# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_5_al_Zn3Bi2SCN12_C2c
_database_code_depnum_ccdc_archive 'CCDC 1986920'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2018-04-20
_audit_creation_method           
;
Olex2 1.2
(compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5337)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        'zinc(II) hexathiocyantosbismuthate(III)'
_chemical_formula_moiety         'C12 Bi2 N12 S12 Zn3'
_chemical_formula_sum            'C12 Bi2 N12 S12 Zn3'
_chemical_formula_weight         1311.03
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 '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'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   26.3104(4)
_cell_length_b                   8.45870(10)
_cell_length_c                   15.7403(3)
_cell_angle_alpha                90
_cell_angle_beta                 93.6300(10)
_cell_angle_gamma                90
_cell_volume                     3496.00(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    109
_cell_measurement_reflns_used    4170
_cell_measurement_theta_min      0.998
_cell_measurement_theta_max      27.485
_exptl_absorpt_coefficient_mu    12.807
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.55
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.491
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2416
_exptl_crystal_preparation       'precipitated from solution'
_exptl_crystal_recrystallization_method ?
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            7507
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.505
_diffrn_reflns_theta_min         3.538
_diffrn_ambient_temperature      109
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ω/2θ
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3471
_reflns_number_total             3975
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.161
_refine_diff_density_min         -1.545
_refine_diff_density_rms         0.166
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     189
_refine_ls_number_reflns         3975
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0259
_refine_ls_restrained_S_all      1.067
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0238P)²+15.7967P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0568
_refine_ls_wR_factor_ref         0.0596
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_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
Bi2 Bi 0.5000 0.5000 0.5000 0.01540(7) Uani 1 2 d S T P . .
Bi1 Bi 0.7500 -0.2500 0.5000 0.01738(7) Uani 1 2 d S T P . .
Zn1 Zn 0.67431(2) 0.25886(6) 0.31517(3) 0.01643(11) Uani 1 1 d . . . . .
Zn2 Zn 0.5000 1.01523(8) 0.2500 0.02196(16) Uani 1 2 d S T P . .
S2 S 0.70895(5) 0.80357(13) 0.33035(7) 0.0231(2) Uani 1 1 d . . . . .
S1 S 0.81435(4) 0.00871(14) 0.46789(7) 0.0245(2) Uani 1 1 d . . . . .
S3 S 0.54049(4) 0.18947(13) 0.50105(7) 0.0238(2) Uani 1 1 d . . . . .
S4 S 0.67417(5) 0.02959(15) 0.04183(7) 0.0299(3) Uani 1 1 d . . . . .
S6 S 0.56219(5) 1.48483(15) 0.15328(8) 0.0292(3) Uani 1 1 d . . . . .
S5 S 0.58429(5) 0.62431(17) 0.42073(10) 0.0411(4) Uani 1 1 d . . . . .
N2 N 0.68707(15) 0.4837(4) 0.2984(2) 0.0216(8) Uani 1 1 d . . . . .
N1 N 0.73411(14) 0.1720(4) 0.3811(2) 0.0212(8) Uani 1 1 d . . . . .
N5 N 0.53844(16) 0.8732(5) 0.3287(2) 0.0283(9) Uani 1 1 d . . . . .
N4 N 0.66693(14) 0.1485(4) 0.2062(2) 0.0206(8) Uani 1 1 d . . . . .
N3 N 0.61430(14) 0.2272(4) 0.3817(2) 0.0206(8) Uani 1 1 d . . . . .
N6 N 0.54206(16) 1.1675(5) 0.1912(3) 0.0314(10) Uani 1 1 d . . . . .
C1 C 0.76720(17) 0.1069(5) 0.4169(3) 0.0191(9) Uani 1 1 d . . . . .
C5 C 0.55710(17) 0.7693(5) 0.3668(3) 0.0214(9) Uani 1 1 d . . . . .
C6 C 0.55006(18) 1.2981(6) 0.1751(3) 0.0272(11) Uani 1 1 d . . . . .
C4 C 0.66975(16) 0.0993(5) 0.1387(3) 0.0196(9) Uani 1 1 d . . . . .
C2 C 0.69649(16) 0.6154(5) 0.3116(3) 0.0188(9) Uani 1 1 d . . . . .
C3 C 0.58395(18) 0.2136(5) 0.4308(3) 0.0196(9) Uani 1 1 d . . . . .


_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
Bi2 S3 2.8341(11) . ?
Bi2 S3 2.8341(11) 5_666 ?
Bi2 S6 2.8310(12) 6_576 ?
Bi2 S6 2.8310(12) 2_645 ?
Bi2 S5 2.8161(12) . ?
Bi2 S5 2.8161(12) 5_666 ?
Bi1 S2 2.8525(11) 7_656 ?
Bi1 S2 2.8525(11) 1_545 ?
Bi1 S1 2.8320(12) 7_646 ?
Bi1 S1 2.8319(12) . ?
Bi1 S4 2.8383(12) 4_645 ?
Bi1 S4 2.8383(12) 6_556 ?
Zn1 N2 1.952(4) . ?
Zn1 N1 1.971(4) . ?
Zn1 N4 1.952(4) . ?
Zn1 N3 1.968(4) . ?
Zn2 N5 1.961(4) 2_655 ?
Zn2 N5 1.961(4) . ?
Zn2 N6 1.968(4) . ?
Zn2 N6 1.968(4) 2_655 ?
S2 Bi1 2.8526(11) 1_565 ?
S2 C2 1.648(5) . ?
S1 C1 1.658(5) . ?
S3 C3 1.653(5) . ?
S4 Bi1 2.8383(12) 4_655 ?
S4 C4 1.646(4) . ?
S6 Bi2 2.8310(12) 2_665 ?
S6 C6 1.652(5) . ?
S5 C5 1.631(5) . ?
N2 C2 1.157(6) . ?
N1 C1 1.147(6) . ?
N5 C5 1.155(6) . ?
N4 C4 1.147(5) . ?
N3 C3 1.151(6) . ?
N6 C6 1.155(7) . ?

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
S3 Bi2 S3 180.0 . 5_666 ?
S6 Bi2 S3 80.81(3) 2_645 5_666 ?
S6 Bi2 S3 80.81(3) 6_576 . ?
S6 Bi2 S3 99.19(3) 6_576 5_666 ?
S6 Bi2 S3 99.19(3) 2_645 . ?
S6 Bi2 S6 180.0 6_576 2_645 ?
S5 Bi2 S3 92.43(4) . . ?
S5 Bi2 S3 92.43(4) 5_666 5_666 ?
S5 Bi2 S3 87.57(4) 5_666 . ?
S5 Bi2 S3 87.57(4) . 5_666 ?
S5 Bi2 S6 93.91(4) . 2_645 ?
S5 Bi2 S6 86.09(4) . 6_576 ?
S5 Bi2 S6 93.91(4) 5_666 6_576 ?
S5 Bi2 S6 86.09(4) 5_666 2_645 ?
S5 Bi2 S5 180.00(6) 5_666 . ?
S2 Bi1 S2 180.0 7_656 1_545 ?
S1 Bi1 S2 95.43(3) 7_646 1_545 ?
S1 Bi1 S2 84.57(3) 7_646 7_656 ?
S1 Bi1 S2 84.57(3) . 1_545 ?
S1 Bi1 S2 95.43(3) . 7_656 ?
S1 Bi1 S1 180.0 . 7_646 ?
S1 Bi1 S4 91.67(4) 7_646 6_556 ?
S1 Bi1 S4 91.67(4) . 4_645 ?
S1 Bi1 S4 88.33(4) 7_646 4_645 ?
S1 Bi1 S4 88.33(4) . 6_556 ?
S4 Bi1 S2 96.73(3) 4_645 1_545 ?
S4 Bi1 S2 83.27(3) 4_645 7_656 ?
S4 Bi1 S2 96.73(3) 6_556 7_656 ?
S4 Bi1 S2 83.27(3) 6_556 1_545 ?
S4 Bi1 S4 180.00(4) 6_556 4_645 ?
N2 Zn1 N1 107.21(16) . . ?
N2 Zn1 N3 110.81(15) . . ?
N4 Zn1 N2 110.81(15) . . ?
N4 Zn1 N1 108.44(15) . . ?
N4 Zn1 N3 111.37(15) . . ?
N3 Zn1 N1 108.03(15) . . ?
N5 Zn2 N5 104.4(2) 2_655 . ?
N5 Zn2 N6 112.76(17) . 2_655 ?
N5 Zn2 N6 114.57(17) 2_655 2_655 ?
N5 Zn2 N6 112.76(17) 2_655 . ?
N5 Zn2 N6 114.57(17) . . ?
N6 Zn2 N6 98.2(3) . 2_655 ?
C2 S2 Bi1 94.21(15) . 1_565 ?
C1 S1 Bi1 92.07(15) . . ?
C3 S3 Bi2 99.07(16) . . ?
C4 S4 Bi1 94.12(16) . 4_655 ?
C6 S6 Bi2 96.40(17) . 2_665 ?
C5 S5 Bi2 100.36(16) . . ?
C2 N2 Zn1 161.8(3) . . ?
C1 N1 Zn1 173.2(4) . . ?
C5 N5 Zn2 168.3(4) . . ?
C4 N4 Zn1 168.1(4) . . ?
C3 N3 Zn1 170.0(4) . . ?
C6 N6 Zn2 147.6(4) . . ?
N1 C1 S1 178.6(4) . . ?
N5 C5 S5 179.1(5) . . ?
N6 C6 S6 179.1(5) . . ?
N4 C4 S4 179.5(5) . . ?
N2 C2 S2 179.1(4) . . ?
N3 C3 S3 178.7(4) . . ?

_olex2_submission_special_instructions 'No special instructions were received'

#==============================================================================
# start Validation Reply Forms
#==============================================================================

_vrf_PLAT241_ALERT_2_C           
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of         S5 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to.
;

_vrf_PLAT242_ALERT_2_C           
;
PROBLEM:  Low    'MainMol' Ueq as Compared to Neighbors of        Bi2 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to.
;

_vrf_PLAT910_ALERT_3_C           
;
PROBLEM: Missing # of FCF Reflection(s) Below Theta(Min).          9 Note 
RESPONSE: These are low angle reflection obscured by the beam stop
;

#==============================================================================
#==============================================================================

# end Validation Reply Forms

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_6_be_Zn3Bi2SCN12_P21c
_database_code_depnum_ccdc_archive 'CCDC 1986921'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2018-05-25
_audit_creation_method           
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5497)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        'zinc hexathiocyanatobismuthate'
_chemical_formula_moiety         'Bi2 C12 N12 S12 Zn3'
_chemical_formula_sum            'C12 Bi2 N12 S12 Zn3'
_chemical_formula_weight         1311.03
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 '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'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   17.7331(6)
_cell_length_b                   13.6501(4)
_cell_length_c                   16.4375(4)
_cell_angle_alpha                90
_cell_angle_beta                 114.3971(12)
_cell_angle_gamma                90.00
_cell_volume                     3623.55(19)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    5894
_cell_measurement_temperature    180
_cell_measurement_theta_max      27.485
_cell_measurement_theta_min      0.998
_shelx_estimated_absorpt_T_max   0.790
_shelx_estimated_absorpt_T_min   0.191
_exptl_absorpt_coefficient_mu    12.357
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.544
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.403
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2416
_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method ?
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_exptl_special_details           
;
?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0697
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            12934
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.451
_diffrn_reflns_theta_min         2.061
_diffrn_ambient_temperature      180
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ω/2θ
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      -0.01477
_diffrn_orient_matrix_UB_12      -0.00672
_diffrn_orient_matrix_UB_13      0.06480
_diffrn_orient_matrix_UB_21      -0.05024
_diffrn_orient_matrix_UB_22      -0.05064
_diffrn_orient_matrix_UB_23      -0.01671
_diffrn_orient_matrix_UB_31      0.03345
_diffrn_orient_matrix_UB_32      -0.04293
_diffrn_orient_matrix_UB_33      0.02954
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  all
_diffrn_source                   'fine-focus sealed tube'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5919
_reflns_number_total             7822
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction        'Denzo and Scalepak (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.670
_refine_diff_density_min         -2.363
_refine_diff_density_rms         0.249
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     370
_refine_ls_number_reflns         7822
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0507
_refine_ls_restrained_S_all      1.046
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0521P)²+19.2509P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1206
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_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
Bi1 Bi 0.07918(2) 0.83822(2) 0.31715(2) 0.02589(11) Uani 1 1 d . . . . .
Bi2 Bi 0.60802(2) 0.68925(3) 0.61231(2) 0.02773(11) Uani 1 1 d . . . . .
Zn1 Zn 0.39202(7) 0.87617(8) 0.27339(7) 0.0292(2) Uani 1 1 d . . . . .
Zn2 Zn 0.84944(7) 0.83929(7) 0.46262(7) 0.0285(2) Uani 1 1 d . . . . .
Zn3 Zn 0.82080(7) 0.48486(8) 0.45414(7) 0.0312(3) Uani 1 1 d . . . . .
S9 S 0.80970(16) 0.49471(19) 0.16216(16) 0.0350(6) Uani 1 1 d . . . . .
S8 S 1.03785(17) 0.68985(19) 0.63420(17) 0.0366(6) Uani 1 1 d . . . . .
S11 S 1.05032(16) 1.02954(18) 0.69093(17) 0.0361(6) Uani 1 1 d . . . . .
S10 S 0.98691(18) 0.66894(18) 0.31328(19) 0.0384(6) Uani 1 1 d . . . . .
S1 S 0.18895(19) 0.68819(19) 0.3208(2) 0.0443(7) Uani 1 1 d . . . . .
S7 S 0.8519(2) 0.14190(19) 0.49418(18) 0.0484(8) Uani 1 1 d . . . . .
S4 S 0.63277(18) 0.8651(2) 0.54394(18) 0.0458(7) Uani 1 1 d . . . . .
S6 S 0.56307(17) 0.5816(2) 0.45264(18) 0.0424(7) Uani 1 1 d . . . . .
S5 S 0.77955(19) 0.6650(3) 0.67146(19) 0.0524(8) Uani 1 1 d . . . . .
S3 S 0.43396(19) 0.7763(3) 0.01964(19) 0.0522(8) Uani 1 1 d . . . . .
S2 S 0.3762(3) 1.2189(2) 0.22782(19) 0.0560(9) Uani 1 1 d . . . . .
S12 S 0.6222(2) 0.9826(2) 0.2233(2) 0.0575(9) Uani 1 1 d . . . . .
N7 N 0.8210(6) 0.3415(6) 0.4665(6) 0.041(2) Uani 1 1 d . . . . .
N11 N 0.9364(5) 0.9240(6) 0.5461(5) 0.0335(19) Uani 1 1 d . . . . .
N1 N 0.3029(5) 0.8028(6) 0.2864(6) 0.036(2) Uani 1 1 d . . . . .
N12 N 0.7593(6) 0.9127(6) 0.3727(6) 0.043(2) Uani 1 1 d . . . . .
N4 N 0.4951(6) 0.8539(7) 0.3806(6) 0.043(2) Uani 1 1 d . . . . .
N5 N 0.8100(5) 0.7610(6) 0.5383(6) 0.0336(19) Uani 1 1 d . . . . .
N2 N 0.3800(5) 1.0198(6) 0.2656(5) 0.037(2) Uani 1 1 d . . . . .
N9 N 0.8228(5) 0.5104(5) 0.3374(5) 0.0331(19) Uani 1 1 d . . . . .
N3 N 0.4032(5) 0.8323(6) 0.1666(6) 0.037(2) Uani 1 1 d . . . . .
C7 C 0.8330(6) 0.2590(7) 0.4785(6) 0.029(2) Uani 1 1 d . . . . .
N6 N 0.7182(6) 0.5326(6) 0.4601(5) 0.0349(19) Uani 1 1 d . . . . .
C9 C 0.8181(6) 0.5030(6) 0.2650(6) 0.027(2) Uani 1 1 d . . . . .
C11 C 0.9844(5) 0.9685(6) 0.6066(6) 0.0221(18) Uani 1 1 d . . . . .
N10 N 0.9005(6) 0.7520(6) 0.4054(5) 0.037(2) Uani 1 1 d . . . . .
N8 N 0.9177(6) 0.5487(7) 0.5457(6) 0.040(2) Uani 1 1 d . . . . .
C10 C 0.9359(6) 0.7181(7) 0.3680(6) 0.027(2) Uani 1 1 d . . . . .
C1 C 0.2561(6) 0.7562(7) 0.3005(6) 0.031(2) Uani 1 1 d . . . . .
C8 C 0.9677(7) 0.6054(7) 0.5843(7) 0.035(2) Uani 1 1 d . . . . .
C4 C 0.5509(6) 0.8582(7) 0.4466(7) 0.032(2) Uani 1 1 d . . . . .
C2 C 0.3784(7) 1.1018(8) 0.2517(6) 0.033(2) Uani 1 1 d . . . . .
C12 C 0.7031(7) 0.9410(7) 0.3101(7) 0.039(2) Uani 1 1 d . . . . .
C3 C 0.4153(7) 0.8090(8) 0.1066(7) 0.039(2) Uani 1 1 d . . . . .
C5 C 0.7969(6) 0.7222(7) 0.5923(7) 0.034(2) Uani 1 1 d . . . . .
C6 C 0.6541(7) 0.5525(7) 0.4573(6) 0.032(2) Uani 1 1 d . . . . .


