Crystal structure of 2-cyano-N′-(cyclo­hexyl­idene)acetohydrazide

In the title compound, C₉H₁₃N₃O, the cyclo­hexyl­idene ring adopts a chair conformation and the bond-angle sum at the C atom linked to the N atom is 359.6°. The cyano­acetohydrazide grouping is close to planar (r.m.s. deviation for the non-H atoms = 0.031 Å) and subtends a dihedral angle of 64.08 (4)° with the four C atoms forming the seat of the chair. The C=O and N—H groups are in a syn conformation (O—C—N—H = −5°). In the crystal, inversion dimers linked by pairs of N—H...O hydrogen bonds generate R₂²(8) loops; this dimer linkage is reinforced by a pair of C—H...O inter­actions, which generate R₂²(14) loops. The dimers are linked by C—H...N_c (c = cyanide) inter­actions into [100] ladders, which feature C(4) chains and R₄⁴(20) loops.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.101
• Data-to-parameter ratio = 17.7

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Alert level C
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1     ..  H6B     ..       1.93 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C8     --  C9      ..        8.4 su
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          2 Why ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
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   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check


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Related literature

For background to the role of hydrazides as potential anti-cancer agents, see: Sechi et al. (2008); Manivel et al. (2009); Mohareb et al. (2011).

S1. Experimental

Cyclohexanone (0.98 g, 0.01 mol) was added to a solution of cyanoacetylhydrazine (0.99 g, 0.01 mol) in 1,4-dioxane (20 ml). The mixture was heated under reflux for 2 h and then poured into a beaker containing an ice/water mixture: the solid product was collected by filtration. Yellow slabs of the title compound were obtained by slow evaporation of an ethanol solution.

S2. Refinement

The N-bound H atom was located in a difference map and its position was freely refined. The C-bound H atoms were placed in idealized locations (C—H = 0.99 Å) and refined as riding atoms. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases.

Computing details

Data collection: CrystalClear (Rigaku, 2012); cell refinement: CrystalClear (Rigaku, 2012); data reduction: CrystalClear (Rigaku, 2012); 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound showing 50% displacement ellipsoids.
	Fig. 2. An inversion dimer in the crystal of the title compound, with N—H···O and C—H···O hydrogen bonds indicated by double-dashed lines. Symmetry code: (i) –x, 1–y, –z.
	Fig. 3. Part of a [100] double chain in the crystal of the title compound, with hydrogen bonds indicated by double-dashed lines. Symmetry codes: (i) –x, 1–y, –z; (ii) 1 + x, y, z.

2-Cyano-N'-(cyclohexylidene)acetohydrazide

Crystal data

C9H13N3O	Z = 2
Mr = 179.22	F(000) = 192
Triclinic, P1	Dx = 1.267 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8420 (2) Å	Cell parameters from 5790 reflections
b = 9.7407 (7) Å	θ = 2.6–27.5°
c = 10.7071 (8) Å	µ = 0.09 mm^−1
α = 73.917 (9)°	T = 100 K
β = 82.819 (10)°	Cut slab, yellow
γ = 75.980 (9)°	0.13 × 0.12 × 0.04 mm
V = 469.87 (5) Å^3

Data collection

Rigaku Mercury CCD diffractometer	1789 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω scans	h = −6→5
6176 measured reflections	k = −12→11
2136 independent reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 0.0762P] where P = (Fo^2 + 2Fc^2)/3
2136 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5886 (2)	0.25153 (11)	0.23432 (10)	0.0172 (2)
C2	0.7514 (2)	0.14590 (11)	0.34545 (10)	0.0201 (2)
H2A	0.6664	0.1673	0.4289	0.024*
H2B	0.9522	0.1560	0.3350	0.024*
C3	0.7394 (2)	−0.01067 (12)	0.34647 (11)	0.0264 (3)
H3A	0.8587	−0.0815	0.4150	0.032*
H3B	0.5406	−0.0233	0.3673	0.032*
C4	0.8456 (3)	−0.04206 (13)	0.21466 (12)	0.0290 (3)
H4A	0.8225	−0.1407	0.2159	0.035*
H4B	1.0513	−0.0415	0.1989	0.035*
C5	0.6822 (2)	0.07141 (13)	0.10418 (11)	0.0272 (3)
H5A	0.4801	0.0636	0.1148	0.033*
H5B	0.7631	0.0511	0.0199	0.033*
C6	0.6986 (2)	0.22686 (12)	0.10284 (10)	0.0217 (2)
H6A	0.8983	0.2385	0.0843	0.026*
H6B	0.5815	0.2992	0.0343	0.026*
C7	−0.0539 (2)	0.51593 (11)	0.19148 (10)	0.0173 (2)
C8	−0.1182 (2)	0.51675 (11)	0.33402 (10)	0.0188 (2)
H8A	−0.1150	0.4156	0.3873	0.023*
H8B	0.0320	0.5522	0.3629	0.023*
C9	−0.3962 (2)	0.61033 (11)	0.35514 (10)	0.0190 (2)
N1	0.36168 (17)	0.33947 (9)	0.26408 (8)	0.0176 (2)
N2	0.19288 (17)	0.42828 (9)	0.16325 (8)	0.0183 (2)
H1	0.227 (3)	0.4221 (14)	0.0801 (14)	0.022*
N3	−0.61224 (19)	0.68227 (10)	0.37675 (9)	0.0251 (2)
O1	−0.21717 (15)	0.59183 (8)	0.10701 (7)	0.0228 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0182 (4)	0.0185 (5)	0.0157 (5)	−0.0059 (4)	−0.0009 (4)	−0.0038 (4)
C2	0.0207 (5)	0.0225 (5)	0.0153 (5)	−0.0025 (4)	−0.0019 (4)	−0.0038 (4)
C3	0.0310 (6)	0.0197 (5)	0.0229 (6)	−0.0032 (4)	0.0056 (5)	−0.0016 (4)
C4	0.0347 (6)	0.0210 (5)	0.0309 (6)	−0.0078 (4)	0.0109 (5)	−0.0102 (5)
C5	0.0217 (5)	0.0400 (7)	0.0266 (6)	−0.0090 (5)	0.0045 (4)	−0.0201 (5)
C6	0.0179 (5)	0.0282 (6)	0.0150 (5)	−0.0001 (4)	0.0000 (4)	−0.0036 (4)
C7	0.0189 (5)	0.0185 (5)	0.0151 (5)	−0.0058 (4)	0.0002 (4)	−0.0043 (4)
C8	0.0192 (5)	0.0217 (5)	0.0155 (5)	−0.0036 (4)	−0.0009 (4)	−0.0057 (4)
C9	0.0241 (5)	0.0199 (5)	0.0149 (5)	−0.0085 (4)	0.0000 (4)	−0.0050 (4)
N1	0.0196 (4)	0.0185 (4)	0.0142 (4)	−0.0041 (3)	−0.0031 (3)	−0.0027 (3)
N2	0.0196 (4)	0.0215 (5)	0.0118 (4)	−0.0018 (3)	−0.0011 (3)	−0.0034 (3)
N3	0.0253 (5)	0.0255 (5)	0.0240 (5)	−0.0037 (4)	0.0020 (4)	−0.0087 (4)
O1	0.0221 (4)	0.0263 (4)	0.0163 (4)	0.0009 (3)	−0.0027 (3)	−0.0043 (3)

