The molecule of the title compound, PhNHC(=S)C(=O)NHPh or C
14H
12N
2OS, 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
CCDC reference: 170942
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
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%).
All H atoms were refined in the isotropic approximation; the C—H bonds are in
the range 0.82–1.00 Å.
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).
Ns,
No–diphenyl(thiooxamide)
top
Crystal data top
C14H12N2OS | F(000) = 536 |
Mr = 256.32 | Dx = 1.390 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.026 (5) Å | Cell parameters from 25 reflections |
b = 14.682 (9) Å | θ = 13.0–15.0° |
c = 20.728 (12) Å | µ = 0.25 mm−1 |
β = 90.27 (2)° | T = 293 K |
V = 1225.1 (17) Å3 | Prism, yellow |
Z = 4 | 0.38 × 0.12 × 0.06 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.070 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = −4→4 |
ω scans | k = 0→17 |
2089 measured reflections | l = 0→24 |
2051 independent reflections | 2 standard reflections every 200 reflections |
1287 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | All 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 = 0.95 | Δρmax = 0.20 e Å−3 |
2051 reflections | Δρmin = −0.24 e Å−3 |
212 parameters | |
Crystal data top
C14H12N2OS | V = 1225.1 (17) Å3 |
Mr = 256.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.026 (5) Å | µ = 0.25 mm−1 |
b = 14.682 (9) Å | T = 293 K |
c = 20.728 (12) Å | 0.38 × 0.12 × 0.06 mm |
β = 90.27 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.070 |
2089 measured reflections | 2 standard reflections every 200 reflections |
2051 independent reflections | intensity decay: none |
1287 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 212 parameters |
wR(F2) = 0.117 | All H-atom parameters refined |
S = 0.95 | Δρmax = 0.20 e Å−3 |
2051 reflections | Δρmin = −0.24 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.0159 (2) | 0.52917 (6) | 0.19947 (4) | 0.0492 (3) | |
O1 | 0.4961 (6) | 0.59769 (14) | 0.04385 (9) | 0.0481 (6) | |
C1 | 0.3512 (7) | 0.6064 (2) | 0.09566 (14) | 0.0343 (7) | |
N1 | 0.3027 (7) | 0.68254 (17) | 0.12771 (13) | 0.0393 (6) | |
C2 | 0.2154 (7) | 0.5217 (2) | 0.12978 (13) | 0.0344 (7) | |
N2 | 0.2675 (6) | 0.44728 (16) | 0.09655 (13) | 0.0364 (6) | |
C3 | 0.3995 (7) | 0.77316 (19) | 0.11471 (13) | 0.0335 (7) | |
C4 | 0.5592 (8) | 0.7986 (2) | 0.05864 (15) | 0.0405 (8) | |
C5 | 0.6408 (9) | 0.8888 (2) | 0.04948 (17) | 0.0504 (9) | |
C6 | 0.5705 (10) | 0.9530 (3) | 0.09524 (18) | 0.0556 (10) | |
C7 | 0.4131 (9) | 0.9272 (2) | 0.15077 (17) | 0.0517 (9) | |
C8 | 0.3238 (8) | 0.8381 (2) | 0.16104 (16) | 0.0428 (8) | |
C9 | 0.1870 (7) | 0.35680 (19) | 0.11627 (13) | 0.0337 (7) | |
C10 | 0.0085 (8) | 0.3011 (2) | 0.07459 (15) | 0.0388 (7) | |
C11 | −0.0629 (9) | 0.2130 (2) | 0.09314 (17) | 0.0485 (9) | |
C12 | 0.0412 (9) | 0.1809 (2) | 0.15159 (17) | 0.0453 (9) | |
C13 | 0.2195 (9) | 0.2361 (2) | 0.19245 (16) | 0.0461 (8) | |
C14 | 0.2958 (8) | 0.3245 (2) | 0.17498 (16) | 0.0432 (8) | |
