2-Chloro-5-nitro­benzaldehyde thio­semicarbazone

Hao, Y.-M.

doi:10.1107/S1600536810035701

organic compounds

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Volume 66| Part 10| October 2010| Page o2528

doi:10.1107/S1600536810035701

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2-Chloro-5-nitrobenzaldehyde thiosemicarbazone

Yu-Mei Hao ^a ^*

^aDepartment of Chemistry, Baicheng Normal University, Baicheng 137000, People's Republic of China
^*Correspondence e-mail: jyxygzb@163.com

(Received 5 September 2010; accepted 6 September 2010; online 11 September 2010)

The title Schiff base compound, C₈H₇ClN₄O₂S, was prepared by the reaction of equimolar quantities of 2-chloro-5-nitrobenzaldehyde with thiosemicarbazide in methanol. The molecule adopts a trans configuration with respect to the azomethine group and the dihedral angle between the benzene ring and the thiosemicarbazide group is 6.8 (3)°. In the crystal, molecules are linked through intermolecular N—H⋯S hydrogen bonds, forming chains propagating in [010].

Related literature

For the crystal structures of similar Schiff base compounds, see: Ferrari et al. (1999 ); Shanmuga Sundara Raj et al. (2000 ); Chattopadhyay et al. (1988 ). For a similar compound reported by the author, see: Hao (2010 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₇ClN₄O₂S
M_r = 258.69
Monoclinic, P 2₁ /c
a = 11.611 (2) Å
b = 8.439 (2) Å
c = 12.016 (3) Å
β = 113.909 (2)°
V = 1076.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 298 K
0.18 × 0.17 × 0.17 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.909, T_max = 0.914
6657 measured reflections
2344 independent reflections
1573 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.111
S = 1.02
2344 reflections
154 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯S1ⁱ	0.89 (1)	2.53 (1)	3.408 (2)	173 (2)
N3—H3⋯S1ⁱⁱ	0.90 (1)	2.46 (1)	3.3266 (19)	161 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035701/hb5633sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035701/hb5633Isup2.hkl

checkCIF report

Comment top

Recently, the crystal structures of a number of Schiff base compounds bearing the hydrazone groups derived from the thiosemicarbazide with aldehydes have been reported (Ferrari et al., 1999; Shanmuga Sundara Raj et al., 2000; Chattopadhyay et al., 1988). Recently, the author has reported a Schiff base compound derived from the thiosemicarbazide with 2-hydroxy-4-methoxybenzaldehyde (Hao, 2010), in this paper, the title new Schiff base compound, (I), Fig. 1, is reported.

The molecule of the title compound adopts a trans configuration with respect to the azomethine group. All the bond lengths are within normal values (Allen et al., 1987). The dihedral angle between the C1-C6 benzene ring and the plane defined by N2-N3-C8-S1-N4 is 6.8 (3)°, indicating the planar of the molecule. In the crystal structure, molecules are linked through intermolecular N—H···S hydrogen bonds (Table 1), to form chains (Fig. 2).

Related literature top

For the crystal structures of similar Schiff base compounds, see: Ferrari et al. (1999); Shanmuga Sundara Raj et al. (2000); Chattopadhyay et al. (1988). For a similar compound reported by the author, see: Hao (2010). For reference structural data, see: Allen et al. (1987).

Experimental top

2-Chloro-5-nitrobenzaldehyde (0.1 mmol, 18.6 mg) and thiosemicarbazide (0.1 mmol, 9.1 mg) were refluxed in methanol (30 ml) for 30 min to give a clear yellow solution. Yellow blocks of (I) were formed by slow evaporation of the solvent over several days at room temperature.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability ellipsoids.
	Fig. 2. Crystal packing of the title compound with hydrogen bonds drawn as dashed lines.

