(3R,4S)-3,4-Isopropylidenedioxy-5-phenylsulfonylmethyl-3,4-dihydro-2H-pyrrole 1-oxide.

The title compound, C(14)H(17)NO(5)S, was prepared by oxidation of (2R,3S,4R)-2-phenyl-sulfonyl-methyl-1-hy-droxy-3,4-iso-pro-pyl-idene-dioxy-pyrrolidine. Its crystal structure confirms unequivocally its configuration. Two inter-molecular C-H⋯O inter-actions help to establish the packing.

Related literature

For the preparation, see: Flores et al. (2010 ▶). For the standard oxidation of hydroxyl­amines to nitro­nes with manganese dioxide, see: Cicchi et al. (2001 ▶). For background to organocatalysts, see: Berkessel & Groger (2005 ▶); Macmillan (2008 ▶). For analogues of the organocatalyst l-proline, see: Andrey et al. (2004 ▶); Cobb et al. (2004 ▶); Tanaka et al. (2004 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

C14H17NO5S

M = 311.35

Orthorhombic,

a = 5.6424 (2) Å

b = 15.5592 (7) Å

c = 16.9097 (8) Å

V = 1484.52 (11) Å3

Z = 4

Cu Kα radiation

μ = 2.14 mm−1

T = 298 K

0.10 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.815, T max = 0.880

8018 measured reflections

2487 independent reflections

2159 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.06

2487 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack (1983 ▶),

Flack parameter: 0.06 (2)

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010737/bt5495sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010737/bt5495Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H17NO5S	F(000) = 656
Mr = 311.35	Dx = 1.393 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1922 reflections
a = 5.6424 (2) Å	θ = 3.9–55.3°
b = 15.5592 (7) Å	µ = 2.14 mm−1
c = 16.9097 (8) Å	T = 298 K
V = 1484.52 (11) Å3	Prismatic, colourless
Z = 4	0.10 × 0.08 × 0.06 mm

Bruker APEXII CCD area-detector diffractometer	2487 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
graphite	Rint = 0.030
phi and ω scans	θmax = 67.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −6→5
Tmin = 0.815, Tmax = 0.880	k = −18→15
8018 measured reflections	l = −18→19

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0335P)2 + 0.1514P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2487 reflections	Δρmax = 0.14 e Å−3
192 parameters	Δρmin = −0.15 e Å−3
0 restraints	Absolute structure: Flack (1983), 907 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (2)

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.

	x	y	z	Uiso*/Ueq
S1	0.89076 (11)	0.02630 (4)	0.36234 (4)	0.05643 (18)
O1	0.8060 (3)	0.16596 (13)	0.57625 (11)	0.0614 (5)
O2	0.9722 (5)	0.10911 (14)	0.68680 (13)	0.0894 (7)
O3	1.3072 (4)	−0.05736 (13)	0.53437 (13)	0.0813 (6)
O4	0.9927 (4)	0.05353 (13)	0.28901 (11)	0.0739 (6)
O5	0.6496 (3)	0.04808 (13)	0.37996 (14)	0.0738 (6)
N1	1.1197 (4)	−0.01709 (14)	0.55737 (13)	0.0619 (6)
C1	0.8010 (4)	0.07555 (18)	0.56728 (16)	0.0587 (7)
H1	0.6470	0.0557	0.5477	0.070*
C2	0.9998 (4)	0.04067 (16)	0.51895 (15)	0.0521 (6)
C3	1.0217 (6)	−0.03387 (19)	0.63738 (19)	0.0805 (8)
H3A	1.1460	−0.0341	0.6770	0.097*
H3B	0.9384	−0.0884	0.6390	0.097*
C4	0.8538 (5)	0.0402 (2)	0.64986 (17)	0.0729 (8)
H4	0.7099	0.0231	0.6782	0.088*
C5	0.9533 (4)	0.18574 (16)	0.64286 (17)	0.0549 (6)
C6	1.1963 (5)	0.2119 (3)	0.6143 (2)	0.0922 (11)
H6A	1.2918	0.2289	0.6586	0.138*
H6B	1.1819	0.2592	0.5782	0.138*
H6C	1.2698	0.1642	0.5878	0.138*
C7	0.8367 (6)	0.2541 (2)	0.6910 (2)	0.0864 (10)
H7A	0.6857	0.2338	0.7094	0.130*
H7B	0.8143	0.3045	0.6591	0.130*
H7C	0.9351	0.2680	0.7355	0.130*
C8	1.0714 (4)	0.06909 (17)	0.43949 (14)	0.0520 (6)
H8A	1.2345	0.0520	0.4304	0.062*
H8B	1.0648	0.1313	0.4374	0.062*
C9	0.9226 (4)	−0.08537 (16)	0.37208 (15)	0.0523 (6)
C10	1.1198 (5)	−0.12509 (19)	0.33956 (16)	0.0653 (7)
H10	1.2338	−0.0933	0.3127	0.078*
C11	1.1429 (5)	−0.2125 (2)	0.3480 (2)	0.0754 (9)
H11	1.2732	−0.2400	0.3257	0.090*
C12	0.9786 (6)	−0.26022 (19)	0.38851 (18)	0.0705 (8)
H12	0.9981	−0.3193	0.3941	0.085*
C13	0.7836 (5)	−0.21963 (19)	0.42093 (19)	0.0703 (8)
H13	0.6707	−0.2516	0.4481	0.084*
C14	0.7551 (4)	−0.13237 (18)	0.41327 (17)	0.0609 (7)
H14	0.6245	−0.1051	0.4356	0.073*

