(1R,3S,5R,6S)-6-Acet­oxy-8-methyl-3-(p-tolyl­sulfon­yloxy)-8-azoniabicyclo­[3.2.1]octane (2R,3R)-2,3-bis­(benzo­yloxy)-3-carboxy­propanoate

Yang, L.-M.; Xie, Y.-F.; Gu, Y.-F.; Chen, H.-Z.; Lu, Y.

doi:10.1107/S1600536809012732

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1037

doi:10.1107/S1600536809012732

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(1R,3S,5R,6S)-6-Acetoxy-8-methyl-3-(p-tolylsulfonyloxy)-8-azoniabicyclo[3.2.1]octane (2R,3R)-2,3-bis(benzoyloxy)-3-carboxypropanoate

Li-Min Yang,^a Yi-Fan Xie,^a Ya-Fang Gu,^a Hong-Zhuan Chen ^a and Yang Lu ^a ^*

^aDepartment of Pharmacy, Shanghai Jiao Tong University School of Medicine, South Chongqing Road 280, Shanghai 200025, People's Republic of China
^*Correspondence e-mail: huaxue@shsmu.edu.cn

(Received 6 January 2009; accepted 3 April 2009; online 18 April 2009)

The title compound, C₁₇H₂₄NO₅S⁺·C₁₈H₁₃O₈⁻, is the key intermediate during the preparation of lesatropane [systematic name (1R,3S,5R,6S)-6-acetoxy-3-(4-methylphenylsulfonyloxy)tropane], a potential antiglaucoma agent. The tertiary N atom of the tropane ring is involved in intermolecular N—H⋯O hydrogen bonding, and the carboxylate groups are involved in intermolecular O—H⋯O hydrogen bonding.

Related literature

For the crystal structure of lesatropane, see: Yang et al. (2008 ). For its improved agonistic activity compared to its racemic counterpart, see: Zhu et al. (2008 ). For synthetic details, see: Yang & Wang (1998 ).

Experimental

Crystal data

C₁₇H₂₄NO₅S⁺·C₁₈H₁₃O₈⁻
M_r = 711.72
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.4153 (5) Å
b = 19.2664 (12) Å
c = 24.7388 (16) Å
V = 3534.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.31 × 0.16 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.863, T_max = 1.000 (expected range = 0.852–0.987)
18779 measured reflections
6550 independent reflections
5135 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.125
S = 1.06
6550 reflections
459 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 3094 Friedel pairs
Flack parameter: 0.03 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.860 (18)	1.89 (2)	2.699 (4)	156 (3)
O4—H4⋯O2ⁱ	0.82	1.66	2.460 (3)	164
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012732/ww2139sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012732/ww2139Isup2.hkl

checkCIF report

Comment top

6β-Acetoxy-3α-paramethylbenzene sulfonyloxy tropane is a potent muscarinic receptor agonist and has been shown to be a promising candidate as a new antiglaucoma agent. The pharmacology results suggest that the (1R,3S,5R,6S) isomer (lesatropane), the crystal structure has been reported (Yang et al., 2008), displays an improved agonistic activity compared to its racemic counterpart (Zhu et al., 2008). The enantiopure isomer was obtained by the optical resolution of the racemic tropane alkaloids with the chiral acid (Yang & Wang, 1998). We report here the crystal structure of the diastereoisomeric salt, (1R,3S,5R,6S)-6-acetoxy-3-paramethylbenzene sulfonyloxytropane and (-)-O',O'-dibenzyl-L-tartaric acid (1/1), formed during the resolution. The three-dimensional structure of the title compound is shown in Fig.1. X-ray structure analytical data showed that the diastereoisomeric salt is produced by the formation of hydrogen bonds. The nitrogen atom of the tropane alkaloid is protonated to form the cation and the chiral acid is deprotonated to form anion. Each anion interacts with a cation (via N atom) forming N–H···O hydrogen bond, and chiral acid anions are linked by O–H···O hydrogen bond with each other (Fig. 2).

Related literature top

For the crystal structure of lesatropane, see: Yang et al. (2008). For its improved agonistic activity compared to its racemic counterpart, see: Zhu et al. (2008). For synthetic details, see: Yang & Wang (1998).

Experimental top

Rac 6β-acetoxy-3α-paramethylbenzene sulfonyloxytropane (586.3 mg, 1.66 mmol) and (-)-2,3-dibenzoyl-L-tartaric acid (728.3 mg, 2.03 mmol) were dissolved in methanol. After disposing at room temperature for 12 h, the title compound as precipitate was collected by filtration. Three recrystallizations of the crude product from anhydrous ethanol gave pure colorless crystals, 30% yield, m.p. 443–445 K, [α]_D²⁰ -14.23 (c = 0.084, EtOH).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SHELXTL (Sheldrick, 2080); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The intermolecular N–H···O and O–H···O hydrogen bonds (dashed lines).

