Ethyl 4-(3-butyrylthio-ureido)benzoate.

The title compound, C(14)H(18)N(2)O(3)S, crystallizes in the thio-amide form with an intra-molecular N-H⋯O hydrogen bond associated with the thio-urea unit. With the benzoic acid and the butyrylthio-ureido units, the mol-ecule consists of two planar building blocks connected by the common NH function adjacent to the aromatic ring. The inter-planar angle is 33.38 (3)°. Mol-ecules are connected in chains parallel to [110] by classical hydrogen bonds of the N-H⋯O type from the other NH group to the benzoate C=O of a neighboring mol-ecule.

Related literature

For related literature, see: del Campo et al. (2002 ▶); D’hooghe et al. (2005 ▶); Dušek (1985 ▶); Huebner et al. (1953 ▶); Rodriguez-Fernandez et al. (2005 ▶); Xu et al. (2004 ▶); Zeng et al. (2003 ▶).

Experimental

Crystal data

C14H18N2O3S

M = 294.36

Triclinic,

a = 7.9817 (4) Å

b = 9.8843 (6) Å

c = 11.0759 (6) Å

α = 114.472 (6)°

β = 101.156 (4)°

γ = 102.277 (5)°

V = 737.15 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.23 mm−1

T = 100 (2) K

0.28 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur S diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.944, T max = 1.000 (expected range = 0.918–0.973)

15025 measured reflections

4104 independent reflections

3045 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.096

S = 0.96

4104 reflections

191 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017868/im2072sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017868/im2072Isup2.hkl

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

C14H18N2O3S	Z = 2
Mr = 294.36	F000 = 312
Triclinic, P1	Dx = 1.326 Mg m−3
Hall symbol: -P 1	Melting point: 412 K
a = 7.9817 (4) Å	Mo Kα radiation λ = 0.71073 Å
b = 9.8843 (6) Å	Cell parameters from 7295 reflections
c = 11.0759 (6) Å	θ = 2.8–30.7º
α = 114.472 (6)º	µ = 0.23 mm−1
β = 101.156 (4)º	T = 100 (2) K
γ = 102.277 (5)º	Pyramid, colourless
V = 737.15 (7) Å3	0.28 × 0.18 × 0.12 mm

Oxford Diffraction Xcalibur S diffractometer	4104 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3045 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.036
Detector resolution: 16.1057 pixels mm-1	θmax = 30.8º
T = 100(2) K	θmin = 2.8º
ω scans	h = −10→11
Absorption correction: multi-scan(CrysAlis RED; Oxford Diffraction, 2008)	k = −14→13
Tmin = 0.944, Tmax = 1.000	l = −15→15
15025 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.059P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96	(Δ/σ)max = 0.001
4104 reflections	Δρmax = 0.45 e Å−3
191 parameters	Δρmin = −0.24 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)- 7.3219 (0.0010) x + 3.9334 (0.0038) y + 4.1423 (0.0037) z = 2.1058 (0.0010)* -0.1410 (0.0006) S * -0.1556 (0.0012) C1 * -0.0747 (0.0014) C2 * 0.1521 (0.0012) C3 * 0.1191 (0.0012) C4 * -0.0053 (0.0010) C5 * 0.0111 (0.0008) O1 * 0.2033 (0.0010) N1 * -0.1089 (0.0009) N2Rms deviation of fitted atoms = 0.1249- 6.2227 (0.0013) x + 7.6804 (0.0015) y - 1.8402 (0.0041) z = 2.0195 (0.0017)Angle to previous plane (with approximate e.s.d.) = 33.38 (0.03)* -0.0510 (0.0011) C6 * -0.1492 (0.0011) C7 * -0.0777 (0.0011) C8 * 0.0751 (0.0012) C9 * 0.1972 (0.0012) C10 * 0.1468 (0.0011) C11 * 0.0732 (0.0011) C12 * 0.0367 (0.0013) C13 * -0.2621 (0.0011) C14 * 0.0788 (0.0009) O2 * 0.0421 (0.0010) O3 * -0.1099 (0.0009) N2Rms deviation of fitted atoms = 0.1266

