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Acta Cryst. (2011). E67, o20    [ doi:10.1107/S1600536810049743 ]

2,4-Dichlorobenzaldehyde 4-methylthiosemicarbazone

R. Li

Abstract top

The molecule of the title compound, C9H9Cl2N3S, has an E configuration about the C=N bond. In the crystal, molecules are linked through intermolecular N-H...S hydrogen bonds, forming zigzag chains along the a axis.

Comment top

Thiosemicarbazone and its derivatives are important materials for the preparation of Schiff bases (Casas et al., 2001; Beraldo et al., 2001; Jouad et al., 2002; Swearingen et al., 2002). As a continuation of the work on the structures of such compounds (Li, 2010), in this paper, the title new Schiff base compound derived from the condensation of 2,4-dichlorobenzaldehyde with 4-methylthiosemicarbazone is reported.

The molecule of the title compound, Fig. 1, possesses an E configuration about the C7═N1 bond. The bond lengths have normal values (Allen et al., 1987), and are comparable to those observed in similar compounds (Selvanayagam et al., 2002; Karakurt et al., 2003; Bernhardt et al., 2003; Sampath et al., 2003).

In the crystal, molecules are linked through intermolecular N—H···S hydrogen bonds (Table 1), to form zigzag chains along the a axis (Fig. 2).

Related literature top

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 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 top

The title compound was prepared by the Schiff base condensation of equimolar quantities of 2,4-dichlorobenzaldehyde (0.174 g, 1 mmol) with 4-methylthiosemicarbazone (0.105 g, 1 mmol) in methanol. The excess methanol was removed by distillation. Colourless block shaped single crystals were obatined by slow evaporation of an ethanol solution of the product in air.

