# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_a
_database_code_depnum_ccdc_archive 'CCDC 1517380'
_audit_update_record             
;
2016-11-15 deposited with the CCDC.
2017-06-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba6 Li2 S16 Sn4 Zn'
_chemical_formula_weight         1891.01

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Sn Sn -0.6537 1.4246 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   I-43d

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

_cell_length_a                   14.5924(3)
_cell_length_b                   14.5924(3)
_cell_length_c                   14.5924(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3107.28(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5391
_cell_measurement_theta_min      2.7918
_cell_measurement_theta_max      27.4391

_exptl_crystal_description       Prism
_exptl_crystal_colour            Light-yellow
_exptl_crystal_size_max          0.2000
_exptl_crystal_size_mid          0.2000
_exptl_crystal_size_min          0.2000
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    4.042
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3312
_exptl_absorpt_coefficient_mu    12.450
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.6904
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  Saturn724
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean 28.5714
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12103
_diffrn_reflns_av_R_equivalents  0.0498
_diffrn_reflns_av_sigmaI/netI    0.0213
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.42
_diffrn_reflns_theta_max         27.44
_reflns_number_total             587
_reflns_number_gt                587
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0147P)²+2.0874P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    .
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.00084(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_number_reflns         587
_refine_ls_number_parameters     25
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0124
_refine_ls_R_factor_gt           0.0124
_refine_ls_wR_factor_ref         0.0281
_refine_ls_wR_factor_gt          0.0281
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_restrained_S_all      0.983
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ba1 Ba 0.0000 0.2500 0.01427(2) 0.01572(9) Uani 1 2 d S . .
Sn1 Sn 0.023379(14) 0.523379(14) -0.023379(14) 0.01025(10) Uani 1 3 d S . .
S1 S -0.13350(5) 0.36650(5) 0.13350(5) 0.0165(3) Uani 1 3 d S . .
S2 S 0.06631(6) 0.08033(6) -0.11452(5) 0.01389(19) Uani 1 1 d . . .
Zn1 Zn 0.1250 0.0000 -0.2500 0.0135(6) Uani 0.311(3) 4 d SP . 1
Li1 Li 0.1250 0.0000 -0.2500 0.0135(6) Uani 0.69 4 d SP . 2

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
Ba1 0.01918(16) 0.01133(14) 0.01664(15) 0.000 0.000 0.00139(11)
Sn1 0.01025(10) 0.01025(10) 0.01025(10) -0.00004(8) -0.00004(8) 0.00004(8)
S1 0.0165(3) 0.0165(3) 0.0165(3) 0.0031(3) 0.0031(3) -0.0031(3)
S2 0.0143(4) 0.0123(4) 0.0150(4) 0.0029(3) 0.0038(3) 0.0009(3)
Zn1 0.0181(11) 0.0112(8) 0.0112(8) 0.000 0.000 0.000
Li1 0.0181(11) 0.0112(8) 0.0112(8) 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
Ba1 S1 3.1165(5) 26_454 ?
Ba1 S1 3.1165(5) . ?
Ba1 S2 3.2555(8) . ?
Ba1 S2 3.2555(8) 26_454 ?
Ba1 S2 3.3026(8) 31_454 ?
Ba1 S2 3.3026(8) 5 ?
Ba1 S2 3.4411(9) 15_454 ?
Ba1 S2 3.4411(9) 40_444 ?
Ba1 Sn1 4.0413(3) . ?
Ba1 Sn1 4.0413(3) 26_454 ?
Ba1 Ba1 4.0645(7) 15_454 ?
Ba1 Li1 4.0840 5 ?
Sn1 S1 2.3535(14) 37_454 ?
Sn1 S2 2.4025(8) 26_454 ?
Sn1 S2 2.4025(8) 36_454 ?
Sn1 S2 2.4025(8) 31_454 ?
Sn1 Ba1 4.0413(3) 11_455 ?
Sn1 Ba1 4.0413(3) 31_454 ?
S1 Sn1 2.3535(14) 13_455 ?
S1 Ba1 3.1165(5) 31_454 ?
S1 Ba1 3.1165(5) 11_455 ?
S2 Sn1 2.4025(8) 26_454 ?
S2 Zn1 2.4527(8) . ?
S2 Ba1 3.3026(8) 9 ?
S2 Ba1 3.4411(9) 15_454 ?
Zn1 S2 2.4527(8) 28_444 ?
Zn1 S2 2.4527(8) 42_444 ?
Zn1 S2 2.4527(8) 19_544 ?

