Crystal structure of ethyl (2S,2'R)-1'-benzyl-3-oxo-3H-di-spiro-[1-benzo-thio-phene-2,3'-pyrrolidine-2',11''-indeno[1,2-b]quinoxaline]-4'-carboxyl-ate.

In the title compound, C35H27N3O3S, the spiro-linked five-membered rings both adopt twisted conformations. The pyrrolidine ring makes dihedral angles of 80.5 (1) and 77.4 (9)° with the benzo-thio-phene ring system and the quinoxaline ring system, respectively. The S atom and C=O unit of the benzo-thio-phene ring system are disordered over two opposite orientations in a 0.768 (4):0.232 (4) ratio. The atoms of the ethyl side chain are disordered over two sets of sites in a 0.680 (16):0.320 (16) ratio. In the crystal, mol-ecules are linked by C-H⋯O, C-H⋯N and π-π inter-actions [shortest centroid-centroid distance = 3.4145 (19) Å], resulting in a three-dimensional network.

Related literature

For general background to spiro compounds and their biological activity, see: Pradhan et al. (2006 ▸); Saeedi et al. (2010 ▸); Dandia et al. (2011 ▸); He et al. (2003 ▸). For uses of pyrrolidine and quinoxaline derivatives, see: Raj et al. (2003 ▸); Zarranz et al. (2003 ▸). For a related structure, see: Kannan et al. (2013 ▸).

Experimental

Crystal data

C35H27N3O3S

M = 569.66

Monoclinic,

a = 11.3893 (5) Å

b = 15.1181 (7) Å

c = 16.7136 (7) Å

β = 100.766 (2)°

V = 2827.2 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.16 mm−1

T = 293 K

0.24 × 0.20 × 0.19 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.963, T max = 0.971

26003 measured reflections

7078 independent reflections

4934 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.128

S = 1.07

7078 reflections

440 parameters

82 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.18 e Å−3

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 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015003187/hb7364sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003187/hb7364Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015003187/hb7364fig1.tif

The mol­ecular structure showing displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015003187/hb7364fig2.tif

The packing of the title compound, viewed along the C-axis.

CCDC reference: 1049572

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

C35H27N3O3S	Z = 4
Mr = 569.66	F(000) = 1192
Monoclinic, P21/c	Dx = 1.338 Mg m−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.3893 (5) Å	Cell parameters from 7078 reflections
b = 15.1181 (7) Å	µ = 0.16 mm−1
c = 16.7136 (7) Å	T = 293 K
β = 100.766 (2)°	Block, colourless
V = 2827.2 (2) Å3	0.24 × 0.20 × 0.19 mm

Bruker SMART APEXII CCD diffractometer	7078 independent reflections
Radiation source: fine-focus sealed tube	4934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and φ scans	θmax = 28.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→15
Tmin = 0.963, Tmax = 0.971	k = −20→15
26003 measured reflections	l = −22→22

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.8872P] where P = (Fo2 + 2Fc2)/3
7078 reflections	(Δ/σ)max = 0.001
440 parameters	Δρmax = 0.21 e Å−3
82 restraints	Δρmin = −0.18 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	Occ. (<1)
C1	0.94305 (15)	0.59196 (11)	0.32387 (10)	0.0390 (4)
C2	1.02494 (16)	0.61651 (12)	0.27599 (11)	0.0474 (4)
H2	1.0270	0.6742	0.2569	0.057*
C3	1.10351 (18)	0.55315 (14)	0.25723 (12)	0.0536 (5)
H3	1.1592	0.5689	0.2255	0.064*
C4	1.10079 (19)	0.46711 (14)	0.28464 (12)	0.0557 (5)
H4	1.1534	0.4255	0.2703	0.067*
C5	1.02072 (18)	0.44219 (12)	0.33317 (12)	0.0504 (4)
H5	1.0191	0.3844	0.3520	0.060*
C6	0.94291 (15)	0.50536 (11)	0.35315 (10)	0.0400 (4)
C7	0.85854 (15)	0.50023 (11)	0.40909 (10)	0.0387 (4)
C8	0.74977 (16)	0.44736 (12)	0.49827 (11)	0.0441 (4)
C9	0.70512 (19)	0.37615 (14)	0.53845 (13)	0.0586 (5)
H9	0.7266	0.3184	0.5285	0.070*
C10	0.6306 (2)	0.39205 (16)	0.59184 (14)	0.0643 (6)
H10	0.6010	0.3448	0.6177	0.077*
C11	0.59810 (19)	0.47810 (16)	0.60827 (13)	0.0627 (6)
H11	0.5490	0.4878	0.6461	0.075*
C12	0.63773 (19)	0.54804 (14)	0.56935 (12)	0.0559 (5)
H12	0.6151	0.6052	0.5804	0.067*
C13	0.71247 (16)	0.53441 (12)	0.51270 (10)	0.0427 (4)
C14	0.81360 (15)	0.58677 (10)	0.41819 (10)	0.0378 (4)
C15	0.85285 (15)	0.64971 (10)	0.35577 (10)	0.0371 (4)
C16	0.74095 (15)	0.67850 (10)	0.29184 (10)	0.0369 (4)
C18	0.60427 (17)	0.61769 (11)	0.16969 (10)	0.0455 (4)
C19	0.5082 (2)	0.57525 (14)	0.12280 (13)	0.0624 (6)
H19	0.4675	0.5308	0.1449	0.075*
C20	0.4738 (2)	0.60023 (18)	0.04237 (14)	0.0769 (7)
H20	0.4089	0.5727	0.0098	0.092*
C21	0.5351 (2)	0.66581 (17)	0.01002 (13)	0.0723 (7)
H21	0.5104	0.6822	−0.0441	0.087*
C22	0.6315 (2)	0.70724 (14)	0.05597 (12)	0.0562 (5)
H22	0.6731	0.7507	0.0334	0.067*
C23	0.66571 (16)	0.68277 (11)	0.13706 (10)	0.0440 (4)
C24	0.68928 (15)	0.75054 (10)	0.34217 (10)	0.0399 (4)
H24	0.6505	0.7203	0.3821	0.048*
C25	0.59899 (18)	0.81252 (12)	0.29378 (12)	0.0486 (4)
C28	0.80035 (16)	0.79654 (11)	0.38832 (12)	0.0469 (4)
H28A	0.8121	0.8530	0.3633	0.056*
H28B	0.7934	0.8066	0.4446	0.056*
C29	0.99701 (19)	0.73891 (12)	0.45364 (12)	0.0520 (5)
H29A	1.0523	0.6910	0.4498	0.062*
H29B	0.9653	0.7307	0.5031	0.062*
C30	1.06247 (16)	0.82614 (12)	0.45754 (11)	0.0473 (4)
C31	1.0953 (2)	0.86170 (15)	0.38916 (14)	0.0678 (6)
H31	1.0783	0.8308	0.3402	0.081*
C32	1.1527 (2)	0.94207 (17)	0.39172 (16)	0.0754 (7)
H32	1.1738	0.9649	0.3447	0.091*
C33	1.1787 (2)	0.98798 (16)	0.46243 (18)	0.0767 (7)
H33	1.2177	1.0422	0.4643	0.092*
C34	1.1471 (3)	0.95415 (17)	0.53055 (17)	0.0869 (8)
