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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107064074/gg3133sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107064074/gg3133Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107064074/gg3133IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107064074/gg3133IIIsup4.hkl
Contains datablock III

CCDC references: 677221; 677222; 677223

Comment top

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 ππ 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 ππ 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 top

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

Experimental top

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].

Refinement top

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 Uiso(H) = kUeq(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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] 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).
[Figure 5] 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 top
Crystal data top
C20H18N4SZ = 2
Mr = 346.45F(000) = 364
Triclinic, P1Dx = 1.357 Mg m3
Hall symbol: -P 1Melting point: 397 K
a = 4.8076 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.6397 (5) ÅCell parameters from 3861 reflections
c = 15.5010 (7) Åθ = 3.9–27.5°
α = 92.164 (4)°µ = 0.20 mm1
β = 96.217 (5)°T = 120 K
γ = 100.087 (4)°Block, colourless
V = 847.56 (8) Å30.62 × 0.42 × 0.05 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3861 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2858 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.9°
ϕ & ω scansh = 65
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1514
Tmin = 0.886, Tmax = 0.990l = 2020
13384 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0358P)2 + 0.5471P]
where P = (Fo2 + 2Fc2)/3
3861 reflections(Δ/σ)max < 0.001
264 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C20H18N4Sγ = 100.087 (4)°
Mr = 346.45V = 847.56 (8) Å3
Triclinic, P1Z = 2
a = 4.8076 (3) ÅMo Kα radiation
b = 11.6397 (5) ŵ = 0.20 mm1
c = 15.5010 (7) ÅT = 120 K
α = 92.164 (4)°0.62 × 0.42 × 0.05 mm
β = 96.217 (5)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3861 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2858 reflections with I > 2σ(I)
Tmin = 0.886, Tmax = 0.990Rint = 0.036
13384 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.07Δρmax = 0.32 e Å3
3861 reflectionsΔρmin = 0.31 e Å3
264 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S20.04044 (10)0.12973 (4)0.88304 (3)0.02346 (13)
N10.2504 (3)0.12197 (12)0.74638 (9)0.0205 (3)
N30.3530 (3)0.29352 (12)0.84366 (9)0.0205 (3)
N50.6002 (3)0.28969 (12)0.72425 (9)0.0198 (3)
N60.7943 (3)0.32813 (13)0.66880 (9)0.0223 (3)
C20.2117 (4)0.18407 (15)0.81480 (11)0.0198 (4)
C40.5499 (4)0.34551 (15)0.79871 (11)0.0204 (4)
C70.7655 (4)0.23854 (15)0.60945 (11)0.0201 (4)
C80.5600 (4)0.14299 (15)0.62612 (11)0.0218 (4)
C8A0.4533 (4)0.17628 (15)0.69945 (11)0.0199 (4)
C210.1931 (4)0.01242 (15)0.83150 (12)0.0233 (4)
C220.4076 (4)0.07243 (16)0.88777 (13)0.0272 (4)
C410.7133 (4)0.46165 (15)0.83175 (11)0.0214 (4)
C440.9966 (4)0.67626 (16)0.90758 (12)0.0228 (4)
C42A0.5785 (8)0.5260 (3)0.8903 (2)0.0213 (7)0.50
C43A0.7261 (8)0.6316 (3)0.9284 (2)0.0226 (8)0.50
C45A1.1151 (9)0.6162 (3)0.8466 (3)0.0243 (8)0.50
C46A0.9653 (9)0.5094 (3)0.8076 (3)0.0226 (8)0.50
C42B0.7396 (8)0.4838 (3)0.9233 (2)0.0223 (7)0.50
C43B0.8778 (8)0.5926 (3)0.9601 (2)0.0236 (8)0.50
C45B0.9883 (9)0.6516 (3)0.8191 (3)0.0233 (8)0.50
C46B0.8559 (9)0.5429 (3)0.7819 (3)0.0215 (8)0.50
C710.9426 (4)0.24787 (15)0.53764 (11)0.0212 (4)
