Ethyl 7-(2-chloro-phen-yl)-5-trifluoro-meth-yl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxyl-ate.

In the title compound, C(15)H(12)ClF(3)N(4)O(2), the dihydro-pyrimidine ring exhibits an envelope conformation. The dihedral angle between the mean planes of the dihydro-pyrimidine and phenyl rings is 83.94 (6)°. The OCH(2)CH(3) group is disordered over two sites with occupancies of 0.155 (3) and 0.845 (3). The crystal packing is stabilized by inter-molecular N-H⋯N hydrogen bonds.

Related literature

For the anti­cancer activity, inhibition of the MDM2-p53 protein–protein inter­action and the anti­tuberculosis and dehydrogenase inhibitory activity of [1,2,4]triazolo [1,5-a]pyrimidine derivatives, see: Zhang et al. (2007 ▶); Allen et al. (2009 ▶); Pereyaslavskaya et al. (2008 ▶); Gujjar et al. (2009 ▶). For the bioactivity of trifluoro­methyl­ated mol­ecules, see: Kirk, (2006 ▶). For the preparation of trifluoro­methyl­ated [1,2,4]triazolo[1,5-a]pyrimidine derivatives, see Pryadeina et al. (2004 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H12ClF3N4O2

M = 372.74

Monoclinic,

a = 9.8927 (12) Å

b = 6.8055 (6) Å

c = 24.403 (3) Å

β = 99.237 (9)°

V = 1621.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 113 K

0.26 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: multi-scan (CrystalClear;Rigaku/MSC, 2002 ▶) T min = 0.930, T max = 0.945

14364 measured reflections

3835 independent reflections

3058 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.121

S = 1.08

3835 reflections

242 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 e Å−3

Δρmin = −0.40 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536810037712/hg2715sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037712/hg2715Isup2.hkl

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

C15H12ClF3N4O2	F(000) = 760
Mr = 372.74	Dx = 1.527 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 3832 reflections
a = 9.8927 (12) Å	θ = 2.4–27.9°
b = 6.8055 (6) Å	µ = 0.28 mm−1
c = 24.403 (3) Å	T = 113 K
β = 99.237 (9)°	Block, colorless
V = 1621.6 (3) Å3	0.26 × 0.22 × 0.20 mm
Z = 4

