Crystal structure of 1,5-diethyl-3',5'-di-phenyl-1,5-di-hydro-3'H-spiro-[pyra-zolo[3,4-d]pyrimidine-4,2'-[1,3,4]thia-diazole].

In the title compound, C22H22N6S, the pyrazolo-[3,4-d]pyrimidine rings system is almost planar, with the r.m.s. deviation for the fitted atoms being 0.011 Å. The two phenyl groups linked to the thia-diazole ring are nearly perpendicular to the fused-ring system as indicated by the dihedral angles of 86.93 (10) and 83.35 (11)°. However, the phenyl rings are almost coplanar with the thia-diazole ring (r.m.s. deviation = 0.015 Å), forming dihedral angles of 10.44 (11) and 10.06 (12)°. In the crystal, mol-ecules are connected into a supra-molecular layer in the ac plane via C-H⋯π inter-actions.

Related literature

For biological properties of pyrazolo­[3,4-d]pyrimidine derivatives, see: Chern et al. (2004 ▸); Schenone et al. (2009 ▸); Dinér et al. (2012 ▸); Taliani et al. (2010 ▸); Trivedi et al. (2012 ▸). For related structures, see: El Fal et al. (2014 ▸, 2015 ▸); Ahoya et al. (2011 ▸); Anothane et al. (2012 ▸).

Experimental

Crystal data

C22H22N6S

M = 402.51

Orthorhombic,

a = 14.501 (5) Å

b = 22.898 (5) Å

c = 12.468 (4) Å

V = 4140 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.18 mm−1

T = 296 K

0.37 × 0.34 × 0.29 mm

Data collection

Bruker X8 APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.589, T max = 0.746

25025 measured reflections

4224 independent reflections

2566 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.138

S = 1.00

4224 reflections

262 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015017405/tk5387sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017405/tk5387Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015017405/tk5387Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015017405/tk5387fig1.tif

Mol­ecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

CCDC reference: 1425539

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H22N6S	Dx = 1.292 Mg m−3
Mr = 402.51	Melting point: 468 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 14.501 (5) Å	Cell parameters from 4224 reflections
b = 22.898 (5) Å	θ = 2.3–26.4°
c = 12.468 (4) Å	µ = 0.18 mm−1
V = 4140 (2) Å3	T = 296 K
Z = 8	Block, yellow
F(000) = 1696	0.37 × 0.34 × 0.29 mm

Bruker X8 APEX diffractometer	4224 independent reflections
Radiation source: fine-focus sealed tube	2566 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
φ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→17
Tmin = 0.589, Tmax = 0.746	k = −24→28
25025 measured reflections	l = −15→15

