(E)-1-(4-Chloro­benzyl­idene)thio­semi­carbazide

Saeed, A.; Mahmood, S.; Bolte, M.; Rauf, A.; Subhan, M.

doi:10.1107/S1600536811004120

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o649

doi:10.1107/S1600536811004120

Open

access

(E)-1-(4-Chlorobenzylidene)thiosemicarbazide

Aamer Saeed,^a ^* Shams-ul Mahmood,^a Michael Bolte,^b Abdul Rauf ^c and Mohammad Subhan ^d

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, ^cDepartment of Chemistry, Islamia Islamia College University, Peshawar, Pakistan, and ^dDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 20 January 2011; accepted 2 February 2011; online 19 February 2011)

In the crystal of the title compound, C₈H₈ClN₃S, molecules are connected by N—H⋯S hydrogen bonds into strips parallel to the (112) planes and running along [1 $[\overline{1}]$ 0]. One of the amino H atoms is not involved in a classical hydrogen bond. In addition, there is a rather short intermolecular Cl⋯S distance of 3.3814 (5) Å.

Related literature

For background to Schiff bases, see: Mobinikhaledi et al. (2010 ); Hamaker et al. (2010 ); Mirkhani et al. (2010 ); Thangadurai et al. (2002 ). Ji & Lu (2010a ,b ); Lü et al. (2008 ). For a related structure, see: Zhang & Li (2008 ). For bioactivity, see: Chohan et al. (2004 ).

Experimental

Crystal data

C₈H₈ClN₃S
M_r = 213.68
Triclinic, $[P \overline 1]$
a = 5.7611 (5) Å
b = 7.8329 (7) Å
c = 11.2016 (10) Å
α = 83.852 (7)°
β = 75.373 (7)°
γ = 76.353 (7)°
V = 474.69 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 173 K
0.38 × 0.35 × 0.27 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995 ) T_min = 0.811, T_max = 0.860
8657 measured reflections
2179 independent reflections
2054 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.079
S = 1.10
2179 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.863 (19)	2.628 (19)	3.4288 (12)	154.7 (16)
N3—H3A⋯S1ⁱⁱ	0.877 (19)	2.65 (2)	3.5119 (12)	170.1 (17)
Symmetry codes: (i) -x+3, -y+1, -z; (ii) -x+4, -y, -z.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004120/bg2386sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004120/bg2386Isup2.hkl

checkCIF report

Comment top

Schiff bases derived from semicarbazide and aromatic aldehydes are an important class of organic compounds because of their applications in many fields including inorganic, biological, and analytical chemistry (Mobinikhaledi et al., 2010; Thangadurai et al., 2002). Schiff bases are known to be versatile ligands in coordination chemistry (Ji & Lu, 2010a,2010b; Hamaker et al., 2010; Mirkhani et al., 2010). Shiff bases and their complexes are also important in material science applications like organic light emitting diodes (Lü et al., 2008).

The title compound features an essentially planar molecule: the largest deviation of a torsion angle from 0 or 180Å is 13.02 (19)° for N1—C1—C11—C12. Bond lengths and angles do not show any unusual values. In the crystal, the molecules are connected by N—H···S hydrogen bonds into strips parallel to the (1 1 2) planes and running along [1 1 0]. One of the amino H atoms is not involved in a classical hydrogen bond. In addition there is a rather short intermolecular Cl···Sⁱ distance of 3.3814 (5)Å (symmetry operator (i): x - 2, y, z + 1).

Related literature top

For background to Schiff bases, see: Mobinikhaledi et al. (2010); Hamaker et al. (2010); Mirkhani et al. (2010); Thangadurai et al. (2002). Ji & Lu (2010a,b); Lü et al. (2008). For a related structure, see: Zhang & Li (2008). For please specify, see: Chohan et al. (2004).

