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Acta Cryst. (2009). E65, o2447    [ doi:10.1107/S1600536809035880 ]

1-[2-(2,4-Dinitrobenzylideneamino)phenyl]-3-phenylthiourea

M. Umadevi, S. Devaraj, M. Kandaswamy, G. Chakkaravarthi and V. Manivannan

Abstract top

In the title compound, C20H15N5O4S, the central benzene ring makes dihedral angles of 59.5 (1) and 51.7 (1)°, respectively, with the terminal phenyl and benzene rings. The molecular structure exhibits weak intramolecular N-H...N and C-H...S interactions. In the crystal structure, molecules are linked by weak intermolecular N-H...S and C-H...O interactions, forming a chain along [1\overline{1}1].

Comment top

Thioureas are known to exhibit antiviral, antibacterial, anticancer (Madan & Taneja, 1991; Manjula et al., 2009), antifungal, antitubercular, antithyroidal, herbicidal and insecticidal (Huebner et al., 1953) activities.

The geometric parameters in (I), (Fig. 1) agree with the reported values of similar structures (Gayathri et al., 2007, 2008). The benzene ring C1—C6 makes the dihedral angle of 59.5 (1)° with the phenyl ring C15—C20 and 51.7 (1)° with the dinitrobenzene ring C8—C13.

The molecular structure of (I) exhibits weak intramolecular N—H···N, C—H···S and C—H···O interactions and the crystal structure is stabilized by weak intermolecular N—H···S and C—H···O interactions (Table 1 and Fig. 2). The intermolecular N5—H5A···S1 interaction generates an eight-membered ring, with graph-set motif R22(8) and the C12—H12···O3 interaction generates a ten-membered ring, with graph-set motif R22(10) (Bernstein, 1995).

Related literature top

For the biological activity of thioureas, see: Huebner et al. (1953); Madan & Taneja (1991); Manjula et al. (2009). For related structures, see: Gayathri et al. (2007, 2008). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

To the solution of 1-(2-aminophenyl)-3-phenylthiourea (0.3 g, 1.2 mmol) in methanol (25 ml), 2,4-dinitrobenzaldehyde (0.36 g, 1.2 mmol) in methanol (25 ml) was added under stirring. The resulting mixture was refluxed for 3 h and cooled to room temperature. The solid product was collected by filtration and washed with cold methanol. The microcrystalline compound was recrystallized from hot chloroform.

Refinement top

H atoms were positioned geometrically and refined using riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), and with N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.
1-[2-(2,4-Dinitrobenzylideneamino)phenyl]-3-phenylthiourea top
Crystal data top
C20H15N5O4SF(000) = 872
Mr = 421.43Dx = 1.446 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9702 reflections
a = 8.362 (5) Åθ = 2.2–32.3°
b = 18.767 (3) ŵ = 0.21 mm−1
c = 12.379 (4) ÅT = 295 K
β = 94.827 (5)°Prism, orange
V = 1935.7 (14) Å30.20 × 0.16 × 0.16 mm
Z = 4
Data collection top
Bruker Kappa APEXII
diffractometer		6878 independent reflections
Radiation source: fine-focus sealed tube4509 reflections with I > 2σ(I)
graphiteRint = 0.028
ω and φ scansθmax = 32.3°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.960, Tmax = 0.968k = −28→26
28336 measured reflectionsl = −9→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0628P)2 + 0.3472P]
where P = (Fo2 + 2Fc2)/3
6878 reflections(Δ/σ)max < 0.001
271 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.37 e Å−3
Crystal data top
C20H15N5O4SV = 1935.7 (14) Å3
Mr = 421.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.362 (5) ŵ = 0.21 mm−1
b = 18.767 (3) ÅT = 295 K
c = 12.379 (4) Å0.20 × 0.16 × 0.16 mm
β = 94.827 (5)°
Data collection top
Bruker Kappa APEXII
diffractometer		4509 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.028
Tmin = 0.960, Tmax = 0.968θmax = 32.3°
28336 measured reflectionsStandard reflections: 0
6878 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.137Δρmax = 0.25 e Å−3
S = 1.02Δρmin = −0.37 e Å−3
6878 reflectionsAbsolute structure: ?
271 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.62398 (16)0.29698 (7)0.34283 (10)0.0381 (3)
C20.65955 (15)0.23913 (7)0.41328 (9)0.0360 (3)
C30.76661 (18)0.24941 (8)0.50420 (11)0.0448 (3)
H30.78600.21270.55410.054*
C40.84381 (19)0.31360 (9)0.52044 (12)0.0511 (4)
H40.91490.32000.58160.061*
C50.8174 (2)0.36867 (9)0.44751 (13)0.0560 (4)
H50.87400.41110.45760.067*
C60.70627 (19)0.36049 (8)0.35919 (12)0.0496 (4)
H60.68680.39790.31060.060*
C70.42126 (16)0.33645 (8)0.21914 (10)0.0412 (3)
H70.43210.38090.25220.049*
C80.30541 (16)0.32650 (7)0.12401 (10)0.0381 (3)
C90.32496 (18)0.26958 (8)0.05491 (11)0.0459 (3)
H90.40400.23590.07390.055*
C100.23061 (19)0.26145 (9)−0.04113 (11)0.0478 (3)
H100.24410.2225−0.08590.057*
C110.11616 (16)0.31229 (8)−0.06909 (10)0.0425 (3)
C120.08777 (17)0.36881 (8)−0.00335 (11)0.0424 (3)
H120.00870.4023−0.02340.051*
C130.18123 (16)0.37421 (8)0.09399 (10)0.0393 (3)
C140.57689 (16)0.11081 (7)0.42739 (10)0.0387 (3)
C150.41735 (19)0.06746 (7)0.26115 (11)0.0435 (3)
C160.2548 (2)0.05512 (8)0.24467 (12)0.0471 (3)
H160.19550.04570.30340.057*
C170.1798 (2)0.05672 (10)0.14094 (14)0.0606 (4)
H170.07000.04820.12980.073*
C180.2668 (3)0.07077 (10)0.05446 (13)0.0687 (5)
H180.21610.0721−0.01530.082*
C190.4278 (3)0.08286 (11)0.07051 (14)0.0703 (5)
H190.48620.09230.01140.084*
C200.5058 (2)0.08133 (10)0.17423 (13)0.0599 (4)
H200.61570.08950.18490.072*
N10.01932 (16)0.30558 (9)−0.17349 (10)0.0534 (3)
N20.14010 (17)0.43172 (8)0.16707 (11)0.0542 (3)
N30.50634 (14)0.28461 (6)0.25608 (9)0.0406 (3)
N40.58017 (14)0.17574 (6)0.38222 (8)0.0409 (3)
