An enanti­opure azasteroidal derivative bearing an isoborneol sulfinyl residue

Aversa, M.C.; Barattucci, A.; Bonaccorsi, P.; Faggi, C.; Giannetto, P.

doi:10.1107/S1600536807029613

An enantiopure azasteroidal derivative bearing an isoborneol sulfinyl residue

M. C. Aversa, A. Barattucci, P. Bonaccorsi, C. Faggi and P. Giannetto

The title compound (systematic name (3aR,3bS,11aS,R_S)-3a,3b,4,5,11,11a-hexahydro-10-{[[(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-yl]methyl]sulfinyl}-7-methoxy-2-phenyl-1H-naphth[2,1-e]isoindole-1,3(2H)-dione), C₃₃H₃₇NO₅S, is an enantiopure sulfinyl adduct which represents a 16-azasteroid analogue and displays an estrone-like skeleton. The structure exhibits a strong intramolecular hydrogen bond and a C—H

π intermolecular interaction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029613/bg2066sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029613/bg2066Isup2.hkl Contains datablock I

CCDC reference: 655040

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.029
wR factor = 0.072
Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          4
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         13

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           72.32
           From the CIF: _reflns_number_total               4772
           Count of symmetry unique reflns         3016
           Completeness (_total/calc)            158.22%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1756
           Fraction of Friedel pairs measured     0.582
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1'    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2'    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3A    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3B    = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4'    = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C11A   = .          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   8 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The Diels–Alder (DA) reaction is one of the best examined and well appreciated complexity-generating reactions. Some of us (Aversa et al., 2001) have described the synthesis of enantiopure 4-[1-(alkyl sulfinyl)vinyl]-1,2-dihydronaphthalenes and their DA reactions with N-phenyl maleimide (NPM). The main product (I) of the NPM cycloaddition to (1S,2R,4R)-1-{[(R)-[1-(3,4-dihydro-6-methoxy-1- naphthalenyl)ethenyl]sulfinyl]methyl}-7,7-dimethylbicyclo[2.2.1]heptan-2-ol is easily separated from their diastereomers and obtained as crystals suitable for X-ray analysis, which allows the assignment of (R), (S) and (S) configurations respectively to the new stereogenic centres 3a, 3 b and 11a, generated during the DA cycloaddition. The results here reported confirm the structure previously assigned to adduct (I) just through comparison with an analogous compound which structure had been determined by X-ray studies (Aversa et al., 2001). On the basis of our recent studies (Aversa et al., 2005) an unquestionable confirmation of structure (I) appeared to be desiderable, and this has been possible with the low temperature data set presented herein. A strong intramolecular hydrogen bond is formed (O4–HO4···O2, Fig 1 and Table 1) and this may be an important factor in determining the preferred face of approach by the dienophile and thus the corresponding configurations of the new stereogenic centres. The most important intermolecular interaction is a C—H···π one where the hydrogen atom H11c points to the geometrical centroid of the [C13—C18]ⁱ phenyl ring, i: -x + 2;y + 0,5;-z + 2 (Fig 2), with a H···Ct(Ph) distance of 2.81 Å and a C11a—H11c–Ct(Ph) angle of 142°.

Related literature top

For related literature, see: Aversa et al. (2001, 2005).

Experimental top

The preparation of adduct I was previously described in detail (Aversa et al., 2001). Crystals suitable for X-ray analysis were obtained by spontaneous slow evaporation of the chromatographic column eluent (petrol/EtOAc 7:3).

Structure description top

For related literature, see: Aversa et al. (2001, 2005).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. Molecular structure of (I) showing the intramolecular hydrogen bond (dashed line) between O4—HO4 and O2. All non-H atoms have been labelled. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Packing diagram of (I) drawn along the b axis. The CH-π intermolecular interaction between centroid Ctⁱ (i: -x + 2;y + 0,5;-z + 2) and C11a—H11c is shown in broken lines.

