(μ-3-Acetyl-5-carboxyl­ato-4-methyl­pyrazolido-1:2κ4 N 2,O 3:N 1,O 5)-μ-chlorido-tetra­pyridine-1κ2 N,2κ2 N-chlorido-1κCl-dicopper(II) propan-2-ol solvate

Sergey Malinkin; Larisa Penkova; Vadim A Pavlenko; Matti Haukka; Igor O Fritsky

doi:10.1107/S1600536809038276

. 2009 Sep 26;65(Pt 10):m1247–m1248. doi: 10.1107/S1600536809038276

(μ-3-Acetyl-5-carboxylato-4-methylpyrazolido-1:2κ⁴ N ²,O ³:N ¹,O ⁵)-μ-chlorido-tetrapyridine-1κ² N,2κ² N-chlorido-1κCl-dicopper(II) propan-2-ol solvate

Sergey Malinkin ^a,^*, Larisa Penkova ^a, Vadim A Pavlenko ^a, Matti Haukka ^b, Igor O Fritsky ^a

PMCID: PMC2970235 PMID: 21577764

Abstract

The title compound, [Cu₂(C₇H₆N₂O₃)Cl₂(C₅H₅N)₄]·C₃H₈O, is a binuclear pyrazolate complex, in which the two Cu^II atoms have different coordination numbers and are connected by a bridging Cl atom. One Cu^II atom has a distorted square-pyramidal coordination environment formed by two pyridine N atoms, one bridging Cl atom and an N,O-chelating pyrazolate ligand. The other Cu^II atom adopts an octahedral geometry defined by two pyridine N atoms at the axial positions, two Cl atoms and the coordinated pyrazolate ligand in the equatorial plane. An O—H⋯O hydrogen bond connects the complex molecules and propan-2-ol solvent molecules into pairs. These pairs form columns along the a axis.

Related literature

For other 3,5-substituted-1H-pyrazolate complexes, see: Driessen et al. (2003 ▶); Eisenwiener et al. (2007 ▶); King et al. (2004 ▶); Li (2005 ▶); Penkova et al. (2008 ▶); Tretyakov et al. (2008 ▶).

Experimental

Crystal data

[Cu₂(C₇H₆N₂O₃)Cl₂(C₅H₅N)₄]·C₃H₈O
M _r = 740.61
Monoclinic,
a = 16.4130 (4) Å
b = 12.6351 (2) Å
c = 16.5739 (4) Å
β = 107.2145 (12)°
V = 3283.12 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.50 mm⁻¹
T = 100 K
0.24 × 0.16 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.718, T _max = 0.832
45344 measured reflections
8719 independent reflections
6355 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.086
S = 1.03
8719 reflections
402 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038276/hy2229sup1.cif

e-65-m1247-sup1.cif^{(28.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038276/hy2229Isup2.hkl

e-65-m1247-Isup2.hkl^{(426.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1	1.9814 (18)
Cu1—N3	2.0609 (18)
Cu1—N4	2.0371 (18)
Cu1—O1	2.5878 (17)
Cu1—Cl1	2.2634 (6)
Cu1—Cl2	2.8621 (6)
Cu2—N2	1.9549 (18)
Cu2—N5	2.0097 (18)
Cu2—N6	2.1987 (18)
Cu2—O2	2.0340 (16)
Cu2—Cl2	2.3036 (6)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H3O⋯O3	0.95	1.82	2.734 (3)	160

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Acknowledgments

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. F28/241-2009).

supplementary crystallographic information

Comment

Pyrazole-based chelating ligands form a variety of coordination complexes providing various coordination geometries and nuclearities (Eisenwiener et al., 2007). In the synthesis of supramolecular inorganic architectures by design, the assembly of molecular units in predefined arrangements is a key goal (Tretyakov et al., 2008). Linear bi- and trinuclear copper(II) complexes are of interest as models for the active sites of multicopper proteins, like ascorbate oxidase, ceruloplasmin and laccase (Driessen et al., 2003), and are also of interest for a better understanding of the magnetic properties of multicopper compounds (Penkova et al., 2008). The preparation and crystal structure of the title compound, a novel binuclear pyrazolate complex based on 5-acetyl-4-methyl-1H-pyrazol-3-carboxylic acid incorporating two Cu centres in different coordination environments, are reported herein. The complex was obtained as a product of the hydrolytic cleavage of L (see Scheme 2) in the presence of Cu ions.

In the molecular structure, the Cu^II atoms adopt different types of coordination geometries (Fig. 1). The geometry around Cu2 is distorted square-pyramidal. The Cu2—N2 bond distance is 1.9549 (18) Å (Table 1), close to those observed in the pyrazolato-bridged, linear trinuclear Cu^II complex reported by Driessen et al. (2003) [average Cu—N = 1.965 (5) Å]. The carboxylate group is in the basal plane with Cu2—O2 distance similar to that observed in the structure reported by Li (2005) [Cu—O = 2.016 (3) Å]. The N atom of a pyridine molecule occupies the apical position with Cu2—N6 distance of 2.1987 (18) Å. The Cu1 atom is situated in a slightly distorted octahedral environment formed by two N atoms belonging to the pyridine molecules occupying the axial positions, two Cl atoms (one of which is bridging) and N and O atoms of the pyrazolate ligand providing an N,O-chelating coordination mode with Cu—N = 1.9814 (18) Å.

The pyrazolate ring and one Cl atom bridge two Cu^II ions. The intermetallic separation Cu1—Cu2 is 3.9067 (4) Å, which is similar to that seen in the structure reported by King et al. (2004) (3.962 Å).

The crystal packing is presented in Fig. 2. An O—H···O hydrogen bond connects the complex molecule and propan-2-ol solvent molecule in pair. These units are stacked along the crystallographic b axis, forming a column-like structure. The two pyridine molecules interact through an intramolecular π–stacking interaction with a distance of 3.869 (1) Å between the centroids of the pyridine rings in the complex.

Experimental

Copper(II) chloride dihydrate (0.05 g, 0.29 mmol) was dissolved in DMF (4 ml), and mixed with solution of L (0.078 g, 0.29 mmol) in DMF (3 ml). Then to the reaction mixture pyridine was added within 24 h . Blue block-shaped crystals of the title compound were obtained upon slow diffusion of propan-2-ol vapour into dark-green solution during two weeks (the solution turns blue over time). Analysis calculated for C₃₀H₃₄Cl₂Cu₂N₆O₄: C 48.61, H 4.59, N 11.34%; found: C 48.45, H 4.70, N 11.43%.