Crystal structure of ethyl 5-acetyl-2-{[(di-methyl-amino)-methyl-idene]amino}-4-methyl-thio-phene-3-carboxyl-ate.

In the title thio-phene derivative, C13H18N2O3S, the dihedral angles between the thio-phene ring and the [(di-methyl-amino)-methyl-idene]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 R 2 (2)(16) loops. The dimers are linked by another weak C-H⋯O inter-action, forming chains along [001]. In addition, weak C-H⋯π inter-actions are observed, which link the chains into (001) layers.

Related literature

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

Crystal data

C13H18N2O3S

M = 282.35

Orthorhombic,

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

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▸) T min = 0.958, T max = 0.963

15478 measured reflections

3012 independent reflections

2140 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 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

Data collection: SMART (Bruker, 1998 ▸); cell refinement: SAINT-Plus (Bruker, 1998 ▸); data reduction: SAINT-Plus; 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 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016217/hb7483sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016217/hb7483Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016217/hb7483Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016217/hb7483fig1.tif

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.

Click here for additional data file.

. DOI: 10.1107/S2056989015016217/hb7483fig2.tif

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.

Click here for additional data file.

. DOI: 10.1107/S2056989015016217/hb7483fig3.tif

Unit cell packing depicting C—H⋯π inter­actions with dotted lines.

CCDC reference: 1421360

Additional supporting information: crystallographic information; 3D view; checkCIF report

C13H18N2O3S	F(000) = 1200
Mr = 282.35	Dx = 1.354 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3012 reflections
a = 12.218 (3) Å	θ = 2.1–27.0°
b = 7.332 (2) Å	µ = 0.24 mm−1
c = 30.923 (8) Å	T = 100 K
V = 2769.9 (13) Å3	Block, colorless
Z = 8	0.29 × 0.26 × 0.10 mm

Bruker SMART APEX CCD diffractometer	3012 independent reflections
Radiation source: fine-focus sealed tube	2140 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −14→15
Tmin = 0.958, Tmax = 0.963	k = −9→9
15478 measured reflections	l = −39→35

