(2S,3R,4S,5R)-Diethyl 2-(10,10-di­methyl-3,3-dioxo-3[lambda]⁶-thia-4-aza­tri­cyclo­[5.2.1.0^1,5]decan-4-ylcarbon­yl)-5-phenyl­pyrrolidine-3,4-dicarboxyl­ate: a novel isomorphous-by-addition compound

The title compound, C₂₇H₃₆N₂O₇S, (I), is isomorphous by addition with the dimethyl ester analogue [Garner, Dogan, Youngs, Kennedy, Protasiewicz & Zaniewski (2001). Tetra­hedron, 57, 71-85], (II), by replacing two methyl ester H atoms with two methyl groups. With the exception of the conformation of one of the ester groups, the mol­ecules are almost superimposable. Likewise, apart from a slightly larger c axis in (I), few differences in the cell packing of (I) and (II) are found, with both dominated by the same C-H...O hydrogen bonds. Full synthetic and spectroscopic details of (I) are given. The mol­ecular synthesis is important as an example of chiral auxiliary-assisted 1,3-dipolar cyclo­addition of an azomethine ylid.

S1. Comment

Pyrrolidine substructures are found in many biologically active compounds, leading to a point where there is a clear need for an arsenal of `decorated' scaffolds that will enable modern combinatorial access to refined libraries of compounds for (bio)assay and drug development (Schreiber, 2000). The title compound, (I), was prepared as part of a broader research programme designed to explore preparative routes to chiral pyrrolidine scaffolds and to address specifically the potential of chiral auxiliary-assisted 1,3-dipolar cycloaddition of azomethine ylids to various dipolarophiles (see first reaction scheme).

Our work sought to capitalize upon the findings of Garner & co-workers (Garner & Kaniskan, 2005; Garner et al., 2001, 2006) and others (Padwa et al., 1985), who demonstrated that a diastereofacial bias was indeed possible utilizing a chiral auxiliary on an ylid dipole. The synthetic route to (I) employed the glycyl sultam chiral auxiliary, (2), which was prepared from enantiomerically pure (+)-camphor 10-sulfonic acid (Davis et al., 1988; Oppolzer et al., 1989; Hoppe & Beckmann, 1979). The 1,3-dipolar cycloaddition was carried out with diethyl maleate and benzaldehyde in the presence of silver acetate (see second reaction scheme) to yield the title compound, (I). This structural study was undertaken to confirm the relative conformation of the 3,4-ester groups, given that the absolute configuration was established by the stereochemistry of the starting (+)-camphor enantiomer. In this case the absolute configuration was successfully confirmed by the observed X-ray anomalous dispersion effects [4033 Bijvoet pairs, Flack x parameter 0.00 (7) (Flack, 1983); Hooft y parameter 0.00 (4) (Hooft et al., 2008)].

The asymmetric unit of (I) is shown in Fig. 1, with selected dimensions compared with the dimethyl ester analogue, (II) [Garner et al., 2001; Cambridge Structural Database (Version 5.29 with November 2007 updates; Allen, 2002) refcode MIPPOQ], in Table 2. The cell dimensions, molecular packing and alignment of (I) are closely related to those of the dimethyl analogue (Figs. 2 and 3). As the opposite enantiomer is reported for (II), all comparisons here involve using the inverted molecule [conversion (x, 1 - y, z)] for (II); atom labelling here does not match the arbitrary labelling found in the archived CIF of (II) (there were no labels given in the original paper). The two structures are isomorphous through replacement of one H atom of each of the ester dimethyl groups with a methyl group (Fig. 2). To the best of our knowledge, this is a novel case; more usual isomorphous organic crystals involve larger group `interchanges', such as Cl for CH₃ in 2,2'-derivatives of 5'5'-dipropoxybenzidines (El-Shafei et al., 2004) or, more commonly, of related transition metals such as Co^II/Ni^II (e.g. Li et al., 2007). It is possible that our literature survey has not picked up previous cases of this phenomenon, though we note there have been many studies of polymorphs of the same compound (e.g. Kálmán et al., 2004).

The definition of isomorphicity is well tested by these two structures. It is obvious that (I) and (II) have different conformations with respect to rotation about the C4—C9 bond, as shown by the dihedral angles (Table 2) and in Fig. 2. Minor `displacement' differences involving the phenyl ring (C12–C17) and the location of the N1 H atom are noted, although in the latter case the position in (II) was a calculated one rather than its refined position in (I). Indeed, the position of the N1 H atom (H1) in (I) seems to fulfil the distance criteria, but not the expected N—H···O interaction angle criteria based on normal intermolecular interactions [at 110 (2)°; see Desiraju & Steiner, 1999]. Atom H1 is also under the influence of atom O4, with an intramolecular H1···O4 distance of 2.60 (4) Å. The five- and six-membered rings in (I) and (II), as expected from the close overlap (Fig. 2), are almost identical, e.g. the N1/C2–C5 ring in (I) is in an envelope conformation, with Cremer & Pople (1975) parameters Q₂ = 0.391 (2) Å and ϕ₂ = 150.3 (3)°, whilst the inverted molecule of (II) has a slight twist on C5—N1, with Q₂ = 0.397 (4) Å and ϕ₂ = 160.8 (6)°. The S1/N2/C18/C19/C24 rings are similar, each being in a twisted C18—C19 bond conformation.

Examination of Fig. 3 shows how the a and b cell axes of (I) and (II) are similar, with a relatively minor alteration in the direction and size of the c axis, consistent with the molecular orientation and addition of the extra methyl group. The molecules are in the same relative orientation in the unit cells and details of the three-dimensional cell packing illustrate only minor differences between the two cells. The interactions are mainly of the C—H···O type (the donor O atom being either a carboxyl O atom or an O atom bound to S), with one C—H.. π interaction (Table 1). We note the differences first. The orientation of the O5—C10 bond in (II) allows a C10—H···O2 interaction which is missing in (I). Likewise, the orientation and presence of methyl C8 only in (I) sets up an interaction with O2 (entry 2, Table 1). The phenyl C16—H16···O5 interaction in (I) (entry 3, Table 1) is found in (II), but changed, with the donor atom being O4 (since the ester conformation is rotated; see Fig. 2). One final difference involves a close intramolecular interaction in (I) (entry 9, Table 2) which is missing from (II). The remaining five inter- and intramolecular interactions (Table 1, where Cg1 represents the centroid of phenyl ring C12–C17) are duplicated in both structures, under the same symmetry designations, with an average difference in H···donor distance of 0.10 (7) Å. Similar methylene C—H···O═S distances have been observed before (e.g. H···O = 2.330 Å; James et al., 2005).

In summary, the relationship between the title compound, (I), and the antipode of the previously reported compound, (II), can be described as being a novel case of `isomorphous by addition', given the subtle though distinct differences in the molecules and packing.

S2. Experimental

Benzaldehyde (69.0 µl, 0.68 mmol) was dissolved in tetrahydrofuran (1 ml) and added to a solution of the glycyl sultam (2) (Davis et al., 1988; Oppolzer et al., 1989; Hoppe & Beckmann, 1979) (185 mg, 0.68 mmol) in tetrahydrofuran (1 ml) (see second reaction scheme). Diethyl maleate (329 µl, 2.04 mmol) was added to the reaction solution, followed by silver acetate (5.70 mg, 34.0 µmol). After being stirred under argon in the dark for 3 h, the reaction mixture was diluted with dichloromethane (100 ml) and washed with saturated ammonium chloride solution (50 ml). The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography (silica gel, ethyl acetate–petroleum spirit 3:7, then 4:6 and 1:1) to give the product, (I) (182 mg, 50%), as a pale-yellow solid. Analysis: R_f = 0.18 (ethyl acetate–petroleum spirit 3:7); [α]²² = -39.9 (c = 1.5, CHCl₃); HRMS (ES+): calculated for C₂₇H₃₆N₂O₇²³NaS (MNa+): 555.2141; found: 555.2127; microanalysis requires: C 60.88, H 6.81, N 5.26%; found: C 60.57, H 6.99, N 5.17%. For details of ¹H and ¹³C NMR data, see the archived CIF. The crystallization solvent was ethanol.

S3. Refinement

A total of 11 reflections within 2θ = 50° were omitted either as outliers or because they were partially screened by the backstop. The H atom on N1 was located and refined with an isotropic displacement parameter. Water H atoms were located and refined with U_iso(H) = 1.2U_eq(O). All C-bound H atoms were constrained to their expected geometries, with C—H = 0.98, 0.99 or 1.00 Å. Methyl H atoms were refined with U_iso(H) = 1.5U_eq(C); all other H atoms were refined with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006) and SADABS (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Figures

	Fig. 1. The molecular structure of the asymmetric unit of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Overlapped view of (I) (thick bonds, shaded) and the inverted enantiomer of (II) (thin bonds). Selected labels are given. Note the conformational difference along the C4—C9—O5—C10—C11 ester chain.
	Fig. 3. Cell packing diagram of (I) and the inverted cell of (II), using the same bond styles as in Fig. 2. The axes of (I) and (II) are unprimed and primed, respectively. The view with overlap of the ac diagonal and the b axis illustrates that the cell expansion is mainly along the c axis in (I).

