1''-Allyl-5''-(4-meth-oxy-benzyl-idene)-7'-(4-methoxy-phen-yl)-1',3',5',6',7',7a'-hexa-hydro-dispiro-[ace-naphthyl-ene-1,5'-pyrrolo-[1,2-c][1,3]thia-zole-6',3''-piperidine]-2,4''(1H)-dione.

In the title compound, C39H36N2O4S, the piperidine ring adopts a twisted half-chair conformation. In the pyrrolo-thia-zole fused-ring system, the pyrrole ring adopts an envelope conformation (with the C atom bound to the thia-zole ring being the flap atom) and the thia-zole ring also exhibits an envelope conformation (with the N atom bound to the pyrrole ring as the flap). The mol-ecular structure features a weak intra-molecular C-H⋯O inter-action. In the crystal, a C-H⋯O inter-action forms a linear chain along the diagonal of the ac plane, generating a C(14) graph-set motif. A weak C-H⋯π inter-action also occurs.

Related literature

For the importance of hetrocyclic rings, see: Guengerich et al. (1973 ▶); Lalezari & Schwartz (1988 ▶); Tsuge & Kanemasa (1989 ▶); Puder et al. (2000 ▶); Nair & Suja (2007 ▶). For related ace­naphthyl­ene structures, see: Suresh et al. (2011 ▶). For additional conformation analysis, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C39H36N2O4S

M = 628.76

Monoclinic,

a = 11.3956 (7) Å

b = 20.1346 (12) Å

c = 14.3860 (8) Å

β = 103.153 (1)°

V = 3214.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 293 K

0.21 × 0.19 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.967, T max = 0.974

26225 measured reflections

5979 independent reflections

4873 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.104

S = 1.07

5979 reflections

415 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813020084/gw2135sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020084/gw2135Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C39H36N2O4S	F(000) = 1328
Mr = 628.76	Dx = 1.299 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2000 reflections
a = 11.3956 (7) Å	θ = 2–31°
b = 20.1346 (12) Å	µ = 0.15 mm−1
c = 14.3860 (8) Å	T = 293 K
β = 103.153 (1)°	Block, yellow
V = 3214.2 (3) Å3	0.21 × 0.19 × 0.18 mm
Z = 4

