2-Ethyl­sulfanyl-7-(furan-2-yl)-4-(thio­phen-2-yl)pyrazolo­[1,5-a][1,3,5]triazine: π-stacked chains of hydrogen-bonded R₂²(10) dimers

In the title compound, C₁₅H₁₂N₄OS₂, the bond distances in the fused heterocyclic system show evidence for aromatic-type delocalization in the pyrazole ring with some bond fixation in the triazine ring. The thio­phenyl substituent is slightly disordered over two sets of atomic sites having occupancies of 0.934 (4) and 0.066 (4). The non-H atoms in the entire mol­ecule are nearly coplanar, with the planes of the furanyl substituent and the major orientation of the thio­phenyl substituent making dihedral angles of 5.72 (17) and 1.8 (3)°, respectively, with that of the fused ring system. Mol­ecules are linked into centrosymmetric R₂²(10) dimers by C—H...O hydrogen bonds and these dimers are further linked into chains by a single π–π stacking inter­action. Comparisons are made with some related 4,7-di­aryl-2-(ethyl­sulfan­yl)pyra­zolo­[1,5-a][1,3,5]triazines which contain variously substituted aryl groups in place of the furanyl and thio­phenyl substituents in the title compound.

S1. Introduction

The pyrazolo­[1,5-a][1,3,5]triazine ring can be found in the structures of a number of different biologically active compounds, including anti-inflammatory (Raboisson et al., 2008), anti­tumoural (Popowycz et al., 2009), anti­depressant (Gilligan et al., 2009; Saito et al., 2011) and anti­viral agents (Gudmundsson et al., 2009). In addition, the presence of the furan-2-yl or thio­phen-2-yl moieties in the structure of some analogues of pyrazolo­triazines, such as purines, pyrazolo­pyrimidines and triazolotriazines, are important determinants of their biological properties (Braendvang & Gundersen, 2007; Gillespie et al., 2008; Federico et al., 2011). The insertion of the thio­phen-2-yl and furan-2-yl units into such compounds has been usually mediated by a C—C coupling process based on the Stille reaction (Braendvang & Gundersen 2007; Gillespie et al., 2008). Accordingly, it is of inter­est to incorporate furanyl and thio­phenyl substituents into a pyrazolo­[1,5-a][1,3,5]triazine. [A missing N atom was added to (I); please check the other structures]

Pyrazolo­[1,5-a][1,3,5]triazines can be readily synthesized from 5-amino­pyrazoles and an appropriate bis-electrophilic reagent (Insuasty et al., 2006, 2012) and we report here the molecular and supra­molecular structure of 2-ethyl­sulfanyl-7-(furan-2-yl)-4-(thio­phen-2-yl)pyrazolo­[1,5-a][1,3,5]triazine, (I) (Fig. 1), which was obtained from the reaction of S,S-di­ethyl 2-thenoylimidodi­thio­carbonate with the commercially available 5-amino-3-(furan-2-yl)-1H-pyrazole (see Scheme) using microwave irradiation under solvent-free conditions, as an alternative method to the usual Stille reaction. The purposes of the present study are: (i) the confirmation of the molecular constitution of the title compound as (I), rather than the alternative (Ia) (see Scheme); (ii) the exploration of the supra­molecular assembly in (I); (iii) the comparison of (I) with the related compounds (II)–(IV) (Insuasty et al., 2008), which each carry two aryl substituents in place of the furanyl and thio­phenyl substituents present in (I).

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of S,S-di­ethyl 2-thenoylimidodi­thio­carbonate (0.015 mol) and 5-amino-3-(furan-2-yl)-1H-pyrazole (0.015 mol) was subjected to microwave irradiation in absence of solvent (maximum power 300 W, for 12 min at a temperature of 433 K), using a focused microwave reactor (CEM discover). When the reaction was complete, as indicated by thin-layer chromatography, the crude product was dissolved in chloro­form (3.0 ml) and purified by column chromatography on silica gel, using a mixture of hexanes/ethyl acetate (9:1 v/v) as eluent to give the title compound, (I). After removal of the solvent under reduced pressure, crystallization from ethyl acetate, at ambient temperature and in the presence of air, provided yellow crystals suitable for single-crystal X-ray diffraction (yield 91%, m.p. 382 K). MS (70 eV) m/z (%): 328 (100, M⁺), 313 (22), 268 (38), 219 (35), 191 (93), 94 (55), 27 (29). Analysis found: C 54.8, H 3.7, N 17.0%; C₁₅H₁₂N₄OS₂ requires: C 54.9, H 3.7, N 17.1%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (heterocyclic), 0.98 (CH₃) or 0.99 Å (CH₂) and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms. Five low-angle reflections (100, 110, 101, 011 and 011) which had been attenuated by the beam stop were omitted from the final refinements. Examination of the refined structure at this stage revealed significant differences between the two S—C distances [1.720 (3) and 1.696 (4) Å for S41—C42 and S41—C45, respectively] and between the two formal C—C double bonds (1.415 (5) Å and 1.362 (5) Å for C42—C43 and C44—C45 respectively) in the thio­phenyl unit, suggesting that this ring might, in fact, exhibit orientational disorder, effectively involving a rotation about the C4—C42 bond (cf. Fig. 1). This disorder was modelled using two orientations having unequal occupancies. The bonded distances and the one-angle non-bonded distances in the minor orientation were constrained to be identical to the corresponding distances in the major orientation subject to uncertainties of 0.005 Å and 0.01 Å respectively, and the anisotropic displacement parameters of pairs of atoms occupying the same approximate volume of physical space were constrained to be equal: in addition, the atomic coordinates of atoms C42 and C52 (cf. Fig. 1) were constrained to be identical. Under these conditions the refined site occupancies were 0.934 (4) and 0.066 Å, with no unsatisfactory features in the bonded distances for the thio­phenyl ring, and significantly lower R values.

S3. Results and discussion

Within the molecule of (I), the thio­phen-2-yl group exhibits orientational disorder over two sets of atomic sites, with refined occupancies of 0.934 (4) and 0.066 (4), such that the two orientations are related by a rotation of approximately 180° and the exocyclic bond from atom C4 (Fig. 1 and Table 2). Because of the low occupancy of the minor disorder component, the discussion here will concentrate primarily on the major form. The non-H atoms in the molecule of (I) do not deviated markedly from coplanarity. Thus, in the pyrazolo­triazine system, the maximum deviation from the mean plane of the fused ring atoms is only 0.013 (3) Å for atom C4, with an r.m.s. deviation of 0.0089 Å. The dihedral angles between this fused system and furanyl and thio­phenyl substituents are 5.5 (2) and 0.95 (18)°, respectively. Similarly the ethyl­sulfanyl substituent lies close to the fused ring plane, with deviations from it of 0.090 (4) and 0.109 (4) Å for atoms C21 and C22, respectively.

The pyrazolo­triazine system exhibits some inter­esting bond distances (Table 2). While there is clear evidence for some bond fixation in the triazine ring, in the pyrazole ring the N5—N6 distance is inter­mediate between the C2—N3 distance on the one hand and the N1—C2 and N3—C4 distances on the other. Similarly, the C7—C8 and C8—C8A distances differ by only ca 0.04 Å, even though these are formally single and double bonds, respectively. Accordingly, the best single representation of the electronic structure in the fused ring component of (I) contains a delocalized 6π system in the pyrazole ring (cf. Scheme). In the furanyl and thio­phenyl substituents, the corresponding pairs of bonds in each ring have very similar distances (Table 2), indicating that no un-modelled disorder remains.

