Methyl (E) 3 acet­amido 2 pentenoate

Acta Cryst.(2002). E58, o1421±o1422 DOI: 10.1107/S1600536802021396 Chen, Guo and Zhou C₈H₁₃NO₃

o1421

organic papers

Acta Crystallographica Section E

Structure Reports

Online ISSN 1600-5368

Methyl (

E

)-3-acetamido-2-pentenoate

Xuanhua Chen,a,b_Rongwei

Guoa,b_{* and Zhongyuan Zhou}b

a_{Department of Chemistry, Central China}

Normal University, Wuhan, People's Republic of China, andb_{Department of Applied Biology}

and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 294 K

Mean(C±C) = 0.004 AÊ

Rfactor = 0.059

wRfactor = 0.155

Data-to-parameter ratio = 19.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C8H13NO3, is anEisomer and there are two molecules in the asymmetric unit. The molecules are assembled into chains, along the a axis, via intermolecular interactions.

Comment

The title compound, (I), is one of the products obtained from reaction of methyl 3-amine-2-pentenoate with acetic anhy-dride under re¯ux for 24 h. This prochiral ole®n is a model substrate studied in the asymmetric hydrogenation reaction (Hackler & Wickiser, 1985; Lubellet al., 1991).

The structure determination of (I) was conducted in order to obtain more stereochemical information about the beha-viour of these kinds of substrates in hydrogenation reactions. The crystal structure of (I) contains two independent mol-ecules in the asymmetric unit (Fig. 1). A pairwise comparison between these two molecules shows no signi®cant differences in their bond lengths or angles, although the conformations of the two molecules are different. The C1ÐC2 bond distance of 1.338 (3) AÊ is indicative of double-bond character. The angles C1ÐC2ÐC3 [125.1 (2)_{] and C2ÐC1ÐC5 [124.8 (2)] are} larger, and N1ÐC1ÐC5 [112.0 (2)_{] smaller than 120. This} results in a close mutual repulsion between the ethyl group on C1 and carbonyl group on C3.

Received 1 November 2002 Accepted 20 November 2002 Online 30 November 2002

Figure 1

The molecules are interconnected by NÐH O hydrogen bonding in the crystal (Table 2). As illustrated in Fig. 2, the hydrogen bonding links the molecules along theaaxis.

Experimental

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 at room temperature.1_H

NMR (400 MHz, acetone-d6, Bruker):1.09±1.12 (t, J= 7.5 Hz, 3H),

2.06 (s, 3H), 2.71±2.77 (q, J= 7.5 Hz, 2H), 3.59 (s, 3H), 6.87 (s, 1H), 8.75 (br, 1H).

Crystal data C8H13NO3

Mr= 171.19

Monoclinic,P21=n

a= 9.718 (7) AÊ

b= 12.673 (9) AÊ

c= 15.653 (7) AÊ

= 104.825 (15)

V= 1864 (2) AÊ3

Z= 8

Dx= 1.220 Mg mÿ3

MoKradiation Cell parameters from 2920

re¯ections

= 1±27.5 = 0.09 mmÿ1

T= 294 (2) K Needle, colorless 0.380.120.10 mm Data collection

Siemens SMART CCD area-detector diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.965,Tmax= 0.991

12544 measured re¯ections

4308 independent re¯ections 1544 re¯ections withI> 2(I)

Rint= 0.057

max= 27.6

h=ÿ12!12

k=ÿ15!16

l=ÿ16!20 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.059}

wR(F2_{) = 0.156}

S= 1.06 4308 re¯ections 223 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.05P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.17 e AÊÿ3

min=ÿ0.19 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC3 1.190 (3)

O3ÐC7 1.219 (3)

N1ÐC7 1.355 (3)

N1ÐC1 1.391 (3)

C1ÐC2 1.338 (3)

C2ÐC3 1.445 (4)

O4ÐC11 1.198 (3)

O6ÐC15 1.222 (3)

N2ÐC15 1.356 (3)

N2ÐC9 1.388 (3)

C9ÐC10 1.334 (3)

C10ÐC11 1.443 (3)

C2ÐC1ÐC5 124.8 (2) N1ÐC1ÐC5 112.0 (2) C1ÐC2ÐC3 125.1 (2) O1ÐC3ÐO2 120.9 (3)

