organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages o762-o763

Crystal structure of ethyl 5-acetyl-2-{[(di­methyl­amino)­methyl­­idene]amino}-4-methyl­thio­phene-3-carboxyl­ate

CROSSMARK_Color_square_no_text.svg

aDepartment of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore 560 001, Karnataka, India
*Correspondence e-mail: noorsb@rediffmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 August 2015; accepted 31 August 2015; online 17 September 2015)

In the title thio­phene derivative, C13H18N2O3S, the dihedral angles between the thio­phene ring and the [(di­methyl­amino)­methyl­idene]amino side chain (r.m.s. deviation = 0.009 Å) and the –CO2 ester group are 3.01 (16) and 59.9 (3)°, respectively. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R22(16) loops. The dimers are linked by another weak C—H⋯O inter­action, forming chains along [001]. In addition, weak C—H⋯π inter­actions are observed, which link the chains into (001) layers.

1. Related literature

For background to the applications of thio­phene derivatives, see: Sabnis et al. (1999[Sabnis, R. W., Rangnekar, D. W. & Sonawane, N. D. (1999). J. Heterocycl. Chem. 36, 333-345.]). For a related structure, see: Mukhtar et al. (2010[Mukhtar, A., Tahir, M. N., Khan, M. A. & Khan, M. N. (2010). Acta Cryst. E66, o2652.]). For further synthetic details, see: Gewald et al. (1966[Gewald, K., Schinke, E. & Böttcher, H. (1966). Chem. Ber. 99, 94-100.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C13H18N2O3S

  • Mr = 282.35

  • Orthorhombic, P b c a

  • a = 12.218 (3) Å

  • b = 7.332 (2) Å

  • c = 30.923 (8) Å

  • V = 2769.9 (13) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 100 K

  • 0.29 × 0.26 × 0.10 mm

2.2. Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1998[Bruker. (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.958, Tmax = 0.963

  • 15478 measured reflections

  • 3012 independent reflections

  • 2140 reflections with I > 2σ(I)

  • Rint = 0.076

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 0.173

  • S = 1.19

  • 3012 reflections

  • 177 parameters

  • H-atom parameters constrained

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2/C3/C4/C5/S1 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C9—H9A⋯O2i 0.99 2.45 3.270 (3) 139
C11—H11⋯O1ii 0.95 2.47 3.312 (4) 147
C7—H7CCgiii 0.98 2.86 3.693 (2) 143
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x+1, -y, -z+1; (iii) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z].

Data collection: SMART (Bruker, 1998[Bruker. (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 1998[Bruker. (1998). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Comment top

Thiophene belongs to a class of heterocyclic compounds containing a five membered ring made up of one sulfur as heteroatom, that are widely used as building blocks in many agrochemicals and pharmaceuticals. 2-Aminothiophenes attract special attention because of their applications in pharmaceuticals, agriculture, pesticides and dyes (Sabnis et al., 1999). The most convergent and well established classical approach for the preparation of 2-aminothiophenes is Gewald's method (Gewald et al., 1966), which involves the multicomponent condensation of a ketone with an activated nitrile and elemental sulfur in the presence of diethylamine as a catalyst. Herein, we report the structure of the title compound, (I).

The molecular structure of the compound is shown in Fig. 1. In the title compound, C13H18N2O3S, a thiophene derivative with dimethylamino- methyleneamino, acetyl, methyl and ethyl carboxylate substituents attached to a central thiophene ring. The thiophene ring and all the substituents are almost planar except the carboxyl group (C10/C9/O3/C8), it is slightly deviating from the plane at -83.474 (3)°. The carbonyl group of the exocyclic ester at C3 and acetyl at C5 adopts a trans orientation with C3=C2 and C5=C4 double bond respectively. The crystal structure features C—H···O interactions. The C11—H11···O1 hydrogen bonds resulting in a centrosymmetric head to head dimer with graph set R22(16) notation, which are in turn linked by another weak C9—H9A···O2 interactions to form chains of rings along [001] (Table.1; Fig. 2). In addition, weak C—H···π interactions of the type C7—H7C···Cg [Cg being the centroid of the thiophene ring (C2/C3/C4/C5/S1)] link the chains into layers parallel to (001) with a distance 2.864 Å is also observed (Fig. 3).

Related literature top

For background to the applications of thiophene derivatives, see: Sabnis et al. (1999). For a related structure, see: Mukhtar et al. (2010). For further synthetic details, see: Gewald et al. (1966).

