4-Phenyl-2,6-bis­(4-tol­yl)pyridine

Ma, Y.; Liu, B.; Xue, C.

doi:10.1107/S1600536810031764

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2322

https://doi.org/10.1107/S1600536810031764

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4-Phenyl-2,6-bis(4-tolyl)pyridine

Yajun Ma,^a ^* Buming Liu ^a and Chenghu Xue ^a

^aSchool of Chemistry and Chemical Engineering, Yu Lin University, Yulin 719000, People's Republic of China
^*Correspondence e-mail: yulinmyj@126.com

(Received 17 July 2010; accepted 7 August 2010; online 18 August 2010)

The title molecule, C₂₅H₂₁N, situated on the crystallographic twofold axis has a symmetry point group 2. The interplanar angles between the central pyridyl ring and the phenyl and the methylphenyl rings are 32.8 (2) and 23.7 (2)°, respectively. In the crystal packing, the central pyridyl rings of adjacent molecules are involved in π–π interactions, forming one-dimensional arrays along the c axis with centroid–centroid distances of 3.714 (1) Å.

Related literature

For the synthesis of Kröhnke-type pyridines, see: Cave & Raston (2001 ); Kröhnke (1976 ).

Experimental

Crystal data

C₂₅H₂₁N
M_r = 335.43
Orthorhombic, P c c a
a = 21.234 (3) Å
b = 12.0489 (15) Å
c = 7.3601 (10) Å
V = 1883.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 295 K
0.24 × 0.16 × 0.14 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.984, T_max = 0.991
6295 measured reflections
1833 independent reflections
1130 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.179
S = 1.02
1833 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810031764/fb2207sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031764/fb2207Isup2.hkl

checkCIF report

Comment top

The Kröhnke type pyridines with different substituents as well as their syntheses have been widely studied. The reason is a prominent functionalization of the Kröhnke type pyridines as building blocks in both organic and inorganic supramolecular chemistry (Cave & Raston, 2001; Kröhnke, 1976). In this article, the synthesis and the crystal structure of a new Kröhnke type pyridine compound, 4-phenyl-2,6-bis-(4-tolyl)-pyridine, is presented.

The title molecule shows symmetry 2. The two-fold axis passes through the central pyridine N1, C10, C11, C14 and H14 atoms (Fig. 1). The interplanar angle between central pyridyl ring (N1—C10) and the phenyl ring (C11—C14) is 32.8 (2)°, while the interplanar angle between the central pyridyl ring and methylphenyl ring (C2—C7) equals to 23.7 (2)°. The central pyridyl rings of the adjacent molecules are connected by intermolecular π-electron ring···π-electron ring interactions to form one-dimensional arrays along the c axis. The pertinent centroid-to-centroid distances equal to 3.714 (1) Å (Fig. 2). The centroid coordinates are 0.00000 (3), 0.52074 (7), 0.25000 (7) (Spek, 2009).

Related literature top

For the synthesis of Kröhnke-type pyridines, see: Cave & Raston (2001); Kröhnke (1976).

Experimental top

The mixture of benzaldehyde (1.06 g, 10 mmol), 4-methylacetophenone (2.68 g, 20 mmol) and NaOH (0.80 g, 20 mmol) in water (20 ml) and 95% ethanol (20 ml) was stirred for 3 h at room temperature, then the solution of ammonium acetate (7.70 g, 100 mmol) in 95% ethanol (60 ml) was added, and further refluxed at 343 K for 8 h. The resulting solution was cooled, solvent reduced to 20 ml to give a white precipitate which was collected by filtration and washed with ethanol. Recrystallization from 95% ethanol gave colorless prism crystals of the title compound with sizes of about 2.0 × 0.5 × 0.1 mm. Yield: 0.41 g (12%).

Structure description top

For the synthesis of Kröhnke-type pyridines, see: Cave & Raston (2001); Kröhnke (1976).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The title molecule with displacement ellipsoids drawn at the 30% probability level. The H atoms are shown as spheres of arbitrary radii. The atoms labelled by "A" are related to their counterparts by the rotation by 180° about the crystallographic two-fold axis.
	Fig. 2. Packing diagram of the title compound showing the intermolecular π-electron ring···π-electron ring interactions as dashed lines. The H atoms have been omitted for clarity.

