(R)-4-Isopropyl-3-isopropyl­sulfanyl-5,5-diphenyl-1,3-oxazolidin-2-one

Pozza Silveira, G.; Bonfante de Carvallho, C.; Oliver, A.

doi:10.1107/S160053681202569X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2048

https://doi.org/10.1107/S160053681202569X

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(R)-4-Isopropyl-3-isopropylsulfanyl-5,5-diphenyl-1,3-oxazolidin-2-one

Gustavo Pozza Silveira,^a Cassandra Bonfante de Carvallho ^a and Allen Oliver ^b ^*

^aDepartamento de Química, Instituto de Química, Universidade Federal do Rio, Grande do Sul, Porto Alegre/RS 91501-970, Brazil, and ^bDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre, Dame, IN 46556-5670, USA
^*Correspondence e-mail: gustavo.silveira@iq.ufrgs.br

(Received 4 June 2012; accepted 5 June 2012; online 13 June 2012)

The title compound, C₂₁H₂₅NO₂S, consists of a five-membered heterocyclic ring, with pendant phenyl groups, an isopropyl group and a thioether residue. The thioether bonds to the heterocycle via the N atom. The absolute configuration results from an inversion of the configuration of substrate during the synthesis.

Related literature

For background to the preparation of chiral auxiliaries containing sulfilimine functionalities, see: Celentano et al. (1998 ). For a related structure, see: Valle et al. (1992 ). For the synthesis, see: Hintermann & Seebach (1998 ); Derbesy & Harpp (1995 ). For the structural characterization and absolute configuration analysis, see: Flack (1983 ); Hooft et al. (2008 ). For a description of the Cambridge Structural Database, see Allen (2002 ).

Experimental

Crystal data

C₂₁H₂₅NO₂S
M_r = 355.48
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0621 (1) Å
b = 17.2963 (3) Å
c = 18.5398 (3) Å
V = 1943.93 (6) Å³
Z = 4
Cu Kα radiation
μ = 1.58 mm⁻¹
T = 100 K
0.50 × 0.23 × 0.21 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 2008 ) T_min = 0.720, T_max = 0.964
18292 measured reflections
3008 independent reflections
2887 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.071
S = 1.06
3008 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983), 1165 Friedel pairs
Flack parameter: 0.039 (15)

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681202569X/tk5109sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202569X/tk5109Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202569X/tk5109Isup3.cml

checkCIF report

Comment top

Oxazolindinone compounds, such as the title compound, (R)-4-isopropyl-3-(isopropylthio)-5,5-diphenyloxazolidin-2-one (I), are synthesized as precursors for the preparation of chiral auxiliaries containing sulfilimine functionalities. Eventually, these auxiliaries are applied to the synthesis of new sulfimines in a high enantiomeric ratio (Celentano et al., 1998). To the best of our knowledge, the only other N-thioether-containing oxazolindinone is a dione (Valle et al., 1992). All other oxazoldininones that exhibit an N—S bond are sulfinyl- or sulfonyl-containing compounds (Allen, 2002).

An interesting feature of this compound is the conversion of S-isopropyl isopropanesulfonothioate to an R-isomer during the synthesis. Confirmation of the correct absolute stereochemistry of (I) was determined as described below.

Related literature top

For background to the preparation of chiral auxiliaries containing sulfilimine functionalities, see: Celentano et al. (1998). For a related structure, see: Valle et al. (1992). For the synthesis, see: Hintermann & Seebach (1998); Derbesy & Harpp (1995). For the structural characterization and absolute configuration analysis, see: Flack (1983); Hooft et al. (2008). For a description of the Cambridge Structural Database, see Allen (2002).