The supra­molecular assembly in compound (I) is dominated by a single C—H···O hydrogen bond (Table 3); inversion-related pairs of molecules are thereby linked to form cyclic centrosymmetric dimers (Fig. 2) characterized by an R₂²(10) motif (Bernstein et al., 1995). Dimers of this type are weakly linked by a π–π stacking inter­action. The thio­phenyl ring in the molecule at (x, y, z) and the triazine ring in the molecule at (-x, -y+1, -z+1) make a dihedral angle of only 1.83 (17)°; the ring-centroid separation is 3.794 (2) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other is 3.3980 (14) Å, corresponding to a ring-centroid offset of ca 1.69 Å. This inter­action links the hydrogen-bonded dimers into a π-stacked chain running parallel to the [110] direction (Fig. 2). There is also a C—H···π contact in the structure of (I) (Table 3); if significant, this would link the hydrogen-bonded dimers into a chain running parallel to the [010] direction, so generating a sheet lying parallel to (001).

It is of inter­est briefly to compare the molecular structure and the supra­molecular assembly in (I) with those of the related compounds (II)–(IV) (Insuasty et al., 2008) (see Scheme). In each of compounds (II)–(IV) the pattern of the bond distances in the fused heterocyclic component is very similar to that found here in (I), consistent with aromatic-type delocalization in their pyrazole rings. However, in each of compounds (I)–(IV), the conformation of the ethyl­sulfanyl substituent differ, as shown by the relevant torsion angles. Thus, the torsion angle N1—C2—S21—C21 has values of -0.74 (16), 15.00 (16) and 179.6 (2)° in (II)–(IV), respectively, as opposed to a value of -178.2 (3)° in (I), and the torsion angle C2—S21—C21—C22 has values of 177.01 (12), 74.19 (14) and -80.3 (3)° in (II)–(IV) as opposed to a value of 179.5 (3)° in (I). It seems likely that these different conformations for the ethyl­sulfanyl group, depending only on rotations about single bonds, reflect the free space available in the molecular assemblies dominated by the effects of the various ring systems. On the other hand, the orientations of the various aryl rings in compounds (II)–(IV) relative to the fused heterocyclic component are all fairly similar; in compounds (II) and (IV), the aryl rings are nearly coplanar with the heterocyclic system, while in (II), the unsubstituted phenyl ring is disordered over two sets of atomic sites having equal occupancy [cf. the unequal occupancies of the two thio­phenyl orientations in (I)], making dihedral angles of 20.77 (13) and 25.99 (13)° with the heterocyclic system.

The patterns of supra­molecular assembly also differ in the four compounds. By contrast with (I), there are no hydrogen bonds in any of the structures of (II)–(IV) and, indeed, there are no direction-specific inter­molecular inter­actions of any kind in the structure of (II). In compounds (III) and (IV), however, the molecules are linked into centrosymmetric dimers, by means of different types of π–π stacking inter­action in the two cases.

Related literature

For related literature, see: Bernstein et al. (1995); Braendvang & Gundersen (2007); Federico et al. (2011); Gillespie et al. (2008); Gilligan et al. (2009); Gudmundsson et al. (2009); Insuasty et al. (2006, 2008, 2012); Popowycz et al. (2009); Raboisson et al. (2008); Saito et al. (2011).

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The major and minor orientations of the disordered thiophenyl group have occupancies of 0.934 (4) and 0.066 (4), respectively, and the atomic coordinates of the C42 and C52 sites were constrained to be identical.
	Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a π-stacked chain of hydrogen-bonded R2^2(10) dimers running parallel to the [110] direction. Hydrogen bonds are shown as dashed and and, for the sake of clarity, only the major orientation of the disordered thiophenyl substituent is shown and H atoms not involved in the motif shown have been omitted.