_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
Bi1 S9 2.830(2) 2_655 ?
Bi1 S8 2.812(2) 4_475 ?
Bi1 S11 2.881(3) 3_676 ?
Bi1 S10 2.817(2) 1_455 ?
Bi1 S1 2.809(3) . ?
Bi1 S7 2.838(3) 3_666 ?
Bi2 S4 2.762(3) . ?
Bi2 S6 2.820(3) . ?
Bi2 S5 2.804(3) . ?
Bi2 S3 2.861(3) 4_576 ?
Bi2 S2 2.819(3) 3_676 ?
Bi2 S12 2.917(3) 4_576 ?
Zn1 N1 1.956(9) . ?
Zn1 N4 1.969(10) . ?
Zn1 N2 1.971(9) . ?
Zn1 N3 1.940(8) . ?
Zn2 N11 1.962(9) . ?
Zn2 N12 1.947(10) . ?
Zn2 N5 1.973(8) . ?
Zn2 N10 1.957(8) . ?
Zn3 N7 1.967(8) . ?
Zn3 N9 1.965(8) . ?
Zn3 N6 1.973(9) . ?
Zn3 N8 1.959(10) . ?
S9 Bi1 2.830(2) 2_645 ?
S9 C9 1.638(9) . ?
S8 Bi1 2.812(2) 4_676 ?
S8 C8 1.646(12) . ?
S11 Bi1 2.881(3) 3_676 ?
S11 C11 1.626(9) . ?
S10 Bi1 2.817(2) 1_655 ?
S10 C10 1.658(9) . ?
S1 C1 1.649(10) . ?
S7 Bi1 2.838(3) 3_666 ?
S7 C7 1.632(9) . ?
S4 C4 1.661(11) . ?
S6 C6 1.634(11) . ?
S5 C5 1.652(11) . ?
S3 Bi2 2.861(3) 4_575 ?
S3 C3 1.656(10) . ?
S2 Bi2 2.819(3) 3_676 ?
S2 C2 1.643(11) . ?
S12 Bi2 2.917(3) 4_575 ?
S12 C12 1.651(12) . ?
N7 C7 1.148(12) . ?
N11 C11 1.177(11) . ?
N1 C1 1.143(12) . ?
N12 C12 1.163(14) . ?
N4 C4 1.128(13) . ?
N5 C5 1.138(12) . ?
N2 C2 1.139(12) . ?
N9 C9 1.163(11) . ?
N3 C3 1.138(12) . ?
N6 C6 1.151(12) . ?
N10 C10 1.142(11) . ?
N8 C8 1.150(13) . ?

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
S9 Bi1 S11 91.99(8) 2_655 3_676 ?
S9 Bi1 S7 80.35(8) 2_655 3_666 ?
S8 Bi1 S9 95.30(7) 4_475 2_655 ?
S8 Bi1 S11 100.68(8) 4_475 3_676 ?
S8 Bi1 S10 88.38(8) 4_475 1_455 ?
S8 Bi1 S7 170.43(9) 4_475 3_666 ?
S10 Bi1 S9 172.35(8) 1_455 2_655 ?
S10 Bi1 S11 93.92(7) 1_455 3_676 ?
S10 Bi1 S7 95.00(8) 1_455 3_666 ?
S1 Bi1 S9 96.07(8) . 2_655 ?
S1 Bi1 S8 78.22(9) . 4_475 ?
S1 Bi1 S11 171.92(8) . 3_676 ?
S1 Bi1 S10 78.08(8) . 1_455 ?
S1 Bi1 S7 93.70(9) . 3_666 ?
S7 Bi1 S11 88.04(8) 3_666 3_676 ?
S4 Bi2 S6 96.06(9) . . ?
S4 Bi2 S5 84.93(9) . . ?
S4 Bi2 S3 87.62(9) . 4_576 ?
S4 Bi2 S2 91.22(9) . 3_676 ?
S4 Bi2 S12 165.03(9) . 4_576 ?
S6 Bi2 S3 76.23(9) . 4_576 ?
S6 Bi2 S12 94.66(9) . 4_576 ?
S5 Bi2 S6 96.34(9) . . ?
S5 Bi2 S3 168.88(7) . 4_576 ?
S5 Bi2 S2 93.06(11) . 3_676 ?
S5 Bi2 S12 83.52(9) . 4_576 ?
S3 Bi2 S12 105.10(9) 4_576 4_576 ?
S2 Bi2 S6 168.57(10) 3_676 . ?
S2 Bi2 S3 95.34(10) 3_676 4_576 ?
S2 Bi2 S12 79.93(9) 3_676 4_576 ?
N1 Zn1 N4 108.4(4) . . ?
N1 Zn1 N2 116.4(4) . . ?
N4 Zn1 N2 104.3(4) . . ?
N3 Zn1 N1 109.3(4) . . ?
N3 Zn1 N4 111.0(4) . . ?
N3 Zn1 N2 107.3(3) . . ?
N11 Zn2 N5 105.0(3) . . ?
N12 Zn2 N11 112.9(4) . . ?
N12 Zn2 N5 111.3(4) . . ?
N12 Zn2 N10 110.2(4) . . ?
N10 Zn2 N11 108.0(3) . . ?
N10 Zn2 N5 109.2(3) . . ?
N7 Zn3 N6 106.6(4) . . ?
N9 Zn3 N7 106.1(3) . . ?
N9 Zn3 N6 112.3(3) . . ?
N8 Zn3 N7 113.5(4) . . ?
N8 Zn3 N9 107.9(4) . . ?
N8 Zn3 N6 110.4(3) . . ?
C9 S9 Bi1 99.6(3) . 2_645 ?
C8 S8 Bi1 104.3(3) . 4_676 ?
C11 S11 Bi1 90.2(3) . 3_676 ?
C10 S10 Bi1 95.6(3) . 1_655 ?
C1 S1 Bi1 97.9(3) . . ?
C7 S7 Bi1 92.7(3) . 3_666 ?
C4 S4 Bi2 96.9(3) . . ?
C6 S6 Bi2 100.9(3) . . ?
C5 S5 Bi2 101.5(4) . . ?
C3 S3 Bi2 93.0(4) . 4_575 ?
C2 S2 Bi2 103.1(3) . 3_676 ?
C12 S12 Bi2 94.8(4) . 4_575 ?
C7 N7 Zn3 170.4(9) . . ?
C11 N11 Zn2 168.8(7) . . ?
C1 N1 Zn1 173.9(9) . . ?
C12 N12 Zn2 167.6(8) . . ?
C4 N4 Zn1 166.8(9) . . ?
C5 N5 Zn2 169.7(8) . . ?
C2 N2 Zn1 169.3(8) . . ?
C9 N9 Zn3 164.2(7) . . ?
C3 N3 Zn1 175.2(9) . . ?
N7 C7 S7 178.3(9) . . ?
C6 N6 Zn3 172.7(8) . . ?
N9 C9 S9 178.6(9) . . ?
N11 C11 S11 179.4(8) . . ?
C10 N10 Zn2 166.4(8) . . ?
C8 N8 Zn3 162.7(8) . . ?
N10 C10 S10 179.7(10) . . ?
N1 C1 S1 179.6(9) . . ?
N8 C8 S8 176.8(9) . . ?
N4 C4 S4 179.7(12) . . ?
N2 C2 S2 177.7(9) . . ?
N12 C12 S12 178.3(10) . . ?
N3 C3 S3 179.2(11) . . ?
N5 C5 S5 179.0(9) . . ?
N6 C6 S6 179.5(10) . . ?

_olex2_submission_special_instructions 'No special instructions were received'

#==============================================================================
# start Validation Reply Forms
#==============================================================================
_vrf_PLAT971_ALERT_2_C           
;
PROBLEM: Check Calcd Resid. Dens.  0.93A   From Bi1             1.60 eA-3  
RESPONSE: It is common for residual density to remain near heavy atoms, due to 
fourier termination ripples. The size of the positive and negative ripples are
 less than 3% of the number of electrons on the heaviest atom (Bi) and 
 approximately equal. The low symmetry of the structure means the multi-scan
 absorption correction may not be optimal.
;

_vrf_PLAT972_ALERT_2_C           
;
PROBLEM: Check Calcd Resid. Dens.  0.93A   From Bi1             1.60 eA-3  
		 Check Calcd Resid. Dens.  1.25A   From Bi1            -2.26 eA-3  
		 Check Calcd Resid. Dens.  1.31A   From Bi2            -2.21 eA-3  
		 Check Calcd Resid. Dens.  1.27A   From Bi2            -1.84 eA-3  
		 Check Calcd Resid. Dens.  0.79A   From Bi2            -1.79 eA-3  
		 Check Calcd Resid. Dens.  1.43A   From Bi1            -1.76 eA-3  
		 Check Calcd Resid. Dens.  0.89A   From Bi2            -1.70 eA-3  
		 Check Calcd Resid. Dens.  0.82A   From Bi1            -1.61 eA-3   
		 
RESPONSE: It is common for residual density to remain near heavy atoms, due to 
fourier termination ripples. The size of the positive and negative ripples are
 less than 3% of the number of electrons on the heaviest atom (Bi) and 
 approximately equal. The low symmetry of the structure means the multi-scan
 absorption correction may not be optimal.
;

_vrf_PLAT973_ALERT_2_C           
;
PROBLEM: Check Calcd Positive Resid. Density on       Bi1       1.28 eA-3  
RESPONSE: It is common for residual density to remain near heavy atoms, due to 
fourier termination ripples. The size of the positive and negative ripples are
 less than 3% of the number of electrons on the heaviest atom (Bi) and 
 approximately equal. The low symmetry of the structure means the multi-scan
 absorption correction may not be optimal.	 
;

#==============================================================================
#==============================================================================
_vrf_PLAT242_ALERT_2_C           
;
PROBLEM:  Low    'MainMol' Ueq as Compared to Neighbors of        Bi2 Check 
		Low    'MainMol' Ueq as Compared to Neighbors of         C7 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to, and for 
ends of ligands show more pronounced motion the ends.
;

_vrf_PLAT241_ALERT_2_C           
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of         S1 Check  
		High   'MainMol' Ueq as Compared to Neighbors of         S4 Check 
		High   'MainMol' Ueq as Compared to Neighbors of         S5 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to.
;

#==============================================================================
#==============================================================================

_vrf_PLAT029_ALERT_3_C           
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.978 Why?
RESPONSE: A small fraction of high angle reflections are 
missing as they are weak.
;
_vrf_PLAT911_ALERT_3_C           
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.600        143 Report
RESPONSE: A small fraction of high angle reflections are missing 
as they are weak.
;

#==============================================================================
# end Validation Reply Forms
#==============================================================================

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1a
_database_code_depnum_ccdc_archive 'CCDC 1986925'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
#===============================================================================
_audit_creation_method           SHELXL-2018/1
_chemical_name_systematic        
'manganese hexathiocyanatobismuthate thiocyanate heptahydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C7 H14 Bi Mn2 N7 O7 S7'
_chemical_formula_sum            'C7 H14 Bi Mn2 N7 O7 S7'
_chemical_formula_weight         851.53

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'
Bi Bi -4.0111 8.9310 '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'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   8.3065(2)
_cell_length_b                   25.8428(6)
_cell_length_c                   12.2664(3)
_cell_angle_alpha                90
_cell_angle_beta                 90.2358(13)
_cell_angle_gamma                90
_cell_volume                     2633.12(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    9893
_cell_measurement_theta_min      3.42
_cell_measurement_theta_max      66.59

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.148
_exptl_crystal_F_000             1624
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    26.169
_shelx_estimated_absorpt_T_min   0.121
_shelx_estimated_absorpt_T_max   0.780
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3997
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_process_details   'SADABS (Bruker, 2014)'

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     1.5418
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Incoatec I\mS Cu microsource'
_diffrn_measurement_device_type  'Bruker D8-QUEST PHOTON-100'
_diffrn_measurement_method       'ω and φ-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            33300
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_av_R_equivalents  0.0797
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.420
_diffrn_reflns_theta_max         66.654
_diffrn_reflns_theta_full        66.654
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4657
_reflns_number_gt                3697
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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_data_collection       'APEX3 (Bruker, 2016)'
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_reduction        SAINT
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  SHELXL

_refine_special_details          ?

