# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2021

####################################################################### 
# 
# 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_La4Ge3S12
_database_code_depnum_ccdc_archive 'CCDC 2095324'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ge3 La4 S12'
_chemical_formula_weight         1158.13

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   19.427(3)
_cell_length_b                   19.427(3)
_cell_length_c                   8.0753(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2639.2(10)
_cell_formula_units_Z            6
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    1096
_cell_measurement_theta_min      4.079
_cell_measurement_theta_max      25.673

_exptl_crystal_description       Block
_exptl_crystal_colour            yellow-green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.372
_exptl_crystal_F_000             3096
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    15.942
_shelx_estimated_absorpt_T_min   0.12
_shelx_estimated_absorpt_T_max   0.498
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.140
_exptl_absorpt_correction_T_max  0.450
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4781
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         4.079
_diffrn_reflns_theta_max         25.673
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_point_group_measured_fraction_full 0.985
_reflns_number_total             1096
_reflns_number_gt                1016
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.957
_reflns_Friedel_fraction_max     0.973
_reflns_Friedel_fraction_full    0.973

_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)+371.1302P] 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
_refine_ls_extinction_coef       0.00056(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 450 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1096
_refine_ls_number_parameters     59
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0323
_refine_ls_wR_factor_ref         0.0763
_refine_ls_wR_factor_gt          0.0634
_refine_ls_goodness_of_fit_ref   0.891
_refine_ls_restrained_S_all      0.891
_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
La1 La 0.56401(7) 0.66945(9) 0.97069(15) 0.0113(3) Uani 1 1 d . . . . .
La2 La 0.3333 0.6667 0.6736(2) 0.0092(5) Uani 1 3 d S T P . .
Ge1 Ge 0.34629(12) 0.47923(13) 1.0210(3) 0.0074(5) Uani 1 1 d . . . . .
S1 S 0.2470(3) 0.4661(3) 1.1771(7) 0.0110(11) Uani 1 1 d . . . . .
S2 S 0.3939(3) 0.6029(3) 0.9226(6) 0.0101(11) Uani 1 1 d . . . . .
S3 S 0.6039(3) 0.6631(3) 1.3253(6) 0.0117(12) Uani 1 1 d . . . . .
S4 S 0.5113(3) 0.5572(3) 0.6789(6) 0.0123(11) 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
La1 S3 2.868(5) 14_654 ?
La1 S2 2.911(5) . ?
La1 S4 2.945(6) 9_565 ?
La1 S3 2.985(5) . ?
La1 S1 3.013(5) 2_665 ?
La1 S4 3.021(6) . ?
La1 S1 3.089(5) 4_664 ?
La2 S2 2.901(5) 2_665 ?
La2 S2 2.901(5) 3_565 ?
La2 S2 2.901(5) . ?
La2 S2 2.913(5) 5_554 ?
La2 S2 2.913(5) 6_564 ?
La2 S2 2.913(5) 4_664 ?
La2 S1 3.386(6) 6_564 ?
La2 S1 3.386(6) 5_554 ?
La2 S1 3.386(6) 4_664 ?
La2 La2 4.0376(7) 4_664 ?
La2 La2 4.0377(6) 4_665 ?
Ge1 S4 2.197(6) 4_665 ?
Ge1 S3 2.200(5) 4_664 ?
Ge1 S1 2.209(6) . ?
Ge1 S2 2.244(6) . ?
S1 La1 3.013(5) 3_565 ?
S1 La1 3.089(5) 4_665 ?
S1 La2 3.386(6) 4_665 ?
S2 La2 2.913(5) 4_665 ?
S3 Ge1 2.200(5) 4_665 ?
S3 La1 2.868(5) 9_565 ?
S4 Ge1 2.197(6) 4_664 ?
S4 La1 2.945(6) 14_654 ?

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 La1 S2 135.80(17) 14_654 . ?
S3 La1 S4 82.38(16) 14_654 9_565 ?
S2 La1 S4 141.80(16) . 9_565 ?
S3 La1 S3 70.69(14) 14_654 . ?
S2 La1 S3 111.71(14) . . ?
S4 La1 S3 77.79(15) 9_565 . ?
S3 La1 S1 135.06(16) 14_654 2_665 ?
S2 La1 S1 78.92(15) . 2_665 ?
S4 La1 S1 70.00(15) 9_565 2_665 ?
S3 La1 S1 69.30(15) . 2_665 ?
S3 La1 S4 78.39(15) 14_654 . ?
S2 La1 S4 71.07(15) . . ?
S4 La1 S4 128.55(19) 9_565 . ?
S3 La1 S4 136.05(16) . . ?
S1 La1 S4 146.42(16) 2_665 . ?
S3 La1 S1 129.15(15) 14_654 4_664 ?
S2 La1 S1 70.13(15) . 4_664 ?
S4 La1 S1 84.62(15) 9_565 4_664 ?
S3 La1 S1 151.52(16) . 4_664 ?
S1 La1 S1 83.76(6) 2_665 4_664 ?
S4 La1 S1 72.27(15) . 4_664 ?
S2 La2 S2 77.27(16) 2_665 3_565 ?
S2 La2 S2 77.27(16) 2_665 . ?
S2 La2 S2 77.27(16) 3_565 . ?
S2 La2 S2 139.0(2) 2_665 5_554 ?
S2 La2 S2 87.99(15) 3_565 5_554 ?
S2 La2 S2 136.7(2) . 5_554 ?
S2 La2 S2 87.99(15) 2_665 6_564 ?
S2 La2 S2 136.7(2) 3_565 6_564 ?
S2 La2 S2 139.0(2) . 6_564 ?
S2 La2 S2 76.90(16) 5_554 6_564 ?
S2 La2 S2 136.7(2) 2_665 4_664 ?
S2 La2 S2 139.0(2) 3_565 4_664 ?
S2 La2 S2 87.99(15) . 4_664 ?
S2 La2 S2 76.90(16) 5_554 4_664 ?
S2 La2 S2 76.90(16) 6_564 4_664 ?
S2 La2 S1 66.04(13) 2_665 6_564 ?
S2 La2 S1 71.06(14) 3_565 6_564 ?
S2 La2 S1 135.54(15) . 6_564 ?
S2 La2 S1 73.00(14) 5_554 6_564 ?
S2 La2 S1 65.73(14) 6_564 6_564 ?
S2 La2 S1 136.09(15) 4_664 6_564 ?
S2 La2 S1 135.54(15) 2_665 5_554 ?
S2 La2 S1 66.04(13) 3_565 5_554 ?
S2 La2 S1 71.06(14) . 5_554 ?
S2 La2 S1 65.73(14) 5_554 5_554 ?
S2 La2 S1 136.09(15) 6_564 5_554 ?
S2 La2 S1 73.00(14) 4_664 5_554 ?
S1 La2 S1 119.993(5) 6_564 5_554 ?
S2 La2 S1 71.06(14) 2_665 4_664 ?
S2 La2 S1 135.54(15) 3_565 4_664 ?
S2 La2 S1 66.04(13) . 4_664 ?
S2 La2 S1 136.09(15) 5_554 4_664 ?
S2 La2 S1 73.00(14) 6_564 4_664 ?
S2 La2 S1 65.73(14) 4_664 4_664 ?
S1 La2 S1 119.993(5) 6_564 4_664 ?
S1 La2 S1 119.993(4) 5_554 4_664 ?
S2 La2 La2 133.87(10) 2_665 4_664 ?
S2 La2 La2 133.87(10) 3_565 4_664 ?
S2 La2 La2 133.87(10) . 4_664 ?
S2 La2 La2 45.89(10) 5_554 4_664 ?
S2 La2 La2 45.89(10) 6_564 4_664 ?
S2 La2 La2 45.90(10) 4_664 4_664 ?
S1 La2 La2 90.47(10) 6_564 4_664 ?
S1 La2 La2 90.47(10) 5_554 4_664 ?
S1 La2 La2 90.47(10) 4_664 4_664 ?
S2 La2 La2 46.13(10) 2_665 4_665 ?
S2 La2 La2 46.13(10) 3_565 4_665 ?
S2 La2 La2 46.13(10) . 4_665 ?
S2 La2 La2 134.11(10) 5_554 4_665 ?
S2 La2 La2 134.11(10) 6_564 4_665 ?
S2 La2 La2 134.11(10) 4_664 4_665 ?
S1 La2 La2 89.53(10) 6_564 4_665 ?
S1 La2 La2 89.53(10) 5_554 4_665 ?
S1 La2 La2 89.53(10) 4_664 4_665 ?
La2 La2 La2 180.0 4_664 4_665 ?
S4 Ge1 S3 103.4(2) 4_665 4_664 ?
S4 Ge1 S1 109.7(2) 4_665 . ?
S3 Ge1 S1 125.3(2) 4_664 . ?
S4 Ge1 S2 103.8(2) 4_665 . ?
S3 Ge1 S2 111.7(2) 4_664 . ?
S1 Ge1 S2 101.2(2) . . ?
Ge1 S1 La1 111.5(2) . 3_565 ?
Ge1 S1 La1 87.09(18) . 4_665 ?
La1 S1 La1 154.5(2) 3_565 4_665 ?
Ge1 S1 La2 87.76(18) . 4_665 ?
La1 S1 La2 95.58(14) 3_565 4_665 ?
La1 S1 La2 102.67(15) 4_665 4_665 ?
Ge1 S2 La2 131.7(2) . . ?
Ge1 S2 La1 101.34(19) . . ?
La2 S2 La1 121.02(18) . . ?
Ge1 S2 La2 99.85(18) . 4_665 ?
La2 S2 La2 87.97(15) . 4_665 ?
La1 S2 La2 109.17(17) . 4_665 ?
Ge1 S3 La1 128.9(2) 4_665 9_565 ?
Ge1 S3 La1 119.9(2) 4_665 . ?
La1 S3 La1 97.97(15) 9_565 . ?
Ge1 S4 La1 104.9(2) 4_664 14_654 ?
Ge1 S4 La1 89.03(18) 4_664 . ?
La1 S4 La1 95.53(17) 14_654 . ?

