Ethyl 2-amino-6-methyl-4,5,6,7-tetra­hydro­thieno[2,3-c]pyridine-3-carboxyl­ate monohydrate

The title compound, C₁₁H₁₆N₂O₂S·H₂O, is stabilized by a number of inter- and intra­molecular O—H...O, O—H...N, N—H...O and C—H...O hydrogen bonds. Delocalization in the thio­phene system is indicated by the C—S bond distances.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.056
• wR factor = 0.137
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT354_ALERT_3_C Short   O-H Bond (0.82A)   O3     -   H3B    ...       0.71 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: ...all the six authors are contributed for publication. JS & SM Synthesis, CK, MKK & PR data collection solution refinement, Calculations& Manuscript prepartion MVK, CK, PR, Communication MKK

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Ethyl 2-amino-6-methyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate monohydrate

Crystal data

C11H16N2O2S·H2O	F(000) = 552
Mr = 258.34	Dx = 1.263 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 260 reflections
a = 9.670 (2) Å	θ = 2.2–27.5°
b = 11.514 (3) Å	µ = 0.24 mm^−1
c = 12.219 (3) Å	T = 291 K
β = 93.074 (4)°	Block, colourless
V = 1358.4 (6) Å^3	0.31 × 0.28 × 0.21 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2526 independent reflections
Radiation source: fine-focus sealed tube	2115 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.930, Tmax = 0.955	k = −13→13
9867 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0691P)^2 + 0.1443P] where P = (Fo^2 + 2Fc^2)/3
2526 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.13 e Å^−3

