(Z)-2-(1-Phenyl­sulfonyl-1H-indol-3-yl­methyl­ene)-1-aza­bi­cyclo­[2.2.2]­octan-3-one and (Z)-(S)-2-(1-phenyl­sulfonyl-1H-indol-3-yl­methyl­ene)-1-aza­bi­cyclo­[2.2.2]­octan-3-ol

The title compounds, C₂₂H₂₀N₂O₃S, (I), and C₂₂H₂₂N₂O₃S, (II), crystallize in space groups P and P2₁2₁2₁, respectively. The indole rings are planar and the benzene ring of the phenylsulfonyl group makes a dihedral angle with the mean plane of the indole ring of 90.2 (2)° in (I) and 94.0 (2)° in (II). In both mol­ecules, the double bond connecting the aza-bicyclic and indole moieties has a Z geometry. Compound (II) was obtained as an enantiomerically pure crystal and has the 3S configuration.

S1. Comment

Glutamate cysteine ligase, the rate-limiting enzyme in the synthesis of glutathione, is a novel target of chemoprevention paradigms. GCLC and GCLM, the genes encoding glutamate cysteine ligase subunits, are induced by indoles, such as indomethacin (Sekhar et al., 2002). In this regard, novel functionalized indole analogues and other structurally related compounds have been synthesized and utilized for comparative structure analysis of GCLC induction (Sekhar et al., 2003). The second of the title compounds, (II), was found to be ten times more active than indomethacin in inducing GCLC, whereas the first of the title compounds, (I), is inactive. Aldol condensation of 1-benzenesulfonyl-1H-indole-3-carboxaldehyde with 1-aza-bicyclo[2.2.2]octan-3-one affords (I) as a single geometric isomer. Compound (I) was reduced to the corresponding alcohol with sodium borohydride in methanol. The compositions of (I) and (II) were initially identified by NMR spectroscopy. In order to confirm the double-bond geometry of these compounds, and to obtain more detailed information about the structural conformation of the molecules that may be of value in structure–activity analysis, their X-ray structure determination has also been carried out.

X-ray analysis confirms the molecular structure and atom connectivity for (I) and (II), as illustrated in Figs. 1 and 2. Selected geometric parameters are presented in Table 1 and Table 2, respectively. For each structure, the indole ring is planar, with bond distances and angles comparable to those reported previously for other indole derivatives (Mason et al., 2003; Zarza et al., 1988). The geometries around the S atoms are distorted from ideal tetrahedral, the largest deviations being in the O—S—O [O2—S1—O1 in (I) is 121.08 (6)°, and in (II) is 120.64 (9)°] and O—S—N angles [O2—S1—N1 and O1—S1—N1 in (I) are 106.87 (6) and 105.68 (5)°, and in (II) are 106.61 (9) and 105.48 (8)°]. This type of deviation in the sulfonyl group has been reported previously and is due to the repulsive interaction between the short S=O bonds (Seshadri et al., 2002). The S—O, S—C and S—N distances are comparable to those found in N-phenylsulfonamides (Gomes et al., 1993). The conformation of the phenylsulfonyl group with respect to the indole ring is described by the O1—S1—N1—C2, O2—S1—N1—C9 and N1—S1—C19—C20 torsion angles. The phenyl ring linked to the sulfonyl group is orthogonal to the indole ring system, forming dihedral angles of 90.2 (2)° in (I) and 94.0 (2)° in (II).

Compounds (I) and (II) are both Z isomers; the C11—C18 bond is in a trans disposition with respect to the C3—C10 bond. The double bond has a nearly planar arrangement, with an r.m.s. deviation from the mean plane passing through atoms N12, C11, C18, C10 and C3 of 0.008 (11) Å in (I) and 0.0021 (11) Å in (II), respectively. Deviations from ideal geometry are observed in the bond angles around atoms C3, C10 and C11. While the C10—C11—C18 angle is close to the ideal value of 120°, the C2—C3—C10, C3—C10—C11 and N12—C11—C18 angles are more distorted in both molecules as a consequence of the strain induced by the double-bond linkage at C10—C11. In both molecules, the azabicyclic system exhibits very small distortions around atoms N12, C13, C14, C15, C16 and C17. The value of the C2—C3—C10—C11 torsion angle [−2.2 (2)° in (I) and 21.0 (3)° in (II)] indicates that the deviation of the indole ring from the plane of the double bond connected to the azabicyclic ring is greater in (II) than it is in (I). The C3—C10 bond length, when compared with the standard value for a single bond connecting a C_ar atom to a Csp² atom [1.470 (15) Å; Wilson, 1992], suggests extensive conjugation, beginning at atom O18 and extending through to the aromatic ring in (I), which is also evident from the C11—C18 bond lengths and C18—O18. However, in the case of (II), where the carbonyl group has been reduced to the corresponding alcohol, the C11—C18 and C18—O18 bond lengths are purely single-bond character, and conjugation begins at C11 and extends to the aromatic ring. This extended conjugation in (I) and (II) explains the difference in the C2—C3—C10—C11 torsion angle.

In the crystal structure of (II), the H atom attached to atom O18 is involved in an intermolecular hydrogen bond [2.30 Å] with atom O18 of another molecule (Table 3), thus forming an infinite chain running in the a direction. In addition to C—H.·O and C—H..π weak interactions, Van der Waals forces contribute to the stabilization of the crystal structures of (I) and (II).

S2. Experimental

To a stirred solution of diisopropylamine (1.923 g, 19 mmol) in THF (20 ml) at 273 K under nitrogen was added a solution of 2.0 M n-butyllithium (9 ml, 18.8 mmol) and the mixture stirred at 273 K for 30 min. To this solution at 273 K, was added 1-aza-bicyclo[2.2.2]octan-3-one hydrochloride (1.5 g, 9.28 mmol) in one portion and stirring was continued until the mixture completely dissolved (20 min). The temperature was lowered to 195 K and a solution of 1-benzenesulfonyl-1H-indole-3-carboxaldehyde (2.63 g, 9.2 mmol) in THF (30 ml) was added dropwise. Stirring was continued for 30 min at this temperature and then at 273 K for 90 min. The reaction mixture was poured into aqueous saturated NaHCO₃ solution at 273 K and the resulting solution was extracted with CHCl₃ (3 τimes 15 ml). The combined organic extracts were dried over anhydrous Na₂SO₄, filtered and evaporated to afford a yellow solid. Crystallization from methanol gave a yellow crystalline product suitable for X-ray analysis. ¹H NMR (CDCl₃): δ 1.85- 1.91 (m, 4H), 2.49 (p, 1H), 2.78–2.87 (m, 2H), 3.02–3.11 (m, 2H), 7.07 (s, 1H), 7.10–7.21 (m, 2H), 7.27–7.32 (m, 2H), 7.36–7.42 (m, 1H), 7.56– 7.59 (dd, 1H), 7.73–7.76 (m, 2H), 7.79–7.82 (dd, J = 1.5, 7.7 Hz,1H), 8.52 (s, 1H). ¹³C NMR (CDCl₃): δ 26.4, 40.7, 47.5, 113.7, 115.0, 116.1, 119.4, 124.0, 125.3, 127.0, 129.5, 130.5, 134.2, 134.5, 138.0, 144.9, 205.3. To a stirred solution of (I) (0.392 g, 1 mmol) in methanol (15 ml) at 273 K was added NaBH₄ (0.379 g, 10 mmol) over 15 min and stirring was continued for 2 h at room temperature. Water (50 ml) was added and the mixture was extracted with CHCl₃ (3 τimes 10 ml). The combined organic layers were dried over Na₂SO₄ and evaporated to give (II) as a colourless solid. Crystallization from methanol afforded colourless needles, suitable for X-ray analysis. ¹H NMR (CDCl₃): δ 1.46–1.61 (m, 2H), 1.72– 1.90 (m, 4H), 2.05–2.08 (p, 1H), 4.38 (s, 1H), 6.42 (d, 1H), 7.21–7.32 (m, 2H), 7.37–7.43 (m, 2H), 7.47–7.52 (m, 1H), 7.6 (d, 1H), 7.86 (d, 2H), 7.98 (d, 1H), 8.42 (s, 1H). ¹³C NMR (CDCl₃): δ 19.4, 25.7, 31.5, 46.9, 48.0, 71.4, 110.9, 111.0, 113.8, 117.5, 119.1, 123.4, 124.7, 126.4, 126.8, 129.3, 130.7, 133.8, 134.6, 138.3, 153.2.

S3. Refinement

All H atoms were located in difference Fourier syntheses, and were subsequently positioned geometrically and treated as riding, with bond distances to parent atoms of 0.95 (C_ar—H), 0.99 (C_sec—H), 1.00 (C_tert—H) and 0.89 Å (O—H). The absolute structure of (II) was determined by refinement of the Flack (Flack, 1983; Bernardinelli & Flack, 1985) parameter, the value of which indicates the probable correctness of the assignment.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures.

Figures

	Fig. 1. A view of the molecule (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. A view of the molecule (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms, except that linked to atom O18, have been omitted for clarity.

(I) (Z)-2-(1-Benzenesulfonyl-1H-indol-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-one

Crystal data

C22H20N2O3S	Z = 2
Mr = 392.46	F(000) = 412
Triclinic, P1	Dx = 1.433 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7070 (1) Å	Cell parameters from 4073 reflections
b = 10.7080 (2) Å	θ = 1.0–27.5°
c = 12.3080 (2) Å	µ = 0.21 mm^−1
α = 94.5900 (7)°	T = 90 K
β = 104.1170 (7)°	Irregular wedge, yellow
γ = 110.1160 (7)°	0.35 × 0.25 × 0.15 mm
V = 909.86 (3) Å^3

Data collection

Nonius KappaCCD diffractometer	3720 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 27.5°, θmin = 1.7°
Detector resolution: 18 pixels mm^-1	h = −9→9
ω scans at fixed χ = 55°	k = −13→13
8085 measured reflections	l = −15→15
4145 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0439P)^2 + 0.4878P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4145 reflections	Δρmax = 0.36 e Å^−3
254 parameters	Δρmin = −0.49 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (3)

Special details

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.

