(3R,6S,7aS)-3-Phenyl-6-(phenyl­sulfan­yl)perhydro­pyrrolo[1,2-c]oxazol-5-one

Gainsford, G.J.; Luxenburger, A.; Woolhouse, A.D.

doi:10.1107/S1600536809011623

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o943

doi:10.1107/S1600536809011623

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(3R,6S,7aS)-3-Phenyl-6-(phenylsulfanyl)perhydropyrrolo[1,2-c]oxazol-5-one

Graeme J. Gainsford,^a ^* Andreas Luxenburger ^a and Anthony D. Woolhouse ^a

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 2 March 2009; accepted 29 March 2009; online 2 April 2009)

Molecules of the title compound [systematic name: (2R,5S,7S)-2-phenyl-7-phenylsulfanyl-1-aza-3-oxabicyclo[3.3.0]octan-8-one], C₁₈H₁₇NO₂S, form high quality crystals even though they are only packed using C—H⋯O(carbonyl) and weak C—H⋯S interactions. The dihedral angle between the aromatic rings is 85.53 (5)°. The fused rings adopt envelope and twist conformations.

Related literature

For related structures, see Nagasaka & Imai (1995 ); Anwar et al. (2003 ); Bailey et al. (2000 ); McCarthy et al. (1999 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₈H₁₇NO₂S
M_r = 311.39
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.3884 (3) Å
b = 11.2227 (7) Å
c = 25.3308 (16) Å
V = 1531.81 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 121 K
0.75 × 0.39 × 0.30 mm

Data collection

Bruker–Nonius APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.829, T_max = 0.937
45370 measured reflections
5948 independent reflections
5711 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.087
S = 1.11
5948 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 2508 Friedel pairs
Flack parameter: 0.01 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7A—H7A⋯O5ⁱ	1.00	2.55	3.4305 (13)	147
C7—H72⋯O5ⁱⁱ	0.99	2.62	3.3493 (16)	131
C1—H1B⋯O5ⁱⁱ	0.99	2.71	3.1513 (13)	108
C1—H1A⋯S1ⁱⁱ	0.99	3.00	3.9512 (14)	162
C4—H4⋯S1ⁱⁱⁱ	0.95	2.98	3.7531 (13)	139
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT and SADABS (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011623/er2064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011623/er2064Isup2.hkl

checkCIF report

Comment top

During the course of our efforts to delineate, in detail, the conversion of the bicyclic lactam 1 into its highly prized, chiral α,β-unsaturated derivative 5 employing sulfur chemistry (Fig. 3), we were able to isolate and separate the three anticipated products (2,3 & 4) from the rapid quenching of the lithium enolate of 1 with the electrophile, PhSSPh: the two 6-(phenylthio)-mono-adducts 2 and 3 were found to be predominant in the mixture with up to 10% only of the 6,6-bis(phenylthio)-adduct. In order to be able to unequivocally assign structures to each of the mono-adducts, we carried out an X-ray crystallographic study of the title cis(endo-) adduct 2 (Scheme) so that structural inferences made on the basis of nOe experiments could be corroborated (see bottom right entry in fig. 3).

The 2-(p-methoxyphenyl) derivative is described (molecule 21b) by Nagasaka & Imai (1995). Related compounds in the Cambridge Structural Database [C.S.D. Version 5.30 with November 2008 updates (Allen, 2002)] have been reported by Anwar et al. (2003) (IJAGUV) and Bailey et al. (2000) (QINMEF & QINMEJ).

The asymmetric unit is shown in Figure 1. The 5-membered fused rings (N4,C5,C6,C7,C7a) and (C1,O2,C3,N4,C7a) are best described as having envelope (on C6) and twist (on C1—O2) conformations (Spek, 2009). The 3-phenyl (C2,C4,C9—C12) and 6-phenylthio (C13—C18) phenyl rings subtend angles of 85.53 (5)° to each other and 71.74 (5) and 39.74 (5)° respectively to the mean plane through the fused ring (octan-8-one) atoms. The corresponding three angles for the 6-benzyl closest structural relative (QINMEF) are 80.14 (7), 71.18 (6) and 36.82 (7)° while the interplanar angles found for the 3-phenyl rings in IJAGUV & QINMIJ structures are 74.1 (4) and 76.73 (7)%, respectively.