(2S,3R,4S,5R)-Diethyl 2-(10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-azatricyclo[5.2.1.0^1,5]decan-4- ylcarbonyl)-5-phenylpyrrolidine-3,4-dicarboxylate

Crystal data

C27H36N2O7S	F(000) = 568
Mr = 532.64	Dx = 1.298 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9945 reflections
a = 13.7194 (9) Å	θ = 2.4–31.1°
b = 6.9464 (4) Å	µ = 0.17 mm^−1
c = 14.9703 (9) Å	T = 122 K
β = 107.148 (2)°	Plate, colourless
V = 1363.25 (14) Å^3	0.45 × 0.24 × 0.06 mm
Z = 2

Data collection

Bruker Nonius APEX2 CCD area-detector diffractometer	9045 independent reflections
Radiation source: fine-focus sealed tube	6778 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 8.192 pixels mm^-1	θmax = 32.6°, θmin = 2.8°
ϕ and ω scans	h = −20→20
Absorption correction: multi-scan (Blessing, 1995)	k = −10→9
Tmin = 0.665, Tmax = 1.0	l = −22→22
28357 measured 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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.152	w = 1/[σ^2(Fo^2) + (0.0797P)^2 + 0.153P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
8865 reflections	Δρmax = 0.44 e Å^−3
342 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

Special details

Experimental. (I) ¹H NMR (500 MHz, CDCl₃, δ, p.p.m.): 7.36–7.21 (series of m 5H, Ph), 4.54 (dd, 10.9, 9.3 Hz, 1H, H-2), 4.43 (dd, 12.8, 7.2 Hz, 1H, H-5), 4.06–3.95 (m, 4H), 3.74 (dd, 9.0, 7.2 Hz, 1H, H-4), 3.69–3.56 (m, 3H), 3.48 (s, 2H, CH₂SO₂), 2.51–2.44 (m, 1H), 2.10 (dd, 13.8, 8.0 Hz, 1H), 1.96–1.82 (m, 3H), 1.48–1.35 (m, 2H), 1.16 (t, 7.2 Hz, 3H, CH₃), 1.14 (s, 3H, CH₃), 0.96 (s, 3H, CH₃), 0.77 (t, 7.1 Hz, 3H, CH₃); ¹³C NMR (125 MHz, CDCl₃, δ, p.p.m.): 170.47, 169.77, 167.63, 136.87, 128.03 (2 C), 127.35, 126.79 (2 C), 65.65, 64.54, 62.29, 60.79, 60.28, 54.21, 53.01, 52.10, 48.41, 47.73, 44.53, 37.20, 32.89, 26.55, 20.10, 20.08, 13.90, 13.49; FT–IR (KBr, ν, cm^-1): 2959, 1751, 1462, 1394, 1336, 1195, 1134, 1061, 998, 972, 841, 809, 762, 539.

