organic compounds
of 1-benzyl-2-hydroxy-5-oxopyrrolidin-3-yl acetate
aDepartmento de Física, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, bDepartmento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, cDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, 05508-900 São Paulo-SP, Brazil, and dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: julio@power.ufscar.br
In the title compound, C13H15NO4, the oxopyrrolidin-3-yl ring has an with the C atom bearing the acetate group being the flap. The acetate and phenyl groups are inclined with respect to the central ring, forming dihedral angles of 50.20 (12) and 87.40 (9)°, respectively, with the least-squares plane through the ring. The dihedral angle between the acetate group and the phenyl ring is 63.22 (8)°, indicating a twisted conformation in the molecule. In the crystal, supramolecular chains along the b axis are formed by (hydroxy)O—H⋯O(ring carbonyl) hydrogen bonds. The chains are consolidated into the three-dimensional architecture by C—H⋯O interactions.
Keywords: crystal structure; oxopyrrolidin-3-yl; hydrogen bonding; conformation.
CCDC reference: 1412190
1. Related literature
For the synthesis of symmetrical 1,4-dioxanes, including the title compound, via Lewis-acid-catalysed N-acyliminium ion cyclodimerization, and for a related structure, see: Ali et al. (2015).
2. Experimental
2.1. Crystal data
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2.3. Refinement
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 1412190
https://doi.org/10.1107/S2056989015013353/hg5452sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013353/hg5452Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015013353/hg5452Isup3.cml
The title compound was prepared as described in the literature (Ali et al., 2015) and crystals were obtained from the slow evaporation of its methanol solution.
Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and were included in the
in the riding model approximation, with Uiso(H) = 1.2–1.5Ueq(C). The O-bound H-atom was treated similarly with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).For the synthesis of symmetrical 1,4-dioxanes, including the title compound, via Lewis-acid-catalysed N-acyliminium ion cyclodimerization, and for a related structure, see: Ali et al. (2015).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level. | |
Fig. 2. A view of the supramolecular chain along the b axis mediated by O—H···O hydrogen bonding shown as orange dashed lines. | |
Fig. 3. A view in projection down the b axis of the unit-cell contents. The O—H···O and C—H···O interactions shown as orange and blue dashed lines, respectively. |
C13H15NO4 | Dx = 1.290 Mg m−3 |
Mr = 249.26 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 3310 reflections |