(3aR,3 bS,11aS,R_S)-3a,3 b,4,5,11,11a-hexahydro-10- {[[(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1] hept-1-yl]methyl]sulfinyl}-7-methoxy-2-phenyl-1H-naphth[2,1-e] isoindole-1,3(2H)-dione top

Crystal data top

C₃₃H₃₇NO₅S	F(000) = 596
M_r = 559.70	D_x = 1.320 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 13765 reflections
a = 11.271 (1) Å	θ = 3.9–72.2°
b = 7.137 (1) Å	µ = 1.37 mm⁻¹
c = 17.513 (1) Å	T = 100 K
β = 91.620 (1)°	Prismatic, light yellow
V = 1408.2 (2) Å³	0.28 × 0.21 × 0.16 mm
Z = 2

Data collection top

Oxford Diffraction Excalibur PX Ultra CCD diffractometer	4772 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4326 reflections with I > 2σ(I)
Oxford Diffraction, Enhance ULTRA assembly monochromator	R_int = 0.034
Detector resolution: 8.1241 pixels mm^-1	θ_max = 72.3°, θ_min = 3.9°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −8→6
T_min = 0.710, T_max = 0.803	l = −21→20
20509 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4772 reflections	Δρ_max = 0.15 e Å⁻³
368 parameters	Δρ_min = −0.29 e Å⁻³
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.002 (11)

Crystal data top

C₃₃H₃₇NO₅S	V = 1408.2 (2) Å³
M_r = 559.70	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 11.271 (1) Å	µ = 1.37 mm⁻¹
b = 7.137 (1) Å	T = 100 K
c = 17.513 (1) Å	0.28 × 0.21 × 0.16 mm
β = 91.620 (1)°

Data collection top

Oxford Diffraction Excalibur PX Ultra CCD diffractometer	4772 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	4326 reflections with I > 2σ(I)
T_min = 0.710, T_max = 0.803	R_int = 0.034
20509 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	Δρ_max = 0.15 e Å⁻³
S = 1.04	Δρ_min = −0.29 e Å⁻³
4772 reflections	Absolute structure: Flack (1983)
368 parameters	Absolute structure parameter: −0.002 (11)
1 restraint

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	0.81555 (3)	0.41507 (5)	0.70796 (2)	0.01779 (9)
N2	1.13302 (12)	0.2560 (2)	0.92663 (8)	0.0216 (3)
O1	0.97546 (11)	0.4534 (2)	0.94801 (7)	0.0343 (3)
O2	0.83893 (11)	0.60772 (17)	0.74147 (7)	0.0261 (3)
O3	1.24918 (12)	0.0105 (2)	0.88840 (8)	0.0332 (3)
O4	0.61320 (13)	0.76651 (19)	0.74012 (8)	0.0318 (3)
O5	1.18741 (11)	0.27852 (19)	0.45217 (7)	0.0265 (3)
C1	1.01297 (15)	0.3044 (3)	0.92662 (9)	0.0240 (4)
C3	1.15251 (16)	0.0808 (3)	0.89372 (9)	0.0234 (4)
C3A	1.03364 (15)	−0.0007 (3)	0.86789 (10)	0.0225 (4)
H3A	1.0231	−0.1239	0.8941	0.027*
C3B	1.01803 (15)	−0.0319 (2)	0.78048 (9)	0.0203 (4)
H3B	0.9472	−0.1154	0.7742	0.024*
C4	1.11951 (15)	−0.1389 (2)	0.74457 (10)	0.0228 (4)
H4A	1.1247	−0.2667	0.7664	0.027*
H4B	1.1956	−0.0740	0.7559	0.027*
C5	1.09750 (15)	−0.1504 (2)	0.65824 (10)	0.0224 (4)
H5A	1.1608	−0.2255	0.6349	0.027*
H5B	1.0205	−0.2127	0.6470	0.027*
C5A	1.09625 (14)	0.0440 (2)	0.62493 (9)	0.0177 (3)
C6	1.14288 (14)	0.0803 (3)	0.55369 (9)	0.0206 (3)
H6	1.1762	−0.0195	0.5254	0.025*
C7	1.14154 (14)	0.2594 (3)	0.52332 (9)	0.0199 (3)
C8	1.09805 (13)	0.4080 (3)	0.56590 (8)	0.0181 (3)
H8	1.0993	0.5320	0.5462	0.022*
C9	1.05288 (13)	0.3728 (2)	0.63736 (9)	0.0181 (3)
H9	1.0260	0.4747	0.6671	0.022*
C9A	1.04601 (13)	0.1914 (2)	0.66660 (9)	0.0163 (3)
C9B	0.98456 (14)	0.1480 (2)	0.73786 (9)	0.0170 (3)
C10	0.89132 (14)	0.2434 (2)	0.76548 (9)	0.0177 (3)
C11	0.84265 (15)	0.1932 (3)	0.84179 (9)	0.0226 (4)
H11A	0.7862	0.0877	0.8355	0.027*
H11B	0.7988	0.3016	0.8621	0.027*
C11A	0.94198 (15)	0.1377 (3)	0.89859 (9)	0.0231 (4)
H11C	0.9046	0.0785	0.9437	0.028*
C12	1.20323 (16)	0.4640 (3)	0.42401 (10)	0.0276 (4)
H12A	1.1266	0.5291	0.4221	0.041*
H12B	1.2351	0.4585	0.3726	0.041*
H12C	1.2588	0.5319	0.4580	0.041*
C13	1.22603 (15)	0.3608 (3)	0.96544 (9)	0.0227 (4)
C14	1.25390 (16)	0.5396 (3)	0.94238 (10)	0.0260 (4)
H14	1.2117	0.5963	0.9007	0.031*
C15	1.34454 (16)	0.6360 (3)	0.98083 (11)	0.0306 (4)
H15	1.3644	0.7594	0.9655	0.037*
C16	1.40612 (16)	0.5528 (3)	1.04146 (11)	0.0316 (4)
H16	1.4691	0.6183	1.0669	0.038*