2-Ethylsulfanyl-7-(furan-2-yl)-4-(thiophen-2-yl)pyrazolo[1,5-a][1,3,5]triazine

Crystal data

C15H12N4OS2	Z = 2
Mr = 328.41	F(000) = 340
Triclinic, P1	Dx = 1.523 Mg m^−3
a = 7.4999 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8965 (5) Å	Cell parameters from 3294 reflections
c = 11.2806 (9) Å	θ = 2.8–27.5°
α = 83.338 (6)°	µ = 0.38 mm^−1
β = 73.354 (5)°	T = 120 K
γ = 86.406 (6)°	Block, colourless
V = 715.92 (8) Å^3	0.39 × 0.21 × 0.11 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	3289 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2068 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.6°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.522, Tmax = 0.746	l = −14→14
15356 measured reflections

Refinement

Refinement on F^2	10 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0613P)^2 + 0.8572P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3289 reflections	Δρmax = 0.40 e Å^−3
213 parameters	Δρmin = −0.45 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.3567 (4)	0.6622 (3)	0.3251 (2)	0.0221 (6)
C2	0.2931 (4)	0.5363 (4)	0.3043 (3)	0.0220 (7)
N3	0.2207 (4)	0.4175 (3)	0.3907 (2)	0.0215 (6)
C4	0.2142 (4)	0.4281 (3)	0.5075 (3)	0.0199 (6)
N5	0.2743 (4)	0.5560 (3)	0.5386 (2)	0.0204 (6)
N6	0.2739 (4)	0.5888 (3)	0.6545 (2)	0.0234 (6)
C7	0.3459 (4)	0.7271 (3)	0.6323 (3)	0.0221 (7)
C8	0.3941 (4)	0.7845 (3)	0.5056 (3)	0.0225 (7)
H8	0.4476	0.8790	0.4697	0.027*
C8A	0.3468 (5)	0.6740 (4)	0.4453 (3)	0.0232 (7)
S21	0.30545 (13)	0.51970 (9)	0.14970 (8)	0.0268 (2)
C21	0.2002 (5)	0.3394 (4)	0.1598 (3)	0.0275 (8)
H21A	0.2719	0.2577	0.1949	0.033*
H21B	0.0712	0.3415	0.2151	0.033*
C22	0.1994 (6)	0.3094 (4)	0.0297 (3)	0.0359 (9)
H22A	0.1239	0.3884	−0.0030	0.054*
H22B	0.1465	0.2104	0.0335	0.054*
H22C	0.3272	0.3102	−0.0249	0.054*
S41	0.08077 (15)	0.14564 (10)	0.54666 (8)	0.0251 (3)	0.934 (4)
C42	0.1431 (4)	0.3023 (3)	0.5997 (3)	0.0219 (7)	0.934 (4)
C43	0.1183 (9)	0.2814 (6)	0.7253 (5)	0.0220 (9)	0.934 (4)
H43	0.1487	0.3546	0.7708	0.026*	0.934 (4)
C44	0.0425 (17)	0.1396 (8)	0.7807 (4)	0.0262 (8)	0.934 (4)
H44	0.0137	0.1073	0.8672	0.031*	0.934 (4)
C45	0.0162 (14)	0.0554 (6)	0.6936 (5)	0.0289 (12)	0.934 (4)
H45	−0.0329	−0.0432	0.7129	0.035*	0.934 (4)
S51	0.128 (4)	0.297 (3)	0.7547 (9)	0.0220 (9)	0.066 (4)
C52	0.1431 (4)	0.3023 (3)	0.5997 (3)	0.0219 (7)	0.066 (4)
C53	0.064 (9)	0.179 (4)	0.576 (3)	0.0251 (3)	0.066 (4)
H53	0.0486	0.1668	0.4969	0.030*	0.066 (4)
C54	0.01 (2)	0.072 (9)	0.682 (4)	0.0289 (12)	0.066 (4)
H54	−0.0458	−0.0226	0.6811	0.035*	0.066 (4)
C55	0.03 (3)	0.123 (10)	0.785 (4)	0.0262 (8)	0.066 (4)
H55	0.0020	0.0674	0.8646	0.031*	0.066 (4)
O71	0.4518 (3)	0.9367 (2)	0.7047 (2)	0.0272 (5)
C72	0.3638 (5)	0.8002 (3)	0.7358 (3)	0.0218 (7)
C73	0.3124 (5)	0.7677 (4)	0.8608 (3)	0.0252 (7)
H73	0.2502	0.6801	0.9061	0.030*
C74	0.3690 (5)	0.8893 (4)	0.9119 (3)	0.0278 (8)
H74	0.3517	0.8990	0.9975	0.033*
C75	0.4521 (5)	0.9883 (4)	0.8145 (3)	0.0287 (8)
H75	0.5036	1.0808	0.8211	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0263 (15)	0.0196 (13)	0.0205 (14)	−0.0038 (11)	−0.0065 (11)	−0.0011 (11)
C2	0.0189 (16)	0.0225 (16)	0.0229 (16)	0.0000 (13)	−0.0037 (13)	−0.0017 (12)
N3	0.0226 (15)	0.0199 (13)	0.0222 (14)	−0.0007 (11)	−0.0066 (11)	−0.0024 (11)
C4	0.0159 (15)	0.0202 (15)	0.0235 (16)	0.0001 (12)	−0.0056 (12)	−0.0028 (12)
N5	0.0233 (15)	0.0186 (13)	0.0191 (13)	−0.0028 (11)	−0.0052 (11)	−0.0022 (10)
N6	0.0265 (15)	0.0240 (14)	0.0192 (14)	−0.0030 (12)	−0.0058 (11)	−0.0011 (11)
C7	0.0201 (17)	0.0184 (15)	0.0269 (17)	−0.0018 (13)	−0.0051 (13)	−0.0023 (13)
C8	0.0239 (17)	0.0190 (15)	0.0232 (16)	−0.0002 (13)	−0.0051 (13)	−0.0001 (12)
C8A	0.0240 (18)	0.0220 (16)	0.0215 (16)	−0.0005 (13)	−0.0041 (13)	0.0000 (13)
S21	0.0347 (5)	0.0250 (4)	0.0200 (4)	−0.0045 (4)	−0.0057 (3)	−0.0025 (3)
C21	0.0279 (19)	0.0293 (18)	0.0245 (17)	−0.0047 (15)	−0.0049 (14)	−0.0041 (14)
C22	0.040 (2)	0.041 (2)	0.0263 (19)	−0.0061 (17)	−0.0058 (16)	−0.0085 (16)
S41	0.0321 (6)	0.0208 (5)	0.0231 (5)	−0.0059 (4)	−0.0074 (4)	−0.0031 (3)
C42	0.0204 (17)	0.0221 (16)	0.0225 (16)	−0.0032 (13)	−0.0045 (13)	−0.0024 (13)
C43	0.029 (2)	0.021 (2)	0.018 (2)	−0.0044 (15)	−0.008 (2)	−0.0053 (19)
C44	0.030 (2)	0.025 (2)	0.0218 (17)	−0.0025 (19)	−0.0056 (15)	0.0022 (13)
C45	0.031 (2)	0.021 (2)	0.033 (2)	−0.002 (2)	−0.0081 (18)	0.0022 (14)
S51	0.029 (2)	0.021 (2)	0.018 (2)	−0.0044 (15)	−0.008 (2)	−0.0053 (19)
C52	0.0204 (17)	0.0221 (16)	0.0225 (16)	−0.0032 (13)	−0.0045 (13)	−0.0024 (13)
C53	0.0321 (6)	0.0208 (5)	0.0231 (5)	−0.0059 (4)	−0.0074 (4)	−0.0031 (3)
C54	0.031 (2)	0.021 (2)	0.033 (2)	−0.002 (2)	−0.0081 (18)	0.0022 (14)
C55	0.030 (2)	0.025 (2)	0.0218 (17)	−0.0025 (19)	−0.0056 (15)	0.0022 (13)
O71	0.0328 (14)	0.0225 (12)	0.0270 (12)	−0.0081 (10)	−0.0076 (10)	−0.0036 (9)
C72	0.0244 (17)	0.0161 (15)	0.0246 (16)	−0.0012 (13)	−0.0069 (13)	−0.0004 (12)
C73	0.0266 (18)	0.0248 (17)	0.0249 (17)	−0.0058 (14)	−0.0089 (14)	0.0014 (13)
C74	0.0301 (19)	0.0320 (18)	0.0206 (16)	−0.0015 (15)	−0.0057 (14)	−0.0033 (14)
C75	0.037 (2)	0.0218 (17)	0.0321 (19)	−0.0060 (15)	−0.0137 (16)	−0.0094 (14)

