Bis{2-hydr­oxy-N-[2-(2-pyrid­yl)eth­yl]benzamide}copper(I) tetra­fluoridoborate

Zhaodong Wang; Douglas R Powell; Robert P Houser

doi:10.1107/S1600536810001364

. 2010 Jan 16;66(Pt 2):m173. doi: 10.1107/S1600536810001364

Bis{2-hydroxy-N-[2-(2-pyridyl)ethyl]benzamide}copper(I) tetrafluoridoborate

Zhaodong Wang ^a, Douglas R Powell ^a, Robert P Houser ^a,^*

PMCID: PMC2979673 PMID: 21579646

Abstract

The title complex, [Cu(C₁₄H₁₄N₂O₂)₂]BF₄, is a monomeric copper(I) species with linear two-coordinate geometry around the Cu^I atom. The asymmetric unit contains two half-cations that sit on crystallographic twofold rotation axes. The selected crystal was non-merohedrally twinned by a twofold rotation about an axis normal to the (100) family of planes. The ratio of the twin components refined to 0.4123 (6). Two 2-hydroxy-N-[2-(2-pyridyl)ethyl]benzamide ligands coordinate to each Cu^I atom via the pyridyl N atom. Intramolecular hydrogen bonding between the phenol OH groups and the amide O atoms imparts rigidity and planarity to the non-coordinating end of the ligand. The cationic complex is linked to the BF₄ ⁻ anions via hydrogen bonding between the amide NH groups in the cations and BF₄ ⁻ anions.

Related literature

For the synthesis and coordination chemistry of 2-hydroxy-N-(2-(2-pyridyl)ethyl)benzamide, see: Wang et al. (2009 ▶). For the copper(I) coordination chemistry of pyridylamides, see Yang et al. (2007 ▶) and references therein.

Experimental

Crystal data

[Cu(C₁₄H₁₄N₂O₂)₂]BF₄
M _r = 634.89
Monoclinic,
a = 21.943 (5) Å
b = 17.586 (4) Å
c = 14.607 (2) Å
β = 107.988 (8)°
V = 5361.2 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.12 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (TWINABS; Bruker, 2001 ▶) T _min = 0.714, T _max = 0.905
10344 measured reflections
10344 independent reflections
8548 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.096
S = 1.00
10344 reflections
393 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810001364/bt5166sup1.cif

e-66-0m173-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001364/bt5166Isup2.hkl

e-66-0m173-Isup2.hkl^{(505.9KB, hkl)}

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

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

Cu1A—N1A	1.8872 (16)
Cu1B—N1B	1.8874 (17)

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N1A—Cu1A—N1Aⁱ	178.45 (9)
N1B—Cu1B—N1Bⁱⁱ	177.71 (9)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9A—H9A⋯F1ⁱⁱⁱ	0.72 (2)	2.23 (2)	2.923 (2)	161 (2)
O18A—H18A⋯O11A	0.83 (1)	1.79 (2)	2.554 (2)	152 (3)
N9B—H9B⋯F2^iv	0.82 (1)	2.16 (1)	2.937 (2)	159 (2)
O18B—H18B⋯O11B	0.81 (1)	1.81 (2)	2.549 (2)	153 (2)

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

Acknowledgments

The National Science Foundation (CHE-0094079) supported this work. We also thank the NSF (CHE-0130835) and the University of Oklahoma for the purchase of a CCD equipped X-ray diffractometer.

supplementary crystallographic information

Comment

Our laboratory has synthesized copper(I) and copper(II) complexes of pyridylmethylamide ligands that display different coordination modes depending on whether or not the amide group is protonated (Wang, et al. 2009, and references therein). The synthesis of copper(I) complexes with these ligands is limited to the neutral form of the ligand, where the amide group is not deprotonated (Yang, et al. 2007, and references therein). Attempts to synthesize copper(I) species in the presence of base results in disproportionation of the copper(I) to copper(0) and copper(II). The title complex was synthesized with the phenol-substituted ligand 2-hydroxy-N-(2-(2-pyridyl)ethyl)benzamide. Copper(II) complexes with 2-hydroxy-N-(2-(2-pyridyl)ethyl)benzamide are either mononuclear, when synthesized in the absence of base ([Cu(C₁₄H₁₄N₂O₂)₂Cl₂]), or a tetracopper cluster, in the presence of base ([Cu₄(C₁₄H₁₂N₂O₂)₄]) (Wang, et al. 2009). The ligand in the tetracopper cluster is a dianion with the amide NH and the phenol OH both deprotonated. The title complex differs from both copper(II) complexes in that the ligand only coordinates via the pyridyl N atom.

Experimental

2-hydroxy-N-(2-(2-pyridyl)ethyl)benzamide was synthesized using a previously reported procedure (Wang, et al. 2009). The title complex, [Cu(C₁₄H₁₄N₂O₂)₂]BF₄, was synthesized using the following procedure: A solution of [Cu(CH₃CN)₄]BF₄ (0.0778 g, 0.250 mmol) in CH₃CN was added to a solution of 2-hydroxy-N-(2-(2-pyridyl)ethyl)benzamide (0.121 g, 0.500 mmol) in CH₃CN. The resulting light yellow solution was filtered, and vapor diffusion of diethyl ether produced light yellow crystals of the title complex (0.114 g, 72% yield).