Intermolecular stacking in pyrazolo[3,4-d]pyrimidine-based pentamethylene-linked flexible ­molecules

The crystal structures of 1-{5-[4,6-bis­(methyl­sulfanyl)-2H-py­razolo­[3,4-d]­pyrimidin-2-yl]­pentyl}-6-methyl­sulfanyl-4-(pyr­rolidin-1-yl)-1H-pyrazolo­[3,4-d]­pyrimidine, C₂₂H₂₉N₉S₃, and 6-methyl­sulfanyl-1-{5-[6-methyl­sulfanyl-4-(pyrrolidin-1-yl)-2H-pyrazolo­[3,4-d]­pyrimidin-2-yl]­pentyl}-4-(pyrrolidin-1-yl)-1H-pyrazolo­[3,4-d]­pyrimidine, C₂₅H₃₄N₁₀S₂, which differ in having either a pyrrolidine substituent or a methylsulfanyl group, show intermolecular stacking due to aromatic π–π interactions between the pyrazolo­[3,4-d]­pyrimidine rings.

S1. Comment

Interactions between aromatic moieties are known to play an important role in chemistry (Tsuzuki et al., 2002; Hunter et al., 2001) and biology. They play a significant role in molecular recognition, stabilization of DNA/RNA structures (Hobza & Sponer, 1999) and crystal engineering (Desiraju, 1995). Use of a polymethylene, and especially a trimethylene (propylene) linker for studying intramolecular π–π interactions was pioneered by Leonard (Browne et al., 1968) and early work has been reviewed by Leonard (1979).

In 1995, we reported the first synthesis (Avasthi et al., 1995) and crystal structure determination (Biswas et al., 1995) of a trimethylene-linked molecule based on the pyrazolo[3,4-d]pyrimidine core, which is isomeric with the biologically important purine system. The robustness of the U-motif formed due to intramolecular stacking has been further demonstrated by crystal structure determinations of other closely related propylene-linked compounds (Maulik et al., 1998; Avasthi, Aswal & Maulik, 2001; Avasthi, Rawat et al., 2001). Interestingly, no intramolecular stacking is observed when the trimethylene linker is replaced by an ethylene (Avasthi, Rawat et al., 2001) or tetramethylene linker (Maulik et al., 2000). Importantly, bis-compounds involving ethylene, trimethylene, tetramethylene and pentamethylene linkers based on the pyrazolo[3,4-d]pyrimidine core show varying and unusual degrees of upfield shifts in their high-resolution (400 MHz) ¹H NMR spectra when compared with those of monomeric compounds (Garg et al., 1989). These observations indicate the possibility of intramolecular stacking in solution (Avasthi et al., 1995). Here, we report the structures of two pentamethylene-linked flexible molecules, 1-{5-[4,6-bis(methylsulfanyl)-2H-pyrazolo[3,4-d]pyrimidin-2-yl]pentyl}- 6-methylsulfanyl-4-(pyrrolidin-1-yl)-1H-pyrazolo[3,4-d]pyrimidine, (II), and 6-methylsulfanyl-1-{5-[6-methylsulfanyl-4-(pyrrolidin-1-yl)-2H- pyrazolo[3,4-d]pyrimidin-2-yl]pentyl}-4-(pyrrolidin-1-yl)-1H- pyrazolo[3,4-d]pyrimidine, (III), based on the same pyrazolo[3,4-d]pyrimidine core. Although many attempts have been made to crystallize the parent compound, 4,6-dimethylthio-1-[5-(4,6-dimethylthio-2H-pyrazolo-[3,4-d]pyrimidin-2-yl)- pentyl-1H-pyrazolo[3,4-d]pyrimidine, (I) (Avasthi et al., 1995), none of these proved successful. \sch

The crystal structure of (II) (Fig. 1) does not show any intramolecular stacking [N1···N2' 6.656 (3) Å]. The C—C—C angles in the five-atom linker bridge range between 111.3 (2) and 114.0 (2)°. The planar pyrazolo[3,4-d]pyrimidine rings are twisted [dihedral angle 62.82 (4)°] Interestingly, this twist allows intermolecular stacking (Fig. 2) between the pyrazolo[3,4-d]pyrimidine rings related by the symmetry operation (1 − x, 1 − y, 1 − z) about the body centre of the cell, with an interplanar separation of 3.534 (2) Å in a `parallel-displaced' orientation, the rings being parallel by symmetry. In addition, the other pyrazolo[3,4-d]pyrimidine ring, carrying a pyrrolidino group, similarly interacts with a neighbouring molecule, related by the symmetry operation (2 − x, −y, −z), at an interplanar distance of 3.512 (2) Å (Fig. 2). These two stacking interactions link the molecules into chains running parallel to [100].

The molecular structure and conformation of (III), which differs from (II) in having an additional pyrrolidino group, rather than a thiomethyl group, at position C4', is shown in Fig. 3. The planar pyrazolo[3,4-d]pyrimidine rings are closer to coplanarity [dihedral angles 8.3 (1) and 5.70 (4)° for the two molecules of the asymmetric unit]. Again, the crystal structure does not show any intramolecular stacking [N1···N2' 5.824 (3) and 5.797 (4) Å for the two molecules of the asymmetric unit]. The C—C—C angles in the five-atom linker range from 112.7 (3) to 113.6 (3)° for one molecule and from 113.0 (3) to 114.2 (3)° for the other. However, intermolecular stacking due to aromatic π–π interactions is still present, with the two molecules in the asymmetric unit stacking (Fig. 4) through partial overlap of their pyrazolo[3,4-d]pyrimidine rings. The average intermolecular spacing is 3.506 (4) Å and the minimum atom-atom distance is 3.580 (4) Å for N5'-C3''. In addition, there is also a face-to-face overlap of the pyrazolo[3,4-d]pyrimidine rings related by (1 − x, 1 − y, 1 − z), with an interplanar separation of 3.430 (2) Å; the rings are parallel by symmetry (Fig. 5). Thus, the crystal structures of (II) and (III) are stabilized mainly by aromatic π–π interactions.

S2. Experimental

Compounds (II) and (III) were prepared by refluxing a solution of (I) with pyrrolidine in benzene. Diffraction quality crystals of (II) were obtained from ethyl acetate solution, while crystals of (III) were isolated from chloroform-ethyl acetate (1:1) by slow evaporation of the solvent at room temperature.

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (II) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A crystal packing diagram for (II), showing the intermolecular π–π stacking between pyrazolo[3,4-d]pyrimidine rings.
	Fig. 3. A view of the structure of one of the independent molecules of (III) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A view of the molecules of (III) in one asymmetric unit, showing the partial overlapping of the rings due to intermolecular stacking.
	Fig. 5. A stereo crystal packing diagram for (III), showing the intermolecular π–π stacking between pyrazolo[3,4-d]pyrimidine rings.

(II) 1-{5-[4,6-bis(methylsulfanyl)-2H-pyrazolo[3,4-d]pyrimidin-2-yl]pentyl}- 6-methylsulfanyl-4-(pyrrolidin-1-yl)-1H-pyrazolo[3,4-d]pyrimidine

Crystal data

C22H29N9S3	F(000) = 544
Mr = 515.72	Dx = 1.336 Mg m^−3
Triclinic, P1	Melting point = 421–422 K
a = 10.1195 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.865 (1) Å	Cell parameters from 39 reflections
c = 12.271 (1) Å	θ = 4.9–12.5°
α = 70.563 (7)°	µ = 0.32 mm^−1
β = 70.092 (8)°	T = 293 K
γ = 73.452 (7)°	Block, colourless
V = 1281.7 (2) Å^3	0.44 × 0.30 × 0.22 mm
Z = 2

