[5-(Pyridin-2-yl)-1H-tetra­zole-κ2 N 4,N 5]bis(triphenyl­phosphane-κP)copper(I) tetra­fluoridoborate

Lei Lu; Ping Yang; Bing Li; Lin-Fang Shi; Hua-Ru Cao

doi:10.1107/S1600536812047605

. 2012 Nov 28;68(Pt 12):m1527. doi: 10.1107/S1600536812047605

[5-(Pyridin-2-yl)-1H-tetrazole-κ² N ⁴,N ⁵]bis(triphenylphosphane-κP)copper(I) tetrafluoridoborate

Lei Lu ^a, Ping Yang ^a, Bing Li ^a, Lin-Fang Shi ^a,^*, Hua-Ru Cao ^a

PMCID: PMC3588771 PMID: 23468736

Abstract

In the title Cu^I compound, [Cu(C₆H₅N₅)(C₁₈H₁₅P)₂]BF₄, the Cu^I cation is N,N′-chelated by a 5-(pyridin-2-yl)-1H-tetrazole ligand and coordinated by two triphenylphosphane ligands in a distorted tetrahedral geometry. The tetrazole and pyridine rings are essentially coplanar [dihedral angle = 4.1 (3)°]. The tetrafluoridoborate anion links to the complex cation via an N—H⋯F hydrogen bond.

Related literature

For applications of Cu^I complexes, see: Jia et al. (2005 ▶); Tsuboyama et al. (2007 ▶); Zhang et al. (2004 ▶). For the synthesis, see: Kuang et al. (2002 ▶); Demko & Sharpless (2001 ▶).

Experimental

Crystal data

[Cu(C₆H₅N₅)(C₁₈H₁₅P)₂]BF₄
M _r = 822.05
Triclinic,
a = 9.6640 (19) Å
b = 13.052 (3) Å
c = 15.947 (3) Å
α = 88.66 (3)°
β = 84.80 (3)°
γ = 85.72 (3)°
V = 1997.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 293 K
0.29 × 0.17 × 0.16 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.908, T _max = 0.947
19069 measured reflections
8838 independent reflections
4984 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.166
S = 1.14
8838 reflections
496 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −1.12 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

Click here for additional data file.^{(26.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047605/xu5633sup1.cif

e-68-m1527-sup1.cif^{(26.4KB, cif)}

Click here for additional data file.^{(432.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047605/xu5633Isup2.hkl

e-68-m1527-Isup2.hkl^{(432.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu—P1	2.2575 (13)
Cu—P2	2.2538 (14)
Cu—N1	2.185 (4)
Cu—N2	2.103 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H55⋯F4ⁱ	0.86	1.80	2.650 (7)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Foundation of Zhejiang Province (grant No. LY12B02013), the Foundation of Zhejiang Education Committee (Y201119787), the National Natural Science Foundation of China (No. 51103136) and the National Natural Science Foundation of China (No. 21207117).

supplementary crystallographic information

Comment

Many copper(I) complexes have been utilized in solar energy conversion, biological probing, and organic light-emitting devices (Jia et al., 2005; Tsuboyama et al., 2007; Zhang et al., 2004). Therefore, it is pressing to explore new Cu(I) complexes served as luminescent materials. In this article, we have successfully synthesized a novel mixed ligand Cu(I) complex.

Scheme 1 and Figure 1 display the four-coordinated environment of complex [Cu(PPh₃)₂(L)]BF₄, the coordination geometry at the Cu atom is a distorted tetrahedron. The distances of N1 and N2 to Cu1 are 2.185 (4), and 2.103 (4) Å, respectively, and the Cu—P bond lengths are 2.2575 (13) and 2.2538 (14) Å. The counter tetrafluoroboronate ion links with the complex cation via N—H···F hydrogen bonds (Table 1).

Experimental

The 5-(2-Pyridyl)tetrazole ligand was synthesized according to the literature method (Demko & Sharpless, 2001) with some minor modification. The specific synthetic procedure is as follows: (i) To a 100 ml round-bottomed flask was added 2-cyanopyridine (0.52 g, 5 mmol), sodium azide (0.36 g, 5.5 mmol), zinc bromide (1.15 g, 5 mmol), and water (30 ml). The reaction mixture was refluxed for 5 h, cooled to room temperature. Then the mixture was basified by addition of 2.5 equiv of NaOH, filtered, acidified to pH = 1, and filtered, and the solid was washed with water then 5-(2-Pyridyl)tetrazole (0.58 g, 78%) was obtained.

[Cu(PPh₃)₂(L)]BF₄ was synthesized according to the following procedure (Kuang et al., 2002): To a 100 ml flask was added [Cu(CH₃CN)₄]BF₄ 0.314 g (1 mmol), triphenylphosphane 0.522 g(2 mmol) and 10 ml dichioromethane, kept stirring for 1 h. Then 0.148 g 5-(2-Pyridyl)tetrazole was added and stirred for another hour. After the evaporation of solvent, the product was obtained as a light green powder. Single crystals of complex [Cu(PPh₃)₂(L)]BF₄ suitable for X-ray diffraction studies were grown from slow evaporation of a CH₂Cl₂ solution.