# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2023

####################################################################### 
# 
# 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 2278142'
loop_
_audit_author_name
_audit_author_address
Wu
;Hebei University
China
;
_audit_update_record             
;
2023-07-03 deposited with the CCDC.	2023-08-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Na6 P4 S16 Sn3'
_chemical_formula_weight         1130.85

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Na Na 0.0362 0.0249 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Sn Sn -0.6537 1.4246 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           160
_space_group_name_H-M_alt        'R 3 m :H'
_space_group_name_Hall           'R 3 -2"'

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

_cell_length_a                   19.304(4)
_cell_length_b                   19.304(4)
_cell_length_c                   6.181(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1994.6(11)
_cell_formula_units_Z            3
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    675
_cell_measurement_theta_min      3.51
_cell_measurement_theta_max      24.29

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.824
_exptl_crystal_F_000             1596
_exptl_transmission_factor_min   0.5942
_exptl_transmission_factor_max   0.7456
_exptl_crystal_size_max          0.134
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.061
_exptl_absorpt_coefficient_mu    4.388
_shelx_estimated_absorpt_T_min   0.5942
_shelx_estimated_absorpt_T_max   0.7456
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5942
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10264
_diffrn_reflns_av_unetI/netI     0.0874
_diffrn_reflns_av_R_equivalents  0.1048
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         2.110
_diffrn_reflns_theta_max         27.501
_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 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1109
_reflns_number_gt                907
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.977
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    1.000

_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       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.0220P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   none
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 363 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(6)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1109
_refine_ls_number_parameters     56
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0427
_refine_ls_wR_factor_ref         0.0783
_refine_ls_wR_factor_gt          0.0724
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_restrained_S_all      0.994
_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
Sn1 Sn 0.08987(3) 0.91013(3) 0.8607(2) 0.0234(4) Uani 1 2 d S T P . .
P1 P 0.000000 1.000000 0.5811(12) 0.0134(15) Uani 1 6 d S T P . .
P2 P 0.17508(13) 0.82492(13) 0.5580(7) 0.0161(10) Uani 1 2 d S T P . .
Na1 Na -0.0190(4) 0.7656(4) 0.3247(9) 0.0458(17) Uani 1 1 d . . . . .
S1 S 0.000000 1.000000 0.9053(14) 0.0162(15) Uani 1 6 d S T P . .
S2 S 0.06331(18) 0.76561(18) 0.6993(5) 0.0193(7) Uani 1 1 d . . . . .
S3 S 0.05809(13) 0.94191(13) 0.4649(7) 0.0220(10) Uani 1 2 d S T P . .
S4 S 0.16406(15) 0.83594(15) 0.2347(9) 0.0248(10) Uani 1 2 d S T P . .
S5 S 0.23429(13) 0.76571(13) 0.6291(8) 0.0211(10) Uani 1 2 d S T P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Sn1 0.0299(6) 0.0299(6) 0.0183(6) 0.0003(3) -0.0003(3) 0.0208(7)
P1 0.011(2) 0.011(2) 0.017(4) 0.000 0.000 0.0057(11)
P2 0.0191(18) 0.0191(18) 0.012(2) 0.0009(9) -0.0009(9) 0.011(2)
Na1 0.040(4) 0.049(4) 0.032(3) -0.001(3) -0.015(3) 0.010(3)
S1 0.016(2) 0.016(2) 0.016(3) 0.000 0.000 0.0081(12)
S2 0.0161(16) 0.0162(16) 0.0231(16) 0.0005(13) 0.0014(13) 0.0061(14)
S3 0.028(2) 0.028(2) 0.020(2) -0.0021(9) 0.0021(9) 0.021(2)
S4 0.0325(19) 0.0325(19) 0.0140(19) 0.0014(9) -0.0014(9) 0.020(2)
S5 0.0224(19) 0.0224(19) 0.026(3) 0.0014(9) -0.0014(9) 0.017(2)

_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
Sn1 S3 2.667(5) . ?
Sn1 S2 2.759(3) 4_665 ?
Sn1 S2 2.759(3) . ?
P1 S1 2.004(12) . ?
P1 S3 2.070(5) 3_465 ?
P1 S3 2.070(5) 2_675 ?
P1 S3 2.071(5) . ?
P2 S5 2.028(6) . ?
P2 S4 2.032(7) . ?
P2 S2 2.064(4) 4_665 ?
P2 S2 2.064(4) . ?
Na1 S2 2.809(6) . ?
Na1 S2 2.895(7) 8_564 ?
Na1 S4 2.981(7) 8_565 ?
Na1 S5 2.996(7) 8_564 ?
Na1 S3 3.079(7) . ?
Na1 S4 3.138(7) . ?
Na1 Na1 3.790(13) 5_455 ?
Na1 Na1 4.207(11) 8_565 ?
Na1 Na1 4.208(11) 15_454 ?

