Adduct Formation between Alkali Metal Ions and Divalent Metal Salicylaldimine Complexes Having Methoxy Substituents. A Structural Investigation

Sodium, potassium, and cesium salts (iodides, nitrates, acetates, and tetraphenylborates) form 1/1, 1/2 and 2/3 adducts with ML_n [M = Co, Ni, Cu, and Zn; n = 1−4; H₂L₁ = N,N‘-(3-methoxysalicylidene)ethane-1,2-diamine; H₂L₂, H₂L₃, and H₂L₄ are the -propane-1,2-diamine, -o-phenylenediamine, and -propane-1,3-diamine analogues of H₂L₁). Metal salicylaldimine, alkali metal, and anion all exert influence on stoichiometry and reactivity. Sodium ions tend to reside within the planes of the salicylaldimine oxygens, as in Na(NO₃)(MeOH)·NiL₄ (1), Na(NO₃)(MeOH)·CuL₁ (2; both with unusual seven-coordinated sodium), and Na·(NiL₄)₂I·EtOH·H₂O (3; with dodecahedral sodium coordination geometry). Potassium and cesium tend to locate between salicylaldimine ligands as in KI·NiL₄ (4) and [Cs(NO₃)·NiL₄]₃·MeOH (5; structures with infinite sandwich assemblies), CsI·(NiL₂)₂·H₂O (6), CsI₃·(NiL₄)₂ (7; simple sandwich structures), and [K(MeCN)]₂·(NiL₄)₃ (8; a triple-decker sandwich structure). Crystal data for 1 are the following:  triclinic, P1, a = 7.3554(6) Å, b = 11.2778(10) Å, c = 13.562(2) Å, α = 96.364(10)°, β = 101.924(9)°, γ = 96.809(10)°, Z = 2. For 2, triclinic, P1, a = 7.2247(7) Å, b = 11.0427(6) Å, c = 13.5610(12) Å, α = 94.804(5)°, β = 98.669(7)°, γ = 99.26(6)°, Z = 2. For 3, orthorhombic, Pbca, a = 14.4648(19) Å, b = 20.968(3) Å, c = 28.404(3) Å, Z = 8. For 4, triclinic, P1, a = 12.4904(17) Å, b = 13.9363(13) Å, c = 14.1060(12) Å, α = 61.033(7)°, β = 89.567(9)°, γ = 71.579(10)°, Z = 2. For 5, monoclinic. P2₁/n, a = 12.5910(2) Å, b = 23.4880(2) Å, c = 22.6660(2) Å, β = 99.3500(1)°, Z = 4. For 6, orthorhombic, Pbca, a = 15.752(3) Å, b = 23.276(8) Å, c = 25.206(6) Å, Z = 8. For 7, triclinic, P1, a = 9.6809(11) Å, b = 10.0015(13) Å, c = 11.2686(13) Å, α = 101.03°, β = 90.97°, γ = 100.55°, Z = 2. For 8, monoclinic, C2/c, a = 29.573(5) Å, b = 18.047(3) Å, c = 23.184(3) Å, β = 122.860(10)°, Z = 8.