Ethyl 2-benzamido-4,5,6,7-tetra-hydro-1-benzothio-phene-3-carboxyl-ate.

The mol-ecule of the title compound, C(18)H(19)NO(3)S, adopts an approximately planar conformation: the thio-phene and phenyl rings form a dihedral angle of 8.13 (11)° while the ethyl ester group (r.m.s. deviation = 0.0217 Å) is inclined at 1.25 (14) and 8.61 (13)°, respectively, to the thio-phene and phenyl rings. An intra-molecular N-H⋯O hydrogen bond with an S(6) ring motif occurs as well as an intra-molecular S⋯O hypervalent inter-action [S⋯O = 2.7369 (18) Å]. The cyclo-hexene ring adopts a half-chair conformation and is disordered over two positions with site occupation factors of 0.641 (6) and 0.359 (6). In the crystal, inversion dimers linked by pairs of O-H⋯O hydrogen bonds generate R(2) (2)(10) loops.

Related literature

For background on thio­phene derivatives, see: Dupin et al. (2002 ▶); Khan & Rolim (1983 ▶); Sabnis et al. (1999 ▶). For related structures, see: Harrison et al. (2006 ▶); Yathirajan et al. (2007 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C18H19NO3S

M = 329.40

Monoclinic,

a = 8.1061 (2) Å

b = 10.6593 (3) Å

c = 19.0554 (5) Å

β = 92.500 (1)°

V = 1644.92 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 296 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.953, T max = 0.958

12204 measured reflections

2964 independent reflections

2052 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.01

2964 reflections

210 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Crystal structure: contains datablocks text, I. DOI: 10.1107/S1600536810037761/gk2302sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037761/gk2302Isup2.hkl

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

C18H19NO3S	F(000) = 696
Mr = 329.40	Dx = 1.330 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2052 reflections
a = 8.1061 (2) Å	θ = 2.5–25.3°
b = 10.6593 (3) Å	µ = 0.21 mm−1
c = 19.0554 (5) Å	T = 296 K
β = 92.500 (1)°	Prism, colorless
V = 1644.92 (8) Å3	0.25 × 0.20 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	2964 independent reflections
Radiation source: fine-focus sealed tube	2052 reflections with I > 2σ(I)
graphite	Rint = 0.037
Detector resolution: 8.10 pixels mm-1	θmax = 25.3°, θmin = 2.5°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
Tmin = 0.953, Tmax = 0.958	l = −22→22
12204 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0503P)2 + 0.4332P] where P = (Fo2 + 2Fc2)/3
2964 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.16 e Å−3
6 restraints	Δρmin = −0.19 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	Occ. (<1)
S1	0.75739 (8)	0.64947 (6)	0.09851 (3)	0.0685 (2)
O1	0.9000 (2)	0.82309 (16)	0.01442 (9)	0.0875 (7)
O2	0.8026 (2)	0.41537 (14)	−0.09850 (7)	0.0658 (6)
O3	0.6816 (2)	0.26412 (14)	−0.03830 (7)	0.0666 (6)
N1	0.8625 (2)	0.63457 (16)	−0.03524 (8)	0.0527 (6)
C1	0.9770 (3)	0.8019 (2)	−0.10411 (11)	0.0545 (7)
C2	0.9702 (3)	0.7346 (2)	−0.16629 (12)	0.0679 (9)
C3	1.0262 (3)	0.7864 (3)	−0.22706 (13)	0.0781 (10)
C4	1.0909 (3)	0.9047 (3)	−0.22675 (14)	0.0804 (11)
C5	1.1013 (3)	0.9711 (3)	−0.16569 (16)	0.0830 (11)
C6	1.0438 (3)	0.9216 (2)	−0.10479 (13)	0.0697 (9)
C7	0.9121 (3)	0.7563 (2)	−0.03689 (12)	0.0582 (8)
C8	0.7865 (2)	0.5770 (2)	0.01970 (10)	0.0484 (7)
C9	0.7256 (2)	0.45660 (19)	0.01795 (10)	0.0464 (7)
C10	0.6520 (2)	0.4227 (2)	0.08292 (10)	0.0505 (7)
C11	0.5695 (3)	0.2999 (2)	0.09967 (11)	0.0615 (8)
C12A	0.5302 (8)	0.2864 (5)	0.1768 (3)	0.0771 (13)	0.641 (6)
C13A	0.4684 (7)	0.4071 (4)	0.2069 (3)	0.0771 (13)	0.641 (6)
C14	0.5952 (3)	0.5146 (3)	0.20270 (12)	0.0820 (10)
C15	0.6620 (3)	0.5167 (2)	0.12986 (11)	0.0601 (8)
C16	0.7408 (3)	0.3798 (2)	−0.04470 (11)	0.0518 (7)
C17	0.6953 (4)	0.1819 (2)	−0.09806 (13)	0.0804 (10)
C18	0.6130 (4)	0.0615 (3)	−0.08052 (16)	0.1017 (13)
C12B	0.4639 (11)	0.3191 (11)	0.1642 (4)	0.0771 (13)	0.359 (6)
C13B	0.5564 (13)	0.3883 (8)	0.2231 (4)	0.0771 (13)	0.359 (6)
H1	0.88006	0.58943	−0.07157	0.0632*
H4	1.12771	0.93963	−0.26797	0.0964*
H2	0.92751	0.65362	−0.16705	0.0815*
H3	1.01981	0.74051	−0.26860	0.0936*
H11A	0.64111	0.23142	0.08692	0.0738*
H11B	0.46774	0.29269	0.07120	0.0738*
H12A	0.44709	0.22178	0.18136	0.0926*	0.641 (6)
H12B	0.62887	0.26010	0.20338	0.0926*	0.641 (6)
H13A	0.44302	0.39369	0.25557	0.0926*	0.641 (6)
H13B	0.36703	0.43138	0.18147	0.0926*	0.641 (6)
H14A	0.54276	0.59409	0.21247	0.0985*
H14B	0.68476	0.50168	0.23738	0.0985*
H17A	0.81052	0.16736	−0.10724	0.0962*
H17B	0.64183	0.21915	−0.13955	0.0962*
H18A	0.66559	0.02642	−0.03888	0.1525*
H18B	0.62180	0.00366	−0.11881	0.1525*
H18C	0.49861	0.07682	−0.07259	0.1525*
H5	1.14776	1.05084	−0.16517	0.0996*
H6	1.04969	0.96880	−0.06371	0.0837*
H12C	0.36549	0.36616	0.15021	0.0926*	0.359 (6)
H12D	0.42929	0.23798	0.18130	0.0926*	0.359 (6)
H13C	0.48949	0.39036	0.26402	0.0926*	0.359 (6)
H13D	0.65770	0.34371	0.23564	0.0926*	0.359 (6)

