organic compounds
2-Amino-4-(4-bromophenyl)-8-trifluoromethyl-3,4-dihydropyrimido[1,2-a][1,3,5]triazin-6(5H)-one†
aDepartment of Pharmacy, Faculty of Science, National University of Singapore, 18 Science Drive 4, Singapore 117543, Singapore, and bDepartment of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
*Correspondence e-mail: phada@nus.edu.sg
The title compound, C13H9BrF3N5O, crystallizes with two independent molecules in the The pyrimidine rings of the molecules are planar [maximum deviations 0.053 (3) and 0.012 (3) Å], while the triazine rings adopt flattened half-boat conformations with the p-bromophenyl rings in the flagpole positions. The crystal packing is stabilized by a three-dimensional network of intermolecular N—H⋯N, N—H⋯O and N—H⋯F hydrogen bonds.
Related literature
For the a][1,3,5]triazin-5-amine, see: Dolzhenko et al. (2007). For the preparation of benzo-fused analogues, see: Dolzhenko et al. (2008a). For the previous report in this series, see: Dolzhenko et al. (2008b).
of 7,7-dimethyl-2-phenyl-6,7-dihydro-1,2,4-triazolo[1,5-Experimental
Crystal data
|
Data collection: SMART (Bruker, 2001); cell 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.
Supporting information
10.1107/S1600536809007612/ng2543sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809007612/ng2543Isup2.hkl
2-Amino-4-(4-bromophenyl)-8-trifluoromethyl-3,4-dihydro-6H-pyrimido[1,2-a][1,3,5]triazin-6-one was synthesized from 6-oxo-4-trifluoromethyl-1,6-dihydropyrimidin-2-yl guanidine and p-bromobenzaldehyde according to general method reported by Dolzhenko et al. (2008a). Single crystals suitable for crystallographic analysis were grown by slow evaporation of the solution in ethyl acetate / methanol.
N-bound H atoms were located in a difference map and refined freely. C-bound H atoms were positioned geometrically (C—H = 0.94 or 0.99 Å) and were constrained in a riding motion approximation with Uiso(H) = 1.2Ueq(C). One of the BrC6H4 parts is disordered into two parts at 89:11 ratio.
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).Fig. 1. The synthesis of 2-amino-4-(4-bromophenyl)-8-trifluoromethyl-3,4-dihydro-6H-pyrimido[1,2-a][1,3,5]triazin-6-one | |
Fig. 2. Tautomerism in the title compound | |
Fig. 3. The molecular structure of 2-amino-4-(4-bromophenyl)-8-trifluoromethyl-3,4-dihydro-6H-pyrimido[1,2-a][1,3,5]triazin-6-one with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 4. Molecular parking in the crystal, viewed along the a axis. Hydrogen bonds are shown as dashed lines. |
C13H9BrF3N5O | Dx = 1.682 Mg m−3 |
Mr = 388.16 | Melting point: 516 K |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 5069 reflections |
a = 10.0531 (4) Å | θ = 2.4–25.1° |
b = 29.9108 (13) Å | µ = 2.73 mm−1 |
c = 10.1945 (4) Å | T = 223 K |
V = 3065.4 (2) Å3 | Block, colourless |
Z = 8 | 0.46 × 0.34 × 0.20 mm |
F(000) = 1536 |
Bruker SMART APEX CCD diffractometer | 6287 independent reflections |
Radiation source: fine-focus sealed tube | 4979 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −12→13 |
Tmin = 0.367, Tmax = 0.612 | k = −38→38 |
20728 measured reflections | l = −13→11 |
