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Acta Cryst. (2008). E64, m159    [ doi:10.1107/S1600536807065439 ]

Bis(acetylacetonato)oxido(triphenylphosphine oxide)vanadium(IV)

H. Chen, Y. Si, C. Chen and Q. Liu

Abstract top

In the structure of the title compound, [V(C5H7O2)2O(C18H15OP)], the V atom adopts a slightly distorted octahedral geometry with its coordination completed by four O atoms of two acetylacetonate (acac) ligands, one oxo group and one O atom of the triphenylphosphine oxide (OPPh3) ligand.

Comment top

The crystal consists of monomeric units of VO(acac)2(OPPh3) packed together without contact significantly shorter than the sum of the van der Waals radii. Each V center is six-coordinated by four O atoms of two acac ligands, one oxo group and one O atom of OPPh3 ligand to furnish a slightly distorted octahedral geometry. The four acac O atoms define the equatorial plane. The oxo group and the O atom from OPPh3 ligand occupy the axial sites in a trans configuration. The V—O(acac) bond distances [1.9974 (13) Å-2.0085 (14) Å] are a little longer than those observed in [VO(acac)2] [1.966 (6) Å-1.986 (6) Å, Shuter et al., 1995; Hoshino et al., 2005] and the bond length of V—O(OPPh3) is 2.2586 (13) Å, significantly longer than those found in [VOCl2(OPPh3)2] [1.986 (5) Å and 2.002 (5) Å, Caira & Gellatly, 1980] and [VCl3(NPPh3)(OPPh3)](1.928 (6) Å, Rübenstahl et al., 1993).

The presence of OPPh3 ligand in the compound was unexpected since the original reactant was PPh3. It has been shown in earlier studies that some metal oxo-complexes might react with PPh3 to give rise to OPPh3 due to their catalytic and redox properties (Scott et al., 1992; Zhu et al., 1996; Mévellec et al., 2001). Thus, it was speculated that PPh3 was oxidized to OPPh3 by oxovanadium complex in this experiment.

Related literature top

For related literature, see: Hoshino et al. (2005); Mévellec et al. (2001); Rübenstahl et al. (1993); Shuter et al. (1995); Zhu et al. (1996).

For related literature, see: Caira & Gellatly (1980); Rigaku/MSC (2004); Scott et al. (1992).

Experimental top

The title compound was obtained unintentionally when we attempted to synthesize vanadium coordination complexes containing 3,5-pyrazoledicarboxylato ligand (H3pdc). To the mixture of H3pdc (0.5 mmol), NaOH (1 mmol) and VO(acac)2 (0.5 mmol) in 10 ml H2O was added a CHCl3 solution (5 ml) of PPh3 (0.25 mmol). The resulting solution was allowed to stand at room temperature for six weeks to deposit green crystals of X-ray quality.

