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The mol­ecule of the title compound, PhNHC(=S)C(=O)NHPh or C14H12N2OS, consists of two planar fragments, one of which includes the central NHC(=S)C(=O)NH chain together with the Ph substituent on the C=O side; the second Ph ring, the one on the C=S side, all by itself, makes up the second planar fragment. Its plane is twisted about the N—C bond by 52.87 (9)° with respect to the plane of the first fragment. The C=S and C=O double bonds adopt the transoid conformation with the torsion angle S=C—C=O equal to −179.6 (2)°. The mol­ecules in the crystal are linked into centrosymmetric dimers due to the N—H...O hydrogen bond involving the thio­amide NH group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012752/ya6029sup1.cif
Contains datablocks id35, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012752/ya6029Isup2.hkl
Contains datablock I

CCDC reference: 170942

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.047
  • wR factor = 0.117
  • Data-to-parameter ratio = 9.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 2051 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2160 Completeness (_total/calc) 94.95% Alert C: < 95% complete PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(1) - C(2) = 1.53 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

The molecular structure of the title compound, (I), is shown in Fig. 1. The molecule consists of two planar fragments: the C9—C14 phenyl ring makes up one of them and the C3—C8 phenyl ring together with the N1–C1(O1)–C2(S1)–N2 chain atoms attached to C3 forms the other one. The intermolecular hydrogen bond [N2—H2···O1i 2.42 (3) Å, N2···O1i 3.136 (4) Å and N2—H2···O1i 148 (3)°; symmetry code: (i) 1 - x, 1 - y, -z] links the molecules in crystal into centrosymmetric dimers. In the thiooxamide part of the molecule, the S and O atoms are trans with respect to each other; the torsion angle S1—C2—C1—O1 is -179.6 (2)°. The conjugation between the thioamide and amide moieties of the molecule is weak, as the C1—C2 bond [1.532 (4) Å] is significantly longer than the standard Csp2—Csp2 bond length in conjugated systems (1.46–1.48 Å; Allen et al., 1987). The bond distances C1O1 [1.231 (3) Å] and N1—C3 [1.413 (4) Å] are longer than the standard bond lengths for CO (1.22 Å) and CAr—Nsp2 (1.36 Å) (Allen et al., 1987). This effect may be explained by a weak delocalization of electron density on amide group. The bond angle C1–N1–C3 has an abnormal value of 131.5 (3)°. This large bond angle may be explained by steric strain in the planar fragment O1–C1–N1–C3–C4–H4. The second phenyl ring (C9–C14) is twisted about the N2–C9 bond with respect to the planar moiety N2–C2(S1)–C1(O1)–N1–(C3–C8) by 52.87 (9)°. Due to this twisting, the C2—N2—C9 bond angle is not distorted and has a generally accepted value of 126.1 (3)°. Only one related structure (Krayushkin et al., 1996) (with n-butyl instead of phenyl as in our case) was found in Cambridge Structural Database (Allen & Kennard, 1993). The main structural features of this molecule are essentially identical with those of the title compound.

Experimental top

A mixture of 0.5 g (2 mmol) 3-benzoxazolo[3,2-a]pyridinium-2-olate and 10 ml thionyl chloride (SOCl2) was kept under reflux for 1 h. Thionyl chloride was evaporated and the precipitate obtained was washed with benzene (3 × 10 ml) and dissolved in dichloromethane CH2Cl2 (20 ml). 0.4 g (4.3 mmol) aniline (C6H7N) was added to this solution. After heating at 313 K for 1 h and leaving to stand overnight at room temperature, the dichloromethane was evaporated, and the residue washed with water (3 × 20 ml) and recrystallized from a mixture of chloroform and diethyl ether (4:1). The yield was 0.2 g (37%).

