_measured_fraction_theta_max  0.997
_diffrn_measurement_device_type    'Bruker APEX-II CCD'
_diffrn_measurement_method         'φ and ω scans'
_diffrn_radiation_type             CuK\a
_diffrn_radiation_wavelength       1.54178
_diffrn_source                     ?
_diffrn_standards_number           0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  409
_reflns_number_total               570
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT V8.38A (?, 2016)'
_computing_data_collection         ?
_computing_data_reduction          'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics      'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement    'XL (Sheldrick, 2008)'
_computing_structure_solution      'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max           1.194
_refine_diff_density_min           -0.416
_refine_diff_density_rms           0.111
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     1.399
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       71
_refine_ls_number_reflns           570
_refine_ls_number_restraints       36
_refine_ls_R_factor_all            0.1373
_refine_ls_R_factor_gt             0.1125
_refine_ls_restrained_S_all        1.361
_refine_ls_shift/su_max            0.000
_refine_ls_shift/su_mean           0.000
_refine_ls_structure_factor_coef   Fsqd
_refine_ls_weighting_details      
 'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.3075
_refine_ls_wR_factor_ref           0.3324
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{N1, O1}
3. Restrained distances
 C3-C4
 1.54 with sigma of 0.02
 N2-C3
 1.56 with sigma of 0.02
 N2-C3 \\sim N2-C5
 with sigma of 0.01
 C5-C6 \\sim C3-C4
 with sigma of 0.01
 C4-N2 \\sim N2-C6
 with sigma of 0.01
4. Restrained planarity
 C4, C3, N2, C5, C6
 with sigma of 0.01
5. Rigid bond restraints
 N2, C3, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C3 \\sim C4: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
N2 \\sim C5 \\sim C6: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(N1) = Uanis(O1)
7. Others
 Fixed Sof: N1(0.31667) H1(0.31667) O1(0.68333) C4(0.33333) H4A(0.33333)
 H4B(0.33333) H4C(0.33333) C3(0.33333) H3A(0.33333) H3B(0.33333) C5(0.33333)
 H5A(0.33333) H5B(0.33333) C6(0.33333) H6A(0.33333) H6B(0.33333) H6C(0.33333)
8.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
8.c Aromatic/amide H refined with riding coordinates:
 N1(H1)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
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
 Zn1 Zn 0.333333 0.666667 0.500000 0.0773(19) Uani 1 6 d S T P . .
 Cl1 Cl 0.3862(6) 0.3862(6) 0.7688(6) 0.155(3) Uani 1 2 d S T P . .
 N1 N 0.3546(6) 0.5519(7) 0.6121(7) 0.079(3) Uani 0.3167 1 d . . . A 1
 H1 H 0.318593 0.524312 0.686500 0.095 Uiso 0.3167 1 calc R . . A 1
 O1 O 0.3546(6) 0.5519(7) 0.6121(7) 0.079(3) Uani 0.6833 1 d . . . A 2
 C1 C 0.4226(9) 0.5244(9) 0.5662(10) 0.071(3) Uani 1 1 d . . . . .
 C2 C 0.4493(12) 0.4493(12) 0.6245(16) 0.084(5) Uani 1 2 d S T P A .
 N2 N 0.666667 0.333333 0.000000 0.125(7) Uani 1 6 d DS TU P . .
 C4 C 0.846(3) 0.489(2) 0.109(4) 0.131(11) Uani 0.3333 1 d D U . B -1
 H4A H 0.872441 0.532541 0.189895 0.196 Uiso 0.3333 1 calc R . . B -1
 H4B H 0.885124 0.447538 0.095596 0.196 Uiso 0.3333 1 calc R . . B -1
 H4C H 0.860973 0.538799 0.033429 0.196 Uiso 0.3333 1 calc R . . B -1
 C3 C 0.720(3) 0.407(2) 0.119(2) 0.128(10) Uani 0.3333 1 d D U . B -1
 H3A H 0.706862 0.359509 0.196961 0.154 Uiso 0.3333 1 calc R . . B -1
 H3B H 0.682782 0.450502 0.134976 0.154 Uiso 0.3333 1 calc R . . B -1
 C5 C 0.5447(15) 0.259(3) 0.027(3) 0.127(7) Uani 0.3333 1 d D U . B -1
 H5A H 0.512378 0.307082 0.045873 0.153 Uiso 0.3333 1 calc R . . B -1
 H5B H 0.536464 0.216053 0.107689 0.153 Uiso 0.3333 1 calc R . . B -1
 C6 C 0.476(3) 0.178(2) -0.085(4) 0.130(10) Uani 0.3333 1 d D U . B -1
 H6A H 0.398359 0.134071 -0.057176 0.195 Uiso 0.3333 1 calc R . . B -1
 H6B H 0.480863 0.219353 -0.164814 0.195 Uiso 0.3333 1 calc R . . B -1
 H6C H 0.505022 0.128046 -0.102808 0.195 Uiso 0.3333 1 calc R . . B -1


_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
 Zn1 N1 2.102(8) 6_566 ?
 Zn1 N1 2.102(8) . ?
 Zn1 N1 2.102(8) 4_666 ?
 Zn1 N1 2.102(8) 3_565 ?
 Zn1 N1 2.102(8) 5_556 ?
 Zn1 N1 2.102(8) 2_665 ?
 Zn1 O1 2.102(8) . ?
 Cl1 C2 1.707(15) . ?
 N1 C1 1.277(12) . ?
 O1 C1 1.277(12) . ?
 C1 C1 1.531(19) 4_666 ?
 C1 C2 1.405(13) . ?
 N2 C3 1.518(16) . ?
 N2 C5 1.510(17) . ?
 C4 C3 1.548(19) . ?
 C5 C6 1.55(2) . ?

