Crystal structure of ethyl 1',5-dimethyl-2'',3-dioxo-3H-di-spiro-[benzo[b]thiophene-2,3'-pyrrolidine-2',3''-indoline]-4'-carboxyl-ate.

The title compound, C23H22N2O4S, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. They have very similar conformations with the pyrrolidine ring having a twisted conformation, on the Cspiro-Cspiro bond, in both mol-ecules. In mol-ecule A, the mean planes of the benzo-thio-phene and indoline ring systems are inclined to the mean plane of the pyrrolidine ring by 87.59 (10) and 84.51 (11)°, respectively, and to one another by 72.69 (7)°. The corresponding angles in mol-ecule B are 87.15 (10), 84.58 (10) and 72.07 (7)°, respectively. In the crystal, the A and B mol-ecules are linked to one another by two N-H⋯O hydrogen bonds, forming a dimer. These dimers are linked via C-H⋯O hydrogen bonds, forming a three-dimensional structure.

Related literature

For examples of the biological activity of indole derivatives, see: Singh et al. (2000 ▸); Chai et al. (2006 ▸); n class="Chemical">Nieto et al. (2005 ▸); Andreani et al. (2001 ▸). For the biological activity of indole alkaloids extracted from plants, see: Quetin-Leclercq (1994 ▸); Mukhopadhyay et al. (1981 ▸). For details of highly functionalized pyrrolidines as the main structural element of many natural and synthetic pharmacologically active compounds, see: Waldmann (1995 ▸). For the crystal structure of a related compound, see: Ganesh et al. (2012 ▸).

Experimental

Crystal data

C23H22N2O4S

M = 422.50

Monoclinic,

a = 16.311 (5) Å

b = 11.103 (5) Å

c = 23.585 (5) Å

β = 98.354 (5)°

V = 4226 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 293 K

0.20 × 0.19 × 0.18 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.964, T max = 0.967

36508 measured reflections

10504 independent reflections

5696 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.182

S = 1.07

10504 reflections

541 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97 and PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001528/su5064sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001528/su5064Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015001528/su5064fig1.tif

The mol­ecular structure of the two independent mol­ecules (A and B) of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015001528/su5064fig2.tif

A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table for details; n class="Disease">H atoms not involved in these inter­actions have been omitted for clarity).

CCDC reference: 1045103

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

C23H22N2O4S	F(000) = 1776
Mr = 422.50	Dx = 1.328 Mg m−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 5696 reflections
a = 16.311 (5) Å	θ = 1.4–28.4°
b = 11.103 (5) Å	µ = 0.19 mm−1
c = 23.585 (5) Å	T = 293 K
β = 98.354 (5)°	Block, colourless
V = 4226 (2) Å3	0.20 × 0.19 × 0.18 mm
Z = 8

Bruker SMART APEXII area-detector diffractometer	10504 independent reflections
Radiation source: fine-focus sealed tube	5696 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω and φ scans	θmax = 28.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −21→21
Tmin = 0.964, Tmax = 0.967	k = −10→14
36508 measured reflections	l = −31→28

