A stacked pyrazolo[3,4-d]pyrimidine-based flexible molecule: the effect of a bulky benzyl group on intermolecular stacking in comparison with methyl and ethyl groups

In the crystal structure of 1,1'-(1,3-propane­diyl)­bis(5-benzyl-6-methyl­sulfanyl-4,5-di­hydro-1H-pyrazolo­[3,4-d]­pyrimidin-4-one), C₂₉H₂₈N₈O₂S₂, the pairs of pyrazolo­[3,4-d]­pyrimidine rings stack as a result of intramolecular [pi]-[pi] interactions between the heterocyclic rings. The folded mol­ecules are further stacked in pairs, due to intermolecular aromatic [pi]-[pi] interactions and C-H...O hydrogen bonds.

S1. Comment

Interactions between aromatic units play a significant role in chemistry (Hunter et al., 2001; Tsuzuki et al., 2002), crystal engineering (Desiraju, 1995) and biology. In recent years, we have reported the convenient syntheses (Avasthi et al., 1995, 1998; Avasthi, Rawat et al., 2001) and the X-ray structures (Biswas et al., 1995; Maulik et al., 1998, 2000; Avasthi, Rawat et al., 2001; Avasthi, Aswal & Maulik, 2001) of several novel `propylene linker' compounds based on the pyrazolo[3,4-d]pyrimidine core, which is isomeric with biologically important purine, as flexible new models for studying aromatic π–π interactions (APPI). Two of these compounds, 1,1'-(1,3-propanediyl)bis(5-methyl-6-methylthio-4,5-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one), (I), and 1,1'-(1,3-propanediyl)bis(5-ethyl-6-methylthio-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one), (II), show inter- and intramolecular stacking due to APPI (Maulik et al., 1998; Avasthi, Aswal & Maulik, 2001) when studied using X-ray crystallography. Since the X-ray structures of (I) and (II) are quite similar, in having a U-motif for the demonstration of inter- and intramolecular stacking, it was considered worthwhile to replace the N-methyl/ethyl group of (I) and (II) with a bulky N-benzyl group, to determine the robustness of the U-motif and its consequence for the intermolecular stacking from a crystal engineering point of view. In this communication, we report the X-ray structure of 1,1'-(1,3-propanediyl)bis(5-benzyl-6-methylthio-4,5-dihydro-1H-pyrazolo [3,4-d]pyrimidin-4-one), (III), the synthesis of which has been described earlier by Avasthi et al. (1998). \sch

The molecular structure and conformation of (III) are shown in Fig. 1. The structure is folded at the centre of the bridge [C10—C11—C12 114.0 (2)°] due to intramolecular APPI between the pyrazolo[3,4-d]pyrimidine rings. For comparison, the folding angles in (I) and (II) are 115.2 (2) and 114.9 (2)°, respectively. In compound (III), as in (I) and (II), the folded pyrazolo[3,4-d]pyrimidine rings are positioned in such a way that only part of the pyrimidinyl rings overlap. The overlapping six-membered rings are separated by an average distance of 3.428 (3) Å [3.37 (1) Å in (I) and 3.415 (3) Å in (II)], thus confirming the presence of intramolecular APPI.

The pyrazolo[3,4-d]pyrimidine rings in (III) are nearly planar [maximum deviation -0.048 (2) Å] and the angle between the least-squares planes is 14.5 (1)° [12.4 (5)° in (I) and 12.5 (1)° in (II)]. The crystal packing (Fig. 2) shows further independent intermolecular stacking between the pyrazolo[3,4-d]pyrimidine systems due to π–π interactions. Pairs of pyrazolo[3,4-d]pyrimidine rings (related by symmetry code 1 - x, 1 - y, -z) overlap, with an interplanar separation of 3.370 (2) Å in a `parallel displaced' orientation [the dihedral angle of a stacking pair is 1.0 (1)°].

Interestingly, these stacked pyrazolo[3,4-d]pyrimidine rings are also connected by intermolecular C—H···O hydrogen bonding (Table 1; Desiraju & Steiner, 1999). Thus, the combination of intra- and intermolecular APPI and intermolecular hydrogen bonding results in the formation of a stacked-dimeric unit of (III). The continuous intermolecular stacking present in (I) and (II) is absent in (III). The crystal structure of (III) is stabilized mainly by C—H···O bonding, π–π interactions and van der Waals forces.

