The crystal structure of 1,5-dibenzyl-1H-pyrazolo-[3,4-d]pyrimidine-4(5H)-thione.

In the title compound, C19H16N4S, the pyrazolo-[3,4-d]pyrimidine ring is close to being planar, with the greatest deviation from the mean plane being 0.023 (2) Å for the C atom bearing the thione S atom. The two phenyl rings are nearly perpendicular to the fused ring system [dihedral angles = 71.4 (2) and 78.1 (2)°], but are oriented in opposite directions; the dihedral angle between the phenyl rings is 32.22 (16)°. In the crystal, linear supra-molecular chains along [101] are sustained by C-H⋯S inter-actions.

Related literature

For pharmacological and biochemical properties of pyrazolo­[1,5-a]pyrimidine, see: Orlikova et al. (2014 ▸); Yuan et al. (2013 ▸); Rashad et al. (2011 ▸). For related structures, see: El Fal et al. (2013 ▸, 2014 ▸); Alsubari et al. (2011 ▸); Ramli et al. (2012 ▸).

Experimental

Crystal data

C19H16N4S

M = 332.42

Monoclinic,

a = 4.4953 (12) Å

b = 29.140 (8) Å

c = 6.3889 (16) Å

β = 97.860 (9)°

V = 829.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.20 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

9214 measured reflections

3582 independent reflections

2406 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.084

S = 0.97

3582 reflections

217 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.12 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▸), 1730 Friedel pairs

Absolute structure parameter: −0.11 (7)

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: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901402828X/tk5354sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402828X/tk5354Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901402828X/tk5354Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901402828X/tk5354fig1.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: 1041681

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

C19H16N4S	F(000) = 348
Mr = 332.42	Dx = 1.332 Mg m−3
Monoclinic, P21	Melting point: 563 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 4.4953 (12) Å	Cell parameters from 3582 reflections
b = 29.140 (8) Å	θ = 2.8–27.1°
c = 6.3889 (16) Å	µ = 0.20 mm−1
β = 97.860 (9)°	T = 296 K
V = 829.0 (4) Å3	Block, yellow
Z = 2	0.37 × 0.34 × 0.29 mm

Bruker X8 APEX diffractometer	3582 independent reflections
Radiation source: fine-focus sealed tube	2406 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 27.1°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
Tmin = 0.589, Tmax = 0.746	k = −37→37
9214 measured reflections	l = −8→8