(1R,3S,5R,6S)-6-Acetoxy-8-methyl-3-(p- tolylsulfonyloxy)-8-azoniabicyclo[3.2.1]octane (2R,3R)-2,3-bis(benzoyloxy)-3-carboxypropanoate top

Crystal data top

C₁₇H₂₄NO₅S⁺·C₁₈H₁₃O₈⁻	D_x = 1.338 Mg m⁻³
M_r = 711.72	Melting point: 445 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3212 reflections
a = 7.4153 (5) Å	θ = 4.5–39.6°
b = 19.2664 (12) Å	µ = 0.16 mm⁻¹
c = 24.7388 (16) Å	T = 293 K
V = 3534.3 (4) Å³	Prismatic, colorless
Z = 4	0.31 × 0.16 × 0.08 mm
F(000) = 1496

Data collection top

Bruker SMART CCD area-detector diffractometer	6550 independent reflections
Radiation source: fine-focus sealed tube	5135 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→8
T_min = 0.863, T_max = 1.000	k = −23→22
18779 measured reflections	l = −29→25

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)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0406P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
6550 reflections	Δρ_max = 0.19 e Å⁻³
459 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3094 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (12)

Crystal data top

C₁₇H₂₄NO₅S⁺·C₁₈H₁₃O₈⁻	V = 3534.3 (4) Å³
M_r = 711.72	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.4153 (5) Å	µ = 0.16 mm⁻¹
b = 19.2664 (12) Å	T = 293 K
c = 24.7388 (16) Å	0.31 × 0.16 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	6550 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	5135 reflections with I > 2σ(I)
T_min = 0.863, T_max = 1.000	R_int = 0.081
18779 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.125	Δρ_max = 0.19 e Å⁻³
S = 1.06	Δρ_min = −0.17 e Å⁻³
6550 reflections	Absolute structure: Flack (1983), 3094 Friedel pairs
459 parameters	Absolute structure parameter: 0.03 (12)
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	0.43913 (19)	0.80222 (5)	0.07318 (5)	0.0665 (4)
O1	0.8630 (3)	0.65740 (12)	0.25014 (9)	0.0447 (6)
O2	0.9488 (3)	0.64372 (13)	0.33606 (9)	0.0503 (7)
O3	0.3089 (4)	0.53125 (14)	0.33986 (11)	0.0635 (8)
O4	0.2542 (3)	0.63195 (15)	0.29838 (11)	0.0607 (8)
H4	0.1541	0.6282	0.3121	0.091*
O5	0.6110 (3)	0.64586 (10)	0.37312 (8)	0.0344 (5)
O6	0.6373 (5)	0.76048 (13)	0.37990 (11)	0.0713 (9)
O7	0.6535 (3)	0.52908 (11)	0.29852 (8)	0.0381 (6)
O8	0.4990 (4)	0.47399 (14)	0.23402 (11)	0.0665 (8)
O9	0.3342 (3)	0.51778 (11)	0.09819 (9)	0.0437 (6)
O10	0.6199 (4)	0.54125 (18)	0.11767 (14)	0.0864 (10)
O11	0.3041 (4)	0.74042 (11)	0.08365 (9)	0.0567 (8)
O12	0.5495 (5)	0.81346 (16)	0.12012 (13)	0.0827 (10)
O13	0.5200 (6)	0.78393 (14)	0.02309 (13)	0.1013 (14)
N1	0.0691 (4)	0.60385 (15)	0.17050 (12)	0.0403 (7)
C1	0.5418 (4)	0.58904 (15)	0.28989 (13)	0.0312 (7)
H1	0.5325	0.5974	0.2509	0.037*
C2	0.6353 (4)	0.65030 (16)	0.31564 (11)	0.0308 (7)
H2	0.5784	0.6931	0.3026	0.037*
C3	0.8340 (4)	0.65123 (16)	0.29961 (14)	0.0337 (8)
C4	0.3536 (5)	0.57930 (19)	0.31248 (13)	0.0382 (8)
C5	0.6121 (5)	0.70611 (18)	0.40081 (14)	0.0425 (9)
C6	0.5822 (5)	0.69397 (18)	0.45963 (14)	0.0431 (9)
C7	0.5218 (6)	0.6320 (2)	0.48022 (15)	0.0561 (11)
H7	0.5015	0.5949	0.4570	0.067*
C8	0.4907 (7)	0.6240 (2)	0.53502 (18)	0.0750 (14)
H8	0.4476	0.5821	0.5485	0.090*
C9	0.5241 (7)	0.6785 (3)	0.56931 (18)	0.0791 (15)
H9	0.5055	0.6732	0.6063	0.095*
C10	0.5841 (7)	0.7403 (3)	0.54952 (18)	0.0780 (15)
H10	0.6052	0.7771	0.5730	0.094*
C11	0.6139 (6)	0.7486 (2)	0.49489 (17)	0.0663 (12)
H11	0.6553	0.7909	0.4817	0.080*
C12	0.6235 (5)	0.47548 (18)	0.26441 (14)	0.0431 (9)
C13	0.7706 (6)	0.42341 (17)	0.26702 (14)	0.0464 (10)
C14	0.7538 (7)	0.36354 (19)	0.23575 (15)	0.0697 (14)
H14	0.6463	0.3543	0.2178	0.084*
C15	0.8981 (10)	0.3175 (2)	0.2315 (2)	0.0876 (19)
H15	0.8885	0.2781	0.2100	0.105*
C16	1.0522 (10)	0.3306 (3)	0.2589 (2)	0.093 (2)
H16	1.1479	0.2996	0.2560	0.111*
C17	1.0715 (7)	0.3883 (2)	0.2910 (2)	0.0732 (14)
H17	1.1785	0.3962	0.3096	0.088*
C18	0.9293 (6)	0.43443 (18)	0.29510 (16)	0.0529 (11)
H18	0.9405	0.4734	0.3170	0.064*
C19	0.2672 (5)	0.61242 (17)	0.16238 (12)	0.0380 (8)
H19	0.3349	0.5816	0.1865	0.046*
C20	0.3139 (5)	0.68767 (17)	0.17330 (13)	0.0448 (9)
H20A	0.4423	0.6944	0.1680	0.054*
H20B	0.2865	0.6984	0.2107	0.054*
C21	0.2105 (6)	0.73772 (18)	0.13658 (14)	0.0509 (11)
H21	0.2102	0.7841	0.1529	0.061*
C22	0.0196 (6)	0.71503 (18)	0.12643 (15)	0.0533 (10)
H22A	−0.0239	0.7379	0.0940	0.064*
H22B	−0.0548	0.7305	0.1563	0.064*
C23	−0.0048 (5)	0.63679 (18)	0.11971 (14)	0.0450 (9)
H23	−0.1322	0.6249	0.1146	0.054*
C24	0.1113 (5)	0.60421 (18)	0.07602 (13)	0.0459 (10)
H24A	0.1233	0.6353	0.0454	0.055*
H24B	0.0591	0.5608	0.0637	0.055*
C25	0.2953 (5)	0.59160 (16)	0.10286 (13)	0.0365 (8)
H25	0.3898	0.6197	0.0859	0.044*
C26	0.5068 (6)	0.4997 (2)	0.10702 (16)	0.0547 (11)
C27	0.5346 (8)	0.4234 (2)	0.10171 (19)	0.0869 (16)
H27A	0.6415	0.4101	0.1210	0.130*
H27B	0.5478	0.4116	0.0642	0.130*
H27C	0.4325	0.3993	0.1165	0.130*
C28	0.0126 (6)	0.53036 (19)	0.17885 (16)	0.0608 (11)
H28A	0.0494	0.5030	0.1484	0.091*
H28B	−0.1162	0.5282	0.1825	0.091*
H28C	0.0682	0.5126	0.2110	0.091*
C29	0.2935 (7)	0.87247 (18)	0.06412 (14)	0.0555 (11)
C30	0.3384 (7)	0.93614 (18)	0.08560 (15)	0.0591 (12)
H30	0.4453	0.9419	0.1047	0.071*
C31	0.2217 (8)	0.9912 (2)	0.07822 (17)	0.0699 (14)
H31	0.2523	1.0342	0.0925	0.084*
C32	0.0617 (8)	0.9846 (2)	0.05054 (16)	0.0696 (14)
C33	0.0230 (9)	0.9193 (2)	0.03008 (17)	0.0857 (17)
H33	−0.0847	0.9128	0.0115	0.103*
C34	0.1363 (8)	0.8643 (2)	0.03609 (16)	0.0794 (17)
H34	0.1069	0.8214	0.0212	0.095*
C35	−0.0664 (10)	1.0455 (3)	0.04588 (19)	0.111 (2)
H35A	−0.1094	1.0580	0.0812	0.167*
H35B	−0.1667	1.0329	0.0234	0.167*
H35C	−0.0043	1.0843	0.0301	0.167*
H1A	0.032 (5)	0.6269 (16)	0.1981 (11)	0.054 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0980 (10)	0.0401 (5)	0.0614 (7)	−0.0053 (6)	0.0372 (7)	0.0059 (5)
O1	0.0397 (14)	0.0591 (15)	0.0352 (13)	−0.0003 (13)	0.0084 (11)	0.0051 (11)
O2	0.0320 (14)	0.0785 (18)	0.0404 (14)	0.0036 (14)	0.0004 (12)	−0.0020 (13)
O3	0.0570 (19)	0.0574 (17)	0.076 (2)	−0.0078 (15)	0.0169 (15)	0.0155 (15)
O4	0.0278 (14)	0.087 (2)	0.0668 (18)	0.0102 (15)	0.0113 (13)	0.0265 (16)
O5	0.0368 (13)	0.0345 (12)	0.0318 (12)	0.0018 (11)	0.0078 (10)	−0.0011 (10)
