Three 4,7-diaryl-2-ethyl­sulfanyl­pyrazolo[1,5-a][1,3,5]triazines

The mol­ecular dimensions of 2-ethyl­sulfanyl-7-(4-methyl­phen­yl)-4-phenyl­pyrazolo[1,5-a][1,3,5]triazine, C₂₀H₁₈N₄S, (I), 7-(4-chloro­phen­yl)-2-ethyl­sulfanyl-4-phenyl­pyrazolo[1,5-a][1,3,5]triazine, C₁₉H₁₅ClN₄S, (II), and 4,7-bis­(4-chloro­phen­yl)-2-(ethyl­sulfan­yl)pyrazolo[1,5-a][1,3,5]triazine, C₁₉H₁₄Cl₂N₄S, (III), show evidence for some aromatic delocalization in the pyrazole rings. The conformations adopted by the ethyl­sulfanyl substituents are different in all three compounds. There are no hydrogen bonds in any of the crystal structures, but pairs of mol­ecules in (II) and (III) are linked into centrosymmetric dimers by π-stacking inter­actions.

S1. Comment

Compounds having a pyrazolo[1,5-a][1,3,5]triazine residue are of great interest in the treatment and prevention of central nervous system disorders (Bös et al., 1999), metabolic and peripheral disorders (Darrow et al., 2001), and Parkinson's and Alzheimer's diseases (Bös et al., 1999). Recently, a pyrazolotriazine derivative has been reported to be a powerful corticotrophin releasing factor type 1 (CFR1) receptor antagonist (He et al., 2000), playing an important role in modulating the endocrinal, autonomic and immune responses to stress (Kumar et al., 2004).

Pyrazolo[1,5-a][1,3,5]triazines can be readily synthesized from 5-aminopyrazoles and an appropriate biselectrophilic reagent (Insuasty et al., 2006). We report here the structure of three 4,7-diaryl-2-ethylsulfanylpyrazolo[1,5-a][1,3,5] triazines (Figs. 1–3), which were all obtained in good yields from the reactions of S,S-diethyl aroyliminodithiocarbonates with the appropriate 5-amino-3-arylpyrazoles (see scheme) using microwave radiation under solvent-free conditions.

Compounds (I)–(III) are all very similar in composition and constitution, but they show some marked differences both in molecular conformation and in crystal packing. Although analogous compounds containing 4-methylphenyl and 4-chlorophenyl substituents are often isomorphous and isostructural, no such similarities are apparent when compounds (I) and (II) are compared. These two compounds crystallize in different crystal systems with markedly different cell dimensions; in addition, compound (I) exhibits orientational disorder in the unsubstituted phenyl ring, while compound (II) is fully ordered; furthermore, the structure of (II) contains a π–π stacking interaction which is absent from the structure of (I).

The bond distances within the heterocyclic portions of compounds (I)–(III) do not differ significantly from one compound to another (Table 1); however, the values themselves show some interesting features. In each compound the N1—C2 and N3—C4 bonds are significantly shorter than any of the other C—N bonds, and the differences between the C7—C8 and C8—C8A bond distances, 0.034 (4)–0.037 (4) Å, are much less than the difference, ca 0.15 Å, between typical single and double bonds of this type (Allen et al., 1987). These observations are consistent with a measure of aromatic delocalization within the pyrazole ring, allied to strong bond fixation in the triazine ring, as opposed to the fully localized form (A) (see scheme). In compounds (I)–(III), the conformations of the ethylsulfanyl substituents are all different, as shown by the relevant torsion angles (Table 1): only in (I) are the non-H atoms of this substituent effectively coplanar with the adjacent triazine ring. The ring components in compounds (II) and (III) are almost coplanar, as shown by the dihedral angles (Table 1), but in compound (I), both of the aryl rings are displaced significantly further from the plane of the heterocyclic component than in either of (II) and (III).

There are no hydrogen bonds of any kind in the structures of compounds (I) and (II); however, in compounds (II) and (III), pairs of molecules are linked into centrosymmetric dimers by means of π–π stacking interactions. In compound (II), the triazine ring and the unsubstituted phenyl ring in a pair of molecules related by inversion make a dihedral angle of 4.8 (2)°. The interplanar spacing is ca 3.39 Å, and the corresponding centroid separation is 3.551 (2) Å (Fig. 4). In compound (III), the two independent rings of a centrosymmetrically related pair of molecules make a dihedral angle of 5.6 (2)°; here the interplanar spacing is ca 3.53 Å, with a ring-centroid separation of 3.711 (2) Å (Fig. 5). In neither orientation of the molecule of compound (I) are there any stacking interactions.

Related literature

For related literature, see: Allen et al. (1987).

S2. Experimental

Equimolar quantities (2 mmol of each component) of an S,S-diethyl aroyliminodithiocarbonate and the appropriate 5-amino-3-arylpyrazole (see scheme) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 10–15 min to give the products (I) –(III). The compounds were purified by column chromatography on silica gel, using a mixture of hexanes and ethyl acetate (4:1 v/v) as eluant. After removal of the solvent, crystallization from ethyl acetate solutions provided crystals of (I)–(III) suitable for single-crystal X-ray diffraction [(I) yield 60%, m.p. 397 K; (II) yield 63%, m.p. 407 K; (III) yield 71%, m.p. 431 K].

S3. Refinement

Crystals of (I) are triclinic; the space group P1 was selected and confirmed by the structure analysis. For (II) and (III), the space groups P2₁/c and P2₁/n, respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances of 0.95 Å (aromatic and heteroaromatic), 0.98 Å (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups and k = 1.2 for all other H atoms. In (I), the unsubstituted phenyl ring was found to exhibit orientational disorder; this was modelled using two sets of sites, labelled A and B, respectively, for atoms C42, C42, C45 and C46. Refinement of the site-occupancy factors for these two sets of atoms gave values that were identical within experimental uncertainly, and so these occupancies were fixed at 0.5 during the final refinements.

Computing details

For all compounds, 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: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A molecule of (I), showing the atom-labelling scheme. For clarity, only one orientation of the disordered phenyl ring is shown. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a centrosymmetric π-stacked dimer. For clarity, H atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).
	Fig. 5. Part of the crystal structure of (III), showing the formation of a centrosymmetric π-stacked dimer. For clarity, H atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).

