# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_x1
# Added during the CSD deposition process: Saturday 15 July 2023 06:42 PM
# end Validation Reply Form

_database_code_depnum_ccdc_archive 'CCDC 2281773'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2023-07-15 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_ATOM007_x1                  
;
PROBLEM: _atom_site_aniso_label is missing
RESPONSE: This error originates from a system error of our  instrument, whenever for any crystals, we tried to refine the  structure anisotropically, it will result in negative thermal  displacement parameters (NDP). Hence, to avoid this issue, we  refined our structure isotropically. The accuracy of the  structure model was verified by powder X-ray diffraction and  many attempts to collect single-crystal diffraction data. All  single crystal data can only be solved by this structure model.   The experimental PXRD pattern matches well with the theoretical model calculated from this structure model."
;
_vrf_THETM01_x1                  
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: "This error originates from the heavily twined nature of our crystals.  For each data we collected, at least three domains were found, to get good refinement and low R-value, we separated these domains and removed high-angle data, which resulted in this error. The accuracy of the structure model was verified by powder X-ray diffraction and many attempts to collect single-crystal diffraction data. All single crystal data can only be solved by this structure model.  The experimental PXRD pattern matches well with the theoretical model calculated from this structure model. "
;
_vrf_PLAT090_x1                  
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       2.23 Note
RESPONSE: This error originates from the heavily twined nature  of our crystals. For each data we collected, at least three  domains were found, to get good refinement and low R-value, we  separated these domains and removed high-angle data, which  resulted in this error. The accuracy of the structure model was  verified by powder X-ray diffraction and many attempts to  collect single-crystal diffraction data. All single crystal  data can only be solved by this structure model.  The  experimental PXRD pattern matches well with the theoretical  model calculated from this structure model."
;

_audit_creation_method           SHELXL-2019/1
_shelx_SHELXL_version_number     2019/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'As Br2 La3 S5'
_chemical_formula_weight         811.77

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
As As -0.9300 1.0051 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_H-M_alt        'C c'
_space_group_name_Hall           'C -2yc'

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

_cell_length_a                   22.3092(14)
_cell_length_b                   7.1387(5)
_cell_length_c                   7.1638(5)
_cell_angle_alpha                90
_cell_angle_beta                 98.471(2)
_cell_angle_gamma                90
_cell_volume                     1128.45(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    165
_cell_measurement_theta_min      2.007
_cell_measurement_theta_max      25.997

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.778
_exptl_crystal_F_000             1416
_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    105.859
_shelx_estimated_absorpt_T_min   0.143
_shelx_estimated_absorpt_T_max   0.417
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  1.10
_exptl_absorpt_correction_T_max  3.20
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker X8 PROSPECTOR'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            508
_diffrn_reflns_av_unetI/netI     0.0525
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_l_min       -4
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_theta_min         2.007
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_full        25.997
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measured_fraction_theta_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.771
_diffrn_reflns_point_group_measured_fraction_full 0.771
_reflns_number_total             165
_reflns_number_gt                163
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.571
_reflns_Friedel_fraction_max     0.566
_reflns_Friedel_fraction_full    0.566

