# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2013

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
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#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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#  data retrieval see:
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#  from this site to visualise CIF-encoded structures and 
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data_ZTOF-2

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '[Zn6Ti2(ondc)6(dabco)(CO3)(OH2)3]'
_chemical_formula_sum            'C79 H48 N2 O36 Ti2 Zn6'
_chemical_formula_weight         2089.21

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 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'
N N 0.0059 0.0032 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0105 0.0059 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2937 1.3976 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2746 0.4347 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P6(3)/m

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

_cell_length_a                   20.171(3)
_cell_length_b                   20.171(3)
_cell_length_c                   26.197(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     9231(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'Hexagonal prism'
_exptl_crystal_colour            Orange
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.752
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2096
_exptl_absorpt_coefficient_mu    0.820
_exptl_absorpt_correction_type   semi-empirical
_exptl_absorpt_correction_T_min  0.7245
_exptl_absorpt_correction_T_max  0.8531
_exptl_absorpt_process_details   'HKL3000 Scalepack'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.69999
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_source         'PLSII 2D bending magnet'
_diffrn_radiation_monochromator  'Si(111) double crystal monochromator'
_diffrn_measurement_device_type  'ADSC Q210 CCD area detector'
_diffrn_measurement_method       'omega scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            106147
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_sigmaI/netI    0.0266
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_theta_min         1.91
_diffrn_reflns_theta_max         31.00
_reflns_number_total             10470
_reflns_number_gt                6300
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'PAL ADSC Quantum-210 ADX Program'
_computing_cell_refinement       HKL3000
_computing_data_reduction        HKL3000
_computing_structure_solution    'Bruker SHELXTL-XS'
_computing_structure_refinement  'Bruker SHELXTL-XL'
_computing_molecular_graphics    'Diamond 3'
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F^2^ against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F^2^, conventional R-factors R are based 
 on F, with F set to zero for negative F^2^. The threshold expression of 
 F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F^2^ 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/[\s^2^(Fo^2^)+(0.1898P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/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       0.050(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         10470
_refine_ls_number_parameters     195
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1081
_refine_ls_R_factor_gt           0.0850
_refine_ls_wR_factor_ref         0.2647
_refine_ls_wR_factor_gt          0.2453
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_restrained_S_all      0.997
_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
Zn1 Zn -1.0000 -1.0000 0.624052(15) 0.05502(18) Uani 1 3 d S . .
Zn2 Zn -1.0000 -1.0000 0.5000 0.0504(2) Uani 1 6 d S . .
Zn3 Zn -0.62189(3) -0.43463(3) 0.7500 0.0694(2) Uani 1 2 d S . .
Ti1 Ti -0.6667 -0.3333 0.59294(3) 0.0643(2) Uani 1 3 d S . .
N1 N -1.0000 -1.0000 0.70179(13) 0.0561(8) Uani 1 3 d S . .
O1 O -0.94162(12) -0.89015(11) 0.61408(6) 0.0630(5) Uani 1 1 d . . .
O2 O -1.00635(10) -0.91622(10) 0.54160(6) 0.0572(4) Uani 1 1 d . . .
O3 O -0.67721(13) -0.50017(12) 0.69112(7) 0.0723(5) Uani 1 1 d . . .
O4 O -0.64911(11) -0.40054(12) 0.64177(8) 0.0677(5) Uani 1 1 d . . .
O5 O -0.72753(13) -0.42361(12) 0.55713(7) 0.0688(5) Uani 1 1 d . . .
O6 O -0.60214(18) -0.33119(18) 0.7500 0.0727(7) Uani 1 2 d S . .
O7 O -0.5232(2) -0.4360(3) 0.7500 0.1177(14) Uani 1 2 d S . .
C1 C -0.91861(18) -0.78627(17) 0.56153(8) 0.0627(6) Uani 1 1 d . . .
C2 C -0.86760(18) -0.73522(17) 0.59568(10) 0.0659(7) Uani 1 1 d . . .
H2 H -0.8575 -0.7536 0.6264 0.079 Uiso 1 1 calc R . .
C3 C -0.82964(17) -0.65601(16) 0.58637(9) 0.0617(6) Uani 1 1 d . . .
C4 C -0.77812(19) -0.60235(17) 0.62097(10) 0.0696(7) Uani 1 1 d . . .
H4 H -0.7672 -0.6200 0.6517 0.083 Uiso 1 1 calc R . .
C5 C -0.74274(19) -0.52524(18) 0.61215(11) 0.0688(7) Uani 1 1 d . . .
C6 C -0.75809(17) -0.49778(18) 0.56535(11) 0.0663(6) Uani 1 1 d . . .
C7 C -0.80854(17) -0.54918(17) 0.53080(11) 0.0682(7) Uani 1 1 d . . .
H7 H -0.8195 -0.5309 0.5004 0.082 Uiso 1 1 calc R . .
C8 C -0.84440(17) -0.62855(16) 0.53956(10) 0.0639(6) Uani 1 1 d . . .
C9 C -0.8979(2) -0.6840(2) 0.50457(10) 0.0727(8) Uani 1 1 d . . .
H9 H -0.9083 -0.6671 0.4733 0.087 Uiso 1 1 calc R . .
C10 C -0.93385(19) -0.75983(17) 0.51484(11) 0.0701(7) Uani 1 1 d . . .
H10 H -0.9692 -0.7955 0.4910 0.084 Uiso 1 1 calc R . .
C11 C -0.95840(16) -0.86942(16) 0.57250(9) 0.0598(6) Uani 1 1 d . . .
C12 C -0.68777(18) -0.47189(18) 0.65036(11) 0.0697(7) Uani 1 1 d . . .
C13 C -0.6667 -0.3333 0.7500 0.0661(15) Uani 1 6 d S . .
C14 C -1.03657(18) -1.07951(17) 0.72036(9) 0.0676(7) Uani 1 1 d . . .
H14A H -1.0082 -1.1044 0.7076 0.081 Uiso 1 1 calc R . .
H14B H -1.0898 -1.1087 0.7075 0.081 Uiso 1 1 calc R . .