a = 26.504 (2) Å | θ = 2.8–25.3° |
b = 6.3668 (5) Å | µ = 0.10 mm−1 |
c = 7.6040 (6) Å | T = 293 K |
V = 1283.14 (17) Å3 | Block, colourless |
Z = 4 | 0.56 × 0.40 × 0.36 mm |
F(000) = 528 |
Bruker APEXII CCD diffractometer | 2087 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.014 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25.3°, θmin = 2.8° |
Tmin = 0.673, Tmax = 0.745 | h = −31→26 |
4917 measured reflections | k = −5→7 |
2246 independent reflections | l = −9→7 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.1542P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2246 reflections | Δρmax = 0.10 e Å−3 |
165 parameters | Δρmin = −0.18 e Å−3 |
C13H15NO4 | V = 1283.14 (17) Å3 |
Mr = 249.26 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 26.504 (2) Å | µ = 0.10 mm−1 |
b = 6.3668 (5) Å | T = 293 K |
c = 7.6040 (6) Å | 0.56 × 0.40 × 0.36 mm |
Bruker APEXII CCD diffractometer | 2246 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2087 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.745 | Rint = 0.014 |
4917 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.10 e Å−3 |
2246 reflections | Δρmin = −0.18 e Å−3 |
165 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.04798 (6) | 0.8021 (3) | 0.0393 (2) | 0.0590 (4) | |
O2 | 0.10250 (7) | 0.5494 (3) | −0.0319 (3) | 0.0797 (6) | |
O3 | 0.05817 (6) | 0.6595 (2) | 0.3698 (2) | 0.0626 (5) | |
H3O | 0.0678 | 0.5486 | 0.4131 | 0.094* | |
O4 | 0.09632 (7) | 1.2919 (2) | 0.4745 (3) | 0.0736 (5) | |
N1 | 0.11194 (6) | 0.9434 (3) | 0.4315 (3) | 0.0528 (5) | |
C1 | 0.08701 (8) | 0.8984 (3) | 0.1433 (3) | 0.0540 (5) | |
H1 | 0.1175 | 0.9160 | 0.0717 | 0.065* | |
C2 | 0.09990 (8) | 0.7747 (3) | 0.3111 (3) | 0.0497 (5) | |
H2 | 0.1291 | 0.6831 | 0.2924 | 0.060* | |
C4 | 0.09357 (8) | 1.1311 (3) | 0.3844 (3) | 0.0547 (5) | |
C5 | 0.06905 (10) | 1.1103 (4) | 0.2074 (4) | 0.0614 (6) | |
H5A | 0.0799 | 1.2216 | 0.1289 | 0.074* | |
H5B | 0.0326 | 1.1139 | 0.2173 | 0.074* | |
C6 | 0.06079 (10) | 0.6229 (4) | −0.0410 (3) | 0.0594 (6) | |
C7 | 0.01803 (12) | 0.5271 (5) | −0.1385 (4) | 0.0792 (8) | |
H7A | 0.0041 | 0.4141 | −0.0706 | 0.119* | |
H7B | 0.0299 | 0.4738 | −0.2492 | 0.119* | |
H7C | −0.0075 | 0.6314 | −0.1589 | 0.119* | |
C8 | 0.13462 (9) | 0.9012 (4) | 0.6024 (3) | 0.0605 (6) | |
H8A | 0.1153 | 0.7925 | 0.6613 | 0.073* | |
H8B | 0.1328 | 1.0272 | 0.6738 | 0.073* | |
C9 | 0.18888 (8) | 0.8323 (4) | 0.5891 (3) | 0.0525 (5) | |
C10 | 0.20395 (10) | 0.6420 (4) | 0.6570 (4) | 0.0707 (7) | |
H10 | 0.1803 | 0.5528 | 0.7079 | 0.085* | |
C11 | 0.25400 (13) | 0.5831 (6) | 0.6500 (5) | 0.0973 (11) | |
H11 | 0.2643 | 0.4563 | 0.6991 | 0.117* | |
C12 | 0.28864 (12) | 0.7121 (8) | 0.5703 (5) | 0.1080 (14) | |
