The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-amino-phenyl)arsonic acid

摘要

(4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg-(H_2O)_6](C_6H_7AsNO_3)?4H_2O, (I), catena-poly[[[diaquacalcium]-bis[μ_2-hydrogen (4-aminophenyl)arsonato-κ~2O:O/]-[diaquacalcium]-bis[μ_2-hydrogen (4-amino-phenyl)arsonato-κ~2O:O]] dihydrate], {[Ca(C_6H_7AsNO_3)_2(H_2O)_2]?2H_2O}_n, (II), catena-poly[[triaquastrontium]-bis[μ_2-hydrogen (4-aminophenyl)arsonato-κ~2O:O/]], [Sr(C_6H_7AsNO_3)_2(H_2O)_3]_n, (III), and catena-poly[[triaquabarium]-bis[μ_2-hy-drogen (4-aminophenyl)arsonato-κ~2O:O']], [Ba(C_6H_7AsNO_3)_2(H_2O)_3]_n, (IV). In the structure of magnesium salt (I), the centrosymmetric octahedral [Mg(H_2O)_6]~2+ cation, the two hydrogen p-arsanilate anions and the four water molecules of solvation form a three-dimensional network structure through inter-species O—H and N—H hydrogen-bonding interactions with water and arsonate O-atom and amine N-atom acceptors. In one-dimensional coordination polymer (II), the distorted octahedral CaO_6 coordination polyhedron comprises two trans-related water molecules and four arsonate O-atom donors from bridging hydrogen arsanilate ligands. One bridging extension is four-membered via a single O atom and the other is eight-membered via O:O'-bridging, both across inversion centres, giving a chain coordination polymer extending along the [100] direction. Extensive hydrogen-bonding involving O—H???O, O — H ??? N and N—H ??? O interactions gives an overall three-dimensional structure. The structures of the polymeric Sr and Ba complexes (III) and (IV), respectively, are isotypic and are based on irregular MO_7 coordination polyhedra about the M~2+ centres, which lie on twofold rotation axes along with one of the coordinated water molecules. The coordination centres are linked through inversion-related arsonate O:O'-bridges, giving eight-membered ring motifs and forming coordination polymeric chains extending along the [100] direction. Inter-chain N—H ??? O and O—H ??? O hydrogen-bonding interactions extend the structures into three dimensions and the crystal packing includes π-π ring interactions [minimum ring centroid separations = 3.4666 (17) A for (III) and 3.4855 (8) A for (IV)].