3-[2-(4,4-Dimethyl-2,6-dioxocyclo-hexyl-idene)hydrazin-yl]benzonitrile.

The title compound, C(15)H(15)N(3)O(2), contains benzonitrile and 4,4-dimethyl-2,6-dioxocyclo-hexyl-idene 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. Intra-molecular N-H⋯O hydrogen bonding helps to stabilize the mol-ecular structure, and weak inter-molecular 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 = 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

Δρmax = 0.12 e Å−3

Δρmin = −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.

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

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

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

C15H15N3O2	F(000) = 1136
Mr = 269.30	Dx = 1.320 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8472 reflections
a = 12.9496 (8) Å	θ = 1.6–27.3°
b = 8.6028 (6) Å	µ = 0.09 mm−1
c = 24.324 (2) Å	T = 296 K
V = 2709.8 (3) Å3	Prism, yellow
Z = 8	0.80 × 0.36 × 0.14 mm

Stoe IPDS II diffractometer	2880 independent reflections
Radiation source: fine-focus sealed tube	1557 reflections with I > 2σ(I)
plane graphite	Rint = 0.052
Detector resolution: 6.67 pixels mm-1	θmax = 26.8°, θmin = 1.7°
rotation method scans	h = −16→16
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→7
Tmin = 0.959, Tmax = 0.991	l = −30→27
10586 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: mixed
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ2(Fo2) + (0.0393P)2] where P = (Fo2 + 2Fc2)/3
2880 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.80305 (13)	0.3690 (2)	0.40962 (7)	0.0361 (5)
C2	0.74316 (13)	0.2806 (2)	0.36821 (7)	0.0389 (5)
C3	0.79117 (13)	0.2623 (3)	0.31243 (8)	0.0488 (6)
H3A	0.7759	0.3541	0.2908	0.059*
H3B	0.7595	0.1741	0.2942	0.059*
C4	0.90833 (12)	0.2382 (3)	0.31345 (7)	0.0397 (5)
C5	0.95623 (13)	0.3737 (3)	0.34490 (7)	0.0435 (5)
H5A	1.0302	0.3573	0.3473	0.052*
H5B	0.9449	0.4685	0.3242	0.052*
C6	0.91435 (13)	0.3956 (2)	0.40184 (7)	0.0386 (5)
C7	0.95030 (15)	0.2359 (3)	0.25490 (8)	0.0609 (7)
H7A	1.0241	0.2257	0.2559	0.091*
H7B	0.9321	0.3309	0.2366	0.091*
H7C	0.9211	0.1495	0.2353	0.091*
C8	0.93372 (16)	0.0846 (3)	0.34174 (9)	0.0588 (6)
H8A	1.0073	0.0732	0.3444	0.088*
H8B	0.9058	0.0001	0.3207	0.088*
H8C	0.9041	0.0838	0.3779	0.088*