C721.1076 (4)0.35338 (17)0.52152 (13)0.0301 (4)
C731.2746 (5)0.3593 (2)0.45401 (14)0.0407 (6)
C741.2865 (4)0.26156 (19)0.40143 (12)0.0310 (5)
C751.1190 (4)0.15722 (18)0.41701 (12)0.0298 (4)
C760.9495 (4)0.15008 (17)0.48404 (12)0.0284 (4)
C771.4771 (5)0.2691 (2)0.33016 (15)0.0502 (7)
H80.50640.07040.59330.026*
H21A0.28790.00400.77270.028*
H21B0.04230.05930.82580.028*
H22A0.30950.08510.94440.041*
H22B0.50260.14780.85930.041*
H22C0.54930.02310.89590.041*
H441.08330.74990.93180.027*
H42A0.39080.49670.90280.026*0.50
H43A0.64220.67380.96900.027*0.50
H45A1.29790.64740.83110.029*0.50
H46A1.04320.47050.76350.027*0.50
H42B0.66320.42470.95920.027*0.50
H43B0.89010.60911.02100.028*0.50
H45B1.07380.70950.78380.028*0.50
H46B0.86340.52440.72210.026*0.50
H721.10590.42170.55690.036*
H731.38430.43240.44330.049*
H751.12010.08930.38120.036*
H760.83610.07730.49360.034*
H77A1.36810.28110.27510.075*
H77B1.55160.19630.32480.075*
H77C1.63560.33480.34420.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S20.0257 (3)0.0195 (2)0.0242 (2)0.00043 (18)0.00539 (18)0.00027 (17)
N10.0213 (8)0.0182 (7)0.0217 (8)0.0035 (6)0.0014 (6)0.0002 (6)
N30.0230 (8)0.0164 (7)0.0217 (8)0.0018 (6)0.0039 (6)0.0016 (6)
N50.0241 (8)0.0169 (7)0.0182 (7)0.0025 (6)0.0042 (6)0.0008 (6)
N60.0279 (8)0.0194 (8)0.0200 (7)0.0029 (6)0.0075 (6)0.0008 (6)
C20.0207 (9)0.0195 (9)0.0196 (9)0.0057 (7)0.0003 (7)0.0028 (7)
C40.0240 (9)0.0189 (9)0.0189 (9)0.0047 (7)0.0035 (7)0.0014 (7)
C70.0252 (9)0.0182 (9)0.0174 (8)0.0072 (7)0.0003 (7)0.0003 (7)
C80.0262 (9)0.0182 (9)0.0205 (9)0.0045 (7)0.0009 (7)0.0023 (7)
C8A0.0203 (9)0.0172 (8)0.0212 (9)0.0030 (7)0.0008 (7)0.0011 (7)
C210.0244 (10)0.0183 (9)0.0265 (10)0.0019 (7)0.0035 (8)0.0019 (7)
C220.0260 (10)0.0236 (9)0.0305 (10)0.0013 (8)0.0058 (8)0.0014 (8)
C410.0258 (9)0.0176 (9)0.0214 (9)0.0037 (7)0.0065 (7)0.0002 (7)
C440.0248 (9)0.0180 (9)0.0244 (9)0.0006 (7)0.0041 (8)0.0027 (7)
C42A0.0242 (19)0.0188 (17)0.0209 (18)0.0020 (15)0.0049 (15)0.0026 (14)
C43A0.031 (2)0.0172 (17)0.0211 (18)0.0056 (16)0.0069 (16)0.0018 (14)
C45A0.024 (2)0.0219 (19)0.025 (2)0.0026 (17)0.0044 (16)0.0017 (15)
C46A0.029 (2)0.019 (2)0.021 (2)0.0042 (17)0.0090 (17)0.0001 (16)
C42B0.0214 (18)0.0236 (19)0.0221 (18)0.0038 (15)0.0042 (15)0.0014 (15)
C43B0.0218 (19)0.0255 (19)0.0234 (19)0.0038 (16)0.0028 (15)0.0005 (15)
C45B0.024 (2)0.022 (2)0.024 (2)0.0035 (17)0.0061 (16)0.0046 (16)
C46B0.028 (2)0.019 (2)0.0190 (19)0.0050 (17)0.0080 (17)0.0034 (15)
C710.0228 (9)0.0240 (9)0.0172 (8)0.0069 (7)0.0005 (7)0.0004 (7)
C720.0330 (11)0.0273 (10)0.0274 (10)0.0018 (8)0.0076 (8)0.0086 (8)
C730.0387 (12)0.0423 (13)0.0341 (12)0.0149 (10)0.0134 (10)0.0122 (10)
C740.0236 (10)0.0490 (13)0.0196 (9)0.0059 (9)0.0022 (8)0.0047 (9)
C750.0392 (12)0.0328 (11)0.0209 (9)0.0171 (9)0.0034 (8)0.0027 (8)
C760.0411 (12)0.0218 (9)0.0246 (10)0.0095 (8)0.0071 (8)0.0020 (7)
C770.0350 (12)0.0790 (19)0.0324 (12)0.0025 (12)0.0137 (10)0.0169 (12)
Geometric parameters (Å, º) top
S2—C21.7461 (18)C44—C43A1.391 (4)
S2—C211.8062 (18)C44—H440.93
N1—C21.309 (2)C42A—C43A1.382 (5)
N1—C8A1.361 (2)C42A—H42A0.95
N3—C41.312 (2)C43A—H43A0.95
N3—C21.368 (2)C45A—C46A1.402 (5)
N5—N61.366 (2)C45A—H45A0.95
N5—C41.368 (2)C46A—H46A0.95
N5—C8A1.402 (2)C42B—C43B1.392 (5)
N6—C71.342 (2)C42B—H42B0.95
C4—C411.482 (2)C43B—H43B0.95
C7—C81.404 (3)C45B—C46B1.386 (5)
C7—C711.469 (2)C45B—H45B0.95
C8—C8A1.367 (2)C46B—H46B0.95
C8—H80.95C71—C721.388 (3)
C21—C221.517 (2)C71—C761.391 (3)
C21—H21A0.99C72—C731.383 (3)
C21—H21B0.99C72—H720.95
C22—H22A0.98C73—C741.387 (3)
C22—H22B0.98C73—H730.95
C22—H22C0.98C74—C751.380 (3)
C41—C46A1.340 (4)C74—C771.505 (3)
