# Supplementary Information (SI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_EuZnGeS4
_database_code_depnum_ccdc_archive 'CCDC 2385100'
loop_
_audit_author_name
_audit_author_address
'Hua Lin'
;Fujian Institute of Research on the Structure of Matter, CAS
China
;
_audit_update_record             
;
2024-09-19 deposited with the CCDC.	2025-02-12 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            'Eu Ge S4 Zn'
_chemical_formula_weight         418.16

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Eu Eu -0.1578 3.6682 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.1547 1.8001 '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'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_H-M_alt        'F d d 2'
_space_group_name_Hall           'F 2 -2d'

_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, z'
'x+1/4, -y+1/4, z+1/4'
'-x+1/4, y+1/4, z+1/4'
'x, y+1/2, z+1/2'
'-x, -y+1/2, z+1/2'
'x+1/4, -y+3/4, z+3/4'
'-x+1/4, y+3/4, z+3/4'
'x+1/2, y, z+1/2'
'-x+1/2, -y, z+1/2'
'x+3/4, -y+1/4, z+3/4'
'-x+3/4, y+1/4, z+3/4'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'x+3/4, -y+3/4, z+1/4'
'-x+3/4, y+3/4, z+1/4'

_cell_length_a                   20.6941(8)
_cell_length_b                   20.4059(6)
_cell_length_c                   12.2283(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5163.8(3)
_cell_formula_units_Z            32
_cell_measurement_temperature    250(2)
_cell_measurement_reflns_used    5125
_cell_measurement_theta_min      3.5200
_cell_measurement_theta_max      30.1210

_exptl_crystal_description       Prism
_exptl_crystal_colour            Yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.303
_exptl_crystal_F_000             6048
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.1400
_exptl_crystal_size_mid          0.1200
_exptl_crystal_size_min          0.1100
_exptl_absorpt_coefficient_mu    19.067
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.32753
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      250(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            7753
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.177
_diffrn_reflns_theta_max         25.019
_diffrn_reflns_theta_full        25.019
_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 0.976
_diffrn_reflns_point_group_measured_fraction_full 0.976
_reflns_number_total             2234
_reflns_number_gt                1658
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.859
_reflns_Friedel_fraction_max     0.950
_reflns_Friedel_fraction_full    0.951

_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)+(0.0122P)²] 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       0.000385(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 742 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(13)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2234
_refine_ls_number_parameters     129
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0187
_refine_ls_wR_factor_ref         0.0474
_refine_ls_wR_factor_gt          0.0450
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_restrained_S_all      1.083
_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
Eu1 Eu 0.7500 0.2500 0.89018(12) 0.0109(2) Uani 1 2 d S T P . .
Eu2 Eu 0.50182(2) 0.24850(4) 0.89260(10) 0.0104(2) Uani 1 1 d . . . . .
Eu3 Eu 0.7500 0.2500 0.39447(11) 0.0107(2) Uani 1 2 d S T P . .
Zn1 Zn 0.62463(9) 0.32375(6) 0.10610(10) 0.0130(3) Uani 1 1 d . . . . .
Zn2 Zn 0.62585(9) 0.36206(6) 0.63913(11) 0.0125(3) Uani 1 1 d . . . . .
Ge1 Ge 0.62476(7) 0.38716(5) 0.39133(9) 0.0085(2) Uani 1 1 d . . . . .
Ge2 Ge 0.62490(8) 0.18157(5) 0.68289(8) 0.0084(3) Uani 1 1 d . . . . .
S1 S 0.6235(2) 0.20508(13) 0.5074(2) 0.0094(6) Uani 1 1 d . . . . .
S2 S 0.6252(2) 0.27880(12) 0.7652(2) 0.0106(6) Uani 1 1 d . . . . .
S3 S 0.70874(18) 0.12891(16) 0.7543(3) 0.0103(8) Uani 1 1 d . . . . .
S4 S 0.70854(19) 0.37987(16) 0.5049(3) 0.0102(8) Uani 1 1 d . . . . .
S5 S 0.54225(19) 0.37912(17) 0.5075(3) 0.0103(8) Uani 1 1 d . . . . .
S6 S 0.54166(18) 0.12869(16) 0.7566(3) 0.0092(8) Uani 1 1 d . . . . .
S7 S 0.6244(2) 0.29685(13) 0.2881(2) 0.0093(6) Uani 1 1 d . . . . .
