organic papers
Acta Cryst.(2006). E62, o1913–o1914 doi:10.1107/S1600536806012918 Zhenget al. C
14H8Cl4N2
o1913
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
N
,
N
000-Bis(2,6-dichlorobenzylidene)hydrazine
Peng-Wu Zheng,a* Qiao-Mei Qiu,bYu-Yan Lincand Ke-Fan Liud
aSchool of Pharmacy, Jiangxi Science and
Technology Normal University, Nanchang 330013, People’s Republic of China,bShenzhen
Municipal Dongshen Water Resource Protection Office, Shenzhen, Guangdong 518113, People’s Republic of China,cShenzhen Academy of Metrology and Quality Inspection, Shenzhen, Guangdong 518109, People’s Republic of China, anddShenzhen Environ-mental Management System Certification Centre, Shenzhen, Guangdong 518033, People’s Republic of China
Correspondence e-mail: nczhengpw@yahoo.com.cn
Key indicators
Single-crystal X-ray study
T= 294 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.040
wRfactor = 0.105
Data-to-parameter ratio = 16.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 7 April 2006 Accepted 9 April 2006
#2006 International Union of Crystallography
All rights reserved
The title compound, C14H8Cl4N2, was synthesized by the reaction of 2,6-dichlorobenzaldehyde with hydrazine hydrate. The two benzene rings are nearly parallel, forming a dihedral angle of 2.9 (4). A weak intermolecular C—H N hydrogen
bond links the molecules into an infinite chain running along [100].
Comment
Recently, a number of azine compounds containing both a diimine linkage and an N—N bond have been investigated in terms of their solid state structures and coordination chem-istry (Xu et al., 1997; Armstrong et al., 1998; Kesslen et al., 1999; Duan et al., 2005; Kundu et al., 2005; Zheng et al., 2005a,b). We report here the crystal structure of the title compound, (I), where two 2,6-dichlorobenzylidene units are directly linked through the imine N atoms.
The title molecule crystallizes in anE,Econfiguration but is not centrosymmetric (Fig. 1). The molecule is not planar, the mean deviation being 0.1586 (3) A˚ , while a planar molecule is observed for benzalazine (Burke-Laing & Laing, 1976). This configuration is different from that found in a number of analogous azine compounds in which there is a crystal-lographically imposed centre of symmetry at the mid-point of the N—N bond (Liuet al., 2004; S¸engu¨let al., 2004; Duanet al., 2005; Zhenget al., 2005a,b). The two benzene rings in (I) are nearly parallel, making a dihedral angle of 2.9 (4). The N—N
bond length (Table 1) is slightly longer than that observed in related azine compounds (Liuet al., 2004; S¸engu¨let al., 2004; Duanet al., 2005; Xuet al., 2005; Zheng et al., 2005a,b). The C7—N1—N2—C8 torsion angle indicates that the C N— N C linkage is not a planar system. The C N—N angles are significantly smaller than the ideal value of 120expected for
sp2-hybridized N atoms. This is probably a consequence of repulsion between the nitrogen lone pairs and the adjacent C N bonds. The four C—Cl bond lengths are slightly different but are similar to those of Csp2—Cl bonds in related compounds (Jiang & Hu, 2004; Zhenget al., 2005a).
running along [100]. Furthermore, a weak Cl Cliicontact is observed between chains [Cl Clii = 3.356 (3) A˚ ; van der Waals radii for Cl = 1.75 A˚ ; symmetry code: (ii) 1x,y,z].
Experimental
The title compound was synthesized by the reaction of 2,6-dichlorobenzaldehyde with hydrazine hydrate in refluxing ethanol (Liu et al., 2004). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a tetrahydrofuran solution.