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	0.07934 (4)	0.93952 (9)	0.61405 (4)	0.03675 (14)
O1	0.27730 (15)	0.6868 (3)	0.80728 (12)	0.0458 (4)
O2	0.32184 (14)	1.1253 (3)	0.82909 (12)	0.0428 (4)
O3	0.30407 (13)	1.2927 (2)	0.95095 (12)	0.0389 (4)
O4	0.34070 (12)	0.8740 (3)	1.02648 (12)	0.0389 (4)
O5	0.29460 (13)	1.0339 (3)	1.13736 (11)	0.0393 (4)
O6	0.06336 (18)	1.1328 (3)	0.63870 (14)	0.0574 (6)
O7	0.00084 (16)	0.8042 (4)	0.61412 (14)	0.0614 (6)
N1	0.13186 (17)	0.7295 (3)	0.89631 (13)	0.0329 (4)
H1	0.189 (3)	0.681 (5)	0.918 (2)	0.048 (9)*
N2	0.19230 (14)	0.8616 (3)	0.68200 (11)	0.0288 (4)
C1	0.21041 (18)	0.7993 (3)	0.77461 (14)	0.0310 (4)
C2	0.14185 (17)	0.8782 (3)	0.82942 (14)	0.0296 (4)
H2	0.0728	0.9013	0.7845	0.036*
C3	0.17717 (16)	1.0691 (3)	0.88665 (14)	0.0269 (4)
H3	0.1224	1.1668	0.8617	0.032*
C4	0.17594 (16)	1.0197 (3)	0.98665 (13)	0.0256 (4)
H4	0.1449	1.1269	1.0137	0.031*
C5	0.10625 (16)	0.8380 (3)	0.96977 (14)	0.0283 (4)
H5	0.0341	0.8829	0.9439	0.034*
C6	0.27688 (16)	1.1600 (3)	0.88365 (14)	0.0288 (4)
C7	0.4022 (2)	1.3896 (4)	0.96583 (19)	0.0451 (6)
H7A	0.4420	1.3255	0.9288	0.054*
H7B	0.3912	1.5255	0.9454	0.054*
C8	0.4580 (3)	1.3807 (6)	1.0653 (2)	0.0659 (9)
H8A	0.4153	1.4325	1.1018	0.099*
H8B	0.5206	1.4570	1.0775	0.099*
H8C	0.4755	1.2465	1.0834	0.099*
C9	0.27969 (16)	0.9680 (3)	1.05071 (14)	0.0284 (4)
C10	0.3908 (2)	0.9865 (5)	1.20564 (18)	0.0521 (7)
H10A	0.4061	1.0825	1.2568	0.063*
H10B	0.4462	0.9914	1.1757	0.063*
C11	0.3868 (3)	0.7894 (5)	1.2453 (2)	0.0631 (9)
H11A	0.3256	0.7782	1.2661	0.095*
H11B	0.4476	0.7688	1.2985	0.095*
H11C	0.3844	0.6925	1.1971	0.095*
C12	0.11312 (16)	0.7253 (3)	1.05784 (14)	0.0288 (4)
C13	0.07141 (18)	0.8063 (4)	1.12370 (16)	0.0353 (5)
H13	0.0372	0.9266	1.1109	0.042*
C14	0.07933 (19)	0.7134 (4)	1.20752 (16)	0.0407 (5)
H14	0.0516	0.7714	1.2521	0.049*
C15	0.1273 (2)	0.5371 (4)	1.22632 (17)	0.0442 (6)
H15	0.1319	0.4723	1.2833	0.053*
C16	0.1686 (2)	0.4557 (4)	1.16146 (17)	0.0420 (5)
H16	0.2024	0.3350	1.1745	0.050*
C17	0.16150 (18)	0.5476 (3)	1.07775 (16)	0.0339 (4)
H17	0.1898	0.4891	1.0337	0.041*
C18	0.25698 (19)	0.7786 (3)	0.62864 (15)	0.0330 (5)
H18	0.2465	0.6361	0.6227	0.040*
C19	0.22260 (19)	0.8740 (3)	0.53016 (14)	0.0331 (4)
C20	0.2568 (3)	0.7300 (4)	0.46702 (18)	0.0474 (6)
H20A	0.2332	0.5979	0.4745	0.057*
H20B	0.2313	0.7678	0.4004	0.057*
C21	0.3735 (3)	0.7452 (5)	0.5038 (2)	0.0553 (8)
H21A	0.4028	0.7788	0.4527	0.066*
H21B	0.4039	0.6225	0.5325	0.066*
C22	0.3927 (2)	0.9071 (4)	0.57729 (18)	0.0464 (6)
H22	0.4604	0.9723	0.5896	0.056*
C23	0.3707 (2)	0.8242 (4)	0.66523 (17)	0.0439 (6)
H23A	0.4114	0.7067	0.6877	0.053*
H23B	0.3849	0.9202	0.7164	0.053*
C24	0.1098 (2)	0.9219 (4)	0.50592 (15)	0.0424 (5)
H24A	0.0686	0.8195	0.4662	0.051*
H24B	0.0953	1.0453	0.4715	0.051*
C25	0.2996 (2)	1.0404 (4)	0.53731 (17)	0.0402 (5)
C26	0.2916 (3)	1.2079 (4)	0.6028 (2)	0.0493 (6)
H26A	0.3466	1.3005	0.6065	0.074*
H26B	0.2977	1.1573	0.6653	0.074*
