Folded conformations due to arene inter­actions in dissymmetric and symmetric butyl­idene-linker models based on pyrazolo­[3,4-d]pyrimidine, purine and 7-de­aza­purine

The butyl­idene-linker models 1-[2-(2,6-di­methyl­sulfanyl-9H-purin-9-yl)-2-methyl­idene­propyl]-4,6-bis­(methyl­sulfanyl)-1H-pyrazolo­[3,4-d]pyrimidine, C₁₈H₂₀N₈S₄, (XI), 7,7′-(2-methylidene­propane-1,3-diyl)­bis­[3-methyl-2-methyl­sulfanyl-3H-pyrrolo­[2,3-d]pyrimidin-4(7H)-one], C₂₀H₂₂N₆O₂S₂, (XIV), and 7-[2-(4,6-di­methyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidin-1-yl)-2-methyl­idene­propyl]-3-methyl-2-methyl­sulfanyl-3H-pyrrolo­[2,3-d]pyrimidin-4(7H)-one, C₁₉H₂₁N₇OS₃, (XV), show folded conformations in solution, as shown by ¹H NMR analysis. This folding carries over to the crystalline state. Intra­molecular π–π inter­actions are observed in all three compounds, but only (XIV) shows additional intra­molecular C—H...π inter­actions in the solid state. As far as can be established, this is the first report incorporating the pyrrolo­[2,3-d]pyrimidine nucleus for such a study. In addition to the π–π inter­actions, the crystal structures are also stabilized by other weak inter­molecular C—H...S/N/O and/or S...N/S inter­actions.

S1. Introduction

Aromatic inter­actions play a key role in the chemical (Hunter et al., 2001; Grimme et al., 2008; Mati & Cockroft, 2010) and biological sciences (Krueger & Kool, 2007), for example, in molecular recognition (Hunter, 1994), DNA/RNA structures (Hobza & Sponer, 1999), crystal engineering (Desiraju, 1995) and drug development (Salonen et al., 2011). Pyrazolo­[3,4-d]pyrimidine (PP) is an important core from the medicinal point of view (Chauhan & Kumar, 2013) and is isomeric with purine. In our previous work, we used the PP core for studying intra­molecular arene inter­actions in truly flexible 1,3-bis­(4,6-di­methyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidin-1-yl)propane, (I) (see Scheme 2), both by ¹H NMR in solution (Avasthi et al., 1995) and by X-ray crystallography in the solid state (Biswas et al., 1995). Further work on 12 symmetric and two dissymmetric propyl­ene-linker compounds (Scheme 1), related to the two parent compounds (I) and (III), established that the unusual U motif is indeed robust for studying arene inter­actions at both the molecular and supra­molecular levels (Avasthi et al., 2009; Avasthi & Kumar, 2012). In addition, the propyl­ene/Leonard linker has been also used to demonstrate intra­molecular cation–π inter­actions (Richter et al., 2008) and anion–π inter­actions (Zhao et al., 2014). Recently, we observed that the PP core is suitable to adopt a folded conformation via intra­molecular π–π inter­actions, even for ethyl­ene-linker compounds (Avasthi et al., 2012).

All our efforts to crystallize compound (II) (Fig. 1) were unsuccessful, whereas the corresponding butyl­idene linker compound (VI) (Scheme 2) crystallizes readily due to the reduced flexibility of the linker. In our on-going studies, we have used butyl­idene as an alternative to propyl­ene as a linker for studying arene inter­actions in two symmetric and one dissymmetric flexible compounds based on PP, purine and carbazole systems (Avasthi et al., 2011). One of the main reasons for selecting the butyl­idene linker was the limited success of the propyl­ene linker with dissymmetric compounds, due to difficulties in growing diffraction-quality crystals compared with symmetric flexible compounds. From a practical point of view, dissymmetric compounds are more abundant and can give valuable information about two different arenes involved in arene inter­actions. Vögtle refers to singly linked molecules that adopt π-stacked conformations as `protophanes' (Vögtle, 1993).

The present work describes two dissymmetric and one symmetric butyl­idene linker models for studying π–π inter­actions. Our strategy to avoid ionizable protons (e.g. O/N/S—H), used earlier for propyl­ene linker compounds, is also followed here. Thus, strong classical hydrogen bonds do not occur, so that weak arene inter­actions and nonclassical hydrogen bonds (e.g. C—H···O/N/S) can be observed without their inter­ference.

S2. Experimental

S2.1. Synthesis and crystallization

To a stirred solution of compound (VII) (Falco & Hitchings, 1956; Taylor et al., 1966) (1.00 g, 4.71 mmol) in di­methyl­formamide (DMF; 15 ml) at room temperature was added potassium carbonate (0.98 g, 7.09 mmol) and, after 30 min of stirring, methallyl dichloride (2.18 ml, 18.88 mmol) was added. The resultant reaction mixture was stirred for 3 h at room temperature and then water–EtOAc (1:1 v/v, 200 ml) was added. The organic layer was separated and the aqueous layer again extracted with EtOAc (3 × 100 ml). The organic layers were combined and washed with water (4 × 100 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica-gel column chromatography (2–20% EtOAc–hexane) to give pure (VIII) and (IX). For (VIII): yield 52%; viscous liquid; MS (ESI) m/z 301 [M + H]⁺; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 2.62 (s, 3H, SMe), 2.69 (s, 3H, SMe), 4.01 (s, 2H, CH₂Cl), 5.12 (s, 2H, NCH₂), 5.14 (s, 1H, CH), 5.36 (s, 1H, CH), 7.96 (s, 1H, ArH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 11.8, 14.3, 45.4, 48.7, 109.2, 118.6, 132.2, 140.1, 152.1, 165.0, 169.1. HRMS (ESI), calculated for C₁₁H₁₄ClN₄S₂ (M + H) 301.0348; found 301.0345. For (IX): yield 29%; viscous liquid; MS (ESI) m/z 301 [M + H]⁺; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 2.62 (s, 3H, SMe), 2.68 (s, 3H, SMe), 3.98 (s, 2H, CH₂Cl), 5.07 (s, 2H, NCH₂), 5.27 (s, 1H, CH), 5.44 (s, 1H, CH), 8.00 (s, 1H, ArH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 11.9, 14.2, 45.1, 55.6, 109.1, 120.1, 124.4, 139.1, 158.9, 166.4, 168.8. HRMS (ESI), calculated for C₁₁H₁₄ClN₄S₂ (M + H) 301.0348; found 301.0344.

To a stirred solution of compound (X) (Dille & Christensen, 1954) (0.50 g, 2.35 mmol) in DMF (20 ml) at room temperature was added potassium carbonate (0.50 g, 3.62 mmol). After 30 min of stirring, 1-(2-chloro­methyl­allyl)-4,6-di­methyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidine, (VIII) (0.85 g, 2.82 mmol), was added. The resultant reaction mixture was stirred for 20 h at room temperature and then all volatiles were removed under reduced pressure. The residue was added to water–CHCl₃ (1:1 v/v, 100 ml). The organic layer was separated and the aqueous layer again extracted with chloro­form (3 × 100 ml). The combined organic layers were washed with water (2 × 100 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica-gel column chromatography (10–60% EtOAc–hexane) to give pure (XI) and (XII). For (XI): yield 77%; m.p. 423–425 K; MS (ESI) m/z 477 [M + H]⁺; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 2.45 (s, 3H, SMe), 2.49 (s, 3H, SMe), 2.69 (s, 3H, SMe), 2.70 (s, 3H, SMe), 4.65 (s, 2H, NCH₂), 4.93 (s, 2H, NCH₂), 5.35 (s, 1H, CH) 5.44 (s, 1H, CH), 7.80 (s, 1H, ArH), 7.94 (s, 1H, ArH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 11.8, 12.0, 14.2, 14.5, 45.3, 48.7, 109.2, 119.5, 128.2, 132.6, 138.4, 140.7, 149.0, 152.0, 161.2, 165.0, 165.2, 169.2. HRMS (ESI), calculated for C₁₈H₂₁N₈S₄ (M + H) 477.0772; found 477.0738. For (XII): yield 5%; m.p. 457–459 K; MS (ESI) m/z 477 [M + H]⁺; ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.55 (s, 3H, SMe), 2.58 (s, 3H, SMe), 2.64 (s, 3H, SMe), 2.70 (s, 3H, SMe), 4.83 (s, 1H, CH), 4.89 (s, 2H, NCH₂), 5.06 (s, 2H, NCH₂), 5.38 (s, 1H, CH), 7.95 (s, 1H, ArH), 7.97 (s, 1H, ArH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 11.9, 12.2, 14.3, 14.5, 49.4, 49.5, 109.3, 114.0, 117.9, 132.5, 139.2, 140.9, 146.6, 152.2, 153.8, 165.1, 165.5, 169.4. HRMS (ESI), calculated for C₁₈H₂₁N₈S₄ (M + H) 477.0772; found 477.0761.