(I) 2-ethylsulfanyl-7-(4-methylphenyl)-4-phenylpyrazolo[1,5-a][1,3,5]triazine

Crystal data

C20H18N4S	Z = 2
Mr = 346.45	F(000) = 364
Triclinic, P1	Dx = 1.357 Mg m^−3
Hall symbol: -P 1	Melting point: 397 K
a = 4.8076 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6397 (5) Å	Cell parameters from 3861 reflections
c = 15.5010 (7) Å	θ = 3.9–27.5°
α = 92.164 (4)°	µ = 0.20 mm^−1
β = 96.217 (5)°	T = 120 K
γ = 100.087 (4)°	Block, colourless
V = 847.56 (8) Å^3	0.62 × 0.42 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	3861 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2858 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.9°
ϕ & ω scans	h = −6→5
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→14
Tmin = 0.886, Tmax = 0.990	l = −20→20
13384 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 0.5471P] where P = (Fo^2 + 2Fc^2)/3
3861 reflections	(Δ/σ)max < 0.001
264 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S2	−0.04044 (10)	0.12973 (4)	0.88304 (3)	0.02346 (13)
N1	0.2504 (3)	0.12197 (12)	0.74638 (9)	0.0205 (3)
N3	0.3530 (3)	0.29352 (12)	0.84366 (9)	0.0205 (3)
N5	0.6002 (3)	0.28969 (12)	0.72425 (9)	0.0198 (3)
N6	0.7943 (3)	0.32813 (13)	0.66880 (9)	0.0223 (3)
C2	0.2117 (4)	0.18407 (15)	0.81480 (11)	0.0198 (4)
C4	0.5499 (4)	0.34551 (15)	0.79871 (11)	0.0204 (4)
C7	0.7655 (4)	0.23854 (15)	0.60945 (11)	0.0201 (4)
C8	0.5600 (4)	0.14299 (15)	0.62612 (11)	0.0218 (4)
C8A	0.4533 (4)	0.17628 (15)	0.69945 (11)	0.0199 (4)
C21	−0.1931 (4)	−0.01242 (15)	0.83150 (12)	0.0233 (4)
C22	−0.4076 (4)	−0.07243 (16)	0.88777 (13)	0.0272 (4)
C41	0.7133 (4)	0.46165 (15)	0.83175 (11)	0.0214 (4)
C44	0.9966 (4)	0.67626 (16)	0.90758 (12)	0.0228 (4)
C42A	0.5785 (8)	0.5260 (3)	0.8903 (2)	0.0213 (7)	0.50
C43A	0.7261 (8)	0.6316 (3)	0.9284 (2)	0.0226 (8)	0.50
C45A	1.1151 (9)	0.6162 (3)	0.8466 (3)	0.0243 (8)	0.50
C46A	0.9653 (9)	0.5094 (3)	0.8076 (3)	0.0226 (8)	0.50
C42B	0.7396 (8)	0.4838 (3)	0.9233 (2)	0.0223 (7)	0.50
C43B	0.8778 (8)	0.5926 (3)	0.9601 (2)	0.0236 (8)	0.50
C45B	0.9883 (9)	0.6516 (3)	0.8191 (3)	0.0233 (8)	0.50
C46B	0.8559 (9)	0.5429 (3)	0.7819 (3)	0.0215 (8)	0.50
C71	0.9426 (4)	0.24787 (15)	0.53764 (11)	0.0212 (4)
C72	1.1076 (4)	0.35338 (17)	0.52152 (13)	0.0301 (4)
C73	1.2746 (5)	0.3593 (2)	0.45401 (14)	0.0407 (6)
C74	1.2865 (4)	0.26156 (19)	0.40143 (12)	0.0310 (5)
C75	1.1190 (4)	0.15722 (18)	0.41701 (12)	0.0298 (4)
C76	0.9495 (4)	0.15008 (17)	0.48404 (12)	0.0284 (4)
C77	1.4771 (5)	0.2691 (2)	0.33016 (15)	0.0502 (7)
H8	0.5064	0.0704	0.5933	0.026*
H21A	−0.2879	−0.0040	0.7727	0.028*
H21B	−0.0423	−0.0593	0.8258	0.028*
H22A	−0.3095	−0.0851	0.9444	0.041*
H22B	−0.5026	−0.1478	0.8593	0.041*
H22C	−0.5493	−0.0231	0.8959	0.041*
H44	1.0833	0.7499	0.9318	0.027*
