organic compounds
1-{[(Z)-Cyclopentylidene]amino}-3-phenylthiourea
aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and eKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
*Correspondence e-mail: shaabankamel@yahoo.com
The sample of the title compound, C12H15N3S, chosen for study consisted of triclinic crystals twinned by a 180° rotation about the a axis. The five-membered ring adopts a twisted conformation. The dihedral angle between the phenyl ring and the mean plane of the thiourea unit is 78.22 (8)°. In the crystal, molecules are linked via pairs of N—H⋯S hydrogen bonds forming inversion dimers.
CCDC reference: 994387
Related literature
For the use of thiourea as a building-block in the synthesis of heterocycles, see: Yin et al. (2008). For the diverse biological properties of thiourea-containing compounds and their metal complexes, see: Saeed et al. (2010); Solomon et al. (2010); Karakuş & Rollas (2002); Abdullah & Salh (2010). For the synthesis of the title compound, see: Akkurt et al. (2014). For structural studies on thiourea derivatives, see: Struga et al. (2009). For ring-puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013); data reduction: SAINT and CELL_NOW (Sheldrick, 2008a); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).
Supporting information
CCDC reference: 994387
10.1107/S1600536814007028/sj5395sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814007028/sj5395Isup2.hkl
The title compound was prepared according to our previously reported method (Akkurt et al., 2014). Colourless crystals suitable for X-ray diffraction were obtained by crystallization of (I) from ethanol.
H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. The crystal used proved to be twinned by a 180° rotation about a, CELL_NOW, (Sheldrick, 2008a) and the final structure was refined as a 2-component twin with a refined value for the minor twin fraction of 0.23070 (18).
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013) and CELL_NOW (Sheldrick, 2008a); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).Fig. 1. Perspective view of I with 50% probability displacement ellipsoids. | |
Fig. 2. Packing viewed down the a axis and showing N—H···S interactions. |
C12H15N3S | Z = 2 |
Mr = 233.33 | F(000) = 248 |
Triclinic, P1 | Dx = 1.304 Mg m−3 |
a = 7.3997 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 7.5790 (1) Å | Cell parameters from 8773 reflections |
c = 11.4657 (2) Å | θ = 4.0–70.0° |
α = 93.0220 (9)° | µ = 2.21 mm−1 |
β = 105.4530 (9)° | T = 100 K |
γ = 104.7070 (8)° | Plate, colourless |
V = 594.45 (2) Å3 | 0.21 × 0.10 × 0.04 mm |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 11360 independent reflections |
Radiation source: INCOATEC IµS micro–focus source | 9454 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.026 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 70.0°, θmin = 4.0° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | k = −9→9 |
Tmin = 0.65, Tmax = 0.92 | l = −13→13 |
11363 measured reflections |
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)] = 0.040 | Hydrogen site location: mixed |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.1956P] where P = (Fo2 + 2Fc2)/3 |
11360 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C12H15N3S | γ = 104.7070 (8)° |
Mr = 233.33 | V = 594.45 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3997 (2) Å | Cu Kα radiation |
b = 7.5790 (1) Å | µ = 2.21 mm−1 |
c = 11.4657 (2) Å | T = 100 K |
α = 93.0220 (9)° | 0.21 × 0.10 × 0.04 mm |
β = 105.4530 (9)° |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 11360 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | 9454 reflections with I > 2σ(I) |
Tmin = 0.65, Tmax = 0.92 | Rint = 0.026 |
11363 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.28 e Å−3 |
11360 reflections | Δρmin = −0.20 e Å−3 |
146 parameters |
Experimental. Analysis of 985 reflections having I/σ(I) > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008a) showed the crystal to belong to the triclinic system and to be twinned by a 180° rotation about the a axis. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW. |
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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. Refined as a 2-component twin. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.89113 (8) | 1.01459 (7) | 0.81488 (4) | 0.02372 (18) | |
N1 | 0.7313 (2) | 0.5215 (2) | 0.90890 (15) | 0.0216 (4) | |
N2 | 0.8223 (3) | 0.7082 (2) | 0.91604 (15) | 0.0213 (4) | |
H2 | 0.8859 | 0.7824 | 0.9880 | 0.026* | |
N3 | 0.7179 (2) | 0.6693 (2) | 0.70759 (14) | 0.0226 (4) | |
H3 | 0.6668 | 0.5483 | 0.7126 | 0.027* | |
C1 | 0.7350 (3) | 0.4552 (3) | 1.01002 (18) | 0.0201 (5) | |
C2 | 0.8303 (3) | 0.5512 (3) | 1.13816 (17) | 0.0221 (5) | |
H2A | 0.7989 | 0.6695 | 1.1480 | 0.027* | |
H2B | 0.9739 | 0.5749 | 1.1600 | 0.027* | |
C3 | 0.7435 (3) | 0.4160 (3) | 1.21708 (19) | 0.0274 (5) | |
H3A | 0.8400 | 0.4244 | 1.2973 | 0.033* | |
H3B | 0.6258 | 0.4424 | 1.2306 | 0.033* | |
C4 | 0.6913 (3) | 0.2257 (3) | 1.14529 (19) | 0.0280 (5) | |
H4A | 0.5820 | 0.1399 | 1.1656 | 0.034* | |
H4B | 0.8049 | 0.1748 | 1.1635 | 0.034* | |
C5 | 0.6317 (3) | 0.2559 (3) | 1.01077 (19) | 0.0242 (5) | |
H5A | 0.6742 | 0.1736 | 0.9604 | 0.029* | |
H5B | 0.4885 | 0.2326 | 0.9791 | 0.029* | |
C6 | 0.8052 (3) | 0.7858 (3) | 0.81110 (18) | 0.0201 (5) | |
C7 | 0.6780 (3) | 0.7262 (3) | 0.58782 (18) | 0.0240 (5) | |
C8 | 0.8249 (4) | 0.7674 (3) | 0.5318 (2) | 0.0358 (6) | |
H8 | 0.9527 | 0.7619 | 0.5729 | 0.043* | |
C9 | 0.7831 (5) | 0.8171 (4) | 0.4146 (2) | 0.0453 (7) | |
H9 | 0.8827 | 0.8458 | 0.3751 | 0.054* | |
C10 | 0.5971 (5) | 0.8248 (3) | 0.3557 (2) | 0.0448 (7) | |
