Synthesis and Crystal Structures of Lithium, Sodium, and Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

2‐(Methylthio)aniline (H 2 L 1 ) and 2‐(phenylthio)aniline (H 2 L 2 ) were treated with n ‐butyllithium to yield the corresponding anilides [LiHL 1 ] and [LiHL 2 ]. Recrystallization from diethyl ether and THF afforded the solvates [LiHL 1 (Et 2 O)] and [LiHL 2 (THF) 2 ]. The X‐ray crystal structure determination revealed dimeric molecules which exhibit a centrosymmetric Li 2 N 2 ring. In the case of [LiHL 1 (Et 2 O)] the SMe group is involved in Li coordination and in the case of [LiHL 2 (THF) 2 ] the SPh group is part of an intramolecular N–H ··· S hydrogen bridge. The sodium anilides [NaHL 1 (DME)] and [NaHL 2 (DME)] were obtained from the reaction of H 2 L 1 and H 2 L 2 with sodium amide in DME as solvent. Like in the case of the lithium amides the sodium derivatives [NaHL 1 (DME)] and [NaHL 2 (DME)] display centrosymmetric Na 2 N 2 cores. The coordination sphere of the sodium atoms is completed by DME molecules, which act as chelating ligands. In the case of [NaHL 1 (DME)] the DME molecules enable additionally a linkage of the dimeric subunits to give a chain structure. The potassium derivatives [KNHL 1 ] and [KNHL 2 (DME)] were obtained from H 2 L 1 and H 2 L 2 and potassium hydride in DME as solvent. [KNHL 1 ] displays a distinct structure based on [(KNHL 1 ) 2 ] dimers, which are linked by additional [KNHL 1 ] units to give a 3D coordination polymer with {4.8.16(3)} topology. [KNHL 2 (DME)] forms dimers linked by bridging DME molecules to give a chain‐like coordination polymer.