Geometric parameters (Å, º)

N1—C2	1.315 (4)	C42—C43	1.366 (6)
C2—N3	1.375 (4)	C43—C44	1.418 (6)
C2—S21	1.743 (3)	C43—H43	0.9500
N3—C4	1.319 (4)	C44—C45	1.366 (5)
C4—N5	1.366 (4)	C45—S41	1.705 (4)
C4—C42	1.451 (4)	C44—H44	0.9500
N5—N6	1.372 (4)	C45—H45	0.9500
N6—C7	1.342 (4)	S51—C55	1.706 (7)
C7—C8	1.411 (4)	C53—C54	1.419 (7)
C7—C72	1.443 (4)	C53—H53	0.9500
C8—C8A	1.375 (5)	C54—C55	1.366 (7)
C8A—N1	1.352 (4)	C54—H54	0.9500
N5—C8A	1.412 (4)	C55—H55	0.9500
C8—H8	0.9500	O71—C72	1.379 (4)
S21—C21	1.810 (3)	C72—C73	1.352 (4)
C21—C22	1.523 (5)	C73—C74	1.423 (5)
C21—H21A	0.9900	C73—H73	0.9500
C21—H21B	0.9900	C74—C75	1.351 (5)
C22—H22A	0.9800	C75—O71	1.371 (4)
C22—H22B	0.9800	C74—H74	0.9500
C22—H22C	0.9800	C75—H75	0.9500
S41—C42	1.719 (3)
C2—N1—C8A	115.2 (3)	C45—S41—C42	91.32 (18)
N1—C2—N3	127.1 (3)	C43—C42—C4	131.8 (3)
N1—C2—S21	115.6 (2)	C43—C42—S41	111.3 (3)
N3—C2—S21	117.3 (2)	C4—C42—S41	116.9 (2)
C4—N3—C2	117.7 (3)	C42—C43—C44	113.2 (4)
N3—C4—N5	119.6 (3)	C42—C43—H43	123.4
N3—C4—C42	118.6 (3)	C44—C43—H43	123.4
N5—C4—C42	121.8 (3)	C45—C44—C43	111.2 (4)
C4—N5—N6	127.9 (3)	C45—C44—H44	124.4
C4—N5—C8A	119.9 (3)	C43—C44—H44	124.4
N6—N5—C8A	112.3 (3)	C44—C45—S41	113.0 (3)
C7—N6—N5	103.2 (2)	C44—C45—H45	123.5
N6—C7—C8	113.7 (3)	S41—C45—H45	123.5
N6—C7—C72	118.7 (3)	C54—C53—H53	123.5
C8—C7—C72	127.6 (3)	C55—C54—C53	111.1 (7)
C8A—C8—C7	105.1 (3)	C55—C54—H54	124.4
C8A—C8—H8	127.4	C53—C54—H54	124.4
C7—C8—H8	127.4	C54—C55—S51	112.9 (6)
N1—C8A—C8	133.6 (3)	C54—C55—H55	123.6
N1—C8A—N5	120.6 (3)	S51—C55—H55	123.6
C8—C8A—N5	105.7 (3)	C75—O71—C72	106.4 (2)
C2—S21—C21	102.51 (15)	C73—C72—O71	109.7 (3)
C22—C21—S21	108.6 (2)	C73—C72—C7	135.1 (3)
C22—C21—H21A	110.0	O71—C72—C7	115.3 (3)
S21—C21—H21A	110.0	C72—C73—C74	107.1 (3)
