Crystal structure of methyl 1-methyl-3,5-diphenyl-7-tosyl-3,6,7,11b-tetra-hydro-pyrazolo-[4',3':5,6]pyrano[3,4-c]quinoline-5a(5H)-carboxyl-ate.

In the title compound, C35H31N3O5S, the piperidine ring adopts an envelope conformation, with the methine C atom as the flap, and the pyran ring adopts a sofa conformation. The mean planes of these two rings are almost normal to one another, making a dihedral angle of 85.96 (5)°. The two phenyl rings, one attached to the pyrazole ring and the other to the pyran ring, are inclined to one another by 65.41 (11)°. They are inclined to the mean planes of the rings to which they are attached by 12.59 (11) and 70.09 (9)°, respectively. There is an intra-molecular C-H⋯π inter-action involving the tosyl-ate methyl group and the phenyl ring attached to the pyrazole ring. In the crystal, mol-ecules are linked by C-H⋯π inter-actions, forming ribbons parallel to (10-2). The ribbons are linked by slipped parallel π-π inter-actions involving inversion-related pyrazole rings [inter-centroid distance = 3.672 (2) Å], forming slabs parallel to (001). A preliminary report of this structure has been published [Bakthadoss et al. (2014 ▶). Eur. J. Org. Chem. pp. 1505-1513].

Related literature

For biological activity of sulfonamide compounds, see: Genç et al. (2008 ▶); Özbek et al. (2007 ▶); Briganti et al. (1997 ▶); Borne et al. (1974 ▶); De Clercq (2001 ▶). For details of the Thrope–Ingold effect, see: Bassindale (1984 ▶). For a preliminary report of this structure, see: Bakthadoss et al. (2014 ▶).

Experimental

Crystal data

C35H31N3O5S

M = 605.69

Triclinic,

a = 10.781 (5) Å

b = 11.682 (5) Å

c = 14.560 (5) Å

α = 112.708 (5)°

β = 91.908 (5)°

γ = 113.180 (5)°

V = 1517.5 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.16 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.979, T max = 0.983

23138 measured reflections

6308 independent reflections

5070 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.118

S = 1.04

6308 reflections

406 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.46 e Å−3

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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681402515X/su5015sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402515X/su5015Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681402515X/su5015Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681402515X/su5015fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level (H atoms have been omitted for clarity).

Click here for additional data file.

b . DOI: 10.1107/S160053681402515X/su5015fig2.tif

A partial view along the b axis of the crystal packing of the title compound, showing the π-π inter­action (red circles represent the centroids of the pyrazole rings; H atoms have been omitted for clarity).

Click here for additional data file.

c . DOI: 10.1107/S160053681402515X/su5015fig3.tif

A view along the c axis of the crystal packing of the title compound, showing the C—H⋯π inter­actions as dashed lines (H atoms as silver balls; see Table 1 for details; H atoms not involved in these inter­actions have been omitted for clarity).

CCDC reference: 1034400

Additional supporting information: crystallographic information; 3D view; checkCIF report

C35H31N3O5S	Z = 2
Mr = 605.69	F(000) = 636
Triclinic, P1	Dx = 1.326 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.781 (5) Å	Cell parameters from 8834 reflections
b = 11.682 (5) Å	θ = 2.1–31.2°
c = 14.560 (5) Å	µ = 0.16 mm−1
α = 112.708 (5)°	T = 293 K
β = 91.908 (5)°	Block, colourless
γ = 113.180 (5)°	0.25 × 0.20 × 0.20 mm
V = 1517.5 (11) Å3

Bruker Kappa APEXII CCD diffractometer	6308 independent reflections
Radiation source: fine-focus sealed tube	5070 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω and φ scan	θmax = 26.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
Tmin = 0.979, Tmax = 0.983	k = −14→14
23138 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.0517P)2 + 0.4727P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
6308 reflections	Δρmax = 0.29 e Å−3
406 parameters	Δρmin = −0.46 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0095 (12)