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
 N1 Zn1 N1 97.4(4) 6_566 3_565 ?
 N1 Zn1 N1 93.5(3) 5_556 4_666 ?
 N1 Zn1 N1 97.4(4) 5_556 . ?
 N1 Zn1 N1 93.5(3) 6_566 5_556 ?
 N1 Zn1 N1 166.0(4) 6_566 . ?
 N1 Zn1 N1 77.1(4) 3_565 5_556 ?
 N1 Zn1 N1 166.0(4) 3_565 4_666 ?
 N1 Zn1 N1 77.1(4) 6_566 2_665 ?
 N1 Zn1 N1 97.4(4) 2_665 4_666 ?
 N1 Zn1 N1 93.5(3) 3_565 2_665 ?
 N1 Zn1 N1 93.5(3) 3_565 . ?
 N1 Zn1 N1 166.0(4) 5_556 2_665 ?
 N1 Zn1 N1 77.1(4) 4_666 . ?
 N1 Zn1 N1 93.5(3) 6_566 4_666 ?
 N1 Zn1 N1 93.5(3) 2_665 . ?
 C1 N1 Zn1 116.2(6) . . ?
 C1 O1 Zn1 116.2(6) . . ?
 N1 C1 C1 115.3(5) . 4_666 ?
 N1 C1 C2 125.7(10) . . ?
 O1 C1 C1 115.3(5) . 4_666 ?
 O1 C1 C2 125.7(10) . . ?
 C2 C1 C1 119.0(7) . 4_666 ?
 C1 C2 Cl1 119.0(7) . . ?
 C1 C2 Cl1 119.0(7) 10 . ?
 C1 C2 C1 122.0(14) . 10 ?
 C5 N2 C3 109(2) . . ?
 N2 C3 C4 116(2) . . ?
 N2 C5 C6 116(2) . . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.000 0.000 -0.504 708.0 211.7 ?

_olex2_submission_special_instructions  'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_3
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The crystal diffracted to a resolution of 1.05 A
;
_vrf_PLAT341_3
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0175 Ang.  
RESPONSE: The crystal diffracted to a resolution of 1.05 A
;
# end Validation Reply Form

data_4
_audit_creation_date               2019-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2016/6'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
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. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety           'C18 Cl6 Mn2 O12, 6(C0.67 H2.67 N0.33)'
_chemical_formula_sum              'C22 H16 Cl6 Mn2 N2 O12'
_chemical_formula_weight           822.98
_chemical_melting_point            ?
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'
 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Mn' 'Mn' 0.3368 0.7283 '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'

_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.
;
_space_group_crystal_system        'trigonal'
_space_group_IT_number             162
_space_group_name_H-M_alt          'P -3 1 m'
_space_group_name_Hall             '-P 3 2'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-y, x-y, z'
 '-x+y, -x, z'
 '-y, -x, -z'
 '-x+y, y, -z'
 'x, x-y, -z'
 '-x, -y, -z'
 'y, -x+y, -z'
 'x-y, x, -z'
 'y, x, z'
 'x-y, -y, z'
 '-x, -x+y, z'

_cell_length_a                     14.017(4)
_cell_length_b                     14.017(4)
_cell_length_c                     8.970(2)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  120
_cell_volume                       1526.3(9)
_cell_formula_units_Z              0.99996
_cell_measurement_reflns_used      7963
_cell_measurement_temperature      250(2)
_cell_measurement_theta_max        20.88
_cell_measurement_theta_min        2.82
_shelx_estimated_absorpt_T_max     0.894
_shelx_estimated_absorpt_T_min     0.837
_exptl_absorpt_coefficient_mu      0.708
_exptl_absorpt_correction_T_max    0.7446
_exptl_absorpt_correction_T_min    0.5425
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1256 before and 0.1048 after correction. The Ratio of minimum to maximum transmission is 0.7286. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              brown
_exptl_crystal_colour_primary      brown
_exptl_crystal_density_diffrn      0.895
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         hexagonal
_exptl_crystal_F_000               410
_exptl_crystal_size_max            0.26
_exptl_crystal_size_mid            0.192
_exptl_crystal_size_min            0.162
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.0743
_diffrn_reflns_av_unetI/netI       0.0246
_diffrn_reflns_Laue_measured_fraction_full  0.971
_diffrn_reflns_Laue_measured_fraction_max  0.971
_diffrn_reflns_limit_h_max         13
_diffrn_reflns_limit_h_min         -13
_diffrn_reflns_limit_k_max         14
_diffrn_reflns_limit_k_min         -13
_diffrn_reflns_limit_l_max         8
_diffrn_reflns_limit_l_min         -8
_diffrn_reflns_number              10280
_diffrn_reflns_point_group_measured_fraction_full  0.971
_diffrn_reflns_point_group_measured_fraction_max  0.971
_diffrn_reflns_theta_full          20.789
_diffrn_reflns_theta_max           20.789
_diffrn_reflns_theta_min           2.824
_diffrn_ambient_temperature        250.01
_diffrn_detector_area_resol_mean   ?
_diffrn_measured_fraction_theta_full  0.971
_diffrn_measured_fraction_theta_max  0.971
_diffrn_measurement_device_type    'Bruker APEX-II CCD'
_diffrn_measurement_method         'φ and ω scans'
_diffrn_radiation_type             MoK\a
_diffrn_radiation_wavelength       0.71073
_diffrn_source                     ?
_diffrn_standards_number           0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  461
_reflns_number_total               572
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT V8.38A (?, 2016)'
_computing_data_collection         ?
_computing_data_reduction          'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics      'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement    'XL (Sheldrick, 2008)'
_computing_structure_solution      'XT (Sheldrick, 2015)'
_refine_diff_density_max           1.681
_refine_diff_density_min           -0.526
_refine_diff_density_rms           0.177
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     2.113
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       48
_refine_ls_number_reflns           572
_refine_ls_number_restraints       9
_refine_ls_R_factor_all            0.1590
_refine_ls_R_factor_gt             0.1492
_refine_ls_restrained_S_all        2.109
_refine_ls_shift/su_max            0.000
_refine_ls_shift/su_mean           0.000
_refine_ls_structure_factor_coef   Fsqd
_refine_ls_weighting_details      
 'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.3761
_refine_ls_wR_factor_ref           0.4383
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C4
 1.48 with sigma of 0.02
 C4_$1-C4_$2
 2.4 with sigma of 0.02
3. Rigid bond restraints
 C4, N1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N1 \\sim C4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Others
 Fixed Sof: N1(0.16667) H1A(0.16667) H1B(0.16667) C4(0.33333) H4A(0.33333)
 H4B(0.33333) H4C(0.33333)
6.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B)
6.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
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
 Mn01 Mn 0.666667 0.333333 0.500000 0.0850(19) Uani 1 6 d S T P . .
 Cl00 Cl 1.000000 0.3899(3) 0.8085(5) 0.137(2) Uani 1 2 d S T P . .
 O003 O 0.8079(5) 0.3587(4) 0.6262(6) 0.093(2) Uani 1 1 d . . . . .
 C004 C 1.000000 0.4476(6) 0.6398(9) 0.078(3) Uani 1 2 d S T P . .
 C005 C 0.8998(6) 0.4236(5) 0.5756(7) 0.079(2) Uani 1 1 d . . . . .
 N1 N 1.000000 0.728(3) 0.736(5) 0.178(18) Uani 0.3333 2 d DS TU P . .
 H1A H 1.000000 0.723212 0.636002 0.214 Uiso 0.3333 2 calc RS T P . .
 H1B H 0.999999 0.790078 0.760780 0.214 Uiso 0.3333 2 calc RS T P . .
 C4 C 0.9010(8) 0.631(3) 0.798(4) 0.171(14) Uani 0.3333 1 d D U . . .
 H4A H 0.835246 0.628126 0.758774 0.256 Uiso 0.3333 1 calc R . . . .
 H4B H 0.901440 0.564137 0.770662 0.256 Uiso 0.3333 1 calc R . . . .
 H4C H 0.901439 0.636690 0.906052 0.256 Uiso 0.3333 1 calc R . . . .