Refinement top

H atoms bound to C atoms were located by geometry, and their positions and thermal parameters were constrained to ride on their parent atoms during the structure refinement.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing atom labels and 20% probability ellipsoids for non-H atoms.
Bis(acetylacetonato)oxido(triphenylphosphine oxide)vanadium(IV) top
Crystal data top
[V(C5H7O2)2O(C18H15OP)]Z = 2
Mr = 543.42F000 = 566
Triclinic, P1Dx = 1.369 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 10.153 (3) ÅCell parameters from 3761 reflections
b = 10.353 (3) Åθ = 2.1–27.5º
c = 13.407 (4) ŵ = 0.48 mm−1
α = 101.677 (2)ºT = 294 (2) K
β = 90.693 (5)ºPrism, green
γ = 106.688 (4)º0.28 × 0.20 × 0.18 mm
V = 1318.2 (7) Å3
Data collection top
Rigaku Saturn70 CCD
diffractometer		5899 independent reflections
Radiation source: fine-focus sealed tube4756 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 294(2) Kθmax = 27.5º
ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→13
Tmin = 0.860, Tmax = 0.920k = −13→13
10251 measured reflectionsl = −16→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0785P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.001
5899 reflectionsΔρmax = 0.43 e Å−3
329 parametersΔρmin = −0.54 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[V(C5H7O2)2O(C18H15OP)]γ = 106.688 (4)º
Mr = 543.42V = 1318.2 (7) Å3
Triclinic, P1Z = 2
a = 10.153 (3) ÅMo Kα
b = 10.353 (3) ŵ = 0.48 mm−1
c = 13.407 (4) ÅT = 294 (2) K
α = 101.677 (2)º0.28 × 0.20 × 0.18 mm
β = 90.693 (5)º
Data collection top
Rigaku Saturn70 CCD
diffractometer		5899 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4756 reflections with I > 2σ(I)
Tmin = 0.860, Tmax = 0.920Rint = 0.020
10251 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036329 parameters
wR(F2) = 0.121H-atom parameters constrained
S = 1.13Δρmax = 0.43 e Å−3
5899 reflectionsΔρmin = −0.54 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V11.03517 (3)0.82224 (3)0.22396 (2)0.02967 (11)
P10.67969 (4)0.83817 (4)0.24257 (3)0.02730 (12)
O10.99298 (14)0.67895 (14)0.30948 (10)0.0436 (3)
O20.92589 (13)0.67788 (13)0.10557 (9)0.0400 (3)
O30.82442 (11)0.83840 (13)0.26469 (9)0.0351 (3)
O41.02709 (13)0.96524 (13)0.14587 (9)0.0362 (3)
O51.08719 (12)0.96846 (13)0.35241 (9)0.0361 (3)
O61.18499 (13)0.81385 (16)0.19582 (11)0.0494 (3)
C10.9215 (3)0.4673 (3)0.3614 (2)0.0727 (8)
H1A1.01230.47590.38850.109*
H1B0.87480.37210.33220.109*
H1C0.87050.50100.41530.109*
C20.9323 (2)0.5508 (2)0.27993 (16)0.0455 (5)
C30.8760 (2)0.4847 (2)0.18191 (18)0.0530 (5)
H3A0.83690.38940.16920.064*
C40.87320 (19)0.5503 (2)0.10003 (15)0.0413 (4)
C50.8031 (2)0.4665 (2)−0.00156 (18)0.0592 (6)
H5A0.76960.5239−0.03700.089*
H5B0.72720.39130.00890.089*
H5C0.86780.4307−0.04140.089*
C61.0415 (2)1.1785 (2)0.10245 (15)0.0472 (5)
