1-[1-(4-Chloro­phen­yl)ethyl­idene]carbono­hydrazide

Du, L.; Du, L.; Wang, S.

doi:10.1107/S1600536809030384

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2130

doi:10.1107/S1600536809030384

Open

access

1-[1-(4-Chlorophenyl)ethylidene]carbonohydrazide

Lingyun Du,^a ^* Lei Du ^a and Shuhao Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: dulingyun@lcu.edu.cn

(Received 7 July 2009; accepted 31 July 2009; online 12 August 2009)

The molecular skeleton of the title molecule, C₉H₁₁ClN₄O, is essentially planar, the dihedral angle between the ring and the and N/N/C plane being 6.7 (3)°. In the crystal, intermolecular N—H⋯O and N—H⋯N hydrogen bonds link the molecules into ribbons propagated along [010].

Related literature

For the biological activity of carbonohydrazide derivatives, see: Loncle et al. (2004 ). For related structures, see Meyers et al. (1995 ).

Experimental

Crystal data

C₉H₁₁ClN₄O
M_r = 226.67
Monoclinic, P 2₁ /c
a = 14.6429 (14) Å
b = 9.6041 (12) Å
c = 7.4327 (9) Å
β = 90.102 (1)°
V = 1045.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.875, T_max = 0.960
4419 measured reflections
1837 independent reflections
1085 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.01
1837 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.86	2.24	3.024 (3)	152
N3—H3⋯O1ⁱⁱ	0.86	2.09	2.850 (3)	147
N4—H4A⋯O1ⁱⁱⁱ	0.89	2.34	3.206 (3)	164
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030384/cv2587sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030384/cv2587Isup2.hkl

checkCIF report

Comment top

A number of carbonohydrazide derivatives have been claimed to possess a bioactivity such as antibacterial, antifungal, anticonvulsant and anticancer activities (Loncle et al., 2004). We describe in this paper a user-friendly, solvent-free protocol for the synthesis of substituted carbonohydrazide starting from the fragrant ketones and carbohydrazide under solvent-free conditions in this paper. Using this method, which can be considered as a a general method for the synthesis of substituted carbonohydrazides, we obtained the title compound, (I). We present here its crystal structure.

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in bis(3-fluorophenylmethine)carbonohydrazide (Meyers et al., 1995). The N4/N3/C1 and N2/N1/C1 planes form a dihedral angle of 4.09 (4)°, while ring C4-C9 and N2/N1/C1 plane form a dihedral angle of 2.64 (29)°.

In the crystal, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into ribbons propagated in direction [010].

Related literature top

For the biological activity of carbonohydrazide derivatives, see: Loncle et al. (2004). For similar crystal structures, see Meyers et al. (1995).

Experimental top

p-Chloroacetophenone (5.0 mmol) and carbohydrazide (5.0 mmol) were mixed in 50 ml flash under sovlent-free condtions After stirring 3 h at 373 K, the resulting mixture was cooled to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid. Elemental analysis: calculated for C₉H₁₁ClN₄O: C 47.69, H 4.89, N 24.72%; found: C 47.63, H 4.75, N 24.64%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

1-[1-(4-Chlorophenyl)ethylidene]carbonohydrazide top

Crystal data top

C₉H₁₁ClN₄O	F(000) = 472
M_r = 226.67	D_x = 1.440 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.6429 (14) Å	Cell parameters from 963 reflections
b = 9.6041 (12) Å	θ = 2.5–22.7°
c = 7.4327 (9) Å	µ = 0.34 mm⁻¹
β = 90.102 (1)°	T = 298 K
V = 1045.3 (2) Å³	Needle, colourless
Z = 4	0.40 × 0.30 × 0.12 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1837 independent reflections
Radiation source: fine-focus sealed tube	1085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→17
T_min = 0.875, T_max = 0.960	k = −11→11
4419 measured reflections	l = −7→8