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-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 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.8067 (2)	0.2414 (4)	0.37436 (9)	0.0219 (6)
H1A	0.8527	0.3124	0.3942	0.033*
H1B	0.7973	0.3089	0.3473	0.033*
H1C	0.8419	0.1240	0.3684	0.033*
C2	0.5031 (2)	0.1973 (4)	0.39447 (9)	0.0194 (6)
C3	0.5979 (2)	0.2312 (4)	0.37104 (9)	0.0193 (6)
C4	0.6967 (2)	0.2091 (4)	0.39477 (9)	0.0196 (6)
C5	0.6764 (2)	0.1574 (4)	0.43709 (9)	0.0190 (6)
C6	0.7476 (2)	0.1108 (4)	0.47350 (9)	0.0211 (6)
C7	0.8697 (2)	0.1198 (4)	0.46853 (9)	0.0252 (7)
H7A	0.9048	0.0694	0.4944	0.038*
H7B	0.8923	0.2471	0.4648	0.038*
H7C	0.8919	0.0488	0.4431	0.038*
C8	0.5956 (2)	0.2660 (4)	0.32370 (9)	0.0203 (6)
C9	0.5315 (2)	0.4612 (4)	0.26762 (9)	0.0251 (7)
H9A	0.4661	0.5384	0.2628	0.030*
H9B	0.5215	0.3467	0.2511	0.030*
C10	0.6313 (2)	0.5590 (5)	0.25110 (10)	0.0321 (7)
H10A	0.6411	0.6730	0.2672	0.048*
H10B	0.6219	0.5864	0.2203	0.048*
H10C	0.6958	0.4814	0.2550	0.048*
C11	0.3149 (2)	0.1822 (4)	0.40202 (9)	0.0216 (6)
H11	0.3262	0.1544	0.4317	0.026*
C13	0.1194 (2)	0.1650 (4)	0.41533 (10)	0.0287 (7)
H13A	0.1452	0.1305	0.4442	0.043*
H13B	0.0736	0.0673	0.4035	0.043*
H13C	0.0765	0.2776	0.4173	0.043*
C12	0.1888 (2)	0.2409 (5)	0.34251 (10)	0.0323 (8)
H12A	0.2567	0.2747	0.3277	0.048*
H12B	0.1377	0.3439	0.3418	0.048*
H12C	0.1558	0.1356	0.3280	0.048*
N1	0.40009 (18)	0.2074 (3)	0.37699 (7)	0.0216 (5)
N2	0.21291 (18)	0.1943 (3)	0.38709 (7)	0.0218 (5)
O1	0.70690 (16)	0.0608 (3)	0.50809 (6)	0.0285 (5)
O2	0.63937 (18)	0.1686 (3)	0.29724 (6)	0.0308 (5)
O3	0.54047 (16)	0.4187 (3)	0.31356 (6)	0.0244 (5)
S1	0.53616 (5)	0.13387 (10)	0.44751 (2)	0.0202 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0151 (15)	0.0206 (15)	0.0301 (16)	−0.0008 (11)	0.0015 (11)	−0.0017 (12)
C2	0.0147 (14)	0.0169 (14)	0.0267 (15)	0.0005 (11)	−0.0003 (11)	−0.0026 (11)
C3	0.0166 (15)	0.0142 (14)	0.0270 (15)	0.0008 (10)	0.0002 (11)	−0.0016 (11)
C4	0.0154 (15)	0.0127 (14)	0.0308 (15)	−0.0002 (10)	−0.0009 (11)	−0.0039 (11)
C5	0.0125 (14)	0.0223 (15)	0.0220 (14)	0.0018 (11)	0.0012 (11)	−0.0017 (11)
C6	0.0176 (15)	0.0189 (15)	0.0268 (15)	0.0001 (11)	−0.0015 (12)	−0.0001 (11)
C7	0.0170 (15)	0.0281 (16)	0.0304 (16)	−0.0015 (12)	−0.0037 (12)	0.0031 (12)
C8	0.0133 (14)	0.0197 (15)	0.0278 (16)	−0.0041 (11)	−0.0025 (12)	−0.0015 (12)
C9	0.0231 (16)	0.0261 (16)	0.0262 (15)	−0.0016 (12)	−0.0041 (12)	0.0043 (12)
C10	0.0262 (17)	0.0424 (19)	0.0276 (16)	−0.0008 (14)	−0.0002 (14)	0.0053 (14)
C11	0.0165 (15)	0.0236 (15)	0.0248 (15)	0.0010 (11)	−0.0026 (12)	0.0007 (12)
C13	0.0131 (15)	0.0363 (18)	0.0368 (18)	−0.0005 (12)	0.0015 (13)	0.0009 (14)
C12	0.0196 (16)	0.043 (2)	0.0341 (18)	0.0057 (13)	−0.0040 (13)	−0.0024 (15)
N1	0.0140 (13)	0.0235 (13)	0.0275 (13)	0.0013 (10)	−0.0003 (10)	0.0009 (10)
N2	0.0130 (12)	0.0285 (14)	0.0240 (12)	0.0006 (10)	0.0000 (10)	0.0005 (10)
O1	0.0216 (11)	0.0385 (13)	0.0254 (11)	−0.0008 (9)	−0.0010 (9)	0.0059 (9)
O2	0.0307 (12)	0.0372 (13)	0.0245 (11)	0.0088 (10)	−0.0012 (9)	−0.0060 (9)
O3	0.0225 (11)	0.0257 (11)	0.0251 (11)	0.0029 (8)	0.0001 (8)	0.0028 (9)
S1	0.0121 (4)	0.0250 (4)	0.0237 (4)	−0.0003 (3)	0.0004 (3)	0.0017 (3)

C1—C4	1.504 (4)	C9—O3	1.458 (3)
C1—H1A	0.9800	C9—C10	1.504 (4)
C1—H1B	0.9800	C9—H9A	0.9900
C1—H1C	0.9800	C9—H9B	0.9900
C2—N1	1.372 (3)	C10—H10A	0.9800
C2—C3	1.388 (4)	C10—H10B	0.9800
C2—S1	1.752 (3)	C10—H10C	0.9800
C3—C4	1.422 (4)	C11—N1	1.310 (3)
C3—C8	1.486 (4)	C11—N2	1.332 (3)
C4—C5	1.385 (4)	C11—H11	0.9500
C5—C6	1.464 (4)	C13—N2	1.454 (4)
C5—S1	1.752 (3)	C13—H13A	0.9800
C6—O1	1.235 (3)	C13—H13B	0.9800
C6—C7	1.501 (4)	C13—H13C	0.9800
C7—H7A	0.9800	C12—N2	1.450 (4)
C7—H7B	0.9800	C12—H12A	0.9800
C7—H7C	0.9800	C12—H12B	0.9800
C8—O2	1.210 (3)	C12—H12C	0.9800
C8—O3	1.343 (3)
C4—C1—H1A	109.5	C10—C9—H9A	109.2
C4—C1—H1B	109.5	O3—C9—H9B	109.2
H1A—C1—H1B	109.5	C10—C9—H9B	109.2
C4—C1—H1C	109.5	H9A—C9—H9B	107.9
H1A—C1—H1C	109.5	C9—C10—H10A	109.5
H1B—C1—H1C	109.5	C9—C10—H10B	109.5
N1—C2—C3	123.4 (3)	H10A—C10—H10B	109.5
N1—C2—S1	126.5 (2)	C9—C10—H10C	109.5
C3—C2—S1	110.1 (2)	H10A—C10—H10C	109.5
C2—C3—C4	114.7 (3)	H10B—C10—H10C	109.5
C2—C3—C8	122.0 (2)	N1—C11—N2	121.9 (3)
C4—C3—C8	122.9 (2)	N1—C11—H11	119.0
C5—C4—C3	111.5 (2)	N2—C11—H11	119.0
C5—C4—C1	126.8 (2)	N2—C13—H13A	109.5
C3—C4—C1	121.6 (3)	N2—C13—H13B	109.5
C4—C5—C6	133.2 (3)	H13A—C13—H13B	109.5
C4—C5—S1	112.1 (2)	N2—C13—H13C	109.5
C6—C5—S1	114.7 (2)	H13A—C13—H13C	109.5
O1—C6—C5	119.7 (3)	H13B—C13—H13C	109.5
O1—C6—C7	120.2 (2)	N2—C12—H12A	109.5
C5—C6—C7	120.1 (2)	N2—C12—H12B	109.5
C6—C7—H7A	109.5	H12A—C12—H12B	109.5
C6—C7—H7B	109.5	N2—C12—H12C	109.5
H7A—C7—H7B	109.5	H12A—C12—H12C	109.5
C6—C7—H7C	109.5	H12B—C12—H12C	109.5
H7A—C7—H7C	109.5	C11—N1—C2	119.2 (2)
H7B—C7—H7C	109.5	C11—N2—C12	122.3 (2)
O2—C8—O3	123.7 (3)	C11—N2—C13	121.1 (2)
O2—C8—C3	123.8 (3)	C12—N2—C13	116.5 (2)
O3—C8—C3	112.5 (2)	C8—O3—C9	116.3 (2)
O3—C9—C10	111.8 (2)	C2—S1—C5	91.56 (13)
O3—C9—H9A	109.2
N1—C2—C3—C4	−178.5 (2)	C2—C3—C8—O2	−117.1 (3)
S1—C2—C3—C4	−0.6 (3)	C4—C3—C8—O2	55.5 (4)
N1—C2—C3—C8	−5.4 (4)	C2—C3—C8—O3	63.5 (3)
S1—C2—C3—C8	172.5 (2)	C4—C3—C8—O3	−124.0 (3)
C2—C3—C4—C5	0.0 (3)	N2—C11—N1—C2	178.5 (2)
C8—C3—C4—C5	−173.0 (2)	C3—C2—N1—C11	−176.6 (3)
C2—C3—C4—C1	−179.7 (2)	S1—C2—N1—C11	5.8 (4)
C8—C3—C4—C1	7.3 (4)	N1—C11—N2—C12	−1.7 (4)
C3—C4—C5—C6	177.1 (3)	N1—C11—N2—C13	179.7 (3)
C1—C4—C5—C6	−3.2 (5)	O2—C8—O3—C9	2.1 (4)
C3—C4—C5—S1	0.6 (3)	C3—C8—O3—C9	−178.4 (2)
C1—C4—C5—S1	−179.8 (2)	C10—C9—O3—C8	−83.4 (3)
C4—C5—C6—O1	−176.9 (3)	N1—C2—S1—C5	178.6 (2)
S1—C5—C6—O1	−0.4 (3)	C3—C2—S1—C5	0.7 (2)
C4—C5—C6—C7	1.8 (5)	C4—C5—S1—C2	−0.8 (2)
S1—C5—C6—C7	178.2 (2)	C6—C5—S1—C2	−178.0 (2)

D—H···A	D—H	H···A	D···A	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—H7C···Cgiii	0.98	2.86	3.693 (2)	143

Table 1

Hydrogen-bond geometry (, )

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

DHA	DH	HA	D A	DHA
C9H9AO2i	0.99	2.45	3.270(3)	139
C11H11O1ii	0.95	2.47	3.312(4)	147
C7H7C Cg iii	0.98	2.86	3.693(2)	143

Symmetry codes: (i) ; (ii) ; (iii) .