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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2774.
Published online 2009 October 17. doi:  10.1107/S160053680904183X
PMCID: PMC2970993

Ethyl 4-[3-(2-methyl­benzo­yl)thio­ureido]benzoate

Abstract

The mol­ecular conformation of the title compound, C18H18N2O3S, is stabilized by an intra­molecular N—H(...)O hydrogen bond. The crystal packing shows centrosymmetric dimers connected by N—H(...)S hydrogen bonds. The terminal eth­oxy substituents are statistically disordered [occupancy ratio 0.527 (5):0.473 (5)].

Related literature

For the use of thio­urea derivatives in organic synthesis and analysis, see: Eynde & Watte (2003 [triangle]); Fu et al. (1999 [triangle]); Rashdan et al. (2006 [triangle]); Maryanoff et al. (1986 [triangle]); Wang et al.(2005 [triangle]); Saeed et al. (2008 [triangle]); Koch, (2001 [triangle]). For their bioactivity and pharmaceutical applications, see: Upadhyaya & Srivastava (1982 [triangle]); Ramadas et al. (1998 [triangle]); Blum & Hayes (1979 [triangle]); DeBeer et al. (1936 [triangle]). For related structures, see: Saeed & Flörke (2007a [triangle],b [triangle]); Saeed et al. (2009 [triangle]).

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Object name is e-65-o2774-scheme1.jpg

Experimental

Crystal data

  • C18H18N2O3S
  • M r = 342.40
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2774-efi1.jpg
  • a = 7.4555 (3) Å
  • b = 7.6311 (4) Å
  • c = 15.2468 (8) Å
  • α = 96.456 (4)°
  • β = 103.860 (5)°
  • γ = 92.908 (4)°
  • V = 834.13 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 173 K
  • 0.33 × 0.32 × 0.28 mm

Data collection

  • Stoe IPDS II two-circle-diffractometer
  • Absorption correction: multi-scan (MULABS; Spek, 2009 [triangle]; Blessing, 1995 [triangle]) T min = 0.933, T max = 0.943
  • 22798 measured reflections
  • 4659 independent reflections
  • 4311 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.100
  • S = 1.04
  • 4659 reflections
  • 246 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904183X/im2145sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904183X/im2145Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The background of this study has been described in our earlier paper concerning the crystal structure of 1-(2-Chloro-5-nitrophenyl)-3-(2,2-dimethylpropionyl)thiourea (Saeed et al., 2009). As part of our work on the structure of thioureas, we report here the structure of the title derivative, I, Fig 1.

The molecular conformation of the title compound, C18H18N2O3S, is stabilized by intramolecular N—H···O hydrogen bonds. The crystal packing shows centrosymmetric dimers connected by N—H···S hydrogen bonds (Table 1). Terminal ethoxy substituents are statistically disordered.

Experimental

A solution of 2-methylbenzoyl chloride (10 mmol) in acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (10 mmol) in acetone (30 ml) and the reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 4-aminobenzoic acid ethyl ester (10 mmol) in acetone (10 ml) was added and the resulting mixture refluxed for 3 h. The reaction mixture was poured into cold water and the precipitated thiourea was recrystallized from aqueous ethanol. Anal. calcd. for C18H18N2O3S: C, 63.14; H, 5.30; N, 8.18; S, 9.36% found: C, 63.26; H, 5.34; N, 8.21; S, 9.27%;

Refinement

H atoms were positioned geometrically and refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 Ueq(C,N) or U(H) = 1.5 Ueq(Cmethyl)] using a riding model with C—H(aromatic) = 0.95 Å, CH(methyl) = 0.98 Å, or CH(methylene) = 0.99 Å, respectively. H atoms bonded to N were set to the position where they were found in the difference map. The ethoxy group is disordered over two positions with a site occupation factor of 0.527 (5) for the major occupied site.

Figures

Fig. 1.
Perspective view of the title compound. The disordered atoms of the minor occupied site have been omitted for clarity. Displacement ellipsoids are shown at the 50 % probability level.
Fig. 2.
Packing diagram of the title compound. Hydrogen bonds shown as dashed lines. The minor occupied sites are omitted for clarity.

