2-{[(4-Methyl­phen­yl)sulfon­yl]amino}­phenyl 4-methyl­benzene­sulfonate

The title compound, C₂₀H₁₉NO₅S₂, crystallizes as an almost 2:1 mixture of two mol­ecular orientations (described as Orient-A and Orient-B). The consequences of these two orientations is the formation of three types of N—H...O hydrogen-bonded dimers in which the (Orient-A + Orient-A) dimers are likely to be the most stable, while the mixed (Orient-A + Orient-B) dimers are more frequent. Extra inter­actions in the form of C—H...O and C—H...π inter­actions act to further stabilize these dimers and probably allow the less energetically favourable (Orient-A + Orient-B) and (Orient-B + Orient-B) hydrogen-bonded dimers to exist by preventing their conversion to (Orient-A + Orient-A)-only hydrogen-bonded dimers during the crystal-growth process.

S1. Comment

Benzannulated heterocycles are interesting compounds that play important structural roles in natural products and man-made pharmaceuticals. Our research group has used ring-closing metathesis (RCM) and isomerization-RCM strategies to synthesize benzannulated heterocycles (van Otterlo, Morgans et al., 2004, 2005; van Otterlo, Ngidi et al., 2004, 2005).

During the synthesis of heterocycles, such as (IV), containing both N and O atoms in the benzofused portion, 2-aminophenol, (I), has to be protected initially as its ditosyl derivative, (II). Selective cleavage of the S—O bond, with magnesium in methanol (Sridhar et al., 1998), then affords compound (III), which can be converted to the protected 6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine, (IV), via a number of steps (van Otterlo, Morgans et al., 2004 or van Otterlo, Ngidi et al., 2004 ????; Ibrahim et al., 2002). As compound (II) is crystalline it was decided that it would be interesting to investigate its structure in the solid state.

The title compound crystallizes as a disordered arrangement in which atoms N1 and O5 are swapped around in two orientations such that the molecule shown in Fig. 1(a) (Orient-A) is superimposed on the molecule shown in Fig. 1(b) (Orient-B). The ratio Orient-A to Orient-B is about 0.63 (2):0.37 (2). Visually the molecule has a pseudo-twofold axis passing through the aromatic ring defined by atoms C8–C13, and one would therefore expect the molecule to crystallize on a twofold axis (a special position in space groups containing this symmetry) leading to the observed orientational disorder. However, the compound crystallizes instead in the space group P1 with one molecule in the assymetric unit. Comparison of some geometric parameters between the sulfonyl groups and the attached benzene rings (C1–C6 versus C14–C19) indicates that the torsion angles on the two sides differ by more than 10° (Table 1) and hence indicate the absence of a molecular twofold axis.

The crystal structure of (II) is stabilized by both intramolecular and intermolecular classical and weak hydrogen bonding (Table 2; for simplicity the very extensive intramolecular hydrogen bonding has been omitted from this table but can be found in the CIF). The dominant intermolecular interaction in the structure is an N—H···O hydrogen bond between a pair of molecules forming a hydrogen-bonded dimer. The morphology of this hydrogen-bonded network differs significantly between the two molecular orientations, though the overall appearance is very similar (Fig. 2). For Orient-A, the N—H···O hydrogen bonding (between N1 and O2ⁱ; symmetry codes as in Table 2) results in a hydrogen-bonded dimer that can be described by the R²₂(8) graph set (Fig. 2a). For the alternative orientation (Orient-B) the N—H···O hydrogen bonding (between N1A and O2ⁱ in this case) results in a hydrogen-bonded dimer that can be described by the R²₂(14) graph set (Fig. 2b). Interestingly, the hydrogen-bond dimer formed by a pair of Orient-A molecules has a D···A distance of 3.038 (16) Å versus 3.31 (3) Å in the dimer formed by a pair of Orient-B molecules. The shorter D···A distance between Orient-A molecules implies that this orientation is more stable and this assumption is coroborated by the higher frequency of Orient-A (63% occurance). Nevertheless the frequency of the Orient-B orientation is still very high. Rather than the extremes of Orient-A– and Orient-B-only dimers, it is likely that the `real' average situation in a crystal is a hydrogen-bonded relationship in which Orient-A is about 26% (frequency of Orient-A minus frequency of Orient-B) of the time hydrogen bonded to other Orient-A molecules and the rest of the time hydrogen bonded to Orient-B molecules (37% of the time – the frequency of Orient-B). This Orient-A + Orient-B arrangement would probably not be as energetically unfavourable as Orient-B-only hydrogen-bonded dimers, being made up of one hydrogen bond of each type of orientation, i.e. one 3.0 Å and one 3.3 Å intermolecular N—H···O bond. These hydrogen-bonded dimers are further stabilized by C—H···π [C18—H18···Cg(C1–C6)ⁱ] and C—H···O (C2—H2···O2) interactions (Fig. 2). The stabilization due to these extra weak interactions is probably also a significant contributor to the stability of the Orient-B dimers as it would probably make the conversion of Orient-B + Orient-B (if they exist) and Orient-B + Orient-A dimers to Orient-A-only dimers quite difficult.

