A novel heterocyclic sulfon­amide: N-benzyl-5-[N-benzyl-N-(tert-butyl­oxy­carbonyl)­amino]-N-(tert-butyl­oxycarbonyl)-1,3,4-thia­diazo­le-2-sulfon­amide

The title compound, C₂₆H₃₂N₄O₆S₂, is a heterocyclic sulfon­amide which is a 1,3,4-thia­diazo­le derivative. Structural data for this compound are compared with those of related compounds.

S1. Comment

Since Davenport (1945) reported that thiophene-2-sulfonamide is a carbonic anhydrase (CA) inhibitor 40 times more active than other sulfonamides, many heterocyclic sulfonamides have been prepared. We have obtained and determined the crystal structures of several 1,3,4-thiadiazolesulfonamides following the method proposed by Young et al. (1956) with minor modifications (Alzuet et al., 1991a; Pedregosa et al., 1993). The results obtained by our group with these sulfonamides have rendered data which indicate a notable increase in CA inhibitory properties (Chufán et al., 2000). In addition, Kreb's (1948) investigations on compounds presenting the modified sulfonamido group has led to the conclusion that substitution within the sulfonamido group drastically affects inhibitory activity and increases lipoaffinity (Duffel et al., 1986). Based on these investigations, it was interesting to prepare compounds with the substituted sulfonamido group and to determine their crystal structures. Furthermore, following our programme for systematic studies on unsubstituted and substituted heterocyclic sulfonamides and their metal complexes (Alzuet et al., 1991b; Pedregosa et al., 1995), we will study the role of these bulky groups in CA inhibition and lipoaffinity.

In this work, we obtained the crystal structure of the title compound, (III), and compared it with related compounds, such as acetazolamide (5-acetylamino-1,3,4-thiadiazole-2-sulfonamide; Mathew & Palenik, 1974), 5-amino-1,3,4-thiadiazole-2-sulfonamide (Pedregosa et al., 1993), 5-tert-butyloxycarbonylamino-1,3,4-thiadiazole-2-sulfonamide (Pedregosa et al., 1995), 5-amino-1,3,4-thiadiazole-2-thiol (Downie et al., 1972) and 5-tert-butyloxycarbonylamino-1,3,4-thiadiazole-2-sulfonyl chloride (Pedregosa et al., 1996). The main features of the new structure are planarity of the 1,3,4-thiadiazole ring, distorted tetrahedral geometry in the sulfonamide group and coplanar arrangement of the disubstituted 5-amino group and the 1,3,4-thiadiazole ring are in agreement with the compared compounds.

S2. Experimental

The synthesis of (III) was performed in three steps. In the first step, the acid hydrolysis of acetazolamide (I) to give 5-amino-1,3,4-thiadiazole-2-sulfonamide was performed following the literature procedure of Supuran et al. (1990). In the second step (group protection), the product (0.5 g, 2.77 mmol) of the previous reaction, triethylamine (Et₃N, Aldrich, 1 ml, 7.2 mmol), 4-dimethyl-aminopyridine (4-DMAP, Aldrich, 100 mg, 4.6 mmol) and di-tert-butyldicarbonate [(BOC)₂O, Aldrich, 1.2 g, 5.54 mmol] were added in order and with permanent stirring at room temperature to CH₂Cl₂ (50 ml, Merck) under an inert argon atmosphere. The reaction was followed by thin-layer chromatography (TLC). After 18 h, the solvent was removed by vacuum extraction. The obtained solid (II) was purified by treatment with 1 N HCl, filtered and washed with distilled water (3–4 times) and hexane (3–4 times). Recrystallization from ethanol/dichloromethane (1:1) rendered crystals that were washed with ethanol/hexane (1:20) giving 0.9 g (86%) of (II) (m.p. 436–438 K). Finally, the third step consisted of deprotonation of (II). Lithium diisopropylamide (LDA) was prepared by addition of diisopropylamine (2 ml, 14.28 mmol) and n-butyllithium (1.32 ml, 14.23 mmol) to tetrahydrofuran (50 ml, Supelco) on an acetone/solid CO₂ cold bath (213 K) under an inert argon atmosphere. The mixture was stabilized at 213 K for 30 min. Subsequently, (II) (0.5 g, 1.32 mmol) was added. After 30 min of stabilization at the same temperature, benzylbromide (0.4 ml, 3.29 mmol) was added. The reaction was followed by TLC. After 24 h, when the bath reached room temperature, the solvent was removed by vacuum extraction. The obtained solid (III), was purified with 1 N HCl and washed with distilled water and hexane. Recrystallization was performed as described in step two and 0.55 g (75% yield) of (III) were isolated (m.p. 389–391 K).