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
Zn1 0.0689(2) 0.0689(2) 0.0273(2) 0.000 0.000 0.03444(12)
Zn2 0.0627(3) 0.0627(3) 0.0257(3) 0.000 0.000 0.03134(13)
Zn3 0.0745(3) 0.0770(3) 0.0470(3) 0.000 0.000 0.0305(2)
Ti1 0.0642(3) 0.0642(3) 0.0644(5) 0.000 0.000 0.03212(16)
N1 0.0691(13) 0.0691(13) 0.0301(13) 0.000 0.000 0.0346(7)
O1 0.0813(12) 0.0640(10) 0.0340(7) -0.0003(7) -0.0008(7) 0.0291(9)
O2 0.0698(10) 0.0671(10) 0.0365(7) -0.0066(7) -0.0013(7) 0.0354(8)
O3 0.0870(14) 0.0732(12) 0.0554(10) -0.0095(8) -0.0185(9) 0.0392(10)
O4 0.0727(11) 0.0686(11) 0.0621(10) -0.0056(9) -0.0097(9) 0.0357(9)
O5 0.0730(11) 0.0682(11) 0.0616(10) 0.0023(8) -0.0078(8) 0.0326(10)
O6 0.0805(18) 0.0765(17) 0.0617(15) 0.000 0.000 0.0397(15)
O7 0.083(2) 0.155(4) 0.113(3) 0.000 0.000 0.058(3)
C1 0.0817(17) 0.0677(15) 0.0382(10) -0.0025(9) -0.0018(10) 0.0369(13)
C2 0.0829(17) 0.0701(15) 0.0444(11) 0.0022(11) -0.0070(11) 0.0380(14)
C3 0.0747(16) 0.0630(14) 0.0456(11) -0.0024(10) -0.0059(10) 0.0330(12)
C4 0.0804(18) 0.0684(16) 0.0536(14) -0.0020(11) -0.0155(12) 0.0325(14)
C5 0.0795(18) 0.0720(16) 0.0575(14) -0.0050(12) -0.0095(13) 0.0397(14)
C6 0.0654(15) 0.0685(16) 0.0622(15) -0.0020(12) -0.0055(11) 0.0313(13)
C7 0.0758(17) 0.0765(17) 0.0563(14) 0.0017(12) -0.0057(12) 0.0411(14)
C8 0.0733(15) 0.0684(15) 0.0465(12) 0.0051(10) -0.0068(11) 0.0328(13)
C9 0.089(2) 0.0717(17) 0.0498(13) 0.0043(11) -0.0151(12) 0.0344(16)
C10 0.0858(19) 0.0676(15) 0.0461(11) -0.0023(11) -0.0135(13) 0.0304(14)
C11 0.0760(16) 0.0731(15) 0.0363(9) -0.0060(10) -0.0039(10) 0.0417(13)
C12 0.0745(17) 0.0737(17) 0.0640(16) -0.0065(13) -0.0081(13) 0.0394(14)
C13 0.069(2) 0.069(2) 0.059(3) 0.000 0.000 0.0347(12)
C14 0.0862(18) 0.0744(16) 0.0321(9) 0.0039(10) 0.0030(10) 0.0325(14)

