Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004391/ya6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004391/ya6013Isup2.hkl |
CCDC reference: 162801
Compound (I) was obtained from VO(acac)2 (0.400 g, 1.50 mmol) and a slight excess (ca 1.75 mmol) of K[SnPh3] prepared from Ph3SnH and KH, in tetrahydrofuran solution under an argon atmosphere. The deep-purple solution was stirred at room temperature for 1 h, concentrated, hexane added, and the mixture left in a freezer for 3 d. After filtering off an amorphous brown precipitate, the solution was left for a further period after which dark-orange brown crystals of (I) were deposited and collected [m. p. 460–461 K; literature 459–462 K (Morosin & Montgomery, 1969)].
Refinement was started on the basis of coordinates for non-H atoms extracted from the Cambridge Structural Database (Allen & Kennard, 1993) (VAACAC: Morosin & Montgomery, 1969) by means of the EPSRC's chemical database service at Daresbury (Fletcher et al., 1996). The non-standard space group setting and atom labels of the original determination were retained, but the cell dimensions were adjusted appropriately for the new intensity data. In the final stages, H atoms were placed in calculated positions (C—H = 0.96 and 0.93 Å for methyl and alkene H atoms, respectively) and refined in a riding-model approximation. Methyl groups were treated as rigid bodies. The incompleteness (92.95% complete) of the intensity data available for this rerefinement is due to the presence of a few defective frames in the raw intensity data.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of (I) showing the labelling scheme. Non-H atoms are shown as 50% probability ellipsoids. H atoms have been omitted for clarity. |
[V(C5H7O2)3] | Dx = 1.334 Mg m−3 Dm = 1.33 Mg m−3 Dm measured by flotation in CCl4/EtOH (Morosin & Montgomery, 1969) |
Mr = 348.26 | Melting point = 460–461 K |
Orthorhombic, Pcab | Mo Kα radiation, λ = 0.71073 Å |
a = 15.4466 (7) Å | Cell parameters from 4494 reflections |
b = 16.6228 (8) Å | θ = 2.4–26.4° |
c = 13.5016 (6) Å | µ = 0.60 mm−1 |
V = 3466.7 (3) Å3 | T = 297 K |
Z = 8 | Block, dark orange–brown |
F(000) = 1456 | 0.30 × 0.20 × 0.10 mm |
Bruker SMART 1000 area-detector diffractometer | 5155 independent reflections |
Radiation source: fine-focus sealed tube | 2251 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ and ω scans | θmax = 31.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −22→14 |
Tmin = 0.445, Tmax = 0.928 | k = −23→24 |
28129 measured reflections | l = −17→18 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0658P)2] where P = (Fo2 + 2Fc2)/3 |
5155 reflections | (Δ/σ)max = 0.003 |
205 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[V(C5H7O2)3] | V = 3466.7 (3) Å3 |
Mr = 348.26 | Z = 8 |