Data collection

Bruker P4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 1.8°
Graphite monochromator	h = −1→12
θ/2θ scans	k = −13→14
5878 measured reflections	l = −14→15
4980 independent reflections	3 standard reflections every 97 reflections
3921 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 0.4512P] where P = (Fo^2 + 2Fc^2)/3
4980 reflections	(Δ/σ)max < 0.001
310 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	1.18627 (7)	0.02545 (6)	0.22455 (6)	0.06775 (19)
S2	0.16158 (6)	0.59877 (7)	0.56461 (6)	0.0679 (2)
S3	0.60172 (7)	0.60176 (6)	0.69669 (5)	0.06484 (19)
N1	0.85463 (19)	0.29772 (17)	−0.02980 (16)	0.0566 (4)
N2	0.8494 (2)	0.3126 (2)	−0.14374 (18)	0.0677 (5)
C3	0.9591 (3)	0.2345 (2)	−0.1880 (2)	0.0626 (6)
H3	0.9815	0.2252	−0.2650	0.075*
C3A	1.0386 (2)	0.16631 (19)	−0.10465 (18)	0.0493 (5)
C4	1.1624 (2)	0.07312 (18)	−0.09477 (19)	0.0492 (5)
N5	1.20050 (19)	0.03564 (15)	0.00867 (16)	0.0516 (4)
C6	1.1194 (2)	0.08781 (18)	0.09716 (19)	0.0494 (5)
N7	1.00264 (18)	0.17427 (16)	0.10119 (15)	0.0510 (4)
C7A	0.9674 (2)	0.21054 (19)	−0.00398 (18)	0.0484 (5)
C8	0.7487 (2)	0.3724 (2)	0.0439 (2)	0.0596 (6)
H8A	0.7610	0.3435	0.1243	0.071*
H8B	0.6540	0.3638	0.0494	0.071*
C9	0.7583 (3)	0.5049 (2)	−0.0044 (2)	0.0636 (6)
H9A	0.7624	0.5308	−0.0891	0.076*
H9B	0.8458	0.5159	0.0034	0.076*
C10	0.6301 (3)	0.5836 (2)	0.0625 (2)	0.0587 (5)
H10A	0.5437	0.5767	0.0496	0.070*
H10B	0.6218	0.5528	0.1479	0.070*
C11	0.6407 (3)	0.7155 (2)	0.0237 (2)	0.0674 (6)
H11A	0.6528	0.7452	−0.0623	0.081*
H11B	0.7255	0.7224	0.0393	0.081*
C12	0.5120 (3)	0.7959 (2)	0.0858 (2)	0.0614 (6)
H12A	0.5273	0.8791	0.0573	0.074*
H12B	0.4281	0.7947	0.0653	0.074*
N13	1.2428 (2)	0.02022 (16)	−0.18237 (16)	0.0552 (4)
C14	1.2164 (3)	0.0507 (2)	−0.2987 (2)	0.0667 (6)
H14A	1.2272	0.1336	−0.3434	0.080*
H14B	1.1214	0.0409	−0.2907	0.080*
C15	1.3319 (4)	−0.0414 (3)	−0.3587 (3)	0.0991 (10)
H15A	1.2992	−0.1168	−0.3392	0.119*
H15B	1.3592	−0.0091	−0.4453	0.119*
C16	1.4544 (4)	−0.0610 (3)	−0.3079 (3)	0.0953 (10)
H16A	1.5076	0.0046	−0.3481	0.114*
H16B	1.5191	−0.1378	−0.3150	0.114*
C17	1.3810 (3)	−0.0620 (2)	−0.1779 (2)	0.0691 (7)
H17A	1.3679	−0.1434	−0.1293	0.083*
H17B	1.4355	−0.0321	−0.1456	0.083*
C18	1.0701 (4)	0.1167 (3)	0.3233 (3)	0.0889 (9)
H18A	1.0764	0.2007	0.2853	0.133*
H18B	1.0982	0.0911	0.3964	0.133*
H18C	0.9732	0.1072	0.3411	0.133*
N1'	0.5874 (2)	0.75833 (17)	0.26537 (17)	0.0562 (4)
N2'	0.48609 (19)	0.75607 (15)	0.21614 (16)	0.0523 (4)
C3'	0.3732 (2)	0.71212 (19)	0.2958 (2)	0.0523 (5)
H3'	0.2939	0.7030	0.2799	0.063*
C3'A	0.3978 (2)	0.68271 (17)	0.40750 (19)	0.0464 (4)
C4'	0.3308 (2)	0.63228 (18)	0.5291 (2)	0.0486 (5)
N5'	0.39478 (17)	0.61134 (15)	0.61292 (16)	0.0508 (4)
C6'	0.5269 (2)	0.64238 (18)	0.57572 (19)	0.0489 (5)
C7'A	0.5325 (2)	0.71265 (17)	0.38228 (19)	0.0475 (5)
N7'	0.59894 (19)	0.69349 (16)	0.46833 (16)	0.0530 (4)
C19	0.1303 (3)	0.5208 (3)	0.7209 (3)	0.0829 (8)
H19A	0.2090	0.4544	0.7327	0.124*
H19B	0.0434	0.4900	0.7480	0.124*
H19C	0.1219	0.5763	0.7658	0.124*
C20	0.7739 (3)	0.6421 (3)	0.6226 (3)	0.0867 (9)
H20A	0.8269	0.5947	0.5659	0.130*
H20B	0.8250	0.6260	0.6809	0.130*
H20C	0.7622	0.7271	0.5812	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0764 (4)	0.0638 (4)	0.0609 (4)	−0.0052 (3)	−0.0309 (3)	−0.0081 (3)
S2	0.0382 (3)	0.0921 (5)	0.0735 (4)	−0.0197 (3)	−0.0125 (3)	−0.0184 (3)
S3	0.0592 (4)	0.0803 (4)	0.0587 (3)	−0.0253 (3)	−0.0242 (3)	−0.0044 (3)
N1	0.0493 (10)	0.0643 (11)	0.0561 (11)	−0.0028 (9)	−0.0177 (8)	−0.0190 (9)
N2	0.0626 (12)	0.0816 (14)	0.0638 (12)	−0.0034 (11)	−0.0293 (10)	−0.0217 (11)
C3	0.0617 (14)	0.0739 (15)	0.0570 (13)	−0.0101 (12)	−0.0208 (11)	−0.0211 (11)
C3A	0.0462 (11)	0.0539 (12)	0.0504 (11)	−0.0161 (9)	−0.0115 (9)	−0.0130 (9)
C4	0.0495 (11)	0.0458 (11)	0.0522 (12)	−0.0187 (9)	−0.0088 (9)	−0.0097 (9)
N5	0.0510 (10)	0.0470 (9)	0.0531 (10)	−0.0108 (8)	−0.0126 (8)	−0.0089 (8)
C6	0.0502 (11)	0.0456 (11)	0.0518 (11)	−0.0169 (9)	−0.0152 (9)	−0.0044 (9)
N7	0.0492 (10)	0.0528 (10)	0.0487 (10)	−0.0108 (8)	−0.0120 (8)	−0.0110 (8)
C7A	0.0408 (10)	0.0513 (11)	0.0525 (11)	−0.0121 (9)	−0.0120 (9)	−0.0109 (9)
C8	0.0460 (12)	0.0664 (14)	0.0607 (13)	−0.0051 (10)	−0.0127 (10)	−0.0164 (11)
C9	0.0639 (14)	0.0651 (14)	0.0531 (13)	−0.0096 (11)	−0.0107 (11)	−0.0121 (11)
C10	0.0580 (13)	0.0583 (13)	0.0570 (13)	−0.0153 (10)	−0.0152 (10)	−0.0084 (10)
C11	0.0776 (16)	0.0595 (14)	0.0526 (13)	−0.0140 (12)	−0.0123 (12)	−0.0037 (10)
C12	0.0740 (15)	0.0499 (12)	0.0544 (13)	−0.0051 (11)	−0.0245 (11)	−0.0046 (10)
N13	0.0583 (11)	0.0529 (10)	0.0528 (10)	−0.0149 (8)	−0.0072 (8)	−0.0163 (8)
C14	0.0711 (16)	0.0722 (15)	0.0566 (14)	−0.0236 (13)	−0.0063 (12)	−0.0198 (12)
C15	0.098 (2)	0.122 (3)	0.080 (2)	−0.017 (2)	−0.0018 (17)	−0.0565 (19)
C16	0.086 (2)	0.093 (2)	0.090 (2)	0.0027 (17)	−0.0020 (17)	−0.0413 (17)
C17	0.0706 (16)	0.0509 (13)	0.0736 (16)	−0.0043 (11)	−0.0089 (13)	−0.0180 (11)
C18	0.109 (2)	0.096 (2)	0.0755 (18)	−0.0083 (18)	−0.0412 (17)	−0.0342 (16)
N1'	0.0545 (10)	0.0570 (10)	0.0579 (11)	−0.0184 (8)	−0.0180 (9)	−0.0067 (8)
N2'	0.0535 (10)	0.0469 (9)	0.0540 (10)	−0.0047 (8)	−0.0202 (8)	−0.0087 (8)
C3'	0.0436 (11)	0.0489 (11)	0.0655 (13)	−0.0020 (9)	−0.0218 (10)	−0.0149 (10)
C3'A	0.0371 (10)	0.0436 (10)	0.0579 (12)	−0.0033 (8)	−0.0157 (9)	−0.0135 (9)
C4'	0.0350 (10)	0.0460 (11)	0.0623 (13)	−0.0033 (8)	−0.0128 (9)	−0.0153 (9)
N5'	0.0405 (9)	0.0526 (10)	0.0576 (10)	−0.0107 (7)	−0.0135 (8)	−0.0108 (8)
C6'	0.0432 (11)	0.0465 (11)	0.0584 (12)	−0.0100 (9)	−0.0164 (9)	−0.0118 (9)
C7'A	0.0452 (11)	0.0414 (10)	0.0549 (12)	−0.0105 (8)	−0.0145 (9)	−0.0084 (9)
N7'	0.0481 (10)	0.0583 (10)	0.0556 (10)	−0.0202 (8)	−0.0171 (8)	−0.0071 (8)
C19	0.0522 (14)	0.105 (2)	0.0798 (18)	−0.0300 (14)	−0.0112 (13)	−0.0035 (15)
C20	0.0601 (16)	0.129 (3)	0.0815 (18)	−0.0391 (16)	−0.0287 (14)	−0.0141 (17)

Geometric parameters (Å, º)