To a stirred solution of compound (XIII) (Tolman et al., 1970) (0.30 g, 1.50 mmol) in DMF (15 ml) at room temperature was added caesium carbonate (0.60 g, 2.00 mmol) and, after 30 min of stirring, methallyl dichloride (0.09 ml, 0.77 mmol) was added. The resultant reaction mixture was stirred for 15 h at room temperature, and then all volatiles were removed under reduced pressure. The residue was added to water–CHCl₃ (1:1 v/v, 100 ml). The organic layer was separated and the aqueous layer again extracted with chloro­form (3 × 100 ml). The combined organic layers were washed with water (2 × 100 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica-gel column chromatography (10–30% EtOAc–hexane) to give pure (XIV). For (XIV): yield 83%; m.p. 439–441 K; MS m/z 443 [M + H]⁺; ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.20 (s, 6H, 2 × SMe), 3.51 (s, 6H, 2 × Me), 4.49 (s, 4H, 2 × NCH₂), 5.41 (s, 2H, CH₂), 6.70 (d, J = 3.4 Hz, 2H, ArH), 6.66 (d, J = 3.4 Hz, 2H, ArH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 14.4, 29.8, 45.3, 103.4, 103.5, 118.8, 120.3, 141.0, 146.5, 156.3, 158.9. HRMS (ESI), calculated for C₂₀H₂₃N₆O₂S₂ (M + H) 443.1324; found 443.1324.

To a stirred solution of compound (XIII) (Tolman et al., 1970) (0.30 g, 1.50 mmol) in DMF (15 ml) at room temperature was added caesium carbonate (0.60 g, 2.00 mmol). After 30 min of stirring, 1-(2-chloro­methyl­allyl)-4,6-di­methyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidine, (VIII) (0.60 g, 2.00 mmol), was added. The resultant reaction mixture was stirred for 15 h at room temperature, and then all volatiles were removed under reduced pressure. The residue was added to water–CHCl₃ (1:1 v/v, 100 ml). The organic layer was separated and the aqueous layer again extracted with chloro­form (3 × 100 ml). The combined organic layers were washed with water (2 × 100 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica-gel column chromatography (10–30% EtOAc–hexane) to give pure (XV). For (XV): yield 85%; mp 421–423 K; MS (ESI) m/z 460 [M + H]⁺; ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.21 (s, 3H, SMe), 2.34 (s, 3H, SMe), 2.69 (s, 3H, SMe), 3.50 (s, 3H, NMe), 4.51 (s, 2H, NCH₂), 4.80 (s, 2H, NCH₂), 5.39 (s, 1H), 5.44 (s, 1H), 6.67 (d, J = 3.2 Hz, 1H, ArH), 6.74 (d, J = 3.4 Hz ,1H, ArH), 7.95 (s, 1H, ArH); ¹³C NMR (50 MHz, CDCl₃, δ, p.p.m.): 12.1, 13.7, 14.9, 29.8, 45.9, 48.2, 103.5, 103.8, 109.0, 118.8, 120.6, 132.4, 140.0, 146.3, 152.0, 156.3, 158.9, 164.6, 169.0. HRMS (ESI), calculated for C₁₉H₂₂N₇OS₃ (M + H) 460.1048; found 460.1025.

Single crystals suitable for X-ray diffraction were grown by slow evaporation at room temperature from a mixture of n-hexane and ethyl acetate for all three compounds, viz. (XI), (XIV) and (XV) [Solvent ratio for each?].

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and treated as riding on their parent C atom, with C—H = 0.97 (methyl­ene), 0.93 (aromatic) or 0.96 Å (methyl), and with U_iso(H) = 1.5U_eq(C).

S3. Results and discussion

In this study, we have selected the purine system because of its importance from a biological point of view (Baraldi et al., 2008) and its presence in DNA and RNA structures. The main difference between the PP and purine cores is that the H atom of purine, between two N atoms, is more acidic than that of the PP core.

We have synthesized the dissymmetric compound (XI) based on both purine and PP systems (Scheme 1). Compound (XI) shows an up-field shift for the 6-methyl­sulfanyl protons in its ¹H NMR spectrum, strongly indicating that it adopts a folded conformation in CDCl₃ solution. The molecular structure and conformation of (XI) are shown in Fig. 1. The structure is folded at the centre of the bridge [C8—C9—C10 = 117.69 (18)°] via intra­molecular π–π inter­actions between PP and purine rings. The four important distances describing the stacked conformation of (XI) are N1···N12, Cg(XC)···Cg(XC'), Cg(XB)···Cg(XB') and Cg(XA)···Cg(XA') of 3.254 (3), 3.588 (2), 3.8185 (17) and 4.441 (2) Å, respectively (Cg denotes a ring centroid, and XA, XB, XC and their primed counterparts are defined in Fig. 1 [Added text OK?]). The inter­planar spacing between Cg(XC') and the plane formed by the C14a/C15/N16/C17/N18/C18a ring in (XI) is 3.3499 (8) Å. Both the purine and PP rings exist in a gauche conformation [N1—C8—C9—C10 = 39.8 (3)° and N12—C10—C9—C8 = 53.2 (3)°]. For the purpose of comparison, the data for two earlier symmetric butyl­idene-linker compounds, viz. (V) and (VI) in Scheme 1, are given in Table 2 (Avasthi et al., 2011). It is worth mentioning that all four distances in the first four columns of Table 2 for dissymmetric compound (XI) are less than the corresponding distances in two earlier symmetric butyl­idene linker compounds [(V) and (VI)]. We believe that the involvement of the two different electron-deficient ring systems (PP and purine) is responsible for the smaller distances in (XI) compared with the corresponding distances in two symmetric compounds [(V) and (VI)] having similar arene systems. Another question of inter­est is how this compound will pack in a vertical column via π–π inter­actions, as there are two distinct possibilities of two similar or different faces approaching each other.

At the supra­molecular level, Fig. 2 shows the inter­molecular C—H···S dimerization of (XI) and part of the infinite parallel vertical stacks which are formed via inter­molecular π–π inter­actions. Hydrogen-bonding parameters are given in Table 3 and inter­molecular π–π inter­action distances are given in Table 4.

Fig. 3 shows the dimerization via inter­molecular S···N and S···S inter­actions, with distances of 3.400 and 3.379 Å, respectively. These inter­actions can be considered as σ-hole bonds (Politzer et al., 2013). Such dimerization via S···N and S···S inter­actions was not observed in the symmetric butyl­idene linker compound of purine, (VI).

We have synthesized two more models, (XIV) and (XV) (Scheme 1), based on 7-de­aza­purine and the PP core. The pyrrolo­[2,3-d]pyrimidine core is an another biologically important system (Wang et al., 2012) and it is structurally related to the biologically important purine. Chemically, this nucleus has only three N atoms compared with the two earlier systems (purine and PP), which have four N atoms. In addition, 7-de­aza­purine has two H atoms, compared with only one H atom in the five-membered ring of the two earlier systems (purine and PP).

Compound (XIV) is symmetric and has 7H-pyrrolo­[2,3-d]pyrimidine on both termini of the linker, while compound (XV) has 7H-pyrrolo­[2,3-d]pyrimidine on one terminus and PP on the other. These new compounds, (XIV) and (XV), were synthesized in order to study the effect of 7-de­aza­purine on intra­molecular π–π inter­actions. Proton NMR analysis of symmetric (XIV) and dissymmetric (XV) showed an up-field shift for the methyl­sulfanyl protons, strongly indicating the presence of a folded conformation in CDCl₃ solution. This folding is carried over to the solid state, as shown by X-ray crystallography for both (XIV) (Fig. 4) and (XV) (Fig. 7), via intra­molecular π–π inter­actions. The four important distances describing the stacked conformation of (XIV) and (XV) are given in Table 2. Compound (XIV) is stabilized by additional intra­molecular C—H···π inter­actions between the methyl­sulfanyl group and the six-membered pyrimidine ring, with distances H20···Cg(XC) = 2.968 Å, C20···Cg(XC) = 3.7333 (2) Å and C20—H20···Cg(XC) = 137.58°, and H22···Cg(XC') = 3.005 Å, C22···Cg(XC') = 3.868 (2) Å and C22—H22···Cg(XC') = 150.38°. The inter­planar spacings between Cg(XC') and the plane formed by the C14a/C15/N16/C17/N18/C18a ring in (XIV) and (XV) are 3.4599 (7) and 3.3251 (5) Å, respectively. For (XIV), both rings adopt a symmetric conformation about the central butyl­idene spacer group. Specifically, both 7H-pyrrolo­[2,3-d]pyrimidine rings exist in a gauche conformation [N1—C8—C9—C10 = -63.4 (2)° and N12—C10—C9—C8 = -55.0 (2)°]. For (XV), both the 7H-pyrrolo­[2,3-d]pyrimidine and the PP rings exist in a gauche conformation [N1—C8—C9—C10 = -50.91 (17)° and N12—C10—C9—C8 = -49.44 (18)°]. Symmetric (XIV) is closely related to folded propyl­ene-linker (III) (see Scheme 2) (Maulik et al., 1998), as both compounds have similar pyrimidine portions. All four distances of (III) are smaller than those of (XIV) (Table 2), indicating decreased π–π stacking in (XIV). Dissymmetric (XV) is closely related to folded propyl­ene-linker (IV) (Scheme 2) (Avasthi et al., 2006), as both compounds have a similar PP portion at one terminus of the linker. On careful analysis of the crystal structures of the three compounds, it is clear that arene inter­action decreases on decreasing the number of ring N atoms.