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 Sn1 S2 87.31(11) . 4_665 ?
S3 Sn1 S2 87.31(11) . . ?
S2 Sn1 S2 73.53(13) 4_665 . ?
S1 P1 S3 110.3(2) . 3_465 ?
S1 P1 S3 110.3(2) . 2_675 ?
S3 P1 S3 108.7(3) 3_465 2_675 ?
S1 P1 S3 110.3(2) . . ?
S3 P1 S3 108.6(3) 3_465 . ?
S3 P1 S3 108.6(3) 2_675 . ?
S5 P2 S4 112.9(3) . . ?
S5 P2 S2 108.86(18) . 4_665 ?
S4 P2 S2 109.83(18) . 4_665 ?
S5 P2 S2 108.86(18) . . ?
S4 P2 S2 109.83(18) . . ?
S2 P2 S2 106.3(3) 4_665 . ?
S2 Na1 S2 124.2(3) . 8_564 ?
S2 Na1 S4 86.78(19) . 8_565 ?
S2 Na1 S4 78.87(19) 8_564 8_565 ?
S2 Na1 S5 167.0(3) . 8_564 ?
S2 Na1 S5 68.78(15) 8_564 8_564 ?
S4 Na1 S5 95.4(2) 8_565 8_564 ?
S2 Na1 S3 78.88(18) . . ?
S2 Na1 S3 156.0(2) 8_564 . ?
S4 Na1 S3 111.9(2) 8_565 . ?
S5 Na1 S3 88.4(2) 8_564 . ?
S2 Na1 S4 68.36(17) . . ?
S2 Na1 S4 104.9(2) 8_564 . ?
S4 Na1 S4 152.5(3) 8_565 . ?
S5 Na1 S4 111.6(2) 8_564 . ?
S3 Na1 S4 75.78(17) . . ?
S2 Na1 Na1 124.47(14) . 5_455 ?
S2 Na1 Na1 85.17(14) 8_564 5_455 ?
S4 Na1 Na1 50.53(14) 8_565 5_455 ?
S5 Na1 Na1 50.76(14) 8_564 5_455 ?
S3 Na1 Na1 86.03(14) . 5_455 ?
S4 Na1 Na1 155.52(14) . 5_455 ?
S2 Na1 Na1 61.45(7) . 8_565 ?
S2 Na1 Na1 69.3(2) 8_564 8_565 ?
S4 Na1 Na1 48.13(17) 8_565 8_565 ?
S5 Na1 Na1 128.6(2) 8_564 8_565 ?
S3 Na1 Na1 134.12(14) . 8_565 ?
S4 Na1 Na1 106.89(19) . 8_565 ?
Na1 Na1 Na1 97.52(14) 5_455 8_565 ?
S2 Na1 Na1 86.8(2) . 15_454 ?
S2 Na1 Na1 61.06(8) 8_564 15_454 ?
S4 Na1 Na1 125.3(2) 8_565 15_454 ?
S5 Na1 Na1 102.24(11) 8_564 15_454 ?
S3 Na1 Na1 119.9(3) . 15_454 ?
S4 Na1 Na1 45.0(2) . 15_454 ?
Na1 Na1 Na1 144.29(11) 5_455 15_454 ?
Na1 Na1 Na1 81.93(11) 8_565 15_454 ?
P2 S2 Sn1 88.73(15) . . ?
P2 S2 Na1 94.9(2) . . ?
Sn1 S2 Na1 96.72(17) . . ?
P2 S2 Na1 90.1(2) . 15_455 ?
Sn1 S2 Na1 112.37(16) . 15_455 ?
Na1 S2 Na1 150.6(2) . 15_455 ?
P1 S3 Sn1 93.2(3) . . ?
P1 S3 Na1 127.06(14) . 4_665 ?
Sn1 S3 Na1 92.50(15) . 4_665 ?
P1 S3 Na1 127.06(14) . . ?
Sn1 S3 Na1 92.50(15) . . ?
Na1 S3 Na1 105.2(3) 4_665 . ?
P2 S4 Na1 113.0(2) . 15_454 ?
P2 S4 Na1 113.0(2) . 18_564 ?
Na1 S4 Na1 78.9(3) 15_454 18_564 ?
P2 S4 Na1 86.24(19) . . ?
Na1 S4 Na1 86.8(2) 15_454 . ?
Na1 S4 Na1 159.4(3) 18_564 . ?
P2 S4 Na1 86.24(19) . 4_665 ?
Na1 S4 Na1 159.4(3) 15_454 4_665 ?
Na1 S4 Na1 86.9(2) 18_564 4_665 ?
Na1 S4 Na1 102.4(3) . 4_665 ?
P2 S5 Na1 88.0(2) . 18_565 ?
P2 S5 Na1 88.0(2) . 15_455 ?
Na1 S5 Na1 78.5(3) 18_565 15_455 ?