O1ÐC3ÐC2 129.4 (3) O2ÐC3ÐC2 109.7 (2) O3ÐC7ÐN1 123.0 (2) O3ÐC7ÐC8 121.7 (2)

N1ÐC1ÐC2ÐC3 ÿ176.8 (3) C5ÐC1ÐC2ÐC3 2.6 (4) C4ÐO2ÐC3ÐO1 0.3 (4)

C4ÐO2ÐC3ÐC2 ÿ179.4 (2) C1ÐN1ÐC7ÐO3 ÿ4.0 (5) C1ÐN1ÐC7ÐC8 175.5 (3)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1A O6 0.86 2.11 2.967 (3) 173 N2ÐH2A O3i _{0.86 2.08 2.936 (3) 174}

Symmetry code: (i)xÿ1;y;z.

H atoms were included in the riding-model approximation, with Uisovalues equal toUeqof the atom to which they are bound.

Data collection: SMART (Siemens, 1995); cell re®nement: SMART; data reduction: SAINT (Siemens, 1995) and SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

We thank the Hong Kong Polytechnic University ASD Fund for ®nancial support of this study.

References

Hackler, R. E. & Wickiser, D. I. (1985). UK Patent GB 2141712.

Lubell, W. D., Kitamura, M. & Noyori, R. (1991).Tetrahedron: Asymmetry,2, 543±554.

Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Siemens (1995).SAINT(Version 5.0),SMART(Version 5.0) and SHELXTL-NT(Version 5.10). Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Zhu, G. X., Chen, Z. G. & Zhang, X. M. (1999).J. Org. Chem.64, 6907±6910. Figure 2

supporting information

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supporting information

Acta Cryst. (2002). E58, o1421–o1422 [doi:10.1107/S1600536802021396]

Methyl (

E

)-3-acetamido-2-pentenoate

Xuanhua Chen, Rongwei Guo and Zhongyuan Zhou

S1. Comment

The title compound, (I), is one of the products obtained from reaction of methyl 3-amine-2-pentenoate with acetic

anhydride at reflux for 24 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 behaviours of these kinds of substrates in hydrogenation reaction. The crystal

structure of (I) contains two independent molecules in the asymmetric unit (Fig. 1). A pairwise comparison between these

two molecules shows no significant differences in their bond lengths or angles although the conformations of the two

molecules are different (Table 1). The C1—C2 bond distance of 1.338 (3) Å is indicative of double-bond character. The

angles of C1—C2—C3 [125.1 (2)°], C2—C1—C5 [124.8 (2)°] are larger and N1—C1—C5 [112.0 (2)°] smaller than

120°. This results in a close mutual repulsion between the ethyl group on C1 and carbonyl group on C3.

The molecules are interconnected by N—H···O hydrogen bonding in the crystal (Table 2). As illustrated in Fig. 2, the

hydrogen bonding links the molecules along the a axis.

S2. Experimental

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 at room temperature. 1_{H NMR (400 MHz, acetone-d} 6,

Bruker): δ 1.09–1.12 (t, J = 7.5 Hz, 3H), 2.06 (s, 3H), 2.71–2.77 (q, J = 7.5 Hz, 2H), 3.59 (s, 3H), 6.87 (s, 1H), 8.75 (br,

1H).

S3. Refinement

H atoms were included in the riding-model approximation, with Uiso values equal to Ueq of the atom to which they were

Figure 1

The molecular structure of (I), showing ellipsoids at the 50% probability level (Siemens, 1995).

Figure 2

Packing diagram for (I). Hydrogen bonds are indicated by dashed lines.

