Dimethyl 2-[2-(2,4,6-tri-chloro-phen-yl)hydrazin-1-yl-idene]butane-dioate.

In the title compound, C12H11Cl3N2O4, the dihedral angle between the aromatic ring and the hydrazine (NH-N=C) grouping is 52.2 (3)°. The butanedioate groups exhibit planar conformations. An intra-molecular N-H⋯O hydrogen bond links the N-H group of the hydrazine to one of the meth-oxy groups of the butane-dioate moiety. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and π-π inter-actions are also observed [centroid-centroid separation = 3.535 (1) Å].

Related literature

For the pharmacological activity of halo-substituted derivatives, see: Kees et al. (1996 ▶). For the use of the title compound in the synthesis of pyrazoles, see: Palacios et al. (1999 ▶). For the biological activity of pyrazoles, see: Palacios et al. (1999 ▶); Lee et al. (2003 ▶); Nithinchandra et al. (2012 ▶); Genin et al. (2000 ▶); Reddy et al. (2008 ▶); Kees et al. (1996 ▶). For a related structure, see: Huang et al. (2011 ▶).

Experimental

Crystal data

C12H11Cl3N2O4

M = 353.58

Orthorhombic,

a = 7.0182 (5) Å

b = 16.0165 (12) Å

c = 26.7488 (15) Å

V = 3006.8 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.63 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.716, T max = 1.000

7083 measured reflections

2954 independent reflections

1844 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.118

S = 1.03

2954 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S160053681303242X/sj5364sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681303242X/sj5364Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681303242X/sj5364Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H11Cl3N2O4	F(000) = 1440
Mr = 353.58	Dx = 1.562 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1944 reflections
a = 7.0182 (5) Å	θ = 3.9–27.4°
b = 16.0165 (12) Å	µ = 0.63 mm−1
c = 26.7488 (15) Å	T = 293 K
V = 3006.8 (4) Å3	Block, white
Z = 8	0.30 × 0.20 × 0.20 mm

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2954 independent reflections
Radiation source: fine-focus sealed tube	1844 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.9°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −19→11
Tmin = 0.716, Tmax = 1.000	l = −32→30
7083 measured reflections

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)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.0358P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.006
2954 reflections	Δρmax = 0.26 e Å−3
195 parameters	Δρmin = −0.24 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (4)

Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01–02-2013 CrysAlis171. NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Cl7	0.13759 (16)	0.09353 (6)	0.31855 (3)	0.0641 (3)
Cl9	0.09570 (15)	−0.23591 (5)	0.27554 (3)	0.0589 (3)
Cl8	0.16340 (14)	−0.01155 (7)	0.12827 (3)	0.0640 (3)
O21	0.4517 (4)	−0.22006 (15)	0.47244 (7)	0.0604 (7)
N11	0.2602 (4)	−0.14140 (16)	0.36258 (8)	0.0385 (6)
N10	0.1266 (4)	−0.08714 (18)	0.34507 (9)	0.0406 (7)
O19	0.5314 (3)	−0.24056 (15)	0.39230 (8)	0.0572 (7)
O15	0.2372 (4)	0.01540 (15)	0.43653 (8)	0.0582 (7)
C3	0.1464 (4)	0.0307 (2)	0.22574 (11)	0.0443 (8)
H3	0.1510	0.0859	0.2150	0.053*
C12	0.2654 (4)	−0.15507 (19)	0.41006 (10)	0.0385 (8)
C1	0.1339 (4)	−0.0696 (2)	0.29355 (10)	0.0344 (7)
O17	0.2154 (4)	−0.02745 (18)	0.51588 (9)	0.0796 (9)
C6	0.1257 (4)	−0.13302 (19)	0.25794 (11)	0.0385 (8)
C5	0.1340 (4)	−0.1159 (2)	0.20686 (11)	0.0429 (8)
H5	0.1315	−0.1589	0.1835	0.051*
C13	0.1318 (5)	−0.1207 (2)	0.44935 (11)	0.0459 (9)
H13A	0.0081	−0.1111	0.4342	0.055*
H13B	0.1158	−0.1622	0.4754	0.055*
C4	0.1460 (4)	−0.0342 (2)	0.19178 (12)	0.0459 (9)
C2	0.1399 (4)	0.0117 (2)	0.27610 (11)	0.0401 (8)
C18	0.4236 (5)	−0.2085 (2)	0.42838 (12)	0.0437 (8)
C14	0.1996 (5)	−0.0411 (2)	0.47251 (12)	0.0508 (9)
C16	0.3100 (6)	0.0954 (2)	0.45282 (14)	0.0744 (12)
H16A	0.3322	0.1303	0.4242	0.112*
H16B	0.4275	0.0874	0.4706	0.112*
H16C	0.2187	0.1217	0.4744	0.112*
C20	0.6937 (6)	−0.2892 (3)	0.40768 (13)	0.0762 (13)
H20A	0.7602	−0.3090	0.3787	0.114*
H20B	0.6515	−0.3358	0.4273	0.114*
H20C	0.7775	−0.2550	0.4273	0.114*
H10	0.096 (5)	−0.044 (2)	0.3640 (11)	0.050 (10)*