_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
 Mn01 O003 2.151(6) 4_666 ?
 Mn01 O003 2.151(6) 5_656 ?
 Mn01 O003 2.151(6) 6_556 ?
 Mn01 O003 2.151(6) . ?
 Mn01 O003 2.151(6) 2_655 ?
 Mn01 O003 2.151(6) 3_665 ?
 Cl00 C004 1.716(8) . ?
 O003 C005 1.234(8) . ?
 C004 C005 1.395(8) . ?
 C004 C005 1.395(8) 12_765 ?
 C005 C005 1.543(13) 6_556 ?
 N1 C4 1.483(18) . ?
 N1 C4 1.483(18) 12_765 ?

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
 O003 Mn01 O003 98.3(3) 4_666 . ?
 O003 Mn01 O003 98.3(3) 3_665 5_656 ?
 O003 Mn01 O003 98.3(3) 6_556 2_655 ?
 O003 Mn01 O003 74.2(2) 4_666 3_665 ?
 O003 Mn01 O003 163.6(3) 4_666 2_655 ?
 O003 Mn01 O003 94.8(2) . 3_665 ?
 O003 Mn01 O003 163.6(3) . 5_656 ?
 O003 Mn01 O003 94.8(2) 4_666 6_556 ?
 O003 Mn01 O003 94.8(2) 6_556 5_656 ?
 O003 Mn01 O003 74.2(2) . 6_556 ?
 O003 Mn01 O003 94.8(2) 3_665 2_655 ?
 O003 Mn01 O003 163.6(3) 3_665 6_556 ?
 O003 Mn01 O003 74.2(2) 5_656 2_655 ?
 O003 Mn01 O003 94.8(2) 4_666 5_656 ?
 O003 Mn01 O003 94.8(2) . 2_655 ?
 C005 O003 Mn01 117.6(4) . . ?
 C005 C004 Cl00 119.2(4) . . ?
 C005 C004 Cl00 119.2(4) 12_765 . ?
 C005 C004 C005 121.4(8) . 12_765 ?
 O003 C005 C004 125.4(6) . . ?
 O003 C005 C005 115.2(4) . 6_556 ?
 C004 C005 C005 119.2(4) . 6_556 ?
 C4 N1 C4 108(2) 12_765 . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.000 0.000 -0.557 379.8 53.1 ?
 2 0.333 0.667 0.000 84.5 32.2 ?
 3 0.667 0.333 0.000 84.5 31.7 ?

_olex2_submission_special_instructions  'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_4
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Due to weak diffraction, data is collected to 1.00 A
;
# end Validation Reply Form

data_5
_audit_creation_date               2019-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2016/6'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
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. (2008). Acta Cryst. A64, 112-122.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety          
 'C18 H2.4 Br2.4 Cl3.6 Mn2 N2.4 O9.6, 2(C8 H20 N1)'
_chemical_formula_sum              'C34 H42.40 Br2.40 Cl3.60 Mn2 N4.40 O9.60'
_chemical_formula_weight           1095.65
_chemical_melting_point            ?
loop_
  _atom_type_symbol
  _atom_type_description
  _atom_type_scat_dispersion_real
  _atom_type_scat_dispersion_imag
  _atom_type_scat_source
 'C' 'C' 0.0181 0.0091 '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' -0.6763 1.2805
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Mn' 'Mn' -0.5299 2.8052
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system        'trigonal'
_space_group_IT_number             162
_space_group_name_H-M_alt          'P -3 1 m'
_space_group_name_Hall             '-P 3 2'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-y, x-y, z'
 '-x+y, -x, z'
 '-y, -x, -z'
 '-x+y, y, -z'
 'x, x-y, -z'
 '-x, -y, -z'
 'y, -x+y, -z'
 'x-y, x, -z'
 'y, x, z'
 'x-y, -y, z'
 '-x, -x+y, z'

