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The phenyl and benzoyl groups in the title compound, C14H12N2OS, lie cis and trans, respectively, to the S atom across the thio­urea C—N bonds. The mol­ecules are packed as dimers, via N—H...S intermolecular hydrogen bonds, and arranged parallel to the a and c axes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023711/ob6205sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023711/ob6205Isup2.hkl
Contains datablock I

CCDC reference: 204686

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.125
  • Data-to-parameter ratio = 17.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Although some arylbenzoylthioureas such as 3,4-dimethylphenylbenzoylthiourea (Shanmuga Sundara Raj et al., 1999) and 2,6-dimethylphenylbenzoylthiourea (Usman et al., 2002) have been reported, the structure of its unsubstituted phenyl analogue is still not available. Therefore the X-ray crystallographic investigation of the title compound, (I), was carried out.

The C—C bond lengths and bond angles of the phenyl and the benzoyl groups are in the normal ranges (Allen et al., 1987). The central carbonyl-thiourea moiety, (S1/C8/N1/N2/C7/O1) is also in agreement with most benzoylthiourea derivatives (Shanmuga Sundara Raj et al., 1999; Usman et al., 2002; Kaminsky et al., 2002). However, the N2—C9 bond length of 1.408 (2) Å is shorter than in the bulky 2,6-dimethylphenylbenzoylthiourea [1.436 (2) Å] and the C8—N2—C9 bond angle of 133.16 (14)° is larger compared to 123.2 (2)° and 127.9 (2)° in 2,6- (Usman et al., 2002) and 3,4-dimethylphenylbenzoylthiourea (Shanmuga Sundara Raj et al., 1999) respectively. The phenyl and the benzoyl substituents in the molecule lie cis and trans, respectively, to S atom across the thiourea C—N bonds.

The O1/C7/N1/C8/N2 plane has a maximum deviation of 0.035 (1) Å at the atom N1. However, the central carbonyl-thiourea (S1/C8/N1/N2/C7/O1) moiety connecting the two phenyl rings is slightly less planar, with S1 atom deviating by 0.145 (1) Å. The phenyl (C1—C6) and (C9—C14) rings are essentially planar. The two rings make dihedral angles of 28.78 (9)° and 7.52 (9)°, respectively, with the carbonyl-thiourea plane. The dihedral angle between the two aromatic rings is 33.3 (1)°.

As in most benzoylthiourea derivatives, the intramolecular hydrogen bonding N2—H2B···O1 maintains the six-membered ring formation of the N2/C8/N1/C7/O1 plane and the presence of a weak interaction of C14—H14A···S1 (Table 2). In the lattice, the molecules are packed as dimers via weak N1—H1B···S1' interactions and arranged parallel to the a and c axes (Fig. 2).

Experimental top

A solution of analine (0.16 g, 1.40 mmol) in acetone (50 ml) was added dropwise to 50 ml of an acetone solution containing an equimolar amount of benzoylthiocyanate in a two-neck round-bottomed flask. The solution was refluxed for about 1 h and then cooled in ice. The white precipitate which formed was filtered off and washed with ethanol-distilled water, then dried in a vacuum (yield 79%). Recrystallization from DMSO yielded single crystals of (I) suitable for X-ray analysis.

