2-Benzyl-3-phenyl-1-(pyridin-2-yl)propan-1-one

Naveed Umar, M.; Shoaib, M.; Ng, S.W.

doi:10.1107/S1600536812003686

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o575

doi:10.1107/S1600536812003686

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2-Benzyl-3-phenyl-1-(pyridin-2-yl)propan-1-one

Muhammad Naveed Umar,^a Mohammad Shoaib ^a and Seik Weng Ng ^b ^*

^aSchool of Chemistry, University of Malakand, Khyber Pakhtunkhwa, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 26 January 2012; accepted 27 January 2012; online 4 February 2012)

Molecules of the title compound, C₂₁H₁₉NO, assume an approximate propellar shape, with the three aromatic rings being nearly perpendicularly aligned with respect to the plane formed by the C atoms that are connected to the methine C atom [dihedral angles: pyridyl 79.82 (4)°, phenyl 80.12 (3)° and phenyl 86.93 (3)°].

Related literature

For background to fast aldol reactions, see: Nugent et al. (2010 ).

Experimental

Crystal data

C₂₁H₁₉NO
M_r = 301.37
Monoclinic, P 2₁ /n
a = 15.1569 (3) Å
b = 5.6333 (1) Å
c = 19.5468 (4) Å
β = 109.295 (2)°
V = 1575.22 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.60 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.840, T_max = 0.942
25210 measured reflections
3299 independent reflections
3133 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.04
3299 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003686/bt5803sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003686/bt5803Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003686/bt5803Isup3.cml

checkCIF report

Comment top

2-Benzyl-3-phenyl-1-(pyridin-2-yl)propan-1-one (Scheme I), in the optically active form, was synthesized for use in fast aldol condensations (Nugent et al., 2010). The molecule assumes an approximate propellar shape (Fig. 1), with the three aromatic rings being nearly perpendicularly aligned at with respect to the plane formed by the C atoms that are connected to the methine C atom [dihedral angles: pyridyl 79.82 (4), phenyl 80.12 (3), phenyl 86.93 (3)°].

Related literature top

For background to fast aldol reactions, see: Nugent et al. (2010).

Experimental top

In a 250 ml flask was added sodium borohydride (4 equiv, 1.2 mg, 48 mmol) in anhydrous toluene (40 ml) followed by the addition of 18-crown-6 (0.1 equiv, 0.32 mg, 1.2 mmol), and acetyl pyridine (1 equiv, 1.35 ml, 12 mmol). Benzyl bromide (2.5 equiv, 3.6 ml, 30 mmol) was added. The reaction mixture was stirred at 323 K for 5 h under an inert atmosphere. The reaction was monitored by TLC and GC. The reaction was quenched by adding saturated ammonium chloride. The organic compound was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and the solvent removed to give a yellow oil. This was submitted to flash chromatography and eluted with 5% ethyl acetate/hexane to give the desired ketone product (70% yield).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₂₁H₁₉NO at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Benzyl-3-phenyl-1-(pyridin-2-yl)propan-1-one top

Crystal data top

C₂₁H₁₉NO	F(000) = 640
M_r = 301.37	D_x = 1.271 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 14175 reflections
a = 15.1569 (3) Å	θ = 3.1–76.1°
b = 5.6333 (1) Å	µ = 0.60 mm⁻¹
c = 19.5468 (4) Å	T = 100 K
β = 109.295 (2)°	Block, colourless
V = 1575.22 (5) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	3299 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3133 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.3°, θ_min = 3.2°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→5
T_min = 0.840, T_max = 0.942	l = −24→24
25210 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0537P)² + 0.5533P] where P = (F_o² + 2F_c²)/3
3299 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₁H₁₉NO	V = 1575.22 (5) Å³
M_r = 301.37	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 15.1569 (3) Å	µ = 0.60 mm⁻¹
b = 5.6333 (1) Å	T = 100 K
c = 19.5468 (4) Å	0.30 × 0.20 × 0.10 mm
β = 109.295 (2)°

