1,5-Bis(2-chloro­benzyl­idene)carbonohydrazide

Li, K.; Jiao, J.; Wang, Y.; Wei, G.-D.; Wang, D.

doi:10.1107/S1600536809026014

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1846

doi:10.1107/S1600536809026014

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1,5-Bis(2-chlorobenzylidene)carbonohydrazide

Kaozhen Li,^a ^* Jing Jiao,^a Yong Wang,^b Guo-Dong Wei ^c and Daqi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China, ^bShandong Wuxun High School, Guanxian, Shandong Province 252500, People's Republic of China, and ^cShandong Donge Experimental High School, Donge, Shandong Province 252200, People's Republic of China
^*Correspondence e-mail: lkzlc@163.com

(Received 24 June 2009; accepted 4 July 2009; online 11 July 2009)

In the title molecule, C₁₅H₁₂Cl₂N₄O, the two benzene rings are inclined at a dihedral angle of 14.5 (2)°. In the crystal, intermolecular N—H⋯O hydrogen bonds link molecules into chains propagated in [001].

Related literature

For related structures, see: Meyers et al. (1995 ); Li et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₂Cl₂N₄O
M_r = 335.19
Monoclinic, P 2₁ /c
a = 10.7889 (11) Å
b = 15.7117 (19) Å
c = 9.0543 (10) Å
β = 90.978 (1)°
V = 1534.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 K
0.49 × 0.43 × 0.42 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.817, T_max = 0.840
7395 measured reflections
2684 independent reflections
1698 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.186
S = 1.05
2684 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.15	2.925 (4)	149
N3—H3⋯O1ⁱ	0.86	2.06	2.863 (4)	154
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536809026014/cv2581sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026014/cv2581Isup2.hkl

checkCIF report

Comment top

In continuation of our ongoing program directed to the development of environmentally benign methods of chemical synthesis (Li et al., 2008), we present here a user-friendly, solvent-free protocol for the synthesis of substituted carbonohydrazide starting from the fragrant aldehydes and carbohydrazide under solvent-free conditions. Using this method, we obtained the title compound, (I).

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). Two benzene rings - C3-C8 and C10-C15, respectively - form a dihedral angle of 14.46 (22)°. Intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains propagated in direction [001].

Related literature top

For the crystal structures of related compounds, see: Meyers et al. (1995); Li et al. (2008).

Experimental top

o-Chlorobenzaldehyde (10 mmol) and carbohydrazide (5.0 mmol) were mixed in 50 ml flash under sovlent-free condtions After stirring 2 h at 373 K, tthe resulting mixture was cooled to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid. Elemental analysis: calculated for C₁₅H₁₂Cl₂N₄O: C 53.75, H 3.61, N 16.72%; found: C 53.61, H 3.47, N 16.86%.

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. View of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

1,5-Bis(2-chlorobenzylidene)carbonohydrazide top

Crystal data top

C₁₅H₁₂Cl₂N₄O	F(000) = 688
M_r = 335.19	D_x = 1.451 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7889 (11) Å	Cell parameters from 2356 reflections
b = 15.7117 (19) Å	θ = 2.3–24.5°
c = 9.0543 (10) Å	µ = 0.43 mm⁻¹
β = 90.978 (1)°	T = 298 K
V = 1534.6 (3) Å³	Block, colourless
Z = 4	0.49 × 0.43 × 0.42 mm

Data collection top

Bruker SMART APEX CCD area detector diffractometer	2684 independent reflections
Radiation source: fine-focus sealed tube	1698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→9
T_min = 0.817, T_max = 0.840	k = −18→16
7395 measured reflections	l = −10→10

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.078P)² + 1.6963P] where P = (F_o² + 2F_c²)/3
2684 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₅H₁₂Cl₂N₄O	V = 1534.6 (3) Å³
M_r = 335.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.7889 (11) Å	µ = 0.43 mm⁻¹
b = 15.7117 (19) Å	T = 298 K
c = 9.0543 (10) Å	0.49 × 0.43 × 0.42 mm
β = 90.978 (1)°