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0442P)²+9.0260P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4657
_refine_ls_number_parameters     280
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0547
_refine_ls_R_factor_gt           0.0376
_refine_ls_wR_factor_ref         0.0927
_refine_ls_wR_factor_gt          0.0850
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_restrained_S_all      1.024
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         2.364
_refine_diff_density_min         -1.633
_refine_diff_density_rms         0.175

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
Bi1 Bi 0.46267(3) 0.33398(2) -0.06442(2) 0.01974(10) Uani 1 1 d . . . . .
Mn1 Mn 0.000000 0.500000 0.000000 0.0225(3) Uani 1 2 d S . P . .
Mn2 Mn 0.45803(13) 0.33836(4) 0.42985(9) 0.0212(2) Uani 1 1 d . . . . .
Mn3 Mn 1.000000 0.500000 0.500000 0.0261(4) Uani 1 2 d S . P . .
S1 S 0.2578(3) 0.64835(8) 0.19041(17) 0.0393(5) Uani 1 1 d . . . . .
S2 S 0.5290(2) 0.42551(8) 0.04917(18) 0.0354(5) Uani 1 1 d . . . . .
S3 S -0.0551(3) 0.25683(8) 0.30785(18) 0.0384(5) Uani 1 1 d . . . . .
S4 S 0.7029(3) 0.17764(8) 0.57996(17) 0.0375(5) Uani 1 1 d . . . . .
S5 S 0.6706(3) 0.27926(9) 0.07523(16) 0.0404(5) Uani 1 1 d . . . . .
S6 S 0.2170(3) 0.37149(10) 0.79439(16) 0.0437(6) Uani 1 1 d . . . . .
N1 N 0.1044(8) 0.5724(3) 0.0621(6) 0.0325(15) Uani 1 1 d . . . . .
N2 N 0.2096(8) 0.4591(3) 0.0638(6) 0.0359(16) Uani 1 1 d . . . . .
N3 N 0.2257(9) 0.3040(3) 0.3825(5) 0.0347(16) Uani 1 1 d . . . . .
N4 N 0.5704(8) 0.2683(3) 0.4918(6) 0.0337(16) Uani 1 1 d . . . . .
N5 N 0.5604(9) 0.3223(3) 0.2697(6) 0.044(2) Uani 1 1 d . . . . .
N6 N 0.3650(9) 0.3579(3) 0.5919(5) 0.0375(17) Uani 1 1 d . . . . .
C1 C 0.1687(9) 0.6037(3) 0.1147(6) 0.0284(17) Uani 1 1 d . . . . .
C2 C 0.3402(10) 0.4454(3) 0.0577(6) 0.0272(17) Uani 1 1 d . . . . .
C3 C 0.1109(9) 0.2843(3) 0.3518(6) 0.0248(16) Uani 1 1 d . . . . .
C4 C 0.6246(9) 0.2311(3) 0.5270(6) 0.0265(17) Uani 1 1 d . . . . .
C5 C 0.6016(10) 0.3053(3) 0.1897(6) 0.0308(18) Uani 1 1 d . . . . .
C6 C 0.3080(10) 0.3634(3) 0.6758(6) 0.0291(18) Uani 1 1 d . . . . .
O1 O -0.1217(6) 0.4911(2) 0.1632(4) 0.0311(12) Uani 1 1 d . . . . .
H11 H -0.130512 0.459725 0.183096 0.047 Uiso 1 1 d R U . . .
H12 H -0.206412 0.508886 0.173077 0.047 Uiso 1 1 d R U . . .
O4 O 1.0802(8) 0.5283(2) 0.3401(5) 0.0478(16) Uani 1 1 d . . . . .
H41 H 1.020586 0.517470 0.288506 0.072 Uiso 1 1 d R U . . .
H42 H 1.180266 0.525999 0.326826 0.072 Uiso 1 1 d R U . . .
O5 O 0.9428(7) 0.5790(2) 0.5505(5) 0.0477(16) Uani 1 1 d . . . . .
H51 H 0.964569 0.605415 0.512136 0.071 Uiso 1 1 d R U . . .
H52 H 0.987438 0.587325 0.610436 0.071 Uiso 1 1 d R U . . .
S7 S 0.4893(3) 0.51881(9) 0.2857(2) 0.0536(6) Uani 0.528(16) 1 d . . P A 1
N7 N 0.751(2) 0.5015(9) 0.4344(16) 0.054(5) Uiso 0.528(16) 1 d . . P A 1
C7 C 0.6465(17) 0.5084(6) 0.3722(12) 0.028(4) Uiso 0.528(16) 1 d . . P A 1
O2 O 0.3676(18) 0.4104(6) 0.3604(12) 0.032(4) Uiso 0.528(16) 1 d . . P A 1
H21 H 0.273569 0.413541 0.386721 0.049 Uiso 0.528(16) 1 d R U P A 1
H22 H 0.402039 0.439951 0.341050 0.049 Uiso 0.528(16) 1 d R U P A 1
O3 O 0.6700(16) 0.3838(5) 0.4980(13) 0.054(4) Uiso 0.528(16) 1 d . . P A 1
H31 H 0.755010 0.369920 0.523187 0.081 Uiso 0.528(16) 1 d R U P A 1
H32 H 0.691022 0.415060 0.481528 0.081 Uiso 0.528(16) 1 d R U P A 1
S7A S 0.4893(3) 0.51881(9) 0.2857(2) 0.0536(6) Uani 0.472(16) 1 d . . P A 2
N7A N 0.391(3) 0.4179(8) 0.3796(17) 0.035(6) Uiso 0.472(16) 1 d . . P A 2
C7A C 0.424(2) 0.4590(7) 0.3343(14) 0.035(5) Uiso 0.472(16) 1 d . . P A 2
O2A O 1.2352(18) 0.5165(7) 0.5559(12) 0.040(4) Uiso 0.472(16) 1 d . . P A 2
H21A H 1.254408 0.549031 0.555855 0.061 Uiso 0.472(16) 1 d R U P A 2
H22A H 1.309608 0.506781 0.598775 0.061 Uiso 0.472(16) 1 d R U P A 2
O3A O 0.7002(13) 0.3753(4) 0.4450(11) 0.025(3) Uiso 0.472(16) 1 d . . P A 2
H31A H 0.775363 0.364025 0.485857 0.038 Uiso 0.472(16) 1 d R U P A 2
H32A H 0.756903 0.380274 0.388517 0.038 Uiso 0.472(16) 1 d R U P A 2
O1W O -0.0973(9) 0.3926(2) 0.2425(5) 0.0567(18) Uani 1 1 d . . . . .
H1W H -0.027710 0.376476 0.204963 0.085 Uiso 1 1 d R U . . .
H2W H -0.183040 0.374966 0.249243 0.085 Uiso 1 1 d R U . . .
O2W O 0.9511(7) 0.3388(2) 0.5774(4) 0.0406(14) Uani 1 1 d . . . . .
H3W H 1.003835 0.310592 0.576683 0.061 Uiso 1 1 d R U . . .
H4W H 0.898266 0.342042 0.636213 0.061 Uiso 1 1 d 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
Bi1 S2 2.7988(19) . ?
Bi1 S5 2.809(2) . ?
Bi1 S4 2.813(2) 4_565 ?
Bi1 S3 2.825(2) 4_665 ?
Bi1 S1 2.832(2) 3_665 ?
Bi1 S6 2.842(2) 1_554 ?
Mn1 N2 2.179(7) 3_565 ?
Mn1 N2 2.179(7) . ?
Mn1 N1 2.198(7) . ?
Mn1 N1 2.198(7) 3_565 ?
Mn1 O1 2.258(5) . ?
Mn1 O1 2.258(5) 3_565 ?
Mn2 N4 2.172(7) . ?
Mn2 O2 2.180(14) . ?
Mn2 N5 2.184(7) . ?
Mn2 N6 2.195(7) . ?
Mn2 N3 2.200(7) . ?
Mn2 N7A 2.22(2) . ?
Mn2 O3A 2.233(11) . ?
Mn2 O3 2.273(13) . ?
Mn3 O2A 2.112(15) 3_766 ?
Mn3 O2A 2.112(15) . ?
Mn3 O5 2.185(6) 3_766 ?
Mn3 O5 2.185(6) . ?
Mn3 O4 2.199(6) 3_766 ?
Mn3 O4 2.199(6) . ?
Mn3 N7 2.22(2) 3_766 ?
Mn3 N7 2.22(2) . ?
S1 C1 1.655(8) . ?
S2 C2 1.654(8) . ?
S3 C3 1.639(8) . ?
S4 C4 1.659(8) . ?
S5 C5 1.661(8) . ?
S6 C6 1.655(8) . ?
N1 C1 1.162(10) . ?
N2 C2 1.144(10) . ?
N3 C3 1.144(9) . ?
N4 C4 1.145(10) . ?
N5 C5 1.129(10) . ?
N6 C6 1.143(9) . ?
O1 H11 0.8495 . ?
O1 H12 0.8499 . ?
O4 H41 0.8499 . ?
O4 H42 0.8500 . ?
O5 H51 0.8497 . ?
O5 H52 0.8501 . ?
S7 C7 1.700(15) . ?
N7 C7 1.17(2) . ?
O2 H21 0.8500 . ?
O2 H22 0.8495 . ?
O3 H31 0.8500 . ?
O3 H32 0.8500 . ?
S7A C7A 1.745(18) . ?
N7A C7A 1.23(3) . ?
O2A H21A 0.8549 . ?
O2A H22A 0.8479 . ?
O3A H31A 0.8500 . ?
O3A H32A 0.8500 . ?
O1W H1W 0.8501 . ?
O1W H2W 0.8499 . ?
O2W H3W 0.8500 . ?
O2W H4W 0.8500 . ?

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
S2 Bi1 S5 90.15(6) . . ?
S2 Bi1 S4 85.80(6) . 4_565 ?
S5 Bi1 S4 91.93(7) . 4_565 ?
S2 Bi1 S3 171.03(6) . 4_665 ?
S5 Bi1 S3 87.16(6) . 4_665 ?
S4 Bi1 S3 102.83(6) 4_565 4_665 ?
S2 Bi1 S1 88.58(6) . 3_665 ?
S5 Bi1 S1 84.86(7) . 3_665 ?
S4 Bi1 S1 173.52(6) 4_565 3_665 ?
S3 Bi1 S1 82.66(6) 4_665 3_665 ?
S2 Bi1 S6 98.89(7) . 1_554 ?
S5 Bi1 S6 168.96(7) . 1_554 ?
S4 Bi1 S6 82.49(7) 4_565 1_554 ?
S3 Bi1 S6 84.82(6) 4_665 1_554 ?
S1 Bi1 S6 101.59(7) 3_665 1_554 ?
N2 Mn1 N2 180.0 3_565 . ?
N2 Mn1 N1 91.4(2) 3_565 . ?
N2 Mn1 N1 88.6(2) . . ?
N2 Mn1 N1 88.6(2) 3_565 3_565 ?
N2 Mn1 N1 91.4(2) . 3_565 ?
N1 Mn1 N1 180.0 . 3_565 ?
N2 Mn1 O1 90.4(2) 3_565 . ?
N2 Mn1 O1 89.6(2) . . ?
N1 Mn1 O1 87.5(2) . . ?
N1 Mn1 O1 92.5(2) 3_565 . ?
N2 Mn1 O1 89.6(2) 3_565 3_565 ?
N2 Mn1 O1 90.4(2) . 3_565 ?
N1 Mn1 O1 92.5(2) . 3_565 ?
N1 Mn1 O1 87.5(2) 3_565 3_565 ?
O1 Mn1 O1 180.0(2) . 3_565 ?
N4 Mn2 O2 174.4(4) . . ?
N4 Mn2 N5 89.3(3) . . ?
O2 Mn2 N5 86.9(4) . . ?
N4 Mn2 N6 91.6(2) . . ?
O2 Mn2 N6 92.0(4) . . ?
N5 Mn2 N6 176.9(3) . . ?
N4 Mn2 N3 97.6(3) . . ?
O2 Mn2 N3 86.6(4) . . ?
N5 Mn2 N3 91.7(3) . . ?
N6 Mn2 N3 91.1(3) . . ?
N4 Mn2 N7A 167.8(6) . . ?
N5 Mn2 N7A 91.4(6) . . ?
N6 Mn2 N7A 87.1(6) . . ?
N3 Mn2 N7A 94.6(6) . . ?
N4 Mn2 O3A 86.6(3) . . ?
N5 Mn2 O3A 78.6(4) . . ?
N6 Mn2 O3A 98.4(4) . . ?
N3 Mn2 O3A 169.5(4) . . ?
N7A Mn2 O3A 81.6(6) . . ?
N4 Mn2 O3 88.4(4) . . ?
O2 Mn2 O3 88.1(5) . . ?
N5 Mn2 O3 97.2(5) . . ?
N6 Mn2 O3 79.8(5) . . ?
N3 Mn2 O3 169.4(5) . . ?
O2A Mn3 O2A 180.0 3_766 . ?
O2A Mn3 O5 94.5(5) 3_766 . ?
O2A Mn3 O5 85.5(5) . . ?
O5 Mn3 O5 180.0 3_766 . ?
O5 Mn3 O4 90.5(2) 3_766 3_766 ?
O5 Mn3 O4 89.5(2) . 3_766 ?
O2A Mn3 O4 93.5(4) 3_766 . ?
O2A Mn3 O4 86.5(4) . . ?
O5 Mn3 O4 89.5(2) 3_766 . ?
O5 Mn3 O4 90.5(2) . . ?
O4 Mn3 O4 180.0 3_766 . ?
O5 Mn3 N7 83.3(6) 3_766 3_766 ?
O5 Mn3 N7 96.7(6) . 3_766 ?
O4 Mn3 N7 87.5(5) 3_766 3_766 ?
O4 Mn3 N7 92.5(5) . 3_766 ?
O5 Mn3 N7 96.7(6) 3_766 . ?
O5 Mn3 N7 83.3(6) . . ?
O4 Mn3 N7 92.5(5) 3_766 . ?
O4 Mn3 N7 87.5(5) . . ?
N7 Mn3 N7 180.0 3_766 . ?
C1 S1 Bi1 99.9(3) . 3_665 ?
C2 S2 Bi1 96.3(3) . . ?
C3 S3 Bi1 97.8(3) . 4_566 ?
C4 S4 Bi1 98.2(3) . 4_666 ?
C5 S5 Bi1 95.6(3) . . ?
C6 S6 Bi1 99.4(3) . 1_556 ?
C1 N1 Mn1 164.6(7) . . ?
C2 N2 Mn1 152.0(7) . . ?
C3 N3 Mn2 174.9(7) . . ?
C4 N4 Mn2 177.3(6) . . ?
C5 N5 Mn2 167.5(8) . . ?
C6 N6 Mn2 173.0(7) . . ?
N1 C1 S1 179.2(7) . . ?
N2 C2 S2 179.9(9) . . ?
N3 C3 S3 179.2(8) . . ?
N4 C4 S4 179.1(7) . . ?
N5 C5 S5 177.1(8) . . ?
N6 C6 S6 177.2(7) . . ?
Mn1 O1 H11 113.1 . . ?
Mn1 O1 H12 116.4 . . ?
H11 O1 H12 113.8 . . ?
Mn3 O4 H41 112.2 . . ?
Mn3 O4 H42 116.6 . . ?
H41 O4 H42 113.6 . . ?
Mn3 O5 H51 123.2 . . ?
Mn3 O5 H52 112.8 . . ?
H51 O5 H52 100.5 . . ?
C7 N7 Mn3 158.5(16) . . ?
N7 C7 S7 177.8(16) . . ?
Mn2 O2 H21 104.4 . . ?
Mn2 O2 H22 139.5 . . ?
H21 O2 H22 109.4 . . ?
Mn2 O3 H31 123.8 . . ?
Mn2 O3 H32 124.3 . . ?
H31 O3 H32 108.4 . . ?
C7A N7A Mn2 150.2(17) . . ?
N7A C7A S7A 171.9(18) . . ?
Mn3 O2A H21A 111.8 . . ?
Mn3 O2A H22A 144.3 . . ?
H21A O2A H22A 99.0 . . ?
Mn2 O3A H31A 124.3 . . ?
Mn2 O3A H32A 120.0 . . ?
H31A O3A H32A 97.1 . . ?
H1W O1W H2W 111.2 . . ?
H3W O2W H4W 111.2 . . ?