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0318P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max < 0.001
3582 reflections	Δρmax = 0.14 e Å−3
217 parameters	Δρmin = −0.12 e Å−3
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 1730 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.11 (7)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on all data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.5941 (5)	0.48633 (8)	0.9980 (3)	0.0412 (6)
C2	0.4720 (5)	0.44502 (8)	1.0570 (3)	0.0411 (6)
C3	0.5145 (7)	0.41623 (9)	1.2377 (4)	0.0586 (7)
H3	0.6506	0.4222	1.3578	0.070*
C4	0.2489 (6)	0.42310 (9)	0.9208 (4)	0.0457 (6)
C5	0.2551 (6)	0.47501 (9)	0.6716 (4)	0.0488 (6)
H5	0.1885	0.4864	0.5375	0.059*
C6	0.5892 (5)	0.54088 (9)	0.6906 (4)	0.0477 (6)
H6A	0.6197	0.5330	0.5476	0.057*
H6B	0.7826	0.5495	0.7672	0.057*
C7	0.3812 (5)	0.58142 (8)	0.6832 (4)	0.0425 (6)
C8	0.3274 (6)	0.60388 (9)	0.8650 (4)	0.0545 (7)
H8	0.4188	0.5935	0.9959	0.065*
C9	0.1404 (7)	0.64137 (10)	0.8546 (5)	0.0651 (8)
H9	0.1070	0.6563	0.9780	0.078*
C10	0.0034 (7)	0.65686 (11)	0.6635 (5)	0.0700 (8)
H10	−0.1242	0.6821	0.6569	0.084*
C11	0.0546 (7)	0.63514 (11)	0.4817 (5)	0.0701 (9)
H11	−0.0375	0.6458	0.3515	0.084*
C12	0.2421 (6)	0.59761 (9)	0.4912 (4)	0.0551 (7)
H12	0.2754	0.5830	0.3671	0.066*
C13	−0.0331 (7)	0.34855 (9)	0.9311 (5)	0.0701 (9)
H13A	−0.1746	0.3609	0.8167	0.084*
H13B	−0.1461	0.3374	1.0396	0.084*
C14	0.1353 (6)	0.30957 (9)	0.8500 (5)	0.0538 (7)
C15	0.1948 (7)	0.27009 (11)	0.9677 (5)	0.0701 (8)
H15	0.1235	0.2673	1.0970	0.084*
C16	0.3567 (8)	0.23521 (11)	0.8969 (8)	0.0926 (12)
H16	0.3946	0.2088	0.9778	0.111*
C17	0.4635 (8)	0.23889 (15)	0.7078 (9)	0.0961 (13)
H17	0.5758	0.2152	0.6605	0.115*
C18	0.4049 (8)	0.27764 (16)	0.5874 (6)	0.0898 (11)
H18	0.4766	0.2801	0.4581	0.108*
C19	0.2406 (7)	0.31279 (11)	0.6575 (5)	0.0705 (8)
H19	0.2000	0.3389	0.5748	0.085*
N1	0.3381 (6)	0.38019 (8)	1.2147 (4)	0.0633 (6)
N2	0.1709 (5)	0.38498 (7)	1.0188 (4)	0.0575 (6)
N3	0.1303 (5)	0.43742 (7)	0.7249 (3)	0.0529 (5)
N4	0.4758 (4)	0.49978 (6)	0.7928 (3)	0.0422 (5)
S1	0.85051 (15)	0.51743 (3)	1.14918 (10)	0.0571 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0382 (13)	0.0485 (15)	0.0369 (13)	0.0091 (11)	0.0049 (10)	−0.0077 (11)
C2	0.0406 (14)	0.0454 (15)	0.0366 (13)	0.0074 (11)	0.0030 (11)	−0.0022 (11)
C3	0.0693 (19)	0.0591 (18)	0.0468 (16)	0.0095 (16)	0.0061 (14)	0.0028 (14)
C4	0.0446 (15)	0.0458 (16)	0.0474 (15)	0.0080 (12)	0.0087 (13)	−0.0024 (13)
C5	0.0507 (16)	0.0561 (18)	0.0367 (13)	0.0104 (14)	−0.0046 (11)	−0.0056 (12)
C6	0.0459 (15)	0.0593 (16)	0.0395 (14)	−0.0032 (13)	0.0116 (12)	0.0003 (12)
C7	0.0424 (15)	0.0473 (14)	0.0375 (14)	−0.0095 (12)	0.0049 (11)	0.0009 (12)
C8	0.0618 (18)	0.0591 (18)	0.0412 (15)	−0.0018 (14)	0.0023 (13)	0.0010 (13)
C9	0.071 (2)	0.0571 (19)	0.069 (2)	−0.0002 (16)	0.0151 (17)	−0.0094 (15)
C10	0.071 (2)	0.0573 (19)	0.082 (2)	0.0038 (16)	0.0097 (17)	0.0114 (18)
C11	0.073 (2)	0.073 (2)	0.0607 (19)	0.0017 (18)	−0.0028 (16)	0.0207 (17)
C12	0.0593 (18)	0.0584 (18)	0.0467 (15)	−0.0083 (15)	0.0040 (13)	0.0037 (13)
C13	0.0531 (18)	0.0551 (19)	0.102 (2)	−0.0104 (15)	0.0102 (17)	−0.0024 (16)
C14	0.0479 (16)	0.0475 (16)	0.0647 (18)	−0.0101 (12)	0.0028 (14)	−0.0036 (14)
C15	0.074 (2)	0.0588 (19)	0.076 (2)	−0.0095 (17)	0.0032 (16)	0.0059 (17)
C16	0.079 (3)	0.053 (2)	0.140 (4)	0.0019 (19)	−0.006 (3)	0.003 (2)
C17	0.062 (2)	0.080 (3)	0.144 (4)	0.000 (2)	0.004 (3)	−0.041 (3)
C18	0.076 (3)	0.116 (3)	0.077 (2)	−0.014 (2)	0.0093 (19)	−0.036 (3)
C19	0.069 (2)	0.069 (2)	0.072 (2)	−0.0072 (16)	0.0068 (17)	−0.0002 (16)
N1	0.0782 (18)	0.0568 (16)	0.0564 (15)	−0.0011 (13)	0.0142 (13)	0.0070 (12)
N2	0.0550 (15)	0.0504 (14)	0.0681 (16)	0.0002 (11)	0.0118 (12)	0.0033 (13)
N3	0.0503 (13)	0.0496 (14)	0.0558 (14)	0.0029 (11)	−0.0034 (11)	−0.0043 (11)
N4	0.0406 (11)	0.0509 (12)	0.0342 (10)	0.0034 (9)	0.0021 (9)	−0.0013 (9)
S1	0.0536 (4)	0.0676 (4)	0.0463 (4)	−0.0042 (4)	−0.0073 (3)	−0.0052 (4)

