Ethyl 7'-(6-benz-yloxy-2,2-dimethyl-tetra-hydro-furo[3,2-d][1,3]dioxol-5-yl)-2-oxo-5',6',7',7a'-tetra-hydro-1'H,2H-spiro-[acenaphthyl-ene-1,5'-pyrrolo-[1,2-c][1,3]thia-zole]-6'-carboxyl-ate.

In the title compound, C(34)H(35)NO(7)S, the acenaphthyl-ene unit is essentially planar (r.m.s. deviation = 0.0335 Å). The pyrrolo-thia-zole ring system is folded about the bridging N-C bond; the thia-zolidine and pyrrolidine rings adopt S- and C-envelope conformations, respectively, with a 'butterfly' angle between the mean planes of 51.38 (10)°. The dioxolane and tetra-hydro-furan rings adopt O- and a C-envelope conformations, respectively, with a 'butterfly' angle between the mean planes of 57.12 (10)°. Two C atoms are each disordered over two positions with site-occupancy factors of 0.450 (7) and 0.550 (7). The crystal packing is stabilized by C-H⋯O inter-actions, generating an R(2) (2)(14) graph-set ring motif.

Related literature

For the biological properties of spiro­heterocycles, see: Kilonda et al. (1995 ▶); Ferguson et al. (2005 ▶). For a related structure, see: Jagadeesan et al. (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C34H35NO7S

M = 601.69

Monoclinic,

a = 8.588 (5) Å

b = 20.446 (5) Å

c = 8.851 (5) Å

β = 93.282 (5)°

V = 1551.6 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.15 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.955, T max = 0.970

13521 measured reflections

5470 independent reflections

4678 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.083

S = 1.03

5470 reflections

400 parameters

5 restraints

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 2630 Friedel pairs

Flack parameter: 0.04 (7)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812032291/pv2565sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032291/pv2565Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812032291/pv2565Isup3.cml

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

C34H35NO7S	F(000) = 636
Mr = 601.69	Dx = 1.288 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5470 reflections
a = 8.588 (5) Å	θ = 2.3–25.0°
b = 20.446 (5) Å	µ = 0.15 mm−1
c = 8.851 (5) Å	T = 293 K
β = 93.282 (5)°	Block, colourless
V = 1551.6 (13) Å3	0.30 × 0.20 × 0.20 mm
Z = 2

Bruker Kappa APEXII CCD diffractometer	5470 independent reflections
Radiation source: fine-focus sealed tube	4678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.955, Tmax = 0.970	k = −24→24
13521 measured reflections	l = −10→10

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.0365P)2 + 0.1903P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
5470 reflections	Δρmax = 0.17 e Å−3
400 parameters	Δρmin = −0.16 e Å−3
5 restraints	Absolute structure: Flack (1983), 2630 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.04 (7)