Bruker Kappa APEXII diffractometer	5979 independent reflections
Radiation source: fine-focus sealed tube	4873 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 0 pixels mm-1	θmax = 25.5°, θmin = 2.0°
ω and φ scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −24→23
Tmin = 0.967, Tmax = 0.974	l = −17→17
26225 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.8433P] where P = (Fo2 + 2Fc2)/3
5979 reflections	(Δ/σ)max < 0.001
415 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.38453 (15)	0.24423 (8)	0.61103 (12)	0.0465 (4)
H1A	0.3731	0.1988	0.5882	0.056*
H1B	0.4268	0.2429	0.6776	0.056*
C2	0.27822 (14)	0.34635 (7)	0.62444 (11)	0.0406 (3)
H2A	0.3379	0.3536	0.6834	0.049*
H2B	0.2018	0.3640	0.6320	0.049*
C3	0.31686 (13)	0.38124 (7)	0.54151 (10)	0.0376 (3)
C4	0.44181 (13)	0.35396 (7)	0.53899 (11)	0.0409 (3)
C5	0.46034 (14)	0.28104 (7)	0.55445 (11)	0.0430 (3)
C6	0.19271 (16)	0.23989 (9)	0.65863 (13)	0.0536 (4)
H6A	0.1854	0.1940	0.6377	0.064*
H6B	0.1125	0.2590	0.6438	0.064*
C7	0.23879 (18)	0.24090 (10)	0.76404 (14)	0.0617 (5)
H7	0.2569	0.2823	0.7922	0.074*
C8	0.2563 (2)	0.19024 (12)	0.82035 (18)	0.0892 (7)
H8A	0.2396	0.1477	0.7957	0.107*
H8B	0.2855	0.1962	0.8856	0.107*
C9	0.31827 (13)	0.45865 (7)	0.54978 (10)	0.0387 (3)
H9	0.3782	0.4748	0.5160	0.046*
C10	0.19504 (14)	0.47781 (7)	0.48948 (11)	0.0417 (3)
H10	0.1316	0.4678	0.5233	0.050*
C11	0.17877 (16)	0.54723 (8)	0.44674 (13)	0.0532 (4)
H11A	0.2551	0.5650	0.4390	0.064*
H11B	0.1456	0.5770	0.4872	0.064*
C12	0.07720 (16)	0.44611 (9)	0.33773 (12)	0.0545 (4)
H12A	0.0076	0.4290	0.3582	0.065*
H12B	0.0802	0.4264	0.2768	0.065*
C13	0.22302 (13)	0.36619 (7)	0.44231 (10)	0.0404 (3)
C14	0.11388 (14)	0.32178 (8)	0.45544 (11)	0.0449 (4)
C15	0.11378 (15)	0.26054 (8)	0.39828 (12)	0.0482 (4)
C16	0.20475 (15)	0.26712 (8)	0.34768 (11)	0.0465 (4)
C17	0.26952 (15)	0.32703 (8)	0.36735 (11)	0.0438 (3)
C18	0.35670 (17)	0.34039 (9)	0.31920 (12)	0.0551 (4)
H18	0.4003	0.3798	0.3299	0.066*
C19	0.3800 (2)	0.29318 (11)	0.25234 (13)	0.0674 (5)
H19	0.4395	0.3025	0.2194	0.081*
C20	0.3185 (2)	0.23472 (10)	0.23449 (13)	0.0688 (6)
H20	0.3373	0.2048	0.1908	0.083*
C21	0.22627 (18)	0.21948 (8)	0.28235 (12)	0.0570 (5)
C22	0.1515 (2)	0.16223 (9)	0.27252 (14)	0.0697 (6)
H22	0.1620	0.1287	0.2307	0.084*
C23	0.0649 (2)	0.15566 (9)	0.32311 (16)	0.0711 (6)
H23	0.0186	0.1172	0.3156	0.085*
C24	0.04265 (17)	0.20495 (9)	0.38639 (14)	0.0606 (5)
H24	−0.0184	0.1999	0.4191	0.073*
C51	0.53982 (15)	0.25243 (8)	0.51160 (12)	0.0492 (4)