C17	1.37598 (16)	0.3747 (3)	1.06485 (10)	0.0302 (4)
H17	1.4176	0.3187	1.1069	0.036*
C18	1.28532 (16)	0.2770 (3)	1.02726 (10)	0.0265 (4)
H18	1.2641	0.1548	1.0435	0.032*
C1'	0.57486 (14)	0.4506 (2)	0.67893 (9)	0.0185 (3)
C2'	0.58386 (15)	0.6673 (3)	0.67131 (10)	0.0232 (4)
H2'	0.6426	0.6992	0.6316	0.028*
C3'	0.45756 (16)	0.7237 (3)	0.64210 (11)	0.0289 (4)
H3'1	0.4163	0.7994	0.6806	0.035*
H3'2	0.4607	0.7956	0.5939	0.035*
C4'	0.39582 (15)	0.5338 (3)	0.62942 (10)	0.0242 (4)
H4'	0.3074	0.5414	0.6244	0.029*
C5'	0.45540 (16)	0.4398 (3)	0.56100 (10)	0.0296 (4)
H5'1	0.4645	0.5292	0.5183	0.036*
H5'2	0.4093	0.3299	0.5425	0.036*
C6'	0.57822 (15)	0.3798 (3)	0.59575 (9)	0.0253 (4)
H6'1	0.5879	0.2420	0.5941	0.030*
H6'2	0.6438	0.4391	0.5681	0.030*
C7'	0.44189 (13)	0.4178 (3)	0.69833 (9)	0.0228 (3)
C8'	0.40543 (17)	0.4955 (4)	0.77559 (11)	0.0366 (5)
H8'1	0.4343	0.6244	0.7813	0.055*
H8'2	0.4399	0.4178	0.8167	0.055*
H8'3	0.3187	0.4940	0.7784	0.055*
C9'	0.40350 (17)	0.2118 (3)	0.69455 (13)	0.0370 (5)
H9'1	0.3173	0.2034	0.6997	0.056*
H9'2	0.4432	0.1419	0.7361	0.056*
H9'3	0.4255	0.1583	0.6454	0.056*
C10'	0.66464 (13)	0.3585 (2)	0.73332 (9)	0.0197 (4)
H10A	0.6536	0.2209	0.7318	0.024*
H10B	0.6509	0.4015	0.7861	0.024*
HO4	0.685 (2)	0.737 (4)	0.7490 (14)	0.045 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01489 (17)	0.0198 (2)	0.01866 (17)	−0.00013 (16)	0.00063 (13)	0.00070 (17)
N2	0.0214 (7)	0.0257 (8)	0.0176 (7)	0.0045 (6)	−0.0016 (5)	−0.0007 (6)
O1	0.0288 (7)	0.0459 (9)	0.0279 (7)	0.0129 (6)	−0.0060 (5)	−0.0163 (6)
O2	0.0236 (6)	0.0199 (7)	0.0345 (7)	−0.0041 (5)	−0.0025 (5)	−0.0017 (6)
O3	0.0254 (7)	0.0359 (8)	0.0377 (8)	0.0110 (6)	−0.0074 (5)	−0.0087 (6)
O4	0.0296 (7)	0.0253 (7)	0.0400 (8)	0.0047 (6)	−0.0070 (6)	−0.0128 (6)
O5	0.0313 (7)	0.0279 (7)	0.0207 (6)	0.0029 (5)	0.0089 (5)	0.0025 (5)
C1	0.0237 (9)	0.0365 (11)	0.0117 (8)	0.0061 (8)	−0.0005 (6)	0.0003 (8)
C3	0.0278 (9)	0.0241 (9)	0.0182 (8)	0.0038 (8)	−0.0019 (6)	0.0011 (7)
C3A	0.0238 (8)	0.0235 (9)	0.0200 (8)	0.0024 (7)	−0.0008 (7)	0.0049 (7)
C3B	0.0219 (8)	0.0195 (9)	0.0195 (8)	−0.0027 (6)	−0.0005 (6)	0.0026 (6)