_cell_length_a                     14.1160(5)
_cell_length_b                     14.1160(5)
_cell_length_c                     9.9697(10)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  120
_cell_volume                       1720.4(2)
_cell_formula_units_Z              0.99996
_cell_measurement_reflns_used      1129
_cell_measurement_temperature      100(2)
_cell_measurement_theta_max        50.258
_cell_measurement_theta_min        5.726
_shelx_estimated_absorpt_T_max     0.576
_shelx_estimated_absorpt_T_min     0.118
_exptl_absorpt_coefficient_mu      6.205
_exptl_absorpt_correction_T_max    0.7500
_exptl_absorpt_correction_T_min    0.3338
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1323 before and 0.0709 after correction. The Ratio of minimum to maximum transmission is 0.4451. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              'dark brown'
_exptl_crystal_colour_modifier     dark
_exptl_crystal_colour_primary      brown
_exptl_crystal_density_diffrn      1.057
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         hexagonal
_exptl_crystal_F_000               549
_exptl_crystal_preparation         ?
_exptl_crystal_size_max            0.6
_exptl_crystal_size_mid            0.5
_exptl_crystal_size_min            0.1
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.0857
_diffrn_reflns_av_unetI/netI       0.0669
_diffrn_reflns_Laue_measured_fraction_full  0.984
_diffrn_reflns_Laue_measured_fraction_max  0.982
_diffrn_reflns_limit_h_max         8
_diffrn_reflns_limit_h_min         -14
_diffrn_reflns_limit_k_max         13
_diffrn_reflns_limit_k_min         -10
_diffrn_reflns_limit_l_max         9
_diffrn_reflns_limit_l_min         -9
_diffrn_reflns_number              2931
_diffrn_reflns_point_group_measured_fraction_full  0.984
_diffrn_reflns_point_group_measured_fraction_max  0.982
_diffrn_reflns_theta_full          50.487
_diffrn_reflns_theta_max           50.487
_diffrn_reflns_theta_min           5.726
_diffrn_ambient_temperature        100.02
_diffrn_detector_area_resol_mean   8
_diffrn_measured_fraction_theta_full  0.984
_diffrn_measured_fraction_theta_max  0.982
_diffrn_measurement_device_type    'CCD area detector'
_diffrn_measurement_method         'phi and omega scans'
_diffrn_radiation_monochromator    'graphite'
_diffrn_radiation_type             CuK\a
_diffrn_radiation_wavelength       1.54178
_diffrn_source                     microsource
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  493
_reflns_number_total               658
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection         'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction          'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics      'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement    'XL (Sheldrick, 2008)'
_computing_structure_solution      'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max           0.759
_refine_diff_density_min           -0.627
_refine_diff_density_rms           0.085
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     1.283
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       75
_refine_ls_number_reflns           658
_refine_ls_number_restraints       40
_refine_ls_R_factor_all            0.1197
_refine_ls_R_factor_gt             0.0962
_refine_ls_restrained_S_all        1.254
_refine_ls_shift/su_max            0.000
_refine_ls_shift/su_mean           0.000
_refine_ls_structure_factor_coef   Fsqd
_refine_ls_weighting_details      
 'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.2713
_refine_ls_wR_factor_ref           0.3105
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{N1A, N1B, O1}
{H1A, H1B}
{Cl1, Br1}
3. Restrained distances
 N2-C3
 1.56 with sigma of 0.01
 C4-C3
 1.54 with sigma of 0.01
 N2-C3 \\sim N2-C5
 with sigma of 0.01
 N2-C4 \\sim N2-C6
 with sigma of 0.01
 C3-C6 \\sim C5-C4
 with sigma of 0.01
 Br2-C2 \\sim Cl1-C2
 with sigma of 0.02
4. Restrained planarity
 N2, C3, C4, C5, C6
 with sigma of 0.001
5. Rigid bond restraints
 N2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(N1A) = Uanis(N1B) = Uanis(O1)
Uanis(Cl1) = Uanis(Br1) = Uanis(Br2)
7. Others
 1*[Sof(Br1)+Sof(N1A)+Sof(H1A)]+1*[Sof(Br2)+Sof(N1B)+Sof(H1B)]=0.4 with esd of
 0.001
 Sof(Br1)=Sof(N1A)=Sof(H1A)=0.5*FVAR(2)
 Sof(Br2)=Sof(N1B)=Sof(H1B)=0.5*FVAR(3)
 Fixed Sof: Cl1(0.3) O1(0.8) C3(0.33333) H3A(0.33333) H3B(0.33333) C4(0.33333)
 H4A(0.33333) H4B(0.33333) H4C(0.33333) C5(0.33333) H5A(0.33333) H5B(0.33333)
 C6(0.33333) H6A(0.33333) H6B(0.33333) H6C(0.33333)
 Fixed X: H1A(0.67185) H1B(0.67185)
 Fixed Y: H1A(0.472229) H1B(0.472229)
 Fixed Z: H1A(0.694429) H1B(0.694429)
8.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
;
_atom_sites_solution_hydrogens     mixed
_atom_sites_solution_primary       direct
_atom_sites_solution_secondary     ?
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
 Mn1 Mn 0.666667 0.333333 0.500000 0.0645(13) Uani 1 6 d S T P . .
 Br1 Br 0.5890(5) 0.5890(5) 0.7983(5) 0.120(2) Uani 0.132(4) 2 d S T P . .
 Br2 Br 0.6529(7) 0.6529(7) 0.7405(8) 0.120(2) Uani 0.267(4) 2 d DS T P . .
 Cl1 Cl 0.5890(5) 0.5890(5) 0.7983(5) 0.120(2) Uani 0.6 2 d DS T P . .
 N1A N 0.6389(5) 0.4455(5) 0.6157(6) 0.081(2) Uani 0.0662(18) 1 d . . . A 1
 H1A H 0.671850 0.472229 0.694429 0.097 Uiso 0.0662(18) 1 d R . . A 1
 N1B N 0.6389(5) 0.4455(5) 0.6157(6) 0.081(2) Uani 0.1335(18) 1 d . . . A 2
 H1B H 0.671850 0.472229 0.694429 0.097 Uiso 0.1335(18) 1 d R . . A 2
 O1 O 0.6389(5) 0.4455(5) 0.6157(6) 0.081(2) Uani 0.8 1 d . . . A 3
 C1 C 0.5763(7) 0.4747(7) 0.5684(8) 0.073(2) Uani 1 1 d . . . . .
 C2 C 0.5526(10) 0.5526(10) 0.6277(11) 0.086(4) Uani 1 2 d DS T P A .
 N2 N 0.666667 0.333333 1.000000 0.090(5) Uani 1 6 d DS TU P . .
 C3 C 0.6894(12) 0.4141(12) 1.1184(14) 0.091(7) Uani 0.3333 1 d D U . B -1
 H3A H 0.660098 0.371477 1.202077 0.109 Uiso 0.3333 1 calc R . . B -1
 H3B H 0.769518 0.461059 1.129478 0.109 Uiso 0.3333 1 calc R . . B -1
 C4 C 0.6388(11) 0.4878(11) 1.0990(19) 0.117(12) Uani 0.3333 1 d D U . B -1
 H4A H 0.656148 0.536297 1.176673 0.175 Uiso 0.3333 1 calc R . . B -1
 H4B H 0.668751 0.531855 1.017625 0.175 Uiso 0.3333 1 calc R . . B -1
 H4C H 0.559211 0.442175 1.090304 0.175 Uiso 0.3333 1 calc R . . B -1
 C5 C 0.7212(14) 0.2637(14) 1.030(2) 0.105(9) Uani 0.3333 1 d D U . B -1
 H5A H 0.691303 0.223808 1.115551 0.126 Uiso 0.3333 1 calc R . . B -1
 H5B H 0.800712 0.313382 1.042958 0.126 Uiso 0.3333 1 calc R . . B -1
 C6 C 0.7040(14) 0.1805(11) 0.920(2) 0.110(11) Uani 0.3333 1 d D U . B -1
 H6A H 0.740488 0.139572 0.945158 0.165 Uiso 0.3333 1 calc R . . B -1
 H6B H 0.625592 0.129614 0.907784 0.165 Uiso 0.3333 1 calc R . . B -1
 H6C H 0.735132 0.219295 0.835106 0.165 Uiso 0.3333 1 calc R . . B -1