H42A	0.3908	0.4967	0.9028	0.026*	0.50
H43A	0.6422	0.6738	0.9690	0.027*	0.50
H45A	1.2979	0.6474	0.8311	0.029*	0.50
H46A	1.0432	0.4705	0.7635	0.027*	0.50
H42B	0.6632	0.4247	0.9592	0.027*	0.50
H43B	0.8901	0.6091	1.0210	0.028*	0.50
H45B	1.0738	0.7095	0.7838	0.028*	0.50
H46B	0.8634	0.5244	0.7221	0.026*	0.50
H72	1.1059	0.4217	0.5569	0.036*
H73	1.3843	0.4324	0.4433	0.049*
H75	1.1201	0.0893	0.3812	0.036*
H76	0.8361	0.0773	0.4936	0.034*
H77A	1.3681	0.2811	0.2751	0.075*
H77B	1.5516	0.1963	0.3248	0.075*
H77C	1.6356	0.3348	0.3442	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0257 (3)	0.0195 (2)	0.0242 (2)	0.00043 (18)	0.00539 (18)	−0.00027 (17)
N1	0.0213 (8)	0.0182 (7)	0.0217 (8)	0.0035 (6)	0.0014 (6)	−0.0002 (6)
N3	0.0230 (8)	0.0164 (7)	0.0217 (8)	0.0018 (6)	0.0039 (6)	0.0016 (6)
N5	0.0241 (8)	0.0169 (7)	0.0182 (7)	0.0025 (6)	0.0042 (6)	0.0008 (6)
N6	0.0279 (8)	0.0194 (8)	0.0200 (7)	0.0029 (6)	0.0075 (6)	0.0008 (6)
C2	0.0207 (9)	0.0195 (9)	0.0196 (9)	0.0057 (7)	−0.0003 (7)	0.0028 (7)
C4	0.0240 (9)	0.0189 (9)	0.0189 (9)	0.0047 (7)	0.0035 (7)	0.0014 (7)
C7	0.0252 (9)	0.0182 (9)	0.0174 (8)	0.0072 (7)	−0.0003 (7)	0.0003 (7)
C8	0.0262 (9)	0.0182 (9)	0.0205 (9)	0.0045 (7)	0.0009 (7)	−0.0023 (7)
C8A	0.0203 (9)	0.0172 (8)	0.0212 (9)	0.0030 (7)	−0.0008 (7)	0.0011 (7)
C21	0.0244 (10)	0.0183 (9)	0.0265 (10)	0.0019 (7)	0.0035 (8)	0.0019 (7)
C22	0.0260 (10)	0.0236 (9)	0.0305 (10)	−0.0013 (8)	0.0058 (8)	0.0014 (8)
C41	0.0258 (9)	0.0176 (9)	0.0214 (9)	0.0037 (7)	0.0065 (7)	0.0002 (7)
C44	0.0248 (9)	0.0180 (9)	0.0244 (9)	0.0006 (7)	0.0041 (8)	−0.0027 (7)
C42A	0.0242 (19)	0.0188 (17)	0.0209 (18)	0.0020 (15)	0.0049 (15)	0.0026 (14)
C43A	0.031 (2)	0.0172 (17)	0.0211 (18)	0.0056 (16)	0.0069 (16)	−0.0018 (14)
C45A	0.024 (2)	0.0219 (19)	0.025 (2)	−0.0026 (17)	0.0044 (16)	0.0017 (15)
C46A	0.029 (2)	0.019 (2)	0.021 (2)	0.0042 (17)	0.0090 (17)	0.0001 (16)
C42B	0.0214 (18)	0.0236 (19)	0.0221 (18)	0.0038 (15)	0.0042 (15)	0.0014 (15)
C43B	0.0218 (19)	0.0255 (19)	0.0234 (19)	0.0038 (16)	0.0028 (15)	−0.0005 (15)
C45B	0.024 (2)	0.022 (2)	0.024 (2)	0.0035 (17)	0.0061 (16)	0.0046 (16)
C46B	0.028 (2)	0.019 (2)	0.0190 (19)	0.0050 (17)	0.0080 (17)	0.0034 (15)
C71	0.0228 (9)	0.0240 (9)	0.0172 (8)	0.0069 (7)	0.0005 (7)	0.0004 (7)
C72	0.0330 (11)	0.0273 (10)	0.0274 (10)	−0.0018 (8)	0.0076 (8)	−0.0086 (8)
C73	0.0387 (12)	0.0423 (13)	0.0341 (12)	−0.0149 (10)	0.0134 (10)	−0.0122 (10)
C74	0.0236 (10)	0.0490 (13)	0.0196 (9)	0.0059 (9)	0.0022 (8)	−0.0047 (9)
C75	0.0392 (12)	0.0328 (11)	0.0209 (9)	0.0171 (9)	0.0034 (8)	−0.0027 (8)
C76	0.0411 (12)	0.0218 (9)	0.0246 (10)	0.0095 (8)	0.0071 (8)	0.0020 (7)
C77	0.0350 (12)	0.0790 (19)	0.0324 (12)	−0.0025 (12)	0.0137 (10)	−0.0169 (12)

Geometric parameters (Å, º)

S2—C2	1.7461 (18)	C44—C43A	1.391 (4)
S2—C21	1.8062 (18)	C44—H44	0.93
N1—C2	1.309 (2)	C42A—C43A	1.382 (5)
N1—C8A	1.361 (2)	C42A—H42A	0.95
N3—C4	1.312 (2)	C43A—H43A	0.95
N3—C2	1.368 (2)	C45A—C46A	1.402 (5)
N5—N6	1.366 (2)	C45A—H45A	0.95
N5—C4	1.368 (2)	C46A—H46A	0.95
N5—C8A	1.402 (2)	C42B—C43B	1.392 (5)
N6—C7	1.342 (2)	C42B—H42B	0.95
C4—C41	1.482 (2)	C43B—H43B	0.95
C7—C8	1.404 (3)	C45B—C46B	1.386 (5)
C7—C71	1.469 (2)	C45B—H45B	0.95
C8—C8A	1.367 (2)	C46B—H46B	0.95
C8—H8	0.95	C71—C72	1.388 (3)
C21—C22	1.517 (2)	C71—C76	1.391 (3)
C21—H21A	0.99	C72—C73	1.383 (3)
C21—H21B	0.99	C72—H72	0.95
C22—H22A	0.98	C73—C74	1.387 (3)
C22—H22B	0.98	C73—H73	0.95
C22—H22C	0.98	C74—C75	1.380 (3)
C41—C46A	1.340 (4)	C74—C77	1.505 (3)
C41—C46B	1.380 (4)	C75—C76	1.385 (3)
C41—C42B	1.421 (4)	C75—H75	0.95
C41—C42A	1.433 (4)	C76—H76	0.95
C44—C43B	1.379 (4)	C77—H77A	0.98
C44—C45A	1.383 (4)	C77—H77B	0.98
C44—C45B	1.385 (4)	C77—H77C	0.98
C2—S2—C21	102.54 (8)	C43A—C42A—H42A	120.6
C2—N1—C8A	114.23 (15)	C41—C42A—H42A	120.6
C4—N3—C2	118.17 (15)	C42A—C43A—C44	120.4 (3)
N6—N5—C4	128.05 (15)	C42A—C43A—H43A	119.8
N6—N5—C8A	111.81 (14)	C44—C43A—H43A	119.8
C4—N5—C8A	120.06 (15)	C44—C45A—C46A	120.0 (3)
C7—N6—N5	103.82 (14)	C44—C45A—H45A	120.0
N1—C2—N3	127.56 (16)	C46A—C45A—H45A	120.0
N1—C2—S2	121.09 (14)	C41—C46A—C45A	120.7 (3)
N3—C2—S2	111.34 (12)	C41—C46A—H46A	119.7
N3—C4—N5	118.91 (16)	C45A—C46A—H46A	119.7
N3—C4—C41	118.51 (15)	C43B—C42B—C41	119.6 (3)
N5—C4—C41	122.56 (15)	C43B—C42B—H42B	120.2
N6—C7—C8	112.74 (16)	C41—C42B—H42B	120.2
N6—C7—C71	119.77 (16)	C44—C43B—C42B	119.7 (3)
C8—C7—C71	127.49 (16)	C44—C43B—H43B	120.2
C8A—C8—C7	105.61 (16)	C42B—C43B—H43B	120.2
C8A—C8—H8	127.2	C44—C45B—C46B	120.3 (3)
C7—C8—H8	127.2	C44—C45B—H45B	119.8
N1—C8A—C8	133.00 (16)	C46B—C45B—H45B	119.8
N1—C8A—N5	120.98 (15)	C41—C46B—C45B	120.0 (3)
C8—C8A—N5	106.02 (15)	C41—C46B—H46B	120.0
C22—C21—S2	107.87 (13)	C45B—C46B—H46B	120.0
C22—C21—H21A	110.1	C72—C71—C76	118.22 (17)
S2—C21—H21A	110.1	C72—C71—C7	121.35 (16)
C22—C21—H21B	110.1	C76—C71—C7	120.43 (17)
S2—C21—H21B	110.1	C73—C72—C71	120.08 (18)
H21A—C21—H21B	108.4	C73—C72—H72	120.0
C21—C22—H22A	109.5	C71—C72—H72	120.0
C21—C22—H22B	109.5	C72—C73—C74	121.9 (2)
H22A—C22—H22B	109.5	C72—C73—H73	119.0
C21—C22—H22C	109.5	C74—C73—H73	119.0
H22A—C22—H22C	109.5	C75—C74—C73	117.74 (18)
H22B—C22—H22C	109.5	C75—C74—C77	121.18 (19)
C46B—C41—C42B	119.2 (3)	C73—C74—C77	121.1 (2)
C46A—C41—C42A	120.0 (3)	C74—C75—C76	120.99 (18)
C46A—C41—C4	124.4 (2)	C74—C75—H75	119.5
C46B—C41—C4	125.2 (2)	C76—C75—H75	119.5
C42B—C41—C4	115.4 (2)	C75—C76—C71	121.03 (19)
C42A—C41—C4	115.6 (2)	C75—C76—H76	119.5
C43B—C44—C45B	120.6 (3)	C71—C76—H76	119.5
C45A—C44—C43A	119.7 (3)	C74—C77—H77A	109.5
C43B—C44—H44	119.7	C74—C77—H77B	109.5
C45A—C44—H44	122.5	H77A—C77—H77B	109.5
C45B—C44—H44	119.7	C74—C77—H77C	109.5
C43A—C44—H44	117.5	H77A—C77—H77C	109.5
C43A—C42A—C41	118.9 (3)	H77B—C77—H77C	109.5
C4—N5—N6—C7	177.08 (16)	N5—C4—C41—C42A	159.0 (2)
C8A—N5—N6—C7	0.38 (18)	C46A—C41—C42A—C43A	−7.1 (5)
C8A—N1—C2—N3	−1.1 (3)	C46B—C41—C42A—C43A	−40.8 (4)
C8A—N1—C2—S2	179.74 (12)	C42B—C41—C42A—C43A	74.6 (4)
C4—N3—C2—N1	0.7 (3)	C4—C41—C42A—C43A	175.7 (3)
C4—N3—C2—S2	179.91 (13)	C41—C42A—C43A—C44	2.4 (5)
C21—S2—C2—N1	−0.74 (16)	C45A—C44—C43A—C42A	1.8 (5)
C21—S2—C2—N3	179.98 (12)	C43A—C44—C45A—C46A	−1.5 (5)
C2—N3—C4—N5	1.6 (2)	C42A—C41—C46A—C45A	7.5 (6)
C2—N3—C4—C41	−177.15 (15)	C4—C41—C46A—C45A	−175.5 (3)
N6—N5—C4—N3	−179.81 (15)	C44—C45A—C46A—C41	−3.2 (6)
C8A—N5—C4—N3	−3.4 (2)	C46B—C41—C42B—C43B	8.1 (5)
N6—N5—C4—C41	−1.1 (3)	C4—C41—C42B—C43B	−177.0 (3)
C8A—N5—C4—C41	175.37 (15)	C45A—C44—C43B—C42B	−39.1 (4)
N5—N6—C7—C8	−0.73 (19)	C45B—C44—C43B—C42B	−2.2 (5)
N5—N6—C7—C71	179.84 (14)	C41—C42B—C43B—C44	−2.3 (5)
N6—C7—C8—C8A	0.8 (2)	C43B—C44—C45B—C46B	1.1 (5)
C71—C7—C8—C8A	−179.81 (16)	C42B—C41—C46B—C45B	−9.3 (5)
C2—N1—C8A—C8	179.07 (18)	C4—C41—C46B—C45B	176.3 (3)
C2—N1—C8A—N5	−0.7 (2)	C44—C45B—C46B—C41	4.8 (6)
C7—C8—C8A—N1	179.66 (18)	N6—C7—C71—C72	−10.2 (3)
C7—C8—C8A—N5	−0.52 (19)	C8—C7—C71—C72	170.43 (18)
N6—N5—C8A—N1	179.95 (15)	N6—C7—C71—C76	169.48 (17)
C4—N5—C8A—N1	3.0 (2)	C8—C7—C71—C76	−9.8 (3)
N6—N5—C8A—C8	0.10 (19)	C76—C71—C72—C73	−0.4 (3)
C4—N5—C8A—C8	−176.90 (15)	C7—C71—C72—C73	179.32 (19)
C2—S2—C21—C22	177.01 (12)	C71—C72—C73—C74	−0.9 (3)
N3—C4—C41—C46A	160.6 (3)	C72—C73—C74—C75	1.7 (3)
N5—C4—C41—C46A	−18.1 (4)	C72—C73—C74—C77	−177.9 (2)
N3—C4—C41—C46B	−158.0 (3)	C73—C74—C75—C76	−1.3 (3)
N5—C4—C41—C46B	23.3 (3)	C77—C74—C75—C76	178.4 (2)
N3—C4—C41—C42B	27.4 (3)	C74—C75—C76—C71	0.1 (3)
N5—C4—C41—C42B	−151.3 (2)	C72—C71—C76—C75	0.8 (3)
N3—C4—C41—C42A	−22.2 (3)	C7—C71—C76—C75	−178.93 (17)