S8 S 0.6235(2) 0.46787(12) 0.2728(2) 0.0102(6) 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
Eu1 S2 3.058(4) 14_655 ?
Eu1 S2 3.058(4) . ?
Eu1 S8 3.098(4) 7 ?
Eu1 S8 3.098(4) 8_645 ?
Eu1 S3 3.098(3) . ?
Eu1 S3 3.098(3) 14_655 ?
Eu1 S6 3.109(3) 4_655 ?
Eu1 S6 3.109(3) 3 ?
Eu2 S7 3.053(4) 6_655 ?
Eu2 S2 3.054(4) . ?
Eu2 S6 3.070(3) . ?
Eu2 S8 3.095(4) 8_645 ?
Eu2 S5 3.096(3) 6_655 ?
Eu2 S1 3.098(4) 6_655 ?
Eu2 S3 3.100(3) 4_655 ?
Eu2 S4 3.130(3) 15_455 ?
Eu3 S7 3.059(4) 14_655 ?
Eu3 S7 3.059(4) . ?
Eu3 S4 3.096(3) 14_655 ?
Eu3 S4 3.096(3) . ?
Eu3 S1 3.098(4) . ?
Eu3 S1 3.098(4) 14_655 ?
Eu3 S5 3.107(3) 8_644 ?
Eu3 S5 3.107(3) 7_554 ?
Zn1 S7 2.292(3) . ?
Zn1 S8 2.389(3) 8_644 ?
Zn1 S6 2.396(4) 4_654 ?
Zn1 S3 2.407(4) 4_654 ?
Zn2 S2 2.294(3) . ?
Zn2 S1 2.386(3) 4_655 ?
Zn2 S5 2.388(4) . ?
Zn2 S4 2.399(4) . ?
Ge1 S8 2.194(3) . ?
Ge1 S4 2.226(4) . ?
Ge1 S5 2.227(4) . ?
Ge1 S7 2.234(3) . ?
Ge2 S1 2.199(3) . ?
Ge2 S3 2.220(4) . ?
Ge2 S6 2.223(4) . ?
Ge2 S2 2.225(2) . ?
S1 Zn2 2.386(3) 8_644 ?
S1 Eu2 3.098(4) 6_654 ?
S3 Zn1 2.407(4) 8_645 ?
S3 Eu2 3.100(3) 8_644 ?
S4 Eu2 3.130(3) 7_554 ?
S5 Eu2 3.096(3) 6_654 ?
S5 Eu3 3.107(3) 15_455 ?
S6 Zn1 2.396(4) 8_645 ?
S6 Eu1 3.109(3) 11_454 ?
S7 Eu2 3.053(4) 6_654 ?
S8 Zn1 2.389(3) 4_655 ?
S8 Eu2 3.095(4) 4_654 ?
S8 Eu1 3.098(4) 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
S2 Eu1 S2 120.03(13) 14_655 . ?
S2 Eu1 S8 66.76(7) 14_655 7 ?
S2 Eu1 S8 156.64(5) . 7 ?
S2 Eu1 S8 156.63(5) 14_655 8_645 ?
S2 Eu1 S8 66.76(7) . 8_645 ?
S8 Eu1 S8 116.85(13) 7 8_645 ?
S2 Eu1 S3 79.13(10) 14_655 . ?
S2 Eu1 S3 69.66(8) . . ?
S8 Eu1 S3 132.62(9) 7 . ?
S8 Eu1 S3 83.38(8) 8_645 . ?
S2 Eu1 S3 69.66(8) 14_655 14_655 ?
S2 Eu1 S3 79.13(10) . 14_655 ?
S8 Eu1 S3 83.38(8) 7 14_655 ?
S8 Eu1 S3 132.62(9) 8_645 14_655 ?
S3 Eu1 S3 115.11(13) . 14_655 ?
S2 Eu1 S6 128.70(9) 14_655 4_655 ?
S2 Eu1 S6 80.35(8) . 4_655 ?
S8 Eu1 S6 79.06(10) 7 4_655 ?
S8 Eu1 S6 73.16(9) 8_645 4_655 ?
S3 Eu1 S6 147.46(5) . 4_655 ?
S3 Eu1 S6 69.40(10) 14_655 4_655 ?
S2 Eu1 S6 80.35(8) 14_655 3 ?
S2 Eu1 S6 128.70(9) . 3 ?
S8 Eu1 S6 73.16(9) 7 3 ?
S8 Eu1 S6 79.06(10) 8_645 3 ?