H4A0.52160.17910.32190.049*
N50.49272 (17)0.06127 (7)0.36821 (10)0.0529 (3)
H5A0.48320.02060.39900.064*
O10.0455 (2)0.25501 (10)−0.23077 (11)0.0917 (5)
O2−0.08088 (15)0.35115 (8)−0.19739 (9)0.0652 (3)
O30.0704 (2)0.48301 (8)0.12851 (13)0.0930 (5)
O40.1705 (2)0.42321 (9)0.26429 (11)0.0902 (5)
S10.66368 (5)0.08789 (2)0.55035 (3)0.04838 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0389 (7)0.0402 (7)0.0341 (5)0.0022 (5)−0.0038 (5)0.0060 (5)
C20.0366 (7)0.0377 (7)0.0330 (5)0.0040 (5)−0.0017 (5)0.0047 (5)
C30.0487 (8)0.0449 (8)0.0384 (6)0.0049 (6)−0.0100 (5)0.0062 (5)
C40.0529 (9)0.0506 (9)0.0465 (7)0.0005 (7)−0.0159 (6)−0.0013 (6)
C50.0595 (10)0.0439 (8)0.0609 (9)−0.0082 (7)−0.0171 (7)0.0021 (7)
C60.0544 (9)0.0403 (8)0.0516 (8)−0.0045 (6)−0.0108 (6)0.0107 (6)
C70.0429 (7)0.0426 (7)0.0368 (6)0.0018 (6)−0.0041 (5)0.0065 (5)
C80.0371 (7)0.0428 (7)0.0335 (5)0.0017 (5)−0.0012 (5)0.0091 (5)
C90.0442 (8)0.0509 (8)0.0416 (6)0.0108 (6)−0.0018 (5)0.0056 (6)
C100.0498 (8)0.0550 (9)0.0381 (6)0.0062 (7)0.0015 (6)−0.0022 (6)
C110.0374 (7)0.0572 (9)0.0322 (5)−0.0021 (6)−0.0015 (5)0.0077 (5)
C120.0375 (7)0.0482 (8)0.0405 (6)0.0042 (6)−0.0030 (5)0.0106 (5)
C130.0403 (7)0.0408 (7)0.0364 (6)0.0024 (6)0.0002 (5)0.0062 (5)
C140.0401 (7)0.0392 (7)0.0364 (6)0.0017 (5)−0.0001 (5)0.0072 (5)
C150.0586 (9)0.0340 (7)0.0369 (6)−0.0010 (6)−0.0032 (6)0.0032 (5)
C160.0558 (9)0.0397 (7)0.0455 (7)0.0040 (7)0.0019 (6)−0.0005 (6)
C170.0665 (11)0.0515 (10)0.0602 (9)0.0048 (8)−0.0163 (8)−0.0025 (7)
C180.1052 (16)0.0567 (11)0.0405 (7)0.0006 (10)−0.0150 (8)−0.0024 (7)
C190.1034 (17)0.0702 (12)0.0388 (7)−0.0056 (11)0.0143 (9)0.0021 (7)
C200.0657 (11)0.0657 (11)0.0489 (8)−0.0085 (9)0.0079 (7)0.0050 (7)
N10.0498 (7)0.0732 (10)0.0357 (5)−0.0006 (7)−0.0040 (5)0.0038 (6)
N20.0549 (8)0.0525 (8)0.0531 (7)0.0126 (6)−0.0072 (6)−0.0041 (6)
N30.0413 (6)0.0429 (6)0.0360 (5)−0.0013 (5)−0.0064 (4)0.0103 (4)
N40.0464 (6)0.0384 (6)0.0358 (5)−0.0013 (5)−0.0096 (4)0.0074 (4)
N50.0704 (9)0.0438 (7)0.0420 (6)−0.0131 (6)−0.0106 (6)0.0141 (5)
O10.1080 (12)0.1083 (13)0.0534 (7)0.0283 (10)−0.0248 (7)−0.0255 (8)
O20.0583 (7)0.0850 (9)0.0490 (6)0.0074 (6)−0.0157 (5)0.0116 (6)
O30.1231 (13)0.0625 (9)0.0886 (10)0.0423 (9)−0.0200 (9)−0.0069 (7)
O40.1129 (13)0.1065 (12)0.0489 (7)0.0467 (10)−0.0073 (7)−0.0162 (7)
S10.0547 (2)0.0481 (2)0.04016 (17)−0.00134 (16)−0.00860 (14)0.01530 (14)
Geometric parameters (Å, °) top
C1—C61.383 (2)C12—H120.9300
C1—C21.4085 (17)C13—N21.468 (2)
C1—N31.4132 (16)C14—N41.3419 (17)
C2—C31.3914 (18)C14—N51.3452 (19)
C2—N41.4003 (17)C14—S11.6860 (13)
C3—C41.374 (2)C15—C161.377 (2)
C3—H30.9300C15—C201.381 (2)
C4—C51.378 (2)C15—N51.4236 (17)
C4—H40.9300C16—C171.381 (2)
C5—C61.383 (2)C16—H160.9300
C5—H50.9300C17—C181.370 (3)
C6—H60.9300C17—H170.9300
C7—N31.2678 (17)C18—C191.363 (3)
C7—C81.4725 (18)C18—H180.9300
C7—H70.9300C19—C201.391 (2)
C8—C91.387 (2)C19—H190.9300
C8—C131.3975 (19)C20—H200.9300
C9—C101.379 (2)N1—O11.215 (2)
C9—H90.9300N1—O21.2162 (19)
C10—C111.375 (2)N2—O31.2031 (18)
C10—H100.9300N2—O41.2194 (18)
C11—C121.370 (2)N4—H4A0.8600
C11—N11.4716 (17)N5—H5A0.8600
C12—C131.3837 (18)
C6—C1—C2119.82 (12)C12—C13—N2116.50 (12)
