# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_c_sq
_database_code_depnum_ccdc_archive 'CCDC 1417354'
_audit_update_record             
;
2015-10-08 deposited with the CCDC.
2015-10-30 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         'Ge3 In6 S17,4(C6H14NO),1.5(H2O)'
_chemical_formula_sum            'C24 H59 Ge3 In6 N4 O5.50 S17'
_chemical_formula_weight         1943.46

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
In In -0.7276 1.3100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 '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'
C C 0.0033 0.0016 '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'

_space_group_crystal_system      cubic
_space_group_IT_number           199
_space_group_name_H-M_alt        'I 21 3'
_space_group_name_Hall           'I 2b 2c 3'

_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'
'-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'
'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'

_cell_length_a                   18.6836(9)
_cell_length_b                   18.6836(9)
_cell_length_c                   18.6836(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     6522.0(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    153(2)
_cell_measurement_reflns_used    2478
_cell_measurement_theta_min      2.18
_cell_measurement_theta_max      19.96

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.979
_exptl_crystal_F_000             3748
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.170
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    4.019
_shelx_estimated_absorpt_T_min   0.548
_shelx_estimated_absorpt_T_max   0.584
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5223
_exptl_absorpt_correction_T_max  0.5631
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      153(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17606
_diffrn_reflns_av_unetI/netI     0.0496
_diffrn_reflns_av_R_equivalents  0.0899
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         1.541
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2155
_reflns_number_gt                1859
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          
;
Refined as a 2-component inversion twin.
Due to the large pore voids(\~64.0% - see PLATON SQUEEZE details below)  
contained in the structure, disordered solvent molecules could not be 
modeled as discrete atomic sites, even data collected at 153K. 
SQUEEZE process in the PLATON software was applied to calculate the 
contribution to the diffraction from the solvent region.
The Following ALERT was generated by PLATON checkcif Alert level A
CHEMW03_ALERT_2_A ALERT: The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.90 <> 1.10
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_weight 1943.46
TEST: Calculate formula weight from _atom_site_*
atom mass num sum
S 32.07 17.00 545.12
Ge 72.59 3.00 217.77
In 114.8 6.00 688.92
O 16.00 0.00 0.00
N 14.01 0.00 0.00
C 12.01 0.00 0.00
H 1.01 0.00 0.00
Calculated formula weight 1451.81

RESPONSE:This alert may caused by the difference of the calculated 
and reported formula.The contributions of the disordered H+-DMMP(C6H14NO) 
and water molecules removed by the SQUEEZE process were included 
in the overall formula.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0191P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2155
_refine_ls_number_parameters     42
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0320
_refine_ls_wR_factor_ref         0.0530
_refine_ls_wR_factor_gt          0.0509
_refine_ls_goodness_of_fit_ref   0.948
_refine_ls_restrained_S_all      0.948
_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
In1 In 0.13925(3) 0.48506(3) 0.84774(3) 0.04131(16) Uani 1 1 d . . . . .
Ge2 Ge -0.03051(6) 0.5000 0.7500 0.0430(3) Uani 1 2 d S T P . .
S1 S 0.03404(12) 0.41839(12) 0.80414(13) 0.0579(6) Uani 1 1 d . . . . .
S2 S 0.10521(11) 0.60521(11) 0.89479(11) 0.0401(9) Uani 1 3 d S T P . .
S4 S -0.09979(11) 0.44171(13) 0.67436(13) 0.0589(7) Uani 1 1 d . . . . .
S3 S 0.22256(17) 0.5000 0.7500 0.108(2) Uani 1 2 d S T P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
In1 S3 2.416(2) . ?
In1 S4 2.455(2) 17_455 ?
In1 S1 2.466(2) . ?
In1 S2 2.4932(8) . ?
Ge2 S1 2.192(2) . ?
Ge2 S1 2.192(2) 16_456 ?
Ge2 S4 2.204(2) 16_456 ?
Ge2 S4 2.204(2) . ?
S2 In1 2.4933(8) 8_656 ?
S2 In1 2.4933(8) 11_466 ?
S4 In1 2.455(2) 21_445 ?
S3 In1 2.416(2) 16_456 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
S3 In1 S4 116.30(8) . 17_455 ?
S3 In1 S1 108.80(8) . . ?
S4 In1 S1 97.06(8) 17_455 . ?
S3 In1 S2 109.08(9) . . ?
S4 In1 S2 113.42(8) 17_455 . ?
S1 In1 S2 111.59(7) . . ?
S1 Ge2 S1 113.22(13) . 16_456 ?
S1 Ge2 S4 111.78(9) . 16_456 ?
S1 Ge2 S4 105.98(8) 16_456 16_456 ?
S1 Ge2 S4 105.98(8) . . ?
S1 Ge2 S4 111.78(9) 16_456 . ?
S4 Ge2 S4 108.08(13) 16_456 . ?
Ge2 S1 In1 103.87(9) . . ?
In1 S2 In1 117.21(5) . 8_656 ?
In1 S2 In1 117.21(5) . 11_466 ?
In1 S2 In1 117.21(5) 8_656 11_466 ?
Ge2 S4 In1 98.36(8) . 21_445 ?
In1 S3 In1 99.77(11) . 16_456 ?

_refine_diff_density_max         0.383
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.066



