Éthyl 5-méthylthio-3-(4-nitrophényl)-3a-phényl-3a,4-dihydro-3H-[1,2,4]­triazolo[4,3-a][1,5]benzodiazépine-1-carboxylate

Condensation of N-p-nitrophenyl-C-ethoxycarbonylnitril­im­ine with 2-methylthio-4-phenyl-3H-1,5-benzodiazepine leads to the title compound, C₂₆H₂₃N₅O₄S. It has been established that 1,3-dipolar cycloaddition occurs on the C4 =N5 double bond of the 1,5-benzodiazepine.

S1. Comment

Développant nos travaux de recherche concernant la synthèse des dérivés de benzodiazépines (Baouid et al., 1994, 1996; Benelbaghdadi et al., 1997, 1998; Essaber et al., 1998), nous décrivons ici le comportement de la N-p-nitrophényl-C-éthoxycarbonylnitrilimine générée in situ à partir de la N-p-nitrophénylhydrazono-α-bromoglyoxylate d'éthyle (Huisgen & Koch, 1955; Sharp & Hamilton, 1946) en présence de la triéthylamine vis-à-vis de la 2-méthylthio-4-phényl-3H-1,5-benzodiazépine (Nardi et al., 1973; Cortes et al., 1991). Cette condensation dipolaire conduit à un seul cycloadduit avec un bon rendement. La spectroscopie de masse nous indique qu'on a une monocycloaddition du dipôle sur l'un des deux sites dipolarophiles carbone-azote de la 1,5-benzodiazépine. L'analyse des spectres de RMN ¹H et ¹³C ne permet pas de trancher entre ces deux structures isomères. Seule l'étude cristallographique par diffraction des rayons X a permis de déterminer la structure exacte du produit obtenu. Les résultats de cette analyse montrent bien que la condensation s'est effectuée sur la double liaison C4═N5 de la benzodiazépine aboutissant à la éthyle 5-méthylthio-3-(4-nitrophényl)-3a-phényl-3a,11-dihydro-4H- [1,2,4]triazolo[3,4-d][1,5]benzodiazépine-1-carboxylate, (I). Cette réaction de cycloaddition dipolaire est à la fois péri et régiosélective.

Le coeur de la mol'ecule est composé des 3 cycles fusionnés de la benzodiazépine et du cycle triazolo à 5 chaînons. Ce fragment porte: (i) un groupe thiométhyle, attaché à la diazépine; (ii) un bras carboxyméthyle et le nitrophényle, attachés au cycle triazolo; (iii) un cycle phényle, à la jonction triazolo-diazépine. La benzodiazépine comporte un fragment plan composé du cycle C42/C41/C7/C8/C9/C10 et de N6/C41/C42/N11 [angle entre ces 2 plans: 3(1)°, en moyenne entre les deux molécules. Le cycle triazolo est plan, quasi-perpendiculaire à ce fragment et au cycle phényle. Par contre, le cycle nitrophényle est légérement tourné par rapport au cycle triazolo: 10 (2)° en moyenne].

S2. Experimental

A une solution de 1,5-benzodiazépine (0.5 g, 1.98 mmol) et N-p-nitrophénylhydrazono-α-bromoglyoxylate d'éthyle (0.626 g, 1.98 mmol) dans 20 ml de benzène anhydre, on ajoute lentement et sous agitation à température ambiante une solution de 0.3 ml de triéthylamine contenue dans 2 ml de benzène. Le mélange réactionnel est agité à température ambiante pendant deux jours. Après traitement du mélange réactionnel, le résidu obtenu est chromatographié sur gel de silice avec un gradient d'éluant hexane-acétate d'éthyle. Le produit purifié est recristallisé dans l'éthanol pour conduire au composé étudié (p.f.: 490–491 K).

S3. Refinement

La maille du cristal contient deux molécules indépendantes, numérotées de 1 à 43 (molécule 1) e t de 51 à 93 (molécule 2). Dans le cas de la molécule 1, les atomes de carbone terminaux du bras carboxyméthyle attaché à C1 sont fortement agités et en particulier l'atome C14: (i) dans le cas isotrope, la carte de densité différence fait apparaître deux positions situées de part et d'autre de la position moyenne, à 0.3 Å de ce lle-ci; (ii) dans le cas anisotrope, cet atome montre un ellipsoide d'agitation thermique très allongé, avec un rapport de 4 entre les axes principaux. Il na pas semblé raisonnable de placer les deux atomes d hydrogène liés à cet atome C14.

