1-(4-Chloro­benzyl­idene)-4-ethyl­thio­semicarbazide

Li, Y.-F.

doi:10.1107/S1600536810047446

organic compounds

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https://doi.org/10.1107/S1600536810047446

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1-(4-Chlorobenzylidene)-4-ethylthiosemicarbazide

Yu-Feng Li ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 11 November 2010; accepted 16 November 2010; online 20 November 2010)

In the title compound, C₁₀H₁₂ClN₃S, the dihedral angle between the benzene ring and the thiourea unit is 2.35 (19)°. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops.

Related literature

For related structures, see: Li & Jian (2010 ); Li & Meng (2010 ).

Experimental

Crystal data

C₁₀H₁₂ClN₃S
M_r = 241.75
Monoclinic, P 2₁ /c
a = 4.6769 (10) Å
b = 26.727 (6) Å
c = 9.791 (3) Å
β = 102.59 (3)°
V = 1194.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
11437 measured reflections
2723 independent reflections
1388 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.272
S = 1.09
2723 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.59	3.383 (4)	154
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536810047446/hb5737sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047446/hb5737Isup2.hkl

checkCIF report

Related literature top

For related structures, see: Li & Jian (2010); Li & Meng (2010).

Experimental top

A mixture of 4-ethylthiosemicarbazide (0.1 mol) and 4-chlorobenzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 2 h to afford the title compound (0.089 mol, yield 89%). Colourless bars were obtained by recrystallization from ethanol at room temperature.

Structure description top

For related structures, see: Li & Jian (2010); Li & Meng (2010).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 structure of the title compound showing 30% probability displacement ellipsoids.

1-(4-Chlorobenzylidene)-4-ethylthiosemicarbazide top

Crystal data top

C₁₀H₁₂ClN₃S	F(000) = 504
M_r = 241.75	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2723 reflections
a = 4.6769 (10) Å	θ = 3.1–27.5°
b = 26.727 (6) Å	µ = 0.47 mm⁻¹
c = 9.791 (3) Å	T = 293 K
β = 102.59 (3)°	Bar, colorless
V = 1194.4 (5) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1388 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.066
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
phi and ω scans	h = −6→5
11437 measured reflections	k = −34→34
2723 independent reflections	l = −12→12

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.272	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.1156P)² + 1.1747P] where P = (F_o² + 2F_c²)/3
2723 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₀H₁₂ClN₃S	V = 1194.4 (5) Å³
M_r = 241.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.6769 (10) Å	µ = 0.47 mm⁻¹
b = 26.727 (6) Å	T = 293 K
c = 9.791 (3) Å	0.22 × 0.20 × 0.18 mm
β = 102.59 (3)°

Data collection top

Bruker SMART CCD diffractometer	1388 reflections with I > 2σ(I)
11437 measured reflections	R_int = 0.066
2723 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.272	H-atom parameters constrained
S = 1.09	Δρ_max = 0.33 e Å⁻³
2723 reflections	Δρ_min = −0.34 e Å⁻³
136 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
S1	1.2104 (3)	−0.01352 (5)	0.72223 (14)	0.0738 (5)
Cl1	−0.3450 (4)	0.27875 (6)	0.46099 (18)	0.1022 (6)
N2	0.7928 (8)	0.04912 (15)	0.6097 (4)	0.0637 (10)
H2A	0.7695	0.0311	0.5354	0.076*
N3	0.6207 (8)	0.09071 (14)	0.6128 (4)	0.0616 (10)
C5	0.2251 (9)	0.14199 (17)	0.4970 (5)	0.0576 (11)
C4	0.4166 (10)	0.09865 (18)	0.5041 (5)	0.0622 (11)
H4A	0.3907	0.0765	0.4291	0.075*
N1	1.0195 (10)	0.06662 (17)	0.8346 (4)	0.0789 (13)
H1A	0.8985	0.0912	0.8260	0.095*
C10	0.0157 (10)	0.15053 (19)	0.3771 (5)	0.0664 (12)
H10A	−0.0066	0.1281	0.3028	0.080*
C6	0.2528 (11)	0.1751 (2)	0.6072 (5)	0.0723 (13)
H6A	0.3933	0.1695	0.6889	0.087*
C9	−0.1627 (11)	0.1925 (2)	0.3665 (5)	0.0709 (13)
H9A	−0.3045	0.1983	0.2853	0.085*
C3	0.9998 (10)	0.03689 (17)	0.7250 (5)	0.0602 (11)
C8	−0.1287 (11)	0.22552 (19)	0.4764 (5)	0.0679 (12)
C7	0.0731 (14)	0.2164 (2)	0.5967 (6)	0.0836 (16)
H7A	0.0898	0.2382	0.6721	0.100*
C2	1.2242 (16)	0.0617 (2)	0.9669 (6)	0.096 (2)
H2B	1.1446	0.0383	1.0247	0.116*
H2C	1.4045	0.0475	0.9506	0.116*
C1	1.290 (2)	0.1061 (3)	1.0404 (9)	0.130 (3)
H1B	1.4287	0.0997	1.1264	0.196*
H1C	1.1142	0.1199	1.0606	0.196*
H1D	1.3723	0.1294	0.9851	0.196*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0781 (9)	0.0700 (8)	0.0700 (8)	0.0180 (6)	0.0089 (6)	0.0022 (6)
Cl1	0.1142 (13)	0.0852 (11)	0.1023 (12)	0.0396 (9)	0.0129 (9)	0.0139 (8)
N2	0.060 (2)	0.069 (2)	0.061 (2)	0.0125 (19)	0.0087 (17)	−0.0022 (18)
N3	0.060 (2)	0.062 (2)	0.063 (2)	0.0073 (19)	0.0145 (18)	0.0012 (17)
C5	0.054 (2)	0.062 (3)	0.055 (2)	−0.002 (2)	0.0104 (19)	0.0026 (19)
C4	0.057 (3)	0.069 (3)	0.059 (3)	0.008 (2)	0.010 (2)	−0.001 (2)
N1	0.087 (3)	0.079 (3)	0.063 (3)	0.025 (2)	0.000 (2)	−0.008 (2)
C10	0.063 (3)	0.070 (3)	0.062 (3)	0.002 (2)	0.006 (2)	−0.001 (2)
C6	0.072 (3)	0.077 (3)	0.060 (3)	0.014 (3)	−0.003 (2)	−0.004 (2)
C9	0.066 (3)	0.077 (3)	0.064 (3)	0.009 (3)	0.001 (2)	0.013 (2)
C3	0.057 (2)	0.063 (3)	0.062 (3)	0.006 (2)	0.013 (2)	0.005 (2)
C8	0.068 (3)	0.067 (3)	0.067 (3)	0.011 (2)	0.011 (2)	0.012 (2)
C7	0.098 (4)	0.079 (4)	0.068 (3)	0.025 (3)	0.005 (3)	−0.011 (3)
C2	0.111 (5)	0.085 (4)	0.077 (4)	0.012 (4)	−0.014 (3)	−0.005 (3)
C1	0.153 (7)	0.094 (5)	0.112 (6)	−0.002 (5)	−0.039 (5)	−0.022 (4)