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.

	x	y	z	Uiso*/Ueq
S	0.47787 (5)	0.62325 (4)	0.72720 (3)	0.02040 (10)
O1	0.11708 (12)	0.45529 (11)	0.28568 (9)	0.0208 (2)
O2	1.03683 (13)	1.25923 (10)	0.60929 (9)	0.0217 (2)
O3	1.04639 (12)	1.31498 (10)	0.82958 (9)	0.0200 (2)
N1	0.20683 (14)	0.45249 (13)	0.49337 (11)	0.0164 (2)
H01	0.186 (2)	0.3993 (17)	0.5294 (16)	0.020 (4)*
N2	0.38248 (15)	0.68105 (13)	0.51142 (11)	0.0168 (2)
H02	0.318 (2)	0.6327 (19)	0.4292 (16)	0.034 (5)*
C1	−0.2318 (2)	−0.03015 (17)	0.08970 (15)	0.0334 (4)
H1A	−0.1512	−0.0873	0.1061	0.050*
H1B	−0.2954	−0.0787	−0.0107	0.050*
H1C	−0.3200	−0.0343	0.1396	0.050*
C2	−0.1213 (2)	0.14034 (17)	0.14262 (14)	0.0313 (3)
H2A	−0.0333	0.1442	0.0912	0.038*
H2B	−0.2027	0.1971	0.1238	0.038*
C3	−0.02144 (18)	0.22120 (15)	0.29715 (13)	0.0195 (3)
H3A	−0.1110	0.2245	0.3480	0.023*
H3B	0.0497	0.1574	0.3162	0.023*
C4	0.10397 (16)	0.38601 (15)	0.35434 (13)	0.0161 (3)
C5	0.35361 (16)	0.58945 (14)	0.57240 (12)	0.0152 (2)
C6	0.52972 (17)	0.81999 (14)	0.56141 (13)	0.0158 (2)
C7	0.60248 (17)	0.84283 (15)	0.46402 (13)	0.0177 (3)
H7	0.5545	0.7659	0.3681	0.021*
C8	0.74473 (18)	0.97773 (15)	0.50722 (13)	0.0174 (3)
H8	0.7932	0.9937	0.4405	0.021*
C9	0.81749 (17)	1.09026 (14)	0.64780 (13)	0.0162 (3)
C10	0.74195 (17)	1.06811 (14)	0.74442 (13)	0.0176 (3)
H10	0.7898	1.1453	0.8402	0.021*
C11	0.59726 (18)	0.93406 (15)	0.70161 (13)	0.0183 (3)
H11	0.5448	0.9203	0.7675	0.022*
C12	0.97646 (17)	1.22913 (14)	0.69088 (13)	0.0168 (3)
C13	1.20350 (18)	1.45409 (16)	0.88185 (14)	0.0237 (3)
H13A	1.1674	1.5352	0.8632	0.028*
H13B	1.2942	1.4265	0.8350	0.028*
C14	1.28094 (19)	1.51477 (17)	1.03564 (14)	0.0267 (3)
H14A	1.1882	1.5369	1.0802	0.040*
H14B	1.3836	1.6116	1.0751	0.040*
H14C	1.3218	1.4356	1.0525	0.040*

