organic compounds
1-(Naphthalen-1-yl)-3-[(thiophen-2-yl)carbonyl]thiourea
aDepartment of Chemistry, M. M. V., Banaras Hindu University, Varanasi 221 005, India, bSchool of Studies in Chemistry, Jiwaji University, Gwalior 474 011, India, and cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com
In the title compound, C16H12N2OS2, the dihedral angles between the mean planes of the central thiourea core and the thiophene ring and the naphthalene ring system are 1.8 (2) and 6.45 (18)°, respectively. The molecule adopts a trans–cis conformation with respect to the position of thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. Both the thiophene ring and the sulfanylidene S atom are disordered over two sets of sites with occupancies of 0.862 (3):0.138 (3) and 0.977 (3):0.023 (3), respectively. An intramolecular N—H⋯O hydrogen bond is observed. The crystal packing features two N—H⋯S hydrogen bonds.
Related literature
For heterocyclic thiourea derivatives, metal complexes and their applications, see: D'hooghe et al. (2005); Aly et al. (2007); Estévez-Hernández et al. (2007); Saeed et al. (2008a,b,c). For related structures, see: Singh et al. (2012); Koch (2001); Pérez et al. (2008). For the synthesis, see: Otazo-Sánchez et al. (2001).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812035350/bq2371sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812035350/bq2371Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812035350/bq2371Isup3.cml
The title compound was synthesized according to a previous report (Otazo-Sánchez et al., 2001), by converting furoyl choride into furoyl isothiocyanate and then condensing with α-naphthylamine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (M.P.: 459 K). Anal. Calc. for C16H12N2OS2 (%): C, 61.51; H, 3.87; N, 8.97. Found: C, 61.20; H, 3.80; N, 9.10.
H1 was located by a Fourier map and refined isotropically. All of the remaining H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.93 Å (CH). Isotropic displacement parameters for these atoms were set to 1.20 (CH) times Ueq of the parent atom. Both the thiophene ring and the thio S are disordered over two positions with occupancies of 0.867 (3)/0.133 (3) and 0.84 (3)/0.16 (3), respectively.
Aroylythiourea and its derivatives are an important class of organic compounds due to their ability to form a variety of
(D'hooghe et al., 2005) and metal complexes that can be used as ionophores in potentiometric and amperometric sensors (Aly et al., 2007; Estévez-Hernández et al., 2007) and as epoxy resin curing agents and accelerators (Saeed et al., 2008a, 2008b, 2008c). The title compound, N-(naphthalen-1-yl)-3-oxo-3-(thiophen-2-yl)propanethioamide is an important precursor with O and S as potential donor sites, and can be used to form heterocycles and metal complexes. We have reported recently the synthesis and of methyl 2-(thiophene-2-carboxamido)benzoate (Singh et al., 2012). We herein report the synthesis and of the biologically active title compound.In the title compound (Fig.1) the bond lengths and angles are within the ranges observed for similar compounds (Koch, 2001; Pérez et al., 2008). The C11—S1B [1.661 (3) Å] and C12—O1 [1.230 (3) Å] bonds show typical double-bond character. However, the C—N bond lengths, C12—N2 [1.376 (4) Å], C11—N1 [1.326 (4) Å], C11—N2 [1.397 (4) Å] and C1—N1 [1.419 (4) Å] are all shorter than the normal C—N single-bond length of about 1.48 Å and indicate some degree of delocalization. The central thiourea fragment (N1/C11/N2/C12/O1) makes a dihedral angle of 2.03 (41)° with the major part of the 2-thiophenoyl group (S2/C13/C14/C15/C16) and 6.51 (16)° with the naphthalene ring (C1/C2/C3/C4/C5/C6/C7/C8/C9/C10), respectively. Thus, the conformation is almost planar and adopts a trans-cis configuration with respect to the position of the thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. This geometry is stabilized by both an N1—H1···O1 intramolecular hydrogen bond and two intermolecular N—H···S hydrogen bonds (Fig.2). In addition, both the thiophene ring and the thio S are disordered over two positions with occupancies of 0.862 (3)/0.138 (3) and 0.977 (3)/0.023 (3), respectively.