Rigaku Saturn diffractometer	3835 independent reflections
Radiation source: rotating anode	3058 reflections with I > 2σ(I)
confocal	Rint = 0.043
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 2.4°
ω scans	h = −13→13
Absorption correction: multi-scan CrystalClear	k = −8→8
Tmin = 0.930, Tmax = 0.945	l = −32→32
14364 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0596P)2 + 0.2191P] where P = (Fo2 + 2Fc2)/3
3835 reflections	(Δ/σ)max = 0.001
242 parameters	Δρmax = 0.27 e Å−3
6 restraints	Δρmin = −0.40 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cl1	−0.02142 (6)	1.41310 (7)	0.14247 (2)	0.04311 (18)
F1	0.35904 (10)	0.54406 (16)	0.01321 (5)	0.0375 (3)
F2	0.44949 (11)	0.82808 (16)	0.01419 (5)	0.0334 (3)
F3	0.47647 (11)	0.65227 (16)	0.08811 (5)	0.0329 (3)
O1	0.33660 (14)	1.2697 (2)	0.11875 (6)	0.0369 (3)
N1	0.14288 (14)	0.6813 (2)	0.03869 (6)	0.0211 (3)
N2	0.00227 (14)	0.9257 (2)	0.06666 (6)	0.0213 (3)
N3	−0.13449 (15)	0.9673 (2)	0.06434 (6)	0.0261 (3)
N4	−0.10446 (14)	0.6764 (2)	0.02200 (6)	0.0228 (3)
C1	0.01658 (17)	0.7543 (2)	0.04212 (7)	0.0198 (3)
C2	0.11062 (17)	1.0474 (2)	0.09691 (7)	0.0205 (3)
H2	0.1003	1.1842	0.0819	0.025*
C3	0.24727 (17)	0.9649 (2)	0.08603 (7)	0.0215 (4)
C4	0.25580 (16)	0.7931 (2)	0.05905 (7)	0.0199 (3)
C5	0.09913 (17)	1.0529 (2)	0.15815 (7)	0.0217 (4)
C6	0.04123 (19)	1.2105 (3)	0.18215 (8)	0.0274 (4)
C7	0.0304 (2)	1.2109 (3)	0.23816 (8)	0.0356 (5)
H7	−0.0083	1.3206	0.2541	0.043*
C8	0.0765 (2)	1.0501 (3)	0.27056 (8)	0.0381 (5)
H8	0.0690	1.0490	0.3089	0.046*
C9	0.1329 (2)	0.8925 (3)	0.24762 (8)	0.0355 (5)
H9	0.1644	0.7823	0.2700	0.043*
C10	0.14409 (19)	0.8941 (3)	0.19169 (8)	0.0284 (4)
H10	0.1833	0.7842	0.1761	0.034*
C11	0.36016 (18)	1.1040 (3)	0.10611 (7)	0.0249 (4)
O2	0.48511 (16)	1.0381 (3)	0.10610 (10)	0.0390 (6)	0.845 (3)
C12	0.5990 (2)	1.1697 (4)	0.12467 (11)	0.0315 (6)	0.845 (3)
H12A	0.5678	1.3077	0.1199	0.038*	0.845 (3)
H12B	0.6721	1.1489	0.1019	0.038*	0.845 (3)
C13	0.6540 (3)	1.1316 (5)	0.18435 (12)	0.0518 (8)	0.845 (3)
H13A	0.5832	1.1607	0.2070	0.078*	0.845 (3)
H13B	0.7338	1.2157	0.1960	0.078*	0.845 (3)
H13C	0.6812	0.9934	0.1892	0.078*	0.845 (3)
O2'	0.4728 (9)	0.9900 (15)	0.1298 (5)	0.0390 (6)	0.155 (3)
C12'	0.5996 (11)	1.0954 (19)	0.1454 (7)	0.0315 (6)	0.155 (3)
H12C	0.5860	1.2056	0.1704	0.038*	0.155 (3)
H12D	0.6309	1.1499	0.1120	0.038*	0.155 (3)
C13'	0.7072 (14)	0.952 (2)	0.1752 (7)	0.0518 (8)	0.155 (3)