C4	0.0260 (8)	0.0186 (9)	0.0239 (9)	0.0025 (7)	−0.0015 (7)	0.0032 (7)
C5	0.0247 (9)	0.0167 (8)	0.0258 (9)	0.0019 (7)	0.0013 (7)	−0.0007 (7)
C5A	0.0149 (7)	0.0170 (8)	0.0212 (8)	−0.0004 (6)	−0.0017 (6)	−0.0012 (7)
C6	0.0182 (8)	0.0217 (9)	0.0220 (8)	0.0025 (7)	0.0019 (6)	−0.0032 (7)
C7	0.0160 (7)	0.0271 (9)	0.0166 (7)	−0.0013 (7)	0.0016 (6)	−0.0006 (7)
C8	0.0160 (7)	0.0174 (8)	0.0209 (7)	−0.0010 (7)	−0.0004 (6)	0.0043 (8)
C9	0.0131 (7)	0.0205 (9)	0.0207 (8)	0.0005 (6)	0.0002 (6)	−0.0019 (6)
C9A	0.0143 (7)	0.0177 (8)	0.0168 (8)	−0.0024 (6)	−0.0003 (6)	−0.0005 (6)
C9B	0.0162 (7)	0.0168 (8)	0.0179 (8)	−0.0018 (6)	−0.0024 (6)	−0.0002 (7)
C10	0.0175 (7)	0.0197 (9)	0.0159 (7)	−0.0027 (7)	−0.0012 (6)	0.0002 (7)
C11	0.0184 (8)	0.0307 (10)	0.0187 (8)	−0.0010 (7)	0.0008 (6)	0.0031 (7)
C11A	0.0217 (8)	0.0309 (10)	0.0167 (8)	0.0024 (7)	0.0015 (6)	0.0046 (7)
C12	0.0264 (9)	0.0332 (11)	0.0234 (9)	0.0041 (7)	0.0060 (7)	0.0095 (8)
C13	0.0198 (8)	0.0318 (10)	0.0165 (8)	0.0044 (7)	0.0006 (6)	−0.0051 (7)
C14	0.0249 (9)	0.0340 (11)	0.0192 (8)	0.0052 (8)	0.0030 (7)	−0.0001 (8)
C15	0.0283 (9)	0.0327 (11)	0.0314 (10)	−0.0017 (8)	0.0080 (8)	−0.0025 (9)
C16	0.0220 (9)	0.0436 (12)	0.0294 (10)	−0.0001 (8)	0.0020 (7)	−0.0104 (9)
C17	0.0266 (9)	0.0403 (12)	0.0233 (9)	0.0085 (8)	−0.0043 (7)	−0.0033 (8)
C18	0.0265 (9)	0.0308 (10)	0.0222 (9)	0.0054 (8)	−0.0019 (7)	0.0010 (8)
C1'	0.0151 (7)	0.0200 (9)	0.0204 (8)	0.0013 (6)	0.0021 (6)	−0.0021 (7)
C2'	0.0230 (9)	0.0212 (9)	0.0253 (9)	0.0008 (7)	−0.0003 (7)	−0.0009 (7)
C3'	0.0263 (9)	0.0239 (9)	0.0363 (10)	0.0062 (8)	−0.0041 (8)	0.0003 (8)
C4'	0.0181 (8)	0.0265 (10)	0.0280 (9)	0.0053 (7)	−0.0019 (7)	−0.0021 (8)
C5'	0.0252 (9)	0.0367 (11)	0.0265 (9)	0.0060 (8)	−0.0068 (7)	−0.0059 (9)
C6'	0.0201 (8)	0.0327 (11)	0.0229 (8)	0.0055 (7)	−0.0016 (6)	−0.0074 (8)
C7'	0.0136 (7)	0.0268 (9)	0.0281 (8)	−0.0001 (8)	0.0023 (6)	0.0028 (9)
C8'	0.0228 (9)	0.0575 (14)	0.0300 (10)	0.0061 (9)	0.0098 (8)	0.0031 (9)
C9'	0.0211 (9)	0.0320 (11)	0.0576 (13)	−0.0065 (8)	−0.0051 (9)	0.0112 (10)
C10'	0.0155 (7)	0.0223 (9)	0.0214 (8)	0.0000 (6)	0.0010 (6)	−0.0010 (7)

Geometric parameters (Å, º) top

S1—O2	1.5151 (13)	C12—H12A	0.9800
S1—C10	1.7879 (17)	C12—H12B	0.9800
S1—C10'	1.8156 (16)	C12—H12C	0.9800
N2—C1	1.396 (2)	C13—C14	1.377 (3)
N2—C3	1.397 (2)	C13—C18	1.391 (2)
N2—C13	1.442 (2)	C14—C15	1.390 (3)
O1—C1	1.208 (2)	C14—H14	0.9500
O3—C3	1.206 (2)	C15—C16	1.386 (3)
O4—C2'	1.428 (2)	C15—H15	0.9500
O4—HO4	0.85 (3)	C16—C17	1.381 (3)
O5—C7	1.3695 (19)	C16—H16	0.9500
O5—C12	1.426 (2)	C17—C18	1.388 (3)
C1—C11A	1.509 (3)	C17—H17	0.9500
C3—C3A	1.518 (2)	C18—H18	0.9500
C3A—C11A	1.537 (2)	C1'—C10'	1.519 (2)
C3A—C3B	1.552 (2)	C1'—C6'	1.543 (2)
C3A—H3A	1.0000	C1'—C2'	1.556 (3)
C3B—C4	1.526 (2)	C1'—C7'	1.564 (2)
C3B—C9B	1.527 (2)	C2'—C3'	1.552 (2)
C3B—H3B	1.0000	C2'—H2'	1.0000
C4—C5	1.527 (2)	C3'—C4'	1.537 (3)
C4—H4A	0.9900	C3'—H3'1	0.9900
C4—H4B	0.9900	C3'—H3'2	0.9900
C5—C5A	1.505 (2)	C4'—C7'	1.541 (2)
C5—H5A	0.9900	C4'—C5'	1.543 (2)
C5—H5B	0.9900	C4'—H4'	1.0000
C5A—C6	1.392 (2)	C5'—C6'	1.556 (2)
C5A—C9A	1.408 (2)	C5'—H5'1	0.9900
C6—C7	1.384 (3)	C5'—H5'2	0.9900
C6—H6	0.9500	C6'—H6'1	0.9900
C7—C8	1.394 (2)	C6'—H6'2	0.9900
C8—C9	1.387 (2)	C7'—C8'	1.529 (3)
C8—H8	0.9500	C7'—C9'	1.534 (3)
C9—C9A	1.395 (2)	C8'—H8'1	0.9800
C9—H9	0.9500	C8'—H8'2	0.9800
C9A—C9B	1.477 (2)	C8'—H8'3	0.9800
C9B—C10	1.353 (2)	C9'—H9'1	0.9800
C10—C11	1.502 (2)	C9'—H9'2	0.9800
C11—C11A	1.529 (2)	C9'—H9'3	0.9800
C11—H11A	0.9900	C10'—H10A	0.9900
C11—H11B	0.9900	C10'—H10B	0.9900
C11A—H11C	1.0000