(I)

Crystal data

C8H13NO3

Mr = 171.19 Monoclinic, P21/n Hall symbol: -P 2yn

a = 9.718 (7) Å

b = 12.673 (9) Å

c = 15.653 (7) Å

supporting information

sup-3

V = 1864 (2) Å3

Z = 8

F(000) = 736

Dx = 1.220 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2920 reflections

θ = 1–27.5°

µ = 0.09 mm−1

T = 294 K Needle, colorless 0.38 × 0.12 × 0.10 mm

Data collection

Siemens CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.965, Tmax = 0.991

12544 measured reflections 4308 independent reflections 1544 reflections with I > 2σ(I)

Rint = 0.057

θmax = 27.6°, θmin = 2.7°

h = −12→12

k = −15→16

l = −16→20

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.059}

wR(F2_{) = 0.156}

S = 1.06 4308 reflections 223 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.17 e Å−3 Δρmin = −0.19 e Å−3

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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

O1 0.9833 (2) 0.69319 (16) 0.09679 (19) 0.1094 (9) O2 1.18911 (19) 0.62579 (15) 0.08953 (14) 0.0753 (6) O3 1.10959 (18) 0.30060 (14) 0.17560 (15) 0.0760 (7) N1 0.8894 (2) 0.36964 (16) 0.15820 (14) 0.0540 (6)

H1A 0.8036 0.3530 0.1580 0.065*

C1 0.9105 (2) 0.4745 (2) 0.13860 (18) 0.0507 (7)

C2 1.0278 (3) 0.5087 (2) 0.11740 (17) 0.0516 (7)

H2 1.0956 0.4587 0.1130 0.062*

C3 1.0572 (3) 0.6175 (2) 0.10079 (19) 0.0593 (8)

C4 1.2351 (4) 0.7300 (3) 0.0731 (2) 0.0991 (12)

H4B 1.3160 0.7250 0.0487 0.149*

H4C 1.2608 0.7687 0.1276 0.149*

C5 0.7856 (3) 0.5444 (2) 0.1451 (2) 0.0661 (9)

H5A 0.7403 0.5150 0.1883 0.079*

H5B 0.8202 0.6143 0.1649 0.079*

C6 0.6797 (3) 0.5522 (3) 0.0579 (2) 0.1045 (13)

H6A 0.7240 0.5828 0.0156 0.157*

H6B 0.6016 0.5958 0.0634 0.157*

H6C 0.6451 0.4830 0.0385 0.157*

C7 0.9857 (3) 0.2902 (2) 0.17752 (19) 0.0571 (8)

C8 0.9303 (3) 0.1880 (2) 0.2023 (2) 0.0834 (11)

H8A 0.8976 0.1452 0.1505 0.125*

H8B 0.8528 0.2013 0.2285 0.125*

H8C 1.0049 0.1516 0.2440 0.125*

O4 0.4679 (2) −0.10593 (16) 0.11316 (17) 0.0964 (8) O5 0.68342 (19) −0.04784 (14) 0.11396 (13) 0.0686 (6) O6 0.60226 (18) 0.29268 (14) 0.16089 (14) 0.0742 (7) N2 0.3890 (2) 0.22289 (16) 0.16423 (14) 0.0524 (6)

H2A 0.3053 0.2408 0.1677 0.063*

C9 0.4066 (2) 0.1162 (2) 0.14978 (17) 0.0459 (7)

C10 0.5211 (3) 0.07784 (19) 0.12828 (17) 0.0485 (7)

H10 0.5885 0.1258 0.1194 0.058*

C11 0.5477 (3) −0.0328 (2) 0.11787 (18) 0.0555 (8) C12 0.7239 (3) −0.1552 (2) 0.1038 (2) 0.0859 (11)

H12A 0.7171 −0.1954 0.1546 0.129*

H12B 0.8202 −0.1570 0.0986 0.129*

H12C 0.6616 −0.1848 0.0517 0.129*

C13 0.2837 (3) 0.0516 (2) 0.16213 (18) 0.0543 (8)

H13A 0.2458 0.0842 0.2074 0.065*

H13B 0.3178 −0.0181 0.1828 0.065*

C14 0.1658 (3) 0.0409 (2) 0.0786 (2) 0.0779 (10)

H14A 0.1314 0.1096 0.0578 0.117*

H14B 0.0895 0.0002 0.0906 0.117*

H14C 0.2015 0.0059 0.0343 0.117*

C15 0.4841 (3) 0.3031 (2) 0.17365 (19) 0.0549 (8)

C16 0.4349 (3) 0.4060 (2) 0.2011 (2) 0.0767 (10)