Finally, all the hydrogen-bonded dimers interact further with neighbouring dimers through C—H···O interactions (C16—H16···O1 and C20—H20C···O1) to form layers perpendicular to the (100) direction.

Related literature

For related literature, see: Ibrahim et al. (2002); Otterlo, Morgans, Khanye, Aderibigbe, Michael & Billing (2004); Otterlo, Morgans, Madeley, Kuzvidza, Moleele, Thornton & de Koning (2005); Otterlo, Ngidi, Kuzvidza, Morgans, Moleele & de Koning (2005); Otterlo, Ngidi, de Koning & Fernandes (2004); Sridhar et al. (1998).

S2. Experimental

p-Toluenesulfonyl chloride (11.80 g, 62 mmol) was added to 2-aminophenol (2.25 g, 21 mmol) dissolved in pyridine (50 ml) and stirred under N₂ for 60 h. The pyridine was evaporated and CH₂Cl₂ (100 ml) was added to the resulting residue. The organic phase was then washed with HCl (0.5 M, 2 × 50 ml), water (50 ml) and brine (50 ml), after which it was dried (MgSO₄) and evaporated under reduced pressure to afford compound (II) as a yellow solid. This solid was recrystalized from hot EtOH to give white crystals of (II) (6.43 g, 87%, mp. 410–412 K).

NMR: δ_H (300 MHz, CDCl₃) 7.69 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.64 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.55 (dd, 1H, J = 8.1 and 1.3 Hz, Ar—H), 7.35 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.19 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.20–7.15 (m partially under d, 1H, Ar—H), 7.08 (br s, 1H, NH), 6.98 (dt, 1H, J = 1.3 and 8.0 Hz, Ar—H), 6.81 (dd, 1H,J = 8.3 and 1.3 Hz, Ar—H), 2.48 (s, 3H, Ar—CH₃), 2.36 (s, 3H, Ar—CH₃); δ_C(75 MHz, CDCl₃) 146.4 (Ar—O), 144.0 (Ar—N), 140.2 (Ar—S), 136.2 (Ar—S), 131.4 (Ar—C), 130.1 (Ar—CH), 130.0 (Ar—C), 129.6 (Ar—CH), 128.4 (Ar—CH), 127.9 (Ar—CH), 127.3 (Ar—CH), 125.5 (Ar—CH), 123.3 (Ar—CH), 123.0 (Ar—CH), 21.8 (Ar—CH₃), 21.5 (Ar—CH₃); ν_max (thin film, NaCl plate, cm^-1): 3361, 3020, 1599, 1495, 1340, 1293, 1215.

S3. Refinement

The molecule was found to exhibit orientational disorder with the N1 and O5 positions being disordered. Each of these atoms was refined over two positions as N1 and N1A, and O5 and O5A, using SADI restraints, while constraining the sum of the final occupancies to unity. The final occupancy was 0.63 (2) for N1 and O5, and 0.37 (2) for N1A and O5A. NH H atoms (H1 and H1A) were first located in a Fourier difference map and then positioned geometrically (N—H = 0.92 Å) with isotropic displacement parameters equal to 1.2 times U_eq of the parent atoms. H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H bond lengths of 0.95 (aromatic CH) or 0.98 Å (CH₃), and isotropic displacement parameters equal to 1.2 (CH) or 1.5 (CH₃) times U_eq of the parent atom.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXTL.