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.0625P)2 + 0.732P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
4224 reflections	Δρmax = 0.31 e Å−3
262 parameters	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.48041 (15)	0.16398 (10)	0.52664 (19)	0.0383 (5)
C2	0.54607 (15)	0.07863 (9)	0.63901 (19)	0.0363 (5)
C3	0.49773 (15)	0.04386 (10)	0.72025 (19)	0.0373 (5)
C4	0.41299 (17)	0.04978 (11)	0.7732 (2)	0.0511 (7)
H4	0.3727	0.0809	0.7631	0.061*
C5	0.53365 (15)	−0.00752 (10)	0.75801 (19)	0.0377 (5)
C6	0.65913 (16)	−0.00200 (10)	0.6605 (2)	0.0413 (6)
H6	0.7162	−0.0164	0.6392	0.050*
C7	0.69620 (18)	0.07699 (12)	0.5361 (2)	0.0554 (7)
H7A	0.7560	0.0814	0.5700	0.066*
H7B	0.6733	0.1158	0.5199	0.066*
C8	0.7081 (3)	0.04447 (17)	0.4342 (3)	0.1022 (13)
H8A	0.7498	0.0654	0.3884	0.153*
H8B	0.6495	0.0406	0.3992	0.153*
H8C	0.7327	0.0064	0.4492	0.153*
C9	0.4750 (2)	−0.08616 (13)	0.8837 (3)	0.0726 (9)
H9A	0.4554	−0.0814	0.9576	0.087*
H9B	0.5377	−0.1009	0.8841	0.087*
C10	0.4139 (3)	−0.12911 (14)	0.8295 (3)	0.0962 (13)
H10A	0.4166	−0.1657	0.8668	0.144*
H10B	0.4340	−0.1345	0.7568	0.144*
H10C	0.3517	−0.1148	0.8298	0.144*
C11	0.61067 (15)	0.15818 (10)	0.76316 (19)	0.0383 (6)
C12	0.66082 (17)	0.11905 (11)	0.8257 (2)	0.0478 (6)
H12	0.6632	0.0797	0.8072	0.057*
C13	0.70698 (17)	0.13906 (13)	0.9156 (2)	0.0538 (7)
H13	0.7404	0.1128	0.9571	0.065*
C14	0.70444 (18)	0.19696 (13)	0.9449 (2)	0.0576 (8)
H14	0.7357	0.2099	1.0054	0.069*
C15	0.65481 (18)	0.23514 (13)	0.8829 (2)	0.0577 (8)
H15	0.6524	0.2744	0.9021	0.069*
C16	0.60827 (16)	0.21655 (11)	0.7924 (2)	0.0479 (7)
H16	0.5753	0.2432	0.7512	0.058*
C17	0.43453 (15)	0.20319 (10)	0.4501 (2)	0.0399 (6)
C18	0.39468 (17)	0.18210 (12)	0.3574 (2)	0.0505 (7)
H18	0.3970	0.1423	0.3424	0.061*
C19	0.35137 (19)	0.21958 (14)	0.2866 (2)	0.0623 (8)
H19	0.3252	0.2051	0.2239	0.075*
C20	0.3471 (2)	0.27838 (14)	0.3090 (3)	0.0665 (9)
H20	0.3182	0.3037	0.2614	0.080*
C21	0.38543 (19)	0.29943 (13)	0.4014 (3)	0.0646 (8)
H21	0.3823	0.3392	0.4165	0.077*
C22	0.42870 (18)	0.26235 (11)	0.4724 (2)	0.0527 (7)
H22	0.4540	0.2771	0.5354	0.063*
N1	0.52713 (13)	0.18375 (8)	0.60593 (16)	0.0414 (5)
N2	0.56296 (14)	0.14038 (8)	0.67014 (16)	0.0444 (5)
N3	0.63253 (12)	0.04874 (8)	0.61271 (16)	0.0396 (5)
N4	0.61620 (13)	−0.03289 (9)	0.73112 (17)	0.0430 (5)
N5	0.47290 (14)	−0.02945 (9)	0.82976 (18)	0.0523 (6)
N6	0.39730 (15)	0.00565 (10)	0.8391 (2)	0.0618 (7)
S1	0.47272 (5)	0.08793 (3)	0.51716 (6)	0.0486 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0362 (12)	0.0355 (13)	0.0431 (14)	0.0013 (10)	−0.0001 (11)	0.0032 (11)
C2	0.0380 (12)	0.0283 (12)	0.0425 (14)	0.0008 (10)	−0.0069 (10)	−0.0008 (10)
C3	0.0362 (12)	0.0305 (12)	0.0453 (15)	0.0006 (10)	−0.0020 (10)	−0.0003 (11)
C4	0.0440 (14)	0.0471 (16)	0.0621 (19)	0.0096 (12)	0.0070 (12)	0.0006 (14)
C5	0.0365 (12)	0.0331 (13)	0.0435 (14)	−0.0019 (10)	−0.0020 (10)	0.0033 (11)
C6	0.0332 (12)	0.0411 (14)	0.0496 (15)	0.0055 (11)	−0.0048 (11)	−0.0022 (12)
C7	0.0491 (15)	0.0602 (18)	0.0568 (19)	−0.0083 (13)	0.0078 (12)	0.0152 (15)
C8	0.127 (3)	0.107 (3)	0.073 (3)	−0.015 (2)	0.048 (2)	−0.004 (2)
C9	0.070 (2)	0.066 (2)	0.082 (2)	0.0031 (17)	0.0156 (17)	0.0367 (18)
C10	0.118 (3)	0.054 (2)	0.117 (3)	−0.008 (2)	0.038 (3)	0.014 (2)
C11	0.0373 (12)	0.0403 (14)	0.0372 (14)	−0.0053 (10)	0.0004 (10)	−0.0034 (11)
C12	0.0557 (15)	0.0409 (15)	0.0469 (16)	−0.0021 (13)	−0.0091 (12)	0.0008 (12)
C13	0.0506 (15)	0.068 (2)	0.0425 (16)	−0.0036 (14)	−0.0098 (12)	0.0037 (14)
C14	0.0461 (15)	0.075 (2)	0.0516 (18)	−0.0088 (15)	−0.0046 (12)	−0.0178 (15)
C15	0.0515 (15)	0.0553 (18)	0.066 (2)	−0.0024 (14)	−0.0024 (14)	−0.0238 (15)
C16	0.0451 (14)	0.0396 (15)	0.0591 (18)	0.0003 (11)	−0.0071 (12)	−0.0098 (13)
C17	0.0360 (12)	0.0388 (14)	0.0449 (15)	0.0055 (11)	0.0022 (10)	0.0085 (11)
C18	0.0537 (15)	0.0487 (16)	0.0491 (17)	0.0087 (13)	−0.0019 (13)	0.0070 (13)
C19	0.0596 (17)	0.074 (2)	0.0532 (19)	0.0092 (15)	−0.0122 (14)	0.0101 (16)
C20	0.0640 (18)	0.061 (2)	0.074 (2)	0.0148 (16)	−0.0108 (16)	0.0262 (17)
C21	0.0640 (18)	0.0450 (17)	0.085 (2)	0.0131 (14)	−0.0074 (17)	0.0128 (16)
C22	0.0547 (15)	0.0406 (16)	0.0627 (19)	0.0054 (13)	−0.0086 (13)	0.0080 (13)
N1	0.0478 (11)	0.0308 (11)	0.0457 (12)	0.0023 (9)	−0.0042 (10)	0.0065 (9)
N2	0.0595 (13)	0.0278 (11)	0.0461 (13)	−0.0011 (9)	−0.0168 (10)	0.0046 (9)
N3	0.0373 (10)	0.0369 (11)	0.0446 (12)	−0.0005 (9)	0.0006 (8)	0.0041 (9)
N4	0.0377 (11)	0.0395 (12)	0.0519 (14)	0.0061 (9)	−0.0012 (9)	0.0091 (10)
N5	0.0481 (12)	0.0468 (13)	0.0619 (15)	0.0026 (10)	0.0098 (11)	0.0169 (11)
N6	0.0516 (13)	0.0624 (16)	0.0714 (17)	0.0052 (12)	0.0180 (12)	0.0111 (13)
S1	0.0567 (4)	0.0362 (4)	0.0531 (4)	−0.0001 (3)	−0.0217 (3)	0.0025 (3)