The molecular packing is provided by mainly weak C–H···O interactions (entries 1–3, Table 1, involving a bifurcated O) as partly shown in Figure 2. The weak, just significant, C—H···S interactions have been observed before contributing to dimer formation in CUQXUH with a C—H···S angles of 140° (McCarthy et al., 1999).

These crystals were of superb quality, confirmed by the final agreement indices and difference density maps, which raises the issue of how many of the weak intermolecular interactions may just be fortuitous, with packing largely determined by the overall molecular shape and van der Waal's forces.

Related literature top

For related structures, see Nagasaka & Imai (1995); Anwar et al. (2003); Bailey et al. (2000); McCarthy et al. (1999). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a solution of the lactam 1 (19.7 g, 97.0 mmol) in dry THF (180 ml) was added dropwise LiHMDS (1 M solution in hexanes; 116 ml, 116 mmol) at -78 °C and the solution was stirred for further 60 min before a concentrated solution of diphenylsulfide (25.4 g, 116 mmol) in dry THF (25 ml) was added rapidly in one single portion at the same temperature. After being stirred for 3 h the reaction mixture was quenched at -78 °C with saturated aqueous ammonium chloride solution (50 ml) and allowed to warm to ambient temperature before being diluted with ethyl acetate (400 ml). The separated organic phase was washed with water and brine, dried over MgSO₄ and concentrated to give a crude oil, the composition of which was determined by HPLC analysis. Based on this analysis the two diastereomeric phenylthioethers 2 and 3 were formed in 40% and 49% yield, respectively. In addition, the reaction provided the bis(phenylthio)-adduct 4 in 9% as the by-product and 2% of the starting material remained unreacted. The crude product was finally fractionated by flash column chromatography (silica gel, 10% and 20% ethyl acetate/petroleum ether) to yield the three adducts 2, 3 and 4.

(2): (3R,6S,7aS)-3-Phenyl-6-(phenylthio)tetrahydropyrrolo [1,2-c]oxazol-5(1H)-one was recrystallized from ethyl acetate/petroleum ether to give colourless crystals, R_f = 0.44 (30% ethyl acetate/petroleum ether); m.p. 97–98 °C, [α]²¹_D=+215.6 (c 0.545, CHCl₃); FTIR (neat) 1692 (C=O) cm^-1; ¹H NMR (500 MHz, CDCl₃) δ 7.57–7.53 (m, 2H), 7.46–7.42 (m, 2H), 7.38–7.27 (m, 6H), 6.29 (s, 1H, H3), 4.26 (t, J=9.7 Hz, 1H, H6), 4.17 (dd, J=8.2, 6.2 Hz, 1H, H1α), 4.06–3.99 (m, 1H, H7aα), 3.21 (t, J=8.1 Hz, 1H, H1β), 2.81 (ddd, J=13.5, 9.2, 7.3 Hz, 1H, H7α), 1.93 (ddd, J=13.5, 10.2, 6.4 Hz, 1H, H7β); ¹³C NMR (125 MHz, CDCl₃) δ 173.54, 138.18, 132.91, 132.85, 128.94, 128.55, 128.29, 127.89, 125.82, 87.18, 71.88, 55.73, 51.06, 32.03; HRMS (ES+) m/z calcd for C₁₈H₁₇NO₂SNa⁺ 334.0878, obsd 334.0872; Anal. calcd for C₁₈H₁₇NO₂S: C, 69.43; H, 5.50; N, 4.50. Found: C, 69.32; H, 5.63; N, 4.63.

