supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

hg2385 scheme

Acta Cryst. (2008). E64, o812    [ doi:10.1107/S1600536808006806 ]

(R)-1-(4-Bromobenzoyl)-4-(1-phenylpropyl)thiosemicarbazide

M. Serwer, M. Khawar Rauf, M. Ebihara and S. Hameed

Abstract top

The title compound, C17H18BrN3OS, is an important intermediate for the synthesis of biologically active heterocyclic compounds. The thiourea group is approximately planar. The crystal structure is stabilized by intermolecular N-H...O hydrogen-bonding interactions.

Comment top

Thiosemicarbazides have attracted much attention partly because of their biological activities such as antifungal (Mohareb et al., 2007), antibacterial (Kucukguzel et al., 2006), antiamoebic (Singh et al., 2005) antitubercular (Cardia et al.,2006), corrosion inhibitors (Singh et al., 2003) and partly because of their use as intermediates in the synthesis of many biologically active heterocyclic compounds like 1,3,4-oxadiazoles (Dolman et al., 2006), 1,3,4-thiadiazoles (Jalilian et al.,2000) and 1,2,4-triazole (Akhtar et al., 2007; Akhtar et al., 2006). The other important biologically active compounds synthesized from thiosemicarbazides include thiazoles, thiazines, thiadiazines, pyrazines and indazoles (Hassan et al., 2006). The C2—S1 and C1—O1 bonds both show the expected full double-bond character, while the short values for the C1—N1, C2—N2, N1—N2,C2—N3 and C9—N3 bond lengths also indicate partial double-bond character. The thiourea group is approximately planar. The crystal packing is stabilized by N(1)—H(1)···O(1) and N(3)—H(3)···S(1) hydrogen bonds.

Related literature top

For related literature, see: Akhtar et al. (2006, 2007); Cardia et al. (2006); Dolman et al. (2006); Hassan et al. (2006); Jalilian et al. (2000); Kucukguzel et al. (2006); Mohareb et al. (2007); Singh et al. (2003, 2005).

Experimental top

The 4-bromobenzoic acid hydrazide (0.0068 moles) was dissolved in methanol (30ml) and a solution of 0.0066 moles of R-(+)-1-phenylpropylisothiocyanate, separately dissolved in 10 ml of methanol, was added drop wise with continuous stirring. The reaction mixture was refluxed and after consumption of the starting materials (tlc), the mixture was cooled to room temperature and methanol evaporated in vacuo. The crude thiosemicarbazide was recrystallized from a mixture of ethyl acetate and petroleum ether. Yield: 85%; m.p 160-161 °C; Rf: 0.34 (Petroleum ether: acetone; 6:4); IR (νmax, KBr, cm-1): 3378, 3273, 3191, 3033, 2967, 2877, 1669, 1238, 1591, 1528, 699; 1H-NMR (Acetone-d6): δ 9.81 (1H, s), 8.58 (1H, s), 8.06 (1H, s), 0.97 (3H, t, J = 7.5 Hz), 1.92-1.82 (2H, m), 5.58 (1H, dd, J = 15.6, 7.2 Hz), 7.39 (2H, dd, J = 7.2, 1.5 Hz ), 7.30 (2H, dt, J = 7.5, 3.0 Hz), 7.22 (1H, dt, J = 7.2, 3.0 Hz), 7.92 (2H, d, J = 8.4 Hz), 7.72 (2H, d, J = 8.7 Hz); 13C-NMR (Acetone-d6):δ 183.51, 165.60, 142.88, 133.20, 131.64, 129.61, 128.10, 126.87, 126.74,126.12, 59.55, 28.21, 10.47; EIMS: (m/z %) 214 (20), 183 (100), 155 (55),104 (10), 76 (50), 50 (45). Elemental analysis for C17H18N3SOBr (391):C, 52.05; H, 4.62; N, 10.71; S, 8.17. Found: C, 51.96; H, 4.70; N, 10.82; S, 8.07.

