# 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_a01
_database_code_depnum_ccdc_archive 'CCDC 1044471'
_audit_update_record             
;
2015-01-20 deposited with the CCDC.
2015-03-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        Zr-TCPS
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C28 H16 O16 Si Zr3 '
_chemical_formula_sum            'C28 H16 O16 Si Zr3'
_chemical_formula_weight         910.16

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'I 4/m'

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

_cell_length_a                   15.228(3)
_cell_length_b                   15.228(3)
_cell_length_c                   28.791(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     6676(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3362
_cell_measurement_theta_min      1.41
_cell_measurement_theta_max      26.00

_exptl_crystal_description       diamond-like
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.906
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1784.0
_exptl_absorpt_coefficient_mu    0.514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.904
_exptl_absorpt_correction_T_max  0.950
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2003)'

_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  'Bruker Apex2 CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            24824
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_sigmaI/netI    0.0219
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         1.41
_diffrn_reflns_theta_max         26.00
_reflns_number_total             3362
_reflns_number_gt                2899
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2005)'
_computing_cell_refinement       'SAINT (Bruker, 2005)'
_computing_data_reduction        SAINT
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    SHELXTL
_computing_publication_material  SHELXTL

loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.013 -0.004 -0.004 4157 1288 ' '
_platon_squeeze_details          ?

_refine_special_details          SQUEEZE

_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)+(0.0656P)²+3.3121P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3362
_refine_ls_number_parameters     114
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0343
_refine_ls_wR_factor_ref         0.1114
_refine_ls_wR_factor_gt          0.1090
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_restrained_S_all      1.165
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.003

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
Zr1 Zr 0.84321(2) 0.05007(2) 0.5000 0.03748(14) Uani 1 2 d S . .
Zr2 Zr 1.0000 0.0000 0.414565(13) 0.03231(14) Uani 1 4 d S . .
Si1 Si 0.5000 0.0000 0.2500 0.0359(3) Uani 1 4 d S . .
O1 O 0.78109(13) 0.06858(17) 0.42933(7) 0.0642(6) Uani 1 1 d . . .
O2 O 0.88158(12) 0.03373(12) 0.37516(6) 0.0440(4) Uani 1 1 d . . .
O3 O 0.89678(19) -0.05376(15) 0.54138(7) 0.0853(10) Uani 1 1 d . . .
O1W O 0.7167(2) -0.0214(3) 0.5000 0.0746(9) Uani 1 2 d S . .
O2W O 0.7817(2) 0.1797(2) 0.5000 0.0652(8) Uani 1 2 d S . .
C1 C 0.6785(2) -0.0073(3) 0.28007(10) 0.0752(11) Uani 1 1 d . . .
H1A H 0.6886 -0.0378 0.2526 0.090 Uiso 1 1 calc R . .
C2 C 0.7473(2) 0.0048(3) 0.31068(11) 0.0774(11) Uani 1 1 d . . .
H2A H 0.8030 -0.0159 0.3032 0.093 Uiso 1 1 calc R . .
C3 C 0.73345(18) 0.04776(19) 0.35253(9) 0.0486(6) Uani 1 1 d . . .
C4 C 0.6515(2) 0.0817(2) 0.36121(11) 0.0660(9) Uani 1 1 d . . .
H4A H 0.6413 0.1124 0.3886 0.079 Uiso 1 1 calc R . .
C5 C 0.5844(2) 0.0708(2) 0.32971(11) 0.0640(9) Uani 1 1 d . . .
H5A H 0.5298 0.0954 0.3360 0.077 Uiso 1 1 calc R . .
C6 C 0.59598(16) 0.02413(18) 0.28885(8) 0.0422(5) Uani 1 1 d . . .
C7 C 0.80363(18) 0.05131(19) 0.38818(9) 0.0485(6) Uani 1 1 d . . .


