Aqua­{N-[(4-methyl­phen­yl)sulfon­yl]glycinato(2−)-κ2 N,O}(1,10-phenan­throline)copper(II)

Miao-Ling Huang

doi:10.1107/S1600536810036135

. 2010 Sep 15;66(Pt 10):m1255. doi: 10.1107/S1600536810036135

Aqua{N-[(4-methylphenyl)sulfonyl]glycinato(2−)-κ² N,O}(1,10-phenanthroline)copper(II)

Miao-Ling Huang ^a,^*

PMCID: PMC2983433 PMID: 21587403

Abstract

In the title complex, [Cu(C₉H₉NO₄S)(C₁₂H₈N₂)(H₂O)], the Cu^II ion is coordinated in a distorted square-pyramidal geometry by the two N atoms from a 1,10-phenanthroline ligand, one N atom from the deprotonated amino group of an N-tosylglycinate ligand, one O atom from the carboxylate part of the N-tosylglycinate ligand and a water O atom. Intermolecular O—H⋯O hydrogen bonds involving the water H atoms link neighboring molecules into supramolecular chains along [010]. Weak π–π stacking interactions [centroid–centroid distances of 3.456 (1) and 3.691 (1) Å] between the benzene rings of 1,10-phenanthroline ligands of adjacent molecules extend the chains into a layer structure parallel to (001).

Related literature

For the coordination chemistry of N-sulfonyl amino acids, see: Liang et al. (2004 ▶); Ma et al. (2008 ▶). For related structures, see: Battaglia et al. (1983 ▶); Antolini et al. (1985 ▶); Menabue & Saladini (1991 ▶).

Experimental

Crystal data

[Cu(C₉H₉NO₄S)(C₁₂H₈N₂)(H₂O)]
M _r = 488.99
Monoclinic,
a = 14.0788 (11) Å
b = 7.0588 (6) Å
c = 20.6993 (17) Å
β = 103.826 (1)°
V = 1997.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 296 K
0.32 × 0.29 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.693, T _max = 0.747
14609 measured reflections
3713 independent reflections
3341 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.065
S = 1.06
3713 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036135/zq2057sup1.cif

e-66-m1255-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036135/zq2057Isup2.hkl

e-66-m1255-Isup2.hkl^{(182.1KB, 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
O5—H1W⋯O2ⁱ	0.85	1.87	2.717 (2)	175
O5—H2W⋯O4ⁱⁱ	0.85	2.00	2.847 (2)	174

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

Acknowledgments

This work was supported by the Education Department Foundation of Fujian Province of China (grant No. 2008 F5053) and the Master Construction Project of Quanzhou Normal University.

supplementary crystallographic information

Comment

As a kind of amino acid derivatives, the N-protected amino acid plays an important role in participating in the process of the life activity. The substitution of an Ar—SO₂-group on the amine nitrogen of amino acids, such as glycine and B-alanine, increases the coordination donors behavior of amino acids to three types of O, N donors from carboxyl, sulfoxyl and amine respectively, which may lead to different coordination modes, thus is of great interest in studying the coordination chemistry of N-sulfonyl- amino acids for many chemical workers (Ma et al., 2008; Liang et al., 2004; Battaglia et al., 1983; Menabue et al., 1991; Antolini et al., 1985). In order to continue the research, we synthesized the title complex [Cu(C₉H₉NO₄S)(C₁₂H₈N₂)(H₂O)] and characterized it by an elemental analysis and a single-crystal X-ray diffraction analysis.

The molecular structure and crystal packing diagram of the title compound are presented in Figs. 1 and 2, respectively. The asymmetric unit contains one copper cation, one Ts-gly anion, one phen molecule and one coordinated water molecule. The central copper ion adopts a distorted square-pyramidal geometry by two N(N2, N3) atoms of the 1,10-phenanthroline ligand, one N(N1) and one O(O1) atoms of the Ts-gly ion occupying basal site, while the apical position is occupied by another O atom of a water molecule. The Cu—O1 bond distance of 1.9269 (13) Å is shorter than those of other N-protected glycine complexes (1.933–1.967 Å) [Battaglia, et al., 1983; Antolini, et al., 1985; Menabue & Saladini, 1991]. Furthermore, the C—O bond distance for the coordinated O atom (1.282 (2) Å) is significantly longer than that for the uncoordinated O atom (1.233 (2) Å), which is similar to previously reported complexes (Battaglia, et al., 1983; Antolini, et al., 1985).

Intermolecular hydrogen bonds involving the water H atoms, O(5)—H(1W)···O(2)ⁱ, O(5)—H(2W)···O(4)ⁱⁱ(Table 1), link the neighboring molecules into one-dimensional supramolecular chains. Weak π-π stacking interactions between benzene rings of 1,10-phenanthroline ligands from adjacent molecules (centroid distances of 3.456Å and 3.691 Å) extend the one-dimensional chains into a two-dimensional layer structure.

Experimental

To a solution of Ts-gly (1 mmol) in water-DMF 1:1 (10 ml), an aqueous solution (5 ml) of CuCl₂.2H₂O (1 mmol) and a solution of 1,10-phenanthroline (1 mmol) in ethanol (95%, 5 ml) was added. After refluxing for 12 h at 343 K, the mixture was filtered off while hot. The green single crystals suitable for a X-ray analysis were obtained by slow evaporation of the filtrate at room temperature after 41 days. IR(KBr): 3442(vs), 1638(vs), 1586(s), 1518(s), 1493(m), 1434(s), 1382(vs), 1348(m), 1319(m), 1243(vs), 1132(vs), 1112(vs), 1078(s), 1007(s), 967(s), 940(m), 847(s), 820(m), 723(s),663(s), 589(s), 545(m) cm^-1.