For heterocyclic derivatives, metal complexes and their applications, see: D'hooghe et al. (2005); Aly et al. (2007); Estévez-Hernández et al. (2007); Saeed et al. (2008a,b,c). For related structures, see: Singh et al. (2012); Koch (2001); Pérez et al. (2008). For the synthesis, see: Otazo-Sánchez et al. (2001).
Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell
CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C16H12N2OS2 | F(000) = 648 |
Mr = 312.40 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.929 (2) Å | Cell parameters from 1174 reflections |
b = 5.9086 (8) Å | θ = 3.3–27.3° |
c = 17.071 (3) Å | µ = 0.36 mm−1 |
β = 104.030 (14)° | T = 173 K |
V = 1460.9 (4) Å3 | Prism, colorless |
Z = 4 | 0.35 × 0.25 × 0.15 mm |
Oxford Diffraction Xcalibur Eos diffractometer | 2625 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1626 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 16.0938 pixels mm-1 | θmax = 25.5°, θmin = 3.7° |
ω scans | h = −18→10 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | k = −6→7 |
Tmin = 0.712, Tmax = 1.000 | l = −17→20 |
4822 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.3695P] where P = (Fo2 + 2Fc2)/3 |
2625 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.33 e Å−3 |
10 restraints | Δρmin = −0.31 e Å−3 |
C16H12N2OS2 | V = 1460.9 (4) Å3 |
Mr = 312.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.929 (2) Å | µ = 0.36 mm−1 |
b = 5.9086 (8) Å | T = 173 K |
c = 17.071 (3) Å | 0.35 × 0.25 × 0.15 mm |
β = 104.030 (14)° |
Oxford Diffraction Xcalibur Eos diffractometer | 2625 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | 1626 reflections with I > 2σ(I) |
Tmin = 0.712, Tmax = 1.000 | Rint = 0.052 |
4822 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 10 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.33 e Å−3 |
2625 reflections | Δρmin = −0.31 e Å−3 |
210 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1A | 0.962 (3) | 0.732 (11) | 0.421 (4) | 0.0764 (5) | 0.023 (3) |
S1B | 0.98334 (7) | 0.6323 (3) | 0.38685 (9) | 0.0764 (5) | 0.977 (3) |
S2A | 0.66455 (8) | −0.0348 (2) | 0.46547 (8) | 0.0582 (4) | 0.862 (3) |
C13A | 0.7707 (3) | 0.0902 (7) | 0.4715 (3) | 0.0404 (11) | 0.862 (3) |
C14A | 0.8378 (4) | −0.0413 (13) | 0.5210 (5) | 0.0655 (19) | 0.862 (3) |
H14A | 0.9018 | −0.0083 | 0.5310 | 0.079* | 0.862 (3) |
C15A | 0.8041 (4) | −0.2228 (11) | 0.5543 (4) | 0.0655 (15) | 0.862 (3) |
H15A | 0.8419 | −0.3270 | 0.5900 | 0.079* | 0.862 (3) |
