1-Benzyl­idene­amino-3-(4-methyl­phen­yl)thio­urea

Zhang, Y.-L.; Xu, Z.-H.; Zhang, F.-J.; Yang, F.-L.

doi:10.1107/S160053681100198X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o449

doi:10.1107/S160053681100198X

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1-Benzylideneamino-3-(4-methylphenyl)thiourea

Yan-Ling Zhang,^a Zhi-Hong Xu,^a Fu-Juan Zhang ^a and Feng-Ling Yang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China
^*Correspondence e-mail: zhangyanling315@126.com

(Received 11 January 2011; accepted 13 January 2011; online 22 January 2011)

In the title compound, C₁₅H₁₅N₃S, the almost planar 2-benzylidenehydrazinecarbothioamide unit (r.m.s. deviation = 0.0351 Å) is aligned at a dihedral angle of 64.42 (6)° with respect to the plane of the tolyl ring. The molecule exhibits an E configuration for the azomethine linkage. In the crystal, intermolecular N—H⋯S hydrogen bonds about centers of inversion lead to the formation of dimers.

Related literature

For biological applications of thiosemicarbazones, see: Hu et al. (2006 ).

Experimental

Crystal data

C₁₅H₁₅N₃S
M_r = 269.36
Monoclinic, P 2₁ /c
a = 10.2359 (3) Å
b = 16.0648 (3) Å
c = 9.9703 (3) Å
β = 117.154 (4)°
V = 1458.81 (7) Å³
Z = 4
Cu Kα radiation
μ = 1.88 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.603, T_max = 0.729
12637 measured reflections
2605 independent reflections
2253 reflections with I > 2σ(I)
R_int = 0.026
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.120
S = 1.05
2605 reflections
181 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 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—H2⋯S1ⁱ	0.88 (2)	2.48 (2)	3.3522 (15)	170.3 (17)
Symmetry code: (i) -x, -y, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100198X/ng5104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100198X/ng5104Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones have attracted our attention because of their biological applications (Hu et al., 2006). A few single-crystal reports about them are presented. Detailed information on their molecular and crystal structures is necessary to understand their anticancer activity. The molecular structure of (I) is shown in Fig 1. The molecules exhibit an E configuration.The thiosemicarbazide and benzaldehyde unit are located on opposite sides of the N1=C7 bond.The 2-benzylidenehydrazinecarbothioamide unit has a planar configuration and subtends an angle of 64.42 (6)° with respect to the plane of the tolyl ring.In the crystal structure of the title compound, there is N(2)—H(2)···S(1)#1 hydrogen-bond interactions in molecules which leads to a supramolecular architecture (Fig. 2).

Related literature top

For biological applications of thiosemicarbazones, see: Hu et al. (2006).

Experimental top

N-(p-Tolyl)hydrazinecarbothioamide (2.7 g,15 mmol) and benzaldehyde (1.6 g, 15 mmol) was dissolved in 95% ethanol (20 ml) and the solution was refluxed for 6.5 h. Fine colorless crystals appeared on cooling. They were filtered and washed by 95% ethanol to give 2.6 g of the title compound in 65% yield. Single crystals suitable for X-ray measurements were obtained from 2-propanol by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed line.

