# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2022

####################################################################### 
# 
# 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_Cs2ZnAs4S8
_database_code_depnum_ccdc_archive 'CCDC 2167064'
loop_
_audit_author_name
_audit_author_address
'Hua Lin'
;Fujian Institute of Research on the Structure of Matter, CAS
China
;
_audit_update_record             
;
2022-04-18 deposited with the CCDC.	2022-09-20 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            'As4 Cs2 S8 Zn'
_chemical_formula_weight         887.35

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'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
As As 0.0499 2.0058 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.3680 2.1192 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_H-M_alt        'I 41/a'
_space_group_name_Hall           '-I 4ad'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+3/4, x+1/4, z+1/4'
'y+3/4, -x+3/4, z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+5/4, x+3/4, z+3/4'
'y+5/4, -x+5/4, z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-3/4, -x-1/4, -z-1/4'
'-y-3/4, x-3/4, -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'

_cell_length_a                   11.0828(5)
_cell_length_b                   11.0828(5)
_cell_length_c                   13.2303(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1625.06(18)
_cell_formula_units_Z            4
_cell_measurement_temperature    170(2)
_cell_measurement_reflns_used    987
_cell_measurement_theta_min      3.2347
_cell_measurement_theta_max      29.2589

_exptl_crystal_description       Block
_exptl_crystal_colour            Yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.627
_exptl_crystal_F_000             1600
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.1300
_exptl_crystal_size_mid          0.1200
_exptl_crystal_size_min          0.0800
_exptl_absorpt_coefficient_mu    15.004
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.62254
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      170(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       'Enhance (Mo) X-ray Source'
_diffrn_detector_area_resol_mean 10.3592
_diffrn_reflns_number            17053
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_av_R_equivalents  0.0592
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.397
_diffrn_reflns_theta_max         40.377
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2564
_reflns_number_gt                2139
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

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

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0229P)²+1.1118P] 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       0.00030(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2564
_refine_ls_number_parameters     36
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0265
_refine_ls_wR_factor_ref         0.0645
_refine_ls_wR_factor_gt          0.0603
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.039
_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
Cs Cs 0.0000 0.2500 0.45521(2) 0.02597(6) Uani 1 2 d S T P . .
As As 0.16243(2) 0.01798(2) 0.00487(2) 0.01245(5) Uani 1 1 d . . . . .
Zn Zn 0.0000 0.2500 0.1250 0.01320(8) Uani 1 4 d S T P . .
S2 S 0.17589(5) 0.21445(4) 0.03310(3) 0.01605(9) Uani 1 1 d . . . . .
S1 S 0.31599(5) 0.51563(5) 0.10909(3) 0.01892(10) Uani 1 1 d . . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cs 0.01884(9) 0.03601(12) 0.02304(9) 0.000 0.000 0.00134(7)
As 0.01219(8) 0.01638(9) 0.00879(7) -0.00120(5) -0.00058(5) -0.00023(6)
Zn 0.01362(11) 0.01362(11) 0.01236(15) 0.000 0.000 0.000
S2 0.01600(19) 0.01491(19) 0.01724(18) 0.00234(14) 0.00410(14) 0.00143(15)
S1 0.0161(2) 0.0283(3) 0.01233(17) 0.00591(16) -0.00273(14) -0.00409(18)

_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
Cs S2 3.6170(5) 13 ?
Cs S2 3.6170(5) 10_556 ?
Cs S1 3.6810(6) 13 ?
Cs S1 3.6810(6) 10_556 ?
Cs S2 3.7277(5) 15 ?
Cs S2 3.7277(5) 12_666 ?
Cs S1 3.8795(5) 2_565 ?
Cs S1 3.8795(5) 5_445 ?
Cs S1 4.1160(6) 16_656 ?
Cs S1 4.1160(6) 11_566 ?
Cs As 4.1927(3) 15 ?
Cs As 4.1927(3) 12_666 ?
As S2 2.2143(5) . ?
As S1 2.2738(5) 14_545 ?
As S1 2.3267(5) 15 ?
As Cs 4.1927(3) 15 ?
Zn S2 2.3309(5) . ?
Zn S2 2.3309(5) 12_666 ?
Zn S2 2.3309(5) 6_454 ?
Zn S2 2.3309(5) 15 ?
Zn Cs 4.3688(3) 15 ?
S2 Cs 3.6169(5) 13 ?
S2 Cs 3.7278(5) 15 ?
S1 As 2.2738(5) 14 ?
S1 As 2.3267(5) 12_666 ?
S1 Cs 3.6810(6) 13 ?
S1 Cs 3.8795(5) 5_554 ?
S1 Cs 4.1160(6) 11_666 ?

