8-Methyl-2-[4-(trifluoro-meth-yl)phen-yl]-8H-pyrazolo-[4,3-e][1,2,4]triazolo[1,5-c]pyrimidin-5-amine methanol disolvate.

In the title compound, C(14)H(10)F(3)N(7)·2CH(4)O, the heterocyclic ring system is essentially planar (r.m.s. deviation = 0.009 Å) and makes a dihedral angle of 6.91 (8)° with the attached benzene ring. In the crystal, the main mol-ecules form centrosymmetric R(2) (2)(8) dimers via pairs of N-H⋯N hydrogen bonds between the amino groups and pyrimidine N atoms. One of the independent methanol mol-ecules and its inversion equivalent are linked to the dimers via O-H⋯N and N-H⋯O hydrogen bonds, forming R(4) (4)(16) graph-set motifs. The dimers along with the hydrogen-bonded methanol mol-ecules are stacked along the a axis, with π-π inter-actions between the pyrazole and triazole rings [centroid-centroid distance = 3.4953 (10) Å].

Related literature

For reviews on pyrazolo­[4,3-e][1,2,4]triazolo[1,5-c]pyrimidine adenosine receptor antagonists, see: Baraldi et al. (2006 ▶); Cacciari et al. (2007 ▶). For the general method used for the synthesis of the title compound, see: Dolzhenko et al. (2009 ▶); Cheong et al. (2010 ▶). For the crystal structures of related pyrazolo­[4,3-e][1,2,4]triazolo[1,5-c]pyrimidines, see: Ferretti et al. (2006 ▶); Mezheritsky et al. (2004 ▶); Tyurin et al. (2005 ▶); Xiao & Shi (2007 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C14H10F3N7·2CH4O

M = 397.37

Monoclinic,

a = 4.6179 (3) Å

b = 17.1149 (10) Å

c = 22.7627 (13) Å

β = 94.323 (1)°

V = 1793.93 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 223 K

0.58 × 0.32 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.932, T max = 0.985

12385 measured reflections

4076 independent reflections

3538 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.145

S = 1.05

4076 reflections

266 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024591/ci5111sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024591/ci5111Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H10F3N7·2CH4O	F(000) = 824
Mr = 397.37	Dx = 1.471 Mg m−3
Monoclinic, P21/n	Melting point: 573 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 4.6179 (3) Å	Cell parameters from 4421 reflections
b = 17.1149 (10) Å	θ = 2.4–27.2°
c = 22.7627 (13) Å	µ = 0.12 mm−1
β = 94.323 (1)°	T = 223 K
V = 1793.93 (19) Å3	Block, colourless
Z = 4	0.58 × 0.32 × 0.12 mm

Bruker SMART APEX CCD diffractometer	4076 independent reflections
Radiation source: fine-focus sealed tube	3538 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −5→5
Tmin = 0.932, Tmax = 0.985	k = −21→22
12385 measured reflections	l = −23→29

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0746P)2 + 0.7421P] where P = (Fo2 + 2Fc2)/3
4076 reflections	(Δ/σ)max = 0.001
266 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.21 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.

