# Supplementary Information (SI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC) in cooperation with FIZ Karlsruhe.
# 
# Please note that these data are only for research purposes or private use.
# For detailed information please see under Terms & Conditions.
# Full information about CCDC and FIZ Karlsruhe 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 FIZ Karlsruhe. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
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data_KBiP2S6
_audit_block_doi                 10.25505/fiz.icsd.cc2b8nq0
_database_code_depnum_ccdc_archive 'CCDC 2153282'
loop_
_citation_id
_citation_doi
_citation_year
1 10.1021/acsmaterialslett.2c00409 2022
loop_
_audit_author_name
_audit_author_address
'Hua Lin'
;Fujian Institute of Research on the Structure of Matter, CAS
China
;
_audit_update_record             
;
2022-02-19 deposited with the CCDC.	2025-11-17 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            'Bi K P2 S6'
_chemical_formula_weight         502.38

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
P P 0.1023 0.0942 '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'
K K 0.2009 0.2494 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   6.629(3)
_cell_length_b                   7.416(3)
_cell_length_c                   9.919(5)
_cell_angle_alpha                90
_cell_angle_beta                 92.097(8)
_cell_angle_gamma                90
_cell_volume                     487.3(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2615
_cell_measurement_theta_min      2.0545
_cell_measurement_theta_max      36.3056

_exptl_crystal_description       Prism
_exptl_crystal_colour            Red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.424
_exptl_crystal_F_000             456
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.1000
_exptl_crystal_size_mid          0.0800
_exptl_crystal_size_min          0.0700
_exptl_absorpt_coefficient_mu    20.054
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.4342
_exptl_absorpt_correction_T_max  1.0000
_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                   ?
_diffrn_measurement_device_type  Saturn724
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean 28.5714
_diffrn_reflns_number            3497
_diffrn_reflns_av_unetI/netI     0.0645
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.054
_diffrn_reflns_theta_max         24.981
_diffrn_reflns_theta_full        24.981
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_point_group_measured_fraction_full 0.932
_reflns_number_total             1593
_reflns_number_gt                1555
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_max     0.866
_reflns_Friedel_fraction_full    0.866

_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)+(0.0382P)²+0.2368P] 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       0.0071(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 618 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.028(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1593
_refine_ls_number_parameters     92
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0391
_refine_ls_R_factor_gt           0.0373
_refine_ls_wR_factor_ref         0.0872
_refine_ls_wR_factor_gt          0.0863
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.091
_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
K K 0.2024(5) 0.7501(7) 0.0021(4) 0.0312(10) Uani 1 1 d . . . . .
Bi Bi 0.29386(7) 0.00000(14) 0.48024(5) 0.0251(3) Uani 1 1 d . . . . .
P1 P 0.1874(6) 0.4608(6) 0.3257(4) 0.0204(11) Uani 1 1 d . . . . .
P2 P 0.2957(6) 0.2328(6) 0.2000(4) 0.0188(9) Uani 1 1 d . . . . .
S1 S 0.5519(6) 0.1500(6) 0.3062(4) 0.0223(9) Uani 1 1 d . . . . .
S2 S 0.4138(6) 0.6476(6) 0.3254(4) 0.0213(9) Uani 1 1 d . . . . .
S3 S 0.0846(6) 0.0404(6) 0.2311(4) 0.0227(10) Uani 1 1 d . . . . .
S4 S 0.0748(6) 0.0462(5) 0.7545(4) 0.0221(10) Uani 1 1 d . . . . .
S5 S 0.1599(7) 0.3440(7) 0.5138(4) 0.0219(9) Uani 1 1 d . . . . .
S6 S 0.3229(7) 0.3137(7) 0.0127(4) 0.0273(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
K S6 3.191(6) 2_655 ?
K S3 3.246(6) 1_565 ?
K S3 3.326(6) 2 ?
K S6 3.334(8) . ?
K S4 3.379(6) 1_564 ?
K S4 3.438(6) 2_556 ?
K S6 3.512(6) 2 ?
K S2 3.535(6) . ?
K S1 3.594(6) 2_655 ?
K P2 3.802(6) 2 ?
K P1 3.866(6) . ?
K K 4.577(5) 2 ?
Bi S1 2.713(4) . ?
Bi S5 2.726(5) . ?
Bi S3 2.806(4) . ?
Bi S2 2.898(4) 2_646 ?
P1 S4 1.989(6) 2_556 ?
P1 S2 2.043(6) . ?
P1 S5 2.071(6) . ?
P1 P2 2.235(6) . ?
P2 S6 1.967(6) . ?
P2 S3 2.030(6) . ?
P2 S1 2.059(6) . ?
P2 K 3.802(6) 2_545 ?
S1 K 3.594(6) 2_645 ?
S2 Bi 2.898(4) 2_656 ?
S3 K 3.246(6) 1_545 ?
S3 K 3.326(6) 2_545 ?
S4 P1 1.989(6) 2_546 ?
S4 K 3.379(6) 1_546 ?
S4 K 3.438(6) 2_546 ?
S6 K 3.191(6) 2_645 ?
S6 K 3.512(6) 2_545 ?

