Green chemistry synthesis: 2‐amino‐3‐[(E)‐(2‐pyridyl)methylideneamino]but‐2‐enedinitrile monohydrate and 5‐cyano‐2‐(2‐pyridyl)‐1‐(2‐pyridylmethyl)‐1H‐imidazole‐4‐carboxamide

The title compounds, C₁₀H₉N₅O·H₂O (L1·H₂O) and C₁₆H₁₂N₆O (L2), were synthesized by solvent‐free aldol condensation at room temperature. L1, prepared by grinding picolinaldehyde with 2,3‐diamino‐3‐isocyanoacrylonitrile in a 1:1 molar ratio, crystallized as a monohydrate. L2 was prepared by grinding picolinaldehyde with 2,3‐diamino‐3‐isocyanoacrylonitrile in a 2:1 molar ratio. By varying the conditions of crystallization it was possible to obtain two polymorphs, viz. L2‐I and L2‐II; both crystallized in the monoclinic space group P2₁/c. They differ in the orientation of one pyridine ring with respect to the plane of the imidazole ring. In L2‐I, this ring is oriented towards and above the imidazole ring, while in L2‐II it is rotated away from and below the imidazole ring. In all three molecules, there is a short intramolecular N—H...N contact inherent to the planarity of the systems. In L1·H₂O, this involves an amino H atom and the C=N N atom, while in L2 it involves an amino H atom and an imidazole N atom. In the crystal structure of L1·H₂O, there are N—H...O and O—H...O intermolecular hydrogen bonds which link the molecules to form two‐dimensional networks which stack along [001]. These networks are further linked via intermolecular N—H...N(cyano) hydrogen bonds to form an extended three‐dimensional network. In the crystal structure of L2‐I, symmetry‐related molecules are linked via N—H...N hydrogen bonds, leading to the formation of dimers centred about inversion centres. These dimers are further linked via N—H...O hydrogen bonds involving the amide group, also centred about inversion centres, to form a one‐dimensional arrangement propagating in [100]. In the crystal structure of L2‐II, the presence of intermolecular N—H...O hydrogen bonds involving the amide group results in the formation of dimers centred about inversion centres. These are linked via N—H...N hydrogen bonds involving the second amide H atom and the cyano N atom, to form two‐dimensional networks in the bc plane. In L2‐I and L2‐II, C—H...π and π–π interactions are also present.