# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2008


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Philip Lightfoot'
_publ_contact_author_address     
;
Department of Chemistry
University of St Andrews
St Andrews
Fife
KY16 9ST
UNITED KINGDOM
;

_publ_contact_author_email       PL@ST-ANDREWS.AC.UK

_publ_section_title              
;
A new hybrid framework material based on a
'superoctahedral' [V7O6F30]14- polyanion
;
loop_
_publ_author_name
'Philip Lightfoot'
'Thushitha Mahenthirarajah'

data_I
_database_code_depnum_ccdc_archive 'CCDC 669272'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '3(C20 H20 Cu F8 N4 O2 V2), 8(C H6 N), F6 V'
_chemical_formula_sum            'C68 H108 Cu3 F30 N20 O6 V7'
_chemical_formula_weight         2418.97

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'
N N 0.0061 0.0033 '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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   'P n -3 n'
_symmetry_space_group_name_Hall  '-P 4a 2bc 3'

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

_cell_length_a                   16.4943(14)
_cell_length_b                   16.4943(14)
_cell_length_c                   16.4943(14)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     4487.5(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    25150
_cell_measurement_theta_min      3.0
_cell_measurement_theta_max      25.3

_exptl_crystal_description       prism
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.790
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2444
_exptl_absorpt_coefficient_mu    1.512
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_T_max  0.89
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  'confocal optics'
_diffrn_measurement_device_type  'CCD Area Detector'
_diffrn_measurement_method       dtprofit.ref
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            25150
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_sigmaI/netI    0.0096
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.03
_diffrn_reflns_theta_max         25.32
_reflns_number_total             694
_reflns_number_gt                644
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear (rigaku Corp., 2004)'
_computing_cell_refinement       'CrystalClear (rigaku Corp., 2004)'
_computing_data_reduction        'CrystalClear (rigaku Corp., 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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^)+(0.0538P)^2^+4.6111P] 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     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         694
_refine_ls_number_parameters     64
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0340
_refine_ls_wR_factor_ref         0.1008
_refine_ls_wR_factor_gt          0.0988
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_restrained_S_all      1.183
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.7500 0.2500 0.2500 0.0102(3) Uani 1 8 d S . .
V1 V 0.51442(5) 0.2500 0.2500 0.0161(3) Uani 1 4 d S . .
V2 V 0.2500 0.2500 0.2500 0.0269(5) Uani 1 24 d S . .
F1 F 0.49362(9) 0.36289(8) 0.24372(8) 0.0234(4) Uani 1 1 d . . .
F2 F 0.3678(2) 0.2500 0.2500 0.0292(8) Uani 1 4 d S . .
O1 O 0.61408(19) 0.2500 0.2500 0.0174(7) Uani 1 4 d S . .
N1 N 0.7500 0.33729(11) 0.16271(11) 0.0127(6) Uani 1 2 d S . .
N2 N 0.38118(13) 0.38118(13) 0.11882(13) 0.0169(8) Uani 1 3 d S . .
C1 C 0.69232(13) 0.39545(13) 0.04315(13) 0.0174(5) Uani 1 1 d . . .
H1 H 0.6533 0.3931 0.0025 0.021 Uiso 1 1 calc R . .
C2 C 0.69331(13) 0.33759(14) 0.10439(12) 0.0159(5) Uani 1 1 d . . .
H2 H 0.6534 0.2978 0.1050 0.019 Uiso 1 1 calc R . .
C3 C 0.7500 0.45678(13) 0.04322(13) 0.0170(7) Uani 1 2 d S . .
H3 H 0.7500 0.4966 0.0034 0.020 Uiso 1 2 calc SR . .
C4 C 0.43250(16) 0.43250(16) 0.06750(16) 0.0294(11) Uani 1 3 d S . .
H4 H 0.4004(18) 0.3705(19) 0.1633(17) 0.032(8) Uiso 1 1 d . . .
H5 H 0.407(2) 0.437(2) 0.0135(19) 0.062(11) Uiso 1 1 d . . .

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
Cu1 0.0154(4) 0.0076(3) 0.0076(3) 0.000 0.000 0.000
V1 0.0173(4) 0.0155(3) 0.0155(3) 0.000 0.000 0.000
V2 0.0269(5) 0.0269(5) 0.0269(5) 0.000 0.000 0.000
F1 0.0265(8) 0.0145(8) 0.0293(9) 0.0009(5) -0.0054(6) 0.0000(5)
F2 0.0362(18) 0.0258(10) 0.0258(10) 0.000 0.000 0.000
O1 0.0122(15) 0.0201(11) 0.0201(11) 0.000 0.000 0.000
N1 0.0174(13) 0.0103(8) 0.0103(8) -0.0015(10) -0.0007(7) -0.0007(7)
N2 0.0169(8) 0.0169(8) 0.0169(8) -0.0017(9) -0.0017(9) 0.0017(9)
C1 0.0208(12) 0.0178(11) 0.0136(11) 0.0000(8) -0.0036(9) 0.0038(9)
C2 0.0191(11) 0.0142(11) 0.0145(11) -0.0008(9) -0.0007(8) -0.0014(8)
C3 0.0271(18) 0.0120(10) 0.0120(10) 0.0028(12) 0.0027(9) 0.0027(9)
C4 0.0294(11) 0.0294(11) 0.0294(11) 0.0045(11) 0.0045(11) -0.0045(11)

_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
Cu1 N1 2.036(3) 3_655 ?
Cu1 N1 2.036(3) 4_655 ?
Cu1 N1 2.036(3) 2 ?
Cu1 N1 2.036(3) . ?
Cu1 O1 2.242(3) . ?
Cu1 O1 2.242(3) 3_655 ?
V1 O1 1.644(3) . ?
V1 F1 1.8963(13) 24 ?
V1 F1 1.8963(13) 2 ?
V1 F1 1.8963(13) . ?
V1 F1 1.8963(13) 23 ?
V1 F2 2.419(3) . ?
V2 F2 1.943(3) 11 ?
V2 F2 1.943(3) 7 ?
V2 F2 1.943(3) 3 ?
V2 F2 1.943(3) 5 ?
V2 F2 1.943(3) . ?
V2 F2 1.943(3) 9 ?
N1 C2 1.341(3) 21_655 ?
N1 C2 1.341(3) . ?
N2 C4 1.466(6) . ?
N2 H4 0.82(3) . ?
C1 C3 1.389(3) . ?
C1 C2 1.390(3) . ?
C1 H1 0.9300 . ?
C2 H2 0.9300 . ?
C3 C1 1.389(3) 21_655 ?
C3 H3 0.9300 . ?
C4 H5 0.99(3) . ?

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
N1 Cu1 N1 180.00(14) 3_655 4_655 ?
N1 Cu1 N1 90.0 3_655 2 ?
N1 Cu1 N1 90.0 4_655 2 ?
N1 Cu1 N1 90.0 3_655 . ?
N1 Cu1 N1 90.0 4_655 . ?
N1 Cu1 N1 180.00(7) 2 . ?
N1 Cu1 O1 90.0 3_655 . ?
N1 Cu1 O1 90.0 4_655 . ?
N1 Cu1 O1 90.0 2 . ?
N1 Cu1 O1 90.0 . . ?
N1 Cu1 O1 90.0 3_655 3_655 ?
N1 Cu1 O1 90.0 4_655 3_655 ?
N1 Cu1 O1 90.0 2 3_655 ?
N1 Cu1 O1 90.0 . 3_655 ?
O1 Cu1 O1 180.0 . 3_655 ?
O1 V1 F1 100.42(5) . 24 ?
O1 V1 F1 100.42(5) . 2 ?
F1 V1 F1 88.124(19) 24 2 ?
O1 V1 F1 100.42(5) . . ?
F1 V1 F1 88.124(18) 24 . ?
F1 V1 F1 159.15(10) 2 . ?
O1 V1 F1 100.42(5) . 23 ?
F1 V1 F1 159.15(10) 24 23 ?
F1 V1 F1 88.124(18) 2 23 ?
F1 V1 F1 88.124(18) . 23 ?
O1 V1 F2 180.0 . . ?
F1 V1 F2 79.58(5) 24 . ?
F1 V1 F2 79.58(5) 2 . ?
F1 V1 F2 79.58(5) . . ?
F1 V1 F2 79.58(5) 23 . ?
F2 V2 F2 90.0 11 7 ?
F2 V2 F2 90.0 11 3 ?
F2 V2 F2 90.0 7 3 ?
F2 V2 F2 90.0 11 5 ?
F2 V2 F2 180.0 7 5 ?
F2 V2 F2 90.0 3 5 ?
F2 V2 F2 90.0 11 . ?
F2 V2 F2 90.0 7 . ?
F2 V2 F2 180.0 3 . ?
F2 V2 F2 90.0 5 . ?
F2 V2 F2 180.0 11 9 ?
F2 V2 F2 90.0 7 9 ?
F2 V2 F2 90.0 3 9 ?
F2 V2 F2 90.0 5 9 ?
F2 V2 F2 90.0 . 9 ?
V2 F2 V1 180.0 . . ?
V1 O1 Cu1 180.0 . . ?
C2 N1 C2 118.7(3) 21_655 . ?
C2 N1 Cu1 120.64(14) 21_655 . ?
C2 N1 Cu1 120.64(14) . . ?
C4 N2 H4 115(2) . . ?
C3 C1 C2 119.4(2) . . ?
C3 C1 H1 120.3 . . ?
C2 C1 H1 120.3 . . ?
N1 C2 C1 122.1(2) . . ?
N1 C2 H2 118.9 . . ?
C1 C2 H2 118.9 . . ?
C1 C3 C1 118.1(3) . 21_655 ?
C1 C3 H3 121.0 . . ?
C1 C3 H3 121.0 21_655 . ?
N2 C4 H5 108(2) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N2 H4 F1 0.82(3) 2.03(3) 2.7884(15) 153(3) .
N2 H4 F2 0.82(3) 2.51(3) 3.068(3) 127(3) .

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        25.32
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.069