Refinement top

H atom on the N atom was refined isotropically. Other H atoms were placed in idealized positions and treated as riding atoms with C—H distance in the range 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C).

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and TEXSAN (Molecular Structure Corporation & Rigaku, 2004).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. Showing hydrogen bonded molecules through N—H···O.
(R)-1-(4-Bromobenzoyl)-4-(1-phenylpropyl)thiosemicarbazide top
Crystal data top
C17H18BrN3OSF000 = 800
Mr = 392.31Dx = 1.552 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71070 Å
Hall symbol: P 2ac 2abCell parameters from 4820 reflections
a = 6.263 (3) Åθ = 3.1–27.5º
b = 9.698 (5) ŵ = 2.58 mm−1
c = 27.651 (15) ÅT = 123 (2) K
V = 1679.5 (15) Å3Block, colourles
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		3824 independent reflections
Radiation source: fine-focus sealed tube3516 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.057
T = 123(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: integration
(NUMABS; Higashi, 1999)		h = −8→8
Tmin = 0.512, Tmax = 0.627k = −12→8
13732 measured reflectionsl = −26→35
Refinement top
Refinement on F2H atoms treated by a mixture of
independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + 1.3691P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.048(Δ/σ)max < 0.001
wR(F2) = 0.074Δρmax = 0.34 e Å−3
S = 1.13Δρmin = −0.35 e Å−3
3824 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
219 parametersExtinction coefficient: 0.0018 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1584 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.020 (10)
Hydrogen site location: inferred from neighbouring sites
Crystal data top
C17H18BrN3OSV = 1679.5 (15) Å3
Mr = 392.31Z = 4
Orthorhombic, P212121Mo Kα
a = 6.263 (3) ŵ = 2.58 mm−1
b = 9.698 (5) ÅT = 123 (2) K
c = 27.651 (15) Å0.30 × 0.25 × 0.20 mm
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		3824 independent reflections
Absorption correction: integration
(NUMABS; Higashi, 1999)		3516 reflections with I > 2σ(I)
Tmin = 0.512, Tmax = 0.627Rint = 0.057
13732 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.074Δρmax = 0.34 e Å−3
S = 1.13Δρmin = −0.35 e Å−3
3824 reflectionsAbsolute structure: Flack (1983), 1584 Friedel pairs
219 parametersFlack parameter: 0.020 (10)
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
xyzUiso*/Ueq
C10.0742 (6)0.2098 (3)0.24009 (12)0.0141 (8)
O10.0089 (4)0.0922 (2)0.23367 (10)0.0260 (7)
N1−0.0306 (5)0.3005 (3)0.26956 (12)0.0144 (7)
H10.006 (6)0.384 (4)0.2666 (13)0.017*
C2−0.2924 (6)0.2804 (3)0.33209 (13)0.0124 (8)
S1−0.55059 (15)0.30911 (9)0.34643 (4)0.0169 (2)
N2−0.2383 (5)0.2701 (3)0.28467 (12)0.0144 (7)
H2−0.319 (7)0.288 (4)0.2668 (15)0.017*
N3−0.1369 (5)0.2639 (3)0.36436 (12)0.0146 (6)