Crystal data

C18H18N2O3SZ = 2
Mr = 342.40F(000) = 360
Triclinic, P1Dx = 1.363 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4555 (3) ÅCell parameters from 42517 reflections
b = 7.6311 (4) Åθ = 3.4–29.9°
c = 15.2468 (8) ŵ = 0.21 mm1
α = 96.456 (4)°T = 173 K
β = 103.860 (5)°Block, colourless
γ = 92.908 (4)°0.33 × 0.32 × 0.28 mm
V = 834.13 (7) Å3

Data collection

Stoe IPDS II two-circle-diffractometer4659 independent reflections
Radiation source: fine-focus sealed tube4311 reflections with I > 2σ(I)
graphiteRint = 0.057
ω scansθmax = 29.6°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)h = −10→10
Tmin = 0.933, Tmax = 0.943k = −10→10
22798 measured reflectionsl = −21→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0517P)2 + 0.2098P] where P = (Fo2 + 2Fc2)/3
4659 reflections(Δ/σ)max = 0.002
246 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.37 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/UeqOcc. (<1)
S11.09603 (4)0.22920 (4)0.599200 (16)0.02926 (8)
O10.54635 (11)0.37544 (11)0.42973 (5)0.03282 (18)
O21.1748 (4)1.1151 (2)0.86115 (13)0.0302 (5)0.527 (5)
O2A1.0912 (4)1.1206 (2)0.88161 (14)0.0309 (6)0.473 (5)
O31.23261 (17)0.91072 (12)0.96012 (6)0.0521 (3)
N10.82261 (12)0.44800 (11)0.57980 (5)0.02358 (17)
H10.72820.47280.54780.028*
N20.77873 (12)0.19546 (11)0.47488 (6)0.02420 (17)
H20.82420.09560.45700.029*
C10.89035 (13)0.29850 (13)0.55169 (6)0.02227 (18)
C20.61524 (13)0.23496 (13)0.41838 (6)0.02368 (18)
C110.90732 (12)0.57062 (12)0.65792 (6)0.02124 (17)
C120.98398 (14)0.51635 (13)0.74226 (7)0.02457 (19)
H120.98400.39410.74900.029*
C131.06022 (14)0.64342 (13)0.81625 (7)0.02587 (19)
H131.11310.60750.87390.031*
C141.06025 (15)0.82288 (13)0.80705 (7)0.0273 (2)
C150.97895 (15)0.87601 (13)0.72331 (7)0.0286 (2)
H150.97550.99830.71700.034*
C160.90262 (14)0.74958 (13)0.64881 (6)0.02458 (19)
H160.84710.78560.59150.029*
C171.1522 (2)0.95152 (16)0.88788 (9)0.0456 (3)
C181.2785 (4)1.2514 (3)0.93166 (16)0.0336 (6)0.527 (5)
H18A1.32221.35040.90330.040*0.527 (5)
H18B1.38861.20240.96810.040*0.527 (5)
C191.1602 (4)1.3183 (4)0.9924 (2)0.0404 (6)0.527 (5)
H19A1.23191.41071.03940.061*0.527 (5)
H19B1.11931.22061.02150.061*0.527 (5)
H19C1.05181.36730.95640.061*0.527 (5)
C18A1.1603 (4)1.2562 (4)0.9587 (2)0.0324 (6)0.473 (5)
H18C1.16391.20481.01580.039*0.473 (5)
H18D1.07511.35190.95530.039*0.473 (5)
C19A1.3507 (5)1.3318 (4)0.9602 (2)0.0419 (8)0.473 (5)
H19D1.39421.42261.01310.063*0.473 (5)
