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The structure of the title salt, (C8H10NO)2[CoCl4], is isotypic with the analogous cuprate(II) structure. The asymmetric unit contains one 4-acetyl­anilinium cation and one half of a tetra­chlorido­cobaltate(II) anion for which the CoII atom and two Cl− ligands lie on a mirror plane. The Co—Cl distances in the distorted tetra­hedral anion range from 2.2519 (6) to 2.2954 (9) Å and the Cl—Co—Cl angles range from 106.53 (2) to 110.81 (4)°. In the crystal, cations are self-assembled by inter­molecular N—H⋯O hydrogen-bonding inter­actions, leading to a C(8) chain motif with the chains running parallel to the b axis. π–π stacking inter­actions between benzene rings, with a centroid-to-centroid distance of 3.709 Å, are also observed along this direction. The CoCl4 2− anions are sandwiched between the cationic chains and inter­act with each other through inter­molecular N—H⋯Cl hydrogen-bonding inter­actions, forming a three-dimensional network structure.

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The structure of the title salt, (C8H10NO)2[HgCl4], is isotypic with that of the cuprate(II) and cobaltate(II) analogues. The asymmetric unit contains one 4-acetyl­anilinium cation and one half of a tetra­chlorido­mercurate(II) anion (point group symmetry m). The Hg—Cl distances are in the range 2.4308 (7)–2.5244 (11) Å and the Cl—Hg—Cl angles in the range of 104.66 (2)–122.94 (4)°, indicating a considerable distortion of the tetra­hedral anion. In the crystal, cations are linked by an inter­molecular N—H⋯O hydrogen-bonding inter­action, leading to a C(8) chain motif with the chains extending parallel to the b axis. There is also a π–π stacking inter­action with a centroid-to-centroid distance of 3.735 (2) Å between neighbouring benzene rings along this direction. The anions lie between the chains and inter­act with the cations through inter­molecular N—H⋯Cl hydrogen bonds, leading to the formation of a three-dimensional network structure.