Two enanti­omerically pure cyclic arenesulfonamide hydro­chloride salts

The crystal structures of N-[(1R)-1-(1-naphth­yl)eth­yl]-3,4-dihydro-2H-1,2-benzothia­zin-4-aminium 1,1-dioxide chloride, C₂₀H₂₁N₂O₂S⁺·Cl⁻, (I), a six-membered cyclic sulfonamide, and (1R)-N-[(5,5-dioxo-6,7-dihydro­dibenzo[d,f][1,2]thia­zepin-7-yl)meth­yl]-1-(1-naphth­yl)ethanaminium chloride, C₂₆H₂₅N₂O₂S⁺·Cl⁻, (II), a seven-membered cyclic sulfonamide, both representative of a novel family of agonists of the extracellular calcium sensing receptor (CaSR) of possible clinical importance, are reported. The known chirality of the naphthyl­ethyl­amine precursor has enabled assignment of the absolute configuration of both compounds, which is crucial for the receptor recognition. The crystal structures, though different, reveal for these agonists a notable absence of intra­molecular π–π stacking between their respective aromatic groups. This suggests a common structural feature that allows CaSR agonists to be distinguished from antagonists, since in the latter, such inter­actions have been shown to be important. The connectivities between mol­ecules in the crystal structures are also different, but both involve hydrogen bonding mediated by chloride ions as a common dominant feature.

S1. Comment

The extracellular calcium sensing receptor (CaSR) (Hofer & Brown, 2003), identified a little over a decade ago (Brown et al., 1993), belongs to family 3 of the G-protein coupled receptors (GPCR). CaSR responds to extracellular calcium levels, thereby maintaining calcium homeostasis in the organism (Brown & MacLeod, 2001). Failure to maintain constant extracellular ionized calcium levels is associated with several disorders, such as hyperparathyroidism and osteoporosis (Brown et al., 1998). Recently, several small synthetic ligands of CaSR have been developed, which act selectively at this receptor as agonists or calcimimetics. These include cinacalcet (Harrington & Fotsch, 2007), presently used clinically, and calindol, developed in our own laboratory (Kessler et al., 2004).

In our continuing search for novel chemical families of CaSR ligands, two cyclic sulfonamide (sultam) compounds, (I) and (II), were recently synthesized using the aziridine-based chemistry developed by our group (Dauban & Dodd, 2000). While the (R)-naphthylethylamine moieties of both these compounds are common to that of calindol and cinacalcet, the sultam rings represent a major structural difference with known CaSR ligands. Compound (I) contains a six-membered sulfonamide ring fused to a benzene ring, and compound (II) contains a seven-membered sulfonamide ring joining the phenyl rings of a biphenyl motif. Furthermore, the attachment of the (R)-naphthylethylamine moiety to the stereogenic benzylic position of the sultam platforms differs in the two compounds by the presence of an additional methylene group in (II).

Compounds (I) and (II) were each obtained as diastereomeric mixtures which could be separated by chromatography. In both cases, only one diastereomer of each compound was observed to be significantly active as a calcimimetic. However, attribution of the absolute configuration at the ring stereogenic center was not possible by the usual NMR techniques. Because suitable crystals of the less active isomers of (I) and (II) could be prepared as hydrochloride salts, X-ray crystallography of these sultams was used to determine their absolute configurations. In both cases, the (R)-naphthylethylamine used for the synthesis of (I) and (II) allowed determination of the absolute configurations assigned here, and which were confirmed by the joint anomalous dispersion effect of the Cl and S atoms present in both crystal structures. Though IUPAC nomenclature conventions attribute (S) and (R) configurations for C4 in (I) and C3 in (II), respectively, both compounds display the same spatial arrangement at the sultam stereogenic centres (Figs. 1 and 2), indicating a strong stereochemical bias by CaSR.

These two compounds crystallized in different Sohncke space groups, viz. P1 for (I) and P2₁ for (II), in each case having two crystallographically independent molecules, A and B, in the asymmetric unit (Figs. 1 and 2). The two molecules in the asymmetric unit differ primarily in the orientation of the naphthylethylamine fragment with respect to the sulfonamide ring. These differences are more pronounced in (I) than in (II), despite the presence of a linker shorter by one methylene unit. For (I), the overlay of the sulfonamide ring atoms highlights the deviation around the C4—N11 bond, with a change in the C14—C12—N11—C4 torsion angle from -26.9 (4) to 56.3 (4)° (Fig. 3). For (II), the molecules almost superimpose and the N15—C16—C18—C19 torsion angles between the two ring systems are 36.1 (4) and 38.7 (4)° (Fig. 4).

The molecular dimensions in each of the two structures are essentially in agreement with expected values, in particular, those found among the few examples of six-membered and seven-membered sultams [only 32 and six, respectively, reported to date in the Cambridge Structural Database (Version 5.29, January 2008 update; Allen, 2002), despite the widespread biological importance of this family of compounds]. On the basis of the C—N bond distance range of 1.488 (4)–1.551 (4) Å around N11 (N11') for (I) [N15 (N15') for (II)], compounds (I) and (II), characterized as ammonium cations, have their positive charge localized on these N atoms rather than on the sulfonamide atom N2 (N2'). However, each Cl^- anion acts as an acceptor for several hydrogen bonds from both types of NH groups, including N2 and N2', and the N···Cl distances are in the expected ranges, 3.064 (6)–3.307 (3) Å (Table 1) (Steiner, 1998).

The asymmetric unit of (I) consists of a µ-chloro-like dimer in which the two chloride ions link the two cations via N—H···Cl hydrogen bonds around a pseudo-inversion centre, forming an R²₄(8) motif (Bernstein et al., 1995); the amine groups and the two chloride ions form a quasi-square plane lying almost parallel to the naphthalene group, themselves almost parallel to (121), with N11—Cl1(Cl1')—N11' bridging angles equal to 88.5° (94.3°) and Cl1—N11(N11')—Cl1' angles equal to 88.7° (87.8°) [please provide s.u. values]. The anion separation is 4.366 (5) Å.

The cations are composed of two bicyclic units articulated around an ethylamine linker, displaying an overall bent conformation at the amine group. The six-membered sultam unit fused to the benzene ring adopts a half-chair conformation, as assessed by the ring-puckering angles θ and ϕ (Cremer & Pople, 1975), which, for the atom sequence S1/N2/C3/C4/C4A/C5 are 130.5 (4) and 267.1 (5)° for (IA), and 128.3 (4) and 284.3 (5)° for (IB), with atoms N2 and C3 deviating from the S1/C8A/C4A/C4 mean plane by 0.401 (8) and -0.366 (11) Å in (IA), and 0.205 (10) and -0.532 (12) Å in (IB), respectively. The dihedral angles between the mean planes of the two ring systems are equal to 66.3° for (IA) and 60.9° for (IB), implying that the two ring systems are rather maintained orthogonal to each other instead of being oriented face-to-face. Weak intra- and intermolecular edge-to-face interactions and nonconventional C—H···O bonds (only C4—H4···O2'ⁱ is reported in Table 1) contribute to stabilize these conformers as head-to-tail dimers, as shown in Fig. 5. The sultam rings lie on top of each other with a centre-to-centre distance above 4 Å along b, and the naphthalene rings are pushed toward the opposite parallel sides. Contiguous dimers then connect into [111] chains by intermolecular offset π–π stacking of their naphthalene ringc sytems. The mean planes of two adjacent naphthalene ring systems are rotated by ~36° relative to each other, barely inclined at 8.38°, and the shortest centroid–centroid distance between two naphthyl moieties is observed to be 3.869 (3) Å. The combination of these different types of interactions generates a sheet lying parallel to (101) (Fig. 5). Single C—H ··· O hydrogen-bonded C(13) and C(7) (Bernstein et al., 1995) chains join, respectively, molecules (IA) and (IB) along the c and a axes (Table 1), thereby generating the three-dimensional framework.

In the crystal structure of (II), the molecules, which comprise a more voluminous sultam moiety linked to the naphthalene ring system via a three-atom arm, exhibit an unfolded conformation. The linker is nearly maximally extended along the a direction of the crystal. The most remote phenyl ring is nearly parallel to the naphthalene group whereas the second one is tilted by ca 51°. The heterocyclic seven-membered ring is in a boat-shaped conformation, with an approximate mirror plane through S1 and the mid-point of the C4A—C7A bond (Fig. 2), with Cremer–Pople puckering angles of θ(2) = 1.103 (3) Å for (IIA) [1.098 (3) Å for (IIB)], θ(3) = 0.179 (3) Å [0.182 (3) Å], ϕ(2) = 352.16 (17) Å [350.52 (19) Å] and ϕ(3) = missing value? [312.3 (11) Å].

Fig. 6 shows the contents of the unit cell, viewed down the b-axis direction. Unlike (I), no intermolecular π–π stacking interactions between rings are present in the crystal structure of (II). However, similarly to (I), the intermolecular organization is dominated by hydrogen-bonding interactions between the Cl^- anions and the N atoms (Table 2). The interactions with the amine N15 (N15') N atoms form infinite C²₂(4) (Bernstein et al., 1995) chains that zigzag around the helicoidal axes in the positions (0, y, 1/2) and (1/2, y, 0), in a trapezoidal fashion parallel to (100). The chloride ions are separated by 4.777 (5) Å and the amine N atoms by 5.082 (5) Å. The N—Cl—N angles range between 79.4 and 108.1°, whereas the Cl—N—Cl angles are between 73.2 and 99.1° [s.u. values?]. The one-dimensional character of the crystal structure is evidenced by the fact that the molecules all lie parallel to (010) and form infinite C(7) (Bernstein et al., 1995) chains via single C—H ···O(sulfonamide) hydrogen bonds extending along [010]. Chains containing the same conformers are related to one another by the 2₁ screw axes and then held by N—H···Cl interactions. Conformers (IIA) thereby occupy the regions at z ≈ 1/2, 3/2 etc., and conformers (IIB) the regions at z ≈ 0, 1 etc. The resulting columns dovetail with a b/2 spacing being adjacent columns, forming edge-to-face C—H ··· π (arene) contacts directed along a.

In conclusion, the crystal structures of the sultam derivatives (I) and (II) help to shed some light on the possible mode of interaction of these cyclic sulfonamide agonists of the calcium sensing receptor. In particular, these structures must be compared with known arene-type CaSR antagonists (or calcilytics), in which intramolecular π–π stacking has been observed and invoked as an important structural feature for their activity (Gavai et al., 2005; Kessler et al., 2006). In contrast, the crystal structures of both of the CaSR agonists described here revealed a notable absence of this feature between the various aromatic rings. The presence of extended conformations versus horseshoe-like conformations suggests a possible structural parameter that allows differentiation of these two classes of CaSR ligands.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Brown & MacLeod (2001); Brown et al. (1993, 1998); Cremer & Pople (1975); Dauban & Dodd (2000); Flack (1983); Gavai et al. (2005); Harrington & Fotsch (2007); Hofer & Brown (2003); Kessler et al. (2004, 2006); Kiefer et al. (2008); Steiner (1998).

