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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3185.
Published online 2009 November 25. doi:  10.1107/S1600536809048351
PMCID: PMC2971795

(E,E)-2,5-Bis(5-chloro-2-methoxyphenyl)-3,4-diazahexa-2,4-diene

Abstract

The title compound, C18H18Cl2N2O2, was synthesized by the reaction of 1-(5-chloro-2-methoxy­phen­yl)ethanone with hydrazine hydrate. The mol­ecule lies on a crystallographic twofold axis passing through the mid-point of the N—N bond with one half-mol­ecule in the asymmetric unit. The dihedral angle between the two aromatic rings is 44.33 (4)°. In the crystal, inter­molecular C—H(...)O inter­actions link the mol­ecules into columns along the c axis

Related literature

For azine compounds containing both a diimine linkage and N—N bonding, see: Kesslen et al. (1999 [triangle]); Kundu et al. (2005 [triangle]). For related structures, see: Glaser et al. (1995 [triangle]); Hunig et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3185-scheme1.jpg

Experimental

Crystal data

  • C18H18Cl2N2O2
  • M r = 365.24
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3185-efi1.jpg
  • a = 7.9030 (19) Å
  • b = 27.862 (7) Å
  • c = 3.9819 (10) Å
  • V = 876.8 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.38 mm−1
  • T = 295 K
  • 0.22 × 0.16 × 0.12 mm

Data collection

  • Bruker APEXII CCD area detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.921, T max = 0.956
  • 4469 measured reflections
  • 1566 independent reflections
  • 1417 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.129
  • S = 1.01
  • 1566 reflections
  • 111 parameters
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.22 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 592 Friedel pairs
  • Flack parameter: 0.08 (12)

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048351/fl2273sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048351/fl2273Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This project was supported by the Postgraduate Foundation of Taishan University (No.Y05–2-09)

supplementary crystallographic information

Comment

Recently, a number of azine compounds containing both a diimine linkage and N—N bonding have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen et al., 1999). As an extension of the work on the structural characterization of azine derivatives, the title compound, (I),was synthesized and its crystal structure is reported here.

The molecule lies on a crystallogrpahic 2-fold axis passing through the mid-point of the N-N bond to give 1/2 molecule per asymmetric unit. (Fig. 1). The dihedral angle between the two aromatic rings is 44.33 (4)°. The N atom and the phenyl ring liie on opposite side of the C8=N1 bond to give an (E, E) conformation with respect to the C8=N1 bond ( and its symmetry related C8a=N1a double bond (Fig. 1.). This configuration agrees with those commonly found in similar compounds (Glaser et al., 1995; Hunig et al., 2000). Intermolecular C—H···O interactions link the molecules into columns along the c axis (Table 1, Fig. 2).

Experimental

An ethanol solution (30 ml) of hydrazine (0.02 mol) and 1-(5-chloro-2-methoxyphenyl)ethanone (0.04 mol) was refluxed and stirred for 6 h; the mixture was cooled and the resulting solid product, (I), was collected by filtration. Colourless crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms,with CH(methyl) = 0.96 Å, C—H(aromatic) = 0.93 Å, and with Uiso(H) =1.5Ueq(Cmethyl) and 1.2Ueq(Caromatic).

Figures

Fig. 1.
The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The crystal packing of (I) , Dashed lines show intermolecular C—H···O interactions .

Crystal data

C18H18Cl2N2O2F(000) = 380
Mr = 365.24Dx = 1.383 Mg m3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 2313 reflections
a = 7.9030 (19) Åθ = 2.7–27.8°
b = 27.862 (7) ŵ = 0.38 mm1
c = 3.9819 (10) ÅT = 295 K
V = 876.8 (4) Å3Block, colourless
Z = 20.22 × 0.16 × 0.12 mm

Data collection

Bruker APEXII CCD area detector diffractometer1566 independent reflections
Radiation source: fine-focus sealed tube1417 reflections with I > 2σ(I)
graphiteRint = 0.019
phi and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −9→8
Tmin = 0.921, Tmax = 0.956k = −33→32
4469 measured reflectionsl = −4→4

