4-Ethyl-1-(4-meth­oxy­benzyl­idene)thio­semicarbazide

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

doi:10.1107/S1600536810022919

organic compounds

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Volume 66| Part 7| July 2010| Page o1714

doi:10.1107/S1600536810022919

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4-Ethyl-1-(4-methoxybenzylidene)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 9 June 2010; accepted 14 June 2010; online 18 June 2010)

In the title compound, C₁₁H₁₅N₃OS, the dihedral angle between the aromatic ring and the thiourea unit is 4.28 (7)° and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal, molecules are linked into (001) sheets by N—H⋯S hydrogen bonds.

Related literature

For background to the reactions and properties of thiosemicarbazones, see: Casas et al. (2000 ); Lobana et al. (2009 ); Quiroga & Ranninger (2004 ). For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₁H₁₅N₃OS
M_r = 237.32
Orthorhombic, P b c a
a = 13.066 (3) Å
b = 10.128 (2) Å
c = 19.224 (4) Å
V = 2543.9 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
22633 measured reflections
2912 independent reflections
2302 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.160
S = 1.05
2912 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.26 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
N1—H1A⋯S1ⁱ	0.86	2.60	3.4080 (17)	156
N3—H3A⋯N2	0.86	2.26	2.634 (2)	106
N3—H3A⋯S1ⁱⁱ	0.86	2.78	3.4670 (17)	137
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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/S1600536810022919/hb5492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022919/hb5492Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones have attracted much attention because they can be utilized as effective ligands to form the compounds with antitumoral drugs. (Quiroga & Ranninger, 2004).They are important versatile coordination agents which have been reported to be coordination compounds (Casas et al., 2000) (Lobana et al., 2009). As part of our search for new thiosemicarbazones compounds we synthesized the title compound (I), and describe its structure here. The dihedral angle between the benzene ring and the thiourea unit is [4.28 (7)°]. Intermolecular N—H···S hydrogen bonds generate chains.

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

Related literature top

For background to the reactions and properties of thiosemicarbazones, see: Casas et al. (2000); Lobana et al. (2009); Quiroga & Ranninger (2004). For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-methoxybenzaldehyde (0.1 mol) and 4-ethylthiosemicarbazide (0.1 mol) was stirred in refluxing ethanol (20 ml) for 2 h to afford the title compound (0.086 mol, yield 86%). 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 (I) showing 30% probability displacement ellipsoids.

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

Crystal data top

C₁₁H₁₅N₃OS	F(000) = 1008
M_r = 237.32	D_x = 1.239 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2302 reflections
a = 13.066 (3) Å	θ = 2.8–25.3°
b = 10.128 (2) Å	µ = 0.24 mm⁻¹
c = 19.224 (4) Å	T = 293 K
V = 2543.9 (9) Å³	Block, colorless
Z = 8	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2302 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
phi and ω scans	h = −16→16
22633 measured reflections	k = −13→13
2912 independent reflections	l = −24→24

