# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_[Ba4Br][In19S32]
_database_code_depnum_ccdc_archive 'CCDC 2288695'
loop_
_audit_author_name
_audit_author_address
'Chunlan Tang'
;Institute of Chemical Materials, China Academy of Engineering Physics
China
;
_audit_update_record             
;
2023-08-15 deposited with the CCDC.	2023-09-22 downloaded from the CCDC.
;
_audit_creation_date             2023-07-24
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2017/1
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.25(Ba16 Br4 In76 S128)'
_chemical_formula_sum            'Ba4 Br In19 S32'
_chemical_formula_weight         3836.77
_chemical_melting_point          ?
_chemical_oxdiff_formula         BaInSBr
_chemical_oxdiff_usercomment     '4/m  RT'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
In In -0.7276 1.3100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           141
_space_group_name_H-M_alt        'I 41/a m d'
_space_group_name_Hall           '-I 4bd 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+1/4, x+3/4, z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'y+1/4, x+3/4, -z+1/4'
'-y+1/4, -x+1/4, -z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+3/4, x+5/4, z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-x+1, y+1/2, -z+1'
'x+1/2, -y+1/2, -z+1/2'
'y+3/4, x+5/4, -z+3/4'
'-y+3/4, -x+3/4, -z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-1/4, -x-3/4, -z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'x-1/2, -y, z-1/2'
'-x, y, z'
'-y-1/4, -x-3/4, z-1/4'
'y-1/4, x-1/4, z-3/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y+1/4, -x-1/4, -z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'x, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'
'-y+1/4, -x-1/4, z+1/4'
'y+1/4, x+1/4, z-1/4'

_cell_length_a                   22.6612(6)
_cell_length_b                   22.6612(6)
_cell_length_c                   10.4980(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5391.0(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    6964
_cell_measurement_temperature    295.34(11)
_cell_measurement_theta_max      26.3770
_cell_measurement_theta_min      2.5740
_shelx_estimated_absorpt_T_max   0.784
_shelx_estimated_absorpt_T_min   0.514
_exptl_absorpt_coefficient_mu    12.806
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78190
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear greenish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    4.727
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             6808
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10819
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.361
_diffrn_reflns_theta_min         2.138
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.34(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     -5.00  65.00   0.50   22.11    --   -4.76  22.00  98.00  140
  2  ω     -1.00  29.00   0.50   22.11    --   -4.76 -99.00-120.00   60
  3  ω    -10.00  24.00   0.50   22.11    --   -4.76 -99.00 -30.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0172168000
_diffrn_orient_matrix_UB_12      -0.0239305000
_diffrn_orient_matrix_UB_13      -0.0228234000
_diffrn_orient_matrix_UB_21      0.0259740000
_diffrn_orient_matrix_UB_22      -0.0171185000
_diffrn_orient_matrix_UB_23      -0.0074019000
_diffrn_orient_matrix_UB_31      -0.0031381000
_diffrn_orient_matrix_UB_32      -0.0106403000
_diffrn_orient_matrix_UB_33      0.0631454000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1331
_reflns_number_total             1456
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.513
_refine_diff_density_rms         0.115
_refine_ls_extinction_coef       0.0000048(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     74
_refine_ls_number_reflns         1456
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0174
_refine_ls_R_factor_gt           0.0149
_refine_ls_restrained_S_all      1.027
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0059P)²+10.4055P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0275
_refine_ls_wR_factor_ref         0.0280
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
Ba1 Ba 0.500000 0.63128(2) 0.71854(2) 0.02263(8) Uani 1 2 d S T P . .
In5 In 0.33057(2) 0.41943(2) 0.125000 0.01109(7) Uani 1 2 d S T P . .
In2 In 0.500000 0.750000 0.375000 0.01119(12) Uani 1 8 d S T P . .
In4 In 0.34323(2) 0.500000 0.500000 0.01383(8) Uani 1 2 d S T P . .
In1 In 0.34055(2) 0.66911(2) 0.50579(2) 0.01330(6) Uani 1 1 d . . . . .