The extinction correction that was refined for this structure is about 2.7su and therefore does not quite meet the arbitrary cut-off of 3su. Nevertheless, we feel that the extinction correction is warranted. Since we know that extinction primarily affects the strong low-angle data, we performed tests in which the extinction parameter was refined for several high-resolution cutoffs. For data truncated at 40,45,50,53 and 54 degrees in 2theta, the extinction:SU ratios were 7.6, 6.2, 4.0, 3.2 and 2.8. From these tests it is readily apparent that an extinction correction is needed because it is the low-angle data that are affected by extinction effects.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.32935 (4)	0.32107 (3)	0.64002 (2)	0.01552 (10)
O1	0.29704 (15)	0.42210 (10)	0.57799 (8)	0.0217 (2)
N1	0.26764 (16)	0.18446 (11)	0.54245 (9)	0.0160 (2)
O2	0.23334 (13)	0.27857 (10)	0.72397 (7)	0.0189 (2)
C2	0.29258 (18)	0.19292 (13)	0.43398 (10)	0.0157 (2)
H2	0.3151	0.2717	0.4004	0.019*
C3	0.27949 (17)	0.07026 (12)	0.38404 (10)	0.0138 (2)
C4	0.25055 (17)	−0.01966 (12)	0.46554 (10)	0.0137 (2)
C5	0.22573 (18)	−0.15570 (13)	0.46092 (11)	0.0162 (2)
H5	0.2275	−0.2069	0.3947	0.019*
C6	0.19853 (19)	−0.21447 (13)	0.55475 (11)	0.0193 (3)
H6	0.1829	−0.3066	0.5531	0.023*
C7	0.19377 (19)	−0.13993 (14)	0.65217 (11)	0.0197 (3)
H7	0.1751	−0.1828	0.7154	0.024*
C8	0.21562 (18)	−0.00533 (13)	0.65859 (10)	0.0174 (3)
H8	0.2103	0.0447	0.7242	0.021*
C9	0.24569 (17)	0.05301 (12)	0.56428 (10)	0.0146 (2)
C10	0.28881 (17)	0.03065 (12)	0.27087 (10)	0.0147 (2)
H10	0.2812	−0.0594	0.2529	0.018*
C11	0.30674 (17)	0.10428 (12)	0.18825 (10)	0.0142 (2)
N12	0.32003 (15)	0.24292 (10)	0.19814 (9)	0.0149 (2)
C13	0.51012 (19)	0.32820 (13)	0.18690 (10)	0.0172 (3)
H13A	0.6136	0.3290	0.2532	0.021*
H13B	0.5169	0.4222	0.1870	0.021*
C14	0.54436 (19)	0.27581 (13)	0.07567 (11)	0.0180 (3)
H14A	0.5761	0.3493	0.0313	0.022*
H14B	0.6539	0.2453	0.0944	0.022*
C15	0.35952 (18)	0.15734 (12)	0.00525 (10)	0.0156 (3)
H15	0.3744	0.1224	−0.0684	0.019*
C16	0.1907 (2)	0.20693 (14)	−0.01534 (11)	0.0199 (3)
H16A	0.0702	0.1333	−0.0624	0.024*
H16B	0.2174	0.2840	−0.0564	0.024*
C17	0.16752 (19)	0.25149 (14)	0.10198 (11)	0.0187 (3)
H17A	0.1734	0.3457	0.1083	0.022*
H17B	0.0393	0.1931	0.1068	0.022*
O18	0.29965 (14)	−0.06823 (9)	0.04749 (8)	0.0199 (2)
C18	0.31991 (17)	0.04895 (12)	0.07698 (10)	0.0146 (2)
C19	0.57933 (18)	0.36889 (12)	0.70246 (10)	0.0154 (2)
C20	0.7078 (2)	0.45363 (13)	0.65299 (11)	0.0202 (3)
H20	0.6619	0.4867	0.5870	0.024*
C21	0.9040 (2)	0.48871 (14)	0.70195 (13)	0.0242 (3)
H21	0.9937	0.5462	0.6692	0.029*
C22	0.9704 (2)	0.44045 (14)	0.79854 (13)	0.0235 (3)
H22	1.1053	0.4654	0.8316	0.028*
C23	0.8411 (2)	0.35594 (13)	0.84723 (12)	0.0206 (3)
H23	0.8875	0.3235	0.9135	0.025*
C24	0.64378 (19)	0.31888 (13)	0.79875 (11)	0.0167 (3)
H24	0.5542	0.2602	0.8309	0.020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02168 (17)	0.01681 (17)	0.01103 (15)	0.01117 (13)	0.00471 (12)	0.00093 (11)
O1	0.0341 (5)	0.0203 (5)	0.0152 (4)	0.0176 (4)	0.0045 (4)	0.0025 (4)
N1	0.0237 (6)	0.0162 (5)	0.0107 (5)	0.0105 (4)	0.0051 (4)	0.0019 (4)
O2	0.0209 (5)	0.0245 (5)	0.0140 (4)	0.0109 (4)	0.0068 (4)	0.0010 (4)
C2	0.0202 (6)	0.0180 (6)	0.0110 (5)	0.0095 (5)	0.0045 (5)	0.0027 (4)
C3	0.0135 (6)	0.0152 (6)	0.0133 (6)	0.0063 (5)	0.0036 (4)	0.0023 (4)
C4	0.0116 (5)	0.0159 (6)	0.0137 (5)	0.0056 (4)	0.0036 (4)	0.0022 (4)
C5	0.0159 (6)	0.0157 (6)	0.0174 (6)	0.0065 (5)	0.0050 (5)	0.0016 (5)
C6	0.0206 (6)	0.0161 (6)	0.0216 (6)	0.0073 (5)	0.0058 (5)	0.0053 (5)
C7	0.0203 (6)	0.0227 (7)	0.0173 (6)	0.0075 (5)	0.0068 (5)	0.0081 (5)
C8	0.0174 (6)	0.0217 (6)	0.0131 (6)	0.0074 (5)	0.0045 (5)	0.0030 (5)
C9	0.0141 (6)	0.0159 (6)	0.0141 (6)	0.0070 (5)	0.0030 (4)	0.0024 (5)
C10	0.0148 (6)	0.0143 (6)	0.0153 (6)	0.0060 (5)	0.0048 (4)	0.0003 (4)
C11	0.0150 (6)	0.0146 (6)	0.0138 (6)	0.0063 (5)	0.0050 (4)	−0.0001 (4)
N12	0.0191 (5)	0.0150 (5)	0.0132 (5)	0.0092 (4)	0.0052 (4)	0.0024 (4)
C13	0.0203 (6)	0.0145 (6)	0.0147 (6)	0.0052 (5)	0.0045 (5)	−0.0004 (5)
C14	0.0183 (6)	0.0158 (6)	0.0183 (6)	0.0036 (5)	0.0075 (5)	0.0000 (5)
C15	0.0185 (6)	0.0166 (6)	0.0119 (5)	0.0062 (5)	0.0060 (5)	0.0002 (4)
C16	0.0220 (7)	0.0265 (7)	0.0138 (6)	0.0128 (6)	0.0044 (5)	0.0039 (5)
C17	0.0214 (6)	0.0233 (6)	0.0161 (6)	0.0138 (5)	0.0057 (5)	0.0043 (5)
O18	0.0253 (5)	0.0150 (4)	0.0204 (5)	0.0068 (4)	0.0107 (4)	−0.0006 (4)
C18	0.0132 (6)	0.0161 (6)	0.0140 (6)	0.0051 (5)	0.0046 (4)	0.0001 (5)
C19	0.0204 (6)	0.0135 (6)	0.0150 (6)	0.0086 (5)	0.0071 (5)	0.0009 (4)
C20	0.0319 (7)	0.0141 (6)	0.0201 (6)	0.0105 (5)	0.0137 (5)	0.0052 (5)
C21	0.0280 (7)	0.0142 (6)	0.0337 (8)	0.0053 (5)	0.0189 (6)	0.0037 (5)
C22	0.0189 (6)	0.0174 (6)	0.0338 (8)	0.0062 (5)	0.0094 (6)	−0.0013 (5)
C23	0.0215 (7)	0.0186 (6)	0.0223 (6)	0.0095 (5)	0.0047 (5)	0.0024 (5)
C24	0.0200 (6)	0.0152 (6)	0.0165 (6)	0.0068 (5)	0.0074 (5)	0.0036 (5)

Geometric parameters (Å, º)

S1—O2	1.4280 (9)	C13—C14	1.5535 (17)
S1—O1	1.4282 (10)	C13—H13A	0.9900
S1—N1	1.6643 (11)	C13—H13B	0.9900
S1—C19	1.7609 (13)	C14—C15	1.5390 (17)
N1—C2	1.4000 (15)	C14—H14A	0.9900
N1—C9	1.4145 (16)	C14—H14B	0.9900
C2—C3	1.3648 (17)	C15—C18	1.5071 (17)
C2—H2	0.9500	C15—C16	1.5408 (18)
C3—C4	1.4487 (17)	C15—H15	1.0000
C3—C10	1.4493 (16)	C16—C17	1.5554 (17)
C4—C5	1.3971 (17)	C16—H16A	0.9900
C4—C9	1.4052 (16)	C16—H16B	0.9900
C5—C6	1.3847 (18)	C17—H17A	0.9900
C5—H5	0.9500	C17—H17B	0.9900
C6—C7	1.4016 (18)	O18—C18	1.2228 (15)
C6—H6	0.9500	C19—C24	1.3912 (17)
C7—C8	1.3858 (19)	C19—C20	1.3926 (18)
C7—H7	0.9500	C20—C21	1.385 (2)
C8—C9	1.3925 (17)	C20—H20	0.9500
C8—H8	0.9500	C21—C22	1.388 (2)
C10—C11	1.3404 (17)	C21—H21	0.9500
C10—H10	0.9500	C22—C23	1.3889 (19)
C11—N12	1.4455 (15)	C22—H22	0.9500
C11—C18	1.4888 (16)	C23—C24	1.3894 (19)
N12—C13	1.4827 (16)	C23—H23	0.9500
N12—C17	1.4844 (16)	C24—H24	0.9500
O2—S1—O1	121.08 (6)	H13A—C13—H13B	107.9
O2—S1—N1	106.87 (6)	C15—C14—C13	108.66 (10)
O1—S1—N1	105.68 (5)	C15—C14—H14A	110.0
O2—S1—C19	108.40 (6)	C13—C14—H14A	110.0
O1—S1—C19	108.92 (6)	C15—C14—H14B	110.0
N1—S1—C19	104.68 (6)	C13—C14—H14B	110.0
C2—N1—C9	108.86 (10)	H14A—C14—H14B	108.3
C2—N1—S1	122.29 (9)	C18—C15—C14	107.34 (10)
C9—N1—S1	125.87 (9)	C18—C15—C16	107.70 (10)
C3—C2—N1	109.33 (11)	C14—C15—C16	108.18 (10)
C3—C2—H2	125.3	C18—C15—H15	111.1
N1—C2—H2	125.3	C14—C15—H15	111.1
C2—C3—C4	107.23 (10)	C16—C15—H15	111.1
C2—C3—C10	128.56 (12)	C15—C16—C17	108.53 (10)
C4—C3—C10	124.20 (11)	C15—C16—H16A	110.0
C5—C4—C9	119.33 (11)	C17—C16—H16A	110.0
C5—C4—C3	132.58 (11)	C15—C16—H16B	110.0
C9—C4—C3	108.08 (11)	C17—C16—H16B	110.0
C6—C5—C4	118.65 (11)	H16A—C16—H16B	108.4
C6—C5—H5	120.7	N12—C17—C16	111.85 (10)
C4—C5—H5	120.7	N12—C17—H17A	109.2
C5—C6—C7	120.94 (12)	C16—C17—H17A	109.2
C5—C6—H6	119.5	N12—C17—H17B	109.2
C7—C6—H6	119.5	C16—C17—H17B	109.2
C8—C7—C6	121.64 (12)	H17A—C17—H17B	107.9
C8—C7—H7	119.2	O18—C18—C11	124.79 (11)
C6—C7—H7	119.2	O18—C18—C15	124.77 (11)
C7—C8—C9	116.79 (12)	C11—C18—C15	110.44 (10)
C7—C8—H8	121.6	C24—C19—C20	121.52 (12)
C9—C8—H8	121.6	C24—C19—S1	119.21 (10)
C8—C9—C4	122.62 (12)	C20—C19—S1	119.26 (10)
C8—C9—N1	130.88 (11)	C21—C20—C19	118.65 (13)
C4—C9—N1	106.44 (10)	C21—C20—H20	120.7
C11—C10—C3	128.56 (12)	C19—C20—H20	120.7
C11—C10—H10	115.7	C20—C21—C22	120.46 (13)
