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Acta Cryst. (2009). E65, o1454    [ doi:10.1107/S1600536809020091 ]

6-Phenyl-5a,6,6a,7,12,13a-hexahydro-5H-benzo[6,7]indolizino[3,2-a]pyrrolizine

B. Gunasekaran, S. Kathiravan, R. Raghunathan, V. Renuga and V. Manivannan

Abstract top

In the title compound, C23H22N2, the central pyrrolidine ring adopts an envelope conformation. The benzene ring of the hexahydropyrroloisoquinoline ring system makes dihedral angles of 83.43 (6) and 61.99 (10)°, respectively, with the phenyl and pyrrole rings. In the crystal structure, weak C-H...[pi] interactions are observed.

Comment top

Pyrrolidine containing compounds are of significant importance because of their biological activities and widespread employment in catalysis (Witherup et al., 1995; Kravchenko et al., 2005). Pyrroles are very useful precursors in porphyrin synthesis (Sobral & Rocha Gonsalves, 2001a,b) and as monomers for polymer chemistry (Brockmann & Tour, 1995), with applications ranging from non linear optical materials (Suslick et al., 1992) to electronic noses (Di Natale et al., 1998).

The geometric parameters of the title molecule (Fig. 1) agree well with reported similar structure (Liu et al., 2007). The phenyl ring (C11—C16) makes a dihedral angle of 83.43 (6)° with C2—C7 ring and 48.72 (6)° with N2/C19—C22 ring, respectively. The sum of the bond angles around N1 [334.71 (32)°] indicate the sp3 hybridized state of atom N1 in the molecule. The pyrrolidine ring [N1/C9/C10/C17/C23] adopts an envelope conformation.

The crystal structure is stabilized by weak C—H···π [C4—H4···Cg3, C13—H13···Cg3 & C18—H18B···Cg6 (Table 1; Cg3 and Cg6 are the centroid of the rings defined by the atoms N2/C19–C22 and C11–C16, respectively.)] interactions.

Related literature top

For biological activity of pyrrolidine derivatives, see: Witherup et al. (1995); Kravchenko et al. (2005). For biological activity of pyrrole derivatives, see: Sobral & Rocha Gonsalves (2001a,b); Brockmann & Tour (1995); Suslick et al. (1992); Di Natale et al. (1998). For a related structure, see: Liu et al. (2007). Cg3 and Cg6 are the centroids of the N2/C19–C22 and C11–C16 rings, respectively.

Experimental top

A mixture of N-allyl pyrrole-2-carbaldehyde (1 mmol) and 1,2,3,4-tetrahydroisoquinolinic acid (1 mmol) was refluxed in 1,2-dichloro benzene (10 ml) for 12 h till the completion of the reaction as evidenced by TLC analysis. The crude mixture was subjected to column chromatography to get the pure product.

Refinement top

H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H, C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for C—H, and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2,

