5-Benz­yloxy-3-methyl-1-tosyl-1H-indole

Pozza Silveira, G.; Oliver, A.G.; Noll, B.C.

doi:10.1107/S1600536813014001

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o979

doi:10.1107/S1600536813014001

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5-Benzyloxy-3-methyl-1-tosyl-1H-indole

Gustavo Pozza Silveira,^a ^* Allen G. Oliver ^b and Bruce C. Noll ^c

^aDepartamento de Química Orgânica, Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre/RS, 91501-970, Brazil, ^bDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA, and ^cBruker ACS Inc., 5465 East Cheryl Parkway, Madison, WI 53711, USA
^*Correspondence e-mail: gustavo.silveira@iq.ufrgs.br

(Received 19 April 2013; accepted 20 May 2013; online 31 May 2013)

The title compound, C₂₃H₂₁NO₃S, represents one of the few examples of a 5-substituted indole with a toluenesulfonyl group bonded to the N atom. The benzyl group adopts a synclinal geometry with respect to the indole ring [dihedral angle = 59.95 (4)°], while the tolyl ring is oriented close to perpendicular to the indole ring, making a dihedral angle of 81.85 (3)°. The indole N atom exhibits a slight pyramidalization.

Related literature

For background to physostigmine and related marine natural products, see: Marino et al. (1989 , 1992 ). For recent, related structural and synthetic studies, see: Pozza Silveira et al. (2012 ); Silveira & Marino (2013 ). For related compounds, see: Xiong et al. (2001 ); Witulski et al. (2000 ). For reference structural data see: Allen et al. (1995 ).

Experimental

Crystal data

C₂₃H₂₁NO₃S
M_r = 391.47
Monoclinic, P 2₁ /n
a = 8.317 (3) Å
b = 15.601 (6) Å
c = 14.752 (5) Å
β = 90.884 (11)°
V = 1914.1 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.39 × 0.33 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.636, T_max = 0.746
30660 measured reflections
6415 independent reflections
5550 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.04
6415 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.42 e Å⁻³

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: SHELXL2012 (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: 10.1107/S1600536813014001/kj2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813014001/kj2226Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813014001/kj2226Isup3.cml

checkCIF report

Comment top

Substituted indoles serve as unique precursors for medicinally important physostigmine alkaloids, which are anticholinesterases and miotics. This alkaloid skeleton has been found in marine alkaloids from Broyoza Flustra foliacea in the flustramines (Marino et al., 1989) The literature presents a great number of enantiocontrolled syntheses for the natural and unnatural physostigmine (Marino et al., 1992) Our interest in physostigmine emanated from our recent asymmetric synthesis of naphthyl lactams (Silveira & Marino, 2013) using chiral vinyl sulfilimines (Pozza Silveira et al., 2012). Herein we report 5-(benzyloxy)-3-methyl-1-tosyl-1H-indole as a potential physostigmine precursor.

The title compound, C₂₃H₂₁NO₃S, exhibits no unusual structural features and represents one of the few examples of an indole with a toluenesulfonyl bonded to the nitrogen and an oxygen bridging moiety bonded in the 5-position on the indole ring. The two other examples are 5-cyano-2-methoxy-4-trifluoromethyl-6-[3'-(N-toluenesulfonyl-5'-µethoxyindolyl)]pyridine (Xiong et al., 2001) and 1-(4-methylphenyl)sulfonyl-3-((E)-2-(benzyl((4-methylphenyl)sulfonyl)αmino)ethenyl)-5-methoxy-1H-indole (Witulski et al., 2000). In both of these examples the 5-position is occupied by a methoxy group.

Bond distances and angles are within normal, acceptable ranges (Allen et al. 1995). The benzyl moiety adopts a syn-clinal geometry with respect to the indole ring (interplanar angle = 59.95 (4)°), while the tolyl ring is oriented close to perpendicular to the indole ring (interplanar angle = 81.85 (3)°). The complement of this angle, 108.15°, is close to the N1—S1—C16 angle (104.19 (5)°). The difference is a consequence of a slight pyramidalization of the indolic nitrogen.

