Ethyl 2-(pyridine-4-carboxamido)-4,5,6,7-tetra-hydro-1-benzothio-phene-3-carboxyl-ate.

In the title compound, C(17)H(18)N(2)O(3)S, the dihedral angles between the thio-phene ring and the ethyl ester group and the pyridine-4-carboxamide unit are 7.1 (2) and 9.47 (11)°, respectively. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds between the tetra-hydro-1-benzothio-phene and the pyridine-4-carboxamide residues generate R(2) (2)(16) loops. There exists positional disorder in three methelene groups of the cyclo-hexane ring and the terminal C atom of the ethyl ester side chain in a 0.691 (14):0.309 (14) occupancy ratio.

Related literature

For related structures, see: Mukhtar et al. (2010a ▶,b ▶).

Experimental

Crystal data

C17H18N2O3S

M = 330.39

Triclinic,

a = 8.5604 (6) Å

b = 9.3481 (7) Å

c = 11.7443 (10) Å

α = 105.121 (3)°

β = 99.748 (2)°

γ = 110.806 (3)°

V = 811.59 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.24 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

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

12176 measured reflections

2914 independent reflections

1842 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.116

S = 1.00

2914 reflections

243 parameters

10 restraints

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.18 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 datablock(s) global, I. DOI: 10.1107/S1600536812025251/hb6838sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025251/hb6838Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812025251/hb6838Isup3.cml

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

C17H18N2O3S	Z = 2
Mr = 330.39	F(000) = 384
Triclinic, P1	Dx = 1.352 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5604 (6) Å	Cell parameters from 1842 reflections
b = 9.3481 (7) Å	θ = 2.5–25.3°
c = 11.7443 (10) Å	µ = 0.22 mm−1
α = 105.121 (3)°	T = 296 K
β = 99.748 (2)°	Prism, colorless
γ = 110.806 (3)°	0.24 × 0.18 × 0.15 mm
V = 811.59 (11) Å3

