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Acta Cryst. (2008). E64, o1796    [ doi:10.1107/S1600536808026020 ]

(±)-Ethyl 6,7-dimethoxy-1-(1H-pyrrol-2-yl)-1,2,3,4-tetrahydroisoquinoline-2-carboxylate

R. P. Nikolova, T. Kolev, S. M. Statkova-Abeghe and B. L. Shivachev

Abstract top

In the title compound, C18H22N2O4, the dihedral angle between the pyrrolyl and quinolinyl fragments is 68.97 (2)°. Two non-classical intramolecular C-H...O hydrogen bonds stabilize the molecular geometry. In the crystal structure, molecules form infinite chains via moderate intermolecular N-H...O(CH3) hydrogen bonds.

Comment top

As part of our research program on tetrahydroisoquinolines (Kolev et al., 2007; Petrova et al., 2007; Petrova et al., 2005) the crystal structure of the title compound,(I), has been solved. The molecule possesses regular geometry with two nearly planar ring systems. The r.m.s. deviation of pyrrolyl and quinolin-2(1H)-fragments is 0.161 (7) Å and 0.002 (2) Å, respectively, and the dihedral angle between their mean planes is 68.97 (2)°. The geometrical parameters of both rings are comparable to those observed in other quinoline derivatives (Rajnikant et al., 2002; Vincente et al., 2005; Shishkina et al., 2005). Two non-classsical intramolecular hydrogen bonds (C7—H7···O4 and C8—H8···O3) stabilize the molecular geometry. Only the methoxy O atoms are realised as hydrogen bond acceptors and together with the only possible donor form a bifurcated hydrogen bond of the N—H···(O,O) type. Thus neighboring molecules are oriented head-to-tail and connected to form infinite chains along the b-axis (Fig. 2).

Related literature top

For related crystal structures, see: Kolev et al. (2007); Petrova et al. (2007); Petrova et al. (2005); Rajnikant et al. (2002); Shishkina et al. (2005); Venkov et al. (2004); Vincente et al. (2005).

Experimental top

The title compound has been obtained following the procedure described by Venkov et al., 2004. Colorless crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation from ethanol/water (2:1) solution.

Refinement top

All H atoms were placed in idealized positions (C—Hmethyl = 0.96 Å, C—Hmethylen = 0.97 Å, C—Haromatic = 0.93Å and N—H = 0.86 Å) and were constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(Cmethyl) or Uiso(H) = 1.2Ueq(Caromatic, Cmethylen ~ or N). The high Rint value (0.11) and relatively low ratio (0.55) of observed to unique reflections may be a result of the poor diffraction quality of the crystal.