S3. Refinement

The H atoms were placed geometrically and treated with a riding model in which the C—H distance, common to all H atoms bonded to the same C, was free to refine.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1989); cell refinement: CAD-4 EXPRESS; data reduction: XRAY80 (Stewart, 1978); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).

(I)

Crystal data

C26H32N4O6S2	F(000) = 1184
Mr = 560.68	Dx = 1.277 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
a = 15.408 (1) Å	Cell parameters from 25 reflections
b = 10.256 (1) Å	θ = 9.5–13.6°
c = 19.402 (1) Å	µ = 0.23 mm^−1
β = 107.91 (1)°	T = 293 K
V = 2917.4 (4) Å^3	Prismatic, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	θmax = 25.0°, θmin = 1.5°
ω/2q scans	h = 0→18
5807 measured reflections	k = 0→12
5114 independent reflections	l = −23→21
3022 reflections with I > 2σ(I)	3 standard reflections every 90 min
Rint = 0.007	intensity decay: none

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0755P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5114 reflections	Δρmax = 0.23 e Å^−3
360 parameters	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
S1	0.74709 (6)	0.23860 (8)	0.07908 (5)	0.0580 (3)
S2	0.80711 (7)	0.50366 (8)	0.04779 (5)	0.0594 (3)
O1	0.85615 (19)	0.5836 (2)	0.10679 (13)	0.0757 (7)
O2	0.71069 (17)	0.5092 (2)	0.02285 (13)	0.0714 (7)
O3	0.77776 (18)	0.3621 (2)	−0.08413 (13)	0.0705 (7)
O4	0.85891 (18)	0.5044 (2)	−0.12896 (13)	0.0743 (7)
O5	0.73106 (16)	−0.1540 (2)	0.15431 (13)	0.0674 (7)
O6	0.66786 (17)	0.0395 (2)	0.11114 (15)	0.0740 (7)
N1	0.91477 (19)	0.1650 (3)	0.11328 (15)	0.0606 (7)
N2	0.9133 (2)	0.2928 (3)	0.08984 (15)	0.0628 (7)
N3	0.81869 (18)	0.0010 (2)	0.13092 (14)	0.0536 (6)
N4	0.85090 (19)	0.5357 (3)	−0.01810 (14)	0.0585 (7)
C1	0.8331 (2)	0.1256 (3)	0.11055 (16)	0.0502 (7)
C2	0.8319 (2)	0.3399 (3)	0.07133 (17)	0.0540 (8)
C3	0.8242 (2)	0.4569 (3)	−0.08026 (18)	0.0585 (8)
C4	0.8442 (3)	0.4416 (4)	−0.20077 (18)	0.0711 (10)
C5	0.8853 (4)	0.3067 (5)	−0.1893 (3)	0.1108 (18)
H5A	0.9511	0.3130	−0.1628	0.166*
H5B	0.8769	0.2647	−0.2368	0.166*
H5C	0.8548	0.2540	−0.1609	0.166*
C6	0.7440 (3)	0.4365 (5)	−0.2411 (2)	0.1034 (16)
H6A	0.7185	0.527	−0.2477	0.155*
H6B	0.7119	0.3836	−0.2127	0.155*
H6C	0.7345	0.3951	−0.2898	0.155*