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
H10	0.3360 (16)	1.4361 (17)	0.3161 (12)	0.040 (4)*
H19	0.5740 (16)	1.5341 (17)	0.3206 (12)	0.039 (4)*
S1	0.28913 (5)	0.93229 (4)	0.10089 (4)	0.05837 (16)
O3	0.63192 (11)	1.40325 (11)	0.34307 (8)	0.0427 (3)
N2	0.44250 (14)	1.28179 (15)	0.50555 (10)	0.0451 (3)
N1	0.56158 (13)	1.32792 (14)	0.47097 (10)	0.0408 (3)
O5	0.39810 (15)	1.50993 (13)	0.17850 (9)	0.0585 (3)
C10	0.33680 (16)	1.34586 (16)	0.28908 (11)	0.0383 (3)
C18	0.53403 (16)	1.35576 (15)	0.39247 (11)	0.0381 (3)
C8	0.42521 (16)	1.19731 (15)	0.15787 (12)	0.0428 (4)
H8A	0.4420	1.1826	0.0901	0.051*
H8B	0.4977	1.1919	0.1947	0.051*
C11	0.19167 (16)	1.23858 (17)	0.23342 (12)	0.0428 (4)
C26	0.68408 (17)	1.33323 (16)	0.51560 (12)	0.0434 (4)
N3	0.29016 (14)	1.08531 (14)	0.14857 (12)	0.0519 (4)
C9	0.43402 (16)	1.34228 (15)	0.21259 (11)	0.0374 (3)
C32	0.34569 (16)	1.28201 (17)	0.44719 (12)	0.0415 (3)
C19	0.58361 (16)	1.45108 (15)	0.27642 (11)	0.0378 (3)
C12	0.17045 (17)	1.10761 (18)	0.16377 (12)	0.0463 (4)
C20	0.69474 (16)	1.48845 (15)	0.21891 (11)	0.0405 (3)
C17	0.39844 (16)	1.32776 (15)	0.37384 (11)	0.0373 (3)
C34	0.39288 (18)	1.38461 (17)	0.13379 (12)	0.0471 (4)
C31	0.6898 (2)	1.31935 (19)	0.60547 (13)	0.0534 (4)
H31	0.6142	1.3067	0.6361	0.064*
O4	0.35987 (19)	1.31515 (16)	0.04410 (10)	0.0804 (5)
O1	0.33189 (16)	0.90828 (14)	0.00616 (10)	0.0696 (4)
C21	0.7437 (2)	1.61657 (19)	0.21789 (15)	0.0584 (5)
H21	0.7050	1.6760	0.2501	0.070*
C33	0.20231 (19)	1.2383 (2)	0.46483 (16)	0.0623 (5)
H33A	0.1976	1.2124	0.5202	0.093*
H33B	0.1391	1.1607	0.4041	0.093*
H33C	0.1779	1.3135	0.4815	0.093*
C5	0.4190 (2)	0.95070 (16)	0.18862 (14)	0.0535 (4)
C25	0.75349 (19)	1.40223 (17)	0.17003 (14)	0.0540 (4)
H25	0.7215	1.3154	0.1694	0.065*
O2	0.16039 (16)	0.83495 (14)	0.10388 (15)	0.0914 (5)
C16	0.08020 (19)	1.2695 (2)	0.24679 (15)	0.0574 (5)
H16	0.0947	1.3581	0.2915	0.069*
C23	0.9079 (2)	1.5709 (2)	0.12211 (15)	0.0671 (6)
H23	0.9800	1.5988	0.0903	0.080*
C13	0.03616 (19)	1.0084 (2)	0.11023 (14)	0.0599 (5)
H13	0.0207	0.9206	0.0631	0.072*
C30	0.8089 (2)	1.3243 (2)	0.64975 (16)	0.0653 (5)
H30	0.8127	1.3152	0.7104	0.078*
C28	0.9133 (2)	1.3542 (3)	0.5160 (2)	0.0762 (6)
H28	0.9890	1.3661	0.4855	0.091*
C14	−0.0727 (2)	1.0410 (3)	0.12734 (16)	0.0709 (6)
H14	−0.1620	0.9738	0.0926	0.085*
C24	0.8596 (2)	1.4436 (2)	0.12183 (15)	0.0648 (5)
H24	0.8983	1.3844	0.0891	0.078*
C29	0.9205 (2)	1.3424 (2)	0.60559 (18)	0.0706 (6)
H29	1.0003	1.3465	0.6360	0.085*
C27	0.7955 (2)	1.3489 (2)	0.46962 (17)	0.0639 (5)
H27	0.7917	1.3558	0.4082	0.077*
C4	0.5298 (2)	0.9284 (2)	0.15784 (17)	0.0696 (6)
H4	0.5400	0.9094	0.0911	0.084*
C2	0.6146 (3)	0.9648 (2)	0.32640 (18)	0.0749 (6)
C6	0.4065 (3)	0.9812 (2)	0.28845 (17)	0.0773 (7)
H6	0.3319	0.9970	0.3099	0.093*
C15	−0.0524 (2)	1.1702 (3)	0.19444 (18)	0.0717 (6)
H15	−0.1270	1.1911	0.2048	0.086*
C22	0.8497 (2)	1.6572 (2)	0.16937 (18)	0.0731 (6)
H22	0.8814	1.7433	0.1689	0.088*
C1	0.7210 (4)	0.9729 (3)	0.4012 (2)	0.1103 (10)
H1A	0.7904	0.9537	0.3676	0.165*
H1B	0.6772	0.9062	0.4272	0.165*
H1C	0.7633	1.0639	0.4566	0.165*
C3	0.6255 (3)	0.9343 (3)	0.2266 (2)	0.0811 (7)
H3	0.6994	0.9173	0.2051	0.097*
C7	0.5029 (3)	0.9882 (3)	0.35505 (18)	0.0877 (8)
H7	0.4935	1.0093	0.4221	0.105*
C35	0.3590 (3)	1.5611 (3)	0.1114 (2)	0.0913 (8)
H35B	0.3666	1.6518	0.1513	0.137*
H35A	0.2653	1.4999	0.0741	0.137*
H35C	0.4193	1.5652	0.0645	0.137*

