supplementary materials
1,4-Bis(2-pyridylmethoxy)benzene
In the title compound, C18H16N2O2, the phenylene ring is located on inversion center. The pyridyl ring makes a dihedral angle of 39.9 (1)° with the phenylene ring. In the crystal, adjacent molecules are linked by intermolecular C-H
N hydrogen bonds, forming a linear chain along the a axis.
The 1,4-bis(2-pyridylmethoxy)benzene was synthesized by the reaction of
p-benzenediol and 2-chloromethylpyridine hydrochloride under nitrogen
atmosphere and alkaline condition (Gao et al., 2004; Gao et
al.,
2006). A solution of Zn(NO3)2.6H2O (0.3 g, 1 mol) in water (5 ml)
was
dropped slowly into a methanol solution (5 mL) of
1,4-bis(2-pyridylmethoxy)benzene (1.46 g, 5 mmol) to give a clear solution.
Colourless nod-shaped crystals of scheme were obtained by slow evaporation of
the clear solution after four days.
H atoms bound to C atoms were placed in calculated positions and treated as
riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C).
Data collection: RAPID-AUTO (Rigaku 1998); cell refinement: RAPID-AUTO (Rigaku 1998); data reduction: CrystalStructure (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 (Sheldrick, 2008).
1,4-Bis(2-pyridylmethoxy)benzene
top
Crystal data top
| C18H16N2O2 | F(000) = 308 |
| Mr = 292.33 | Dx = 1.351 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 5105 reflections |
| a = 9.802 (7) Å | θ = 3.3–24.5° |
| b = 3.988 (2) Å | µ = 0.09 mm−1 |
| c = 18.421 (11) Å | T = 291 K |
| β = 93.77 (3)° | Block, colorless |
| V = 718.6 (8) Å3 | 0.33 × 0.30 × 0.22 mm |
| Z = 2 | |
Data collection top
Rigaku RAXIS-RAPID
diffractometer | 1639 independent reflections |
| Radiation source: fine-focus sealed tube | 1308 reflections with I > 2σ(I) |
| graphite | Rint = 0.024 |
| ω scan | θmax = 27.5°, θmin = 3.8° |
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995) | h = −12→12 |
| Tmin = 0.972, Tmax = 0.980 | k = −5→4 |
| 6515 measured reflections | l = −23→23 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.118 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0651P)2 + 0.0675P]
where P = (Fo2 + 2Fc2)/3 |
| 1639 reflections | (Δ/σ)max = 0.001 |
| 100 parameters | Δρmax = 0.18 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
| C18H16N2O2 | V = 718.6 (8) Å3 |
| Mr = 292.33 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 9.802 (7) Å | µ = 0.09 mm−1 |
| b = 3.988 (2) Å | T = 291 K |
| c = 18.421 (11) Å | 0.33 × 0.30 × 0.22 mm |
| β = 93.77 (3)° | |
Data collection top
Rigaku RAXIS-RAPID
diffractometer | 1639 independent reflections |
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995) | 1308 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.980 | Rint = 0.024 |
| 6515 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.118 | Δρmax = 0.18 e Å−3 |
| S = 1.11 | Δρmin = −0.18 e Å−3 |
