4′-(4-Methylphenyl)-2,2′:6′,2′′-terpyridine

Abstract

There are two crystallographically independent molecules in the asymmetric unit of the title compound, C22H17N3. In each molecule, the three pyridyl groups are nearly coplanar, whereas the tolyl groups are twisted out of the plane of the attached pyridyl rings by ca 28°. The molecular components are assembled through C—H...π and π–π interactions [centroid–centroid distances are 3.677 (4) and 3.707 (7) Å] into a one‐dimensional chain running in the a‐axis direction.

A new polymorph of 4′-tolyl-2,2′:6′,2′′-terpyridine (ttpy) and the single crystal structures of [Fe(ttpy)2][PF6]2 and [Ru(ttpy)2][PF6]2

“…The aryl ring in each independent molecule is twisted out of the plane of the central pyridine ring (angles between least squares planes of rings containing atoms N2 and C16 (molecule A), and N5 and C46 (molecule B) = 29.2(1) and 16.0(1)°, respectively). These twist angles compare with 28.7(4) and 27.8(9)°observed for the crystallographically independent molecules in polymorph I [19]. The packing efficiency in the two polymorphs is approximately equal (68.3% in polymorph I, 68.8% in II) [25].…”

“…The sample crystallizes in the monoclinic C2/c space group (polymorph II) [24], in contrast to the P2 1 /c space group previously reported (polymorph I) [19]. Polymorph II contains two independent molecules in the asymmetric unit.…”

“…1 shows the structure of molecule A, and bond distances and angles within each molecule are similar and unexceptional. The tpy domains are essential planar (angles between least squares planes of rings containing atoms N1 and N2, and N2 and N3 in molecule A = 4.8(1) and 11.64(9)°, and of rings with N4 and N5, and N5 and N6 in molecule B = 9.4(1) and 2.3(1)°), as in polymorph I [19]. The aryl ring in each independent molecule is twisted out of the plane of the central pyridine ring (angles between least squares planes of rings containing atoms N2 and C16 (molecule A), and N5 and C46 (molecule B) = 29.2(1) and 16.0(1)°, respectively).…”

“…The packing efficiency in the two polymorphs is approximately equal (68.3% in polymorph I, 68.8% in II) [25]. This is achieved in polymorph I by a combination of CAHÁÁÁp contacts and p-p stacking interactions that result in the assembly on onedimensional chains [19]. In polymorph II, molecules stack into columns (Fig.…”

“…Many of the metal complexes developed through the use of the ligands ttpy and Brttpy are of importance because of their redox or photophysical properties [4,5,7,9,[14][15][16][17][18]. Despite the interest in the ttpy ligand, its solidstate structure was only reported in 2007 [19], and structural details of homoleptic [M(ttpy) 2 [21], and a report of [Cu 6 (CN) 8 Á Fe(ttpy) 2 ] n in which the [Fe(ttpy) 2 ] 2+ ions are encapsulated within a 3-dimensional anionic network [22]. A cocrystal of ttpy and 1,4-I 2 C 6 F 4 has also been reported [23] The ttpy ligand was prepared by standard procedures [3] and single crystals were grown from a hexane-ethyl acetate (30:2) solution of the compound.…”