Abstract
C15H19N2O5Cl, triclinic, P1̅ (no. 2), a = 8.2232(9) Å, b = 8.5833(10) Å, c = 12.5916(13) Å, β = 100.713(5)°, V = 833.39 Å3, Z = 2, Rgt(F) = 0.0331, wRref(F2) = 0.0870, T = 173 K.
The crystal structure is shown in the figure. For clarity hydrogen atoms not involved in hydrogen bonds are omitted. Tables 1–3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colorless, block, size 0.19×0.21×0.22 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 2.55 cm−1 |
| Diffractometer, scan mode: | Nonius Kappa CCD diffractometer, 1.2° φ scans and ω scans |
| 2θmax: | 55.76° |
| N(hkl)measured, N(hkl)unique: | 29079, 3956 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 3343 |
| N(param)refined: | 217 |
| Programs: | OLEX2 [7], SHELX [8] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | Site | x | y | z | Uiso |
|---|---|---|---|---|---|
| H(1) | 2i | 0.153(2) | 0.474(2) | 0.411(2) | 0.038(4) |
| H(2) | 2i | −0.012(2) | 0.476(2) | 0.345(1) | 0.033(4) |
| H(1A) | 2i | 0.1811 | 0.7386 | 0.4393 | 0.039 |
| H(1B) | 2i | 0.0747 | 0.7215 | 0.3148 | 0.039 |
| H(2A) | 2i | 0.3416 | 0.7883 | 0.2863 | 0.048 |
| H(2B) | 2i | 0.4218 | 0.7057 | 0.3817 | 0.048 |
| H(6A) | 2i | −0.2503 | 0.4221 | 0.0100 | 0.044 |
| H(6B) | 2i | −0.3653 | 0.4571 | 0.0978 | 0.044 |
| H(7A) | 2i | −0.3025 | 0.1473 | 0.0119 | 0.090 |
| H(7B) | 2i | −0.4806 | 0.1981 | −0.0162 | 0.090 |
| H(7C) | 2i | −0.4069 | 0.1794 | 0.1064 | 0.090 |
| H(8) | 2i | 0.2324 | 0.2095 | 0.1805 | 0.026 |
| H(9A) | 2i | 0.4382 | 0.3693 | 0.3448 | 0.032 |
| H(9B) | 2i | 0.3192 | 0.2939 | 0.4180 | 0.032 |
| H(11) | 2i | 0.0310 | 0.1945 | 0.4137 | 0.038 |
| H(12) | 2i | −0.1941 | −0.0171 | 0.4115 | 0.045 |
| H(13) | 2i | −0.3098 | −0.2287 | 0.2521 | 0.043 |
| H(14) | 2i | −0.1981 | −0.2303 | 0.0945 | 0.041 |
| H(15) | 2i | 0.0271 | −0.0194 | 0.0958 | 0.034 |
Atomic displacement parameters (Å2).
| Atom | Site | x | y | z | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|---|---|---|
| Cl(1) | 2i | 0.24337(4) | 0.47941(4) | 0.58480(2) | 0.0242(2) | 0.0428(2) | 0.0225(2) | 0.0037(1) | 0.0060(1) | 0.0046(1) |
| O(1) | 2i | 0.3818(1) | 0.5069(1) | 0.16648(8) | 0.0297(5) | 0.0402(6) | 0.0362(5) | 0.0066(4) | 0.0156(4) | 0.0130(4) |
| O(2) | 2i | 0.0185(1) | 0.3238(1) | 0.04996(8) | 0.0336(5) | 0.0517(6) | 0.0214(5) | 0.0130(5) | 0.0071(4) | 0.0016(4) |
| O(3) | 2i | −0.1367(1) | 0.4202(1) | 0.16694(7) | 0.0233(4) | 0.0451(6) | 0.0232(4) | 0.0114(4) | 0.0044(4) | 0.0036(4) |
| O(4) | 2i | 0.4942(2) | 0.0941(2) | 0.4191(1) | 0.0776(9) | 0.0458(7) | 0.0420(6) | 0.0277(6) | −0.0006(6) | 0.0181(5) |
| O(5) | 2i | 0.4218(1) | 0.0468(1) | 0.24075(9) | 0.0508(6) | 0.0412(6) | 0.0396(6) | 0.0242(5) | 0.0146(5) | 0.0081(5) |
| N(1) | 2i | 0.0985(1) | 0.4969(1) | 0.34737(9) | 0.0229(5) | 0.0253(5) | 0.0202(5) | 0.0056(4) | 0.0059(4) | 0.0031(4) |
| N(2) | 2i | 0.4272(1) | 0.1260(1) | 0.3338(1) | 0.0301(6) | 0.0273(6) | 0.0340(6) | 0.0078(5) | 0.0060(5) | 0.0105(5) |
| C(1) | 2i | 0.1594(2) | 0.6786(2) | 0.3605(1) | 0.0403(8) | 0.0218(6) | 0.0343(7) | 0.0067(5) | 0.0105(6) | 0.0016(5) |
| C(2) | 2i | 0.3230(2) | 0.6932(2) | 0.3196(1) | 0.0432(8) | 0.0266(7) | 0.0458(9) | −0.0034(6) | 0.0165(7) | 0.0011(6) |
| C(3) | 2i | 0.2988(2) | 0.5373(2) | 0.2339(1) | 0.0228(6) | 0.0253(6) | 0.0268(6) | 0.0037(5) | 0.0045(5) | 0.0100(5) |
| C(4) | 2i | 0.1455(2) | 0.4104(1) | 0.24573(9) | 0.0209(5) | 0.0225(6) | 0.0194(5) | 0.0041(4) | 0.0071(4) | 0.0031(4) |
| C(5) | 2i | 0.0008(2) | 0.3792(2) | 0.1412(1) | 0.0232(6) | 0.0233(6) | 0.0228(6) | 0.0043(5) | 0.0060(5) | 0.0060(5) |
| C(6) | 2i | −0.2865(2) | 0.3896(2) | 0.0747(1) | 0.0248(7) | 0.0528(9) | 0.0305(7) | 0.0121(6) | −0.0005(5) | 0.0080(6) |