Refinement top

All H atoms were refined in the isotropic approximation; the C—H bonds are in the range 0.82–1.00 Å.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: WinGX98 (Farrugia, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1998).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1998) view of the molecule of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Ns,No–diphenyl(thiooxamide) top
Crystal data top
C14H12N2OSF(000) = 536
Mr = 256.32Dx = 1.390 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 4.026 (5) ÅCell parameters from 25 reflections
b = 14.682 (9) Åθ = 13.0–15.0°
c = 20.728 (12) ŵ = 0.25 mm1
β = 90.27 (2)°T = 293 K
V = 1225.1 (17) Å3Prism, yellow
Z = 40.38 × 0.12 × 0.06 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.070
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.0°
Graphite monochromatorh = 44
ω scansk = 017
2089 measured reflectionsl = 024
2051 independent reflections2 standard reflections every 200 reflections
1287 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0597P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.117(Δ/σ)max = 0.048
S = 0.95Δρmax = 0.20 e Å3
2051 reflectionsΔρmin = 0.24 e Å3
212 parameters
Crystal data top
C14H12N2OSV = 1225.1 (17) Å3
Mr = 256.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.026 (5) ŵ = 0.25 mm1
b = 14.682 (9) ÅT = 293 K
c = 20.728 (12) Å0.38 × 0.12 × 0.06 mm
β = 90.27 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.070
2089 measured reflections2 standard reflections every 200 reflections
2051 independent reflections intensity decay: none
1287 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.047212 parameters
wR(F2) = 0.117All H-atom parameters refined
S = 0.95Δρmax = 0.20 e Å3
2051 reflectionsΔρmin = 0.24 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.0159 (2)0.52917 (6)0.19947 (4)0.0492 (3)
O10.4961 (6)0.59769 (14)0.04385 (9)0.0481 (6)
C10.3512 (7)0.6064 (2)0.09566 (14)0.0343 (7)
N10.3027 (7)0.68254 (17)0.12771 (13)0.0393 (6)
C20.2154 (7)0.5217 (2)0.12978 (13)0.0344 (7)
N20.2675 (6)0.44728 (16)0.09655 (13)0.0364 (6)
C30.3995 (7)0.77316 (19)0.11471 (13)0.0335 (7)
C40.5592 (8)0.7986 (2)0.05864 (15)0.0405 (8)
C50.6408 (9)0.8888 (2)0.04948 (17)0.0504 (9)
C60.5705 (10)0.9530 (3)0.09524 (18)0.0556 (10)
C70.4131 (9)0.9272 (2)0.15077 (17)0.0517 (9)
C80.3238 (8)0.8381 (2)0.16104 (16)0.0428 (8)
C90.1870 (7)0.35680 (19)0.11627 (13)0.0337 (7)
C100.0085 (8)0.3011 (2)0.07459 (15)0.0388 (7)
C110.0629 (9)0.2130 (2)0.09314 (17)0.0485 (9)
C120.0412 (9)0.1809 (2)0.15159 (17)0.0453 (9)
C130.2195 (9)0.2361 (2)0.19245 (16)0.0461 (8)
C140.2958 (8)0.3245 (2)0.17498 (16)0.0432 (8)
H10.204 (8)0.674 (2)0.1634 (16)0.045 (9)*
H20.349 (9)0.458 (2)0.0615 (16)0.056 (11)*
H40.589 (8)0.760 (2)0.0264 (14)0.046 (9)*
H50.751 (8)0.905 (2)0.0110 (16)0.052 (9)*
H60.602 (8)1.020 (3)0.0899 (15)0.064 (10)*
H70.353 (8)0.972 (2)0.1817 (15)0.051 (9)*
H80.223 (8)0.817 (2)0.2001 (16)0.055 (10)*
H100.077 (8)0.325 (2)0.0346 (14)0.046 (9)*
H110.196 (9)0.178 (3)0.0656 (17)0.067 (11)*
H120.001 (8)0.129 (2)0.1624 (14)0.044 (10)*
H130.293 (7)0.2131 (19)0.2342 (14)0.040 (8)*
H140.431 (8)0.362 (2)0.1998 (14)0.050 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0569 (6)0.0432 (5)0.0478 (5)0.0020 (4)0.0212 (4)0.0003 (4)
O10.0679 (16)0.0380 (12)0.0385 (12)0.0033 (11)0.0155 (11)0.0001 (10)
C10.0342 (17)0.0338 (17)0.0349 (16)0.0005 (13)0.0009 (13)0.0023 (14)
N10.0444 (16)0.0329 (15)0.0406 (15)0.0031 (12)0.0091 (13)0.0004 (12)
C20.0292 (16)0.0360 (17)0.0379 (15)0.0016 (13)0.0020 (13)0.0002 (14)
N20.0418 (16)0.0311 (14)0.0365 (14)0.0023 (11)0.0066 (12)0.0013 (12)
C30.0285 (16)0.0307 (16)0.0412 (16)0.0000 (12)0.0061 (13)0.0024 (13)