H34	1.1647	0.9853	0.5793	0.104*
C35	1.0890 (2)	0.87391 (15)	0.52796 (14)	0.0687 (6)
H35	1.0674	0.8519	0.5751	0.082*
N1	0.74601 (13)	0.60603 (9)	0.47047 (8)	0.0428 (3)
N2	0.82817 (14)	0.43036 (9)	0.44648 (9)	0.0460 (4)
N3	0.89985 (13)	0.73649 (9)	0.38373 (9)	0.0399 (3)
S1	0.78568 (8)	0.73399 (5)	0.20235 (4)	0.0406 (3)	0.768 (4)
C17	0.6529 (4)	0.6080 (3)	0.2563 (3)	0.0435 (10)	0.768 (4)
O3	0.6242 (2)	0.54889 (17)	0.29998 (16)	0.0534 (6)	0.768 (4)
S1'	0.6310 (4)	0.5815 (3)	0.2707 (2)	0.0492 (13)	0.232 (4)
C17'	0.7539 (7)	0.7084 (5)	0.2082 (4)	0.0435 (10)	0.232 (4)
O3'	0.8375 (8)	0.7589 (5)	0.2028 (5)	0.075 (3)	0.232 (4)
O1	0.6076 (16)	0.8911 (4)	0.2969 (10)	0.072 (3)	0.320 (16)
O2	0.5072 (16)	0.7644 (13)	0.2591 (17)	0.067 (4)	0.320 (16)
C26	0.4105 (14)	0.8121 (16)	0.2061 (14)	0.067 (3)	0.320 (16)
H26A	0.3973	0.7864	0.1520	0.080*	0.320 (16)
H26B	0.4333	0.8735	0.2018	0.080*	0.320 (16)
C27	0.2996 (15)	0.8074 (19)	0.2390 (16)	0.133 (7)	0.320 (16)
H27A	0.2866	0.7476	0.2544	0.200*	0.320 (16)
H27B	0.2337	0.8264	0.1981	0.200*	0.320 (16)
H27C	0.3063	0.8451	0.2858	0.200*	0.320 (16)
O1'	0.6159 (7)	0.8878 (3)	0.2794 (6)	0.096 (2)	0.680 (16)
O2'	0.4957 (7)	0.7732 (6)	0.2675 (8)	0.0590 (19)	0.680 (16)
C26'	0.3996 (7)	0.8243 (8)	0.2179 (8)	0.082 (3)	0.680 (16)
H26C	0.4244	0.8455	0.1688	0.099*	0.680 (16)
H26D	0.3788	0.8747	0.2482	0.099*	0.680 (16)
C27'	0.2971 (6)	0.7641 (5)	0.1971 (6)	0.105 (3)	0.680 (16)
H27D	0.3197	0.7137	0.1684	0.158*	0.680 (16)
H27E	0.2322	0.7944	0.1632	0.158*	0.680 (16)
H27F	0.2724	0.7447	0.2461	0.158*	0.680 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0421 (9)	0.0319 (8)	0.0440 (8)	0.0016 (7)	0.0106 (7)	−0.0031 (7)
C2	0.0507 (11)	0.0400 (9)	0.0552 (10)	−0.0001 (8)	0.0195 (8)	0.0010 (8)
C3	0.0509 (11)	0.0558 (12)	0.0591 (11)	0.0034 (9)	0.0231 (9)	−0.0041 (9)
C4	0.0587 (12)	0.0512 (11)	0.0598 (11)	0.0158 (9)	0.0177 (10)	−0.0087 (9)
C5	0.0587 (12)	0.0362 (9)	0.0565 (11)	0.0100 (8)	0.0114 (9)	−0.0017 (8)
C6	0.0435 (10)	0.0322 (8)	0.0444 (8)	0.0022 (7)	0.0089 (7)	−0.0015 (7)
C7	0.0400 (9)	0.0319 (8)	0.0437 (8)	0.0011 (7)	0.0065 (7)	0.0007 (7)
C8	0.0433 (10)	0.0406 (9)	0.0469 (9)	−0.0029 (7)	0.0044 (7)	0.0082 (8)
C9	0.0612 (13)	0.0460 (11)	0.0679 (12)	−0.0066 (9)	0.0103 (10)	0.0155 (10)
C10	0.0624 (13)	0.0644 (14)	0.0676 (13)	−0.0149 (11)	0.0161 (11)	0.0222 (11)
C11	0.0571 (13)	0.0771 (16)	0.0581 (12)	−0.0105 (11)	0.0214 (10)	0.0104 (11)
C12	0.0613 (13)	0.0571 (12)	0.0530 (11)	−0.0035 (10)	0.0200 (9)	0.0040 (9)
C13	0.0440 (10)	0.0429 (9)	0.0412 (8)	−0.0031 (7)	0.0078 (7)	0.0049 (7)
