catena-Poly[[chloridocopper(I)]-μ-η2,σ1-3-(2-allyl-2H-tetra­zol-5-yl)pyridine]

Wei Wang

doi:10.1107/S1600536808013895

. 2008 Jun 7;64(Pt 7):m900–m901. doi: 10.1107/S1600536808013895

catena-Poly[[chloridocopper(I)]-μ-η²,σ¹-3-(2-allyl-2H-tetrazol-5-yl)pyridine]

Wei Wang ^a,^*

PMCID: PMC2961697 PMID: 21202765

Abstract

The title compound, [CuCl(C₉H₉N₅)]_n, prepared by solvothermal synthesis, is a new homometallic Cu^I–olefin coordination polymer in which the Cu^I atoms are linked by the 3-(2-allyl-2H-tetrazol-5-yl)pyridine ligands and are each bonded to one terminal Cl atom. The organic ligand acts as a bidentate ligand bridging two neighboring Cu centers through the bonds to the N atom of the pyridine ring and the double bond of the allyl group. Weak Cu⋯Cl [3.136 (8) Å), C—H⋯Cl and C—H⋯N interactions connect the coordination polymers into a three-dimensional structure.

Related literature

For the solvothermal synthesis and for related structures, see: Ye et al. (2005 ▶,2007 ▶); Wang (2008 ▶).

Experimental

Crystal data

[CuCl(C₉H₉N₅)]
M _r = 286.21
Triclinic,
a = 7.3005 (15) Å
b = 7.6560 (15) Å
c = 9.981 (2) Å
α = 80.51 (3)°
β = 77.00 (3)°
γ = 84.68 (3)°
V = 535.23 (19) Å³
Z = 2
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 293 (2) K
0.2 × 0.15 × 0.1 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.806, T _max = 1.000 (expected range = 0.643–0.797)
5572 measured reflections
2443 independent reflections
1918 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.103
S = 1.16
2443 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶) and SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013895/gk2142sup1.cif

e-64-0m900-sup1.cif^{(15KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013895/gk2142Isup2.hkl

e-64-0m900-Isup2.hkl^{(120KB, hkl)}

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

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

Cu1—N1	1.995 (3)
Cu1—C9ⁱ	2.026 (3)
Cu1—C8ⁱ	2.044 (3)
Cu1—Cl3	2.2408 (10)

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N1—Cu1—C9ⁱ	105.86 (13)
N1—Cu1—C8ⁱ	143.90 (13)
C9ⁱ—Cu1—C8ⁱ	39.16 (14)
N1—Cu1—Cl3	108.44 (9)
C9ⁱ—Cu1—Cl3	145.70 (11)
C8ⁱ—Cu1—Cl3	106.88 (10)

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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
C1—H1A⋯Cl3ⁱⁱ	0.96	2.79	3.675 (4)	154
C2—H2A⋯N4ⁱⁱ	0.96	2.59	3.379 (5)	139
C4—H4A⋯N4	0.96	2.57	2.909 (4)	101
C6—H6A⋯Cl3ⁱⁱⁱ	0.96	2.83	3.607 (4)	139

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

Acknowledgments

This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

Under hydrothermal or solvothermal conditions some interesting reactions occur. Often new compounds can be obtained that cannot be synthesized using conventional solution techniques. In sealed tube, unstable copper(I) salt can exist under vacuum, and thus interesting copper(I) coordination compounds can be obtained (Ye et al., 2005, 2007). The title compound, as colorless block crystals suitable for X-ray analysis, was obtained through solvothermal treatment of CuCl and 3-(2-allyl-2H-tetrazol -5-yl)pyridine in methanol at 75°C. Isostructural product was obtained when CuBr was used for the reaction (Wang, 2008).

The 3-(2-allyl-2H-tetrazol-5-yl) pyridine ligands bind to the copper(I) centers through the N atom of pyridine and double bond of the allyl group (C8—C9 1.364 (5) Å). The copper atom is coordinated to two olefinic organic ligands and one terminal Cl atom in a trigonal environment (Fig 1, Table 1). The organic ligands link the neighboring Cu centers to form a homometallic Cu(I) coordination polymer developing along the c axis. Unfortunately, the N atoms of the tetrazole ring fail to coordinate to Cu(I)(Fig. 1).

Finally, weak Cu—Cl (3.136 Å), C–H···Cl and C–H···N interactions between the coordination polymers lead to the formation of the three-dimensional structure (Fig. 2).

Experimental

A mixture of 3-(2-allyl-2H-tetrazol-5-yl)pyridine(20 mg, 0.2 mmol), CuCl (17.9 mg, 0.2 mmol) were placed in a thick Pyrex tube (ca 20 cm in length). After addition of methanol, the tube was frozen with liquid nitrogen, evacuated under vaccum, sealed with a torch and kept at 348 K. Colorless block-shaped crystals suitable for X-ray analysis were obtained after 5 d (yield 61% based on the organic ligand).