_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
Zn1 O1 1.9379(19) 3_435 ?
Zn1 O1 1.9380(19) . ?
Zn1 O1 1.9380(19) 2_345 ?
Zn1 N1 2.037(3) . ?
Zn2 O2 2.0680(17) 9_456 ?
Zn2 O2 2.0680(17) 3_435 ?
Zn2 O2 2.0680(17) 7_336 ?
Zn2 O2 2.0680(17) 2_345 ?
Zn2 O2 2.0680(17) 8_546 ?
Zn2 O2 2.0680(17) . ?
Zn3 O6 1.919(3) . ?
Zn3 O3 1.9741(19) . ?
Zn3 O3 1.9742(19) 10_557 ?
Zn3 O7 2.005(4) . ?
Ti1 O5 1.862(2) . ?
Ti1 O5 1.862(2) 3_445 ?
Ti1 O5 1.862(2) 2_455 ?
Ti1 O4 2.020(2) 3_445 ?
Ti1 O4 2.020(2) 2_455 ?
Ti1 O4 2.020(2) . ?
N1 C14 1.473(3) . ?
N1 C14 1.473(3) 2_345 ?
N1 C14 1.473(3) 3_435 ?
O1 C11 1.272(3) . ?
O2 C11 1.252(3) . ?
O3 C12 1.277(3) . ?
O4 C12 1.268(4) . ?
O5 C6 1.320(4) . ?
O6 C13 1.281(3) . ?
C1 C2 1.364(4) . ?
C1 C10 1.428(4) . ?
C1 C11 1.481(4) . ?
C2 C3 1.405(4) . ?
C3 C4 1.396(4) . ?
C3 C8 1.437(4) . ?
C4 C5 1.368(4) . ?
C5 C6 1.441(4) . ?
C5 C12 1.482(4) . ?
C6 C7 1.369(4) . ?
C7 C8 1.407(4) . ?
C8 C9 1.431(4) . ?
C9 C10 1.353(4) . ?
C13 O6 1.281(3) 2_455 ?
C13 O6 1.281(3) 3_445 ?
C14 C14 1.553(5) 10_557 ?