C16A | 0.7114 (4) | −0.2380 (12) | 0.5309 (6) | 0.0695 (14) | 0.862 (3) |
H16A | 0.6765 | −0.3515 | 0.5496 | 0.083* | 0.862 (3) |
S2B | 0.8612 (8) | −0.036 (2) | 0.5239 (9) | 0.0582 (4) | 0.138 (3) |
C13B | 0.7593 (17) | 0.051 (5) | 0.4590 (19) | 0.0404 (11) | 0.138 (3) |
C14B | 0.6895 (17) | −0.046 (5) | 0.488 (2) | 0.0655 (19) | 0.138 (3) |
H14B | 0.6294 | 0.0174 | 0.4803 | 0.079* | 0.138 (3) |
C15B | 0.716 (2) | −0.242 (7) | 0.530 (4) | 0.0655 (15) | 0.138 (3) |
H15B | 0.6767 | −0.3658 | 0.5338 | 0.079* | 0.138 (3) |
C16B | 0.807 (2) | −0.233 (7) | 0.566 (3) | 0.0695 (14) | 0.138 (3) |
H16B | 0.8373 | −0.3273 | 0.6097 | 0.083* | 0.138 (3) |
O1 | 0.69721 (14) | 0.3590 (3) | 0.37691 (14) | 0.0546 (6) | |
N1 | 0.79871 (16) | 0.6726 (4) | 0.33310 (16) | 0.0440 (7) | |
H1A | 0.7462 | 0.6094 | 0.3360 | 0.053* | |
N2 | 0.85320 (16) | 0.3884 (4) | 0.42315 (16) | 0.0452 (7) | |
H2A | 0.9009 | 0.3300 | 0.4579 | 0.054* | |
C1 | 0.7879 (2) | 0.8627 (5) | 0.28085 (19) | 0.0432 (8) | |
C2 | 0.8584 (2) | 1.0074 (5) | 0.2753 (2) | 0.0541 (9) | |
H2 | 0.9196 | 0.9774 | 0.3054 | 0.065* | |
C3 | 0.8401 (3) | 1.1985 (5) | 0.2255 (2) | 0.0585 (10) | |
H3 | 0.8894 | 1.2973 | 0.2223 | 0.070* | |
C4 | 0.7537 (3) | 1.2454 (5) | 0.1817 (2) | 0.0570 (9) | |
H4 | 0.7429 | 1.3778 | 0.1492 | 0.068* | |
C5 | 0.6798 (2) | 1.0997 (5) | 0.1838 (2) | 0.0468 (8) | |
C6 | 0.5901 (3) | 1.1427 (6) | 0.1368 (2) | 0.0594 (10) | |
H6 | 0.5788 | 1.2741 | 0.1038 | 0.071* | |
C7 | 0.5189 (3) | 0.9981 (6) | 0.1379 (2) | 0.0659 (11) | |
H7 | 0.4587 | 1.0297 | 0.1060 | 0.079* | |
C8 | 0.5347 (2) | 0.8048 (6) | 0.1857 (2) | 0.0574 (10) | |
H8 | 0.4851 | 0.7044 | 0.1859 | 0.069* | |
C9 | 0.6200 (2) | 0.7578 (5) | 0.2319 (2) | 0.0494 (9) | |
H9 | 0.6291 | 0.6249 | 0.2642 | 0.059* | |
C10 | 0.6962 (2) | 0.9031 (5) | 0.23326 (19) | 0.0416 (8) | |
C11 | 0.8727 (2) | 0.5719 (5) | 0.37841 (19) | 0.0434 (8) | |
C12 | 0.7696 (2) | 0.2864 (5) | 0.4203 (2) | 0.0433 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0282 (5) | 0.1166 (10) | 0.0801 (9) | −0.0049 (6) | 0.0048 (5) | 0.0291 (8) |
S1B | 0.0282 (5) | 0.1166 (10) | 0.0801 (9) | −0.0049 (6) | 0.0048 (5) | 0.0291 (8) |
S2A | 0.0543 (7) | 0.0566 (6) | 0.0598 (9) | −0.0107 (6) | 0.0061 (5) | 0.0071 (6) |
C13A | 0.0405 (19) | 0.035 (2) | 0.041 (2) | −0.0003 (16) | 0.0015 (16) | −0.0068 (18) |
C14A | 0.057 (4) | 0.064 (3) | 0.077 (4) | 0.000 (3) | 0.020 (4) | −0.010 (2) |
C15A | 0.091 (4) | 0.048 (2) | 0.051 (3) | 0.023 (3) | 0.004 (3) | 0.006 (2) |