(3): (3R,6R,7aS)-3-Phenyl-6-(phenylthio)tetrahydropyrrolo [1,2-c]oxazol-5(1H)-one, colourless crystals, R_f = 0.30 (30% ethyl acetate/petroleum ether); m.p. 80 °C; [α]²⁰_D = +102.3 (c 1.05, CHCl₃); FTIR (neat) 1702 (C=O) cm^-1; ¹H NMR (500 MHz, DMSO-d₆) δ 7.52–7.48 (m, 2H); 7.41–7.30 (m, 6H); 7.27–7.23 (m, 2H), 6.05 (s, 1H, H3); 4.22 (dd, J=9.4, 3.3 Hz, 1H, H6); 4.13 (dd, J=8.0, 6.2 Hz, 1H, H1α); 3.90–3.83 (m, 1H, H7aα); 3.47 (t, J=8.4 Hz, 1H, H1β); 2.56 (ddd, J=14.5, 9.2, 5.3 Hz, 1H, H7β); 2.28 (ddd, J=14.2, 7.5, 3.3, 1H, H7α); ¹³C NMR (125 MHz, DMSO-d₆) δ 174.58, 138.57, 132.55, 131.99, 129.02, 128.49, 128.25, 127.76, 125.93, 86.47, 70.97, 57.11, 49.25, 30.66; HRMS (ES+) m/z calcd for C₁₈H₁₇NO₂SNa⁺ 334.0878, obsd 334.0879; Anal. calcd for C₁₈H₁₇NO₂S: C, 69.43; H, 5.50; N, 4.50. Found C, 69.39; H, 5.59; N, 4.55.

(4): (3R,7aS)-3-Phenyl-6,6- bis(phenylthio)tetrahydropyrrolo[1,2-c]oxazol-5(1H)-one, colourless crystals, R_f = 0.54 (30% ethyl acetate/petroleum ether); m.p. 108 °C; [α]²⁰_D = +157.1 (c 0.62, CDCl₃); FTIR (neat) 1698 (C=O) cm^-1; ¹H NMR (500 MHz, CDCl₃) δ 7.71–7.68 (m, 2H), 7.59–7.55 (m, 2H), 7.41–7.29 (m, 9H), 7.25–7.20 (m, 2H), 6.19 (s, 1H), 4.03 (dd, J=8.1, 6.3 Hz, 1H), 3.69–3.63 (m, 1H), 3.09 (t, J=8.1 Hz, 1H), 2.54 (dd, J=14.3, 7.0 Hz, 1H), 2.35 (dd, J=14.3, 6.5 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 171.71, 137.95, 136.65, 136.27, 131.18, 130.44, 129.96, 129.57, 129.01, 128.87, 128.67, 128.35, 126.02, 87.09, 71.78, 68.68, 55.00, 39.79; HRMS (ES+) m/z calcd for C₂₄H₂₁NO₂S₂Na⁺ 442.0911, obsd 442.0191; Anal. calcd for C₂₄H₂₁NO₂S₂: C, 68.70; H, 5.04; N, 3.34. Found C, 68.88; H, 5.29; N, 3.37.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT and SADABS (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), Mercury (Macrae et al., 2006) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the asymmetric unit (Farrugia, 1997); displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Packing diagram (Mercury; Macrae et al.,2006) of the unit cell. Contact atoms are shown as balls; not all interactions and labels are shown for clarity (see Table 1).
	Fig. 3. Preparation of the title compound.

(2R,5S,7S)-2-phenyl-7-phenylsulfanyl-1-aza-3- oxabicyclo[3.3.0]octan-8-one top

Crystal data top

C₁₈H₁₇NO₂S	F(000) = 656
M_r = 311.39	D_x = 1.350 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9806 reflections
a = 5.3884 (3) Å	θ = 3.0–34.4°
b = 11.2227 (7) Å	µ = 0.22 mm⁻¹
c = 25.3308 (16) Å	T = 121 K
V = 1531.81 (16) Å³	Block, colourless
Z = 4	0.75 × 0.39 × 0.30 mm