In3 In 0.250000 0.750000 0.750000 0.01534(10) Uani 1 4 d S T P . .
Br1 Br 0.500000 0.750000 0.875000 0.01638(18) Uani 1 8 d S T P . .
S4 S 0.33296(3) 0.50974(3) 0.25337(6) 0.01094(15) Uani 1 1 d . . . . .
S3 S 0.26100(4) 0.750000 0.51192(8) 0.0105(2) Uani 1 2 d S T P . .
S2 S 0.41592(3) 0.58568(3) 0.49488(6) 0.01176(15) Uani 1 1 d . . . . .
S1 S 0.42166(5) 0.750000 0.53405(9) 0.0129(2) Uani 1 2 d S T P . .
S5 S 0.42320(3) 0.40907(3) 0.00981(7) 0.01406(16) 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
Ba1 Br1 3.1521(3) . ?
Ba1 S3 3.2563(11) 12_454 ?
Ba1 S2 3.1954(7) . ?
Ba1 S2 3.1955(7) 22_655 ?
Ba1 S5 3.4638(8) 17_666 ?
Ba1 S5 3.4638(8) 6_566 ?
In5 S4 2.4509(7) . ?
In5 S4 2.4509(7) 16_554 ?
In5 S5 2.4339(8) 16_554 ?
In5 S5 2.4338(8) . ?
In2 S1 2.4372(10) 19_576 ?
In2 S1 2.4372(10) 10_564 ?
In2 S1 2.4372(10) 28_656 ?
In2 S1 2.4372(10) . ?
In4 S4 2.6089(7) 6_566 ?
In4 S4 2.6090(7) . ?
In4 S4 2.6675(8) 15_445 ?
In4 S4 2.6675(8) 12_454 ?
In4 S2 2.5467(8) 6_566 ?
In4 S2 2.5468(8) . ?
In1 S4 2.6783(7) 15_445 ?
In1 S3 2.5718(7) . ?
In1 S2 2.6349(7) 15_445 ?
In1 S2 2.5505(7) . ?
In1 S1 2.6129(8) . ?
In1 S5 2.6683(7) 11_545 ?
In3 S3 2.5118(9) 25_566 ?
In3 S3 2.5117(9) . ?
In3 S5 2.6991(8) 15_445 ?
In3 S5 2.6991(8) 19_576 ?
In3 S5 2.6991(8) 11_545 ?
In3 S5 2.6991(8) 23_676 ?

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
Br1 Ba1 S3 140.554(18) . 12_454 ?
Br1 Ba1 S2 131.217(15) . . ?
Br1 Ba1 S2 131.217(15) . 22_655 ?
Br1 Ba1 S5 78.247(14) . 6_566 ?
Br1 Ba1 S5 78.247(14) . 17_666 ?
S3 Ba1 S5 67.879(19) 12_454 17_666 ?
S3 Ba1 S5 67.879(19) 12_454 6_566 ?
S2 Ba1 S3 77.440(19) 22_655 12_454 ?
S2 Ba1 S3 77.441(19) . 12_454 ?
S2 Ba1 S2 73.20(3) . 22_655 ?
S2 Ba1 S5 102.709(18) . 6_566 ?
S2 Ba1 S5 145.00(2) . 17_666 ?
S2 Ba1 S5 102.708(18) 22_655 17_666 ?
S2 Ba1 S5 145.00(2) 22_655 6_566 ?
S5 Ba1 S5 60.32(2) 17_666 6_566 ?
S4 In5 S4 109.83(4) . 16_554 ?
S5 In5 S4 116.41(2) 16_554 . ?
S5 In5 S4 109.55(2) . . ?
S5 In5 S4 116.41(2) . 16_554 ?
S5 In5 S4 109.55(2) 16_554 16_554 ?
S5 In5 S5 94.62(4) . 16_554 ?
S1 In2 S1 93.51(5) 28_656 19_576 ?
S1 In2 S1 117.99(3) 19_576 . ?