At the supra­molecular level, the chain motif of (XIV) formed via C—H···O inter­actions is shown in Fig. 5. Hydrogen-bonding parameters are given in Table 3. Fig. 6 shows part of an infinite vertical stack consisting of three molecules attached to each other via inter­molecular π–π, C—H···O and C—H···S inter­actions. Inter­molecular π–π inter­action distances are given in Table 4.

At the supra­molecular level, part of the crystal structure of (XV) showing the formation of a tetra­mer via C—H···O inter­actions between the two C—H···N dimers is shown in Fig. 8. Hydrogen-bonding parameters are given in Table 3. Fig. 8 shows the dimer of (XV) formed via inter­molecular π–π inter­actions. Inter­molecular π–π inter­action distances are given in Table 4.

Perusal of the data given in Table 2 shows that the unusual U-motif formed via intra­molecular π–π inter­actions in the three folded compounds (XI), (XIV) and (XV) is quite robust and similar to earlier butyl­idene-linker compounds. The distance between the two N atoms bearing the butyl­idene linker varies in the broad range 3.254 (3)–3.605 (3) Å and the inter­nal angle at the central atom of the linker is fairly constant for all three compounds [116.59 (17)–117.64 (18) Å], indicating that folding does not cause an appreciable change in the linker. On the other hand, the distance between the two partially overlapping six-membered pyrimidine rings in (XI), (XIV) and (XV) varies in the wide range 3.588 (2)–4.2925 (16) Å and this may be a reflection of the different heterocyclic systems. The angle between the least-squares planes in all three compounds varies in a narrow range between 12.33 (5) and 14.86 (5)°.

In summary, we have reported three new butyl­idene-linker models. The two dissymmetric models show folded conformations due to intra­molecular arene inter­actions in the solid state, whereas the symmetric model shows a folded conformation due to intra­molecular arene and C—H···π inter­actions in the solid state. The 7H-pyrrolo­[2,3-d]pyrimidine core has been used here for the first time for this kind of study. Our results reveal that decreasing the number of N atoms in the arene system has the effect of increasing all intra­molecular inter­action distances, probably indicating reduced arene inter­actions. In addition, the worthiness of the PP core as a novel system for studying arene inter­actions, both in solution and in the solid state, is again demonstrated.

Related literature

For related literature, see: Avasthi & Kumar (2012); Avasthi et al. (1995, 2006, 2009, 2011); Avasthi, Kumar, Aswal, Kant, Raghunandan, Maulik, Khanna & Ravikumar (2012); Baraldi et al. (2008); Biswas et al. (1995); Chauhan & Kumar (2013); Desiraju (1995); Dille & Christensen (1954); Falco & Hitchings (1956); Grimme et al. (2008); Hobza & Sponer (1999); Hunter (1994); Hunter et al. (2001); Krueger & Kool (2007); Mati & Cockroft (2010); Maulik et al. (1998); Politzer et al. (2013); Richter et al. (2008); Salonen et al. (2011); Taylor et al. (1966); Tolman et al. (1970); Vögtle (1993); Wang (2012); Zhao (2014).

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2012) for (XI), (XIV); SMART (Bruker, 2001) for (XV). Cell refinement: CrystalClear-SM Expert (Rigaku, 2012) for (XI), (XIV); SAINT (Bruker, 2001) for (XV). Data reduction: CrystalClear-SM Expert (Rigaku, 2012) for (XI), (XIV); SAINT (Bruker, 2001) for (XV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008) for (XI), (XIV); SHELXTL/PC (Sheldrick, 2008) for (XV). For all compounds, software used to prepare material for publication: PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of (XI), showing π–π interactions (dashed lines) and the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. XA, XB, XC and their primed equivalents indicate the ring centroids and the centres of the C—C bonds. [Added text OK? Significance of curved dashed line at C9 and dashed line between N1 and N12?]

Fig. 2. A view, along the b axis, of the two-dimensional hydrogen-bonded network of (XI), formed as a result of intermolecular C—H···S dimerization, and part of the infinite vertical stack of (XI), formed as a result of intermolecular π–π interactions. Dashed lines indicate the various interactions. Pink dots indicate ring centroids and the centres of the C—C bonds. H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) x + 1, y + 1, z; (ii) -x, -y + 1, -z; (iii) -x, -y + 2, -z.]

Fig. 3. The dimer of (XI), formed via intermolecular S···N and S···S interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted. [Symmetry code: (iii) -x, -y + 2, -z.]

Fig. 4. The molecular structure of (XIV), showing π–π and C—H···π interactions (dashed lines) and the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. XA, XB, XC and their primed equivalents indicate the ring centroids and the centres of the C—C bonds. [Added text OK? Significance of curved dotted line at C9 and dashed line between N1 and N12?]

Fig. 5. The chain motif of compound (XIV), formed via C—H···O interactions (dashed lines). For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted. [Symmetry code: (iv) x + 1, y, z.]

Fig. 6. Part of an infinite vertical stack of (XIV), formed as a result of intermolecular π–π, C—H···O and C—H···S interactions. Dashed lines indicate the various interactions. Pink dots indicate ring centroids and the centres of the C—C bonds. H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (v) -x + 1/2, y + 1/2, z; (vi) -x + 1/2, y - 1/2, z.]

Fig. 7. The molecular structure of (XV), showing π–π interactions (dashed lines) and the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. XA, XB, XC and their primed equivalents indicate the ring centroids and the centres of the C—C bonds. [Added text OK? Significance of curved dashed line at C9 and dashed line between N1 and N12?]

Fig. 8. Part of the crystal structure of (XV), viewed down the c axis, showing the formation of a tetramer via C—H···O interactions between two C—H···N dimers and the dimer formed via intermolecular π–π interactions. Dashed lines indicate the various interactions. Pink dots indicate ring centroids and the centres of the C—C bonds. For the sake of clarity, H atoms not involved in the hydrogen bonding have been omitted. [Symmetry codes: (vii) -x + 2, -y + 1, -z + 1; (viii) x + 1, y, z.]

(XI) 1-[2-(2,6-Dimethylsulfanyl-9H-purin-9-yl)-2-methylidenepropyl]-4,6-bis(methylsulfanyl)-1H-pyrazolo[3,4-d]pyrimidine

Crystal data

C18H20N8S4	Z = 2
Mr = 476.66	F(000) = 496
Triclinic, P1	Dx = 1.458 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 9.285 (4) Å	Cell parameters from 1622 reflections
b = 9.818 (4) Å	θ = 3.1–25.4°
c = 13.400 (6) Å	µ = 0.46 mm^−1
α = 98.707 (7)°	T = 293 K
β = 103.080 (3)°	Block, colourless
γ = 109.593 (4)°	0.26 × 0.23 × 0.11 mm
V = 1086.0 (8) Å^3

Data collection

Rigaku Saturn724+ diffractometer	3891 independent reflections
Radiation source: MicroMax003_Mo	2711 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.027
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.4°, θmin = 3.1°
profile data from ω scans	h = −11→11
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −11→10
Tmin = 0.890, Tmax = 0.951	l = −13→16
8577 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0611P)^2] where P = (Fo^2 + 2Fc^2)/3
3891 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.31 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
C3	0.7765 (3)	0.9487 (3)	0.42829 (19)	0.0518 (6)
H3	0.8396	0.8937	0.4428	0.062*
C4	0.4792 (3)	0.7514 (2)	0.37100 (17)	0.0415 (6)
C6	0.3065 (2)	0.8694 (3)	0.32767 (17)	0.0389 (5)
C8	0.7158 (3)	1.2844 (2)	0.41050 (19)	0.0483 (6)
H8A	0.7740	1.3460	0.4817	0.058*
H8B	0.6094	1.2862	0.3934	0.058*
C9	0.7991 (2)	1.3517 (2)	0.33543 (19)	0.0427 (6)
C10	0.7633 (2)	1.2541 (3)	0.22873 (19)	0.0470 (6)
H10A	0.8164	1.3136	0.1864	0.056*
H10B	0.8063	1.1776	0.2364	0.056*
C11	0.8948 (3)	1.4929 (3)	0.3617 (2)	0.0671 (8)
H11A	0.9420	1.5343	0.3134	0.080*
H11B	0.9155	1.5516	0.4286	0.080*
C13	0.4870 (3)	1.2513 (3)	0.14980 (18)	0.0450 (6)
H13	0.5179	1.3544	0.1685	0.054*
C15	0.2352 (2)	0.8731 (2)	0.04193 (16)	0.0347 (5)
C17	0.4382 (2)	0.7907 (2)	0.09462 (17)	0.0340 (5)
C19	0.3249 (3)	0.4477 (3)	0.3363 (2)	0.0722 (9)
H19A	0.2592	0.4616	0.3797	0.108*
H19B	0.3341	0.3531	0.3358	0.108*
H19C	0.2768	0.4498	0.2654	0.108*
C20	0.1049 (3)	1.0187 (3)	0.2777 (2)	0.0565 (7)
H20A	0.1550	1.0816	0.3482	0.085*
H20B	−0.0030	1.0128	0.2533	0.085*
H20C	0.1637	1.0597	0.2317	0.085*
C21	−0.0585 (3)	0.6442 (3)	−0.0421 (2)	0.0565 (7)
H21A	−0.0190	0.5961	−0.0911	0.085*
H21B	−0.1722	0.6140	−0.0707	0.085*
H21C	−0.0352	0.6164	0.0236	0.085*
C22	0.6901 (2)	0.6996 (3)	0.1464 (2)	0.0553 (7)
H22A	0.7386	0.7648	0.1063	0.083*
H22B	0.7261	0.6186	0.1437	0.083*
H22C	0.7199	0.7543	0.2186	0.083*
C3a	0.6079 (2)	0.8892 (3)	0.39515 (17)	0.0420 (6)
C7a	0.5640 (2)	1.0100 (2)	0.38324 (16)	0.0384 (5)
C14a	0.3474 (2)	1.0184 (2)	0.08651 (16)	0.0343 (5)
C18a	0.5035 (2)	1.0331 (2)	0.13354 (16)	0.0334 (5)
N1	0.7018 (2)	1.1321 (2)	0.40854 (15)	0.0453 (5)
N2	0.8326 (2)	1.0945 (3)	0.43589 (17)	0.0613 (6)
N5	0.3302 (2)	0.7418 (2)	0.33756 (14)	0.0419 (5)
N7	0.4151 (2)	1.00675 (19)	0.34970 (13)	0.0380 (4)
N12	0.5913 (2)	1.18250 (19)	0.17320 (14)	0.0394 (5)
N14	0.3394 (2)	1.1597 (2)	0.09867 (16)	0.0496 (5)
N16	0.28184 (19)	0.75962 (19)	0.04624 (13)	0.0354 (4)
N18	0.55592 (19)	0.92278 (19)	0.14021 (13)	0.0352 (4)
S1	0.51880 (8)	0.59338 (8)	0.38805 (6)	0.0620 (2)
S2	0.10306 (7)	0.83559 (7)	0.27780 (5)	0.0511 (2)
S3	0.03641 (6)	0.84207 (7)	−0.01959 (5)	0.04677 (19)
S4	0.47671 (6)	0.62738 (6)	0.09174 (5)	0.04547 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3	0.0451 (14)	0.0643 (18)	0.0482 (15)	0.0266 (13)	0.0098 (11)	0.0136 (14)
C4	0.0533 (14)	0.0427 (14)	0.0336 (13)	0.0203 (11)	0.0158 (10)	0.0154 (11)
C6	0.0415 (12)	0.0409 (14)	0.0372 (13)	0.0140 (11)	0.0166 (10)	0.0145 (11)
C8	0.0446 (14)	0.0371 (14)	0.0502 (15)	0.0048 (11)	0.0144 (11)	−0.0007 (12)
C9	0.0322 (12)	0.0328 (13)	0.0523 (15)	0.0040 (10)	0.0091 (10)	0.0046 (11)
C10	0.0360 (12)	0.0436 (15)	0.0549 (16)	0.0051 (11)	0.0177 (11)	0.0113 (12)
C11	0.0592 (16)	0.0456 (16)	0.074 (2)	0.0024 (13)	0.0094 (14)	0.0094 (15)
C13	0.0610 (16)	0.0297 (13)	0.0512 (15)	0.0210 (12)	0.0201 (12)	0.0157 (12)
C15	0.0364 (11)	0.0381 (13)	0.0341 (12)	0.0181 (10)	0.0110 (9)	0.0122 (10)
C17	0.0341 (11)	0.0353 (13)	0.0349 (12)	0.0155 (10)	0.0123 (9)	0.0075 (10)
C19	0.093 (2)	0.0430 (16)	0.072 (2)	0.0234 (15)	0.0125 (16)	0.0148 (15)
C20	0.0484 (14)	0.0563 (17)	0.0748 (19)	0.0245 (12)	0.0238 (13)	0.0262 (15)
C21	0.0408 (13)	0.0443 (15)	0.0754 (19)	0.0128 (11)	0.0079 (12)	0.0112 (14)
C22	0.0370 (13)	0.0613 (17)	0.0675 (18)	0.0266 (12)	0.0082 (12)	0.0085 (14)
C3a	0.0408 (13)	0.0518 (15)	0.0346 (13)	0.0173 (11)	0.0110 (10)	0.0156 (11)
C7a	0.0369 (12)	0.0426 (14)	0.0326 (12)	0.0090 (10)	0.0125 (9)	0.0114 (11)
C14a	0.0387 (11)	0.0347 (13)	0.0324 (12)	0.0167 (10)	0.0109 (9)	0.0100 (10)
C18a	0.0394 (12)	0.0324 (12)	0.0303 (12)	0.0134 (10)	0.0145 (9)	0.0080 (10)
N1	0.0372 (11)	0.0479 (12)	0.0450 (12)	0.0093 (9)	0.0127 (8)	0.0108 (10)
N2	0.0442 (12)	0.0781 (18)	0.0558 (15)	0.0232 (12)	0.0083 (10)	0.0111 (13)
N5	0.0426 (11)	0.0413 (12)	0.0444 (12)	0.0149 (9)	0.0144 (9)	0.0185 (10)
N7	0.0370 (10)	0.0404 (11)	0.0373 (11)	0.0120 (8)	0.0147 (8)	0.0127 (9)
N12	0.0405 (10)	0.0325 (11)	0.0405 (11)	0.0080 (8)	0.0140 (8)	0.0071 (9)
N14	0.0598 (13)	0.0417 (12)	0.0528 (13)	0.0241 (10)	0.0172 (10)	0.0163 (10)
N16	0.0315 (9)	0.0363 (11)	0.0374 (11)	0.0151 (8)	0.0064 (8)	0.0071 (9)
N18	0.0347 (9)	0.0351 (11)	0.0357 (10)	0.0140 (8)	0.0115 (8)	0.0055 (8)
S1	0.0702 (5)	0.0555 (5)	0.0710 (5)	0.0337 (4)	0.0170 (4)	0.0294 (4)
S2	0.0361 (3)	0.0474 (4)	0.0674 (5)	0.0107 (3)	0.0135 (3)	0.0223 (3)
S3	0.0375 (3)	0.0436 (4)	0.0568 (4)	0.0204 (3)	0.0020 (3)	0.0126 (3)
S4	0.0364 (3)	0.0357 (4)	0.0637 (4)	0.0190 (3)	0.0087 (3)	0.0079 (3)

Geometric parameters (Å, º)

C3—N2	1.327 (3)	C17—N16	1.355 (3)
C3—C3a	1.408 (3)	C17—S4	1.753 (2)
C3—H3	0.9300	C19—S1	1.782 (3)
C4—N5	1.320 (3)	C19—H19A	0.9600
C4—C3a	1.404 (3)	C19—H19B	0.9600
C4—S1	1.745 (2)	C19—H19C	0.9600
C6—N7	1.325 (3)	C20—S2	1.792 (3)
C6—N5	1.363 (3)	C20—H20A	0.9600
C6—S2	1.751 (2)	C20—H20B	0.9600
C8—N1	1.452 (3)	C20—H20C	0.9600
C8—C9	1.502 (3)	C21—S3	1.787 (2)
C8—H8A	0.9700	C21—H21A	0.9600
C8—H8B	0.9700	C21—H21B	0.9600
C9—C11	1.312 (3)	C21—H21C	0.9600
C9—C10	1.493 (3)	C22—S4	1.791 (2)
C10—N12	1.466 (3)	C22—H22A	0.9600
C10—H10A	0.9700	C22—H22B	0.9600
C10—H10B	0.9700	C22—H22C	0.9600
C11—H11A	0.9300	C3a—C7a	1.396 (3)
C11—H11B	0.9300	C7a—N7	1.341 (3)
C13—N14	1.311 (3)	C7a—N1	1.357 (3)
C13—N12	1.363 (3)	C14a—C18a	1.393 (3)
C13—H13	0.9300	C14a—N14	1.401 (3)
C15—N16	1.328 (3)	C18a—N18	1.334 (3)
C15—C14a	1.393 (3)	C18a—N12	1.366 (3)
C15—S3	1.743 (2)	N1—N2	1.373 (3)
C17—N18	1.326 (3)
N2—C3—C3a	110.4 (2)	H20A—C20—H20B	109.5
N2—C3—H3	124.8	S2—C20—H20C	109.5
C3a—C3—H3	124.8	H20A—C20—H20C	109.5
N5—C4—C3a	120.5 (2)	H20B—C20—H20C	109.5
N5—C4—S1	120.40 (16)	S3—C21—H21A	109.5
C3a—C4—S1	119.06 (18)	S3—C21—H21B	109.5
N7—C6—N5	128.4 (2)	H21A—C21—H21B	109.5
N7—C6—S2	119.80 (17)	S3—C21—H21C	109.5
N5—C6—S2	111.84 (15)	H21A—C21—H21C	109.5
N1—C8—C9	114.2 (2)	H21B—C21—H21C	109.5
N1—C8—H8A	108.7	S4—C22—H22A	109.5
C9—C8—H8A	108.7	S4—C22—H22B	109.5
N1—C8—H8B	108.7	H22A—C22—H22B	109.5
C9—C8—H8B	108.7	S4—C22—H22C	109.5
H8A—C8—H8B	107.6	H22A—C22—H22C	109.5
C11—C9—C10	121.4 (2)	H22B—C22—H22C	109.5
C11—C9—C8	120.8 (2)	C7a—C3a—C4	114.8 (2)
C10—C9—C8	117.69 (18)	C7a—C3a—C3	105.5 (2)
N12—C10—C9	112.72 (18)	C4—C3a—C3	139.6 (2)
N12—C10—H10A	109.0	N7—C7a—N1	126.0 (2)
C9—C10—H10A	109.0	N7—C7a—C3a	127.2 (2)
N12—C10—H10B	109.0	N1—C7a—C3a	106.8 (2)
C9—C10—H10B	109.0	C15—C14a—C18a	116.14 (19)
H10A—C10—H10B	107.8	C15—C14a—N14	134.2 (2)
C9—C11—H11A	120.0	C18a—C14a—N14	109.60 (18)
C9—C11—H11B	120.0	N18—C18a—N12	126.98 (19)
H11A—C11—H11B	120.0	N18—C18a—C14a	126.74 (19)
N14—C13—N12	114.2 (2)	N12—C18a—C14a	106.27 (18)
N14—C13—H13	122.9	C7a—N1—N2	110.7 (2)
N12—C13—H13	122.9	C7a—N1—C8	126.6 (2)
N16—C15—C14a	119.32 (19)	N2—N1—C8	122.70 (19)
N16—C15—S3	120.76 (16)	C3—N2—N1	106.64 (19)
C14a—C15—S3	119.93 (16)	C4—N5—C6	117.80 (18)
N18—C17—N16	128.51 (19)	C6—N7—C7a	111.29 (19)
N18—C17—S4	120.04 (15)	C13—N12—C18a	106.12 (18)
N16—C17—S4	111.45 (15)	C13—N12—C10	127.07 (19)
S1—C19—H19A	109.5	C18a—N12—C10	126.81 (18)
S1—C19—H19B	109.5	C13—N14—C14a	103.79 (19)
H19A—C19—H19B	109.5	C15—N16—C17	118.11 (18)
S1—C19—H19C	109.5	C17—N18—C18a	111.18 (18)
H19A—C19—H19C	109.5	C4—S1—C19	102.54 (12)
H19B—C19—H19C	109.5	C6—S2—C20	102.83 (11)
S2—C20—H20A	109.5	C15—S3—C21	101.63 (10)
S2—C20—H20B	109.5	C17—S4—C22	102.20 (11)
N1—C8—C9—C11	−143.0 (2)	N7—C6—N5—C4	−1.7 (3)
N1—C8—C9—C10	39.8 (3)	S2—C6—N5—C4	177.72 (16)
C11—C9—C10—N12	−124.0 (2)	N5—C6—N7—C7a	1.6 (3)
C8—C9—C10—N12	53.2 (3)	S2—C6—N7—C7a	−177.73 (15)
N5—C4—C3a—C7a	1.4 (3)	N1—C7a—N7—C6	177.5 (2)
S1—C4—C3a—C7a	−177.42 (16)	C3a—C7a—N7—C6	0.1 (3)
N5—C4—C3a—C3	−177.6 (3)	N14—C13—N12—C18a	0.1 (3)
S1—C4—C3a—C3	3.5 (4)	N14—C13—N12—C10	179.55 (19)
N2—C3—C3a—C7a	−0.2 (3)	N18—C18a—N12—C13	−178.4 (2)
N2—C3—C3a—C4	178.9 (3)	C14a—C18a—N12—C13	0.4 (2)
C4—C3a—C7a—N7	−1.5 (3)	N18—C18a—N12—C10	2.1 (3)
C3—C3a—C7a—N7	177.8 (2)	C14a—C18a—N12—C10	−179.06 (19)
C4—C3a—C7a—N1	−179.34 (18)	C9—C10—N12—C13	56.7 (3)
C3—C3a—C7a—N1	0.0 (2)	C9—C10—N12—C18a	−123.9 (2)
N16—C15—C14a—C18a	−0.2 (3)	N12—C13—N14—C14a	−0.6 (3)
S3—C15—C14a—C18a	−179.67 (15)	C15—C14a—N14—C13	178.5 (2)
N16—C15—C14a—N14	−177.8 (2)	C18a—C14a—N14—C13	0.8 (2)
S3—C15—C14a—N14	2.7 (3)	C14a—C15—N16—C17	0.2 (3)
C15—C14a—C18a—N18	−0.1 (3)	S3—C15—N16—C17	179.65 (14)
N14—C14a—C18a—N18	178.1 (2)	N18—C17—N16—C15	0.1 (3)
C15—C14a—C18a—N12	−178.90 (17)	S4—C17—N16—C15	−179.67 (15)
N14—C14a—C18a—N12	−0.7 (2)	N16—C17—N18—C18a	−0.4 (3)
N7—C7a—N1—N2	−177.6 (2)	S4—C17—N18—C18a	179.42 (15)
C3a—C7a—N1—N2	0.2 (3)	N12—C18a—N18—C17	178.92 (18)
N7—C7a—N1—C8	3.9 (4)	C14a—C18a—N18—C17	0.3 (3)
C3a—C7a—N1—C8	−178.2 (2)	N5—C4—S1—C19	6.5 (2)
C9—C8—N1—C7a	−119.2 (2)	C3a—C4—S1—C19	−174.64 (19)
C9—C8—N1—N2	62.6 (3)	N7—C6—S2—C20	−2.8 (2)
C3a—C3—N2—N1	0.4 (3)	N5—C6—S2—C20	177.77 (17)
C7a—N1—N2—C3	−0.4 (3)	N16—C15—S3—C21	9.6 (2)
C8—N1—N2—C3	178.1 (2)	C14a—C15—S3—C21	−170.94 (18)
C3a—C4—N5—C6	−0.1 (3)	N18—C17—S4—C22	−5.8 (2)
S1—C4—N5—C6	178.77 (16)	N16—C17—S4—C22	174.01 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21B···S4^i	0.96	2.94	3.739 (3)	142
C11—H11A···S2^ii	0.93	3.00	3.753 (3)	139

Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y+1, z.

(XIV) 7,7'-(2-Methylidenepropane-1,3-diyl)bis[3-methyl-2-methylsulfanyl-3H-pyrrolo[2,3-d]pyrimidin-4(7H)-one]

Crystal data

C20H22N6O2S2	F(000) = 1856
Mr = 442.56	Dx = 1.454 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5170 reflections
a = 9.859 (2) Å	θ = 3.1–25.4°
b = 13.979 (4) Å	µ = 0.30 mm^−1
c = 29.331 (8) Å	T = 100 K
V = 4042.4 (18) Å^3	Block, colourless
Z = 8	0.34 × 0.15 × 0.10 mm

Data collection

Rigaku Saturn724+ diffractometer	3679 independent reflections
Radiation source: MicroMax003_Mo	3477 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.048
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.4°, θmin = 3.2°
profile data from ω scans	h = −11→11
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −13→16
Tmin = 0.906, Tmax = 0.971	l = −24→35
29394 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0381P)^2 + 3.1679P] where P = (Fo^2 + 2Fc^2)/3
3679 reflections	(Δ/σ)max = 0.001
273 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.26 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
C2	0.3494 (2)	0.80837 (14)	0.46465 (6)	0.0179 (4)
H2	0.4170	0.7980	0.4862	0.021*
C3	0.21560 (19)	0.78887 (13)	0.47078 (6)	0.0170 (4)
H3	0.1756	0.7631	0.4967	0.020*
C4	0.01122 (19)	0.81340 (13)	0.41485 (6)	0.0167 (4)
C6	0.10228 (19)	0.88117 (13)	0.34360 (6)	0.0157 (4)
C8	0.50006 (19)	0.87995 (14)	0.40343 (7)	0.0171 (4)
H8A	0.4884	0.9006	0.3721	0.021*
H8B	0.5650	0.8278	0.4037	0.021*
C9	0.55428 (18)	0.96207 (14)	0.43159 (6)	0.0152 (4)
C10	0.47068 (19)	1.05227 (14)	0.43216 (6)	0.0169 (4)
H10A	0.3851	1.0398	0.4473	0.020*
H10B	0.5182	1.1011	0.4494	0.020*
C11	0.6676 (2)	0.95494 (15)	0.45531 (7)	0.0213 (4)
H11A	0.6973	1.0062	0.4729	0.026*
H11B	0.7177	0.8986	0.4545	0.026*
C13	0.53897 (19)	1.10565 (14)	0.35234 (6)	0.0175 (4)
H13	0.6318	1.0951	0.3549	0.021*
C14	0.47524 (19)	1.14138 (14)	0.31478 (6)	0.0175 (4)
H14	0.5156	1.1588	0.2874	0.021*
C15	0.21495 (19)	1.17628 (13)	0.30182 (6)	0.0168 (4)
C17	0.09597 (19)	1.13006 (13)	0.37213 (6)	0.0160 (4)
C19	−0.14375 (19)	0.85087 (15)	0.35124 (7)	0.0222 (4)
H19A	−0.1744	0.9158	0.3484	0.033*
H19B	−0.2031	0.8166	0.3714	0.033*
H19C	−0.1441	0.8208	0.3218	0.033*
C20	0.2228 (2)	0.94061 (15)	0.26385 (6)	0.0218 (4)
H20A	0.2128	0.9637	0.2332	0.033*
H20B	0.2714	0.8811	0.2635	0.033*
H20C	0.2722	0.9867	0.2815	0.033*
C21	−0.0329 (2)	1.19817 (16)	0.30744 (7)	0.0237 (5)
H21A	−0.0766	1.1432	0.2944	0.036*
H21B	−0.0146	1.2441	0.2839	0.036*
H21C	−0.0911	1.2263	0.3300	0.036*
C22	−0.0066 (2)	1.06902 (15)	0.45295 (7)	0.0225 (4)
H22A	−0.0835	1.0576	0.4723	0.034*
H22B	0.0533	1.1139	0.4674	0.034*
H22C	0.0407	1.0100	0.4478	0.034*
C3a	0.14842 (19)	0.81574 (13)	0.42955 (6)	0.0157 (4)
C7a	0.24702 (19)	0.85040 (13)	0.39984 (6)	0.0144 (4)
C14a	0.33428 (19)	1.14682 (13)	0.32575 (6)	0.0156 (4)
C18a	0.31986 (18)	1.11234 (13)	0.36982 (6)	0.0147 (4)
N1	0.36985 (15)	0.84612 (11)	0.42141 (5)	0.0153 (3)
N5	−0.00545 (15)	0.84994 (11)	0.36983 (5)	0.0161 (3)
N7	0.22875 (15)	0.88281 (11)	0.35666 (5)	0.0156 (3)
N12	0.44438 (15)	1.08748 (12)	0.38615 (5)	0.0154 (3)
N16	0.09511 (16)	1.16887 (11)	0.32889 (5)	0.0167 (3)
N18	0.20314 (15)	1.10188 (11)	0.39404 (5)	0.0156 (3)
O1	−0.08793 (13)	0.78494 (10)	0.43669 (5)	0.0216 (3)
O2	0.20704 (13)	1.20577 (10)	0.26233 (4)	0.0204 (3)
S1	0.05767 (5)	0.92249 (4)	0.288760 (16)	0.02009 (14)
S2	−0.06345 (5)	1.11707 (4)	0.399152 (17)	0.02049 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0220 (10)	0.0156 (10)	0.0161 (9)	0.0006 (8)	−0.0039 (8)	−0.0005 (8)
C3	0.0231 (10)	0.0143 (9)	0.0135 (9)	0.0005 (8)	0.0026 (8)	−0.0003 (7)
C4	0.0196 (10)	0.0127 (10)	0.0177 (9)	0.0012 (8)	0.0021 (8)	−0.0015 (8)
C6	0.0210 (10)	0.0103 (9)	0.0157 (9)	0.0008 (7)	0.0008 (8)	−0.0021 (7)
C8	0.0146 (9)	0.0169 (10)	0.0199 (10)	0.0006 (8)	0.0025 (8)	−0.0014 (8)
C9	0.0150 (9)	0.0162 (10)	0.0144 (9)	−0.0011 (8)	0.0025 (7)	0.0018 (8)
C10	0.0199 (10)	0.0184 (10)	0.0125 (9)	0.0005 (8)	−0.0011 (8)	0.0000 (8)
C11	0.0182 (10)	0.0228 (11)	0.0228 (10)	−0.0003 (8)	−0.0003 (8)	0.0022 (9)
C13	0.0135 (9)	0.0188 (10)	0.0201 (10)	−0.0003 (8)	0.0017 (8)	−0.0005 (8)
C14	0.0189 (9)	0.0174 (10)	0.0162 (9)	−0.0017 (8)	0.0027 (8)	−0.0004 (8)
C15	0.0197 (10)	0.0130 (9)	0.0178 (10)	−0.0011 (8)	−0.0010 (8)	−0.0041 (8)
C17	0.0177 (9)	0.0116 (9)	0.0186 (9)	−0.0010 (7)	0.0001 (8)	−0.0034 (8)
C19	0.0146 (9)	0.0280 (11)	0.0241 (10)	0.0026 (8)	−0.0024 (8)	0.0007 (9)
C20	0.0265 (11)	0.0229 (11)	0.0160 (10)	−0.0029 (9)	0.0029 (8)	0.0018 (8)
C21	0.0192 (10)	0.0311 (12)	0.0208 (10)	0.0046 (9)	−0.0030 (8)	−0.0007 (9)
C22	0.0221 (10)	0.0234 (11)	0.0219 (10)	−0.0026 (9)	0.0059 (8)	0.0002 (9)
C3a	0.0182 (9)	0.0124 (10)	0.0165 (9)	0.0013 (7)	0.0021 (8)	−0.0012 (7)
C7a	0.0162 (9)	0.0110 (9)	0.0160 (9)	0.0006 (7)	−0.0005 (7)	−0.0023 (7)
C14a	0.0203 (10)	0.0119 (9)	0.0145 (9)	−0.0010 (7)	−0.0001 (8)	−0.0009 (7)
C18a	0.0157 (9)	0.0103 (9)	0.0182 (9)	−0.0002 (7)	0.0004 (8)	−0.0020 (7)
N1	0.0156 (8)	0.0154 (8)	0.0150 (8)	−0.0017 (6)	0.0005 (6)	−0.0020 (6)
N5	0.0141 (8)	0.0176 (8)	0.0165 (8)	0.0003 (7)	0.0007 (6)	−0.0006 (7)
N7	0.0168 (8)	0.0145 (8)	0.0157 (8)	−0.0010 (6)	−0.0001 (6)	−0.0016 (6)
N12	0.0158 (8)	0.0162 (8)	0.0141 (8)	0.0016 (6)	−0.0007 (6)	0.0008 (6)
N16	0.0156 (8)	0.0180 (8)	0.0166 (8)	0.0006 (7)	−0.0014 (6)	−0.0014 (7)
N18	0.0147 (8)	0.0145 (8)	0.0177 (8)	−0.0001 (6)	0.0011 (6)	−0.0014 (6)
O1	0.0185 (7)	0.0241 (8)	0.0221 (7)	−0.0008 (6)	0.0053 (6)	0.0036 (6)
O2	0.0233 (7)	0.0234 (8)	0.0145 (7)	0.0009 (6)	−0.0029 (6)	0.0014 (6)
S1	0.0213 (3)	0.0229 (3)	0.0160 (3)	0.0006 (2)	−0.00206 (19)	0.0021 (2)
S2	0.0147 (2)	0.0228 (3)	0.0240 (3)	−0.00095 (19)	0.00240 (19)	−0.0013 (2)

Geometric parameters (Å, º)

C2—C3	1.359 (3)	C15—N16	1.427 (2)
C2—N1	1.388 (2)	C15—C14a	1.430 (3)
C2—H2	0.9300	C17—N18	1.298 (2)
C3—C3a	1.429 (3)	C17—N16	1.379 (2)
C3—H3	0.9300	C17—S2	1.7696 (19)
C4—O1	1.235 (2)	C19—N5	1.468 (2)
C4—C3a	1.420 (3)	C19—H19A	0.9600
C4—N5	1.425 (2)	C19—H19B	0.9600
C6—N7	1.305 (2)	C19—H19C	0.9600
C6—N5	1.382 (2)	C20—S1	1.802 (2)
C6—S1	1.7649 (19)	C20—H20A	0.9600
C8—N1	1.466 (2)	C20—H20B	0.9600
C8—C9	1.512 (3)	C20—H20C	0.9600
C8—H8A	0.9700	C21—N16	1.468 (2)
C8—H8B	0.9700	C21—H21A	0.9600
C9—C11	1.320 (3)	C21—H21B	0.9600
C9—C10	1.506 (3)	C21—H21C	0.9600
C10—N12	1.460 (2)	C22—S2	1.804 (2)
C10—H10A	0.9700	C22—H22A	0.9600
C10—H10B	0.9700	C22—H22B	0.9600
C11—H11A	0.9300	C22—H22C	0.9600
C11—H11B	0.9300	C3a—C7a	1.393 (3)
C13—C14	1.363 (3)	C7a—N7	1.357 (2)
C13—N12	1.385 (2)	C7a—N1	1.368 (2)
C13—H13	0.9300	C14a—C18a	1.387 (3)
C14—C14a	1.429 (3)	C18a—N18	1.360 (2)
C14—H14	0.9300	C18a—N12	1.363 (2)
C15—O2	1.232 (2)
C3—C2—N1	109.78 (17)	H19B—C19—H19C	109.5
C3—C2—H2	125.1	S1—C20—H20A	109.5
N1—C2—H2	125.1	S1—C20—H20B	109.5
C2—C3—C3a	106.57 (17)	H20A—C20—H20B	109.5
C2—C3—H3	126.7	S1—C20—H20C	109.5
C3a—C3—H3	126.7	H20A—C20—H20C	109.5
O1—C4—C3a	127.16 (18)	H20B—C20—H20C	109.5
O1—C4—N5	120.32 (17)	N16—C21—H21A	109.5
C3a—C4—N5	112.52 (16)	N16—C21—H21B	109.5
N7—C6—N5	125.22 (17)	H21A—C21—H21B	109.5
N7—C6—S1	120.00 (14)	N16—C21—H21C	109.5
N5—C6—S1	114.78 (14)	H21A—C21—H21C	109.5
N1—C8—C9	110.98 (15)	H21B—C21—H21C	109.5
N1—C8—H8A	109.4	S2—C22—H22A	109.5
C9—C8—H8A	109.4	S2—C22—H22B	109.5
N1—C8—H8B	109.4	H22A—C22—H22B	109.5
C9—C8—H8B	109.4	S2—C22—H22C	109.5
H8A—C8—H8B	108.0	H22A—C22—H22C	109.5
C11—C9—C10	121.36 (18)	H22B—C22—H22C	109.5
C11—C9—C8	122.00 (18)	C7a—C3a—C4	118.87 (17)
C10—C9—C8	116.63 (16)	C7a—C3a—C3	107.31 (17)
N12—C10—C9	111.66 (15)	C4—C3a—C3	133.82 (18)
N12—C10—H10A	109.3	N7—C7a—N1	124.32 (17)
C9—C10—H10A	109.3	N7—C7a—C3a	127.41 (17)
N12—C10—H10B	109.3	N1—C7a—C3a	108.27 (16)
C9—C10—H10B	109.3	C18a—C14a—C14	106.92 (17)
H10A—C10—H10B	107.9	C18a—C14a—C15	118.23 (17)
C9—C11—H11A	120.0	C14—C14a—C15	134.83 (17)
C9—C11—H11B	120.0	N18—C18a—N12	123.44 (16)
H11A—C11—H11B	120.0	N18—C18a—C14a	127.65 (17)
C14—C13—N12	109.61 (16)	N12—C18a—C14a	108.90 (16)
C14—C13—H13	125.2	C7a—N1—C2	108.08 (15)
N12—C13—H13	125.2	C7a—N1—C8	126.51 (15)
C13—C14—C14a	106.62 (17)	C2—N1—C8	125.34 (16)
C13—C14—H14	126.7	C6—N5—C4	122.69 (16)
C14a—C14—H14	126.7	C6—N5—C19	120.28 (16)
O2—C15—N16	119.67 (17)	C4—N5—C19	117.01 (15)
O2—C15—C14a	127.57 (18)	C6—N7—C7a	113.26 (16)
N16—C15—C14a	112.76 (16)	C18a—N12—C13	107.95 (15)
N18—C17—N16	125.42 (17)	C18a—N12—C10	124.82 (15)
N18—C17—S2	118.04 (14)	C13—N12—C10	127.18 (16)
N16—C17—S2	116.53 (14)	C17—N16—C15	122.34 (16)
N5—C19—H19A	109.5	C17—N16—C21	120.60 (16)
N5—C19—H19B	109.5	C15—N16—C21	116.91 (15)
H19A—C19—H19B	109.5	C17—N18—C18a	113.42 (16)
N5—C19—H19C	109.5	C6—S1—C20	100.97 (9)
H19A—C19—H19C	109.5	C17—S2—C22	98.86 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···S2^i	0.97	2.95	3.730 (2)	138
C10—H10B···O1^ii	0.97	2.69	3.454 (3)	136
C20—H20B···O2^i	0.96	2.46	3.355 (3)	155
C11—H11B···O1^iii	0.93	2.54	3.429 (3)	159

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x+1/2, y+1/2, z; (iii) x+1, y, z.

(XV) 7-[2-(4,6-Dimethylsulfanyl-1H-pyrazolo[3,4-d]pyrimidin-1-yl)-2-\ methylidenepropyl]-3-methyl-2-methylsulfanyl-3H-pyrrolo[2,3-d]\ pyrimidin-4(7H)-one

Crystal data

C19H21N7OS3	F(000) = 960
Mr = 459.61	Dx = 1.388 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5170 reflections
a = 9.5436 (7) Å	θ = 3.1–25.4°
b = 11.5329 (8) Å	µ = 0.36 mm^−1
c = 21.0042 (13) Å	T = 293 K
β = 107.943 (3)°	Block, colourless
V = 2199.4 (3) Å^3	0.18 × 0.16 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5277 independent reflections
Radiation source: fine-focus sealed tube	4550 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 28.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.938, Tmax = 0.968	k = −14→15
25081 measured reflections	l = −26→27

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0605P)^2 + 0.3873P] where P = (Fo^2 + 2Fc^2)/3
5277 reflections	(Δ/σ)max = 0.001
275 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.35 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
C3	1.10811 (15)	0.73675 (14)	0.60517 (8)	0.0522 (3)
H3	1.2007	0.7709	0.6155	0.063*
C4	1.02038 (14)	0.77668 (11)	0.71178 (7)	0.0429 (3)
C6	0.78735 (14)	0.70167 (11)	0.69171 (7)	0.0404 (3)
C8	0.80411 (17)	0.58447 (12)	0.49797 (7)	0.0478 (3)
H8A	0.7139	0.5709	0.5090	0.057*
H8B	0.8451	0.5097	0.4922	0.057*
C9	0.76890 (16)	0.65113 (12)	0.43351 (7)	0.0464 (3)
C10	0.72296 (17)	0.77604 (13)	0.43465 (8)	0.0497 (3)
H10A	0.8081	0.8217	0.4588	0.060*
H10B	0.6881	0.8050	0.3891	0.060*
C11	0.7814 (2)	0.60229 (17)	0.37875 (9)	0.0656 (4)
H11A	0.8124	0.5257	0.3797	0.079*
H11B	0.7593	0.6445	0.3391	0.079*
C13	0.46841 (17)	0.74107 (14)	0.44641 (8)	0.0558 (4)
H13	0.4330	0.6912	0.4102	0.067*
C14	0.39220 (16)	0.77547 (14)	0.48795 (8)	0.0535 (4)
H14	0.2967	0.7541	0.4855	0.064*
C15	0.47415 (15)	0.91180 (12)	0.59270 (8)	0.0471 (3)
C17	0.72861 (14)	0.97423 (10)	0.60644 (7)	0.0399 (3)
C19	1.1171 (2)	0.88562 (16)	0.83306 (9)	0.0661 (5)
H19A	1.0327	0.9357	0.8195	0.099*
H19B	1.1959	0.9243	0.8660	0.099*
H19C	1.0919	0.8157	0.8518	0.099*
C20	0.50805 (18)	0.60967 (18)	0.66398 (9)	0.0660 (5)
H20A	0.4961	0.6441	0.6210	0.099*
H20B	0.4159	0.6120	0.6735	0.099*
H20C	0.5391	0.5306	0.6636	0.099*
C21	0.6057 (2)	1.03194 (16)	0.68946 (9)	0.0615 (4)
H21A	0.6807	0.9992	0.7267	0.092*
H21B	0.5114	1.0227	0.6963	0.092*
H21C	0.6252	1.1129	0.6858	0.092*
C22	0.99998 (19)	1.05366 (16)	0.60710 (11)	0.0680 (5)
H22A	1.0240	0.9746	0.6005	0.102*
H22B	1.0884	1.0952	0.6299	0.102*
H22C	0.9538	1.0893	0.5645	0.102*
C3a	1.01932 (14)	0.73587 (11)	0.64849 (7)	0.0424 (3)
C7a	0.89082 (14)	0.67757 (11)	0.61202 (6)	0.0388 (3)
C14a	0.48664 (14)	0.85051 (11)	0.53603 (7)	0.0432 (3)
C18a	0.61838 (14)	0.85819 (11)	0.52096 (7)	0.0393 (3)
N1	0.90832 (13)	0.64585 (10)	0.55300 (6)	0.0450 (3)
N2	1.04233 (14)	0.68308 (12)	0.54847 (7)	0.0543 (3)
N5	0.90479 (13)	0.75985 (10)	0.73323 (6)	0.0446 (3)
N7	0.77153 (12)	0.65782 (9)	0.63174 (5)	0.0394 (2)
N12	0.60722 (13)	0.79150 (10)	0.46605 (6)	0.0457 (3)
N16	0.60547 (13)	0.97236 (10)	0.62774 (6)	0.0444 (3)
N18	0.74044 (12)	0.91946 (9)	0.55404 (6)	0.0405 (2)
O1	0.36719 (13)	0.91639 (12)	0.61324 (7)	0.0695 (3)
S1	1.17455 (4)	0.85051 (4)	0.76188 (2)	0.05714 (12)
S2	0.64386 (5)	0.68851 (4)	0.72691 (2)	0.05909 (13)
S3	0.87678 (4)	1.05727 (3)	0.65612 (2)	0.05213 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3	0.0366 (7)	0.0552 (8)	0.0666 (9)	−0.0013 (6)	0.0190 (6)	0.0017 (7)
C4	0.0394 (6)	0.0355 (6)	0.0478 (7)	−0.0013 (5)	0.0047 (5)	0.0042 (5)
C6	0.0409 (6)	0.0384 (6)	0.0423 (6)	−0.0023 (5)	0.0135 (5)	0.0050 (5)
C8	0.0532 (8)	0.0440 (7)	0.0496 (7)	−0.0034 (6)	0.0209 (6)	−0.0059 (6)
C9	0.0477 (7)	0.0495 (7)	0.0454 (7)	−0.0039 (6)	0.0193 (6)	−0.0066 (6)
C10	0.0562 (8)	0.0504 (8)	0.0480 (7)	−0.0010 (6)	0.0240 (6)	0.0000 (6)
C11	0.0862 (12)	0.0644 (10)	0.0525 (9)	0.0011 (9)	0.0307 (9)	−0.0090 (8)
C13	0.0481 (8)	0.0562 (9)	0.0573 (9)	−0.0066 (7)	0.0079 (7)	−0.0104 (7)
C14	0.0386 (7)	0.0552 (8)	0.0631 (9)	−0.0058 (6)	0.0104 (6)	−0.0038 (7)
C15	0.0416 (7)	0.0451 (7)	0.0587 (8)	−0.0013 (5)	0.0214 (6)	0.0025 (6)
C17	0.0382 (6)	0.0324 (6)	0.0492 (7)	−0.0001 (5)	0.0137 (5)	0.0034 (5)
C19	0.0668 (11)	0.0543 (9)	0.0669 (10)	−0.0068 (8)	0.0055 (8)	−0.0169 (8)
C20	0.0481 (8)	0.0857 (12)	0.0652 (10)	−0.0212 (8)	0.0189 (7)	0.0009 (9)
C21	0.0677 (10)	0.0660 (10)	0.0588 (9)	−0.0058 (8)	0.0311 (8)	−0.0138 (8)
C22	0.0526 (9)	0.0650 (10)	0.0906 (13)	−0.0173 (8)	0.0281 (9)	−0.0033 (9)
C3a	0.0348 (6)	0.0396 (6)	0.0515 (7)	−0.0005 (5)	0.0112 (5)	0.0047 (5)
C7a	0.0380 (6)	0.0364 (6)	0.0415 (6)	0.0012 (5)	0.0113 (5)	0.0036 (5)
C14a	0.0362 (6)	0.0401 (7)	0.0531 (7)	0.0004 (5)	0.0135 (6)	0.0024 (6)
C18a	0.0379 (6)	0.0342 (6)	0.0459 (7)	0.0024 (5)	0.0131 (5)	0.0031 (5)
N1	0.0414 (6)	0.0490 (6)	0.0477 (6)	−0.0014 (5)	0.0182 (5)	−0.0012 (5)
N2	0.0446 (6)	0.0598 (7)	0.0659 (8)	−0.0001 (6)	0.0277 (6)	−0.0002 (6)
N5	0.0443 (6)	0.0432 (6)	0.0436 (6)	−0.0050 (5)	0.0096 (5)	0.0008 (5)
N7	0.0381 (5)	0.0385 (5)	0.0418 (5)	−0.0033 (4)	0.0124 (4)	0.0026 (4)
N12	0.0433 (6)	0.0457 (6)	0.0484 (6)	−0.0012 (5)	0.0144 (5)	−0.0049 (5)
N16	0.0454 (6)	0.0425 (6)	0.0496 (6)	−0.0021 (5)	0.0212 (5)	−0.0028 (5)
N18	0.0380 (5)	0.0357 (5)	0.0498 (6)	−0.0011 (4)	0.0164 (5)	0.0007 (4)
O1	0.0535 (6)	0.0814 (8)	0.0872 (9)	−0.0120 (6)	0.0416 (6)	−0.0147 (7)
S1	0.0435 (2)	0.0550 (2)	0.0632 (2)	−0.01015 (15)	0.00221 (17)	−0.00193 (17)
S2	0.0554 (2)	0.0764 (3)	0.0528 (2)	−0.01499 (19)	0.02742 (18)	−0.00529 (18)
S3	0.0477 (2)	0.0447 (2)	0.0608 (2)	−0.00816 (14)	0.01203 (16)	−0.00593 (15)

