organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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1,5-Bis(2-chloro­benzyl­­idene)carbonohydrazide

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[Meyers, C. Y., Kolb, V. M. & Robinson, P. D. (1995). Acta Cryst. C51, 775-777.]); Li et al. (2008[Li, K.-Z., Chen, Y.-T., Zhao, C.-W., Wei, G.-D. & He, Q.-P. (2008). Acta Cryst. E64, o1665.]).

[Scheme 1]

Experimental

Crystal data
  • C15H12Cl2N4O

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.817, Tmax = 0.840

  • 7395 measured reflections

  • 2684 independent reflections

  • 1698 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.186

  • S = 1.05

  • 2684 reflections

  • 199 parameters

  • H-atom parameters constrained

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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%.

Refinement top

All H atoms were placed in geometrically idealized positions (N—H 0.86 and C—H 0.93 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2 Ueq(C) (C, N).

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
[Figure 1] 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
C15H12Cl2N4OF(000) = 688
Mr = 335.19Dx = 1.451 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.7889 (11) ÅCell parameters from 2356 reflections
b = 15.7117 (19) Åθ = 2.3–24.5°
c = 9.0543 (10) ŵ = 0.43 mm1
β = 90.978 (1)°T = 298 K
V = 1534.6 (3) Å3Block, colourless
Z = 40.49 × 0.43 × 0.42 mm
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
2684 independent reflections
Radiation source: fine-focus sealed tube1698 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
ϕ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 129
Tmin = 0.817, Tmax = 0.840k = 1816
7395 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.078P)2 + 1.6963P]
where P = (Fo2 + 2Fc2)/3
2684 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C15H12Cl2N4OV = 1534.6 (3) Å3
Mr = 335.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.7889 (11) ŵ = 0.43 mm1
b = 15.7117 (19) ÅT = 298 K
c = 9.0543 (10) Å0.49 × 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)
Tmin = 0.817, Tmax = 0.840Rint = 0.048
7395 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.186H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
2684 reflectionsΔρmin = 0.29 e Å3
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
xyzUiso*/Ueq
Cl10.51332 (15)1.04600 (9)0.84330 (14)0.0807 (5)
Cl20.80060 (18)0.37748 (9)0.60557 (19)0.0947 (6)
N10.7405 (3)0.8270 (2)0.5515 (3)0.0456 (9)
H10.74710.81450.64370.055*
N20.7084 (3)0.9075 (2)0.5094 (3)0.0423 (8)
N30.7868 (3)0.6899 (2)0.5048 (3)0.0464 (9)
H30.78270.68160.59850.056*
N40.8187 (3)0.6250 (2)0.4132 (4)0.0426 (8)
O10.7578 (3)0.78083 (18)0.3143 (3)0.0475 (8)
C10.7618 (4)0.7667 (2)0.4473 (4)0.0378 (9)
C20.6644 (4)0.9532 (2)0.6101 (4)0.0419 (10)
H20.65280.93010.70330.050*
C30.6312 (4)1.0421 (2)0.5826 (4)0.0395 (10)
C40.5660 (4)1.0907 (3)0.6806 (5)0.0453 (10)
C50.5367 (4)1.1746 (3)0.6544 (5)0.0517 (12)
H50.49271.20540.72380.062*
C60.5721 (5)1.2122 (3)0.5267 (6)0.0613 (13)
H60.55271.26880.50760.074*
C70.6368 (5)1.1654 (3)0.4267 (6)0.0680 (15)
H70.66161.19090.33930.082*
C80.6660 (5)1.0818 (3)0.4524 (5)0.0565 (12)
H80.70961.05130.38220.068*
C90.8362 (4)0.5526 (3)0.4735 (5)0.0437 (10)
H90.82310.54590.57410.052*
C100.8763 (4)0.4803 (3)0.3864 (5)0.0431 (10)
C110.8636 (4)0.3978 (3)0.4351 (5)0.0520 (12)
C120.8999 (5)0.3289 (3)0.3534 (6)0.0650 (14)
H120.88900.27390.38910.078*
C130.9525 (5)0.3422 (4)0.2186 (7)0.0732 (16)
H130.97590.29610.16090.088*
C140.9704 (5)0.4233 (4)0.1697 (6)0.0709 (15)
H141.00890.43220.07980.085*
C150.9330 (4)0.4914 (3)0.2500 (5)0.0571 (12)
H150.94520.54610.21370.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1164 (12)0.0797 (10)0.0469 (8)0.0203 (8)0.0270 (7)0.0101 (7)
