Bis[2-(3,4-disulfanylphen­yl)acetato]bis­(2-methyl-1H-imidazole-κN 3)zinc(II)

Qiang Wang; Li-Jun Wang; Jian Hou

doi:10.1107/S1600536809033893

. 2009 Aug 29;65(Pt 9):m1149. doi: 10.1107/S1600536809033893

Bis[2-(3,4-disulfanylphenyl)acetato]bis(2-methyl-1H-imidazole-κN ³)zinc(II)

Qiang Wang ^a,^*, Li-Jun Wang ^a, Jian Hou ^a

PMCID: PMC2970003 PMID: 21577482

Abstract

In the title mononuclear zinc(II) complex, [Zn(C₈H₇O₂S₂)₂(C₄H₆N₂)₂], the Zn^II atom, lying on a twofold axis, is coordinated by two O atoms from two 2-(3,4-disulfanylphenyl)acetate anions and by two N atoms from 2-methylimidazole ligands in a distorted tetrahdral coordination. The crystal structure is stabilized by intermolecular C—H⋯O and N—H⋯O hydrogen bonds and π–π interactions with a centroid–centroid distance of 3.6136 (16) Å.

Related literature

For general background to organometallic complexes and their applications, see: Sommerfeldt et al. (2008 ▶); Huang et al. (2007 ▶); Neville et al. (2008 ▶). Zinc derivatives are of particular interest owing to their unique photosensitizing properties for photodynamic therapy, see: You et al. (2006 ▶); Shi et al. (2008 ▶); Xiao et al. (2008 ▶, 2009 ▶). For related structures, see: Yang et al. (2004 ▶); You et al. (2003 ▶, 2004 ▶); Qiu et al. (2004 ▶, 2007 ▶); Halcrow et al. (2000 ▶).

Experimental

Crystal data

[Zn(C₈H₇O₂S₂)₂(C₄H₆N₂)₂]
M _r = 628.16
Monoclinic,
a = 12.9599 (9) Å
b = 9.3909 (6) Å
c = 21.5549 (12) Å
β = 91.579 (2)°
V = 2622.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.697, T _max = 0.782
15712 measured reflections
3260 independent reflections
3102 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.125
S = 1.12
3260 reflections
175 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033893/rk2159sup1.cif

e-65-m1149-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033893/rk2159Isup2.hkl

e-65-m1149-Isup2.hkl^{(160KB, 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
C12—H12B⋯O1ⁱ	0.96	2.46	3.381 (4)	161
N2—H2⋯O2ⁱⁱ	0.85 (4)	1.94 (4)	2.785 (3)	176 (4)

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

supplementary crystallographic information

Comment

Numerous organometallic complexes have been designed for a number of potential applications, such as in synthetic chemistry (Sommerfeldt et al., 2008), as luminescence materials (Huang et al., 2007) and as magnetic materials (Neville et al., 2008). Zinc derivatives are particularly interesting owing to their unique photosensitizing properties for photodynamic therapy (You et al., 2006; Shi et al., 2008; Xiao et al., 2008; Xiao et al., 2009), magnetic circularly polarized luminescence and magnetic circular dichroism spectra. We have reported the structures of a few zinc(II) complexes (Yang et al., 2004; You et al., 2003, 2004; Qiu et al., 2007). As an extension of our work on the structural characterization of zinc compounds, we report the crystal structure of the title compound, (I), which has been determined in an attempt to understand the structural behaviour of sulfur containing ligands when coordinating to zinc carboxylates.

The present X-ray single-crystal diffraction study reveals that I, bis(3,4-dimercaptophenylaceto)-bis(2-methylimidazole-kappaN³)-zinc, consists of a Zn atom, two 3,4-dimercaptophenylaceto ligands and two 2-methylimidazole ligands. As shown on Fig. 1, the central Zn atom exhibits 4-coordination by two N atoms of position 3 from two imidazole molecules respectively and two O atoms from two 2-(3,4-disulfanylphenyl)acetate anions, forming a slightly distorted square plane. The distortion arises from the N1–Zn1–O1ⁱ axis, which is not perfectly standing in a line. The Zn–O distances is 1.9858 (18)Å is in accord with similar distance reported previously (You et al., 2004; Qiu et al., 2004). The Zn–N distance of 1.972 (2)Å is slightly shorter than other reported distances (Halcrow et al., 2000).

The H-bonding interactions occur between the N–H in imidazole as well as the methyl group (C12–H12B) as donors and O2 together with O1 atom of the carboxyl group as acceptors (Fig. 2, Table 1). These intermolecular H-bonds construct an infinite network. Concurrently, the network are solidated by weak intermolecular π-π interactions between C1-C6 ring and N1/C9/C10/N2/C11 rings with centre to centre distance of 3.6136 (16)Å.

Experimental

The 0.5 mmol of zinc oxide, 1 mmol of 3,4-dimercaptophenylacetic acid and 1 mmol of 2-methylimidazole were dissolved in 10 ml methanol. The result solution was heated to 423 K for 12 h. The reactor was cooled to room temperature at a rate of 10 K h^-1. The mixture was filtered and held at room temperature for 8 d. Colourless block crystals were isolated in 32% yield.