1-Benzylideneamino-3-(4-methylphenyl)thiourea top

Crystal data top

C₁₅H₁₅N₃S	F(000) = 568
M_r = 269.36	D_x = 1.226 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 7009 reflections
a = 10.2359 (3) Å	θ = 4.9–72.1°
b = 16.0648 (3) Å	µ = 1.88 mm⁻¹
c = 9.9703 (3) Å	T = 293 K
β = 117.154 (4)°	Prismatic, colorless
V = 1458.81 (7) Å³	0.30 × 0.20 × 0.18 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2605 independent reflections
Radiation source: fine-focus sealed tube	2253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 67.1°, θ_min = 4.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −12→12
T_min = 0.603, T_max = 0.729	k = −19→19
12637 measured reflections	l = −8→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0727P)² + 0.1569P] where P = (F_o² + 2F_c²)/3
2605 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₅H₁₅N₃S	V = 1458.81 (7) Å³
M_r = 269.36	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.2359 (3) Å	µ = 1.88 mm⁻¹
b = 16.0648 (3) Å	T = 293 K
c = 9.9703 (3) Å	0.30 × 0.20 × 0.18 mm
β = 117.154 (4)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2605 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2253 reflections with I > 2σ(I)
T_min = 0.603, T_max = 0.729	R_int = 0.026
12637 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.19 e Å⁻³
2605 reflections	Δρ_min = −0.21 e Å⁻³
181 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	0.13263 (6)	0.10810 (3)	0.02008 (5)	0.0727 (2)
N1	0.15900 (15)	−0.00305 (8)	0.37897 (15)	0.0546 (3)
N2	0.12114 (16)	0.01805 (8)	0.23296 (16)	0.0566 (3)
N3	0.28187 (16)	0.12678 (9)	0.31818 (17)	0.0599 (4)
C1	0.2093 (2)	−0.05346 (12)	0.6752 (2)	0.0684 (5)
H1	0.2567	−0.0052	0.6694	0.082*
C2	0.2298 (3)	−0.08202 (15)	0.8131 (2)	0.0815 (6)
H2A	0.2905	−0.0528	0.9000	0.098*
C3	0.1610 (3)	−0.15388 (14)	0.8239 (2)	0.0798 (6)
H3A	0.1763	−0.1736	0.9177	0.096*
C4	0.0699 (3)	−0.19596 (13)	0.6949 (2)	0.0765 (5)
H4	0.0226	−0.2441	0.7014	0.092*
C5	0.0481 (2)	−0.16751 (11)	0.5560 (2)	0.0667 (4)
H5	−0.0140	−0.1964	0.4693	0.080*
C6	0.11855 (18)	−0.09582 (10)	0.5445 (2)	0.0560 (4)
C7	0.09253 (18)	−0.06621 (10)	0.39603 (19)	0.0569 (4)
H7	0.0252	−0.0943	0.3110	0.068*