S1 In2 S1 117.99(3) 10_564 19_576 ?
S1 In2 S1 117.99(3) 28_656 . ?
S1 In2 S1 93.51(5) 10_564 . ?
S1 In2 S1 117.99(3) 28_656 10_564 ?
S4 In4 S4 169.76(3) 6_566 . ?
S4 In4 S4 82.18(2) 6_566 12_454 ?
S4 In4 S4 90.54(2) 6_566 15_445 ?
S4 In4 S4 82.18(2) . 15_445 ?
S4 In4 S4 89.64(3) 12_454 15_445 ?
S4 In4 S4 90.54(2) . 12_454 ?
S2 In4 S4 85.48(2) 6_566 12_454 ?
S2 In4 S4 88.41(2) . . ?
S2 In4 S4 98.23(2) 6_566 . ?
S2 In4 S4 88.41(2) 6_566 6_566 ?
S2 In4 S4 175.11(2) . 12_454 ?
S2 In4 S4 85.48(2) . 15_445 ?
S2 In4 S4 175.11(2) 6_566 15_445 ?
S2 In4 S4 98.23(2) . 6_566 ?
S2 In4 S2 99.40(3) 6_566 . ?
S3 In1 S4 92.36(2) . 15_445 ?
S3 In1 S2 90.87(3) . 15_445 ?
S3 In1 S1 89.43(2) . . ?
S3 In1 S5 87.28(3) . 11_545 ?
S2 In1 S4 85.18(2) . 15_445 ?
S2 In1 S4 85.16(2) 15_445 15_445 ?
S2 In1 S3 177.33(3) . . ?
S2 In1 S2 87.87(2) . 15_445 ?
S2 In1 S1 93.10(2) . . ?
S2 In1 S5 177.75(2) 15_445 11_545 ?
S2 In1 S5 93.93(2) . 11_545 ?
S1 In1 S4 175.15(3) . 15_445 ?
S1 In1 S2 99.33(3) . 15_445 ?
S1 In1 S5 81.94(3) . 11_545 ?
S5 In1 S4 93.64(2) 11_545 15_445 ?
S3 In3 S3 180.00(5) . 25_566 ?
S3 In3 S5 92.17(2) 25_566 23_676 ?
S3 In3 S5 92.17(2) . 15_445 ?
S3 In3 S5 87.83(2) 25_566 19_576 ?
S3 In3 S5 87.83(2) . 23_676 ?
S3 In3 S5 92.17(2) . 19_576 ?
S3 In3 S5 87.83(2) 25_566 15_445 ?
S3 In3 S5 92.17(2) 25_566 11_545 ?
S3 In3 S5 87.83(2) . 11_545 ?
S5 In3 S5 180.0 23_676 15_445 ?
S5 In3 S5 99.70(3) 23_676 19_576 ?
S5 In3 S5 80.30(3) 15_445 19_576 ?
S5 In3 S5 80.30(3) 23_676 11_545 ?
S5 In3 S5 99.70(3) 15_445 11_545 ?
S5 In3 S5 180.0 11_545 19_576 ?
Ba1 Br1 Ba1 117.188(10) . 10_564 ?
Ba1 Br1 Ba1 105.756(5) . 19_577 ?
Ba1 Br1 Ba1 105.756(5) 10_564 19_577 ?
Ba1 Br1 Ba1 105.756(5) 28_657 10_564 ?
Ba1 Br1 Ba1 105.756(5) . 28_657 ?
Ba1 Br1 Ba1 117.188(10) 28_657 19_577 ?
In5 S4 In4 124.71(3) . 11_544 ?
In5 S4 In4 118.49(3) . . ?
In5 S4 In1 124.56(3) . 15_445 ?
In4 S4 In4 97.82(2) . 11_544 ?
In4 S4 In1 91.62(2) 11_544 15_445 ?
In4 S4 In1 91.63(2) . 15_445 ?
In1 S3 Ba1 133.672(17) . 11_544 ?
In1 S3 Ba1 133.672(17) 29_565 11_544 ?