C7	0.8959 (3)	0.5312 (5)	−0.2356 (2)	0.121 (2)
H7A	0.957	0.5307	−0.2091	0.182*
H7B	0.8733	0.614	−0.2371	0.182*
H7C	0.8894	0.5031	−0.2820	0.182*
C8	0.9070 (2)	0.6554 (3)	−0.0130 (2)	0.0639 (9)
H8A	0.9484	0.6434	−0.0444	0.077*
H8B	0.9475	0.6659	0.0390	0.077*
C9	0.8525 (2)	0.7789 (3)	−0.03595 (17)	0.0565 (8)
C10	0.8998 (3)	0.8900 (4)	−0.0437 (2)	0.0805 (12)
H10	0.971	0.8846	−0.0373	0.097*
C11	0.8547 (4)	1.0075 (4)	−0.0597 (2)	0.0943 (15)
H11	0.8853	1.076	−0.0641	0.113*
C12	0.7651 (4)	1.0188 (4)	−0.0686 (2)	0.0878 (14)
H12	0.7343	1.105	−0.0796	0.105*
C13	0.7170 (3)	0.9111 (4)	−0.0625 (2)	0.0897 (14)
H13	0.656	0.9172	−0.0685	0.108*
C14	0.7613 (3)	0.7904 (4)	−0.0469 (2)	0.0822 (12)
H14	0.7305	0.723	−0.0442	0.099*
C15	0.7319 (3)	−0.0335 (3)	0.13064 (19)	0.0617 (9)
C16	0.6455 (3)	−0.2134 (4)	0.1612 (2)	0.0690 (10)
C17	0.6114 (3)	−0.1342 (4)	0.2126 (3)	0.1069 (18)
H17A	0.6588	−0.1302	0.2601	0.160*
H17B	0.5561	−0.1753	0.2182	0.160*
H17C	0.5968	−0.045	0.1933	0.160*
C18	0.6792 (3)	−0.3456 (4)	0.1923 (3)	0.0909 (14)
H18A	0.7223	−0.3350	0.2394	0.136*
H18B	0.7078	−0.3888	0.1613	0.136*
H18C	0.6287	−0.3966	0.1958	0.136*
C19	0.5777 (3)	−0.2262 (5)	0.0865 (3)	0.1102 (19)
H19A	0.6029	−0.2761	0.057	0.165*
H19B	0.5633	−0.144	0.0661	0.165*
H19C	0.5251	−0.2664	0.0898	0.165*
C20	0.8973 (2)	−0.0930 (3)	0.15124 (19)	0.0649 (9)
H20A	0.8725	−0.189	0.1328	0.078*
H20B	0.9457	−0.0652	0.1237	0.078*
C21	0.9453 (2)	−0.0976 (3)	0.2313 (2)	0.0632 (9)
C22	0.9241 (3)	−0.1940 (4)	0.2735 (2)	0.0838 (12)
H22	0.877	−0.263	0.2498	0.101*
C23	0.9661 (3)	−0.1968 (6)	0.3474 (3)	0.1036 (17)
H23	0.9498	−0.262	0.3759	0.124*
C24	1.0306 (3)	−0.1070 (6)	0.3795 (3)	0.0994 (15)
H24	1.0637	−0.1104	0.438	0.119*
C25	1.0547 (3)	−0.0116 (5)	0.3388 (3)	0.0894 (13)
H25	1.104	0.055	0.3632	0.107*
C26	1.0121 (2)	−0.0073 (4)	0.2645 (2)	0.0735 (10)
H26	1.0288	0.0567	0.237	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0522 (5)	0.0580 (5)	0.0627 (5)	0.0018 (4)	0.0163 (4)	0.0064 (4)
S2	0.0704 (7)	0.0539 (5)	0.0567 (5)	0.0022 (4)	0.0236 (5)	0.0031 (4)
O1	0.107 (2)	0.0590 (14)	0.0616 (15)	−0.0059 (14)	0.0266 (15)	−0.0099 (12)
O2	0.0675 (17)	0.0697 (15)	0.0802 (17)	0.0114 (13)	0.0274 (14)	0.0150 (13)
O3	0.0841 (18)	0.0625 (14)	0.0633 (15)	−0.0141 (14)	0.0205 (13)	−0.0006 (12)
