The molecules of the title compound, C
15H
13FN
4O, display the characteristic features of 1,2,4-triazole derivatives. The triazole ring is planar and the two benzene rings are nearly parallel, with a dihedral angle of 8.5 (1)°. The crystal structure is stabilized by N—H
O and N—H
N intermolecular hydrogen bonds.
Supporting information
CCDC reference: 214827
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.043
- wR factor = 0.089
- Data-to-parameter ratio = 15.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies
outside the range 0.80 <> 2.00
Goodness of fit given = 0.749
REFLT_03
From the CIF: _diffrn_reflns_theta_max 28.07
From the CIF: _reflns_number_total 2992
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3289
Completeness (_total/calc) 90.97%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The corresponding Schiff base (2.82 g, 0.01 mol) was dissolved in 40 ml of dry dilyme with gentle heating and a solution of NaBH4 (0.003 mol) in 30 ml of dry diglyme was slowly added to the solution with constant stirring. Then the mixture was allowed to cool. In order to precipitate the product, 300 ml of water was added to the solution and the mixture was allowed to stand overnight at 273–278 K. The precipitate was filtered off and washed with cold water. After drying in vacuo, the solid product was recrystallized from ethanol to afford the desired compound (1.46 g, 51%). Calculated: C 63.37, H 4.61, N 19.71%; found: C 63.31, H 5.00, N 19.64%. IR data (KBr/ cm−1): 3290, 3090 (N—H), 1710 (C═O), 1510 (C═N), 830, 740, 670 (aromatic). 1H NMR (CDCl3, δ/p.p.m.): 4.18 (d, CH2), 5.22 (t, NNH), 10.78 (s, NH), 6.80–7.30 (m, 3H), 7.40 (m, 2H), 7.86 (m, 2H).
Only H atoms for N atoms were located from difference Fourier map and refined isotropically. Other H atoms were located geometrically and refined using a riding model, fixing the aromatic CH C—H distance at 0.93 Å and the CH2 C—H distance at 0.97 Å.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997) and PARST (Nardelli, 1995).
4-(
p-Fluorobenzylamino)-3-phenyl-4,5-dihydro-1
H-1,2,4-triazol-5-one
top
Crystal data top
C15H13FN4O | F(000) = 592 |
Mr = 284.29 | Dx = 1.397 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.4560 (19) Å | Cell parameters from 7012 reflections |
b = 6.2183 (7) Å | θ = 2.8–18.9° |
c = 14.8165 (18) Å | µ = 0.10 mm−1 |
β = 108.347 (2)° | T = 293 K |
V = 1351.6 (3) Å3 | Prismatic, colourless |
Z = 4 | 0.42 × 0.17 × 0.16 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1141 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 28.1°, θmin = 2.8° |
