1-(2-Nitro­phen­yl)-3-phenyl­thio­urea

Abstract

The title compound, C₁₃H₁₁N₃O₂S, was prepared by reaction of 2-nitro­benzenamine, KOH and 1-isothio­cyanato­benzene in an ethanol solution at room temperature. The dihedral angles formed between the thiourea plane and the phenyl rings are 61.9 and 31.0°. The dihedral angle between the two phenyl rings is 78.1°. In the crystal structure, there are weak inter­molecular N—H⋯S and C—H⋯S hydrogen-bonding inter­actions.

Related literature

For related literature, see: Reinbold & Morar (1984 ▶); Xue et al. (2004 ▶); Madan & Taneja (1991 ▶).

Experimental

Crystal data

• C₁₃H₁₁N₃O₂S

• M _r = 273.31

• Monoclinic,

• a = 7.3110 (15) Å

• b = 24.113 (5) Å

• c = 7.4320 (15) Å

• β = 90.22 (3)°

• V = 1310.2 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.25 mm⁻¹

• T = 293 (2) K

• 0.25 × 0.20 × 0.18 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: none

• 2964 measured reflections

• 2764 independent reflections

• 2022 reflections with I > 2σ(I)

• R _int = 0.017

• 3 standard reflections every 100 reflections intensity decay: none

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.132

• S = 1.09

• 2764 reflections

• 173 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 1990 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1i	0.86	2.56	3.3744 (19)	158
C3—H3A⋯S1ii	0.93	2.84	3.725 (3)	159

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Thioureas have been studied for many years because of their broad antibiosis and sterilization properties Recent years study shows that thioureas not only can be used to kill insects and adjust plant growth but also have anti-viral activities (Madan et al., 1991; Reinbold et al.,1984). From our early quantum study on these compounds, we find that they have several active centers and can form polyligand complexes with metals easily (Xue et al., 2004).These complexes are widely used as anticancer medicines Therefore study on thioureas has important impact on the future. In order to search for new compounds with higher bioactivity, the title compound was synthesized and we herein report its crystal structure.

In the title compound, bond lengths and angles are generally normal. The C7—S1 bond length of 1.686 (2)Å is indicative of considerable double-bond character. The dihedral angle between the plane (C6—C8/N1/N2/S1) and the plane (C8—C13/N2) is 31.01°. The torsion angles of S1—C7—N2—C8 and N1—C7—N2—C8 are -1.31 and -179.19°, respectively.

In the crystal structure, there are weak intermolecular C—H···S and N—H···S hydrogen bonding interactions. These interactions stabilize the title structure.

Experimental

The title compound was prepared by reaction of 2-nitrobenzenamine (0.05 mol), KOH (0.15 mol) and 1-isothiocyanatobenzene (0.05 mol) in the ethanol solution (40 ml) at room temperature. Single crystals of the title compound suitable for X-ray measurements was obtained by recrystallization from ethanol/acetone (v/v=1:1) at room temperature.

Refinement

The H atoms were fixed geometrically and were treated as riding on the parent C atoms, with C—H = 0.93 Å and N—H = 0.86 Å, and U_iso=1.2 times U_eq of the parent atoms.

Figures

Fig. 1.

The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C13H11N3O2S	F000 = 568
Mr = 273.31	Dx = 1.386 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.3110 (15) Å	θ = 1.7–27.0º
b = 24.113 (5) Å	µ = 0.25 mm−1
c = 7.4320 (15) Å	T = 293 (2) K
β = 90.22 (3)º	Block, yellow
V = 1310.2 (5) Å3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.017
Radiation source: fine-focus sealed tube	θmax = 27.0º
Monochromator: graphite	θmin = 1.7º
T = 293(2) K	h = 0→8
ω scans	k = 0→28
Absorption correction: none	l = −8→8
2964 measured reflections	3 standard reflections
2764 independent reflections	every 100 reflections
2022 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.0588P)2 + 0.4395P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.132	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.31 e Å−3
2764 reflections	Δρmin = −0.41 e Å−3
173 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.115 (6)
Secondary atom site location: difference Fourier map