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	3299 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3133 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.942	R_int = 0.034
25210 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
3299 reflections	Δρ_min = −0.21 e Å⁻³
208 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.52050 (5)	0.37525 (13)	0.78840 (4)	0.01980 (17)
N1	0.46273 (6)	0.74653 (15)	0.63746 (5)	0.0198 (2)
C1	0.42604 (8)	0.7372 (2)	0.56524 (6)	0.0238 (2)
H1	0.4365	0.8677	0.5381	0.029*
C2	0.37344 (8)	0.5477 (2)	0.52749 (6)	0.0238 (2)
H2	0.3482	0.5497	0.4761	0.029*
C3	0.35863 (8)	0.3560 (2)	0.56657 (6)	0.0234 (2)
H3	0.3218	0.2252	0.5425	0.028*
C4	0.39850 (7)	0.35810 (19)	0.64159 (6)	0.0199 (2)
H4	0.3908	0.2274	0.6698	0.024*
C5	0.45003 (7)	0.55637 (17)	0.67445 (5)	0.0156 (2)
C6	0.49749 (6)	0.56118 (17)	0.75561 (5)	0.0149 (2)
C7	0.51069 (7)	0.80051 (17)	0.79253 (5)	0.0146 (2)
H7	0.5282	0.9173	0.7607	0.018*
C8	0.58912 (7)	0.79632 (18)	0.86598 (5)	0.0162 (2)
H8A	0.5892	0.9489	0.8911	0.019*
H8B	0.5763	0.6684	0.8961	0.019*
C9	0.68460 (7)	0.75692 (17)	0.85936 (5)	0.0152 (2)
C10	0.72381 (7)	0.92961 (18)	0.82695 (5)	0.0173 (2)
H10	0.6902	1.0716	0.8093	0.021*
C11	0.81153 (7)	0.89629 (19)	0.82020 (5)	0.0198 (2)
H11	0.8372	1.0150	0.7978	0.024*
C12	0.86173 (7)	0.68974 (19)	0.84614 (5)	0.0204 (2)
H12	0.9218	0.6672	0.8418	0.024*
C13	0.82336 (7)	0.51680 (18)	0.87838 (5)	0.0197 (2)
H13	0.8573	0.3755	0.8963	0.024*
C14	0.73529 (7)	0.54951 (18)	0.88463 (5)	0.0173 (2)
H14	0.7094	0.4293	0.9063	0.021*
C15	0.41552 (7)	0.87940 (17)	0.79944 (5)	0.0163 (2)
H15A	0.4214	1.0450	0.8173	0.020*
H15B	0.3674	0.8773	0.7507	0.020*
C16	0.38254 (7)	0.72582 (17)	0.84959 (5)	0.0159 (2)
C17	0.32976 (7)	0.52092 (18)	0.82459 (5)	0.0180 (2)
H17	0.3112	0.4813	0.7746	0.022*
C18	0.30400 (7)	0.37407 (18)	0.87213 (6)	0.0197 (2)
H18	0.2680	0.2356	0.8544	0.024*
C19	0.33078 (7)	0.42930 (19)	0.94531 (6)	0.0211 (2)
H19	0.3140	0.3278	0.9778	0.025*
C20	0.38230 (8)	0.6343 (2)	0.97072 (6)	0.0220 (2)
H20	0.4005	0.6737	1.0207	0.026*
C21	0.40717 (7)	0.78150 (18)	0.92306 (6)	0.0192 (2)
H21	0.4415	0.9224	0.9408	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0225 (4)	0.0148 (4)	0.0208 (4)	0.0004 (3)	0.0055 (3)	0.0034 (3)
N1	0.0237 (4)	0.0177 (4)	0.0170 (4)	−0.0013 (3)	0.0055 (3)	0.0008 (3)
C1	0.0300 (6)	0.0227 (5)	0.0173 (5)	0.0001 (4)	0.0060 (4)	0.0025 (4)
C2	0.0255 (5)	0.0263 (6)	0.0161 (5)	0.0040 (4)	0.0021 (4)	−0.0016 (4)
C3	0.0218 (5)	0.0211 (5)	0.0235 (5)	−0.0015 (4)	0.0024 (4)	−0.0054 (4)
C4	0.0196 (5)	0.0169 (5)	0.0225 (5)	−0.0012 (4)	0.0061 (4)	−0.0005 (4)
C5	0.0146 (4)	0.0152 (5)	0.0172 (5)	0.0017 (3)	0.0054 (4)	−0.0002 (4)
C6	0.0127 (4)	0.0153 (5)	0.0177 (5)	−0.0008 (3)	0.0062 (4)	0.0008 (4)
C7	0.0156 (4)	0.0140 (4)	0.0138 (4)	−0.0001 (3)	0.0043 (4)	0.0013 (3)
C8	0.0165 (5)	0.0179 (5)	0.0138 (4)	−0.0009 (4)	0.0043 (4)	−0.0007 (3)
C9	0.0163 (5)	0.0173 (5)	0.0110 (4)	−0.0024 (4)	0.0029 (3)	−0.0026 (3)
C10	0.0196 (5)	0.0168 (5)	0.0141 (4)	−0.0011 (4)	0.0037 (4)	−0.0001 (4)
C11	0.0217 (5)	0.0223 (5)	0.0166 (5)	−0.0053 (4)	0.0077 (4)	−0.0015 (4)
C12	0.0172 (5)	0.0250 (5)	0.0196 (5)	−0.0020 (4)	0.0071 (4)	−0.0057 (4)
C13	0.0200 (5)	0.0181 (5)	0.0191 (5)	0.0013 (4)	0.0040 (4)	−0.0027 (4)
C14	0.0197 (5)	0.0169 (5)	0.0147 (4)	−0.0024 (4)	0.0048 (4)	−0.0007 (4)
C15	0.0166 (5)	0.0151 (5)	0.0171 (5)	0.0019 (3)	0.0052 (4)	0.0018 (3)
C16	0.0138 (4)	0.0157 (5)	0.0185 (5)	0.0030 (3)	0.0056 (4)	0.0016 (4)
C17	0.0164 (4)	0.0196 (5)	0.0169 (4)	0.0003 (4)	0.0040 (4)	−0.0003 (4)
C18	0.0169 (5)	0.0183 (5)	0.0230 (5)	−0.0018 (4)	0.0054 (4)	0.0007 (4)
C19	0.0203 (5)	0.0226 (5)	0.0219 (5)	0.0003 (4)	0.0092 (4)	0.0048 (4)
C20	0.0237 (5)	0.0262 (5)	0.0174 (5)	−0.0005 (4)	0.0084 (4)	−0.0007 (4)
C21	0.0197 (5)	0.0177 (5)	0.0204 (5)	−0.0012 (4)	0.0071 (4)	−0.0023 (4)

Geometric parameters (Å, º) top

O1—C6	1.2172 (12)	C10—H10	0.9500
N1—C1	1.3365 (14)	C11—C12	1.3910 (15)
N1—C5	1.3414 (13)	C11—H11	0.9500
C1—C2	1.3897 (16)	C12—C13	1.3881 (15)
C1—H1	0.9500	C12—H12	0.9500
C2—C3	1.3829 (16)	C13—C14	1.3922 (14)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.3893 (15)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.5111 (13)
C4—C5	1.3922 (14)	C15—H15A	0.9900
C4—H4	0.9500	C15—H15B	0.9900
C5—C6	1.5103 (13)	C16—C21	1.3950 (14)
C6—C7	1.5110 (13)	C16—C17	1.3974 (14)
C7—C8	1.5320 (13)	C17—C18	1.3928 (14)
C7—C15	1.5573 (13)	C17—H17	0.9500
C7—H7	1.0000	C18—C19	1.3869 (15)
C8—C9	1.5113 (13)	C18—H18	0.9500
C8—H8A	0.9900	C19—C20	1.3905 (15)
C8—H8B	0.9900	C19—H19	0.9500
C9—C10	1.3963 (14)	C20—C21	1.3892 (15)
C9—C14	1.3960 (14)	C20—H20	0.9500
C10—C11	1.3916 (14)	C21—H21	0.9500

