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The title compound, C16H16N2OS, adopts a trans-cis configuration of the 4-methyl­benzoyl and 4-methyl­phenyl groups, with respect to the thiono S atom across the thio­urea C-N bonds. The dihedral angle between the two groups is 10.36 (8)°. The structure is stabilized by inter­molecular hydrogen bonds which form dimers. There are also intra­molecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049720/bq2038sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049720/bq2038Isup2.hkl
Contains datablock I

CCDC reference: 667414

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.056
  • wR factor = 0.142
  • Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), is isostructural to N-(4-methylbenzoyl)-N'-(4-nitrophenyl)thiourea (II), (Yusof, Hamid et al., 2006), except that the nitro group at the phenyl ring is replaced by methyl group (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methylphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges and comparable to those in (II) and other thiourea derivatives (Yusof, Rahim & Yamin, 2006). The central carbonylthiourea (S1/N1/N2/C8/O1/C9) and both 4-methylphenyl groups [(C1—C6/C7) and (C10—C15/C16)] are all planar separately, with a maximum deviation of 0.039 (2) Å for atom N1 from the least-squares plane. The central carbonylthiourea fragment makes dihedral angles of 22.15 (8)° and 10.36 (8)° [24.67 (10) and 6.65 (10)° in (II)] with two rings [(C1—C6/C7) and (C10—C15/C16)], respectively. The two aryl rings are inclined to each other at an angle of 32.18 (10)° is larger compared in (II), 28.12 (12)°.

There are two intramolecular hydrogen bond, N2—H2···O1 and C11—H11···S1 (Table 1), forming two pseudo-six-membered rings, O1···H2—N2—C9—N1—C8—O1 and S1···H11—C11—C10—N2—C9—S1. In the crystal structure, the molecules are linked by intermolecular interaction, N—H···S (symmetry codes as in Table 1) to form dimers (Fig.2).

Related literature top

For related crystal structures, see: Yusof, Hamid et al. (2006); Yusof, Rahim & Yamin (2006).

Experimental top

To a stirring acetone solution (75 ml) of 4-methylbenzoyl chloride (2.0 g, 13 mmol) and ammoniumthiocyanate (0.98 g, 13 mmol), o-toluidine (1.39 g, 13 mmol) in 40 ml of acetone was added dropwise. The solution mixture was refluxed for 1 h. The resulting solution was poured into a beaker containing some ice blocks. The white precipitate was filtered off and washed with distilled water and cold ethanol before dried under vacuum. Good quality crystals were obtained by recrystallization from acetone.

Refinement top

After their location in the difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C or N atoms with C—H = 0.93–0.97 Å and N—H = 0.86 Å with Uiso(H)= 1.2 (CH2 and NH) or 1.5Ueq(C)(CH3).

Structure description top

The title compound, (I), is isostructural to N-(4-methylbenzoyl)-N'-(4-nitrophenyl)thiourea (II), (Yusof, Hamid et al., 2006), except that the nitro group at the phenyl ring is replaced by methyl group (Fig.1). The molecule maintains its trans-cis configuration with respect to the position of the 4-methylbenzoyl and 4-methylphenyl groups relative to the thiono S1 atom across their C—N bonds, respectively. The bond lengths and angles are in normal ranges and comparable to those in (II) and other thiourea derivatives (Yusof, Rahim & Yamin, 2006). The central carbonylthiourea (S1/N1/N2/C8/O1/C9) and both 4-methylphenyl groups [(C1—C6/C7) and (C10—C15/C16)] are all planar separately, with a maximum deviation of 0.039 (2) Å for atom N1 from the least-squares plane. The central carbonylthiourea fragment makes dihedral angles of 22.15 (8)° and 10.36 (8)° [24.67 (10) and 6.65 (10)° in (II)] with two rings [(C1—C6/C7) and (C10—C15/C16)], respectively. The two aryl rings are inclined to each other at an angle of 32.18 (10)° is larger compared in (II), 28.12 (12)°.

