supplementary materials


Acta Cryst. (2007). E63, o3695    [ doi:10.1107/S1600536807037531 ]

1-(3-Methoxyphenyl)-3-(4-methylbenzoyl)thiourea

A. Saeed and U. Flörke

Abstract top

In the structure of the title compound, C16H16N2O2S, the dihedral angle between the two aromatic ring planes is 48.3 (1)°. Intermolecular N-H...S hydrogen bonds link the molecules into dimers which are stacked along [100].

Comment top

The background to this study has been set out in the previous paper (Saeed & Flörke, 2007). In the molecular structure of the title compound, (I), (Fig. 1) the torsion angles C8—N2—C9—O1 of −5.4 (4)° and C9—N2—C8—N1 of 4.8 (3)° reflect the almost planar conformation of I with respect to the thiocarbonyl and carbonyl parts. The two aromatic rings form a dihedral angle of 48.30 (8)°, the associated N2—C9—C10—C15 torsion angle is −17.5 (3)°. All other bond parameters (Table 1) are typical for these thiourea compounds (Saeed & Flörke, 2006). Also typical is the intramolecular N1—H···O hydrogen bond. The crystal packing is determined by intermolecular N2—H···S hydrogen bonds, forming centrosymmetric dimers which are stacked along [100].

Related literature top

For related literature, see: Saeed & Flörke (2006, 2007).

Experimental top

A solution of 4-methylbenzoyl chloride (1.75 g,10 mmol) in acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (0.97 g,10 mmol) in acetone (30 ml) and the reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 3-methoxyaniline (10 mmol) in acetone (10 ml) was added and the resulting mixture refluxed for 2.0 h. The reaction mixture was poured into cold water when the thiourea was precipitated as a solid. Recrystallized from ethanol as colourless crystals (2.4 g, 8.0 mmol, 80%). m.p. 79°C. IR (KBr) cm-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610 (arom.), 1529 (thioureido I) 1325 II, 1160 III, 744, 762; 1H NMR (CDCl3) ?: 3.89 (3H, s, ArOCH3), 7.31–7.75 (aromatic), 9.19 (1H, s, broad, NH); 12.76 (1H, s, broad, NH); 13 C NMR (CDCl3) ? 55.6 (OCH3), 126.2 (4 CH), 129.0 (2 CH), 129.20 (2CH), 130.7 (C), 132.1 (C),134.8 (C) 142.3 (C), 168.1 (C=O), 178.4 (C=S). EIMS m/e: 300, 168.9,149, 119, 91, 64.9; Analysis calculated for C16H16N2O2S C, 63.98; H, 5.37; N, 9.33; S, 10.67 found C, 64.01; H, 5.32; N, 9.10; S, 10.65

Refinement top

Hydrogen atoms were located in difference syntheses, constrained at idealized positions riding on the C (C—H = 0.95–0.99 Å) or N (N—H = 0.88 Å) atoms with isotropic displacement parameters Uiso(H) = 1.2U(Ceq / Neq) and 1.5(methyl-C). Methyl H atoms were refined on the basis of rigid groups allowed to rotate but not tip.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1.  
1-(3-Methoxyphenyl)-3-(4-methylbenzoyl)thiourea top
Crystal data top
C16H16N2O2SF000 = 632
Mr = 300.37Dx = 1.339 Mg m3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1407 reflections
a = 5.3031 (6) Åθ = 2.5–21.2º
b = 21.159 (2) ŵ = 0.22 mm1
c = 13.2837 (14) ÅT = 120 (2) K
β = 90.027 (15)ºNeedle, colourless
V = 1490.5 (3) Å30.52 × 0.10 × 0.09 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer
3535 independent reflections
Radiation source: sealed tube2050 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.091
T = 120(2) Kθmax = 27.9º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 6→6
Tmin = 0.893, Tmax = 0.980k = 27→27
12383 measured reflectionsl = 17→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0434P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.88(Δ/σ)max < 0.001
3535 reflectionsΔρmax = 0.32 e Å3
190 parametersΔρmin = 0.33 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C16H16N2O2SV = 1490.5 (3) Å3
Mr = 300.37Z = 4
Monoclinic, P21/nMo Kα
a = 5.3031 (6) ŵ = 0.22 mm1
b = 21.159 (2) ÅT = 120 (2) K
c = 13.2837 (14) Å0.52 × 0.10 × 0.09 mm
β = 90.027 (15)º
Data collection top
Bruker SMART APEX
diffractometer
3535 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2050 reflections with I > 2σ(I)
Tmin = 0.893, Tmax = 0.980Rint = 0.091
12383 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045190 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 0.88Δρmax = 0.32 e Å3
3535 reflectionsΔρmin = 0.33 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.32324 (14)1.01213 (3)0.85607 (5)0.0443 (2)
O10.6061 (3)0.81054 (7)0.82493 (11)0.0427 (5)
O20.0758 (3)0.86111 (8)0.42661 (12)0.0484 (5)
N10.3031 (3)0.90015 (8)0.76221 (13)0.0325 (5)
H10.35420.86060.76360.039*
N20.5727 (3)0.90797 (8)0.89643 (13)0.0326 (5)
H20.62530.93090.94760.039*
C10.1346 (4)0.91542 (10)0.68283 (16)0.0302 (5)
C20.0701 (5)0.95549 (10)0.69401 (18)0.0371 (6)
H2A0.10010.97670.75590.044*
C30.2299 (5)0.96387 (11)0.6126 (2)0.0447 (7)
H3A0.37060.99130.61940.054*
C40.1907 (5)0.93341 (11)0.52169 (19)0.0421 (7)
H4A0.30280.93980.46680.050*
C50.0128 (5)0.89387 (10)0.51231 (17)0.0348 (6)
C60.1752 (4)0.88476 (9)0.59290 (17)0.0321 (6)
H6A0.31540.85720.58600.039*
C70.0996 (5)0.86212 (13)0.34504 (18)0.0579 (8)
H7A0.26510.84800.36890.087*
H7B0.04070.83380.29160.087*
H7C0.11320.90520.31870.087*
C80.3948 (4)0.93659 (10)0.83449 (16)0.0304 (5)
C90.6782 (5)0.84850 (10)0.88869 (16)0.0322 (5)
C100.8808 (4)0.83358 (9)0.96113 (15)0.0278 (5)
C110.9470 (5)0.77047 (10)0.97489 (16)0.0360 (6)
H11A0.86250.73840.93780.043*
C121.1343 (5)0.75421 (10)1.04196 (16)0.0362 (6)
H12A1.17830.71101.05000.043*
C131.2603 (4)0.79982 (10)1.09818 (15)0.0317 (5)
C141.1956 (5)0.86231 (10)1.08289 (17)0.0381 (6)
H14A1.28060.89431.11980.046*
C151.0105 (4)0.87923 (10)1.01519 (16)0.0342 (6)
H15A0.97140.92261.00550.041*
C161.4626 (5)0.78203 (11)1.17233 (17)0.0431 (6)
H16A1.62140.80241.15320.065*
H16B1.48480.73601.17220.065*
H16C1.41330.79601.23980.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0624 (5)0.0291 (3)0.0416 (4)0.0117 (3)0.0172 (3)0.0020 (3)
O10.0533 (12)0.0361 (9)0.0387 (10)0.0122 (8)0.0175 (9)0.0076 (7)
O20.0523 (13)0.0539 (11)0.0390 (10)0.0027 (9)0.0230 (9)0.0015 (8)
N10.0388 (13)0.0261 (9)0.0327 (11)0.0039 (9)0.0077 (9)0.0008 (8)
N20.0410 (13)0.0304 (10)0.0264 (10)0.0067 (9)0.0094 (9)0.0023 (8)
C10.0281 (14)0.0267 (11)0.0357 (13)0.0049 (10)0.0084 (11)0.0077 (10)
C20.0311 (15)0.0371 (13)0.0429 (15)0.0004 (11)0.0023 (12)0.0045 (11)