Orthorhombic, Pcab | Mo Kα radiation |
a = 15.4466 (7) Å | µ = 0.60 mm−1 |
b = 16.6228 (8) Å | T = 297 K |
c = 13.5016 (6) Å | 0.30 × 0.20 × 0.10 mm |
Bruker SMART 1000 area-detector diffractometer | 5155 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2251 reflections with I > 2σ(I) |
Tmin = 0.445, Tmax = 0.928 | Rint = 0.055 |
28129 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.29 e Å−3 |
5155 reflections | Δρmin = −0.56 e Å−3 |
205 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. H in calculated positions and refined with a riding model. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0027 (2) | 0.35220 (15) | 0.33680 (19) | 0.0682 (7) | |
C10 | −0.0267 (3) | 0.40889 (19) | 0.4181 (2) | 0.1098 (13) | |
H10A | −0.0192 | 0.3834 | 0.4813 | 0.165* | |
H10B | −0.0867 | 0.4219 | 0.4087 | 0.165* | |
H10C | 0.0072 | 0.4573 | 0.4157 | 0.165* | |
C12 | −0.04869 (19) | 0.33732 (18) | 0.2556 (2) | 0.0772 (9) | |
H12 | −0.1024 | 0.3626 | 0.2533 | 0.093* | |
C2 | −0.02683 (18) | 0.28758 (18) | 0.17693 (19) | 0.0631 (7) | |
C20 | −0.08692 (19) | 0.2776 (2) | 0.0909 (2) | 0.0928 (11) | |
H20A | −0.0720 | 0.3155 | 0.0400 | 0.139* | |
H20B | −0.1454 | 0.2869 | 0.1121 | 0.139* | |
H20C | −0.0819 | 0.2239 | 0.0652 | 0.139* | |
C3 | 0.09410 (19) | 0.07824 (17) | 0.3143 (2) | 0.0713 (8) | |
C30 | 0.0465 (3) | 0.0223 (2) | 0.3825 (3) | 0.1097 (13) | |
H30A | 0.0279 | 0.0513 | 0.4402 | 0.165* | |
H30B | 0.0842 | −0.0207 | 0.4021 | 0.165* | |
H30C | −0.0031 | 0.0006 | 0.3489 | 0.165* | |
C34 | 0.1382 (2) | 0.04789 (18) | 0.2328 (2) | 0.0874 (10) | |
H34 | 0.1323 | −0.0067 | 0.2191 | 0.105* | |
C4 | 0.1899 (2) | 0.09232 (18) | 0.1710 (2) | 0.0687 (8) | |
C40 | 0.2398 (2) | 0.0525 (2) | 0.0882 (2) | 0.1090 (12) | |
H40A | 0.2351 | 0.0843 | 0.0292 | 0.163* | |
H40B | 0.2165 | −0.0001 | 0.0762 | 0.163* | |
H40C | 0.2996 | 0.0479 | 0.1067 | 0.163* | |
C5 | 0.30280 (18) | 0.29429 (18) | 0.36737 (18) | 0.0641 (7) | |
C50 | 0.3605 (2) | 0.2859 (2) | 0.4569 (2) | 0.0983 (11) | |
H50A | 0.3440 | 0.3249 | 0.5059 | 0.147* | |
H50B | 0.4196 | 0.2948 | 0.4378 | 0.147* | |
H50C | 0.3546 | 0.2328 | 0.4839 | 0.147* | |
C56 | 0.3225 (2) | 0.34965 (19) | 0.2937 (2) | 0.0848 (9) | |
H56 | 0.3735 | 0.3789 | 0.3006 | 0.102* | |
C6 | 0.2732 (2) | 0.36462 (16) | 0.2120 (2) | 0.0715 (8) | |
C60 | 0.3030 (3) | 0.4242 (2) | 0.1347 (3) | 0.1221 (15) | |
H60A | 0.2960 | 0.4012 | 0.0699 | 0.183* | |
H60B | 0.3629 | 0.4368 | 0.1454 | 0.183* | |
H60C | 0.2691 | 0.4724 | 0.1395 | 0.183* | |
O1 | 0.07705 (12) | 0.32206 (10) | 0.35069 (12) | 0.0639 (5) | |
O2 | 0.04379 (11) | 0.24907 (11) | 0.17215 (12) | 0.0639 (5) | |
O3 | 0.09151 (13) | 0.15212 (11) | 0.33728 (13) | 0.0676 (5) | |
O4 | 0.20162 (11) | 0.16752 (11) | 0.17940 (12) | 0.0628 (5) | |
O5 | 0.23767 (12) | 0.24903 (11) | 0.36504 (11) | 0.0629 (4) | |
