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Acta Cryst. (2008). E64, o2272    [ doi:10.1107/S1600536808035009 ]

5-Phenyl-7,8-dihydro-1,3-dioxano[4,5-g]isoquinoline

J.-M. Li and D. Liang

Abstract top

In the title compound, C16H13NO2, the two benzene rings make a dihedral angle of 55.5 (2)°. The crystal packing is stabilized by intermolecular C-H...O hydrogen bonds and weak [pi]-[pi] stacking interactions [centroid-centroid distance = 3.595 (3)Å], linking the molecules into ladders of inversion dimers.

Comment top

Isoquinolinones are important compounds from both the synthetic and applied points of view. Their structures are incorporated in several alkaloids (Bentley, 20000 and other pharmacologically important compounds (Jayaraman et al., 2002). Of the variety of methods that have been developed for the synthesis of the isoquinoline ring system, the most commonly used procedure is the Bischler-Napieralski reaction (Bischler & Napieralski, 1893). We now wish to report an effective Bischler-Napieralski procedure for the synthesis of 1,2,3,4-tetrahydro-6,7-dimethoxy-1-phenylisoquinoline the title compound (I) and report its crystal structure here.

In compound (I), all bond lengths in the molecular are normal (Allen et al., 1987). The benzene ring C10–C15 and bonded atoms C7, C9, O1 and O2 are coplanar, the largest deviation from the mean plane being 0.039 (2)Å for atom O1. The other benzene ring, C1–C6, and bonded atoms C7 are also coplanar, the largest deviation from the mean plane being 0.032 (2)Å. The two benzene rings make a dihedral angle of 55.5 (2)°.

The relatively short distance of 3.595 (3) between the centroids of benzene ring C10—C15 and 1,3-dioxole ring C13/C14/C16/O1/O2 [at -x,1 - y,-z] indicates the presence of weak π-π interactions, The crystal packing is stabilized by intermolecular C—H···O hydrogen bonds, linking the molecules into ladders of dimers.

Related literature top

For details of the biological activities of isoquinolinone compounds, see: Bentley (2000); Jayaraman et al. (2002). For the Bischler–Napieralski reaction, see: Bischler & Napieralski (1893). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized by following Bischler-Napieralski procedures: 0.01 mol N-[2-(3, 4-methylenedioxy)phenyl]benzamide (synthesized by β-(3, 4-methylenedioxy)phenethylamine, Benzoyl chloride and Et3N) was dissolved in 20 ml CH3CN, 5 g POCl3 was added dropwise, the mixture was refluxed under N2 for 5 h, after cooled the volatiles were evaporated under vacuum, then water was added and adjusted the pH to 8, after extracted with CH2Cl2, the organic layers was washed with saturated NaCl and dried with Na2SO4, the product was isolated by evaporation of the solvent and recrystalization, 2.31 g, Yield: 92%. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethyl acetate at room temperature.