O2—S1—C10	109.18 (8)	H12B—C12—H12C	109.5
O2—S1—C10'	105.12 (7)	C14—C13—C18	121.20 (17)
C10—S1—C10'	98.37 (8)	C14—C13—N2	120.73 (16)
C1—N2—C3	112.66 (15)	C18—C13—N2	118.06 (16)
C1—N2—C13	124.26 (15)	C13—C14—C15	119.15 (17)
C3—N2—C13	122.55 (14)	C13—C14—H14	120.4
C2'—O4—HO4	103.1 (17)	C15—C14—H14	120.4
C7—O5—C12	117.49 (14)	C16—C15—C14	120.3 (2)
O1—C1—N2	124.44 (18)	C16—C15—H15	119.8
O1—C1—C11A	127.48 (16)	C14—C15—H15	119.8
N2—C1—C11A	108.04 (15)	C17—C16—C15	119.96 (18)
O3—C3—N2	123.88 (17)	C17—C16—H16	120.0
O3—C3—C3A	127.56 (17)	C15—C16—H16	120.0
N2—C3—C3A	108.55 (15)	C16—C17—C18	120.39 (17)
C3—C3A—C11A	104.23 (15)	C16—C17—H17	119.8
C3—C3A—C3B	115.05 (14)	C18—C17—H17	119.8
C11A—C3A—C3B	112.23 (14)	C17—C18—C13	118.96 (18)
C3—C3A—H3A	108.4	C17—C18—H18	120.5
C11A—C3A—H3A	108.4	C13—C18—H18	120.5
C3B—C3A—H3A	108.4	C10'—C1'—C6'	114.61 (13)
C4—C3B—C9B	113.40 (13)	C10'—C1'—C2'	116.10 (14)
C4—C3B—C3A	114.38 (14)	C6'—C1'—C2'	103.96 (14)
C9B—C3B—C3A	112.42 (14)	C10'—C1'—C7'	115.12 (13)
C4—C3B—H3B	105.2	C6'—C1'—C7'	101.84 (13)
C9B—C3B—H3B	105.2	C2'—C1'—C7'	103.44 (14)
C3A—C3B—H3B	105.2	O4—C2'—C3'	109.75 (14)
C3B—C4—C5	109.41 (14)	O4—C2'—C1'	115.75 (15)
C3B—C4—H4A	109.8	C3'—C2'—C1'	102.98 (14)
C5—C4—H4A	109.8	O4—C2'—H2'	109.4
C3B—C4—H4B	109.8	C3'—C2'—H2'	109.4
C5—C4—H4B	109.8	C1'—C2'—H2'	109.4
H4A—C4—H4B	108.2	C4'—C3'—C2'	103.08 (14)
C5A—C5—C4	109.48 (14)	C4'—C3'—H3'1	111.1
C5A—C5—H5A	109.8	C2'—C3'—H3'1	111.1
C4—C5—H5A	109.8	C4'—C3'—H3'2	111.1
C5A—C5—H5B	109.8	C2'—C3'—H3'2	111.1
C4—C5—H5B	109.8	H3'1—C3'—H3'2	109.1
H5A—C5—H5B	108.2	C3'—C4'—C7'	102.67 (14)
C6—C5A—C9A	119.57 (16)	C3'—C4'—C5'	106.87 (15)
C6—C5A—C5	121.28 (15)	C7'—C4'—C5'	103.31 (14)
C9A—C5A—C5	119.15 (14)	C3'—C4'—H4'	114.2
C7—C6—C5A	121.05 (15)	C7'—C4'—H4'	114.2
C7—C6—H6	119.5	C5'—C4'—H4'	114.2
C5A—C6—H6	119.5	C4'—C5'—C6'	102.58 (13)
O5—C7—C6	116.20 (15)	C4'—C5'—H5'1	111.3
O5—C7—C8	123.95 (16)	C6'—C5'—H5'1	111.3
C6—C7—C8	119.83 (15)	C4'—C5'—H5'2	111.3
C9—C8—C7	119.24 (16)	C6'—C5'—H5'2	111.3
C9—C8—H8	120.4	H5'1—C5'—H5'2	109.2
C7—C8—H8	120.4	C1'—C6'—C5'	103.51 (13)
C8—C9—C9A	121.65 (15)	C1'—C6'—H6'1	111.1
C8—C9—H9	119.2	C5'—C6'—H6'1	111.1
C9A—C9—H9	119.2	C1'—C6'—H6'2	111.1
C9—C9A—C5A	118.40 (14)	C5'—C6'—H6'2	111.1
C9—C9A—C9B	122.45 (14)	H6'1—C6'—H6'2	109.0
C5A—C9A—C9B	119.12 (15)	C8'—C7'—C9'	107.64 (17)
C10—C9B—C9A	125.76 (15)	C8'—C7'—C4'	113.91 (16)
C10—C9B—C3B	115.58 (14)	C9'—C7'—C4'	113.12 (15)
C9A—C9B—C3B	118.28 (14)	C8'—C7'—C1'	114.91 (15)
C9B—C10—C11	120.33 (15)	C9'—C7'—C1'	113.89 (15)
C9B—C10—S1	120.45 (12)	C4'—C7'—C1'	93.06 (13)
C11—C10—S1	118.95 (12)	C7'—C8'—H8'1	109.5
C10—C11—C11A	111.20 (13)	C7'—C8'—H8'2	109.5
C10—C11—H11A	109.4	H8'1—C8'—H8'2	109.5
C11A—C11—H11A	109.4	C7'—C8'—H8'3	109.5
C10—C11—H11B	109.4	H8'1—C8'—H8'3	109.5
C11A—C11—H11B	109.4	H8'2—C8'—H8'3	109.5
H11A—C11—H11B	108.0	C7'—C9'—H9'1	109.5
C1—C11A—C11	112.28 (15)	C7'—C9'—H9'2	109.5
C1—C11A—C3A	105.38 (14)	H9'1—C9'—H9'2	109.5
C11—C11A—C3A	115.21 (14)	C7'—C9'—H9'3	109.5
C1—C11A—H11C	107.9	H9'1—C9'—H9'3	109.5
C11—C11A—H11C	107.9	H9'2—C9'—H9'3	109.5
C3A—C11A—H11C	107.9	C1'—C10'—S1	111.24 (11)
O5—C12—H12A	109.5	C1'—C10'—H10A	109.4
O5—C12—H12B	109.5	S1—C10'—H10A	109.4
H12A—C12—H12B	109.5	C1'—C10'—H10B	109.4
O5—C12—H12C	109.5	S1—C10'—H10B	109.4
H12A—C12—H12C	109.5	H10A—C10'—H10B	108.0

