Structures of divalent transition metal salts of 4-aminonaphthalene-1-sulfonate: unexpected variations in layering pattern

Salts of 4-aminonaphthalene-1-sulfonate with divalent Mg, Mn, Co, and Ni cations have been crystallized and their structures determined by single crystal X-ray methods. The Mg and Mn salts are isostructural. Crystal data for hexa-aquamagnesium(II) 4-aminonaphthalene-1-sulfonate dihydrate, [Mg(H2O)6](H2NC10H6SO3)2 ⋅ 2H2O: monoclinic, P21/c, Z = 2, a = 8.622(3), b = 7.043(3), c = 23.178(3) Å, β=93.78(2)°, V = 1404.3(7) Å3; hexa-aquamanganese(II) 4-aminonaphthalene-1-sulfonate dihydrate, [Mn(H2O)6](H2NC10H6SO3)2 ⋅ 2H2O: monoclinic, P21/c, Z = 2, a = 8.652(3), b = 7.031(4), c = 23.402(2) Å, β=93.09(2)°, V = 1421.5(9) Å3. The structures are composed of alternating layers of octahedral metal–aqua complexes and sulfonate anions linked by an extensive network of hydrogen bonds. The extra water molecules of crystallization are located in the hexa-aquametal cation layers. The repeat unit along the c axis is a double layer. The Co and Ni compounds are isostructural with each other, but compared to the Mg and Mn compounds, have a strikingly different structure. Crystal data for hexa-aquacobalt(II) 4-aminonaphthalene-1-sulfonate trihydrate, [Co(H2O)6](H2NC10H6SO3)2 ⋅ 3H2O: orthorhombic, Pbca, Z = 8, a = 8.518(1), b = 14.327(2), c = 45.367(6) Å, V = 5536(1) Å3; hexa-aquanickel(II) 4-aminonaphthalene-1-sulfonate trihydrate, [Ni(H2O)6](H2NC10H6SO3)2 ⋅ 3H2O: orthorhombic, Pbca, Z = 8, a = 8.4976(6), b = 14.288(1), c = 45.076(3) Å, V = 5472.9(7) Å3. These structures also contain layers of octahedral hexa-aquametal complexes and additional water molecules of crystallization sandwiched by layers of sulfonate anions, however the stacking pattern is more complex with a quadruple layer repeat unit and two different types of anion layers.