organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(4S)-Benzyl 4-iso­propyl-5-oxo-1,3-oxazolidine-3-carboxyl­ate

aKey Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, Xiamen University, Xiamen 361005, People's Republic of China
*Correspondence e-mail: t12g21@xmu.edu.cn

(Received 25 January 2008; accepted 14 February 2008; online 12 March 2008)

In the crystal structure of the title compound, C14H17NO4, obtained by the reaction of N-benzoxycarbonyl-L-valine, paraformaldehyde and 4-methyl­benzene­sulfonic acid, mol­ecules are linked by C—H⋯O hydrogen bonds, generating linear chains parallel to the a axis. C—H⋯π inter­actions of stacked benzene rings also provide stability for the crystal structure.

Related literature

For related literature, see: Dorow & Gingrich (1999[Dorow, R. L. & Gingrich, D. E. (1999). Tetrahedron Lett. 40, 467-470.]); Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]); Pavel et al. (1993[Pavel, H., Heinrich, L. S. & Edward, W. S. (1993). J. Am. Chem. Soc. 116, 3500-3506.]); Reddy et al. (2000[Reddy, G. V., Rao, G. V., Sreevani, V. & Iyengar, D. S. (2000). Tetrahedron Lett. 41, 953-954.]).

[Scheme 1]

Experimental

Crystal data
  • C14H17NO4

  • Mr = 263.29

  • Orthorhombic, P 21 21 21

  • a = 6.0528 (2) Å

  • b = 13.1581 (5) Å

  • c = 16.6778 (6) Å

  • V = 1328.28 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 153 (2) K

  • 0.50 × 0.17 × 0.09 mm

Data collection
  • Bruker APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.953, Tmax = 0.991

  • 5718 measured reflections

  • 1368 independent reflections

  • 1100 reflections with I > 2σ(I)

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.062

  • S = 0.99

  • 1368 reflections

  • 172 parameters

  • H-atom parameters constrained

  • Δρmax = 0.12 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C9–C14 benzene ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯O5i 0.97 2.32 3.258 (2) 163
C12—H12ACgii 0.93 3.37 3.963 (3) 124
Symmetry codes: (i) x-1, y, z; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound (I) belongs to a class of 5-oxazolidinone and has been used to synthesize dipeptides and a series of biologically active molecules (Dorow & Gingrich, 1999).

In the compound, the oxazolidine ring is formed by the reaction of N-benzoxycarbonyl-L-valine, paraformaldehyde, and 4-methylbenzenesulfonic acid. The phenyl and the oxazolidine rings make a dihedral angle of 49.7 (1) (Fig. 1). The absolute configuration (S) of the stereocentre C4 remains unchanged during the synthetic procedure. An X-ray crystal structure determination of the molecular structure of compound (I) was carried out to determine its conformation. The bond lengths are within normal ranges (Allen et al., 1987).

The packing is shown in Fig. 2. The occurrence of C—H···O hydrogen bond interactions lead to the formation of linear chains parallel to the a axis. The packing is further stabilized by C—H···π interactions of stacked benzene rings in the chains (Fig. 3), with typical geometry (Pavel et al., 1993).

Related literature top

For related literature, see: Dorow & Gingrich (1999); Allen et al. (1987); Pavel et al. (1993); Reddy et al. (2000).

Experimental top

The title compound was prepared by a method based on one described by Reddy et al. (2000). A mixture of N-benzoxycarbonyl-L-valine (7.53 g, 3 mmol), paraformaldehyde (1.8 g, 6 mmol) and 4-methylbenzenesulfonic acid (PTSA, 0.31 g, 1.8 mmol) in benzene (25 ml) was refluxed, using a Dean–Stark apparatus, for about 1 h. After cooling, the resulting mixture was washed with 0.3 M aqueous K2CO3 solution (30 ml) followed by saturated aqueous NaCl solution (30 ml). The organic layer was separated and dried with Mg2SO4, filtered and concentrated in vacuo to give the crude product as a white solid (5.12 g, 65%). Crystals suitable for X-ray diffraction were obtained from an ethanol solution.

