Ethyl 3-bromo-4-cyano-5-[(2-eth­oxy-2-oxoeth­yl)sulfan­yl]thio­phene-2-carboxyl­ate

Abstract

The title compound, C₁₂H₁₂BrNO₄S₂, was obtained by the Sandmeyer reaction from ethyl 3-amino-4-cyano-5-[(2-eth­oxy-2-oxoeth­yl)sulfan­yl]thio­phene-2-carboxyl­ate. The dihedral angle between the thiophene ring and linked CO₂ ester group is 2.0 (5)°.

Related literature  

For background literature on the use of 3-amino-4-cyano-5-eth­oxy­carbonyl­methyl­sulfanyl-thio­phene-2-carb­oxy­lic acid ethyl ester as an important inter­mediate compound for the synthesis of thieno­pyrimidine derivatives, which are thought to be potential biologically active compounds or pharmaceuticals, see: Liu et al. (2008 ▶). For a related compound, see: Padmavathi et al. (2011 ▶).

Experimental  

Crystal data  

• C₁₂H₁₂BrNO₄S₂

• M _r = 378.26

• Monoclinic,

• a = 8.5896 (17) Å

• b = 10.837 (2) Å

• c = 16.584 (3) Å

• β = 99.44 (3)°

• V = 1522.8 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 2.98 mm⁻¹

• T = 293 K

• 0.20 × 0.18 × 0.12 mm

Data collection  

• Rigaku Saturn diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.587, T _max = 0.716

• 15211 measured reflections

• 3596 independent reflections

• 2224 reflections with I > 2σ(I)

• R _int = 0.067

Refinement  

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.157

• S = 1.00

• 3596 reflections

• 184 parameters

• H-atom parameters constrained

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.71 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

supplementary crystallographic information

Comment

3-Amino-4-cyano-5-ethoxycarbonylmethylsulfanyl-thiophene-2-carboxylic acid ethyl ester is an important intermediate compound for sythesis of thienothienopyrimidines derivatives, which are thought to be potential biological active compounds or pharmaceuticals (Liu, et al.,2008). We obtained the title compound by the Sandmeyer reaction from compound 3-Amino-4-cyano-5-ethoxycarbonylmethylsulfanyl-thiophene-2-carboxylic acid ethyl ester.The crystal for X-ray crystal structure analysis was obtained by recrystallizing the title compound in petroleum ether. In the crystal, the thiophene ring together with its four adjoint groups, i.e. CN, Br, S—CH₂ and COO–,was located at one perfect plane, which is consistent with the crystal of 3-Amino-4-cyano-5-ethoxycarbonylmethylsulfany- thiophene-2-carboxylic acid ethyl ester reported in the literature (Padmavathi et al., 2011). The title compound cyrstal demonstrated a crystal system of monoclinic and a spce group of P2(1)/c. There existed hydrogen bond with length of 2.554 Å between one of –SCH₂ H atom and the O atom of carbonyl adjoined with thiophene ring of neighbor molecule.

Experimental

To a solution of 3-Amino-4-cyano-5-ethoxycarbonylmethylsulfanyl -thiophene-2-carboxylic acid ethyl ester (1.57 g, 5 mmol) in 70% H₂SO₄ (13 mL) was added NaNO₂ (0.4 g,5,7 mmol) in 5 minutes under ice water temperature. After addition, the solution was stirred for 30 min at room temperature. Then, the reaction mixture was transfered to HBr solution containing CuBr (1 g, 7 mmol). After standing overnight, water (100 mL) was added. The precipitate was collected by filtration and recrystallized from petroleum ether to afford the title compound as colourless crystals, yield 50%.

Figures

Fig. 1.

The structure of the title compound showing 30% probability ellipsoids.

Fig. 2.

Packing structure of the title compound.

Crystal data

C12H12BrNO4S2	F(000) = 760
Mr = 378.26	Dx = 1.650 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3404 reflections
a = 8.5896 (17) Å	θ = 3.1–27.9°
b = 10.837 (2) Å	µ = 2.98 mm−1
c = 16.584 (3) Å	T = 293 K
β = 99.44 (3)°	Block, colorless
V = 1522.8 (5) Å3	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	3596 independent reflections
Radiation source: rotating anode	2224 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.067
ω scans	θmax = 27.9°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→11
Tmin = 0.587, Tmax = 0.716	k = −14→14
15211 measured reflections	l = −21→21

Refinement

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)] = 0.052	H-atom parameters constrained
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0817P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.003
3596 reflections	Δρmax = 0.43 e Å−3
184 parameters	Δρmin = −0.71 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (2)

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
Br1	1.34684 (5)	−0.05401 (5)	0.13435 (3)	0.0723 (3)
S1	0.95059 (11)	0.19092 (9)	0.04312 (6)	0.0421 (3)
S2	0.75972 (12)	0.13383 (10)	0.17935 (7)	0.0505 (3)
O1	1.3519 (4)	0.1042 (3)	−0.0246 (2)	0.0703 (9)
O2	1.1477 (3)	0.2261 (3)	−0.07630 (18)	0.0577 (8)
O3	0.4240 (3)	0.3685 (3)	0.10494 (18)	0.0559 (8)
O4	0.4796 (4)	0.2478 (3)	0.2147 (2)	0.0744 (10)
N1	1.0569 (5)	−0.0869 (4)	0.2904 (3)	0.0784 (13)
C1	1.3411 (7)	0.3617 (5)	−0.1215 (3)	0.0825 (16)
H1A	1.2890	0.4277	−0.0980	0.124*
H1B	1.3794	0.3912	−0.1692	0.124*
H1C	1.4282	0.3325	−0.0823	0.124*
C2	1.2285 (6)	0.2598 (5)	−0.1446 (3)	0.0667 (13)
H2A	1.1510	0.2847	−0.1911	0.080*
H2B	1.2845	0.1885	−0.1607	0.080*
C3	1.2245 (5)	0.1481 (4)	−0.0215 (3)	0.0468 (10)
C4	1.1325 (4)	0.1209 (3)	0.0445 (2)	0.0420 (9)
C5	1.1667 (5)	0.0433 (3)	0.1088 (3)	0.0440 (9)
C6	1.0474 (4)	0.0400 (3)	0.1587 (2)	0.0427 (9)
C7	0.9215 (4)	0.1161 (3)	0.1300 (2)	0.0390 (8)
C8	1.0542 (5)	−0.0323 (4)	0.2309 (3)	0.0551 (11)
C9	0.6413 (4)	0.2381 (4)	0.1105 (2)	0.0473 (10)
H9A	0.7050	0.3072	0.0979	0.057*
H9B	0.6003	0.1960	0.0599	0.057*
C10	0.5069 (4)	0.2838 (4)	0.1508 (3)	0.0464 (10)
C11	0.2964 (6)	0.4242 (5)	0.1395 (3)	0.0632 (13)
H11A	0.3373	0.4630	0.1914	0.076*
H11B	0.2205	0.3617	0.1488	0.076*
C12	0.2186 (6)	0.5190 (5)	0.0800 (4)	0.0903 (18)
H12A	0.2957	0.5782	0.0691	0.135*
H12B	0.1371	0.5603	0.1029	0.135*
H12C	0.1733	0.4791	0.0299	0.135*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0499 (4)	0.0728 (4)	0.0911 (5)	0.0186 (2)	0.0023 (3)	0.0000 (3)
S1	0.0381 (5)	0.0419 (5)	0.0472 (6)	0.0045 (4)	0.0093 (4)	0.0038 (4)
S2	0.0452 (6)	0.0526 (6)	0.0570 (7)	0.0040 (5)	0.0186 (5)	0.0114 (5)
O1	0.0539 (19)	0.088 (2)	0.075 (2)	0.0161 (18)	0.0267 (16)	0.0067 (19)
O2	0.0532 (18)	0.0659 (19)	0.0574 (18)	0.0027 (15)	0.0195 (14)	0.0111 (16)
O3	0.0464 (16)	0.0658 (19)	0.0585 (19)	0.0130 (15)	0.0177 (14)	−0.0037 (15)
O4	0.074 (2)	0.088 (2)	0.070 (2)	0.0212 (18)	0.0363 (18)	0.0164 (19)
N1	0.073 (3)	0.077 (3)	0.087 (3)	0.012 (2)	0.020 (2)	0.035 (3)
C1	0.100 (4)	0.089 (4)	0.064 (3)	−0.022 (3)	0.030 (3)	0.002 (3)
C2	0.076 (3)	0.072 (3)	0.056 (3)	−0.004 (3)	0.022 (2)	0.008 (2)
C3	0.040 (2)	0.049 (2)	0.052 (2)	−0.0011 (19)	0.0102 (18)	−0.005 (2)
C4	0.034 (2)	0.039 (2)	0.054 (2)	0.0016 (16)	0.0101 (17)	−0.0058 (18)
C5	0.036 (2)	0.041 (2)	0.054 (2)	−0.0013 (16)	0.0032 (18)	−0.0033 (18)
C6	0.041 (2)	0.039 (2)	0.047 (2)	−0.0030 (17)	0.0034 (18)	0.0045 (17)
C7	0.036 (2)	0.0346 (19)	0.046 (2)	−0.0006 (16)	0.0064 (16)	−0.0012 (16)
C8	0.045 (2)	0.051 (2)	0.070 (3)	0.006 (2)	0.011 (2)	0.011 (2)
C9	0.036 (2)	0.059 (3)	0.048 (2)	0.0034 (19)	0.0114 (18)	0.003 (2)
C10	0.039 (2)	0.053 (2)	0.049 (2)	0.0003 (19)	0.0099 (18)	−0.003 (2)
C11	0.050 (3)	0.070 (3)	0.074 (3)	0.018 (2)	0.023 (2)	−0.008 (3)
C12	0.068 (3)	0.097 (4)	0.108 (5)	0.036 (3)	0.021 (3)	0.015 (4)