_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_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-2019 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2019 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-2019 (Sheldrick, 1997)'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1354P)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-2019/1 (Sheldrick 2019)'
_refine_ls_extinction_coef       0.0019(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.22(7)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         165
_refine_ls_number_parameters     47
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0444
_refine_ls_wR_factor_ref         0.1058
_refine_ls_wR_factor_gt          0.1058
_refine_ls_goodness_of_fit_ref   0.832
_refine_ls_restrained_S_all      0.825
_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 0.1227(5) 0.1977(12) 0.3695(16) 0.019(8) Uiso 1 1 d . . . . .
La2 La -0.0278(5) 0.1974(13) -0.1259(18) 0.018(8) Uiso 1 1 d . . . . .
La3 La 0.2744(6) 0.2081(15) 0.013(2) 0.019(8) Uiso 1 1 d . . . . .
As1 As 0.3189(10) 0.309(2) -0.425(4) 0.023(10) Uiso 1 1 d . . . . .
Br1 Br 0.1161(9) 0.379(3) -0.020(3) 0.019(10) Uiso 1 1 d . . . . .
Br2 Br -0.0165(7) 0.387(3) 0.257(3) 0.034(10) Uiso 1 1 d . . . . .
S1 S -0.148(2) 0.408(7) -0.115(8) 0.020(18) Uiso 1 1 d . . . . .
S2 S 0.201(2) 0.055(6) 0.693(9) 0.002(16) Uiso 1 1 d . . . . .
S3 S -0.116(2) -0.046(6) 0.049(8) 0.01(2) Uiso 1 1 d . . . . .
S4 S 0.2431(18) 0.422(5) 0.354(7) 0.00(2) Uiso 1 1 d . . . . .
S5 S 0.047(3) 0.052(5) 0.615(8) 0.024(18) Uiso 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 S2 2.88(7) . ?
La1 S5 2.81(7) . ?
La1 S5 2.91(6) 2_554 ?
La1 S2 2.92(5) 2_554 ?
La1 Br1 3.06(2) . ?
La1 Br1 3.13(2) 2_565 ?
La1 S4 3.14(4) . ?
La1 Br2 3.37(2) . ?
La2 S5 2.86(7) 1_554 ?
La2 S5 2.84(5) 2_554 ?
La2 S3 3.04(4) . ?
La2 Br2 3.04(3) . ?
La2 S1 3.08(5) . ?
La2 S3 3.02(6) 2_554 ?
La2 Br2 3.10(2) 2_564 ?
La2 Br1 3.44(3) . ?
La3 S2 2.92(5) 2_554 ?
La3 S2 2.83(6) 1_554 ?
La3 S4 2.92(4) 2_564 ?
La3 S4 3.05(5) . ?
La3 S1 2.98(6) 3_545 ?
La3 S3 2.98(5) 3 ?
La3 S1 3.08(5) 4 ?
As1 S4 2.28(5) 1_554 ?
As1 S1 2.26(5) 4_554 ?
As1 S3 2.25(5) 4_554 ?