C3—C10—H10	115.7	C20—C21—H21	119.8
C10—C11—N12	124.48 (11)	C22—C21—H21	119.8
C10—C11—C18	121.74 (11)	C21—C22—C23	120.46 (13)
N12—C11—C18	113.76 (10)	C21—C22—H22	119.8
C11—N12—C13	108.39 (9)	C23—C22—H22	119.8
C11—N12—C17	108.28 (10)	C22—C23—C24	119.86 (13)
C13—N12—C17	108.02 (10)	C22—C23—H23	120.1
N12—C13—C14	111.80 (10)	C24—C23—H23	120.1
N12—C13—H13A	109.3	C23—C24—C19	119.04 (12)
C14—C13—H13A	109.3	C23—C24—H24	120.5
N12—C13—H13B	109.3	C19—C24—H24	120.5
C14—C13—H13B	109.3
O2—S1—N1—C2	162.86 (10)	C10—C11—N12—C17	−125.53 (13)
O1—S1—N1—C2	32.66 (12)	C18—C11—N12—C17	55.99 (13)
C19—S1—N1—C2	−82.28 (11)	C11—N12—C13—C14	54.25 (13)
O2—S1—N1—C9	−38.89 (12)	C17—N12—C13—C14	−62.86 (13)
O1—S1—N1—C9	−169.08 (10)	N12—C13—C14—C15	5.19 (14)
C19—S1—N1—C9	75.97 (11)	C13—C14—C15—C18	−59.93 (13)
C9—N1—C2—C3	2.45 (14)	C13—C14—C15—C16	56.04 (13)
S1—N1—C2—C3	163.95 (9)	C18—C15—C16—C17	54.57 (13)
N1—C2—C3—C4	−1.73 (14)	C14—C15—C16—C17	−61.16 (13)
N1—C2—C3—C10	177.44 (12)	C11—N12—C17—C16	−59.83 (13)
C2—C3—C4—C5	179.22 (13)	C13—N12—C17—C16	57.35 (13)
C10—C3—C4—C5	0.0 (2)	C15—C16—C17—N12	4.01 (15)
C2—C3—C4—C9	0.39 (14)	C10—C11—C18—O18	6.4 (2)
C10—C3—C4—C9	−178.83 (11)	N12—C11—C18—O18	−175.02 (11)
C9—C4—C5—C6	−0.51 (18)	C10—C11—C18—C15	−174.19 (11)
C3—C4—C5—C6	−179.25 (13)	N12—C11—C18—C15	4.34 (14)
C4—C5—C6—C7	0.68 (19)	C14—C15—C18—O18	−124.84 (13)
C5—C6—C7—C8	0.1 (2)	C16—C15—C18—O18	118.88 (13)
C6—C7—C8—C9	−1.01 (19)	C14—C15—C18—C11	55.79 (13)
C7—C8—C9—C4	1.19 (19)	C16—C15—C18—C11	−60.48 (13)
C7—C8—C9—N1	178.02 (12)	O2—S1—C19—C24	22.10 (11)
C5—C4—C9—C8	−0.44 (19)	O1—S1—C19—C24	155.67 (10)
C3—C4—C9—C8	178.58 (11)	N1—S1—C19—C24	−91.68 (10)
C5—C4—C9—N1	−177.94 (11)	O2—S1—C19—C20	−159.20 (10)
C3—C4—C9—N1	1.07 (13)	O1—S1—C19—C20	−25.64 (12)
C2—N1—C9—C8	−179.36 (13)	N1—S1—C19—C20	87.02 (11)
S1—N1—C9—C8	20.0 (2)	C24—C19—C20—C21	−0.33 (19)
C2—N1—C9—C4	−2.14 (14)	S1—C19—C20—C21	−179.00 (10)
S1—N1—C9—C4	−162.81 (9)	C19—C20—C21—C22	−0.18 (19)
C2—C3—C10—C11	−2.2 (2)	C20—C21—C22—C23	0.2 (2)
C4—C3—C10—C11	176.88 (12)	C21—C22—C23—C24	0.3 (2)
C3—C10—C11—N12	−0.2 (2)	C22—C23—C24—C19	−0.77 (19)
C3—C10—C11—C18	178.18 (11)	C20—C19—C24—C23	0.81 (18)
C10—C11—N12—C13	117.53 (13)	S1—C19—C24—C23	179.47 (10)
C18—C11—N12—C13	−60.96 (13)

(II) (Z)-2-(1-Benzenesulfonyl-1H-indol-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-ol

Crystal data

C22H22N2O3S	F(000) = 832
Mr = 394.48	Dx = 1.394 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2500 reflections
a = 6.1300 (1) Å	θ = 1.0–27.5°
b = 12.9500 (2) Å	µ = 0.20 mm^−1
c = 23.6800 (4) Å	T = 90 K
V = 1879.80 (5) Å^3	Block, colourless
Z = 4	0.25 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	3780 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 27.5°, θmin = 1.7°
Detector resolution: 18 pixels mm^-1	h = −7→7
ω scans at fixed χ = 55°	k = −16→16
23509 measured reflections	l = −30→30
4283 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.3905P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.004
4283 reflections	Δρmax = 0.31 e Å^−3
253 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1807 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.85300 (8)	0.85822 (4)	0.817965 (19)	0.01805 (12)
N1	0.7594 (3)	0.92165 (12)	0.87381 (6)	0.0173 (3)
O1	0.7756 (2)	0.91422 (10)	0.77005 (5)	0.0228 (3)
O2	1.0809 (2)	0.84389 (11)	0.82686 (6)	0.0239 (3)
C2	0.5624 (3)	0.97763 (14)	0.87284 (8)	0.0179 (4)
H2	0.4898	1.0003	0.8396	0.021*
C3	0.4916 (3)	0.99447 (14)	0.92649 (8)	0.0173 (4)
C4	0.6452 (3)	0.94269 (13)	0.96380 (8)	0.0168 (4)
C5	0.6561 (3)	0.93322 (14)	1.02269 (8)	0.0198 (4)
H5	0.5473	0.9630	1.0462	0.024*
C6	0.8299 (3)	0.87925 (15)	1.04570 (8)	0.0230 (4)
H6	0.8391	0.8718	1.0855	0.028*
C7	0.9917 (3)	0.83554 (15)	1.01183 (8)	0.0221 (4)
H7	1.1087	0.7991	1.0290	0.027*
C8	0.9845 (3)	0.84442 (14)	0.95353 (8)	0.0191 (4)
H8	1.0949	0.8155	0.9303	0.023*
C9	0.8088 (3)	0.89743 (14)	0.93070 (8)	0.0172 (4)
C10	0.3028 (3)	1.05481 (14)	0.94497 (8)	0.0175 (4)
H10	0.2468	1.0402	0.9815	0.021*
C11	0.2018 (3)	1.12825 (14)	0.91552 (8)	0.0174 (4)
N12	0.2717 (3)	1.15709 (12)	0.85960 (6)	0.0182 (3)
C13	0.0846 (3)	1.14737 (15)	0.82065 (8)	0.0216 (4)
H13A	0.0348	1.0747	0.8201	0.026*
H13B	0.1320	1.1659	0.7820	0.026*
C14	−0.1084 (3)	1.21808 (17)	0.83831 (9)	0.0252 (5)
H14A	−0.1368	1.2701	0.8086	0.030*
H14B	−0.2422	1.1763	0.8436	0.030*
C15	−0.0469 (3)	1.27200 (15)	0.89386 (8)	0.0190 (4)
H15	−0.1704	1.3161	0.9074	0.023*
C16	0.1563 (3)	1.33771 (15)	0.88424 (9)	0.0250 (4)
H16A	0.2022	1.3704	0.9201	0.030*
H16B	0.1247	1.3930	0.8565	0.030*
C17	0.3398 (3)	1.26714 (14)	0.86174 (8)	0.0205 (4)
H17A	0.3819	1.2900	0.8234	0.025*
H17B	0.4694	1.2738	0.8864	0.025*
O18	0.0558 (3)	1.22817 (12)	0.99167 (6)	0.0334 (4)
H18O	−0.0710	1.2555	1.0028	0.050*
C18	0.0043 (3)	1.18768 (15)	0.93727 (8)	0.0209 (4)
H18	−0.1231	1.1398	0.9405	0.025*
C19	0.7254 (3)	0.73631 (14)	0.81901 (8)	0.0171 (4)
C20	0.5214 (3)	0.72557 (16)	0.79437 (8)	0.0205 (4)
H20	0.4450	0.7841	0.7804	0.025*
C21	0.4310 (3)	0.62731 (16)	0.79051 (8)	0.0232 (4)
H21	0.2926	0.6180	0.7732	0.028*
C22	0.5423 (4)	0.54324 (16)	0.81184 (9)	0.0253 (5)
H22	0.4809	0.4762	0.8083	0.030*
C23	0.7414 (4)	0.55531 (17)	0.83818 (9)	0.0269 (5)
H23	0.8137	0.4971	0.8539	0.032*
C24	0.8362 (3)	0.65249 (15)	0.84167 (8)	0.0225 (4)
H24	0.9742	0.6614	0.8592	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0193 (2)	0.0175 (2)	0.0173 (2)	0.00268 (19)	0.00193 (18)	−0.00051 (19)
N1	0.0196 (8)	0.0175 (8)	0.0148 (7)	0.0027 (7)	0.0005 (7)	0.0008 (6)
O1	0.0282 (8)	0.0229 (7)	0.0174 (7)	0.0030 (6)	0.0010 (6)	0.0015 (6)
O2	0.0186 (7)	0.0257 (7)	0.0274 (7)	0.0016 (6)	0.0025 (6)	−0.0016 (6)
C2	0.0181 (9)	0.0159 (9)	0.0196 (9)	0.0020 (8)	−0.0010 (8)	0.0006 (7)
C3	0.0189 (10)	0.0137 (9)	0.0193 (9)	−0.0012 (8)	−0.0004 (8)	0.0015 (7)
C4	0.0184 (9)	0.0114 (8)	0.0206 (9)	−0.0035 (8)	0.0001 (8)	−0.0007 (7)
C5	0.0234 (10)	0.0171 (9)	0.0189 (9)	−0.0026 (9)	0.0002 (8)	−0.0006 (7)
C6	0.0272 (11)	0.0231 (10)	0.0188 (9)	−0.0026 (9)	−0.0055 (9)	0.0018 (8)
C7	0.0235 (10)	0.0189 (10)	0.0240 (10)	0.0012 (8)	−0.0083 (8)	0.0026 (8)
C8	0.0191 (9)	0.0156 (9)	0.0226 (9)	0.0000 (8)	−0.0025 (8)	0.0001 (8)
C9	0.0210 (10)	0.0122 (8)	0.0183 (9)	−0.0024 (8)	−0.0035 (8)	−0.0004 (7)
C10	0.0191 (10)	0.0160 (9)	0.0174 (9)	−0.0009 (8)	0.0021 (8)	−0.0016 (7)
C11	0.0178 (9)	0.0166 (9)	0.0177 (9)	−0.0013 (8)	0.0021 (7)	−0.0016 (7)
N12	0.0192 (8)	0.0176 (8)	0.0177 (8)	0.0021 (7)	0.0024 (6)	0.0026 (7)
C13	0.0241 (10)	0.0218 (10)	0.0189 (9)	−0.0025 (8)	0.0014 (8)	−0.0017 (9)
C14	0.0212 (11)	0.0310 (11)	0.0233 (10)	0.0006 (9)	−0.0026 (8)	−0.0004 (9)
C15	0.0149 (9)	0.0185 (10)	0.0237 (10)	0.0033 (8)	0.0037 (8)	−0.0020 (8)
C16	0.0218 (10)	0.0176 (9)	0.0356 (11)	−0.0029 (9)	0.0056 (9)	−0.0028 (8)
C17	0.0167 (9)	0.0194 (9)	0.0254 (10)	−0.0017 (9)	0.0029 (8)	0.0011 (8)
O18	0.0351 (9)	0.0434 (10)	0.0218 (8)	0.0175 (8)	0.0005 (7)	−0.0079 (7)
C18	0.0194 (10)	0.0231 (10)	0.0202 (10)	0.0016 (9)	0.0038 (8)	0.0006 (8)
C19	0.0190 (9)	0.0174 (9)	0.0149 (8)	0.0027 (7)	0.0026 (8)	−0.0019 (8)
C20	0.0182 (9)	0.0246 (10)	0.0188 (10)	0.0038 (8)	0.0023 (8)	0.0008 (8)
C21	0.0204 (10)	0.0303 (11)	0.0188 (10)	−0.0018 (9)	−0.0016 (8)	−0.0025 (8)
C22	0.0324 (12)	0.0191 (9)	0.0243 (11)	−0.0051 (9)	0.0003 (9)	−0.0031 (8)
C23	0.0301 (12)	0.0200 (10)	0.0305 (11)	0.0026 (9)	−0.0043 (9)	0.0018 (9)
C24	0.0232 (10)	0.0231 (10)	0.0212 (9)	0.0023 (10)	−0.0035 (8)	−0.0012 (8)

