1,4-Bis(pyridin-3-ylmeth­oxy)benzene

Abstract

The asymmetric unit of the centrosymmetric title compound, C₁₈H₁₆N₂O₂, contains one half-mol­ecule. The central benzene ring forms a dihedral angle of 66.8 (1)° with two outer aromatic rings. In the crystal structure, weak inter­molecular C—H⋯N hydrogen bonds link mol­ecules into sheets parallel to (104).

Related literature

For general background to bridging mol­ecules with pyridyl substituents at the terminal positions, see: McMorran & Steel (1998 ▶); Zaman et al. (2005 ▶). For details of the synthesis, see: Gao et al. (2004 ▶). For a related structure, see: Gao et al. (2006 ▶).

Experimental

Crystal data

• C₁₈H₁₆N₂O₂

• M _r = 292.33

• Monoclinic,

• a = 6.852 (5) Å

• b = 5.688 (3) Å

• c = 18.861 (12) Å

• β = 90.60 (3)°

• V = 735.0 (8) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 291 K

• 0.22 × 0.20 × 0.19 mm

Data collection

• Rigaku RAXIS-RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.981, T _max = 0.984

• 6855 measured reflections

• 1684 independent reflections

• 1213 reflections with I > 2σ(I)

• R _int = 0.030

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.118

• S = 1.09

• 1684 reflections

• 100 parameters

• H-atom parameters constrained

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.14 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 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: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1i	0.93	2.57	3.437 (3)	155

Symmetry code: (i) .

supplementary crystallographic information

Comment

The bridging molecules with pyridyl substituents at the terminal positions are hoped to construct interesting supramolecular architectures by intermolecular hydrogen bonding and coordination with metals. McMorran' group have reported the synthesis of a quadruply stranded helicate that encapsulates a hexafluorophosphate anion by the reaction of 1,4-bis(3-pyridylmethoxy)benzene with palladium chlorate (McMorran et al., 1998). Zaman's group have designed a long rigid organic ligand, 1,4-bis[(3-pyridyl)ethynyl]benzene, which reacted with metal salts to form interpenetrating two-dimensional and three-dimensional cross-zigzag chains and metallocyclic chain structures (Zaman et al., 2005). As an extension of our work about bipyridyl aromatic ligands, we report the crystal structure of the title compound here.

In the title compound (Fig. 1), all bond lengths and angles are normal and correpond to those observed in the related compound (Gao et al., 2006). The 1,4-bis(3-pyridylmethoxy)benzene molecule is centrosymmetric. The planes of two terminal pyridyl groups rotate drastically and make dihedral angles of 66.8 (1) ° with the plane of the central benzene ring.

In the crystal structure, the adjacent 1,4-bis(3-pyridylmethoxy)benzene molecules are linked into two-dimensional supramolecular sheets by intermolecular C—H···N hydrogen bonds (Table 1, Figure 2).

Experimental

The 1,4-bis(3-pyridylmethoxy)benzene was synthesized by the reaction of p-benzenediol and 3-chloromethylpyridine hydrochloride under nitrogen atmosphere and alkaline condition (Gao et al., 2004; Gao et al., 2006). Colourless block-shaped crystals of title compound were obtained by slow evaporation of an methanol solution after three days.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and treated as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids at the 30% probability level [symmetry code: (i) -x, 1 - y, -z].

Fig. 2.

A portion of the crystal packing showing the two-dimensional hydrogen bonded (dashed lines) sheet.

Crystal data

C18H16N2O2	F(000) = 308
Mr = 292.33	Dx = 1.321 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4889 reflections
a = 6.852 (5) Å	θ = 3.7–27.5°
b = 5.688 (3) Å	µ = 0.09 mm−1
c = 18.861 (12) Å	T = 291 K
β = 90.60 (3)°	Block, colourless
V = 735.0 (8) Å3	0.22 × 0.20 × 0.19 mm
Z = 2

Data collection

Rigaku RAXIS-RAPID diffractometer	1684 independent reflections
Radiation source: fine-focus sealed tube	1213 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω scan	θmax = 27.5°, θmin = 3.7°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.981, Tmax = 0.984	k = −6→7
6855 measured reflections	l = −24→24