	U11	U22	U33	U12	U13	U23
S1	0.0555 (3)	0.0336 (2)	0.0674 (3)	0.00953 (19)	0.0169 (2)	0.0141 (2)
O3	0.0370 (6)	0.0510 (6)	0.0478 (6)	0.0183 (5)	0.0128 (5)	0.0297 (5)
N2	0.0434 (8)	0.0582 (8)	0.0469 (7)	0.0262 (7)	0.0174 (6)	0.0310 (7)
N1	0.0384 (7)	0.0492 (7)	0.0440 (7)	0.0221 (6)	0.0125 (6)	0.0260 (6)
O5	0.0812 (9)	0.0553 (7)	0.0515 (7)	0.0362 (7)	0.0097 (6)	0.0295 (6)
C10	0.0407 (8)	0.0399 (8)	0.0391 (8)	0.0208 (7)	0.0108 (6)	0.0186 (6)
C18	0.0402 (8)	0.0386 (7)	0.0391 (8)	0.0183 (7)	0.0116 (6)	0.0192 (6)
C8	0.0405 (9)	0.0353 (8)	0.0470 (9)	0.0120 (7)	0.0154 (7)	0.0169 (7)
C11	0.0390 (9)	0.0544 (9)	0.0410 (8)	0.0204 (7)	0.0103 (7)	0.0266 (7)
C26	0.0420 (9)	0.0413 (8)	0.0499 (9)	0.0203 (7)	0.0061 (7)	0.0211 (7)
N3	0.0405 (8)	0.0370 (7)	0.0665 (9)	0.0105 (6)	0.0173 (7)	0.0174 (7)
C9	0.0388 (8)	0.0355 (7)	0.0370 (7)	0.0141 (6)	0.0097 (6)	0.0171 (6)
C32	0.0421 (9)	0.0495 (9)	0.0411 (8)	0.0243 (7)	0.0150 (7)	0.0227 (7)
C19	0.0422 (9)	0.0343 (7)	0.0374 (7)	0.0157 (7)	0.0091 (6)	0.0171 (6)
C12	0.0392 (9)	0.0543 (9)	0.0416 (8)	0.0146 (7)	0.0103 (7)	0.0231 (7)
C20	0.0402 (8)	0.0360 (7)	0.0373 (8)	0.0096 (6)	0.0067 (6)	0.0156 (6)
C17	0.0383 (8)	0.0390 (7)	0.0379 (7)	0.0193 (6)	0.0110 (6)	0.0175 (6)
C34	0.0473 (10)	0.0483 (9)	0.0432 (9)	0.0157 (8)	0.0085 (7)	0.0232 (7)
C31	0.0554 (11)	0.0603 (11)	0.0497 (10)	0.0301 (9)	0.0089 (8)	0.0245 (8)
O4	0.1224 (14)	0.0725 (9)	0.0388 (7)	0.0412 (9)	0.0013 (8)	0.0200 (7)
O1	0.0846 (10)	0.0541 (8)	0.0490 (7)	0.0274 (7)	0.0122 (7)	0.0056 (6)
C21	0.0624 (12)	0.0466 (9)	0.0712 (12)	0.0200 (9)	0.0212 (10)	0.0340 (9)
