The asymmetric unit of the title compound, (C6H9N2)2[CuCl4], consists of one cation and one half-anion, bis­ected by a twofold rotation axis through the metal center. The anion exhibits a geometry that is inter­mediate between a Td and D 4h arrangement about the Cu atom. The crystal structure contains chains of cations alternating with stacks of anions. The cationic groups inter­act via offset face-to-face π–π stacking, forming chains running along the c axis. The anion stacks are parallel to the cation chains, with no significant inter- nor intra­stack Cl⋯Cl inter­actions. There are several anion–cation hydrogen-bonding inter­actions of the (N—H)pyridine⋯Cl and (N—H)amino⋯Cl types, connecting the chains of cations to the stacks of anions. Both the N—H⋯Cl and π–π stacking inter­actions [centroid–centroid distances 3.61 (8) and 3.92 (2) Å] contribute to the formation of a three-dimensional supra­molecular architecture.

The asymmetric unit of the title compound, (C5H8N2)[HgBr4]·H2O, consists of one cation, one anion and one water mol­ecule. The anion exhibits a distorted tetra­hedral arrangement about the Hg atom. The crystal structure contains alternating sheets of cations (in the ac plane) and stacks of anions. Several strong hydrogen-bonding inter­actions (pyN—H⋯Br and C—H⋯Br; py is pyridine), along with O—H⋯Br inter­actions, connect the sheets of cations to the stacks of anions. Cation–cation π–π stacking is also present (C⋯C distances in the range 3.424–3.865 Å). The shortest Br⋯Br distance is 3.9527 (9) Å.

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Key indicators: single-crystal X-ray study; T = 293 K; mean (C-C) = 0.016 Å; R factor = 0.059; wR factor = 0.153; data-to-parameter ratio = 18.8.In the crystal structure of the title compound, (C 6 Table 1 Selected geometric parameters (Å , ).Br1-Cu1

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