AbstractThe ligand 1,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐2,5‐dimethyl‐2,5‐diazahexane (debd), which has been synthesized from 3,5‐dimethylpyrazole, N,N′‐dimethylethanediamine and formaldehyde, partially disintegrates when reacted with zinc dichloride or with zinc dibromide in methanol. The resulting compounds contain the unique bis(pyrazolato)‐bridged tetrahalogenido dizinc(II) anion. The compound [Zn(debd)Cl]2[Zn2(dmpz)2Cl4], with formula C42H70Cl6N16Zn4 and Mr = 1273.36, is obtained from methanol as monoclinic crystals, spacegroup P 21/c with a = 15.990(2) Å, b = 16.394(2) Å, c = 12.006(1) Å, β = 100.61(1)°, V = 3093.4(5) Å3, Zm = 2, Dx = 1.37 g.cm−3, as measured at room temperature with Mo(Kα) radiation to a final R value of 0.062 (wR = 0.065) for 2465 significant [I > 2σ‐(I)] reflections.The asymmetric unit comprises half the formula unit. The cation consists of a Zn2+ ion in a distorted trigonal bipyramidal environment of a chloride ion at 2.221(3) Å, an amine nitrogen at 2.17(1) Å and a pyrazole nitrogen at 2.05(1) Å in the equatorial plane, with an amine nitrogen at 2.27(1) and a pyrazole nitrogen at 2.14(1) Å in the axial positions. The largest distortion is in the axis of the trigonal bipyramide with an N‐Zn‐N angle of 150.2(5)°.The anion consists of two Zn2+ ions, which are bridged by two deprotonatedThe authors realise that the recommended IUPAC term is (de)hydronated instead of (de)protonated to indicate loss/addition of H+. dimethylpyrazole ligands with N‐Zn distances of 1.97(1) and 1.98(1) Å, while each Zn2+ ion is further bound to two chloride ions at 2.276(4) and 2.261(4) Å. The Zn2+ ions are in an almost regular N2Cl2 tetrahedron.