S1—C6	1.765 (2)	N13—C14	1.450 (3)
S1—C18	1.788 (3)	N13—C17	1.466 (3)
S2—C4'	1.745 (2)	C14—C15	1.524 (4)
S2—C19	1.790 (3)	C14—H14A	0.9700
S3—C6'	1.758 (2)	C14—H14B	0.9700
S3—C20	1.788 (3)	C15—C16	1.498 (5)
N1—C7A	1.352 (3)	C15—H15A	0.9700
N1—N2	1.367 (3)	C15—H15B	0.9700
N1—C8	1.444 (3)	C16—C17	1.511 (4)
N2—C3	1.313 (3)	C16—H16A	0.9700
C3—C3A	1.410 (3)	C16—H16B	0.9700
C3—H3	0.9300	C17—H17A	0.9700
C3A—C7A	1.389 (3)	C17—H17B	0.9700
C3A—C4	1.425 (3)	C18—H18A	0.9600
C4—N13	1.332 (3)	C18—H18B	0.9600
C4—N5	1.348 (3)	C18—H18C	0.9600
N5—C6	1.337 (3)	N1'—C7'A	1.331 (3)
C6—N7	1.324 (3)	N1'—N2'	1.365 (2)
N7—C7A	1.354 (3)	N2'—C3'	1.331 (3)
C8—C9	1.503 (3)	C3'—C3'A	1.388 (3)
C8—H8A	0.9700	C3'—H3'	0.9300
C8—H8B	0.9700	C3'A—C4'	1.412 (3)
C9—C10	1.524 (3)	C3'A—C7'A	1.413 (3)
C9—H9A	0.9700	C4'—N5'	1.315 (3)
C9—H9B	0.9700	N5'—C6'	1.373 (3)
C10—C11	1.502 (3)	C6'—N7'	1.304 (3)
C10—H10A	0.9700	C7'A—N7'	1.362 (3)
C10—H10B	0.9700	C19—H19A	0.9600
C11—C12	1.512 (3)	C19—H19B	0.9600
C11—H11A	0.9700	C19—H19C	0.9600
C11—H11B	0.9700	C20—H20A	0.9600
C12—N2'	1.460 (3)	C20—H20B	0.9600
C12—H12A	0.9700	C20—H20C	0.9600
C12—H12B	0.9700
C6—S1—C18	102.28 (12)	N13—C14—H14B	111.3
C4'—S2—C19	102.53 (12)	C15—C14—H14B	111.3
C6'—S3—C20	101.60 (12)	H14A—C14—H14B	109.2
C7A—N1—N2	111.00 (18)	C16—C15—C14	103.9 (2)
C7A—N1—C8	129.12 (19)	C16—C15—H15A	111.0
N2—N1—C8	119.86 (18)	C14—C15—H15A	111.0
C3—N2—N1	105.73 (18)	C16—C15—H15B	111.0
N2—C3—C3A	111.8 (2)	C14—C15—H15B	111.0
N2—C3—H3	124.1	H15A—C15—H15B	109.0
C3A—C3—H3	124.1	C15—C16—C17	103.1 (3)
C7A—C3A—C3	104.15 (19)	C15—C16—H16A	111.2
C7A—C3A—C4	115.58 (19)	C17—C16—H16A	111.2
C3—C3A—C4	140.3 (2)	C15—C16—H16B	111.2
N13—C4—N5	117.85 (19)	C17—C16—H16B	111.2
N13—C4—C3A	123.5 (2)	H16A—C16—H16B	109.1
N5—C4—C3A	118.63 (19)	N13—C17—C16	103.3 (2)
C6—N5—C4	118.02 (18)	N13—C17—H17A	111.1
N7—C6—N5	130.12 (19)	C16—C17—H17A	111.1
N7—C6—S1	118.93 (16)	N13—C17—H17B	111.1
N5—C6—S1	110.95 (15)	C16—C17—H17B	111.1
C6—N7—C7A	110.54 (18)	H17A—C17—H17B	109.1
N1—C7A—N7	125.61 (19)	S1—C18—H18A	109.5
N1—C7A—C3A	107.28 (18)	S1—C18—H18B	109.5
N7—C7A—C3A	127.10 (19)	H18A—C18—H18B	109.5
N1—C8—C9	112.86 (19)	S1—C18—H18C	109.5
N1—C8—H8A	109.0	H18A—C18—H18C	109.5
C9—C8—H8A	109.0	H18B—C18—H18C	109.5
N1—C8—H8B	109.0	C7'A—N1'—N2'	103.07 (17)
C9—C8—H8B	109.0	C3'—N2'—N1'	114.19 (18)
H8A—C8—H8B	107.8	C3'—N2'—C12	126.7 (2)
C8—C9—C10	111.3 (2)	N1'—N2'—C12	119.04 (19)
C8—C9—H9A	109.4	N2'—C3'—C3'A	106.11 (18)
C10—C9—H9A	109.4	N2'—C3'—H3'	126.9
C8—C9—H9B	109.4	C3'A—C3'—H3'	126.9
C10—C9—H9B	109.4	C3'—C3'A—C4'	138.83 (19)
H9A—C9—H9B	108.0	C3'—C3'A—C7'A	104.44 (18)
C11—C10—C9	113.2 (2)	C4'—C3'A—C7'A	116.71 (18)
C11—C10—H10A	108.9	N5'—C4'—C3'A	120.64 (18)
C9—C10—H10A	108.9	N5'—C4'—S2	121.23 (16)
C11—C10—H10B	108.9	C3'A—C4'—S2	118.13 (16)
C9—C10—H10B	108.9	C4'—N5'—C6'	116.62 (18)
H10A—C10—H10B	107.8	N7'—C6'—N5'	129.55 (19)
C10—C11—C12	114.0 (2)	N7'—C6'—S3	119.40 (15)
C10—C11—H11A	108.8	N5'—C6'—S3	111.04 (15)
C12—C11—H11A	108.8	N1'—C7'A—N7'	124.50 (19)
C10—C11—H11B	108.8	N1'—C7'A—C3'A	112.18 (18)
C12—C11—H11B	108.8	N7'—C7'A—C3'A	123.30 (19)
H11A—C11—H11B	107.7	C6'—N7'—C7'A	113.09 (17)
N2'—C12—C11	111.95 (18)	S2—C19—H19A	109.5
N2'—C12—H12A	109.2	S2—C19—H19B	109.5
C11—C12—H12A	109.2	H19A—C19—H19B	109.5
N2'—C12—H12B	109.2	S2—C19—H19C	109.5
C11—C12—H12B	109.2	H19A—C19—H19C	109.5
H12A—C12—H12B	107.9	H19B—C19—H19C	109.5
C4—N13—C14	124.47 (19)	S3—C20—H20A	109.5
C4—N13—C17	122.7 (2)	S3—C20—H20B	109.5
C14—N13—C17	112.16 (18)	H20A—C20—H20B	109.5
N13—C14—C15	102.5 (2)	S3—C20—H20C	109.5
N13—C14—H14A	111.3	H20A—C20—H20C	109.5
C15—C14—H14A	111.3	H20B—C20—H20C	109.5
C7A—N1—N2—C3	0.0 (3)	C4—N13—C14—C15	−176.3 (2)
C8—N1—N2—C3	179.0 (2)	C17—N13—C14—C15	12.7 (3)
N1—N2—C3—C3A	0.1 (3)	N13—C14—C15—C16	−32.0 (3)
N2—C3—C3A—C7A	−0.3 (3)	C14—C15—C16—C17	39.4 (3)
N2—C3—C3A—C4	−179.4 (2)	C4—N13—C17—C16	−159.9 (2)
C7A—C3A—C4—N13	179.70 (19)	C14—N13—C17—C16	11.3 (3)
C3—C3A—C4—N13	−1.2 (4)	C15—C16—C17—N13	−31.0 (3)
C7A—C3A—C4—N5	0.0 (3)	C7'A—N1'—N2'—C3'	0.1 (2)
C3—C3A—C4—N5	179.1 (3)	C7'A—N1'—N2'—C12	−177.63 (18)
N13—C4—N5—C6	−179.47 (18)	C11—C12—N2'—C3'	−114.4 (2)
C3A—C4—N5—C6	0.3 (3)	C11—C12—N2'—N1'	63.1 (3)
C4—N5—C6—N7	−0.2 (3)	N1'—N2'—C3'—C3'A	0.3 (2)
C4—N5—C6—S1	179.53 (14)	C12—N2'—C3'—C3'A	177.88 (19)
C18—S1—C6—N7	−4.5 (2)	N2'—C3'—C3'A—C4'	−178.8 (2)
C18—S1—C6—N5	175.72 (17)	N2'—C3'—C3'A—C7'A	−0.6 (2)
N5—C6—N7—C7A	−0.2 (3)	C3'—C3'A—C4'—N5'	175.9 (2)
S1—C6—N7—C7A	−179.87 (14)	C7'A—C3'A—C4'—N5'	−2.1 (3)
N2—N1—C7A—N7	179.8 (2)	C3'—C3'A—C4'—S2	−4.1 (4)
C8—N1—C7A—N7	1.0 (4)	C7'A—C3'A—C4'—S2	177.90 (14)
N2—N1—C7A—C3A	−0.2 (2)	C19—S2—C4'—N5'	−7.1 (2)
C8—N1—C7A—C3A	−179.1 (2)	C19—S2—C4'—C3'A	172.93 (18)
C6—N7—C7A—N1	−179.6 (2)	C3'A—C4'—N5'—C6'	0.8 (3)
C6—N7—C7A—C3A	0.4 (3)	S2—C4'—N5'—C6'	−179.20 (15)
C3—C3A—C7A—N1	0.3 (2)	C4'—N5'—C6'—N7'	2.1 (3)
C4—C3A—C7A—N1	179.69 (17)	C4'—N5'—C6'—S3	−177.00 (15)
C3—C3A—C7A—N7	−179.8 (2)	C20—S3—C6'—N7'	−2.9 (2)
C4—C3A—C7A—N7	−0.4 (3)	C20—S3—C6'—N5'	176.28 (17)
C7A—N1—C8—C9	113.2 (3)	N2'—N1'—C7'A—N7'	177.85 (19)
N2—N1—C8—C9	−65.6 (3)	N2'—N1'—C7'A—C3'A	−0.5 (2)
N1—C8—C9—C10	170.11 (19)	C3'—C3'A—C7'A—N1'	0.7 (2)
C8—C9—C10—C11	175.6 (2)	C4'—C3'A—C7'A—N1'	179.39 (18)
C9—C10—C11—C12	177.9 (2)	C3'—C3'A—C7'A—N7'	−177.67 (19)
C10—C11—C12—N2'	58.0 (3)	C4'—C3'A—C7'A—N7'	1.0 (3)
N5—C4—N13—C14	−179.7 (2)	N5'—C6'—N7'—C7'A	−3.1 (3)
C3A—C4—N13—C14	0.6 (3)	S3—C6'—N7'—C7'A	175.91 (15)
N5—C4—N13—C17	−9.6 (3)	N1'—C7'A—N7'—C6'	−176.8 (2)
C3A—C4—N13—C17	170.6 (2)	C3'A—C7'A—N7'—C6'	1.4 (3)

(III) 6-methylsulfanyl-1-{5-[6-methylsulfanyl-4-(pyrrolidin-1-yl)-2H- pyrazolo[3,4-d]pyrimidin-2-yl]pentyl}-4-(pyrrolidin-1-yl)-1H- pyrazolo[3,4-d]pyrimidine