Refinement top

The hydrogen atoms were positioned geometrically (C—H = 0.93, 0.98, 0.97 or 0.96 Å for phenyl, tertiary, methylene or methyl H atoms respectively) and were included in the refinement in the riding model approximation. The displacement parameters of methyl H atoms were set to 1.5Ueq(C), while those of other H atoms were set to 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-labeling scheme, showing 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. The packing of the molecules, viewed down the a axis.
[Figure 3] Fig. 3. C—H···π interactions of (I). These and hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x - 1/2, -y + 1/2, -z; (ii) x + 1/2, -y + 1/2, -z.]
(4S)-Benzyl 4-isopropyl-5-oxo-1,3-oxazolidine-3-carboxylate top
Crystal data top
C14H17NO4F(000) = 560
Mr = 263.29Dx = 1.317 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2839 reflections
a = 6.0528 (2) Åθ = 2.9–32.6°
b = 13.1581 (5) ŵ = 0.10 mm1
c = 16.6778 (6) ÅT = 153 K
V = 1328.28 (8) Å3Needle, colourless
Z = 40.50 × 0.17 × 0.09 mm
Data collection top
Bruker APEX CCD
diffractometer
1368 independent reflections
Radiation source: sealed tube1100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 16.1903 pixels mm-1θmax = 25.0°, θmin = 2.9°
ϕ and ω scansh = 77
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 1415
Tmin = 0.953, Tmax = 0.991l = 1919
5718 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0398P)2]
where P = (Fo2 + 2Fc2)/3
1368 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C14H17NO4V = 1328.28 (8) Å3
Mr = 263.29Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.0528 (2) ŵ = 0.10 mm1
b = 13.1581 (5) ÅT = 153 K
c = 16.6778 (6) Å0.50 × 0.17 × 0.09 mm
Data collection top
Bruker APEX CCD
diffractometer
1368 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1100 reflections with I > 2σ(I)
Tmin = 0.953, Tmax = 0.991Rint = 0.028
5718 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.062H-atom parameters constrained
S = 0.99Δρmax = 0.12 e Å3
1368 reflectionsΔρmin = 0.13 e Å3
172 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.4445 (2)0.27913 (11)0.18553 (8)0.0312 (3)
C20.6151 (3)0.24832 (15)0.13165 (12)0.0315 (5)
H2A0.74930.23180.16070.038*
H2B0.64730.30170.09320.038*
N30.5269 (3)0.15900 (11)0.09160 (9)0.0250 (4)
C40.3046 (3)0.13532 (13)0.11905 (11)0.0242 (4)
H4A0.20080.14120.07420.029*
O50.1002 (2)0.23774 (11)0.21593 (8)0.0361 (4)
C50.2637 (3)0.22044 (15)0.17824 (11)0.0261 (4)
O60.7800 (2)0.17466 (10)0.00699 (9)0.0348 (4)
C60.6135 (3)0.13483 (15)0.01957 (12)0.0268 (5)
O70.4976 (2)0.06146 (10)0.01706 (7)0.0308 (3)
C80.5807 (4)0.02766 (16)0.09484 (11)0.0325 (5)
H8A0.65700.08370.12060.039*
H8B0.45660.00890.12860.039*
C90.7346 (4)0.06079 (15)0.08858 (11)0.0287 (5)
C100.9408 (4)0.05173 (17)0.05121 (12)0.0361 (5)
H10A0.98190.00990.02830.043*
C111.0833 (4)0.13326 (18)0.04812 (13)0.0435 (6)
H11A1.21810.12690.02180.052*
C121.0276 (4)0.22421 (19)0.08374 (14)0.0482 (6)
H12A1.12470.27900.08210.058*