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
S6 K S3 101.36(17) 2_655 1_565 ?
S6 K S3 125.27(16) 2_655 2 ?
S3 K S3 130.58(13) 1_565 2 ?
S6 K S6 84.81(14) 2_655 . ?
S3 K S6 133.25(18) 1_565 . ?
S3 K S6 72.45(15) 2 . ?
S6 K S4 95.26(16) 2_655 1_564 ?
S3 K S4 90.99(17) 1_565 1_564 ?
S3 K S4 71.15(13) 2 1_564 ?
S6 K S4 135.00(17) . 1_564 ?
S6 K S4 130.59(17) 2_655 2_556 ?
S3 K S4 69.61(13) 1_565 2_556 ?
S3 K S4 88.61(15) 2 2_556 ?
S6 K S4 71.60(14) . 2_556 ?
S4 K S4 132.09(13) 1_564 2_556 ?
S6 K S6 163.0(3) 2_655 2 ?
S3 K S6 71.12(13) 1_565 2 ?
S3 K S6 59.52(12) 2 2 ?
S6 K S6 111.57(18) . 2 ?
S4 K S6 70.18(13) 1_564 2 ?
S4 K S6 62.19(12) 2_556 2 ?
S6 K S2 73.41(13) 2_655 . ?
S3 K S2 66.74(13) 1_565 . ?
S3 K S2 136.70(19) 2 . ?
S6 K S2 71.11(14) . . ?
S4 K S2 151.57(19) 1_564 . ?
S4 K S2 58.17(11) 2_556 . ?
S6 K S2 115.22(14) 2 . ?
S6 K S1 60.87(12) 2_655 2_655 ?
S3 K S1 149.4(2) 1_565 2_655 ?
S3 K S1 65.01(12) 2 2_655 ?
S6 K S1 73.20(14) . 2_655 ?
S4 K S1 67.98(12) 1_564 2_655 ?
S4 K S1 141.0(2) 2_556 2_655 ?
S6 K S1 118.15(14) 2 2_655 ?
S2 K S1 123.41(15) . 2_655 ?
S6 K P2 145.08(16) 2_655 2 ?
S3 K P2 99.48(14) 1_565 2 ?
S3 K P2 32.22(10) 2 2 ?
S6 K P2 100.73(16) . 2 ?
S4 K P2 56.58(11) 1_564 2 ?
S4 K P2 83.06(12) 2_556 2 ?
S6 K P2 30.89(10) 2 2 ?
S2 K P2 141.15(14) . 2 ?
S1 K P2 87.49(12) 2_655 2 ?
S6 K P1 100.11(15) 2_655 . ?
S3 K P1 76.86(13) 1_565 . ?
S3 K P1 106.64(16) 2 . ?
S6 K P1 56.53(13) . . ?
S4 K P1 161.98(15) 1_564 . ?
S4 K P1 30.90(10) 2_556 . ?
S6 K P1 93.06(13) 2 . ?
S2 K P1 31.64(10) . . ?
S1 K P1 128.19(17) 2_655 . ?
P2 K P1 111.77(13) 2 . ?
S6 K K 117.31(15) 2_655 2 ?
S3 K K 46.59(10) 1_565 2 ?
S3 K K 92.99(16) 2 2 ?
S6 K K 157.88(15) . 2 ?
S4 K K 48.38(10) 1_564 2 ?
S4 K K 91.96(15) 2_556 2 ?
S6 K K 46.41(14) 2 2 ?
S2 K K 113.27(15) . 2 ?
S1 K K 116.33(16) 2_655 2 ?
P2 K K 61.63(13) 2 2 ?
P1 K K 115.09(15) . 2 ?
S1 Bi S5 84.83(13) . . ?
S1 Bi S3 72.45(12) . . ?
S5 Bi S3 81.66(13) . . ?
S1 Bi S2 81.18(12) . 2_646 ?
S5 Bi S2 77.18(13) . 2_646 ?
S3 Bi S2 147.44(12) . 2_646 ?
S4 P1 S2 114.5(3) 2_556 . ?
S4 P1 S5 112.9(2) 2_556 . ?
S2 P1 S5 112.0(3) . . ?
S4 P1 P2 108.2(2) 2_556 . ?
S2 P1 P2 105.1(2) . . ?
S5 P1 P2 103.1(2) . . ?
S4 P1 K 62.59(17) 2_556 . ?
S2 P1 K 65.21(17) . . ?
S5 P1 K 170.4(2) . . ?
P2 P1 K 86.44(18) . . ?
S6 P2 S3 116.4(3) . . ?
S6 P2 S1 118.1(3) . . ?
S3 P2 S1 105.8(3) . . ?
S6 P2 P1 109.8(3) . . ?
S3 P2 P1 102.1(2) . . ?
S1 P2 P1 102.5(2) . . ?
S6 P2 K 66.38(19) . 2_545 ?
S3 P2 K 60.88(17) . 2_545 ?
S1 P2 K 164.6(2) . 2_545 ?
P1 P2 K 88.75(17) . 2_545 ?
P2 S1 Bi 85.42(18) . . ?
P2 S1 K 83.93(18) . 2_645 ?
Bi S1 K 160.38(18) . 2_645 ?
P1 S2 Bi 102.5(2) . 2_656 ?
P1 S2 K 83.15(18) . . ?
Bi S2 K 156.63(16) 2_656 . ?
P2 S3 Bi 83.53(17) . . ?
P2 S3 K 100.1(2) . 1_545 ?
Bi S3 K 114.95(16) . 1_545 ?
P2 S3 K 86.9(2) . 2_545 ?
Bi S3 K 156.08(18) . 2_545 ?
K S3 K 88.27(12) 1_545 2_545 ?
P1 S4 K 106.0(2) 2_546 1_546 ?
P1 S4 K 86.52(19) 2_546 2_546 ?
K S4 K 84.34(11) 1_546 2_546 ?
P1 S5 Bi 104.0(2) . . ?
P2 S6 K 97.0(2) . 2_645 ?
P2 S6 K 107.2(2) . . ?
K S6 K 112.2(2) 2_645 . ?
P2 S6 K 82.73(19) . 2_545 ?
K S6 K 163.0(3) 2_645 2_545 ?
K S6 K 83.87(13) . 2_545 ?

_refine_diff_density_max         1.577
_refine_diff_density_min         -2.361
_refine_diff_density_rms         0.247