Crystal data

C25H34N10S2	F(000) = 1144
Mr = 538.74	Dx = 1.324 Mg m^−3
Triclinic, P1	Melting point = 431–433 K
a = 10.006 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.283 (1) Å	Cell parameters from 41 reflections
c = 18.411 (2) Å	θ = 5.3–12.5°
α = 74.164 (7)°	µ = 0.23 mm^−1
β = 89.970 (9)°	T = 293 K
γ = 86.359 (9)°	Block, colourless
V = 2702.7 (4) Å^3	0.38 × 0.33 × 0.23 mm
Z = 4

Data collection

Bruker P4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.0°
Graphite monochromator	h = −1→12
θ/2θ scans	k = −18→18
12443 measured reflections	l = −22→22
10538 independent reflections	3 standard reflections every 97 reflections
6258 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 0.688P] where P = (Fo^2 + 2Fc^2)/3
10538 reflections	(Δ/σ)max = 0.001
671 parameters	Δρmax = 0.27 e Å^−3
10 restraints	Δρmin = −0.30 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.79844 (9)	0.87520 (7)	0.57598 (5)	0.0779 (3)
S2	0.40059 (8)	0.63881 (6)	0.25424 (5)	0.0677 (2)
S1'	0.22124 (9)	0.86701 (7)	0.07883 (5)	0.0757 (3)
S2'	0.66919 (9)	0.64044 (6)	−0.24553 (5)	0.0673 (2)
N1	0.3827 (3)	0.88458 (17)	0.73087 (14)	0.0587 (6)
N2	0.3591 (3)	0.87786 (18)	0.80541 (15)	0.0655 (7)
C3	0.4777 (3)	0.8722 (2)	0.83693 (18)	0.0632 (8)
H3	0.4917	0.8667	0.8880	0.076*
C3A	0.5820 (3)	0.87551 (19)	0.78485 (16)	0.0517 (7)
C4	0.7231 (3)	0.87579 (19)	0.78103 (16)	0.0518 (7)
N5	0.7824 (2)	0.87691 (17)	0.71474 (13)	0.0577 (6)
C6	0.7031 (3)	0.8807 (2)	0.65598 (16)	0.0573 (8)
N7	0.5709 (3)	0.88628 (17)	0.64923 (13)	0.0575 (6)
C7A	0.5144 (3)	0.88284 (19)	0.71745 (16)	0.0532 (7)
C8	0.2718 (3)	0.8988 (2)	0.67762 (19)	0.0678 (9)
H8A	0.3055	0.9194	0.6268	0.081*
H8B	0.2099	0.9466	0.6856	0.081*
C9	0.1970 (3)	0.8137 (2)	0.68443 (17)	0.0624 (8)
H9A	0.1622	0.7937	0.7350	0.075*
H9B	0.1213	0.8287	0.6493	0.075*
C10	0.2829 (3)	0.7361 (2)	0.66867 (17)	0.0594 (8)
H10A	0.3568	0.7197	0.7049	0.071*
H10B	0.3202	0.7568	0.6187	0.071*
C11	0.2074 (3)	0.6522 (2)	0.67275 (17)	0.0624 (8)
H11A	0.1652	0.6339	0.7215	0.075*
H11B	0.1369	0.6678	0.6344	0.075*
C12	0.2935 (3)	0.5724 (2)	0.66191 (17)	0.0651 (9)
H12A	0.3646	0.5569	0.6999	0.078*
H12B	0.2395	0.5202	0.6695	0.078*
N13	0.8036 (2)	0.87547 (17)	0.83920 (13)	0.0587 (6)
C14	0.9489 (3)	0.8810 (3)	0.83260 (18)	0.0715 (9)
H14A	0.9718	0.9252	0.7863	0.086*
H14B	0.9933	0.8222	0.8341	0.086*
C15	0.9854 (4)	0.9111 (3)	0.90070 (19)	0.0838 (11)
H15A	1.0764	0.8897	0.9176	0.101*
H15B	0.9772	0.9771	0.8896	0.101*
C16	0.8865 (4)	0.8687 (3)	0.95936 (19)	0.0818 (11)
H16A	0.8756	0.9024	0.9969	0.098*
H16B	0.9153	0.8059	0.9845	0.098*
C17	0.7576 (3)	0.8741 (2)	0.91473 (16)	0.0611 (8)
H17A	0.7063	0.8216	0.9358	0.073*
H17B	0.7029	0.9291	0.9139	0.073*
C18	0.6715 (4)	0.8806 (3)	0.50790 (19)	0.0931 (12)
H18A	0.6133	0.8321	0.5266	0.140*
H18B	0.7115	0.8745	0.4620	0.140*
H18C	0.6206	0.9381	0.4982	0.140*
N19	0.7191 (2)	0.63988 (17)	0.45192 (14)	0.0594 (7)
C20	0.8222 (3)	0.6542 (3)	0.3940 (2)	0.0736 (10)
H20A	0.8203	0.7176	0.3651	0.088*
H20B	0.8098	0.6169	0.3598	0.088*
C21	0.9492 (4)	0.6262 (3)	0.4374 (2)	0.0983 (13)
H21A	1.0204	0.6630	0.4127	0.118*
H21B	0.9750	0.5626	0.4420	0.118*
C22	0.9235 (3)	0.6404 (3)	0.5128 (3)	0.0941 (13)
H22A	0.9400	0.7023	0.5128	0.113*
H22B	0.9807	0.5984	0.5511	0.113*
C23	0.7763 (3)	0.6224 (2)	0.52791 (18)	0.0657 (9)
H23A	0.7663	0.5600	0.5571	0.079*
H23B	0.7346	0.6635	0.5545	0.079*
C24	0.2240 (3)	0.6280 (3)	0.24791 (19)	0.0809 (11)
H24A	0.1987	0.5770	0.2877	0.121*
H24B	0.2024	0.6186	0.1999	0.121*
H24C	0.1765	0.6826	0.2528	0.121*
N1'	0.2720 (2)	0.59602 (16)	0.52662 (13)	0.0550 (6)
N2'	0.3524 (2)	0.59044 (16)	0.58748 (13)	0.0540 (6)
C3'	0.4799 (3)	0.60173 (19)	0.57092 (17)	0.0534 (7)
H3'	0.5495	0.6000	0.6049	0.064*
C3'A	0.4904 (3)	0.61657 (18)	0.49343 (16)	0.0481 (7)
C4'	0.5903 (3)	0.63189 (18)	0.43694 (17)	0.0500 (7)
N5'	0.5552 (2)	0.63897 (16)	0.36525 (13)	0.0526 (6)
C6'	0.4244 (3)	0.63145 (19)	0.35078 (16)	0.0499 (7)
N7'	0.3215 (2)	0.61973 (16)	0.39587 (13)	0.0522 (6)
C7'A	0.3580 (3)	0.61184 (18)	0.46885 (16)	0.0468 (7)
N1''	0.6316 (3)	0.89594 (17)	0.22882 (14)	0.0595 (6)
N2''	0.6566 (3)	0.89108 (18)	0.30313 (15)	0.0670 (7)
C3''	0.5395 (3)	0.8809 (2)	0.33569 (18)	0.0633 (8)
H3''	0.5267	0.8761	0.3866	0.076*
C3''A	0.4357 (3)	0.87793 (19)	0.28502 (15)	0.0509 (7)
C4''	0.2951 (3)	0.87252 (19)	0.28286 (16)	0.0521 (7)
N5''	0.2359 (2)	0.87115 (17)	0.21733 (13)	0.0565 (6)
C6''	0.3143 (3)	0.8769 (2)	0.15763 (16)	0.0559 (7)
N7''	0.4440 (3)	0.88800 (16)	0.14956 (13)	0.0572 (6)
C7''A	0.5001 (3)	0.88792 (18)	0.21698 (16)	0.0524 (7)
C8''	0.7383 (3)	0.9125 (2)	0.17478 (19)	0.0685 (9)
H8''1	0.7886	0.9617	0.1822	0.082*
H8''2	0.6995	0.9321	0.1242	0.082*
C9''	0.8330 (3)	0.8296 (2)	0.18127 (18)	0.0637 (8)
H9''1	0.8726	0.8104	0.2317	0.076*
H9''2	0.9048	0.8459	0.1457	0.076*
C10''	0.7642 (3)	0.7504 (2)	0.16600 (17)	0.0587 (8)
H10C	0.6948	0.7326	0.2029	0.070*
H10D	0.7214	0.7705	0.1165	0.070*
C11''	0.8588 (3)	0.6688 (2)	0.16921 (17)	0.0628 (8)
H11C	0.9246	0.6857	0.1300	0.075*
H11D	0.9062	0.6515	0.2175	0.075*
C12''	0.7903 (3)	0.5878 (2)	0.15941 (16)	0.0638 (8)
H12C	0.8559	0.5366	0.1665	0.077*
H12D	0.7236	0.5714	0.1982	0.077*
N13''	0.2162 (2)	0.86998 (17)	0.34131 (12)	0.0588 (6)
C14''	0.0696 (3)	0.8746 (3)	0.33597 (16)	0.0744 (10)
H14C	0.0374	0.8158	0.3367	0.089*
H14D	0.0366	0.9195	0.2904	0.089*
C15''	0.0285 (3)	0.9023 (3)	0.40508 (18)	0.0949 (13)
H15C	−0.0564	0.8781	0.4231	0.114*
H15D	0.0196	0.9682	0.3944	0.114*
C16''	0.1368 (3)	0.8635 (3)	0.46188 (16)	0.0922 (12)
H16C	0.1223	0.8008	0.4885	0.111*
H16D	0.1412	0.8987	0.4983	0.111*
C17''	0.2641 (3)	0.8689 (2)	0.41670 (14)	0.0632 (8)
H17C	0.3083	0.9240	0.4155	0.076*
H17D	0.3258	0.8164	0.4375	0.076*
C18''	0.3480 (4)	0.8746 (3)	0.01009 (19)	0.0897 (12)
H18D	0.3830	0.9338	−0.0012	0.135*
H18E	0.3107	0.8654	−0.0351	0.135*
H18F	0.4189	0.8288	0.0294	0.135*
N19''	0.3472 (2)	0.62778 (17)	−0.04580 (12)	0.0551 (6)
C20''	0.2422 (3)	0.6412 (2)	−0.10351 (15)	0.0653 (8)
H20C	0.2548	0.5967	−0.1322	0.078*
H20D	0.2414	0.7019	−0.1379	0.078*
C21''	0.1168 (3)	0.6285 (4)	−0.0605 (2)	0.1119 (16)
H21C	0.0501	0.6769	−0.0837	0.134*
H21D	0.0821	0.5708	−0.0607	0.134*
C22''	0.1445 (3)	0.6300 (3)	0.0169 (2)	0.1040 (14)
H22C	0.1007	0.5814	0.0521	0.125*
H22D	0.1110	0.6877	0.0246	0.125*
C23''	0.2935 (3)	0.6171 (2)	0.02968 (15)	0.0613 (8)
H23C	0.3253	0.6627	0.0520	0.074*
H23D	0.3189	0.5571	0.0625	0.074*