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of the structure and the atom-numbering scheme of (I) showing 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of the molecular packing in (I). Hydrogen bonds are represented by dotted lines. H atoms not involved in hydrogen bonding interactions have been omitted. [Symmetry code: (i) -x, -1/2 + y, 1/2 - z].
(±)-Ethyl 6,7-dimethoxy-1-(1H-pyrrol-2-yl)-1,2,3,4-tetrahydroisoquinoline- 2-carboxylate top
Crystal data top
C18H22N2O4F000 = 704
Mr = 330.38Dx = 1.321 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 22 reflections
a = 8.403 (3) Åθ = 18.3–18.8º
b = 17.046 (3) ŵ = 0.09 mm−1
c = 11.6486 (13) ÅT = 290 (2) K
β = 95.260 (13)ºPrism, colorless
V = 1661.5 (7) Å30.32 × 0.32 × 0.30 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.110
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 2.1º
T = 290(2) Kh = 0→10
Nonprofiled ω/2θ scansk = −20→20
Absorption correction: nonel = −14→14
6852 measured reflections3 standard reflections
3263 independent reflections every 120 min
1828 reflections with I > 2σ(I) intensity decay: −1%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.065  w = 1/[σ2(Fo2) + (0.0293P)2 + 2.0348P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.156(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.21 e Å−3
3263 reflectionsΔρmin = −0.20 e Å−3
218 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0075 (10)
Secondary atom site location: difference Fourier map
Crystal data top
C18H22N2O4V = 1661.5 (7) Å3
Mr = 330.38Z = 4
Monoclinic, P21/cMo Kα
a = 8.403 (3) ŵ = 0.09 mm−1
b = 17.046 (3) ÅT = 290 (2) K
c = 11.6486 (13) Å0.32 × 0.32 × 0.30 mm
β = 95.260 (13)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.110
Absorption correction: none3 standard reflections
6852 measured reflections every 120 min
3263 independent reflections intensity decay: −1%
1828 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.065218 parameters
wR(F2) = 0.156H-atom parameters constrained
S = 1.07Δρmax = 0.21 e Å−3
3263 reflectionsΔρmin = −0.20 e Å−3
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
O10.2084 (3)0.63581 (14)0.3413 (2)0.0474 (7)
O20.3254 (3)0.65266 (14)0.1467 (2)0.0443 (7)
O30.2237 (3)0.20530 (14)0.1157 (2)0.0476 (7)
O40.2206 (3)0.23765 (16)0.3033 (2)0.0573 (8)
N10.0630 (3)0.30217 (16)0.1633 (2)0.0336 (7)
C20.2399 (4)0.5223 (2)0.0832 (3)0.0339 (8)
H20.28150.52900.01260.041*
C19−0.1547 (4)0.37433 (19)0.2412 (3)0.0339 (8)
C60.1037 (4)0.44139 (19)0.2113 (3)0.0329 (8)
C30.2542 (4)0.58174 (19)0.1623 (3)0.0337 (8)
C13−0.2492 (4)0.4391 (2)0.2366 (3)0.0415 (9)
H13−0.21540.49060.22770.050*
C70.0237 (4)0.36515 (18)0.2422 (3)0.0347 (8)
H70.06590.35030.32040.042*
C90.1515 (4)0.3882 (2)0.0146 (3)0.0408 (9)
H9A0.25640.36570.00850.049*
H9B0.11570.4115−0.05930.049*
C50.1184 (4)0.5026 (2)0.2922 (3)0.0352 (8)
H50.07800.49560.36320.042*
N3−0.2512 (3)0.31109 (17)0.2555 (2)0.0418 (8)
H3−0.21970.26310.26160.050*
C100.1731 (4)0.2482 (2)0.2028 (3)0.0395 (9)
C40.1907 (4)0.5724 (2)0.2694 (3)0.0349 (8)
C180.4219 (5)0.6587 (2)0.0526 (3)0.0555 (11)
H18A0.46480.71090.04990.083*