Experimental top

Step-1: 3.3 g of cyano ethyl acetate was weighed and transferred to RB flask and 5 g of acetyl acetone and 10 to 15 ml of ethanol were added to it. The whole mixture was stirred for 10 min. After stirring 1.6 g of elemental sulfur was added to the mixture and cold condition was maintained by using crushed ice. Later 5 ml of diethyl amine was added drop by drop the solution changes its color to red. After the completion of addition the solution was again kept for stirring (10 min). Ice pack was removed and stirring was continued for about an hour. The precipitated product (1) was filtered, dried and recrystallized from ethanol (yield: 68%, m.p. 430 K)

Step-2: A mixture of compound 1 (10 mmol) and DMF—DMA (5 ml) was stirred at room temperature for 30 minutes. To this was added ethanol and kept in room temperature to give a solid product (title compound) that was collected by filtration. The compound was recrystallized by slow evaporation from ethanol, yielding single crystals suitable for X-ray diffraction studies.

Refinement top

The H atoms were placed at calculated positions in the riding-model approximation with C—H = 0.96° A, 0.97 ° A and 0.93 ° A for methyl, methylene and methyne H-atoms respectively, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for other hydrogen atoms.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); 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) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. Unit cell packing of the title compound showing intermolecular C—H···O interactions with dotted lines. H-atoms not involved in hydrogen bonding have been excluded.
[Figure 3] Fig. 3. Unit cell packing depicting C—H···π interactions with dotted lines.
Ethyl 5-acetyl-2-{[(dimethylamino)methylidene]amino}-4-methylthiophene-3-carboxylate top
Crystal data top
C13H18N2O3SF(000) = 1200
Mr = 282.35Dx = 1.354 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3012 reflections
a = 12.218 (3) Åθ = 2.1–27.0°
b = 7.332 (2) ŵ = 0.24 mm1
c = 30.923 (8) ÅT = 100 K
V = 2769.9 (13) Å3Block, colorless
Z = 80.29 × 0.26 × 0.10 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
3012 independent reflections
Radiation source: fine-focus sealed tube2140 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.076
ω scansθmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1415
Tmin = 0.958, Tmax = 0.963k = 99
15478 measured reflectionsl = 3935
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0811P)2 + 0.3374P]
where P = (Fo2 + 2Fc2)/3
3012 reflections(Δ/σ)max < 0.001
177 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C13H18N2O3SV = 2769.9 (13) Å3
Mr = 282.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.218 (3) ŵ = 0.24 mm1
b = 7.332 (2) ÅT = 100 K
c = 30.923 (8) Å0.29 × 0.26 × 0.10 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
3012 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
2140 reflections with I > 2σ(I)
Tmin = 0.958, Tmax = 0.963Rint = 0.076
15478 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.173H-atom parameters constrained
S = 1.19Δρmax = 0.52 e Å3