_refine_diff_density_max         1.229
_refine_diff_density_min         -1.073
_refine_diff_density_rms         0.281

_shelxl_version_number           2014/6

####################################################################### 
# 
# 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_La4Ge3Se2S10
_database_code_depnum_ccdc_archive 'CCDC 2095326'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 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            'Ge3 La4 S10.10 Se1.90'
_chemical_formula_weight         1247.40

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   19.5575(6)
_cell_length_b                   19.5575(6)
_cell_length_c                   8.1468(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2698.64(19)
_cell_formula_units_Z            6
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    1672
_cell_measurement_theta_min      2.083
_cell_measurement_theta_max      29.568

_exptl_crystal_description       Needle
_exptl_crystal_colour            Yellow-orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.605
_exptl_crystal_F_000             3302
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    19.221
_shelx_estimated_absorpt_T_min   0.310
_shelx_estimated_absorpt_T_max   0.732
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.210
_exptl_absorpt_correction_T_max  0.632
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            11389
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_av_R_equivalents  0.0846
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         2.083
_diffrn_reflns_theta_max         29.568
_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 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1672
_reflns_number_gt                1459
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.972
_reflns_Friedel_fraction_max     0.987
_reflns_Friedel_fraction_full    0.996

_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)+138.8117P] 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       0.00029(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 638 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1672
_refine_ls_number_parameters     62
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0351
_refine_ls_wR_factor_ref         0.0812
_refine_ls_wR_factor_gt          0.0618
_refine_ls_goodness_of_fit_ref   1.189
_refine_ls_restrained_S_all      1.188
_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
La1 La 0.43819(6) 0.33469(7) 0.97798(14) 0.0188(3) Uani 1 1 d . . . . .
La2 La 0.6667 0.3333 1.1813(2) 0.0138(4) Uani 1 3 d S T P . .
Ge1 Ge 0.68003(10) 0.53332(11) 1.0269(2) 0.0125(4) Uani 1 1 d . . . . .
S1 S 0.57954(18) 0.44671(19) 1.1871(4) 0.0165(10) Uani 0.687(16) 1 d . . P . .
Se1 Se 0.57954(18) 0.44671(19) 1.1871(4) 0.0165(10) Uani 0.313(16) 1 d . . P .
.
S2 S 0.4454(2) 0.4896(2) 1.0171(4) 0.0178(12) Uani 0.796(15) 1 d . . P . .
Se2 Se 0.4454(2) 0.4896(2) 1.0171(4) 0.0178(12) Uani 0.204(15) 1 d . . P . .
S3 S 0.3916(2) 0.3286(2) 1.3313(5) 0.0191(13) Uani 0.880(15) 1 d . . P . .
Se3 Se 0.3916(2) 0.3286(2) 1.3313(5) 0.0191(13) Uani 0.120(15) 1 d . . P . .
S4 S 0.5423(2) 0.2691(3) 0.9298(5) 0.0129(8) 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
La1 Se3 2.888(4) 15_554 ?
La1 S3 2.888(4) 15_554 ?
La1 S4 2.924(4) . ?
La1 S2 2.979(4) . ?
La1 S3 3.004(4) . ?
La1 S1 3.048(3) . ?
La1 Se2 3.073(4) 15_554 ?
La1 S2 3.073(4) 15_554 ?
La1 S1 3.118(3) 4_664 ?
La2 S4 2.922(4) 5_655 ?
La2 S4 2.922(4) 4_665 ?
La2 S4 2.922(4) 6 ?
La2 S4 2.939(4) 2_655 ?
La2 S4 2.939(4) . ?
La2 S4 2.939(4) 3_665 ?
La2 Se1 3.406(3) 3_665 ?
La2 Se1 3.406(3) 2_655 ?
La2 La2 4.07340(16) 4_664 ?
La2 La2 4.07340(15) 4_665 ?
Ge1 Se3 2.229(4) 4_664 ?
Ge1 S3 2.229(4) 4_664 ?
Ge1 S4 2.237(5) 3_665 ?
Ge1 S2 2.244(4) 18_554 ?
Ge1 Se2 2.244(4) 18_554 ?
Ge1 S1 2.260(4) . ?
S1 La1 3.118(3) 4_665 ?
S2 Ge1 2.244(4) 12_454 ?
S2 La1 3.073(4) 8 ?
S3 Ge1 2.229(4) 4_665 ?
S3 La1 2.888(4) 8 ?
S4 Ge1 2.237(5) 2_655 ?
S4 La2 2.922(4) 4_664 ?