Experimental top

To a solution of the oxazolidinone (Hintermann & Seebach, 1998) (2.50 g, 8.80 mmol) in dry THF (40 ml) at 273 K was slowly added 1 equiv of n-BuLi (Celentano et al., 1998). The solution turned from colorless to dark-red. After the mixture was left to react for 30 min at 273 K, a solution of S-isopropyl isopropanesulfonothioate (Derbesy & Harpp, 1995) (1.58 g, 9.10 mmol) in dry THF (40 ml) was added by cannula, at once, and the reaction was left stirring overnight at room temperature. The white mixture was quenched with saturated NH₄Cl (50 ml) and extracted with ethyl acetate (50 ml). The organic layer was washed with H₂O (50 ml) and brine, dried with MgSO₄ and then filtered. The solvent was removed at reduced pressure on a rotovap and the colorless oil was purified through flash chromatography with elution by (1:9 ethyl acetate/hexanes) to provide 2.28 g of the oxazolidine sulfide (73% yield) as colorless prisms after slow evaporation.

Structure description top

For background to the preparation of chiral auxiliaries containing sulfilimine functionalities, see: Celentano et al. (1998). For a related structure, see: Valle et al. (1992). For the synthesis, see: Hintermann & Seebach (1998); Derbesy & Harpp (1995). For the structural characterization and absolute configuration analysis, see: Flack (1983); Hooft et al. (2008). For a description of the Cambridge Structural Database, see Allen (2002).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. H atoms are shown as idealized spheres of an arbitrary radius.

(R)-4-Isopropyl-3-isopropylsulfanyl-5,5-diphenyl-1,3-oxazolidin-2-one top

Crystal data top

C₂₁H₂₅NO₂S	F(000) = 760
M_r = 355.48	D_x = 1.215 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9921 reflections
a = 6.0621 (1) Å	θ = 3.5–68.2°
b = 17.2963 (3) Å	µ = 1.58 mm⁻¹
c = 18.5398 (3) Å	T = 100 K
V = 1943.93 (6) Å³	Block, colourless
Z = 4	0.50 × 0.23 × 0.21 mm

Data collection top

Bruker SMART APEX diffractometer	3008 independent reflections
Radiation source: fine-focus sealed tube	2887 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.33 pixels mm^-1	θ_max = 68.3°, θ_min = 3.5°
combination of ω and φ–scans	h = −7→5
Absorption correction: numerical (SADABS; Sheldrick, 2008)	k = −20→19
T_min = 0.720, T_max = 0.964	l = −22→19
18292 measured reflections

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.0409P)² + 0.4225P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.003
3008 reflections	Δρ_max = 0.19 e Å⁻³
230 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1165 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.039 (15)

Crystal data top

C₂₁H₂₅NO₂S	V = 1943.93 (6) Å³
M_r = 355.48	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 6.0621 (1) Å	µ = 1.58 mm⁻¹
b = 17.2963 (3) Å	T = 100 K
c = 18.5398 (3) Å	0.50 × 0.23 × 0.21 mm

Data collection top

Bruker SMART APEX diffractometer	3008 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 2008)	2887 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.964	R_int = 0.026
18292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.071	Δρ_max = 0.19 e Å⁻³
S = 1.06	Δρ_min = −0.16 e Å⁻³
3008 reflections	Absolute structure: Flack (1983), 1165 Friedel pairs
230 parameters	Absolute structure parameter: 0.039 (15)
0 restraints