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	Occ. (<1)
C1	0.6985 (4)	1.0180 (2)	−0.1860 (4)	0.0964 (12)
H1	0.7439	0.9791	−0.1517	0.116*
C2	0.7881 (4)	1.0639 (3)	−0.2530 (5)	0.1233 (17)
H2	0.8946	1.0569	−0.2592	0.148*
C3	0.7226 (6)	1.1190 (2)	−0.3098 (5)	0.1204 (15)
H3	0.7837	1.1503	−0.3544	0.145*
C4	0.5673 (7)	1.12883 (19)	−0.3019 (5)	0.1210 (16)
H4	0.5213	1.1662	−0.3442	0.145*
C5	0.4768 (4)	1.08343 (17)	−0.2310 (4)	0.0861 (10)
H5	0.3703	1.0906	−0.2259	0.103*
C6	0.5424 (3)	1.02855 (15)	−0.1686 (3)	0.0598 (7)
C7	0.4478 (3)	0.97918 (18)	−0.0920 (3)	0.0767 (9)
H7A	0.3442	0.9965	−0.0788	0.092*
H7B	0.4373	0.9401	−0.1540	0.092*
C8	0.4389 (2)	0.91510 (11)	0.1311 (2)	0.0385 (5)
H8	0.3568	0.8941	0.0667	0.046*
C9	0.3749 (2)	0.94455 (12)	0.2722 (2)	0.0444 (5)
H9	0.3382	0.9896	0.2576	0.053*
C10	0.2888 (3)	0.89133 (16)	0.4821 (2)	0.0579 (7)
C11	0.5109 (2)	0.93842 (12)	0.3919 (2)	0.0448 (5)
H11	0.5512	0.9815	0.4227	0.054*
C12	0.5534 (2)	0.86545 (11)	0.2003 (2)	0.0371 (5)
H12	0.4946	0.8287	0.2394	0.045*
C13	0.1895 (4)	0.9367 (2)	0.5694 (3)	0.0944 (12)
H13A	0.2072	0.9285	0.6758	0.142*
H13B	0.0816	0.9295	0.5401	0.142*
H13C	0.2165	0.9812	0.5481	0.142*
C14	0.2592 (5)	0.8205 (2)	0.5147 (5)	0.1105 (13)
H14A	0.3315	0.7940	0.4630	0.166*
H14B	0.1546	0.8094	0.4802	0.166*
H14C	0.2727	0.8129	0.6217	0.166*
C15	0.6747 (2)	0.83868 (11)	0.0969 (2)	0.0348 (5)
H15	0.6642	0.8626	0.0009	0.042*
C16	0.8441 (2)	0.84394 (11)	0.1576 (2)	0.0358 (5)
H16	0.8497	0.8358	0.2669	0.043*
C17	0.9220 (2)	0.90903 (12)	0.1268 (3)	0.0475 (6)
H17A	0.9987	0.9196	0.2078	0.057*
H17B	0.8451	0.9438	0.1190	0.057*
C18	1.0597 (3)	0.81554 (12)	0.0079 (3)	0.0522 (6)
H18A	1.0795	0.7891	−0.0799	0.063*
H18B	1.1515	0.8145	0.0770	0.063*
C19	0.8148 (2)	0.74831 (11)	−0.0048 (2)	0.0346 (5)
C20	0.6583 (2)	0.76627 (10)	0.0622 (2)	0.0361 (5)
H20	0.6520	0.7429	0.1583	0.043*
C21	0.5169 (3)	0.74830 (13)	−0.0381 (3)	0.0469 (6)
C24	0.8642 (2)	0.67578 (11)	0.0284 (2)	0.0402 (5)
C25	0.9027 (3)	0.64571 (11)	−0.1152 (3)	0.0447 (5)
C26	0.9563 (3)	0.58507 (13)	−0.1508 (3)	0.0633 (7)
H26	0.9807	0.5543	−0.0758	0.076*
C27	0.9734 (4)	0.57065 (14)	−0.3031 (3)	0.0784 (9)
H27	1.0113	0.5297	−0.3286	0.094*
C28	0.9366 (4)	0.61442 (15)	−0.4160 (3)	0.0701 (8)
H28	0.9489	0.6026	−0.5160	0.084*
C29	0.8805 (3)	0.67706 (13)	−0.3835 (3)	0.0501 (6)
C30	0.8345 (3)	0.72664 (15)	−0.4870 (3)	0.0603 (7)
H30	0.8428	0.7201	−0.5902	0.072*
