Acta Cryst. (2009). E65, o990-o991 [ doi:10.1107/S1600536809011908 ]
In the solid state, the structure of the title compound, C16H18N4O2, is stabilized by intermolecular N-H
O and O-HO hydrogen bonds. These hydrogen bonds arrange the molecules into a double-layer supramolecular structure. The molecular conformation is is consolidated by an intramolecular N-HN hydrogen bond. The dihedral angle between the aromatic rings is 8.01 (10)°
The synthesis of the title compound included reagents and solvents of reagent grade, which were used without further purification. As a starting material we synthesized 2-[4,5-dihydro-1,3-oxazol-2-yl]aniline by a modification of the Gómez and coworkers methodology (Gómez et al., 2005). 2-[4,5-Dihydro-1,3-oxazol-2-yl]aniline (1.00 g, 6.17 mmol) was dissolved in aqueous HCl 2 M (9.25 ml, 18.50 mmol) and cooled to 268 K. A sodium nitrite solution (0.51 g, 7.40 mmol) in water (6 ml) was slowly added with continuous stirring. A solution of p-toluidine (0.66 g, 6.17 mmol) in methanol (10 ml) was added slowly to the reaction mixture, and stirred for 30 m at 268 K. The resulting mixture was neutralised with a saturated aqueous solution of NaHCO3. A crude yellow-orange was separated by filtration and washed with small portions of water. The product was purified by flash chromatography on neutral alumina (hexane/ethyl acetate, 1:9), and recrystallized from an ethyl acetate/hexane mixture (9 : 1). Orange bar-shaped crystals of (I), suitable for X-ray analysis, were obtained by slow evaporation of the solvent mixture. Yield 47% (0.87 g, 2.90 mmol), based on 2-[4,5-dihydro-1,3-oxazol-2-yl]aniline; m.p., 111–113 °C. IR (KBr pellet, cm-1), 3278, 3233, 1625, 1538, 1269.1H NMR [(CD3)2CO, 200 MHz] δ 12.89 (s), 8.10 (s), 7.93–7.02 (m, 8H), 4.10 (s), 3.74 (dd J = 5.4, 11.0 Hz, 2H), 3.54 (dd, J = 5.4, 11.0 Hz, 2H), 2.35 (s, 3H).13C NMR [(C D3)2CO, 50 MHz] δ 135.4, 133.0, 130.1, 128.4, 121.7,114.9, 61.2, 43.2, 21.0. Anal. Calcd. for C16H18N4O2: C, 64.41; H, 6.08;N, 18.78%. Found C, 64.11; H, 6.44; N, 18.93%. HRESIMS Calcd. for [M+H]+299.1503. Found 299.1519.
Refinement for H atoms was carried out using a riding model, with distances constrained to: 0.93 Å for aromatic CH, 0.98 Å for methine CH. Isotropic U parameters were fixed to Uiso(H)=1.2Ueq(carrier atom) for aromatic CH.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./kp2210fig1thm.gif)
| Fig. 1. The title compound (I) with displacement ellipsoids drawn at the 30% probability level. Intramolecular H-bond is indicated by dashed lines. |
![[Figure 2]](./kp2210fig2thm.gif)
| Fig. 2. Packing of I showing the H-bonds. The molecules are forming a two dimensional network in the (100) plane. H-bonds are indicated by dashed lines. |
![[Figure 3]](./kp2210fig3thm.gif)
| Fig. 3. Packing of I showing the bilayer. The molecules are forming a zig-zag array along the [001] direction. |
| C16H18N4O2 | F(000) = 632 |
| Mr = 298.34 | Dx = 1.299 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 76 reflections |