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 Cs S2 175.100(16) 13 10_556 ?
S2 Cs S1 63.050(11) 13 13 ?
S2 Cs S1 118.228(11) 10_556 13 ?
S2 Cs S1 118.228(11) 13 10_556 ?
S2 Cs S1 63.050(11) 10_556 10_556 ?
S1 Cs S1 153.273(15) 13 10_556 ?
S2 Cs S2 101.426(14) 13 15 ?
S2 Cs S2 82.774(13) 10_556 15 ?
S1 Cs S2 56.279(11) 13 15 ?
S1 Cs S2 99.448(11) 10_556 15 ?
S2 Cs S2 82.774(13) 13 12_666 ?
S2 Cs S2 101.426(14) 10_556 12_666 ?
S1 Cs S2 99.448(11) 13 12_666 ?
S1 Cs S2 56.279(11) 10_556 12_666 ?
S2 Cs S2 64.483(15) 15 12_666 ?
S2 Cs S1 51.870(11) 13 2_565 ?
S2 Cs S1 124.930(11) 10_556 2_565 ?
S1 Cs S1 111.439(13) 13 2_565 ?
S1 Cs S1 82.939(12) 10_556 2_565 ?
S2 Cs S1 148.160(11) 15 2_565 ?
S2 Cs S1 92.189(11) 12_666 2_565 ?
S2 Cs S1 124.930(11) 13 5_445 ?
S2 Cs S1 51.870(11) 10_556 5_445 ?
S1 Cs S1 82.939(12) 13 5_445 ?
S1 Cs S1 111.439(13) 10_556 5_445 ?
S2 Cs S1 92.189(11) 15 5_445 ?
S2 Cs S1 148.160(11) 12_666 5_445 ?
S1 Cs S1 116.693(16) 2_565 5_445 ?
S2 Cs S1 53.255(11) 13 16_656 ?
S2 Cs S1 123.177(11) 10_556 16_656 ?
S1 Cs S1 52.560(8) 13 16_656 ?
S1 Cs S1 152.110(14) 10_556 16_656 ?
S2 Cs S1 108.207(11) 15 16_656 ?
S2 Cs S1 134.206(11) 12_666 16_656 ?
S1 Cs S1 71.746(5) 2_565 16_656 ?
S1 Cs S1 71.746(5) 5_445 16_656 ?
S2 Cs S1 123.177(11) 13 11_566 ?
S2 Cs S1 53.255(11) 10_556 11_566 ?
S1 Cs S1 152.110(14) 13 11_566 ?
S1 Cs S1 52.560(8) 10_556 11_566 ?
S2 Cs S1 134.206(11) 15 11_566 ?
S2 Cs S1 108.207(11) 12_666 11_566 ?
S1 Cs S1 71.746(5) 2_565 11_566 ?
S1 Cs S1 71.746(5) 5_445 11_566 ?
S1 Cs S1 106.706(14) 16_656 11_566 ?
S2 Cs As 133.174(9) 13 15 ?
S2 Cs As 51.131(8) 10_556 15 ?
S1 Cs As 80.977(8) 13 15 ?
S1 Cs As 81.395(8) 10_556 15 ?
S2 Cs As 31.781(8) 15 15 ?
S2 Cs As 74.255(9) 12_666 15 ?
S1 Cs As 163.291(9) 2_565 15 ?
S1 Cs As 74.812(8) 5_445 15 ?
S1 Cs As 124.749(8) 16_656 15 ?
S1 Cs As 102.792(8) 11_566 15 ?
S2 Cs As 51.131(8) 13 12_666 ?
S2 Cs As 133.174(9) 10_556 12_666 ?
S1 Cs As 81.395(8) 13 12_666 ?
S1 Cs As 80.977(8) 10_556 12_666 ?
S2 Cs As 74.255(9) 15 12_666 ?
S2 Cs As 31.781(8) 12_666 12_666 ?
S1 Cs As 74.812(8) 2_565 12_666 ?
S1 Cs As 163.291(9) 5_445 12_666 ?
S1 Cs As 102.792(8) 16_656 12_666 ?
S1 Cs As 124.749(8) 11_566 12_666 ?
As Cs As 96.952(7) 15 12_666 ?
S2 As S1 94.17(2) . 14_545 ?
S2 As S1 103.280(19) . 15 ?
S1 As S1 98.074(13) 14_545 15 ?
S2 As Cs 62.459(14) . 15 ?
S1 As Cs 83.613(16) 14_545 15 ?
S1 As Cs 165.738(14) 15 15 ?
S2 Zn S2 105.787(11) . 12_666 ?
S2 Zn S2 117.12(2) . 6_454 ?
S2 Zn S2 105.789(11) 12_666 6_454 ?
S2 Zn S2 105.789(11) . 15 ?
S2 Zn S2 117.12(2) 12_666 15 ?
S2 Zn S2 105.789(11) 6_454 15 ?
S2 Zn Cs 58.560(12) . 15 ?
S2 Zn Cs 121.441(12) 12_666 15 ?
S2 Zn Cs 58.559(12) 6_454 15 ?
S2 Zn Cs 121.441(12) 15 15 ?
S2 Zn Cs 121.440(12) . . ?
S2 Zn Cs 58.559(12) 12_666 . ?
S2 Zn Cs 121.441(12) 6_454 . ?
S2 Zn Cs 58.559(12) 15 . ?
Cs Zn Cs 180.0 15 . ?
As S2 Zn 101.41(2) . . ?
As S2 Cs 100.440(17) . 13 ?
Zn S2 Cs 142.169(19) . 13 ?
As S2 Cs 85.759(15) . 15 ?
Zn S2 Cs 89.198(15) . 15 ?
Cs S2 Cs 122.954(13) 13 15 ?
As S1 As 102.66(2) 14 12_666 ?
As S1 Cs 105.698(19) 14 13 ?
As S1 Cs 90.414(17) 12_666 13 ?
As S1 Cs 92.167(15) 14 5_554 ?
As S1 Cs 160.96(2) 12_666 5_554 ?
Cs S1 Cs 97.063(12) 13 5_554 ?
As S1 Cs 139.41(2) 14 11_666 ?
As S1 Cs 92.674(15) 12_666 11_666 ?
Cs S1 Cs 111.602(12) 13 11_666 ?
Cs S1 Cs 68.301(11) 5_554 11_666 ?

