Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020937/fl6006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020937/fl6006Isup2.hkl |
CCDC reference: 202293
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.005 Å
- R factor = 0.054
- wR factor = 0.144
- Data-to-parameter ratio = 18.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_735 Alert C D-H Calc 0.87(4), Rep 0.872(19) .... 2.11 su-Ratio O2 -H2O 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Crystals were isolated from a dichloromethane solution (1.5 ml) containing one equivalent of [hydrotris(3,5-dimethylpyrazolyl)borato](pentane-2,4-dionato)oxovanadium(IV) (Beddoes et al., 1990) and six equivalents of 2-hydroxy-2-methylbutanoic acid. After 30 min, the colour of the solution changed from blue to grey to yellow–brown. The solution was left standing in air for four weeks to afford dark-blue crystals of (I) suitable for crystal structure analysis.
Crystal decay was assessed with a recollection of the first 199 reflections at the end of the experiment. The data reduction included the application of Lorentz and polarization corrections. One of the two hydroxycarboxylate ligands is enantiomerically disordered, with the ligand sites being a mixture of both enantiomers having populations refined and then fixed at 0.75 and 0.25. The ethyl residue of one of the enantiomers is further disordered over two sites with occupancies of 0.55 and 0.2. The structure solution in non-centrosymmetric space group Cc has two complex molecules in the asymmetric unit, one of which has ligands that are the same enantiomer, whereas in the second complex, the ligands are racemic. Significant residual peaks between 1 and 1.84 in vicinity of the ethyl and methyl residues in the Cc solution could not be rationally modelled as disorder. Additionally, the Flack parameter (Flack, 1983; Bernardinelli & Flack, 1985; Flack & Bernardinelli, 1999, 2000) refines to 0.48 (4) for the Cc model, Consequently, the disordered centrosymmetic solution was selected as providing the best model for the structure.
In general, the non-H-atom sites were modelled with anisotropic displacement parameters, and a riding model was used for the H atoms. The disordered non-H-atom sites were modelled with isotropic displacement parameters. The hydroxy atoms H2O and H5O, and the pyrazole atom H2N were located and modelled with isotropic displacement parameters. Weak distance restraints were required for the hydroxy H-atom sites. Distance restraints were applied to the disordered residues, and the displacement parameters for atoms C4A and C4C were constrained to be the same, as they were those of C3A and C3B.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and XPREP (Siemens, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN for Windows (Molecular Structure Corporation, 1997), Xtal3.6 (Hall et al., 1999), ORTEPII (Johnson, 1976) and WinGX (Farrugia, 1999).