Computing details

Data collection: KappaCCD Software (Nonius, 1997); data reduction: DENZO and SCALEPAK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); software used to prepare material for publication: maXus.

(I)

Crystal data

C26H23N5O4S	F(000) = 2096
Mr = 501.57	Dx = 1.352 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.4896 (3) Å	Cell parameters from 30522 reflections
b = 14.4128 (5) Å	θ = 1–25.0°
c = 18.6685 (6) Å	µ = 0.17 mm^−1
β = 97.977 (3)°	T = 298 K
V = 4926.8 (3) Å^3	Prism, colourless
Z = 8	0.35 × 0.35 × 0.25 mm

Data collection

KappaCCD diffractometer	Rint = 0.051
Radiation source: fine-focus sealed tube	θmax = 25.0°
ϕ scans	h = 0→22
8666 measured reflections	k = 0→17
8230 independent reflections	l = −22→22
6645 reflections with I > 2.3σ(I)

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters not refined
wR(F^2) = 0.061	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + 0.03000Fo^2]
S = 1.92	(Δ/σ)max = 0.022
6645 reflections	Δρmax = 0.46 e Å^−3
649 parameters	Δρmin = −0.45 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case.

Refinement. Refinement on F².

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

	x	y	z	Uiso*/Ueq
C1	0.90469 (3)	0.11746 (3)	0.25078 (2)	0.0409 (3)
C10	0.87429 (3)	−0.08528 (4)	0.15068 (3)	0.0546 (3)
C12	0.94260 (3)	0.06176 (4)	0.31075 (3)	0.0494 (3)
C14	1.01770 (9)	0.05620 (12)	0.42000 (9)	0.0420 (4)
C15	1.07797 (5)	0.09552 (7)	0.45301 (5)	0.1331 (7)
C17	0.83149 (3)	0.32347 (3)	0.18409 (3)	0.0395 (3)
C18	0.78204 (3)	0.35345 (3)	0.12549 (3)	0.0494 (3)
C19	0.76376 (3)	0.44602 (3)	0.11891 (3)	0.0510 (3)
C20	0.79410 (3)	0.50828 (3)	0.17073 (3)	0.0457 (3)
C21	0.84523 (3)	0.48037 (3)	0.22740 (3)	0.0472 (3)
C22	0.86417 (3)	0.38819 (3)	0.23416 (3)	0.0433 (3)
C26	0.76149 (3)	0.13282 (3)	0.10964 (3)	0.0408 (3)
C27	0.73693 (3)	0.12026 (4)	0.03670 (3)	0.0538 (3)
C28	0.66535 (3)	0.09707 (4)	0.01319 (3)	0.0667 (4)
C29	0.61719 (3)	0.08448 (4)	0.06091 (4)	0.0655 (4)
C30	0.64032 (3)	0.09625 (4)	0.13340 (3)	0.0636 (4)
C31	0.71141 (3)	0.12070 (4)	0.15789 (3)	0.0531 (3)
C33	1.09300 (4)	0.26470 (4)	0.17529 (4)	0.0889 (4)
C4	0.89041 (3)	0.17409 (3)	0.08124 (2)	0.0420 (3)
C41	0.97228 (3)	0.01593 (3)	0.12810 (3)	0.0450 (3)
C42	0.90608 (3)	0.00180 (3)	0.15394 (3)	0.0427 (3)
C43	0.84074 (3)	0.15463 (3)	0.13947 (2)	0.0383 (3)
C5	0.96940 (3)	0.17560 (3)	0.11417 (3)	0.0441 (3)