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0924P)2] where P = (Fo2 + 2Fc2)/3
10504 reflections	(Δ/σ)max = 0.001
541 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.25 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	1.03963 (16)	0.6232 (2)	0.96161 (10)	0.0660 (8)
H1A	1.0658	0.5934	0.9980	0.099*
H1B	1.0403	0.5619	0.9330	0.099*
H1C	0.9833	0.6449	0.9643	0.099*
C1'	0.96287 (16)	0.7862 (2)	0.53352 (10)	0.0622 (7)
H1'1	0.9358	0.8131	0.4968	0.093*
H1'2	1.0185	0.7620	0.5304	0.093*
H1'3	0.9640	0.8506	0.5608	0.093*
C2	1.17418 (14)	0.7110 (2)	0.94672 (10)	0.0551 (6)
H2A	1.1862	0.6279	0.9383	0.066*
H2B	1.2043	0.7319	0.9840	0.066*
C2'	0.82877 (14)	0.7046 (2)	0.55249 (9)	0.0481 (6)
H2'1	0.7976	0.6823	0.5158	0.058*
H2'2	0.8181	0.7886	0.5599	0.058*
C3'	0.80481 (13)	0.62477 (19)	0.60028 (9)	0.0403 (5)
H3'	0.8016	0.6765	0.6335	0.048*
C3	1.19796 (13)	0.7946 (2)	0.90055 (9)	0.0423 (5)
H3	1.2033	0.7453	0.8668	0.051*
C4'	0.72363 (14)	0.5595 (2)	0.58713 (10)	0.0464 (6)
C4	1.27782 (15)	0.8619 (2)	0.91628 (11)	0.0539 (6)
C5'	0.63677 (17)	0.4216 (3)	0.62987 (13)	0.0721 (8)
H5'1	0.5962	0.4496	0.5985	0.087*
H5'2	0.6141	0.4329	0.6653	0.087*
C5	1.3651 (2)	1.0082 (3)	0.87962 (19)	0.1127 (14)
H5A	1.3978	0.9931	0.9167	0.135*
H5B	1.3981	0.9863	0.8502	0.135*
C6	1.3442 (2)	1.1317 (3)	0.87467 (16)	0.1019 (11)
H6A	1.3940	1.1790	0.8789	0.153*
H6B	1.3120	1.1533	0.9041	0.153*
H6C	1.3126	1.1466	0.8377	0.153*
C6'	0.6545 (2)	0.2917 (3)	0.62196 (15)	0.0927 (10)
H6'1	0.6043	0.2462	0.6208	0.139*
H6'2	0.6943	0.2643	0.6533	0.139*
H6'3	0.6764	0.2810	0.5867	0.139*
C7'	0.88089 (12)	0.54207 (18)	0.61532 (8)	0.0342 (5)
C7	1.12099 (12)	0.87597 (18)	0.88528 (8)	0.0340 (5)
C8	1.11405 (12)	0.93915 (19)	0.82729 (8)	0.0352 (5)
C8'	0.88814 (12)	0.48160 (19)	0.67382 (8)	0.0349 (5)
C9'	0.88955 (13)	0.35001 (19)	0.66913 (8)	0.0366 (5)
C9	1.11184 (13)	1.07020 (19)	0.83294 (9)	0.0390 (5)
C10'	0.89327 (14)	0.2689 (2)	0.71447 (9)	0.0472 (6)
H10'	0.8957	0.2973	0.7518	0.057*
C10	1.10808 (15)	1.1524 (2)	0.78791 (10)	0.0505 (6)
H10	1.1063	1.1251	0.7505	0.061*
C11'	0.89341 (15)	0.1460 (2)	0.70409 (10)	0.0507 (6)
C11	1.10697 (15)	1.2746 (2)	0.79895 (11)	0.0554 (6)
C12	1.1061 (2)	1.3648 (3)	0.75117 (12)	0.0791 (9)
H12A	1.1039	1.3231	0.7153	0.119*
H12B	1.1555	1.4129	0.7577	0.119*
H12C	1.0584	1.4159	0.7500	0.119*
C12'	0.8946 (2)	0.0567 (2)	0.75203 (11)	0.0755 (8)
H12D	0.8968	0.0989	0.7878	0.113*
H12E	0.9423	0.0058	0.7533	0.113*
H12F	0.8453	0.0084	0.7457	0.113*
C13	1.10894 (16)	1.3109 (2)	0.85551 (12)	0.0608 (7)
H13	1.1073	1.3930	0.8632	0.073*
C13'	0.89070 (15)	0.1080 (2)	0.64755 (10)	0.0535 (6)
H13'	0.8920	0.0257	0.6403	0.064*
C14	1.11315 (15)	1.2320 (2)	0.90078 (11)	0.0561 (7)
H14	1.1146	1.2597	0.9381	0.067*
C14'	0.88627 (15)	0.1860 (2)	0.60194 (10)	0.0498 (6)
H14'	0.8840	0.1574	0.5647	0.060*
C15'	0.88522 (13)	0.30946 (18)	0.61322 (8)	0.0375 (5)
C15	1.11514 (13)	1.1091 (2)	0.88890 (9)	0.0421 (5)
C16'	0.95153 (12)	0.63320 (18)	0.60834 (8)	0.0347 (5)
C16	1.05081 (12)	0.78321 (18)	0.89070 (8)	0.0357 (5)
C17'	0.96067 (14)	0.72987 (19)	0.65762 (9)	0.0394 (5)
C17	1.04294 (14)	0.68991 (19)	0.83996 (9)	0.0404 (5)
C18'	1.08655 (13)	0.6382 (2)	0.66030 (8)	0.0403 (5)
C18	0.91621 (13)	0.7782 (2)	0.83823 (8)	0.0393 (5)
C19	0.83341 (14)	0.8042 (2)	0.82256 (10)	0.0518 (6)
H19	0.8028	0.7689	0.7905	0.062*
C19'	1.16826 (14)	0.6109 (2)	0.67618 (10)	0.0531 (6)
H19'	1.1991	0.6475	0.7078	0.064*
C20	0.79785 (15)	0.8845 (3)	0.85629 (11)	0.0604 (7)
H20	0.7422	0.9043	0.8465	0.072*
C20'	1.20368 (15)	0.5272 (3)	0.64379 (11)	0.0605 (7)
H20'	1.2592	0.5068	0.6539	0.073*
C21	0.84242 (16)	0.9360 (3)	0.90390 (11)	0.0601 (7)
H21	0.8168	0.9899	0.9259	0.072*
C21'	1.15838 (16)	0.4738 (3)	0.59713 (11)	0.0598 (7)
H21'	1.1835	0.4178	0.5759	0.072*
C22	0.92554 (15)	0.9083 (2)	0.91941 (10)	0.0510 (6)
H22	0.9554	0.9418	0.9522	0.061*
C22'	1.07519 (15)	0.5024 (2)	0.58109 (10)	0.0473 (6)
H22'	1.0449	0.4670	0.5489	0.057*
C23'	1.03826 (12)	0.58414 (19)	0.61354 (8)	0.0363 (5)
C23	0.96336 (12)	0.83105 (19)	0.88591 (8)	0.0365 (5)
N1'	0.91755 (11)	0.68408 (16)	0.55265 (7)	0.0402 (4)
N1	1.08421 (11)	0.72884 (17)	0.94574 (7)	0.0446 (5)
N2	0.96489 (11)	0.69805 (17)	0.81200 (7)	0.0457 (5)
H2	0.9471	0.6583	0.7814	0.055*
N2'	1.03867 (11)	0.72204 (17)	0.68548 (7)	0.0451 (5)
H2'	1.0570	0.7638	0.7154	0.054*
O1'	0.67445 (11)	0.57029 (18)	0.54481 (7)	0.0713 (6)
O1	1.32537 (12)	0.8496 (2)	0.95875 (8)	0.0923 (7)
O2	1.09558 (10)	0.62012 (14)	0.82891 (7)	0.0563 (4)
O2'	0.90884 (10)	0.80189 (14)	0.66769 (7)	0.0550 (4)
O3'	0.89380 (10)	0.53817 (14)	0.71813 (6)	0.0484 (4)
O3	1.11019 (10)	0.88373 (14)	0.78238 (6)	0.0495 (4)
O4'	0.71261 (10)	0.49014 (16)	0.63163 (7)	0.0619 (5)
O4	1.29010 (11)	0.93490 (18)	0.87355 (8)	0.0734 (6)
S1	1.12144 (4)	0.99348 (5)	0.93983 (2)	0.04493 (17)
S1'	0.87786 (4)	0.42250 (5)	0.56126 (2)	0.04015 (16)