Bruker Kappa APEXII CCD diffractometer	2914 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.10 pixels mm-1	θmax = 25.3°, θmin = 2.5°
ω scans	h = −10→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→11
Tmin = 0.953, Tmax = 0.958	l = −14→14
12176 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.049P)2 + 0.1304P] where P = (Fo2 + 2Fc2)/3
2914 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.15 e Å−3
10 restraints	Δρmin = −0.18 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	0.57947 (9)	0.19759 (8)	0.46283 (7)	0.0767 (3)
O1	0.6976 (2)	0.68634 (18)	0.35270 (15)	0.0742 (6)
O2	0.8949 (2)	0.73080 (19)	0.52291 (15)	0.0730 (6)
O3	0.8381 (3)	0.2881 (3)	0.68270 (19)	0.1003 (8)
N1	0.8635 (2)	0.4829 (2)	0.60071 (17)	0.0615 (7)
N2	1.3610 (3)	0.7692 (4)	0.9953 (2)	0.0968 (11)
C1	0.7620 (3)	0.6392 (3)	0.4390 (2)	0.0580 (8)
C2	0.6600 (3)	0.4677 (3)	0.42082 (19)	0.0517 (8)
C3	0.5015 (3)	0.3510 (3)	0.3252 (2)	0.0568 (8)
C4	0.4040 (3)	0.3808 (3)	0.2210 (2)	0.0684 (9)
C5A	0.2613 (14)	0.2210 (11)	0.1232 (9)	0.084 (3)	0.691 (14)
C6A	0.1643 (9)	0.1068 (9)	0.1818 (7)	0.090 (2)	0.691 (14)
C7A	0.2885 (14)	0.0544 (12)	0.2537 (10)	0.093 (5)	0.691 (14)
C8	0.4453 (3)	0.2032 (3)	0.3374 (2)	0.0647 (9)
C9	0.7149 (3)	0.3990 (3)	0.5005 (2)	0.0571 (8)
C10	0.9163 (3)	0.4265 (3)	0.6877 (2)	0.0681 (10)
C11	1.0748 (3)	0.5483 (3)	0.7916 (2)	0.0624 (9)
C12	1.1234 (4)	0.5047 (4)	0.8909 (3)	0.0915 (12)
C13	1.2663 (5)	0.6197 (5)	0.9893 (3)	0.1068 (16)
C14	1.3131 (4)	0.8068 (4)	0.8988 (3)	0.0810 (11)
C15	1.1737 (3)	0.7024 (3)	0.7966 (2)	0.0690 (10)
C16	0.7948 (4)	0.8546 (3)	0.3616 (3)	0.0935 (11)
C17A	0.7281 (10)	0.8628 (10)	0.2439 (6)	0.113 (3)	0.691 (14)
C5B	0.221 (2)	0.242 (2)	0.159 (3)	0.083 (7)	0.310 (14)
C6B	0.225 (2)	0.0756 (16)	0.1323 (18)	0.091 (6)	0.310 (14)
C7B	0.275 (3)	0.054 (2)	0.2566 (18)	0.074 (8)	0.310 (14)
C17B	0.687 (2)	0.894 (2)	0.2657 (6)	0.103 (5)	0.310 (14)
H4A	0.48597	0.43620	0.18225	0.0821*
H4B	0.35058	0.45180	0.25392	0.0821*
H1	0.92888	0.58106	0.60821	0.0738*
H7A	0.23001	−0.00598	0.30131	0.1119*	0.691 (14)
H7B	0.32310	−0.01579	0.19682	0.1119*	0.691 (14)
H12	1.06183	0.40089	0.89190	0.1100*
H13	1.29763	0.58902	1.05578	0.1283*
H14	1.37777	0.91097	0.89972	0.0972*
H15	1.14681	0.73660	0.73125	0.0828*
H16A	0.77654	0.92982	0.42663	0.1120*
H16B	0.91878	0.88177	0.37895	0.1120*
H17A	0.60304	0.82038	0.22283	0.1699*	0.691 (14)
H17B	0.76116	0.79910	0.18235	0.1699*	0.691 (14)
H17C	0.77538	0.97428	0.24783	0.1699*	0.691 (14)
H5A	0.17977	0.24607	0.07281	0.1004*	0.691 (14)
H5B	0.31459	0.16809	0.06985	0.1004*	0.691 (14)
H6A	0.06979	0.01117	0.11859	0.1079*	0.691 (14)
H6B	0.11397	0.16052	0.23733	0.1079*	0.691 (14)
H5C	0.14711	0.25201	0.21193	0.0997*	0.310 (14)
H5D	0.17039	0.25150	0.08217	0.0997*	0.310 (14)
H6C	0.31023	0.06938	0.08848	0.1103*	0.310 (14)
H6D	0.11147	−0.00965	0.08180	0.1103*	0.310 (14)
H7C	0.29232	−0.04536	0.24441	0.0886*	0.310 (14)
H7D	0.18307	0.04701	0.29589	0.0886*	0.310 (14)
H17D	0.56995	0.86379	0.27276	0.1534*	0.310 (14)
H17E	0.68253	0.83476	0.18437	0.1534*	0.310 (14)
H17F	0.73952	1.00931	0.28019	0.1534*	0.310 (14)