2-Chloro-5-nitrobenzaldehyde thiosemicarbazone top

Crystal data top

C₈H₇ClN₄O₂S	F(000) = 528
M_r = 258.69	D_x = 1.596 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1613 reflections
a = 11.611 (2) Å	θ = 2.8–24.7°
b = 8.439 (2) Å	µ = 0.54 mm⁻¹
c = 12.016 (3) Å	T = 298 K
β = 113.909 (2)°	Block, yellow
V = 1076.4 (4) Å³	0.18 × 0.17 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2344 independent reflections
Radiation source: fine-focus sealed tube	1573 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 27.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.909, T_max = 0.914	k = −7→10
6657 measured reflections	l = −14→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.052P)² + 0.1148P] where P = (F_o² + 2F_c²)/3
2344 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.20 e Å⁻³
4 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₈H₇ClN₄O₂S	V = 1076.4 (4) Å³
M_r = 258.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.611 (2) Å	µ = 0.54 mm⁻¹
b = 8.439 (2) Å	T = 298 K
c = 12.016 (3) Å	0.18 × 0.17 × 0.17 mm
β = 113.909 (2)°

Data collection top

Bruker SMART CCD diffractometer	2344 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1573 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.914	R_int = 0.038
6657 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	4 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.20 e Å⁻³
2344 reflections	Δρ_min = −0.17 e Å⁻³
154 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.22502 (8)	−0.41154 (8)	0.48549 (7)	0.0669 (3)
N1	0.11203 (19)	0.1863 (3)	0.67884 (19)	0.0541 (6)
N2	0.33718 (17)	0.0503 (2)	0.40689 (17)	0.0402 (5)
N3	0.39548 (18)	0.0489 (2)	0.32765 (18)	0.0409 (5)
N4	0.4229 (2)	0.3150 (2)	0.3570 (2)	0.0543 (6)
O1	0.13241 (19)	0.3120 (2)	0.64124 (19)	0.0694 (6)
O2	0.0674 (2)	0.1755 (3)	0.7540 (2)	0.0965 (8)
S1	0.50185 (6)	0.18861 (7)	0.19837 (6)	0.0460 (2)
C1	0.2313 (2)	−0.0903 (3)	0.50752 (19)	0.0375 (5)
C2	0.1926 (2)	−0.2336 (3)	0.5392 (2)	0.0424 (6)
C3	0.1273 (2)	−0.2416 (3)	0.6133 (2)	0.0504 (6)
H3A	0.1013	−0.3389	0.6314	0.061*
C4	0.1014 (2)	−0.1031 (3)	0.6600 (2)	0.0506 (6)
H4	0.0584	−0.1054	0.7107	0.061*
C5	0.1405 (2)	0.0385 (3)	0.6300 (2)	0.0422 (6)
C6	0.2036 (2)	0.0480 (3)	0.5549 (2)	0.0406 (5)
H6	0.2275	0.1460	0.5360	0.049*
C7	0.2974 (2)	−0.0829 (3)	0.4273 (2)	0.0407 (5)
H7	0.3105	−0.1747	0.3912	0.049*
C8	0.4371 (2)	0.1867 (2)	0.3007 (2)	0.0382 (5)
H3	0.412 (2)	−0.0446 (19)	0.301 (2)	0.080*
H4B	0.394 (3)	0.312 (3)	0.4146 (19)	0.080*
H4A	0.450 (2)	0.4093 (18)	0.346 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1005 (6)	0.0371 (4)	0.0800 (5)	−0.0034 (3)	0.0541 (4)	0.0020 (3)
N1	0.0526 (13)	0.0621 (15)	0.0564 (14)	0.0075 (11)	0.0311 (11)	−0.0029 (11)
N2	0.0496 (11)	0.0372 (11)	0.0447 (12)	0.0008 (9)	0.0303 (9)	0.0032 (9)
N3	0.0569 (12)	0.0283 (10)	0.0533 (13)	0.0023 (9)	0.0385 (10)	0.0013 (9)
N4	0.0835 (16)	0.0338 (11)	0.0712 (15)	−0.0090 (11)	0.0578 (13)	−0.0081 (11)
O1	0.0868 (14)	0.0503 (12)	0.0874 (15)	0.0001 (10)	0.0521 (12)	−0.0058 (11)
O2	0.143 (2)	0.0869 (16)	0.1135 (18)	0.0285 (15)	0.1077 (17)	0.0100 (14)
S1	0.0628 (4)	0.0345 (3)	0.0580 (4)	−0.0034 (3)	0.0423 (3)	0.0004 (3)
C1	0.0400 (12)	0.0374 (13)	0.0381 (13)	−0.0023 (10)	0.0190 (11)	0.0026 (10)
C2	0.0497 (14)	0.0366 (12)	0.0432 (14)	−0.0023 (10)	0.0213 (11)	0.0017 (10)
C3	0.0563 (15)	0.0509 (15)	0.0503 (15)	−0.0118 (12)	0.0281 (13)	0.0073 (12)
C4	0.0515 (15)	0.0632 (17)	0.0483 (15)	−0.0046 (13)	0.0317 (12)	0.0042 (13)
C5	0.0416 (13)	0.0480 (14)	0.0413 (14)	0.0005 (11)	0.0214 (11)	−0.0010 (11)
C6	0.0431 (13)	0.0384 (13)	0.0457 (14)	−0.0031 (10)	0.0236 (11)	0.0037 (10)
C7	0.0496 (14)	0.0333 (12)	0.0486 (14)	0.0012 (10)	0.0294 (12)	−0.0009 (11)
C8	0.0435 (13)	0.0310 (12)	0.0460 (14)	−0.0001 (10)	0.0243 (11)	0.0023 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.735 (2)	C1—C6	1.393 (3)
N1—O2	1.214 (3)	C1—C2	1.396 (3)
N1—O1	1.214 (3)	C1—C7	1.456 (3)
N1—C5	1.471 (3)	C2—C3	1.386 (3)
N2—C7	1.277 (3)	C3—C4	1.382 (4)
N2—N3	1.374 (2)	C3—H3A	0.9300
N3—C8	1.348 (3)	C4—C5	1.378 (3)
N3—H3	0.899 (10)	C4—H4	0.9300
N4—C8	1.322 (3)	C5—C6	1.376 (3)
N4—H4B	0.88 (3)	C6—H6	0.9300
N4—H4A	0.886 (10)	C7—H7	0.9300
S1—C8	1.681 (2)

