Crystal structure of ethyl 5-[3-(di-methyl-amino)-acrylo-yl]-2-{[(di-methyl-amino)-methyl-idene]-amino}-4-methylthio-phene-3-carb-oxy-late.

In the title compound, C16H23N3O3S, the dihedral angles between the thio-phene ring and the almost planar di-methyl-amino-methyl-ene-amino (r.m.s. deviation = 0.005 Å) and di-methyl-amino-acryloyl (r.m.s. deviation = 0.033 Å) substituents are 6.99 (8) and 6.69 (7)°, respectively. The ester CO2 group subtends a dihedral angle of 44.92 (18)° with the thio-phene ring. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of C-H⋯O hydrogen bonds generate R (2) 2(14) loops. In addition, a weak C-H⋯π inter-action is observed.

Related literature

For the biological activitivity of thio­phene derivatives, see: Rizwan et al. (2014 ▸); Mishra et al. (2011 ▸); Sabnis et al. (1999 ▸). Mabkhot et al. (2013 ▸). For synthetic background, see: Gewald et al. (1966 ▸).

Experimental

Crystal data

C16H23N3O3S

M = 337.43

Triclinic,

a = 7.6954 (5) Å

b = 8.1799 (5) Å

c = 13.9626 (9) Å

α = 95.928 (2)°

β = 103.685 (2)°

γ = 90.137 (2)°

V = 849.07 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.17 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▸) T min = 0.963, T max = 0.967

5876 measured reflections

2991 independent reflections

2646 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.089

S = 1.02

2991 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.19 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/S2056989015018885/hb7489sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018885/hb7489Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018885/hb7489Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015018885/hb7489fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015018885/hb7489fig2.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/S2056989015018885/hb7489fig3.tif

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

CCDC reference: 1430038

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

C16H23N3O3S	Z = 2
Mr = 337.43	F(000) = 360
Triclinic, P1	Dx = 1.320 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6954 (5) Å	Cell parameters from 2991 reflections
b = 8.1799 (5) Å	θ = 2.5–25.0°
c = 13.9626 (9) Å	µ = 0.21 mm−1
α = 95.928 (2)°	T = 100 K
β = 103.685 (2)°	Block, colorless
γ = 90.137 (2)°	0.17 × 0.16 × 0.15 mm
V = 849.07 (9) Å3

Bruker SMART APEX CCD diffractometer	2991 independent reflections
Radiation source: fine-focus sealed tube	2646 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→8
Tmin = 0.963, Tmax = 0.967	k = −9→9
5876 measured reflections	l = −11→16

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.3093P] where P = (Fo2 + 2Fc2)/3
2991 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.19 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
S1	0.02778 (5)	0.86621 (4)	0.39020 (3)	0.01529 (13)
O1	−0.26349 (16)	0.82247 (14)	0.03518 (8)	0.0269 (3)
O2	−0.15686 (14)	1.07646 (13)	0.09662 (7)	0.0181 (3)
O3	−0.41534 (15)	0.62783 (15)	0.39383 (8)	0.0255 (3)
N1	0.15977 (16)	1.01180 (15)	0.25146 (9)	0.0150 (3)
N2	0.44236 (16)	1.13376 (16)	0.31336 (9)	0.0172 (3)
N3	−0.10460 (16)	0.56379 (15)	0.67393 (9)	0.0162 (3)
C1	0.2971 (2)	1.05575 (18)	0.32371 (11)	0.0157 (3)
H1	0.2938	1.0306	0.3882	0.019*
C2	0.0200 (2)	0.93094 (17)	0.27440 (11)	0.0140 (3)
C3	−0.14156 (19)	0.88099 (18)	0.20962 (11)	0.0142 (3)
C4	−0.2563 (2)	0.78787 (18)	0.25248 (11)	0.0147 (3)
C5	−0.18389 (19)	0.77234 (18)	0.35108 (11)	0.0147 (3)
C6	0.4627 (2)	1.1762 (2)	0.21829 (12)	0.0213 (4)
H6A	0.5572	1.1107	0.1983	0.032*
H6B	0.4950	1.2934	0.2238	0.032*
H6C	0.3497	1.1533	0.1685	0.032*
C7	0.5897 (2)	1.1801 (2)	0.39906 (12)	0.0242 (4)
H7A	0.5567	1.1532	0.4593	0.036*
H7B	0.6153	1.2986	0.4042	0.036*
H7C	0.6963	1.1198	0.3913	0.036*
C8	−0.19266 (19)	0.91884 (19)	0.10487 (11)	0.0164 (3)
C9	−0.2086 (2)	1.1249 (2)	−0.00331 (11)	0.0221 (4)
H9A	−0.3396	1.1106	−0.0295	0.027*
H9B	−0.1485	1.0563	−0.0478	0.027*
C10	−0.1529 (3)	1.3026 (2)	0.00224 (13)	0.0306 (4)
H10A	−0.2159	1.3696	0.0449	0.046*
H10B	−0.1830	1.3384	−0.0644	0.046*
H10C	−0.0236	1.3155	0.0299	0.046*
C11	−0.4355 (2)	0.7165 (2)	0.19573 (12)	0.0197 (3)
H11A	−0.4507	0.6055	0.2135	0.030*
H11B	−0.4428	0.7115	0.1245	0.030*
H11C	−0.5302	0.7860	0.2122	0.030*
C12	−0.2594 (2)	0.68572 (18)	0.42080 (11)	0.0158 (3)
C13	−0.1447 (2)	0.67102 (18)	0.51655 (11)	0.0160 (3)
H13	−0.0280	0.7203	0.5334	0.019*
C14	−0.2011 (2)	0.58678 (18)	0.58402 (11)	0.0154 (3)
H14	−0.3192	0.5408	0.5650	0.018*
C15	0.0778 (2)	0.62890 (19)	0.70973 (11)	0.0186 (3)
H15A	0.1460	0.5980	0.6599	0.028*
H15B	0.1339	0.5836	0.7716	0.028*
H15C	0.0765	0.7490	0.7218	0.028*
C16	−0.1802 (2)	0.48165 (19)	0.74298 (11)	0.0195 (3)
H16A	−0.1883	0.5607	0.7994	0.029*
H16B	−0.1032	0.3918	0.7667	0.029*
H16C	−0.3000	0.4372	0.7094	0.029*

	U11	U22	U33	U12	U13	U23
S1	0.0142 (2)	0.0190 (2)	0.0122 (2)	−0.00330 (14)	0.00129 (14)	0.00392 (14)
O1	0.0338 (7)	0.0294 (7)	0.0144 (6)	−0.0129 (5)	0.0000 (5)	0.0008 (5)
O2	0.0211 (6)	0.0210 (6)	0.0116 (5)	−0.0003 (4)	0.0010 (4)	0.0065 (4)
O3	0.0176 (6)	0.0392 (7)	0.0192 (6)	−0.0092 (5)	0.0004 (5)	0.0112 (5)
N1	0.0134 (6)	0.0177 (7)	0.0143 (6)	−0.0007 (5)	0.0030 (5)	0.0040 (5)
N2	0.0133 (6)	0.0213 (7)	0.0166 (7)	−0.0028 (5)	0.0021 (5)	0.0031 (5)
N3	0.0149 (7)	0.0177 (7)	0.0160 (7)	−0.0015 (5)	0.0027 (5)	0.0044 (5)
C1	0.0156 (8)	0.0169 (8)	0.0156 (8)	0.0006 (6)	0.0046 (6)	0.0037 (6)
C2	0.0157 (7)	0.0131 (7)	0.0136 (7)	0.0021 (6)	0.0038 (6)	0.0024 (6)
C3	0.0143 (7)	0.0140 (7)	0.0141 (8)	0.0007 (6)	0.0027 (6)	0.0025 (6)
C4	0.0149 (7)	0.0133 (7)	0.0161 (8)	0.0012 (6)	0.0033 (6)	0.0031 (6)
C5	0.0129 (7)	0.0144 (7)	0.0160 (8)	0.0000 (6)	0.0015 (6)	0.0018 (6)
C6	0.0198 (8)	0.0243 (8)	0.0216 (8)	−0.0025 (7)	0.0073 (7)	0.0051 (7)
C7	0.0169 (8)	0.0336 (9)	0.0199 (9)	−0.0066 (7)	0.0000 (7)	0.0031 (7)
C8	0.0121 (7)	0.0214 (8)	0.0163 (8)	0.0001 (6)	0.0038 (6)	0.0042 (6)
C9	0.0219 (8)	0.0314 (9)	0.0119 (8)	−0.0030 (7)	−0.0011 (6)	0.0094 (7)
C10	0.0370 (10)	0.0328 (10)	0.0211 (9)	−0.0046 (8)	0.0008 (8)	0.0128 (7)
C11	0.0158 (8)	0.0253 (8)	0.0177 (8)	−0.0034 (6)	0.0009 (6)	0.0076 (6)
C12	0.0161 (8)	0.0147 (8)	0.0172 (8)	0.0002 (6)	0.0050 (6)	0.0022 (6)
C13	0.0145 (8)	0.0169 (8)	0.0163 (8)	−0.0027 (6)	0.0024 (6)	0.0033 (6)
C14	0.0151 (7)	0.0145 (7)	0.0158 (8)	0.0001 (6)	0.0024 (6)	0.0013 (6)
C15	0.0164 (8)	0.0215 (8)	0.0164 (8)	−0.0016 (6)	−0.0001 (6)	0.0043 (6)
C16	0.0206 (8)	0.0229 (8)	0.0163 (8)	−0.0007 (6)	0.0049 (6)	0.0070 (6)

S1—C5	1.7401 (15)	C6—H6C	0.9800
S1—C2	1.7405 (15)	C7—H7A	0.9800
O1—C8	1.2058 (19)	C7—H7B	0.9800
O2—C8	1.3399 (19)	C7—H7C	0.9800
O2—C9	1.4541 (18)	C9—C10	1.503 (2)
O3—C12	1.2458 (19)	C9—H9A	0.9900
N1—C1	1.2973 (19)	C9—H9B	0.9900
N1—C2	1.3785 (19)	C10—H10A	0.9800
N2—C1	1.330 (2)	C10—H10B	0.9800
N2—C6	1.449 (2)	C10—H10C	0.9800
N2—C7	1.4574 (19)	C11—H11A	0.9800
N3—C14	1.3308 (19)	C11—H11B	0.9800
N3—C15	1.4538 (19)	C11—H11C	0.9800
N3—C16	1.4547 (19)	C12—C13	1.434 (2)
C1—H1	0.9500	C13—C14	1.370 (2)
C2—C3	1.386 (2)	C13—H13	0.9500
C3—C4	1.435 (2)	C14—H14	0.9500
C3—C8	1.487 (2)	C15—H15A	0.9800
C4—C5	1.377 (2)	C15—H15B	0.9800
C4—C11	1.502 (2)	C15—H15C	0.9800
C5—C12	1.482 (2)	C16—H16A	0.9800
C6—H6A	0.9800	C16—H16B	0.9800
C6—H6B	0.9800	C16—H16C	0.9800
C5—S1—C2	92.90 (7)	O2—C9—C10	107.39 (13)
C8—O2—C9	115.32 (12)	O2—C9—H9A	110.2
C1—N1—C2	117.13 (13)	C10—C9—H9A	110.2
C1—N2—C6	122.52 (13)	O2—C9—H9B	110.2
C1—N2—C7	120.47 (13)	C10—C9—H9B	110.2
C6—N2—C7	117.01 (13)	H9A—C9—H9B	108.5
C14—N3—C15	121.29 (12)	C9—C10—H10A	109.5
C14—N3—C16	121.63 (13)	C9—C10—H10B	109.5
C15—N3—C16	116.97 (12)	H10A—C10—H10B	109.5
N1—C1—N2	124.23 (14)	C9—C10—H10C	109.5
N1—C1—H1	117.9	H10A—C10—H10C	109.5
N2—C1—H1	117.9	H10B—C10—H10C	109.5
N1—C2—C3	126.29 (13)	C4—C11—H11A	109.5
N1—C2—S1	123.88 (11)	C4—C11—H11B	109.5
C3—C2—S1	109.75 (11)	H11A—C11—H11B	109.5
C2—C3—C4	113.91 (13)	C4—C11—H11C	109.5
C2—C3—C8	123.54 (13)	H11A—C11—H11C	109.5
C4—C3—C8	122.55 (13)	H11B—C11—H11C	109.5
C5—C4—C3	112.46 (13)	O3—C12—C13	123.52 (14)
C5—C4—C11	124.08 (14)	O3—C12—C5	119.47 (13)
C3—C4—C11	123.46 (13)	C13—C12—C5	117.00 (13)
C4—C5—C12	128.92 (14)	C14—C13—C12	120.85 (14)
C4—C5—S1	110.95 (11)	C14—C13—H13	119.6
C12—C5—S1	120.09 (11)	C12—C13—H13	119.6
N2—C6—H6A	109.5	N3—C14—C13	125.64 (14)
N2—C6—H6B	109.5	N3—C14—H14	117.2
H6A—C6—H6B	109.5	C13—C14—H14	117.2
N2—C6—H6C	109.5	N3—C15—H15A	109.5
H6A—C6—H6C	109.5	N3—C15—H15B	109.5
H6B—C6—H6C	109.5	H15A—C15—H15B	109.5
N2—C7—H7A	109.5	N3—C15—H15C	109.5
N2—C7—H7B	109.5	H15A—C15—H15C	109.5
H7A—C7—H7B	109.5	H15B—C15—H15C	109.5
N2—C7—H7C	109.5	N3—C16—H16A	109.5
H7A—C7—H7C	109.5	N3—C16—H16B	109.5
H7B—C7—H7C	109.5	H16A—C16—H16B	109.5
O1—C8—O2	123.15 (14)	N3—C16—H16C	109.5
O1—C8—C3	124.90 (14)	H16A—C16—H16C	109.5
O2—C8—C3	111.90 (13)	H16B—C16—H16C	109.5
C2—N1—C1—N2	179.64 (14)	C2—S1—C5—C4	0.96 (12)
C6—N2—C1—N1	−0.8 (2)	C2—S1—C5—C12	179.02 (12)
C7—N2—C1—N1	179.29 (14)	C9—O2—C8—O1	−0.3 (2)
C1—N1—C2—C3	176.62 (14)	C9—O2—C8—C3	−178.01 (12)
C1—N1—C2—S1	−7.12 (19)	C2—C3—C8—O1	136.70 (17)
C5—S1—C2—N1	−176.53 (13)	C4—C3—C8—O1	−42.9 (2)
C5—S1—C2—C3	0.27 (11)	C2—C3—C8—O2	−45.7 (2)
N1—C2—C3—C4	175.30 (13)	C4—C3—C8—O2	134.66 (14)
S1—C2—C3—C4	−1.41 (16)	C8—O2—C9—C10	−178.30 (13)
N1—C2—C3—C8	−4.4 (2)	C4—C5—C12—O3	−6.8 (2)
S1—C2—C3—C8	178.91 (11)	S1—C5—C12—O3	175.57 (12)
C2—C3—C4—C5	2.19 (19)	C4—C5—C12—C13	172.14 (15)
C8—C3—C4—C5	−178.13 (13)	S1—C5—C12—C13	−5.54 (19)
C2—C3—C4—C11	−178.12 (14)	O3—C12—C13—C14	1.6 (2)
C8—C3—C4—C11	1.6 (2)	C5—C12—C13—C14	−177.21 (13)
C3—C4—C5—C12	−179.75 (14)	C15—N3—C14—C13	−0.2 (2)
C11—C4—C5—C12	0.6 (3)	C16—N3—C14—C13	175.89 (14)
C3—C4—C5—S1	−1.90 (16)	C12—C13—C14—N3	178.91 (14)
C11—C4—C5—S1	178.41 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O1	0.98	2.31	3.054 (1)	132
C16—H16C···O3i	0.98	2.35	3.310 (2)	168
C16—H16B···Cgii	0.98	2.74	3.566 (2)	142

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	D⋯A	D—H⋯A
C11—H11B⋯O1	0.98	2.31	3.054 (1)	132
C16—H16C⋯O3i	0.98	2.35	3.310 (2)	168
C16—H16B⋯Cg ii	0.98	2.74	3.566 (2)	142

Symmetry codes: (i) ; (ii) .