Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017361/ww6045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017361/ww6045Isup2.hkl |
CCDC reference: 198978
The title compound was synthesized according to the literature (Zhu et al., 1999). A crystal suitable for X-ray analysis was slowly grown in a mixed solvent of ethyl acetate and hexane (EA/nexane 1:6) at room temperature. 1H NMR (400 MHz, acetone-d6, p.p.m.): δ 2.03 (s, 3H), 2.29 (s, 3H), 3.58 (s, 3H), 6.85 (d, J = 1 Hz, 1H), 8.79 (br, 1H).
H atoms were included in the riding-model approximation with Uiso values equal to Ueq of the atom to which they were bound.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
Fig. 1. The molecular structure of (I), showing ellipsoids at the 30% probability level (Siemens, 1995). | |
Fig. 2. Packing diagram for the title compound. Hydrogen bonds are shown as dotted lines. |
C7H11NO3 | F(000) = 336 |
Mr = 157.17 | Dx = 1.231 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.099 (2) Å | Cell parameters from 1994 reflections |
b = 12.761 (2) Å | θ = 1–27.5° |
c = 8.750 (2) Å | µ = 0.10 mm−1 |
β = 110.268 (4)° | T = 294 K |
V = 848.4 (2) Å3 | Prism, colorless |
Z = 4 | 0.36 × 0.32 × 0.30 mm |
Siemens SMART CCD area-detector diffractometer | 1945 independent reflections |
Radiation source: fine-focus sealed tube | 994 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −10→9 |
Tmin = 0.966, Tmax = 0.972 | k = −14→16 |
5609 measured reflections | l = −7→11 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3 |
1945 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C7H11NO3 | V = 848.4 (2) Å3 |
Mr = 157.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.099 (2) Å | µ = 0.10 mm−1 |
b = 12.761 (2) Å | T = 294 K |
c = 8.750 (2) Å | 0.36 × 0.32 × 0.30 mm |
β = 110.268 (4)° |
Siemens SMART CCD area-detector diffractometer | 1945 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 994 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.972 | Rint = 0.038 |
5609 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.17 e Å−3 |
1945 reflections | Δρmin = −0.15 e Å−3 |
103 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.09296 (17) | 0.26580 (10) | 0.29159 (17) | 0.0679 (5) | |
O3 | −0.05051 (19) | 0.59645 (11) | 0.12587 (18) | 0.0733 (5) | |
O2 | 0.2126 (3) | 0.62923 (12) | 0.3063 (2) | 0.1145 (8) | |
N1 | 0.14590 (18) | 0.32240 (11) | 0.49975 (18) | 0.0516 (5) | |
H1A | 0.2193 | 0.3032 | 0.5926 | 0.062* | |
C4 | 0.0713 (2) | 0.46541 (13) | 0.3085 (2) | 0.0533 (5) | |
H4 | −0.0168 | 0.4234 | 0.2391 | 0.064* | |
C3 | 0.1702 (2) | 0.42467 (14) | 0.4509 (2) | 0.0474 (5) | |
C5 | 0.0906 (3) | 0.57061 (15) | 0.2534 (3) | 0.0599 (6) | |
C2 | 0.0234 (2) | 0.24983 (14) | 0.4215 (2) | 0.0547 (5) | |
C7 | 0.3149 (3) | 0.47864 (16) | 0.5809 (3) | 0.0700 (7) | |
H7A | 0.3282 | 0.5486 | 0.5463 | 0.105* | |
H7B | 0.4228 | 0.4407 | 0.6013 | 0.105* | |
H7C | 0.2871 | 0.4815 | 0.6789 | 0.105* | |
C1 | 0.0434 (3) | 0.14619 (15) | 0.5063 (3) | 0.0801 (8) | |
H1B | −0.0708 | 0.1168 | 0.4889 | 0.120* | |
H1C | 0.1043 | 0.1558 | 0.6209 | 0.120* | |
H1D | 0.1095 | 0.0995 | 0.4634 | 0.120* | |
C6 | −0.0507 (4) | 0.69941 (18) | 0.0564 (3) | 0.0899 (8) | |
H6A | −0.0571 | 0.7519 | 0.1328 | 0.135* | |
H6B | −0.1506 | 0.7059 | −0.0421 | 0.135* | |
H6C | 0.0555 | 0.7087 | 0.0325 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0695 (9) | 0.0526 (8) | 0.0540 (9) | −0.0127 (6) | −0.0139 (7) | 0.0065 (6) |
O3 | 0.0782 (10) | 0.0568 (9) | 0.0756 (10) | 0.0102 (7) | 0.0151 (8) | 0.0231 (7) |
O2 | 0.1207 (14) | 0.0722 (11) | 0.1106 (16) | −0.0385 (11) | −0.0109 (12) | 0.0223 (10) |
N1 | 0.0541 (9) | 0.0419 (9) | 0.0424 (9) | −0.0005 (7) | −0.0043 (7) | 0.0000 (7) |
C4 | 0.0584 (11) | 0.0400 (10) | 0.0519 (12) | −0.0035 (9) | 0.0070 (9) | −0.0023 (9) |