Crystal data
C14H8Cl4N2
Mr= 346.02 Monoclinic,P21=n
a= 4.265 (3) A˚
b= 13.548 (9) A˚
c= 25.593 (17) A˚ = 94.008 (12)
V= 1475.2 (17) A˚3
Z= 4
Dx= 1.558 Mg m 3
MoKradiation = 0.79 mm1
T= 294 (2) K Block, light yellow 0.200.100.06 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.902,Tmax= 0.954
8021 measured reflections 2999 independent reflections 1718 reflections withI> 2(I)
Rint= 0.041
max= 26.3
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.040
wR(F2) = 0.105
S= 0.99 2999 reflections 181 parameters
H-atom parameters constrained
w= 1/[2
(Fo2) + (0.0382P)2
+ 0.7304P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.28 e A˚
3
min=0.34 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
Cl1—C1 1.732 (3)
Cl2—C5 1.745 (3)
Cl3—C10 1.737 (3)
Cl4—C14 1.739 (3)
N1—C7 1.248 (3)
N1—N2 1.424 (3)
N2—C8 1.242 (3)
C7—N1—N2 112.2 (2) C8—N2—N1 112.7 (2)
C7—N1—N2—C8 166.3 (3)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C8—H8 N2i
0.93 2.58 3.487 (3) 166
Symmetry code: (i)x1;y;z.
All H atoms were positioned geometrically and refined as riding, with C—H = 0.93 A˚ andUiso(H) = 1.2Ueq(C).
Data collection:SMART(Bruker, 1997); cell refinement:SAINT
(Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1997); software used to prepare material for
The authors gratefully acknowledge financial support from the Foundation for Excellent Young Teachers of Jiangxi Science and Technology Normal University.
References
Armstrong, J. A., Barnes, J. C. & Weakley, T. J. R. (1998).Acta Cryst.C54, 1923–1925.
Bruker (1997).SMART,SAINTandSHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Burke-Laing, M. & Laing, M. (1976).Acta Cyst.B32, 3216–3224.
Duan, X.-M., Zheng, P.-W. & Zhou, B. (2005).Acta Cryst.E61, o3449–o3451. Jiang, Y. Z. & Hu, W. X. (2004).Chin. J. Struct. Chem.23, 875–877. Kesslen, E. C., Euler, W. B. & Foxman, B. M. (1999).Chem. Mater.11, 336–340. Kundu, N., Chatterjee, P. B., Chaudhury, M. & Tiekink, E. R. T. (2005).Acta
Cryst.E61, m1583–m1585.
Liu, S. L., Chen, Y., Dai, J. F. & Liu, H. W. (2004).Chin. J. Synth. Chem.12, 219–221.
S¸engu¨l, A., Karadayi, N. & Bu¨yu¨kgu¨ngo¨r, O. (2004).Acta Cryst.C60, o507– o508.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
Xu, L. Z., Xu, H. Z., Yang, S. H., Li, C. L. & Zhou, K. (2005).Acta Cryst.E61, o31–o32.
[image:2.610.316.564.70.192.2]Xu, Z., Thompson, L. K. & Miller, D. O. (1997).Inorg. Chem.36, 3985–3995. Zheng, P.-W., Wang, W. & Duan, X.-M. (2005a).Acta Cryst.E61, o3020–o3021.