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 S5 73.5(14) . . ?
S2 La1 S5 121.1(11) . 2_554 ?
S5 La1 S5 79.4(12) . 2_554 ?
S2 La1 S2 78.4(11) . 2_554 ?
S5 La1 S2 119.7(14) . 2_554 ?
S5 La1 S2 71.4(17) 2_554 2_554 ?
S2 La1 Br1 145.8(12) . . ?
S5 La1 Br1 140.6(14) . . ?
S5 La1 Br1 75.1(12) 2_554 . ?
S2 La1 Br1 79.5(12) 2_554 . ?
S2 La1 Br1 100.6(9) . 2_565 ?
S5 La1 Br1 98.2(10) . 2_565 ?
S5 La1 Br1 134.8(10) 2_554 2_565 ?
S2 La1 Br1 139.2(11) 2_554 2_565 ?
Br1 La1 Br1 79.9(4) . 2_565 ?
S2 La1 S4 77.7(12) . . ?
S5 La1 S4 143.7(16) . . ?
S5 La1 S4 135.5(18) 2_554 . ?
S2 La1 S4 74.4(12) 2_554 . ?
Br1 La1 S4 71.3(11) . . ?
Br1 La1 S4 65.7(7) 2_565 . ?
S2 La1 Br2 139.7(12) . . ?
S5 La1 Br2 71.2(12) . . ?
S5 La1 Br2 70.5(10) 2_554 . ?
S2 La1 Br2 137.0(16) 2_554 . ?
Br1 La1 Br2 72.2(6) . . ?
Br1 La1 Br2 66.3(5) 2_565 . ?
S4 La1 Br2 123.3(9) . . ?
S5 La2 S5 79.9(13) 1_554 2_554 ?
S5 La2 S3 122.5(13) 1_554 . ?
S5 La2 S3 75.4(17) 2_554 . ?
S5 La2 Br2 140.3(13) 1_554 . ?
S5 La2 Br2 76.6(14) 2_554 . ?
S3 La2 Br2 81.6(11) . . ?
S5 La2 S1 141.5(15) 1_554 . ?
S5 La2 S1 136.3(15) 2_554 . ?
S3 La2 S1 69.4(13) . . ?
Br2 La2 S1 73.4(12) . . ?
S5 La2 S3 75.3(14) 1_554 2_554 ?
S5 La2 S3 120.0(13) 2_554 2_554 ?
S3 La2 S3 73.9(9) . 2_554 ?
Br2 La2 S3 144.4(11) . 2_554 ?
S1 La2 S3 73.9(10) . 2_554 ?
S5 La2 Br2 95.3(12) 1_554 2_564 ?
S5 La2 Br2 134.5(13) 2_554 2_564 ?
S3 La2 Br2 137.9(11) . 2_564 ?
Br2 La2 Br2 79.5(4) . 2_564 ?
S1 La2 Br2 69.2(10) . 2_564 ?
S3 La2 Br2 101.8(11) 2_554 2_564 ?
S5 La2 Br1 70.6(10) 1_554 . ?
S5 La2 Br1 70.1(11) 2_554 . ?
S3 La2 Br1 140.0(13) . . ?
Br2 La2 Br1 71.5(5) . . ?
S1 La2 Br1 126.6(11) . . ?
S3 La2 Br1 142.0(11) 2_554 . ?
Br2 La2 Br1 65.8(5) 2_564 . ?
S2 La3 S2 79.3(9) 2_554 1_554 ?
S2 La3 S4 129.6(12) 2_554 2_564 ?
S2 La3 S4 87.6(15) 1_554 2_564 ?
S2 La3 S4 76.0(15) 2_554 . ?
S2 La3 S4 131.9(13) 1_554 . ?
S4 La3 S4 77.8(7) 2_564 . ?
S2 La3 S1 93.7(14) 2_554 3_545 ?
S2 La3 S1 76.7(12) 1_554 3_545 ?
S4 La3 S1 130.3(17) 2_564 3_545 ?
S4 La3 S1 144.8(15) . 3_545 ?
S2 La3 S3 148(2) 2_554 3 ?
S2 La3 S3 132(2) 1_554 3 ?
S4 La3 S3 69.3(14) 2_564 3 ?
S4 La3 S3 85.1(13) . 3 ?
S1 La3 S3 86.8(16) 3_545 3 ?
S2 La3 S1 74.0(16) 2_554 4 ?
S2 La3 S1 141.5(13) 1_554 4 ?
S4 La3 S1 130.8(13) 2_564 4 ?
S4 La3 S1 66.8(11) . 4 ?
S1 La3 S1 78.0(11) 3_545 4 ?
S3 La3 S1 74.5(15) 3 4 ?
S4 As1 S1 96(2) 1_554 4_554 ?
S4 As1 S3 95.6(18) 1_554 4_554 ?
S1 As1 S3 101(2) 4_554 4_554 ?
La1 Br1 La1 129.8(7) . 2_564 ?
La1 Br1 La2 87.7(6) . . ?
La1 Br1 La2 112.6(6) 2_564 . ?
La2 Br2 La2 132.2(9) . 2_565 ?
La2 Br2 La1 89.3(7) . . ?
La2 Br2 La1 115.3(7) 2_565 . ?
As1 S1 La3 93(2) 4_455 3_455 ?
As1 S1 La2 92.6(17) 4_455 . ?
La3 S1 La2 155(2) 3_455 . ?
As1 S1 La3 98(2) 4_455 4_454 ?
La3 S1 La3 100.3(14) 3_455 4_454 ?
La2 S1 La3 103.1(18) . 4_454 ?
La3 S2 La1 101(2) 2 . ?
La3 S2 La3 108.1(17) 2 1_556 ?
La1 S2 La3 136.5(15) . 1_556 ?
La3 S2 La1 101.8(12) 2 2 ?
La1 S2 La1 103.7(15) . 2 ?
La3 S2 La1 102(2) 1_556 2 ?
As1 S3 La2 93.9(16) 4_455 . ?
As1 S3 La3 85.6(14) 4_455 3_445 ?
La2 S3 La3 151(2) . 3_445 ?
As1 S3 La2 124(2) 4_455 2 ?
La2 S3 La2 97.6(14) . 2 ?
La3 S3 La2 106.9(15) 3_445 2 ?
As1 S4 La3 86.6(15) 1_556 2_565 ?
As1 S4 La3 98.2(15) 1_556 . ?
La3 S4 La3 134.1(17) 2_565 . ?
As1 S4 La1 110.2(17) 1_556 . ?
La3 S4 La1 127.2(17) 2_565 . ?
La3 S4 La1 94.0(11) . . ?
La2 S5 La2 106(2) 1_556 2 ?
La2 S5 La1 137.1(13) 1_556 . ?
La2 S5 La1 102(2) 2 . ?
La2 S5 La1 99(2) 1_556 2 ?
La2 S5 La1 103.3(12) 2 2 ?
La1 S5 La1 106(2) . 2 ?