C14	0.0429 (9)	0.0303 (8)	0.0407 (8)	−0.0003 (7)	0.0092 (7)	0.0011 (7)
C15	0.0430 (9)	0.0276 (7)	0.0427 (8)	−0.0009 (6)	0.0132 (7)	−0.0006 (7)
C16	0.0413 (9)	0.0288 (7)	0.0429 (8)	0.0002 (6)	0.0138 (7)	0.0020 (7)
C18	0.0559 (11)	0.0356 (9)	0.0466 (9)	0.0025 (8)	0.0141 (8)	−0.0009 (8)
C19	0.0723 (14)	0.0536 (12)	0.0625 (12)	−0.0179 (10)	0.0155 (11)	−0.0037 (10)
C20	0.0792 (17)	0.0868 (18)	0.0602 (13)	−0.0212 (14)	0.0010 (12)	−0.0115 (13)
C21	0.0876 (17)	0.0831 (17)	0.0442 (10)	−0.0041 (14)	0.0072 (11)	0.0019 (11)
C22	0.0730 (14)	0.0482 (11)	0.0522 (10)	0.0000 (10)	0.0240 (10)	0.0044 (9)
C23	0.0527 (11)	0.0344 (9)	0.0470 (9)	0.0019 (7)	0.0151 (8)	−0.0050 (7)
C24	0.0457 (10)	0.0294 (8)	0.0482 (9)	0.0019 (7)	0.0176 (7)	0.0021 (7)
C25	0.0552 (12)	0.0367 (10)	0.0581 (11)	0.0076 (8)	0.0211 (9)	0.0068 (9)
C28	0.0535 (11)	0.0306 (8)	0.0600 (10)	−0.0010 (7)	0.0195 (9)	−0.0061 (8)
C29	0.0638 (12)	0.0362 (9)	0.0516 (10)	−0.0024 (8)	−0.0003 (9)	0.0032 (8)
C30	0.0470 (10)	0.0375 (9)	0.0536 (10)	−0.0009 (8)	−0.0005 (8)	0.0009 (8)
C31	0.0799 (16)	0.0628 (14)	0.0596 (12)	−0.0206 (12)	0.0107 (11)	−0.0028 (11)
C32	0.0779 (16)	0.0680 (15)	0.0792 (15)	−0.0232 (13)	0.0114 (13)	0.0137 (13)
C33	0.0710 (16)	0.0506 (13)	0.1024 (19)	−0.0189 (11)	0.0004 (14)	−0.0009 (13)
C34	0.108 (2)	0.0666 (16)	0.0832 (17)	−0.0315 (15)	0.0093 (15)	−0.0216 (14)
C35	0.0861 (17)	0.0592 (13)	0.0603 (12)	−0.0163 (12)	0.0126 (11)	−0.0088 (11)
N1	0.0508 (9)	0.0363 (7)	0.0438 (7)	0.0002 (6)	0.0153 (6)	0.0020 (6)
N2	0.0523 (9)	0.0323 (7)	0.0536 (8)	0.0013 (6)	0.0108 (7)	0.0073 (6)
N3	0.0432 (8)	0.0269 (6)	0.0494 (8)	−0.0003 (6)	0.0082 (6)	−0.0026 (6)
S1	0.0467 (5)	0.0326 (4)	0.0454 (3)	−0.0077 (3)	0.0158 (3)	0.0044 (3)
C17	0.043 (2)	0.035 (2)	0.0557 (19)	0.0037 (14)	0.0177 (13)	0.0042 (15)
O3	0.0583 (12)	0.0485 (14)	0.0530 (13)	−0.0188 (10)	0.0092 (10)	0.0144 (10)
S1'	0.055 (2)	0.046 (3)	0.044 (2)	−0.0049 (18)	0.0047 (16)	0.0028 (17)
C17'	0.043 (2)	0.035 (2)	0.0557 (19)	0.0037 (14)	0.0177 (13)	0.0042 (15)
O3'	0.074 (6)	0.064 (5)	0.088 (5)	−0.039 (4)	0.016 (4)	0.006 (4)
O1	0.099 (8)	0.021 (4)	0.094 (5)	0.022 (4)	0.013 (4)	−0.018 (4)
O2	0.062 (6)	0.051 (6)	0.081 (6)	0.023 (4)	0.001 (5)	−0.004 (4)
C26	0.071 (7)	0.052 (6)	0.078 (6)	0.023 (5)	0.017 (5)	0.024 (5)
C27	0.074 (8)	0.160 (15)	0.169 (14)	0.047 (9)	0.032 (9)	0.097 (11)
O1'	0.066 (3)	0.054 (3)	0.163 (6)	0.001 (2)	0.009 (3)	0.054 (3)
O2'	0.049 (2)	0.036 (2)	0.088 (4)	0.005 (2)	0.003 (2)	0.015 (3)
C26'	0.054 (3)	0.070 (5)	0.115 (6)	0.018 (3)	−0.005 (3)	0.021 (3)
C27'	0.066 (3)	0.093 (4)	0.140 (6)	−0.001 (3)	−0.022 (3)	0.028 (4)