C31	0.7775 (3)	0.78419 (14)	−0.4354 (3)	0.0606 (7)
H31	0.7448	0.8160	−0.5054	0.073*
C32	0.7663 (3)	0.79738 (13)	−0.2803 (2)	0.0505 (6)
H32	0.7273	0.8373	−0.2490	0.061*
C33	0.8127 (2)	0.75142 (11)	−0.1771 (2)	0.0371 (5)
C34	0.8683 (2)	0.69111 (11)	−0.2306 (2)	0.0411 (5)
N1	0.92549 (18)	0.79087 (9)	0.08164 (18)	0.0381 (4)
O1	0.4185 (2)	0.78642 (10)	−0.0821 (2)	0.0725 (6)
O3	0.8674 (2)	0.65153 (8)	0.15251 (18)	0.0547 (4)
O4	0.52013 (16)	0.96312 (8)	0.05080 (16)	0.0437 (4)
O5	0.62621 (14)	0.90082 (8)	0.32626 (14)	0.0443 (4)
O6	0.44787 (17)	0.90588 (11)	0.51319 (16)	0.0641 (5)
O7	0.26019 (15)	0.90235 (10)	0.32494 (15)	0.0540 (4)
S1	1.01420 (7)	0.89962 (4)	−0.04894 (7)	0.05884 (19)
O2	0.5175 (2)	0.68557 (9)	−0.0717 (2)	0.0714 (5)
C22'	0.3864 (13)	0.6486 (8)	−0.1444 (12)	0.086 (3)	0.450 (7)
H22A	0.2876	0.6703	−0.1319	0.103*	0.450 (7)
H22B	0.3818	0.6044	−0.1052	0.103*	0.450 (7)
C23'	0.4283 (13)	0.6493 (6)	−0.3035 (11)	0.1009 (19)	0.450 (7)
H23A	0.4392	0.6937	−0.3366	0.151*	0.450 (7)
H23B	0.3478	0.6281	−0.3653	0.151*	0.450 (7)
H23C	0.5251	0.6265	−0.3124	0.151*	0.450 (7)
C22	0.3883 (11)	0.6700 (5)	−0.1829 (12)	0.086 (3)	0.550 (7)
H22C	0.2916	0.6651	−0.1326	0.103*	0.550 (7)
H22D	0.3754	0.7047	−0.2572	0.103*	0.550 (7)
C23	0.4290 (11)	0.6083 (4)	−0.2567 (10)	0.1009 (19)	0.550 (7)
H23D	0.5275	0.6131	−0.3016	0.151*	0.550 (7)
H23E	0.3499	0.5977	−0.3338	0.151*	0.550 (7)
H23F	0.4362	0.5739	−0.1828	0.151*	0.550 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0573 (19)	0.134 (3)	0.098 (2)	0.0049 (18)	0.0028 (16)	0.065 (2)
C2	0.079 (2)	0.175 (5)	0.117 (3)	−0.009 (3)	0.015 (2)	0.080 (3)
C3	0.129 (4)	0.115 (4)	0.122 (3)	−0.018 (3)	0.051 (3)	0.036 (3)
C4	0.175 (5)	0.071 (2)	0.125 (3)	0.031 (3)	0.077 (3)	0.037 (2)
C5	0.092 (2)	0.084 (2)	0.087 (2)	0.0304 (19)	0.0397 (19)	0.0205 (19)
C6	0.0566 (15)	0.079 (2)	0.0437 (14)	0.0024 (14)	0.0009 (11)	0.0184 (14)
C7	0.0585 (17)	0.111 (3)	0.0592 (17)	−0.0106 (17)	−0.0081 (13)	0.0336 (17)
C8	0.0280 (9)	0.0504 (15)	0.0372 (11)	−0.0020 (9)	0.0039 (8)	0.0018 (10)
C9	0.0380 (12)	0.0514 (14)	0.0445 (13)	0.0096 (10)	0.0072 (10)	0.0016 (11)
C10	0.0417 (12)	0.090 (2)	0.0424 (12)	0.0033 (14)	0.0073 (10)	0.0081 (14)
C11	0.0417 (12)	0.0520 (14)	0.0411 (12)	0.0047 (10)	0.0071 (10)	−0.0068 (11)
C12	0.0296 (10)	0.0476 (14)	0.0345 (11)	−0.0010 (9)	0.0036 (9)	−0.0028 (9)
C13	0.0661 (18)	0.170 (4)	0.0487 (16)	0.029 (2)	0.0149 (14)	−0.0141 (19)
