Bis(μ-4-chloro-2-oxidobenzoato)bis­[(1,10-phenanthroline)copper(II)] dihydrate

Jing-Jing Nie; Jun-Hua Li; Duan-Jun Xu

doi:10.1107/S1600536810008354

. 2010 Mar 10;66(Pt 4):m387–m388. doi: 10.1107/S1600536810008354

Bis(μ-4-chloro-2-oxidobenzoato)bis[(1,10-phenanthroline)copper(II)] dihydrate

Jing-Jing Nie ^a, Jun-Hua Li ^a, Duan-Jun Xu ^a,^*

PMCID: PMC2983983 PMID: 21580494

Abstract

The structure of the the title compound, [Cu₂(C₇H₃ClO₃)₂(C₁₂H₈N₂)₂]·2H₂O, consists of a dimeric unit involving a planar Cu₂O₂ group arranged around an inversion center. The coordination sphere of the Cu^II atom can be described as an elongated distorted square pyramid where the basal plane is formed by the two N atoms of the 1,10-phenanthroline molecule and the two O atoms of the hydroxychlorobenzoate (hcbe) anion. The long apical Cu—O distance of 2.569 (2) Å involves the O atom of a symmetry-related hcbe anion, building up the dinuclear unit. Each dinuclear unit is connected through O—H⋯O hydrogen bonds involving two water molecules, resulting in an R ₄ ²(8) graph-set motif and building up an infinite chain parallel to (10 Inline graphic ). C—H⋯O interactions further stabilize the chain.

Related literature

For our ongoing investigation of the nature of π–π stacking, see: Su & Xu (2004 ▶); Xu et al. (2007 ▶). For related structures, see: Yang et al. (2006 ▶); Garland et al. (1987 ▶); Li et al. (1995 ▶); Fan & Zhu (2005 ▶); Song et al. (2007 ▶). For a structural discussion on hydrogen bonding, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Cu₂(C₇H₃ClO₃)₂(C₁₂H₈N₂)₂]·2H₂O
M _r = 864.60
Monoclinic,
a = 8.1941 (17) Å
b = 18.851 (4) Å
c = 11.873 (3) Å
β = 105.993 (8)°
V = 1763.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 294 K
0.33 × 0.30 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.656, T _max = 0.730
18894 measured reflections
3163 independent reflections
2162 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.103
S = 1.03
3163 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008354/dn2542sup1.cif

e-66-0m387-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008354/dn2542Isup2.hkl

e-66-0m387-Isup2.hkl^{(152KB, 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—H1A⋯O2	0.90	1.92	2.817 (4)	175
O1W—H1B⋯O2ⁱ	0.88	2.13	2.921 (4)	150
C10—H10⋯O2ⁱⁱ	0.93	2.42	3.277 (5)	153
C17—H17⋯O1Wⁱ	0.93	2.58	3.487 (4)	166

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

Acknowledgments

The work was supported by the ZIJIN project of Zhejiang University, China.

supplementary crystallographic information

Comment

As part of our ongoing investigation on the nature of π-π stacking (Su & Xu, 2004; Xu et al., 2007), the title Cu^II compound incorporating 2-hydroxy-4-chlorobenzoate (hcbe) ligand has recently been prepared in the laboratory and its crystal structure is reported here.

The structure of the the title compound, (C₁₉H₁₁ClCuN₂O₃).(H₂O), consists of a dimeric unit involving a planar Cu₂O₂ group arranged around inversion center The coordination sphere of the Cu^II can be described as an elongated distorted square pyramid where the basal plane is formed by the two N atoms of the 1,10-phenanthroline molecule and the two O atoms of the hydroxychlorobenzoate (hcbe) anion. The long apical Cu-O3 distance of 2.569 (2)A involves the O3 atom of the symmetry related hcbe anion [symmetry code (i) i-x,1-y,1-z] building up the dinuclear unit (Fig. 1).

This apical Cu-O3 distance is 0.674 (3) Å longer than Cu—O3 bond distance in the basal coordination plane, showing the Jahn-Teller distorted square-pyramidal coordination geometry around the Cu^II cation. A patially overlapped arrangement is observed between the nearly parallel C2-C7 phenyl ring and C11-C19 phen ring system [dihedral angle 14.25°]. The centroid to centroid distance is 3.649 (3) Å and the perpendicular distance of the centroid to the rings is 3.456 and 3.571 Å respectively suggesting a weak π-π stacking comparable to that found in the related Cu^II complexes (Garland et al., 1987; Li et al., 1995; Fan & Zhu, 2005; Song et al., 2007) and also to the Ni^II complex of 2,4-dihydroxybenzoate (Yang et al., 2006).

Each dinuclear unit are connected through O-H···O hydrogen bonds involving two water molecules resulting in a R²₄(8) graph set motif ( Etter et al., 1990, Bernstein et al., 1995) and building up an infinite chain parallel to the (1 0 -1) plane. C-H···O interactions further stabilize the chain. (Table 1; Fig. 2).

Experimental

An ethanol-water solution (20 ml, 1:3) containing 2-hydroxy-4-chlorobenzoic acid (0.173 g, 1 mmol), Na₂CO₃ (0.053 g, 0.5 mmol) and CuCl₂.2H₂O (0.085 g, 0.5 mmol) was refluxed for 6 h, then phenanthroline hydrate (0.99 g, 1 mmol) was added into the solution and the mixture was refluxed for further 0.5 h. After cooling to room temperature the solution was filtered. Single crystals of the title compound were obtained from the filtrate after one week.