Data collection top

Bruker–Nonius APEXII CCD area-detector diffractometer	5948 independent reflections
Radiation source: fine-focus sealed tube	5711 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 8.333 pixels mm^-1	θ_max = 34.0°, θ_min = 3.0°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (Blessing, 1995)	k = −17→16
T_min = 0.829, T_max = 0.937	l = −38→38
45370 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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0528P)² + 0.1721P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
5948 reflections	Δρ_max = 0.38 e Å⁻³
199 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2508 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

Crystal data top

C₁₈H₁₇NO₂S	V = 1531.81 (16) Å³
M_r = 311.39	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.3884 (3) Å	µ = 0.22 mm⁻¹
b = 11.2227 (7) Å	T = 121 K
c = 25.3308 (16) Å	0.75 × 0.39 × 0.30 mm

Data collection top

Bruker–Nonius APEXII CCD area-detector diffractometer	5948 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	5711 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.937	R_int = 0.030
45370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.087	Δρ_max = 0.38 e Å⁻³
S = 1.11	Δρ_min = −0.20 e Å⁻³
5948 reflections	Absolute structure: Flack (1983), 2508 Friedel pairs
199 parameters	Absolute structure parameter: 0.01 (4)
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	0.53402 (5)	0.52168 (2)	0.147539 (9)	0.02284 (6)
O2	0.63842 (15)	0.59460 (6)	0.36457 (3)	0.02259 (14)
O5	0.76332 (18)	0.36178 (6)	0.23809 (3)	0.02532 (15)
N4	0.80755 (16)	0.53105 (7)	0.28760 (3)	0.01873 (14)
C1	0.5697 (2)	0.67901 (8)	0.32437 (4)	0.02362 (18)
H1A	0.5735	0.7616	0.3381	0.028*
H1B	0.4020	0.6619	0.3103	0.028*
C2	0.88109 (18)	0.41716 (8)	0.37229 (3)	0.01718 (15)
C3	0.70664 (17)	0.48760 (8)	0.33825 (3)	0.01756 (15)
H3	0.5543	0.4392	0.3313	0.021*
C4	0.8234 (2)	0.29955 (8)	0.38433 (4)	0.02221 (17)
H4	0.6793	0.2640	0.3695	0.027*
C5	0.77799 (18)	0.46990 (8)	0.24169 (3)	0.01866 (15)
C6	0.7641 (2)	0.56099 (8)	0.19659 (4)	0.02006 (16)
H6	0.9305	0.5691	0.1795	0.024*
C7	0.6940 (3)	0.67833 (8)	0.22432 (4)	0.0274 (2)
H71	0.7857	0.7462	0.2087	0.033*
H72	0.5138	0.6938	0.2212	0.033*
C7A	0.7678 (2)	0.66023 (8)	0.28236 (4)	0.02122 (17)
H7A	0.9223	0.7055	0.2911	0.025*
C9	0.9747 (2)	0.23345 (9)	0.41785 (5)	0.02726 (19)
H9	0.9343	0.1531	0.4259	0.033*
C10	1.1843 (2)	0.28528 (10)	0.43943 (4)	0.0288 (2)
H10	1.2878	0.2406	0.4624	0.035*
C11	1.2439 (2)	0.40310 (10)	0.42745 (5)	0.0274 (2)
H11	1.3877	0.4386	0.4424	0.033*
C12	1.09340 (18)	0.46886 (9)	0.39371 (4)	0.02237 (17)
H12	1.1353	0.5489	0.3853	0.027*
C13	0.71008 (18)	0.45302 (7)	0.09728 (4)	0.01856 (15)
C14	0.9116 (2)	0.37876 (9)	0.10770 (4)	0.02280 (18)
H14	0.9565	0.3611	0.1431	0.027*
C15	1.0467 (2)	0.33070 (10)	0.06609 (4)	0.02566 (19)
H15	1.1859	0.2813	0.0732	0.031*
C16	0.9801 (2)	0.35426 (9)	0.01414 (4)	0.02609 (19)
H16	1.0746	0.3221	−0.0142	0.031*
C17	0.7743 (2)	0.42516 (9)	0.00390 (4)	0.02471 (18)
H17	0.7254	0.4397	−0.0316	0.030*
C18	0.63983 (19)	0.47488 (9)	0.04504 (4)	0.02167 (16)
H18	0.5001	0.5238	0.0377	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02433 (10)	0.02516 (10)	0.01902 (10)	0.00568 (8)	−0.00096 (8)	−0.00069 (8)
O2	0.0304 (3)	0.0205 (3)	0.0169 (3)	0.0075 (3)	0.0009 (3)	−0.0014 (2)
O5	0.0404 (4)	0.0151 (3)	0.0205 (3)	0.0020 (3)	−0.0005 (3)	−0.0027 (2)
N4	0.0270 (4)	0.0144 (3)	0.0148 (3)	0.0010 (3)	0.0016 (3)	−0.0007 (2)
C1	0.0323 (5)	0.0203 (4)	0.0183 (4)	0.0070 (3)	−0.0006 (3)	−0.0002 (3)
C2	0.0203 (4)	0.0172 (3)	0.0141 (3)	0.0012 (3)	0.0009 (3)	−0.0011 (2)
C3	0.0218 (4)	0.0166 (3)	0.0143 (3)	0.0006 (3)	0.0007 (3)	−0.0006 (2)
C4	0.0250 (4)	0.0179 (3)	0.0236 (4)	−0.0004 (3)	−0.0009 (3)	−0.0001 (3)
C5	0.0243 (4)	0.0167 (3)	0.0150 (3)	0.0018 (3)	0.0006 (3)	−0.0009 (3)
C6	0.0282 (4)	0.0173 (3)	0.0147 (4)	0.0012 (3)	0.0007 (3)	0.0002 (3)
C7	0.0481 (6)	0.0161 (3)	0.0180 (4)	0.0049 (4)	0.0023 (4)	0.0002 (3)
C7A	0.0305 (5)	0.0140 (3)	0.0191 (4)	−0.0005 (3)	0.0014 (3)	−0.0016 (3)
C9	0.0311 (5)	0.0220 (4)	0.0287 (5)	0.0036 (4)	0.0001 (4)	0.0047 (3)
C10	0.0285 (5)	0.0328 (5)	0.0251 (5)	0.0093 (4)	−0.0033 (4)	0.0021 (4)
C11	0.0213 (4)	0.0334 (5)	0.0276 (5)	0.0029 (4)	−0.0047 (4)	−0.0034 (4)
C12	0.0197 (4)	0.0229 (4)	0.0245 (4)	−0.0016 (3)	0.0002 (3)	−0.0016 (3)
C13	0.0228 (4)	0.0169 (3)	0.0160 (3)	−0.0008 (3)	−0.0019 (3)	0.0000 (3)
C14	0.0280 (5)	0.0238 (4)	0.0167 (4)	0.0053 (3)	−0.0025 (3)	0.0008 (3)
C15	0.0268 (4)	0.0281 (4)	0.0222 (4)	0.0062 (4)	−0.0019 (4)	−0.0027 (3)
C16	0.0301 (5)	0.0293 (4)	0.0189 (4)	0.0002 (4)	0.0015 (4)	−0.0029 (3)
C17	0.0311 (5)	0.0272 (4)	0.0158 (4)	−0.0028 (4)	−0.0047 (4)	0.0004 (3)
C18	0.0251 (4)	0.0216 (4)	0.0183 (4)	−0.0007 (3)	−0.0053 (3)	0.0022 (3)