C33	0.0481 (11)	0.0974 (15)	0.0655 (12)	0.0370 (11)	0.0260 (9)	0.0524 (11)
C5	0.0718 (12)	0.0342 (8)	0.0576 (10)	0.0222 (8)	0.0291 (9)	0.0231 (7)
C25	0.0528 (10)	0.0390 (8)	0.0604 (10)	0.0135 (8)	0.0218 (8)	0.0181 (8)
O2	0.0651 (10)	0.0440 (8)	0.1374 (15)	0.0041 (7)	0.0300 (10)	0.0326 (9)
C16	0.0482 (11)	0.0734 (12)	0.0613 (11)	0.0323 (10)	0.0156 (9)	0.0337 (10)
C23	0.0573 (12)	0.0717 (13)	0.0573 (11)	0.0091 (10)	0.0221 (9)	0.0326 (10)
C13	0.0459 (10)	0.0661 (12)	0.0472 (10)	0.0098 (9)	0.0079 (8)	0.0202 (9)
C30	0.0686 (13)	0.0733 (13)	0.0588 (11)	0.0372 (11)	−0.0015 (10)	0.0284 (10)
C28	0.0486 (12)	0.0986 (17)	0.1131 (19)	0.0394 (12)	0.0253 (12)	0.0689 (15)
C14	0.0384 (10)	0.0953 (17)	0.0600 (12)	0.0134 (10)	0.0042 (9)	0.0325 (12)
C24	0.0549 (11)	0.0579 (11)	0.0605 (11)	0.0144 (9)	0.0250 (9)	0.0149 (9)
C29	0.0519 (12)	0.0750 (13)	0.0912 (15)	0.0313 (11)	−0.0010 (11)	0.0400 (12)
C27	0.0512 (11)	0.0893 (14)	0.0827 (14)	0.0388 (11)	0.0244 (10)	0.0591 (12)
C4	0.0756 (14)	0.0833 (14)	0.0634 (12)	0.0378 (12)	0.0333 (11)	0.0405 (11)
C2	0.1020 (18)	0.0482 (11)	0.0754 (14)	0.0260 (11)	0.0109 (13)	0.0356 (10)
C6	0.123 (2)	0.0769 (14)	0.0718 (14)	0.0663 (15)	0.0543 (14)	0.0453 (12)
C15	0.0422 (11)	0.1032 (18)	0.0780 (14)	0.0350 (12)	0.0131 (10)	0.0444 (14)
C22	0.0742 (14)	0.0611 (12)	0.0874 (15)	0.0142 (11)	0.0269 (12)	0.0508 (12)
C1	0.146 (3)	0.0780 (17)	0.106 (2)	0.0447 (18)	−0.0054 (19)	0.0468 (16)
C3	0.0771 (16)	0.0935 (17)	0.0934 (17)	0.0399 (14)	0.0352 (13)	0.0570 (14)
C7	0.155 (3)	0.0794 (15)	0.0605 (13)	0.0726 (18)	0.0419 (15)	0.0387 (12)
C35	0.134 (2)	0.0933 (17)	0.0816 (16)	0.0638 (17)	0.0154 (15)	0.0578 (14)

