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

Harrison, W.T.A.; Al-Sakka, O.K.; Fleita, D.H.; Saleh, A.; Salem, S.

doi:10.1107/S1600536814009350

organic compounds

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Volume 70| Part 9| September 2014| Page o886

doi:10.1107/S1600536814009350

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

William T. A. Harrison,^a ^* Ola K. Al-Sakka,^b Daisy H. Fleita,^b Amina Saleh ^b,^c and Sara Salem ^b

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Chemistry, American University in Cairo, PO Box 74, New Cairo 11835, Egypt, and ^cInstitute of Chemistry and Chemical Engineering, École Polytechnique Fédérale de Lausanne, Station 6, CH-1015 Lausanne, Switzerland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 2 April 2014; accepted 24 April 2014; online 1 August 2014)

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.

Keywords: crystal structure; hydrazide; cyclohexylidene; inversion dimer.

CCDC reference: 1004279

1. 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 ).

2. Experimental

2.1. Crystal data

C₉H₁₃N₃O
M_r = 179.22
Triclinic, $[P \overline 1]$
a = 4.8420 (2) Å
b = 9.7407 (7) Å
c = 10.7071 (8) Å
α = 73.917 (9)°
β = 82.819 (10)°
γ = 75.980 (9)°
V = 469.87 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.13 × 0.12 × 0.04 mm

2.2. Data collection

Rigaku Mercury CCD diffractometer
6176 measured reflections
2136 independent reflections
1789 reflections with I > 2σ(I)
R_int = 0.024

2.3. Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.101
S = 1.08
2136 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O1ⁱ	0.900 (14)	2.052 (15)	2.9399 (12)	168.4 (11)
C6—H6B⋯O1ⁱ	0.99	2.32	3.2736 (13)	161
C8—H8B⋯N3ⁱⁱ	0.99	2.41	3.3783 (14)	165
Symmetry codes: (i) -x, -y+1, -z; (ii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2012 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

CCDC reference: 1004279

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814009350/su0002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009350/su0002Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009350/su0002Isup3.cml

checkCIF report

Related literature top

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).

Experimental top

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.

Computing details top

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 top

	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 top

Crystal data top

C₉H₁₃N₃O	Z = 2
M_r = 179.22	F(000) = 192
Triclinic, P1	D_x = 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) Å³

Data collection top

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

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0528P)² + 0.0762P] where P = (F_o² + 2F_c²)/3
2136 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₁₃N₃O	γ = 75.980 (9)°
M_r = 179.22	V = 469.87 (5) Å³
Triclinic, P1	Z = 2
a = 4.8420 (2) Å	Mo Kα radiation
b = 9.7407 (7) Å	µ = 0.09 mm⁻¹
c = 10.7071 (8) Å	T = 100 K
α = 73.917 (9)°	0.13 × 0.12 × 0.04 mm
β = 82.819 (10)°

Data collection top

Rigaku Mercury CCD diffractometer	1789 reflections with I > 2σ(I)
6176 measured reflections	R_int = 0.024
2136 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.29 e Å⁻³
2136 reflections	Δρ_min = −0.19 e Å⁻³
121 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.900 (14)	2.052 (15)	2.9399 (12)	168.4 (11)
C6—H6B···O1ⁱ	0.99	2.32	3.2736 (13)	161
C8—H8B···N3ⁱⁱ	0.99	2.41	3.3783 (14)	165

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.900 (14)	2.052 (15)	2.9399 (12)	168.4 (11)
C6—H6B···O1ⁱ	0.99	2.32	3.2736 (13)	161
C8—H8B···N3ⁱⁱ	0.99	2.41	3.3783 (14)	165

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

Acknowledgements

The authors thank the American University in Cairo for financial support.

References

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