In1 S3 In1 90.93(3) . 29_565 ?
In3 S3 Ba1 92.35(3) . 11_544 ?
In3 S3 In1 95.42(3) . . ?
In3 S3 In1 95.42(3) . 29_565 ?
In4 S2 Ba1 128.07(3) . . ?
In4 S2 In1 97.52(3) . . ?
In4 S2 In1 94.05(2) . 15_445 ?
In1 S2 Ba1 97.27(2) . . ?
In1 S2 Ba1 134.75(3) 15_445 . ?
In1 S2 In1 91.84(2) . 15_445 ?
In2 S1 In1 115.76(3) . . ?
In2 S1 In1 115.76(3) . 29_565 ?
In1 S1 In1 89.11(3) 29_565 . ?
In5 S5 Ba1 92.85(2) . 17_666 ?
In5 S5 In1 117.79(3) . 12_453 ?
In5 S5 In3 120.09(3) . 12_453 ?
In1 S5 Ba1 147.26(3) 12_453 17_666 ?
In1 S5 In3 88.96(2) 12_453 12_453 ?
In3 S5 Ba1 84.775(19) 12_453 17_666 ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.447
_oxdiff_exptl_absorpt_empirical_full_min 0.875
####################################################################### 
# 
# 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_[Ba4Cl][In19S32]
_database_code_depnum_ccdc_archive 'CCDC 2288696'
loop_
_audit_author_name
_audit_author_address
'Chunlan Tang'
;Institute of Chemical Materials, China Academy of Engineering Physics
China
;
_audit_update_record             
;
2023-08-15 deposited with the CCDC.	2023-09-22 downloaded from the CCDC.
;
_audit_creation_date             2023-08-14
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2017/1
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.25(Ba16 Cl4 In76 S128)'
_chemical_formula_sum            'Ba4 Cl In19 S32'
_chemical_formula_weight         3792.31
_chemical_melting_point          ?
_chemical_oxdiff_formula         BaInPSCl
_chemical_oxdiff_usercomment     '4/m  0.75 0.5 43S RT'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
In In -0.7276 1.3100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           141
_space_group_name_H-M_alt        'I 41/a m d'
_space_group_name_Hall           '-I 4bd 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+1/4, x+3/4, z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'y+1/4, x+3/4, -z+1/4'
'-y+1/4, -x+1/4, -z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+3/4, x+5/4, z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-x+1, y+1/2, -z+1'
'x+1/2, -y+1/2, -z+1/2'
'y+3/4, x+5/4, -z+3/4'
'-y+3/4, -x+3/4, -z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-1/4, -x-3/4, -z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'x-1/2, -y, z-1/2'
'-x, y, z'
'-y-1/4, -x-3/4, z-1/4'
'y-1/4, x-1/4, z-3/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y+1/4, -x-1/4, -z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'x, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'
'-y+1/4, -x-1/4, z+1/4'
'y+1/4, x+1/4, z-1/4'

_cell_length_a                   22.6105(6)
_cell_length_b                   22.6105(6)
_cell_length_c                   10.4904(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5363.1(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    8172
_cell_measurement_temperature    295.4(3)
_cell_measurement_theta_max      26.3780
_cell_measurement_theta_min      3.2990
_shelx_estimated_absorpt_T_max   0.581
_shelx_estimated_absorpt_T_min   0.442
_exptl_absorpt_coefficient_mu    12.178
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38388
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    4.697
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             6736
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            10826
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.364
_diffrn_reflns_theta_min         2.798
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.4(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -33.00  11.00   0.50   30.00    --   -8.37 -73.00 -67.00   88
  2  ω    -23.00   4.00   0.50   30.00    --   -8.37 -99.00 -90.00   54
  3  ω    -80.00 -41.00   0.50   30.00    --   -8.37 -73.00 -67.00   78
  4  ω    -16.00  20.00   0.50   30.00    --   -8.37 -99.00 150.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0155042000
_diffrn_orient_matrix_UB_12      -0.0098677000
_diffrn_orient_matrix_UB_13      0.0548325000
_diffrn_orient_matrix_UB_21      -0.0185705000
_diffrn_orient_matrix_UB_22      0.0252439000
_diffrn_orient_matrix_UB_23      -0.0033589000
_diffrn_orient_matrix_UB_31      -0.0199512000
_diffrn_orient_matrix_UB_32      -0.0158290000
_diffrn_orient_matrix_UB_33      -0.0393998000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1407
_reflns_number_total             1444
_reflns_odcompleteness_completeness 82.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_refine_diff_density_max         2.039
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.154
_refine_ls_extinction_coef       0.000016(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.238
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     74
_refine_ls_number_reflns         1444
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0180
_refine_ls_R_factor_gt           0.0171
_refine_ls_restrained_S_all      1.238
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0215P)²+7.2481P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0421
_refine_ls_wR_factor_ref         0.0424
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
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
Ba1 Ba 0.000000 0.63499(2) 0.27935(3) 0.02049(9) Uani 1 2 d S T P . .
In1 In 0.15969(2) 0.66916(2) 0.49465(2) 0.01213(8) Uani 1 1 d . . . . .
In2 In 0.000000 0.750000 0.625000 0.01060(13) Uani 1 8 d S T P . .
In3 In 0.250000 0.750000 0.250000 0.01451(11) Uani 1 4 d S T P . .
In4 In 0.15612(2) 0.500000 0.500000 0.01268(9) Uani 1 2 d S T P . .
In5 In 0.16931(2) 0.41931(2) 0.875000 0.01001(9) Uani 1 2 d S T P . .
Cl1 Cl 0.000000 0.750000 0.125000 0.0153(4) Uani 1 8 d S T P . .
S2 S 0.07802(5) 0.750000 0.46454(10) 0.0121(2) Uani 1 2 d S T P . .
S1 S 0.08358(4) 0.58594(3) 0.50463(7) 0.01075(17) Uani 1 1 d . . . . .
S3 S 0.23954(5) 0.750000 0.48824(9) 0.0101(2) Uani 1 2 d S T P . .
S4 S 0.16714(3) 0.50986(4) 0.74671(7) 0.01004(17) Uani 1 1 d . . . . .
S5 S 0.15860(4) 0.32653(4) 0.75989(7) 0.01307(17) 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
Ba1 Cl1 3.0632(3) . ?
Ba1 S2 3.6944(8) . ?
Ba1 S2 3.6943(8) 10_464 ?
Ba1 S1 3.2229(8) 22 ?
Ba1 S1 3.2229(8) . ?
Ba1 S3 3.3169(11) 11_544 ?
Ba1 S5 3.4578(8) 31_564 ?
Ba1 S5 3.4578(8) 12_453 ?
In1 S2 2.6174(8) . ?
In1 S1 2.6327(8) 16 ?
In1 S1 2.5521(8) . ?
In1 S3 2.5700(8) . ?
In1 S4 2.6691(8) 16 ?
In1 S5 2.6721(8) 6_566 ?
In2 S2 2.4384(10) . ?
In2 S2 2.4384(10) 27_466 ?
In2 S2 2.4384(10) 20_667 ?
In2 S2 2.4384(10) 10_464 ?
In3 S3 2.5104(10) . ?
In3 S3 2.5104(10) 25_565 ?
In3 S5 2.6973(8) 6_566 ?
In3 S5 2.6973(8) 30_554 ?
In3 S5 2.6973(8) 26_556 ?
In3 S5 2.6973(8) 2_564 ?
In4 S1 2.5431(8) 6_566 ?
In4 S1 2.5432(8) . ?
In4 S4 2.6096(7) . ?
In4 S4 2.6097(7) 6_566 ?
In4 S4 2.6686(8) 16 ?
In4 S4 2.6686(8) 11_544 ?
In5 S4 2.4506(8) 15_446 ?
In5 S4 2.4506(8) . ?
In5 S5 2.4326(8) . ?
In5 S5 2.4326(8) 15_446 ?

