2,4,6-Tri-p-tolyl­pyridine

Tang, S.-P.; Kuang, D.-Z.; Feng, Y.-L.; Chen, M.-S.; Li, W.

doi:10.1107/S160053680901931X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1412

doi:10.1107/S160053680901931X

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2,4,6-Tri-p-tolylpyridine

Si-Ping Tang,^a ^* Dai-Zhi Kuang,^a Yong-Lan Feng,^a Man-Sheng Chen ^a and Wei Li ^a

^aKey Laboratory of Functional Organometallic Materials, Hengyang Normal University, Hengyang, Hunan 421008, People's Republic of China
^*Correspondence e-mail: sptang88@163.com

(Received 20 May 2009; accepted 21 May 2009; online 29 May 2009)

In the title compound, C₂₆H₂₃N, the complete molecule is generated by crystallographic mirror symmetry, with the N atom and four C atoms lying on the reflection plane. The dihedral angles between the pyridine ring and pendant benzene rings are 2.9 (1), 14.1 (1) and 14.1 (1)°. Neighbouring molecules are stabilized through intermolecular π–π interactions along the c axis [centroid-to-centroid distance = 3.804 (2) Å], forming one-dimensional chains.

Related literature

For the syntheses of related 2,4,6-triarylpyridine compounds, see: Hou et al. (2005 ); Huang et al. (2005 ); Tewari et al. (1981 ); Yang et al. (2005 ).

Experimental

Crystal data

C₂₆H₂₃N
M_r = 349.45
Orthorhombic, P n m a
a = 15.337 (5) Å
b = 20.778 (7) Å
c = 6.322 (2) Å
V = 2014.8 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 295 K
0.24 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.975, T_max = 0.986
7912 measured reflections
2037 independent reflections
924 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.139
wR(F²) = 0.342
S = 1.26
2037 reflections
132 parameters
47 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901931X/at2790sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901931X/at2790Isup2.hkl

checkCIF report

Comment top

2,4,6-Triarylpyridines are used as good building blocks in supramolecular chemistry because of their stacking ability, directional H-bonding and coordination, and which have also been prepared by many procedures (Hou et al., 2005; Huang et al., 2005; Tewari et al., 1981; Yang et al., 2005). We here reported the synthesis and crystal structure of 2,4,6-tri-p-tolylpyridine.

As shown in Fig.1, the title compound is a neutral organic molecule with a mirror symmetry through the methyl C15 atom and N1 atom of the central pyridine. The central pyridine is almost coplanar with the C_11-14 benzene ring with a dihedral angle of 2.9 (1) °, however, which form bigger dihedral angles of 14.1 (1) ° with the other two outer benzene rings, thus the whole molecule is nonplanar. In the crystal packing, neighboring molecules form intermolecular π–π interactions with the centroid- to-centroid distances of 3.804 (2) Å to give a one-dimensional chain along the c-axis.

Related literature top

For the related synthesis of 2,4,6-triarylpyridine compounds, see: Hou et al. (2005); Huang et al. (2005); Tewari et al. (1981); Yang et al. (2005).

Experimental top

The title compound was synthesized with a modified procedure (Yang et al., 2005). A mixture of 5-tri-p-tolyl-pentane-1,5-dione (1.85 g, 5 mmol), ammonium acetate (3.85 g, 50 mmol) and ethanol (60 mL) was refluxed for 20 h. Upon cooling to room temperature, a precipitate was filtered, washed with ethanol/water (1:1) and dried to afford the product, purified by column chromatography on silica with petroleum/ethyl acetate. A white solid was obtained and was further recrystallized from ethanol to give colourless crystals [yield: 0.85 g, 48.6%].

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).

Figures top

Fig. 1. The title molecule with displacement ellipsoids drawn at the 30% probability level, and H atoms as spheres of arbitrary radius.

2,4,6-Tri-p-tolylpyridine top

Crystal data top

C₂₆H₂₃N	F(000) = 744
M_r = 349.45	D_x = 1.152 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 562 reflections
a = 15.337 (5) Å	θ = 2.7–22.4°
b = 20.778 (7) Å	µ = 0.07 mm⁻¹
c = 6.322 (2) Å	T = 295 K
V = 2014.8 (11) Å³	Prism, colourless
Z = 4	0.24 × 0.16 × 0.15 mm

Data collection top

Bruker SMART APEX area-detector diffractometer	2037 independent reflections
Radiation source: fine-focus sealed tube	924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→18
T_min = 0.975, T_max = 0.986	k = −20→25
7912 measured reflections	l = −7→5

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)] = 0.139	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.342	H-atom parameters constrained
S = 1.26	w = 1/[σ²(F_o²) + (0.0923P)² + 1.1054P] where P = (F_o² + 2F_c²)/3
2037 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.27 e Å⁻³
47 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₆H₂₃N	V = 2014.8 (11) Å³
M_r = 349.45	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.337 (5) Å	µ = 0.07 mm⁻¹
b = 20.778 (7) Å	T = 295 K
c = 6.322 (2) Å	0.24 × 0.16 × 0.15 mm

Data collection top

Bruker SMART APEX area-detector diffractometer	2037 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	924 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.986	R_int = 0.067
7912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.139	47 restraints
wR(F²) = 0.342	H-atom parameters constrained
S = 1.26	Δρ_max = 0.27 e Å⁻³
2037 reflections	Δρ_min = −0.20 e Å⁻³
132 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	Occ. (<1)
C1	0.4178 (6)	0.5536 (4)	0.7562 (16)	0.180 (4)
H1A	0.4197	0.5501	0.9076	0.270*
H1B	0.3776	0.5869	0.7165	0.270*
H1C	0.4749	0.5639	0.7038	0.270*
C2	0.3882 (5)	0.4900 (4)	0.6625 (15)	0.139 (3)
C3	0.3948 (6)	0.4331 (5)	0.7686 (15)	0.158 (3)
H3	0.4171	0.4334	0.9053	0.190*
C4	0.3696 (5)	0.3750 (4)	0.6812 (13)	0.143 (3)
H4	0.3750	0.3378	0.7624	0.172*
C5	0.3376 (4)	0.3699 (4)	0.4833 (11)	0.098 (2)
C6	0.3283 (6)	0.4267 (5)	0.3786 (13)	0.139 (3)
H6	0.3050	0.4261	0.2428	0.167*
C7	0.3522 (6)	0.4853 (4)	0.4650 (15)	0.163 (4)
H7	0.3435	0.5226	0.3866	0.196*
C8	0.3116 (4)	0.3075 (3)	0.3878 (9)	0.0859 (18)
C9	0.2622 (3)	0.3058 (2)	0.2112 (8)	0.0646 (14)
H9	0.2455	0.3443	0.1479	0.077*
N1	0.3373 (5)	0.2500	0.4758 (13)	0.123 (3)
C10	0.2366 (5)	0.2500	0.1249 (12)	0.075 (2)
C11	0.1802 (4)	0.2500	−0.0662 (12)	0.0673 (19)
C12	0.1525 (4)	0.3049 (3)	−0.1594 (11)	0.107 (2)
H12	0.1713	0.3442	−0.1057	0.128*
C13	0.0972 (5)	0.3044 (3)	−0.3317 (11)	0.121 (2)
H13	0.0794	0.3438	−0.3873	0.145*
C14	0.0676 (6)	0.2500	−0.4240 (15)	0.103 (3)
C15	0.0081 (6)	0.2500	−0.6115 (15)	0.133 (3)
H15A	0.0335	0.2753	−0.7227	0.199*	0.50
H15B	−0.0472	0.2681	−0.5722	0.199*	0.50
H15C	−0.0001	0.2066	−0.6600	0.199*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.158 (7)	0.165 (7)	0.217 (9)	0.049 (6)	−0.066 (7)	−0.093 (7)
C2	0.111 (5)	0.149 (7)	0.157 (7)	0.030 (5)	−0.054 (5)	−0.053 (5)
C3	0.153 (5)	0.181 (7)	0.141 (6)	−0.015 (5)	−0.063 (5)	−0.029 (5)
C4	0.142 (5)	0.165 (6)	0.122 (5)	−0.027 (4)	−0.049 (5)	−0.006 (5)
C5	0.074 (4)	0.142 (5)	0.078 (4)	0.003 (4)	−0.022 (3)	−0.008 (4)
C6	0.157 (7)	0.141 (7)	0.119 (7)	0.036 (6)	−0.052 (5)	−0.024 (6)
C7	0.186 (9)	0.132 (7)	0.171 (9)	0.057 (6)	−0.061 (8)	−0.042 (6)
C8	0.063 (3)	0.120 (5)	0.075 (4)	0.002 (4)	0.002 (3)	0.001 (4)
C9	0.054 (3)	0.080 (3)	0.060 (3)	0.011 (3)	−0.013 (3)	−0.001 (3)
N1	0.089 (6)	0.180 (9)	0.098 (6)	0.000	0.011 (5)	0.000
C10	0.055 (4)	0.103 (6)	0.065 (5)	0.000	0.011 (4)	0.000
C11	0.060 (4)	0.076 (5)	0.066 (5)	0.000	−0.002 (4)	0.000
C12	0.119 (5)	0.092 (4)	0.110 (5)	−0.002 (4)	−0.037 (4)	0.003 (4)
C13	0.114 (5)	0.141 (6)	0.108 (5)	0.004 (4)	−0.038 (4)	0.031 (4)
C14	0.078 (5)	0.152 (7)	0.079 (5)	0.000	−0.020 (4)	0.000
C15	0.098 (6)	0.216 (9)	0.085 (6)	0.000	−0.022 (5)	0.000