	U11	U22	U33	U12	U13	U23
C1	0.0680 (18)	0.0669 (18)	0.0596 (15)	−0.0137 (15)	−0.0021 (13)	0.0282 (14)
C1'	0.0692 (18)	0.0551 (16)	0.0608 (15)	−0.0119 (14)	0.0045 (13)	0.0244 (13)
C2	0.0465 (15)	0.0608 (16)	0.0547 (14)	0.0004 (12)	−0.0038 (11)	0.0186 (13)
C2'	0.0479 (14)	0.0416 (13)	0.0518 (13)	0.0023 (11)	−0.0030 (11)	0.0053 (11)
C3'	0.0433 (13)	0.0333 (11)	0.0429 (12)	0.0025 (10)	0.0015 (10)	−0.0031 (10)
C3	0.0412 (13)	0.0417 (13)	0.0422 (12)	0.0023 (10)	0.0005 (10)	0.0013 (10)
C4'	0.0414 (14)	0.0476 (14)	0.0489 (13)	−0.0004 (11)	0.0024 (11)	−0.0018 (12)
C4	0.0438 (14)	0.0609 (17)	0.0551 (15)	0.0039 (13)	0.0011 (12)	0.0003 (13)
C5'	0.0544 (17)	0.074 (2)	0.088 (2)	−0.0178 (15)	0.0110 (14)	0.0100 (17)
C5	0.062 (2)	0.085 (3)	0.183 (4)	−0.0248 (19)	−0.006 (2)	0.036 (3)
C6	0.091 (3)	0.082 (3)	0.129 (3)	−0.027 (2)	0.005 (2)	−0.001 (2)
C6'	0.088 (2)	0.071 (2)	0.124 (3)	−0.0207 (19)	0.031 (2)	−0.002 (2)
C7'	0.0416 (12)	0.0284 (10)	0.0318 (10)	−0.0028 (9)	0.0025 (9)	−0.0036 (9)
C7	0.0381 (12)	0.0321 (11)	0.0307 (10)	−0.0015 (9)	0.0010 (8)	−0.0041 (9)
C8	0.0394 (12)	0.0338 (11)	0.0314 (10)	0.0000 (9)	0.0014 (9)	−0.0017 (9)
C8'	0.0408 (12)	0.0328 (11)	0.0305 (10)	−0.0041 (9)	0.0027 (9)	−0.0027 (9)
C9'	0.0461 (13)	0.0296 (11)	0.0328 (10)	−0.0051 (10)	0.0017 (9)	−0.0019 (9)
C9	0.0456 (13)	0.0312 (11)	0.0391 (11)	−0.0022 (10)	0.0023 (10)	−0.0028 (10)
C10'	0.0630 (16)	0.0405 (13)	0.0376 (12)	−0.0029 (11)	0.0054 (11)	0.0011 (10)
C10	0.0672 (17)	0.0376 (13)	0.0457 (13)	−0.0041 (12)	0.0049 (11)	0.0009 (11)
C11'	0.0647 (16)	0.0321 (12)	0.0539 (14)	−0.0030 (11)	0.0041 (12)	0.0081 (11)
C11	0.0610 (17)	0.0373 (13)	0.0673 (16)	−0.0025 (12)	0.0079 (13)	0.0061 (13)
C12	0.101 (2)	0.0467 (16)	0.088 (2)	−0.0008 (16)	0.0110 (18)	0.0204 (15)
C12'	0.112 (2)	0.0482 (16)	0.0651 (17)	−0.0046 (16)	0.0091 (16)	0.0183 (14)
C13	0.0681 (18)	0.0331 (13)	0.0838 (19)	−0.0031 (12)	0.0194 (15)	−0.0085 (14)
C13'	0.0727 (17)	0.0289 (12)	0.0592 (15)	−0.0048 (12)	0.0107 (13)	−0.0027 (12)
C14	0.0659 (17)	0.0421 (14)	0.0626 (16)	−0.0051 (13)	0.0177 (13)	−0.0167 (13)
C14'	0.0699 (17)	0.0329 (12)	0.0471 (13)	−0.0042 (11)	0.0103 (12)	−0.0101 (11)
C15'	0.0446 (13)	0.0305 (11)	0.0367 (11)	−0.0039 (9)	0.0032 (9)	−0.0041 (9)
C15	0.0431 (13)	0.0377 (12)	0.0454 (12)	−0.0044 (10)	0.0059 (10)	−0.0074 (10)