Figures

Fig. 1. Views of the two orientations of the molecule of (II), showing the atom-numbering scheme. These are superimposed on each other in the crystal structure. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown with an arbitrary radius.

Fig. 2. Hydrogen-bonded dimers in the structure of (II). These diagrams represent the extremes in which (a) Orient-A molecules hydorgen bond to other Orient-A molecules and (b) Orient-B molecules hydrogen bond to other Orient-B molecules. The most frequent real situation is probably a combination of the two. Indicated on the diagrams are the N—H···O [N1(A)—H1(A)···O2], C—H···O (C2—H2···O2) and C—H···π interactions for both types of hydrogen-bonded dimer. Molecules (i) and (ii) are in the symmetry positions (x, y, z) and (2 - x, -y, 1 - z), respectively.

2-{[(4-Methylphenyl)sulfonyl]amino}phenyl 4-methylbenzenesulfonate

Crystal data

C20H19NO5S2	Z = 2
Mr = 417.48	F(000) = 436
Triclinic, P1	Dx = 1.430 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7596 (2) Å	Cell parameters from 9133 reflections
b = 10.1025 (2) Å	θ = 2.1–28.3°
c = 10.7227 (2) Å	µ = 0.31 mm^−1
α = 80.173 (1)°	T = 173 K
β = 76.633 (1)°	Irregular, colourless
γ = 71.442 (1)°	0.38 × 0.24 × 0.21 mm
V = 969.68 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4042 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
ϕ and ω scans	h = −12→12
18642 measured reflections	k = −12→13
4684 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0381P)^2 + 0.6327P] where P = (Fo^2 + 2Fc^2)/3
4684 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 0.30 e Å^−3
92 restraints	Δρmin = −0.43 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.83294 (17)	0.16805 (17)	0.30264 (15)	0.0270 (3)
C2	0.7702 (2)	0.06307 (19)	0.36411 (18)	0.0340 (4)
H2	0.8133	−0.0040	0.4282	0.041*
C3	0.6433 (2)	0.0578 (2)	0.33027 (19)	0.0374 (4)
H3	0.5996	−0.0139	0.3717	0.045*
C4	0.5787 (2)	0.1558 (2)	0.23662 (19)	0.0379 (4)
C5	0.6442 (2)	0.2593 (2)	0.17705 (18)	0.0376 (4)
H5	0.6012	0.3267	0.1130	0.045*
C6	0.7708 (2)	0.26678 (19)	0.20879 (16)	0.0328 (4)
H6	0.8146	0.3383	0.1671	0.039*
C7	0.4398 (3)	0.1512 (3)	0.2020 (3)	0.0571 (6)
H7A	0.3647	0.2420	0.2126	0.086*
H7B	0.4041	0.0773	0.2585	0.086*
H7C	0.4599	0.1313	0.1121	0.086*
C8	0.8407 (2)	0.37566 (18)	0.49423 (17)	0.0308 (4)
C9	0.8754 (3)	0.4922 (2)	0.42126 (19)	0.0417 (4)
H9	0.9679	0.4818	0.3647	0.050*
C10	0.7740 (3)	0.6234 (2)	0.4316 (2)	0.0551 (6)
H10	0.7970	0.7033	0.3815	0.066*
C11	0.6405 (3)	0.6391 (2)	0.5136 (2)	0.0589 (7)
H11	0.5710	0.7295	0.5186	0.071*
C12	0.6065 (3)	0.5245 (2)	0.5887 (2)	0.0491 (5)
H12	0.5141	0.5357	0.6457	0.059*
C13	0.7081 (2)	0.3927 (2)	0.58062 (17)	0.0344 (4)
C14	0.81376 (19)	0.26826 (19)	0.84672 (16)	0.0313 (4)
C15	0.8359 (2)	0.3944 (2)	0.85734 (18)	0.0361 (4)
H15	0.7610	0.4805	0.8470	0.043*
C16	0.9687 (2)	0.3930 (2)	0.88319 (19)	0.0440 (5)
H16	0.9847	0.4792	0.8900	0.053*
C17	1.0791 (2)	0.2684 (3)	0.89940 (18)	0.0461 (5)
C18	1.0533 (2)	0.1435 (2)	0.88926 (19)	0.0478 (5)
H18	1.1276	0.0572	0.9007	0.057*
