Hydrated forms of N-[(3R)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methyl­ene­butano­yl]-(1S,2R)-bornane-10,2-sultam and its enanti­omer†

Triazolidinediones react with each enantiomeric bornanesultam derivative of tiglic acid to produce the appropriate ene adduct in high yield and with excellent regioselectivity and diastereo­selectivity. The optically pure products, viz. N-[(3R)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methyl­enebutano­yl]-(1S,2R)-bornane-10,2-sultam 0.15-hydrate, C₁₈H₂₆N₄O₅S·0.15H₂O, and its enantiomer N-[(3S)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methyl­enebutano­yl]-(1R,2S)-born­ane-10,2-sultam 0.35-hydrate, C₁₈H₂₆N₄O₅S·0.35H₂O, have been characterized by spectroscopy and single-crystal X-ray analysis. Their structures are the result of Cβ-re attack of the enophile on the double bond of the alkene.

Comment

The ene reaction of a triazolidinedione (TAD), singlet oxygen (¹O₂) and nitroso­arene with alkenes bearing allylic H atoms has attracted much attention from both the synthetic and the mechanistic points of view, and has recently been reviewed (Vougioukalakis & Orfanopoulos, 2005; Adam & Krebs, 2003). Isotope effect studies suggest that the reaction proceeds in steps through three-membered-ring inter­mediates, namely a perepoxide, a diaziridinium imide and an aziridine N-oxide (Adam, Krebs et al., 2002). The proposal, based on computational results, that there is a biradical inter­mediate (Singleton & Hang, 1999) has subsequently been challenged by stereochemical and stereoisotopic studies (Stratakis et al., 2001; Vassilikogiannakis et al., 2000).

Stereoselective ene reactions employing chiral auxiliaries have been also reported. Asymmetric ene reactions of singlet oxygen, N-phenyl­triazolidinedione and nitroso­arene with tigloyl amides bearing the (1S,2R)-anti­pode of bornane-10,2-sultam as the chiral auxiliary exhibited high chemical yields and excellent diastereoselectivities (Adam et al., 1998). The configurational assignment of the newly formed stereogenic centers in the major products was made by chemical correlation of their structures with those of known compounds, after removal of the chiral auxiliary moiety. The enantiomerically pure acrylic acid derivatives thus obtained are attractive compounds in the synthesis of α-methyl­ene-β-amino acids; these substances and, more especially, the peptides derived from them are of biological and pharmaceutical inter­est.

We have been involved in the development of such stereoselective ene reactions for some time and now communicate our results. These include the X-ray structures of (IIa) and (IIb), the enanti­omeric ene adducts of N-methyl­triazolidinedione, MeTAD, obtained from its reaction with the two chiral tigloyl amides (Ia) and (Ib), each of which bears an anti­pode of bornanesultam. The reactions between (I) and PhTAD are analogous to those shown in the first scheme below.

The structures of the two MeTAD adducts (Fig. 1) establish that the stereochemical outcome of the reaction is consistent with the proposed π-facially diastereoselective enophilic

attack of MeTAD on the tiglic acid derivative (I) (Adam, Degen et al., 2002). Thus, starting with the chiral tiglate (Ia) as the alkene, the major ene product (IIa), obtained by column chromatography and subsequent crystallization, was found to have a newly formed stereogenic centre with an R configuration, whereas the ene product (IIb) from the (Ib) tiglate amide had an S configuration at the new stereogenic centre. Adam, Degen et al. (2002) have argued that electrostatic repulsion between the sulfonyl and carbonyl groups, and steric inter­action between the bornane skeleton and the alkene substituents, give (I), the well defined s-trans conformation shown in the scheme above. Repulsions between the sulfonyl group and the incoming enophile then favour Cβ-re attack on the double bond of the alkene over Cβ-si attack. In addition, the products (II) contain intra­molecular N3—H⋯O2 hydrogen bonds (Fig. 1, and Tables 1 and 2); this source of thermodynamic stability may not be available to the products of Cβ-si attack, in which the positions of the H and MeTAD substituents at C14 would be inter­changed.

The X-ray analyses of (IIa) and (IIb) at 100 K give experimental absolute configurations consistent with conservation of configuration at the stereogenic centres in the starting tiglate amides (Ia) and (Ib). Apart from minor differences involving partially occupied solvent water sites (see below), the two crystal structures are mirror images. Corresponding bond distances and angles agree well and fully support the formulations in the first scheme. The final difference maps are featureless. The X-ray analyses therefore indicate that the samples are optically pure. As we have recently observed in the case of a fenchone derivative (Fraile et al., 2003), crystallization in a space group such as P4₁2₁2, which has only pure rotational symmetry, is not in itself a guarantee of optical purity.

In both (IIa) and (IIb), there are sites on diad axes thought to be partially occupied by water O atoms. The associated H atoms were not located. In (IIa), there is one such site; its contacts [O1W⋯H10B = 2.27 Å and O1W⋯O3(− + y, − x, + z) = 2.841 (4) Å] are consistent with atom O1W donating two and accepting two hydrogen bonds. In (IIb), there are two such sites. Atom O1W has a similar environment to the corresponding site in (IIa) but has a higher occupancy. Atom O2W makes O2W⋯H2A (2.53 Å) and O2W⋯O4(x − 1, y, z) [2.995 (11) Å] contacts, and has very low occupancy. The presence of two hydrate sites and the higher overall water content of (IIb) may explain the slightly greater length of its c axis.

The atomic U^ij values of the main residues are moderately well reproduced by TLS analyses [R2 = (ΣΔU²/ΣU²)^1/2 = 0.173 and 0.170; Schomaker & Trueblood, 1968]. The worst discrepancy in the Hirshfeld (1976) rigid bond test is ΔU = 0.004 (1₁) Ų for C1—C10 in (IIb).

Figure 1 The structures of MeTAD adducts (a) (IIa) and (b) (IIb). The X-ray experiment indicates that the respective configurations at C1, C4, C6 and C14 are SRRR in (IIa) and RSSS in (IIb). Hydrogen bonds are indicated by broken lines and 20% probability displacement ellipsoids are shown.

Experimental

The optically pure tiglic amides (I) were synthesized in high yield according to published procedures (Oppolzer et al., 1988, and references therein) and recrystallized from methanol. The ene reactions were performed in dry CH₂Cl₂ at room temperature. After 24 h, the original pink colour of the solution had disappeared. The solvent was removed, first in a rotary evaporator and then with a high vacuum pump. The remaining material was chromatographed on an SiO₂ column (eluant: EtOAc/n-hexane, 1/3 v/v). The ¹H NMR spectra of the product showed a diastereomeric ratio of ca 95:5 (the same ratio was observed when PhTAD was the enophile). After fractional recrystallization of the crude mixture, it was evident from the ¹H NMR spectra that only the major diastereomer (II) had been isolated. The pure stereoisomers (II) were characterized by ¹H NMR, ¹³C NMR and FT–IR spectroscopy, elemental analysis, and ESI and FAB mass spectrometry. Their optical rotations were also measured; each pair of enantiomeric products showed rotations of nearly identical magnitudes but of opposite signs. For (IIa), 100 mg of (Ia) gave (IIa) in 60% yield (83 mg) after crystallization (EtOAc/n-hexane), [α]_D = −133.8° (c = 0.12, CH₂Cl₂, 290 K). FT–IR (KBr, cm⁻¹): ν 3245.1, 2988.4, 1774.4, 1710.3, 1686.0, 1467.3, 1420.8, 1340.4, 1321.1, 1288.7, 1130.6, 973.6, 771.5, 536.6; ¹H NMR (CDCl₃, 250 MHz): δ 1.01 (s, 3H, CH₃), 1.23 (s, 3H, CH₃), 1.32–1.44 (m, 2H, CH₂), 1.35 (d, J = 6.75 Hz, 3H, CH₃), 1.63 (s, 3H, CH₃), 1.80–2.10 (m, 5H, CH, 2 × CH₂), 3.05 (s, 3H, CH₃), 3.43 (d, J = 13.76 Hz, 1H, CH), 3.57 (d, J = 13.76 Hz, 1H, CH), 4.09 (dd, J = 5.00 and 7.25 Hz, 1H, CH), 5.36 (tq, J = 1.58 and 6.75 Hz, 1H, CH), 5.96 (dd, J = 0.92 and 1.72 Hz, 1H, CH, olefinic), 6.19 (dd, J = 0.92 and 1.44 Hz, 1H, CH, olefinic), 7.51 (s, br, 1H, NH); ¹³C NMR (CDCl₃, 62.9 MHz): δ 13.2, 19.8, 21.4, 25.2, 26.2, 33.2, 38.3, 45.2, 47.7, 48.0, 52.4, 53.6, 66.1, 127.8, 141.1, 155.1, 155.7, 168.4. Analysis calculated for C₁₈H₂₆N₄O₅S: C 52.67, H 6.38, N 13.65, S 7.81%; found: C 52.65, H 6.37, N 13.64, S 7.79%; FAB–MS: calculated for C₁₈H₂₆N₄O₅S [M] = 410.49; found = 411 (100). For (IIb), 100 mg of (Ib) gave (IIb) in 63% yield (87 mg) after crystallization (EtOAc/n-hexane), [α]_D = +133.1° (c = 0.09, CH₂Cl₂, 291 K). Analysis calculated for C₁₈H₂₆N₄O₅S: C 52.67, H 6.38, N 13.65, S 7.81%; found: C 52.66, H 6.36, N 13.64, S 7.78%; FAB–MS: calculated for C₁₈H₂₆N₄O₅S [M] = 410.49; found = 411 (100).

Compound (IIa)

Crystal data

• C₁₈H₂₆N₄O₅S·0.151H₂O

• M_r = 413.21

• Tetragonal, P 4₃ 2₁ 2

• a = 12.2857 (1) Å

• c = 26.1898 (2) Å

• V = 3953.05 (5) ų

• Z = 8

• D_x = 1.388 Mg m⁻³

• Mo Kα radiation

• μ = 0.20 mm⁻¹

• T = 100 K

• Needle, colourless

• 0.45 × 0.20 × 0.20 mm

Data collection

• Nonius KappaCCD diffractometer

• φ and ω scans

• 9977 measured reflections

• 5702 independent reflections

• 5366 reflections with I > 2σ(I)

• R_int = 0.016

• θ_max = 30.0°

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.030

• wR(F²) = 0.077

• S = 1.03

• 5702 reflections

• 267 parameters

• H atoms treated by a mixture of independent and constrained refinement

• w = 1/[σ²(F_o²) + (0.0423P)² + 0.932P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max = 0.001

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

• Absolute structure: Flack (1983), 2381 Friedel pairs

• Flack parameter: −0.02 (5)

Table 1
Hydrogen-bond geometry (Å, °) for (IIa)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.935 (17)	1.914 (17)	2.8254 (14)	164.1 (14)

Compound (IIb)

Crystal data

• C₁₈H₂₆N₄O₅S·0.3485H₂O

• M_r = 416.77

• Tetragonal, P 4₁ 2₁ 2

• a = 12.2794 (2) Å

• c = 26.3417 (5) Å

• V = 3971.90 (12) ų

• Z = 8

• D_x = 1.394 Mg m⁻³

• Mo Kα radiation

• μ = 0.20 mm⁻¹

• T = 100 K

• Needle, colourless

• 0.34 × 0.24 × 0.24 mm

Data collection

• Nonius KappaCCD diffractometer

• φ and ω scans

• 10281 measured reflections

• 5761 independent reflections

• 4925 reflections with I > 2σ(I)

• R_int = 0.029

• θ_max = 30.0°

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.038

• wR(F²) = 0.094

• S = 0.98

• 5761 reflections

• 269 parameters

• H atoms treated by a mixture of independent and constrained refinement

• w = 1/[σ²(F_o²) + (0.051P)² + 0.6973P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

• Absolute structure: Flack (1983), 2399 Friedel pairs

• Flack parameter: −0.04 (6)

Table 2
Hydrogen-bond geometry (Å, °) for (IIb)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.95 (2)	1.91 (2)	2.8263 (18)	161.2 (17)

All C- and N-bonded H atoms were located unambiguously in difference maps. In the final refinement, the positions of C-bonded H atoms were determined by HFIX instructions in SHELXL97 (Sheldrick, 1997); they were then treated as riding on their parent atoms, with C—H distances of 0.95 (=CH₂), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (CH), and U_iso(H) values of 1.5 (meth­yl) or 1.2 times U_eq(C). Apart from one CH₃ group in (IIb), an orientation parameter was refined for each methyl group. The H atom bonded to atom N3 was freely refined. The disordered water H atoms were neither located nor included in the calculations.

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

The ene reaction of a triazolinedione (TAD), singlet oxygen (¹O₂) and nitrosoarene with alkenes bearing allylic H atoms has attracted much attention from both the synthetic and the mechanistic points of view, and has recently been reviewed (Vougioukalakis & Orfanopoulos, 2005; Adam & Krebs, 2003). Isotope effect studies suggest that the reaction proceeds in steps through three-membered-ring intermediates, namely a perepoxide, a diaziridinium imide and an aziridine-N-oxide (Adam, Krebs et al., 2002). The proposal, based on computational results, that there is biradical intermediate (Singleton & Hang, 1999) has subsequently been challenged by stereochemical and stereoisotopic studies (Stratakis et al., 2001; Vassilikogiannakis et al., 2000).

Stereoselective ene reactions employing chiral auxiliaries have been also reported. Asymmetric ene reactions of singlet oxygen, N-phenyltriazolinedione and nitrosoarene with tigloyl amides bearing the (1S,2R)-antipode of bornane-10,2-sultam as the chiral auxiliary exhibited high chemical yields and excellent diastereoselectivities (Adam et al., 1998). The configurational assignment of the newly formed stereogenic centers in the major products was made by chemical correlation of their structures with those of known compounds, after removal of the chiral auxiliary moiety. The enantiomerically pure acrylic acid derivatives thus obtained are attractive compounds in the synthesis of α-methylene-β-amino acids; these substances and, more especially, the peptides derived from them are of biological and pharmaceutical interest.

We have been involved in the development of such stereoselective ene reactions for some time and now communicate our results (Scheme 1). These include the X-ray structures of (2a) and (2b), the enantiomeric ene adducts of N-methyltriazolinedione, MeTAD, obtained from its reaction with the two chiral tigloyl amides (1a) and (1b), each of which bears an antipode of bornanesultam. The reactions between (1) and PhTAD are analogous to those shown in Scheme 1.

The structures of the two MeTAD adducts (Fig. 1) establish that the stereochemical outcome of the reaction is consistent with the proposed π-facially diastereoselective enophilic attack of MeTAD on the tiglic acid derivative (1) (Adam, Degen et al., 2002b). Thus, starting with the chiral tiglate (1a) as the alkene, the major ene product (2a), obtained by column chromatography and subsequent crystallization, was found to have a newly formed stereogenic centre with R configuration, whereas the ene product (2b) from the (1b) tiglate amide had an S configuration at the new stereogenic centre. Adam, Degen et al. (2002) have argued that electrostatic repulsion between the sulfonyl and carbonyl groups and steric interaction between the bornane skeleton and the alkene substituents give (1) the well defined s-trans conformation shown in Scheme 2. Repulsions between the sulfonyl group and the incoming enophile then favour Cβ-re attack on the double bond of the alkene over Cβ-si attack. In addition, the products 2 contain intramolecular N3—H···O2 hydrogen bonds (Fig. 1, and Tables 1 and 2); this source of thermodynamic stability would not be available to the products of Cβ-si attack, in which the positions of the H and MeTAD substituents at C14 would be interchanged.

