Crystal structure of a π complex of AgBF4 with 2-allyl-5-phenyl-2H-tetrazole of the composition [Ag(C10H10N4)(BF4)]

Article abstract of DOI:10.1134/S0022476615010242

By the interaction of AgBF₄ with 2-allyl-5-phenyl-2H-tetrazole (2aphet) in the ethanol solution, a π complex of [Ag(2aphet)(BF₄)] is obtained which is studied using single crystal X-ray diffraction.

Full text of DOI:10.1134/S0022476615010242

Journal of Structural Chemistry. Vol. 56, No. 1, pp. 179-180, 2015.
Original Russian Text © 2015 Yu. I. Slyvka.
CRYSTAL STRUCTURE OF A π COMPLEX OF
AgBF WITH 2-ALLYL-5-PHENYL-2Н-TETRAZOLE
4
OF THE COMPOSITION [Ag(C H N )(BF )]
10 10 4 4
Yu. I. Slyvka
UDC 548.736:661
By the interaction of AgBF with 2-allyl-5-phenyl-2Н-tetrazole (2aphet) in the ethanol solution,
4
a π complex of [Ag(2aphet)(BF )] is obtained which is studied using single crystal X-ray diffraction.
4
DOI: 10.1134/S0022476615010242
Keywords: silver(I), π complex, tetrazole, crystal structure.
Coordination compounds of tetrazole derivatives have found a sufficiently wide application in the organic synthesis
as the precursors and catalysts for producing biologically active substances, corrosion inhibitors, luminophores, and as
efficient tools in crystal engineering of metal complexes [1]. Among the π coordinated compounds of d metals of Ib group
with allyl derivatives of tetrazoles only three crystalline π complexes of Ag(I) have been studied [2, 3], so in the continuation
+
of the investigation of the behavior of other substituted tetrazoles as compared with Ag , this work reports the results of the
synthesis and X-ray diffraction analysis of a new π complex of AgBF with 2-allyl-5-phenyl-2Н-tetrazole (2aphet) of the
4
composition [Ag(2aphet)BF ] (1).
4
Experimental. Synthesis. 5-Phenyltetrazole was obtained according to the known technique [4] from benzonitrile
and sodium azide. 5-Phenyltetrazole was alkylated with allyl chloride in the presence of an equivalent amount of NaHCO in
3
the ethanol solution resulting in a product of N-allyl-5-phenyltertrazole (aphet). Yield was 94 %.
The crystals of the [Ag(2aphet)BF ] compound (1) were synthesized by the interaction of silver(I) tetrafluoroborate
4
(formed in situ from Ag CO and HBF ) with 2-aphet in the ethanol solution. To the solution of 0.27 mmol (0.05 g) of
2 3 4
2-aphet in 0.7 ml of ethanol, at room temperature, 0.36 mmol (0.1 g) of freshly prepared Ag CO was added. The suspension
2 3
was acidified with concentrated HBF to pH ∼ 4, and a newly formed white, slightly rose suspension was left in the dark at
4
room temperature. In 52 h, on the surface of the precipitate from the solution, the colorless prismatic crystals of compound 1
formed.
Single crystal X-ray diffraction study. The array of the integrated reflection intensities for the crystals of
compound 1 was recorded on a single crystal Rigaku AFC7 diffractometer equipped with a coordinate Mercury CCD detector
(MoK radiation, graphite monochromator). The structure was solved and refined using the SHELXS-97 and SHELXL-97
α
software [5]. The details of the single crystal X-ray diffraction study and the main crystal structural data for 1 are as follows:
composition C H N AgBF , M = 380.9 g/mol, triclinic crystals, space group P1 , a = 6.3063(12) Å, b = 7.0074(12) Å,
10 10
4
4
3
c = 14.394(3) Å, α = 80.179(8)°, β = 88.241(7)°, γ = 78.732(6)°, V = 614.7(2) Å , Z = 2,
3
= 2.06 g/cm ,
ρ
calc
–1
μ(MoK ) = 1.683 mm , S = 1.077, R(F) = 0.0544 for 2389 reflections with I ≥ 2σ(I), R = 0.1475 for all 2534 independent
α
w
Franko National University of Lviv, Lviv, Ukraine; y_slyvka@franko.lviv.ua. Translated from Zhurnal Strukturnoi
Khimii, Vol. 56, No. 1, pp. 187-188, January-February, 2015. Original article submitted December 16, 2013.
0022-4766/15/5601-0179 © 2015 by Pleiades Publishing, Ltd.
179

Fig. 1. Fragment of the structure of {Ag(2aphet)BF } (1).
4 n
reflections. Three of four F atoms of the tetrafluoroborate anion are disordered over three sites. The positions of these F
atoms were refined in the isotropic approximation. Atomic coordinates and other parameters of compound 1 were deposited
with the Cambridge Structural Database (No. CCDC 976329) at the address of www.ccdc.cam.ac.uk/data_request/cif.
Results and discussion. In the structure of 1, the 2aphet molecule serves as a bridge-chelate π,σ-ligand and is
coordinated to the Ag(I) atom through the olefinic C=C bond of the allyl group and two N1 and N3 atoms of the tetrazole
n+
core (Fig. 1). Therefore, the linear organometallic cationic chains of the composition {Ag(2aphet)} are formed in the
n
structure. The phenyl ring in 2aphet is turned at 10.4° relative to the plane of the tetrazole core. A distorted trigonal-
bipyramidal environment of the silver atom consists of three mentioned active centers of 2aphet and two F atoms. The
i
i
ii
respective Ag–m (where m is the middle of the C=C bond, i = x–1, y, z), Ag–N1 , Ag–N3, Ag–F1 (іі = 1–x, 1–y, 1–z), and
Ag–F42 distances are 2.330(4) Å, 2.420(4) Å, 2.231(4) Å, 3.05(1) Å, and 2.53(1) Å respectively. As a whole, the topology of
compound 1 is similar to that of the previously studied π-complexes of Cu(І) with 2-allylbenzotriazole [6].
The author is grateful to Dr. Goreshnik (Jožef Stefan Institute, Liubljana, Slovenia) for measuring the crystals of
compound 1 on a diffractometer.
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