C6—C1—N3123.98 (12)C8—C13—N2120.97 (12)
C2—C1—N3116.18 (12)N4—C14—N5115.39 (11)
C3—C2—N4126.71 (12)N4—C14—S1125.83 (11)
C3—C2—C1118.81 (13)N5—C14—S1118.76 (10)
N4—C2—C1114.48 (11)C16—C15—C20120.20 (14)
C4—C3—C2120.16 (13)C16—C15—N5118.58 (13)
C4—C3—H3119.9C20—C15—N5121.10 (15)
C2—C3—H3119.9C15—C16—C17119.97 (15)
C3—C4—C5120.97 (13)C15—C16—H16120.0
C3—C4—H4119.5C17—C16—H16120.0
C5—C4—H4119.5C18—C17—C16120.07 (18)
C4—C5—C6119.67 (15)C18—C17—H17120.0
C4—C5—H5120.2C16—C17—H17120.0
C6—C5—H5120.2C19—C18—C17120.09 (15)
C5—C6—C1120.30 (13)C19—C18—H18120.0
C5—C6—H6119.9C17—C18—H18120.0
C1—C6—H6119.9C18—C19—C20120.80 (17)
N3—C7—C8120.17 (13)C18—C19—H19119.6
N3—C7—H7119.9C20—C19—H19119.6
C8—C7—H7119.9C15—C20—C19118.87 (18)
C9—C8—C13116.94 (12)C15—C20—H20120.6
C9—C8—C7119.16 (12)C19—C20—H20120.6
C13—C8—C7123.75 (13)O1—N1—O2124.14 (13)
C10—C9—C8121.91 (13)O1—N1—C11117.79 (14)
C10—C9—H9119.0O2—N1—C11118.06 (14)
C8—C9—H9119.0O3—N2—O4123.37 (15)
C11—C10—C9118.42 (14)O3—N2—C13118.34 (13)
C11—C10—H10120.8O4—N2—C13118.15 (13)
C9—C10—H10120.8C7—N3—C1118.79 (12)
C12—C11—C10122.65 (12)C14—N4—C2133.07 (11)
C12—C11—N1118.55 (13)C14—N4—H4A113.5
C10—C11—N1118.80 (14)C2—N4—H4A113.5
C11—C12—C13117.43 (13)C14—N5—C15128.38 (12)
C11—C12—H12121.3C14—N5—H5A115.8
C13—C12—H12121.3C15—N5—H5A115.8
C12—C13—C8122.50 (13)
C6—C1—C2—C36.0 (2)N5—C15—C16—C17−176.32 (14)
N3—C1—C2—C3−175.84 (12)C15—C16—C17—C18−0.2 (2)
C6—C1—C2—N4−173.89 (14)C16—C17—C18—C190.3 (3)
N3—C1—C2—N44.25 (18)C17—C18—C19—C20−0.2 (3)
N4—C2—C3—C4175.60 (15)C16—C15—C20—C190.3 (3)
C1—C2—C3—C4−4.3 (2)N5—C15—C20—C19176.38 (16)
C2—C3—C4—C5−0.2 (3)C18—C19—C20—C15−0.1 (3)
C3—C4—C5—C63.0 (3)C12—C11—N1—O1−179.74 (16)
C4—C5—C6—C1−1.2 (3)C10—C11—N1—O1−0.1 (2)
C2—C1—C6—C5−3.3 (2)C12—C11—N1—O20.8 (2)
N3—C1—C6—C5178.69 (15)C10—C11—N1—O2−179.62 (15)
N3—C7—C8—C9−20.9 (2)C12—C13—N2—O3−24.3 (2)
N3—C7—C8—C13163.79 (13)C8—C13—N2—O3157.70 (17)
C13—C8—C9—C102.3 (2)C12—C13—N2—O4151.72 (17)
C7—C8—C9—C10−173.30 (14)C8—C13—N2—O4−26.3 (2)
C8—C9—C10—C111.1 (2)C8—C7—N3—C1175.78 (12)
C9—C10—C11—C12−2.8 (2)C6—C1—N3—C7−31.3 (2)
C9—C10—C11—N1177.57 (13)C2—C1—N3—C7150.61 (13)
C10—C11—C12—C130.9 (2)N5—C14—N4—C2−175.70 (14)
N1—C11—C12—C13−179.52 (12)S1—C14—N4—C25.9 (2)
C11—C12—C13—C82.9 (2)C3—C2—N4—C142.5 (2)
C11—C12—C13—N2−175.14 (13)C1—C2—N4—C14−177.57 (14)
C9—C8—C13—C12−4.4 (2)N4—C14—N5—C155.2 (2)
C7—C8—C13—C12171.00 (13)S1—C14—N5—C15−176.34 (13)
C9—C8—C13—N2173.51 (13)C16—C15—N5—C14−121.98 (17)
C7—C8—C13—N2−11.1 (2)C20—C15—N5—C1461.8 (2)
C20—C15—C16—C17−0.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N30.862.142.614 (2)114
C3—H3···S10.932.553.215 (2)128
C7—H7···O40.932.342.749 (3)106
N4—H4A···N30.862.142.614 (2)114
N5—H5A···S1i0.862.493.284 (2)155
C12—H12···O3ii0.932.573.397 (3)148
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N30.862.142.614 (2)114
C3—H3···S10.932.553.215 (2)128
C7—H7···O40.932.342.749 (3)106
N4—H4A···N30.862.142.614 (2)114
N5—H5A···S1i0.862.493.284 (2)155
C12—H12···O3ii0.932.573.397 (3)148
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z.
Acknowledgements top

The authors wish to acknowledge IIT, Madras for the data collection.

references
References top

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