H26C	0.2255	1.2721	0.5780	0.074*
C27	0.2942 (3)	1.1318 (5)	0.4423 (2)	0.0570 (8)
H27A	0.3054	1.0324	0.4000	0.085*
H27B	0.3469	1.2312	0.4512	0.085*
H27C	0.2268	1.1900	0.4154	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0335 (3)	0.0493 (3)	0.0219 (2)	0.0030 (2)	−0.00038 (19)	−0.0008 (2)
O1	0.0576 (11)	0.0513 (11)	0.0298 (8)	0.0208 (9)	0.0148 (8)	0.0116 (7)
O2	0.0387 (9)	0.0587 (11)	0.0321 (9)	−0.0084 (8)	0.0123 (7)	−0.0094 (8)
O3	0.0399 (9)	0.0390 (8)	0.0397 (9)	−0.0113 (7)	0.0147 (7)	−0.0092 (7)
O4	0.0324 (8)	0.0502 (9)	0.0324 (8)	0.0079 (7)	0.0073 (7)	0.0024 (7)
O5	0.0381 (9)	0.0517 (10)	0.0233 (7)	−0.0024 (8)	0.0015 (6)	−0.0035 (7)
O6	0.0689 (14)	0.0600 (12)	0.0390 (10)	0.0336 (11)	0.0093 (9)	0.0066 (9)
O7	0.0476 (12)	0.0956 (17)	0.0357 (10)	−0.0251 (12)	0.0041 (9)	−0.0101 (11)
N1	0.0423 (11)	0.0323 (9)	0.0238 (9)	−0.0077 (8)	0.0090 (8)	−0.0048 (7)
N2	0.0339 (9)	0.0312 (8)	0.0186 (7)	0.0026 (7)	0.0036 (7)	−0.0012 (6)
C1	0.0402 (12)	0.0295 (9)	0.0214 (9)	0.0019 (8)	0.0061 (8)	−0.0002 (7)
C2	0.0311 (10)	0.0350 (10)	0.0206 (9)	−0.0024 (8)	0.0043 (7)	−0.0009 (7)
C3	0.0267 (9)	0.0293 (9)	0.0217 (9)	0.0035 (7)	0.0024 (7)	0.0012 (7)
C4	0.0279 (10)	0.0271 (9)	0.0215 (9)	0.0001 (7)	0.0066 (7)	−0.0014 (7)
C5	0.0267 (9)	0.0332 (10)	0.0229 (9)	−0.0039 (8)	0.0040 (8)	−0.0015 (7)
C6	0.0289 (10)	0.0301 (9)	0.0236 (9)	0.0027 (8)	0.0017 (8)	0.0030 (7)
C7	0.0450 (14)	0.0446 (13)	0.0429 (13)	−0.0180 (11)	0.0087 (11)	0.0017 (10)
C8	0.0480 (16)	0.094 (3)	0.0508 (17)	−0.0240 (17)	0.0065 (13)	−0.0020 (17)
C9	0.0291 (9)	0.0300 (10)	0.0243 (9)	−0.0045 (8)	0.0053 (7)	0.0021 (7)
C10	0.0424 (14)	0.078 (2)	0.0260 (11)	−0.0135 (13)	−0.0060 (10)	−0.0020 (12)
C11	0.0610 (19)	0.083 (2)	0.0365 (14)	0.0044 (17)	0.0013 (13)	0.0145 (15)
C12	0.0260 (10)	0.0361 (10)	0.0236 (9)	−0.0067 (8)	0.0064 (7)	−0.0021 (8)
C13	0.0332 (11)	0.0409 (12)	0.0323 (11)	−0.0023 (9)	0.0103 (9)	−0.0055 (9)
C14	0.0373 (12)	0.0594 (15)	0.0270 (11)	−0.0105 (11)	0.0117 (9)	−0.0062 (10)
C15	0.0454 (14)	0.0553 (15)	0.0287 (11)	−0.0122 (12)	0.0060 (10)	0.0060 (10)
C16	0.0467 (13)	0.0380 (12)	0.0368 (12)	−0.0044 (11)	0.0054 (10)	0.0062 (10)
C17	0.0378 (12)	0.0334 (10)	0.0316 (11)	−0.0043 (9)	0.0121 (9)	−0.0016 (8)
C18	0.0484 (13)	0.0281 (10)	0.0224 (9)	0.0082 (9)	0.0106 (9)	0.0012 (7)
C19	0.0464 (13)	0.0314 (10)	0.0199 (9)	0.0031 (9)	0.0072 (9)	−0.0002 (8)
C20	0.077 (2)	0.0407 (12)	0.0268 (11)	0.0047 (13)	0.0191 (12)	−0.0043 (10)
C21	0.075 (2)	0.0593 (17)	0.0380 (14)	0.0201 (15)	0.0274 (14)	−0.0004 (12)
C22	0.0480 (14)	0.0584 (16)	0.0362 (12)	0.0027 (12)	0.0177 (11)	−0.0019 (11)
C23	0.0435 (14)	0.0586 (16)	0.0290 (11)	0.0149 (12)	0.0097 (10)	0.0015 (10)
C24	0.0494 (14)	0.0534 (14)	0.0190 (9)	0.0022 (12)	0.0019 (9)	0.0021 (10)
C25	0.0544 (15)	0.0362 (11)	0.0314 (11)	−0.0027 (11)	0.0147 (10)	−0.0010 (9)
C26	0.0735 (19)	0.0310 (12)	0.0479 (15)	−0.0098 (12)	0.0247 (14)	−0.0064 (10)
C27	0.086 (2)	0.0484 (15)	0.0421 (15)	−0.0019 (15)	0.0283 (15)	0.0123 (12)

