5-(Diphenyl­methyl­idene)pyrrolidin-2-one

Hsu, T.-F.; Chen, Y.-R.; Huang, B.-H.; Chen, M.-J.

doi:10.1107/S1600536812043851

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3224

doi:10.1107/S1600536812043851

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5-(Diphenylmethylidene)pyrrolidin-2-one

Tzu-Fang Hsu,^a Yan-Ru Chen,^a Bor-Hunn Huang ^b and Ming-Jen Chen ^a ^*

^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

(Received 16 October 2012; accepted 23 October 2012; online 27 October 2012)

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

C₁₇H₁₅NO
M_r = 249.30
Triclinic, $[P \overline 1]$
a = 7.135 (2) Å
b = 7.885 (2) Å
c = 12.184 (4) Å
α = 89.76 (3)°
β = 75.09 (3)°
γ = 85.65 (2)°
V = 660.4 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.70 × 0.50 × 0.35 mm

Data collection

Agilent Xcalibur (Sapphire3, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.542, T_max = 1.000
5549 measured reflections
2999 independent reflections
1951 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.225
S = 1.06
2999 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812043851/lh5547sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043851/lh5547Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043851/lh5547Isup3.cml

checkCIF report

Comment top

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).

Related literature top

The title compound is a pyrrolidin-2-one derivative. For the preparation of related structures, see: Fujihara et al. (1999); Enders et al. (2008). For a related structure containing intermolecular N—H···O=C hydrogen bonds, see: Asiri et al. (2012).

Experimental top

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 chromatography 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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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.

Figures top

	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).

5-(Diphenylmethylidene)pyrrolidin-2-one top

Crystal data top

C₁₇H₁₅NO	Z = 2
M_r = 249.30	F(000) = 264
Triclinic, P1	D_x = 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

Data collection top

Agilent Xcalibur (Sapphire3, Gemini) diffractometer	2999 independent reflections
Radiation source: fine-focus sealed tube	1951 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 16.0690 pixels mm^-1	θ_max = 29.1°, θ_min = 3.0°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→10
T_min = 0.542, T_max = 1.000	l = −16→16
5549 measured reflections

Refinement top

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(F_o²) + (0.120P)²] where P = (F_o² + 2F_c²)/3
2999 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₇H₁₅NO	γ = 85.65 (2)°
M_r = 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)°

Data collection top

Agilent Xcalibur (Sapphire3, Gemini) diffractometer	2999 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1951 reflections with I > 2σ(I)
T_min = 0.542, T_max = 1.000	R_int = 0.052
5549 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.225	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
2999 reflections	Δρ_min = −0.26 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.542, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5549, 2999, 1951
R_int	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
Δρ_max, Δρ_min (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.

Hydrogen-bond geometry (Å, º) top

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

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