Geometric parameters (Å, º)

S1—O2	1.4247 (15)	C13—H13A	0.9900
S1—O1	1.4276 (14)	C13—H13B	0.9900
S1—N1	1.6591 (16)	C14—C15	1.536 (3)
S1—C19	1.7620 (19)	C14—H14A	0.9900
N1—C2	1.408 (2)	C14—H14B	0.9900
N1—C9	1.416 (2)	C15—C16	1.526 (3)
C2—C3	1.360 (3)	C15—C18	1.532 (3)
C2—H2	0.9500	C15—H15	1.0000
C3—C4	1.455 (3)	C16—C17	1.544 (3)
C3—C10	1.463 (3)	C16—H16A	0.9900
C4—C9	1.401 (3)	C16—H16B	0.9900
C4—C5	1.401 (3)	C17—H17A	0.9900
C5—C6	1.386 (3)	C17—H17B	0.9900
C5—H5	0.9500	O18—C18	1.426 (2)
C6—C7	1.396 (3)	O18—H18O	0.8937
C6—H6	0.9500	C18—H18	1.0000
C7—C8	1.386 (3)	C19—C20	1.387 (3)
C7—H7	0.9500	C19—C24	1.388 (3)
C8—C9	1.387 (3)	C20—C21	1.391 (3)
C8—H8	0.9500	C20—H20	0.9500
C10—C11	1.332 (3)	C21—C22	1.380 (3)
C10—H10	0.9500	C21—H21	0.9500
C11—N12	1.441 (2)	C22—C23	1.380 (3)
C11—C18	1.524 (3)	C22—H22	0.9500
N12—C13	1.477 (2)	C23—C24	1.388 (3)
N12—C17	1.486 (2)	C23—H23	0.9500
C13—C14	1.554 (3)	C24—H24	0.9500
O2—S1—O1	120.64 (9)	C15—C14—H14A	110.1
O2—S1—N1	106.61 (9)	C13—C14—H14A	110.1
O1—S1—N1	105.48 (8)	C15—C14—H14B	110.1
O2—S1—C19	108.44 (9)	C13—C14—H14B	110.1
O1—S1—C19	108.59 (9)	H14A—C14—H14B	108.4
N1—S1—C19	106.19 (9)	C16—C15—C18	109.28 (17)
C2—N1—C9	108.23 (15)	C16—C15—C14	109.02 (17)
C2—N1—S1	122.58 (13)	C18—C15—C14	107.51 (16)
C9—N1—S1	125.08 (13)	C16—C15—H15	110.3
C3—C2—N1	109.93 (17)	C18—C15—H15	110.3
C3—C2—H2	125.0	C14—C15—H15	110.3
N1—C2—H2	125.0	C15—C16—C17	108.45 (15)
C2—C3—C4	106.66 (17)	C15—C16—H16A	110.0
C2—C3—C10	128.12 (17)	C17—C16—H16A	110.0
C4—C3—C10	125.20 (17)	C15—C16—H16B	110.0
C9—C4—C5	119.08 (18)	C17—C16—H16B	110.0
C9—C4—C3	108.43 (16)	H16A—C16—H16B	108.4
C5—C4—C3	132.48 (18)	N12—C17—C16	111.99 (16)
C6—C5—C4	118.16 (19)	N12—C17—H17A	109.2
C6—C5—H5	120.9	C16—C17—H17A	109.2
C4—C5—H5	120.9	N12—C17—H17B	109.2
C5—C6—C7	121.67 (18)	C16—C17—H17B	109.2
C5—C6—H6	119.2	H17A—C17—H17B	107.9
C7—C6—H6	119.2	C18—O18—H18O	102.6
C8—C7—C6	121.07 (19)	O18—C18—C11	108.35 (16)
C8—C7—H7	119.5	O18—C18—C15	112.92 (16)
C6—C7—H7	119.5	C11—C18—C15	107.22 (15)
C7—C8—C9	117.01 (19)	O18—C18—H18	109.4
C7—C8—H8	121.5	C11—C18—H18	109.4
C9—C8—H8	121.5	C15—C18—H18	109.4
C8—C9—C4	123.00 (17)	C20—C19—C24	121.68 (18)
C8—C9—N1	130.28 (18)	C20—C19—S1	118.96 (15)
C4—C9—N1	106.65 (16)	C24—C19—S1	119.28 (15)
C11—C10—C3	126.31 (18)	C19—C20—C21	118.59 (18)
C11—C10—H10	116.8	C19—C20—H20	120.7
C3—C10—H10	116.8	C21—C20—H20	120.7