S2. Experimental

Compound (I) was prepared from the reaction of 1,7 b-dihydroazireno[1,2-b][1,2]benzisothiazole 3,3-dioxide (180 mg, 1.0 mmol), obtained according to the literature procedure (Dauban & Dodd, 2000, Kiefer et al., 2008), with (R)-naphthylethylamine (2 equivalents, 2.0 mmol, 325 µl) dissolved in tetrahydrofuran (THF). The solution was heated to 333 K and stirred for a period of 18 h with monitoring by thin-layer chromatography until completion. The resulting solution was evaporated on a rotary evaporator. The residue was purified by flash chromatography (silica gel, AcOEt/heptane 3:7) to give a mixture of two diastereoisomers in 25% yield, which were separated by high-pressure liquid chromatography (HPLC; t_R1 = 26.8 min; t_R2 = 31.7 min; symmetry column 4.6 × 150 mm, 1 ml min^-1, H₂O + 0.1%HCO₂H/CH₃CN + 0.1%HCO₂H: 80/20). The resulting compounds were transformed into their hydrochloride salts by treatment with MeOH–HCl. White needle-like crystals of the more polar diastereoisomer (corresponding to that having a retention time of 26.8 min) were obtained by slow recrystallization in methanol. ¹H NMR (CDCl₃, 500 MHz): δ 8.19 (1H, br s), 7.94 (H, d, J = 7.3 Hz), 7.84 (1H, d, J = 7.3 Hz), 7.83 (1H, d, J = 6.5 Hz), 7.73 (1H, d, J = 7.3 Hz), 7.61–7.52 (3H, m), 7.50–7.44 (2H, m), 7.15 (1H, d, J = 6.5 Hz), 5.57 (1H, br s), 4.83 (1H, q, J = 6.6 Hz), 3.84 (1H, t, J = 2.3 Hz), 3.75 (1H, d, J = 15.2 Hz), 3.32 (1H, dd, J₁ = 15.2 Hz, J₂ = 2.3 Hz), 1.61 (3H, d, J = 6.6 Hz). ¹³C NMR (CDCl₃, 75.5 MHz): δ 139.4, 137.7, 136.1, 134.2, 132.3, 130.5, 129.6, 129.3, 128.2, 126.4, 125.8, 125.7, 124.9, 123.3, 122.3, 53.6, 53.0, 46.2, 24.0. MS (ES+) 375.1, M + Na. HRMS found: 375.1166; C₂₀H₂₀N₂NaO₂S requires: 375.1143. Compound (II) was prepared according to the same procedure but starting from 4b,5-dihydroazireno[1,2-b]dibenzo[d,f][1,2]thiazepine 7,7-dioxide (75 mg, 0.29 mmol) and (R)-naphthylethylamine (2 equivalents, 0.58 mmol, 95 µl) in THF at 343 K. The residue was purified by flash chromatography (silica gel, AcOEt/heptane 5:5 + 5% NEt₃) to give a mixture of two diastereoisomers in 86% yield, which were separated by HPLC (t_R1 = 16.5 min; t_R2 = 20.7 min; Sunfire column 2, 3 × 150 mm, 0.7 ml min^-1, H₂O + 0.1%HCO₂H /CH₃CN + 0.1%HCO₂H: 79/21). The resulting compounds were transformed into their hydrochloride salts by treatment with MeOH–HCl. White needle-like crystals of the more polar diastereoisomer (corresponding to that having a retention time of 16.5 min) were obtained by slow recrystallization in methanol. ¹H NMR (CDCl₃, 500 MHz): δ 8.21 (1H, br s), 8.02 (1H, d, J = 7.6 Hz), 7.92 (1H, d, J = 7.6 Hz), 7.86 (1H, d, J = 7.6 Hz), 7.74 (1H, d, J = 7.6 Hz), 7.57 (1H, t, J = 7.6 Hz), 7.54–7.48 (3H, m), 7.47–7.40 (3H, m), 7.39–7.32 (3H, m), 7.22 (1H, d, J = 7.6 Hz), 4.71 (1H, q, J = 6.0 Hz), 4.14 (1H, br s), 3.02 (1H, br s), 2.91 (1H, br s), 1.56 (3H, d, J = 6.0 Hz). ¹³C NMR (CDCl₃, 75.5 MHz): δ 138.2 (2C), 133.9 (2C), 133.6, 133.0, 130.8 (2C), 129.9 (2C), 129.6, 129.2 (3C), 128.6, 128.5, 126.7, 125.9, 125.7, 125.6, 123.4, 122.1, 54.3, 54.2, 49.7, 21.9. MS (ES+) 429.1, M + H. HRMS found: 429.1667; C₂₆H₂₅N₂NaO₂S [H₂₄?] requires: 429.1637.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.93 (aromatic), 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine) and N—H distances of 0.90 Å (amine), and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms. Exception was made for the sulfonamide H atoms, which were freely refined at the early stage of the refinement to highlight the sp³ character of the sulfonamide N atom, then constrained to ride. Three floating origin restraints were generated automatically by SHELXL97 (Sheldrick, 2008). Friedel opposites were kept unmerged, and the anomalous scattering contribution, albeit weak, of the chloride anions and S atoms [2356 Bijvoet pairs for (I), 3619 for (II)] was exploited to confirm use of the values of the Flack (1983) parameter. The absolute configuration of each compound was assigned by reference to the unchanging (R)-naphthylethylamine chiral centre from the commercial source.

Computing details

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii. The absolute configurations at atoms C4 (C4') and C12 (C12') are S and R, respectively, with the H atom on C4 pointing above the sulfonamide mean plane, as for the equivalent H atom of (II).
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary size. The absolute configurations at atoms C3 (C3') and C16 (C16') are R and R, respectively, with the H atom of C3 pointing above the sulfonamide mean plane, as for the equivalent H atom of (I).
	Fig. 3. An overlay of atoms of the sulfonamide moieties of the two molecules of (I) in the asymmetric unit (r.m.s. deviation of 0.048 Å), showing differences in the two conformers, resulting in an overall fitting value of 1.675 Å [(IA) is shown with solid lines and (IB) with dashed lines].
	Fig. 4. An overlay of atoms of the sulfonamide moieties of the two molecules of (II) in the asymmetric unit (r.m.s. deviation of 0.023 Å), showing differences in the two conformers resulting in an overall fitting value of 0.204 Å [(IIA) is shown with solid lines and (IIB) with dashed lines].
	Fig. 5. A view of the columnar packing of (I) in the bc plane. The shaded rectangles highlight the head-to-tail dimer. Dashed lines represent N—H···Cl bonds (in purple in the electronic version of the paper) and C—H···O (in black); arrows denote the intermolecular π–π stacking.
	Fig. 6. A view along the b axis of the crystal packing of (II). In grey are the molecules of conformer (IIA) related around the twofold screw axis marked by its symbol, in black those of the conformer (IIB). The dashed lines represent C—H ··· π (arene) interactions and the dotted lines, the hydrogen bonds between N and Cl atoms.

(I) N-[(1R)-1-(1-naphthyl)ethyl]-3,4-dihydro-2H-1,2-benzothiazin-4-aminium 1,1-dioxide chloride

Crystal data

C20H21N2O2S^+·Cl^−	Z = 2
Mr = 388.90	F(000) = 408
Triclinic, P1	Dx = 1.356 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.230 (2) Å	Cell parameters from 2751 reflections
b = 10.927 (2) Å	θ = 1.0–24.1°
c = 11.633 (3) Å	µ = 0.33 mm^−1
α = 103.90 (2)°	T = 293 K
β = 106.62 (3)°	Plate, colourless
γ = 96.94 (2)°	0.15 × 0.10 × 0.05 mm
V = 952.7 (4) Å^3

Data collection

Nonius KappaCCD diffractometer	5771 independent reflections
Radiation source: fine-focus sealed tube	4862 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
phi and ω scans	θmax = 25.3°, θmin = 1.9°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.88, Tmax = 0.98	k = −13→13
7330 measured reflections	l = −13→13

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 0.1452P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.18 e Å^−3
5771 reflections	Δρmin = −0.17 e Å^−3
472 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.018 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2356 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.05 (5)

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.

Checkcif output: 220_ALERT_2_C Large Non-Solvent C U_eq(max)/U_eq(min) ···3.41 Ratio 222_ALERT_3_C Large Non-Solvent H U_eq(max)/U_eq(min) ··· 3.43 Ratio 241_ALERT_2_C Check High U_eq as Compared to Neighbors for C19 241_ALERT_2_C Check High U_eq as Compared to Neighbors for C19' 340_ALERT_3_C Low Bond Precision on C—C Bonds (x 1000) Ang ··· 7 410_ALERT_2_C Short Intra H···H Contact H12'.. H21'.. 1.97 A ng.

This contact has been checked, but does not appear to be very significant (Alert C). In comparison with the other copy in the asymmetric unit the same contact has a value slightly above 2.0 Å.

234_ALERT_4_C Large Hirshfeld Difference C16 – C17.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C18 – C19.. 0.14 A ng. 234_ALERT_4_C Large Hirshfeld Difference C19 – C20.. 0.13 A ng. 234_ALERT_4_C Large Hirshfeld Difference C7' – C8'.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C17' – C17B.. 0.12 A ng. 234_ALERT_4_C Large Hirshfeld Difference C21' – C21B.. 0.11 A ng.

860_ALERT_3_G Note: Number of Least-Squares Restraints ······. 3 three floating origin restraints were generated automatically by the SHELXL97 program.