Refinement top

After checking their presence in the difference map, all H-atoms were fixed geometrically and allowed to ride on the parent C or N atoms, with C—H = 0.93 Å and N—H = 0.86 Å.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound (I), with 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Packing diagram of (I), viewed down the b axis. Dashed lines denote N—H···S hydrogen bonds.
N-Benzoyl- N'-Phenylthiourea top
Crystal data top
C14H12N2OSF(000) = 536
Mr = 256.32Dx = 1.344 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.8492 (11) ÅCell parameters from 2753 reflections
b = 5.1963 (5) Åθ = 1.6–27.6°
c = 19.5971 (18) ŵ = 0.24 mm1
β = 104.484 (2)°T = 293 K
V = 1266.9 (2) Å3Block, colourless
Z = 40.46 × 0.33 × 0.30 mm
Data collection top
Bruker SMART APEX CCD area-detector difrractometer
diffractometer
2917 independent reflections
Radiation source: fine-focus sealed tube2304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 83.66 pixels mm-1θmax = 27.6°, θmin = 1.6°
ω scanh = 1616
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 56
Tmin = 0.896, Tmax = 0.930l = 2025
8234 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0646P)2 + 0.2031P]
where P = (Fo2 + 2Fc2)/3
2917 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C14H12N2OSV = 1266.9 (2) Å3
Mr = 256.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.8492 (11) ŵ = 0.24 mm1
b = 5.1963 (5) ÅT = 293 K
c = 19.5971 (18) Å0.46 × 0.33 × 0.30 mm
β = 104.484 (2)°
Data collection top
Bruker SMART APEX CCD area-detector difrractometer
diffractometer
2917 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2304 reflections with I > 2σ(I)
Tmin = 0.896, Tmax = 0.930Rint = 0.017
8234 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.125H-atom parameters constrained
S = 1.04Δρmax = 0.24 e Å3
2917 reflectionsΔρmin = 0.14 e Å3
163 parameters
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
S10.10979 (3)0.70045 (11)0.08198 (2)0.06806 (19)
N10.17647 (10)0.4294 (3)0.01131 (7)0.0541 (3)
H1B0.11510.35630.01590.065*
C10.10703 (13)0.0163 (3)0.10315 (9)0.0580 (4)
H1A0.08320.01630.06210.070*
C20.06561 (16)0.1910 (4)0.15596 (11)0.0677 (5)
H2A0.01430.30970.15020.081*
C30.09957 (17)0.1906 (4)0.21662 (11)0.0724 (5)
H3A0.07160.30950.25190.087*
C40.17474 (17)0.0155 (5)0.22571 (11)0.0775 (6)
H4A0.19700.01430.26740.093*
C50.21709 (15)0.1579 (4)0.17340 (10)0.0702 (5)
H5A0.26840.27570.17960.084*
C60.18387 (13)0.1585 (3)0.11134 (9)0.0536 (4)
C70.23561 (13)0.3456 (3)0.05654 (9)0.0575 (4)
C80.20285 (12)0.6170 (3)0.04097 (8)0.0512 (4)
C90.35789 (13)0.9072 (3)0.09429 (8)0.0539 (4)
C100.46107 (15)0.9478 (4)0.08782 (11)0.0738 (5)
H10A0.48820.84510.05740.089*
C110.52398 (17)1.1378 (5)0.12570 (13)0.0849 (6)
H11A0.59321.16380.12060.102*
C120.48567 (18)1.2893 (4)0.17092 (12)0.0787 (6)
H12A0.52801.41950.19630.094*
C130.38453 (18)1.2466 (4)0.17824 (12)0.0788 (6)
H13A0.35871.34740.20960.095*
C140.31939 (15)1.0581 (4)0.14048 (10)0.0690 (5)
H14A0.25031.03280.14610.083*
N20.30135 (11)0.7114 (3)0.05072 (7)0.0583 (4)
H2B0.33830.63790.02520.070*
O10.32631 (11)0.4254 (3)0.05285 (8)0.0810 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0541 (3)0.1055 (4)0.0507 (3)0.0062 (2)0.0246 (2)0.0108 (2)
N10.0476 (7)0.0707 (9)0.0465 (7)0.0033 (6)0.0166 (5)0.0008 (6)
C10.0617 (9)0.0591 (10)0.0556 (9)0.0065 (8)0.0189 (8)0.0130 (7)
C20.0697 (11)0.0562 (10)0.0766 (12)0.0064 (8)0.0167 (9)0.0080 (9)
C30.0727 (12)0.0720 (12)0.0700 (12)0.0040 (10)0.0132 (10)0.0122 (9)
C40.0773 (12)0.0974 (15)0.0638 (11)0.0111 (11)0.0286 (10)0.0176 (10)
C50.0664 (11)0.0859 (13)0.0660 (11)0.0157 (10)0.0310 (9)0.0134 (9)
C60.0503 (8)0.0597 (9)0.0526 (9)0.0049 (7)0.0160 (7)0.0010 (7)
C70.0502 (8)0.0697 (10)0.0558 (9)0.0018 (8)0.0197 (7)0.0020 (8)
C80.0481 (8)0.0677 (10)0.0389 (7)0.0038 (7)0.0130 (6)0.0063 (7)