	U11	U22	U33	U12	U13	U23
S1	0.0865 (5)	0.0500 (4)	0.0840 (5)	0.0152 (3)	0.0208 (4)	0.0297 (3)
O1	0.0827 (12)	0.0456 (10)	0.0725 (11)	0.0125 (9)	−0.0016 (9)	0.0224 (8)
O2	0.0732 (11)	0.0510 (10)	0.0704 (11)	0.0079 (9)	−0.0004 (10)	0.0225 (9)
O3	0.1113 (16)	0.0709 (13)	0.1059 (15)	0.0190 (12)	0.0106 (12)	0.0512 (12)
N1	0.0666 (13)	0.0511 (12)	0.0605 (12)	0.0171 (10)	0.0133 (10)	0.0238 (10)
N2	0.0930 (19)	0.110 (2)	0.0823 (17)	0.0380 (17)	0.0115 (14)	0.0410 (16)
C1	0.0664 (16)	0.0493 (14)	0.0562 (14)	0.0225 (13)	0.0151 (13)	0.0193 (12)
C2	0.0573 (14)	0.0414 (13)	0.0528 (13)	0.0167 (11)	0.0177 (11)	0.0152 (10)
C3	0.0581 (14)	0.0496 (14)	0.0562 (14)	0.0177 (12)	0.0194 (12)	0.0133 (11)
C4	0.0658 (16)	0.0581 (15)	0.0681 (16)	0.0203 (13)	0.0112 (13)	0.0147 (12)
C5A	0.074 (4)	0.073 (5)	0.076 (6)	0.019 (3)	0.003 (3)	0.012 (3)
C6A	0.067 (4)	0.072 (4)	0.085 (4)	0.000 (3)	0.003 (3)	0.008 (3)
C7A	0.090 (9)	0.074 (8)	0.098 (9)	0.010 (6)	0.028 (7)	0.037 (6)
C8	0.0640 (16)	0.0470 (15)	0.0688 (16)	0.0117 (13)	0.0176 (13)	0.0156 (12)
C9	0.0635 (15)	0.0458 (13)	0.0590 (14)	0.0177 (12)	0.0229 (13)	0.0178 (12)
C10	0.0803 (18)	0.0627 (17)	0.0696 (17)	0.0299 (15)	0.0245 (14)	0.0343 (14)
C11	0.0681 (16)	0.0712 (18)	0.0609 (15)	0.0365 (14)	0.0223 (13)	0.0306 (13)
C12	0.096 (2)	0.098 (2)	0.086 (2)	0.0341 (19)	0.0211 (19)	0.0535 (19)
C13	0.108 (3)	0.134 (3)	0.083 (2)	0.048 (2)	0.010 (2)	0.060 (2)
C14	0.0760 (19)	0.084 (2)	0.0749 (19)	0.0317 (16)	0.0091 (16)	0.0260 (16)
C15	0.0719 (17)	0.0702 (17)	0.0687 (17)	0.0327 (15)	0.0147 (14)	0.0295 (14)
C16	0.108 (2)	0.0462 (16)	0.097 (2)	0.0126 (15)	−0.0073 (17)	0.0308 (15)
C17A	0.155 (6)	0.062 (5)	0.118 (5)	0.040 (4)	0.010 (4)	0.050 (4)
C5B	0.071 (11)	0.066 (9)	0.081 (14)	0.023 (8)	−0.005 (7)	0.001 (8)
C6B	0.073 (9)	0.074 (9)	0.098 (12)	0.025 (6)	0.004 (7)	0.006 (7)
C7B	0.060 (13)	0.027 (10)	0.083 (18)	−0.002 (9)	0.000 (11)	−0.019 (10)
C17B	0.151 (12)	0.052 (7)	0.076 (8)	0.055 (8)	−0.032 (7)	0.002 (5)