The X-ray analyses of (2a) and (2b) at 100 K give experimental absolute configurations consistent with conservation of configuration at the stereogenic centres in the starting tiglate amides (1a) and (1b). Apart from minor differences involving partially occupied solvent water sites (see below), the two crystal structures are mirror images. Corresponding bond distances and angles agree well and fully support the formulations in Scheme 1. Final difference maps are featureless. The X-ray analyses therefore indicate that the samples are optically pure. As we have recently observed in the case of a fenchone derivative (Fraile et al., 2003), crystallization in a space group such as P4₁2₁2, which has only pure rotational symmetry, is not in itself a guarantee of optical purity.

In both (2a) and (2b), there are sites on diad axes thought to be partially occupied by water O atoms. The associated H atoms were not located. In (2a) there is one such site; its contacts [O1W···H10B = 2.27 Å and O1W···O3(−1/2 + y, 3/2 − x, 1/4 + z) = 2.841 (4) Å] are consistent with atom O1W donating two and accepting two hydrogen bonds. In (2b), there are two such sites. Atom O1W has a similar environment to the corresponding site in (2a) but has a higher occupancy. Atom O2W makes contacts O2W···H2A of 2.53 Å and O2W···O4(x − 1, y, z) of 2.995 (11) Å, and has very low occupancy. The presence of two hydrate sites and the higher overall water content of (2b) may explain the slightly greater length of its c axis.

The atomic U^ij values of the main residues are moderately well reproduced by TLS analyses [R2 = (ΣΔU²/ΣU²)^1/2 = 0.173 and 0.170; Schomaker & Trueblood, 1968]. The worst discrepancy in the Hirshfeld (1976) rigid bond test is ΔU = 0.004 (1₁) Ų for C1—C10 in (2b).

S2. Experimental

The optically pure tiglic amides (1) (Scheme 1) were synthesized in high yield according to published procedures (Oppolzer et al., 1988, and references therein) and recrystallized from methanol. The ene reactions were performed in dry CH₂Cl₂ at room temperature. After 24 h, the original pink colour of the solution had disappeared. The solvent was removed, first in a rotary evaporator and then with a high vacuum pump. The remaining material was chromatographed on an SiO₂ column (eluant EtOAc/n-hexane, 1/3 v/v). The ¹H NMR spectra of the product showed a diastereomeric ratio of ca 95:5 (the same ratio was observed when PhTAD was the enophile). After fractional recrystallization of the crude mixture, it was evident from the ¹H NMR spectra that only the major diastereomer 2 had been isolated (Scheme 1). The pure stereoisomers 2 were characterized by ¹H and ¹³C NMR, and FT–IR spectroscopy, elemental analysis, and ESI and FAB mass spectrometry. Their optical rotations were also measured; each pair of enantiomeric products showed rotations of nearly identical magnitudes but of opposite signs. For (2a), 100 mg of (1a) gave (2a) in 60% yield (83 mg) after crystallization (EtOAc/n-hexane), [α]_D = −133.8° (c = 0.12, CH₂Cl₂, 290 K). FT–IR (KBr, cm⁻¹): ν 3245.1, 2988.4, 1774.4, 1710.3, 1686.0, 1467.3, 1420.8, 1340.4, 1321.1, 1288.7, 1130.6, 973.6, 771.5, 536.6; ¹H NMR (CDCl₃, 250 MHz): 1.01 (s, 3H, CH₃), 1.23 (s, 3H, CH₃), 1.32–1.44 (m, 2H, CH₂), 1.35 (d, J = 6.75 Hz, 3H, CH₃), 1.63 (s, 3H, CH₃), 1.80–2.10 (m, 5H, CH, 2 × CH₂), 3.05 (s, 3H, CH₃), 3.43 (d, J = 13.76 Hz, 1H, CH), 3.57 (d, J = 13.76 Hz, 1H, CH), 4.09 (dd, J = 5.00 and 7.25 Hz, 1H, CH), 5.36 (tq, J = 1.58 and 6.75 Hz, 1H, CH), 5.96 (dd, J = 0.92 and 1.72 Hz, 1H, CH, olefinic), 6.19 (dd, J = 0.92 and 1.44 Hz, 1H, CH, olefinic), 7.51 (s, br, 1H, NH); ¹³C NMR (CDCl₃, 62.9 MHz): 13.2, 19.8, 21.4, 25.2, 26.2, 33.2, 38.3, 45.2, 47.7, 48.0, 52.4, 53.6, 66.1, 127.8, 141.1, 155.1, 155.7, 168.4; Analysis calculated for C₁₈H₂₆N₄O₅S: C 52.67, H 6.38, N 13.65, S 7.81%; found: C 52.65, H 6.37, N 13.64, S 7.79%; FAB MS: calculated for C₁₈H₂₆N₄O₅S [M] = 410.49; found: 411 (100). For (2b), 100 mg of (1b) gave (2b) in 63% yield (87 mg) after crystallization (EtOAc/n-hexane), [α]_D= +133.1° (c = 0.09, CH₂Cl₂, 291 K). Analysis calcualted for C₁₈H₂₆N₄O₅S: C 52.67, H 6.38, N 13.65, S 7.81%; found: C 52.66, H 6.36, N 13.64, S 7.78%; FAB MS: calculated for C₁₈H₂₆O₅N₄S [M] = 410.49; found: 411 (100).

S3. Refinement

All C– and N-bonded H atoms were unambiguously located in difference maps. In the final refinement, the positions of C-bonded H atoms were determined by HFIX instructions in SHELXL97 (Sheldrick, 1997); they were then treated as riding on their parent atoms with C—H distances of 0.95 (═CH₂), 0.98 (CH₃), 0.99 (CH₂) or 1.00 (CH) Å and U_iso(H) values of 1.5 (methyl) or 1.2 times U_eq(C). Apart from one CH₃ group in (2b), an orientation parameter was refined for each methyl group. The H atom bonded to atom N3 was freely refined. The disordered water H atoms were neither located nor included in the calculations.

Computing details

For both compounds, data collection: Collect (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The structures of MeTAD adducts (a) (2a) and (b) (2b). The X-ray experiment indicates that the respective configurations at C1, C4, C6 and C14 are SRRR in (2a) and RSSS in (2b). Hydrogen bonds are indicated by broken lines and 20% probability displacement ellipsoid are shown.

(IIa) N-[(3R)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methylenebutanoyl]- (1S,2R)-bornane-10,2-sultam 0.15-hydrate

Crystal data

C18H26N4O5S·0.151H2O	Dx = 1.388 Mg m^−3
Mr = 413.21	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 5344 reflections
Hall symbol: P 4nw 2abw	θ = 3.4–30.0°
a = 12.2857 (1) Å	µ = 0.20 mm^−1
c = 26.1898 (2) Å	T = 100 K
V = 3953.05 (5) Å^3	Needle, colourless
Z = 8	0.45 × 0.20 × 0.20 mm
F(000) = 1756.08

Data collection

Nonius KappaCCD diffractometer	Rint = 0.016
ϕ and ω scans	θmax = 30.0°, θmin = 3.4°
9977 measured reflections	h = −17→17
5702 independent reflections	k = −12→12
5366 reflections with I > 2σ(I)	l = −35→35