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
Cl1 Ba1 S2 71.365(14) . . ?
Cl1 Ba1 S2 71.365(14) . 10_464 ?
Cl1 Ba1 S1 132.824(15) . 22 ?
Cl1 Ba1 S1 132.823(15) . . ?
Cl1 Ba1 S3 140.621(19) . 11_544 ?
Cl1 Ba1 S5 79.039(14) . 12_453 ?
Cl1 Ba1 S5 79.039(14) . 31_564 ?
S2 Ba1 S2 57.05(3) 10_464 . ?
S1 Ba1 S2 64.952(18) 22 10_464 ?
S1 Ba1 S2 97.85(2) . 10_464 ?
S1 Ba1 S2 97.85(2) 22 . ?
S1 Ba1 S2 64.951(18) . . ?
S1 Ba1 S1 71.80(3) . 22 ?
S1 Ba1 S3 75.76(2) 22 11_544 ?
S1 Ba1 S3 75.76(2) . 11_544 ?
S1 Ba1 S5 102.00(2) 22 31_564 ?
S1 Ba1 S5 142.64(2) . 31_564 ?
S1 Ba1 S5 102.00(2) . 12_453 ?
S1 Ba1 S5 142.64(2) 22 12_453 ?
S3 Ba1 S2 140.019(17) 11_544 10_464 ?
S3 Ba1 S2 140.019(17) 11_544 . ?
S3 Ba1 S5 67.113(19) 11_544 12_453 ?
S3 Ba1 S5 67.113(19) 11_544 31_564 ?
S5 Ba1 S2 150.40(2) 12_453 10_464 ?
S5 Ba1 S2 150.40(2) 31_564 . ?
S5 Ba1 S2 113.05(2) 31_564 10_464 ?
S5 Ba1 S2 113.05(2) 12_453 . ?
S5 Ba1 S5 60.05(3) 31_564 12_453 ?
S2 In1 S1 99.41(3) . 16 ?
S2 In1 S4 174.51(3) . 16 ?
S2 In1 S5 81.22(3) . 6_566 ?
S1 In1 S2 92.53(3) . . ?
S1 In1 S1 88.11(3) . 16 ?
S1 In1 S3 177.64(3) . . ?
S1 In1 S4 85.60(2) 16 16 ?
S1 In1 S4 85.36(3) . 16 ?
S1 In1 S5 93.54(3) . 6_566 ?
S1 In1 S5 178.22(3) 16 6_566 ?
S3 In1 S2 89.76(3) . . ?
S3 In1 S1 90.95(3) . 16 ?
S3 In1 S4 92.41(3) . 16 ?
S3 In1 S5 87.39(3) . 6_566 ?
S4 In1 S5 93.84(2) 16 6_566 ?
S2 In2 S2 118.46(3) 27_466 . ?
S2 In2 S2 92.69(5) 20_667 27_466 ?
S2 In2 S2 118.46(3) 20_667 . ?
S2 In2 S2 92.69(5) 10_464 . ?
S2 In2 S2 118.46(3) 10_464 27_466 ?
S2 In2 S2 118.46(3) 20_667 10_464 ?
S3 In3 S3 180.0 . 25_565 ?
S3 In3 S5 88.06(2) 25_565 2_564 ?
S3 In3 S5 88.06(2) . 6_566 ?
S3 In3 S5 91.94(2) 25_565 6_566 ?
S3 In3 S5 88.06(2) 25_565 30_554 ?
S3 In3 S5 88.06(2) . 26_556 ?
S3 In3 S5 91.94(2) . 2_564 ?
S3 In3 S5 91.94(2) . 30_554 ?
S3 In3 S5 91.94(2) 25_565 26_556 ?
S5 In3 S5 100.19(4) 6_566 2_564 ?
S5 In3 S5 79.81(4) 6_566 26_556 ?
S5 In3 S5 180.00(3) 2_564 26_556 ?
S5 In3 S5 79.81(4) 30_554 2_564 ?
