Aqua­bis­(3,5-dimethyl-1H-pyrazole-κN 2)(oxydiacetato-κ3 O,O′,O′′)copper(II) dihydrate

Yan-Li Wang; Guang-Jun Chang; Bing-Xin Liu

doi:10.1107/S1600536811015169

. 2011 May 7;67(Pt 6):m682. doi: 10.1107/S1600536811015169

Aquabis(3,5-dimethyl-1H-pyrazole-κN ²)(oxydiacetato-κ³ O,O′,O′′)copper(II) dihydrate

Yan-Li Wang ^a, Guang-Jun Chang ^a, Bing-Xin Liu ^a,^*

PMCID: PMC3120427 PMID: 21754590

Abstract

In the title compound, [Cu(C₄H₄O₅)(C₅H₈N₂)₂(H₂O)]·2H₂O, the Cu^II cation assumes a distorted octahedral coordination geometry formed by two 3,5-dimethyl-1H-pyrazole ligands, one oxydiacetate (ODA) dianion and one coordinated water molecule. The tridentate ODA ligand chelates to the Cu cation in a facial configuration with a longer Cu—O bond [2.597 (3) Å], and both chelating rings display envelope conformations. In the molecule, the two pyrazole rings are twisted with respect to each other at a dihedral angle of 57.5 (3)°. Extensive intermolecular O—H⋯O and N—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For background to pyrazole compounds, see: Haanstra et al. (1990 ▶); Mukherjee (2000 ▶). For the structure of a related ODA complex, see: Wu et al. (2003 ▶).

Experimental

Crystal data

[Cu(C₄H₄O₅)(C₅H₈N₂)₂(H₂O)]·2H₂O
M _r = 441.93
Triclinic,
a = 7.5502 (12) Å
b = 10.6264 (17) Å
c = 12.687 (2) Å
α = 92.219 (2)°
β = 104.880 (2)°
γ = 93.769 (2)°
V = 980.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 295 K
0.25 × 0.19 × 0.15 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.767, T _max = 0.840
5085 measured reflections
3389 independent reflections
2663 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.133
S = 1.05
3389 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015169/xu5195sup1.cif

e-67-0m682-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015169/xu5195Isup2.hkl

e-67-0m682-Isup2.hkl^{(162.8KB, 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
O1—H1A⋯O32ⁱ	0.85	2.21	2.798 (5)	126
O1—H1B⋯O32ⁱⁱ	0.85	1.97	2.764 (5)	156
O1W—H1WA⋯O34	0.85	1.93	2.707 (8)	151
O1W—H1WB⋯O35ⁱⁱⁱ	0.85	2.45	3.097 (8)	133
O2W—H2WA⋯O32ⁱⁱ	0.85	2.23	3.024 (8)	156
O2W—H2WB⋯O1W^iv	0.88	1.87	2.741 (10)	171
N12—H12A⋯O34ⁱⁱⁱ	0.77	2.03	2.773 (5)	163
N22—H22A⋯O31ⁱⁱ	0.75	2.20	2.904 (5)	155

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

Acknowledgments

The project was supported by the Foundation of Shanghai University, China.

supplementary crystallographic information

Comment

Complexes with pyrazole-based ligands are a frequent subject of chemical investigations giving an opportunity for a better understanding the relationship between the structure and the activity of the active site of metalloproteins (Haanstra et al. 1990). Nowadays, attention is paid to the design of various pyrazole ligands with special structural properties to fulfill the specific stereochemical requirements of a particular metal-binding site (Mukherjee, 2000). In our systematic studies on transition metal complexes with the pyrazole derivatives, the title compound was prepared and its X-ray structure is presented here

The molecular structure of the title compound is shown in Fig. 1. The complex has a distorted octahedral coordination geometry formed by two 3,5-dimethyl-1H-pyrazole ligands, an oxydiacetate (ODA) dianion and a coordinated water molecule.

Monodentate ligand 3,5-dimethyl-1-H-pyrazole coordinated to the Cu(II) atom by N atoms of pyrazole rings with the 2.015 (4) Å and 1.996 (4) Å of Cu—N bound distance. The adjacent molecules are linked together via O—H···O and N—H···O hydrogen bonding (Table 1) occours between carboxy groups of oxydiacetate dianion and uncoordinated N atom of 3,5-dimethyl-1-H-pyrazole and coordinated water to form the supra-molecular structure as shown in Fig. 2 and Table 1.

The tridentate ODA chelates to Cu(II) atom in a facial configuration, similar to that found in an ODA complex of Cu(II) (Wu et al., 2003). Two carboxyl groups of ODA monodentately coordinate to the Cu(II) atom with the 2.020 (3) Å and 1.959 (3) Å of Cu—O31 and Cu—O33 respectively. Uncoordinated carboxyl oxygen atoms O32 and O34 are hydrogen bonded to the hydrogen atoms of coordinated water of the neighboring complex molecule, as shown in Fig. 2 and Table 1. The uncoordinated carboxyl oxygen atom O32 is hydrogen bonded to the hydrogen atoms of lattice watter molecule and coordinated water of the neighboring complex molecule respectively.

Experimental

An ethanol-water solution (1:1, 20 ml) containing 3,5-dimethyl-pyrazole-1-carboxamide (0.07 g, 0.5 mmol) and CuCl₂^.2H₂O (0.85g, 0.5 mmol) was mixed with an aqueous solution (10 ml) of oxydiacetic acid (0.07g, 0.5 mmol) and NaOH (0.04g, 1 mmol). The mixture was refluxed for 6 h. After cooling to room temperature the solution was filtered. Blue single crystals of (I) were obtained from the filtrate after 30 d.