4-Phenyl-2,6-bis(4-tolyl)pyridine top

Crystal data top

C₂₅H₂₁N	F(000) = 712
M_r = 335.43	D_x = 1.183 Mg m⁻³
Orthorhombic, Pcca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ac	Cell parameters from 1019 reflections
a = 21.234 (3) Å	θ = 2.6–23.3°
b = 12.0489 (15) Å	µ = 0.07 mm⁻¹
c = 7.3601 (10) Å	T = 295 K
V = 1883.1 (4) Å³	Prism, colourless
Z = 4	0.24 × 0.16 × 0.14 mm

Data collection top

Bruker SMART APEX area-detector diffractometer	1833 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
T_min = 0.984, T_max = 0.991	k = −14→12
6295 measured reflections	l = −9→2

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)] = 0.058	Hydrogen site location: difference Fourier map
wR(F²) = 0.179	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.091P)² + 0.1078P] where P = (F_o² + 2F_c²)/3
1833 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³
41 constraints

Crystal data top

C₂₅H₂₁N	V = 1883.1 (4) Å³
M_r = 335.43	Z = 4
Orthorhombic, Pcca	Mo Kα radiation
a = 21.234 (3) Å	µ = 0.07 mm⁻¹
b = 12.0489 (15) Å	T = 295 K
c = 7.3601 (10) Å	0.24 × 0.16 × 0.14 mm

Data collection top

Bruker SMART APEX area-detector diffractometer	1833 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1130 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.991	R_int = 0.030
6295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.02	Δρ_max = 0.13 e Å⁻³
1833 reflections	Δρ_min = −0.12 e Å⁻³
121 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.0000	0.63606 (17)	0.2500	0.0650 (6)
C1	0.28100 (10)	0.8434 (2)	0.3583 (5)	0.1274 (12)
H1A	0.3171	0.7958	0.3474	0.191*
H1B	0.2811	0.8780	0.4758	0.191*
H1C	0.2826	0.8994	0.2657	0.191*
C2	0.22150 (10)	0.7754 (2)	0.3362 (4)	0.0965 (8)
C3	0.16260 (9)	0.81731 (18)	0.3759 (4)	0.0895 (8)
H3	0.1591	0.8899	0.4179	0.107*
C4	0.10883 (9)	0.75416 (17)	0.3549 (3)	0.0778 (6)
H4	0.0699	0.7847	0.3836	0.093*
C5	0.11203 (8)	0.64629 (16)	0.2921 (3)	0.0686 (6)
C6	0.17095 (9)	0.6050 (2)	0.2485 (4)	0.0993 (9)
H6	0.1747	0.5331	0.2036	0.119*
C7	0.22435 (10)	0.6695 (2)	0.2710 (5)	0.1153 (11)
H7	0.2634	0.6397	0.2407	0.138*
C8	0.05366 (8)	0.57880 (17)	0.2701 (2)	0.0637 (5)
C9	0.05510 (8)	0.46379 (17)	0.2715 (2)	0.0670 (6)
H9	0.0932	0.4270	0.2870	0.080*
C10	0.0000	0.4032 (2)	0.2500	0.0640 (7)
C11	0.0000	0.2803 (2)	0.2500	0.0657 (7)
C12	0.04268 (9)	0.22100 (17)	0.3546 (3)	0.0748 (6)
H12	0.0718	0.2590	0.4257	0.090*
C13	0.04258 (10)	0.10657 (18)	0.3546 (3)	0.0882 (7)
H13	0.0715	0.0682	0.4257	0.106*
C14	0.0000	0.0489 (3)	0.2500	0.0930 (10)
H14	0.0000	−0.0283	0.2500	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0574 (12)	0.0664 (14)	0.0710 (15)	0.000	−0.0003 (10)	0.000
C1	0.0739 (15)	0.116 (2)	0.193 (4)	−0.0204 (13)	−0.0066 (18)	−0.0032 (19)
C2	0.0660 (14)	0.0832 (17)	0.140 (2)	−0.0064 (12)	−0.0059 (13)	0.0046 (15)
C3	0.0723 (15)	0.0760 (14)	0.120 (2)	−0.0075 (11)	0.0012 (12)	−0.0090 (13)
C4	0.0614 (12)	0.0758 (14)	0.0961 (15)	0.0008 (10)	0.0040 (10)	−0.0063 (12)
C5	0.0567 (11)	0.0685 (12)	0.0805 (13)	0.0009 (9)	−0.0014 (9)	0.0057 (10)
C6	0.0675 (14)	0.0712 (14)	0.159 (3)	0.0068 (11)	0.0054 (13)	−0.0035 (15)
C7	0.0545 (13)	0.0880 (18)	0.203 (3)	0.0053 (11)	0.0060 (15)	0.0033 (18)
C8	0.0615 (11)	0.0672 (13)	0.0624 (12)	0.0011 (9)	0.0022 (8)	0.0008 (9)
C9	0.0631 (12)	0.0688 (13)	0.0692 (12)	0.0039 (8)	−0.0005 (8)	0.0019 (10)
C10	0.0687 (16)	0.0654 (17)	0.0578 (16)	0.000	0.0033 (12)	0.000
C11	0.0651 (16)	0.0657 (17)	0.0664 (17)	0.000	0.0108 (12)	0.000
C12	0.0748 (13)	0.0701 (13)	0.0795 (14)	0.0034 (10)	0.0063 (10)	0.0007 (11)
C13	0.0885 (15)	0.0759 (15)	0.1001 (19)	0.0089 (12)	0.0109 (12)	0.0086 (13)
C14	0.105 (2)	0.0607 (18)	0.114 (3)	0.000	0.025 (2)	0.000