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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.29415 (18)	0.39444 (15)	0.08467 (15)	0.0548 (5)
N2	0.6910 (3)	0.0207 (2)	0.2670 (2)	0.0760 (7)
O1	0.51741 (18)	−0.12967 (14)	0.15275 (14)	0.0674 (5)
O2	0.32274 (16)	−0.05708 (12)	0.07172 (13)	0.0595 (4)
O3	0.4169 (2)	0.36935 (18)	−0.11546 (17)	0.0645 (5)
S1	0.60326 (7)	0.24039 (5)	0.26417 (5)	0.0636 (3)
C1	0.2309 (3)	0.5103 (2)	0.0740 (2)	0.0744 (7)
H1A	0.1751	0.5244	0.1353	0.112*
H1B	0.1739	0.5140	0.0073	0.112*
H1C	0.3024	0.5680	0.0725	0.112*
C2	0.5909 (2)	0.0942 (2)	0.23095 (18)	0.0556 (6)
C3	0.4703 (2)	0.07060 (18)	0.16800 (16)	0.0480 (5)
C4	0.2522 (2)	0.18358 (19)	0.08182 (19)	0.0549 (6)
H4A	0.1883	0.1256	0.1069	0.066*
H4B	0.2669	0.1683	0.0053	0.066*
C5	0.1891 (2)	0.3036 (2)	0.0930 (2)	0.0613 (6)
H5A	0.1168	0.3147	0.0358	0.074*
H5B	0.1475	0.3096	0.1632	0.074*
C6	0.3918 (2)	0.39054 (19)	0.17991 (19)	0.0582 (6)
H6A	0.3457	0.4132	0.2452	0.070*
H6B	0.4675	0.4441	0.1700	0.070*
C7	0.4462 (2)	0.27006 (18)	0.19256 (18)	0.0524 (5)
C8	0.3876 (2)	0.17382 (18)	0.14745 (16)	0.0472 (5)
C9	0.4422 (2)	−0.04625 (19)	0.13153 (17)	0.0502 (5)
C10	0.2851 (3)	−0.1725 (2)	0.0343 (2)	0.0657 (7)
H10A	0.2792	−0.2247	0.0962	0.079*
H10B	0.3540	−0.2024	−0.0132	0.079*
C11	0.1480 (3)	−0.1631 (3)	−0.0268 (3)	0.0921 (9)
H11A	0.0799	−0.1372	0.0221	0.138*
H11B	0.1217	−0.2377	−0.0562	0.138*
H11C	0.1541	−0.1083	−0.0855	0.138*
H3B	0.434 (3)	0.311 (3)	−0.127 (2)	0.071 (10)*
H3A	0.379 (4)	0.370 (3)	−0.041 (3)	0.139 (14)*
H2A	0.763 (3)	0.047 (2)	0.299 (2)	0.085 (9)*
H2B	0.679 (3)	−0.052 (2)	0.248 (2)	0.072 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0553 (11)	0.0434 (10)	0.0660 (12)	−0.0003 (8)	0.0069 (9)	−0.0039 (8)
N2	0.0734 (15)	0.0617 (15)	0.0895 (16)	0.0030 (12)	−0.0266 (13)	−0.0063 (12)
O1	0.0744 (11)	0.0465 (9)	0.0806 (11)	0.0017 (8)	−0.0019 (9)	−0.0031 (8)
O2	0.0606 (10)	0.0441 (9)	0.0736 (10)	−0.0110 (7)	−0.0005 (8)	−0.0063 (7)
O3	0.0686 (12)	0.0515 (11)	0.0735 (13)	0.0030 (9)	0.0053 (9)	0.0063 (9)
S1	0.0661 (4)	0.0559 (4)	0.0670 (4)	−0.0067 (3)	−0.0126 (3)	−0.0123 (3)
C1	0.0796 (17)	0.0527 (14)	0.0915 (18)	0.0134 (13)	0.0109 (14)	−0.0028 (13)
C2	0.0606 (14)	0.0526 (13)	0.0535 (12)	−0.0029 (11)	0.0006 (10)	−0.0010 (10)
C3	0.0527 (12)	0.0452 (12)	0.0466 (11)	−0.0081 (10)	0.0068 (9)	0.0000 (9)
C4	0.0480 (12)	0.0495 (13)	0.0668 (14)	−0.0112 (10)	0.0004 (10)	−0.0005 (10)
C5	0.0512 (13)	0.0578 (14)	0.0750 (15)	−0.0005 (11)	0.0052 (11)	−0.0018 (12)
C6	0.0631 (15)	0.0486 (13)	0.0634 (14)	−0.0058 (11)	0.0076 (11)	−0.0088 (10)
C7	0.0541 (13)	0.0489 (13)	0.0541 (12)	−0.0056 (10)	0.0029 (10)	−0.0060 (10)
C8	0.0480 (12)	0.0474 (12)	0.0468 (11)	−0.0073 (9)	0.0076 (9)	0.0002 (9)
C9	0.0532 (12)	0.0478 (12)	0.0500 (12)	−0.0061 (10)	0.0082 (10)	0.0014 (10)
C10	0.0719 (16)	0.0493 (14)	0.0762 (16)	−0.0177 (12)	0.0075 (13)	−0.0135 (11)
C11	0.0702 (18)	0.091 (2)	0.114 (2)	−0.0284 (15)	0.0012 (16)	−0.0259 (17)

Geometric parameters (Å, º)

N1—C6	1.460 (3)	C3—C8	1.447 (3)
N1—C1	1.470 (3)	C4—C8	1.503 (3)
N1—C5	1.465 (3)	C4—C5	1.519 (3)
N2—C2	1.342 (3)	C4—H4A	0.9700
N2—H2A	0.84 (3)	C4—H4B	0.9700
N2—H2B	0.87 (3)	C5—H5A	0.9700
O1—C9	1.224 (3)	C5—H5B	0.9700
O2—C9	1.339 (2)	C6—C7	1.489 (3)
O2—C10	1.445 (2)	C6—H6A	0.9700
O3—H3B	0.70 (3)	C6—H6B	0.9700
O3—H3A	0.99 (4)	C7—C8	1.349 (3)
S1—C2	1.734 (2)	C10—C11	1.490 (4)
S1—C7	1.745 (2)	C10—H10A	0.9700
C1—H1A	0.9600	C10—H10B	0.9700
C1—H1B	0.9600	C11—H11A	0.9600
C1—H1C	0.9600	C11—H11B	0.9600
C2—C3	1.389 (3)	C11—H11C	0.9600
C3—C9	1.439 (3)
C6—N1—C1	110.30 (18)	N1—C5—H5B	109.4
C6—N1—C5	110.12 (18)	C4—C5—H5B	109.4
C1—N1—C5	111.54 (19)	H5A—C5—H5B	108.0
C2—N2—H2A	119.5 (19)	N1—C6—C7	108.74 (18)
C2—N2—H2B	115.7 (17)	N1—C6—H6A	109.9
H2A—N2—H2B	124 (3)	C7—C6—H6A	109.9
C9—O2—C10	116.95 (18)	N1—C6—H6B	109.9
H3B—O3—H3A	107 (3)	C7—C6—H6B	109.9
C2—S1—C7	91.46 (10)	H6A—C6—H6B	108.3
N1—C1—H1A	109.5	C8—C7—C6	125.8 (2)
N1—C1—H1B	109.5	C8—C7—S1	112.28 (17)
H1A—C1—H1B	109.5	C6—C7—S1	121.83 (16)
N1—C1—H1C	109.5	C7—C8—C3	112.8 (2)
H1A—C1—H1C	109.5	C7—C8—C4	119.4 (2)
H1B—C1—H1C	109.5	C3—C8—C4	127.72 (18)
N2—C2—C3	128.8 (2)	O1—C9—O2	121.9 (2)
N2—C2—S1	119.76 (19)	O1—C9—C3	124.6 (2)
C3—C2—S1	111.41 (17)	O2—C9—C3	113.53 (19)
C2—C3—C9	119.6 (2)	O2—C10—C11	107.1 (2)
C2—C3—C8	112.02 (19)	O2—C10—H10A	110.3
C9—C3—C8	128.39 (19)	C11—C10—H10A	110.3
C8—C4—C5	111.25 (17)	O2—C10—H10B	110.3
C8—C4—H4A	109.4	C11—C10—H10B	110.3
C5—C4—H4A	109.4	H10A—C10—H10B	108.6
C8—C4—H4B	109.4	C10—C11—H11A	109.5
C5—C4—H4B	109.4	C10—C11—H11B	109.5
H4A—C4—H4B	108.0	H11A—C11—H11B	109.5
N1—C5—C4	111.12 (18)	C10—C11—H11C	109.5
N1—C5—H5A	109.4	H11A—C11—H11C	109.5
C4—C5—H5A	109.4	H11B—C11—H11C	109.5
C7—S1—C2—N2	−179.7 (2)	S1—C7—C8—C3	−1.0 (2)
C7—S1—C2—C3	−0.32 (17)	C6—C7—C8—C4	−2.8 (3)
N2—C2—C3—C9	−1.2 (4)	S1—C7—C8—C4	−179.47 (15)
S1—C2—C3—C9	179.50 (15)	C2—C3—C8—C7	0.7 (3)
N2—C2—C3—C8	179.1 (2)	C9—C3—C8—C7	−178.9 (2)
S1—C2—C3—C8	−0.2 (2)	C2—C3—C8—C4	179.1 (2)
C6—N1—C5—C4	−68.2 (2)	C9—C3—C8—C4	−0.5 (4)
C1—N1—C5—C4	169.03 (19)	C5—C4—C8—C7	−9.6 (3)
C8—C4—C5—N1	43.8 (3)	C5—C4—C8—C3	172.2 (2)
C1—N1—C6—C7	176.08 (19)	C10—O2—C9—O1	0.9 (3)
C5—N1—C6—C7	52.5 (2)	C10—O2—C9—C3	−178.43 (18)
N1—C6—C7—C8	−18.6 (3)	C2—C3—C9—O1	0.7 (3)
N1—C6—C7—S1	157.76 (16)	C8—C3—C9—O1	−179.7 (2)
C2—S1—C7—C8	0.75 (18)	C2—C3—C9—O2	179.97 (18)
C2—S1—C7—C6	−176.0 (2)	C8—C3—C9—O2	−0.4 (3)
C6—C7—C8—C3	175.7 (2)	C9—O2—C10—C11	178.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^i	0.84 (3)	2.02 (3)	2.846 (3)	171.00
N2—H2B···O1	0.88 (2)	2.10 (3)	2.741 (3)	130 (2)
C4—H4A···O2	0.97	2.52	2.858 (2)	100
O3—H3A···N1	1.00 (4)	1.80 (4)	2.790 (3)	170 (3)
O3—H3B···O1^ii	0.71 (3)	2.17 (3)	2.874 (3)	176.00

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z.