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

Abstract

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.

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Ethyl 2-amino-6-benzyl-4,5,6,7-tetra-
hydrothieno[2,3-c]pyridine-3-
carboxylate
Shuang-Ming Meng, Ke-Wei Wang, Hai Xie, Yue-Qin Fan
and Yong Guo*
College of Chemistry and Chemical Engineering, Shanxi Datong University, Datong
037009, People’s Republic of China
Correspondence e-mail: ybsymsm@126.com
Received 7 December 2010; accepted 11 December 2010
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.042; wR factor = 0.107; data-to-parameter ratio = 14.0.
In the title compound, C17H20N2O2S, the tetrahydropyridine
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 thiophene ring. The amino group links
with the carbonyl O atom via intramolecular N—H???O
hydrogen bonding, forming a six-membered ring. In the
crystal, intermolecular N—H???O hydrogen bonds link the
molecules 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
C17H20N2O2SMr= 316.41
Monoclinic, P21=n
a = 12.197 (3) A˚
b = 9.936 (3) A˚
c = 13.775 (4) A˚
? = 103.430 (4)?
V = 1623.8 (8) A˚3
Z = 4
Mo K? radiation
? = 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)
Tmin= 0.953, Tmax= 0.977
8867 measured reflections
2875 independent reflections
2122 reflections with I > 2?(I)
Rint= 0.030
Refinement
R[F2> 2?(F2)] = 0.042
wR(F2) = 0.107
S = 1.04
2875 reflections
205 parameters
3 restraints
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.20 e A˚?3
??min= ?0.17 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N2—H1N???O1i
N2—H2N???O1
Symmetry code: (i) ?x þ3
D—HH???AD???AD—H???A
0.81 (2)
0.81 (1)
2.17 (2)
2.17 (2)
2.972 (2)
2.777 (2)
171 (2)
132 (2)
2;y þ1
2;?z þ3
2.
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.
We thank the Natural Science Foundation of Shanxi
Province, China (No. 2010011018) for supporting this work.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: XU5117).
References
Amr, A. G. E., Mohamed, A. M., Mohamed, S. F., Abdel-Hafez, N. A. &
Hammam, A. E. F. G. (2006). Bioorg. Med. Chem. 14, 5481–5488.
Bruker (1999). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Kidwai, M. & Mishra, A. D. (2003). Bull. Korean Chem.. Soc. 24, 1038–1040.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sherif, S. M. (1996). Monatsh. Chem. 127, 955–962.
organic compounds
o226
Meng et al.
doi:10.1107/S1600536810051986
Acta Cryst. (2011). E67, o226
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
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Acta Cryst. (2011). E67, o226 [ doi:10.1107/S1600536810051986 ]
Ethyl 2-amino-6-benzyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate
S.-M. Meng, K.-W. Wang, H. Xie, Y.-Q. Fan and Y. Guo
Comment
As part of an investigation of the thiophene and it's derivatives systems due to their diverse biological activities (Kidwai et
al., 2003; Amr et al., 2006; Sherif et al., 1996), we present here the crystal structure of the title compound, (I).
In the crystal structure of title compound (Fig.1), all bond lengths and bond angles have standard dimensions.
The fragments (C8 to C12) of piperidine nearly planar (mean deviation from plane within 0.0632 (1) Å) while the the
six-membered piperidine ring exhibits half-chair conformation. The amino group are hydrogen bonded to the carbonyl O
atom of another molecule (Table 1), forming a one-dimensional supramolecular structure (Fig. 2). In addition, there are
intramolecular N—H···O hydrogen-bonding interactions in the crystal.
Experimental
To the solution containing the ethyl 2-cyanoacetate (10 mmol, 1.06 ml), 1-benzylpiperidin-4-one (10 mmol, 1.80 ml) and
powdered sulfur (12 mmol, 0.38 g) in DMF (6 ml), was under stirring triethylamine (1.20 ml) dropwise added. When the
reaction was finished (TLC monitoring) the mixture was filtered with charcoal and poured into crushed ice. The formed
crystals were filtered off and washed with water. The products were crystallized from ethanol.
Refinement
All H atoms bound to C atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å (CH), C—H = 0.97
Å (CH2) and Uiso(H) = 1.2Ueq(C), C—H = 0.96 Å (CH3) and Uiso(H) = 1.5Ueq(C). The H atoms bound to N atoms were
located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(N). The N—H distances were restrained.
Figures
Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the
30% probabilitylevel.
Fig. 2. View of the one-dimensional supra-molecular chain of the title compound formed by
hydrogen bonding (dashed lines). H atoms of C omitted for clarity.

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Ethyl 2-amino-6-benzyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate
Crystal data
C17H20N2O2S
F(000) = 672
Dx = 1.294 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2875 reflections
θ = 2.2–25.1°
µ = 0.21 mm−1
T = 293 K
Block, yellow
Mr = 316.41
Monoclinic, P21/n
Hall symbol: -P 2yn
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
0.25 × 0.19 × 0.14 mm
Data collection
Bruker SMART APEX CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Tmin = 0.953, Tmax = 0.977
8867 measured reflections
2875 independent reflections
2122 reflections with I > 2σ(I)
Rint = 0.030
θmax = 25.1°, θmin = 2.0°
h = −14→14
k = −10→11
l = −16→14
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of independent and
constrained refinement
w = 1/[σ2(Fo2) + (0.0533P)2 + 0.2035P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.20 e Å−3
Δρmin = −0.17 e Å−3
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.107
S = 1.04
2875 reflections
205 parameters
3 restraints
Special details
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 mat-
rix. 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

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