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)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0646P)2 + 2.1384P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6287 reflections | Δρmax = 1.50 e Å−3 |
432 parameters | Δρmin = −0.74 e Å−3 |
16 restraints | Absolute structure: Flack (1983), 2044 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.011 (10) |
C13H9BrF3N5O | V = 3065.4 (2) Å3 |
Mr = 388.16 | Z = 8 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 10.0531 (4) Å | µ = 2.73 mm−1 |
b = 29.9108 (13) Å | T = 223 K |
c = 10.1945 (4) Å | 0.46 × 0.34 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 6287 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4979 reflections with I > 2σ(I) |
Tmin = 0.367, Tmax = 0.612 | Rint = 0.037 |
20728 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.138 | Δρmax = 1.50 e Å−3 |
S = 1.04 | Δρmin = −0.74 e Å−3 |
6287 reflections | Absolute structure: Flack (1983), 2044 Friedel pairs |
432 parameters | Absolute structure parameter: 0.011 (10) |
16 restraints |
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 | Occ. (<1) | |
O1 | 1.0316 (3) | 0.34878 (10) | 1.2353 (3) | 0.0346 (7) | |
F1 | 0.9317 (4) | 0.36022 (11) | 1.7842 (4) | 0.0634 (10) | |
F2 | 0.8409 (4) | 0.30866 (11) | 1.6709 (4) | 0.0750 (12) | |
F3 | 0.7371 (4) | 0.37004 (16) | 1.7065 (5) | 0.0873 (14) | |
N1 | 1.0194 (3) | 0.47967 (11) | 1.2317 (4) | 0.0259 (7) | |
H1N | 1.012 (5) | 0.4927 (15) | 1.156 (3) | 0.031* | |
N2 | 0.9826 (3) | 0.48272 (10) | 1.4583 (3) | 0.0237 (7) | |
N3 | 1.0181 (3) | 0.41352 (10) | 1.3521 (3) | 0.0232 (7) | |
N4 | 0.9342 (4) | 0.41721 (11) | 1.5665 (4) | 0.0290 (7) | |
N5 | 0.9597 (4) | 0.54572 (11) | 1.3299 (4) | 0.0335 (8) | |
H5A | 0.919 (5) | 0.5568 (15) | 1.401 (3) | 0.040* | |
H5B | 0.982 (5) | 0.5632 (14) | 1.262 (4) | 0.040* | |
C1 | 1.0910 (4) | 0.43826 (13) | 1.2510 (4) | 0.0250 (8) | |
H1A | 1.0904 | 0.4209 | 1.1683 | 0.030* | |
C2 | 0.9892 (4) | 0.50251 (13) | 1.3412 (4) | 0.0249 (8) | |
C3 | 0.9789 (4) | 0.43766 (13) | 1.4607 (4) | 0.0258 (8) | |
C4 | 0.9958 (4) | 0.36750 (13) | 1.3367 (5) | 0.0288 (9) | |
C5 | 0.9359 (5) | 0.34747 (15) | 1.4486 (5) | 0.0387 (10) | |
H5 | 0.9122 | 0.3171 | 1.4478 | 0.046* | |
C6 | 0.9137 (5) | 0.37273 (15) | 1.5558 (5) | 0.0358 (10) | |
C7 | 0.8558 (7) | 0.35237 (18) | 1.6796 (6) | 0.0542 (15) | |
C8 | 1.2338 (4) | 0.44558 (14) | 1.2947 (5) | 0.0279 (9) | |
C9 | 1.3053 (5) | 0.41197 (16) | 1.3543 (6) | 0.0454 (13) | |
H9 | 1.2654 | 0.3838 | 1.3664 | 0.054* | |
C10 | 1.4348 (5) | 0.41866 (18) | 1.3968 (6) | 0.0519 (14) | |
H10 | 1.4826 | 0.3954 | 1.4372 | 0.062* | |
C11 | 1.4917 (4) | 0.45984 (18) | 1.3788 (6) | 0.0441 (12) | |
C12 | 1.4249 (5) | 0.49351 (18) | 1.3178 (6) | 0.0450 (12) | |
H12 | 1.4660 | 0.5214 | 1.3044 | 0.054* | |
C13 | 1.2959 (5) | 0.48627 (15) | 1.2758 (5) | 0.0362 (10) | |
H13 | 1.2495 | 0.5095 | 1.2336 | 0.043* | |
Br1 | 1.66612 (4) | 0.47071 (3) | 1.44122 (8) | 0.0697 (2) | |
O2 | 0.7222 (3) | 0.09824 (9) | 0.9889 (3) | 0.0338 (7) | |
F4 | 1.2813 (4) | 0.10516 (13) | 1.0040 (5) | 0.0782 (13) | |
F5 | 1.1837 (3) | 0.05015 (8) | 1.0941 (4) | 0.0578 (10) | |
F6 | 1.2446 (3) | 0.10589 (11) | 1.2081 (5) | 0.0631 (10) | |