C1—C2	1.396 (3)	C10—C11	1.370 (4)
C1—N4	1.402 (3)	C10—H10	0.9300
C1—S1	1.667 (2)	C11—C12	1.377 (4)
C2—C4	1.390 (3)	C11—H11	0.9300
C2—C3	1.419 (3)	C12—H12	0.9300
C3—N1	1.312 (3)	C13—N2	1.463 (3)
C3—H3	0.9300	C13—C14	1.496 (4)
C4—N2	1.345 (3)	C13—H13A	0.9700
C4—N3	1.357 (3)	C13—H13B	0.9700
C5—N3	1.297 (3)	C14—C19	1.380 (4)
C5—N4	1.376 (3)	C14—C15	1.380 (4)
C5—H5	0.9300	C15—C16	1.363 (5)
C6—N4	1.487 (3)	C15—H15	0.9300
C6—C7	1.503 (3)	C16—C17	1.364 (5)
C6—H6A	0.9700	C16—H16	0.9300
C6—H6B	0.9700	C17—C18	1.371 (5)
C7—C12	1.381 (3)	C17—H17	0.9300
C7—C8	1.383 (3)	C18—C19	1.373 (5)
C8—C9	1.374 (4)	C18—H18	0.9300
C8—H8	0.9300	C19—H19	0.9300
C9—C10	1.367 (4)	N1—N2	1.376 (3)
C9—H9	0.9300
C2—C1—N4	112.4 (2)	C11—C12—C7	120.7 (3)
C2—C1—S1	125.35 (18)	C11—C12—H12	119.6
N4—C1—S1	122.28 (18)	C7—C12—H12	119.6
C4—C2—C1	120.3 (2)	N2—C13—C14	111.3 (2)
C4—C2—C3	104.1 (2)	N2—C13—H13A	109.4
C1—C2—C3	135.7 (2)	C14—C13—H13A	109.4
N1—C3—C2	111.7 (3)	N2—C13—H13B	109.4
N1—C3—H3	124.1	C14—C13—H13B	109.4
C2—C3—H3	124.1	H13A—C13—H13B	108.0
N2—C4—N3	126.1 (2)	C19—C14—C15	118.5 (3)
N2—C4—C2	107.4 (2)	C19—C14—C13	120.5 (3)
N3—C4—C2	126.5 (2)	C15—C14—C13	120.9 (3)
N3—C5—N4	126.9 (2)	C16—C15—C14	120.9 (3)
N3—C5—H5	116.6	C16—C15—H15	119.6
N4—C5—H5	116.6	C14—C15—H15	119.6
N4—C6—C7	113.42 (17)	C15—C16—C17	120.3 (4)
N4—C6—H6A	108.9	C15—C16—H16	119.9
C7—C6—H6A	108.9	C17—C16—H16	119.9
N4—C6—H6B	108.9	C16—C17—C18	119.8 (4)
C7—C6—H6B	108.9	C16—C17—H17	120.1
H6A—C6—H6B	107.7	C18—C17—H17	120.1
C12—C7—C8	118.3 (2)	C17—C18—C19	120.1 (4)
C12—C7—C6	120.0 (2)	C17—C18—H18	119.9
C8—C7—C6	121.7 (2)	C19—C18—H18	119.9
C9—C8—C7	120.7 (3)	C18—C19—C14	120.3 (3)
C9—C8—H8	119.6	C18—C19—H19	119.8
C7—C8—H8	119.6	C14—C19—H19	119.8
C10—C9—C8	120.3 (3)	C3—N1—N2	105.5 (2)
C10—C9—H9	119.9	C4—N2—N1	111.2 (2)
C8—C9—H9	119.9	C4—N2—C13	127.6 (2)
C9—C10—C11	119.8 (3)	N1—N2—C13	120.7 (2)
C9—C10—H10	120.1	C5—N3—C4	111.8 (2)
C11—C10—H10	120.1	C5—N4—C1	122.1 (2)
C10—C11—C12	120.1 (3)	C5—N4—C6	116.1 (2)
C10—C11—H11	119.9	C1—N4—C6	121.78 (19)
C12—C11—H11	119.9

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S1i	0.93	2.87	3.784 (3)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C5H5S1i	0.93	2.87	3.784(3)	167

Symmetry code: (i) .