Ethyl 2-amino-6-benzyl-4,5,6,7-tetra-hydro-thieno[2,3-c]pyridine-3-carboxyl-ate.

In the title compound, C(17)H(20)N(2)O(2)S, the tetra-hydro-pyridine ring adopts an envelope conformation with the N atom at the flap position; the phenyl ring makes a dihedral angle of 81.06 (10)° with the thio-phene ring. The amino group links with the carbonyl O atom via intra-molecular N-H⋯O hydrogen bonding, forming a six-membered ring. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into infinite chains running along the b axis.

Related literature

For the biological activity of thio­phene and its derivatives, see: Kidwai & Mishra (2003 ▶); Amr et al. (2006 ▶); Sherif (1996 ▶).

Experimental

Crystal data

C17H20N2O2S

M = 316.41

Monoclinic,

a = 12.197 (3) Å

b = 9.936 (3) Å

c = 13.775 (4) Å

β = 103.430 (4)°

V = 1623.8 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.25 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.953, T max = 0.977

8867 measured reflections

2875 independent reflections

2122 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.107

S = 1.04

2875 reflections

205 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008) ▶; program(s) used to refine structure: SHELXTL ▶; molecular graphics: SHELXTL ▶; software used to prepare material for publication: SHELXTL ▶.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051986/xu5117sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051986/xu5117Isup2.hkl

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

C17H20N2O2S	F(000) = 672
Mr = 316.41	Dx = 1.294 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2875 reflections
a = 12.197 (3) Å	θ = 2.2–25.1°
b = 9.936 (3) Å	µ = 0.21 mm−1
c = 13.775 (4) Å	T = 293 K
β = 103.430 (4)°	Block, yellow
V = 1623.8 (8) Å3	0.25 × 0.19 × 0.14 mm
Z = 4

Bruker SMART APEX CCD diffractometer	2875 independent reflections
Radiation source: fine-focus sealed tube	2122 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −14→14
Tmin = 0.953, Tmax = 0.977	k = −10→11
8867 measured reflections	l = −16→14

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) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.2035P] where P = (Fo2 + 2Fc2)/3
2875 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.20 e Å−3
3 restraints	Δρmin = −0.17 e Å−3

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.

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
C1	0.15299 (16)	0.6448 (2)	0.47716 (17)	0.0480 (5)
H1	0.1593	0.6354	0.4115	0.058*
C2	0.14619 (18)	0.7720 (2)	0.51559 (19)	0.0583 (6)
H2	0.1477	0.8472	0.4757	0.070*
C3	0.13735 (19)	0.7877 (2)	0.6113 (2)	0.0610 (6)
H3	0.1325	0.8734	0.6370	0.073*
C4	0.1356 (2)	0.6766 (3)	0.67014 (19)	0.0630 (6)
H4	0.1300	0.6873	0.7359	0.076*
C5	0.14210 (18)	0.5487 (2)	0.63200 (17)	0.0539 (6)
H5	0.1408	0.4740	0.6724	0.065*
C6	0.15054 (15)	0.5310 (2)	0.53451 (16)	0.0416 (5)
C7	0.15136 (17)	0.3930 (2)	0.48984 (17)	0.0503 (6)
H7A	0.0800	0.3494	0.4889	0.060*
H7B	0.1577	0.4022	0.4212	0.060*
C8	0.23336 (17)	0.17339 (19)	0.49528 (17)	0.0480 (5)
H8A	0.2476	0.1822	0.4292	0.058*
H8B	0.1571	0.1401	0.4878	0.058*
C9	0.31573 (15)	0.07232 (19)	0.55515 (16)	0.0441 (5)
H9A	0.2875	0.0412	0.6115	0.053*
H9B	0.3216	−0.0049	0.5136	0.053*
C10	0.43028 (15)	0.13375 (19)	0.59228 (14)	0.0372 (5)
C11	0.44382 (15)	0.26693 (19)	0.58452 (15)	0.0409 (5)
C12	0.35245 (15)	0.36571 (19)	0.54262 (17)	0.0471 (5)
H12A	0.3633	0.4473	0.5824	0.057*
H12B	0.3552	0.3890	0.4748	0.057*
C13	0.53359 (15)	0.06514 (18)	0.64255 (14)	0.0371 (4)
C14	0.62303 (15)	0.15380 (19)	0.66948 (15)	0.0405 (5)
C15	0.54785 (16)	−0.07575 (19)	0.66775 (14)	0.0400 (5)
C16	0.45439 (19)	−0.28970 (19)	0.65815 (19)	0.0562 (6)
H16A	0.5239	−0.3251	0.6456	0.067*
H16B	0.3921	−0.3307	0.6106	0.067*
C17	0.4472 (2)	−0.3267 (2)	0.7607 (2)	0.0746 (8)
H17A	0.4497	−0.4229	0.7676	0.112*
H17B	0.3777	−0.2935	0.7730	0.112*
H17C	0.5095	−0.2877	0.8080	0.112*
O1	0.63729 (11)	−0.12830 (13)	0.70893 (11)	0.0503 (4)
O2	0.45118 (11)	−0.14512 (13)	0.64303 (12)	0.0540 (4)
S1	0.58197 (4)	0.31782 (5)	0.63602 (5)	0.0502 (2)
N1	0.24303 (12)	0.30618 (15)	0.54336 (13)	0.0417 (4)
N2	0.73186 (14)	0.12651 (18)	0.71338 (16)	0.0544 (5)
H1N	0.7738 (18)	0.1883 (17)	0.7340 (17)	0.065*
H2N	0.7441 (19)	0.0488 (15)	0.7300 (17)	0.065*