C24''	0.8481 (3)	0.6398 (3)	−0.2520 (2)	0.0798 (10)
H24D	0.8781	0.6939	−0.2419	0.120*
H24E	0.8741	0.6383	−0.3018	0.120*
H24F	0.8879	0.5870	−0.2157	0.120*
N31	0.8028 (2)	0.61659 (16)	0.02331 (13)	0.0547 (6)
N32	0.7254 (2)	0.60432 (16)	0.08548 (13)	0.0529 (6)
C33	0.5956 (3)	0.60545 (19)	0.07115 (16)	0.0536 (7)
H33	0.5274	0.5987	0.1062	0.064*
C33A	0.5805 (3)	0.61871 (18)	−0.00640 (15)	0.0465 (6)
C34	0.4779 (3)	0.62670 (18)	−0.06196 (16)	0.0474 (7)
N35	0.5123 (2)	0.63286 (15)	−0.13327 (13)	0.0508 (6)
C36	0.6439 (3)	0.63520 (18)	−0.14966 (15)	0.0488 (7)
N37	0.7482 (2)	0.63378 (16)	−0.10631 (13)	0.0512 (6)
C37A	0.7139 (3)	0.62423 (18)	−0.03266 (16)	0.0464 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0660 (6)	0.1225 (8)	0.0528 (5)	−0.0065 (5)	0.0097 (4)	−0.0367 (5)
S2	0.0585 (5)	0.0933 (6)	0.0551 (5)	−0.0057 (4)	−0.0020 (4)	−0.0267 (4)
S1'	0.0655 (6)	0.1150 (8)	0.0533 (5)	−0.0040 (5)	−0.0025 (4)	−0.0348 (5)
S2'	0.0600 (5)	0.0923 (6)	0.0544 (5)	−0.0052 (4)	0.0047 (4)	−0.0280 (4)
N1	0.0557 (16)	0.0634 (16)	0.0595 (16)	0.0001 (12)	0.0012 (13)	−0.0222 (13)
N2	0.0613 (18)	0.0769 (19)	0.0623 (17)	0.0001 (14)	0.0111 (14)	−0.0268 (14)
C3	0.067 (2)	0.075 (2)	0.0524 (18)	−0.0038 (17)	0.0090 (16)	−0.0250 (16)
C3A	0.0576 (19)	0.0495 (17)	0.0507 (17)	−0.0037 (14)	0.0073 (14)	−0.0184 (13)
C4	0.0588 (19)	0.0488 (17)	0.0490 (17)	−0.0049 (14)	0.0043 (14)	−0.0151 (13)
N5	0.0588 (16)	0.0708 (17)	0.0457 (14)	−0.0072 (13)	0.0059 (12)	−0.0192 (12)
C6	0.061 (2)	0.062 (2)	0.0492 (17)	−0.0050 (15)	0.0083 (15)	−0.0162 (14)
N7	0.0604 (17)	0.0655 (16)	0.0481 (14)	−0.0012 (13)	0.0030 (12)	−0.0187 (12)
C7A	0.0550 (19)	0.0463 (17)	0.0591 (19)	−0.0004 (14)	0.0065 (15)	−0.0167 (14)
C8	0.057 (2)	0.073 (2)	0.075 (2)	0.0088 (17)	0.0003 (17)	−0.0247 (18)
C9	0.0463 (17)	0.084 (2)	0.0575 (18)	0.0027 (16)	0.0028 (14)	−0.0218 (16)
C10	0.0471 (17)	0.076 (2)	0.0587 (18)	−0.0057 (15)	0.0050 (14)	−0.0236 (16)
C11	0.0557 (19)	0.086 (2)	0.0489 (17)	−0.0170 (17)	0.0088 (14)	−0.0218 (16)
C12	0.075 (2)	0.069 (2)	0.0510 (18)	−0.0205 (18)	0.0084 (16)	−0.0119 (15)
N13	0.0579 (16)	0.0728 (17)	0.0482 (14)	−0.0073 (13)	0.0034 (12)	−0.0208 (12)
C14	0.059 (2)	0.093 (3)	0.061 (2)	−0.0052 (18)	0.0022 (16)	−0.0167 (18)
C15	0.069 (2)	0.113 (3)	0.072 (2)	−0.009 (2)	−0.0071 (19)	−0.029 (2)
C16	0.078 (2)	0.109 (3)	0.057 (2)	−0.002 (2)	−0.0026 (18)	−0.022 (2)
C17	0.072 (2)	0.063 (2)	0.0490 (17)	−0.0048 (16)	0.0037 (15)	−0.0164 (15)
C18	0.075 (3)	0.153 (4)	0.055 (2)	−0.001 (2)	0.0025 (18)	−0.038 (2)
N19	0.0426 (14)	0.0691 (17)	0.0689 (17)	−0.0097 (12)	−0.0048 (12)	−0.0216 (13)
C20	0.0497 (19)	0.086 (2)	0.089 (2)	−0.0122 (17)	0.0109 (18)	−0.029 (2)
C21	0.047 (2)	0.125 (4)	0.112 (3)	−0.007 (2)	−0.003 (2)	−0.015 (3)
C22	0.048 (2)	0.126 (3)	0.124 (3)	−0.004 (2)	−0.018 (2)	−0.060 (3)
C23	0.0538 (19)	0.071 (2)	0.075 (2)	−0.0082 (16)	−0.0120 (16)	−0.0236 (17)
C24	0.064 (2)	0.115 (3)	0.067 (2)	−0.014 (2)	−0.0149 (17)	−0.029 (2)
N1'	0.0478 (14)	0.0639 (16)	0.0542 (15)	−0.0081 (12)	0.0005 (12)	−0.0167 (12)
N2'	0.0581 (16)	0.0560 (15)	0.0498 (14)	−0.0100 (12)	0.0008 (12)	−0.0163 (11)
C3'	0.0511 (18)	0.0506 (17)	0.0598 (19)	−0.0064 (14)	−0.0075 (14)	−0.0165 (14)
C3'A	0.0465 (16)	0.0446 (16)	0.0560 (17)	−0.0025 (13)	−0.0054 (13)	−0.0183 (13)
C4'	0.0403 (16)	0.0467 (17)	0.0647 (19)	−0.0029 (12)	−0.0039 (14)	−0.0180 (14)
N5'	0.0419 (14)	0.0584 (15)	0.0594 (15)	−0.0040 (11)	−0.0006 (11)	−0.0190 (12)
C6'	0.0459 (17)	0.0517 (17)	0.0541 (17)	−0.0011 (13)	−0.0025 (14)	−0.0180 (13)
N7'	0.0416 (13)	0.0599 (15)	0.0572 (15)	−0.0025 (11)	−0.0059 (12)	−0.0197 (12)
C7'A	0.0422 (16)	0.0466 (16)	0.0535 (17)	−0.0034 (12)	−0.0039 (13)	−0.0169 (13)
N1''	0.0585 (17)	0.0623 (16)	0.0617 (16)	−0.0110 (13)	0.0043 (13)	−0.0224 (13)
N2''	0.0641 (18)	0.0769 (19)	0.0677 (18)	−0.0112 (14)	−0.0051 (14)	−0.0314 (14)
C3''	0.064 (2)	0.075 (2)	0.0566 (19)	−0.0089 (17)	0.0014 (17)	−0.0264 (16)
C3''A	0.0556 (18)	0.0511 (17)	0.0483 (16)	−0.0029 (14)	−0.0028 (14)	−0.0174 (13)
C4''	0.0574 (19)	0.0501 (17)	0.0487 (17)	−0.0015 (14)	−0.0026 (14)	−0.0139 (13)
N5''	0.0577 (15)	0.0661 (16)	0.0482 (14)	−0.0020 (12)	0.0009 (12)	−0.0204 (12)
C6''	0.058 (2)	0.0594 (19)	0.0516 (17)	0.0008 (15)	−0.0044 (15)	−0.0180 (14)
N7''	0.0620 (17)	0.0608 (16)	0.0490 (14)	−0.0031 (13)	0.0004 (12)	−0.0152 (12)
C7''A	0.0549 (19)	0.0444 (17)	0.0590 (19)	−0.0039 (14)	−0.0029 (15)	−0.0157 (14)
C8''	0.063 (2)	0.070 (2)	0.076 (2)	−0.0176 (18)	0.0111 (17)	−0.0236 (17)
C9''	0.0495 (18)	0.085 (2)	0.0623 (19)	−0.0136 (17)	0.0048 (15)	−0.0285 (17)
C10''	0.0467 (17)	0.074 (2)	0.0593 (18)	−0.0047 (15)	−0.0014 (14)	−0.0246 (16)
C11''	0.0526 (18)	0.086 (2)	0.0532 (17)	0.0029 (17)	−0.0043 (14)	−0.0256 (16)
C12''	0.065 (2)	0.074 (2)	0.0500 (17)	0.0028 (17)	−0.0055 (15)	−0.0143 (15)
N13''	0.0552 (16)	0.0755 (18)	0.0467 (14)	−0.0047 (13)	0.0006 (12)	−0.0184 (12)
C14''	0.058 (2)	0.104 (3)	0.060 (2)	−0.0131 (19)	0.0042 (16)	−0.0203 (19)
C15''	0.069 (2)	0.148 (4)	0.072 (2)	−0.013 (2)	0.016 (2)	−0.036 (2)
C16''	0.083 (3)	0.141 (4)	0.057 (2)	−0.031 (3)	0.014 (2)	−0.029 (2)
C17''	0.067 (2)	0.076 (2)	0.0475 (17)	−0.0073 (17)	−0.0016 (15)	−0.0181 (15)
C18''	0.078 (3)	0.138 (4)	0.057 (2)	−0.008 (2)	0.0040 (18)	−0.035 (2)
N19''	0.0376 (13)	0.0659 (16)	0.0611 (15)	−0.0018 (11)	0.0044 (11)	−0.0163 (12)
C20''	0.0462 (18)	0.072 (2)	0.076 (2)	−0.0018 (15)	−0.0069 (16)	−0.0172 (17)
C21''	0.043 (2)	0.185 (5)	0.097 (3)	0.006 (2)	0.005 (2)	−0.023 (3)
C22''	0.043 (2)	0.170 (4)	0.115 (3)	−0.008 (2)	0.016 (2)	−0.066 (3)
C23''	0.0459 (17)	0.067 (2)	0.073 (2)	−0.0015 (15)	0.0113 (15)	−0.0239 (17)
C24''	0.063 (2)	0.111 (3)	0.070 (2)	−0.002 (2)	0.0188 (17)	−0.033 (2)
N31	0.0437 (14)	0.0662 (16)	0.0557 (15)	−0.0028 (12)	0.0009 (12)	−0.0190 (12)
N32	0.0516 (15)	0.0580 (15)	0.0498 (14)	−0.0018 (12)	−0.0007 (12)	−0.0161 (11)
C33	0.0462 (18)	0.0583 (18)	0.0576 (18)	0.0005 (14)	0.0063 (14)	−0.0189 (14)
C33A	0.0429 (16)	0.0448 (16)	0.0522 (16)	−0.0007 (12)	0.0050 (13)	−0.0146 (13)
C34	0.0396 (16)	0.0438 (16)	0.0584 (18)	−0.0035 (12)	0.0020 (13)	−0.0132 (13)
N35	0.0448 (14)	0.0555 (15)	0.0524 (14)	−0.0032 (11)	0.0025 (11)	−0.0151 (11)
C36	0.0470 (17)	0.0487 (17)	0.0510 (16)	−0.0032 (13)	0.0042 (14)	−0.0141 (13)
N37	0.0430 (14)	0.0634 (16)	0.0487 (14)	−0.0037 (11)	0.0050 (11)	−0.0176 (12)
C37A	0.0400 (15)	0.0443 (16)	0.0557 (17)	−0.0010 (12)	0.0021 (13)	−0.0156 (13)