H1 | 0.204 (8) | 0.674 (2) | 0.1634 (16) | 0.045 (9)* | |
H2 | 0.349 (9) | 0.458 (2) | 0.0615 (16) | 0.056 (11)* | |
H4 | 0.589 (8) | 0.760 (2) | 0.0264 (14) | 0.046 (9)* | |
H5 | 0.751 (8) | 0.905 (2) | 0.0110 (16) | 0.052 (9)* | |
H6 | 0.602 (8) | 1.020 (3) | 0.0899 (15) | 0.064 (10)* | |
H7 | 0.353 (8) | 0.972 (2) | 0.1817 (15) | 0.051 (9)* | |
H8 | 0.223 (8) | 0.817 (2) | 0.2001 (16) | 0.055 (10)* | |
H10 | −0.077 (8) | 0.325 (2) | 0.0346 (14) | 0.046 (9)* | |
H11 | −0.196 (9) | 0.178 (3) | 0.0656 (17) | 0.067 (11)* | |
H12 | 0.001 (8) | 0.129 (2) | 0.1624 (14) | 0.044 (10)* | |
H13 | 0.293 (7) | 0.2131 (19) | 0.2342 (14) | 0.040 (8)* | |
H14 | 0.431 (8) | 0.362 (2) | 0.1998 (14) | 0.050 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0569 (6) | 0.0432 (5) | 0.0478 (5) | −0.0020 (4) | 0.0212 (4) | 0.0003 (4) |
O1 | 0.0679 (16) | 0.0380 (12) | 0.0385 (12) | −0.0033 (11) | 0.0155 (11) | −0.0001 (10) |
C1 | 0.0342 (17) | 0.0338 (17) | 0.0349 (16) | −0.0005 (13) | 0.0009 (13) | 0.0023 (14) |
N1 | 0.0444 (16) | 0.0329 (15) | 0.0406 (15) | −0.0031 (12) | 0.0091 (13) | −0.0004 (12) |
C2 | 0.0292 (16) | 0.0360 (17) | 0.0379 (15) | −0.0016 (13) | −0.0020 (13) | 0.0002 (14) |
N2 | 0.0418 (16) | 0.0311 (14) | 0.0365 (14) | −0.0023 (11) | 0.0066 (12) | 0.0013 (12) |
C3 | 0.0285 (16) | 0.0307 (16) | 0.0412 (16) | 0.0000 (12) | −0.0061 (13) | 0.0024 (13) |
C4 | 0.045 (2) | 0.0351 (18) | 0.0413 (18) | −0.0034 (15) | 0.0042 (15) | 0.0009 (15) |
C5 | 0.055 (2) | 0.045 (2) | 0.051 (2) | −0.0095 (17) | 0.0035 (17) | 0.0075 (17) |
C6 | 0.061 (2) | 0.036 (2) | 0.070 (2) | −0.0113 (17) | −0.0090 (19) | 0.0009 (18) |
C7 | 0.058 (2) | 0.039 (2) | 0.058 (2) | 0.0037 (17) | −0.0013 (18) | −0.0114 (17) |
C8 | 0.045 (2) | 0.0391 (19) | 0.0447 (19) | 0.0044 (15) | 0.0010 (16) | −0.0008 (15) |
C9 | 0.0342 (17) | 0.0298 (16) | 0.0371 (16) | −0.0015 (13) | 0.0084 (13) | 0.0011 (13) |
C10 | 0.0397 (18) | 0.0382 (18) | 0.0386 (17) | 0.0024 (15) | 0.0029 (15) | 0.0006 (15) |
C11 | 0.050 (2) | 0.042 (2) | 0.053 (2) | −0.0106 (16) | 0.0005 (17) | −0.0016 (17) |
C12 | 0.050 (2) | 0.0294 (19) | 0.057 (2) | −0.0048 (15) | 0.0105 (17) | 0.0059 (16) |
C13 | 0.055 (2) | 0.0413 (19) | 0.0416 (19) | 0.0032 (17) | 0.0016 (16) | 0.0095 (16) |
C14 | 0.045 (2) | 0.042 (2) | 0.0427 (18) | −0.0039 (16) | −0.0007 (15) | 0.0025 (16) |
Geometric parameters (Å, º) top
S1—C2 | 1.660 (3) | C6—H6 | 1.00 (4) |
O1—C1 | 1.231 (3) | C7—C8 | 1.373 (5) |
C1—N1 | 1.316 (4) | C7—H7 | 0.95 (3) |
C1—C2 | 1.532 (4) | C8—H8 | 0.96 (3) |
N1—C3 | 1.413 (4) | C9—C14 | 1.376 (4) |
N1—H1 | 0.85 (3) | C9—C10 | 1.388 (4) |
C2—N2 | 1.310 (4) | C10—C11 | 1.380 (5) |
N2—C9 | 1.428 (4) | C10—H10 | 0.96 (3) |
N2—H2 | 0.81 (3) | C11—C12 | 1.364 (5) |
C3—C4 | 1.383 (4) | C11—H11 | 0.94 (4) |
C3—C8 | 1.389 (4) | C12—C13 | 1.372 (5) |
C4—C5 | 1.377 (5) | C12—H12 | 0.82 (3) |
C4—H4 | 0.88 (3) | C13—C14 | 1.382 (5) |
C5—C6 | 1.368 (5) | C13—H13 | 0.97 (3) |
C5—H5 | 0.94 (3) | C14—H14 | 0.93 (3) |
C6—C7 | 1.370 (5) | | |
| | | |
O1—C1—N1 | 126.9 (3) | C8—C7—C6 | 121.1 (3) |
O1—C1—C2 | 119.3 (3) | C8—C7—H7 | 119 (2) |
N1—C1—C2 | 113.7 (2) | C6—C7—H7 | 120 (2) |
C1—N1—C3 | 131.5 (3) | C7—C8—C3 | 119.2 (3) |
C1—N1—H1 | 112 (2) | C7—C8—H8 | 123 (2) |
C3—N1—H1 | 116 (2) | C3—C8—H8 | 117 (2) |
N2—C2—C1 | 112.1 (2) | C14—C9—C10 | 120.6 (3) |
N2—C2—S1 | 126.3 (2) | C14—C9—N2 | 120.2 (3) |
C1—C2—S1 | 121.6 (2) | C10—C9—N2 | 119.2 (3) |
C2—N2—C9 | 126.1 (3) | C11—C10—C9 | 119.1 (3) |
C2—N2—H2 | 112 (3) | C11—C10—H10 | 120.7 (18) |
C9—N2—H2 | 122 (3) | C9—C10—H10 | 120.0 (18) |
C4—C3—C8 | 120.0 (3) | C12—C11—C10 | 120.5 (3) |
C4—C3—N1 | 123.0 (3) | C12—C11—H11 | 122 (2) |
C8—C3—N1 | 117.0 (3) | C10—C11—H11 | 118 (2) |
C3—C4—C5 | 119.2 (3) | C11—C12—C13 | 120.1 (3) |
C3—C4—H4 | 122 (2) | C11—C12—H12 | 120 (2) |
C5—C4—H4 | 118 (2) | C13—C12—H12 | 119 (2) |
C6—C5—C4 | 121.1 (3) | C12—C13—C14 | 120.6 (3) |
C6—C5—H5 | 121 (2) | C12—C13—H13 | 120.0 (17) |
C4—C5—H5 | 118 (2) | C14—C13—H13 | 119.4 (18) |
C5—C6—C7 | 119.3 (3) | C9—C14—C13 | 119.0 (3) |
C5—C6—H6 | 125.1 (19) | C9—C14—H14 | 118.0 (19) |
C7—C6—H6 | 115.2 (19) | C13—C14—H14 | 122.8 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1 | 0.85 (3) | 2.38 (3) | 2.938 (3) | 124 (3) |
N2—H2···O1 | 0.81 (3) | 2.17 (4) | 2.632 (4) | 116 (3) |
C4—H4···O1 | 0.88 (3) | 2.45 (3) | 2.977 (4) | 119 (3) |
N2—H2···O1i | 0.81 (3) | 2.42 (3) | 3.136 (4) | 148 (3) |
C14—H14···S1 | 0.93 (3) | 2.97 (3) | 3.250 (4) | 99 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | C14H12N2OS |
Mr | 256.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 4.026 (5), 14.682 (9), 20.728 (12) |
β (°) | 90.27 (2) |
V (Å3) | 1225.1 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.38 × 0.12 × 0.06 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2089, 2051, 1287 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.117, 0.95 |
No. of reflections | 2051 |
No. of parameters | 212 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.24 |
Selected geometric parameters (Å, º) topS1—C2 | 1.660 (3) | N1—H1 | 0.85 (3) |
O1—C1 | 1.231 (3) | C2—N2 | 1.310 (4) |
C1—N1 | 1.316 (4) | N2—C9 | 1.428 (4) |
C1—C2 | 1.532 (4) | N2—H2 | 0.81 (3) |
N1—C3 | 1.413 (4) | | |
| | | |
O1—C1—N1 | 126.9 (3) | C1—C2—S1 | 121.6 (2) |
O1—C1—C2 | 119.3 (3) | C2—N2—C9 | 126.1 (3) |
N1—C1—C2 | 113.7 (2) | C4—C3—N1 | 123.0 (3) |
C1—N1—C3 | 131.5 (3) | C8—C3—N1 | 117.0 (3) |
N2—C2—C1 | 112.1 (2) | C14—C9—N2 | 120.2 (3) |
N2—C2—S1 | 126.3 (2) | C10—C9—N2 | 119.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1 | 0.85 (3) | 2.38 (3) | 2.938 (3) | 124 (3) |
N2—H2···O1 | 0.81 (3) | 2.17 (4) | 2.632 (4) | 116 (3) |
C4—H4···O1 | 0.88 (3) | 2.45 (3) | 2.977 (4) | 119 (3) |
N2—H2···O1i | 0.81 (3) | 2.42 (3) | 3.136 (4) | 148 (3) |
C14—H14···S1 | 0.93 (3) | 2.97 (3) | 3.250 (4) | 99 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
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 C1═O1 [1.231 (3) Å] and N1—C3 [1.413 (4) Å] are longer than the standard bond lengths for C═O (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.