Related literature top

For background to physostigmine and related marine natural products, see: Marino et al. (1989, 1992). For recent, related structural and synthetic studies, see: Pozza Silveira et al. (2012); Silveira & Marino (2013). For related compounds, see: Xiong et al. (2001); Witulski et al. (2000). For reference structural data see: Allen et al. (1995).

Experimental top

To a stirred solution of dimsylsodium [prepared from 110 mg (2.75 mmol) of NaH 60% dispersion in mineral oil and dimethylsulfoxide dry (0.58 ml) at 338 to 343 K until H₂ is no longer evolved] was added a solution of 5-benzyloxy-3-methylindole (325 mg, 1.37 mmol) in dry THF (0.9 ml) under ice cooling. After stirring at room temperature for 1 h a solution of 4-methylbenzenesulfonyl chloride (225 mg, 1.18 mmol) in THF (0.9 ml) was added to this mixture at 273 K. After being stirred at room temperature for 16 h, the reaction product was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over Na₂SO₄, and evaporated. The remaining residue was recrystallized from ethyl acetate/hexanes to give 482 mg of the desired product as white needle crystals (90%): mp 402 to 403 K. A suitably sized, block-like crystal was cut from a larger, columnar crystal for the diffraction study.

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: SHELXL2012 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Labelling scheme for the title compound. Displacement ellipsoids depicted at 50% probability level. The labeling scheme follows the convention for indoles.

5-Benzyloxy-3-methyl-1-tosyl-1H-indole top

Crystal data top

C₂₃H₂₁NO₃S	D_x = 1.358 Mg m⁻³
M_r = 391.47	Melting point: 402 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.317 (3) Å	Cell parameters from 9980 reflections
b = 15.601 (6) Å	θ = 2.6–31.6°
c = 14.752 (5) Å	µ = 0.19 mm⁻¹
β = 90.884 (11)°	T = 100 K
V = 1914.1 (12) Å³	Block, colourless
Z = 4	0.39 × 0.33 × 0.15 mm
F(000) = 824

Data collection top

Bruker APEXII diffractometer	6415 independent reflections
Radiation source: fine-focus sealed tube	5550 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.33 pixels mm^-1	θ_max = 31.6°, θ_min = 1.9°
combination of ω and ϕ–scans	h = −10→12
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −22→22
T_min = 0.636, T_max = 0.746	l = −21→21
30660 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0536P)² + 0.775P] where P = (F_o² + 2F_c²)/3
6415 reflections	(Δ/σ)_max = 0.001
255 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₂₃H₂₁NO₃S	V = 1914.1 (12) Å³
M_r = 391.47	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.317 (3) Å	µ = 0.19 mm⁻¹
b = 15.601 (6) Å	T = 100 K
c = 14.752 (5) Å	0.39 × 0.33 × 0.15 mm
β = 90.884 (11)°