H51	0.5801	0.2812	0.4790	0.059*
C52	0.57272 (15)	0.18221 (8)	0.50855 (12)	0.0484 (4)
C53	0.58985 (16)	0.13945 (9)	0.58581 (12)	0.0550 (4)
H53	0.5803	0.1555	0.6443	0.066*
C54	0.62084 (17)	0.07332 (9)	0.57851 (12)	0.0550 (4)
H54	0.6328	0.0457	0.6317	0.066*
C55	0.63385 (15)	0.04874 (8)	0.49180 (12)	0.0510 (4)
C56	0.61851 (18)	0.09096 (10)	0.41350 (13)	0.0621 (5)
H56	0.6277	0.0748	0.3550	0.074*
C57	0.58980 (17)	0.15644 (9)	0.42261 (13)	0.0587 (5)
H57	0.5815	0.1844	0.3701	0.070*
C58	0.6933 (2)	−0.05957 (10)	0.55429 (16)	0.0698 (5)
H58A	0.7101	−0.1027	0.5321	0.105*
H58B	0.6274	−0.0626	0.5854	0.105*
H58C	0.7634	−0.0432	0.5986	0.105*
C91	0.35268 (14)	0.48671 (7)	0.65013 (10)	0.0393 (3)
C92	0.26940 (15)	0.49766 (8)	0.70580 (12)	0.0495 (4)
H92	0.1890	0.4866	0.6817	0.059*
C93	0.30398 (16)	0.52474 (9)	0.79634 (12)	0.0536 (4)
H93	0.2466	0.5318	0.8321	0.064*
C94	0.42242 (16)	0.54125 (8)	0.83392 (11)	0.0470 (4)
C95	0.50713 (15)	0.53016 (8)	0.78109 (11)	0.0469 (4)
H95	0.5877	0.5405	0.8062	0.056*
C96	0.47143 (14)	0.50337 (7)	0.68956 (11)	0.0436 (3)
H96	0.5291	0.4965	0.6540	0.052*
C97	0.56944 (19)	0.57887 (11)	0.96906 (14)	0.0698 (5)
H97A	0.5751	0.5985	1.0308	0.105*
H97B	0.6063	0.6078	0.9309	0.105*
H97C	0.6102	0.5368	0.9763	0.105*
N1	0.18725 (12)	0.43348 (6)	0.40858 (9)	0.0439 (3)
N2	0.26677 (11)	0.27556 (6)	0.60308 (9)	0.0431 (3)
O1	0.66222 (13)	−0.01537 (6)	0.47538 (10)	0.0665 (4)
O2	0.44643 (12)	0.56933 (6)	0.92363 (9)	0.0633 (3)
O3	0.03616 (10)	0.34017 (6)	0.49502 (9)	0.0554 (3)
O4	0.52104 (10)	0.38980 (6)	0.52376 (9)	0.0555 (3)
S1	0.07354 (5)	0.53678 (2)	0.33048 (4)	0.06657 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0554 (9)	0.0336 (8)	0.0529 (9)	0.0000 (7)	0.0174 (8)	0.0018 (7)
C2	0.0422 (8)	0.0368 (8)	0.0434 (8)	−0.0017 (6)	0.0109 (6)	0.0005 (6)
C3	0.0391 (7)	0.0334 (7)	0.0405 (8)	−0.0029 (6)	0.0096 (6)	−0.0004 (6)
C4	0.0429 (8)	0.0379 (8)	0.0420 (8)	−0.0020 (6)	0.0096 (6)	0.0003 (6)
C5	0.0432 (8)	0.0387 (8)	0.0466 (8)	0.0007 (6)	0.0091 (7)	0.0008 (6)
C6	0.0536 (10)	0.0450 (9)	0.0655 (11)	−0.0081 (8)	0.0202 (8)	0.0055 (8)
C7	0.0734 (12)	0.0547 (11)	0.0649 (11)	−0.0112 (9)	0.0322 (10)	−0.0002 (9)
C8	0.117 (2)	0.0724 (15)	0.0745 (14)	−0.0065 (14)	0.0144 (14)	0.0113 (12)
C9	0.0414 (8)	0.0326 (7)	0.0427 (8)	−0.0038 (6)	0.0111 (6)	−0.0001 (6)
C10	0.0442 (8)	0.0354 (8)	0.0453 (8)	−0.0010 (6)	0.0095 (7)	−0.0015 (6)
C11	0.0555 (10)	0.0388 (9)	0.0611 (10)	0.0031 (7)	0.0045 (8)	0.0034 (7)
C12	0.0596 (10)	0.0515 (10)	0.0472 (9)	0.0011 (8)	0.0011 (8)	0.0009 (7)