H3−0.024 (6)0.254 (3)0.3547 (15)0.017*
C30.2725 (6)0.2613 (3)0.21649 (13)0.0134 (8)
C40.3408 (6)0.3985 (4)0.21787 (13)0.0156 (8)
H40.26250.46430.23610.019*
C50.5216 (6)0.4390 (3)0.19285 (14)0.0171 (8)
H50.56810.53220.19390.020*
C60.6334 (7)0.3426 (3)0.16636 (12)0.0153 (7)
C70.5710 (6)0.2056 (4)0.16486 (13)0.0197 (8)
H70.65080.14010.14680.024*
C80.3915 (7)0.1659 (3)0.18998 (13)0.0169 (8)
H80.34790.07210.18930.020*
Br10.87772 (7)0.39971 (4)0.131114 (15)0.02482 (12)
C9−0.1593 (6)0.2802 (3)0.41665 (12)0.0152 (8)
H9−0.30330.32170.42240.018*
C10−0.1581 (6)0.1398 (3)0.44199 (13)0.0154 (8)
C11−0.3136 (6)0.0440 (3)0.42905 (14)0.0207 (9)
H11−0.41710.06740.40530.025*
C12−0.3188 (7)−0.0852 (4)0.45040 (15)0.0258 (10)
H12−0.4244−0.15030.44100.031*
C13−0.1711 (7)−0.1193 (4)0.48521 (14)0.0273 (10)
H13−0.1748−0.20780.49990.033*
C14−0.0166 (7)−0.0245 (4)0.49888 (16)0.0305 (11)
H140.0848−0.04750.52310.037*
C15−0.0110 (6)0.1039 (4)0.47705 (14)0.0231 (9)
H150.09560.16830.48630.028*
C160.0052 (6)0.3842 (4)0.43521 (13)0.0200 (8)
H16A0.15060.34750.42960.024*
H16B−0.01370.39660.47050.024*
C17−0.0165 (7)0.5243 (4)0.41003 (15)0.0276 (10)
H17A0.02090.51470.37580.041*
H17B0.07980.59090.42540.041*
H17C−0.16410.55690.41290.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.017 (2)0.0147 (16)0.0109 (19)0.0004 (14)0.0000 (16)0.0045 (13)
O10.0226 (16)0.0156 (12)0.0397 (18)−0.0052 (12)0.0131 (13)−0.0043 (12)
N10.0114 (16)0.0133 (13)0.0185 (19)−0.0054 (12)0.0049 (14)0.0010 (12)
C20.0131 (19)0.0096 (15)0.015 (2)−0.0006 (13)0.0013 (16)−0.0013 (13)
S10.0102 (5)0.0220 (4)0.0184 (5)0.0014 (4)0.0029 (4)0.0007 (4)
N20.0078 (17)0.0215 (16)0.0140 (19)−0.0001 (13)−0.0027 (14)0.0057 (13)
N30.0102 (15)0.0230 (13)0.0105 (16)0.0013 (12)0.0013 (17)−0.0019 (12)
C30.0120 (19)0.0140 (16)0.014 (2)0.0009 (13)−0.0015 (16)0.0044 (13)
C40.015 (2)0.0156 (15)0.0165 (19)0.0032 (17)0.0005 (16)0.0038 (15)
C50.018 (2)0.0155 (17)0.018 (2)−0.0002 (14)−0.0004 (18)0.0023 (14)
C60.0116 (18)0.0256 (16)0.0087 (18)0.0002 (15)0.0002 (18)0.0040 (13)
C70.020 (2)0.0242 (17)0.015 (2)0.0037 (15)0.0044 (17)−0.0027 (15)
C80.016 (2)0.0158 (15)0.019 (2)−0.0009 (15)0.0043 (19)0.0004 (13)
Br10.01688 (19)0.03197 (19)0.0256 (2)−0.00092 (17)0.0097 (2)0.00672 (18)
C90.015 (2)0.0230 (17)0.0078 (19)−0.0003 (15)0.0031 (16)−0.0007 (13)
C100.018 (2)0.0194 (16)0.0090 (18)0.0018 (14)0.0014 (17)−0.0006 (12)
C110.020 (2)0.0270 (18)0.015 (2)−0.0036 (15)−0.0038 (17)0.0045 (15)
C120.028 (3)0.028 (2)0.021 (2)−0.0071 (18)0.0013 (18)−0.0019 (17)
C130.038 (3)0.0230 (19)0.021 (2)0.0071 (18)0.005 (2)0.0009 (16)
C140.035 (3)0.033 (2)0.023 (3)0.0116 (19)−0.011 (2)0.0005 (18)
C150.027 (2)0.0242 (18)0.018 (2)−0.0021 (19)−0.0045 (18)0.0018 (18)
C160.020 (2)0.0275 (18)0.013 (2)−0.0051 (16)0.0007 (16)−0.0030 (16)
C170.032 (3)0.030 (2)0.021 (2)−0.0109 (18)0.004 (2)0.0027 (17)
Geometric parameters (Å, °) top