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0508P)² + 0.3562P] where P = (F_o² + 2F_c²)/3
1837 reflections	(Δ/σ)_max = 0.002
137 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₁₁ClN₄O	V = 1045.3 (2) Å³
M_r = 226.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.6429 (14) Å	µ = 0.34 mm⁻¹
b = 9.6041 (12) Å	T = 298 K
c = 7.4327 (9) Å	0.40 × 0.30 × 0.12 mm
β = 90.102 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1837 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1085 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.960	R_int = 0.037
4419 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.01	Δρ_max = 0.21 e Å⁻³
1837 reflections	Δρ_min = −0.20 e Å⁻³
137 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
Cl1	0.94869 (7)	1.35122 (11)	0.60169 (13)	0.0725 (4)
N1	0.57886 (16)	0.7625 (2)	0.3769 (3)	0.0405 (7)
H1	0.5945	0.6791	0.4057	0.049*
N2	0.63579 (17)	0.8715 (2)	0.4127 (3)	0.0375 (6)
N3	0.47946 (16)	0.9177 (2)	0.2451 (3)	0.0429 (7)
H3	0.5175	0.9828	0.2719	0.051*
N4	0.39947 (16)	0.9500 (2)	0.1494 (3)	0.0434 (7)
H4A	0.4001	0.9058	0.0443	0.065*
H4B	0.3513	0.9224	0.2129	0.065*
O1	0.44329 (14)	0.6900 (2)	0.2677 (3)	0.0460 (6)
C1	0.4970 (2)	0.7867 (3)	0.2949 (4)	0.0358 (7)
C2	0.7519 (2)	0.7025 (3)	0.5085 (4)	0.0518 (9)
H2A	0.7062	0.6479	0.5682	0.078*
H2B	0.8056	0.7075	0.5825	0.078*
H2C	0.7669	0.6601	0.3955	0.078*
C3	0.7158 (2)	0.8469 (3)	0.4762 (4)	0.0357 (7)
C4	0.77306 (19)	0.9705 (3)	0.5105 (4)	0.0353 (7)
C5	0.8596 (2)	0.9605 (3)	0.5861 (4)	0.0458 (8)
H5	0.8821	0.8733	0.6173	0.055*
C6	0.9131 (2)	1.0768 (4)	0.6161 (4)	0.0511 (9)
H6	0.9710	1.0676	0.6663	0.061*
C7	0.8802 (2)	1.2056 (3)	0.5714 (4)	0.0443 (8)
C8	0.7950 (2)	1.2196 (4)	0.4976 (4)	0.0513 (9)
H8	0.7729	1.3074	0.4678	0.062*
C9	0.7423 (2)	1.1031 (3)	0.4676 (4)	0.0475 (9)
H9	0.6845	1.1136	0.4173	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0749 (7)	0.0666 (7)	0.0758 (7)	−0.0359 (5)	−0.0187 (5)	0.0017 (5)
N1	0.0364 (16)	0.0234 (14)	0.0618 (18)	0.0002 (12)	−0.0087 (13)	0.0031 (12)
N2	0.0367 (15)	0.0287 (15)	0.0471 (15)	−0.0058 (12)	−0.0022 (12)	−0.0013 (11)
N3	0.0377 (16)	0.0238 (15)	0.0671 (18)	−0.0020 (12)	−0.0125 (13)	0.0000 (12)
N4	0.0361 (15)	0.0335 (15)	0.0605 (17)	0.0027 (12)	−0.0060 (12)	0.0004 (12)
O1	0.0397 (13)	0.0231 (12)	0.0753 (16)	−0.0055 (10)	−0.0085 (11)	0.0006 (10)
C1	0.0372 (19)	0.0216 (18)	0.0488 (19)	0.0004 (14)	0.0016 (15)	−0.0018 (14)
C2	0.055 (2)	0.043 (2)	0.058 (2)	0.0051 (18)	−0.0117 (17)	−0.0020 (16)
C3	0.0360 (19)	0.0370 (18)	0.0342 (16)	0.0020 (15)	−0.0013 (14)	−0.0022 (14)
C4	0.0332 (18)	0.0379 (19)	0.0349 (17)	−0.0019 (14)	−0.0016 (14)	−0.0011 (14)
C5	0.042 (2)	0.044 (2)	0.051 (2)	−0.0002 (17)	−0.0057 (16)	0.0064 (16)
C6	0.041 (2)	0.061 (3)	0.052 (2)	−0.0070 (19)	−0.0125 (16)	0.0029 (18)
C7	0.045 (2)	0.045 (2)	0.0431 (19)	−0.0125 (17)	−0.0041 (16)	−0.0033 (15)
C8	0.052 (2)	0.037 (2)	0.065 (2)	−0.0075 (17)	−0.0142 (18)	0.0026 (16)
C9	0.0366 (19)	0.042 (2)	0.064 (2)	−0.0034 (16)	−0.0142 (16)	0.0021 (17)