C40.045 (2)0.0351 (18)0.0413 (18)0.0034 (15)0.0042 (15)0.0009 (15)
C50.055 (2)0.045 (2)0.051 (2)0.0095 (17)0.0035 (17)0.0075 (17)
C60.061 (2)0.036 (2)0.070 (2)0.0113 (17)0.0090 (19)0.0009 (18)
C70.058 (2)0.039 (2)0.058 (2)0.0037 (17)0.0013 (18)0.0114 (17)
C80.045 (2)0.0391 (19)0.0447 (19)0.0044 (15)0.0010 (16)0.0008 (15)
C90.0342 (17)0.0298 (16)0.0371 (16)0.0015 (13)0.0084 (13)0.0011 (13)
C100.0397 (18)0.0382 (18)0.0386 (17)0.0024 (15)0.0029 (15)0.0006 (15)
C110.050 (2)0.042 (2)0.053 (2)0.0106 (16)0.0005 (17)0.0016 (17)
C120.050 (2)0.0294 (19)0.057 (2)0.0048 (15)0.0105 (17)0.0059 (16)
C130.055 (2)0.0413 (19)0.0416 (19)0.0032 (17)0.0016 (16)0.0095 (16)
C140.045 (2)0.042 (2)0.0427 (18)0.0039 (16)0.0007 (15)0.0025 (16)
Geometric parameters (Å, º) top
S1—C21.660 (3)C6—H61.00 (4)
O1—C11.231 (3)C7—C81.373 (5)
C1—N11.316 (4)C7—H70.95 (3)
C1—C21.532 (4)C8—H80.96 (3)
N1—C31.413 (4)C9—C141.376 (4)
N1—H10.85 (3)C9—C101.388 (4)
C2—N21.310 (4)C10—C111.380 (5)
N2—C91.428 (4)C10—H100.96 (3)
N2—H20.81 (3)C11—C121.364 (5)
C3—C41.383 (4)C11—H110.94 (4)
C3—C81.389 (4)C12—C131.372 (5)
C4—C51.377 (5)C12—H120.82 (3)
C4—H40.88 (3)C13—C141.382 (5)
C5—C61.368 (5)C13—H130.97 (3)
C5—H50.94 (3)C14—H140.93 (3)
C6—C71.370 (5)
O1—C1—N1126.9 (3)C8—C7—C6121.1 (3)
O1—C1—C2119.3 (3)C8—C7—H7119 (2)
N1—C1—C2113.7 (2)C6—C7—H7120 (2)
C1—N1—C3131.5 (3)C7—C8—C3119.2 (3)
C1—N1—H1112 (2)C7—C8—H8123 (2)
C3—N1—H1116 (2)C3—C8—H8117 (2)
N2—C2—C1112.1 (2)C14—C9—C10120.6 (3)
N2—C2—S1126.3 (2)C14—C9—N2120.2 (3)
C1—C2—S1121.6 (2)C10—C9—N2119.2 (3)
C2—N2—C9126.1 (3)C11—C10—C9119.1 (3)
C2—N2—H2112 (3)C11—C10—H10120.7 (18)
C9—N2—H2122 (3)C9—C10—H10120.0 (18)
C4—C3—C8120.0 (3)C12—C11—C10120.5 (3)
C4—C3—N1123.0 (3)C12—C11—H11122 (2)
C8—C3—N1117.0 (3)C10—C11—H11118 (2)
C3—C4—C5119.2 (3)C11—C12—C13120.1 (3)
C3—C4—H4122 (2)C11—C12—H12120 (2)
C5—C4—H4118 (2)C13—C12—H12119 (2)
C6—C5—C4121.1 (3)C12—C13—C14120.6 (3)
C6—C5—H5121 (2)C12—C13—H13120.0 (17)
C4—C5—H5118 (2)C14—C13—H13119.4 (18)
C5—C6—C7119.3 (3)C9—C14—C13119.0 (3)
C5—C6—H6125.1 (19)C9—C14—H14118.0 (19)
C7—C6—H6115.2 (19)C13—C14—H14122.8 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S10.85 (3)2.38 (3)2.938 (3)124 (3)
N2—H2···O10.81 (3)2.17 (4)2.632 (4)116 (3)
C4—H4···O10.88 (3)2.45 (3)2.977 (4)119 (3)
N2—H2···O1i0.81 (3)2.42 (3)3.136 (4)148 (3)
C14—H14···S10.93 (3)2.97 (3)3.250 (4)99 (2)
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC14H12N2OS
Mr256.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)4.026 (5), 14.682 (9), 20.728 (12)
β (°) 90.27 (2)
V3)1225.1 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.38 × 0.12 × 0.06
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2089, 2051, 1287
Rint0.070
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.117, 0.95
No. of reflections2051
No. of parameters212
No. of restraints?
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.20, 0.24

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, WinGX98 (Farrugia, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1998).

Selected geometric parameters (Å, º) top
S1—C21.660 (3)N1—H10.85 (3)
O1—C11.231 (3)C2—N21.310 (4)
C1—N11.316 (4)N2—C91.428 (4)
C1—C21.532 (4)N2—H20.81 (3)
N1—C31.413 (4)
O1—C1—N1126.9 (3)C1—C2—S1121.6 (2)
O1—C1—C2119.3 (3)C2—N2—C9126.1 (3)
N1—C1—C2113.7 (2)C4—C3—N1123.0 (3)
C1—N1—C3131.5 (3)C8—C3—N1117.0 (3)
N2—C2—C1112.1 (2)C14—C9—N2120.2 (3)
N2—C2—S1126.3 (2)C10—C9—N2119.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S10.85 (3)2.38 (3)2.938 (3)124 (3)
N2—H2···O10.81 (3)2.17 (4)2.632 (4)116 (3)
C4—H4···O10.88 (3)2.45 (3)2.977 (4)119 (3)
N2—H2···O1i0.81 (3)2.42 (3)3.136 (4)148 (3)
C14—H14···S10.93 (3)2.97 (3)3.250 (4)99 (2)
Symmetry code: (i) x+1, y+1, z.
 

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