ϕ and ω scans | h = −20→15 |
7084 measured reflections | k = −8→7 |
2992 independent reflections | l = −18→19 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.75 | w = 1/[σ2(Fo2) + (0.0243P)2] where P = (Fo2 + 2Fc2)/3 |
2992 reflections | (Δ/σ)max < 0.001 |
198 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C15H13FN4O | V = 1351.6 (3) Å3 |
Mr = 284.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.4560 (19) Å | µ = 0.10 mm−1 |
b = 6.2183 (7) Å | T = 293 K |
c = 14.8165 (18) Å | 0.42 × 0.17 × 0.16 mm |
β = 108.347 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1141 reflections with I > 2σ(I) |
7084 measured reflections | Rint = 0.052 |
2992 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.75 | Δρmax = 0.17 e Å−3 |
2992 reflections | Δρmin = −0.15 e Å−3 |
198 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C7 | 0.22194 (14) | 0.1194 (4) | 0.93979 (14) | 0.0345 (6) | |
N3 | 0.16826 (11) | 0.2995 (3) | 0.92399 (12) | 0.0366 (5) | |
O1 | 0.01909 (10) | 0.3726 (2) | 0.82906 (10) | 0.0541 (5) | |
C1 | 0.31638 (14) | 0.1081 (4) | 1.00402 (14) | 0.0372 (6) | |
N2 | 0.09344 (13) | 0.0412 (3) | 0.84005 (13) | 0.0460 (6) | |
N1 | 0.17907 (12) | −0.0415 (3) | 0.88840 (12) | 0.0436 (5) | |
C8 | 0.08448 (15) | 0.2495 (4) | 0.85903 (14) | 0.0396 (6) | |
C6 | 0.37524 (15) | 0.2802 (4) | 1.01647 (15) | 0.0477 (6) | |
H6 | 0.3552 | 0.4078 | 0.9839 | 0.057* | |
F1 | 0.29645 (12) | −0.1225 (3) | 1.31769 (10) | 0.0970 (6) | |
N4 | 0.18831 (13) | 0.4923 (3) | 0.97466 (15) | 0.0459 (6) | |
C15 | 0.26535 (17) | 0.3686 (4) | 1.18395 (16) | 0.0572 (7) | |
H15 | 0.2985 | 0.4913 | 1.1804 | 0.069* | |
C13 | 0.2563 (2) | 0.0345 (5) | 1.25393 (18) | 0.0651 (8) | |
C2 | 0.34768 (15) | −0.0820 (4) | 1.05251 (16) | 0.0528 (7) | |
H2 | 0.3092 | −0.2005 | 1.0438 | 0.063* | |
C5 | 0.46374 (16) | 0.2650 (4) | 1.07686 (17) | 0.0590 (7) | |
H5 | 0.5032 | 0.3813 | 1.0842 | 0.071* | |
C9 | 0.13946 (17) | 0.5077 (4) | 1.04533 (18) | 0.0651 (8) | |
H9A | 0.0750 | 0.4805 | 1.0149 | 0.078* | |
H9B | 0.1461 | 0.6514 | 1.0721 | 0.078* | |
C10 | 0.17765 (17) | 0.3461 (4) | 1.12290 (17) | 0.0526 (7) | |
C12 | 0.1686 (2) | 0.0044 (5) | 1.1979 (2) | 0.0723 (9) | |
H12 | 0.1358 | −0.1173 | 1.2039 | 0.087* | |
C3 | 0.43588 (17) | −0.0950 (4) | 1.11364 (17) | 0.0665 (8) | |
H3 | 0.4564 | −0.2218 | 1.1467 | 0.080* | |
C4 | 0.49315 (17) | 0.0780 (4) | 1.12581 (18) | 0.0677 (8) | |
H4 | 0.5523 | 0.0686 | 1.1675 | 0.081* | |
C14 | 0.30474 (18) | 0.2121 (4) | 1.25028 (17) | 0.0635 (8) | |
H14 | 0.3637 | 0.2292 | 1.2917 | 0.076* | |
C11 | 0.12997 (18) | 0.1627 (5) | 1.1315 (2) | 0.0687 (9) | |