H12 | 0.3222 | 0.6711 | 0.5627 | 0.130* | |
C13 | 0.27379 (11) | 0.9002 (9) | 0.5023 (4) | 0.1085 (14) | |
H13 | 0.2974 | 0.9877 | 0.4491 | 0.130* | |
C14 | 0.22412 (10) | 0.9614 (6) | 0.5120 (4) | 0.0799 (9) | |
H14 | 0.2143 | 1.0905 | 0.4662 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0530 (9) | 0.0571 (9) | 0.0668 (10) | 0.0025 (7) | −0.0072 (7) | 0.0012 (8) |
O2 | 0.0751 (12) | 0.0781 (12) | 0.0861 (13) | 0.0164 (10) | 0.0149 (10) | 0.0015 (11) |
O3 | 0.0543 (8) | 0.0431 (8) | 0.0902 (12) | −0.0007 (7) | 0.0038 (8) | 0.0173 (8) |
O4 | 0.0824 (12) | 0.0420 (8) | 0.0963 (13) | −0.0005 (8) | −0.0194 (10) | 0.0025 (9) |
N1 | 0.0482 (9) | 0.0437 (9) | 0.0664 (11) | 0.0037 (8) | −0.0082 (9) | 0.0093 (8) |
C1 | 0.0446 (11) | 0.0507 (12) | 0.0667 (13) | −0.0019 (9) | −0.0034 (9) | 0.0113 (11) |
C2 | 0.0414 (10) | 0.0410 (10) | 0.0667 (13) | 0.0048 (9) | 0.0002 (9) | 0.0066 (10) |
C4 | 0.0470 (11) | 0.0385 (10) | 0.0785 (15) | −0.0031 (9) | −0.0072 (10) | 0.0097 (11) |
C5 | 0.0593 (13) | 0.0433 (11) | 0.0817 (16) | 0.0010 (10) | −0.0149 (12) | 0.0136 (11) |
C6 | 0.0685 (15) | 0.0562 (12) | 0.0535 (12) | 0.0004 (12) | 0.0092 (11) | 0.0130 (11) |
C7 | 0.103 (2) | 0.0685 (16) | 0.0663 (15) | −0.0102 (16) | −0.0066 (16) | −0.0010 (13) |
C8 | 0.0590 (13) | 0.0645 (14) | 0.0578 (12) | 0.0100 (11) | −0.0006 (10) | 0.0109 (11) |
C9 | 0.0502 (11) | 0.0596 (13) | 0.0478 (10) | −0.0003 (10) | −0.0082 (9) | 0.0043 (11) |
C10 | 0.0658 (15) | 0.0616 (14) | 0.0847 (17) | 0.0089 (12) | −0.0054 (13) | 0.0060 (15) |
C11 | 0.080 (2) | 0.099 (2) | 0.113 (3) | 0.038 (2) | −0.021 (2) | −0.009 (2) |
C12 | 0.0561 (16) | 0.185 (4) | 0.083 (2) | 0.029 (2) | −0.0068 (16) | −0.022 (3) |
C13 | 0.0540 (16) | 0.197 (4) | 0.0745 (19) | −0.027 (2) | −0.0063 (14) | 0.025 (3) |
C14 | 0.0660 (16) | 0.103 (2) | 0.0712 (16) | −0.0153 (15) | −0.0117 (13) | 0.0294 (17) |
O1—C6 | 1.338 (3) | C7—H7A | 0.9600 |
O1—C1 | 1.439 (3) | C7—H7B | 0.9600 |
O2—C6 | 1.202 (3) | C7—H7C | 0.9600 |
O3—C2 | 1.400 (3) | C8—C9 | 1.507 (3) |
O3—H3O | 0.8200 | C8—H8A | 0.9700 |
O4—C4 | 1.234 (3) | C8—H8B | 0.9700 |
N1—C4 | 1.339 (3) | C9—C14 | 1.375 (4) |
N1—C2 | 1.447 (3) | C9—C10 | 1.376 (4) |
N1—C8 | 1.457 (3) | C10—C11 | 1.380 (4) |
C1—C5 | 1.512 (3) | C10—H10 | 0.9300 |
C1—C2 | 1.538 (3) | C11—C12 | 1.373 (5) |
C1—H1 | 0.9800 | C11—H11 | 0.9300 |
C2—H2 | 0.9800 | C12—C13 | 1.363 (6) |
C4—C5 | 1.501 (4) | C12—H12 | 0.9300 |
C5—H5A | 0.9700 | C13—C14 | 1.375 (5) |
C5—H5B | 0.9700 | C13—H13 | 0.9300 |
C6—C7 | 1.486 (4) | C14—H14 | 0.9300 |
C6—O1—C1 | 115.57 (18) | C6—C7—H7B | 109.5 |
C2—O3—H3O | 109.5 | H7A—C7—H7B | 109.5 |
C4—N1—C2 | 114.41 (18) | C6—C7—H7C | 109.5 |
C4—N1—C8 | 123.6 (2) | H7A—C7—H7C | 109.5 |
C2—N1—C8 | 121.22 (18) | H7B—C7—H7C | 109.5 |
