# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry
# This journal is © The Royal Society of Chemistry 2012


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#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
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# 
#  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 
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data_Vacac2(CH3CN)2BF4
_database_code_depnum_ccdc_archive 'CCDC 868968'
#TrackingRef '9789_web_deposit_cif_file_0_JuliaKohl_1330082360.Kohl_Vacac2(CH3CN)2BF4.cif'


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'bis(acetonitrile)bis(acetylacetonato)vanadium(III) tetrafluoroborate'
_chemical_name_common            
'bis(acetonitrile)bis(acetylacetonato)vanadium(III) tetrafluoroborate'
_chemical_formula_moiety         'C14 H20 N2 O4 V 1+, B F4 1-'
_chemical_formula_sum            'C14 H20 B F4 N2 O4 V'
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_exptl_crystal_recrystallization_method 
'diffusion: acetonitrile, diethyl ether, r. t., six weeks'
_chemical_melting_point          ?

_exptl_crystal_description       prism
_exptl_crystal_colour            'dark red'

_diffrn_ambient_temperature      150(2)
_chemical_formula_weight         418.07

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'
B B 0.0013 0.0007 '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'
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   'P 21/c'
_symmetry_int_tables_number      14
_chemical_absolute_configuration .

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

_cell_length_a                   11.9556(10)
_cell_length_b                   5.7003(4)
_cell_length_c                   15.8568(19)
_cell_angle_alpha                90.00
_cell_angle_beta                 119.774(7)
_cell_angle_gamma                90.00
_cell_volume                     937.99(17)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    1444
_cell_measurement_theta_min      3.4334
_cell_measurement_theta_max      32.5296
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.23
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             428
_exptl_absorpt_coefficient_mu    0.587

_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.80760
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           ?

_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 16.3031
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            3866
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_sigmaI/netI    0.0635
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.55
_diffrn_reflns_theta_max         26.00
_reflns_number_total             1832
_reflns_number_gt                1372
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_cell_refinement       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_data_reduction        
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'CIFTAB (Sheldrick, 2008)'

_refine_special_details          
;
Refinement of F² against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F² are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
The tetrafluoroborate moiety is disordered over an inversion center and has
been treated with PART -1. The positional disorder was not further resolved
resulting in somewhat higher displacement parameters.
;

_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)+(0.0570P)²+0.0000P] 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         1832
_refine_ls_number_parameters     142
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0450
_refine_ls_wR_factor_ref         0.1093
_refine_ls_wR_factor_gt          0.1044
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_restrained_S_all      0.980
_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 0.0000 0.5000 1.0000 0.0194(2) Uani 1 2 d S . .
O1 O -0.01892(18) 0.3144(3) 0.88997(13) 0.0239(4) Uani 1 1 d . . .
O2 O -0.15923(18) 0.6633(3) 0.90824(13) 0.0233(4) Uani 1 1 d . . .
N1 N 0.1132(2) 0.7468(4) 0.97843(16) 0.0245(5) Uani 1 1 d . . .
C1 C -0.1174(3) 0.0650(5) 0.7532(2) 0.0347(8) Uani 1 1 d . . .
H1A H -0.0508 0.1005 0.7362 0.052 Uiso 1 1 calc R . .
H1B H -0.2007 0.0465 0.6937 0.052 Uiso 1 1 calc R . .
H1C H -0.0953 -0.0808 0.7909 0.052 Uiso 1 1 calc R . .
C2 C -0.1256(3) 0.2619(4) 0.8126(2) 0.0257(6) Uani 1 1 d . . .
C3 C -0.2405(3) 0.3799(5) 0.78310(19) 0.0277(7) Uani 1 1 d . . .
H3 H -0.3159 0.3212 0.7283 0.033 Uiso 1 1 calc R . .
C4 C -0.2520(3) 0.5792(5) 0.8290(2) 0.0257(6) Uani 1 1 d . . .
C5 C -0.3761(3) 0.7133(5) 0.7864(2) 0.0395(8) Uani 1 1 d . . .
H5A H -0.4253 0.6636 0.8177 0.059 Uiso 1 1 calc R . .
H5B H -0.4266 0.6825 0.7165 0.059 Uiso 1 1 calc R . .
H5C H -0.3576 0.8815 0.7974 0.059 Uiso 1 1 calc R . .
C6 C 0.1788(3) 0.8772(5) 0.96998(19) 0.0241(6) Uani 1 1 d . . .
C7 C 0.2612(3) 1.0422(5) 0.9571(2) 0.0351(7) Uani 1 1 d . . .
H7A H 0.3512 0.9915 0.9957 0.053 Uiso 1 1 calc R . .
H7B H 0.2515 1.1982 0.9786 0.053 Uiso 1 1 calc R . .
H7C H 0.2368 1.0484 0.8883 0.053 Uiso 1 1 calc R . .
B10 B 0.5000 0.5000 1.0000 0.0438(13) Uani 1 2 d S . .
F10 F 0.4753(4) 0.6858(7) 0.9319(3) 0.0587(12) Uani 0.50 1 d P A -1
F11 F 0.4021(6) 0.5341(7) 1.0233(5) 0.0804(16) Uani 0.50 1 d P A -1
F12 F 0.4579(5) 0.2984(8) 0.9372(4) 0.0738(15) Uani 0.50 1 d P A -1
F13 F 0.6120(6) 0.4981(12) 1.0647(5) 0.120(3) Uani 0.50 1 d P A -1