C13	0.0440 (8)	0.0337 (8)	0.0430 (8)	−0.0029 (6)	0.0087 (6)	−0.0014 (6)
C14	0.0440 (8)	0.0407 (8)	0.0478 (9)	−0.0025 (7)	0.0055 (7)	0.0012 (7)
C15	0.0509 (9)	0.0379 (8)	0.0498 (9)	−0.0026 (7)	−0.0009 (7)	0.0005 (7)
C16	0.0544 (9)	0.0375 (8)	0.0423 (8)	0.0051 (7)	−0.0001 (7)	−0.0001 (6)
C17	0.0505 (9)	0.0399 (8)	0.0395 (8)	0.0021 (7)	0.0072 (7)	0.0003 (6)
C18	0.0643 (11)	0.0548 (10)	0.0488 (9)	0.0009 (8)	0.0180 (8)	0.0008 (8)
C19	0.0779 (13)	0.0771 (14)	0.0520 (10)	0.0158 (11)	0.0250 (10)	0.0028 (10)
C20	0.0914 (15)	0.0627 (12)	0.0506 (10)	0.0249 (11)	0.0125 (10)	−0.0084 (9)
C21	0.0739 (12)	0.0434 (9)	0.0460 (9)	0.0142 (8)	−0.0022 (8)	−0.0042 (7)
C22	0.0955 (15)	0.0405 (10)	0.0593 (11)	0.0111 (10)	−0.0115 (11)	−0.0112 (8)
C23	0.0808 (14)	0.0382 (10)	0.0795 (14)	−0.0076 (9)	−0.0122 (12)	−0.0028 (9)
C24	0.0613 (11)	0.0429 (9)	0.0693 (12)	−0.0098 (8)	−0.0023 (9)	0.0015 (8)
C51	0.0485 (9)	0.0439 (9)	0.0577 (10)	0.0040 (7)	0.0173 (8)	0.0070 (7)
C52	0.0483 (9)	0.0452 (9)	0.0549 (9)	0.0072 (7)	0.0186 (7)	0.0043 (7)
C53	0.0671 (11)	0.0534 (10)	0.0463 (9)	0.0131 (8)	0.0167 (8)	0.0016 (8)
C54	0.0660 (11)	0.0510 (10)	0.0508 (9)	0.0150 (8)	0.0188 (8)	0.0104 (8)
C55	0.0496 (9)	0.0465 (9)	0.0590 (10)	0.0106 (7)	0.0165 (8)	0.0008 (8)
C56	0.0767 (13)	0.0643 (12)	0.0499 (10)	0.0217 (10)	0.0240 (9)	0.0023 (8)
C57	0.0690 (11)	0.0576 (11)	0.0558 (10)	0.0189 (9)	0.0274 (9)	0.0145 (8)
C58	0.0730 (13)	0.0476 (10)	0.0859 (14)	0.0111 (9)	0.0122 (11)	0.0092 (10)
C91	0.0463 (8)	0.0280 (7)	0.0438 (8)	−0.0020 (6)	0.0109 (7)	0.0013 (6)
C92	0.0463 (9)	0.0504 (9)	0.0530 (9)	−0.0054 (7)	0.0138 (7)	−0.0041 (7)
C93	0.0591 (10)	0.0536 (10)	0.0529 (10)	0.0009 (8)	0.0227 (8)	−0.0029 (8)
C94	0.0625 (10)	0.0364 (8)	0.0421 (8)	0.0023 (7)	0.0118 (7)	0.0010 (6)
C95	0.0475 (9)	0.0423 (9)	0.0483 (9)	−0.0042 (7)	0.0055 (7)	0.0010 (7)
C96	0.0458 (8)	0.0398 (8)	0.0461 (8)	−0.0025 (7)	0.0124 (7)	−0.0005 (7)
C97	0.0783 (14)	0.0725 (13)	0.0524 (10)	−0.0001 (10)	0.0016 (10)	−0.0124 (9)
N1	0.0498 (7)	0.0362 (7)	0.0430 (7)	0.0006 (6)	0.0050 (6)	−0.0005 (5)
N2	0.0453 (7)	0.0360 (7)	0.0499 (7)	−0.0057 (5)	0.0146 (6)	0.0011 (5)
O1	0.0837 (9)	0.0496 (7)	0.0692 (8)	0.0176 (6)	0.0235 (7)	0.0009 (6)
O2	0.0744 (9)	0.0656 (8)	0.0487 (7)	0.0045 (6)	0.0115 (6)	−0.0123 (6)
O3	0.0458 (6)	0.0555 (7)	0.0666 (7)	−0.0033 (5)	0.0162 (6)	−0.0020 (6)
O4	0.0468 (6)	0.0432 (6)	0.0806 (8)	−0.0049 (5)	0.0233 (6)	0.0039 (6)
S1	0.0707 (3)	0.0522 (3)	0.0670 (3)	0.0060 (2)	−0.0049 (2)	0.0126 (2)

