Ethyl 2-amino­thio­phene-3-carboxyl­ate

The structure of the title compound, C₇H₉NO₂S, forms a supra­molecular network. The planar sheet structure displays both intra- and inter­molecular N—H...O hydrogen bonding. The asymmetric unit consists of two molecules.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.115
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).

Ethyl 2-aminothiophene-3-carboxylate

Crystal data

C7H9NO2S	F(000) = 720
Mr = 171.21	Dx = 1.394 Mg m^−3
Monoclinic, P21/c	Melting point = 320–321 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 10.1838 (1) Å	Cell parameters from 4685 reflections
b = 17.8042 (2) Å	θ = 2.5–72.9°
c = 10.3046 (1) Å	µ = 3.13 mm^−1
β = 119.192 (1)°	T = 100 K
V = 1631.07 (3) Å^3	Acicular, colourless
Z = 8	0.60 × 0.13 × 0.12 mm

Data collection

Bruker SMART 2K/PLATFORM diffractometer	3207 independent reflections
Radiation source: sealed tube	2714 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 5.5 pixels mm^-1	θmax = 72.9°, θmin = 4.9°
ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −21→21
Tmin = 0.477, Tmax = 0.684	l = −12→12
13274 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0808P)^2] where P = (Fo^2 + 2Fc^2)/3
3207 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Experimental. ¹H NMR (CDCl₃, δ, p.p.m.): 1.33 (t, J = 7.1 Hz, 3H), 4.27 (q, J = 7.1 Hz, 2H), 6.17 (d, J = 4.8 Hz, 1H), 6.70 (d, J = 5.8 Hz, 1H), 5.86 (br s, 2H); ¹³C NMR (CDCl₃, δ, p.p.m.): 14.53, 59.77, 106.91, 107.17, 125.93, 162.74, 165.50.

X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.

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
S1	0.37538 (5)	0.19527 (3)	0.08000 (5)	0.02045 (15)
N11	0.47023 (18)	0.09828 (9)	−0.05810 (18)	0.0236 (4)
H11A	0.5358	0.0814	−0.0834	0.028*
H11B	0.3848	0.0743	−0.0871	0.028*
C11	0.5006 (2)	0.16104 (10)	0.02524 (19)	0.0176 (4)
C12	0.6285 (2)	0.20595 (10)	0.08077 (19)	0.0169 (4)
C13	0.6207 (2)	0.26872 (10)	0.16451 (19)	0.0179 (4)
H13	0.6979	0.3054	0.2091	0.022*
C14	0.4928 (2)	0.27047 (10)	0.1736 (2)	0.0205 (4)
H14	0.4697	0.3081	0.2247	0.025*
C15	0.7509 (2)	0.18877 (9)	0.05265 (19)	0.0159 (4)
O15	0.75399 (14)	0.13410 (7)	−0.01872 (14)	0.0196 (3)
O16	0.86169 (14)	0.23974 (7)	0.11152 (14)	0.0195 (3)
C16	0.9822 (2)	0.23249 (10)	0.0755 (2)	0.0200 (4)
H16A	0.9428	0.2387	−0.0327	0.024*
H16B	1.0301	0.1825	0.1055	0.024*
C17	1.0937 (2)	0.29341 (11)	0.1603 (2)	0.0246 (4)
H17A	1.0450	0.3425	0.1283	0.037*
H17B	1.1787	0.2904	0.1409	0.037*
H17C	1.1301	0.2870	0.2669	0.037*
S2	−0.29162 (5)	0.52732 (3)	0.24748 (5)	0.02364 (15)
C21	−0.1165 (2)	0.49248 (10)	0.28793 (19)	0.0182 (4)
N21	−0.06192 (19)	0.42946 (9)	0.36915 (18)	0.0227 (3)
H21A	0.0255	0.4114	0.3863	0.027*
H21B	−0.1137	0.4064	0.4050	0.027*
C22	−0.0520 (2)	0.53645 (10)	0.22249 (19)	0.0178 (4)
C23	−0.1472 (2)	0.59752 (10)	0.1385 (2)	0.0214 (4)
H23	−0.1209	0.6328	0.0859	0.026*
C24	−0.2783 (2)	0.59998 (11)	0.1417 (2)	0.0251 (4)
H24	−0.3539	0.6369	0.0922	0.030*
C25	0.0943 (2)	0.51810 (10)	0.23973 (19)	0.0171 (4)
O25	0.17364 (15)	0.46643 (7)	0.31678 (15)	0.0219 (3)
O26	0.13526 (14)	0.56322 (7)	0.16113 (14)	0.0197 (3)
C26	0.2756 (2)	0.54380 (10)	0.1644 (2)	0.0200 (4)
H26A	0.2695	0.4925	0.1246	0.024*
H26B	0.3601	0.5454	0.2676	0.024*
C27	0.2997 (2)	0.60039 (11)	0.0697 (2)	0.0225 (4)
H27A	0.2118	0.6010	−0.0301	0.034*
H27B	0.3893	0.5868	0.0629	0.034*
H27C	0.3135	0.6503	0.1146	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0175 (2)	0.0244 (3)	0.0206 (2)	−0.00043 (16)	0.0102 (2)	−0.00057 (16)
N11	0.0210 (8)	0.0223 (8)	0.0288 (9)	−0.0054 (6)	0.0132 (7)	−0.0081 (7)
C11	0.0169 (9)	0.0198 (9)	0.0156 (8)	0.0007 (7)	0.0075 (7)	0.0024 (7)
C12	0.0186 (9)	0.0166 (8)	0.0144 (8)	0.0000 (7)	0.0071 (7)	0.0011 (6)
C13	0.0193 (9)	0.0184 (8)	0.0154 (8)	−0.0004 (7)	0.0079 (8)	0.0000 (6)
C14	0.0223 (9)	0.0203 (9)	0.0181 (8)	0.0015 (7)	0.0092 (8)	−0.0006 (7)
C15	0.0161 (8)	0.0162 (8)	0.0139 (8)	−0.0012 (6)	0.0061 (7)	0.0018 (6)
O15	0.0202 (7)	0.0172 (6)	0.0212 (7)	−0.0009 (5)	0.0100 (6)	−0.0026 (5)
O16	0.0179 (6)	0.0196 (6)	0.0210 (6)	−0.0035 (5)	0.0096 (6)	−0.0042 (5)
C16	0.0171 (9)	0.0233 (9)	0.0209 (9)	−0.0016 (7)	0.0103 (8)	−0.0008 (7)
C17	0.0196 (9)	0.0256 (10)	0.0273 (10)	−0.0034 (7)	0.0106 (9)	−0.0042 (8)
S2	0.0202 (3)	0.0266 (3)	0.0268 (3)	0.00413 (17)	0.0135 (2)	0.00392 (18)
C21	0.0161 (8)	0.0205 (9)	0.0161 (8)	0.0005 (7)	0.0064 (7)	−0.0031 (7)
N21	0.0226 (8)	0.0210 (8)	0.0282 (9)	0.0032 (6)	0.0151 (7)	0.0063 (6)
C22	0.0190 (9)	0.0173 (9)	0.0157 (8)	0.0007 (7)	0.0073 (8)	−0.0013 (6)
C23	0.0228 (9)	0.0213 (9)	0.0199 (9)	0.0019 (7)	0.0102 (8)	0.0010 (7)
C24	0.0255 (10)	0.0253 (10)	0.0240 (10)	0.0077 (8)	0.0116 (9)	0.0065 (8)
C25	0.0175 (9)	0.0164 (8)	0.0177 (8)	−0.0022 (7)	0.0088 (8)	−0.0032 (7)
O25	0.0201 (7)	0.0190 (7)	0.0268 (7)	0.0039 (5)	0.0117 (6)	0.0046 (5)
O26	0.0184 (6)	0.0193 (6)	0.0237 (7)	0.0021 (5)	0.0121 (6)	0.0029 (5)
C26	0.0175 (9)	0.0205 (9)	0.0224 (9)	0.0006 (7)	0.0102 (8)	−0.0010 (7)
C27	0.0210 (9)	0.0253 (10)	0.0220 (9)	−0.0006 (7)	0.0111 (8)	0.0011 (7)

Geometric parameters (Å, º)

