5-Phen­yl-1,3,4-thia­diazol-2-yl 2,3,4,6-tetra­-O-acet­yl-1-thio-[beta]-D-glucopyran­oside

The structure of the title compound, C₂₂H₂₄N₂O₉S₂, is described. This compound consists of a sugar ring and a heterocyclic base linked unusually by an S atom. The sugar is in a ⁴C₁ chair conformation and forms dihedral angles of 49.54 (4) and 33.42 (5)° with the thia­diazole and phen­yl rings, respectively. The S atom occupies an equatorial position of the sugar ring and lies 1.807 (2) Å out of the corresponding mean plane.

S1. Comment

1,3,4-Thiadiazole derivatives display a broad spectrum of biological activities, such as fungicidal (Zou et al., 2002), antibacterial (Deibel et al., 2004), antidepressant (Clerici et al., 2001) and antiepileptic (Masereel et al., 2002) properties. However, the application of 1,3,4-thiadiazoles is limited because of their poor solubility, both in organic solvents and in water. In the course of identifying new chemical structures that may serve as leads in the design of novel antiviral agents, we were particularly interested in the linking of thio-1,3,4-thiadiazoles to hydrophilic moieties such as D-glucose. The present structure determination is part of an investigation into the nucleophilic substitution of a bromosugar to a thioheterocyclic compound. Here, we report the X-ray crystal structure determination of the title compound (I) (Fig. 1).

The 2,3,4,6-tetra-O-acetyglucopyranosyl ring of (I) assumes a ⁴C₁ chair conformation, with atoms C2 and C5 displaced from the C1—C3—C4—O1 mean plane. The mean C—C and C—O(hydroxyl) bond lengths of 1.519 (2) and 1.422 (2) Å, respectively, in the sugar moiety compare well with similar averages observed in pyranose sugars (Berman et al., 1967). The two endocyclic C—O bonds, C1—O1 and C5—O1, are nearly equal [1.432 (2) and 1.422 (2) Å, respectively]. The conformation about the exocyclic C1—C6 bond is gauche–trans, with torsion angles O2—C6—C1—O1 = −59.7 (2)° and O2—C6—C1—C2 = 60.9 (2)°.

The heterocyclic phenyl-1,3,4-thiadiazole ring is planar to within experimental error and the lengths of the endocyclic bonds, C15—N1 = 1.299 (2) Å and C16—N2 = 1.306 (2) Å, clearly indicate that they are double bonds. The N1—N2 bond length of 1.375 (2) Å is slightly shorter than the single-bond value of 1.393 (4) Å in the hydrochloride of 5-(4-methoxyphenyl)-4-phenyl-1,3,4-thiadiazolium-2-phenylaminide (Cheung et al., 1992). The large deviation of the bond angle (Value?) in the ring from the value of 120° usually found in trigonal planar arrangements is common in five-membered rings (Downie et al., 1972). The phenyl ring linked to atom C16 forms a dihedral angle of 16.95 (6)° with the heterocyclic plane.

The S atom of the thioglucosidic linkage bridges the sugar and heterocyclic rings. The dihedral angles between the mean plane of the sugar ring and the thiadiazole and phenyl planes are 49.54 (4) and 33.42 (5)°, respectively. The orientation of the thiadiazole moiety relative to the glucose ring may be described by the torsion angles N1—C15—S1—C5 = −106.9 (2)°, S2—C15—S1—C5 = 78.2 (1)°, C15—S1—C5—O1 = −67.1 (1)° and C15—S1—C5—C4 = 176.3 (1)°.

S2. Experimental

2-Phenyl-5-thiol-1,3,4-thiadiazole (0.582 g, 3 mmol), α-acetobromoglucose (1.230 g, 3 mol) and KOH (0.168 g, 3 mmol) were reacted at room temperature for 12 h. The product was obtained via column-chromatograpic purification and the crystals were recrystallized by slow evaporation from petroleum ether–ethyl acetate (4:1) (m.p. 424–426 K). Spectroscopic analysis: ¹H NMR (400 MHz, CDCl₃, δ, p.p.m): 2.018 (s, 3 H), 2.040 (s, 3 H), 2.060 (s, 3 H), 2.088 (s, 3 H), 3.845–3.886 (m, 1 H), 4.166 (dd, J = 2.0 and 12.8 Hz, 1 H), 4.302 (dd, J = 4.8 and 12.8 Hz, 1 H), 5.137–5.205 (m, 2 H), 5.309 (t, J = 9.2 Hz, 1 H), 5.444 (d, J = 10.4 Hz, 1 H), 7.459–7.511 (m, 3 H), 7.899–7.922 (m, 2 H).

