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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o73.
Published online 2007 December 6. doi:  10.1107/S1600536807062113
PMCID: PMC2915030

(3aRS,9bSR)-3-(4-Chloro­phen­yl)-1-methyl-1,2,3,3a,4,9b-hexa­hydro­chromeno[4,3-b]pyrrole-3a-carbonitrile

Abstract

In the mol­ecule of the title compound, C19H17ClN2O, the heterocyclic six-membered ring adopts a half-chair conformation, while the pyrrolidine ring has an envelope conformation. In the crystal structure, C—Cl(...)π [Cl(...)centroid = 3.680 (2) Å] inter­actions and van der Waals forces are present.

Related literature

For general background, see: Caine (1993 [triangle]); Tidey (1992 [triangle]); Carlson (1993 [triangle]); Sokoloff et al. (1990 [triangle]); Wilner (1985 [triangle]); Biava et al. (2005 [triangle]); Fernandes et al. (2004 [triangle]); Borthwick et al. (2000 [triangle]); Jiang et al. (2004 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]). For asymmetry parameters, see: Nardelli (1995 [triangle]).

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Object name is e-64-00o73-scheme1.jpg

Experimental

Crystal data

  • C19H17ClN2O
  • M r = 324.80
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o73-efi1.jpg
  • a = 8.8659 (4) Å
  • b = 7.6009 (3) Å
  • c = 24.2026 (10) Å
  • β = 97.701 (1)°
  • V = 1616.27 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 294 (2) K
  • 0.28 × 0.20 × 0.20 mm

Data collection

  • Bruker Kappa APEX2 diffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle]) T min = 0.935, T max = 0.953
  • 21338 measured reflections
  • 5199 independent reflections
  • 3858 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.138
  • S = 1.03
  • 5199 reflections
  • 208 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062113/hk2395sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062113/hk2395Isup2.hkl

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

Acknowledgments

SN thanks Professor M. N. Ponnuswamy, Department of Crystallography and Biophysics, University of Madras, India, for his guidance and valuable suggestions. SN thanks SRM management, India, for their support.

supplementary crystallographic information

Comment

Chromenopyrrole compounds are used in the treatment of impulsive disorders (Caine, 1993), aggressiveness (Tidey, 1992), parkinson's disease (Carlson, 1993), psychoses, memory disorders (Sokoloff et al., 1990), anxiety and depression (Wilner, 1985). Pyrrole derivatives have good invitro against mycobacteria and candidae (Biava et al., 2005). These derivatives also possess anti-inflammatory (Fernandes et al., 2004) and antiviral (Borthwick et al., 2000) activities. It has also been shown that N-substituted pyrrole derivatives inhibit human immuno deficiency virus type-I (HIV-I) (Jiang et al., 2004). In view of its medicinal importance, the crystal structure determination of the title compound, (I), was carried out.

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The sum of bond angles around atom N1 [330.9 (4)°] indicates sp3 hybridization. Rings A (C6—C11) and D (C13—C18) are, of course, planar and they are oriented at a dihedral angle of 46.7 (5)°. The heterocyclic ring B (O1/C4—C6/C11/C12) adopts a half-chair conformation with asymmetry parameters of ΔC2(C4) = 0.028 (1) (Nardelli, 1995) and puckering parameters of q2 = 0.778 (3) Å, q3 = 0.054 (2) Å and [var phi] = - 26.5 (2)° (Cremer & Pople, 1975). Atom C5 displaced by -0.645 (2) Å from the plane of the other five ring atoms. The pyrrolidine ring C (N1/C2—C4/C12) has an envelope conformation with asymmetry parameters of ΔCs(N1) = 0.030 (1) (Nardelli, 1995) and puckering parameters of q2 = 0.470 (1) Å and [var phi] =175.3 (2)° (Cremer & Pople, 1975). Atom N1 displaced by -0.691 (2) Å from the plane of the other four ring atoms.

In the crystal structure, no significant intermolecular π–π interactions are observed between two chlorophenyl rings as their centroids are seperated by 4.1049 (9) Å. Weak intermolecular C—Cl···π interactions (Spek, 2003), with C16···Cg4 = 3.680 (2) Å and Cl1···Cg4 = 3.858 (8) Å [Cg4 denotes centroid of ring D] and van der Waals forces stabilize the crystal structure (Fig. 2).