Geometric parameters (Å, º) top

C1—C2	1.518 (10)	C9—C10	1.340 (6)
C1—H1A	0.9600	C9—H9	0.9300
C1—H1B	0.9600	N1—C8ⁱ	1.375 (5)
C1—H1C	0.9600	C10—C9ⁱ	1.340 (6)
C2—C3	1.361 (8)	C10—C11	1.486 (10)
C2—C7	1.369 (8)	C11—C12ⁱ	1.352 (6)
C3—C4	1.384 (10)	C11—C12	1.352 (6)
C3—H3	0.9300	C12—C13	1.381 (8)
C4—C5	1.348 (9)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.352 (6)
C5—C6	1.361 (9)	C13—H13	0.9300
C5—C8	1.484 (8)	C14—C13ⁱ	1.352 (6)
C6—C7	1.384 (9)	C14—C15	1.495 (12)
C6—H6	0.9300	C15—H15A	0.9600
C7—H7	0.9300	C15—H15B	0.9600
C8—C9	1.350 (7)	C15—H15C	0.9600
C8—N1	1.375 (5)

C2—C1—H1A	109.5	N1—C8—C5	121.1 (6)
C2—C1—H1B	109.5	C10—C9—C8	121.5 (6)
H1A—C1—H1B	109.5	C10—C9—H9	119.2
C2—C1—H1C	109.5	C8—C9—H9	119.2
H1A—C1—H1C	109.5	C8ⁱ—N1—C8	120.6 (9)
H1B—C1—H1C	109.5	C9—C10—C9ⁱ	119.8 (7)
C3—C2—C7	114.7 (9)	C9—C10—C11	120.1 (4)
C3—C2—C1	122.7 (8)	C9ⁱ—C10—C11	120.1 (4)
C7—C2—C1	122.6 (9)	C12ⁱ—C11—C12	115.0 (8)
C2—C3—C4	122.7 (8)	C12ⁱ—C11—C10	122.5 (4)
C2—C3—H3	118.7	C12—C11—C10	122.5 (4)
C4—C3—H3	118.7	C11—C12—C13	122.1 (6)
C5—C4—C3	122.7 (9)	C11—C12—H12	118.9
C5—C4—H4	118.6	C13—C12—H12	118.9
C3—C4—H4	118.6	C14—C13—C12	123.5 (7)
C4—C5—C6	114.9 (8)	C14—C13—H13	118.2
C4—C5—C8	123.0 (7)	C12—C13—H13	118.2
C6—C5—C8	122.1 (6)	C13—C14—C13ⁱ	113.6 (9)
C5—C6—C7	122.9 (8)	C13—C14—C15	123.2 (4)
C5—C6—H6	118.5	C13ⁱ—C14—C15	123.2 (4)
C7—C6—H6	118.5	C14—C15—H15A	109.5
C2—C7—C6	122.0 (9)	C14—C15—H15B	109.5
C2—C7—H7	119.0	H15A—C15—H15B	109.5
C6—C7—H7	119.0	C14—C15—H15C	109.5
C9—C8—N1	118.2 (7)	H15A—C15—H15C	109.5
C9—C8—C5	120.6 (5)	H15B—C15—H15C	109.5

C7—C2—C3—C4	1.9 (14)	C5—C8—C9—C10	−178.7 (6)
C1—C2—C3—C4	−178.5 (8)	C9—C8—N1—C8ⁱ	−1.3 (11)
C2—C3—C4—C5	0.8 (15)	C5—C8—N1—C8ⁱ	178.9 (5)
C3—C4—C5—C6	−2.7 (12)	C8—C9—C10—C9ⁱ	−1.8 (10)
C3—C4—C5—C8	179.1 (7)	C8—C9—C10—C11	178.3 (5)
C4—C5—C6—C7	1.8 (12)	C9—C10—C11—C12ⁱ	−179.9 (6)
C8—C5—C6—C7	180.0 (7)	C9ⁱ—C10—C11—C12ⁱ	0.2 (10)
C3—C2—C7—C6	−2.8 (14)	C9—C10—C11—C12	−0.2 (10)
C1—C2—C7—C6	177.6 (8)	C9ⁱ—C10—C11—C12	179.9 (6)
C5—C6—C7—C2	1.0 (15)	C12ⁱ—C11—C12—C13	2.5 (12)
C4—C5—C8—C9	164.8 (6)	C10—C11—C12—C13	−177.3 (6)
C6—C5—C8—C9	−13.2 (10)	C11—C12—C13—C14	−1.3 (12)
C4—C5—C8—N1	−15.4 (10)	C12—C13—C14—C13ⁱ	0.0 (15)
C6—C5—C8—N1	166.6 (7)	C12—C13—C14—C15	−179.6 (8)
N1—C8—C9—C10	1.5 (9)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₃N
M_r	349.45
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	295
a, b, c (Å)	15.337 (5), 20.778 (7), 6.322 (2)
V (Å³)	2014.8 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.24 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	7912, 2037, 924
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.139, 0.342, 1.26
No. of reflections	2037
No. of parameters	132
No. of restraints	47
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.20

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

Acknowledgements

The authors thank the Key Discipline Construct Program of Hunan province and the Foundation of Hunan Province Education Office (grant No. 08 C178) for supporting this study.

References

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