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
Se3 La1 S3 0.0 15_554 15_554 ?
Se3 La1 S4 136.94(13) 15_554 . ?
S3 La1 S4 136.94(13) 15_554 . ?
Se3 La1 S2 82.59(11) 15_554 . ?
S3 La1 S2 82.59(11) 15_554 . ?
S4 La1 S2 140.43(12) . . ?
Se3 La1 S3 70.7 15_554 . ?
S3 La1 S3 70.66(11) 15_554 . ?
S4 La1 S3 112.01(11) . . ?
S2 La1 S3 78.30(11) . . ?
Se3 La1 S1 134.29(11) 15_554 . ?
S3 La1 S1 134.29(11) 15_554 . ?
S4 La1 S1 79.05(10) . . ?
S2 La1 S1 69.16(9) . . ?
S3 La1 S1 68.96(10) . . ?
Se3 La1 Se2 78.57(11) 15_554 15_554 ?
S3 La1 Se2 78.57(11) 15_554 15_554 ?
S4 La1 Se2 71.39(11) . 15_554 ?
S2 La1 Se2 128.5 . 15_554 ?
S3 La1 Se2 135.95(11) . 15_554 ?
S1 La1 Se2 147.04(9) . 15_554 ?
Se3 La1 S2 78.57(11) 15_554 15_554 ?
S3 La1 S2 78.57(11) 15_554 15_554 ?
S4 La1 S2 71.39(11) . 15_554 ?
S2 La1 S2 128.53(12) . 15_554 ?
S3 La1 S2 135.95(11) . 15_554 ?
S1 La1 S2 147.04(9) . 15_554 ?
Se2 La1 S2 0.0 15_554 15_554 ?
Se3 La1 S1 129.02(11) 15_554 4_664 ?
S3 La1 S1 129.02(11) 15_554 4_664 ?
S4 La1 S1 70.14(10) . 4_664 ?
S2 La1 S1 83.09(10) . 4_664 ?
S3 La1 S1 150.80(11) . 4_664 ?
S1 La1 S1 83.50(4) . 4_664 ?
Se2 La1 S1 73.14(9) 15_554 4_664 ?
S2 La1 S1 73.14(9) 15_554 4_664 ?
S4 La2 S4 77.29(13) 5_655 4_665 ?
S4 La2 S4 77.29(13) 5_655 6 ?
S4 La2 S4 77.29(13) 4_665 6 ?
S4 La2 S4 88.06(11) 5_655 2_655 ?
S4 La2 S4 136.44(16) 4_665 2_655 ?
S4 La2 S4 139.28(16) 6 2_655 ?
S4 La2 S4 136.44(16) 5_655 . ?
S4 La2 S4 139.28(16) 4_665 . ?
S4 La2 S4 88.07(11) 6 . ?
S4 La2 S4 76.77(12) 2_655 . ?
S4 La2 S4 139.28(16) 5_655 3_665 ?
S4 La2 S4 88.06(11) 4_665 3_665 ?
S4 La2 S4 136.44(16) 6 3_665 ?
S4 La2 S4 76.77(12) 2_655 3_665 ?
S4 La2 S4 76.77(12) . 3_665 ?
S4 La2 Se1 66.11(10) 5_655 3_665 ?
S4 La2 Se1 70.48(10) 4_665 3_665 ?
S4 La2 Se1 135.26(11) 6 3_665 ?
S4 La2 Se1 66.07(10) 2_655 3_665 ?
S4 La2 Se1 136.34(11) . 3_665 ?
S4 La2 Se1 73.21(10) 3_665 3_665 ?
S4 La2 Se1 70.48(10) 5_655 2_655 ?
S4 La2 Se1 135.26(11) 4_665 2_655 ?
S4 La2 Se1 66.11(10) 6 2_655 ?
S4 La2 Se1 73.21(10) 2_655 2_655 ?
S4 La2 Se1 66.08(10) . 2_655 ?
S4 La2 Se1 136.34(11) 3_665 2_655 ?
Se1 La2 Se1 119.981(3) 3_665 2_655 ?
S4 La2 La2 133.85(8) 5_655 4_664 ?
S4 La2 La2 133.85(8) 4_665 4_664 ?
S4 La2 La2 133.85(8) 6 4_664 ?
S4 La2 La2 45.81(8) 2_655 4_664 ?
S4 La2 La2 45.81(8) . 4_664 ?
S4 La2 La2 45.81(8) 3_665 4_664 ?
Se1 La2 La2 90.79(6) 3_665 4_664 ?
Se1 La2 La2 90.79(6) 2_655 4_664 ?
S4 La2 La2 46.15(8) 5_655 4_665 ?
S4 La2 La2 46.15(8) 4_665 4_665 ?
S4 La2 La2 46.15(8) 6 4_665 ?
S4 La2 La2 134.19(8) 2_655 4_665 ?
S4 La2 La2 134.19(8) . 4_665 ?
S4 La2 La2 134.19(8) 3_665 4_665 ?
Se1 La2 La2 89.20(6) 3_665 4_665 ?
Se1 La2 La2 89.21(6) 2_655 4_665 ?
La2 La2 La2 180.0 4_664 4_665 ?
Se3 Ge1 S3 0.0 4_664 4_664 ?
Se3 Ge1 S4 111.94(17) 4_664 3_665 ?
S3 Ge1 S4 111.94(17) 4_664 3_665 ?
Se3 Ge1 S2 102.37(17) 4_664 18_554 ?
S3 Ge1 S2 102.37(17) 4_664 18_554 ?
S4 Ge1 S2 103.72(15) 3_665 18_554 ?
Se3 Ge1 Se2 102.37(17) 4_664 18_554 ?
S3 Ge1 Se2 102.37(17) 4_664 18_554 ?
S4 Ge1 Se2 103.72(15) 3_665 18_554 ?
S2 Ge1 Se2 0.0(2) 18_554 18_554 ?
Se3 Ge1 S1 125.65(15) 4_664 . ?
S3 Ge1 S1 125.65(15) 4_664 . ?
S4 Ge1 S1 101.47(15) 3_665 . ?
S2 Ge1 S1 109.95(14) 18_554 . ?
Se2 Ge1 S1 109.95(14) 18_554 . ?
Ge1 S1 La1 110.62(13) . . ?
Ge1 S1 La1 86.88(11) . 4_665 ?
La1 S1 La1 155.66(12) . 4_665 ?
Ge1 S2 La1 104.64(13) 12_454 . ?
Ge1 S2 La1 88.26(12) 12_454 8 ?
La1 S2 La1 94.74(11) . 8 ?
Ge1 S3 La1 128.20(17) 4_665 8 ?
Ge1 S3 La1 119.32(16) 4_665 . ?
La1 S3 La1 98.18(12) 8 . ?
Ge1 S4 La2 131.87(18) 2_655 4_664 ?
Ge1 S4 La1 100.93(15) 2_655 . ?
La2 S4 La1 121.13(15) 4_664 . ?
Ge1 S4 La2 100.01(15) 2_655 . ?
La2 S4 La2 88.04(11) 4_664 . ?
La1 S4 La2 109.16(14) . . ?

_refine_diff_density_max         2.015
_refine_diff_density_min         -1.892
_refine_diff_density_rms         0.447

####################################################################### 
# 
# 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_la4Ge3Se10S2
_database_code_depnum_ccdc_archive 'CCDC 2095331'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 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            'Ge3 La4 S2.23 Se9.77'
_chemical_formula_weight         1616.26

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   20.0723(12)
_cell_length_b                   20.0723(12)
_cell_length_c                   8.3460(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2912.1(4)
_cell_formula_units_Z            6
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    1821
_cell_measurement_theta_min      2.09
_cell_measurement_theta_max      29.551

_exptl_crystal_description       Needle
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.530
_exptl_crystal_F_000             4151
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.030
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    31.713
_shelx_estimated_absorpt_T_min   0.450
_shelx_estimated_absorpt_T_max   0.742
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.351
_exptl_absorpt_correction_T_max  0.624
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9472
_diffrn_reflns_av_unetI/netI     0.0723
_diffrn_reflns_av_R_equivalents  0.1039
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.029
_diffrn_reflns_theta_max         29.551
_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 0.999
_reflns_number_total             1821
_reflns_number_gt                1555
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.984
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    0.998

_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)+(0.0144P)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       0.00021(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 655 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1821
_refine_ls_number_parameters     62
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0368
_refine_ls_wR_factor_ref         0.0680
_refine_ls_wR_factor_gt          0.0632
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_restrained_S_all      1.021
_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
La1 La 0.56213(6) 0.66732(6) 0.97182(13) 0.0187(3) Uani 1 1 d . . . . .
La2 La 0.3333 0.6667 0.6788(2) 0.0156(4) Uani 1 3 d S T P . .
Ge1 Ge 0.34685(10) 0.48149(10) 1.0251(2) 0.0129(4) Uani 1 1 d . . . . .
Se1 Se 0.24530(9) 0.46716(10) 1.1854(2) 0.0166(4) Uani 1 1 d . . . . .
S2 S 0.39433(14) 0.60466(14) 0.9272(3) 0.0131(9) Uani 0.577(15) 1 d . . P . .
Se2 Se 0.39433(14) 0.60466(14) 0.9272(3) 0.0131(9) Uani 0.423(15) 1 d . . P . .
S3 S 0.60401(9) 0.65991(11) 1.3267(2) 0.0154(6) Uani 0.135(14) 1 d . . P . .
Se3 Se 0.60401(9) 0.65991(11) 1.3267(2) 0.0154(6) Uani 0.865(14) 1 d . . P . .
S4 S 0.50909(10) 0.55265(9) 0.6819(2) 0.0166(6) Uani 0.032(14) 1 d . . P . .
Se4 Se 0.50909(10) 0.55265(9) 0.6819(2) 0.0166(6) Uani 0.968(14) 1 d . . 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
La1 S2 2.971(3) . ?
La1 Se3 2.9745(19) 14_654 ?
La1 S3 2.9745(19) 14_654 ?
La1 Se4 3.086(2) 9_565 ?
La1 S4 3.086(2) 9_565 ?
La1 S3 3.103(2) . ?
La1 Se1 3.1272(19) 2_665 ?
La1 S4 3.136(2) . ?
La1 Se1 3.188(2) 4_664 ?
La2 Se2 2.978(3) 2_665 ?
La2 S2 2.978(3) 2_665 ?
La2 Se2 2.978(3) 3_565 ?
La2 S2 2.978(3) 3_565 ?
La2 S2 2.978(3) . ?
La2 Se2 2.997(3) 5_554 ?
La2 S2 2.997(3) 5_554 ?
La2 Se2 2.997(3) 6_564 ?
La2 S2 2.997(3) 6_564 ?
La2 Se2 2.997(3) 4_664 ?
La2 S2 2.997(3) 4_664 ?
Ge1 S2 2.309(3) . ?
Ge1 Se4 2.332(2) 4_665 ?
Ge1 S4 2.332(2) 4_665 ?
Ge1 Se1 2.333(2) . ?
Ge1 Se3 2.339(3) 4_664 ?
Ge1 S3 2.339(3) 4_664 ?
Se1 La1 3.1271(19) 3_565 ?
Se1 La1 3.188(2) 4_665 ?
Se1 La2 3.4765(17) 4_665 ?
S2 La2 2.997(3) 4_665 ?
S3 Ge1 2.339(3) 4_665 ?
S3 La1 2.9744(19) 9_565 ?
S4 Ge1 2.332(2) 4_664 ?
S4 La1 3.086(2) 14_654 ?