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 0.932P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.030	(Δ/σ)max = 0.001
wR(F^2) = 0.077	Δρmax = 0.39 e Å^−3
S = 1.03	Δρmin = −0.27 e Å^−3
5702 reflections	Absolute structure: Flack (1983), 2335 Friedel pairs
267 parameters	Absolute structure parameter: −0.02 (5)
0 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.61428 (2)	0.92254 (2)	0.896505 (11)	0.01270 (7)
O1	0.59222 (8)	0.80857 (8)	0.90085 (3)	0.01822 (19)
O2	0.52558 (8)	0.99646 (8)	0.90749 (3)	0.01728 (18)
O3	0.62211 (8)	1.06019 (8)	0.76925 (3)	0.0209 (2)
O4	0.23363 (8)	1.16499 (9)	0.91699 (3)	0.0223 (2)
O5	0.31547 (8)	1.21524 (8)	0.74797 (3)	0.01939 (19)
N1	0.66354 (8)	0.95261 (9)	0.83735 (4)	0.0132 (2)
N2	0.37367 (9)	1.08908 (9)	0.80860 (4)	0.0135 (2)
N3	0.33215 (9)	1.06310 (9)	0.85821 (4)	0.0154 (2)
N4	0.25339 (9)	1.21460 (9)	0.83176 (4)	0.0161 (2)
C1	0.82455 (10)	0.97538 (10)	0.89218 (5)	0.0136 (2)
C2	0.90632 (11)	1.06792 (11)	0.90194 (5)	0.0193 (3)
H2A	0.9383	1.0628	0.9366	0.023*
H2B	0.8719	1.1402	0.8977	0.023*
C3	0.99337 (12)	1.04648 (12)	0.85984 (6)	0.0230 (3)
H3A	0.9946	1.1063	0.8345	0.028*
H3B	1.0668	1.0387	0.875	0.028*
C4	0.95569 (10)	0.93844 (11)	0.83488 (5)	0.0187 (2)
H4	1.0151	0.8967	0.8176	0.022*
C5	0.85680 (11)	0.96344 (12)	0.80032 (5)	0.0189 (3)
H5A	0.8309	0.8973	0.7825	0.023*
H5B	0.8741	1.0204	0.7749	0.023*
C6	0.77246 (10)	1.00416 (10)	0.83991 (4)	0.0141 (2)
H6	0.7646	1.0849	0.837	0.017*
C7	0.90135 (10)	0.87756 (10)	0.88016 (5)	0.0159 (2)
C8	0.98037 (12)	0.85064 (13)	0.92385 (6)	0.0247 (3)
H8A	1.0244	0.7872	0.9145	0.037*
H8B	0.9389	0.8344	0.9549	0.037*
H8C	1.0282	0.9131	0.9301	0.037*
C9	0.84461 (12)	0.77121 (11)	0.86580 (5)	0.0213 (3)
H9A	0.8099	0.74	0.8961	0.032*
H9B	0.8983	0.7197	0.8523	0.032*
H9C	0.7892	0.7856	0.8397	0.032*
C10	0.73384 (10)	0.96102 (11)	0.93104 (5)	0.0159 (2)
H10A	0.7212	1.0299	0.9497	0.019*
H10B	0.7535	0.9039	0.956	0.019*
C11	0.59295 (10)	0.98864 (10)	0.79818 (4)	0.0139 (2)
C12	0.48755 (10)	0.92932 (10)	0.79204 (4)	0.0136 (2)
C13	0.48619 (11)	0.82106 (11)	0.79530 (5)	0.0193 (2)
H13A	0.5518	0.7823	0.8015	0.023*
H13B	0.4196	0.7826	0.7914	0.023*
C14	0.39201 (10)	0.99681 (10)	0.77338 (4)	0.0138 (2)
H14	0.4137	1.0286	0.7397	0.017*
C15	0.28804 (11)	0.93206 (12)	0.76440 (5)	0.0201 (3)
H15A	0.23	0.9814	0.7534	0.03*
H15B	0.2664	0.8959	0.7962	0.03*
H15C	0.3009	0.8772	0.7379	0.03*
C16	0.26871 (10)	1.14965 (11)	0.87412 (5)	0.0162 (2)
C17	0.31421 (10)	1.17741 (10)	0.79089 (5)	0.0146 (2)
C18	0.18613 (12)	1.31192 (12)	0.83006 (5)	0.0239 (3)
H18A	0.136	1.3073	0.801	0.036*
H18B	0.2327	1.3761	0.8262	0.036*
H18C	0.1444	1.3179	0.8618	0.036*
H3N	0.3878 (14)	1.0390 (13)	0.8798 (6)	0.018 (4)*
O1W	0.7449 (3)	0.7449 (3)	1.0	0.0243 (16)	0.302 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01191 (13)	0.01340 (14)	0.01279 (12)	−0.00009 (11)	−0.00012 (10)	−0.00006 (10)
O1	0.0217 (5)	0.0149 (4)	0.0181 (4)	−0.0036 (4)	0.0000 (4)	0.0012 (3)
O2	0.0145 (4)	0.0219 (5)	0.0154 (4)	0.0040 (4)	0.0000 (3)	−0.0024 (3)
O3	0.0192 (5)	0.0242 (5)	0.0192 (4)	−0.0042 (4)	−0.0021 (4)	0.0062 (4)
O4	0.0200 (5)	0.0297 (6)	0.0172 (4)	0.0043 (4)	0.0019 (4)	−0.0032 (4)
O5	0.0196 (5)	0.0199 (5)	0.0187 (4)	0.0023 (4)	0.0010 (3)	0.0035 (4)
N1	0.0105 (5)	0.0153 (5)	0.0140 (4)	−0.0014 (4)	0.0007 (4)	0.0011 (4)
N2	0.0137 (5)	0.0146 (5)	0.0124 (4)	0.0008 (4)	0.0013 (4)	−0.0011 (4)
N3	0.0147 (5)	0.0181 (5)	0.0135 (4)	0.0019 (4)	−0.0002 (4)	−0.0002 (4)
N4	0.0139 (5)	0.0159 (5)	0.0184 (5)	0.0034 (4)	0.0004 (4)	−0.0010 (4)
C1	0.0126 (5)	0.0115 (5)	0.0169 (5)	0.0001 (4)	−0.0011 (4)	−0.0016 (4)
C2	0.0167 (6)	0.0136 (6)	0.0277 (6)	−0.0033 (5)	−0.0041 (5)	−0.0027 (5)
C3	0.0161 (6)	0.0204 (6)	0.0327 (7)	−0.0044 (5)	0.0000 (5)	0.0004 (5)
C4	0.0132 (6)	0.0178 (6)	0.0252 (6)	−0.0003 (5)	0.0029 (5)	−0.0013 (5)
C5	0.0147 (6)	0.0215 (6)	0.0206 (6)	−0.0022 (5)	0.0043 (5)	0.0013 (5)
C6	0.0113 (5)	0.0122 (5)	0.0189 (5)	−0.0011 (5)	−0.0007 (4)	0.0007 (4)
C7	0.0141 (6)	0.0124 (5)	0.0213 (6)	0.0016 (5)	−0.0008 (4)	−0.0006 (4)
C8	0.0194 (7)	0.0232 (7)	0.0317 (7)	0.0059 (5)	−0.0063 (6)	0.0040 (6)
C9	0.0234 (7)	0.0119 (6)	0.0287 (6)	0.0004 (5)	0.0017 (5)	−0.0025 (5)
C10	0.0136 (6)	0.0185 (6)	0.0156 (5)	0.0013 (5)	−0.0027 (4)	−0.0030 (4)
C11	0.0139 (5)	0.0147 (5)	0.0132 (5)	0.0015 (4)	0.0010 (4)	−0.0016 (4)
C12	0.0130 (5)	0.0166 (6)	0.0113 (5)	0.0003 (5)	0.0009 (4)	−0.0009 (4)
C13	0.0187 (6)	0.0170 (6)	0.0223 (6)	0.0004 (5)	−0.0031 (5)	−0.0004 (5)
C14	0.0138 (5)	0.0139 (6)	0.0137 (5)	0.0003 (5)	−0.0007 (4)	−0.0016 (4)
C15	0.0160 (6)	0.0199 (6)	0.0243 (6)	−0.0004 (5)	−0.0055 (5)	−0.0040 (5)
C16	0.0117 (6)	0.0194 (6)	0.0176 (5)	−0.0006 (5)	−0.0020 (4)	−0.0027 (5)
C17	0.0108 (5)	0.0148 (6)	0.0183 (5)	−0.0008 (5)	−0.0008 (4)	−0.0008 (4)
C18	0.0248 (7)	0.0203 (7)	0.0266 (6)	0.0103 (6)	0.0012 (5)	−0.0021 (5)
O1W	0.025 (2)	0.025 (2)	0.023 (2)	0.005 (2)	−0.0013 (12)	0.0013 (12)