C1—N1—C5	117.01 (9)	C12—C11—C10	120.20 (9)
N1—C1—C2	123.81 (10)	C12—C11—H11	119.9
N1—C1—H1	118.1	C10—C11—H11	119.9
C2—C1—H1	118.1	C13—C12—C11	119.46 (9)
C3—C2—C1	118.42 (10)	C13—C12—H12	120.3
C3—C2—H2	120.8	C11—C12—H12	120.3
C1—C2—H2	120.8	C12—C13—C14	120.31 (10)
C2—C3—C4	118.89 (10)	C12—C13—H13	119.8
C2—C3—H3	120.6	C14—C13—H13	119.8
C4—C3—H3	120.6	C13—C14—C9	120.75 (9)
C3—C4—C5	118.41 (10)	C13—C14—H14	119.6
C3—C4—H4	120.8	C9—C14—H14	119.6
C5—C4—H4	120.8	C16—C15—C7	114.03 (8)
N1—C5—C4	123.40 (9)	C16—C15—H15A	108.7
N1—C5—C6	116.65 (8)	C7—C15—H15A	108.7
C4—C5—C6	119.92 (9)	C16—C15—H15B	108.7
O1—C6—C5	119.46 (9)	C7—C15—H15B	108.7
O1—C6—C7	123.14 (8)	H15A—C15—H15B	107.6
C5—C6—C7	117.36 (8)	C21—C16—C17	118.25 (9)
C6—C7—C8	111.91 (8)	C21—C16—C15	120.38 (9)
C6—C7—C15	108.41 (8)	C17—C16—C15	121.33 (9)
C8—C7—C15	112.17 (8)	C18—C17—C16	120.77 (9)
C6—C7—H7	108.1	C18—C17—H17	119.6
C8—C7—H7	108.1	C16—C17—H17	119.6
C15—C7—H7	108.1	C19—C18—C17	120.25 (10)
C9—C8—C7	112.99 (8)	C19—C18—H18	119.9
C9—C8—H8A	109.0	C17—C18—H18	119.9
C7—C8—H8A	109.0	C18—C19—C20	119.55 (10)
C9—C8—H8B	109.0	C18—C19—H19	120.2
C7—C8—H8B	109.0	C20—C19—H19	120.2
H8A—C8—H8B	107.8	C21—C20—C19	120.06 (10)
C10—C9—C14	118.47 (9)	C21—C20—H20	120.0
C10—C9—C8	119.98 (9)	C19—C20—H20	120.0
C14—C9—C8	121.55 (9)	C20—C21—C16	121.10 (10)
C11—C10—C9	120.82 (9)	C20—C21—H21	119.5
C11—C10—H10	119.6	C16—C21—H21	119.5
C9—C10—H10	119.6

C5—N1—C1—C2	2.48 (16)	C14—C9—C10—C11	−0.23 (14)
N1—C1—C2—C3	−0.61 (17)	C8—C9—C10—C11	−179.84 (9)
C1—C2—C3—C4	−1.43 (16)	C9—C10—C11—C12	−0.31 (15)
C2—C3—C4—C5	1.50 (16)	C10—C11—C12—C13	0.38 (15)
C1—N1—C5—C4	−2.38 (15)	C11—C12—C13—C14	0.09 (15)
C1—N1—C5—C6	175.79 (9)	C12—C13—C14—C9	−0.64 (15)
C3—C4—C5—N1	0.44 (15)	C10—C9—C14—C13	0.70 (14)
C3—C4—C5—C6	−177.67 (9)	C8—C9—C14—C13	−179.69 (9)
N1—C5—C6—O1	−151.38 (9)	C6—C7—C15—C16	66.21 (10)
C4—C5—C6—O1	26.85 (13)	C8—C7—C15—C16	−57.86 (11)
N1—C5—C6—C7	30.88 (12)	C7—C15—C16—C21	90.50 (11)
C4—C5—C6—C7	−150.88 (9)	C7—C15—C16—C17	−87.20 (11)
O1—C6—C7—C8	24.09 (13)	C21—C16—C17—C18	−1.18 (15)
C5—C6—C7—C8	−158.27 (8)	C15—C16—C17—C18	176.56 (9)
O1—C6—C7—C15	−100.14 (10)	C16—C17—C18—C19	−0.18 (15)
C5—C6—C7—C15	77.51 (10)	C17—C18—C19—C20	0.99 (16)
C6—C7—C8—C9	66.67 (10)	C18—C19—C20—C21	−0.42 (16)
C15—C7—C8—C9	−171.23 (8)	C19—C20—C21—C16	−0.98 (16)
C7—C8—C9—C10	66.63 (11)	C17—C16—C21—C20	1.76 (15)
C7—C8—C9—C14	−112.97 (10)	C15—C16—C21—C20	−176.00 (9)

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉NO
M_r	301.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	15.1569 (3), 5.6333 (1), 19.5468 (4)
β (°)	109.295 (2)
V (Å³)	1575.22 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.840, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	25210, 3299, 3133
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.04
No. of reflections	3299
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank the Higher Education Commission of Pakistan and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

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