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.97 Å and were included in the final cycles of refinement [U_iso(H) = 1.2Ueq(parent atom)].

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

Fig. 1. A view of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

5-Phenyl-1,3,4-thiadiazol-2-yl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-Glucopyranoside

Crystal data

C22H24N2O9S2	F(000) = 1096.0
Mr = 524.56	Dx = 1.440 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7511 reflections
a = 8.010 (2) Å	θ = 3.2–27.5°
b = 10.526 (2) Å	µ = 0.28 mm^−1
c = 28.685 (6) Å	T = 173 K
V = 2418.7 (9) Å^3	Block, colourless
Z = 4	0.35 × 0.25 × 0.20 mm

Data collection

Rigaku/MSC Mercury CCD area-detector diffractometer	5151 reflections with F^2 > 2σ(F^2)
Detector resolution: 28.57 pixels mm^-1	Rint = 0.037
ω scans	θmax = 27.5°
Absorption correction: multi-scan TEXSAN (Molecular Structure Corporation, 1999)	h = −10→9
Tmin = 0.825, Tmax = 0.947	k = −11→13
19569 measured reflections	l = −37→37
5524 independent reflections

Refinement

Refinement on F	w = 1/[σ^2(Fo) + 0.00063|Fo|^2]
R[F^2 > 2σ(F^2)] = 0.033	(Δ/σ)max = 0.001
wR(F^2) = 0.046	Δρmax = 0.25 e Å^−3
S = 1.06	Δρmin = −0.24 e Å^−3
5499 reflections	Absolute structure: Flack (1983), with how many Friedel pairs
317 parameters	Absolute structure parameter: 0.00 (5)
H-atom parameters constrained