H16A 0.5118 0.4394 0.2433 0.115*

H16B 0.3571 0.3942 0.2274 0.115*

H16C 0.4039 0.4507 0.1502 0.115*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C2 0.0353 (15) 0.0428 (17) 0.078 (2) 0.0040 (13) 0.0174 (15) 0.0014 (14) C3 0.0494 (18) 0.049 (2) 0.081 (2) −0.0011 (15) 0.0205 (17) −0.0001 (16) C4 0.093 (3) 0.067 (2) 0.144 (3) −0.039 (2) 0.044 (2) 0.000 (2) C5 0.0452 (17) 0.056 (2) 0.097 (3) 0.0040 (14) 0.0190 (18) 0.0010 (16) C6 0.058 (2) 0.104 (3) 0.132 (4) 0.023 (2) −0.011 (2) −0.009 (2) C7 0.0365 (16) 0.0494 (19) 0.091 (2) 0.0052 (14) 0.0263 (17) 0.0047 (15) C8 0.057 (2) 0.058 (2) 0.146 (3) 0.0071 (16) 0.046 (2) 0.019 (2) O4 0.0780 (16) 0.0512 (14) 0.172 (2) −0.0170 (12) 0.0546 (16) −0.0154 (14) O5 0.0581 (13) 0.0486 (13) 0.1061 (17) 0.0146 (10) 0.0337 (12) −0.0038 (11) O6 0.0350 (11) 0.0538 (13) 0.144 (2) −0.0060 (9) 0.0408 (12) −0.0171 (12) N2 0.0267 (11) 0.0465 (15) 0.0864 (18) 0.0005 (10) 0.0189 (12) −0.0055 (12) C9 0.0323 (14) 0.0467 (18) 0.0577 (18) −0.0035 (13) 0.0099 (13) −0.0001 (14) C10 0.0366 (15) 0.0399 (17) 0.072 (2) −0.0009 (13) 0.0185 (14) −0.0043 (14) C11 0.0519 (18) 0.049 (2) 0.070 (2) 0.0029 (16) 0.0225 (16) 0.0013 (16) C12 0.104 (3) 0.054 (2) 0.110 (3) 0.0340 (19) 0.046 (2) 0.0111 (18) C13 0.0395 (16) 0.0590 (19) 0.066 (2) −0.0068 (13) 0.0170 (15) 0.0015 (14) C14 0.0469 (18) 0.094 (3) 0.089 (3) −0.0220 (16) 0.0105 (18) −0.0117 (19) C15 0.0360 (16) 0.0464 (18) 0.085 (2) −0.0009 (13) 0.0204 (16) −0.0071 (15) C16 0.0472 (18) 0.057 (2) 0.129 (3) 0.0012 (15) 0.0281 (19) −0.0221 (19)

Geometric parameters (Å, º)

O1—C3 1.190 (3) O4—C11 1.198 (3)

O2—C3 1.342 (3) O5—C11 1.349 (3)

O2—C4 1.438 (3) O5—C12 1.436 (3)

O3—C7 1.219 (3) O6—C15 1.222 (3)

N1—C7 1.355 (3) N2—C15 1.356 (3)

N1—C1 1.391 (3) N2—C9 1.388 (3)

N1—H1A 0.8600 N2—H2A 0.8600

C1—C2 1.338 (3) C9—C10 1.334 (3)

C1—C5 1.527 (3) C9—C13 1.500 (3)

C2—C3 1.445 (4) C10—C11 1.443 (3)

C2—H2 0.9300 C10—H10 0.9300

C4—H4A 0.9600 C12—H12A 0.9600

C4—H4B 0.9600 C12—H12B 0.9600

C4—H4C 0.9600 C12—H12C 0.9600

C5—C6 1.488 (4) C13—C14 1.508 (4)

C5—H5A 0.9700 C13—H13A 0.9700

C5—H5B 0.9700 C13—H13B 0.9700

C6—H6A 0.9600 C14—H14A 0.9600

C6—H6B 0.9600 C14—H14B 0.9600

C6—H6C 0.9600 C14—H14C 0.9600

C7—C8 1.492 (4) C15—C16 1.489 (3)

C8—H8A 0.9600 C16—H16A 0.9600

C8—H8B 0.9600 C16—H16B 0.9600

C8—H8C 0.9600 C16—H16C 0.9600

C7—N1—C1 128.8 (2) C15—N2—C9 129.7 (2)