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

	x	y	z	Uiso*/Ueq
Cl1	0.64137 (13)	0.50685 (9)	0.35811 (9)	0.0619 (3)
O2	0.5323 (4)	−0.0135 (3)	0.2199 (3)	0.0710 (8)
S1	0.49663 (12)	0.11285 (9)	0.24750 (8)	0.0534 (2)
N2	0.6775 (4)	0.2155 (3)	0.3233 (3)	0.0498 (7)
H2	0.6643	0.3023	0.3265	0.060*
N11	0.6859 (3)	0.3874 (2)	0.5879 (2)	0.0381 (6)
H11A	0.5966	0.4040	0.6149	0.046*
H11B	0.6768	0.4190	0.5221	0.046*
C3	0.7617 (4)	0.2041 (4)	0.4497 (3)	0.0486 (8)
H3A	0.8770	0.2579	0.4840	0.058*
H3B	0.7741	0.1157	0.4425	0.058*
C4	0.6628 (4)	0.2427 (3)	0.5403 (3)	0.0387 (7)
H4	0.7120	0.2123	0.6129	0.046*
C4A	0.4708 (4)	0.1805 (3)	0.4854 (3)	0.0410 (7)
C5	0.3759 (5)	0.1747 (3)	0.5659 (3)	0.0501 (8)
H5	0.4295	0.2127	0.6515	0.060*
C6	0.2045 (5)	0.1139 (4)	0.5219 (4)	0.0604 (10)
H6	0.1432	0.1125	0.5776	0.072*
C7	0.1233 (5)	0.0550 (4)	0.3960 (4)	0.0685 (12)
H7	0.0081	0.0123	0.3670	0.082*
C8	0.2127 (5)	0.0594 (4)	0.3121 (4)	0.0573 (9)
H8	0.1578	0.0216	0.2266	0.069*
C12	0.8553 (4)	0.4646 (3)	0.6938 (3)	0.0453 (8)
H12	0.8231	0.5341	0.7482	0.054*
C14	0.9326 (4)	0.3827 (3)	0.7737 (3)	0.0458 (8)
C15	1.0795 (4)	0.3383 (4)	0.7653 (4)	0.0565 (10)
H15	1.1315	0.3597	0.7096	0.068*
C16	1.1520 (6)	0.2622 (4)	0.8378 (4)	0.0750 (13)
H16	1.2526	0.2349	0.8314	0.090*
C17	1.0778 (8)	0.2278 (4)	0.9170 (4)	0.0852 (16)
H17	1.1259	0.1749	0.9634	0.102*
C18	0.8488 (10)	0.2371 (6)	1.0154 (5)	0.114 (2)
H18	0.8940	0.1829	1.0612	0.137*
C19	0.7090 (11)	0.2828 (8)	1.0301 (5)	0.132 (3)
H19	0.6583	0.2581	1.0851	0.158*
C20	0.6370 (7)	0.3672 (7)	0.9643 (5)	0.110 (2)
H20	0.5425	0.3997	0.9777	0.132*
C21	0.7089 (5)	0.4007 (5)	0.8799 (4)	0.0736 (13)
H21	0.6617	0.4551	0.8352	0.088*
C13	0.9765 (5)	0.5283 (4)	0.6390 (4)	0.0646 (11)
H13A	0.9228	0.5879	0.6000	0.097*
H13B	1.0009	0.4637	0.5777	0.097*
H13C	1.0825	0.5735	0.7046	0.097*
O1	0.4047 (4)	0.1572 (3)	0.1467 (2)	0.0797 (9)
C8A	0.3870 (4)	0.1215 (3)	0.3584 (3)	0.0439 (8)
C17A	0.9273 (7)	0.2708 (4)	0.9312 (3)	0.0727 (13)
C21A	0.8546 (4)	0.3524 (4)	0.8608 (3)	0.0550 (10)
Cl1'	0.41359 (11)	0.52808 (10)	0.65666 (9)	0.0609 (3)
S1'	0.73816 (11)	0.88927 (9)	0.63088 (9)	0.0539 (2)
O1'	0.8551 (3)	0.8273 (3)	0.7015 (3)	0.0785 (9)
O2'	0.7986 (3)	1.0188 (2)	0.6349 (3)	0.0679 (7)
N2'	0.6702 (4)	0.8014 (3)	0.4864 (3)	0.0616 (8)
H2'	0.6922	0.7198	0.4930	0.074*
N11'	0.3243 (3)	0.6224 (2)	0.4226 (3)	0.0466 (7)
H11C	0.4099	0.5947	0.3965	0.056*
H11D	0.3306	0.6015	0.4938	0.056*
C3'	0.5037 (6)	0.8160 (4)	0.4100 (4)	0.0659 (11)
H3C	0.4816	0.7680	0.3234	0.079*
H3D	0.5082	0.9061	0.4139	0.079*
C4'	0.3565 (5)	0.7691 (3)	0.4524 (3)	0.0488 (8)
H4'	0.2518	0.7915	0.4037	0.059*
C4B	0.3857 (4)	0.8316 (3)	0.5889 (3)	0.0460 (8)
C8B	0.5505 (4)	0.8880 (3)	0.6741 (3)	0.0453 (8)
C5'	0.2455 (5)	0.8378 (4)	0.6330 (4)	0.0596 (10)
H5'	0.1342	0.8004	0.5779	0.072*
C6'	0.2684 (6)	0.8984 (4)	0.7567 (4)	0.0738 (12)
H6'	0.1732	0.9013	0.7844	0.089*
C7'	0.4329 (6)	0.9546 (5)	0.8394 (4)	0.0733 (12)
H7'	0.4483	0.9960	0.9227	0.088*
C8'	0.5744 (5)	0.9494 (4)	0.7986 (4)	0.0626 (10)
H8'	0.6853	0.9869	0.8543	0.075*
C17B	0.0223 (6)	0.7098 (4)	0.0566 (4)	0.0630 (10)
C21B	0.0173 (5)	0.6631 (4)	0.1612 (3)	0.0560 (9)
C12'	0.1529 (5)	0.5512 (4)	0.3246 (3)	0.0564 (9)
H12'	0.0595	0.5779	0.3550	0.068*
C14'	0.1400 (5)	0.5905 (4)	0.2051 (3)	0.0556 (9)
C15'	0.2552 (5)	0.5611 (4)	0.1423 (4)	0.0703 (11)
H15'	0.3311	0.5090	0.1681	0.084*
C16'	0.2623 (6)	0.6067 (5)	0.0414 (4)	0.0790 (14)
H16'	0.3431	0.5865	0.0019	0.095*
C17'	0.1489 (6)	0.6815 (5)	0.0009 (4)	0.0779 (13)
H17'	0.1560	0.7141	−0.0648	0.093*
C18'	−0.0995 (7)	0.7809 (5)	0.0122 (5)	0.0898 (15)
H18'	−0.0974	0.8096	−0.0566	0.108*
C19'	−0.2189 (8)	0.8085 (6)	0.0665 (6)	0.1062 (19)
H19'	−0.2962	0.8583	0.0371	0.127*
C20'	−0.2278 (7)	0.7631 (6)	0.1668 (5)	0.0904 (15)
H20'	−0.3132	0.7810	0.2024	0.108*
C21'	−0.1148 (5)	0.6934 (4)	0.2135 (4)	0.0681 (11)
H21'	−0.1232	0.6647	0.2810	0.082*
C13'	0.1421 (7)	0.4085 (4)	0.3101 (4)	0.0839 (14)
H13D	0.1664	0.3941	0.3910	0.126*
H13E	0.2252	0.3791	0.2724	0.126*
H13F	0.0278	0.3621	0.2578	0.126*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0850 (7)	0.0528 (6)	0.0617 (6)	0.0266 (5)	0.0303 (5)	0.0277 (5)
O2	0.108 (2)	0.0493 (16)	0.0648 (17)	0.0208 (15)	0.0466 (17)	0.0073 (13)
S1	0.0722 (6)	0.0520 (6)	0.0394 (5)	0.0153 (5)	0.0206 (4)	0.0152 (4)
N2	0.0632 (18)	0.0454 (17)	0.0506 (17)	0.0147 (14)	0.0290 (15)	0.0174 (14)
N11	0.0346 (13)	0.0446 (16)	0.0400 (15)	0.0126 (12)	0.0154 (11)	0.0148 (12)
C3	0.0471 (19)	0.050 (2)	0.053 (2)	0.0175 (16)	0.0215 (17)	0.0120 (17)
C4	0.0366 (15)	0.0394 (18)	0.0412 (18)	0.0101 (13)	0.0109 (14)	0.0149 (15)
C4A	0.0448 (18)	0.0367 (18)	0.0442 (19)	0.0113 (15)	0.0165 (16)	0.0125 (15)
C5	0.060 (2)	0.045 (2)	0.052 (2)	0.0126 (17)	0.0279 (18)	0.0125 (17)
C6	0.061 (2)	0.051 (2)	0.077 (3)	0.0100 (19)	0.037 (2)	0.014 (2)
C7	0.045 (2)	0.055 (2)	0.095 (3)	0.0009 (18)	0.021 (2)	0.007 (2)
C8	0.051 (2)	0.054 (2)	0.056 (2)	0.0126 (17)	0.0088 (18)	0.0047 (19)
C12	0.0397 (17)	0.0454 (19)	0.047 (2)	0.0075 (15)	0.0103 (15)	0.0114 (16)
C14	0.0386 (17)	0.049 (2)	0.0412 (19)	0.0056 (15)	0.0044 (15)	0.0085 (16)
C15	0.0437 (19)	0.061 (2)	0.055 (2)	0.0143 (18)	0.0076 (17)	0.0074 (19)
C16	0.072 (3)	0.063 (3)	0.067 (3)	0.025 (2)	−0.009 (2)	0.010 (3)
C17	0.112 (4)	0.055 (3)	0.053 (3)	0.012 (3)	−0.025 (3)	0.017 (2)
C18	0.153 (6)	0.106 (5)	0.041 (3)	−0.052 (4)	−0.001 (3)	0.020 (3)
C19	0.158 (7)	0.144 (6)	0.049 (3)	−0.082 (6)	0.031 (4)	0.007 (3)
C20	0.088 (4)	0.158 (6)	0.060 (3)	−0.037 (4)	0.035 (3)	0.003 (4)
C21	0.053 (2)	0.106 (4)	0.047 (2)	−0.011 (2)	0.0181 (19)	0.006 (2)
C13	0.051 (2)	0.064 (3)	0.077 (3)	−0.0001 (19)	0.016 (2)	0.029 (2)
O1	0.099 (2)	0.094 (2)	0.0492 (16)	0.0189 (18)	0.0152 (15)	0.0382 (16)
C8A	0.0486 (19)	0.0398 (18)	0.044 (2)	0.0150 (15)	0.0126 (16)	0.0129 (16)
C17A	0.095 (3)	0.061 (3)	0.032 (2)	−0.020 (3)	−0.006 (2)	0.010 (2)
C21A	0.048 (2)	0.066 (2)	0.0345 (19)	−0.0105 (17)	0.0039 (16)	0.0080 (18)
Cl1'	0.0580 (5)	0.0753 (7)	0.0694 (6)	0.0346 (5)	0.0308 (5)	0.0349 (5)
S1'	0.0475 (5)	0.0472 (5)	0.0665 (6)	0.0090 (4)	0.0156 (4)	0.0194 (5)
O1'	0.0545 (16)	0.087 (2)	0.107 (2)	0.0309 (15)	0.0229 (16)	0.0481 (19)
O2'	0.0646 (15)	0.0443 (15)	0.0832 (19)	−0.0052 (12)	0.0154 (14)	0.0157 (14)
N2'	0.072 (2)	0.0456 (18)	0.066 (2)	0.0016 (15)	0.0313 (18)	0.0094 (16)
N11'	0.0525 (16)	0.0345 (15)	0.0442 (16)	0.0073 (12)	0.0039 (13)	0.0108 (13)
C3'	0.101 (3)	0.043 (2)	0.050 (2)	0.001 (2)	0.023 (2)	0.0168 (18)
C4'	0.060 (2)	0.0350 (18)	0.0432 (19)	0.0112 (16)	0.0019 (17)	0.0134 (16)
C4B	0.0464 (18)	0.0359 (18)	0.049 (2)	0.0092 (15)	0.0058 (16)	0.0115 (15)
C8B	0.0458 (18)	0.0403 (18)	0.045 (2)	0.0101 (15)	0.0082 (16)	0.0118 (16)
C5'	0.044 (2)	0.051 (2)	0.074 (3)	0.0041 (17)	0.0115 (19)	0.012 (2)
C6'	0.069 (3)	0.074 (3)	0.081 (3)	0.014 (2)	0.035 (2)	0.013 (2)
C7'	0.078 (3)	0.082 (3)	0.049 (2)	0.020 (2)	0.018 (2)	0.003 (2)
C8'	0.054 (2)	0.064 (3)	0.058 (2)	0.0115 (19)	0.0110 (19)	0.004 (2)
C17B	0.078 (3)	0.059 (2)	0.046 (2)	0.005 (2)	0.016 (2)	0.0140 (19)
C21B	0.059 (2)	0.051 (2)	0.042 (2)	−0.0003 (17)	0.0014 (17)	0.0083 (17)
C12'	0.051 (2)	0.056 (2)	0.049 (2)	0.0030 (18)	0.0020 (17)	0.0134 (18)
C14'	0.056 (2)	0.050 (2)	0.045 (2)	0.0013 (17)	0.0047 (17)	0.0041 (17)
C15'	0.067 (2)	0.075 (3)	0.051 (2)	0.016 (2)	0.008 (2)	−0.001 (2)
C16'	0.076 (3)	0.097 (4)	0.049 (3)	0.007 (3)	0.020 (2)	−0.002 (2)
C17'	0.090 (3)	0.083 (3)	0.047 (2)	−0.002 (3)	0.016 (2)	0.012 (2)
C18'	0.113 (4)	0.094 (4)	0.068 (3)	0.034 (3)	0.017 (3)	0.041 (3)
C19'	0.109 (4)	0.131 (5)	0.097 (4)	0.062 (4)	0.026 (3)	0.058 (4)
C20'	0.082 (3)	0.114 (4)	0.089 (4)	0.038 (3)	0.027 (3)	0.046 (3)
C21'	0.058 (2)	0.082 (3)	0.067 (3)	0.015 (2)	0.019 (2)	0.030 (2)
C13'	0.103 (3)	0.050 (3)	0.070 (3)	−0.014 (2)	0.002 (3)	0.010 (2)

Geometric parameters (Å, º)