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 > 2σ(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
O1S	0.5063 (3)	0.68580 (11)	0.08136 (7)	0.0581 (4)
H1S	0.4507	0.6882	0.0459	0.087*
C1S	0.8079 (5)	0.68768 (18)	0.08766 (13)	0.0684 (7)
H1S1	0.8735	0.7415	0.0887	0.103*
H1S2	0.8852	0.6611	0.0546	0.103*
H1S3	0.8756	0.6617	0.1240	0.103*
C2S	0.1594 (6)	0.15803 (13)	0.27649 (11)	0.0581 (6)
H2S1	0.2028	0.1917	0.3103	0.087*
H2S2	0.1779	0.1038	0.2887	0.087*
H2S3	−0.0374	0.1678	0.2602	0.087*
F1	1.4952 (3)	0.39342 (8)	0.43457 (6)	0.0616 (4)
F2	1.2039 (3)	0.48312 (8)	0.45616 (5)	0.0550 (4)
F3	1.5562 (3)	0.50993 (9)	0.40469 (6)	0.0642 (4)
N1	−0.3122 (3)	0.23144 (9)	0.07561 (7)	0.0362 (3)
N2	−0.2997 (3)	0.29563 (9)	0.04026 (7)	0.0375 (4)
N3	−0.0193 (3)	0.41222 (8)	0.04749 (6)	0.0365 (4)
N4	0.3019 (3)	0.41895 (8)	0.13254 (6)	0.0296 (3)
N5	0.5146 (3)	0.45421 (8)	0.16847 (6)	0.0309 (3)
N6	0.3934 (3)	0.33542 (8)	0.20487 (6)	0.0286 (3)
N7	0.2815 (4)	0.51915 (10)	0.06445 (8)	0.0461 (4)
H7A	0.402 (5)	0.5454 (13)	0.0863 (10)	0.044 (6)*
H7B	0.204 (5)	0.5402 (14)	0.0312 (11)	0.052 (6)*
C1	−0.1317 (4)	0.23497 (10)	0.12400 (8)	0.0343 (4)
H1	−0.1081	0.1971	0.1539	0.041*
C2	0.0145 (4)	0.30557 (9)	0.12153 (7)	0.0301 (4)
C3	−0.0985 (4)	0.34097 (10)	0.06864 (7)	0.0322 (4)
C4	0.1813 (4)	0.45034 (10)	0.07964 (7)	0.0336 (4)
C5	0.2331 (4)	0.34778 (9)	0.15530 (7)	0.0276 (3)
C6	0.5597 (4)	0.40191 (9)	0.21105 (7)	0.0269 (3)
C7	0.7738 (3)	0.41460 (9)	0.26155 (7)	0.0274 (3)
C8	0.9154 (4)	0.48630 (10)	0.26875 (7)	0.0326 (4)
H8	0.8786	0.5261	0.2407	0.039*
C9	1.1098 (4)	0.49892 (10)	0.31706 (8)	0.0343 (4)
H9	1.2041	0.5474	0.3221	0.041*
C10	1.1650 (4)	0.43965 (10)	0.35808 (7)	0.0307 (4)
C11	1.0299 (4)	0.36786 (10)	0.35067 (8)	0.0343 (4)
H11	1.0710	0.3277	0.3782	0.041*
C12	0.8337 (4)	0.35550 (10)	0.30243 (8)	0.0331 (4)
H12	0.7407	0.3068	0.2974	0.040*
C13	1.3561 (4)	0.45625 (11)	0.41268 (8)	0.0368 (4)
C14	−0.5043 (5)	0.16731 (12)	0.05670 (10)	0.0464 (5)
H14A	−0.4241	0.1396	0.0245	0.070*
H14B	−0.6940	0.1879	0.0436	0.070*
H14C	−0.5229	0.1317	0.0894	0.070*
O2S	0.3553 (4)	0.17366 (9)	0.23347 (8)	0.0626 (5)
H2S	0.3819	0.2215	0.2314	0.094*