Geometric parameters (Å, º)

C1—N1	1.2845 (13)	C5—H5A	0.99
C1—C2	1.5032 (14)	C5—H5B	0.99
C1—C6	1.5036 (14)	C6—H6A	0.99
C2—C3	1.5371 (15)	C6—H6B	0.99
C2—H2A	0.99	C7—O1	1.2306 (12)
C2—H2B	0.99	C7—N2	1.3442 (13)
C3—C4	1.5269 (16)	C7—C8	1.5209 (14)
C3—H3A	0.99	C8—C9	1.4622 (14)
C3—H3B	0.99	C8—H8A	0.99
C4—C5	1.5273 (17)	C8—H8B	0.99
C4—H4A	0.99	C9—N3	1.1457 (13)
C4—H4B	0.99	N1—N2	1.3938 (12)
C5—C6	1.5314 (16)	N2—H1	0.900 (14)
N1—C1—C2	116.83 (9)	C4—C5—H5B	109.4
N1—C1—C6	128.63 (9)	C6—C5—H5B	109.4
C2—C1—C6	114.13 (8)	H5A—C5—H5B	108.0
C1—C2—C3	108.83 (9)	C1—C6—C5	108.10 (9)
C1—C2—H2A	109.9	C1—C6—H6A	110.1
C3—C2—H2A	109.9	C5—C6—H6A	110.1
C1—C2—H2B	109.9	C1—C6—H6B	110.1
C3—C2—H2B	109.9	C5—C6—H6B	110.1
H2A—C2—H2B	108.3	H6A—C6—H6B	108.4
C4—C3—C2	111.01 (9)	O1—C7—N2	122.06 (9)
C4—C3—H3A	109.4	O1—C7—C8	121.97 (9)
C2—C3—H3A	109.4	N2—C7—C8	115.97 (9)
C4—C3—H3B	109.4	C9—C8—C7	111.64 (8)
C2—C3—H3B	109.4	C9—C8—H8A	109.3
H3A—C3—H3B	108.0	C7—C8—H8A	109.3
C3—C4—C5	111.44 (9)	C9—C8—H8B	109.3
C3—C4—H4A	109.3	C7—C8—H8B	109.3
C5—C4—H4A	109.3	H8A—C8—H8B	108.0
C3—C4—H4B	109.3	N3—C9—C8	177.32 (11)
C5—C4—H4B	109.3	C1—N1—N2	117.65 (9)
H4A—C4—H4B	108.0	C7—N2—N1	119.30 (9)
C4—C5—C6	111.25 (9)	C7—N2—H1	116.5 (8)
C4—C5—H5A	109.4	N1—N2—H1	123.6 (8)
C6—C5—H5A	109.4
N1—C1—C2—C3	114.56 (10)	O1—C7—C8—C9	3.02 (14)
C6—C1—C2—C3	−58.72 (11)	N2—C7—C8—C9	−177.51 (9)
C1—C2—C3—C4	54.68 (12)	C2—C1—N1—N2	−173.88 (8)
C2—C3—C4—C5	−54.91 (12)	C6—C1—N1—N2	−1.72 (16)
C3—C4—C5—C6	55.98 (12)	O1—C7—N2—N1	−176.79 (9)
N1—C1—C6—C5	−113.10 (12)	C8—C7—N2—N1	3.75 (13)
C2—C1—C6—C5	59.23 (11)	C1—N1—N2—C7	176.44 (9)
C4—C5—C6—C1	−56.13 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1^i	0.900 (14)	2.052 (15)	2.9399 (12)	168.4 (11)
C6—H6B···O1^i	0.99	2.32	3.2736 (13)	161
C8—H8B···N3^ii	0.99	2.41	3.3783 (14)	165

Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y, z.