C51	0.42422 (3)	0.19792 (3)	0.19852 (3)	0.0415 (3)
C54	0.47615 (3)	0.40707 (3)	0.25519 (3)	0.0464 (3)
C55	0.42454 (3)	0.37238 (3)	0.30462 (3)	0.0493 (3)
C57	0.26121 (3)	0.42922 (4)	0.19671 (3)	0.0583 (3)
C58	0.23167 (3)	0.44492 (4)	0.12668 (4)	0.0611 (4)
C59	0.26410 (3)	0.41177 (4)	0.07033 (3)	0.0573 (3)
C60	0.32748 (3)	0.35970 (3)	0.08476 (3)	0.0492 (3)
C62	0.36437 (3)	0.12813 (4)	0.18310 (3)	0.0520 (3)
C64	0.25227 (3)	0.09189 (4)	0.11121 (4)	0.0730 (4)
C65	0.21012 (4)	0.12504 (5)	0.04481 (4)	0.0996 (5)
C67	0.59802 (3)	0.25061 (3)	0.27728 (3)	0.0385 (3)
C68	0.64677 (3)	0.32468 (3)	0.27616 (3)	0.0470 (3)
C69	0.71435 (3)	0.32137 (3)	0.31746 (3)	0.0483 (3)
C7	1.00735 (3)	−0.05923 (4)	0.10082 (3)	0.0581 (3)
C70	0.73432 (3)	0.24414 (4)	0.35858 (3)	0.0440 (3)
C71	0.68727 (3)	0.17044 (3)	0.36094 (3)	0.0475 (3)
C72	0.61894 (3)	0.17361 (3)	0.32095 (3)	0.0446 (3)
C76	0.52759 (3)	0.37289 (3)	0.13671 (3)	0.0435 (3)
C77	0.54589 (3)	0.46554 (4)	0.13124 (3)	0.0539 (3)
C78	0.57529 (3)	0.49655 (4)	0.07102 (4)	0.0653 (4)
C79	0.58762 (3)	0.43580 (5)	0.01736 (3)	0.0740 (4)
C8	0.97597 (4)	−0.14518 (4)	0.09804 (3)	0.0676 (4)
C80	0.57105 (3)	0.34387 (5)	0.02324 (3)	0.0696 (4)
C81	0.54223 (3)	0.31441 (4)	0.08295 (3)	0.0629 (4)
C83	0.38918 (4)	0.31706 (5)	0.43563 (3)	0.0982 (5)
C9	0.90975 (4)	−0.15879 (4)	0.12298 (3)	0.0681 (4)
C91	0.32578 (3)	0.37806 (3)	0.21263 (3)	0.0458 (3)
C92	0.35753 (2)	0.34276 (3)	0.15517 (3)	0.0394 (3)
C93	0.49133 (3)	0.33431 (3)	0.19938 (3)	0.0417 (3)
N11	0.87125 (2)	0.07729 (2)	0.18731 (19)	0.0394 (2)
N2	0.89114 (2)	0.20370 (3)	0.25833 (19)	0.0441 (2)
N23	0.77206 (3)	0.60551 (3)	0.16375 (3)	0.0652 (3)
N3	0.84679 (2)	0.22967 (3)	0.19484 (19)	0.0421 (2)
N52	0.48578 (2)	0.17381 (3)	0.23451 (2)	0.0445 (2)
N53	0.53019 (2)	0.25172 (3)	0.23479 (2)	0.0439 (2)
N56	0.35523 (3)	0.36180 (3)	0.28594 (2)	0.0526 (3)
N6	1.00786 (2)	0.10377 (3)	0.13323 (2)	0.0493 (2)
N61	0.42210 (2)	0.28654 (3)	0.16941 (2)	0.0426 (2)
N73	0.80634 (3)	0.24121 (4)	0.40192 (2)	0.0569 (3)
O13	0.98764 (3)	0.11005 (3)	0.35651 (2)	0.0817 (3)
O16	0.93182 (2)	−0.01937 (3)	0.31609 (2)	0.0756 (3)
O24	0.73324 (3)	0.63024 (3)	0.10855 (2)	0.0887 (3)
O25	0.79329 (3)	0.65838 (3)	0.21276 (3)	0.0996 (3)
O63	0.3155 (19)	0.15270 (2)	0.12930 (19)	0.0596 (2)
O66	0.36250 (2)	0.05854 (3)	0.21749 (3)	0.0972 (3)
O74	0.84424 (2)	0.31092 (3)	0.40529 (19)	0.0673 (2)