	U11	U22	U33	U12	U13	U23
O1S	0.0507 (9)	0.0792 (12)	0.0434 (8)	−0.0125 (8)	−0.0029 (7)	−0.0038 (8)
C1S	0.0505 (14)	0.0805 (18)	0.0727 (17)	0.0068 (12)	−0.0050 (12)	−0.0207 (14)
C2S	0.0740 (16)	0.0445 (12)	0.0554 (13)	0.0039 (11)	0.0027 (12)	0.0023 (10)
F1	0.0664 (9)	0.0601 (8)	0.0537 (8)	0.0231 (7)	−0.0252 (6)	−0.0033 (6)
F2	0.0506 (7)	0.0806 (9)	0.0333 (6)	0.0123 (6)	0.0006 (5)	−0.0145 (6)
F3	0.0544 (8)	0.0857 (10)	0.0502 (7)	−0.0294 (7)	−0.0117 (6)	0.0062 (7)
N1	0.0395 (8)	0.0307 (8)	0.0381 (8)	−0.0050 (6)	0.0010 (6)	−0.0035 (6)
N2	0.0428 (9)	0.0336 (8)	0.0348 (8)	−0.0033 (6)	−0.0047 (6)	−0.0025 (6)
N3	0.0491 (9)	0.0286 (7)	0.0300 (7)	−0.0014 (6)	−0.0081 (6)	0.0023 (6)
N4	0.0391 (8)	0.0237 (7)	0.0254 (7)	−0.0008 (5)	−0.0027 (5)	−0.0003 (5)
N5	0.0385 (8)	0.0260 (7)	0.0273 (7)	−0.0014 (6)	−0.0036 (6)	−0.0018 (5)
N6	0.0343 (7)	0.0250 (7)	0.0264 (7)	0.0006 (5)	0.0011 (5)	0.0003 (5)
N7	0.0665 (12)	0.0316 (8)	0.0369 (9)	−0.0117 (8)	−0.0177 (8)	0.0086 (7)
C1	0.0389 (9)	0.0310 (9)	0.0332 (9)	−0.0026 (7)	0.0030 (7)	−0.0004 (7)
C2	0.0350 (9)	0.0278 (8)	0.0274 (8)	0.0001 (6)	0.0019 (6)	−0.0020 (6)
C3	0.0382 (9)	0.0286 (8)	0.0292 (8)	0.0018 (7)	−0.0014 (7)	−0.0029 (6)
C4	0.0441 (10)	0.0277 (8)	0.0279 (8)	0.0018 (7)	−0.0037 (7)	0.0018 (6)
C5	0.0335 (8)	0.0232 (7)	0.0264 (7)	0.0026 (6)	0.0040 (6)	−0.0013 (6)
C6	0.0322 (8)	0.0234 (7)	0.0253 (7)	0.0024 (6)	0.0031 (6)	−0.0008 (6)
C7	0.0295 (8)	0.0277 (8)	0.0252 (7)	0.0032 (6)	0.0029 (6)	−0.0008 (6)
C8	0.0402 (9)	0.0272 (8)	0.0299 (8)	−0.0004 (7)	−0.0010 (7)	0.0052 (6)
C9	0.0374 (9)	0.0300 (8)	0.0349 (9)	−0.0041 (7)	−0.0011 (7)	−0.0002 (7)
C10	0.0281 (8)	0.0361 (9)	0.0279 (8)	0.0051 (7)	0.0022 (6)	−0.0005 (7)
C11	0.0398 (9)	0.0312 (9)	0.0314 (8)	0.0042 (7)	−0.0016 (7)	0.0068 (7)
C12	0.0394 (9)	0.0252 (8)	0.0344 (9)	−0.0010 (7)	0.0000 (7)	0.0021 (6)
C13	0.0350 (9)	0.0426 (10)	0.0323 (9)	0.0037 (7)	0.0002 (7)	−0.0005 (7)
C14	0.0476 (11)	0.0386 (10)	0.0526 (12)	−0.0119 (9)	0.0009 (9)	−0.0091 (8)
O2S	0.0839 (12)	0.0294 (7)	0.0764 (11)	0.0002 (8)	0.0186 (9)	0.0034 (7)

