[2-(1-{2-[Aza­nid­yl(ethyl­sulfan­yl)methyl­idene-κN]hydrazin-1-yl­idene-κN 1}eth­yl)phenolato-κO](dimethyl sulfoxide-κO)dioxidomolybdenum(VI)

Reza Takjoo; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812026566

. 2012 Jun 20;68(Pt 7):m944–m945. doi: 10.1107/S1600536812026566

[2-(1-{2-[Azanidyl(ethylsulfanyl)methylidene-κN]hydrazin-1-ylidene-κN ¹}ethyl)phenolato-κO](dimethyl sulfoxide-κO)dioxidomolybdenum(VI)

Reza Takjoo ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3393203 PMID: 22807771

Abstract

The Mo^VI atom in the title complex, [Mo(C₁₁H₁₃N₃OS)O₂(C₂H₆OS)], is N,N′,O-coordinated by the dianionic tridentate ligand, two mutually cis oxide O atoms and a dimethyl sulfoxide O atom, defining a distorted octahedral N₂O₄ donor set. The most prominent feature of the crystal packing is the formation of inversion dimers via pairs of N—H⋯O hydrogen bonds and eight-membered {⋯HNMoO}₂ loops. The Schiff base ligand is disordered over two orientations of equal occupancy.

Related literature

For the coordination chemistry and medicinal applications of thiosemicarbazone derivatives, see: Ahmadi et al. (2012 ▶); Dilworth & Hueting (2012 ▶). For related structures, see: Ceylan et al. (2009 ▶); Takjoo et al. (2012 ▶).

Experimental

Crystal data

[Mo(C₁₁H₁₃N₃OS)O₂(C₂H₆OS)]
M _r = 441.37
Triclinic,
a = 8.0411 (3) Å
b = 9.7243 (3) Å
c = 12.0849 (4) Å
α = 73.387 (3)°
β = 84.465 (3)°
γ = 86.077 (3)°
V = 900.47 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 100 K
0.35 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.691, T _max = 1.000
13626 measured reflections
4149 independent reflections
3811 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.072
S = 1.03
4149 reflections
234 parameters
100 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026566/hb6848sup1.cif

e-68-0m944-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026566/hb6848Isup2.hkl

e-68-0m944-Isup2.hkl^{(203.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mo—O1	2.011 (7)
Mo—O2	2.2747 (16)
Mo—O3	1.7133 (16)
Mo—O4	1.7021 (18)
Mo—N1	2.193 (6)
Mo—N3	1.933 (15)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3n⋯O3ⁱ	0.88	2.23	3.090 (15)	166
N3′—H3n′⋯O3ⁱ	0.88	1.94	2.816 (16)	171

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to the Ferdowsi University of Mashhad for financial support, and thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/3).

supplementary crystallographic information

Comment

Schiff bases derived from S-alkyl esters of thiosemicarbazone are capable of complexing both transition and main group metals (Ahmadi et al., 2012) and these may be used as therapeutic and imaging agents (Dilworth & Hueting, 2012). Herein, the crystal and molecular structure of the title complex, (I), is described, which was determined as a part of on-going studies (Takjoo et al., 2012).

The Mo^VI atom in (I), Fig. 1, exists within a distorted octahedral N₂O₄ donor set defined by the N,N,O atoms of the dinegative tridentate ligand, two oxo-O atoms and a DMSO-O atom, Table 1; the oxo-O atoms are cis. The dihedral angle between the five- and six-membered chelate rings is 11.34 (19) Å indicating some bending in the Schiff base ligand (the comparable angle in the second conformation of the disordered ligand is 7.81 (17)°). The molecular structure resembles that of the complex where the Mo atom is coordinated by methanol rather than DMSO (Ceylan et al., 2009).

While whole molecule disorder of the Schiff base ligands precludes a detailed analysis of the crystal packing, a common feature of both orientations is the formation of N—H···O hydrogen bonds between centrosymmetrically related molecules to form a dimeric aggregate via an eight-membered {···HNMoO}₂ synthon, Fig. 2 and Table 2.

Experimental

An ethanolic solution (3 ml) of molybdenyl acetylacetonate (0.33 g, 1 mmol) was added drop-wise to an ethanolic solution (3 ml) of 1-(2-hydroxyphenyl)ethanone S-ethylisothiosemicarbazone hydrobromide (0.32 g, 1 mmol) under stirring. The clear solution was stirred for 1 h and yellow precipitate was appeared. The product was then filtered, washed with cold ethanol and dried in air. The resulting compound was dissolved in DMSO (2 ml) and by slow evaporation of the solvent orange prisms appeared after one week. M.pt. 427 K. Yield: 33%.