4,4′-(1,2,4,5-Tetra­zine-3,6-di­yl)dibenzo­nitrile

Grzegorz Dutkiewicz; Teresa Borowiak; Jarosław Spychała

doi:10.1107/S1600536809008599

. 2009 Mar 25;65(Pt 4):o824. doi: 10.1107/S1600536809008599

4,4′-(1,2,4,5-Tetrazine-3,6-diyl)dibenzonitrile

Grzegorz Dutkiewicz ^a, Teresa Borowiak ^a,^*, Jarosław Spychała ^a

PMCID: PMC2968976 PMID: 21582544

Abstract

Molecules of the title compound, C₁₆H₈N₆, lie on crystallographic inversion centres. A dihedral angle of 16.1 (1)° is formed between the central tetrazine ring and the plane of each cyanophenyl group. The molecules form stacks along [100] with a perpendicular interplanar separation of 3.25 (1) Å. C—H⋯N interactions are formed between molecules in neighbouring stacks.

Related literature

For synthesis details, see: Spychała et al. (1994 ▶, 2000 ▶). For related structures and discussion, see: Higashi & Osaki (1981 ▶); Infantes et al. (2003 ▶).

Experimental

Crystal data

C₁₆H₈N₆
M _r = 284.28
Monoclinic,
a = 4.8447 (5) Å
b = 12.1054 (12) Å
c = 11.6927 (11) Å
β = 94.363 (8)°
V = 683.75 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.45 × 0.2 × 0.1 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.925, T _max = 0.991
5912 measured reflections
1768 independent reflections
1094 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.135
S = 1.06
1768 reflections
116 parameters
All H-atom parameters refined
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008599/bi2354sup1.cif

e-65-0o824-sup1.cif^{(14KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008599/bi2354Isup2.hkl

e-65-0o824-Isup2.hkl^{(87.1KB, 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
C6—H6⋯N10ⁱ	0.989 (17)	2.539 (17)	3.370 (2)	141.6 (13)
C8—H8⋯N2ⁱⁱ	0.956 (17)	2.850 (17)	3.6106 (19)	137.2 (12)
C9—H9⋯N10ⁱⁱⁱ	0.993 (17)	2.754 (17)	3.431 (2)	125.8 (12)

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

Acknowledgments

This work was supported by funds from Adam Mickiewicz University, Faculty of Chemistry.

supplementary crystallographic information

Comment

Infantes et al. (2003) have found that the supramolecular structures of some substituted phenyl derivatives of 1,2,4,5-tetrazine are comparable to those of their carboxylic acid analogues. Being inspired by that, we have compared the supramolecular structures of the title compound 3,6-bis(4-cyanophenyl)-1,2,4,5-tetrazine (hereafter I) and p-cyanobenzoic acid (Higashi & Osaki, 1981) (hereafter II).

In (I), the tetrazine molecule is located on a crystallographic inversion centre (Fig. 1). The phenyl rings are twisted with respect to the tetrazine ring by 16.1 (1)° in opposite directions. The cyano-groups are coplanar with their phenyl rings. Two C6—H6···N10(cyano) interactions related by a centre of inversion can be considered to link the molecules into 1-D chains (Fig. 2). The chains are "stepped" rather than flat (Fig. 3). Each molecule interacts with the neighbouring chain through C8—H8···N2(tetrazine) and C9—H9···N10(cyano) interactions (Fig. 2), and the molecules are stacked along [100] with a perpendicular interplanar spacing of 3.25 (1) Å. This structure contrasts with the layered structures of other phenyl-derivatives of 1,2,4,5 tetrazines described in the paper by Infantes et al. (2003).

In the crystal structure of (II), similar 1-D chains are formed through the well-known centrosymmetric carboxylic acid dimer on one side of the molecule and centrosymmetric C—H···N(cyano) interactions on the other side of the molecule. The latter interactions are closely comparable to those in (I), except that the chains in (II) lie in approximately flat layers parallel to the (201) planes. The distinction between the two structures arises because of differences between the lateral C—H···O interactions between chains in (II) and the C—H···N(tetrazine) and C—H···N(cyano) interactions in (I).

Experimental

The title compound was obtained from a multi-step procedure starting from 4-amidinobenzamide hydrochloride and anhydrous hydrazine. Dehydration of the biscarbamoyl intermediate compound to the appropriate biscyano red product was effected by means of phosphorus oxychloride in the same way as described for 2,4-bis(4- carbamoylphenyl)-1,3,5-triazine (Spychała et al., 1994; Spychała (2000). M.p. 568–570 K (acetone); δ_H (CDCl₃, TMS) 7.94 (d, 4H, J = 8.8 Hz, CH), 8.82 (d, 4H, J = 8.8 Hz, CH); δ_C (DMSO-d₆) 114.7, 117.8, 128.2, 133.0, 135.6, 162.4; MS (EI) 284 (M⁺, C₁₆H₈N₆; 13), 128 (100), 102 (9), 101 (33), 100 (7), 77 (9), 76 (12), 75 (16), 74 (4), 64 (11).

Single crystals were grown from hot acetone by slow cooling.