Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017373/ww6044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017373/ww6044Isup2.hkl |
CCDC reference: 198977
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.053
- wR factor = 0.153
- Data-to-parameter ratio = 19.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized according theliterature (Zhu et al., 1999) A crystal suitable for X-ray analysis was grown slowly from a mixture of ethyl acetate and hexane at room temperature. 1H NMR (400 MHz, acetone-d6, p.p.m.): δ 1.24 (t, J = 7.1 Hz, 3H), 2.06 (s, 3H), 2.33 (s, 3H), 4.09 (q, J = 7.1 Hz, 2H), 6.89 (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 (I). The hydrogen bonds are indicated by dashed lines. |
C8H13NO3 | F(000) = 736 |
Mr = 171.19 | Dx = 1.212 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.006 (4) Å | Cell parameters from 2174 reflections |
b = 9.545 (2) Å | θ = 1–27.5° |
c = 11.922 (2) Å | µ = 0.09 mm−1 |
β = 124.479 (4)° | T = 294 K |
V = 1876.7 (6) Å3 | Plate, colorless |
Z = 8 | 0.34 × 0.28 × 0.10 mm |
Siemens SMART CCD area-detector diffractometer | 2162 independent reflections |
Radiation source: fine-focus sealed tube | 1053 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ϕ and ω scans | θmax = 27.6°, θmin = 3.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −22→25 |
Tmin = 0.969, Tmax = 0.991 | k = −12→12 |
6283 measured reflections | l = −15→15 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3 |
2162 reflections | (Δ/σ)max < 0.001 |
112 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C8H13NO3 | V = 1876.7 (6) Å3 |
Mr = 171.19 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.006 (4) Å | µ = 0.09 mm−1 |
b = 9.545 (2) Å | T = 294 K |
c = 11.922 (2) Å | 0.34 × 0.28 × 0.10 mm |
β = 124.479 (4)° |
Siemens SMART CCD area-detector diffractometer | 2162 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1053 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.991 | Rint = 0.035 |
6283 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.20 e Å−3 |
2162 reflections | Δρmin = −0.16 e Å−3 |
112 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 | 0.24031 (10) | 0.98771 (15) | 0.21996 (17) | 0.0769 (5) | |
O2 | 0.43183 (11) | 0.88023 (17) | 0.06239 (18) | 0.0906 (6) | |
O3 | 0.40086 (9) | 1.09940 (14) | 0.08209 (14) | 0.0692 (5) | |
N1 | 0.27942 (10) | 0.77021 (15) | 0.20365 (16) | 0.0551 (5) | |
H1A | 0.2724 | 0.6830 | 0.2123 | 0.066* | |
C1 | 0.19104 (15) | 0.7954 (2) | 0.2785 (3) | 0.0819 (8) | |
H1B | 0.1506 | 0.8600 | 0.2661 | 0.123* | |
H1C | 0.2267 | 0.7718 | 0.3732 | 0.123* | |
H1D | 0.1652 | 0.7120 | 0.2267 | 0.123* | |
C2 | 0.23847 (12) | 0.8610 (2) | 0.2317 (2) | 0.0564 (6) | |
C3 | 0.33135 (12) | 0.79732 (19) | 0.16286 (19) | 0.0518 (5) | |
C4 | 0.34191 (12) | 0.9254 (2) | 0.1309 (2) | 0.0592 (6) | |
