Methyl 3-amino­but-2-enoate

Abstract

The title compound, C₅H₉NO₂, is almost planar (r.m.s. deviation for the non-H atoms = 0.036 Å) and an intra­molecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, N—H⋯O inter­actions link the mol­ecules into C(6) chains propagating along [010].

Related literature  

For further synthetic details, see: Rakshit et al. (2010 ▶); Vanden Eynde et al. (1995 ▶).

Experimental  

Crystal data  

• C₅H₉NO₂

• M _r = 115.13

• Monoclinic,

• a = 8.3020 (12) Å

• b = 9.7232 (14) Å

• c = 7.665 (1) Å

• β = 97.855 (13)°

• V = 612.93 (15) ų

• Z = 4

• Cu Kα radiation

• μ = 0.81 mm⁻¹

• T = 113 K

• 0.18 × 0.16 × 0.10 mm

Data collection  

• Rigaku Saturn944 CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ▶) T _min = 0.868, T _max = 0.924

• 6605 measured reflections

• 1175 independent reflections

• 1019 reflections with I > 2σ(I)

• R _int = 0.071

Refinement  

• R[F ² > 2σ(F ²)] = 0.067

• wR(F ²) = 0.141

• S = 1.20

• 1175 reflections

• 84 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

Data collection: CrystalClear (Rigaku, 2009 ▶); 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: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202288X/hb6788Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.84 (2)	2.05 (2)	2.8778 (16)	168.9 (19)
N1—H1B⋯O1	0.89 (2)	2.08 (2)	2.7168 (16)	127.7 (15)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Nifedipine was found to be a highly effective calcium antagonist. Consequently,many compounds which were similar in structure to nifedipine have already been used as therapeutic agents for treatment of cerebral circulatory disorder,hypertension and so on. The title compound (I) is an intermediate for the synthesis of this family of compounds and its structure is reported here. As shown in Fig. 1, in each molecular unit, almost non-hydrogen atoms in the same plane, and the deviation is 0.036 nm. The length of the double bond is slightly longer than the normal double bond of ethylene likewise, the bond between carbon and nitrogen are shorter than normal C—N bond. A short intermolecular N—H···O interaction (Table 1) occurs [symmetry code:(i)-x + 1,y - 1/2,-z + 1/2], and relatively strong intramolecular N—H···O hydrogen bonds also exists.

Experimental

Impoved from the published methods by Rakshit et al. (2010) and Vanden Eynde et al. (1995) a modification of the synthetic procedure was used to prepare the title compound from methyl acetoacetate and ammonium acetate. Colorless prisms of (I) were obtained by recrystallizing from a ethyl acetate solution. mp: 355 K. Analysis, calculated for C₅H₉NO₂: C 52.16, H 7.88, N 12.17; found: C 52.15, H 7.87, N 12.16.

Figures

Fig. 1.

The molecular structure of (I), with 30% probability displacement ellipsoids.

Fig. 2.

Packing diagram for (I).

Crystal data

C5H9NO2	Dx = 1.248 Mg m−3
Mr = 115.13	Melting point: 355 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54187 Å
a = 8.3020 (12) Å	Cell parameters from 670 reflections
b = 9.7232 (14) Å	θ = 27.9–71.6°
c = 7.665 (1) Å	µ = 0.81 mm−1
β = 97.855 (13)°	T = 113 K
V = 612.93 (15) Å3	Prism, colorless
Z = 4	0.18 × 0.16 × 0.10 mm
F(000) = 248

Data collection

Rigaku Saturn944 CCD diffractometer	1175 independent reflections
Radiation source: fine-focus sealed tube	1019 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.071
Detector resolution: 14.629 pixels mm-1	θmax = 71.9°, θmin = 5.4°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −11→9
Tmin = 0.868, Tmax = 0.924	l = −9→9
6605 measured reflections