H11 | 0.0704 | 0.1452 | 1.0916 | 0.082* | |
H4N | 0.1767 (15) | 0.605 (4) | 0.9312 (15) | 0.073 (9)* | |
H2N | 0.0557 (14) | −0.036 (3) | 0.7922 (14) | 0.055 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C7 | 0.0332 (14) | 0.0336 (14) | 0.0323 (13) | 0.0038 (12) | 0.0041 (11) | 0.0014 (11) |
N3 | 0.0328 (12) | 0.0332 (12) | 0.0356 (10) | −0.0001 (9) | −0.0011 (9) | −0.0020 (9) |
O1 | 0.0422 (10) | 0.0549 (11) | 0.0515 (10) | 0.0134 (9) | −0.0049 (8) | 0.0053 (9) |
C1 | 0.0318 (13) | 0.0373 (14) | 0.0386 (13) | 0.0038 (12) | 0.0056 (11) | 0.0003 (12) |
N2 | 0.0403 (14) | 0.0422 (14) | 0.0418 (12) | −0.0042 (11) | −0.0069 (11) | −0.0086 (11) |
N1 | 0.0344 (12) | 0.0433 (13) | 0.0430 (11) | 0.0033 (10) | −0.0022 (10) | −0.0065 (10) |
C8 | 0.0358 (15) | 0.0424 (16) | 0.0340 (13) | −0.0008 (13) | 0.0015 (12) | 0.0016 (13) |
C6 | 0.0372 (15) | 0.0455 (16) | 0.0540 (15) | 0.0027 (12) | 0.0050 (13) | 0.0061 (13) |
F1 | 0.1351 (16) | 0.0824 (13) | 0.0735 (11) | −0.0195 (11) | 0.0329 (11) | 0.0105 (10) |
N4 | 0.0462 (13) | 0.0344 (13) | 0.0472 (13) | 0.0027 (11) | 0.0005 (11) | −0.0046 (12) |
C15 | 0.0537 (18) | 0.0592 (18) | 0.0543 (16) | −0.0166 (15) | 0.0110 (15) | −0.0046 (15) |
C13 | 0.083 (2) | 0.069 (2) | 0.0455 (18) | −0.0149 (19) | 0.0242 (17) | −0.0048 (16) |
C2 | 0.0419 (16) | 0.0431 (16) | 0.0623 (16) | 0.0010 (13) | 0.0005 (14) | 0.0005 (13) |
C5 | 0.0357 (16) | 0.0535 (18) | 0.0786 (19) | −0.0041 (13) | 0.0049 (15) | −0.0043 (16) |
C9 | 0.0481 (17) | 0.070 (2) | 0.0690 (18) | 0.0136 (15) | 0.0071 (16) | −0.0269 (17) |
C10 | 0.0422 (17) | 0.0638 (19) | 0.0528 (17) | −0.0024 (15) | 0.0162 (14) | −0.0187 (15) |
C12 | 0.084 (2) | 0.082 (2) | 0.065 (2) | −0.036 (2) | 0.0438 (19) | −0.0231 (19) |
C3 | 0.0490 (17) | 0.0516 (18) | 0.0791 (19) | 0.0120 (14) | −0.0085 (16) | 0.0107 (15) |
C4 | 0.0406 (17) | 0.064 (2) | 0.078 (2) | 0.0055 (15) | −0.0105 (15) | −0.0028 (16) |
C14 | 0.067 (2) | 0.070 (2) | 0.0470 (16) | −0.0236 (17) | 0.0094 (15) | −0.0043 (15) |
C11 | 0.0495 (18) | 0.098 (3) | 0.063 (2) | −0.0199 (19) | 0.0242 (16) | −0.0335 (19) |
Geometric parameters (Å, º) top
C7—N1 | 1.305 (2) | C15—H15 | 0.9300 |
C7—N3 | 1.369 (2) | C13—C14 | 1.345 (3) |
C7—C1 | 1.472 (3) | C13—C12 | 1.362 (3) |
N3—C8 | 1.384 (2) | C2—C3 | 1.381 (3) |
N3—N4 | 1.397 (2) | C2—H2 | 0.9300 |
O1—C8 | 1.234 (2) | C5—C4 | 1.370 (3) |
C1—C6 | 1.379 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.389 (3) | C9—C10 | 1.501 (3) |
N2—C8 | 1.342 (3) | C9—H9A | 0.9700 |
N2—N1 | 1.390 (2) | C9—H9B | 0.9700 |
N2—H2N | 0.901 (19) | C10—C11 | 1.385 (3) |
