organic compounds
2,5-Dioxopyrrolidin-1-yl 2-methylprop-2-enoate
aChemistry Department, United States Naval Academy, 572M Holloway Road, Annapolis, Maryland 21401, USA, and bDepartment of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA
*Correspondence e-mail: wpearson@usna.edu
In the title compound, C8H9NO4, the pyrrolidine ring (r.m.s. deviation 0.014 Å) is almost normal to the mean plane of the propenoate group (r.m.s deviation 0.028 Å), making a dihedral angle of 86.58 (4)°. In the crystal, molecules are linked via pairs of weak C—H⋯O hydrogen bonds, forming inversion dimers which stack along the c axis.
CCDC reference: 990423
Related literature
For synthetic procedures, see: Batz et al. (1972); Rathfon & Tew (2008). For polymerization and controlled (ATRP) polymerizations to form homo- and copolymers, see: Batz et al. (1972); Rathfon & Tew (2008). For a background on post-polymerization modification to create functional polymers, see: Gauthier et al. (2009). For a review of topochemical polymerization in crystals, see: Matsumoto (2003). For a disscussion addressing the conformation of methyl substituents on see: Deslongchamps & Deslongchamps (2011).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Supporting information
CCDC reference: 990423
10.1107/S1600536814005170/zq2217sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005170/zq2217Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005170/zq2217Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536814005170/zq2217Isup4.cml
Crystals of the title compound, C8H9NO4, were grown unintentionally from slow evaporation of a solution of the compound in 1:4 ethyl acetate:hexanes at 0 °C.
Although all of the H-atoms were located in difference maps, H-atoms were placed at idealized positions and refined with a riding model having Uiso(H) = 1.2 times Ueq(C).
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C8H9NO4 | F(000) = 384 |
Mr = 183.16 | Dx = 1.397 Mg m−3 Dm = 1.337 (2) Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6137 (8) Å | Cell parameters from 8309 reflections |
b = 10.9317 (9) Å | θ = 2.2–25.3° |
c = 8.4911 (7) Å | µ = 0.11 mm−1 |
β = 102.522 (2)° | T = 173 K |
V = 871.14 (12) Å3 | Parallelpiped, colourless |
Z = 4 | 0.24 × 0.14 × 0.07 mm |
Bruker Kappa APEXII DUO diffractometer | 1595 independent reflections |
Radiation source: a micro-focus source with X-ray optics for beam focussing and collimation | 1353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 512 pixels mm-1 | θmax = 25.3°, θmin = 2.2° |
combination of ω and phi scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −13→13 |
Tmin = 0.884, Tmax = 1.000 | l = −10→10 |
20817 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0278P)2 + 0.472P] where P = (Fo2 + 2Fc2)/3 |
1595 reflections | (Δ/σ)max < 0.001 |
119 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C8H9NO4 | V = 871.14 (12) Å3 |
Mr = 183.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6137 (8) Å | µ = 0.11 mm−1 |
b = 10.9317 (9) Å | T = 173 K |
c = 8.4911 (7) Å | 0.24 × 0.14 × 0.07 mm |
β = 102.522 (2)° |
Bruker Kappa APEXII DUO diffractometer | 1595 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1353 reflections with I > 2σ(I) |
Tmin = 0.884, Tmax = 1.000 | Rint = 0.042 |
20817 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.19 e Å−3 |
1595 reflections | Δρmin = −0.17 e Å−3 |