C16A | 0.090 (4) | 0.053 (3) | 0.063 (3) | −0.015 (3) | 0.015 (3) | 0.002 (2) |
S2B | 0.0543 (7) | 0.0566 (6) | 0.0598 (9) | −0.0107 (6) | 0.0061 (5) | 0.0071 (6) |
C13B | 0.0405 (19) | 0.035 (2) | 0.041 (2) | −0.0003 (16) | 0.0015 (16) | −0.0068 (18) |
C14B | 0.057 (4) | 0.064 (3) | 0.077 (4) | 0.000 (3) | 0.020 (4) | −0.010 (2) |
C15B | 0.091 (4) | 0.048 (2) | 0.051 (3) | 0.023 (3) | 0.004 (3) | 0.006 (2) |
C16B | 0.090 (4) | 0.053 (3) | 0.063 (3) | −0.015 (3) | 0.015 (3) | 0.002 (2) |
O1 | 0.0340 (12) | 0.0537 (13) | 0.0694 (16) | −0.0034 (10) | −0.0006 (11) | 0.0150 (12) |
N1 | 0.0286 (13) | 0.0453 (14) | 0.0541 (17) | −0.0030 (11) | 0.0021 (12) | 0.0007 (13) |
N2 | 0.0302 (13) | 0.0547 (15) | 0.0472 (16) | 0.0030 (12) | 0.0026 (11) | 0.0113 (13) |
C1 | 0.0381 (17) | 0.0383 (15) | 0.0503 (19) | −0.0019 (14) | 0.0050 (14) | −0.0047 (14) |
C2 | 0.0455 (19) | 0.0503 (18) | 0.067 (2) | −0.0095 (16) | 0.0136 (17) | −0.0035 (17) |
C3 | 0.063 (2) | 0.0504 (18) | 0.068 (2) | −0.0188 (18) | 0.0281 (19) | −0.0075 (18) |
C4 | 0.072 (2) | 0.0452 (17) | 0.059 (2) | −0.0030 (19) | 0.0254 (19) | 0.0032 (16) |
C5 | 0.0516 (19) | 0.0406 (16) | 0.050 (2) | 0.0058 (16) | 0.0165 (16) | −0.0023 (15) |
C6 | 0.062 (2) | 0.057 (2) | 0.059 (2) | 0.0175 (19) | 0.0146 (19) | 0.0156 (18) |
C7 | 0.051 (2) | 0.075 (2) | 0.067 (3) | 0.018 (2) | 0.0062 (19) | 0.017 (2) |
C8 | 0.0409 (19) | 0.064 (2) | 0.065 (2) | 0.0007 (17) | 0.0078 (17) | 0.0111 (19) |
C9 | 0.0421 (18) | 0.0506 (17) | 0.052 (2) | −0.0010 (16) | 0.0044 (15) | 0.0080 (16) |
C10 | 0.0387 (17) | 0.0380 (15) | 0.0477 (19) | 0.0024 (14) | 0.0092 (14) | −0.0061 (14) |
C11 | 0.0342 (16) | 0.0593 (18) | 0.0356 (17) | −0.0004 (15) | 0.0065 (13) | 0.0002 (15) |
C12 | 0.0322 (16) | 0.0423 (16) | 0.0513 (19) | 0.0028 (14) | 0.0023 (14) | −0.0017 (15) |
S1A—C11 | 1.65 (5) | N1—H1A | 0.8800 |
S1B—C11 | 1.661 (3) | N2—C12 | 1.376 (4) |
S2A—C16A | 1.674 (6) | N2—C11 | 1.397 (4) |
S2A—C13A | 1.729 (4) | N2—H2A | 0.8800 |
C13A—C14A | 1.383 (7) | C1—C2 | 1.377 (4) |
C13A—C12 | 1.449 (5) | C1—C10 | 1.432 (4) |
C14A—C15A | 1.365 (8) | C2—C3 | 1.401 (5) |
C14A—H14A | 0.9500 | C2—H2 | 0.9500 |
C15A—C16A | 1.347 (6) | C3—C4 | 1.353 (5) |
C15A—H15A | 0.9500 | C3—H3 | 0.9500 |
C16A—H16A | 0.9500 | C4—C5 | 1.408 (5) |
S2B—C16B | 1.67 (2) | C4—H4 | 0.9500 |
S2B—C13B | 1.728 (19) | C5—C6 | 1.407 (4) |
C13B—C14B | 1.39 (2) | C5—C10 | 1.422 (4) |
C13B—C12 | 1.56 (3) | C6—C7 | 1.367 (5) |
C14B—C15B | 1.37 (2) | C6—H6 | 0.9500 |
C14B—H14B | 0.9500 | C7—C8 | 1.390 (5) |