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 La1 Se3 139.00(7) . 14_654 ?
S2 La1 S3 139.00(7) . 14_654 ?
Se3 La1 S3 0.0 14_654 14_654 ?
S2 La1 Se4 139.13(7) . 9_565 ?
Se3 La1 Se4 81.87(5) 14_654 9_565 ?
S3 La1 Se4 81.87(5) 14_654 9_565 ?
S2 La1 S4 139.13(7) . 9_565 ?
Se3 La1 S4 81.87(5) 14_654 9_565 ?
S3 La1 S4 81.87(5) 14_654 9_565 ?
Se4 La1 S4 0.0 9_565 9_565 ?
S2 La1 S3 112.11(7) . . ?
Se3 La1 S3 69.6 14_654 . ?
S3 La1 S3 69.56(5) 14_654 . ?
Se4 La1 S3 77.94(5) 9_565 . ?
S4 La1 S3 77.94(5) 9_565 . ?
S2 La1 Se1 78.24(6) . 2_665 ?
Se3 La1 Se1 132.93(6) 14_654 2_665 ?
S3 La1 Se1 132.93(6) 14_654 2_665 ?
Se4 La1 Se1 68.58(5) 9_565 2_665 ?
S4 La1 Se1 68.58(5) 9_565 2_665 ?
S3 La1 Se1 69.00(5) . 2_665 ?
S2 La1 S4 72.28(6) . . ?
Se3 La1 S4 79.09(5) 14_654 . ?
S3 La1 S4 79.09(5) 14_654 . ?
Se4 La1 S4 129.8 9_565 . ?
S4 La1 S4 129.78(7) 9_565 . ?
S3 La1 S4 134.59(6) . . ?
Se1 La1 S4 147.82(5) 2_665 . ?
S2 La1 Se1 69.94(6) . 4_664 ?
Se3 La1 Se1 129.46(6) 14_654 4_664 ?
S3 La1 Se1 129.46(6) 14_654 4_664 ?
Se4 La1 Se1 82.82(5) 9_565 4_664 ?
S4 La1 Se1 82.82(5) 9_565 4_664 ?
S3 La1 Se1 150.56(6) . 4_664 ?
Se1 La1 Se1 83.35(3) 2_665 4_664 ?
S4 La1 Se1 74.76(5) . 4_664 ?
Se2 La2 S2 0.0 2_665 2_665 ?
Se2 La2 Se2 76.89(8) 2_665 3_565 ?
S2 La2 Se2 76.89(8) 2_665 3_565 ?
Se2 La2 S2 76.9 2_665 3_565 ?
S2 La2 S2 76.89(8) 2_665 3_565 ?
Se2 La2 S2 0.0 3_565 3_565 ?
Se2 La2 S2 76.9 2_665 . ?
S2 La2 S2 76.89(8) 2_665 . ?
Se2 La2 S2 76.9 3_565 . ?
S2 La2 S2 76.89(8) 3_565 . ?
Se2 La2 Se2 138.42(9) 2_665 5_554 ?
S2 La2 Se2 138.42(9) 2_665 5_554 ?
Se2 La2 Se2 88.60(6) 3_565 5_554 ?
S2 La2 Se2 88.60(6) 3_565 5_554 ?
S2 La2 Se2 137.7 . 5_554 ?
Se2 La2 S2 138.4 2_665 5_554 ?
S2 La2 S2 138.42(9) 2_665 5_554 ?
Se2 La2 S2 88.6 3_565 5_554 ?
S2 La2 S2 88.60(6) 3_565 5_554 ?
S2 La2 S2 137.70(9) . 5_554 ?
Se2 La2 S2 0.0 5_554 5_554 ?
Se2 La2 Se2 88.60(6) 2_665 6_564 ?
S2 La2 Se2 88.60(6) 2_665 6_564 ?
Se2 La2 Se2 137.70(9) 3_565 6_564 ?
S2 La2 Se2 137.70(9) 3_565 6_564 ?
S2 La2 Se2 138.4 . 6_564 ?
Se2 La2 Se2 76.32(8) 5_554 6_564 ?
S2 La2 Se2 76.32(8) 5_554 6_564 ?
Se2 La2 S2 88.6 2_665 6_564 ?
S2 La2 S2 88.60(6) 2_665 6_564 ?
Se2 La2 S2 137.7 3_565 6_564 ?
S2 La2 S2 137.70(9) 3_565 6_564 ?
S2 La2 S2 138.42(9) . 6_564 ?
Se2 La2 S2 76.3 5_554 6_564 ?
S2 La2 S2 76.32(8) 5_554 6_564 ?
Se2 La2 S2 0.0 6_564 6_564 ?
Se2 La2 Se2 137.70(9) 2_665 4_664 ?
S2 La2 Se2 137.70(9) 2_665 4_664 ?
Se2 La2 Se2 138.42(9) 3_565 4_664 ?
S2 La2 Se2 138.42(9) 3_565 4_664 ?
S2 La2 Se2 88.6 . 4_664 ?
Se2 La2 Se2 76.32(8) 5_554 4_664 ?
S2 La2 Se2 76.32(8) 5_554 4_664 ?
Se2 La2 Se2 76.32(8) 6_564 4_664 ?
S2 La2 Se2 76.32(8) 6_564 4_664 ?
Se2 La2 S2 137.7 2_665 4_664 ?
S2 La2 S2 137.70(9) 2_665 4_664 ?
Se2 La2 S2 138.4 3_565 4_664 ?
S2 La2 S2 138.42(9) 3_565 4_664 ?
S2 La2 S2 88.60(6) . 4_664 ?
Se2 La2 S2 76.3 5_554 4_664 ?
S2 La2 S2 76.32(8) 5_554 4_664 ?
Se2 La2 S2 76.3 6_564 4_664 ?
S2 La2 S2 76.32(8) 6_564 4_664 ?
Se2 La2 S2 0.0 4_664 4_664 ?
S2 Ge1 Se4 103.57(10) . 4_665 ?
S2 Ge1 S4 103.57(10) . 4_665 ?
Se4 Ge1 S4 0.0 4_665 4_665 ?
S2 Ge1 Se1 101.68(10) . . ?
Se4 Ge1 Se1 110.79(10) 4_665 . ?
S4 Ge1 Se1 110.79(10) 4_665 . ?
S2 Ge1 Se3 112.13(11) . 4_664 ?
Se4 Ge1 Se3 100.79(9) 4_665 4_664 ?
S4 Ge1 Se3 100.79(9) 4_665 4_664 ?
Se1 Ge1 Se3 126.08(10) . 4_664 ?
S2 Ge1 S3 112.13(11) . 4_664 ?
Se4 Ge1 S3 100.79(9) 4_665 4_664 ?
S4 Ge1 S3 100.79(9) 4_665 4_664 ?
Se1 Ge1 S3 126.08(10) . 4_664 ?
Se3 Ge1 S3 0.0 4_664 4_664 ?
Ge1 Se1 La1 110.13(8) . 3_565 ?
Ge1 Se1 La1 85.73(7) . 4_665 ?
La1 Se1 La1 156.73(7) 3_565 4_665 ?
Ge1 Se1 La2 86.52(6) . 4_665 ?
La1 Se1 La2 95.67(5) 3_565 4_665 ?
La1 Se1 La2 102.40(5) 4_665 4_665 ?
Ge1 S2 La1 100.51(9) . . ?
Ge1 S2 La2 131.14(11) . . ?
La1 S2 La2 121.75(9) . . ?
Ge1 S2 La2 99.27(10) . 4_665 ?
La1 S2 La2 110.38(8) . 4_665 ?
La2 S2 La2 88.60(6) . 4_665 ?
Ge1 S3 La1 127.53(9) 4_665 9_565 ?
Ge1 S3 La1 118.02(8) 4_665 . ?
La1 S3 La1 97.96(6) 9_565 . ?
Ge1 S4 La1 104.21(7) 4_664 14_654 ?
Ge1 S4 La1 86.97(7) 4_664 . ?
La1 S4 La1 94.95(6) 14_654 . ?

_refine_diff_density_max         1.551
_refine_diff_density_min         -1.463
_refine_diff_density_rms         0.328

####################################################################### 
# 
# 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_x1
_database_code_depnum_ccdc_archive 'CCDC 2095329'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 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            'Ge3 La4 S4.25 Se7.75'
_chemical_formula_weight         1521.60

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   19.8976(12)
_cell_length_b                   19.8976(12)
_cell_length_c                   8.2984(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2845.3(4)
_cell_formula_units_Z            6
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    1399
_cell_measurement_theta_min      2.047
_cell_measurement_theta_max      29.518

_exptl_crystal_description       Block
_exptl_crystal_colour            Red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.328
_exptl_crystal_F_000             3933
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.040
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    28.806
_shelx_estimated_absorpt_T_min   0.392
_shelx_estimated_absorpt_T_max   0.762
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.280
_exptl_absorpt_correction_T_max  0.826
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16591
_diffrn_reflns_av_unetI/netI     0.0803
_diffrn_reflns_av_R_equivalents  0.1472
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.047
_diffrn_reflns_theta_max         29.518
_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 0.992
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1755
_reflns_number_gt                1399
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.970
_reflns_Friedel_fraction_max     0.984
_reflns_Friedel_fraction_full    0.998