Geometric parameters (Å, º) top

S1—C13	1.7648 (10)	C7—H71	0.9900
S1—C6	1.8098 (10)	C7—H72	0.9900
O2—C3	1.4217 (11)	C7A—H7A	1.0000
O2—C1	1.4393 (12)	C9—C10	1.3831 (17)
O5—C5	1.2194 (11)	C9—H9	0.9500
N4—C5	1.3598 (11)	C10—C11	1.3940 (17)
N4—C7A	1.4716 (11)	C10—H10	0.9500
N4—C3	1.4762 (11)	C11—C12	1.3901 (15)
C1—C7A	1.5218 (15)	C11—H11	0.9500
C1—H1A	0.9900	C12—H12	0.9500
C1—H1B	0.9900	C13—C14	1.3942 (13)
C2—C4	1.3900 (12)	C13—C18	1.3981 (12)
C2—C12	1.3927 (13)	C14—C15	1.3899 (14)
C2—C3	1.5007 (13)	C14—H14	0.9500
C3—H3	1.0000	C15—C16	1.3896 (14)
C4—C9	1.3913 (15)	C15—H15	0.9500
C4—H4	0.9500	C16—C17	1.3892 (16)
C5—C6	1.5348 (13)	C16—H16	0.9500
C6—C7	1.5395 (13)	C17—C18	1.3866 (15)
C6—H6	1.0000	C17—H17	0.9500
C7—C7A	1.5363 (14)	C18—H18	0.9500

C13—S1—C6	103.50 (5)	H71—C7—H72	108.8
C3—O2—C1	106.90 (7)	N4—C7A—C1	100.10 (8)
C5—N4—C7A	113.75 (8)	N4—C7A—C7	104.74 (7)
C5—N4—C3	122.24 (8)	C1—C7A—C7	118.00 (10)
C7A—N4—C3	110.50 (7)	N4—C7A—H7A	111.1
O2—C1—C7A	102.90 (8)	C1—C7A—H7A	111.1
O2—C1—H1A	111.2	C7—C7A—H7A	111.1
C7A—C1—H1A	111.2	C10—C9—C4	119.71 (10)
O2—C1—H1B	111.2	C10—C9—H9	120.1
C7A—C1—H1B	111.2	C4—C9—H9	120.1
H1A—C1—H1B	109.1	C9—C10—C11	120.05 (10)
C4—C2—C12	119.60 (9)	C9—C10—H10	120.0
C4—C2—C3	119.09 (9)	C11—C10—H10	120.0
C12—C2—C3	121.26 (8)	C12—C11—C10	120.22 (10)
O2—C3—N4	102.93 (7)	C12—C11—H11	119.9
O2—C3—C2	109.72 (7)	C10—C11—H11	119.9
N4—C3—C2	116.27 (8)	C11—C12—C2	119.82 (9)
O2—C3—H3	109.2	C11—C12—H12	120.1
N4—C3—H3	109.2	C2—C12—H12	120.1
C2—C3—H3	109.2	C14—C13—C18	119.67 (9)
C2—C4—C9	120.59 (10)	C14—C13—S1	122.90 (7)
C2—C4—H4	119.7	C18—C13—S1	117.43 (7)
C9—C4—H4	119.7	C15—C14—C13	119.76 (9)
O5—C5—N4	125.01 (9)	C15—C14—H14	120.1
O5—C5—C6	127.15 (8)	C13—C14—H14	120.1
N4—C5—C6	107.84 (7)	C16—C15—C14	120.60 (10)
C5—C6—C7	104.01 (7)	C16—C15—H15	119.7
C5—C6—S1	112.46 (6)	C14—C15—H15	119.7
C7—C6—S1	110.72 (8)	C17—C16—C15	119.47 (10)
C5—C6—H6	109.8	C17—C16—H16	120.3
C7—C6—H6	109.8	C15—C16—H16	120.3
S1—C6—H6	109.8	C18—C17—C16	120.49 (9)
C7A—C7—C6	105.07 (8)	C18—C17—H17	119.8
C7A—C7—H71	110.7	C16—C17—H17	119.8
C6—C7—H71	110.7	C17—C18—C13	119.95 (9)
C7A—C7—H72	110.7	C17—C18—H18	120.0
C6—C7—H72	110.7	C13—C18—H18	120.0