_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
 Mn1 N1A 2.147(6) 3_665 ?
 Mn1 N1A 2.147(6) 4_666 ?
 Mn1 N1A 2.147(6) . ?
 Mn1 N1A 2.147(6) 6_556 ?
 Mn1 N1A 2.147(6) 5_656 ?
 Mn1 N1A 2.147(6) 2_655 ?
 Mn1 N1B 2.147(6) . ?
 Mn1 O1 2.147(6) . ?
 Br2 Cl1 1.071(9) . ?
 Br2 C2 1.807(14) . ?
 Cl1 C2 1.776(11) . ?
 N1A H1A 0.894(5) . ?
 N1A C1 1.239(10) . ?
 N1B H1B 0.894(5) . ?
 N1B C1 1.239(10) . ?
 O1 C1 1.239(10) . ?
 C1 C1 1.542(16) 4_666 ?
 C1 C2 1.429(10) . ?
 N2 C3 1.559(9) . ?
 N2 C5 1.551(12) . ?
 C3 H3A 0.9900 . ?
 C3 H3B 0.9900 . ?
 C3 C4 1.541(10) . ?
 C4 H4A 0.9800 . ?
 C4 H4B 0.9800 . ?
 C4 H4C 0.9800 . ?
 C5 H5A 0.9900 . ?
 C5 H5B 0.9900 . ?
 C5 C6 1.54(2) . ?
 C6 H6A 0.9800 . ?
 C6 H6B 0.9800 . ?
 C6 H6C 0.9800 . ?

