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Reactions exchanging the cation in (nBu4N)[Ni(dmit)2] to cis‐cyclohexane‐1,4‐diammonium (cis‐CHDA) in the presence of [18]crown‐6, benzo[18]crown‐6 (B[18]crown‐6) and dibenzo[18]crown‐6 (DB[18]crown‐6) yielded crystals of the monovalent [Ni(dmit)2] complex, namely (cis‐CHDA)([18]crown‐6)2[Ni(dmit)2]2 (1), (cis‐CHDA)(B[18]crown‐6)2[Ni(dmit)2]2 (2) and (cis‐CHDA)(DB[18]crown‐6)2[Ni(dmit)2]2 (3). The two ammonium groups (–NH3+) of the cis‐CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich‐type supramolecular cationic structures. The lateral [Ni(dmit)2]− anion arrangements through S–S contacts along the short and long axis of [Ni(dmit)2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis‐CHDA dication. The temperature‐ and frequency‐dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis‐CHDA dication was consistent with the dielectric responses.

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