Ethyl 3-amino-5-anilino-4-cyano-thio-phene-2-carboxyl-ate.

In the title compound, C14H13N3O2S, the dihedral angle between the thio-phene and phenyl rings is 24.95 (8)°. The mol-ecular structure is consolidated by intra-molecular N-H⋯O and C-H⋯S inter-actions. The crystal structure features N-H⋯N and N-H⋯O hydrogen bonds forming centrosymmetric R 2 (2)(12) dimers, which are linked into a two-dimensional network parallel to (011) with an S(6)R 2 (2) S(6) motif. In addition, π-π stacking inter-actions [centroid-centroid distance = 3.7013 (12) Å] occur between the thio-phene and phenyl rings of adjacent mol-ecules.

Related literature

For pharmaceutical and industrial applications of amino-thio­phene-containingg compounds, see: Inversen et al. (2000 ▶); Webb et al. (2000 ▶). For the synthesis of multi-substituted thiphene compounds, see: El-Sharkawy et al. (2012 ▶); Huang et al. (2011 ▶). For the crystal structure of a related compound, see: Mabkhot et al. (2013 ▶).

Experimental

Crystal data

C14H13N3O2S

M = 287.34

Monoclinic,

a = 8.6121 (15) Å

b = 10.6579 (15) Å

c = 14.328 (3) Å

β = 92.580 (3)°

V = 1313.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.55 × 0.04 × 0.03 mm

Data collection

Rigaku AFC12 (Right, Saturn724+) diffractometer

Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012 ▶) T min = 0.887, T max = 1.000

8995 measured reflections

2996 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.088

S = 1.07

2996 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CrystalClear-SM Expert (Rigaku, 2012 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018734/pv2639sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018734/pv2639Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018734/pv2639Isup3.cml

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

C14H13N3O2S	F(000) = 600
Mr = 287.34	Dx = 1.453 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 4552 reflections
a = 8.6121 (15) Å	θ = 2.4–30.2°
b = 10.6579 (15) Å	µ = 0.25 mm−1
c = 14.328 (3) Å	T = 100 K
β = 92.580 (3)°	Rod, light brown
V = 1313.8 (4) Å3	0.55 × 0.04 × 0.03 mm
Z = 4

Rigaku AFC12 (Right, Saturn724+) diffractometer	2996 independent reflections
Radiation source: Rotating Anode	2728 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.025
profile data from ω–scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	h = −7→11
Tmin = 0.887, Tmax = 1.000	k = −10→13
8995 measured reflections	l = −18→17

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088	W = 1/[Σ2(FO2) + (0.036P)2 + 0.9009P] WHERE P = (FO2 + 2FC2)/3
S = 1.07	(Δ/σ)max = 0.001
2996 reflections	Δρmax = 0.32 e Å−3
194 parameters	Δρmin = −0.26 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
S1	0.24094 (5)	0.56107 (3)	0.02889 (3)	0.0127 (1)
O1	0.25546 (13)	0.32279 (10)	−0.06700 (7)	0.0146 (3)
O2	0.09078 (14)	0.36573 (10)	−0.19090 (7)	0.0165 (3)
N1	0.19895 (16)	0.80331 (12)	0.08703 (9)	0.0139 (4)
N2	−0.03010 (18)	0.94889 (13)	−0.10133 (9)	0.0198 (4)
N3	−0.01723 (17)	0.62007 (13)	−0.20023 (9)	0.0147 (4)
C1	0.16973 (18)	0.71241 (14)	0.02243 (10)	0.0122 (4)
C2	0.08009 (18)	0.73139 (14)	−0.05985 (10)	0.0128 (4)
C3	0.06672 (18)	0.62244 (14)	−0.11815 (10)	0.0126 (4)
C4	0.14784 (19)	0.52211 (14)	−0.07826 (10)	0.0130 (4)
C5	0.01734 (19)	0.85067 (15)	−0.08401 (10)	0.0143 (4)
C6	0.15918 (18)	0.39930 (14)	−0.11823 (10)	0.0129 (4)
C7	0.2663 (2)	0.19549 (14)	−0.10206 (11)	0.0168 (4)
C8	0.3668 (2)	0.12347 (15)	−0.03187 (11)	0.0199 (5)
C9	0.28921 (18)	0.79947 (14)	0.17173 (10)	0.0130 (4)
C10	0.3166 (2)	0.69024 (14)	0.22309 (11)	0.0162 (4)
C11	0.4088 (2)	0.69608 (15)	0.30549 (11)	0.0191 (5)
C12	0.4702 (2)	0.80873 (15)	0.33839 (11)	0.0176 (5)
C13	0.43678 (19)	0.91814 (15)	0.28866 (11)	0.0164 (4)
C14	0.34788 (19)	0.91355 (15)	0.20580 (11)	0.0153 (4)
H3NA	−0.004 (2)	0.554 (2)	−0.2350 (14)	0.024 (5)*
H1N	0.158 (2)	0.8734 (18)	0.0753 (12)	0.012 (4)*
H3NB	−0.039 (2)	0.6900 (19)	−0.2278 (13)	0.018 (5)*
H7A	0.31360	0.19520	−0.16380	0.0200*
H7B	0.16180	0.15710	−0.10890	0.0200*
H8A	0.47190	0.15900	−0.02890	0.0300*
H8B	0.37140	0.03520	−0.05080	0.0300*
H8C	0.32240	0.12940	0.02980	0.0300*
H10	0.27300	0.61270	0.20230	0.0190*
H11	0.43010	0.62130	0.33980	0.0230*
H12	0.53430	0.81110	0.39410	0.0210*
H13	0.47510	0.99640	0.31160	0.0200*
H14	0.32660	0.98860	0.17180	0.0180*