	U11	U22	U33	U12	U13	U23
S1	0.0836 (4)	0.0704 (4)	0.0522 (3)	−0.0085 (3)	0.0127 (3)	−0.0147 (3)
O1	0.1332 (16)	0.0676 (12)	0.0634 (10)	−0.0298 (11)	0.0243 (10)	−0.0167 (9)
O2	0.0950 (11)	0.0567 (10)	0.0472 (9)	−0.0046 (8)	0.0196 (8)	−0.0014 (7)
O3	0.0983 (12)	0.0495 (9)	0.0532 (9)	−0.0073 (8)	0.0168 (8)	−0.0036 (7)
N1	0.0610 (11)	0.0512 (11)	0.0463 (10)	−0.0008 (8)	0.0086 (8)	−0.0027 (8)
C1	0.0553 (12)	0.0529 (13)	0.0555 (13)	−0.0032 (10)	0.0045 (10)	0.0017 (11)
C2	0.0746 (15)	0.0689 (16)	0.0609 (14)	−0.0185 (12)	0.0098 (12)	−0.0028 (13)
C3	0.0868 (18)	0.089 (2)	0.0591 (15)	−0.0080 (15)	0.0115 (13)	−0.0011 (14)
C4	0.0936 (19)	0.0776 (19)	0.0714 (17)	0.0040 (15)	0.0196 (14)	0.0237 (16)
C5	0.101 (2)	0.0565 (16)	0.093 (2)	−0.0055 (14)	0.0221 (16)	0.0151 (15)
C6	0.0878 (17)	0.0550 (15)	0.0670 (15)	−0.0053 (12)	0.0108 (13)	0.0003 (12)
C7	0.0642 (14)	0.0529 (14)	0.0576 (13)	−0.0069 (11)	0.0053 (10)	−0.0027 (12)
C8	0.0476 (11)	0.0559 (13)	0.0418 (11)	0.0043 (10)	0.0031 (9)	−0.0007 (9)
C9	0.0489 (11)	0.0482 (12)	0.0420 (11)	0.0049 (9)	0.0025 (9)	0.0029 (9)
C10	0.0485 (12)	0.0593 (14)	0.0439 (11)	0.0080 (10)	0.0039 (9)	0.0047 (10)
C11	0.0621 (13)	0.0656 (15)	0.0576 (13)	0.0034 (11)	0.0117 (10)	0.0105 (11)
C12A	0.076 (3)	0.098 (2)	0.0587 (18)	0.004 (2)	0.0198 (18)	0.0171 (15)
C13A	0.076 (3)	0.098 (2)	0.0587 (18)	0.004 (2)	0.0198 (18)	0.0171 (15)
C14	0.0943 (18)	0.105 (2)	0.0479 (13)	0.0045 (16)	0.0172 (12)	−0.0045 (14)
C15	0.0626 (14)	0.0730 (16)	0.0452 (12)	0.0009 (11)	0.0096 (10)	−0.0011 (11)
C16	0.0594 (13)	0.0505 (13)	0.0456 (12)	0.0025 (10)	0.0044 (10)	0.0043 (10)
C17	0.127 (2)	0.0565 (15)	0.0587 (15)	−0.0111 (15)	0.0169 (14)	−0.0116 (12)
C18	0.154 (3)	0.0614 (18)	0.090 (2)	−0.0203 (18)	0.0097 (19)	−0.0084 (16)
C12B	0.076 (3)	0.098 (2)	0.0587 (18)	0.004 (2)	0.0198 (18)	0.0171 (15)
C13B	0.076 (3)	0.098 (2)	0.0587 (18)	0.004 (2)	0.0198 (18)	0.0171 (15)