	U11	U22	U33	U12	U13	U23
C1	0.0413 (11)	0.0530 (14)	0.0484 (13)	−0.0033 (10)	0.0078 (10)	0.0019 (10)
C2	0.0566 (14)	0.0454 (14)	0.0690 (17)	−0.0080 (11)	0.0066 (12)	0.0068 (12)
C3	0.0595 (15)	0.0463 (14)	0.0756 (19)	−0.0028 (11)	0.0125 (13)	−0.0119 (12)
C4	0.0689 (16)	0.0696 (17)	0.0550 (15)	0.0006 (13)	0.0232 (12)	−0.0077 (13)
C5	0.0573 (14)	0.0506 (14)	0.0553 (15)	0.0017 (11)	0.0157 (11)	0.0094 (11)
C6	0.0290 (10)	0.0431 (12)	0.0510 (13)	0.0035 (8)	0.0058 (9)	0.0013 (10)
C7	0.0397 (11)	0.0476 (13)	0.0586 (14)	0.0062 (10)	0.0012 (10)	−0.0040 (10)
C8	0.0384 (11)	0.0411 (12)	0.0595 (14)	−0.0027 (9)	0.0009 (10)	−0.0071 (10)
C9	0.0378 (11)	0.0329 (11)	0.0592 (14)	−0.0022 (8)	0.0063 (10)	−0.0038 (9)
C10	0.0346 (10)	0.0327 (10)	0.0445 (12)	−0.0012 (8)	0.0100 (9)	−0.0014 (8)
C11	0.0332 (10)	0.0334 (11)	0.0561 (13)	−0.0011 (8)	0.0100 (9)	0.0031 (9)
C12	0.0373 (11)	0.0359 (11)	0.0667 (15)	0.0017 (9)	0.0090 (10)	0.0065 (10)
C13	0.0356 (10)	0.0296 (10)	0.0459 (12)	−0.0007 (8)	0.0090 (9)	−0.0015 (8)
C14	0.0355 (10)	0.0358 (11)	0.0495 (13)	0.0015 (8)	0.0087 (9)	0.0003 (9)
C15	0.0387 (11)	0.0353 (11)	0.0456 (12)	−0.0004 (9)	0.0088 (9)	−0.0041 (9)
C16	0.0553 (14)	0.0261 (11)	0.0791 (18)	−0.0048 (9)	−0.0010 (12)	−0.0014 (10)
C17	0.0791 (18)	0.0546 (15)	0.083 (2)	−0.0141 (13)	0.0051 (15)	0.0115 (14)
O1	0.0399 (8)	0.0375 (8)	0.0689 (10)	0.0062 (6)	0.0032 (7)	0.0037 (7)
O2	0.0413 (8)	0.0291 (8)	0.0841 (11)	−0.0039 (6)	−0.0006 (7)	0.0050 (7)
S1	0.0357 (3)	0.0324 (3)	0.0794 (4)	−0.0055 (2)	0.0068 (3)	0.0047 (3)
N1	0.0319 (8)	0.0328 (9)	0.0576 (11)	0.0020 (7)	0.0048 (8)	−0.0008 (8)
N2	0.0363 (10)	0.0392 (10)	0.0810 (15)	−0.0036 (8)	−0.0002 (9)	0.0014 (10)