Data collection top

Bruker APEXII diffractometer	6415 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5550 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.746	R_int = 0.026
30660 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.04	Δρ_max = 0.59 e Å⁻³
6415 reflections	Δρ_min = −0.42 e Å⁻³
255 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.84082 (10)	0.26302 (5)	0.60391 (6)	0.01478 (15)
O1	0.35145 (9)	0.40007 (6)	0.39442 (5)	0.02043 (16)
S1	0.98068 (3)	0.19050 (2)	0.58368 (2)	0.01438 (6)
O2	1.08199 (9)	0.19022 (5)	0.66274 (5)	0.01998 (15)
C2	0.77142 (12)	0.27143 (6)	0.69017 (6)	0.01592 (17)
H2	0.8203	0.2534	0.7456	0.019*
O3	1.04493 (9)	0.21088 (5)	0.49733 (5)	0.01909 (15)
C3	0.62522 (12)	0.30883 (6)	0.68241 (6)	0.01519 (17)
C3'	0.59545 (12)	0.32359 (6)	0.58690 (6)	0.01410 (17)
C4	0.46627 (12)	0.36208 (7)	0.54150 (6)	0.01652 (18)
H4	0.3777	0.3846	0.5737	0.020*
C5	0.47154 (12)	0.36630 (7)	0.44789 (6)	0.01665 (18)
C6	0.60430 (13)	0.33495 (7)	0.40057 (7)	0.01818 (19)
H6	0.6050	0.3390	0.3363	0.022*
C7	0.73415 (12)	0.29828 (7)	0.44561 (7)	0.01689 (18)
H7	0.8246	0.2777	0.4136	0.020*
C7'	0.72720 (12)	0.29276 (6)	0.53938 (6)	0.01406 (16)
C8	0.51260 (13)	0.33196 (7)	0.75577 (7)	0.0202 (2)
H8A	0.5623	0.3187	0.8148	0.030*
H8B	0.4129	0.2991	0.7484	0.030*
H8C	0.4884	0.3934	0.7525	0.030*
C9	0.21302 (12)	0.42980 (7)	0.44164 (7)	0.01792 (18)
H9A	0.2426	0.4792	0.4806	0.022*
H9B	0.1713	0.3836	0.4808	0.022*
C10	0.08711 (11)	0.45595 (6)	0.37411 (6)	0.01452 (17)
C11	0.02533 (13)	0.53835 (7)	0.37424 (7)	0.01724 (18)
H11	0.0674	0.5795	0.4157	0.021*
C12	−0.09749 (14)	0.56142 (7)	0.31438 (7)	0.0217 (2)
H12	−0.1390	0.6181	0.3148	0.026*
C13	−0.15915 (13)	0.50175 (8)	0.25425 (7)	0.0240 (2)
H13	−0.2447	0.5171	0.2140	0.029*
C14	−0.09673 (13)	0.41950 (8)	0.25233 (7)	0.0222 (2)
H14	−0.1380	0.3788	0.2101	0.027*
C15	0.02576 (13)	0.39676 (7)	0.31194 (7)	0.01826 (18)
H15	0.0685	0.3403	0.3105	0.022*
C16	0.87513 (12)	0.09408 (6)	0.57724 (6)	0.01472 (17)
C17	0.82732 (14)	0.06170 (7)	0.49366 (7)	0.0208 (2)
H17	0.8571	0.0897	0.4392	0.025*
C18	0.73530 (15)	−0.01231 (7)	0.49093 (7)	0.0232 (2)
H18	0.7026	−0.0352	0.4339	0.028*
C19	0.68993 (13)	−0.05376 (7)	0.56976 (7)	0.01902 (19)
C20	0.73877 (14)	−0.01942 (7)	0.65257 (7)	0.0206 (2)
H20	0.7076	−0.0469	0.7070	0.025*