_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
Zr1 O3 2.130(2) 4_665 ?
Zr1 O3 2.130(2) 11_666 ?
Zr1 O3 2.141(2) 10_556 ?
Zr1 O3 2.141(2) . ?
Zr1 O2W 2.185(3) . ?
Zr1 O1W 2.212(3) . ?
Zr1 O1 2.2614(19) . ?
Zr1 O1 2.2614(19) 10_556 ?
Zr1 Zr2 3.5117(6) 9_756 ?
Zr1 Zr2 3.5117(6) . ?
Zr1 Zr1 3.5445(8) 11_666 ?
Zr1 Zr1 3.5445(8) 3_645 ?
Zr2 O3 2.179(2) 9_756 ?
Zr2 O3 2.179(2) 11_666 ?
Zr2 O3 2.179(2) 10_556 ?
Zr2 O3 2.179(2) 12_646 ?
Zr2 O2 2.1915(17) . ?
Zr2 O2 2.1915(17) 3_645 ?
Zr2 O2 2.1915(17) 4_665 ?
Zr2 O2 2.1915(17) 2_755 ?
Zr2 Zr1 3.5117(6) 11_666 ?
Zr2 Zr1 3.5117(6) 9_756 ?
Zr2 Zr1 3.5117(6) 3_645 ?
Si1 C6 1.877(2) . ?
Si1 C6 1.877(2) 16_545 ?
Si1 C6 1.877(2) 2_655 ?
Si1 C6 1.877(2) 15 ?
O1 C7 1.261(3) . ?
O2 C7 1.273(3) . ?
O3 Zr1 2.130(2) 3_645 ?
O3 Zr2 2.179(2) 9_756 ?
C1 C6 1.368(4) . ?
C1 C2 1.381(4) . ?
C2 C3 1.387(4) . ?
C3 C4 1.374(4) . ?
C3 C7 1.483(4) . ?
C4 C5 1.377(4) . ?
C5 C6 1.386(4) . ?