C41—C46B1.380 (4)C75—C761.385 (3)
C41—C42B1.421 (4)C75—H750.95
C41—C42A1.433 (4)C76—H760.95
C44—C43B1.379 (4)C77—H77A0.98
C44—C45A1.383 (4)C77—H77B0.98
C44—C45B1.385 (4)C77—H77C0.98
C2—S2—C21102.54 (8)C43A—C42A—H42A120.6
C2—N1—C8A114.23 (15)C41—C42A—H42A120.6
C4—N3—C2118.17 (15)C42A—C43A—C44120.4 (3)
N6—N5—C4128.05 (15)C42A—C43A—H43A119.8
N6—N5—C8A111.81 (14)C44—C43A—H43A119.8
C4—N5—C8A120.06 (15)C44—C45A—C46A120.0 (3)
C7—N6—N5103.82 (14)C44—C45A—H45A120.0
N1—C2—N3127.56 (16)C46A—C45A—H45A120.0
N1—C2—S2121.09 (14)C41—C46A—C45A120.7 (3)
N3—C2—S2111.34 (12)C41—C46A—H46A119.7
N3—C4—N5118.91 (16)C45A—C46A—H46A119.7
N3—C4—C41118.51 (15)C43B—C42B—C41119.6 (3)
N5—C4—C41122.56 (15)C43B—C42B—H42B120.2
N6—C7—C8112.74 (16)C41—C42B—H42B120.2
N6—C7—C71119.77 (16)C44—C43B—C42B119.7 (3)
C8—C7—C71127.49 (16)C44—C43B—H43B120.2
C8A—C8—C7105.61 (16)C42B—C43B—H43B120.2
C8A—C8—H8127.2C44—C45B—C46B120.3 (3)
C7—C8—H8127.2C44—C45B—H45B119.8
N1—C8A—C8133.00 (16)C46B—C45B—H45B119.8
N1—C8A—N5120.98 (15)C41—C46B—C45B120.0 (3)
C8—C8A—N5106.02 (15)C41—C46B—H46B120.0
C22—C21—S2107.87 (13)C45B—C46B—H46B120.0
C22—C21—H21A110.1C72—C71—C76118.22 (17)
S2—C21—H21A110.1C72—C71—C7121.35 (16)
C22—C21—H21B110.1C76—C71—C7120.43 (17)
S2—C21—H21B110.1C73—C72—C71120.08 (18)
H21A—C21—H21B108.4C73—C72—H72120.0
C21—C22—H22A109.5C71—C72—H72120.0
C21—C22—H22B109.5C72—C73—C74121.9 (2)
H22A—C22—H22B109.5C72—C73—H73119.0
C21—C22—H22C109.5C74—C73—H73119.0
H22A—C22—H22C109.5C75—C74—C73117.74 (18)
H22B—C22—H22C109.5C75—C74—C77121.18 (19)
C46B—C41—C42B119.2 (3)C73—C74—C77121.1 (2)
C46A—C41—C42A120.0 (3)C74—C75—C76120.99 (18)
C46A—C41—C4124.4 (2)C74—C75—H75119.5
C46B—C41—C4125.2 (2)C76—C75—H75119.5
C42B—C41—C4115.4 (2)C75—C76—C71121.03 (19)
C42A—C41—C4115.6 (2)C75—C76—H76119.5
C43B—C44—C45B120.6 (3)C71—C76—H76119.5
C45A—C44—C43A119.7 (3)C74—C77—H77A109.5
C43B—C44—H44119.7C74—C77—H77B109.5
C45A—C44—H44122.5H77A—C77—H77B109.5
C45B—C44—H44119.7C74—C77—H77C109.5
C43A—C44—H44117.5H77A—C77—H77C109.5
C43A—C42A—C41118.9 (3)H77B—C77—H77C109.5
C4—N5—N6—C7177.08 (16)N5—C4—C41—C42A159.0 (2)
C8A—N5—N6—C70.38 (18)C46A—C41—C42A—C43A7.1 (5)
C8A—N1—C2—N31.1 (3)C46B—C41—C42A—C43A40.8 (4)
C8A—N1—C2—S2179.74 (12)C42B—C41—C42A—C43A74.6 (4)
C4—N3—C2—N10.7 (3)C4—C41—C42A—C43A175.7 (3)
C4—N3—C2—S2179.91 (13)C41—C42A—C43A—C442.4 (5)
C21—S2—C2—N10.74 (16)C45A—C44—C43A—C42A1.8 (5)
C21—S2—C2—N3179.98 (12)C43A—C44—C45A—C46A1.5 (5)
C2—N3—C4—N51.6 (2)C42A—C41—C46A—C45A7.5 (6)
C2—N3—C4—C41177.15 (15)C4—C41—C46A—C45A175.5 (3)
N6—N5—C4—N3179.81 (15)C44—C45A—C46A—C413.2 (6)
C8A—N5—C4—N33.4 (2)C46B—C41—C42B—C43B8.1 (5)
N6—N5—C4—C411.1 (3)C4—C41—C42B—C43B177.0 (3)
C8A—N5—C4—C41175.37 (15)C45A—C44—C43B—C42B39.1 (4)
N5—N6—C7—C80.73 (19)C45B—C44—C43B—C42B2.2 (5)
N5—N6—C7—C71179.84 (14)C41—C42B—C43B—C442.3 (5)
N6—C7—C8—C8A0.8 (2)C43B—C44—C45B—C46B1.1 (5)
C71—C7—C8—C8A179.81 (16)C42B—C41—C46B—C45B9.3 (5)
C2—N1—C8A—C8179.07 (18)C4—C41—C46B—C45B176.3 (3)
C2—N1—C8A—N50.7 (2)C44—C45B—C46B—C414.8 (6)
C7—C8—C8A—N1179.66 (18)N6—C7—C71—C7210.2 (3)
C7—C8—C8A—N50.52 (19)C8—C7—C71—C72170.43 (18)
N6—N5—C8A—N1179.95 (15)N6—C7—C71—C76169.48 (17)
C4—N5—C8A—N13.0 (2)C8—C7—C71—C769.8 (3)
N6—N5—C8A—C80.10 (19)C76—C71—C72—C730.4 (3)
C4—N5—C8A—C8176.90 (15)C7—C71—C72—C73179.32 (19)
C2—S2—C21—C22177.01 (12)C71—C72—C73—C740.9 (3)
N3—C4—C41—C46A160.6 (3)C72—C73—C74—C751.7 (3)
N5—C4—C41—C46A18.1 (4)C72—C73—C74—C77177.9 (2)
N3—C4—C41—C46B158.0 (3)C73—C74—C75—C761.3 (3)
N5—C4—C41—C46B23.3 (3)C77—C74—C75—C76178.4 (2)
N3—C4—C41—C42B27.4 (3)C74—C75—C76—C710.1 (3)
N5—C4—C41—C42B151.3 (2)C72—C71—C76—C750.8 (3)
