# Electronic Supplementary Material (ESI) for ChemComm.
# 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_i41a
_database_code_depnum_ccdc_archive 'CCDC 1033513'
_audit_update_record             
;
2015-01-29 deposited with the CCDC.
2015-01-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;

# start Validation Reply Form
_vrf_PLAT602_i41a                
;
PROBLEM: A VERY LARGE Solvent Accessible VOID(S) in Structure!
RESPONSE:
During the structure analysis, it was found that the unit cell possesses large voids. Disordered extra-framework species (template and water molecules) inside large cavities cuold not be determined as well-defined atoms in the difference electron density map.

;
# end Validation Reply Form 

_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ge3.88 In22.12 O Se50'
_chemical_formula_weight         6785.47

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
Se Se -0.0929 2.2259 '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'

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_H-M   I4(1)/a

loop_
_symmetry_equiv_pos_as_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                   22.4956(10)
_cell_length_b                   22.4956(10)
_cell_length_c                   37.984(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     19222(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       diamond
_exptl_crystal_colour            orange-yellow
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.345
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             11664
_exptl_absorpt_coefficient_mu    12.667
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            52257
_diffrn_reflns_av_R_equivalents  0.1378
_diffrn_reflns_av_sigmaI/netI    0.0938
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_theta_min         1.67
_diffrn_reflns_theta_max         24.39
_reflns_number_total             7813
_reflns_number_gt                3787
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.1132P)²+450.8231P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.000050(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         7813
_refine_ls_number_parameters     175
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1548
_refine_ls_R_factor_gt           0.0691
_refine_ls_wR_factor_ref         0.2609
_refine_ls_wR_factor_gt          0.2078
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.043
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
In1 In 1.0000 0.2500 0.54516(5) 0.0576(6) Uani 1 2 d S . .
In2 In 0.86835(7) 0.24048(7) 0.62400(4) 0.0554(5) Uani 1 1 d . . .
In3 In 0.86539(7) 0.36633(7) 0.55023(4) 0.0624(5) Uani 1 1 d . . .
In4 In 0.72725(7) 0.37740(7) 0.48378(4) 0.0545(5) Uani 0.76 1 d P . .
Ge1 Ge 0.72725(7) 0.37740(7) 0.48378(4) 0.0545(5) Uani 0.24 1 d P . .
In5 In 0.57874(7) 0.28856(8) 0.48634(4) 0.0591(5) Uani 0.76 1 d P . .
Ge2 Ge 0.57874(7) 0.28856(8) 0.48634(4) 0.0591(5) Uani 0.24 1 d P . .
In6 In 0.69419(8) 0.25836(8) 0.41295(4) 0.0641(5) Uani 0.76 1 d P . .
Ge3 Ge 0.69419(8) 0.25836(8) 0.41295(4) 0.0641(5) Uani 0.24 1 d P . .
In7 In 0.60615(8) 0.40602(9) 0.41125(4) 0.0668(6) Uani 0.76 1 d P . .
Ge4 Ge 0.60615(8) 0.40602(9) 0.41125(4) 0.0668(6) Uani 0.24 1 d P . .
Se2 Se 0.93788(10) 0.17649(10) 0.58410(6) 0.0581(6) Uani 1 1 d . . .
Se4 Se 0.79585(10) 0.29936(11) 0.58645(6) 0.0685(7) Uani 1 1 d . . .
Se3 Se 0.80760(10) 0.16925(11) 0.66039(6) 0.0675(7) Uani 1 1 d . . .
Se11 Se 0.64704(12) 0.33014(11) 0.37175(6) 0.0759(8) Uani 1 1 d . . .
Se7 Se 0.67845(11) 0.45980(12) 0.44762(7) 0.0740(7) Uani 1 1 d . . .
Se5 Se 0.80305(11) 0.44107(11) 0.51532(7) 0.0711(7) Uani 1 1 d . . .
Se10 Se 0.52608(11) 0.36067(12) 0.44661(6) 0.0724(7) Uani 1 1 d . . .
Se8 Se 0.78026(11) 0.30029(12) 0.44600(6) 0.0732(7) Uani 1 1 d . . .
Se13 Se 0.62331(12) 0.20567(12) 0.45142(7) 0.0834(8) Uani 1 1 d . . .
Se6 Se 0.65422(11) 0.33179(12) 0.52751(6) 0.0731(7) Uani 1 1 d . . .
Se12 Se 0.73980(12) 0.18189(13) 0.37405(7) 0.0880(9) Uani 1 1 d . . .
Se1 Se 1.07108(13) 0.19242(12) 0.50673(6) 0.0799(8) Uani 1 1 d . . .
Se9 Se 0.5000 0.2500 0.52681(10) 0.1010(14) Uani 1 2 d S . .
O1 O 0.0000 0.2500 0.1250 0.123(14) Uiso 1 4 d S . .