_refine_diff_density_max         0.894
_refine_diff_density_min         -0.667
_refine_diff_density_rms         0.218

_shelx_res_file                  
;
TITL wjc038_0m in Cc
    x1.res
    created by SHELXL-2019/1 at 10:30:14 on 13-Jul-2023
CELL 1.54178  22.30920   7.13870   7.16380  90.0000  98.4714  90.0000
ZERR    4.00   0.00140   0.00050   0.00050   0.0000   0.0024   0.0000
LATT -7
SYMM X, -Y, 0.5+Z
SFAC S AS BR LA
UNIT 20 4 8 12
TEMP 23.000
SIZE 0.01 0.02 0.03

L.S. 14
BOND
acta
TWIN
omit -2 52
FMAP 2
PLAN -5

WGHT    0.135400
EXTI    0.001933
BASF   0.21888
FVAR       0.06514
LA1   4    0.122688    0.197749    0.369482    11.00000    0.01924
LA2   4   -0.027795    0.197391   -0.125924    11.00000    0.01829
LA3   4    0.274413    0.208086    0.012911    11.00000    0.01885
AS1   2    0.318919    0.308970   -0.425383    11.00000    0.02334
BR1   3    0.116113    0.378873   -0.019903    11.00000    0.01930
BR2   3   -0.016537    0.387206    0.257009    11.00000    0.03433
S1    1   -0.147678    0.408247   -0.114601    11.00000    0.01985
S2    1    0.200964    0.054892    0.693114    11.00000    0.00206
S3    1   -0.116362   -0.045915    0.049428    11.00000    0.01056
S4    1    0.243135    0.422208    0.354457    11.00000    0.00245
S5    1    0.046615    0.052471    0.614662    11.00000    0.02414
HKLF 4




REM  wjc038_0m in Cc
REM wR2 = 0.1058, GooF = S = 0.832, Restrained GooF = 0.825 for all data
REM R1 = 0.0444 for 163 Fo > 4sig(Fo) and 0.0444 for all 165 data
REM 47 parameters refined using 2 restraints

END

WGHT      0.0918      0.0000

REM Highest difference peak  0.894,  deepest hole -0.667,  1-sigma level  0.218
Q1    1   0.1254  0.1861  0.8162  11.00000  0.05    0.89
Q2    1  -0.0277  0.1850 -0.5924  11.00000  0.05    0.88
Q3    1   0.2731  0.1890  0.5053  11.00000  0.05    0.65
Q4    1   0.1198  0.2999  0.5201  11.00000  0.05    0.60
Q5    1  -0.0207  0.2995 -0.3018  11.00000  0.05    0.55
;
_shelx_res_checksum              39070
####################################################################### 
# 
# 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
# Added during the CSD deposition process: Saturday 15 July 2023 06:46 PM
# end Validation Reply Form