H10 | 0.5690 | 0.8582 | 0.2755 | 0.054* | |
C11 | 0.4526 (4) | 0.7845 (3) | 0.4123 (2) | 0.0410 (7) | |
H11 | 0.3249 | 0.7906 | 0.3714 | 0.049* | |
C12 | 0.4930 (4) | 0.7346 (3) | 0.5295 (2) | 0.0309 (5) | |
H12 | 0.3933 | 0.7066 | 0.5690 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0326 (3) | 0.0182 (3) | 0.0185 (3) | 0.0051 (2) | 0.0058 (2) | 0.0045 (2) |
N1 | 0.0248 (10) | 0.0173 (9) | 0.0231 (9) | 0.0043 (8) | 0.0089 (8) | 0.0044 (7) |
N2 | 0.0278 (10) | 0.0178 (9) | 0.0159 (9) | 0.0025 (7) | 0.0058 (7) | 0.0029 (7) |
N3 | 0.0303 (10) | 0.0178 (9) | 0.0165 (9) | 0.0016 (8) | 0.0056 (8) | 0.0036 (7) |
C1 | 0.0203 (11) | 0.0204 (11) | 0.0229 (11) | 0.0082 (9) | 0.0091 (9) | 0.0057 (9) |
C2 | 0.0244 (11) | 0.0220 (11) | 0.0208 (11) | 0.0067 (9) | 0.0070 (9) | 0.0062 (9) |
C3 | 0.0293 (12) | 0.0298 (12) | 0.0225 (11) | 0.0056 (10) | 0.0078 (10) | 0.0104 (9) |
C4 | 0.0264 (12) | 0.0257 (12) | 0.0333 (13) | 0.0064 (10) | 0.0097 (10) | 0.0135 (10) |
C5 | 0.0263 (12) | 0.0198 (11) | 0.0276 (12) | 0.0053 (9) | 0.0104 (10) | 0.0053 (9) |
C6 | 0.0197 (11) | 0.0235 (11) | 0.0196 (10) | 0.0076 (9) | 0.0076 (9) | 0.0062 (9) |
C7 | 0.0369 (13) | 0.0156 (10) | 0.0161 (10) | 0.0031 (10) | 0.0064 (10) | 0.0015 (8) |
C8 | 0.0437 (15) | 0.0386 (14) | 0.0242 (12) | 0.0061 (12) | 0.0133 (11) | 0.0051 (10) |
C9 | 0.073 (2) | 0.0360 (14) | 0.0241 (13) | −0.0004 (14) | 0.0238 (14) | 0.0033 (11) |
C10 | 0.088 (2) | 0.0192 (12) | 0.0158 (12) | 0.0041 (13) | 0.0058 (14) | 0.0039 (9) |
C11 | 0.0595 (18) | 0.0246 (13) | 0.0279 (13) | 0.0113 (12) | −0.0054 (13) | 0.0043 (10) |
C12 | 0.0402 (15) | 0.0224 (11) | 0.0269 (12) | 0.0075 (11) | 0.0054 (11) | 0.0040 (9) |
S1—C6 | 1.682 (2) | C4—C5 | 1.533 (3) |
N1—C1 | 1.284 (2) | C4—H4A | 0.9900 |
N1—N2 | 1.392 (2) | C4—H4B | 0.9900 |
N2—C6 | 1.357 (2) | C5—H5A | 0.9900 |
N2—H2 | 0.9098 | C5—H5B | 0.9900 |
N3—C6 | 1.341 (3) | C7—C12 | 1.373 (3) |
N3—C7 | 1.439 (2) | C7—C8 | 1.382 (3) |
N3—H3 | 0.9098 | C8—C9 | 1.391 (3) |
C1—C2 | 1.503 (3) | C8—H8 | 0.9500 |
C1—C5 | 1.512 (3) | C9—C10 | 1.379 (4) |
C2—C3 | 1.535 (3) | C9—H9 | 0.9500 |
C2—H2A | 0.9900 | C10—C11 | 1.373 (4) |
C2—H2B | 0.9900 | C10—H10 | 0.9500 |
C3—C4 | 1.526 (3) | C11—C12 | 1.391 (3) |
C3—H3A | 0.9900 | C11—H11 | 0.9500 |
C3—H3B | 0.9900 | C12—H12 | 0.9500 |
C1—N1—N2 | 117.12 (17) | C1—C5—C4 | 104.55 (17) |
C6—N2—N1 | 118.43 (17) | C1—C5—H5A | 110.8 |
C6—N2—H2 | 118.3 | C4—C5—H5A | 110.8 |
N1—N2—H2 | 123.1 | C1—C5—H5B | 110.8 |
C6—N3—C7 | 123.96 (16) | C4—C5—H5B | 110.8 |
C6—N3—H3 | 118.7 | H5A—C5—H5B | 108.9 |
C7—N3—H3 | 116.9 | N3—C6—N2 | 115.83 (18) |
N1—C1—C2 | 128.72 (18) | N3—C6—S1 | 123.58 (14) |
N1—C1—C5 | 120.66 (18) | N2—C6—S1 | 120.59 (16) |
C2—C1—C5 | 110.61 (16) | C12—C7—C8 | 120.89 (19) |
C1—C2—C3 | 104.01 (17) | C12—C7—N3 | 119.41 (19) |
C1—C2—H2A | 111.0 | C8—C7—N3 | 119.68 (19) |
C3—C2—H2A | 111.0 | C7—C8—C9 | 119.1 (2) |
