4-Ethyl-1-(4-methyl­benzyl­idene)thio­semicarbazide

Li, Y.-F.; Jian, F.-F.

doi:10.1107/S1600536810017988

organic compounds

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Volume 66| Part 6| June 2010| Page o1399

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4-Ethyl-1-(4-methylbenzylidene)thiosemicarbazide

Yu-Feng Li ^a and Fang-Fang Jian ^b ^*

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

(Received 13 May 2010; accepted 15 May 2010; online 22 May 2010)

In the title compound, C₁₁H₁₅N₃S, an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S bonds occur, generating an R₂²(8) loop.

Related literature

For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₁H₁₅N₃S
M_r = 221.32
Monoclinic, P 2₁ /c
a = 8.5777 (17) Å
b = 13.620 (3) Å
c = 10.364 (2) Å
β = 90.00 (3)°
V = 1210.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
11225 measured reflections
2724 independent reflections
1811 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.144
S = 1.10
2724 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 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	2.69	3.505 (2)	158
N3—H3A⋯N1	0.86	2.21	2.605 (2)	108
Symmetry code: (i) -x, -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: https://doi.org/10.1107/S1600536810017988/hb5448sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017988/hb5448Isup2.hkl

checkCIF report

Related literature top

For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-methylbenzaldehyde (0.10 mol), and 4-ethylthiosemicarbazide (0.10 mol) was stirred in refluxing ethanol (10 ml) for 4 h to afford the title compound (0.078 mol, yield 78%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Structure description top

For a related structure, see: Li & Jian (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 (I) showing 30% probability displacement ellipsoids.

4-Ethyl-1-(4-methylbenzylidene)thiosemicarbazide top

Crystal data top

C₁₁H₁₅N₃S	F(000) = 472
M_r = 221.32	D_x = 1.214 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1811 reflections
a = 8.5777 (17) Å	θ = 3.7–25.4°
b = 13.620 (3) Å	µ = 0.24 mm⁻¹
c = 10.364 (2) Å	T = 293 K
β = 90.00 (3)°	Block, colorless
V = 1210.8 (4) Å³	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1811 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
phi and ω scans	h = −10→11
11225 measured reflections	k = −17→17
2724 independent reflections	l = −13→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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0722P)² + 0.0957P] where P = (F_o² + 2F_c²)/3
2724 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₅N₃S	V = 1210.8 (4) Å³
M_r = 221.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5777 (17) Å	µ = 0.24 mm⁻¹
b = 13.620 (3) Å	T = 293 K
c = 10.364 (2) Å	0.23 × 0.20 × 0.18 mm
β = 90.00 (3)°

Data collection top

Bruker SMART CCD diffractometer	1811 reflections with I > 2σ(I)
11225 measured reflections	R_int = 0.035
2724 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.10	Δρ_max = 0.22 e Å⁻³
2724 reflections	Δρ_min = −0.21 e Å⁻³
136 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 > 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	0.18659 (7)	0.61350 (4)	0.05705 (5)	0.0646 (2)
N2	0.02730 (19)	0.59199 (13)	−0.15745 (14)	0.0517 (4)
H2A	−0.0314	0.5527	−0.1144	0.062*
N1	−0.00273 (18)	0.61045 (12)	−0.28521 (14)	0.0471 (4)
C5	−0.1597 (2)	0.57835 (14)	−0.47004 (17)	0.0454 (4)
C6	−0.0800 (2)	0.64307 (15)	−0.55008 (18)	0.0514 (5)
H6A	0.0041	0.6785	−0.5179	0.062*
C8	−0.2494 (2)	0.60447 (16)	−0.72820 (18)	0.0535 (5)
C4	−0.1162 (2)	0.56386 (15)	−0.33565 (18)	0.0494 (5)
H4A	−0.1724	0.5196	−0.2855	0.059*
C3	0.1500 (2)	0.63616 (15)	−0.09996 (17)	0.0486 (5)
N3	0.2320 (2)	0.69703 (14)	−0.17353 (16)	0.0586 (5)
H3A	0.1966	0.7095	−0.2494	0.070*
C7	−0.1245 (2)	0.65502 (17)	−0.67644 (18)	0.0556 (5)
H7A	−0.0691	0.6983	−0.7285	0.067*
C10	−0.2838 (2)	0.52628 (17)	−0.52182 (19)	0.0582 (5)
H10A	−0.3384	0.4819	−0.4706	0.070*
C9	−0.3270 (2)	0.53994 (18)	−0.6490 (2)	0.0618 (6)
H9A	−0.4107	0.5045	−0.6819	0.074*
C11	−0.2989 (3)	0.6213 (2)	−0.8660 (2)	0.0747 (7)
H11A	−0.3868	0.5803	−0.8857	0.112*
H11B	−0.2142	0.6054	−0.9228	0.112*
H11C	−0.3272	0.6890	−0.8774	0.112*
C2	0.3779 (3)	0.7445 (2)	−0.1356 (2)	0.0759 (7)
H2B	0.3760	0.7574	−0.0436	0.091*
H2C	0.3869	0.8071	−0.1798	0.091*
C1	0.5171 (3)	0.6822 (2)	−0.1673 (3)	0.0875 (9)
H1B	0.6104	0.7152	−0.1403	0.131*
H1C	0.5210	0.6710	−0.2587	0.131*
H1D	0.5089	0.6204	−0.1232	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0854 (4)	0.0693 (4)	0.0392 (3)	−0.0124 (3)	−0.0082 (2)	0.0033 (2)
N2	0.0574 (10)	0.0600 (11)	0.0377 (8)	−0.0058 (8)	−0.0014 (7)	0.0049 (7)
N1	0.0559 (9)	0.0484 (9)	0.0372 (8)	0.0019 (7)	−0.0015 (7)	0.0003 (6)
C5	0.0449 (10)	0.0467 (11)	0.0445 (9)	0.0024 (8)	−0.0011 (7)	−0.0003 (7)
C6	0.0552 (11)	0.0497 (11)	0.0493 (10)	−0.0063 (9)	−0.0042 (8)	0.0026 (8)
C8	0.0596 (12)	0.0557 (12)	0.0451 (10)	0.0138 (10)	−0.0061 (9)	−0.0064 (8)
C4	0.0509 (11)	0.0510 (12)	0.0463 (10)	−0.0008 (9)	0.0016 (8)	0.0047 (8)
C3	0.0561 (11)	0.0490 (11)	0.0406 (9)	0.0019 (9)	−0.0004 (8)	−0.0009 (8)
N3	0.0645 (10)	0.0658 (11)	0.0455 (8)	−0.0144 (9)	−0.0061 (7)	0.0078 (7)
C7	0.0654 (12)	0.0525 (12)	0.0488 (10)	0.0008 (10)	0.0009 (9)	0.0059 (8)
C10	0.0551 (11)	0.0631 (14)	0.0563 (11)	−0.0121 (10)	−0.0008 (9)	0.0036 (9)
C9	0.0572 (12)	0.0670 (15)	0.0611 (12)	−0.0059 (10)	−0.0120 (10)	−0.0078 (10)
C11	0.0885 (16)	0.0861 (19)	0.0494 (12)	0.0190 (14)	−0.0140 (11)	−0.0061 (11)
C2	0.0977 (18)	0.0733 (17)	0.0569 (13)	−0.0359 (15)	−0.0120 (12)	0.0062 (11)
C1	0.0677 (16)	0.095 (2)	0.099 (2)	−0.0246 (15)	−0.0174 (14)	0.0220 (15)

