# Electronic Supplementary Material (ESI) for Dalton Transactions
# 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.
#
#  This CIF is provided on the understanding that it is used for bona
#  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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_vbhd

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H9 N2 O7 V'
_chemical_formula_weight         368.17

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbcn

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

_cell_length_a                   16.9290(13)
_cell_length_b                   11.0728(9)
_cell_length_c                   15.1442(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2838.8(4)
_cell_formula_units_Z            8
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      2.41
_cell_measurement_theta_max      27.45

_exptl_crystal_description       Needle
_exptl_crystal_colour            Red
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.723
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1488
_exptl_absorpt_coefficient_mu    0.742
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  2.41
_exptl_absorpt_correction_T_max  27.45
_exptl_absorpt_process_details   Sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      273(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_reflns_number            21460
_diffrn_reflns_av_R_equivalents  0.0949
_diffrn_reflns_av_sigmaI/netI    0.0463
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         2.41
_diffrn_reflns_theta_max         27.45
_reflns_number_total             3236
_reflns_number_gt                2679
_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, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'murcury 3.1'

_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^)+(0.1000P)^2^+0.7149P] 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         3236
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0359
_refine_ls_wR_factor_ref         0.1180
_refine_ls_wR_factor_gt          0.1075
_refine_ls_goodness_of_fit_ref   0.818
_refine_ls_restrained_S_all      0.818
_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
V1 V 0.714643(19) 0.71853(3) 0.17825(2) 0.03165(14) Uani 1 1 d . . .
O6 O 0.73205(8) 0.59534(12) 0.09803(9) 0.0356(3) Uani 1 1 d . . .
O7 O 0.60370(8) 0.62232(12) 0.17367(8) 0.0363(3) Uani 1 1 d . . .
C1 C 0.60589(11) 0.53354(16) 0.12198(11) 0.0302(4) Uani 1 1 d . . .
C2 C 0.53831(11) 0.45293(16) 0.10638(11) 0.0311(4) Uani 1 1 d . . .
C3 C 0.46609(12) 0.48271(19) 0.14379(14) 0.0399(4) Uani 1 1 d . . .
H7 H 0.4613 0.5518 0.1783 0.048 Uiso 1 1 calc R . .
C6 C 0.47934(13) 0.27886(18) 0.03949(16) 0.0463(5) Uani 1 1 d . . .
H4 H 0.4836 0.2109 0.0037 0.056 Uiso 1 1 calc R . .
C7 C 0.54482(12) 0.35043(17) 0.05478(13) 0.0397(4) Uani 1 1 d . . .
H3 H 0.5933 0.3296 0.0303 0.048 Uiso 1 1 calc R . .
C4 C 0.40099(12) 0.4091(2) 0.12964(15) 0.0465(5) Uani 1 1 d . . .