C9	0.72958 (12)	0.5914 (2)	0.52616 (7)	0.0370 (5)
C10	0.77582 (13)	0.6709 (2)	0.56870 (7)	0.0405 (5)
H10	0.8472	0.6696	0.5727	0.049*
C11	0.71482 (13)	0.7530 (2)	0.60557 (7)	0.0406 (5)
C12	0.60825 (14)	0.7562 (3)	0.59960 (8)	0.0450 (5)
H12	0.5675	0.8108	0.6245	0.054*
C13	0.56389 (14)	0.6779 (3)	0.55664 (8)	0.0504 (6)
H13	0.4926	0.6804	0.5523	0.060*
C14	0.62310 (13)	0.5957 (3)	0.51986 (8)	0.0453 (5)
H14	0.5919	0.5431	0.4909	0.054*
C15	0.76084 (15)	0.8376 (3)	0.65054 (8)	0.0503 (6)
N1	0.74838 (11)	0.42725 (19)	0.45015 (6)	0.0387 (4)
N2	0.79244 (12)	0.5078 (2)	0.48910 (6)	0.0397 (4)
N3	0.79474 (14)	0.9049 (3)	0.68665 (8)	0.0735 (7)
O1	0.65786 (9)	0.22775 (17)	0.37853 (5)	0.0507 (4)
O2	0.96910 (9)	0.43863 (18)	0.44021 (5)	0.0494 (4)
H2	0.8663 (18)	0.515 (3)	0.4890 (8)	0.074 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0351 (9)	0.0363 (13)	0.0368 (10)	0.0015 (8)	0.0046 (8)	0.0001 (9)
C2	0.0371 (9)	0.0341 (12)	0.0455 (11)	0.0054 (9)	0.0010 (8)	0.0010 (9)
C3	0.0438 (10)	0.0592 (17)	0.0434 (12)	0.0017 (10)	−0.0014 (8)	−0.0087 (11)
C4	0.0385 (9)	0.0420 (14)	0.0387 (10)	0.0006 (9)	0.0065 (8)	−0.0021 (10)
C5	0.0389 (10)	0.0464 (14)	0.0451 (11)	−0.0030 (9)	0.0089 (8)	−0.0006 (10)
C6	0.0384 (10)	0.0360 (13)	0.0414 (10)	0.0003 (9)	0.0040 (8)	−0.0010 (10)
C7	0.0595 (12)	0.077 (2)	0.0459 (12)	−0.0031 (13)	0.0112 (10)	−0.0101 (13)
C8	0.0562 (12)	0.0484 (17)	0.0716 (14)	0.0059 (11)	0.0163 (11)	0.0012 (13)
C9	0.0356 (9)	0.0393 (13)	0.0363 (10)	0.0030 (9)	0.0056 (7)	0.0026 (9)
C10	0.0335 (10)	0.0483 (15)	0.0398 (11)	0.0022 (8)	0.0017 (8)	0.0014 (10)
C11	0.0428 (10)	0.0431 (14)	0.0359 (10)	0.0019 (9)	0.0022 (8)	−0.0008 (10)
C12	0.0433 (10)	0.0483 (14)	0.0435 (11)	0.0081 (10)	0.0080 (8)	−0.0057 (11)
C13	0.0336 (9)	0.0605 (16)	0.0570 (13)	0.0036 (9)	0.0051 (9)	−0.0092 (12)
C14	0.0361 (10)	0.0544 (16)	0.0455 (11)	−0.0017 (10)	0.0026 (8)	−0.0101 (11)
C15	0.0438 (11)	0.0629 (17)	0.0443 (12)	0.0019 (10)	0.0076 (10)	−0.0035 (12)
N1	0.0400 (7)	0.0382 (11)	0.0377 (8)	0.0007 (8)	0.0046 (7)	−0.0002 (8)
N2	0.0347 (8)	0.0449 (12)	0.0394 (9)	0.0023 (7)	0.0049 (7)	−0.0047 (8)
N3	0.0686 (12)	0.097 (2)	0.0553 (12)	−0.0122 (12)	0.0018 (10)	−0.0218 (13)
O1	0.0372 (7)	0.0493 (10)	0.0656 (9)	−0.0065 (6)	0.0061 (6)	−0.0052 (8)
O2	0.0378 (7)	0.0661 (12)	0.0443 (8)	−0.0018 (7)	0.0005 (6)	−0.0118 (8)