Geometric parameters (Å, º)

S1—O1	1.4306 (10)	C4—H4	1
S1—O2	1.4475 (10)	C5—C6	1.5489 (17)
S1—N1	1.7037 (10)	C5—H5A	0.99
S1—C10	1.7887 (13)	C5—H5B	0.99
O3—C11	1.2146 (15)	C6—H6	1
O4—C16	1.2173 (16)	C7—C9	1.5280 (19)
O5—C17	1.2164 (15)	C7—C8	1.5366 (18)
N1—C11	1.4143 (15)	C8—H8A	0.98
N1—C6	1.4820 (16)	C8—H8B	0.98
N2—C17	1.3881 (16)	C8—H8C	0.98
N2—N3	1.4318 (14)	C9—H9A	0.98
N2—C14	1.4789 (15)	C9—H9B	0.98
N3—C16	1.3826 (17)	C9—H9C	0.98
N3—H3N	0.935 (17)	C10—H10A	0.99
N4—C16	1.3795 (16)	C10—H10B	0.99
N4—C17	1.3830 (16)	C11—C12	1.4946 (17)
N4—C18	1.4541 (17)	C12—C13	1.3330 (18)
C1—C10	1.5196 (17)	C12—C14	1.5179 (17)
C1—C2	1.5385 (17)	C13—H13A	0.95
C1—C6	1.5519 (16)	C13—H13B	0.95
C1—C7	1.5600 (17)	C14—C15	1.5230 (18)
C2—C3	1.5584 (19)	C14—H14	1
C2—H2A	0.99	C15—H15A	0.98
C2—H2B	0.99	C15—H15B	0.98
C3—C4	1.5504 (19)	C15—H15C	0.98
C3—H3A	0.99	C18—H18A	0.98
C3—H3B	0.99	C18—H18B	0.98
C4—C5	1.5457 (19)	C18—H18C	0.98
C4—C7	1.5529 (18)
O1—S1—O2	117.10 (6)	C8—C7—C4	113.62 (11)
O1—S1—N1	110.60 (5)	C9—C7—C1	115.63 (11)
O2—S1—N1	108.18 (5)	C8—C7—C1	113.43 (11)
O1—S1—C10	111.97 (6)	C4—C7—C1	92.47 (9)
O2—S1—C10	110.60 (6)	C7—C8—H8A	109.5
N1—S1—C10	96.36 (6)	C7—C8—H8B	109.5
C11—N1—C6	116.92 (10)	H8A—C8—H8B	109.5
C11—N1—S1	120.64 (8)	C7—C8—H8C	109.5
C6—N1—S1	111.85 (7)	H8A—C8—H8C	109.5
C17—N2—N3	106.86 (9)	H8B—C8—H8C	109.5
C17—N2—C14	118.10 (9)	C7—C9—H9A	109.5
N3—N2—C14	116.71 (10)	C7—C9—H9B	109.5
C16—N3—N2	107.63 (10)	H9A—C9—H9B	109.5
C16—N3—H3N	118.2 (10)	C7—C9—H9C	109.5
N2—N3—H3N	111.1 (10)	H9A—C9—H9C	109.5
C16—N4—C17	110.95 (10)	H9B—C9—H9C	109.5
C16—N4—C18	125.30 (11)	C1—C10—S1	107.11 (8)
C17—N4—C18	123.71 (11)	C1—C10—H10A	110.3
C10—C1—C2	116.97 (10)	S1—C10—H10A	110.3
C10—C1—C6	108.35 (10)	C1—C10—H10B	110.3
C2—C1—C6	104.33 (10)	S1—C10—H10B	110.3
C10—C1—C7	119.29 (10)	H10A—C10—H10B	108.5
C2—C1—C7	102.00 (10)	O3—C11—N1	119.88 (11)
C6—C1—C7	104.30 (9)	O3—C11—C12	122.77 (11)
C1—C2—C3	101.87 (10)	N1—C11—C12	117.18 (10)
C1—C2—H2A	111.4	C13—C12—C11	119.37 (12)
C3—C2—H2A	111.4	C13—C12—C14	123.78 (12)
C1—C2—H2B	111.4	C11—C12—C14	116.00 (11)
C3—C2—H2B	111.4	C12—C13—H13A	120
H2A—C2—H2B	109.3	C12—C13—H13B	120
C4—C3—C2	103.78 (11)	H13A—C13—H13B	120
C4—C3—H3A	111	N2—C14—C12	109.62 (9)
C2—C3—H3A	111	N2—C14—C15	111.64 (10)
C4—C3—H3B	111	C12—C14—C15	114.39 (11)
C2—C3—H3B	111	N2—C14—H14	106.9
H3A—C3—H3B	109	C12—C14—H14	106.9
C5—C4—C3	108.14 (11)	C15—C14—H14	106.9
C5—C4—C7	101.83 (10)	C14—C15—H15A	109.5
C3—C4—C7	102.63 (11)	C14—C15—H15B	109.5
C5—C4—H4	114.3	H15A—C15—H15B	109.5
C3—C4—H4	114.3	C14—C15—H15C	109.5
C7—C4—H4	114.3	H15A—C15—H15C	109.5
C4—C5—C6	101.43 (10)	H15B—C15—H15C	109.5
C4—C5—H5A	111.5	O4—C16—N4	127.15 (12)
C6—C5—H5A	111.5	O4—C16—N3	126.62 (12)
C4—C5—H5B	111.5	N4—C16—N3	106.23 (10)
C6—C5—H5B	111.5	O5—C17—N4	126.57 (12)
H5A—C5—H5B	109.3	O5—C17—N2	126.93 (11)
N1—C6—C5	115.83 (10)	N4—C17—N2	106.49 (10)
N1—C6—C1	108.36 (9)	N4—C18—H18A	109.5
C5—C6—C1	103.94 (10)	N4—C18—H18B	109.5
N1—C6—H6	109.5	H18A—C18—H18B	109.5
C5—C6—H6	109.5	N4—C18—H18C	109.5
C1—C6—H6	109.5	H18A—C18—H18C	109.5
C9—C7—C8	106.70 (11)	H18B—C18—H18C	109.5
C9—C7—C4	114.83 (11)
O1—S1—N1—C11	94.88 (10)	C10—C1—C7—C4	171.46 (11)
O2—S1—N1—C11	−34.59 (11)	C2—C1—C7—C4	−57.94 (11)
C10—S1—N1—C11	−148.76 (10)	C6—C1—C7—C4	50.43 (11)
O1—S1—N1—C6	−121.56 (9)	C2—C1—C10—S1	143.21 (10)
O2—S1—N1—C6	108.96 (9)	C6—C1—C10—S1	25.74 (12)
C10—S1—N1—C6	−5.20 (9)	C7—C1—C10—S1	−93.23 (11)
C17—N2—N3—C16	−13.96 (13)	O1—S1—C10—C1	102.76 (9)
C14—N2—N3—C16	−148.68 (11)	O2—S1—C10—C1	−124.67 (8)
C10—C1—C2—C3	172.25 (11)	N1—S1—C10—C1	−12.50 (9)
C6—C1—C2—C3	−68.11 (12)	C6—N1—C11—O3	−1.37 (17)
C7—C1—C2—C3	40.24 (12)	S1—N1—C11—O3	140.43 (10)
C1—C2—C3—C4	−5.13 (13)	C6—N1—C11—C12	173.95 (10)
C2—C3—C4—C5	75.38 (13)	S1—N1—C11—C12	−44.25 (14)
C2—C3—C4—C7	−31.74 (13)	O3—C11—C12—C13	133.07 (13)
C3—C4—C5—C6	−63.15 (13)	N1—C11—C12—C13	−42.10 (16)
C7—C4—C5—C6	44.53 (12)	O3—C11—C12—C14	−36.78 (16)
C11—N1—C6—C5	−77.66 (13)	N1—C11—C12—C14	148.05 (10)
S1—N1—C6—C5	137.31 (9)	C17—N2—C14—C12	160.55 (11)
C11—N1—C6—C1	166.06 (10)	N3—N2—C14—C12	−69.89 (13)
S1—N1—C6—C1	21.04 (12)	C17—N2—C14—C15	−71.64 (13)
C4—C5—C6—N1	−129.82 (11)	N3—N2—C14—C15	57.93 (13)
C4—C5—C6—C1	−11.08 (12)	C13—C12—C14—N2	133.24 (12)
C10—C1—C6—N1	−29.93 (13)	C11—C12—C14—N2	−57.41 (13)
C2—C1—C6—N1	−155.23 (10)	C13—C12—C14—C15	6.97 (17)
C7—C1—C6—N1	98.12 (11)	C11—C12—C14—C15	176.33 (10)
C10—C1—C6—C5	−153.68 (10)	C17—N4—C16—O4	174.00 (13)
C2—C1—C6—C5	81.03 (11)	C18—N4—C16—O4	−3.7 (2)
C7—C1—C6—C5	−25.62 (12)	C17—N4—C16—N3	−6.01 (15)
C5—C4—C7—C9	61.87 (13)	C18—N4—C16—N3	176.29 (12)
C3—C4—C7—C9	173.77 (11)	N2—N3—C16—O4	−167.90 (13)
C5—C4—C7—C8	−174.89 (11)	N2—N3—C16—N4	12.11 (13)
C3—C4—C7—C8	−62.99 (14)	C16—N4—C17—O5	177.58 (13)
C5—C4—C7—C1	−57.93 (11)	C18—N4—C17—O5	−4.7 (2)
C3—C4—C7—C1	53.96 (11)	C16—N4—C17—N2	−2.72 (14)
C10—C1—C7—C9	52.31 (15)	C18—N4—C17—N2	175.02 (12)
C2—C1—C7—C9	−177.08 (11)	N3—N2—C17—O5	−170.24 (13)
C6—C1—C7—C9	−68.71 (13)	C14—N2—C17—O5	−36.26 (19)
C10—C1—C7—C8	−71.42 (15)	N3—N2—C17—N4	10.06 (13)
C2—C1—C7—C8	59.18 (13)	C14—N2—C17—N4	144.04 (11)
C6—C1—C7—C8	167.55 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.935 (17)	1.914 (17)	2.8254 (14)	164.1 (14)