H6A1.12701.19860.07050.071*
H6B1.02561.26330.13590.071*
H6C0.96741.12790.05160.071*
C71.04857 (17)1.09364 (18)0.17968 (13)0.0327 (4)
C81.07829 (19)1.15850 (19)0.28267 (13)0.0401 (4)
H8A1.08701.25240.29980.048*
C91.09605 (17)1.09559 (18)0.36203 (13)0.0340 (4)
C101.1309 (2)1.1816 (2)0.46922 (14)0.0505 (5)
H10A1.06371.14280.51320.076*
H10B1.13041.27430.46950.076*
H10C1.22071.18260.49330.076*
C110.55910 (16)0.68625 (17)0.27131 (12)0.0304 (3)
C120.6134 (2)0.60577 (19)0.32063 (14)0.0391 (4)
H12A0.70830.62770.33380.047*
C130.5260 (3)0.4921 (2)0.35045 (18)0.0571 (6)
H13A0.56250.43840.38400.069*
C140.3867 (3)0.4591 (2)0.33060 (19)0.0631 (6)
H14A0.32870.38260.35040.076*
C150.3312 (2)0.5391 (2)0.28087 (18)0.0569 (6)
H15A0.23620.51620.26770.068*
C160.41669 (19)0.6524 (2)0.25089 (15)0.0422 (4)
H16A0.37970.70580.21740.051*
C170.63977 (17)0.8411 (2)0.11197 (13)0.0352 (4)
C180.5849 (2)0.7194 (2)0.04015 (15)0.0501 (5)
H18A0.56020.63550.06060.060*
C190.5666 (3)0.7217 (3)−0.06184 (16)0.0685 (7)
H19A0.52920.6396−0.10950.082*
C200.6035 (3)0.8446 (4)−0.09268 (18)0.0713 (8)
H20A0.59090.8457−0.16130.086*
C210.6593 (3)0.9662 (3)−0.02260 (19)0.0661 (7)
H21A0.68551.0495−0.04390.079*
C220.6762 (2)0.9647 (2)0.07985 (16)0.0500 (5)
H22A0.71241.04740.12730.060*
C230.64143 (17)0.98229 (17)0.32429 (13)0.0312 (3)
C240.5175 (2)1.0118 (2)0.31082 (15)0.0437 (4)
H24A0.45640.96330.25440.052*
C250.4863 (2)1.1131 (2)0.38136 (18)0.0561 (6)
H25A0.40341.13240.37250.067*
C260.5757 (3)1.1861 (2)0.46471 (17)0.0586 (6)
H26A0.55311.25400.51200.070*
C270.6997 (3)1.1587 (2)0.47836 (16)0.0553 (5)
H27A0.76071.20820.53460.066*
C280.7323 (2)1.0569 (2)0.40744 (14)0.0418 (4)
H28A0.81581.03870.41600.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.03094 (17)0.03182 (17)0.02627 (16)0.01119 (12)−0.00037 (11)0.00367 (11)
P10.0250 (2)0.0323 (2)0.0259 (2)0.01010 (16)0.00204 (15)0.00692 (16)
O10.0561 (8)0.0432 (8)0.0388 (7)0.0234 (6)0.0012 (6)0.0130 (6)
O20.0475 (7)0.0360 (7)0.0329 (6)0.0116 (5)−0.0029 (5)0.0007 (5)
O30.0262 (6)0.0453 (7)0.0358 (6)0.0128 (5)0.0023 (5)0.0099 (5)
O40.0463 (7)0.0355 (7)0.0256 (6)0.0104 (5)0.0017 (5)0.0067 (5)
O50.0389 (7)0.0384 (7)0.0272 (6)0.0084 (5)−0.0035 (5)0.0033 (5)
O60.0390 (7)0.0614 (9)0.0501 (8)0.0230 (6)0.0053 (6)0.0055 (7)
C10.109 (2)0.0606 (15)0.0722 (17)0.0456 (15)0.0271 (15)0.0363 (13)
C20.0548 (12)0.0396 (10)0.0547 (12)0.0276 (9)0.0176 (9)0.0182 (9)
C30.0662 (14)0.0304 (10)0.0608 (13)0.0135 (9)0.0143 (10)0.0069 (9)
C40.0365 (9)0.0378 (10)0.0458 (10)0.0131 (8)0.0070 (8)−0.0032 (8)
C50.0543 (13)0.0488 (12)0.0575 (13)0.0070 (10)0.0008 (10)−0.0149 (10)
C60.0613 (13)0.0421 (11)0.0405 (10)0.0155 (9)0.0030 (9)0.0138 (9)
C70.0303 (8)0.0335 (9)0.0334 (8)0.0064 (7)0.0058 (6)0.0090 (7)
C80.0503 (11)0.0301 (9)0.0354 (9)0.0074 (7)0.0024 (8)0.0036 (7)
