2,6-Bis(4-methoxy­phen­yl)-4-phenyl­pyridine

Dong, X.

doi:10.1107/S1600536809051277

organic compounds

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Volume 66| Part 1| January 2010| Page o38

doi:10.1107/S1600536809051277

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2,6-Bis(4-methoxyphenyl)-4-phenylpyridine

Xiaoning Dong ^a ^*

^aCollege of Life Sciences and Chemisrey, Tianshui Normal University, Tianshui, 741000, People's Republic of China
^*Correspondence e-mail: xndong@163.com

(Received 8 November 2009; accepted 28 November 2009; online 4 December 2009)

In the title compound, C₂₅H₂₁NO₂, which was synthesized by the condensation of 2,6-bis(4-methoxyphenyl)-4-phenylpyridinium tetrafluoroborate with ammonia under microwave irradiation and solvent-free conditions, the angles between the central pyridine ring and the three benzene rings are 22.3 (2), 35.3 (2) and 19.8 (2)°. In the crystal, intermolecular C—H⋯π hydrogen-bond interactions link the molecules.

Related literature

For the biological properties of pyridines, see Keys & Hamilton (1987 ); Chen et al.(1995 ). For related structures, see: Ondráček et al. (1994 ).

Experimental

Crystal data

C₂₅H₂₁NO₂
M_r = 367.43
Monoclinic, P 2₁ /n
a = 6.379 (3) Å
b = 15.538 (8) Å
c = 20.51 (1) Å
β = 94.281 (7)°
V = 2027.3 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.41 × 0.18 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.994
10098 measured reflections
3566 independent reflections
1522 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.099
wR(F²) = 0.191
S = 1.04
3566 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25C⋯Cg1ⁱ	0.96	2.82	3.605	140
Symmetry code: (i) -x, -y, -z. Cg1 is the centroid of the C19–C24 ring.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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/S1600536809051277/bq2177sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051277/bq2177Isup2.hkl

checkCIF report

Comment top

It was well known that pyridine ring systems have represented an important class of compounds not only for their theoretical interest but also because they displayed strong biological activity (Keys, et al., 1987). Moreover, pyridine derivatives have remarkable versatility in synthetic organic chemistry as intermediates in the preparation of nature products and as ligands recently used in asymmetric synthesis (Chen, et al., 1995).

In this paper, we present a new crystal, 2,6-bis(4'-methoxyphenyl)-4-phenylpyridine, (I), which was synthesized using benzaldehyde and 4-methoxylacetophenone as starting material.

In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in reported the compound (Ondráček et al., 1994). The angles between the center pyridine ring and benzene rings (c6 - c11), (c13 - c18) and (c19 - c24) are 22.28 (19)°, 35.29 (18)° and 19.81 (20)°, respectively, which show the pyridine ring and three benzene rings aren't coplanar. Moreover, the crystal supramolecular structure was built from the connections of C—H···π hydrogen bonding interactions, as shown in Table 1 and Fig. 2.

Related literature top

For the biological properties of pyridines, see Keys & Hamilton (1987); Chen et al.(1995). For related structures, see: Ondráček et al. (1994). Cg1 is the centroid of the C19–C24 ring

Experimental top

Benzaldehyde (0.3 mmol) and 4-methoxylacetophenone (0.6 mmol), ammonia (1.0 mmol) under boron trifluoride ether (0.1 mmol) catalyzed, the mixture were mixed in 50 ml flash. After eradiating 3 min at 375 W, the mixture then cooled slowly to room temperature affording the title compound, then recrystallized from ethanol, affording the title compound as a colorless crystalline solid. Elemental analysis: calculated for C₂₅H₂₁NO₂: C 81.72, H 5.76, N 3.81%; found: C 81.68, H 5.75, N 3.72%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. ORTEP drawing of the title complex with atomic numbering scheme and thermal ellipsoids at 30% probability level.
	Fig. 2. The one-dimensional chain structure was built by the C—H···π H-bond interactions (dashed lines).

2,6-Bis(4-methoxyphenyl)-4-phenylpyridine top

Crystal data top

C₂₅H₂₁NO₂	F(000) = 776
M_r = 367.43	D_x = 1.204 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 964 reflections
a = 6.379 (3) Å	θ = 2.6–25.1°
b = 15.538 (8) Å	µ = 0.08 mm⁻¹
c = 20.51 (1) Å	T = 298 K
β = 94.281 (7)°	Needle, colourless
V = 2027.3 (17) Å³	0.41 × 0.18 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3566 independent reflections
Radiation source: fine-focus sealed tube	1522 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.970, T_max = 0.994	k = −18→16
10098 measured reflections	l = −24→22