_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)+(0.0260P)²+176.1860P] 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       0.00031(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 575 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1755
_refine_ls_number_parameters     63
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0391
_refine_ls_wR_factor_ref         0.0840
_refine_ls_wR_factor_gt          0.0709
_refine_ls_goodness_of_fit_ref   0.913
_refine_ls_restrained_S_all      0.913
_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
La1 La 0.43908(7) 0.33400(8) 0.02710(15) 0.0200(3) Uani 1 1 d . . . . .
La2 La 0.6667 0.3333 0.3209(2) 0.0155(5) Uani 1 3 d S T P . .
Ge1 Ge 0.65278(12) 0.51812(12) -0.0231(3) 0.0142(5) Uani 1 1 d . . . . .
S1 S 0.75433(12) 0.53228(13) -0.1854(3) 0.0175(8) Uani 0.067(19) 1 d . . P . .
Se1 Se 0.75433(12) 0.53228(13) -0.1854(3) 0.0175(8) Uani 0.933(19) 1 d . . P .
.
S2 S 0.6063(2) 0.3959(2) 0.0723(5) 0.0143(14) Uani 0.864(18) 1 d . . P . .
Se2 Se 0.6063(2) 0.3959(2) 0.0723(5) 0.0143(14) Uani 0.136(18) 1 d . . P . .
S3 S 0.39621(13) 0.34008(15) -0.3270(3) 0.0178(9) Uani 0.320(18) 1 d . . P . .
Se3 Se 0.39621(13) 0.34008(15) -0.3270(3) 0.0178(9) Uani 0.680(18) 1 d . . P .
.
S4 S 0.49129(13) 0.44805(12) 0.3201(3) 0.0178(8) Uani 0.165(18) 1 d . . P . .
Se4 Se 0.49129(13) 0.44805(12) 0.3201(3) 0.0178(8) Uani 0.835(18) 1 d . . 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
La1 S2 2.937(4) . ?
La1 Se3 2.954(3) 8 ?
La1 S3 2.954(3) 8 ?
La1 S3 3.079(3) . ?
La1 Se4 3.083(3) 15_554 ?
La1 S4 3.083(3) 15_554 ?
La1 S1 3.109(2) 2_655 ?
La1 Se1 3.109(2) 2_655 ?
La1 S4 3.128(3) . ?
La2 Se2 2.957(4) 2_655 ?
La2 S2 2.957(4) 2_655 ?
La2 Se2 2.957(4) 3_665 ?
La2 S2 2.957(4) 3_665 ?
La2 S2 2.957(4) . ?
La2 Se2 2.973(4) 5_655 ?
La2 S2 2.973(4) 5_655 ?
La2 Se2 2.973(4) 6 ?
La2 S2 2.973(4) 6 ?
La2 Se2 2.973(4) 4_665 ?
La2 S2 2.973(4) 4_665 ?
Ge1 S2 2.269(4) . ?
Ge1 Se3 2.309(3) 4_665 ?
Ge1 S3 2.309(3) 4_665 ?
Ge1 Se4 2.319(3) 4_664 ?
Ge1 S4 2.319(3) 4_664 ?
Ge1 S1 2.325(3) . ?
S1 La1 3.109(2) 3_665 ?
S1 La1 3.179(2) 4_664 ?
S2 La2 2.973(4) 4_664 ?
S3 Ge1 2.309(3) 4_664 ?
S3 La1 2.954(3) 15_554 ?
S4 Ge1 2.319(3) 4_665 ?
S4 La1 3.083(3) 8 ?

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 La1 Se3 139.61(10) . 8 ?
S2 La1 S3 139.61(10) . 8 ?
Se3 La1 S3 0.0 8 8 ?
S2 La1 S3 112.53(10) . . ?
Se3 La1 S3 69.7 8 . ?
S3 La1 S3 69.70(7) 8 . ?
S2 La1 Se4 138.66(10) . 15_554 ?
Se3 La1 Se4 81.71(7) 8 15_554 ?
S3 La1 Se4 81.71(7) 8 15_554 ?
S3 La1 Se4 78.06(7) . 15_554 ?
S2 La1 S4 138.66(10) . 15_554 ?
Se3 La1 S4 81.71(7) 8 15_554 ?
S3 La1 S4 81.71(7) 8 15_554 ?
S3 La1 S4 78.06(7) . 15_554 ?
Se4 La1 S4 0.0 15_554 15_554 ?
S2 La1 S1 78.34(9) . 2_655 ?
Se3 La1 S1 132.77(8) 8 2_655 ?
S3 La1 S1 132.77(8) 8 2_655 ?
S3 La1 S1 68.93(7) . 2_655 ?
Se4 La1 S1 68.39(6) 15_554 2_655 ?
S4 La1 S1 68.39(6) 15_554 2_655 ?
S2 La1 Se1 78.34(9) . 2_655 ?
Se3 La1 Se1 132.77(8) 8 2_655 ?
S3 La1 Se1 132.77(8) 8 2_655 ?
S3 La1 Se1 68.93(7) . 2_655 ?
Se4 La1 Se1 68.39(6) 15_554 2_655 ?
S4 La1 Se1 68.39(6) 15_554 2_655 ?
S1 La1 Se1 0.00(9) 2_655 2_655 ?
S2 La1 S4 72.60(9) . . ?
Se3 La1 S4 79.23(7) 8 . ?
S3 La1 S4 79.23(7) 8 . ?
S3 La1 S4 135.35(8) . . ?
Se4 La1 S4 128.9 15_554 . ?
S4 La1 S4 128.89(8) 15_554 . ?
S1 La1 S4 147.93(7) 2_655 . ?
Se1 La1 S4 147.93(7) 2_655 . ?
Se2 La2 S2 0.0 2_655 2_655 ?
Se2 La2 Se2 76.70(12) 2_655 3_665 ?
S2 La2 Se2 76.70(12) 2_655 3_665 ?
Se2 La2 S2 76.7 2_655 3_665 ?
S2 La2 S2 76.70(12) 2_655 3_665 ?
Se2 La2 S2 0.0 3_665 3_665 ?
Se2 La2 S2 76.7 2_655 . ?
S2 La2 S2 76.70(12) 2_655 . ?
Se2 La2 S2 76.7 3_665 . ?
S2 La2 S2 76.70(12) 3_665 . ?
Se2 La2 Se2 138.91(15) 2_655 5_655 ?
S2 La2 Se2 138.91(15) 2_655 5_655 ?
Se2 La2 Se2 88.80(10) 3_665 5_655 ?
S2 La2 Se2 88.80(10) 3_665 5_655 ?
S2 La2 Se2 137.4 . 5_655 ?
Se2 La2 S2 138.9 2_655 5_655 ?
S2 La2 S2 138.91(15) 2_655 5_655 ?
Se2 La2 S2 88.8 3_665 5_655 ?
S2 La2 S2 88.80(10) 3_665 5_655 ?
S2 La2 S2 137.36(15) . 5_655 ?
Se2 La2 S2 0.0 5_655 5_655 ?
Se2 La2 Se2 88.80(10) 2_655 6 ?
S2 La2 Se2 88.80(10) 2_655 6 ?
Se2 La2 Se2 137.36(15) 3_665 6 ?
S2 La2 Se2 137.36(15) 3_665 6 ?
S2 La2 Se2 138.9 . 6 ?
Se2 La2 Se2 76.21(12) 5_655 6 ?
S2 La2 Se2 76.21(12) 5_655 6 ?
Se2 La2 S2 88.8 2_655 6 ?
S2 La2 S2 88.80(10) 2_655 6 ?
Se2 La2 S2 137.4 3_665 6 ?
S2 La2 S2 137.36(15) 3_665 6 ?
S2 La2 S2 138.91(15) . 6 ?
Se2 La2 S2 76.2 5_655 6 ?
S2 La2 S2 76.21(12) 5_655 6 ?
Se2 La2 S2 0.0 6 6 ?
Se2 La2 Se2 137.36(15) 2_655 4_665 ?
S2 La2 Se2 137.36(15) 2_655 4_665 ?
Se2 La2 Se2 138.91(15) 3_665 4_665 ?
S2 La2 Se2 138.91(15) 3_665 4_665 ?
S2 La2 Se2 88.8 . 4_665 ?
Se2 La2 Se2 76.21(12) 5_655 4_665 ?
S2 La2 Se2 76.21(12) 5_655 4_665 ?
Se2 La2 Se2 76.21(12) 6 4_665 ?
S2 La2 Se2 76.21(12) 6 4_665 ?
Se2 La2 S2 137.4 2_655 4_665 ?
S2 La2 S2 137.36(15) 2_655 4_665 ?
Se2 La2 S2 138.9 3_665 4_665 ?
S2 La2 S2 138.91(15) 3_665 4_665 ?
S2 La2 S2 88.80(10) . 4_665 ?
Se2 La2 S2 76.2 5_655 4_665 ?
S2 La2 S2 76.21(12) 5_655 4_665 ?
Se2 La2 S2 76.2 6 4_665 ?
S2 La2 S2 76.21(12) 6 4_665 ?
Se2 La2 S2 0.0 4_665 4_665 ?
S2 Ge1 Se3 112.79(15) . 4_665 ?
S2 Ge1 S3 112.79(15) . 4_665 ?
Se3 Ge1 S3 0.0 4_665 4_665 ?
S2 Ge1 Se4 103.68(14) . 4_664 ?
Se3 Ge1 Se4 100.75(12) 4_665 4_664 ?
S3 Ge1 Se4 100.75(12) 4_665 4_664 ?
S2 Ge1 S4 103.68(14) . 4_664 ?
Se3 Ge1 S4 100.75(12) 4_665 4_664 ?
S3 Ge1 S4 100.75(12) 4_665 4_664 ?
Se4 Ge1 S4 0.0 4_664 4_664 ?
S2 Ge1 S1 101.29(14) . . ?
Se3 Ge1 S1 126.14(12) 4_665 . ?
S3 Ge1 S1 126.14(12) 4_665 . ?
Se4 Ge1 S1 110.41(12) 4_664 . ?
S4 Ge1 S1 110.41(12) 4_664 . ?
Ge1 S1 La1 109.96(10) . 3_665 ?
Ge1 S1 La1 86.09(8) . 4_664 ?
La1 S1 La1 156.95(9) 3_665 4_664 ?
Ge1 S2 La1 100.04(14) . . ?
Ge1 S2 La2 131.36(17) . . ?
La1 S2 La2 121.73(14) . . ?
Ge1 S2 La2 99.83(15) . 4_664 ?
La1 S2 La2 110.18(13) . 4_664 ?
La2 S2 La2 88.79(10) . 4_664 ?
Ge1 S3 La1 127.48(12) 4_664 15_554 ?
Ge1 S3 La1 117.67(11) 4_664 . ?
La1 S3 La1 98.35(8) 15_554 . ?
Ge1 S4 La1 104.35(9) 4_665 8 ?
Ge1 S4 La1 87.41(9) 4_665 . ?
La1 S4 La1 94.65(7) 8 . ?

