{4,4′-Dimethyl-2,2′-[2,2-dimethyl­propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenolato}copper(II) monohydrate

Hadi Kargar; Reza Kia; Fatemeh Ganji; Valiollah Mirkhani

doi:10.1107/S1600536812034502

. 2012 Aug 11;68(Pt 9):m1172. doi: 10.1107/S1600536812034502

{4,4′-Dimethyl-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}copper(II) monohydrate

Hadi Kargar ^a,^*, Reza Kia ^b, Fatemeh Ganji ^a, Valiollah Mirkhani ^c

PMCID: PMC3435595 PMID: 22969468

Abstract

The asymmetric unit of the title compound, [Cu(C₂₁H₂₄N₂O₂)]·H₂O, comprises half of a Schiff base complex and half of a water molecule. The whole compound is generated by crystallographic twofold rotation symmetry. The geometry around the Cu^II atom, located on a twofold axis, is distorted square-planar, which is supported by the N₂O₂ donor atoms of the coordinating Schiff base ligand. The dihedral angle between the symmetry-related benzene rings is 47.5 (4)°. In the crystal, the water molecule that is hydrogen bonded to the coordinated O atoms links the molecules via O—H⋯O interactions into chains parallel to [001]. The crystal structure is further stabilized by C—H⋯π interactions, and by π–π interactions involving inversion-related chelate rings [centroid–centroid distance = 3.480 (4) Å].

Related literature

For applications of Schiff bases in coordination chemistry, see: Granovski et al. (1993 ▶); Blower (1998 ▶). For related structures, see: Ghaemi et al. (2011 ▶); Kargar et al. (2011 ▶, 2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C₂₁H₂₄N₂O₂)]·H₂O
M _r = 417.98
Monoclinic,
a = 13.353 (5) Å
b = 15.986 (5) Å
c = 10.023 (5) Å
β = 104.696 (5)°
V = 2069.5 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 296 K
0.11 × 0.08 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.891, T _max = 0.948
4967 measured reflections
1779 independent reflections
1053 reflections with I > 2σ(I)
R _int = 0.101

Refinement

R[F ² > 2σ(F ²)] = 0.084
wR(F ²) = 0.209
S = 0.95
1779 reflections
125 parameters
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812034502/su2488sup1.cif

e-68-m1172-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034502/su2488Isup2.hkl

e-68-m1172-Isup2.hkl^{(87.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1	0.85	2.46	2.783 (7)	103
O1W—H1W1⋯O1ⁱ	0.85	2.44	2.783 (7)	105
C3—H3⋯O1W ⁱⁱ	0.93	2.55	3.48 (1)	173
C8—H8B⋯Cg1ⁱⁱⁱ	0.97	2.83	3.693 (9)	148
C11—H11B⋯Cg1^iv	0.96	2.98	3.850 (12)	151

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

Acknowledgments

HK and FG thank PNU for financial support.

supplementary crystallographic information

Comment

Schiff base complexes are one of the most important stereochemical models in transition metal coordination chemistry, with the ease of preparation and structural variations (Granovski et al., 1993; Blower, 1998). In continuation of our work on the structural analysis of Schiff base metal complexes (Kargar et al., 2012; Kargar et al., 2011; Ghaemi, et al., (2011), we synthesized the title compound and report herein on its crystal structure.

The asymmetric unit of the title compound, Fig. 1, comprises half of a Schiff base complex and half a water molecule. The Cu1 and C9 atoms of the complex and the O atom of the water molecule lie on a two-fold rotation axis which generates the whole complex. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to those reported for related structures (Kargar et al., 2012; Kargar et al., 2011; Ghaemi et al., (2011). The geometry around the Cu^II atom is distorted square-planar which is supported by the N₂O₂ donor atoms of the coordinated Schiff base ligand. The dihedral angle between the substituted benzene rings is 47.5 (4)°.

In the crystal, the water molecule that is hydrogen bonded to the coordinated O atoms, O1, mediates linking of molecules by C—H···O interactions (Table 1 and Fig. 2). The crystal structure is further stabilized by C-H···π interactions (Table 1), and by π-π interactions involving inversion related chelate rings [Cg···Cgⁱ = 3.480 (4) Å; Cg is the centroid of the Cu1/O1/C1/C6/C7/N1 ring; symmetry code: (i) 1 - x, -y, -1 - z].

Experimental

The title compound was synthesized by adding 5-methyl-salicylaldehyde-2,2-dimethyl-1,3-propanediamine (2 mmol) to a solution of CuCl₂. 4H₂O (2.1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Dark-green single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.