H6 H 0.3527 0.4278 0.1556 0.056 Uiso 1 1 calc R . .
C5 C 0.40812(12) 0.30779(19) 0.07690(16) 0.0459(5) Uani 1 1 d . . .
H5 H 0.3643 0.2590 0.0667 0.055 Uiso 1 1 calc R . .
N1 N 0.67375(9) 0.51576(14) 0.08027(10) 0.0342(4) Uani 1 1 d . . .
H1 H 0.6803 0.4569 0.0440 0.041 Uiso 1 1 calc R . .
C8 C 0.71107(10) 0.68100(19) 0.36611(12) 0.0333(4) Uani 1 1 d . . .
C9 C 0.67229(11) 0.80175(17) 0.35607(11) 0.0308(4) Uani 1 1 d . . .
C13 C 0.62660(11) 0.92810(16) 0.24375(11) 0.0311(4) Uani 1 1 d . . .
C14 C 0.62167(11) 0.93071(18) 0.14450(12) 0.0357(4) Uani 1 1 d . . .
C10 C 0.64496(12) 0.87943(18) 0.42007(11) 0.0372(4) Uani 1 1 d . . .
H12 H 0.6517 0.8621 0.4797 0.045 Uiso 1 1 calc R . .
C12 C 0.59699(13) 1.00893(18) 0.30426(14) 0.0401(5) Uani 1 1 d . . .
H10 H 0.5708 1.0784 0.2860 0.048 Uiso 1 1 calc R . .
C11 C 0.60724(13) 0.98398(18) 0.39327(13) 0.0425(5) Uani 1 1 d . . .
H11 H 0.5886 1.0381 0.4353 0.051 Uiso 1 1 calc R . .
O4 O 0.66071(9) 0.84079(12) 0.10877(8) 0.0401(3) Uani 1 1 d . . .
O5 O 0.58415(9) 1.00596(15) 0.10477(10) 0.0526(4) Uani 1 1 d . . .
O2 O 0.72157(8) 0.63488(14) 0.43835(9) 0.0460(4) Uani 1 1 d . . .
O3 O 0.72959(8) 0.63264(12) 0.29099(10) 0.0381(3) Uani 1 1 d . . .
O1 O 0.80146(10) 0.77042(15) 0.17112(10) 0.0471(4) Uani 1 1 d . . .
N2 N 0.66373(9) 0.82849(13) 0.27054(9) 0.0288(3) Uani 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
V1 0.0340(2) 0.0314(2) 0.0295(2) -0.00393(12) 0.00646(11) -0.00436(12)
O6 0.0336(7) 0.0357(7) 0.0375(7) -0.0077(6) 0.0094(5) -0.0045(5)
O7 0.0356(7) 0.0356(7) 0.0378(7) -0.0108(5) 0.0085(5) -0.0055(6)
C1 0.0337(9) 0.0302(8) 0.0269(8) 0.0012(7) 0.0008(7) 0.0009(7)
C2 0.0334(9) 0.0300(9) 0.0300(8) 0.0029(7) -0.0016(7) -0.0009(7)
C3 0.0382(11) 0.0389(10) 0.0425(10) -0.0043(8) 0.0028(8) 0.0011(8)
C6 0.0440(12) 0.0364(11) 0.0585(13) -0.0097(9) 0.0012(10) -0.0050(9)
C7 0.0354(10) 0.0347(10) 0.0490(11) -0.0063(8) 0.0033(8) -0.0002(8)
C4 0.0325(10) 0.0478(12) 0.0592(13) 0.0009(10) 0.0060(9) -0.0001(9)
C5 0.0375(11) 0.0392(10) 0.0609(13) 0.0027(10) -0.0051(9) -0.0080(9)
N1 0.0349(9) 0.0312(8) 0.0366(8) -0.0090(6) 0.0048(6) -0.0026(6)
C8 0.0281(9) 0.0376(10) 0.0341(9) 0.0043(8) -0.0009(7) -0.0070(7)
C9 0.0317(9) 0.0346(9) 0.0261(8) 0.0014(7) -0.0010(7) -0.0069(7)
C13 0.0317(9) 0.0312(9) 0.0305(8) 0.0006(7) 0.0000(7) -0.0032(7)
C14 0.0362(10) 0.0403(10) 0.0307(9) 0.0047(8) -0.0008(7) -0.0065(8)
C10 0.0443(11) 0.0422(10) 0.0251(8) -0.0029(7) 0.0006(7) -0.0075(8)
C12 0.0433(11) 0.0346(10) 0.0425(10) -0.0015(8) 0.0023(8) 0.0052(8)
C11 0.0535(12) 0.0377(10) 0.0363(10) -0.0103(8) 0.0068(9) -0.0005(9)
O4 0.0528(9) 0.0418(8) 0.0256(6) 0.0010(5) 0.0030(5) -0.0023(7)
O5 0.0532(9) 0.0656(10) 0.0390(8) 0.0162(7) -0.0027(7) 0.0116(8)
O2 0.0447(8) 0.0536(9) 0.0396(8) 0.0180(7) -0.0030(6) -0.0027(6)
O3 0.0403(8) 0.0340(7) 0.0399(7) 0.0026(6) 0.0026(6) 0.0039(6)
O1 0.0414(9) 0.0491(10) 0.0508(9) -0.0031(7) 0.0097(7) -0.0119(7)
N2 0.0323(8) 0.0299(7) 0.0242(7) -0.0017(6) 0.0006(5) -0.0041(6)