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0997P)² + 0.2868P] where P = (F_o² + 2F_c²)/3
2912 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₁H₁₅N₃OS	V = 2543.9 (9) Å³
M_r = 237.32	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.066 (3) Å	µ = 0.24 mm⁻¹
b = 10.128 (2) Å	T = 293 K
c = 19.224 (4) Å	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2302 reflections with I > 2σ(I)
22633 measured reflections	R_int = 0.044
2912 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
2912 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	0.12047 (4)	1.04218 (4)	0.57631 (3)	0.0768 (2)
N1	0.09565 (11)	0.83299 (14)	0.49802 (8)	0.0648 (4)
H1A	0.0548	0.8818	0.4742	0.078*
N2	0.11117 (10)	0.70368 (14)	0.47913 (8)	0.0598 (3)
C9	0.12596 (13)	0.30355 (18)	0.41061 (9)	0.0637 (4)
H9A	0.1545	0.2367	0.4375	0.076*
C3	0.14420 (12)	0.88334 (15)	0.55374 (9)	0.0596 (4)
N3	0.21067 (12)	0.80566 (14)	0.58550 (9)	0.0719 (4)
H3A	0.2271	0.7331	0.5651	0.086*
O1	0.09603 (11)	0.15651 (14)	0.31258 (7)	0.0803 (4)
C5	0.07418 (12)	0.53144 (16)	0.39807 (8)	0.0576 (4)
C10	0.11699 (13)	0.42999 (18)	0.43678 (9)	0.0621 (4)
H10A	0.1403	0.4476	0.4815	0.075*
C4	0.06596 (13)	0.66625 (17)	0.42425 (9)	0.0626 (4)
H4A	0.0262	0.7267	0.3999	0.075*
C8	0.09189 (12)	0.27751 (17)	0.34373 (9)	0.0621 (4)
C6	0.04087 (15)	0.5032 (2)	0.33114 (10)	0.0719 (5)
H6A	0.0115	0.5696	0.3044	0.086*
C11	0.14227 (19)	0.05082 (19)	0.34942 (13)	0.0866 (6)
H11A	0.1397	−0.0278	0.3216	0.130*
H11B	0.1061	0.0363	0.3922	0.130*
H11C	0.2123	0.0725	0.3594	0.130*
C2	0.25846 (16)	0.8338 (2)	0.65277 (13)	0.0910 (7)
H2B	0.2628	0.9285	0.6594	0.109*
H2C	0.3275	0.7984	0.6532	0.109*
C7	0.05071 (16)	0.3784 (2)	0.30398 (10)	0.0769 (5)
H7A	0.0296	0.3616	0.2586	0.092*
C1	0.1984 (3)	0.7743 (4)	0.71090 (15)	0.1455 (13)
H1B	0.2311	0.7943	0.7544	0.218*
H1C	0.1952	0.6803	0.7049	0.218*
H1D	0.1304	0.8100	0.7108	0.218*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0653 (3)	0.0441 (3)	0.1211 (5)	0.00297 (16)	−0.0100 (2)	−0.0109 (2)
N1	0.0687 (8)	0.0469 (7)	0.0786 (9)	0.0078 (6)	−0.0085 (7)	0.0005 (6)
N2	0.0596 (7)	0.0479 (7)	0.0720 (8)	0.0022 (5)	−0.0015 (6)	−0.0004 (6)
C9	0.0672 (9)	0.0567 (10)	0.0673 (9)	0.0013 (7)	−0.0052 (7)	0.0071 (7)
C3	0.0526 (7)	0.0447 (8)	0.0814 (10)	−0.0024 (6)	0.0014 (7)	−0.0002 (7)
N3	0.0716 (9)	0.0512 (8)	0.0929 (10)	0.0102 (6)	−0.0169 (8)	−0.0137 (7)
O1	0.0857 (8)	0.0647 (8)	0.0905 (9)	0.0036 (6)	−0.0126 (7)	−0.0171 (7)
C5	0.0515 (8)	0.0583 (9)	0.0632 (8)	0.0022 (6)	−0.0032 (6)	−0.0007 (6)
C10	0.0695 (10)	0.0594 (10)	0.0575 (8)	−0.0005 (7)	−0.0070 (7)	0.0017 (7)
C4	0.0604 (9)	0.0585 (9)	0.0688 (9)	0.0067 (7)	−0.0063 (7)	0.0016 (7)
C8	0.0547 (8)	0.0613 (10)	0.0702 (9)	−0.0008 (7)	−0.0022 (7)	−0.0071 (7)
C6	0.0762 (11)	0.0698 (10)	0.0697 (10)	0.0143 (9)	−0.0188 (8)	0.0012 (8)
C11	0.0946 (14)	0.0568 (11)	0.1083 (16)	0.0024 (9)	0.0065 (13)	−0.0021 (10)
C2	0.0766 (12)	0.0677 (12)	0.1285 (18)	0.0107 (9)	−0.0402 (13)	−0.0265 (11)
C7	0.0856 (12)	0.0772 (12)	0.0679 (10)	0.0109 (9)	−0.0231 (9)	−0.0102 (9)
C1	0.120 (2)	0.232 (4)	0.0849 (16)	−0.025 (2)	−0.0161 (16)	−0.032 (2)