	U11	U22	U33	U12	U13	U23
S1	0.0162 (2)	0.0097 (2)	0.0119 (2)	0.0022 (1)	−0.0026 (1)	−0.0003 (1)
O1	0.0197 (6)	0.0098 (5)	0.0139 (5)	0.0033 (4)	−0.0035 (4)	−0.0016 (4)
O2	0.0231 (6)	0.0123 (5)	0.0138 (5)	0.0014 (4)	−0.0039 (4)	−0.0009 (4)
N1	0.0181 (7)	0.0095 (6)	0.0136 (6)	0.0043 (5)	−0.0033 (5)	−0.0007 (5)
N2	0.0284 (8)	0.0151 (7)	0.0153 (7)	0.0043 (6)	−0.0062 (6)	−0.0022 (5)
N3	0.0196 (8)	0.0114 (7)	0.0128 (6)	0.0016 (5)	−0.0035 (5)	0.0004 (5)
C1	0.0126 (8)	0.0106 (7)	0.0136 (7)	0.0009 (6)	0.0017 (6)	0.0006 (5)
C2	0.0140 (8)	0.0116 (7)	0.0127 (7)	0.0011 (6)	−0.0001 (6)	0.0011 (5)
C3	0.0134 (8)	0.0110 (7)	0.0134 (7)	−0.0005 (6)	0.0019 (6)	0.0006 (6)
C4	0.0151 (8)	0.0128 (7)	0.0108 (7)	−0.0008 (6)	−0.0017 (6)	−0.0002 (5)
C5	0.0162 (8)	0.0157 (8)	0.0108 (7)	0.0011 (6)	−0.0015 (6)	−0.0026 (6)
C6	0.0138 (8)	0.0129 (7)	0.0121 (7)	0.0004 (6)	0.0010 (6)	0.0021 (5)
C7	0.0235 (9)	0.0106 (7)	0.0161 (7)	0.0037 (6)	−0.0022 (6)	−0.0026 (6)
C8	0.0262 (9)	0.0149 (8)	0.0184 (8)	0.0057 (7)	−0.0025 (7)	−0.0012 (6)
C9	0.0144 (8)	0.0142 (7)	0.0105 (7)	0.0016 (6)	0.0007 (6)	−0.0011 (6)
C10	0.0217 (9)	0.0121 (7)	0.0147 (7)	0.0010 (6)	−0.0001 (6)	−0.0013 (6)
C11	0.0264 (9)	0.0161 (8)	0.0148 (7)	0.0048 (7)	−0.0002 (7)	0.0021 (6)
C12	0.0193 (9)	0.0209 (8)	0.0123 (7)	0.0028 (6)	−0.0017 (6)	−0.0006 (6)
C13	0.0169 (8)	0.0158 (8)	0.0164 (7)	−0.0016 (6)	−0.0003 (6)	−0.0014 (6)
C14	0.0183 (8)	0.0128 (7)	0.0147 (7)	0.0004 (6)	0.0003 (6)	0.0019 (6)

