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

Meneghetti, F.; Bombieri, G.; Maggio, B.; Daidone, G.

doi:10.1107/S1600536808010180

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o863

doi:10.1107/S1600536808010180

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

Fiorella Meneghetti,^a ^* Gabriella Bombieri,^a Benedetta Maggio ^b and Giuseppe Daidone ^b

^aInstitute of Pharmaceutical and Toxicological Chemistry `P. Pratesi', University of Milan, via L. Mangiagalli 25, 20133 Milan, Italy, and ^bDepartment of Pharmaceutical and Technological Chemistry, University of Palermo, via Archirafi 32, 90123 Palermo, Italy
^*Correspondence e-mail: fiorella.meneghetti@unimi.it

(Received 19 March 2008; accepted 14 April 2008; online 16 April 2008)

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 ). For related literature, see: Daidone et al. (1980 , 1993 , 1998 ).

Experimental

Crystal data

C₁₈H₁₅N₃O
M_r = 289.33
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.113
S = 1.01
2815 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯N1ⁱ	0.93	2.59	3.457 (3)	156
Symmetry code: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; 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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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).

Figures top

	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.

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

Crystal data top

C₁₈H₁₅N₃O	F(000) = 608
M_r = 289.33	D_x = 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 = 9–10°
b = 19.256 (3) Å	µ = 0.09 mm⁻¹
c = 9.270 (3) Å	T = 293 K
β = 94.66 (3)°	Prism, colorless
V = 1435.0 (6) Å³	0.6 × 0.5 × 0.4 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.031
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 3.1°
Graphite monochromator	h = −9→9
Non–profiled ω/2θ scans	k = 0→23
2984 measured reflections	l = 0→11
2815 independent reflections	3 standard reflections every 120 min
1751 reflections with I > 2σ(I)	intensity decay: 3%

Refinement top

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + 1.3459P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.006
2815 reflections	Δρ_max = 0.16 e Å⁻³
202 parameters	Δρ_min = −0.15 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: 0.043 (3)

Crystal data top

C₁₈H₁₅N₃O	V = 1435.0 (6) Å³
M_r = 289.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.066 (2) Å	µ = 0.09 mm⁻¹
b = 19.256 (3) Å	T = 293 K
c = 9.270 (3) Å	0.6 × 0.5 × 0.4 mm
β = 94.66 (3)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.031
2984 measured reflections	3 standard reflections every 120 min
2815 independent reflections	intensity decay: 3%
1751 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	Δρ_max = 0.16 e Å⁻³
2815 reflections	Δρ_min = −0.15 e Å⁻³
202 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	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.93	2.59	3.457 (3)	156

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅N₃O
M_r	289.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.066 (2), 19.256 (3), 9.270 (3)
β (°)	94.66 (3)
V (Å³)	1435.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.6 × 0.5 × 0.4

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2984, 2815, 1751
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.113, 1.01
No. of reflections	2815
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.15

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.93	2.59	3.457 (3)	155.8

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

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Daidone, G., Maggio, B., Raffa, D., Plescia, S., Benetollo, F. & Bombieri, G. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 2891–2898. Web of Science CSD CrossRef Google Scholar
Daidone, G., Plescia, S. & Fabra, J. (1980). J. Heterocycl. Chem. 17, 1409–1411. CrossRef CAS Google Scholar
Daidone, G., Plescia, S., Maggio, B., Spirio, V., Benetollo, F. & Bombieri, G. (1993). J. Chem. Soc. Perkin Trans. 1, pp. 285–291. CSD CrossRef Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Maggio, B., Daidone, G., Raffa, D., Plescia, S., Bombieri, G. & Meneghetti, F. (2005). Helv. Chim. Acta, 88, 2272–2281. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536808010180

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