| 1639 reflections | Absolute structure: ? |
| 100 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| C1 | 1.12833 (12) | 0.4754 (4) | 0.84073 (7) | 0.0494 (4) | |
| H1 | 1.2127 | 0.5728 | 0.8536 | 0.059* | |
| C2 | 1.09220 (13) | 0.4307 (4) | 0.76808 (7) | 0.0478 (4) | |
| H2 | 1.1505 | 0.4972 | 0.7329 | 0.057* | |
| C3 | 0.96805 (14) | 0.2856 (4) | 0.74848 (7) | 0.0484 (4) | |
| H3 | 0.9408 | 0.2502 | 0.6998 | 0.058* | |
| C4 | 0.88466 (12) | 0.1935 (4) | 0.80254 (6) | 0.0430 (3) | |
| H4 | 0.7999 | 0.0958 | 0.7908 | 0.052* | |
| C5 | 0.92844 (11) | 0.2482 (3) | 0.87452 (6) | 0.0339 (3) | |
| C6 | 0.84341 (11) | 0.1455 (3) | 0.93572 (6) | 0.0381 (3) | |
| H6A | 0.8602 | −0.0879 | 0.9481 | 0.046* | |
| H6B | 0.8667 | 0.2812 | 0.9785 | 0.046* | |
| C7 | 0.60652 (11) | 0.0920 (3) | 0.95792 (6) | 0.0360 (3) | |
| C8 | 0.47231 (12) | 0.1610 (3) | 0.93481 (6) | 0.0393 (3) | |
| H8 | 0.4536 | 0.2702 | 0.8907 | 0.047* | |
| C9 | 0.63449 (11) | −0.0704 (3) | 1.02374 (6) | 0.0388 (3) | |
| H9 | 0.7243 | −0.1181 | 1.0399 | 0.047* | |
| N1 | 1.04938 (10) | 0.3872 (3) | 0.89418 (5) | 0.0442 (3) | |
| O1 | 0.70397 (8) | 0.1927 (3) | 0.91212 (4) | 0.0492 (3) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C1 | 0.0300 (6) | 0.0620 (9) | 0.0568 (8) | −0.0047 (6) | 0.0072 (5) | 0.0111 (7) |
| C2 | 0.0370 (6) | 0.0591 (9) | 0.0492 (7) | 0.0080 (6) | 0.0182 (5) | 0.0146 (6) |
| C3 | 0.0462 (7) | 0.0630 (9) | 0.0368 (6) | 0.0055 (6) | 0.0087 (5) | 0.0019 (6) |
| C4 | 0.0337 (6) | 0.0543 (8) | 0.0413 (6) | −0.0031 (5) | 0.0042 (5) | −0.0005 (6) |
| C5 | 0.0270 (5) | 0.0373 (6) | 0.0380 (6) | 0.0033 (4) | 0.0059 (4) | 0.0035 (5) |
| C6 | 0.0280 (6) | 0.0491 (7) | 0.0375 (6) | 0.0003 (5) | 0.0054 (4) | 0.0043 (5) |
| C7 | 0.0289 (6) | 0.0473 (7) | 0.0325 (6) | 0.0002 (5) | 0.0080 (4) | 0.0012 (5) |
| C8 | 0.0327 (6) | 0.0541 (7) | 0.0313 (5) | 0.0025 (5) | 0.0046 (4) | 0.0070 (5) |
| C9 | 0.0262 (5) | 0.0547 (8) | 0.0357 (6) | 0.0029 (5) | 0.0035 (4) | 0.0041 (5) |
| N1 | 0.0306 (5) | 0.0593 (7) | 0.0430 (6) | −0.0050 (5) | 0.0044 (4) | 0.0050 (5) |
| O1 | 0.0272 (4) | 0.0811 (7) | 0.0401 (5) | 0.0027 (4) | 0.0090 (3) | 0.0173 (5) |
Geometric parameters (Å, °) top
| C1—N1 | 1.3388 (16) | C6—O1 | 1.4192 (16) |
| C1—C2 | 1.373 (2) | C6—H6A | 0.9700 |
| C1—H1 | 0.9300 | C6—H6B | 0.9700 |
| C2—C3 | 1.374 (2) | C7—O1 | 1.3754 (15) |
| C2—H2 | 0.9300 | C7—C8 | 1.3834 (18) |
| C3—C4 | 1.3791 (18) | C7—C9 | 1.3861 (18) |
| C3—H3 | 0.9300 | C8—C9i | 1.3836 (17) |
| C4—C5 | 1.3838 (18) | C8—H8 | 0.9300 |
| C4—H4 | 0.9300 | C9—C8i | 1.3837 (17) |
| C5—N1 | 1.3369 (17) | C9—H9 | 0.9300 |
| C5—C6 | 1.5023 (17) | | |
| | | |
| N1—C1—C2 | 123.93 (12) | O1—C6—H6A | 110.2 |
| N1—C1—H1 | 118.0 | C5—C6—H6A | 110.2 |
| C2—C1—H1 | 118.0 | O1—C6—H6B | 110.2 |
| C1—C2—C3 | 118.55 (11) | C5—C6—H6B | 110.2 |
| C1—C2—H2 | 120.7 | H6A—C6—H6B | 108.5 |