C1—N1	1.313 (2)	C8—H8A	0.9600
C1—C6	1.472 (2)	C8—H8B	0.9600
C1—C2	1.481 (3)	C8—H8C	0.9600
C2—O1	1.221 (2)	C9—C10	1.377 (2)
C2—C3	1.501 (2)	C9—C14	1.388 (2)
C3—C4	1.532 (2)	C9—N2	1.412 (2)
C3—H3A	0.9700	C10—C11	1.388 (2)
C3—H3B	0.9700	C10—H10	0.9300
C4—C7	1.524 (2)	C11—C12	1.388 (2)
C4—C8	1.526 (3)	C11—C15	1.442 (3)
C4—C5	1.526 (3)	C12—C13	1.370 (3)
C5—C6	1.499 (2)	C12—H12	0.9300
C5—H5A	0.9700	C13—C14	1.374 (3)
C5—H5B	0.9700	C13—H13	0.9300
C6—O2	1.229 (2)	C14—H14	0.9300
C7—H7A	0.9600	C15—N3	1.140 (2)
C7—H7B	0.9600	N1—N2	1.305 (2)
C7—H7C	0.9600	N2—H2	0.96 (2)
N1—C1—C6	124.40 (17)	H7A—C7—H7C	109.5
N1—C1—C2	115.10 (15)	H7B—C7—H7C	109.5
C6—C1—C2	120.35 (16)	C4—C8—H8A	109.5
O1—C2—C1	121.69 (17)	C4—C8—H8B	109.5
O1—C2—C3	121.42 (17)	H8A—C8—H8B	109.5
C1—C2—C3	116.87 (16)	C4—C8—H8C	109.5
C2—C3—C4	114.21 (15)	H8A—C8—H8C	109.5
C2—C3—H3A	108.7	H8B—C8—H8C	109.5
C4—C3—H3A	108.7	C10—C9—C14	120.13 (17)
C2—C3—H3B	108.7	C10—C9—N2	118.83 (15)
C4—C3—H3B	108.7	C14—C9—N2	121.04 (18)
H3A—C3—H3B	107.6	C9—C10—C11	119.38 (16)
C7—C4—C8	109.47 (18)	C9—C10—H10	120.3
C7—C4—C5	109.47 (16)	C11—C10—H10	120.3
C8—C4—C5	110.37 (17)	C12—C11—C10	120.55 (18)
C7—C4—C3	109.86 (16)	C12—C11—C15	118.70 (17)
C8—C4—C3	109.75 (16)	C10—C11—C15	120.75 (16)
C5—C4—C3	107.90 (16)	C13—C12—C11	119.15 (18)
C6—C5—C4	114.32 (16)	C13—C12—H12	120.4
C6—C5—H5A	108.7	C11—C12—H12	120.4
C4—C5—H5A	108.7	C12—C13—C14	121.05 (18)
C6—C5—H5B	108.7	C12—C13—H13	119.5
C4—C5—H5B	108.7	C14—C13—H13	119.5
H5A—C5—H5B	107.6	C13—C14—C9	119.74 (19)
O2—C6—C1	120.94 (16)	C13—C14—H14	120.1
O2—C6—C5	122.05 (15)	C9—C14—H14	120.1
C1—C6—C5	116.97 (16)	N3—C15—C11	178.2 (2)
C4—C7—H7A	109.5	N2—N1—C1	120.80 (15)
C4—C7—H7B	109.5	N1—N2—C9	118.82 (16)
H7A—C7—H7B	109.5	N1—N2—H2	118.0 (13)
C4—C7—H7C	109.5	C9—N2—H2	122.9 (13)
N1—C1—C2—O1	−20.3 (3)	C4—C5—C6—C1	−38.1 (2)
C6—C1—C2—O1	163.84 (18)	C14—C9—C10—C11	1.0 (3)
N1—C1—C2—C3	158.29 (18)	N2—C9—C10—C11	−179.69 (19)
C6—C1—C2—C3	−17.5 (3)	C9—C10—C11—C12	−0.4 (3)
O1—C2—C3—C4	−143.91 (19)	C9—C10—C11—C15	−179.95 (19)
C1—C2—C3—C4	37.5 (3)	C10—C11—C12—C13	−0.3 (3)
C2—C3—C4—C7	−174.81 (19)	C15—C11—C12—C13	179.2 (2)
C2—C3—C4—C8	64.8 (2)	C11—C12—C13—C14	0.5 (3)
C2—C3—C4—C5	−55.5 (2)	C12—C13—C14—C9	0.0 (3)
C7—C4—C5—C6	175.37 (17)	C10—C9—C14—C13	−0.8 (3)
C8—C4—C5—C6	−64.1 (2)	N2—C9—C14—C13	179.9 (2)
C3—C4—C5—C6	55.8 (2)	C6—C1—N1—N2	−4.2 (3)
N1—C1—C6—O2	20.1 (3)	C2—C1—N1—N2	−179.81 (17)
C2—C1—C6—O2	−164.49 (19)	C1—N1—N2—C9	168.70 (18)
N1—C1—C6—C5	−157.67 (19)	C10—C9—N2—N1	177.20 (18)
C2—C1—C6—C5	17.8 (3)	C14—C9—N2—N1	−3.5 (3)
C4—C5—C6—O2	144.2 (2)

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

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)

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

Symmetry code: (i) .

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 ▶)