3012 reflectionsΔρmin = 0.33 e Å3
177 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å2) top
xyzUiso*/Ueq
C10.8067 (2)0.2414 (4)0.37436 (9)0.0219 (6)
H1A0.85270.31240.39420.033*
H1B0.79730.30890.34730.033*
H1C0.84190.12400.36840.033*
C20.5031 (2)0.1973 (4)0.39447 (9)0.0194 (6)
C30.5979 (2)0.2312 (4)0.37104 (9)0.0193 (6)
C40.6967 (2)0.2091 (4)0.39477 (9)0.0196 (6)
C50.6764 (2)0.1574 (4)0.43709 (9)0.0190 (6)
C60.7476 (2)0.1108 (4)0.47350 (9)0.0211 (6)
C70.8697 (2)0.1198 (4)0.46853 (9)0.0252 (7)
H7A0.90480.06940.49440.038*
H7B0.89230.24710.46480.038*
H7C0.89190.04880.44310.038*
C80.5956 (2)0.2660 (4)0.32370 (9)0.0203 (6)
C90.5315 (2)0.4612 (4)0.26762 (9)0.0251 (7)
H9A0.46610.53840.26280.030*
H9B0.52150.34670.25110.030*
C100.6313 (2)0.5590 (5)0.25110 (10)0.0321 (7)
H10A0.64110.67300.26720.048*
H10B0.62190.58640.22030.048*
H10C0.69580.48140.25500.048*
C110.3149 (2)0.1822 (4)0.40202 (9)0.0216 (6)
H110.32620.15440.43170.026*
C130.1194 (2)0.1650 (4)0.41533 (10)0.0287 (7)
H13A0.14520.13050.44420.043*
H13B0.07360.06730.40350.043*
H13C0.07650.27760.41730.043*
C120.1888 (2)0.2409 (5)0.34251 (10)0.0323 (8)
H12A0.25670.27470.32770.048*
H12B0.13770.34390.34180.048*
H12C0.15580.13560.32800.048*
N10.40009 (18)0.2074 (3)0.37699 (7)0.0216 (5)
N20.21291 (18)0.1943 (3)0.38709 (7)0.0218 (5)
O10.70690 (16)0.0608 (3)0.50809 (6)0.0285 (5)
O20.63937 (18)0.1686 (3)0.29724 (6)0.0308 (5)
O30.54047 (16)0.4187 (3)0.31356 (6)0.0244 (5)
S10.53616 (5)0.13387 (10)0.44751 (2)0.0202 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0151 (15)0.0206 (15)0.0301 (16)0.0008 (11)0.0015 (11)0.0017 (12)
C20.0147 (14)0.0169 (14)0.0267 (15)0.0005 (11)0.0003 (11)0.0026 (11)
C30.0166 (15)0.0142 (14)0.0270 (15)0.0008 (10)0.0002 (11)0.0016 (11)
C40.0154 (15)0.0127 (14)0.0308 (15)0.0002 (10)0.0009 (11)0.0039 (11)
C50.0125 (14)0.0223 (15)0.0220 (14)0.0018 (11)0.0012 (11)0.0017 (11)
C60.0176 (15)0.0189 (15)0.0268 (15)0.0001 (11)0.0015 (12)0.0001 (11)
C70.0170 (15)0.0281 (16)0.0304 (16)0.0015 (12)0.0037 (12)0.0031 (12)
C80.0133 (14)0.0197 (15)0.0278 (16)0.0041 (11)0.0025 (12)0.0015 (12)
C90.0231 (16)0.0261 (16)0.0262 (15)0.0016 (12)0.0041 (12)0.0043 (12)
C100.0262 (17)0.0424 (19)0.0276 (16)0.0008 (14)0.0002 (14)0.0053 (14)
C110.0165 (15)0.0236 (15)0.0248 (15)0.0010 (11)0.0026 (12)0.0007 (12)
C130.0131 (15)0.0363 (18)0.0368 (18)0.0005 (12)0.0015 (13)0.0009 (14)
C120.0196 (16)0.043 (2)0.0341 (18)0.0057 (13)0.0040 (13)0.0024 (15)
N10.0140 (13)0.0235 (13)0.0275 (13)0.0013 (10)0.0003 (10)0.0009 (10)
N20.0130 (12)0.0285 (14)0.0240 (12)0.0006 (10)0.0000 (10)0.0005 (10)
O10.0216 (11)0.0385 (13)0.0254 (11)0.0008 (9)0.0010 (9)0.0059 (9)
O20.0307 (12)0.0372 (13)0.0245 (11)0.0088 (10)0.0012 (9)0.0060 (9)
O30.0225 (11)0.0257 (11)0.0251 (11)0.0029 (8)0.0001 (8)0.0028 (9)
S10.0121 (4)0.0250 (4)0.0237 (4)0.0003 (3)0.0004 (3)0.0017 (3)
Geometric parameters (Å, º) top
C1—C41.504 (4)C9—O31.458 (3)
C1—H1A0.9800C9—C101.504 (4)
C1—H1B0.9800C9—H9A0.9900
C1—H1C0.9800C9—H9B0.9900
C2—N11.372 (3)C10—H10A0.9800
C2—C31.388 (4)C10—H10B0.9800
C2—S11.752 (3)C10—H10C0.9800
C3—C41.422 (4)C11—N11.310 (3)
C3—C81.486 (4)C11—N21.332 (3)
