organic compounds
5-(Diphenylmethylidene)pyrrolidin-2-one
aDepartment of Applied Cosmetology and Graduate Institute of Cosmetic Science, Hungkuang University, Taichung 433, Taiwan, and bDepartment of Chemistry, National Chung Hsing University, Taichung 402, Taiwan
*Correspondence e-mail: mjchen@sunrise.hk.edu.tw
In the title compound, C17H15NO, the dihedral angle between the phenyl rings is 80.1 (2)°. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers.
Related literature
The title compound is a pyrrolidin-2-one derivative. For the preparation of related structures, see: Fujihara & Tomioka (1999); Enders & Han (2008). For a related structure containing intermolecular N—H⋯O=C hydrogen bonds, see: Asiri et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXL97.
Supporting information
10.1107/S1600536812043851/lh5547sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043851/lh5547Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043851/lh5547Isup3.cml
To a mixture of 5-(hydroxydiphenylmethyl)pyrrolidin-2-one (148 mg, 0.55 mmole) and boron trifluoride etherate (0.4 ml, 3.17 mmole) in 5.5 ml of dichloromethane was added excess calcium hydride. The reaction mixture was stirred at 298 K for 24 h under N2 atmosphere. The resulting mixture was partitioned between dichloromethane (10 ml) and H2O (10 ml). The organic layer was dried over MgSO4 and concentrated in vacuo. The residue was separated by
over silica gel and eluted with hexane/ethyl acetate (6/4) to afford 100 mg of the title compound (I) in 73% yield. Single crystals suitable for X-ray measurements were obtained by recrystallization from a dichloromethane/hexane solution of the title compound at room temperature.All H atoms were placed in geometrically idealized positions and treated as riding on their parent atoms, with C—H = 0.93 or 0.97 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C, N).
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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: SHELXL97 (Sheldrick, 2008.Fig. 1. The molecular structure of (I), with ellipsoids for non-H atoms shown at the 50% probability level. | |
Fig. 2. A hydrogen-bonded (dashed lines) dimer of (I). |
C17H15NO | Z = 2 |
Mr = 249.30 | F(000) = 264 |
Triclinic, P1 | Dx = 1.254 Mg m−3 |
Hall symbol: -P 1 | Melting point: 472 K |
a = 7.135 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.885 (2) Å | Cell parameters from 1065 reflections |
c = 12.184 (4) Å | θ = 3.0–29.0° |
α = 89.76 (3)° | µ = 0.08 mm−1 |
β = 75.09 (3)° | T = 293 K |
γ = 85.65 (2)° | Parallelpiped, colourless |
V = 660.4 (4) Å3 | 0.70 × 0.50 × 0.35 mm |
Agilent Xcalibur (Sapphire3, Gemini) diffractometer | 2999 independent reflections |
Radiation source: fine-focus sealed tube | 1951 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 16.0690 pixels mm-1 | θmax = 29.1°, θmin = 3.0° |
ω scans | h = −8→9 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −10→10 |