N6 | 0.7243 (3) | 0.22885 (11) | 1.0553 (4) | 0.0271 (8) | |
H6N | 0.653 (3) | 0.2463 (13) | 1.073 (5) | 0.032* | |
N7 | 0.9576 (3) | 0.22901 (10) | 1.0690 (4) | 0.0261 (7) | |
N8 | 0.8395 (3) | 0.16152 (10) | 1.0287 (4) | 0.0237 (7) | |
N9 | 1.0675 (3) | 0.16188 (11) | 1.0790 (4) | 0.0288 (8) | |
N10 | 0.8364 (4) | 0.29270 (11) | 1.1091 (4) | 0.0319 (8) | |
H10A | 0.909 (3) | 0.3050 (15) | 1.144 (5) | 0.038* | |
H10B | 0.762 (3) | 0.3090 (15) | 1.104 (6) | 0.038* | |
C20 | 1.1928 (5) | 0.09342 (14) | 1.0926 (6) | 0.0377 (11) | |
C14 | 0.7273 (4) | 0.18807 (12) | 0.9806 (5) | 0.0258 (9) | |
H14 | 0.6443 | 0.1713 | 0.9985 | 0.031* | |
C15 | 0.8407 (4) | 0.25037 (12) | 1.0759 (4) | 0.0231 (8) | |
C16 | 0.9555 (4) | 0.18357 (12) | 1.0582 (4) | 0.0246 (8) | |
C17 | 0.8279 (4) | 0.11509 (13) | 1.0201 (4) | 0.0255 (8) | |
C18 | 0.9505 (4) | 0.09218 (13) | 1.0451 (5) | 0.0287 (9) | |
H18 | 0.9540 | 0.0608 | 1.0441 | 0.034* | |
C19 | 1.0602 (4) | 0.11631 (13) | 1.0699 (4) | 0.0291 (9) | |
Br2 | 0.74894 (14) | 0.22662 (3) | 0.38715 (10) | 0.0924 (5) | 0.899 (3) |
C21 | 0.7359 (4) | 0.19636 (19) | 0.8349 (3) | 0.0312 (13) | 0.899 (3) |
C22 | 0.6379 (4) | 0.22284 (19) | 0.7782 (4) | 0.0475 (14) | 0.899 (3) |
H22 | 0.5695 | 0.2348 | 0.8304 | 0.057* | 0.899 (3) |
C23 | 0.6409 (4) | 0.23160 (16) | 0.6443 (4) | 0.0599 (19) | 0.899 (3) |
H23 | 0.5747 | 0.2495 | 0.6060 | 0.072* | 0.899 (3) |
C24 | 0.7420 (4) | 0.21389 (14) | 0.5671 (3) | 0.0509 (16) | 0.899 (3) |
C25 | 0.8400 (4) | 0.18741 (14) | 0.6238 (3) | 0.0621 (19) | 0.899 (3) |
H25 | 0.9084 | 0.1754 | 0.5716 | 0.075* | 0.899 (3) |
C26 | 0.8370 (4) | 0.17865 (16) | 0.7577 (3) | 0.0463 (16) | 0.899 (3) |
H26 | 0.9033 | 0.1607 | 0.7960 | 0.056* | 0.899 (3) |
Br3 | 0.8608 (7) | 0.21715 (19) | 0.3838 (6) | 0.054 (2)* | 0.101 (3) |
C21A | 0.756 (6) | 0.197 (3) | 0.829 (2) | 0.045* | 0.101 (3) |
C22A | 0.668 (5) | 0.219 (3) | 0.747 (3) | 0.062* | 0.101 (3) |
H22A | 0.5867 | 0.2298 | 0.7806 | 0.075* | 0.101 (3) |
C23A | 0.699 (4) | 0.225 (2) | 0.616 (2) | 0.062* | 0.101 (3) |
H23A | 0.6392 | 0.2402 | 0.5601 | 0.075* | 0.101 (3) |
C24A | 0.818 (3) | 0.2090 (17) | 0.5660 (15) | 0.062* | 0.101 (3) |
C25A | 0.907 (4) | 0.1867 (17) | 0.6480 (18) | 0.062* | 0.101 (3) |
H25A | 0.9876 | 0.1758 | 0.6145 | 0.075* | 0.101 (3) |
C26A | 0.875 (5) | 0.181 (2) | 0.7796 (19) | 0.062* | 0.101 (3) |
H26A | 0.9351 | 0.1654 | 0.8350 | 0.075* | 0.101 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0404 (17) | 0.0260 (14) | 0.0375 (18) | −0.0012 (12) | −0.0011 (14) | −0.0105 (13) |
F1 | 0.103 (3) | 0.0442 (17) | 0.0428 (19) | −0.0128 (17) | 0.0068 (19) | 0.0091 (14) |
F2 | 0.119 (3) | 0.0427 (17) | 0.063 (2) | −0.039 (2) | 0.021 (2) | 0.0051 (17) |
F3 | 0.071 (3) | 0.101 (3) | 0.090 (3) | 0.004 (2) | 0.044 (2) | 0.032 (3) |
N1 | 0.0288 (17) | 0.0241 (16) | 0.0247 (18) | 0.0042 (13) | −0.0028 (14) | −0.0010 (14) |
N2 | 0.0241 (15) | 0.0214 (15) | 0.0255 (19) | 0.0018 (12) | 0.0019 (14) | 0.0007 (14) |
N3 | 0.0235 (16) | 0.0197 (14) | 0.0265 (19) | 0.0033 (12) | −0.0003 (13) | −0.0010 (13) |
N4 | 0.0333 (18) | 0.0281 (16) | 0.0258 (18) | −0.0022 (14) | 0.0025 (15) | 0.0023 (15) |