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.20879 (9)	0.56603 (3)	0.96789 (9)	0.0669 (3)
O1	−0.0828 (3)	0.79863 (8)	1.3139 (4)	0.1026 (8)
O2	−0.1250 (3)	0.71304 (8)	1.3693 (3)	0.0785 (6)
N1	−0.0460 (3)	0.55266 (7)	1.2122 (3)	0.0556 (5)
H1A	−0.0549	0.5206	1.1619	0.067*
N2	0.0901 (2)	0.63776 (7)	1.2248 (2)	0.0482 (4)
H2A	0.0145	0.6425	1.3119	0.058*
N3	−0.0333 (3)	0.75057 (8)	1.3045 (3)	0.0577 (5)
C1	−0.1032 (4)	0.57222 (10)	1.5305 (3)	0.0622 (6)
H1B	0.0220	0.5731	1.5528	0.075*
C2	−0.2268 (5)	0.58020 (11)	1.6701 (4)	0.0767 (8)
H2B	−0.1840	0.5866	1.7863	0.092*
C3	−0.4120 (5)	0.57870 (12)	1.6372 (5)	0.0844 (10)
H3A	−0.4939	0.5848	1.7305	0.101*
C4	−0.4759 (4)	0.56819 (12)	1.4666 (5)	0.0853 (10)
H4A	−0.6013	0.5663	1.4458	0.102*
C5	−0.3554 (3)	0.56029 (10)	1.3246 (4)	0.0635 (6)
H5A	−0.3990	0.5533	1.2091	0.076*
C6	−0.1685 (3)	0.56302 (8)	1.3585 (3)	0.0477 (5)
C7	0.0815 (3)	0.58703 (9)	1.1440 (3)	0.0462 (5)
C8	0.2032 (3)	0.68340 (8)	1.1878 (2)	0.0423 (5)
C9	0.3819 (3)	0.67718 (9)	1.1219 (3)	0.0509 (5)
H9A	0.4277	0.6417	1.1030	0.061*
C10	0.4912 (3)	0.72225 (11)	1.0846 (3)	0.0601 (6)
H10A	0.6086	0.7167	1.0403	0.072*
C11	0.4284 (4)	0.77548 (10)	1.1125 (3)	0.0649 (7)
H11A	0.5015	0.8057	1.0836	0.078*
C12	0.2561 (4)	0.78358 (9)	1.1834 (3)	0.0599 (6)
H12A	0.2143	0.8193	1.2058	0.072*
C13	0.1449 (3)	0.73817 (8)	1.2216 (3)	0.0465 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0690 (4)	0.0677 (4)	0.0644 (4)	−0.0224 (3)	0.0339 (3)	−0.0228 (3)
O1	0.0986 (16)	0.0629 (12)	0.147 (2)	0.0267 (11)	0.0178 (14)	−0.0059 (12)
O2	0.0682 (11)	0.0700 (12)	0.0977 (14)	0.0081 (9)	0.0318 (10)	−0.0063 (10)
N1	0.0613 (12)	0.0468 (10)	0.0589 (11)	−0.0139 (8)	0.0251 (9)	−0.0121 (8)
N2	0.0478 (10)	0.0446 (9)	0.0523 (10)	−0.0057 (7)	0.0190 (8)	−0.0050 (7)
N3	0.0621 (12)	0.0547 (11)	0.0562 (11)	0.0099 (10)	−0.0038 (9)	−0.0074 (9)
C1	0.0589 (14)	0.0683 (15)	0.0595 (15)	−0.0087 (11)	0.0147 (11)	−0.0049 (11)
C2	0.104 (2)	0.0671 (16)	0.0595 (15)	−0.0087 (15)	0.0338 (15)	−0.0044 (12)
C3	0.092 (2)	0.0666 (17)	0.095 (2)	0.0051 (15)	0.0597 (19)	0.0042 (15)
C4	0.0514 (15)	0.0791 (19)	0.126 (3)	0.0074 (13)	0.0338 (16)	0.0107 (18)
C5	0.0527 (14)	0.0594 (14)	0.0787 (17)	0.0021 (11)	0.0120 (12)	0.0061 (12)
C6	0.0504 (12)	0.0376 (10)	0.0552 (12)	−0.0051 (8)	0.0195 (9)	0.0013 (8)
C7	0.0441 (11)	0.0480 (11)	0.0466 (11)	−0.0048 (9)	0.0117 (8)	−0.0016 (9)
C8	0.0460 (11)	0.0449 (10)	0.0362 (10)	−0.0060 (8)	0.0024 (8)	0.0019 (8)
C9	0.0464 (11)	0.0558 (12)	0.0505 (12)	−0.0058 (9)	0.0070 (9)	−0.0018 (9)
C10	0.0529 (13)	0.0753 (17)	0.0522 (13)	−0.0214 (11)	0.0042 (10)	−0.0002 (11)
C11	0.0758 (17)	0.0615 (15)	0.0575 (14)	−0.0303 (13)	−0.0017 (12)	0.0054 (11)
C12	0.0816 (17)	0.0441 (11)	0.0540 (13)	−0.0103 (11)	−0.0096 (12)	0.0012 (9)
C13	0.0517 (12)	0.0484 (11)	0.0394 (10)	−0.0013 (9)	−0.0041 (9)	−0.0005 (8)