Tmin = 0.542, Tmax = 1.000 | l = −16→16 |
5549 measured reflections |
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.225 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.120P)2] where P = (Fo2 + 2Fc2)/3 |
2999 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C17H15NO | γ = 85.65 (2)° |
Mr = 249.30 | V = 660.4 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.135 (2) Å | Mo Kα radiation |
b = 7.885 (2) Å | µ = 0.08 mm−1 |
c = 12.184 (4) Å | T = 293 K |
α = 89.76 (3)° | 0.70 × 0.50 × 0.35 mm |
β = 75.09 (3)° |
Agilent Xcalibur (Sapphire3, Gemini) diffractometer | 2999 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1951 reflections with I > 2σ(I) |
Tmin = 0.542, Tmax = 1.000 | Rint = 0.052 |
5549 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.225 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.31 e Å−3 |
2999 reflections | Δρmin = −0.26 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O | −0.0325 (2) | 0.7022 (2) | 0.55977 (15) | 0.0575 (5) | |
N | 0.2544 (2) | 0.5943 (2) | 0.44030 (15) | 0.0405 (5) | |
H0A | 0.2224 | 0.4921 | 0.4353 | 0.049* | |
C1 | 0.1353 (3) | 0.7169 (3) | 0.50609 (19) | 0.0420 (5) | |
C2 | 0.2440 (3) | 0.8758 (3) | 0.4967 (2) | 0.0473 (6) | |
H2A | 0.2382 | 0.9216 | 0.5714 | 0.057* | |
H2B | 0.1898 | 0.9622 | 0.4543 | 0.057* | |
C3 | 0.4522 (3) | 0.8183 (3) | 0.4343 (2) | 0.0451 (6) | |
H3A | 0.5058 | 0.8992 | 0.3766 | 0.054* | |
H3B | 0.5342 | 0.8050 | 0.4865 | 0.054* | |
C4 | 0.4348 (3) | 0.6490 (3) | 0.38089 (18) | 0.0375 (5) | |
C5 | 0.5618 (3) | 0.5669 (3) | 0.29326 (18) | 0.0384 (5) | |
C6 | 0.5291 (3) | 0.3990 (3) | 0.24831 (18) | 0.0389 (5) | |
C7 | 0.3610 (3) | 0.3647 (3) | 0.2184 (2) | 0.0505 (6) | |
H7A | 0.2597 | 0.4492 | 0.2276 | 0.061* | |
C8 | 0.3409 (4) | 0.2072 (4) | 0.1751 (3) | 0.0627 (7) | |
H8A | 0.2263 | 0.1873 | 0.1560 | 0.075* | |
C9 | 0.4876 (4) | 0.0803 (3) | 0.1600 (2) | 0.0590 (7) | |
H9A | 0.4736 | −0.0256 | 0.1310 | 0.071* | |
C10 | 0.6556 (4) | 0.1125 (3) | 0.1885 (2) | 0.0543 (7) | |
H10A | 0.7564 | 0.0274 | 0.1785 | 0.065* | |
C11 | 0.6774 (3) | 0.2689 (3) | 0.2319 (2) | 0.0455 (6) | |
H11A | 0.7927 | 0.2878 | 0.2504 | 0.055* | |
C12 | 0.7457 (3) | 0.6416 (3) | 0.23349 (19) | 0.0398 (5) | |
C13 | 0.8740 (3) | 0.7062 (3) | 0.2886 (2) | 0.0477 (6) | |
H13A | 0.8460 | 0.7022 | 0.3675 | 0.057* | |
C14 | 1.0422 (3) | 0.7762 (3) | 0.2293 (2) | 0.0554 (7) | |
H14A | 1.1248 | 0.8193 | 0.2684 | 0.066* | |
C15 | 1.0873 (3) | 0.7819 (3) | 0.1129 (2) | 0.0581 (7) | |
H15A | 1.1997 | 0.8295 | 0.0728 | 0.070* | |
C16 | 0.9655 (4) | 0.7170 (3) | 0.0561 (2) | 0.0577 (7) | |
H16A | 0.9962 | 0.7195 | −0.0228 | 0.069* | |
C17 | 0.7963 (3) | 0.6473 (3) | 0.1157 (2) | 0.0499 (6) | |
H17A | 0.7153 | 0.6036 | 0.0758 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O | 0.0476 (10) | 0.0429 (10) | 0.0693 (12) | −0.0101 (7) | 0.0101 (8) | −0.0171 (8) |
N | 0.0425 (10) | 0.0255 (9) | 0.0486 (11) | −0.0054 (7) | −0.0022 (8) | −0.0062 (8) |
