# Supplementary Information (SI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2026

####################################################################### 
# 
# 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 2546389'
loop_
_audit_author_name
_audit_author_address
'Mingzhi Zhang'
;Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter
China
;
_audit_update_record             
;
2026-04-15 deposited with the CCDC.	2026-06-10 downloaded from the CCDC.
;
_audit_creation_date             2026-04-14
_audit_creation_method           
;
Olex2 1.5
(compiled 2026.04.10 svn.r48fbca5a for OlexSys, GUI svn.r7537)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Ag4 P2 S6'
_chemical_formula_sum            'Ag4 P2 S6'
_chemical_formula_weight         685.78
_chemical_melting_point          ?
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'
Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      trigonal
_space_group_IT_number           147
_space_group_name_H-M_alt        'P -3'
_space_group_name_Hall           '-P 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'

_cell_length_a                   10.8903(11)
_cell_length_b                   10.8903(11)
_cell_length_c                   7.0537(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     724.5(2)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    2150
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.7200
_cell_measurement_theta_min      3.5320
_shelx_estimated_absorpt_T_max   0.911
_shelx_estimated_absorpt_T_min   0.911
_exptl_absorpt_coefficient_mu    9.546
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    4.716
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             942
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            4466
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.888
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                772
_reflns_number_total             853
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         1.167
_refine_diff_density_min         -0.826
_refine_diff_density_rms         0.251
_refine_ls_extinction_coef       0.0023(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.278
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     60
_refine_ls_number_reflns         853
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0558
_refine_ls_restrained_S_all      1.278
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+22.6002P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1103
_refine_ls_wR_factor_ref         0.1123
_refine_special_details          ?
_olex2_refinement_description    
;
1. Uiso/Uaniso restraints and constraints
Uanis(Ag2A) = Uanis(Ag2B)
2. Others
 Sof(Ag2B)=1-FVAR(1)
 Sof(Ag2A)=FVAR(1)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     ?
_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
Ag1 Ag 0.73991(15) 0.08820(16) 0.00971(19) 0.0454(5) Uani 1 1 d . . . . .
Ag2A Ag 0.6575(10) 0.0183(5) 0.5914(11) 0.0431(13) Uani 0.72(2) 1 d . . P . .
Ag2B Ag 0.6188(17) 0.0050(13) 0.551(2) 0.0431(13) Uani 0.28(2) 1 d . . P . .
S1 S 0.7593(3) 0.2198(3) 0.3499(5) 0.0202(8) Uani 1 1 d . . . . .
S2 S 0.5542(3) 0.1279(3) 0.8322(5) 0.0207(8) Uani 1 1 d . . . . .
S3 S 0.7985(3) -0.0653(4) 0.2416(5) 0.0227(8) Uani 1 1 d . . . . .
P1 P 0.666667 0.333333 0.4333(8) 0.0129(11) Uani 1 3 d S T P . .
P2 P 0.666667 0.333333 0.7553(8) 0.0135(11) Uani 1 3 d S T P . .
P3 P 1.000000 0.000000 0.1611(8) 0.0142(12) Uani 1 3 d S T P . .


_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
Ag1 Ag2A 3.067(9) 1_554 ?
Ag1 S1 2.749(3) . ?
Ag1 S2 2.592(4) 1_554 ?
Ag1 S3 2.635(4) . ?
Ag1 S3 2.609(4) 5_665 ?
Ag2A Ag2B 3.06(2) 4_656 ?
Ag2A S1 2.481(5) 6_546 ?
Ag2A S1 2.552(6) . ?
Ag2A S2 2.630(6) . ?
Ag2A S3 2.876(11) 5_666 ?
Ag2B Ag2B 2.63(3) 4_656 ?
Ag2B S1 2.499(13) . ?
Ag2B S1 2.467(13) 6_546 ?
Ag2B S2 2.678(14) . ?
S1 P1 2.034(3) . ?
S2 P2 2.015(3) . ?
S3 P3 2.021(4) . ?
P1 P2 2.271(8) . ?
P3 P3 2.273(11) 4_755 ?