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
O3 Zr1 O3 68.03(12) 4_665 11_666 ?
O3 Zr1 O3 108.13(17) 4_665 10_556 ?
O3 Zr1 O3 71.86(13) 11_666 10_556 ?
O3 Zr1 O3 71.86(13) 4_665 . ?
O3 Zr1 O3 108.13(17) 11_666 . ?
O3 Zr1 O3 67.61(11) 10_556 . ?
O3 Zr1 O2W 88.43(11) 4_665 . ?
O3 Zr1 O2W 88.43(11) 11_666 . ?
O3 Zr1 O2W 146.15(5) 10_556 . ?
O3 Zr1 O2W 146.15(5) . . ?
O3 Zr1 O1W 145.93(6) 4_665 . ?
O3 Zr1 O1W 145.93(6) 11_666 . ?
O3 Zr1 O1W 88.20(12) 10_556 . ?
O3 Zr1 O1W 88.20(12) . . ?
O2W Zr1 O1W 94.07(13) . . ?
O3 Zr1 O1 139.82(8) 4_665 . ?
O3 Zr1 O1 75.96(9) 11_666 . ?
O3 Zr1 O1 75.57(9) 10_556 . ?
O3 Zr1 O1 138.76(8) . . ?
O2W Zr1 O1 73.02(7) . . ?
O1W Zr1 O1 72.37(7) . . ?
O3 Zr1 O1 75.96(9) 4_665 10_556 ?
O3 Zr1 O1 139.82(8) 11_666 10_556 ?
O3 Zr1 O1 138.76(8) 10_556 10_556 ?
O3 Zr1 O1 75.57(9) . 10_556 ?
O2W Zr1 O1 73.02(7) . 10_556 ?
O1W Zr1 O1 72.37(7) . 10_556 ?
O1 Zr1 O1 128.25(10) . 10_556 ?
O3 Zr1 Zr2 35.89(7) 4_665 9_756 ?
O3 Zr1 Zr2 88.48(8) 11_666 9_756 ?
O3 Zr1 Zr2 88.30(8) 10_556 9_756 ?
O3 Zr1 Zr2 35.99(7) . 9_756 ?
O2W Zr1 Zr2 119.19(6) . 9_756 ?
O1W Zr1 Zr2 119.02(6) . 9_756 ?
O1 Zr1 Zr2 160.33(5) . 9_756 ?
O1 Zr1 Zr2 71.41(5) 10_556 9_756 ?
O3 Zr1 Zr2 88.48(8) 4_665 . ?
O3 Zr1 Zr2 35.89(7) 11_666 . ?
O3 Zr1 Zr2 35.99(7) 10_556 . ?
O3 Zr1 Zr2 88.30(8) . . ?
O2W Zr1 Zr2 119.19(6) . . ?
O1W Zr1 Zr2 119.02(6) . . ?
O1 Zr1 Zr2 71.41(5) . . ?
O1 Zr1 Zr2 160.33(5) 10_556 . ?
Zr2 Zr1 Zr2 88.925(19) 9_756 . ?
O3 Zr1 Zr1 34.01(6) 4_665 11_666 ?
O3 Zr1 Zr1 34.01(6) 11_666 11_666 ?
O3 Zr1 Zr1 90.00(8) 10_556 11_666 ?
O3 Zr1 Zr1 90.00(8) . 11_666 ?
O2W Zr1 Zr1 88.11(9) . 11_666 ?
O1W Zr1 Zr1 177.83(10) . 11_666 ?
O1 Zr1 Zr1 108.34(6) . 11_666 ?
O1 Zr1 Zr1 108.34(6) 10_556 11_666 ?
Zr2 Zr1 Zr1 59.691(6) 9_756 11_666 ?
Zr2 Zr1 Zr1 59.691(6) . 11_666 ?
O3 Zr1 Zr1 90.00(8) 4_665 3_645 ?
O3 Zr1 Zr1 90.00(8) 11_666 3_645 ?
O3 Zr1 Zr1 33.81(6) 10_556 3_645 ?
O3 Zr1 Zr1 33.81(6) . 3_645 ?
O2W Zr1 Zr1 178.11(10) . 3_645 ?
O1W Zr1 Zr1 87.83(10) . 3_645 ?
O1 Zr1 Zr1 107.61(6) . 3_645 ?
O1 Zr1 Zr1 107.61(6) 10_556 3_645 ?
Zr2 Zr1 Zr1 59.691(6) 9_756 3_645 ?
Zr2 Zr1 Zr1 59.691(6) . 3_645 ?
Zr1 Zr1 Zr1 90.0 11_666 3_645 ?
O3 Zr2 O3 70.20(8) 9_756 11_666 ?
O3 Zr2 O3 108.81(16) 9_756 10_556 ?
O3 Zr2 O3 70.20(8) 11_666 10_556 ?
O3 Zr2 O3 70.20(8) 9_756 12_646 ?
O3 Zr2 O3 108.81(16) 11_666 12_646 ?
O3 Zr2 O3 70.20(8) 10_556 12_646 ?
O3 Zr2 O2 143.77(7) 9_756 . ?
O3 Zr2 O2 79.81(8) 11_666 . ?
O3 Zr2 O2 78.22(8) 10_556 . ?
O3 Zr2 O2 141.21(7) 12_646 . ?
O3 Zr2 O2 141.21(7) 9_756 3_645 ?
O3 Zr2 O2 143.77(7) 11_666 3_645 ?
O3 Zr2 O2 79.81(8) 10_556 3_645 ?
O3 Zr2 O2 78.22(8) 12_646 3_645 ?
O2 Zr2 O2 74.46(4) . 3_645 ?