(IIb) N-[(3S)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methylenebutanoyl]- (1R,2S)-bornane-10,2-sultam 0.35-hydrate

Crystal data

C18H26N4O5S·0.3485H2O	Dx = 1.394 Mg m^−3
Mr = 416.77	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 5248 reflections
Hall symbol: P 4abw 2nw	θ = 3.4–30.0°
a = 12.2794 (2) Å	µ = 0.20 mm^−1
c = 26.3417 (5) Å	T = 100 K
V = 3971.90 (12) Å^3	Needle, colourless
Z = 8	0.34 × 0.24 × 0.24 mm
F(000) = 1771.9

Data collection

Nonius KappaCCD diffractometer	Rint = 0.029
ϕ and ω scans	θmax = 30.0°, θmin = 3.4°
10281 measured reflections	h = −17→17
5761 independent reflections	k = −12→12
4925 reflections with I > 2σ(I)	l = −37→27

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.6973P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.038	(Δ/σ)max < 0.001
wR(F^2) = 0.094	Δρmax = 0.33 e Å^−3
S = 0.98	Δρmin = −0.30 e Å^−3
5761 reflections	Absolute structure: Flack (1983), 3379 Friedel pairs
269 parameters	Absolute structure parameter: −0.04 (6)
0 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.38527 (3)	0.07511 (3)	0.103784 (15)	0.01338 (9)
O1	0.40787 (10)	0.18889 (10)	0.09908 (4)	0.0184 (2)
O2	0.47348 (9)	0.00080 (10)	0.09299 (4)	0.0177 (2)
O3	0.37676 (10)	−0.05788 (10)	0.23180 (4)	0.0218 (3)
O4	0.76523 (10)	−0.16679 (11)	0.08385 (4)	0.0230 (3)
O5	0.68529 (10)	−0.21530 (10)	0.25216 (4)	0.0203 (3)
N1	0.33637 (11)	0.04596 (11)	0.16285 (5)	0.0142 (3)
N2	0.62621 (11)	−0.08994 (11)	0.19168 (5)	0.0144 (3)
N3	0.66731 (11)	−0.06448 (12)	0.14220 (5)	0.0161 (3)
N4	0.74621 (12)	−0.21573 (12)	0.16868 (5)	0.0167 (3)
C1	0.17483 (13)	0.02332 (13)	0.10865 (6)	0.0138 (3)
C2	0.09266 (13)	−0.06889 (14)	0.09953 (7)	0.0199 (3)
H2A	0.1269	−0.1412	0.104	0.024*
H2B	0.0605	−0.0644	0.0651	0.024*
C3	0.00588 (15)	−0.04660 (15)	0.14128 (7)	0.0242 (4)
H3A	−0.0676	−0.0388	0.1263	0.029*
H3B	0.0045	−0.1061	0.1666	0.029*
C4	0.04432 (13)	0.06202 (14)	0.16570 (7)	0.0194 (3)
H4	−0.0148	0.1044	0.1828	0.023*
C5	0.14316 (14)	0.03666 (14)	0.19997 (6)	0.0190 (3)
H5A	0.1256	−0.0199	0.2255	0.023*
H5B	0.1697	0.1028	0.2175	0.023*
C6	0.22687 (13)	−0.00505 (14)	0.16073 (6)	0.0150 (3)
H6	0.2343	−0.0859	0.1639	0.018*
C7	0.09856 (13)	0.12166 (13)	0.12032 (6)	0.0167 (3)
C8	0.01985 (16)	0.14852 (16)	0.07690 (7)	0.0251 (4)
H8A	−0.0248	0.2115	0.0863	0.038*
H8B	−0.0275	0.0857	0.0705	0.038*
H8C	0.0615	0.1655	0.0462	0.038*
C9	0.15605 (15)	0.22784 (14)	0.13415 (7)	0.0212 (4)
H9A	0.1902	0.2587	0.1038	0.032*
H9B	0.212	0.2133	0.1598	0.032*
H9C	0.1028	0.2797	0.1478	0.032*
C10	0.26551 (13)	0.03631 (14)	0.06993 (6)	0.0161 (3)
H10A	0.246	0.0929	0.0448	0.019*
H10B	0.2778	−0.0332	0.0517	0.019*
C11	0.40659 (13)	0.01171 (13)	0.20213 (6)	0.0146 (3)
C12	0.51276 (13)	0.07025 (13)	0.20754 (6)	0.0141 (3)
C13	0.51451 (15)	0.17838 (14)	0.20345 (6)	0.0198 (3)
H13A	0.4489	0.2172	0.1972	0.024*
H13B	0.5813	0.2167	0.2068	0.024*
C14	0.60771 (13)	0.00279 (13)	0.22633 (6)	0.0146 (3)
H14	0.5856	−0.0286	0.2598	0.018*
C15	0.71181 (14)	0.06715 (15)	0.23541 (7)	0.0206 (4)
H15A	0.7696	0.0176	0.2466	0.031*
H15B	0.6989	0.1223	0.2616	0.031*
H15C	0.734	0.103	0.2038	0.031*
C16	0.73065 (13)	−0.15109 (14)	0.12648 (6)	0.0168 (3)
C17	0.68562 (13)	−0.17799 (13)	0.20934 (6)	0.0147 (3)
C18	0.81322 (16)	−0.31329 (15)	0.17042 (7)	0.0252 (4)
H18A	0.8719	−0.3032	0.1952	0.038*
H18B	0.8446	−0.3268	0.1368	0.038*
H18C	0.7683	−0.3756	0.1805	0.038*
H3N	0.6124 (16)	−0.0387 (16)	0.1196 (7)	0.020 (5)*
O1W	0.25438 (19)	0.25438 (19)	0	0.0274 (12)	0.593 (8)
O2W	−0.0894 (13)	−0.0894 (13)	0	0.043 (8)*	0.104 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01218 (18)	0.01333 (19)	0.01463 (17)	0.00008 (15)	−0.00015 (15)	−0.00003 (15)
O1	0.0205 (6)	0.0155 (6)	0.0191 (6)	−0.0032 (5)	0.0000 (5)	0.0011 (5)
O2	0.0151 (6)	0.0214 (6)	0.0167 (5)	0.0038 (5)	−0.0005 (4)	−0.0021 (5)
O3	0.0194 (6)	0.0254 (7)	0.0206 (6)	−0.0038 (5)	−0.0024 (5)	0.0062 (5)
O4	0.0208 (6)	0.0301 (7)	0.0182 (6)	0.0049 (6)	0.0025 (5)	−0.0037 (5)
O5	0.0205 (6)	0.0219 (6)	0.0186 (6)	0.0024 (5)	0.0011 (5)	0.0032 (5)
N1	0.0122 (6)	0.0148 (7)	0.0155 (6)	−0.0016 (5)	0.0003 (5)	0.0011 (5)
N2	0.0150 (6)	0.0152 (7)	0.0130 (6)	0.0013 (5)	0.0021 (5)	−0.0004 (5)
N3	0.0156 (6)	0.0193 (7)	0.0134 (6)	0.0024 (6)	−0.0010 (5)	0.0004 (6)
N4	0.0142 (7)	0.0160 (7)	0.0200 (7)	0.0026 (6)	0.0001 (5)	−0.0010 (6)
C1	0.0120 (7)	0.0104 (7)	0.0191 (8)	0.0001 (6)	−0.0003 (6)	−0.0008 (6)
C2	0.0167 (8)	0.0127 (7)	0.0304 (9)	−0.0032 (7)	−0.0044 (7)	−0.0033 (7)
C3	0.0168 (8)	0.0205 (9)	0.0353 (10)	−0.0058 (7)	−0.0004 (8)	0.0002 (8)
C4	0.0138 (8)	0.0172 (8)	0.0271 (9)	0.0010 (7)	0.0028 (7)	−0.0012 (7)
C5	0.0151 (8)	0.0193 (8)	0.0227 (8)	−0.0026 (7)	0.0039 (7)	0.0008 (7)
C6	0.0120 (7)	0.0119 (7)	0.0212 (8)	−0.0021 (6)	−0.0013 (6)	−0.0001 (6)
C7	0.0142 (8)	0.0123 (7)	0.0235 (8)	0.0014 (7)	−0.0007 (6)	−0.0016 (6)
C8	0.0196 (9)	0.0221 (9)	0.0335 (10)	0.0050 (7)	−0.0053 (8)	0.0043 (8)
C9	0.0221 (9)	0.0119 (8)	0.0295 (9)	0.0005 (7)	0.0032 (7)	−0.0005 (7)
C10	0.0146 (8)	0.0172 (8)	0.0165 (8)	0.0013 (6)	−0.0037 (6)	−0.0030 (6)
C11	0.0146 (7)	0.0139 (7)	0.0153 (7)	0.0017 (6)	0.0016 (6)	−0.0035 (6)
C12	0.0127 (7)	0.0166 (7)	0.0130 (7)	0.0007 (6)	0.0002 (6)	−0.0007 (6)
C13	0.0175 (8)	0.0176 (8)	0.0242 (9)	−0.0007 (7)	−0.0026 (7)	−0.0006 (7)
C14	0.0152 (7)	0.0137 (7)	0.0150 (7)	−0.0005 (6)	−0.0004 (6)	−0.0017 (6)
C15	0.0158 (8)	0.0213 (8)	0.0247 (8)	0.0023 (7)	−0.0045 (7)	−0.0039 (7)
C16	0.0118 (8)	0.0209 (8)	0.0176 (8)	−0.0013 (7)	−0.0025 (6)	−0.0031 (7)
C17	0.0100 (7)	0.0144 (7)	0.0196 (8)	−0.0011 (6)	−0.0006 (6)	−0.0008 (6)
C18	0.0253 (9)	0.0209 (9)	0.0294 (9)	0.0114 (8)	0.0008 (8)	−0.0026 (7)
O1W	0.0245 (14)	0.0245 (14)	0.033 (2)	0.0033 (14)	−0.0015 (9)	0.0015 (9)

Geometric parameters (Å, º)