O1S—C1S	1.390 (3)	N7—C4	1.321 (2)
O1S—H1S	0.83	N7—H7A	0.85 (2)
C1S—H1S1	0.97	N7—H7B	0.89 (2)
C1S—H1S2	0.97	C1—C2	1.387 (2)
C1S—H1S3	0.97	C1—H1	0.94
C2S—O2S	1.408 (3)	C2—C3	1.412 (2)
C2S—H2S1	0.97	C2—C5	1.419 (2)
C2S—H2S2	0.97	C6—C7	1.475 (2)
C2S—H2S3	0.97	C7—C12	1.388 (2)
F1—C13	1.330 (2)	C7—C8	1.394 (2)
F2—C13	1.338 (2)	C8—C9	1.383 (2)
F3—C13	1.325 (2)	C8—H8	0.94
N1—C1	1.331 (2)	C9—C10	1.389 (2)
N1—N2	1.366 (2)	C9—H9	0.94
N1—C14	1.456 (2)	C10—C11	1.382 (3)
N2—C3	1.339 (2)	C10—C13	1.496 (2)
N3—C4	1.310 (2)	C11—C12	1.386 (2)
N3—C3	1.371 (2)	C11—H11	0.94
N4—N5	1.3698 (19)	C12—H12	0.94
N4—C5	1.370 (2)	C14—H14A	0.97
N4—C4	1.396 (2)	C14—H14B	0.97
N5—C6	1.324 (2)	C14—H14C	0.97
N6—C5	1.319 (2)	O2S—H2S	0.83
N6—C6	1.374 (2)
C1S—O1S—H1S	109.5	N6—C5—N4	109.56 (14)
O1S—C1S—H1S1	109.5	N6—C5—C2	135.39 (15)
O1S—C1S—H1S2	109.5	N4—C5—C2	115.05 (14)
H1S1—C1S—H1S2	109.5	N5—C6—N6	115.41 (14)
O1S—C1S—H1S3	109.5	N5—C6—C7	122.01 (14)
H1S1—C1S—H1S3	109.5	N6—C6—C7	122.58 (14)
H1S2—C1S—H1S3	109.5	C12—C7—C8	119.65 (15)
O2S—C2S—H2S1	109.5	C12—C7—C6	120.21 (15)
O2S—C2S—H2S2	109.5	C8—C7—C6	120.14 (14)
H2S1—C2S—H2S2	109.5	C9—C8—C7	120.09 (15)
O2S—C2S—H2S3	109.5	C9—C8—H8	120.0
H2S1—C2S—H2S3	109.5	C7—C8—H8	120.0
H2S2—C2S—H2S3	109.5	C8—C9—C10	119.71 (16)
C1—N1—N2	113.54 (14)	C8—C9—H9	120.1
C1—N1—C14	127.47 (16)	C10—C9—H9	120.1
N2—N1—C14	118.95 (15)	C11—C10—C9	120.58 (16)
C3—N2—N1	103.90 (14)	C11—C10—C13	120.16 (16)
C4—N3—C3	116.28 (14)	C9—C10—C13	119.11 (16)
N5—N4—C5	110.01 (13)	C10—C11—C12	119.62 (15)
N5—N4—C4	124.55 (14)	C10—C11—H11	120.2
C5—N4—C4	125.41 (14)	C12—C11—H11	120.2
C6—N5—N4	101.84 (13)	C11—C12—C7	120.34 (16)
C5—N6—C6	103.18 (13)	C11—C12—H12	119.8
C4—N7—H7A	123.1 (15)	C7—C12—H12	119.8
C4—N7—H7B	117.2 (15)	F3—C13—F1	106.84 (16)
H7A—N7—H7B	119 (2)	F3—C13—F2	105.89 (16)
N1—C1—C2	106.40 (15)	F1—C13—F2	105.45 (15)
N1—C1—H1	126.8	F3—C13—C10	113.04 (15)
C2—C1—H1	126.8	F1—C13—C10	113.31 (15)
C1—C2—C3	104.97 (15)	F2—C13—C10	111.71 (14)
C1—C2—C5	138.58 (16)	N1—C14—H14A	109.5