Fig. 1. ORTEPII (Johnson, 1976; Hall et al., 1999) projection of (I), with displacement ellipsoids shown at the 20% probability level. |
[VO(C5H9O3)2(C5H8N2)] | F(000) = 1672 |
Mr = 397.32 | Dx = 1.343 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.99 (1) Å | Cell parameters from 1023 reflections |
b = 10.140 (5) Å | θ = 2.9–27.7° |
c = 20.24 (1) Å | µ = 0.54 mm−1 |
β = 114.215 (7)° | T = 150 K |
V = 3929 (3) Å3 | Prismatic, blue |
Z = 8 | 0.46 × 0.28 × 0.19 mm |
Siemens SMART 1000 CCD diffractometer | 4642 independent reflections |
Radiation source: sealed tube | 3825 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 28.3°, θmin = 2.2° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −27→25 |
Tmin = 0.817, Tmax = 0.904 | k = −13→13 |
18722 measured reflections | l = −26→26 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.49 | w = 1/[σ2(Fo2) + (0.05P)2 + 5P] where P = (Fo2 + 2Fc2)/3 |
4641 reflections | (Δ/σ)max = 0.001 |
248 parameters | Δρmax = 1.43 e Å−3 |
10 restraints | Δρmin = −0.75 e Å−3 |
[VO(C5H9O3)2(C5H8N2)] | V = 3929 (3) Å3 |
Mr = 397.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.99 (1) Å | µ = 0.54 mm−1 |
b = 10.140 (5) Å | T = 150 K |
c = 20.24 (1) Å | 0.46 × 0.28 × 0.19 mm |
β = 114.215 (7)° |
Siemens SMART 1000 CCD diffractometer | 4642 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3825 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.904 | Rint = 0.023 |
18722 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 10 restraints |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.49 | Δρmax = 1.43 e Å−3 |
4641 reflections | Δρmin = −0.75 e Å−3 |
248 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. 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 > σ(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
V1 | 0.353447 (19) | 0.63503 (4) | 0.13653 (2) | 0.02355 (14) | |
O1 | 0.29873 (9) | 0.5430 (2) | 0.15073 (10) | 0.0338 (4) | |
O2 | 0.42568 (9) | 0.7467 (2) | 0.10306 (9) | 0.0284 (4) | |
H2O | 0.4657 (14) | 0.782 (4) | 0.1309 (18) | 0.058 (11)* | |
O3 | 0.30985 (9) | 0.63833 (18) | 0.02819 (9) | 0.0268 (4) | |
O4 | 0.31533 (9) | 0.6762 (2) | −0.07779 (10) | 0.0362 (5) | |
O5 | 0.31578 (9) | 0.8150 (2) | 0.14480 (10) | 0.0306 (4) | |
H5O | 0.2694 (11) | 0.825 (5) | 0.124 (2) | 0.072 (13)* | |
O6 | 0.42098 (8) | 0.68980 (19) | 0.23586 (9) | 0.0269 (4) | |