O6 | 0.20096 (12) | 0.33224 (10) | 0.19387 (12) | 0.0627 (5) | |
V1 | 0.14153 (3) | 0.24589 (2) | 0.26686 (3) | 0.04841 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.089 (2) | 0.0534 (15) | 0.0618 (16) | 0.0145 (15) | 0.0148 (15) | 0.0007 (13) |
C10 | 0.145 (3) | 0.089 (2) | 0.095 (2) | 0.049 (2) | 0.016 (2) | −0.026 (2) |
C12 | 0.070 (2) | 0.092 (2) | 0.0691 (18) | 0.0257 (17) | 0.0046 (14) | 0.0003 (16) |
C2 | 0.0541 (16) | 0.0823 (18) | 0.0528 (15) | −0.0015 (14) | 0.0057 (12) | 0.0116 (14) |
C20 | 0.0601 (18) | 0.156 (3) | 0.0627 (18) | 0.0012 (19) | −0.0039 (14) | 0.0033 (19) |
C3 | 0.075 (2) | 0.0570 (16) | 0.082 (2) | −0.0139 (14) | −0.0026 (15) | 0.0083 (15) |
C30 | 0.124 (3) | 0.076 (2) | 0.128 (3) | −0.030 (2) | 0.018 (2) | 0.029 (2) |
C34 | 0.106 (3) | 0.0528 (16) | 0.103 (3) | −0.0063 (18) | 0.004 (2) | −0.0144 (17) |
C4 | 0.0735 (19) | 0.0649 (18) | 0.0677 (18) | 0.0122 (15) | −0.0068 (14) | −0.0160 (14) |
C40 | 0.122 (3) | 0.110 (3) | 0.095 (2) | 0.027 (2) | 0.010 (2) | −0.045 (2) |
C5 | 0.0614 (17) | 0.0791 (19) | 0.0518 (14) | 0.0041 (15) | −0.0030 (12) | −0.0080 (14) |
C50 | 0.087 (2) | 0.147 (3) | 0.0603 (18) | −0.002 (2) | −0.0179 (16) | −0.012 (2) |
C56 | 0.079 (2) | 0.096 (2) | 0.0796 (19) | −0.0326 (19) | −0.0105 (17) | 0.0092 (18) |
C6 | 0.079 (2) | 0.0649 (17) | 0.0703 (18) | −0.0147 (15) | 0.0067 (15) | 0.0115 (14) |
C60 | 0.129 (3) | 0.119 (3) | 0.119 (3) | −0.044 (3) | 0.008 (2) | 0.054 (3) |
O1 | 0.0699 (12) | 0.0649 (11) | 0.0570 (10) | 0.0080 (10) | 0.0041 (9) | −0.0123 (9) |
O2 | 0.0572 (10) | 0.0844 (13) | 0.0502 (10) | 0.0034 (10) | 0.0023 (7) | −0.0079 (9) |
O3 | 0.0838 (13) | 0.0585 (11) | 0.0606 (11) | −0.0119 (10) | 0.0159 (9) | 0.0029 (9) |
O4 | 0.0683 (12) | 0.0633 (11) | 0.0568 (10) | 0.0062 (9) | 0.0126 (8) | −0.0058 (9) |
O5 | 0.0677 (11) | 0.0739 (11) | 0.0471 (9) | −0.0018 (10) | −0.0016 (8) | 0.0092 (9) |
O6 | 0.0695 (12) | 0.0643 (11) | 0.0545 (9) | −0.0074 (9) | −0.0014 (9) | 0.0149 (9) |
V1 | 0.0532 (2) | 0.0484 (2) | 0.0436 (2) | −0.0010 (2) | 0.00513 (16) | −0.00006 (18) |
C1—O1 | 1.267 (3) | C40—H40A | 0.9600 |
C1—C12 | 1.376 (4) | C40—H40B | 0.9600 |
C1—C10 | 1.516 (3) | C40—H40C | 0.9600 |
C10—H10A | 0.9600 | C5—O5 | 1.257 (3) |
C10—H10B | 0.9600 | C5—C56 | 1.389 (4) |
C10—H10C | 0.9600 | C5—C50 | 1.508 (4) |
C12—C2 | 1.388 (4) | C50—H50A | 0.9600 |
C12—H12 | 0.9300 | C50—H50B | 0.9600 |
C2—O2 | 1.266 (3) | C50—H50C | 0.9600 |
C2—C20 | 1.497 (4) | C56—C6 | 1.363 (4) |
C20—H20A | 0.9600 | C56—H56 | 0.9300 |
C20—H20B | 0.9600 | C6—O6 | 1.263 (3) |
C20—H20C | 0.9600 | C6—C60 | 1.511 (4) |
C3—O3 | 1.267 (3) | C60—H60A | 0.9600 |
C3—C34 | 1.390 (4) | C60—H60B | 0.9600 |
C3—C30 | 1.501 (4) | C60—H60C | 0.9600 |
C30—H30A | 0.9600 | O1—V1 | 1.9688 (17) |
C30—H30B | 0.9600 | O2—V1 | 1.9793 (17) |