	U11	U22	U33	U12	U13	U23
Cl7	0.0891 (8)	0.0417 (5)	0.0615 (6)	−0.0035 (5)	0.0025 (5)	−0.0015 (4)
Cl9	0.0786 (7)	0.0401 (5)	0.0580 (6)	−0.0024 (5)	−0.0102 (4)	0.0033 (4)
Cl8	0.0631 (6)	0.0898 (8)	0.0393 (5)	−0.0039 (6)	−0.0063 (4)	0.0186 (5)
O21	0.0808 (18)	0.0676 (18)	0.0327 (13)	0.0156 (15)	−0.0090 (12)	0.0032 (11)
N11	0.0441 (16)	0.0355 (15)	0.0359 (14)	0.0012 (13)	−0.0024 (11)	0.0004 (12)
N10	0.0456 (16)	0.0408 (16)	0.0353 (16)	0.0085 (14)	0.0012 (12)	0.0040 (14)
O19	0.0691 (16)	0.0619 (17)	0.0406 (13)	0.0275 (14)	0.0008 (12)	0.0060 (11)
O15	0.0717 (18)	0.0510 (16)	0.0519 (14)	−0.0054 (14)	0.0097 (13)	−0.0132 (12)
C3	0.0340 (17)	0.050 (2)	0.049 (2)	−0.0022 (17)	−0.0002 (14)	0.0149 (18)
C12	0.0480 (19)	0.0361 (18)	0.0314 (16)	−0.0027 (16)	−0.0009 (13)	0.0017 (13)
C1	0.0289 (16)	0.0398 (19)	0.0344 (17)	0.0020 (15)	0.0001 (12)	0.0065 (14)
O17	0.109 (2)	0.090 (2)	0.0399 (14)	0.018 (2)	−0.0080 (14)	−0.0129 (15)
C6	0.0330 (16)	0.0365 (19)	0.0461 (19)	0.0000 (15)	−0.0038 (14)	0.0096 (15)
C5	0.0390 (18)	0.055 (2)	0.0346 (18)	0.0054 (18)	−0.0061 (14)	−0.0010 (16)
C13	0.055 (2)	0.050 (2)	0.0328 (17)	0.0003 (18)	0.0049 (14)	−0.0002 (16)
C4	0.0306 (17)	0.060 (2)	0.0470 (19)	−0.0008 (18)	−0.0043 (14)	0.0105 (19)
C2	0.0366 (17)	0.0421 (19)	0.0415 (19)	−0.0009 (16)	0.0009 (14)	0.0031 (15)
C18	0.058 (2)	0.0343 (18)	0.0390 (19)	−0.0038 (17)	−0.0011 (16)	−0.0001 (15)
C14	0.049 (2)	0.062 (2)	0.041 (2)	0.014 (2)	0.0062 (16)	−0.0017 (18)
C16	0.091 (3)	0.045 (2)	0.087 (3)	0.000 (2)	0.001 (2)	−0.016 (2)
C20	0.081 (3)	0.081 (3)	0.067 (3)	0.043 (3)	−0.002 (2)	0.008 (2)