C90.0511 (8)0.0615 (10)0.0484 (8)0.0055 (7)0.0114 (7)0.0046 (7)
C100.0583 (10)0.0895 (14)0.0781 (13)0.0046 (10)0.0253 (9)0.0133 (11)
C110.0613 (11)0.0952 (16)0.0981 (16)0.0161 (11)0.0196 (11)0.0085 (13)
C120.0789 (14)0.0693 (12)0.0823 (14)0.0067 (10)0.0096 (11)0.0059 (10)
C130.0805 (14)0.0768 (13)0.0799 (14)0.0027 (11)0.0215 (11)0.0171 (10)
C140.0611 (10)0.0782 (12)0.0705 (12)0.0001 (9)0.0212 (9)0.0106 (9)
N20.0475 (7)0.0749 (9)0.0554 (8)0.0015 (6)0.0183 (6)0.0090 (7)
O10.0571 (7)0.1070 (11)0.0874 (10)0.0149 (7)0.0339 (7)0.0355 (8)
Geometric parameters (Å, º) top
S1—C81.6567 (15)C7—O11.222 (2)
N1—C71.3746 (19)C8—N21.326 (2)
N1—C81.393 (2)C9—C101.379 (2)
N1—H1B0.8600C9—C141.379 (2)
C1—C21.380 (3)C9—N21.408 (2)
C1—C61.380 (2)C10—C111.371 (3)
C1—H1A0.9300C10—H10A0.9300
C2—C31.365 (3)C11—C121.366 (3)
C2—H2A0.9300C11—H11A0.9300
C3—C41.371 (3)C12—C131.361 (3)
C3—H3A0.9300C12—H12A0.9300
C4—C51.371 (3)C13—C141.378 (3)
C4—H4A0.9300C13—H13A0.9300
C5—C61.386 (2)C14—H14A0.9300
C5—H5A0.9300N2—H2B0.8600
C6—C71.478 (2)
C7—N1—C8128.58 (14)N2—C8—N1114.38 (14)
C7—N1—H1B115.7N2—C8—S1127.73 (13)
C8—N1—H1B115.7N1—C8—S1117.88 (12)
C2—C1—C6119.93 (16)C10—C9—C14118.97 (17)
C2—C1—H1A120.0C10—C9—N2114.63 (15)
C6—C1—H1A120.0C14—C9—N2126.40 (15)
C3—C2—C1120.32 (18)C11—C10—C9120.69 (19)
C3—C2—H2A119.8C11—C10—H10A119.7
C1—C2—H2A119.8C9—C10—H10A119.7
C2—C3—C4120.23 (19)C12—C11—C10120.5 (2)
C2—C3—H3A119.9C12—C11—H11A119.8
C4—C3—H3A119.9C10—C11—H11A119.8
C3—C4—C5120.00 (18)C13—C12—C11118.9 (2)
C3—C4—H4A120.0C13—C12—H12A120.6
C5—C4—H4A120.0C11—C12—H12A120.6
C4—C5—C6120.40 (18)C12—C13—C14121.8 (2)
C4—C5—H5A119.8C12—C13—H13A119.1
C6—C5—H5A119.8C14—C13—H13A119.1
C1—C6—C5119.13 (16)C13—C14—C9119.15 (18)
C1—C6—C7123.60 (15)C13—C14—H14A120.4
C5—C6—C7117.25 (15)C9—C14—H14A120.4
O1—C7—N1121.83 (16)C8—N2—C9133.16 (14)
O1—C7—C6121.02 (15)C8—N2—H2B113.4
N1—C7—C6117.13 (14)C9—N2—H2B113.4
C6—C1—C2—C30.6 (3)C7—N1—C8—N25.2 (2)
C1—C2—C3—C40.3 (3)C7—N1—C8—S1173.54 (14)
C2—C3—C4—C50.8 (3)C14—C9—C10—C111.1 (3)
C3—C4—C5—C60.4 (3)N2—C9—C10—C11178.10 (19)
C2—C1—C6—C51.0 (3)C9—C10—C11—C120.4 (3)
C2—C1—C6—C7177.57 (16)C10—C11—C12—C130.7 (4)
C4—C5—C6—C10.5 (3)C11—C12—C13—C141.1 (3)
C4—C5—C6—C7178.14 (19)C12—C13—C14—C90.4 (3)
C8—N1—C7—O13.7 (3)C10—C9—C14—C130.7 (3)
C8—N1—C7—C6174.84 (15)N2—C9—C14—C13178.43 (18)
C1—C6—C7—O1152.07 (18)N1—C8—N2—C9176.40 (16)
C5—C6—C7—O126.5 (3)S1—C8—N2—C92.2 (3)
C1—C6—C7—N129.3 (2)C10—C9—N2—C8179.38 (18)
C5—C6—C7—N1152.08 (17)C14—C9—N2—C80.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···S1i0.862.873.6544 (14)152
N2—H2B···O10.861.862.599 (2)143
C14—H14A···S10.932.593.237 (2)127
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC14H12N2OS
Mr256.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)12.8492 (11), 5.1963 (5), 19.5971 (18)
β (°) 104.484 (2)
V3)1266.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.46 × 0.33 × 0.30
Data collection
DiffractometerBruker SMART APEX CCD area-detector difrractometer
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.896, 0.930
No. of measured, independent and
observed [I > 2σ(I)] reflections
8234, 2917, 2304
Rint0.017
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.125, 1.04
No. of reflections2917
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.14

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
S1—C81.6567 (15)C7—O11.222 (2)
N1—C71.3746 (19)C8—N21.326 (2)
N1—C81.393 (2)C9—N21.408 (2)
C7—N1—C8128.58 (14)N2—C8—S1127.73 (13)
O1—C7—N1121.83 (16)N1—C8—S1117.88 (12)
N2—C8—N1114.38 (14)C8—N2—C9133.16 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···S1i0.862.873.6544 (14)152
N2—H2B···O10.861.862.599 (2)143
C14—H14A···S10.932.593.237 (2)127
Symmetry code: (i) x, y+1, z.
 

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