Bis(3-meth­oxy-6-methyl-2-pyrid­yl) ether

Jiang, Y.-Y.; Lan, H.-H.; Deng, D.-S.; Ji, B.-M.

doi:10.1107/S160053680706775X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o369

doi:10.1107/S160053680706775X

Open

access

Bis(3-methoxy-6-methyl-2-pyridyl) ether

Yuan-Yuan Jiang,^a Hong-Hong Lan,^b Dong-Sheng Deng ^c and Bao-Ming Ji ^c ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China, ^bDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: lyhxxjbm@126.com

(Received 7 December 2007; accepted 19 December 2007; online 4 January 2008)

In the molecule of the title compound, C₁₄H₁₆N₂O₃, the dihedral angle between the pyridyl rings is 87.74 (3)°. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into infinite zigzag chains.

Related literature

For related literature, see: Jung et al. (1997 ); Dunne et al. (1995 ); Wang et al. (2001 ); Goulle et al. (1993 ); Gilat et al. (1995 ); Kawai et al. (1995 ); Gütlich et al. (1994 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₆N₂O₃
M_r = 260.29
Monoclinic, P 2₁ /c
a = 12.146 (2) Å
b = 7.5372 (15) Å
c = 14.669 (3) Å
β = 94.577 (3)°
V = 1338.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.29 × 0.21 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.974, T_max = 0.988
8226 measured reflections
2477 independent reflections
1229 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.146
S = 1.01
2477 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.93	2.52	3.358 (3)	150
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706775X/hk2409sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680706775X/hk2409Isup2.hkl

checkCIF report

Comment top

2,2'-Dipyridylether and its derivatives are a kind of extensively studied (Jung et al., 1997; Dunne et al., 1995; Wang et al., 2001; Goulle et al., 1993) multifuntional organic ligands. Most research in this area has focused on conjugated organic molecules undergoing frequency-sensitive reversible bond-forming reactions, for the design of inorganic or organometallic switches (Gilat et al., 1995; Kawai et al., 1995; Gütlich et al., 1994). As part of our ongoing studies, we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/C1/C2/C4—C6) and B (N2/C9/C10/C12—C14) are, of course, planar and the dihedral angle between them is A/B = 87.74 (3)°.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into infinite zigzag chains (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Jung et al. (1997); Dunne et al. (1995); Wang et al. (2001); Goulle et al. (1993); Gilat et al. (1995); Kawai et al. (1995); Gütlich et al. (1994). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 2-iodo-3-methoxy-6-methylpyridine (250 mg, 1 mmol) and active Cu powder (511 mg, 8 mmol) were added to a solution of DMF (10 ml). The resulting mixture was heated at 428 K for 24 h under nitrogen atmosphere. After the active Cu powder was filtered, the filtrate was washed with water (3 × 20 ml), and the aqueous layer was extracted by ethyl acetate (3 × 20 ml). The combined organic layer was dried over anhydrous MgSO₄, and the solvent was removed in vacuo to give the crude product. After purification by silica gel chromatography, a clear solution was set aside to crystallize.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Bis(3-methoxy-6-methyl-2-pyridyl) ether top

Crystal data top

C₁₄H₁₆N₂O₃	F(000) = 552
M_r = 260.29	D_x = 1.292 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1190 reflections
a = 12.146 (2) Å	θ = 2.8–20.3°
b = 7.5372 (15) Å	µ = 0.09 mm⁻¹
c = 14.669 (3) Å	T = 294 K
β = 94.577 (3)°	Block, colorless
V = 1338.6 (4) Å³	0.29 × 0.21 × 0.13 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2477 independent reflections
Radiation source: fine-focus sealed tube	1229 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.974, T_max = 0.988	k = −9→8
8226 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0653P)² + 0.0571P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2477 reflections	Δρ_max = 0.13 e Å⁻³
177 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0071 (19)

