1-(3,4-Dimethyl­benzyl­idene)-4-ethyl­thio­semicarbazide

Li, Y.-F.; Meng, F.-Y.

doi:10.1107/S1600536810038389

organic compounds

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Volume 66| Part 10| October 2010| Page o2685

doi:10.1107/S1600536810038389

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1-(3,4-Dimethylbenzylidene)-4-ethylthiosemicarbazide

Yu-Feng Li ^a ^* and Fan-Yong Meng ^b

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

(Received 20 September 2010; accepted 25 September 2010; online 30 September 2010)

The title compound, C₁₂H₁₇N₃S, was prepared by the reaction of 4-ethylthiosemicarbazide and 3,4-dimethylbenzaldehyde. The dihedral angle between the thiourea unit and the benzene ring is 7.09 (8)°. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds occur.

Related literature

For applications of Schiff base compounds, see: Casas et al. (2000 ); Habermehl et al. (2006 ). For the structure of 4-ethyl-1-(4-methylbenzylidene)thiosemicarbazide, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₂H₁₇N₃S
M_r = 235.35
Monoclinic, P 2₁ /c
a = 8.6659 (17) Å
b = 15.207 (3) Å
c = 9.993 (2) Å
β = 93.47 (3)°
V = 1314.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
12215 measured reflections
3006 independent reflections
2429 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.206
S = 1.05
3006 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.39 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	2.65	3.4929 (18)	168
Symmetry code: (i) -x+2, -y, -z+2.

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/S1600536810038389/lh5136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038389/lh5136Isup2.hkl

checkCIF report

Comment top

Schiff-bases have attracted attention because they can be utilized as effective ligands in coordination chemistry (Casas et al., 2000). They are important intermediates which have been reported to form chiral coordination compounds with many interesting properties (Habermehl et al., 2006). As part of our research on new Schiff-base compounds we synthesized the title compound (I), and have determined its crystal structure. The molecular structure is shown in Fig. 1. The dihedral angle between the benzene ring and the thiourea unit is 7.09 (8)°. The bond lengths and angles agree with those observed in 4-Ethyl-1-(4-methylbenzylidene)thiosemicarbazide (Li & Jian, 2010). In the crystal structure, centrosymmetric dimers are formed by pairs of intermolecular N—H···S hydrogen bonds.

Related literature top

For applications of Schiff base compounds, see: Casas et al. (2000); Habermehl et al. (2006). For the structure of 4-ethyl-1-(4-methylbenzylidene)thiosemicarbazide, see: Li & Jian (2010).

Experimental top

A mixture of the 4-ethylthiosemicarbazide (0.1 mol) and 3,4-dimethylbenzaldehyde (0.1 mol) was stirred in refluxing ethanol (30 mL) for 2 h to afford the title compound (0.085 mol, yield 85%). Single crystals suitable for X-ray measurements were obtained by recrystallization of a solution of the title compound in 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 molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

1-(3,4-Dimethylbenzylidene)-4-ethylthiosemicarbazide top

Crystal data top

C₁₂H₁₇N₃S	F(000) = 504
M_r = 235.35	D_x = 1.189 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2429 reflections
a = 8.6659 (17) Å	θ = 3.3–27.5°
b = 15.207 (3) Å	µ = 0.23 mm⁻¹
c = 9.993 (2) Å	T = 293 K
β = 93.47 (3)°	Block, colorless
V = 1314.5 (5) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2429 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −11→11
12215 measured reflections	k = −19→19
3006 independent reflections	l = −12→11

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1293P)² + 0.2681P] where P = (F_o² + 2F_c²)/3
3006 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₂H₁₇N₃S	V = 1314.5 (5) Å³
M_r = 235.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6659 (17) Å	µ = 0.23 mm⁻¹
b = 15.207 (3) Å	T = 293 K
c = 9.993 (2) Å	0.22 × 0.20 × 0.18 mm
β = 93.47 (3)°