_database_code_depnum_ccdc_archive 'CCDC 2281774'
loop_
_audit_author_name
_audit_author_address
'Jian Wang'
;Wichita State University
United States of America
;
_audit_update_record             
;
2023-07-15 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_ATOM007_x1                  
;
PROBLEM: _atom_site_aniso_label is missing
RESPONSE: "This error originates from a system error of our instrument, whenever for any crystals, we tried to refine the structure anisotropically, it will result in negative thermal displacement parameters (NDP). Hence, to avoid this issue, we refined our structure isotropically. The accuracy of the structure model was verified by powder X-ray diffraction and many attempts to collect single-crystal diffraction data. All single crystal data can only be solved by this structure model.  The experimental PXRD pattern matches well with the theoretical model calculated from this structure model."
;
_vrf_THETM01_x1                  
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: "This error originates from the heavily twined nature of our crystals. For each data we collected, at least three domains were found, to get good refinement and low R-value, we separated these domains and removed high-angle data, which resulted in this error. The accuracy of the structure model was verified by powder X-ray diffraction and many attempts to collect single-crystal diffraction data. All single crystal data can only be solved by this structure model.  The experimental PXRD pattern matches well with the theoretical model calculated from this structure model. "
;
_vrf_PLAT972_x1                  
;
PROBLEM: Check Calcd Resid. Dens.  0.62Ang From La2            -2.59 eA-3
RESPONSE: "This error originates from the heavily twined nature of our crystals. For each data we collected, at least three domains were found, to get good refinement and low R-value, we separated these domains and removed high-angle data, which resulted in this error. The accuracy of the structure model was verified by powder X-ray diffraction and many attempts to collect single-crystal diffraction data. All single crystal data can only be solved by this structure model.  The experimental PXRD pattern matches well with the theoretical model calculated from this structure model. "
;
_vrf_PLAT972_x1_2                
;
PROBLEM: Check Calcd Resid. Dens.  0.65Ang From La2            -2.21 eA-3
RESPONSE: "This error originates from the heavily twined nature of our crystals.
;

_audit_creation_method           SHELXL-2019/1
_shelx_SHELXL_version_number     2019/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'As2 Cl3 La5 S9'
_chemical_formula_weight         1239.28

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
As As -0.9300 1.0051 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           57
_space_group_name_H-M_alt        'P b c m'
_space_group_name_Hall           '-P 2c 2b'

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

_cell_length_a                   7.0472(3)
_cell_length_b                   7.1152(3)
_cell_length_c                   37.1137(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1860.96(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4561
_cell_measurement_theta_min      2.381
_cell_measurement_theta_max      51.179

_exptl_crystal_description       Block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.423
_exptl_crystal_F_000             2184
_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    103.931
_shelx_estimated_absorpt_T_min   0.147
_shelx_estimated_absorpt_T_max   0.423
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  1.03
_exptl_absorpt_correction_T_max  3.09
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker X8 PROSPECTOR'
_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4561
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_theta_min         2.381
_diffrn_reflns_theta_max         51.179
_diffrn_reflns_theta_full        51.179
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1019
_reflns_number_gt                957
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_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-2019 (Sheldrick, 2019)'
_computing_structure_refinement  'SHELXL-2019 (Sheldrick, 2019)'
_computing_molecular_graphics    ?
_computing_publication_material  'SHELXL-2019 (Sheldrick, 2019)'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0736P)²+35.3120P] 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-2019/1 (Sheldrick 2019)'
_refine_ls_extinction_coef       0.00015(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1019
_refine_ls_number_parameters     43
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0398
_refine_ls_wR_factor_ref         0.1138
_refine_ls_wR_factor_gt          0.1123
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_restrained_S_all      1.046
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
La1 La 0.79282(15) 0.19329(15) 0.750000 0.0030(4) Uiso 1 2 d S . P . .
La2 La 1.20520(11) 0.27459(11) 0.83927(2) 0.0044(4) Uiso 1 1 d . . . . .
La3 La 0.71453(11) 0.04165(10) 0.95753(2) 0.0036(4) Uiso 1 1 d . . . . .
As1 As 0.6919(2) 0.3080(2) 0.86781(4) 0.0064(5) Uiso 1 1 d . . . . .
S1 S 0.9173(5) 0.1059(4) 0.88787(8) 0.0059(8) Uiso 1 1 d . . . . .
S2 S 1.4525(5) 0.2479(4) 0.90716(8) 0.0052(8) Uiso 1 1 d . . . . .
S3 S 0.5801(4) 0.1247(5) 0.67708(8) 0.0060(8) Uiso 1 1 d . . . . .
S4 S 0.6137(7) -0.1684(7) 0.750000 0.0114(12) Uiso 1 2 d S . P . .
S5 S 1.1120(5) -0.0903(5) 0.96471(8) 0.0087(8) Uiso 1 1 d . . . . .
Cl1 Cl 0.5538(7) -0.250000 1.000000 0.0067(11) Uiso 1 2 d S . P . .
Cl2 Cl 1.0579(5) -0.0207(4) 0.70333(8) 0.0078(8) Uiso 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 S4 2.867(5) . ?
La1 Cl2 2.872(3) 3_756 ?
La1 Cl2 2.872(3) 8_765 ?
La1 Cl2 2.968(3) 6_557 ?
La1 Cl2 2.968(3) . ?
La1 S4 3.029(5) 3_656 ?
La1 S3 3.132(3) . ?
La1 S3 3.132(3) 6_557 ?
La2 Cl2 2.827(3) 6_557 ?
La2 Cl2 2.839(3) 3_756 ?
La2 S3 2.913(3) 6_657 ?
La2 S1 2.968(3) . ?
La2 S3 2.977(3) 3_756 ?
La2 S2 3.069(3) . ?
La2 S1 3.091(3) 8_765 ?
La2 As1 3.5592(16) 8_755 ?
La3 Cl1 2.841(2) . ?
La3 Cl1 2.874(3) 5_657 ?
La3 S5 2.902(4) 8_765 ?
La3 S5 2.966(4) . ?
La3 S1 2.989(3) . ?
La3 S2 3.010(3) 1_455 ?
La3 S2 3.041(3) 8_755 ?
La3 S5 3.153(3) 5_757 ?
As1 S3 2.258(3) 6_557 ?
As1 S1 2.269(3) . ?
As1 S2 2.272(4) 1_455 ?