S1—O2	1.4217 (16)	C33—H33B	0.9600
S1—O1	1.4279 (15)	C33—H33C	0.9600
S1—N3	1.6442 (16)	C5—C4	1.373 (3)
S1—C5	1.752 (2)	C5—C6	1.382 (3)
O3—C18	1.3552 (18)	C25—C24	1.384 (2)
O3—C19	1.4627 (18)	C25—H25	0.9300
N2—C32	1.325 (2)	C16—C15	1.382 (3)
N2—N1	1.3784 (18)	C16—H16	0.9300
N1—C18	1.3567 (19)	C23—C24	1.367 (3)
N1—C26	1.420 (2)	C23—C22	1.369 (3)
O5—C34	1.329 (2)	C23—H23	0.9300
O5—C35	1.453 (2)	C13—C14	1.372 (3)
C10—C11	1.504 (2)	C13—H13	0.9300
C10—C17	1.506 (2)	C30—C29	1.365 (3)
C10—C9	1.555 (2)	C30—H30	0.9300
C10—H10	0.977 (16)	C28—C29	1.367 (3)
C18—C17	1.359 (2)	C28—C27	1.385 (3)
C8—N3	1.483 (2)	C28—H28	0.9300
C8—C9	1.529 (2)	C14—C15	1.367 (3)
C8—H8A	0.9700	C14—H14	0.9300
C8—H8B	0.9700	C24—H24	0.9300
C11—C16	1.384 (2)	C29—H29	0.9300
C11—C12	1.390 (2)	C27—H27	0.9300
C26—C27	1.378 (3)	C4—C3	1.376 (3)
C26—C31	1.382 (2)	C4—H4	0.9300
N3—C12	1.422 (2)	C2—C3	1.377 (3)
C9—C34	1.528 (2)	C2—C7	1.380 (4)
C9—C19	1.567 (2)	C2—C1	1.505 (4)
C32—C17	1.411 (2)	C6—C7	1.354 (4)
C32—C33	1.491 (2)	C6—H6	0.9300
C19—C20	1.505 (2)	C15—H15	0.9300
C19—H19	0.983 (16)	C22—H22	0.9300
C12—C13	1.398 (3)	C1—H1A	0.9600
C20—C25	1.379 (2)	C1—H1B	0.9600
C20—C21	1.384 (2)	C1—H1C	0.9600
C34—O4	1.189 (2)	C3—H3	0.9300
C31—C30	1.387 (3)	C7—H7	0.9300
C31—H31	0.9300	C35—H35B	0.9600
C21—C22	1.384 (3)	C35—H35A	0.9600
C21—H21	0.9300	C35—H35C	0.9600
C33—H33A	0.9600
O2—S1—O1	119.29 (10)	H33A—C33—H33B	109.5
O2—S1—N3	108.19 (9)	C32—C33—H33C	109.5
O1—S1—N3	108.89 (8)	H33A—C33—H33C	109.5
O2—S1—C5	108.09 (11)	H33B—C33—H33C	109.5
O1—S1—C5	107.78 (9)	C4—C5—C6	119.6 (2)
N3—S1—C5	103.47 (8)	C4—C5—S1	120.53 (15)
C18—O3—C19	111.44 (12)	C6—C5—S1	119.75 (17)
C32—N2—N1	105.70 (12)	C20—C25—C24	120.66 (17)
C18—N1—N2	109.14 (12)	C20—C25—H25	119.7
C18—N1—C26	131.38 (13)	C24—C25—H25	119.7
N2—N1—C26	119.42 (12)	C15—C16—C11	120.7 (2)
C34—O5—C35	116.36 (16)	C15—C16—H16	119.6
C11—C10—C17	115.19 (13)	C11—C16—H16	119.6