_refine_diff_density_max         0.829
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.169

_shelx_res_file                  
;
TITL 1 in R3m
    1.res
    created by SHELXL-2018/3 at 12:34:07 on 26-May-2023
CELL 0.71073  19.3038  19.3038   6.1808  90.000  90.000 120.000
ZERR   3.00   0.0043   0.0043   0.0022   0.000   0.000   0.000
LATT -3
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -Y, -X, Z
SYMM -X+Y, Y, Z
SYMM X, X-Y, Z
SFAC Na P  S  Sn
UNIT 18 12 48 9
L.S. 20
ACTA
BOND
FMAP 2
PLAN 5
FREE S1   S4
FREE Sn1  S1
TEMP 0
WGHT    0.022000
EXTI    0.000386
FVAR       0.05165
MOLE 1
SN1   4    0.089867    0.910133    0.860733    10.50000    0.02991    0.02991 =
         0.01831    0.00028   -0.00028    0.02083
P1    2    0.000000    1.000000    0.581052    10.16667    0.01136    0.01136 =
         0.01749    0.00000    0.00000    0.00568
P2    2    0.175077    0.824923    0.558016    10.50000    0.01909    0.01909 =
         0.01240    0.00092   -0.00092    0.01124
NA1   1   -0.019024    0.765630    0.324689    11.00000    0.03999    0.04928 =
         0.03155   -0.00096   -0.01455    0.00995
S1    3    0.000000    1.000000    0.905298    10.16667    0.01627    0.01627 =
         0.01596    0.00000    0.00000    0.00814
S2    3    0.063308    0.765614    0.699315    11.00000    0.01607    0.01619 =
         0.02306    0.00050    0.00141    0.00607
S3    3    0.058087    0.941913    0.464932    10.50000    0.02808    0.02808 =
         0.01987   -0.00215    0.00215    0.02147
S4    3    0.164063    0.835937    0.234660    10.50000    0.03251    0.03251 =
         0.01398    0.00142   -0.00142    0.01979
S5    3    0.234287    0.765714    0.629057    10.50000    0.02242    0.02242 =
         0.02620    0.00141   -0.00141    0.01691
HKLF 4




REM  1 in R3m
REM wR2 = 0.078341, GooF = S = 0.99470, Restrained GooF = 0.99422 for all data
REM R1 = 0.042659 for 907 Fo > 4sig(Fo) and 0.062891 for all 1109 data
REM 56 parameters refined using 1 restraints

END

WGHT      0.0220      0.0000

REM Highest difference peak  0.829,  deepest hole -0.720,  1-sigma level  0.169
Q1    1   0.0000  1.0000  1.1732  10.16667  0.05    0.83
Q2    1   0.1444  0.8556  0.3031  10.50000  0.05    0.74
Q3    1   0.1292  0.8708  0.1410  10.50000  0.05    0.66
Q4    1  -0.0171  0.7665  0.1001  11.00000  0.05    0.66
Q5    1   0.0492  0.9048  0.6748  11.00000  0.05    0.65
;
_shelx_res_checksum              19943
