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ISSN: 2056-9890

1,2-Bis(2-chloro­benzyl­­idene)hydrazine

aDepartment of Chemistry, Lishui College, 323000 Lishui, ZheJiang, People's Republic of China
*Correspondence e-mail: zjlsxyhx@126.com

(Received 13 November 2007; accepted 22 November 2007; online 6 December 2007)

The title Schiff base compound, C14H10Cl2N2, crystallizes with one half-mol­ecule in the asymmetric unit. The mid-point of the N—N bond [1.418 (3) Å] lies on an inversion centre. The mol­ecular skeleton is approximately planar, the largest deviation from the mean plane being 0.143 (4) Å for the N-bonded C atom. The crystal packing exhibits no classical inter­molecular hydrogen bonds.

Related literature

For related literature, see: Alemi & Shaabani (2000[Alemi, A. A. & Shaabani, B. (2000). Acta Chim. Slov. 47, 363-369.]); Alizadeh et al. (1999[Alizadeh, N., Ershad, S., Naeimi, H., Sharghi, H. & Shamsipur, M. (1999). Pol. J. Chem. 73, 915-925.]); Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C14H10Cl2N2

  • Mr = 277.14

  • Monoclinic, P 21 /c

  • a = 3.9449 (17) Å

  • b = 13.548 (6) Å

  • c = 11.993 (5) Å

  • β = 93.931 (6)°

  • V = 639.5 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.49 mm−1

  • T = 298 (2) K

  • 0.29 × 0.25 × 0.17 mm

Data collection
  • Bruker APEXII area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.871, Tmax = 0.922

  • 3767 measured reflections

  • 1119 independent reflections

  • 738 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.066

  • S = 0.97

  • 1119 reflections

  • 82 parameters

  • H-atom parameters constrained

  • Δρmax = 0.13 e Å−3

  • Δρmin = −0.14 e Å−3

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Winconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Winconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes, (Alizadeh et al., 1999). Schiff bases exhibiting olvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optically active) materials (Alemi & Shaabani, 2000). In this paper, we report the synthesis and crystal structure of the title compound, (I).

The molecular structure of the title compound has crystallographically imposed inversion symmetry located in the middle of the N—N bond (Fig. 1). The molecule is approximately planar with the largest deviation from the plane being 0.143 (4) for C7. The C7—N1 of 1.272 (2)Å is indicative of a C?N double bond. The other C—N, C—Cl, and C—C distances show no remarkable features (Allen, 2002).

Related literature top

For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Allen (2002).

Experimental top

Under nitrogen, a mixture of 2-chlorobenzaldehyde (2.8 g, 20 mmol), Na2SO4 (3.0 g) and hydrazine (30% in water, 10 mmol) in absolute ethanol (70 ml) was refluxed for about 3 h to yield a yellow precipitate. The product was collected by vacuum filtration and washed with ethanol. The crude solid was redissolved in CH2Cl2 (100 ml) and washed with water (2*10 ml)and brine(10 ml). After dried over Na2SO4, the solvent was removed under vacuum, and yellow solid was isolated in yield 90% (2.5 g). Colourless single crystals of the compound suitable for X-ray analysis were grown from CH2Cl2 and absolute ethanol(3:1) by slow evaporation of the solvent at room temperature over a period of about two weeks.

Refinement top

All H atoms were placed in calculated positions (C—H = 0.93 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Structure description top

Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes, (Alizadeh et al., 1999). Schiff bases exhibiting olvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optically active) materials (Alemi & Shaabani, 2000). In this paper, we report the synthesis and crystal structure of the title compound, (I).

The molecular structure of the title compound has crystallographically imposed inversion symmetry located in the middle of the N—N bond (Fig. 1). The molecule is approximately planar with the largest deviation from the plane being 0.143 (4) for C7. The C7—N1 of 1.272 (2)Å is indicative of a C?N double bond. The other C—N, C—Cl, and C—C distances show no remarkable features (Allen, 2002).

