# Supplementary Information (SI) for Dalton Transactions.
# 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).
# 
# 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_12_a
_database_code_depnum_ccdc_archive 'CCDC 2356801'
loop_
_audit_author_name
_audit_author_address
NaCaGaS
;Tianjin University of Technology
China
;
_audit_update_record             
;
2024-05-21 deposited with the CCDC.	2025-03-04 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/1
_shelx_SHELXL_version_number     2019/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ca0.44 Ga1.33 Na0.44 S2.67'
_chemical_formula_weight         206.48

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ca Ca 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ga Ga 0.2307 1.6083 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Na Na 0.0362 0.0249 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

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

_cell_length_a                   6.9613(5)
_cell_length_b                   14.6439(9)
_cell_length_c                   20.1221(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2051.3(2)
_cell_formula_units_Z            18
_cell_measurement_temperature    297(2)
_cell_measurement_reflns_used    3568
_cell_measurement_theta_min      2.46
_cell_measurement_theta_max      27.36

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            PALE_YELLOW
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.009
_exptl_crystal_F_000             1760
_exptl_transmission_factor_min   0.4997
_exptl_transmission_factor_max   0.7456
_exptl_crystal_size_max          0.183
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.106
_exptl_absorpt_coefficient_mu    9.515
_shelx_estimated_absorpt_T_min   0.0362
_shelx_estimated_absorpt_T_max   0.1125
_exptl_absorpt_correction_type   'Numerical Mu From Formula'
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      297(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-III CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17376
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         2.024
_diffrn_reflns_theta_max         27.502
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             2350
_reflns_number_gt                2090
_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       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2019/1 (Sheldrick, 2019)'
_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)+(0.0089P)²+5.2819P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2350
_refine_ls_number_parameters     100
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0278
_refine_ls_R_factor_gt           0.0212
_refine_ls_wR_factor_ref         0.0468
_refine_ls_wR_factor_gt          0.0387
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_restrained_S_all      1.142
_refine_ls_shift/su_max          0.001
_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
Na1 Na 0.4895(2) 0.49660(12) 0.18451(8) 0.0332(4) Uani 1 1 d . . . . .
Ca1 Ca 1.08472(11) 0.80758(5) 0.41704(4) 0.01844(16) Uani 1 1 d . . . . .
Ga1 Ga 0.82860(5) 0.73750(2) 0.26703(2) 0.01191(9) Uani 1 1 d . . . . .
Ga2 Ga 0.52040(5) 0.61302(2) 0.38105(2) 0.01195(9) Uani 1 1 d . . . . .
Ga3 Ga 0.80966(5) 0.45028(2) 0.48563(2) 0.01260(9) Uani 1 1 d . . . . .
S1 S 0.88127(12) 0.56936(6) 0.55317(4) 0.01545(18) Uani 1 1 d . . . . .
S2 S 0.62891(13) 0.46835(5) 0.39331(4) 0.01568(18) Uani 1 1 d . . . . .
S3 S 0.59414(13) 0.82936(6) 0.22751(4) 0.01617(18) Uani 1 1 d . . . . .
S4 S 0.65896(13) 0.32794(5) 0.53330(4) 0.01387(18) Uani 1 1 d . . . . .
S5 S 0.33758(13) 0.60354(6) 0.28939(4) 0.01631(19) Uani 1 1 d . . . . .
S6 S 0.78418(16) 0.70041(8) 0.37484(5) 0.0313(3) 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
Na1 S5 2.8326(18) . ?
Na1 S5 2.9327(18) 6_656 ?
Na1 S1 2.9540(18) 2_664 ?
Na1 S2 2.9871(19) 6_556 ?
Na1 S3 3.078(2) 3_645 ?
Ca1 S6 2.7498(12) . ?
Ca1 S1 2.8050(11) 4_566 ?
Ca1 S2 2.8253(11) 8_765 ?
Ca1 S4 2.8498(11) 5_766 ?
Ca1 S4 2.9051(12) 8_765 ?
Ca1 S3 2.9267(12) 6_656 ?
Ca1 Ga1 3.6530(8) . ?
Ca1 Ga3 3.7161(8) 8_765 ?
Ga1 S6 2.2578(10) . ?
Ga1 S3 2.2596(9) . ?
Ga1 S5 2.2673(9) 6_656 ?
Ga1 S3 2.2889(9) 6_656 ?
Ga2 S6 2.2417(10) . ?
Ga2 S5 2.2452(9) . ?
Ga2 S2 2.2626(9) . ?
Ga2 S4 2.2971(9) 5_666 ?
Ga3 S2 2.2593(9) . ?
Ga3 S1 2.2663(9) . ?
Ga3 S4 2.2869(9) . ?
Ga3 S1 2.3069(9) 5_766 ?