C14	0.119 (3)	0.109 (3)	0.105 (3)	−0.024 (2)	0.013 (2)	0.036 (2)
C15	0.0286 (10)	0.0455 (13)	0.0305 (10)	0.0004 (9)	0.0021 (8)	0.0014 (9)
C16	0.0313 (10)	0.0418 (12)	0.0345 (11)	−0.0003 (9)	0.0028 (9)	−0.0012 (9)
C17	0.0340 (10)	0.0476 (15)	0.0608 (14)	−0.0032 (11)	0.0013 (9)	−0.0043 (12)
C18	0.0345 (12)	0.0582 (16)	0.0648 (15)	−0.0015 (11)	0.0107 (10)	−0.0054 (13)
C19	0.0321 (10)	0.0377 (11)	0.0346 (11)	0.0023 (9)	0.0052 (8)	0.0009 (9)
C20	0.0321 (10)	0.0452 (13)	0.0317 (11)	−0.0022 (9)	0.0065 (8)	−0.0009 (9)
C21	0.0345 (12)	0.0538 (15)	0.0527 (14)	−0.0048 (11)	0.0055 (10)	−0.0127 (12)
C24	0.0371 (11)	0.0436 (13)	0.0401 (12)	0.0022 (10)	0.0035 (9)	0.0069 (10)
C25	0.0463 (13)	0.0412 (13)	0.0468 (13)	0.0013 (10)	0.0054 (10)	0.0007 (10)
C26	0.089 (2)	0.0420 (15)	0.0600 (17)	0.0096 (14)	0.0137 (14)	0.0007 (12)
C27	0.117 (2)	0.0443 (16)	0.076 (2)	0.0183 (17)	0.0216 (18)	−0.0119 (15)
C28	0.094 (2)	0.0634 (19)	0.0549 (16)	0.0003 (16)	0.0226 (15)	−0.0207 (15)
C29	0.0542 (14)	0.0567 (16)	0.0404 (13)	−0.0010 (12)	0.0104 (10)	−0.0077 (12)
C30	0.0706 (17)	0.078 (2)	0.0330 (13)	0.0014 (15)	0.0098 (12)	−0.0029 (13)
C31	0.0716 (17)	0.0724 (19)	0.0383 (13)	0.0173 (15)	0.0068 (11)	0.0142 (13)
C32	0.0549 (14)	0.0560 (16)	0.0416 (13)	0.0129 (12)	0.0100 (10)	0.0027 (12)
C33	0.0342 (11)	0.0409 (12)	0.0367 (11)	0.0032 (9)	0.0061 (8)	0.0009 (10)
C34	0.0391 (11)	0.0434 (14)	0.0414 (12)	−0.0023 (10)	0.0073 (9)	−0.0011 (10)
N1	0.0274 (8)	0.0453 (11)	0.0420 (10)	0.0013 (8)	0.0058 (7)	−0.0026 (9)
O1	0.0433 (10)	0.0815 (14)	0.0902 (14)	0.0097 (10)	−0.0177 (9)	−0.0275 (12)
O3	0.0681 (11)	0.0518 (10)	0.0443 (10)	0.0055 (8)	0.0057 (8)	0.0112 (8)
O4	0.0403 (8)	0.0511 (10)	0.0394 (8)	−0.0005 (7)	0.0001 (6)	0.0072 (7)
O5	0.0342 (7)	0.0624 (10)	0.0358 (7)	0.0096 (8)	−0.0017 (6)	−0.0075 (8)
O6	0.0459 (9)	0.1101 (15)	0.0364 (8)	0.0056 (10)	0.0033 (6)	0.0089 (10)
O7	0.0340 (7)	0.0880 (12)	0.0405 (8)	−0.0025 (9)	0.0080 (6)	0.0014 (9)
S1	0.0471 (3)	0.0637 (4)	0.0672 (4)	−0.0115 (3)	0.0167 (3)	0.0101 (4)
O2	0.0556 (11)	0.0612 (13)	0.0963 (14)	−0.0141 (9)	−0.0061 (10)	−0.0252 (11)
C22'	0.079 (2)	0.057 (7)	0.119 (5)	−0.017 (3)	−0.024 (3)	−0.027 (5)
C23'	0.121 (4)	0.081 (5)	0.096 (4)	0.002 (5)	−0.032 (4)	−0.024 (4)
C22	0.079 (2)	0.057 (7)	0.119 (5)	−0.017 (3)	−0.024 (3)	−0.027 (5)
C23	0.121 (4)	0.081 (5)	0.096 (4)	0.002 (5)	−0.032 (4)	−0.024 (4)