119 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. CheckCIF detected one Alert level C stating that a large K value of 2.279 was detected in the Analysis of Variance. Examination of the SHELX output does reveal one large K value (1.967) for the Fc/Fc(max of 0.000). Examination of the K values as a function of resolution shows no large K values from inf to 0.83 Å. Our conclusion is that the large K value results from very weak relections in the 0.80 - 0.60 A region and should have a neglibile effect upon the final structural results while the inclusion of the data would minimize termination effects in the calculation of electron density. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.82074 (17) | 0.05447 (15) | 0.09507 (19) | 0.0323 (4) | |
H1A | 0.8376 | 0.0287 | −0.0110 | 0.039* | |
H1B | 0.7895 | −0.0176 | 0.1490 | 0.039* | |
C2 | 0.95609 (18) | 0.10915 (15) | 0.19895 (19) | 0.0326 (4) | |
H2A | 0.9894 | 0.0594 | 0.2973 | 0.039* | |
H2B | 1.0329 | 0.1126 | 0.1380 | 0.039* | |
C3 | 0.91646 (17) | 0.23566 (15) | 0.24251 (18) | 0.0301 (4) | |
C4 | 0.71008 (17) | 0.15357 (14) | 0.07441 (18) | 0.0283 (4) | |
C5 | 0.72829 (16) | 0.44523 (14) | 0.06764 (17) | 0.0261 (3) | |
C6 | 0.66346 (16) | 0.56484 (14) | 0.09024 (18) | 0.0270 (4) | |
C7 | 0.6865 (2) | 0.66054 (16) | −0.0276 (2) | 0.0420 (4) | |
H7A | 0.6435 | 0.7377 | −0.0037 | 0.063* | |
H7B | 0.6422 | 0.6342 | −0.1373 | 0.063* | |
H7C | 0.7890 | 0.6723 | −0.0188 | 0.063* | |
C8 | 0.59118 (17) | 0.58160 (15) | 0.20439 (19) | 0.0324 (4) | |
H8A | 0.5800 | 0.5160 | 0.2740 | 0.039* | |
H8B | 0.5504 | 0.6592 | 0.2168 | 0.039* | |
N1 | 0.77548 (14) | 0.25062 (11) | 0.16597 (15) | 0.0289 (3) | |
O1 | 0.98688 (13) | 0.31280 (11) | 0.32386 (15) | 0.0441 (3) | |
O2 | 0.58963 (13) | 0.15423 (11) | −0.00275 (15) | 0.0408 (3) | |
O3 | 0.70452 (12) | 0.35922 (9) | 0.17939 (13) | 0.0319 (3) | |
O4 | 0.79410 (13) | 0.42090 (11) | −0.03174 (14) | 0.0402 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0440 (10) | 0.0246 (8) | 0.0283 (8) | 0.0082 (7) | 0.0076 (7) | −0.0019 (7) |
C2 | 0.0377 (9) | 0.0288 (9) | 0.0328 (8) | 0.0099 (7) | 0.0108 (7) | 0.0026 (7) |
C3 | 0.0382 (9) | 0.0269 (9) | 0.0264 (8) | 0.0032 (7) | 0.0097 (7) | 0.0037 (7) |
C4 | 0.0385 (9) | 0.0254 (8) | 0.0234 (7) | 0.0048 (7) | 0.0118 (7) | 0.0025 (6) |
C5 | 0.0296 (8) | 0.0246 (8) | 0.0225 (7) | 0.0025 (6) | 0.0021 (6) | 0.0002 (6) |
C6 | 0.0273 (8) | 0.0210 (8) | 0.0281 (8) | 0.0019 (6) | −0.0042 (6) | −0.0022 (6) |
C7 | 0.0430 (10) | 0.0295 (9) | 0.0516 (11) | 0.0068 (8) | 0.0064 (8) | 0.0112 (8) |
C8 | 0.0356 (9) | 0.0258 (8) | 0.0321 (8) | 0.0068 (7) | −0.0009 (7) | −0.0079 (7) |
N1 | 0.0389 (8) | 0.0183 (7) | 0.0296 (7) | 0.0104 (5) | 0.0078 (6) | 0.0001 (5) |
O1 | 0.0487 (8) | 0.0335 (7) | 0.0470 (7) | −0.0019 (6) | 0.0033 (6) | −0.0072 (6) |
O2 | 0.0366 (7) | 0.0415 (7) | 0.0429 (7) | 0.0065 (5) | 0.0053 (6) | −0.0038 (6) |
O3 | 0.0460 (7) | 0.0209 (6) | 0.0323 (6) | 0.0125 (5) | 0.0164 (5) | 0.0030 (5) |
O4 | 0.0551 (8) | 0.0342 (7) | 0.0370 (7) | 0.0107 (6) | 0.0226 (6) | 0.0050 (5) |
C1—C4 | 1.502 (2) | C5—O4 | 1.1894 (18) |
C1—C2 | 1.527 (2) | C5—O3 | 1.3895 (18) |
C1—H1A | 0.9900 | C5—C6 | 1.479 (2) |
C1—H1B | 0.9900 | C6—C8 | 1.322 (2) |
C2—C3 | 1.502 (2) | C6—C7 | 1.497 (2) |
C2—H2A | 0.9900 | C7—H7A | 0.9800 |
C2—H2B | 0.9900 | C7—H7B | 0.9800 |
C3—O1 | 1.202 (2) | C7—H7C | 0.9800 |
C3—N1 | 1.380 (2) | C8—H8A | 0.9500 |
C4—O2 | 1.2005 (19) | C8—H8B | 0.9500 |
C4—N1 | 1.383 (2) | N1—O3 | 1.3862 (15) |
C4—C1—C2 | 106.17 (13) | O4—C5—C6 | 126.43 (14) |
C4—C1—H1A | 110.5 | O3—C5—C6 | 111.92 (12) |