C1—N2	1.464 (2)	C18—C19	1.420 (3)
C1—C5	1.509 (2)	C18—H18	0.9300
C1—H1A	0.9700	C19—C20	1.364 (3)
C1—H1B	0.9700	C19—H19	0.9300
C2—N2	1.4578 (19)	C20—C21	1.415 (3)
C2—C3	1.533 (2)	C20—H20	0.9300
C2—H2A	0.9700	C21—C22	1.421 (3)
C2—H2B	0.9700	C22—C23	1.359 (3)
C3—C4	1.534 (2)	C22—H22	0.9300
C3—C9	1.5629 (19)	C23—C24	1.408 (3)
C3—C13	1.605 (2)	C23—H23	0.9300
C4—O4	1.2141 (18)	C24—H24	0.9300
C4—C5	1.493 (2)	C51—C52	1.466 (2)
C5—C51	1.336 (2)	C51—H51	0.9300
C6—N2	1.474 (2)	C52—C53	1.384 (2)
C6—C7	1.488 (3)	C52—C57	1.395 (2)
C6—H6A	0.9700	C53—C54	1.388 (2)
C6—H6B	0.9700	C53—H53	0.9300
C7—C8	1.290 (3)	C54—C55	1.381 (2)
C7—H7	0.9300	C54—H54	0.9300
C8—H8A	0.9300	C55—O1	1.364 (2)
C8—H8B	0.9300	C55—C56	1.390 (2)
C9—C91	1.516 (2)	C56—C57	1.372 (3)
C9—C10	1.523 (2)	C56—H56	0.9300
C9—H9	0.9800	C57—H57	0.9300
C10—N1	1.4533 (19)	C58—O1	1.422 (2)
C10—C11	1.521 (2)	C58—H58A	0.9600
C10—H10	0.9800	C58—H58B	0.9600
C11—S1	1.8349 (18)	C58—H58C	0.9600
C11—H11A	0.9700	C91—C96	1.384 (2)
C11—H11B	0.9700	C91—C92	1.392 (2)
C12—N1	1.447 (2)	C92—C93	1.384 (2)
C12—S1	1.8285 (18)	C92—H92	0.9300
C12—H12A	0.9700	C93—C94	1.376 (2)
C12—H12B	0.9700	C93—H93	0.9300
C13—N1	1.4654 (19)	C94—C95	1.376 (2)
C13—C17	1.525 (2)	C94—O2	1.3782 (19)
C13—C14	1.578 (2)	C95—C96	1.395 (2)
C14—O3	1.2145 (19)	C95—H95	0.9300
C14—C15	1.482 (2)	C96—H96	0.9300
C15—C24	1.370 (2)	C97—O2	1.418 (2)
C15—C16	1.402 (2)	C97—H97A	0.9600
C16—C21	1.403 (2)	C97—H97B	0.9600
C16—C17	1.409 (2)	C97—H97C	0.9600
C17—C18	1.361 (2)
N2—C1—C5	111.93 (12)	C19—C18—H18	120.6
N2—C1—H1A	109.2	C20—C19—C18	122.58 (19)
C5—C1—H1A	109.2	C20—C19—H19	118.7
N2—C1—H1B	109.2	C18—C19—H19	118.7
C5—C1—H1B	109.2	C19—C20—C21	120.13 (17)
H1A—C1—H1B	107.9	C19—C20—H20	119.9
N2—C2—C3	108.17 (12)	C21—C20—H20	119.9
N2—C2—H2A	110.1	C16—C21—C20	116.11 (17)
C3—C2—H2A	110.1	C16—C21—C22	115.39 (19)
N2—C2—H2B	110.1	C20—C21—C22	128.50 (18)
C3—C2—H2B	110.1	C23—C22—C21	121.18 (18)
H2A—C2—H2B	108.4	C23—C22—H22	119.4
C2—C3—C4	106.66 (12)	C21—C22—H22	119.4
C2—C3—C9	113.43 (12)	C22—C23—C24	122.47 (18)
C4—C3—C9	111.42 (12)	C22—C23—H23	118.8
C2—C3—C13	110.74 (11)	C24—C23—H23	118.8