_refine_diff_density_max         1.541
_refine_diff_density_min         -1.863
_refine_diff_density_rms         0.373

####################################################################### 
# 
# 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_x1_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2095328'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 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            'Ge3 La4 S6.34 Se5.66'
_chemical_formula_weight         1423.43

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   19.7766(11)
_cell_length_b                   19.7766(11)
_cell_length_c                   8.2448(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2792.6(3)
_cell_formula_units_Z            6
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    1566
_cell_measurement_theta_min      2.060
_cell_measurement_theta_max      29.642

_exptl_crystal_description       Block
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.078
_exptl_crystal_F_000             3707
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.040
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    25.491
_shelx_estimated_absorpt_T_min   0.429
_shelx_estimated_absorpt_T_max   0.785
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.253
_exptl_absorpt_correction_T_max  0.853
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            6237
_diffrn_reflns_av_unetI/netI     0.0558
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.060
_diffrn_reflns_theta_max         29.642
_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 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1749
_reflns_number_gt                1566
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.979
_reflns_Friedel_fraction_max     0.993
_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)] 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       0.00031(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 683 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1749
_refine_ls_number_parameters     63
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0296
_refine_ls_wR_factor_ref         0.0457
_refine_ls_wR_factor_gt          0.0439
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_restrained_S_all      1.005
_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
La1 La 0.56130(4) 0.66595(5) 0.97383(8) 0.01846(18) Uani 1 1 d . . . . .
La2 La 0.3333 0.6667 0.67836(12) 0.0115(2) Uani 1 3 d S T P . .
Ge1 Ge 0.34722(7) 0.48143(6) 1.02229(14) 0.0118(3) Uani 1 1 d . . . . .
S1 S 0.24572(7) 0.46723(8) 1.18522(16) 0.0142(5) Uani 0.240(9) 1 d . . P . .
Se1 Se 0.24572(7) 0.46723(8) 1.18522(16) 0.0142(5) Uani 0.760(9) 1 d . . P . .
S2 S 0.39365(15) 0.60361(14) 0.9275(3) 0.0119(9) Uani 0.965(9) 1 d . . P . .
Se2 Se 0.39365(15) 0.60361(14) 0.9275(3) 0.0119(9) Uani 0.035(9) 1 d . . P . .
S3 S 0.60387(9) 0.66028(10) 1.3274(2) 0.0170(6) Uani 0.535(9) 1 d . . P . .
Se3 Se 0.60387(9) 0.66028(10) 1.3274(2) 0.0170(6) Uani 0.465(9) 1 d . . P . .
S4 S 0.50915(8) 0.55226(8) 0.67890(18) 0.0150(5) Uani 0.374(8) 1 d . . P . .
Se4 Se 0.50915(8) 0.55226(8) 0.67890(18) 0.0150(5) Uani 0.626(8) 1 d . . 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
La1 Se3 2.9257(17) 14_654 ?
La1 S3 2.9257(17) 14_654 ?
La1 S2 2.928(3) . ?
La1 S3 3.0514(18) . ?
La1 Se4 3.0540(16) 9_565 ?
La1 S4 3.0540(16) 9_565 ?
La1 S1 3.0928(14) 2_665 ?
La1 Se1 3.0928(14) 2_665 ?
La1 S4 3.1166(16) . ?
La2 Se2 2.947(3) 2_665 ?
La2 S2 2.947(3) 2_665 ?
La2 Se2 2.947(3) 3_565 ?
La2 S2 2.947(3) 3_565 ?
La2 S2 2.947(3) . ?
La2 Se2 2.957(3) 5_554 ?
La2 S2 2.957(3) 5_554 ?
La2 Se2 2.957(3) 6_564 ?
La2 S2 2.957(3) 6_564 ?
La2 Se2 2.957(3) 4_664 ?
La2 S2 2.957(3) 4_664 ?
Ge1 S2 2.253(3) . ?
Ge1 Se3 2.280(2) 4_664 ?
Ge1 S3 2.280(2) 4_664 ?
Ge1 Se4 2.2986(18) 4_665 ?
Ge1 S4 2.2986(18) 4_665 ?
Ge1 S1 2.3128(18) . ?
S1 La1 3.0928(14) 3_565 ?
S1 La1 3.1652(15) 4_665 ?
S2 La2 2.957(3) 4_665 ?
S3 Ge1 2.280(2) 4_665 ?
S3 La1 2.9256(17) 9_565 ?
S4 Ge1 2.2987(18) 4_664 ?
S4 La1 3.0541(16) 14_654 ?