_refine_diff_density_max         1.826
_refine_diff_density_min         -1.271
_refine_diff_density_rms         0.191

_shelx_res_file                  
;

    B.res created by SHELXL-2014/7


TITL b in I4(1)/a
CELL 0.71073  11.0828  11.0828  13.2303  90.000  90.000  90.000
ZERR   4.00   0.0005   0.0005   0.0008   0.000   0.000   0.000
LATT  2
SYMM 0.5-X, -Y, 0.5+Z
SYMM 0.75-Y, 0.25+X, 0.25+Z
SYMM 0.75+Y, 0.75-X, 0.75+Z
SFAC S ZN AS CS
UNIT 32 4 16 8
TEMP -103.150

L.S. 20
ACTA
BOND
FMAP 2
PLAN 20

WGHT    0.022900    1.111800
EXTI    0.000301
FVAR       0.04399
CS    4    0.000000    0.250000    0.455214    10.50000    0.01884    0.03601 =
         0.02304    0.00000    0.00000    0.00134
AS    3    0.162432    0.017977    0.004871    11.00000    0.01219    0.01638 =
         0.00879   -0.00120   -0.00058   -0.00023
ZN    2    0.000000    0.250000    0.125000    10.25000    0.01362    0.01362 =
         0.01236    0.00000    0.00000    0.00000
S2    1    0.175886    0.214450    0.033103    11.00000    0.01600    0.01491 =
         0.01724    0.00234    0.00410    0.00143
S1    1    0.315989    0.515634    0.109090    11.00000    0.01610    0.02834 =
         0.01233    0.00591   -0.00273   -0.00409
HKLF 4

REM  b in I4(1)/a
REM R1 =  0.0265 for    2139 Fo > 4sig(Fo)  and  0.0369 for all    2564 data
REM     36 parameters refined using      0 restraints