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 Na1 S5 83.09(5) . 6_656 ?
S5 Na1 S1 163.94(8) . 2_664 ?
S5 Na1 S1 94.77(5) 6_656 2_664 ?
S5 Na1 S2 98.83(6) . 6_556 ?
S5 Na1 S2 149.56(7) 6_656 6_556 ?
S1 Na1 S2 75.03(4) 2_664 6_556 ?
S5 Na1 S3 86.60(5) . 3_645 ?
S5 Na1 S3 118.56(6) 6_656 3_645 ?
S1 Na1 S3 108.18(6) 2_664 3_645 ?
S2 Na1 S3 91.86(5) 6_556 3_645 ?
S6 Ca1 S1 173.03(4) . 4_566 ?
S6 Ca1 S2 91.32(4) . 8_765 ?
S1 Ca1 S2 83.58(3) 4_566 8_765 ?
S6 Ca1 S4 100.79(4) . 5_766 ?
S1 Ca1 S4 84.93(3) 4_566 5_766 ?
S2 Ca1 S4 165.73(4) 8_765 5_766 ?
S6 Ca1 S4 82.12(3) . 8_765 ?
S1 Ca1 S4 101.05(3) 4_566 8_765 ?
S2 Ca1 S4 75.12(3) 8_765 8_765 ?
S4 Ca1 S4 98.90(3) 5_766 8_765 ?
S6 Ca1 S3 76.84(3) . 6_656 ?
S1 Ca1 S3 97.23(3) 4_566 6_656 ?
S2 Ca1 S3 75.70(3) 8_765 6_656 ?
S4 Ca1 S3 114.22(3) 5_766 6_656 ?
S4 Ca1 S3 143.34(4) 8_765 6_656 ?
S6 Ca1 Ga1 38.11(2) . . ?
S1 Ca1 Ga1 135.75(3) 4_566 . ?
S2 Ca1 Ga1 80.65(3) 8_765 . ?
S4 Ca1 Ga1 113.56(3) 5_766 . ?
S4 Ca1 Ga1 114.16(3) 8_765 . ?
S3 Ca1 Ga1 38.77(2) 6_656 . ?
S6 Ca1 Ga3 82.73(3) . 8_765 ?
S1 Ca1 Ga3 95.92(3) 4_566 8_765 ?
S2 Ca1 Ga3 37.37(2) 8_765 8_765 ?
S4 Ca1 Ga3 136.38(3) 5_766 8_765 ?
S4 Ca1 Ga3 37.980(19) 8_765 8_765 ?
S3 Ca1 Ga3 108.93(3) 6_656 8_765 ?
Ga1 Ca1 Ga3 95.989(19) . 8_765 ?
S6 Ga1 S3 112.49(4) . . ?
S6 Ga1 S5 106.06(4) . 6_656 ?
S3 Ga1 S5 111.03(4) . 6_656 ?
S6 Ga1 S3 101.88(4) . 6_656 ?
S3 Ga1 S3 104.50(4) . 6_656 ?
S5 Ga1 S3 120.68(4) 6_656 6_656 ?
S6 Ga1 Ca1 48.73(3) . . ?
S3 Ga1 Ca1 118.43(3) . . ?
S5 Ga1 Ca1 130.04(3) 6_656 . ?
S3 Ga1 Ca1 53.20(3) 6_656 . ?
S6 Ga2 S5 116.99(4) . . ?
S6 Ga2 S2 105.49(4) . . ?
S5 Ga2 S2 102.76(3) . . ?
S6 Ga2 S4 105.79(4) . 5_666 ?
S5 Ga2 S4 109.36(4) . 5_666 ?
S2 Ga2 S4 116.87(3) . 5_666 ?
S2 Ga3 S1 121.70(3) . . ?
S2 Ga3 S4 100.44(3) . . ?
S1 Ga3 S4 116.88(3) . . ?
S2 Ga3 S1 104.81(4) . 5_766 ?
S1 Ga3 S1 95.38(3) . 5_766 ?
S4 Ga3 S1 118.18(3) . 5_766 ?
S2 Ga3 Ca1 49.38(2) . 8_755 ?
S1 Ga3 Ca1 144.87(3) . 8_755 ?
S4 Ga3 Ca1 51.42(3) . 8_755 ?
S1 Ga3 Ca1 119.55(3) 5_766 8_755 ?
Ga3 S1 Ga3 84.62(3) . 5_766 ?
Ga3 S1 Ca1 117.43(4) . 4_466 ?
Ga3 S1 Ca1 147.01(4) 5_766 4_466 ?
Ga3 S1 Na1 110.60(5) . 2_665 ?
Ga3 S1 Na1 88.74(4) 5_766 2_665 ?
Ca1 S1 Na1 104.07(5) 4_466 2_665 ?
Ga3 S2 Ga2 112.66(4) . . ?
Ga3 S2 Ca1 93.24(3) . 8_755 ?
Ga2 S2 Ca1 128.53(4) . 8_755 ?
Ga3 S2 Na1 88.82(4) . 6_656 ?
Ga2 S2 Na1 95.38(4) . 6_656 ?
Ca1 S2 Na1 130.26(5) 8_755 6_656 ?
Ga1 S3 Ga1 102.51(3) . 6_556 ?
Ga1 S3 Ca1 107.52(4) . 6_556 ?
Ga1 S3 Ca1 88.03(3) 6_556 6_556 ?
Ga1 S3 Na1 114.07(5) . 3_655 ?
Ga1 S3 Na1 106.70(5) 6_556 3_655 ?
Ca1 S3 Na1 130.85(4) 6_556 3_655 ?
Ga3 S4 Ga2 105.62(3) . 5_666 ?
Ga3 S4 Ca1 113.92(4) . 5_766 ?
Ga2 S4 Ca1 109.83(4) 5_666 5_766 ?
Ga3 S4 Ca1 90.60(3) . 8_755 ?
Ga2 S4 Ca1 108.99(4) 5_666 8_755 ?
Ca1 S4 Ca1 125.21(3) 5_766 8_755 ?
Ga2 S5 Ga1 111.93(4) . 6_556 ?
Ga2 S5 Na1 115.76(5) . . ?
Ga1 S5 Na1 96.64(5) 6_556 . ?
Ga2 S5 Na1 110.75(5) . 6_556 ?
Ga1 S5 Na1 121.93(5) 6_556 6_556 ?
Na1 S5 Na1 98.44(6) . 6_556 ?
Ga2 S6 Ga1 107.64(4) . . ?
Ga2 S6 Ca1 158.73(5) . . ?
Ga1 S6 Ca1 93.16(4) . . ?

_refine_diff_density_max         0.511
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.119



