Crystal structure of tris­(N-methyl­salicylaldiminato-κ2 N,O)vanadium(III)

Jessica Hilbert; Sven Kabus; Christian Näther; Wolfgang Bensch

doi:10.1107/S2056989015021453

. 2015 Nov 18;71(Pt 12):m225. doi: 10.1107/S2056989015021453

Crystal structure of tris(N-methylsalicylaldiminato-κ² N,O)vanadium(III)

Jessica Hilbert ^a,^*, Sven Kabus ^a, Christian Näther ^a, Wolfgang Bensch ^a

PMCID: PMC4719845 PMID: 26870436

Abstract

The structure of the title complex, [V(C₈H₈NO)₃], comprises neutral and discrete complexes, in which the V^III cation is coordinated by three anionic N-methylalicylaldiminate ligands within a slightly distorted mer-N₃O₃ octahedral geometry. In the crystal structure, the molecules are linked via C—H⋯O hydrogen bonds into supramolecular chains that extend along the c axis.

Keywords: crystal structure, vanadium(III), N-methylsalicylaldiminate

Related literature

For structures of discrete complexes of Mo and V with N-methylsaldicylaldiminate as the ligand, see: Davies & Gatehouse (1974 ▸); Cornman et al. (1997 ▸). For the synthesis of the starting material, see: Bonadies & Carrano (1986 ▸). graphic file with name e-71-0m225-scheme1.jpg

Experimental

Crystal data

[V(C₈H₈NO)₃]
M _r = 453.40
Monoclinic,
a = 7.7414 (3) Å
b = 26.0018 (7) Å
c = 11.1004 (4) Å
β = 103.265 (3)°
V = 2174.79 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 170 K
0.24 × 0.14 × 0.06 mm

Data collection

STOE IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008 ▸) T _min = 0.919, T _max = 0.974
18648 measured reflections
4741 independent reflections
4054 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.102
S = 1.07
4741 reflections
283 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: X-AREA (Stoe, 2008 ▸); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▸) and DIAMOND (Brandenburg, 1999 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015021453/tk5408sup1.cif

e-71-0m225-sup1.cif^{(636.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021453/tk5408Isup2.hkl

e-71-0m225-Isup2.hkl^{(377.6KB, hkl)}

Click here for additional data file.^{(373.6KB, tif)}

. DOI: 10.1107/S2056989015021453/tk5408fig1.tif

The molecular structure of the title complex with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.5MB, tif)}

a . DOI: 10.1107/S2056989015021453/tk5408fig2.tif

Unit cell contents of the crystal structure of the title complex viewed in projection down the a axis with hydrogen bonds shown as dashed lines. For clarity, all H atoms except those that participates in hydrogen bonding are omitted.

CCDC reference: 1436532

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C27—H27⋯O21ⁱ	0.95	2.56	3.431 (2)	153

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the State of Schleswig-Holstein.

supplementary crystallographic information

S1. Synthesis and crystallization

Most of the chemicals are commercially available: Sn (Fluka, 99.9%), S (Alfa Aesar, 99.5%), and methylamine (abcr, 40% aqueous solution). (N,N'-Disalicylideneethylenediamine)oxovanadium(IV) was prepared following the procedure of Bonadies & Carrano (1986): (N,N'-disalicylideneethylenediamine)oxovanadium (IV) (83.8 mg, 0.25 mmol ), Sn (29.7 mg, 0.25 mmol) and S (24.1 mg, 0.75 mmol) were reacted in a glass tube (inner volume 11 mL) with methylamine (1.5 mL) and H₂O (0.5 mL) under solvothermal conditions at 120 °C for 24 h. Afterwards, the solid residue was filtered off, washed with water and ethanol, and dried over silica gel. The product contains red blocks of the title complex and a small amount of brown blocks of bis(N-methylsaldicylaliminato)oxovanadium(IV) (Cornman et al. (1997)). Even if Sn and S are not contained in the final product, they are needed for product formation, as otherwise only (N,N'-disalicylideneethylenediamine)oxovanadium(IV) is isolated.

S2. Refinement

The C—H H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_eq(H) = 1.2 U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms.