# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_shelxl
_database_code_depnum_ccdc_archive 'CCDC 1863982'
_audit_update_record             
;
2018-09-21 deposited with the CCDC.
2018-11-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'Si2.63 Ge5.88 O21 H2, C8 H24 N2'
_chemical_formula_sum            'C8 H26 Ge5.88 N2 O21 Si2.63'
_chemical_formula_weight         1014.60

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0020 0.0010 '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'
N N 0.0040 0.0020 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0080 0.0040 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.0640 0.0530 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.2720 1.4270 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           66
_space_group_name_H-M_alt        'C c c m'
_space_group_name_Hall           '-C 2 2c'

_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, -y, z'
'-x, y, -z+1/2'
'x, -y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x, y, -z'
'x, -y, z-1/2'
'-x, y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'
'-x+1/2, y+1/2, z-1/2'

_cell_length_a                   12.895(3)
_cell_length_b                   20.421(4)
_cell_length_c                   20.281(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5340.6(19)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    24276
_cell_measurement_theta_min      1.629
_cell_measurement_theta_max      21.129

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.524
_exptl_crystal_F_000             3958
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.010
_exptl_crystal_size_mid          0.000
_exptl_crystal_size_min          0.000
_exptl_absorpt_coefficient_mu    4.548
_shelx_estimated_absorpt_T_min   0.956
_shelx_estimated_absorpt_T_max   1.000
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.881
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.620
_diffrn_radiation_type           synchrotron
_diffrn_source                   synchrotron
_diffrn_measurement_device_type  'MX225-HS CCD area detector'
_diffrn_measurement_method       'omega scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4224
_diffrn_reflns_av_unetI/netI     0.1904
_diffrn_reflns_av_R_equivalents  0.1410
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         1.629
_diffrn_reflns_theta_max         21.129
_diffrn_reflns_theta_full        21.839
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 0.904
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 0.904
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 0.904
_reflns_number_total             2272
_reflns_number_gt                1058
_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       'PAL BL2D-SMDC Program'
_computing_cell_refinement       'HKL3000sm (Otwinowski & Minor, 1997)'
_computing_data_reduction        'HKL3000sm (Otwinowski & Minor, 1997)'
_computing_structure_solution    'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    Mercury
_computing_publication_material  WinGX