C21	0.83179 (13)	0.05392 (7)	0.65732 (7)	0.01885 (19)
H21	0.8655	0.0765	0.7143	0.023*
C22	0.59305 (15)	−0.13461 (8)	0.56597 (9)	0.0263 (2)
H22A	0.5294	−0.1360	0.5095	0.040*
H22B	0.5209	−0.1366	0.6178	0.040*
H22C	0.6654	−0.1842	0.5681	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0144 (4)	0.0164 (4)	0.0135 (3)	0.0039 (3)	−0.0007 (3)	0.0004 (3)
O1	0.0149 (3)	0.0329 (4)	0.0135 (3)	0.0072 (3)	−0.0001 (3)	0.0038 (3)
S1	0.01210 (11)	0.01661 (11)	0.01444 (11)	0.00244 (8)	0.00002 (8)	0.00062 (7)
O2	0.0160 (3)	0.0249 (4)	0.0189 (3)	0.0024 (3)	−0.0046 (3)	0.0003 (3)
C2	0.0187 (4)	0.0165 (4)	0.0125 (4)	0.0018 (3)	−0.0011 (3)	0.0009 (3)
O3	0.0167 (3)	0.0226 (3)	0.0180 (3)	0.0019 (3)	0.0042 (3)	0.0027 (3)
C3	0.0174 (4)	0.0165 (4)	0.0116 (4)	0.0017 (3)	−0.0001 (3)	0.0003 (3)
C3'	0.0146 (4)	0.0158 (4)	0.0119 (4)	0.0009 (3)	0.0003 (3)	0.0002 (3)
C4	0.0149 (4)	0.0211 (4)	0.0135 (4)	0.0037 (3)	0.0005 (3)	0.0011 (3)
C5	0.0148 (4)	0.0214 (4)	0.0137 (4)	0.0021 (3)	−0.0011 (3)	0.0027 (3)
C6	0.0172 (4)	0.0249 (5)	0.0124 (4)	0.0024 (4)	0.0010 (3)	0.0021 (3)
C7	0.0154 (4)	0.0219 (4)	0.0135 (4)	0.0027 (3)	0.0021 (3)	0.0011 (3)
C7'	0.0139 (4)	0.0152 (4)	0.0130 (4)	0.0011 (3)	−0.0007 (3)	0.0010 (3)
C8	0.0221 (5)	0.0251 (5)	0.0136 (4)	0.0054 (4)	0.0027 (3)	−0.0001 (3)
C9	0.0151 (4)	0.0245 (5)	0.0142 (4)	0.0038 (4)	0.0000 (3)	0.0008 (3)
C10	0.0123 (4)	0.0173 (4)	0.0140 (4)	0.0002 (3)	0.0002 (3)	0.0024 (3)
C11	0.0183 (5)	0.0173 (4)	0.0161 (4)	0.0017 (3)	0.0008 (3)	−0.0004 (3)
C12	0.0221 (5)	0.0246 (5)	0.0186 (4)	0.0094 (4)	0.0021 (4)	0.0036 (4)
C13	0.0169 (5)	0.0378 (6)	0.0171 (4)	0.0061 (4)	−0.0024 (4)	0.0019 (4)
C14	0.0182 (5)	0.0293 (5)	0.0191 (4)	−0.0035 (4)	−0.0025 (4)	−0.0031 (4)
C15	0.0181 (5)	0.0166 (4)	0.0201 (4)	−0.0013 (3)	−0.0003 (3)	0.0003 (3)
C16	0.0146 (4)	0.0155 (4)	0.0140 (4)	0.0031 (3)	0.0007 (3)	0.0000 (3)
C17	0.0269 (5)	0.0216 (5)	0.0140 (4)	−0.0009 (4)	−0.0005 (4)	0.0006 (3)
C18	0.0292 (6)	0.0226 (5)	0.0178 (4)	−0.0022 (4)	−0.0025 (4)	−0.0025 (4)
C19	0.0169 (4)	0.0171 (4)	0.0231 (5)	0.0021 (3)	0.0019 (4)	−0.0016 (3)
C20	0.0231 (5)	0.0202 (4)	0.0187 (4)	0.0007 (4)	0.0054 (4)	0.0007 (4)
C21	0.0228 (5)	0.0196 (4)	0.0142 (4)	0.0009 (4)	0.0023 (3)	−0.0007 (3)
C22	0.0227 (5)	0.0219 (5)	0.0344 (6)	−0.0032 (4)	0.0025 (4)	−0.0030 (4)