_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 Se1 2.523(3) 6_654 ?
In1 Se1 2.523(3) . ?
In1 Se2 2.622(2) 6_654 ?
In1 Se2 2.622(2) . ?
In2 Se3 2.519(3) . ?
In2 Se4 2.539(3) . ?
In2 Se2 2.611(3) . ?
In2 Se2 2.615(3) 15_666 ?
In3 Se1 2.553(3) 6_654 ?
In3 Se5 2.560(3) . ?
In3 Se4 2.571(3) . ?
In3 Se3 2.575(3) 15_666 ?
In4 Se5 2.529(3) . ?
In4 Se8 2.548(3) . ?
In4 Se6 2.552(3) . ?
In4 Se7 2.555(3) . ?
In5 Se13 2.498(3) . ?
In5 Se9 2.501(3) . ?
In5 Se6 2.505(3) . ?
In5 Se10 2.512(3) . ?
In6 Se13 2.466(3) . ?
In6 Se11 2.486(3) . ?
In6 Se12 2.489(3) . ?
In6 Se8 2.493(3) . ?
In7 Se11 2.452(3) . ?
In7 Se7 2.453(3) . ?
In7 Se12 2.466(3) 16_656 ?
In7 Se10 2.468(3) . ?
Se2 In2 2.615(3) 12_757 ?
Se3 In3 2.575(3) 12_757 ?
Se12 Ge4 2.466(3) 11_666 ?
Se12 In7 2.466(3) 11_666 ?
Se1 In3 2.553(3) 6_654 ?
Se9 Ge2 2.501(3) 6_554 ?
Se9 In5 2.501(3) 6_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
Se1 In1 Se1 109.30(14) 6_654 . ?
Se1 In1 Se2 109.90(8) 6_654 6_654 ?
Se1 In1 Se2 108.21(8) . 6_654 ?
Se1 In1 Se2 108.21(8) 6_654 . ?
Se1 In1 Se2 109.90(8) . . ?
Se2 In1 Se2 111.31(12) 6_654 . ?
Se3 In2 Se4 106.95(9) . . ?
Se3 In2 Se2 107.03(9) . . ?
Se4 In2 Se2 110.27(9) . . ?
Se3 In2 Se2 109.22(9) . 15_666 ?
Se4 In2 Se2 109.98(9) . 15_666 ?
Se2 In2 Se2 113.16(11) . 15_666 ?
Se1 In3 Se5 108.14(10) 6_654 . ?
Se1 In3 Se4 112.55(11) 6_654 . ?
Se5 In3 Se4 109.19(10) . . ?
Se1 In3 Se3 117.15(10) 6_654 15_666 ?
Se5 In3 Se3 97.02(9) . 15_666 ?
Se4 In3 Se3 111.40(10) . 15_666 ?
Se5 In4 Se8 109.69(10) . . ?
Se5 In4 Se6 110.70(10) . . ?
Se8 In4 Se6 113.22(10) . . ?
Se5 In4 Se7 97.68(9) . . ?
Se8 In4 Se7 113.10(10) . . ?
Se6 In4 Se7 111.41(10) . . ?
Se13 In5 Se9 110.60(9) . . ?
Se13 In5 Se6 110.44(11) . . ?
Se9 In5 Se6 103.36(11) . . ?
Se13 In5 Se10 110.62(11) . . ?
Se9 In5 Se10 105.02(9) . . ?
Se6 In5 Se10 116.35(11) . . ?
Se13 In6 Se11 114.16(12) . . ?
Se13 In6 Se12 106.62(11) . . ?
Se11 In6 Se12 104.54(11) . . ?
Se13 In6 Se8 112.69(11) . . ?
Se11 In6 Se8 113.74(11) . . ?
Se12 In6 Se8 103.90(11) . . ?
Se11 In7 Se7 116.05(11) . . ?
Se11 In7 Se12 109.24(11) . 16_656 ?
Se7 In7 Se12 99.17(11) . 16_656 ?
Se11 In7 Se10 108.61(11) . . ?
Se7 In7 Se10 112.42(11) . . ?
Se12 In7 Se10 111.01(11) 16_656 . ?
In2 Se2 In2 106.96(8) . 12_757 ?
In2 Se2 In1 107.40(9) . . ?
In2 Se2 In1 109.29(9) 12_757 . ?
In2 Se4 In3 102.44(9) . . ?
In2 Se3 In3 104.92(9) . 12_757 ?
In7 Se11 In6 103.12(10) . . ?
In7 Se7 In4 103.29(11) . . ?
In4 Se5 In3 104.06(10) . . ?
In7 Se10 In5 104.46(10) . . ?
In6 Se8 In4 100.24(10) . . ?
In6 Se13 In5 102.43(11) . . ?
In5 Se6 In4 100.73(10) . . ?
Ge4 Se12 In7 0.00(12) 11_666 11_666 ?
Ge4 Se12 In6 104.34(12) 11_666 . ?
In7 Se12 In6 104.34(12) 11_666 . ?
In1 Se1 In3 104.24(10) . 6_654 ?
Ge2 Se9 In5 0.00(11) 6_554 6_554 ?
Ge2 Se9 In5 104.14(16) 6_554 . ?
In5 Se9 In5 104.14(16) 6_554 . ?

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        24.39
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         2.237
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.322