| a = 16.846 (2) Å | θ = 4.7–12.0° |
| b = 12.2053 (17) Å | µ = 0.09 mm−1 |
| c = 7.4302 (11) Å | T = 298 K |
| β = 93.212 (13)° | Neele, yellow |
| V = 1525.3 (4) Å3 | 0.40 × 0.22 × 0.14 mm |
| Z = 4 |
| Bruker P4 diffractometer | Rint = 0.044 |
| Radiation source: fine-focus sealed tube | θmax = 26.3°, θmin = 2.1° |
| graphite | h = −20→20 |
| 2θ/ω scans | k = −15→1 |
| 4153 measured reflections | l = −9→1 |
| 3067 independent reflections | 3 standard reflections every 97 reflections |
| 1778 reflections with I > 2σ(I) | intensity decay: 2.8% |
| 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)] = 0.055 | H-atom parameters constrained |
| wR(F2) = 0.188 | w = 1/[σ2(Fo2) + (0.1035P)2 + 0.0651P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 3067 reflections | Δρmax = 0.57 e Å−3 |
| 201 parameters | Δρmin = −0.22 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.008 (3) |
| C16H18N4O2 | V = 1525.3 (4) Å3 |
| Mr = 298.34 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 16.846 (2) Å | µ = 0.09 mm−1 |
| b = 12.2053 (17) Å | T = 298 K |
| c = 7.4302 (11) Å | 0.40 × 0.22 × 0.14 mm |
| β = 93.212 (13)° |
| Bruker P4 diffractometer | Rint = 0.044 |
| 4153 measured reflections | θmax = 26.3° |
| 3067 independent reflections | 3 standard reflections every 97 reflections |
| 1778 reflections with I > 2σ(I) | intensity decay: 2.8% |
| R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
| wR(F2) = 0.188 | Δρmax = 0.57 e Å−3 |
| S = 1.04 | Δρmin = −0.22 e Å−3 |
| 3067 reflections | Absolute structure: ? |
| 201 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.69940 (11) | 0.33793 (15) | −0.0017 (3) | 0.0484 (5) | |
| N2 | 0.76320 (11) | 0.39013 (16) | 0.0332 (3) | 0.0481 (5) | |
| N4 | 0.54570 (10) | 0.30472 (15) | −0.1084 (3) | 0.0456 (5) | |
| H4A | 0.5790 | 0.3480 | −0.0525 | 0.055* | |
| O1 | 0.51316 (10) | 0.13062 (14) | −0.1750 (2) | 0.0574 (5) | |
| O2 | 0.39653 (10) | 0.39859 (16) | 0.0593 (3) | 0.0651 (6) | |
| H2B | 0.4341 | 0.3834 | 0.1299 | 0.098* | |
| N3 | 0.75322 (11) | 0.49670 (16) | 0.0124 (3) | 0.0521 (6) | |
| H3A | 0.7066 | 0.5219 | −0.0175 | 0.063* | |
| C1 | 0.70741 (13) | 0.22274 (19) | 0.0146 (3) | 0.0434 (6) | |
| C2 | 0.64042 (13) | 0.15801 (18) | −0.0313 (3) | 0.0424 (6) | |
| C3 | 0.64717 (15) | 0.0445 (2) | −0.0087 (4) | 0.0550 (7) | |
| H3B | 0.6029 | 0.0006 | −0.0346 | 0.066* | |
| C4 | 0.71719 (17) | −0.0036 (2) | 0.0504 (4) | 0.0646 (8) | |
| H4B | 0.7200 | −0.0792 | 0.0651 | 0.078* | |
| C5 | 0.78345 (15) | 0.0601 (2) | 0.0881 (4) | 0.0654 (8) | |
| H5A | 0.8317 | 0.0275 | 0.1237 | 0.078* | |
| C6 | 0.77816 (14) | 0.1716 (2) | 0.0729 (4) | 0.0577 (7) | |
| H6A | 0.8228 | 0.2141 | 0.1022 | 0.069* | |
| C7 | 0.81680 (13) | 0.56925 (19) | 0.0379 (3) | 0.0472 (6) | |
| C8 | 0.80588 (14) | 0.6767 (2) | −0.0132 (4) | 0.0552 (7) | |
| H8A | 0.7569 | 0.6993 | −0.0642 | 0.066* | |
| C9 | 0.86733 (16) | 0.7513 (2) | 0.0109 (4) | 0.0608 (7) | |
| H9A | 0.8588 | 0.8240 | −0.0227 | 0.073* | |
| C10 | 0.94103 (16) | 0.7200 (3) | 0.0839 (4) | 0.0622 (8) | |
| C11 | 0.95105 (16) | 0.6126 (3) | 0.1297 (4) | 0.0682 (8) | |
| H11A | 1.0006 | 0.5896 | 0.1771 | 0.082* | |
| C12 | 0.89054 (14) | 0.5364 (2) | 0.1086 (4) | 0.0608 (7) | |
| H12A | 0.8994 | 0.4637 | 0.1416 | 0.073* | |
| C13 | 0.56158 (13) | 0.19811 (19) | −0.1101 (3) | 0.0420 (5) | |
| C14 | 0.47468 (13) | 0.3509 (2) | −0.1968 (3) | 0.0495 (6) | |
| H14A | 0.4671 | 0.3186 | −0.3157 | 0.059* | |
| H14B | 0.4829 | 0.4289 | −0.2126 | 0.059* | |
| C15 | 0.40087 (15) | 0.3347 (2) | −0.0995 (4) | 0.0617 (8) | |
| H15A | 0.3555 | 0.3523 | −0.1806 | 0.074* | |
| H15B | 0.3968 | 0.2580 | −0.0676 | 0.074* | |
| C16 | 1.0073 (2) | 0.8027 (3) | 0.1157 (5) | 0.0921 (11) | |
| H16A | 1.0569 | 0.7649 | 0.1374 | 0.138* | |
| H16B | 0.9968 | 0.8470 | 0.2184 | 0.138* | |
| H16C | 1.0101 | 0.8486 | 0.0113 | 0.138* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0424 (10) | 0.0407 (11) | 0.0617 (13) | −0.0019 (9) | 0.0007 (9) | −0.0026 (9) |
| N2 | 0.0432 (11) | 0.0418 (11) | 0.0585 (13) | −0.0002 (9) | −0.0026 (9) | −0.0039 (9) |
| N4 | 0.0368 (10) | 0.0412 (11) | 0.0581 (13) | 0.0021 (8) | −0.0039 (9) | −0.0023 (9) |
| O1 | 0.0554 (10) | 0.0464 (10) | 0.0678 (12) | −0.0062 (8) | −0.0189 (9) | −0.0037 (8) |
| O2 | 0.0477 (10) | 0.0882 (14) | 0.0579 (12) | 0.0226 (9) | −0.0101 (8) | −0.0129 (10) |
| N3 | 0.0373 (10) | 0.0382 (11) | 0.0796 (15) | 0.0020 (8) | −0.0072 (10) | −0.0020 (10) |
| C1 | 0.0409 (12) | 0.0430 (13) | 0.0461 (13) | 0.0018 (10) | 0.0015 (10) | 0.0002 (10) |
| C2 | 0.0438 (12) | 0.0405 (13) | 0.0428 (13) | 0.0027 (10) | 0.0001 (10) | −0.0001 (10) |
| C3 | 0.0560 (15) | 0.0425 (14) | 0.0654 (17) | −0.0017 (11) | −0.0071 (12) | −0.0009 (12) |
| C4 | 0.0697 (18) | 0.0407 (14) | 0.082 (2) | 0.0094 (13) | −0.0100 (15) | 0.0012 (14) |
| C5 | 0.0509 (15) | 0.0536 (16) | 0.090 (2) | 0.0143 (12) | −0.0097 (14) | 0.0021 (15) |
| C6 | 0.0426 (13) | 0.0525 (16) | 0.0771 (19) | 0.0020 (11) | −0.0053 (12) | 0.0019 (13) |
| C7 | 0.0385 (12) | 0.0428 (13) | 0.0603 (15) | −0.0017 (10) | 0.0020 (11) | −0.0070 (11) |
| C8 | 0.0420 (13) | 0.0508 (15) | 0.0726 (18) | 0.0000 (11) | 0.0029 (12) | 0.0010 (13) |
| C9 | 0.0587 (16) | 0.0510 (16) | 0.0737 (18) | −0.0109 (12) | 0.0113 (14) | −0.0017 (13) |
| C10 | 0.0525 (15) | 0.0679 (18) | 0.0669 (18) | −0.0196 (13) | 0.0083 (13) | −0.0146 (15) |
| C11 | 0.0412 (14) | 0.078 (2) | 0.084 (2) | −0.0023 (13) | −0.0095 (13) | −0.0153 (17) |
| C12 | 0.0469 (14) | 0.0481 (14) | 0.086 (2) | 0.0037 (12) | −0.0122 (13) | −0.0078 (14) |
| C13 | 0.0422 (12) | 0.0436 (13) | 0.0398 (12) | −0.0002 (10) | −0.0004 (10) | 0.0004 (10) |
| C14 | 0.0487 (14) | 0.0481 (14) | 0.0508 (15) | 0.0031 (11) | −0.0051 (11) | 0.0011 (11) |
| C15 | 0.0456 (14) | 0.0737 (19) | 0.0643 (18) | 0.0056 (13) | −0.0097 (12) | 0.0006 (15) |
| C16 | 0.073 (2) | 0.103 (3) | 0.100 (3) | −0.043 (2) | 0.0043 (18) | −0.016 (2) |
| N1—N2 | 1.264 (3) | C6—H6A | 0.9300 |
| N1—C1 | 1.417 (3) | C7—C8 | 1.375 (4) |
| N2—N3 | 1.319 (3) | C7—C12 | 1.381 (3) |