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
6-Phenyl-5a,6,6a,7,12,13a-hexahydro-5H-benzo[6,7]indolizino[3,2- a]pyrrolizine top
Crystal data top
C23H22N2F(000) = 696
Mr = 326.43Dx = 1.268 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6264 reflections
a = 14.0694 (14) Åθ = 2.0–28.4°
b = 5.9300 (5) ŵ = 0.07 mm−1
c = 21.177 (2) ÅT = 293 K
β = 104.563 (3)°Needle, yellow
V = 1710.1 (3) Å30.20 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker KappaAPEXII
diffractometer		4266 independent reflections
Radiation source: fine-focus sealed tube3049 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 0 pixels mm-1θmax = 28.4°, θmin = 2.0°
ω and φ scansh = −18→17
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −7→4
Tmin = 0.985, Tmax = 0.989l = −28→28
20373 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0757P)2 + 0.3733P]
where P = (Fo2 + 2Fc2)/3
4266 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.17 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C23H22N2V = 1710.1 (3) Å3
Mr = 326.43Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.0694 (14) ŵ = 0.07 mm−1
b = 5.9300 (5) ÅT = 293 K
c = 21.177 (2) Å0.20 × 0.20 × 0.15 mm
β = 104.563 (3)°
Data collection top
Bruker KappaAPEXII
diffractometer		4266 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3049 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.989Rint = 0.032
20373 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.149Δρmax = 0.17 e Å−3
S = 1.01Δρmin = −0.23 e Å−3
4266 reflectionsAbsolute structure: ?
226 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
N10.42095 (9)0.02857 (19)0.64155 (6)0.0319 (3)
N20.26180 (10)0.2368 (2)0.50434 (6)0.0447 (3)
C90.42973 (10)0.2650 (2)0.66188 (7)0.0308 (3)
H90.36390.33020.65480.037*
C20.38439 (10)−0.0647 (2)0.74598 (7)0.0353 (3)
C80.48113 (11)0.2811 (3)0.73313 (7)0.0380 (3)
H8A0.47600.43430.74800.046*
H8B0.55020.24700.73900.046*
C100.48203 (10)0.3722 (2)0.61376 (7)0.0347 (3)
H100.46480.53260.60950.042*
C10.35781 (11)−0.0995 (2)0.67344 (7)0.0367 (3)
H1A0.3630−0.25860.66420.044*
H1B0.2901−0.05420.65560.044*
C230.39150 (11)0.0267 (2)0.56953 (7)0.0348 (3)
H230.4220−0.10110.55280.042*
C170.43198 (12)0.2536 (3)0.54943 (8)0.0400 (4)
H170.47960.22480.52360.048*
C70.43830 (10)0.1217 (2)0.77408 (7)0.0357 (3)
C110.59247 (11)0.3523 (2)0.63345 (7)0.0375 (3)
C60.45606 (12)0.1552 (3)0.84096 (8)0.0476 (4)
H60.49070.28200.85980.057*
C220.28437 (11)0.0379 (3)0.53632 (7)0.0392 (3)
C30.35068 (12)−0.2155 (3)0.78562 (8)0.0479 (4)
H30.3141−0.34030.76710.057*
C120.64174 (12)0.1645 (3)0.61992 (8)0.0472 (4)
H120.60620.04140.59910.057*
C140.79640 (14)0.3355 (4)0.66854 (11)0.0724 (6)
H140.86470.33050.67960.087*
C50.42305 (13)0.0033 (4)0.87978 (8)0.0555 (5)
H50.43620.02660.92460.067*
C160.64758 (13)0.5309 (3)0.66614 (9)0.0531 (4)
H160.61580.65850.67620.064*
C40.37077 (14)−0.1825 (4)0.85217 (9)0.0573 (5)
H40.3489−0.28630.87830.069*
C210.19983 (13)−0.0869 (3)0.52436 (8)0.0544 (5)
H210.1929−0.23100.53990.065*
C200.12558 (14)0.0442 (4)0.48407 (9)0.0637 (6)
H200.06030.00170.46830.076*
C190.16540 (13)0.2435 (4)0.47212 (9)0.0579 (5)
H190.13290.36160.44680.069*
C180.34333 (14)0.3849 (3)0.50884 (10)0.0663 (6)
H18A0.33410.52460.53040.080*
H18B0.35200.41950.46590.080*
C130.74311 (14)0.1569 (4)0.63685 (10)0.0634 (5)
H130.77540.03020.62670.076*
C150.74889 (15)0.5212 (4)0.68388 (11)0.0696 (6)
H150.78490.64090.70630.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0392 (6)0.0291 (6)0.0299 (6)−0.0006 (5)0.0136 (5)0.0012 (4)
N20.0475 (8)0.0488 (8)0.0345 (7)−0.0014 (6)0.0043 (6)0.0001 (6)
C90.0322 (7)0.0279 (6)0.0335 (8)0.0011 (5)0.0103 (6)0.0010 (5)
C20.0359 (7)0.0397 (7)0.0328 (8)0.0054 (6)0.0133 (6)0.0054 (6)
C80.0399 (8)0.0399 (8)0.0338 (8)−0.0039 (6)0.0085 (6)−0.0013 (6)
C100.0406 (8)0.0294 (7)0.0356 (8)−0.0011 (5)0.0127 (6)0.0035 (5)
C10.0450 (8)0.0321 (7)0.0358 (8)−0.0041 (6)0.0157 (6)0.0006 (6)
C230.0443 (8)0.0327 (7)0.0314 (7)−0.0013 (6)0.0167 (6)−0.0013 (5)
C170.0456 (8)0.0423 (8)0.0343 (8)−0.0065 (6)0.0143 (7)0.0043 (6)
C70.0325 (7)0.0436 (8)0.0317 (8)0.0064 (6)0.0095 (6)0.0033 (6)
C110.0399 (8)0.0385 (8)0.0373 (8)−0.0059 (6)0.0158 (6)0.0057 (6)
C60.0465 (9)0.0617 (10)0.0339 (8)−0.0002 (7)0.0086 (7)−0.0013 (7)
C220.0477 (9)0.0414 (8)0.0305 (7)−0.0066 (6)0.0132 (6)−0.0036 (6)
C30.0492 (9)0.0544 (10)0.0439 (9)−0.0047 (7)0.0187 (8)0.0083 (7)
C120.0464 (9)0.0467 (9)0.0530 (10)−0.0005 (7)0.0210 (8)0.0029 (7)
C140.0384 (10)0.1029 (18)0.0768 (15)−0.0080 (11)0.0159 (10)0.0205 (13)
C50.0539 (10)0.0837 (13)0.0305 (8)0.0026 (9)0.0138 (7)0.0060 (8)
C160.0524 (10)0.0499 (10)0.0568 (11)−0.0141 (8)0.0136 (8)−0.0027 (8)
C40.0572 (11)0.0792 (13)0.0411 (10)−0.0012 (9)0.0227 (8)0.0172 (9)
C210.0581 (11)0.0679 (12)0.0391 (9)−0.0228 (9)0.0157 (8)−0.0059 (8)
C200.0449 (10)0.1055 (17)0.0405 (10)−0.0142 (10)0.0105 (8)−0.0098 (10)
C190.0474 (10)0.0791 (13)0.0413 (10)0.0060 (9)0.0006 (8)−0.0050 (9)
C180.0655 (12)0.0555 (11)0.0623 (12)−0.0168 (9)−0.0126 (10)0.0245 (9)
C130.0515 (11)0.0744 (13)0.0722 (14)0.0120 (9)0.0303 (10)0.0125 (10)
C150.0526 (11)0.0799 (14)0.0719 (14)−0.0276 (11)0.0074 (10)0.0018 (11)
Geometric parameters (Å, °) top
N1—C11.4574 (17)C11—C121.380 (2)
N1—C91.4625 (17)C11—C161.390 (2)
N1—C231.4764 (18)C6—C51.377 (2)
N2—C191.357 (2)C6—H60.9300
N2—C221.358 (2)C22—C211.369 (2)
N2—C181.429 (2)C3—C41.380 (2)
C9—C81.503 (2)C3—H30.9300
C9—C101.5366 (19)C12—C131.381 (2)
C9—H90.9800C12—H120.9300
C2—C71.387 (2)C14—C151.369 (3)
C2—C31.389 (2)C14—C131.372 (3)
C2—C11.501 (2)C14—H140.9300
C8—C71.507 (2)C5—C41.371 (3)
C8—H8A0.9700C5—H50.9300
C8—H8B0.9700C16—C151.381 (3)
C10—C111.509 (2)C16—H160.9300
C10—C171.537 (2)C4—H40.9300
C10—H100.9800C21—C201.405 (3)
C1—H1A0.9700C21—H210.9300
C1—H1B0.9700C20—C191.359 (3)
C23—C221.496 (2)C20—H200.9300
C23—C171.561 (2)C19—H190.9300
C23—H230.9800C18—H18A0.9700
C17—C181.537 (2)C18—H18B0.9700
C17—H170.9800C13—H130.9300
C7—C61.389 (2)C15—H150.9300
C1—N1—C9112.29 (11)C12—C11—C16118.18 (15)
C1—N1—C23115.43 (11)C12—C11—C10122.81 (14)
C9—N1—C23106.99 (10)C16—C11—C10119.01 (14)
C19—N2—C22110.79 (15)C5—C6—C7120.94 (17)
C19—N2—C18134.42 (16)C5—C6—H6119.5
C22—N2—C18114.69 (14)C7—C6—H6119.5
N1—C9—C8109.89 (11)N2—C22—C21107.09 (15)
N1—C9—C10102.73 (11)N2—C22—C23110.77 (13)
C8—C9—C10116.72 (12)C21—C22—C23142.08 (16)
N1—C9—H9109.1C4—C3—C2120.85 (17)
C8—C9—H9109.1C4—C3—H3119.6
C10—C9—H9109.1C2—C3—H3119.6
C7—C2—C3119.11 (14)C11—C12—C13120.81 (17)
C7—C2—C1121.14 (12)C11—C12—H12119.6
C3—C2—C1119.67 (14)C13—C12—H12119.6
C9—C8—C7112.12 (12)C15—C14—C13119.86 (18)
C9—C8—H8A109.2C15—C14—H14120.1
C7—C8—H8A109.2C13—C14—H14120.1
C9—C8—H8B109.2C4—C5—C6119.76 (16)
C7—C8—H8B109.2C4—C5—H5120.1
H8A—C8—H8B107.9C6—C5—H5120.1
C11—C10—C9114.59 (11)C15—C16—C11120.79 (19)
C11—C10—C17114.82 (12)C15—C16—H16119.6
C9—C10—C17102.09 (11)C11—C16—H16119.6
C11—C10—H10108.3C5—C4—C3119.97 (16)
C9—C10—H10108.3C5—C4—H4120.0
C17—C10—H10108.3C3—C4—H4120.0
N1—C1—C2112.25 (12)C22—C21—C20106.99 (17)
N1—C1—H1A109.2C22—C21—H21126.5
C2—C1—H1A109.2C20—C21—H21126.5
N1—C1—H1B109.2C19—C20—C21108.40 (17)
C2—C1—H1B109.2C19—C20—H20125.8
H1A—C1—H1B107.9C21—C20—H20125.8
N1—C23—C22118.24 (11)N2—C19—C20106.73 (17)
N1—C23—C17104.38 (11)N2—C19—H19126.6
C22—C23—C17103.13 (12)C20—C19—H19126.6
N1—C23—H23110.2N2—C18—C17104.54 (13)
C22—C23—H23110.2N2—C18—H18A110.8
C17—C23—H23110.2C17—C18—H18A110.8
C18—C17—C10112.99 (14)N2—C18—H18B110.8
C18—C17—C23106.78 (13)C17—C18—H18B110.8
C10—C17—C23105.64 (11)H18A—C18—H18B108.9
C18—C17—H17110.4C14—C13—C12120.24 (19)
C10—C17—H17110.4C14—C13—H13119.9
C23—C17—H17110.4C12—C13—H13119.9
C2—C7—C6119.35 (14)C14—C15—C16120.1 (2)
C2—C7—C8120.50 (13)C14—C15—H15120.0
C6—C7—C8120.09 (14)C16—C15—H15120.0
C1—N1—C9—C865.15 (15)C17—C10—C11—C16146.25 (14)
C23—N1—C9—C8−167.22 (11)C2—C7—C6—C51.6 (2)
C1—N1—C9—C10−169.97 (11)C8—C7—C6—C5−175.69 (15)
C23—N1—C9—C10−42.33 (13)C19—N2—C22—C21−0.11 (19)
N1—C9—C8—C7−48.57 (15)C18—N2—C22—C21−177.00 (16)
C10—C9—C8—C7−164.97 (12)C19—N2—C22—C23177.62 (13)
N1—C9—C10—C11−84.82 (14)C18—N2—C22—C230.7 (2)
C8—C9—C10—C1135.46 (17)N1—C23—C22—N2112.17 (14)
N1—C9—C10—C1739.94 (13)C17—C23—C22—N2−2.34 (15)
C8—C9—C10—C17160.22 (12)N1—C23—C22—C21−71.4 (3)
C9—N1—C1—C2−49.38 (16)C17—C23—C22—C21174.1 (2)
C23—N1—C1—C2−172.38 (11)C7—C2—C3—C4−0.4 (2)
C7—C2—C1—N120.18 (19)C1—C2—C3—C4−177.42 (15)
C3—C2—C1—N1−162.92 (13)C16—C11—C12—C13−1.7 (2)
C1—N1—C23—C2238.60 (17)C10—C11—C12—C13177.70 (15)
C9—N1—C23—C22−87.17 (14)C7—C6—C5—C4−0.8 (3)
C1—N1—C23—C17152.43 (12)C12—C11—C16—C150.7 (3)
C9—N1—C23—C1726.66 (14)C10—C11—C16—C15−178.73 (16)
C11—C10—C17—C18−142.72 (14)C6—C5—C4—C3−0.6 (3)
C9—C10—C17—C1892.68 (14)C2—C3—C4—C51.3 (3)
C11—C10—C17—C23100.90 (14)N2—C22—C21—C20−0.04 (19)
C9—C10—C17—C23−23.71 (14)C23—C22—C21—C20−176.58 (19)
N1—C23—C17—C18−121.16 (14)C22—C21—C20—C190.2 (2)
C22—C23—C17—C183.00 (16)C22—N2—C19—C200.2 (2)
N1—C23—C17—C10−0.62 (14)C18—N2—C19—C20176.3 (2)
C22—C23—C17—C10123.53 (12)C21—C20—C19—N2−0.2 (2)
C3—C2—C7—C6−1.0 (2)C19—N2—C18—C17−174.65 (17)
C1—C2—C7—C6175.95 (13)C22—N2—C18—C171.3 (2)
C3—C2—C7—C8176.34 (14)C10—C17—C18—N2−118.36 (16)
C1—C2—C7—C8−6.7 (2)C23—C17—C18—N2−2.7 (2)
C9—C8—C7—C220.92 (19)C15—C14—C13—C120.5 (3)
C9—C8—C7—C6−161.79 (13)C11—C12—C13—C141.2 (3)
C9—C10—C11—C1284.56 (17)C13—C14—C15—C16−1.5 (3)
C17—C10—C11—C12−33.18 (19)C11—C16—C15—C140.9 (3)
C9—C10—C11—C16−96.00 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg3i0.932.883.7250 (3)152
C13—H13···Cg3ii0.932.943.5626 (3)126
C18—H18B···Cg6iii0.972.793.6726 (4)152
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg3i0.932.883.7250 (3)152
C13—H13···Cg3ii0.932.943.5626 (3)126
C18—H18B···Cg6iii0.972.793.6726 (4)152
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank AMET University management, India, for their kind support.

references
References top

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