O75	0.82564 (2)	0.16950 (3)	0.43423 (2)	0.0878 (3)
S32	1.006026 (8)	0.286879 (9)	0.124887 (8)	0.05863 (8)
S82	0.464768 (9)	0.350181 (12)	0.392611 (8)	0.07061 (10)
H10	0.828161	−0.094915	0.167607	0.0500*
H15A	1.096398	0.059159	0.494671	0.0500*
H15B	1.066668	0.156904	0.468077	0.0500*
H15C	1.114370	0.099109	0.421054	0.0500*
H18	0.760677	0.310028	0.089667	0.0500*
H19	0.729823	0.467161	0.078604	0.0500*
H21	0.867019	0.525207	0.261850	0.0500*
H22	0.900070	0.368268	0.273266	0.0500*
H27	0.770631	0.128179	0.002421	0.0500*
H28	0.649557	0.089886	−0.037702	0.0500*
H29	0.567561	0.067498	0.043923	0.0500*
H30	0.606907	0.087548	0.167865	0.0500*
H31	0.726836	0.129498	0.208688	0.0500*
H33A	1.118769	0.322218	0.184657	0.0500*
H33B	1.120327	0.224509	0.148010	0.0500*
H33C	1.087012	0.235528	0.220313	0.0500*
H4A	0.877334	0.233135	0.059405	0.0500*
H4B	0.882945	0.126375	0.045091	0.0500*
H54A	0.455583	0.460745	0.229556	0.0500*
H54B	0.521904	0.423315	0.283229	0.0500*
H57	0.237685	0.453563	0.235415	0.0500*
H58	0.187055	0.479656	0.117353	0.0500*
H59	0.242979	0.424698	0.021427	0.0500*
H60	0.35041	0.33546	0.04563	0.0500*
H64A	0.268425	0.029491	0.104840	0.0500*
H64B	0.222877	0.093384	0.149787	0.0500*
H65A	0.168235	0.085843	0.032306	0.0500*
H65B	0.239912	0.123520	0.006625	0.0500*
H65C	0.194365	0.187413	0.051573	0.0500*
H68	0.632854	0.377935	0.246545	0.0500*
H69	0.747549	0.372589	0.317508	0.0500*
H7	1.053610	−0.050697	0.083888	0.0500*
H71	0.702003	0.117354	0.390454	0.0500*
H72	0.585635	0.122865	0.322917	0.0500*
H77	0.538408	0.508426	0.168865	0.0500*
H78	0.586935	0.561099	0.067126	0.0500*
H79	0.607962	0.457471	−0.024182	0.0500*
H8	0.999759	−0.196829	0.078727	0.0500*
H80	0.579479	0.301112	−0.014156	0.0500*
H81	0.531337	0.249904	0.088512	0.0500*
H83A	0.405562	0.303100	0.485529	0.0500*
H83B	0.366537	0.263121	0.412093	0.0500*
H83C	0.354465	0.366923	0.432549	0.0500*
H9	0.888277	−0.219549	0.120896	0.0500*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0526 (3)	0.0380 (3)	0.0308 (3)	0.0034 (2)	0.0030 (2)	0.0047 (2)
C10	0.0682 (4)	0.0411 (3)	0.0541 (3)	0.0001 (3)	0.0136 (3)	0.0019 (3)
C12	0.0572 (4)	0.0462 (3)	0.0431 (3)	−0.0011 (3)	0.0011 (3)	0.0111 (3)
C14	0.2001 (10)	0.1520 (8)	0.0962 (6)	−0.1018 (7)	−0.0908 (6)	0.0949 (6)
C15	0.1182 (7)	0.1733 (9)	0.1070 (7)	0.0279 (6)	0.0262 (5)	0.0877 (7)
C17	0.0447 (3)	0.0345 (3)	0.0384 (3)	0.0060 (2)	0.0055 (2)	0.0035 (2)