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

	x	y	z	U_iso*/U_eq
S1	0.98999 (7)	0.85676 (3)	0.12949 (2)	0.02269 (12)
O1	1.4437 (2)	0.84260 (8)	0.20523 (7)	0.0278 (3)
O2	1.2940 (2)	0.88301 (7)	0.30979 (6)	0.0219 (3)
N1	1.0729 (2)	0.87582 (9)	0.21499 (7)	0.0209 (3)
C1	1.2833 (3)	0.86441 (11)	0.23819 (9)	0.0215 (4)
C2	0.9378 (3)	0.91505 (11)	0.26982 (8)	0.0201 (4)
H2A	0.7868	0.8918	0.2706	0.024*
C3	1.0683 (3)	0.88855 (11)	0.33765 (9)	0.0204 (4)
C4	0.8825 (3)	0.75865 (11)	0.13766 (10)	0.0262 (4)
H4A	0.7905	0.7549	0.1823	0.031*
C5	1.0669 (3)	0.69929 (12)	0.14156 (11)	0.0344 (5)
H5A	1.0033	0.6473	0.1440	0.052*
H5B	1.1563	0.7087	0.1847	0.052*
H5C	1.1600	0.7036	0.0985	0.052*
C6	0.7353 (4)	0.74711 (14)	0.07179 (11)	0.0376 (5)
H6A	0.6752	0.6945	0.0722	0.056*
H6B	0.8223	0.7549	0.0278	0.056*
H6C	0.6140	0.7845	0.0731	0.056*
C7	0.9201 (3)	1.00311 (11)	0.25872 (9)	0.0213 (4)
H7A	0.8672	1.0257	0.3053	0.026*
C8	1.1389 (3)	1.04238 (12)	0.24058 (10)	0.0283 (4)
H8A	1.2449	1.0330	0.2795	0.042*
H8B	1.1153	1.0981	0.2352	0.042*
H8C	1.1969	1.0212	0.1954	0.042*
C9	0.7481 (3)	1.02356 (12)	0.20090 (10)	0.0303 (5)
H9A	0.6098	0.9964	0.2112	0.045*
H9B	0.8029	1.0079	0.1534	0.045*
H9C	0.7218	1.0795	0.2012	0.045*
C10	1.0041 (3)	0.80762 (10)	0.36471 (8)	0.0215 (4)
C11	1.1590 (3)	0.76845 (12)	0.40647 (10)	0.0275 (5)
H11A	1.2999	0.7909	0.4145	0.033*
C12	1.1099 (4)	0.69714 (12)	0.43639 (10)	0.0345 (5)
H12A	1.2176	0.6709	0.4644	0.041*
C13	0.9050 (4)	0.66396 (12)	0.42565 (10)	0.0327 (5)
H13A	0.8709	0.6152	0.4464	0.039*
C14	0.7502 (3)	0.70267 (12)	0.38436 (10)	0.0300 (5)
H14A	0.6095	0.6800	0.3765	0.036*
C15	0.7983 (3)	0.77417 (11)	0.35432 (9)	0.0249 (4)
H15A	0.6900	0.8004	0.3265	0.030*
C16	1.0661 (3)	0.94454 (11)	0.40064 (9)	0.0205 (4)
C17	0.8725 (3)	0.95254 (12)	0.44058 (9)	0.0250 (4)
H17A	0.7449	0.9241	0.4271	0.030*
C18	0.8645 (3)	1.00158 (12)	0.49972 (9)	0.0287 (5)
H18A	0.7311	1.0070	0.5261	0.034*
C19	1.0499 (3)	1.04269 (12)	0.52041 (9)	0.0299 (5)
H19A	1.0454	1.0756	0.5614	0.036*
C20	1.2420 (3)	1.03529 (11)	0.48068 (9)	0.0266 (4)
H20A	1.3690	1.0639	0.4943	0.032*
C21	1.2520 (3)	0.98667 (11)	0.42123 (9)	0.0249 (4)
H21A	1.3852	0.9821	0.3946	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0304 (2)	0.0230 (3)	0.01463 (18)	−0.00277 (19)	−0.00080 (17)	0.00131 (18)
O1	0.0247 (7)	0.0330 (9)	0.0257 (6)	0.0008 (5)	0.0016 (5)	−0.0044 (6)
O2	0.0207 (6)	0.0255 (8)	0.0193 (5)	0.0003 (5)	−0.0009 (5)	−0.0012 (5)
N1	0.0228 (8)	0.0238 (9)	0.0160 (6)	0.0004 (6)	0.0001 (5)	−0.0017 (7)
C1	0.0253 (9)	0.0182 (11)	0.0208 (8)	−0.0043 (8)	0.0007 (7)	−0.0007 (8)
C2	0.0231 (9)	0.0195 (10)	0.0177 (8)	−0.0017 (7)	−0.0001 (6)	−0.0002 (8)
C3	0.0196 (9)	0.0220 (11)	0.0196 (8)	0.0000 (7)	0.0006 (6)	0.0008 (8)
C4	0.0327 (11)	0.0224 (11)	0.0236 (8)	−0.0059 (8)	0.0022 (8)	−0.0020 (9)
C5	0.0399 (12)	0.0245 (12)	0.0389 (11)	0.0001 (9)	−0.0032 (9)	0.0033 (10)
C6	0.0386 (12)	0.0356 (13)	0.0386 (11)	0.0019 (10)	−0.0097 (9)	−0.0143 (10)
C7	0.0257 (9)	0.0209 (11)	0.0173 (7)	0.0008 (7)	−0.0006 (7)	0.0011 (8)
C8	0.0340 (11)	0.0229 (11)	0.0280 (9)	−0.0017 (8)	0.0006 (8)	0.0064 (9)
C9	0.0315 (11)	0.0273 (13)	0.0320 (9)	0.0032 (8)	−0.0049 (8)	0.0033 (9)
C10	0.0318 (9)	0.0180 (10)	0.0148 (7)	0.0020 (8)	0.0030 (8)	−0.0020 (7)
C11	0.0350 (11)	0.0249 (12)	0.0227 (8)	0.0008 (8)	−0.0038 (8)	0.0019 (9)
C12	0.0510 (13)	0.0273 (13)	0.0252 (9)	0.0087 (10)	−0.0037 (9)	0.0036 (10)
C13	0.0575 (13)	0.0169 (12)	0.0236 (9)	0.0020 (9)	0.0091 (9)	0.0017 (9)
C14	0.0382 (11)	0.0240 (12)	0.0277 (9)	−0.0029 (8)	0.0068 (8)	−0.0015 (9)
C15	0.0291 (10)	0.0218 (11)	0.0237 (8)	0.0009 (8)	0.0024 (7)	0.0006 (9)
C16	0.0269 (10)	0.0179 (10)	0.0167 (7)	0.0017 (7)	−0.0033 (6)	0.0044 (8)
C17	0.0284 (10)	0.0232 (11)	0.0234 (9)	0.0005 (8)	−0.0008 (7)	0.0035 (9)
C18	0.0401 (11)	0.0256 (12)	0.0204 (8)	0.0071 (9)	0.0045 (8)	0.0010 (9)
C19	0.0483 (13)	0.0224 (11)	0.0190 (8)	0.0074 (9)	−0.0063 (8)	−0.0014 (9)
C20	0.0367 (11)	0.0187 (11)	0.0244 (9)	−0.0006 (8)	−0.0117 (8)	−0.0003 (8)
C21	0.0298 (10)	0.0217 (11)	0.0231 (8)	0.0016 (8)	−0.0035 (7)	0.0023 (9)