C4—C3—C13	110.21 (11)	C15—C24—C23	117.92 (19)
C9—C3—C13	104.43 (11)	C15—C24—H24	121.0
O4—C4—C5	121.71 (14)	C23—C24—H24	121.0
O4—C4—C3	121.59 (13)	C5—C51—C52	129.37 (15)
C5—C4—C3	116.69 (12)	C5—C51—H51	115.3
C51—C5—C4	116.29 (14)	C52—C51—H51	115.3
C51—C5—C1	124.63 (14)	C53—C52—C57	117.24 (15)
C4—C5—C1	118.97 (13)	C53—C52—C51	124.48 (15)
N2—C6—C7	115.66 (14)	C57—C52—C51	118.27 (15)
N2—C6—H6A	108.4	C52—C53—C54	121.87 (16)
C7—C6—H6A	108.4	C52—C53—H53	119.1
N2—C6—H6B	108.4	C54—C53—H53	119.1
C7—C6—H6B	108.4	C55—C54—C53	119.58 (16)
H6A—C6—H6B	107.4	C55—C54—H54	120.2
C8—C7—C6	126.7 (2)	C53—C54—H54	120.2
C8—C7—H7	116.6	O1—C55—C54	125.01 (16)
C6—C7—H7	116.6	O1—C55—C56	115.43 (15)
C7—C8—H8A	120.0	C54—C55—C56	119.55 (16)
C7—C8—H8B	120.0	C57—C56—C55	119.94 (16)
H8A—C8—H8B	120.0	C57—C56—H56	120.0
C91—C9—C10	116.94 (12)	C55—C56—H56	120.0
C91—C9—C3	116.10 (12)	C56—C57—C52	121.78 (16)
C10—C9—C3	102.54 (11)	C56—C57—H57	119.1
C91—C9—H9	106.9	C52—C57—H57	119.1
C10—C9—H9	106.9	O1—C58—H58A	109.5
C3—C9—H9	106.9	O1—C58—H58B	109.5
N1—C10—C11	105.13 (12)	H58A—C58—H58B	109.5
N1—C10—C9	100.42 (12)	O1—C58—H58C	109.5
C11—C10—C9	118.34 (13)	H58A—C58—H58C	109.5
N1—C10—H10	110.7	H58B—C58—H58C	109.5
C11—C10—H10	110.7	C96—C91—C92	117.19 (14)
C9—C10—H10	110.7	C96—C91—C9	119.82 (13)
C10—C11—S1	104.91 (11)	C92—C91—C9	122.99 (14)
C10—C11—H11A	110.8	C93—C92—C91	121.24 (16)
S1—C11—H11A	110.8	C93—C92—H92	119.4
C10—C11—H11B	110.8	C91—C92—H92	119.4
S1—C11—H11B	110.8	C94—C93—C92	120.59 (16)
H11A—C11—H11B	108.8	C94—C93—H93	119.7
N1—C12—S1	102.73 (11)	C92—C93—H93	119.7
N1—C12—H12A	111.2	C93—C94—C95	119.52 (15)
S1—C12—H12A	111.2	C93—C94—O2	115.79 (15)
N1—C12—H12B	111.2	C95—C94—O2	124.68 (16)
S1—C12—H12B	111.2	C94—C95—C96	119.57 (15)
H12A—C12—H12B	109.1	C94—C95—H95	120.2
N1—C13—C17	111.04 (12)	C96—C95—H95	120.2
N1—C13—C14	113.34 (12)	C91—C96—C95	121.90 (15)
C17—C13—C14	101.65 (12)	C91—C96—H96	119.1
N1—C13—C3	101.45 (11)	C95—C96—H96	119.1
C17—C13—C3	117.25 (12)	O2—C97—H97A	109.5
C14—C13—C3	112.61 (12)	O2—C97—H97B	109.5
O3—C14—C15	127.24 (15)	H97A—C97—H97B	109.5
O3—C14—C13	124.21 (14)	O2—C97—H97C	109.5
C15—C14—C13	107.82 (13)	H97A—C97—H97C	109.5
