1,2-Bis(2-chloro­benzyl­idene)hydrazine

Zhang, C.-N.; Zheng, Y.-F.

doi:10.1107/S1600536807062150

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o36

https://doi.org/10.1107/S1600536807062150

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1,2-Bis(2-chlorobenzylidene)hydrazine

Chun-Niu Zhang ^a and Yun-Fa Zheng ^a ^*

^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 ); Alizadeh et al. (1999 ); Allen (2002 ).

Experimental

Crystal data

C₁₄H₁₀Cl₂N₂
M_r = 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 ) T_min = 0.871, T_max = 0.922
3767 measured reflections
1119 independent reflections
738 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.066
S = 0.97
1119 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807062150/cv2367sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062150/cv2367Isup2.hkl

checkCIF report

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.

Structure description top

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

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

C₁₄H₁₀Cl₂N₂	F(000) = 284
M_r = 277.14	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1119 reflections
a = 3.9449 (17) Å	θ = 2.3–25.2°
b = 13.548 (6) Å	µ = 0.49 mm⁻¹
c = 11.993 (5) Å	T = 298 K
β = 93.931 (6)°	Block, colourless
V = 639.5 (5) Å³	0.29 × 0.25 × 0.17 mm
Z = 2

Data collection top

Bruker APEXII area-detector diffractometer	1119 independent reflections
Radiation source: fine-focus sealed tube	738 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
φ and ω scan	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −4→4
T_min = 0.871, T_max = 0.922	k = −16→16
3767 measured reflections	l = −13→14

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.03P)²] where P = (F_o² + 2F_c²)/3
1119 reflections	(Δ/σ)_max = 0.001
82 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₄H₁₀Cl₂N₂	V = 639.5 (5) Å³
M_r = 277.14	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9449 (17) Å	µ = 0.49 mm⁻¹
b = 13.548 (6) Å	T = 298 K
c = 11.993 (5) Å	0.29 × 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)
T_min = 0.871, T_max = 0.922	R_int = 0.037
3767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 0.97	Δρ_max = 0.13 e Å⁻³
1119 reflections	Δρ_min = −0.14 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl1	0.47589 (13)	0.61367 (3)	0.83542 (4)	0.0708 (2)
C1	0.0082 (4)	0.75417 (13)	0.57454 (14)	0.0566 (5)
H1	−0.0887	0.7395	0.5036	0.068*
C7	0.1598 (4)	0.57711 (12)	0.59883 (13)	0.0500 (4)
H7	0.3006	0.5310	0.6361	0.060*
C6	0.1555 (4)	0.67868 (12)	0.64024 (13)	0.0458 (4)
C4	0.2921 (4)	0.80006 (13)	0.78504 (14)	0.0595 (5)
H4	0.3884	0.8156	0.8558	0.071*
C5	0.2958 (4)	0.70373 (12)	0.74636 (13)	0.0499 (4)
C3	0.1449 (5)	0.87235 (13)	0.71780 (17)	0.0653 (5)
H3	0.1408	0.9370	0.7436	0.078*
C2	0.0033 (5)	0.85042 (13)	0.61264 (16)	0.0644 (5)
H2	−0.0950	0.9000	0.5676	0.077*
N1	−0.0248 (4)	0.55045 (9)	0.51295 (11)	0.0567 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0842 (4)	0.0692 (3)	0.0563 (3)	0.0015 (3)	−0.0145 (2)	−0.0021 (2)
C1	0.0631 (12)	0.0559 (11)	0.0499 (11)	−0.0027 (9)	−0.0024 (9)	−0.0033 (8)
C7	0.0549 (12)	0.0494 (10)	0.0449 (10)	−0.0040 (8)	−0.0021 (8)	−0.0021 (8)
C6	0.0446 (11)	0.0467 (10)	0.0464 (9)	−0.0065 (8)	0.0050 (8)	−0.0043 (8)
C4	0.0617 (13)	0.0614 (12)	0.0552 (11)	−0.0110 (10)	0.0037 (9)	−0.0167 (9)
C5	0.0483 (11)	0.0529 (10)	0.0482 (10)	−0.0053 (8)	0.0015 (8)	−0.0020 (8)
C3	0.0707 (14)	0.0491 (11)	0.0767 (13)	−0.0049 (10)	0.0103 (11)	−0.0142 (10)
C2	0.0714 (15)	0.0538 (12)	0.0681 (12)	0.0018 (9)	0.0058 (10)	0.0023 (10)
N1	0.0687 (10)	0.0462 (8)	0.0539 (9)	−0.0061 (8)	−0.0050 (8)	−0.0069 (7)

Geometric parameters (Å, º) top

Cl1—C5	1.7406 (16)	C4—C3	1.372 (2)
C1—C2	1.382 (2)	C4—C5	1.385 (2)
C1—C6	1.393 (2)	C4—H4	0.9300
C1—H1	0.9300	C3—C2	1.376 (3)
C7—N1	1.272 (2)	C3—H3	0.9300
C7—C6	1.463 (2)	C2—H2	0.9300
C7—H7	0.9300	N1—N1ⁱ	1.418 (2)
C6—C5	1.394 (2)

C2—C1—C6	121.35 (16)	C5—C4—H4	120.4
C2—C1—H1	119.3	C4—C5—C6	121.48 (15)
C6—C1—H1	119.3	C4—C5—Cl1	117.90 (13)
N1—C7—C6	121.49 (15)	C6—C5—Cl1	120.60 (13)
N1—C7—H7	119.3	C4—C3—C2	120.89 (17)
C6—C7—H7	119.3	C4—C3—H3	119.6
C1—C6—C5	117.48 (15)	C2—C3—H3	119.6
C1—C6—C7	120.82 (14)	C3—C2—C1	119.50 (17)
C5—C6—C7	121.70 (15)	C3—C2—H2	120.3
C3—C4—C5	119.29 (16)	C1—C2—H2	120.3
C3—C4—H4	120.4	C7—N1—N1ⁱ	111.78 (16)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl1	0.93	2.69	3.060 (2)	105

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀Cl₂N₂
M_r	277.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	3.9449 (17), 13.548 (6), 11.993 (5)
β (°)	93.931 (6)
V (Å³)	639.5 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.29 × 0.25 × 0.17

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.871, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	3767, 1119, 738
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.066, 0.97
No. of reflections	1119
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

Alemi, A. A. & Shaabani, B. (2000). Acta Chim. Slov. 47, 363–369. CAS Google Scholar
Alizadeh, N., Ershad, S., Naeimi, H., Sharghi, H. & Shamsipur, M. (1999). Pol. J. Chem. 73, 915–925. CAS Google Scholar
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Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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