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
S4 La1 Cl2 142.89(6) . 3_756 ?
S4 La1 Cl2 142.89(6) . 8_765 ?
Cl2 La1 Cl2 74.18(12) 3_756 8_765 ?
S4 La1 Cl2 79.43(10) . 6_557 ?
Cl2 La1 Cl2 77.34(6) 3_756 6_557 ?
Cl2 La1 Cl2 119.01(6) 8_765 6_557 ?
S4 La1 Cl2 79.43(10) . . ?
Cl2 La1 Cl2 119.01(6) 3_756 . ?
Cl2 La1 Cl2 77.34(6) 8_765 . ?
Cl2 La1 Cl2 71.42(12) 6_557 . ?
S4 La1 S4 82.83(8) . 3_656 ?
Cl2 La1 S4 96.68(10) 3_756 3_656 ?
Cl2 La1 S4 96.68(10) 8_765 3_656 ?
Cl2 La1 S4 139.63(8) 6_557 3_656 ?
Cl2 La1 S4 139.63(8) . 3_656 ?
S4 La1 S3 69.47(8) . . ?
Cl2 La1 S3 143.80(9) 3_756 . ?
Cl2 La1 S3 76.39(9) 8_765 . ?
Cl2 La1 S3 136.52(9) 6_557 . ?
Cl2 La1 S3 73.56(8) . . ?
S4 La1 S3 66.29(7) 3_656 . ?
S4 La1 S3 69.47(8) . 6_557 ?
Cl2 La1 S3 76.39(9) 3_756 6_557 ?
Cl2 La1 S3 143.80(9) 8_765 6_557 ?
Cl2 La1 S3 73.56(8) 6_557 6_557 ?
Cl2 La1 S3 136.52(9) . 6_557 ?
S4 La1 S3 66.30(7) 3_656 6_557 ?
S3 La1 S3 119.55(12) . 6_557 ?
Cl2 La2 Cl2 80.21(6) 6_557 3_756 ?
Cl2 La2 S3 86.82(10) 6_557 6_657 ?
Cl2 La2 S3 131.62(9) 3_756 6_657 ?
Cl2 La2 S1 77.77(9) 6_557 . ?
Cl2 La2 S1 95.71(10) 3_756 . ?
S3 La2 S1 126.75(9) 6_657 . ?
Cl2 La2 S3 134.00(9) 6_557 3_756 ?
Cl2 La2 S3 77.83(9) 3_756 3_756 ?
S3 La2 S3 78.64(5) 6_657 3_756 ?
S1 La2 S3 144.06(8) . 3_756 ?
Cl2 La2 S2 128.43(9) 6_557 . ?
Cl2 La2 S2 149.29(8) 3_756 . ?
S3 La2 S2 68.50(9) 6_657 . ?
S1 La2 S2 82.19(8) . . ?
S3 La2 S2 86.02(9) 3_756 . ?
Cl2 La2 S1 142.23(10) 6_557 8_765 ?
Cl2 La2 S1 75.60(8) 3_756 8_765 ?
S3 La2 S1 130.85(9) 6_657 8_765 ?
S1 La2 S1 76.28(7) . 8_765 ?
S3 La2 S1 67.84(9) 3_756 8_765 ?
S2 La2 S1 74.15(8) . 8_765 ?
Cl2 La2 As1 63.14(7) 6_557 8_755 ?
Cl2 La2 As1 141.03(7) 3_756 8_755 ?
S3 La2 As1 62.33(7) 6_657 8_755 ?
S1 La2 As1 65.24(7) . 8_755 ?
S3 La2 As1 137.52(7) 3_756 8_755 ?
S2 La2 As1 65.30(6) . 8_755 ?
S1 La2 As1 126.47(6) 8_765 8_755 ?
Cl1 La3 Cl1 79.05(3) . 5_657 ?
Cl1 La3 S5 140.89(7) . 8_765 ?
Cl1 La3 S5 76.19(9) 5_657 8_765 ?
Cl1 La3 S5 95.48(11) . . ?
Cl1 La3 S5 137.33(9) 5_657 . ?
S5 La3 S5 83.08(6) 8_765 . ?