C18	0.0636 (4)	0.0372 (3)	0.0437 (3)	0.0057 (3)	−0.0099 (3)	−0.0042 (2)
C19	0.0560 (3)	0.0441 (3)	0.0496 (3)	0.0075 (3)	−0.0072 (3)	0.0037 (3)
C20	0.0496 (3)	0.0325 (3)	0.0542 (3)	0.0073 (2)	0.0075 (3)	0.0027 (2)
C21	0.0539 (3)	0.0398 (3)	0.0467 (3)	−0.0001 (2)	0.0043 (3)	−0.0035 (2)
C22	0.0510 (3)	0.0421 (3)	0.0350 (3)	0.0027 (2)	−0.0006 (2)	0.0004 (2)
C26	0.0501 (3)	0.0333 (3)	0.0382 (3)	0.0070 (2)	0.0074 (2)	0.0019 (2)
C27	0.0535 (4)	0.0672 (4)	0.0396 (3)	−0.0028 (3)	0.0055 (3)	−0.0063 (3)
C28	0.0617 (4)	0.0854 (4)	0.0505 (4)	−0.0044 (3)	−0.0020 (3)	−0.0119 (3)
C29	0.0505 (4)	0.0675 (4)	0.0759 (5)	−0.0033 (3)	−0.0011 (3)	−0.0129 (3)
C30	0.0532 (4)	0.0629 (4)	0.0757 (5)	0.0024 (3)	0.0244 (3)	−0.0007 (3)
C31	0.0612 (4)	0.0543 (3)	0.0431 (3)	0.0046 (3)	0.0087 (3)	−0.0016 (3)
C33	0.0659 (4)	0.0581 (4)	0.1383 (6)	−0.0068 (3)	−0.0045 (4)	−0.0178 (4)
C4	0.0512 (3)	0.0392 (3)	0.0344 (3)	0.0016 (2)	0.0034 (2)	0.0008 (2)
C41	0.0512 (3)	0.0367 (3)	0.0454 (3)	0.0085 (2)	0.0007 (3)	−0.0011 (2)
C42	0.0540 (3)	0.0346 (3)	0.0378 (3)	0.0073 (2)	0.0015 (2)	0.0024 (2)
C43	0.0521 (3)	0.0328 (3)	0.0290 (3)	0.0060 (2)	0.0030 (2)	−0.0005 (2)
C5	0.0523 (3)	0.0430 (3)	0.0363 (3)	0.0018 (3)	0.0084 (2)	0.0000 (2)
C51	0.0434 (3)	0.0321 (3)	0.0473 (3)	−0.0010 (2)	0.0010 (2)	−0.0014 (2)
C54	0.0427 (3)	0.0403 (3)	0.0541 (3)	−0.0033 (2)	−0.0010 (3)	−0.0010 (2)
C55	0.0577 (4)	0.0420 (3)	0.0472 (3)	−0.0036 (3)	0.0076 (3)	−0.0031 (2)
C57	0.0432 (3)	0.0614 (4)	0.0707 (4)	0.0008 (3)	0.0189 (3)	−0.0034 (3)
C58	0.0398 (3)	0.0613 (4)	0.0790 (4)	0.0074 (3)	−0.0066 (3)	0.0053 (3)
C59	0.0555 (4)	0.0581 (4)	0.0549 (4)	0.0035 (3)	−0.0077 (3)	0.0124 (3)
C60	0.0483 (3)	0.0498 (3)	0.0484 (3)	−0.0020 (3)	0.0053 (3)	−0.0022 (3)
C62	0.0460 (3)	0.0369 (3)	0.0701 (4)	−0.0019 (3)	−0.0059 (3)	0.0051 (3)
C64	0.0532 (4)	0.0672 (4)	0.0937 (5)	−0.0198 (3)	−0.0143 (3)	−0.0040 (4)
C65	0.0758 (5)	0.1260 (6)	0.0918 (5)	−0.0294 (4)	−0.0129 (4)	−0.0100 (5)
C67	0.0365 (3)	0.0384 (3)	0.0393 (3)	0.0032 (2)	0.0010 (2)	−0.0011 (2)
C68	0.0438 (3)	0.0403 (3)	0.0554 (3)	−0.0029 (2)	0.0030 (3)	0.0065 (2)
C69	0.0431 (3)	0.0498 (3)	0.0512 (3)	−0.0075 (2)	0.0075 (3)	−0.0065 (3)
C7	0.0552 (4)	0.0491 (3)	0.0692 (4)	0.0101 (3)	0.0107 (3)	−0.0086 (3)
C70	0.0354 (3)	0.0576 (3)	0.0375 (3)	0.0016 (3)	−0.0003 (2)	−0.0082 (3)
C71	0.0500 (3)	0.0497 (3)	0.0411 (3)	0.0033 (3)	0.0002 (2)	0.0036 (2)