C11—C10—C9	109.36 (13)	C24—C23—C22	119.68 (18)
C17—C10—C9	106.39 (12)	C24—C23—H23	120.2
C11—C10—H10	107.5 (10)	C22—C23—H23	120.2
C17—C10—H10	109.8 (9)	C14—C13—C12	119.8 (2)
C9—C10—H10	108.4 (9)	C14—C13—H13	120.1
O3—C18—N1	122.47 (14)	C12—C13—H13	120.1
O3—C18—C17	127.94 (14)	C29—C30—C31	120.89 (19)
N1—C18—C17	109.59 (13)	C29—C30—H30	119.6
N3—C8—C9	113.72 (13)	C31—C30—H30	119.6
N3—C8—H8A	108.8	C29—C28—C27	121.4 (2)
C9—C8—H8A	108.8	C29—C28—H28	119.3
N3—C8—H8B	108.8	C27—C28—H28	119.3
C9—C8—H8B	108.8	C15—C14—C13	121.25 (19)
H8A—C8—H8B	107.7	C15—C14—H14	119.4
C16—C11—C12	119.56 (16)	C13—C14—H14	119.4
C16—C11—C10	121.39 (16)	C23—C24—C25	120.4 (2)
C12—C11—C10	118.99 (14)	C23—C24—H24	119.8
C27—C26—C31	119.75 (16)	C25—C24—H24	119.8
C27—C26—N1	121.13 (15)	C30—C29—C28	119.08 (19)
C31—C26—N1	119.11 (15)	C30—C29—H29	120.5
C12—N3—C8	122.18 (14)	C28—C29—H29	120.5
C12—N3—S1	124.35 (11)	C26—C27—C28	119.28 (19)
C8—N3—S1	112.69 (11)	C26—C27—H27	120.4
C34—C9—C8	109.29 (13)	C28—C27—H27	120.4
C34—C9—C10	109.65 (13)	C5—C4—C3	119.4 (2)
C8—C9—C10	110.66 (12)	C5—C4—H4	120.3
C34—C9—C19	109.12 (12)	C3—C4—H4	120.3
C8—C9—C19	111.53 (13)	C3—C2—C7	117.4 (2)
C10—C9—C19	106.54 (12)	C3—C2—C1	121.1 (3)
N2—C32—C17	111.64 (14)	C7—C2—C1	121.4 (2)
N2—C32—C33	119.83 (14)	C7—C6—C5	119.9 (2)
C17—C32—C33	128.53 (15)	C7—C6—H6	120.1
O3—C19—C20	106.54 (12)	C5—C6—H6	120.1
O3—C19—C9	109.95 (11)	C14—C15—C16	119.4 (2)
C20—C19—C9	117.66 (12)	C14—C15—H15	120.3
O3—C19—H19	107.2 (9)	C16—C15—H15	120.3
C20—C19—H19	109.9 (9)	C23—C22—C21	120.24 (18)
C9—C19—H19	105.2 (10)	C23—C22—H22	119.9
C11—C12—C13	119.26 (17)	C21—C22—H22	119.9
C11—C12—N3	116.79 (15)	C2—C1—H1A	109.5
C13—C12—N3	123.90 (17)	C2—C1—H1B	109.5
C25—C20—C21	118.44 (16)	H1A—C1—H1B	109.5
C25—C20—C19	122.73 (14)	C2—C1—H1C	109.5
C21—C20—C19	118.79 (15)	H1A—C1—H1C	109.5
C18—C17—C32	103.92 (13)	H1B—C1—H1C	109.5
C18—C17—C10	121.65 (13)	C4—C3—C2	121.6 (2)