C1—C2—H2B | 111.0 | C7—C8—H8 | 120.4 |
C3—C2—H2B | 111.0 | C9—C8—H8 | 120.4 |
H2A—C2—H2B | 109.0 | C10—C9—C8 | 120.0 (3) |
C4—C3—C2 | 105.41 (17) | C10—C9—H9 | 120.0 |
C4—C3—H3A | 110.7 | C8—C9—H9 | 120.0 |
C2—C3—H3A | 110.7 | C11—C10—C9 | 120.4 (2) |
C4—C3—H3B | 110.7 | C11—C10—H10 | 119.8 |
C2—C3—H3B | 110.7 | C9—C10—H10 | 119.8 |
H3A—C3—H3B | 108.8 | C10—C11—C12 | 120.0 (2) |
C3—C4—C5 | 105.07 (16) | C10—C11—H11 | 120.0 |
C3—C4—H4A | 110.7 | C12—C11—H11 | 120.0 |
C5—C4—H4A | 110.7 | C7—C12—C11 | 119.6 (2) |
C3—C4—H4B | 110.7 | C7—C12—H12 | 120.2 |
C5—C4—H4B | 110.7 | C11—C12—H12 | 120.2 |
H4A—C4—H4B | 108.8 | ||
C1—N1—N2—C6 | −173.97 (17) | N1—N2—C6—N3 | −6.8 (3) |
N2—N1—C1—C2 | −1.9 (3) | N1—N2—C6—S1 | 173.42 (14) |
N2—N1—C1—C5 | 177.10 (17) | C6—N3—C7—C12 | −100.6 (2) |
N1—C1—C2—C3 | 166.7 (2) | C6—N3—C7—C8 | 80.9 (3) |
C5—C1—C2—C3 | −12.4 (2) | C12—C7—C8—C9 | −0.3 (3) |
C1—C2—C3—C4 | 27.7 (2) | N3—C7—C8—C9 | 178.2 (2) |
C2—C3—C4—C5 | −32.9 (2) | C7—C8—C9—C10 | 0.0 (4) |
N1—C1—C5—C4 | 173.24 (18) | C8—C9—C10—C11 | 0.3 (4) |
C2—C1—C5—C4 | −7.6 (2) | C9—C10—C11—C12 | −0.3 (4) |
C3—C4—C5—C1 | 24.8 (2) | C8—C7—C12—C11 | 0.3 (3) |
C7—N3—C6—N2 | 176.88 (18) | N3—C7—C12—C11 | −178.16 (19) |
C7—N3—C6—S1 | −3.4 (3) | C10—C11—C12—C7 | 0.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1i | 0.91 | 2.56 | 3.4636 (18) | 172 |
Symmetry code: (i) −x+2, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S1i | 0.91 | 2.56 | 3.4636 (18) | 172 |
Symmetry code: (i) −x+2, −y+2, −z+2. |
Acknowledgements
The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
For the past few decades, thiourea derivatives have attracted great attention not only because they are important building blocks in the synthesis of heterocycles and organo-metal complexes (Yin et al., 2008) but also due to their broad spectrum of biological activities such as anti-bacterial, anti-cancer (Saeed et al., 2010), anti-malarial (Solomon et al., 2010), anti-tuberculosis (Karakuş & Rollas 2002) anti-convulsion, analgesic and HDL-elevating properties. In addition, metal complex of thiourea derivatives exhibit anti-inflammatory, anti-cancer and anti-fungal activities (Abdullah & Salh, 2010). Furthermore, the thiourea structure contains a central hydrophilic part and two hydrophobic moieties forming a butterfly-like conformation. This conformation is a part of the structure of an anti-HIV agent (Struga et al., 2009).
Fig. 1 shows a perspective view of the title compound (I). The five-membered ring (C1–C5) adopts a twisted conformation, [the puckering parameters (Cremer & Pople, 1975) are Q(2) = 0.316 (2) Å and ϕ(2) = 85.7 (4)°]. The dihedral angle between the phenyl ring and the least-squares plane of the thiourea moiety is 78.22 (8)°.
In the crystal structure, the molecules are connected by weak N—H···S interactions (Fig. 2 and Table 1).