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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o863.
Published online 2008 April 16. doi:  10.1107/S1600536808010180
PMCID: PMC2961101

1,4-Dimethyl-3-phenyl-3H-pyrazolo[3,4-c]isoquinolin-5(4H)-one

Abstract

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.

Related literature

Pyrazole rings are useful templates to investigate the role of the aryl­diazo­nium group in the Pschorr reaction pathway (Maggio et al., 2005 [triangle]). For related literature, see: Daidone et al. (1980 [triangle], 1993 [triangle], 1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o863-scheme1.jpg

Experimental

Crystal data

  • C18H15N3O
  • M r = 289.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o863-efi1.jpg
  • a = 8.066 (2) Å
  • b = 19.256 (3) Å
  • c = 9.270 (3) Å
  • β = 94.66 (3)°
  • V = 1435.0 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.6 × 0.5 × 0.4 mm

Data collection

  • Enraf–Nonius TurboCAD-4 diffractometer
  • Absorption correction: none
  • 2984 measured reflections
  • 2815 independent reflections
  • 1751 reflections with I > 2σ(I)
  • R int = 0.031
  • 3 standard reflections frequency: 120 min intensity decay: 3%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.113
  • S = 1.01
  • 2815 reflections
  • 202 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010180/fj2107sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010180/fj2107Isup2.hkl

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

supplementary crystallographic information

Comment

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 [var phi]2=-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).

Experimental

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.

Refinement

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).

Figures

Fig. 1.
The chemical reaction scheme.
Fig. 2.
The molecular structure of the title compound, showing atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 3.
Intermolecular interactions of the title compound, showing the molecular chains along the c axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C18H15N3OF000 = 608
Mr = 289.33Dx = 1.339 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 8.066 (2) Åθ = 9–10º
b = 19.256 (3) ŵ = 0.09 mm1
c = 9.270 (3) ÅT = 293 (2) K
β = 94.66 (3)ºPrism, colorless
V = 1435.0 (6) Å30.6 × 0.5 × 0.4 mm
Z = 4

Data collection

Enraf–Nonius TurboCAD-4 diffractometerθmax = 26.0º
Monochromator: graphiteθmin = 3.1º
T = 293(2) Kh = −9→9
Non–profiled ω/2θ scansk = 0→23
Absorption correction: nonel = 0→11
2984 measured reflections3 standard reflections
2815 independent reflections every 120 min
1751 reflections with I > 2σ(I) intensity decay: 3%
Rint = 0.031