C130.8260 (4)0.23316 (17)0.12188 (15)0.0467 (6)
H13A0.78820.29410.14660.056*
C140.6801 (4)0.15252 (15)0.12363 (12)0.0365 (5)
H14A0.54380.16000.14870.044*
C150.2829 (3)0.02961 (14)0.15749 (11)0.0266 (5)
H15A0.33760.02020.11860.032*
C160.4247 (4)0.02032 (17)0.23247 (13)0.0378 (5)
H16A0.40750.04640.25500.057*
H16B0.37910.07030.27100.057*
H16C0.57690.03120.21870.057*
C170.0424 (3)0.00377 (16)0.17484 (13)0.0375 (5)
H17A0.03380.06250.19880.056*
H17B0.04010.00430.12570.056*
H17C0.01820.05320.21100.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0307 (8)0.0288 (7)0.0341 (7)0.0021 (7)0.0004 (6)0.0064 (6)
C20.0256 (11)0.0325 (12)0.0363 (11)0.0034 (10)0.0005 (9)0.0050 (10)
N30.0244 (9)0.0243 (8)0.0261 (9)0.0028 (7)0.0006 (7)0.0013 (7)
C40.0224 (10)0.0257 (10)0.0244 (10)0.0005 (9)0.0020 (8)0.0008 (9)
O50.0331 (8)0.0374 (8)0.0378 (8)0.0059 (7)0.0048 (7)0.0036 (7)
C50.0274 (11)0.0248 (10)0.0261 (10)0.0032 (9)0.0033 (10)0.0028 (9)
O60.0328 (8)0.0344 (8)0.0372 (8)0.0060 (7)0.0088 (7)0.0012 (7)
C60.0267 (11)0.0232 (11)0.0304 (11)0.0002 (10)0.0014 (9)0.0039 (9)
O70.0325 (8)0.0313 (7)0.0286 (7)0.0057 (7)0.0029 (6)0.0055 (6)
C80.0396 (12)0.0346 (11)0.0232 (10)0.0033 (10)0.0023 (9)0.0027 (9)
C90.0375 (12)0.0298 (11)0.0187 (9)0.0039 (10)0.0045 (9)0.0003 (9)
C100.0414 (13)0.0358 (12)0.0310 (11)0.0023 (11)0.0010 (10)0.0037 (10)
C110.0388 (13)0.0509 (15)0.0408 (13)0.0027 (13)0.0022 (11)0.0038 (12)
C120.0554 (17)0.0377 (14)0.0514 (14)0.0107 (13)0.0094 (13)0.0075 (12)
C130.0624 (16)0.0283 (12)0.0493 (13)0.0039 (12)0.0102 (13)0.0045 (12)
C140.0430 (13)0.0360 (12)0.0305 (11)0.0070 (11)0.0022 (10)0.0017 (11)
C150.0299 (11)0.0212 (10)0.0288 (10)0.0002 (9)0.0049 (9)0.0012 (8)
C160.0353 (12)0.0364 (12)0.0419 (12)0.0045 (10)0.0002 (10)0.0116 (10)
C170.0365 (13)0.0365 (13)0.0395 (12)0.0090 (11)0.0019 (10)0.0004 (10)
Geometric parameters (Å, º) top
O1—C51.345 (2)C10—C111.378 (3)
O1—C21.428 (2)C10—H10A0.930
C2—N31.454 (2)C11—C121.378 (4)
C2—H2A0.970C11—H11A0.930
C2—H2B0.970C12—C131.381 (4)
N3—C61.349 (2)C12—H12A0.930
N3—C41.455 (2)C13—C141.381 (3)
C4—C51.513 (3)C13—H13A0.930
C4—C151.537 (2)C14—H14A0.930
C4—H4A0.980C15—C161.522 (3)
O5—C51.194 (2)C15—C171.523 (3)
O6—C61.219 (2)C15—H15A0.980
C6—O71.340 (2)C16—H16A0.960
O7—C81.461 (2)C16—H16B0.960
C8—C91.495 (3)C16—H16C0.960
C8—H8A0.970C17—H17A0.960
C8—H8B0.970C17—H17B0.960
C9—C141.381 (3)C17—H17C0.960
C9—C101.400 (3)
C5—O1—C2111.63 (15)C11—C10—H10A119.7
O1—C2—N3104.66 (15)C9—C10—H10A119.7
O1—C2—H2A110.8C10—C11—C12120.5 (2)
N3—C2—H2A110.8C10—C11—H11A119.8
O1—C2—H2B110.8C12—C11—H11A119.8
N3—C2—H2B110.8C11—C12—C13119.3 (2)
H2A—C2—H2B108.9C11—C12—H12A120.4
C6—N3—C2117.21 (16)C13—C12—H12A120.4
C6—N3—C4126.09 (16)C14—C13—C12120.6 (2)
C2—N3—C4111.61 (15)C14—C13—H13A119.7
N3—C4—C5101.42 (15)C12—C13—H13A119.7
N3—C4—C15113.81 (15)C13—C14—C9120.7 (2)
C5—C4—C15112.56 (15)C13—C14—H14A119.7
N3—C4—H4A109.6C9—C14—H14A119.7
C5—C4—H4A109.6C16—C15—C17111.42 (17)
C15—C4—H4A109.6C16—C15—C4111.55 (16)
O5—C5—O1121.14 (18)C17—C15—C4111.28 (16)