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)] = 0.099	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0521P)² + 0.3542P] where P = (F_o² + 2F_c²)/3
3566 reflections	(Δ/σ)_max < 0.001
255 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₅H₂₁NO₂	V = 2027.3 (17) Å³
M_r = 367.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.379 (3) Å	µ = 0.08 mm⁻¹
b = 15.538 (8) Å	T = 298 K
c = 20.51 (1) Å	0.41 × 0.18 × 0.08 mm
β = 94.281 (7)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3566 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1522 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.994	R_int = 0.109
10098 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.099	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.04	Δρ_max = 0.17 e Å⁻³
3566 reflections	Δρ_min = −0.16 e Å⁻³
255 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
N1	0.2077 (6)	0.7947 (2)	0.20968 (17)	0.0595 (10)
O1	−0.0669 (6)	0.8942 (2)	0.49408 (14)	0.0804 (11)
O2	−0.0509 (6)	0.9151 (2)	−0.08307 (14)	0.0762 (10)
C1	0.2860 (7)	0.7601 (3)	0.2683 (2)	0.0539 (12)
C2	0.4486 (7)	0.7015 (3)	0.2720 (2)	0.0608 (13)
H2	0.4984	0.6806	0.3127	0.073*
C3	0.5412 (7)	0.6725 (3)	0.2161 (2)	0.0569 (12)
C4	0.4592 (7)	0.7086 (3)	0.1567 (2)	0.0602 (13)
H4	0.5156	0.6927	0.1180	0.072*
C5	0.2955 (7)	0.7675 (3)	0.1551 (2)	0.0550 (12)
C6	0.1864 (7)	0.7938 (3)	0.3266 (2)	0.0542 (12)
C7	−0.0101 (8)	0.8304 (3)	0.3224 (2)	0.0724 (15)
H7	−0.0854	0.8318	0.2817	0.087*
C8	−0.1032 (8)	0.8657 (3)	0.3762 (2)	0.0759 (16)
H8	−0.2356	0.8909	0.3712	0.091*
C9	0.0074 (8)	0.8620 (3)	0.4375 (2)	0.0613 (13)
C10	0.2024 (8)	0.8247 (3)	0.4432 (2)	0.0637 (14)
H10	0.2753	0.8216	0.4841	0.076*
C11	0.2932 (7)	0.7916 (3)	0.3894 (2)	0.0619 (13)
H11	0.4268	0.7675	0.3947	0.074*
C12	−0.2641 (9)	0.9374 (4)	0.4904 (2)	0.105 (2)
H12A	−0.2614	0.9843	0.4600	0.157*
H12B	−0.2906	0.9592	0.5328	0.157*
H12C	−0.3734	0.8978	0.4759	0.157*
C13	0.7134 (7)	0.6082 (3)	0.2196 (2)	0.0548 (12)
C14	0.7190 (8)	0.5414 (3)	0.2660 (2)	0.0671 (14)
H14	0.6117	0.5367	0.2940	0.081*
C15	0.8826 (9)	0.4826 (3)	0.2703 (2)	0.0787 (16)
H15	0.8830	0.4387	0.3011	0.094*
C16	1.0438 (9)	0.4878 (3)	0.2299 (3)	0.0758 (16)
H16	1.1541	0.4486	0.2335	0.091*
C17	1.0390 (9)	0.5529 (4)	0.1837 (3)	0.0803 (16)
H17	1.1473	0.5573	0.1560	0.096*
C18	0.8745 (8)	0.6116 (3)	0.1782 (2)	0.0685 (14)
H18	0.8727	0.6539	0.1462	0.082*
C19	0.2008 (8)	0.8072 (3)	0.0924 (2)	0.0543 (12)
C20	0.0029 (8)	0.8437 (3)	0.0891 (2)	0.0613 (13)
H20	−0.0715	0.8438	0.1264	0.074*
C21	−0.0899 (7)	0.8807 (3)	0.0316 (2)	0.0645 (13)
H21	−0.2233	0.9050	0.0307	0.077*
C22	0.0210 (8)	0.8803 (3)	−0.0238 (2)	0.0605 (13)
C23	0.2184 (8)	0.8437 (3)	−0.0216 (2)	0.0661 (14)
H23	0.2922	0.8432	−0.0590	0.079*
C24	0.3083 (7)	0.8077 (3)	0.0356 (2)	0.0641 (13)
H24	0.4419	0.7835	0.0362	0.077*
C25	−0.2637 (9)	0.9444 (4)	−0.0914 (2)	0.0928 (18)
H25A	−0.3566	0.8985	−0.0813	0.139*
H25B	−0.2949	0.9623	−0.1359	0.139*
H25C	−0.2826	0.9921	−0.0627	0.139*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.071 (3)	0.063 (3)	0.045 (2)	0.004 (2)	0.001 (2)	0.001 (2)
O1	0.098 (3)	0.090 (3)	0.056 (2)	0.012 (2)	0.022 (2)	−0.0092 (19)
O2	0.093 (3)	0.089 (3)	0.045 (2)	0.004 (2)	−0.0074 (18)	0.0110 (17)
C1	0.068 (3)	0.055 (3)	0.039 (3)	0.007 (3)	0.005 (2)	0.001 (2)
C2	0.076 (4)	0.063 (3)	0.042 (3)	0.011 (3)	0.001 (2)	0.002 (2)
C3	0.068 (3)	0.058 (3)	0.044 (3)	0.002 (3)	0.001 (2)	0.000 (2)
C4	0.074 (4)	0.065 (3)	0.042 (3)	0.007 (3)	0.008 (3)	−0.002 (2)
C5	0.065 (3)	0.058 (3)	0.042 (3)	0.002 (3)	0.003 (2)	0.000 (2)
C6	0.059 (3)	0.059 (3)	0.044 (3)	0.009 (3)	0.000 (2)	0.002 (2)
C7	0.076 (4)	0.098 (4)	0.042 (3)	0.010 (3)	0.001 (3)	−0.002 (3)
C8	0.068 (4)	0.101 (4)	0.058 (3)	0.022 (3)	0.000 (3)	−0.002 (3)
C9	0.069 (4)	0.072 (4)	0.045 (3)	0.002 (3)	0.013 (3)	−0.001 (3)
C10	0.077 (4)	0.076 (4)	0.037 (3)	0.007 (3)	0.001 (3)	−0.001 (2)
C11	0.069 (3)	0.066 (3)	0.049 (3)	0.013 (3)	−0.002 (3)	0.003 (3)
C12	0.092 (5)	0.138 (5)	0.089 (4)	0.011 (4)	0.033 (4)	−0.029 (4)
C13	0.063 (3)	0.054 (3)	0.046 (3)	0.004 (3)	−0.002 (2)	−0.008 (2)
C14	0.072 (4)	0.072 (4)	0.057 (3)	0.010 (3)	0.006 (3)	0.006 (3)
C15	0.092 (5)	0.073 (4)	0.070 (4)	0.008 (4)	−0.007 (4)	0.005 (3)
C16	0.082 (4)	0.066 (4)	0.077 (4)	0.015 (3)	−0.011 (3)	−0.016 (3)
C17	0.076 (4)	0.091 (4)	0.074 (4)	0.004 (3)	0.007 (3)	−0.015 (3)
C18	0.074 (4)	0.068 (4)	0.064 (3)	0.008 (3)	0.010 (3)	0.002 (3)
C19	0.064 (3)	0.059 (3)	0.040 (3)	0.001 (2)	0.003 (2)	0.000 (2)
C20	0.068 (4)	0.076 (4)	0.041 (3)	0.000 (3)	0.011 (2)	0.004 (2)
C21	0.069 (3)	0.076 (4)	0.047 (3)	0.009 (3)	−0.004 (3)	0.004 (3)
C22	0.078 (4)	0.065 (3)	0.037 (3)	−0.002 (3)	−0.002 (3)	0.001 (2)
C23	0.073 (4)	0.084 (4)	0.041 (3)	0.007 (3)	0.006 (3)	−0.002 (3)
C24	0.065 (3)	0.077 (4)	0.049 (3)	0.006 (3)	−0.003 (3)	0.003 (3)
C25	0.089 (5)	0.114 (5)	0.070 (4)	0.009 (4)	−0.024 (3)	0.015 (3)