Geometric parameters (Å, º) top

S1—C3	1.6948 (17)	C10—H10A	0.9300
N1—C3	1.345 (2)	C4—H4A	0.9300
N1—N2	1.3742 (19)	C8—C7	1.385 (3)
N1—H1A	0.8600	C6—C7	1.373 (3)
N2—C4	1.267 (2)	C6—H6A	0.9300
C9—C10	1.381 (2)	C11—H11A	0.9600
C9—C8	1.386 (3)	C11—H11B	0.9600
C9—H9A	0.9300	C11—H11C	0.9600
C3—N3	1.321 (2)	C2—C1	1.492 (4)
N3—C2	1.464 (2)	C2—H2B	0.9700
N3—H3A	0.8600	C2—H2C	0.9700
O1—C8	1.365 (2)	C7—H7A	0.9300
O1—C11	1.419 (3)	C1—H1B	0.9600
C5—C10	1.387 (2)	C1—H1C	0.9600
C5—C6	1.388 (2)	C1—H1D	0.9600
C5—C4	1.459 (2)

C3—N1—N2	120.14 (13)	C7—C8—C9	119.75 (16)
C3—N1—H1A	119.9	C7—C6—C5	120.86 (16)
N2—N1—H1A	119.9	C7—C6—H6A	119.6
C4—N2—N1	115.87 (14)	C5—C6—H6A	119.6
C10—C9—C8	119.16 (16)	O1—C11—H11A	109.5
C10—C9—H9A	120.4	O1—C11—H11B	109.5
C8—C9—H9A	120.4	H11A—C11—H11B	109.5
N3—C3—N1	116.89 (14)	O1—C11—H11C	109.5
N3—C3—S1	124.54 (13)	H11A—C11—H11C	109.5
N1—C3—S1	118.51 (12)	H11B—C11—H11C	109.5
C3—N3—C2	124.95 (15)	N3—C2—C1	111.03 (19)
C3—N3—H3A	117.5	N3—C2—H2B	109.4
C2—N3—H3A	117.5	C1—C2—H2B	109.4
C8—O1—C11	118.37 (16)	N3—C2—H2C	109.4
C10—C5—C6	118.11 (16)	C1—C2—H2C	109.4
C10—C5—C4	122.54 (15)	H2B—C2—H2C	108.0
C6—C5—C4	119.32 (15)	C6—C7—C8	120.37 (16)
C9—C10—C5	121.73 (16)	C6—C7—H7A	119.8
C9—C10—H10A	119.1	C8—C7—H7A	119.8
C5—C10—H10A	119.1	C2—C1—H1B	109.5
N2—C4—C5	122.20 (15)	C2—C1—H1C	109.5
N2—C4—H4A	118.9	H1B—C1—H1C	109.5
C5—C4—H4A	118.9	C2—C1—H1D	109.5
O1—C8—C7	115.83 (15)	H1B—C1—H1D	109.5
O1—C8—C9	124.41 (16)	H1C—C1—H1D	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.60	3.4080 (17)	156
N3—H3A···N2	0.86	2.26	2.634 (2)	106
N3—H3A···S1ⁱⁱ	0.86	2.78	3.4670 (17)	137

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₃OS
M_r	237.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	13.066 (3), 10.128 (2), 19.224 (4)
V (Å³)	2543.9 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
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	22633, 2912, 2302
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.160, 1.05
No. of reflections	2912
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −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
N1—H1A···S1ⁱ	0.86	2.60	3.4080 (17)	156
N3—H3A···N2	0.86	2.26	2.634 (2)	106
N3—H3A···S1ⁱⁱ	0.86	2.78	3.4670 (17)	137

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1/2, y−1/2, z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Garcia-T, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261. Web of Science CrossRef CAS Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lobana, T. S., Khanna, S., Hundal, G., Kaur, P., Thakur, B., Attri, S. & Butcher, R. J. (2009). Polyhedron, 28, 1583–1593. Web of Science CSD CrossRef CAS Google Scholar
Quiroga, A. G. & Ranninger, C. N. (2004). Coord. Chem. Rev. 248, 119–133. Web of Science CrossRef CAS 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 7| July 2010| Page o1714

doi:10.1107/S1600536810022919

Open

access