O2—N1—O1	123.3 (2)	C4—C3—H3A	120.5
O2—N1—C5	117.8 (2)	C2—C3—H3A	120.5
O1—N1—C5	118.9 (2)	C5—C4—C3	118.6 (2)
C7—N2—N3	116.36 (19)	C5—C4—H4	120.7
C8—N3—N2	118.95 (18)	C3—C4—H4	120.7
C8—N3—H3	121.7 (18)	C6—C5—C4	122.8 (2)
N2—N3—H3	119.1 (18)	C6—C5—N1	118.5 (2)
C8—N4—H4B	122.8 (17)	C4—C5—N1	118.6 (2)
C8—N4—H4A	122.1 (17)	C5—C6—C1	119.5 (2)
H4B—N4—H4A	115 (2)	C5—C6—H6	120.3
C6—C1—C2	117.5 (2)	C1—C6—H6	120.3
C6—C1—C7	120.4 (2)	N2—C7—C1	119.6 (2)
C2—C1—C7	122.1 (2)	N2—C7—H7	120.2
C3—C2—C1	122.6 (2)	C1—C7—H7	120.2
C3—C2—Cl1	117.04 (19)	N4—C8—N3	116.9 (2)
C1—C2—Cl1	120.40 (18)	N4—C8—S1	123.49 (17)
C4—C3—C2	119.1 (2)	N3—C8—S1	119.59 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···S1ⁱ	0.89 (1)	2.53 (1)	3.408 (2)	173 (2)
N3—H3···S1ⁱⁱ	0.90 (1)	2.46 (1)	3.3266 (19)	161 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₇ClN₄O₂S
M_r	258.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.611 (2), 8.439 (2), 12.016 (3)
β (°)	113.909 (2)
V (Å³)	1076.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.18 × 0.17 × 0.17

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.909, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	6657, 2344, 1573
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 1.02
No. of reflections	2344
No. of parameters	154
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
N4—H4A···S1ⁱ	0.886 (10)	2.527 (11)	3.408 (2)	173 (2)
N3—H3···S1ⁱⁱ	0.899 (10)	2.463 (13)	3.3266 (19)	161 (2)

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

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. CrossRef Web of Science Google Scholar
Bruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chattopadhyay, D., Mazumdar, S. K., Banerjee, T., Ghosh, S. & Mak, T. C. W. (1988). Acta Cryst. C44, 1025–1028. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ferrari, M. B., Capacchi, S., Pelosi, G., Reffo, G., Tarasconi, P., Albertini, R., Pinelli, S. & Lunghi, P. (1999). Inorg. Chim. Acta, 286, 134–141. Google Scholar
Hao, Y.-M. (2010). Acta Cryst. E66, o2211. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shanmuga Sundara Raj, S., Fun, H.-K., Zhang, X.-J., Tian, Y.-P., Xie, F.-X. & Ma, J.-L. (2000). Acta Cryst. C56, 1238–1239. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). 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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2528

doi:10.1107/S1600536810035701

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