C3—C2—C5	116.45 (15)	N1—C14—H14B	109.5
N2—C3—N3	122.67 (15)	H14A—C14—H14B	109.5
N2—C3—C2	111.18 (15)	N1—C14—H14C	109.5
N3—C3—C2	126.15 (15)	H14A—C14—H14C	109.5
N3—C4—N7	122.99 (16)	H14B—C14—H14C	109.5
N3—C4—N4	120.64 (15)	C2S—O2S—H2S	109.5
N7—C4—N4	116.37 (16)
C1—N1—N2—C3	0.3 (2)	C1—C2—C5—N6	0.6 (4)
C14—N1—N2—C3	−177.53 (16)	C3—C2—C5—N6	−178.44 (18)
C5—N4—N5—C6	−0.34 (17)	C1—C2—C5—N4	−179.5 (2)
C4—N4—N5—C6	−178.42 (15)	C3—C2—C5—N4	1.4 (2)
N2—N1—C1—C2	−0.4 (2)	N4—N5—C6—N6	0.51 (18)
C14—N1—C1—C2	177.22 (17)	N4—N5—C6—C7	−179.41 (14)
N1—C1—C2—C3	0.29 (19)	C5—N6—C6—N5	−0.49 (19)
N1—C1—C2—C5	−178.9 (2)	C5—N6—C6—C7	179.44 (14)
N1—N2—C3—N3	179.97 (16)	N5—C6—C7—C12	−174.11 (16)
N1—N2—C3—C2	−0.1 (2)	N6—C6—C7—C12	6.0 (2)
C4—N3—C3—N2	−179.75 (17)	N5—C6—C7—C8	6.4 (2)
C4—N3—C3—C2	0.3 (3)	N6—C6—C7—C8	−173.47 (15)
C1—C2—C3—N2	−0.1 (2)	C12—C7—C8—C9	−1.4 (3)
C5—C2—C3—N2	179.25 (15)	C6—C7—C8—C9	178.09 (16)
C1—C2—C3—N3	179.81 (17)	C7—C8—C9—C10	0.5 (3)
C5—C2—C3—N3	−0.8 (3)	C8—C9—C10—C11	0.8 (3)
C3—N3—C4—N7	179.18 (18)	C8—C9—C10—C13	−174.85 (16)
C3—N3—C4—N4	−0.5 (3)	C9—C10—C11—C12	−1.2 (3)
N5—N4—C4—N3	179.14 (16)	C13—C10—C11—C12	174.37 (16)
C5—N4—C4—N3	1.3 (3)	C10—C11—C12—C7	0.4 (3)
N5—N4—C4—N7	−0.6 (3)	C8—C7—C12—C11	0.9 (3)
C5—N4—C4—N7	−178.36 (17)	C6—C7—C12—C11	−178.53 (16)
C6—N6—C5—N4	0.23 (17)	C11—C10—C13—F3	154.07 (17)
C6—N6—C5—C2	−179.89 (18)	C9—C10—C13—F3	−30.3 (2)
N5—N4—C5—N6	0.06 (19)	C11—C10—C13—F1	32.3 (2)
C4—N4—C5—N6	178.13 (15)	C9—C10—C13—F1	−152.04 (17)
N5—N4—C5—C2	−179.84 (14)	C11—C10—C13—F2	−86.6 (2)
C4—N4—C5—C2	−1.8 (2)	C9—C10—C13—F2	89.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···N2i	0.83	2.05	2.877 (2)	175
O2S—H2S···N6	0.83	2.04	2.853 (2)	165
N7—H7A···O1S	0.85 (2)	2.46 (2)	3.050 (2)	128 (2)
N7—H7B···N3i	0.89 (2)	2.09 (3)	2.979 (2)	179 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯N2i	0.83	2.05	2.877 (2)	175
O2S—H2S⋯N6	0.83	2.04	2.853 (2)	165
N7—H7A⋯O1S	0.85 (2)	2.46 (2)	3.050 (2)	128 (2)
N7—H7B⋯N3i	0.89 (2)	2.09 (3)	2.979 (2)	179 (2)

Symmetry code: (i) .