Oxido[2-{(E)-[((1E)-{(E)-2-[1-(2-oxidophenyl)ethylidene]hydrazin-1-ylidene}(prop-2-en-1-ylsulfanyl)methyl)imino]methyl}phenolato]vanadium(IV)

The VIV atom in the title complex, [V(C19H17N3O2S)O], is coordinated by two N and two O atoms of the dianionic tetradentate Schiff base ligand and the terminal oxide O atom. The N2O3 donor set defines a square-pyramidal coordination geometry with the oxide O atom in the apical site. Some buckling in the tetradentate ligand is indicated by the dihedral angle of 17.92 (19)° between the six-membered chelate rings. Supramolecular chains are formed along the b axis via C—H⋯O contacts in the crystal. The chains are connected into a layer in the ab plane via C—H⋯π interactions. The atoms comprising the –SCH2—CH=CH2 and methyl substituents were found to be disordered in a 0.916 (2):0.088 (2) ratio. The crystal studied was found to be twinned by nonmerohedry with a 28.1 (4)% minor twin component.

The V IV atom in the title complex, [V(C 19 H 17 N 3 O 2 S)O], is coordinated by two N and two O atoms of the dianionic tetradentate Schiff base ligand and the terminal oxide O atom. The N 2 O 3 donor set defines a square-pyramidal coordination geometry with the oxide O atom in the apical site. Some buckling in the tetradentate ligand is indicated by the dihedral angle of 17.92 (19) between the six-membered chelate rings. Supramolecular chains are formed along the b axis via C-HÁ Á ÁO contacts in the crystal. The chains are connected into a layer in the ab plane via C-HÁ Á Á interactions. The atoms comprising the -SCH 2 -CH CH 2 and methyl substituents were found to be disordered in a 0.916 (2):0.088 (2) ratio. The crystal studied was found to be twinned by nonmerohedry with a 28.1 (4)% minor twin component.

Related literature
For background to the synthesis and characterization of isothiosemicarbazides, see: Ahmadi et al. (2012). For additional structural analysis, see: Addison et al. (1984). For the treatment of data from a twinned crystal, see: Spek (2009).
Cg1 is the centroid of the C1-C6 benzene ring.   Table 1. The resulting N 2 O 3 donor set defines a coordination geometry close to a square pyramidal geometry. This is quantified by the value of τ = 0.12 which compares to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal geometries, respectively (Addison et al., 1984). In this description, the V IV atom lies 0.590 (2) Å out of the plane of the Schiff base donor atoms [r.m.s. deviation = 0.056 Å] in the direction of the apical oxo-O3 atom. The five-membered chelate ring has an envelope conformation with the V IV atom being the flap atom. The sixmembered chelate rings are more planar, having r.m.s. deviations of 0.266 and 0.150 Å, respectively, for the O1-and O2rings. The dihedral angle between the latter chelate rings is 17.92 (19)° indicating some buckling in the tetradentate ligand.
In the crystal packing, supramolecular chains are formed along the b axis via C-H···O contacts, Table 2. These are connected into a layer in the ab plane via C-H..π interactions, Fig. 2 and Table 2. Layers stack without specific intermolecular interactions between them, Fig. 3.

Refinement
Nitrogen-and carbon-bound H-atoms were placed in calculated positions [N-H = 0.88 Å and C-H = 0.95-0.99 Å, U iso (H) = 1.2-1.5U eq (N,C)] and were included in the refinement in the riding model approximation.
The C9═N2 linkage is necessarily disordered with respect to N9′═C2′ linkage; the C9/N9′ atoms occupy the same site and were given the same displacement parameters; the N(2)/C(2′) pair of atoms were treated similarly. The -CH 2 -CH═CH 2 unit is disordered with respect to the methylene atom only. The S-C pair of distances were restrained to within 0.01 Å of each other, as were the pair of C-C distances. The anisotropic displacement parameters of the primed atoms supplementary materials were set to those of the unprimed ones. The C-C methyl distance of the minor component was restrained to 1.54±0.01 Å.

Figure 1
The molecular structure of (I) showing displacement ellipsoids at the 70% probability level. Only the major disorder component is shown.