C32—C17—C10	134.42 (14)	C4—C3—H3	119.2
O4—C34—O5	123.95 (16)	C2—C3—H3	119.2
O4—C34—C9	124.90 (16)	C6—C7—C2	122.0 (2)
O5—C34—C9	111.15 (13)	C6—C7—H7	119.0
C26—C31—C30	119.63 (18)	C2—C7—H7	119.0
C26—C31—H31	120.2	O5—C35—H35B	109.5
C30—C31—H31	120.2	O5—C35—H35A	109.5
C20—C21—C22	120.60 (19)	H35B—C35—H35A	109.5
C20—C21—H21	119.7	O5—C35—H35C	109.5
C22—C21—H21	119.7	H35B—C35—H35C	109.5
C32—C33—H33A	109.5	H35A—C35—H35C	109.5
C32—C33—H33B	109.5
C32—N2—N1—C18	0.31 (17)	O3—C18—C17—C10	0.9 (2)
C32—N2—N1—C26	−177.06 (14)	N1—C18—C17—C10	−178.65 (13)
C19—O3—C18—N1	−168.50 (13)	N2—C32—C17—C18	−0.31 (18)
C19—O3—C18—C17	12.0 (2)	C33—C32—C17—C18	179.12 (18)
N2—N1—C18—O3	179.90 (13)	N2—C32—C17—C10	178.67 (16)
C26—N1—C18—O3	−3.2 (3)	C33—C32—C17—C10	−1.9 (3)
N2—N1—C18—C17	−0.52 (17)	C11—C10—C17—C18	142.60 (15)
C26—N1—C18—C17	176.42 (15)	C9—C10—C17—C18	21.25 (19)
C17—C10—C11—C16	107.29 (17)	C11—C10—C17—C32	−36.2 (2)
C9—C10—C11—C16	−132.99 (15)	C9—C10—C17—C32	−157.59 (17)
C17—C10—C11—C12	−75.64 (18)	C35—O5—C34—O4	0.7 (3)
C9—C10—C11—C12	44.08 (18)	C35—O5—C34—C9	−179.09 (17)
C18—N1—C26—C27	−11.1 (3)	C8—C9—C34—O4	−0.3 (2)
N2—N1—C26—C27	165.55 (16)	C10—C9—C34—O4	−121.7 (2)
C18—N1—C26—C31	170.30 (16)	C19—C9—C34—O4	121.9 (2)
N2—N1—C26—C31	−13.0 (2)	C8—C9—C34—O5	179.48 (13)
C9—C8—N3—C12	15.9 (2)	C10—C9—C34—O5	58.02 (17)
C9—C8—N3—S1	−173.73 (11)	C19—C9—C34—O5	−58.32 (18)
O2—S1—N3—C12	−15.17 (18)	C27—C26—C31—C30	1.4 (3)
O1—S1—N3—C12	115.88 (15)	N1—C26—C31—C30	179.97 (16)
C5—S1—N3—C12	−129.68 (15)	C25—C20—C21—C22	−0.4 (3)
O2—S1—N3—C8	174.75 (13)	C19—C20—C21—C22	177.39 (18)
O1—S1—N3—C8	−54.20 (15)	O2—S1—C5—C4	124.05 (17)
C5—S1—N3—C8	60.24 (14)	O1—S1—C5—C4	−6.13 (18)
N3—C8—C9—C34	−92.95 (16)	N3—S1—C5—C4	−121.37 (16)
N3—C8—C9—C10	27.89 (18)	O2—S1—C5—C6	−52.72 (18)
N3—C8—C9—C19	146.30 (14)	O1—S1—C5—C6	177.09 (15)
C11—C10—C9—C34	64.66 (16)	N3—S1—C5—C6	61.85 (16)