Crystal data top

C₁₄H₁₆N₂O₃	V = 1338.6 (4) Å³
M_r = 260.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.146 (2) Å	µ = 0.09 mm⁻¹
b = 7.5372 (15) Å	T = 294 K
c = 14.669 (3) Å	0.29 × 0.21 × 0.13 mm
β = 94.577 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2477 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1229 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.988	R_int = 0.041
8226 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.01	Δρ_max = 0.13 e Å⁻³
2477 reflections	Δρ_min = −0.11 e Å⁻³
177 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	0.77209 (13)	0.0344 (2)	0.12530 (11)	0.0774 (6)
O2	0.97934 (14)	0.1001 (2)	0.10596 (15)	0.0854 (6)
O3	0.72046 (17)	−0.3036 (3)	0.15773 (14)	0.0996 (7)
N1	0.79139 (16)	0.0722 (3)	0.28290 (16)	0.0669 (6)
N2	0.59034 (19)	0.1178 (3)	0.11932 (13)	0.0747 (7)
C1	0.9468 (2)	0.1105 (3)	0.1925 (2)	0.0677 (7)
C2	0.8363 (2)	0.0727 (3)	0.2043 (2)	0.0630 (7)
C4	0.8564 (2)	0.1129 (3)	0.3590 (2)	0.0736 (8)
C5	0.9660 (3)	0.1532 (4)	0.3532 (2)	0.0884 (9)
H5	1.0099	0.1810	0.4061	0.106*
C6	1.0115 (2)	0.1529 (3)	0.2703 (2)	0.0837 (9)
H6	1.0856	0.1813	0.2671	0.100*
C7	0.8040 (2)	0.1079 (4)	0.44789 (19)	0.0953 (9)
H7A	0.7319	0.1603	0.4401	0.143*
H7B	0.8489	0.1731	0.4932	0.143*
H7C	0.7978	−0.0130	0.4674	0.143*
C8	1.0953 (2)	0.1180 (4)	0.0964 (2)	0.0986 (10)
H8A	1.1190	0.2350	0.1148	0.148*
H8B	1.1096	0.0990	0.0337	0.148*
H8C	1.1352	0.0318	0.1343	0.148*
C9	0.6354 (2)	−0.1871 (4)	0.14619 (17)	0.0750 (8)
C10	0.6628 (2)	−0.0120 (4)	0.13349 (16)	0.0660 (7)
C12	0.4831 (2)	0.0807 (5)	0.11836 (18)	0.0813 (9)
C13	0.4500 (3)	−0.0916 (5)	0.1311 (2)	0.0928 (10)
H13	0.3749	−0.1166	0.1301	0.111*
C14	0.5245 (3)	−0.2276 (5)	0.14539 (19)	0.0889 (9)
H14	0.5010	−0.3433	0.1542	0.107*
C15	0.4036 (2)	0.2307 (5)	0.1025 (2)	0.1091 (11)
H15A	0.3917	0.2861	0.1598	0.164*
H15B	0.3347	0.1862	0.0749	0.164*
H15C	0.4332	0.3160	0.0624	0.164*
C16	0.6933 (3)	−0.4891 (4)	0.1585 (2)	0.1124 (11)
H16A	0.6520	−0.5143	0.2100	0.169*
H16B	0.7601	−0.5579	0.1627	0.169*
H16C	0.6498	−0.5190	0.1031	0.169*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0539 (11)	0.1004 (15)	0.0774 (12)	−0.0163 (10)	0.0011 (9)	0.0035 (10)
O2	0.0556 (12)	0.0860 (14)	0.1149 (16)	−0.0083 (9)	0.0090 (10)	0.0070 (12)
O3	0.0906 (15)	0.0842 (15)	0.1229 (17)	0.0000 (12)	0.0017 (12)	0.0031 (12)
N1	0.0656 (14)	0.0569 (14)	0.0764 (15)	−0.0016 (10)	−0.0059 (12)	0.0004 (11)
N2	0.0645 (15)	0.0939 (18)	0.0648 (14)	−0.0066 (14)	0.0002 (11)	−0.0061 (12)
C1	0.0533 (16)	0.0486 (15)	0.100 (2)	−0.0005 (12)	0.0001 (16)	0.0009 (15)
C2	0.0559 (16)	0.0473 (15)	0.083 (2)	−0.0043 (12)	−0.0124 (15)	0.0040 (14)
C4	0.078 (2)	0.0514 (16)	0.088 (2)	0.0046 (14)	−0.0149 (17)	−0.0074 (14)
C5	0.082 (2)	0.068 (2)	0.108 (3)	−0.0014 (16)	−0.0298 (19)	−0.0185 (18)
C6	0.0581 (17)	0.0625 (19)	0.128 (3)	−0.0084 (14)	−0.0108 (19)	−0.0091 (18)
C7	0.111 (2)	0.087 (2)	0.086 (2)	0.0068 (18)	−0.0066 (18)	−0.0127 (17)
C8	0.0561 (18)	0.091 (2)	0.150 (3)	−0.0090 (16)	0.0203 (17)	0.006 (2)
C9	0.0730 (19)	0.077 (2)	0.0749 (19)	−0.0030 (17)	0.0040 (15)	−0.0077 (16)
C10	0.0541 (16)	0.080 (2)	0.0635 (17)	−0.0112 (15)	0.0030 (12)	−0.0036 (15)
C12	0.064 (2)	0.112 (3)	0.0676 (18)	−0.0007 (18)	0.0036 (14)	−0.0150 (17)
C13	0.0588 (18)	0.127 (3)	0.094 (2)	−0.019 (2)	0.0089 (16)	−0.032 (2)
C14	0.075 (2)	0.099 (2)	0.093 (2)	−0.0320 (19)	0.0139 (17)	−0.0205 (19)
C15	0.079 (2)	0.145 (3)	0.102 (2)	0.030 (2)	−0.0016 (17)	−0.009 (2)
C16	0.146 (3)	0.071 (2)	0.124 (3)	−0.006 (2)	0.037 (2)	0.000 (2)