END

WGHT      0.0182      1.4957

REM Highest difference peak  1.826,  deepest hole -1.271,  1-sigma level  0.191
Q1    1   0.0000  0.2500  0.5044  10.50000  0.05    1.83
Q2    1   0.0000  0.2500  0.3936  10.50000  0.05    1.01
Q3    1  -0.0369  0.1923  0.4518  11.00000  0.05    0.75
Q4    1   0.1587  0.0187  0.0539  11.00000  0.05    0.74
Q5    1   0.0000  0.2500  0.0682  10.50000  0.05    0.66
Q6    1   0.1647  0.0130 -0.0517  11.00000  0.05    0.65
Q7    1   0.0192  0.2765  0.3544  11.00000  0.05    0.64
Q8    1   0.2913  0.5657  0.1326  11.00000  0.05    0.64
Q9    1   0.0562  0.3313  0.0124  11.00000  0.05    0.64
Q10   1   0.0834  0.0021 -0.0249  11.00000  0.05    0.62
Q11   1   0.0427  0.1776  0.4752  11.00000  0.05    0.60
Q12   1   0.2454  0.0888  0.0955  11.00000  0.05    0.58
Q13   1   0.1959  0.0700  0.0034  11.00000  0.05    0.54
Q14   1   0.0436  0.2326  0.5862  11.00000  0.05    0.54
Q15   1   0.2357  0.0198  0.0597  11.00000  0.05    0.54
Q16   1   0.1031  0.0520  0.0101  11.00000  0.05    0.54
Q17   1  -0.0813  0.2114  0.4984  11.00000  0.05    0.54
Q18   1   0.0094  0.1888  0.4098  11.00000  0.05    0.54
Q19   1   0.0011  0.0293  0.0521  11.00000  0.05    0.53
Q20   1   0.1332  0.2015  0.1236  11.00000  0.05    0.52
;
_shelx_res_checksum              73613
####################################################################### 
# 
# 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_[(NH4)Cs]CdAs4S8
_database_code_depnum_ccdc_archive 'CCDC 2167065'
loop_
_audit_author_name
_audit_author_address
'Hua Lin'
;Fujian Institute of Research on the Structure of Matter, CAS
China
;
_audit_update_record             
;
2022-04-18 deposited with the CCDC.	2022-09-20 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            'As4 H4 Cd Cs N S8'
_chemical_formula_weight         819.51

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
As As 0.0499 2.0058 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.3680 2.1192 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           85
_space_group_name_H-M_alt        'P 4/n'
_space_group_name_Hall           '-P 4a'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y+1/2, z'
'-y+1/2, x, z'
'y, -x+1/2, z'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'y-1/2, -x, -z'
'-y, x-1/2, -z'

_cell_length_a                   10.3879(2)
_cell_length_b                   10.3879(2)
_cell_length_c                   7.7691(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     838.35(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    170(2)
_cell_measurement_reflns_used    956
_cell_measurement_theta_min      3.2355
_cell_measurement_theta_max      29.3666

_exptl_crystal_description       Block
_exptl_crystal_colour            Orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.246
_exptl_crystal_F_000             748
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.1100
_exptl_crystal_size_mid          0.0900
_exptl_crystal_size_min          0.0500
_exptl_absorpt_coefficient_mu    12.243
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.61243
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      170(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       'Enhance (Mo) X-ray Source'
_diffrn_detector_area_resol_mean 10.3592
_diffrn_reflns_number            13193
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.622
_diffrn_reflns_theta_max         30.593
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1294
_reflns_number_gt                1184
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

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

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0095P)²+0.4068P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.00124(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1294
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0189
_refine_ls_R_factor_gt           0.0152
_refine_ls_wR_factor_ref         0.0316
_refine_ls_wR_factor_gt          0.0300
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_restrained_S_all      1.071
_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
Cs Cs 0.2500 0.2500 0.68028(3) 0.02210(7) Uani 1 4 d S T P . .
Cd Cd 0.2500 0.7500 0.0000 0.01361(7) Uani 1 4 d S T P . .
As As 0.04860(2) 0.15875(2) 0.14479(2) 0.01204(6) Uani 1 1 d . . . . .
S2 S 0.16315(4) 0.02562(4) 0.31813(6) 0.01556(10) Uani 1 1 d . . . . .
S1 S 0.07233(4) 0.64420(4) 0.17643(6) 0.01402(9) Uani 1 1 d . . . . .
N N 0.2500 0.7500 0.5000 0.0082(5) Uani 1 4 d S T P . .
H H 0.2013(19) 0.724(2) 0.446(3) 0.014(6) Uiso 1 1 d . . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cs 0.02241(9) 0.02241(9) 0.02149(13) 0.000 0.000 0.000
Cd 0.01276(8) 0.01276(8) 0.01529(13) 0.000 0.000 0.000
As 0.01092(9) 0.01138(9) 0.01383(10) 0.00084(6) 0.00014(6) 0.00035(6)
S2 0.0129(2) 0.0158(2) 0.0179(2) 0.00438(17) 0.00088(16) 0.00236(16)
S1 0.0120(2) 0.0126(2) 0.0174(2) 0.00169(16) 0.00110(16) 0.00158(15)
N 0.0094(8) 0.0094(8) 0.0057(13) 0.000 0.000 0.000

_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
Cs S1 3.6957(5) 8_666 ?
Cs S1 3.6957(5) 7_556 ?
Cs S1 3.6957(5) 6_656 ?
Cs S1 3.6957(5) 5_566 ?
Cs S2 3.7634(5) . ?
Cs S2 3.7634(5) 4 ?
Cs S2 3.7634(5) 3 ?
Cs S2 3.7634(5) 2 ?
Cs As 4.2777(3) 2_556 ?
Cs As 4.2777(3) 4_556 ?
Cs As 4.2777(3) 3_556 ?
Cs As 4.2777(3) 1_556 ?
Cd S1 2.5481(5) . ?
Cd S1 2.5481(5) 2_565 ?
Cd S1 2.5481(5) 8_665 ?
Cd S1 2.5481(5) 7_565 ?
As S1 2.2086(5) 3 ?
As S2 2.2676(5) . ?
As S2 2.3008(5) 4 ?
As Cs 4.2777(3) 1_554 ?
S2 As 2.3007(5) 3 ?
S1 As 2.2086(5) 4 ?
S1 Cs 3.6957(5) 5_566 ?
N H 0.709(17) . ?

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
S1 Cs S1 144.937(16) 8_666 7_556 ?
S1 Cs S1 84.794(5) 8_666 6_656 ?
S1 Cs S1 84.794(5) 7_556 6_656 ?
S1 Cs S1 84.794(5) 8_666 5_566 ?
S1 Cs S1 84.794(5) 7_556 5_566 ?
S1 Cs S1 144.937(16) 6_656 5_566 ?
S1 Cs S2 149.050(12) 8_666 . ?
S1 Cs S2 65.970(10) 7_556 . ?
S1 Cs S2 104.966(10) 6_656 . ?
S1 Cs S2 101.079(10) 5_566 . ?
S1 Cs S2 101.079(10) 8_666 4 ?
S1 Cs S2 104.966(10) 7_556 4 ?
S1 Cs S2 149.051(12) 6_656 4 ?
S1 Cs S2 65.970(10) 5_566 4 ?
S2 Cs S2 56.018(9) . 4 ?
S1 Cs S2 104.966(10) 8_666 3 ?
S1 Cs S2 101.079(10) 7_556 3 ?
S1 Cs S2 65.970(10) 6_656 3 ?
S1 Cs S2 149.051(12) 5_566 3 ?
S2 Cs S2 56.017(9) . 3 ?
S2 Cs S2 83.231(15) 4 3 ?
S1 Cs S2 65.970(10) 8_666 2 ?
S1 Cs S2 149.051(12) 7_556 2 ?
S1 Cs S2 101.079(10) 6_656 2 ?
S1 Cs S2 104.966(10) 5_566 2 ?
S2 Cs S2 83.231(15) . 2 ?
S2 Cs S2 56.018(9) 4 2 ?
S2 Cs S2 56.018(9) 3 2 ?
S1 Cs As 53.108(8) 8_666 2_556 ?
S1 Cs As 95.282(9) 7_556 2_556 ?
S1 Cs As 50.851(8) 6_656 2_556 ?
S1 Cs As 97.070(9) 5_566 2_556 ?
S2 Cs As 152.276(7) . 2_556 ?
S2 Cs As 151.702(8) 4 2_556 ?
S2 Cs As 112.392(7) 3 2_556 ?
S2 Cs As 112.100(8) 2 2_556 ?
S1 Cs As 50.851(8) 8_666 4_556 ?
S1 Cs As 97.070(9) 7_556 4_556 ?
S1 Cs As 95.282(9) 6_656 4_556 ?
S1 Cs As 53.108(8) 5_566 4_556 ?
S2 Cs As 151.702(8) . 4_556 ?
S2 Cs As 112.100(8) 4 4_556 ?
S2 Cs As 152.276(7) 3 4_556 ?
S2 Cs As 112.392(7) 2 4_556 ?
As Cs As 44.626(4) 2_556 4_556 ?
S1 Cs As 97.070(9) 8_666 3_556 ?
S1 Cs As 50.851(8) 7_556 3_556 ?
S1 Cs As 53.108(8) 6_656 3_556 ?
S1 Cs As 95.282(9) 5_566 3_556 ?
S2 Cs As 112.392(7) . 3_556 ?
S2 Cs As 152.276(7) 4 3_556 ?
S2 Cs As 112.100(8) 3 3_556 ?
S2 Cs As 151.702(8) 2 3_556 ?
As Cs As 44.626(4) 2_556 3_556 ?
As Cs As 64.949(6) 4_556 3_556 ?
S1 Cs As 95.282(9) 8_666 1_556 ?
S1 Cs As 53.108(8) 7_556 1_556 ?
S1 Cs As 97.070(9) 6_656 1_556 ?
S1 Cs As 50.851(8) 5_566 1_556 ?
S2 Cs As 112.100(8) . 1_556 ?
S2 Cs As 112.392(7) 4 1_556 ?
S2 Cs As 151.702(8) 3 1_556 ?
S2 Cs As 152.276(7) 2 1_556 ?
As Cs As 64.949(6) 2_556 1_556 ?
As Cs As 44.626(4) 4_556 1_556 ?
As Cs As 44.626(4) 3_556 1_556 ?
S1 Cd S1 114.91(2) . 2_565 ?
S1 Cd S1 106.819(10) . 8_665 ?
S1 Cd S1 106.820(10) 2_565 8_665 ?
S1 Cd S1 106.821(10) . 7_565 ?
S1 Cd S1 106.820(10) 2_565 7_565 ?
S1 Cd S1 114.91(2) 8_665 7_565 ?
S1 As S2 99.315(18) 3 . ?
S1 As S2 99.650(18) 3 4 ?
S2 As S2 101.38(2) . 4 ?
S1 As Cs 128.865(14) 3 1_554 ?
S2 As Cs 112.304(13) . 1_554 ?
S2 As Cs 111.491(13) 4 1_554 ?
As S2 As 90.634(18) . 3 ?
As S2 Cs 101.074(16) . . ?
As S2 Cs 100.403(16) 3 . ?
As S1 Cd 92.111(16) 4 . ?
As S1 Cs 132.181(18) 4 5_566 ?
Cd S1 Cs 133.630(16) . 5_566 ?