Geometric parameters (Å, º)

S1—O6	1.426 (2)	C12—C17	1.391 (3)
S1—O7	1.430 (2)	C12—C13	1.396 (3)
S1—N2	1.6733 (18)	C13—C14	1.386 (3)
S1—C24	1.791 (2)	C13—H13	0.9500
O1—C1	1.195 (3)	C14—C15	1.380 (4)
O2—C6	1.184 (3)	C14—H14	0.9500
O3—C6	1.335 (3)	C15—C16	1.382 (4)
O3—C7	1.463 (3)	C15—H15	0.9500
O4—C9	1.199 (3)	C16—C17	1.384 (3)
O5—C9	1.333 (3)	C16—H16	0.9500
O5—C10	1.449 (3)	C17—H17	0.9500
N1—C5	1.459 (3)	C18—C23	1.527 (4)
N1—C2	1.473 (3)	C18—C19	1.557 (3)
N1—H1	0.82 (3)	C18—H18	1.0000
N2—C1	1.403 (3)	C19—C24	1.519 (4)
N2—C18	1.475 (3)	C19—C20	1.542 (3)
C1—C2	1.521 (3)	C19—C25	1.548 (4)
C2—C3	1.575 (3)	C20—C21	1.536 (5)
C2—H2	1.0000	C20—H20A	0.9900
C3—C6	1.519 (3)	C20—H20B	0.9900
C3—C4	1.541 (3)	C21—C22	1.541 (4)
C3—H3	1.0000	C21—H21A	0.9900
C4—C9	1.507 (3)	C21—H21B	0.9900
C4—C5	1.558 (3)	C22—C23	1.546 (4)
C4—H4	1.0000	C22—C25	1.548 (4)
C5—C12	1.512 (3)	C22—H22	1.0000
C5—H5	1.0000	C23—H23A	0.9900
C7—C8	1.462 (4)	C23—H23B	0.9900
C7—H7A	0.9900	C24—H24A	0.9900
C7—H7B	0.9900	C24—H24B	0.9900
C8—H8A	0.9800	C25—C27	1.539 (4)
C8—H8B	0.9800	C25—C26	1.546 (4)
C8—H8C	0.9800	C26—H26A	0.9800
C10—C11	1.499 (5)	C26—H26B	0.9800
C10—H10A	0.9900	C26—H26C	0.9800
C10—H10B	0.9900	C27—H27A	0.9800
C11—H11A	0.9800	C27—H27B	0.9800
C11—H11B	0.9800	C27—H27C	0.9800
C11—H11C	0.9800
O6—S1—O7	116.45 (15)	C14—C13—H13	119.6
O6—S1—N2	109.42 (11)	C12—C13—H13	119.6
O7—S1—N2	110.47 (12)	C15—C14—C13	120.2 (2)
O6—S1—C24	113.12 (14)	C15—C14—H14	119.9
O7—S1—C24	109.39 (13)	C13—C14—H14	119.9
N2—S1—C24	96.11 (10)	C14—C15—C16	119.3 (2)
C6—O3—C7	118.20 (19)	C14—C15—H15	120.3
C9—O5—C10	117.0 (2)	C16—C15—H15	120.3
C5—N1—C2	103.95 (18)	C15—C16—C17	120.9 (3)
C5—N1—H1	109 (2)	C15—C16—H16	119.6
C2—N1—H1	107 (2)	C17—C16—H16	119.6
C1—N2—C18	117.06 (17)	C16—C17—C12	120.4 (2)
C1—N2—S1	124.26 (16)	C16—C17—H17	119.8
C18—N2—S1	113.23 (13)	C12—C17—H17	119.8
O1—C1—N2	119.8 (2)	N2—C18—C23	116.02 (19)
O1—C1—C2	122.5 (2)	N2—C18—C19	106.46 (17)
N2—C1—C2	117.67 (19)	C23—C18—C19	104.09 (19)
N1—C2—C1	108.06 (18)	N2—C18—H18	110.0
N1—C2—C3	107.22 (16)	C23—C18—H18	110.0
C1—C2—C3	117.18 (18)	C19—C18—H18	110.0
N1—C2—H2	108.0	C24—C19—C20	117.9 (2)
C1—C2—H2	108.0	C24—C19—C25	118.7 (2)
C3—C2—H2	108.0	C20—C19—C25	101.7 (2)
C6—C3—C4	112.90 (16)	C24—C19—C18	108.80 (19)
C6—C3—C2	117.97 (18)	C20—C19—C18	104.01 (18)
C4—C3—C2	104.56 (16)	C25—C19—C18	104.03 (18)
C6—C3—H3	106.9	C21—C20—C19	102.1 (2)