Geometric parameters (Å, º) top

O1—C2	1.374 (3)	C7—H7C	0.9600
O1—C10	1.388 (3)	C8—H8A	0.9600
O2—C1	1.361 (3)	C8—H8B	0.9600
O2—C8	1.433 (3)	C8—H8C	0.9600
O3—C9	1.356 (3)	C9—C14	1.381 (4)
O3—C16	1.437 (3)	C10—N2	1.321 (3)
N1—C2	1.315 (3)	C10—C9	1.377 (4)
N1—C4	1.350 (3)	C12—C13	1.377 (4)
N2—C12	1.331 (3)	C12—C15	1.493 (4)
C1—C6	1.371 (4)	C13—C14	1.372 (4)
C2—C1	1.396 (3)	C13—H13	0.9300
C4—C5	1.375 (4)	C14—H14	0.9300
C4—C7	1.496 (3)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C5	1.376 (4)	C15—H15C	0.9600
C6—H6	0.9300	C16—H16A	0.9600
C7—H7A	0.9600	C16—H16B	0.9600
C7—H7B	0.9600	C16—H16C	0.9600

C2—O1—C10	117.5 (2)	H8A—C8—H8C	109.5
C1—O2—C8	116.6 (2)	H8B—C8—H8C	109.5
C9—O3—C16	117.3 (2)	O3—C9—C10	116.6 (2)
C2—N1—C4	118.0 (2)	O3—C9—C14	126.2 (3)
C10—N2—C12	119.0 (3)	C10—C9—C14	117.1 (3)
O2—C1—C6	126.9 (3)	N2—C10—C9	124.5 (2)
O2—C1—C2	117.2 (2)	N2—C10—O1	115.4 (2)
C6—C1—C2	115.9 (3)	C9—C10—O1	119.7 (3)
N1—C2—O1	119.5 (2)	N2—C12—C13	119.6 (3)
N1—C2—C1	125.4 (3)	N2—C12—C15	117.6 (3)
O1—C2—C1	115.1 (3)	C13—C12—C15	122.9 (3)
N1—C4—C5	120.3 (3)	C14—C13—C12	121.9 (3)
N1—C4—C7	117.0 (3)	C14—C13—H13	119.0
C5—C4—C7	122.7 (3)	C12—C13—H13	119.0
C4—C5—C6	120.9 (3)	C13—C14—C9	117.9 (3)
C4—C5—H5	119.5	C13—C14—H14	121.1
C6—C5—H5	119.5	C9—C14—H14	121.1
C1—C6—C5	119.5 (3)	C12—C15—H15A	109.5
C1—C6—H6	120.3	C12—C15—H15B	109.5
C5—C6—H6	120.3	H15A—C15—H15B	109.5
C4—C7—H7A	109.5	C12—C15—H15C	109.5
C4—C7—H7B	109.5	H15A—C15—H15C	109.5
H7A—C7—H7B	109.5	H15B—C15—H15C	109.5
C4—C7—H7C	109.5	O3—C16—H16A	109.5
H7A—C7—H7C	109.5	O3—C16—H16B	109.5
H7B—C7—H7C	109.5	H16A—C16—H16B	109.5
O2—C8—H8A	109.5	O3—C16—H16C	109.5
O2—C8—H8B	109.5	H16A—C16—H16C	109.5
H8A—C8—H8B	109.5	H16B—C16—H16C	109.5
O2—C8—H8C	109.5