C16'	0.0413 (12)	0.0295 (11)	0.0321 (10)	−0.0038 (9)	0.0011 (9)	−0.0017 (9)
C16	0.0403 (12)	0.0341 (11)	0.0313 (10)	−0.0015 (9)	0.0007 (9)	0.0008 (9)
C17'	0.0488 (14)	0.0272 (11)	0.0416 (12)	−0.0034 (10)	0.0042 (10)	−0.0020 (9)
C17	0.0504 (14)	0.0301 (11)	0.0398 (12)	−0.0060 (11)	0.0034 (10)	−0.0007 (10)
C18'	0.0408 (13)	0.0432 (13)	0.0363 (11)	−0.0063 (11)	0.0036 (9)	0.0058 (10)
C18	0.0427 (13)	0.0392 (12)	0.0349 (11)	−0.0066 (10)	0.0016 (9)	0.0043 (10)
C19	0.0426 (14)	0.0632 (17)	0.0464 (13)	−0.0103 (12)	−0.0045 (11)	0.0105 (13)
C19'	0.0423 (14)	0.0670 (17)	0.0472 (13)	−0.0072 (13)	−0.0031 (11)	0.0079 (13)
C20	0.0394 (14)	0.0703 (18)	0.0709 (17)	0.0032 (13)	0.0059 (13)	0.0201 (15)
C20'	0.0389 (14)	0.0718 (19)	0.0712 (18)	0.0064 (14)	0.0092 (13)	0.0229 (15)
C21	0.0509 (16)	0.0629 (17)	0.0695 (17)	0.0054 (13)	0.0185 (13)	−0.0007 (14)
C21'	0.0541 (17)	0.0604 (17)	0.0690 (17)	0.0113 (14)	0.0223 (14)	0.0025 (14)
C22	0.0498 (15)	0.0563 (15)	0.0474 (13)	−0.0016 (12)	0.0092 (11)	−0.0077 (12)
C22'	0.0500 (15)	0.0474 (14)	0.0452 (13)	0.0014 (11)	0.0095 (11)	−0.0024 (11)
C23'	0.0401 (12)	0.0349 (11)	0.0336 (10)	−0.0020 (10)	0.0045 (9)	0.0037 (9)
C23	0.0394 (12)	0.0377 (11)	0.0319 (10)	−0.0026 (10)	0.0036 (9)	0.0030 (9)
N1'	0.0428 (11)	0.0383 (10)	0.0377 (9)	−0.0041 (8)	−0.0007 (8)	0.0072 (8)
N1	0.0453 (11)	0.0495 (12)	0.0365 (9)	−0.0072 (9)	−0.0023 (8)	0.0109 (9)
N2	0.0532 (12)	0.0453 (11)	0.0356 (9)	−0.0079 (9)	−0.0038 (9)	−0.0108 (9)
N2'	0.0494 (12)	0.0452 (11)	0.0379 (10)	−0.0093 (9)	−0.0029 (8)	−0.0096 (9)
O1'	0.0528 (11)	0.0899 (15)	0.0651 (12)	−0.0163 (10)	−0.0122 (9)	0.0105 (11)
O1	0.0568 (12)	0.138 (2)	0.0736 (13)	−0.0199 (13)	−0.0199 (10)	0.0183 (14)
O2	0.0621 (11)	0.0367 (9)	0.0693 (11)	0.0060 (8)	0.0072 (9)	−0.0138 (8)
O2'	0.0594 (11)	0.0365 (9)	0.0672 (11)	0.0033 (8)	0.0028 (8)	−0.0148 (8)
O3'	0.0742 (11)	0.0388 (9)	0.0315 (8)	−0.0085 (8)	0.0049 (7)	−0.0114 (7)
O3	0.0749 (12)	0.0410 (9)	0.0325 (8)	−0.0065 (8)	0.0068 (7)	−0.0079 (7)
O4'	0.0516 (11)	0.0670 (12)	0.0649 (11)	−0.0160 (9)	0.0008 (8)	0.0121 (9)
O4	0.0516 (11)	0.0732 (13)	0.0909 (14)	−0.0201 (10)	−0.0042 (9)	0.0250 (11)
S1	0.0582 (4)	0.0439 (3)	0.0318 (3)	−0.0069 (3)	0.0039 (2)	−0.0096 (2)
S1'	0.0562 (4)	0.0333 (3)	0.0298 (3)	−0.0054 (3)	0.0026 (2)	−0.0052 (2)