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
S1	0.27622 (5)	0.20966 (4)	0.68265 (2)	0.0300 (1)
S2	−0.05465 (6)	0.13378 (4)	0.72770 (2)	0.0343 (1)
O1	0.1245 (1)	0.0409 (1)	0.62962 (4)	0.0259 (3)
O2	0.0702 (2)	−0.2128 (1)	0.61743 (5)	0.0377 (3)
O3	−0.0567 (2)	−0.3742 (1)	0.58108 (8)	0.0690 (6)
O4	0.1401 (2)	−0.0523 (1)	0.50689 (4)	0.0268 (3)
O5	0.2289 (2)	−0.2543 (1)	0.50827 (6)	0.0525 (4)
O6	0.4793 (1)	0.0391 (1)	0.52769 (4)	0.0245 (3)
O7	0.4833 (2)	0.2033 (1)	0.47712 (5)	0.0378 (3)
O8	0.4728 (1)	0.2408 (1)	0.59405 (4)	0.0261 (3)
O9	0.6921 (2)	0.1407 (2)	0.62615 (8)	0.0667 (6)
N1	0.0320 (2)	0.3625 (1)	0.71316 (7)	0.0439 (5)
N2	−0.1200 (2)	0.3682 (1)	0.73523 (7)	0.0466 (5)
C1	0.0629 (2)	−0.0035 (1)	0.58570 (6)	0.0241 (4)
C2	0.2089 (2)	−0.0298 (1)	0.55251 (5)	0.0224 (4)
C3	0.3279 (2)	0.0825 (1)	0.54928 (6)	0.0221 (3)
C4	0.3733 (2)	0.1283 (1)	0.59786 (5)	0.0222 (3)
C5	0.2145 (2)	0.1563 (1)	0.62533 (6)	0.0237 (4)
C6	−0.0385 (2)	−0.1212 (2)	0.59557 (6)	0.0332 (4)
C7	0.0485 (2)	−0.3363 (2)	0.60692 (7)	0.0343 (4)
C8	0.1716 (3)	−0.4169 (2)	0.63204 (7)	0.0472 (6)
C9	0.1569 (2)	−0.1711 (2)	0.48867 (6)	0.0290 (4)
C10	0.0727 (2)	−0.1824 (2)	0.44275 (7)	0.0383 (5)
C11	0.5506 (2)	0.1125 (1)	0.49426 (6)	0.0246 (4)
C12	0.7215 (2)	0.0655 (2)	0.48357 (7)	0.0316 (4)
C13	0.6316 (2)	0.2361 (2)	0.61116 (7)	0.0350 (5)
C14	0.7128 (3)	0.3628 (2)	0.60825 (8)	0.0471 (6)
C15	0.0809 (2)	0.2461 (1)	0.70673 (6)	0.0255 (4)
C16	−0.1812 (2)	0.2566 (1)	0.74498 (6)	0.0251 (4)
C17	−0.3421 (2)	0.2403 (2)	0.76863 (6)	0.0266 (4)
C18	−0.4251 (2)	0.1241 (2)	0.76842 (7)	0.0355 (5)
C19	−0.5789 (3)	0.1125 (2)	0.79038 (7)	0.0432 (5)
C20	−0.6484 (3)	0.2145 (2)	0.81284 (7)	0.0467 (6)
C21	−0.5659 (3)	0.3302 (2)	0.81388 (8)	0.0474 (6)
C22	−0.4124 (3)	0.3431 (2)	0.79225 (7)	0.0380 (5)
H1	−0.0089	0.0609	0.5722	0.0289*
H2	0.2693	−0.1045	0.5629	0.0269*
H3)	0.2783	0.1508	0.5313	0.0266*
H4	0.4368	0.0628	0.6137	0.0267*
H5	0.1478	0.2203	0.6097	0.0284*
H6	−0.0822	−0.1556	0.5667	0.0399*
H7	−0.1303	−0.1007	0.6163	0.0399*
H8	0.1914	−0.4940	0.6144	0.0566*
H9	0.2756	−0.3707	0.6356	0.0566*
H10	0.1280	−0.4386	0.6626	0.0566*
H11	−0.0379	−0.1453	0.4446	0.0460*
H12	0.1375	−0.1378	0.4193	0.0460*
H13	0.0636	−0.2713	0.4343	0.0460*
H14	0.7198	−0.0264	0.4812	0.0379*
H15	0.7588	0.1015	0.4542	0.0379*
H16	0.7972	0.0909	0.5083	0.0379*
H17	0.8246	0.3577	0.6211	0.0565*
H18	0.7187	0.3894	0.5759	0.0565*
H19	0.6480	0.4241	0.6259	0.0565*
H20	−0.3756	0.0514	0.7529	0.0426*
H21	−0.6374	0.0318	0.7898	0.0518*
H22	−0.7559	0.2057	0.8281	0.0561*
H23	−0.6157	0.4022	0.8298	0.0569*