There are two intramolecular hydrogen bond, N2—H2···O1 and C11—H11···S1 (Table 1), forming two pseudo-six-membered rings, O1···H2—N2—C9—N1—C8—O1 and S1···H11—C11—C10—N2—C9—S1. In the crystal structure, the molecules are linked by intermolecular interaction, N—H···S (symmetry codes as in Table 1) to form dimers (Fig.2).

For related crystal structures, see: Yusof, Hamid et al. (2006); Yusof, Rahim & Yamin (2006).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. : The molecule of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. : Packing diagram of compound,(I), viewed down the b axis. The dashed lines denote the N—H···S hydrogen bonds.
N-(4-Methylbenzoyl)-N'-(4-methylphenyl)thiourea top
Crystal data top
C16H16N2OSF(000) = 600
Mr = 284.37Dx = 1.296 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 693 reflections
a = 12.191 (2) Åθ = 1.7–25.9°
b = 6.4315 (12) ŵ = 0.22 mm1
c = 18.911 (4) ÅT = 298 K
β = 100.713 (3)°Block, colourless
V = 1456.9 (5) Å30.25 × 0.22 × 0.16 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2838 independent reflections
Radiation source: fine-focus sealed tube1942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 83.66 pixels mm-1θmax = 25.9°, θmin = 1.7°
ω scansh = 1215
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
k = 77
Tmin = 0.947, Tmax = 0.966l = 2223
7857 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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.067P)2 + 0.2946P]
where P = (Fo2 + 2Fc2)/3
2838 reflections(Δ/σ)max < 0.001
183 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C16H16N2OSV = 1456.9 (5) Å3
Mr = 284.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.191 (2) ŵ = 0.22 mm1
b = 6.4315 (12) ÅT = 298 K
c = 18.911 (4) Å0.25 × 0.22 × 0.16 mm
β = 100.713 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2838 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1942 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.966Rint = 0.034
7857 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.142H-atom parameters constrained
S = 1.03Δρmax = 0.19 e Å3
2838 reflectionsΔρmin = 0.13 e Å3
183 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
S10.59737 (6)0.13899 (12)1.08812 (4)0.0657 (3)
O10.84014 (16)0.0690 (3)0.94662 (11)0.0680 (6)
N10.68101 (17)0.0707 (3)0.99280 (11)0.0490 (5)
H10.61810.13380.98950.059*
N20.79159 (16)0.1988 (3)1.04329 (11)0.0486 (5)
H20.83540.14631.01720.058*
C10.7480 (2)0.3785 (4)0.84506 (15)0.0565 (7)
H1A0.80030.29020.83090.068*
C20.7117 (2)0.5499 (4)0.80403 (15)0.0597 (7)
H2A0.73990.57590.76250.072*
C30.6340 (2)0.6845 (4)0.82327 (13)0.0495 (6)
C40.5938 (2)0.6419 (4)0.88529 (14)0.0534 (7)
H40.54120.73030.89910.064*
C50.6303 (2)0.4701 (4)0.92731 (13)0.0501 (7)