C1—C2	1.388 (2)	C22—C23	1.389 (3)
C1—C6	1.398 (2)	C22—H22	0.9300
C1—C15	1.519 (2)	C23—C17'	1.459 (7)
C2—C3	1.386 (3)	C23—S1	1.7609 (19)
C2—H2	0.9300	C24—C25	1.510 (2)
C3—C4	1.381 (3)	C24—C28	1.521 (2)
C3—H3	0.9300	C24—H24	0.9800
C4—C5	1.381 (3)	C25—O1'	1.186 (4)
C4—H4	0.9300	C25—O1	1.193 (6)
C5—C6	1.385 (2)	C25—O2	1.316 (8)
C5—H5	0.9300	C25—O2'	1.318 (4)
C6—C7	1.463 (2)	C28—N3	1.465 (2)
C7—N2	1.306 (2)	C28—H28A	0.9700
C7—C14	1.423 (2)	C28—H28B	0.9700
C8—N2	1.379 (2)	C29—N3	1.452 (2)
C8—C9	1.413 (3)	C29—C30	1.510 (3)
C8—C13	1.417 (3)	C29—H29A	0.9700
C9—C10	1.363 (3)	C29—H29B	0.9700
C9—H9	0.9300	C30—C35	1.366 (3)
C10—C11	1.394 (3)	C30—C31	1.376 (3)
C10—H10	0.9300	C31—C32	1.377 (3)
C11—C12	1.362 (3)	C31—H31	0.9300
C11—H11	0.9300	C32—C33	1.355 (3)
C12—C13	1.402 (3)	C32—H32	0.9300
C12—H12	0.9300	C33—C34	1.357 (4)
C13—N1	1.385 (2)	C33—H33	0.9300
C14—N1	1.301 (2)	C34—C35	1.379 (3)
C14—C15	1.539 (2)	C34—H34	0.9300
C15—N3	1.460 (2)	C35—H35	0.9300
C15—C16	1.564 (2)	C17—O3	1.237 (4)
C16—C17'	1.501 (7)	C17'—O3'	1.237 (9)
C16—C17	1.507 (4)	O2—C26	1.466 (8)
C16—C24	1.557 (2)	C26—C27	1.469 (11)
C16—S1	1.8668 (17)	C26—H26A	0.9700
C16—S1'	1.918 (4)	C26—H26B	0.9700
C18—C23	1.377 (3)	C27—H27A	0.9600
C18—C19	1.379 (3)	C27—H27B	0.9600
C18—C17	1.457 (5)	C27—H27C	0.9600
C18—S1'	1.746 (4)	O2'—C26'	1.463 (5)
C19—C20	1.381 (3)	C26'—C27'	1.471 (9)
C19—H19	0.9300	C26'—H26C	0.9700
C20—C21	1.380 (3)	C26'—H26D	0.9700
C20—H20	0.9300	C27'—H27D	0.9600
C21—C22	1.368 (3)	C27'—H27E	0.9600
C21—H21	0.9300	C27'—H27F	0.9600
C2—C1—C6	119.80 (16)	C22—C23—C17'	138.6 (4)
C2—C1—C15	128.32 (15)	C18—C23—S1	117.48 (14)
C6—C1—C15	111.75 (14)	C22—C23—S1	122.10 (15)
C3—C2—C1	118.51 (17)	C17'—C23—S1	16.6 (3)
C3—C2—H2	120.7	C25—C24—C28	113.99 (14)
C1—C2—H2	120.7	C25—C24—C16	115.66 (14)
C4—C3—C2	121.35 (19)	C28—C24—C16	103.37 (13)
C4—C3—H3	119.3	C25—C24—H24	107.8
C2—C3—H3	119.3	C28—C24—H24	107.8
C5—C4—C3	120.65 (18)	C16—C24—H24	107.8
C5—C4—H4	119.7	O1'—C25—O1	15.8 (10)
C3—C4—H4	119.7	O1'—C25—O2	125.9 (10)
C4—C5—C6	118.41 (18)	O1—C25—O2	128.5 (13)
C4—C5—H5	120.8	O1'—C25—O2'	122.2 (6)
C6—C5—H5	120.8	O1—C25—O2'	121.6 (10)
C5—C6—C1	121.24 (17)	O2—C25—O2'	11 (2)
C5—C6—C7	130.07 (16)	O1'—C25—C24	125.7 (4)
C1—C6—C7	108.50 (14)	O1—C25—C24	123.6 (9)
N2—C7—C14	124.02 (16)	O2—C25—C24	107.4 (10)
N2—C7—C6	127.80 (15)	O2'—C25—C24	112.0 (4)
C14—C7—C6	108.17 (14)	N3—C28—C24	105.56 (13)
N2—C8—C9	119.28 (17)	N3—C28—H28A	110.6
N2—C8—C13	121.99 (15)	C24—C28—H28A	110.6
