supplementary materials


pk2493 scheme

Acta Cryst. (2013). E69, o1513    [ doi:10.1107/S1600536813023489 ]

(6,6-Dimethyl-1-phenyl-6,7-dihydro-5H-pyrrolizin-2-yl)(thiophen-2-yl)methanone

Y. Liu, J. Zhong, W. Sun, F. Zhang and H. Liu

Abstract top

In the title compound, C20H19NOS, the pyrrolizine ring is essentially planar (r.m.s. deviation = 0.001 Å) while the fused dihydro-pyrrolizine ring adopts an envelope comformation with the C atom bearing the methyl substituents as the flap. The dihedral angles between the pyrrolizine and the phenyl and thiophene rings are 34.54 (7) and 44.93 (7)°, respectively. In the crystal, weak C-H...O hydrogen bonds link the molecules into infinite zigzag chains parallel to the b-axis direction.

Comment top

The title compound, (I) (Fig. 1), 6-(2-thenoyl-)-7-phenyl-2,2-dimethyl- 2,3-dihydro-1H-pyrrolizine was synthesized from 5-phenyl- 3,3-dimethyl-3,4-dihydro-1H-pyrrolizine and 3-bromo-2-thenoylethanone according to a general literature of Dannhardt et al. (1979).

Compared with the structure of C20H17ON (Liu et al., 2007), the thenoyl group results in a larger calculated density for the crystal. The 2,3-dihydro-1H-pyrrolizine ring A (C1/C2/C3/N4 /C5/C6/C7/C8) adopts an almost planar conformation except the carbon atom which links to the methyl groups, with the mean deviation from the least-squares plane being 0.1064 Å, The dihedral angle between the pyrrolizine and phenyl rings (C14—C19) is 34.54 (7)°, the dihedral angle between pyrrolizine and thiophene rings (C10/C11/C12/C13/S1) is 44.93 (7)°, and the dihedral angle between phenyl and thiophene rings is 68.72 (6)°.

In the crystal, weak intermolecular C—H···O (Table 1) hydrogen bonds can be found, linking adjacent molecules along the b axis to form one-dimensional zigzag chains, which contributes to the stable packing of molecules in the crystal. No π-π stacking interactions were found in this crystal structure.

Related literature top

For the synthesis of the title compound, see: Dannhardt & Obergrusberger (1979). For a similar structure, see: Liu et al. (2007).

Experimental top

A stirred solution of 5-phenyl-3,3-dimethyl-3,4-dihydro-1H-pyrrolizine in CH2Cl2 was treated with a solution of 3-bromo-2-thenoylethanone. The mixture was stirred for 4 h at room temperature, an aqueous solution of NaHCO3 was added and stirred for 3 h. Then water was added to form a clear aqueous layer, the organic layer was separated and dried (anhydrous Na2SO4) before the solvent was evaporated. The solution was evaporated under reduced pressure and purified by chromatography on a silica gel column, eluting with a petroleum ether/acetone mixture to give 32% yield of light yellow solid. The purity of the title compound was verified by elemental analysis: calculated for C20H19NOS: C 74.73, H 5.96, N 4.36; found C 74.59, H 5.98, N 4.35. EI—MS m/z: 322(M+H)+.

The crystal appropriate for X-ray data collection was obtained from DMF-H2O solution at room temperature after about a week.