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.129w = 1/[σ2(Fo2) + (0.1019P)2 + 0.021P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1566 reflectionsΔρmax = 0.12 e Å3
111 parametersΔρmin = −0.22 e Å3
0 restraintsAbsolute structure: Flack (1983), 592 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.08 (12)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
Cl10.35358 (10)0.29469 (2)0.1116 (2)0.0643 (3)
O10.9306 (2)0.40920 (6)0.5876 (6)0.0520 (5)
N10.5044 (3)0.47464 (6)0.4965 (5)0.0367 (5)
C10.6541 (3)0.40440 (7)0.3671 (6)0.0333 (5)
C20.8000 (3)0.38071 (8)0.4798 (6)0.0373 (6)
C30.8050 (4)0.33068 (10)0.4871 (7)0.0487 (7)
H30.90060.31500.56740.058*
C40.6670 (3)0.30434 (8)0.3743 (7)0.0468 (7)
H40.67020.27100.37700.056*
C50.5261 (4)0.32784 (9)0.2588 (7)0.0429 (6)
C60.5175 (3)0.37744 (8)0.2532 (6)0.0381 (6)
H60.42080.39270.17360.046*
C71.0770 (4)0.38654 (12)0.7221 (9)0.0611 (8)
H7A1.04530.36710.91110.092*
H7B1.15650.41060.79290.092*
H7C1.12790.36670.55320.092*
C80.6407 (3)0.45789 (8)0.3653 (6)0.0330 (5)
C90.7746 (3)0.48801 (9)0.2056 (7)0.0413 (6)
H9A0.72440.50810.03690.062*
H9B0.85800.46760.10390.062*
H9C0.82740.50770.37340.062*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0758 (5)0.0434 (4)0.0738 (5)−0.0196 (3)−0.0095 (5)−0.0004 (4)
O10.0404 (9)0.0499 (10)0.0656 (13)0.0104 (8)−0.0170 (10)−0.0051 (10)
N10.0331 (10)0.0273 (9)0.0497 (12)0.0040 (8)−0.0013 (9)0.0009 (9)
C10.0368 (12)0.0316 (12)0.0315 (11)0.0055 (9)0.0014 (11)0.0012 (9)
C20.0404 (13)0.0386 (12)0.0329 (12)0.0102 (10)−0.0014 (10)−0.0024 (10)
C30.0568 (16)0.0408 (13)0.0485 (15)0.0213 (12)−0.0006 (13)0.0047 (12)
C40.0618 (17)0.0286 (11)0.0500 (15)0.0080 (11)0.0084 (15)0.0008 (11)
C50.0567 (16)0.0327 (12)0.0392 (13)−0.0037 (12)0.0022 (12)0.0010 (10)
C60.0382 (13)0.0343 (12)0.0420 (13)0.0049 (10)−0.0002 (11)0.0035 (10)
C70.0409 (14)0.082 (2)0.0605 (19)0.0158 (15)−0.0150 (13)−0.0022 (17)
C80.0340 (11)0.0311 (11)0.0337 (11)0.0024 (9)−0.0040 (11)−0.0019 (9)
C90.0400 (12)0.0362 (13)0.0475 (15)−0.0018 (11)0.0057 (11)−0.0039 (11)

Geometric parameters (Å, °)

Cl1—C51.748 (3)C4—C51.371 (4)
O1—C21.371 (3)C4—H40.9300
O1—C71.422 (3)C5—C61.384 (3)
N1—C81.285 (3)C6—H60.9300
N1—N1i1.415 (3)C7—H7A0.9600
C1—C61.391 (3)C7—H7B0.9600
C1—C21.403 (3)C7—H7C0.9600
C1—C81.494 (3)C8—C91.493 (3)
C2—C31.395 (4)C9—H9A0.9600
C3—C41.389 (4)C9—H9B0.9600
C3—H30.9300C9—H9C0.9600
C2—O1—C7118.2 (2)C5—C6—H6120.1
C8—N1—N1i113.8 (2)C1—C6—H6120.1
C6—C1—C2119.2 (2)O1—C7—H7A109.5
C6—C1—C8118.9 (2)O1—C7—H7B109.5
C2—C1—C8121.9 (2)H7A—C7—H7B109.5
O1—C2—C3123.4 (2)O1—C7—H7C109.5
O1—C2—C1116.53 (19)H7A—C7—H7C109.5
C3—C2—C1120.0 (2)H7B—C7—H7C109.5
C4—C3—C2119.9 (2)N1—C8—C9124.3 (2)
C4—C3—H3120.0N1—C8—C1114.8 (2)
C2—C3—H3120.0C9—C8—C1120.9 (2)
C5—C4—C3119.6 (2)C8—C9—H9A109.5
C5—C4—H4120.2C8—C9—H9B109.5
C3—C4—H4120.2H9A—C9—H9B109.5
C4—C5—C6121.5 (3)C8—C9—H9C109.5
C4—C5—Cl1119.57 (19)H9A—C9—H9C109.5
C6—C5—Cl1118.9 (2)H9B—C9—H9C109.5
C5—C6—C1119.7 (2)
C7—O1—C2—C3−1.7 (4)C4—C5—C6—C1−0.1 (4)
C7—O1—C2—C1176.4 (2)Cl1—C5—C6—C1−179.54 (19)
C6—C1—C2—O1179.7 (2)C2—C1—C6—C51.3 (4)
C8—C1—C2—O1−0.2 (3)C8—C1—C6—C5−178.8 (2)
C6—C1—C2—C3−2.1 (4)N1i—N1—C8—C9−3.8 (3)
C8—C1—C2—C3178.0 (2)N1i—N1—C8—C1179.13 (16)
O1—C2—C3—C4179.8 (2)C6—C1—C8—N148.8 (3)
C1—C2—C3—C41.7 (4)C2—C1—C8—N1−131.3 (2)
C2—C3—C4—C5−0.5 (4)C6—C1—C8—C9−128.4 (2)
C3—C4—C5—C6−0.3 (4)C2—C1—C8—C951.5 (3)
C3—C4—C5—Cl1179.2 (2)

Symmetry codes: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9B···O1ii0.962.683.521 (3)146

Symmetry codes: (ii) x, y, z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2273).

References

  • Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Glaser, R., Chen, G. S., Anthamatten, M. & Barnes, C. L. (1995). J. Chem. Soc. Perkin Trans. 2, pp. 1449–1458.
  • Hunig, S., Kemmer, M. & Wenner, H. (2000). Chem. Eur. J. 6, 2618–2632. [PubMed]
  • 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.
  • Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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