	U11	U22	U33	U12	U13	U23
S	0.02247 (18)	0.01856 (17)	0.01304 (16)	−0.00118 (13)	−0.00170 (12)	0.00807 (12)
O1	0.0212 (5)	0.0233 (5)	0.0159 (5)	0.0035 (4)	0.0012 (4)	0.0114 (4)
O2	0.0249 (5)	0.0201 (5)	0.0190 (5)	0.0014 (4)	0.0087 (4)	0.0103 (4)
O3	0.0195 (5)	0.0196 (5)	0.0147 (4)	−0.0025 (4)	0.0005 (4)	0.0091 (4)
N1	0.0176 (5)	0.0163 (5)	0.0118 (5)	0.0002 (4)	0.0020 (4)	0.0072 (4)
N2	0.0179 (5)	0.0166 (5)	0.0114 (5)	0.0007 (4)	0.0007 (4)	0.0069 (4)
C1	0.0376 (9)	0.0212 (7)	0.0205 (7)	0.0011 (6)	−0.0044 (6)	0.0010 (6)
C2	0.0431 (9)	0.0214 (7)	0.0159 (7)	0.0027 (6)	−0.0031 (6)	0.0059 (6)
C3	0.0197 (6)	0.0180 (6)	0.0138 (6)	0.0018 (5)	0.0023 (5)	0.0046 (5)
C4	0.0147 (6)	0.0193 (6)	0.0126 (6)	0.0058 (5)	0.0036 (5)	0.0062 (5)
C5	0.0153 (6)	0.0146 (6)	0.0138 (6)	0.0040 (5)	0.0046 (5)	0.0055 (5)
C6	0.0153 (6)	0.0149 (6)	0.0166 (6)	0.0032 (5)	0.0030 (5)	0.0085 (5)
C7	0.0218 (7)	0.0169 (6)	0.0128 (6)	0.0053 (5)	0.0041 (5)	0.0066 (5)
C8	0.0220 (6)	0.0178 (6)	0.0155 (6)	0.0063 (5)	0.0071 (5)	0.0102 (5)
C9	0.0174 (6)	0.0152 (6)	0.0169 (6)	0.0043 (5)	0.0045 (5)	0.0093 (5)
C10	0.0215 (6)	0.0159 (6)	0.0132 (6)	0.0043 (5)	0.0040 (5)	0.0065 (5)
C11	0.0215 (6)	0.0188 (6)	0.0157 (6)	0.0050 (5)	0.0073 (5)	0.0093 (5)
C12	0.0186 (6)	0.0165 (6)	0.0170 (6)	0.0063 (5)	0.0048 (5)	0.0096 (5)
C13	0.0192 (7)	0.0222 (7)	0.0232 (7)	−0.0037 (5)	−0.0011 (5)	0.0135 (6)
C14	0.0227 (7)	0.0281 (8)	0.0198 (7)	0.0003 (6)	0.0025 (5)	0.0086 (6)

