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Crystal structures of three 4-substituted-2,2 ′ -bipyridines synthesized by Sonogashira and Suzuki – Miyaura cross-coupling reactions

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ABSTRACT

71: Facile synthetic routes for three 4-substituted 2,2′-bi­pyridine derivatives, 4-[2-(4-methyl­phenyl)­ethyn­yl]-2,2′-bi­pyridine, C19H14N2, (I), 4-[2-(pyridin-3-yl)ethyn­yl]-2,2′-bi­pyridine, C17H11N3, (II), and 4-(indol-4-yl)-2,2′-bi­pyridine, C18H13N3, (III), via Sonogashira and Suzuki–Miyaura cross-coupling reactions, respect­ively, are described. As indicated by X-ray analysis, the 2,2′-bi­pyridine core, the ethyl­ene linkage and the substituents of (I) and (II) are almost planar [dihedral angles between the two ring systems: 8.98 (5) and 9.90 (6)° for the two mol­ecules of (I) in the asymmetric unit and 2.66 (14)° for (II)], allowing π-conjugation. On the contrary, in (III), the indole substituent ring is rotated significantly out of the bi­pyridine plane [dihedral angle = 55.82 (3)°], due to steric hindrance. The crystal packings of (I) and (II) are dominated by π–π inter­actions, resulting in layers of mol­ecules parallel to (30-2) in (I) and columns of mol­ecules along the a axis in (II). The packing of (III) exhibits zigzag chains of mol­ecules along the c axis inter­acting through N—H⋯N hydrogen bonds and π–π inter­actions. The contributions of unknown disordered solvent mol­ecules to the diffraction intensities in (II) were removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C, 9–18] algorithm of PLATON. The given chemical formula and other crystal data do not take into account these solvent mol­ecules.

No MeSH data available.


Crystal packing of (III) showing N—H⋯N hydrogen bonds (blue dotted lines) and π–π (gray dotted lines) inter­actions·[Symmetry codes: (i) x, −y + , z + ; (ii) x, −y + , z − ; (iii) x, −y + , z − ; (iv) x, −y + , z + ].
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fig4: Crystal packing of (III) showing N—H⋯N hydrogen bonds (blue dotted lines) and π–π (gray dotted lines) inter­actions·[Symmetry codes: (i) x, −y + , z + ; (ii) x, −y + , z − ; (iii) x, −y + , z − ; (iv) x, −y + , z + ].

Mentions: The mol­ecules in the crystal packing of (III) are arranged in zigzag chains running along the c axis by hydrogen-bonding inter­actions in a head-to-tail manner between N13—H13⋯N7i [symmetry code: (i) x, −y + , z + ; Table 3 ▸, Fig. 4 ▸]. These chains inter­act by π–π stacking between pyridine rings [Cg2⋯Cg3i = 3.6920 (8) Å; Cg2 and Cg3 are the centroids of the N1/C2–C6 and N7/C8–C12 rings, respectively; symmetry code: (i) x, −y + , z + ] and C—H⋯π inter­actions (Table 3 ▸).


Crystal structures of three 4-substituted-2,2 ′ -bipyridines synthesized by Sonogashira and Suzuki – Miyaura cross-coupling reactions
Crystal packing of (III) showing N—H⋯N hydrogen bonds (blue dotted lines) and π–π (gray dotted lines) inter­actions·[Symmetry codes: (i) x, −y + , z + ; (ii) x, −y + , z − ; (iii) x, −y + , z − ; (iv) x, −y + , z + ].
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5382633&req=5

fig4: Crystal packing of (III) showing N—H⋯N hydrogen bonds (blue dotted lines) and π–π (gray dotted lines) inter­actions·[Symmetry codes: (i) x, −y + , z + ; (ii) x, −y + , z − ; (iii) x, −y + , z − ; (iv) x, −y + , z + ].
Mentions: The mol­ecules in the crystal packing of (III) are arranged in zigzag chains running along the c axis by hydrogen-bonding inter­actions in a head-to-tail manner between N13—H13⋯N7i [symmetry code: (i) x, −y + , z + ; Table 3 ▸, Fig. 4 ▸]. These chains inter­act by π–π stacking between pyridine rings [Cg2⋯Cg3i = 3.6920 (8) Å; Cg2 and Cg3 are the centroids of the N1/C2–C6 and N7/C8–C12 rings, respectively; symmetry code: (i) x, −y + , z + ] and C—H⋯π inter­actions (Table 3 ▸).

View Article: PubMed Central - HTML - PubMed

ABSTRACT

71: Facile synthetic routes for three 4-substituted 2,2′-bi­pyridine derivatives, 4-[2-(4-methyl­phenyl)­ethyn­yl]-2,2′-bi­pyridine, C19H14N2, (I), 4-[2-(pyridin-3-yl)ethyn­yl]-2,2′-bi­pyridine, C17H11N3, (II), and 4-(indol-4-yl)-2,2′-bi­pyridine, C18H13N3, (III), via Sonogashira and Suzuki–Miyaura cross-coupling reactions, respect­ively, are described. As indicated by X-ray analysis, the 2,2′-bi­pyridine core, the ethyl­ene linkage and the substituents of (I) and (II) are almost planar [dihedral angles between the two ring systems: 8.98 (5) and 9.90 (6)° for the two mol­ecules of (I) in the asymmetric unit and 2.66 (14)° for (II)], allowing π-conjugation. On the contrary, in (III), the indole substituent ring is rotated significantly out of the bi­pyridine plane [dihedral angle = 55.82 (3)°], due to steric hindrance. The crystal packings of (I) and (II) are dominated by π–π inter­actions, resulting in layers of mol­ecules parallel to (30-2) in (I) and columns of mol­ecules along the a axis in (II). The packing of (III) exhibits zigzag chains of mol­ecules along the c axis inter­acting through N—H⋯N hydrogen bonds and π–π inter­actions. The contributions of unknown disordered solvent mol­ecules to the diffraction intensities in (II) were removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C, 9–18] algorithm of PLATON. The given chemical formula and other crystal data do not take into account these solvent mol­ecules.

No MeSH data available.