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.01Δρmax = 0.16 e Å3
2815 reflectionsΔρmin = −0.15 e Å3
202 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.043 (3)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
O10.62196 (18)0.08361 (7)0.50784 (16)0.0628 (4)
N10.93284 (19)−0.15752 (8)0.28089 (16)0.0508 (4)
N20.89261 (18)−0.12641 (8)0.40852 (16)0.0447 (4)
C10.8813 (2)−0.11483 (10)0.1753 (2)0.0470 (5)
C20.8049 (2)−0.05543 (9)0.22995 (19)0.0415 (4)
C30.8148 (2)−0.06473 (9)0.37789 (19)0.0395 (4)
C40.9007 (2)−0.17029 (9)0.53322 (19)0.0417 (4)
C50.7563 (2)−0.19339 (10)0.5872 (2)0.0504 (5)
H50.6535−0.17790.54690.060*
C60.7650 (3)−0.23975 (11)0.7016 (2)0.0571 (6)
H60.6680−0.25510.73910.068*
C70.9167 (3)−0.26301 (10)0.7598 (2)0.0586 (6)
H70.9222−0.29480.83550.070*
C81.0615 (3)−0.23927 (10)0.7063 (2)0.0592 (6)
H81.1642−0.25450.74710.071*
C91.0537 (2)−0.19281 (10)0.5918 (2)0.0496 (5)
H91.1506−0.17700.55490.060*
N30.76230 (18)−0.01656 (8)0.47488 (16)0.0427 (4)
C100.6777 (2)0.04286 (10)0.4218 (2)0.0460 (5)
C110.6673 (2)0.05442 (9)0.2651 (2)0.0458 (5)
C120.7305 (2)0.00692 (10)0.1681 (2)0.0446 (5)
C130.7159 (3)0.02280 (11)0.0198 (2)0.0581 (6)
H130.7562−0.0083−0.04570.070*
C140.6434 (3)0.08330 (12)−0.0299 (3)0.0681 (6)
H140.63480.0929−0.12860.082*
C150.5829 (3)0.13036 (12)0.0653 (3)0.0665 (6)
H150.53450.17160.03090.080*
C160.5943 (2)0.11612 (11)0.2113 (2)0.0586 (6)
H160.55300.14790.27490.070*
C180.7939 (3)−0.02364 (10)0.63194 (19)0.0529 (5)
H18A0.7052−0.04960.66940.079*
H18B0.80000.02160.67560.079*
H18C0.8972−0.04760.65390.079*
C170.9067 (3)−0.13436 (12)0.0218 (2)0.0668 (6)
H17A0.9664−0.17750.02080.100*
H17B0.9694−0.0987−0.02140.100*
H17C0.8006−0.1394−0.03200.100*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0762 (10)0.0510 (9)0.0636 (10)0.0104 (7)0.0201 (8)−0.0068 (7)
N10.0585 (10)0.0518 (10)0.0430 (10)0.0078 (8)0.0096 (8)−0.0067 (8)
N20.0528 (10)0.0429 (9)0.0388 (9)0.0041 (7)0.0070 (7)−0.0005 (7)
C10.0490 (11)0.0520 (11)0.0405 (11)−0.0016 (9)0.0060 (8)−0.0056 (10)
C20.0444 (10)0.0429 (11)0.0374 (10)−0.0027 (8)0.0055 (8)−0.0014 (9)
C30.0380 (10)0.0400 (10)0.0409 (11)−0.0038 (8)0.0046 (8)−0.0025 (9)
C40.0468 (11)0.0382 (10)0.0402 (11)−0.0012 (8)0.0030 (8)−0.0032 (8)
C50.0464 (11)0.0561 (12)0.0484 (12)−0.0026 (10)0.0030 (9)−0.0014 (10)
C60.0665 (14)0.0578 (13)0.0481 (12)−0.0148 (11)0.0118 (11)−0.0022 (11)
C70.0893 (17)0.0431 (12)0.0426 (12)−0.0036 (11)0.0014 (11)0.0009 (9)
C80.0641 (14)0.0507 (13)0.0600 (14)0.0091 (10)−0.0116 (11)−0.0007 (11)
C90.0482 (11)0.0452 (11)0.0549 (12)−0.0022 (9)0.0007 (9)−0.0025 (10)
N30.0488 (9)0.0420 (9)0.0380 (9)−0.0013 (7)0.0075 (7)−0.0034 (7)
C100.0455 (11)0.0400 (11)0.0534 (12)−0.0023 (9)0.0094 (9)−0.0030 (9)
C110.0437 (10)0.0436 (11)0.0501 (12)−0.0026 (9)0.0048 (9)0.0044 (10)
C120.0438 (11)0.0467 (11)0.0433 (11)−0.0080 (9)0.0024 (9)0.0015 (9)
C130.0686 (14)0.0578 (14)0.0480 (13)−0.0017 (11)0.0056 (10)0.0050 (11)
C140.0792 (16)0.0678 (15)0.0565 (15)−0.0022 (13)0.0006 (12)0.0168 (12)
C150.0652 (14)0.0598 (14)0.0735 (16)0.0044 (11)0.0000 (12)0.0256 (13)
C160.0551 (13)0.0503 (12)0.0713 (15)0.0030 (10)0.0098 (11)0.0067 (11)
C180.0676 (13)0.0530 (12)0.0386 (11)−0.0022 (10)0.0076 (9)−0.0058 (9)
C170.0786 (15)0.0777 (16)0.0449 (13)0.0079 (12)0.0099 (11)−0.0136 (11)