O7 | 0.45414 (12) | 0.8532 (3) | 0.31638 (13) | 0.0605 (8) | |
N1 | 0.41967 (10) | 0.4779 (2) | 0.13702 (11) | 0.0248 (4) | |
N2 | 0.49072 (10) | 0.4852 (2) | 0.17117 (11) | 0.0237 (4) | |
H2N | 0.5094 (17) | 0.552 (3) | 0.1942 (18) | 0.032 (8)* | |
C1 | 0.41223 (14) | 0.7466 (3) | 0.02750 (14) | 0.0422 (7) | |
C2 | 0.33993 (12) | 0.6829 (3) | −0.01067 (14) | 0.0281 (5) | |
C3A | 0.4654 (2) | 0.6492 (4) | 0.0166 (2) | 0.0385 (8)* | 0.75 |
H3A1 | 0.5132 | 0.6811 | 0.0440 | 0.058* | 0.75 |
H3A2 | 0.4559 | 0.6445 | −0.0349 | 0.058* | 0.75 |
H3A3 | 0.4604 | 0.5613 | 0.0340 | 0.058* | 0.75 |
C4A | 0.4199 (4) | 0.8715 (5) | −0.0069 (4) | 0.0432 (15)* | 0.55 |
H4A1 | 0.4678 | 0.9067 | 0.0184 | 0.052* | 0.55 |
H4A2 | 0.4106 | 0.8563 | −0.0583 | 0.052* | 0.55 |
C5A | 0.3685 (4) | 0.9652 (8) | −0.0012 (4) | 0.0607 (18)* | 0.55 |
H5A1 | 0.3211 | 0.9349 | −0.0316 | 0.091* | 0.55 |
H5A2 | 0.3760 | 1.0526 | −0.0174 | 0.091* | 0.55 |
H5A3 | 0.3743 | 0.9704 | 0.0493 | 0.091* | 0.55 |
C3B | 0.3958 (8) | 0.8940 (6) | 0.0143 (8) | 0.0385 (8)* | 0.25 |
H3B1 | 0.3572 | 0.9168 | 0.0276 | 0.058* | 0.25 |
H3B2 | 0.3824 | 0.9140 | −0.0371 | 0.058* | 0.25 |
H3B3 | 0.4372 | 0.9455 | 0.0438 | 0.058* | 0.25 |
C4B | 0.4703 (4) | 0.7170 (15) | 0.0073 (6) | 0.042 (3)* | 0.25 |
H4B1 | 0.4697 | 0.7895 | −0.0257 | 0.050* | 0.25 |
H4B2 | 0.4552 | 0.6372 | −0.0233 | 0.050* | 0.25 |
C5B | 0.5460 (5) | 0.6947 (15) | 0.0541 (7) | 0.052 (3)* | 0.25 |
H5B1 | 0.5520 | 0.6769 | 0.1039 | 0.078* | 0.25 |
H5B2 | 0.5727 | 0.7735 | 0.0533 | 0.078* | 0.25 |
H5B3 | 0.5628 | 0.6191 | 0.0357 | 0.078* | 0.25 |
C4C | 0.4109 (12) | 0.8890 (9) | 0.0052 (13) | 0.0432 (15)* | 0.20 |
H4C1 | 0.3911 | 0.9356 | 0.0355 | 0.052* | 0.20 |
H4C2 | 0.4609 | 0.9138 | 0.0255 | 0.052* | 0.20 |
C5C | 0.3824 (10) | 0.9582 (19) | −0.0613 (10) | 0.051 (4)* | 0.20 |
H5C1 | 0.4189 | 0.9737 | −0.0787 | 0.076* | 0.20 |
H5C2 | 0.3637 | 1.0430 | −0.0541 | 0.076* | 0.20 |
H5C3 | 0.3447 | 0.9060 | −0.0971 | 0.076* | 0.20 |
C6 | 0.34779 (16) | 0.8847 (4) | 0.21220 (17) | 0.0506 (9) | |
C7 | 0.41299 (14) | 0.8046 (3) | 0.25925 (15) | 0.0383 (7) | |
C8 | 0.3737 (3) | 1.0243 (4) | 0.1949 (3) | 0.0800 (15) | |
H8A | 0.4031 | 1.0099 | 0.1684 | 0.120* | |
H8B | 0.4007 | 1.0705 | 0.2404 | 0.120* | |
H8C | 0.3331 | 1.0778 | 0.1653 | 0.120* | |
C9 | 0.3014 (2) | 0.9029 (5) | 0.2500 (2) | 0.0685 (13) | |
H9A | 0.3257 | 0.9574 | 0.2938 | 0.082* | |
H9B | 0.2590 | 0.9512 | 0.2179 | 0.082* | |
C10 | 0.28087 (19) | 0.7781 (5) | 0.2711 (2) | 0.0689 (12) | |
H10A | 0.2579 | 0.7228 | 0.2281 | 0.103* | |
H10B | 0.2485 | 0.7948 | 0.2938 | 0.103* | |
H10C | 0.3224 | 0.7326 | 0.3056 | 0.103* | |
