2-Methyl-2-phenyl-1-(pyrrolidin-1-yl)propan-1-one

Ren, D.

doi:10.1107/S1600536813009975

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o773

https://doi.org/10.1107/S1600536813009975

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2-Methyl-2-phenyl-1-(pyrrolidin-1-yl)propan-1-one

Dong-mei Ren ^a ^*

^aSecurity and Environment Engineering College, Capital University of Economics and Business, Beijing 10070, People's Republic of China
^*Correspondence e-mail: nanoren@126.com

(Received 21 March 2013; accepted 11 April 2013; online 20 April 2013)

In the title compound, C₁₄H₁₉NO, the dihedral angle between the benzene ring and the plane of the amide group is 80.6 (1)°. In the crystal, molecules are connected via weak C—H⋯O hydrogen bonds, forming chains along the c-axis direction. The conformation of the five-memebred ring is an envelope, with one of the ring C atoms adjacent to the ring N atom as the flap atom.

Related literature

For background to the applications of the title compound as an intermediate in organic synthesis, an important organic synthesis intermediate, see: Richard et al. (2001 ). For the synthetic procedure, see: Richard et al. (1995 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₉NO
M_r = 217.30
Monoclinic, P 2₁ /c
a = 8.2330 (16) Å
b = 12.534 (3) Å
c = 12.192 (2) Å
β = 97.96 (3)°
V = 1246.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.979, T_max = 0.993
2283 measured reflections
2283 independent reflections
1316 reflections with I > 2σ(I)
R_int = 0.000
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.152
S = 1.00
2283 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.97	2.58	3.510 (4)	160
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813009975/bq2384sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813009975/bq2384Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813009975/bq2384Isup3.cml

checkCIF report

Comment top

The title compound is an important intermediate in the synthesis of [(piperidinoalkanoyl)phenyl]propionates, which can be utilized to synthesize antihistaminics. And we report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. There is a intermolecular contact C—H···O in the title compound, forming molecular chains along c axis direction (Table 1, Fig. 2). The dihedral angles between the benzene ring and the plane of amide is 80.6 (1)°.

Related literature top

For background to the applications of the title compound, an important organic synthesis intermediate, see: Richard et al. (2001). For the synthetic procedure, see: Richard et al. (1995). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Richard et al., 1995). The crystals were obtained by dissolving (I) (0.1 g) in methanol (30 ml) and evaporating the solvent slowly at room temperature for about 8 d.

Structure description top

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) showing C-H···O bonds with dashed lines.

2-Methyl-2-phenyl-1-(pyrrolidin-1-yl)propan-1-one top

Crystal data top

C₁₄H₁₉NO	F(000) = 472
M_r = 217.30	D_x = 1.158 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.2330 (16) Å	θ = 10–13°
b = 12.534 (3) Å	µ = 0.07 mm⁻¹
c = 12.192 (2) Å	T = 293 K
β = 97.96 (3)°	Block, colorless
V = 1246.0 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1316 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.979, T_max = 0.993	l = 0→14
2283 measured reflections	3 standard reflections every 200 reflections
2283 independent reflections	intensity decay: 1%

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.060P)² + 0.270P] where P = (F_o² + 2F_c²)/3
2283 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₉NO	V = 1246.0 (4) Å³
M_r = 217.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2330 (16) Å	µ = 0.07 mm⁻¹
b = 12.534 (3) Å	T = 293 K
c = 12.192 (2) Å	0.30 × 0.20 × 0.10 mm
β = 97.96 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1316 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.979, T_max = 0.993	3 standard reflections every 200 reflections
2283 measured reflections	intensity decay: 1%
2283 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	Δρ_max = 0.17 e Å⁻³
2283 reflections	Δρ_min = −0.22 e Å⁻³
147 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
O1	0.1927 (2)	0.24083 (17)	0.16560 (15)	0.0730 (7)
N1	0.2387 (2)	0.34793 (18)	0.31203 (16)	0.0491 (6)
C1	0.2993 (4)	0.3817 (2)	0.4267 (2)	0.0633 (8)
H1A	0.2614	0.3334	0.4799	0.076*
H1B	0.4182	0.3838	0.4391	0.076*
C2	0.2319 (4)	0.4866 (3)	0.4358 (3)	0.0842 (10)
H2A	0.1506	0.4843	0.4863	0.101*
H2B	0.3185	0.5349	0.4665	0.101*
C3	0.1581 (4)	0.5259 (3)	0.3317 (3)	0.0819 (10)
H3A	0.2195	0.5864	0.3098	0.098*
H3B	0.0468	0.5490	0.3363	0.098*
C4	0.1570 (3)	0.4378 (2)	0.2480 (2)	0.0620 (8)
H4A	0.0457	0.4192	0.2170	0.074*
H4B	0.2171	0.4585	0.1883	0.074*
C5	0.2512 (3)	0.2526 (2)	0.2639 (2)	0.0457 (6)
C6	0.3330 (3)	0.1583 (2)	0.33080 (19)	0.0429 (6)
C7	0.2188 (3)	0.1215 (2)	0.4117 (2)	0.0551 (7)
H7A	0.2114	0.1762	0.4660	0.083*
H7B	0.2613	0.0574	0.4480	0.083*
H7C	0.1118	0.1078	0.3720	0.083*
C8	0.3515 (3)	0.0672 (2)	0.2504 (2)	0.0614 (8)
H8A	0.4202	0.0898	0.1972	0.092*
H8B	0.2455	0.0477	0.2127	0.092*
H8C	0.4004	0.0069	0.2907	0.092*
C9	0.5076 (3)	0.1884 (2)	0.38690 (19)	0.0414 (6)
C10	0.5641 (3)	0.1624 (2)	0.4966 (2)	0.0530 (7)
H10A	0.4940	0.1289	0.5394	0.064*
C11	0.7227 (3)	0.1857 (2)	0.5426 (2)	0.0624 (8)
H11A	0.7586	0.1675	0.6159	0.075*
C12	0.8267 (3)	0.2348 (3)	0.4818 (3)	0.0654 (9)
H12A	0.9334	0.2507	0.5132	0.078*
C13	0.7727 (3)	0.2613 (3)	0.3722 (2)	0.0658 (9)
H13A	0.8433	0.2947	0.3298	0.079*
C14	0.6134 (3)	0.2378 (2)	0.3264 (2)	0.0561 (8)
H14A	0.5778	0.2559	0.2530	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0851 (15)	0.0855 (15)	0.0406 (11)	0.0132 (12)	−0.0194 (10)	−0.0072 (11)
N1	0.0442 (13)	0.0590 (15)	0.0403 (12)	0.0075 (11)	−0.0073 (9)	0.0037 (11)
C1	0.079 (2)	0.0611 (19)	0.0433 (16)	0.0133 (17)	−0.0134 (14)	−0.0069 (14)
C2	0.104 (3)	0.076 (2)	0.070 (2)	0.027 (2)	0.0001 (19)	−0.0062 (18)
C3	0.095 (3)	0.062 (2)	0.082 (2)	0.0266 (19)	−0.0103 (19)	−0.0001 (19)
C4	0.0570 (18)	0.070 (2)	0.0553 (17)	0.0153 (15)	−0.0052 (14)	0.0161 (16)
C5	0.0368 (14)	0.0610 (18)	0.0364 (14)	0.0011 (13)	−0.0049 (11)	−0.0054 (14)
C6	0.0370 (14)	0.0497 (16)	0.0403 (14)	0.0045 (12)	−0.0009 (11)	−0.0053 (12)
C7	0.0466 (15)	0.0592 (18)	0.0589 (17)	−0.0028 (14)	0.0051 (13)	−0.0004 (14)
C8	0.0596 (18)	0.0657 (19)	0.0565 (17)	0.0064 (15)	−0.0005 (14)	−0.0222 (15)
C9	0.0386 (14)	0.0446 (15)	0.0386 (13)	0.0083 (12)	−0.0028 (11)	−0.0041 (12)
C10	0.0465 (15)	0.0663 (19)	0.0438 (15)	0.0067 (14)	−0.0016 (12)	0.0058 (14)
C11	0.0492 (17)	0.080 (2)	0.0519 (17)	0.0116 (16)	−0.0151 (14)	−0.0049 (16)
C12	0.0390 (16)	0.082 (2)	0.071 (2)	0.0110 (15)	−0.0092 (15)	−0.0231 (18)
C13	0.0397 (16)	0.087 (2)	0.071 (2)	−0.0079 (15)	0.0058 (14)	−0.0049 (18)
C14	0.0466 (16)	0.075 (2)	0.0453 (15)	−0.0055 (14)	0.0011 (12)	0.0074 (15)

Geometric parameters (Å, º) top

O1—C5	1.237 (3)	C6—C9	1.550 (3)
N1—C5	1.342 (3)	C7—H7A	0.9600
N1—C4	1.479 (3)	C7—H7B	0.9600
N1—C1	1.480 (3)	C7—H7C	0.9600
C1—C2	1.437 (4)	C8—H8A	0.9600
C1—H1A	0.9700	C8—H8B	0.9600
C1—H1B	0.9700	C8—H8C	0.9600
C2—C3	1.418 (4)	C9—C14	1.366 (3)
C2—H2A	0.9700	C9—C10	1.392 (3)
C2—H2B	0.9700	C10—C11	1.380 (4)
C3—C4	1.502 (4)	C10—H10A	0.9300
C3—H3A	0.9700	C11—C12	1.356 (4)
C3—H3B	0.9700	C11—H11A	0.9300
C4—H4A	0.9700	C12—C13	1.388 (4)
C4—H4B	0.9700	C12—H12A	0.9300
C5—C6	1.537 (3)	C13—C14	1.384 (3)
C6—C7	1.526 (3)	C13—H13A	0.9300
C6—C8	1.526 (3)	C14—H14A	0.9300

C5—N1—C4	120.3 (2)	C7—C6—C9	113.9 (2)
C5—N1—C1	129.2 (2)	C8—C6—C9	107.25 (19)
C4—N1—C1	110.5 (2)	C5—C6—C9	111.0 (2)
C2—C1—N1	104.6 (2)	C6—C7—H7A	109.5
C2—C1—H1A	110.8	C6—C7—H7B	109.5
N1—C1—H1A	110.8	H7A—C7—H7B	109.5
C2—C1—H1B	110.8	C6—C7—H7C	109.5
N1—C1—H1B	110.8	H7A—C7—H7C	109.5
H1A—C1—H1B	108.9	H7B—C7—H7C	109.5
C3—C2—C1	111.7 (3)	C6—C8—H8A	109.5
C3—C2—H2A	109.3	C6—C8—H8B	109.5
C1—C2—H2A	109.3	H8A—C8—H8B	109.5
C3—C2—H2B	109.3	C6—C8—H8C	109.5
C1—C2—H2B	109.3	H8A—C8—H8C	109.5
H2A—C2—H2B	107.9	H8B—C8—H8C	109.5
C2—C3—C4	108.4 (3)	C14—C9—C10	118.1 (2)
C2—C3—H3A	110.0	C14—C9—C6	119.6 (2)
C4—C3—H3A	110.0	C10—C9—C6	122.2 (2)
C2—C3—H3B	110.0	C11—C10—C9	120.9 (3)
C4—C3—H3B	110.0	C11—C10—H10A	119.6
H3A—C3—H3B	108.4	C9—C10—H10A	119.6
N1—C4—C3	104.0 (2)	C12—C11—C10	120.5 (3)
N1—C4—H4A	111.0	C12—C11—H11A	119.8
C3—C4—H4A	111.0	C10—C11—H11A	119.8
N1—C4—H4B	111.0	C11—C12—C13	119.5 (3)
C3—C4—H4B	111.0	C11—C12—H12A	120.2
H4A—C4—H4B	109.0	C13—C12—H12A	120.2
O1—C5—N1	119.1 (2)	C14—C13—C12	119.8 (3)
O1—C5—C6	120.4 (2)	C14—C13—H13A	120.1
N1—C5—C6	120.4 (2)	C12—C13—H13A	120.1
C7—C6—C8	108.3 (2)	C9—C14—C13	121.2 (3)
C7—C6—C5	108.2 (2)	C9—C14—H14A	119.4
C8—C6—C5	108.0 (2)	C13—C14—H14A	119.4

C5—N1—C1—C2	−172.4 (3)	N1—C5—C6—C9	−54.4 (3)
C4—N1—C1—C2	8.5 (3)	C7—C6—C9—C14	−170.0 (2)
N1—C1—C2—C3	−9.5 (4)	C8—C6—C9—C14	70.1 (3)
C1—C2—C3—C4	7.0 (4)	C5—C6—C9—C14	−47.7 (3)
C5—N1—C4—C3	176.3 (2)	C7—C6—C9—C10	13.0 (3)
C1—N1—C4—C3	−4.6 (3)	C8—C6—C9—C10	−106.8 (3)
C2—C3—C4—N1	−1.3 (4)	C5—C6—C9—C10	135.4 (2)
C4—N1—C5—O1	−0.5 (4)	C14—C9—C10—C11	−0.2 (4)
C1—N1—C5—O1	−179.4 (3)	C6—C9—C10—C11	176.8 (2)
C4—N1—C5—C6	−178.8 (2)	C9—C10—C11—C12	0.3 (4)
C1—N1—C5—C6	2.2 (4)	C10—C11—C12—C13	−0.3 (5)
O1—C5—C6—C7	−107.0 (3)	C11—C12—C13—C14	0.3 (5)
N1—C5—C6—C7	71.3 (3)	C10—C9—C14—C13	0.2 (4)
O1—C5—C6—C8	10.0 (3)	C6—C9—C14—C13	−176.9 (3)
N1—C5—C6—C8	−171.7 (2)	C12—C13—C14—C9	−0.2 (4)
O1—C5—C6—C9	127.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.97	2.58	3.510 (4)	160

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₉NO
M_r	217.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.2330 (16), 12.534 (3), 12.192 (2)
β (°)	97.96 (3)
V (Å³)	1246.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.979, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	2283, 2283, 1316
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.152, 1.00
No. of reflections	2283
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.22

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.97	2.58	3.510 (4)	160

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

This study was financially supported by Scientific Research Project of Beijing Education Commission and the Scientific Research Level Project of Beijing Education Commission Foundation. The authors thank the Center of Testing and Analysis, Beijing University of Science and Technology.

References

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