2,4-Dichloro-benzaldehyde 4-methyl-thio-semicarbazone.

The mol-ecule of the title compound, C(9)H(9)Cl(2)N(3)S, has an E configuration about the C=N bond. In the crystal, mol-ecules are linked through inter-molecular N-H⋯S hydrogen bonds, forming zigzag chains along the a axis.

Related literature

For background to Schiff bases derived from thio­semicarbazone and its derivatives, see: Casas et al. (2001 ▶); Beraldo et al. (2001 ▶); Jouad et al. (2002 ▶); Swearingen et al. (2002 ▶). For a similar structure reported recently by the author, see: Li (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶). For similar structures, see: Selvanayagam et al. (2002 ▶); Karakurt et al. (2003 ▶); Bernhardt et al. (2003 ▶); Sampath et al. (2003 ▶).

Experimental

Crystal data

C9H9Cl2N3S

M = 262.15

Monoclinic,

a = 13.444 (3) Å

b = 9.3299 (19) Å

c = 18.499 (4) Å

β = 92.160 (2)°

V = 2318.7 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.71 mm−1

T = 298 K

0.18 × 0.17 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.883, T max = 0.913

7167 measured reflections

2518 independent reflections

1956 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.092

S = 1.05

2518 reflections

143 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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/S1600536810049743/hg2763sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049743/hg2763Isup2.hkl

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

C9H9Cl2N3S	F(000) = 1072
Mr = 262.15	Dx = 1.502 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2253 reflections
a = 13.444 (3) Å	θ = 2.6–27.3°
b = 9.3299 (19) Å	µ = 0.71 mm−1
c = 18.499 (4) Å	T = 298 K
β = 92.160 (2)°	Block, colourless
V = 2318.7 (8) Å3	0.18 × 0.17 × 0.13 mm
Z = 8

Bruker APEXII CCD area-detector diffractometer	2518 independent reflections
Radiation source: fine-focus sealed tube	1956 reflections with I > 2σ(I)
graphite	Rint = 0.029
ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −16→17
Tmin = 0.883, Tmax = 0.913	k = −11→11
7167 measured reflections	l = −12→23

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0407P)2 + 0.9729P] where P = (Fo2 + 2Fc2)/3
2518 reflections	(Δ/σ)max < 0.001
143 parameters	Δρmax = 0.23 e Å−3
2 restraints	Δρmin = −0.35 e Å−3

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
Cl1	−0.06826 (4)	0.82058 (6)	1.03663 (3)	0.05201 (18)
Cl2	0.14697 (5)	0.37973 (7)	1.13869 (4)	0.0674 (2)
N1	0.13058 (12)	0.83265 (18)	0.85768 (9)	0.0383 (4)
N2	0.10483 (12)	0.93140 (19)	0.80525 (9)	0.0410 (4)
N3	0.24558 (13)	0.8704 (2)	0.74802 (10)	0.0433 (4)
S1	0.12967 (4)	1.06871 (6)	0.68333 (3)	0.04588 (17)
C1	0.09166 (13)	0.7175 (2)	0.96685 (10)	0.0317 (4)
C2	0.03225 (14)	0.7064 (2)	1.02693 (10)	0.0344 (4)
C3	0.04938 (16)	0.6053 (2)	1.08024 (11)	0.0409 (5)
H3A	0.0089	0.6004	1.1198	0.049*
C4	0.12731 (16)	0.5122 (2)	1.07367 (11)	0.0422 (5)
C5	0.18905 (16)	0.5198 (2)	1.01613 (12)	0.0452 (5)
H5	0.2421	0.4566	1.0127	0.054*
C6	0.17114 (14)	0.6221 (2)	0.96390 (11)	0.0396 (5)
H6	0.2134	0.6280	0.9253	0.047*
C7	0.07061 (14)	0.8209 (2)	0.90939 (10)	0.0349 (4)
H7	0.0139	0.8779	0.9103	0.042*
C8	0.16428 (14)	0.9497 (2)	0.74839 (11)	0.0360 (5)
C9	0.32200 (18)	0.8847 (3)	0.69507 (14)	0.0600 (7)
H9A	0.2927	0.8722	0.6473	0.090*
H9B	0.3723	0.8131	0.7039	0.090*
H9C	0.3515	0.9782	0.6990	0.090*
H2	0.0484 (12)	0.982 (2)	0.8085 (14)	0.080*
H3	0.258 (2)	0.810 (2)	0.7848 (10)	0.080*