C1—C2	1.370 (5)	C17—H17B	0.9700
C1—C6	1.375 (4)	C18—N1	1.447 (3)
C1—H1	0.9300	C18—S1	1.827 (3)
C2—C3	1.344 (6)	C18—H18A	0.9700
C2—H2	0.9300	C18—H18B	0.9700
C3—C4	1.354 (6)	C19—N1	1.471 (3)
C3—H3	0.9300	C19—C33	1.525 (3)
C4—C5	1.384 (5)	C19—C20	1.544 (3)
C4—H4	0.9300	C19—C24	1.566 (3)
C5—C6	1.359 (4)	C20—C21	1.508 (3)
C5—H5	0.9300	C20—H20	0.9800
C6—C7	1.484 (4)	C21—O1	1.198 (3)
C7—O4	1.415 (3)	C21—O2	1.317 (3)
C7—H7A	0.9700	C24—O3	1.204 (3)
C7—H7B	0.9700	C24—C25	1.466 (3)
C8—O4	1.419 (3)	C25—C26	1.366 (3)
C8—C9	1.517 (3)	C25—C34	1.399 (3)
C8—C12	1.518 (3)	C26—C27	1.396 (4)
C8—H8	0.9800	C26—H26	0.9300
C9—O7	1.409 (3)	C27—C28	1.365 (4)
C9—C11	1.537 (3)	C27—H27	0.9300
C9—H9	0.9800	C28—C29	1.404 (4)
C10—O6	1.410 (3)	C28—H28	0.9300
C10—O7	1.417 (3)	C29—C34	1.393 (3)
C10—C14	1.501 (4)	C29—C30	1.408 (4)
C10—C13	1.503 (4)	C30—C31	1.363 (4)
C11—O6	1.398 (3)	C30—H30	0.9300
C11—O5	1.406 (3)	C31—C32	1.408 (3)
C11—H11	0.9800	C31—H31	0.9300
C12—O5	1.441 (2)	C32—C33	1.355 (3)
C12—C15	1.526 (3)	C32—H32	0.9300
C12—H12	0.9800	C33—C34	1.414 (3)
C13—H13A	0.9600	O2—C22'	1.473 (7)
C13—H13B	0.9600	O2—C22	1.475 (6)
C13—H13C	0.9600	C22'—C23'	1.474 (10)
C14—H14A	0.9600	C22'—H22A	0.9700
C14—H14B	0.9600	C22'—H22B	0.9700
C14—H14C	0.9600	C23'—H23A	0.9600
C15—C20	1.517 (3)	C23'—H23B	0.9600
C15—C16	1.526 (3)	C23'—H23C	0.9600
C15—H15	0.9800	C22—C23	1.471 (9)
C16—N1	1.474 (3)	C22—H22C	0.9700
C16—C17	1.521 (3)	C22—H22D	0.9700
C16—H16	0.9800	C23—H23D	0.9600
C17—S1	1.795 (2)	C23—H23E	0.9600
C17—H17A	0.9700	C23—H23F	0.9600
C2—C1—C6	121.1 (4)	H17A—C17—H17B	108.6
C2—C1—H1	119.4	N1—C18—S1	106.80 (15)
C6—C1—H1	119.4	N1—C18—H18A	110.4
C3—C2—C1	120.1 (4)	S1—C18—H18A	110.4
C3—C2—H2	119.9	N1—C18—H18B	110.4
C1—C2—H2	119.9	S1—C18—H18B	110.4
C2—C3—C4	119.9 (4)	H18A—C18—H18B	108.6
C2—C3—H3	120.1	N1—C19—C33	117.75 (17)
C4—C3—H3	120.1	N1—C19—C20	102.15 (16)
C3—C4—C5	120.3 (4)	C33—C19—C20	114.44 (16)
C3—C4—H4	119.9	N1—C19—C24	107.62 (16)
C5—C4—H4	119.9	C33—C19—C24	102.38 (16)
C6—C5—C4	120.5 (3)	C20—C19—C24	112.68 (17)
C6—C5—H5	119.8	C21—C20—C15	114.78 (18)
C4—C5—H5	119.8	C21—C20—C19	113.89 (17)