C24—C15—C16	119.92 (16)	H97B—C97—H97C	109.5
C24—C15—C14	132.45 (17)	C12—N1—C10	109.96 (13)
C16—C15—C14	107.60 (13)	C12—N1—C13	121.79 (12)
C15—C16—C21	123.09 (16)	C10—N1—C13	109.94 (12)
C15—C16—C17	113.08 (14)	C2—N2—C1	111.62 (12)
C21—C16—C17	123.81 (17)	C2—N2—C6	113.38 (12)
C18—C17—C16	118.48 (15)	C1—N2—C6	112.06 (12)
C18—C17—C13	131.99 (15)	C55—O1—C58	118.67 (15)
C16—C17—C13	109.53 (14)	C94—O2—C97	116.86 (14)
C17—C18—C19	118.88 (17)	C12—S1—C11	93.49 (7)
C17—C18—H18	120.6
N2—C2—C3—C4	−63.55 (14)	C15—C16—C21—C20	177.70 (15)
N2—C2—C3—C9	173.41 (12)	C17—C16—C21—C20	−0.5 (2)
N2—C2—C3—C13	56.38 (15)	C15—C16—C21—C22	−1.9 (2)
C2—C3—C4—O4	−139.41 (15)	C17—C16—C21—C22	179.93 (15)
C9—C3—C4—O4	−15.1 (2)	C19—C20—C21—C16	−0.6 (3)
C13—C3—C4—O4	100.31 (16)	C19—C20—C21—C22	178.93 (19)
C2—C3—C4—C5	41.65 (17)	C16—C21—C22—C23	0.6 (3)
C9—C3—C4—C5	165.93 (12)	C20—C21—C22—C23	−178.87 (19)
C13—C3—C4—C5	−78.62 (15)	C21—C22—C23—C24	1.1 (3)
O4—C4—C5—C51	−28.6 (2)	C16—C15—C24—C23	0.4 (2)
C3—C4—C5—C51	150.36 (14)	C14—C15—C24—C23	177.97 (17)
O4—C4—C5—C1	155.09 (15)	C22—C23—C24—C15	−1.6 (3)
C3—C4—C5—C1	−26.0 (2)	C4—C5—C51—C52	−176.30 (16)
N2—C1—C5—C51	−147.40 (16)	C1—C5—C51—C52	−0.2 (3)
N2—C1—C5—C4	28.6 (2)	C5—C51—C52—C53	−41.8 (3)
N2—C6—C7—C8	−127.7 (2)	C5—C51—C52—C57	139.11 (19)
C2—C3—C9—C91	33.48 (17)	C57—C52—C53—C54	−1.0 (3)
C4—C3—C9—C91	−86.90 (15)	C51—C52—C53—C54	179.92 (17)
C13—C3—C9—C91	154.14 (12)	C52—C53—C54—C55	−0.8 (3)
C2—C3—C9—C10	−95.26 (14)	C53—C54—C55—O1	−178.99 (17)
C4—C3—C9—C10	144.36 (12)	C53—C54—C55—C56	1.5 (3)
C13—C3—C9—C10	25.40 (14)	O1—C55—C56—C57	179.99 (18)
C91—C9—C10—N1	−170.48 (12)	C54—C55—C56—C57	−0.5 (3)
C3—C9—C10—N1	−42.27 (13)	C55—C56—C57—C52	−1.4 (3)
C91—C9—C10—C11	75.89 (18)	C53—C52—C57—C56	2.1 (3)
C3—C9—C10—C11	−155.90 (13)	C51—C52—C57—C56	−178.78 (18)
N1—C10—C11—S1	33.74 (15)	C10—C9—C91—C96	−145.25 (14)
C9—C10—C11—S1	144.77 (12)	C3—C9—C91—C96	93.40 (16)
C2—C3—C13—N1	123.33 (12)	C10—C9—C91—C92	33.9 (2)
C4—C3—C13—N1	−118.89 (12)	C3—C9—C91—C92	−87.40 (18)
C9—C3—C13—N1	0.89 (14)	C96—C91—C92—C93	0.7 (2)
C2—C3—C13—C17	−115.57 (14)	C9—C91—C92—C93	−178.55 (15)