O2—S1	1.426 (3)	S1'—O1'	1.426 (3)
S1—O1	1.427 (3)	S1'—O2'	1.428 (3)
S1—N2	1.620 (3)	S1'—N2'	1.618 (3)
S1—C8A	1.765 (3)	S1'—C8B	1.755 (3)
N2—C3	1.478 (5)	N2'—C3'	1.455 (6)
N2—H2	0.9600	N2'—H2'	0.9477
N11—C4	1.513 (4)	N11'—C12'	1.511 (4)
N11—C12	1.551 (4)	N11'—C4'	1.529 (4)
N11—H11A	0.9000	N11'—H11C	0.9000
N11—H11B	0.9000	N11'—H11D	0.9000
C3—C4	1.521 (4)	C3'—C4'	1.513 (5)
C3—H3A	0.9700	C3'—H3C	0.9700
C3—H3B	0.9700	C3'—H3D	0.9700
C4—C4A	1.523 (4)	C4'—C4B	1.505 (5)
C4—H4	0.9800	C4'—H4'	0.9800
C4A—C8A	1.387 (4)	C4B—C8B	1.392 (5)
C4A—C5	1.388 (4)	C4B—C5'	1.393 (5)
C5—C6	1.375 (5)	C8B—C8'	1.388 (5)
C5—H5	0.9300	C5'—C6'	1.379 (6)
C6—C7	1.375 (6)	C5'—H5'	0.9300
C6—H6	0.9300	C6'—C7'	1.380 (6)
C7—C8	1.385 (6)	C6'—H6'	0.9300
C7—H7	0.9300	C7'—C8'	1.380 (5)
C8—C8A	1.399 (5)	C7'—H7'	0.9300
C8—H8	0.9300	C8'—H8'	0.9300
C12—C14	1.507 (5)	C17B—C18'	1.400 (7)
C12—C13	1.514 (5)	C17B—C17'	1.403 (6)
C12—H12	0.9800	C17B—C21B	1.437 (5)
C14—C15	1.376 (5)	C21B—C14'	1.415 (5)
C14—C21A	1.425 (5)	C21B—C21'	1.425 (5)
C15—C16	1.389 (6)	C12'—C13'	1.516 (6)
C15—H15	0.9300	C12'—C14'	1.531 (5)
C16—C17	1.340 (7)	C12'—H12'	0.9800
C16—H16	0.9300	C14'—C15'	1.375 (5)
C17—C17A	1.414 (7)	C15'—C16'	1.393 (7)
C17—H17	0.9300	C15'—H15'	0.9300
C18—C19	1.346 (10)	C16'—C17'	1.371 (7)
C18—C17A	1.411 (7)	C16'—H16'	0.9300
C18—H18	0.9300	C17'—H17'	0.9300
C19—C20	1.415 (10)	C18'—C19'	1.339 (7)
C19—H19	0.9300	C18'—H18'	0.9300
C20—C21	1.379 (6)	C19'—C20'	1.390 (7)
C20—H20	0.9300	C19'—H19'	0.9300
C21—C21A	1.419 (6)	C20'—C21'	1.349 (6)
C21—H21	0.9300	C20'—H20'	0.9300
C13—H13A	0.9600	C21'—H21'	0.9300
C13—H13B	0.9600	C13'—H13D	0.9600
C13—H13C	0.9600	C13'—H13E	0.9600
C17A—C21A	1.422 (6)	C13'—H13F	0.9600
O2—S1—O1	118.82 (19)	O1'—S1'—O2'	118.33 (17)
O2—S1—N2	108.80 (18)	O1'—S1'—N2'	107.53 (19)
O1—S1—N2	107.58 (18)	O2'—S1'—N2'	108.52 (18)
O2—S1—C8A	106.63 (15)	O1'—S1'—C8B	110.57 (17)
O1—S1—C8A	110.18 (17)	O2'—S1'—C8B	106.75 (17)
N2—S1—C8A	103.84 (15)	N2'—S1'—C8B	104.25 (16)
C3—N2—S1	113.3 (2)	C3'—N2'—S1'	115.6 (3)
C3—N2—H2	111.3	C3'—N2'—H2'	121.8
S1—N2—H2	111.9	S1'—N2'—H2'	102.9
C4—N11—C12	118.7 (2)	C12'—N11'—C4'	115.3 (3)
C4—N11—H11A	107.6	C12'—N11'—H11C	108.4
C12—N11—H11A	107.6	C4'—N11'—H11C	108.4
C4—N11—H11B	107.6	C12'—N11'—H11D	108.4
C12—N11—H11B	107.6	C4'—N11'—H11D	108.4
H11A—N11—H11B	107.1	H11C—N11'—H11D	107.5
N2—C3—C4	113.7 (3)	N2'—C3'—C4'	112.3 (3)
N2—C3—H3A	108.8	N2'—C3'—H3C	109.1
C4—C3—H3A	108.8	C4'—C3'—H3C	109.1
N2—C3—H3B	108.8	N2'—C3'—H3D	109.1
C4—C3—H3B	108.8	C4'—C3'—H3D	109.1
H3A—C3—H3B	107.7	H3C—C3'—H3D	107.9
N11—C4—C3	111.8 (3)	C4B—C4'—C3'	112.9 (3)
N11—C4—C4A	110.2 (2)	C4B—C4'—N11'	111.1 (3)
C3—C4—C4A	113.0 (3)	C3'—C4'—N11'	109.8 (3)
N11—C4—H4	107.2	C4B—C4'—H4'	107.6
C3—C4—H4	107.2	C3'—C4'—H4'	107.6
C4A—C4—H4	107.2	N11'—C4'—H4'	107.6
C8A—C4A—C5	117.6 (3)	C8B—C4B—C5'	117.8 (3)
C8A—C4A—C4	123.2 (3)	C8B—C4B—C4'	122.0 (3)
C5—C4A—C4	119.0 (3)	C5'—C4B—C4'	120.2 (3)
C6—C5—C4A	121.5 (3)	C8'—C8B—C4B	121.1 (3)
C6—C5—H5	119.3	C8'—C8B—S1'	116.2 (3)
C4A—C5—H5	119.3	C4B—C8B—S1'	122.6 (3)
C5—C6—C7	120.4 (3)	C6'—C5'—C4B	121.3 (3)
C5—C6—H6	119.8	C6'—C5'—H5'	119.3
C7—C6—H6	119.8	C4B—C5'—H5'	119.3
C6—C7—C8	120.1 (3)	C5'—C6'—C7'	119.9 (4)
C6—C7—H7	119.9	C5'—C6'—H6'	120.0
C8—C7—H7	119.9	C7'—C6'—H6'	120.0
C7—C8—C8A	118.8 (3)	C8'—C7'—C6'	120.0 (4)
C7—C8—H8	120.6	C8'—C7'—H7'	120.0
C8A—C8—H8	120.6	C6'—C7'—H7'	120.0
C14—C12—C13	115.1 (3)	C7'—C8'—C8B	119.8 (4)
C14—C12—N11	111.2 (3)	C7'—C8'—H8'	120.1
C13—C12—N11	109.9 (3)	C8B—C8'—H8'	120.1
C14—C12—H12	106.7	C18'—C17B—C17'	121.8 (4)
C13—C12—H12	106.7	C18'—C17B—C21B	119.5 (4)
N11—C12—H12	106.7	C17'—C17B—C21B	118.8 (4)
C15—C14—C21A	119.4 (4)	C14'—C21B—C21'	124.3 (4)
C15—C14—C12	120.9 (3)	C14'—C21B—C17B	119.2 (4)
C21A—C14—C12	119.7 (3)	C21'—C21B—C17B	116.5 (4)
C14—C15—C16	121.6 (4)	N11'—C12'—C13'	107.8 (3)
C14—C15—H15	119.2	N11'—C12'—C14'	108.3 (3)
C16—C15—H15	119.2	C13'—C12'—C14'	115.1 (3)
C17—C16—C15	120.4 (4)	N11'—C12'—H12'	108.5
C17—C16—H16	119.8	C13'—C12'—H12'	108.5
C15—C16—H16	119.8	C14'—C12'—H12'	108.5
C16—C17—C17A	121.0 (4)	C15'—C14'—C21B	119.0 (4)
C16—C17—H17	119.5	C15'—C14'—C12'	119.8 (4)
C17A—C17—H17	119.5	C21B—C14'—C12'	121.1 (3)
C19—C18—C17A	120.6 (7)	C14'—C15'—C16'	122.3 (4)
C19—C18—H18	119.7	C14'—C15'—H15'	118.8
C17A—C18—H18	119.7	C16'—C15'—H15'	118.8
C18—C19—C20	121.9 (6)	C17'—C16'—C15'	119.4 (4)
C18—C19—H19	119.0	C17'—C16'—H16'	120.3
C20—C19—H19	119.0	C15'—C16'—H16'	120.3
C21—C20—C19	119.0 (6)	C16'—C17'—C17B	121.2 (4)
C21—C20—H20	120.5	C16'—C17'—H17'	119.4
C19—C20—H20	120.5	C17B—C17'—H17'	119.4
C20—C21—C21A	120.4 (5)	C19'—C18'—C17B	121.4 (5)
C20—C21—H21	119.8	C19'—C18'—H18'	119.3
C21A—C21—H21	119.8	C17B—C18'—H18'	119.3
C12—C13—H13A	109.5	C18'—C19'—C20'	120.2 (5)
C12—C13—H13B	109.5	C18'—C19'—H19'	119.9
H13A—C13—H13B	109.5	C20'—C19'—H19'	119.9
C12—C13—H13C	109.5	C21'—C20'—C19'	121.2 (5)
H13A—C13—H13C	109.5	C21'—C20'—H20'	119.4
H13B—C13—H13C	109.5	C19'—C20'—H20'	119.4
C4A—C8A—C8	121.6 (3)	C20'—C21'—C21B	121.2 (4)
C4A—C8A—S1	122.1 (2)	C20'—C21'—H21'	119.4
C8—C8A—S1	116.2 (3)	C21B—C21'—H21'	119.4
C18—C17A—C17	121.8 (6)	C12'—C13'—H13D	109.5
C18—C17A—C21A	118.8 (6)	C12'—C13'—H13E	109.5
C17—C17A—C21A	119.4 (4)	H13D—C13'—H13E	109.5
C21—C21A—C17A	119.3 (4)	C12'—C13'—H13F	109.5
C21—C21A—C14	122.6 (4)	H13D—C13'—H13F	109.5
C17A—C21A—C14	118.1 (4)	H13E—C13'—H13F	109.5
O2—S1—N2—C3	−67.2 (3)	O1'—S1'—N2'—C3'	155.8 (3)
O1—S1—N2—C3	162.9 (2)	O2'—S1'—N2'—C3'	−75.1 (3)
C8A—S1—N2—C3	46.1 (3)	C8B—S1'—N2'—C3'	38.4 (3)
S1—N2—C3—C4	−67.8 (3)	S1'—N2'—C3'—C4'	−65.9 (4)
C12—N11—C4—C3	−79.2 (3)	N2'—C3'—C4'—C4B	54.7 (4)
C12—N11—C4—C4A	154.3 (2)	N2'—C3'—C4'—N11'	−70.0 (4)
N2—C3—C4—N11	−76.4 (4)	C12'—N11'—C4'—C4B	121.0 (3)
N2—C3—C4—C4A	48.5 (4)	C12'—N11'—C4'—C3'	−113.3 (3)
N11—C4—C4A—C8A	110.9 (3)	C3'—C4'—C4B—C8B	−21.6 (5)
C3—C4—C4A—C8A	−14.9 (4)	N11'—C4'—C4B—C8B	102.3 (4)
N11—C4—C4A—C5	−73.3 (4)	C3'—C4'—C4B—C5'	156.5 (3)
C3—C4—C4A—C5	160.8 (3)	N11'—C4'—C4B—C5'	−79.6 (4)
C8A—C4A—C5—C6	−0.7 (5)	C5'—C4B—C8B—C8'	−0.6 (5)
C4—C4A—C5—C6	−176.6 (3)	C4'—C4B—C8B—C8'	177.5 (3)
C4A—C5—C6—C7	1.1 (6)	C5'—C4B—C8B—S1'	−179.0 (3)
C5—C6—C7—C8	−1.5 (6)	C4'—C4B—C8B—S1'	−1.0 (5)
C6—C7—C8—C8A	1.6 (6)	O1'—S1'—C8B—C8'	60.1 (3)
C4—N11—C12—C14	−26.9 (4)	O2'—S1'—C8B—C8'	−69.9 (3)
C4—N11—C12—C13	101.7 (4)	N2'—S1'—C8B—C8'	175.4 (3)
C13—C12—C14—C15	−19.0 (5)	O1'—S1'—C8B—C4B	−121.4 (3)
N11—C12—C14—C15	106.8 (3)	O2'—S1'—C8B—C4B	108.7 (3)
C13—C12—C14—C21A	160.0 (3)	N2'—S1'—C8B—C4B	−6.1 (3)
N11—C12—C14—C21A	−74.2 (4)	C8B—C4B—C5'—C6'	0.4 (6)
C21A—C14—C15—C16	1.3 (5)	C4'—C4B—C5'—C6'	−177.8 (4)
C12—C14—C15—C16	−179.7 (3)	C4B—C5'—C6'—C7'	0.2 (7)
C14—C15—C16—C17	1.3 (6)	C5'—C6'—C7'—C8'	−0.5 (7)
C15—C16—C17—C17A	−1.7 (6)	C6'—C7'—C8'—C8B	0.3 (7)
C17A—C18—C19—C20	−1.1 (9)	C4B—C8B—C8'—C7'	0.2 (6)
C18—C19—C20—C21	2.0 (9)	S1'—C8B—C8'—C7'	178.8 (3)
C19—C20—C21—C21A	−0.9 (7)	C18'—C17B—C21B—C14'	179.6 (4)
C5—C4A—C8A—C8	0.7 (5)	C17'—C17B—C21B—C14'	0.2 (5)
C4—C4A—C8A—C8	176.5 (3)	C18'—C17B—C21B—C21'	0.0 (6)
C5—C4A—C8A—S1	−175.7 (3)	C17'—C17B—C21B—C21'	−179.4 (4)
C4—C4A—C8A—S1	0.1 (5)	C4'—N11'—C12'—C13'	−178.5 (3)
C7—C8—C8A—C4A	−1.1 (5)	C4'—N11'—C12'—C14'	56.3 (4)
C7—C8—C8A—S1	175.5 (3)	C21'—C21B—C14'—C15'	176.3 (4)
O2—S1—C8A—C4A	100.4 (3)	C17B—C21B—C14'—C15'	−3.3 (5)
O1—S1—C8A—C4A	−129.4 (3)	C21'—C21B—C14'—C12'	−7.2 (5)
N2—S1—C8A—C4A	−14.4 (3)	C17B—C21B—C14'—C12'	173.3 (3)
O2—S1—C8A—C8	−76.2 (3)	N11'—C12'—C14'—C15'	63.8 (4)
O1—S1—C8A—C8	54.0 (3)	C13'—C12'—C14'—C15'	−56.9 (5)
N2—S1—C8A—C8	169.0 (3)	N11'—C12'—C14'—C21B	−112.7 (4)
C19—C18—C17A—C17	177.8 (5)	C13'—C12'—C14'—C21B	126.6 (4)
C19—C18—C17A—C21A	−0.9 (7)	C21B—C14'—C15'—C16'	3.9 (6)
C16—C17—C17A—C18	−179.1 (4)	C12'—C14'—C15'—C16'	−172.7 (4)
C16—C17—C17A—C21A	−0.4 (6)	C14'—C15'—C16'—C17'	−1.3 (6)
C20—C21—C21A—C17A	−1.0 (5)	C15'—C16'—C17'—C17B	−2.0 (7)
C20—C21—C21A—C14	179.3 (4)	C18'—C17B—C17'—C16'	−176.9 (5)
C18—C17A—C21A—C21	1.9 (5)	C21B—C17B—C17'—C16'	2.5 (6)
C17—C17A—C21A—C21	−176.8 (4)	C17'—C17B—C18'—C19'	−179.4 (5)
C18—C17A—C21A—C14	−178.4 (4)	C21B—C17B—C18'—C19'	1.2 (8)
C17—C17A—C21A—C14	2.9 (5)	C17B—C18'—C19'—C20'	−2.1 (9)
C15—C14—C21A—C21	176.4 (3)	C18'—C19'—C20'—C21'	1.6 (9)
C12—C14—C21A—C21	−2.6 (5)	C19'—C20'—C21'—C21B	−0.4 (8)
C15—C14—C21A—C17A	−3.3 (5)	C14'—C21B—C21'—C20'	−179.9 (4)
C12—C14—C21A—C17A	177.6 (3)	C17B—C21B—C21'—C20'	−0.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.96	2.22	3.172 (3)	173
N11—H11B···Cl1	0.90	2.30	3.195 (3)	176
N11—H11A···Cl1′	0.90	2.22	3.049 (2)	153
N2′—H2′···Cl1	0.95	2.39	3.154 (3)	138
N11′—H11D···Cl1′	0.90	2.20	3.067 (3)	163
N11′—H11C···Cl1	0.90	2.34	3.229 (3)	170
C4—H4···O2′^i	0.98	2.36	3.114 (4)	133
C19—H19···O1^ii	0.93	2.60	3.465 (7)	155
C6′—H6′···O1′^iii	0.93	2.47	3.234 (5)	139

Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) x−1, y, z.

(II) (1R)-N-[(5,5-dioxo-6,7-dihydrodibenzo[d,f][1,2]thiazepin-7-yl)methyl]-1-(1-naphthyl)ethanaminium chloride

Crystal data

C26H25N2O2S^+·Cl^−	F(000) = 976
Mr = 464.99	Dx = 1.305 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 4252 reflections
a = 15.295 (4) Å	θ = 1.0–25.0°
b = 7.764 (3) Å	µ = 0.28 mm^−1
c = 20.264 (6) Å	T = 293 K
β = 100.48 (2)°	Prism, colourless
V = 2366.2 (13) Å^3	0.50 × 0.22 × 0.13 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	8155 independent reflections
Radiation source: fine-focus sealed tube	5732 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
phi and ω scans	θmax = 25.1°, θmin = 1.0°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −18→18
Tmin = 0.89, Tmax = 0.97	k = −8→9
14090 measured reflections	l = −24→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.2294P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
8155 reflections	Δρmax = 0.18 e Å^−3
579 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack (1983), 3619 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.11 (6)

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 except three low resolution reflections truncated by the beamstop. 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.

Checkcif output

340_ALERT_3_C Low Bond Precision on C—C Bonds (x 1000) Ang ··· 6 234_ALERT_4_C Large Hirshfeld Difference C22 – C23.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C24 – C25.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference N15' – C16'.. 0.10 A ng. 234_ALERT_4_C Large Hirshfeld Difference C8' – C9'.. 0.12 A ng. 234_ALERT_4_C Large Hirshfeld Difference C9' – C10'.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C11' – C11B.. 0.11 A ng. 234_ALERT_4_C Large Hirshfeld Difference C19' – C20'.. 0.13 A ng.

791_ALERT_4_G The Model has Chirality at C3 R 791_ALERT_4_G The Model has Chirality at C3' R 791_ALERT_4_G The Model has Chirality at C16 R 791_ALERT_4_G The Model has Chirality at C16' R