O4	0.094 (2)	0.0754 (16)	0.0604 (15)	−0.0146 (14)	0.0345 (14)	−0.0021 (12)
O5	0.0669 (16)	0.0627 (14)	0.0765 (16)	−0.0036 (12)	0.0276 (13)	0.0110 (12)
O6	0.0517 (15)	0.0693 (15)	0.100 (2)	0.0018 (13)	0.0220 (14)	0.0160 (14)
N1	0.0543 (18)	0.0579 (16)	0.0687 (18)	0.0007 (14)	0.0178 (15)	0.0089 (14)
N2	0.0604 (19)	0.0608 (17)	0.0687 (18)	−0.0045 (15)	0.0219 (15)	0.0048 (14)
N3	0.0497 (17)	0.0519 (14)	0.0582 (16)	−0.0002 (13)	0.0150 (13)	0.0039 (12)
N4	0.070 (2)	0.0557 (15)	0.0529 (16)	−0.0068 (14)	0.0239 (14)	0.0010 (13)
C1	0.051 (2)	0.0530 (17)	0.0442 (17)	0.0015 (15)	0.0113 (15)	0.0007 (14)
C2	0.057 (2)	0.0536 (18)	0.0507 (18)	−0.0038 (16)	0.0162 (17)	0.0011 (15)
C3	0.061 (2)	0.060 (2)	0.053 (2)	0.0046 (17)	0.0164 (17)	0.0069 (16)
C4	0.068 (3)	0.096 (3)	0.0475 (19)	0.003 (2)	0.0156 (19)	−0.0003 (19)
C5	0.118 (4)	0.122 (4)	0.090 (3)	0.037 (3)	0.028 (3)	−0.016 (3)
C6	0.075 (3)	0.157 (5)	0.071 (3)	0.009 (3)	0.011 (2)	0.015 (3)
C7	0.123 (4)	0.179 (6)	0.074 (3)	−0.044 (4)	0.049 (3)	−0.001 (3)
C8	0.060 (2)	0.062 (2)	0.067 (2)	−0.0085 (18)	0.0148 (18)	−0.0003 (17)
C9	0.064 (2)	0.0566 (19)	0.0454 (18)	−0.0134 (17)	0.0121 (16)	−0.0027 (14)
C10	0.084 (3)	0.071 (3)	0.076 (3)	−0.014 (2)	0.009 (2)	0.008 (2)
C11	0.120 (5)	0.065 (3)	0.081 (3)	−0.024 (3)	0.005 (3)	0.006 (2)
C12	0.135 (5)	0.065 (3)	0.057 (2)	0.015 (3)	0.019 (3)	0.0042 (19)
C13	0.089 (3)	0.094 (3)	0.088 (3)	0.021 (3)	0.031 (3)	0.027 (3)
C14	0.077 (3)	0.072 (2)	0.098 (3)	0.006 (2)	0.028 (2)	0.028 (2)
C15	0.066 (3)	0.062 (2)	0.059 (2)	−0.0017 (19)	0.0220 (19)	0.0016 (17)
C16	0.062 (2)	0.072 (2)	0.078 (3)	−0.0116 (19)	0.029 (2)	0.010 (2)
C17	0.126 (4)	0.096 (3)	0.131 (4)	0.002 (3)	0.087 (4)	0.001 (3)
C18	0.098 (3)	0.073 (3)	0.120 (4)	−0.011 (2)	0.060 (3)	0.015 (2)
C19	0.093 (4)	0.118 (4)	0.111 (4)	−0.038 (3)	0.018 (3)	0.012 (3)
C20	0.070 (2)	0.0580 (19)	0.071 (2)	0.0067 (18)	0.027 (2)	−0.0013 (17)
C21	0.048 (2)	0.070 (2)	0.070 (2)	0.0102 (18)	0.0169 (18)	0.0037 (19)
C22	0.065 (3)	0.092 (3)	0.085 (3)	0.000 (2)	0.009 (2)	0.024 (2)
C23	0.067 (3)	0.141 (4)	0.092 (3)	−0.004 (3)	0.008 (3)	0.042 (3)
C24	0.065 (3)	0.145 (5)	0.076 (3)	0.011 (3)	0.005 (2)	0.020 (3)
C25	0.058 (3)	0.112 (3)	0.087 (3)	0.003 (2)	0.005 (2)	−0.001 (3)
C26	0.048 (2)	0.081 (2)	0.087 (3)	0.003 (2)	0.013 (2)	0.002 (2)

