# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_a
_database_code_depnum_ccdc_archive 'CCDC 2032746'
_audit_update_record             
;
2020-09-18 deposited with the CCDC.	2020-10-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Bi4 I6 O24 Se'
_chemical_formula_weight         2060.28

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'
I I -0.4742 1.8119 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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'
'-y, x-y, z'
'-x+y, -x, z'
'-y, -x, z+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'-y+2/3, -x+1/3, z+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-y+1/3, -x+2/3, z+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   9.568
_cell_length_b                   9.568
_cell_length_c                   37.542
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2976.1
_cell_formula_units_Z            6
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2077
_cell_measurement_theta_min      2.5371
_cell_measurement_theta_max      26.4652

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            Colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    6.897
_exptl_crystal_F_000             2712
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    46.661
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            7374
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_av_R_equivalents  0.0985
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_theta_min         2.687
_diffrn_reflns_theta_max         26.346
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             1349
_reflns_number_gt                1267
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.984
_reflns_Friedel_fraction_max     0.991
_reflns_Friedel_fraction_full    0.992

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0101P)²+944.5448P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.000172(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 539 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.026(9)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1349
_refine_ls_number_parameters     107
_refine_ls_number_restraints     37
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0464
_refine_ls_wR_factor_ref         0.0997
_refine_ls_wR_factor_gt          0.0959
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_restrained_S_all      1.082
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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 -0.3892(2) -0.2974(2) -0.09332(3) 0.0198(5) Uani 1 1 d . . . . .
Bi2 Bi 0.0000 0.0000 -0.17442(7) 0.0174(6) Uani 1 3 d S T P . .
Se1 Se 0.0000 0.0000 -0.04734(15) 0.0061(12) Uani 1 3 d S T P . .
I1 I -0.4168(3) -0.3176(3) -0.20051(7) 0.0161(6) Uani 1 1 d . . . . .
I2 I -0.2938(4) 0.0856(4) -0.13634(8) 0.0256(7) Uani 1 1 d . . . . .
O1 O -0.475(3) -0.349(3) -0.1536(7) 0.018(6) Uani 1 1 d . . . . .
O2 O -0.6667 -0.3333 -0.0778(11) 0.007(8) Uani 1 3 d S T P . .
O3 O -0.6667 -0.3333 -0.2114(12) 0.022(11) Uani 1 3 d S T P . .
O4 O 0.0000 0.0000 -0.0035(11) 0.014(9) Uani 1 3 d S T P . .
O5 O -0.344(3) -0.100(3) -0.2048(6) 0.011(5) Uani 1 1 d . U . . .
O6 O -0.167(3) 0.263(3) -0.1137(6) 0.010(5) Uani 1 1 d . U . . .
O7 O -0.126(3) -0.176(3) -0.0622(6) 0.012(5) Uani 1 1 d . U . . .
O8 O -0.186(3) -0.024(3) -0.1328(7) 0.010(5) Uani 1 1 d . U . . .
O9 O -0.430(3) -0.029(3) -0.0994(6) 0.007(5) Uani 1 1 d . U . . .
O10 O -0.203(3) -0.279(3) -0.1928(7) 0.019(6) Uani 1 1 d . 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 O6 2.27(2) 2 ?
Bi1 O1 2.38(3) . ?
Bi1 O9 2.38(2) 3_445 ?
Bi1 O5 2.38(2) 17_444 ?
Bi1 O7 2.47(2) . ?
Bi1 O2 2.568(10) . ?
Bi2 O8 2.29(2) . ?
Bi2 O8 2.29(2) 3 ?
Bi2 O8 2.29(2) 2 ?
Bi2 O10 2.49(3) 2 ?
Bi2 O10 2.49(3) 3 ?
Bi2 O10 2.49(3) . ?
Bi2 O2 2.63(4) 10_444 ?
Se1 O7 1.61(3) . ?
Se1 O7 1.61(2) 2 ?
Se1 O7 1.61(2) 3 ?
Se1 O4 1.65(4) . ?
I1 O1 1.83(3) . ?
I1 O5 1.84(3) . ?
I1 O10 1.91(3) . ?
I1 O3 2.355(8) . ?
I2 O6 1.74(2) . ?
I2 O8 1.81(3) . ?
I2 O9 1.84(2) . ?
O2 Bi1 2.568(10) 2_455 ?
O2 Bi1 2.568(10) 3_445 ?
O2 Bi2 2.63(4) 16_444 ?
O3 I1 2.355(8) 2_455 ?
O3 I1 2.355(8) 3_445 ?
O5 Bi1 2.38(2) 11_454 ?
O6 Bi1 2.27(2) 3 ?
O9 Bi1 2.38(2) 2_455 ?

