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Materials 2021, 14, 1786 12 of 1290 In TbCP3 crystal structure, the Haip− and aip2−ligands interconnect the Tb3+ centers In TbCP3 crystal structure, the Haip − and aip 2− ligands interconnect the Tb 3+ centers by unidentate bridging and chelate modes (Supplementary Material: Figure S5b), promot- by unidentate bridging and chelate modes (Supplementary Material: Figure S5b), promot- ing the formation of an interesting 1D CP (coordination chain) with a distorted ladder ing the formation of an interesting 1D CP (coordination chain) with a distorted ladder structure along the a-axis of the unit cell, and the phen ligands of adjacent metallic centers structure along the a-axis of the unit cell, and the phen ligands of adjacent metallic centers oriented in opposite directions (Figure 6a). Ligand arrangement imposes inter-ladder oriented in opposite directions (Figure 6a). Ligand arrangement imposes inter-ladder Tb···Tb distances of 4.270(1), 8.250(2), 10.350(2) Å and 13.514(3) Å. The neighboring 1D Tb···Tb distances of 4.270(1), 8.250(2), 10.350(2) Å and 13.514(3) Å. The neighboring 1D ladders are involved in an extensive network of strong N−H···O and O−H···O intermolec- ladders are involved in an extensive network of strong N−H···O and O−H···O intermolec- ular interactions (not shown), leading to an overall crystalline packing arrangement with voids occupied by uncoordinated water molecules (Figure 6b; more details concerning the geometric information of the H-bonds can be consulted in Table 5). Figure 6. Structural features of the crystal structure of TbCP3, {[Tb(Haip)(aip)(phen)]·H2O}n: (a) 1D Figure 6. Structural features of the crystal structure of TbCP3, {[Tb(Haip)(aip)(phen)]·H2O}n: (a) 1D CP with ladder arrangement (coordination chain). (b) Extended packing viewed in the [100] direc- CP with ladder arrangement (coordination chain). (b) Extended packing viewed in the [100] direction tion of the unit cell, with the different coordination ladders drawn in distinct colors, and the crys- of the unit cell, with the different coordination ladders drawn in distinct colors, and the crystallization tallization water molecules depicted in the space fill model (orange/yellow color scheme). H-at- water molecules depicted in the space fill model (orange/yellow color scheme). H-atoms, except for oms, except for those belonging to water molecules, have been omitted for clarity. those belonging to water molecules, have been omitted for clarity. Table 5. Geometric information (distances in Å and angles in degrees) for the D–H···O hydrogen Table 5. Geometric information (distances in Å and angles in degrees) for the D–H···O hydrogen bond interactions found in the crystal structure of TbCP3, [Tb(Haip)(aip)(phen)]·H2O. bond interactions found in the crystal structure of TbCP3, [Tb(Haip)(aip)(phen)]·H2O. D–H···O D–H···O N1−H1N···O1W N2−H2A···O1Wvii N2−H2C···Ov8iivii d (H···O) d (H···O) d (D···O) d (D···O) ∠ (DHO) ∠ (DHO) v 2.18(4) 2.984(8) 156(7) v N1−H1N···O1W vi 2.18(4) 2.984(8) 156(7) N1−H2N···O1 2.06(3) 2.888(7) 162(7) N1−H2N···O1vi N2−H2A···O1Wvii 2.06(3) 2.888(7) 162(7) N2−H2C···O8 O1OW1−WH−1HW1W····O··O7 7 1.77 2.682(3) 176.9 2.36 3.085(8) 136.1 2.36 3.085(8) 136.1 1.77 1.871(2.8)7(2) 2.682(3) 176.9 116677((77)) 2.726.746(74)(7) Symmetry transformations used to generate equivalent atoms: (v) −x, −y+1, −z; (vi) x+1, −y+3/2, z+1/2; (vii) −x+1, Symmetry transformations used to generate equivalent atoms: (v) −x, −y+1, −z; (vi) x+1, −y+3/2, z+1/2; (vii) y+1/2, −z+1/2. −x+1, y+1/2, −z+1/2.PDF Image | Green Chemistry with Supercritical CO2 and Enzymes
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