For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Allen (2002).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids [symmetry code (i):-x, 1 - y, 1 - z].
1,2-Bis(2-chlorobenzylidene)hydrazine top
Crystal data top
C14H10Cl2N2F(000) = 284
Mr = 277.14Dx = 1.439 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1119 reflections
a = 3.9449 (17) Åθ = 2.3–25.2°
b = 13.548 (6) ŵ = 0.49 mm1
c = 11.993 (5) ÅT = 298 K
β = 93.931 (6)°Block, colourless
V = 639.5 (5) Å30.29 × 0.25 × 0.17 mm
Z = 2
Data collection top
Bruker APEXII area-detector
diffractometer
1119 independent reflections
Radiation source: fine-focus sealed tube738 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
φ and ω scanθmax = 25.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 44
Tmin = 0.871, Tmax = 0.922k = 1616
3767 measured reflectionsl = 1314
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.03P)2]
where P = (Fo2 + 2Fc2)/3
1119 reflections(Δ/σ)max = 0.001
82 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C14H10Cl2N2V = 639.5 (5) Å3
Mr = 277.14Z = 2
Monoclinic, P21/cMo Kα radiation
a = 3.9449 (17) ŵ = 0.49 mm1
b = 13.548 (6) ÅT = 298 K
c = 11.993 (5) Å0.29 × 0.25 × 0.17 mm
β = 93.931 (6)°
Data collection top
Bruker APEXII area-detector
diffractometer
1119 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
738 reflections with I > 2σ(I)
Tmin = 0.871, Tmax = 0.922Rint = 0.037
3767 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 0.97Δρmax = 0.13 e Å3
1119 reflectionsΔρmin = 0.14 e Å3
82 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
Cl10.47589 (13)0.61367 (3)0.83542 (4)0.0708 (2)
C10.0082 (4)0.75417 (13)0.57454 (14)0.0566 (5)
H10.08870.73950.50360.068*
C70.1598 (4)0.57711 (12)0.59883 (13)0.0500 (4)
H70.30060.53100.63610.060*
C60.1555 (4)0.67868 (12)0.64024 (13)0.0458 (4)
C40.2921 (4)0.80006 (13)0.78504 (14)0.0595 (5)
H40.38840.81560.85580.071*
C50.2958 (4)0.70373 (12)0.74636 (13)0.0499 (4)
C30.1449 (5)0.87235 (13)0.71780 (17)0.0653 (5)
H30.14080.93700.74360.078*
C20.0033 (5)0.85042 (13)0.61264 (16)0.0644 (5)
H20.09500.90000.56760.077*
N10.0248 (4)0.55045 (9)0.51295 (11)0.0567 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0842 (4)0.0692 (3)0.0563 (3)0.0015 (3)0.0145 (2)0.0021 (2)
C10.0631 (12)0.0559 (11)0.0499 (11)0.0027 (9)0.0024 (9)0.0033 (8)
C70.0549 (12)0.0494 (10)0.0449 (10)0.0040 (8)0.0021 (8)0.0021 (8)
C60.0446 (11)0.0467 (10)0.0464 (9)0.0065 (8)0.0050 (8)0.0043 (8)
C40.0617 (13)0.0614 (12)0.0552 (11)0.0110 (10)0.0037 (9)0.0167 (9)
C50.0483 (11)0.0529 (10)0.0482 (10)0.0053 (8)0.0015 (8)0.0020 (8)
C30.0707 (14)0.0491 (11)0.0767 (13)0.0049 (10)0.0103 (11)0.0142 (10)
C20.0714 (15)0.0538 (12)0.0681 (12)0.0018 (9)0.0058 (10)0.0023 (10)
N10.0687 (10)0.0462 (8)0.0539 (9)0.0061 (8)0.0050 (8)0.0069 (7)
Geometric parameters (Å, º) top
Cl1—C51.7406 (16)C4—C31.372 (2)
C1—C21.382 (2)C4—C51.385 (2)
C1—C61.393 (2)C4—H40.9300
C1—H10.9300C3—C21.376 (3)
C7—N11.272 (2)C3—H30.9300
C7—C61.463 (2)C2—H20.9300
C7—H70.9300N1—N1i1.418 (2)
C6—C51.394 (2)
C2—C1—C6121.35 (16)C5—C4—H4120.4
C2—C1—H1119.3C4—C5—C6121.48 (15)
C6—C1—H1119.3C4—C5—Cl1117.90 (13)
N1—C7—C6121.49 (15)C6—C5—Cl1120.60 (13)
N1—C7—H7119.3C4—C3—C2120.89 (17)
C6—C7—H7119.3C4—C3—H3119.6
C1—C6—C5117.48 (15)C2—C3—H3119.6
C1—C6—C7120.82 (14)C3—C2—C1119.50 (17)
C5—C6—C7121.70 (15)C3—C2—H2120.3
C3—C4—C5119.29 (16)C1—C2—H2120.3
C3—C4—H4120.4C7—N1—N1i111.78 (16)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···Cl10.932.693.060 (2)105

Experimental details

Crystal data
Chemical formulaC14H10Cl2N2
Mr277.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)3.9449 (17), 13.548 (6), 11.993 (5)
β (°) 93.931 (6)
V3)639.5 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.29 × 0.25 × 0.17
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.871, 0.922
No. of measured, independent and
observed [I > 2σ(I)] reflections
3767, 1119, 738
Rint0.037
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.066, 0.97
No. of reflections1119
No. of parameters82
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.13, 0.14

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).

 

Acknowledgements

The authors are grateful to the Natural Science Foundation of Zhejiang Province for financial support.

References

First citationAlemi, A. A. & Shaabani, B. (2000). Acta Chim. Slov. 47, 363–369.  CAS Google Scholar
First citationAlizadeh, N., Ershad, S., Naeimi, H., Sharghi, H. & Shamsipur, M. (1999). Pol. J. Chem. 73, 915–925.  CAS Google Scholar
First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Winconsin, USA.  Google Scholar
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.  Google Scholar

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ISSN: 2056-9890
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