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Spectroscopic and Structural Investigation of two N-Benzylpiperazinium Tetrachlorocuprates(II), one Hemihydrate and one Anhydrous:Two Compounds containing Unequally Flattened (2-) Tetrahedra
Antolini, Luciano,Menabue, Ledi,Pellacani, Gian Carlo,Saladini, Monica,Marcotrigiano, Giuseppe,Porzio, William
, p. 1753 - 1759 (1981)
Two compounds *0.5H2O (yellow) and (green) (2+ = N-benzylpiperazinium dication) have been prepared and investigated by means of electronic and vibrational spectra, magneti moments, d.s.c. and crystal-structure measurements.The crystal structures were determined by threedimensional X-ray diffraction.The two compounds crystallize in the space groups P21/a (yellow) and P21 (green) with unit-cell dimensions a = 17.015(1), b = 16.977(2), c = 11.377(2) Angstroem, β = 97.156(4) deg, Z = 8 and a = 12.075 7(3), b = 28.479 8(10), c = 9.925 8(9) Angstroem, β = 109.54(1) deg, Z = 8, for the yellow and green compounds respectively.The structures have been refined to R 0.036 and 0.067, respectively.The yellow complex consists on two crystallographically independent 2- anions with moderately flattened tetrahedral geometry, two 2+ cations, and a water molecule of crystallization.The green complex consists of four independent discrete 2- anions, unequally flattened , and four independent 2+ cations, which bridge the anions through hydrogen bonds involving their N-bonded H atoms.The role of hydrogen bonding in the flattening of the tetrahedral 2- ions is discussed.The spectroscopic and magnetic properties of the complexes are explained in the light of their known crystal structures.The transformation of the yellow form to the green form by heating (quasi-irreversible thermochromism) is also discussed.