C9—C8—C13	118.73 (17)	N3—C28—H28B	110.6
C10—C9—C8	120.0 (2)	C24—C28—H28B	110.6
C10—C9—H9	120.0	H28A—C28—H28B	108.8
C8—C9—H9	120.0	N3—C29—C30	110.65 (14)
C9—C10—C11	120.96 (19)	N3—C29—H29A	109.5
C9—C10—H10	119.5	C30—C29—H29A	109.5
C11—C10—H10	119.5	N3—C29—H29B	109.5
C12—C11—C10	120.4 (2)	C30—C29—H29B	109.5
C12—C11—H11	119.8	H29A—C29—H29B	108.1
C10—C11—H11	119.8	C35—C30—C31	117.29 (19)
C11—C12—C13	120.4 (2)	C35—C30—C29	121.79 (19)
C11—C12—H12	119.8	C31—C30—C29	120.90 (17)
C13—C12—H12	119.8	C30—C31—C32	121.3 (2)
N1—C13—C12	119.31 (17)	C30—C31—H31	119.3
N1—C13—C8	121.29 (16)	C32—C31—H31	119.3
C12—C13—C8	119.38 (16)	C33—C32—C31	120.3 (2)
N1—C14—C7	123.18 (15)	C33—C32—H32	119.9
N1—C14—C15	126.89 (14)	C31—C32—H32	119.9
C7—C14—C15	109.89 (14)	C32—C33—C34	119.4 (2)
N3—C15—C1	113.41 (13)	C32—C33—H33	120.3
N3—C15—C14	118.30 (13)	C34—C33—H33	120.3
C1—C15—C14	100.59 (12)	C33—C34—C35	120.4 (2)
N3—C15—C16	99.89 (12)	C33—C34—H34	119.8
C1—C15—C16	116.01 (13)	C35—C34—H34	119.8
C14—C15—C16	109.41 (13)	C30—C35—C34	121.3 (2)
C17'—C16—C17	91.1 (4)	C30—C35—H35	119.3
C17'—C16—C24	113.9 (3)	C34—C35—H35	119.3
C17—C16—C24	114.6 (2)	C14—N1—C13	114.93 (14)
C17'—C16—C15	120.7 (3)	C7—N2—C8	114.20 (15)
C17—C16—C15	118.0 (2)	C29—N3—C15	117.32 (13)
C24—C16—C15	99.64 (12)	C29—N3—C28	115.01 (15)
C17'—C16—S1	14.2 (3)	C15—N3—C28	109.42 (13)
C17—C16—S1	105.23 (18)	C23—S1—C16	90.15 (9)
C24—C16—S1	107.81 (10)	O3—C17—C18	124.5 (4)
C15—C16—S1	111.28 (11)	O3—C17—C16	120.5 (4)
C17'—C16—S1'	103.4 (3)	C18—C17—C16	115.0 (3)
C17—C16—S1'	12.4 (2)	C18—S1'—C16	85.91 (18)
C24—C16—S1'	109.57 (17)	O3'—C17'—C23	121.7 (7)
C15—C16—S1'	109.50 (16)	O3'—C17'—C16	117.7 (7)
S1—C16—S1'	117.53 (14)	C23—C17'—C16	120.5 (6)
C23—C18—C19	121.00 (17)	C25—O2—C26	116.1 (16)
C23—C18—C17	109.8 (2)	O2—C26—C27	110.6 (17)
C19—C18—C17	129.2 (2)	O2—C26—H26A	109.5
C23—C18—S1'	126.63 (19)	C27—C26—H26A	109.5
C19—C18—S1'	112.34 (19)	O2—C26—H26B	109.5
C17—C18—S1'	16.89 (18)	C27—C26—H26B	109.5
C18—C19—C20	118.5 (2)	H26A—C26—H26B	108.1
C18—C19—H19	120.8	C25—O2'—C26'	118.5 (6)
C20—C19—H19	120.8	O2'—C26'—C27'	106.5 (7)
C21—C20—C19	120.4 (2)	O2'—C26'—H26C	110.4
C21—C20—H20	119.8	C27'—C26'—H26C	110.4
C19—C20—H20	119.8	O2'—C26'—H26D	110.4
C22—C21—C20	121.4 (2)	C27'—C26'—H26D	110.4
C22—C21—H21	119.3	H26C—C26'—H26D	108.6
C20—C21—H21	119.3	C26'—C27'—H27D	109.5
C21—C22—C23	118.37 (19)	C26'—C27'—H27E	109.5
C21—C22—H22	120.8	H27D—C27'—H27E	109.5
C23—C22—H22	120.8	C26'—C27'—H27F	109.5
C18—C23—C22	120.41 (17)	H27D—C27'—H27F	109.5