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0606P)2 + 0.0635P] where P = (Fo2 + 2Fc2)/3
1684 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.14 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8460 (2)	−0.0288 (3)	0.20865 (8)	0.0485 (4)
H1	0.9650	−0.0611	0.2307	0.058*
C2	0.7721 (2)	−0.1906 (3)	0.16191 (8)	0.0530 (4)
H2	0.8404	−0.3281	0.1524	0.064*
C3	0.5951 (2)	−0.1469 (3)	0.12921 (8)	0.0484 (4)
H3	0.5422	−0.2545	0.0972	0.058*
C4	0.49744 (18)	0.0588 (2)	0.14460 (7)	0.0367 (3)
C5	0.5857 (2)	0.2119 (3)	0.19208 (7)	0.0428 (4)
H5	0.5213	0.3517	0.2022	0.051*
C6	0.30072 (19)	0.1158 (3)	0.11378 (7)	0.0433 (4)
H6A	0.2437	−0.0233	0.0922	0.052*
H6B	0.2144	0.1704	0.1507	0.052*
C7	0.15874 (17)	0.3913 (2)	0.03246 (7)	0.0368 (3)
C8	−0.02824 (18)	0.3034 (3)	0.04198 (7)	0.0408 (3)
H8	−0.0477	0.1710	0.0700	0.049*
C9	−0.18583 (18)	0.4142 (3)	0.00955 (7)	0.0408 (3)
H9	−0.3112	0.3563	0.0163	0.049*
N1	0.75686 (17)	0.1729 (2)	0.22431 (7)	0.0510 (4)
O1	0.32526 (13)	0.29466 (19)	0.06180 (5)	0.0509 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0308 (7)	0.0572 (9)	0.0571 (9)	0.0002 (6)	−0.0101 (6)	0.0171 (7)
C2	0.0439 (9)	0.0449 (8)	0.0700 (10)	0.0117 (7)	−0.0063 (7)	0.0064 (8)
C3	0.0487 (8)	0.0432 (8)	0.0532 (8)	0.0035 (7)	−0.0108 (6)	−0.0038 (7)
C4	0.0308 (6)	0.0395 (7)	0.0396 (7)	−0.0005 (5)	−0.0056 (5)	0.0083 (6)
C5	0.0371 (7)	0.0388 (7)	0.0525 (8)	0.0016 (6)	−0.0069 (6)	0.0008 (6)
C6	0.0334 (7)	0.0482 (8)	0.0482 (8)	−0.0010 (6)	−0.0093 (6)	0.0109 (6)
C7	0.0264 (6)	0.0465 (8)	0.0374 (6)	0.0056 (5)	−0.0046 (5)	0.0038 (6)
C8	0.0308 (7)	0.0475 (8)	0.0438 (7)	−0.0007 (6)	−0.0045 (5)	0.0111 (6)
C9	0.0250 (6)	0.0530 (8)	0.0444 (7)	−0.0016 (6)	−0.0030 (5)	0.0073 (6)
N1	0.0394 (7)	0.0538 (8)	0.0596 (8)	−0.0056 (6)	−0.0145 (6)	0.0004 (6)
O1	0.0269 (5)	0.0683 (7)	0.0573 (6)	0.0058 (4)	−0.0048 (4)	0.0267 (5)

Geometric parameters (Å, °)

C1—N1	1.334 (2)	C6—O1	1.4239 (17)
C1—C2	1.368 (2)	C6—H6A	0.9700
C1—H1	0.9300	C6—H6B	0.9700
C2—C3	1.378 (2)	C7—C9i	1.374 (2)
C2—H2	0.9300	C7—O1	1.3773 (17)
C3—C4	1.380 (2)	C7—C8	1.389 (2)
C3—H3	0.9300	C8—C9	1.3869 (19)
C4—C5	1.3839 (19)	C8—H8	0.9300
C4—C6	1.4979 (19)	C9—C7i	1.374 (2)
C5—N1	1.3336 (19)	C9—H9	0.9300
C5—H5	0.9300
N1—C1—C2	123.64 (13)	O1—C6—H6A	110.1
N1—C1—H1	118.2	C4—C6—H6A	110.1
C2—C1—H1	118.2	O1—C6—H6B	110.1
C1—C2—C3	119.03 (14)	C4—C6—H6B	110.1
C1—C2—H2	120.5	H6A—C6—H6B	108.4
C3—C2—H2	120.5	C9i—C7—O1	115.88 (11)
C2—C3—C4	119.04 (14)	C9i—C7—C8	119.64 (12)
C2—C3—H3	120.5	O1—C7—C8	124.47 (13)
C4—C3—H3	120.5	C9—C8—C7	119.64 (14)
C3—C4—C5	117.37 (13)	C9—C8—H8	120.2
C3—C4—C6	122.56 (13)	C7—C8—H8	120.2
C5—C4—C6	120.04 (13)	C7i—C9—C8	120.71 (12)
N1—C5—C4	124.50 (14)	C7i—C9—H9	119.6
N1—C5—H5	117.7	C8—C9—H9	119.6
C4—C5—H5	117.7	C5—N1—C1	116.41 (13)
O1—C6—C4	108.04 (11)	C7—O1—C6	117.28 (10)

Symmetry codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1ii	0.93	2.57	3.437 (3)	155

Symmetry codes: (ii) −x+2, y−1/2, −z+1/2.