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

Chang, J.-G.; Lu, J.; Zhao, R.-G.

doi:10.1107/S1600536809048351

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3185

doi:10.1107/S1600536809048351

Open

access

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

Jian-Guo Chang,^a ^* Jie Lu ^b and Ren-Gao Zhao ^a

^aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China, and ^bDepartment of Architecture and Mechanical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: tsucjg@163.com

(Received 25 September 2009; accepted 14 November 2009; online 25 November 2009)

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 ); Kundu et al. (2005 ). For related structures, see: Glaser et al. (1995 ); Hunig et al. (2000 ).

Experimental

Crystal data

C₁₈H₁₈Cl₂N₂O₂
M_r = 365.24
Orthorhombic, P 2₁ 2₁ 2
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 ) 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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.129
S = 1.01
1566 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), 592 Friedel pairs
Flack parameter: 0.08 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O1ⁱ	0.96	2.68	3.521 (3)	146
Symmetry code: (i) x, y, z-1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

For azine compounds containing both a diimine linkage and

N—N bonding, see: Kesslen et al. (1999); Kundu et al. (2005). For related structures, see: Glaser et al. (1995); Hunig et al. (2000).

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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

	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 .

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

Crystal data top

C₁₈H₁₈Cl₂N₂O₂	F(000) = 380
M_r = 365.24	D_x = 1.383 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 2313 reflections
a = 7.9030 (19) Å	θ = 2.7–27.8°
b = 27.862 (7) Å	µ = 0.38 mm⁻¹
c = 3.9819 (10) Å	T = 295 K
V = 876.8 (4) Å³	Block, colourless
Z = 2	0.22 × 0.16 × 0.12 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	1566 independent reflections
Radiation source: fine-focus sealed tube	1417 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→8
T_min = 0.921, T_max = 0.956	k = −33→32
4469 measured reflections	l = −4→4

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.1019P)² + 0.021P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1566 reflections	Δρ_max = 0.12 e Å⁻³
111 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 592 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (12)

Crystal data top

C₁₈H₁₈Cl₂N₂O₂	V = 876.8 (4) Å³
M_r = 365.24	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 7.9030 (19) Å	µ = 0.38 mm⁻¹
b = 27.862 (7) Å	T = 295 K
c = 3.9819 (10) Å	0.22 × 0.16 × 0.12 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	1566 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1417 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.956	R_int = 0.019
4469 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.129	Δρ_max = 0.12 e Å⁻³
S = 1.01	Δρ_min = −0.22 e Å⁻³
1566 reflections	Absolute structure: Flack (1983), 592 Friedel pairs
111 parameters	Absolute structure parameter: 0.08 (12)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.35358 (10)	0.29469 (2)	0.1116 (2)	0.0643 (3)
O1	0.9306 (2)	0.40920 (6)	0.5876 (6)	0.0520 (5)
N1	0.5044 (3)	0.47464 (6)	0.4965 (5)	0.0367 (5)
C1	0.6541 (3)	0.40440 (7)	0.3671 (6)	0.0333 (5)
C2	0.8000 (3)	0.38071 (8)	0.4798 (6)	0.0373 (6)
C3	0.8050 (4)	0.33068 (10)	0.4871 (7)	0.0487 (7)
H3	0.9006	0.3150	0.5674	0.058*
C4	0.6670 (3)	0.30434 (8)	0.3743 (7)	0.0468 (7)
H4	0.6702	0.2710	0.3770	0.056*
C5	0.5261 (4)	0.32784 (9)	0.2588 (7)	0.0429 (6)
C6	0.5175 (3)	0.37744 (8)	0.2532 (6)	0.0381 (6)
H6	0.4208	0.3927	0.1736	0.046*
C7	1.0770 (4)	0.38654 (12)	0.7221 (9)	0.0611 (8)
H7A	1.0453	0.3671	0.9111	0.092*
H7B	1.1565	0.4106	0.7929	0.092*
H7C	1.1279	0.3667	0.5532	0.092*
C8	0.6407 (3)	0.45789 (8)	0.3653 (6)	0.0330 (5)
C9	0.7746 (3)	0.48801 (9)	0.2056 (7)	0.0413 (6)
H9A	0.7244	0.5081	0.0369	0.062*
H9B	0.8580	0.4676	0.1039	0.062*
H9C	0.8274	0.5077	0.3734	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0758 (5)	0.0434 (4)	0.0738 (5)	−0.0196 (3)	−0.0095 (5)	−0.0004 (4)
O1	0.0404 (9)	0.0499 (10)	0.0656 (13)	0.0104 (8)	−0.0170 (10)	−0.0051 (10)
N1	0.0331 (10)	0.0273 (9)	0.0497 (12)	0.0040 (8)	−0.0013 (9)	0.0009 (9)
C1	0.0368 (12)	0.0316 (12)	0.0315 (11)	0.0055 (9)	0.0014 (11)	0.0012 (9)
C2	0.0404 (13)	0.0386 (12)	0.0329 (12)	0.0102 (10)	−0.0014 (10)	−0.0024 (10)
C3	0.0568 (16)	0.0408 (13)	0.0485 (15)	0.0213 (12)	−0.0006 (13)	0.0047 (12)
C4	0.0618 (17)	0.0286 (11)	0.0500 (15)	0.0080 (11)	0.0084 (15)	0.0008 (11)
C5	0.0567 (16)	0.0327 (12)	0.0392 (13)	−0.0037 (12)	0.0022 (12)	0.0010 (10)
C6	0.0382 (13)	0.0343 (12)	0.0420 (13)	0.0049 (10)	−0.0002 (11)	0.0035 (10)
C7	0.0409 (14)	0.082 (2)	0.0605 (19)	0.0158 (15)	−0.0150 (13)	−0.0022 (17)
C8	0.0340 (11)	0.0311 (11)	0.0337 (11)	0.0024 (9)	−0.0040 (11)	−0.0019 (9)
C9	0.0400 (12)	0.0362 (13)	0.0475 (15)	−0.0018 (11)	0.0057 (11)	−0.0039 (11)

