Cyclo­hexa­none 2-nitro­phenyl­hydrazone

Yang, B.; Niu, J.

doi:10.1107/S1600536810016156

organic compounds

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Volume 66| Part 6| June 2010| Page o1300

https://doi.org/10.1107/S1600536810016156

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Cyclohexanone 2-nitrophenylhydrazone

Bao-he Yang ^a ^* and Jun-long Niu ^b

^aDepartment of Physics, Zhengzhou Normal University, Zhengzhou 450044, People's Republic of China, and ^bDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China
^*Correspondence e-mail: ybaohe@126.com

(Received 30 April 2010; accepted 3 May 2010; online 8 May 2010)

In the title Schiff base compound, C₁₂H₁₅N₃O₂, obtained from a condensation reaction of cyclohexanone and 2-nitrophenylhydrazine, the phenylhydrazone group is planar, the largest deviation from the mean plane being 0.0252 (12) Å, and the nitro fragment is twisted slightly with respect to the mean plane, making a dihedral angle of 6.96 (17)°. The cycloheaxanone ring displays a chair conformation. An intramolecular N—H⋯O hydrogen bond helps to stabilize the molecular structure.

Related literature

For the important role played by hydrazone derivatives in the development of various proteins and enzymes, see: Kahwa et al. (1986 ); Santos et al. (2001 ). For puckering parameters, see Cremer & Pople (1975 ). For a related structure, see: Shan et al. (2003 ).

Experimental

Crystal data

C₁₂H₁₅N₃O₂
M_r = 233.27
Monoclinic, P 2₁ /c
a = 8.519 (5) Å
b = 19.609 (7) Å
c = 7.822 (4) Å
β = 112.110 (7)°
V = 1210.6 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.973, T_max = 0.977
4958 measured reflections
2472 independent reflections
739 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.066
S = 0.64
2472 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.09 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	1.98	2.599 (2)	128

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810016156/dn2561sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016156/dn2561Isup2.hkl

checkCIF report

Comment top

The chemistry of Schiff base has attracted a great deal of interest in recent years. These compounds play an important role in the development of various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). In this paper, we synthesized the title compound and reported its crystal structure.

In the title compound, the phenylhydrazone group is planar with the largest deviation from the mean plane being 0.0252 (12)Å, the nitro fragment is sligthly twisted with respect to this mean plane making a dihedral angle of 6.96 (17)° (Fig. 1). The cycloheaxanone displays a chair conformation as confirmed by the ring puckering parameters, θ= 5.6 (3)° and φ=195 (3)° (Cremer & Pople, 1975). The C-N and N-N distances within the hydrazone moity agree with related compound (Shan et al., 2003).

Intramolecular N—H···O hydrogen bond stabilizes the crystal structure.

Related literature top

For the important role played by hydrazone derivatives in the development of various proteins and enzymes, see: Kahwa et al. (1986); Santos et al. (2001). For puckering parameters, see Cremer & Pople (1975). For a related structure, see: Shan et al. (2003).

Experimental top

2-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous ethanol (15 ml), The mixture was stirred for several minitutes at 351k, cyclohexanone (1 mmol, 0.098 g) in ethanol (8 mm l) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized from methanol/dicholomethane(1:1), red single crystals of (I) was obtained after 3 d.

Structure description top

Intramolecular N—H···O hydrogen bond stabilizes the crystal structure.

For the important role played by hydrazone derivatives in the development of various proteins and enzymes, see: Kahwa et al. (1986); Santos et al. (2001). For puckering parameters, see Cremer & Pople (1975). For a related structure, see: Shan et al. (2003).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular view of (I) with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small sphere of arbitrary radii. Intramolecular hydrogen bond is shown as dashed lines.

Cyclohexanone 2-nitrophenylhydrazone top

Crystal data top

C₁₂H₁₅N₃O₂	F(000) = 496
M_r = 233.27	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 666 reflections
a = 8.519 (5) Å	θ = 3.0–26.3°
b = 19.609 (7) Å	µ = 0.09 mm⁻¹
c = 7.822 (4) Å	T = 293 K
β = 112.110 (7)°	Block, red
V = 1210.6 (10) Å³	0.23 × 0.20 × 0.19 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2472 independent reflections
Radiation source: fine-focus sealed tube	739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 26.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→8
T_min = 0.973, T_max = 0.977	k = −24→23
4958 measured reflections	l = −8→9