C8	0.18293 (17)	0.08400 (9)	0.20078 (19)	0.0532 (4)
C9	0.35959 (17)	0.19777 (10)	0.30466 (18)	0.0542 (4)
C10	0.4599 (2)	0.18975 (13)	0.2504 (3)	0.0838 (6)
H10	0.4801	0.1375	0.2241	0.101*
C11	0.5311 (3)	0.25904 (16)	0.2346 (3)	0.0938 (8)
H11	0.5983	0.2529	0.1965	0.113*
C12	0.5053 (2)	0.33670 (13)	0.2737 (2)	0.0750 (5)
C13	0.4092 (2)	0.34307 (11)	0.3338 (3)	0.0790 (5)
H13	0.3933	0.3948	0.3656	0.095*
C14	0.3353 (2)	0.27444 (11)	0.3483 (2)	0.0670 (5)
H14	0.2692	0.2804	0.3877	0.080*
C15	0.5825 (3)	0.41238 (18)	0.2529 (3)	0.1188 (11)
H15B	0.6778	0.3966	0.2653	0.178*
H15C	0.5928	0.4538	0.3265	0.178*
H15A	0.5257	0.4347	0.1536	0.178*
H2	0.054 (2)	−0.0105 (12)	0.158 (2)	0.067 (5)*
H3	0.294 (2)	0.1122 (12)	0.410 (3)	0.069 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0880 (4)	0.0664 (3)	0.0596 (3)	−0.0262 (2)	0.0302 (2)	0.00300 (19)
N1	0.0597 (7)	0.0492 (7)	0.0585 (8)	0.0007 (5)	0.0303 (6)	0.0018 (5)
N2	0.0642 (8)	0.0480 (7)	0.0573 (8)	−0.0075 (6)	0.0275 (7)	0.0007 (6)
N3	0.0670 (8)	0.0561 (7)	0.0596 (8)	−0.0104 (6)	0.0315 (7)	−0.0027 (6)
C1	0.0754 (11)	0.0668 (10)	0.0659 (11)	−0.0117 (8)	0.0349 (9)	−0.0038 (8)
C2	0.0902 (14)	0.0930 (14)	0.0586 (11)	−0.0119 (11)	0.0317 (10)	−0.0073 (10)
C3	0.0928 (14)	0.0919 (14)	0.0675 (12)	0.0027 (11)	0.0476 (11)	0.0111 (10)
C4	0.0926 (14)	0.0691 (11)	0.0825 (13)	−0.0089 (10)	0.0527 (12)	0.0085 (9)
C5	0.0784 (11)	0.0588 (9)	0.0701 (11)	−0.0105 (8)	0.0401 (9)	−0.0037 (8)
C6	0.0627 (9)	0.0510 (8)	0.0620 (9)	0.0003 (6)	0.0352 (8)	−0.0008 (7)
C7	0.0656 (9)	0.0496 (8)	0.0593 (9)	−0.0042 (7)	0.0317 (7)	−0.0034 (7)
C8	0.0561 (8)	0.0444 (7)	0.0634 (9)	0.0003 (6)	0.0309 (7)	0.0010 (6)
C9	0.0535 (8)	0.0537 (8)	0.0560 (8)	−0.0063 (6)	0.0257 (7)	−0.0044 (6)
C10	0.0799 (13)	0.0721 (12)	0.1209 (18)	−0.0164 (10)	0.0643 (13)	−0.0325 (12)
C11	0.0858 (14)	0.1098 (17)	0.1139 (18)	−0.0380 (13)	0.0699 (14)	−0.0354 (14)
C12	0.0735 (11)	0.0781 (12)	0.0649 (11)	−0.0267 (9)	0.0242 (9)	−0.0005 (9)
C13	0.0830 (13)	0.0539 (10)	0.0972 (15)	−0.0054 (9)	0.0387 (11)	−0.0048 (9)
C14	0.0668 (10)	0.0599 (10)	0.0840 (12)	−0.0036 (8)	0.0427 (9)	−0.0096 (8)
C15	0.123 (2)	0.117 (2)	0.1007 (19)	−0.0629 (18)	0.0376 (16)	0.0096 (15)