H19E1.34691.38490.90430.063*0.473 (5)
H19F1.43561.23750.96440.063*0.473 (5)
C210.53091 (13)0.08983 (13)0.34332 (7)0.02406 (19)
C220.50526 (15)−0.08026 (14)0.36571 (8)0.0294 (2)
H220.5425−0.10130.42750.035*
C230.42550 (17)−0.21929 (16)0.29831 (9)0.0373 (3)
H230.4064−0.33490.31360.045*
C240.37444 (18)−0.18683 (18)0.20872 (9)0.0419 (3)
H240.3212−0.28120.16210.050*
C250.40002 (17)−0.01808 (17)0.18616 (8)0.0369 (3)
H250.36470.00110.12410.044*
C260.47678 (14)0.12474 (15)0.25293 (7)0.0277 (2)
C270.49622 (18)0.30658 (17)0.22573 (8)0.0363 (2)
H27A0.38520.36780.22910.054*
H27B0.51090.29690.16320.054*
H27C0.60530.37370.26710.054*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.02783 (13)0.03461 (14)0.02109 (12)0.01339 (10)−0.00154 (9)−0.00282 (9)
O10.0292 (4)0.0317 (4)0.0296 (4)0.0119 (3)−0.0037 (3)−0.0098 (3)
O20.0369 (11)0.0226 (7)0.0255 (8)−0.0031 (6)0.0009 (7)−0.0036 (6)
O2A0.0409 (14)0.0227 (8)0.0229 (8)0.0024 (7)−0.0005 (8)−0.0048 (6)
O30.0761 (7)0.0317 (4)0.0293 (4)−0.0019 (4)−0.0204 (4)−0.0010 (3)
N10.0232 (4)0.0242 (4)0.0187 (3)0.0062 (3)−0.0018 (3)−0.0032 (3)
N20.0249 (4)0.0245 (4)0.0195 (4)0.0070 (3)0.0007 (3)−0.0045 (3)
C10.0242 (4)0.0250 (4)0.0161 (4)0.0044 (3)0.0029 (3)−0.0004 (3)
C20.0224 (4)0.0264 (4)0.0199 (4)0.0046 (3)0.0031 (3)−0.0032 (3)
C110.0198 (4)0.0235 (4)0.0180 (4)0.0019 (3)0.0021 (3)−0.0020 (3)
C120.0290 (4)0.0217 (4)0.0205 (4)0.0023 (3)0.0022 (3)0.0007 (3)
C130.0305 (5)0.0248 (4)0.0188 (4)0.0020 (4)−0.0003 (3)0.0017 (3)
C140.0304 (5)0.0234 (4)0.0219 (4)−0.0016 (4)−0.0035 (4)−0.0004 (3)
C150.0337 (5)0.0215 (4)0.0252 (5)−0.0009 (4)−0.0020 (4)0.0024 (3)
C160.0262 (4)0.0253 (4)0.0193 (4)0.0023 (3)0.0002 (3)0.0025 (3)
C170.0634 (8)0.0239 (5)0.0322 (6)−0.0038 (5)−0.0185 (6)−0.0001 (4)
C180.0361 (12)0.0261 (11)0.0317 (11)−0.0045 (10)0.0014 (9)−0.0073 (9)
C190.0509 (14)0.0331 (13)0.0341 (14)0.0081 (11)0.0081 (11)−0.0053 (11)
C18A0.0436 (14)0.0228 (12)0.0262 (13)0.0009 (10)0.0060 (10)−0.0101 (10)
C19A0.0430 (15)0.0352 (15)0.0415 (15)−0.0034 (13)0.0032 (12)−0.0028 (12)
C210.0200 (4)0.0269 (4)0.0222 (4)0.0034 (3)0.0035 (3)−0.0065 (3)
C220.0272 (5)0.0292 (5)0.0310 (5)0.0026 (4)0.0085 (4)−0.0031 (4)
C230.0334 (5)0.0283 (5)0.0479 (7)−0.0032 (4)0.0129 (5)−0.0090 (5)
C240.0357 (6)0.0405 (6)0.0406 (6)−0.0035 (5)0.0054 (5)−0.0208 (5)
C250.0342 (5)0.0455 (6)0.0244 (5)0.0044 (5)0.0018 (4)−0.0121 (4)
C260.0243 (4)0.0336 (5)0.0222 (4)0.0049 (4)0.0036 (3)−0.0053 (4)
C270.0398 (6)0.0395 (6)0.0283 (5)0.0073 (5)0.0056 (4)0.0034 (4)

