(E)-1-(4-Methyl­phen­yl)-3-[(1-phenyl­ethyl­idene)amino]­thio­urea

Zhang, Y.-L.; Wu, C.-Z.; Zhang, F.-J.

doi:10.1107/S1600536811019404

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1547

doi:10.1107/S1600536811019404

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(E)-1-(4-Methylphenyl)-3-[(1-phenylethylidene)amino]thiourea

Yan-Ling Zhang,^a ^* Chang-Zeng Wu ^a and Fu-Juan Zhang ^a

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

(Received 19 May 2011; accepted 23 May 2011; online 28 May 2011)

In the title compound, C₁₆H₁₇N₃S, the aminothiourea unit is nearly planar (r.m.s. deviation = 0.0425 Å), and is twisted with respect to the tolyl and phenyl rings by 57.84 (7) and 15.88 (14)°, respectively; the tolyl and phenyl rings are twisted by 65.64 (11)° to each other. Intermolecular N—H⋯S and weak C—H⋯S hydrogen bonds are present in the crystal structure.

Related literature

The title compound is a derivative of thiosemicarbazone. For applications of thiosemicarbazones in the biological field, see: Hu et al. (2006 ).

Experimental

Crystal data

C₁₆H₁₇N₃S
M_r = 283.39
Monoclinic, P 2₁ /c
a = 10.5881 (3) Å
b = 5.7355 (2) Å
c = 26.9746 (7) Å
β = 108.670 (2)°
V = 1551.91 (8) Å³
Z = 4
Cu Kα radiation
μ = 1.79 mm⁻¹
T = 291 K
0.25 × 0.18 × 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 = 0.60, T_max = 0.73
15835 measured reflections
2945 independent reflections
2587 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.126
S = 1.06
2945 reflections
191 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.90 (2)	2.86 (2)	3.7456 (16)	167.8 (19)
C16—H16B⋯S1ⁱ	0.96	2.74	3.471 (2)	133
Symmetry code: (i) -x+2, -y, -z+1.

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: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; 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/S1600536811019404/xu5214sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019404/xu5214Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019404/xu5214Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones have attracted our attention because of their biological applications (Hu et al., 2006). A few single-crystal structures were reported. For understanding their anticancer activity, it is necessary to have detailed information on their geometries.

The molecular structure of (I) is shown in Fig 1. The molecules reveal an E configuration. The dihedral angles formed by the tolyl and phenyl rings with the almost planar aminothiourea unit (r.m.s. deviation = 0.0425 Å) are 57.84 (7) and 15.88 (14)°, respectively. Intermolecular N—H···S and C—H···S interactions occur in the crystal structure (Table 1).

Related literature top

The title compound is a derivative of thiosemicarbazone. For applications of thiosemicarbazones in the biological field, see: Hu et al. (2006).

Experimental top

N-(p-Tolyl)thiosemicarbazide (2.7 g, 15 mmol) and acetophenone (1.8 g, 15 mmol) was dissolved in 95% ethanol (20 ml), and the solution was refluxed for 3 h. Fine colorless crystals appeared on cooling. They were filtered and washed by 95% ethanol to give 2.9 g of the title compound in 69.0% yield. Single crystals suitable for X-ray measurements were obtained from ether 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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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.