C72	0.0445 (3)	0.0420 (3)	0.0456 (3)	−0.0041 (2)	0.0002 (2)	0.0004 (2)
C76	0.0497 (3)	0.0347 (3)	0.0442 (3)	0.0001 (2)	0.0001 (2)	0.0044 (2)
C77	0.0517 (3)	0.0508 (3)	0.0574 (4)	−0.0011 (3)	0.0034 (3)	0.0051 (3)
C78	0.0604 (4)	0.0602 (4)	0.0741 (4)	−0.0067 (3)	0.0090 (3)	0.0231 (3)
C79	0.0640 (4)	0.1009 (5)	0.0563 (4)	−0.0006 (4)	0.0122 (3)	0.0227 (4)
C8	0.0770 (5)	0.0434 (3)	0.0811 (4)	0.0148 (3)	0.0117 (4)	−0.0164 (3)
C80	0.0746 (4)	0.0803 (5)	0.0535 (4)	0.0014 (4)	0.0154 (3)	−0.0026 (3)
C81	0.0758 (4)	0.0563 (4)	0.0566 (4)	0.0070 (3)	0.0193 (3)	0.0044 (3)
C83	0.1268 (6)	0.1125 (6)	0.0535 (4)	−0.0233 (5)	0.0122 (4)	0.0199 (4)
C9	0.0900 (5)	0.0339 (3)	0.0789 (4)	−0.0027 (3)	0.0124 (4)	−0.0092 (3)
C91	0.0428 (3)	0.0446 (3)	0.0489 (3)	−0.0049 (2)	0.0048 (3)	0.0054 (3)
C92	0.0343 (3)	0.0327 (3)	0.0493 (3)	0.0019 (2)	−0.0004 (2)	−0.0002 (2)
C93	0.0378 (3)	0.0353 (3)	0.0501 (3)	0.0010 (2)	−0.0006 (2)	0.0011 (2)
N11	0.0520 (3)	0.0339 (2)	0.0308 (2)	0.00802 (19)	0.00172 (19)	0.00169 (18)
N2	0.0601 (3)	0.0419 (3)	0.0284 (2)	0.0061 (2)	−0.00006 (19)	0.00391 (19)
N23	0.0722 (4)	0.0406 (3)	0.0802 (4)	0.0096 (3)	0.0030 (3)	−0.0024 (3)
N3	0.0595 (3)	0.0351 (2)	0.0294 (2)	0.00760 (19)	−0.0031 (2)	−0.00106 (18)
N52	0.0425 (3)	0.0331 (2)	0.0557 (3)	−0.00435 (19)	−0.0024 (2)	0.00121 (19)
N53	0.0373 (2)	0.0323 (2)	0.0592 (3)	−0.00382 (18)	−0.0070 (2)	0.00538 (19)
N56	0.0593 (3)	0.0511 (3)	0.0465 (3)	−0.0054 (2)	0.0092 (2)	0.0003 (2)
N6	0.0519 (3)	0.0414 (3)	0.0536 (3)	0.0021 (2)	0.0083 (2)	−0.0026 (2)
N61	0.0376 (2)	0.0344 (2)	0.0539 (3)	−0.00050 (19)	−0.00069 (19)	−0.0013 (2)
N73	0.0488 (3)	0.0790 (4)	0.0409 (3)	0.0001 (3)	−0.0011 (2)	−0.0092 (3)
O13	0.1166 (4)	0.0686 (3)	0.0518 (3)	−0.0258 (3)	−0.0328 (2)	0.0290 (2)
O16	0.0911 (3)	0.0510 (3)	0.0785 (3)	−0.0047 (2)	−0.0196 (2)	0.0232 (2)
O24	0.1178 (4)	0.0533 (3)	0.0875 (3)	0.0319 (3)	−0.0237 (3)	0.0063 (2)
O25	0.1371 (4)	0.0440 (2)	0.1086 (4)	0.0158 (3)	−0.0296 (3)	−0.0201 (3)
O63	0.0516 (2)	0.0517 (2)	0.0711 (3)	−0.01361 (18)	−0.0143 (2)	0.0033 (2)
O66	0.0809 (3)	0.0608 (3)	0.1398 (4)	−0.0270 (2)	−0.0397 (3)	0.0440 (3)
O74	0.0490 (2)	0.0987 (3)	0.0524 (2)	−0.0200 (2)	0.00217 (18)	−0.0114 (2)
O75	0.0733 (3)	0.0896 (3)	0.0925 (3)	0.0046 (3)	−0.0341 (2)	0.0118 (3)
S32	0.05907 (9)	0.04210 (8)	0.07317 (10)	−0.00397 (7)	0.00738 (7)	0.00471 (7)
S82	0.08421 (12)	0.07756 (11)	0.04688 (9)	−0.00392 (9)	−0.00422 (8)	0.00364 (8)