C6—C5 | 1.382 (3) | C12—C11 | 1.386 (3) |
C6—H6 | 0.9300 | C12—H12 | 0.9300 |
F1—C13 | 1.364 (3) | C3—C4 | 1.368 (3) |
N4—C9 | 1.474 (3) | C3—H3 | 0.9300 |
N4—H4N | 0.93 (2) | C4—H4 | 0.9300 |
C15—C10 | 1.380 (3) | C14—H14 | 0.9300 |
C15—C14 | 1.381 (3) | C11—H11 | 0.9300 |
| | | |
N1—C7—N3 | 111.00 (18) | C3—C2—H2 | 120.0 |
N1—C7—C1 | 124.0 (2) | C1—C2—H2 | 120.0 |
N3—C7—C1 | 125.0 (2) | C4—C5—C6 | 119.8 (2) |
C7—N3—C8 | 108.61 (18) | C4—C5—H5 | 120.1 |
C7—N3—N4 | 126.17 (18) | C6—C5—H5 | 120.1 |
C8—N3—N4 | 124.57 (18) | N4—C9—C10 | 109.5 (2) |
C6—C1—C2 | 118.9 (2) | N4—C9—H9A | 109.8 |
C6—C1—C7 | 121.9 (2) | C10—C9—H9A | 109.8 |
C2—C1—C7 | 119.2 (2) | N4—C9—H9B | 109.8 |
C8—N2—N1 | 113.18 (18) | C10—C9—H9B | 109.8 |
C8—N2—H2N | 126.4 (13) | H9A—C9—H9B | 108.2 |
N1—N2—H2N | 119.0 (13) | C15—C10—C11 | 117.7 (3) |
C7—N1—N2 | 104.07 (17) | C15—C10—C9 | 120.2 (3) |
O1—C8—N2 | 130.6 (2) | C11—C10—C9 | 122.0 (3) |
O1—C8—N3 | 126.3 (2) | C13—C12—C11 | 117.3 (3) |
N2—C8—N3 | 103.1 (2) | C13—C12—H12 | 121.3 |
C1—C6—C5 | 120.7 (2) | C11—C12—H12 | 121.3 |
C1—C6—H6 | 119.6 | C4—C3—C2 | 120.3 (2) |
C5—C6—H6 | 119.6 | C4—C3—H3 | 119.9 |
N3—N4—C9 | 111.17 (19) | C2—C3—H3 | 119.9 |
N3—N4—H4N | 108.3 (14) | C3—C4—C5 | 120.3 (2) |
C9—N4—H4N | 114.3 (14) | C3—C4—H4 | 119.9 |
C10—C15—C14 | 121.1 (3) | C5—C4—H4 | 119.9 |
C10—C15—H15 | 119.4 | C13—C14—C15 | 118.8 (3) |
C14—C15—H15 | 119.4 | C13—C14—H14 | 120.6 |
C14—C13—C12 | 123.2 (3) | C15—C14—H14 | 120.6 |
C14—C13—F1 | 118.6 (3) | C10—C11—C12 | 121.8 (3) |
C12—C13—F1 | 118.2 (3) | C10—C11—H11 | 119.1 |
C3—C2—C1 | 120.0 (2) | C12—C11—H11 | 119.1 |
| | | |
N1—C7—N3—C8 | 1.1 (2) | C8—N3—N4—C9 | 69.2 (3) |
C1—C7—N3—C8 | 179.51 (19) | C6—C1—C2—C3 | 1.4 (3) |
N1—C7—N3—N4 | 172.1 (2) | C7—C1—C2—C3 | −179.5 (2) |
C1—C7—N3—N4 | −9.4 (3) | C1—C6—C5—C4 | −0.8 (4) |
N1—C7—C1—C6 | 144.1 (2) | N3—N4—C9—C10 | 68.9 (2) |
N3—C7—C1—C6 | −34.1 (3) | C14—C15—C10—C11 | 1.0 (4) |
N1—C7—C1—C2 | −34.9 (3) | C14—C15—C10—C9 | −174.1 (2) |
N3—C7—C1—C2 | 146.8 (2) | N4—C9—C10—C15 | 67.4 (3) |
N3—C7—N1—N2 | −1.6 (2) | N4—C9—C10—C11 | −107.5 (3) |
C1—C7—N1—N2 | 179.90 (18) | C14—C13—C12—C11 | 2.8 (4) |
C8—N2—N1—C7 | 1.7 (2) | F1—C13—C12—C11 | −178.0 (2) |
N1—N2—C8—O1 | 179.8 (2) | C1—C2—C3—C4 | −0.8 (4) |
N1—N2—C8—N3 | −1.1 (2) | C2—C3—C4—C5 | −0.6 (4) |
C7—N3—C8—O1 | 179.2 (2) | C6—C5—C4—C3 | 1.4 (4) |
N4—N3—C8—O1 | 8.0 (3) | C12—C13—C14—C15 | −2.7 (4) |
C7—N3—C8—N2 | 0.0 (2) | F1—C13—C14—C15 | 178.1 (2) |
N4—N3—C8—N2 | −171.2 (2) | C10—C15—C14—C13 | 0.7 (4) |
C2—C1—C6—C5 | −0.6 (3) | C15—C10—C11—C12 | −0.9 (4) |