# start Validation Reply Form
_vrf_PLAT201_1a                  
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          2 Report
RESPONSE: Partially occupied water atoms which cannot be refined in a 
stable manner due to the near overlap of an N atom.
;
_vrf_PLAT420_1a                  
;
PROBLEM: D-H Without Acceptor       O1       --H12      .     Please Check 
RESPONSE: No acceptor atoms present in structure that would facilitate
this.
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_2_Bi2Co3NCS12
_database_code_depnum_ccdc_archive 'CCDC 1986922'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2019-08-02
_audit_creation_method           
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'Bi6 C36 Co8 N36 S36, (H2 O1)12, Co1, (H2 O1)26'
_chemical_formula_sum            'C36 Bi6 Co9 N36 O38 S36 H76'
_chemical_formula_weight         4535.4663
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 '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'
S S 0.1246 0.1234 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   12.0209(2)
_cell_length_b                   12.1613(2)
_cell_length_c                   23.8319(4)
_cell_angle_alpha                94.2000(10)
_cell_angle_beta                 94.0030(10)
_cell_angle_gamma                91.4520(10)
_cell_volume                     3464.52(10)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    12220
_cell_measurement_temperature    180
_cell_measurement_theta_max      26.022
_cell_measurement_theta_min      0.998
_shelx_estimated_absorpt_T_max   0.913
_shelx_estimated_absorpt_T_min   0.403
_exptl_absorpt_coefficient_mu    9.248
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.74
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.149
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             2089
_exptl_crystal_preparation       'evaporated from aqueous solution'
_exptl_crystal_recrystallization_method ?
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0562
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21789
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.098
_diffrn_reflns_theta_min         1.680
_diffrn_ambient_temperature      180
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ?
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                11011
_reflns_number_total             13585
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction        'Denzo and Scalepak (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         2.497
_refine_diff_density_min         -2.441
_refine_diff_density_rms         0.202
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     736
_refine_ls_number_reflns         13585
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0791
_refine_ls_R_factor_gt           0.0587
_refine_ls_restrained_S_all      1.129
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0071P)²+60.4338P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1201
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_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
Bi2 Bi 0.01859(3) 0.53222(3) 0.75399(2) 0.02949(11) Uani 1 1 d . . . . .
Bi1 Bi 0.500000 0.500000 1.000000 0.03024(14) Uani 1 2 d S T P . .
Bi4 Bi 1.000000 1.000000 0.500000 0.03136(14) Uani 1 2 d S T P . .
Bi3 Bi 0.55740(3) 1.01767(3) 0.76007(2) 0.02998(11) Uani 1 1 d . . . . .
Co2 Co 0.000000 0.500000 1.000000 0.0251(4) Uani 1 2 d S T P . .
Co1 Co 0.500000 1.000000 1.000000 0.0239(4) Uani 1 2 d S T P . .
Co4 Co 1.05274(11) 1.03614(11) 0.76066(6) 0.0247(3) Uani 1 1 d . . . . .
Co6 Co 0.000000 0.500000 0.500000 0.0319(5) Uani 1 2 d S T P . .
Co3 Co 0.51776(13) 0.50225(12) 0.74646(7) 0.0342(4) Uani 1 1 d . . . . .
Co5 Co 0.500000 1.000000 0.500000 0.0581(8) Uani 1 2 d S T P . .
S3 S 0.3482(2) 0.3467(2) 0.94385(14) 0.0374(7) Uani 1 1 d . . . . .
S11 S 1.4300(2) 1.1746(2) 0.82617(13) 0.0336(6) Uani 1 1 d . . . . .
S8 S 0.1670(2) 0.4474(3) 0.83234(12) 0.0411(7) Uani 1 1 d . . . . .
S7 S 0.6447(2) 0.3850(3) 0.92924(13) 0.0428(7) Uani 1 1 d . . . . .
S1 S 0.7296(3) 1.0813(3) 0.84568(14) 0.0490(8) Uani 1 1 d . . . . .
S12 S 0.8599(2) 1.3841(2) 0.79238(16) 0.0439(8) Uani 1 1 d . . . . .
S13 S 0.6851(2) 0.8540(3) 0.71572(16) 0.0474(8) Uani 1 1 d . . . . .
S5 S 0.8676(3) 0.6258(3) 0.67378(14) 0.0486(8) Uani 1 1 d . . . . .
S2 S 0.4017(4) 0.6307(3) 0.91914(14) 0.0543(9) Uani 1 1 d . . . . .
S4 S -0.0514(3) 0.7036(3) 0.83076(14) 0.0530(9) Uani 1 1 d . . . . .
S6 S 0.4517(3) 0.8721(3) 0.82578(13) 0.0440(7) Uani 1 1 d . . . . .
S14 S 1.1815(3) 0.6677(2) 0.70899(17) 0.0527(9) Uani 1 1 d . . . . .
S9 S 0.6677(3) 0.1501(3) 0.68739(17) 0.0605(10) Uani 1 1 d . . . . .
S18 S 0.0893(4) 0.3611(3) 0.68188(14) 0.0604(10) Uani 1 1 d . . . . .
S16 S 0.3817(3) 0.9341(5) 0.68501(15) 0.0802(15) Uani 1 1 d . . . . .
S10 S 1.1775(4) 1.0858(5) 0.57416(17) 0.0965(19) Uani 1 1 d . . . . .
S17 S 0.0687(5) 0.1330(3) 0.41586(17) 0.0781(14) Uani 1 1 d . . . . .
S15 S 0.8750(3) 1.1528(3) 0.5600(2) 0.0726(12) Uani 1 1 d . . . . .
O1 O 0.3623(6) 1.0488(6) 0.9437(3) 0.0300(16) Uani 1 1 d . . . . .
O2 O -0.0727(6) 0.3606(6) 0.9478(3) 0.0357(18) Uani 1 1 d . . . . .
O4 O 1.0264(6) 1.0073(6) 0.8496(3) 0.0340(17) Uani 1 1 d . . . . .
O4W O 0.7903(7) 0.8436(7) 0.9887(4) 0.056(2) Uani 1 1 d . . . . .
N10 N 1.0871(8) 1.0646(7) 0.6785(4) 0.034(2) Uani 1 1 d . . . . .
O1W O 0.2087(7) 0.8869(7) 0.8902(4) 0.046(2) Uani 1 1 d . . . . .
N11 N 1.2112(8) 1.1024(7) 0.7908(4) 0.033(2) Uani 1 1 d . . . . .
N12 N 0.9775(8) 1.1881(7) 0.7758(4) 0.033(2) Uani 1 1 d . . . . .
N3 N 0.1552(7) 0.4439(7) 0.9817(4) 0.032(2) Uani 1 1 d . . . . .
N14 N 1.1200(8) 0.8766(8) 0.7502(4) 0.038(2) Uani 1 1 d . . . . .
O2W O 0.1720(10) 0.8059(9) 0.9944(5) 0.078(3) Uani 1 1 d . . . . .
N1 N 0.6082(8) 1.0249(7) 0.9370(4) 0.035(2) Uani 1 1 d . . . . .
O3W O 0.9192(7) 0.7886(7) 1.0910(4) 0.047(2) Uani 1 1 d . . . . .
O6 O -0.1612(10) 0.4337(11) 0.5115(5) 0.088(4) Uani 1 1 d . . . . .
N4 N -0.0100(8) 0.5954(8) 0.9300(4) 0.039(2) Uani 1 1 d . . . . .
N8 N 0.3611(8) 0.4563(8) 0.7736(5) 0.043(2) Uani 1 1 d . . . . .
C5 C 0.7499(11) 0.5841(10) 0.7001(5) 0.043(3) Uani 1 1 d . . . . .
N2 N 0.4703(8) 0.8372(7) 0.9712(4) 0.034(2) Uani 1 1 d . . . . .
N13 N 0.8945(8) 0.9606(8) 0.7391(4) 0.036(2) Uani 1 1 d . . . . .
N9 N 0.5542(9) 0.3432(9) 0.7161(5) 0.048(3) Uani 1 1 d . . . . .
N6 N 0.4858(9) 0.6661(8) 0.7705(5) 0.052(3) Uani 1 1 d . . . . .
C13 C 0.8090(9) 0.9187(8) 0.7293(5) 0.030(2) Uani 1 1 d . . . . .
N5 N 0.6677(9) 0.5550(8) 0.7172(5) 0.052(3) Uani 1 1 d . . . . .
N7 N 0.5899(9) 0.4736(9) 0.8259(4) 0.046(3) Uani 1 1 d . . . . .
N18 N 0.0536(12) 0.4587(9) 0.5796(4) 0.061(4) Uani 1 1 d . . . . .
C11 C 1.3007(9) 1.1321(8) 0.8052(4) 0.024(2) Uani 1 1 d . . . . .
C14 C 1.1443(8) 0.7912(8) 0.7331(4) 0.027(2) Uani 1 1 d . . . . .
O5W O 0.9159(8) 1.0124(9) 0.9682(5) 0.074(3) Uani 1 1 d . . . . .
C01M C 0.9307(9) 1.2698(8) 0.7821(4) 0.028(2) Uani 1 1 d . . . . .
C8 C 0.2815(9) 0.4525(9) 0.7971(5) 0.033(2) Uani 1 1 d . . . . .
C7 C 0.6106(9) 0.4370(9) 0.8686(5) 0.034(3) Uani 1 1 d . . . . .
C10 C 1.1224(11) 1.0726(11) 0.6359(5) 0.049(3) Uani 1 1 d . . . . .
C3 C 0.2359(8) 0.4057(8) 0.9674(4) 0.027(2) Uani 1 1 d . . . . .
C4 C -0.0254(10) 0.6392(9) 0.8891(5) 0.036(3) Uani 1 1 d . . . . .
C1 C 0.6596(9) 1.0473(9) 0.8996(5) 0.032(2) Uani 1 1 d . . . . .
N17 N 0.0383(11) 0.3441(9) 0.4673(5) 0.060(3) Uani 1 1 d . . . . .
N16 N 0.4687(10) 0.9575(15) 0.5805(5) 0.088(5) Uani 1 1 d . . . . .
O3 O 0.4309(11) 0.5242(12) 0.6661(5) 0.101(4) Uani 1 1 d . . . . .
C2 C 0.4419(9) 0.7518(8) 0.9506(4) 0.029(2) Uani 1 1 d . . . . .
O6W O 0.6993(10) 0.7241(12) 0.8947(6) 0.101(4) Uani 1 1 d . . . . .
O5 O 0.4434(11) 1.1596(13) 0.5206(6) 0.107(5) Uani 1 1 d . . . . .
C6 C 0.4723(9) 0.7503(10) 0.7918(5) 0.035(3) Uani 1 1 d . . . . .
N15 N 0.6630(10) 1.0515(15) 0.5282(5) 0.084(5) Uani 1 1 d . . . . .
O10W O 0.7740(14) 0.3703(12) 0.6157(6) 0.126(6) Uani 1 1 d . . . . .
C9 C 0.6010(11) 0.2636(10) 0.7052(5) 0.040(3) Uani 1 1 d . . . . .
O13W O 0.2388(12) 0.7364(14) 0.5726(6) 0.118(5) Uani 1 1 d . . . . .
O7W O 0.6592(14) 0.7525(14) 0.5734(7) 0.130(6) Uani 1 1 d . . . . .
C18 C 0.0678(12) 0.4213(10) 0.6210(6) 0.048(3) Uani 1 1 d . . . . .
C15 C 0.7508(13) 1.0944(14) 0.5417(7) 0.062(4) Uani 1 1 d . . . . .
C16 C 0.4337(12) 0.9493(18) 0.6238(7) 0.082(6) Uani 1 1 d . . . . .
C17 C 0.0511(12) 0.2575(11) 0.4476(6) 0.052(3) Uani 1 1 d . . . . .
O12W O 0.3408(16) 0.317(2) 0.6141(12) 0.210(11) Uani 1 1 d . . . . .
Co7 Co 0.500000 0.500000 0.500000 0.1065(13) Uani 1 2 d S T P . .
O8W O 0.6816(11) 0.5952(14) 0.4871(9) 0.152(8) Uani 1 1 d . . . A 1
O9W O 0.452(2) 0.6507(16) 0.5809(8) 0.179(9) Uani 1 1 d . . . B 1
O11W O 0.575(2) 0.3683(18) 0.5690(8) 0.198(10) Uani 1 1 d . . . . .