H24	−0.3536	0.4236	0.7935	0.0456*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0261 (2)	0.0371 (2)	0.0269 (2)	0.0004 (2)	0.0008 (2)	−0.0063 (2)
S2	0.0336 (2)	0.0195 (2)	0.0496 (3)	0.0004 (2)	0.0098 (2)	−0.0001 (2)
O1	0.0282 (6)	0.0245 (5)	0.0250 (6)	−0.0034 (5)	0.0033 (5)	0.0010 (4)
O2	0.0568 (8)	0.0265 (6)	0.0298 (6)	−0.0114 (6)	−0.0055 (6)	0.0038 (5)
O3	0.0485 (9)	0.0416 (8)	0.117 (2)	−0.0038 (8)	−0.027 (1)	−0.0244 (10)
O4	0.0298 (6)	0.0244 (5)	0.0262 (6)	0.0032 (5)	−0.0034 (5)	−0.0031 (4)
O5	0.086 (1)	0.0249 (6)	0.0467 (9)	0.0127 (7)	−0.0112 (8)	−0.0048 (6)
O6	0.0257 (6)	0.0205 (5)	0.0274 (6)	0.0032 (4)	0.0062 (5)	0.0022 (4)
O7	0.0398 (7)	0.0314 (6)	0.0422 (7)	0.0059 (6)	0.0084 (6)	0.0143 (6)
O8	0.0254 (6)	0.0207 (5)	0.0323 (6)	−0.0035 (4)	0.0004 (5)	0.0018 (4)
O9	0.0392 (9)	0.0521 (9)	0.109 (2)	−0.0028 (7)	−0.0309 (9)	0.020 (1)
N1	0.0446 (9)	0.0257 (7)	0.062 (1)	−0.0017 (7)	0.0295 (8)	−0.0003 (7)
N2	0.0466 (10)	0.0242 (7)	0.069 (1)	0.0010 (7)	0.0314 (9)	0.0031 (8)
C1	0.0233 (7)	0.0225 (7)	0.0264 (8)	−0.0022 (6)	0.0004 (7)	−0.0013 (6)
C2	0.0232 (7)	0.0207 (7)	0.0234 (7)	0.0014 (6)	−0.0009 (6)	0.0007 (6)
C3	0.0238 (7)	0.0169 (6)	0.0257 (7)	0.0043 (6)	0.0022 (6)	0.0012 (6)
C4	0.0241 (7)	0.0164 (6)	0.0261 (7)	0.0004 (6)	0.0012 (6)	0.0015 (6)
C5	0.0240 (7)	0.0221 (7)	0.0249 (7)	0.0001 (6)	−0.0002 (6)	0.0006 (6)
C6	0.0309 (8)	0.0331 (8)	0.0358 (9)	−0.0075 (8)	0.0034 (7)	0.0019 (7)
C7	0.0356 (9)	0.0294 (8)	0.0378 (9)	−0.0112 (7)	0.0117 (8)	−0.0036 (7)
C8	0.074 (2)	0.0338 (9)	0.0335 (10)	−0.0056 (10)	−0.003 (1)	0.0040 (8)
C9	0.0280 (8)	0.0265 (8)	0.0327 (9)	−0.0041 (6)	0.0058 (7)	−0.0063 (7)
C10	0.0312 (9)	0.050 (1)	0.0340 (9)	−0.0054 (8)	0.0024 (8)	−0.0130 (8)
C11	0.0283 (7)	0.0210 (7)	0.0245 (7)	−0.0034 (6)	0.0015 (6)	−0.0014 (6)
C12	0.0280 (8)	0.0273 (8)	0.0396 (9)	−0.0026 (7)	0.0078 (8)	0.0000 (7)
C13	0.0273 (8)	0.0396 (10)	0.0381 (10)	−0.0056 (8)	−0.0023 (8)	−0.0018 (8)
C14	0.040 (1)	0.045 (1)	0.056 (1)	−0.0165 (10)	0.0018 (10)	−0.0071 (10)
C15	0.0294 (8)	0.0239 (7)	0.0233 (8)	−0.0012 (6)	0.0030 (6)	−0.0016 (6)
C16	0.0295 (8)	0.0220 (7)	0.0237 (7)	0.0015 (6)	0.0013 (6)	0.0001 (6)
C17	0.0280 (8)	0.0291 (8)	0.0227 (7)	−0.0003 (6)	−0.0008 (6)	0.0041 (6)
C18	0.0385 (10)	0.0379 (9)	0.0301 (9)	−0.0099 (8)	0.0003 (7)	−0.0036 (7)
C19	0.041 (1)	0.053 (1)	0.0354 (10)	−0.0194 (10)	0.0014 (8)	0.0008 (9)
C20	0.0342 (10)	0.073 (1)	0.0329 (10)	−0.010 (1)	0.0070 (8)	0.001 (1)
C21	0.043 (1)	0.054 (1)	0.045 (1)	0.0030 (9)	0.017 (1)	0.0016 (9)
C22	0.040 (1)	0.0340 (9)	0.041 (1)	0.0001 (8)	0.0133 (8)	0.0017 (8)

