1-Benzyl­idene-4-ethyl­thio­semicarbazide

Li, Y.-F.; Zhang, Y.-C.

doi:10.1107/S1600536810038444

organic compounds

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Volume 66| Part 10| October 2010| Page o2686

doi:10.1107/S1600536810038444

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1-Benzylidene-4-ethylthiosemicarbazide

Yu-Feng Li ^a ^* and Yun-Cheng Zhang ^b

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

(Received 25 September 2010; accepted 26 September 2010; online 30 September 2010)

The title compound, C₁₀H₁₃N₃S, was prepared by the reaction of 4-ethylthiosemicarbazide and benzaldehyde. The dihedral angle between the benzene ring and the thiourea unit is 8.96 (7)° and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops.

Related literature

For background to the coordination chemistry of Schiff bases, see: Habermehl et al. (2006 ). For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₀H₁₃N₃S
M_r = 207.30
Monoclinic, P 2₁ /c
a = 8.4899 (17) Å
b = 13.467 (3) Å
c = 10.015 (2) Å
β = 96.04 (3)°
V = 1138.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
10048 measured reflections
2596 independent reflections
2118 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.152
S = 1.09
2596 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N3	0.86	2.23	2.628 (2)	108
N2—H2A⋯S1ⁱ	0.86	2.74	3.5565 (16)	158
Symmetry code: (i) -x+1, -y+1, -z.

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: 10.1107/S1600536810038444/hb5654sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038444/hb5654Isup2.hkl

checkCIF report

Comment top

Schiff bases are important intermediates which have been reported to be chiral coordination compound with many interesting properties (Habermehl et al., 2006). As part of our research for new Schiff-base compounds we synthesized the title compound (I), and describe its structure here. In the molecule structure, the dihedral angle between the benzene ring and the thiourea unit is 8.96 (7)°.

Bond lengths and angles agree with those observed in a related structure (Li & Jian, 2010).

Related literature top

For background to the coordination chemistry of Schiff bases, see: Habermehl et al. (2006). For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-ethylthiosemicarbazide (0.1 mol) and benzaldehyde (0.1 mol) was stirred in refluxing ethanol (25 mL) for 2 h to afford the title compound (0.079 mol, yield 79%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

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-Benzylidene-4-ethylthiosemicarbazide top

Crystal data top

C₁₀H₁₃N₃S	F(000) = 440
M_r = 207.30	D_x = 1.209 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2596 reflections
a = 8.4899 (17) Å	θ = 3.0–27.5°
b = 13.467 (3) Å	µ = 0.25 mm⁻¹
c = 10.015 (2) Å	T = 293 K
β = 96.04 (3)°	Block, colorless
V = 1138.7 (4) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2118 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
phi and ω scans	h = −10→9
10048 measured reflections	k = −17→17
2596 independent reflections	l = −13→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0834P)² + 0.1728P] where P = (F_o² + 2F_c²)/3
2596 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₀H₁₃N₃S	V = 1138.7 (4) Å³
M_r = 207.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4899 (17) Å	µ = 0.25 mm⁻¹
b = 13.467 (3) Å	T = 293 K
c = 10.015 (2) Å	0.22 × 0.20 × 0.18 mm
β = 96.04 (3)°

Data collection top

Bruker SMART CCD diffractometer	2118 reflections with I > 2σ(I)
10048 measured reflections	R_int = 0.031
2596 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
2596 reflections	Δρ_min = −0.40 e Å⁻³
127 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	0.28967 (7)	0.39580 (4)	−0.07292 (4)	0.0744 (2)
N1	0.25491 (17)	0.29999 (11)	0.15603 (14)	0.0596 (4)
H1A	0.2916	0.2862	0.2372	0.072*
N2	0.46620 (17)	0.40411 (10)	0.15771 (13)	0.0537 (3)
H2A	0.5279	0.4416	0.1171	0.064*
N3	0.50010 (15)	0.38467 (9)	0.29257 (13)	0.0479 (3)
C4	0.61893 (18)	0.43036 (12)	0.35133 (16)	0.0504 (4)
H4A	0.6768	0.4724	0.3014	0.061*
C3	0.3357 (2)	0.36416 (12)	0.08914 (15)	0.0516 (4)
C5	0.66728 (17)	0.41886 (11)	0.49435 (16)	0.0473 (3)
C6	0.5847 (2)	0.35906 (13)	0.57650 (17)	0.0566 (4)
H6A	0.4966	0.3235	0.5399	0.068*
C10	0.7983 (2)	0.47106 (14)	0.55174 (19)	0.0624 (4)
H10A	0.8542	0.5117	0.4983	0.075*
C7	0.6330 (3)	0.35251 (16)	0.71139 (19)	0.0721 (5)
H7A	0.5773	0.3125	0.7658	0.087*
C9	0.8465 (2)	0.46324 (17)	0.6869 (2)	0.0765 (6)
H9A	0.9356	0.4977	0.7238	0.092*
C8	0.7637 (3)	0.40488 (16)	0.7670 (2)	0.0775 (6)
H8A	0.7953	0.4005	0.8586	0.093*
C1	−0.0363 (3)	0.3091 (2)	0.1253 (3)	0.1024 (9)
H1B	−0.1290	0.2740	0.0876	0.154*
H1C	−0.0324	0.3729	0.0832	0.154*
H1D	−0.0405	0.3176	0.2200	0.154*
C2	0.1083 (3)	0.25096 (16)	0.1020 (2)	0.0777 (6)
H2B	0.1027	0.1862	0.1435	0.093*
H2C	0.1102	0.2410	0.0063	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0973 (4)	0.0820 (4)	0.0422 (3)	−0.0240 (3)	−0.0006 (2)	0.00516 (19)
N1	0.0682 (9)	0.0602 (8)	0.0491 (7)	−0.0158 (7)	0.0001 (6)	0.0046 (6)
N2	0.0586 (8)	0.0584 (8)	0.0443 (7)	−0.0070 (6)	0.0066 (6)	0.0044 (5)
N3	0.0514 (7)	0.0472 (7)	0.0451 (7)	0.0009 (5)	0.0046 (5)	0.0014 (5)
C4	0.0470 (8)	0.0513 (8)	0.0534 (8)	−0.0022 (6)	0.0070 (6)	0.0066 (7)
C3	0.0598 (9)	0.0503 (8)	0.0450 (8)	−0.0013 (7)	0.0070 (6)	−0.0036 (6)
C5	0.0444 (7)	0.0436 (7)	0.0533 (8)	0.0039 (6)	0.0026 (6)	0.0001 (6)
C6	0.0599 (9)	0.0524 (8)	0.0572 (9)	−0.0016 (7)	0.0049 (7)	0.0063 (7)
C10	0.0529 (9)	0.0616 (10)	0.0714 (11)	−0.0050 (8)	0.0000 (8)	−0.0015 (8)
C7	0.0932 (14)	0.0654 (11)	0.0584 (10)	0.0106 (10)	0.0110 (9)	0.0107 (9)
C9	0.0693 (12)	0.0740 (12)	0.0806 (13)	0.0041 (10)	−0.0182 (10)	−0.0179 (10)
C8	0.0976 (15)	0.0781 (13)	0.0528 (10)	0.0246 (11)	−0.0108 (10)	−0.0087 (9)
C1	0.0765 (14)	0.0977 (18)	0.126 (2)	−0.0322 (14)	−0.0217 (14)	0.0169 (15)
C2	0.0950 (15)	0.0722 (12)	0.0629 (11)	−0.0365 (11)	−0.0059 (10)	0.0025 (9)

