W0349
Structural Chemistry of Layered Metal Naphthalenesulfonate
Salts. Philip J. Squattrito, Jill E. Morris, Kristin Kirschbaum, A. Alan
Pinkerton, Dept. of Chemistry, Central Michigan Univ., Mt. Pleasant, MI, 48859
and Dept. of Chemistry, Univ. of Toledo, Toledo, OH, 43606.
This paper presents recently obtained structural results of
metal salts of amine-substituted naphthalenesulfonate anions with a view towards
discerning trends in the type of layered structure observed as a function of the
substitution pattern of the anion. 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. 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 hexaaquametal cation layers. The repeat unit along the stacking axis is a
double layer. Crystal data for
[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)o, V = 1404.3(7)
Å3;
[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)o, V = 1421.5(9)
Å3. The Co and Ni compounds are isostructural with each other,
but compared to the Mg and Mn compounds, have a strikingly different structure.
They also contain layers of octahedral hexaaquametal complexes and additional
water molecules of crystallization sandwiched by layers of sulfonate anions,
however the stacking pattern is more complex with a novel quadruple layer repeat
unit and two different types of anion layers. Crystal data for
[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;
[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. The difference in structure between the two sets of
divalent cations is unexpected, as sulfonate salts of these ions are usually all
isostructural. These structures will be compared with those of other substituted
naphthalenesulfonate salts recently characterized in our laboratory.