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

	x	y	z	Uiso*/Ueq
Cl1	0.48525 (7)	0.85993 (11)	0.06579 (4)	0.0578 (3)
S1	0.79490 (6)	0.34067 (11)	0.03221 (5)	0.0548 (3)
O2	0.78249 (19)	0.2739 (4)	−0.03463 (14)	0.0762 (9)
O1	0.85402 (18)	0.2539 (3)	0.08520 (15)	0.0668 (8)
N2	0.69581 (17)	0.3491 (4)	0.05154 (14)	0.0516 (8)
H2	0.6486	0.3519	0.0116	0.062*
N15	0.50914 (16)	0.4545 (3)	0.08190 (13)	0.0410 (7)
H15A	0.5150	0.4287	0.0396	0.049*
H15B	0.5013	0.5691	0.0841	0.049*
C3	0.6767 (2)	0.4670 (4)	0.10442 (15)	0.0403 (8)
H3	0.6652	0.5818	0.0846	0.048*
C4	0.7534 (2)	0.3996 (5)	0.22363 (17)	0.0531 (9)
H4	0.7049	0.3313	0.2283	0.064*
C5	0.8232 (2)	0.4194 (5)	0.27756 (18)	0.0595 (10)
H5	0.8214	0.3649	0.3182	0.071*
C6	0.8950 (3)	0.5200 (5)	0.2705 (2)	0.0584 (10)
H6	0.9415	0.5349	0.3067	0.070*
C7	0.8983 (2)	0.5980 (5)	0.21059 (19)	0.0547 (10)
H7	0.9474	0.6651	0.2064	0.066*
C8	0.8746 (2)	0.8217 (4)	0.08621 (19)	0.0529 (9)
H8	0.8807	0.8930	0.1236	0.063*
C9	0.8977 (2)	0.8839 (5)	0.0278 (2)	0.0610 (11)
H9	0.9208	0.9946	0.0269	0.073*
C10	0.8869 (3)	0.7831 (5)	−0.0290 (2)	0.0659 (11)
H10	0.9032	0.8250	−0.0680	0.079*
C11	0.8517 (3)	0.6194 (5)	−0.0278 (2)	0.0594 (10)
H11	0.8421	0.5523	−0.0665	0.071*
C14	0.5925 (2)	0.4066 (5)	0.12817 (16)	0.0477 (9)
H14A	0.5947	0.2823	0.1331	0.057*
H14B	0.5915	0.4558	0.1720	0.057*
C16	0.4275 (2)	0.3651 (4)	0.09725 (16)	0.0424 (8)
H16	0.4348	0.2410	0.0912	0.051*
C17	0.3474 (2)	0.4248 (6)	0.04628 (19)	0.0658 (11)
H17A	0.2959	0.3603	0.0522	0.099*
H17B	0.3587	0.4066	0.0017	0.099*
H17C	0.3373	0.5451	0.0528	0.099*
C18	0.4157 (2)	0.3960 (4)	0.16918 (17)	0.0428 (8)
C19	0.4369 (3)	0.5496 (5)	0.2007 (2)	0.0554 (10)
H19	0.4580	0.6390	0.1773	0.066*
C20	0.4278 (3)	0.5760 (5)	0.2678 (2)	0.0658 (12)
H20	0.4444	0.6806	0.2887	0.079*
C21	0.3948 (3)	0.4486 (6)	0.3017 (2)	0.0667 (12)
H21	0.3894	0.4671	0.3462	0.080*
C22	0.3333 (3)	0.1549 (6)	0.3068 (2)	0.0695 (12)
H22	0.3261	0.1722	0.3510	0.083*
C23	0.3101 (3)	0.0033 (6)	0.2767 (2)	0.0740 (13)
H23	0.2880	−0.0838	0.3006	0.089*
C24	0.3183 (3)	−0.0260 (5)	0.2103 (2)	0.0675 (12)
H24	0.3011	−0.1312	0.1902	0.081*
C25	0.3516 (2)	0.0991 (4)	0.1749 (2)	0.0521 (9)
H25	0.3566	0.0780	0.1306	0.063*
Cl1'	0.99298 (7)	0.90502 (13)	0.56547 (4)	0.0629 (3)
S1'	0.70754 (7)	0.89593 (15)	0.48265 (6)	0.0724 (4)
O1'	0.6477 (2)	0.7933 (4)	0.43710 (19)	0.0915 (11)
O2'	0.7273 (2)	0.8506 (5)	0.55231 (16)	0.1090 (13)
C3'	0.8155 (2)	1.0053 (4)	0.39928 (16)	0.0435 (8)
H3'	0.8252	1.1255	0.4136	0.052*
C3B	0.7343 (2)	0.9975 (4)	0.34289 (18)	0.0463 (9)
N2'	0.80313 (19)	0.9011 (4)	0.45786 (15)	0.0615 (9)
H2'	0.8393	0.9070	0.4922	0.074*
C4'	0.7342 (2)	0.9022 (5)	0.28492 (19)	0.0620 (10)
H4'	0.7839	0.8365	0.2810	0.074*
C4A	0.7553 (2)	0.4809 (4)	0.16275 (17)	0.0408 (8)
C5'	0.6621 (3)	0.9026 (6)	0.2328 (2)	0.0727 (12)
H5'	0.6636	0.8391	0.1942	0.087*
C6'	0.5879 (3)	0.9976 (6)	0.2385 (2)	0.0710 (12)
H6'	0.5393	0.9991	0.2035	0.085*
C7'	0.5857 (3)	1.0894 (5)	0.2954 (2)	0.0655 (11)
H7'	0.5350	1.1527	0.2987	0.079*
C7A	0.8291 (2)	0.5789 (4)	0.15508 (17)	0.0431 (8)
C7B	0.6578 (2)	1.0910 (4)	0.34908 (18)	0.0482 (9)
C8'	0.6091 (3)	1.3485 (5)	0.4081 (2)	0.0678 (11)
H8'	0.5971	1.4053	0.3670	0.081*
C8A	0.8423 (2)	0.6550 (4)	0.09046 (17)	0.0419 (8)
C8B	0.6471 (2)	1.1841 (5)	0.4121 (2)	0.0507 (10)
C9'	0.5891 (3)	1.4273 (6)	0.4651 (3)	0.0788 (14)
H9'	0.5629	1.5358	0.4617	0.095*
C10'	0.6075 (3)	1.3470 (7)	0.5261 (3)	0.0875 (15)
H10'	0.5923	1.3994	0.5637	0.105*
C11'	0.6486 (3)	1.1884 (7)	0.5318 (3)	0.0795 (14)
H11'	0.6643	1.1358	0.5735	0.095*
C11A	0.8309 (2)	0.5560 (4)	0.03134 (18)	0.0450 (9)
C11B	0.6663 (2)	1.1087 (5)	0.4747 (2)	0.0570 (10)
C14'	0.8986 (2)	0.9409 (5)	0.37463 (17)	0.0496 (9)
H14C	0.8977	0.8160	0.3736	0.059*
H14D	0.8968	0.9811	0.3291	0.059*
N15'	0.98325 (17)	0.9991 (4)	0.41705 (13)	0.0445 (7)
H15C	0.9816	0.9755	0.4603	0.053*
H15D	0.9880	1.1140	0.4131	0.053*
C16'	1.0644 (2)	0.9145 (5)	0.39831 (16)	0.0453 (8)
H16'	1.0611	0.7905	0.4067	0.054*
C17'	1.1470 (2)	0.9853 (6)	0.4442 (2)	0.0733 (13)
H17D	1.1988	0.9271	0.4350	0.110*
H17E	1.1419	0.9670	0.4902	0.110*
H17F	1.1521	1.1065	0.4361	0.110*
C18'	1.0678 (2)	0.9404 (4)	0.32454 (18)	0.0472 (9)
C19'	1.0428 (3)	1.0933 (5)	0.2931 (2)	0.0587 (10)
H19'	1.0253	1.1836	0.3178	0.070*
C20'	1.0427 (3)	1.1174 (6)	0.2249 (2)	0.0734 (12)
H20'	1.0244	1.2220	0.2047	0.088*
C21'	1.0692 (3)	0.9893 (7)	0.1884 (2)	0.0725 (13)
H21'	1.0666	1.0052	0.1426	0.087*
C21A	0.3686 (2)	0.2889 (5)	0.27170 (19)	0.0529 (10)
C21B	1.1011 (2)	0.8306 (6)	0.2182 (2)	0.0598 (11)
C22'	1.1327 (3)	0.6971 (8)	0.1814 (3)	0.0801 (15)
H22'	1.1324	0.7121	0.1358	0.096*
C23'	1.1637 (3)	0.5460 (7)	0.2116 (3)	0.0839 (15)
H23'	1.1854	0.4603	0.1869	0.101*
C24'	1.1628 (3)	0.5206 (6)	0.2794 (3)	0.0738 (13)
H24'	1.1835	0.4170	0.2995	0.089*
C25'	1.1322 (2)	0.6454 (5)	0.3171 (2)	0.0577 (10)
H25'	1.1322	0.6256	0.3623	0.069*
C25A	0.3784 (2)	0.2594 (4)	0.20383 (18)	0.0425 (8)
C25B	1.1003 (2)	0.8048 (5)	0.28783 (18)	0.0502 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0746 (7)	0.0584 (6)	0.0395 (5)	0.0002 (5)	0.0085 (5)	0.0039 (4)
S1	0.0539 (6)	0.0529 (6)	0.0615 (7)	−0.0053 (4)	0.0207 (5)	−0.0168 (5)
O2	0.085 (2)	0.0836 (19)	0.067 (2)	−0.0207 (15)	0.0330 (17)	−0.0386 (16)
O1	0.0636 (18)	0.0510 (15)	0.086 (2)	0.0111 (13)	0.0136 (16)	−0.0015 (14)
N2	0.0386 (16)	0.070 (2)	0.0468 (18)	−0.0110 (14)	0.0083 (13)	−0.0178 (15)
N15	0.0407 (16)	0.0490 (17)	0.0330 (16)	−0.0036 (12)	0.0057 (13)	0.0013 (12)
C3	0.043 (2)	0.0456 (19)	0.0312 (19)	−0.0042 (14)	0.0041 (16)	−0.0005 (14)
C4	0.045 (2)	0.062 (2)	0.049 (2)	−0.0104 (17)	0.0016 (18)	0.0119 (19)
C5	0.059 (3)	0.072 (3)	0.042 (2)	−0.004 (2)	−0.0040 (19)	0.011 (2)
C6	0.053 (2)	0.069 (2)	0.045 (3)	−0.0024 (19)	−0.0126 (19)	0.0016 (19)
C7	0.038 (2)	0.070 (2)	0.053 (3)	−0.0074 (17)	−0.0001 (19)	−0.008 (2)
C8	0.049 (2)	0.049 (2)	0.061 (3)	−0.0025 (17)	0.0104 (19)	−0.0040 (18)
C9	0.057 (2)	0.051 (2)	0.079 (3)	0.0002 (18)	0.025 (2)	0.015 (2)
C10	0.065 (3)	0.074 (3)	0.065 (3)	0.005 (2)	0.028 (2)	0.016 (2)
C11	0.059 (3)	0.071 (3)	0.054 (3)	0.004 (2)	0.024 (2)	−0.006 (2)
C14	0.0355 (19)	0.068 (2)	0.039 (2)	−0.0024 (16)	0.0049 (16)	0.0071 (18)
C16	0.0351 (18)	0.050 (2)	0.042 (2)	−0.0034 (15)	0.0061 (15)	0.0037 (16)
C17	0.042 (2)	0.091 (3)	0.060 (3)	−0.005 (2)	−0.0001 (19)	0.010 (2)
C18	0.0348 (18)	0.050 (2)	0.045 (2)	0.0049 (15)	0.0116 (15)	0.0042 (16)
C19	0.065 (3)	0.047 (2)	0.057 (3)	0.0034 (17)	0.018 (2)	−0.0038 (18)
C20	0.079 (3)	0.060 (3)	0.063 (3)	0.010 (2)	0.027 (2)	−0.011 (2)
C21	0.071 (3)	0.085 (3)	0.047 (3)	0.021 (2)	0.021 (2)	−0.001 (2)
C22	0.056 (3)	0.095 (3)	0.063 (3)	0.017 (2)	0.025 (2)	0.030 (3)
C23	0.056 (3)	0.083 (3)	0.086 (4)	−0.004 (2)	0.022 (3)	0.033 (3)
C24	0.056 (3)	0.065 (3)	0.081 (3)	−0.0052 (19)	0.012 (2)	0.013 (2)
C25	0.046 (2)	0.050 (2)	0.062 (3)	−0.0014 (16)	0.0140 (19)	0.0070 (18)
Cl1'	0.0778 (7)	0.0712 (8)	0.0371 (5)	0.0038 (5)	0.0033 (5)	0.0047 (5)
S1'	0.0594 (7)	0.0818 (9)	0.0820 (8)	0.0098 (6)	0.0289 (6)	0.0368 (7)
O1'	0.071 (2)	0.0602 (19)	0.148 (3)	−0.0085 (15)	0.031 (2)	0.0243 (19)
O2'	0.101 (2)	0.151 (3)	0.087 (2)	0.042 (2)	0.049 (2)	0.073 (2)
C3'	0.039 (2)	0.055 (2)	0.037 (2)	0.0024 (15)	0.0054 (16)	0.0035 (16)
C3B	0.037 (2)	0.051 (2)	0.048 (2)	0.0011 (15)	0.0001 (17)	0.0067 (17)
N2'	0.0470 (19)	0.086 (2)	0.052 (2)	0.0112 (16)	0.0126 (15)	0.0251 (18)
C4'	0.046 (2)	0.074 (3)	0.061 (3)	0.0043 (19)	−0.003 (2)	−0.012 (2)
C4A	0.0357 (19)	0.0448 (18)	0.040 (2)	−0.0005 (14)	0.0025 (16)	−0.0016 (15)
C5'	0.053 (3)	0.091 (3)	0.065 (3)	0.003 (2)	−0.012 (2)	−0.020 (2)
C6'	0.049 (3)	0.092 (3)	0.064 (3)	−0.003 (2)	−0.011 (2)	−0.005 (2)
C7'	0.043 (2)	0.080 (3)	0.069 (3)	0.0111 (19)	−0.002 (2)	0.007 (2)
C7A	0.040 (2)	0.0455 (19)	0.044 (2)	0.0001 (15)	0.0073 (17)	−0.0017 (15)
C7B	0.041 (2)	0.052 (2)	0.051 (2)	−0.0008 (16)	0.0049 (18)	0.0084 (17)
C8'	0.065 (3)	0.060 (3)	0.082 (3)	0.004 (2)	0.023 (2)	0.004 (2)
C8A	0.036 (2)	0.049 (2)	0.041 (2)	−0.0005 (15)	0.0095 (16)	0.0014 (16)
C8B	0.036 (2)	0.052 (2)	0.065 (3)	−0.0011 (16)	0.0114 (19)	0.0051 (19)
C9'	0.066 (3)	0.054 (3)	0.123 (4)	−0.001 (2)	0.034 (3)	−0.010 (3)
C10'	0.070 (3)	0.098 (4)	0.102 (4)	−0.018 (3)	0.035 (3)	−0.035 (3)
C11'	0.062 (3)	0.112 (4)	0.069 (3)	−0.008 (3)	0.023 (2)	0.000 (3)
C11A	0.044 (2)	0.046 (2)	0.047 (2)	−0.0002 (15)	0.0144 (17)	−0.0043 (16)
C11B	0.044 (2)	0.075 (3)	0.056 (3)	−0.0027 (18)	0.018 (2)	0.009 (2)
C14'	0.037 (2)	0.073 (3)	0.035 (2)	0.0017 (16)	−0.0024 (16)	−0.0048 (17)
N15'	0.0412 (17)	0.0571 (17)	0.0342 (17)	−0.0001 (13)	0.0045 (14)	0.0025 (13)
C16'	0.0357 (19)	0.059 (2)	0.040 (2)	0.0064 (16)	0.0053 (16)	−0.0048 (17)
C17'	0.039 (2)	0.112 (4)	0.065 (3)	0.005 (2)	−0.002 (2)	−0.016 (3)
C18'	0.037 (2)	0.059 (2)	0.047 (2)	−0.0070 (16)	0.0101 (17)	−0.0053 (18)
C19'	0.066 (3)	0.067 (3)	0.047 (3)	−0.0065 (19)	0.018 (2)	0.0055 (19)
C20'	0.077 (3)	0.082 (3)	0.063 (3)	−0.015 (2)	0.019 (3)	0.011 (2)
C21'	0.070 (3)	0.107 (4)	0.041 (3)	−0.032 (3)	0.012 (2)	0.002 (3)
C21A	0.044 (2)	0.067 (3)	0.052 (3)	0.0138 (18)	0.0198 (19)	0.0105 (19)
C21B	0.050 (2)	0.086 (3)	0.048 (3)	−0.024 (2)	0.0206 (19)	−0.016 (2)
C22'	0.068 (3)	0.113 (4)	0.067 (3)	−0.036 (3)	0.032 (3)	−0.036 (3)
C23'	0.071 (3)	0.098 (4)	0.089 (4)	−0.018 (3)	0.033 (3)	−0.045 (3)
C24'	0.062 (3)	0.074 (3)	0.091 (4)	−0.005 (2)	0.027 (3)	−0.022 (3)
C25'	0.049 (2)	0.063 (3)	0.064 (3)	−0.0062 (18)	0.016 (2)	−0.012 (2)
C25A	0.035 (2)	0.049 (2)	0.045 (2)	0.0111 (15)	0.0110 (17)	0.0097 (16)
C25B	0.038 (2)	0.067 (2)	0.047 (2)	−0.0185 (17)	0.0131 (17)	−0.0122 (18)

