Bis(1,10-phenanthroline-κ2 N,N′)[2-(4-sulfonato­anilino)acetato-κO]copper(II) dihydrate

Yue Lu; Xing Li; Yue Bing; Mei-Qin Zha; Yin-Xin Li

doi:10.1107/S160053681100746X

. 2011 Mar 9;67(Pt 4):m402–m403. doi: 10.1107/S160053681100746X

Bis(1,10-phenanthroline-κ² N,N′)[2-(4-sulfonatoanilino)acetato-κO]copper(II) dihydrate

Yue Lu ^a, Xing Li ^a,^*, Yue Bing ^a, Mei-Qin Zha ^a, Yin-Xin Li ^a

PMCID: PMC3100003 PMID: 21753937

Abstract

In the title compound, [Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O, the Cu^II ion is coordinated by four N atoms from two 1,10-phenanthroline (phen) ligands and one O atom from a 2-(4-sulfonatoanilino)acetate (spia) ligand in a distorted square-pyramidal geometry. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds, as well as π–π interactions between phen ligands and between phen and spia ligands [centroid–centroid distances = 3.663 (3), 3.768 (3) and 3.565 (3) Å], result in a three-dimensional supramolecular structure.

Related literature

For metal complexes with flexible or semi-rigid ligands, see: Chu et al. (2008 ▶); Xu et al. (2006a ▶,b ▶); Yong et al. (2004 ▶, 2005 ▶).

Experimental

Crystal data

[Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O
M _r = 689.19
Triclinic,
a = 9.3437 (19) Å
b = 13.274 (3) Å
c = 13.880 (3) Å
α = 64.61 (3)°
β = 88.77 (3)°
γ = 69.83 (3)°
V = 1443.6 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 293 K
0.24 × 0.18 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.825, T _max = 0.931
14102 measured reflections
6590 independent reflections
5238 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.130
S = 1.11
6590 reflections
409 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −1.99 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: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100746X/hy2409sup1.cif

e-67-0m402-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100746X/hy2409Isup2.hkl

e-67-0m402-Isup2.hkl^{(317.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O2	1.993 (2)
Cu1—N1	1.999 (2)
Cu1—N2	2.049 (2)
Cu1—N3	2.005 (2)
Cu1—N4	2.212 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O2ⁱ	0.86	2.35	3.173 (4)	160
O6—H6A⋯O4	0.76	2.11	2.850 (5)	166
O6—H6B⋯O1ⁱⁱ	0.86	2.15	2.963 (5)	156
O7—H7B⋯O3ⁱⁱⁱ	0.72	2.24	2.915 (4)	156
O7—H7A⋯O5^iv	0.76	2.11	2.785 (4)	148

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

Acknowledgments

This work was supported by the Ningbo Natural Science Foundation of China (2010A610060), the ’Qianjiang Talent’ Projects of Zhejiang Province (2009R10032), the Ningbo University Foundation (XK1066) and the K. C. Wong Magna Fund in Ningbo University.

supplementary crystallographic information

Comment

Flexible or semi-rigid ligands can adopt various conformations and coordination modes according to the geometric requirements of different metal ions, which have attracted more attention in the fields of supramolecular chemistry (Chu et al., 2008; Xu et al., 2006a,b; Yong et al., 2004, 2005). Here we use N-(4-sulfanilicphenyl)iminoacetic acid (H₂spia) and CuSO₄.5H₂O to prepare a copper compound with the spia ligand. The title compound is a mononuclear complex, with five-coordinated Cu^II ions. As shown in Fig. 1, the Cu^II ion is coordinated by one O atom from an spia ligand and four N atoms from two 1,10-phenanthroline ligands. There are two uncoordinated water molecules in the asymmetric unit.

Experimental

H₂spia was prepared following the method described by Yong et al. (2005). A solution of KOH (2.694 g, 48 mmol) in water (5 ml) was added dropwise to chloroacetic acid sodium salt (2.796 g, 24 mmol) in water (5 ml) with stirring. Sulfanilic acid (1.044 g, 6 mmol) was slowly added to the reaction mixture and KI (0.025 g) was added as catalyst. Then the mixture was refluxed at about 80°C for 30 h. The reaction solution was cooled to room temperature and acidified with HCl (6 mol/L) until the desired white acidic material precipitated (pH = 3), which was filtered, washed with water and dried in air.

The title compound was prepared by a solvent evaporation method. A mixture of CuSO₄.5H₂O (0.025 g, 0.1 mmol), H₂spia (0.029 g, 0.1 mmol), and 1,10-phenanthroline (0.040 g, 0.20 mmol) in 15 ml of water was heated for 30 min. One drop of KOH solution was added to adjust pH to 5, and then the mixture was filtered. Dark green single crystals suitable for X-ray analysis were obtained by slow evaporation of solvent at room temperature.