C4—C51.385 (4)C11—H110.9500
C5—C61.464 (4)C13—N21.454 (4)
C5—S11.752 (3)C13—H13A0.9800
C6—O11.235 (3)C13—H13B0.9800
C6—C71.501 (4)C13—H13C0.9800
C7—H7A0.9800C12—N21.450 (4)
C7—H7B0.9800C12—H12A0.9800
C7—H7C0.9800C12—H12B0.9800
C8—O21.210 (3)C12—H12C0.9800
C8—O31.343 (3)
C4—C1—H1A109.5C10—C9—H9A109.2
C4—C1—H1B109.5O3—C9—H9B109.2
H1A—C1—H1B109.5C10—C9—H9B109.2
C4—C1—H1C109.5H9A—C9—H9B107.9
H1A—C1—H1C109.5C9—C10—H10A109.5
H1B—C1—H1C109.5C9—C10—H10B109.5
N1—C2—C3123.4 (3)H10A—C10—H10B109.5
N1—C2—S1126.5 (2)C9—C10—H10C109.5
C3—C2—S1110.1 (2)H10A—C10—H10C109.5
C2—C3—C4114.7 (3)H10B—C10—H10C109.5
C2—C3—C8122.0 (2)N1—C11—N2121.9 (3)
C4—C3—C8122.9 (2)N1—C11—H11119.0
C5—C4—C3111.5 (2)N2—C11—H11119.0
C5—C4—C1126.8 (2)N2—C13—H13A109.5
C3—C4—C1121.6 (3)N2—C13—H13B109.5
C4—C5—C6133.2 (3)H13A—C13—H13B109.5
C4—C5—S1112.1 (2)N2—C13—H13C109.5
C6—C5—S1114.7 (2)H13A—C13—H13C109.5
O1—C6—C5119.7 (3)H13B—C13—H13C109.5
O1—C6—C7120.2 (2)N2—C12—H12A109.5
C5—C6—C7120.1 (2)N2—C12—H12B109.5
C6—C7—H7A109.5H12A—C12—H12B109.5
C6—C7—H7B109.5N2—C12—H12C109.5
H7A—C7—H7B109.5H12A—C12—H12C109.5
C6—C7—H7C109.5H12B—C12—H12C109.5
H7A—C7—H7C109.5C11—N1—C2119.2 (2)
H7B—C7—H7C109.5C11—N2—C12122.3 (2)
O2—C8—O3123.7 (3)C11—N2—C13121.1 (2)
O2—C8—C3123.8 (3)C12—N2—C13116.5 (2)
O3—C8—C3112.5 (2)C8—O3—C9116.3 (2)
O3—C9—C10111.8 (2)C2—S1—C591.56 (13)
O3—C9—H9A109.2
N1—C2—C3—C4178.5 (2)C2—C3—C8—O2117.1 (3)
S1—C2—C3—C40.6 (3)C4—C3—C8—O255.5 (4)
N1—C2—C3—C85.4 (4)C2—C3—C8—O363.5 (3)
S1—C2—C3—C8172.5 (2)C4—C3—C8—O3124.0 (3)
C2—C3—C4—C50.0 (3)N2—C11—N1—C2178.5 (2)
C8—C3—C4—C5173.0 (2)C3—C2—N1—C11176.6 (3)
C2—C3—C4—C1179.7 (2)S1—C2—N1—C115.8 (4)
C8—C3—C4—C17.3 (4)N1—C11—N2—C121.7 (4)
C3—C4—C5—C6177.1 (3)N1—C11—N2—C13179.7 (3)
C1—C4—C5—C63.2 (5)O2—C8—O3—C92.1 (4)
C3—C4—C5—S10.6 (3)C3—C8—O3—C9178.4 (2)
C1—C4—C5—S1179.8 (2)C10—C9—O3—C883.4 (3)
C4—C5—C6—O1176.9 (3)N1—C2—S1—C5178.6 (2)
S1—C5—C6—O10.4 (3)C3—C2—S1—C50.7 (2)
C4—C5—C6—C71.8 (5)C4—C5—S1—C20.8 (2)
S1—C5—C6—C7178.2 (2)C6—C5—S1—C2178.0 (2)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C2/C3/C4/C5/S1 ring .
D—H···AD—HH···AD···AD—H···A
C9—H9A···O2i0.992.453.270 (3)139
C11—H11···O1ii0.952.473.312 (4)147
C7—H7C···Cgiii0.982.863.693 (2)143
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y, z+1; (iii) x+1/2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C2/C3/C4/C5/S1 ring .
D—H···AD—HH···AD···AD—H···A
C9—H9A···O2i0.992.453.270 (3)139
C11—H11···O1ii0.952.473.312 (4)147
C7—H7C···Cgiii0.982.863.693 (2)143
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y, z+1; (iii) x+1/2, y+3/2, z.
 

Acknowledgements

NLP thanks the University Grants Commission (UGC), India for a CSIR–NET fellowship and MSK thanks the UGC for a UGC–BSR Meritorious fellowship.

References

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First citationMukhtar, A., Tahir, M. N., Khan, M. A. & Khan, M. N. (2010). Acta Cryst. E66, o2652.  Web of Science CSD CrossRef IUCr Journals Google Scholar
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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages o762-o763
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