Crystal structure of 1-benzyl-2-hy­droxy-5-oxopyrrolidin-3-yl acetate

Abstract

In the title compound, C₁₃H₁₅NO₄, the oxopyrrolidin-3-yl ring has an envelope conformation, 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.

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 ▸).

Experimental  

Crystal data  

• C₁₃H₁₅NO₄

• M _r = 249.26

• Orthorhombic,

• a = 26.504 (2) Å

• b = 6.3668 (5) Å

• c = 7.6040 (6) Å

• V = 1283.14 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.56 × 0.40 × 0.36 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.673, T _max = 0.745

• 4917 measured reflections

• 2246 independent reflections

• 2087 reflections with I > 2σ(I)

• R _int = 0.014

Refinement  

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.093

• S = 1.06

• 2246 reflections

• 165 parameters

• H-atom parameters constrained

• Δρ_max = 0.10 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: 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 ▸).

Supplementary Material

CCDC reference: 1412190

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O3H3OO4i	0.82	1.86	2.671(2)	170
C5H5AO2ii	0.97	2.49	3.452(3)	170
C5H5BO3iii	0.97	2.51	3.437(3)	160
C12H12O2iv	0.93	2.54	3.421(4)	158

Symmetry code: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

S3. Experimental

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.

S4. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The O-bound H-atom was treated similarly with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O).

Figures

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.

Crystal data

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

Data collection

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

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

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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.