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The synthesis of the Mannich base N,N′‐tetra(antipyryl‐4‐methyl)‐1,2‐ethanediamine (TAMEN) (1), its crystal structure as well as the synthesis and the crystal structure of the copper complex [Cu(TAMEN)](ClO4)2·H2O·DMF (2) are reported. C50H56N10O4·2C2H5OH (TAMEN·2EtOH) crystallizes with triclinic symmetry, space group $P{\bar 1}$, lattice parameters: a = 877.3(1), b = 1078.1(1), c = 1433.3(2) pm, α = 71.93(1), β = 82.16(1), γ = 84.54(1)° and Z = 1. The copper complex [Cu(TAMEN)](ClO4)2·H2O·DMF also crystallizes with triclinic symmetry, space group $P{\bar 1}$, lattice parameters: a = 1279.2(2), b = 1485.6(2), c = 1513.6(2) pm, α = 98.04(1), β = 101.24(1), γ = 94.66(1)° and Z = 2. The copper(II) atom is six‐coordinate with an elongated pseudo‐octahedral geometry due to a strong Jahn‐Teller effect.

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