Geometric parameters (Å, º) top

N1—C5	1.356 (5)	C12—H12B	0.9600
N1—C1	1.376 (5)	C12—H12C	0.9600
O1—C9	1.379 (5)	C13—C18	1.381 (6)
O1—C12	1.423 (5)	C13—C14	1.406 (6)
O2—C22	1.378 (5)	C14—C15	1.385 (6)
O2—C25	1.430 (5)	C14—H14	0.9300
C1—C2	1.378 (5)	C15—C16	1.370 (6)
C1—C6	1.491 (5)	C15—H15	0.9300
C2—C3	1.402 (5)	C16—C17	1.384 (6)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.406 (5)	C17—C18	1.388 (6)
C3—C13	1.483 (6)	C17—H17	0.9300
C4—C5	1.387 (5)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.381 (6)
C5—C19	1.512 (6)	C19—C24	1.394 (5)
C6—C7	1.373 (6)	C20—C21	1.403 (5)
C6—C11	1.412 (5)	C20—H20	0.9300
C7—C8	1.404 (6)	C21—C22	1.382 (6)
C7—H7	0.9300	C21—H21	0.9300
C8—C9	1.396 (5)	C22—C23	1.379 (6)
C8—H8	0.9300	C23—C24	1.385 (5)
C9—C10	1.369 (6)	C23—H23	0.9300
C10—C11	1.383 (5)	C24—H24	0.9300
C10—H10	0.9300	C25—H25A	0.9600
C11—H11	0.9300	C25—H25B	0.9600
C12—H12A	0.9600	C25—H25C	0.9600