Geometric parameters (Å, º)

S1—O2	1.430 (3)	C3'—N2'	1.477 (4)
S1—O1	1.439 (3)	C3'—C3B	1.529 (5)
S1—N2	1.634 (3)	C3'—C14'	1.531 (5)
S1—C11A	1.761 (3)	C3'—H3'	0.9800
N2—C3	1.479 (4)	C3B—C4'	1.388 (5)
N2—H2	0.9820	C3B—C7B	1.402 (5)
N15—C14	1.486 (4)	N2'—H2'	0.8070
N15—C16	1.509 (4)	C4'—C5'	1.381 (5)
N15—H15A	0.9000	C4'—H4'	0.9300
N15—H15B	0.9000	C4A—C7A	1.394 (4)
C3—C14	1.527 (4)	C5'—C6'	1.375 (6)
C3—C4A	1.529 (4)	C5'—H5'	0.9300
C3—H3	0.9800	C6'—C7'	1.360 (6)
C4—C5	1.391 (5)	C6'—H6'	0.9300
C4—C4A	1.391 (5)	C7'—C7B	1.402 (5)
C4—H4	0.9300	C7'—H7'	0.9300
C5—C6	1.377 (5)	C7A—C8A	1.483 (5)
C5—H5	0.9300	C7B—C8B	1.502 (5)
C6—C7	1.366 (5)	C8'—C9'	1.390 (6)
C6—H6	0.9300	C8'—C8B	1.399 (5)
C7—C7A	1.405 (5)	C8'—H8'	0.9300
C7—H7	0.9300	C8A—C11A	1.407 (5)
C8—C9	1.382 (5)	C8B—C11B	1.380 (5)
C8—C8A	1.393 (5)	C9'—C10'	1.368 (7)
C8—H8	0.9300	C9'—H9'	0.9300
C9—C10	1.377 (6)	C10'—C11'	1.378 (7)
C9—H9	0.9300	C10'—H10'	0.9300
C10—C11	1.382 (6)	C11'—C11B	1.381 (6)
C10—H10	0.9300	C11'—H11'	0.9300
C11—C11A	1.386 (5)	C14'—N15'	1.488 (4)
C11—H11	0.9300	C14'—H14C	0.9700
C14—H14A	0.9700	C14'—H14D	0.9700
C14—H14B	0.9700	N15'—C16'	1.513 (4)
C16—C18	1.520 (4)	N15'—H15C	0.9000
C16—C17	1.524 (5)	N15'—H15D	0.9000
C16—H16	0.9800	C16'—C18'	1.519 (5)
C17—H17A	0.9600	C16'—C17'	1.528 (5)
C17—H17B	0.9600	C16'—H16'	0.9800
C17—H17C	0.9600	C17'—H17D	0.9600
C18—C19	1.364 (5)	C17'—H17E	0.9600
C18—C25A	1.445 (4)	C17'—H17F	0.9600
C19—C20	1.406 (5)	C18'—C19'	1.369 (5)
C19—H19	0.9300	C18'—C25B	1.429 (5)
C20—C21	1.354 (6)	C19'—C20'	1.394 (6)
C20—H20	0.9300	C19'—H19'	0.9300
C21—C21A	1.407 (6)	C20'—C21'	1.345 (6)
C21—H21	0.9300	C20'—H20'	0.9300
C22—C23	1.344 (6)	C21'—C21B	1.419 (6)
C22—C21A	1.422 (5)	C21'—H21'	0.9300
C22—H22	0.9300	C21A—C25A	1.429 (5)
C23—C24	1.391 (6)	C21B—C22'	1.413 (6)
C23—H23	0.9300	C21B—C25B	1.428 (5)
C24—C25	1.360 (5)	C22'—C23'	1.368 (7)
C24—H24	0.9300	C22'—H22'	0.9300
C25—C25A	1.405 (5)	C23'—C24'	1.389 (7)
C25—H25	0.9300	C23'—H23'	0.9300
S1'—O1'	1.421 (4)	C24'—C25'	1.369 (5)
S1'—O2'	1.433 (3)	C24'—H24'	0.9300
S1'—N2'	1.631 (3)	C25'—C25B	1.420 (5)
S1'—C11B	1.765 (4)	C25'—H25'	0.9300
O2—S1—O1	119.60 (18)	C5'—C4'—C3B	121.5 (4)
O2—S1—N2	105.81 (16)	C5'—C4'—H4'	119.2
O1—S1—N2	108.93 (17)	C3B—C4'—H4'	119.2
O2—S1—C11A	108.81 (18)	C4—C4A—C7A	119.7 (3)
O1—S1—C11A	107.24 (17)	C4—C4A—C3	120.9 (3)
N2—S1—C11A	105.64 (16)	C7A—C4A—C3	119.4 (3)
C3—N2—S1	120.9 (2)	C6'—C5'—C4'	119.6 (4)
C3—N2—H2	111.8	C6'—C5'—H5'	120.2
S1—N2—H2	112.3	C4'—C5'—H5'	120.2
C14—N15—C16	113.7 (2)	C7'—C6'—C5'	120.0 (4)
C14—N15—H15A	108.8	C7'—C6'—H6'	120.0
C16—N15—H15A	108.8	C5'—C6'—H6'	120.0
C14—N15—H15B	108.8	C6'—C7'—C7B	121.6 (4)
C16—N15—H15B	108.8	C6'—C7'—H7'	119.2
H15A—N15—H15B	107.7	C7B—C7'—H7'	119.2
N2—C3—C14	109.1 (3)	C4A—C7A—C7	118.4 (3)
N2—C3—C4A	111.9 (3)	C4A—C7A—C8A	124.0 (3)
C14—C3—C4A	111.5 (3)	C7—C7A—C8A	117.5 (3)
N2—C3—H3	108.1	C3B—C7B—C7'	118.5 (3)
C14—C3—H3	108.1	C3B—C7B—C8B	123.2 (3)
C4A—C3—H3	108.1	C7'—C7B—C8B	118.1 (3)
C5—C4—C4A	120.7 (3)	C9'—C8'—C8B	120.4 (4)
C5—C4—H4	119.7	C9'—C8'—H8'	119.8
C4A—C4—H4	119.7	C8B—C8'—H8'	119.8
C6—C5—C4	119.6 (3)	C8—C8A—C11A	116.5 (3)
C6—C5—H5	120.2	C8—C8A—C7A	122.1 (3)
C4—C5—H5	120.2	C11A—C8A—C7A	121.2 (3)
C7—C6—C5	120.2 (3)	C11B—C8B—C8'	117.2 (4)
C7—C6—H6	119.9	C11B—C8B—C7B	122.7 (3)
C5—C6—H6	119.9	C8'—C8B—C7B	119.9 (4)
C6—C7—C7A	121.4 (3)	C10'—C9'—C8'	120.7 (4)
C6—C7—H7	119.3	C10'—C9'—H9'	119.7
C7A—C7—H7	119.3	C8'—C9'—H9'	119.7
C9—C8—C8A	121.8 (3)	C9'—C10'—C11'	119.9 (5)
C9—C8—H8	119.1	C9'—C10'—H10'	120.0
C8A—C8—H8	119.1	C11'—C10'—H10'	120.0
C10—C9—C8	120.4 (4)	C10'—C11'—C11B	119.1 (5)
C10—C9—H9	119.8	C10'—C11'—H11'	120.4
C8—C9—H9	119.8	C11B—C11'—H11'	120.4
C9—C10—C11	119.8 (4)	C11—C11A—C8A	122.0 (3)
C9—C10—H10	120.1	C11—C11A—S1	117.9 (3)
C11—C10—H10	120.1	C8A—C11A—S1	120.0 (3)
C10—C11—C11A	119.5 (4)	C8B—C11B—C11'	122.6 (4)
C10—C11—H11	120.2	C8B—C11B—S1'	119.6 (3)
C11A—C11—H11	120.2	C11'—C11B—S1'	117.7 (3)
N15—C14—C3	113.6 (3)	N15'—C14'—C3'	113.5 (3)
N15—C14—H14A	108.9	N15'—C14'—H14C	108.9
C3—C14—H14A	108.9	C3'—C14'—H14C	108.9
N15—C14—H14B	108.9	N15'—C14'—H14D	108.9
C3—C14—H14B	108.9	C3'—C14'—H14D	108.9
H14A—C14—H14B	107.7	H14C—C14'—H14D	107.7
N15—C16—C18	111.8 (3)	C14'—N15'—C16'	113.0 (3)
N15—C16—C17	108.3 (3)	C14'—N15'—H15C	109.0
C18—C16—C17	112.4 (3)	C16'—N15'—H15C	109.0
N15—C16—H16	108.1	C14'—N15'—H15D	109.0
C18—C16—H16	108.1	C16'—N15'—H15D	109.0
C17—C16—H16	108.1	H15C—N15'—H15D	107.8
C16—C17—H17A	109.5	N15'—C16'—C18'	111.5 (3)
C16—C17—H17B	109.5	N15'—C16'—C17'	108.4 (3)
H17A—C17—H17B	109.5	C18'—C16'—C17'	112.2 (3)
C16—C17—H17C	109.5	N15'—C16'—H16'	108.2
H17A—C17—H17C	109.5	C18'—C16'—H16'	108.2
H17B—C17—H17C	109.5	C17'—C16'—H16'	108.2
C19—C18—C25A	119.7 (3)	C16'—C17'—H17D	109.5
C19—C18—C16	121.8 (3)	C16'—C17'—H17E	109.5
C25A—C18—C16	118.5 (3)	H17D—C17'—H17E	109.5
C18—C19—C20	121.5 (4)	C16'—C17'—H17F	109.5
C18—C19—H19	119.2	H17D—C17'—H17F	109.5
C20—C19—H19	119.2	H17E—C17'—H17F	109.5
C21—C20—C19	119.8 (4)	C19'—C18'—C25B	119.3 (3)
C21—C20—H20	120.1	C19'—C18'—C16'	121.1 (3)
C19—C20—H20	120.1	C25B—C18'—C16'	119.5 (3)
C20—C21—C21A	121.8 (4)	C18'—C19'—C20'	121.9 (4)
C20—C21—H21	119.1	C18'—C19'—H19'	119.1
C21A—C21—H21	119.1	C20'—C19'—H19'	119.1
C23—C22—C21A	120.4 (4)	C21'—C20'—C19'	120.0 (4)
C23—C22—H22	119.8	C21'—C20'—H20'	120.0
C21A—C22—H22	119.8	C19'—C20'—H20'	120.0
C22—C23—C24	121.3 (4)	C20'—C21'—C21B	121.5 (4)
C22—C23—H23	119.3	C20'—C21'—H21'	119.3