	U11	U22	U33	U12	U13	U23
S1	0.0530 (3)	0.0692 (4)	0.0471 (3)	−0.0058 (3)	−0.0062 (3)	0.0034 (3)
O1	0.0476 (9)	0.0863 (13)	0.0503 (11)	0.0057 (8)	−0.0094 (9)	0.0002 (9)
O2	0.1365 (19)	0.0753 (12)	0.0565 (12)	−0.0047 (13)	−0.0356 (13)	0.0064 (10)
O3	0.0906 (14)	0.0759 (13)	0.0774 (15)	0.0194 (11)	0.0000 (12)	0.0008 (11)
O4	0.0948 (13)	0.0849 (13)	0.0421 (11)	−0.0213 (11)	−0.0065 (11)	0.0110 (9)
O5	0.0455 (9)	0.0819 (13)	0.0939 (16)	0.0066 (8)	−0.0109 (10)	−0.0017 (11)
N1	0.0731 (13)	0.0599 (12)	0.0528 (13)	−0.0067 (12)	0.0011 (13)	0.0040 (11)
C1	0.0440 (13)	0.0819 (18)	0.0503 (16)	−0.0131 (12)	0.0022 (12)	−0.0013 (14)
C2	0.0494 (12)	0.0638 (15)	0.0431 (13)	−0.0127 (12)	−0.0020 (12)	0.0028 (12)
C3	0.116 (2)	0.0678 (17)	0.0573 (17)	−0.0182 (17)	0.0092 (19)	0.0161 (16)
C4	0.0835 (18)	0.087 (2)	0.0485 (15)	−0.0228 (16)	0.0111 (16)	0.0062 (15)
C5	0.0470 (12)	0.0704 (15)	0.0471 (14)	0.0057 (11)	−0.0093 (13)	0.0006 (13)
C6	0.0543 (16)	0.135 (3)	0.087 (3)	−0.0178 (17)	−0.0027 (17)	−0.017 (2)
C7	0.077 (2)	0.117 (3)	0.065 (2)	0.0361 (18)	−0.0159 (17)	−0.0214 (19)
C8	0.0454 (13)	0.0655 (14)	0.0451 (14)	−0.0080 (11)	0.0019 (12)	0.0038 (11)
C9	0.0469 (13)	0.0682 (14)	0.0418 (14)	−0.0061 (11)	0.0018 (12)	−0.0013 (11)
C10	0.0524 (14)	0.0823 (18)	0.0612 (17)	−0.0056 (14)	0.0119 (15)	0.0050 (14)
C11	0.0662 (17)	0.0833 (19)	0.077 (2)	0.0129 (15)	0.0121 (18)	−0.0042 (16)
C12	0.0748 (18)	0.0687 (16)	0.068 (2)	−0.0018 (14)	−0.0025 (17)	0.0036 (15)
C13	0.0686 (17)	0.080 (2)	0.062 (2)	−0.0203 (15)	0.0052 (17)	0.0047 (15)
C14	0.0471 (13)	0.0774 (18)	0.0581 (18)	−0.0093 (13)	0.0092 (14)	−0.0027 (14)