C1—N1	1.457 (3)	C10—C11	1.381 (3)
C1—H1A	0.9600	C10—H10	0.9300
C1—H1B	0.9600	C11'—C13'	1.393 (3)
C1—H1C	0.9600	C11'—C12'	1.502 (3)
C1'—N1'	1.460 (3)	C11—C13	1.390 (3)
C1'—H1'1	0.9600	C11—C12	1.506 (3)
C1'—H1'2	0.9600	C12—H12A	0.9600
C1'—H1'3	0.9600	C12—H12B	0.9600
C2—N1	1.478 (3)	C12—H12C	0.9600
C2—C3	1.523 (3)	C12'—H12D	0.9600
C2—H2A	0.9700	C12'—H12E	0.9600
C2—H2B	0.9700	C12'—H12F	0.9600
C2'—N1'	1.465 (3)	C13—C14	1.375 (3)
C2'—C3'	1.529 (3)	C13—H13	0.9300
C2'—H2'1	0.9700	C13'—C14'	1.375 (3)
C2'—H2'2	0.9700	C13'—H13'	0.9300
C3'—C4'	1.502 (3)	C14—C15	1.394 (3)
C3'—C7'	1.543 (3)	C14—H14	0.9300
C3'—H3'	0.9800	C14'—C15'	1.397 (3)
C3—C4	1.501 (3)	C14'—H14'	0.9300
C3—C7	1.546 (3)	C15'—S1'	1.746 (2)
C3—H3	0.9800	C15—S1	1.751 (2)
C4'—O1'	1.192 (2)	C16'—N1'	1.463 (2)
C4'—O4'	1.335 (3)	C16'—C23'	1.504 (3)
C4—O1	1.182 (3)	C16'—C17'	1.573 (3)
C4—O4	1.331 (3)	C16—N1	1.463 (2)
C5'—O4'	1.448 (3)	C16—C23	1.511 (3)
C5'—C6'	1.488 (4)	C16—C17	1.574 (3)
C5'—H5'1	0.9700	C17'—O2'	1.212 (2)
C5'—H5'2	0.9700	C17'—N2'	1.347 (3)
C5—C6	1.413 (5)	C17—O2	1.213 (3)
C5—O4	1.458 (3)	C17—N2	1.349 (3)
C5—H5A	0.9700	C18'—C19'	1.365 (3)
C5—H5B	0.9700	C18'—C23'	1.394 (3)
C6—H6A	0.9600	C18'—N2'	1.402 (3)
C6—H6B	0.9600	C18—C19	1.378 (3)
C6—H6C	0.9600	C18—N2	1.395 (3)
C6'—H6'1	0.9600	C18—C23	1.396 (3)
C6'—H6'2	0.9600	C19—C20	1.378 (4)
C6'—H6'3	0.9600	C19—H19	0.9300
C7'—C8'	1.524 (3)	C19'—C20'	1.382 (4)
C7'—C16'	1.560 (3)	C19'—H19'	0.9300
C7'—S1'	1.836 (2)	C20—C21	1.371 (4)
C7—C8	1.527 (3)	C20—H20	0.9300
C7—C16	1.559 (3)	C20'—C21'	1.368 (4)
C7—S1	1.832 (2)	C20'—H20'	0.9300
C8—O3	1.219 (2)	C21—C22	1.387 (3)
C8—C9	1.462 (3)	C21—H21	0.9300
C8'—O3'	1.211 (2)	C21'—C22'	1.391 (3)
C8'—C9'	1.466 (3)	C21'—H21'	0.9300
C9'—C15'	1.385 (3)	C22—C23	1.372 (3)
C9'—C10'	1.392 (3)	C22—H22	0.9300
C9—C15	1.382 (3)	C22'—C23'	1.380 (3)
C9—C10	1.395 (3)	C22'—H22'	0.9300
C10'—C11'	1.387 (3)	N2—H2	0.8600
C10'—H10'	0.9300	N2'—H2'	0.8600
N1—C1—H1A	109.5	C13—C11—C12	121.4 (2)
N1—C1—H1B	109.5	C11—C12—H12A	109.5
H1A—C1—H1B	109.5	C11—C12—H12B	109.5
N1—C1—H1C	109.5	H12A—C12—H12B	109.5
H1A—C1—H1C	109.5	C11—C12—H12C	109.5
H1B—C1—H1C	109.5	H12A—C12—H12C	109.5
N1'—C1'—H1'1	109.5	H12B—C12—H12C	109.5
N1'—C1'—H1'2	109.5	C11'—C12'—H12D	109.5
H1'1—C1'—H1'2	109.5	C11'—C12'—H12E	109.5
N1'—C1'—H1'3	109.5	H12D—C12'—H12E	109.5
H1'1—C1'—H1'3	109.5	C11'—C12'—H12F	109.5
H1'2—C1'—H1'3	109.5	H12D—C12'—H12F	109.5
N1—C2—C3	105.23 (17)	H12E—C12'—H12F	109.5
N1—C2—H2A	110.7	C14—C13—C11	123.5 (2)
C3—C2—H2A	110.7	C14—C13—H13	118.3
N1—C2—H2B	110.7	C11—C13—H13	118.3
C3—C2—H2B	110.7	C14'—C13'—C11'	123.3 (2)
H2A—C2—H2B	108.8	C14'—C13'—H13'	118.4
N1'—C2'—C3'	105.46 (17)	C11'—C13'—H13'	118.4
N1'—C2'—H2'1	110.6	C13—C14—C15	117.9 (2)
C3'—C2'—H2'1	110.6	C13—C14—H14	121.1
N1'—C2'—H2'2	110.6	C15—C14—H14	121.1
C3'—C2'—H2'2	110.6	C13'—C14'—C15'	118.0 (2)
H2'1—C2'—H2'2	108.8	C13'—C14'—H14'	121.0
C4'—C3'—C2'	116.09 (18)	C15'—C14'—H14'	121.0
C4'—C3'—C7'	114.57 (18)	C9'—C15'—C14'	120.0 (2)
C2'—C3'—C7'	103.36 (16)	C9'—C15'—S1'	115.04 (16)
C4'—C3'—H3'	107.4	C14'—C15'—S1'	124.97 (16)
C2'—C3'—H3'	107.4	C9—C15—C14	119.9 (2)
C7'—C3'—H3'	107.4	C9—C15—S1	114.58 (17)
C4—C3—C2	115.39 (19)	C14—C15—S1	125.48 (18)
C4—C3—C7	114.41 (19)	N1'—C16'—C23'	116.25 (16)
C2—C3—C7	103.89 (17)	N1'—C16'—C7'	98.97 (15)
C4—C3—H3	107.6	C23'—C16'—C7'	117.18 (17)
C2—C3—H3	107.6	N1'—C16'—C17'	112.51 (17)
C7—C3—H3	107.6	C23'—C16'—C17'	101.53 (16)
O1'—C4'—O4'	124.4 (2)	C7'—C16'—C17'	110.89 (15)
O1'—C4'—C3'	126.2 (2)	N1—C16—C23	115.93 (16)
O4'—C4'—C3'	109.35 (19)	N1—C16—C7	99.34 (15)
O1—C4—O4	124.0 (2)	C23—C16—C7	117.27 (17)
O1—C4—C3	126.2 (2)	N1—C16—C17	112.44 (17)
O4—C4—C3	109.7 (2)	C23—C16—C17	101.69 (16)
O4'—C5'—C6'	109.4 (2)	C7—C16—C17	110.62 (15)
O4'—C5'—H5'1	109.8	O2'—C17'—N2'	125.7 (2)
C6'—C5'—H5'1	109.8	O2'—C17'—C16'	126.9 (2)
O4'—C5'—H5'2	109.8	N2'—C17'—C16'	107.32 (18)
C6'—C5'—H5'2	109.8	O2—C17—N2	125.8 (2)
H5'1—C5'—H5'2	108.2	O2—C17—C16	127.0 (2)
C6—C5—O4	110.2 (3)	N2—C17—C16	107.13 (18)
C6—C5—H5A	109.6	C19'—C18'—C23'	122.6 (2)
O4—C5—H5A	109.6	C19'—C18'—N2'	127.8 (2)
C6—C5—H5B	109.6	C23'—C18'—N2'	109.61 (19)
O4—C5—H5B	109.6	C19—C18—N2	127.8 (2)
H5A—C5—H5B	108.1	C19—C18—C23	122.1 (2)
C5—C6—H6A	109.5	N2—C18—C23	110.04 (18)
C5—C6—H6B	109.5	C18—C19—C20	117.3 (2)
H6A—C6—H6B	109.5	C18—C19—H19	121.3
C5—C6—H6C	109.5	C20—C19—H19	121.3
H6A—C6—H6C	109.5	C18'—C19'—C20'	117.9 (2)
H6B—C6—H6C	109.5	C18'—C19'—H19'	121.1
C5'—C6'—H6'1	109.5	C20'—C19'—H19'	121.1
C5'—C6'—H6'2	109.5	C21—C20—C19	121.7 (2)
H6'1—C6'—H6'2	109.5	C21—C20—H20	119.2
C5'—C6'—H6'3	109.5	C19—C20—H20	119.2
H6'1—C6'—H6'3	109.5	C21'—C20'—C19'	121.1 (2)
H6'2—C6'—H6'3	109.5	C21'—C20'—H20'	119.5
C8'—C7'—C3'	115.11 (16)	C19'—C20'—H20'	119.5
C8'—C7'—C16'	114.84 (16)	C20—C21—C22	120.3 (2)
C3'—C7'—C16'	99.87 (16)	C20—C21—H21	119.8
C8'—C7'—S1'	107.51 (14)	C22—C21—H21	119.8
C3'—C7'—S1'	109.33 (13)	C20'—C21'—C22'	120.7 (2)
C16'—C7'—S1'	109.96 (13)	C20'—C21'—H21'	119.6
C8—C7—C3	115.41 (16)	C22'—C21'—H21'	119.6
C8—C7—C16	114.67 (15)	C23—C22—C21	119.4 (2)
C3—C7—C16	100.14 (16)	C23—C22—H22	120.3
C8—C7—S1	107.12 (14)	C21—C22—H22	120.3
C3—C7—S1	109.40 (13)	C23'—C22'—C21'	119.1 (2)
C16—C7—S1	109.94 (13)	C23'—C22'—H22'	120.5
O3—C8—C9	125.66 (19)	C21'—C22'—H22'	120.5
O3—C8—C7	122.30 (19)	C22'—C23'—C18'	118.7 (2)
C9—C8—C7	112.04 (16)	C22'—C23'—C16'	132.36 (19)
O3'—C8'—C9'	125.59 (19)	C18'—C23'—C16'	108.97 (18)
O3'—C8'—C7'	122.6 (2)	C22—C23—C18	119.1 (2)
C9'—C8'—C7'	111.77 (16)	C22—C23—C16	132.47 (19)
C15'—C9'—C10'	120.8 (2)	C18—C23—C16	108.43 (18)
C15'—C9'—C8'	113.37 (18)	C1'—N1'—C16'	115.75 (17)
C10'—C9'—C8'	125.86 (18)	C1'—N1'—C2'	115.02 (18)