C11 | 0.40598 (13) | 0.3559 (3) | 0.10894 (15) | 0.0300 (6) | |
C12 | 0.46825 (14) | 0.2870 (3) | 0.12626 (15) | 0.0323 (6) | |
H12 | 0.4731 | 0.1986 | 0.1133 | 0.039* | |
C13 | 0.52163 (13) | 0.3725 (3) | 0.16594 (13) | 0.0261 (5) | |
C14 | 0.33226 (15) | 0.3121 (3) | 0.06475 (19) | 0.0440 (7) | |
H14A | 0.3062 | 0.3110 | 0.0953 | 0.066* | |
H14B | 0.3326 | 0.2233 | 0.0458 | 0.066* | |
H14C | 0.3099 | 0.3734 | 0.0243 | 0.066* | |
C15 | 0.59932 (14) | 0.3585 (3) | 0.19824 (16) | 0.0342 (6) | |
H15A | 0.6204 | 0.4392 | 0.1896 | 0.051* | |
H15B | 0.6124 | 0.2835 | 0.1758 | 0.051* | |
H15C | 0.6162 | 0.3434 | 0.2505 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0145 (2) | 0.0307 (2) | 0.0211 (2) | 0.00167 (15) | 0.00283 (15) | −0.00032 (16) |
O1 | 0.0212 (8) | 0.0443 (11) | 0.0342 (10) | −0.0012 (8) | 0.0097 (8) | 0.0007 (9) |
O2 | 0.0180 (8) | 0.0381 (10) | 0.0219 (8) | −0.0034 (7) | 0.0009 (7) | −0.0007 (7) |
O3 | 0.0166 (8) | 0.0345 (10) | 0.0231 (8) | 0.0000 (7) | 0.0017 (7) | −0.0014 (7) |
O4 | 0.0201 (8) | 0.0601 (13) | 0.0221 (9) | 0.0052 (8) | 0.0021 (7) | −0.0015 (9) |
O5 | 0.0177 (8) | 0.0389 (10) | 0.0248 (9) | 0.0079 (7) | −0.0018 (7) | −0.0039 (8) |
O6 | 0.0174 (8) | 0.0355 (10) | 0.0221 (8) | 0.0053 (7) | 0.0023 (6) | 0.0003 (7) |
O7 | 0.0371 (12) | 0.0727 (17) | 0.0410 (13) | 0.0260 (12) | −0.0152 (10) | −0.0262 (12) |
N1 | 0.0162 (9) | 0.0301 (11) | 0.0229 (10) | −0.0012 (8) | 0.0029 (8) | −0.0007 (8) |
N2 | 0.0170 (9) | 0.0293 (11) | 0.0205 (10) | 0.0004 (8) | 0.0035 (8) | −0.0014 (8) |
C1 | 0.0274 (13) | 0.067 (2) | 0.0224 (13) | −0.0141 (14) | 0.0006 (10) | 0.0075 (13) |
C2 | 0.0173 (10) | 0.0369 (14) | 0.0236 (12) | 0.0049 (10) | 0.0018 (9) | 0.0002 (10) |
C6 | 0.0329 (15) | 0.057 (2) | 0.0360 (16) | 0.0229 (14) | −0.0120 (12) | −0.0193 (14) |
C7 | 0.0234 (12) | 0.0509 (18) | 0.0281 (13) | 0.0130 (12) | −0.0023 (10) | −0.0093 (12) |
C8 | 0.086 (3) | 0.040 (2) | 0.068 (3) | 0.017 (2) | −0.014 (2) | −0.0039 (19) |
C9 | 0.0445 (19) | 0.098 (3) | 0.046 (2) | 0.032 (2) | 0.0013 (16) | −0.016 (2) |
C10 | 0.0344 (17) | 0.095 (3) | 0.072 (3) | 0.016 (2) | 0.0159 (18) | −0.007 (2) |
C11 | 0.0237 (12) | 0.0302 (13) | 0.0311 (13) | −0.0034 (10) | 0.0063 (10) | −0.0018 (10) |
C12 | 0.0306 (13) | 0.0289 (13) | 0.0357 (14) | 0.0015 (10) | 0.0120 (11) | −0.0044 (11) |
C13 | 0.0235 (11) | 0.0322 (13) | 0.0220 (11) | 0.0033 (10) | 0.0088 (9) | 0.0022 (10) |
C14 | 0.0265 (14) | 0.0402 (16) | 0.0531 (19) | −0.0075 (12) | 0.0040 (13) | −0.0092 (14) |
C15 | 0.0225 (12) | 0.0420 (16) | 0.0351 (14) | 0.0071 (11) | 0.0088 (11) | −0.0004 (12) |
V1—O1 | 1.595 (2) | C4B—C5B | 1.496 (4) |
V1—O3 | 2.000 (2) | C4B—H4B1 | 0.9900 |
