Acta Cryst. (2008). E64, o863 [ doi:10.1107/S1600536808010180 ]
The title compound, C18H15N3O, is the product of the thermal decomposition of the diazonium salt derived from 2-amino-N-methyl-N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)benzamide. It is characterized by a trans orientation of the methyl groups with respect to the tricyclic ring system. The molecule has a nearly planar phenylpyrazolo[3,4-c]isoquinolin-5-one system, the largest deviation from the mean plane being 0.066 (2) Å for the O atom. The dihedral angle between the phenyl substituent and the heterotricycle is 67 (1)°. The packing is stabilized by C-H
N hydrogen-bond interactions, with the formation of molecular chains along the c axis.
The title compound was obtained as the product of the thermal decomposition of the diazonium salt derived from 2-amino-N-methyl-N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)benzamide.
All non-H-atoms were refined anisotropically. Hydrogen atoms were introduced at calculated positions, in their described geometries and allowed to ride on the attached carbon atom with fixed isotropic thermal parameters (1.2Ueq and 1.5Ueq of the parent carbon atom for aromatic H-atoms and methyls H-atoms, respectively).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./fj2107fig1thm.gif)
| Fig. 1. The chemical reaction scheme. |
![[Figure 2]](./fj2107fig2thm.gif)
| Fig. 2. The molecular structure of the title compound, showing atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 3]](./fj2107fig3thm.gif)
| Fig. 3. Intermolecular interactions of the title compound, showing the molecular chains along the c axis. Hydrogen bonds are shown as dashed lines. |
| C18H15N3O | F000 = 608 |
| Mr = 289.33 | Dx = 1.339 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 25 reflections |
| a = 8.066 (2) Å | θ = 9–10º |
| b = 19.256 (3) Å | µ = 0.09 mm−1 |
| c = 9.270 (3) Å | T = 293 (2) K |
| β = 94.66 (3)º | Prism, colorless |
| V = 1435.0 (6) Å3 | 0.6 × 0.5 × 0.4 mm |
| Z = 4 |
| Enraf–Nonius TurboCAD-4 diffractometer | θmax = 26.0º |
| Monochromator: graphite | θmin = 3.1º |
| T = 293(2) K | h = −9→9 |
| Non–profiled ω/2θ scans | k = 0→23 |
| Absorption correction: none | l = 0→11 |
| 2984 measured reflections | 3 standard reflections |
| 2815 independent reflections | every 120 min |
| 1751 reflections with I > 2σ(I) | intensity decay: 3% |
| Rint = 0.031 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + 1.3459P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.113 | (Δ/σ)max = 0.006 |
| S = 1.01 | Δρmax = 0.16 e Å−3 |
| 2815 reflections | Δρmin = −0.15 e Å−3 |
| 202 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.043 (3) |
| Secondary atom site location: difference Fourier map |
| C18H15N3O | V = 1435.0 (6) Å3 |
| Mr = 289.33 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 8.066 (2) Å | µ = 0.09 mm−1 |
| b = 19.256 (3) Å | T = 293 (2) K |
| c = 9.270 (3) Å | 0.6 × 0.5 × 0.4 mm |
| β = 94.66 (3)º |
| Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.031 |
| Absorption correction: none | 3 standard reflections |
| 2984 measured reflections | every 120 min |
| 2815 independent reflections | intensity decay: 3% |
| 1751 reflections with I > 2σ(I) |
| R[F2 > 2σ(F2)] = 0.048 | 202 parameters |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.16 e Å−3 |
| 2815 reflections | Δρmin = −0.15 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 > 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 | ||
| O1 | 0.62196 (18) | 0.08361 (7) | 0.50784 (16) | 0.0628 (4) | |
| N1 | 0.93284 (19) | −0.15752 (8) | 0.28089 (16) | 0.0508 (4) | |
| N2 | 0.89261 (18) | −0.12641 (8) | 0.40852 (16) | 0.0447 (4) | |
| C1 | 0.8813 (2) | −0.11483 (10) | 0.1753 (2) | 0.0470 (5) | |
| C2 | 0.8049 (2) | −0.05543 (9) | 0.22995 (19) | 0.0415 (4) | |
| C3 | 0.8148 (2) | −0.06473 (9) | 0.37789 (19) | 0.0395 (4) | |
| C4 | 0.9007 (2) | −0.17029 (9) | 0.53322 (19) | 0.0417 (4) | |
| C5 | 0.7563 (2) | −0.19339 (10) | 0.5872 (2) | 0.0504 (5) | |
| H5 | 0.6535 | −0.1779 | 0.5469 | 0.060* | |
| C6 | 0.7650 (3) | −0.23975 (11) | 0.7016 (2) | 0.0571 (6) | |
| H6 | 0.6680 | −0.2551 | 0.7391 | 0.068* | |
| C7 | 0.9167 (3) | −0.26301 (10) | 0.7598 (2) | 0.0586 (6) | |
| H7 | 0.9222 | −0.2948 | 0.8355 | 0.070* | |
| C8 | 1.0615 (3) | −0.23927 (10) | 0.7063 (2) | 0.0592 (6) | |
| H8 | 1.1642 | −0.2545 | 0.7471 | 0.071* | |
| C9 | 1.0537 (2) | −0.19281 (10) | 0.5918 (2) | 0.0496 (5) | |
| H9 | 1.1506 | −0.1770 | 0.5549 | 0.060* | |
| N3 | 0.76230 (18) | −0.01656 (8) | 0.47488 (16) | 0.0427 (4) | |
| C10 | 0.6777 (2) | 0.04286 (10) | 0.4218 (2) | 0.0460 (5) | |
| C11 | 0.6673 (2) | 0.05442 (9) | 0.2651 (2) | 0.0458 (5) | |
| C12 | 0.7305 (2) | 0.00692 (10) | 0.1681 (2) | 0.0446 (5) | |
| C13 | 0.7159 (3) | 0.02280 (11) | 0.0198 (2) | 0.0581 (6) | |
| H13 | 0.7562 | −0.0083 | −0.0457 | 0.070* | |
| C14 | 0.6434 (3) | 0.08330 (12) | −0.0299 (3) | 0.0681 (6) | |
| H14 | 0.6348 | 0.0929 | −0.1286 | 0.082* | |
| C15 | 0.5829 (3) | 0.13036 (12) | 0.0653 (3) | 0.0665 (6) | |
| H15 | 0.5345 | 0.1716 | 0.0309 | 0.080* | |
| C16 | 0.5943 (2) | 0.11612 (11) | 0.2113 (2) | 0.0586 (6) | |
| H16 | 0.5530 | 0.1479 | 0.2749 | 0.070* | |
| C18 | 0.7939 (3) | −0.02364 (10) | 0.63194 (19) | 0.0529 (5) | |
| H18A | 0.7052 | −0.0496 | 0.6694 | 0.079* | |
| H18B | 0.8000 | 0.0216 | 0.6756 | 0.079* | |
| H18C | 0.8972 | −0.0476 | 0.6539 | 0.079* | |
| C17 | 0.9067 (3) | −0.13436 (12) | 0.0218 (2) | 0.0668 (6) | |
| H17A | 0.9664 | −0.1775 | 0.0208 | 0.100* | |
| H17B | 0.9694 | −0.0987 | −0.0214 | 0.100* | |
| H17C | 0.8006 | −0.1394 | −0.0320 | 0.100* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0762 (10) | 0.0510 (9) | 0.0636 (10) | 0.0104 (7) | 0.0201 (8) | −0.0068 (7) |
| N1 | 0.0585 (10) | 0.0518 (10) | 0.0430 (10) | 0.0078 (8) | 0.0096 (8) | −0.0067 (8) |
| N2 | 0.0528 (10) | 0.0429 (9) | 0.0388 (9) | 0.0041 (7) | 0.0070 (7) | −0.0005 (7) |
| C1 | 0.0490 (11) | 0.0520 (11) | 0.0405 (11) | −0.0016 (9) | 0.0060 (8) | −0.0056 (10) |
| C2 | 0.0444 (10) | 0.0429 (11) | 0.0374 (10) | −0.0027 (8) | 0.0055 (8) | −0.0014 (9) |