C4—C3—C13—C17	2.21 (17)	C91—C92—C93—C94	−0.4 (3)
C9—C3—C13—C17	121.99 (13)	C92—C93—C94—C95	−0.5 (3)
C2—C3—C13—C14	1.85 (17)	C92—C93—C94—O2	178.49 (15)
C4—C3—C13—C14	119.63 (13)	C93—C94—C95—C96	1.1 (2)
C9—C3—C13—C14	−120.59 (13)	O2—C94—C95—C96	−177.86 (15)
N1—C13—C14—O3	−46.1 (2)	C92—C91—C96—C95	−0.1 (2)
C17—C13—C14—O3	−165.29 (15)	C9—C91—C96—C95	179.13 (14)
C3—C13—C14—O3	68.39 (19)	C94—C95—C96—C91	−0.8 (2)
N1—C13—C14—C15	124.83 (13)	S1—C12—N1—C10	45.17 (15)
C17—C13—C14—C15	5.60 (15)	S1—C12—N1—C13	175.85 (11)
C3—C13—C14—C15	−120.72 (13)	C11—C10—N1—C12	−53.36 (16)
O3—C14—C15—C24	−11.9 (3)	C9—C10—N1—C12	−176.71 (12)
C13—C14—C15—C24	177.56 (17)	C11—C10—N1—C13	169.93 (12)
O3—C14—C15—C16	165.89 (16)	C9—C10—N1—C13	46.58 (14)
C13—C14—C15—C16	−4.64 (17)	C17—C13—N1—C12	74.54 (18)
C24—C15—C16—C21	1.4 (2)	C14—C13—N1—C12	−39.15 (19)
C14—C15—C16—C21	−176.74 (14)	C3—C13—N1—C12	−160.12 (13)
C24—C15—C16—C17	179.76 (15)	C17—C13—N1—C10	−154.78 (12)
C14—C15—C16—C17	1.63 (18)	C14—C13—N1—C10	91.54 (14)
C15—C16—C17—C18	−177.11 (15)	C3—C13—N1—C10	−29.43 (15)
C21—C16—C17—C18	1.2 (2)	C3—C2—N2—C1	71.71 (15)
C15—C16—C17—C13	2.21 (18)	C3—C2—N2—C6	−160.60 (13)
C21—C16—C17—C13	−179.43 (14)	C5—C1—N2—C2	−51.34 (17)
N1—C13—C17—C18	53.6 (2)	C5—C1—N2—C6	−179.74 (13)
C14—C13—C17—C18	174.48 (17)	C7—C6—N2—C2	−61.56 (19)
C3—C13—C17—C18	−62.3 (2)	C7—C6—N2—C1	65.90 (19)
N1—C13—C17—C16	−125.56 (13)	C54—C55—O1—C58	−6.9 (3)
C14—C13—C17—C16	−4.72 (16)	C56—C55—O1—C58	172.63 (17)
C3—C13—C17—C16	118.49 (14)	C93—C94—O2—C97	172.07 (16)
C16—C17—C18—C19	−0.9 (2)	C95—C94—O2—C97	−9.0 (2)
C13—C17—C18—C19	179.97 (16)	N1—C12—S1—C11	−19.62 (13)
C17—C18—C19—C20	−0.2 (3)	C10—C11—S1—C12	−8.01 (13)
C18—C19—C20—C21	0.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O3	0.97	2.45	2.9587 (19)	113
C93—H93···O1i	0.93	2.49	3.343 (2)	153
C58—H58B···Cg1ii	0.96	2.85	3.487 (2)	125

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C52–C57 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O3	0.97	2.45	2.9587 (19)	113
C93—H93⋯O1i	0.93	2.49	3.343 (2)	153
C58—H58B⋯Cg1ii	0.96	2.85	3.487 (2)	125

Symmetry codes: (i) ; (ii) .