S1—C8	1.733 (3)	C16—C17A	1.436 (8)
S1—C9	1.711 (3)	C16—C17B	1.537 (14)
O1—C1	1.320 (3)	C4—H4A	0.9700
O1—C16	1.460 (3)	C4—H4B	0.9700
O2—C1	1.219 (3)	C5A—H5A	0.9700
O3—C10	1.207 (4)	C5A—H5B	0.9700
N1—C9	1.386 (3)	C5B—H5D	0.9700
N1—C10	1.349 (3)	C5B—H5C	0.9700
N2—C13	1.319 (6)	C6A—H6B	0.9700
N2—C14	1.315 (4)	C6A—H6A	0.9700
N1—H1	0.8600	C6B—H6D	0.9700
C1—C2	1.464 (4)	C6B—H6C	0.9700
C2—C3	1.444 (3)	C7A—H7B	0.9700
C2—C9	1.374 (4)	C7A—H7A	0.9700
C3—C4	1.506 (3)	C7B—H7D	0.9700
C3—C8	1.347 (4)	C7B—H7C	0.9700
C4—C5B	1.53 (2)	C12—H12	0.9300
C4—C5A	1.542 (11)	C13—H13	0.9300
C5A—C6A	1.500 (13)	C14—H14	0.9300
C5B—C6B	1.52 (3)	C15—H15	0.9300
C6A—C7A	1.538 (14)	C16—H16A	0.9700
C6B—C7B	1.54 (3)	C16—H16B	0.9700
C7A—C8	1.489 (12)	C17A—H17C	0.9600
C7B—C8	1.54 (2)	C17A—H17A	0.9600
C10—C11	1.498 (3)	C17A—H17B	0.9600
C11—C12	1.380 (4)	C17B—H17D	0.9600
C11—C15	1.367 (4)	C17B—H17E	0.9600
C12—C13	1.388 (5)	C17B—H17F	0.9600
C14—C15	1.376 (4)
C8—S1—C9	90.88 (13)	H5A—C5A—H5B	108.00
C1—O1—C16	116.6 (2)	C4—C5B—H5C	109.00
C9—N1—C10	126.8 (2)	C4—C5B—H5D	109.00
C13—N2—C14	115.6 (3)	C6B—C5B—H5C	109.00
C10—N1—H1	117.00	C6B—C5B—H5D	109.00
C9—N1—H1	117.00	H5C—C5B—H5D	108.00
O1—C1—C2	113.0 (2)	H6A—C6A—H6B	108.00
O2—C1—C2	124.7 (2)	C5A—C6A—H6A	110.00
O1—C1—O2	122.3 (2)	C5A—C6A—H6B	110.00
C3—C2—C9	111.7 (2)	C7A—C6A—H6A	110.00
C1—C2—C3	128.5 (2)	C7A—C6A—H6B	110.00
C1—C2—C9	119.8 (2)	C7B—C6B—H6C	110.00
C4—C3—C8	121.2 (2)	C7B—C6B—H6D	110.00
C2—C3—C8	111.9 (2)	C5B—C6B—H6D	110.00
C2—C3—C4	126.9 (2)	C5B—C6B—H6C	110.00
C3—C4—C5B	110.8 (10)	H6C—C6B—H6D	108.00
C3—C4—C5A	112.2 (4)	C6A—C7A—H7A	110.00
C4—C5A—C6A	111.4 (7)	C6A—C7A—H7B	110.00
C4—C5B—C6B	111.8 (14)	H7A—C7A—H7B	108.00
C5A—C6A—C7A	110.2 (8)	C8—C7A—H7B	110.00
C5B—C6B—C7B	107.5 (18)	C8—C7A—H7A	110.00
C6A—C7A—C8	108.7 (8)	C6B—C7B—H7C	110.00
C6B—C7B—C8	107.5 (13)	C8—C7B—H7D	110.00
C3—C8—C7B	125.6 (8)	C8—C7B—H7C	110.00
C3—C8—C7A	126.1 (5)	C6B—C7B—H7D	110.00
S1—C8—C3	112.96 (19)	H7C—C7B—H7D	109.00
S1—C8—C7A	121.0 (5)	C11—C12—H12	121.00
S1—C8—C7B	121.3 (8)	C13—C12—H12	121.00
S1—C9—N1	123.36 (19)	C12—C13—H13	118.00
S1—C9—C2	112.64 (19)	N2—C13—H13	118.00
N1—C9—C2	124.0 (2)	C15—C14—H14	118.00
N1—C10—C11	115.4 (2)	N2—C14—H14	118.00