Data collection top

Bruker SMART CCD diffractometer	2429 reflections with I > 2σ(I)
12215 measured reflections	R_int = 0.056
3006 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.206	H-atom parameters constrained
S = 1.05	Δρ_max = 0.39 e Å⁻³
3006 reflections	Δρ_min = −0.34 e Å⁻³
145 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	0.84996 (8)	0.11266 (4)	0.92188 (6)	0.0702 (3)
N1	1.02915 (18)	0.11306 (10)	1.28935 (16)	0.0480 (4)
N2	0.9879 (2)	0.08927 (11)	1.15935 (16)	0.0532 (4)
H2A	1.0235	0.0415	1.1269	0.064*
C9	1.1228 (2)	0.06157 (13)	1.35388 (19)	0.0513 (4)
H9A	1.1574	0.0115	1.3114	0.062*
N3	0.8377 (2)	0.21192 (12)	1.14109 (18)	0.0581 (4)
H3A	0.8630	0.2193	1.2249	0.070*
C4	1.1328 (3)	0.15253 (16)	1.5627 (2)	0.0597 (5)
H4A	1.0691	0.1947	1.5206	0.072*
C8	1.2782 (2)	0.01920 (13)	1.5576 (2)	0.0544 (5)
H8A	1.3120	−0.0293	1.5108	0.065*
C3	1.1773 (2)	0.07867 (13)	1.49181 (19)	0.0487 (4)
C10	0.8916 (2)	0.14075 (13)	1.08270 (19)	0.0485 (4)
C7	1.3299 (2)	0.03031 (14)	1.6911 (2)	0.0571 (5)
C6	1.2793 (3)	0.10241 (17)	1.7607 (2)	0.0644 (6)
C5	1.1829 (3)	0.16286 (18)	1.6946 (2)	0.0708 (6)
H5A	1.1511	0.2120	1.7409	0.085*
C2	1.4415 (3)	−0.0353 (2)	1.7562 (3)	0.0837 (8)
H2B	1.4651	−0.0188	1.8480	0.126*
H2C	1.5348	−0.0360	1.7092	0.126*
H2D	1.3956	−0.0927	1.7530	0.126*
C12	0.5844 (3)	0.2822 (2)	1.1272 (4)	0.0950 (9)
H12A	0.5239	0.3265	1.0800	0.143*
H12B	0.5935	0.2963	1.2210	0.143*
H12C	0.5348	0.2261	1.1149	0.143*
C11	0.7391 (3)	0.27866 (18)	1.0749 (3)	0.0787 (7)
H11A	0.7289	0.2663	0.9796	0.094*
H11B	0.7881	0.3357	1.0868	0.094*
C1	1.3292 (4)	0.1167 (3)	1.9069 (3)	0.0973 (11)
H1B	1.2832	0.1698	1.9380	0.146*
H1C	1.4397	0.1216	1.9166	0.146*
H1D	1.2962	0.0679	1.9589	0.146*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0834 (5)	0.0734 (4)	0.0509 (4)	0.0196 (3)	−0.0188 (3)	−0.0005 (2)
N1	0.0472 (8)	0.0524 (8)	0.0437 (8)	0.0018 (6)	−0.0027 (6)	0.0016 (6)
N2	0.0575 (9)	0.0541 (8)	0.0464 (8)	0.0123 (7)	−0.0088 (7)	−0.0005 (7)
C9	0.0536 (10)	0.0496 (9)	0.0496 (10)	0.0050 (7)	−0.0049 (8)	0.0006 (8)
N3	0.0575 (9)	0.0611 (10)	0.0554 (9)	0.0163 (8)	0.0018 (7)	0.0074 (7)
C4	0.0582 (11)	0.0668 (13)	0.0535 (11)	0.0141 (9)	−0.0015 (8)	−0.0024 (9)
C8	0.0552 (10)	0.0493 (9)	0.0572 (11)	−0.0028 (8)	−0.0075 (8)	0.0059 (8)
C3	0.0461 (9)	0.0515 (9)	0.0481 (9)	−0.0020 (7)	−0.0019 (7)	0.0045 (8)
C10	0.0414 (9)	0.0526 (9)	0.0510 (10)	0.0036 (7)	−0.0019 (7)	0.0086 (8)
C7	0.0505 (10)	0.0641 (11)	0.0554 (11)	−0.0114 (8)	−0.0088 (8)	0.0156 (9)
C6	0.0523 (11)	0.0943 (16)	0.0459 (11)	−0.0092 (10)	−0.0025 (8)	0.0010 (10)
C5	0.0677 (14)	0.0861 (16)	0.0580 (12)	0.0112 (11)	0.0003 (10)	−0.0162 (11)
C2	0.0802 (16)	0.0911 (18)	0.0768 (16)	0.0046 (13)	−0.0208 (13)	0.0262 (14)
C12	0.0636 (15)	0.0908 (19)	0.128 (3)	0.0270 (14)	−0.0117 (15)	−0.0062 (18)
C11	0.0817 (16)	0.0739 (15)	0.0810 (16)	0.0347 (13)	0.0081 (12)	0.0185 (12)
C1	0.089 (2)	0.150 (3)	0.0508 (14)	−0.0023 (18)	−0.0132 (13)	−0.0072 (15)