Geometric parameters (Å, °)

S1—C7	1.686 (2)	C3—H3A	0.9300
O1—N3	1.216 (3)	C4—C5	1.391 (4)
O2—N3	1.226 (3)	C4—H4A	0.9300
N1—C7	1.348 (3)	C5—C6	1.390 (3)
N1—C6	1.433 (3)	C5—H5A	0.9300
N1—H1A	0.8600	C8—C9	1.405 (3)
N2—C7	1.364 (3)	C8—C13	1.411 (3)
N2—C8	1.404 (2)	C9—C10	1.378 (3)
N2—H2A	0.8600	C9—H9A	0.9300
N3—C13	1.474 (3)	C10—C11	1.379 (4)
C1—C6	1.381 (4)	C10—H10A	0.9300
C1—C2	1.392 (3)	C11—C12	1.381 (4)
C1—H1B	0.9300	C11—H11A	0.9300
C2—C3	1.375 (5)	C12—C13	1.394 (3)
C2—H2B	0.9300	C12—H12A	0.9300
C3—C4	1.373 (5)
C7—N1—C6	127.83 (17)	C1—C6—C5	120.8 (2)
C7—N1—H1A	116.1	C1—C6—N1	121.0 (2)
C6—N1—H1A	116.1	C5—C6—N1	118.1 (2)
C7—N2—C8	129.97 (16)	N1—C7—N2	114.60 (17)
C7—N2—H2A	115.0	N1—C7—S1	119.45 (16)
C8—N2—H2A	115.0	N2—C7—S1	125.92 (15)
O1—N3—O2	121.2 (2)	N2—C8—C9	122.26 (18)
O1—N3—C13	118.8 (2)	N2—C8—C13	121.35 (18)
O2—N3—C13	120.00 (18)	C9—C8—C13	116.35 (18)
C6—C1—C2	119.3 (3)	C10—C9—C8	121.8 (2)
C6—C1—H1B	120.4	C10—C9—H9A	119.1
C2—C1—H1B	120.4	C8—C9—H9A	119.1
C3—C2—C1	120.3 (3)	C9—C10—C11	120.7 (2)
C3—C2—H2B	119.8	C9—C10—H10A	119.7
C1—C2—H2B	119.8	C11—C10—H10A	119.7
C4—C3—C2	120.0 (2)	C10—C11—C12	119.6 (2)
C4—C3—H3A	120.0	C10—C11—H11A	120.2
C2—C3—H3A	120.0	C12—C11—H11A	120.2
C3—C4—C5	120.8 (3)	C11—C12—C13	120.0 (2)
C3—C4—H4A	119.6	C11—C12—H12A	120.0
C5—C4—H4A	119.6	C13—C12—H12A	120.0
C6—C5—C4	118.8 (3)	C12—C13—C8	121.5 (2)
C6—C5—H5A	120.6	C12—C13—N3	116.3 (2)
C4—C5—H5A	120.6	C8—C13—N3	122.17 (18)
C6—C1—C2—C3	0.3 (4)	N2—C8—C9—C10	179.4 (2)
C1—C2—C3—C4	1.3 (4)	C13—C8—C9—C10	−2.8 (3)
C2—C3—C4—C5	−1.6 (4)	C8—C9—C10—C11	0.5 (3)
C3—C4—C5—C6	0.2 (4)	C9—C10—C11—C12	1.9 (4)
C2—C1—C6—C5	−1.6 (3)	C10—C11—C12—C13	−1.9 (4)
C2—C1—C6—N1	−177.8 (2)	C11—C12—C13—C8	−0.6 (3)
C4—C5—C6—C1	1.4 (3)	C11—C12—C13—N3	177.4 (2)
C4—C5—C6—N1	177.6 (2)	N2—C8—C13—C12	−179.37 (19)
C7—N1—C6—C1	−63.3 (3)	C9—C8—C13—C12	2.9 (3)
C7—N1—C6—C5	120.4 (3)	N2—C8—C13—N3	2.8 (3)
C6—N1—C7—N2	−1.0 (3)	C9—C8—C13—N3	−174.95 (18)
C6—N1—C7—S1	−179.05 (19)	O1—N3—C13—C12	9.1 (3)
C8—N2—C7—N1	−179.2 (2)	O2—N3—C13—C12	−167.8 (2)
C8—N2—C7—S1	−1.3 (3)	O1—N3—C13—C8	−172.9 (2)
C7—N2—C8—C9	−31.8 (3)	O2—N3—C13—C8	10.2 (3)
C7—N2—C8—C13	150.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.86	2.56	3.3744 (19)	158
C3—H3A···S1ii	0.93	2.84	3.725 (3)	159

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