C30—H30C | 0.9600 | O3—V1 | 1.9825 (17) |
C34—C4 | 1.370 (4) | O4—V1 | 1.9881 (16) |
C34—H34 | 0.9300 | O5—V1 | 1.9912 (18) |
C4—O4 | 1.268 (3) | O6—V1 | 1.9683 (17) |
C4—C40 | 1.510 (4) | ||
O1—C1—C12 | 124.7 (2) | O5—C5—C56 | 123.7 (3) |
O1—C1—C10 | 114.2 (3) | O5—C5—C50 | 116.0 (3) |
C12—C1—C10 | 121.0 (3) | C56—C5—C50 | 120.4 (3) |
C1—C10—H10A | 109.5 | C5—C50—H50A | 109.5 |
C1—C10—H10B | 109.5 | C5—C50—H50B | 109.5 |
H10A—C10—H10B | 109.5 | H50A—C50—H50B | 109.5 |
C1—C10—H10C | 109.5 | C5—C50—H50C | 109.5 |
H10A—C10—H10C | 109.5 | H50A—C50—H50C | 109.5 |
H10B—C10—H10C | 109.5 | H50B—C50—H50C | 109.5 |
C1—C12—C2 | 125.2 (3) | C6—C56—C5 | 125.3 (3) |
C1—C12—H12 | 117.4 | C6—C56—H56 | 117.3 |
C2—C12—H12 | 117.4 | C5—C56—H56 | 117.3 |
O2—C2—C12 | 123.3 (3) | O6—C6—C56 | 125.0 (3) |
O2—C2—C20 | 116.0 (2) | O6—C6—C60 | 114.5 (3) |
C12—C2—C20 | 120.7 (3) | C56—C6—C60 | 120.6 (3) |
C2—C20—H20A | 109.5 | C6—C60—H60A | 109.5 |
C2—C20—H20B | 109.5 | C6—C60—H60B | 109.5 |
H20A—C20—H20B | 109.5 | H60A—C60—H60B | 109.5 |
C2—C20—H20C | 109.5 | C6—C60—H60C | 109.5 |
H20A—C20—H20C | 109.5 | H60A—C60—H60C | 109.5 |
H20B—C20—H20C | 109.5 | H60B—C60—H60C | 109.5 |
O3—C3—C34 | 124.1 (3) | C1—O1—V1 | 128.90 (17) |
O3—C3—C30 | 115.7 (3) | C2—O2—V1 | 129.61 (17) |
C34—C3—C30 | 120.1 (3) | C3—O3—V1 | 129.20 (18) |
C3—C30—H30A | 109.5 | C4—O4—V1 | 129.24 (18) |
C3—C30—H30B | 109.5 | C5—O5—V1 | 129.00 (17) |
H30A—C30—H30B | 109.5 | C6—O6—V1 | 128.74 (17) |
C3—C30—H30C | 109.5 | O6—V1—O1 | 93.14 (8) |
H30A—C30—H30C | 109.5 | O6—V1—O2 | 90.73 (7) |
H30B—C30—H30C | 109.5 | O1—V1—O2 | 88.18 (7) |
C4—C34—C3 | 124.9 (3) | O6—V1—O3 | 174.40 (8) |
C4—C34—H34 | 117.5 | O1—V1—O3 | 91.87 (8) |
C3—C34—H34 | 117.5 | O2—V1—O3 | 91.92 (8) |
O4—C4—C34 | 124.0 (3) | O6—V1—O4 | 87.87 (7) |
O4—C4—C40 | 115.2 (3) | O1—V1—O4 | 177.41 (8) |
C34—C4—C40 | 120.7 (3) | O2—V1—O4 | 89.42 (7) |
C4—C40—H40A | 109.5 | O3—V1—O4 | 87.23 (8) |
C4—C40—H40B | 109.5 | O6—V1—O5 | 88.07 (7) |
H40A—C40—H40B | 109.5 | O1—V1—O5 | 88.73 (7) |
C4—C40—H40C | 109.5 | O2—V1—O5 | 176.62 (7) |
H40A—C40—H40C | 109.5 | O3—V1—O5 | 89.54 (8) |
H40B—C40—H40C | 109.5 | O4—V1—O5 | 93.69 (7) |
O1—C1—C12—C2 | −0.3 (5) | C6—O6—V1—O1 | 92.0 (2) |
C10—C1—C12—C2 | 178.9 (3) | C6—O6—V1—O2 | −179.8 (2) |
C1—C12—C2—O2 | 1.0 (5) | C6—O6—V1—O4 | −90.4 (2) |
C1—C12—C2—C20 | −178.3 (3) | C6—O6—V1—O5 | 3.4 (2) |
O3—C3—C34—C4 | 5.2 (5) | C1—O1—V1—O6 | 91.9 (2) |
C30—C3—C34—C4 | −173.9 (3) | C1—O1—V1—O2 | 1.3 (2) |
C3—C34—C4—O4 | −2.2 (5) | C1—O1—V1—O3 | −90.6 (2) |
C3—C34—C4—C40 | 175.9 (3) | C1—O1—V1—O5 | 179.9 (2) |
O5—C5—C56—C6 | 2.7 (5) | C2—O2—V1—O6 | −93.8 (2) |
C50—C5—C56—C6 | −177.1 (3) | C2—O2—V1—O1 | −0.6 (2) |
C5—C56—C6—O6 | 2.8 (5) | C2—O2—V1—O3 | 91.2 (2) |
C5—C56—C6—C60 | −177.7 (3) | C2—O2—V1—O4 | 178.4 (2) |