H13D	0.6847	0.9190	0.2117	0.078*	0.155 (3)
H13E	0.7979	1.0133	0.1796	0.078*	0.155 (3)
H13F	0.7076	0.8317	0.1530	0.078*	0.155 (3)
C14	0.38686 (17)	0.7050 (2)	0.04419 (7)	0.0225 (4)
C15	−0.19178 (18)	0.8142 (3)	0.03716 (7)	0.0255 (4)
H15	−0.2884	0.8001	0.0285	0.031*
H1	0.146 (2)	0.567 (3)	0.0203 (9)	0.039 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0546 (4)	0.0261 (3)	0.0533 (4)	0.0094 (2)	0.0228 (3)	0.0025 (2)
F1	0.0217 (6)	0.0361 (6)	0.0564 (8)	−0.0049 (5)	0.0118 (5)	−0.0233 (5)
F2	0.0250 (6)	0.0366 (6)	0.0418 (7)	−0.0032 (4)	0.0153 (5)	0.0102 (5)
F3	0.0249 (6)	0.0370 (6)	0.0359 (6)	0.0063 (5)	0.0023 (5)	0.0070 (5)
O1	0.0310 (8)	0.0290 (7)	0.0506 (9)	−0.0071 (6)	0.0063 (6)	−0.0098 (6)
N1	0.0169 (7)	0.0207 (7)	0.0259 (8)	−0.0011 (5)	0.0038 (6)	−0.0039 (6)
N2	0.0150 (7)	0.0256 (7)	0.0231 (7)	0.0003 (5)	0.0022 (6)	−0.0043 (6)
N3	0.0169 (7)	0.0317 (8)	0.0293 (8)	0.0022 (6)	0.0026 (6)	−0.0046 (6)
N4	0.0172 (7)	0.0261 (8)	0.0245 (8)	−0.0008 (6)	0.0017 (6)	−0.0028 (6)
C1	0.0175 (8)	0.0224 (8)	0.0191 (8)	−0.0011 (6)	0.0022 (6)	−0.0002 (6)
C2	0.0194 (8)	0.0210 (8)	0.0208 (8)	−0.0021 (6)	0.0022 (6)	−0.0027 (6)
C3	0.0186 (8)	0.0250 (8)	0.0207 (8)	−0.0015 (7)	0.0030 (7)	−0.0007 (6)
C4	0.0168 (8)	0.0235 (8)	0.0194 (8)	−0.0023 (6)	0.0030 (6)	0.0023 (6)
C5	0.0177 (8)	0.0269 (9)	0.0205 (8)	−0.0036 (7)	0.0027 (7)	−0.0028 (7)
C6	0.0251 (9)	0.0283 (9)	0.0295 (10)	−0.0030 (7)	0.0069 (7)	−0.0045 (7)
C7	0.0325 (11)	0.0440 (12)	0.0329 (11)	−0.0062 (9)	0.0134 (8)	−0.0141 (9)
C8	0.0311 (11)	0.0631 (14)	0.0207 (9)	−0.0098 (10)	0.0057 (8)	−0.0034 (9)
C9	0.0281 (10)	0.0525 (12)	0.0260 (10)	0.0015 (9)	0.0043 (8)	0.0104 (9)
C10	0.0249 (9)	0.0341 (10)	0.0263 (9)	0.0022 (8)	0.0046 (7)	0.0019 (8)
C11	0.0215 (9)	0.0318 (10)	0.0217 (9)	−0.0031 (7)	0.0051 (7)	−0.0037 (7)
O2	0.0174 (8)	0.0325 (10)	0.0652 (16)	−0.0059 (7)	0.0001 (8)	−0.0180 (10)
C12	0.0184 (10)	0.0282 (14)	0.0467 (16)	−0.0069 (9)	0.0016 (10)	−0.0065 (11)
C13	0.0329 (15)	0.070 (2)	0.0506 (17)	−0.0184 (13)	0.0010 (12)	−0.0013 (15)
O2'	0.0174 (8)	0.0325 (10)	0.0652 (16)	−0.0059 (7)	0.0001 (8)	−0.0180 (10)
C12'	0.0184 (10)	0.0282 (14)	0.0467 (16)	−0.0069 (9)	0.0016 (10)	−0.0065 (11)
C13'	0.0329 (15)	0.070 (2)	0.0506 (17)	−0.0184 (13)	0.0010 (12)	−0.0013 (15)
C14	0.0197 (8)	0.0227 (8)	0.0258 (9)	−0.0040 (6)	0.0059 (7)	−0.0004 (7)
C15	0.0165 (8)	0.0313 (9)	0.0282 (9)	0.0003 (7)	0.0020 (7)	−0.0029 (7)