Geometric parameters (Å, º) top

Cl1—C5	1.748 (3)	C4—C5	1.371 (4)
O1—C2	1.371 (3)	C4—H4	0.9300
O1—C7	1.422 (3)	C5—C6	1.384 (3)
N1—C8	1.285 (3)	C6—H6	0.9300
N1—N1ⁱ	1.415 (3)	C7—H7A	0.9600
C1—C6	1.391 (3)	C7—H7B	0.9600
C1—C2	1.403 (3)	C7—H7C	0.9600
C1—C8	1.494 (3)	C8—C9	1.493 (3)
C2—C3	1.395 (4)	C9—H9A	0.9600
C3—C4	1.389 (4)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600

C2—O1—C7	118.2 (2)	C5—C6—H6	120.1
C8—N1—N1ⁱ	113.8 (2)	C1—C6—H6	120.1
C6—C1—C2	119.2 (2)	O1—C7—H7A	109.5
C6—C1—C8	118.9 (2)	O1—C7—H7B	109.5
C2—C1—C8	121.9 (2)	H7A—C7—H7B	109.5
O1—C2—C3	123.4 (2)	O1—C7—H7C	109.5
O1—C2—C1	116.53 (19)	H7A—C7—H7C	109.5
C3—C2—C1	120.0 (2)	H7B—C7—H7C	109.5
C4—C3—C2	119.9 (2)	N1—C8—C9	124.3 (2)
C4—C3—H3	120.0	N1—C8—C1	114.8 (2)
C2—C3—H3	120.0	C9—C8—C1	120.9 (2)
C5—C4—C3	119.6 (2)	C8—C9—H9A	109.5
C5—C4—H4	120.2	C8—C9—H9B	109.5
C3—C4—H4	120.2	H9A—C9—H9B	109.5
C4—C5—C6	121.5 (3)	C8—C9—H9C	109.5
C4—C5—Cl1	119.57 (19)	H9A—C9—H9C	109.5
C6—C5—Cl1	118.9 (2)	H9B—C9—H9C	109.5
C5—C6—C1	119.7 (2)

C7—O1—C2—C3	−1.7 (4)	C4—C5—C6—C1	−0.1 (4)
C7—O1—C2—C1	176.4 (2)	Cl1—C5—C6—C1	−179.54 (19)
C6—C1—C2—O1	179.7 (2)	C2—C1—C6—C5	1.3 (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—C3	178.0 (2)	N1ⁱ—N1—C8—C1	179.13 (16)
O1—C2—C3—C4	179.8 (2)	C6—C1—C8—N1	48.8 (3)
C1—C2—C3—C4	1.7 (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—C9	51.5 (3)
C3—C4—C5—Cl1	179.2 (2)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O1ⁱⁱ	0.96	2.68	3.521 (3)	146

Symmetry code: (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈Cl₂N₂O₂
M_r	365.24
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	295
a, b, c (Å)	7.9030 (19), 27.862 (7), 3.9819 (10)
V (Å³)	876.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.22 × 0.16 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.921, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	4469, 1566, 1417
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.129, 1.01
No. of reflections	1566
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.22
Absolute structure	Flack (1983), 592 Friedel pairs
Absolute structure parameter	0.08 (12)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O1ⁱ	0.96	2.68	3.521 (3)	146.0

Symmetry code: (i) x, y, z−1.

Acknowledgements

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

References

Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Glaser, R., Chen, G. S., Anthamatten, M. & Barnes, C. L. (1995). J. Chem. Soc. Perkin Trans. 2, pp. 1449–1458. CSD CrossRef Google Scholar
Hunig, S., Kemmer, M. & Wenner, H. (2000). Chem. Eur. J. 6, 2618–2632. CrossRef PubMed CAS Google Scholar
Kesslen, E. C., Euler, W. B. & Foxman, B. M. (1999). Chem. Mater. 11, 336–340. Web of Science CSD CrossRef CAS Google Scholar
Kundu, N., Chatterjee, P. B., Chaudhury, M. & Tiekink, E. R. T. (2005). Acta Cryst. E61, m1583–m1585. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar