Methyl (2E)-2-cyano-3-(dimethyl­amino)­prop-2-enoate

Kant, R.; Gupta, V.K.; Kapoor, K.; Patil, D.R.; Salunkhe, D.K.; Deshmukh, M.B.

doi:10.1107/S1600536812042304

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3121

doi:10.1107/S1600536812042304

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Methyl (2E)-2-cyano-3-(dimethylamino)prop-2-enoate

Rajni Kant,^a ^* Vivek K. Gupta,^a Kamini Kapoor,^a D. R. Patil,^b D. K. Salunkhe ^b and Madhukar B. Deshmukh ^b

^aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bDepartment of Chemistry, Shivaji University, Kolhapur, 416 004, India
^*Correspondence e-mail: rkvk.paper11@gmail.com

(Received 5 October 2012; accepted 9 October 2012; online 13 October 2012)

In the title compound, C₇H₁₀N₂O₂, the dimethylamino group is twisted slightly relative to the acrylate fragment, forming a dihedral angle of 11.6 (1)°. In the crystal, molecules are linked via pairs of bifurcated C—H/H⋯O hydrogen bonds, forming inversion dimers, which are further connected by C—H⋯N hydrogen bonds into chains along the a-axis direction.

Related literature

For applications of enamines, see: Huang et al. (2007 ); Michael et al. (1999 ). For a related structure, see: Gupta et al. (2007 ).

Experimental

Crystal data

C₇H₁₀N₂O₂
M_r = 154.17
Triclinic, $[P \overline 1]$
a = 7.1102 (5) Å
b = 7.8170 (5) Å
c = 8.2454 (6) Å
α = 97.270 (6)°
β = 93.431 (6)°
γ = 115.680 (7)°
V = 406.31 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.830, T_max = 1.000
6682 measured reflections
1593 independent reflections
1126 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.03
1593 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.56	3.370 (2)	146
C4—H4A⋯O1ⁱ	0.96	2.58	3.415 (3)	145
C7—H7C⋯N2ⁱⁱ	0.96	2.58	3.535 (3)	172
Symmetry codes: (i) -x, -y+1, -z+2; (ii) x-1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536812042304/gk2525sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042304/gk2525Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042304/gk2525Isup3.cml

checkCIF report

Comment top

Enamines are the multipurpose synthetic intermediates used for the synthesis of a variety of organic derivatives, bioactive natural products and their analogs (Huang et al., 2007; Michael et al., 1999).

In (I)(Fig.1), all bond lengths and angles are normal and correspond to those observed in the related structure (Gupta et al., 2007). The dihedral angle between dimethylamino and acrylate fragment is 11.6 (1)°. In the crystal, C3—H3···O1 and C4—H4A···O1 hydrogen bonds link molecules to form dimers. Dimers are further connected by C—H···N hydrogen bonds into chains along the a axis (Fig. 2, Table 1.).

Related literature top

For applications of enamines, see: Huang et al. (2007); Michael et al. (1999). For a related structure, see: Gupta et al. (2007).

Experimental top

In a 50 ml round bottom flask the mixture of 5 mmole of methyl cyanoacetate and 5 mmole of dimethylformamide dimethyl acetal was stirred at room temperature for 1–1.5 h. After completion of reaction, the reaction mixture was poured on ice cold water and the separated solid was precipated after 15 minutes and recrystallized from ethanol. Yield: 87%; m.p. 378–380 K. IR(KBr): 2205, 1695, 1621, 1433, 1373, 1287, 1216 1/cm

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing arrangement of molecules viewed down the a axis. The dotted lines show intermolecular C—H···O and C—H···N hydrogen bonds.