_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
Bi2 S8 2.764(3) . ?
Bi2 S12 2.833(3) 1_445 ?
Bi2 S5 2.860(3) 1_455 ?
Bi2 S4 2.854(3) . ?
Bi2 S14 2.844(3) 1_455 ?
Bi2 S18 2.788(3) . ?
Bi1 S3 2.778(3) 2_667 ?
Bi1 S3 2.778(3) . ?
Bi1 S7 2.830(3) 2_667 ?
Bi1 S7 2.830(3) . ?
Bi1 S2 2.804(3) 2_667 ?
Bi1 S2 2.804(3) . ?
Bi4 S10 2.802(4) 2_776 ?
Bi4 S10 2.802(4) . ?
Bi4 S17 2.821(4) 1_665 ?
Bi4 S17 2.821(4) 2_666 ?
Bi4 S15 2.794(4) . ?
Bi4 S15 2.794(4) 2_776 ?
Bi3 S11 2.917(3) 1_455 ?
Bi3 S1 2.854(3) . ?
Bi3 S13 2.741(3) . ?
Bi3 S6 2.787(3) . ?
Bi3 S9 2.823(4) 1_565 ?
Bi3 S16 2.791(4) . ?
Co2 O2 2.156(7) 2_567 ?
Co2 O2 2.156(7) . ?
Co2 N3 2.067(9) 2_567 ?
Co2 N3 2.067(9) . ?
Co2 N4 2.099(10) 2_567 ?
Co2 N4 2.099(10) . ?
Co1 O1 2.180(7) . ?
Co1 O1 2.180(7) 2_677 ?
Co1 N1 2.088(10) 2_677 ?
Co1 N1 2.088(10) . ?
Co1 N2 2.061(9) 2_677 ?
Co1 N2 2.061(9) . ?
Co4 O4 2.215(7) . ?
Co4 N10 2.081(9) . ?
Co4 N11 2.108(10) . ?
Co4 N12 2.097(9) . ?
Co4 N14 2.125(9) . ?
Co4 N13 2.106(10) . ?
Co6 O6 2.123(11) . ?
Co6 O6 2.123(11) 2_566 ?
Co6 N18 2.061(10) 2_566 ?
Co6 N18 2.061(10) . ?
Co6 N17 2.072(11) . ?
Co6 N17 2.072(11) 2_566 ?
Co3 N8 2.109(10) . ?
Co3 N9 2.083(11) . ?
Co3 N6 2.085(11) . ?
Co3 N5 2.081(10) . ?
Co3 N7 2.083(11) . ?
Co3 O3 2.153(11) . ?
Co5 N16 2.081(12) 2_676 ?
Co5 N16 2.081(12) . ?
Co5 O5 2.109(15) 2_676 ?
Co5 O5 2.109(15) . ?
Co5 N15 2.092(13) . ?
Co5 N15 2.092(13) 2_676 ?
S3 C3 1.658(10) . ?
S11 C11 1.658(11) . ?
S8 C8 1.663(12) . ?
S7 C7 1.649(12) . ?
S1 C1 1.657(12) . ?
S12 C01M 1.660(11) . ?
S13 C13 1.667(12) . ?
S5 C5 1.670(14) . ?
S2 C2 1.648(11) . ?
S4 C4 1.660(12) . ?
S6 C6 1.668(13) . ?
S14 C14 1.652(11) . ?
S9 C9 1.657(12) . ?
S18 C18 1.679(14) . ?
S16 C16 1.647(16) . ?
S10 C10 1.672(14) . ?
S17 C17 1.667(14) . ?
S15 C15 1.653(17) . ?
N10 C10 1.136(15) . ?
N11 C11 1.147(13) . ?
N12 C01M 1.160(13) . ?
N3 C3 1.148(13) . ?
N14 C14 1.140(13) . ?
N1 C1 1.162(14) . ?
N4 C4 1.150(14) . ?
N8 C8 1.144(14) . ?
C5 N5 1.151(15) . ?
N2 C2 1.149(13) . ?
N13 C13 1.137(13) . ?
N9 C9 1.154(15) . ?
N6 C6 1.130(15) . ?
N7 C7 1.155(15) . ?
N18 C18 1.121(16) . ?
N17 C17 1.140(16) . ?
N16 C16 1.151(18) . ?
N15 C15 1.179(19) . ?

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
S8 Bi2 S12 85.27(9) . 1_445 ?
S8 Bi2 S5 178.45(11) . 1_455 ?
S8 Bi2 S4 94.46(10) . . ?
S8 Bi2 S14 94.83(11) . 1_455 ?
S8 Bi2 S18 83.85(10) . . ?
S12 Bi2 S5 95.89(10) 1_445 1_455 ?
S12 Bi2 S4 90.09(10) 1_445 . ?
S12 Bi2 S14 175.55(10) 1_445 1_455 ?
S4 Bi2 S5 84.53(10) . 1_455 ?
S14 Bi2 S5 84.09(10) 1_455 1_455 ?
S14 Bi2 S4 94.33(10) 1_455 . ?
S18 Bi2 S12 89.11(11) . 1_445 ?
S18 Bi2 S5 97.18(11) . 1_455 ?
S18 Bi2 S4 178.19(9) . . ?
S18 Bi2 S14 86.47(11) . 1_455 ?
S3 Bi1 S3 180.00(9) . 2_667 ?
S3 Bi1 S7 99.43(9) . 2_667 ?
S3 Bi1 S7 99.43(9) 2_667 . ?
S3 Bi1 S7 80.57(9) . . ?
S3 Bi1 S7 80.57(9) 2_667 2_667 ?
S3 Bi1 S2 99.80(9) 2_667 . ?
S3 Bi1 S2 99.80(9) . 2_667 ?
S3 Bi1 S2 80.20(9) 2_667 2_667 ?
S3 Bi1 S2 80.20(9) . . ?
S7 Bi1 S7 180.0 . 2_667 ?
S2 Bi1 S7 82.42(10) . 2_667 ?
S2 Bi1 S7 82.42(10) 2_667 . ?
S2 Bi1 S7 97.58(10) 2_667 2_667 ?
S2 Bi1 S7 97.58(10) . . ?
S2 Bi1 S2 180.0 2_667 . ?
S10 Bi4 S10 180.0 2_776 . ?
S10 Bi4 S17 89.55(14) . 2_666 ?
S10 Bi4 S17 90.45(15) 2_776 2_666 ?
S10 Bi4 S17 90.45(15) . 1_665 ?
S10 Bi4 S17 89.55(14) 2_776 1_665 ?
S17 Bi4 S17 180.0 1_665 2_666 ?
S15 Bi4 S10 83.99(15) 2_776 2_776 ?
S15 Bi4 S10 83.99(15) . . ?
S15 Bi4 S10 96.01(15) 2_776 . ?
S15 Bi4 S10 96.01(15) . 2_776 ?
S15 Bi4 S17 80.74(13) 2_776 1_665 ?
S15 Bi4 S17 99.26(13) . 1_665 ?
S15 Bi4 S17 80.74(13) . 2_666 ?
S15 Bi4 S17 99.26(13) 2_776 2_666 ?
S15 Bi4 S15 180.00(14) . 2_776 ?
S1 Bi3 S11 82.64(9) . 1_455 ?
S13 Bi3 S11 169.84(10) . 1_455 ?
S13 Bi3 S1 91.11(10) . . ?
S13 Bi3 S6 91.86(10) . . ?
S13 Bi3 S9 83.92(10) . 1_565 ?
S13 Bi3 S16 87.75(13) . . ?
S6 Bi3 S11 80.65(9) . 1_455 ?
S6 Bi3 S1 94.01(10) . . ?
S6 Bi3 S9 175.32(10) . 1_565 ?
S6 Bi3 S16 78.79(11) . . ?
S9 Bi3 S11 103.78(9) 1_565 1_455 ?
S9 Bi3 S1 88.11(11) 1_565 . ?
S16 Bi3 S11 97.43(12) . 1_455 ?
S16 Bi3 S1 172.67(11) . . ?
S16 Bi3 S9 98.96(12) . 1_565 ?
O2 Co2 O2 180.0(4) . 2_567 ?
N3 Co2 O2 92.0(3) . 2_567 ?
N3 Co2 O2 88.0(3) 2_567 2_567 ?
N3 Co2 O2 88.0(3) . . ?
N3 Co2 O2 92.0(3) 2_567 . ?
N3 Co2 N3 180.0(5) 2_567 . ?
N3 Co2 N4 87.7(3) . 2_567 ?
N3 Co2 N4 92.3(3) 2_567 2_567 ?
N3 Co2 N4 87.7(3) 2_567 . ?
N3 Co2 N4 92.3(3) . . ?
N4 Co2 O2 90.3(3) . 2_567 ?
N4 Co2 O2 90.3(3) 2_567 . ?
N4 Co2 O2 89.7(3) . . ?
N4 Co2 O2 89.7(3) 2_567 2_567 ?
N4 Co2 N4 180.0(5) . 2_567 ?
O1 Co1 O1 180.0 2_677 . ?
N1 Co1 O1 89.0(3) . . ?
N1 Co1 O1 91.0(3) . 2_677 ?
N1 Co1 O1 91.0(3) 2_677 . ?
N1 Co1 O1 89.0(3) 2_677 2_677 ?
N1 Co1 N1 180.0(5) . 2_677 ?
N2 Co1 O1 90.2(3) 2_677 2_677 ?
N2 Co1 O1 89.8(3) 2_677 . ?
N2 Co1 O1 89.8(3) . 2_677 ?
N2 Co1 O1 90.2(3) . . ?
N2 Co1 N1 91.9(4) 2_677 2_677 ?
N2 Co1 N1 88.1(4) . 2_677 ?
N2 Co1 N1 91.9(4) . . ?
N2 Co1 N1 88.1(4) 2_677 . ?
N2 Co1 N2 180.0 . 2_677 ?
N10 Co4 O4 176.7(3) . . ?
N10 Co4 N11 90.4(4) . . ?
N10 Co4 N12 94.3(4) . . ?
N10 Co4 N14 89.9(4) . . ?
N10 Co4 N13 95.7(4) . . ?
N11 Co4 O4 86.4(3) . . ?
N11 Co4 N14 90.2(4) . . ?
N12 Co4 O4 86.6(3) . . ?
N12 Co4 N11 92.1(3) . . ?
N12 Co4 N14 175.2(3) . . ?
N12 Co4 N13 89.8(4) . . ?
N14 Co4 O4 89.3(3) . . ?
N13 Co4 O4 87.4(3) . . ?
N13 Co4 N11 173.4(4) . . ?
N13 Co4 N14 87.4(4) . . ?
O6 Co6 O6 180.0(3) . 2_566 ?
N18 Co6 O6 89.6(5) 2_566 2_566 ?
N18 Co6 O6 90.4(5) 2_566 . ?
N18 Co6 O6 89.6(5) . . ?
N18 Co6 O6 90.4(5) . 2_566 ?
N18 Co6 N18 180.0 2_566 . ?
N18 Co6 N17 90.2(4) . 2_566 ?
N18 Co6 N17 89.8(4) 2_566 2_566 ?
N18 Co6 N17 90.2(4) 2_566 . ?
N18 Co6 N17 89.8(4) . . ?
N17 Co6 O6 92.8(5) . 2_566 ?
N17 Co6 O6 87.2(5) . . ?
N17 Co6 O6 87.2(5) 2_566 2_566 ?
N17 Co6 O6 92.8(5) 2_566 . ?
N17 Co6 N17 180.0(3) . 2_566 ?
N8 Co3 O3 86.5(5) . . ?
N9 Co3 N8 94.6(4) . . ?
N9 Co3 N6 175.1(4) . . ?
N9 Co3 O3 88.6(5) . . ?
N6 Co3 N8 88.8(4) . . ?
N6 Co3 O3 88.1(5) . . ?
N5 Co3 N8 176.6(4) . . ?
N5 Co3 N9 87.6(4) . . ?
N5 Co3 N6 88.9(4) . . ?
N5 Co3 N7 93.7(5) . . ?
N5 Co3 O3 91.0(5) . . ?
N7 Co3 N8 88.9(4) . . ?
N7 Co3 N9 90.5(4) . . ?
N7 Co3 N6 93.1(5) . . ?
N7 Co3 O3 175.1(5) . . ?
N16 Co5 N16 180.0(6) . 2_676 ?
N16 Co5 O5 90.7(6) . 2_676 ?
N16 Co5 O5 89.3(6) . . ?
N16 Co5 O5 89.3(6) 2_676 2_676 ?
N16 Co5 O5 90.7(6) 2_676 . ?
N16 Co5 N15 90.6(5) . . ?
N16 Co5 N15 90.6(5) 2_676 2_676 ?
N16 Co5 N15 89.4(5) 2_676 . ?
N16 Co5 N15 89.4(5) . 2_676 ?
O5 Co5 O5 180.0(7) . 2_676 ?
N15 Co5 O5 90.3(6) 2_676 2_676 ?
N15 Co5 O5 90.3(6) . . ?
N15 Co5 O5 89.7(6) 2_676 . ?
N15 Co5 O5 89.7(6) . 2_676 ?
N15 Co5 N15 180.0 . 2_676 ?
C3 S3 Bi1 95.4(4) . . ?
C11 S11 Bi3 100.8(3) . 1_655 ?
C8 S8 Bi2 98.9(4) . . ?
C7 S7 Bi1 100.6(4) . . ?
C1 S1 Bi3 96.4(4) . . ?
C01M S12 Bi2 97.3(4) . 1_665 ?
C13 S13 Bi3 97.6(4) . . ?
C5 S5 Bi2 97.0(4) . 1_655 ?
C2 S2 Bi1 97.4(4) . . ?
C4 S4 Bi2 96.7(4) . . ?
C6 S6 Bi3 102.0(4) . . ?
C14 S14 Bi2 100.6(4) . 1_655 ?
C9 S9 Bi3 94.9(4) . 1_545 ?
C18 S18 Bi2 98.0(4) . . ?
C16 S16 Bi3 101.3(6) . . ?
C10 S10 Bi4 100.1(5) . . ?
C17 S17 Bi4 99.7(5) . 1_445 ?
C15 S15 Bi4 97.2(5) . . ?
C10 N10 Co4 168.6(10) . . ?
C11 N11 Co4 175.1(8) . . ?
C01M N12 Co4 176.0(9) . . ?
C3 N3 Co2 173.2(9) . . ?
C14 N14 Co4 165.0(10) . . ?
C1 N1 Co1 172.1(9) . . ?
C4 N4 Co2 171.9(10) . . ?
C8 N8 Co3 163.9(10) . . ?
N5 C5 S5 178.7(13) . . ?
C2 N2 Co1 170.7(9) . . ?
C13 N13 Co4 177.6(10) . . ?
C9 N9 Co3 162.5(11) . . ?
C6 N6 Co3 169.3(11) . . ?
N13 C13 S13 178.4(11) . . ?
C5 N5 Co3 178.9(12) . . ?
C7 N7 Co3 163.3(11) . . ?
C18 N18 Co6 167.1(13) . . ?
N11 C11 S11 179.8(11) . . ?
N14 C14 S14 179.1(11) . . ?
N12 C01M S12 177.7(10) . . ?
N8 C8 S8 179.0(11) . . ?
N7 C7 S7 178.1(11) . . ?
N10 C10 S10 178.4(12) . . ?
N3 C3 S3 176.7(10) . . ?
N4 C4 S4 178.2(11) . . ?
N1 C1 S1 178.3(11) . . ?
C17 N17 Co6 174.7(13) . . ?
C16 N16 Co5 165.6(15) . . ?
N2 C2 S2 178.2(10) . . ?
N6 C6 S6 177.6(11) . . ?
C15 N15 Co5 170.8(16) . . ?
N9 C9 S9 178.2(11) . . ?
N18 C18 S18 178.1(12) . . ?
N15 C15 S15 179.0(16) . . ?
N16 C16 S16 178(2) . . ?
N17 C17 S17 177.4(13) . . ?

_olex2_submission_special_instructions 'No special instructions were received'

# start Validation Reply Form
_vrf_PLAT241_import              
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of        S10 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to.
;
_vrf_PLAT242_import              
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of        Bi4 Check 
RESPONSE: It is common for thiocyanate bound to heavy metals to show 
significantly more thermal motion than the metal it is bound to.
;
_vrf_PLAT306_import              
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W Check 
RESPONSE: Hydrogen bonds are present throughout but it was not possible to 
locate the hydrogen atoms of the water cluster in the difference map.
The range of different  possible hydrogen positions precluded placing 
them geometrically.
;
_vrf_PLAT043_2_Bi2Co3NCS12       
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      52.33 Check 
RESPONSE: It was not possible to locate the hydrogen atoms of the water 
cluster in the difference map. The range of different  possible hydrogen
 positions precluded placing them geometrically.
;
# end Validation Reply Form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_4_Ni6Bi5NCS30_3NH4
_database_code_depnum_ccdc_archive 'CCDC 1986923'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
_audit_creation_date             2019-01-09
_audit_creation_method           
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C30 H74 Bi5 N33 Ni6 O16 S30'
_chemical_formula_sum            'C30 H74 Bi5 N33 Ni6 O16 S30'
_chemical_formula_weight         3512.13
_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'
Bi Bi -4.1077 10.2566 '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'
Ni Ni 0.3393 1.1124 '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'
S S 0.1246 0.1234 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   11.8567(2)
_cell_length_b                   11.8653(2)
_cell_length_c                   18.3824(4)
_cell_angle_alpha                84.0731(7)
_cell_angle_beta                 76.7140(7)
_cell_angle_gamma                85.1942(8)
_cell_volume                     2498.60(8)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    10868
_cell_measurement_temperature    111
_cell_measurement_theta_max      27.485
_cell_measurement_theta_min      0.998
_shelx_estimated_absorpt_T_max   0.620
_shelx_estimated_absorpt_T_min   0.418
_exptl_absorpt_coefficient_mu    10.562
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.290
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1610
_exptl_crystal_preparation       'precipitated from acidic solution'
_exptl_crystal_recrystallization_method ?
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_special_details           
;
?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0752
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            20614
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.479
_diffrn_reflns_theta_min         2.983
_diffrn_ambient_temperature      111
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius Kappa'
_diffrn_measurement_method       ω/2θ
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      0.05014
_diffrn_orient_matrix_UB_12      -0.02513
_diffrn_orient_matrix_UB_13      -0.06629
_diffrn_orient_matrix_UB_21      -0.06661
_diffrn_orient_matrix_UB_22      -0.04567
_diffrn_orient_matrix_UB_23      -0.02617
_diffrn_orient_matrix_UB_31      -0.02052
_diffrn_orient_matrix_UB_32      0.04912
_diffrn_orient_matrix_UB_33      -0.01774
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  all
_diffrn_source                   'fine-focus sealed tube'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                8490
_reflns_number_total             11356
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction        'Denzo and Scalepak (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.222
_refine_diff_density_min         -1.096
_refine_diff_density_rms         0.218
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         11356
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0433
_refine_ls_restrained_S_all      1.036
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+14.5070P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0664
_refine_ls_wR_factor_ref         0.0742
_refine_special_details          ?
_olex2_refinement_description    
;
1. Restrained distances
 N17-H17C
 0.88 with sigma of 0.02
 N17-H17A
 0.88 with sigma of 0.02
 N17-H17B
 0.88 with sigma of 0.02
 N17-H17D
 0.88 with sigma of 0.02
2. Others
 Fixed Sof: N16A(0.5) O4WA(0.5) O5WA(0.5) O4W(0.5) O5W(0.5)
;
_atom_sites_solution_hydrogens   difmap
_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
Bi1 Bi 0.21498(2) 0.98918(2) 0.17885(2) 0.01621(7) Uani 1 1 d . . . . .
Bi2 Bi 0.67566(2) 0.48829(2) 0.16736(2) 0.01918(7) Uani 1 1 d . . . . .
Bi3 Bi 1.000000 0.500000 0.500000 0.01950(9) Uani 1 2 d S T P . .
Ni2 Ni 0.69617(7) 0.98100(7) 0.17601(5) 0.01552(19) Uani 1 1 d . . . . .
Ni4 Ni 1.000000 1.000000 0.500000 0.0178(3) Uani 1 2 d S T P . .
Ni1 Ni 0.17859(7) 0.51400(7) 0.16337(5) 0.01568(19) Uani 1 1 d . . . . .
Ni3 Ni 0.500000 0.500000 0.500000 0.0195(3) Uani 1 2 d S T P . .
S9 S 1.03723(15) 0.83564(14) 0.26935(10) 0.0208(4) Uani 1 1 d . . . . .
S11 S 0.92852(15) 0.96057(16) -0.07459(10) 0.0230(4) Uani 1 1 d . . . . .
S3 S 0.05520(17) 0.13818(15) 0.26197(10) 0.0262(4) Uani 1 1 d . . . . .
S5 S 0.58073(15) 0.39366(15) 0.06604(10) 0.0232(4) Uani 1 1 d . . . . .
S7 S 0.34608(16) 1.16192(15) 0.10947(12) 0.0272(4) Uani 1 1 d . . . . .
S8 S 0.48783(15) 0.63476(14) 0.21919(11) 0.0230(4) Uani 1 1 d . . . . .
S1 S 0.23529(17) 0.33428(16) -0.05801(11) 0.0293(4) Uani 1 1 d . . . . .
S2 S -0.22446(15) 0.57136(16) 0.27863(10) 0.0240(4) Uani 1 1 d . . . . .
S6 S 0.37529(16) 0.85739(15) 0.07650(11) 0.0255(4) Uani 1 1 d . . . . .
S10 S 0.88163(16) 1.33767(15) 0.11780(12) 0.0269(4) Uani 1 1 d . . . . .
S4 S 0.18170(16) 0.62587(17) 0.40886(10) 0.0256(4) Uani 1 1 d . . . . .
S15 S 1.33388(16) 0.92375(18) 0.29656(10) 0.0293(4) Uani 1 1 d . . . . .
S12 S 0.5607(2) 0.32004(17) 0.26791(11) 0.0362(5) Uani 1 1 d . . . . .
S13 S 0.86354(18) 0.67729(17) 0.44674(15) 0.0416(6) Uani 1 1 d . . . . .
S14 S 1.0563(2) 0.61999(17) 0.60957(12) 0.0484(7) Uani 1 1 d . . . . .
O1 O 0.6196(4) 1.0083(4) 0.2905(3) 0.0221(11) Uani 1 1 d . . . . .
O2 O 0.5577(4) 0.3450(4) 0.5555(3) 0.0250(11) Uani 1 1 d . . . . .
O1W O 0.6253(4) 0.7994(4) 0.3719(3) 0.0296(12) Uani 1 1 d . . . . .
N3 N 0.1310(5) 0.3541(5) 0.2031(3) 0.0218(13) Uani 1 1 d . . . . .
O3 O 1.1005(4) 1.0379(4) 0.5753(3) 0.0231(11) Uani 1 1 d . . . . .
N11 N 0.7728(5) 0.9584(5) 0.0662(3) 0.0222(13) Uani 1 1 d . . . . .
N6 N 0.2318(5) 0.6742(5) 0.1192(3) 0.0233(14) Uani 1 1 d . . . . .
N10 N 0.7704(5) 1.1328(5) 0.1638(3) 0.0218(13) Uani 1 1 d . . . . .
N8 N 0.6156(5) 0.8305(5) 0.1933(3) 0.0182(12) Uani 1 1 d . . . . .
N4 N 0.1945(5) 0.5484(5) 0.2665(3) 0.0226(13) Uani 1 1 d . . . . .
N1 N 0.1582(5) 0.4790(5) 0.0580(3) 0.0232(14) Uani 1 1 d . . . . .
N2 N 0.0056(5) 0.5735(5) 0.1913(3) 0.0228(13) Uani 1 1 d . . . . .
N7 N 0.5504(5) 1.0616(5) 0.1490(3) 0.0212(13) Uani 1 1 d . . . . .
N17 N 0.0242(7) 0.7517(6) 0.0585(5) 0.0322(16) Uani 1 1 d D . . . .
N9 N 0.8386(5) 0.9043(5) 0.2118(3) 0.0206(13) Uani 1 1 d . . . . .
N13 N 0.6574(5) 0.5622(5) 0.4794(3) 0.0252(14) Uani 1 1 d . . . . .
N5 N 0.3485(5) 0.4556(5) 0.1337(3) 0.0186(12) Uani 1 1 d . . . . .
N14 N 1.0145(5) 0.8361(5) 0.5388(3) 0.0234(14) Uani 1 1 d . . . . .
O2W O 0.7727(5) 0.1263(5) 0.3489(3) 0.0404(14) Uani 1 1 d . . . . .
N12 N 0.5382(5) 0.4273(5) 0.4005(4) 0.0286(15) Uani 1 1 d . . . . .
N15 N 1.1491(5) 0.9723(5) 0.4180(3) 0.0223(13) Uani 1 1 d . . . . .
C1 C 0.1883(6) 0.4214(6) 0.0098(4) 0.0196(15) Uani 1 1 d . . . . .
C4 C 0.1880(6) 0.5794(6) 0.3256(4) 0.0195(15) Uani 1 1 d . . . . .
C3 C 0.1015(6) 0.2653(6) 0.2252(4) 0.0171(15) Uani 1 1 d . . . . .
C8 C 0.5641(6) 0.7506(6) 0.2033(4) 0.0195(15) Uani 1 1 d . . . . .
C11 C 0.8329(6) 0.9611(5) 0.0076(4) 0.0194(15) Uani 1 1 d . . . . .
C6 C 0.2925(6) 0.7477(6) 0.1017(4) 0.0161(14) Uani 1 1 d . . . . .
C14 C 1.0318(6) 0.7464(6) 0.5679(4) 0.0224(16) Uani 1 1 d . . . . .
O3W O 0.5976(6) 0.1509(6) 0.4751(4) 0.074(2) Uani 1 1 d . . . . .
C10 C 0.8151(6) 1.2173(6) 0.1453(4) 0.0186(15) Uani 1 1 d . . . . .
C12 C 0.5491(6) 0.3845(6) 0.3458(4) 0.0259(17) Uani 1 1 d . . . . .
C9 C 0.9202(6) 0.8775(5) 0.2352(4) 0.0155(14) Uani 1 1 d . . . . .
C2 C -0.0893(7) 0.5733(5) 0.2266(4) 0.0201(15) Uani 1 1 d . . . . .
C5 C 0.4432(6) 0.4307(5) 0.1057(4) 0.0175(15) Uani 1 1 d . . . . .
C7 C 0.4675(6) 1.1027(6) 0.1333(4) 0.0219(16) Uani 1 1 d . . . . .
C15 C 1.2236(6) 0.9536(6) 0.3676(4) 0.0217(16) Uani 1 1 d . . . . .
C13 C 0.7415(7) 0.6080(6) 0.4673(4) 0.0256(17) Uani 1 1 d . . . . .
N16A N 1.4304(15) 1.1403(13) 0.3817(10) 0.061(5) Uani 0.5 1 d . . . A 1
O4WA O 1.354(2) 1.1103(16) 0.4774(10) 0.070(6) Uani 0.5 1 d . . . B 2
O5WA O 1.2857(17) 1.2209(15) 0.3594(10) 0.067(5) Uani 0.5 1 d . . . C 2
O4W O 1.3280(14) 1.0683(15) 0.5151(11) 0.063(5) Uani 0.5 1 d . . . D 1
O5W O 1.278(2) 1.2874(19) 0.3360(15) 0.107(8) Uani 0.5 1 d . . . E 1
H17A H 0.049(5) 0.709(5) 0.094(3) 0.016(18) Uiso 1 1 d D . . . .
H17B H 0.058(9) 0.736(10) 0.012(3) 0.10(5) Uiso 1 1 d D . . . .
H17C H 0.028(6) 0.825(2) 0.061(4) 0.02(2) Uiso 1 1 d D . . . .
H17D H -0.051(3) 0.745(8) 0.077(5) 0.06(3) Uiso 1 1 d D . . . .


_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
Bi1 S9 2.9889(18) 1_455 ?
Bi1 S11 2.8314(17) 2_675 ?
Bi1 S3 2.7777(18) 1_565 ?
Bi1 S7 2.7068(19) . ?
Bi1 S6 2.8397(18) . ?
Bi1 S15 2.8536(19) 1_455 ?
Bi2 S5 2.7575(18) . ?
Bi2 S8 2.7578(17) . ?
Bi2 S1 2.848(2) 2_665 ?
Bi2 S2 2.8780(18) 1_655 ?
Bi2 S10 2.9275(18) 1_545 ?
Bi2 S12 2.792(2) . ?
Bi3 S4 2.8359(19) 1_655 ?
Bi3 S4 2.8359(19) 2_666 ?
Bi3 S13 2.7809(19) . ?
Bi3 S13 2.7810(19) 2_766 ?
Bi3 S14 2.810(2) . ?
Bi3 S14 2.810(2) 2_766 ?
Ni2 O1 2.138(4) . ?
Ni2 N11 2.050(6) . ?
Ni2 N10 2.040(6) . ?
Ni2 N8 2.057(6) . ?
Ni2 N7 2.042(6) . ?
Ni2 N9 2.060(6) . ?
Ni4 O3 2.125(5) . ?
Ni4 O3 2.125(5) 2_776 ?
Ni4 N14 2.008(6) 2_776 ?
Ni4 N14 2.008(6) . ?
Ni4 N15 2.070(6) . ?
Ni4 N15 2.070(6) 2_776 ?
Ni1 N3 2.038(6) . ?
Ni1 N6 2.078(6) . ?
Ni1 N4 2.033(6) . ?
Ni1 N1 2.093(6) . ?
Ni1 N2 2.078(6) . ?
Ni1 N5 2.043(6) . ?
Ni3 O2 2.148(5) 2_666 ?
Ni3 O2 2.148(5) . ?
Ni3 N13 2.005(6) . ?
Ni3 N13 2.005(6) 2_666 ?
Ni3 N12 2.043(6) 2_666 ?
Ni3 N12 2.043(6) . ?
S9 C9 1.669(7) . ?
S11 C11 1.668(7) . ?
S3 C3 1.670(8) . ?
S5 C5 1.669(7) . ?
S7 C7 1.677(8) . ?
S8 C8 1.672(7) . ?
S1 C1 1.668(7) . ?
S2 C2 1.667(8) . ?
S6 C6 1.659(7) . ?
S10 C10 1.665(8) . ?
S4 C4 1.663(8) . ?
S15 C15 1.666(8) . ?
S12 C12 1.665(8) . ?
S13 C13 1.672(8) . ?
S14 C14 1.648(7) . ?
N3 C3 1.143(8) . ?
N11 C11 1.145(8) . ?
N6 C6 1.150(8) . ?
N10 C10 1.157(8) . ?
N8 C8 1.147(8) . ?
N4 C4 1.167(9) . ?
N1 C1 1.149(8) . ?
N2 C2 1.162(9) . ?
N7 C7 1.144(8) . ?
N9 C9 1.155(8) . ?
N13 C13 1.141(9) . ?
N5 C5 1.150(8) . ?
N14 C14 1.164(8) . ?
N12 C12 1.149(9) . ?
N15 C15 1.149(9) . ?