C22—C21—H21B	110.0	C72—C73—H73	126.4
S21—C21—H21B	110.0	C74—C73—H73	126.4
H21A—C21—H21B	108.3	C75—C74—C73	106.3 (3)
C21—C22—H22A	109.5	C75—C74—H74	126.8
C21—C22—H22B	109.5	C73—C74—H74	126.8
H22A—C22—H22B	109.5	C74—C75—O71	110.5 (3)
C21—C22—H22C	109.5	C74—C75—H75	124.7
H22A—C22—H22C	109.5	O71—C75—H75	124.7
H22B—C22—H22C	109.5
C8A—N1—C2—N3	−0.6 (5)	N3—C2—S21—C21	2.5 (3)
C8A—N1—C2—S21	−179.9 (2)	C2—S21—C21—C22	179.5 (3)
N1—C2—N3—C4	−0.5 (5)	N3—C4—C42—C43	−179.3 (5)
S21—C2—N3—C4	178.8 (2)	N5—C4—C42—C43	0.9 (7)
C2—N3—C4—N5	1.6 (4)	N3—C4—C42—S41	2.3 (4)
C2—N3—C4—C42	−178.3 (3)	N5—C4—C42—S41	−177.6 (2)
N3—C4—N5—N6	178.2 (3)	C45—S41—C42—C43	1.5 (5)
C42—C4—N5—N6	−1.9 (5)	C45—S41—C42—C4	−179.8 (4)
N3—C4—N5—C8A	−1.5 (4)	C4—C42—C43—C44	179.6 (7)
C42—C4—N5—C8A	178.4 (3)	S41—C42—C43—C44	−1.9 (8)
C4—N5—N6—C7	−179.7 (3)	C42—C43—C44—C45	1.4 (12)
C8A—N5—N6—C7	0.1 (3)	C43—C44—C45—S41	−0.3 (13)
N5—N6—C7—C8	−0.4 (3)	C42—S41—C45—C44	−0.7 (8)
N5—N6—C7—C72	178.9 (3)	C53—C54—C55—S51	0 (19)
N6—C7—C8—C8A	0.5 (4)	C75—O71—C72—C73	−0.5 (4)
C72—C7—C8—C8A	−178.7 (3)	C75—O71—C72—C7	179.0 (3)
C2—N1—C8A—C8	−178.9 (4)	N6—C7—C72—C73	−5.4 (6)
C2—N1—C8A—N5	0.7 (4)	C8—C7—C72—C73	173.8 (4)
C7—C8—C8A—N1	179.2 (3)	N6—C7—C72—O71	175.3 (3)
C7—C8—C8A—N5	−0.4 (3)	C8—C7—C72—O71	−5.5 (5)
C4—N5—C8A—N1	0.3 (4)	O71—C72—C73—C74	0.4 (4)
N6—N5—C8A—N1	−179.4 (3)	C7—C72—C73—C74	−178.9 (4)
C4—N5—C8A—C8	−180.0 (3)	C72—C73—C74—C75	−0.2 (4)
N6—N5—C8A—C8	0.2 (4)	C73—C74—C75—O71	−0.1 (4)
N1—C2—S21—C21	−178.1 (2)	C72—O71—C75—C74	0.3 (4)

Hydrogen-bond geometry (Å, º)

Cg1 represents the centroid of the O71/C72–C75 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O71^i	0.95	2.38	3.246 (4)	151
C22—H22A···Cg1^ii	0.99	2.73	3.615 (4)	148

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