O3 Zr2 O2 79.81(8) 9_756 4_665 ?
O3 Zr2 O2 78.22(8) 11_666 4_665 ?
O3 Zr2 O2 141.21(7) 10_556 4_665 ?
O3 Zr2 O2 143.77(7) 12_646 4_665 ?
O2 Zr2 O2 74.46(4) . 4_665 ?
O2 Zr2 O2 117.65(9) 3_645 4_665 ?
O3 Zr2 O2 78.22(8) 9_756 2_755 ?
O3 Zr2 O2 141.21(7) 11_666 2_755 ?
O3 Zr2 O2 143.77(7) 10_556 2_755 ?
O3 Zr2 O2 79.81(8) 12_646 2_755 ?
O2 Zr2 O2 117.65(9) . 2_755 ?
O2 Zr2 O2 74.46(4) 3_645 2_755 ?
O2 Zr2 O2 74.46(4) 4_665 2_755 ?
O3 Zr2 Zr1 34.95(6) 9_756 11_666 ?
O3 Zr2 Zr1 35.27(6) 11_666 11_666 ?
O3 Zr2 Zr1 90.25(8) 10_556 11_666 ?
O3 Zr2 Zr1 90.06(7) 12_646 11_666 ?
O2 Zr2 Zr1 112.45(5) . 11_666 ?
O2 Zr2 Zr1 166.64(5) 3_645 11_666 ?
O2 Zr2 Zr1 75.66(5) 4_665 11_666 ?
O2 Zr2 Zr1 110.08(5) 2_755 11_666 ?
O3 Zr2 Zr1 35.27(6) 9_756 9_756 ?
O3 Zr2 Zr1 90.25(8) 11_666 9_756 ?
O3 Zr2 Zr1 90.06(7) 10_556 9_756 ?
O3 Zr2 Zr1 34.95(6) 12_646 9_756 ?
O2 Zr2 Zr1 166.64(5) . 9_756 ?
O2 Zr2 Zr1 110.08(5) 3_645 9_756 ?
O2 Zr2 Zr1 112.45(5) 4_665 9_756 ?
O2 Zr2 Zr1 75.66(5) 2_755 9_756 ?
Zr1 Zr2 Zr1 60.618(11) 11_666 9_756 ?
O3 Zr2 Zr1 90.25(8) 9_756 3_645 ?
O3 Zr2 Zr1 90.06(7) 11_666 3_645 ?
O3 Zr2 Zr1 34.95(6) 10_556 3_645 ?
O3 Zr2 Zr1 35.27(6) 12_646 3_645 ?
O2 Zr2 Zr1 110.08(5) . 3_645 ?
O2 Zr2 Zr1 75.66(5) 3_645 3_645 ?
O2 Zr2 Zr1 166.64(5) 4_665 3_645 ?
O2 Zr2 Zr1 112.45(5) 2_755 3_645 ?
Zr1 Zr2 Zr1 91.075(19) 11_666 3_645 ?
Zr1 Zr2 Zr1 60.618(11) 9_756 3_645 ?
O3 Zr2 Zr1 90.06(7) 9_756 . ?
O3 Zr2 Zr1 34.95(6) 11_666 . ?
O3 Zr2 Zr1 35.27(6) 10_556 . ?
O3 Zr2 Zr1 90.25(8) 12_646 . ?
O2 Zr2 Zr1 75.66(5) . . ?
O2 Zr2 Zr1 112.45(5) 3_645 . ?
O2 Zr2 Zr1 110.08(5) 4_665 . ?
O2 Zr2 Zr1 166.64(5) 2_755 . ?
Zr1 Zr2 Zr1 60.618(11) 11_666 . ?
Zr1 Zr2 Zr1 91.075(19) 9_756 . ?
Zr1 Zr2 Zr1 60.618(11) 3_645 . ?
C6 Si1 C6 110.80(7) . 16_545 ?
C6 Si1 C6 106.84(15) . 2_655 ?
C6 Si1 C6 110.80(7) 16_545 2_655 ?
C6 Si1 C6 110.80(7) . 15 ?
C6 Si1 C6 106.84(15) 16_545 15 ?
C6 Si1 C6 110.80(7) 2_655 15 ?
C7 O1 Zr1 134.86(18) . . ?
C7 O2 Zr2 131.60(16) . . ?
Zr1 O3 Zr1 112.18(10) 3_645 . ?
Zr1 O3 Zr2 109.16(11) 3_645 9_756 ?
Zr1 O3 Zr2 108.74(11) . 9_756 ?
C6 C1 C2 122.1(3) . . ?
C1 C2 C3 120.1(3) . . ?
C4 C3 C2 118.3(3) . . ?
C4 C3 C7 121.0(2) . . ?
C2 C3 C7 120.6(3) . . ?
C5 C4 C3 120.6(3) . . ?
C4 C5 C6 121.8(3) . . ?
C1 C6 C5 117.0(2) . . ?
C1 C6 Si1 122.5(2) . . ?
C5 C6 Si1 120.5(2) . . ?
O1 C7 O2 125.0(2) . . ?
O1 C7 C3 117.5(2) . . ?
O2 C7 C3 117.4(2) . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.540
_refine_diff_density_min         -0.781
_refine_diff_density_rms         0.081
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: DMF/formic acid'
_exptl_crystal_preparation       'Luminescent, semiconductor'