Figure 1
[image:2.610.314.562.235.422.2]View of the molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
Figure 2
supporting information
sup-1 Acta Cryst. (2006). E62, o1913–o1914
supporting information
Acta Cryst. (2006). E62, o1913–o1914 [https://doi.org/10.1107/S1600536806012918]
N
,
N
′
-Bis(2,6-dichlorobenzylidene)hydrazine
Peng-Wu Zheng, Qiao-Mei Qiu, Yu-Yan Lin and Ke-Fan Liu
N,N′-Bis(2,6-dichlorobenzylidene)hydrazine
Crystal data
C14H8Cl4N2
Mr = 346.02
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 4.265 (3) Å
b = 13.548 (9) Å
c = 25.593 (17) Å
β = 94.008 (12)°
V = 1475.2 (17) Å3
Z = 4
F(000) = 696
Dx = 1.558 Mg m−3
Melting point = 428–429 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2167 reflections
θ = 2.8–25.4°
µ = 0.79 mm−1
T = 294 K
Block, light yellow 0.20 × 0.10 × 0.06 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.902, Tmax = 0.954
8021 measured reflections 2999 independent reflections 1718 reflections with I > 2σ(I)
Rint = 0.041
θmax = 26.3°, θmin = 1.6°
h = −5→5
k = −16→16
l = −31→31
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.040
wR(F2) = 0.105
S = 0.99 2999 reflections 181 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0382P)2 + 0.7304P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.28 e Å−3
Δρmin = −0.34 e Å−3
Special details
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)
x y z Uiso*/Ueq
Cl1 0.3727 (2) 0.10137 (7) −0.03267 (4) 0.0727 (3) Cl2 −0.2341 (2) 0.38720 (6) 0.07086 (3) 0.0637 (3) Cl3 0.3099 (2) −0.09400 (7) 0.16006 (3) 0.0674 (3) Cl4 −0.3065 (2) 0.16937 (6) 0.27618 (3) 0.0631 (3) N1 −0.0261 (6) 0.1810 (2) 0.10135 (10) 0.0582 (8) N2 0.1116 (6) 0.1243 (2) 0.14383 (10) 0.0589 (8) C1 0.1699 (6) 0.2120 (2) −0.03094 (11) 0.0410 (7) C2 0.1070 (7) 0.2617 (2) −0.07756 (11) 0.0478 (8) H2 0.1782 0.2370 −0.1085 0.057* C3 −0.0605 (7) 0.3473 (2) −0.07783 (12) 0.0535 (8) H3 −0.1039 0.3810 −0.1092 0.064* C4 −0.1662 (7) 0.3844 (2) −0.03221 (12) 0.0502 (8) H4 −0.2808 0.4428 −0.0326 0.060* C5 −0.1005 (6) 0.3340 (2) 0.01445 (11) 0.0404 (7) C6 0.0689 (6) 0.2463 (2) 0.01691 (10) 0.0348 (6) C7 0.1552 (7) 0.1912 (2) 0.06552 (11) 0.0431 (7) H7 0.3539 0.1628 0.0697 0.052* C8 −0.0837 (7) 0.0967 (2) 0.17452 (11) 0.0424 (7) H8 −0.2923 0.1159 0.1682 0.051* C9 0.0030 (6) 0.0344 (2) 0.22064 (10) 0.0343 (6) C10 0.1758 (6) −0.0529 (2) 0.21880 (11) 0.0418 (7) C11 0.2390 (7) −0.1112 (2) 0.26281 (13) 0.0559 (9) H11 0.3525 −0.1695 0.2604 0.067* C12 0.1327 (8) −0.0823 (3) 0.31005 (13) 0.0620 (10) H12 0.1757 −0.1212 0.3396 0.074* C13 −0.0353 (8) 0.0028 (3) 0.31381 (11) 0.0548 (9) H13 −0.1068 0.0220 0.3458 0.066* C14 −0.0981 (6) 0.0602 (2) 0.26964 (11) 0.0410 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2006). E62, o1913–o1914