Geometric parameters (Å, º) top

S1—C8	1.6776 (17)	C5—H5	0.9300
N1—C7	1.276 (2)	C6—C7	1.459 (2)
N1—N2	1.367 (2)	C7—H7	0.9300
N2—C8	1.346 (2)	C9—C14	1.366 (2)
N2—H2	0.88 (2)	C9—C10	1.368 (3)
N3—C8	1.336 (2)	C10—C11	1.378 (3)
N3—C9	1.432 (2)	C10—H10	0.9300
N3—H3	0.90 (2)	C11—C12	1.368 (3)
C1—C2	1.371 (3)	C11—H11	0.9300
C1—C6	1.386 (3)	C12—C13	1.370 (3)
C1—H1	0.9300	C12—C15	1.515 (3)
C2—C3	1.382 (3)	C13—C14	1.381 (3)
C2—H2A	0.9300	C13—H13	0.9300
C3—C4	1.374 (3)	C14—H14	0.9300
C3—H3A	0.9300	C15—H15B	0.9600
C4—C5	1.376 (3)	C15—H15C	0.9600
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.391 (2)

C7—N1—N2	115.46 (14)	N3—C8—N2	116.54 (15)
C8—N2—N1	120.89 (14)	N3—C8—S1	124.09 (12)
C8—N2—H2	118.7 (13)	N2—C8—S1	119.37 (13)
N1—N2—H2	120.4 (13)	C14—C9—C10	119.28 (16)
C8—N3—C9	123.97 (14)	C14—C9—N3	119.92 (15)
C8—N3—H3	117.3 (13)	C10—C9—N3	120.80 (15)
C9—N3—H3	118.6 (13)	C9—C10—C11	120.03 (18)
C2—C1—C6	120.59 (18)	C9—C10—H10	120.0
C2—C1—H1	119.7	C11—C10—H10	120.0
C6—C1—H1	119.7	C12—C11—C10	121.56 (19)
C1—C2—C3	120.49 (19)	C12—C11—H11	119.2
C1—C2—H2A	119.8	C10—C11—H11	119.2
C3—C2—H2A	119.8	C11—C12—C13	117.60 (18)
C4—C3—C2	119.36 (18)	C11—C12—C15	120.8 (2)
C4—C3—H3A	120.3	C13—C12—C15	121.6 (2)
C2—C3—H3A	120.3	C12—C13—C14	121.51 (19)
C3—C4—C5	120.53 (18)	C12—C13—H13	119.2
C3—C4—H4	119.7	C14—C13—H13	119.2
C5—C4—H4	119.7	C9—C14—C13	119.93 (17)
C4—C5—C6	120.38 (18)	C9—C14—H14	120.0
C4—C5—H5	119.8	C13—C14—H14	120.0
C6—C5—H5	119.8	C12—C15—H15B	109.5
C1—C6—C5	118.64 (16)	C12—C15—H15C	109.5
C1—C6—C7	121.86 (15)	H15B—C15—H15C	109.5
C5—C6—C7	119.48 (15)	C12—C15—H15A	109.5
N1—C7—C6	122.22 (15)	H15B—C15—H15A	109.5
N1—C7—H7	118.9	H15C—C15—H15A	109.5
C6—C7—H7	118.9

C7—N1—N2—C8	179.41 (15)	N1—N2—C8—N3	0.1 (2)
C6—C1—C2—C3	0.4 (3)	N1—N2—C8—S1	−179.63 (11)
C1—C2—C3—C4	−0.9 (4)	C8—N3—C9—C14	113.67 (19)
C2—C3—C4—C5	0.6 (3)	C8—N3—C9—C10	−67.3 (2)
C3—C4—C5—C6	0.2 (3)	C14—C9—C10—C11	−2.5 (3)
C2—C1—C6—C5	0.4 (3)	N3—C9—C10—C11	178.4 (2)
C2—C1—C6—C7	178.92 (18)	C9—C10—C11—C12	0.7 (4)
C4—C5—C6—C1	−0.7 (3)	C10—C11—C12—C13	2.0 (4)
C4—C5—C6—C7	−179.28 (17)	C10—C11—C12—C15	−178.9 (2)
N2—N1—C7—C6	−178.88 (14)	C11—C12—C13—C14	−3.0 (3)
C1—C6—C7—N1	4.7 (3)	C15—C12—C13—C14	177.9 (2)
C5—C6—C7—N1	−176.80 (16)	C10—C9—C14—C13	1.6 (3)
C9—N3—C8—N2	179.12 (14)	N3—C9—C14—C13	−179.34 (18)
C9—N3—C8—S1	−1.2 (2)	C12—C13—C14—C9	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.88 (2)	2.48 (2)	3.3522 (15)	170.3 (17)

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃S
M_r	269.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.2359 (3), 16.0648 (3), 9.9703 (3)
β (°)	117.154 (4)
V (Å³)	1458.81 (7)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.88
Crystal size (mm)	0.30 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.603, 0.729
No. of measured, independent and observed [I > 2σ(I)] reflections	12637, 2605, 2253
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.120, 1.05
No. of reflections	2605
No. of parameters	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.88 (2)	2.48 (2)	3.3522 (15)	170.3 (17)

Symmetry code: (i) −x, −y, −z.

Acknowledgements

The authors thank the Natural Science Foundation of the Education Department of Henan Province (2010B150029), the Natural Science Foundation of Henan Province (082300420110) and the Scientific Research Foundation of Xuchang University of Henan Province (2009086) for supporting this work.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
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