Geometric parameters (Å, º)

S1—C5	1.807 (2)	C17—C18	1.392 (2)
S1—C15	1.753 (2)	C17—C22	1.396 (2)
S2—C15	1.715 (2)	C18—C19	1.389 (3)
S2—C16	1.716 (2)	C19—C20	1.370 (3)
O1—C1	1.431 (2)	C20—C21	1.386 (3)
O1—C5	1.418 (2)	C21—C22	1.384 (3)
O2—C6	1.442 (2)	C1—H1	0.9700
O2—C7	1.346 (2)	C2—H2	0.9700
O3—C7	1.191 (3)	C3—H3	0.9700
O4—C2	1.440 (2)	C4—H4	0.9700
O4—C9	1.362 (2)	C5—H5	0.9700
O5—C9	1.190 (2)	C6—H6	0.9700
O6—C3	1.436 (2)	C6—H7	0.9700
O6—C11	1.357 (2)	C8—H8	0.9700
O7—C11	1.202 (2)	C8—H9	0.9700
O8—C4	1.433 (2)	C8—H10	0.9700
O8—C13	1.364 (2)	C10—H11	0.9700
O9—C13	1.195 (3)	C10—H12	0.9700
N1—N2	1.374 (2)	C10—H13	0.9700
N1—C15	1.299 (2)	C12—H14	0.9700
N2—C16	1.303 (2)	C12—H15	0.9700
C1—C2	1.533 (2)	C12—H16	0.9700
C1—C6	1.509 (2)	C14—H17	0.9700
C2—C3	1.521 (2)	C14—H18	0.9700
C3—C4	1.518 (2)	C14—H19	0.9700
C4—C5	1.525 (2)	C18—H20	0.9700
C7—C8	1.487 (3)	C19—H21	0.9700
C9—C10	1.484 (3)	C20—H22	0.9700
C11—C12	1.487 (2)	C21—H23	0.9700
C13—C14	1.486 (3)	C22—H24	0.9700
C16—C17	1.467 (2)
S1···O8	3.0077 (14)	C13···O6	3.394 (2)
S1···C13	3.519 (2)	C13···S1	3.519 (2)
S1···C18^i	3.548 (2)	C14···O3^xi	3.418 (3)
S1···C19^i	3.456 (2)	C14···O7^vii	3.343 (3)
S2···O1	3.3061 (15)	C17···C8^viii	3.567 (3)
S2···N2	2.5317 (13)	C18···C8^viii	3.530 (3)
S2···N1^ii	3.3264 (17)	C18···S1^xii	3.548 (2)
S2···N2^ii	3.3019 (16)	C19···S1^xii	3.456 (2)
S1···H24^ii	3.1500	C7···H22^xiii	3.0300
S2···H20	2.8100	C9···H6	2.9500
O1···S2	3.3061 (15)	C12···H8^v	2.9200
O1···O2	2.7281 (17)	C12···H3^vii	3.0500
O2···O1	2.7281 (17)	C14···H12^vii	3.0600
O3···C9^iii	3.081 (3)	C17···H9^viii	3.0300
O3···C14^iv	3.418 (3)	C18···H9^viii	3.0000
O3···C10^iii	3.104 (2)	C21···H20^x	3.0500
O4···O6	2.9434 (19)	C22···H20^x	3.0600
O5···C7	3.293 (3)	H1···H5	2.3600
O5···C12^iii	3.285 (2)	H1···H16^xii	2.4200
O5···C10^v	3.163 (2)	H1···O7^vi	2.8600
O6···O4	2.9434 (19)	H2···O2	2.5100
O6···C13	3.394 (2)	H2···O5	2.2500
O6···O8	2.8520 (17)	H3···O7	2.3300
O7···C14^vi	3.343 (3)	H3···H5	2.5900
O7···C12^vi	3.405 (2)	H3···O7^vi	2.8300
O8···C11	3.226 (2)	H3···C12^vi	3.0500
O8···O6	2.8520 (17)	H4···O9	2.2300
O8···S1	3.0077 (14)	H5···H1	2.3600
O2···H2	2.5100	H5···H3	2.5900
O3···H12^iii	2.4500	H6···O3	2.3500
O3···H6	2.3500	H6···O4	2.7000
O4···H6	2.7000	H6···C9	2.9500
O5···H2	2.2500	H6···O5^iii	2.8000
O5···H14^iii	2.3300	H7···H23^xiii	2.5600
O5···H6^v	2.8000	H8···C12^iii	2.9200
O5···H11^v	2.5400	H8···H15^iii	2.3300