C2—C1—H1A | 110.5 | C8—C6—C5 | 121.40 (15) |
C4—C1—H1B | 110.5 | C8—C6—C7 | 124.80 (15) |
C2—C1—H1B | 110.5 | C5—C6—C7 | 113.80 (14) |
H1A—C1—H1B | 108.7 | C6—C7—H7A | 109.5 |
C3—C2—C1 | 105.84 (13) | C6—C7—H7B | 109.5 |
C3—C2—H2A | 110.6 | H7A—C7—H7B | 109.5 |
C1—C2—H2A | 110.6 | C6—C7—H7C | 109.5 |
C3—C2—H2B | 110.6 | H7A—C7—H7C | 109.5 |
C1—C2—H2B | 110.6 | H7B—C7—H7C | 109.5 |
H2A—C2—H2B | 108.7 | C6—C8—H8A | 120.0 |
O1—C3—N1 | 124.12 (15) | C6—C8—H8B | 120.0 |
O1—C3—C2 | 130.27 (15) | H8A—C8—H8B | 120.0 |
N1—C3—C2 | 105.60 (13) | C3—N1—C4 | 117.01 (13) |
O2—C4—N1 | 124.70 (14) | C3—N1—O3 | 120.89 (13) |
O2—C4—C1 | 130.03 (15) | C4—N1—O3 | 122.09 (13) |
N1—C4—C1 | 105.28 (13) | N1—O3—C5 | 111.51 (11) |
O4—C5—O3 | 121.65 (14) | ||
C4—C1—C2—C3 | 3.14 (16) | O1—C3—N1—O3 | −0.2 (2) |
C1—C2—C3—O1 | 179.04 (17) | C2—C3—N1—O3 | −179.34 (12) |
C1—C2—C3—N1 | −1.86 (16) | O2—C4—N1—C3 | −177.73 (15) |
C2—C1—C4—O2 | 176.76 (16) | C1—C4—N1—C3 | 2.28 (18) |
C2—C1—C4—N1 | −3.24 (16) | O2—C4—N1—O3 | 1.3 (2) |
O4—C5—C6—C8 | 179.43 (16) | C1—C4—N1—O3 | −178.65 (12) |
O3—C5—C6—C8 | −0.8 (2) | C3—N1—O3—C5 | 84.50 (16) |
O4—C5—C6—C7 | 0.1 (2) | C4—N1—O3—C5 | −94.54 (16) |
O3—C5—C6—C7 | 179.94 (13) | O4—C5—O3—N1 | 4.8 (2) |
O1—C3—N1—C4 | 178.91 (15) | C6—C5—O3—N1 | −175.03 (11) |
C2—C3—N1—C4 | −0.25 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2i | 0.98 | 2.54 | 3.393 (2) | 145 |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2i | 0.98 | 2.54 | 3.393 (2) | 145 |
Symmetry code: (i) −x+1, −y+1, −z. |
Acknowledgements
WHP and SL thank Joseph Urban for his assistance in interpreting the conformational nature of the methyl H atoms in this structure. SL thanks NSF CHE1110911 for sabbatical support through the ROA program. LI thanks the NSF (grant No. CHE-1110911) for financial support.
References
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The title compound is a monomer for free radical polymerization (Batz et al., 1972) and controlled free radical (ATRP) polymerizations (Rathfon & Tew, 2008) to form homo- and copolymers. After preliminary polymerization, these polymers serve as candidates to undergo post-polymerization modification to create functional polymers (Gauthier et al., 2009). A structure determination was undertaken to investigate the possibility of free radical, topochemical polymerization of this monomer while being exposed to X-ray radiation (Matsumoto, 2003). The molecular unit is shown in Figure 1. The crystal structure reveals that no polymerization has taken place. The asymmetric unit consists of a single monomer unit packed into a monoclinic cell with a volume of 871 Å3. While analysis of the intermolecular contacts within the unit cell reveals a close contact of 3.487 Å between the carbons of adjacent double bonds (C6 and C8), this contact occurs between a pair of adjacent molecules but is not maintained with additional molecules in order to achieve a favorable pathway for polymerization. Figure 2 shows the packing in the unit cell. The molecule is composed of two planar regions. Least-squares planar analysis reveals r.m.s. deviation from planarity for the pyrrolidine ring of 0.014 Å and 0.028 Å for the propenoate portion. The two planes are essentially normal to each other with an angle of 86.58 (4) degrees between least-squares planes. The conformation of the methyl H atoms is found to be syn to the vinylic proton. This is the preferred configuration by approximately 2 kcal/mol (Deslongchamps & Deslongchamps, 2011).