C1—C2	1.380 (3)	C10—C11	1.341 (3)
C1—C6	1.383 (3)	C10—C13	1.458 (3)
C1—H1	0.9300	C11—C12	1.497 (3)
C2—C3	1.357 (3)	C11—S1	1.7445 (19)
C2—H2	0.9300	C12—N1	1.462 (2)
C3—C4	1.372 (3)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.384 (3)	C13—C14	1.384 (3)
C4—H4	0.9300	C13—C15	1.443 (3)
C5—C6	1.382 (3)	C14—N2	1.352 (2)
C5—H5	0.9300	C14—S1	1.736 (2)
C6—C7	1.505 (3)	C15—O1	1.224 (2)
C7—N1	1.468 (2)	C15—O2	1.340 (2)
C7—H7A	0.9700	C16—O2	1.451 (2)
C7—H7B	0.9700	C16—C17	1.482 (3)
C8—N1	1.469 (2)	C16—H16A	0.9700
C8—C9	1.521 (3)	C16—H16B	0.9700
C8—H8A	0.9700	C17—H17A	0.9600
C8—H8B	0.9700	C17—H17B	0.9600
C9—C10	1.501 (3)	C17—H17C	0.9600
C9—H9A	0.9700	N2—H1N	0.807 (15)
C9—H9B	0.9700	N2—H2N	0.809 (14)
C2—C1—C6	121.2 (2)	C10—C11—C12	125.70 (17)
C2—C1—H1	119.4	C10—C11—S1	112.26 (14)
C6—C1—H1	119.4	C12—C11—S1	121.95 (14)
C3—C2—C1	120.2 (2)	N1—C12—C11	109.34 (16)
C3—C2—H2	119.9	N1—C12—H12A	109.8
C1—C2—H2	119.9	C11—C12—H12A	109.8
C2—C3—C4	119.8 (2)	N1—C12—H12B	109.8
C2—C3—H3	120.1	C11—C12—H12B	109.8
C4—C3—H3	120.1	H12A—C12—H12B	108.3
C3—C4—C5	120.3 (2)	C14—C13—C15	120.63 (17)
C3—C4—H4	119.9	C14—C13—C10	111.72 (17)
C5—C4—H4	119.9	C15—C13—C10	127.61 (17)
C6—C5—C4	120.6 (2)	N2—C14—C13	128.54 (18)
C6—C5—H5	119.7	N2—C14—S1	119.99 (15)
C4—C5—H5	119.7	C13—C14—S1	111.45 (14)
C5—C6—C1	117.87 (19)	O1—C15—O2	122.38 (18)
C5—C6—C7	121.5 (2)	O1—C15—C13	124.76 (18)
C1—C6—C7	120.6 (2)	O2—C15—C13	112.84 (16)
N1—C7—C6	114.01 (16)	O2—C16—C17	112.14 (19)
N1—C7—H7A	108.8	O2—C16—H16A	109.2
C6—C7—H7A	108.8	C17—C16—H16A	109.2
N1—C7—H7B	108.8	O2—C16—H16B	109.2
C6—C7—H7B	108.8	C17—C16—H16B	109.2
H7A—C7—H7B	107.6	H16A—C16—H16B	107.9
N1—C8—C9	112.02 (16)	C16—C17—H17A	109.5
N1—C8—H8A	109.2	C16—C17—H17B	109.5
C9—C8—H8A	109.2	H17A—C17—H17B	109.5
N1—C8—H8B	109.2	C16—C17—H17C	109.5
