Ethyl 2-amino-4,5-dimethyl-thio-phene-3-carboxyl-ate.

In the title compound, C(9)H(13)NO(2)S, the mean planes of thio-phene ring [maximum deviation = 0.0042 (10) Å] and eth-oxy-carbonyl group [0.0242 (15) Å] are almost coplanar [dihedral angle between them = 0.68 (11)°]. The H atoms of the two methyl groups attached to the thio-phene ring are each disordered over two orientations with site-occupancy ratios of 0.77 (4):0.23 (4) and 0.84 (4):0.16 (4). An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds into an infinite wave-like chain running parallel to the b-axis direction. The crystal structure also features C-H⋯π inter-actions.

Related literature

For the synthesis, see: Gewald (1965) ▶. For background to biologically active compounds prepared from the title compound, see: Alqasoumi et al. (2009 ▶); Ghorab et al. (2006, ▶ 2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C9H13NO2S

M = 199.26

Monoclinic,

a = 7.9487 (2) Å

b = 9.8939 (3) Å

c = 13.4348 (4) Å

β = 106.143 (2)°

V = 1014.90 (5) Å3

Z = 4

Cu Kα radiation

μ = 2.59 mm−1

T = 296 K

0.92 × 0.26 × 0.08 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.199, T max = 0.820

6429 measured reflections

1671 independent reflections

1504 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.104

S = 1.07

1671 reflections

132 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026268/hb6845sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026268/hb6845Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812026268/hb6845Isup3.cml

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

C9H13NO2S	F(000) = 424
Mr = 199.26	Dx = 1.304 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 1386 reflections
a = 7.9487 (2) Å	θ = 3.4–70.2°
b = 9.8939 (3) Å	µ = 2.59 mm−1
c = 13.4348 (4) Å	T = 296 K
β = 106.143 (2)°	Plate, brown
V = 1014.90 (5) Å3	0.92 × 0.26 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	1671 independent reflections
Radiation source: fine-focus sealed tube	1504 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 65.0°, θmin = 5.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→8
Tmin = 0.199, Tmax = 0.820	k = −11→11
6429 measured reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0573P)2 + 0.1221P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
1671 reflections	Δρmax = 0.19 e Å−3
132 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0041 (9)