Geometric parameters (Å, º)

C1—C12	1.4737 (6)	C8—C9	1.3831 (8)
C15—C14	1.324 (2)	C81—C80	1.3682 (7)
C17—C18	1.3936 (6)	C9—C10	1.3835 (7)
C17—C22	1.3973 (6)	C92—C60	1.3760 (6)
C19—C18	1.3776 (7)	C92—C91	1.3888 (6)
C20—C19	1.3804 (7)	C93—C54	1.5316 (6)
C20—N23	1.4602 (6)	C93—C76	1.5313 (6)
C21—C20	1.3775 (7)	N11—C1	1.3850 (5)
C21—C22	1.3752 (6)	N11—C42	1.4486 (5)
C26—C27	1.3862 (6)	N11—C43	1.4894 (5)
C26—C31	1.3896 (6)	N2—C1	1.2796 (5)
C26—C43	1.5263 (6)	N23—O25	1.2133 (5)
C27—C28	1.3766 (8)	N3—C17	1.3901 (5)
C28—C29	1.3564 (8)	N3—C43	1.4895 (5)
C30—C29	1.3722 (7)	N3—N2	1.3957 (5)
C31—C30	1.3763 (7)	N52—C51	1.2867 (5)
C4—C43	1.5429 (6)	N52—N53	1.3907 (5)
C4—C5	1.5041 (7)	N53—C67	1.3879 (5)
C41—C7	1.3947 (6)	N53—C93	1.4961 (5)
C42—C10	1.3837 (7)	N56—C55	1.2895 (6)
C42—C41	1.3914 (7)	N56—C91	1.4204 (6)
C51—C62	1.4936 (6)	N6—C41	1.4237 (6)
C54—C55	1.5022 (7)	N6—C5	1.2782 (6)
C57—C58	1.3640 (7)	N61—C51	1.3866 (5)
C57—C91	1.3997 (7)	N61—C92	1.4368 (5)
C58—C59	1.3675 (7)	N61—C93	1.4923 (5)
C60—C59	1.3862 (7)	N73—C70	1.4597 (6)
C64—C65	1.4506 (9)	O13—C12	1.3079 (6)
C67—C68	1.3992 (6)	O13—C14	1.4596 (14)
C67—C72	1.3995 (6)	O16—C12	1.1927 (6)
C69—C68	1.3750 (7)	O24—N23	1.2243 (6)
C69—C70	1.3734 (7)	O63—C62	1.3028 (6)
C70—C71	1.3775 (7)	O63—C64	1.4634 (6)
C72—C71	1.3762 (6)	O66—C62	1.1940 (6)
C76—C81	1.3661 (7)	O74—N73	1.2216 (5)
C77—C76	1.3849 (7)	O75—N73	1.2246 (5)
C77—C78	1.3887 (7)	S32—C33	1.7759 (7)
C79—C78	1.3732 (8)	S32—C5	1.7418 (5)
C79—C80	1.3678 (8)	S82—C55	1.7364 (5)
C8—C7	1.3659 (7)	S82—C83	1.7715 (7)
C1—N11—C42	120.63 (4)	C92—N61—C51	124.73 (4)
C1—N11—C43	106.69 (3)	C92—N61—C93	117.18 (3)
C12—O13—C14	112.54 (7)	C93—C54—C55	112.46 (4)
C17—C18—C19	119.77 (4)	C93—C76—C77	122.95 (5)
C17—C22—C21	120.18 (4)	C93—C76—C81	119.32 (4)
C17—N3—C43	127.73 (4)	N11—C1—C12	122.08 (4)
C20—C19—C18	119.75 (4)	N11—C1—N2	115.43 (4)
C20—N23—O25	118.58 (5)	N11—C42—C10	119.25 (5)
C21—C20—C19	121.16 (4)	N11—C42—C41	120.28 (4)
C21—C20—N23	120.14 (5)	N11—C43—C26	109.22 (4)
C22—C17—C18	119.59 (4)	N11—C43—C4	110.22 (3)
C22—C21—C20	119.44 (4)	N2—C1—C12	121.69 (4)
