{2-[1-(2-Amino-2-methyl­propyl­imino)eth­yl]phenolato-κ3 N,N′,O}dioxidovanadium(V)

Grzegorz Romanowski; Michał Wera; Artur Sikorski

doi:10.1107/S1600536808042839

. 2009 Jan 14;65(Pt 2):m190. doi: 10.1107/S1600536808042839

{2-[1-(2-Amino-2-methylpropylimino)ethyl]phenolato-κ³ N,N′,O}dioxidovanadium(V)

Grzegorz Romanowski ^a,^*, Michał Wera ^a, Artur Sikorski ^a

PMCID: PMC2968252 PMID: 21581791

Abstract

In the crystal structure of the title compound, [V(C₁₂H₁₇N₂O)O₂], the vanadium(V) centre is five-coordinate in a distorted square-pyramidal environment. The three atoms of the deprotonated Schiff base and a double-bonded O atom comprise the basal plane. N—H⋯O hydrogen bonds lead to a zigzag chain structure parallel to [001].

Related literature

For general background, see: Carter-Franklin et al. (2003 ▶); Eady (2003 ▶); Evangelou (2002 ▶); Mendz (1991 ▶); Mokry & Carrano (1993 ▶); Parekh et al. (2006 ▶); Rehder et al. (2002 ▶, 2003 ▶); Shahzadi et al. (2007 ▶). For related structures, see: Kwiatkowski et al. (2003 ▶, 2007 ▶); Rao et al. (1981 ▶). For synthesis, see: Kwiatkowski et al. (2003 ▶). For the calculation of square-pyramidal geometries, see: Holmes (1984 ▶).

Experimental

Crystal data

[V(C₁₂H₁₇N₂O)O₂]
M _r = 288.22
Orthorhombic,
a = 11.1198 (6) Å
b = 15.7408 (8) Å
c = 7.6448 (3) Å
V = 1338.10 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 295 (2) K
0.20 × 0.04 × 0.04 mm

Data collection

Oxford Diffraction Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.941, T _max = 0.964
11574 measured reflections
2126 independent reflections
1387 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.051
S = 0.83
2126 reflections
167 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ▶), 849 Friedel pairs
Flack parameter: 0.23 (2)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042839/ng2526sup1.cif

e-65-0m190-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042839/ng2526Isup2.hkl

e-65-0m190-Isup2.hkl^{(104.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11A⋯O14ⁱ	0.90	2.08	2.942 (4)	159
N11—H11B⋯O15ⁱⁱ	0.90	2.29	3.173 (4)	168

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

Acknowledgments

This scientific work has been supported by Funds for Science in Years 2007–2009 as a research project (N N204 0355 33 and DS/8210–4–0086–9).

supplementary crystallographic information

Comment

Vanadium(IV) and (V) complexes with Schiff bases are excellent model compounds for some biological enzymes, viz.: haloperoxidases (Carter-Franklin et al., 2003; Rehder et al., 2003), phosphomutases (Mendz, 1991) and nitrogenases (Eady, 2003). Their various pharmocological properties also has been reported, especially as an antidiabetes (Rehder et al., 2002), anticancer (Evangelou, 2002), antifungal and antibacterial (Parekh et al., 2006; Shahzadi et al., 2007) agents.

The crystal structure of (I) consists of monomeric complex molecules (Fig. 1) with a distorted square pyramidal geometry about vanadium with O15 at the apex. By the use of the dihedral angle method and the unit bond lengths, it was estimated that the structure is displaced by 76.1% along the Berry coordinate from the ideal trigonal bipyramidal (0%) toward the ideal square pyramidal (100%) geometry (Holmes, 1984). In contrast to this structure, the similar monomeric complex, but derived from 4,6-dimetoxysalicylaldehyde (Kwiatkowski et al., 2003), reveals a distorted trigonal bipyramidal environment with the degree of the distortion of 41.2% along the Berry coordinate. The vanadium atom is displaced from the mean plane passing through the four basal atoms, N8, N11, O13 and O14, by ca 0.51 (1) Å towards O15. The bond lengths V12—N8 of 2.171 (3) Å, V12—N11 of 2.118 (2) Å, V12—O13 of 1.883 (2) Å, V12—O14 of 1.635 (2) Å, V12—O15 of 1.615 (2) Å and the O=V=O angle of 109.9° are similar to the values in other cis-VO₂⁺ complexes (Mokry & Carrano, 1993; Kwiatkowski et al., 2003; Kwiatkowski et al., 2007). The six-membered chelate ring (V12, O13, C1, C2, C7, N8) is concluded to be an envelope on V12 atom. The ring puckering analysis shows that the five-membered chelate ring defined by V12, N11, C10, C9, N8 atoms adopts a twisted conformation on C10 and N11 atoms, with P = 282.7 (2)° and Tau₍_M₎ = 49.9 (2)° for reference bond V12—N8 (Rao et al., 1981).

The crystal structure of the monomeric complex (I) is stabilized by the C—H···O, N—H···O hydrogen bonds and C—H···π interactions. Hydrogen bonds between dioxidovanadium oxygen atoms and nitrogen and carbon atoms of neighbouring molecules result in formation of infinite chains and closed loops, extending in the a direction (Tables 1 and 2, Fig. 2).

Experimental

The complex (I) were obtained in a template/complexation reactions analogous to those described for preparation of dioxidovanadium(V) complexes with Schiff base ligands (Kwiatkowski et al., 2003). A solution of 1 mmol of 2-methyl-1,2-diaminopropane in 10 ml of absolute ethanol was added under stirring to a freshly filtered solution of vanadium(V) oxytriethoxide (1 mmol) in 50 ml of absolute EtOH producing a yellow suspension of the intermediate. 2-Acetylphenol (1 mmol) dissolved in absolute EtOH was added to the aforementioned suspension. After refluxing (70 ml) of the resulting mixture for 2 h and its cooling to room temperature the separated solids were filtered off, washed several times with EtOH and dried over molecular sieves.