C90.0284 (8)0.0369 (9)0.0293 (8)0.0025 (7)0.0028 (6)0.0009 (7)
C100.0628 (13)0.0468 (12)0.0293 (9)0.0048 (10)0.0019 (9)−0.0036 (8)
C110.0319 (8)0.0315 (8)0.0255 (7)0.0081 (6)0.0024 (6)0.0028 (6)
C120.0424 (10)0.0367 (9)0.0388 (9)0.0121 (8)0.0007 (7)0.0093 (8)
C130.0698 (15)0.0438 (12)0.0578 (13)0.0088 (10)−0.0015 (11)0.0234 (10)
C140.0636 (15)0.0494 (13)0.0627 (14)−0.0100 (11)0.0071 (11)0.0199 (11)
C150.0384 (11)0.0588 (14)0.0606 (14)−0.0038 (9)0.0048 (9)0.0098 (11)
C160.0348 (9)0.0454 (10)0.0438 (10)0.0079 (8)0.0005 (7)0.0094 (8)
C170.0304 (8)0.0509 (10)0.0290 (8)0.0168 (7)0.0053 (6)0.0124 (7)
C180.0569 (12)0.0578 (13)0.0329 (10)0.0144 (10)0.0025 (8)0.0074 (9)
C190.0749 (17)0.094 (2)0.0305 (11)0.0219 (14)−0.0027 (10)0.0045 (12)
C200.0749 (17)0.123 (3)0.0339 (11)0.0500 (17)0.0091 (11)0.0268 (14)
C210.0741 (16)0.0909 (19)0.0579 (15)0.0409 (14)0.0198 (12)0.0467 (15)
C220.0551 (12)0.0578 (13)0.0453 (11)0.0215 (10)0.0105 (9)0.0223 (10)
C230.0318 (8)0.0304 (8)0.0332 (8)0.0102 (6)0.0067 (6)0.0089 (7)
C240.0405 (10)0.0460 (11)0.0486 (11)0.0209 (8)0.0008 (8)0.0070 (9)
C250.0600 (13)0.0589 (14)0.0630 (14)0.0375 (11)0.0162 (11)0.0140 (11)
C260.0888 (17)0.0462 (12)0.0477 (12)0.0324 (12)0.0226 (12)0.0068 (10)
C270.0743 (15)0.0441 (12)0.0398 (11)0.0125 (10)−0.0013 (10)−0.0009 (9)
C280.0427 (10)0.0404 (10)0.0401 (10)0.0110 (8)0.0003 (8)0.0059 (8)
Geometric parameters (Å, °) top
V1—O61.5937 (13)C10—H10C0.9600
V1—O41.9974 (13)C11—C121.383 (2)
V1—O51.9999 (12)C11—C161.396 (2)
V1—O12.0085 (14)C12—C131.390 (3)
V1—O22.0072 (13)C12—H12A0.9300
V1—O32.2586 (13)C13—C141.365 (4)
P1—O31.4948 (12)C13—H13A0.9300
P1—C171.8006 (18)C14—C151.389 (3)
P1—C231.8052 (17)C14—H14A0.9300
P1—C111.8088 (17)C15—C161.381 (3)
O1—C21.268 (2)C15—H15A0.9300
O2—C41.261 (2)C16—H16A0.9300
O4—C71.268 (2)C17—C181.385 (3)
O5—C91.273 (2)C17—C221.384 (3)
C1—C21.511 (3)C18—C191.384 (3)
C1—H1A0.9600C18—H18A0.9300
C1—H1B0.9600C19—C201.368 (4)
C1—H1C0.9600C19—H19A0.9300
C2—C31.384 (3)C20—C211.374 (4)
C3—C41.407 (3)C20—H20A0.9300
C3—H3A0.9300C21—C221.386 (3)
C4—C51.503 (3)C21—H21A0.9300
C5—H5A0.9600C22—H22A0.9300
C5—H5B0.9600C23—C281.381 (3)
C5—H5C0.9600C23—C241.395 (2)
C6—C71.500 (3)C24—C251.375 (3)
C6—H6A0.9600C24—H24A0.9300
C6—H6B0.9600C25—C261.372 (3)
C6—H6C0.9600C25—H25A0.9300
C7—C81.395 (2)C26—C271.386 (3)
C8—C91.390 (3)C26—H26A0.9300
C8—H8A0.9300C27—C281.388 (3)
C9—C101.507 (2)C27—H27A0.9300
C10—H10A0.9600C28—H28A0.9300
C10—H10B0.9600
O6—V1—O497.10 (7)C8—C9—C10119.21 (17)
O6—V1—O599.20 (6)C9—C10—H10A109.5
O4—V1—O589.73 (6)C9—C10—H10B109.5
O6—V1—O197.80 (7)H10A—C10—H10B109.5
O4—V1—O1165.07 (5)C9—C10—H10C109.5
O5—V1—O188.84 (6)H10A—C10—H10C109.5
O6—V1—O298.11 (7)H10B—C10—H10C109.5
O4—V1—O288.28 (6)C12—C11—C16119.89 (17)
O5—V1—O2162.69 (5)C12—C11—P1116.84 (13)
O1—V1—O288.67 (6)C16—C11—P1123.18 (14)