(II) 7-(4-chlorophenyl)-2-ethylsulfanyl-4-phenylpyrazolo[1,5-a][1,3,5]triazine

Crystal data

C19H15ClN4S	F(000) = 760
Mr = 366.86	Dx = 1.459 Mg m^−3
Monoclinic, P21/c	Melting point: 407 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.829 (1) Å	Cell parameters from 3822 reflections
b = 7.5703 (5) Å	θ = 4.2–27.5°
c = 19.5297 (5) Å	µ = 0.36 mm^−1
β = 107.200 (3)°	T = 120 K
V = 1670.61 (18) Å^3	Plate, colourless
Z = 4	0.56 × 0.34 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	3822 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 4.2°
ϕ & ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.822, Tmax = 0.982	l = −25→25
37866 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0328P)^2 + 1.4467P] where P = (Fo^2 + 2Fc^2)/3
3822 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl74	0.30933 (4)	1.48852 (6)	0.73815 (3)	0.02895 (13)
S2	0.11011 (4)	0.15742 (6)	0.38792 (2)	0.02328 (12)
N1	0.11559 (13)	0.4691 (2)	0.45226 (8)	0.0196 (3)
N3	0.29107 (13)	0.29190 (19)	0.48366 (7)	0.0191 (3)
N5	0.29545 (12)	0.56219 (19)	0.53887 (7)	0.0171 (3)
N6	0.34053 (13)	0.70054 (19)	0.58327 (7)	0.0182 (3)
C2	0.17618 (15)	0.3284 (2)	0.44699 (9)	0.0182 (3)
C4	0.35187 (15)	0.4096 (2)	0.52928 (9)	0.0171 (3)
C7	0.24957 (15)	0.8130 (2)	0.57227 (9)	0.0179 (3)
C8	0.14656 (15)	0.7511 (2)	0.52129 (9)	0.0201 (4)
C8A	0.17681 (15)	0.5898 (2)	0.50008 (9)	0.0182 (3)
C21	−0.02137 (15)	0.2667 (2)	0.33248 (9)	0.0207 (4)
C22	0.00496 (17)	0.3957 (3)	0.28002 (10)	0.0253 (4)
C41	0.47747 (15)	0.3725 (2)	0.56738 (9)	0.0184 (3)
C42	0.52485 (16)	0.2186 (2)	0.54762 (10)	0.0236 (4)
C43	0.64089 (17)	0.1712 (2)	0.58079 (10)	0.0253 (4)
C44	0.71193 (16)	0.2774 (3)	0.63389 (10)	0.0236 (4)
C45	0.66627 (17)	0.4298 (3)	0.65377 (10)	0.0273 (4)
C46	0.54960 (16)	0.4785 (3)	0.62090 (10)	0.0245 (4)
C71	0.26470 (15)	0.9795 (2)	0.61253 (9)	0.0179 (3)
C72	0.37400 (15)	1.0255 (2)	0.66016 (9)	0.0200 (4)
C73	0.38800 (16)	1.1816 (2)	0.69867 (9)	0.0217 (4)
C74	0.29183 (16)	1.2929 (2)	0.68918 (9)	0.0205 (4)
C75	0.18241 (16)	1.2523 (2)	0.64193 (10)	0.0226 (4)
C76	0.16963 (16)	1.0946 (2)	0.60436 (9)	0.0218 (4)
H8	0.0720	0.8087	0.5050	0.024*
H21A	−0.0776	0.1764	0.3055	0.025*
H21B	−0.0600	0.3307	0.3637	0.025*
H22A	0.0435	0.3333	0.2490	0.038*
H22B	0.0576	0.4888	0.3065	0.038*
H22C	−0.0691	0.4487	0.2506	0.038*
H42	0.4767	0.1456	0.5109	0.028*
H43	0.6719	0.0656	0.5671	0.030*
H44	0.7919	0.2454	0.6566	0.028*
H45	0.7151	0.5025	0.6904	0.033*
H46	0.5190	0.5840	0.6349	0.029*
H72	0.4397	0.9486	0.6662	0.024*
H73	0.4626	1.2118	0.7312	0.026*
H75	0.1174	1.3308	0.6354	0.027*
H76	0.0946	1.0643	0.5724	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl74	0.0253 (2)	0.0254 (2)	0.0348 (3)	−0.00032 (19)	0.00681 (19)	−0.01148 (19)
S2	0.0218 (2)	0.0192 (2)	0.0246 (2)	0.00180 (18)	0.00026 (17)	−0.00373 (18)
N1	0.0169 (7)	0.0203 (7)	0.0202 (7)	0.0013 (6)	0.0034 (6)	−0.0016 (6)
N3	0.0185 (7)	0.0192 (7)	0.0187 (7)	0.0012 (6)	0.0043 (6)	0.0015 (6)
N5	0.0177 (7)	0.0163 (7)	0.0169 (7)	0.0007 (6)	0.0044 (6)	0.0002 (6)
N6	0.0187 (7)	0.0165 (7)	0.0185 (7)	0.0010 (6)	0.0040 (6)	−0.0017 (6)
C2	0.0199 (8)	0.0183 (8)	0.0162 (8)	−0.0003 (7)	0.0049 (7)	0.0010 (7)
C4	0.0189 (8)	0.0175 (8)	0.0163 (8)	0.0019 (7)	0.0073 (7)	0.0028 (7)
C7	0.0174 (8)	0.0189 (8)	0.0176 (8)	0.0013 (7)	0.0056 (7)	0.0025 (7)
C8	0.0172 (8)	0.0213 (9)	0.0199 (8)	0.0036 (7)	0.0023 (7)	0.0002 (7)
C8A	0.0150 (8)	0.0217 (8)	0.0174 (8)	0.0009 (7)	0.0040 (7)	0.0013 (7)
C21	0.0182 (8)	0.0212 (9)	0.0206 (8)	−0.0001 (7)	0.0026 (7)	−0.0019 (7)
C22	0.0238 (9)	0.0284 (10)	0.0228 (9)	−0.0005 (8)	0.0057 (7)	0.0010 (8)
C41	0.0179 (8)	0.0212 (9)	0.0160 (8)	0.0012 (7)	0.0051 (7)	0.0039 (7)
C42	0.0206 (9)	0.0217 (9)	0.0259 (9)	0.0020 (7)	0.0030 (7)	−0.0020 (8)
C43	0.0230 (9)	0.0213 (9)	0.0306 (10)	0.0056 (7)	0.0064 (8)	0.0011 (8)
C44	0.0169 (8)	0.0271 (9)	0.0258 (9)	0.0051 (7)	0.0049 (7)	0.0074 (8)
C45	0.0200 (9)	0.0321 (10)	0.0252 (9)	0.0007 (8)	−0.0005 (7)	−0.0044 (8)
C46	0.0204 (9)	0.0253 (9)	0.0252 (9)	0.0046 (7)	0.0029 (7)	−0.0031 (8)
C71	0.0195 (8)	0.0196 (8)	0.0150 (8)	0.0006 (7)	0.0058 (7)	0.0017 (7)
C72	0.0179 (8)	0.0206 (9)	0.0211 (8)	0.0028 (7)	0.0049 (7)	0.0020 (7)
C73	0.0180 (8)	0.0241 (9)	0.0208 (9)	−0.0010 (7)	0.0024 (7)	0.0001 (7)
C74	0.0234 (9)	0.0195 (8)	0.0196 (8)	0.0002 (7)	0.0080 (7)	−0.0010 (7)
C75	0.0197 (9)	0.0227 (9)	0.0251 (9)	0.0035 (7)	0.0063 (7)	−0.0010 (7)
C76	0.0177 (8)	0.0239 (9)	0.0223 (9)	0.0010 (7)	0.0035 (7)	−0.0011 (7)

Geometric parameters (Å, º)