C17—C10—C9—C34	−170.33 (12)	C21—C20—C25—C24	0.5 (3)
C11—C10—C9—C8	−55.97 (16)	C19—C20—C25—C24	−177.17 (17)
C17—C10—C9—C8	69.04 (15)	C12—C11—C16—C15	2.4 (3)
C11—C10—C9—C19	−177.37 (12)	C10—C11—C16—C15	179.42 (17)
C17—C10—C9—C19	−52.37 (15)	C11—C12—C13—C14	−0.4 (3)
N1—N2—C32—C17	0.00 (18)	N3—C12—C13—C14	−177.57 (17)
N1—N2—C32—C33	−179.48 (16)	C26—C31—C30—C29	−0.2 (3)
C18—O3—C19—C20	−174.85 (12)	C12—C13—C14—C15	1.5 (3)
C18—O3—C19—C9	−46.32 (16)	C22—C23—C24—C25	−0.8 (3)
C34—C9—C19—O3	−172.63 (12)	C20—C25—C24—C23	0.1 (3)
C8—C9—C19—O3	−51.79 (16)	C31—C30—C29—C28	−0.6 (3)
C10—C9—C19—O3	69.06 (15)	C27—C28—C29—C30	0.3 (4)
C34—C9—C19—C20	−50.48 (18)	C31—C26—C27—C28	−1.7 (3)
C8—C9—C19—C20	70.36 (16)	N1—C26—C27—C28	179.71 (19)
C10—C9—C19—C20	−168.78 (13)	C29—C28—C27—C26	0.9 (4)
C16—C11—C12—C13	−1.5 (2)	C6—C5—C4—C3	1.2 (3)
C10—C11—C12—C13	−178.65 (14)	S1—C5—C4—C3	−175.61 (17)
C16—C11—C12—N3	175.88 (15)	C4—C5—C6—C7	−0.4 (3)
C10—C11—C12—N3	−1.3 (2)	S1—C5—C6—C7	176.45 (18)
C8—N3—C12—C11	−31.4 (2)	C13—C14—C15—C16	−0.7 (3)
S1—N3—C12—C11	159.43 (13)	C11—C16—C15—C14	−1.3 (3)
C8—N3—C12—C13	145.87 (17)	C24—C23—C22—C21	0.9 (3)
S1—N3—C12—C13	−23.3 (2)	C20—C21—C22—C23	−0.3 (3)
O3—C19—C20—C25	48.67 (19)	C5—C4—C3—C2	−1.3 (4)
C9—C19—C20—C25	−75.2 (2)	C7—C2—C3—C4	0.6 (3)
O3—C19—C20—C21	−129.00 (16)	C1—C2—C3—C4	−179.1 (2)
C9—C19—C20—C21	107.12 (17)	C5—C6—C7—C2	−0.4 (4)
O3—C18—C17—C32	−179.96 (15)	C3—C2—C7—C6	0.3 (4)
N1—C18—C17—C32	0.49 (17)	C1—C2—C7—C6	180.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cg7	0.96	2.80	3.682 (4)	154
C29—H29···Cg6i	0.93	2.94	3.734 (3)	144
C35—H35B···Cg4ii	0.96	2.97	3.853 (4)	154

Table 1

Hydrogen-bond geometry (, )

Cg4, Cg6 and Cg7 are the centroids of rings C2C7, C20C25 and C26C31, respectively.

DHA	DH	HA	D A	DHA
C1H1C Cg7	0.96	2.80	3.682(4)	154
C29H29Cg6i	0.93	2.94	3.734(3)	144
C35H35B Cg4ii	0.96	2.97	3.853(4)	154

Symmetry codes: (i) ; (ii) .