_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)+(0.1792P)²+164.4099P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2272
_refine_ls_number_parameters     199
_refine_ls_number_restraints     315
_refine_ls_R_factor_all          0.1983
_refine_ls_R_factor_gt           0.1031
_refine_ls_wR_factor_ref         0.3558
_refine_ls_wR_factor_gt          0.3090
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_restrained_S_all      1.036
_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
C1 C -0.285(3) 0.3075(14) 0.1732(18) 0.103(16) Uani 1.0000(10) 1 d D U P . .
H1A H -0.3431 0.2934 0.1455 0.154 Uiso 1.0000(10) 1 calc R U P . .
H1B H -0.3070 0.3443 0.2009 0.154 Uiso 1.0000(10) 1 calc R U P . .
H1C H -0.2271 0.3213 0.1452 0.154 Uiso 1.0000(10) 1 calc R U P . .
C2 C -0.158(2) 0.2723(18) 0.2613(17) 0.14(2) Uani 1.0000(10) 1 d D U P . .
H2A H -0.1008 0.2863 0.2332 0.213 Uiso 1.0000(10) 1 calc R U P . .
H2B H -0.1806 0.3089 0.2892 0.213 Uiso 1.0000(10) 1 calc R U P . .
H2C H -0.1360 0.2358 0.2892 0.213 Uiso 1.0000(10) 1 calc R U P . .
C3 C -0.355(4) 0.518(3) 0.0000 0.12(2) Uani 1.0000(10) 2 d DS TU P . .
H3A H -0.4198 0.5018 0.0200 0.179 Uiso 0.500(1) 1 calc DR U P . .
H3B H -0.3690 0.5317 -0.0454 0.179 Uiso 0.500(1) 1 calc R U P . .
H3C H -0.3292 0.5551 0.0255 0.179 Uiso 0.500(1) 1 calc R U P . .
C4 C -0.291(3) 0.4228(18) -0.0601(13) 0.109(17) Uani 1.0000(10) 1 d D U P . .
H4A H -0.3608 0.4040 -0.0599 0.163 Uiso 1.0000(10) 1 calc R U P . .
H4B H -0.2819 0.4498 -0.0997 0.163 Uiso 1.0000(10) 1 calc R U P . .
H4C H -0.2395 0.3874 -0.0603 0.163 Uiso 1.0000(10) 1 calc R U P . .
C5 C -0.170(4) 0.493(2) 0.0000 0.081(15) Uani 1.0000(10) 2 d DS TU P . .
H5A H -0.1607 0.5200 0.0395 0.121 Uiso 0.500(1) 1 calc R U P . .
H5B H -0.1184 0.4577 0.0000 0.121 Uiso 1.0000(10) 2 calc R U P . .
H5C H -0.1608 0.5201 -0.0394 0.121 Uiso 0.500(1) 1 calc R U P . .
N1 N -0.2500 0.2500 0.2176(15) 0.055(10) Uani 1.0000(10) 2 d DS TU P . .
N2 N -0.276(2) 0.4642(15) 0.0000 0.071(12) Uani 1.0000(10) 2 d DS TU P . .
O1 O 0.1323(14) 0.3731(8) 0.1069(8) 0.022(4) Uani 1 1 d . U . . .
H1 H 0.1876 0.3518 0.1021 0.033 Uiso 1 1 calc R U . . .
O2 O -0.0674(14) 0.3657(8) 0.1262(9) 0.026(4) Uani 1 1 d . U . . .
O3 O -0.039(2) 0.3543(12) 0.0000 0.024(5) Uani 1 2 d S TU P . .
O4 O 0.0045(14) 0.2508(8) 0.1044(8) 0.018(3) Uani 1 1 d . U . . .
O5 O 0.1192(19) 0.2900(11) 0.0000 0.015(4) Uani 1 2 d S TU P . .
O6 O 0.2016(13) 0.1924(7) 0.0668(8) 0.015(3) Uani 1 1 d . U . . .
O7 O 0.317(3) 0.0463(17) 0.2987(16) 0.095(7) Uani 1 1 d . U . . .
O8 O 0.5000 0.093(2) 0.2500 0.089(8) Uani 1 2 d S TU P . .
O9 O 0.5000 0.0000 0.342(2) 0.086(8) Uani 1 2 d S TU P . .
O10 O 0.172(2) 0.0505(14) 0.2024(15) 0.074(6) Uani 1 1 d . U . . .
O11 O 0.0000 0.0916(13) 0.2500 0.050(7) Uani 1 2 d S TU P . .
O12 O 0.0000 0.0000 0.1531(14) 0.050(7) Uani 1 2 d S TU P . .
O13 O 0.0415(17) 0.1187(8) 0.1283(9) 0.037(4) Uani 1 1 d . U . . .
O14 O 0.014(2) 0.1561(11) 0.0000 0.019(4) Uani 1 2 d S TU P . .
T1 Si 0.0563(6) 0.0668(3) 0.1829(3) 0.0189(16) Uani 1 1 d . U . . .
T2SI Si 0.2484 0.0000 0.2500 0.078(3) Uani 0.5406(10) 2 d S TU P A 1
T3SI Si 0.4415 0.0676 0.3196 0.0643(19) Uani 0.5408(10) 1 d . U P A 1
T2GE Ge 0.2484 0.0000 0.2500 0.078(3) Uani 0.4594(10) 2 d S TU P A 2
T3GE Ge 0.4415 0.0676 0.3196 0.0643(19) Uani 0.4592(10) 1 d . U P A 2
Ge1 Ge 0.0692(2) 0.18328(13) 0.07370(14) 0.0212(8) Uani 1 1 d . U . . .
Ge2 Ge 0.2500 0.2500 0.0000 0.0086(12) Uani 1 4 d S TU P . .
Ge3 Ge 0.0293(2) 0.32951(13) 0.07164(13) 0.0179(8) Uani 1 1 d . U . . .