S1—C8	1.714 (2)	C13B—C14	1.440 (9)
S1—C15	1.732 (2)	C14—C15	1.512 (3)
O1—C7	1.217 (3)	C17—C18	1.491 (4)
O2—C16	1.221 (3)	C2—H2	0.9300
O3—C16	1.331 (3)	C3—H3	0.9300
O3—C17	1.445 (3)	C4—H4	0.9300
N1—C7	1.359 (3)	C5—H5	0.9300
N1—C8	1.381 (2)	C6—H6	0.9300
N1—H1	0.8600	C11—H11A	0.9700
C1—C2	1.384 (3)	C11—H11B	0.9700
C1—C6	1.386 (3)	C12A—H12A	0.9700
C1—C7	1.488 (3)	C12A—H12B	0.9700
C2—C3	1.378 (3)	C12B—H12D	0.9700
C3—C4	1.366 (4)	C12B—H12C	0.9700
C4—C5	1.361 (4)	C13A—H13B	0.9700
C5—C6	1.375 (4)	C13A—H13A	0.9700
C8—C9	1.375 (3)	C13B—H13C	0.9700
C9—C10	1.444 (3)	C13B—H13D	0.9700
C9—C16	1.457 (3)	C14—H14A	0.9700
C10—C15	1.343 (3)	C14—H14B	0.9700
C10—C11	1.510 (3)	C17—H17A	0.9700
C11—C12A	1.524 (6)	C17—H17B	0.9700
C11—C12B	1.542 (8)	C18—H18B	0.9600
C12A—C13A	1.503 (7)	C18—H18C	0.9600
C12B—C13B	1.514 (12)	C18—H18A	0.9600
C13A—C14	1.544 (6)
C8—S1—C15	90.83 (10)	C1—C6—H6	120.00
C16—O3—C17	116.70 (17)	C5—C6—H6	120.00
C7—N1—C8	125.72 (18)	C10—C11—H11A	109.00
C7—N1—H1	117.00	C10—C11—H11B	109.00
C8—N1—H1	117.00	C12A—C11—H11A	109.00
C2—C1—C6	118.0 (2)	C12A—C11—H11B	109.00
C2—C1—C7	124.4 (2)	H11A—C11—H11B	108.00
C6—C1—C7	117.5 (2)	C12B—C11—H11A	131.00
C1—C2—C3	120.6 (2)	C12B—C11—H11B	88.00
C2—C3—C4	120.5 (2)	C11—C12A—H12A	109.00
C3—C4—C5	119.6 (3)	C11—C12A—H12B	109.00
C4—C5—C6	120.8 (3)	C13A—C12A—H12A	109.00
C1—C6—C5	120.5 (2)	C13A—C12A—H12B	109.00
O1—C7—C1	123.0 (2)	H12A—C12A—H12B	108.00
O1—C7—N1	120.4 (2)	C13B—C12B—H12C	109.00
N1—C7—C1	116.61 (19)	C11—C12B—H12C	109.00
S1—C8—C9	112.26 (14)	C11—C12B—H12D	109.00
S1—C8—N1	123.14 (16)	C13B—C12B—H12D	109.00
N1—C8—C9	124.60 (18)	H12C—C12B—H12D	108.00
C8—C9—C16	120.08 (17)	C12A—C13A—H13A	109.00
C10—C9—C16	127.95 (18)	C14—C13A—H13A	109.00
C8—C9—C10	111.98 (17)	C14—C13A—H13B	109.00
C11—C10—C15	121.34 (18)	C12A—C13A—H13B	109.00
C9—C10—C11	126.98 (18)	H13A—C13A—H13B	108.00
C9—C10—C15	111.67 (19)	C14—C13B—H13C	109.00
C10—C11—C12B	108.7 (5)	C14—C13B—H13D	109.00
C10—C11—C12A	113.5 (3)	C12B—C13B—H13C	109.00
C11—C12A—C13A	112.0 (4)	C12B—C13B—H13D	109.00
C11—C12B—C13B	112.4 (7)	H13C—C13B—H13D	108.00
C12A—C13A—C14	112.4 (4)	C13A—C14—H14A	110.00