S2. Experimental

Compound (III) was synthesized using the method described by Avasthi et al. (1998). Diffraction quality crystals of (III) were obtained by slow evaporation of an ethyl acetate solution at room temperature.

Computing details

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 displacement ellipsoid plot (30% probability) showing the molecular structure of (III) with the atom-labelling scheme.
	Fig. 2. A crystal-packing diagram for (III) showing the intra- and intermolecular π–π stacking between the pyrazolo[3,4-d]pyrimidine rings, and the intermolecular C—H···O hydrogen bonding (dashed lines).

1,1'-(1,3-propanediyl)bis(5-benzyl-6-methylthio-4,5-dihydro-1H-pyrazolo [3,4-d]pyrimidine-4-one)

Crystal data

C29H28N8O2S2	Z = 2
Mr = 584.71	F(000) = 612
Triclinic, P1	Dx = 1.379 Mg m^−3
Hall symbol: -P 1	Melting point: 433 K
a = 9.150 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.491 (1) Å	Cell parameters from 38 reflections
c = 16.839 (2) Å	θ = 4.8–12.5°
α = 83.01 (1)°	µ = 0.23 mm^−1
β = 85.26 (1)°	T = 293 K
γ = 76.39 (1)°	Rectangular, colourless
V = 1408.5 (3) Å^3	0.35 × 0.28 × 0.25 mm