V1—O6 | 2.0054 (19) | C4B—H4B2 | 0.9900 |
V1—O5 | 2.023 (2) | C5B—H5B1 | 0.9800 |
V1—N1 | 2.112 (2) | C5B—H5B2 | 0.9800 |
V1—O2 | 2.209 (2) | C5B—H5B3 | 0.9800 |
O2—C1 | 1.437 (3) | C4C—C5C | 1.41 (3) |
O2—H2O | 0.872 (19) | C4C—H4C1 | 0.9900 |
O3—C2 | 1.276 (3) | C4C—H4C2 | 0.9900 |
O4—C2 | 1.241 (3) | C5C—H5C1 | 0.9800 |
O5—C6 | 1.435 (3) | C5C—H5C2 | 0.9800 |
O5—H5O | 0.89 (2) | C5C—H5C3 | 0.9800 |
O6—C7 | 1.293 (4) | C6—C9 | 1.476 (6) |
O7—C7 | 1.228 (3) | C6—C7 | 1.540 (4) |
N1—C11 | 1.343 (3) | C6—C8 | 1.606 (6) |
N1—N2 | 1.364 (3) | C8—H8A | 0.9800 |
N2—C13 | 1.339 (3) | C8—H8B | 0.9800 |
N2—H2N | 0.82 (4) | C8—H8C | 0.9800 |
C1—C4B | 1.465 (5) | C9—C10 | 1.457 (5) |
C1—C4A | 1.485 (4) | C9—H9A | 0.9900 |
C1—C4C | 1.510 (5) | C9—H9B | 0.9900 |
C1—C3B | 1.533 (5) | C10—H10A | 0.9800 |
C1—C2 | 1.535 (4) | C10—H10B | 0.9800 |
C1—C3A | 1.572 (4) | C10—H10C | 0.9800 |
C3A—H3A1 | 0.9800 | C11—C12 | 1.394 (4) |
C3A—H3A2 | 0.9800 | C11—C14 | 1.502 (4) |
C3A—H3A3 | 0.9800 | C12—C13 | 1.384 (4) |
C4A—C5A | 1.477 (10) | C12—H12 | 0.9500 |
C4A—H4A1 | 0.9900 | C13—C15 | 1.494 (4) |
C4A—H4A2 | 0.9900 | C14—H14A | 0.9800 |
C5A—H5A1 | 0.9800 | C14—H14B | 0.9800 |
C5A—H5A2 | 0.9800 | C14—H14C | 0.9800 |
C5A—H5A3 | 0.9800 | C15—H15A | 0.9800 |
C3B—H3B1 | 0.9800 | C15—H15B | 0.9800 |
C3B—H3B2 | 0.9800 | C15—H15C | 0.9800 |
C3B—H3B3 | 0.9800 | ||
O1—V1—O3 | 99.67 (9) | C5B—C4B—H4B2 | 104.8 |
O1—V1—O6 | 104.27 (9) | H4B1—C4B—H4B2 | 105.8 |
O3—V1—O6 | 155.76 (8) | C4B—C5B—H5B1 | 109.5 |
O1—V1—O5 | 100.26 (10) | C4B—C5B—H5B2 | 109.5 |
O3—V1—O5 | 93.27 (7) | H5B1—C5B—H5B2 | 109.5 |
O6—V1—O5 | 78.86 (7) | C4B—C5B—H5B3 | 109.5 |
O1—V1—N1 | 94.54 (10) | H5B1—C5B—H5B3 | 109.5 |
O3—V1—N1 | 91.27 (8) | H5B2—C5B—H5B3 | 109.5 |
O6—V1—N1 | 90.63 (8) | C5C—C4C—C1 | 135.1 (19) |
O5—V1—N1 | 163.55 (8) | C5C—C4C—H4C1 | 103.4 |
O1—V1—O2 | 172.12 (9) | C1—C4C—H4C1 | 103.4 |
O3—V1—O2 | 73.63 (7) | C5C—C4C—H4C2 | 103.4 |
O6—V1—O2 | 82.75 (8) | C1—C4C—H4C2 | 103.4 |
O5—V1—O2 | 84.48 (8) | H4C1—C4C—H4C2 | 105.2 |
N1—V1—O2 | 81.65 (8) | O5—C6—C9 | 113.8 (3) |
C1—O2—V1 | 117.78 (15) | O5—C6—C7 | 106.2 (2) |
C1—O2—H2O | 114 (3) | C9—C6—C7 | 110.7 (3) |
V1—O2—H2O | 128 (3) | O5—C6—C8 | 107.2 (3) |
C2—O3—V1 | 124.20 (15) | C9—C6—C8 | 110.9 (3) |
C6—O5—V1 | 118.46 (16) | C7—C6—C8 | 107.8 (3) |
C6—O5—H5O | 113 (3) | O7—C7—O6 | 124.0 (3) |
V1—O5—H5O | 117 (3) | O7—C7—C6 | 118.3 (3) |
C7—O6—V1 | 118.16 (16) | O6—C7—C6 | 117.7 (2) |
C11—N1—N2 | 105.3 (2) | C6—C8—H8A | 109.5 |
C11—N1—V1 | 131.84 (17) | C6—C8—H8B | 109.5 |
N2—N1—V1 | 122.85 (16) | H8A—C8—H8B | 109.5 |
C13—N2—N1 | 112.2 (2) | C6—C8—H8C | 109.5 |