_refine_diff_density_max         0.818
_refine_diff_density_min         -0.552
_refine_diff_density_rms         0.107

_shelx_res_file                  
;

    A.res created by SHELXL-2014/7


TITL a in P4/n
CELL 0.71073 10.3879 10.3879 7.7691 90 90 90
ZERR 2 0.0002 0.0002 0.0002 0 0 0
LATT 1
SYMM 0.5-X,0.5-Y,+Z
SYMM 0.5-Y,+X,+Z
SYMM +Y,0.5-X,+Z
SFAC As Cd Cs H S N
UNIT 8 2 2 8 16 2

L.S. 20
PLAN  2
TEMP -103.15
CONF
fmap 2
acta
MORE -1
BOND $H
REM <olex2.extras>
REM <HklSrc "%.\\a.hkl">
REM </olex2.extras>

WGHT    0.009500    0.406800
EXTI    0.001243
FVAR       0.07694
CS    3    0.250000    0.250000    0.680277    10.25000    0.02241    0.02241 =
         0.02149    0.00000    0.00000    0.00000
CD    2    0.250000    0.750000    0.000000    10.25000    0.01276    0.01276 =
         0.01529    0.00000    0.00000    0.00000
AS    1    0.048601    0.158751    0.144789    11.00000    0.01092    0.01138 =
         0.01383    0.00084    0.00014    0.00035
S2    5    0.163146    0.025622    0.318128    11.00000    0.01293    0.01583 =
         0.01792    0.00438    0.00088    0.00236
S1    5    0.072331    0.644204    0.176431    11.00000    0.01205    0.01258 =
         0.01743    0.00169    0.00110    0.00158
N     6    0.250000    0.750000    0.500000    10.25000    0.00945    0.00945 =
         0.00573    0.00000    0.00000    0.00000
H     4    0.201317    0.724354    0.446019    11.00000    0.01362
HKLF 4

REM  a in P4/n
REM R1 =  0.0152 for    1184 Fo > 4sig(Fo)  and  0.0189 for all    1294 data
REM     40 parameters refined using      0 restraints

END

WGHT      0.0095      0.3851

REM Highest difference peak  0.818,  deepest hole -0.552,  1-sigma level  0.107
Q1    1   0.2500  0.2500  0.7594  10.25000  0.05    0.82
Q2    1   0.2500  0.7500 -0.1049  10.50000  0.05    0.65
;
_shelx_res_checksum              22203