N3—C4—C41—C42A22.2 (3)C7—C71—C76—C75178.93 (17)
(II) 7-(4-chlorophenyl)-2-ethylsulfanyl-4-phenylpyrazolo[1,5-a][1,3,5]triazine top
Crystal data top
C19H15ClN4SF(000) = 760
Mr = 366.86Dx = 1.459 Mg m3
Monoclinic, P21/cMelting point: 407 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 11.829 (1) ÅCell parameters from 3822 reflections
b = 7.5703 (5) Åθ = 4.2–27.5°
c = 19.5297 (5) ŵ = 0.36 mm1
β = 107.200 (3)°T = 120 K
V = 1670.61 (18) Å3Plate, colourless
Z = 40.56 × 0.34 × 0.05 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3822 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2968 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 4.2°
ϕ & ω scansh = 1515
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 99
Tmin = 0.822, Tmax = 0.982l = 2525
37866 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0328P)2 + 1.4467P]
where P = (Fo2 + 2Fc2)/3
3822 reflections(Δ/σ)max = 0.001
227 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C19H15ClN4SV = 1670.61 (18) Å3
Mr = 366.86Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.829 (1) ŵ = 0.36 mm1
b = 7.5703 (5) ÅT = 120 K
c = 19.5297 (5) Å0.56 × 0.34 × 0.05 mm
β = 107.200 (3)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3822 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2968 reflections with I > 2σ(I)
Tmin = 0.822, Tmax = 0.982Rint = 0.039
37866 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.10Δρmax = 0.29 e Å3
3822 reflectionsΔρmin = 0.34 e Å3
227 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl740.30933 (4)1.48852 (6)0.73815 (3)0.02895 (13)
S20.11011 (4)0.15742 (6)0.38792 (2)0.02328 (12)
N10.11559 (13)0.4691 (2)0.45226 (8)0.0196 (3)
N30.29107 (13)0.29190 (19)0.48366 (7)0.0191 (3)
N50.29545 (12)0.56219 (19)0.53887 (7)0.0171 (3)
N60.34053 (13)0.70054 (19)0.58327 (7)0.0182 (3)
C20.17618 (15)0.3284 (2)0.44699 (9)0.0182 (3)
C40.35187 (15)0.4096 (2)0.52928 (9)0.0171 (3)
C70.24957 (15)0.8130 (2)0.57227 (9)0.0179 (3)
C80.14656 (15)0.7511 (2)0.52129 (9)0.0201 (4)
C8A0.17681 (15)0.5898 (2)0.50008 (9)0.0182 (3)
C210.02137 (15)0.2667 (2)0.33248 (9)0.0207 (4)
C220.00496 (17)0.3957 (3)0.28002 (10)0.0253 (4)
C410.47747 (15)0.3725 (2)0.56738 (9)0.0184 (3)
C420.52485 (16)0.2186 (2)0.54762 (10)0.0236 (4)
C430.64089 (17)0.1712 (2)0.58079 (10)0.0253 (4)
C440.71193 (16)0.2774 (3)0.63389 (10)0.0236 (4)
C450.66627 (17)0.4298 (3)0.65377 (10)0.0273 (4)
C460.54960 (16)0.4785 (3)0.62090 (10)0.0245 (4)
C710.26470 (15)0.9795 (2)0.61253 (9)0.0179 (3)
C720.37400 (15)1.0255 (2)0.66016 (9)0.0200 (4)
C730.38800 (16)1.1816 (2)0.69867 (9)0.0217 (4)
C740.29183 (16)1.2929 (2)0.68918 (9)0.0205 (4)
C750.18241 (16)1.2523 (2)0.64193 (10)0.0226 (4)
C760.16963 (16)1.0946 (2)0.60436 (9)0.0218 (4)
H80.07200.80870.50500.024*
H21A0.07760.17640.30550.025*
H21B0.06000.33070.36370.025*
H22A0.04350.33330.24900.038*
H22B0.05760.48880.30650.038*
H22C0.06910.44870.25060.038*
H420.47670.14560.51090.028*
H430.67190.06560.56710.030*
H440.79190.24540.65660.028*
H450.71510.50250.69040.033*
H460.51900.58400.63490.029*
H720.43970.94860.66620.024*
H730.46261.21180.73120.026*
H750.11741.33080.63540.027*
H760.09461.06430.57240.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl740.0253 (2)0.0254 (2)0.0348 (3)0.00032 (19)0.00681 (19)0.01148 (19)
S20.0218 (2)0.0192 (2)0.0246 (2)0.00180 (18)0.00026 (17)0.00373 (18)
N10.0169 (7)0.0203 (7)0.0202 (7)0.0013 (6)0.0034 (6)0.0016 (6)
N30.0185 (7)0.0192 (7)0.0187 (7)0.0012 (6)0.0043 (6)0.0015 (6)
N50.0177 (7)0.0163 (7)0.0169 (7)0.0007 (6)0.0044 (6)0.0002 (6)
N60.0187 (7)0.0165 (7)0.0185 (7)0.0010 (6)0.0040 (6)0.0017 (6)
C20.0199 (8)0.0183 (8)0.0162 (8)0.0003 (7)0.0049 (7)0.0010 (7)
C40.0189 (8)0.0175 (8)0.0163 (8)0.0019 (7)0.0073 (7)0.0028 (7)
C70.0174 (8)0.0189 (8)0.0176 (8)0.0013 (7)0.0056 (7)0.0025 (7)
C80.0172 (8)0.0213 (9)0.0199 (8)0.0036 (7)0.0023 (7)0.0002 (7)
C8A0.0150 (8)0.0217 (8)0.0174 (8)0.0009 (7)0.0040 (7)0.0013 (7)
C210.0182 (8)0.0212 (9)0.0206 (8)0.0001 (7)0.0026 (7)0.0019 (7)
C220.0238 (9)0.0284 (10)0.0228 (9)0.0005 (8)0.0057 (7)0.0010 (8)
C410.0179 (8)0.0212 (9)0.0160 (8)0.0012 (7)0.0051 (7)0.0039 (7)
C420.0206 (9)0.0217 (9)0.0259 (9)0.0020 (7)0.0030 (7)0.0020 (8)
C430.0230 (9)0.0213 (9)0.0306 (10)0.0056 (7)0.0064 (8)0.0011 (8)
C440.0169 (8)0.0271 (9)0.0258 (9)0.0051 (7)0.0049 (7)0.0074 (8)
C450.0200 (9)0.0321 (10)0.0252 (9)0.0007 (8)0.0005 (7)0.0044 (8)
C460.0204 (9)0.0253 (9)0.0252 (9)0.0046 (7)0.0029 (7)0.0031 (8)
C710.0195 (8)0.0196 (8)0.0150 (8)0.0006 (7)0.0058 (7)0.0017 (7)
C720.0179 (8)0.0206 (9)0.0211 (8)0.0028 (7)0.0049 (7)0.0020 (7)
C730.0180 (8)0.0241 (9)0.0208 (9)0.0010 (7)0.0024 (7)0.0001 (7)
C740.0234 (9)0.0195 (8)0.0196 (8)0.0002 (7)0.0080 (7)0.0010 (7)
C750.0197 (9)0.0227 (9)0.0251 (9)0.0035 (7)0.0063 (7)0.0010 (7)
C760.0177 (8)0.0239 (9)0.0223 (9)0.0010 (7)0.0035 (7)0.0011 (7)
Geometric parameters (Å, º) top
Cl74—C741.7417 (18)C41—C461.392 (2)
S2—C21.7558 (17)C41—C421.396 (2)
S2—C211.8110 (18)C42—C431.381 (3)
N1—C21.305 (2)C42—H420.95
N1—C8A1.354 (2)C43—C441.383 (3)
N3—C41.314 (2)C43—H430.95
N3—C21.364 (2)C44—C451.378 (3)
N5—N61.3636 (19)C44—H440.95
N5—C41.374 (2)C45—C461.389 (3)
N5—C8A1.399 (2)C45—H450.95
N6—C71.339 (2)C46—H460.95
C4—C411.479 (2)C71—C761.394 (2)
C7—C81.406 (2)C71—C721.395 (2)
C7—C711.468 (2)C72—C731.384 (2)
C8—C8A1.370 (2)C72—H720.95
C8—H80.95C73—C741.384 (2)
C21—C221.513 (3)C73—H730.95
C21—H21A0.99C74—C751.384 (3)
C21—H21B0.99C75—C761.386 (3)
C22—H22A0.98C75—H750.95
C22—H22B0.98C76—H760.95
C22—H22C0.98
C2—S2—C21101.12 (8)C46—C41—C4124.75 (16)
C2—N1—C8A114.29 (15)C42—C41—C4116.45 (16)
C4—N3—C2118.64 (15)C43—C42—C41120.80 (17)
N6—N5—C4128.16 (14)C43—C42—H42119.6
N6—N5—C8A111.74 (13)C41—C42—H42119.6
C4—N5—C8A120.11 (14)C42—C43—C44119.99 (17)
C7—N6—N5104.00 (13)C42—C43—H43120.0
N1—C2—N3127.52 (16)C44—C43—H43120.0
N1—C2—S2120.35 (13)C45—C44—C43119.76 (17)
N3—C2—S2112.12 (12)C45—C44—H44120.1
N3—C4—N5118.16 (15)C43—C44—H44120.1
N3—C4—C41118.64 (15)C44—C45—C46120.70 (18)
N5—C4—C41123.20 (15)C44—C45—H45119.7
N6—C7—C8112.87 (15)C46—C45—H45119.7
N6—C7—C71119.68 (15)C45—C46—C41119.95 (17)
C8—C7—C71127.45 (16)C45—C46—H46120.0
C8A—C8—C7105.18 (15)C41—C46—H46120.0
C8A—C8—H8127.4C76—C71—C72118.53 (16)
C7—C8—H8127.4C76—C71—C7120.58 (16)
N1—C8A—C8132.53 (16)C72—C71—C7120.89 (15)
N1—C8A—N5121.25 (15)C73—C72—C71120.92 (16)
C8—C8A—N5106.22 (15)C73—C72—H72119.5
C22—C21—S2112.79 (13)C71—C72—H72119.5
C22—C21—H21A109.0C74—C73—C72119.06 (16)
S2—C21—H21A109.0C74—C73—H73120.5
C22—C21—H21B109.0C72—C73—H73120.5
S2—C21—H21B109.0C73—C74—C75121.58 (17)
H21A—C21—H21B107.8C73—C74—Cl74119.01 (14)
C21—C22—H22A109.5C75—C74—Cl74119.41 (14)
C21—C22—H22B109.5C74—C75—C76118.60 (17)
H22A—C22—H22B109.5C74—C75—H75120.7
C21—C22—H22C109.5C76—C75—H75120.7
H22A—C22—H22C109.5C75—C76—C71121.30 (17)
H22B—C22—H22C109.5C75—C76—H76119.3
C46—C41—C42118.80 (16)C71—C76—H76119.3
C4—N5—N6—C7179.82 (16)N3—C4—C41—C46174.86 (17)
C8A—N5—N6—C70.40 (18)N5—C4—C41—C465.6 (3)
C8A—N1—C2—N30.1 (3)N3—C4—C41—C424.7 (2)
C8A—N1—C2—S2179.52 (12)N5—C4—C41—C42174.88 (16)
C4—N3—C2—N11.2 (3)C46—C41—C42—C430.5 (3)
C4—N3—C2—S2179.26 (12)C4—C41—C42—C43179.10 (17)
C21—S2—C2—N115.00 (16)C41—C42—C43—C440.5 (3)
C21—S2—C2—N3165.47 (12)C42—C43—C44—C450.4 (3)
C2—N3—C4—N51.4 (2)C43—C44—C45—C460.2 (3)