C7—N1—H1A 115.6 C15—N2—H2A 115.1

C1—N1—H1A 115.6 C9—N2—H2A 115.1

C2—C1—N1 123.2 (2) C10—C9—N2 122.8 (2)

C2—C1—C5 124.8 (2) C10—C9—C13 125.2 (2)

N1—C1—C5 112.0 (2) N2—C9—C13 112.0 (2)

C1—C2—C3 125.1 (2) C9—C10—C11 124.6 (2)

C1—C2—H2 117.5 C9—C10—H10 117.7

C3—C2—H2 117.5 C11—C10—H10 117.7

O1—C3—O2 120.9 (3) O4—C11—O5 120.9 (3)

O1—C3—C2 129.4 (3) O4—C11—C10 128.8 (3)

O2—C3—C2 109.7 (2) O5—C11—C10 110.3 (2)

O2—C4—H4A 109.5 O5—C12—H12A 109.5

O2—C4—H4B 109.5 O5—C12—H12B 109.5

H4A—C4—H4B 109.5 H12A—C12—H12B 109.5

O2—C4—H4C 109.5 O5—C12—H12C 109.5

H4A—C4—H4C 109.5 H12A—C12—H12C 109.5

H4B—C4—H4C 109.5 H12B—C12—H12C 109.5

C6—C5—C1 110.6 (2) C9—C13—C14 113.0 (2)

C6—C5—H5A 109.5 C9—C13—H13A 109.0

C1—C5—H5A 109.5 C14—C13—H13A 109.0

C6—C5—H5B 109.5 C9—C13—H13B 109.0

C1—C5—H5B 109.5 C14—C13—H13B 109.0

H5A—C5—H5B 108.1 H13A—C13—H13B 107.8

C5—C6—H6A 109.5 C13—C14—H14A 109.5

C5—C6—H6B 109.5 C13—C14—H14B 109.5

H6A—C6—H6B 109.5 H14A—C14—H14B 109.5

C5—C6—H6C 109.5 C13—C14—H14C 109.5

H6A—C6—H6C 109.5 H14A—C14—H14C 109.5

H6B—C6—H6C 109.5 H14B—C14—H14C 109.5

O3—C7—N1 123.0 (2) O6—C15—N2 123.0 (2)

O3—C7—C8 121.7 (2) O6—C15—C16 121.7 (2)

N1—C7—C8 115.4 (2) N2—C15—C16 115.3 (2)

C7—C8—H8A 109.5 C15—C16—H16A 109.5

C7—C8—H8B 109.5 C15—C16—H16B 109.5

H8A—C8—H8B 109.5 H16A—C16—H16B 109.5

C7—C8—H8C 109.5 C15—C16—H16C 109.5

H8A—C8—H8C 109.5 H16A—C16—H16C 109.5

H8B—C8—H8C 109.5 H16B—C16—H16C 109.5

C7—N1—C1—C2 14.8 (4) C15—N2—C9—C10 −11.3 (4)

C7—N1—C1—C5 −164.6 (3) C15—N2—C9—C13 168.1 (3)

N1—C1—C2—C3 −176.8 (3) N2—C9—C10—C11 176.1 (2)

C5—C1—C2—C3 2.6 (4) C13—C9—C10—C11 −3.2 (4)

C4—O2—C3—O1 0.3 (4) C12—O5—C11—O4 0.1 (4)

C4—O2—C3—C2 −179.4 (2) C12—O5—C11—C10 179.8 (2)

C1—C2—C3—O1 −5.5 (5) C9—C10—C11—O4 12.2 (5)

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C2—C1—C5—C6 88.7 (3) C10—C9—C13—C14 −91.6 (3)

N1—C1—C5—C6 −91.8 (3) N2—C9—C13—C14 89.0 (3)

C1—N1—C7—O3 −4.0 (5) C9—N2—C15—O6 8.2 (5)

C1—N1—C7—C8 175.5 (3) C9—N2—C15—C16 −171.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1A···O6 0.86 2.11 2.967 (3) 173

N2—H2A···O3i _{0.86 2.08 2.936 (3) 174}