{5,5′-Dimeth­oxy-2,2′-[1,1′-(2,2-dimethyl­propane-1,3-diyldinitrilo)­diethyl­idyne]diphenolato-κ4 O,N,N′,O′}copper(II) monohydrate

Akbar Ghaemi; Saeed Rayati; Ehsan Elahi; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S160053681103889X

. 2011 Sep 30;67(Pt 10):m1445–m1446. doi: 10.1107/S160053681103889X

{5,5′-Dimethoxy-2,2′-[1,1′-(2,2-dimethylpropane-1,3-diyldinitrilo)diethylidyne]diphenolato-κ⁴ O,N,N′,O′}copper(II) monohydrate

Akbar Ghaemi ^a,^‡, Saeed Rayati ^b, Ehsan Elahi ^a, Seik Weng Ng ^c,^d, Edward R T Tiekink ^c,^*

PMCID: PMC3201301 PMID: 22058715

Abstract

The tetradentate dianion in the title complex hydrate, [Cu(C₂₃H₂₈N₂O₄)]·H₂O, provides the Cu^II atom with a cis-N₂O₂ donor set. There is a significant twist from a regular square-planar geometry with the dihedral angle formed between the two six-membered CuOC₃N chelate rings being 32.14 (8)°. The water molecule forms hydrogen bonds to each of the coordinating O atoms of a given complex molecule. Supramolecular layers in the bc plane are formed in the crystal packing through C—H⋯O and C—H⋯π interactions.

Related literature

For the catalytic potential of Schiff base complexes of Cu^II, see: Gupta & Sutar (2008 ▶); Rayati et al. (2010 ▶). For the structure of the ligand, see: Ghaemi et al. (2011 ▶). For crystallization conditions, see: Harrowfield et al. (1996 ▶).

Experimental

Crystal data

[Cu(C₂₃H₂₈N₂O₄)]·H₂O
M _r = 478.03
Triclinic,
a = 10.4721 (7) Å
b = 10.8023 (9) Å
c = 10.8487 (7) Å
α = 106.699 (7)°
β = 99.823 (5)°
γ = 100.035 (6)°
V = 1125.37 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 294 K
0.40 × 0.40 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.643, T _max = 1.000
11143 measured reflections
5034 independent reflections
4332 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.105
S = 0.99
5034 reflections
285 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) general, I. DOI: 10.1107/S160053681103889X/hg5100sup1.cif

e-67-m1445-sup1.cif^{(24.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103889X/hg5100Isup2.hkl

e-67-m1445-Isup2.hkl^{(246.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu—O2	1.8825 (16)
Cu—O3	1.8776 (15)
Cu—N1	1.9597 (17)
Cu—N2	1.9524 (18)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w⋯O2	0.84	2.12	2.832 (3)	142
O1w—H2w⋯O3	0.84	2.32	3.035 (3)	143
C7—H7c⋯O1wⁱ	0.96	2.55	3.476 (5)	163
C16—H16c⋯O2ⁱⁱ	0.96	2.52	3.409 (3)	153
C14—H14b⋯Cg1ⁱⁱ	0.97	2.62	3.426 (2)	141

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

Acknowledgments

We gratefully acknowledge practical support of this study by K. N. Toosi University of Technology, Islamic Azad University (Saveh Branch), and thank the University of Malaya for supporting the crystallographic facility.

supplementary crystallographic information

Comment

Synthetic copper(II) Schiff base complexes have long been of great interest because of their potential as catalysts in the oxidation of various organic compounds (Gupta & Sutar, 2008). In continuation of research in this field (Rayati et al., 2010), the title complex, (I), was investigated.

The tetradentate dianion in the title monohydrate, (I), Fig. 1, provides a cis-N₂O₂ donor set, Table 1. Three six-membered chelate rings are formed as a result of coordination of the dianion. The CuNC₃N ring adopts a half-chair conformation. While the CuOC₃N chelate ring containing the O3 atom approaches planarity with a r.m.s. deviation of 0.031 Å, the other ring displays significant distortions. Thus, the r.m.s. deviation for the O2-containing CuOC₃N chelate ring is 0.163 Å with maximum deviations of 0.162 (2) Å for atom O2 and -0.159 (1) Å for the Cu atom. The dihedral angle formed between the two CuOC₃N chelate rings is 32.14 (8)° indicating a significant distortion from a regular square planar geometry. Each of the methoxy groups is co-planar with the benzene ring to which it is attached as seen in the values of the C7—O1—C3—C2 and C23—O4—C20—C19 of -0.8 (4) and -179.3 (3)°, respectively. The water molecule of solvation is associated with the complex, forming a bridge via its hydrogen atoms between the two coordinated oxygen atoms, Table 2.

The crystal packing features C—H···O and C—H···π interactions, Table 2, that assemble molecules into layers in the bc plane, Fig. 2, which stack along the a axis, Fig. 3.

Experimental

The title complex was obtained by the template method in a branch tube (Harrowfield et al., 1996). The recently described (Ghaemi et al., 2011) N,N'-bis(2-hydroxy-4-methoxyacetophenone)-2,2-dimethylpropane-1,3-diamine (0.40 g, 1 mmol) and copper(II) acetate monohydrate (0.199 g, 1 mmol) were placed in the main arm of a branched tube. Ethanol was added to fill both arms. The tube was sealed and the main arm immersed in an oil bath at 333 K while the other was held at ambient temperature. After one week, crystals deposited in the cooler arm. These were filtered off and air dried. Yield: 75%. FT—IR data: ν(C═N) 1595 cm^-1.