Cl20.1447 (15)0.0585 (9)0.0822 (11)0.0191 (9)0.0411 (10)0.0013 (7)
N10.075 (3)0.042 (2)0.0196 (17)0.0078 (17)0.0050 (16)0.0013 (14)
N20.061 (2)0.0383 (19)0.0277 (19)0.0013 (16)0.0016 (16)0.0000 (15)
N30.079 (3)0.041 (2)0.0188 (17)0.0157 (17)0.0018 (16)0.0016 (14)
N40.054 (2)0.044 (2)0.0292 (18)0.0058 (16)0.0002 (16)0.0069 (15)
O10.071 (2)0.0476 (17)0.0244 (15)0.0036 (14)0.0041 (13)0.0021 (12)
C10.047 (2)0.044 (2)0.022 (2)0.0017 (18)0.0001 (17)0.0020 (17)
C20.057 (3)0.039 (2)0.030 (2)0.0028 (19)0.0057 (19)0.0030 (19)
C30.044 (2)0.040 (2)0.034 (2)0.0051 (18)0.0049 (18)0.0037 (18)
C40.055 (3)0.045 (2)0.035 (2)0.000 (2)0.0050 (19)0.0016 (19)
C50.059 (3)0.044 (3)0.053 (3)0.002 (2)0.005 (2)0.010 (2)
C60.079 (4)0.033 (2)0.072 (4)0.001 (2)0.007 (3)0.006 (2)
C70.093 (4)0.050 (3)0.061 (3)0.001 (3)0.022 (3)0.014 (2)
C80.078 (3)0.043 (3)0.048 (3)0.004 (2)0.013 (2)0.009 (2)
C90.055 (3)0.046 (2)0.030 (2)0.004 (2)0.0016 (18)0.0003 (19)
C100.046 (3)0.045 (2)0.039 (2)0.0059 (19)0.0049 (19)0.0026 (19)
C110.056 (3)0.045 (3)0.055 (3)0.004 (2)0.004 (2)0.007 (2)
C120.075 (3)0.042 (3)0.078 (4)0.001 (2)0.006 (3)0.011 (2)
C130.078 (4)0.062 (3)0.080 (4)0.016 (3)0.003 (3)0.033 (3)
C140.076 (4)0.085 (4)0.052 (3)0.019 (3)0.015 (3)0.010 (3)
C150.067 (3)0.061 (3)0.044 (3)0.013 (2)0.000 (2)0.002 (2)
Geometric parameters (Å, º) top
Cl1—C41.737 (4)C6—C71.367 (7)
Cl2—C111.727 (5)C6—H60.9300
N1—C11.360 (5)C7—C81.370 (7)
N1—N21.364 (5)C7—H70.9300
N1—H10.8600C8—H80.9300
N2—C21.260 (5)C9—C101.452 (6)
N3—C11.339 (5)C9—H90.9300
N3—N41.361 (4)C10—C111.377 (6)
N3—H30.8600C10—C151.398 (6)
N4—C91.275 (5)C11—C121.373 (6)
O1—C11.224 (4)C12—C131.371 (8)
C2—C31.461 (5)C12—H120.9300
C2—H20.9300C13—C141.365 (8)
C3—C41.374 (6)C13—H130.9300
C3—C81.391 (6)C14—C151.358 (7)
C4—C51.374 (6)C14—H140.9300
C5—C61.360 (7)C15—H150.9300
C5—H50.9300
C1—N1—N2119.8 (3)C6—C7—H7119.3
C1—N1—H1120.1C8—C7—H7119.3
N2—N1—H1120.1C7—C8—C3120.6 (4)
C2—N2—N1115.0 (3)C7—C8—H8119.7
C1—N3—N4119.3 (3)C3—C8—H8119.7
C1—N3—H3120.4N4—C9—C10120.6 (4)
N4—N3—H3120.4N4—C9—H9119.7
C9—N4—N3116.4 (3)C10—C9—H9119.7
O1—C1—N3123.3 (4)C11—C10—C15116.6 (4)
O1—C1—N1123.5 (4)C11—C10—C9122.0 (4)
N3—C1—N1113.2 (3)C15—C10—C9121.5 (4)
N2—C2—C3121.0 (4)C12—C11—C10122.6 (4)
N2—C2—H2119.5C12—C11—Cl2117.1 (4)
C3—C2—H2119.5C10—C11—Cl2120.2 (3)
C4—C3—C8116.5 (4)C13—C12—C11119.1 (5)
C4—C3—C2123.2 (4)C13—C12—H12120.5
C8—C3—C2120.3 (4)C11—C12—H12120.5
C3—C4—C5122.7 (4)C14—C13—C12119.6 (5)
C3—C4—Cl1120.1 (3)C14—C13—H13120.2
C5—C4—Cl1117.2 (3)C12—C13—H13120.2
C6—C5—C4119.7 (4)C15—C14—C13121.1 (5)
C6—C5—H5120.1C15—C14—H14119.5
C4—C5—H5120.1C13—C14—H14119.5
C5—C6—C7119.0 (4)C14—C15—C10120.9 (5)
C5—C6—H6120.5C14—C15—H15119.5
C7—C6—H6120.5C10—C15—H15119.5
C6—C7—C8121.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.152.925 (4)149
N3—H3···O1i0.862.062.863 (4)154
Symmetry code: (i) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H12Cl2N4O
Mr335.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)10.7889 (11), 15.7117 (19), 9.0543 (10)
β (°) 90.978 (1)
V3)1534.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.49 × 0.43 × 0.42
Data collection
DiffractometerBruker SMART APEX CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.817, 0.840
No. of measured, independent and
observed [I > 2σ(I)] reflections
7395, 2684, 1698
Rint0.048
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.186, 1.05
No. of reflections2684
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.152.925 (4)149.2
N3—H3···O1i0.862.062.863 (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

First citationLi, 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
First citationMeyers, C. Y., Kolb, V. M. & Robinson, P. D. (1995). Acta Cryst. C51, 775–777.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar

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