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 Ba1 S1 112.12(2) 26_454 . ?
S1 Ba1 S2 73.84(2) 26_454 . ?
S1 Ba1 S2 157.36(2) . . ?
S1 Ba1 S2 157.36(2) 26_454 26_454 ?
S1 Ba1 S2 73.84(2) . 26_454 ?
S2 Ba1 S2 109.48(3) . 26_454 ?
S1 Ba1 S2 87.90(3) 26_454 31_454 ?
S1 Ba1 S2 73.18(2) . 31_454 ?
S2 Ba1 S2 129.45(2) . 31_454 ?
S2 Ba1 S2 72.64(3) 26_454 31_454 ?
S1 Ba1 S2 73.18(2) 26_454 5 ?
S1 Ba1 S2 87.90(3) . 5 ?
S2 Ba1 S2 72.64(3) . 5 ?
S2 Ba1 S2 129.45(2) 26_454 5 ?
S2 Ba1 S2 146.06(3) 31_454 5 ?
S1 Ba1 S2 130.61(3) 26_454 15_454 ?
S1 Ba1 S2 93.333(15) . 15_454 ?
S2 Ba1 S2 68.494(10) . 15_454 ?
S2 Ba1 S2 68.494(10) 26_454 15_454 ?
S2 Ba1 S2 141.05(3) 31_454 15_454 ?
S2 Ba1 S2 65.99(2) 5 15_454 ?
S1 Ba1 S2 93.333(15) 26_454 40_444 ?
S1 Ba1 S2 130.61(3) . 40_444 ?
S2 Ba1 S2 68.494(10) . 40_444 ?
S2 Ba1 S2 68.494(10) 26_454 40_444 ?
S2 Ba1 S2 65.99(2) 31_454 40_444 ?
S2 Ba1 S2 141.05(3) 5 40_444 ?
S2 Ba1 S2 101.16(3) 15_454 40_444 ?
S1 Ba1 Sn1 124.16(2) 26_454 . ?
S1 Ba1 Sn1 65.81(2) . . ?
S2 Ba1 Sn1 130.327(17) . . ?
S2 Ba1 Sn1 36.476(14) 26_454 . ?
S2 Ba1 Sn1 36.466(14) 31_454 . ?
S2 Ba1 Sn1 152.076(15) 5 . ?
S2 Ba1 Sn1 104.595(14) 15_454 . ?
S2 Ba1 Sn1 64.873(14) 40_444 . ?
S1 Ba1 Sn1 65.81(2) 26_454 26_454 ?
S1 Ba1 Sn1 124.16(2) . 26_454 ?
S2 Ba1 Sn1 36.476(14) . 26_454 ?
S2 Ba1 Sn1 130.327(17) 26_454 26_454 ?
S2 Ba1 Sn1 152.076(15) 31_454 26_454 ?
S2 Ba1 Sn1 36.466(14) 5 26_454 ?
S2 Ba1 Sn1 64.873(14) 15_454 26_454 ?
S2 Ba1 Sn1 104.595(14) 40_444 26_454 ?
Sn1 Ba1 Sn1 164.374(11) . 26_454 ?
S1 Ba1 Ba1 123.938(12) 26_454 15_454 ?
S1 Ba1 Ba1 123.938(12) . 15_454 ?
S2 Ba1 Ba1 54.740(15) . 15_454 ?
S2 Ba1 Ba1 54.740(15) 26_454 15_454 ?
S2 Ba1 Ba1 106.971(15) 31_454 15_454 ?
S2 Ba1 Ba1 106.971(15) 5 15_454 ?
S2 Ba1 Ba1 50.579(13) 15_454 15_454 ?
S2 Ba1 Ba1 50.579(13) 40_444 15_454 ?
Sn1 Ba1 Ba1 82.187(5) . 15_454 ?
Sn1 Ba1 Ba1 82.187(5) 26_454 15_454 ?
S1 Ba1 Li1 110.074(19) 26_454 5 ?
S1 Ba1 Li1 73.363(17) . 5 ?
S2 Ba1 Li1 84.053(14) . 5 ?
S2 Ba1 Li1 92.565(15) 26_454 5 ?
S2 Ba1 Li1 146.036(14) 31_454 5 ?
S2 Ba1 Li1 36.906(13) 5 5 ?
S2 Ba1 Li1 36.806(13) 15_454 5 ?
S2 Ba1 Li1 137.385(15) 40_444 5 ?
Sn1 Ba1 Li1 120.621(3) . 5 ?
Sn1 Ba1 Li1 58.452(3) 26_454 5 ?
Ba1 Ba1 Li1 87.078(5) 15_454 5 ?
S1 Sn1 S2 111.01(2) 37_454 26_454 ?
S1 Sn1 S2 111.01(2) 37_454 36_454 ?
S2 Sn1 S2 107.89(2) 26_454 36_454 ?
S1 Sn1 S2 111.01(2) 37_454 31_454 ?
S2 Sn1 S2 107.89(2) 26_454 31_454 ?
S2 Sn1 S2 107.89(2) 36_454 31_454 ?
S1 Sn1 Ba1 134.197(5) 37_454 11_455 ?
S2 Sn1 Ba1 54.79(2) 26_454 11_455 ?
S2 Sn1 Ba1 53.66(2) 36_454 11_455 ?
S2 Sn1 Ba1 114.79(2) 31_454 11_455 ?
S1 Sn1 Ba1 134.197(5) 37_454 . ?
S2 Sn1 Ba1 53.66(2) 26_454 . ?
S2 Sn1 Ba1 114.79(2) 36_454 . ?
S2 Sn1 Ba1 54.79(2) 31_454 . ?
Ba1 Sn1 Ba1 76.762(8) 11_455 . ?
S1 Sn1 Ba1 134.197(5) 37_454 31_454 ?
S2 Sn1 Ba1 114.79(2) 26_454 31_454 ?
S2 Sn1 Ba1 54.79(2) 36_454 31_454 ?
S2 Sn1 Ba1 53.66(2) 31_454 31_454 ?
Ba1 Sn1 Ba1 76.762(8) 11_455 31_454 ?
Ba1 Sn1 Ba1 76.762(8) . 31_454 ?
Sn1 S1 Ba1 111.61(2) 13_455 31_454 ?
Sn1 S1 Ba1 111.61(2) 13_455 11_455 ?
Ba1 S1 Ba1 107.25(3) 31_454 11_455 ?
Sn1 S1 Ba1 111.61(2) 13_455 . ?
Ba1 S1 Ba1 107.25(3) 31_454 . ?
Ba1 S1 Ba1 107.25(3) 11_455 . ?
Sn1 S2 Zn1 109.59(3) 26_454 . ?
Sn1 S2 Ba1 89.86(2) 26_454 . ?
Zn1 S2 Ba1 158.84(3) . . ?
Sn1 S2 Ba1 88.75(2) 26_454 9 ?
Zn1 S2 Ba1 89.14(2) . 9 ?
Ba1 S2 Ba1 99.85(2) . 9 ?
Sn1 S2 Ba1 130.66(3) 26_454 15_454 ?
Zn1 S2 Ba1 86.00(2) . 15_454 ?
Ba1 S2 Ba1 74.682(19) . 15_454 ?
Ba1 S2 Ba1 139.43(3) 9 15_454 ?
S2 Zn1 S2 97.004(12) 28_444 42_444 ?
S2 Zn1 S2 139.13(4) 28_444 . ?
S2 Zn1 S2 97.004(12) 42_444 . ?
S2 Zn1 S2 97.003(12) 28_444 19_544 ?
S2 Zn1 S2 139.13(4) 42_444 19_544 ?
S2 Zn1 S2 97.003(12) . 19_544 ?