C26—C27—C28	120.96 (5)	N2—N3—C17	117.85 (4)
C26—C31—C30	120.56 (5)	N2—N3—C43	111.93 (3)
C26—C43—C4	114.56 (4)	N23—C20—C19	118.69 (5)
C27—C26—C31	117.61 (4)	N3—C17—C18	120.87 (4)
C27—C28—C29	120.85 (5)	N3—C17—C22	119.50 (4)
C30—C29—C28	119.21 (5)	N3—C43—C26	112.24 (4)
C31—C30—C29	120.79 (5)	N3—C43—C4	111.24 (4)
C41—C42—C10	120.42 (5)	N3—C43—N11	98.13 (3)
C41—C7—C8	120.11 (5)	N3—N2—C1	105.54 (4)
C41—N6—C5	117.87 (4)	N52—C51—C62	119.79 (4)
C42—C10—C9	119.39 (5)	N52—C51—N61	115.36 (4)
C42—C41—C7	119.27 (5)	N52—N53—C67	118.63 (3)
C42—N11—C43	117.27 (3)	N52—N53—C93	113.18 (3)
C43—C26—C27	123.53 (4)	N53—C67—C68	121.04 (4)
C43—C26—C31	118.80 (4)	N53—C67—C72	119.79 (4)
C43—C4—C5	110.72 (4)	N53—C93—C54	111.49 (4)
C5—S32—C33	101.78 (3)	N53—C93—C76	113.09 (4)
C51—C62—O66	122.55 (5)	N53—N52—C51	105.25 (4)
C51—N61—C93	107.57 (4)	N56—C55—C54	124.43 (4)
C55—S82—C83	102.55 (3)	N56—C91—C57	119.54 (5)
C57—C58—C59	121.30 (5)	N6—C41—C42	121.82 (4)
C60—C59—C58	119.26 (5)	N6—C41—C7	118.77 (5)
C60—C92—C91	120.99 (4)	N6—C5—C4	124.97 (4)
C62—O63—C64	117.47 (4)	N61—C51—C62	124.40 (4)
C67—C68—C69	120.16 (4)	N61—C92—C60	119.46 (4)
C67—C72—C71	120.07 (4)	N61—C92—C91	119.54 (4)
C67—N53—C93	127.03 (4)	N61—C93—C54	110.01 (4)
C68—C67—C72	119.16 (4)	N61—C93—C76	108.95 (4)
C68—C69—C70	119.63 (5)	N61—C93—N53	97.65 (3)
C69—C70—C71	121.39 (4)	N73—C70—C71	119.45 (5)
C69—C70—N73	119.15 (5)	O13—C12—C1	113.51 (4)
C72—C71—C70	119.57 (5)	O13—C14—C15	110.59 (10)
C76—C77—C78	119.81 (5)	O16—C12—C1	122.02 (5)
C76—C81—C80	123.13 (5)	O16—C12—O13	124.46 (5)
C76—C93—C54	114.34 (4)	O24—N23—C20	118.57 (5)
C77—C76—C81	117.73 (5)	O24—N23—O25	122.84 (5)
C77—C78—C79	120.57 (6)	O63—C62—C51	112.40 (4)
C78—C79—C80	119.83 (6)	O63—C62—O66	125.05 (5)
C8—C9—C10	120.32 (5)	O63—C64—C65	108.50 (5)
C81—C80—C79	118.87 (6)	O74—N73—C70	118.52 (5)
C9—C8—C7	120.47 (5)	O74—N73—O75	122.88 (5)
C91—C57—C58	120.47 (5)	O75—N73—C70	118.59 (5)
C91—N56—C55	118.35 (4)	S32—C5—C4	113.60 (3)
C92—C60—C59	120.01 (5)	S32—C5—N6	121.43 (4)
C92—C91—C57	117.94 (5)	S82—C55—C54	114.66 (4)
C92—C91—N56	122.49 (4)	S82—C55—N56	120.88 (4)