C19	0.9218 (2)	0.1423 (2)	0.86295 (18)	0.0403 (4)
H19	0.9056	0.0561	0.8561	0.048*
C20	1.2236 (3)	0.2679 (4)	0.9266 (3)	0.0734 (9)
H20A	1.2460	0.3552	0.8865	0.110*
H20B	1.3017	0.1876	0.8912	0.110*
H20C	1.2174	0.2604	1.0200	0.110*
O1	1.05129 (14)	0.27385 (14)	0.25118 (13)	0.0368 (3)
O2	1.08672 (13)	0.03836 (13)	0.36976 (12)	0.0336 (3)
O3	0.53655 (15)	0.38933 (16)	0.85213 (14)	0.0454 (3)
O4	0.62582 (18)	0.13181 (17)	0.85563 (16)	0.0542 (4)
S1	0.99357 (4)	0.17685 (4)	0.34376 (4)	0.02779 (11)
S2	0.64780 (5)	0.26562 (5)	0.81305 (4)	0.03651 (13)
O5	0.6795 (12)	0.2733 (10)	0.6568 (7)	0.0342 (18)	0.627 (18)
N1	0.9470 (19)	0.2391 (14)	0.4861 (12)	0.031 (3)	0.627 (18)
H1	0.9072	0.1771	0.5447	0.037*	0.627 (18)
O5A	0.937 (3)	0.2394 (16)	0.4788 (16)	0.025 (2)	0.373 (18)
N1A	0.667 (3)	0.274 (2)	0.6553 (17)	0.041 (5)*	0.373 (18)
H1A	0.7459	0.1981	0.6314	0.050*	0.373 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0233 (7)	0.0296 (8)	0.0265 (8)	−0.0030 (6)	−0.0052 (6)	−0.0076 (6)
C2	0.0334 (9)	0.0323 (9)	0.0364 (9)	−0.0077 (7)	−0.0100 (7)	−0.0027 (7)
C3	0.0325 (9)	0.0374 (10)	0.0449 (10)	−0.0119 (8)	−0.0070 (8)	−0.0081 (8)
C4	0.0293 (9)	0.0449 (11)	0.0409 (10)	−0.0030 (8)	−0.0091 (7)	−0.0199 (8)
C5	0.0353 (9)	0.0421 (10)	0.0315 (9)	0.0006 (8)	−0.0132 (7)	−0.0066 (7)
C6	0.0343 (9)	0.0342 (9)	0.0270 (8)	−0.0051 (7)	−0.0068 (7)	−0.0037 (7)
C7	0.0415 (12)	0.0698 (16)	0.0691 (15)	−0.0122 (11)	−0.0239 (11)	−0.0210 (12)
C8	0.0336 (9)	0.0281 (8)	0.0327 (8)	−0.0047 (7)	−0.0136 (7)	−0.0070 (7)
C9	0.0575 (12)	0.0340 (10)	0.0340 (9)	−0.0140 (9)	−0.0078 (9)	−0.0046 (7)
C10	0.0935 (19)	0.0294 (10)	0.0350 (10)	−0.0087 (11)	−0.0111 (11)	−0.0034 (8)
C11	0.0829 (18)	0.0366 (11)	0.0390 (11)	0.0131 (11)	−0.0149 (11)	−0.0098 (9)
C12	0.0488 (12)	0.0508 (12)	0.0374 (10)	0.0050 (10)	−0.0097 (9)	−0.0132 (9)
C13	0.0372 (9)	0.0386 (10)	0.0304 (8)	−0.0090 (8)	−0.0137 (7)	−0.0053 (7)
C14	0.0324 (9)	0.0362 (9)	0.0257 (8)	−0.0136 (7)	−0.0004 (6)	−0.0039 (7)
C15	0.0418 (10)	0.0336 (9)	0.0358 (9)	−0.0152 (8)	−0.0118 (8)	0.0030 (7)
C16	0.0526 (12)	0.0527 (12)	0.0372 (10)	−0.0301 (10)	−0.0153 (9)	0.0054 (9)
C17	0.0362 (10)	0.0763 (15)	0.0257 (9)	−0.0188 (10)	−0.0061 (7)	0.0005 (9)
C18	0.0407 (11)	0.0570 (13)	0.0329 (10)	0.0027 (9)	−0.0051 (8)	−0.0058 (9)
C19	0.0447 (11)	0.0368 (10)	0.0337 (9)	−0.0064 (8)	−0.0006 (8)	−0.0086 (8)
C20	0.0438 (13)	0.133 (3)	0.0496 (14)	−0.0303 (15)	−0.0161 (11)	−0.0071 (15)
O1	0.0328 (7)	0.0374 (7)	0.0382 (7)	−0.0119 (5)	−0.0017 (5)	−0.0029 (5)
O2	0.0259 (6)	0.0327 (6)	0.0372 (7)	−0.0002 (5)	−0.0059 (5)	−0.0065 (5)
O3	0.0319 (7)	0.0587 (9)	0.0428 (8)	−0.0107 (6)	0.0017 (6)	−0.0144 (7)
O4	0.0597 (10)	0.0574 (10)	0.0540 (9)	−0.0395 (8)	0.0081 (7)	−0.0107 (7)
S1	0.02313 (19)	0.0290 (2)	0.0296 (2)	−0.00452 (15)	−0.00455 (15)	−0.00514 (15)
S2	0.0331 (2)	0.0453 (3)	0.0349 (2)	−0.0199 (2)	0.00177 (18)	−0.00891 (19)
O5	0.030 (2)	0.047 (3)	0.034 (2)	−0.0181 (16)	−0.0047 (11)	−0.0140 (11)
N1	0.032 (5)	0.032 (3)	0.029 (3)	−0.004 (2)	−0.010 (2)	−0.011 (3)
O5A	0.021 (3)	0.024 (4)	0.034 (5)	−0.007 (3)	−0.015 (3)	0.004 (3)