O5—C5—C4128.30 (19)C16—C15—H15A107.4
O1—C5—C4110.55 (16)C17—C15—H15A107.4
O6—C6—O7125.19 (18)C4—C15—H15A107.4
O6—C6—N3122.92 (18)C15—C16—H16A109.5
O7—C6—N3111.88 (17)C15—C16—H16B109.5
C6—O7—C8116.37 (15)H16A—C16—H16B109.5
O7—C8—C9112.93 (16)C15—C16—H16C109.5
O7—C8—H8A109.0H16A—C16—H16C109.5
C9—C8—H8A109.0H16B—C16—H16C109.5
O7—C8—H8B109.0C15—C17—H17A109.5
C9—C8—H8B109.0C15—C17—H17B109.5
H8A—C8—H8B107.8H17A—C17—H17B109.5
C14—C9—C10118.4 (2)C15—C17—H17C109.5
C14—C9—C8120.14 (19)H17A—C17—H17C109.5
C10—C9—C8121.37 (18)H17B—C17—H17C109.5
C11—C10—C9120.6 (2)
C5—O1—C2—N33.0 (2)O6—C6—O7—C80.1 (3)
O1—C2—N3—C6157.15 (15)N3—C6—O7—C8178.52 (15)
O1—C2—N3—C40.8 (2)C6—O7—C8—C992.1 (2)
C6—N3—C4—C5152.48 (17)O7—C8—C9—C14117.2 (2)
C2—N3—C4—C51.34 (19)O7—C8—C9—C1066.2 (2)
C6—N3—C4—C1586.4 (2)C14—C9—C10—C111.4 (3)
C2—N3—C4—C15119.80 (17)C8—C9—C10—C11178.02 (19)
C2—O1—C5—O5176.54 (18)C9—C10—C11—C121.8 (3)
C2—O1—C5—C44.0 (2)C10—C11—C12—C130.7 (4)
N3—C4—C5—O5177.38 (19)C11—C12—C13—C140.8 (4)
C15—C4—C5—O560.6 (3)C12—C13—C14—C91.2 (3)
N3—C4—C5—O13.20 (19)C10—C9—C14—C130.1 (3)
C15—C4—C5—O1118.80 (17)C8—C9—C14—C13176.57 (19)
C2—N3—C6—O611.0 (3)N3—C4—C15—C1662.4 (2)
C4—N3—C6—O6163.56 (17)C5—C4—C15—C1652.3 (2)
C2—N3—C6—O7170.34 (15)N3—C4—C15—C17172.49 (16)
C4—N3—C6—O717.8 (2)C5—C4—C15—C1772.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O5i0.972.323.258 (2)163
C12—H12A···Cgii0.933.373.963 (3)124
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC14H17NO4
Mr263.29
Crystal system, space groupOrthorhombic, P212121
Temperature (K)153
a, b, c (Å)6.0528 (2), 13.1581 (5), 16.6778 (6)
V3)1328.28 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.50 × 0.17 × 0.09
Data collection
DiffractometerBruker APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.953, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
5718, 1368, 1100
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.062, 0.99
No. of reflections1368
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.12, 0.13

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O5i0.972.323.258 (2)163.4
C12—H12A···Cgii0.933.373.963 (3)123.6
Symmetry codes: (i) x1, y, z; (ii) x1/2, y+1/2, z.
 

Acknowledgements

The authors acknowledge financial support from the Key Foundation of Science and Technology Project of Fujian Province, China (Key grant No. 2002H011).

References

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First citationBruker (2001). SAINT (Version 6.22), SMART (Version 5.625) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDorow, R. L. & Gingrich, D. E. (1999). Tetrahedron Lett. 40, 467–470.  Web of Science CrossRef CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationPavel, H., Heinrich, L. S. & Edward, W. S. (1993). J. Am. Chem. Soc. 116, 3500–3506.  Google Scholar
First citationReddy, G. V., Rao, G. V., Sreevani, V. & Iyengar, D. S. (2000). Tetrahedron Lett. 41, 953–954.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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