| N4—C13 | 1.329 (3) | C8—C9 | 1.383 (3) |
| N4—C14 | 1.447 (3) | C8—H8A | 0.9300 |
| N4—H4A | 0.8600 | C9—C10 | 1.381 (4) |
| O1—C13 | 1.238 (3) | C9—H9A | 0.9300 |
| O2—C15 | 1.420 (3) | C10—C11 | 1.363 (4) |
| O2—H2B | 0.8200 | C10—C16 | 1.513 (4) |
| N3—C7 | 1.395 (3) | C11—C12 | 1.382 (4) |
| N3—H3A | 0.8600 | C11—H11A | 0.9300 |
| C1—C6 | 1.393 (3) | C12—H12A | 0.9300 |
| C1—C2 | 1.404 (3) | C14—C15 | 1.486 (4) |
| C2—C3 | 1.400 (3) | C14—H14A | 0.9700 |
| C2—C13 | 1.503 (3) | C14—H14B | 0.9700 |
| C3—C4 | 1.368 (3) | C15—H15A | 0.9700 |
| C3—H3B | 0.9300 | C15—H15B | 0.9700 |
| C4—C5 | 1.376 (4) | C16—H16A | 0.9600 |
| C4—H4B | 0.9300 | C16—H16B | 0.9600 |
| C5—C6 | 1.367 (4) | C16—H16C | 0.9600 |
| C5—H5A | 0.9300 | ||
| N2—N1—C1 | 114.01 (19) | C10—C9—C8 | 121.2 (3) |
| N1—N2—N3 | 111.82 (19) | C10—C9—H9A | 119.4 |
| C13—N4—C14 | 122.64 (19) | C8—C9—H9A | 119.4 |
| C13—N4—H4A | 118.7 | C11—C10—C9 | 117.4 (2) |
| C14—N4—H4A | 118.7 | C11—C10—C16 | 121.5 (3) |
| C15—O2—H2B | 109.5 | C9—C10—C16 | 121.0 (3) |
| N2—N3—C7 | 121.21 (19) | C10—C11—C12 | 122.6 (3) |
| N2—N3—H3A | 119.4 | C10—C11—H11A | 118.7 |
| C7—N3—H3A | 119.4 | C12—C11—H11A | 118.7 |
| C6—C1—C2 | 119.0 (2) | C7—C12—C11 | 119.3 (3) |
| C6—C1—N1 | 123.2 (2) | C7—C12—H12A | 120.3 |
| C2—C1—N1 | 117.79 (19) | C11—C12—H12A | 120.3 |
| C3—C2—C1 | 118.0 (2) | O1—C13—N4 | 121.8 (2) |
| C3—C2—C13 | 115.7 (2) | O1—C13—C2 | 118.9 (2) |
| C1—C2—C13 | 126.3 (2) | N4—C13—C2 | 119.3 (2) |
| C4—C3—C2 | 121.7 (2) | N4—C14—C15 | 114.9 (2) |
| C4—C3—H3B | 119.1 | N4—C14—H14A | 108.5 |
| C2—C3—H3B | 119.1 | C15—C14—H14A | 108.5 |
| C3—C4—C5 | 119.9 (3) | N4—C14—H14B | 108.5 |
| C3—C4—H4B | 120.1 | C15—C14—H14B | 108.5 |
| C5—C4—H4B | 120.1 | H14A—C14—H14B | 107.5 |
| C6—C5—C4 | 119.8 (2) | O2—C15—C14 | 114.5 (2) |
| C6—C5—H5A | 120.1 | O2—C15—H15A | 108.6 |
| C4—C5—H5A | 120.1 | C14—C15—H15A | 108.6 |
| C5—C6—C1 | 121.5 (2) | O2—C15—H15B | 108.6 |
| C5—C6—H6A | 119.3 | C14—C15—H15B | 108.6 |
| C1—C6—H6A | 119.3 | H15A—C15—H15B | 107.6 |
| C8—C7—C12 | 119.1 (2) | C10—C16—H16A | 109.5 |
| C8—C7—N3 | 118.6 (2) | C10—C16—H16B | 109.5 |
| C12—C7—N3 | 122.3 (2) | H16A—C16—H16B | 109.5 |
| C7—C8—C9 | 120.3 (2) | C10—C16—H16C | 109.5 |
| C7—C8—H8A | 119.8 | H16A—C16—H16C | 109.5 |
| C9—C8—H8A | 119.8 | H16B—C16—H16C | 109.5 |
| C1—N1—N2—N3 | 178.6 (2) | N3—C7—C8—C9 | 179.6 (2) |
| N1—N2—N3—C7 | −177.7 (2) | C7—C8—C9—C10 | 0.9 (4) |
| N2—N1—C1—C6 | 3.2 (3) | C8—C9—C10—C11 | 0.6 (4) |
| N2—N1—C1—C2 | −176.6 (2) | C8—C9—C10—C16 | −178.0 (3) |
| C6—C1—C2—C3 | 2.7 (3) | C9—C10—C11—C12 | −1.2 (4) |
| N1—C1—C2—C3 | −177.6 (2) | C16—C10—C11—C12 | 177.4 (3) |
| C6—C1—C2—C13 | −174.8 (2) | C8—C7—C12—C11 | 1.3 (4) |
| N1—C1—C2—C13 | 5.0 (3) | N3—C7—C12—C11 | 179.8 (2) |
| C1—C2—C3—C4 | −2.1 (4) | C10—C11—C12—C7 | 0.2 (5) |
| C13—C2—C3—C4 | 175.6 (2) | C14—N4—C13—O1 | −6.1 (4) |
| C2—C3—C4—C5 | −0.5 (4) | C14—N4—C13—C2 | 173.9 (2) |
| C3—C4—C5—C6 | 2.5 (5) | C3—C2—C13—O1 | −11.0 (3) |
| C4—C5—C6—C1 | −2.0 (5) | C1—C2—C13—O1 | 166.5 (2) |
| C2—C1—C6—C5 | −0.7 (4) | C3—C2—C13—N4 | 169.0 (2) |
| N1—C1—C6—C5 | 179.5 (3) | C1—C2—C13—N4 | −13.5 (3) |
| N2—N3—C7—C8 | 169.7 (2) | C13—N4—C14—C15 | 76.5 (3) |
| N2—N3—C7—C12 | −8.8 (4) | N4—C14—C15—O2 | 71.8 (3) |
| C12—C7—C8—C9 | −1.9 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N1 | 0.86 | 2.05 | 2.696 (3) | 132 |
| O2—H2B···O1i | 0.82 | 1.92 | 2.729 (2) | 169 |
| N3—H3A···O2ii | 0.86 | 2.00 | 2.851 (2) | 170 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N1 | 0.86 | 2.05 | 2.696 (3) | 132 |
| O2—H2B···O1i | 0.82 | 1.92 | 2.729 (2) | 169 |
| N3—H3A···O2ii | 0.86 | 2.00 | 2.851 (2) | 170 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z. |
We gratefully acknowledge support for this project by Consejo Nacional de Ciencia y Tecnología (CONACyT grant 60467), Consejo del Sistema Nacional de EducaciónTecnológica (COSNET grant 486–02-P) and a graduate scholarship from CONACyT for F. Rocha-Alonzo. The authors are indebted to Adrián Ochoa Terán and Ignacio Rivero Espejel for their support in this work. We acknowledge Universidad Autónoma de Nuevo-León (Monterrey, México) for diffractometer time.
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The synthesis of alternative ligands to stabilize dinuclear complexes and control their reactivity is an area of great importance in coordination and organometallic chemistry (for recent literature see: Das et al., 2008; Estevan et al., 2006; Jie et al., 2007; Müller & Vogt, 2007; Schilling et al., 2008). In this context, we have focused our attention to the synthesis of 1,3-bis(aryl)triazenes as precursors for triazenido ligands bearing Lewis basic ortho substituents such as ester, methoxy and methylmercapto groups (Nuricumbo-Escobar et al., 2007; Ríos-Moreno et al., 2003; Rodríguez et al., 1999; Tejel et al., 2004); it has been found that the nature of the substituent produces a dramatic impact on their coordination chemistry and reactivity. As part of our ongoing research, we have synthesized the title compound (I, Fig. 1) using the diazonium salt N-coupling methodology.
The molecular structure of (I) shows the characteristic trans stereochemistry about N═N of the diazoamino group of free triazenes. The N1═N2 bond [1.264 (3) Å] is longer than the typical value for N═N bond (1.222 Å), whereas the N2—N3 bond [1.320 (3) Å] is shorter than typical value for a Nsp3—Nsp2 single bond (1.420 Å) (Allen et al., 1987). In addition, the C7—N3 bond [1.395 (3) Å] is shorter than the characteristic Caryl—NH single bonds for secondary aromatic amines (1.419 Å) (Orpen, et al., 1989). An intramolecular N1—H···N4 hydrogen bond is observed (Fig. 1 and Table 1).
In the crystal structure, adjacent units are arranged into a two-dimensional network along the (100) plane via intermolecular N— H···O and O—H···O hydrogen bond interactions (Fig. 2 and Table 1). These layers are linked together via intermolecular N—H···O and O—H···O hydrogen bonds forming a zig-zag bilayered array along the [001] direction (Fig. 3).