S3 Eu1 S6 69.40(10) . 3 ?
S3 Eu1 S6 147.46(5) 14_655 3 ?
S6 Eu1 S6 125.51(14) 4_655 3 ?
S7 Eu2 S2 124.28(10) 6_655 . ?
S7 Eu2 S6 76.20(10) 6_655 . ?
S2 Eu2 S6 70.14(8) . . ?
S7 Eu2 S8 150.18(8) 6_655 8_645 ?
S2 Eu2 S8 66.84(7) . 8_645 ?
S6 Eu2 S8 83.92(8) . 8_645 ?
S7 Eu2 S5 71.52(8) 6_655 6_655 ?
S2 Eu2 S5 130.39(10) . 6_655 ?
S6 Eu2 S5 69.83(11) . 6_655 ?
S8 Eu2 S5 80.92(10) 8_645 6_655 ?
S7 Eu2 S1 64.26(6) 6_655 6_655 ?
S2 Eu2 S1 150.36(7) . 6_655 ?
S6 Eu2 S1 135.56(10) . 6_655 ?
S8 Eu2 S1 121.77(10) 8_645 6_655 ?
S5 Eu2 S1 78.75(9) 6_655 6_655 ?
S7 Eu2 S3 132.07(10) 6_655 4_655 ?
S2 Eu2 S3 80.26(8) . 4_655 ?
S6 Eu2 S3 148.38(6) . 4_655 ?
S8 Eu2 S3 74.18(9) 8_645 4_655 ?
S5 Eu2 S3 126.84(12) 6_655 4_655 ?
S1 Eu2 S3 76.02(10) 6_655 4_655 ?
S7 Eu2 S4 76.72(9) 6_655 15_455 ?
S2 Eu2 S4 78.71(10) . 15_455 ?
S6 Eu2 S4 114.64(11) . 15_455 ?
S8 Eu2 S4 132.47(10) 8_645 15_455 ?
S5 Eu2 S4 145.77(6) 6_655 15_455 ?
S1 Eu2 S4 76.21(9) 6_655 15_455 ?
S3 Eu2 S4 68.38(11) 4_655 15_455 ?
S7 Eu3 S7 129.65(12) 14_655 . ?
S7 Eu3 S4 71.50(8) 14_655 14_655 ?
S7 Eu3 S4 133.51(9) . 14_655 ?
S7 Eu3 S4 133.51(9) 14_655 . ?
S7 Eu3 S4 71.50(8) . . ?
S4 Eu3 S4 128.27(14) 14_655 . ?
S7 Eu3 S1 144.56(5) 14_655 . ?
S7 Eu3 S1 64.18(6) . . ?
S4 Eu3 S1 77.67(10) 14_655 . ?
S4 Eu3 S1 79.91(9) . . ?
S7 Eu3 S1 64.18(6) 14_655 14_655 ?
S7 Eu3 S1 144.56(5) . 14_655 ?
S4 Eu3 S1 79.91(9) 14_655 14_655 ?
S4 Eu3 S1 77.67(10) . 14_655 ?
S1 Eu3 S1 127.07(12) . 14_655 ?
S7 Eu3 S5 76.21(10) 14_655 8_644 ?
S7 Eu3 S5 77.28(9) . 8_644 ?
S4 Eu3 S5 68.50(10) 14_655 8_644 ?
S4 Eu3 S5 146.80(6) . 8_644 ?
S1 Eu3 S5 76.56(8) . 8_644 ?
S1 Eu3 S5 135.47(9) 14_655 8_644 ?
S7 Eu3 S5 77.28(9) 14_655 7_554 ?
S7 Eu3 S5 76.21(10) . 7_554 ?
S4 Eu3 S5 146.80(6) 14_655 7_554 ?
S4 Eu3 S5 68.50(10) . 7_554 ?
S1 Eu3 S5 135.47(9) . 7_554 ?
S1 Eu3 S5 76.56(8) 14_655 7_554 ?
S5 Eu3 S5 114.76(14) 8_644 7_554 ?
S7 Zn1 S8 101.38(9) . 8_644 ?
S7 Zn1 S6 127.34(15) . 4_654 ?
S8 Zn1 S6 101.25(14) 8_644 4_654 ?
S7 Zn1 S3 127.81(15) . 4_654 ?
S8 Zn1 S3 102.35(13) 8_644 4_654 ?
S6 Zn1 S3 92.10(9) 4_654 4_654 ?