C3 0.064 (2) 0.062 (2) 0.0344 (17) 0.0029 (18) −0.0002 (15) 0.0183 (16) C4 0.056 (2) 0.0442 (18) 0.0505 (19) 0.0073 (16) 0.0012 (16) 0.0125 (16) C5 0.0414 (16) 0.0443 (17) 0.0357 (16) −0.0010 (14) 0.0044 (13) 0.0008 (14) C6 0.0322 (15) 0.0397 (16) 0.0324 (15) −0.0011 (13) 0.0020 (12) 0.0056 (13) C7 0.0362 (16) 0.0548 (19) 0.0383 (17) 0.0046 (14) 0.0020 (14) 0.0118 (14) C8 0.0340 (15) 0.0555 (19) 0.0378 (16) 0.0005 (14) 0.0027 (13) 0.0073 (14) C9 0.0300 (14) 0.0439 (17) 0.0287 (15) −0.0080 (13) 0.0007 (12) 0.0036 (13) C10 0.0375 (16) 0.0482 (18) 0.0394 (17) −0.0074 (14) −0.0001 (13) −0.0006 (14) C11 0.054 (2) 0.0478 (19) 0.065 (2) −0.0007 (16) −0.0025 (17) 0.0124 (17) C12 0.063 (2) 0.077 (3) 0.045 (2) −0.008 (2) −0.0027 (17) 0.0270 (19) C13 0.059 (2) 0.074 (2) 0.0315 (17) −0.0167 (19) 0.0042 (15) 0.0066 (17) C14 0.0390 (16) 0.0426 (17) 0.0414 (17) −0.0128 (13) 0.0039 (14) 0.0013 (14)
Geometric parameters (Å, º)
Cl1—C1 1.732 (3) C5—C6 1.390 (4) Cl2—C5 1.745 (3) C6—C7 1.475 (4) Cl3—C10 1.737 (3) C7—H7 0.9300 Cl4—C14 1.739 (3) C8—C9 1.476 (4) N1—C7 1.248 (3) C8—H8 0.9300 N1—N2 1.424 (3) C9—C10 1.396 (4) N2—C8 1.242 (3) C9—C14 1.399 (4) C1—C2 1.380 (4) C10—C11 1.387 (4) C1—C6 1.405 (4) C11—C12 1.378 (5) C2—C3 1.362 (4) C11—H11 0.9300 C2—H2 0.9300 C12—C13 1.365 (5) C3—C4 1.375 (4) C12—H12 0.9300 C3—H3 0.9300 C13—C14 1.383 (4) C4—C5 1.387 (4) C13—H13 0.9300 C4—H4 0.9300
C5—C6—C1 115.7 (2) C12—C13—H13 120.3 C5—C6—C7 124.7 (2) C14—C13—H13 120.3 C1—C6—C7 119.6 (2) C13—C14—C9 122.6 (3) N1—C7—C6 123.0 (3) C13—C14—Cl4 118.1 (2) N1—C7—H7 118.5 C9—C14—Cl4 119.4 (2)
C7—N1—N2—C8 −166.3 (3) N1—N2—C8—C9 178.1 (3) C6—C1—C2—C3 −0.3 (4) N2—C8—C9—C10 −50.5 (4) Cl1—C1—C2—C3 178.0 (2) N2—C8—C9—C14 131.7 (3) C1—C2—C3—C4 0.1 (5) C14—C9—C10—C11 1.0 (4) C2—C3—C4—C5 0.1 (5) C8—C9—C10—C11 −177.0 (3) C3—C4—C5—C6 −0.2 (5) C14—C9—C10—Cl3 179.0 (2) C3—C4—C5—Cl2 178.5 (2) C8—C9—C10—Cl3 1.1 (4) C4—C5—C6—C1 0.1 (4) C9—C10—C11—C12 −0.8 (5) Cl2—C5—C6—C1 −178.6 (2) Cl3—C10—C11—C12 −178.9 (2) C4—C5—C6—C7 177.8 (3) C10—C11—C12—C13 0.3 (5) Cl2—C5—C6—C7 −0.8 (4) C11—C12—C13—C14 0.0 (5) C2—C1—C6—C5 0.2 (4) C12—C13—C14—C9 0.3 (5) Cl1—C1—C6—C5 −178.0 (2) C12—C13—C14—Cl4 −178.8 (2) C2—C1—C6—C7 −177.7 (3) C10—C9—C14—C13 −0.7 (4) Cl1—C1—C6—C7 4.1 (4) C8—C9—C14—C13 177.3 (3) N2—N1—C7—C6 179.6 (3) C10—C9—C14—Cl4 178.40 (19) C5—C6—C7—N1 39.9 (5) C8—C9—C14—Cl4 −3.6 (4) C1—C6—C7—N1 −142.4 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C8—H8···N2i 0.93 2.58 3.487 (3) 166