Geometric parameters (Å, º)

Br1—C5	1.864 (4)	C2—H2A	0.9700
S1—C7	1.707 (4)	C2—H2B	0.9700
S1—C4	1.734 (4)	C3—C4	1.480 (6)
S2—C7	1.735 (4)	C4—C5	1.352 (5)
S2—C9	1.798 (4)	C5—C6	1.418 (6)
O1—C3	1.202 (5)	C6—C7	1.381 (5)
O2—C3	1.335 (5)	C6—C8	1.425 (6)
O2—C2	1.468 (5)	C9—C10	1.509 (5)
O3—C10	1.323 (5)	C9—H9A	0.9700
O3—C11	1.449 (5)	C9—H9B	0.9700
O4—C10	1.188 (5)	C11—C12	1.504 (7)
N1—C8	1.147 (6)	C11—H11A	0.9700
C1—C2	1.477 (7)	C11—H11B	0.9700
C1—H1A	0.9600	C12—H12A	0.9600
C1—H1B	0.9600	C12—H12B	0.9600
C1—H1C	0.9600	C12—H12C	0.9600
C7—S1—C4	92.15 (19)	C5—C6—C8	124.7 (4)
C7—S2—C9	100.55 (18)	C6—C7—S1	111.1 (3)
C3—O2—C2	116.1 (3)	C6—C7—S2	123.1 (3)
C10—O3—C11	115.6 (3)	S1—C7—S2	125.8 (2)
C2—C1—H1A	109.5	N1—C8—C6	177.4 (5)
C2—C1—H1B	109.5	C10—C9—S2	108.6 (3)
H1A—C1—H1B	109.5	C10—C9—H9A	110.0
C2—C1—H1C	109.5	S2—C9—H9A	110.0
H1A—C1—H1C	109.5	C10—C9—H9B	110.0
H1B—C1—H1C	109.5	S2—C9—H9B	110.0
O2—C2—C1	111.0 (4)	H9A—C9—H9B	108.4
O2—C2—H2A	109.4	O4—C10—O3	125.0 (4)
C1—C2—H2A	109.4	O4—C10—C9	124.4 (4)
O2—C2—H2B	109.4	O3—C10—C9	110.6 (4)
C1—C2—H2B	109.4	O3—C11—C12	108.0 (4)
H2A—C2—H2B	108.0	O3—C11—H11A	110.1
O1—C3—O2	124.9 (4)	C12—C11—H11A	110.1
O1—C3—C4	123.6 (4)	O3—C11—H11B	110.1
O2—C3—C4	111.4 (3)	C12—C11—H11B	110.1
C5—C4—C3	129.3 (3)	H11A—C11—H11B	108.4
C5—C4—S1	111.1 (3)	C11—C12—H12A	109.5
C3—C4—S1	119.5 (3)	C11—C12—H12B	109.5
C4—C5—C6	113.1 (3)	H12A—C12—H12B	109.5
C4—C5—Br1	126.6 (3)	C11—C12—H12C	109.5
C6—C5—Br1	120.4 (3)	H12A—C12—H12C	109.5
C7—C6—C5	112.6 (3)	H12B—C12—H12C	109.5
C7—C6—C8	122.7 (4)
C3—O2—C2—C1	−83.9 (5)	C5—C6—C7—S1	−0.2 (4)
C2—O2—C3—O1	−0.4 (6)	C8—C6—C7—S1	179.4 (3)
C2—O2—C3—C4	179.9 (3)	C5—C6—C7—S2	−178.6 (3)
O1—C3—C4—C5	−2.5 (7)	C8—C6—C7—S2	0.9 (6)
O2—C3—C4—C5	177.2 (4)	C4—S1—C7—C6	−0.1 (3)
O1—C3—C4—S1	179.4 (4)	C4—S1—C7—S2	178.3 (3)
O2—C3—C4—S1	−1.0 (5)	C9—S2—C7—C6	−178.3 (3)
C7—S1—C4—C5	0.4 (3)	C9—S2—C7—S1	3.5 (3)
C7—S1—C4—C3	178.9 (3)	C7—C6—C8—N1	−36 (12)
C3—C4—C5—C6	−178.9 (4)	C5—C6—C8—N1	144 (11)
S1—C4—C5—C6	−0.6 (4)	C7—S2—C9—C10	−169.7 (3)
C3—C4—C5—Br1	0.6 (6)	C11—O3—C10—O4	3.5 (6)
S1—C4—C5—Br1	178.9 (2)	C11—O3—C10—C9	−176.8 (4)
C4—C5—C6—C7	0.5 (5)	S2—C9—C10—O4	−5.4 (6)
Br1—C5—C6—C7	−179.0 (3)	S2—C9—C10—O3	174.9 (3)
C4—C5—C6—C8	−179.0 (4)	C10—O3—C11—C12	178.9 (4)
Br1—C5—C6—C8	1.5 (5)