C3 | 0.0464 (10) | 0.0415 (10) | 0.0486 (11) | 0.0006 (8) | 0.0093 (9) | −0.0035 (8) |
C5 | 0.0692 (13) | 0.0455 (11) | 0.0579 (13) | 0.0008 (10) | 0.0131 (11) | 0.0001 (10) |
C2 | 0.0570 (12) | 0.0461 (11) | 0.0483 (12) | −0.0005 (9) | 0.0022 (10) | 0.0020 (9) |
C7 | 0.0639 (13) | 0.0614 (13) | 0.0670 (15) | −0.0114 (10) | 0.0001 (11) | −0.0047 (11) |
C1 | 0.0893 (16) | 0.0497 (13) | 0.0733 (16) | −0.0098 (11) | −0.0076 (13) | 0.0115 (11) |
C6 | 0.121 (2) | 0.0606 (14) | 0.0913 (19) | 0.0254 (14) | 0.0415 (17) | 0.0321 (13) |
O1—C2 | 1.216 (2) | C2—C1 | 1.498 (3) |
O3—C5 | 1.333 (2) | C7—H7A | 0.9600 |
O3—C6 | 1.447 (3) | C7—H7B | 0.9600 |
O2—C5 | 1.197 (2) | C7—H7C | 0.9600 |
N1—C2 | 1.357 (2) | C1—H1B | 0.9600 |
N1—C3 | 1.408 (2) | C1—H1C | 0.9600 |
N1—H1A | 0.8600 | C1—H1D | 0.9600 |
C4—C3 | 1.332 (2) | C6—H6A | 0.9600 |
C4—C5 | 1.453 (3) | C6—H6B | 0.9600 |
C4—H4 | 0.9300 | C6—H6C | 0.9600 |
C3—C7 | 1.489 (2) | ||
C5—O3—C6 | 116.86 (17) | C3—C7—H7B | 109.5 |
C2—N1—C3 | 129.36 (15) | H7A—C7—H7B | 109.5 |
C2—N1—H1A | 115.3 | C3—C7—H7C | 109.5 |
C3—N1—H1A | 115.3 | H7A—C7—H7C | 109.5 |
C3—C4—C5 | 124.88 (17) | H7B—C7—H7C | 109.5 |
C3—C4—H4 | 117.6 | C2—C1—H1B | 109.5 |
C5—C4—H4 | 117.6 | C2—C1—H1C | 109.5 |
C4—C3—N1 | 122.94 (15) | H1B—C1—H1C | 109.5 |
C4—C3—C7 | 126.40 (17) | C2—C1—H1D | 109.5 |
N1—C3—C7 | 110.64 (15) | H1B—C1—H1D | 109.5 |
O2—C5—O3 | 121.52 (19) | H1C—C1—H1D | 109.5 |
O2—C5—C4 | 128.2 (2) | O3—C6—H6A | 109.5 |
O3—C5—C4 | 110.27 (17) | O3—C6—H6B | 109.5 |
O1—C2—N1 | 123.49 (17) | H6A—C6—H6B | 109.5 |
O1—C2—C1 | 121.80 (17) | O3—C6—H6C | 109.5 |
N1—C2—C1 | 114.70 (16) | H6A—C6—H6C | 109.5 |
C3—C7—H7A | 109.5 | H6B—C6—H6C | 109.5 |
C5—C4—C3—N1 | 179.54 (18) | C6—O3—C5—C4 | −179.80 (19) |
C5—C4—C3—C7 | 1.4 (3) | C3—C4—C5—O2 | 15.9 (4) |
C2—N1—C3—C4 | −2.1 (3) | C3—C4—C5—O3 | −165.59 (19) |
C2—N1—C3—C7 | 176.35 (19) | C3—N1—C2—O1 | −2.3 (3) |
C6—O3—C5—O2 | −1.2 (3) | C3—N1—C2—C1 | 176.73 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.07 | 2.9188 (19) | 169 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C7H11NO3 |
Mr | 157.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 8.099 (2), 12.761 (2), 8.750 (2) |
β (°) | 110.268 (4) |
V (Å3) | 848.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.36 × 0.32 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.966, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5609, 1945, 994 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.148, 1.01 |
No. of reflections | 1945 |
No. of parameters | 103 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.15 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL-NT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.07 | 2.9188 (19) | 169 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
The title compound, (I), is one of the isomers of methyl 3-acetamido-2-butenoate, a prochiral olefinic substrate for producing β-amino acids and derivatives by asymmetric hydrogenation (Hackler et al., 1985; Lubell et al., 1991). The E isomer gives a much higher enantiomeric excess than the Z isomer in the asymmetric hydrogenation reaction (Burk et al., 1996). The structure determination of (I) was conducted in order to obtain more knowledge about β-amino acids and their derivatives.
Fig. 1 shows a perspective view of the molecule. The deviations of the angles C4—C3—C7 [126.40 (17)°], C3—C4—C5 [124.88 (17)°] and N1—C3—C7 [110.64 (15)°] from the value of 120° results in a close approach between the methyl group on C3 and the carbonyl group on C4 (Table 1). The molecules are connected through an intermolecular hydrogen bond (Table 2). In the packing, the molecules are connected by an N—H···O hydrogen bond and linking along [101] (Fig. 2).