	U11	U22	U33	U12	U13	U23
Cl1	0.0503 (3)	0.0534 (3)	0.0537 (4)	0.0147 (3)	0.0206 (3)	0.0003 (3)
Cl2	0.0850 (5)	0.0555 (4)	0.0599 (4)	−0.0016 (3)	−0.0195 (3)	0.0188 (3)
N1	0.0368 (9)	0.0442 (9)	0.0341 (9)	0.0010 (7)	0.0054 (7)	0.0026 (8)
N2	0.0372 (10)	0.0511 (10)	0.0355 (10)	0.0040 (8)	0.0097 (8)	0.0096 (8)
N3	0.0419 (10)	0.0483 (10)	0.0407 (11)	0.0016 (8)	0.0141 (8)	0.0049 (8)
S1	0.0463 (3)	0.0495 (3)	0.0421 (3)	−0.0076 (3)	0.0037 (2)	0.0102 (2)
C1	0.0299 (10)	0.0328 (10)	0.0325 (10)	−0.0020 (8)	0.0020 (8)	−0.0036 (8)
C2	0.0329 (10)	0.0361 (10)	0.0346 (11)	0.0016 (8)	0.0043 (8)	−0.0048 (8)
C3	0.0474 (12)	0.0436 (12)	0.0319 (11)	−0.0050 (10)	0.0047 (9)	−0.0011 (9)
C4	0.0453 (13)	0.0393 (11)	0.0412 (12)	−0.0031 (10)	−0.0107 (10)	0.0048 (9)
C5	0.0357 (12)	0.0435 (12)	0.0560 (14)	0.0076 (9)	−0.0039 (10)	−0.0027 (11)
C6	0.0335 (11)	0.0433 (11)	0.0422 (12)	0.0017 (9)	0.0051 (9)	−0.0029 (9)
C7	0.0325 (11)	0.0382 (10)	0.0343 (11)	0.0002 (8)	0.0067 (8)	−0.0038 (9)
C8	0.0357 (11)	0.0378 (11)	0.0348 (11)	−0.0091 (9)	0.0032 (8)	−0.0022 (8)
C9	0.0550 (15)	0.0684 (16)	0.0587 (16)	0.0019 (13)	0.0281 (12)	0.0064 (13)

Cl1—C2	1.735 (2)	C1—C7	1.455 (3)
Cl2—C4	1.738 (2)	C2—C3	1.378 (3)
N1—C7	1.279 (2)	C3—C4	1.370 (3)
N1—N2	1.373 (2)	C3—H3A	0.9300
N2—C8	1.356 (2)	C4—C5	1.376 (3)
N2—H2	0.898 (10)	C5—C6	1.373 (3)
N3—C8	1.320 (3)	C5—H5	0.9300
N3—C9	1.452 (3)	C6—H6	0.9300
N3—H3	0.893 (10)	C7—H7	0.9300
S1—C8	1.690 (2)	C9—H9A	0.9600
C1—C6	1.393 (3)	C9—H9B	0.9600
C1—C2	1.397 (3)	C9—H9C	0.9600
C7—N1—N2	115.91 (17)	C6—C5—C4	119.05 (19)
C8—N2—N1	119.51 (17)	C6—C5—H5	120.5
C8—N2—H2	120.7 (17)	C4—C5—H5	120.5
N1—N2—H2	119.8 (17)	C5—C6—C1	122.07 (19)
C8—N3—C9	123.97 (19)	C5—C6—H6	119.0
C8—N3—H3	118.4 (18)	C1—C6—H6	119.0
C9—N3—H3	117.3 (18)	N1—C7—C1	119.52 (18)
C6—C1—C2	116.50 (18)	N1—C7—H7	120.2
C6—C1—C7	121.54 (17)	C1—C7—H7	120.2
C2—C1—C7	121.95 (17)	N3—C8—N2	116.47 (18)
C3—C2—C1	122.36 (18)	N3—C8—S1	124.78 (15)
C3—C2—Cl1	117.13 (15)	N2—C8—S1	118.75 (15)
C1—C2—Cl1	120.50 (15)	N3—C9—H9A	109.5
C4—C3—C2	118.59 (19)	N3—C9—H9B	109.5
C4—C3—H3A	120.7	H9A—C9—H9B	109.5
C2—C3—H3A	120.7	N3—C9—H9C	109.5
C3—C4—C5	121.40 (19)	H9A—C9—H9C	109.5
C3—C4—Cl2	119.12 (17)	H9B—C9—H9C	109.5
C5—C4—Cl2	119.47 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1i	0.90 (1)	2.54 (1)	3.4169 (18)	167 (2)
N3—H3···S1ii	0.89 (1)	2.77 (2)	3.491 (2)	139 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1i	0.90 (1)	2.54 (1)	3.4169 (18)	167 (2)
N3—H3⋯S1ii	0.89 (1)	2.77 (2)	3.491 (2)	139 (2)

Symmetry codes: (i) ; (ii) .