Bis(di-2-pyridylmethane­diol-κ3 N,O,N′)copper(II) dl-tartrate

Jun Zhao; Dong-Sheng Li; Wen-Wen Dong; Dan-Jun Wang; Li Guo

doi:10.1107/S1600536808034983

. 2008 Nov 8;64(Pt 12):m1488–m1489. doi: 10.1107/S1600536808034983

Bis(di-2-pyridylmethanediol-κ³ N,O,N′)copper(II) dl-tartrate

Jun Zhao ^a, Dong-Sheng Li ^a,^*, Wen-Wen Dong ^a, Dan-Jun Wang ^b, Li Guo ^b

PMCID: PMC2960086 PMID: 21581112

Abstract

The reaction of di-2-pyridyl ketone with copper dichloride dihydrate and tartaric acid in water afforded the title compound, [Cu(C₁₁H₁₀N₂O₂)₂]C₄H₄O₆. The Cu^II atom lies on an inversion center N,O,N′-chelated by two di-2-pyridylmethanediol ligands in a tetragonally distorted octahedral geometry. The tartrate anion is also located on an inversion center and has disordered hydroxyl groups, each with an occupancy factor of 0.5. The hydroxyl groups of the complex cation are hydrogen bonded to the carboxylate groups of the anion, thus connecting the two building units.

Related literature

For backgroung on di-2-pyridylketone complexes, see: Deveson et al. (1996 ▶); Sommerer et al. (1993 ▶); Wang et al. (1986 ▶).

Experimental

Crystal data

[Cu(C₁₁H₁₀N₂O₂)₂]C₄H₄O₆
M _r = 616.03
Triclinic,
a = 7.7893 (8) Å
b = 8.1068 (8) Å
c = 11.3136 (12) Å
α = 105.973 (1)°
β = 90.431 (1)°
γ = 110.584 (1)°
V = 638.65 (11) Å³
Z = 1
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 293 (2) K
0.45 × 0.30 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.726, T _max = 0.850
3231 measured reflections
2235 independent reflections
1978 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.091
S = 1.03
2235 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 I, global. DOI: 10.1107/S1600536808034983/hy2156sup1.cif

e-64-m1488-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034983/hy2156Isup2.hkl

e-64-m1488-Isup2.hkl^{(109.8KB, hkl)}

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

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

Cu1—N1	2.003 (2)
Cu1—N2	2.019 (2)
Cu1—O1	2.3920 (19)

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N1—Cu1—N2ⁱ	91.08 (9)
N1—Cu1—N2	88.92 (9)
N1—Cu1—O1ⁱ	104.11 (8)
N2—Cu1—O1ⁱ	106.37 (8)
N1—Cu1—O1	75.89 (8)
N2—Cu1—O1	73.63 (8)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱⁱ	0.85	1.73	2.582 (3)	178
O2—H2A⋯O4ⁱⁱ	0.82	1.84	2.648 (3)	170
O5—H5⋯O3	0.82	2.15	2.641 (5)	119
O6—H6⋯O4	0.82	2.22	2.693 (5)	118
C2—H2⋯O5ⁱⁱⁱ	0.93	2.38	3.249 (6)	156
C3—H3⋯O4^iv	0.93	2.50	3.217 (4)	134
C4—H4⋯O5	0.93	2.45	3.258 (5)	146

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

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (grant No. 20773104), the Program for New Century Excellent Talents in Universities (NCET-06–0891), the Key Project of the Chinese Ministry of Education (grant No. 208143) and the Important Project of Hubei Provincial Education Office (09HB81).

supplementary crystallographic information

Comment

Di-2-pyridylketone (dpk) functions either as a bidentate N,N'-donor or as a tridentate N,O,N'-donor towards metal ions, depending on the reaction medium used in the synthesis of the complexes (Deveson et al., 1996), and several mononuclear and polynuclear transition metal–dpk complexes have been reported (Sommerer et al., 1993; Wang et al., 1986). The structural investigations clearly demonstrate that in each case hydration occurs across the ketone double bond in the ligand and that the resulting hydroxyl group coordinates to metal.

In the title compound, two dipyridin-2-yl-methanediol ligands, each in a tridentate fashion, are bonded to the Cu^II atom lying on an inversion center (Fig. 1). The pyridyl N atoms are strongly coordinated to the metal in the equatorial plane, while the hydroxyl groups are relatively weakly coordinated in the axial positions (Table 1). The two Cu—O(hydroxy) bonds [2.392 (2) Å], being in a trans arrangement, significantly exceed the Cu—N bond distances, a feature which can be attributed to the Jahn-Teller effect and usually manifests in d⁹ metal systems. The tartrate anion is located on an inversion center with disordered hydroxyl groups, each has an occupancy factor of 0.5. The hydroxyl groups of the complex cation as donors are involved in hydrogen bonds with the tartrate anion (Table 2).

Experimental

A mixture of di-2-pyridylketone (0.184 g, 1 mmol), CuCl₂.2H₂O (0.067 g, 0.5 mmol), tartaric acid (0.075 g, 0.5 mmol) and water (18 ml) in a 25 ml Teflon-lined stainless steel reactor was heated from 298 to 453 K in 2 h and maintained at 453 K for 72 h. After the mixture was cooled to 298 K, blue crystals of the title compound were obtained.