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
S11 Bi1 S9 88.60(5) 2_675 1_455 ?
S11 Bi1 S6 91.07(5) 2_675 . ?
S11 Bi1 S15 172.33(6) 2_675 1_455 ?
S3 Bi1 S9 77.18(5) 1_565 1_455 ?
S3 Bi1 S11 82.81(5) 1_565 2_675 ?
S3 Bi1 S6 172.17(5) 1_565 . ?
S3 Bi1 S15 94.19(6) 1_565 1_455 ?
S7 Bi1 S9 168.46(5) . 1_455 ?
S7 Bi1 S11 88.97(6) . 2_675 ?
S7 Bi1 S3 91.32(6) . 1_565 ?
S7 Bi1 S6 83.65(6) . . ?
S7 Bi1 S15 98.18(6) . 1_455 ?
S6 Bi1 S9 107.68(5) . 1_455 ?
S6 Bi1 S15 92.47(5) . 1_455 ?
S15 Bi1 S9 83.84(5) 1_455 1_455 ?
S5 Bi2 S8 96.88(5) . . ?
S5 Bi2 S1 91.53(6) . 2_665 ?
S5 Bi2 S2 175.95(5) . 1_655 ?
S5 Bi2 S10 86.21(5) . 1_545 ?
S5 Bi2 S12 83.10(6) . . ?
S8 Bi2 S1 88.11(5) . 2_665 ?
S8 Bi2 S2 85.02(5) . 1_655 ?
S8 Bi2 S10 176.90(5) . 1_545 ?
S8 Bi2 S12 87.08(6) . . ?
S1 Bi2 S2 92.10(5) 2_665 1_655 ?
S1 Bi2 S10 91.76(5) 2_665 1_545 ?
S2 Bi2 S10 91.90(5) 1_655 1_545 ?
S12 Bi2 S1 172.31(6) . 2_665 ?
S12 Bi2 S2 93.45(6) . 1_655 ?
S12 Bi2 S10 93.37(6) . 1_545 ?
S4 Bi3 S4 180.00(7) 2_666 1_655 ?
S13 Bi3 S4 82.00(6) 2_766 2_666 ?
S13 Bi3 S4 82.01(6) . 1_655 ?
S13 Bi3 S4 97.99(6) 2_766 1_655 ?
S13 Bi3 S4 97.99(6) . 2_666 ?
S13 Bi3 S13 180.00(9) . 2_766 ?
S13 Bi3 S14 95.42(7) . . ?
S13 Bi3 S14 95.42(7) 2_766 2_766 ?
S13 Bi3 S14 84.58(7) 2_766 . ?
S13 Bi3 S14 84.58(7) . 2_766 ?
S14 Bi3 S4 80.36(6) . 1_655 ?
S14 Bi3 S4 80.36(6) 2_766 2_666 ?
S14 Bi3 S4 99.64(6) . 2_666 ?
S14 Bi3 S4 99.64(6) 2_766 1_655 ?
S14 Bi3 S14 180.0 . 2_766 ?
N11 Ni2 O1 178.4(2) . . ?
N11 Ni2 N8 93.7(2) . . ?
N11 Ni2 N9 91.8(2) . . ?
N10 Ni2 O1 89.3(2) . . ?
N10 Ni2 N11 89.2(2) . . ?
N10 Ni2 N8 177.0(2) . . ?
N10 Ni2 N7 90.1(2) . . ?
N10 Ni2 N9 88.9(2) . . ?
N8 Ni2 O1 87.9(2) . . ?
N8 Ni2 N9 91.8(2) . . ?
N7 Ni2 O1 87.8(2) . . ?
N7 Ni2 N11 92.7(2) . . ?
N7 Ni2 N8 89.0(2) . . ?
N7 Ni2 N9 175.4(2) . . ?
N9 Ni2 O1 87.7(2) . . ?
O3 Ni4 O3 180.0 2_776 . ?
N14 Ni4 O3 88.2(2) 2_776 2_776 ?
N14 Ni4 O3 91.8(2) . 2_776 ?
N14 Ni4 O3 88.2(2) . . ?
N14 Ni4 O3 91.8(2) 2_776 . ?
N14 Ni4 N14 180.0 2_776 . ?
N14 Ni4 N15 91.2(2) 2_776 . ?
N14 Ni4 N15 88.8(2) 2_776 2_776 ?
N14 Ni4 N15 91.2(2) . 2_776 ?
N14 Ni4 N15 88.8(2) . . ?
N15 Ni4 O3 89.2(2) 2_776 . ?
N15 Ni4 O3 90.8(2) . . ?
N15 Ni4 O3 90.8(2) 2_776 2_776 ?
N15 Ni4 O3 89.2(2) . 2_776 ?
N15 Ni4 N15 180.0 2_776 . ?
N3 Ni1 N6 177.7(2) . . ?
N3 Ni1 N1 88.3(2) . . ?
N3 Ni1 N2 89.6(2) . . ?
N3 Ni1 N5 90.6(2) . . ?
N6 Ni1 N1 90.2(2) . . ?
N4 Ni1 N3 91.4(2) . . ?
N4 Ni1 N6 90.2(2) . . ?
N4 Ni1 N1 178.7(2) . . ?
N4 Ni1 N2 88.6(2) . . ?
N4 Ni1 N5 92.6(2) . . ?
N2 Ni1 N6 92.2(2) . . ?
N2 Ni1 N1 90.2(2) . . ?
N5 Ni1 N6 87.6(2) . . ?
N5 Ni1 N1 88.7(2) . . ?
N5 Ni1 N2 178.8(2) . . ?
O2 Ni3 O2 180.0 . 2_666 ?
N13 Ni3 O2 87.6(2) 2_666 . ?
N13 Ni3 O2 87.6(2) . 2_666 ?
N13 Ni3 O2 92.4(2) . . ?
N13 Ni3 O2 92.4(2) 2_666 2_666 ?
N13 Ni3 N13 180.0 . 2_666 ?
N13 Ni3 N12 91.9(2) 2_666 2_666 ?
N13 Ni3 N12 88.1(2) . 2_666 ?
N13 Ni3 N12 88.1(2) 2_666 . ?
N13 Ni3 N12 91.9(2) . . ?
N12 Ni3 O2 89.8(2) 2_666 . ?
N12 Ni3 O2 90.2(2) . . ?
N12 Ni3 O2 90.2(2) 2_666 2_666 ?
N12 Ni3 O2 89.8(2) . 2_666 ?
N12 Ni3 N12 180.0 2_666 . ?
C9 S9 Bi1 102.5(2) . 1_655 ?
C11 S11 Bi1 102.5(2) . 2_675 ?
C3 S3 Bi1 102.9(2) . 1_545 ?
C5 S5 Bi2 95.4(2) . . ?
C7 S7 Bi1 94.0(2) . . ?
C8 S8 Bi2 95.0(2) . . ?
C1 S1 Bi2 93.7(3) . 2_665 ?
C2 S2 Bi2 96.0(2) . 1_455 ?
C6 S6 Bi1 90.3(2) . . ?
C10 S10 Bi2 95.7(2) . 1_565 ?
C4 S4 Bi3 100.8(2) . 1_455 ?
C15 S15 Bi1 97.0(2) . 1_655 ?
C12 S12 Bi2 97.3(3) . . ?
C13 S13 Bi3 95.5(2) . . ?
C14 S14 Bi3 94.9(3) . . ?
C3 N3 Ni1 178.3(6) . . ?
C11 N11 Ni2 164.9(6) . . ?
C6 N6 Ni1 158.1(5) . . ?
C10 N10 Ni2 169.5(6) . . ?
C8 N8 Ni2 175.7(5) . . ?
C4 N4 Ni1 169.2(5) . . ?
C1 N1 Ni1 145.5(6) . . ?
C2 N2 Ni1 154.6(6) . . ?
C7 N7 Ni2 177.3(6) . . ?
C9 N9 Ni2 169.5(5) . . ?
C13 N13 Ni3 173.2(6) . . ?
C5 N5 Ni1 169.0(6) . . ?
C14 N14 Ni4 170.3(6) . . ?
C12 N12 Ni3 173.7(6) . . ?
C15 N15 Ni4 172.1(6) . . ?
N1 C1 S1 177.5(7) . . ?
N4 C4 S4 178.4(7) . . ?
N3 C3 S3 176.9(6) . . ?
N8 C8 S8 179.2(7) . . ?
N11 C11 S11 175.6(7) . . ?
N6 C6 S6 177.6(6) . . ?
N14 C14 S14 179.6(6) . . ?
N10 C10 S10 179.0(7) . . ?
N12 C12 S12 178.0(8) . . ?
N9 C9 S9 178.7(6) . . ?
N2 C2 S2 178.9(7) . . ?
N5 C5 S5 179.3(7) . . ?
N7 C7 S7 179.3(7) . . ?
N15 C15 S15 178.0(7) . . ?
N13 C13 S13 178.0(7) . . ?

_olex2_submission_special_instructions 'No special instructions were received'

# start Validation Reply Form
_vrf_PLAT043_4_Ni6Bi5NCS30_3NH4  
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      66.59 Check 
RESPONSE: It was not possible to locate the hydrogen atoms of the water cluster
 in the difference map, and the range of different possible hydrogen positions
 precluded placing them geometrically.
;
_vrf_PLAT306_4_Ni6Bi5NCS30_3NH4  
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......        O1W Check 
RESPONSE: Hydrogen bond present but it was not possible to locate the hydrogen 
 atoms of the water cluster in the difference map. The range of different
 possible hydrogen positions precluded placing them geometrically.
;
_vrf_PLAT430_4_Ni6Bi5NCS30_3NH4  
;
PROBLEM: Short Inter D...A Contact  O1       ..O1W      .       2.76 Ang.  
RESPONSE: Hydrogen bond present but it was not possible to locate the hydrogen 
 atoms of the water cluster in the difference map. The range of different
 possible hydrogen positions precluded placing them geometrically.
;
_vrf_PLAT910_4_Ni6Bi5NCS30_3NH4  
;
PROBLEM: Missing # of FCF Reflection(s) Below Theta(Min).         17 Note  
RESPONSE: Due to beam-stop occluding the reflections.
;
# end Validation Reply Form


####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1
_database_code_depnum_ccdc_archive 'CCDC 1986924'
loop_
_audit_author_name
_audit_author_address
'Matthew J. Cliffe'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2020-02-27 deposited with the CCDC.	2020-04-09 downloaded from the CCDC.
;
#===============================================================================
_audit_creation_method           SHELXL-2018/1
_chemical_name_systematic        
'manganese hexathiocyanatobismuthate thiocyanate heptahydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C7 H10 Bi Mn2 N7 O5 S7, 2(H2 O)'
_chemical_formula_sum            'C7 H14 Bi Mn2 N7 O7 S7'
_chemical_formula_weight         851.53

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'
Bi Bi -4.0111 8.9310 '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'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   8.3698(3)
_cell_length_b                   26.0037(9)
_cell_length_c                   12.2466(4)
_cell_angle_alpha                90
_cell_angle_beta                 91.208(2)
_cell_angle_gamma                90
_cell_volume                     2664.83(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    300(2)
_cell_measurement_reflns_used    6808
_cell_measurement_theta_min      3.40
_cell_measurement_theta_max      66.60

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.122
_exptl_crystal_F_000             1624
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    25.858
_shelx_estimated_absorpt_T_min   0.122
_shelx_estimated_absorpt_T_max   0.782
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3751
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_process_details   'SADABS (Bruker, 2014)'

_diffrn_ambient_temperature      300(2)
_diffrn_radiation_wavelength     1.5418
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Incoatec I\mS Cu microsource'
_diffrn_measurement_device_type  'Bruker D8-QUEST PHOTON-100'
_diffrn_measurement_method       'ω and φ-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            30850
_diffrn_reflns_av_unetI/netI     0.0734
_diffrn_reflns_av_R_equivalents  0.1315
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.399
_diffrn_reflns_theta_max         66.717
_diffrn_reflns_theta_full        66.717
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4712
_reflns_number_gt                3248
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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_data_collection       'APEX3 (Bruker, 2016)'
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_reduction        SAINT
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  SHELXL

_refine_special_details          ?