S5 In3 S5 100.19(4) 30_554 26_556 ?
S5 In3 S5 180.0 30_554 6_566 ?
S1 In4 S1 99.69(4) 6_566 . ?
S1 In4 S4 85.55(2) . 16 ?
S1 In4 S4 174.75(2) . 11_544 ?
S1 In4 S4 98.38(3) . 6_566 ?
S1 In4 S4 88.70(2) . . ?
S1 In4 S4 85.55(2) 6_566 11_544 ?
S1 In4 S4 174.76(2) 6_566 16 ?
S1 In4 S4 98.38(3) 6_566 . ?
S1 In4 S4 88.70(2) 6_566 6_566 ?
S4 In4 S4 89.21(3) 16 11_544 ?
S4 In4 S4 90.28(2) . 11_544 ?
S4 In4 S4 169.04(4) . 6_566 ?
S4 In4 S4 81.91(3) . 16 ?
S4 In4 S4 90.28(2) 6_566 16 ?
S4 In4 S4 81.91(3) 6_566 11_544 ?
S4 In5 S4 109.57(4) 15_446 . ?
S5 In5 S4 109.79(3) 15_446 . ?
S5 In5 S4 116.48(3) . . ?
S5 In5 S4 109.78(3) . 15_446 ?
S5 In5 S4 116.48(3) 15_446 15_446 ?
S5 In5 S5 94.29(4) . 15_446 ?
Ba1 Cl1 Ba1 106.224(5) . 27_465 ?
Ba1 Cl1 Ba1 106.223(5) 10_464 20_666 ?
Ba1 Cl1 Ba1 106.223(5) 27_465 10_464 ?
Ba1 Cl1 Ba1 106.224(5) . 20_666 ?
Ba1 Cl1 Ba1 116.182(11) . 10_464 ?
Ba1 Cl1 Ba1 116.182(11) 27_465 20_666 ?
Ba1 S2 Ba1 89.48(2) . 10_464 ?
In1 S2 Ba1 153.11(4) . 10_464 ?
In1 S2 Ba1 153.11(4) 29_565 . ?
In1 S2 Ba1 84.768(11) . . ?
In1 S2 Ba1 84.768(11) 29_565 10_464 ?
In1 S2 In1 88.59(3) . 29_565 ?
In2 S2 Ba1 91.00(2) . 10_464 ?
In2 S2 Ba1 91.00(2) . . ?
In2 S2 In1 115.29(3) . . ?
In2 S2 In1 115.28(3) . 29_565 ?
In1 S1 Ba1 134.90(3) 16 . ?
In1 S1 Ba1 96.41(2) . . ?
In1 S1 In1 91.67(2) . 16 ?
In4 S1 Ba1 128.83(3) . . ?
In4 S1 In1 97.34(3) . . ?
In4 S1 In1 93.61(2) . 16 ?
In1 S3 Ba1 133.878(19) 29_565 12_454 ?
In1 S3 Ba1 133.879(19) . 12_454 ?
In1 S3 In1 90.67(4) . 29_565 ?
In3 S3 Ba1 92.07(3) . 12_454 ?
In3 S3 In1 95.29(3) . 29_565 ?
In3 S3 In1 95.29(3) . . ?
In4 S4 In1 91.26(2) . 16 ?
In4 S4 In1 91.59(3) 12_454 16 ?
In4 S4 In4 98.09(3) . 12_454 ?
In5 S4 In1 124.43(3) . 16 ?
In5 S4 In4 118.37(3) . . ?
In5 S4 In4 125.01(3) . 12_454 ?
In1 S5 Ba1 146.91(3) 6_566 11_545 ?
In1 S5 In3 88.73(2) 6_566 2_565 ?
In3 S5 Ba1 85.92(2) 2_565 11_545 ?
In5 S5 Ba1 93.10(2) . 11_545 ?
In5 S5 In1 117.62(3) . 6_566 ?
In5 S5 In3 119.74(3) . 2_565 ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.086
_oxdiff_exptl_absorpt_empirical_full_min 0.611