C12B—C13B—C14	111.2 (7)	C13A—C14—H14B	110.00
C13A—C14—C15	108.9 (3)	C15—C14—H14A	110.00
C13B—C14—C15	110.7 (4)	C13B—C14—H14A	131.00
S1—C15—C10	113.26 (16)	C13B—C14—H14B	81.00
S1—C15—C14	120.80 (18)	C15—C14—H14B	110.00
C10—C15—C14	125.9 (2)	H14A—C14—H14B	108.00
O2—C16—C9	124.47 (19)	C18—C17—H17A	110.00
O3—C16—C9	113.69 (18)	O3—C17—H17A	110.00
O2—C16—O3	121.84 (19)	O3—C17—H17B	110.00
O3—C17—C18	107.2 (2)	H17A—C17—H17B	109.00
C1—C2—H2	120.00	C18—C17—H17B	110.00
C3—C2—H2	120.00	C17—C18—H18C	109.00
C2—C3—H3	120.00	C17—C18—H18B	109.00
C4—C3—H3	120.00	H18B—C18—H18C	109.00
C3—C4—H4	120.00	H18A—C18—H18B	109.00
C5—C4—H4	120.00	H18A—C18—H18C	109.00
C4—C5—H5	120.00	C17—C18—H18A	109.00
C6—C5—H5	120.00
C15—S1—C8—N1	179.88 (17)	S1—C8—C9—C10	0.33 (19)
C15—S1—C8—C9	−0.02 (15)	S1—C8—C9—C16	−179.36 (15)
C8—S1—C15—C10	−0.32 (18)	N1—C8—C9—C10	−179.57 (16)
C8—S1—C15—C14	−178.7 (2)	N1—C8—C9—C16	0.8 (3)
C17—O3—C16—O2	0.5 (3)	C8—C9—C10—C11	178.53 (18)
C17—O3—C16—C9	−178.9 (2)	C8—C9—C10—C15	−0.6 (2)
C16—O3—C17—C18	−176.8 (2)	C16—C9—C10—C11	−1.8 (3)
C8—N1—C7—O1	4.4 (3)	C16—C9—C10—C15	179.1 (2)
C8—N1—C7—C1	−174.38 (19)	C8—C9—C16—O2	−1.6 (3)
C7—N1—C8—S1	−5.3 (3)	C8—C9—C16—O3	177.88 (18)
C7—N1—C8—C9	174.55 (19)	C10—C9—C16—O2	178.8 (2)
C6—C1—C2—C3	−0.9 (4)	C10—C9—C16—O3	−1.8 (3)
C7—C1—C2—C3	176.9 (2)	C9—C10—C11—C12A	170.4 (3)
C2—C1—C6—C5	0.0 (4)	C15—C10—C11—C12A	−10.6 (4)
C7—C1—C6—C5	−178.0 (2)	C9—C10—C15—S1	0.6 (2)
C2—C1—C7—O1	−170.1 (2)	C9—C10—C15—C14	178.9 (2)
C2—C1—C7—N1	8.6 (3)	C11—C10—C15—S1	−178.60 (16)
C6—C1—C7—O1	7.7 (4)	C11—C10—C15—C14	−0.3 (3)
C6—C1—C7—N1	−173.6 (2)	C10—C11—C12A—C13A	39.9 (5)
C1—C2—C3—C4	0.7 (4)	C11—C12A—C13A—C14	−59.8 (6)
C2—C3—C4—C5	0.6 (4)	C12A—C13A—C14—C15	46.7 (5)
C3—C4—C5—C6	−1.6 (4)	C13A—C14—C15—S1	160.7 (3)
C4—C5—C6—C1	1.3 (4)	C13A—C14—C15—C10	−17.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.02	2.664 (2)	131
C6—H6···O1i	0.93	2.44	3.242 (3)	145
C11—H11A···O3	0.97	2.45	2.845 (3)	104

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.02	2.664 (2)	131
C6—H6⋯O1i	0.93	2.44	3.242 (3)	145

Symmetry code: (i) .