Geometric parameters (Å, º)

S1—C18	1.768 (4)	C4'—N5'	1.340 (4)
S1—C6	1.773 (3)	N5'—C6'	1.354 (3)
S2—C6'	1.765 (3)	C6'—N7'	1.312 (4)
S2—C24	1.791 (3)	N7'—C7'A	1.364 (3)
S1'—C6''	1.770 (3)	N1''—C7''A	1.352 (4)
S1'—C18''	1.778 (4)	N1''—N2''	1.372 (3)
S2'—C36	1.764 (3)	N1''—C8''	1.446 (4)
S2'—C24''	1.794 (3)	N2''—C3''	1.314 (4)
N1—C7A	1.340 (4)	C3''—C3''A	1.407 (4)
N1—N2	1.369 (3)	C3''—H3''	0.9300
N1—C8	1.447 (4)	C3''A—C7''A	1.384 (4)
N2—C3	1.309 (4)	C3''A—C4''	1.416 (4)
C3—C3A	1.411 (4)	C4''—N13''	1.328 (3)
C3—H3	0.9300	C4''—N5''	1.350 (4)
C3A—C7A	1.388 (4)	N5''—C6''	1.336 (4)
C3A—C4	1.413 (4)	C6''—N7''	1.322 (4)
C4—N13	1.339 (4)	N7''—C7''A	1.362 (4)
C4—N5	1.353 (4)	C8''—C9''	1.512 (4)
N5—C6	1.328 (4)	C8''—H8''1	0.9700
C6—N7	1.324 (4)	C8''—H8''2	0.9700
N7—C7A	1.367 (4)	C9''—C10''	1.519 (4)
C8—C9	1.518 (4)	C9''—H9''1	0.9700
C8—H8A	0.9700	C9''—H9''2	0.9700
C8—H8B	0.9700	C10''—C11''	1.505 (4)
C9—C10	1.512 (4)	C10''—H10C	0.9700
C9—H9A	0.9700	C10''—H10D	0.9700
C9—H9B	0.9700	C11''—C12''	1.505 (4)
C10—C11	1.513 (4)	C11''—H11C	0.9700
C10—H10A	0.9700	C11''—H11D	0.9700
C10—H10B	0.9700	C12''—N32	1.459 (4)
C11—C12	1.505 (4)	C12''—H12C	0.9700
C11—H11A	0.9700	C12''—H12D	0.9700
C11—H11B	0.9700	N13''—C17''	1.464 (3)
C12—N2'	1.454 (4)	N13''—C14''	1.466 (3)
C12—H12A	0.9700	C14''—C15''	1.496 (4)
C12—H12B	0.9700	C14''—H14C	0.9700
N13—C17	1.460 (4)	C14''—H14D	0.9700
N13—C14	1.465 (4)	C15''—C16''	1.484 (4)
C14—C15	1.501 (5)	C15''—H15C	0.9700
C14—H14A	0.9700	C15''—H15D	0.9700
C14—H14B	0.9700	C16''—C17''	1.515 (3)
C15—C16	1.504 (5)	C16''—H16C	0.9700
C15—H15A	0.9700	C16''—H16D	0.9700
C15—H15B	0.9700	C17''—H17C	0.9700
C16—C17	1.516 (4)	C17''—H17D	0.9700
C16—H16A	0.9700	C18''—H18D	0.9600
C16—H16B	0.9700	C18''—H18E	0.9600
C17—H17A	0.9700	C18''—H18F	0.9600
C17—H17B	0.9700	N19''—C34	1.341 (3)
C18—H18A	0.9600	N19''—C23''	1.460 (3)
C18—H18B	0.9600	N19''—C20''	1.459 (3)
C18—H18C	0.9600	C20''—C21''	1.478 (4)
N19—C4'	1.338 (3)	C20''—H20C	0.9700
N19—C23	1.460 (4)	C20''—H20D	0.9700
N19—C20	1.466 (4)	C21''—C22''	1.457 (4)
C20—C21	1.478 (5)	C21''—H21C	0.9700
C20—H20A	0.9700	C21''—H21D	0.9700
C20—H20B	0.9700	C22''—C23''	1.502 (3)
C21—C22	1.483 (6)	C22''—H22C	0.9700
C21—H21A	0.9700	C22''—H22D	0.9700
C21—H21B	0.9700	C23''—H23C	0.9700
C22—C23	1.528 (5)	C23''—H23D	0.9700
C22—H22A	0.9700	C24''—H24D	0.9600
C22—H22B	0.9700	C24''—H24E	0.9600
C23—H23A	0.9700	C24''—H24F	0.9600
C23—H23B	0.9700	N31—C37A	1.338 (3)
C24—H24A	0.9600	N31—N32	1.358 (3)
C24—H24B	0.9600	N32—C33	1.324 (3)
C24—H24C	0.9600	C33—C33A	1.393 (4)
N1'—C7'A	1.347 (4)	C33—H33	0.9300
N1'—N2'	1.360 (3)	C33A—C37A	1.419 (4)
N2'—C3'	1.323 (4)	C33A—C34	1.426 (4)
C3'—C3'A	1.387 (4)	C34—N35	1.337 (3)
C3'—H3'	0.9300	N35—C36	1.351 (3)
C3'A—C7'A	1.413 (4)	C36—N37	1.310 (3)
C3'A—C4'	1.425 (4)	N37—C37A	1.370 (3)
C18—S1—C6	101.69 (17)	N1'—C7'A—C3'A	111.9 (2)
C6'—S2—C24	102.36 (15)	N7'—C7'A—C3'A	124.3 (3)
C6''—S1'—C18''	101.43 (16)	C7''A—N1''—N2''	110.7 (2)
C36—S2'—C24''	102.25 (15)	C7''A—N1''—C8''	129.0 (3)
C7A—N1—N2	111.0 (2)	N2''—N1''—C8''	120.2 (3)
C7A—N1—C8	128.7 (3)	C3''—N2''—N1''	105.1 (2)
N2—N1—C8	120.1 (3)	N2''—C3''—C3''A	112.6 (3)
C3—N2—N1	105.2 (2)	N2''—C3''—H3''	123.7
N2—C3—C3A	112.5 (3)	C3''A—C3''—H3''	123.7
N2—C3—H3	123.8	C7''A—C3''A—C3''	103.6 (3)
C3A—C3—H3	123.8	C7''A—C3''A—C4''	116.0 (3)
C7A—C3A—C3	103.2 (3)	C3''—C3''A—C4''	140.3 (3)
C7A—C3A—C4	116.1 (3)	N13''—C4''—N5''	117.2 (3)
C3—C3A—C4	140.7 (3)	N13''—C4''—C3''A	124.1 (3)
N13—C4—N5	116.9 (3)	N5''—C4''—C3''A	118.6 (3)
N13—C4—C3A	124.2 (3)	C6''—N5''—C4''	117.5 (3)
N5—C4—C3A	118.9 (3)	N7''—C6''—N5''	130.9 (3)
C6—N5—C4	117.4 (3)	N7''—C6''—S1'	118.1 (2)
N7—C6—N5	131.0 (3)	N5''—C6''—S1'	111.0 (2)
N7—C6—S1	118.1 (2)	C6''—N7''—C7''A	109.7 (2)
N5—C6—S1	110.9 (2)	N1''—C7''A—N7''	125.0 (3)
C6—N7—C7A	110.0 (2)	N1''—C7''A—C3''A	108.0 (2)
N1—C7A—N7	125.5 (3)	N7''—C7''A—C3''A	127.0 (3)
N1—C7A—C3A	108.1 (3)	N1''—C8''—C9''	113.0 (3)
N7—C7A—C3A	126.5 (3)	N1''—C8''—H8''1	109.0
N1—C8—C9	113.1 (3)	C9''—C8''—H8''1	109.0
N1—C8—H8A	109.0	N1''—C8''—H8''2	109.0
C9—C8—H8A	109.0	C9''—C8''—H8''2	109.0
N1—C8—H8B	109.0	H8''1—C8''—H8''2	107.8
C9—C8—H8B	109.0	C8''—C9''—C10''	112.7 (3)
H8A—C8—H8B	107.8	C8''—C9''—H9''1	109.0
C10—C9—C8	113.4 (2)	C10''—C9''—H9''1	109.0
C10—C9—H9A	108.9	C8''—C9''—H9''2	109.0
C8—C9—H9A	108.9	C10''—C9''—H9''2	109.0
C10—C9—H9B	108.9	H9''1—C9''—H9''2	107.8
C8—C9—H9B	108.9	C11''—C10''—C9''	113.1 (2)
H9A—C9—H9B	107.7	C11''—C10''—H10C	109.0
C9—C10—C11	113.6 (3)	C9''—C10''—H10C	109.0
C9—C10—H10A	108.9	C11''—C10''—H10D	109.0
