3-[2-(4,4-Dimethyl-2,6-dioxocyclo­hexyl­idene)hydrazin­yl]benzonitrile

Naki Çolak; Didem Aksakal; Ömer Andaç; Orhan Büyükgüngör

doi:10.1107/S1600536810013164

. 2010 Apr 24;66(Pt 5):o1165–o1166. doi: 10.1107/S1600536810013164

3-[2-(4,4-Dimethyl-2,6-dioxocyclohexylidene)hydrazinyl]benzonitrile

Naki Çolak ^a, Didem Aksakal ^a, Ömer Andaç ^b, Orhan Büyükgüngör ^c,^*

PMCID: PMC2979068 PMID: 21579208

Abstract

The title compound, C₁₅H₁₅N₃O₂, contains benzonitrile and 4,4-dimethyl-2,6-dioxocyclohexylidene groups connected via a hydrazinyl group. The structure is in the hydrazone tautomeric form in the solid state. The benzonitrile and hydrazinyl groups (3-hydrazinylbenzonitrile) are essentially coplanar with an r.m.s. deviation of 0.016 Å. Intramolecular N—H⋯O hydrogen bonding helps to stabilize the molecular structure, and weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

The title compound is a tautomeric form of the azo compound; for the applications of azo compounds, see: Kobrakov et al. (2004 ▶); Karcı et al. (2004 ▶); Gale et al. (1998 ▶). For related structures of hydrazone derivatives, see: Kelemen et al. (1982 ▶); Saylam et al. (2008 ▶); Seferoğlu et al. (2008 ▶; 2009 ▶); Batchelor et al. (1997 ▶); de Lima et al. (2009 ▶); de Souza et al. (2010 ▶); Özbey et al. (1997 ▶); Alpaslan et al. (2005 ▶). For additional structural analaysis, see: Spek (2003 ▶).

Experimental

Crystal data

C₁₅H₁₅N₃O₂
M _r = 269.30
Orthorhombic,
a = 12.9496 (8) Å
b = 8.6028 (6) Å
c = 24.324 (2) Å
V = 2709.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.80 × 0.36 × 0.14 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.959, T _max = 0.991
10586 measured reflections
2880 independent reflections
1557 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.090
S = 0.85
2880 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013164/xu2749sup1.cif

e-66-o1165-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013164/xu2749Isup2.hkl

e-66-o1165-Isup2.hkl^{(137.8KB, 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
N2—H2⋯O2	0.95 (2)	1.91 (2)	2.6461 (19)	132.6 (18)
C10—H10⋯O2ⁱ	0.93	2.57	3.442 (2)	156

Open in a new tab

Symmetry code: (i) Inline graphic .

Table 2. Selected bonds compared with related hydrazone compounds (Å).

Nsp³—Csp²	Nsp²—Csp²	Nsp³—Nsp²	Reference
1.412	1.313	1.305	Current work
1.406	1.313	1.300	Alpaslan et al. (2005 ▶)
1.382	1.289	1.364	de Lima et al. (2009 ▶)
1.347	1.282	1.378	de Souza et al. (2010 ▶)
1.376–1.384	1.300–1.325	1.319–1.325	Özbey et al. (1997 ▶)

Open in a new tab

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

It has been known for many years that the azo compounds are a widely used class of dyes due to their application 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 are known to exist in the azo-hydrazone tautomeric forms (Saylam et al., 2008; Seferoğlu et al., 2008; Seferoğlu et al., 2009). The dyes may exist in two possible tautomeric forms, namely azo form A and hydrazone form B as depicted in Figure 3. It is suggested that in a real azo compound the N=N double bond should have a length of 1.20–1.28 Å and the bond length of N–N single bonds, as in hydrazone tautomers, should be more than 1.4 Å (Kelemen et al., 1982). In the title compound, N–N bond length is 1.304 Å, between the suggested N=N double bond and N–N single bond lengths. The bond lengths of N(sp3)–C(sp2), N(sp2)–C(sp2) and N(sp3)–N(sp2) in related hydrazone tatutomers are listed in Table 2. Comparing to related bond lengths in in Table 2, C1–N1(N(sp2)–C(sp2)) and N2–C9(N(sp3)–C(sp2)) are slightly longer, and N1–N2(N(sp3)–N(sp2)) is shorter than the expected values. Also, carbonyl oxygens slightly deviates from the least-squares plane (N1, C1, C2, C6) by -0.305 (3)Å for O1 and -0.297 (3)Å for O2. From the bond lengths and these deviations, it can be concluded that the compound exists both in azo and hydrazone tautomeric forms, and is mainly in the hydrazone tautomeric form, i.e. it is close to being real hydrazone pigments. C11–C15 bond length is longer for C(sp2)-C(sp1) but in agreement with previously reported value (Batchelor et al., 1997).

Experimental

A hydrochloric acid solution (2.5 ml) of 3-aminobenzonitrile (1.18 g, 0.010 mol) and an aqueous solution (10 ml) of sodium nitrite (0.69 g, 0.010 mol) were mixed and stirred at 273 K for 1 h, followed by the addition of ethanol solution (10 ml) of the coupling component 5,5-dimethylcyclohexane-1,3-dione (1.40 g, 0.010 mol) and continued stirring at 273 K for 4 h. The resulting product was filtered and washed with water, dried, and crystallized from ethanol gave fine crystals of benzonitrile, 3-[2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl].