New open frameworks based on metal pyridylphosphonates.

A family of new 1D, 2D, and 3D coordination networks based on metal-pyridylphosphonates have been synthesized under hydro(solvo)thermal conditions. Zn(3-pyridylphosphonate)(bromide), 1, adopts a 1D ladder structure, while Co(4-pyridylphosphonate)(H(2)O)(3), 2, adopts a 2D grid structure. [Cu(2)(4-pyridylphosphonate)(2)]-2H(2)O, 3, [Cd(3-pyridylphosphonate)(2)]-DMSO, 4, Cd(4-pyridylphosphonate)(2), 5, and Cd(ethyl 4-pyridylphosphonate)(2), 6, all adopt 3D framework structures. While 3 possesses open channels that are occupied by water molecules, 4 exhibits cavities that accommodate DMSO guest molecules. The present work demonstrates that interesting open frameworks can be readily synthesized on the basis of metal pyridylphosphonates. Crystal data for 1: monoclinic space group C2/c; a = 15.267(4), b = 11.903(2), c = 10.380(2) A; beta = 98.68(2) degrees; Z = 8. Crystal data for 2: monoclinic space group P2(1)/c; a = 9.634(12), b = 7.611(9), c = 11.901(1) A; beta = 97.830(2) degrees; Z = 4. Crystal data for 3: triclinic spacegroup P one macro; a = 7.464(8), b = 9.203(1), c = 11.602(2) A; alpha = 100.289(1) degrees; beta = 104.532(1) degrees, gamma = 94.569(1) degrees; Z = 2. Crystal data for 4: tetragonal space group I4(1)/a; a = 15.114(2), b = 15.114(2), c = 13.128(3) A; Z = 8. Crystal data for 5: monoclinic space group P2(1)/c; a = 8.344(2), b = 10.589(2), c = 14.384(3) A; beta = 91.77(3) degrees; Z = 4. Crystal data for 6: monoclinic space group P2(1)/n; a = 5.606(1), b = 11.198(1), c = 14.176(2) A; beta = 94.518(1) degrees; Z = 2.

Three-dimensional open frameworks based on cobalt(II) and nickel(II) m-pyridinecarboxylates.

Three-dimensional open frameworks [Co2(nicotinate)4(mu-H2O)]-CH3CH2OH-H2O, 1, and [Ni2(nicotinate)4(mu-H2O)]-CH3CH2OH-H2O, 2, were obtained by hydro(solvo)thermal reactions between 3-cyanopyridine and cobalt(II) nitrate and nickel(II) perchlorate, respectively. Both 1 and 2 exhibit complicated 3-D structures based on [M2(nicotinate)4(mu-H2O)] (M = Co or Ni) building blocks and possess open channels that are occupied by removable solvent molecules. 3-D open frameworks [M2L4(mu-H2O)]-HL-(H2O)x (where M = Co, x = 2, 3, and M = Ni, x = 1, 4, and L = trans-3-(3-pyridyl)acrylate) were similarly prepared with trans-3-(3-pyridyl)acrylic acid in place of 3-cyanopyridine. Compounds 3 and 4 are isostructural and exhibit network topologies similar to that of 1 with open channels occupied by disordered trans-3-(3-pyridyl)acrylic acid and water guest molecules. Crystal data for 1: triclinic space group Ponebar, a = 10.534(1) A, b = 11.907(1) A, c = 14.046(1) A, alpha = 106.645(1) degrees, beta = 101.977(1) degrees, gamma = 112.078(1) degrees, and Z = 4. Crystal data for 2: tetragonal space group P4/ncc, a = 20.089(1) A, c = 14.016(1) A, and Z = 4. Crystal data for 3: monoclinic space group C2/c, a = 14.082(2) A, b = 15.278(2) A, c = 18.537(2) A, beta = 105.360(2) degrees, and Z = 2. Crystal data for 4: monoclinic space group C2/c, a = 14.082(1) A, b = 15.250(1) A, c = 18.606(1) A, beta = 106.747(1) degrees, and Z = 2.

Pillared, 3D metal-organic frameworks with rectangular channels. Synthesis and characterization of coordination polymers based on tricadmium carboxylates.

Hydro(solvo)thermal reactions between cadmium(II) perchlorate and 4-pyridinecarboxaldehyde in the presence of various guest molecules have resulted in a series of 3-D coordination polymers based on tricadmium carboxylates [Cd6(isonicotinate)10(H2O)2](ClO4)2(EtOH)4(H2O)4, 1, [Cd3(isonicotinate)5 (EtOH)](ClO4)(EtOH)(4-nitroaniline)0.5, 2, and [Cd6(isonicotinate)11](ClO4)(EtOH)2(H2O)2(4-cyanopyridine)0.5, 3. X-ray single crystal structure determinations show that they exhibit similar pillared, 3D framework structures based on tricadmium carboxylate building blocks. Rectangular channels are clearly present in these polymeric networks and are occupied by perchlorate anions and disordered guest molecules. Quantitative NMR and X-ray powder diffraction studies and thermogravimetric analyses (TGA) reveal that these coordination networks are capable of accommodating different guest molecules. More significantly, the guest molecules can be readily removed via evacuation to result in nanoporous polymeric coordination networks retaining the framework structures of the pristine solids. Crystal data for 1: monoclinic space group P2(1)/n, a = 19.041(1) A, b = 23.654(1) A, c = 21.568(1) A, beta = 95.440(1) degrees, and Z = 4. Crystal data for 2: triclinic space group P1, a = 12.050(1) A, b = 12.277(1) A, c = 19.103(1) A, alpha = 91.669(1) degrees, beta = 96.850(1) degrees, gamma = 117.945(1) degrees, and Z = 2. Crystal data for 3: monoclinic space group P2(1)/n, a = 19.038(1) A, b = 23.834(1) A, c = 21.756(1) A, beta = 97.580(1) degrees, and Z = 4.