C11—C10—H10A	108.9	C9''—C10''—H10D	109.0
C9—C10—H10B	108.9	H10C—C10''—H10D	107.8
C11—C10—H10B	108.9	C12''—C11''—C10''	113.6 (3)
H10A—C10—H10B	107.7	C12''—C11''—H11C	108.9
C12—C11—C10	114.2 (3)	C10''—C11''—H11C	108.9
C12—C11—H11A	108.7	C12''—C11''—H11D	108.9
C10—C11—H11A	108.7	C10''—C11''—H11D	108.9
C12—C11—H11B	108.7	H11C—C11''—H11D	107.7
C10—C11—H11B	108.7	N32—C12''—C11''	113.2 (3)
H11A—C11—H11B	107.6	N32—C12''—H12C	108.9
N2'—C12—C11	113.0 (3)	C11''—C12''—H12C	108.9
N2'—C12—H12A	109.0	N32—C12''—H12D	108.9
C11—C12—H12A	109.0	C11''—C12''—H12D	108.9
N2'—C12—H12B	109.0	H12C—C12''—H12D	107.7
C11—C12—H12B	109.0	C4''—N13''—C17''	124.3 (2)
H12A—C12—H12B	107.8	C4''—N13''—C14''	123.4 (2)
C4—N13—C17	124.6 (3)	C17''—N13''—C14''	112.22 (19)
C4—N13—C14	123.1 (2)	N13''—C14''—C15''	102.6 (2)
C17—N13—C14	112.3 (2)	N13''—C14''—H14C	111.2
N13—C14—C15	102.5 (3)	C15''—C14''—H14C	111.2
N13—C14—H14A	111.3	N13''—C14''—H14D	111.2
C15—C14—H14A	111.3	C15''—C14''—H14D	111.2
N13—C14—H14B	111.3	H14C—C14''—H14D	109.2
C15—C14—H14B	111.3	C14''—C15''—C16''	105.5 (3)
H14A—C14—H14B	109.2	C14''—C15''—H15C	110.6
C16—C15—C14	104.5 (3)	C16''—C15''—H15C	110.6
C16—C15—H15A	110.9	C14''—C15''—H15D	110.6
C14—C15—H15A	110.9	C16''—C15''—H15D	110.6
C16—C15—H15B	110.9	H15C—C15''—H15D	108.8
C14—C15—H15B	110.9	C15''—C16''—C17''	104.9 (2)
H15A—C15—H15B	108.9	C15''—C16''—H16C	110.8
C15—C16—C17	104.0 (3)	C17''—C16''—H16C	110.8
C15—C16—H16A	111.0	C15''—C16''—H16D	110.8
C17—C16—H16A	111.0	C17''—C16''—H16D	110.8
C15—C16—H16B	111.0	H16C—C16''—H16D	108.8
C17—C16—H16B	111.0	N13''—C17''—C16''	103.2 (2)
H16A—C16—H16B	109.0	N13''—C17''—H17C	111.1
N13—C17—C16	103.5 (3)	C16''—C17''—H17C	111.1
N13—C17—H17A	111.1	N13''—C17''—H17D	111.1
C16—C17—H17A	111.1	C16''—C17''—H17D	111.1
N13—C17—H17B	111.1	H17C—C17''—H17D	109.1
C16—C17—H17B	111.1	S1'—C18''—H18D	109.5
H17A—C17—H17B	109.0	S1'—C18''—H18E	109.5
S1—C18—H18A	109.5	H18D—C18''—H18E	109.5
S1—C18—H18B	109.5	S1'—C18''—H18F	109.5
H18A—C18—H18B	109.5	H18D—C18''—H18F	109.5
S1—C18—H18C	109.5	H18E—C18''—H18F	109.5
H18A—C18—H18C	109.5	C34—N19''—C23''	124.8 (2)
H18B—C18—H18C	109.5	C34—N19''—C20''	122.6 (2)
C4'—N19—C23	124.3 (3)	C23''—N19''—C20''	112.56 (18)
C4'—N19—C20	123.0 (3)	N19''—C20''—C21''	104.3 (2)
C23—N19—C20	112.2 (2)	N19''—C20''—H20C	110.9
N19—C20—C21	104.0 (3)	C21''—C20''—H20C	110.9
N19—C20—H20A	110.9	N19''—C20''—H20D	110.9
C21—C20—H20A	110.9	C21''—C20''—H20D	110.9
N19—C20—H20B	110.9	H20C—C20''—H20D	108.9
C21—C20—H20B	110.9	C22''—C21''—C20''	109.0 (2)
H20A—C20—H20B	109.0	C22''—C21''—H21C	109.9
C20—C21—C22	105.9 (3)	C20''—C21''—H21C	109.9
C20—C21—H21A	110.5	C22''—C21''—H21D	109.9
C22—C21—H21A	110.5	C20''—C21''—H21D	109.9
C20—C21—H21B	110.5	H21C—C21''—H21D	108.3
C22—C21—H21B	110.5	C21''—C22''—C23''	107.8 (2)
H21A—C21—H21B	108.7	C21''—C22''—H22C	110.1
C21—C22—C23	105.4 (3)	C23''—C22''—H22C	110.1
C21—C22—H22A	110.7	C21''—C22''—H22D	110.1
C23—C22—H22A	110.7	C23''—C22''—H22D	110.1
C21—C22—H22B	110.7	H22C—C22''—H22D	108.5
C23—C22—H22B	110.7	N19''—C23''—C22''	104.1 (2)
H22A—C22—H22B	108.8	N19''—C23''—H23C	110.9
N19—C23—C22	102.7 (3)	C22''—C23''—H23C	110.9
N19—C23—H23A	111.2	N19''—C23''—H23D	110.9
C22—C23—H23A	111.2	C22''—C23''—H23D	110.9
N19—C23—H23B	111.2	H23C—C23''—H23D	109.0
C22—C23—H23B	111.2	S2'—C24''—H24D	109.5
H23A—C23—H23B	109.1	S2'—C24''—H24E	109.5
S2—C24—H24A	109.5	H24D—C24''—H24E	109.5
S2—C24—H24B	109.5	S2'—C24''—H24F	109.5
H24A—C24—H24B	109.5	H24D—C24''—H24F	109.5
S2—C24—H24C	109.5	H24E—C24''—H24F	109.5
H24A—C24—H24C	109.5	C37A—N31—N32	103.3 (2)
H24B—C24—H24C	109.5	C33—N32—N31	114.1 (2)
C7'A—N1'—N2'	103.1 (2)	C33—N32—C12''	126.9 (3)
C3'—N2'—N1'	114.0 (2)	N31—N32—C12''	118.9 (2)
C3'—N2'—C12	127.0 (3)	N32—C33—C33A	107.0 (2)
N1'—N2'—C12	119.0 (2)	N32—C33—H33	126.5
N2'—C3'—C3'A	107.1 (2)	C33A—C33—H33	126.5
N2'—C3'—H3'	126.4	C33—C33A—C37A	103.5 (2)
C3'A—C3'—H3'	126.4	C33—C33A—C34	140.1 (3)
C3'—C3'A—C7'A	103.9 (3)	C37A—C33A—C34	116.4 (2)
C3'—C3'A—C4'	139.4 (3)	N35—C34—N19''	118.1 (2)
C7'A—C3'A—C4'	116.6 (3)	N35—C34—C33A	119.1 (2)
N19—C4'—N5'	117.8 (3)	N19''—C34—C33A	122.8 (3)
N19—C4'—C3'A	123.0 (3)	C34—N35—C36	117.7 (2)
N5'—C4'—C3'A	119.2 (2)	N37—C36—N35	130.3 (3)
C4'—N5'—C6'	117.2 (2)	N37—C36—S2'	118.8 (2)
N7'—C6'—N5'	130.6 (3)	N35—C36—S2'	110.9 (2)
N7'—C6'—S2	119.5 (2)	C36—N37—C37A	112.2 (2)
N5'—C6'—S2	109.9 (2)	N31—C37A—N37	123.8 (2)
C6'—N7'—C7'A	112.1 (2)	N31—C37A—C33A	112.1 (2)
N1'—C7'A—N7'	123.8 (2)	N37—C37A—C33A	124.1 (2)
C7A—N1—N2—C3	0.1 (3)	C7''A—N1''—N2''—C3''	−0.5 (3)
C8—N1—N2—C3	−175.4 (3)	C8''—N1''—N2''—C3''	176.5 (3)