O7···H3^vii	2.8300	H9···C17^ii	3.0300
O7···H1^vii	2.8600	H9···C18^ii	3.0000
O7···H3	2.3300	H10···N1^xiv	2.6600
O7···H16^vi	2.6600	H11···H14^xii	2.5400
O7···H18^vi	2.7900	H11···O5^iii	2.5400
O8···H15^vi	2.7600	H12···O3^v	2.4500
O9···H4	2.2300	H12···C14^vi	3.0600
O9···H23^ii	2.8800	H12···H19^vi	2.6000
N1···S2	2.5400 (14)	H14···H11^i	2.5400
N1···S2^viii	3.3264 (17)	H14···O5^v	2.3300
N2···S2	2.5317 (13)	H15···O8^vii	2.7600
N2···S2^viii	3.3019 (16)	H15···H8^v	2.3300
N1···H10^ix	2.6600	H16···H1^i	2.4200
N2···H24	2.5800	H16···O7^vii	2.6600
N2···H21^x	2.6900	H18···O7^vii	2.7900
C6···C9	3.483 (3)	H19···H12^vii	2.6000
C7···O5	3.293 (3)	H20···S2	2.8100
C8···C17^ii	3.567 (3)	H20···C21^xiii	3.0500
C8···C18^ii	3.530 (3)	H20···C22^xiii	3.0600
C9···C6	3.483 (3)	H21···N2^xiii	2.6900
C9···O3^v	3.081 (3)	H22···C7^x	3.0300
C10···O5^iii	3.163 (2)	H23···O9^viii	2.8800
C10···O3^v	3.104 (2)	H23···H7^x	2.5600
C11···O8	3.226 (2)	H24···N2	2.5800
C12···O7^vii	3.405 (2)	H24···S1^viii	3.1500
C12···O5^v	3.285 (2)
C5—S1—C15	100.53 (8)	C6—C1—H1	109.00
C15—S2—C16	87.45 (8)	O4—C2—H2	110.00
C1—O1—C5	112.2 (1)	C1—C2—H2	110.00
C6—O2—C7	118.0 (2)	C3—C2—H2	110.00
C2—O4—C9	117.5 (1)	O6—C3—H3	111.00
C3—O6—C11	118.6 (1)	C2—C3—H3	111.00
C4—O8—C13	117.5 (1)	C4—C3—H3	111.00
N2—N1—C15	112.0 (1)	O8—C4—H4	109.00
N1—N2—C16	113.1 (1)	C3—C4—H4	109.00
O1—C1—C2	110.0 (1)	C5—C4—H4	109.00
O1—C1—C6	106.8 (1)	S1—C5—H5	111.00
C2—C1—C6	112.3 (1)	O1—C5—H5	111.00
O4—C2—C1	107.6 (1)	C4—C5—H5	111.00
O4—C2—C3	108.2 (1)	O2—C6—H6	110.00
C1—C2—C3	112.0 (1)	O2—C6—H7	110.00
O6—C3—C2	108.0 (1)	C1—C6—H6	110.00
O6—C3—C4	107.1 (1)	C1—C6—H7	110.00
C2—C3—C4	109.9 (1)	H6—C6—H7	109.00
O8—C4—C3	109.0 (1)	C7—C8—H8	109.00
O8—C4—C5	110.1 (1)	C7—C8—H9	110.00
C3—C4—C5	109.6 (1)	C7—C8—H10	109.00
S1—C5—O1	109.1 (1)	H8—C8—H9	110.00
S1—C5—C4	107.6 (1)	H8—C8—H10	109.00
O1—C5—C4	107.7 (1)	H9—C8—H10	109.00
O2—C6—C1	107.8 (1)	C9—C10—H11	110.00
O2—C7—O3	123.7 (2)	C9—C10—H12	109.00
O2—C7—C8	110.9 (2)	C9—C10—H13	109.00
O3—C7—C8	125.4 (2)	H11—C10—H12	109.00
O4—C9—O5	122.9 (2)	H11—C10—H13	109.00
O4—C9—C10	111.6 (2)	H12—C10—H13	109.00
O5—C9—C10	125.5 (2)	C11—C12—H14	109.00
O6—C11—O7	123.5 (2)	C11—C12—H15	109.00
O6—C11—C12	110.1 (1)	C11—C12—H16	109.00
O7—C11—C12	126.4 (2)	H14—C12—H15	109.00
O8—C13—O9	122.5 (2)	H14—C12—H16	110.00
O8—C13—C14	110.8 (2)	H15—C12—H16	110.00
O9—C13—C14	126.7 (2)	C13—C14—H17	109.00
S1—C15—S2	123.53 (9)	C13—C14—H18	110.00