O6	0.121 (3)	0.0339 (14)	0.0589 (18)	−0.0120 (16)	0.0077 (18)	−0.0011 (13)
O7	0.0399 (14)	0.0359 (12)	0.0385 (13)	0.0052 (11)	−0.0030 (11)	−0.0047 (10)
O8	0.075 (2)	0.0667 (18)	0.0578 (18)	−0.0039 (17)	−0.0186 (16)	−0.0172 (15)
O9	0.0515 (17)	0.0386 (13)	0.0409 (14)	0.0016 (12)	−0.0038 (12)	−0.0042 (11)
O10	0.053 (2)	0.086 (2)	0.120 (3)	−0.0026 (19)	−0.015 (2)	0.012 (2)
O11	0.095 (2)	0.0355 (13)	0.0397 (15)	−0.0029 (14)	0.0216 (14)	−0.0002 (11)
O12	0.077 (2)	0.077 (2)	0.093 (2)	−0.0141 (19)	−0.003 (2)	0.0102 (18)
O13	0.159 (4)	0.0518 (18)	0.093 (2)	0.002 (2)	0.081 (2)	0.0111 (16)
N1	0.0452 (19)	0.0415 (17)	0.0341 (17)	−0.0024 (14)	0.0082 (14)	0.0053 (14)
C1	0.0264 (18)	0.0359 (16)	0.0314 (17)	0.0040 (15)	−0.0011 (14)	0.0034 (14)
C2	0.0279 (18)	0.0348 (17)	0.0299 (17)	0.0031 (15)	0.0025 (14)	0.0021 (14)
C3	0.0327 (19)	0.0298 (16)	0.038 (2)	0.0031 (15)	0.0062 (16)	0.0033 (15)
C4	0.034 (2)	0.048 (2)	0.0325 (19)	−0.0028 (18)	0.0006 (16)	0.0029 (16)
C5	0.039 (2)	0.041 (2)	0.047 (2)	−0.0050 (18)	0.0061 (17)	−0.0086 (18)
C6	0.037 (2)	0.047 (2)	0.045 (2)	−0.0001 (18)	0.0039 (17)	−0.0130 (18)
C7	0.067 (3)	0.058 (2)	0.044 (2)	0.007 (2)	0.007 (2)	−0.0068 (19)
C8	0.093 (4)	0.078 (3)	0.054 (3)	0.010 (3)	0.015 (3)	0.007 (2)
C9	0.084 (4)	0.115 (4)	0.038 (3)	0.016 (3)	0.002 (2)	0.001 (3)
C10	0.074 (4)	0.106 (4)	0.054 (3)	0.001 (3)	0.002 (3)	−0.037 (3)
C11	0.073 (3)	0.075 (3)	0.050 (3)	−0.013 (3)	0.007 (2)	−0.020 (2)
C12	0.053 (2)	0.045 (2)	0.031 (2)	−0.0080 (19)	0.0071 (18)	−0.0013 (17)
C13	0.074 (3)	0.0310 (18)	0.035 (2)	0.0024 (19)	0.018 (2)	0.0075 (16)
C14	0.123 (4)	0.046 (2)	0.040 (2)	0.006 (3)	0.020 (2)	0.0053 (19)
C15	0.158 (6)	0.039 (2)	0.066 (3)	0.033 (3)	0.036 (4)	0.004 (2)
C16	0.132 (6)	0.057 (3)	0.090 (4)	0.038 (4)	0.054 (4)	0.026 (3)
C17	0.075 (3)	0.055 (3)	0.089 (3)	0.023 (2)	0.025 (3)	0.026 (2)
C18	0.063 (3)	0.039 (2)	0.057 (2)	0.004 (2)	0.020 (2)	0.0065 (18)
C19	0.048 (2)	0.0395 (18)	0.0269 (18)	−0.0054 (17)	−0.0006 (16)	0.0074 (15)
C20	0.061 (3)	0.043 (2)	0.0304 (19)	−0.0098 (19)	−0.0002 (17)	−0.0058 (16)
C21	0.075 (3)	0.0370 (19)	0.041 (2)	−0.002 (2)	0.026 (2)	0.0010 (16)
C22	0.066 (3)	0.050 (2)	0.043 (2)	0.013 (2)	0.006 (2)	0.0064 (18)
C23	0.037 (2)	0.053 (2)	0.045 (2)	0.0005 (18)	−0.0034 (17)	0.0060 (18)
C24	0.063 (3)	0.0428 (19)	0.0320 (19)	0.0073 (19)	−0.0083 (18)	0.0002 (16)
C25	0.048 (2)	0.0293 (17)	0.0320 (19)	−0.0012 (17)	0.0033 (16)	0.0030 (14)
C26	0.053 (3)	0.062 (3)	0.049 (2)	0.003 (2)	−0.002 (2)	−0.003 (2)
C27	0.114 (5)	0.066 (3)	0.081 (3)	0.034 (3)	−0.019 (3)	−0.010 (3)
C28	0.060 (3)	0.056 (2)	0.066 (3)	−0.013 (2)	0.013 (2)	0.020 (2)
C29	0.099 (4)	0.039 (2)	0.028 (2)	−0.012 (2)	0.013 (2)	−0.0027 (16)
C30	0.094 (4)	0.037 (2)	0.047 (2)	−0.015 (2)	0.013 (2)	−0.0071 (17)
C31	0.127 (5)	0.037 (2)	0.045 (3)	−0.012 (3)	0.017 (3)	−0.0121 (19)
C32	0.123 (5)	0.052 (3)	0.034 (2)	0.006 (3)	0.000 (3)	0.0035 (19)
C33	0.141 (5)	0.068 (3)	0.048 (3)	−0.005 (3)	−0.037 (3)	0.004 (2)
C34	0.157 (5)	0.035 (2)	0.047 (3)	−0.011 (3)	−0.026 (3)	0.0005 (19)
C35	0.183 (7)	0.086 (4)	0.064 (3)	0.055 (4)	0.009 (4)	0.004 (3)

Geometric parameters (Å, º) top

S1—O13	1.421 (3)	C15—C16	1.353 (7)
S1—O12	1.437 (3)	C15—H15	0.9300
S1—O11	1.577 (3)	C16—C17	1.372 (7)
S1—C29	1.746 (4)	C16—H16	0.9300
O1—C3	1.248 (4)	C17—C18	1.383 (5)
O2—C3	1.249 (4)	C17—H17	0.9300
O3—C4	1.194 (4)	C18—H18	0.9300
O4—C4	1.301 (4)	C19—C20	1.515 (5)
O4—H4	0.8200	C19—C25	1.540 (4)
O5—C5	1.348 (4)	C19—H19	0.9800
O5—C2	1.436 (3)	C20—C21	1.530 (5)
O6—C5	1.183 (4)	C20—H20A	0.9700
O7—C12	1.352 (4)	C20—H20B	0.9700
O7—C1	1.437 (3)	C21—C22	1.503 (6)
O8—C12	1.191 (4)	C21—H21	0.9800
O9—C26	1.344 (5)	C22—C23	1.527 (5)
O9—C25	1.456 (4)	C22—H22A	0.9700
O10—C26	1.189 (5)	C22—H22B	0.9700
O11—C21	1.483 (4)	C23—C24	1.518 (5)
N1—C28	1.491 (4)	C23—H23	0.9800
N1—C19	1.492 (5)	C24—C25	1.537 (5)
N1—C23	1.511 (4)	C24—H24A	0.9700
N1—H1A	0.860 (18)	C24—H24B	0.9700
C1—C2	1.510 (4)	C25—H25	0.9800
C1—C4	1.515 (5)	C26—C27	1.490 (5)
C1—H1	0.9800	C27—H27A	0.9600
C2—C3	1.525 (4)	C27—H27B	0.9600
C2—H2	0.9800	C27—H27C	0.9600
C5—C6	1.491 (5)	C28—H28A	0.9600
C6—C7	1.373 (5)	C28—H28B	0.9600
C6—C11	1.387 (5)	C28—H28C	0.9600
C7—C8	1.384 (5)	C29—C34	1.365 (6)
C7—H7	0.9300	C29—C30	1.378 (5)
C8—C9	1.373 (6)	C30—C31	1.381 (6)
C8—H8	0.9300	C30—H30	0.9300
C9—C10	1.362 (6)	C31—C32	1.375 (7)
C9—H9	0.9300	C31—H31	0.9300
C10—C11	1.379 (6)	C32—C33	1.386 (6)
C10—H10	0.9300	C32—C35	1.515 (7)
C11—H11	0.9300	C33—C34	1.360 (7)
C12—C13	1.484 (5)	C33—H33	0.9300
C13—C18	1.383 (5)	C34—H34	0.9300
C13—C14	1.394 (5)	C35—H35A	0.9600
C14—C15	1.393 (7)	C35—H35B	0.9600
C14—H14	0.9300	C35—H35C	0.9600