H18B0.35800.6479−0.01820.083*
H18C0.50800.62160.06260.083*
C10.1642 (4)0.45151 (19)0.1057 (3)0.0323 (8)
C15−0.4056 (5)0.3361 (2)0.2588 (3)0.0498 (10)
H15−0.49360.30420.26720.060*
C80.0366 (4)0.3237 (2)0.0414 (3)0.0356 (8)
H8A−0.07250.34150.02400.043*
H8B0.05290.2782−0.00610.043*
C170.1649 (5)0.6268 (2)0.4555 (3)0.0527 (11)
H17A0.18160.67540.49650.079*
H17B0.22940.58650.49410.079*
H17C0.05430.61230.45320.079*
C14−0.4078 (5)0.4148 (2)0.2476 (3)0.0491 (10)
H14−0.49710.44710.24710.059*
C110.3387 (6)0.1452 (3)0.1464 (4)0.0675 (14)
H11A0.29720.10940.20100.081*
H11B0.43610.16850.18240.081*
C120.3725 (6)0.1029 (3)0.0433 (4)0.0812 (16)
H12A0.45080.06300.06330.122*
H12B0.41290.1387−0.01060.122*
H12C0.27610.07900.00900.122*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0666 (18)0.0391 (15)0.0374 (14)−0.0089 (13)0.0099 (13)−0.0089 (12)
O20.0514 (15)0.0414 (15)0.0412 (14)−0.0117 (12)0.0110 (12)−0.0012 (12)
O30.0551 (17)0.0418 (15)0.0455 (15)0.0201 (13)0.0028 (13)−0.0023 (13)
O40.073 (2)0.0578 (18)0.0403 (16)0.0254 (15)0.0029 (14)0.0079 (14)
N10.0403 (17)0.0308 (16)0.0298 (14)0.0073 (14)0.0035 (13)0.0008 (13)
C20.0360 (19)0.039 (2)0.0275 (17)0.0023 (16)0.0060 (15)0.0038 (15)
C190.043 (2)0.0306 (19)0.0297 (18)−0.0011 (16)0.0094 (16)0.0005 (15)
C60.0326 (19)0.0323 (19)0.0339 (18)0.0051 (15)0.0040 (16)−0.0011 (15)
C30.0330 (19)0.0326 (19)0.0351 (19)−0.0019 (15)0.0009 (16)0.0030 (16)
C130.046 (2)0.037 (2)0.043 (2)0.0064 (18)0.0088 (18)0.0034 (17)
C70.044 (2)0.0297 (18)0.0317 (18)0.0025 (16)0.0092 (16)0.0011 (15)
C90.047 (2)0.042 (2)0.0335 (19)0.0006 (18)0.0074 (18)−0.0034 (17)
C50.037 (2)0.041 (2)0.0289 (17)0.0009 (17)0.0065 (15)0.0007 (17)
N30.0453 (19)0.0350 (17)0.0460 (18)−0.0009 (15)0.0084 (15)0.0054 (15)
C100.043 (2)0.037 (2)0.039 (2)0.0001 (18)0.0094 (18)0.0029 (17)
C40.041 (2)0.0339 (19)0.0297 (18)0.0008 (16)0.0014 (16)−0.0043 (16)
C180.053 (3)0.064 (3)0.052 (2)−0.016 (2)0.016 (2)0.000 (2)
C10.0322 (19)0.0352 (19)0.0299 (17)0.0062 (15)0.0043 (15)0.0019 (15)
C150.041 (2)0.060 (3)0.050 (2)−0.009 (2)0.0124 (19)−0.001 (2)
C80.041 (2)0.0345 (19)0.0306 (18)0.0032 (16)−0.0010 (15)−0.0055 (16)
C170.067 (3)0.054 (3)0.038 (2)−0.003 (2)0.009 (2)−0.011 (2)
C140.044 (2)0.057 (3)0.047 (2)0.013 (2)0.009 (2)0.000 (2)
C110.077 (3)0.052 (3)0.073 (3)0.030 (2)0.006 (3)−0.004 (2)
C120.083 (4)0.076 (3)0.084 (4)0.035 (3)0.004 (3)−0.023 (3)
Geometric parameters (Å, °) top
O1—C41.367 (4)C9—C81.515 (5)
O1—C171.420 (4)C9—H9A0.9700
O2—C31.369 (4)C9—H9B0.9700
O2—C181.426 (4)C5—C41.374 (5)
O3—C101.350 (4)C5—H50.9300
O3—C111.431 (5)N3—C151.369 (5)
O4—C101.216 (4)N3—H30.8600
N1—C101.355 (4)C18—H18A0.9600
N1—C81.464 (4)C18—H18B0.9600
N1—C71.470 (4)C18—H18C0.9600
C2—C31.367 (5)C15—C141.349 (5)
C2—C11.399 (4)C15—H150.9300
C2—H20.9300C8—H8A0.9700
C19—C131.359 (5)C8—H8B0.9700
C19—N31.368 (4)C17—H17A0.9600
C19—C71.506 (5)C17—H17B0.9600
C6—C11.385 (4)C17—H17C0.9600
C6—C51.403 (4)C14—H140.9300
C6—C71.521 (4)C11—C121.451 (6)
C3—C41.410 (4)C11—H11A0.9700
C13—C141.413 (5)C11—H11B0.9700
C13—H130.9300C12—H12A0.9600
C7—H70.9800C12—H12B0.9600
C9—C11.510 (4)C12—H12C0.9600
C4—O1—C17117.8 (3)O1—C4—C5126.3 (3)
C3—O2—C18116.9 (3)O1—C4—C3115.1 (3)
C10—O3—C11116.9 (3)C5—C4—C3118.6 (3)
C10—N1—C8122.5 (3)O2—C18—H18A109.5
C10—N1—C7118.0 (3)O2—C18—H18B109.5
C8—N1—C7113.6 (3)H18A—C18—H18B109.5
C3—C2—C1121.8 (3)O2—C18—H18C109.5
C3—C2—H2119.1H18A—C18—H18C109.5
C1—C2—H2119.1H18B—C18—H18C109.5
C13—C19—N3107.1 (3)C6—C1—C2118.9 (3)
C13—C19—C7131.5 (3)C6—C1—C9121.8 (3)
N3—C19—C7121.2 (3)C2—C1—C9119.3 (3)
C1—C6—C5119.2 (3)C14—C15—N3108.2 (3)
C1—C6—C7121.5 (3)C14—C15—H15125.9
C5—C6—C7119.3 (3)N3—C15—H15125.9
O2—C3—C2125.3 (3)N1—C8—C9109.8 (3)
O2—C3—C4115.0 (3)N1—C8—H8A109.7
C2—C3—C4119.7 (3)C9—C8—H8A109.7
C19—C13—C14108.1 (3)N1—C8—H8B109.7
C19—C13—H13125.9C9—C8—H8B109.7
C14—C13—H13125.9H8A—C8—H8B108.2
N1—C7—C19110.6 (3)O1—C17—H17A109.5
N1—C7—C6110.3 (2)O1—C17—H17B109.5
C19—C7—C6111.7 (3)H17A—C17—H17B109.5
N1—C7—H7108.0O1—C17—H17C109.5
C19—C7—H7108.0H17A—C17—H17C109.5
C6—C7—H7108.0H17B—C17—H17C109.5
C1—C9—C8112.3 (3)C15—C14—C13107.2 (3)
C1—C9—H9A109.1C15—C14—H14126.4
C8—C9—H9A109.1C13—C14—H14126.4
C1—C9—H9B109.1O3—C11—C12109.2 (4)
C8—C9—H9B109.1O3—C11—H11A109.8
H9A—C9—H9B107.9C12—C11—H11A109.8
C4—C5—C6121.8 (3)O3—C11—H11B109.8
C4—C5—H5119.1C12—C11—H11B109.8
C6—C5—H5119.1H11A—C11—H11B108.3
C19—N3—C15109.4 (3)C11—C12—H12A109.5
C19—N3—H3125.3C11—C12—H12B109.5
C15—N3—H3125.3H12A—C12—H12B109.5
O4—C10—O3123.1 (3)C11—C12—H12C109.5
O4—C10—N1125.5 (3)H12A—C12—H12C109.5
O3—C10—N1111.4 (3)H12B—C12—H12C109.5
C18—O2—C3—C2−14.4 (5)C8—N1—C10—O3−14.8 (5)
C18—O2—C3—C4166.3 (3)C7—N1—C10—O3−166.0 (3)
C1—C2—C3—O2−179.6 (3)C17—O1—C4—C57.6 (5)
C1—C2—C3—C4−0.4 (5)C17—O1—C4—C3−172.4 (3)
N3—C19—C13—C14−0.4 (4)C6—C5—C4—O1178.8 (3)
C7—C19—C13—C14−175.2 (4)C6—C5—C4—C3−1.2 (5)
C10—N1—C7—C19−132.3 (3)O2—C3—C4—O10.6 (5)
C8—N1—C7—C1974.0 (3)C2—C3—C4—O1−178.7 (3)
C10—N1—C7—C6103.6 (3)O2—C3—C4—C5−179.4 (3)
C8—N1—C7—C6−50.1 (4)C2—C3—C4—C51.3 (5)
C13—C19—C7—N1−135.5 (4)C5—C6—C1—C20.7 (5)
N3—C19—C7—N150.3 (4)C7—C6—C1—C2−178.5 (3)
C13—C19—C7—C6−12.3 (5)C5—C6—C1—C9−179.6 (3)
N3—C19—C7—C6173.6 (3)C7—C6—C1—C91.2 (5)
C1—C6—C7—N116.3 (5)C3—C2—C1—C6−0.6 (5)
C5—C6—C7—N1−162.9 (3)C3—C2—C1—C9179.7 (3)
C1—C6—C7—C19−107.1 (4)C8—C9—C1—C612.8 (5)
C5—C6—C7—C1973.7 (4)C8—C9—C1—C2−167.5 (3)
C1—C6—C5—C40.2 (5)C19—N3—C15—C14−0.5 (4)
C7—C6—C5—C4179.4 (3)C10—N1—C8—C9−86.6 (4)
C13—C19—N3—C150.6 (4)C7—N1—C8—C965.8 (4)
C7—C19—N3—C15176.0 (3)C1—C9—C8—N1−44.0 (4)
C11—O3—C10—O40.0 (5)N3—C15—C14—C130.2 (5)
C11—O3—C10—N1−179.1 (3)C19—C13—C14—C150.1 (4)
C8—N1—C10—O4166.2 (4)C10—O3—C11—C12177.0 (4)
C7—N1—C10—O415.0 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.862.493.225 (4)145
N3—H3···O2i0.862.383.018 (4)132
C7—H7···O40.982.342.784 (4)107
C8—H8B···O30.972.292.653 (4)101
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.862.493.225 (4)145
N3—H3···O2i0.862.383.018 (4)132
C7—H7···O40.982.342.784 (4)107
C8—H8B···O30.972.292.653 (4)101
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Acknowledgements top

This work was supported by the National Science Fund of Bulgaria (Project TK357&TK358).

references
References top

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