C9—C8—H8B	109.2	H17A—C17—H17C	109.5
H8A—C8—H8B	107.9	H17B—C17—H17C	109.5
C10—C9—C8	111.19 (16)	C15—O2—C16	118.70 (15)
C10—C9—H9A	109.4	C14—S1—C11	91.59 (9)
C8—C9—H9A	109.4	C12—N1—C7	110.42 (15)
C10—C9—H9B	109.4	C12—N1—C8	109.76 (16)
C8—C9—H9B	109.4	C7—N1—C8	109.22 (15)
H9A—C9—H9B	108.0	C14—N2—H1N	118.7 (16)
C11—C10—C13	112.98 (16)	C14—N2—H2N	114.6 (16)
C11—C10—C9	119.74 (17)	H1N—N2—H2N	124 (2)
C13—C10—C9	127.21 (17)
C6—C1—C2—C3	0.3 (3)	C9—C10—C13—C15	−0.3 (3)
C1—C2—C3—C4	0.2 (4)	C15—C13—C14—N2	5.0 (3)
C2—C3—C4—C5	−0.4 (4)	C10—C13—C14—N2	−177.1 (2)
C3—C4—C5—C6	0.1 (4)	C15—C13—C14—S1	−176.97 (15)
C4—C5—C6—C1	0.4 (3)	C10—C13—C14—S1	0.9 (2)
C4—C5—C6—C7	−176.62 (19)	C14—C13—C15—O1	−3.6 (3)
C2—C1—C6—C5	−0.6 (3)	C10—C13—C15—O1	178.95 (19)
C2—C1—C6—C7	176.49 (19)	C14—C13—C15—O2	175.16 (18)
C5—C6—C7—N1	−58.6 (3)	C10—C13—C15—O2	−2.3 (3)
C1—C6—C7—N1	124.5 (2)	O1—C15—O2—C16	−5.2 (3)
N1—C8—C9—C10	−43.7 (2)	C13—C15—O2—C16	176.01 (18)
C8—C9—C10—C11	10.4 (3)	C17—C16—O2—C15	86.3 (2)
C8—C9—C10—C13	−172.76 (19)	N2—C14—S1—C11	177.73 (18)
C13—C10—C11—C12	−175.99 (19)	C13—C14—S1—C11	−0.45 (17)
C9—C10—C11—C12	1.2 (3)	C10—C11—S1—C14	−0.11 (17)
C13—C10—C11—S1	0.6 (2)	C12—C11—S1—C14	176.65 (18)
C9—C10—C11—S1	177.86 (15)	C11—C12—N1—C7	−171.98 (17)
C10—C11—C12—N1	19.4 (3)	C11—C12—N1—C8	−51.5 (2)
S1—C11—C12—N1	−156.87 (15)	C6—C7—N1—C12	−61.0 (2)
C11—C10—C13—C14	−1.0 (3)	C6—C7—N1—C8	178.23 (18)
C9—C10—C13—C14	−177.97 (19)	C9—C8—N1—C12	66.7 (2)
C11—C10—C13—C15	176.68 (19)	C9—C8—N1—C7	−172.09 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O1i	0.81 (2)	2.17 (2)	2.972 (2)	171 (2)
N2—H2N···O1	0.81 (1)	2.17 (2)	2.777 (2)	132 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O1i	0.81 (2)	2.17 (2)	2.972 (2)	171 (2)
N2—H2N⋯O1	0.81 (1)	2.17 (2)	2.777 (2)	132 (2)

Symmetry code: (i) .