Geometric parameters (Å, º)

S1—C2	1.712 (3)	C9—C10	1.386 (5)
S1—C1	1.725 (3)	C10—C11	1.378 (6)
S2—O2	1.415 (2)	C10—H10	1.07 (4)
S2—O1	1.422 (2)	C11—C12	1.343 (6)
S2—N4	1.652 (3)	C11—H11	0.87 (4)
S2—C2	1.752 (3)	C12—C13	1.355 (6)
O3—C3	1.196 (4)	C12—H12	1.00 (4)
O4—C3	1.314 (4)	C13—C14	1.401 (5)
O4—C4	1.488 (4)	C13—H13	0.91 (4)
O5—C15	1.320 (4)	C14—H14	0.85 (4)
O5—C16	1.495 (4)	C16—C17	1.502 (5)
O6—C15	1.203 (4)	C16—C19	1.509 (5)
N1—C1	1.307 (4)	C16—C18	1.509 (5)
N1—N2	1.385 (4)	C17—H17A	0.98 (3)
N2—C2	1.288 (4)	C17—H17B	0.98 (3)
N3—C1	1.376 (4)	C17—H17C	0.98 (3)
N3—C15	1.381 (4)	C18—H18A	0.96 (2)
N3—C20	1.503 (4)	C18—H18B	0.96 (2)
N4—C3	1.404 (4)	C18—H18C	0.96 (2)
N4—C8	1.487 (4)	C19—H19A	0.93 (3)
C4—C6	1.502 (5)	C19—H19B	0.93 (3)
C4—C7	1.506 (5)	C19—H19C	0.93 (3)
C4—C5	1.509 (6)	C20—C21	1.501 (5)
C5—H5A	0.99 (3)	C20—H20A	1.08 (2)
C5—H5B	0.98 (3)	C20—H20B	1.08 (2)
C5—H5C	0.98 (3)	C21—C22	1.385 (5)
C6—H6A	1.01 (3)	C21—C26	1.388 (5)
C6—H6B	1.01 (3)	C22—C23	1.379 (6)
C6—H6C	1.01 (3)	C22—H22	1.02 (4)
C7—H7A	0.92 (3)	C23—C24	1.358 (6)
C7—H7B	0.92 (3)	C23—H23	0.95 (4)
C7—H7C	0.92 (3)	C24—C25	1.378 (6)
C8—C9	1.509 (5)	C24—H24	1.10 (5)
C8—H8A	1.02 (2)	C25—C26	1.390 (6)
C8—H8B	1.02 (2)	C25—H25	1.02 (4)
C9—C14	1.360 (5)	C26—H26	0.93 (4)
C2—S1—C1	85.10 (16)	C12—C11—H11	118.9
O2—S2—O1	119.62 (16)	C10—C11—H11	118.9
O2—S2—N4	111.29 (15)	C11—C12—C13	119.1 (4)
O1—S2—N4	105.43 (15)	C11—C12—H12	120.4
O2—S2—C2	104.46 (15)	C13—C12—H12	120.4
O1—S2—C2	108.87 (15)	C12—C13—C14	119.7 (4)
N4—S2—C2	106.52 (14)	C12—C13—H13	120.1
C3—O4—C4	122.3 (3)	C14—C13—H13	120.1
C15—O5—C16	121.1 (3)	C9—C14—C13	121.5 (4)
C1—N1—N2	111.2 (3)	C9—C14—H14	119.3
C2—N2—N1	111.3 (3)	C13—C14—H14	119.3
C1—N3—C15	118.6 (3)	O6—C15—O5	126.6 (3)