C2—N3—C4—C41178.15 (14)C44—C45—C46—C410.2 (3)
N6—N5—C4—N3179.61 (15)C42—C41—C46—C450.3 (3)
C8A—N5—C4—N30.6 (2)C4—C41—C46—C45179.25 (17)
N6—N5—C4—C410.8 (3)N6—C7—C71—C76176.97 (16)
C8A—N5—C4—C41178.93 (15)C8—C7—C71—C762.4 (3)
N5—N6—C7—C80.40 (19)N6—C7—C71—C722.5 (2)
N5—N6—C7—C71179.04 (14)C8—C7—C71—C72178.13 (17)
N6—C7—C8—C8A0.2 (2)C76—C71—C72—C730.2 (3)
C71—C7—C8—C8A179.14 (16)C7—C71—C72—C73179.33 (16)
C2—N1—C8A—C8179.84 (18)C71—C72—C73—C740.3 (3)
C2—N1—C8A—N50.8 (2)C72—C73—C74—C750.3 (3)
C7—C8—C8A—N1179.42 (18)C72—C73—C74—Cl74179.56 (13)
C7—C8—C8A—N50.01 (18)C73—C74—C75—C761.0 (3)
N6—N5—C8A—N1179.25 (14)Cl74—C74—C75—C76178.89 (14)
C4—N5—C8A—N10.5 (2)C74—C75—C76—C711.1 (3)
N6—N5—C8A—C80.26 (19)C72—C71—C76—C750.5 (3)
C4—N5—C8A—C8179.94 (14)C7—C71—C76—C75179.97 (16)
C2—S2—C21—C2274.19 (14)
(III) 4,7-bis(4-chlorophenyl)-2-(ethylsulfanyl)pyrazolo[1,5-a][1,3,5]triazine top
Crystal data top
C19H14Cl2N4SF(000) = 824
Mr = 401.30Dx = 1.506 Mg m3
Monoclinic, P21/nMelting point: 431 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 7.7117 (4) ÅCell parameters from 4039 reflections
b = 8.3261 (10) Åθ = 3.8–27.5°
c = 27.678 (3) ŵ = 0.50 mm1
β = 94.978 (5)°T = 120 K
V = 1770.5 (3) Å3Block, colourless
Z = 40.47 × 0.24 × 0.14 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
4039 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2513 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.8°
ϕ & ω scansh = 109
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1010
Tmin = 0.801, Tmax = 0.934l = 3535
39992 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0669P)2 + 2.3365P]
where P = (Fo2 + 2Fc2)/3
4039 reflections(Δ/σ)max = 0.001
236 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.50 e Å3
Crystal data top
C19H14Cl2N4SV = 1770.5 (3) Å3
Mr = 401.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.7117 (4) ŵ = 0.50 mm1
b = 8.3261 (10) ÅT = 120 K
c = 27.678 (3) Å0.47 × 0.24 × 0.14 mm
β = 94.978 (5)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
4039 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2513 reflections with I > 2σ(I)
Tmin = 0.801, Tmax = 0.934Rint = 0.074
39992 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.155H-atom parameters constrained
S = 1.06Δρmax = 0.49 e Å3
4039 reflectionsΔρmin = 0.50 e Å3
236 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl440.53273 (13)1.12947 (11)0.60946 (4)0.0411 (3)
Cl740.22872 (11)0.40819 (10)0.24961 (3)0.0321 (2)
S20.04836 (12)0.15969 (10)0.66827 (3)0.0309 (2)
N10.0733 (4)0.1695 (3)0.57532 (9)0.0266 (6)
N30.1761 (3)0.4036 (3)0.61961 (9)0.0246 (6)
N50.1896 (3)0.3984 (3)0.53699 (9)0.0232 (6)
N60.2241 (3)0.4522 (3)0.49218 (9)0.0261 (6)
C20.1072 (4)0.2537 (4)0.61535 (11)0.0247 (7)
C40.2173 (4)0.4770 (4)0.58032 (11)0.0226 (7)
C70.1756 (4)0.3309 (4)0.46263 (11)0.0231 (7)
C80.1101 (4)0.1987 (4)0.48683 (12)0.0267 (7)
C8A0.1188 (4)0.2430 (4)0.53469 (11)0.0246 (7)
C210.1133 (4)0.3048 (4)0.71493 (12)0.0309 (8)
C220.3047 (5)0.3023 (5)0.73139 (14)0.0416 (9)
C410.2931 (4)0.6389 (4)0.58507 (11)0.0232 (7)
C420.3323 (5)0.6989 (4)0.63179 (12)0.0305 (8)
C430.4045 (4)0.8488 (4)0.63955 (12)0.0319 (8)
C440.4367 (4)0.9424 (4)0.60021 (12)0.0294 (8)
C450.3941 (5)0.8896 (4)0.55373 (13)0.0373 (9)
C460.3246 (5)0.7378 (4)0.54619 (13)0.0329 (8)
C710.1915 (4)0.3480 (4)0.41023 (11)0.0236 (7)
C720.2596 (4)0.4885 (4)0.39204 (12)0.0284 (7)
C730.2706 (4)0.5079 (4)0.34288 (12)0.0282 (7)
C740.2146 (4)0.3844 (4)0.31188 (11)0.0244 (7)
C750.1490 (4)0.2433 (4)0.32887 (12)0.0286 (8)
C760.1372 (4)0.2263 (4)0.37806 (12)0.0265 (7)
H80.06870.09990.47300.032*
H21A0.08190.41350.70260.037*
H21B0.04660.28430.74330.037*
H22A0.37180.33120.70420.062*
H22B0.33800.19440.74290.062*
H22C0.32870.37970.75780.062*
H420.30860.63490.65890.037*
H430.43190.88730.67160.038*
H450.41230.95700.52690.045*
H460.29790.70020.51400.040*
H720.29880.57190.41370.034*
H730.31580.60430.33050.034*
H750.11250.15920.30710.034*
H760.09120.12990.39010.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl440.0467 (6)0.0273 (5)0.0496 (6)0.0131 (4)0.0052 (4)0.0066 (4)
Cl740.0413 (5)0.0331 (5)0.0230 (4)0.0003 (4)0.0088 (3)0.0005 (3)
S20.0435 (6)0.0257 (5)0.0241 (4)0.0081 (4)0.0062 (4)0.0008 (3)
N10.0339 (16)0.0232 (15)0.0226 (14)0.0047 (12)0.0028 (12)0.0005 (11)
N30.0280 (15)0.0212 (14)0.0247 (14)0.0016 (12)0.0036 (11)0.0003 (11)
N50.0298 (15)0.0199 (13)0.0199 (13)0.0026 (11)0.0032 (11)0.0009 (11)
N60.0315 (15)0.0241 (14)0.0222 (14)0.0032 (12)0.0003 (11)0.0008 (11)
C20.0256 (18)0.0249 (17)0.0238 (17)0.0001 (14)0.0028 (13)0.0006 (13)
C40.0233 (17)0.0221 (16)0.0222 (16)0.0017 (13)0.0004 (13)0.0002 (13)
C70.0231 (17)0.0217 (16)0.0239 (16)0.0031 (13)0.0006 (13)0.0002 (13)
C80.0319 (19)0.0212 (17)0.0270 (17)0.0066 (14)0.0024 (14)0.0035 (13)
C8A0.0279 (18)0.0203 (16)0.0258 (17)0.0031 (13)0.0028 (14)0.0001 (13)
C210.036 (2)0.0332 (19)0.0237 (17)0.0018 (16)0.0059 (14)0.0034 (14)
C220.038 (2)0.045 (2)0.040 (2)0.0008 (18)0.0042 (17)0.0019 (18)
C410.0216 (16)0.0218 (17)0.0265 (16)0.0021 (13)0.0033 (13)0.0014 (13)
C420.037 (2)0.0243 (17)0.0299 (18)0.0023 (15)0.0035 (15)0.0014 (14)
C430.037 (2)0.0306 (19)0.0282 (18)0.0041 (16)0.0018 (15)0.0053 (15)
C440.0298 (19)0.0219 (17)0.0362 (19)0.0017 (14)0.0012 (15)0.0050 (14)
C450.046 (2)0.0303 (19)0.036 (2)0.0108 (17)0.0088 (17)0.0030 (16)
C460.043 (2)0.0262 (18)0.0297 (19)0.0108 (16)0.0034 (16)0.0047 (15)
C710.0249 (17)0.0222 (16)0.0235 (16)0.0006 (13)0.0013 (13)0.0024 (13)
C720.0347 (19)0.0245 (17)0.0254 (17)0.0034 (15)0.0006 (14)0.0030 (14)
C730.0336 (19)0.0230 (17)0.0280 (17)0.0021 (15)0.0016 (14)0.0033 (14)
C740.0265 (17)0.0236 (17)0.0235 (16)0.0041 (13)0.0047 (13)0.0007 (13)
C750.036 (2)0.0219 (17)0.0275 (18)0.0016 (14)0.0008 (15)0.0034 (14)
C760.0301 (18)0.0228 (17)0.0266 (17)0.0019 (14)0.0028 (14)0.0009 (14)
Geometric parameters (Å, º) top
Cl44—C441.734 (3)C22—H22C0.98
Cl74—C741.748 (3)C41—C461.393 (5)
S2—C21.755 (3)C41—C421.395 (4)
S2—C211.807 (3)C42—C431.376 (5)
N1—C21.318 (4)C42—H420.95
N1—C8A1.353 (4)C43—C441.379 (5)
N3—C41.310 (4)C43—H430.95
N3—C21.358 (4)C44—C451.372 (5)
N5—N61.366 (3)C45—C461.382 (5)
N5—C41.366 (4)C45—H450.95
N5—C8A1.403 (4)C46—H460.95
N6—C71.333 (4)C71—C761.389 (4)
C4—C411.471 (4)C71—C721.394 (5)
C7—C81.405 (4)C72—C731.380 (4)
C7—C711.473 (4)C72—H720.95
C8—C8A1.371 (4)C73—C741.384 (5)
C8—H80.95C73—H730.95
C21—C221.506 (5)C74—C751.378 (5)
C21—H21A0.99C75—C761.379 (4)
C21—H21B0.99C75—H750.95
C22—H22A0.98C76—H760.95
C22—H22B0.98
C2—S2—C21102.87 (16)C46—C41—C4124.6 (3)
C2—N1—C8A114.3 (3)C42—C41—C4117.6 (3)
C4—N3—C2118.5 (3)C43—C42—C41121.5 (3)
N6—N5—C4127.7 (3)C43—C42—H42119.3
N6—N5—C8A111.5 (2)C41—C42—H42119.3
C4—N5—C8A120.8 (3)C42—C43—C44119.2 (3)
C7—N6—N5104.0 (2)C42—C43—H43120.4
N1—C2—N3127.6 (3)C44—C43—H43120.4
N1—C2—S2114.7 (2)C45—C44—C43121.0 (3)
N3—C2—S2117.7 (2)C45—C44—Cl44119.4 (3)
N3—C4—N5118.3 (3)C43—C44—Cl44119.7 (3)
N3—C4—C41118.4 (3)C44—C45—C46119.5 (3)
N5—C4—C41123.2 (3)C44—C45—H45120.2
N6—C7—C8113.2 (3)C46—C45—H45120.2
N6—C7—C71119.2 (3)C45—C46—C41121.0 (3)
C8—C7—C71127.5 (3)C45—C46—H46119.5
C8A—C8—C7105.1 (3)C41—C46—H46119.5
C8A—C8—H8127.5C76—C71—C72118.8 (3)
C7—C8—H8127.5C76—C71—C7121.0 (3)
N1—C8A—C8133.4 (3)C72—C71—C7120.2 (3)
N1—C8A—N5120.5 (3)C73—C72—C71120.8 (3)