Geometric parameters (Å, º) top

Cl1—C7	1.735 (3)	C2—H2B	0.9600
N1—C1	1.364 (4)	C2—H2C	0.9600
N1—N2	1.364 (3)	C3—C4	1.476 (4)
N1—H1	0.8600	C4—C5	1.388 (4)
N2—C3	1.285 (4)	C4—C9	1.387 (4)
N3—C1	1.336 (3)	C5—C6	1.382 (4)
N3—N4	1.404 (3)	C5—H5	0.9300
N3—H3	0.8600	C6—C7	1.368 (4)
N4—H4A	0.8900	C6—H6	0.9300
N4—H4B	0.8900	C7—C8	1.369 (4)
O1—C1	1.234 (3)	C8—C9	1.378 (4)
C2—C3	1.502 (4)	C8—H8	0.9300
C2—H2A	0.9600	C9—H9	0.9300

C1—N1—N2	119.5 (2)	N2—C3—C2	123.3 (3)
C1—N1—H1	120.2	C4—C3—C2	121.1 (3)
N2—N1—H1	120.3	C5—C4—C9	116.9 (3)
C3—N2—N1	119.1 (2)	C5—C4—C3	122.1 (3)
C1—N3—N4	120.5 (2)	C9—C4—C3	121.0 (3)
C1—N3—H3	119.7	C6—C5—C4	121.7 (3)
N4—N3—H3	119.7	C6—C5—H5	119.1
N3—N4—H4A	109.2	C4—C5—H5	119.1
N3—N4—H4B	109.1	C7—C6—C5	119.5 (3)
H4A—N4—H4B	109.5	C7—C6—H6	120.2
O1—C1—N3	122.8 (3)	C5—C6—H6	120.2
O1—C1—N1	120.3 (3)	C6—C7—C8	120.4 (3)
N3—C1—N1	116.9 (3)	C6—C7—Cl1	119.6 (2)
C3—C2—H2A	109.5	C8—C7—Cl1	119.9 (3)
C3—C2—H2B	109.5	C7—C8—C9	119.7 (3)
H2A—C2—H2B	109.5	C7—C8—H8	120.2
C3—C2—H2C	109.5	C9—C8—H8	120.2
H2A—C2—H2C	109.5	C8—C9—C4	121.8 (3)
H2B—C2—H2C	109.5	C8—C9—H9	119.1
N2—C3—C4	115.6 (3)	C4—C9—H9	119.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.86	2.24	3.024 (3)	152
N3—H3···O1ⁱⁱ	0.86	2.09	2.850 (3)	147
N4—H4A···O1ⁱⁱⁱ	0.89	2.34	3.206 (3)	164

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁ClN₄O
M_r	226.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.6429 (14), 9.6041 (12), 7.4327 (9)
β (°)	90.102 (1)
V (Å³)	1045.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.40 × 0.30 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.875, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	4419, 1837, 1085
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.01
No. of reflections	1837
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.86	2.24	3.024 (3)	151.6
N3—H3···O1ⁱⁱ	0.86	2.09	2.850 (3)	146.7
N4—H4A···O1ⁱⁱⁱ	0.89	2.34	3.206 (3)	164.3

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2.

Acknowledgements

The authors acknowledge financial support by the Science Foundation of China (grant No. 20877037).

References

Loncle, C., Brunel, J. M., Vidal, N., Dherbomez, M. & Letourneux, Y. (2004). Eur. J. Med. Chem. 39, 1067–1071. Web of Science CrossRef PubMed CAS Google Scholar
Meyers, C. Y., Kolb, V. M. & Robinson, P. D. (1995). Acta Cryst. C51, 775–777. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar