Structure and thermal reactivity of Zn(II) salts of isocinchomeronic acid (2,5-pyridinedicarboxylic acid)

E. E. SILEO; O. E. PIRO; G. RIGOTTI; M. A. BLESA; A. S. DE ARAUJO; E. E. CASTELLANO

STRUCTURAL CHEMISTRY

Springer

Año: 2008 vol. 19 p. 651 - 657

1040-0400

Abstract. The synthesis, an improved refined crystal and molecular structure re-determination, and the thermal decomposition behavior of two Zn(II) derivatives of isocinchomeronic acid (2,5-pyridinedicarboxylic acid or H22,5-pydc) are presented. [Zn(2,5-pydc)(H2O)3Zn(2,5-pydc)(H2O)2]2 (1) crystallizes in the triclinic P-1 space group with a = 7.106(2), b = 11.450(2), c = 11.869(1) A ° , alpha = 107.29(1), beta = 104.08(1), gamma = 90.32(2), and Z = 2. [Zn(2,5-pydc)(H2O)2].H2O (2) is orthorhombic (P212121 space group), with a = 7.342(1), b = 9.430(1), c =13.834(2) A ° , and Z = 4. The structures were refined to agreement R1-factors of 0.0315 (1) and 0.0336 (2). Complex (1) is arranged as molecular Zn4(2,5-pydc)4(H2O)10 tetramers, the cages of which define channels that remain unblocked by anions. Compound (2) is polymeric with Zn(2,5-pydc)(H2O)2 and Zn(2,5-pydc)(H2O)3 units linked through bridging ligands. Both compounds were synthesized under mild conditions in aqueous media, without need to resort to hydrothermal media. Changing the pH from 4.51 to 5.75 suffices to direct the chemical processes toward the orthorhombic compound rather than to the triclinic one.The synthesis, an improved refined crystal and molecular structure re-determination, and the thermal decomposition behavior of two Zn(II) derivatives of isocinchomeronic acid (2,5-pyridinedicarboxylic acid or H22,5-pydc) are presented. [Zn(2,5-pydc)(H2O)3Zn(2,5-pydc)(H2O)2]2 (1) crystallizes in the triclinic P-1 space group with a = 7.106(2), b = 11.450(2), c = 11.869(1) A ° , alpha = 107.29(1), beta = 104.08(1), gamma = 90.32(2), and Z = 2. [Zn(2,5-pydc)(H2O)2].H2O (2) is orthorhombic (P212121 space group), with a = 7.342(1), b = 9.430(1), c =13.834(2) A ° , and Z = 4. The structures were refined to agreement R1-factors of 0.0315 (1) and 0.0336 (2). Complex (1) is arranged as molecular Zn4(2,5-pydc)4(H2O)10 tetramers, the cages of which define channels that remain unblocked by anions. Compound (2) is polymeric with Zn(2,5-pydc)(H2O)2 and Zn(2,5-pydc)(H2O)3 units linked through bridging ligands. Both compounds were synthesized under mild conditions in aqueous media, without need to resort to hydrothermal media. Changing the pH from 4.51 to 5.75 suffices to direct the chemical processes toward the orthorhombic compound rather than to the triclinic one.