O1—C1—C5 | 109.34 (18) | N1—C8—C9 | 112.81 (19) |
O1—C1—C2 | 113.42 (17) | N1—C8—H8A | 109.0 |
C5—C1—C2 | 105.0 (2) | C9—C8—H8A | 109.0 |
O1—C1—H1 | 109.6 | N1—C8—H8B | 109.0 |
C5—C1—H1 | 109.6 | C9—C8—H8B | 109.0 |
C2—C1—H1 | 109.6 | H8A—C8—H8B | 107.8 |
O3—C2—N1 | 111.19 (18) | C14—C9—C10 | 119.3 (2) |
O3—C2—C1 | 110.93 (17) | C14—C9—C8 | 120.2 (2) |
N1—C2—C1 | 101.18 (17) | C10—C9—C8 | 120.5 (2) |
O3—C2—H2 | 111.1 | C9—C10—C11 | 120.3 (3) |
N1—C2—H2 | 111.1 | C9—C10—H10 | 119.9 |
C1—C2—H2 | 111.1 | C11—C10—H10 | 119.9 |
O4—C4—N1 | 124.8 (2) | C12—C11—C10 | 119.8 (3) |
O4—C4—C5 | 126.6 (2) | C12—C11—H11 | 120.1 |
N1—C4—C5 | 108.6 (2) | C10—C11—H11 | 120.1 |
C4—C5—C1 | 103.40 (18) | C13—C12—C11 | 120.0 (3) |
C4—C5—H5A | 111.1 | C13—C12—H12 | 120.0 |
C1—C5—H5A | 111.1 | C11—C12—H12 | 120.0 |
C4—C5—H5B | 111.1 | C12—C13—C14 | 120.3 (3) |
C1—C5—H5B | 111.1 | C12—C13—H13 | 119.8 |
H5A—C5—H5B | 109.0 | C14—C13—H13 | 119.8 |
O2—C6—O1 | 122.6 (2) | C13—C14—C9 | 120.3 (3) |
O2—C6—C7 | 124.8 (3) | C13—C14—H14 | 119.9 |
O1—C6—C7 | 112.6 (2) | C9—C14—H14 | 119.9 |
C6—C7—H7A | 109.5 | ||
C6—O1—C1—C5 | 173.36 (18) | O1—C1—C5—C4 | 146.44 (18) |
C6—O1—C1—C2 | −69.8 (2) | C2—C1—C5—C4 | 24.4 (2) |
C4—N1—C2—O3 | −97.9 (2) | C1—O1—C6—O2 | −2.1 (3) |
C8—N1—C2—O3 | 72.3 (2) | C1—O1—C6—C7 | 177.2 (2) |
C4—N1—C2—C1 | 20.0 (2) | C4—N1—C8—C9 | −119.2 (2) |
C8—N1—C2—C1 | −169.84 (18) | C2—N1—C8—C9 | 71.6 (3) |
O1—C1—C2—O3 | −27.8 (3) | N1—C8—C9—C14 | 59.4 (3) |
C5—C1—C2—O3 | 91.5 (2) | N1—C8—C9—C10 | −121.9 (2) |
O1—C1—C2—N1 | −145.88 (18) | C14—C9—C10—C11 | 1.0 (4) |
C5—C1—C2—N1 | −26.6 (2) | C8—C9—C10—C11 | −177.7 (3) |
C2—N1—C4—O4 | 174.5 (2) | C9—C10—C11—C12 | −1.9 (5) |
C8—N1—C4—O4 | 4.6 (4) | C10—C11—C12—C13 | 1.6 (6) |
C2—N1—C4—C5 | −4.9 (3) | C11—C12—C13—C14 | −0.4 (6) |
C8—N1—C4—C5 | −174.8 (2) | C12—C13—C14—C9 | −0.6 (5) |
O4—C4—C5—C1 | 167.7 (2) | C10—C9—C14—C13 | 0.3 (4) |
N1—C4—C5—C1 | −13.0 (3) | C8—C9—C14—C13 | 179.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O4i | 0.82 | 1.86 | 2.671 (2) | 170 |
C5—H5A···O2ii | 0.97 | 2.49 | 3.452 (3) | 170 |
C5—H5B···O3iii | 0.97 | 2.51 | 3.437 (3) | 160 |
C12—H12···O2iv | 0.93 | 2.54 | 3.421 (4) | 158 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O4i | 0.82 | 1.86 | 2.671 (2) | 170 |
C5—H5A···O2ii | 0.97 | 2.49 | 3.452 (3) | 170 |
C5—H5B···O3iii | 0.97 | 2.51 | 3.437 (3) | 160 |
C12—H12···O2iv | 0.93 | 2.54 | 3.421 (4) | 158 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z+1/2. |
Acknowledgements
We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013-2 to JZS, 306121/2013-2 to IC and 308320/2010-7 to HAS), FAPESP (2012/17954-4 and 2013/21925-2) and CAPES are acknowledged for financial support.
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