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
 N1A Mn1 N1A 100.6(4) 3_665 6_556 ?
 N1A Mn1 N1A 93.8(2) 5_656 4_666 ?
 N1A Mn1 N1A 100.7(4) 5_656 . ?
 N1A Mn1 N1A 74.4(3) 3_665 5_656 ?
 N1A Mn1 N1A 93.8(2) 3_665 . ?
 N1A Mn1 N1A 93.8(2) 6_556 5_656 ?
 N1A Mn1 N1A 93.8(2) 6_556 4_666 ?
 N1A Mn1 N1A 93.8(2) 3_665 2_655 ?
 N1A Mn1 N1A 100.7(4) 2_655 4_666 ?
 N1A Mn1 N1A 74.4(3) 6_556 2_655 ?
 N1A Mn1 N1A 161.8(3) 6_556 . ?
 N1A Mn1 N1A 161.8(3) 5_656 2_655 ?
 N1A Mn1 N1A 93.8(2) 2_655 . ?
 N1A Mn1 N1A 161.8(3) 3_665 4_666 ?
 N1A Mn1 N1A 74.4(3) 4_666 . ?
 Cl1 Br2 C2 71.0(6) . . ?
 Br2 Cl1 C2 74.2(6) . . ?
 Mn1 N1A H1A 122.3(5) . . ?
 C1 N1A Mn1 117.6(5) . . ?
 C1 N1A H1A 120.0(7) . . ?
 Mn1 N1B H1B 122.3(5) . . ?
 C1 N1B Mn1 117.6(5) . . ?
 C1 N1B H1B 120.0(7) . . ?
 C1 O1 Mn1 117.6(5) . . ?
 N1A C1 C1 115.2(4) . 4_666 ?
 N1A C1 C2 125.3(7) . . ?
 N1B C1 C1 115.2(4) . 4_666 ?
 N1B C1 C2 125.3(7) . . ?
 O1 C1 C1 115.2(4) . 4_666 ?
 O1 C1 C2 125.3(7) . . ?
 C2 C1 C1 119.4(5) . 4_666 ?
 Cl1 C2 Br2 34.8(4) . . ?
 C1 C2 Br2 117.9(6) 10 . ?
 C1 C2 Br2 117.9(6) . . ?
 C1 C2 Cl1 118.3(5) . . ?
 C1 C2 Cl1 118.3(5) 10 . ?
 C1 C2 C1 120.9(10) 10 . ?
 C5 N2 C3 109.3(12) . . ?
 N2 C3 H3A 108.8 . . ?
 N2 C3 H3B 108.8 . . ?
 H3A C3 H3B 107.7 . . ?
 C4 C3 N2 113.8(11) . . ?
 C4 C3 H3A 108.8 . . ?
 C4 C3 H3B 108.8 . . ?
 C3 C4 H4A 109.5 . . ?
 C3 C4 H4B 109.5 . . ?
 C3 C4 H4C 109.5 . . ?
 H4A C4 H4B 109.5 . . ?
 H4A C4 H4C 109.5 . . ?
 H4B C4 H4C 109.5 . . ?
 N2 C5 H5A 108.8 . . ?
 N2 C5 H5B 108.8 . . ?
 N2 C5 C6 113.9(16) . . ?
 H5A C5 H5B 107.7 . . ?
 C6 C5 H5A 108.8 . . ?
 C6 C5 H5B 108.8 . . ?
 C5 C6 H6A 109.5 . . ?
 C5 C6 H6B 109.5 . . ?
 C5 C6 H6C 109.5 . . ?
 H6A C6 H6B 109.5 . . ?
 H6A C6 H6C 109.5 . . ?
 H6B C6 H6C 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
 Mn1 N1A C1 C1 0.9(11) . . . 4_666 ?
 Mn1 N1A C1 C2 -176.7(8) . . . . ?
 Mn1 N1B C1 C1 0.9(11) . . . 4_666 ?
 Mn1 N1B C1 C2 -176.7(8) . . . . ?
 Mn1 O1 C1 C1 0.9(11) . . . 4_666 ?
 Mn1 O1 C1 C2 -176.7(8) . . . . ?
 Br2 Cl1 C2 C1 99.0(10) . . . . ?
 Br2 Cl1 C2 C1 -99.0(10) . . . 10 ?
 Cl1 Br2 C2 C1 100.3(9) . . . 10 ?
 Cl1 Br2 C2 C1 -100.3(9) . . . . ?
 N1A C1 C2 Br2 24.5(15) . . . . ?
 N1A C1 C2 Cl1 -15.1(16) . . . . ?
 N1A C1 C2 C1 -176.7(7) . . . 10 ?
 N1B C1 C2 Br2 24.5(15) . . . . ?
 N1B C1 C2 Cl1 -15.1(16) . . . . ?
 N1B C1 C2 C1 -176.7(7) . . . 10 ?
 O1 C1 C2 Br2 24.5(15) . . . . ?
 O1 C1 C2 Cl1 -15.1(16) . . . . ?
 O1 C1 C2 C1 -176.7(7) . . . 10 ?
 C1 C1 C2 Br2 -153.0(9) 4_666 . . . ?
 C1 C1 C2 Cl1 167.4(9) 4_666 . . . ?
 C1 C1 C2 C1 5.8(19) 4_666 . . 10 ?
 C3 N2 C5 C6 180.00(3) . . . . ?
 C5 N2 C3 C4 180.00(2) . . . . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.000 0.000 -0.755 674.2 133.2 ?

_olex2_submission_special_instructions  'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_5
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Due to weak diffraction, data is collected to 1.00 A
;
# end Validation Reply Form

data_6
_audit_creation_date               2019-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number       '2016/6'
_audit_contact_author_address      ?
_audit_contact_author_email        ?
_audit_contact_author_name         ''
_audit_contact_author_phone        ?
_publ_contact_author_id_orcid      ?
_publ_section_references
;
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. (2008). Acta Cryst. A64, 112-122.

Sheldrick, G.M. (2015). Acta Cryst. A71, 3-8.
;
_chemical_name_common              ?
_chemical_name_systematic          ?
_chemical_formula_moiety           'C18 H3 Cl6 Mn2 N3 O9, 2(C8 H20 N1)'
_chemical_formula_sum              'C34 H43 Cl6 Mn2 N5 O9'
_chemical_formula_weight           988.35
_chemical_melting_point            ?
loop_
  _atom_type_symbol
  _atom_type_description
  _atom_type_scat_dispersion_real
  _atom_type_scat_dispersion_imag
  _atom_type_scat_source
 'C' 'C' 0.0181 0.0091 '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'
 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Mn' 'Mn' -0.5299 2.8052
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N' 'N' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system        'trigonal'
_space_group_IT_number             162
_space_group_name_H-M_alt          'P -3 1 m'
_space_group_name_Hall             '-P 3 2'
loop_
  _space_group_symop_operation_xyz
 'x, y, z'
 '-y, x-y, z'
 '-x+y, -x, z'
 '-y, -x, -z'
 '-x+y, y, -z'
 'x, x-y, -z'
 '-x, -y, -z'
 'y, -x+y, -z'
 'x-y, x, -z'
 'y, x, z'
 'x-y, -y, z'
 '-x, -x+y, z'