O6—V1—O3178.95 (7)C11—C12—C13119.93 (19)
O4—V1—O382.22 (5)C11—C12—H12A120.0
O5—V1—O380.01 (5)C13—C12—H12A120.0
O1—V1—O382.89 (5)C14—C13—C12120.2 (2)
O2—V1—O382.68 (5)C14—C13—H13A119.9
O3—P1—C17114.02 (7)C12—C13—H13A119.9
O3—P1—C23111.29 (8)C13—C14—C15120.3 (2)
C17—P1—C23108.27 (8)C13—C14—H14A119.9
O3—P1—C11110.17 (8)C15—C14—H14A119.8
C17—P1—C11107.56 (8)C16—C15—C14120.2 (2)
C23—P1—C11105.08 (8)C16—C15—H15A119.9
C2—O1—V1127.40 (13)C14—C15—H15A119.9
C4—O2—V1128.54 (13)C15—C16—C11119.5 (2)
P1—O3—V1155.14 (8)C15—C16—H16A120.3
C7—O4—V1128.12 (11)C11—C16—H16A120.3
C9—O5—V1126.73 (11)C18—C17—C22118.85 (18)
C2—C1—H1A109.5C18—C17—P1120.72 (15)
C2—C1—H1B109.5C22—C17—P1120.12 (15)
H1A—C1—H1B109.5C17—C18—C19120.4 (2)
C2—C1—H1C109.5C17—C18—H18A119.8
H1A—C1—H1C109.5C19—C18—H18A119.8
H1B—C1—H1C109.5C20—C19—C18120.2 (2)
O1—C2—C3125.62 (19)C20—C19—H19A119.9
O1—C2—C1115.3 (2)C18—C19—H19A119.9
C3—C2—C1119.1 (2)C21—C20—C19120.2 (2)
C2—C3—C4125.09 (19)C21—C20—H20A119.9
C2—C3—H3A117.5C19—C20—H20A119.9
C4—C3—H3A117.5C20—C21—C22119.9 (2)
O2—C4—C3124.22 (18)C20—C21—H21A120.0
O2—C4—C5116.27 (19)C22—C21—H21A120.0
C3—C4—C5119.5 (2)C17—C22—C21120.4 (2)
C4—C5—H5A109.5C17—C22—H22A119.8
C4—C5—H5B109.5C21—C22—H22A119.8
H5A—C5—H5B109.5C28—C23—C24119.53 (16)
C4—C5—H5C109.5C28—C23—P1118.53 (13)
H5A—C5—H5C109.5C24—C23—P1121.68 (14)
H5B—C5—H5C109.5C25—C24—C23119.65 (19)
C7—C6—H6A109.5C25—C24—H24A120.2
C7—C6—H6B109.5C23—C24—H24A120.2
H6A—C6—H6B109.5C26—C25—C24120.9 (2)
C7—C6—H6C109.5C26—C25—H25A119.6
H6A—C6—H6C109.5C24—C25—H25A119.6
H6B—C6—H6C109.5C25—C26—C27120.00 (19)
O4—C7—C8123.98 (16)C25—C26—H26A120.0
O4—C7—C6116.74 (15)C27—C26—H26A120.0
C8—C7—C6119.28 (16)C28—C27—C26119.5 (2)
C7—C8—C9125.95 (17)C28—C27—H27A120.2
C7—C8—H8A117.0C26—C27—H27A120.2
C9—C8—H8A117.0C23—C28—C27120.39 (19)
O5—C9—C8125.33 (16)C23—C28—H28A119.8
O5—C9—C10115.46 (17)C27—C28—H28A119.8
Acknowledgements top

We are grateful to the National Nature Science Foundation of China (No. 20471061) for financial support of this work.

references
References top

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Caira, M. & Gellatly, B. J. (1980). Acta Cryst. B36, 1198–1201.

Hoshino, M., Sekine, A., Uekusa, H. & Ohashi, Y. (2005). Chem. Lett. 34, 1228–1229.

Mévellec, F., Roucoux, A., Noiret, N. & Patin, H. (2001). Dalton Trans. pp. 3603–3610.

Rigaku/MSC (2004). CrystalClear. Version 1.3.6. Rigaku/MSC, The Woodlands, Texas, USA

Rübenstahl, T., Dehnicke, K. & Krautscheid, H. (1993). Z. Anorg. Allg. Chem. 619, 1023–1026.

Scott, S. L., Bakac, A. & Espenson, J. H. (1992). J. Am. Chem. Soc. 114, 4205–4213.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Shuter, E., Rettig, S. J. & Orvig, C. (1995). Acta Cryst. C51, 12–14.

Zhu, Z., Al-Ajlouni, A. M. & Espenson, J. H. (1996). Inorg. Chem. 35, 1408–1409.