Geometric parameters (Å, º) top

S1—N1	1.6952 (14)	C20—C21	1.388 (3)
S1—C4	1.8240 (19)	C2—H2A	1.0000
O1—C1	1.209 (2)	C4—H4A	1.0000
O2—C1	1.367 (2)	C5—H5A	0.9800
O2—C3	1.466 (2)	C5—H5B	0.9800
N1—C1	1.361 (2)	C5—H5C	0.9800
N1—C2	1.471 (2)	C6—H6A	0.9800
C2—C7	1.541 (3)	C6—H6B	0.9800
C2—C3	1.555 (2)	C6—H6C	0.9800
C3—C16	1.517 (3)	C7—H7A	1.0000
C3—C10	1.537 (3)	C8—H8A	0.9800
C4—C5	1.519 (3)	C8—H8B	0.9800
C4—C6	1.525 (3)	C8—H8C	0.9800
C7—C8	1.528 (3)	C9—H9A	0.9800
C7—C9	1.537 (2)	C9—H9B	0.9800
C10—C15	1.388 (3)	C9—H9C	0.9800
C10—C11	1.393 (3)	C11—H11A	0.9500
C11—C12	1.385 (3)	C12—H12A	0.9500
C12—C13	1.383 (3)	C13—H13A	0.9500
C13—C14	1.384 (3)	C14—H14A	0.9500
C14—C15	1.387 (3)	C15—H15A	0.9500
C16—C17	1.395 (2)	C17—H17A	0.9500
C16—C21	1.395 (3)	C18—H18A	0.9500
C17—C18	1.387 (3)	C19—H19A	0.9500
C18—C19	1.385 (3)	C20—H20A	0.9500
C19—C20	1.384 (3)	C21—H21A	0.9500