S2 Zn2 S1 100.49(11) . 4_655 ?
S2 Zn2 S5 123.81(14) . . ?
S1 Zn2 S5 107.24(13) 4_655 . ?
S2 Zn2 S4 125.19(14) . . ?
S1 Zn2 S4 106.87(13) 4_655 . ?
S5 Zn2 S4 91.92(11) . . ?
S8 Ge1 S4 118.12(14) . . ?
S8 Ge1 S5 117.88(14) . . ?
S4 Ge1 S5 101.20(12) . . ?
S8 Ge1 S7 104.23(11) . . ?
S4 Ge1 S7 107.45(13) . . ?
S5 Ge1 S7 107.31(13) . . ?
S1 Ge2 S3 119.96(15) . . ?
S1 Ge2 S6 119.42(15) . . ?
S3 Ge2 S6 102.20(10) . . ?
S1 Ge2 S2 104.30(9) . . ?
S3 Ge2 S2 104.59(15) . . ?
S6 Ge2 S2 104.56(14) . . ?
Ge2 S1 Zn2 114.69(11) . 8_644 ?
Ge2 S1 Eu3 119.25(17) . . ?
Zn2 S1 Eu3 87.75(12) 8_644 . ?
Ge2 S1 Eu2 121.31(17) . 6_654 ?
Zn2 S1 Eu2 88.47(12) 8_644 6_654 ?
Eu3 S1 Eu2 114.52(9) . 6_654 ?
Ge2 S2 Zn2 110.89(12) . . ?
Ge2 S2 Eu2 92.76(12) . . ?
Zn2 S2 Eu2 119.85(16) . . ?
Ge2 S2 Eu1 93.26(13) . . ?
Zn2 S2 Eu1 118.23(16) . . ?
Eu2 S2 Eu1 114.34(9) . . ?
Ge2 S3 Zn1 82.50(14) . 8_645 ?
Ge2 S3 Eu1 92.31(11) . . ?
Zn1 S3 Eu1 107.03(12) 8_645 . ?
Ge2 S3 Eu2 116.62(13) . 8_644 ?
Zn1 S3 Eu2 90.87(11) 8_645 8_644 ?
Eu1 S3 Eu2 148.04(13) . 8_644 ?
Ge1 S4 Zn2 83.19(15) . . ?
Ge1 S4 Eu3 90.05(11) . . ?
Zn2 S4 Eu3 111.50(13) . . ?
Ge1 S4 Eu2 120.36(13) . 7_554 ?
Zn2 S4 Eu2 87.49(11) . 7_554 ?
Eu3 S4 Eu2 146.53(14) . 7_554 ?
Ge1 S5 Zn2 83.41(14) . . ?
Ge1 S5 Eu2 89.90(11) . 6_654 ?
Zn2 S5 Eu2 113.37(13) . 6_654 ?
Ge1 S5 Eu3 120.07(14) . 15_455 ?
Zn2 S5 Eu3 87.49(11) . 15_455 ?
Eu2 S5 Eu3 146.04(13) 6_654 15_455 ?
Ge2 S6 Zn1 82.69(14) . 8_645 ?
Ge2 S6 Eu2 92.36(11) . . ?
Zn1 S6 Eu2 106.95(12) 8_645 . ?
Ge2 S6 Eu1 116.06(13) . 11_454 ?
Zn1 S6 Eu1 92.16(11) 8_645 11_454 ?
Eu2 S6 Eu1 147.81(13) . 11_454 ?
Ge1 S7 Zn1 110.57(11) . . ?
Ge1 S7 Eu2 90.91(12) . 6_654 ?
Zn1 S7 Eu2 118.73(16) . 6_654 ?
Ge1 S7 Eu3 90.85(12) . . ?
Zn1 S7 Eu3 119.10(16) . . ?
Eu2 S7 Eu3 117.01(9) 6_654 . ?
Ge1 S8 Zn1 113.41(12) . 4_655 ?
Ge1 S8 Eu2 118.79(16) . 4_654 ?
Zn1 S8 Eu2 91.34(12) 4_655 4_654 ?
Ge1 S8 Eu1 120.96(17) . 15_454 ?
Zn1 S8 Eu1 92.58(12) 4_655 15_454 ?
Eu2 S8 Eu1 112.06(9) 4_654 15_454 ?


_refine_diff_density_max         0.638
_refine_diff_density_min         -0.773
_refine_diff_density_rms         0.145