(E)-1-(4-Methylphenyl)-3-[(1-phenylethylidene)amino]thiourea top

Crystal data top

C₁₆H₁₇N₃S	F(000) = 600
M_r = 283.39	D_x = 1.213 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.5418 Å
a = 10.5881 (3) Å	Cell parameters from 6724 reflections
b = 5.7355 (2) Å	θ = 3.5–70.9°
c = 26.9746 (7) Å	µ = 1.79 mm⁻¹
β = 108.670 (2)°	T = 291 K
V = 1551.91 (8) Å³	Prismatic, colorless
Z = 4	0.25 × 0.18 × 0.18 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2945 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 16.2312 pixels mm^-1	θ_max = 70.9°, θ_min = 3.5°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −7→6
T_min = 0.60, T_max = 0.73	l = −28→31
15835 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0693P)² + 0.2489P] where P = (F_o² + 2F_c²)/3
2945 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₆H₁₇N₃S	V = 1551.91 (8) Å³
M_r = 283.39	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.5881 (3) Å	µ = 1.79 mm⁻¹
b = 5.7355 (2) Å	T = 291 K
c = 26.9746 (7) Å	0.25 × 0.18 × 0.18 mm
β = 108.670 (2)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2945 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2587 reflections with I > 2σ(I)
T_min = 0.60, T_max = 0.73	R_int = 0.041
15835 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.23 e Å⁻³
2945 reflections	Δρ_min = −0.24 e Å⁻³
191 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	1.08154 (5)	0.02598 (9)	0.436028 (18)	0.05334 (18)
N1	0.82552 (14)	0.5213 (3)	0.42960 (6)	0.0465 (3)
N2	0.90859 (14)	0.3341 (3)	0.44695 (6)	0.0499 (4)
N3	0.99833 (16)	0.4238 (3)	0.38311 (6)	0.0510 (4)
C1	1.06088 (19)	0.2091 (4)	0.31610 (7)	0.0559 (5)
H1	1.0044	0.0876	0.3179	0.067*
C2	1.1318 (2)	0.1997 (4)	0.28098 (7)	0.0656 (6)
H2A	1.1229	0.0699	0.2595	0.079*
C3	1.2149 (2)	0.3777 (5)	0.27725 (7)	0.0651 (6)
C4	1.2278 (2)	0.5681 (4)	0.30964 (8)	0.0630 (5)
H4	1.2841	0.6896	0.3077	0.076*
C5	1.15789 (19)	0.5810 (4)	0.34519 (7)	0.0520 (4)
H5	1.1672	0.7109	0.3667	0.062*
C6	1.07490 (16)	0.4014 (3)	0.34853 (6)	0.0443 (4)
C7	1.2928 (3)	0.3658 (8)	0.23886 (12)	0.1137 (13)
H7A	1.2491	0.4593	0.2087	0.171*
H7B	1.2971	0.2070	0.2283	0.171*
H7C	1.3814	0.4237	0.2553	0.171*
C8	0.99248 (15)	0.2719 (3)	0.42007 (6)	0.0440 (4)