N1—N2—C3—C3A	0.3 (4)	N1''—N2''—C3''—C3''A	0.5 (4)
N2—C3—C3A—C7A	−0.6 (4)	N2''—C3''—C3''A—C7''A	−0.3 (4)
N2—C3—C3A—C4	177.4 (4)	N2''—C3''—C3''A—C4''	−176.6 (4)
C7A—C3A—C4—N13	175.3 (3)	C7''A—C3''A—C4''—N13''	−174.6 (3)
C3—C3A—C4—N13	−2.5 (6)	C3''—C3''A—C4''—N13''	1.4 (6)
C7A—C3A—C4—N5	−4.3 (4)	C7''A—C3''A—C4''—N5''	4.4 (4)
C3—C3A—C4—N5	177.8 (3)	C3''—C3''A—C4''—N5''	−179.7 (3)
N13—C4—N5—C6	−177.5 (3)	N13''—C4''—N5''—C6''	177.7 (3)
C3A—C4—N5—C6	2.1 (4)	C3''A—C4''—N5''—C6''	−1.4 (4)
C4—N5—C6—N7	2.2 (5)	C4''—N5''—C6''—N7''	−3.3 (5)
C4—N5—C6—S1	−176.7 (2)	C4''—N5''—C6''—S1'	176.4 (2)
C18—S1—C6—N7	0.5 (3)	C18''—S1'—C6''—N7''	0.8 (3)
C18—S1—C6—N5	179.6 (2)	C18''—S1'—C6''—N5''	−178.9 (2)
N5—C6—N7—C7A	−3.5 (5)	N5''—C6''—N7''—C7''A	3.9 (5)
S1—C6—N7—C7A	175.4 (2)	S1'—C6''—N7''—C7''A	−175.8 (2)
N2—N1—C7A—N7	178.5 (3)	N2''—N1''—C7''A—N7''	−178.5 (3)
C8—N1—C7A—N7	−6.4 (5)	C8''—N1''—C7''A—N7''	4.9 (5)
N2—N1—C7A—C3A	−0.5 (3)	N2''—N1''—C7''A—C3''A	0.3 (3)
C8—N1—C7A—C3A	174.5 (3)	C8''—N1''—C7''A—C3''A	−176.3 (3)
C6—N7—C7A—N1	−178.3 (3)	C6''—N7''—C7''A—N1''	178.6 (3)
C6—N7—C7A—C3A	0.6 (4)	C6''—N7''—C7''A—C3''A	0.1 (4)
C3—C3A—C7A—N1	0.7 (3)	C3''—C3''A—C7''A—N1''	0.0 (3)
C4—C3A—C7A—N1	−177.9 (2)	C4''—C3''A—C7''A—N1''	177.3 (2)
C3—C3A—C7A—N7	−178.4 (3)	C3''—C3''A—C7''A—N7''	178.7 (3)
C4—C3A—C7A—N7	3.0 (4)	C4''—C3''A—C7''A—N7''	−3.9 (4)
C7A—N1—C8—C9	110.2 (3)	C7''A—N1''—C8''—C9''	−107.7 (4)
N2—N1—C8—C9	−75.1 (3)	N2''—N1''—C8''—C9''	75.9 (4)
N1—C8—C9—C10	−61.8 (4)	N1''—C8''—C9''—C10''	61.9 (4)
C8—C9—C10—C11	−178.0 (3)	C8''—C9''—C10''—C11''	177.7 (3)
C9—C10—C11—C12	−176.4 (3)	C9''—C10''—C11''—C12''	176.1 (3)
C10—C11—C12—N2'	−63.4 (3)	C10''—C11''—C12''—N32	63.6 (4)
N5—C4—N13—C17	−179.9 (3)	N5''—C4''—N13''—C17''	178.6 (3)
C3A—C4—N13—C17	0.5 (5)	C3''A—C4''—N13''—C17''	−2.5 (5)
N5—C4—N13—C14	3.2 (4)	N5''—C4''—N13''—C14''	−6.0 (4)
C3A—C4—N13—C14	−176.4 (3)	C3''A—C4''—N13''—C14''	173.0 (3)
C4—N13—C14—C15	160.9 (3)	C4''—N13''—C14''—C15''	−160.8 (3)
C17—N13—C14—C15	−16.4 (4)	C17''—N13''—C14''—C15''	15.1 (4)
N13—C14—C15—C16	32.3 (4)	N13''—C14''—C15''—C16''	−30.3 (4)
C14—C15—C16—C17	−36.8 (4)	C14''—C15''—C16''—C17''	34.6 (4)
C4—N13—C17—C16	176.8 (3)	C4''—N13''—C17''—C16''	−178.6 (3)
C14—N13—C17—C16	−6.1 (4)	C14''—N13''—C17''—C16''	5.5 (4)
C15—C16—C17—N13	26.1 (4)	C15''—C16''—C17''—N13''	−24.3 (4)
C4'—N19—C20—C21	−160.3 (3)	C34—N19''—C20''—C21''	174.7 (3)
C23—N19—C20—C21	11.4 (4)	C23''—N19''—C20''—C21''	−6.1 (4)
N19—C20—C21—C22	−26.6 (4)	N19''—C20''—C21''—C22''	13.3 (5)
C20—C21—C22—C23	32.1 (5)	C20''—C21''—C22''—C23''	−15.7 (5)
C4'—N19—C23—C22	179.5 (3)	C34—N19''—C23''—C22''	176.1 (3)
C20—N19—C23—C22	7.9 (4)	C20''—N19''—C23''—C22''	−3.2 (4)
C21—C22—C23—N19	−24.2 (4)	C21''—C22''—C23''—N19''	11.4 (5)
C7'A—N1'—N2'—C3'	0.1 (3)	C37A—N31—N32—C33	−1.0 (3)
C7'A—N1'—N2'—C12	−179.3 (2)	C37A—N31—N32—C12''	176.4 (2)
C11—C12—N2'—C3'	109.3 (3)	C11''—C12''—N32—C33	−115.7 (3)
C11—C12—N2'—N1'	−71.4 (3)	C11''—C12''—N32—N31	67.2 (3)
N1'—N2'—C3'—C3'A	0.2 (3)	N31—N32—C33—C33A	0.5 (3)
C12—N2'—C3'—C3'A	179.6 (3)	C12''—N32—C33—C33A	−176.8 (3)
N2'—C3'—C3'A—C7'A	−0.4 (3)	N32—C33—C33A—C37A	0.3 (3)
N2'—C3'—C3'A—C4'	−178.6 (3)	N32—C33—C33A—C34	179.5 (3)
C23—N19—C4'—N5'	−171.9 (3)	C23''—N19''—C34—N35	176.8 (3)
C20—N19—C4'—N5'	−1.2 (4)	C20''—N19''—C34—N35	−4.0 (4)
C23—N19—C4'—C3'A	8.3 (4)	C23''—N19''—C34—C33A	−2.8 (4)
C20—N19—C4'—C3'A	179.0 (3)	C20''—N19''—C34—C33A	176.4 (3)
C3'—C3'A—C4'—N19	−3.4 (5)	C33—C33A—C34—N35	−174.9 (3)
C7'A—C3'A—C4'—N19	178.5 (3)	C37A—C33A—C34—N35	4.2 (4)
C3'—C3'A—C4'—N5'	176.7 (3)	C33—C33A—C34—N19''	4.7 (5)
C7'A—C3'A—C4'—N5'	−1.4 (4)	C37A—C33A—C34—N19''	−176.2 (3)
N19—C4'—N5'—C6'	−179.5 (2)	N19''—C34—N35—C36	177.5 (2)
C3'A—C4'—N5'—C6'	0.3 (4)	C33A—C34—N35—C36	−2.8 (4)
C4'—N5'—C6'—N7'	1.5 (5)	C34—N35—C36—N37	−1.2 (4)
C4'—N5'—C6'—S2	−178.0 (2)	C34—N35—C36—S2'	178.5 (2)
C24—S2—C6'—N7'	0.7 (3)	C24''—S2'—C36—N37	1.2 (3)
C24—S2—C6'—N5'	−179.7 (2)	C24''—S2'—C36—N35	−178.6 (2)
N5'—C6'—N7'—C7'A	−2.0 (4)	N35—C36—N37—C37A	3.3 (4)
S2—C6'—N7'—C7'A	177.55 (19)	S2'—C36—N37—C37A	−176.38 (19)
N2'—N1'—C7'A—N7'	178.0 (2)	N32—N31—C37A—N37	−177.1 (2)
N2'—N1'—C7'A—C3'A	−0.3 (3)	N32—N31—C37A—C33A	1.2 (3)
C6'—N7'—C7'A—N1'	−177.5 (3)	C36—N37—C37A—N31	176.7 (3)
C6'—N7'—C7'A—C3'A	0.6 (4)	C36—N37—C37A—C33A	−1.4 (4)
C3'—C3'A—C7'A—N1'	0.5 (3)	C33—C33A—C37A—N31	−0.9 (3)
C4'—C3'A—C7'A—N1'	179.2 (2)	C34—C33A—C37A—N31	179.6 (2)
C3'—C3'A—C7'A—N7'	−177.8 (3)	C33—C33A—C37A—N37	177.4 (3)
C4'—C3'A—C7'A—N7'	0.9 (4)	C34—C33A—C37A—N37	−2.0 (4)