O13—S1—O12	120.1 (2)	C20—C19—C25	112.9 (3)
O13—S1—O11	102.92 (17)	N1—C19—H19	110.8
O12—S1—O11	110.05 (17)	C20—C19—H19	110.8
O13—S1—C29	109.95 (19)	C25—C19—H19	110.8
O12—S1—C29	109.84 (19)	C19—C20—C21	112.5 (3)
O11—S1—C29	102.33 (19)	C19—C20—H20A	109.1
C4—O4—H4	109.5	C21—C20—H20A	109.1
C5—O5—C2	116.8 (2)	C19—C20—H20B	109.1
C12—O7—C1	115.2 (3)	C21—C20—H20B	109.1
C26—O9—C25	115.4 (3)	H20A—C20—H20B	107.8
C21—O11—S1	117.9 (2)	O11—C21—C22	107.7 (3)
C28—N1—C19	113.6 (3)	O11—C21—C20	108.2 (3)
C28—N1—C23	114.4 (3)	C22—C21—C20	112.8 (3)
C19—N1—C23	101.5 (3)	O11—C21—H21	109.4
C28—N1—H1A	107 (2)	C22—C21—H21	109.4
C19—N1—H1A	111 (3)	C20—C21—H21	109.4
C23—N1—H1A	109 (2)	C21—C22—C23	114.6 (3)
O7—C1—C2	107.5 (2)	C21—C22—H22A	108.6
O7—C1—C4	112.1 (3)	C23—C22—H22A	108.6
C2—C1—C4	111.4 (3)	C21—C22—H22B	108.6
O7—C1—H1	108.6	C23—C22—H22B	108.6
C2—C1—H1	108.6	H22A—C22—H22B	107.6
C4—C1—H1	108.6	N1—C23—C24	102.3 (3)
O5—C2—C1	108.3 (2)	N1—C23—C22	106.3 (3)
O5—C2—C3	112.3 (3)	C24—C23—C22	114.7 (3)
C1—C2—C3	110.1 (3)	N1—C23—H23	111.0
O5—C2—H2	108.7	C24—C23—H23	111.0
C1—C2—H2	108.7	C22—C23—H23	111.0
C3—C2—H2	108.7	C23—C24—C25	105.2 (3)
O1—C3—O2	127.0 (3)	C23—C24—H24A	110.7
O1—C3—C2	115.0 (3)	C25—C24—H24A	110.7
O2—C3—C2	118.0 (3)	C23—C24—H24B	110.7
O3—C4—O4	126.8 (3)	C25—C24—H24B	110.7
O3—C4—C1	124.1 (3)	H24A—C24—H24B	108.8
O4—C4—C1	109.0 (3)	O9—C25—C24	107.2 (3)
O6—C5—O5	122.8 (3)	O9—C25—C19	110.9 (2)
O6—C5—C6	126.1 (3)	C24—C25—C19	104.6 (3)
O5—C5—C6	111.1 (3)	O9—C25—H25	111.3
C7—C6—C11	118.8 (4)	C24—C25—H25	111.3
C7—C6—C5	123.2 (3)	C19—C25—H25	111.3
C11—C6—C5	118.0 (4)	O10—C26—O9	122.2 (4)
C6—C7—C8	121.0 (4)	O10—C26—C27	125.9 (4)
C6—C7—H7	119.5	O9—C26—C27	111.9 (4)
C8—C7—H7	119.5	C26—C27—H27A	109.5
C9—C8—C7	119.3 (4)	C26—C27—H27B	109.5
C9—C8—H8	120.3	H27A—C27—H27B	109.5
C7—C8—H8	120.3	C26—C27—H27C	109.5
C10—C9—C8	120.4 (4)	H27A—C27—H27C	109.5
C10—C9—H9	119.8	H27B—C27—H27C	109.5
C8—C9—H9	119.8	N1—C28—H28A	109.5
C9—C10—C11	120.4 (4)	N1—C28—H28B	109.5
C9—C10—H10	119.8	H28A—C28—H28B	109.5
C11—C10—H10	119.8	N1—C28—H28C	109.5
C10—C11—C6	120.1 (4)	H28A—C28—H28C	109.5
C10—C11—H11	119.9	H28B—C28—H28C	109.5
C6—C11—H11	119.9	C34—C29—C30	120.3 (4)
O8—C12—O7	122.7 (4)	C34—C29—S1	120.3 (3)
O8—C12—C13	125.5 (3)	C30—C29—S1	119.4 (4)
O7—C12—C13	111.6 (3)	C29—C30—C31	118.8 (4)
C18—C13—C14	118.8 (4)	C29—C30—H30	120.6
C18—C13—C12	122.9 (3)	C31—C30—H30	120.6
C14—C13—C12	118.0 (4)	C32—C31—C30	122.4 (4)
C15—C14—C13	120.0 (5)	C32—C31—H31	118.8
C15—C14—H14	120.0	C30—C31—H31	118.8
C13—C14—H14	120.0	C31—C32—C33	116.4 (5)
C16—C15—C14	119.5 (5)	C31—C32—C35	120.5 (4)
C16—C15—H15	120.3	C33—C32—C35	123.1 (5)
C14—C15—H15	120.3	C34—C33—C32	122.6 (5)
C15—C16—C17	121.9 (5)	C34—C33—H33	118.7
C15—C16—H16	119.0	C32—C33—H33	118.7
C17—C16—H16	119.0	C33—C34—C29	119.5 (4)
C16—C17—C18	118.9 (5)	C33—C34—H34	120.2
C16—C17—H17	120.5	C29—C34—H34	120.2
C18—C17—H17	120.5	C32—C35—H35A	109.5
C13—C18—C17	120.9 (4)	C32—C35—H35B	109.5
C13—C18—H18	119.6	H35A—C35—H35B	109.5
C17—C18—H18	119.6	C32—C35—H35C	109.5
N1—C19—C20	107.9 (3)	H35A—C35—H35C	109.5
N1—C19—C25	103.5 (3)	H35B—C35—H35C	109.5

O13—S1—O11—C21	172.7 (3)	C28—N1—C19—C20	−161.2 (3)
O12—S1—O11—C21	43.5 (3)	C23—N1—C19—C20	75.6 (3)
C29—S1—O11—C21	−73.2 (3)	C28—N1—C19—C25	79.0 (3)
C12—O7—C1—C2	−159.4 (3)	C23—N1—C19—C25	−44.2 (3)
C12—O7—C1—C4	77.9 (3)	N1—C19—C20—C21	−58.4 (4)
C5—O5—C2—C1	−152.1 (3)	C25—C19—C20—C21	55.3 (4)
C5—O5—C2—C3	86.1 (3)	S1—O11—C21—C22	140.3 (3)
O7—C1—C2—O5	−76.2 (3)	S1—O11—C21—C20	−97.5 (3)
C4—C1—C2—O5	47.0 (3)	C19—C20—C21—O11	−81.1 (4)
O7—C1—C2—C3	47.0 (3)	C19—C20—C21—C22	37.9 (4)
C4—C1—C2—C3	170.1 (3)	O11—C21—C22—C23	81.2 (4)
O5—C2—C3—O1	−177.7 (3)	C20—C21—C22—C23	−38.1 (4)
C1—C2—C3—O1	61.6 (4)	C28—N1—C23—C24	−75.5 (4)
O5—C2—C3—O2	4.5 (4)	C19—N1—C23—C24	47.2 (3)
C1—C2—C3—O2	−116.2 (3)	C28—N1—C23—C22	163.8 (3)
O7—C1—C4—O3	8.4 (5)	C19—N1—C23—C22	−73.5 (3)
C2—C1—C4—O3	−112.1 (4)	C21—C22—C23—N1	56.9 (4)
O7—C1—C4—O4	−173.3 (3)	C21—C22—C23—C24	−55.3 (4)
C2—C1—C4—O4	66.2 (3)	N1—C23—C24—C25	−31.6 (3)
C2—O5—C5—O6	−2.3 (5)	C22—C23—C24—C25	83.1 (4)
C2—O5—C5—C6	179.0 (3)	C26—O9—C25—C24	164.0 (3)
O6—C5—C6—C7	167.8 (4)	C26—O9—C25—C19	−82.3 (4)
O5—C5—C6—C7	−13.5 (5)	C23—C24—C25—O9	122.5 (3)
O6—C5—C6—C11	−10.9 (6)	C23—C24—C25—C19	4.7 (3)
O5—C5—C6—C11	167.8 (3)	N1—C19—C25—O9	−90.9 (3)
C11—C6—C7—C8	0.8 (6)	C20—C19—C25—O9	152.8 (3)
C5—C6—C7—C8	−177.9 (4)	N1—C19—C25—C24	24.4 (3)
C6—C7—C8—C9	−1.2 (7)	C20—C19—C25—C24	−92.0 (3)
C7—C8—C9—C10	1.2 (8)	C25—O9—C26—O10	−0.3 (6)
C8—C9—C10—C11	−0.7 (8)	C25—O9—C26—C27	179.7 (3)
C9—C10—C11—C6	0.2 (8)	O13—S1—C29—C34	69.6 (4)
C7—C6—C11—C10	−0.3 (7)	O12—S1—C29—C34	−156.1 (3)
C5—C6—C11—C10	178.5 (4)	O11—S1—C29—C34	−39.3 (4)
C1—O7—C12—O8	−9.3 (5)	O13—S1—C29—C30	−110.6 (3)
C1—O7—C12—C13	166.2 (3)	O12—S1—C29—C30	23.7 (4)
O8—C12—C13—C18	166.6 (4)	O11—S1—C29—C30	140.6 (3)
O7—C12—C13—C18	−8.7 (5)	C34—C29—C30—C31	0.0 (6)
O8—C12—C13—C14	−7.5 (5)	S1—C29—C30—C31	−179.8 (3)
O7—C12—C13—C14	177.1 (3)	C29—C30—C31—C32	0.5 (6)
C18—C13—C14—C15	−2.6 (5)	C30—C31—C32—C33	−0.1 (7)
C12—C13—C14—C15	171.8 (4)	C30—C31—C32—C35	176.9 (4)
C13—C14—C15—C16	1.6 (7)	C31—C32—C33—C34	−0.8 (7)
C14—C15—C16—C17	−0.2 (8)	C35—C32—C33—C34	−177.7 (5)
C15—C16—C17—C18	−0.3 (7)	C32—C33—C34—C29	1.2 (8)
C14—C13—C18—C17	2.2 (5)	C30—C29—C34—C33	−0.9 (7)
C12—C13—C18—C17	−171.9 (3)	S1—C29—C34—C33	179.0 (4)
C16—C17—C18—C13	−0.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86 (2)	1.89 (2)	2.699 (4)	156 (3)
O4—H4···O2ⁱ	0.82	1.66	2.460 (3)	164

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₄NO₅S⁺·C₁₈H₁₃O₈⁻
M_r	711.72
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.4153 (5), 19.2664 (12), 24.7388 (16)
V (Å³)	3534.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.31 × 0.16 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.863, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18779, 6550, 5135
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.125, 1.06
No. of reflections	6550
No. of parameters	459
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)	0.19, −0.17
Absolute structure	Flack (1983), 3094 Friedel pairs
Absolute structure parameter	0.03 (12)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2080), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.860 (18)	1.89 (2)	2.699 (4)	156 (3)
O4—H4···O2ⁱ	0.82	1.66	2.460 (3)	164.3

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work was supported by the Fund of the Science and Technology Commission of Shanghai Municipality (Key item, grant No. 06DZ19001) and the Shanghai Municipal Education Commission Fund (grant No. 06BZ009). We thank the Shanghai Institute of Organic Chemistry for the X-ray data collection and analysis.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L. & Wang, H. (1998). Acta Pharm. Sin. 33, 832–835. CAS Google Scholar
Yang, L.-M., Zhu, L., Niu, Y.-Y., Chen, H.-Z. & Lu, Y. (2008). Acta Cryst. E64, o2331. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhu, L., Yang, L.-M., Cui, Y.-Y., Zheng, P.-L., Niu, Y.-Y., Wang, H., Lu, Y., Ren, Q.-S., Wei, P.-J. & Chen, H.-Z. (2008). Acta Pharmacol. Sin. 29, 177–184. Web of Science CrossRef PubMed Google Scholar

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Volume 65| Part 5| May 2009| Page o1037

doi:10.1107/S1600536809012732

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(1R,3S,5R,6S)-6-Acet­­oxy-8-methyl-3-(p-tolyl­sulfon­yl­oxy)-8-azoniabi­cyclo­[3.2.1]octane (2R,3R)-2,3-bis­­(benzo­yl­oxy)-3-carb­oxy­propanoate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1R,3S,5R,6S)-6-Acetoxy-8-methyl-3-(p-tolylsulfonyloxy)-8-azoniabicyclo[3.2.1]octane (2R,3R)-2,3-bis(benzoyloxy)-3-carboxypropanoate