Data collection

Bruker P4 diffractometer	Rint = 0.021
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 2.2°
Graphite monochromator	h = −1→11
θ/2θ scans	k = −11→11
6623 measured reflections	l = −20→20
5527 independent reflections	3 standard reflections every 97 reflections
3716 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.5548P] where P = (Fo^2 + 2Fc^2)/3
5527 reflections	(Δ/σ)max < 0.001
372 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.28 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
S2	0.67773 (9)	0.46166 (7)	0.33325 (4)	0.0603 (2)
S1	0.38237 (8)	0.11449 (7)	0.20404 (4)	0.0616 (2)
N1	0.7371 (2)	0.3705 (2)	0.03235 (11)	0.0444 (5)
N2	0.7509 (2)	0.5115 (2)	0.01271 (12)	0.0532 (5)
C3	0.6415 (3)	0.5910 (3)	0.05519 (15)	0.0520 (6)
H3	0.6241	0.6918	0.0541	0.062*
C4	0.5545 (3)	0.5049 (2)	0.10221 (13)	0.0429 (5)
C5	0.4223 (3)	0.5301 (3)	0.15497 (14)	0.0453 (6)
N6	0.3744 (2)	0.3985 (2)	0.18224 (11)	0.0431 (5)
C7	0.4543 (3)	0.2640 (2)	0.16165 (13)	0.0420 (5)
N8	0.5757 (2)	0.2405 (2)	0.11473 (11)	0.0431 (5)
C9	0.6195 (3)	0.3648 (2)	0.08509 (13)	0.0397 (5)
C10	0.8353 (3)	0.2499 (3)	−0.00598 (14)	0.0478 (6)
H10A	0.8081	0.2555	−0.0609	0.057*
H10B	0.8190	0.1586	0.0216	0.057*
C11	1.0006 (3)	0.2504 (3)	−0.00567 (13)	0.0476 (6)
H11A	1.0598	0.1628	−0.0268	0.057*
H11B	1.0198	0.3333	−0.0412	0.057*
C12	1.0529 (3)	0.2580 (3)	0.07640 (13)	0.0471 (6)
H12A	1.1617	0.2433	0.0732	0.056*
H12B	1.0104	0.3544	0.0928	0.056*
N13	1.0095 (2)	0.1497 (2)	0.13662 (11)	0.0446 (5)
N14	1.0544 (3)	0.0044 (2)	0.12774 (12)	0.0563 (6)
C15	0.9861 (3)	−0.0610 (3)	0.18839 (15)	0.0560 (7)
H15	0.9966	−0.1614	0.1978	0.067*
C16	0.8954 (3)	0.0396 (2)	0.23711 (13)	0.0435 (6)
C17	0.7914 (3)	0.0338 (3)	0.30458 (14)	0.0465 (6)
N18	0.7237 (2)	0.1749 (2)	0.32790 (10)	0.0425 (5)
C19	0.7621 (3)	0.3004 (2)	0.29037 (13)	0.0408 (5)
N20	0.8541 (2)	0.3057 (2)	0.22766 (11)	0.0409 (4)
C21	0.9151 (3)	0.1734 (2)	0.20196 (13)	0.0397 (5)
O22	0.3506 (2)	0.64677 (19)	0.17553 (10)	0.0596 (5)
C23	0.2242 (3)	0.4163 (3)	0.22530 (14)	0.0505 (6)
H23A	0.1740	0.3465	0.2085	0.061*
H23B	0.1652	0.5130	0.2087	0.061*
C24	0.2233 (3)	0.3970 (3)	0.31561 (14)	0.0465 (6)
C25	0.1778 (3)	0.2807 (3)	0.35928 (16)	0.0597 (7)
H25	0.1507	0.2114	0.3325	0.072*