Geometric parameters (Å, º)

C1—C2	1.387 (2)	C13—N1A	1.435 (17)
C1—C6	1.389 (2)	C14—C19	1.384 (3)
C1—S1	1.7555 (17)	C14—C15	1.386 (2)
C2—C3	1.387 (3)	C14—S2	1.7481 (18)
C2—H2	0.9500	C15—C16	1.381 (3)
C3—C4	1.393 (3)	C15—H15	0.9500
C3—H3	0.9500	C16—C17	1.387 (3)
C4—C5	1.386 (3)	C16—H16	0.9500
C4—C7	1.502 (3)	C17—C18	1.389 (3)
C5—C6	1.382 (3)	C17—C20	1.503 (3)
C5—H5	0.9500	C18—C19	1.380 (3)
C6—H6	0.9500	C18—H18	0.9500
C7—H7A	0.9800	C19—H19	0.9500
C7—H7B	0.9800	C20—H20A	0.9800
C7—H7C	0.9800	C20—H20B	0.9800
C8—C13	1.386 (3)	C20—H20C	0.9800
C8—C9	1.389 (3)	O1—S1	1.4226 (13)
C8—O5A	1.409 (15)	O2—S1	1.4270 (12)
C8—N1	1.441 (12)	O3—S2	1.4217 (15)
C9—C10	1.383 (3)	O4—S2	1.4179 (15)
C9—H9	0.9500	S1—O5A	1.588 (15)
C10—C11	1.372 (4)	S1—N1	1.660 (11)
C10—H10	0.9500	S2—O5	1.625 (7)
C11—C12	1.380 (3)	S2—N1A	1.648 (18)
C11—H11	0.9500	O5—H1A	0.8644
C12—C13	1.386 (3)	N1—H1	0.9200
C12—H12	0.9500	O5A—H1	0.9195
C13—O5	1.405 (8)	N1A—H1A	0.9200
C2—C1—C6	121.09 (16)	C16—C15—H15	120.5
C2—C1—S1	119.65 (13)	C14—C15—H15	120.5
C6—C1—S1	119.26 (14)	C15—C16—C17	121.5 (2)
C1—C2—C3	118.80 (17)	C15—C16—H16	119.3
C1—C2—H2	120.6	C17—C16—H16	119.3
C3—C2—H2	120.6	C16—C17—C18	118.33 (19)
C2—C3—C4	121.21 (18)	C16—C17—C20	121.1 (2)
C2—C3—H3	119.4	C18—C17—C20	120.6 (2)
C4—C3—H3	119.4	C19—C18—C17	121.28 (19)
C5—C4—C3	118.54 (17)	C19—C18—H18	119.4
C5—C4—C7	120.44 (19)	C17—C18—H18	119.4
C3—C4—C7	121.0 (2)	C18—C19—C14	119.13 (19)
C6—C5—C4	121.42 (17)	C18—C19—H19	120.4
C6—C5—H5	119.3	C14—C19—H19	120.4
C4—C5—H5	119.3	C17—C20—H20A	109.5
C5—C6—C1	118.95 (17)	C17—C20—H20B	109.5
C5—C6—H6	120.5	H20A—C20—H20B	109.5
C1—C6—H6	120.5	C17—C20—H20C	109.5
C4—C7—H7A	109.5	H20A—C20—H20C	109.5
C4—C7—H7B	109.5	H20B—C20—H20C	109.5
H7A—C7—H7B	109.5	O1—S1—O2	119.24 (8)
C4—C7—H7C	109.5	O1—S1—O5A	109.2 (7)