Refinement top

The amino H atoms were located in a difference map and refined with N—H distance restrained to 0.90 (1) Å. The remaining H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C9).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed along the b axis.
2,4-Dichlorobenzaldehyde 4-methylthiosemicarbazone top
Crystal data top
C9H9Cl2N3SF(000) = 1072
Mr = 262.15Dx = 1.502 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2253 reflections
a = 13.444 (3) Åθ = 2.6–27.3°
b = 9.3299 (19) ŵ = 0.71 mm−1
c = 18.499 (4) ÅT = 298 K
β = 92.160 (2)°Block, colourless
V = 2318.7 (8) Å30.18 × 0.17 × 0.13 mm
Z = 8
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2518 independent reflections
Radiation source: fine-focus sealed tube1956 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −16→17
Tmin = 0.883, Tmax = 0.913k = −11→11
7167 measured reflectionsl = −12→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H 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 parametersΔρmax = 0.23 e Å−3
2 restraintsΔρmin = −0.35 e Å−3
Crystal data top
C9H9Cl2N3SV = 2318.7 (8) Å3
Mr = 262.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.444 (3) ŵ = 0.71 mm−1
b = 9.3299 (19) ÅT = 298 K
c = 18.499 (4) Å0.18 × 0.17 × 0.13 mm
β = 92.160 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2518 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1956 reflections with I > 2σ(I)
Tmin = 0.883, Tmax = 0.913Rint = 0.029
7167 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092Δρmax = 0.23 e Å−3
S = 1.05Δρmin = −0.35 e Å−3
2518 reflectionsAbsolute structure: ?
143 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl1−0.06826 (4)0.82058 (6)1.03663 (3)0.05201 (18)
Cl20.14697 (5)0.37973 (7)1.13869 (4)0.0674 (2)
N10.13058 (12)0.83265 (18)0.85768 (9)0.0383 (4)
N20.10483 (12)0.93140 (19)0.80525 (9)0.0410 (4)
N30.24558 (13)0.8704 (2)0.74802 (10)0.0433 (4)
S10.12967 (4)1.06871 (6)0.68333 (3)0.04588 (17)
C10.09166 (13)0.7175 (2)0.96685 (10)0.0317 (4)
C20.03225 (14)0.7064 (2)1.02693 (10)0.0344 (4)
C30.04938 (16)0.6053 (2)1.08024 (11)0.0409 (5)
H3A0.00890.60041.11980.049*
C40.12731 (16)0.5122 (2)1.07367 (11)0.0422 (5)
C50.18905 (16)0.5198 (2)1.01613 (12)0.0452 (5)
H50.24210.45661.01270.054*
C60.17114 (14)0.6221 (2)0.96390 (11)0.0396 (5)
H60.21340.62800.92530.047*
C70.07061 (14)0.8209 (2)0.90939 (10)0.0349 (4)
H70.01390.87790.91030.042*
C80.16428 (14)0.9497 (2)0.74839 (11)0.0360 (5)
C90.32200 (18)0.8847 (3)0.69507 (14)0.0600 (7)
H9A0.29270.87220.64730.090*
H9B0.37230.81310.70390.090*
H9C0.35150.97820.69900.090*
H20.0484 (12)0.982 (2)0.8085 (14)0.080*
H30.258 (2)0.810 (2)0.7848 (10)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0503 (3)0.0534 (3)0.0537 (4)0.0147 (3)0.0206 (3)0.0003 (3)
Cl20.0850 (5)0.0555 (4)0.0599 (4)−0.0016 (3)−0.0195 (3)0.0188 (3)
N10.0368 (9)0.0442 (9)0.0341 (9)0.0010 (7)0.0054 (7)0.0026 (8)
N20.0372 (10)0.0511 (10)0.0355 (10)0.0040 (8)0.0097 (8)0.0096 (8)
N30.0419 (10)0.0483 (10)0.0407 (11)0.0016 (8)0.0141 (8)0.0049 (8)
S10.0463 (3)0.0495 (3)0.0421 (3)−0.0076 (3)0.0037 (2)0.0102 (2)
C10.0299 (10)0.0328 (10)0.0325 (10)−0.0020 (8)0.0020 (8)−0.0036 (8)
C20.0329 (10)0.0361 (10)0.0346 (11)0.0016 (8)0.0043 (8)−0.0048 (8)
C30.0474 (12)0.0436 (12)0.0319 (11)−0.0050 (10)0.0047 (9)−0.0011 (9)
C40.0453 (13)0.0393 (11)0.0412 (12)−0.0031 (10)−0.0107 (10)0.0048 (9)
C50.0357 (12)0.0435 (12)0.0560 (14)0.0076 (9)−0.0039 (10)−0.0027 (11)
C60.0335 (11)0.0433 (11)0.0422 (12)0.0017 (9)0.0051 (9)−0.0029 (9)
C70.0325 (11)0.0382 (10)0.0343 (11)0.0002 (8)0.0067 (8)−0.0038 (9)
C80.0357 (11)0.0378 (11)0.0348 (11)−0.0091 (9)0.0032 (8)−0.0022 (8)
C90.0550 (15)0.0684 (16)0.0587 (16)0.0019 (13)0.0281 (12)0.0064 (13)
Geometric parameters (Å, °) top
Cl1—C21.735 (2)C1—C71.455 (3)
Cl2—C41.738 (2)C2—C31.378 (3)
N1—C71.279 (2)C3—C41.370 (3)
N1—N21.373 (2)C3—H3A0.9300
N2—C81.356 (2)C4—C51.376 (3)
N2—H20.898 (10)C5—C61.373 (3)
N3—C81.320 (3)C5—H50.9300
N3—C91.452 (3)C6—H60.9300
N3—H30.893 (10)C7—H70.9300
S1—C81.690 (2)C9—H9A0.9600
C1—C61.393 (3)C9—H9B0.9600
C1—C21.397 (3)C9—H9C0.9600
C7—N1—N2115.91 (17)C6—C5—C4119.05 (19)
C8—N2—N1119.51 (17)C6—C5—H5120.5
C8—N2—H2120.7 (17)C4—C5—H5120.5
N1—N2—H2119.8 (17)C5—C6—C1122.07 (19)
C8—N3—C9123.97 (19)C5—C6—H6119.0
C8—N3—H3118.4 (18)C1—C6—H6119.0
C9—N3—H3117.3 (18)N1—C7—C1119.52 (18)
C6—C1—C2116.50 (18)N1—C7—H7120.2
C6—C1—C7121.54 (17)C1—C7—H7120.2
C2—C1—C7121.95 (17)N3—C8—N2116.47 (18)
C3—C2—C1122.36 (18)N3—C8—S1124.78 (15)
C3—C2—Cl1117.13 (15)N2—C8—S1118.75 (15)
C1—C2—Cl1120.50 (15)N3—C9—H9A109.5
C4—C3—C2118.59 (19)N3—C9—H9B109.5
C4—C3—H3A120.7H9A—C9—H9B109.5
C2—C3—H3A120.7N3—C9—H9C109.5
C3—C4—C5121.40 (19)H9A—C9—H9C109.5
C3—C4—Cl2119.12 (17)H9B—C9—H9C109.5
C5—C4—Cl2119.47 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.90 (1)2.54 (1)3.4169 (18)167 (2)
N3—H3···S1ii0.89 (1)2.77 (2)3.491 (2)139 (2)
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.90 (1)2.54 (1)3.4169 (18)167 (2)
N3—H3···S1ii0.89 (1)2.77 (2)3.491 (2)139 (2)
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.
Acknowledgements top

No acknowledgements are required.

references
References top

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