C26	0.1719 (3)	0.2650 (4)	0.44179 (17)	0.0695 (8)
H26	0.1429	0.1848	0.4703	0.083*
C27	0.2089 (3)	0.3685 (4)	0.48160 (17)	0.0711 (8)
H27	0.2014	0.3606	0.5373	0.085*
C28	0.2567 (4)	0.4832 (3)	0.43936 (18)	0.0757 (9)
H28	0.2847	0.5516	0.4665	0.091*
C29	0.2637 (3)	0.4982 (3)	0.35668 (16)	0.0613 (7)
H29	0.2960	0.5768	0.3284	0.074*
C30	0.4974 (4)	−0.0284 (3)	0.1524 (2)	0.0816 (10)
H30A	0.4913	−0.0023	0.0957	0.122*
H30B	0.4629	−0.1165	0.1673	0.122*
H30C	0.5999	−0.0433	0.1664	0.122*
O31	0.7568 (2)	−0.07369 (19)	0.34170 (11)	0.0630 (5)
C32	0.6071 (3)	0.1810 (3)	0.39392 (13)	0.0475 (6)
H32A	0.5521	0.1066	0.3899	0.057*
H32B	0.5363	0.2749	0.3872	0.057*
C33	0.6653 (3)	0.1599 (2)	0.47692 (13)	0.0420 (5)
C34	0.5623 (3)	0.1525 (3)	0.54158 (14)	0.0527 (6)
H34	0.4620	0.1580	0.5328	0.063*
C35	0.6076 (3)	0.1371 (3)	0.61875 (15)	0.0593 (7)
H35	0.5373	0.1331	0.6616	0.071*
C36	0.7550 (3)	0.1277 (3)	0.63308 (15)	0.0564 (7)
H36	0.7848	0.1176	0.6854	0.068*
C37	0.8583 (3)	0.1333 (3)	0.56950 (16)	0.0567 (7)
H37	0.9588	0.1260	0.5786	0.068*
C38	0.8128 (3)	0.1499 (3)	0.49152 (15)	0.0514 (6)
H38	0.8833	0.1543	0.4487	0.062*
C39	0.7735 (4)	0.5868 (3)	0.27542 (18)	0.0750 (9)
H39A	0.8801	0.5523	0.2801	0.112*
H39B	0.7411	0.6808	0.2949	0.112*
H39C	0.7506	0.5945	0.2202	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0736 (5)	0.0494 (4)	0.0572 (4)	−0.0115 (3)	0.0108 (4)	−0.0176 (3)
S1	0.0661 (5)	0.0512 (4)	0.0691 (5)	−0.0244 (3)	0.0048 (4)	0.0034 (3)
N1	0.0502 (12)	0.0412 (11)	0.0441 (11)	−0.0156 (9)	−0.0007 (10)	−0.0040 (9)
N2	0.0625 (14)	0.0466 (12)	0.0538 (12)	−0.0224 (11)	0.0039 (11)	−0.0035 (10)
C3	0.0659 (17)	0.0395 (13)	0.0533 (15)	−0.0187 (13)	−0.0043 (13)	−0.0019 (11)
C4	0.0492 (14)	0.0403 (13)	0.0409 (12)	−0.0132 (11)	−0.0051 (11)	−0.0034 (10)
C5	0.0536 (15)	0.0414 (14)	0.0405 (13)	−0.0101 (12)	−0.0083 (11)	−0.0007 (10)
N6	0.0451 (12)	0.0463 (11)	0.0391 (10)	−0.0131 (9)	−0.0027 (9)	−0.0033 (8)
C7	0.0477 (14)	0.0392 (13)	0.0396 (12)	−0.0111 (11)	−0.0102 (11)	0.0006 (10)
N8	0.0490 (12)	0.0371 (10)	0.0431 (11)	−0.0117 (9)	−0.0010 (10)	−0.0018 (8)
C9	0.0446 (13)	0.0395 (13)	0.0369 (12)	−0.0134 (11)	−0.0066 (10)	−0.0012 (9)
C10	0.0532 (15)	0.0517 (14)	0.0405 (13)	−0.0134 (12)	−0.0013 (11)	−0.0104 (11)
C11	0.0518 (15)	0.0568 (15)	0.0353 (12)	−0.0158 (12)	0.0055 (11)	−0.0077 (11)
C12	0.0505 (15)	0.0552 (15)	0.0387 (12)	−0.0192 (12)	−0.0002 (11)	−0.0053 (11)
N13	0.0544 (12)	0.0450 (11)	0.0362 (10)	−0.0132 (9)	0.0012 (9)	−0.0106 (8)
N14	0.0733 (15)	0.0474 (12)	0.0461 (12)	−0.0058 (11)	0.0008 (11)	−0.0152 (10)
C15	0.081 (2)	0.0435 (14)	0.0432 (14)	−0.0125 (14)	−0.0006 (14)	−0.0088 (11)
C16	0.0544 (15)	0.0392 (13)	0.0383 (12)	−0.0112 (11)	−0.0057 (11)	−0.0071 (10)
C17	0.0603 (16)	0.0424 (13)	0.0405 (13)	−0.0173 (12)	−0.0085 (12)	−0.0037 (11)
N18	0.0496 (12)	0.0435 (11)	0.0365 (10)	−0.0156 (9)	0.0013 (9)	−0.0055 (8)
C19	0.0481 (14)	0.0406 (12)	0.0362 (12)	−0.0122 (11)	−0.0080 (11)	−0.0060 (10)
N20	0.0504 (12)	0.0392 (10)	0.0355 (10)	−0.0136 (9)	−0.0022 (9)	−0.0069 (8)
C21	0.0467 (14)	0.0426 (13)	0.0329 (11)	−0.0139 (11)	−0.0041 (10)	−0.0077 (9)
O22	0.0723 (13)	0.0427 (10)	0.0591 (11)	−0.0042 (9)	0.0022 (9)	−0.0080 (8)
C23	0.0429 (14)	0.0603 (16)	0.0485 (14)	−0.0124 (12)	−0.0037 (11)	−0.0044 (12)
C24	0.0386 (13)	0.0513 (15)	0.0479 (14)	−0.0066 (11)	0.0010 (11)	−0.0082 (11)
C25	0.0583 (17)	0.0747 (19)	0.0548 (16)	−0.0324 (15)	−0.0010 (13)	−0.0079 (14)
C26	0.0681 (19)	0.088 (2)	0.0554 (17)	−0.0338 (17)	0.0072 (15)	0.0047 (16)
C27	0.077 (2)	0.087 (2)	0.0445 (15)	−0.0102 (18)	0.0067 (15)	−0.0111 (15)
C28	0.110 (3)	0.0599 (18)	0.0581 (18)	−0.0128 (18)	−0.0041 (18)	−0.0234 (15)
C29	0.083 (2)	0.0482 (15)	0.0524 (16)	−0.0137 (14)	0.0005 (14)	−0.0104 (12)
C30	0.108 (3)	0.0469 (17)	0.094 (2)	−0.0310 (17)	0.011 (2)	−0.0091 (16)
O31	0.0846 (14)	0.0471 (10)	0.0605 (11)	−0.0279 (10)	0.0071 (10)	−0.0005 (9)
C32	0.0462 (14)	0.0553 (15)	0.0432 (13)	−0.0175 (12)	0.0038 (11)	−0.0056 (11)
C33	0.0492 (15)	0.0363 (12)	0.0413 (12)	−0.0131 (11)	0.0018 (11)	−0.0029 (9)
C34	0.0468 (15)	0.0636 (16)	0.0467 (14)	−0.0158 (13)	0.0027 (12)	0.0011 (12)
C35	0.0630 (18)	0.0670 (18)	0.0443 (15)	−0.0161 (14)	0.0101 (13)	0.0022 (12)
C36	0.075 (2)	0.0559 (16)	0.0397 (14)	−0.0177 (14)	−0.0088 (14)	0.0012 (11)
C37	0.0527 (16)	0.0631 (17)	0.0558 (16)	−0.0147 (13)	−0.0097 (13)	−0.0038 (13)
C38	0.0495 (16)	0.0608 (16)	0.0440 (14)	−0.0143 (13)	0.0035 (12)	−0.0063 (12)
C39	0.107 (3)	0.0441 (16)	0.076 (2)	−0.0199 (16)	0.0072 (18)	−0.0157 (14)