C1—N1	1.281 (3)	C10—H10B	0.9600
C1—C17	1.469 (3)	C10—H10C	0.9600
C1—S1	1.749 (2)	C11—C16	1.386 (3)
C2—N3	1.466 (3)	C11—C12	1.393 (3)
C2—C3	1.467 (3)	C11—N2	1.411 (3)
C2—N2	1.487 (3)	C12—C13	1.383 (3)
C2—S1	1.867 (2)	C12—H12	0.9300
C3—C5	1.370 (3)	C13—C14	1.376 (4)
C3—C4	1.401 (3)	C13—H13	0.9300
C4—N6	1.323 (3)	C14—C15	1.371 (4)
C4—H4	0.9300	C14—H14	0.9300
C5—N5	1.352 (3)	C15—C16	1.381 (4)
C5—N4	1.372 (3)	C15—H15	0.9300
C6—N4	1.290 (3)	C16—H16	0.9300
C6—N3	1.361 (3)	C17—C18	1.379 (4)
C6—H6	0.9300	C17—C22	1.386 (3)
C7—N3	1.478 (3)	C18—C19	1.382 (4)
C7—C8	1.482 (4)	C18—H18	0.9300
C7—H7A	0.9700	C19—C20	1.377 (4)
C7—H7B	0.9700	C19—H19	0.9300
C8—H8A	0.9600	C20—C21	1.368 (4)
C8—H8B	0.9600	C20—H20	0.9300
C8—H8C	0.9600	C21—C22	1.378 (4)
C9—N5	1.463 (3)	C21—H21	0.9300
C9—C10	1.486 (5)	C22—H22	0.9300
C9—H9A	0.9700	N1—N2	1.377 (3)
C9—H9B	0.9700	N5—N6	1.364 (3)
C10—H10A	0.9600
N1—C1—C17	121.6 (2)	C12—C11—N2	122.1 (2)
N1—C1—S1	115.96 (18)	C13—C12—C11	119.6 (2)
C17—C1—S1	122.39 (18)	C13—C12—H12	120.2
N3—C2—C3	108.05 (18)	C11—C12—H12	120.2
N3—C2—N2	111.20 (18)	C14—C13—C12	121.4 (3)
C3—C2—N2	114.5 (2)	C14—C13—H13	119.3
N3—C2—S1	111.02 (16)	C12—C13—H13	119.3
C3—C2—S1	110.59 (15)	C15—C14—C13	118.6 (3)
N2—C2—S1	101.41 (14)	C15—C14—H14	120.7
C5—C3—C4	104.8 (2)	C13—C14—H14	120.7
C5—C3—C2	121.5 (2)	C14—C15—C16	121.3 (3)
C4—C3—C2	133.8 (2)	C14—C15—H15	119.3
N6—C4—C3	111.7 (2)	C16—C15—H15	119.3
N6—C4—H4	124.2	C15—C16—C11	120.0 (3)
C3—C4—H4	124.2	C15—C16—H16	120.0
N5—C5—C3	107.4 (2)	C11—C16—H16	120.0
N5—C5—N4	124.9 (2)	C18—C17—C22	119.0 (2)
C3—C5—N4	127.7 (2)	C18—C17—C1	121.3 (2)
N4—C6—N3	129.0 (2)	C22—C17—C1	119.6 (2)
N4—C6—H6	115.5	C17—C18—C19	120.6 (3)
N3—C6—H6	115.5	C17—C18—H18	119.7
N3—C7—C8	114.0 (2)	C19—C18—H18	119.7
N3—C7—H7A	108.8	C20—C19—C18	119.9 (3)
C8—C7—H7A	108.8	C20—C19—H19	120.1
N3—C7—H7B	108.8	C18—C19—H19	120.1
C8—C7—H7B	108.8	C21—C20—C19	119.8 (3)
H7A—C7—H7B	107.6	C21—C20—H20	120.1
C7—C8—H8A	109.5	C19—C20—H20	120.1
C7—C8—H8B	109.5	C20—C21—C22	120.6 (3)
H8A—C8—H8B	109.5	C20—C21—H21	119.7
C7—C8—H8C	109.5	C22—C21—H21	119.7
H8A—C8—H8C	109.5	C21—C22—C17	120.1 (3)
H8B—C8—H8C	109.5	C21—C22—H22	120.0
N5—C9—C10	111.5 (3)	C17—C22—H22	120.0
N5—C9—H9A	109.3	C1—N1—N2	113.15 (19)
C10—C9—H9A	109.3	N1—N2—C11	117.04 (18)
N5—C9—H9B	109.3	N1—N2—C2	118.15 (18)
C10—C9—H9B	109.3	C11—N2—C2	124.77 (19)
H9A—C9—H9B	108.0	C6—N3—C2	122.90 (19)
C9—C10—H10A	109.5	C6—N3—C7	118.6 (2)
C9—C10—H10B	109.5	C2—N3—C7	118.34 (19)
H10A—C10—H10B	109.5	C6—N4—C5	110.84 (19)
C9—C10—H10C	109.5	C5—N5—N6	111.18 (19)
H10A—C10—H10C	109.5	C5—N5—C9	128.3 (2)
H10B—C10—H10C	109.5	N6—N5—C9	120.0 (2)
C16—C11—C12	119.1 (2)	C4—N6—N5	105.0 (2)
C16—C11—N2	118.9 (2)	C1—S1—C2	91.28 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Cg1i	0.93	2.75	3.615 (3)	155
C20—H20···Cg2ii	0.93	2.77	3.564 (4)	144

Table 1

Hydrogen-bond geometry (, )

Cg1 and Cg2 are the centroids of the C17C22 and C11C16 rings, respectively.

DHA	DH	HA	D A	DHA
C14H14Cg1i	0.93	2.75	3.615 (3)	155
C20H20Cg2ii	0.93	2.77	3.564 (4)	144

Symmetry codes: (i) ; (ii) .