_cell_length_a                     14.1380(11)
_cell_length_b                     14.1380(11)
_cell_length_c                     10.1420(12)
_cell_angle_alpha                  90
_cell_angle_beta                   90
_cell_angle_gamma                  120
_cell_volume                       1755.6(3)
_cell_formula_units_Z              0.99996
_cell_measurement_reflns_used      2790
_cell_measurement_temperature      100(2)
_cell_measurement_theta_max        51.35
_cell_measurement_theta_min        3.61
_shelx_estimated_absorpt_T_max     0.563
_shelx_estimated_absorpt_T_min     0.261
_exptl_absorpt_coefficient_mu      5.316
_exptl_absorpt_correction_T_max    0.7511
_exptl_absorpt_correction_T_min    0.5093
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details    
 'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1413 before and 0.0970 after correction. The Ratio of minimum to maximum transmission is 0.6781. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details     ?
_exptl_crystal_colour              brown
_exptl_crystal_colour_primary      brown
_exptl_crystal_density_diffrn      0.935
_exptl_crystal_density_meas        ?
_exptl_crystal_density_method      ?
_exptl_crystal_description         hexagonal
_exptl_crystal_F_000               506
_exptl_crystal_size_max            0.346
_exptl_crystal_size_mid            0.307
_exptl_crystal_size_min            0.122
_exptl_transmission_factor_max     ?
_exptl_transmission_factor_min     ?
_diffrn_reflns_av_R_equivalents    0.0930
_diffrn_reflns_av_unetI/netI       0.0400
_diffrn_reflns_Laue_measured_fraction_full  0.995
_diffrn_reflns_Laue_measured_fraction_max  0.995
_diffrn_reflns_limit_h_max         12
_diffrn_reflns_limit_h_min         -9
_diffrn_reflns_limit_k_max         9
_diffrn_reflns_limit_k_min         -13
_diffrn_reflns_limit_l_max         9
_diffrn_reflns_limit_l_min         -9
_diffrn_reflns_number              7061
_diffrn_reflns_point_group_measured_fraction_full  0.995
_diffrn_reflns_point_group_measured_fraction_max  0.995
_diffrn_reflns_theta_full          47.110
_diffrn_reflns_theta_max           47.110
_diffrn_reflns_theta_min           5.664
_diffrn_ambient_temperature        99.99
_diffrn_detector_area_resol_mean   ?
_diffrn_measured_fraction_theta_full  0.995
_diffrn_measured_fraction_theta_max  0.995
_diffrn_measurement_device_type    'Bruker APEX-II CCD'
_diffrn_measurement_method         'φ and ω scans'
_diffrn_radiation_type             CuK\a
_diffrn_radiation_wavelength       1.54178
_diffrn_source                     ?
_diffrn_standards_number           0
_reflns_Friedel_coverage           0.000
_reflns_Friedel_fraction_full      .
_reflns_Friedel_fraction_max       .
_reflns_number_gt                  402
_reflns_number_total               589
_reflns_special_details
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;
_reflns_threshold_expression       'I > 2σ(I)'
_computing_cell_refinement         'SAINT V8.38A (?, 2016)'
_computing_data_collection         ?
_computing_data_reduction          'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics      'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material    'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement    'XL (Sheldrick, 2008)'
_computing_structure_solution      'XT (Sheldrick, 2015)'
_refine_diff_density_max           2.102
_refine_diff_density_min           -0.548
_refine_diff_density_rms           0.193
_refine_ls_extinction_coef         .
_refine_ls_extinction_method       none
_refine_ls_goodness_of_fit_ref     1.841
_refine_ls_hydrogen_treatment      constr
_refine_ls_matrix_type             full
_refine_ls_number_parameters       38
_refine_ls_number_reflns           589
_refine_ls_number_restraints       12
_refine_ls_R_factor_all            0.1924
_refine_ls_R_factor_gt             0.1680
_refine_ls_restrained_S_all        1.857
_refine_ls_shift/su_max            0.000
_refine_ls_shift/su_mean           0.000
_refine_ls_structure_factor_coef   Fsqd
_refine_ls_weighting_details      
 'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme        calc
_refine_ls_wR_factor_gt            0.4226
_refine_ls_wR_factor_ref           0.4455
_refine_special_details            ?
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{O1, N1}
3. Restrained distances
 N2-C3
 1.56 with sigma of 0.01
 C4-C3
 1.54 with sigma of 0.01
 C5-C3
 2.58 with sigma of 0.01
 N2-C3 \\sim N2-C5
 with sigma of 0.01
 N2-C4 \\sim N2-C6
 with sigma of 0.01
 C3-C6 \\sim C5-C4
 with sigma of 0.01
4. Restrained planarity
 N2, C3, C4, C5, C6
 with sigma of 0.001
5. Rigid bond restraints
 N2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(O1) = Uanis(N1)
7. Others
 Fixed Sof: O1(0.75) N1(0.25) H1(0.25) C3(0.33333) H3A(0.33333) H3B(0.33333)
 C4(0.33333) H4A(0.33333) H4B(0.33333) H4C(0.33333) C5(0.33333) H5A(0.33333)
 H5B(0.33333) C6(0.33333) H6A(0.33333) H6B(0.33333) H6C(0.33333)
 Fixed X: N2(0.33333) C3(0.414129) C4(0.48782) C5(0.2637) C6(0.18047)
 Fixed Y: N2(0.66667) C3(0.689429) C4(0.63877) C5(0.72121) C6(0.70404)
 Fixed Z: N2(0.5) C3(0.61843) C4(0.59899) C5(0.53029) C6(0.419499)
8.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C)
8.c Aromatic/amide H refined with riding coordinates:
 N1(H1)
;
_atom_sites_solution_hydrogens     geom
_atom_sites_solution_primary       dual
_atom_sites_solution_secondary     ?
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
 Mn1 Mn 0.333333 0.666667 1.000000 0.096(3) Uani 1 6 d S T P . .
 Cl1 Cl 0.000000 0.3761(5) 0.7399(6) 0.125(3) Uani 1 2 d S T P . .
 O1 O 0.1926(8) 0.5476(8) 0.8914(9) 0.093(4) Uani 0.75 1 d . . . . .
 N1 N 0.1926(8) 0.5476(8) 0.8914(9) 0.093(4) Uani 0.25 1 d . . . . .
 H1 H 0.200066 0.517836 0.818847 0.112 Uiso 0.25 1 calc R . . . .
 C1 C 0.000000 0.4415(13) 0.880(2) 0.088(6) Uani 1 2 d S T P . .
 C2 C 0.0978(12) 0.5214(11) 0.9358(14) 0.087(4) Uani 1 1 d . . . . .
 N2 N 0.333330 0.666670 0.500000 0.49(5) Uiso 0.1667 1 d DS TU P A -1
 C3 C 0.414129 0.689429 0.618430 0.49(5) Uiso 0.3333 1 d D U . A -1
 H3A H 0.460888 0.769352 0.629793 0.585 Uiso 0.3333 1 calc R . . A -1
 H3B H 0.371130 0.659721 0.700301 0.585 Uiso 0.3333 1 calc R . . A -1
 C4 C 0.487820 0.638770 0.598990 0.50(6) Uiso 0.3333 1 d D U . A -1
 H4A H 0.535970 0.655674 0.675528 0.747 Uiso 0.3333 1 calc R . . A -1
 H4B H 0.442220 0.559383 0.589832 0.747 Uiso 0.3333 1 calc R . . A -1
 H4C H 0.532046 0.669097 0.519271 0.747 Uiso 0.3333 1 calc R . . A -1
 C5 C 0.263700 0.721210 0.530290 0.49(5) Uiso 0.3333 1 d D U . A -1
 H5A H 0.313208 0.800542 0.543251 0.594 Uiso 0.3333 1 calc R . . A -1
 H5B H 0.223456 0.690913 0.613756 0.594 Uiso 0.3333 1 calc R . . A -1
 C6 C 0.180470 0.704040 0.419499 0.51(5) Uiso 0.3333 1 d D U . A -1
 H6A H 0.139288 0.740160 0.444307 0.763 Uiso 0.3333 1 calc R . . A -1
 H6B H 0.219758 0.735429 0.336921 0.763 Uiso 0.3333 1 calc R . . A -1
 H6C H 0.129935 0.625714 0.407483 0.763 Uiso 0.3333 1 calc R . . A -1