H50.60270.44480.96920.060*
C60.7078 (2)0.3359 (4)0.90707 (13)0.0448 (6)
C70.5932 (3)0.8713 (4)0.77817 (15)0.0727 (9)
H7A0.55100.95950.80420.109*
H7B0.65600.94700.76740.109*
H7C0.54660.82680.73410.109*
C80.7503 (2)0.1490 (4)0.94979 (13)0.0473 (6)
C90.6967 (2)0.0950 (4)1.04097 (13)0.0449 (6)
C100.8334 (2)0.3817 (4)1.08134 (13)0.0449 (6)
C110.7742 (2)0.5094 (4)1.11914 (15)0.0584 (7)
H110.70090.47731.12220.070*
C120.8244 (2)0.6855 (4)1.15247 (15)0.0602 (7)
H120.78400.76901.17860.072*
C130.9316 (2)0.7415 (4)1.14847 (14)0.0544 (7)
C140.9888 (2)0.6136 (4)1.11015 (15)0.0617 (8)
H141.06170.64761.10650.074*
C150.9414 (2)0.4356 (4)1.07668 (14)0.0548 (7)
H150.98230.35191.05100.066*
C160.9857 (3)0.9309 (5)1.18721 (17)0.0805 (10)
H16A0.93001.03521.18910.121*
H16B1.04090.98481.16190.121*
H16C1.02060.89331.23530.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0614 (5)0.0779 (6)0.0643 (5)0.0172 (4)0.0283 (4)0.0237 (4)
O10.0564 (12)0.0650 (12)0.0889 (14)0.0144 (10)0.0302 (11)0.0285 (11)
N10.0489 (13)0.0450 (12)0.0554 (13)0.0083 (10)0.0156 (10)0.0085 (10)
N20.0452 (12)0.0474 (12)0.0553 (13)0.0022 (10)0.0149 (10)0.0120 (10)
C10.0582 (17)0.0533 (16)0.0614 (17)0.0063 (13)0.0202 (14)0.0059 (14)
C20.073 (2)0.0571 (17)0.0522 (16)0.0044 (15)0.0188 (14)0.0098 (14)
C30.0616 (17)0.0395 (14)0.0446 (14)0.0017 (12)0.0025 (12)0.0025 (11)
C40.0641 (18)0.0410 (14)0.0561 (16)0.0064 (13)0.0132 (14)0.0040 (13)
C50.0627 (18)0.0434 (15)0.0464 (14)0.0010 (12)0.0162 (13)0.0008 (12)
C60.0471 (15)0.0398 (13)0.0473 (14)0.0032 (11)0.0085 (11)0.0018 (11)
C70.103 (3)0.0542 (18)0.0598 (18)0.0137 (16)0.0113 (17)0.0091 (14)
C80.0473 (15)0.0448 (14)0.0506 (15)0.0025 (12)0.0114 (12)0.0041 (12)
C90.0471 (15)0.0428 (14)0.0438 (14)0.0023 (11)0.0060 (11)0.0021 (11)
C100.0488 (15)0.0422 (14)0.0422 (14)0.0004 (11)0.0044 (11)0.0028 (11)
C110.0535 (17)0.0552 (17)0.0682 (18)0.0002 (13)0.0160 (14)0.0141 (14)
C120.070 (2)0.0499 (16)0.0617 (18)0.0018 (14)0.0150 (15)0.0135 (14)
C130.071 (2)0.0419 (15)0.0456 (15)0.0040 (14)0.0004 (13)0.0008 (12)
C140.0545 (17)0.0600 (18)0.0694 (19)0.0130 (14)0.0080 (15)0.0029 (15)
C150.0545 (17)0.0492 (16)0.0624 (17)0.0016 (13)0.0156 (14)0.0079 (13)
C160.102 (3)0.0566 (19)0.077 (2)0.0188 (17)0.0010 (19)0.0088 (16)
Geometric parameters (Å, º) top
S1—C91.656 (2)C6—C81.487 (3)
O1—C81.222 (3)C7—H7A0.9600
N1—C81.372 (3)C7—H7B0.9600
N1—C91.392 (3)C7—H7C0.9600
N1—H10.8600C10—C111.377 (3)
N2—C91.329 (3)C10—C151.380 (3)
N2—C101.423 (3)C11—C121.382 (4)
N2—H20.8600C11—H110.9300
C1—C21.373 (4)C12—C131.371 (4)
C1—C61.380 (3)C12—H120.9300
C1—H1A0.9300C13—C141.370 (4)
C2—C31.381 (4)C13—C161.509 (4)
C2—H2A0.9300C14—C151.382 (4)
C3—C41.380 (3)C14—H140.9300
C3—C71.503 (3)C15—H150.9300
C4—C51.385 (3)C16—H16A0.9600