C13—N2—H2N | 128 (2) | H8A—C8—H8C | 109.5 |
N1—N2—H2N | 120 (2) | H8B—C8—H8C | 109.5 |
O2—C1—C4B | 118.3 (5) | C10—C9—C6 | 112.4 (4) |
O2—C1—C4A | 119.1 (4) | C10—C9—H9A | 109.1 |
O2—C1—C4C | 106.8 (9) | C6—C9—H9A | 109.1 |
O2—C1—C3B | 96.7 (6) | C10—C9—H9B | 109.1 |
O2—C1—C2 | 104.9 (2) | C6—C9—H9B | 109.1 |
C4B—C1—C2 | 122.5 (5) | H9A—C9—H9B | 107.9 |
C4A—C1—C2 | 113.4 (4) | C9—C10—H10A | 109.5 |
C4C—C1—C2 | 111.0 (10) | C9—C10—H10B | 109.5 |
C3B—C1—C2 | 102.6 (6) | H10A—C10—H10B | 109.5 |
O2—C1—C3A | 108.0 (2) | C9—C10—H10C | 109.5 |
C2—C1—C3A | 106.1 (3) | H10A—C10—H10C | 109.5 |
O4—C2—O3 | 124.5 (2) | H10B—C10—H10C | 109.5 |
O4—C2—C1 | 117.1 (2) | N1—C11—C12 | 109.9 (2) |
O3—C2—C1 | 118.4 (2) | N1—C11—C14 | 120.9 (2) |
C1—C3A—H3A1 | 109.5 | C12—C11—C14 | 129.2 (3) |
C1—C3A—H3A2 | 109.5 | C13—C12—C11 | 106.5 (2) |
C1—C3A—H3A3 | 109.5 | C13—C12—H12 | 126.7 |
C5A—C4A—C1 | 106.9 (5) | C11—C12—H12 | 126.7 |
C5A—C4A—H4A1 | 110.3 | N2—C13—C12 | 106.1 (2) |
C1—C4A—H4A1 | 110.3 | N2—C13—C15 | 121.6 (2) |
C5A—C4A—H4A2 | 110.3 | C12—C13—C15 | 132.3 (3) |
C1—C4A—H4A2 | 110.3 | C11—C14—H14A | 109.5 |
H4A1—C4A—H4A2 | 108.6 | C11—C14—H14B | 109.5 |
C1—C3B—H3B1 | 109.5 | H14A—C14—H14B | 109.5 |
C1—C3B—H3B2 | 109.5 | C11—C14—H14C | 109.5 |
H3B1—C3B—H3B2 | 109.5 | H14A—C14—H14C | 109.5 |
C1—C3B—H3B3 | 109.5 | H14B—C14—H14C | 109.5 |
H3B1—C3B—H3B3 | 109.5 | C13—C15—H15A | 109.5 |
H3B2—C3B—H3B3 | 109.5 | C13—C15—H15B | 109.5 |
C1—C4B—C5B | 130.1 (10) | H15A—C15—H15B | 109.5 |
C1—C4B—H4B1 | 104.8 | C13—C15—H15C | 109.5 |
C5B—C4B—H4B1 | 104.8 | H15A—C15—H15C | 109.5 |
C1—C4B—H4B2 | 104.8 | H15B—C15—H15C | 109.5 |
O3—V1—O2—C1 | −9.46 (18) | C4C—C1—C2—O4 | 62.3 (10) |
O6—V1—O2—C1 | 176.05 (19) | C3B—C1—C2—O4 | 76.7 (6) |
O5—V1—O2—C1 | −104.51 (18) | C3A—C1—C2—O4 | −68.5 (3) |
N1—V1—O2—C1 | 84.35 (19) | O2—C1—C2—O3 | −4.0 (3) |
O1—V1—O3—C2 | −168.4 (2) | C4B—C1—C2—O3 | 134.7 (7) |
O6—V1—O3—C2 | 20.8 (3) | C4A—C1—C2—O3 | −135.6 (4) |
O5—V1—O3—C2 | 90.6 (2) | C4C—C1—C2—O3 | −119.1 (10) |
N1—V1—O3—C2 | −73.6 (2) | C3B—C1—C2—O3 | −104.6 (6) |
O2—V1—O3—C2 | 7.34 (19) | C3A—C1—C2—O3 | 110.2 (3) |
O1—V1—O5—C6 | 98.2 (2) | O2—C1—C4A—C5A | −61.9 (6) |
O3—V1—O5—C6 | −161.4 (2) | C2—C1—C4A—C5A | 62.3 (6) |
O6—V1—O5—C6 | −4.5 (2) | C3A—C1—C4A—C5A | 177.5 (5) |
N1—V1—O5—C6 | −55.6 (4) | O2—C1—C4B—C5B | −4.9 (18) |
O2—V1—O5—C6 | −88.2 (2) | C3B—C1—C4B—C5B | 103.3 (16) |
O1—V1—O6—C7 | −99.0 (2) | C2—C1—C4B—C5B | −138.5 (13) |
O3—V1—O6—C7 | 71.7 (3) | O2—C1—C4C—C5C | −159 (2) |
O5—V1—O6—C7 | −1.1 (2) | C2—C1—C4C—C5C | −45 (3) |
N1—V1—O6—C7 | 166.2 (2) | V1—O5—C6—C9 | −114.0 (3) |
O2—V1—O6—C7 | 84.7 (2) | V1—O5—C6—C7 | 8.0 (4) |