Experimental top

Semicarbazide, 0.137 g (1 mmol) dissolved in 5 ml e thanol was added dropwise to a solution of 4-chlorobenzaldehyde, 0.122 g (1.1 mmol) in 10 ml e thanol at room temperature with continuous stirring. The reaction mixture was refluxed for 4 h and completion monitored by TLC. The reaction mixture was concentrated and the resulting product was separated. Colourless single crystals of the compound, suitable for X-ray crystallography, were grown by slow evaporation from a (2:1) ethyl acetate-ethanol solution. Anal.: calcd. for C₈H₈N₃SCl: C, 44.95; H, 3.74; N, 19.66; S, 14.98%; found: C, 45.01; H, 3.61; N, 19.81; S, 14.83%.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing with intermolecular hydrogen bonds indicated as dashed lines.

(E)-1-(4-Chlorobenzylidene)thiosemicarbazide top

Crystal data top

C₈H₈ClN₃S	Z = 2
M_r = 213.68	F(000) = 220
Triclinic, P1	D_x = 1.495 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7611 (5) Å	Cell parameters from 7492 reflections
b = 7.8329 (7) Å	θ = 3.4–27.8°
c = 11.2016 (10) Å	µ = 0.58 mm⁻¹
α = 83.852 (7)°	T = 173 K
β = 75.373 (7)°	Block, colourless
γ = 76.353 (7)°	0.38 × 0.35 × 0.27 mm
V = 474.69 (7) Å³

Data collection top

Stoe IPDS II two-circle diffractometer	2179 independent reflections
Radiation source: fine-focus sealed tube	2054 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scans	θ_max = 27.7°, θ_min = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −7→7
T_min = 0.811, T_max = 0.860	k = −10→10
8657 measured reflections	l = −14→14

Refinement top

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0425P)² + 0.1107P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2179 reflections	Δρ_max = 0.39 e Å⁻³
131 parameters	Δρ_min = −0.27 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: 0.061 (7)

Crystal data top

C₈H₈ClN₃S	γ = 76.353 (7)°
M_r = 213.68	V = 474.69 (7) Å³
Triclinic, P1	Z = 2
a = 5.7611 (5) Å	Mo Kα radiation
b = 7.8329 (7) Å	µ = 0.58 mm⁻¹
c = 11.2016 (10) Å	T = 173 K
α = 83.852 (7)°	0.38 × 0.35 × 0.27 mm
β = 75.373 (7)°