C3—O2—C1—C7A	−42.19 (10)	C5—N4—C7A—C1	124.87 (9)
C1—O2—C3—N4	30.62 (10)	C3—N4—C7A—C1	−17.02 (10)
C1—O2—C3—C2	155.00 (8)	C5—N4—C7A—C7	2.19 (12)
C5—N4—C3—O2	−145.28 (9)	C3—N4—C7A—C7	−139.70 (9)
C7A—N4—C3—O2	−7.18 (10)	O2—C1—C7A—N4	34.70 (9)
C5—N4—C3—C2	94.76 (11)	O2—C1—C7A—C7	147.49 (8)
C7A—N4—C3—C2	−127.14 (9)	C6—C7—C7A—N4	−14.67 (12)
C4—C2—C3—O2	125.46 (9)	C6—C7—C7A—C1	−124.87 (9)
C12—C2—C3—O2	−51.84 (11)	C2—C4—C9—C10	0.09 (16)
C4—C2—C3—N4	−118.31 (9)	C4—C9—C10—C11	−0.26 (17)
C12—C2—C3—N4	64.39 (11)	C9—C10—C11—C12	−0.13 (17)
C12—C2—C4—C9	0.47 (15)	C10—C11—C12—C2	0.70 (16)
C3—C2—C4—C9	−176.88 (9)	C4—C2—C12—C11	−0.86 (14)
C7A—N4—C5—O5	−167.92 (11)	C3—C2—C12—C11	176.43 (9)
C3—N4—C5—O5	−31.03 (16)	C6—S1—C13—C14	37.85 (9)
C7A—N4—C5—C6	11.47 (12)	C6—S1—C13—C18	−142.53 (7)
C3—N4—C5—C6	148.36 (8)	C18—C13—C14—C15	2.42 (15)
O5—C5—C6—C7	159.26 (12)	S1—C13—C14—C15	−177.97 (8)
N4—C5—C6—C7	−20.11 (11)	C13—C14—C15—C16	−1.15 (17)
O5—C5—C6—S1	39.41 (14)	C14—C15—C16—C17	−0.94 (17)
N4—C5—C6—S1	−139.96 (7)	C15—C16—C17—C18	1.75 (16)
C13—S1—C6—C5	−98.36 (7)	C16—C17—C18—C13	−0.48 (15)
C13—S1—C6—C7	145.76 (7)	C14—C13—C18—C17	−1.62 (14)
C5—C6—C7—C7A	20.79 (12)	S1—C13—C18—C17	178.75 (8)
S1—C6—C7—C7A	141.81 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7A—H7A···O5ⁱ	1.00	2.55	3.4305 (13)	147
C7—H72···O5ⁱⁱ	0.99	2.62	3.3493 (16)	131
C1—H1B···O5ⁱⁱ	0.99	2.71	3.1513 (13)	108
C1—H1A···S1ⁱⁱ	0.99	3.00	3.9512 (14)	162
C4—H4···S1ⁱⁱⁱ	0.95	2.98	3.7531 (13)	139

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇NO₂S
M_r	311.39
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	121
a, b, c (Å)	5.3884 (3), 11.2227 (7), 25.3308 (16)
V (Å³)	1531.81 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.75 × 0.39 × 0.30

Data collection
Diffractometer	Bruker–Nonius APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.829, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	45370, 5948, 5711
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.787

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.087, 1.11
No. of reflections	5948
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.20
Absolute structure	Flack (1983), 2508 Friedel pairs
Absolute structure parameter	0.01 (4)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SAINT and SADABS (Bruker, 2006), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), Mercury (Macrae et al., 2006) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7A—H7A···O5ⁱ	1.00	2.55	3.4305 (13)	147
C7—H72···O5ⁱⁱ	0.99	2.62	3.3493 (16)	131
C1—H1B···O5ⁱⁱ	0.99	2.71	3.1513 (13)	108
C1—H1A···S1ⁱⁱ	0.99	3.00	3.9512 (14)	162
C4—H4···S1ⁱⁱⁱ	0.95	2.98	3.7531 (13)	139

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2.

Acknowledgements

We thank Dr J. Wikaira of the University of Canterbury for her assistance in data collection, as well as the New Zealand Foundation for Science and Technology and New Zealand Pharmaceuticals Ltd for financial support.

References

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