Refinement top

All H atoms were placed in geometically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 (0.97 for CH2)Å for CH, and Uiso(H) = 1.2 (1.5 for CH3) Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) showing displacement ellipsoids drawn at the 30% probability level.
(6,6-Dimethyl-1-phenyl-6,7-dihydro-5H-pyrrolizin-2-yl)(thiophen-2-yl)methanone top
Crystal data top
C20H19NOSF(000) = 1360
Mr = 321.42Dx = 1.256 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 17698 reflections
a = 16.251 (3) Åθ = 3.1–27.5°
b = 10.473 (2) ŵ = 0.19 mm1
c = 19.973 (4) ÅT = 296 K
V = 3399.3 (11) Å3Prismatic, colorless
Z = 80.22 × 0.19 × 0.12 mm
Data collection top
Bruker APEXII CCD
diffractometer
2743 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.070
Graphite monochromatorθmax = 27.5°, θmin = 3.1°
φ and ω scansh = 2120
30107 measured reflectionsk = 1313
3894 independent reflectionsl = 2525
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)] = 0.046H-atom parameters constrained
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0601P)2 + 0.6291P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3894 reflectionsΔρmax = 0.20 e Å3
209 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0049 (11)
Crystal data top
C20H19NOSV = 3399.3 (11) Å3
Mr = 321.42Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 16.251 (3) ŵ = 0.19 mm1
b = 10.473 (2) ÅT = 296 K
c = 19.973 (4) Å0.22 × 0.19 × 0.12 mm
Data collection top
Bruker APEXII CCD
diffractometer
2743 reflections with I > 2σ(I)
30107 measured reflectionsRint = 0.070
3894 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.131Δρmax = 0.20 e Å3
S = 1.03Δρmin = 0.25 e Å3
3894 reflectionsAbsolute structure: ?
209 parametersAbsolute structure 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
S10.20601 (3)0.94554 (5)0.16441 (3)0.0689 (2)
N40.05241 (9)0.72368 (14)0.07701 (7)0.0509 (4)
O10.06950 (8)0.76239 (12)0.14671 (6)0.0612 (4)
C10.06376 (11)0.60225 (16)0.10279 (8)0.0492 (4)
H1A0.12190.62320.10190.059*
H1B0.05730.51080.09710.059*
C20.02331 (12)0.64795 (16)0.16906 (8)0.0494 (4)
C30.06294 (12)0.6923 (2)0.14784 (9)0.0597 (5)
H3A0.10310.62470.15370.072*
H3B0.08010.76650.17330.072*
C50.09527 (12)0.78755 (17)0.02986 (9)0.0542 (4)
H5A0.14510.82940.03610.065*
C60.05165 (10)0.77953 (16)0.02961 (8)0.0471 (4)
C70.02153 (10)0.70597 (15)0.01645 (8)0.0434 (4)
C80.01806 (10)0.67366 (15)0.05008 (8)0.0442 (4)
C90.08533 (11)0.81958 (16)0.09447 (9)0.0484 (4)
C100.14245 (11)0.92911 (17)0.09620 (9)0.0524 (4)
C110.15343 (13)1.02868 (18)0.05123 (10)0.0645 (5)
H11A0.12371.03830.01170.077*
C120.21582 (15)1.1140 (2)0.07320 (14)0.0796 (7)
H12A0.23201.18600.04930.096*
C130.24891 (14)1.0797 (2)0.13224 (15)0.0806 (7)
H13A0.29091.12480.15320.097*
C140.09238 (10)0.67833 (16)0.06018 (8)0.0461 (4)
C150.13925 (11)0.56785 (18)0.04985 (9)0.0569 (5)
H15A0.12430.51130.01610.068*
C160.20727 (12)0.5415 (2)0.08900 (11)0.0722 (6)
H16A0.23770.46780.08130.087*