O1—V1—N1—C11 | 41.0 (2) | V1—O5—C6—C8 | 123.0 (3) |
O3—V1—N1—C11 | −58.8 (2) | V1—O6—C7—O7 | −173.8 (3) |
O6—V1—N1—C11 | 145.3 (2) | V1—O6—C7—C6 | 6.1 (4) |
O5—V1—N1—C11 | −164.9 (3) | O5—C6—C7—O7 | 171.0 (3) |
O2—V1—N1—C11 | −132.1 (2) | C9—C6—C7—O7 | −65.1 (5) |
O1—V1—N1—N2 | −137.31 (19) | C8—C6—C7—O7 | 56.4 (4) |
O3—V1—N1—N2 | 122.89 (18) | O5—C6—C7—O6 | −8.9 (4) |
O6—V1—N1—N2 | −32.94 (18) | C9—C6—C7—O6 | 115.0 (3) |
O5—V1—N1—N2 | 16.8 (4) | C8—C6—C7—O6 | −123.5 (3) |
O2—V1—N1—N2 | 49.64 (18) | O5—C6—C9—C10 | 63.1 (4) |
C11—N1—N2—C13 | −0.5 (3) | C7—C6—C9—C10 | −56.4 (4) |
V1—N1—N2—C13 | 178.21 (16) | C8—C6—C9—C10 | −176.0 (3) |
V1—O2—C1—C4B | −131.2 (7) | N2—N1—C11—C12 | 0.6 (3) |
V1—O2—C1—C4A | 137.9 (4) | V1—N1—C11—C12 | −177.86 (19) |
V1—O2—C1—C4C | 127.5 (9) | N2—N1—C11—C14 | −178.1 (3) |
V1—O2—C1—C3B | 114.6 (6) | V1—N1—C11—C14 | 3.4 (4) |
V1—O2—C1—C2 | 9.6 (3) | N1—C11—C12—C13 | −0.6 (3) |
V1—O2—C1—C3A | −103.3 (2) | C14—C11—C12—C13 | 178.0 (3) |
V1—O3—C2—O4 | 174.3 (2) | N1—N2—C13—C12 | 0.1 (3) |
V1—O3—C2—C1 | −4.3 (3) | N1—N2—C13—C15 | 178.9 (2) |
O2—C1—C2—O4 | 177.3 (2) | C11—C12—C13—N2 | 0.3 (3) |
C4B—C1—C2—O4 | −44.0 (7) | C11—C12—C13—C15 | −178.4 (3) |
C4A—C1—C2—O4 | 45.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O4i | 0.89 (2) | 1.64 (2) | 2.522 (3) | 171 (5) |
O2—H2O···O7ii | 0.87 (2) | 1.74 (2) | 2.611 (3) | 178 (4) |
N2—H2N···O6ii | 0.82 (4) | 2.10 (4) | 2.902 (3) | 165 (3) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [VO(C5H9O3)2(C5H8N2)] |
Mr | 397.32 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 20.99 (1), 10.140 (5), 20.24 (1) |
β (°) | 114.215 (7) |
V (Å3) | 3929 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.46 × 0.28 × 0.19 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.817, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18722, 4642, 3825 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.144, 1.49 |
No. of reflections | 4641 |
No. of parameters | 248 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.43, −0.75 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and XPREP (Siemens, 1995), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), TEXSAN for Windows (Molecular Structure Corporation, 1997), Xtal3.6 (Hall et al., 1999), ORTEPII (Johnson, 1976) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O4i | 0.89 (2) | 1.64 (2) | 2.522 (3) | 171 (5) |
O2—H2O···O7ii | 0.872 (19) | 1.74 (2) | 2.611 (3) | 178 (4) |
N2—H2N···O6ii | 0.82 (4) | 2.10 (4) | 2.902 (3) | 165 (3) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x+1, y, −z+1/2. |