Geometric parameters (Å, º)

S2—C19	1.755 (2)	N18—C32	1.473 (3)
S2—C39	1.787 (3)	C19—N20	1.299 (3)
S1—C7	1.752 (2)	N20—C21	1.356 (3)
S1—C30	1.779 (3)	C23—C24	1.509 (3)
N1—C9	1.344 (3)	C23—H23A	0.9700
N1—N2	1.371 (3)	C23—H23B	0.9700
N1—C10	1.461 (3)	C24—C25	1.379 (4)
N2—C3	1.319 (3)	C24—C29	1.381 (4)
C3—C4	1.405 (3)	C25—C26	1.377 (4)
C3—H3	0.9300	C25—H25	0.9300
C4—C9	1.378 (3)	C26—C27	1.372 (4)
C4—C5	1.431 (3)	C26—H26	0.9300
C5—O22	1.221 (3)	C27—C28	1.366 (4)
C5—N6	1.431 (3)	C27—H27	0.9300
N6—C7	1.383 (3)	C28—C29	1.380 (4)
N6—C23	1.483 (3)	C28—H28	0.9300
C7—N8	1.300 (3)	C29—H29	0.9300
N8—C9	1.360 (3)	C30—H30A	0.9600
C10—C11	1.515 (3)	C30—H30B	0.9600
C10—H10A	0.9700	C30—H30C	0.9600
C10—H10B	0.9700	C32—C33	1.511 (3)
C11—C12	1.514 (3)	C32—H32A	0.9700
C11—H11A	0.9700	C32—H32B	0.9700
C11—H11B	0.9700	C33—C38	1.372 (3)
C12—N13	1.454 (3)	C33—C34	1.386 (3)
C12—H12A	0.9700	C34—C35	1.377 (4)
C12—H12B	0.9700	C34—H34	0.9300
N13—C21	1.349 (3)	C35—C36	1.370 (4)
N13—N14	1.366 (3)	C35—H35	0.9300
N14—C15	1.320 (3)	C36—C37	1.373 (4)
C15—C16	1.407 (3)	C36—H36	0.9300
C15—H15	0.9300	C37—C38	1.390 (3)
C16—C21	1.379 (3)	C37—H37	0.9300
C16—C17	1.425 (3)	C38—H38	0.9300
C17—O31	1.223 (3)	C39—H39A	0.9600
C17—N18	1.424 (3)	C39—H39B	0.9600
N18—C19	1.385 (3)	C39—H39C	0.9600
C19—S2—C39	100.58 (12)	N13—C21—N20	125.2 (2)
C7—S1—C30	101.29 (13)	N13—C21—C16	107.4 (2)
C9—N1—N2	110.91 (19)	N20—C21—C16	127.4 (2)
C9—N1—C10	127.47 (19)	N6—C23—C24	116.1 (2)
N2—N1—C10	121.48 (19)	N6—C23—H23A	108.3
C3—N2—N1	105.21 (19)	C24—C23—H23A	108.3
N2—C3—C4	111.7 (2)	N6—C23—H23B	108.3
N2—C3—H3	124.1	C24—C23—H23B	108.3
C4—C3—H3	124.1	H23A—C23—H23B	107.4
C9—C4—C3	104.3 (2)	C25—C24—C29	118.3 (2)
C9—C4—C5	119.2 (2)	C25—C24—C23	121.0 (2)
C3—C4—C5	136.4 (2)	C29—C24—C23	120.7 (2)
O22—C5—N6	120.5 (2)	C26—C25—C24	121.3 (3)
O22—C5—C4	127.4 (2)	C26—C25—H25	119.4
N6—C5—C4	112.1 (2)	C24—C25—H25	119.4
C7—N6—C5	122.22 (19)	C27—C26—C25	119.6 (3)
C7—N6—C23	121.31 (19)	C27—C26—H26	120.2
C5—N6—C23	116.03 (19)	C25—C26—H26	120.2
N8—C7—N6	125.8 (2)	C28—C27—C26	120.0 (3)
N8—C7—S1	118.57 (17)	C28—C27—H27	120.0
N6—C7—S1	115.64 (17)	C26—C27—H27	120.0
C7—N8—C9	113.07 (19)	C27—C28—C29	120.4 (3)
N1—C9—N8	124.6 (2)	C27—C28—H28	119.8
N1—C9—C4	107.81 (19)	C29—C28—H28	119.8
N8—C9—C4	127.5 (2)	C28—C29—C24	120.4 (3)
N1—C10—C11	112.93 (19)	C28—C29—H29	119.8
N1—C10—H10A	109.0	C24—C29—H29	119.8
C11—C10—H10A	109.0	S1—C30—H30A	109.5
N1—C10—H10B	109.0	S1—C30—H30B	109.5
C11—C10—H10B	109.0	H30A—C30—H30B	109.5
H10A—C10—H10B	107.8	S1—C30—H30C	109.5
C12—C11—C10	113.96 (19)	H30A—C30—H30C	109.5
C12—C11—H11A	108.8	H30B—C30—H30C	109.5
C10—C11—H11A	108.8	N18—C32—C33	115.0 (2)
C12—C11—H11B	108.8	N18—C32—H32A	108.5
C10—C11—H11B	108.8	C33—C32—H32A	108.5
H11A—C11—H11B	107.7	N18—C32—H32B	108.5
N13—C12—C11	112.60 (19)	C33—C32—H32B	108.5
N13—C12—H12A	109.1	H32A—C32—H32B	107.5
C11—C12—H12A	109.1	C38—C33—C34	118.7 (2)
N13—C12—H12B	109.1	C38—C33—C32	123.7 (2)
C11—C12—H12B	109.1	C34—C33—C32	117.6 (2)
H12A—C12—H12B	107.8	C35—C34—C33	120.4 (2)
C21—N13—N14	111.28 (19)	C35—C34—H34	119.8
C21—N13—C12	127.6 (2)	C33—C34—H34	119.8
N14—N13—C12	120.88 (19)	C36—C35—C34	120.8 (2)
C15—N14—N13	105.16 (19)	C36—C35—H35	119.6
N14—C15—C16	111.8 (2)	C34—C35—H35	119.6
N14—C15—H15	124.1	C35—C36—C37	119.3 (2)
C16—C15—H15	124.1	C35—C36—H36	120.3
C21—C16—C15	104.3 (2)	C37—C36—H36	120.3
C21—C16—C17	119.1 (2)	C36—C37—C38	120.1 (3)
C15—C16—C17	136.4 (2)	C36—C37—H37	120.0
O31—C17—N18	119.8 (2)	C38—C37—H37	120.0
O31—C17—C16	128.1 (2)	C33—C38—C37	120.8 (2)
N18—C17—C16	112.1 (2)	C33—C38—H38	119.6
C19—N18—C17	122.64 (19)	C37—C38—H38	119.6
C19—N18—C32	121.25 (19)	S2—C39—H39A	109.5
C17—N18—C32	116.11 (19)	S2—C39—H39B	109.5
N20—C19—N18	125.0 (2)	H39A—C39—H39B	109.5
N20—C19—S2	119.29 (17)	S2—C39—H39C	109.5
N18—C19—S2	115.69 (17)	H39A—C39—H39C	109.5
C19—N20—C21	113.46 (19)	H39B—C39—H39C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O22^i	0.97	2.47	3.367 (3)	154

Symmetry code: (i) −x+1, −y+1, −z.