N5 | 0.047 (2) | 0.0229 (17) | 0.031 (2) | 0.0074 (15) | 0.0066 (18) | 0.0020 (16) |
C1 | 0.0256 (19) | 0.0257 (19) | 0.024 (2) | 0.0051 (15) | 0.0029 (15) | −0.0009 (16) |
C2 | 0.0203 (18) | 0.0254 (18) | 0.029 (2) | 0.0001 (14) | −0.0008 (16) | 0.0024 (16) |
C3 | 0.0210 (17) | 0.0277 (19) | 0.029 (2) | 0.0016 (14) | −0.0037 (16) | −0.0034 (17) |
C4 | 0.027 (2) | 0.0196 (18) | 0.040 (2) | 0.0005 (15) | −0.0060 (18) | −0.0055 (18) |
C5 | 0.047 (2) | 0.028 (2) | 0.041 (3) | −0.0088 (18) | −0.003 (2) | 0.002 (2) |
C6 | 0.034 (2) | 0.032 (2) | 0.041 (3) | −0.0076 (18) | 0.000 (2) | 0.005 (2) |
C7 | 0.071 (4) | 0.041 (3) | 0.050 (4) | −0.013 (3) | 0.016 (3) | 0.005 (3) |
C8 | 0.027 (2) | 0.031 (2) | 0.026 (2) | 0.0038 (16) | 0.0029 (17) | −0.0034 (17) |
C9 | 0.034 (2) | 0.037 (2) | 0.065 (4) | −0.0027 (19) | −0.006 (2) | 0.019 (2) |
C10 | 0.035 (2) | 0.059 (3) | 0.062 (4) | 0.012 (2) | −0.008 (2) | 0.018 (3) |
C11 | 0.020 (2) | 0.067 (3) | 0.045 (3) | 0.000 (2) | −0.009 (2) | −0.015 (3) |
C12 | 0.033 (2) | 0.044 (3) | 0.058 (3) | −0.009 (2) | 0.006 (2) | −0.012 (2) |
C13 | 0.029 (2) | 0.033 (2) | 0.047 (3) | −0.0071 (18) | −0.001 (2) | 0.000 (2) |
Br1 | 0.0269 (2) | 0.1078 (5) | 0.0743 (4) | 0.0028 (3) | −0.0111 (3) | −0.0396 (4) |
O2 | 0.0328 (16) | 0.0275 (14) | 0.0410 (19) | −0.0115 (12) | −0.0019 (13) | −0.0060 (13) |
F4 | 0.054 (2) | 0.075 (2) | 0.105 (3) | 0.0289 (17) | 0.040 (2) | 0.035 (2) |
F5 | 0.0513 (18) | 0.0253 (13) | 0.097 (3) | 0.0075 (12) | −0.0090 (18) | −0.0024 (16) |
F6 | 0.0541 (19) | 0.0514 (17) | 0.084 (3) | 0.0087 (15) | −0.0318 (19) | −0.0024 (19) |
N6 | 0.0182 (16) | 0.0241 (16) | 0.039 (2) | 0.0027 (12) | −0.0038 (14) | −0.0013 (15) |
N7 | 0.0238 (16) | 0.0228 (15) | 0.0317 (19) | −0.0017 (12) | −0.0012 (14) | −0.0055 (15) |
N8 | 0.0236 (16) | 0.0170 (14) | 0.0306 (19) | −0.0037 (13) | 0.0000 (13) | −0.0022 (13) |
N9 | 0.0234 (16) | 0.0271 (16) | 0.036 (2) | −0.0004 (13) | −0.0010 (15) | −0.0021 (16) |
N10 | 0.0282 (18) | 0.0223 (17) | 0.045 (2) | −0.0005 (13) | −0.0071 (16) | −0.0066 (16) |
C20 | 0.036 (2) | 0.024 (2) | 0.053 (3) | 0.0041 (17) | 0.004 (2) | 0.006 (2) |
C14 | 0.0235 (19) | 0.0188 (18) | 0.035 (2) | −0.0034 (14) | −0.0021 (16) | 0.0006 (16) |
C15 | 0.0263 (19) | 0.0203 (17) | 0.0227 (19) | 0.0001 (14) | −0.0019 (16) | 0.0032 (16) |
C16 | 0.0223 (18) | 0.0272 (19) | 0.024 (2) | −0.0066 (15) | 0.0011 (16) | −0.0003 (16) |
C17 | 0.033 (2) | 0.0238 (18) | 0.0199 (19) | −0.0006 (16) | 0.0032 (16) | −0.0034 (16) |
C18 | 0.032 (2) | 0.0179 (17) | 0.036 (2) | −0.0016 (16) | −0.0008 (18) | 0.0034 (17) |
C19 | 0.031 (2) | 0.028 (2) | 0.028 (2) | 0.0018 (16) | 0.0023 (18) | 0.0035 (18) |
Br2 | 0.1629 (13) | 0.0842 (6) | 0.0300 (3) | −0.0488 (7) | −0.0104 (5) | 0.0130 (4) |
C21 | 0.044 (3) | 0.019 (2) | 0.030 (3) | −0.017 (2) | −0.012 (2) | −0.0023 (19) |
C22 | 0.053 (4) | 0.051 (4) | 0.039 (3) | 0.004 (3) | −0.011 (3) | 0.008 (3) |
C23 | 0.084 (5) | 0.051 (4) | 0.045 (4) | −0.008 (4) | −0.024 (4) | 0.012 (3) |
C24 | 0.087 (5) | 0.043 (3) | 0.023 (3) | −0.027 (3) | −0.007 (3) | 0.000 (3) |
C25 | 0.092 (6) | 0.063 (4) | 0.031 (3) | −0.010 (4) | 0.006 (3) | −0.011 (3) |
C26 | 0.065 (4) | 0.046 (3) | 0.028 (3) | 0.001 (3) | −0.003 (3) | −0.004 (2) |
