(1R,2R)-1,2-Diphenyl-1,2-bis­(1H-tetra­zol-1-yl)ethane

Franz Werner; Kurt Mereiter; Kenji Tokuno; Yuki Inagaki; Miki Hasegawa

doi:10.1107/S160053680904094X

. 2009 Oct 13;65(Pt 11):o2726–o2727. doi: 10.1107/S160053680904094X

(1R,2R)-1,2-Diphenyl-1,2-bis(1H-tetrazol-1-yl)ethane

Franz Werner ^a,^*,^‡, Kurt Mereiter ^b, Kenji Tokuno ^a, Yuki Inagaki ^a, Miki Hasegawa ^a,^*

PMCID: PMC2970974 PMID: 21578323

Abstract

The title compound, C₁₆H₁₄N₈, is a new chiral ligand designed for applications in supramolecular chemistry and Fe²⁺ spin-crossover complexes. The crystal structure shows a herring-bone arrangement of the molecules, which are mutually linked via intermolecular C—H⋯N interactions mainly donated by the alkyl and tetrazole H atoms.

Related literature

For the general synthetic procedure, see: Kamiya & Saito (1973 ▶). For the crystal structure of the chiral starting material, see: Jones et al. (2003 ▶). For studies on the crystal structures and packing of di-tetrazolylalkanes, see: Grunert et al. (2005 ▶); Absmeier et al. (2006 ▶). For supramolecular compounds made up of di-tetrazolylalkanes, see: Liu et al. (2008 ▶, 2009 ▶); Yu et al. (2008 ▶). For Fe²⁺ spin-crossover complexes based on di-tetrazolylalkanes, see: Grunert et al. (2004 ▶); Quesada et al. (2007 ▶); Bialonska et al. (2008 ▶). The absolute structure of the title compound could not be determined from the diffraction data but was known from the chiral precursor compound (1R,2R)-(+)-1,2-diphenyl-1,2-ethanediamine, see: Jones et al. (2003 ▶).

Experimental

Crystal data

C₁₆H₁₄N₈
M _r = 318.35
Orthorhombic,
a = 8.3088 (4) Å
b = 11.2802 (6) Å
c = 16.5187 (9) Å
V = 1548.21 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.65 × 0.55 × 0.46 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.86, T _max = 0.96
17102 measured reflections
2551 independent reflections
2475 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.092
S = 1.10
2551 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904094X/su2147sup1.cif

e-65-o2726-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904094X/su2147Isup2.hkl

e-65-o2726-Isup2.hkl^{(125.4KB, hkl)}

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⋯N7ⁱ	0.95	2.70	3.430 (2)	134
C2—H2⋯N7ⁱ	1.00	2.55	3.392 (2)	142
C2—H2⋯N8ⁱ	1.00	2.53	3.506 (2)	165
C3—H3⋯N3ⁱⁱ	1.00	2.46	3.351 (2)	149
C4—H4⋯N3ⁱⁱ	0.95	2.63	3.315 (2)	130
C4—H4⋯N4ⁱⁱ	0.95	2.67	3.543 (2)	154
C6—H6⋯N2	0.95	2.62	3.256 (2)	124
C7—H7⋯N6ⁱⁱⁱ	0.95	2.63	3.339 (2)	132
C12—H12⋯N2ⁱⁱ	0.95	2.71	3.655 (2)	171
C13—H13⋯N7^iv	0.95	2.74	3.379 (2)	125

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

Acknowledgments

FW is grateful to the Japan Society for the Promotion of Science for financial support through a fellowship. MH acknowledges support from a Grant-in-Aid for Young Scientists A (No. 20685011) and a High-Tech Research Center project for private universities with the matching fund subsidy of MEXT in Japan.

supplementary crystallographic information

Comment

Bifunctional molecules containing two 1H-tetrazol-1-yl groups at both ends of suitable spacer moieties like flexible alkanes or stiff arenes are of growing interest in supramolecular chemistry (Liu et al., 2008, 2009; Yu et al., 2008) and in the construction of new Fe²⁺-based spin-crossover complexes (Grunert et al., 2004; Quesada et al., 2007; Bialonska et al., 2008). In continuation of a previous study on the crystal structures and packing of α-ω-bis(tetrazol-1-yl)-alkanes (Grunert et al., 2005; Absmeier et al., 2006) the title compound, (1R,2R)-1,2-diphenyl-1,2-di-(1H-tetrazol-1-yl)ethane, became of interest as an example for a chiral bis-tetrazolyl ligand. It was obtained by a standard reaction (Kamiya & Saito, 1973) from the chiral starting material (1R,2R)-(+)-1,2-diphenyl-1,2-ethanediamine (cf. experimental).

The title compound crystallizes in the orthorhombic chiral space group P2₁2₁2₁, with one molecule in the asymmetric unit (Fig. 1). Bond lengths and bond angles in the molecule are normal. The two tetrazole rings are attached to the central ethane group in a (-)-synclinal geometry [N1—C2—C3—N5 = -53.3 (1)°], the two phenyl rings in a (+)-synclinal geometry [N1—C2—C3—N5 = 60.6 (1)°]. The point group symmetry of the free molecule is C₂. In the solid state state it deviates significantly from this symmetry by intermolecular forces, as can be seen particularly from the distinctly differing torsion angles angles [C2—C3—N5—C4 = 114.3 (1)° and C3—C2—N1—C1 = 157.8 (1)°] involving the tetrazolyl groups. The corresponding angles involving the phenyl rings differ less [C3—C2—C5—C6 = 76.0 (1)° and C2—C3—C11—C16 = 52.6 (2)°].

In the crystal the molecules are stacked in a typical herring-bone manner (Fig. 2). π-π-stacking is absent but adjacent molecules are linked by weak intermolecular C—H···N interactions (Table 1) between mainly the alkyl CH groups and the tetrazole nitrogen atoms. These are accompanied by somewhat longer C—H···N interactions of the tetrazole CH groups and some phenyl CH groups (Table 1).

Experimental

The title compound was prepared according to the general procedure given by (Kamiya & Saito, 1973). A solution of 2.0 g of (1R,2R)-(+)-1,2-diphenyl-1,2-ethanediamine (9.42 mmol, Kanto Chemical), 1.41 g of sodium azide (21.7 mmol, Wako, min. 98.0%) and 4.19 g of triethyl orthoformate (28.3 mmol, Sigma-Aldrich, 98%) in 120 ml of glacial acetic acid (Kanto Chemical, 99.5%), was stirred for 2 h at a temperature of 343 - 353 K. After cooling down to rt the solvent was distilled off and 20 ml of distilled water were added, whereupon a yellow solid precipitated. The suspension was stored in the refrigerator overnight, then the product was obtained by suction filtration and was washed with distilled water. Drying under vacuum yielded 0.291 g (9.7%) of the title compound as a colourless microcrystalline powder. Crystals suitable for X-ray difraction were obtained by recrystallization from methanol. Elemental analysis (Micro Corder JM10, J-Science Lab): C (calculated 60.37%/found 59.96%), H (4.43/4.56), N (35.20/34.80). NMR (Bruker DPX-200): ¹H (DMSO-d₆): δ 7.26–7.37 (m, 3 H, Ph—H), 7.50 (s, 1 H, CH), 7.66–7.70 (m, 2 H, Ph—H), 9.55 (s, 1 H, tetrazole). ¹³C (DMSO-d₆): δ 63.8 (CH); 128.5, 129.1, 129.5, 134.0 (Ph); 143.7 (tetrazole).