| C(7) | 2i | −0.3769(2) | 0.2134(3) | 0.0413(2) | 0.0360(9) | 0.066(1) | 0.064(1) | −0.0067(8) | −0.0061(8) | 0.014(1) |
| C(8) | 2i | 0.1964(2) | 0.2466(1) | 0.2511(1) | 0.0213(5) | 0.0220(6) | 0.0220(6) | 0.0045(4) | 0.0063(4) | 0.0035(4) |
| C(9) | 2i | 0.3523(2) | 0.2728(2) | 0.3457(1) | 0.0243(6) | 0.0238(6) | 0.0291(6) | 0.0060(5) | 0.0036(5) | 0.0047(5) |
| C(10) | 2i | 0.0500(2) | 0.1110(2) | 0.2537(1) | 0.0226(6) | 0.0215(6) | 0.0248(6) | 0.0043(5) | 0.0055(5) | 0.0051(5) |
| C(11) | 2i | −0.0158(2) | 0.1092(2) | 0.3484(1) | 0.0358(7) | 0.0271(7) | 0.0293(7) | 0.0025(5) | 0.0127(6) | 0.0022(5) |
| C(12) | 2i | −0.1495(2) | −0.0172(2) | 0.3471(1) | 0.0401(8) | 0.0333(7) | 0.0419(8) | 0.0043(6) | 0.0223(7) | 0.0090(6) |
| C(13) | 2i | −0.2180(2) | −0.1431(2) | 0.2528(1) | 0.0267(7) | 0.0283(7) | 0.0511(9) | 0.0011(5) | 0.0117(6) | 0.0096(6) |
| C(14) | 2i | −0.1521(2) | −0.1437(2) | 0.1593(1) | 0.0305(7) | 0.0273(7) | 0.0363(7) | −0.0005(5) | 0.0025(6) | 0.0008(6) |
| C(15) | 2i | −0.0182(2) | −0.0176(2) | 0.1600(1) | 0.0303(7) | 0.0272(6) | 0.0255(6) | 0.0035(5) | 0.0064(5) | 0.0035(5) |
Source of material
1-tert-Butyl-2-ethyl-3-oxopyrrolidine-1,2-dicarboxylate (0.1 g, 0.39 mM), nitrostyrene (0.069 g, 0.47 mM) and L-proline (20 mol %) in DMSO (2 mL) was stirred for 72 h at RT. The reaction progress was monitored by TLC. (Rf = 0.3 using 15% ethyl acetate/hexane). The reaction was quenched with water and the product was extracted using dichloromethane. The solvent was completely evaporated and the residual oil was purified using a silica column. Pure fractions were concentrated and treated with 20% trifluoroacetic acid in DCM and stirred for 4 h. The solution was basified with saturated NaHCO3. The organic layer was separated and then concentrated to dryness. Yield 72%. m.p = 449 K. Crystals suitable for X-ray analysis were grown in methanolic HCl and ethyl acetate.
Experimental details
X-ray single crystal diffraction data were collected on a Nonius κ-CCD diffractometer. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). Absorption correction was performed using SADABS [1]. All hydrogen atoms, except H3, were placed in idealised positions and refined in riding models with Uiso assigned the values to be 1.2 or 1.5 times those of their parent atoms and the constraint distances of C—H ranging from 0.95 Å to 1.00 Å. The hydrogen atoms H1 and H2 were located in the electron difference maps and refined freely.
Discussion
Oxopyrrolidine moieties have a proline backbone and are used in a wide range of applications such as ACE inhibitors, antibacterial, antitumor and asymmetric catalysis [2–5]. Here we report for the first time the single crystal structure of a 4-oxopyrrolidine derivative. The five membered oxopyrrolidine ring N(1)–C(1) bond is twisted with the pseudorotation parameters P (188.6(1)°), τ (M) (34.3(1)°) [6], puckering amplitude Q of 0.3246(14) Å, and φ is 26.5(3)°. The nitrogen of oxopyrrolidine is protonated and two adjacent molecules with quaternary nitrogen are interconnected through N(+)-H⋯Cl(−) hydrogen bonds to form a cyclic motif classified by the graph set descriptor R24(8) in which the chloride ions are hydrogen bonded to the hydrogen of quaternay nitrogen of oxopyrrolidine moieties in a bifurcated manner. Such dimeric units grow further along the a axis.
Acknowledgements:
The authors wish to thank Dr. Hong Su from the Chemistry Department of the University of Cape Town for assistance with the X-ray data collection and refinement.
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©2016 Nilay Bhatt et al., published by De Gruyter.
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