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
Se3 La1 S3 0.0 14_654 14_654 ?
Se3 La1 S2 139.33(7) 14_654 . ?
S3 La1 S2 139.33(7) 14_654 . ?
Se3 La1 S3 70.0 14_654 . ?
S3 La1 S3 69.98(5) 14_654 . ?
S2 La1 S3 112.60(6) . . ?
Se3 La1 Se4 81.93(5) 14_654 9_565 ?
S3 La1 Se4 81.93(5) 14_654 9_565 ?
S2 La1 Se4 138.70(6) . 9_565 ?
S3 La1 Se4 78.29(5) . 9_565 ?
Se3 La1 S4 81.93(5) 14_654 9_565 ?
S3 La1 S4 81.93(5) 14_654 9_565 ?
S2 La1 S4 138.70(6) . 9_565 ?
S3 La1 S4 78.29(5) . 9_565 ?
Se4 La1 S4 0.0 9_565 9_565 ?
Se3 La1 S1 133.07(5) 14_654 2_665 ?
S3 La1 S1 133.07(5) 14_654 2_665 ?
S2 La1 S1 78.51(6) . 2_665 ?
S3 La1 S1 68.97(5) . 2_665 ?
Se4 La1 S1 68.41(4) 9_565 2_665 ?
S4 La1 S1 68.41(4) 9_565 2_665 ?
Se3 La1 Se1 133.07(5) 14_654 2_665 ?
S3 La1 Se1 133.07(5) 14_654 2_665 ?
S2 La1 Se1 78.51(6) . 2_665 ?
S3 La1 Se1 68.97(5) . 2_665 ?
Se4 La1 Se1 68.41(4) 9_565 2_665 ?
S4 La1 Se1 68.41(4) 9_565 2_665 ?
S1 La1 Se1 0.00(5) 2_665 2_665 ?
Se3 La1 S4 79.20(5) 14_654 . ?
S3 La1 S4 79.20(5) 14_654 . ?
S2 La1 S4 72.41(6) . . ?
S3 La1 S4 135.78(5) . . ?
Se4 La1 S4 128.5 9_565 . ?
S4 La1 S4 128.46(5) 9_565 . ?
S1 La1 S4 147.69(4) 2_665 . ?
Se1 La1 S4 147.69(4) 2_665 . ?
Se2 La2 S2 0.0 2_665 2_665 ?
Se2 La2 Se2 76.78(8) 2_665 3_565 ?
S2 La2 Se2 76.78(8) 2_665 3_565 ?
Se2 La2 S2 76.8 2_665 3_565 ?
S2 La2 S2 76.78(8) 2_665 3_565 ?
Se2 La2 S2 0.0 3_565 3_565 ?
Se2 La2 S2 76.8 2_665 . ?
S2 La2 S2 76.78(8) 2_665 . ?
Se2 La2 S2 76.8 3_565 . ?
S2 La2 S2 76.78(8) 3_565 . ?
Se2 La2 Se2 139.03(9) 2_665 5_554 ?
S2 La2 Se2 139.03(9) 2_665 5_554 ?
Se2 La2 Se2 88.58(6) 3_565 5_554 ?
S2 La2 Se2 88.58(6) 3_565 5_554 ?
S2 La2 Se2 137.1 . 5_554 ?
Se2 La2 S2 139.0 2_665 5_554 ?
S2 La2 S2 139.03(9) 2_665 5_554 ?
Se2 La2 S2 88.6 3_565 5_554 ?
S2 La2 S2 88.58(6) 3_565 5_554 ?
S2 La2 S2 137.08(9) . 5_554 ?
Se2 La2 S2 0.0 5_554 5_554 ?
Se2 La2 Se2 88.58(6) 2_665 6_564 ?
S2 La2 Se2 88.58(6) 2_665 6_564 ?
Se2 La2 Se2 137.08(9) 3_565 6_564 ?
S2 La2 Se2 137.08(9) 3_565 6_564 ?
S2 La2 Se2 139.0 . 6_564 ?
Se2 La2 Se2 76.47(8) 5_554 6_564 ?
S2 La2 Se2 76.47(8) 5_554 6_564 ?
Se2 La2 S2 88.6 2_665 6_564 ?
S2 La2 S2 88.58(6) 2_665 6_564 ?
Se2 La2 S2 137.1 3_565 6_564 ?
S2 La2 S2 137.08(9) 3_565 6_564 ?
S2 La2 S2 139.03(9) . 6_564 ?
Se2 La2 S2 76.5 5_554 6_564 ?
S2 La2 S2 76.47(8) 5_554 6_564 ?
Se2 La2 S2 0.0 6_564 6_564 ?
Se2 La2 Se2 137.08(9) 2_665 4_664 ?
S2 La2 Se2 137.08(9) 2_665 4_664 ?
Se2 La2 Se2 139.03(9) 3_565 4_664 ?
S2 La2 Se2 139.03(9) 3_565 4_664 ?
S2 La2 Se2 88.6 . 4_664 ?
Se2 La2 Se2 76.47(8) 5_554 4_664 ?
S2 La2 Se2 76.47(8) 5_554 4_664 ?
Se2 La2 Se2 76.47(8) 6_564 4_664 ?
S2 La2 Se2 76.47(8) 6_564 4_664 ?
Se2 La2 S2 137.1 2_665 4_664 ?
S2 La2 S2 137.08(9) 2_665 4_664 ?
Se2 La2 S2 139.0 3_565 4_664 ?
S2 La2 S2 139.03(9) 3_565 4_664 ?
S2 La2 S2 88.58(6) . 4_664 ?
Se2 La2 S2 76.5 5_554 4_664 ?
S2 La2 S2 76.47(8) 5_554 4_664 ?
Se2 La2 S2 76.5 6_564 4_664 ?
S2 La2 S2 76.47(8) 6_564 4_664 ?
Se2 La2 S2 0.0 4_664 4_664 ?
S2 Ge1 Se3 112.94(9) . 4_664 ?
S2 Ge1 S3 112.94(9) . 4_664 ?
Se3 Ge1 S3 0.0 4_664 4_664 ?
S2 Ge1 Se4 103.63(8) . 4_665 ?
Se3 Ge1 Se4 100.93(8) 4_664 4_665 ?
S3 Ge1 Se4 100.93(8) 4_664 4_665 ?
S2 Ge1 S4 103.63(8) . 4_665 ?
Se3 Ge1 S4 100.93(8) 4_664 4_665 ?
S3 Ge1 S4 100.93(8) 4_664 4_665 ?
Se4 Ge1 S4 0.0 4_665 4_665 ?
S2 Ge1 S1 101.26(8) . . ?
Se3 Ge1 S1 126.02(7) 4_664 . ?
S3 Ge1 S1 126.02(7) 4_664 . ?
Se4 Ge1 S1 110.27(7) 4_665 . ?
S4 Ge1 S1 110.27(7) 4_665 . ?
Ge1 S1 La1 110.11(6) . 3_565 ?
Ge1 S1 La1 86.30(5) . 4_665 ?
La1 S1 La1 156.79(5) 3_565 4_665 ?
Ge1 S2 La1 100.07(9) . . ?
Ge1 S2 La2 131.42(11) . . ?
La1 S2 La2 121.71(9) . . ?
Ge1 S2 La2 100.12(9) . 4_665 ?
La1 S2 La2 109.99(8) . 4_665 ?
La2 S2 La2 88.57(6) . 4_665 ?
Ge1 S3 La1 127.61(7) 4_665 9_565 ?
Ge1 S3 La1 117.83(7) 4_665 . ?
La1 S3 La1 98.44(5) 9_565 . ?
Ge1 S4 La1 104.46(6) 4_664 14_654 ?
Ge1 S4 La1 87.70(5) 4_664 . ?
La1 S4 La1 94.37(4) 14_654 . ?

_refine_diff_density_max         0.927
_refine_diff_density_min         -0.881
_refine_diff_density_rms         0.224

####################################################################### 
# 
# 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_x1_CCDC2
_database_code_depnum_ccdc_archive 'CCDC 2095327'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-09-10 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            'Ge3 La4 S7.77 Se4.22'
_chemical_formula_weight         1356.28

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_H-M_alt        'R 3 c :H'
_space_group_name_Hall           'R 3 -2"c'

_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+1/2'
'-x+y, y, z+1/2'
'x, x-y, z+1/2'
'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+5/6'
'-x+y+2/3, y+1/3, z+5/6'
'x+2/3, x-y+1/3, z+5/6'
'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+7/6'
'-x+y+1/3, y+2/3, z+7/6'
'x+1/3, x-y+2/3, z+7/6'

_cell_length_a                   19.6679(12)
_cell_length_b                   19.6679(12)
_cell_length_c                   8.1950(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2745.3(4)
_cell_formula_units_Z            6
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    1665
_cell_measurement_theta_min      2.071
_cell_measurement_theta_max      30.612

_exptl_crystal_description       Block
_exptl_crystal_colour            yellow-orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.922
_exptl_crystal_F_000             3552
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.040
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    23.247
_shelx_estimated_absorpt_T_min   0.457
_shelx_estimated_absorpt_T_max   0.801
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.230
_exptl_absorpt_correction_T_max  0.823
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX II CCD area-detector'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9826
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_av_R_equivalents  0.0756
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.071
_diffrn_reflns_theta_max         30.612
_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 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1874
_reflns_number_gt                1665
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.981
_reflns_Friedel_fraction_max     0.996
_reflns_Friedel_fraction_full    0.996

_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       'SMART V5.625 (Bruker, 2000)'
_computing_cell_refinement       'SMART V5.625 (Bruker, 2000)'
_computing_data_reduction        'SAINT V6.32 (Bruker, 2001)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_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)+56.6826P] 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       0.000090(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 725 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1874
_refine_ls_number_parameters     63
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0323
_refine_ls_wR_factor_ref         0.0597
_refine_ls_wR_factor_gt          0.0518
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_restrained_S_all      1.058
_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
La1 La 0.43797(5) 0.33346(6) 0.02593(9) 0.01817(19) Uani 1 1 d . . . . .
La2 La 0.6667 0.3333 0.32203(13) 0.0112(3) Uani 1 3 d S T P . .
Ge1 Ge 0.65285(8) 0.51901(8) -0.02245(15) 0.0114(3) Uani 1 1 d . . . . .
S1 S 0.75416(10) 0.53323(10) -0.1847(2) 0.0153(6) Uani 0.366(11) 1 d . . P . .
Se1 Se 0.75416(10) 0.53323(10) -0.1847(2) 0.0153(6) Uani 0.634(11) 1 d . . P .
.
S2 S 0.60615(18) 0.39664(18) 0.0732(3) 0.0118(9) Uani 0.977(11) 1 d . . P . .
Se2 Se 0.60615(18) 0.39664(18) 0.0732(3) 0.0118(9) Uani 0.023(11) 1 d . . P . .
S3 S 0.39643(13) 0.33939(14) -0.3276(3) 0.0150(7) Uani 0.724(10) 1 d . . P . .
Se3 Se 0.39643(13) 0.33939(14) -0.3276(3) 0.0150(7) Uani 0.276(10) 1 d . . P .
.
S4 S 0.49060(11) 0.44729(11) 0.3208(2) 0.0156(6) Uani 0.522(11) 1 d . . P . .
Se4 Se 0.49060(11) 0.44729(11) 0.3208(2) 0.0156(6) Uani 0.478(11) 1 d . . 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
La1 Se3 2.908(2) 8 ?
La1 S3 2.908(2) 8 ?
La1 S2 2.920(3) . ?
La1 Se4 3.023(2) 15_554 ?
La1 S4 3.023(2) 15_554 ?
La1 S3 3.028(2) . ?
La1 S1 3.0745(18) 2_655 ?
La1 Se1 3.0745(18) 2_655 ?
La1 S4 3.100(2) . ?
La2 Se2 2.934(3) 2_655 ?
La2 S2 2.934(3) 2_655 ?
La2 Se2 2.934(3) 3_665 ?
La2 S2 2.934(3) 3_665 ?
La2 S2 2.934(3) . ?
La2 Se2 2.947(3) 5_655 ?
La2 S2 2.947(3) 5_655 ?
La2 Se2 2.947(3) 6 ?
La2 S2 2.947(3) 6 ?
La2 Se2 2.947(3) 4_665 ?
La2 S2 2.947(3) 4_665 ?
Ge1 S2 2.245(3) . ?
Ge1 Se3 2.255(3) 4_665 ?
Ge1 S3 2.255(3) 4_665 ?
Ge1 Se4 2.279(2) 4_664 ?
Ge1 S4 2.279(2) 4_664 ?
Ge1 S1 2.293(2) . ?
S1 La1 3.0746(18) 3_665 ?
S1 La1 3.1445(19) 4_664 ?
S2 La2 2.947(3) 4_664 ?
S3 Ge1 2.255(3) 4_664 ?
S3 La1 2.908(2) 15_554 ?
S4 Ge1 2.279(2) 4_665 ?
S4 La1 3.023(2) 8 ?