O1—C4 | 1.229 (5) | N6—H6N | 0.902 (19) |
F1—C7 | 1.331 (8) | N7—C15 | 1.339 (5) |
F2—C7 | 1.319 (6) | N7—C16 | 1.364 (5) |
F3—C7 | 1.334 (7) | N8—C16 | 1.373 (5) |
N1—C2 | 1.344 (6) | N8—C17 | 1.396 (5) |
N1—C1 | 1.446 (5) | N8—C14 | 1.464 (5) |
N1—H1N | 0.87 (2) | N9—C16 | 1.317 (5) |
N2—C2 | 1.334 (6) | N9—C19 | 1.368 (5) |
N2—C3 | 1.348 (5) | N10—C15 | 1.311 (5) |
N3—C3 | 1.379 (5) | N10—H10A | 0.89 (2) |
N3—C4 | 1.403 (5) | N10—H10B | 0.90 (2) |
N3—C1 | 1.465 (5) | C20—C19 | 1.516 (6) |
N4—C3 | 1.318 (6) | C14—C21 | 1.509 (5) |
N4—C6 | 1.351 (6) | C14—C21A | 1.591 (9) |
N5—C2 | 1.331 (5) | C14—H14 | 0.9900 |
N5—H5A | 0.895 (14) | C17—C18 | 1.433 (6) |
N5—H5B | 0.892 (14) | C18—C19 | 1.343 (6) |
C1—C8 | 1.519 (6) | C18—H18 | 0.9400 |
C1—H1A | 0.9900 | Br2—C24 | 1.875 (3) |
C4—C5 | 1.423 (7) | C21—C22 | 1.3900 |
C5—C6 | 1.347 (8) | C21—C26 | 1.3900 |
C5—H5 | 0.9400 | C22—C23 | 1.3900 |
C6—C7 | 1.517 (7) | C22—H22 | 0.9400 |
C8—C9 | 1.377 (6) | C23—C24 | 1.3900 |
C8—C13 | 1.381 (6) | C23—H23 | 0.9400 |
C9—C10 | 1.387 (7) | C24—C25 | 1.3900 |
C9—H9 | 0.9400 | C25—C26 | 1.3900 |
C10—C11 | 1.371 (8) | C25—H25 | 0.9400 |
C10—H10 | 0.9400 | C26—H26 | 0.9400 |
C11—C12 | 1.361 (8) | Br3—C24A | 1.921 (7) |
C11—Br1 | 1.893 (4) | C21A—C22A | 1.3900 |
C12—C13 | 1.383 (7) | C21A—C26A | 1.3900 |
C12—H12 | 0.9400 | C22A—C23A | 1.3900 |
C13—H13 | 0.9400 | C22A—H22A | 0.9400 |
O2—C17 | 1.219 (5) | C23A—C24A | 1.3900 |
F4—C20 | 1.316 (6) | C23A—H23A | 0.9400 |
F5—C20 | 1.298 (5) | C24A—C25A | 1.3900 |
F6—C20 | 1.341 (7) | C25A—C26A | 1.3900 |
N6—C15 | 1.352 (5) | C25A—H25A | 0.9400 |
N6—C14 | 1.439 (5) | C26A—H26A | 0.9400 |
C2—N1—C1 | 115.8 (4) | F5—C20—F4 | 108.7 (4) |
C2—N1—H1N | 119 (3) | F5—C20—F6 | 107.1 (4) |
C1—N1—H1N | 123 (3) | F4—C20—F6 | 105.4 (4) |
C2—N2—C3 | 117.5 (3) | F5—C20—C19 | 113.0 (4) |
C3—N3—C4 | 123.9 (4) | F4—C20—C19 | 111.7 (4) |
C3—N3—C1 | 116.3 (3) | F6—C20—C19 | 110.5 (4) |
C4—N3—C1 | 119.7 (3) | N6—C14—N8 | 107.3 (3) |
C3—N4—C6 | 116.3 (4) | N6—C14—C21 | 112.5 (4) |
C2—N5—H5A | 113 (3) | N8—C14—C21 | 112.0 (4) |
C2—N5—H5B | 126 (4) | N6—C14—C21A | 112 (3) |
H5A—N5—H5B | 121 (5) | N8—C14—C21A | 106 (2) |
N1—C1—N3 | 106.2 (3) | C21—C14—C21A | 7 (2) |
N1—C1—C8 | 112.7 (3) | N6—C14—H14 | 108.3 |
N3—C1—C8 | 109.8 (3) | N8—C14—H14 | 108.3 |
N1—C1—H1A | 109.3 | C21—C14—H14 | 108.3 |
N3—C1—H1A | 109.3 | C21A—C14—H14 | 114.4 |
C8—C1—H1A | 109.3 | N10—C15—N7 | 120.2 (3) |
N5—C2—N2 | 119.8 (4) | N10—C15—N6 | 118.1 (3) |
N5—C2—N1 | 118.1 (4) | N7—C15—N6 | 121.6 (3) |
N2—C2—N1 | 122.0 (4) | N9—C16—N7 | 117.7 (3) |
N4—C3—N2 | 119.2 (4) | N9—C16—N8 | 121.7 (3) |
N4—C3—N3 | 120.7 (3) | N7—C16—N8 | 120.6 (3) |
N2—C3—N3 | 120.0 (4) | O2—C17—N8 | 120.0 (4) |
O1—C4—N3 | 119.7 (4) | O2—C17—C18 | 126.8 (4) |
O1—C4—C5 | 127.3 (4) | N8—C17—C18 | 113.1 (3) |
N3—C4—C5 | 113.0 (4) | C19—C18—C17 | 118.9 (4) |
C6—C5—C4 | 119.0 (4) | C19—C18—H18 | 120.6 |
C6—C5—H5 | 120.5 | C17—C18—H18 | 120.6 |
C4—C5—H5 | 120.5 | C18—C19—N9 | 126.3 (4) |
C5—C6—N4 | 126.3 (4) | C18—C19—C20 | 120.6 (4) |
C5—C6—C7 | 120.9 (4) | N9—C19—C20 | 113.1 (4) |
N4—C6—C7 | 112.8 (4) | C22—C21—C26 | 120.0 |