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
O1 Zn1 O1 118.21(2) 3_435 . ?
O1 Zn1 O1 118.21(2) 3_435 2_345 ?
O1 Zn1 O1 118.21(2) . 2_345 ?
O1 Zn1 N1 97.75(5) 3_435 . ?
O1 Zn1 N1 97.75(5) . . ?
O1 Zn1 N1 97.75(5) 2_345 . ?
O2 Zn2 O2 180.00(9) 9_456 3_435 ?
O2 Zn2 O2 94.78(6) 9_456 7_336 ?
O2 Zn2 O2 85.22(6) 3_435 7_336 ?
O2 Zn2 O2 85.22(6) 9_456 2_345 ?
O2 Zn2 O2 94.78(6) 3_435 2_345 ?
O2 Zn2 O2 85.22(6) 7_336 2_345 ?
O2 Zn2 O2 94.78(6) 9_456 8_546 ?
O2 Zn2 O2 85.22(6) 3_435 8_546 ?
O2 Zn2 O2 94.78(6) 7_336 8_546 ?
O2 Zn2 O2 180.00(7) 2_345 8_546 ?
O2 Zn2 O2 85.22(6) 9_456 . ?
O2 Zn2 O2 94.78(6) 3_435 . ?
O2 Zn2 O2 180.00(9) 7_336 . ?
O2 Zn2 O2 94.78(6) 2_345 . ?
O2 Zn2 O2 85.22(6) 8_546 . ?
O6 Zn3 O3 117.95(8) . . ?
O6 Zn3 O3 117.95(8) . 10_557 ?
O3 Zn3 O3 102.78(13) . 10_557 ?
O6 Zn3 O7 110.34(18) . . ?
O3 Zn3 O7 102.90(12) . . ?
O3 Zn3 O7 102.90(12) 10_557 . ?
O5 Ti1 O5 96.85(9) . 3_445 ?
O5 Ti1 O5 96.85(9) . 2_455 ?
O5 Ti1 O5 96.85(9) 3_445 2_455 ?
O5 Ti1 O4 93.51(9) . 3_445 ?
O5 Ti1 O4 85.06(8) 3_445 3_445 ?
O5 Ti1 O4 169.15(9) 2_455 3_445 ?
O5 Ti1 O4 169.15(9) . 2_455 ?
O5 Ti1 O4 93.51(9) 3_445 2_455 ?
O5 Ti1 O4 85.06(8) 2_455 2_455 ?
O4 Ti1 O4 84.17(9) 3_445 2_455 ?
O5 Ti1 O4 85.06(8) . . ?
O5 Ti1 O4 169.15(9) 3_445 . ?
O5 Ti1 O4 93.51(9) 2_455 . ?
O4 Ti1 O4 84.16(9) 3_445 . ?
O4 Ti1 O4 84.17(9) 2_455 . ?
C14 N1 C14 109.65(15) . 2_345 ?
C14 N1 C14 109.66(15) . 3_435 ?
C14 N1 C14 109.65(15) 2_345 3_435 ?
C14 N1 Zn1 109.28(15) . . ?
C14 N1 Zn1 109.29(15) 2_345 . ?
C14 N1 Zn1 109.29(15) 3_435 . ?
C11 O1 Zn1 112.45(17) . . ?
C11 O2 Zn2 128.06(17) . . ?
C12 O3 Zn3 121.24(19) . . ?
C12 O4 Ti1 131.27(19) . . ?
C6 O5 Ti1 137.06(18) . . ?
C13 O6 Zn3 107.97(19) . . ?
C2 C1 C10 120.1(3) . . ?
C2 C1 C11 120.3(2) . . ?
C10 C1 C11 119.6(2) . . ?
C1 C2 C3 121.4(2) . . ?
C4 C3 C2 122.7(2) . . ?
C4 C3 C8 118.2(3) . . ?
C2 C3 C8 119.1(2) . . ?
C5 C4 C3 122.3(3) . . ?
C4 C5 C6 119.4(3) . . ?
C4 C5 C12 119.1(3) . . ?
C6 C5 C12 121.5(3) . . ?
O5 C6 C7 120.0(3) . . ?
O5 C6 C5 120.4(3) . . ?
C7 C6 C5 119.5(3) . . ?
C6 C7 C8 121.2(3) . . ?
C7 C8 C9 122.8(2) . . ?
C7 C8 C3 119.3(2) . . ?
C9 C8 C3 117.8(2) . . ?
C10 C9 C8 121.7(2) . . ?
C9 C10 C1 119.9(3) . . ?
O2 C11 O1 122.5(2) . . ?
O2 C11 C1 120.3(2) . . ?
O1 C11 C1 117.1(2) . . ?
O4 C12 O3 120.7(3) . . ?
O4 C12 C5 121.1(3) . . ?
O3 C12 C5 118.1(3) . . ?
O6 C13 O6 120.000(1) 2_455 3_445 ?
O6 C13 O6 120.001(1) 2_455 . ?
O6 C13 O6 119.999(1) 3_445 . ?
N1 C14 C14 109.28(15) . 10_557 ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        31.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         2.022
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.160

# SQUEEZE RESULTS (APPEND TO CIF)
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
1 -0.024 0.426 -0.004 6135.0 845.2
_platon_squeeze_details          
; ?
;
_database_code_depnum_ccdc_archive 'CCDC 959096'