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) = 0.066	H-atom parameters constrained
S = 0.64	w = 1/[σ²(F_o²) + (0.0244P)²] where P = (F_o² + 2F_c²)/3
2472 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.09 e Å⁻³
0 restraints	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₁₂H₁₅N₃O₂	V = 1210.6 (10) Å³
M_r = 233.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.519 (5) Å	µ = 0.09 mm⁻¹
b = 19.609 (7) Å	T = 293 K
c = 7.822 (4) Å	0.23 × 0.20 × 0.19 mm
β = 112.110 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2472 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	739 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.977	R_int = 0.035
4958 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 0.64	Δρ_max = 0.09 e Å⁻³
2472 reflections	Δρ_min = −0.11 e Å⁻³
155 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.0513 (2)	0.70011 (9)	0.6282 (2)	0.1024 (6)
O2	0.0322 (2)	0.60900 (8)	0.7886 (2)	0.0979 (6)
N1	0.0275 (3)	0.64621 (11)	0.6599 (3)	0.0736 (6)
N2	0.19470 (18)	0.51469 (9)	0.6890 (2)	0.0621 (5)
H2	0.1484	0.5239	0.7669	0.075*
N3	0.2696 (2)	0.45142 (10)	0.6925 (2)	0.0614 (5)
C1	0.1174 (3)	0.62570 (13)	0.5443 (3)	0.0567 (6)
C2	0.1241 (3)	0.67296 (11)	0.4156 (3)	0.0716 (6)
H2B	0.0729	0.7153	0.4079	0.086*
C3	0.2056 (3)	0.65756 (14)	0.2998 (3)	0.0802 (7)
H3B	0.2101	0.6890	0.2128	0.096*
C4	0.2813 (3)	0.59436 (15)	0.3146 (3)	0.0795 (7)
H4A	0.3373	0.5836	0.2365	0.095*
C5	0.2757 (2)	0.54760 (11)	0.4404 (3)	0.0664 (6)
H5A	0.3268	0.5053	0.4454	0.080*
C6	0.1950 (2)	0.56162 (12)	0.5625 (3)	0.0540 (5)
C7	0.2737 (2)	0.41110 (11)	0.8199 (3)	0.0577 (6)
C8	0.2140 (3)	0.42256 (10)	0.9746 (3)	0.0716 (6)
H8A	0.1145	0.3949	0.9554	0.086*
H8B	0.1826	0.4700	0.9762	0.086*
C9	0.3519 (3)	0.40421 (11)	1.1584 (3)	0.0783 (7)
H9A	0.4436	0.4370	1.1866	0.094*
H9B	0.3064	0.4071	1.2547	0.094*
C10	0.4207 (3)	0.33364 (11)	1.1574 (3)	0.0890 (7)
H10A	0.3317	0.3004	1.1402	0.107*
H10B	0.5111	0.3247	1.2755	0.107*
C11	0.4880 (3)	0.32612 (11)	1.0044 (3)	0.0859 (7)
H11A	0.5276	0.2798	1.0032	0.103*
H11B	0.5832	0.3567	1.0270	0.103*
C12	0.3504 (3)	0.34250 (10)	0.8190 (3)	0.0722 (6)
H12A	0.3981	0.3415	0.7243	0.087*
H12B	0.2626	0.3080	0.7891	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1178 (15)	0.0768 (11)	0.1168 (14)	0.0302 (11)	0.0489 (12)	−0.0068 (10)
O2	0.1121 (15)	0.1044 (14)	0.1003 (13)	0.0261 (10)	0.0662 (12)	0.0126 (11)
N1	0.0680 (15)	0.0692 (16)	0.0808 (15)	0.0008 (12)	0.0246 (14)	−0.0132 (13)
N2	0.0626 (14)	0.0648 (12)	0.0657 (12)	0.0003 (10)	0.0319 (11)	0.0026 (10)
N3	0.0617 (12)	0.0553 (12)	0.0665 (12)	0.0020 (10)	0.0234 (10)	−0.0003 (10)
C1	0.0491 (16)	0.0625 (16)	0.0589 (14)	−0.0032 (13)	0.0207 (13)	−0.0044 (14)
C2	0.0627 (17)	0.0662 (16)	0.0706 (16)	−0.0056 (13)	0.0077 (14)	−0.0003 (15)
C3	0.0862 (19)	0.081 (2)	0.0700 (17)	−0.0111 (16)	0.0258 (15)	0.0096 (15)
C4	0.0774 (19)	0.096 (2)	0.0720 (17)	−0.0038 (16)	0.0365 (15)	0.0006 (16)
C5	0.0650 (17)	0.0712 (17)	0.0686 (15)	0.0002 (12)	0.0314 (14)	−0.0004 (14)
C6	0.0413 (14)	0.0648 (17)	0.0554 (14)	−0.0098 (13)	0.0175 (12)	−0.0061 (13)
C7	0.0491 (14)	0.0576 (15)	0.0613 (14)	−0.0049 (12)	0.0150 (12)	−0.0030 (13)
C8	0.0701 (17)	0.0780 (16)	0.0674 (15)	−0.0056 (12)	0.0266 (15)	0.0073 (13)
C9	0.0760 (18)	0.0897 (17)	0.0644 (16)	−0.0126 (14)	0.0210 (15)	0.0007 (14)
C10	0.0890 (19)	0.0827 (18)	0.0785 (17)	−0.0061 (15)	0.0123 (15)	0.0160 (15)
C11	0.0792 (19)	0.0711 (16)	0.0945 (19)	0.0097 (14)	0.0181 (18)	0.0029 (15)
C12	0.0732 (17)	0.0607 (15)	0.0778 (16)	−0.0054 (13)	0.0226 (15)	−0.0030 (13)

Geometric parameters (Å, º) top

O1—N1	1.2262 (19)	C7—C8	1.496 (2)
O2—N1	1.2319 (19)	C7—C12	1.497 (2)
N1—C1	1.445 (2)	C8—C9	1.518 (3)
N2—C6	1.352 (2)	C8—H8A	0.9700
N2—N3	1.3906 (18)	C8—H8B	0.9700
N2—H2	0.8600	C9—C10	1.504 (2)
N3—C7	1.262 (2)	C9—H9A	0.9700
C1—C2	1.385 (2)	C9—H9B	0.9700
C1—C6	1.402 (2)	C10—C11	1.516 (3)
C2—C3	1.366 (3)	C10—H10A	0.9700
C2—H2B	0.9300	C10—H10B	0.9700
C3—C4	1.381 (3)	C11—C12	1.517 (3)
C3—H3B	0.9300	C11—H11A	0.9700
C4—C5	1.359 (2)	C11—H11B	0.9700
C4—H4A	0.9300	C12—H12A	0.9700
C5—C6	1.398 (2)	C12—H12B	0.9700
C5—H5A	0.9300

O1—N1—O2	121.5 (2)	C7—C8—H8A	109.5
O1—N1—C1	119.5 (2)	C9—C8—H8A	109.5
O2—N1—C1	119.0 (2)	C7—C8—H8B	109.5
C6—N2—N3	119.62 (17)	C9—C8—H8B	109.5
C6—N2—H2	120.2	H8A—C8—H8B	108.1
N3—N2—H2	120.2	C10—C9—C8	112.17 (17)
C7—N3—N2	116.77 (17)	C10—C9—H9A	109.2
C2—C1—C6	121.8 (2)	C8—C9—H9A	109.2
C2—C1—N1	116.4 (2)	C10—C9—H9B	109.2
C6—C1—N1	121.8 (2)	C8—C9—H9B	109.2
C3—C2—C1	120.2 (2)	H9A—C9—H9B	107.9
C3—C2—H2B	119.9	C9—C10—C11	110.93 (18)
C1—C2—H2B	119.9	C9—C10—H10A	109.5
C2—C3—C4	118.7 (2)	C11—C10—H10A	109.5
C2—C3—H3B	120.6	C9—C10—H10B	109.5
C4—C3—H3B	120.6	C11—C10—H10B	109.5
C5—C4—C3	121.6 (2)	H10A—C10—H10B	108.0
C5—C4—H4A	119.2	C10—C11—C12	110.38 (18)
C3—C4—H4A	119.2	C10—C11—H11A	109.6
C4—C5—C6	121.5 (2)	C12—C11—H11A	109.6
C4—C5—H5A	119.3	C10—C11—H11B	109.6
C6—C5—H5A	119.3	C12—C11—H11B	109.6
N2—C6—C5	120.2 (2)	H11A—C11—H11B	108.1
N2—C6—C1	123.6 (2)	C7—C12—C11	111.55 (17)
C5—C6—C1	116.2 (2)	C7—C12—H12A	109.3
N3—C7—C8	128.90 (19)	C11—C12—H12A	109.3
N3—C7—C12	116.2 (2)	C7—C12—H12B	109.3
C8—C7—C12	114.9 (2)	C11—C12—H12B	109.3
C7—C8—C9	110.68 (17)	H12A—C12—H12B	108.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.98	2.599 (2)	128

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₃O₂
M_r	233.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.519 (5), 19.609 (7), 7.822 (4)
β (°)	112.110 (7)
V (Å³)	1210.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.973, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	4958, 2472, 739
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.066, 0.64
No. of reflections	2472
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.09, −0.11

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.98	2.599 (2)	128.0

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185. CrossRef CAS Web of Science Google Scholar
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844. Web of Science CrossRef Google Scholar
Shan, S., Xu, D.-J. & Hu, W.-X. (2003). Acta Cryst. E59, o1173–o1174. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1300

https://doi.org/10.1107/S1600536810016156

Open

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