Cl1 La3 S1 141.45(7) . . ?
Cl1 La3 S1 135.25(7) 5_657 . ?
S5 La3 S1 74.94(9) 8_765 . ?
S5 La3 S1 71.01(9) . . ?
Cl1 La3 S2 117.13(11) . 1_455 ?
Cl1 La3 S2 71.66(7) 5_657 1_455 ?
S5 La3 S2 82.85(9) 8_765 1_455 ?
S5 La3 S2 142.15(9) . 1_455 ?
S1 La3 S2 71.44(9) . 1_455 ?
Cl1 La3 S2 71.62(7) . 8_755 ?
Cl1 La3 S2 115.92(10) 5_657 8_755 ?
S5 La3 S2 147.10(9) 8_765 8_755 ?
S5 La3 S2 101.72(9) . 8_755 ?
S1 La3 S2 76.03(9) . 8_755 ?
S2 La3 S2 73.49(6) 1_455 8_755 ?
Cl1 La3 S5 74.15(8) . 5_757 ?
Cl1 La3 S5 72.33(9) 5_657 5_757 ?
S5 La3 S5 69.74(11) 8_765 5_757 ?
S5 La3 S5 65.57(11) . 5_757 ?
S1 La3 S5 126.12(10) . 5_757 ?
S2 La3 S5 138.84(9) 1_455 5_757 ?
S2 La3 S5 142.00(9) 8_755 5_757 ?
S3 As1 S1 96.89(12) 6_557 . ?
S3 As1 S2 96.09(12) 6_557 1_455 ?
S1 As1 S2 100.94(12) . 1_455 ?
S3 As1 La2 112.98(10) 6_557 8_765 ?
S1 As1 La2 123.11(10) . 8_765 ?
S2 As1 La2 121.23(9) 1_455 8_765 ?
As1 S1 La2 91.31(11) . . ?
As1 S1 La3 92.63(11) . . ?
La2 S1 La3 156.09(12) . . ?
As1 S1 La2 95.54(11) . 8_755 ?
La2 S1 La2 98.32(9) . 8_755 ?
La3 S1 La2 104.74(10) . 8_755 ?
As1 S2 La3 92.02(11) 1_655 1_655 ?
As1 S2 La3 123.56(13) 1_655 8_765 ?
La3 S2 La3 101.00(9) 1_655 8_765 ?
As1 S2 La2 83.24(10) 1_655 . ?
La3 S2 La2 152.68(11) 1_655 . ?
La3 S2 La2 104.02(10) 8_765 . ?
As1 S3 La2 87.20(10) 6_557 6_457 ?
As1 S3 La2 98.96(11) 6_557 3_746 ?
La2 S3 La2 136.46(12) 6_457 3_746 ?
As1 S3 La1 112.36(12) 6_557 . ?
La2 S3 La1 123.85(11) 6_457 . ?
La2 S3 La1 93.63(9) 3_746 . ?
La1 S4 La1 135.08(18) . 3_646 ?
La3 S5 La3 132.45(12) 8_755 . ?
La3 S5 La3 91.14(10) 8_755 5_757 ?
La3 S5 La3 114.43(11) . 5_757 ?
La3 Cl1 La3 133.02(18) . 4_547 ?
La3 Cl1 La3 109.55(4) . 8_655 ?
La3 Cl1 La3 100.95(4) 4_547 8_655 ?
La3 Cl1 La3 100.95(4) . 5_657 ?
La3 Cl1 La3 109.55(4) 4_547 5_657 ?
La3 Cl1 La3 97.70(14) 8_655 5_657 ?
La2 Cl2 La2 108.05(10) 6_557 3_746 ?
La2 Cl2 La1 136.83(13) 6_557 3_746 ?
La2 Cl2 La1 102.22(10) 3_746 3_746 ?
La2 Cl2 La1 100.15(9) 6_557 . ?
La2 Cl2 La1 100.21(11) 3_746 . ?
La1 Cl2 La1 104.01(9) 3_746 . ?

