1-(2,2-Diphenyl­eth­yl)-1H-tetra­zole

Myrvete Tafili-Kryeziu; Kurt Mereiter; Wolfgang Linert; Franz Werner

doi:10.1107/S1600536812027675

. 2012 Jun 27;68(Pt 7):o2231. doi: 10.1107/S1600536812027675

1-(2,2-Diphenylethyl)-1H-tetrazole

Myrvete Tafili-Kryeziu ^a, Kurt Mereiter ^b, Wolfgang Linert ^a, Franz Werner ^c,^*

PMCID: PMC3394022 PMID: 22798887

Abstract

The crystal structure of the title compound, C₁₅H₁₄N₄, contains chains of coplanar tetrazole rings with the chain direction along b. These are formed through weak hydrogen bonds, donated by the tetrazole H atoms and by one of the H atoms of the methylene group, and accepted by two neighbouring N atoms of the adjacent tetrazole ring. The chains are connected to each other in a staircase-like manner via weak hydrogen bonds, donated from the second H atom of the methylene group and accepted by the N atom next to the C atom in the tetrazole ring. The resulting layers are parallel to the bc plane.

Related literature

For the synthesis, see Kamiya & Saito (1973 ▶). For crystal structure studies of 1H-tetrazol-1-yl compounds, see Absmeier et al. (2006 ▶); Grunert et al. (2005 ▶); Werner et al. (2009 ▶).

Experimental

Crystal data

C₁₅H₁₄N₄
M _r = 250.30
Monoclinic,
a = 12.5289 (6) Å
b = 10.4157 (5) Å
c = 11.0085 (5) Å
β = 107.906 (1)°
V = 1366.99 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.45 × 0.40 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b ▶) T _min = 0.89, T _max = 0.97
18385 measured reflections
3984 independent reflections
3230 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.148
S = 1.04
3984 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a ▶); molecular graphics: ATOMS (Dowty, 2006 ▶), Mercury (Macrae et al., 2006 ▶) and VESTA (Momma & Izumi, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027675/fj2563sup1.cif

e-68-o2231-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027675/fj2563Isup2.hkl

e-68-o2231-Isup2.hkl^{(195.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027675/fj2563Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3ⁱ	0.93	2.61	3.4690 (19)	153
C2—H2B⋯N4ⁱ	0.97	2.50	3.4622 (17)	174
C2—H2A⋯N4ⁱⁱ	0.97	2.56	3.5155 (17)	169

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

Acknowledgments

Thanks for financial support are due to the "Fonds zur Förderung der Wissenschaftlichen Forschung in Österreich" (project 19335-N17).

supplementary crystallographic information

Comment

In continuation of the crystallographic characterization of 1H–tetrazol–1–yl compounds, intended as potential ligands for Fe(II) spin crossover complexes (Absmeier et al., 2006; Grunert et al., 2005; Werner et al., 2009), the title compound was prepared.

At 296 K the title compound crystallizes in the monoclinic space group P2₁/c (No. 14), with one molecule in the asymmetric unit (Fig. 1). Bond lenghts and bond angles in the molecule adopt typical values. The point group symmetry of the free molecule is C_s. Owing to intermolecular interactions this symmetry is lowered to C₁ in the crystalline solid, which can be readily seen from the (+)-synclinal arrangement of the tetrazolyl ring and the phenyl ring C10_···C15 [N1—C2—C3—C10 = 60.68 (12)°] and the out–of–plane (plane defined by N1, C2 and C3) twist of the tetrazolyl ring [N2—N1—C2—C3 = 63.98 (14)°].

In the crystal the main type of interaction are three sets of weak hydrogen bonds between the tetrazolyl rings (C1—H1···N3) and the tetrazolyl rings and the methylenic H atoms (C2—H2A···N4 and C2—H2B···N4). Through the coplanar interactions C1—H1···N3 and C2—H2B···N4 chains of tetrazolyl rings are formed parallel to the b-axis (Fig. 2), whereas C2—H2A···N4 connects these chains in a staircase-like manner (Fig. 3) resulting in the formation of layers parallel to the bc-plane with the phenyl rings pointing outwards. The layers are loosely held together by C—H···π interactions (Fig. 4).

Experimental

The title compound was prepared according to the general procedure given by Kamiya & Saito (1973). All chemicals were used as supplied without further purification. Elemental analyses were performed on a Perkin Elmer 2400 CHN Elemental Analyzer. NMR-spectra were measured in DMSO-d₆ with a Bruker DPX-200 spectrometer at 200 MHz (¹H) and 50 MHz (¹³C) respectively. The chemical shifts (see Fig. 5 for the atom assignment) are calibrated to the solvent.

2,2-Diphenylethylamine (4.93 g, 25 mmol, Aldrich, 96%), NaN₃ (3.25 g, 50 mmol, Fluka, 99%) and triethyl orthoformate (7.42 g, 50 mmol, Acros, 98%) were dissolved in 60 ml of acetic acid (Fluka, 99.8%) and heated to 85–90°C for 24 h. After evaporation of acetic acid under reduced pressure, 70 ml of 2 N hydrochloric acid was added to the residue. The solution was extracted three times with dichloromethane, the combined organic layers were washed with water and saturated aqueous solutions of NaHCO₃ and NaCl. The organic phase was dried with Na₂SO₄, filtered and the solvent was evaporated under reduced pressure. The raw product was recrystallized from methanol. Yield 2.88 g (46%), m.p. 115°C. Single crystals were grown by slow evaporation from a solution of the tetrazole in methanol at room temperature over two days.

Elemental analysis C₁₅H₁₄N₄ Calc.: C 71.98, H 5.64, N 22.38. Found: C 72.10, H 5.38, N 21.91%. ¹H-NMR (DMSO-d₆) δ [p.p.m.]: 4.73 (t, ³J=8.4 Hz, 1H, Hc), 5.21 (d, ³J=8.5 Hz, 2H, Hb), 7.15, 7.19, 7.22, 7.25, 7.29, 7.32, 7.36, 7.40 (m, 10H, He–g), 9.24 (s, 1H, Ha). ¹³C-NMR (DMSO-d₆) δ [p.p.m.]: 50.5, 50.8 (Cb–c), 127.0 (Cg), 127.8 (Ce), 128.7 (Cf), 140.7 (Cd), 144.0 (Ca).