trans-Bis(1,3-diphenyl­propane-1,3-dionato)(methanol)oxidovanadium(IV) methanol disolvate

Carla Pretorius; Johan A Venter; Andreas Roodt

doi:10.1107/S1600536812044686

. 2012 Oct 3;68(Pt 12):m1442–m1443. doi: 10.1107/S1600536812044686

trans-Bis(1,3-diphenylpropane-1,3-dionato)(methanol)oxidovanadium(IV) methanol disolvate

Carla Pretorius ^a,^*, Johan A Venter ^a, Andreas Roodt ^a

PMCID: PMC3588710 PMID: 23468675

Abstract

In the title compound, [V(C₁₅H₁₁O₂)₂O(CH₃OH)]·2CH₃OH, the V^IV atom is coordinated by two 1,3-diphenylpropane-1,3-dionate ligands and an oxide ligand in an axial position. The sixth position is occupied by the O atom of a methanol group bonded trans to the oxide atom. The octahedral geometry is significantly distorted, with the V^IV atom lying 0.330 (3) Å above the equatorial plane formed by the O atoms of the two β-diketonate ligands. In the crystal, O—H⋯O hydrogen bonds between the coordinating methanol group in the complex and the two methanol solvent molecules lead to the formation of polymeric chains along the c-axis direction. Weak C—H⋯O contacts are also observed.

Related literature

For synthetic background, see: Schilde et al. (1995 ▶). For other methanol-substituted vanadium complexes, see: Gao et al. (1998 ▶); Chen et al. (2004 ▶); Tasiopoulos et al. (1999 ▶). For methoxy-substituted vanadium complexes, see: Bansse et al. (1992 ▶). graphic file with name e-68-m1442-scheme1.jpg

Experimental

Crystal data

[V(C₁₅H₁₁O₂)₂O(CH₄O)]·2CH₄O
M _r = 609.54
Monoclinic,
a = 16.1411 (1) Å
b = 10.7450 (6) Å
c = 18.5378 (13) Å
β = 113.579 (2)°
V = 2946.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 100 K
0.47 × 0.07 × 0.05 mm

Data collection

Bruker APEXII KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.968, T _max = 0.981
38614 measured reflections
7317 independent reflections
5545 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.102
S = 1.03
7317 reflections
412 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), publCIF (Westrip, 2010 ▶), PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(34KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044686/sj5267sup1.cif

e-68-m1442-sup1.cif^{(34KB, cif)}

Click here for additional data file.^{(350.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044686/sj5267Isup2.hkl

e-68-m1442-Isup2.hkl^{(350.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

O1—V1	1.5965 (13)
O2—V1	1.9972 (12)
O3—V1	2.0045 (12)
O4—V1	1.9847 (12)
O5—V1	1.9935 (12)
O6—V1	2.3020 (15)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O7	0.82 (3)	1.83 (3)	2.644 (2)	169 (3)
O7—H7A⋯O8ⁱ	0.87 (3)	1.90 (3)	2.749 (2)	168 (3)
O8—H8A⋯O3	0.90 (3)	1.96 (3)	2.853 (2)	178 (3)
C13—H13⋯O1ⁱⁱ	0.95	2.58	3.487 (2)	160
C32—H32B⋯O1ⁱ	0.98 (3)	2.43 (3)	3.360 (3)	159 (2)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

Financial assistance from the University of the Free State Strategic Academic Cluster Initiative (Materials and Nanosciences), SASOL and the South African National Research Foundation (SA-NRF/THRIP) is gratefully acknowledged.

supplementary crystallographic information

Comment

The complex has two coordinated 1,3-diphenylpropane-1,3-dionato (dbm) ligands in the equatorial plane, the same as in the [VO(dbm)₂] structure described by Schilde (Schilde et al., 1995). The oxido group is in the axial position and no significant change in bond length is reported for the O1—V1 bond of 1.5964 (3) Å as compared to the [VO(dbm)₂] structure (1.5922 (4) Å). The sixth coordination position at the vanadium centre trans to the oxido is occupied by a methanol molecule. The rather long bond length of 2.302 (2) Å is similar to methanol coordination in structures by Gao (2.346 Å) (Gao et al., 1998), Chen (2.333 Å) (Chen et al., 2004) and Tasiopoulos (2.301 Å) (Tasiopoulos et al., 1999). A methoxy group bonded to a vanadium metal centre would have a V-OMe bond length of approximately 1.755 Å (Bansse et al., 1992).

Intermolecular O6—H6A···O7 hydrogen bonding in the order of 2.644 (2) Å was observed with a methanol solvent molecule. Additional intermolecular hydrogen bonding was also noted between O7—H7A···O8ⁱ of the order 2.749 (2) Å and O8—H8A···O3 in the order of 2.853 (2) Å. These interactions eventually lead to the formation of polymeric chains of the complex along the c-axis, as illustrated in Figure 2.

Weaker intermolecular hydrogen bonding was also noted between C13—H13···O1ⁱⁱ in the order of 3.487 (2) Å and C32—H32B···O1ⁱ in the order of 3.360 (3) Å.

Experimental

V₂O₅ (1.0 g, 5.5 mmol) was added to a mixture of ethanol, water and sulfuric acid (5 cm³, 2 cm³ and 2 cm³ respectively) and refluxed for one hour, after which the yellow mixture turned a brilliant blue colour. A solution of 1,3-diphenylpropane-1,3-dione (4.93 g, 22 mmol) in ethanol (10 cm³) was added to the reaction mixture which was then stirred for ca 10 min. A saturated solution of sodium carbonate in water (20 cm³) was added to the mixture and the resulting green precipitate was collected by filtration. The precipitate was recrystallized from methanol and, after two weeks, small red needle-like crystals of [VO(dbm)₂(MeOH)] were formed (yield: 2.35 g, 70%).