H4 | 0.3128 | 0.9984 | 0.1356 | 0.071* | |
C5 | 0.39601 (13) | 0.9594 (2) | 0.0889 (2) | 0.0623 (6) | |
C6 | 0.45348 (14) | 1.1505 (2) | 0.0444 (2) | 0.0752 (7) | |
H6A | 0.4350 | 1.1172 | −0.0457 | 0.090* | |
H6B | 0.5084 | 1.1174 | 0.1085 | 0.090* | |
C7 | 0.45111 (17) | 1.3072 (3) | 0.0457 (3) | 0.0932 (9) | |
H7A | 0.3961 | 1.3385 | −0.0140 | 0.140* | |
H7B | 0.4830 | 1.3443 | 0.0155 | 0.140* | |
H7C | 0.4728 | 1.3392 | 0.1365 | 0.140* | |
C8 | 0.37290 (14) | 0.6677 (2) | 0.1617 (2) | 0.0690 (6) | |
H8A | 0.4154 | 0.6928 | 0.1509 | 0.104* | |
H8B | 0.3344 | 0.6087 | 0.0874 | 0.104* | |
H8C | 0.3956 | 0.6182 | 0.2459 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1022 (13) | 0.0467 (9) | 0.1292 (14) | 0.0032 (8) | 0.0939 (12) | 0.0030 (8) |
O2 | 0.1093 (14) | 0.0831 (11) | 0.1347 (15) | 0.0115 (10) | 0.1024 (14) | 0.0118 (10) |
O3 | 0.0809 (11) | 0.0683 (10) | 0.0891 (11) | −0.0093 (8) | 0.0667 (10) | 0.0011 (7) |
N1 | 0.0636 (11) | 0.0454 (8) | 0.0789 (11) | −0.0032 (8) | 0.0538 (10) | −0.0026 (8) |
C1 | 0.1037 (19) | 0.0548 (12) | 0.141 (2) | −0.0015 (12) | 0.1015 (19) | 0.0013 (13) |
C2 | 0.0624 (13) | 0.0481 (12) | 0.0771 (14) | −0.0016 (10) | 0.0505 (12) | −0.0029 (10) |
C3 | 0.0489 (11) | 0.0585 (12) | 0.0567 (12) | −0.0010 (9) | 0.0350 (11) | −0.0044 (9) |
C4 | 0.0662 (14) | 0.0564 (12) | 0.0786 (14) | −0.0033 (10) | 0.0552 (13) | −0.0036 (10) |
C5 | 0.0644 (14) | 0.0699 (14) | 0.0705 (14) | −0.0014 (11) | 0.0489 (13) | 0.0012 (11) |
C6 | 0.0704 (16) | 0.0911 (17) | 0.0808 (16) | −0.0113 (13) | 0.0529 (14) | 0.0127 (13) |
C7 | 0.103 (2) | 0.0963 (19) | 0.0912 (18) | −0.0282 (15) | 0.0613 (18) | 0.0042 (14) |
C8 | 0.0747 (15) | 0.0631 (13) | 0.0928 (16) | 0.0095 (11) | 0.0615 (14) | 0.0032 (11) |
O1—C2 | 1.220 (2) | C3—C8 | 1.495 (3) |
O2—C5 | 1.200 (2) | C4—C5 | 1.463 (3) |
O3—C5 | 1.345 (2) | C4—H4 | 0.9300 |
O3—C6 | 1.444 (2) | C6—C7 | 1.496 (3) |
N1—C2 | 1.358 (2) | C6—H6A | 0.9700 |
N1—C3 | 1.398 (2) | C6—H6B | 0.9700 |
N1—H1A | 0.8600 | C7—H7A | 0.9600 |
C1—C2 | 1.485 (3) | C7—H7B | 0.9600 |
C1—H1B | 0.9600 | C7—H7C | 0.9600 |
C1—H1C | 0.9600 | C8—H8A | 0.9600 |
C1—H1D | 0.9600 | C8—H8B | 0.9600 |
C3—C4 | 1.333 (3) | C8—H8C | 0.9600 |
C5—O3—C6 | 116.38 (17) | O2—C5—C4 | 128.1 (2) |
C2—N1—C3 | 129.64 (16) | O3—C5—C4 | 109.46 (17) |
C2—N1—H1A | 115.2 | O3—C6—C7 | 107.52 (19) |
C3—N1—H1A | 115.2 | O3—C6—H6A | 110.2 |
C2—C1—H1B | 109.5 | C7—C6—H6A | 110.2 |
C2—C1—H1C | 109.5 | O3—C6—H6B | 110.2 |
H1B—C1—H1C | 109.5 | C7—C6—H6B | 110.2 |
C2—C1—H1D | 109.5 | H6A—C6—H6B | 108.5 |
H1B—C1—H1D | 109.5 | C6—C7—H7A | 109.5 |
H1C—C1—H1D | 109.5 | C6—C7—H7B | 109.5 |
O1—C2—N1 | 122.88 (17) | H7A—C7—H7B | 109.5 |
O1—C2—C1 | 121.88 (17) | C6—C7—H7C | 109.5 |
N1—C2—C1 | 115.24 (17) | H7A—C7—H7C | 109.5 |
C4—C3—N1 | 122.61 (17) | H7B—C7—H7C | 109.5 |