C8—C8A—N5106.2 (3)C73—C72—H72119.6
C22—C21—S2114.2 (3)C71—C72—H72119.6
C22—C21—H21A108.7C72—C73—C74118.8 (3)
S2—C21—H21A108.7C72—C73—H73120.6
C22—C21—H21B108.7C74—C73—H73120.6
S2—C21—H21B108.7C75—C74—C73121.7 (3)
H21A—C21—H21B107.6C75—C74—Cl74119.3 (2)
C21—C22—H22A109.5C73—C74—Cl74119.0 (2)
C21—C22—H22B109.5C74—C75—C76118.8 (3)
H22A—C22—H22B109.5C74—C75—H75120.6
C21—C22—H22C109.5C76—C75—H75120.6
H22A—C22—H22C109.5C75—C76—C71121.1 (3)
H22B—C22—H22C109.5C75—C76—H76119.5
C46—C41—C42117.8 (3)C71—C76—H76119.5
C4—N5—N6—C7179.3 (3)N5—C4—C41—C468.4 (5)
C8A—N5—N6—C70.2 (3)N3—C4—C41—C426.1 (4)
C8A—N1—C2—N32.1 (5)N5—C4—C41—C42173.2 (3)
C8A—N1—C2—S2179.9 (2)C46—C41—C42—C431.9 (5)
C4—N3—C2—N10.8 (5)C4—C41—C42—C43179.6 (3)
C4—N3—C2—S2178.6 (2)C41—C42—C43—C440.8 (5)
C21—S2—C2—N1179.6 (2)C42—C43—C44—C451.5 (5)
C21—S2—C2—N32.3 (3)C42—C43—C44—Cl44178.4 (3)
C2—N3—C4—N50.3 (4)C43—C44—C45—C462.7 (6)
C2—N3—C4—C41179.5 (3)Cl44—C44—C45—C46177.2 (3)
N6—N5—C4—N3179.6 (3)C44—C45—C46—C411.6 (6)
C8A—N5—C4—N30.1 (4)C42—C41—C46—C450.7 (5)
N6—N5—C4—C410.3 (5)C4—C41—C46—C45179.1 (3)
C8A—N5—C4—C41179.2 (3)N6—C7—C71—C76177.9 (3)
N5—N6—C7—C80.0 (4)C8—C7—C71—C760.7 (5)
N5—N6—C7—C71178.8 (3)N6—C7—C71—C721.2 (5)
N6—C7—C8—C8A0.2 (4)C8—C7—C71—C72179.9 (3)
C71—C7—C8—C8A178.5 (3)C76—C71—C72—C731.0 (5)
C2—N1—C8A—C8178.6 (4)C7—C71—C72—C73178.2 (3)
C2—N1—C8A—N52.3 (4)C71—C72—C73—C740.7 (5)
C7—C8—C8A—N1178.9 (4)C72—C73—C74—C750.2 (5)
C7—C8—C8A—N50.3 (4)C72—C73—C74—Cl74179.9 (3)
N6—N5—C8A—N1179.0 (3)C73—C74—C75—C760.8 (5)
C4—N5—C8A—N11.4 (5)Cl74—C74—C75—C76179.5 (2)
N6—N5—C8A—C80.3 (4)C74—C75—C76—C710.5 (5)
C4—N5—C8A—C8179.2 (3)C72—C71—C76—C750.3 (5)
C2—S2—C21—C2280.3 (3)C7—C71—C76—C75178.8 (3)
N3—C4—C41—C46172.4 (3)

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC20H18N4SC19H15ClN4SC19H14Cl2N4S
Mr346.45366.86401.30
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/n
Temperature (K)120120120
a, b, c (Å)4.8076 (3), 11.6397 (5), 15.5010 (7)11.829 (1), 7.5703 (5), 19.5297 (5)7.7117 (4), 8.3261 (10), 27.678 (3)
α, β, γ (°)92.164 (4), 96.217 (5), 100.087 (4)90, 107.200 (3), 9090, 94.978 (5), 90
V3)847.56 (8)1670.61 (18)1770.5 (3)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.200.360.50
Crystal size (mm)0.62 × 0.42 × 0.050.56 × 0.34 × 0.050.47 × 0.24 × 0.14
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.886, 0.9900.822, 0.9820.801, 0.934
No. of measured, independent and
observed [I > 2σ(I)] reflections
13384, 3861, 2858 37866, 3822, 2968 39992, 4039, 2513
Rint0.0360.0390.074
(sin θ/λ)max1)0.6500.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.106, 1.07 0.036, 0.092, 1.10 0.055, 0.155, 1.06
No. of reflections386138224039
No. of parameters264227236
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.310.29, 0.340.49, 0.50

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, °) for compounds (I)–(III) top
Parameter(I)(II)(III)
N1—C21.309 (2)1.305 (2)1.318 (4)
C2—N31.368 (2)1.364 (2)1.358 (4)
N3—C41.312 (2)1.314 (2)1.310 (4)
C4—N51.368 (2)1.374 (2)1.366 (4)
N5—N61.366 (2)1.3636 (19)1.366 (3)
N6—C71.342 (2)1.339 (2)1.333 (4)
C7—C81.404 (3)1.406 (2)1.405 (4)
C8—C8A1.367 (2)1.370 (2)1.371 (4)
C8A—N11.361 (2)1.354 (2)1.353 (4)
N5—C8A1.402 (2)1.399 (2)1.403 (4)
N1—C2—S2—C21-0.74 (16)15.00 (16)179.6 (2)
C2—S2—C21—C22177.01 (12)74.19 (14)-80.3 (3)
(triazine)/(C41–C46)i4.78 (8)7.58 (15)(9)
(pyrazole)/(C71–C76)10.20 (10)2.63 (9)2.52 (16)
i These dihedral angles in compound (I) are 20.77 (13)° for one orientation of the disordered phenyl ring and 25.99 (13)° for the other.
 

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