S1—C15—N1	122.1 (1)	C13—C14—H19	109.00
S2—C15—N1	114.2 (1)	H17—C14—H18	110.00
S2—C16—N2	113.3 (1)	H17—C14—H19	109.00
S2—C16—C17	124.4 (1)	H18—C14—H19	109.00
N2—C16—C17	122.3 (1)	C17—C18—H20	120.00
C16—C17—C18	121.4 (2)	C19—C18—H20	120.00
C16—C17—C22	119.2 (1)	C18—C19—H21	120.00
C18—C17—C22	119.4 (2)	C20—C19—H21	120.00
C17—C18—C19	119.9 (2)	C19—C20—H22	120.00
C18—C19—C20	120.3 (2)	C21—C20—H22	120.00
C19—C20—C21	120.3 (2)	C20—C21—H23	120.00
C20—C21—C22	120.0 (2)	C22—C21—H23	120.00
C17—C22—C21	120.0 (2)	C17—C22—H24	120.00
O1—C1—H1	109.00	C21—C22—H24	120.00
C2—C1—H1	109.00
S1—C5—O1—C1	176.6 (1)	N2—C16—C17—C18	163.6 (2)
S1—C5—C4—O8	−60.2 (1)	N2—C16—C17—C22	−17.1 (3)
S1—C5—C4—C3	179.84 (10)	C1—O1—C5—C4	−67.0 (2)
S1—C15—S2—C16	175.9 (1)	C1—C2—O4—C9	−113.7 (1)
S1—C15—N1—N2	−176.0 (1)	C1—C2—C3—C4	49.0 (2)
S2—C15—S1—C5	78.1 (1)	C1—C6—O2—C7	−143.7 (2)
S2—C15—N1—N2	−0.6 (2)	C2—O4—C9—C10	177.0 (1)
S2—C16—N2—N1	0.2 (2)	C2—C1—O1—C5	61.4 (2)
S2—C16—C17—C18	−16.7 (2)	C2—C3—O6—C11	136.0 (1)
S2—C16—C17—C22	162.6 (1)	C2—C3—C4—C5	−54.2 (2)
O1—C1—C2—O4	−170.1 (1)	C3—O6—C11—C12	168.3 (1)
O1—C1—C2—C3	−51.3 (2)	C3—C2—O4—C9	125.0 (1)
O1—C1—C6—O2	−59.6 (2)	C3—C2—C1—C6	−170.1 (1)
O1—C5—S1—C15	−67.2 (1)	C3—C4—O8—C13	−117.8 (2)
O1—C5—C4—O8	−177.7 (1)	C4—O8—C13—C14	−175.2 (2)
O1—C5—C4—C3	62.4 (2)	C4—C3—O6—C11	−105.7 (1)
O2—C6—C1—C2	61.0 (2)	C4—C5—S1—C15	176.3 (1)
O3—C7—O2—C6	−1.0 (3)	C5—O1—C1—C6	−176.6 (1)
O4—C2—C1—C6	71.1 (2)	C5—C4—O8—C13	121.9 (1)
O4—C2—C3—O6	−76.1 (1)	C6—O2—C7—C8	179.4 (2)
O4—C2—C3—C4	167.4 (1)	C15—S2—C16—C17	179.9 (2)
O5—C9—O4—C2	−2.0 (2)	C15—N1—N2—C16	0.2 (3)
O6—C3—C2—C1	165.5 (1)	C16—C17—C18—C19	−178.7 (2)
O6—C3—C4—O8	68.2 (1)	C16—C17—C22—C21	178.6 (2)
O6—C3—C4—C5	−171.2 (1)	C17—C18—C19—C20	−0.9 (3)
O7—C11—O6—C3	−10.4 (2)	C17—C22—C21—C20	1.2 (3)
O8—C4—C3—C2	−174.8 (1)	C18—C17—C22—C21	−2.1 (3)
O9—C13—O8—C4	4.8 (3)	C18—C19—C20—C21	0.0 (3)
N1—N2—C16—C17	179.9 (2)	C19—C18—C17—C22	2.0 (3)
N1—C15—S1—C5	−107.0 (2)	C19—C20—C21—C22	−0.1 (4)
N1—C15—S2—C16	0.5 (2)	C19—C20—C21—C22	−0.1 (4)
N2—C16—S2—C15	−0.4 (2)

Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z+3/2; (iii) x−1/2, −y−1/2, −z+1; (iv) x−1, y−1, z; (v) x+1/2, −y−1/2, −z+1; (vi) x−1/2, −y+1/2, −z+1; (vii) x+1/2, −y+1/2, −z+1; (viii) −x, y+1/2, −z+3/2; (ix) x, y+1, z; (x) −x−1, y+1/2, −z+3/2; (xi) x+1, y+1, z; (xii) x−1, y, z; (xiii) −x−1, y−1/2, −z+3/2; (xiv) x, y−1, z.