Geometric parameters (Å, º)

C3—N2	1.317 (2)	C15—N16	1.4254 (18)
C3—C3a	1.4215 (19)	C17—N18	1.3037 (17)
C3—H3	0.9300	C17—N16	1.3806 (17)
C4—N5	1.3281 (18)	C17—S3	1.7597 (13)
C4—C3a	1.407 (2)	C19—S1	1.790 (2)
C4—S1	1.7445 (13)	C19—H19A	0.9600
C6—N7	1.3222 (17)	C19—H19B	0.9600
C6—N5	1.3655 (17)	C19—H19C	0.9600
C6—S2	1.7518 (13)	C20—S2	1.7884 (18)
C8—N1	1.4552 (18)	C20—H20A	0.9600
C8—C9	1.502 (2)	C20—H20B	0.9600
C8—H8A	0.9700	C20—H20C	0.9600
C8—H8B	0.9700	C21—N16	1.4664 (19)
C9—C11	1.319 (2)	C21—H21A	0.9600
C9—C10	1.508 (2)	C21—H21B	0.9600
C10—N12	1.4615 (18)	C21—H21C	0.9600
C10—H10A	0.9700	C22—S3	1.7861 (18)
C10—H10B	0.9700	C22—H22A	0.9600
C11—H11A	0.9300	C22—H22B	0.9600
C11—H11B	0.9300	C22—H22C	0.9600
C13—C14	1.356 (2)	C3a—C7a	1.4014 (18)
C13—N12	1.3880 (19)	C7a—N7	1.3453 (16)
C13—H13	0.9300	C7a—N1	1.3514 (17)
C14—C14a	1.421 (2)	C14a—C18a	1.3906 (18)
C14—H14	0.9300	C18a—N18	1.3566 (17)
C15—O1	1.2256 (17)	C18a—N12	1.3628 (17)
C15—C14a	1.421 (2)	N1—N2	1.3799 (16)
N2—C3—C3a	111.30 (12)	S2—C20—H20B	109.5
N2—C3—H3	124.3	H20A—C20—H20B	109.5
C3a—C3—H3	124.3	S2—C20—H20C	109.5
N5—C4—C3a	120.43 (12)	H20A—C20—H20C	109.5
N5—C4—S1	120.07 (11)	H20B—C20—H20C	109.5
C3a—C4—S1	119.50 (11)	N16—C21—H21A	109.5
N7—C6—N5	128.81 (12)	N16—C21—H21B	109.5
N7—C6—S2	119.62 (10)	H21A—C21—H21B	109.5
N5—C6—S2	111.57 (10)	N16—C21—H21C	109.5
N1—C8—C9	112.04 (12)	H21A—C21—H21C	109.5
N1—C8—H8A	109.2	H21B—C21—H21C	109.5
C9—C8—H8A	109.2	S3—C22—H22A	109.5
N1—C8—H8B	109.2	S3—C22—H22B	109.5
C9—C8—H8B	109.2	H22A—C22—H22B	109.5
H8A—C8—H8B	107.9	S3—C22—H22C	109.5
C11—C9—C8	120.81 (15)	H22A—C22—H22C	109.5
C11—C9—C10	121.79 (15)	H22B—C22—H22C	109.5
C8—C9—C10	117.38 (12)	C7a—C3a—C4	115.29 (12)
N12—C10—C9	112.80 (12)	C7a—C3a—C3	104.33 (12)
N12—C10—H10A	109.0	C4—C3a—C3	140.34 (13)
C9—C10—H10A	109.0	N7—C7a—N1	126.30 (12)
N12—C10—H10B	109.0	N7—C7a—C3a	126.44 (12)
C9—C10—H10B	109.0	N1—C7a—C3a	107.25 (12)
H10A—C10—H10B	107.8	C18a—C14a—C15	118.30 (12)
C9—C11—H11A	120.0	C18a—C14a—C14	107.28 (12)
C9—C11—H11B	120.0	C15—C14a—C14	134.40 (13)
H11A—C11—H11B	120.0	N18—C18a—N12	123.93 (12)
C14—C13—N12	109.76 (13)	N18—C18a—C14a	127.63 (12)
C14—C13—H13	125.1	N12—C18a—C14a	108.43 (12)
N12—C13—H13	125.1	C7a—N1—N2	110.98 (12)
C13—C14—C14a	106.67 (13)	C7a—N1—C8	127.80 (12)
C13—C14—H14	126.7	N2—N1—C8	121.19 (12)
C14a—C14—H14	126.7	C3—N2—N1	106.12 (12)
O1—C15—C14a	127.62 (14)	C4—N5—C6	117.35 (12)
O1—C15—N16	119.49 (14)	C6—N7—C7a	111.68 (11)
C14a—C15—N16	112.90 (12)	C18a—N12—C13	107.86 (12)
N18—C17—N16	124.74 (12)	C18a—N12—C10	125.30 (12)
N18—C17—S3	120.11 (10)	C13—N12—C10	126.83 (13)
N16—C17—S3	115.15 (10)	C17—N16—C15	122.76 (12)
S1—C19—H19A	109.5	C17—N16—C21	120.62 (12)
S1—C19—H19B	109.5	C15—N16—C21	116.61 (12)
H19A—C19—H19B	109.5	C17—N18—C18a	113.62 (11)
S1—C19—H19C	109.5	C4—S1—C19	101.29 (8)
H19A—C19—H19C	109.5	C6—S2—C20	102.41 (7)
H19B—C19—H19C	109.5	C17—S3—C22	101.35 (8)
S2—C20—H20A	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^i	0.93	2.32	3.1901 (19)	155
C8—H8B···N2^ii	0.97	2.72	3.674 (2)	169

Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1.