Geometric parameters (Å, º) top

N1—C7'	1.4096 (13)	C17—C18	1.3855 (16)
N1—C2	1.4116 (13)	C18—C19	1.3881 (16)
N1—S1	1.6531 (9)	C19—C20	1.3889 (16)
O1—C5	1.3687 (12)	C19—C22	1.4973 (16)
O1—C9	1.4320 (13)	C20—C21	1.3824 (16)
S1—O3	1.4249 (9)	C2—H2	0.9500
S1—O2	1.4284 (9)	C4—H4	0.9500
S1—C16	1.7436 (11)	C6—H6	0.9500
C2—C3	1.3521 (14)	C7—H7	0.9500
C3—C3'	1.4454 (14)	C8—H8A	0.9800
C3—C8	1.4866 (14)	C8—H8B	0.9800
C3'—C4	1.3933 (14)	C8—H8C	0.9800
C3'—C7'	1.3955 (13)	C9—H9A	0.9900
C4—C5	1.3839 (14)	C9—H9B	0.9900
C5—C6	1.4035 (14)	C11—H11	0.9500
C6—C7	1.3831 (14)	C12—H12	0.9500
C7—C7'	1.3880 (14)	C13—H13	0.9500
C9—C10	1.4912 (14)	C14—H14	0.9500
C10—C11	1.3844 (14)	C15—H15	0.9500
C10—C15	1.3928 (14)	C17—H17	0.9500
C11—C12	1.3874 (15)	C18—H18	0.9500
C12—C13	1.3793 (17)	C20—H20	0.9500
C13—C14	1.3847 (18)	C21—H21	0.9500
C14—C15	1.3818 (15)	C22—H22A	0.9800
C16—C17	1.3852 (14)	C22—H22B	0.9800
C16—C21	1.3897 (14)	C22—H22C	0.9800

C7'—N1—C2	107.40 (8)	C20—C21—C16	118.84 (10)
C7'—N1—S1	124.73 (7)	C3—C2—H2	125.0
C2—N1—S1	121.67 (7)	N1—C2—H2	125.0
C5—O1—C9	115.43 (8)	C5—C4—H4	121.2
O3—S1—O2	120.40 (5)	C3'—C4—H4	121.2
O3—S1—N1	106.46 (5)	C7—C6—H6	119.3
O2—S1—N1	105.22 (5)	C5—C6—H6	119.3
O3—S1—C16	109.83 (5)	C6—C7—H7	121.3
O2—S1—C16	109.39 (5)	C7'—C7—H7	121.3
N1—S1—C16	104.19 (5)	C3—C8—H8A	109.5
C3—C2—N1	110.09 (8)	C3—C8—H8B	109.5
C2—C3—C3'	106.96 (9)	H8A—C8—H8B	109.5
C2—C3—C8	128.25 (9)	C3—C8—H8C	109.5
C3'—C3—C8	124.79 (9)	H8A—C8—H8C	109.5
C4—C3'—C7'	120.85 (9)	H8B—C8—H8C	109.5
C4—C3'—C3	131.03 (9)	O1—C9—H9A	109.9
C7'—C3'—C3	108.11 (9)	C10—C9—H9A	109.9
C5—C4—C3'	117.65 (9)	O1—C9—H9B	109.9
O1—C5—C4	124.01 (9)	C10—C9—H9B	109.9
O1—C5—C6	114.85 (9)	H9A—C9—H9B	108.3
C4—C5—C6	121.14 (9)	C10—C11—H11	119.7
C7—C6—C5	121.30 (9)	C12—C11—H11	119.7
C6—C7—C7'	117.41 (9)	C13—C12—H12	120.1
C7—C7'—C3'	121.62 (9)	C11—C12—H12	120.1
C7—C7'—N1	130.97 (9)	C12—C13—H13	119.9
C3'—C7'—N1	107.32 (8)	C14—C13—H13	119.9
O1—C9—C10	108.98 (8)	C15—C14—H14	120.1
C11—C10—C15	118.98 (9)	C13—C14—H14	120.1
C11—C10—C9	120.67 (9)	C14—C15—H15	119.7
C15—C10—C9	120.32 (9)	C10—C15—H15	119.7
C10—C11—C12	120.64 (10)	C16—C17—H17	120.6
C13—C12—C11	119.80 (10)	C18—C17—H17	120.6
C12—C13—C14	120.18 (10)	C17—C18—H18	119.3
C15—C14—C13	119.86 (10)	C19—C18—H18	119.3
C14—C15—C10	120.52 (10)	C21—C20—H20	119.3
C17—C16—C21	121.18 (10)	C19—C20—H20	119.3
C17—C16—S1	120.03 (8)	C20—C21—H21	120.6
C21—C16—S1	118.66 (8)	C16—C21—H21	120.6
C16—C17—C18	118.73 (10)	C19—C22—H22A	109.5
C17—C18—C19	121.41 (10)	C19—C22—H22B	109.5
C18—C19—C20	118.53 (10)	H22A—C22—H22B	109.5
C18—C19—C22	120.95 (10)	C19—C22—H22C	109.5
C20—C19—C22	120.52 (10)	H22A—C22—H22C	109.5
C21—C20—C19	121.32 (10)	H22B—C22—H22C	109.5