Data collection top

Bruker SMART APEX CCD area detector diffractometer	2684 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1698 reflections with I > 2σ(I)
T_min = 0.817, T_max = 0.840	R_int = 0.048
7395 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
2684 reflections	Δρ_min = −0.29 e Å⁻³
199 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	0.51332 (15)	1.04600 (9)	0.84330 (14)	0.0807 (5)
Cl2	0.80060 (18)	0.37748 (9)	0.60557 (19)	0.0947 (6)
N1	0.7405 (3)	0.8270 (2)	0.5515 (3)	0.0456 (9)
H1	0.7471	0.8145	0.6437	0.055*
N2	0.7084 (3)	0.9075 (2)	0.5094 (3)	0.0423 (8)
N3	0.7868 (3)	0.6899 (2)	0.5048 (3)	0.0464 (9)
H3	0.7827	0.6816	0.5985	0.056*
N4	0.8187 (3)	0.6250 (2)	0.4132 (4)	0.0426 (8)
O1	0.7578 (3)	0.78083 (18)	0.3143 (3)	0.0475 (8)
C1	0.7618 (4)	0.7667 (2)	0.4473 (4)	0.0378 (9)
C2	0.6644 (4)	0.9532 (2)	0.6101 (4)	0.0419 (10)
H2	0.6528	0.9301	0.7033	0.050*
C3	0.6312 (4)	1.0421 (2)	0.5826 (4)	0.0395 (10)
C4	0.5660 (4)	1.0907 (3)	0.6806 (5)	0.0453 (10)
C5	0.5367 (4)	1.1746 (3)	0.6544 (5)	0.0517 (12)
H5	0.4927	1.2054	0.7238	0.062*
C6	0.5721 (5)	1.2122 (3)	0.5267 (6)	0.0613 (13)
H6	0.5527	1.2688	0.5076	0.074*
C7	0.6368 (5)	1.1654 (3)	0.4267 (6)	0.0680 (15)
H7	0.6616	1.1909	0.3393	0.082*
C8	0.6660 (5)	1.0818 (3)	0.4524 (5)	0.0565 (12)
H8	0.7096	1.0513	0.3822	0.068*
C9	0.8362 (4)	0.5526 (3)	0.4735 (5)	0.0437 (10)
H9	0.8231	0.5459	0.5741	0.052*
C10	0.8763 (4)	0.4803 (3)	0.3864 (5)	0.0431 (10)
C11	0.8636 (4)	0.3978 (3)	0.4351 (5)	0.0520 (12)
C12	0.8999 (5)	0.3289 (3)	0.3534 (6)	0.0650 (14)
H12	0.8890	0.2739	0.3891	0.078*
C13	0.9525 (5)	0.3422 (4)	0.2186 (7)	0.0732 (16)
H13	0.9759	0.2961	0.1609	0.088*
C14	0.9704 (5)	0.4233 (4)	0.1697 (6)	0.0709 (15)
H14	1.0089	0.4322	0.0798	0.085*
C15	0.9330 (4)	0.4914 (3)	0.2500 (5)	0.0571 (12)
H15	0.9452	0.5461	0.2137	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1164 (12)	0.0797 (10)	0.0469 (8)	0.0203 (8)	0.0270 (7)	0.0101 (7)
Cl2	0.1447 (15)	0.0585 (9)	0.0822 (11)	−0.0191 (9)	0.0411 (10)	0.0013 (7)
N1	0.075 (3)	0.042 (2)	0.0196 (17)	0.0078 (17)	−0.0050 (16)	0.0013 (14)
N2	0.061 (2)	0.0383 (19)	0.0277 (19)	0.0013 (16)	−0.0016 (16)	0.0000 (15)
N3	0.079 (3)	0.041 (2)	0.0188 (17)	0.0157 (17)	0.0018 (16)	−0.0016 (14)
N4	0.054 (2)	0.044 (2)	0.0292 (18)	0.0058 (16)	0.0002 (16)	−0.0069 (15)
O1	0.071 (2)	0.0476 (17)	0.0244 (15)	0.0036 (14)	0.0041 (13)	0.0021 (12)
C1	0.047 (2)	0.044 (2)	0.022 (2)	0.0017 (18)	0.0001 (17)	−0.0020 (17)
C2	0.057 (3)	0.039 (2)	0.030 (2)	−0.0028 (19)	−0.0057 (19)	0.0030 (19)
C3	0.044 (2)	0.040 (2)	0.034 (2)	−0.0051 (18)	−0.0049 (18)	−0.0037 (18)
C4	0.055 (3)	0.045 (2)	0.035 (2)	0.000 (2)	−0.0050 (19)	−0.0016 (19)
C5	0.059 (3)	0.044 (3)	0.053 (3)	0.002 (2)	−0.005 (2)	−0.010 (2)
C6	0.079 (4)	0.033 (2)	0.072 (4)	0.001 (2)	−0.007 (3)	0.006 (2)
C7	0.093 (4)	0.050 (3)	0.061 (3)	0.001 (3)	0.022 (3)	0.014 (2)
C8	0.078 (3)	0.043 (3)	0.048 (3)	0.004 (2)	0.013 (2)	0.009 (2)
C9	0.055 (3)	0.046 (2)	0.030 (2)	0.004 (2)	−0.0016 (18)	−0.0003 (19)
C10	0.046 (3)	0.045 (2)	0.039 (2)	0.0059 (19)	−0.0049 (19)	−0.0026 (19)
C11	0.056 (3)	0.045 (3)	0.055 (3)	−0.004 (2)	0.004 (2)	−0.007 (2)
C12	0.075 (3)	0.042 (3)	0.078 (4)	0.001 (2)	0.006 (3)	−0.011 (2)
C13	0.078 (4)	0.062 (3)	0.080 (4)	0.016 (3)	−0.003 (3)	−0.033 (3)
C14	0.076 (4)	0.085 (4)	0.052 (3)	0.019 (3)	0.015 (3)	−0.010 (3)
C15	0.067 (3)	0.061 (3)	0.044 (3)	0.013 (2)	0.000 (2)	−0.002 (2)

Geometric parameters (Å, º) top

Cl1—C4	1.737 (4)	C6—C7	1.367 (7)
Cl2—C11	1.727 (5)	C6—H6	0.9300
N1—C1	1.360 (5)	C7—C8	1.370 (7)
N1—N2	1.364 (5)	C7—H7	0.9300
N1—H1	0.8600	C8—H8	0.9300
N2—C2	1.260 (5)	C9—C10	1.452 (6)
N3—C1	1.339 (5)	C9—H9	0.9300
N3—N4	1.361 (4)	C10—C11	1.377 (6)
N3—H3	0.8600	C10—C15	1.398 (6)
N4—C9	1.275 (5)	C11—C12	1.373 (6)
O1—C1	1.224 (4)	C12—C13	1.371 (8)
C2—C3	1.461 (5)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.365 (8)
C3—C4	1.374 (6)	C13—H13	0.9300
C3—C8	1.391 (6)	C14—C15	1.358 (7)
C4—C5	1.374 (6)	C14—H14	0.9300
C5—C6	1.360 (7)	C15—H15	0.9300
C5—H5	0.9300

C1—N1—N2	119.8 (3)	C6—C7—H7	119.3
C1—N1—H1	120.1	C8—C7—H7	119.3
N2—N1—H1	120.1	C7—C8—C3	120.6 (4)
C2—N2—N1	115.0 (3)	C7—C8—H8	119.7
C1—N3—N4	119.3 (3)	C3—C8—H8	119.7
C1—N3—H3	120.4	N4—C9—C10	120.6 (4)
N4—N3—H3	120.4	N4—C9—H9	119.7
C9—N4—N3	116.4 (3)	C10—C9—H9	119.7
O1—C1—N3	123.3 (4)	C11—C10—C15	116.6 (4)
O1—C1—N1	123.5 (4)	C11—C10—C9	122.0 (4)
N3—C1—N1	113.2 (3)	C15—C10—C9	121.5 (4)
N2—C2—C3	121.0 (4)	C12—C11—C10	122.6 (4)
N2—C2—H2	119.5	C12—C11—Cl2	117.1 (4)
C3—C2—H2	119.5	C10—C11—Cl2	120.2 (3)
C4—C3—C8	116.5 (4)	C13—C12—C11	119.1 (5)
C4—C3—C2	123.2 (4)	C13—C12—H12	120.5
C8—C3—C2	120.3 (4)	C11—C12—H12	120.5
C3—C4—C5	122.7 (4)	C14—C13—C12	119.6 (5)
C3—C4—Cl1	120.1 (3)	C14—C13—H13	120.2
C5—C4—Cl1	117.2 (3)	C12—C13—H13	120.2
C6—C5—C4	119.7 (4)	C15—C14—C13	121.1 (5)
C6—C5—H5	120.1	C15—C14—H14	119.5
C4—C5—H5	120.1	C13—C14—H14	119.5
C5—C6—C7	119.0 (4)	C14—C15—C10	120.9 (5)
C5—C6—H6	120.5	C14—C15—H15	119.5
C7—C6—H6	120.5	C10—C15—H15	119.5
C6—C7—C8	121.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.15	2.925 (4)	149
N3—H3···O1ⁱ	0.86	2.06	2.863 (4)	154

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂Cl₂N₄O
M_r	335.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.7889 (11), 15.7117 (19), 9.0543 (10)
β (°)	90.978 (1)
V (Å³)	1534.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.49 × 0.43 × 0.42

Data collection
Diffractometer	Bruker SMART APEX CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.817, 0.840
No. of measured, independent and observed [I > 2σ(I)] reflections	7395, 2684, 1698
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.186, 1.05
No. of reflections	2684
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.29

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···O1ⁱ	0.86	2.15	2.925 (4)	149.2
N3—H3···O1ⁱ	0.86	2.06	2.863 (4)	154.3

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors acknowledge financial support by the University Student Science and Technology Culture Foundation of Liaocheng University (grant No. SRT08040HX2).

References

Li, K.-Z., Chen, Y.-T., Zhao, C.-W., Wei, G.-D. & He, Q.-P. (2008). Acta Cryst. E64, o1665. Web of Science CSD CrossRef IUCr Journals Google Scholar
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