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 0.0183(3) 0.0209(3) 0.0192(3) -0.0006(3) 0.0094(3) -0.0030(3)
O1 0.0239(11) 0.0252(10) 0.0227(10) -0.0014(7) 0.0117(9) -0.0023(8)
O2 0.0194(10) 0.0239(9) 0.0241(10) 0.0015(7) 0.0090(9) -0.0005(8)
N1 0.0246(13) 0.0249(12) 0.0246(13) -0.0015(9) 0.0126(11) -0.0029(10)
C1 0.045(2) 0.0341(16) 0.0271(16) -0.0045(12) 0.0195(16) -0.0052(14)
C2 0.0331(17) 0.0257(14) 0.0203(14) 0.0012(11) 0.0147(13) -0.0081(12)
C3 0.0236(16) 0.0343(16) 0.0215(14) -0.0020(12) 0.0083(13) -0.0078(13)
C4 0.0205(15) 0.0302(14) 0.0257(15) 0.0054(12) 0.0111(13) -0.0046(11)
C5 0.0268(17) 0.0444(18) 0.0393(19) 0.0067(14) 0.0103(16) 0.0056(14)
C6 0.0221(15) 0.0250(15) 0.0257(15) -0.0019(11) 0.0123(13) -0.0014(12)
C7 0.0384(18) 0.0299(17) 0.0486(19) -0.0024(13) 0.0305(17) -0.0090(13)
B10 0.029(3) 0.041(3) 0.056(3) 0.003(3) 0.016(3) -0.014(3)
F10 0.033(2) 0.074(3) 0.049(3) 0.032(2) 0.005(2) -0.008(2)
F11 0.125(5) 0.048(3) 0.124(5) -0.011(3) 0.104(4) -0.016(3)
F12 0.102(4) 0.052(3) 0.106(4) -0.028(3) 0.080(4) -0.035(3)
F13 0.066(4) 0.118(5) 0.094(4) 0.052(4) -0.023(4) -0.018(4)

_geom_special_details            
;
All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'s 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 1.9551(17) . ?
V1 O2 1.9638(18) . ?
V1 N1 2.095(2) . ?
O1 C2 1.291(3) . ?
O2 C4 1.286(3) . ?
N1 C6 1.136(3) . ?
C1 C2 1.500(4) . ?
C2 C3 1.386(4) . ?
C3 C4 1.392(4) . ?
C4 C5 1.500(4) . ?
C6 C7 1.448(4) . ?
B10 F13 1.217(5) . ?
B10 F11 1.405(5) . ?
B10 F10 1.434(4) . ?
B10 F12 1.438(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
O1 V1 O2 87.43(7) . . ?
O1 V1 N1 90.89(8) . . ?
O2 V1 N1 91.59(8) . . ?
C2 O1 V1 126.53(17) . . ?
C6 N1 V1 177.2(2) . . ?
O1 C2 C3 123.7(2) . . ?
O1 C2 C1 115.4(3) . . ?
C3 C2 C1 120.9(3) . . ?
C2 C3 C4 123.9(3) . . ?
O2 C4 C3 123.6(3) . . ?
O2 C4 C5 115.5(2) . . ?
N1 C6 C7 178.8(3) . . ?
F13 B10 F11 119.3(4) . . ?
F13 B10 F10 111.8(3) . . ?
F11 B10 F10 102.0(3) . . ?
F13 B10 F12 115.9(4) . . ?
F11 B10 F12 104.0(3) . . ?
F10 B10 F12 101.4(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O2 V1 O1 C2 -28.7(2) . . . . ?
O2 V1 O1 C2 151.3(2) 3_567 . . . ?
N1 V1 O1 C2 59.7(2) 3_567 . . . ?
N1 V1 O1 C2 -120.3(2) . . . . ?
O1 V1 O2 C4 -152.0(2) 3_567 . . . ?
O1 V1 O2 C4 28.0(2) . . . . ?
N1 V1 O2 C4 -61.1(2) 3_567 . . . ?
N1 V1 O2 C4 118.9(2) . . . . ?
V1 O1 C2 C3 18.3(4) . . . . ?
V1 O1 C2 C1 -163.44(17) . . . . ?
O1 C2 C3 C4 5.2(4) . . . . ?
C1 C2 C3 C4 -173.0(2) . . . . ?
V1 O2 C4 C3 -16.9(4) . . . . ?
V1 O2 C4 C5 164.16(19) . . . . ?
C2 C3 C4 O2 -5.9(4) . . . . ?
C2 C3 C4 C5 173.0(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.066