C5—C6—C1	117.9 (3)	C15—C20—C19	103.72 (16)
C5—C6—C7	121.5 (3)	C21—C20—H20	108.0
C1—C6—C7	120.5 (3)	C15—C20—H20	108.0
O4—C7—C6	110.0 (2)	C19—C20—H20	108.0
O4—C7—H7A	109.7	O1—C21—O2	124.9 (2)
C6—C7—H7A	109.7	O1—C21—C20	124.2 (2)
O4—C7—H7B	109.7	O2—C21—C20	110.9 (2)
C6—C7—H7B	109.7	O3—C24—C25	128.6 (2)
H7A—C7—H7B	108.2	O3—C24—C19	123.6 (2)
O4—C8—C9	110.44 (18)	C25—C24—C19	107.87 (18)
O4—C8—C12	109.82 (16)	C26—C25—C34	119.6 (2)
C9—C8—C12	100.97 (16)	C26—C25—C24	132.6 (2)
O4—C8—H8	111.7	C34—C25—C24	107.80 (19)
C9—C8—H8	111.7	C25—C26—C27	118.0 (3)
C12—C8—H8	111.7	C25—C26—H26	121.0
O7—C9—C8	108.83 (19)	C27—C26—H26	121.0
O7—C9—C11	103.87 (17)	C28—C27—C26	122.4 (3)
C8—C9—C11	103.81 (17)	C28—C27—H27	118.8
O7—C9—H9	113.2	C26—C27—H27	118.8
C8—C9—H9	113.2	C27—C28—C29	121.1 (2)
C11—C9—H9	113.2	C27—C28—H28	119.5
O6—C10—O7	105.64 (17)	C29—C28—H28	119.5
O6—C10—C14	109.8 (3)	C34—C29—C28	115.6 (2)
O7—C10—C14	108.7 (3)	C34—C29—C30	116.7 (2)
O6—C10—C13	110.0 (2)	C28—C29—C30	127.6 (2)
O7—C10—C13	109.6 (2)	C31—C30—C29	119.8 (2)
C14—C10—C13	112.9 (3)	C31—C30—H30	120.1
O6—C11—O5	111.7 (2)	C29—C30—H30	120.1
O6—C11—C9	104.83 (17)	C30—C31—C32	122.5 (2)
O5—C11—C9	106.55 (16)	C30—C31—H31	118.7
O6—C11—H11	111.2	C32—C31—H31	118.7
O5—C11—H11	111.2	C33—C32—C31	119.4 (2)
C9—C11—H11	111.2	C33—C32—H32	120.3
O5—C12—C8	102.65 (17)	C31—C32—H32	120.3
O5—C12—C15	111.29 (15)	C32—C33—C34	118.1 (2)
C8—C12—C15	116.53 (17)	C32—C33—C19	133.6 (2)
O5—C12—H12	108.7	C34—C33—C19	108.30 (18)
C8—C12—H12	108.7	C29—C34—C25	123.2 (2)
C15—C12—H12	108.7	C29—C34—C33	123.4 (2)
C10—C13—H13A	109.5	C25—C34—C33	113.27 (19)
C10—C13—H13B	109.5	C18—N1—C19	118.65 (18)
H13A—C13—H13B	109.5	C18—N1—C16	111.09 (18)
C10—C13—H13C	109.5	C19—N1—C16	111.32 (15)
H13A—C13—H13C	109.5	C7—O4—C8	113.87 (18)
H13B—C13—H13C	109.5	C11—O5—C12	108.05 (15)
C10—C14—H14A	109.5	C11—O6—C10	111.37 (16)
C10—C14—H14B	109.5	C9—O7—C10	109.72 (17)
H14A—C14—H14B	109.5	C17—S1—C18	87.71 (11)
C10—C14—H14C	109.5	C21—O2—C22'	125.8 (7)
H14A—C14—H14C	109.5	C21—O2—C22	110.4 (4)
H14B—C14—H14C	109.5	O2—C22'—C23'	101.0 (8)
C20—C15—C16	102.45 (16)	O2—C22'—H22A	111.6