C7—C1—C6—C5 | −179.7 (2) | C9—C10—C11—C12 | 174.2 (2) |
C7—N3—N4—C9 | −100.5 (2) | C13—C12—C11—C10 | −0.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.90 (2) | 1.89 (2) | 2.768 (2) | 164 (2) |
N4—H4N···N1ii | 0.94 (2) | 2.28 (2) | 3.153 (3) | 154 (2) |
C6—H6···N4 | 0.93 (1) | 2.59 (1) | 3.056 (3) | 111 (1) |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C15H13FN4O |
Mr | 284.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.4560 (19), 6.2183 (7), 14.8165 (18) |
β (°) | 108.347 (2) |
V (Å3) | 1351.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.42 × 0.17 × 0.16 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7084, 2992, 1141 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.662 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.089, 0.75 |
No. of reflections | 2992 |
No. of parameters | 198 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.15 |
Selected geometric parameters (Å, º) topC7—N1 | 1.305 (2) | N2—C8 | 1.342 (3) |
C7—N3 | 1.369 (2) | N2—N1 | 1.390 (2) |
N3—C8 | 1.384 (2) | F1—C13 | 1.364 (3) |
N3—N4 | 1.397 (2) | N4—C9 | 1.474 (3) |
O1—C8 | 1.234 (2) | | |
| | | |
N3—C7—C1 | 125.0 (2) | N3—N4—C9 | 111.17 (19) |
C8—N3—N4 | 124.57 (18) | N4—C9—C10 | 109.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.90 (2) | 1.89 (2) | 2.768 (2) | 164 (2) |
N4—H4N···N1ii | 0.94 (2) | 2.28 (2) | 3.153 (3) | 154 (2) |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x, y+1, z. |
1,2,4-Triazole and its derivatives are starting materials for the synthesis of many heterocycles (Desenko, 1995). Apart from its extensive chemical significance, the 1,2,4-triazole nucleus is also found to be associated with diverse medicinal properties, such as analgesic, anti-asthmatic, diuretic and antifungal activities (Mohamed et al., 1993). The title compound, (I), is shown in Fig. 1. Its bond lengths and angles are normal (Table 1) and correspond to those from the known structures (Puviarasan et al., 1999; Liu et al., 1999; Zhu et al., 2000).
In (I), two benzyl rings are planar within experimental error. Two phenyl rings, C1–C6 and C10–C15, are nearly parallel with the dihedral angle of 171.5 (1)°. Atom F1 is 0.051 (1) Å out from the C10–C15 fluorobenzyl ring. Also 1,2,4-triazole ring is planar. The maximum deviation from the planarity is 0.009 (1) Å for atom N1. The dihedral angles between the triazole ring and the C1–C6 and C10–C15 rings are 34.55 (1) and 42.91 (1)°, respectively.
In the crystal structure, the molecules are linked by intermolecular N—H···O and N—H···N contacts (Table 2) resulting in an infinite network structure (Fig. 2).