C7'—N1—S1—O3	42.42 (9)	S1—N1—C7'—C7	−27.34 (16)
C2—N1—S1—O3	−168.81 (8)	C2—N1—C7'—C3'	3.62 (11)
C7'—N1—S1—O2	171.26 (8)	S1—N1—C7'—C3'	156.08 (7)
C2—N1—S1—O2	−39.96 (9)	C5—O1—C9—C10	−174.12 (9)
C7'—N1—S1—C16	−73.66 (9)	O1—C9—C10—C11	−122.47 (10)
C2—N1—S1—C16	75.11 (9)	O1—C9—C10—C15	59.84 (12)
C7'—N1—C2—C3	−3.23 (11)	C15—C10—C11—C12	0.98 (15)
S1—N1—C2—C3	−156.71 (8)	C9—C10—C11—C12	−176.74 (10)
N1—C2—C3—C3'	1.52 (11)	C10—C11—C12—C13	0.17 (16)
N1—C2—C3—C8	−178.24 (10)	C11—C12—C13—C14	−1.24 (17)
C2—C3—C3'—C4	−178.08 (11)	C12—C13—C14—C15	1.14 (17)
C8—C3—C3'—C4	1.69 (18)	C13—C14—C15—C10	0.02 (16)
C2—C3—C3'—C7'	0.77 (11)	C11—C10—C15—C14	−1.07 (15)
C8—C3—C3'—C7'	−179.46 (10)	C9—C10—C15—C14	176.66 (10)
C7'—C3'—C4—C5	1.80 (15)	O3—S1—C16—C17	−17.23 (10)
C3—C3'—C4—C5	−179.47 (10)	O2—S1—C16—C17	−151.44 (9)
C9—O1—C5—C4	−1.70 (15)	N1—S1—C16—C17	96.46 (9)
C9—O1—C5—C6	178.08 (9)	O3—S1—C16—C21	166.80 (8)
C3'—C4—C5—O1	178.12 (10)	O2—S1—C16—C21	32.59 (10)
C3'—C4—C5—C6	−1.65 (16)	N1—S1—C16—C21	−79.50 (9)
O1—C5—C6—C7	−179.40 (10)	C21—C16—C17—C18	−0.29 (16)
C4—C5—C6—C7	0.38 (17)	S1—C16—C17—C18	−176.15 (9)
C5—C6—C7—C7'	0.75 (16)	C16—C17—C18—C19	0.40 (17)
C6—C7—C7'—C3'	−0.59 (15)	C17—C18—C19—C20	0.04 (17)
C6—C7—C7'—N1	−176.76 (10)	C17—C18—C19—C22	−178.85 (11)
C4—C3'—C7'—C7	−0.71 (15)	C18—C19—C20—C21	−0.61 (17)
C3—C3'—C7'—C7	−179.70 (9)	C22—C19—C20—C21	178.29 (10)
C4—C3'—C7'—N1	176.26 (9)	C19—C20—C21—C16	0.71 (16)
C3—C3'—C7'—N1	−2.73 (11)	C17—C16—C21—C20	−0.25 (16)
C2—N1—C7'—C7	−179.80 (11)	S1—C16—C21—C20	175.66 (8)

Experimental details

Crystal data
Chemical formula	C₂₃H₂₁NO₃S
M_r	391.47
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.317 (3), 15.601 (6), 14.752 (5)
β (°)	90.884 (11)
V (Å³)	1914.1 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.39 × 0.33 × 0.15

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.636, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	30660, 6415, 5550
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.738

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.04
No. of reflections	6415
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.42

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2012 (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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