_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
C1 N1 1.55(3) . ?
C2 N1 1.54(3) . ?
C3 N2 1.50(3) . ?
C4 N2 1.50(3) . ?
C5 N2 1.49(3) . ?
N1 C2 1.54(3) 6_455 ?
N1 C1 1.55(3) 6_455 ?
N2 C4 1.50(3) 10 ?
O1 Ge3 1.751(17) . ?
O2 T3GE 1.756(18) 8_455 ?
O2 T3SI 1.756(18) 8_455 ?
O2 Ge3 1.823(17) . ?
O3 Ge3 1.772(14) 10 ?
O3 Ge3 1.772(14) . ?
O4 Ge1 1.728(17) . ?
O4 Ge3 1.768(16) . ?
O5 Ge2 1.87(2) . ?
O5 Ge3 2.026(16) 10 ?
O5 Ge3 2.026(16) . ?
O6 Ge1 1.724(17) . ?
O6 Ge2 1.900(15) . ?
O7 T2GE 1.63(3) . ?
O7 T2SI 1.63(3) . ?
O7 T3GE 1.71(3) . ?
O7 T3SI 1.71(3) . ?
O8 T3GE 1.684(13) 3_655 ?
O8 T3SI 1.684(13) 3_655 ?
O8 T3SI 1.684(13) . ?
O8 T3GE 1.684(13) . ?
O9 T3GE 1.637(12) 2_655 ?
O9 T3SI 1.637(12) 2_655 ?
O9 T3SI 1.637(12) . ?
O9 T3GE 1.637(12) . ?
O10 T1 1.57(3) . ?
O10 T2GE 1.73(3) . ?
O10 T2SI 1.73(3) . ?
O11 T1 1.623(11) 3 ?
O11 T1 1.623(11) . ?
O12 T1 1.659(12) . ?
O12 T1 1.660(12) 2 ?
O13 T1 1.545(19) . ?
O13 Ge1 1.758(17) . ?
O14 Ge1 1.745(12) 10 ?
O14 Ge1 1.745(12) . ?
T2SI O7 1.63(3) 4 ?
T2SI O10 1.73(3) 4 ?
T3SI O2 1.756(18) 8 ?
T2GE O7 1.63(3) 4 ?
T2GE O10 1.73(3) 4 ?
T3GE O2 1.756(18) 8 ?
Ge2 O5 1.87(2) 13 ?
Ge2 O6 1.900(15) 10 ?
Ge2 O6 1.900(15) 6 ?
Ge2 O6 1.900(15) 13 ?
Ge3 Ge3 2.906(5) 10 ?

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
C2 N1 C2 110.0(11) . 6_455 ?
C2 N1 C1 109.5(5) . 6_455 ?
C2 N1 C1 109.4(5) 6_455 6_455 ?
C2 N1 C1 109.4(5) . . ?
C2 N1 C1 109.5(5) 6_455 . ?
C1 N1 C1 108.9(11) 6_455 . ?
C5 N2 C4 109.8(8) . . ?
C5 N2 C4 109.8(8) . 10 ?
C4 N2 C4 109.2(12) . 10 ?
C5 N2 C3 109.8(12) . . ?
C4 N2 C3 109.1(8) . . ?
C4 N2 C3 109.1(8) 10 . ?
T3GE O2 Ge3 130.5(11) 8_455 . ?
T3SI O2 Ge3 130.5(11) 8_455 . ?
Ge3 O3 Ge3 110.2(13) 10 . ?
Ge1 O4 Ge3 120.2(10) . . ?
Ge2 O5 Ge3 133.5(5) . 10 ?
Ge2 O5 Ge3 133.5(5) . . ?
Ge3 O5 Ge3 91.6(10) 10 . ?
Ge1 O6 Ge2 116.8(8) . . ?
T2GE O7 T3GE 144(2) . . ?
T2SI O7 T3SI 144(2) . . ?
T3SI O8 T3SI 144(3) 3_655 . ?
T3GE O8 T3GE 144(3) 3_655 . ?
T3SI O9 T3SI 148(3) 2_655 . ?
T3GE O9 T3GE 148(3) 2_655 . ?
T1 O10 T2GE 144.0(19) . . ?
T1 O10 T2SI 144.0(19) . . ?
T1 O11 T1 143.6(19) 3 . ?
T1 O12 T1 137.3(19) . 2 ?
T1 O13 Ge1 160.2(15) . . ?
Ge1 O14 Ge1 117.9(13) 10 . ?
O13 T1 O10 116.2(14) . . ?
O13 T1 O11 109.4(12) . . ?
O10 T1 O11 106.1(12) . . ?
O13 T1 O12 104.4(12) . . ?
O10 T1 O12 109.3(11) . . ?
O11 T1 O12 111.5(12) . . ?
O7 T2SI O7 114(2) 4 . ?
O7 T2SI O10 107.8(15) 4 4 ?
O7 T2SI O10 108.7(15) . 4 ?
O7 T2SI O10 108.7(15) 4 . ?
O7 T2SI O10 107.8(15) . . ?
O10 T2SI O10 109.9(19) 4 . ?
O9 T3SI O8 106.9(17) . . ?
O9 T3SI O7 106.6(12) . . ?
O8 T3SI O7 107.0(11) . . ?
O9 T3SI O2 120.7(15) . 8 ?
O8 T3SI O2 108.1(15) . 8 ?
O7 T3SI O2 106.9(13) . 8 ?
O7 T2GE O7 114(2) 4 . ?
O7 T2GE O10 107.8(15) 4 4 ?
O7 T2GE O10 108.7(15) . 4 ?
O7 T2GE O10 108.7(15) 4 . ?
O7 T2GE O10 107.8(15) . . ?
O10 T2GE O10 109.9(19) 4 . ?
O9 T3GE O8 106.9(17) . . ?
O9 T3GE O7 106.6(12) . . ?
O8 T3GE O7 107.0(11) . . ?
O9 T3GE O2 120.7(15) . 8 ?
O8 T3GE O2 108.1(15) . 8 ?
O7 T3GE O2 106.9(13) . 8 ?
O6 Ge1 O4 114.9(8) . . ?
O6 Ge1 O14 111.6(9) . . ?
O4 Ge1 O14 111.4(10) . . ?
O6 Ge1 O13 109.5(9) . . ?
O4 Ge1 O13 105.9(9) . . ?
O14 Ge1 O13 102.7(9) . . ?
O5 Ge2 O5 180.0 . 13 ?
O5 Ge2 O6 88.5(7) . 10 ?
O5 Ge2 O6 91.5(7) 13 10 ?
O5 Ge2 O6 91.5(7) . 6 ?
O5 Ge2 O6 88.5(7) 13 6 ?
O6 Ge2 O6 180.0(10) 10 6 ?
O5 Ge2 O6 91.5(7) . 13 ?
O5 Ge2 O6 88.5(7) 13 13 ?
O6 Ge2 O6 89.0(9) 10 13 ?
O6 Ge2 O6 91.0(9) 6 13 ?
O5 Ge2 O6 88.5(7) . . ?
O5 Ge2 O6 91.5(7) 13 . ?
O6 Ge2 O6 91.0(9) 10 . ?
O6 Ge2 O6 89.0(9) 6 . ?
O6 Ge2 O6 180.0 13 . ?
O1 Ge3 O4 116.5(8) . . ?
O1 Ge3 O3 124.4(10) . . ?
O4 Ge3 O3 118.6(10) . . ?
O1 Ge3 O2 93.7(8) . . ?
O4 Ge3 O2 90.9(8) . . ?
O3 Ge3 O2 92.5(9) . . ?
O1 Ge3 O5 93.5(9) . . ?
O4 Ge3 O5 90.6(8) . . ?
O3 Ge3 O5 79.0(8) . . ?
O2 Ge3 O5 171.0(8) . . ?
O1 Ge3 Ge3 114.1(6) . 10 ?
O4 Ge3 Ge3 112.1(5) . 10 ?
O3 Ge3 Ge3 34.9(7) . 10 ?
O2 Ge3 Ge3 127.4(6) . 10 ?
O5 Ge3 Ge3 44.2(5) . 10 ?

