{2,2′-[Ethyl­enebis(nitrilo­methyl­idyne)]diphenolato-κ4 O,N,N′,O′}oxido­vanadium(IV)

Cheng Wang; Ji-Hong Yuan; Gang Xie; Ming-Juan Yu; Jing Li

doi:10.1107/S1600536808010611

. 2008 May 7;64(Pt 6):m775–m776. doi: 10.1107/S1600536808010611

{2,2′-[Ethylenebis(nitrilomethylidyne)]diphenolato-κ⁴ O,N,N′,O′}oxidovanadium(IV)

Cheng Wang ^a,^*, Ji-Hong Yuan ^a, Gang Xie ^a, Ming-Juan Yu ^b, Jing Li ^b

PMCID: PMC2961374 PMID: 21202467

Abstract

The title compound, [V(C₁₆H₁₄N₂O₂)O], was synthesized by the reaction of vanadyl(IV) sulfate and N,N′-bis(salicylidene)ethylenediamine under hydrothermal conditions. The asymmetric unit contains two molecules. Each V^IV atom is coordinated in a square-pyramidal geometry by two N atoms and two O atoms from a ligand in the basal plane and by an oxide O atom in the apical position. Weak C—H⋯O hydrogen bonds lead to a three-dimensional supramolecular structure.

Related literature

For related literature, see: Butler & Walker (1993 ▶); Deng et al. (2007 ▶); Martinez et al. (2001 ▶); Sun et al. (1996 ▶).

Experimental

Crystal data

[V(C₁₆H₁₄N₂O₂)O]
M _r = 333.23
Monoclinic,
a = 13.648 (3) Å
b = 6.8085 (14) Å
c = 15.952 (3) Å
β = 98.24 (3)°
V = 1466.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 (2) K
0.32 × 0.21 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.809, T _max = 0.930
14358 measured reflections
6102 independent reflections
4561 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.109
S = 1.03
6102 reflections
397 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ▶), 2456 Friedel pairs
Flack parameter: 0.01 (2)

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010611/hy2124sup1.cif

e-64-0m775-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010611/hy2124Isup2.hkl

e-64-0m775-Isup2.hkl^{(298.7KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

V1—O1	1.584 (3)
V1—O4	1.922 (3)
V1—O3	1.931 (2)
V1—N1	2.058 (3)
V1—N2	2.059 (3)
V2—O2	1.582 (3)
V2—O5	1.917 (3)
V2—O6	1.926 (2)
V2—N3	2.056 (3)
V2—N4	2.067 (3)

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O1—V1—O4	111.65 (15)
O1—V1—O3	106.38 (13)
O4—V1—O3	88.68 (10)
O1—V1—N1	107.53 (15)
O4—V1—N1	140.24 (11)
O3—V1—N1	86.73 (11)
O1—V1—N2	102.72 (13)
O4—V1—N2	86.65 (11)
O3—V1—N2	150.17 (11)
N1—V1—N2	78.34 (12)
O2—V2—O5	109.95 (15)
O2—V2—O6	106.92 (15)
O5—V2—O6	88.01 (11)
O2—V2—N3	105.39 (15)
O5—V2—N3	87.24 (12)
O6—V2—N3	147.00 (12)
O2—V2—N4	107.48 (17)
O5—V2—N4	142.21 (13)
O6—V2—N4	86.06 (13)
N3—V2—N4	78.04 (14)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O4ⁱ	0.97	2.55	3.139 (3)	119
C14—H14⋯O3ⁱⁱ	0.93	2.56	3.364 (3)	145
C24—H24B⋯O1ⁱⁱⁱ	0.97	2.34	3.178 (3)	144

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

Acknowledgments

This study was supported in part by the Natural Science Foundation of Heilongjiang Province (grant No. EJG0506–01, B200606 and WC03115) and the Youth Innovation Foundation of Harbin.

supplementary crystallographic information

Comment

In the past few decades, there has been increased interest in coordination chemistry and biochemistry of oxovanadium. The main reason is that the function of vanadium in biological system has been recognized, such as the regulation of carbohydrate metabolism (Butler & Walker, 1993; Martinez et al., 2001; Sun et al., 1996). Generally, Schiff base is coordinated to vanadium through O and N atoms (Deng et al., 2007), similar to those in the biological systems. Therefore, it is important to intensively study the relationship of syntheses and structural properties of vanadium-schiff base complexes. We report here the crystal structure of the title compound, a vanadium complex with a schiff-base ligand, N,N'-bis(salicylidene)ethylenediamine (H₂salen).

In the asymmetric unit, there are two crystallographically independent molecules (Fig. 1). Each V^IV atom is coordinated by two N atoms and two O atoms from a salen ligand in the equatorial plane and an oxido O atom in the apical position, resulting in a five-coordinated square-pyramidal geometry (Table 1). The V ?O bond lengths are 1.582 (2) and 1.583 (2) Å, which are in the normal range. In the crystal structure, though each salen ligand contains two phenyl ring with dihedral angles of 156.3 (4)° and 164.1 (4)°, respectively, there are no π–π interactions between the molecules. In virtue of weak intermolecular C—H···O hydrogen bonds (Table 2), a three-dimensional hydrogen-bonding network is constructed (Fig. 2).

Experimental

A mixture of VOSO₄.4H₂O (1.175 g, 5 mmol), H₂salen (0.725 g, 5 mmol), triethylamine (0.20 mmol) and methanol (0.50 mol) in water was stirred for 1 h, and then heated at 413 K for 3 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. After the reaction mixture was slowly cooled to room temperature at a rate of 5 K h^-1, black block crystals of the title compound were collected by filtration, washed with distilled water and dried in air.