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å, with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 40% probability displacement ellipsoids for non-H atoms.
5-Phenyl-7,8-dihydro-1,3-dioxano[4,5-g]isoquinoline top
Crystal data top
C16H13NO2Z = 2
Mr = 251.27F(000) = 264
Triclinic, P1Dx = 1.340 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.5005 (17) ÅCell parameters from 1451 reflections
b = 8.5297 (17) Åθ = 2.5–23.4°
c = 10.143 (2) ŵ = 0.09 mm−1
α = 109.07 (3)°T = 293 K
β = 109.44 (2)°Block, colorless
γ = 99.70 (3)°0.28 × 0.10 × 0.08 mm
V = 622.9 (2) Å3
Data collection top
Rigaku R-AXIS RAPID IP area-detector
diffractometer		2145 independent reflections
Radiation source: Rotating Anode1275 reflections with I > 2σ(I)
graphiteRint = 0.037
ω oscillation scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→10
Tmin = 0.976, Tmax = 0.993k = −10→10
4801 measured reflectionsl = −11→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.144 w = 1/[σ2(Fo2) + (0.0514P)2 + 0.1397P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
2145 reflectionsΔρmax = 0.20 e Å−3
173 parametersΔρmin = −0.20 e Å−3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.048 (8)
Crystal data top
C16H13NO2γ = 99.70 (3)°
Mr = 251.27V = 622.9 (2) Å3
Triclinic, P1Z = 2
a = 8.5005 (17) ÅMo Kα radiation
b = 8.5297 (17) ŵ = 0.09 mm−1
c = 10.143 (2) ÅT = 293 K
α = 109.07 (3)°0.28 × 0.10 × 0.08 mm
β = 109.44 (2)°
Data collection top
Rigaku R-AXIS RAPID IP area-detector
diffractometer		2145 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1275 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.993Rint = 0.037
4801 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.144Δρmax = 0.20 e Å−3
S = 1.13Δρmin = −0.20 e Å−3
2145 reflectionsAbsolute structure: ?
173 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O10.9151 (2)0.7157 (2)1.18121 (17)0.0688 (6)
O20.6920 (2)0.4574 (2)1.01260 (17)0.0656 (6)
N10.8054 (3)0.6182 (3)0.5069 (2)0.0638 (6)
C10.5553 (3)0.2889 (4)0.3031 (3)0.0614 (7)
H1B0.52960.38080.27950.074*
C20.4741 (4)0.1204 (4)0.1932 (3)0.0734 (8)
H2A0.39380.09960.09610.088*
C30.5097 (4)−0.0172 (4)0.2247 (3)0.0772 (9)
H3A0.4550−0.13080.14960.093*
C40.6281 (4)0.0149 (4)0.3695 (3)0.0692 (8)
H4A0.6521−0.07790.39240.083*
C50.7107 (3)0.1825 (3)0.4798 (3)0.0579 (7)
H5A0.79140.20220.57650.069*
C60.6756 (3)0.3230 (3)0.4491 (2)0.0511 (6)
C70.7705 (3)0.5073 (3)0.5614 (2)0.0521 (6)
C80.9013 (4)0.7997 (3)0.6168 (3)0.0679 (8)
H8A0.81870.85700.64060.081*
H8B0.95730.86000.57020.081*
C91.0385 (4)0.8139 (3)0.7632 (3)0.0604 (7)
H9A1.12790.76640.74240.072*
H9B1.09430.93540.83510.072*
C100.9508 (3)0.7137 (3)0.8300 (2)0.0497 (6)
C110.8169 (3)0.5585 (3)0.7272 (2)0.0468 (6)
C120.7220 (3)0.4618 (3)0.7802 (2)0.0490 (6)
H12A0.63260.35750.71300.059*
C130.7659 (3)0.5266 (3)0.9336 (2)0.0492 (6)
C140.8994 (3)0.6795 (3)1.0347 (2)0.0510 (6)
C150.9955 (3)0.7752 (3)0.9871 (2)0.0525 (6)
H15A1.08710.87711.05660.063*
C160.7728 (4)0.5854 (4)1.1664 (3)0.0713 (8)
H16A0.81590.53181.23630.086*
H16B0.68820.63791.19180.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0833 (14)0.0751 (12)0.0399 (9)0.0155 (10)0.0240 (9)0.0202 (8)
O20.0861 (14)0.0677 (11)0.0470 (10)0.0158 (10)0.0377 (9)0.0221 (9)
N10.0805 (16)0.0671 (14)0.0497 (12)0.0199 (12)0.0329 (11)0.0267 (11)
C10.0513 (15)0.0779 (18)0.0514 (15)0.0196 (13)0.0185 (12)0.0255 (14)
C20.0562 (17)0.091 (2)0.0482 (15)0.0073 (15)0.0087 (12)0.0213 (15)
C30.080 (2)0.0689 (18)0.0552 (16)0.0037 (16)0.0187 (14)0.0116 (14)
C40.079 (2)0.0613 (16)0.0564 (16)0.0162 (14)0.0246 (14)0.0179 (13)
C50.0633 (16)0.0625 (15)0.0404 (13)0.0169 (13)0.0184 (11)0.0168 (12)
C60.0522 (15)0.0630 (15)0.0383 (12)0.0164 (12)0.0232 (10)0.0173 (11)
C70.0588 (16)0.0615 (15)0.0433 (12)0.0229 (12)0.0272 (11)0.0221 (12)
C80.087 (2)0.0622 (16)0.0626 (16)0.0183 (14)0.0396 (15)0.0296 (14)