Cl74—C74	1.7417 (18)	C41—C46	1.392 (2)
S2—C2	1.7558 (17)	C41—C42	1.396 (2)
S2—C21	1.8110 (18)	C42—C43	1.381 (3)
N1—C2	1.305 (2)	C42—H42	0.95
N1—C8A	1.354 (2)	C43—C44	1.383 (3)
N3—C4	1.314 (2)	C43—H43	0.95
N3—C2	1.364 (2)	C44—C45	1.378 (3)
N5—N6	1.3636 (19)	C44—H44	0.95
N5—C4	1.374 (2)	C45—C46	1.389 (3)
N5—C8A	1.399 (2)	C45—H45	0.95
N6—C7	1.339 (2)	C46—H46	0.95
C4—C41	1.479 (2)	C71—C76	1.394 (2)
C7—C8	1.406 (2)	C71—C72	1.395 (2)
C7—C71	1.468 (2)	C72—C73	1.384 (2)
C8—C8A	1.370 (2)	C72—H72	0.95
C8—H8	0.95	C73—C74	1.384 (2)
C21—C22	1.513 (3)	C73—H73	0.95
C21—H21A	0.99	C74—C75	1.384 (3)
C21—H21B	0.99	C75—C76	1.386 (3)
C22—H22A	0.98	C75—H75	0.95
C22—H22B	0.98	C76—H76	0.95
C22—H22C	0.98
C2—S2—C21	101.12 (8)	C46—C41—C4	124.75 (16)
C2—N1—C8A	114.29 (15)	C42—C41—C4	116.45 (16)
C4—N3—C2	118.64 (15)	C43—C42—C41	120.80 (17)
N6—N5—C4	128.16 (14)	C43—C42—H42	119.6
N6—N5—C8A	111.74 (13)	C41—C42—H42	119.6
C4—N5—C8A	120.11 (14)	C42—C43—C44	119.99 (17)
C7—N6—N5	104.00 (13)	C42—C43—H43	120.0
N1—C2—N3	127.52 (16)	C44—C43—H43	120.0
N1—C2—S2	120.35 (13)	C45—C44—C43	119.76 (17)
N3—C2—S2	112.12 (12)	C45—C44—H44	120.1
N3—C4—N5	118.16 (15)	C43—C44—H44	120.1
N3—C4—C41	118.64 (15)	C44—C45—C46	120.70 (18)
N5—C4—C41	123.20 (15)	C44—C45—H45	119.7
N6—C7—C8	112.87 (15)	C46—C45—H45	119.7
N6—C7—C71	119.68 (15)	C45—C46—C41	119.95 (17)
C8—C7—C71	127.45 (16)	C45—C46—H46	120.0
C8A—C8—C7	105.18 (15)	C41—C46—H46	120.0
C8A—C8—H8	127.4	C76—C71—C72	118.53 (16)
C7—C8—H8	127.4	C76—C71—C7	120.58 (16)
N1—C8A—C8	132.53 (16)	C72—C71—C7	120.89 (15)
N1—C8A—N5	121.25 (15)	C73—C72—C71	120.92 (16)
C8—C8A—N5	106.22 (15)	C73—C72—H72	119.5
C22—C21—S2	112.79 (13)	C71—C72—H72	119.5
C22—C21—H21A	109.0	C74—C73—C72	119.06 (16)
S2—C21—H21A	109.0	C74—C73—H73	120.5
C22—C21—H21B	109.0	C72—C73—H73	120.5
S2—C21—H21B	109.0	C73—C74—C75	121.58 (17)
H21A—C21—H21B	107.8	C73—C74—Cl74	119.01 (14)
C21—C22—H22A	109.5	C75—C74—Cl74	119.41 (14)
C21—C22—H22B	109.5	C74—C75—C76	118.60 (17)
H22A—C22—H22B	109.5	C74—C75—H75	120.7
C21—C22—H22C	109.5	C76—C75—H75	120.7
H22A—C22—H22C	109.5	C75—C76—C71	121.30 (17)
H22B—C22—H22C	109.5	C75—C76—H76	119.3
C46—C41—C42	118.80 (16)	C71—C76—H76	119.3
C4—N5—N6—C7	−179.82 (16)	N3—C4—C41—C46	−174.86 (17)
C8A—N5—N6—C7	0.40 (18)	N5—C4—C41—C46	5.6 (3)
C8A—N1—C2—N3	0.1 (3)	N3—C4—C41—C42	4.7 (2)
C8A—N1—C2—S2	179.52 (12)	N5—C4—C41—C42	−174.88 (16)
C4—N3—C2—N1	−1.2 (3)	C46—C41—C42—C43	0.5 (3)
C4—N3—C2—S2	179.26 (12)	C4—C41—C42—C43	−179.10 (17)
C21—S2—C2—N1	15.00 (16)	C41—C42—C43—C44	−0.5 (3)
C21—S2—C2—N3	−165.47 (12)	C42—C43—C44—C45	0.4 (3)
C2—N3—C4—N5	1.4 (2)	C43—C44—C45—C46	−0.2 (3)
C2—N3—C4—C41	−178.15 (14)	C44—C45—C46—C41	0.2 (3)
N6—N5—C4—N3	179.61 (15)	C42—C41—C46—C45	−0.3 (3)
C8A—N5—C4—N3	−0.6 (2)	C4—C41—C46—C45	179.25 (17)
N6—N5—C4—C41	−0.8 (3)	N6—C7—C71—C76	−176.97 (16)
C8A—N5—C4—C41	178.93 (15)	C8—C7—C71—C76	2.4 (3)
N5—N6—C7—C8	−0.40 (19)	N6—C7—C71—C72	2.5 (2)
N5—N6—C7—C71	179.04 (14)	C8—C7—C71—C72	−178.13 (17)
N6—C7—C8—C8A	0.2 (2)	C76—C71—C72—C73	0.2 (3)
C71—C7—C8—C8A	−179.14 (16)	C7—C71—C72—C73	−179.33 (16)
C2—N1—C8A—C8	−179.84 (18)	C71—C72—C73—C74	−0.3 (3)
C2—N1—C8A—N5	0.8 (2)	C72—C73—C74—C75	−0.3 (3)
C7—C8—C8A—N1	−179.42 (18)	C72—C73—C74—Cl74	179.56 (13)
C7—C8—C8A—N5	0.01 (18)	C73—C74—C75—C76	1.0 (3)
N6—N5—C8A—N1	179.25 (14)	Cl74—C74—C75—C76	−178.89 (14)
C4—N5—C8A—N1	−0.5 (2)	C74—C75—C76—C71	−1.1 (3)
N6—N5—C8A—C8	−0.26 (19)	C72—C71—C76—C75	0.5 (3)
C4—N5—C8A—C8	179.94 (14)	C7—C71—C76—C75	−179.97 (16)
C2—S2—C21—C22	74.19 (14)

(III) 4,7-bis(4-chlorophenyl)-2-(ethylsulfanyl)pyrazolo[1,5-a][1,3,5]triazine

Crystal data

C19H14Cl2N4S	F(000) = 824
Mr = 401.30	Dx = 1.506 Mg m^−3
Monoclinic, P21/n	Melting point: 431 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.7117 (4) Å	Cell parameters from 4039 reflections
b = 8.3261 (10) Å	θ = 3.8–27.5°
c = 27.678 (3) Å	µ = 0.50 mm^−1
β = 94.978 (5)°	T = 120 K
V = 1770.5 (3) Å^3	Block, colourless
Z = 4	0.47 × 0.24 × 0.14 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	4039 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.8°
ϕ & ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.801, Tmax = 0.934	l = −35→35
39992 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0669P)^2 + 2.3365P] where P = (Fo^2 + 2Fc^2)/3
4039 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl44	0.53273 (13)	1.12947 (11)	0.60946 (4)	0.0411 (3)
Cl74	0.22872 (11)	0.40819 (10)	0.24961 (3)	0.0321 (2)
S2	0.04836 (12)	0.15969 (10)	0.66827 (3)	0.0309 (2)
N1	0.0733 (4)	0.1695 (3)	0.57532 (9)	0.0266 (6)
N3	0.1761 (3)	0.4036 (3)	0.61961 (9)	0.0246 (6)
N5	0.1896 (3)	0.3984 (3)	0.53699 (9)	0.0232 (6)
N6	0.2241 (3)	0.4522 (3)	0.49218 (9)	0.0261 (6)
C2	0.1072 (4)	0.2537 (4)	0.61535 (11)	0.0247 (7)
C4	0.2173 (4)	0.4770 (4)	0.58032 (11)	0.0226 (7)
C7	0.1756 (4)	0.3309 (4)	0.46263 (11)	0.0231 (7)
C8	0.1101 (4)	0.1987 (4)	0.48683 (12)	0.0267 (7)
C8A	0.1188 (4)	0.2430 (4)	0.53469 (11)	0.0246 (7)
C21	0.1133 (4)	0.3048 (4)	0.71493 (12)	0.0309 (8)
C22	0.3047 (5)	0.3023 (5)	0.73139 (14)	0.0416 (9)
C41	0.2931 (4)	0.6389 (4)	0.58507 (11)	0.0232 (7)
C42	0.3323 (5)	0.6989 (4)	0.63179 (12)	0.0305 (8)
C43	0.4045 (4)	0.8488 (4)	0.63955 (12)	0.0319 (8)
C44	0.4367 (4)	0.9424 (4)	0.60021 (12)	0.0294 (8)
C45	0.3941 (5)	0.8896 (4)	0.55373 (13)	0.0373 (9)
C46	0.3246 (5)	0.7378 (4)	0.54619 (13)	0.0329 (8)
C71	0.1915 (4)	0.3480 (4)	0.41023 (11)	0.0236 (7)
C72	0.2596 (4)	0.4885 (4)	0.39204 (12)	0.0284 (7)
C73	0.2706 (4)	0.5079 (4)	0.34288 (12)	0.0282 (7)
C74	0.2146 (4)	0.3844 (4)	0.31188 (11)	0.0244 (7)
C75	0.1490 (4)	0.2433 (4)	0.32887 (12)	0.0286 (8)
C76	0.1372 (4)	0.2263 (4)	0.37806 (12)	0.0265 (7)
H8	0.0687	0.0999	0.4730	0.032*
H21A	0.0819	0.4135	0.7026	0.037*
H21B	0.0466	0.2843	0.7433	0.037*
H22A	0.3718	0.3312	0.7042	0.062*
H22B	0.3380	0.1944	0.7429	0.062*
H22C	0.3287	0.3797	0.7578	0.062*
H42	0.3086	0.6349	0.6589	0.037*
H43	0.4319	0.8873	0.6716	0.038*
H45	0.4123	0.9570	0.5269	0.045*
H46	0.2979	0.7002	0.5140	0.040*
H72	0.2988	0.5719	0.4137	0.034*
H73	0.3158	0.6043	0.3305	0.034*
H75	0.1125	0.1592	0.3071	0.034*
H76	0.0912	0.1299	0.3901	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl44	0.0467 (6)	0.0273 (5)	0.0496 (6)	−0.0131 (4)	0.0052 (4)	−0.0066 (4)
Cl74	0.0413 (5)	0.0331 (5)	0.0230 (4)	−0.0003 (4)	0.0088 (3)	0.0005 (3)
S2	0.0435 (6)	0.0257 (5)	0.0241 (4)	−0.0081 (4)	0.0062 (4)	−0.0008 (3)
N1	0.0339 (16)	0.0232 (15)	0.0226 (14)	−0.0047 (12)	0.0028 (12)	0.0005 (11)
N3	0.0280 (15)	0.0212 (14)	0.0247 (14)	−0.0016 (12)	0.0036 (11)	0.0003 (11)
N5	0.0298 (15)	0.0199 (13)	0.0199 (13)	−0.0026 (11)	0.0032 (11)	−0.0009 (11)
N6	0.0315 (15)	0.0241 (14)	0.0222 (14)	−0.0032 (12)	0.0003 (11)	0.0008 (11)
C2	0.0256 (18)	0.0249 (17)	0.0238 (17)	0.0001 (14)	0.0028 (13)	−0.0006 (13)
C4	0.0233 (17)	0.0221 (16)	0.0222 (16)	0.0017 (13)	0.0004 (13)	−0.0002 (13)
C7	0.0231 (17)	0.0217 (16)	0.0239 (16)	−0.0031 (13)	−0.0006 (13)	−0.0002 (13)
C8	0.0319 (19)	0.0212 (17)	0.0270 (17)	−0.0066 (14)	0.0024 (14)	−0.0035 (13)
C8A	0.0279 (18)	0.0203 (16)	0.0258 (17)	−0.0031 (13)	0.0028 (14)	−0.0001 (13)
C21	0.036 (2)	0.0332 (19)	0.0237 (17)	−0.0018 (16)	0.0059 (14)	−0.0034 (14)
C22	0.038 (2)	0.045 (2)	0.040 (2)	0.0008 (18)	−0.0042 (17)	−0.0019 (18)
C41	0.0216 (16)	0.0218 (17)	0.0265 (16)	−0.0021 (13)	0.0033 (13)	−0.0014 (13)
C42	0.037 (2)	0.0243 (17)	0.0299 (18)	−0.0023 (15)	0.0035 (15)	0.0014 (14)
C43	0.037 (2)	0.0306 (19)	0.0282 (18)	−0.0041 (16)	0.0018 (15)	−0.0053 (15)
C44	0.0298 (19)	0.0219 (17)	0.0362 (19)	−0.0017 (14)	0.0012 (15)	−0.0050 (14)
C45	0.046 (2)	0.0303 (19)	0.036 (2)	−0.0108 (17)	0.0088 (17)	0.0030 (16)
C46	0.043 (2)	0.0262 (18)	0.0297 (19)	−0.0108 (16)	0.0034 (16)	−0.0047 (15)
C71	0.0249 (17)	0.0222 (16)	0.0235 (16)	−0.0006 (13)	0.0013 (13)	−0.0024 (13)
C72	0.0347 (19)	0.0245 (17)	0.0254 (17)	−0.0034 (15)	−0.0006 (14)	−0.0030 (14)
C73	0.0336 (19)	0.0230 (17)	0.0280 (17)	−0.0021 (15)	0.0016 (14)	0.0033 (14)
C74	0.0265 (17)	0.0236 (17)	0.0235 (16)	0.0041 (13)	0.0047 (13)	−0.0007 (13)
C75	0.036 (2)	0.0219 (17)	0.0275 (18)	0.0016 (14)	0.0008 (15)	−0.0034 (14)
C76	0.0301 (18)	0.0228 (17)	0.0266 (17)	−0.0019 (14)	0.0028 (14)	0.0009 (14)

Geometric parameters (Å, º)

Cl44—C44	1.734 (3)	C22—H22C	0.98
Cl74—C74	1.748 (3)	C41—C46	1.393 (5)
S2—C2	1.755 (3)	C41—C42	1.395 (4)
S2—C21	1.807 (3)	C42—C43	1.376 (5)
N1—C2	1.318 (4)	C42—H42	0.95
N1—C8A	1.353 (4)	C43—C44	1.379 (5)
N3—C4	1.310 (4)	C43—H43	0.95
N3—C2	1.358 (4)	C44—C45	1.372 (5)
N5—N6	1.366 (3)	C45—C46	1.382 (5)
N5—C4	1.366 (4)	C45—H45	0.95
N5—C8A	1.403 (4)	C46—H46	0.95
N6—C7	1.333 (4)	C71—C76	1.389 (4)
C4—C41	1.471 (4)	C71—C72	1.394 (5)
C7—C8	1.405 (4)	C72—C73	1.380 (4)
C7—C71	1.473 (4)	C72—H72	0.95
C8—C8A	1.371 (4)	C73—C74	1.384 (5)
C8—H8	0.95	C73—H73	0.95
C21—C22	1.506 (5)	C74—C75	1.378 (5)
C21—H21A	0.99	C75—C76	1.379 (4)
C21—H21B	0.99	C75—H75	0.95
C22—H22A	0.98	C76—H76	0.95
C22—H22B	0.98
C2—S2—C21	102.87 (16)	C46—C41—C4	124.6 (3)
C2—N1—C8A	114.3 (3)	C42—C41—C4	117.6 (3)
C4—N3—C2	118.5 (3)	C43—C42—C41	121.5 (3)
N6—N5—C4	127.7 (3)	C43—C42—H42	119.3
N6—N5—C8A	111.5 (2)	C41—C42—H42	119.3
C4—N5—C8A	120.8 (3)	C42—C43—C44	119.2 (3)
C7—N6—N5	104.0 (2)	C42—C43—H43	120.4
N1—C2—N3	127.6 (3)	C44—C43—H43	120.4
N1—C2—S2	114.7 (2)	C45—C44—C43	121.0 (3)
N3—C2—S2	117.7 (2)	C45—C44—Cl44	119.4 (3)
N3—C4—N5	118.3 (3)	C43—C44—Cl44	119.7 (3)
N3—C4—C41	118.4 (3)	C44—C45—C46	119.5 (3)
N5—C4—C41	123.2 (3)	C44—C45—H45	120.2
N6—C7—C8	113.2 (3)	C46—C45—H45	120.2
N6—C7—C71	119.2 (3)	C45—C46—C41	121.0 (3)
C8—C7—C71	127.5 (3)	C45—C46—H46	119.5
C8A—C8—C7	105.1 (3)	C41—C46—H46	119.5
C8A—C8—H8	127.5	C76—C71—C72	118.8 (3)
C7—C8—H8	127.5	C76—C71—C7	121.0 (3)
N1—C8A—C8	133.4 (3)	C72—C71—C7	120.2 (3)
N1—C8A—N5	120.5 (3)	C73—C72—C71	120.8 (3)
C8—C8A—N5	106.2 (3)	C73—C72—H72	119.6
C22—C21—S2	114.2 (3)	C71—C72—H72	119.6
C22—C21—H21A	108.7	C72—C73—C74	118.8 (3)
S2—C21—H21A	108.7	C72—C73—H73	120.6
C22—C21—H21B	108.7	C74—C73—H73	120.6
S2—C21—H21B	108.7	C75—C74—C73	121.7 (3)
H21A—C21—H21B	107.6	C75—C74—Cl74	119.3 (2)
C21—C22—H22A	109.5	C73—C74—Cl74	119.0 (2)
C21—C22—H22B	109.5	C74—C75—C76	118.8 (3)
H22A—C22—H22B	109.5	C74—C75—H75	120.6
C21—C22—H22C	109.5	C76—C75—H75	120.6
H22A—C22—H22C	109.5	C75—C76—C71	121.1 (3)
H22B—C22—H22C	109.5	C75—C76—H76	119.5
C46—C41—C42	117.8 (3)	C71—C76—H76	119.5
C4—N5—N6—C7	179.3 (3)	N5—C4—C41—C46	8.4 (5)
C8A—N5—N6—C7	−0.2 (3)	N3—C4—C41—C42	6.1 (4)
C8A—N1—C2—N3	2.1 (5)	N5—C4—C41—C42	−173.2 (3)
C8A—N1—C2—S2	179.9 (2)	C46—C41—C42—C43	−1.9 (5)
C4—N3—C2—N1	−0.8 (5)	C4—C41—C42—C43	179.6 (3)
C4—N3—C2—S2	−178.6 (2)	C41—C42—C43—C44	0.8 (5)
C21—S2—C2—N1	179.6 (2)	C42—C43—C44—C45	1.5 (5)
C21—S2—C2—N3	−2.3 (3)	C42—C43—C44—Cl44	−178.4 (3)
C2—N3—C4—N5	−0.3 (4)	C43—C44—C45—C46	−2.7 (6)
C2—N3—C4—C41	−179.5 (3)	Cl44—C44—C45—C46	177.2 (3)
N6—N5—C4—N3	−179.6 (3)	C44—C45—C46—C41	1.6 (6)
C8A—N5—C4—N3	−0.1 (4)	C42—C41—C46—C45	0.7 (5)
N6—N5—C4—C41	−0.3 (5)	C4—C41—C46—C45	179.1 (3)
C8A—N5—C4—C41	179.2 (3)	N6—C7—C71—C76	−177.9 (3)
N5—N6—C7—C8	0.0 (4)	C8—C7—C71—C76	0.7 (5)
N5—N6—C7—C71	178.8 (3)	N6—C7—C71—C72	1.2 (5)
N6—C7—C8—C8A	0.2 (4)	C8—C7—C71—C72	179.9 (3)
C71—C7—C8—C8A	−178.5 (3)	C76—C71—C72—C73	1.0 (5)
C2—N1—C8A—C8	178.6 (4)	C7—C71—C72—C73	−178.2 (3)
C2—N1—C8A—N5	−2.3 (4)	C71—C72—C73—C74	−0.7 (5)
C7—C8—C8A—N1	178.9 (4)	C72—C73—C74—C75	−0.2 (5)
C7—C8—C8A—N5	−0.3 (4)	C72—C73—C74—Cl74	−179.9 (3)
N6—N5—C8A—N1	−179.0 (3)	C73—C74—C75—C76	0.8 (5)
C4—N5—C8A—N1	1.4 (5)	Cl74—C74—C75—C76	−179.5 (2)
N6—N5—C8A—C8	0.3 (4)	C74—C75—C76—C71	−0.5 (5)
C4—N5—C8A—C8	−179.2 (3)	C72—C71—C76—C75	−0.3 (5)
C2—S2—C21—C22	−80.3 (3)	C7—C71—C76—C75	178.8 (3)
N3—C4—C41—C46	−172.4 (3)