C30.0281 (16)0.0392 (14)0.0667 (19)0.0018 (12)0.0078 (14)0.0118 (13)
C40.0345 (16)0.0438 (14)0.0479 (17)0.0037 (12)0.0199 (13)0.0147 (12)
C50.0366 (16)0.0316 (12)0.0362 (15)0.0092 (11)0.0106 (12)0.0068 (10)
C60.0306 (15)0.0281 (11)0.0376 (14)0.0010 (10)0.0091 (11)0.0036 (10)
C70.060 (2)0.076 (2)0.0387 (16)0.0074 (15)0.0272 (15)0.0082 (13)
C80.0335 (15)0.0318 (12)0.0259 (12)0.0034 (10)0.0014 (11)0.0029 (9)
C90.0377 (15)0.0315 (12)0.0274 (13)0.0043 (11)0.0006 (11)0.0007 (10)
C100.0300 (14)0.0309 (12)0.0224 (12)0.0049 (10)0.0026 (10)0.0005 (9)
C110.0426 (16)0.0319 (12)0.0337 (14)0.0029 (11)0.0105 (12)0.0056 (10)
C120.0409 (16)0.0303 (12)0.0375 (14)0.0075 (11)0.0073 (12)0.0016 (10)
C130.0291 (14)0.0442 (13)0.0217 (12)0.0018 (11)0.0011 (10)0.0008 (10)
C140.0402 (16)0.0358 (13)0.0382 (14)0.0041 (11)0.0054 (12)0.0068 (11)
C150.0390 (16)0.0270 (12)0.0366 (14)0.0007 (10)0.0030 (12)0.0003 (10)
C160.0375 (16)0.0543 (16)0.0374 (15)0.0000 (12)0.0074 (12)0.0000 (12)
Geometric parameters (Å, °) top
S1—C81.668 (2)C6—H6A0.9500
O1—C91.228 (2)C7—H7A0.9800
O2—C51.374 (3)C7—H7B0.9800
O2—C71.428 (3)C7—H7C0.9800
N1—C81.324 (3)C9—C101.477 (3)
N1—C11.419 (3)C10—C151.386 (3)
N1—H10.8800C10—C111.393 (3)
N2—C91.381 (3)C11—C121.378 (3)
N2—C81.391 (3)C11—H11A0.9500
N2—H20.8800C12—C131.391 (3)
C1—C61.376 (3)C12—H12A0.9500
C1—C21.385 (3)C13—C141.381 (3)
C2—C31.385 (3)C13—C161.504 (3)
C2—H2A0.9500C14—C151.379 (3)
C3—C41.385 (3)C14—H14A0.9500
C3—H3A0.9500C15—H15A0.9500
C4—C51.371 (3)C16—H16A0.9800
C4—H4A0.9500C16—H16B0.9800
C5—C61.387 (3)C16—H16C0.9800
C5—O2—C7117.6 (2)N1—C8—N2115.12 (18)
C8—N1—C1129.59 (18)N1—C8—S1126.83 (17)
C8—N1—H1115.2N2—C8—S1118.03 (16)
C1—N1—H1115.2O1—C9—N2121.4 (2)
C9—N2—C8128.87 (18)O1—C9—C10122.4 (2)
C9—N2—H2115.6N2—C9—C10116.18 (19)
C8—N2—H2115.6C15—C10—C11118.4 (2)
C6—C1—C2120.3 (2)C15—C10—C9123.34 (19)
C6—C1—N1116.0 (2)C11—C10—C9118.28 (19)
C2—C1—N1123.6 (2)C12—C11—C10120.4 (2)
C3—C2—C1118.3 (2)C12—C11—H11A119.8
C3—C2—H2A120.9C10—C11—H11A119.8
C1—C2—H2A120.9C11—C12—C13121.3 (2)
C2—C3—C4122.0 (2)C11—C12—H12A119.3
C2—C3—H3A119.0C13—C12—H12A119.3
C4—C3—H3A119.0C14—C13—C12117.8 (2)
C5—C4—C3118.8 (2)C14—C13—C16120.9 (2)
C5—C4—H4A120.6C12—C13—C16121.4 (2)
C3—C4—H4A120.6C15—C14—C13121.4 (2)
C4—C5—O2125.0 (2)C15—C14—H14A119.3
C4—C5—C6120.2 (2)C13—C14—H14A119.3
O2—C5—C6114.7 (2)C14—C15—C10120.7 (2)
C1—C6—C5120.5 (2)C14—C15—H15A119.7
C1—C6—H6A119.8C10—C15—H15A119.7
C5—C6—H6A119.8C13—C16—H16A109.5
O2—C7—H7A109.5C13—C16—H16B109.5
O2—C7—H7B109.5H16A—C16—H16B109.5
H7A—C7—H7B109.5C13—C16—H16C109.5
O2—C7—H7C109.5H16A—C16—H16C109.5
H7A—C7—H7C109.5H16B—C16—H16C109.5
H7B—C7—H7C109.5
C8—N1—C1—C6144.9 (2)C9—N2—C8—S1173.97 (18)
C8—N1—C1—C239.0 (3)C8—N2—C9—O15.4 (4)
C6—C1—C2—C30.3 (3)C8—N2—C9—C10174.6 (2)
N1—C1—C2—C3176.2 (2)O1—C9—C10—C15162.5 (2)
C1—C2—C3—C40.2 (3)N2—C9—C10—C1517.5 (3)
C2—C3—C4—C50.1 (4)O1—C9—C10—C1116.7 (3)
C3—C4—C5—O2179.4 (2)N2—C9—C10—C11163.3 (2)
C3—C4—C5—C60.1 (3)C15—C10—C11—C121.0 (3)
C7—O2—C5—C48.0 (3)C9—C10—C11—C12179.7 (2)
C7—O2—C5—C6172.4 (2)C10—C11—C12—C130.6 (4)
C2—C1—C6—C50.4 (3)C11—C12—C13—C141.5 (4)
N1—C1—C6—C5176.56 (19)C11—C12—C13—C16179.2 (2)
C4—C5—C6—C10.3 (3)C12—C13—C14—C150.8 (4)
O2—C5—C6—C1179.32 (18)C16—C13—C14—C15180.0 (2)
C1—N1—C8—N2175.1 (2)C13—C14—C15—C100.9 (4)
C1—N1—C8—S13.5 (4)C11—C10—C15—C141.7 (3)
C9—N2—C8—N14.8 (3)C9—C10—C15—C14179.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.882.893.7376 (19)163
N1—H1···O10.881.892.621 (2)140
Symmetry codes: (i) −x+1, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.882.893.7376 (19)163
N1—H1···O10.881.892.621 (2)140
Symmetry codes: (i) −x+1, −y+2, −z+2.
references
References top

Bruker (2002). SMART (Version 5.62), SAINT (Version 6.02), SHELXTL (Version 6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

Saeed, A. & Flörke, U. (2006). Acta Cryst. E62, o2924–o2925.

Saeed, A. & Flörke, U. (2007). Acta Cryst. E63, o1390–o1392.