4-[2-(2,2-Dimethyl-4,6-dioxo-1,3-dioxan-5-yl­idene)hydrazin-1-yl]benzo­nitrile

Naki Çolak; Yılmaz Yıldırır; Barış Tercan; Emel Ermiş; Tuncer Hökelek

doi:10.1107/S1600536810024025

. 2010 Jun 26;66(Pt 7):o1784–o1785. doi: 10.1107/S1600536810024025

4-[2-(2,2-Dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)hydrazin-1-yl]benzonitrile

Naki Çolak ^a, Yılmaz Yıldırır ^b, Barış Tercan ^c, Emel Ermiş ^d, Tuncer Hökelek ^e,^*

PMCID: PMC3007023 PMID: 21587996

Abstract

In the title compound, C₁₃H₁₁N₃O₄, the dioxane ring adopts an envelope conformation with the C atom bonded to the dimethyl group in the flap position [deviation = 0.613 (1) Å]. The nitrile group and the attached benzene ring are roughly coplanar [maximum deviation = 0.087 (1) Å]. An intramolecular N—H⋯O hydrogen bond involving the hydrazinyl group generates an S(6) ring. The N—N and C—N bond lengths indicate that the compound may be a mixture of the azo and hydrazone tautomeric forms but the presence of the N-bound H atom supports the hydrazone form. The crystal structure is stabilized by weak intermolecular C—H⋯O, C—H⋯N and C—H⋯π interactions.

Related literature

For the applications of related azo compounds, see: Branger et al. (1997 ▶); Buchel et al. (1995 ▶); Gale et al. (1998 ▶); Ikeda & Tsutsumi (1995 ▶); Kang et al. (2000 ▶); Karcı et al. (2004 ▶); Kim et al. (1995 ▶); Kobrakov et al. (2004 ▶); Natansohn et al. (1992 ▶); Rochon et al. (1995 ▶). For related hydrazone structures, see: Çolak et al. (2010 ▶); Pavlovic et al. (2009 ▶); Seferoğlu et al. (2008 ▶); Seferoğlu et al. (2009 ▶); Wojciechowski & Szymezak (2007 ▶).

Experimental

Crystal data

C₁₃H₁₁N₃O₄
M _r = 273.25
Monoclinic,
a = 9.7617 (2) Å
b = 11.0023 (2) Å
c = 11.4753 (3) Å
β = 93.796 (1)°
V = 1229.76 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.46 × 0.43 × 0.29 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.950, T _max = 0.968
11746 measured reflections
3098 independent reflections
2591 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.108
S = 1.04
3098 reflections
225 parameters
All H-atom parameters refined
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024025/ci5104sup1.cif

e-66-o1784-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024025/ci5104Isup2.hkl

e-66-o1784-Isup2.hkl^{(148.9KB, hkl)}

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

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.92 (2)	1.958 (16)	2.6674 (13)	132 (1)
C9—H9⋯N1ⁱ	0.94 (2)	2.624 (15)	3.5320 (16)	164 (1)
C10—H10⋯N3ⁱⁱ	0.99 (2)	2.485 (15)	3.3876 (16)	152 (1)
C12—H123⋯O2ⁱⁱⁱ	0.97 (2)	2.527 (17)	3.4454 (15)	159 (1)
C12—H122⋯Cg1^iv	0.98 (2)	2.491 (15)	3.4575 (13)	171 (1)

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer.

supplementary crystallographic information

Comment

It has been known for many years that the azo compounds are widely used class of dyes due to their applications in various fields such as the dyeing of textile fibers, the coloring of different materials, colored plastics and electrochemical sensors (Kobrakov et al., 2004; Karcı et al., 2004; Gale et al., 1998). Azo dyes have been attracting intensive interest for their potential use in optical data storage (Natansohn et al., 1992), optical switching (Ikeda & Tsutsumi, 1995), polarization holography (Kim et al., 1995; Rochon et al., 1995), optical modulation (Buchel et al., 1995), nonlinear optics (Branger et al., 1997) and photolabile surfactants (Kang et al., 2000).

The dyes may exist in two possible tautomeric forms, namely azo form and hydrazone form. The azo-hydrazone tautomerism is quite interesting from a theoretical and practical point of view because the two tautomers have different properties. Azo dyes are known to exist in the azo-hydrazone tautomeric forms (Çolak et al., 2010; Pavlovic et al., 2009; Seferoğlu et al., 2009; Seferoğlu et al., 2008; Wojciechowski & Szymezak, 2007). We herein report the crystal structure of the title compound, (I).

The title compound, (I), contains benzonitrile and 2,2-dimethyl-1,3-dioxane -4,6-dione groups connected via a hydrazinyl group (Fig. 1). In (I), N1—N2 [1.3082 (14) Å] bond length is between the N═N double bond [1.20–1.28 Å for a real azo compound] and N—N single bond [longer than 1.4 Å] lengths. The N1—C3 and N2—C5 bond lengths are 1.3116 (14) and 1.4075 (14) Å, respectively. The carbonyl O atoms O3 and O4 slightly deviate from the N1/C2–C4 plane by 0.255 (2) and 0.259 (2) Å, respectively. So, the title compound may exist both in azo and hydrazone tautomeric forms, and is mainly in the hydrazone tautomeric form. The C8—C13 [1.4418 (15) Å] bond length is longer for a C(sp²)—C(sp¹) bond, but in agreement with the previously reported value [1.442 (3) Å; Çolak et al., 2010).

An intramolecular N2—H2···O3 hydrogen bond (Table 1) results in the formation of a nearly planar [with a maximum deviation of 0.056 (1) Å for atom C4] six-membered ring C (O3/N1/N2/H2/C3/C4), which is oriented with respect to the benzonitrile ring B (C5–C10) at a dihedral angle of 7.8 (43)°. Atoms N1, N2, N3 and C13 are displaced by -0.162 (2), 0.038 (2), 0.049 (2) and 0.028 (2) Å from the plane of ring B, respectively. The benzonitrile and hydrazinyl groups (4-hydrazinylbenzonitrile) are essentially coplanar [with a maximum deviation of -0.087 (1) Å for atom N1]. The dioxane ring A (O1/O2/C1–C4) is not planar having envelope conformation with atom C1 displaced by 0.613 (1) Å from the plane of the other ring atoms.

In the crystal structure, weak C—H···O and C—H···N hydrogen bonds (Table 1) may be effective in the stabilization of the crystal packing. There also exists a weak C—H···π interaction (Table 1).

Experimental

A hydrochloric acid solution (2.5 ml) of 4-aminobenzonitrile (1.18 g, 10 mmol) and an aqueous solution (10 ml) of sodium nitrite (0.69 g, 10 mmol) were mixed and stirred at 273 K for 1 h. To this solution, an ethanol solution (10 ml) of the coupling component 2,2-dimethyl-1,3-dioxane-4,6-dione (1.44 g, 10 mmol) was added and the stirring was continued at 273 K for 4 h. The resulting product was filtered and washed with water, dried and crystallized from ethanol (yield 1.88 g, 69%; m.p. 440–442 K).