Cl7—C2	1.735 (3)	C12—C13	1.512 (4)
Cl9—C6	1.727 (3)	C1—C2	1.383 (4)
Cl8—C4	1.741 (3)	C1—C6	1.394 (4)
O21—C18	1.209 (3)	O17—C14	1.186 (3)
N11—C12	1.289 (3)	C6—C5	1.395 (4)
N11—N10	1.362 (3)	C5—C4	1.372 (5)
N10—C1	1.407 (4)	C5—H5	0.9300
N10—H10	0.88 (3)	C13—C14	1.495 (5)
O19—C18	1.329 (4)	C13—H13A	0.9700
O19—C20	1.440 (4)	C13—H13B	0.9700
O15—C14	1.348 (4)	C16—H16A	0.9600
O15—C16	1.447 (4)	C16—H16B	0.9600
C3—C2	1.382 (4)	C16—H16C	0.9600
C3—C4	1.380 (5)	C20—H20A	0.9600
C3—H3	0.9300	C20—H20B	0.9600
C12—C18	1.485 (4)	C20—H20C	0.9600
C12—N11—N10	117.8 (3)	H13A—C13—H13B	107.7
N11—N10—C1	116.1 (2)	C5—C4—C3	121.7 (3)
N11—N10—H10	118 (2)	C5—C4—Cl8	119.3 (3)
C1—N10—H10	115 (2)	C3—C4—Cl8	119.0 (3)
C18—O19—C20	116.9 (3)	C3—C2—C1	122.5 (3)
C14—O15—C16	116.7 (3)	C3—C2—Cl7	118.1 (3)
C2—C3—C4	118.4 (3)	C1—C2—Cl7	119.3 (2)
C2—C3—H3	120.8	O21—C18—O19	123.7 (3)
C4—C3—H3	120.8	O21—C18—C12	122.2 (3)
N11—C12—C18	116.4 (3)	O19—C18—C12	114.1 (3)
N11—C12—C13	127.3 (3)	O17—C14—O15	123.8 (4)
C18—C12—C13	116.3 (3)	O17—C14—C13	126.4 (4)
C2—C1—C6	117.1 (3)	O15—C14—C13	109.8 (3)
C2—C1—N10	121.3 (3)	O15—C16—H16A	109.5
C6—C1—N10	121.5 (3)	O15—C16—H16B	109.5
C1—C6—C5	121.6 (3)	H16A—C16—H16B	109.5
C1—C6—Cl9	120.9 (2)	O15—C16—H16C	109.5
C5—C6—Cl9	117.4 (3)	H16A—C16—H16C	109.5
C4—C5—C6	118.5 (3)	H16B—C16—H16C	109.5
C4—C5—H5	120.7	O19—C20—H20A	109.5
C6—C5—H5	120.7	O19—C20—H20B	109.5
C14—C13—C12	113.6 (3)	H20A—C20—H20B	109.5
C14—C13—H13A	108.8	O19—C20—H20C	109.5
C12—C13—H13A	108.8	H20A—C20—H20C	109.5
C14—C13—H13B	108.8	H20B—C20—H20C	109.5
C12—C13—H13B	108.8
C12—N11—N10—C1	175.9 (3)	C4—C3—C2—C1	0.3 (5)
N10—N11—C12—C18	−174.7 (3)	C4—C3—C2—Cl7	−179.3 (2)
N10—N11—C12—C13	3.4 (5)	C6—C1—C2—C3	−2.9 (5)
N11—N10—C1—C2	−127.5 (3)	N10—C1—C2—C3	−179.8 (3)
N11—N10—C1—C6	55.8 (4)	C6—C1—C2—Cl7	176.7 (2)
C2—C1—C6—C5	3.5 (4)	N10—C1—C2—Cl7	−0.2 (4)
N10—C1—C6—C5	−179.6 (3)	C20—O19—C18—O21	−2.2 (5)
C2—C1—C6—Cl9	−174.0 (2)	C20—O19—C18—C12	176.6 (3)
N10—C1—C6—Cl9	2.9 (4)	N11—C12—C18—O21	173.9 (3)
C1—C6—C5—C4	−1.6 (4)	C13—C12—C18—O21	−4.3 (5)
Cl9—C6—C5—C4	176.0 (2)	N11—C12—C18—O19	−4.9 (4)
N11—C12—C13—C14	−92.3 (4)	C13—C12—C18—O19	176.8 (3)
C18—C12—C13—C14	85.7 (4)	C16—O15—C14—O17	3.2 (5)
C6—C5—C4—C3	−1.2 (5)	C16—O15—C14—C13	−178.2 (3)
C6—C5—C4—Cl8	178.2 (2)	C12—C13—C14—O17	−127.7 (4)
C2—C3—C4—C5	1.8 (5)	C12—C13—C14—O15	53.8 (4)
C2—C3—C4—Cl8	−177.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10···O15	0.87 (3)	2.38 (3)	3.047 (3)	133 (3)
C5—H5···O19i	0.93	2.51	3.397 (4)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10⋯O15	0.87 (3)	2.38 (3)	3.047 (3)	133 (3)
C5—H5⋯O19i	0.93	2.51	3.397 (4)	159

Symmetry code: (i) .