S1—O1	1.4298 (12)	C4—H4	1
S1—O2	1.4446 (12)	C5—C6	1.545 (2)
S1—N1	1.7057 (13)	C5—H5A	0.99
S1—C10	1.7846 (17)	C5—H5B	0.99
O3—C11	1.215 (2)	C6—H6	1
O4—C16	1.216 (2)	C7—C9	1.527 (2)
O5—C17	1.217 (2)	C7—C8	1.533 (2)
N1—C11	1.411 (2)	C8—H8A	0.98
N1—C6	1.484 (2)	C8—H8B	0.98
N2—C17	1.385 (2)	C8—H8C	0.98
N2—N3	1.4321 (18)	C9—H9A	0.98
N2—C14	1.477 (2)	C9—H9B	0.98
N3—C16	1.381 (2)	C9—H9C	0.98
N3—H3N	0.95 (2)	C10—H10A	0.99
N4—C16	1.379 (2)	C10—H10B	0.99
N4—C17	1.384 (2)	C11—C12	1.496 (2)
N4—C18	1.454 (2)	C12—C13	1.332 (2)
C1—C10	1.519 (2)	C12—C14	1.514 (2)
C1—C2	1.536 (2)	C13—H13A	0.95
C1—C6	1.553 (2)	C13—H13B	0.95
C1—C7	1.559 (2)	C14—C15	1.522 (2)
C2—C3	1.556 (3)	C14—H14	1
C2—H2A	0.99	C15—H15A	0.98
C2—H2B	0.99	C15—H15B	0.98
C3—C4	1.554 (2)	C15—H15C	0.98
C3—H3A	0.99	C18—H18A	0.98
C3—H3B	0.99	C18—H18B	0.98
C4—C5	1.544 (2)	C18—H18C	0.98
C4—C7	1.552 (2)
O1—S1—O2	117.04 (8)	C8—C7—C4	113.92 (14)
O1—S1—N1	110.64 (7)	C9—C7—C1	115.52 (13)
O2—S1—N1	108.12 (7)	C8—C7—C1	113.47 (14)
O1—S1—C10	112.18 (8)	C4—C7—C1	92.53 (12)
O2—S1—C10	110.54 (8)	C7—C8—H8A	109.5
N1—S1—C10	96.30 (7)	C7—C8—H8B	109.5
C11—N1—C6	117.08 (13)	H8A—C8—H8B	109.5
C11—N1—S1	121.08 (11)	C7—C8—H8C	109.5
C6—N1—S1	111.92 (10)	H8A—C8—H8C	109.5
C17—N2—N3	106.89 (12)	H8B—C8—H8C	109.5
C17—N2—C14	118.38 (13)	C7—C9—H9A	109.5
N3—N2—C14	116.64 (13)	C7—C9—H9B	109.5
C16—N3—N2	107.65 (13)	H9A—C9—H9B	109.5
C16—N3—H3N	117.8 (11)	C7—C9—H9C	109.5
N2—N3—H3N	113.0 (12)	H9A—C9—H9C	109.5
C16—N4—C17	110.89 (13)	H9B—C9—H9C	109.5
C16—N4—C18	125.30 (14)	C1—C10—S1	107.26 (11)
C17—N4—C18	123.76 (14)	C1—C10—H10A	110.3
C10—C1—C2	117.01 (14)	S1—C10—H10A	110.3
C10—C1—C6	108.37 (13)	C1—C10—H10B	110.3
C2—C1—C6	104.08 (13)	S1—C10—H10B	110.3
C10—C1—C7	119.44 (14)	H10A—C10—H10B	108.5
C2—C1—C7	101.97 (13)	O3—C11—N1	119.82 (15)
C6—C1—C7	104.29 (13)	O3—C11—C12	122.66 (15)
C1—C2—C3	102.10 (13)	N1—C11—C12	117.34 (13)
C1—C2—H2A	111.3	C13—C12—C11	119.04 (15)
C3—C2—H2A	111.3	C13—C12—C14	124.01 (15)
C1—C2—H2B	111.3	C11—C12—C14	116.08 (14)
C3—C2—H2B	111.3	C12—C13—H13A	120
H2A—C2—H2B	109.2	C12—C13—H13B	120
C4—C3—C2	103.63 (14)	H13A—C13—H13B	120
C4—C3—H3A	111	N2—C14—C12	109.77 (12)
C2—C3—H3A	111	N2—C14—C15	111.61 (14)
C4—C3—H3B	111	C12—C14—C15	114.48 (14)
C2—C3—H3B	111	N2—C14—H14	106.9
H3A—C3—H3B	109	C12—C14—H14	106.9
C5—C4—C7	102.00 (13)	C15—C14—H14	106.9
C5—C4—C3	107.92 (14)	C14—C15—H15A	109.5
C7—C4—C3	102.50 (14)	C14—C15—H15B	109.5
C5—C4—H4	114.4	H15A—C15—H15B	109.5
C7—C4—H4	114.4	C14—C15—H15C	109.5
C3—C4—H4	114.4	H15A—C15—H15C	109.5
C4—C5—C6	101.46 (13)	H15B—C15—H15C	109.5
C4—C5—H5A	111.5	O4—C16—N4	127.21 (16)
C6—C5—H5A	111.5	O4—C16—N3	126.55 (16)
C4—C5—H5B	111.5	N4—C16—N3	106.23 (14)