C24—C23—H23	119.3	C21B—C21'—H21'	119.3
C25—C24—C23	120.1 (4)	C21—C21A—C22	122.2 (4)
C25—C24—H24	119.9	C21—C21A—C25A	119.1 (3)
C23—C24—H24	119.9	C22—C21A—C25A	118.7 (4)
C24—C25—C25A	121.4 (4)	C22'—C21B—C21'	122.4 (4)
C24—C25—H25	119.3	C22'—C21B—C25B	119.0 (4)
C25A—C25—H25	119.3	C21'—C21B—C25B	118.6 (4)
O1'—S1'—O2'	119.8 (2)	C23'—C22'—C21B	121.1 (5)
O1'—S1'—N2'	108.8 (2)	C23'—C22'—H22'	119.4
O2'—S1'—N2'	105.65 (18)	C21B—C22'—H22'	119.4
O1'—S1'—C11B	106.76 (19)	C22'—C23'—C24'	120.0 (4)
O2'—S1'—C11B	109.1 (2)	C22'—C23'—H23'	120.0
N2'—S1'—C11B	105.90 (18)	C24'—C23'—H23'	120.0
N2'—C3'—C3B	111.9 (3)	C25'—C24'—C23'	121.1 (5)
N2'—C3'—C14'	108.6 (3)	C25'—C24'—H24'	119.4
C3B—C3'—C14'	110.7 (3)	C23'—C24'—H24'	119.4
N2'—C3'—H3'	108.5	C24'—C25'—C25B	120.7 (4)
C3B—C3'—H3'	108.5	C24'—C25'—H25'	119.6
C14'—C3'—H3'	108.5	C25B—C25'—H25'	119.6
C4'—C3B—C7B	118.7 (3)	C25—C25A—C21A	118.0 (3)
C4'—C3B—C3'	122.0 (3)	C25—C25A—C18	124.0 (3)
C7B—C3B—C3'	119.4 (3)	C21A—C25A—C18	118.0 (3)
C3'—N2'—S1'	121.0 (2)	C25'—C25B—C21B	118.1 (4)
C3'—N2'—H2'	119.5	C25'—C25B—C18'	123.4 (3)
S1'—N2'—H2'	104.4	C21B—C25B—C18'	118.5 (4)
O2—S1—N2—C3	−157.2 (3)	C8B—C8'—C9'—C10'	1.1 (6)
O1—S1—N2—C3	73.0 (3)	C8'—C9'—C10'—C11'	1.9 (7)
C11A—S1—N2—C3	−41.9 (3)	C9'—C10'—C11'—C11B	−3.5 (7)
S1—N2—C3—C14	−160.9 (2)	C10—C11—C11A—C8A	1.6 (6)
S1—N2—C3—C4A	−37.0 (4)	C10—C11—C11A—S1	−174.9 (3)
C4A—C4—C5—C6	−0.2 (6)	C8—C8A—C11A—C11	0.9 (5)
C4—C5—C6—C7	−0.9 (6)	C7A—C8A—C11A—C11	−173.2 (3)
C5—C6—C7—C7A	0.3 (6)	C8—C8A—C11A—S1	177.4 (3)
C8A—C8—C9—C10	1.9 (6)	C7A—C8A—C11A—S1	3.2 (4)
C8—C9—C10—C11	0.7 (6)	O2—S1—C11A—C11	−7.6 (3)
C9—C10—C11—C11A	−2.5 (6)	O1—S1—C11A—C11	123.1 (3)
C16—N15—C14—C3	168.1 (3)	N2—S1—C11A—C11	−120.8 (3)
N2—C3—C14—N15	−78.5 (4)	O2—S1—C11A—C8A	175.8 (3)
C4A—C3—C14—N15	157.4 (3)	O1—S1—C11A—C8A	−53.5 (3)
C14—N15—C16—C18	55.9 (4)	N2—S1—C11A—C8A	62.6 (3)
C14—N15—C16—C17	−179.8 (3)	C8'—C8B—C11B—C11'	0.6 (6)
N15—C16—C18—C19	36.1 (4)	C7B—C8B—C11B—C11'	−173.8 (4)
C17—C16—C18—C19	−85.9 (4)	C8'—C8B—C11B—S1'	175.8 (3)
N15—C16—C18—C25A	−145.7 (3)	C7B—C8B—C11B—S1'	1.4 (5)
C17—C16—C18—C25A	92.2 (4)	C10'—C11'—C11B—C8B	2.2 (6)
C25A—C18—C19—C20	3.4 (5)	C10'—C11'—C11B—S1'	−173.0 (3)
C16—C18—C19—C20	−178.5 (3)	O1'—S1'—C11B—C8B	−52.5 (3)
C18—C19—C20—C21	−1.9 (6)	O2'—S1'—C11B—C8B	176.6 (3)
C19—C20—C21—C21A	−0.3 (6)	N2'—S1'—C11B—C8B	63.3 (3)
C21A—C22—C23—C24	−1.2 (6)	O1'—S1'—C11B—C11'	122.9 (3)
C22—C23—C24—C25	0.9 (6)	O2'—S1'—C11B—C11'	−8.0 (4)
C23—C24—C25—C25A	0.2 (6)	N2'—S1'—C11B—C11'	−121.3 (3)
N2'—C3'—C3B—C4'	−105.5 (4)	N2'—C3'—C14'—N15'	−76.7 (4)
C14'—C3'—C3B—C4'	15.8 (5)	C3B—C3'—C14'—N15'	160.1 (3)
N2'—C3'—C3B—C7B	75.5 (4)	C3'—C14'—N15'—C16'	171.8 (3)
C14'—C3'—C3B—C7B	−163.2 (3)	C14'—N15'—C16'—C18'	55.2 (4)
C3B—C3'—N2'—S1'	−39.4 (4)	C14'—N15'—C16'—C17'	179.2 (3)
C14'—C3'—N2'—S1'	−161.8 (3)	N15'—C16'—C18'—C19'	38.7 (4)
O1'—S1'—N2'—C3'	74.4 (3)	C17'—C16'—C18'—C19'	−83.2 (4)
O2'—S1'—N2'—C3'	−155.8 (3)	N15'—C16'—C18'—C25B	−143.2 (3)
C11B—S1'—N2'—C3'	−40.1 (4)	C17'—C16'—C18'—C25B	94.9 (4)
C7B—C3B—C4'—C5'	2.2 (6)	C25B—C18'—C19'—C20'	4.1 (6)
C3'—C3B—C4'—C5'	−176.8 (4)	C16'—C18'—C19'—C20'	−177.8 (3)
C5—C4—C4A—C7A	2.0 (6)	C18'—C19'—C20'—C21'	−1.1 (6)
C5—C4—C4A—C3	−176.9 (3)	C19'—C20'—C21'—C21B	−2.7 (7)
N2—C3—C4A—C4	−105.3 (4)	C20—C21—C21A—C22	−179.5 (4)
C14—C3—C4A—C4	17.2 (4)	C20—C21—C21A—C25A	1.1 (6)
N2—C3—C4A—C7A	75.9 (4)	C23—C22—C21A—C21	−179.1 (4)
C14—C3—C4A—C7A	−161.6 (3)	C23—C22—C21A—C25A	0.3 (6)
C3B—C4'—C5'—C6'	−0.8 (7)	C20'—C21'—C21B—C22'	−177.4 (4)
C4'—C5'—C6'—C7'	−0.5 (7)	C20'—C21'—C21B—C25B	3.3 (6)
C5'—C6'—C7'—C7B	0.3 (7)	C21'—C21B—C22'—C23'	179.5 (4)
C4—C4A—C7A—C7	−2.5 (5)	C25B—C21B—C22'—C23'	−1.2 (6)
C3—C4A—C7A—C7	176.4 (3)	C21B—C22'—C23'—C24'	1.3 (7)
C4—C4A—C7A—C8A	173.1 (3)	C22'—C23'—C24'—C25'	−0.7 (7)
C3—C4A—C7A—C8A	−8.0 (5)	C23'—C24'—C25'—C25B	0.0 (6)
C6—C7—C7A—C4A	1.4 (5)	C24—C25—C25A—C21A	−0.9 (5)
C6—C7—C7A—C8A	−174.5 (3)	C24—C25—C25A—C18	178.8 (3)
C4'—C3B—C7B—C7'	−2.3 (5)	C21—C21A—C25A—C25	−179.8 (3)
C3'—C3B—C7B—C7'	176.7 (3)	C22—C21A—C25A—C25	0.7 (5)
C4'—C3B—C7B—C8B	173.8 (3)	C21—C21A—C25A—C18	0.4 (5)
C3'—C3B—C7B—C8B	−7.2 (5)	C22—C21A—C25A—C18	−179.1 (3)
C6'—C7'—C7B—C3B	1.1 (6)	C19—C18—C25A—C25	177.7 (3)
C6'—C7'—C7B—C8B	−175.2 (4)	C16—C18—C25A—C25	−0.5 (5)
C9—C8—C8A—C11A	−2.7 (5)	C19—C18—C25A—C21A	−2.6 (5)
C9—C8—C8A—C7A	171.4 (3)	C16—C18—C25A—C21A	179.2 (3)
C4A—C7A—C8A—C8	137.8 (3)	C24'—C25'—C25B—C21B	0.1 (5)
C7—C7A—C8A—C8	−46.6 (5)	C24'—C25'—C25B—C18'	−179.7 (3)
C4A—C7A—C8A—C11A	−48.4 (5)	C22'—C21B—C25B—C25'	0.5 (5)
C7—C7A—C8A—C11A	127.2 (3)	C21'—C21B—C25B—C25'	179.9 (3)
C9'—C8'—C8B—C11B	−2.3 (5)	C22'—C21B—C25B—C18'	−179.7 (3)
C9'—C8'—C8B—C7B	172.3 (3)	C21'—C21B—C25B—C18'	−0.4 (5)
C3B—C7B—C8B—C11B	−47.6 (5)	C19'—C18'—C25B—C25'	176.6 (3)
C7'—C7B—C8B—C11B	128.4 (4)	C16'—C18'—C25B—C25'	−1.6 (5)
C3B—C7B—C8B—C8'	138.1 (4)	C19'—C18'—C25B—C21B	−3.2 (5)
C7'—C7B—C8B—C8'	−45.8 (5)	C16'—C18'—C25B—C21B	178.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1^i	0.98	2.34	3.307 (3)	167
N15—H15B···Cl1	0.90	2.29	3.179 (3)	168
N15—H15A···Cl1^i	0.90	2.20	3.098 (3)	174
N2′—H2′···Cl1′	0.81	2.54	3.299 (3)	157
N15′—H15C···Cl1′	0.90	2.18	3.072 (3)	173
N15′—H15D···Cl1′^ii	0.90	2.31	3.185 (3)	164
C7—H7···Cg13	0.93	2.80	3.569 (4)	140
C7′—H7′···Cg4^iii	0.93	2.96	3.684 (5)	136
C9′—H9′···O1′^iii	0.93	2.48	3.064 (6)	121

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