C20—C15—C12	114.38 (17)	C23'—C22'—H22A	111.6
C16—C15—C12	115.66 (16)	O2—C22'—H22B	111.6
C20—C15—H15	108.0	C23'—C22'—H22B	111.6
C16—C15—H15	108.0	H22A—C22'—H22B	109.4
C12—C15—H15	108.0	C23—C22—O2	107.0 (7)
N1—C16—C17	109.70 (16)	C23—C22—H22C	110.3
N1—C16—C15	104.77 (16)	O2—C22—H22C	110.3
C17—C16—C15	114.75 (18)	C23—C22—H22D	110.3
N1—C16—H16	109.1	O2—C22—H22D	110.3
C17—C16—H16	109.1	H22C—C22—H22D	108.6
C15—C16—H16	109.1	C22—C23—H23D	109.5
C16—C17—S1	106.38 (15)	C22—C23—H23E	109.5
C16—C17—H17A	110.5	H23D—C23—H23E	109.5
S1—C17—H17A	110.5	C22—C23—H23F	109.5
C16—C17—H17B	110.5	H23D—C23—H23F	109.5
S1—C17—H17B	110.5	H23E—C23—H23F	109.5
C6—C1—C2—C3	−3.2 (7)	C28—C29—C30—C31	177.8 (3)
C1—C2—C3—C4	−0.6 (8)	C29—C30—C31—C32	1.8 (4)
C2—C3—C4—C5	2.2 (8)	C30—C31—C32—C33	−0.3 (4)
C3—C4—C5—C6	0.0 (7)	C31—C32—C33—C34	−1.2 (3)
C4—C5—C6—C1	−3.6 (5)	C31—C32—C33—C19	−178.8 (2)
C4—C5—C6—C7	180.0 (4)	N1—C19—C33—C32	−69.6 (3)
C2—C1—C6—C5	5.3 (6)	C20—C19—C33—C32	50.4 (3)
C2—C1—C6—C7	−178.3 (4)	C24—C19—C33—C32	172.7 (2)
C5—C6—C7—O4	−131.1 (3)	N1—C19—C33—C34	112.6 (2)
C1—C6—C7—O4	52.6 (4)	C20—C19—C33—C34	−127.35 (19)
O4—C8—C9—O7	163.47 (15)	C24—C19—C33—C34	−5.1 (2)
C12—C8—C9—O7	−80.38 (19)	C28—C29—C34—C25	−2.6 (3)
O4—C8—C9—C11	−86.4 (2)	C30—C29—C34—C25	176.9 (2)
C12—C8—C9—C11	29.8 (2)	C28—C29—C34—C33	−179.3 (2)
O7—C9—C11—O6	−12.6 (2)	C30—C29—C34—C33	0.1 (3)
C8—C9—C11—O6	−126.3 (2)	C26—C25—C34—C29	2.4 (4)
O7—C9—C11—O5	105.99 (19)	C24—C25—C34—C29	−175.3 (2)
C8—C9—C11—O5	−7.8 (2)	C26—C25—C34—C33	179.4 (2)
O4—C8—C12—O5	74.99 (18)	C24—C25—C34—C33	1.7 (3)
C9—C8—C12—O5	−41.62 (19)	C32—C33—C34—C29	1.3 (3)
O4—C8—C12—C15	−46.9 (2)	C19—C33—C34—C29	179.4 (2)
C9—C8—C12—C15	−163.49 (18)	C32—C33—C34—C25	−175.8 (2)
O5—C12—C15—C20	128.42 (18)	C19—C33—C34—C25	2.4 (3)
C8—C12—C15—C20	−114.4 (2)	S1—C18—N1—C19	100.49 (19)
O5—C12—C15—C16	9.7 (3)	S1—C18—N1—C16	−30.4 (2)
C8—C12—C15—C16	126.9 (2)	C33—C19—N1—C18	−21.1 (3)
C20—C15—C16—N1	29.11 (19)	C20—C19—N1—C18	−147.37 (18)
C12—C15—C16—N1	154.21 (17)	C24—C19—N1—C18	93.8 (2)
C20—C15—C16—C17	149.47 (18)	C33—C19—N1—C16	109.69 (19)
C12—C15—C16—C17	−85.4 (2)	C20—C19—N1—C16	−16.6 (2)