Experimental

For the preparation of the title compound, a solution of (Z)-2-((2-formyl- phenoxy)methyl)-3-(4-chlorophenyl)acrylonitrile (1 mmol) and sarcosine (1 mmol) in anhydrous methanol (10 ml) was refluxed. Completion of the reaction was evidenced by thin layer chromatography analysis. The solvent was removed in vacuum. The crude product was subjected to column chromatography on silica gel (100–200 mesh) using petroleum ether-ethylacetate (7:3) as the eluent. Compound was recrystallized from methanol.

Refinement

H atoms were positioned geometrically, with C—H = 0.93, 0.98, 0.97 and 0.96 Å for aromatic, methine, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A packing diagram of (I). Hydrogen atoms are omited for clarity.

Crystal data

C19H17ClN2OF000 = 680
Mr = 324.80Dx = 1.335 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7082 reflections
a = 8.8659 (4) Åθ = 1.7–25.0º
b = 7.6009 (3) ŵ = 0.24 mm1
c = 24.2026 (10) ÅT = 294 (2) K
β = 97.701 (1)ºPrism, colourless
V = 1616.27 (12) Å30.28 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker APEX2 kappa diffractometer5199 independent reflections
Radiation source: fine-focus sealed tube3858 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 294(2) Kθmax = 31.2º
[var phi] and ω scansθmin = 1.7º
Absorption correction: multi-scan(Blessing, 1995)h = −12→11
Tmin = 0.935, Tmax = 0.953k = −10→11
21338 measured reflectionsl = −35→35

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.138  w = 1/[σ2(Fo2) + (0.0639P)2 + 0.427P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
5199 reflectionsΔρmax = 0.29 e Å3
208 parametersΔρmin = −0.29 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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
Cl10.81942 (5)−0.45073 (7)0.00516 (2)0.06969 (17)
O10.33531 (13)0.11121 (15)0.24679 (4)0.0509 (3)
N10.07255 (13)−0.04341 (16)0.12043 (5)0.0419 (3)
N20.57906 (16)0.1425 (2)0.13922 (7)0.0626 (4)
C20.14526 (17)−0.1758 (2)0.08910 (6)0.0484 (3)
H2A0.1547−0.13430.05180.058*
H2B0.0876−0.28460.08640.058*
C30.30137 (16)−0.20196 (17)0.12296 (5)0.0388 (3)
H30.2894−0.29090.15140.047*
C40.32937 (14)−0.02060 (16)0.15421 (5)0.0336 (2)
C50.32588 (18)−0.04940 (19)0.21657 (5)0.0434 (3)
H5A0.2323−0.10940.22190.052*
H5B0.4103−0.12450.23120.052*
C60.23237 (16)0.23694 (18)0.22598 (5)0.0399 (3)
C70.20691 (19)0.3728 (2)0.26234 (6)0.0511 (4)
H70.25630.37240.29880.061*
C80.1087 (2)0.5073 (2)0.24431 (8)0.0579 (4)