C15—C9—C10	120.9 (2)	C16'—N1'—C2'	107.92 (15)
C15—C9—C8	113.59 (19)	C1—N1—C16	115.13 (17)
C10—C9—C8	125.51 (19)	C1—N1—C2	114.82 (19)
C11'—C10'—C9'	120.1 (2)	C16—N1—C2	108.06 (16)
C11'—C10'—H10'	119.9	C17—N2—C18	112.54 (17)
C9'—C10'—H10'	119.9	C17—N2—H2	123.7
C11—C10—C9	120.0 (2)	C18—N2—H2	123.7
C11—C10—H10	120.0	C17'—N2'—C18'	112.40 (17)
C9—C10—H10	120.0	C17'—N2'—H2'	123.8
C10'—C11'—C13'	117.8 (2)	C18'—N2'—H2'	123.8
C10'—C11'—C12'	121.1 (2)	C4'—O4'—C5'	119.5 (2)
C13'—C11'—C12'	121.1 (2)	C4—O4—C5	118.8 (2)
C10—C11—C13	117.8 (2)	C15—S1—C7	92.67 (10)
C10—C11—C12	120.7 (2)	C15'—S1'—C7'	92.30 (9)
N1'—C2'—C3'—C4'	−138.63 (19)	S1—C7—C16—C17	173.63 (13)
N1'—C2'—C3'—C7'	−12.3 (2)	N1'—C16'—C17'—O2'	48.1 (3)
N1—C2—C3—C4	138.1 (2)	C23'—C16'—C17'—O2'	173.1 (2)
N1—C2—C3—C7	12.1 (2)	C7'—C16'—C17'—O2'	−61.7 (3)
C2'—C3'—C4'—O1'	−5.2 (3)	N1'—C16'—C17'—N2'	−129.14 (18)
C7'—C3'—C4'—O1'	−125.6 (3)	C23'—C16'—C17'—N2'	−4.2 (2)
C2'—C3'—C4'—O4'	177.55 (18)	C7'—C16'—C17'—N2'	121.06 (18)
C7'—C3'—C4'—O4'	57.1 (2)	N1—C16—C17—O2	−48.7 (3)
C2—C3—C4—O1	5.5 (4)	C23—C16—C17—O2	−173.4 (2)
C7—C3—C4—O1	125.9 (3)	C7—C16—C17—O2	61.3 (3)
C2—C3—C4—O4	−177.6 (2)	N1—C16—C17—N2	128.69 (18)
C7—C3—C4—O4	−57.2 (3)	C23—C16—C17—N2	4.0 (2)
C4'—C3'—C7'—C8'	−72.2 (2)	C7—C16—C17—N2	−121.25 (18)
C2'—C3'—C7'—C8'	160.55 (17)	N2—C18—C19—C20	178.2 (2)
C4'—C3'—C7'—C16'	164.28 (17)	C23—C18—C19—C20	−0.6 (3)
C2'—C3'—C7'—C16'	37.01 (19)	C23'—C18'—C19'—C20'	0.7 (3)
C4'—C3'—C7'—S1'	48.9 (2)	N2'—C18'—C19'—C20'	−178.0 (2)
C2'—C3'—C7'—S1'	−78.35 (17)	C18—C19—C20—C21	−0.6 (4)
C4—C3—C7—C8	73.3 (2)	C18'—C19'—C20'—C21'	0.3 (4)
C2—C3—C7—C8	−160.00 (18)	C19—C20—C21—C22	0.1 (4)
C4—C3—C7—C16	−163.00 (17)	C19'—C20'—C21'—C22'	−0.1 (4)
C2—C3—C7—C16	−36.33 (19)	C20—C21—C22—C23	1.6 (4)
C4—C3—C7—S1	−47.5 (2)	C20'—C21'—C22'—C23'	−1.2 (4)
C2—C3—C7—S1	79.15 (18)	C21'—C22'—C23'—C18'	2.1 (3)
C3—C7—C8—O3	59.8 (3)	C21'—C22'—C23'—C16'	−179.6 (2)
C16—C7—C8—O3	−55.9 (3)	C19'—C18'—C23'—C22'	−1.9 (3)
S1—C7—C8—O3	−178.13 (17)	N2'—C18'—C23'—C22'	176.99 (18)
C3—C7—C8—C9	−120.8 (2)	C19'—C18'—C23'—C16'	179.44 (19)
C16—C7—C8—C9	123.53 (19)	N2'—C18'—C23'—C16'	−1.7 (2)
S1—C7—C8—C9	1.3 (2)	N1'—C16'—C23'—C22'	−52.5 (3)
C3'—C7'—C8'—O3'	−60.0 (3)	C7'—C16'—C23'—C22'	64.1 (3)
C16'—C7'—C8'—O3'	55.2 (3)	C17'—C16'—C23'—C22'	−175.0 (2)
S1'—C7'—C8'—O3'	177.89 (17)	N1'—C16'—C23'—C18'	125.88 (19)
C3'—C7'—C8'—C9'	121.49 (19)	C7'—C16'—C23'—C18'	−117.47 (19)
C16'—C7'—C8'—C9'	−123.31 (19)	C17'—C16'—C23'—C18'	3.5 (2)
S1'—C7'—C8'—C9'	−0.6 (2)	C21—C22—C23—C18	−2.7 (3)
O3'—C8'—C9'—C15'	−177.6 (2)	C21—C22—C23—C16	−179.9 (2)
C7'—C8'—C9'—C15'	0.9 (2)	C19—C18—C23—C22	2.2 (3)
O3'—C8'—C9'—C10'	3.5 (4)	N2—C18—C23—C22	−176.70 (18)
C7'—C8'—C9'—C10'	−178.0 (2)	C19—C18—C23—C16	−179.95 (19)
O3—C8—C9—C15	178.4 (2)	N2—C18—C23—C16	1.1 (2)
C7—C8—C9—C15	−0.9 (3)	N1—C16—C23—C22	52.1 (3)