Data collection top

Stoe IPDS II two-circle diffractometer	2179 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	2054 reflections with I > 2σ(I)
T_min = 0.811, T_max = 0.860	R_int = 0.055
8657 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.39 e Å⁻³
2179 reflections	Δρ_min = −0.27 e Å⁻³
131 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	0.16691 (5)	0.24404 (4)	0.64870 (3)	0.02702 (12)
S1	1.79101 (5)	0.26359 (4)	−0.06509 (3)	0.02625 (12)
N1	1.18834 (19)	0.23473 (14)	0.18778 (10)	0.0215 (2)
N2	1.35359 (19)	0.28547 (14)	0.08531 (10)	0.0220 (2)
H2	1.322 (3)	0.392 (3)	0.0550 (17)	0.033 (4)*
N3	1.6366 (2)	0.03361 (14)	0.11273 (11)	0.0256 (2)
H3A	1.787 (3)	−0.030 (3)	0.0942 (17)	0.037 (5)*
H3B	1.529 (4)	0.002 (2)	0.1674 (19)	0.037 (5)*
C1	0.9739 (2)	0.33723 (16)	0.20735 (11)	0.0206 (2)
H1	0.9408	0.4333	0.1503	0.025*
C2	1.5844 (2)	0.18669 (15)	0.05230 (11)	0.0200 (2)
C11	0.7791 (2)	0.30948 (15)	0.31550 (11)	0.0194 (2)
C12	0.8261 (2)	0.19449 (17)	0.41513 (12)	0.0258 (3)
H12	0.9887	0.1297	0.4129	0.031*
C13	0.6388 (2)	0.17389 (17)	0.51702 (12)	0.0275 (3)
H13	0.6721	0.0962	0.5847	0.033*
C14	0.4012 (2)	0.26838 (16)	0.51905 (11)	0.0209 (2)
C15	0.3492 (2)	0.38356 (16)	0.42174 (11)	0.0221 (2)
H15	0.1859	0.4470	0.4241	0.027*
C16	0.5394 (2)	0.40491 (16)	0.32075 (11)	0.0216 (2)
H16	0.5060	0.4855	0.2544	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02137 (17)	0.02970 (19)	0.02380 (18)	−0.00376 (12)	0.00323 (12)	0.00098 (12)
S1	0.01985 (17)	0.02394 (18)	0.02535 (18)	0.00043 (12)	0.00505 (12)	0.00406 (12)
N1	0.0187 (5)	0.0228 (5)	0.0206 (5)	−0.0050 (4)	0.0009 (4)	−0.0024 (4)
N2	0.0171 (5)	0.0214 (5)	0.0217 (5)	−0.0008 (4)	0.0018 (4)	0.0005 (4)
N3	0.0193 (5)	0.0236 (5)	0.0260 (5)	0.0001 (4)	0.0024 (4)	0.0035 (4)
C1	0.0185 (5)	0.0218 (5)	0.0206 (5)	−0.0041 (4)	−0.0026 (4)	−0.0023 (4)
C2	0.0192 (5)	0.0212 (5)	0.0177 (5)	−0.0023 (4)	−0.0021 (4)	−0.0023 (4)
C11	0.0165 (5)	0.0190 (5)	0.0215 (6)	−0.0035 (4)	−0.0016 (4)	−0.0040 (4)
C12	0.0167 (5)	0.0248 (6)	0.0298 (6)	0.0024 (4)	−0.0023 (5)	0.0017 (5)
C13	0.0223 (6)	0.0259 (6)	0.0278 (6)	0.0011 (5)	−0.0031 (5)	0.0064 (5)
C14	0.0173 (5)	0.0216 (5)	0.0209 (5)	−0.0031 (4)	0.0003 (4)	−0.0032 (4)
C15	0.0148 (5)	0.0260 (6)	0.0233 (6)	−0.0005 (4)	−0.0034 (4)	−0.0027 (5)
C16	0.0183 (5)	0.0248 (6)	0.0201 (5)	−0.0016 (4)	−0.0047 (4)	−0.0010 (4)

Geometric parameters (Å, º) top

Cl1—C14	1.7435 (12)	C11—C16	1.3967 (16)
S1—C2	1.6992 (12)	C11—C12	1.3972 (18)
N1—C1	1.2853 (16)	C12—C13	1.3835 (18)
N1—N2	1.3824 (14)	C12—H12	0.9500
N2—C2	1.3530 (15)	C13—C14	1.3898 (17)
N2—H2	0.863 (19)	C13—H13	0.9500
N3—C2	1.3211 (16)	C14—C15	1.3851 (17)
N3—H3A	0.877 (19)	C15—C16	1.3886 (17)
N3—H3B	0.82 (2)	C15—H15	0.9500
C1—C11	1.4648 (16)	C16—H16	0.9500
C1—H1	0.9500

C1—N1—N2	114.01 (10)	C13—C12—C11	120.82 (11)
C2—N2—N1	120.12 (10)	C13—C12—H12	119.6
C2—N2—H2	119.3 (12)	C11—C12—H12	119.6
N1—N2—H2	118.7 (12)	C12—C13—C14	119.15 (12)
C2—N3—H3A	118.9 (13)	C12—C13—H13	120.4
C2—N3—H3B	119.0 (13)	C14—C13—H13	120.4
H3A—N3—H3B	122.1 (18)	C15—C14—C13	121.30 (11)
N1—C1—C11	121.62 (11)	C15—C14—Cl1	119.81 (9)
N1—C1—H1	119.2	C13—C14—Cl1	118.88 (10)
C11—C1—H1	119.2	C14—C15—C16	119.00 (11)
N3—C2—N2	117.92 (11)	C14—C15—H15	120.5
N3—C2—S1	123.29 (9)	C16—C15—H15	120.5
N2—C2—S1	118.78 (9)	C15—C16—C11	120.85 (11)
C16—C11—C12	118.86 (11)	C15—C16—H16	119.6
C16—C11—C1	118.86 (11)	C11—C16—H16	119.6
C12—C11—C1	122.26 (10)