Methyl (2E)-2-cyano-3-(dimethylamino)prop-2-enoate top

Crystal data top

C₇H₁₀N₂O₂	Z = 2
M_r = 154.17	F(000) = 164
Triclinic, P1	D_x = 1.260 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1102 (5) Å	Cell parameters from 2720 reflections
b = 7.8170 (5) Å	θ = 3.5–29.0°
c = 8.2454 (6) Å	µ = 0.09 mm⁻¹
α = 97.270 (6)°	T = 293 K
β = 93.431 (6)°	Block, white
γ = 115.680 (7)°	0.3 × 0.2 × 0.2 mm
V = 406.31 (5) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1593 independent reflections
Radiation source: fine-focus sealed tube	1126 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scan	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −9→9
T_min = 0.830, T_max = 1.000	l = −10→10
6682 measured reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0618P)² + 0.0587P] where P = (F_o² + 2F_c²)/3
1593 reflections	(Δ/σ)_max = 0.001
103 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₇H₁₀N₂O₂	γ = 115.680 (7)°
M_r = 154.17	V = 406.31 (5) Å³
Triclinic, P1	Z = 2
a = 7.1102 (5) Å	Mo Kα radiation
b = 7.8170 (5) Å	µ = 0.09 mm⁻¹
c = 8.2454 (6) Å	T = 293 K
α = 97.270 (6)°	0.3 × 0.2 × 0.2 mm
β = 93.431 (6)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1593 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1126 reflections with I > 2σ(I)
T_min = 0.830, T_max = 1.000	R_int = 0.047
6682 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	Δρ_max = 0.17 e Å⁻³
1593 reflections	Δρ_min = −0.13 e Å⁻³
103 parameters

Special details top

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.0160 (2)	0.6248 (2)	0.82511 (17)	0.0648 (5)
O2	0.20619 (19)	0.77535 (19)	0.63425 (16)	0.0535 (4)
C1	0.1860 (3)	0.7109 (2)	0.7792 (2)	0.0438 (4)
C2	0.3885 (3)	0.7570 (2)	0.8695 (2)	0.0405 (4)
N1	0.5414 (2)	0.7293 (2)	1.13299 (19)	0.0475 (4)
N2	0.7150 (3)	0.9493 (3)	0.7343 (2)	0.0733 (6)
C3	0.3876 (3)	0.7106 (2)	1.0252 (2)	0.0423 (4)
H3	0.2552	0.6567	1.0599	0.051*
C4	0.5009 (3)	0.6883 (3)	1.2987 (3)	0.0666 (6)
H4A	0.3525	0.6365	1.3051	0.100*
H4B	0.5737	0.8051	1.3773	0.100*
H4C	0.5498	0.5964	1.3228	0.100*
C5	0.7594 (3)	0.7984 (3)	1.1018 (3)	0.0616 (6)
H5A	0.7642	0.7414	0.9929	0.092*
H5B	0.8346	0.7633	1.1813	0.092*
H5C	0.8230	0.9360	1.1107	0.092*
C6	0.5718 (3)	0.8620 (3)	0.7958 (2)	0.0478 (5)
C7	0.0158 (3)	0.7445 (3)	0.5374 (3)	0.0611 (6)
H7A	−0.0765	0.6090	0.5118	0.092*
H7B	0.0491	0.7950	0.4371	0.092*
H7C	−0.0524	0.8090	0.5988	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0394 (8)	0.0845 (10)	0.0603 (9)	0.0136 (7)	0.0073 (7)	0.0287 (8)
O2	0.0476 (8)	0.0646 (9)	0.0472 (8)	0.0215 (6)	0.0059 (6)	0.0186 (6)
C1	0.0443 (11)	0.0417 (9)	0.0417 (10)	0.0157 (8)	0.0064 (8)	0.0071 (7)
C2	0.0356 (9)	0.0396 (9)	0.0435 (10)	0.0140 (7)	0.0079 (8)	0.0061 (7)
N1	0.0395 (8)	0.0516 (9)	0.0457 (9)	0.0151 (7)	0.0027 (7)	0.0095 (7)
N2	0.0502 (11)	0.0953 (15)	0.0766 (13)	0.0263 (10)	0.0241 (10)	0.0380 (11)
C3	0.0369 (10)	0.0385 (9)	0.0467 (10)	0.0122 (8)	0.0069 (8)	0.0073 (7)
C4	0.0583 (13)	0.0804 (15)	0.0516 (12)	0.0205 (11)	0.0027 (10)	0.0200 (11)
C5	0.0422 (11)	0.0738 (14)	0.0650 (14)	0.0223 (10)	0.0028 (10)	0.0140 (11)
C6	0.0430 (10)	0.0534 (11)	0.0475 (11)	0.0210 (9)	0.0086 (9)	0.0114 (9)
C7	0.0567 (13)	0.0726 (14)	0.0569 (13)	0.0298 (11)	0.0024 (10)	0.0200 (11)

Geometric parameters (Å, º) top

O1—C1	1.213 (2)	C3—H3	0.9300
O2—C1	1.346 (2)	C4—H4A	0.9600
O2—C7	1.438 (2)	C4—H4B	0.9600
C1—C2	1.454 (2)	C4—H4C	0.9600
C2—C3	1.377 (2)	C5—H5A	0.9600
C2—C6	1.427 (2)	C5—H5B	0.9600
N1—C3	1.311 (2)	C5—H5C	0.9600
N1—C5	1.455 (2)	C7—H7A	0.9600
N1—C4	1.460 (2)	C7—H7B	0.9600
N2—C6	1.143 (2)	C7—H7C	0.9600

C1—O2—C7	116.82 (15)	N1—C4—H4C	109.5
O1—C1—O2	122.40 (17)	H4A—C4—H4C	109.5
O1—C1—C2	125.53 (17)	H4B—C4—H4C	109.5
O2—C1—C2	112.07 (15)	N1—C5—H5A	109.5
C3—C2—C6	125.51 (17)	N1—C5—H5B	109.5
C3—C2—C1	117.00 (15)	H5A—C5—H5B	109.5
C6—C2—C1	117.21 (16)	N1—C5—H5C	109.5
C3—N1—C5	124.10 (16)	H5A—C5—H5C	109.5
C3—N1—C4	120.07 (15)	H5B—C5—H5C	109.5
C5—N1—C4	115.77 (16)	N2—C6—C2	177.6 (2)
N1—C3—C2	131.07 (16)	O2—C7—H7A	109.5
N1—C3—H3	114.5	O2—C7—H7B	109.5
C2—C3—H3	114.5	H7A—C7—H7B	109.5
N1—C4—H4A	109.5	O2—C7—H7C	109.5
N1—C4—H4B	109.5	H7A—C7—H7C	109.5
H4A—C4—H4B	109.5	H7B—C7—H7C	109.5

C7—O2—C1—O1	2.5 (3)	O2—C1—C2—C6	0.9 (2)
C7—O2—C1—C2	−177.56 (15)	C5—N1—C3—C2	−4.1 (3)
O1—C1—C2—C3	−4.8 (3)	C4—N1—C3—C2	173.00 (19)
O2—C1—C2—C3	175.27 (15)	C6—C2—C3—N1	−8.1 (3)
O1—C1—C2—C6	−179.14 (17)	C1—C2—C3—N1	178.06 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.56	3.370 (2)	146
C4—H4A···O1ⁱ	0.96	2.58	3.415 (3)	145
C7—H7C···N2ⁱⁱ	0.96	2.58	3.535 (3)	172

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N₂O₂
M_r	154.17
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1102 (5), 7.8170 (5), 8.2454 (6)
α, β, γ (°)	97.270 (6), 93.431 (6), 115.680 (7)
V (Å³)	406.31 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.830, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6682, 1593, 1126
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.03
No. of reflections	1593
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.56	3.370 (2)	146
C4—H4A···O1ⁱ	0.96	2.58	3.415 (3)	145
C7—H7C···N2ⁱⁱ	0.96	2.58	3.535 (3)	172

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1, y, z.

Acknowledgements

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.

References

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