Geometric parameters (Å, º) top

N1—C8	1.340 (2)	C6—H6	0.9300
N1—C8ⁱ	1.340 (2)	C7—H7	0.9300
C1—C2	1.515 (3)	C8—C9	1.386 (3)
C1—H1A	0.9600	C9—C10	1.388 (2)
C1—H1B	0.9600	C9—H9	0.9300
C1—H1C	0.9600	C10—C9ⁱ	1.388 (2)
C2—C7	1.365 (3)	C10—C11	1.480 (4)
C2—C3	1.380 (3)	C11—C12	1.387 (2)
C3—C4	1.381 (3)	C11—C12ⁱ	1.387 (2)
C3—H3	0.9300	C12—C13	1.379 (3)
C4—C5	1.381 (3)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.376 (3)
C5—C6	1.384 (3)	C13—H13	0.9300
C5—C8	1.491 (2)	C14—C13ⁱ	1.376 (3)
C6—C7	1.384 (3)	C14—H14	0.9300

C8—N1—C8ⁱ	118.0 (2)	C2—C7—H7	119.0
C2—C1—H1A	109.5	C6—C7—H7	119.0
C2—C1—H1B	109.5	N1—C8—C9	122.30 (17)
H1A—C1—H1B	109.5	N1—C8—C5	115.96 (18)
C2—C1—H1C	109.5	C9—C8—C5	121.73 (16)
H1A—C1—H1C	109.5	C8—C9—C10	120.43 (18)
H1B—C1—H1C	109.5	C8—C9—H9	119.8
C7—C2—C3	117.2 (2)	C10—C9—H9	119.8
C7—C2—C1	120.4 (2)	C9—C10—C9ⁱ	116.5 (2)
C3—C2—C1	122.3 (2)	C9—C10—C11	121.74 (12)
C2—C3—C4	121.6 (2)	C9ⁱ—C10—C11	121.74 (12)
C2—C3—H3	119.2	C12—C11—C12ⁱ	118.0 (3)
C4—C3—H3	119.2	C12—C11—C10	121.01 (13)
C3—C4—C5	121.02 (19)	C12ⁱ—C11—C10	121.01 (13)
C3—C4—H4	119.5	C13—C12—C11	120.9 (2)
C5—C4—H4	119.5	C13—C12—H12	119.5
C4—C5—C6	117.42 (19)	C11—C12—H12	119.5
C4—C5—C8	120.58 (17)	C14—C13—C12	120.4 (2)
C6—C5—C8	122.0 (2)	C14—C13—H13	119.8
C5—C6—C7	120.7 (2)	C12—C13—H13	119.8
C5—C6—H6	119.6	C13—C14—C13ⁱ	119.3 (3)
C7—C6—H6	119.6	C13—C14—H14	120.4
C2—C7—C6	122.0 (2)	C13ⁱ—C14—H14	120.4

C7—C2—C3—C4	1.5 (4)	C4—C5—C8—C9	−156.5 (2)
C1—C2—C3—C4	180.0 (2)	C6—C5—C8—C9	24.5 (3)
C2—C3—C4—C5	−0.4 (4)	N1—C8—C9—C10	0.7 (2)
C3—C4—C5—C6	−1.0 (3)	C5—C8—C9—C10	−179.76 (15)
C3—C4—C5—C8	179.96 (19)	C8—C9—C10—C9ⁱ	−0.31 (12)
C4—C5—C6—C7	1.2 (4)	C8—C9—C10—C11	179.69 (12)
C8—C5—C6—C7	−179.8 (2)	C9—C10—C11—C12	32.62 (13)
C3—C2—C7—C6	−1.3 (4)	C9ⁱ—C10—C11—C12	−147.38 (13)
C1—C2—C7—C6	−179.8 (3)	C9—C10—C11—C12ⁱ	−147.38 (13)
C5—C6—C7—C2	0.0 (5)	C9ⁱ—C10—C11—C12ⁱ	32.62 (12)
C8ⁱ—N1—C8—C9	−0.33 (12)	C12ⁱ—C11—C12—C13	−0.07 (14)
C8ⁱ—N1—C8—C5	−179.93 (18)	C10—C11—C12—C13	179.93 (14)
C4—C5—C8—N1	23.1 (3)	C11—C12—C13—C14	0.1 (3)
C6—C5—C8—N1	−155.9 (2)	C12—C13—C14—C13ⁱ	−0.07 (14)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₁N
M_r	335.43
Crystal system, space group	Orthorhombic, Pcca
Temperature (K)	295
a, b, c (Å)	21.234 (3), 12.0489 (15), 7.3601 (10)
V (Å³)	1883.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.24 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.984, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	6295, 1833, 1130
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.179, 1.02
No. of reflections	1833
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

This work was supported by grants from the fundamental research projects of natural science of Shaanxi Province (Nos. 2010K14-02-23) and the scientific research plan projects of Shaanxi Education Department (Nos. 09JK837).

References

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