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
O6 Bi1 O1 77.9(10) 2 . ?
O6 Bi1 O9 75.6(8) 2 3_445 ?
O1 Bi1 O9 70.4(8) . 3_445 ?
O6 Bi1 O5 87.3(8) 2 17_444 ?
O1 Bi1 O5 141.1(8) . 17_444 ?
O9 Bi1 O5 71.1(8) 3_445 17_444 ?
O6 Bi1 O7 73.8(8) 2 . ?
O1 Bi1 O7 135.5(9) . . ?
O9 Bi1 O7 131.6(8) 3_445 . ?
O5 Bi1 O7 70.9(8) 17_444 . ?
O6 Bi1 O2 143.4(7) 2 . ?
O1 Bi1 O2 87.7(11) . . ?
O9 Bi1 O2 67.9(6) 3_445 . ?
O5 Bi1 O2 83.2(10) 17_444 . ?
O7 Bi1 O2 134.2(10) . . ?
O8 Bi2 O8 78.6(10) . 3 ?
O8 Bi2 O8 78.6(10) . 2 ?
O8 Bi2 O8 78.6(10) 3 2 ?
O8 Bi2 O10 152.2(9) . 2 ?
O8 Bi2 O10 75.7(9) 3 2 ?
O8 Bi2 O10 86.0(9) 2 2 ?
O8 Bi2 O10 75.7(9) . 3 ?
O8 Bi2 O10 86.0(9) 3 3 ?
O8 Bi2 O10 152.2(9) 2 3 ?
O10 Bi2 O10 112.6(5) 2 3 ?
O8 Bi2 O10 86.0(9) . . ?
O8 Bi2 O10 152.2(9) 3 . ?
O8 Bi2 O10 75.7(9) 2 . ?
O10 Bi2 O10 112.6(5) 2 . ?
O10 Bi2 O10 112.6(5) 3 . ?
O8 Bi2 O2 133.0(6) . 10_444 ?
O8 Bi2 O2 133.0(6) 3 10_444 ?
O8 Bi2 O2 133.0(6) 2 10_444 ?
O10 Bi2 O2 73.9(6) 2 10_444 ?
O10 Bi2 O2 73.9(6) 3 10_444 ?
O10 Bi2 O2 73.9(6) . 10_444 ?
O7 Se1 O7 108.6(9) . 2 ?
O7 Se1 O7 108.6(9) . 3 ?
O7 Se1 O7 108.6(9) 2 3 ?
O7 Se1 O4 110.4(9) . . ?
O7 Se1 O4 110.4(9) 2 . ?
O7 Se1 O4 110.4(9) 3 . ?
O1 I1 O5 100.4(11) . . ?
O1 I1 O10 95.5(12) . . ?
O5 I1 O10 91.8(11) . . ?
O1 I1 O3 86.5(14) . . ?
O5 I1 O3 81.7(8) . . ?
O10 I1 O3 173.4(9) . . ?
O6 I2 O8 102.0(11) . . ?
O6 I2 O9 98.9(11) . . ?
O8 I2 O9 92.1(11) . . ?
I1 O1 Bi1 147.0(15) . . ?
Bi1 O2 Bi1 115.0(7) 2_455 3_445 ?
Bi1 O2 Bi1 115.0(7) 2_455 . ?
Bi1 O2 Bi1 115.0(7) 3_445 . ?
Bi1 O2 Bi2 103.1(9) 2_455 16_444 ?
Bi1 O2 Bi2 103.1(9) 3_445 16_444 ?
Bi1 O2 Bi2 103.1(9) . 16_444 ?
I1 O3 I1 117.1(6) 2_455 3_445 ?
I1 O3 I1 117.1(6) 2_455 . ?
I1 O3 I1 117.1(6) 3_445 . ?
I1 O5 Bi1 120.8(12) . 11_454 ?
I2 O6 Bi1 136.7(13) . 3 ?
Se1 O7 Bi1 135.4(13) . . ?
I2 O8 Bi2 122.1(13) . . ?
I2 O9 Bi1 125.5(11) . 2_455 ?
I1 O10 Bi2 115.7(13) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O5 I1 O1 Bi1 -68(3) . . . . ?
O10 I1 O1 Bi1 25(3) . . . . ?
O3 I1 O1 Bi1 -149(3) . . . . ?
O1 I1 O5 Bi1 179.4(13) . . . 11_454 ?
O10 I1 O5 Bi1 83.4(14) . . . 11_454 ?
O3 I1 O5 Bi1 -95.8(16) . . . 11_454 ?
O8 I2 O6 Bi1 14(2) . . . 3 ?
O9 I2 O6 Bi1 107.8(19) . . . 3 ?
O7 Se1 O7 Bi1 -129.0(6) 2 . . . ?
O7 Se1 O7 Bi1 -11(3) 3 . . . ?
O4 Se1 O7 Bi1 109.9(16) . . . . ?
O6 I2 O8 Bi2 -89.6(15) . . . . ?
O9 I2 O8 Bi2 170.8(14) . . . . ?
O6 I2 O9 Bi1 108.3(15) . . . 2_455 ?
O8 I2 O9 Bi1 -149.2(14) . . . 2_455 ?

_refine_diff_density_max         4.558
_refine_diff_density_min         -3.015
_refine_diff_density_rms         0.532