| C3 | 0.0380 (10) | 0.0400 (10) | 0.0409 (11) | −0.0038 (8) | 0.0046 (8) | −0.0025 (9) |
| C4 | 0.0468 (11) | 0.0382 (10) | 0.0402 (11) | −0.0012 (8) | 0.0030 (8) | −0.0032 (8) |
| C5 | 0.0464 (11) | 0.0561 (12) | 0.0484 (12) | −0.0026 (10) | 0.0030 (9) | −0.0014 (10) |
| C6 | 0.0665 (14) | 0.0578 (13) | 0.0481 (12) | −0.0148 (11) | 0.0118 (11) | −0.0022 (11) |
| C7 | 0.0893 (17) | 0.0431 (12) | 0.0426 (12) | −0.0036 (11) | 0.0014 (11) | 0.0009 (9) |
| C8 | 0.0641 (14) | 0.0507 (13) | 0.0600 (14) | 0.0091 (10) | −0.0116 (11) | −0.0007 (11) |
| C9 | 0.0482 (11) | 0.0452 (11) | 0.0549 (12) | −0.0022 (9) | 0.0007 (9) | −0.0025 (10) |
| N3 | 0.0488 (9) | 0.0420 (9) | 0.0380 (9) | −0.0013 (7) | 0.0075 (7) | −0.0034 (7) |
| C10 | 0.0455 (11) | 0.0400 (11) | 0.0534 (12) | −0.0023 (9) | 0.0094 (9) | −0.0030 (9) |
| C11 | 0.0437 (10) | 0.0436 (11) | 0.0501 (12) | −0.0026 (9) | 0.0048 (9) | 0.0044 (10) |
| C12 | 0.0438 (11) | 0.0467 (11) | 0.0433 (11) | −0.0080 (9) | 0.0024 (9) | 0.0015 (9) |
| C13 | 0.0686 (14) | 0.0578 (14) | 0.0480 (13) | −0.0017 (11) | 0.0056 (10) | 0.0050 (11) |
| C14 | 0.0792 (16) | 0.0678 (15) | 0.0565 (15) | −0.0022 (13) | 0.0006 (12) | 0.0168 (12) |
| C15 | 0.0652 (14) | 0.0598 (14) | 0.0735 (16) | 0.0044 (11) | 0.0000 (12) | 0.0256 (13) |
| C16 | 0.0551 (13) | 0.0503 (12) | 0.0713 (15) | 0.0030 (10) | 0.0098 (11) | 0.0067 (11) |
| C18 | 0.0676 (13) | 0.0530 (12) | 0.0386 (11) | −0.0022 (10) | 0.0076 (9) | −0.0058 (9) |
| C17 | 0.0786 (15) | 0.0777 (16) | 0.0449 (13) | 0.0079 (12) | 0.0099 (11) | −0.0136 (11) |
| O1—C10 | 1.230 (2) | C9—H9 | 0.9300 |
| N1—C1 | 1.319 (2) | N3—C10 | 1.401 (2) |
| N1—N2 | 1.3879 (19) | N3—C18 | 1.464 (2) |
| N2—C3 | 1.362 (2) | C10—C11 | 1.466 (3) |
| N2—C4 | 1.429 (2) | C11—C16 | 1.400 (3) |
| C1—C2 | 1.412 (2) | C11—C12 | 1.407 (2) |
| C1—C17 | 1.502 (2) | C12—C13 | 1.404 (3) |
| C2—C3 | 1.379 (2) | C13—C14 | 1.366 (3) |
| C2—C12 | 1.440 (3) | C13—H13 | 0.9300 |
| C3—N3 | 1.382 (2) | C14—C15 | 1.382 (3) |
| C4—C9 | 1.377 (2) | C14—H14 | 0.9300 |
| C4—C5 | 1.378 (2) | C15—C16 | 1.376 (3) |
| C5—C6 | 1.384 (3) | C15—H15 | 0.9300 |
| C5—H5 | 0.9300 | C16—H16 | 0.9300 |
| C6—C7 | 1.371 (3) | C18—H18A | 0.9600 |
| C6—H6 | 0.9300 | C18—H18B | 0.9600 |
| C7—C8 | 1.383 (3) | C18—H18C | 0.9600 |
| C7—H7 | 0.9300 | C17—H17A | 0.9600 |
| C8—C9 | 1.385 (3) | C17—H17B | 0.9600 |
| C8—H8 | 0.9300 | C17—H17C | 0.9600 |
| C1—N1—N2 | 106.38 (15) | O1—C10—N3 | 119.15 (18) |
| C3—N2—N1 | 109.53 (14) | O1—C10—C11 | 123.45 (18) |
| C3—N2—C4 | 132.37 (15) | N3—C10—C11 | 117.34 (17) |
| N1—N2—C4 | 115.84 (14) | C16—C11—C12 | 119.19 (18) |
| N1—C1—C2 | 111.02 (16) | C16—C11—C10 | 118.10 (18) |
| N1—C1—C17 | 119.19 (17) | C12—C11—C10 | 122.70 (17) |
| C2—C1—C17 | 129.78 (18) | C13—C12—C11 | 118.58 (18) |
| C3—C2—C1 | 105.07 (16) | C13—C12—C2 | 124.78 (18) |
| C3—C2—C12 | 119.52 (17) | C11—C12—C2 | 116.64 (17) |
| C1—C2—C12 | 135.39 (17) | C14—C13—C12 | 121.0 (2) |
| N2—C3—C2 | 107.99 (16) | C14—C13—H13 | 119.5 |
| N2—C3—N3 | 127.58 (16) | C12—C13—H13 | 119.5 |
| C2—C3—N3 | 124.33 (17) | C13—C14—C15 | 120.5 (2) |
| C9—C4—C5 | 120.77 (17) | C13—C14—H14 | 119.8 |
| C9—C4—N2 | 119.08 (16) | C15—C14—H14 | 119.8 |
| C5—C4—N2 | 119.99 (16) | C16—C15—C14 | 119.9 (2) |
| C4—C5—C6 | 119.64 (19) | C16—C15—H15 | 120.0 |
| C4—C5—H5 | 120.2 | C14—C15—H15 | 120.0 |
| C6—C5—H5 | 120.2 | C15—C16—C11 | 120.8 (2) |
| C7—C6—C5 | 120.03 (19) | C15—C16—H16 | 119.6 |
| C7—C6—H6 | 120.0 | C11—C16—H16 | 119.6 |
| C5—C6—H6 | 120.0 | N3—C18—H18A | 109.5 |
| C6—C7—C8 | 120.2 (2) | N3—C18—H18B | 109.5 |
| C6—C7—H7 | 119.9 | H18A—C18—H18B | 109.5 |
| C8—C7—H7 | 119.9 | N3—C18—H18C | 109.5 |
| C7—C8—C9 | 120.1 (2) | H18A—C18—H18C | 109.5 |
| C7—C8—H8 | 120.0 | H18B—C18—H18C | 109.5 |
| C9—C8—H8 | 120.0 | C1—C17—H17A | 109.5 |
| C4—C9—C8 | 119.28 (19) | C1—C17—H17B | 109.5 |
| C4—C9—H9 | 120.4 | H17A—C17—H17B | 109.5 |
| C8—C9—H9 | 120.4 | C1—C17—H17C | 109.5 |
| C3—N3—C10 | 119.09 (16) | H17A—C17—H17C | 109.5 |
| C3—N3—C18 | 123.15 (16) | H17B—C17—H17C | 109.5 |
| C10—N3—C18 | 117.75 (15) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···N1i | 0.93 | 2.59 | 3.457 (3) | 156 |
| Symmetry codes: (i) x−1/2, −y−1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···N1i | 0.93 | 2.59 | 3.457 (3) | 156 |
| Symmetry codes: (i) x−1/2, −y−1/2, z+1/2. |
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
Daidone, G., Maggio, B., Raffa, D., Plescia, S., Benetollo, F. & Bombieri, G. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 2891–2898.
Daidone, G., Plescia, S. & Fabra, J. (1980). J. Heterocycl. Chem. 17, 1409–1411.
Daidone, G., Plescia, S., Maggio, B., Spirio, V., Benetollo, F. & Bombieri, G. (1993). J. Chem. Soc. Perkin Trans. 1, pp. 285–291.
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Maggio, B., Daidone, G., Raffa, D., Plescia, S., Bombieri, G. & Meneghetti, F. (2005). Helv. Chim. Acta, 88, 2272–2281.
PARST95not mentioned in CIF; should this be omitted or should
a citation be added?
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
On the basis of our studies on the non classical Pschorr reaction (Maggio et al., 2005), we have hypothesized that the product of thermal decomposition of the diazonium hydrogen sulfate (1) (Daidone et al., 1980) could be one of the two possible isomers 2 and 3 (Fig. 1). Single-crystal X-ray analysis on the reaction product (Fig. 2) allows to assign the formation of isomer 2, having the two methyl groups trans oriented with respect to the tricyclic ring. The molecule is characterized by a quite planar phenylpyrazolo[3,4-c]isoquinolin-5-one moiety, having as highest deviation from planarity O1 atom (out of plane of 0.066 (2) Å). The non aromatic ring of the tricyclic framework has puckering parameter of φ2=-69.4 (2)° and QT=0.059 (3) Å. The phenyl substituent is inclined with respect to the heterotricycle of 67 (1)°, with a torsion angle N1—N2—C4—C5 of -106.1 (3)°. The molecular packing is determined by intermolecular C6—H6···N1i interactions of 2.56 (2)Å and 158 (1)° [symmetry code: (i) x - 1/2, -y - 1/2, z + 1/2], with the formation of chains developing along the c axis (Fig. 3).