{6,6′-Dieth­oxy-2,2′-[2,2-dimethyl­propane-1,3-diylbis(nitrilo­methyl­idyne)]diphenolato}copper(II) monohydrate

Hadi Kargar; Reza Kia; Hoong-Kun Fun; Arezoo Jamshidvand

doi:10.1107/S1600536809012859

. 2009 Apr 10;65(Pt 5):m515–m516. doi: 10.1107/S1600536809012859

{6,6′-Diethoxy-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethylidyne)]diphenolato}copper(II) monohydrate

Hadi Kargar ^a, Reza Kia ^b,^‡, Hoong-Kun Fun ^b,^*, Arezoo Jamshidvand ^a

PMCID: PMC2977574 PMID: 21583760

Abstract

In the title complex, [Cu(C₂₃H₂₈N₂O₄)]·H₂O, the Cu^II ion has a distorted planar geometry, coordinated by the N₂O₂ unit of the tetradentate Schiff base ligand. The asymmetric unit comprises one complex molecule and a water molecule of crystallization. The water H atoms form bifurcated O—H⋯(O,O) intermolecular hydrogen bonds with the O atoms of the phenolate and ethoxy groups with R₁²(5) and R₁²(6) ring motifs, which may, in part, influence the molecular configuration. The dihedral angle between the two O—Cu—N coordination planes is 31.02 (6)° and the dihedral angle between the two benzene rings is 34.98 (7)°. In the crystal structure, molecules are linked together by intermolecular C—H⋯O interactions, forming extended chains along the a axis. The crystal structure is further stabilized by intermolecular C—H⋯π and π–π [centroid–centroid = 3.5068 (13) Å] interactions.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see Allen et al. (1987 ▶). For related structures see, for example: Clark et al. (1968 ▶, 1969 ▶, 1970 ▶). For applications and bioactivity of Cu(II) and Ni(II) Schiff base complexes see, for example: Elmali et al. (2000 ▶); Blower (1998 ▶); Granovski et al. (1993 ▶); Li & Chang (1991 ▶); Shahrokhian et al. (2000 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Cu(C₂₃H₂₈N₂O₄)]·H₂O
M _r = 478.03
Triclinic,
a = 9.427 (3) Å
b = 10.805 (3) Å
c = 12.771 (4) Å
α = 114.554 (13)°
β = 99.479 (14)°
γ = 102.676 (14)°
V = 1105.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 100 K
0.50 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.628, T _max = 0.861
36656 measured reflections
7929 independent reflections
6977 reflections with I > 2σI)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.077
S = 1.05
7929 reflections
290 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012859/kj2122sup1.cif

e-65-0m515-sup1.cif^{(25KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012859/kj2122Isup2.hkl

e-65-0m515-Isup2.hkl^{(387.9KB, 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
O1W—H2W1⋯O2ⁱ	0.78 (2)	2.41 (2)	2.9959 (18)	132.8 (18)
O1W—H2W1⋯O4ⁱ	0.78 (2)	2.27 (2)	3.0097 (19)	159 (2)
O1W—H1W1⋯O1ⁱ	0.75 (2)	2.20 (2)	2.8749 (16)	151 (2)
O1W—H1W1⋯O3ⁱ	0.75 (2)	2.54 (2)	3.1684 (19)	143 (2)
C7—H7A⋯O1W	0.95	2.56	3.451 (2)	157
C10—H10B⋯O2ⁱⁱ	0.99	2.57	3.476 (2)	151
C8—H8B⋯Cg1ⁱ	0.99	2.78	3.4918 (19)	129
C13—H13A⋯Cg1ⁱⁱ	0.95	2.85	3.3718 (18)	116
C18—H18B⋯Cg2ⁱⁱⁱ	0.99	2.79	3.718 (2)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C1–C6 and C12–C17 benzene rings.

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK and AJ thank PNU for financial support. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Schiff base complexes are some of the most important stereochemical models in transition metal coordination chemistry, with their ease of preparation and structural variations (Granovski et al., 1993). Metal derivatives of Schiff bases have been studied extensively, and copper(II) and Ni(II) complexes play a major role in both synthetic and structural research (Elmali et al., 2000; Blower, 1998; Granovski et al., 1993; Li & Chang, 1991; Shahrokhian et al., 2000). Tetradentate Schiff base metal complexes may form trans or cis planar or tetrahedral structures (Elmali et al., 2000).

The Cu^II ion of the title compound (Fig. 1), shows a distorted planar geometry which is coordinated by two imine N atoms and two phenol O atoms of the tetradentate Schiff base ligand. The bond lengths (Allen et al.,, 1987) and angles are within normal ranges and are comparable with the related structures (Clark et al., 1968, 1969, 1970). The asymmetric unit of the title compound comprises one molecule of complex and a water molecule of crystallization. The water H atoms form bifurcated O—H···(O,O) intermolecular hydrogen bonds with the O atoms of the phenolato and ethoxy groups with R₁²(5) and R₁²(6) ring motifs (Bernstein et al., 1995), which may, in part, influence the molecular configuration. The dihedral angle between the two benzene rings is 34.98 (7)°. In the crystal structure, the molecules are linked together by intermolecular C—H···O interactions, forming 1-D extended chains along the a axis (Fig. 2). The crystal structure is further stabilized by intermolecular C—H···π (Table 1) and π–π interactions [Cg3···Cg3ⁱ = 3.5068 (13) Å, Cg3 is the centroid of the Cu1/O1/C1/C6/C7/N1 ring, symmetry operation i = 1-x, 1-y, 1-z].

Experimental

A chloroform solution (40 ml) of [N,N'-Bis(3-ethoxy-salicylidene)-2, 2-dimethyl-1,3-propanediamin (1 mmol, 399 mg) was added to an ethanol solution (20 ml) of CuCl₂.4H₂O (1.05 mmol, 216 mg). The mixture was refluxed for 30 min and then filtered. After keeping the filtrate in air, green plate-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent.