Aqua­[4-chloro-2-(2-pyridylmethyl­imino­meth­yl)phenolato]copper(II) nitrate monohydrate

Qing Liang; Xiaodan Chen; Huaihong Zhang; Zhihong Zou

doi:10.1107/S1600536809052350

. 2009 Dec 12;66(Pt 1):m40. doi: 10.1107/S1600536809052350

Aqua[4-chloro-2-(2-pyridylmethyliminomethyl)phenolato]copper(II) nitrate monohydrate

Qing Liang ^a, Xiaodan Chen ^a, Huaihong Zhang ^a, Zhihong Zou ^a,^*

PMCID: PMC2980213 PMID: 21579939

Abstract

In the title mononuclear complex, [Cu(C₁₃H₁₀ClN₂O)(H₂O)]NO₃·H₂O, the Cu^II atom is four-coordinated by two N atoms and one O atom of the tridentate Schiff base ligand and one O atom from the coordinated water molecule in a slightly distorted square-planar configuration. The nitrate ion interacts with the copper center [Cu1⋯O3 = 2.579 (4) Å]. In the crystal, the cations, anions and water molecules are linked by O—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For the role of copper proteins in fundamental biological processes, see: Arnesano et al. (2004 ▶). For the chemistry of copper compounds, see: Bosnich (1968 ▶); Costes et al. (1995 ▶); Downing & Urbach (1969 ▶); Ganeshpure et al. (1996 ▶). For related structures, see: Sun et al. (2005 ▶); You et al. (2004 ▶).

Experimental

Crystal data

[Cu(C₁₃H₁₀ClN₂O)(H₂O)]NO₃·H₂O
M _r = 407.26
Triclinic,
a = 7.892 (2) Å
b = 8.9741 (12) Å
c = 11.8929 (15) Å
α = 106.841 (2)°
β = 102.198 (1)°
γ = 92.897 (1)°
V = 782.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 298 K
0.47 × 0.41 × 0.30 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.520, T _max = 0.645
4114 measured reflections
2714 independent reflections
2280 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.074
S = 1.06
2714 reflections
218 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536809052350/zq2021sup1.cif

e-66-00m40-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052350/zq2021Isup2.hkl

e-66-00m40-Isup2.hkl^{(133.2KB, hkl)}

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

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

Cu1—O1	1.889 (2)
Cu1—N1	1.936 (3)
Cu1—O2	1.975 (2)
Cu1—N2	1.982 (3)

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O1—Cu1—N1	93.94 (10)
O1—Cu1—O2	88.85 (9)
N1—Cu1—O2	171.60 (10)
O1—Cu1—N2	176.81 (10)
N1—Cu1—N2	82.98 (11)
O2—Cu1—N2	94.32 (10)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2a⋯O5	0.85	1.83	2.676 (4)	173
O2—H2a⋯N3	0.85	2.52	3.253 (4)	146
O2—H2a⋯O3	0.85	2.57	3.052 (4)	117
O2—H2b⋯O6ⁱ	0.85	1.81	2.657 (4)	174
O6—H6a⋯O1ⁱⁱ	0.85	2.08	2.915 (3)	166
O6—H6b⋯O4	0.85	1.93	2.782 (5)	177

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

supplementary crystallographic information

Comment

Metals ions are vital for living organisms because they are involved in many fundamental biological processes, e.g. copper proteins known to be involved in a crucial role, such as respiration, iron transport, oxidative stress protection, blood clotting and pigmentation (Arnesano et al., 2004). The study of copper compounds is of great interest in various aspects of chemistry (Downing & Urbach, 1969; Ganeshpure et al., 1996; Bosnich, 1968; Costes et al., 1995). The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. The Cu^II atom is four- coordinated by two nitrogen atoms and one oxygen atom of the tridentate Schiff base ligand, and one oxygen atom from the coordinated water molecule, forming a slightly distorted square-planar coordination configuration. The four coordinating atoms around the Cu centre are approximately coplanar. The Cu1—N2 bond [1.982 (2) Å; Table 1] is a little longer than the value [1.977 (4) Å] observed in a similar copper(II) complex (Sun et al., 2005). The Cu1—N1 bond length [1.936 (2) Å] is comparable with the corresponding value [1.934 (4) Å] observed in the same complex mentioned above (Sun et al., 2005). The Cu1—O1 bond length is 1.889 (18) Å. The nitrate ion is in interaction with the copper center [Cu1···O3 = 2.579 (4) Å]. The bond angles around the Cu^II centre show some deviations from ideal square-planar geometry. The Schiff base ligands from adjacent molecules are almost parallel due to by π-π interactions leading to the formation of two-dimensional parallel layers (Fig.2). The cations, anions and solvent water molecules are linked by O-H···O hydrogen bonds.

Experimental

2-Aminomethylpyridine (0.1 mmol, 10.8 mg) and 5-chloro-salicylaldehyde (0.1 mmol, 15.6 mg) were dissolved in methanol (10 ml). The mixture was stirred for 1 h to give a clear yellow solution. To this solution was added a water solution (10 ml) of Cu(NO₃)2.3H₂O (0.1 mmol, 24.2 mg), with stirring. The mixture was stirred for 10 min to give a deep green solution, which was allowed to evaporate slowly in the open at room temperature. After 5 days, deep blue block-shaped crystals suitable for an X-ray diffraction study were formed at the bottom of the vessel.