C1—N3—C20	118.8 (3)	O6—C15—N3	122.8 (3)
C15—N3—C20	122.6 (3)	O5—C15—N3	110.6 (3)
C3—N4—C8	122.9 (3)	O5—C16—C17	109.7 (3)
C3—N4—S2	117.9 (2)	O5—C16—C19	108.6 (3)
C8—N4—S2	118.7 (2)	C17—C16—C19	113.9 (4)
N1—C1—N3	121.0 (3)	O5—C16—C18	101.4 (3)
N1—C1—S1	115.6 (2)	C17—C16—C18	111.5 (3)
N3—C1—S1	123.4 (2)	C19—C16—C18	111.0 (4)
N2—C2—S1	116.9 (2)	C16—C17—H17A	109.5
N2—C2—S2	123.2 (2)	C16—C17—H17B	109.5
S1—C2—S2	119.6 (2)	H17A—C17—H17B	109.5
O3—C3—O4	128.6 (3)	C16—C17—H17C	109.5
O3—C3—N4	122.3 (3)	H17A—C17—H17C	109.5
O4—C3—N4	109.1 (3)	H17B—C17—H17C	109.5
O4—C4—C6	109.8 (3)	C16—C18—H18A	109.5
O4—C4—C7	101.9 (3)	C16—C18—H18B	109.5
C6—C4—C7	112.9 (4)	H18A—C18—H18B	109.5
O4—C4—C5	108.9 (3)	C16—C18—H18C	109.5
C6—C4—C5	111.3 (4)	H18A—C18—H18C	109.5
C7—C4—C5	111.7 (4)	H18B—C18—H18C	109.5
C4—C5—H5A	109.5	C16—C19—H19A	109.5
C4—C5—H5B	109.5	C16—C19—H19B	109.5
H5A—C5—H5B	109.5	H19A—C19—H19B	109.5
C4—C5—H5C	109.5	C16—C19—H19C	109.5
H5A—C5—H5C	109.5	H19A—C19—H19C	109.5
H5B—C5—H5C	109.5	H19B—C19—H19C	109.5
C4—C6—H6A	109.5	C21—C20—N3	113.1 (3)
C4—C6—H6B	109.5	C21—C20—H20A	109.0
H6A—C6—H6B	109.5	N3—C20—H20A	109.0
C4—C6—H6C	109.5	C21—C20—H20B	109.0
H6A—C6—H6C	109.5	N3—C20—H20B	109.0
H6B—C6—H6C	109.5	H20A—C20—H20B	107.8
C4—C7—H7A	109.5	C22—C21—C26	118.5 (4)
C4—C7—H7B	109.5	C22—C21—C20	120.3 (4)
H7A—C7—H7B	109.5	C26—C21—C20	121.2 (3)
C4—C7—H7C	109.5	C23—C22—C21	120.6 (4)
H7A—C7—H7C	109.5	C23—C22—H22	119.7
H7B—C7—H7C	109.5	C21—C22—H22	119.7
N4—C8—C9	114.4 (3)	C24—C23—C22	120.4 (5)
N4—C8—H8A	108.7	C24—C23—H23	119.8
C9—C8—H8A	108.7	C22—C23—H23	119.8
N4—C8—H8B	108.7	C23—C24—C25	120.4 (5)
C9—C8—H8B	108.7	C23—C24—H24	119.8
H8A—C8—H8B	107.6	C25—C24—H24	119.8
C14—C9—C10	117.6 (4)	C24—C25—C26	119.5 (5)
C14—C9—C8	125.0 (3)	C24—C25—H25	120.2
C10—C9—C8	117.3 (3)	C26—C25—H25	120.2
C11—C10—C9	119.9 (4)	C21—C26—C25	120.5 (4)
C11—C10—H10	120.1	C21—C26—H26	119.8
C9—C10—H10	120.1	C25—C26—H26	119.8
C12—C11—C10	122.1 (4)
C1—N1—N2—C2	0.0 (4)	C3—N4—C8—C9	91.2 (4)
O2—S2—N4—C3	−57.6 (3)	S2—N4—C8—C9	−80.9 (3)
O1—S2—N4—C3	171.2 (3)	N4—C8—C9—C14	12.7 (5)
C2—S2—N4—C3	55.6 (3)	N4—C8—C9—C10	−169.9 (3)
O2—S2—N4—C8	114.8 (3)	C14—C9—C10—C11	2.1 (6)
O1—S2—N4—C8	−16.3 (3)	C8—C9—C10—C11	−175.6 (4)
C2—S2—N4—C8	−131.9 (3)	C9—C10—C11—C12	−0.4 (7)
N2—N1—C1—N3	179.5 (3)	C10—C11—C12—C13	−0.7 (7)
N2—N1—C1—S1	0.3 (4)	C11—C12—C13—C14	0.1 (7)
C15—N3—C1—N1	176.6 (3)	C10—C9—C14—C13	−2.6 (6)
C20—N3—C1—N1	−4.5 (4)	C8—C9—C14—C13	174.8 (4)
C15—N3—C1—S1	−4.2 (4)	C12—C13—C14—C9	1.6 (7)
C20—N3—C1—S1	174.6 (2)	C16—O5—C15—O6	−1.6 (5)
C2—S1—C1—N1	−0.3 (3)	C16—O5—C15—N3	178.3 (3)
C2—S1—C1—N3	−179.5 (3)	C1—N3—C15—O6	2.4 (5)
N1—N2—C2—S1	−0.2 (4)	C20—N3—C15—O6	−176.4 (3)
N1—N2—C2—S2	173.4 (2)	C1—N3—C15—O5	−177.5 (3)
C1—S1—C2—N2	0.3 (3)	C20—N3—C15—O5	3.7 (4)
C1—S1—C2—S2	−173.6 (2)	C15—O5—C16—C17	−59.8 (4)
O2—S2—C2—N2	172.9 (3)	C15—O5—C16—C19	65.3 (4)
O1—S2—C2—N2	−58.3 (3)	C15—O5—C16—C18	−177.8 (3)
N4—S2—C2—N2	55.0 (3)	C1—N3—C20—C21	94.7 (4)
O2—S2—C2—S1	−13.7 (2)	C15—N3—C20—C21	−86.5 (4)
O1—S2—C2—S1	115.2 (2)	N3—C20—C21—C22	97.0 (4)
N4—S2—C2—S1	−131.5 (2)	N3—C20—C21—C26	−83.7 (4)
C4—O4—C3—O3	−0.2 (6)	C26—C21—C22—C23	2.5 (6)
C4—O4—C3—N4	179.0 (3)	C20—C21—C22—C23	−178.2 (4)
C8—N4—C3—O3	−178.7 (3)	C21—C22—C23—C24	−1.7 (7)
S2—N4—C3—O3	−6.6 (5)	C22—C23—C24—C25	0.2 (8)
C8—N4—C3—O4	2.0 (4)	C23—C24—C25—C26	0.4 (7)
S2—N4—C3—O4	174.1 (2)	C22—C21—C26—C25	−1.8 (6)
C3—O4—C4—C6	59.8 (5)	C20—C21—C26—C25	178.9 (3)
C3—O4—C4—C7	179.7 (3)	C24—C25—C26—C21	0.4 (6)
C3—O4—C4—C5	−62.2 (5)