Novel intercalation host system based on transition metal (Fe2+, Co2+, Mn2+)-chloranilate coordination polymers. Single crystal structures and properties

The new iron(II), cobalt(II), and manganese(II) intercalation compounds {[M (CA)(H2O)(2)](G)}(n) (M = Fe2+, Co2+, Mn2+; H(2)CA = chloranilic acid (C6H2 O4Cl2); G = H2O and phenazine (C12H8N2; phz)) have been synthesized and cha racterized. {[Fe(CA)(H2O)(2)](H2O)}(n) (1a) crystallizes in the monoclinic space group C2/c (No. 15) with a = 4.914(2) Angstrom, b = 14.222(2) Angstro m, c = 13.987(2) Angstrom, beta = 94.98(2)degrees, V = 973.8(4) Angstrom(3) , and Z = 4. {[Fe(CA)(H2O)(2)](phz)}(n) (2a) crystallizes in the triclinic space group P (1) over bar (No. 2) with a 8.079(2) Angstrom, b = 11.366(3) Angstrom, c = 5.055(2) Angstrom, alpha = 96.57(3)degrees, beta = 98.70(3)de grees, gamma = 83.07(2)degrees, V = 453.3(3) Angstrom(3), and Z = 1. {[M(CA )(H2O)(2)](H2O)}(n) (M = Co2+ (1b), Mn2+ (1c)) are isomorphous to 1a. For 1 a-c, crystal structures consist of uncoordinated guest water molecules and one-dimensional zigzag [M(CA)(H2O)(2)](k) chains. Two water molecules occup ying cis positions and two chloranilate filling the remaining sites in a bi s bidentate fashion create the octahedral environment around the metal ion to form a zigzag chain (type I), which extends along the diagonal between t he a and c axes. The adjacent chains are interlinked by hydrogen bonds, thu s forming layers, which spread out along the ac plane. Water molecules are intercalated between the ([M(CA)(H2O)(2)](k))(l) layers. The intercalation mode of the water molecules is different from those in {[M(CA)(H2O)(2)](phz )}(n) (M = Fe2+ (2a), Co2+ (2b), Mn2+ (2c)), which are isomorphous each oth er. The crystal structures of 2a-c consist of uncoordinated phenazine molec ules and straight [M(CA)(H2O)(2)](k) chains (type II). Infinite, nearly cop lanar linear chains are formed by metal ions and the bis-chelating CA(2-) a nions, which extend along the a direction, and are linked by hydrogen bonds between the coordinated water and the oxygen atoms of the CA(2-) on the ad jacent chains, forming a two-dimensional sheet, which spreads out along the ac plane. The intercalated phenazines are stacked along the c axis perpend icular to the [M(CA)(H2O)(2)](k) chain, and the planes of the phenazine mol ecules are tilted to the stacking direction, forming a segregated columnar structure between the {[M(CA)(H2O)(2)](k)}(l) layers. The Fe-57 Mossbauer s pectra of 1a and 2a consist of a single quadrupole doublet with IS = 1.16 m m/s (1a), 1.16 mm/s (2a) and QS = 2.53 mm/s (1a), 1.46 mm/s (2a) at 298 K, indicating that the oxidation state of the iron in both complexes is two. T he magnetic susceptibilities were measured from 2 to 300 K and analyzed by a one-dimensional Heisenberg-exchange model to yield J = -0.74 cm(-1), g = 2.01, rho = 1.4% (1c) and J = -0.65 cm(-1), g = 2.02, rho = 9.0% (2c).