C1 | 0.0452 (13) | 0.0324 (12) | 0.0446 (12) | −0.0053 (9) | −0.0039 (10) | −0.0067 (9) |
C2 | 0.0496 (14) | 0.0324 (12) | 0.0553 (14) | −0.0083 (10) | −0.0036 (10) | −0.0102 (10) |
C3 | 0.0464 (13) | 0.0327 (12) | 0.0519 (14) | −0.0048 (9) | −0.0045 (10) | −0.0102 (10) |
C4 | 0.0385 (11) | 0.0258 (11) | 0.0471 (12) | −0.0032 (8) | −0.0089 (9) | −0.0018 (9) |
C5 | 0.0414 (12) | 0.0249 (11) | 0.0464 (12) | 0.0024 (8) | −0.0084 (9) | −0.0025 (9) |
C6 | 0.0439 (12) | 0.0270 (11) | 0.0409 (11) | 0.0011 (8) | −0.0030 (9) | −0.0027 (9) |
C7 | 0.0465 (14) | 0.0396 (14) | 0.0648 (16) | 0.0055 (10) | −0.0153 (11) | −0.0127 (11) |
C8 | 0.0571 (16) | 0.0543 (17) | 0.0803 (19) | −0.0059 (12) | −0.0232 (14) | −0.0149 (14) |
C9 | 0.0744 (18) | 0.0344 (14) | 0.0628 (17) | −0.0023 (12) | −0.0083 (13) | −0.0152 (11) |
C10 | 0.0607 (16) | 0.0270 (12) | 0.0652 (16) | 0.0085 (10) | −0.0016 (12) | −0.0015 (11) |
C11 | 0.0450 (13) | 0.0302 (12) | 0.0581 (14) | 0.0008 (9) | −0.0088 (10) | −0.0010 (10) |
C12 | 0.0401 (12) | 0.0241 (11) | 0.0509 (13) | 0.0065 (8) | −0.0062 (9) | −0.0026 (9) |
C13 | 0.0438 (13) | 0.0441 (14) | 0.0544 (14) | 0.0011 (10) | −0.0124 (10) | 0.0026 (11) |
C14 | 0.0420 (14) | 0.0516 (16) | 0.0744 (19) | −0.0060 (11) | −0.0176 (12) | 0.0064 (13) |
C15 | 0.0418 (13) | 0.0478 (15) | 0.0752 (19) | −0.0010 (11) | 0.0012 (12) | 0.0058 (13) |
C16 | 0.0631 (16) | 0.0500 (16) | 0.0502 (15) | −0.0026 (12) | 0.0026 (12) | −0.0028 (12) |
C17 | 0.0515 (14) | 0.0410 (14) | 0.0532 (14) | −0.0054 (10) | −0.0055 (11) | −0.0088 (11) |
O—C1 | 1.222 (3) | C8—C9 | 1.369 (4) |
N—C1 | 1.353 (3) | C8—H8A | 0.9300 |
N—C4 | 1.404 (3) | C9—C10 | 1.373 (3) |
N—H0A | 0.8600 | C9—H9A | 0.9300 |
C1—C2 | 1.512 (3) | C10—C11 | 1.379 (3) |
C2—C3 | 1.520 (3) | C10—H10A | 0.9300 |
C2—H2A | 0.9700 | C11—H11A | 0.9300 |
C2—H2B | 0.9700 | C12—C17 | 1.389 (3) |
C3—C4 | 1.515 (3) | C12—C13 | 1.393 (3) |
C3—H3A | 0.9700 | C13—C14 | 1.385 (3) |
C3—H3B | 0.9700 | C13—H13A | 0.9300 |
C4—C5 | 1.341 (3) | C14—C15 | 1.373 (4) |
C5—C12 | 1.490 (3) | C14—H14A | 0.9300 |
C5—C6 | 1.492 (3) | C15—C16 | 1.369 (4) |
C6—C7 | 1.386 (3) | C15—H15A | 0.9300 |
C6—C11 | 1.393 (3) | C16—C17 | 1.390 (3) |
C7—C8 | 1.383 (4) | C16—H16A | 0.9300 |
C7—H7A | 0.9300 | C17—H17A | 0.9300 |
C1—N—C4 | 113.85 (18) | C9—C8—C7 | 120.8 (2) |
C1—N—H0A | 123.1 | C9—C8—H8A | 119.6 |
C4—N—H0A | 123.1 | C7—C8—H8A | 119.6 |
O—C1—N | 125.5 (2) | C8—C9—C10 | 118.6 (2) |
O—C1—C2 | 126.6 (2) | C8—C9—H9A | 120.7 |
N—C1—C2 | 107.83 (19) | C10—C9—H9A | 120.7 |
C1—C2—C3 | 104.76 (19) | C9—C10—C11 | 121.1 (2) |
C1—C2—H2A | 110.8 | C9—C10—H10A | 119.4 |
C3—C2—H2A | 110.8 | C11—C10—H10A | 119.4 |
C1—C2—H2B | 110.8 | C10—C11—C6 | 120.9 (2) |
C3—C2—H2B | 110.8 | C10—C11—H11A | 119.5 |
H2A—C2—H2B | 108.9 | C6—C11—H11A | 119.5 |
C4—C3—C2 | 103.89 (16) | C17—C12—C13 | 116.8 (2) |
C4—C3—H3A | 111.0 | C17—C12—C5 | 119.22 (19) |
C2—C3—H3A | 111.0 | C13—C12—C5 | 123.9 (2) |
C4—C3—H3B | 111.0 | C14—C13—C12 | 121.8 (2) |
C2—C3—H3B | 111.0 | C14—C13—H13A | 119.1 |
H3A—C3—H3B | 109.0 | C12—C13—H13A | 119.1 |
C5—C4—N | 125.92 (19) | C15—C14—C13 | 120.1 (2) |
C5—C4—C3 | 128.01 (19) | C15—C14—H14A | 120.0 |
N—C4—C3 | 106.06 (18) | C13—C14—H14A | 120.0 |
C4—C5—C12 | 121.04 (19) | C16—C15—C14 | 119.5 (2) |
C4—C5—C6 | 123.16 (19) | C16—C15—H15A | 120.2 |
C12—C5—C6 | 115.79 (19) | C14—C15—H15A | 120.2 |
C7—C6—C11 | 117.2 (2) | C15—C16—C17 | 120.5 (2) |
C7—C6—C5 | 124.03 (19) | C15—C16—H16A | 119.8 |
C11—C6—C5 | 118.74 (18) | C17—C16—H16A | 119.8 |
C8—C7—C6 | 121.3 (2) | C12—C17—C16 | 121.3 (2) |
C8—C7—H7A | 119.4 | C12—C17—H17A | 119.3 |
C6—C7—H7A | 119.4 | C16—C17—H17A | 119.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···Oi | 0.86 | 2.11 | 2.921 (2) | 157 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C17H15NO |
Mr | 249.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.135 (2), 7.885 (2), 12.184 (4) |
α, β, γ (°) | 89.76 (3), 75.09 (3), 85.65 (2) |
V (Å3) | 660.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.70 × 0.50 × 0.35 |
Data collection | |
Diffractometer | Agilent Xcalibur (Sapphire3, Gemini) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.542, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5549, 2999, 1951 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.684 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.225, 1.06 |
No. of reflections | 2999 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0A···Oi | 0.86 | 2.11 | 2.921 (2) | 156.6 |
Symmetry code: (i) −x, −y+1, −z+1. |
Acknowledgements
We gratefully acknowledge financial support in part from the National Science Council, Taiwan (NSC 99–2119-M-241- 001-MY2). Helpful comments from the reviewers were also greatly appreciated.
References
Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Asiri, A. M., Zayed, M. E. M., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o2020. CSD CrossRef IUCr Journals Google Scholar
Enders, D. & Han, J. (2008). Tetrahedron Asymmetry, 19, 1367–1371. Web of Science CrossRef CAS Google Scholar
Fujihara, H. & Tomioka, K. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2377–2382. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The title compound (I) is the side product obtained from the attempted synthesis of 5-(diphenylmethyl)pyrrolidin-2-one (Fujihara et al., 1999; Enders et al., 2008). We found that adding excess calcium hydride to the reaction mixture could improve the yield of (I). Herein we report the synthesis and crystal structure of the (I). The molecular structure of (I) is shown in Fig. 1. The two phenyl rings form a dihedral angle of 80.1 (2)°. In the crystal, pairs of molecules are linked by N—H···O hydrogen bonds to form inversion dimers (Fig. 2). The intermolecular N—H···O=C hydrogen bonds are similar to those in 3-[(E)-benzylidene]indolin-2-one (Asiri et al., 2012).