O3—C10—C11	122.7 (2)	C11—C15—H15	120.00
O3—C10—N1	121.8 (2)	C14—C15—H15	120.00
C10—C11—C15	124.5 (2)	O1—C16—H16A	111.00
C10—C11—C12	118.4 (3)	O1—C16—H16B	111.00
C12—C11—C15	117.1 (2)	C17A—C16—H16A	111.00
C11—C12—C13	118.4 (3)	C17A—C16—H16B	111.00
N2—C13—C12	124.8 (3)	H16A—C16—H16B	109.00
N2—C14—C15	124.4 (3)	C17B—C16—H16A	89.00
C11—C15—C14	119.7 (3)	C17B—C16—H16B	126.00
O1—C16—C17B	108.9 (7)	C16—C17A—H17A	109.00
O1—C16—C17A	105.7 (4)	C16—C17A—H17B	109.00
C3—C4—H4A	109.00	C16—C17A—H17C	109.00
C3—C4—H4B	109.00	H17A—C17A—H17B	109.00
C5A—C4—H4A	109.00	H17A—C17A—H17C	109.00
C5A—C4—H4B	109.00	H17B—C17A—H17C	110.00
H4A—C4—H4B	108.00	C16—C17B—H17D	110.00
C5B—C4—H4A	128.00	C16—C17B—H17E	110.00
C5B—C4—H4B	89.00	C16—C17B—H17F	110.00
C4—C5A—H5A	109.00	H17D—C17B—H17E	109.00
C4—C5A—H5B	109.00	H17D—C17B—H17F	109.00
C6A—C5A—H5A	109.00	H17E—C17B—H17F	109.00
C6A—C5A—H5B	109.00
C9—S1—C8—C3	0.1 (2)	C3—C2—C9—S1	−0.2 (3)
C9—S1—C8—C7A	178.7 (6)	C3—C2—C9—N1	179.9 (2)
C8—S1—C9—N1	−180.0 (2)	C2—C3—C4—C5A	169.0 (5)
C8—S1—C9—C2	0.1 (2)	C8—C3—C4—C5A	−10.4 (6)
C16—O1—C1—O2	0.6 (4)	C2—C3—C8—S1	−0.2 (3)
C16—O1—C1—C2	−178.1 (2)	C2—C3—C8—C7A	−178.7 (6)
C1—O1—C16—C17A	165.1 (4)	C4—C3—C8—S1	179.3 (2)
C10—N1—C9—S1	−5.8 (4)	C4—C3—C8—C7A	0.8 (7)
C10—N1—C9—C2	174.1 (2)	C3—C4—C5A—C6A	41.5 (9)
C9—N1—C10—O3	3.3 (4)	C4—C5A—C6A—C7A	−63.6 (10)
C9—N1—C10—C11	−175.2 (2)	C5A—C6A—C7A—C8	51.1 (10)
C14—N2—C13—C12	−0.6 (6)	C6A—C7A—C8—S1	160.6 (5)
C13—N2—C14—C15	0.6 (5)	C6A—C7A—C8—C3	−21.0 (10)
O1—C1—C2—C3	−1.7 (4)	O3—C10—C11—C12	−6.1 (4)
O1—C1—C2—C9	177.4 (2)	O3—C10—C11—C15	175.4 (3)
O2—C1—C2—C3	179.6 (3)	N1—C10—C11—C12	172.3 (3)
O2—C1—C2—C9	−1.3 (4)	N1—C10—C11—C15	−6.2 (4)
C1—C2—C3—C4	−0.1 (4)	C10—C11—C12—C13	−177.6 (3)
C1—C2—C3—C8	179.4 (3)	C15—C11—C12—C13	1.0 (5)
C9—C2—C3—C4	−179.3 (2)	C10—C11—C15—C14	177.5 (3)
C9—C2—C3—C8	0.2 (3)	C12—C11—C15—C14	−1.0 (4)
C1—C2—C9—S1	−179.41 (19)	C11—C12—C13—N2	−0.3 (6)
C1—C2—C9—N1	0.6 (4)	N2—C14—C15—C11	0.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.99	2.650 (3)	132
C7A—H7A···O3i	0.97	2.56	3.323 (12)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.99	2.650 (3)	132
C7A—H7A⋯O3i	0.97	2.56	3.323 (12)	136

Symmetry code: (i) .