C9	0.74014 (16)	0.5714 (3)	0.45287 (7)	0.0437 (4)
C10	0.64955 (15)	0.7680 (3)	0.43048 (6)	0.0452 (4)
C11	0.6772 (2)	0.9235 (4)	0.39573 (7)	0.0584 (5)
H11	0.7547	0.9058	0.3869	0.070*
C12	0.5910 (3)	1.1032 (5)	0.37429 (9)	0.0761 (7)
H12	0.6102	1.2057	0.3510	0.091*
C13	0.4749 (2)	1.1320 (5)	0.38739 (9)	0.0783 (8)
H13	0.4162	1.2526	0.3726	0.094*
C14	0.4478 (2)	0.9828 (5)	0.42192 (12)	0.0773 (7)
H14	0.3707	1.0024	0.4309	0.093*
C15	0.53386 (19)	0.8031 (4)	0.44367 (10)	0.0665 (6)
H15	0.5146	0.7037	0.4675	0.080*
C16	0.7269 (2)	0.4397 (4)	0.49895 (8)	0.0570 (5)
H16A	0.6858	0.5377	0.5182	0.086*
H16B	0.8137	0.3932	0.5212	0.086*
H16C	0.6728	0.3038	0.4869	0.086*
H2	0.904 (2)	0.230 (4)	0.4714 (8)	0.058 (6)*
H3	0.960 (2)	0.548 (4)	0.3831 (8)	0.053 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0594 (3)	0.0488 (3)	0.0626 (3)	0.01893 (19)	0.0347 (2)	0.01199 (19)
N1	0.0428 (7)	0.0442 (9)	0.0593 (8)	0.0093 (6)	0.0257 (6)	0.0052 (6)
N2	0.0502 (8)	0.0488 (9)	0.0607 (8)	0.0150 (7)	0.0319 (6)	0.0117 (7)
N3	0.0550 (8)	0.0492 (10)	0.0578 (8)	0.0193 (7)	0.0305 (7)	0.0099 (7)
C1	0.0614 (10)	0.0575 (12)	0.0464 (8)	0.0029 (9)	0.0138 (7)	−0.0037 (8)
C2	0.0828 (13)	0.0722 (15)	0.0404 (8)	0.0195 (11)	0.0177 (8)	−0.0086 (8)
C3	0.0717 (12)	0.0870 (17)	0.0436 (9)	0.0292 (12)	0.0282 (8)	0.0116 (9)
C4	0.0648 (11)	0.0709 (14)	0.0624 (11)	0.0067 (10)	0.0333 (9)	0.0157 (10)
C5	0.0624 (10)	0.0480 (11)	0.0518 (9)	0.0075 (8)	0.0268 (8)	0.0018 (7)
C6	0.0450 (8)	0.0503 (10)	0.0395 (7)	0.0137 (7)	0.0162 (6)	0.0063 (6)
C7	0.130 (3)	0.159 (3)	0.0798 (16)	0.037 (2)	0.0733 (18)	0.0119 (19)
C8	0.0398 (7)	0.0478 (10)	0.0487 (8)	0.0052 (7)	0.0201 (6)	0.0017 (7)
C9	0.0392 (7)	0.0441 (10)	0.0535 (8)	0.0035 (7)	0.0229 (6)	0.0005 (7)
C10	0.0375 (7)	0.0506 (10)	0.0490 (8)	0.0058 (7)	0.0159 (6)	−0.0033 (7)
C11	0.0623 (11)	0.0632 (13)	0.0556 (10)	0.0202 (9)	0.0273 (8)	0.0082 (9)
C12	0.0911 (16)	0.0768 (17)	0.0577 (11)	0.0305 (13)	0.0201 (10)	0.0146 (11)
C13	0.0655 (12)	0.0806 (18)	0.0706 (13)	0.0360 (12)	−0.0040 (10)	−0.0071 (12)
C14	0.0433 (10)	0.0823 (18)	0.1062 (18)	0.0183 (10)	0.0237 (11)	−0.0094 (14)
C15	0.0480 (10)	0.0686 (15)	0.0930 (14)	0.0100 (9)	0.0367 (10)	0.0057 (12)
C16	0.0595 (10)	0.0586 (12)	0.0638 (10)	0.0104 (9)	0.0351 (8)	0.0095 (9)