H7A—C7—H7C	109.5	O2—S1—O5A	105.4 (6)
H7B—C7—H7C	109.5	O1—S1—N1	108.0 (6)
C13—C8—C9	119.80 (17)	O2—S1—N1	102.8 (5)
C13—C8—O5A	119.3 (9)	O1—S1—C1	108.54 (8)
C9—C8—O5A	120.9 (9)	O2—S1—C1	109.69 (8)
C13—C8—N1	120.3 (7)	O5A—S1—C1	103.7 (10)
C9—C8—N1	119.7 (7)	N1—S1—C1	107.9 (7)
C10—C9—C8	119.4 (2)	O4—S2—O3	120.34 (9)
C10—C9—H9	120.3	O4—S2—O5	104.2 (3)
C8—C9—H9	120.3	O3—S2—O5	108.8 (4)
C11—C10—C9	120.6 (2)	O4—S2—N1A	102.8 (7)
C11—C10—H10	119.7	O3—S2—N1A	106.7 (9)
C9—C10—H10	119.7	O4—S2—C14	109.95 (10)
C10—C11—C12	120.4 (2)	O3—S2—C14	108.62 (9)
C10—C11—H11	119.8	O5—S2—C14	103.5 (4)
C12—C11—H11	119.8	N1A—S2—C14	107.6 (8)
C11—C12—C13	119.5 (2)	C13—O5—S2	120.3 (6)
C11—C12—H12	120.2	C13—O5—H1A	110.3
C13—C12—H12	120.2	S2—O5—H1A	110.1
C8—C13—C12	120.15 (19)	C8—N1—S1	116.3 (9)
C8—C13—O5	118.2 (5)	C8—N1—H1	107.1
C12—C13—O5	121.6 (5)	S1—N1—H1	107.3
C8—C13—N1A	121.2 (11)	C8—O5A—S1	123.1 (12)
C12—C13—N1A	118.4 (11)	C8—O5A—H1	109.7
C19—C14—C15	120.88 (18)	S1—O5A—H1	113.1
C19—C14—S2	118.77 (15)	C13—N1A—S2	117.0 (13)
C15—C14—S2	120.35 (14)	C13—N1A—H1A	104.4
C16—C15—C14	118.92 (18)	S2—N1A—H1A	105.1
C6—C1—C2—C3	0.0 (3)	C6—C1—S1—O2	−143.28 (13)
S1—C1—C2—C3	−179.98 (14)	C2—C1—S1—O5A	−75.4 (6)
C1—C2—C3—C4	−0.2 (3)	C6—C1—S1—O5A	104.5 (6)
C2—C3—C4—C5	0.2 (3)	C2—C1—S1—N1	−74.6 (6)
C2—C3—C4—C7	−178.92 (19)	C6—C1—S1—N1	105.4 (5)
C3—C4—C5—C6	0.0 (3)	C19—C14—S2—O4	22.65 (17)
C7—C4—C5—C6	179.05 (18)	C15—C14—S2—O4	−157.10 (15)
C4—C5—C6—C1	−0.1 (3)	C19—C14—S2—O3	156.22 (14)
C2—C1—C6—C5	0.1 (3)	C15—C14—S2—O3	−23.53 (17)
S1—C1—C6—C5	−179.90 (13)	C19—C14—S2—O5	−88.2 (4)
C13—C8—C9—C10	−2.9 (3)	C15—C14—S2—O5	92.0 (4)
O5A—C8—C9—C10	175.1 (11)	C19—C14—S2—N1A	−88.6 (9)
N1—C8—C9—C10	−178.6 (7)	C15—C14—S2—N1A	91.6 (8)
C8—C9—C10—C11	0.4 (3)	C8—C13—O5—S2	121.1 (7)
C9—C10—C11—C12	1.2 (4)	C12—C13—O5—S2	−60.0 (9)