S1—C1	1.7266 (16)	C7—C8	1.507 (2)
S1—C4	1.7497 (16)	C9—C14	1.396 (2)
O1—C6	1.3552 (19)	C9—C10	1.392 (2)
O1—C7	1.4512 (19)	C10—C11	1.394 (2)
O2—C6	1.2264 (18)	C11—C12	1.386 (2)
N1—C1	1.356 (2)	C12—C13	1.390 (2)
N1—C9	1.412 (2)	C13—C14	1.384 (2)
N2—C5	1.147 (2)	C7—H7A	0.9900
N3—C3	1.353 (2)	C7—H7B	0.9900
N1—H1N	0.84 (2)	C8—H8A	0.9800
N3—H3NB	0.86 (2)	C8—H8B	0.9800
N3—H3NA	0.87 (2)	C8—H8C	0.9800
C1—C2	1.395 (2)	C10—H10	0.9500
C2—C3	1.432 (2)	C11—H11	0.9500
C2—C5	1.418 (2)	C12—H12	0.9500
C3—C4	1.386 (2)	C13—H13	0.9500
C4—C6	1.434 (2)	C14—H14	0.9500
C1—S1—C4	91.55 (7)	N1—C9—C14	116.86 (13)
C6—O1—C7	114.99 (11)	C9—C10—C11	119.14 (14)
C1—N1—C9	130.11 (13)	C10—C11—C12	121.38 (15)
C1—N1—H1N	115.8 (12)	C11—C12—C13	119.04 (15)
C9—N1—H1N	114.1 (12)	C12—C13—C14	120.25 (15)
C3—N3—H3NA	115.7 (13)	C9—C14—C13	120.54 (14)
H3NA—N3—H3NB	117.9 (19)	O1—C7—H7A	110.00
C3—N3—H3NB	118.7 (13)	O1—C7—H7B	110.00
S1—C1—C2	111.26 (11)	C8—C7—H7A	110.00
N1—C1—C2	123.52 (14)	C8—C7—H7B	110.00
S1—C1—N1	125.20 (11)	H7A—C7—H7B	109.00
C1—C2—C5	121.79 (14)	C7—C8—H8A	109.00
C3—C2—C5	124.39 (13)	C7—C8—H8B	109.00
C1—C2—C3	113.73 (13)	C7—C8—H8C	109.00
C2—C3—C4	111.05 (13)	H8A—C8—H8B	110.00
N3—C3—C2	123.23 (14)	H8A—C8—H8C	109.00
N3—C3—C4	125.71 (14)	H8B—C8—H8C	109.00
S1—C4—C3	112.41 (11)	C9—C10—H10	120.00
S1—C4—C6	122.03 (11)	C11—C10—H10	120.00
C3—C4—C6	125.56 (14)	C10—C11—H11	119.00
N2—C5—C2	177.72 (16)	C12—C11—H11	119.00
O2—C6—C4	124.52 (14)	C11—C12—H12	120.00
O1—C6—C4	112.58 (12)	C13—C12—H12	120.00
O1—C6—O2	122.90 (13)	C12—C13—H13	120.00
O1—C7—C8	106.81 (12)	C14—C13—H13	120.00
N1—C9—C10	123.53 (14)	C9—C14—H14	120.00
C10—C9—C14	119.57 (14)	C13—C14—H14	120.00
C4—S1—C1—N1	−179.31 (14)	C1—C2—C3—C4	−0.1 (2)
C4—S1—C1—C2	−0.86 (12)	N3—C3—C4—C6	1.4 (3)
C1—S1—C4—C6	−179.95 (13)	N3—C3—C4—S1	−179.43 (13)
C1—S1—C4—C3	0.82 (13)	C2—C3—C4—S1	−0.55 (17)
C7—O1—C6—O2	−2.8 (2)	C2—C3—C4—C6	−179.75 (15)
C7—O1—C6—C4	177.50 (13)	C3—C4—C6—O1	175.42 (14)
C6—O1—C7—C8	−175.31 (13)	C3—C4—C6—O2	−4.3 (3)
C9—N1—C1—C2	−178.43 (15)	S1—C4—C6—O1	−3.71 (19)
C9—N1—C1—S1	−0.2 (2)	S1—C4—C6—O2	176.63 (13)
C1—N1—C9—C14	155.95 (16)	N1—C9—C10—C11	179.34 (15)
C1—N1—C9—C10	−26.5 (3)	C14—C9—C10—C11	−3.1 (2)
N1—C1—C2—C3	179.20 (14)	N1—C9—C14—C13	179.64 (14)
S1—C1—C2—C5	−175.79 (12)	C10—C9—C14—C13	2.0 (2)
N1—C1—C2—C5	2.7 (2)	C9—C10—C11—C12	1.7 (3)
S1—C1—C2—C3	0.72 (17)	C10—C11—C12—C13	1.0 (3)
C5—C2—C3—C4	176.30 (15)	C11—C12—C13—C14	−2.2 (2)
C1—C2—C3—N3	178.81 (14)	C12—C13—C14—C9	0.8 (2)
C5—C2—C3—N3	−4.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3NA···O2	0.87 (2)	2.25 (2)	2.8671 (19)	128.0 (17)
N1—H1N···N2i	0.84 (2)	2.23 (2)	3.026 (2)	158.1 (16)
N3—H3NB···O2ii	0.86 (2)	2.24 (2)	3.0985 (18)	175.9 (17)
C10—H10···S1	0.95	2.55	3.1463 (17)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3NA⋯O2	0.87 (2)	2.25 (2)	2.8671 (19)	128.0 (17)
N1—H1N⋯N2i	0.84 (2)	2.23 (2)	3.026 (2)	158.1 (16)
N3—H3NB⋯O2ii	0.86 (2)	2.24 (2)	3.0985 (18)	175.9 (17)
C10—H10⋯S1	0.95	2.55	3.1463 (17)	121

Symmetry codes: (i) ; (ii) .