Aqua­bis(3,5-dimethyl-1H-pyrazole-κN)(oxalato-κ2 O,O′)copper(II)

Andrii I Buvailo; Stefania V Tomyn; Matti Haukka; Vadim A Pavlenko; Igor O Fritsky

doi:10.1107/S1600536807058928

. 2007 Dec 6;64(Pt 1):m37–m38. doi: 10.1107/S1600536807058928

Aquabis(3,5-dimethyl-1H-pyrazole-κN)(oxalato-κ² O,O′)copper(II)

Andrii I Buvailo ^a, Stefania V Tomyn ^a, Matti Haukka ^b, Vadim A Pavlenko ^a, Igor O Fritsky ^a,^*

PMCID: PMC2914925 PMID: 21200611

Abstract

In the title compound, [Cu(C₂O₄)(C₅H₈N₂)₂(H₂O)], the Cu^II atom is coordinated in a slightly distorted square-pyramidal geometry by two N atoms belonging to the two 3,5-dimethyl-1H-pyrazole ligands, two O atoms of the oxalate anion providing an O,O′-chelating coordination mode, and an O atom of the water molecule occupying the apical position. The crystal packing shows a well defined layer structure. Intra-layer connections are realised through a system of hydrogen bonds while the nature of the inter-layer interactions is completely hydrophobic, including no hydrogen-bonding interactions.

Related literature

For related literature on metal oxalates and 1H-pyrazole complexes, see: Abdeljalil et al. (2006 ▶); Bataille & Louër (1999 ▶); Castillo et al. (2001 ▶); Naumov et al. (1995 ▶); Raptis et al. (1999 ▶); Strotmeyer et al. (2003 ▶); Tomyn et al. (2007 ▶); Warda (1998 ▶).

Experimental

Crystal data

[Cu(C₂O₄)(C₅H₈N₂)₂(H₂O)]
M _r = 361.84
Triclinic,
a = 8.2597 (6) Å
b = 8.4010 (8) Å
c = 12.2288 (11) Å
α = 77.007 (4)°
β = 89.189 (6)°
γ = 62.436 (5)°
V = 729.00 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 120 (2) K
0.23 × 0.13 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.720, T _max = 0.888
11529 measured reflections
3765 independent reflections
3186 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.070
wR(F ²) = 0.175
S = 1.12
3765 reflections
204 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807058928/hy2100sup1.cif

e-64-00m37-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807058928/hy2100Isup2.hkl

e-64-00m37-Isup2.hkl^{(552.3KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O2	1.946 (2)
Cu1—O5	1.971 (2)
Cu1—N2	1.975 (3)
Cu1—N3	2.002 (2)
Cu1—O1	2.283 (2)

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O2—Cu1—O5	84.54 (9)
O2—Cu1—N2	172.35 (10)
O5—Cu1—N2	92.59 (9)
O2—Cu1—N3	88.41 (10)
O5—Cu1—N3	170.11 (10)
N2—Cu1—N3	93.53 (10)
O2—Cu1—O1	89.05 (9)
O5—Cu1—O1	91.85 (9)
N2—Cu1—O1	98.15 (10)
N3—Cu1—O1	94.96 (9)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.99	1.88	2.798 (3)	153
O1—H2⋯O5ⁱⁱ	0.97	1.97	2.923 (3)	168
N1—H3⋯O3ⁱⁱⁱ	0.88	2.03	2.857 (3)	156
N4—H18⋯O3ⁱ	0.88	1.97	2.845 (3)	175

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

Acknowledgments

The authors thank NATO for financial support (grant CBP. NUKR. CLG 982019). AIB thanks the DAAD for a scholarship under the Leonhard-Euler-Stipendium Programme.

supplementary crystallographic information

Comment

1H-Pyrazole and its 3,5-substituted derivatives have been widely used as bridging ligands in molecular magnetism and supramolecular chemistry for obtaining discrete oligonuclear complexes of high nuclearity and coordination polymers (Abdeljalil et al., 2006; Raptis et al., 1999; Warda, 1998). On the other hand, oxalate is an important polynucleative ligand as it can exhibit various bridging modes, which, together with the varied coordination preferences of metal ions, can result in the formation of oligonuclear species or compounds containing one-, two- and three-dimensional coordination polymers and frameworks (Castillo et al., 2001; Naumov et al., 1995; Bataille & Louër, 1999; Strotmeyer et al., 2003; Tomyn et al., 2007). Simultanetous use of 1H-pyrazole derivatives and oxalates can result in the creation of new molecular topologies or in obtaining mononuclear complexes with vacant donor atoms, which can be used as building blocks for the preparation of oligonuclear assemblies or coordination polymers.

The molecular structure of the title compound (Fig. 1) consists of a Cu^II ion as the central atom possessing a slightly distorted square-pyramidal geometry. The four equatorial positions are occupied by two N atoms belonging to the two monodentately coordinated 3,5-dimethyl-1H-pyrazole molecules and two O atoms of the oxalate anion coordinated in an O,O'-chelate mode forming a five-membered chelate ring. The axial position is occupied by the O atom of the water molecule (Table 1). A crystal packing diagram (Fig. 2) depicts a well defined layer structure along the c-axis direction. Each layer is formed with the help of O1—H···O and N—H···O hydrogen bonds (Table 2) while the nature of inter-layer interactions is utterly hydrophobic including no hydrogen bonding interactions.

Experimental

Cu(NO₃)₂.3H₂O (0.242 g, 1 mmol) and 3,5-dimethyl-1H-pyrazole (0.961 g, 1 mmol) were dissolved in water (10 ml), and then a powder of K₂C₂O₄.H₂O (0.184 g, 1 mmol) was added to the obtained solution. The resulting mixture was stirred at 358 K for 25 min and filtered. Blue needle-like crystals suitable for X-ray analysis were formed from the filtrate in several minutes. They were filtered off and washed with diethyl ester (yield 67%). Analysis calculated for C₁₂H₁₈CuN₄O₅: C 39.83, H 5.01, N 15.48%; found: C 39.11, H 5.13, N 15.42%.