C10—C11—C12—C13	−0.2 (4)	N1A—C13—O5—S2	−108 (16)
C9—C8—C13—C12	3.9 (3)	O4—S2—O5—C13	−179.4 (7)
O5A—C8—C13—C12	−174.2 (11)	O3—S2—O5—C13	51.1 (9)
N1—C8—C13—C12	179.6 (7)	N1A—S2—O5—C13	110 (16)
C9—C8—C13—O5	−177.3 (4)	C14—S2—O5—C13	−64.3 (8)
O5A—C8—C13—O5	4.7 (12)	C13—C8—N1—S1	120.4 (9)
N1—C8—C13—O5	−1.6 (8)	C9—C8—N1—S1	−63.9 (14)
C9—C8—C13—N1A	178.6 (9)	O5A—C8—N1—S1	40 (14)
O5A—C8—C13—N1A	0.6 (12)	O1—S1—N1—C8	58.4 (13)
N1—C8—C13—N1A	−5.7 (13)	O2—S1—N1—C8	−174.6 (11)
C11—C12—C13—C8	−2.3 (3)	O5A—S1—N1—C8	−47 (15)
C11—C12—C13—O5	178.9 (4)	C1—S1—N1—C8	−58.8 (13)
C11—C12—C13—N1A	−177.2 (9)	C13—C8—O5A—S1	123.3 (15)
C19—C14—C15—C16	0.7 (3)	C9—C8—O5A—S1	−55 (2)
S2—C14—C15—C16	−179.58 (14)	N1—C8—O5A—S1	−134 (17)
C14—C15—C16—C17	−0.4 (3)	O1—S1—O5A—C8	51 (2)
C15—C16—C17—C18	−0.1 (3)	O2—S1—O5A—C8	180.0 (16)
C15—C16—C17—C20	179.60 (19)	N1—S1—O5A—C8	126 (17)
C16—C17—C18—C19	0.4 (3)	C1—S1—O5A—C8	−65 (2)
C20—C17—C18—C19	−179.31 (19)	C8—C13—N1A—S2	116.5 (14)
C17—C18—C19—C14	−0.1 (3)	C12—C13—N1A—S2	−68.7 (17)
C15—C14—C19—C18	−0.4 (3)	O5—C13—N1A—S2	65 (14)
S2—C14—C19—C18	179.85 (14)	O4—S2—N1A—C13	−173.3 (14)
C2—C1—S1—O1	168.59 (13)	O3—S2—N1A—C13	59.2 (18)
C6—C1—S1—O1	−11.43 (16)	O5—S2—N1A—C13	−63 (14)
C2—C1—S1—O2	36.74 (16)	C14—S2—N1A—C13	−57.2 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.92	2.20	3.038 (16)	151
N1A—H1A···O2^i	0.92	2.43	3.31 (3)	162
C2—H2···O2^i	0.95	2.50	3.328 (2)	145
C16—H16···O1^ii	0.95	2.65	3.391 (2)	135
C20—H20C···O1^iii	0.98	2.63	3.499 (3)	148
C18—H18···Cg1^i	0.95	2.93	3.642 (2)	133
N1—H1···O5	0.92	2.26	2.779 (18)	115
N1A—H1A···O5A	0.92	2.27	2.82 (3)	118
C6—H6···O1	0.95	2.53	2.901 (3)	104
C9—H9···O1	0.95	2.43	2.942 (2)	114
C12—H12···O3	0.95	2.46	2.949 (3)	112
C19—H19···O4	0.95	2.59	2.944 (3)	102

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