Geometric parameters (Å, º) top

S1—C3	1.673 (5)	C10—H10A	0.9300
Cl1—C8	1.733 (5)	C6—C7	1.379 (7)
N2—C3	1.357 (6)	C6—H6A	0.9300
N2—N3	1.377 (5)	C9—C8	1.373 (7)
N2—H2A	0.8600	C9—H9A	0.9300
N3—C4	1.283 (6)	C8—C7	1.361 (7)
C5—C10	1.374 (6)	C7—H7A	0.9300
C5—C6	1.379 (7)	C2—C1	1.386 (9)
C5—C4	1.457 (6)	C2—H2B	0.9700
C4—H4A	0.9300	C2—H2C	0.9700
N1—C3	1.322 (6)	C1—H1B	0.9600
N1—C2	1.439 (7)	C1—H1C	0.9600
N1—H1A	0.8600	C1—H1D	0.9600
C10—C9	1.389 (7)

C3—N2—N3	119.4 (4)	N1—C3—N2	116.2 (4)
C3—N2—H2A	120.3	N1—C3—S1	124.1 (4)
N3—N2—H2A	120.3	N2—C3—S1	119.7 (4)
C4—N3—N2	116.6 (4)	C7—C8—C9	120.3 (5)
C10—C5—C6	119.3 (4)	C7—C8—Cl1	120.2 (4)
C10—C5—C4	119.3 (4)	C9—C8—Cl1	119.5 (4)
C6—C5—C4	121.4 (4)	C8—C7—C6	120.2 (5)
N3—C4—C5	120.6 (4)	C8—C7—H7A	119.9
N3—C4—H4A	119.7	C6—C7—H7A	119.9
C5—C4—H4A	119.7	C1—C2—N1	114.7 (6)
C3—N1—C2	126.2 (5)	C1—C2—H2B	108.6
C3—N1—H1A	116.9	N1—C2—H2B	108.6
C2—N1—H1A	116.9	C1—C2—H2C	108.6
C5—C10—C9	120.2 (5)	N1—C2—H2C	108.6
C5—C10—H10A	119.9	H2B—C2—H2C	107.6
C9—C10—H10A	119.9	C2—C1—H1B	109.5
C5—C6—C7	120.3 (5)	C2—C1—H1C	109.5
C5—C6—H6A	119.9	H1B—C1—H1C	109.5
C7—C6—H6A	119.9	C2—C1—H1D	109.5
C8—C9—C10	119.7 (4)	H1B—C1—H1D	109.5
C8—C9—H9A	120.2	H1C—C1—H1D	109.5
C10—C9—H9A	120.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.59	3.383 (4)	154

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂ClN₃S
M_r	241.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.6769 (10), 26.727 (6), 9.791 (3)
β (°)	102.59 (3)
V (Å³)	1194.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11437, 2723, 1388
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.272, 1.09
No. of reflections	2723
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.34

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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—H2A···S1ⁱ	0.86	2.59	3.383 (4)	154

Symmetry code: (i) −x+2, −y, −z+1.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y.-F. & Meng, F.-Y. (2010). Acta Cryst. E66, o2685. Web of Science CSD CrossRef IUCr Journals 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
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3256

https://doi.org/10.1107/S1600536810047446

Open

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