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
S1 Ag1 Ag2A 154.94(14) . 1_554 ?
S2 Ag1 Ag2A 54.62(16) 1_554 1_554 ?
S2 Ag1 S1 101.38(11) 1_554 . ?
S2 Ag1 S3 105.22(11) 1_554 5_665 ?
S2 Ag1 S3 149.57(12) 1_554 . ?
S3 Ag1 Ag2A 60.25(17) 5_665 1_554 ?
S3 Ag1 Ag2A 124.98(13) . 1_554 ?
S3 Ag1 S1 130.25(12) 5_665 . ?
S3 Ag1 S1 79.00(11) . . ?
S3 Ag1 S3 96.79(14) 5_665 . ?
Ag2B Ag2A Ag1 119.31(15) 4_656 1_556 ?
S1 Ag2A Ag1 92.4(2) 6_546 1_556 ?
S1 Ag2A Ag1 118.8(3) . 1_556 ?
S1 Ag2A Ag2B 91.8(4) 6_546 4_656 ?
S1 Ag2A Ag2B 80.7(3) . 4_656 ?
S1 Ag2A S1 147.6(3) 6_546 . ?
S1 Ag2A S2 108.2(2) 6_546 . ?
S1 Ag2A S2 98.12(18) . . ?
S1 Ag2A S3 105.7(3) 6_546 5_666 ?
S1 Ag2A S3 89.0(2) . 5_666 ?
S2 Ag2A Ag1 53.46(16) . 1_556 ?
S2 Ag2A Ag2B 67.9(2) . 4_656 ?
S2 Ag2A S3 97.2(3) . 5_666 ?
S3 Ag2A Ag1 52.0(2) 5_666 1_556 ?
S3 Ag2A Ag2B 160.13(19) 5_666 4_656 ?
Ag2B Ag2B Ag2A 4.0(4) 4_656 4_656 ?
Ag2B Ag2B S2 74.0(6) 4_656 . ?
S1 Ag2B Ag2A 90.5(4) . 4_656 ?
S1 Ag2B Ag2A 101.9(5) 6_546 4_656 ?
S1 Ag2B Ag2B 90.8(7) . 4_656 ?
S1 Ag2B Ag2B 103.2(7) 6_546 4_656 ?
S1 Ag2B S1 153.5(7) 6_546 . ?
S1 Ag2B S2 98.2(4) . . ?
S1 Ag2B S2 107.1(5) 6_546 . ?
S2 Ag2B Ag2A 77.9(3) . 4_656 ?
Ag2A S1 Ag1 103.6(3) 5_666 . ?
Ag2A S1 Ag1 104.31(19) . . ?
Ag2A S1 Ag2A 106.9(3) 5_666 . ?
Ag2A S1 Ag2B 117.3(4) 5_666 . ?
Ag2B S1 Ag1 98.9(3) . . ?
Ag2B S1 Ag1 113.8(4) 5_666 . ?
Ag2B S1 Ag2A 10.9(2) 5_666 5_666 ?
Ag2B S1 Ag2A 106.7(4) 5_666 . ?
Ag2B S1 Ag2A 10.6(2) . . ?
Ag2B S1 Ag2B 117.3(5) 5_666 . ?
P1 S1 Ag1 129.6(2) . . ?
P1 S1 Ag2A 109.4(3) . 5_666 ?
P1 S1 Ag2A 101.3(2) . . ?
P1 S1 Ag2B 99.0(4) . 5_666 ?
P1 S1 Ag2B 98.5(4) . . ?
Ag1 S2 Ag2A 71.9(3) 1_556 . ?
Ag1 S2 Ag2B 81.5(4) 1_556 . ?
Ag2A S2 Ag2B 10.1(2) . . ?
P2 S2 Ag1 102.91(15) . 1_556 ?
P2 S2 Ag2A 99.74(19) . . ?
P2 S2 Ag2B 100.9(3) . . ?
Ag1 S3 Ag1 81.36(10) 6_545 . ?
Ag1 S3 Ag2A 67.80(14) 6_545 6_546 ?
Ag1 S3 Ag2A 135.21(16) . 6_546 ?
P3 S3 Ag1 102.21(18) . 6_545 ?
P3 S3 Ag1 99.62(17) . . ?
P3 S3 Ag2A 117.63(17) . 6_546 ?
S1 P1 S1 111.99(15) . 2_655 ?
S1 P1 S1 111.99(15) 3_665 2_655 ?
S1 P1 S1 111.99(15) 3_665 . ?
S1 P1 P2 106.81(17) 3_665 . ?
S1 P1 P2 106.81(17) . . ?
S1 P1 P2 106.81(17) 2_655 . ?
S2 P2 S2 113.02(15) . 3_665 ?
S2 P2 S2 113.02(15) 2_655 3_665 ?
S2 P2 S2 113.02(15) . 2_655 ?
S2 P2 P1 105.64(18) . . ?
S2 P2 P1 105.64(18) 3_665 . ?
S2 P2 P1 105.64(18) 2_655 . ?
S3 P3 S3 112.43(16) 2_645 . ?
S3 P3 S3 112.43(16) 2_645 3_765 ?
S3 P3 S3 112.43(16) . 3_765 ?
S3 P3 P3 106.32(18) 2_645 4_755 ?
S3 P3 P3 106.32(18) 3_765 4_755 ?
S3 P3 P3 106.32(18) . 4_755 ?

_olex2_submission_special_instructions 'No special instructions were received'