C1—N1—N2—C2	−178.33 (11)	C11—C12—C13—C14	0.5 (2)
N2—N1—C1—C11	−176.64 (10)	C12—C13—C14—C15	−0.6 (2)
N1—N2—C2—N3	6.86 (18)	C12—C13—C14—Cl1	−179.11 (10)
N1—N2—C2—S1	−173.83 (8)	C13—C14—C15—C16	−0.29 (19)
N1—C1—C11—C16	−168.81 (11)	Cl1—C14—C15—C16	178.22 (9)
N1—C1—C11—C12	13.02 (19)	C14—C15—C16—C11	1.31 (18)
C16—C11—C12—C13	0.53 (19)	C12—C11—C16—C15	−1.43 (18)
C1—C11—C12—C13	178.70 (12)	C1—C11—C16—C15	−179.66 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.863 (19)	2.628 (19)	3.4288 (12)	154.7 (16)
N3—H3A···S1ⁱⁱ	0.877 (19)	2.65 (2)	3.5119 (12)	170.1 (17)

Symmetry codes: (i) −x+3, −y+1, −z; (ii) −x+4, −y, −z.

Experimental details

Crystal data
Chemical formula	C₈H₈ClN₃S
M_r	213.68
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	5.7611 (5), 7.8329 (7), 11.2016 (10)
α, β, γ (°)	83.852 (7), 75.373 (7), 76.353 (7)
V (Å³)	474.69 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.38 × 0.35 × 0.27

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.811, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	8657, 2179, 2054
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.079, 1.10
No. of reflections	2179
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.27

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.863 (19)	2.628 (19)	3.4288 (12)	154.7 (16)
N3—H3A···S1ⁱⁱ	0.877 (19)	2.65 (2)	3.5119 (12)	170.1 (17)

Symmetry codes: (i) −x+3, −y+1, −z; (ii) −x+4, −y, −z.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Chohan, Z. H., Pervez, H., Rauf, A., Khan, K. M., Maharvi, G. M. & Supuran, C. T. (2004). J. Enzyme Inhib. Med. Chem. 19, 161–168. Web of Science CrossRef PubMed CAS Google Scholar
Hamaker, C. G., Maryashina, O. S., Daley, D. K. & Wadler, A. L. (2010). J. Chem. Crystallogr. 40, 34–39. Web of Science CSD CrossRef CAS Google Scholar
Ji, X.-H. & Lu, J.-F. (2010a). Acta Cryst. E66, m881. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ji, X.-H. & Lu, J.-F. (2010b). Acta Cryst. E66, m883–m884. Web of Science CrossRef IUCr Journals Google Scholar
Lü, X., Wong, W.-Y. & Wong, W.-K. (2008). Eur. J. Inorg. Chem. pp. 523–528. Google Scholar
Mirkhani, V., Kia, R., Milic, D., Vartooni, A. R. & Matkovic-Calogovic, D. (2010). Transition Met. Chem. 35, 81–87. Web of Science CSD CrossRef CAS Google Scholar
Mobinikhaledi, A., Forughifar, N. & Kalhor, M. (2010). Turk. J. Chem. 34, 367–373. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Thangadurai, T. D., Gowri, M. & Natarajan, K. (2002). Synth. Reac. Inorg. Met. Org. Chem. 32, 329–343. Web of Science CrossRef CAS Google Scholar
Zhang, X. & Li, Z. (2008). Acta Cryst. E64, o1159. Web of Science CSD CrossRef IUCr Journals 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 3| March 2011| Page o649

doi:10.1107/S1600536811004120

Open

access