_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
 Mn1 O1 2.158(10) 6_567 ?
 Mn1 O1 2.158(10) 2_665 ?
 Mn1 O1 2.158(10) . ?
 Mn1 O1 2.158(10) 3_565 ?
 Mn1 O1 2.158(10) 4_667 ?
 Mn1 O1 2.158(10) 5_557 ?
 Cl1 C1 1.70(2) . ?
 O1 C2 1.280(14) . ?
 C1 C2 1.395(16) 12 ?
 C1 C2 1.395(16) . ?
 C2 C2 1.52(3) 6_567 ?
 N2 C3 1.57594(12) . ?
 N2 C5 1.55471(12) . ?
 C3 H3A 0.9900 . ?
 C3 H3B 0.9900 . ?
 C3 C4 1.54384(12) . ?
 C4 H4A 0.9800 . ?
 C4 H4B 0.9800 . ?
 C4 H4C 0.9800 . ?
 C5 H5A 0.9900 . ?
 C5 H5B 0.9900 . ?
 C5 C6 1.55579(11) . ?
 C6 H6A 0.9800 . ?
 C6 H6B 0.9800 . ?
 C6 H6C 0.9800 . ?

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
 O1 Mn1 O1 95.0(5) 6_567 3_565 ?
 O1 Mn1 O1 95.0(5) 4_667 2_665 ?
 O1 Mn1 O1 95.0(5) . 5_557 ?
 O1 Mn1 O1 96.3(3) 6_567 4_667 ?
 O1 Mn1 O1 96.3(4) 6_567 5_557 ?
 O1 Mn1 O1 74.0(5) 3_565 4_667 ?
 O1 Mn1 O1 96.3(4) 3_565 2_665 ?
 O1 Mn1 O1 74.0(5) 6_567 . ?
 O1 Mn1 O1 96.3(3) . 2_665 ?
 O1 Mn1 O1 96.3(3) 3_565 . ?
 O1 Mn1 O1 165.9(5) 3_565 5_557 ?
 O1 Mn1 O1 165.9(5) 4_667 . ?
 O1 Mn1 O1 74.0(5) 2_665 5_557 ?
 O1 Mn1 O1 165.9(5) 6_567 2_665 ?
 O1 Mn1 O1 96.3(3) 4_667 5_557 ?
 C2 O1 Mn1 118.0(8) . . ?
 C2 C1 Cl1 120.7(9) 12 . ?
 C2 C1 Cl1 120.7(9) . . ?
 C2 C1 C2 118.3(18) . 12 ?
 O1 C2 C1 124.2(12) . . ?
 O1 C2 C2 115.0(7) . 6_567 ?
 C1 C2 C2 120.6(9) . 6_567 ?
 C5 N2 C3 108.797(4) . . ?
 N2 C3 H3A 108.9 . . ?
 N2 C3 H3B 108.9 . . ?
 H3A C3 H3B 107.7 . . ?
 C4 C3 N2 113.350(4) . . ?
 C4 C3 H3A 108.9 . . ?
 C4 C3 H3B 108.9 . . ?
 C3 C4 H4A 109.5 . . ?
 C3 C4 H4B 109.5 . . ?
 C3 C4 H4C 109.5 . . ?
 H4A C4 H4B 109.5 . . ?
 H4A C4 H4C 109.5 . . ?
 H4B C4 H4C 109.5 . . ?
 N2 C5 H5A 108.9 . . ?
 N2 C5 H5B 108.9 . . ?
 N2 C5 C6 113.389(4) . . ?
 H5A C5 H5B 107.7 . . ?
 C6 C5 H5A 108.9 . . ?
 C6 C5 H5B 108.9 . . ?
 C5 C6 H6A 109.5 . . ?
 C5 C6 H6B 109.5 . . ?
 C5 C6 H6C 109.5 . . ?
 H6A C6 H6B 109.5 . . ?
 H6A C6 H6C 109.5 . . ?
 H6B C6 H6C 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
 Mn1 O1 C2 C1 -176.3(12) . . . . ?
 Mn1 O1 C2 C2 -2(2) . . . 6_567 ?
 Cl1 C1 C2 O1 -4(2) . . . . ?
 Cl1 C1 C2 C2 -177.4(14) . . . 6_567 ?
 C2 C1 C2 O1 -177.9(10) 12 . . . ?
 C2 C1 C2 C2 8(3) 12 . . 6_567 ?
 C3 N2 C5 C6 180.0 . . . . ?
 C5 N2 C3 C4 180.0 . . . . ?

_smtbx_masks_special_details       ?
loop_
  _smtbx_masks_void_nr
  _smtbx_masks_void_average_x
  _smtbx_masks_void_average_y
  _smtbx_masks_void_average_z
  _smtbx_masks_void_volume
  _smtbx_masks_void_count_electrons
  _smtbx_masks_void_content
 1 0.000 0.000 -0.554 761.9 430.3 ?

_olex2_submission_special_instructions  'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_6
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Due to weak diffraction, data is collected to 1.05 A
;
# end Validation Reply Form