C4—C3—C8 | 125.27 (18) | C3—C8—H8A | 109.5 |
N1—C3—C8 | 112.12 (16) | C3—C8—H8B | 109.5 |
C3—C4—C5 | 124.71 (19) | H8A—C8—H8B | 109.5 |
C3—C4—H4 | 117.6 | C3—C8—H8C | 109.5 |
C5—C4—H4 | 117.6 | H8A—C8—H8C | 109.5 |
O2—C5—O3 | 122.39 (18) | H8B—C8—H8C | 109.5 |
C3—N1—C2—O1 | 2.3 (3) | C6—O3—C5—O2 | −1.5 (3) |
C3—N1—C2—C1 | −177.4 (2) | C6—O3—C5—C4 | 178.83 (17) |
C2—N1—C3—C4 | −7.3 (3) | C3—C4—C5—O2 | 8.7 (4) |
C2—N1—C3—C8 | 171.98 (19) | C3—C4—C5—O3 | −171.69 (19) |
N1—C3—C4—C5 | 179.42 (18) | C5—O3—C6—C7 | −178.91 (19) |
C8—C3—C4—C5 | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.10 | 2.943 (2) | 165 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H13NO3 |
Mr | 171.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 294 |
a, b, c (Å) | 20.006 (4), 9.545 (2), 11.922 (2) |
β (°) | 124.479 (4) |
V (Å3) | 1876.7 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.34 × 0.28 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.969, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6283, 2162, 1053 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.153, 1.05 |
No. of reflections | 2162 |
No. of parameters | 112 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL-NT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
O1—C2 | 1.220 (2) | C3—C4 | 1.333 (3) |
O2—C5 | 1.200 (2) | C3—C8 | 1.495 (3) |
N1—C2 | 1.358 (2) | C4—C5 | 1.463 (3) |
N1—C3 | 1.398 (2) | ||
O1—C2—N1 | 122.88 (17) | C3—C4—C5 | 124.71 (19) |
O1—C2—C1 | 121.88 (17) | O2—C5—C4 | 128.1 (2) |
C4—C3—C8 | 125.27 (18) | O3—C5—C4 | 109.46 (17) |
N1—C3—C8 | 112.12 (16) | ||
C3—N1—C2—O1 | 2.3 (3) | C6—O3—C5—C4 | 178.83 (17) |
C8—C3—C4—C5 | 0.2 (3) | C3—C4—C5—O3 | −171.69 (19) |
C6—O3—C5—O2 | −1.5 (3) | C5—O3—C6—C7 | −178.91 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.10 | 2.943 (2) | 165 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
The title compound, (I), is one of the products obtained from ethyl 3-amine-2-butenoate on reflux with acetic anhydride for a period of 48 h. This prochiral olefin is a model substrate studied in the asymmetric hydrogenation reaction (Hackler et al., 1985; Lubell et al., 1991). The structure determination of (I) was conducted in order to obtain more stereochemical information about the behaviour of these kinds of substrates in hydrogenation reactions.
The crystal structure of (I) (Fig. 1) shows that the molecule is nearly planar. The angles C3—C4—C5 [124.71 (19)°] and C4—C3—C8 [125.27 (18)°] are wider and N1—C3—C8 [112.12 (16)°] narrower than the value of 120°. This results in a close mutual repulsion between the methyl group on C3 and the carbonyl group on C4 (Table 1). The molecules in the crystal structure are interconnected by N—H···O hydrogen bonding (Table 2). As shown in the packing diagram (Fig. 2), the N—H···O hydrogen bond links the molecules along b axis.