_refine_diff_density_max         1.710
_refine_diff_density_min         -3.314
_refine_diff_density_rms         0.360

_shelxl_version_number           2014-3


# start Validation Reply Form
_vrf_DIFMN02_shelxl              
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*1.00
RESPONSE: We expected the Si/Ge ratio from the average T-O bond distances and 
applied occupancy restraints on T2 and T3. However, the Si/Ge ratios are 
statistical, so such electron deficiency may arise near the 
substitutionally disordered sites. 
;
_vrf_PLAT084_shelxl              
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.36 Report
RESPONSE: We made several attempts to obtain better quality data for this 
structure. Due to the small size of the crystal, the signal-to-noise ratio
 of the data is rather low. However, simulated powder pattern from the
 structural solution and measured powder pattern are exactly matched, 
 so we are confident the structural characterization is valid.
;
_vrf_PLAT098_shelxl              
;
PROBLEM: Large Reported Min.  (Negative) Residual Density      -3.31 eA-3  
RESPONSE: We expected the Si/Ge ratio from the average T-O bond distances and
 applied occupancy restraints on T2GE. However, the Si/Ge ratios are 
 statistical, so such electron deficiency may arise near T2GE sites. 

;
_vrf_PLAT213_shelxl              
;
PROBLEM: Atom Ge2             has ADP max/min Ratio .....        5.0 oblate
RESPONSE: These alerts are generated because there is a large 
amount of disorder in the structure. This alert may arise from 
dynamic disorder of Ge-O bonding which has flexible bonding 
nature than rigid Si-O bond.
;
_vrf_PLAT220_shelxl              
;
PROBLEM: Non-Solvent  Resd 1 Ge   Ueq(max)/Ueq(min) Range        9.0 Ratio 
RESPONSE: These alerts are generated because there is a large 
amount of disorder in the structure. In  particular, lots of 
substitutional disorder in the natrolite chain may exhibit 
such unusual ratios. 
;
_vrf_PLAT972_shelxl              
;
PROBLEM: Check Calcd Resid. Dens.  0.55A   From T2GE           -2.92 eA-3  
RESPONSE: We expected the Si/Ge ratio from the average 
T-O bond distances and applied occupancy restraints 
on T2GE. However, the Si/Ge ratios are statistical, 
so such electron deficiency may arise near T2GE sites. 
;
# end Validation Reply Form