C6—C5—H5B	111.5	O5—C17—N4	126.36 (15)
H5A—C5—H5B	109.3	O5—C17—N2	127.10 (15)
N1—C6—C5	115.96 (13)	N4—C17—N2	106.54 (13)
N1—C6—C1	108.13 (12)	N4—C18—H18A	109.5
C5—C6—C1	104.05 (13)	N4—C18—H18B	109.5
N1—C6—H6	109.5	H18A—C18—H18B	109.5
C5—C6—H6	109.5	N4—C18—H18C	109.5
C1—C6—H6	109.5	H18A—C18—H18C	109.5
C9—C7—C8	106.61 (14)	H18B—C18—H18C	109.5
C9—C7—C4	114.68 (14)
O1—S1—N1—C11	−93.88 (13)	C10—C1—C7—C4	−171.29 (14)
O2—S1—N1—C11	35.49 (14)	C2—C1—C7—C4	57.96 (15)
C10—S1—N1—C11	149.54 (13)	C6—C1—C7—C4	−50.14 (14)
O1—S1—N1—C6	121.48 (11)	C2—C1—C10—S1	−143.26 (13)
O2—S1—N1—C6	−109.15 (11)	C6—C1—C10—S1	−26.06 (15)
C10—S1—N1—C6	4.90 (12)	C7—C1—C10—S1	93.02 (15)
C17—N2—N3—C16	13.86 (17)	O1—S1—C10—C1	−102.49 (12)
C14—N2—N3—C16	148.94 (14)	O2—S1—C10—C1	124.89 (11)
C10—C1—C2—C3	−172.41 (14)	N1—S1—C10—C1	12.84 (12)
C6—C1—C2—C3	68.07 (15)	C6—N1—C11—O3	1.1 (2)
C7—C1—C2—C3	−40.18 (16)	S1—N1—C11—O3	−141.82 (13)
C1—C2—C3—C4	5.05 (17)	C6—N1—C11—C12	−174.26 (13)
C2—C3—C4—C5	−75.39 (16)	S1—N1—C11—C12	42.82 (18)
C2—C3—C4—C7	31.80 (17)	O3—C11—C12—C13	−132.38 (18)
C7—C4—C5—C6	−44.34 (16)	N1—C11—C12—C13	42.8 (2)
C3—C4—C5—C6	63.20 (16)	O3—C11—C12—C14	37.4 (2)
C11—N1—C6—C5	76.68 (18)	N1—C11—C12—C14	−147.36 (14)
S1—N1—C6—C5	−137.14 (12)	C17—N2—C14—C12	−160.88 (14)
C11—N1—C6—C1	−166.99 (13)	N3—N2—C14—C12	69.30 (17)
S1—N1—C6—C1	−20.81 (15)	C17—N2—C14—C15	71.11 (18)
C4—C5—C6—N1	129.61 (14)	N3—N2—C14—C15	−58.71 (17)
C4—C5—C6—C1	11.01 (16)	C13—C12—C14—N2	−132.46 (16)
C10—C1—C6—N1	29.94 (17)	C11—C12—C14—N2	58.30 (17)
C2—C1—C6—N1	155.16 (13)	C13—C12—C14—C15	−6.1 (2)
C7—C1—C6—N1	−98.31 (14)	C11—C12—C14—C15	−175.29 (13)
C10—C1—C6—C5	153.77 (13)	C17—N4—C16—O4	−173.92 (17)
C2—C1—C6—C5	−81.00 (15)	C18—N4—C16—O4	3.7 (3)
C7—C1—C6—C5	25.52 (15)	C17—N4—C16—N3	5.91 (18)
C5—C4—C7—C9	−61.98 (17)	C18—N4—C16—N3	−176.52 (16)
C3—C4—C7—C9	−173.65 (14)	N2—N3—C16—O4	167.85 (16)
C5—C4—C7—C8	174.80 (14)	N2—N3—C16—N4	−11.98 (17)
C3—C4—C7—C8	63.13 (17)	C16—N4—C17—O5	−177.12 (16)
C5—C4—C7—C1	57.69 (14)	C18—N4—C17—O5	5.3 (3)
C3—C4—C7—C1	−53.98 (14)	C16—N4—C17—N2	2.76 (18)
C10—C1—C7—C9	−52.3 (2)	C18—N4—C17—N2	−174.86 (15)
C2—C1—C7—C9	176.92 (14)	N3—N2—C17—O5	169.86 (16)
C6—C1—C7—C9	68.82 (17)	C14—N2—C17—O5	35.7 (2)
C10—C1—C7—C8	71.22 (19)	N3—N2—C17—N4	−10.02 (16)
C2—C1—C7—C8	−59.53 (17)	C14—N2—C17—N4	−144.17 (14)
C6—C1—C7—C8	−167.63 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.95 (2)	1.91 (2)	2.8263 (18)	161.2 (17)

 

Footnotes

†Part of this work was presented as a poster at the 13th Inter­national Conference on Organic Synthesis (ICOS-13), Warsaw, Poland, July 1–5, 2000; Y. Elemes: Highly Diastereoselective Ene Reactions with the Aid of a Chiral Auxiliary, p. 265.