| C3—C2—H2 | 120.7 | O1—C7—C8 | 115.96 (11) |
| C2—C3—C4 | 118.62 (12) | O1—C7—C9 | 124.59 (11) |
| C2—C3—H3 | 120.7 | C8—C7—C9 | 119.44 (11) |
| C4—C3—H3 | 120.7 | C7—C8—C9i | 121.12 (11) |
| C3—C4—C5 | 119.27 (12) | C7—C8—H8 | 119.4 |
| C3—C4—H4 | 120.4 | C9i—C8—H8 | 119.4 |
| C5—C4—H4 | 120.4 | C8i—C9—C7 | 119.43 (11) |
| N1—C5—C4 | 122.58 (11) | C8i—C9—H9 | 120.3 |
| N1—C5—C6 | 115.82 (11) | C7—C9—H9 | 120.3 |
| C4—C5—C6 | 121.58 (11) | C5—N1—C1 | 117.05 (11) |
| O1—C6—C5 | 107.74 (10) | C7—O1—C6 | 117.84 (9) |
| Symmetry codes: (i) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C9—H9···N1ii | 0.93 | 2.68 | 3.587 (2) | 165 |
| Symmetry codes: (ii) −x+2, −y, −z+2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C9—H9···N1i | 0.93 | 2.68 | 3.587 (2) | 165 |
| Symmetry codes: (i) −x+2, −y, −z+2. |
The authors thank the Specialized Research Funds for Technological Innovative
Talent in Harbin (RC2009XK018007) and Heilongjiang University for supporting
this study.
Gao, C.-M., Cao, D. & Zhu, L. (2004). Photogr. Sci. Photochem. 22, 103–107.
Gao, J.-S., Liu, Y., Hou, G.-F., Yu, Y.-H. & Yan, P.-F. (2006). Acta Cryst. E62, o5645–o5646.
Hartshorn, C.-M. & Steel, P.-J. (1998). J. Chem. Soc. Dalton Trans. pp. 3927–3933.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Oh, M., Stern, C.-L. & Mirkin, C.-A. (2005). Inorg. Chem. 44, 2647–2653.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./ng2637fig1thm.gif)
![[Figure 2]](./ng2637fig2thm.gif)
The bipyridyl ligand is generally used as bridge units to construct metal-organic framework. Hartshorn's group have reported the syntheses of the silver and palladium complexes with the 1,4-bis(2-pyridylmethoxy)benzene ligand, which assemble into one-dimensional zigzag chain in the former and an M2L2 26-membered macrocycle in the latter (Hartshorn et al., 1998). Oh's group have investeigated how metal-ligand stoichiometry can be used to influence the formation of polymeric structures, in which they reacted silver salts with the 1,4-bis(2-pyridylmethoxy)benzene ligand in 1:1 ratio to form one-dimensional zigzag chain and in 1:2 ratio to yield a two-dimensional porous network. Herein we synthesized the same ligand and hoped to obtain the fluorescent material by reacting the ligand with d10 metal, but we get a lot of crystals of the ligand itself and report its crystal structure here.
The X-ray single-crystal analysis of the title compound shows that the 1,4-bis(2-pyridylmethoxy)benzene molecule is centrosymmetric. The planes of two terminal pyridyl groups are parallel and make dihedral angles of 39.9 (1) ° with the plane of the central benzene ring (Figure 1). In the crystal structure, the 1,4-bis(2-pyridylmethoxy)benzene molecules are linked by intermolecular C—H···N hydrogen bonds into one dimensional chains along a axis direction (Table 1, Figure 2).