C4—C3—H3	106.9	C21—C20—H20A	111.4
C2—C3—H3	106.9	C19—C20—H20A	111.4
C9—C4—C3	113.12 (17)	C21—C20—H20B	111.4
C9—C4—C5	109.23 (17)	C19—C20—H20B	111.4
C3—C4—C5	101.81 (15)	H20A—C20—H20B	109.2
C9—C4—H4	110.8	C20—C21—C22	104.3 (2)
C3—C4—H4	110.8	C20—C21—H21A	110.9
C5—C4—H4	110.8	C22—C21—H21A	110.9
N1—C5—C12	114.99 (18)	C20—C21—H21B	110.9
N1—C5—C4	105.55 (17)	C22—C21—H21B	110.9
C12—C5—C4	113.61 (16)	H21A—C21—H21B	108.9
N1—C5—H5	107.4	C21—C22—C23	107.6 (2)
C12—C5—H5	107.4	C21—C22—C25	102.3 (2)
C4—C5—H5	107.4	C23—C22—C25	101.9 (2)
O2—C6—O3	125.1 (2)	C21—C22—H22	114.6
O2—C6—C3	126.3 (2)	C23—C22—H22	114.6
O3—C6—C3	108.57 (18)	C25—C22—H22	114.6
C8—C7—O3	108.5 (2)	C18—C23—C22	102.0 (2)
C8—C7—H7A	110.0	C18—C23—H23A	111.4
O3—C7—H7A	110.0	C22—C23—H23A	111.4
C8—C7—H7B	110.0	C18—C23—H23B	111.4
O3—C7—H7B	110.0	C22—C23—H23B	111.4
H7A—C7—H7B	108.4	H23A—C23—H23B	109.2
C7—C8—H8A	109.5	C19—C24—S1	106.96 (14)
C7—C8—H8B	109.5	C19—C24—H24A	110.3
H8A—C8—H8B	109.5	S1—C24—H24A	110.3
C7—C8—H8C	109.5	C19—C24—H24B	110.3
H8A—C8—H8C	109.5	S1—C24—H24B	110.3
H8B—C8—H8C	109.5	H24A—C24—H24B	108.6
O4—C9—O5	124.1 (2)	C27—C25—C26	106.4 (2)
O4—C9—C4	123.37 (19)	C27—C25—C19	113.5 (2)
O5—C9—C4	112.49 (18)	C26—C25—C19	115.6 (2)
O5—C10—C11	110.8 (2)	C27—C25—C22	114.4 (2)
O5—C10—H10A	109.5	C26—C25—C22	114.2 (2)
C11—C10—H10A	109.5	C19—C25—C22	92.78 (19)
O5—C10—H10B	109.5	C25—C26—H26A	109.5
C11—C10—H10B	109.5	C25—C26—H26B	109.5
H10A—C10—H10B	108.1	H26A—C26—H26B	109.5
C10—C11—H11A	109.5	C25—C26—H26C	109.5
C10—C11—H11B	109.5	H26A—C26—H26C	109.5
H11A—C11—H11B	109.5	H26B—C26—H26C	109.5
C10—C11—H11C	109.5	C25—C27—H27A	109.5
H11A—C11—H11C	109.5	C25—C27—H27B	109.5
H11B—C11—H11C	109.5	H27A—C27—H27B	109.5
C17—C12—C13	118.4 (2)	C25—C27—H27C	109.5
C17—C12—C5	123.32 (19)	H27A—C27—H27C	109.5
C13—C12—C5	118.3 (2)	H27B—C27—H27C	109.5
C14—C13—C12	120.8 (2)
O6—S1—N2—C1	78.4 (2)	C5—C12—C13—C14	−177.2 (2)
O7—S1—N2—C1	−51.1 (2)	C12—C13—C14—C15	−1.1 (4)
C24—S1—N2—C1	−164.42 (19)	C13—C14—C15—C16	1.0 (4)
O6—S1—N2—C18	−128.53 (17)	C14—C15—C16—C17	−0.7 (4)
O7—S1—N2—C18	101.99 (18)	C15—C16—C17—C12	0.6 (4)
C24—S1—N2—C18	−11.37 (18)	C13—C12—C17—C16	−0.7 (3)
C18—N2—C1—O1	1.5 (3)	C5—C12—C17—C16	177.4 (2)
S1—N2—C1—O1	153.6 (2)	C1—N2—C18—C23	−63.7 (3)
C18—N2—C1—C2	−177.87 (19)	S1—N2—C18—C23	141.17 (18)
S1—N2—C1—C2	−25.7 (3)	C1—N2—C18—C19	−178.96 (18)
C5—N1—C2—C1	155.96 (18)	S1—N2—C18—C19	25.9 (2)
C5—N1—C2—C3	28.8 (2)	N2—C18—C19—C24	−30.7 (3)
O1—C1—C2—N1	−30.7 (3)	C23—C18—C19—C24	−153.7 (2)
N2—C1—C2—N1	148.7 (2)	N2—C18—C19—C20	−157.2 (2)
O1—C1—C2—C3	90.5 (3)	C23—C18—C19—C20	79.7 (2)
N2—C1—C2—C3	−90.2 (2)	N2—C18—C19—C25	96.7 (2)
N1—C2—C3—C6	121.3 (2)	C23—C18—C19—C25	−26.4 (2)
C1—C2—C3—C6	−0.3 (3)	C24—C19—C20—C21	171.3 (2)
N1—C2—C3—C4	−5.1 (2)	C25—C19—C20—C21	39.7 (2)
C1—C2—C3—C4	−126.71 (19)	C18—C19—C20—C21	−68.2 (2)
C6—C3—C4—C9	−31.2 (2)	C19—C20—C21—C22	−4.6 (3)
C2—C3—C4—C9	98.27 (19)	C20—C21—C22—C23	75.0 (3)
C6—C3—C4—C5	−148.27 (17)	C20—C21—C22—C25	−31.9 (3)
C2—C3—C4—C5	−18.8 (2)	N2—C18—C23—C22	−126.6 (2)
C2—N1—C5—C12	−167.74 (18)	C19—C18—C23—C22	−10.0 (2)
C2—N1—C5—C4	−41.7 (2)	C21—C22—C23—C18	−63.8 (3)
C9—C4—C5—N1	−82.2 (2)	C25—C22—C23—C18	43.3 (3)
C3—C4—C5—N1	37.7 (2)	C20—C19—C24—S1	140.92 (19)
C9—C4—C5—C12	44.7 (2)	C25—C19—C24—S1	−95.7 (2)
C3—C4—C5—C12	164.57 (17)	C18—C19—C24—S1	22.9 (2)
C7—O3—C6—O2	−6.9 (3)	O6—S1—C24—C19	106.7 (2)
C7—O3—C6—C3	175.54 (19)	O7—S1—C24—C19	−121.7 (2)
C4—C3—C6—O2	138.0 (2)	N2—S1—C24—C19	−7.44 (19)
C2—C3—C6—O2	15.8 (3)	C24—C19—C25—C27	−70.4 (3)
C4—C3—C6—O3	−44.5 (2)	C20—C19—C25—C27	60.8 (3)
C2—C3—C6—O3	−166.73 (17)	C18—C19—C25—C27	168.6 (2)
C6—O3—C7—C8	−129.9 (3)	C24—C19—C25—C26	52.9 (3)
C10—O5—C9—O4	−0.4 (3)	C20—C19—C25—C26	−176.0 (2)
C10—O5—C9—C4	177.9 (2)	C18—C19—C25—C26	−68.1 (3)
C3—C4—C9—O4	−38.9 (3)	C24—C19—C25—C22	171.42 (19)
C5—C4—C9—O4	73.7 (3)	C20—C19—C25—C22	−57.4 (2)
C3—C4—C9—O5	142.72 (18)	C18—C19—C25—C22	50.4 (2)
C5—C4—C9—O5	−104.7 (2)	C21—C22—C25—C27	−63.4 (3)
C9—O5—C10—C11	−82.9 (3)	C23—C22—C25—C27	−174.6 (2)
N1—C5—C12—C17	14.1 (3)	C21—C22—C25—C26	173.7 (2)
C4—C5—C12—C17	−107.7 (2)	C23—C22—C25—C26	62.5 (3)
N1—C5—C12—C13	−167.9 (2)	C21—C22—C25—C19	54.0 (2)
C4—C5—C12—C13	70.4 (2)	C23—C22—C25—C19	−57.2 (2)
C17—C12—C13—C14	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1^i	0.99	2.46	3.230 (3)	134
C8—H8B···O2^ii	0.98	2.49	3.420 (4)	158
C16—H16···O5^iii	0.95	2.59	3.474 (3)	155
C24—H24A···O6^iv	0.99	2.40	3.366 (3)	166
C24—H24B···O7^v	0.99	2.37	3.313 (4)	159
C5—H5···Cg1^vi	1.0	2.74	3.679 (2)	157
N1—H1···O1	0.83 (4)	2.32 (4)	2.723 (3)	110 (2)
C7—H7A···O2	0.99	2.33	2.729 (3)	103
C23—H23B···O2	0.99	2.55	3.437 (3)	149
C26—H26B···O2	0.98	2.39	3.339 (3)	164

Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+2; (iii) x, y−1, z; (iv) −x, y−1/2, −z+1; (v) −x, y+1/2, −z+1; (vi) −x, y+1/2, −z+2.