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	Occ. (<1)
S1	0.19746 (6)	0.19752 (4)	0.58473 (4)	0.0611 (2)
O1	0.31318 (16)	0.65860 (11)	0.49116 (9)	0.0545 (3)
O2	0.44541 (19)	0.61171 (12)	0.65701 (9)	0.0667 (4)
N1	0.3976 (3)	0.35938 (18)	0.72936 (12)	0.0726 (5)
C1	0.3045 (2)	0.34698 (16)	0.62875 (12)	0.0520 (4)
C2	0.2743 (2)	0.44243 (15)	0.55082 (11)	0.0458 (4)
C3	0.1625 (2)	0.39154 (16)	0.45331 (12)	0.0481 (4)
C4	0.1130 (2)	0.26238 (18)	0.46019 (14)	0.0554 (4)
C5	0.0030 (3)	0.1727 (2)	0.37724 (19)	0.0763 (6)
H5A	0.0682	0.1482	0.3296	0.114*	0.77 (4)
H5B	−0.1014	0.2200	0.3408	0.114*	0.77 (4)
H5C	−0.0282	0.0926	0.4083	0.114*	0.77 (4)
H5D	−0.0262	0.2197	0.3122	0.114*	0.23 (4)
H5E	−0.1025	0.1489	0.3945	0.114*	0.23 (4)
H5F	0.0673	0.0922	0.3720	0.114*	0.23 (4)
C6	0.1078 (2)	0.46993 (19)	0.35388 (13)	0.0622 (5)
H6A	0.0388	0.4131	0.2999	0.093*	0.84 (4)
H6B	0.2100	0.5001	0.3355	0.093*	0.84 (4)
H6C	0.0396	0.5468	0.3627	0.093*	0.84 (4)
H6D	−0.0103	0.4465	0.3171	0.093*	0.16 (4)
H6E	0.1843	0.4485	0.3120	0.093*	0.16 (4)
H6F	0.1145	0.5650	0.3689	0.093*	0.16 (4)
C7	0.3521 (2)	0.57551 (15)	0.57265 (11)	0.0469 (4)
C8	0.3871 (3)	0.79279 (16)	0.50551 (15)	0.0568 (4)
H8A	0.5139	0.7884	0.5241	0.068*
H8B	0.3524	0.8395	0.5602	0.068*
C9	0.3179 (3)	0.8652 (2)	0.40444 (17)	0.0718 (6)
H9A	0.3617	0.9561	0.4109	0.108*
H9B	0.1923	0.8668	0.3862	0.108*
H9C	0.3554	0.8190	0.3515	0.108*
H1N1	0.453 (3)	0.438 (3)	0.7431 (19)	0.084 (7)*
H2N1	0.435 (3)	0.291 (2)	0.7699 (19)	0.068 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0783 (4)	0.0381 (3)	0.0662 (3)	−0.00222 (17)	0.0189 (2)	0.00472 (17)
O1	0.0677 (7)	0.0409 (6)	0.0480 (6)	−0.0061 (5)	0.0046 (5)	0.0053 (5)
O2	0.0971 (10)	0.0438 (6)	0.0460 (7)	−0.0060 (6)	−0.0019 (6)	−0.0041 (5)
N1	0.1166 (14)	0.0449 (9)	0.0439 (8)	0.0066 (9)	0.0018 (8)	0.0056 (7)
C1	0.0693 (10)	0.0379 (8)	0.0470 (9)	0.0063 (7)	0.0132 (7)	0.0005 (6)
C2	0.0556 (9)	0.0371 (8)	0.0422 (8)	0.0051 (6)	0.0094 (6)	0.0001 (6)
C3	0.0503 (9)	0.0433 (8)	0.0470 (8)	0.0018 (6)	0.0075 (6)	−0.0021 (6)
C4	0.0558 (10)	0.0467 (9)	0.0603 (10)	−0.0014 (7)	0.0106 (7)	−0.0046 (7)
C5	0.0745 (13)	0.0581 (11)	0.0847 (15)	−0.0130 (9)	0.0031 (10)	−0.0155 (10)
C6	0.0696 (11)	0.0604 (11)	0.0455 (9)	−0.0006 (8)	−0.0024 (7)	0.0013 (7)
C7	0.0578 (9)	0.0382 (8)	0.0414 (8)	0.0048 (6)	0.0081 (6)	0.0001 (6)
C8	0.0671 (11)	0.0406 (9)	0.0592 (10)	−0.0047 (7)	0.0121 (8)	0.0038 (7)
C9	0.0820 (14)	0.0516 (11)	0.0755 (13)	−0.0027 (9)	0.0114 (10)	0.0196 (9)