Geometric parameters (Å, º) top

S1—C3	1.6858 (18)	N3—C2	1.462 (3)
N2—C3	1.351 (2)	N3—H3A	0.8600
N2—N1	1.372 (2)	C7—H7A	0.9300
N2—H2A	0.8600	C10—C9	1.381 (3)
N1—C4	1.274 (2)	C10—H10A	0.9300
C5—C10	1.388 (3)	C9—H9A	0.9300
C5—C6	1.390 (3)	C11—H11A	0.9600
C5—C4	1.455 (2)	C11—H11B	0.9600
C6—C7	1.374 (3)	C11—H11C	0.9600
C6—H6A	0.9300	C2—C1	1.502 (4)
C8—C9	1.375 (3)	C2—H2B	0.9700
C8—C7	1.381 (3)	C2—H2C	0.9700
C8—C11	1.508 (3)	C1—H1B	0.9600
C4—H4A	0.9300	C1—H1C	0.9600
C3—N3	1.328 (3)	C1—H1D	0.9600

C3—N2—N1	119.36 (16)	C9—C10—C5	120.4 (2)
C3—N2—H2A	120.3	C9—C10—H10A	119.8
N1—N2—H2A	120.3	C5—C10—H10A	119.8
C4—N1—N2	116.63 (16)	C8—C9—C10	121.75 (19)
C10—C5—C6	118.08 (17)	C8—C9—H9A	119.1
C10—C5—C4	119.85 (18)	C10—C9—H9A	119.1
C6—C5—C4	122.08 (17)	C8—C11—H11A	109.5
C7—C6—C5	120.48 (18)	C8—C11—H11B	109.5
C7—C6—H6A	119.8	H11A—C11—H11B	109.5
C5—C6—H6A	119.8	C8—C11—H11C	109.5
C9—C8—C7	117.52 (18)	H11A—C11—H11C	109.5
C9—C8—C11	121.8 (2)	H11B—C11—H11C	109.5
C7—C8—C11	120.7 (2)	N3—C2—C1	111.8 (2)
N1—C4—C5	121.40 (18)	N3—C2—H2B	109.3
N1—C4—H4A	119.3	C1—C2—H2B	109.3
C5—C4—H4A	119.3	N3—C2—H2C	109.3
N3—C3—N2	115.95 (16)	C1—C2—H2C	109.3
N3—C3—S1	124.73 (15)	H2B—C2—H2C	107.9
N2—C3—S1	119.30 (15)	C2—C1—H1B	109.5
C3—N3—C2	125.12 (17)	C2—C1—H1C	109.5
C3—N3—H3A	117.4	H1B—C1—H1C	109.5
C2—N3—H3A	117.4	C2—C1—H1D	109.5
C6—C7—C8	121.8 (2)	H1B—C1—H1D	109.5
C6—C7—H7A	119.1	H1C—C1—H1D	109.5
C8—C7—H7A	119.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.69	3.505 (2)	158
N3—H3A···N1	0.86	2.21	2.605 (2)	108

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₃S
M_r	221.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.5777 (17), 13.620 (3), 10.364 (2)
β (°)	90, 90.00 (3), 90
V (Å³)	1210.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11225, 2724, 1811
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.144, 1.10
No. of reflections	2724
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21

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	2.69	3.505 (2)	158
N3—H3A···N1	0.86	2.21	2.605 (2)	108

Symmetry code: (i) −x, −y+1, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1397. 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

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 66| Part 6| June 2010| Page o1399

https://doi.org/10.1107/S1600536810017988

Open

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