Geometric parameters (Å, °)

O1—C101.230 (2)C9—H90.9300
N1—C11.319 (2)N3—C101.401 (2)
N1—N21.3879 (19)N3—C181.464 (2)
N2—C31.362 (2)C10—C111.466 (3)
N2—C41.429 (2)C11—C161.400 (3)
C1—C21.412 (2)C11—C121.407 (2)
C1—C171.502 (2)C12—C131.404 (3)
C2—C31.379 (2)C13—C141.366 (3)
C2—C121.440 (3)C13—H130.9300
C3—N31.382 (2)C14—C151.382 (3)
C4—C91.377 (2)C14—H140.9300
C4—C51.378 (2)C15—C161.376 (3)
C5—C61.384 (3)C15—H150.9300
C5—H50.9300C16—H160.9300
C6—C71.371 (3)C18—H18A0.9600
C6—H60.9300C18—H18B0.9600
C7—C81.383 (3)C18—H18C0.9600
C7—H70.9300C17—H17A0.9600
C8—C91.385 (3)C17—H17B0.9600
C8—H80.9300C17—H17C0.9600
C1—N1—N2106.38 (15)O1—C10—N3119.15 (18)
C3—N2—N1109.53 (14)O1—C10—C11123.45 (18)
C3—N2—C4132.37 (15)N3—C10—C11117.34 (17)
N1—N2—C4115.84 (14)C16—C11—C12119.19 (18)
N1—C1—C2111.02 (16)C16—C11—C10118.10 (18)
N1—C1—C17119.19 (17)C12—C11—C10122.70 (17)
C2—C1—C17129.78 (18)C13—C12—C11118.58 (18)
C3—C2—C1105.07 (16)C13—C12—C2124.78 (18)
C3—C2—C12119.52 (17)C11—C12—C2116.64 (17)
C1—C2—C12135.39 (17)C14—C13—C12121.0 (2)
N2—C3—C2107.99 (16)C14—C13—H13119.5
N2—C3—N3127.58 (16)C12—C13—H13119.5
C2—C3—N3124.33 (17)C13—C14—C15120.5 (2)
C9—C4—C5120.77 (17)C13—C14—H14119.8
C9—C4—N2119.08 (16)C15—C14—H14119.8
C5—C4—N2119.99 (16)C16—C15—C14119.9 (2)
C4—C5—C6119.64 (19)C16—C15—H15120.0
C4—C5—H5120.2C14—C15—H15120.0
C6—C5—H5120.2C15—C16—C11120.8 (2)
C7—C6—C5120.03 (19)C15—C16—H16119.6
C7—C6—H6120.0C11—C16—H16119.6
C5—C6—H6120.0N3—C18—H18A109.5
C6—C7—C8120.2 (2)N3—C18—H18B109.5
C6—C7—H7119.9H18A—C18—H18B109.5
C8—C7—H7119.9N3—C18—H18C109.5
C7—C8—C9120.1 (2)H18A—C18—H18C109.5
C7—C8—H8120.0H18B—C18—H18C109.5
C9—C8—H8120.0C1—C17—H17A109.5
C4—C9—C8119.28 (19)C1—C17—H17B109.5
C4—C9—H9120.4H17A—C17—H17B109.5
C8—C9—H9120.4C1—C17—H17C109.5
C3—N3—C10119.09 (16)H17A—C17—H17C109.5
C3—N3—C18123.15 (16)H17B—C17—H17C109.5
C10—N3—C18117.75 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···N1i0.932.593.457 (3)156

Symmetry codes: (i) x−1/2, −y−1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2107).

References

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  • 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.
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  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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