C12—C1—O1—V1 | −1.0 (4) | C3—O3—V1—O1 | 168.6 (2) |
C10—C1—O1—V1 | 179.73 (19) | C3—O3—V1—O2 | 80.4 (2) |
C12—C2—O2—V1 | −0.2 (4) | C3—O3—V1—O4 | −9.0 (2) |
C20—C2—O2—V1 | 179.01 (19) | C3—O3—V1—O5 | −102.7 (2) |
C34—C3—O3—V1 | 2.9 (5) | C4—O4—V1—O6 | −170.8 (2) |
C30—C3—O3—V1 | −177.9 (2) | C4—O4—V1—O2 | −80.1 (2) |
C34—C4—O4—V1 | −8.8 (4) | C4—O4—V1—O3 | 11.9 (2) |
C40—C4—O4—V1 | 173.02 (19) | C4—O4—V1—O5 | 101.2 (2) |
C56—C5—O5—V1 | −4.6 (4) | C5—O5—V1—O6 | 1.7 (2) |
C50—C5—O5—V1 | 175.20 (19) | C5—O5—V1—O1 | −91.4 (2) |
C56—C6—O6—V1 | −5.8 (4) | C5—O5—V1—O3 | 176.7 (2) |
C60—C6—O6—V1 | 174.6 (2) | C5—O5—V1—O4 | 89.5 (2) |
Experimental details
Crystal data | |
Chemical formula | [V(C5H7O2)3] |
Mr | 348.26 |
Crystal system, space group | Orthorhombic, Pcab |
Temperature (K) | 297 |
a, b, c (Å) | 15.4466 (7), 16.6228 (8), 13.5016 (6) |
V (Å3) | 3466.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.445, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28129, 5155, 2251 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.725 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.139, 0.94 |
No. of reflections | 5155 |
No. of parameters | 205 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.56 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
VAACAC | this work | |||
min. | max. | min. | max. | |
V-O | 1.967 (8) | 1.995 (8) | 1.9688 (17) | 1.9912 (18) |
C-O | 1.235 (14) | 1.268 (14) | 1.257 (3) | 1.268 (3) |
endo C-C | 1.376 (19) | 1.408 (19) | 1.363 (4) | 1.390 (4) |
C-Me | 1.497 (21) | 1.528 (21) | 1.497 (4) | 1.516 (3) |
ligand bite | 87.5 (6) | 88.4 (6) | 87.23 (8) | 88.18 (7) |
There are at least two previous reports of the preparation of the title compound, (I), which is also known as tris(acetylacetonato)vanadium(III). Grdenic & Korper-Colig (1964) prepared it by reaction of VO(acac)2 with Zn and 2,4-pentanedione (Hacac). It has also been obtained (Morosin & Montgomery, 1969) by the reaction of V2(SO4)3 (obtained by the electrolytic reduction of VOSO4) with Hacac in sodium carbonate solution. Morosin & Montgomery described two crystalline forms of the material, a monoclinic β form [REFCODE in Cambridge Structural Database (Allen & Kennard, 1993): VAACAC01], and the orthorhombic α form (VAACAC) whose stucture was determined and refined on the basis of 3061 reflections with 1361 classed as observed [I>3σ(I)]. The improved precision of the rerefinement of the α form (I) presented here is attributed to a more extensive and better quality set of intensity data (see Tables) in conjunction with the use of up-to-date software (SHELXL97; Sheldrick, 1997).
Fig. 1 shows the molecule and atom labelling scheme [identical to that used by Morosin & Montgomery (1969)] and Table 1 compares selected bond distances and angles between their determination and this work.