_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
V1 O1 1.5818(16) . ?
V1 O6 1.8502(13) . ?
V1 O4 1.9425(14) . ?
V1 O3 1.9707(15) . ?
V1 N2 2.0442(14) . ?
V1 O7 2.1604(14) . ?
O6 N1 1.350(2) . ?
O7 C1 1.257(2) . ?
C1 N1 1.326(2) . ?
C1 C2 1.470(3) . ?
C2 C7 1.382(3) . ?
C2 C3 1.387(3) . ?
C3 C4 1.388(3) . ?
C3 H7 0.9300 . ?
C6 C5 1.370(3) . ?
C6 C7 1.382(3) . ?
C6 H4 0.9300 . ?
C7 H3 0.9300 . ?
C4 C5 1.382(3) . ?
C4 H6 0.9300 . ?
C5 H5 0.9300 . ?
N1 H1 0.8600 . ?
C8 O2 1.220(2) . ?
C8 O3 1.296(2) . ?
C8 C9 1.497(3) . ?
C9 N2 1.337(2) . ?
C9 C10 1.376(3) . ?
C13 N2 1.333(2) . ?
C13 C12 1.376(3) . ?
C13 C14 1.506(2) . ?
C14 O5 1.208(2) . ?
C14 O4 1.312(2) . ?
C10 C11 1.383(3) . ?
C10 H12 0.9300 . ?
C12 C11 1.387(3) . ?
C12 H10 0.9300 . ?
C11 H11 0.9300 . ?

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 V1 O6 94.30(7) . . ?
O1 V1 O4 98.43(8) . . ?
O6 V1 O4 103.48(6) . . ?
O1 V1 O3 96.61(7) . . ?
O6 V1 O3 101.11(6) . . ?
O4 V1 O3 149.99(6) . . ?
O1 V1 N2 102.83(7) . . ?
O6 V1 N2 162.78(6) . . ?
O4 V1 N2 75.94(6) . . ?
O3 V1 N2 75.48(6) . . ?
O1 V1 O7 169.98(7) . . ?
O6 V1 O7 75.75(5) . . ?
O4 V1 O7 85.28(6) . . ?
O3 V1 O7 84.34(6) . . ?
N2 V1 O7 87.08(5) . . ?
N1 O6 V1 119.70(10) . . ?
C1 O7 V1 112.33(11) . . ?
O7 C1 N1 116.00(16) . . ?
O7 C1 C2 123.50(16) . . ?
N1 C1 C2 120.50(16) . . ?
C7 C2 C3 119.76(18) . . ?
C7 C2 C1 121.82(17) . . ?
C3 C2 C1 118.41(16) . . ?
C2 C3 C4 119.81(19) . . ?
C2 C3 H7 120.1 . . ?
C4 C3 H7 120.1 . . ?
C5 C6 C7 120.16(19) . . ?
C5 C6 H4 119.9 . . ?
C7 C6 H4 119.9 . . ?
C6 C7 C2 120.10(19) . . ?
C6 C7 H3 119.9 . . ?
C2 C7 H3 119.9 . . ?
C5 C4 C3 119.78(19) . . ?
C5 C4 H6 120.1 . . ?
C3 C4 H6 120.1 . . ?
C6 C5 C4 120.37(19) . . ?
C6 C5 H5 119.8 . . ?
C4 C5 H5 119.8 . . ?
C1 N1 O6 116.21(14) . . ?
C1 N1 H1 121.9 . . ?
O6 N1 H1 121.9 . . ?
O2 C8 O3 125.4(2) . . ?
O2 C8 C9 121.91(18) . . ?
O3 C8 C9 112.70(16) . . ?
N2 C9 C10 120.51(17) . . ?
N2 C9 C8 110.11(15) . . ?
C10 C9 C8 129.36(16) . . ?
N2 C13 C12 120.50(17) . . ?
N2 C13 C14 110.24(15) . . ?
C12 C13 C14 129.23(17) . . ?
O5 C14 O4 125.65(18) . . ?
O5 C14 C13 122.65(18) . . ?
O4 C14 C13 111.67(16) . . ?
C9 C10 C11 118.15(17) . . ?
C9 C10 H12 120.9 . . ?
C11 C10 H12 120.9 . . ?
C13 C12 C11 118.19(18) . . ?
C13 C12 H10 120.9 . . ?
C11 C12 H10 120.9 . . ?
C10 C11 C12 120.65(18) . . ?
C10 C11 H11 119.7 . . ?
C12 C11 H11 119.7 . . ?
C14 O4 V1 122.84(11) . . ?
C8 O3 V1 122.01(13) . . ?
C13 N2 C9 121.97(15) . . ?
C13 N2 V1 118.92(11) . . ?
C9 N2 V1 119.01(12) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        27.45
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.391
_refine_diff_density_rms         0.142
_database_code_depnum_ccdc_archive 'CCDC 870238'
#######################################################################
#
#                 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.
#
#  This CIF is provided on the understanding that it is used for bona
#  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
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_sw

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H13 N2 O7 V'
_chemical_formula_weight         444.26

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P21/n

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

_cell_length_a                   12.3056(3)
_cell_length_b                   6.0449(2)
_cell_length_c                   26.4794(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 102.664(2)
_cell_angle_gamma                90.00
_cell_volume                     1921.78(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       Needle
_exptl_crystal_colour            Black
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             904
_exptl_absorpt_coefficient_mu    0.563
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.964
_exptl_absorpt_correction_T_max  0.976
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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_reflns_number            16721
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_sigmaI/netI    0.0411
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_theta_min         1.58
_diffrn_reflns_theta_max         27.55
_reflns_number_total             4414
_reflns_number_gt                3193
_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, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'murcury 2.4'

_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^)+(0.0452P)^2^+0.3563P] 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         4414
_refine_ls_number_parameters     271
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0390
_refine_ls_wR_factor_ref         0.1019
_refine_ls_wR_factor_gt          0.0918
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_restrained_S_all      1.034
_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
V1 V 0.37702(3) 1.05159(7) 0.151679(12) 0.03465(12) Uani 1 1 d . . .
O7 O 0.42838(11) 0.7915(3) 0.10682(5) 0.0407(4) Uani 1 1 d . . .
O4 O 0.29689(12) 1.1465(3) 0.08298(6) 0.0514(4) Uani 1 1 d . . .
O6 O 0.53018(11) 1.0908(2) 0.16037(5) 0.0354(3) Uani 1 1 d . . .
O3 O 0.39278(11) 0.8584(3) 0.21096(5) 0.0373(4) Uani 1 1 d . . .
O5 O 0.14571(15) 1.1283(4) 0.01891(7) 0.0935(8) Uani 1 1 d . . .
N1 N 0.59172(13) 0.9295(3) 0.14339(6) 0.0350(4) Uani 1 1 d . . .
N2 N 0.22912(12) 0.8811(3) 0.13937(6) 0.0338(4) Uani 1 1 d . . .
C5 C 0.6630(3) 0.2945(5) 0.02678(9) 0.0628(8) Uani 1 1 d . . .
H5 H 0.6907 0.1855 0.0082 0.075 Uiso 1 1 calc R . .
C12 C 0.8829(2) 1.1104(5) 0.19028(10) 0.0600(7) Uani 1 1 d . . .
H12 H 0.9274 1.2332 0.1885 0.072 Uiso 1 1 calc R . .
C4 C 0.5632(2) 0.2615(4) 0.04157(8) 0.0553(7) Uani 1 1 d . . .
H4 H 0.5235 0.1310 0.0328 0.066 Uiso 1 1 calc R . .
C11 C 0.9275(2) 0.9290(6) 0.21748(10) 0.0606(8) Uani 1 1 d . . .
H11 H 1.0025 0.9287 0.2340 0.073 Uiso 1 1 calc R . .
C16 C 0.11931(18) 0.6064(5) 0.16604(9) 0.0501(6) Uani 1 1 d . . .
H16 H 0.1082 0.5027 0.1903 0.060 Uiso 1 1 calc R . .
C3 C 0.52309(19) 0.4219(4) 0.06923(7) 0.0426(6) Uani 1 1 d . . .
H3 H 0.4548 0.4018 0.0782 0.051 Uiso 1 1 calc R . .
C6 C 0.7212(2) 0.4874(5) 0.03933(9) 0.0552(7) Uani 1 1 d . . .
H6 H 0.7869 0.5106 0.0282 0.066 Uiso 1 1 calc R . .
C19 C 0.15582(17) 0.9103(4) 0.09476(8) 0.0442(6) Uani 1 1 d . . .
C10 C 0.8635(2) 0.7472(5) 0.22081(8) 0.0552(7) Uani 1 1 d . . .
H10 H 0.8950 0.6237 0.2393 0.066 Uiso 1 1 calc R . .
C7 C 0.68321(18) 0.6472(4) 0.06825(8) 0.0429(5) Uani 1 1 d . . .
H7 H 0.7237 0.7766 0.0773 0.051 Uiso 1 1 calc R . .
C18 C 0.0588(2) 0.7892(5) 0.08395(9) 0.0649(8) Uani 1 1 d . . .
H18 H 0.0065 0.8093 0.0531 0.078 Uiso 1 1 calc R . .
C20 C 0.19812(19) 1.0753(5) 0.06137(8) 0.0556(7) Uani 1 1 d . . .
O1 O 0.36037(12) 1.2783(3) 0.17849(6) 0.0501(4) Uani 1 1 d . . .
C9 C 0.75122(18) 0.7467(4) 0.19658(7) 0.0432(6) Uani 1 1 d . . .
H9 H 0.7064 0.6254 0.1993 0.052 Uiso 1 1 calc R . .
C8 C 0.70806(15) 0.9292(4) 0.16851(7) 0.0341(5) Uani 1 1 d . . .
C17 C 0.0415(2) 0.6374(6) 0.12019(10) 0.0703(9) Uani 1 1 d . . .
H17 H -0.0237 0.5542 0.1137 0.084 Uiso 1 1 calc R . .
C13 C 0.77093(18) 1.1136(4) 0.16509(9) 0.0473(6) Uani 1 1 d . . .
H13 H 0.7397 1.2372 0.1465 0.057 Uiso 1 1 calc R . .
C1 C 0.53198(16) 0.7784(4) 0.11228(7) 0.0335(5) Uani 1 1 d . . .
C15 C 0.21341(15) 0.7347(4) 0.17424(7) 0.0332(5) Uani 1 1 d . . .
C2 C 0.58308(17) 0.6128(4) 0.08387(7) 0.0350(5) Uani 1 1 d . . .
C14 C 0.31151(16) 0.7322(4) 0.21968(7) 0.0328(5) Uani 1 1 d . . .
O2 O 0.31412(12) 0.6283(3) 0.25858(5) 0.0414(4) Uani 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
V1 0.02540(18) 0.0422(3) 0.03449(18) 0.00206(17) 0.00250(12) -0.00229(17)
O7 0.0276(7) 0.0536(11) 0.0400(7) -0.0097(7) 0.0054(5) -0.0101(7)
O4 0.0346(8) 0.0677(12) 0.0475(8) 0.0209(9) -0.0001(6) -0.0103(9)
O6 0.0281(7) 0.0374(9) 0.0392(7) -0.0049(7) 0.0043(5) -0.0026(7)
O3 0.0284(7) 0.0484(10) 0.0317(6) 0.0012(7) -0.0005(5) -0.0010(7)
O5 0.0572(11) 0.146(2) 0.0625(11) 0.0575(14) -0.0188(9) -0.0289(14)
N1 0.0263(8) 0.0386(11) 0.0381(8) -0.0053(8) 0.0026(6) -0.0022(8)
N2 0.0246(8) 0.0436(11) 0.0314(7) 0.0038(8) 0.0024(6) 0.0016(8)
C5 0.091(2) 0.0570(19) 0.0392(11) -0.0057(13) 0.0128(12) 0.0200(18)
C12 0.0371(13) 0.067(2) 0.0731(16) -0.0110(16) 0.0050(11) -0.0216(14)
C4 0.0854(19) 0.0373(15) 0.0377(11) -0.0040(12) 0.0015(12) -0.0057(15)
C11 0.0284(11) 0.088(2) 0.0589(14) -0.0113(16) -0.0053(10) -0.0017(15)
C16 0.0408(12) 0.0583(18) 0.0482(12) 0.0143(12) 0.0034(9) -0.0136(13)
C3 0.0519(13) 0.0404(15) 0.0322(9) 0.0033(10) 0.0022(9) -0.0096(12)
C6 0.0575(15) 0.066(2) 0.0457(12) -0.0021(14) 0.0191(11) 0.0081(15)
C19 0.0291(10) 0.0615(18) 0.0377(10) 0.0115(11) -0.0019(8) -0.0028(11)
C10 0.0455(13) 0.071(2) 0.0421(11) 0.0029(13) -0.0066(10) 0.0130(15)
C7 0.0412(12) 0.0471(15) 0.0403(10) 0.0002(11) 0.0089(9) -0.0043(12)
C18 0.0410(13) 0.095(2) 0.0491(12) 0.0194(15) -0.0122(10) -0.0188(15)
C20 0.0368(12) 0.080(2) 0.0451(12) 0.0220(14) -0.0014(9) -0.0069(14)
O1 0.0436(9) 0.0456(11) 0.0606(9) -0.0055(9) 0.0102(7) 0.0034(8)
C9 0.0404(12) 0.0509(16) 0.0358(10) 0.0053(11) 0.0032(8) -0.0055(12)
C8 0.0253(9) 0.0431(14) 0.0320(9) -0.0046(10) 0.0024(7) -0.0027(10)
C17 0.0424(14) 0.095(2) 0.0636(15) 0.0230(17) -0.0102(11) -0.0299(16)
C13 0.0361(12) 0.0460(15) 0.0560(13) 0.0000(12) 0.0017(9) -0.0079(12)
C1 0.0325(10) 0.0399(13) 0.0272(8) 0.0021(9) 0.0043(7) -0.0077(10)
C15 0.0291(10) 0.0390(13) 0.0311(8) 0.0016(10) 0.0058(7) 0.0023(10)
C2 0.0367(11) 0.0383(13) 0.0278(8) 0.0008(9) 0.0022(8) -0.0043(10)
C14 0.0319(10) 0.0341(13) 0.0318(9) -0.0036(10) 0.0057(7) 0.0059(10)
O2 0.0435(8) 0.0466(10) 0.0329(7) 0.0081(7) 0.0057(6) 0.0049(8)

_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
V1 O1 1.5775(17) . ?
V1 O6 1.8632(13) . ?
V1 O3 1.9318(14) . ?
V1 O4 1.9555(14) . ?
V1 N2 2.0545(17) . ?
V1 O7 2.1473(15) . ?
O7 C1 1.254(2) . ?
O4 C20 1.298(3) . ?
O6 N1 1.369(2) . ?
O3 C14 1.318(2) . ?
O5 C20 1.210(3) . ?
N1 C1 1.337(3) . ?
N1 C8 1.440(2) . ?
N2 C15 1.323(3) . ?
N2 C19 1.332(2) . ?
C5 C6 1.371(4) . ?
C5 C4 1.382(4) . ?
C5 H5 0.9300 . ?
C12 C11 1.360(4) . ?
C12 C13 1.393(3) . ?
C12 H12 0.9300 . ?
C4 C3 1.371(3) . ?
C4 H4 0.9300 . ?
C11 C10 1.367(4) . ?
C11 H11 0.9300 . ?
C16 C15 1.371(3) . ?
C16 C17 1.385(3) . ?
C16 H16 0.9300 . ?
C3 C2 1.379(3) . ?
C3 H3 0.9300 . ?
C6 C7 1.376(3) . ?
C6 H6 0.9300 . ?
C19 C18 1.376(3) . ?
C19 C20 1.500(3) . ?
C10 C9 1.390(3) . ?
C10 H10 0.9300 . ?
C7 C2 1.399(3) . ?
C7 H7 0.9300 . ?
C18 C17 1.378(4) . ?
C18 H18 0.9300 . ?
C9 C8 1.370(3) . ?
C9 H9 0.9300 . ?
C8 C13 1.371(3) . ?
C17 H17 0.9300 . ?
C13 H13 0.9300 . ?
C1 C2 1.473(3) . ?
C15 C14 1.506(3) . ?
C14 O2 1.201(2) . ?

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 V1 O6 93.52(7) . . ?
O1 V1 O3 99.17(8) . . ?
O6 V1 O3 93.33(6) . . ?
O1 V1 O4 94.31(8) . . ?
O6 V1 O4 111.57(6) . . ?
O3 V1 O4 150.87(7) . . ?
O1 V1 N2 108.02(8) . . ?
O6 V1 N2 156.99(7) . . ?
O3 V1 N2 75.71(6) . . ?
O4 V1 N2 75.59(6) . . ?
O1 V1 O7 165.49(7) . . ?
O6 V1 O7 75.47(6) . . ?
O3 V1 O7 91.00(6) . . ?
O4 V1 O7 81.36(7) . . ?
N2 V1 O7 84.42(6) . . ?
C1 O7 V1 113.44(13) . . ?
C20 O4 V1 123.06(14) . . ?
N1 O6 V1 119.08(11) . . ?
C14 O3 V1 123.19(12) . . ?
C1 N1 O6 114.83(15) . . ?
C1 N1 C8 129.79(18) . . ?
O6 N1 C8 114.50(15) . . ?
C15 N2 C19 122.25(18) . . ?
C15 N2 V1 118.99(12) . . ?
C19 N2 V1 118.58(14) . . ?
C6 C5 C4 120.2(3) . . ?
C6 C5 H5 119.9 . . ?
C4 C5 H5 119.9 . . ?
C11 C12 C13 120.5(3) . . ?
C11 C12 H12 119.8 . . ?
C13 C12 H12 119.8 . . ?
C3 C4 C5 119.7(3) . . ?
C3 C4 H4 120.2 . . ?
C5 C4 H4 120.2 . . ?
C10 C11 C12 120.7(2) . . ?
C10 C11 H11 119.6 . . ?
C12 C11 H11 119.6 . . ?
C15 C16 C17 117.4(2) . . ?
C15 C16 H16 121.3 . . ?
C17 C16 H16 121.3 . . ?
C4 C3 C2 120.6(2) . . ?
C4 C3 H3 119.7 . . ?
C2 C3 H3 119.7 . . ?
C5 C6 C7 120.6(2) . . ?
C5 C6 H6 119.7 . . ?
C7 C6 H6 119.7 . . ?
N2 C19 C18 120.1(2) . . ?
N2 C19 C20 110.86(19) . . ?
C18 C19 C20 128.95(19) . . ?
C11 C10 C9 120.0(3) . . ?
C11 C10 H10 120.0 . . ?
C9 C10 H10 120.0 . . ?
C6 C7 C2 119.3(2) . . ?
C6 C7 H7 120.4 . . ?
C2 C7 H7 120.4 . . ?
C19 C18 C17 118.0(2) . . ?
C19 C18 H18 121.0 . . ?
C17 C18 H18 121.0 . . ?
O5 C20 O4 125.4(2) . . ?
O5 C20 C19 122.7(2) . . ?
O4 C20 C19 111.89(18) . . ?
C8 C9 C10 118.5(2) . . ?
C8 C9 H9 120.8 . . ?
C10 C9 H9 120.8 . . ?
C9 C8 C13 122.2(2) . . ?
C9 C8 N1 118.64(19) . . ?
C13 C8 N1 119.1(2) . . ?
C18 C17 C16 121.2(2) . . ?
C18 C17 H17 119.4 . . ?
C16 C17 H17 119.4 . . ?
C8 C13 C12 118.0(2) . . ?
C8 C13 H13 121.0 . . ?
C12 C13 H13 121.0 . . ?
O7 C1 N1 115.82(19) . . ?
O7 C1 C2 121.41(18) . . ?
N1 C1 C2 122.70(17) . . ?
N2 C15 C16 121.03(18) . . ?
N2 C15 C14 110.49(17) . . ?
C16 C15 C14 128.46(19) . . ?
C3 C2 C7 119.6(2) . . ?
C3 C2 C1 116.74(19) . . ?
C7 C2 C1 123.5(2) . . ?
O2 C14 O3 125.06(18) . . ?
O2 C14 C15 123.82(19) . . ?
O3 C14 C15 111.12(16) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        27.55
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.052
_database_code_depnum_ccdc_archive 'CCDC 870239'