N1—C16—C17—S1	25.76 (19)	C24—C19—N1—C16	−135.40 (17)
C15—C16—C17—S1	−91.84 (18)	C17—C16—N1—C18	3.3 (2)
C16—C15—C20—C21	−164.34 (17)	C15—C16—N1—C18	126.92 (18)
C12—C15—C20—C21	69.7 (2)	C17—C16—N1—C19	−131.35 (17)
C16—C15—C20—C19	−39.46 (19)	C15—C16—N1—C19	−7.7 (2)
C12—C15—C20—C19	−165.40 (15)	C6—C7—O4—C8	−178.8 (2)
N1—C19—C20—C21	160.00 (19)	C9—C8—O4—C7	−113.4 (2)
C33—C19—C20—C21	31.6 (3)	C12—C8—O4—C7	136.1 (2)
C24—C19—C20—C21	−84.8 (2)	O6—C11—O5—C12	94.59 (19)
N1—C19—C20—C15	34.54 (19)	C9—C11—O5—C12	−19.3 (2)
C33—C19—C20—C15	−93.84 (19)	C8—C12—O5—C11	38.9 (2)
C24—C19—C20—C15	149.72 (17)	C15—C12—O5—C11	164.21 (18)
C15—C20—C21—O1	−4.0 (3)	O5—C11—O6—C10	−115.1 (2)
C19—C20—C21—O1	−123.3 (3)	C9—C11—O6—C10	−0.1 (3)
C15—C20—C21—O2	175.35 (19)	O7—C10—O6—C11	12.7 (3)
C19—C20—C21—O2	56.0 (3)	C14—C10—O6—C11	129.8 (3)
N1—C19—C24—O3	61.5 (3)	C13—C10—O6—C11	−105.4 (3)
C33—C19—C24—O3	−173.8 (2)	C8—C9—O7—C10	131.1 (2)
C20—C19—C24—O3	−50.3 (3)	C11—C9—O7—C10	21.0 (2)
N1—C19—C24—C25	−118.61 (18)	O6—C10—O7—C9	−21.5 (3)
C33—C19—C24—C25	6.1 (2)	C14—C10—O7—C9	−139.2 (2)
C20—C19—C24—C25	129.55 (18)	C13—C10—O7—C9	97.0 (3)
O3—C24—C25—C26	−2.4 (4)	C16—C17—S1—C18	−36.36 (15)
C19—C24—C25—C26	177.7 (3)	N1—C18—S1—C17	38.98 (17)
O3—C24—C25—C34	174.8 (2)	O1—C21—O2—C22'	−11.9 (7)
C19—C24—C25—C34	−5.0 (2)	C20—C21—O2—C22'	168.8 (6)
C34—C25—C26—C27	−0.5 (4)	O1—C21—O2—C22	5.5 (6)
C24—C25—C26—C27	176.5 (3)	C20—C21—O2—C22	−173.8 (6)
C25—C26—C27—C28	−0.9 (5)	C21—O2—C22'—C23'	97.2 (11)
C26—C27—C28—C29	0.7 (5)	C22—O2—C22'—C23'	47.9 (17)
C27—C28—C29—C34	1.1 (4)	C21—O2—C22—C23	159.1 (8)
C27—C28—C29—C30	−178.4 (3)	C22'—O2—C22—C23	−62 (2)
C34—C29—C30—C31	−1.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3i	0.93	2.51	3.375 (4)	155
C17—H17A···O7ii	0.97	2.44	3.309 (3)	148
C23—H23F···O4iii	0.96	2.57	3.497 (9)	163
C31—H31···O5iv	0.93	2.47	3.393 (4)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3i	0.93	2.51	3.375 (4)	155
C17—H17A⋯O7ii	0.97	2.44	3.309 (3)	148
C23—H23F⋯O4iii	0.96	2.57	3.497 (9)	163
C31—H31⋯O5iv	0.93	2.47	3.393 (4)	173

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .