{4-Bromo-2-[3-(diethyl­ammonio)propyl­imino­meth­yl]phenolato}diiodidozinc(II) methanol solvate

Xue-Wen Zhu; Zhi-Gang Yin; Xu-Zhao Yang; Gang-Sen Li; Chun-Xia Zhang

doi:10.1107/S1600536809038446

. 2009 Oct 3;65(Pt 11):m1293–m1294. doi: 10.1107/S1600536809038446

{4-Bromo-2-[3-(diethylammonio)propyliminomethyl]phenolato}diiodidozinc(II) methanol solvate

Xue-Wen Zhu ^a,^*, Zhi-Gang Yin ^a, Xu-Zhao Yang ^a, Gang-Sen Li ^a, Chun-Xia Zhang ^a

PMCID: PMC2971364 PMID: 21578061

Abstract

In the title complex, [ZnI₂(C₁₄H₂₁BrN₂O)]·CH₃OH, the asymmetric unit consists of a mononuclear zinc(II) complex molecule and a methanol solvent molecule. The compound was derived from the zwitterionic form of the Schiff base 4-bromo-2-[3-(diethylamino)propyliminomethyl]phenol. The Zn^II atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand and by two iodide ions in a distorted tetrahedral coordination. In the crystal structure, the methanol molecules are linked to the Schiff base molecules through N—H⋯O and O—H⋯O hydrogen bonds. One I atom is disordered over two positions in a 0.702 (19):0.298 (19) ratio.

Related literature

For background to the chemistry of Schiff base complexes, see: Ali et al. (2008 ▶); Biswas et al. (2008 ▶); Chen et al. (2008 ▶); Darensbourg & Frantz (2007 ▶); Habibi et al. (2007 ▶); Kawamoto et al. (2008 ▶); Lipscomb & Sträter (1996 ▶); Tomat et al. (2007 ▶); Wu et al. (2008 ▶); Yuan et al. (2007 ▶). For related structures, see: Zhu (2008 ▶); Zhu & Yang (2008a ▶,b ▶,c ▶); Qiu (2006a ▶,b ▶); Wei et al. (2007 ▶); Zhu et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[ZnI₂(C₁₄H₂₁BrN₂O)]·CH₄O
M _r = 664.45
Monoclinic,
a = 10.869 (2) Å
b = 17.562 (3) Å
c = 11.377 (2) Å
β = 94.358 (3)°
V = 2165.4 (7) Å³
Z = 4
Mo Kα radiation
μ = 5.84 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.388, T _max = 0.437
14106 measured reflections
4664 independent reflections
3499 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.105
S = 1.06
4664 reflections
225 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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/S1600536809038446/bx2241sup1.cif

e-65-m1293-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038446/bx2241Isup2.hkl

e-65-m1293-Isup2.hkl^{(233.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Zn1—O1	1.958 (4)
Zn1—N1	2.032 (5)
Zn1—I2′	2.545 (6)
Zn1—I1	2.5627 (9)
Zn1—I2	2.5768 (18)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.86	2.640 (6)	158
N2—H2A⋯O2	0.91 (6)	1.81 (6)	2.716 (7)	173 (8)

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Schiff bases have widely been used as versatile ligands in coordination chemistry (Biswas et al., 2008; Wu et al., 2008; Kawamoto et al., 2008; Ali et al., 2008; Habibi et al., 2007), and their metal complexes are of great interest in many fields (Chen et al., 2008; Yuan et al., 2007; Tomat et al., 2007; Darensbourg & Frantz, 2007). Zinc(II) is an important element in biological systems and functions as the active site of hydrolytic enzymes, such as carboxypeptidase and carbonic anhydrase where it is in a hard-donor coordination environment of nitrogen and oxygen ligands (Lipscomb & Sträter, 1996). Recently, we have reported a few Schiff base zinc complexes (Zhu, 2008; Zhu & Yang, 2008a,b,c). In this paper, the title new zinc(II) complex, Fig. 1, is reported.

The complex consists of a mononuclear zinc(II) complex molecule and a methanol molecule. The Zn^II atom is four-coordinated by the imine N and phenolate O atoms of the zwitterionic form of the Schiff base ligand, and by two I^- ions, in a distorted tetrahedral coordination. The coordinate bond lengths (Table 1) are typical and comparable to the corresponding values observed in the Schiff base zinc complexes we reported previously and other similar Schiff base zinc complexes (Zhu et al., 2007; Wei et al., 2007; Qiu, 2006a,b). I2 atom is disordered over two positions [0.702(19/0.298 (19)].

In the crystal structure, the methanol molecules are linked to the Schiff base molecules through O—H···O and N—H···O hydrogen bonds generating a graph-set motif C²₂(10) chain along [100] direction (Table 2, Fig. 2). (Bernstein et al., 1995)

Experimental

The Schiff base compound was prepared by the condensation of equimolar amounts of 5-bromosalicylaldehyde with N,N-diethylpropane-1,3-diamine in a methanol solution. The complex was prepared by the following method. To an anhydrous methanol solution (5 ml) of ZnI₂ (31.9 mg, 0.1 mmol) was added a methanol solution (10 ml) of the Schiff base compound (31.3 mg, 0.1 mmol) with stirring. The mixture was stirred for 30 min at room temperature and filtered. Upon keeping the filtrate in air for a few days, colorless block-shaped crystals were formed.