trans-Dichloridobis[(6-nicotinoyl-2-pyridyl-κN 6)(3-pyridyl-κN)methanone]copper(II)

Hong Qiang; Fan Zhang

doi:10.1107/S1600536811017685

. 2011 May 14;67(Pt 6):m758. doi: 10.1107/S1600536811017685

trans-Dichloridobis[(6-nicotinoyl-2-pyridyl-κN ⁶)(3-pyridyl-κN)methanone]copper(II)

Hong Qiang ^a,^*, Fan Zhang ^a

PMCID: PMC3120631 PMID: 21754646

Abstract

In the title complex, [CuCl₂(C₁₇H₁₁N₃O₂)₂], the Cu^II ion is located on an inversion center. It exhibits a distorted octahedral coordination geometry defined by two chloride anions at trans sites and four 3-pyridyl N atoms at equatorial sites from two (6-nicotinoyl-2-pyridyl)(3-pyridyl)methanone ligands. The (6-nicotinoyl-2-pyridyl)(3-pyridyl)methanone ligand can be viewed as having two pendant 3-pyridyl rings attached to a central pyridyl skeleton via separate carbonyl bridges, acting in a κ² N,N′-chelating mode with its 3-pyridyl N atoms bound to the Cu^II ion. The pendant 3-pyridyl rings make a dihedral angle of 80.76 (5)°. In the crystal, molecules are linked through intermolecular C—H⋯π and C—H⋯O interactions, forming a three-dimentional framework.

Related literature

For transition metal complexes with di-pyrid-2-yl ketone, see: Papaefstathiou & Perlepes (2002 ▶); Efthymiou et al. (2006 ▶). For the crystal structure of an analogous Cu^II complex, see: Wan et al. (2008 ▶). For C—H⋯π interactions, see: Umezawa et al. (1998 ▶).

Experimental

Crystal data

[CuCl₂(C₁₇H₁₁N₃O₂)₂]
M _r = 713.02
Monoclinic,
a = 18.728 (3) Å
b = 11.8971 (18) Å
c = 16.695 (3) Å
β = 121.522 (3)°
V = 3170.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.848, T _max = 1.000
11215 measured reflections
3937 independent reflections
3361 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.084
S = 1.04
3937 reflections
215 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017685/zq2102sup1.cif

e-67-0m758-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017685/zq2102Isup2.hkl

e-67-0m758-Isup2.hkl^{(193.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C13–C17,N3 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O1ⁱ	0.93	2.61	3.418 (2)	146
C2—H2A⋯Cg1ⁱⁱ	0.93	2.73	3.621 (3)	162

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

Acknowledgments

The authors are grateful for financial support from the Science and Technology program, Beijing Municipal Education Commission.

supplementary crystallographic information

Comment

Di-pyridin-2-yl-methanone (di-pyrid-2-yl ketone, DPK), (C₅H₄N)₂CO, is an extraordinarily versatile ligand among the thousands of basic building blocks that have been used in coordination chemistry and materials science (Papaefstathiou & Perlepes, 2002; Efthymiou et al., 2006). Herein, we report the mononuclear Cu^II complex with the oligo-pyridyl ketone ligand (6-nicotinoyl-2-pyridyl)(3-pyridyl)methanone (abbreviated as L), a member of the pyridinylmethanone family.

In the crystal structure of the title complex, the center Cu^II adopts an octahedral coordination geometry with two chlorido depositing in trans to each other, and two 2,6-pyridinediylbis(3-pyridinyl)methanone ligands bound to the ion by four 3-pyridyl N atoms (Fig. 1). The Cu1—N3 and Cu1—Cl1 bond lengths equal 2.0412 (12) Å and 2.3087 (4) Å, respectively, while the Cu-N1 exhibits weak bonding with the Cu-N1 distance of 2.615 (1) Å. The latter Cu—N bonds are remarkably longer than that (about 2.03 Å) in the similar complex Cu(L)₂(BF₄)₂ (Wan et al. 2008). The pendant 3-pyridyl rings exhibit a dihedral angle of 80.76 (5)°. The mononuclear complex units link each other through the intermolecular C2—H2A···π and C13—H13A···O1ⁱⁱ interactions to form a three-dimentional framework, as shown in Fig. 2. For the C—H···π interaction (Umezawa et al. 1998), the C2···Cg1 distance (where Cg1 is the centroid of the ring containing N3ⁱ; i: -x+1, -y, 0.5-z) is 3.621 (3) Å, and the C2—H2A···Cg1 angle is 161.8° . For the C—H···O interaction, the C13···O1ⁱⁱ distance is 3.418 (2) Å, and the C13—H13A···O1ⁱⁱ angle is 146.2° (ii: x+0.5, y-0.5, z).

Experimental

The (6-nicotinoyl-2-pyridyl)(3-pyridyl)methanone ligand was obtained following the reaction procedure as reported in literature (Wan et al., 2008). Reaction of (6-nicotinoyl-2-pyridyl)(3-pyridyl)methanone (29 mg, 0.1 mmol) with CuCl₂ (7 mg, 0.05 mmol) in acetonitrile formed trans-[Cu(C₁₇H₁₁N₃O₂)₂Cl₂] as a blue solution, which was left stand in air for four days to obtain block-like crystals (yield 13.1mg, 61%).