F2—C7—F1 | 107.1 (5) | C22—C21—C14 | 117.5 (3) |
F2—C7—F3 | 107.7 (5) | C26—C21—C14 | 122.5 (3) |
F1—C7—F3 | 106.2 (5) | C21—C22—C23 | 120.0 |
F2—C7—C6 | 112.7 (5) | C21—C22—H22 | 120.0 |
F1—C7—C6 | 112.1 (4) | C23—C22—H22 | 120.0 |
F3—C7—C6 | 110.8 (5) | C24—C23—C22 | 120.0 |
C9—C8—C13 | 118.0 (4) | C24—C23—H23 | 120.0 |
C9—C8—C1 | 121.2 (4) | C22—C23—H23 | 120.0 |
C13—C8—C1 | 120.9 (4) | C23—C24—C25 | 120.0 |
C8—C9—C10 | 121.5 (4) | C23—C24—Br2 | 120.2 (2) |
C8—C9—H9 | 119.2 | C25—C24—Br2 | 119.7 (2) |
C10—C9—H9 | 119.2 | C24—C25—C26 | 120.0 |
C11—C10—C9 | 118.7 (5) | C24—C25—H25 | 120.0 |
C11—C10—H10 | 120.7 | C26—C25—H25 | 120.0 |
C9—C10—H10 | 120.7 | C25—C26—C21 | 120.0 |
C12—C11—C10 | 121.3 (4) | C25—C26—H26 | 120.0 |
C12—C11—Br1 | 118.9 (4) | C21—C26—H26 | 120.0 |
C10—C11—Br1 | 119.7 (4) | C22A—C21A—C26A | 120.0 |
C11—C12—C13 | 119.3 (5) | C22A—C21A—C14 | 123 (3) |
C11—C12—H12 | 120.4 | C26A—C21A—C14 | 117 (3) |
C13—C12—H12 | 120.4 | C21A—C22A—C23A | 120.0 |
C8—C13—C12 | 121.2 (5) | C21A—C22A—H22A | 120.0 |
C8—C13—H13 | 119.4 | C23A—C22A—H22A | 120.0 |
C12—C13—H13 | 119.4 | C24A—C23A—C22A | 120.0 |
C15—N6—C14 | 117.9 (3) | C24A—C23A—H23A | 120.0 |
C15—N6—H6N | 112 (3) | C22A—C23A—H23A | 120.0 |
C14—N6—H6N | 128 (3) | C23A—C24A—C25A | 120.0 |
C15—N7—C16 | 117.8 (3) | C23A—C24A—Br3 | 119.9 (4) |
C16—N8—C17 | 124.2 (3) | C25A—C24A—Br3 | 120.0 (4) |
C16—N8—C14 | 117.9 (3) | C26A—C25A—C24A | 120.0 |
C17—N8—C14 | 117.0 (3) | C26A—C25A—H25A | 120.0 |
C16—N9—C19 | 115.7 (3) | C24A—C25A—H25A | 120.0 |
C15—N10—H10A | 118 (3) | C25A—C26A—C21A | 120.0 |
C15—N10—H10B | 122 (3) | C25A—C26A—H26A | 120.0 |
H10A—N10—H10B | 119 (5) | C21A—C26A—H26A | 120.0 |
C2—N1—C1—N3 | 49.4 (5) | C14—N6—C15—N10 | 160.7 (4) |
C2—N1—C1—C8 | −70.9 (5) | C14—N6—C15—N7 | −22.5 (6) |
C3—N3—C1—N1 | −45.3 (4) | C19—N9—C16—N7 | 178.7 (4) |
C4—N3—C1—N1 | 136.7 (4) | C19—N9—C16—N8 | −0.3 (6) |
C3—N3—C1—C8 | 76.9 (4) | C15—N7—C16—N9 | −166.1 (4) |
C4—N3—C1—C8 | −101.0 (4) | C15—N7—C16—N8 | 12.9 (6) |
C3—N2—C2—N5 | 163.1 (4) | C17—N8—C16—N9 | 1.2 (6) |
C3—N2—C2—N1 | −13.9 (6) | C14—N8—C16—N9 | −167.5 (4) |
C1—N1—C2—N5 | 160.7 (4) | C17—N8—C16—N7 | −177.8 (4) |
C1—N1—C2—N2 | −22.3 (6) | C14—N8—C16—N7 | 13.5 (6) |
C6—N4—C3—N2 | 170.1 (4) | C16—N8—C17—O2 | −177.5 (4) |
C6—N4—C3—N3 | −8.0 (6) | C14—N8—C17—O2 | −8.7 (6) |
C2—N2—C3—N4 | −160.4 (4) | C16—N8—C17—C18 | −0.2 (6) |
C2—N2—C3—N3 | 17.8 (5) | C14—N8—C17—C18 | 168.6 (4) |
C4—N3—C3—N4 | 9.9 (6) | O2—C17—C18—C19 | 175.5 (4) |
C1—N3—C3—N4 | −167.9 (4) | N8—C17—C18—C19 | −1.6 (6) |
C4—N3—C3—N2 | −168.2 (3) | C17—C18—C19—N9 | 2.6 (7) |
C1—N3—C3—N2 | 13.9 (5) | C17—C18—C19—C20 | −178.1 (4) |
C3—N3—C4—O1 | 178.5 (4) | C16—N9—C19—C18 | −1.6 (7) |
C1—N3—C4—O1 | −3.8 (6) | C16—N9—C19—C20 | 179.1 (4) |
C3—N3—C4—C5 | −3.8 (5) | F5—C20—C19—C18 | −4.4 (7) |
C1—N3—C4—C5 | 174.0 (4) | F4—C20—C19—C18 | 118.5 (5) |
O1—C4—C5—C6 | 174.3 (4) | F6—C20—C19—C18 | −124.5 (5) |
N3—C4—C5—C6 | −3.2 (6) | F5—C20—C19—N9 | 175.0 (4) |
C4—C5—C6—N4 | 5.0 (8) | F4—C20—C19—N9 | −62.1 (6) |
C4—C5—C6—C7 | −177.2 (5) | F6—C20—C19—N9 | 54.9 (5) |
C3—N4—C6—C5 | 0.8 (7) | N6—C14—C21—C22 | −56.3 (4) |
C3—N4—C6—C7 | −177.1 (4) | N8—C14—C21—C22 | −177.3 (3) |