_refine_diff_density_max         2.380
_refine_diff_density_min         -2.390
_refine_diff_density_rms         0.375

_shelx_res_file                  
;
TITL x1 in Pbcm
    x1.res
    created by SHELXL-2019/1 at 10:07:07 on 13-Jul-2023
CELL 1.54178   7.04720   7.11520  37.11370  90.0000  90.0000  90.0000
ZERR    4.00   0.00030   0.00030   0.00130   0.0000   0.0000   0.0000
LATT  1
SYMM -X, -Y, 0.5+Z
SYMM -X, 0.5+Y, 0.5-Z
SYMM X, 0.5-Y, -Z
SFAC S CL AS LA
UNIT 36 12 8 20
TEMP 23.000
SIZE 0.01 0.02 0.03

L.S. 14
BOND
acta
twin
FMAP 2
PLAN -5

WGHT    0.073600   35.311996
EXTI    0.000151
BASF   1.20056
FVAR       0.03600
LA1   4    0.792815    0.193294    0.750000    10.50000    0.00303
LA2   4    1.205199    0.274591    0.839268    11.00000    0.00445
LA3   4    0.714531    0.041649    0.957526    11.00000    0.00363
AS1   3    0.691887    0.308047    0.867814    11.00000    0.00635
S1    1    0.917327    0.105893    0.887866    11.00000    0.00590
S2    1    1.452454    0.247852    0.907162    11.00000    0.00520
S3    1    0.580084    0.124661    0.677079    11.00000    0.00603
S4    1    0.613667   -0.168432    0.750000    10.50000    0.01142
S5    1    1.112033   -0.090262    0.964710    11.00000    0.00867
CL1   2    0.553804   -0.250000    1.000000    10.50000    0.00674
CL2   2    1.057859   -0.020705    0.703327    11.00000    0.00784
HKLF 4




REM  x1 in Pbcm
REM wR2 = 0.1138, GooF = S = 1.046, Restrained GooF = 1.046 for all data
REM R1 = 0.0398 for 957 Fo > 4sig(Fo) and 0.0414 for all 1019 data
REM 43 parameters refined using 0 restraints

END

WGHT      0.0734     35.4605

REM Highest difference peak  2.380,  deepest hole -2.390,  1-sigma level  0.375
Q1    1   0.7934  0.2813  0.7500  10.50000  0.05    2.38
Q2    1   0.7906 -0.1546  0.6674  11.00000  0.05    2.38
Q3    1   0.7138  0.1287  0.9582  11.00000  0.05    2.37
Q4    1   0.8013  0.1082  0.7500  10.50000  0.05    2.32
Q5    1   0.8014 -0.2963  0.6513  11.00000  0.05    2.31
;
_shelx_res_checksum              75372