C18—C23—C17'	100.9 (3)	H27E—C27'—H27F	109.5
C6—C1—C2—C3	1.2 (3)	C28—C24—C25—O2'	−168.1 (7)
C15—C1—C2—C3	176.76 (17)	C16—C24—C25—O2'	72.3 (7)
C1—C2—C3—C4	0.5 (3)	C25—C24—C28—N3	−143.07 (15)
C2—C3—C4—C5	−1.3 (3)	C16—C24—C28—N3	−16.71 (17)
C3—C4—C5—C6	0.4 (3)	N3—C29—C30—C35	132.1 (2)
C4—C5—C6—C1	1.3 (3)	N3—C29—C30—C31	−46.3 (3)
C4—C5—C6—C7	−173.14 (18)	C35—C30—C31—C32	0.1 (3)
C2—C1—C6—C5	−2.1 (3)	C29—C30—C31—C32	178.6 (2)
C15—C1—C6—C5	−178.35 (16)	C30—C31—C32—C33	0.2 (4)
C2—C1—C6—C7	173.39 (15)	C31—C32—C33—C34	−0.3 (4)
C15—C1—C6—C7	−2.86 (19)	C32—C33—C34—C35	−0.1 (4)
C5—C6—C7—N2	−8.4 (3)	C31—C30—C35—C34	−0.5 (4)
C1—C6—C7—N2	176.64 (17)	C29—C30—C35—C34	−178.9 (2)
C5—C6—C7—C14	170.72 (18)	C33—C34—C35—C30	0.5 (4)
C1—C6—C7—C14	−4.24 (19)	C7—C14—N1—C13	−5.0 (2)
N2—C8—C9—C10	177.88 (18)	C15—C14—N1—C13	172.37 (15)
C13—C8—C9—C10	−2.0 (3)	C12—C13—N1—C14	−178.80 (16)
C8—C9—C10—C11	−0.6 (3)	C8—C13—N1—C14	−0.4 (2)
C9—C10—C11—C12	1.8 (3)	C14—C7—N2—C8	−1.6 (2)
C10—C11—C12—C13	−0.5 (3)	C6—C7—N2—C8	177.39 (16)
C11—C12—C13—N1	176.31 (18)	C9—C8—N2—C7	176.33 (16)
C11—C12—C13—C8	−2.1 (3)	C13—C8—N2—C7	−3.8 (2)
N2—C8—C13—N1	5.0 (3)	C30—C29—N3—C15	160.74 (15)
C9—C8—C13—N1	−175.06 (17)	C30—C29—N3—C28	−68.4 (2)
N2—C8—C13—C12	−176.56 (16)	C1—C15—N3—C29	−64.6 (2)
C9—C8—C13—C12	3.3 (3)	C14—C15—N3—C29	52.8 (2)
N2—C7—C14—N1	6.5 (3)	C16—C15—N3—C29	171.26 (15)
C6—C7—C14—N1	−172.68 (15)	C1—C15—N3—C28	161.98 (14)
N2—C7—C14—C15	−171.27 (16)	C14—C15—N3—C28	−80.61 (18)
C6—C7—C14—C15	9.57 (18)	C16—C15—N3—C28	37.89 (16)
C2—C1—C15—N3	−40.5 (2)	C24—C28—N3—C29	−148.29 (15)
C6—C1—C15—N3	135.37 (15)	C24—C28—N3—C15	−13.75 (18)
C2—C1—C15—C14	−167.82 (17)	C18—C23—S1—C16	−9.81 (15)
C6—C1—C15—C14	8.03 (18)	C22—C23—S1—C16	169.01 (16)
C2—C1—C15—C16	74.3 (2)	C17'—C23—S1—C16	−7.5 (10)
C6—C1—C15—C16	−109.83 (16)	C17'—C16—S1—C23	8.5 (12)
N1—C14—C15—N3	47.8 (2)	C17—C16—S1—C23	13.5 (2)
C7—C14—C15—N3	−134.57 (15)	C24—C16—S1—C23	−109.24 (12)
N1—C14—C15—C1	171.82 (16)	C15—C16—S1—C23	142.47 (12)
C7—C14—C15—C1	−10.54 (17)	S1'—C16—S1—C23	15.10 (17)
N1—C14—C15—C16	−65.6 (2)	C23—C18—C17—O3	−172.3 (5)
C7—C14—C15—C16	112.06 (15)	C19—C18—C17—O3	11.1 (7)
N3—C15—C16—C17'	79.5 (4)	S1'—C18—C17—O3	5.5 (7)
C1—C15—C16—C17'	−42.7 (4)	C23—C18—C17—C16	9.5 (4)
C14—C15—C16—C17'	−155.6 (4)	C19—C18—C17—C16	−167.1 (2)
N3—C15—C16—C17	−170.5 (2)	S1'—C18—C17—C16	−172.7 (14)
C1—C15—C16—C17	67.2 (3)	C17'—C16—C17—O3	167.2 (6)
C14—C15—C16—C17	−45.6 (3)	C24—C16—C17—O3	−75.7 (5)
N3—C15—C16—C24	−45.81 (14)	C15—C16—C17—O3	41.2 (6)
C1—C15—C16—C24	−168.07 (13)	S1—C16—C17—O3	166.0 (4)
C14—C15—C16—C24	79.06 (14)	S1'—C16—C17—O3	−7.3 (10)
N3—C15—C16—S1	67.71 (13)	C17'—C16—C17—C18	−14.5 (4)
C1—C15—C16—S1	−54.55 (16)	C24—C16—C17—C18	102.5 (3)
C14—C15—C16—S1	−167.42 (10)	C15—C16—C17—C18	−140.5 (3)
N3—C15—C16—S1'	−160.68 (16)	S1—C16—C17—C18	−15.7 (4)
C1—C15—C16—S1'	77.06 (19)	S1'—C16—C17—C18	171.0 (17)
C14—C15—C16—S1'	−35.81 (19)	C23—C18—S1'—C16	7.8 (3)
C23—C18—C19—C20	−0.8 (3)	C19—C18—S1'—C16	−170.09 (17)
C17—C18—C19—C20	175.5 (3)	C17—C18—S1'—C16	5.2 (10)
S1'—C18—C19—C20	177.3 (2)	C17'—C16—S1'—C18	−12.4 (4)
C18—C19—C20—C21	0.4 (4)	C17—C16—S1'—C18	−6.8 (13)
C19—C20—C21—C22	0.5 (4)	C24—C16—S1'—C18	109.36 (17)
C20—C21—C22—C23	−1.0 (4)	C15—C16—S1'—C18	−142.32 (16)
C19—C18—C23—C22	0.3 (3)	S1—C16—S1'—C18	−14.1 (2)
C17—C18—C23—C22	−176.7 (3)	C18—C23—C17'—O3'	171.1 (7)
S1'—C18—C23—C22	−177.5 (2)	C22—C23—C17'—O3'	−11.3 (10)
C19—C18—C23—C17'	178.5 (3)	S1—C23—C17'—O3'	−6.8 (7)
C17—C18—C23—C17'	1.5 (4)	C18—C23—C17'—C16	−13.0 (6)
S1'—C18—C23—C17'	0.7 (4)	C22—C23—C17'—C16	164.7 (3)
C19—C18—C23—S1	179.12 (16)	S1—C23—C17'—C16	169.1 (15)
C17—C18—C23—S1	2.2 (3)	C17—C16—C17'—O3'	−167.1 (7)
S1'—C18—C23—S1	1.4 (3)	C24—C16—C17'—O3'	75.2 (7)
C21—C22—C23—C18	0.6 (3)	C15—C16—C17'—O3'	−43.2 (8)
C21—C22—C23—C17'	−176.7 (5)	S1—C16—C17'—O3'	8.1 (8)
C21—C22—C23—S1	−178.15 (17)	S1'—C16—C17'—O3'	−165.9 (6)
C17'—C16—C24—C25	33.8 (4)	C17—C16—C17'—C23	16.8 (5)
C17—C16—C24—C25	−69.3 (2)	C24—C16—C17'—C23	−100.9 (5)
C15—C16—C24—C25	163.65 (14)	C15—C16—C17'—C23	140.7 (4)
S1—C16—C24—C25	47.47 (17)	S1—C16—C17'—C23	−168.0 (16)
S1'—C16—C24—C25	−81.5 (2)	S1'—C16—C17'—C23	18.0 (6)
C17'—C16—C24—C28	−91.5 (4)	O1'—C25—O2—C26	−9 (3)
C17—C16—C24—C28	165.4 (2)	O1—C25—O2—C26	11 (4)
C15—C16—C24—C28	38.36 (15)	O2'—C25—O2—C26	65 (7)
S1—C16—C24—C28	−77.82 (14)	C24—C25—O2—C26	−177.7 (19)
S1'—C16—C24—C28	153.18 (16)	C25—O2—C26—C27	−116 (3)
C28—C24—C25—O1'	12.4 (7)	O1'—C25—O2'—C26'	0.9 (16)
C16—C24—C25—O1'	−107.2 (6)	O1—C25—O2'—C26'	19.6 (17)
C28—C24—C25—O1	−6.7 (9)	O2—C25—O2'—C26'	−112 (8)
C16—C24—C25—O1	−126.3 (9)	C24—C25—O2'—C26'	−178.6 (9)
C28—C24—C25—O2	−178.4 (16)	C25—O2'—C26'—C27'	179.5 (13)
C16—C24—C25—O2	61.9 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O3i	0.93	2.38	3.222 (3)	150
C22—H22···N1ii	0.93	2.61	3.523 (3)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C11H11O3i	0.93	2.38	3.222(3)	150
C22H22N1ii	0.93	2.61	3.523(3)	167

Symmetry codes: (i) ; (ii) .