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)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.141	w = 1/[σ2(Fo2) + (0.0954P)2] where P = (Fo2 + 2Fc2)/3
S = 1.20	(Δ/σ)max < 0.001
1175 reflections	Δρmax = 0.36 e Å−3
84 parameters	Δρmin = −0.51 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: 0.32 (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
O1	0.36825 (11)	0.18110 (10)	0.32340 (12)	0.0327 (4)
O2	0.12958 (12)	0.21372 (10)	0.42596 (13)	0.0357 (4)
N1	0.45092 (13)	−0.08490 (14)	0.27315 (14)	0.0320 (4)
C1	0.24663 (14)	0.13160 (14)	0.37507 (15)	0.0279 (4)
C2	0.21064 (14)	−0.01182 (15)	0.38684 (15)	0.0294 (4)
H2	0.1142	−0.0387	0.4317	0.035*
C3	0.31094 (14)	−0.11148 (14)	0.33542 (15)	0.0285 (4)
C4	0.26670 (18)	−0.26132 (15)	0.34523 (18)	0.0348 (4)
H4A	0.2644	−0.3035	0.2288	0.042*
H4B	0.1592	−0.2697	0.3836	0.042*
H4C	0.3477	−0.3083	0.4297	0.042*
C5	0.15619 (19)	0.35898 (16)	0.4094 (2)	0.0400 (5)
H5A	0.2563	0.3854	0.4849	0.048*
H5B	0.0641	0.4096	0.4455	0.048*
H5C	0.1663	0.3810	0.2866	0.048*
H1B	0.487 (2)	0.002 (2)	0.269 (3)	0.048 (5)*
H1A	0.515 (2)	−0.147 (2)	0.249 (2)	0.046 (5)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0298 (6)	0.0295 (6)	0.0403 (6)	−0.0019 (4)	0.0102 (4)	−0.0002 (4)
O2	0.0328 (6)	0.0327 (7)	0.0437 (6)	0.0049 (4)	0.0128 (4)	−0.0031 (4)
N1	0.0287 (6)	0.0280 (8)	0.0409 (7)	0.0012 (5)	0.0109 (5)	−0.0021 (5)
C1	0.0263 (6)	0.0312 (9)	0.0262 (6)	0.0009 (5)	0.0040 (5)	−0.0015 (5)
C2	0.0259 (6)	0.0325 (9)	0.0311 (7)	−0.0039 (5)	0.0080 (5)	−0.0006 (5)
C3	0.0299 (7)	0.0301 (8)	0.0252 (6)	−0.0030 (5)	0.0024 (5)	−0.0002 (5)
C4	0.0423 (8)	0.0294 (8)	0.0335 (7)	−0.0043 (6)	0.0078 (6)	−0.0007 (5)
C5	0.0457 (8)	0.0316 (9)	0.0436 (8)	0.0095 (6)	0.0097 (6)	−0.0031 (6)

Geometric parameters (Å, º)

O1—C1	1.2317 (16)	C2—H2	0.9500
O2—C1	1.3557 (15)	C3—C4	1.5069 (18)
O2—C5	1.4379 (18)	C4—H4A	0.9800
N1—C3	1.3404 (17)	C4—H4B	0.9800
N1—H1B	0.89 (2)	C4—H4C	0.9800
N1—H1A	0.84 (2)	C5—H5A	0.9800
C1—C2	1.432 (2)	C5—H5B	0.9800
C2—C3	1.3702 (19)	C5—H5C	0.9800
C1—O2—C5	115.36 (11)	C3—C4—H4A	109.5
C3—N1—H1B	120.4 (12)	C3—C4—H4B	109.5
C3—N1—H1A	123.3 (14)	H4A—C4—H4B	109.5
H1B—N1—H1A	115.8 (18)	C3—C4—H4C	109.5
O1—C1—O2	120.91 (13)	H4A—C4—H4C	109.5
O1—C1—C2	126.03 (12)	H4B—C4—H4C	109.5
O2—C1—C2	113.05 (11)	O2—C5—H5A	109.5
C3—C2—C1	122.04 (12)	O2—C5—H5B	109.5
C3—C2—H2	119.0	H5A—C5—H5B	109.5
C1—C2—H2	119.0	O2—C5—H5C	109.5
N1—C3—C2	123.82 (13)	H5A—C5—H5C	109.5
N1—C3—C4	115.67 (12)	H5B—C5—H5C	109.5
C2—C3—C4	120.50 (12)
C5—O2—C1—O1	1.92 (16)	O2—C1—C2—C3	177.61 (10)
C5—O2—C1—C2	−177.39 (11)	C1—C2—C3—N1	1.13 (19)
O1—C1—C2—C3	−1.7 (2)	C1—C2—C3—C4	−178.35 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.84 (2)	2.05 (2)	2.8778 (16)	168.9 (19)
N1—H1B···O1	0.89 (2)	2.08 (2)	2.7168 (16)	127.7 (15)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.