H80.09080.59700.26880.069*
C90.0368 (2)0.5099 (2)0.19038 (8)0.0577 (4)
H9−0.02940.60110.17830.069*
C100.06331 (17)0.3757 (2)0.15411 (6)0.0468 (3)
H100.01610.37950.11740.056*
C110.15891 (14)0.23538 (17)0.17135 (5)0.0352 (3)
C120.19023 (14)0.09239 (17)0.13132 (5)0.0335 (2)
H120.20810.14580.09590.040*
C130.42773 (15)−0.26473 (16)0.09160 (5)0.0366 (3)
C140.44773 (19)−0.2015 (2)0.03930 (6)0.0487 (3)
H140.3799−0.11880.02200.058*
C150.56716 (19)−0.2597 (2)0.01243 (6)0.0502 (4)
H150.5793−0.2168−0.02270.060*
C160.66710 (16)−0.3812 (2)0.03828 (6)0.0443 (3)
C170.64861 (19)−0.4491 (2)0.08934 (7)0.0525 (4)
H170.7159−0.53320.10610.063*
C180.52856 (18)−0.3910 (2)0.11562 (6)0.0469 (3)
H180.5153−0.43770.15020.056*
C190.47093 (15)0.06885 (18)0.14530 (6)0.0405 (3)
C20−0.07204 (18)0.0173 (3)0.09117 (8)0.0615 (5)
H20A−0.11490.10380.11340.092*
H20B−0.1407−0.08040.08460.092*
H20C−0.05600.06850.05620.092*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0478 (2)0.0821 (3)0.0832 (3)0.0010 (2)0.0237 (2)−0.0308 (2)
O10.0589 (6)0.0565 (6)0.0342 (5)0.0075 (5)−0.0052 (4)−0.0084 (4)
N10.0318 (5)0.0495 (7)0.0443 (6)−0.0025 (5)0.0050 (4)−0.0124 (5)
N20.0406 (7)0.0581 (8)0.0890 (11)−0.0015 (6)0.0083 (7)0.0112 (8)
C20.0416 (7)0.0525 (8)0.0515 (8)−0.0031 (6)0.0073 (6)−0.0189 (7)
C30.0421 (7)0.0355 (6)0.0402 (6)0.0001 (5)0.0110 (5)−0.0038 (5)
C40.0324 (6)0.0360 (6)0.0325 (5)0.0017 (5)0.0049 (4)−0.0006 (4)
C50.0511 (8)0.0443 (7)0.0341 (6)0.0052 (6)0.0028 (5)0.0021 (5)
C60.0395 (7)0.0438 (7)0.0371 (6)−0.0040 (5)0.0083 (5)−0.0069 (5)
C70.0539 (9)0.0562 (9)0.0450 (7)−0.0103 (7)0.0130 (6)−0.0184 (6)
C80.0607 (10)0.0504 (8)0.0675 (10)−0.0045 (7)0.0269 (8)−0.0207 (8)
C90.0559 (10)0.0471 (8)0.0736 (11)0.0119 (7)0.0217 (8)−0.0053 (7)
C100.0446 (7)0.0477 (8)0.0490 (7)0.0076 (6)0.0096 (6)−0.0002 (6)
C110.0326 (6)0.0383 (6)0.0357 (6)−0.0011 (5)0.0088 (5)−0.0031 (5)
C120.0316 (5)0.0396 (6)0.0294 (5)0.0025 (5)0.0043 (4)−0.0021 (4)
C130.0407 (7)0.0325 (6)0.0372 (6)0.0011 (5)0.0073 (5)−0.0031 (5)
C140.0540 (8)0.0475 (8)0.0468 (7)0.0123 (7)0.0146 (6)0.0108 (6)
C150.0550 (9)0.0543 (8)0.0442 (7)0.0015 (7)0.0177 (6)0.0032 (6)
C160.0371 (7)0.0453 (7)0.0517 (7)−0.0033 (6)0.0100 (6)−0.0168 (6)
C170.0453 (8)0.0535 (9)0.0573 (9)0.0148 (7)0.0016 (6)0.0003 (7)
C180.0507 (8)0.0507 (8)0.0388 (6)0.0079 (6)0.0043 (6)0.0037 (6)
C190.0346 (6)0.0396 (7)0.0467 (7)0.0047 (5)0.0031 (5)0.0015 (5)
C200.0334 (7)0.0812 (12)0.0671 (10)0.0026 (7)−0.0031 (7)−0.0231 (9)

Geometric parameters (Å, °)

C2—N11.4610 (18)C10—C111.3909 (19)
C2—C31.524 (2)C10—H100.9300
C2—H2A0.9700C11—C121.5063 (17)
C2—H2B0.9700C12—N11.4662 (17)
C3—C131.5122 (18)C12—H120.9800
C3—C41.5760 (18)C13—C181.3852 (19)
C3—H30.9800C13—C141.3873 (18)
C4—C191.4684 (18)C14—C151.387 (2)
C4—C51.5296 (17)C14—H140.9300
C4—C121.5438 (17)C15—C161.372 (2)
C5—O11.4197 (17)C15—H150.9300
C5—H5A0.9700C16—C171.369 (2)
C5—H5B0.9700C16—Cl11.7423 (14)
C6—O11.3700 (18)C17—C181.384 (2)
C6—C111.3935 (18)C17—H170.9300
C6—C71.3945 (19)C18—H180.9300
C7—C81.376 (3)C19—N21.1368 (19)
C7—H70.9300C20—N11.454 (2)
C8—C91.374 (3)C20—H20A0.9600
C8—H80.9300C20—H20B0.9600
C9—C101.386 (2)C20—H20C0.9600
C9—H90.9300
C6—O1—C5114.84 (10)C8—C9—H9120.2
C20—N1—C2112.77 (11)C10—C9—H9120.2
C20—N1—C12115.08 (13)C9—C10—C11121.50 (14)
C2—N1—C12103.02 (10)C11—C10—H10119.2
N1—C2—C3104.05 (11)C10—C11—C6117.81 (12)
N1—C2—H2A110.9C10—C11—C12121.18 (12)
C3—C2—H2A110.9C6—C11—C12120.89 (11)
N1—C2—H2B110.9N1—C12—C11115.81 (10)
C3—C2—H2B110.9N1—C12—C4100.84 (10)
H2A—C2—H2B109.0C11—C12—C4112.20 (10)
C13—C3—C2116.85 (11)N1—C12—H12109.2
C13—C3—C4115.92 (11)C11—C12—H12109.2
C2—C3—C4102.55 (11)C4—C12—H12109.2
C13—C3—H3107.0C18—C13—C14117.95 (13)
C2—C3—H3107.0C18—C13—C3119.19 (12)
C4—C3—H3107.0C14—C13—C3122.86 (12)
C19—C4—C5109.99 (11)C15—C14—C13121.09 (14)
C19—C4—C12110.32 (10)C15—C14—H14119.5
C5—C4—C12108.23 (10)C13—C14—H14119.5
C19—C4—C3114.67 (11)C16—C15—C14119.20 (13)
C5—C4—C3109.00 (10)C16—C15—H15120.4
C12—C4—C3104.33 (10)C14—C15—H15120.4
O1—C5—C4112.18 (11)C17—C16—C15121.16 (13)
O1—C5—H5A109.2C17—C16—Cl1119.66 (12)
C4—C5—H5A109.2C15—C16—Cl1119.18 (12)
O1—C5—H5B109.2C16—C17—C18119.15 (14)
C4—C5—H5B109.2C16—C17—H17120.4
H5A—C5—H5B107.9C18—C17—H17120.4
O1—C6—C11123.13 (11)C17—C18—C13121.41 (14)
O1—C6—C7116.14 (12)C17—C18—H18119.3
C11—C6—C7120.70 (14)C13—C18—H18119.3
C8—C7—C6119.94 (14)N2—C19—C4177.88 (17)
C8—C7—H7120.0N1—C20—H20A109.5
C6—C7—H7120.0N1—C20—H20B109.5
C9—C8—C7120.36 (14)H20A—C20—H20B109.5
C9—C8—H8119.8N1—C20—H20C109.5
C7—C8—H8119.8H20A—C20—H20C109.5
C8—C9—C10119.64 (16)H20B—C20—H20C109.5
N1—C2—C3—C13−153.76 (12)C3—C4—C12—N131.53 (11)
N1—C2—C3—C4−25.83 (14)C19—C4—C12—C11−80.99 (13)
C13—C3—C4—C194.02 (16)C5—C4—C12—C1139.40 (14)
C2—C3—C4—C19−124.49 (12)C3—C4—C12—C11155.38 (10)
C13—C3—C4—C5−119.76 (12)C2—C3—C13—C18−138.60 (14)
C2—C3—C4—C5111.72 (12)C4—C3—C13—C18100.27 (15)
C13—C3—C4—C12124.80 (12)C2—C3—C13—C1441.3 (2)
C2—C3—C4—C12−3.72 (13)C4—C3—C13—C14−79.83 (17)
C19—C4—C5—O159.31 (15)C18—C13—C14—C15−1.5 (2)
C12—C4—C5—O1−61.28 (15)C3—C13—C14—C15178.56 (14)
C3—C4—C5—O1−174.18 (11)C13—C14—C15—C16−0.2 (3)
O1—C6—C7—C8178.08 (14)C14—C15—C16—C171.7 (2)
C11—C6—C7—C8−0.2 (2)C14—C15—C16—Cl1−178.65 (13)
C6—C7—C8—C9−0.8 (2)C15—C16—C17—C18−1.3 (2)
C7—C8—C9—C100.2 (3)Cl1—C16—C17—C18179.04 (12)
C8—C9—C10—C111.5 (3)C16—C17—C18—C13−0.5 (2)
C9—C10—C11—C6−2.4 (2)C14—C13—C18—C171.9 (2)
C9—C10—C11—C12−178.46 (14)C3—C13—C18—C17−178.16 (14)
O1—C6—C11—C10−176.39 (13)C3—C2—N1—C20172.67 (14)
C7—C6—C11—C101.7 (2)C3—C2—N1—C1247.99 (14)
O1—C6—C11—C12−0.3 (2)C11—C12—N1—C2066.39 (15)
C7—C6—C11—C12177.82 (12)C4—C12—N1—C20−172.28 (11)
C10—C11—C12—N1−80.29 (16)C11—C12—N1—C2−170.45 (11)
C6—C11—C12—N1103.76 (14)C4—C12—N1—C2−49.13 (12)
C10—C11—C12—C4164.69 (12)C11—C6—O1—C5−20.14 (19)
C6—C11—C12—C4−11.26 (17)C7—C6—O1—C5161.65 (13)
C19—C4—C12—N1155.17 (10)C4—C5—O1—C651.71 (16)
C5—C4—C12—N1−84.44 (12)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2395).

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