Geometric parameters (Å, °)

S1—C11.6709 (10)C18—H18A0.9900
O1—C21.2247 (12)C18—H18B0.9900
O2—C171.370 (2)C19—H19A0.9800
O2—C181.451 (3)C19—H19B0.9800
O2A—C171.395 (2)C19—H19C0.9800
O2A—C18A1.449 (4)C18A—C19A1.499 (4)
O3—C171.2038 (15)C18A—H18C0.9900
N1—C11.3388 (12)C18A—H18D0.9900
N1—C111.4220 (11)C19A—H19D0.9800
N1—H10.7998C19A—H19E0.9800
N2—C21.3824 (12)C19A—H19F0.9800
N2—C11.3936 (12)C21—C221.3941 (15)
N2—H20.8911C21—C261.4001 (14)
C2—C211.4937 (13)C22—C231.3904 (15)
C11—C161.3895 (13)C22—H220.9500
C11—C121.3941 (13)C23—C241.382 (2)
C12—C131.3881 (13)C23—H230.9500
C12—H120.9500C24—C251.385 (2)
C13—C141.3923 (14)C24—H240.9500
C13—H130.9500C25—C261.4000 (14)
C14—C151.3900 (14)C25—H250.9500
C14—C171.4858 (14)C26—C271.5021 (17)
C15—C161.3904 (13)C27—H27A0.9800
C15—H150.9500C27—H27B0.9800
C16—H160.9500C27—H27C0.9800
C18—C191.493 (4)
C17—O2—C18115.67 (16)C18—C19—H19A109.5
C17—O2A—C18A118.32 (17)C18—C19—H19B109.5
C1—N1—C11126.33 (8)H19A—C19—H19B109.5
C1—N1—H1116.3C18—C19—H19C109.5
C11—N1—H1117.2H19A—C19—H19C109.5
C2—N2—C1128.53 (8)H19B—C19—H19C109.5
C2—N2—H2115.7O2A—C18A—C19A111.2 (4)
C1—N2—H2115.5O2A—C18A—H18C109.4
N1—C1—N2116.03 (8)C19A—C18A—H18C109.4
N1—C1—S1125.74 (7)O2A—C18A—H18D109.4
N2—C1—S1118.21 (7)C19A—C18A—H18D109.4
O1—C2—N2122.79 (9)H18C—C18A—H18D108.0
O1—C2—C21123.60 (9)C18A—C19A—H19D109.5
N2—C2—C21113.61 (8)C18A—C19A—H19E109.5
C16—C11—C12120.35 (8)H19D—C19A—H19E109.5
C16—C11—N1117.45 (8)C18A—C19A—H19F109.5
C12—C11—N1122.11 (9)H19D—C19A—H19F109.5
C13—C12—C11119.08 (9)H19E—C19A—H19F109.5
C13—C12—H12120.5C22—C21—C26120.98 (9)
C11—C12—H12120.5C22—C21—C2118.37 (9)
C12—C13—C14120.85 (9)C26—C21—C2120.65 (9)
C12—C13—H13119.6C23—C22—C21120.47 (11)
C14—C13—H13119.6C23—C22—H22119.8
C15—C14—C13119.70 (9)C21—C22—H22119.8
C15—C14—C17122.23 (10)C24—C23—C22119.01 (12)
C13—C14—C17118.05 (9)C24—C23—H23120.5
C14—C15—C16119.80 (9)C22—C23—H23120.5
C14—C15—H15120.1C23—C24—C25120.70 (10)
C16—C15—H15120.1C23—C24—H24119.7
C11—C16—C15120.18 (9)C25—C24—H24119.7
C11—C16—H16119.9C24—C25—C26121.39 (11)
C15—C16—H16119.9C24—C25—H25119.3
O3—C17—O2124.17 (12)C26—C25—H25119.3
O3—C17—O2A120.61 (13)C25—C26—C21117.44 (11)
O3—C17—C14124.28 (11)C25—C26—C27119.59 (10)
O2—C17—C14109.38 (11)C21—C26—C27122.97 (9)
O2A—C17—C14112.60 (11)C26—C27—H27A109.5
O2—C18—C19110.5 (3)C26—C27—H27B109.5
O2—C18—H18A109.6H27A—C27—H27B109.5
C19—C18—H18A109.6C26—C27—H27C109.5
O2—C18—H18B109.6H27A—C27—H27C109.5
C19—C18—H18B109.6H27B—C27—H27C109.5
H18A—C18—H18B108.1
C11—N1—C1—N2177.55 (9)C15—C14—C17—O3−175.89 (16)
C11—N1—C1—S1−3.80 (15)C13—C14—C17—O32.8 (2)
C2—N2—C1—N16.94 (15)C15—C14—C17—O2−12.1 (2)
C2—N2—C1—S1−171.82 (9)C13—C14—C17—O2166.59 (17)
C1—N2—C2—O10.83 (17)C15—C14—C17—O2A22.0 (2)
C1—N2—C2—C21−178.64 (9)C13—C14—C17—O2A−159.3 (2)
C1—N1—C11—C16137.72 (11)C17—O2—C18—C19−77.4 (3)
C1—N1—C11—C12−45.70 (15)C17—O2A—C18A—C19A79.8 (3)
C16—C11—C12—C13−1.85 (15)O1—C2—C21—C22−128.25 (12)
N1—C11—C12—C13−178.34 (9)N2—C2—C21—C2251.21 (12)
C11—C12—C13—C140.19 (16)O1—C2—C21—C2650.88 (15)
C12—C13—C14—C151.59 (17)N2—C2—C21—C26−129.66 (10)
C12—C13—C14—C17−177.10 (12)C26—C21—C22—C230.19 (16)
C13—C14—C15—C16−1.71 (17)C2—C21—C22—C23179.32 (9)
C17—C14—C15—C16176.93 (12)C21—C22—C23—C240.89 (17)
C12—C11—C16—C151.74 (15)C22—C23—C24—C25−0.76 (19)
N1—C11—C16—C15178.39 (9)C23—C24—C25—C26−0.44 (19)
C14—C15—C16—C110.06 (17)C24—C25—C26—C211.48 (17)
C18—O2—C17—O3−10.6 (4)C24—C25—C26—C27−177.99 (11)
C18—O2—C17—O2A83.6 (3)C22—C21—C26—C25−1.35 (15)
C18—O2—C17—C14−174.5 (2)C2—C21—C26—C25179.54 (9)
C18A—O2A—C17—O313.0 (4)C22—C21—C26—C27178.11 (10)
C18A—O2A—C17—O2−93.5 (4)C2—C21—C26—C27−1.00 (15)
C18A—O2A—C17—C14175.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O10.802.012.669 (1)139
N2—H2···S1i0.892.673.5551 (9)170

Symmetry codes: (i) −x+2, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2145).

References

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