C5—C6—C7—F2 | 4.5 (8) | C21A—C14—C21—C22 | −147 (25) |
N4—C6—C7—F2 | −177.4 (5) | N6—C14—C21—C26 | 123.7 (4) |
C5—C6—C7—F1 | 125.4 (5) | N8—C14—C21—C26 | 2.6 (5) |
N4—C6—C7—F1 | −56.6 (6) | C21A—C14—C21—C26 | 33 (24) |
C5—C6—C7—F3 | −116.3 (6) | C26—C21—C22—C23 | 0.0 |
N4—C6—C7—F3 | 61.8 (6) | C14—C21—C22—C23 | 180.0 (5) |
N1—C1—C8—C9 | 160.8 (5) | C21—C22—C23—C24 | 0.0 |
N3—C1—C8—C9 | 42.5 (6) | C22—C23—C24—C25 | 0.0 |
N1—C1—C8—C13 | −19.2 (6) | C22—C23—C24—Br2 | −178.6 (3) |
N3—C1—C8—C13 | −137.5 (4) | C23—C24—C25—C26 | 0.0 |
C13—C8—C9—C10 | 1.3 (8) | Br2—C24—C25—C26 | 178.6 (3) |
C1—C8—C9—C10 | −178.7 (5) | C24—C25—C26—C21 | 0.0 |
C8—C9—C10—C11 | 0.1 (9) | C22—C21—C26—C25 | 0.0 |
C9—C10—C11—C12 | −1.5 (9) | C14—C21—C26—C25 | −180.0 (5) |
C9—C10—C11—Br1 | 177.8 (5) | N6—C14—C21A—C22A | −66 (4) |
C10—C11—C12—C13 | 1.4 (9) | N8—C14—C21A—C22A | 177 (3) |
Br1—C11—C12—C13 | −177.9 (4) | C21—C14—C21A—C22A | 26 (22) |
C9—C8—C13—C12 | −1.4 (8) | N6—C14—C21A—C26A | 114 (3) |
C1—C8—C13—C12 | 178.6 (5) | N8—C14—C21A—C26A | −3 (4) |
C11—C12—C13—C8 | 0.1 (8) | C21—C14—C21A—C26A | −154 (27) |
C15—N6—C14—N8 | 44.6 (5) | C26A—C21A—C22A—C23A | 0.0 |
C15—N6—C14—C21 | −79.0 (5) | C14—C21A—C22A—C23A | −180 (6) |
C15—N6—C14—C21A | −71 (2) | C21A—C22A—C23A—C24A | 0.0 |
C16—N8—C14—N6 | −40.1 (5) | C22A—C23A—C24A—C25A | 0.0 |
C17—N8—C14—N6 | 150.4 (3) | C22A—C23A—C24A—Br3 | 179 (4) |
C16—N8—C14—C21 | 83.9 (5) | C23A—C24A—C25A—C26A | 0.0 |
C17—N8—C14—C21 | −85.6 (5) | Br3—C24A—C25A—C26A | −179 (4) |
C16—N8—C14—C21A | 80 (3) | C24A—C25A—C26A—C21A | 0.0 |
C17—N8—C14—C21A | −89 (3) | C22A—C21A—C26A—C25A | 0.0 |
C16—N7—C15—N10 | 168.1 (4) | C14—C21A—C26A—C25A | 180 (6) |
C16—N7—C15—N6 | −8.7 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2i | 0.87 (2) | 2.15 (2) | 3.005 (5) | 171 (5) |
N5—H5A···O2ii | 0.90 (1) | 2.09 (3) | 2.905 (5) | 152 (5) |
N5—H5B···N4i | 0.89 (1) | 2.25 (2) | 3.095 (6) | 159 (5) |
N5—H5B···F1i | 0.89 (1) | 2.46 (4) | 3.054 (5) | 124 (4) |
N6—H6N···N7iii | 0.90 (2) | 2.10 (3) | 2.967 (5) | 160 (5) |
N10—H10A···O1 | 0.89 (2) | 2.03 (3) | 2.885 (5) | 162 (5) |
N10—H10B···N9iii | 0.90 (2) | 2.15 (2) | 3.041 (5) | 171 (5) |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+3/2, y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C13H9BrF3N5O |
Mr | 388.16 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 223 |
a, b, c (Å) | 10.0531 (4), 29.9108 (13), 10.1945 (4) |
V (Å3) | 3065.4 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.73 |
Crystal size (mm) | 0.46 × 0.34 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.367, 0.612 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20728, 6287, 4979 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.138, 1.04 |
No. of reflections | 6287 |
No. of parameters | 432 |
No. of restraints | 16 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.50, −0.74 |
Absolute structure | Flack (1983), 2044 Friedel pairs |
Absolute structure parameter | 0.011 (10) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2i | 0.87 (2) | 2.15 (2) | 3.005 (5) | 171 (5) |
N5—H5A···O2ii | 0.895 (14) | 2.09 (3) | 2.905 (5) | 152 (5) |
N5—H5B···N4i | 0.892 (14) | 2.25 (2) | 3.095 (6) | 159 (5) |
