The Effect of pH on the Dimensionality of Coordination Polymers

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Abstract

Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H(3)pdc) yielded seven new compounds. At a lower pH level three one-dimensional structures [Ca(Hpdc)(H(2)O)(4)].2H(2)O (1), [Ca(Hpdc)(H(2)O)(4)].H(2)O (2), and [Ba(H(2)pdc)(2)(H(2)O)(4)].2H(2)O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl(2) (M = Ca, Ba) with H(3)pdc in water (1, 6) or in water/Et(3)N (2) at 150 degrees C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc(2-) ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H(2)pdc(-) ligands. A dimer molecule [Sr(H(3)pdc)(H(2)pdc)(2)(H(2)O)(3)](2).2(H(3)pdc).4H(2)O (4) was obtained from a similar hydrothermal reaction using Sr(ClO(4))(2).6H(2)O instead of MCl(2). This compound contains [2+2] metallomacrocycles. At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H(2)O)] (Ca 3, Sr 5, Ba 7 ) were isolated by reactions of MCl(2) (M = Ca, Sr, Ba) with H(3)pdc in water/Et(3)N or in M(OH)(2) (M = Ca, Sr, Ba) with H(3)pdc in water under hydro(solvo)thermal conditions (150 degrees C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P2(1)/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) A, beta = 98.91(3) degrees, Z = 4; for 2, 3, and 5, monoclinic, space group P2(1)/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) A, beta = 96.73(3) degrees, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) A, beta = 103.65(3) degrees, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) A, beta = 98.96(3) degrees (5); for 4 and 7, triclinic, space group P1 (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) A, alpha = 71.54(3), beta = 98.96(3), gamma = 89.03(3) degrees, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) A, alpha = 74.69(3), beta = 73.39(3), gamma = 85.29(3) degrees, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) A, beta = 123.56(3) degrees, Z = 4.

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