S1—C11	1.7377 (18)	S2—C21	1.7363 (19)
S1—C14	1.7398 (19)	S2—C24	1.739 (2)
N11—C11	1.350 (2)	C21—N21	1.347 (2)
N11—H11A	0.88	C21—C22	1.390 (3)
N11—H11B	0.88	N21—H21A	0.88
C11—C12	1.391 (2)	N21—H21B	0.88
C12—C13	1.438 (2)	C22—C23	1.433 (2)
C12—C15	1.443 (3)	C22—C25	1.449 (3)
C13—C14	1.351 (3)	C23—C24	1.351 (3)
C13—H13	0.95	C23—H23	0.95
C14—H14	0.95	C24—H24	0.95
C15—O15	1.230 (2)	C25—O25	1.226 (2)
C15—O16	1.341 (2)	C25—O26	1.343 (2)
O16—C16	1.451 (2)	O26—C26	1.455 (2)
C16—C17	1.504 (2)	C26—C27	1.503 (2)
C16—H16A	0.99	C26—H26A	0.99
C16—H16B	0.99	C26—H26B	0.99
C17—H17A	0.98	C27—H27A	0.98
C17—H17B	0.98	C27—H27B	0.98
C17—H17C	0.98	C27—H27C	0.98
C11—S1—C14	92.01 (9)	C21—S2—C24	91.77 (9)
C11—N11—H11A	120	N21—C21—C22	128.42 (18)
C11—N11—H11B	120	N21—C21—S2	120.72 (14)
H11A—N11—H11B	120	C22—C21—S2	110.84 (14)
N11—C11—C12	128.00 (17)	C21—N21—H21A	120
N11—C11—S1	121.32 (14)	C21—N21—H21B	120
C12—C11—S1	110.68 (13)	H21A—N21—H21B	120
C11—C12—C13	112.26 (16)	C21—C22—C23	112.29 (17)
C11—C12—C15	121.49 (16)	C21—C22—C25	120.97 (16)
C13—C12—C15	126.25 (16)	C23—C22—C25	126.72 (17)
C14—C13—C12	113.38 (16)	C24—C23—C22	113.31 (17)
C14—C13—H13	123.3	C24—C23—H23	123.3
C12—C13—H13	123.3	C22—C23—H23	123.3
C13—C14—S1	111.66 (14)	C23—C24—S2	111.78 (15)
C13—C14—H14	124.2	C23—C24—H24	124.1
S1—C14—H14	124.2	S2—C24—H24	124.1
O15—C15—O16	123.02 (17)	O25—C25—O26	122.62 (16)
O15—C15—C12	124.37 (16)	O25—C25—C22	124.17 (17)
O16—C15—C12	112.61 (15)	O26—C25—C22	113.21 (15)
C15—O16—C16	117.02 (14)	C25—O26—C26	115.75 (14)
O16—C16—C17	106.27 (14)	O26—C26—C27	107.16 (15)
O16—C16—H16A	110.5	O26—C26—H26A	110.3
C17—C16—H16A	110.5	C27—C26—H26A	110.3
O16—C16—H16B	110.5	O26—C26—H26B	110.3
C17—C16—H16B	110.5	C27—C26—H26B	110.3
H16A—C16—H16B	108.7	H26A—C26—H26B	108.5
C16—C17—H17A	109.5	C26—C27—H27A	109.5
C16—C17—H17B	109.5	C26—C27—H27B	109.5
H17A—C17—H17B	109.5	H27A—C27—H27B	109.5
C16—C17—H17C	109.5	C26—C27—H27C	109.5
H17A—C17—H17C	109.5	H27A—C27—H27C	109.5
H17B—C17—H17C	109.5	H27B—C27—H27C	109.5
C14—S1—C11—N11	−179.77 (16)	C24—S2—C21—N21	−177.61 (16)
C14—S1—C11—C12	1.15 (14)	C24—S2—C21—C22	0.56 (14)
N11—C11—C12—C13	179.65 (17)	N21—C21—C22—C23	177.24 (18)
S1—C11—C12—C13	−1.34 (18)	S2—C21—C22—C23	−0.7 (2)
N11—C11—C12—C15	0.1 (3)	N21—C21—C22—C25	−1.6 (3)
S1—C11—C12—C15	179.10 (13)	S2—C21—C22—C25	−179.55 (13)
C11—C12—C13—C14	0.9 (2)	C21—C22—C23—C24	0.6 (2)
C15—C12—C13—C14	−179.60 (17)	C25—C22—C23—C24	179.32 (17)
C12—C13—C14—S1	0.0 (2)	C22—C23—C24—S2	−0.2 (2)
C11—S1—C14—C13	−0.67 (15)	C21—S2—C24—C23	−0.22 (16)
C11—C12—C15—O15	−1.1 (3)	C21—C22—C25—O25	−3.7 (3)
C13—C12—C15—O15	179.42 (17)	C23—C22—C25—O25	177.64 (17)
C11—C12—C15—O16	178.12 (15)	C21—C22—C25—O26	175.68 (15)
C13—C12—C15—O16	−1.4 (2)	C23—C22—C25—O26	−2.9 (3)
O15—C15—O16—C16	6.0 (2)	O25—C25—O26—C26	4.2 (2)
C12—C15—O16—C16	−173.19 (14)	C22—C25—O26—C26	−175.22 (14)
C15—O16—C16—C17	−177.35 (15)	C25—O26—C26—C27	179.64 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O15	0.88	2.19	2.789 (2)	124
N11—H11B···O25^i	0.88	2.01	2.883 (2)	170
N21—H21A···O25	0.88	2.19	2.782 (2)	124
N21—H21B···O15^ii	0.88	1.99	2.871 (2)	173

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