C10—C11—N12	121.89 (17)	C22—C21—C20	120.05 (19)
C10—C11—C18	123.55 (17)	C22—C21—H21	120.0
N12—C11—C18	114.56 (16)	C20—C21—H21	120.0
C11—N12—C13	108.73 (15)	C23—C22—C21	120.88 (19)
C11—N12—C17	107.51 (15)	C23—C22—H22	119.6
C13—N12—C17	108.74 (15)	C21—C22—H22	119.6
N12—C13—C14	111.90 (15)	C22—C23—C24	120.0 (2)
N12—C13—H13A	109.2	C22—C23—H23	120.0
C14—C13—H13A	109.2	C24—C23—H23	120.0
N12—C13—H13B	109.2	C23—C24—C19	118.76 (19)
C14—C13—H13B	109.2	C23—C24—H24	120.6
H13A—C13—H13B	107.9	C19—C24—H24	120.6
C15—C14—C13	108.15 (16)
O2—S1—N1—C2	159.41 (14)	C10—C11—N12—C17	−117.8 (2)
O1—S1—N1—C2	30.04 (17)	C18—C11—N12—C17	62.7 (2)
C19—S1—N1—C2	−85.10 (16)	C11—N12—C13—C14	59.9 (2)
O2—S1—N1—C9	−46.13 (18)	C17—N12—C13—C14	−56.9 (2)
O1—S1—N1—C9	−175.51 (16)	N12—C13—C14—C15	−3.4 (2)
C19—S1—N1—C9	69.35 (18)	C13—C14—C15—C16	61.0 (2)
C9—N1—C2—C3	3.2 (2)	C13—C14—C15—C18	−57.3 (2)
S1—N1—C2—C3	161.37 (14)	C18—C15—C16—C17	60.3 (2)
N1—C2—C3—C4	−2.7 (2)	C14—C15—C16—C17	−57.0 (2)
N1—C2—C3—C10	175.66 (17)	C11—N12—C17—C16	−56.1 (2)
C2—C3—C4—C9	1.2 (2)	C13—N12—C17—C16	61.4 (2)
C10—C3—C4—C9	−177.18 (17)	C15—C16—C17—N12	−3.7 (2)
C2—C3—C4—C5	−179.9 (2)	C10—C11—C18—O18	52.0 (2)
C10—C3—C4—C5	1.7 (3)	N12—C11—C18—O18	−128.56 (17)
C9—C4—C5—C6	0.1 (3)	C10—C11—C18—C15	174.13 (18)
C3—C4—C5—C6	−178.66 (19)	N12—C11—C18—C15	−6.4 (2)
C4—C5—C6—C7	0.4 (3)	C16—C15—C18—O18	64.1 (2)
C5—C6—C7—C8	−0.1 (3)	C14—C15—C18—O18	−177.69 (16)
C6—C7—C8—C9	−0.7 (3)	C16—C15—C18—C11	−55.1 (2)
C7—C8—C9—C4	1.2 (3)	C14—C15—C18—C11	63.04 (19)
C7—C8—C9—N1	178.00 (18)	O2—S1—C19—C20	−160.00 (15)
C5—C4—C9—C8	−1.0 (3)	O1—S1—C19—C20	−27.24 (17)
C3—C4—C9—C8	178.10 (17)	N1—S1—C19—C20	85.76 (16)
C5—C4—C9—N1	−178.40 (17)	O2—S1—C19—C24	16.56 (18)
C3—C4—C9—N1	0.7 (2)	O1—S1—C19—C24	149.31 (15)
C2—N1—C9—C8	−179.47 (19)	N1—S1—C19—C24	−97.68 (16)
S1—N1—C9—C8	23.0 (3)	C24—C19—C20—C21	−2.6 (3)
C2—N1—C9—C4	−2.3 (2)	S1—C19—C20—C21	173.88 (15)
S1—N1—C9—C4	−159.80 (14)	C19—C20—C21—C22	1.1 (3)
C2—C3—C10—C11	−21.0 (3)	C20—C21—C22—C23	1.3 (3)
C4—C3—C10—C11	157.08 (19)	C21—C22—C23—C24	−2.4 (3)
C3—C10—C11—N12	0.1 (3)	C22—C23—C24—C19	0.9 (3)
C3—C10—C11—C18	179.54 (18)	C20—C19—C24—C23	1.6 (3)
C10—C11—N12—C13	124.66 (19)	S1—C19—C24—C23	−174.88 (16)
C18—C11—N12—C13	−54.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O18—H18O···O18^i	0.89	2.30	3.142 (3)	157

Symmetry code: (i) x−1/2, −y+5/2, −z+2.