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0867P)²+0.2708P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4712
_refine_ls_number_parameters     280
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0913
_refine_ls_R_factor_gt           0.0553
_refine_ls_wR_factor_ref         0.1544
_refine_ls_wR_factor_gt          0.1326
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_restrained_S_all      1.017
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_diff_density_max         3.391
_refine_diff_density_min         -1.432
_refine_diff_density_rms         0.217

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
Bi1 Bi 0.46300(5) 0.33413(2) -0.05778(3) 0.03613(16) Uani 1 1 d . . . . .
Mn1 Mn 0.000000 0.500000 0.000000 0.0401(6) Uani 1 2 d S . P . .
Mn2 Mn 0.4559(2) 0.33707(7) 0.44039(15) 0.0405(4) Uani 1 1 d . . . . .
Mn3 Mn 1.000000 0.500000 0.500000 0.0520(7) Uani 1 2 d S . P . .
S1 S 0.2630(5) 0.64848(16) 0.1849(3) 0.0641(10) Uani 1 1 d . . . . .
S2 S 0.5235(4) 0.42659(15) 0.0546(4) 0.0642(10) Uani 1 1 d . . . . .
S3 S -0.0568(5) 0.25741(16) 0.3210(4) 0.0678(11) Uani 1 1 d . . . . .
S4 S 0.7088(5) 0.17822(15) 0.5867(3) 0.0671(11) Uani 1 1 d . . . . .
S5 S 0.6742(6) 0.28450(19) 0.0870(3) 0.0772(14) Uani 1 1 d . . . . .
S6 S 0.2109(5) 0.36863(18) 0.8008(3) 0.0666(11) Uani 1 1 d . . . . .
N1 N 0.1096(14) 0.5715(4) 0.0622(10) 0.055(3) Uani 1 1 d . . . . .
N2 N 0.2080(16) 0.4585(5) 0.0670(11) 0.064(3) Uani 1 1 d . . . . .
N3 N 0.2313(17) 0.3017(5) 0.3896(10) 0.065(3) Uani 1 1 d . . . . .
N4 N 0.5734(16) 0.2675(5) 0.5007(11) 0.068(4) Uani 1 1 d . . . . .
N5 N 0.5639(18) 0.3254(6) 0.2815(10) 0.071(4) Uani 1 1 d . . . . .
N6 N 0.3520(17) 0.3550(5) 0.5989(10) 0.062(3) Uani 1 1 d . . . . .
C1 C 0.1744(16) 0.6025(5) 0.1102(11) 0.047(3) Uani 1 1 d . . . . .
C2 C 0.3387(15) 0.4454(5) 0.0616(10) 0.042(3) Uani 1 1 d . . . . .
C3 C 0.1153(16) 0.2834(5) 0.3607(9) 0.042(3) Uani 1 1 d . . . . .
C4 C 0.6300(15) 0.2311(5) 0.5354(10) 0.043(3) Uani 1 1 d . . . . .
C5 C 0.6060(18) 0.3080(6) 0.2035(11) 0.055(4) Uani 1 1 d . . . . .
C6 C 0.2983(17) 0.3611(6) 0.6843(11) 0.053(3) Uani 1 1 d . . . . .
O1 O -0.1243(11) 0.4929(4) 0.1613(7) 0.060(3) Uani 1 1 d . . . . .
H11 H -0.133080 0.461517 0.181175 0.090 Uiso 1 1 d R U . . .
H12 H -0.208980 0.510678 0.171156 0.090 Uiso 1 1 d R U . . .
O4 O 1.0846(15) 0.5269(5) 0.3404(9) 0.087(4) Uani 1 1 d . . . . .
H41 H 1.024992 0.516075 0.288765 0.130 Uiso 1 1 d R U . . .
H42 H 1.184675 0.524605 0.327085 0.130 Uiso 1 1 d R U . . .
O5 O 0.9632(14) 0.5803(5) 0.5510(10) 0.080(3) Uani 1 1 d . . . . .
H51 H 0.984976 0.606733 0.512652 0.119 Uiso 1 1 d R U . . .
H52 H 1.007846 0.588643 0.610952 0.119 Uiso 1 1 d R U . . .
S7 S 0.4959(6) 0.51949(17) 0.2891(4) 0.0790(13) Uani 0.70(3) 1 d . . P A 1
N7 N 0.750(3) 0.5059(10) 0.4329(19) 0.067(6) Uiso 0.70(3) 1 d . . P A 1
C7 C 0.644(2) 0.5090(7) 0.3740(15) 0.044(5) Uiso 0.70(3) 1 d . . P A 1
O2 O 0.351(2) 0.4093(7) 0.3670(15) 0.063(5) Uiso 0.70(3) 1 d . . P A 1
H21 H 0.256759 0.412453 0.393299 0.094 Uiso 0.70(3) 1 d R U P A 1
H22 H 0.385229 0.438863 0.347630 0.094 Uiso 0.70(3) 1 d R U P A 1
O3 O 0.657(3) 0.3860(8) 0.5125(18) 0.080(6) Uiso 0.70(3) 1 d . . P A 1
H31 H 0.742108 0.372121 0.537736 0.121 Uiso 0.70(3) 1 d R U P A 1
H32 H 0.678118 0.417261 0.496077 0.121 Uiso 0.70(3) 1 d R U P A 1
S7A S 0.4959(6) 0.51949(17) 0.2891(4) 0.0790(13) Uani 0.30(3) 1 d . . P A 2
N7A N 0.397(5) 0.4150(13) 0.397(3) 0.034(8) Uiso 0.30(3) 1 d . . P A 2
C7A C 0.425(9) 0.459(3) 0.353(6) 0.10(3) Uiso 0.30(3) 1 d . . P A 2
O2A O 1.232(5) 0.515(2) 0.565(3) 0.070(12) Uiso 0.30(3) 1 d . . P A 2
H21A H 1.251192 0.547070 0.564661 0.105 Uiso 0.30(3) 1 d R U P A 2
H22A H 1.306392 0.504820 0.607581 0.105 Uiso 0.30(3) 1 d R U P A 2
O3A O 0.688(4) 0.3772(14) 0.474(3) 0.053(9) Uiso 0.30(3) 1 d . . P A 2
H31A H 0.763153 0.366002 0.514956 0.079 Uiso 0.30(3) 1 d R U P A 2
H32A H 0.744693 0.382251 0.417616 0.079 Uiso 0.30(3) 1 d R U P A 2
O1W O -0.093(2) 0.3935(5) 0.2382(12) 0.117(5) Uani 1 1 d . . . . .
H1W H -0.023510 0.377356 0.200704 0.175 Uiso 1 1 d R U . . .
H2W H -0.178840 0.375846 0.244984 0.175 Uiso 1 1 d R U . . .
O2W O 0.9432(19) 0.3383(6) 0.5820(11) 0.107(5) Uani 1 1 d . . . . .
H3W H 0.995855 0.310139 0.581256 0.161 Uiso 1 1 d R U . . .
H4W H 0.890285 0.341589 0.640786 0.161 Uiso 1 1 d 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
Bi1 S5 2.793(4) . ?
Bi1 S3 2.808(4) 4_665 ?
Bi1 S2 2.811(4) . ?
Bi1 S4 2.814(4) 4_565 ?
Bi1 S1 2.835(4) 3_665 ?
Bi1 S6 2.847(4) 1_554 ?
Mn1 N2 2.192(13) 3_565 ?
Mn1 N2 2.192(13) . ?
Mn1 N1 2.203(12) 3_565 ?
Mn1 N1 2.203(12) . ?
Mn1 O1 2.259(9) . ?
Mn1 O1 2.259(9) 3_565 ?
Mn2 N7A 2.15(3) . ?
Mn2 N3 2.172(14) . ?
Mn2 N4 2.180(14) . ?
Mn2 N5 2.183(13) . ?
Mn2 N6 2.194(12) . ?
Mn2 O3A 2.24(3) . ?
Mn2 O2 2.254(17) . ?
Mn2 O3 2.27(2) . ?
Mn3 O2A 2.12(4) . ?
Mn3 O2A 2.12(4) 3_766 ?
Mn3 O5 2.203(11) . ?
Mn3 O5 2.203(11) 3_766 ?
Mn3 O4 2.207(11) 3_766 ?
Mn3 O4 2.207(11) . ?
Mn3 N7 2.23(3) 3_766 ?
Mn3 N7 2.23(3) . ?
S1 C1 1.669(14) . ?
S2 C2 1.627(12) . ?
S3 C3 1.655(14) . ?
S4 C4 1.643(13) . ?
S5 C5 1.664(14) . ?
S6 C6 1.629(14) . ?
N1 C1 1.129(17) . ?
N2 C2 1.149(17) . ?
N3 C3 1.131(17) . ?
N4 C4 1.138(18) . ?
N5 C5 1.121(18) . ?
N6 C6 1.157(17) . ?
O1 H11 0.8546 . ?
O1 H12 0.8576 . ?
O4 H41 0.8456 . ?
O4 H42 0.8589 . ?
O5 H51 0.8547 . ?
O5 H52 0.8452 . ?
S7 C7 1.621(18) . ?
N7 C7 1.14(3) . ?
O2 H21 0.8603 . ?
O2 H22 0.8558 . ?
O3 H31 0.8508 . ?
O3 H32 0.8557 . ?
S7A C7A 1.86(8) . ?
N7A C7A 1.29(8) . ?
O2A H21A 0.8603 . ?
O2A H22A 0.8447 . ?
O3A H31A 0.8474 . ?
O3A H32A 0.8578 . ?
O1W H1W 0.8592 . ?
O1W H2W 0.8571 . ?
O2W H3W 0.8557 . ?
O2W H4W 0.8571 . ?

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
S5 Bi1 S3 88.47(12) . 4_665 ?
S5 Bi1 S2 88.81(13) . . ?
S3 Bi1 S2 172.64(12) 4_665 . ?
S5 Bi1 S4 91.43(14) . 4_565 ?
S3 Bi1 S4 101.47(12) 4_665 4_565 ?
S2 Bi1 S4 85.44(11) . 4_565 ?
S5 Bi1 S1 85.04(14) . 3_665 ?
S3 Bi1 S1 83.36(12) 4_665 3_665 ?
S2 Bi1 S1 89.59(11) . 3_665 ?
S4 Bi1 S1 173.97(11) 4_565 3_665 ?
S5 Bi1 S6 169.40(15) . 1_554 ?
S3 Bi1 S6 84.88(12) 4_665 1_554 ?
S2 Bi1 S6 98.75(13) . 1_554 ?
S4 Bi1 S6 81.84(13) 4_565 1_554 ?
S1 Bi1 S6 102.33(12) 3_665 1_554 ?
N2 Mn1 N2 180.0 3_565 . ?
N2 Mn1 N1 88.0(4) 3_565 3_565 ?
N2 Mn1 N1 92.0(4) . 3_565 ?
N2 Mn1 N1 92.0(4) 3_565 . ?
N2 Mn1 N1 88.0(4) . . ?
N1 Mn1 N1 180.0(5) 3_565 . ?
N2 Mn1 O1 89.5(5) 3_565 . ?
N2 Mn1 O1 90.5(5) . . ?
N1 Mn1 O1 92.1(4) 3_565 . ?
N1 Mn1 O1 87.9(4) . . ?
N2 Mn1 O1 90.5(5) 3_565 3_565 ?
N2 Mn1 O1 89.5(5) . 3_565 ?
N1 Mn1 O1 87.9(4) 3_565 3_565 ?
N1 Mn1 O1 92.1(4) . 3_565 ?
O1 Mn1 O1 180.0 . 3_565 ?
N7A Mn2 N3 97.7(12) . . ?
N7A Mn2 N4 165.0(12) . . ?
N3 Mn2 N4 97.3(5) . . ?
N7A Mn2 N5 90.3(10) . . ?
N3 Mn2 N5 93.3(5) . . ?
N4 Mn2 N5 89.7(5) . . ?
N7A Mn2 N6 85.8(10) . . ?
N3 Mn2 N6 89.2(5) . . ?
N4 Mn2 N6 93.5(5) . . ?
N5 Mn2 N6 175.6(6) . . ?
N7A Mn2 O3A 78.5(14) . . ?
N3 Mn2 O3A 173.7(11) . . ?
N4 Mn2 O3A 86.6(10) . . ?
N5 Mn2 O3A 81.7(12) . . ?
N6 Mn2 O3A 95.5(12) . . ?
N3 Mn2 O2 84.9(6) . . ?
N4 Mn2 O2 175.1(6) . . ?
N5 Mn2 O2 85.7(6) . . ?
N6 Mn2 O2 91.0(6) . . ?
N3 Mn2 O3 167.8(7) . . ?
N4 Mn2 O3 90.4(7) . . ?
N5 Mn2 O3 96.1(8) . . ?
N6 Mn2 O3 80.8(7) . . ?
O2 Mn2 O3 88.2(7) . . ?
O2A Mn3 O2A 180.0 . 3_766 ?
O2A Mn3 O5 81.8(15) . . ?
O2A Mn3 O5 98.2(15) 3_766 . ?
O5 Mn3 O5 180.0 . 3_766 ?
O5 Mn3 O4 90.0(5) . 3_766 ?
O5 Mn3 O4 90.0(5) 3_766 3_766 ?
O2A Mn3 O4 88.1(12) . . ?
O2A Mn3 O4 91.9(12) 3_766 . ?
O5 Mn3 O4 90.0(5) . . ?
O5 Mn3 O4 90.0(5) 3_766 . ?
O4 Mn3 O4 180.0 3_766 . ?
O5 Mn3 N7 95.5(7) . 3_766 ?
O5 Mn3 N7 84.5(7) 3_766 3_766 ?
O4 Mn3 N7 88.1(7) 3_766 3_766 ?
O4 Mn3 N7 91.9(7) . 3_766 ?
O5 Mn3 N7 84.5(7) . . ?
O5 Mn3 N7 95.5(7) 3_766 . ?
O4 Mn3 N7 91.9(7) 3_766 . ?
O4 Mn3 N7 88.1(7) . . ?
N7 Mn3 N7 180.0 3_766 . ?
C1 S1 Bi1 99.7(4) . 3_665 ?
C2 S2 Bi1 97.0(5) . . ?
C3 S3 Bi1 98.6(4) . 4_566 ?
C4 S4 Bi1 99.1(4) . 4_666 ?
C5 S5 Bi1 98.6(5) . . ?
C6 S6 Bi1 98.8(5) . 1_556 ?
C1 N1 Mn1 167.0(12) . . ?
C2 N2 Mn1 151.0(13) . . ?
C3 N3 Mn2 178.4(12) . . ?
C4 N4 Mn2 177.2(12) . . ?
C5 N5 Mn2 163.6(15) . . ?
C6 N6 Mn2 175.4(13) . . ?
N1 C1 S1 177.3(12) . . ?
N2 C2 S2 179.7(15) . . ?
N3 C3 S3 178.5(14) . . ?
N4 C4 S4 179.0(13) . . ?
N5 C5 S5 177.3(17) . . ?
N6 C6 S6 176.1(14) . . ?
Mn1 O1 H11 111.8 . . ?
Mn1 O1 H12 118.5 . . ?
H11 O1 H12 113.5 . . ?
Mn3 O4 H41 111.2 . . ?
Mn3 O4 H42 118.6 . . ?
H41 O4 H42 113.4 . . ?
Mn3 O5 H51 125.0 . . ?
Mn3 O5 H52 115.4 . . ?
H51 O5 H52 100.1 . . ?
C7 N7 Mn3 162(2) . . ?
N7 C7 S7 174(2) . . ?
Mn2 O2 H21 106.4 . . ?
Mn2 O2 H22 136.7 . . ?
H21 O2 H22 109.6 . . ?
Mn2 O3 H31 120.6 . . ?
Mn2 O3 H32 126.5 . . ?
H31 O3 H32 108.3 . . ?
C7A N7A Mn2 154(4) . . ?
N7A C7A S7A 172(6) . . ?
Mn3 O2A H21A 110.2 . . ?
Mn3 O2A H22A 146.9 . . ?
H21A O2A H22A 99.2 . . ?
Mn2 O3A H31A 125.4 . . ?
Mn2 O3A H32A 114.5 . . ?
H31A O3A H32A 96.4 . . ?
H1W O1W H2W 111.6 . . ?
H3W O2W H4W 111.7 . . ?


# start Validation Reply Form
_vrf_PLAT201_1                   
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          2 Report
RESPONSE: Partially occupied water atoms which cannot be refined in a 
stable manner due to the near overlap of an N atom.
;
_vrf_PLAT420_1                   
;
PROBLEM: D-H Without Acceptor       O1       --H12      .     Please Check 
RESPONSE: No acceptor atoms present in structure that would facilitate
this.
;
_vrf_PLAT971_1                   
;
PROBLEM: Check Calcd Resid. Dens.  0.96A   From Bi1             3.41 eA-3  
RESPONSE: It is common for residual density to remain near heavy atoms, due to 
fourier termination ripples. The size of the ripples are 4% of the number
of electrons on the heaviest atom (Bi).
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: water'