C15B—C16B | 1.350 (18) | C7—H7 | 0.9500 |
C15B—H15B | 0.9500 | C8—C9 | 1.354 (4) |
C16B—H16B | 0.9500 | C8—H8 | 0.9500 |
O1—C12 | 1.230 (3) | C9—C10 | 1.421 (4) |
N1—C11 | 1.326 (4) | C9—H9 | 0.9500 |
N1—C1 | 1.419 (4) | ||
C16A—S2A—C13A | 92.2 (2) | C3—C2—H2 | 119.9 |
C14A—C13A—C12 | 136.0 (5) | C4—C3—C2 | 121.3 (3) |
C14A—C13A—S2A | 108.3 (4) | C4—C3—H3 | 119.3 |
C12—C13A—S2A | 115.4 (3) | C2—C3—H3 | 119.3 |
C15A—C14A—C13A | 114.2 (5) | C3—C4—C5 | 120.6 (3) |
C15A—C14A—H14A | 122.9 | C3—C4—H4 | 119.7 |
C13A—C14A—H14A | 122.9 | C5—C4—H4 | 119.7 |
C16A—C15A—C14A | 112.6 (5) | C4—C5—C6 | 121.3 (3) |
C16A—C15A—H15A | 123.7 | C4—C5—C10 | 119.4 (3) |
C14A—C15A—H15A | 123.7 | C6—C5—C10 | 119.3 (3) |
C15A—C16A—S2A | 112.5 (5) | C7—C6—C5 | 121.0 (3) |
C15A—C16A—H16A | 123.7 | C7—C6—H6 | 119.5 |
S2A—C16A—H16A | 123.7 | C5—C6—H6 | 119.5 |
C16B—S2B—C13B | 92.5 (12) | C6—C7—C8 | 119.9 (3) |
C14B—C13B—C12 | 133 (2) | C6—C7—H7 | 120.0 |
C14B—C13B—S2B | 105.6 (15) | C8—C7—H7 | 120.0 |
C12—C13B—S2B | 112.0 (16) | C9—C8—C7 | 120.8 (3) |
C15B—C14B—C13B | 113 (2) | C9—C8—H8 | 119.6 |
C15B—C14B—H14B | 123.6 | C7—C8—H8 | 119.6 |
C13B—C14B—H14B | 123.6 | C8—C9—C10 | 121.4 (3) |
C16B—C15B—C14B | 110 (2) | C8—C9—H9 | 119.3 |
C16B—C15B—H15B | 125.2 | C10—C9—H9 | 119.3 |
C14B—C15B—H15B | 125.2 | C9—C10—C5 | 117.5 (3) |
C15B—C16B—S2B | 112 (2) | C9—C10—C1 | 124.0 (3) |
C15B—C16B—H16B | 124.2 | C5—C10—C1 | 118.5 (3) |
S2B—C16B—H16B | 124.2 | N1—C11—N2 | 114.4 (3) |
C11—N1—C1 | 132.4 (3) | N1—C11—S1A | 118 (2) |
C11—N1—H1A | 113.8 | N2—C11—S1A | 117.1 (18) |
C1—N1—H1A | 113.8 | N1—C11—S1B | 128.6 (3) |
C12—N2—C11 | 128.9 (2) | N2—C11—S1B | 117.0 (2) |
C12—N2—H2A | 115.5 | S1A—C11—S1B | 33 (3) |
C11—N2—H2A | 115.5 | O1—C12—N2 | 121.7 (3) |
C2—C1—N1 | 124.2 (3) | O1—C12—C13A | 121.5 (3) |
C2—C1—C10 | 119.9 (3) | N2—C12—C13A | 116.8 (3) |
N1—C1—C10 | 115.9 (3) | O1—C12—C13B | 113.8 (9) |
C1—C2—C3 | 120.2 (3) | N2—C12—C13B | 123.8 (9) |
C1—C2—H2 | 119.9 | C13A—C12—C13B | 11.9 (13) |
C16A—S2A—C13A—C14A | 3.3 (6) | C4—C5—C10—C9 | −178.4 (3) |
C16A—S2A—C13A—C12 | 178.1 (5) | C6—C5—C10—C9 | 0.4 (5) |
C12—C13A—C14A—C15A | −176.1 (6) | C4—C5—C10—C1 | 1.4 (4) |
S2A—C13A—C14A—C15A | −2.9 (8) | C6—C5—C10—C1 | −179.8 (3) |
C13A—C14A—C15A—C16A | 0.8 (11) | C2—C1—C10—C9 | 176.9 (3) |
C14A—C15A—C16A—S2A | 1.9 (11) | N1—C1—C10—C9 | −4.5 (5) |
C13A—S2A—C16A—C15A | −3.0 (8) | C2—C1—C10—C5 | −2.8 (5) |
C16B—S2B—C13B—C14B | 13 (4) | N1—C1—C10—C5 | 175.8 (3) |
C16B—S2B—C13B—C12 | 164 (3) | C1—N1—C11—N2 | 178.7 (3) |
C12—C13B—C14B—C15B | −169 (4) | C1—N1—C11—S1A | 35 (3) |
S2B—C13B—C14B—C15B | −27 (5) | C1—N1—C11—S1B | −2.6 (5) |
C13B—C14B—C15B—C16B | 30 (6) | C12—N2—C11—N1 | 7.1 (5) |
C14B—C15B—C16B—S2B | −19 (7) | C12—N2—C11—S1A | 151 (3) |
C13B—S2B—C16B—C15B | 3 (5) | C12—N2—C11—S1B | −171.6 (3) |
C11—N1—C1—C2 | −9.6 (5) | C11—N2—C12—O1 | −3.4 (5) |
C11—N1—C1—C10 | 171.8 (3) | C11—N2—C12—C13A | 177.1 (3) |
N1—C1—C2—C3 | −176.2 (3) | C11—N2—C12—C13B | 165.9 (17) |
C10—C1—C2—C3 | 2.3 (5) | C14A—C13A—C12—O1 | 174.0 (6) |
C1—C2—C3—C4 | −0.2 (5) | S2A—C13A—C12—O1 | 1.2 (5) |
C2—C3—C4—C5 | −1.3 (5) | C14A—C13A—C12—N2 | −6.5 (8) |
C3—C4—C5—C6 | −178.1 (3) | S2A—C13A—C12—N2 | −179.4 (3) |
C3—C4—C5—C10 | 0.7 (5) | C14A—C13A—C12—C13B | 122 (7) |
C4—C5—C6—C7 | 178.6 (4) | S2A—C13A—C12—C13B | −51 (6) |
C10—C5—C6—C7 | −0.2 (5) | C14B—C13B—C12—O1 | −36 (4) |
C5—C6—C7—C8 | −0.3 (6) | S2B—C13B—C12—O1 | −176.6 (15) |
C6—C7—C8—C9 | 0.4 (6) | C14B—C13B—C12—N2 | 154 (3) |
C7—C8—C9—C10 | −0.2 (5) | S2B—C13B—C12—N2 | 13 (3) |
C8—C9—C10—C5 | −0.3 (5) | C14B—C13B—C12—C13A | 96 (9) |
C8—C9—C10—C1 | 180.0 (3) | S2B—C13B—C12—C13A | −44 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.88 | 1.86 | 2.615 (3) | 143 |
N2—H2A···S2B | 0.88 | 2.57 | 3.026 (14) | 113 |
N2—H2A···S1Ai | 0.88 | 2.56 | 3.41 (4) | 164 |
N2—H2A···S1Bi | 0.88 | 2.80 | 3.557 (3) | 145 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H12N2OS2 |
Mr | 312.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.929 (2), 5.9086 (8), 17.071 (3) |
β (°) | 104.030 (14) |
V (Å3) | 1460.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.35 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.712, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4822, 2625, 1626 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.165, 1.09 |
No. of reflections | 2625 |
No. of parameters | 210 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.31 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.88 | 1.86 | 2.615 (3) | 142.7 |
N2—H2A···S2B | 0.88 | 2.57 | 3.026 (14) | 112.9 |
N2—H2A···S1Ai | 0.88 | 2.56 | 3.41 (4) | 163.7 |
N2—H2A···S1Bi | 0.88 | 2.80 | 3.557 (3) | 145.2 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Acknowledgements
DPS and SP are grateful to Banaras Hindu University, Varanasi, for financial support. RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. SKG wishes to acknowledge the USIEF for the award of a Fulbright–Nehru Senior Research Fellowship.
References
Aly, A. A., Ahmed, E. K., El-Mokadem, K. M. & Hegazy, M. E. F. (2007). J. Sulfur Chem. 28, 73–93. CrossRef CAS Google Scholar
D'hooghe, M., Waterinckx, A. & De Kimpe, N. (2005). J. Org. Chem. 70, 227–232. Web of Science PubMed CAS Google Scholar
Estévez-Hernández, O., Hidalgo-Hidalgo de Cisneros, J. L., Reguera, E. & Naranjo-Rodríguez, I. (2007). Sens. Actuators B Chem. 120, 766–772. Google Scholar
Koch, K. R. (2001). Coord. Chem. Rev. 216–217, 473–488. Web of Science CrossRef CAS Google Scholar
Otazo-Sánchez, E., Pérez-Marín, L., Estévez-Hernández, O., Rojas-Lima, S. & Alonso-Chamorro, J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211–2218. Google Scholar
Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Pérez, H., Mascarenhas, Y., Estévez-Hernández, O., Santos Jr, S. & Duque, J. (2008). Acta Cryst. E64, o513. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saeed, S., Bhatti, M. H., Tahir, M. K. & Jones, P. G. (2008a). Acta Cryst. E64, o1369. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saeed, S., Bhatti, M. H., Yunus, U. & Jones, P. G. (2008b). Acta Cryst. E64, o1485. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saeed, S., Bhatti, M. H., Yunus, U. & Jones, P. G. (2008c). Acta Cryst. E64, o1566. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Singh, D. P., Pratap, S., Butcher, R. J. & Gupta, S. K. (2012). Acta Cryst. E68, o1765. CSD CrossRef IUCr Journals Google Scholar
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.
Aroylythiourea and its derivatives are an important class of organic compounds due to their ability to form a variety of heterocyclic compounds (D'hooghe et al., 2005) and metal complexes that can be used as ionophores in potentiometric and amperometric sensors (Aly et al., 2007; Estévez-Hernández et al., 2007) and as epoxy resin curing agents and accelerators (Saeed et al., 2008a, 2008b, 2008c). The title compound, N-(naphthalen-1-yl)-3-oxo-3-(thiophen-2-yl)propanethioamide is an important precursor with O and S as potential donor sites, and can be used to form heterocycles and metal complexes. We have reported recently the synthesis and crystal structure of methyl 2-(thiophene-2-carboxamido)benzoate (Singh et al., 2012). We herein report the synthesis and crystal structure of the biologically active title compound.
In the title compound (Fig.1) the bond lengths and angles are within the ranges observed for similar compounds (Koch, 2001; Pérez et al., 2008). The C11—S1B [1.661 (3) Å] and C12—O1 [1.230 (3) Å] bonds show typical double-bond character. However, the C—N bond lengths, C12—N2 [1.376 (4) Å], C11—N1 [1.326 (4) Å], C11—N2 [1.397 (4) Å] and C1—N1 [1.419 (4) Å] are all shorter than the normal C—N single-bond length of about 1.48 Å and indicate some degree of delocalization. The central thiourea fragment (N1/C11/N2/C12/O1) makes a dihedral angle of 2.03 (41)° with the major part of the 2-thiophenoyl group (S2/C13/C14/C15/C16) and 6.51 (16)° with the naphthalene ring (C1/C2/C3/C4/C5/C6/C7/C8/C9/C10), respectively. Thus, the conformation is almost planar and adopts a trans-cis configuration with respect to the position of the thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. This geometry is stabilized by both an N1—H1···O1 intramolecular hydrogen bond and two intermolecular N—H···S hydrogen bonds (Fig.2). In addition, both the thiophene ring and the thio S are disordered over two positions with occupancies of 0.862 (3)/0.138 (3) and 0.977 (3)/0.023 (3), respectively.