S—C5	1.6617 (13)	C13—C14	1.4939 (18)
O1—C4	1.2207 (15)	N1—H01	0.791 (13)
O2—C12	1.2114 (15)	N2—H02	0.823 (15)
O3—C12	1.3336 (15)	C1—H1A	0.9800
O3—C13	1.4576 (15)	C1—H1B	0.9800
N1—C5	1.3850 (16)	C1—H1C	0.9800
N1—C4	1.3856 (16)	C2—H2A	0.9900
N2—C5	1.3443 (16)	C2—H2B	0.9900
N2—C6	1.4161 (16)	C3—H3A	0.9900
C1—C2	1.520 (2)	C3—H3B	0.9900
C2—C3	1.5071 (18)	C7—H7	0.9500
C3—C4	1.5044 (17)	C8—H8	0.9500
C6—C11	1.3929 (17)	C10—H10	0.9500
C6—C7	1.3930 (17)	C11—H11	0.9500
C7—C8	1.3833 (17)	C13—H13A	0.9900
C8—C9	1.3926 (17)	C13—H13B	0.9900
C9—C10	1.3944 (17)	C14—H14A	0.9800
C9—C12	1.4846 (17)	C14—H14B	0.9800
C10—C11	1.3896 (17)	C14—H14C	0.9800
C12—O3—C13	116.02 (10)	C2—C1—H1C	109.5
C5—N1—C4	129.07 (11)	H1A—C1—H1C	109.5
C5—N2—C6	127.24 (11)	H1B—C1—H1C	109.5
C3—C2—C1	111.68 (12)	C3—C2—H2A	109.3
C4—C3—C2	114.61 (11)	C1—C2—H2A	109.3
O1—C4—N1	122.53 (12)	C3—C2—H2B	109.3
O1—C4—C3	123.91 (11)	C1—C2—H2B	109.3
N1—C4—C3	113.56 (11)	H2A—C2—H2B	107.9
N2—C5—N1	114.66 (11)	C4—C3—H3A	108.6
N2—C5—S	126.56 (9)	C2—C3—H3A	108.6
N1—C5—S	118.75 (9)	C4—C3—H3B	108.6
C11—C6—C7	120.20 (11)	C2—C3—H3B	108.6
C11—C6—N2	122.15 (11)	H3A—C3—H3B	107.6
C7—C6—N2	117.61 (11)	C8—C7—H7	120.1
C8—C7—C6	119.86 (11)	C6—C7—H7	120.1
C7—C8—C9	120.51 (11)	C7—C8—H8	119.7
C8—C9—C10	119.35 (12)	C9—C8—H8	119.7
C8—C9—C12	118.79 (11)	C11—C10—H10	119.7
C10—C9—C12	121.84 (11)	C9—C10—H10	119.7
C11—C10—C9	120.51 (12)	C10—C11—H11	120.2
C10—C11—C6	119.52 (11)	C6—C11—H11	120.2
O2—C12—O3	124.13 (12)	O3—C13—H13A	110.2
O2—C12—C9	123.78 (11)	C14—C13—H13A	110.2
O3—C12—C9	112.08 (10)	O3—C13—H13B	110.2
O3—C13—C14	107.33 (10)	C14—C13—H13B	110.2
C5—N1—H01	115.6 (11)	H13A—C13—H13B	108.5
C4—N1—H01	114.8 (11)	C13—C14—H14A	109.5
C5—N2—H02	109.4 (11)	C13—C14—H14B	109.5
C6—N2—H02	121.4 (11)	H14A—C14—H14B	109.5
C2—C1—H1A	109.5	C13—C14—H14C	109.5
C2—C1—H1B	109.5	H14A—C14—H14C	109.5
H1A—C1—H1B	109.5	H14B—C14—H14C	109.5
C1—C2—C3—C4	174.75 (13)	C7—C8—C9—C10	−1.97 (19)
C5—N1—C4—O1	−10.3 (2)	C7—C8—C9—C12	176.71 (11)
C5—N1—C4—C3	168.79 (12)	C8—C9—C10—C11	0.99 (19)
C2—C3—C4—O1	4.85 (19)	C12—C9—C10—C11	−177.65 (12)
C2—C3—C4—N1	−174.24 (12)	C9—C10—C11—C6	1.1 (2)
C6—N2—C5—N1	−174.22 (11)	C7—C6—C11—C10	−2.31 (19)
C6—N2—C5—S	4.13 (19)	N2—C6—C11—C10	−179.92 (12)
C4—N1—C5—N2	10.80 (19)	C13—O3—C12—O2	1.00 (18)
C4—N1—C5—S	−167.69 (10)	C13—O3—C12—C9	179.95 (10)
C5—N2—C6—C11	−42.44 (19)	C8—C9—C12—O2	7.60 (19)
C5—N2—C6—C7	139.90 (13)	C10—C9—C12—O2	−173.76 (13)
C11—C6—C7—C8	1.35 (19)	C8—C9—C12—O3	−171.36 (12)
N2—C6—C7—C8	179.06 (11)	C10—C9—C12—O3	7.28 (17)
C6—C7—C8—C9	0.81 (19)	C12—O3—C13—C14	−169.36 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H02···O1	0.82 (2)	1.92 (2)	2.653 (1)	148 (2)
N1—H01···O2i	0.79 (1)	2.20 (1)	2.957 (1)	160 (2)
C13—H13A···O1ii	0.99	2.58	3.363 (2)	136
C1—H1B···Siii	0.98	3.00	3.854 (2)	147
C13—H13B···Siv	0.99	2.96	3.577 (1)	122
C14—H14C···Sv	0.98	2.98	3.821 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H02⋯O1	0.82 (2)	1.92 (2)	2.653 (1)	148 (2)
N1—H01⋯O2i	0.79 (1)	2.20 (1)	2.957 (1)	160 (2)
C13—H13A⋯O1ii	0.99	2.58	3.363 (2)	136
C1—H1B⋯Siii	0.98	3.00	3.854 (2)	147
C13—H13B⋯Siv	0.99	2.96	3.577 (1)	122
C14—H14C⋯Sv	0.98	2.98	3.821 (2)	144

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .