(N,N-Diethyl­nicotinamide-κN 1)bis­[4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dionato-κ2 O,O′]copper(II)

Abel M Maharramov; Vusala I Mardanova; Famil Chyraqov; Atash V Gurbanov; Seik Weng Ng

doi:10.1107/S1600536811014401

. 2011 May 7;67(Pt 6):m708–m709. doi: 10.1107/S1600536811014401

(N,N-Diethylnicotinamide-κN ¹)bis[4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dionato-κ² O,O′]copper(II)

Abel M Maharramov ^a, Vusala I Mardanova ^a, Famil Chyraqov ^a, Atash V Gurbanov ^a, Seik Weng Ng ^b,^*

PMCID: PMC3120436 PMID: 21754609

Abstract

In the title compound, [Cu(C₈H₄F₃O₂S)₂(C₁₀H₁₄N₂O)], the Cu^II atom exists in a distorted CuNO₄ square-pyramidal geometry; the metal atom lies above a square plane defined by four O atoms of the two chelating anionic ligands, displaced in the direction of the axial occupant, the pyridine N atom, by 0.179 (1) Å. Weak intermolecular C—H⋯O and C—H⋯F hydrogen bonding is present in the crystal structure. One thienyl ring is disordered over two orientations in an occupancy ratio of 0.69 (1):0.31.

Related literature

For the related crystal structure of bis[4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dionato]copper(II), see: Lecomte et al. (1988 ▶); Wang et al. (1996 ▶); Xu et al. (2010 ▶). For some adducts with N-heterocycles, see: Gou et al. (1991 ▶); Li et al. (1994 ▶); Liu et al. (1986 ▶); Yu et al. (1988 ▶).

Experimental

Crystal data

[Cu(C₈H₄F₃O₂S)₂(C₁₀H₁₄N₂O)]
M _r = 684.12
Triclinic,
a = 11.4324 (5) Å
b = 12.8606 (5) Å
c = 13.0104 (5) Å
α = 62.837 (1)°
β = 64.110 (1)°
γ = 88.783 (1)°
V = 1492.72 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.618, T _max = 0.746
16434 measured reflections
6849 independent reflections
5423 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.152
S = 1.05
6849 reflections
392 parameters
80 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014401/xu5194sup1.cif

e-67-0m708-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014401/xu5194Isup2.hkl

e-67-0m708-Isup2.hkl^{(335.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.9432 (19)
Cu1—O2	1.942 (2)
Cu1—O3	1.944 (2)
Cu1—O4	1.934 (2)
Cu1—N1	2.262 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O5ⁱ	0.93	2.49	3.358 (7)	156
C19—H19⋯O5ⁱⁱ	0.93	2.56	3.338 (6)	141
C24—H24C⋯F1ⁱⁱⁱ	0.96	2.36	3.233 (13)	151

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

Acknowledgments

We thank Baku State University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Square-planar bis[4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dionato]copper is a Lewis acid that forms adducts with a number of N-heterocycles. The parent Lewis acid exists as a square-planar molecule; its crystal structure has been determined several times (Lecomte et al., 1988; Wang et al., 1996; Xu et al., 2010). For most adducts, the Cu atom exists in a six-coordinate geometry, e.g., the pyridine adduct (Liu et al., 1986). The 4,4'-bipyridine adduct exists in two forms; in one form, the Cu atom is octahedrally coordinated (Gou et al., 1991). The other is a dinuclear adduct in which the Cu atom shows the square-pyramidal coordination. In the title N,N-diethylbenzamide adduct (Scheme I), the Cu atom is similarly five-coordinate. The metal atom lies above the square plane defined by the O atoms of the two chelating anionic ligands in the direction of the axial occupant by 0.179 (1) Å.

Experimental

Bis[4,4,4-trifluoro-1-(thien-2-yl)butane-1,3-dionato]copper was synthesized by using a literature procedure (Lecomte et al., 1988; Wang et al., 1996; Xu et al., 2010). A solution of theonyltrifluoroacetylacetone (0.44 g, 0.002 mol) in ethanol (50 ml) and N,N-diethylnicotinamide (0.18 g, 0.001 mol) was added to a solution of copper sulfate pentahydrate (0.25 g, 0.001 mol) dissolved in water (50 ml). The resulting green solution has heated for a hour and then set aside for a week. The solid was filtered and recrystallized from ethanol (80%, m.p. 515 K); yield 65%. CHN&S elemental analysis. Found: C 45.69, H 3.31, S 9.48, F 16.75%; calculated for C₂₆H₂₂N₂O₅CuF₆S₂: C 45.61, H 3.22, S 9.36, F 16.67%.