C3—N2—C1—O1	−175.54 (17)	O1—C1—C11A—C3A	171.81 (17)
C13—N2—C1—O1	12.7 (3)	N2—C1—C11A—C3A	−10.36 (17)
C3—N2—C1—C11A	6.54 (18)	C10—C11—C11A—C1	73.88 (19)
C13—N2—C1—C11A	−165.26 (15)	C10—C11—C11A—C3A	−46.8 (2)
C1—N2—C3—O3	−179.26 (16)	C3—C3A—C11A—C1	10.09 (17)
C13—N2—C3—O3	−7.3 (3)	C3B—C3A—C11A—C1	−115.05 (15)
C1—N2—C3—C3A	0.23 (19)	C3—C3A—C11A—C11	134.44 (16)
C13—N2—C3—C3A	172.19 (14)	C3B—C3A—C11A—C11	9.3 (2)
O3—C3—C3A—C11A	172.82 (17)	C1—N2—C13—C14	−66.1 (2)
N2—C3—C3A—C11A	−6.65 (18)	C3—N2—C13—C14	122.91 (18)
O3—C3—C3A—C3B	−63.9 (2)	C1—N2—C13—C18	113.06 (19)
N2—C3—C3A—C3B	116.67 (16)	C3—N2—C13—C18	−58.0 (2)
C3—C3A—C3B—C4	50.4 (2)	C18—C13—C14—C15	1.3 (2)
C11A—C3A—C3B—C4	169.37 (14)	N2—C13—C14—C15	−179.61 (16)
C3—C3A—C3B—C9B	−80.78 (18)	C13—C14—C15—C16	0.1 (3)
C11A—C3A—C3B—C9B	38.17 (19)	C14—C15—C16—C17	−1.2 (3)
C9B—C3B—C4—C5	−45.98 (19)	C15—C16—C17—C18	0.9 (3)
C3A—C3B—C4—C5	−176.70 (14)	C16—C17—C18—C13	0.4 (3)
C3B—C4—C5—C5A	62.43 (18)	C14—C13—C18—C17	−1.6 (3)
C4—C5—C5A—C6	143.70 (15)	N2—C13—C18—C17	179.29 (15)
C4—C5—C5A—C9A	−36.8 (2)	C10'—C1'—C2'—O4	−37.7 (2)
C9A—C5A—C6—C7	0.5 (2)	C6'—C1'—C2'—O4	−164.56 (14)
C5—C5A—C6—C7	−179.98 (15)	C7'—C1'—C2'—O4	89.37 (16)
C12—O5—C7—C6	−171.10 (15)	C10'—C1'—C2'—C3'	−157.47 (14)
C12—O5—C7—C8	7.1 (2)	C6'—C1'—C2'—C3'	75.70 (15)
C5A—C6—C7—O5	−178.65 (14)	C7'—C1'—C2'—C3'	−30.38 (17)
C5A—C6—C7—C8	3.0 (2)	O4—C2'—C3'—C4'	−128.89 (15)
O5—C7—C8—C9	179.66 (14)	C1'—C2'—C3'—C4'	−5.09 (18)
C6—C7—C8—C9	−2.2 (2)	C2'—C3'—C4'—C7'	39.58 (17)
C7—C8—C9—C9A	−2.3 (2)	C2'—C3'—C4'—C5'	−68.77 (17)
C8—C9—C9A—C5A	5.8 (2)	C3'—C4'—C5'—C6'	73.14 (18)
C8—C9—C9A—C9B	−172.02 (14)	C7'—C4'—C5'—C6'	−34.75 (19)
C6—C5A—C9A—C9	−4.8 (2)	C10'—C1'—C6'—C5'	161.04 (15)
C5—C5A—C9A—C9	175.66 (15)	C2'—C1'—C6'—C5'	−71.19 (17)
C6—C5A—C9A—C9B	173.03 (14)	C7'—C1'—C6'—C5'	36.08 (18)
C5—C5A—C9A—C9B	−6.5 (2)	C4'—C5'—C6'—C1'	−1.26 (19)
C9—C9A—C9B—C10	29.3 (2)	C3'—C4'—C7'—C8'	63.04 (18)
C5A—C9A—C9B—C10	−148.51 (17)	C5'—C4'—C7'—C8'	174.07 (16)
C9—C9A—C9B—C3B	−158.17 (15)	C3'—C4'—C7'—C9'	−173.62 (15)
C5A—C9A—C9B—C3B	24.0 (2)	C5'—C4'—C7'—C9'	−62.58 (18)
C4—C3B—C9B—C10	177.05 (14)	C3'—C4'—C7'—C1'	−55.98 (15)
C3A—C3B—C9B—C10	−51.26 (19)	C5'—C4'—C7'—C1'	55.05 (16)
C4—C3B—C9B—C9A	3.7 (2)	C10'—C1'—C7'—C8'	62.0 (2)
C3A—C3B—C9B—C9A	135.43 (15)	C6'—C1'—C7'—C8'	−173.41 (17)
C9A—C9B—C10—C11	−175.47 (15)	C2'—C1'—C7'—C8'	−65.73 (19)
C3B—C9B—C10—C11	11.8 (2)	C10'—C1'—C7'—C9'	−62.9 (2)
C9A—C9B—C10—S1	10.6 (2)	C6'—C1'—C7'—C9'	61.76 (18)
C3B—C9B—C10—S1	−162.16 (12)	C2'—C1'—C7'—C9'	169.43 (16)
O2—S1—C10—C9B	−111.63 (14)	C10'—C1'—C7'—C4'	−179.85 (14)
C10'—S1—C10—C9B	139.08 (14)	C6'—C1'—C7'—C4'	−55.23 (15)
O2—S1—C10—C11	74.32 (14)	C2'—C1'—C7'—C4'	52.45 (15)
C10'—S1—C10—C11	−34.97 (15)	C6'—C1'—C10'—S1	65.08 (17)
C9B—C10—C11—C11A	37.0 (2)	C2'—C1'—C10'—S1	−56.24 (17)
S1—C10—C11—C11A	−148.90 (13)	C7'—C1'—C10'—S1	−177.27 (12)
O1—C1—C11A—C11	45.6 (2)	O2—S1—C10'—C1'	81.13 (12)
N2—C1—C11A—C11	−136.53 (14)	C10—S1—C10'—C1'	−166.30 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—HO4···O2	0.85 (3)	1.97 (3)	2.7847 (19)	161 (2)
C11A—H11C···Ct(Ph)	1.00	2.81	3.645 (1)	142

Experimental details

Crystal data
Chemical formula	C₃₃H₃₇NO₅S
M_r	559.70
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	11.271 (1), 7.137 (1), 17.513 (1)
β (°)	91.620 (1)
V (Å³)	1408.2 (2)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.37
Crystal size (mm)	0.28 × 0.21 × 0.16

Data collection
Diffractometer	Oxford Diffraction Excalibur PX Ultra CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.710, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	20509, 4772, 4326
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.04
No. of reflections	4772
No. of parameters	368
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.29
Absolute structure	Flack (1983)
Absolute structure parameter	−0.002 (11)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP (Farrugia, 1997), SHELXL97.