_diffrn_measured_fraction_theta_max 0.982
_diffrn_reflns_theta_full        27.44
_diffrn_measured_fraction_theta_full 0.982
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.113
####################################################################### 
# 
# 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_a
_database_code_depnum_ccdc_archive 'CCDC 1525057'
_audit_update_record             
;
2016-12-30 deposited with the CCDC.
2017-06-23 downloaded from the CCDC.
;
_audit_creation_method           'Created with Diamond (www.crystalimpact.com)'
_audit_creation_date             16-12-30
_chemical_formula_sum            'Ag2 Ba6 Cd S16 Sn4'
_chemical_formula_weight         2139.900
_refine_ls_R_factor_all          0.008
_cell_length_a                   14.7383(6)
_cell_length_b                   14.7383(6)
_cell_length_c                   14.7383(6)
_cell_angle_alpha                90.000
_cell_angle_beta                 90.000
_cell_angle_gamma                90.000
_cell_volume                     3201.4(2)
_cell_formula_units_Z            4
_symmetry_int_tables_number      220
_symmetry_space_group_name_H-M   'I -4 3 d'
_symmetry_space_group_name_Hall  I_-4bd_2c_3

loop_
_atom_type_symbol
_atom_type_oxidation_number
_atom_type_radius_bond
Ba ? 1.200
Sn ? 1.200
Cd ? 1.200
Ag ? 1.200
S ? 1.200


loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_attached_hydrogens
_atom_site_calc_flag
_atom_site_thermal_displace_type
_atom_site_u_iso_or_equiv
Ba1 Ba 0.0000 0.2500 0.0179(0) 1.000 24 d ? d Uani 0.01873(7)
Sn1 Sn 0.0214(0) 0.5214(0) -0.0214(0) 1.000 16 c ? d Uani 0.01132(8)
Cd1 Cd -0.1250 0.5000 -0.2500 0.330 12 a ? d Uani 0.054(2)
Ag1 Ag -0.1250 0.5000 -0.2500 0.670 12 a ? d Uani 0.0197(6)
S1 S -0.1365(0) 0.3634(0) 0.1365(0) 1.000 16 c ? d Uani 0.0178(2)
S2 S -0.0658(0) 0.4146(0) -0.1088(0) 1.000 48 e ? d Uani 0.01395(13)


loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
Ba1 0.02800(14) 0.01144(11) 0.01674(12) 0.00353(8) 0.00000 0.00000
Sn1 0.01132(8) 0.01132(8) 0.01132(8) -0.00050(6) 0.00050(6) 0.00050(6)
Cd1 0.109(4) 0.026(2) 0.026(2) 0.00000 0.00000 0.00000
Ag1 0.0330(7) 0.0131(9) 0.0131(9) 0.00000 0.00000 0.00000
S1 0.0178(2) 0.0178(2) 0.0178(2) -0.0039(3) 0.0039(3) 0.0039(3)
S2 0.0163(3) 0.0122(3) 0.0134(3) 0.0003(2) -0.0031(2) -0.0012(2)


_geom_bond_publ_flag             Ba1


_geom_angle_publ_flag            S1