C170.22995 (12)0.6230 (3)0.13876 (11)0.0808 (8)
H17A0.27510.60390.16560.097*
C180.18603 (13)0.7339 (3)0.14950 (10)0.0761 (7)
H18A0.20250.79030.18290.091*
C190.11707 (11)0.7617 (2)0.11052 (9)0.0592 (5)
H19A0.08750.83630.11820.071*
C200.01924 (18)0.5406 (2)0.22061 (11)0.0838 (7)
H20A0.00610.57180.26090.126*
H20B0.07390.51140.23050.126*
H20C0.01270.47120.20300.126*
C210.07040 (13)0.76133 (19)0.19715 (10)0.0665 (5)
H21A0.04500.78900.23800.100*
H21B0.06970.82990.16530.100*
H21C0.12630.73670.20590.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0568 (3)0.0595 (3)0.0903 (4)0.0037 (2)0.0164 (3)0.0125 (3)
N40.0503 (8)0.0583 (9)0.0442 (8)0.0047 (7)0.0079 (6)0.0023 (7)
O10.0671 (9)0.0656 (8)0.0510 (7)0.0096 (7)0.0037 (6)0.0062 (6)
C10.0562 (10)0.0472 (9)0.0441 (9)0.0030 (8)0.0003 (7)0.0017 (7)
C20.0630 (11)0.0439 (9)0.0412 (9)0.0014 (8)0.0037 (8)0.0021 (7)
C30.0573 (11)0.0773 (13)0.0446 (10)0.0031 (10)0.0102 (8)0.0047 (9)
C50.0503 (10)0.0589 (10)0.0534 (10)0.0108 (8)0.0017 (8)0.0029 (8)
C60.0488 (9)0.0461 (9)0.0464 (9)0.0030 (7)0.0019 (7)0.0029 (7)
C70.0457 (9)0.0418 (8)0.0427 (8)0.0019 (7)0.0032 (7)0.0047 (7)
C80.0457 (9)0.0434 (8)0.0436 (9)0.0001 (7)0.0033 (7)0.0055 (7)
C90.0477 (9)0.0484 (9)0.0491 (10)0.0014 (8)0.0009 (8)0.0011 (8)
C100.0477 (10)0.0490 (9)0.0605 (11)0.0021 (8)0.0036 (8)0.0086 (8)
C110.0735 (13)0.0483 (10)0.0716 (13)0.0088 (9)0.0124 (10)0.0058 (9)
C120.0830 (16)0.0533 (12)0.1026 (18)0.0138 (11)0.0246 (14)0.0115 (12)
C130.0539 (12)0.0616 (13)0.126 (2)0.0075 (10)0.0059 (14)0.0283 (14)
C140.0432 (9)0.0569 (10)0.0382 (8)0.0063 (8)0.0021 (7)0.0100 (7)
C150.0527 (10)0.0629 (11)0.0552 (10)0.0034 (9)0.0019 (8)0.0143 (9)
C160.0492 (11)0.0956 (16)0.0717 (13)0.0099 (11)0.0008 (10)0.0301 (12)
C170.0427 (11)0.139 (2)0.0613 (13)0.0102 (14)0.0061 (9)0.0335 (15)
C180.0584 (12)0.126 (2)0.0443 (11)0.0307 (14)0.0038 (9)0.0037 (12)
C190.0518 (10)0.0795 (13)0.0463 (10)0.0127 (10)0.0005 (8)0.0003 (9)
C200.130 (2)0.0623 (13)0.0588 (12)0.0102 (13)0.0248 (13)0.0127 (10)
C210.0714 (13)0.0656 (12)0.0625 (12)0.0036 (10)0.0002 (10)0.0190 (10)
Geometric parameters (Å, º) top
S1—C131.695 (3)C11—C121.421 (3)
S1—C101.7182 (19)C11—H11A0.9300
N4—C51.349 (2)C12—C131.345 (3)
N4—C81.370 (2)C12—H12A0.9300
N4—C31.462 (2)C13—H13A0.9300
O1—C91.230 (2)C14—C191.391 (3)
C1—C81.490 (2)C14—C151.401 (3)
C1—C21.553 (2)C15—C161.382 (3)
C1—H1A0.9700C15—H15A0.9300
C1—H1B0.9700C16—C171.361 (3)
C2—C211.520 (2)C16—H16A0.9300
C2—C201.526 (2)C17—C181.380 (4)
C2—C31.536 (3)C17—H17A0.9300
C3—H3A0.9700C18—C191.395 (3)
C3—H3B0.9700C18—H18A0.9300
C5—C61.386 (2)C19—H19A0.9300
C5—H5A0.9300C20—H20A0.9600
C6—C71.441 (2)C20—H20B0.9600
C6—C91.468 (2)C20—H20C0.9600
C7—C81.372 (2)C21—H21A0.9600
C7—C141.474 (2)C21—H21B0.9600
C9—C101.476 (2)C21—H21C0.9600
C10—C111.388 (3)
C13—S1—C1091.71 (12)C10—C11—C12111.4 (2)
C5—N4—C8110.32 (14)C10—C11—H11A124.3
C5—N4—C3136.60 (15)C12—C11—H11A124.3
C8—N4—C3113.07 (14)C13—C12—C11112.8 (2)