O3—C8—C9—C10	−2.6 (4)	C7—C16—C23—C22	−64.9 (3)
C7—C8—C9—C10	178.1 (2)	C17—C16—C23—C22	174.4 (2)
C15'—C9'—C10'—C11'	0.6 (3)	N1—C16—C23—C18	−125.32 (19)
C8'—C9'—C10'—C11'	179.4 (2)	C7—C16—C23—C18	117.70 (19)
C15—C9—C10—C11	−0.5 (4)	C17—C16—C23—C18	−3.0 (2)
C8—C9—C10—C11	−179.5 (2)	C23'—C16'—N1'—C1'	−60.5 (2)
C9'—C10'—C11'—C13'	0.7 (4)	C7'—C16'—N1'—C1'	173.11 (18)
C9'—C10'—C11'—C12'	−178.0 (2)	C17'—C16'—N1'—C1'	56.0 (2)
C9—C10—C11—C13	−0.6 (4)	C23'—C16'—N1'—C2'	169.02 (17)
C9—C10—C11—C12	177.7 (2)	C7'—C16'—N1'—C2'	42.61 (19)
C10—C11—C13—C14	1.0 (4)	C17'—C16'—N1'—C2'	−74.5 (2)
C12—C11—C13—C14	−177.3 (3)	C3'—C2'—N1'—C1'	−150.53 (18)
C10'—C11'—C13'—C14'	−1.3 (4)	C3'—C2'—N1'—C16'	−19.6 (2)
C12'—C11'—C13'—C14'	177.4 (2)	C23—C16—N1—C1	61.8 (3)
C11—C13—C14—C15	−0.3 (4)	C7—C16—N1—C1	−171.59 (19)
C11'—C13'—C14'—C15'	0.6 (4)	C17—C16—N1—C1	−54.6 (2)
C10'—C9'—C15'—C14'	−1.3 (3)	C23—C16—N1—C2	−168.35 (18)
C8'—C9'—C15'—C14'	179.7 (2)	C7—C16—N1—C2	−41.7 (2)
C10'—C9'—C15'—S1'	178.21 (17)	C17—C16—N1—C2	75.3 (2)
C8'—C9'—C15'—S1'	−0.7 (2)	C3—C2—N1—C1	149.20 (19)
C13'—C14'—C15'—C9'	0.7 (3)	C3—C2—N1—C16	19.2 (2)
C13'—C14'—C15'—S1'	−178.73 (18)	O2—C17—N2—C18	173.8 (2)
C10—C9—C15—C14	1.2 (3)	C16—C17—N2—C18	−3.7 (2)
C8—C9—C15—C14	−179.7 (2)	C19—C18—N2—C17	−177.1 (2)
C10—C9—C15—S1	−178.93 (18)	C23—C18—N2—C17	1.8 (2)
C8—C9—C15—S1	0.2 (2)	O2'—C17'—N2'—C18'	−173.8 (2)
C13—C14—C15—C9	−0.8 (4)	C16'—C17'—N2'—C18'	3.5 (2)
C13—C14—C15—S1	179.36 (19)	C19'—C18'—N2'—C17'	177.5 (2)
C8'—C7'—C16'—N1'	−171.82 (16)	C23'—C18'—N2'—C17'	−1.3 (2)
C3'—C7'—C16'—N1'	−48.09 (17)	O1'—C4'—O4'—C5'	0.3 (4)
S1'—C7'—C16'—N1'	66.79 (16)	C3'—C4'—O4'—C5'	177.6 (2)
C8'—C7'—C16'—C23'	62.4 (2)	C6'—C5'—O4'—C4'	107.4 (3)
C3'—C7'—C16'—C23'	−173.85 (16)	O1—C4—O4—C5	−2.3 (4)
S1'—C7'—C16'—C23'	−58.97 (19)	C3—C4—O4—C5	−179.3 (2)
C8'—C7'—C16'—C17'	−53.5 (2)	C6—C5—O4—C4	−121.2 (3)
C3'—C7'—C16'—C17'	70.28 (19)	C9—C15—S1—C7	0.53 (18)
S1'—C7'—C16'—C17'	−174.85 (13)	C14—C15—S1—C7	−179.6 (2)
C8—C7—C16—N1	171.27 (16)	C8—C7—S1—C15	−0.99 (15)
C3—C7—C16—N1	47.09 (17)	C3—C7—S1—C15	124.78 (15)
S1—C7—C16—N1	−67.99 (16)	C16—C7—S1—C15	−126.18 (14)
C8—C7—C16—C23	−63.0 (2)	C9'—C15'—S1'—C7'	0.32 (17)
C3—C7—C16—C23	172.77 (16)	C14'—C15'—S1'—C7'	179.8 (2)
S1—C7—C16—C23	57.69 (19)	C8'—C7'—S1'—C15'	0.17 (15)
C8—C7—C16—C17	52.9 (2)	C3'—C7'—S1'—C15'	−125.44 (15)
C3—C7—C16—C17	−71.29 (19)	C16'—C7'—S1'—C15'	125.85 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3′	0.86	2.09	2.941 (3)	168
N2′—H2′···O3	0.86	2.15	3.005 (3)	172
C13′—H13′···O2′i	0.93	2.57	3.439 (3)	155
C14′—H14′···01ii	0.93	2.54	3.402 (3)	154

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2O3	0.86	2.09	2.941(3)	168
N2H2O3	0.86	2.15	3.005(3)	172
C13H13O2i	0.93	2.57	3.439(3)	155
C14H1401ii	0.93	2.54	3.402(3)	154

Symmetry codes: (i) ; (ii) .