Three crystalline complexes containing fluorine anion water cluster were reported. The fluoride anions and water molecules are H-bonded to each other in an alternating fashion within the fluoride–water hybrid cluster, where a fluoride anion plays the important role.

C10H16N6O3, monoclinic, P 2 1 / c $P{2}_{1}/c$ (no. 14), a = 7.2312(1) Å, b = 17.7721(3) Å, c = 11.0146(2) Å, β = 104.557°, V = 1370.08(4) Å3, Z = 4, R gt (F) = 0.0532, wR ref (F 2) = 0.1537, T = 170.0 K.

C6H12N6O4, monoclinic, P21/n (no. 14), a = 7.3652(3) Å, b = 16.8683(7) Å, c = 8.3779(3) Å, β = 101.525(4)°, V = 1019.87(7) Å3, Z = 4, R gt (F) = 0.0349, wR ref (F 2) = 0.1018, T = 170 K.

C17H14N2OFCl, triclinic, P1̄ (no. 2), a = 8.2387(19) Å, b = 9.764(2) Å, c = 10.644(3) Å, α = 72.023(4)°, β = 72.770(4)°, γ = 78.581(4)°, V = 772.5(3) Å3, Z = 2, Rgt(F) = 0.0444, wRref(F2) = 0.1099, T = 294.15 K.

C24H34N6Cl2Zn, monoclinic, P21/c (no. 14), a = 9.513(3) Å, b = 9.546(3) Å, c = 30.956(10) Å, β = 101.228(9)°, V = 2757.3(15) Å3, Z = 4, Rgt(F) = 0.0452, wRref(F2) = 0.1299, T = 293 K.