C1—O11.224 (4)C8—H80.9500
C1—N11.367 (4)C9—C161.531 (5)
C1—C31.489 (5)C9—C101.532 (4)
N1—N21.397 (4)C9—H91.0000
N1—H10.84 (4)C10—C151.382 (5)
C2—N31.330 (5)C10—C111.393 (5)
C2—N21.358 (5)C11—C121.386 (5)
C2—S11.688 (4)C11—H110.9500
N2—H20.73 (4)C12—C131.376 (6)
N3—C91.461 (5)C12—H120.9500
N3—H30.76 (4)C13—C141.387 (6)
C3—C81.396 (5)C13—H130.9500
C3—C41.398 (5)C14—C151.384 (5)
C4—C51.384 (5)C14—H140.9500
C4—H40.9500C15—H150.9500
C5—C61.379 (5)C16—C171.532 (5)
C5—H50.9500C16—H16A0.9900
C6—C71.386 (5)C16—H16B0.9900
C6—Br11.897 (4)C17—H17A0.9800
C7—C81.376 (5)C17—H17B0.9800
C7—H70.9500C17—H17C0.9800
O1—C1—N1121.7 (3)C16—C9—C10115.4 (3)
O1—C1—C3121.8 (3)N3—C9—H9106.8
N1—C1—C3116.5 (3)C16—C9—H9106.8
C1—N1—N2119.3 (3)C10—C9—H9106.8
C1—N1—H1115 (3)C15—C10—C11118.6 (3)
N2—N1—H1119 (3)C15—C10—C9123.3 (3)
N3—C2—N2117.1 (3)C11—C10—C9118.2 (3)
N3—C2—S1124.3 (3)C12—C11—C10120.7 (4)
N2—C2—S1118.6 (3)C12—C11—H11119.6
C2—N2—N1120.4 (3)C10—C11—H11119.6
C2—N2—H2118 (3)C13—C12—C11120.0 (4)
N1—N2—H2113 (3)C13—C12—H12120.0
C2—N3—C9125.5 (3)C11—C12—H12120.0
C2—N3—H3117 (3)C12—C13—C14120.0 (4)
C9—N3—H3117 (3)C12—C13—H13120.0
C8—C3—C4118.8 (3)C14—C13—H13120.0
C8—C3—C1117.0 (3)C15—C14—C13119.7 (4)
C4—C3—C1124.2 (3)C15—C14—H14120.2
C5—C4—C3120.4 (3)C13—C14—H14120.2
C5—C4—H4119.8C10—C15—C14121.1 (4)
C3—C4—H4119.8C10—C15—H15119.5
C6—C5—C4119.2 (3)C14—C15—H15119.5
C6—C5—H5120.4C9—C16—C17111.8 (3)
C4—C5—H5120.4C9—C16—H16A109.3
C5—C6—C7121.5 (4)C17—C16—H16A109.3
C5—C6—Br1119.0 (3)C9—C16—H16B109.3
C7—C6—Br1119.5 (3)C17—C16—H16B109.3
C8—C7—C6118.9 (3)H16A—C16—H16B107.9
C8—C7—H7120.5C16—C17—H17A109.5
C6—C7—H7120.5C16—C17—H17B109.5
C7—C8—C3121.0 (3)H17A—C17—H17B109.5
C7—C8—H8119.5C16—C17—H17C109.5
C3—C8—H8119.5H17A—C17—H17C109.5
N3—C9—C16109.8 (3)H17B—C17—H17C109.5
N3—C9—C10110.8 (3)
O1—C1—N1—N2−13.7 (5)C4—C3—C8—C7−1.1 (6)
C3—C1—N1—N2166.7 (3)C1—C3—C8—C7176.6 (3)
N3—C2—N2—N1−26.7 (4)C2—N3—C9—C16−125.2 (3)
S1—C2—N2—N1154.7 (2)C2—N3—C9—C10106.1 (4)
C1—N1—N2—C2131.2 (3)N3—C9—C10—C15121.4 (4)
N2—C2—N3—C9175.6 (3)C16—C9—C10—C15−4.2 (5)
S1—C2—N3—C9−6.0 (4)N3—C9—C10—C11−58.7 (4)
O1—C1—C3—C8−5.4 (5)C16—C9—C10—C11175.7 (3)
N1—C1—C3—C8174.2 (3)C15—C10—C11—C12−0.8 (6)
O1—C1—C3—C4172.1 (3)C9—C10—C11—C12179.3 (3)
N1—C1—C3—C4−8.3 (5)C10—C11—C12—C130.8 (6)
C8—C3—C4—C50.8 (5)C11—C12—C13—C14−0.1 (6)
C1—C3—C4—C5−176.7 (3)C12—C13—C14—C15−0.5 (6)
C3—C4—C5—C60.2 (5)C11—C10—C15—C140.2 (6)
C4—C5—C6—C7−1.1 (6)C9—C10—C15—C14−180.0 (4)
C4—C5—C6—Br1178.7 (3)C13—C14—C15—C100.5 (6)
C5—C6—C7—C80.8 (6)N3—C9—C16—C1757.4 (4)
Br1—C6—C7—C8−179.0 (3)C10—C9—C16—C17−176.5 (3)
C6—C7—C8—C30.3 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.84 (4)2.03 (4)2.834 (4)161 (4)
Symmetry codes: (i) −x, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.84 (4)2.03 (4)2.834 (4)161 (4)
Symmetry codes: (i) −x, y+1/2, −z+1/2.
Acknowledgements top

MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International support initiative program for Doctoral Fellowships at Gifu University, Japan.

references
References top

Akhtar, T., Hameed, S., Al-Masoudi, N. A. & Khan, K. M. (2007). Heteroat. Chem. 18, 316–322.

Akhtar, T., Hameed, S., Lu, X., Yasin, K. A. & Khan, M. H. (2006). Anal. Sci. X-Ray Struct. Anal. Online, 22, 307–308.

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.

Cardia, M. C., Distinto, S., Maccioni, E., Plumitallo, A., Saddi, M., Sanna, M. L. & DeLogu, A. (2006). J. Heterocycl. Chem. 43, 1337–1342.

Dolman, S. J., Gosselin, F., O'Shea, P. D. & Davies, I. W. (2006). J. Org. Chem. 71, 9548–9551.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Hassan, A. A., Mourad, A. E., El-Shaieb, K. M. & Abou-Zeid, A. H. (2006). J. Heterocycl. Chem. 43, 471–476.

Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.

Jalilian, A. R., Sattari, S., Bineshmarvasti, M., Shafiee, A. & Daneshtalab, M. (2000). Arch. Pharm. Pharm. Med. Chem. 333, 347–354.

Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tenessee, USA.

Kucukguzel, G., Kocatepa, A., DeClercq, E., Sahin, F. & Gulluce, M. (2006). Eur. J. Med. Chem. 41, 353–359.

Mohareb, R. M., Ho, J. Z. & Mohamed, A. A. (2007). Phosphorus Sulfur Silicon Relat. Elem. 182, 1661–1681.

Molecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Molecular Structure Corporation & Rigaku (2004). TEXSAN. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Singh, S., Husain, K., Athar, F. & Azam, A. (2005). Eur. J. Pharm. Sci. 25, 255–262.

Singh, M. M., Rastogi, R. B., Upadhyay, B. N. & Yadav, M. (2003). Mater. Chem. Phys. 80, 283–293.