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In support of our ongoing research program into the bioinorganic chemistry of vanadium, the crystal structure of the title compound, (I) (Fig. 1), has been determined to characterize this potential synthon for complexes that model the active site of V-containing haloperoxidases. The heteroleptic oxovanadium(IV) VO2+ complex (I) (µeff = 1.67 BM) is coordinated by two 2-hydroxy-2-methylbutanoate ligands and a 3,5-dimethylpyrazole ligand. The complex has pseudo-octahedral coordination geometry, with the axial oxo group trans to the hydroxy donor atom of one of the hydroxy acid chelates [O1—V1—O2 = 172.12°]. The V atom lies 0.338 (1) Å above the plane defined by atoms O3, O5, O6 and N1 toward the oxo group.
Protonation of the hydroxy groups is indicated by a close contact distance of 2.522 (3) Å between O5 and O4 on a nearby complex at (1/2 − x, 1/2 − y, −z) and a distance of 2.611 (3) Å between O2 and O7 on another complex at (1 − x, y, 1/2 − z). A further hydrogen-bond interaction occurs between N2 and O6 on a neighbouring complex at (1 − x, y, 1/2 − z), with the donor–acceptor distance being 2.902 (3) Å. The V1—O2 bond length is 2.209 (2) Å and is significantly longer than the V1—O5 metal-to-hydroxy donor distance of 2.023 (2) Å for the second 2-hydroxy-2-methylbutanoate ligand located exclusively in the equatorial plane. The difference in bond lengths presumably reflects the trans influence of the axial oxo group. Similar bond-length differences trans and equatorial to a vanadium oxo group are found for similar complexes reported in the literature. A VO3+ complex described by Mondal et al. (1998) has an oxo–metal to trans hydroxy donor atom distance of 2.314 Å. In a square-pyramidal VO2+ complex related to (I), there is an equatorial hydroxy donor-to-metal distance of 1.987 (2) Å (Barr-David et al., 1992).
The axial tert-α hydroxy acid is enantiomerically disordered with populations for the two isomers refined and then fixed at 0.75 (R isomer in the asymmetric unit) and 0.25 (S isomer in the asymmetric unit). The ethyl residue of the predominant enantiomer is further disordered over two orientations, with site occupancies of 0.55 and 0.2. The hydroxy acid ligand located exclusively in the equatorial plane has an S configuration at C6 in the asymmetric unit.
The V1—N1 bond length [2.112 (2) Å] in (I) is very close to the V—Nε (H486) bond length (2.11 Å) found in the crystal structure of the V-haloperoxidase obtained from Ascophyllum nodosum (Weyand et al., 1999). The VO2+ motif of (I), together with the oxygen-rich coordination sphere and the single V—N(pyrazole) bond, may be a suitable precursor for model complexes of the active site of V-haloperoxidases.