C90.0646 (17)0.0594 (15)0.0592 (15)0.0142 (12)0.0327 (13)0.0223 (12)
C100.0498 (14)0.0533 (13)0.0471 (13)0.0170 (11)0.0226 (11)0.0190 (11)
C110.0517 (14)0.0525 (13)0.0393 (12)0.0180 (11)0.0220 (10)0.0186 (10)
C120.0533 (15)0.0522 (13)0.0427 (12)0.0180 (11)0.0221 (10)0.0178 (11)
C130.0587 (15)0.0553 (14)0.0405 (12)0.0199 (11)0.0273 (11)0.0202 (11)
C140.0596 (16)0.0587 (14)0.0359 (12)0.0255 (12)0.0197 (11)0.0178 (11)
C150.0507 (14)0.0560 (14)0.0458 (13)0.0150 (11)0.0187 (11)0.0171 (11)
C160.087 (2)0.0816 (19)0.0449 (14)0.0216 (16)0.0341 (14)0.0215 (14)
Geometric parameters (Å, °) top
O1—C141.370 (3)C7—C111.481 (3)
O1—C161.427 (3)C8—C91.504 (4)
O2—C131.381 (3)C8—H8A0.9700
O2—C161.421 (3)C8—H8B0.9700
N1—C71.283 (3)C9—C101.499 (3)
N1—C81.465 (3)C9—H9A0.9700
C1—C21.375 (4)C9—H9B0.9700
C1—C61.391 (3)C10—C111.391 (3)
C1—H1B0.9300C10—C151.394 (3)
C2—C31.368 (4)C11—C121.406 (3)
C2—H2A0.9300C12—C131.359 (3)
C3—C41.380 (4)C12—H12A0.9300
C3—H3A0.9300C13—C141.376 (3)
C4—C51.372 (3)C14—C151.364 (3)
C4—H4A0.9300C15—H15A0.9300
C5—C61.387 (3)C16—H16A0.9700
C5—H5A0.9300C16—H16B0.9700
C6—C71.487 (3)
C14—O1—C16105.44 (18)C10—C9—C8108.3 (2)
C13—O2—C16105.24 (18)C10—C9—H9A110.0
C7—N1—C8117.11 (19)C8—C9—H9A110.0
C2—C1—C6120.6 (3)C10—C9—H9B110.0
C2—C1—H1B119.7C8—C9—H9B110.0
C6—C1—H1B119.7H9A—C9—H9B108.4
C3—C2—C1120.9 (3)C11—C10—C15121.1 (2)
C3—C2—H2A119.6C11—C10—C9116.9 (2)
C1—C2—H2A119.6C15—C10—C9122.0 (2)
C2—C3—C4119.1 (3)C10—C11—C12120.3 (2)
C2—C3—H3A120.5C10—C11—C7117.7 (2)
C4—C3—H3A120.5C12—C11—C7121.8 (2)
C5—C4—C3120.5 (3)C13—C12—C11117.4 (2)
C5—C4—H4A119.7C13—C12—H12A121.3
C3—C4—H4A119.7C11—C12—H12A121.3
C4—C5—C6120.9 (2)C12—C13—C14121.9 (2)
C4—C5—H5A119.6C12—C13—O2128.3 (2)
C6—C5—H5A119.6C14—C13—O2109.77 (19)
C5—C6—C1118.0 (2)C15—C14—O1127.9 (2)
C5—C6—C7122.7 (2)C15—C14—C13122.1 (2)
C1—C6—C7119.0 (2)O1—C14—C13110.0 (2)
N1—C7—C11122.4 (2)C14—C15—C10117.2 (2)
N1—C7—C6116.7 (2)C14—C15—H15A121.4
C11—C7—C6120.8 (2)C10—C15—H15A121.4
N1—C8—C9112.5 (2)O2—C16—O1108.54 (19)
N1—C8—H8A109.1O2—C16—H16A110.0
C9—C8—H8A109.1O1—C16—H16A110.0
N1—C8—H8B109.1O2—C16—H16B110.0
C9—C8—H8B109.1O1—C16—H16B110.0
H8A—C8—H8B107.8H16A—C16—H16B108.4
C6—C1—C2—C3−0.1 (4)N1—C7—C11—C10−22.2 (4)
C1—C2—C3—C40.5 (5)C6—C7—C11—C10159.5 (2)
C2—C3—C4—C5−0.8 (5)N1—C7—C11—C12153.3 (3)
C3—C4—C5—C60.9 (4)C6—C7—C11—C12−25.0 (4)
C4—C5—C6—C1−0.5 (4)C10—C11—C12—C130.3 (4)
C4—C5—C6—C7−175.7 (2)C7—C11—C12—C13−175.0 (2)
C2—C1—C6—C50.1 (4)C11—C12—C13—C14−0.9 (4)
C2—C1—C6—C7175.6 (2)C11—C12—C13—O2179.4 (2)
C8—N1—C7—C112.5 (4)C16—O2—C13—C12−173.7 (3)
C8—N1—C7—C6−179.1 (2)C16—O2—C13—C146.5 (3)
C5—C6—C7—N1142.5 (3)C16—O1—C14—C15174.1 (3)
C1—C6—C7—N1−32.7 (3)C16—O1—C14—C13−5.3 (3)
C5—C6—C7—C11−39.2 (3)C12—C13—C14—C150.0 (4)
C1—C6—C7—C11145.6 (2)O2—C13—C14—C15179.8 (2)
C7—N1—C8—C937.6 (3)C12—C13—C14—O1179.4 (2)
N1—C8—C9—C10−56.4 (3)O2—C13—C14—O1−0.8 (3)
C8—C9—C10—C1137.8 (3)O1—C14—C15—C10−178.0 (2)
C8—C9—C10—C15−139.8 (3)C13—C14—C15—C101.3 (4)
C15—C10—C11—C121.0 (4)C11—C10—C15—C14−1.8 (4)
C9—C10—C11—C12−176.6 (2)C9—C10—C15—C14175.7 (2)
C15—C10—C11—C7176.5 (2)C13—O2—C16—O1−9.7 (3)
C9—C10—C11—C7−1.1 (3)C14—O1—C16—O29.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.932.553.465 (4)169
Symmetry codes: (i) −x+1, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.932.553.465 (4)169
Symmetry codes: (i) −x+1, −y, −z+1.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bentley, K. B. (2000). Nat. Prod. Rep. 17, 247–268.

Bischler, A. & Napieralski, B. (1893). Chem. Ber. 26, 1903.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Jayaraman, M., Fox, B. M., Hollingshead, M., Kohlhagen, G., Pommier, Y. & Cushman, M. (2002). J. Med. Chem. 44, 242–249.

Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Takyo, Japan

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.