S1—O4	1.4310 (19)	C5—C6	1.510 (4)
S1—O5	1.4334 (18)	C6—H6A	0.9600
S1—C9	1.755 (3)	C6—H6B	0.9600
S1—C8	1.784 (2)	C6—H6C	0.9600
O1—C1	1.415 (3)	C7—H7A	0.9600
O1—C5	1.433 (3)	C7—H7B	0.9600
O2—C5	1.409 (3)	C7—H7C	0.9600
O2—C4	1.409 (4)	C8—H8A	0.9700
O3—N1	1.290 (3)	C8—H8B	0.9700
N1—C2	1.299 (3)	C9—C14	1.383 (3)
N1—C3	1.485 (4)	C9—C10	1.387 (3)
C1—C2	1.490 (4)	C10—C11	1.374 (4)
C1—C4	1.530 (4)	C10—H10	0.9300
C1—H1	0.9800	C11—C12	1.371 (4)
C2—C8	1.471 (3)	C11—H11	0.9300
C3—C4	1.506 (5)	C12—C13	1.382 (4)
C3—H3A	0.9700	C12—H12	0.9300
C3—H3B	0.9700	C13—C14	1.373 (4)
C4—H4	0.9800	C13—H13	0.9300
C5—C7	1.492 (4)	C14—H14	0.9300
O4—S1—O5	119.46 (14)	C7—C5—C6	112.5 (3)
O4—S1—C9	109.47 (13)	C5—C6—H6A	109.5
O5—S1—C9	108.16 (12)	C5—C6—H6B	109.5
O4—S1—C8	107.06 (11)	H6A—C6—H6B	109.5
O5—S1—C8	107.58 (13)	C5—C6—H6C	109.5
C9—S1—C8	104.02 (12)	H6A—C6—H6C	109.5
C1—O1—C5	108.01 (19)	H6B—C6—H6C	109.5
C5—O2—C4	112.0 (2)	C5—C7—H7A	109.5
O3—N1—C2	127.8 (2)	C5—C7—H7B	109.5
O3—N1—C3	119.7 (2)	H7A—C7—H7B	109.5
C2—N1—C3	112.5 (2)	C5—C7—H7C	109.5
O1—C1—C2	113.9 (2)	H7A—C7—H7C	109.5
O1—C1—C4	104.8 (2)	H7B—C7—H7C	109.5
C2—C1—C4	102.9 (2)	C2—C8—S1	113.50 (17)
O1—C1—H1	111.6	C2—C8—H8A	108.9
C2—C1—H1	111.6	S1—C8—H8A	108.9
C4—C1—H1	111.6	C2—C8—H8B	108.9
N1—C2—C8	121.4 (2)	S1—C8—H8B	108.9
N1—C2—C1	111.7 (2)	H8A—C8—H8B	107.7
C8—C2—C1	126.8 (2)	C14—C9—C10	120.8 (3)
N1—C3—C4	103.1 (2)	C14—C9—S1	120.1 (2)
N1—C3—H3A	111.1	C10—C9—S1	119.10 (19)
C4—C3—H3A	111.1	C11—C10—C9	118.4 (3)
N1—C3—H3B	111.1	C11—C10—H10	120.8
C4—C3—H3B	111.1	C9—C10—H10	120.8
H3A—C3—H3B	109.1	C12—C11—C10	121.6 (3)
O2—C4—C3	110.3 (3)	C12—C11—H11	119.2
O2—C4—C1	102.9 (2)	C10—C11—H11	119.2
C3—C4—C1	105.6 (2)	C11—C12—C13	119.3 (3)
O2—C4—H4	112.5	C11—C12—H12	120.4
C3—C4—H4	112.5	C13—C12—H12	120.4
C1—C4—H4	112.5	C14—C13—C12	120.5 (3)
O2—C5—O1	106.07 (19)	C14—C13—H13	119.8
O2—C5—C7	110.4 (3)	C12—C13—H13	119.8
O1—C5—C7	109.1 (2)	C13—C14—C9	119.4 (3)
O2—C5—C6	109.1 (2)	C13—C14—H14	120.3
O1—C5—C6	109.4 (2)	C9—C14—H14	120.3

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4i	0.98	2.50	3.389 (2)	151
C12—H12···O3ii	0.93	2.51	3.270 (4)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O4i	0.98	2.50	3.389 (2)	151
C12—H12⋯O3ii	0.93	2.51	3.270 (4)	139

Symmetry codes: (i) ; (ii) .