2,4-Dichloro­benzaldehyde 4-methyl­thio­semicarbazone

Li, R.

doi:10.1107/S1600536810049743

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o20

https://doi.org/10.1107/S1600536810049743

Open

access

2,4-Dichlorobenzaldehyde 4-methylthiosemicarbazone

Rongchun Li ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: rongchunli01@126.com

(Received 28 November 2010; accepted 29 November 2010; online 4 December 2010)

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.

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_r = 262.15
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.092
S = 1.05
2518 reflections
143 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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) $[-x, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810049743/hg2763sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049743/hg2763Isup2.hkl

checkCIF report

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.

Structure description top

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).

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).

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

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis.

2,4-Dichlorobenzaldehyde 4-methylthiosemicarbazone top

Crystal data top

C₉H₉Cl₂N₃S	F(000) = 1072
M_r = 262.15	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0407P)² + 0.9729P] where P = (F_o² + 2F_c²)/3
2518 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.23 e Å⁻³
2 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₉H₉Cl₂N₃S	V = 2318.7 (8) Å³
M_r = 262.15	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.444 (3) Å	µ = 0.71 mm⁻¹
b = 9.3299 (19) Å	T = 298 K
c = 18.499 (4) Å	0.18 × 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)
T_min = 0.883, T_max = 0.913	R_int = 0.029
7167 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.23 e Å⁻³
2518 reflections	Δρ_min = −0.35 e Å⁻³
143 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x, y, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₉H₉Cl₂N₃S
M_r	262.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	13.444 (3), 9.3299 (19), 18.499 (4)
β (°)	92.160 (2)
V (Å³)	2318.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.18 × 0.17 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.883, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	7167, 2518, 1956
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.092, 1.05
No. of reflections	2518
No. of parameters	143
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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
N2—H2···S1ⁱ	0.898 (10)	2.536 (12)	3.4169 (18)	167 (2)
N3—H3···S1ⁱⁱ	0.893 (10)	2.765 (19)	3.491 (2)	139 (2)

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Beraldo, H., Lima, R., Teixeira, L. R., Moura, A. A. & West, D. X. (2001). J. Mol. Struct. 559, 99–106. Web of Science CSD CrossRef CAS Google Scholar
Bernhardt, P. V., Caldwell, L. M., Lovejoy, D. B. & Richardson, D. R. (2003). Acta Cryst. C59, o629–o633. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Castineiras, A., Lobana, T. S., Sanchez, A., Sordo, J. & Garcia-Tasende, M. S. (2001). J. Chem. Crystallogr. 31, 329–332. Web of Science CSD CrossRef CAS Google Scholar
Jouad, E. M., Allain, M., Khan, M. A. & Bouet, G. M. (2002). J. Mol. Struct. 604, 205–209. Web of Science CSD CrossRef CAS Google Scholar
Karakurt, T., Dinçer, M., Yılmaz, I. & Çukurovalı, A. (2003). Acta Cryst. E59, o1997–o1999. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, R. (2010). Acta Cryst. E66, o3324. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sampath, N., Malathy Sony, S. M., Ponnuswamy, M. N. & Nethaji, M. (2003). Acta Cryst. C59, o346–o348. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Selvanayagam, S., Yogavel, M., Rajakannan, V., Velmurugan, D., Shanmuga Sundara Raj, S. & Fun, H.-K. (2002). Acta Cryst. E58, o1336–o1338. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). 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
Swearingen, J. K., Kaminsky, W. & West, D. X. (2002). Transition Met. Chem. 27, 724–731. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o20

https://doi.org/10.1107/S1600536810049743

Open

access