C4—H40.9300C16—H16B0.9600
C5—C61.385 (3)C16—H16C0.9600
C5—H50.9300
C8—N1—C9130.1 (2)O1—C8—N1122.1 (2)
C8—N1—H1115.0O1—C8—C6122.6 (2)
C9—N1—H1115.0N1—C8—C6115.4 (2)
C9—N2—C10131.3 (2)N2—C9—N1114.8 (2)
C9—N2—H2114.4N2—C9—S1127.98 (19)
C10—N2—H2114.4N1—C9—S1117.23 (18)
C2—C1—C6120.7 (2)C11—C10—C15118.8 (2)
C2—C1—H1A119.6C11—C10—N2125.6 (2)
C6—C1—H1A119.6C15—C10—N2115.6 (2)
C1—C2—C3121.3 (3)C10—C11—C12119.7 (3)
C1—C2—H2A119.4C10—C11—H11120.2
C3—C2—H2A119.4C12—C11—H11120.2
C4—C3—C2118.0 (2)C13—C12—C11122.4 (3)
C4—C3—C7120.6 (2)C13—C12—H12118.8
C2—C3—C7121.5 (2)C11—C12—H12118.8
C3—C4—C5121.3 (2)C14—C13—C12117.1 (3)
C3—C4—H4119.4C14—C13—C16121.5 (3)
C5—C4—H4119.4C12—C13—C16121.4 (3)
C4—C5—C6120.1 (2)C13—C14—C15121.9 (3)
C4—C5—H5120.0C13—C14—H14119.0
C6—C5—H5120.0C15—C14—H14119.0
C1—C6—C5118.7 (2)C10—C15—C14120.1 (2)
C1—C6—C8118.6 (2)C10—C15—H15119.9
C5—C6—C8122.7 (2)C14—C15—H15119.9
C3—C7—H7A109.5C13—C16—H16A109.5
C3—C7—H7B109.5C13—C16—H16B109.5
H7A—C7—H7B109.5H16A—C16—H16B109.5
C3—C7—H7C109.5C13—C16—H16C109.5
H7A—C7—H7C109.5H16A—C16—H16C109.5
H7B—C7—H7C109.5H16B—C16—H16C109.5
C6—C1—C2—C30.1 (4)C10—N2—C9—N1175.3 (2)
C1—C2—C3—C40.1 (4)C10—N2—C9—S14.9 (4)
C1—C2—C3—C7179.5 (3)C8—N1—C9—N23.3 (4)
C2—C3—C4—C50.2 (4)C8—N1—C9—S1176.5 (2)
C7—C3—C4—C5179.8 (2)C9—N2—C10—C118.7 (4)
C3—C4—C5—C60.6 (4)C9—N2—C10—C15173.8 (2)
C2—C1—C6—C50.3 (4)C15—C10—C11—C121.2 (4)
C2—C1—C6—C8179.7 (2)N2—C10—C11—C12178.6 (2)
C4—C5—C6—C10.6 (4)C10—C11—C12—C131.2 (4)
C4—C5—C6—C8180.0 (2)C11—C12—C13—C140.6 (4)
C9—N1—C8—O13.3 (4)C11—C12—C13—C16178.1 (3)
C9—N1—C8—C6177.2 (2)C12—C13—C14—C150.1 (4)
C1—C6—C8—O123.2 (4)C16—C13—C14—C15177.6 (3)
C5—C6—C8—O1156.2 (3)C11—C10—C15—C140.7 (4)
C1—C6—C8—N1156.3 (2)N2—C10—C15—C14178.3 (2)
C5—C6—C8—N124.3 (3)C13—C14—C15—C100.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.861.932.657 (3)141
C11—H11···S10.932.543.193 (3)128
N1—H1···S1i0.862.763.482 (2)142
Symmetry code: (i) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC16H16N2OS
Mr284.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)12.191 (2), 6.4315 (12), 18.911 (4)
β (°) 100.713 (3)
V3)1456.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.25 × 0.22 × 0.16
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.947, 0.966
No. of measured, independent and
observed [I > 2σ(I)] reflections
7857, 2838, 1942
Rint0.034
(sin θ/λ)max1)0.615
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.142, 1.03
No. of reflections2838
No. of parameters183
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.13

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.861.932.657 (3)141
C11—H11···S10.932.543.193 (3)128
N1—H1···S1i0.862.763.482 (2)142
Symmetry code: (i) x+1, y, z+2.
 

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