Geometric parameters (Å, º) top

S1—C10	1.681 (2)	C7—C2	1.509 (3)
N1—C9	1.275 (2)	C6—C5	1.383 (3)
N1—N2	1.375 (2)	C6—C1	1.514 (3)
N2—C10	1.349 (2)	C5—H5A	0.9300
N2—H2A	0.8600	C2—H2B	0.9600
C9—C3	1.453 (3)	C2—H2C	0.9600
C9—H9A	0.9300	C2—H2D	0.9600
N3—C10	1.328 (3)	C12—C11	1.468 (4)
N3—C11	1.459 (3)	C12—H12A	0.9600
N3—H3A	0.8600	C12—H12B	0.9600
C4—C5	1.371 (3)	C12—H12C	0.9600
C4—C3	1.395 (3)	C11—H11A	0.9700
C4—H4A	0.9300	C11—H11B	0.9700
C8—C7	1.392 (3)	C1—H1B	0.9600
C8—C3	1.395 (3)	C1—H1C	0.9600
C8—H8A	0.9300	C1—H1D	0.9600
C7—C6	1.384 (3)

C9—N1—N2	115.95 (16)	C4—C5—C6	122.0 (2)
C10—N2—N1	120.03 (16)	C4—C5—H5A	119.0
C10—N2—H2A	120.0	C6—C5—H5A	119.0
N1—N2—H2A	120.0	C7—C2—H2B	109.5
N1—C9—C3	122.03 (18)	C7—C2—H2C	109.5
N1—C9—H9A	119.0	H2B—C2—H2C	109.5
C3—C9—H9A	119.0	C7—C2—H2D	109.5
C10—N3—C11	125.4 (2)	H2B—C2—H2D	109.5
C10—N3—H3A	117.3	H2C—C2—H2D	109.5
C11—N3—H3A	117.3	C11—C12—H12A	109.5
C5—C4—C3	119.9 (2)	C11—C12—H12B	109.5
C5—C4—H4A	120.0	H12A—C12—H12B	109.5
C3—C4—H4A	120.0	C11—C12—H12C	109.5
C7—C8—C3	121.9 (2)	H12A—C12—H12C	109.5
C7—C8—H8A	119.0	H12B—C12—H12C	109.5
C3—C8—H8A	119.0	N3—C11—C12	112.7 (2)
C8—C3—C4	117.90 (18)	N3—C11—H11A	109.0
C8—C3—C9	119.30 (18)	C12—C11—H11A	109.0
C4—C3—C9	122.80 (18)	N3—C11—H11B	109.0
N3—C10—N2	116.46 (17)	C12—C11—H11B	109.0
N3—C10—S1	124.51 (14)	H11A—C11—H11B	107.8
N2—C10—S1	119.02 (15)	C6—C1—H1B	109.5
C6—C7—C8	119.00 (19)	C6—C1—H1C	109.5
C6—C7—C2	121.4 (2)	H1B—C1—H1C	109.5
C8—C7—C2	119.6 (2)	C6—C1—H1D	109.5
C5—C6—C7	119.1 (2)	H1B—C1—H1D	109.5
C5—C6—C1	119.6 (2)	H1C—C1—H1D	109.5
C7—C6—C1	121.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.65	3.4929 (18)	168

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇N₃S
M_r	235.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.6659 (17), 15.207 (3), 9.993 (2)
β (°)	93.47 (3)
V (Å³)	1314.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
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	12215, 3006, 2429
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.206, 1.05
No. of reflections	3006
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −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	2.65	3.4929 (18)	168.4

Symmetry code: (i) −x+2, −y, −z+2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Garcia-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261. Web of Science CrossRef CAS 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
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2685

doi:10.1107/S1600536810038389

Open

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