N1—S1—C4	102.07 (8)	C4—C5—H5B	109.5
C1—O2—C3	108.25 (12)	H5A—C5—H5B	109.5
C1—N1—C2	111.72 (13)	C4—C5—H5C	109.5
C1—N1—S1	123.04 (12)	H5A—C5—H5C	109.5
C2—N1—S1	124.82 (11)	H5B—C5—H5C	109.5
O1—C1—N1	129.76 (16)	C4—C6—H6A	109.5
O1—C1—O2	121.74 (15)	C4—C6—H6B	109.5
N1—C1—O2	108.50 (14)	H6A—C6—H6B	109.5
N1—C2—C7	113.74 (14)	C4—C6—H6C	109.5
N1—C2—C3	98.05 (13)	H6A—C6—H6C	109.5
C7—C2—C3	115.78 (14)	H6B—C6—H6C	109.5
O2—C3—C16	108.72 (14)	C8—C7—H7A	107.1
O2—C3—C10	106.96 (14)	C9—C7—H7A	107.1
C16—C3—C10	109.14 (14)	C2—C7—H7A	107.1
O2—C3—C2	102.07 (12)	C7—C8—H8A	109.5
C16—C3—C2	115.48 (15)	C7—C8—H8B	109.5
C10—C3—C2	113.81 (15)	H8A—C8—H8B	109.5
C5—C4—C6	112.33 (16)	C7—C8—H8C	109.5
C5—C4—S1	111.71 (13)	H8A—C8—H8C	109.5
C6—C4—S1	105.32 (14)	H8B—C8—H8C	109.5
C8—C7—C9	109.46 (15)	C7—C9—H9A	109.5
C8—C7—C2	114.11 (15)	C7—C9—H9B	109.5
C9—C7—C2	111.60 (15)	H9A—C9—H9B	109.5
C15—C10—C11	118.71 (17)	C7—C9—H9C	109.5
C15—C10—C3	124.17 (16)	H9A—C9—H9C	109.5
C11—C10—C3	116.97 (17)	H9B—C9—H9C	109.5
C12—C11—C10	120.71 (19)	C12—C11—H11A	119.6
C13—C12—C11	120.3 (2)	C10—C11—H11A	119.6
C12—C13—C14	119.21 (19)	C13—C12—H12A	119.8
C13—C14—C15	120.7 (2)	C11—C12—H12A	119.8
C14—C15—C10	120.31 (18)	C12—C13—H13A	120.4
C17—C16—C21	118.85 (17)	C14—C13—H13A	120.4
C17—C16—C3	118.63 (16)	C13—C14—H14A	119.6
C21—C16—C3	122.49 (15)	C15—C14—H14A	119.6
C18—C17—C16	120.67 (18)	C14—C15—H15A	119.8
C19—C18—C17	120.29 (18)	C10—C15—H15A	119.8
C18—C19—C20	119.23 (17)	C18—C17—H17A	119.7
C19—C20—C21	121.05 (19)	C16—C17—H17A	119.7
C20—C21—C16	119.90 (18)	C19—C18—H18A	119.9
N1—C2—H2A	109.6	C17—C18—H18A	119.9
C7—C2—H2A	109.6	C18—C19—H19A	120.4
C3—C2—H2A	109.6	C20—C19—H19A	120.4
C5—C4—H4A	109.1	C19—C20—H20A	119.5
C6—C4—H4A	109.1	C21—C20—H20A	119.5
S1—C4—H4A	109.1	C20—C21—H21A	120.0
C4—C5—H5A	109.5	C16—C21—H21A	120.0

C4—S1—N1—C1	94.18 (16)	C16—C3—C10—C15	103.39 (18)
C4—S1—N1—C2	−93.83 (15)	C2—C3—C10—C15	−27.2 (2)
C2—N1—C1—O1	−170.44 (19)	O2—C3—C10—C11	45.47 (19)
S1—N1—C1—O1	2.5 (3)	C16—C3—C10—C11	−71.98 (19)
C2—N1—C1—O2	8.9 (2)	C2—C3—C10—C11	157.40 (15)
S1—N1—C1—O2	−178.19 (11)	C15—C10—C11—C12	0.7 (3)
C3—O2—C1—O1	−166.32 (17)	C3—C10—C11—C12	176.36 (16)
C3—O2—C1—N1	14.3 (2)	C10—C11—C12—C13	−0.5 (3)
C1—N1—C2—C7	96.89 (17)	C11—C12—C13—C14	0.3 (3)
S1—N1—C2—C7	−75.89 (17)	C12—C13—C14—C15	−0.4 (3)
C1—N1—C2—C3	−25.94 (18)	C13—C14—C15—C10	0.7 (3)
S1—N1—C2—C3	161.28 (13)	C11—C10—C15—C14	−0.8 (3)
C1—O2—C3—C16	−152.32 (15)	C3—C10—C15—C14	−176.10 (16)
C1—O2—C3—C10	89.95 (16)	O2—C3—C16—C17	−173.21 (15)
C1—O2—C3—C2	−29.84 (18)	C10—C3—C16—C17	−56.9 (2)
N1—C2—C3—O2	31.85 (15)	C2—C3—C16—C17	72.8 (2)
C7—C2—C3—O2	−89.47 (16)	O2—C3—C16—C21	5.0 (2)
N1—C2—C3—C16	149.59 (15)	C10—C3—C16—C21	121.36 (18)
C7—C2—C3—C16	28.3 (2)	C2—C3—C16—C21	−108.93 (19)
N1—C2—C3—C10	−83.01 (16)	C21—C16—C17—C18	0.1 (3)
C7—C2—C3—C10	155.67 (14)	C3—C16—C17—C18	178.38 (17)
N1—S1—C4—C5	−76.73 (14)	C16—C17—C18—C19	−0.7 (3)
N1—S1—C4—C6	161.06 (13)	C17—C18—C19—C20	1.1 (3)
N1—C2—C7—C8	−44.64 (18)	C18—C19—C20—C21	−0.9 (3)
C3—C2—C7—C8	67.84 (19)	C19—C20—C21—C16	0.2 (3)
N1—C2—C7—C9	80.09 (18)	C17—C16—C21—C20	0.2 (3)
C3—C2—C7—C9	−167.43 (14)	C3—C16—C21—C20	−178.05 (17)
O2—C3—C10—C15	−139.16 (16)

Experimental details

Crystal data
Chemical formula	C₂₁H₂₅NO₂S
M_r	355.48
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	6.0621 (1), 17.2963 (3), 18.5398 (3)
V (Å³)	1943.93 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.50 × 0.23 × 0.21

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Numerical (SADABS; Sheldrick, 2008)
T_min, T_max	0.720, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	18292, 3008, 2887
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.071, 1.06
No. of reflections	3008
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16
Absolute structure	Flack (1983), 1165 Friedel pairs
Absolute structure parameter	0.039 (15)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

We thank the University of Notre Dame for its generous support of this program.

References

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