Bis(1,10-phenanthroline-κ2 N,N′)(phenyl­acetato-κO)copper(II) phenyl­acetate hexa­hydrate

Bing-Tian Tu; Hong-Zhen Xie; Ying-Tao Ren; Jing-Zhong Chen

doi:10.1107/S1600536808032480

. 2008 Oct 31;64(Pt 11):m1475. doi: 10.1107/S1600536808032480

Bis(1,10-phenanthroline-κ² N,N′)(phenylacetato-κO)copper(II) phenylacetate hexahydrate

Bing-Tian Tu ^a, Hong-Zhen Xie ^b,^*, Ying-Tao Ren ^a,^b, Jing-Zhong Chen ^a

PMCID: PMC2959544 PMID: 21580909

Abstract

In the title compound, [Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O, the Cu atom is in a distorted square-pyramidal coordination environment. The six crystallographically independent uncoordinated water molecules are interconnected by hydrogen bonds, completing dodecawater (H₂O)₁₂ clusters which are hydrogen bonded to the carboxylate groups of phenylacetate anions, building up one-dimensional anionic chains propagating along [100]. Between the cationic and anionic chains are hydrogen bonds from water molecules to the carboxylate O atoms belonging to the phenylacetato ligands.

Related literature

For general background, see: Kuroda-Sowa et al. (1997 ▶); Lehn (2007 ▶); Li et al. (2008 ▶). For related structures, see: Addison & Rao (1984 ▶); Baruah et al. (2007 ▶); Liu & Xu (2005 ▶); Ma et al. (2005 ▶); Sugimori et al. (1997 ▶); Zheng et al. (2001 ▶).

Experimental

Crystal data

[Cu(C₈H₇O₂)(C₁₂H₈N₂)₂](C₈H₇O₂)·6H₂O
M _r = 802.33
Triclinic,
a = 11.499 (2) Å
b = 11.903 (2) Å
c = 16.066 (3) Å
α = 71.00 (3)°
β = 72.97 (3)°
γ = 68.93 (3)°
V = 1901.3 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 293 (2) K
0.37 × 0.35 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.793, T _max = 0.902
18689 measured reflections
8680 independent reflections
7070 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.08
8680 reflections
496 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032480/pk2118sup1.cif

e-64-m1475-sup1.cif^{(28.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808032480/pk2118Isup2.hkl

e-64-m1475-Isup2.hkl^{(419.2KB, hkl)}

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

Acknowledgments

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).

supplementary crystallographic information

Comment

Construction of supramolecular architectures with interesting physical properties has grown rapidly owing to their potential use as new functional materials (Lehn, 2007). The most efficient and widely used approach for designing such materials is the self-assembly of organic ligands and metal ions (Kuroda-Sowa et al., 1997; Li et al., 2008). Here, we report a Cu(II) complex [Cu(C₁₂H₈N₂)₂(C₈H₇O₂)](C₈H₇O₂).6H₂O from the self-assembly of Cu(OH)₂, phenylacetatic acid and phenanthroline.

The title compound consists of [Cu(C₁₂H₈N₂)₂(C₈H₇O₂)]²⁺ complex cations, phenylacetate anions, and water molecules of crystallization (Fig.1). The Cu atoms are each coordinated by two phenanthroline ligands and one phenylacetato ligand to complete a square-pyramidal CuN₄O chromophore with the phenylacetic oxygen atom at the equatorial site. The equatorial Cu–N bond lengths fall in the range 2.002–2.060 Å and the Cu–O bond distance is equal to 2.001 (1) Å, while the axial Cu–N bond distance is 2.187 (2) Å. According to Addison's definition (Addison & Rao, 1984), the τ index about the central Cu atom is 0.233 Å, suggesting that the square pyramidal coordination geometry is slightly distorted with the Cu atom deviated from the basal plane by 0.1779 (8) Å towards the apical N1 atom. Within each complex cation, both phenanthroline ligands exhibit nearly perfect coplanarity and constitute an orthogonal system with the coordinating carboxylate group of the phenylacetate anion. The complex cation displays a similar configuration to those observed in a succinato complex [Cu(phen)₂(C₄H₄O₄)] previously reported by us (Zheng et al., 2001) and all the bonding parameters are normal (Baruah et al., 2007). As far as the phenylacetato ligand is concerned, the phenyl plane is found to be nearly perpendicular to the single bonded carbon backbone (dihedral angle: 89.5 (1)°), which is significantly larger than the corresponding one of 68.6 (2)° in the non-coordinating phenylacetate anion, and the carboxylate group is twisted from the single bonded carbon backbone by 70.4 (2)° in the former coordinating one, and is considerably larger the 60.7 (2)° in the non-coordinating anion. As expected, the C–O bond distance for the coordinating oxygen atom is 1.281 (2) Å, which is longer than those for non-coordinating ones (1.247–1.254 Å). The complex cations are distributed in such a way that the symmetry-related phenanthroline ligands are oriented antiparallel with a mean interplanar distance of 3.39 (2) Å, indicating a significant face-to-face π-π stacking interaction (Sugimori et al., 1997). Owing to such intercationic π-π stacking interactions and weak intercationic C–H···O interactions with the uncoordinating carboxylate oxygen atom, two centrosymmetrically related complex cations form dimers, which are further assembled via interdimeric π-π stacking interactions into 1D chains extending along the [101] direction. Furthermore, the resulting chains are arranged in planes parallel to (010), between which the lattice water molecules and the phenylacetate anions are sandwiched.

Out of the six crystallographically distinct lattice water molecules, three water molecules together with their centrosymmetry-related partners are hydrogen bonded to one another to generate chair-like hexawater clusters (Fig.2), to which the remaining lattice water molecules are associated by hydrogen bonds to complete dodecawater (H₂O)₁₂ clusters similar to those reported in the literature (Liu & Xu, 2005; Ma et al., 2005). The resulting dodecawater (H₂O)₁₂ clusters are hydrogen bonded to the carboxylate groups of phenylacetate anions to build up 1D anionic chains propagating along [100]. Between the cationic and anionic chains exist hydrogen bonds from water molecules to the carboxylate oxygen atoms belonging to the phenylacetato ligands.

Experimental

Dropwise addition of 2.0 mL(1.0 M) of NaOH to a aqueous solution of CuCl₂.2H₂O (0.170 g, 1.00 mmol) in 5.0 mL of H₂O gave a blue precipitate, which was separated by centrifugation and washed with water until no Cl anions were detectable in the supernatant. The collected blue precipitate was transferred to a mixture of ethanol and water (1:1 V/V, 10 mL), to which phenanthroline (0.198 g, 1.00 mmol) and phenylacetic acid (0.136 g, 1.00 mmol) were added successively. The resulting blue solution (pH = 7.52) was allowed to stand at room temperature. Blue blocklike crystals were grown by slow evaporation for over 7 days.