C10—O1—C2—N1	−3.1 (3)	O1—C2—C1—O2	−2.0 (3)
C10—O1—C2—C1	177.2 (2)	N1—C2—C1—C6	−1.1 (4)
C2—O1—C10—N2	97.5 (3)	O1—C2—C1—C6	178.6 (2)
C2—O1—C10—C9	−88.9 (3)	N1—C4—C5—C6	0.0 (4)
C8—O2—C1—C6	6.7 (4)	C7—C4—C5—C6	178.7 (3)
C8—O2—C1—C2	−172.6 (2)	C1—C6—C5—C4	−0.5 (4)
C16—O3—C9—C10	−171.7 (2)	O3—C9—C14—C13	−178.9 (3)
C16—O3—C9—C14	7.9 (4)	C10—C9—C14—C13	0.7 (4)
C2—N1—C4—C5	0.0 (4)	C9—C10—N2—C12	1.1 (4)
C2—N1—C4—C7	−178.8 (2)	O1—C10—N2—C12	174.4 (2)
C4—N1—C2—O1	−179.1 (2)	N2—C10—C9—O3	178.5 (2)
C4—N1—C2—C1	0.6 (4)	O1—C10—C9—O3	5.4 (4)
C10—N2—C12—C13	−0.7 (4)	N2—C10—C9—C14	−1.1 (4)
C10—N2—C12—C15	179.8 (2)	O1—C10—C9—C14	−174.2 (2)
O2—C1—C6—C5	−178.4 (2)	N2—C12—C13—C14	0.3 (4)
C2—C1—C6—C5	1.0 (4)	C15—C12—C13—C14	179.8 (3)
N1—C2—C1—O2	178.3 (2)	C12—C13—C14—C9	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.93	2.52	3.358 (3)	150

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂O₃
M_r	260.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.146 (2), 7.5372 (15), 14.669 (3)
β (°)	94.577 (3)
V (Å³)	1338.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.21 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.974, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	8226, 2477, 1229
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.147, 1.01
No. of reflections	2477
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.11

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.93	2.52	3.358 (3)	150.0

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the Henan Innovation Project for University Prominent Research Talents (grant No. 2005 KYCX021) and the Natural Science Foundation of Henan Province.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2004). SHELXTL, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dunne, S. J., von Nagy-Felsobuki, E. I. & Mackay, M. F. (1995). Acta Cryst. C51, 1454–1457. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Gilat, S. L., Kawai, S. H. & Lehn, J.-M. (1995). Chem. Eur. J. 1, 275–284. CrossRef CAS Web of Science Google Scholar
Goulle, V., Harriman, A. & Lehn, J.-M. (1993). J. Chem. Soc. Chem. Commun. pp. 1034–1035. CrossRef Web of Science Google Scholar
Gütlich, P., Hauser, A. & Spiering, H. (1994). Angew. Chem. Int. Ed. Engl. 33, 2024–2054. CrossRef Web of Science Google Scholar
Jung, O.-S., Jo, D. H., Lee, Y.-A., Conklin, B. J. & Pierpont, C. G. (1997). Inorg. Chem. 36, 19–24. CSD CrossRef CAS Web of Science Google Scholar
Kawai, S. H., Gilat, S. L., Ponsinet, R. & (1995). Chem. Eur. J. 1, 285–293. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Wang, H. F., Tomizawa, H. & Miki, E. (2001). Inorg. Chim. Acta, 321, 215–220. Web of Science CSD CrossRef CAS Google Scholar