Cl1—C6	1.7407 (19)	C7—H7	0.9500
F1—C14	1.3339 (19)	C8—C9	1.369 (3)
F2—C14	1.3293 (19)	C8—H8	0.9500
F3—C14	1.326 (2)	C9—C10	1.387 (3)
O1—C11	1.202 (2)	C9—H9	0.9500
N1—C1	1.359 (2)	C10—H10	0.9500
N1—C4	1.377 (2)	C11—O2	1.315 (2)
N1—H1	0.90 (2)	C11—O2'	1.404 (8)
N2—C1	1.329 (2)	O2—C12	1.453 (3)
N2—N3	1.3744 (19)	C12—C13	1.493 (4)
N2—C2	1.458 (2)	C12—H12A	0.9900
N3—C15	1.314 (2)	C12—H12B	0.9900
N4—C1	1.329 (2)	C13—H13A	0.9800
N4—C15	1.366 (2)	C13—H13B	0.9800
C2—C5	1.517 (2)	C13—H13C	0.9800
C2—C3	1.526 (2)	O2'—C12'	1.442 (9)
C2—H2	1.0000	C12'—C13'	1.539 (9)
C3—C4	1.351 (2)	C12'—H12C	0.9900
C3—C11	1.486 (2)	C12'—H12D	0.9900
C4—C14	1.524 (2)	C13'—H13D	0.9800
C5—C10	1.385 (2)	C13'—H13E	0.9800
C5—C6	1.389 (2)	C13'—H13F	0.9800
C6—C7	1.388 (3)	C15—H15	0.9500
C7—C8	1.384 (3)
C1—N1—C4	118.45 (14)	C5—C10—C9	121.27 (18)
C1—N1—H1	116.7 (14)	C5—C10—H10	119.4
C4—N1—H1	124.6 (14)	C9—C10—H10	119.4
C1—N2—N3	109.72 (13)	O1—C11—O2	122.77 (17)
C1—N2—C2	127.16 (14)	O1—C11—O2'	125.9 (5)
N3—N2—C2	122.86 (13)	O2—C11—O2'	29.2 (5)
C15—N3—N2	101.51 (14)	O1—C11—C3	121.07 (16)
C1—N4—C15	101.41 (14)	O2—C11—C3	116.05 (16)
N4—C1—N2	111.19 (15)	O2'—C11—C3	106.8 (4)
N4—C1—N1	127.88 (15)	C11—O2—C12	118.11 (18)
N2—C1—N1	120.91 (15)	O2—C12—C13	109.9 (2)
N2—C2—C5	110.32 (13)	O2—C12—H12A	109.7
N2—C2—C3	107.61 (13)	C13—C12—H12A	109.7
C5—C2—C3	112.88 (14)	O2—C12—H12B	109.7
N2—C2—H2	108.6	C13—C12—H12B	109.7
C5—C2—H2	108.6	H12A—C12—H12B	108.2
C3—C2—H2	108.6	C11—O2'—C12'	115.7 (8)
C4—C3—C11	127.56 (16)	O2'—C12'—C13'	108.4 (10)
C4—C3—C2	121.99 (15)	O2'—C12'—H12C	110.0
C11—C3—C2	110.36 (14)	C13'—C12'—H12C	110.0
C3—C4—N1	122.93 (16)	O2'—C12'—H12D	110.0
C3—C4—C14	125.36 (15)	C13'—C12'—H12D	110.0
N1—C4—C14	111.62 (14)	H12C—C12'—H12D	108.4
C10—C5—C6	117.92 (16)	C12'—C13'—H13D	109.5
C10—C5—C2	119.70 (15)	C12'—C13'—H13E	109.5
C6—C5—C2	122.36 (15)	H13D—C13'—H13E	109.5
C7—C6—C5	121.26 (18)	C12'—C13'—H13F	109.5
C7—C6—Cl1	117.98 (15)	H13D—C13'—H13F	109.5
C5—C6—Cl1	120.75 (14)	H13E—C13'—H13F	109.5
C8—C7—C6	119.36 (18)	F3—C14—F2	107.78 (13)
C8—C7—H7	120.3	F3—C14—F1	106.64 (14)
C6—C7—H7	120.3	F2—C14—F1	106.11 (14)
C9—C8—C7	120.29 (18)	F3—C14—C4	113.45 (14)
C9—C8—H8	119.9	F2—C14—C4	111.87 (14)
C7—C8—H8	119.9	F1—C14—C4	110.60 (13)
C8—C9—C10	119.89 (19)	N3—C15—N4	116.16 (15)
C8—C9—H9	120.1	N3—C15—H15	121.9
C10—C9—H9	120.1	N4—C15—H15	121.9
C1—N2—N3—C15	−0.87 (18)	C2—C5—C6—Cl1	−0.2 (2)
C2—N2—N3—C15	−175.36 (15)	C5—C6—C7—C8	−0.9 (3)
C15—N4—C1—N2	−0.70 (18)	Cl1—C6—C7—C8	178.59 (15)
C15—N4—C1—N1	−179.05 (17)	C6—C7—C8—C9	0.3 (3)
N3—N2—C1—N4	1.04 (19)	C7—C8—C9—C10	0.1 (3)
C2—N2—C1—N4	175.24 (15)	C6—C5—C10—C9	−0.5 (3)
N3—N2—C1—N1	179.53 (15)	C2—C5—C10—C9	−178.84 (16)
C2—N2—C1—N1	−6.3 (3)	C8—C9—C10—C5	0.0 (3)
C4—N1—C1—N4	175.37 (16)	C4—C3—C11—O1	163.90 (19)
C4—N1—C1—N2	−2.8 (2)	C2—C3—C11—O1	−12.7 (2)
C1—N2—C2—C5	−112.47 (18)	C4—C3—C11—O2	−12.5 (3)
N3—N2—C2—C5	61.02 (19)	C2—C3—C11—O2	170.95 (18)
C1—N2—C2—C3	11.1 (2)	C4—C3—C11—O2'	−42.3 (6)
N3—N2—C2—C3	−175.44 (14)	C2—C3—C11—O2'	141.1 (6)
N2—C2—C3—C4	−8.1 (2)	O1—C11—O2—C12	2.9 (3)
C5—C2—C3—C4	113.82 (18)	O2'—C11—O2—C12	−103.3 (10)
N2—C2—C3—C11	168.67 (13)	C3—C11—O2—C12	179.19 (18)
C5—C2—C3—C11	−69.36 (18)	C11—O2—C12—C13	96.5 (3)
C11—C3—C4—N1	−175.26 (16)	O1—C11—O2'—C12'	−35.7 (14)
C2—C3—C4—N1	1.0 (3)	O2—C11—O2'—C12'	58.5 (11)
C11—C3—C4—C14	0.8 (3)	C3—C11—O2'—C12'	172.2 (10)
C2—C3—C4—C14	177.07 (15)	C11—O2'—C12'—C13'	174.9 (12)
C1—N1—C4—C3	5.2 (2)	C3—C4—C14—F3	66.0 (2)
C1—N1—C4—C14	−171.36 (14)	N1—C4—C14—F3	−117.51 (15)
N2—C2—C5—C10	77.54 (19)	C3—C4—C14—F2	−56.2 (2)
C3—C2—C5—C10	−42.9 (2)	N1—C4—C14—F2	120.30 (15)
N2—C2—C5—C6	−100.70 (18)	C3—C4—C14—F1	−174.22 (16)
C3—C2—C5—C6	138.88 (17)	N1—C4—C14—F1	2.25 (19)
C10—C5—C6—C7	0.9 (3)	N2—N3—C15—N4	0.5 (2)
C2—C5—C6—C7	179.21 (16)	C1—N4—C15—N3	0.1 (2)
C10—C5—C6—Cl1	−178.49 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4i	0.90 (2)	1.96 (2)	2.843 (2)	166.3 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4i	0.90 (2)	1.96 (2)	2.843 (2)	166.3 (19)

Symmetry code: (i) .