C5—N1—C1	117.0 (4)	C18—C13—C14	117.4 (4)
C9—O1—C12	119.0 (4)	C18—C13—C3	121.8 (4)
C22—O2—C25	118.8 (4)	C14—C13—C3	120.7 (4)
N1—C1—C2	121.9 (4)	C15—C14—C13	120.7 (5)
N1—C1—C6	114.5 (4)	C15—C14—H14	119.6
C2—C1—C6	123.5 (4)	C13—C14—H14	119.6
C1—C2—C3	121.9 (4)	C16—C15—C14	121.2 (5)
C1—C2—H2	119.1	C16—C15—H15	119.4
C3—C2—H2	119.1	C14—C15—H15	119.4
C2—C3—C4	115.3 (4)	C15—C16—C17	118.5 (5)
C2—C3—C13	122.2 (4)	C15—C16—H16	120.7
C4—C3—C13	122.4 (4)	C17—C16—H16	120.7
C5—C4—C3	121.0 (4)	C16—C17—C18	120.9 (5)
C5—C4—H4	119.5	C16—C17—H17	119.6
C3—C4—H4	119.5	C18—C17—H17	119.6
N1—C5—C4	122.8 (4)	C13—C18—C17	121.2 (5)
N1—C5—C19	114.4 (4)	C13—C18—H18	119.4
C4—C5—C19	122.8 (4)	C17—C18—H18	119.4
C7—C6—C11	116.3 (4)	C20—C19—C24	117.5 (4)
C7—C6—C1	122.4 (4)	C20—C19—C5	121.0 (4)
C11—C6—C1	121.2 (4)	C24—C19—C5	121.5 (4)
C6—C7—C8	123.3 (4)	C19—C20—C21	122.4 (4)
C6—C7—H7	118.3	C19—C20—H20	118.8
C8—C7—H7	118.3	C21—C20—H20	118.8
C9—C8—C7	118.5 (4)	C22—C21—C20	118.6 (5)
C9—C8—H8	120.7	C22—C21—H21	120.7
C7—C8—H8	120.7	C20—C21—H21	120.7
C10—C9—O1	116.7 (4)	O2—C22—C23	115.7 (4)
C10—C9—C8	119.3 (4)	O2—C22—C21	124.5 (5)
O1—C9—C8	124.1 (5)	C23—C22—C21	119.8 (4)
C9—C10—C11	121.4 (4)	C22—C23—C24	120.9 (4)
C9—C10—H10	119.3	C22—C23—H23	119.5
C11—C10—H10	119.3	C24—C23—H23	119.5
C10—C11—C6	121.1 (4)	C23—C24—C19	120.7 (4)
C10—C11—H11	119.4	C23—C24—H24	119.6
C6—C11—H11	119.4	C19—C24—H24	119.6
O1—C12—H12A	109.5	O2—C25—H25A	109.5
O1—C12—H12B	109.5	O2—C25—H25B	109.5
H12A—C12—H12B	109.5	H25A—C25—H25B	109.5
O1—C12—H12C	109.5	O2—C25—H25C	109.5
H12A—C12—H12C	109.5	H25A—C25—H25C	109.5
H12B—C12—H12C	109.5	H25B—C25—H25C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25C···Cg1ⁱ	0.96	2.82	3.605	140

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₁NO₂
M_r	367.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.379 (3), 15.538 (8), 20.51 (1)
β (°)	94.281 (7)
V (Å³)	2027.3 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.41 × 0.18 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	10098, 3566, 1522
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.099, 0.191, 1.04
No. of reflections	3566
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
C25—H25C···Cg1ⁱ	0.96	2.82	3.605	139.6

Symmetry code: (i) −x, −y, −z.

Acknowledgements

The author acknowledges the support of the Foundation of Tianshui Normal University.

References

Chen, C., Tagami, K. & Kishi, Y. (1995). J. Org. Chem. 60, 5386–5387. CrossRef CAS Web of Science Google Scholar
Keys, L. D. & Hamilton, G. A. (1987). J. Am. Chem. Soc. 109, 2156–2163. CrossRef CAS Web of Science Google Scholar
Ondráček, J., Novotný, J., Petrů, M., Lhoták, P. & Kuthan, J. (1994). Acta Cryst. C50, 1809–1811. CSD CrossRef Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Systems, Inc., Madison, Wisconsin, USA. Google Scholar