Geometric parameters (Å, º) top

S1—C3	1.6838 (16)	C10—C9	1.376 (3)
N1—C3	1.328 (2)	C10—H10A	0.9300
N1—C2	1.462 (2)	C7—C8	1.382 (3)
N1—H1A	0.8600	C7—H7A	0.9300
N2—C3	1.352 (2)	C9—C8	1.370 (3)
N2—N3	1.3761 (18)	C9—H9A	0.9300
N2—H2A	0.8600	C8—H8A	0.9300
N3—C4	1.272 (2)	C1—C2	1.495 (4)
C4—C5	1.456 (2)	C1—H1B	0.9600
C4—H4A	0.9300	C1—H1C	0.9600
C5—C10	1.389 (2)	C1—H1D	0.9600
C5—C6	1.392 (2)	C2—H2B	0.9700
C6—C7	1.373 (2)	C2—H2C	0.9700
C6—H6A	0.9300

C3—N1—C2	124.92 (15)	C6—C7—C8	120.6 (2)
C3—N1—H1A	117.5	C6—C7—H7A	119.7
C2—N1—H1A	117.5	C8—C7—H7A	119.7
C3—N2—N3	119.89 (13)	C8—C9—C10	120.19 (19)
C3—N2—H2A	120.1	C8—C9—H9A	119.9
N3—N2—H2A	120.1	C10—C9—H9A	119.9
C4—N3—N2	115.84 (13)	C9—C8—C7	119.75 (19)
N3—C4—C5	122.10 (14)	C9—C8—H8A	120.1
N3—C4—H4A	118.9	C7—C8—H8A	120.1
C5—C4—H4A	118.9	C2—C1—H1B	109.5
N1—C3—N2	116.22 (14)	C2—C1—H1C	109.5
N1—C3—S1	124.84 (13)	H1B—C1—H1C	109.5
N2—C3—S1	118.92 (13)	C2—C1—H1D	109.5
C10—C5—C6	118.67 (15)	H1B—C1—H1D	109.5
C10—C5—C4	118.95 (15)	H1C—C1—H1D	109.5
C6—C5—C4	122.37 (14)	N1—C2—C1	112.78 (18)
C7—C6—C5	120.11 (17)	N1—C2—H2B	109.0
C7—C6—H6A	119.9	C1—C2—H2B	109.0
C5—C6—H6A	119.9	N1—C2—H2C	109.0
C9—C10—C5	120.71 (18)	C1—C2—H2C	109.0
C9—C10—H10A	119.6	H2B—C2—H2C	107.8
C5—C10—H10A	119.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.86	2.23	2.628 (2)	108
N2—H2A···S1ⁱ	0.86	2.74	3.5565 (16)	158

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃S
M_r	207.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.4899 (17), 13.467 (3), 10.015 (2)
β (°)	96.04 (3)
V (Å³)	1138.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10048, 2596, 2118
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.152, 1.09
No. of reflections	2596
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.40

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
N1—H1A···N3	0.86	2.23	2.628 (2)	108
N2—H2A···S1ⁱ	0.86	2.74	3.5565 (16)	158

Symmetry code: (i) −x+1, −y+1, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Habermehl, N. C., Angus, P. M. & Kilah, N. L. (2006). Inorg. Chem. 45, 1445–1462. Web of Science CSD CrossRef PubMed CAS Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. 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 10| October 2010| Page o2686

doi:10.1107/S1600536810038444

Open

access