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organic compounds
2,3-Dihydro-1H-pyrrolizin-1-one
aPharmaceutical Research Center, PCSIR Laboratories Complex, Karachi 75280, Pakistan, and bDepartment of Pharmaceutical Engineering, Biotechnology College, Tianjin University of Science and Technology, Tianjin 300457, People's Republic of China
*Correspondence e-mail: usfle8pcsir@yahoo.com
There are two nearly identical molecules in the 7H7NO. The molecules are nearly planar (r.m.s. deviations of 0.025 and 0.017 Å) and oriented at a dihedral angle of 28.98 (3)°. The two molecules are linked by a C—H⋯O hydrogen bond. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into zigzag chains along the c axis.
of the title compound, CRelated literature
For general background to 2,3-dihydropyrrolizine derivatives and their biological activity, see: Skvortsov & Astakhova (1992). For the preparation, see: Braunholtz et al. (1962
); Clemo & Ramage (1931
). For natural sources, see: Meinwald & Meinwald (1965
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEP-3 (Farrugia, 1997
); software used to prepare material for publication: publCIF (Westrip, 2010
).
Supporting information
10.1107/S1600536810034902/bq2209sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810034902/bq2209Isup2.hkl
The preparation of title compound was carried out as described in the procedure reported in literature (Braunholtz et al., 1962). Purified by Flash
Petroleum Ether:Ethyl Acetate = 3:1.All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.95 and 0.99Å for aromatic and methylene respectively. Uiso(H) values were taken to be equal to 1.2 Ueq(C) for all hydrogen atoms.
Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell
CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010). ![]() | Fig. 1. Displacement ellipsoid plot (80% probability level) showing atom numbering scheme. |
![]() | Fig. 2. The packing showing the zigzg chains. Dashed lines indicate hydrogen bonds |
C7H7NO | F(000) = 512 |
Mr = 121.14 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/c | Melting point: 327(1) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71075 Å |
a = 11.301 (1) Å | Cell parameters from 3403 reflections |
b = 7.1730 (7) Å | θ = 1.8–28.1° |
c = 14.3760 (16) Å | µ = 0.09 mm−1 |
β = 90.989 (5)° | T = 113 K |
V = 1165.2 (2) Å3 | Prism, colorless |
Z = 8 | 0.12 × 0.06 × 0.04 mm |
Rigaku Saturn724 CCD camera diffractometer | 2284 independent reflections |
Radiation source: rotating anode | 2003 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.051 |
ω scans | θmax = 26.0°, θmin = 1.8° |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009) | h = −13→13 |
Tmin = 0.989, Tmax = 0.996 | k = −8→8 |
10183 measured reflections | l = −17→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.043P)2 + 0.3505P] where P = (Fo2 + 2Fc2)/3 |
2284 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C7H7NO | V = 1165.2 (2) Å3 |
Mr = 121.14 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.301 (1) Å | µ = 0.09 mm−1 |
b = 7.1730 (7) Å | T = 113 K |
c = 14.3760 (16) Å | 0.12 × 0.06 × 0.04 mm |
β = 90.989 (5)° |
Rigaku Saturn724 CCD camera diffractometer | 2284 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009) | 2003 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.996 | Rint = 0.051 |
10183 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.19 e Å−3 |
2284 reflections | Δρmin = −0.30 e Å−3 |
163 parameters |
Experimental. Single crystals suitable for X-ray crystallography were grown by slow cooling of a hot saturated solution of Petroleum Ether. |
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 RSHELXS-97 -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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.84120 (12) | 0.0832 (2) | 0.57308 (9) | 0.0293 (4) | |
O2 | 0.49964 (11) | 0.0828 (2) | 0.17318 (10) | 0.0329 (4) | |
N1 | 0.72173 (13) | 0.1521 (2) | 0.35032 (11) | 0.0181 (4) | |
N2 | 0.20229 (13) | 0.1557 (2) | 0.11650 (11) | 0.0190 (4) | |
C1 | 0.78107 (17) | 0.0987 (3) | 0.50200 (13) | 0.0214 (4) | |
C2 | 0.64640 (16) | 0.0776 (3) | 0.49734 (13) | 0.0229 (5) | |
H2A | 0.6086 | 0.1646 | 0.5413 | 0.027* | |
H2B | 0.6233 | −0.0513 | 0.5136 | 0.027* | |
C3 | 0.60795 (16) | 0.1231 (3) | 0.39650 (13) | 0.0222 (4) | |
H3A | 0.5634 | 0.0183 | 0.3680 | 0.027* | |
H3B | 0.5586 | 0.2371 | 0.3938 | 0.027* | |
C4 | 0.81910 (16) | 0.1386 (3) | 0.40853 (13) | 0.0186 (4) | |
C5 | 0.91883 (17) | 0.1737 (3) | 0.35603 (13) | 0.0226 (4) | |
H5 | 0.9988 | 0.1728 | 0.3775 | 0.027* | |
C6 | 0.87834 (16) | 0.2109 (3) | 0.26502 (13) | 0.0218 (4) | |
H6 | 0.9265 | 0.2405 | 0.2136 | 0.026* | |
C7 | 0.75535 (16) | 0.1968 (3) | 0.26317 (13) | 0.0209 (4) | |
H7 | 0.7046 | 0.2152 | 0.2106 | 0.025* | |
C8 | 0.39292 (16) | 0.1181 (3) | 0.16955 (14) | 0.0219 (4) | |
C9 | 0.32016 (16) | 0.1840 (3) | 0.25181 (13) | 0.0223 (4) | |
H9A | 0.3490 | 0.3065 | 0.2743 | 0.027* | |
H9B | 0.3260 | 0.0934 | 0.3036 | 0.027* | |
C10 | 0.19132 (16) | 0.1993 (3) | 0.21584 (13) | 0.0208 (4) | |
H10A | 0.1395 | 0.1084 | 0.2472 | 0.025* | |
H10B | 0.1596 | 0.3265 | 0.2250 | 0.025* | |
C11 | 0.31432 (15) | 0.1065 (3) | 0.09001 (13) | 0.0186 (4) | |
C12 | 0.30999 (17) | 0.0643 (3) | −0.00456 (14) | 0.0223 (4) | |
H12 | 0.3741 | 0.0258 | −0.0419 | 0.027* | |
C13 | 0.19207 (17) | 0.0901 (3) | −0.03344 (14) | 0.0239 (5) | |
H13 | 0.1615 | 0.0721 | −0.0948 | 0.029* | |
C14 | 0.12721 (17) | 0.1468 (3) | 0.04322 (14) | 0.0238 (5) | |
H14 | 0.0450 | 0.1741 | 0.0435 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0349 (8) | 0.0343 (9) | 0.0185 (8) | 0.0044 (6) | −0.0039 (6) | −0.0005 (6) |
O2 | 0.0195 (7) | 0.0467 (10) | 0.0324 (9) | 0.0055 (6) | −0.0011 (6) | −0.0079 (7) |
N1 | 0.0169 (7) | 0.0209 (8) | 0.0165 (8) | 0.0002 (6) | 0.0003 (6) | −0.0004 (7) |
N2 | 0.0187 (8) | 0.0195 (9) | 0.0188 (9) | 0.0013 (6) | 0.0020 (7) | −0.0012 (7) |
C1 | 0.0263 (10) | 0.0175 (10) | 0.0203 (11) | 0.0021 (8) | −0.0006 (8) | −0.0020 (8) |
C2 | 0.0280 (10) | 0.0213 (10) | 0.0196 (10) | −0.0017 (8) | 0.0044 (8) | 0.0000 (8) |
C3 | 0.0179 (9) | 0.0247 (10) | 0.0241 (11) | −0.0019 (8) | 0.0032 (8) | 0.0006 (8) |
C4 | 0.0198 (9) | 0.0198 (10) | 0.0160 (10) | 0.0012 (7) | −0.0031 (8) | −0.0022 (8) |
C5 | 0.0189 (9) | 0.0254 (10) | 0.0233 (11) | −0.0002 (8) | −0.0016 (8) | −0.0033 (9) |
C6 | 0.0224 (10) | 0.0237 (10) | 0.0193 (10) | −0.0013 (8) | 0.0032 (8) | −0.0003 (8) |
C7 | 0.0238 (10) | 0.0227 (10) | 0.0161 (10) | 0.0015 (8) | −0.0015 (8) | 0.0016 (8) |
C8 | 0.0207 (9) | 0.0200 (10) | 0.0249 (11) | −0.0004 (8) | 0.0007 (8) | 0.0004 (8) |
C9 | 0.0230 (10) | 0.0251 (10) | 0.0187 (10) | −0.0004 (8) | 0.0007 (8) | −0.0008 (8) |
C10 | 0.0222 (10) | 0.0228 (10) | 0.0177 (10) | 0.0015 (8) | 0.0043 (8) | −0.0020 (8) |
C11 | 0.0190 (9) | 0.0183 (10) | 0.0184 (10) | 0.0016 (7) | 0.0030 (8) | 0.0000 (8) |
C12 | 0.0267 (10) | 0.0199 (10) | 0.0204 (10) | 0.0004 (8) | 0.0039 (8) | −0.0003 (8) |
C13 | 0.0307 (11) | 0.0233 (11) | 0.0176 (10) | 0.0011 (8) | −0.0024 (8) | 0.0005 (8) |
C14 | 0.0222 (10) | 0.0244 (11) | 0.0246 (11) | 0.0008 (8) | −0.0044 (8) | 0.0001 (9) |
O1—C1 | 1.222 (2) | C5—H5 | 0.9500 |
O2—C8 | 1.232 (2) | C6—C7 | 1.393 (2) |
N1—C7 | 1.354 (2) | C6—H6 | 0.9500 |
N1—C4 | 1.374 (2) | C7—H7 | 0.9500 |
N1—C3 | 1.472 (2) | C8—C11 | 1.438 (3) |
N2—C14 | 1.343 (2) | C8—C9 | 1.527 (3) |
N2—C11 | 1.374 (2) | C9—C10 | 1.541 (3) |
N2—C10 | 1.469 (2) | C9—H9A | 0.9900 |
C1—C4 | 1.446 (3) | C9—H9B | 0.9900 |
C1—C2 | 1.530 (3) | C10—H10A | 0.9900 |
C2—C3 | 1.541 (3) | C10—H10B | 0.9900 |
C2—H2A | 0.9900 | C11—C12 | 1.393 (3) |
C2—H2B | 0.9900 | C12—C13 | 1.401 (3) |
C3—H3A | 0.9900 | C12—H12 | 0.9500 |
C3—H3B | 0.9900 | C13—C14 | 1.395 (3) |
C4—C5 | 1.390 (3) | C13—H13 | 0.9500 |
C5—C6 | 1.404 (3) | C14—H14 | 0.9500 |
C7—N1—C4 | 110.21 (16) | N1—C7—C6 | 107.17 (17) |
C7—N1—C3 | 135.39 (16) | N1—C7—H7 | 126.4 |
C4—N1—C3 | 114.33 (15) | C6—C7—H7 | 126.4 |
C14—N2—C11 | 110.07 (16) | O2—C8—C11 | 127.76 (18) |
C14—N2—C10 | 135.23 (16) | O2—C8—C9 | 124.78 (18) |
C11—N2—C10 | 114.68 (15) | C11—C8—C9 | 107.47 (15) |
O1—C1—C4 | 128.66 (18) | C8—C9—C10 | 106.29 (15) |
O1—C1—C2 | 124.46 (18) | C8—C9—H9A | 110.5 |
C4—C1—C2 | 106.88 (16) | C10—C9—H9A | 110.5 |
C1—C2—C3 | 106.52 (15) | C8—C9—H9B | 110.5 |
C1—C2—H2A | 110.4 | C10—C9—H9B | 110.5 |
C3—C2—H2A | 110.4 | H9A—C9—H9B | 108.7 |
C1—C2—H2B | 110.4 | N2—C10—C9 | 102.47 (14) |
C3—C2—H2B | 110.4 | N2—C10—H10A | 111.3 |
H2A—C2—H2B | 108.6 | C9—C10—H10A | 111.3 |
N1—C3—C2 | 102.70 (14) | N2—C10—H10B | 111.3 |
N1—C3—H3A | 111.2 | C9—C10—H10B | 111.3 |
C2—C3—H3A | 111.2 | H10A—C10—H10B | 109.2 |
N1—C3—H3B | 111.2 | N2—C11—C12 | 108.01 (16) |
C2—C3—H3B | 111.2 | N2—C11—C8 | 108.92 (16) |
H3A—C3—H3B | 109.1 | C12—C11—C8 | 143.08 (18) |
N1—C4—C5 | 107.75 (16) | C11—C12—C13 | 106.13 (17) |
N1—C4—C1 | 109.38 (16) | C11—C12—H12 | 126.9 |
C5—C4—C1 | 142.83 (17) | C13—C12—H12 | 126.9 |
C4—C5—C6 | 106.62 (16) | C14—C13—C12 | 108.33 (17) |
C4—C5—H5 | 126.7 | C14—C13—H13 | 125.8 |
C6—C5—H5 | 126.7 | C12—C13—H13 | 125.8 |
C7—C6—C5 | 108.24 (17) | N2—C14—C13 | 107.47 (17) |
C7—C6—H6 | 125.9 | N2—C14—H14 | 126.3 |
C5—C6—H6 | 125.9 | C13—C14—H14 | 126.3 |
O1—C1—C2—C3 | 175.74 (18) | O2—C8—C9—C10 | −176.94 (19) |
C4—C1—C2—C3 | −4.4 (2) | C11—C8—C9—C10 | 3.2 (2) |
C7—N1—C3—C2 | −179.46 (19) | C14—N2—C10—C9 | −178.40 (19) |
C4—N1—C3—C2 | −2.6 (2) | C11—N2—C10—C9 | 3.8 (2) |
C1—C2—C3—N1 | 4.14 (19) | C8—C9—C10—N2 | −4.05 (19) |
C7—N1—C4—C5 | −0.8 (2) | C14—N2—C11—C12 | 0.0 (2) |
C3—N1—C4—C5 | −178.45 (15) | C10—N2—C11—C12 | 178.29 (15) |
C7—N1—C4—C1 | 177.53 (15) | C14—N2—C11—C8 | 179.72 (15) |
C3—N1—C4—C1 | −0.1 (2) | C10—N2—C11—C8 | −2.0 (2) |
O1—C1—C4—N1 | −177.28 (18) | O2—C8—C11—N2 | 179.24 (19) |
C2—C1—C4—N1 | 2.8 (2) | C9—C8—C11—N2 | −0.9 (2) |
O1—C1—C4—C5 | 0.1 (4) | O2—C8—C11—C12 | −1.2 (4) |
C2—C1—C4—C5 | −179.7 (2) | C9—C8—C11—C12 | 178.7 (2) |
N1—C4—C5—C6 | 0.7 (2) | N2—C11—C12—C13 | 0.1 (2) |
C1—C4—C5—C6 | −176.7 (2) | C8—C11—C12—C13 | −179.6 (2) |
C4—C5—C6—C7 | −0.4 (2) | C11—C12—C13—C14 | −0.1 (2) |
C4—N1—C7—C6 | 0.6 (2) | C11—N2—C14—C13 | 0.0 (2) |
C3—N1—C7—C6 | 177.51 (19) | C10—N2—C14—C13 | −177.84 (19) |
C5—C6—C7—N1 | −0.1 (2) | C12—C13—C14—N2 | 0.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.95 | 2.55 | 3.151 (2) | 121 |
C7—H7···O2 | 0.95 | 2.55 | 3.250 (2) | 130 |
C12—H12···O2ii | 0.95 | 2.51 | 3.435 (2) | 165 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C7H7NO |
Mr | 121.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 113 |
a, b, c (Å) | 11.301 (1), 7.1730 (7), 14.3760 (16) |
β (°) | 90.989 (5) |
V (Å3) | 1165.2 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.12 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Rigaku Saturn724 CCD camera diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2009) |
Tmin, Tmax | 0.989, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10183, 2284, 2003 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.118, 1.16 |
No. of reflections | 2284 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.30 |
Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.95 | 2.55 | 3.151 (2) | 121 |
C7—H7···O2 | 0.95 | 2.55 | 3.250 (2) | 130 |
C12—H12···O2ii | 0.95 | 2.51 | 3.435 (2) | 165 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z. |
Acknowledgements
YA is grateful to the Pakistan Council of Scientific & Industrial Research, Ministry of Science & Technology, Government of Pakistan, for financial support. PY is grateful to Tianjin University of Science & Technology for research funding (research grant No. 2009 0431).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Derivatives of 2,3-dihydropyrrolizine became known through studies of their synthesis (Clemo et al., 1931) and isolation from natural source (Meinwald et al., 1965). Synthetic dihydropyrrolizines that are of interest as pharmaceuticals have been reported. The most important of these, Ketorolac, is a non steroid analgesic. Depending on their structure, derivatives of 2,3-dihydropyrrolizine have shown merit as analgesics, anti-inflammatory agents, myorelaxants, inhibitors of thrombocyte aggregation, fibrinolytics, temperature-lowering substances and drugs for the treatment of glaucoma and conjunctivitis (Skvortsov et al., 1992).
The ORTEP (Farrugia, 1997) drawing of the molecule is shown in Fig. 1. The sums of the three angles at N1 and C4 are 359.93 and 359.96 respectively, indicating that two rings are almost planer with an r.m.s. deviation of 0.05 Å. Molecules are held together in crystal packing by weak C—H···O hydrogen bonds (Table 1), in the form of zigzag infinite one dimensional polymeric chains (Fig. 2.).