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
Se3 La1 S3 0.0 8 8 ?
Se3 La1 S2 138.64(8) 8 . ?
S3 La1 S2 138.64(8) 8 . ?
Se3 La1 Se4 82.29(6) 8 15_554 ?
S3 La1 Se4 82.29(6) 8 15_554 ?
S2 La1 Se4 139.03(8) . 15_554 ?
Se3 La1 S4 82.29(6) 8 15_554 ?
S3 La1 S4 82.29(6) 8 15_554 ?
S2 La1 S4 139.03(8) . 15_554 ?
Se4 La1 S4 0.0 15_554 15_554 ?
Se3 La1 S3 70.3 8 . ?
S3 La1 S3 70.27(6) 8 . ?
S2 La1 S3 112.38(7) . . ?
Se4 La1 S3 78.45(6) 15_554 . ?
S4 La1 S3 78.45(6) 15_554 . ?
Se3 La1 S1 133.47(6) 8 2_655 ?
S3 La1 S1 133.47(6) 8 2_655 ?
S2 La1 S1 78.68(7) . 2_655 ?
Se4 La1 S1 68.52(5) 15_554 2_655 ?
S4 La1 S1 68.52(5) 15_554 2_655 ?
S3 La1 S1 68.95(6) . 2_655 ?
Se3 La1 Se1 133.47(6) 8 2_655 ?
S3 La1 Se1 133.47(6) 8 2_655 ?
S2 La1 Se1 78.68(7) . 2_655 ?
Se4 La1 Se1 68.52(5) 15_554 2_655 ?
S4 La1 Se1 68.52(5) 15_554 2_655 ?
S3 La1 Se1 68.95(6) . 2_655 ?
S1 La1 Se1 0.00(7) 2_655 2_655 ?
Se3 La1 S4 79.06(6) 8 . ?
S3 La1 S4 79.06(6) 8 . ?
S2 La1 S4 72.00(7) . . ?
Se4 La1 S4 128.6 15_554 . ?
S4 La1 S4 128.58(7) 15_554 . ?
S3 La1 S4 135.82(7) . . ?
S1 La1 S4 147.42(5) 2_655 . ?
Se1 La1 S4 147.42(5) 2_655 . ?
Se2 La2 S2 0.0 2_655 2_655 ?
Se2 La2 Se2 77.02(9) 2_655 3_665 ?
S2 La2 Se2 77.02(9) 2_655 3_665 ?
Se2 La2 S2 77.0 2_655 3_665 ?
S2 La2 S2 77.02(9) 2_655 3_665 ?
Se2 La2 S2 0.0 3_665 3_665 ?
Se2 La2 S2 77.0 2_655 . ?
S2 La2 S2 77.02(9) 2_655 . ?
Se2 La2 S2 77.0 3_665 . ?
S2 La2 S2 77.02(9) 3_665 . ?
Se2 La2 Se2 138.95(11) 2_655 5_655 ?
S2 La2 Se2 138.95(11) 2_655 5_655 ?
Se2 La2 Se2 88.34(8) 3_665 5_655 ?
S2 La2 Se2 88.34(8) 3_665 5_655 ?
S2 La2 Se2 137.0 . 5_655 ?
Se2 La2 S2 139.0 2_655 5_655 ?
S2 La2 S2 138.95(11) 2_655 5_655 ?
Se2 La2 S2 88.3 3_665 5_655 ?
S2 La2 S2 88.34(8) 3_665 5_655 ?
S2 La2 S2 136.98(11) . 5_655 ?
Se2 La2 S2 0.0 5_655 5_655 ?
Se2 La2 Se2 88.34(8) 2_655 6 ?
S2 La2 Se2 88.34(8) 2_655 6 ?
Se2 La2 Se2 136.98(11) 3_665 6 ?
S2 La2 Se2 136.98(11) 3_665 6 ?
S2 La2 Se2 139.0 . 6 ?
Se2 La2 Se2 76.60(9) 5_655 6 ?
S2 La2 Se2 76.60(9) 5_655 6 ?
Se2 La2 S2 88.3 2_655 6 ?
S2 La2 S2 88.34(8) 2_655 6 ?
Se2 La2 S2 137.0 3_665 6 ?
S2 La2 S2 136.98(11) 3_665 6 ?
S2 La2 S2 138.96(12) . 6 ?
Se2 La2 S2 76.6 5_655 6 ?
S2 La2 S2 76.60(9) 5_655 6 ?
Se2 La2 S2 0.0 6 6 ?
Se2 La2 Se2 136.98(11) 2_655 4_665 ?
S2 La2 Se2 136.98(11) 2_655 4_665 ?
Se2 La2 Se2 138.95(12) 3_665 4_665 ?
S2 La2 Se2 138.95(12) 3_665 4_665 ?
S2 La2 Se2 88.3 . 4_665 ?
Se2 La2 Se2 76.60(9) 5_655 4_665 ?
S2 La2 Se2 76.60(9) 5_655 4_665 ?
Se2 La2 Se2 76.60(9) 6 4_665 ?
S2 La2 Se2 76.60(9) 6 4_665 ?
Se2 La2 S2 137.0 2_655 4_665 ?
S2 La2 S2 136.98(11) 2_655 4_665 ?
Se2 La2 S2 139.0 3_665 4_665 ?
S2 La2 S2 138.95(12) 3_665 4_665 ?
S2 La2 S2 88.34(8) . 4_665 ?
Se2 La2 S2 76.6 5_655 4_665 ?
S2 La2 S2 76.60(9) 5_655 4_665 ?
Se2 La2 S2 76.6 6 4_665 ?
S2 La2 S2 76.60(9) 6 4_665 ?
Se2 La2 S2 0.0 4_665 4_665 ?
S2 Ge1 Se3 112.57(11) . 4_665 ?
S2 Ge1 S3 112.57(11) . 4_665 ?
Se3 Ge1 S3 0.0 4_665 4_665 ?
S2 Ge1 Se4 103.57(10) . 4_664 ?
Se3 Ge1 Se4 101.38(10) 4_665 4_664 ?
S3 Ge1 Se4 101.38(10) 4_665 4_664 ?
S2 Ge1 S4 103.57(10) . 4_664 ?
Se3 Ge1 S4 101.38(10) 4_665 4_664 ?
S3 Ge1 S4 101.38(10) 4_665 4_664 ?
Se4 Ge1 S4 0.0 4_664 4_664 ?
S2 Ge1 S1 101.43(10) . . ?
Se3 Ge1 S1 125.90(10) 4_665 . ?
S3 Ge1 S1 125.90(10) 4_665 . ?
Se4 Ge1 S1 110.21(8) 4_664 . ?
S4 Ge1 S1 110.21(8) 4_664 . ?
Ge1 S1 La1 110.31(7) . 3_665 ?
Ge1 S1 La1 86.46(6) . 4_664 ?
La1 S1 La1 156.43(7) 3_665 4_664 ?
Ge1 S2 La1 100.32(11) . . ?
Ge1 S2 La2 131.48(13) . . ?
La1 S2 La2 121.69(10) . . ?
Ge1 S2 La2 100.01(10) . 4_664 ?
La1 S2 La2 109.77(10) . 4_664 ?
La2 S2 La2 88.33(8) . 4_664 ?
Ge1 S3 La1 127.77(10) 4_664 15_554 ?
Ge1 S3 La1 118.43(10) 4_664 . ?
La1 S3 La1 98.25(7) 15_554 . ?
Ge1 S4 La1 104.38(7) 4_665 8 ?
Ge1 S4 La1 87.80(7) 4_665 . ?
La1 S4 La1 94.30(6) 8 . ?

_refine_diff_density_max         1.106
_refine_diff_density_min         -1.150
_refine_diff_density_rms         0.280