C8—C1—C2103.68 (14)C13—C12—H12A123.6
C8—C1—H1A111.0C11—C12—H12A123.6
C2—C1—H1A111.0C12—C13—S1112.92 (18)
C8—C1—H1B111.0C12—C13—H13A123.5
C2—C1—H1B111.0S1—C13—H13A123.5
H1A—C1—H1B109.0C19—C14—C15117.93 (17)
C21—C2—C20110.38 (17)C19—C14—C7122.04 (16)
C21—C2—C3108.98 (15)C15—C14—C7119.98 (15)
C20—C2—C3111.67 (17)C16—C15—C14121.1 (2)
C21—C2—C1110.00 (15)C16—C15—H15A119.5
C20—C2—C1111.50 (15)C14—C15—H15A119.5
C3—C2—C1104.13 (13)C17—C16—C15120.3 (2)
N4—C3—C2103.18 (14)C17—C16—H16A119.8
N4—C3—H3A111.1C15—C16—H16A119.8
C2—C3—H3A111.1C16—C17—C18120.1 (2)
N4—C3—H3B111.1C16—C17—H17A120.0
C2—C3—H3B111.1C18—C17—H17A120.0
H3A—C3—H3B109.1C17—C18—C19120.3 (2)
N4—C5—C6107.72 (15)C17—C18—H18A119.9
N4—C5—H5A126.1C19—C18—H18A119.9
C6—C5—H5A126.1C14—C19—C18120.3 (2)
C5—C6—C7107.35 (15)C14—C19—H19A119.9
C5—C6—C9123.27 (16)C18—C19—H19A119.9
C7—C6—C9128.43 (15)C2—C20—H20A109.5
C8—C7—C6105.94 (14)C2—C20—H20B109.5
C8—C7—C14123.88 (15)H20A—C20—H20B109.5
C6—C7—C14129.90 (15)C2—C20—H20C109.5
N4—C8—C7108.68 (15)H20A—C20—H20C109.5
N4—C8—C1109.35 (14)H20B—C20—H20C109.5
C7—C8—C1141.97 (15)C2—C21—H21A109.5
O1—C9—C6122.11 (16)C2—C21—H21B109.5
O1—C9—C10119.34 (16)H21A—C21—H21B109.5
C6—C9—C10118.51 (15)C2—C21—H21C109.5
C11—C10—C9130.52 (17)H21A—C21—H21C109.5
C11—C10—S1111.14 (14)H21B—C21—H21C109.5
C9—C10—S1118.32 (13)
C8—C1—C2—C2192.43 (17)C7—C6—C9—O123.5 (3)
C8—C1—C2—C20144.77 (18)C5—C6—C9—C1033.8 (3)
C8—C1—C2—C324.22 (18)C7—C6—C9—C10158.85 (16)
C5—N4—C3—C2165.6 (2)O1—C9—C10—C11160.14 (19)
C8—N4—C3—C216.3 (2)C6—C9—C10—C1122.1 (3)
C21—C2—C3—N492.99 (17)O1—C9—C10—S117.9 (2)
C20—C2—C3—N4144.81 (16)C6—C9—C10—S1159.86 (13)
C1—C2—C3—N424.36 (18)C13—S1—C10—C111.90 (15)
C8—N4—C5—C60.2 (2)C13—S1—C10—C9179.73 (15)
C3—N4—C5—C6178.29 (19)C9—C10—C11—C12179.87 (18)
N4—C5—C6—C70.1 (2)S1—C10—C11—C121.8 (2)
N4—C5—C6—C9169.72 (16)C10—C11—C12—C130.6 (3)
C5—C6—C7—C80.02 (19)C11—C12—C13—S10.8 (3)
C9—C6—C7—C8168.92 (17)C10—S1—C13—C121.57 (19)
C5—C6—C7—C14173.97 (16)C8—C7—C14—C19144.22 (17)
C9—C6—C7—C1417.1 (3)C6—C7—C14—C1928.8 (3)
C5—N4—C8—C70.2 (2)C8—C7—C14—C1533.1 (2)
C3—N4—C8—C7178.78 (15)C6—C7—C14—C15153.90 (17)
C5—N4—C8—C1179.28 (15)C19—C14—C15—C160.8 (3)
C3—N4—C8—C10.7 (2)C7—C14—C15—C16178.23 (16)
C6—C7—C8—N40.11 (18)C14—C15—C16—C170.2 (3)
C14—C7—C8—N4174.33 (14)C15—C16—C17—C181.4 (3)
C6—C7—C8—C1179.0 (2)C16—C17—C18—C191.5 (3)
C14—C7—C8—C16.5 (3)C15—C14—C19—C180.7 (3)
C2—C1—C8—N415.16 (18)C7—C14—C19—C18178.01 (16)
C2—C1—C8—C7165.7 (2)C17—C18—C19—C140.5 (3)
C5—C6—C9—O1143.84 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1i0.932.693.529 (3)150
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1i0.932.693.529 (3)150.4
Symmetry code: (i) x+1/2, y+1/2, z.
references
References top

Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dannhardt, G. & Obergrusberger, R. (1979). Arch. Pharm. 312, 896–907.

Liu, Y., Hu, Y., Li, X. & Chen, W. (2007). Acta Cryst. E63, o1106–o1107.

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