S1—C1	1.7264 (17)	C5—H5C	0.9600
S1—C4	1.7429 (18)	C5—H5D	0.9600
O1—C7	1.3348 (19)	C5—H5E	0.9600
O1—C8	1.4429 (19)	C5—H5F	0.9600
O2—C7	1.2228 (19)	C6—H6A	0.9600
N1—C1	1.354 (2)	C6—H6B	0.9600
N1—H1N1	0.88 (3)	C6—H6C	0.9600
N1—H2N1	0.87 (2)	C6—H6D	0.9600
C1—C2	1.381 (2)	C6—H6E	0.9600
C2—C7	1.450 (2)	C6—H6F	0.9600
C2—C3	1.453 (2)	C8—C9	1.498 (3)
C3—C4	1.348 (2)	C8—H8A	0.9700
C3—C6	1.501 (2)	C8—H8B	0.9700
C4—C5	1.501 (3)	C9—H9A	0.9600
C5—H5A	0.9600	C9—H9B	0.9600
C5—H5B	0.9600	C9—H9C	0.9600
C1—S1—C4	92.01 (8)	H5E—C5—H5F	109.5
C7—O1—C8	117.66 (13)	C3—C6—H6A	109.5
C1—N1—H1N1	112.9 (16)	C3—C6—H6B	109.5
C1—N1—H2N1	123.7 (15)	C3—C6—H6C	109.5
H1N1—N1—H2N1	119 (2)	C3—C6—H6D	109.5
N1—C1—C2	128.80 (17)	C3—C6—H6E	109.5
N1—C1—S1	120.01 (14)	H6D—C6—H6E	109.5
C2—C1—S1	111.16 (12)	C3—C6—H6F	109.5
C1—C2—C7	119.57 (14)	H6D—C6—H6F	109.5
C1—C2—C3	112.36 (14)	H6E—C6—H6F	109.5
C7—C2—C3	128.07 (13)	O2—C7—O1	121.49 (14)
C4—C3—C2	112.56 (14)	O2—C7—C2	124.63 (14)
C4—C3—C6	122.22 (15)	O1—C7—C2	113.88 (13)
C2—C3—C6	125.21 (15)	O1—C8—C9	106.59 (15)
C3—C4—C5	129.10 (18)	O1—C8—H8A	110.4
C3—C4—S1	111.91 (12)	C9—C8—H8A	110.4
C5—C4—S1	118.99 (15)	O1—C8—H8B	110.4
C4—C5—H5A	109.5	C9—C8—H8B	110.4
C4—C5—H5B	109.5	H8A—C8—H8B	108.6
C4—C5—H5C	109.5	C8—C9—H9A	109.5
C4—C5—H5D	109.5	C8—C9—H9B	109.5
C4—C5—H5E	109.5	H9A—C9—H9B	109.5
H5D—C5—H5E	109.5	C8—C9—H9C	109.5
C4—C5—H5F	109.5	H9A—C9—H9C	109.5
H5D—C5—H5F	109.5	H9B—C9—H9C	109.5
C4—S1—C1—N1	178.55 (17)	C2—C3—C4—S1	0.56 (19)
C4—S1—C1—C2	0.60 (14)	C6—C3—C4—S1	179.60 (14)
N1—C1—C2—C7	1.8 (3)	C1—S1—C4—C3	−0.67 (15)
S1—C1—C2—C7	179.54 (12)	C1—S1—C4—C5	178.19 (17)
N1—C1—C2—C3	−178.12 (19)	C8—O1—C7—O2	0.8 (2)
S1—C1—C2—C3	−0.40 (18)	C8—O1—C7—C2	−179.18 (15)
C1—C2—C3—C4	−0.1 (2)	C1—C2—C7—O2	0.0 (3)
C7—C2—C3—C4	179.95 (16)	C3—C2—C7—O2	179.97 (16)
C1—C2—C3—C6	−179.12 (16)	C1—C2—C7—O1	−179.94 (14)
C7—C2—C3—C6	0.9 (3)	C3—C2—C7—O1	0.0 (2)
C2—C3—C4—C5	−178.16 (19)	C7—O1—C8—C9	−177.97 (15)
C6—C3—C4—C5	0.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.89 (3)	2.06 (3)	2.744 (2)	133 (2)
N1—H2N1···O2i	0.87 (2)	2.12 (2)	2.972 (2)	167 (2)
C8—H8A···Cg1ii	0.97	2.78	3.600 (2)	142

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of S1/C1–C4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.89 (3)	2.06 (3)	2.744 (2)	133 (2)
N1—H2N1⋯O2i	0.87 (2)	2.12 (2)	2.972 (2)	167 (2)
C8—H8A⋯Cg1ii	0.97	2.78	3.600 (2)	142

Symmetry codes: (i) ; (ii) .