Geometric parameters (Å, º) top

S1—C8	1.6746 (18)	C7—H7A	0.9600
N1—N2	1.372 (2)	C7—H7B	0.9600
N1—C9	1.287 (2)	C7—H7C	0.9600
N2—C8	1.362 (2)	C9—C10	1.478 (2)
N2—H2	0.90 (2)	C9—C16	1.499 (2)
N3—C6	1.424 (2)	C10—C11	1.391 (3)
N3—C8	1.340 (2)	C10—C15	1.395 (2)
N3—H3	0.82 (2)	C11—H11	0.9300
C1—H1	0.9300	C11—C12	1.375 (3)
C1—C2	1.386 (3)	C12—H12	0.9300
C1—C6	1.386 (3)	C12—C13	1.393 (4)
C2—H2A	0.9300	C13—H13	0.9300
C2—C3	1.373 (4)	C13—C14	1.361 (4)
C3—C4	1.378 (4)	C14—H14	0.9300
C3—C7	1.517 (3)	C14—C15	1.376 (3)
C4—H4	0.9300	C15—H15	0.9300
C4—C5	1.388 (3)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C5—C6	1.376 (3)	C16—H16C	0.9600

C9—N1—N2	118.83 (15)	N2—C8—S1	119.57 (13)
N1—N2—H2	126.2 (14)	N3—C8—S1	125.62 (12)
C8—N2—N1	118.67 (15)	N3—C8—N2	114.78 (16)
C8—N2—H2	114.3 (14)	N1—C9—C10	115.87 (15)
C6—N3—H3	117.8 (16)	N1—C9—C16	123.94 (16)
C8—N3—C6	126.88 (15)	C10—C9—C16	120.17 (14)
C8—N3—H3	115.0 (16)	C11—C10—C9	121.03 (15)
C2—C1—H1	120.3	C11—C10—C15	118.04 (18)
C2—C1—C6	119.4 (2)	C15—C10—C9	120.93 (17)
C6—C1—H1	120.3	C10—C11—H11	119.7
C1—C2—H2A	119.3	C12—C11—C10	120.6 (2)
C3—C2—C1	121.4 (2)	C12—C11—H11	119.7
C3—C2—H2A	119.3	C11—C12—H12	119.9
C2—C3—C4	118.58 (18)	C11—C12—C13	120.2 (2)
C2—C3—C7	121.2 (3)	C13—C12—H12	119.9
C4—C3—C7	120.2 (3)	C12—C13—H13	120.2
C3—C4—H4	119.5	C14—C13—C12	119.7 (2)
C3—C4—C5	121.0 (2)	C14—C13—H13	120.2
C5—C4—H4	119.5	C13—C14—H14	119.8
C4—C5—H5	120.1	C13—C14—C15	120.5 (2)
C6—C5—C4	119.86 (19)	C15—C14—H14	119.8
C6—C5—H5	120.1	C10—C15—H15	119.5
C1—C6—N3	121.13 (18)	C14—C15—C10	121.0 (2)
C5—C6—N3	119.00 (17)	C14—C15—H15	119.5
C5—C6—C1	119.75 (16)	C9—C16—H16A	109.5
C3—C7—H7A	109.5	C9—C16—H16B	109.5
C3—C7—H7B	109.5	C9—C16—H16C	109.5
C3—C7—H7C	109.5	H16A—C16—H16B	109.5
H7A—C7—H7B	109.5	H16A—C16—H16C	109.5
H7A—C7—H7C	109.5	H16B—C16—H16C	109.5
H7B—C7—H7C	109.5

N1—N2—C8—S1	−172.72 (13)	C6—C1—C2—C3	−0.6 (3)
N1—N2—C8—N3	9.3 (2)	C7—C3—C4—C5	−179.6 (2)
N1—C9—C10—C11	−15.8 (3)	C8—N3—C6—C1	56.4 (3)
N1—C9—C10—C15	164.35 (19)	C8—N3—C6—C5	−127.6 (2)
N2—N1—C9—C10	−177.12 (15)	C9—N1—N2—C8	175.59 (16)
N2—N1—C9—C16	1.2 (3)	C9—C10—C11—C12	178.7 (2)
C1—C2—C3—C4	0.4 (3)	C9—C10—C15—C14	−178.5 (2)
C1—C2—C3—C7	179.7 (2)	C10—C11—C12—C13	0.3 (4)
C2—C1—C6—N3	176.51 (16)	C11—C10—C15—C14	1.6 (3)
C2—C1—C6—C5	0.6 (3)	C11—C12—C13—C14	0.6 (4)
C2—C3—C4—C5	−0.3 (3)	C12—C13—C14—C15	−0.4 (4)
C3—C4—C5—C6	0.3 (3)	C13—C14—C15—C10	−0.8 (4)
C4—C5—C6—N3	−176.47 (16)	C15—C10—C11—C12	−1.4 (3)
C4—C5—C6—C1	−0.4 (3)	C16—C9—C10—C11	165.88 (19)
C6—N3—C8—S1	3.6 (3)	C16—C9—C10—C15	−14.0 (3)
C6—N3—C8—N2	−178.56 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.90 (2)	2.86 (2)	3.7456 (16)	167.8 (19)
C16—H16B···S1ⁱ	0.96	2.74	3.471 (2)	133

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇N₃S
M_r	283.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	10.5881 (3), 5.7355 (2), 26.9746 (7)
β (°)	108.670 (2)
V (Å³)	1551.91 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.25 × 0.18 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.60, 0.73
No. of measured, independent and observed [I > 2σ(I)] reflections	15835, 2945, 2587
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.126, 1.06
No. of reflections	2945
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXTL (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	0.90 (2)	2.86 (2)	3.7456 (16)	167.8 (19)
C16—H16B···S1ⁱ	0.96	2.74	3.471 (2)	133

Symmetry code: (i) −x+2, −y, −z+1.

Acknowledgements

The authors thank the Natural Science Foundation of Henan Province (112102310538, 082300420110), the Natural Science Foundation of the Education Department of Henan Province (2010B150029) and the Scientific Research Foundation of Xuchang University of Henan Province, China (2009086) for supporting this work.

References

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Hu, W.-X., Zhou, W., Xia, C.-N. & Wen, X. (2006). Bioorg. Med. Chem. Lett. 16, 2213–2218. Web of Science CrossRef PubMed CAS Google Scholar
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