N5—H5B···F1i | 0.892 (14) | 2.46 (4) | 3.054 (5) | 124 (4) |
N6—H6N···N7iii | 0.902 (19) | 2.10 (3) | 2.967 (5) | 160 (5) |
N10—H10A···O1 | 0.89 (2) | 2.03 (3) | 2.885 (5) | 162 (5) |
N10—H10B···N9iii | 0.90 (2) | 2.15 (2) | 3.041 (5) | 171 (5) |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+3/2, y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z. |
Footnotes
†Part 13 in the series `Fused heterocyclic systems with an s-triazine ring'. For Part 12, see Dolzhenko et al. (2008b).
Acknowledgements
This work was supported by the National Medical Research Council, Singapore (grant Nos. NMRC/NIG/0019/2008 and NMRC/NIG/0020/2008).
References
Bruker (2001). SMART and SAINT. Bruker AXS GmbH, Karlsruhe, Germany. Google Scholar
Dolzhenko, A. V., Dolzhenko, A. V. & Chui, W. K. (2008a). J. Heterocycl. Chem. 45, 173-176. CrossRef CAS Google Scholar
Dolzhenko, A. V., Pastorin, G., Dolzhenko, A. V. & Chui, W. K. (2008b). Tetrahedron Lett. 49, 7180-7183. Web of Science CrossRef CAS Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2007). Acta Cryst. E63, o2796. Web of Science CSD CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound was synthesized via thermal cyclocondensation of 6-oxo-4-trifluoromethyl-1,6-dihydropyrimidin-2-yl guanidine with p-bromobenzaldehyde (Fig.1) using the methodology that we successfully applied previously for the preparation of its benzofused analogues (Dolzhenko et al., 2008a). In general, the synthesized compound might be involved in tautomerism with four possible tautomers (Fig. 2). However, only one tautomeric form viz. 2-amino-4-(4-bromophenyl)-8-trifluoromethyl-3,4-dihydro-6H-pyrimido[1,2-a][1,3,5]triazin-6-one was found in the crystal.
The compound crystallized with two independent molecules (A and B) in the asymmetric unit (Fig. 3). The pyrimidine rings in the molecules are planar with maximum deviations 0.0525 (26) Å (C3) and 0.0118 (32) Å (C18) from the planes C3/N3/C4—C6/N4 and C16/N8/C17—C19/N9 of molecules A and B, respectively. Similarly to structurally related 7,7-dimethyl-2-phenyl-6,7-dyhydro-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine (Dolzhenko et al., 2007), the triazine rings in the molecules adopt flattened half-boat conformations with atoms N2 and N7 at the sterns and sp3-hybridized atoms C1 and C14 at the bows with p-bromophenyl rings as flagpoles. However, the molecules are significantly different in the geometry at bridgehead nitrogen atoms (N3 and N8) and sp3-hybridized atoms C1 and C14 of the triazine rings.The torsion angles C4—N3—C1—N1 and C17—N8—C14—N6 are 136.7 (4)° and 150.4 (3)°, respectively. In molecule B, the bond N8—C14 is located almost in the phenyl ring (C21—C26) plane: the torsion angle N8—C14—C21—C26 is 2.6 (5)°. The corresponding torsion angle N3—C1—C8—C9 of molecule A is 42.5 (6)°. The N1—C2, N2—C2, N5—C2 bond distances in A and N6—C15, N7—C15, N10—C15 in B are similar that suggests guanidine-like electron delocalization in N1/N2/N5/C2 and N6/N7/N10/C15 fragments of the molecules.
The crystal packing is stabilized by three-dimensional network of intramolecular N—H···N, N—H···O and N—H···F hydrogen bonds (Table 1, Fig. 4).