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

The title compound, C(18)H(18)Cl(2)N(2)O(2), was synthesized by the reaction of 1-(5-chloro-2-methoxy-phen-yl)ethanone with hydrazine hydrate. The mol-ecule lies on a crystallographic twofold axis passing through the mid-point of the N-N bond with one half-mol-ecule in the asymmetric unit. The dihedral angle between the two aromatic rings is 44.33 (4)°. In the crystal, inter-molecular C-H⋯O inter-actions link the mol-ecules 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 = 365.24

Orthorhombic,

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[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 ▶), 592 Friedel pairs

Flack parameter: 0.08 (12)

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.

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

C18H18Cl2N2O2	F(000) = 380
Mr = 365.24	Dx = 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

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

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(Fo2) + (0.1019P)2 + 0.021P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
1566 reflections	Δρmax = 0.12 e Å−3
111 parameters	Δρmin = −0.22 e Å−3
0 restraints	Absolute structure: Flack (1983), 592 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (12)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .