CRYSTAL AND MOLECULAR STRUCTURE OF 5-COORDINATE COMPLEX CHLOROTRIS(O-METHYLTHIOPHENYL)PHOSPHINENICKEL(2) PERCHLORATE

The crystal and molecular structure of chlorotris(o-methylthiophenyl)phosphinenickel(II) perchlorate, [Ni(TSP)Cl] [ClO4], has been determined from three-dimensional single-crystal X-ray data collected by standard film techniques. The structure has been refined by least-squares methods to a conventional R factor of 0.090 for 1499 nonzero reflections. The complex crystallizes in space group C2/c of the monoclinic system with a cell of dimensions a = 22.93 ± 0.04, b = 12.08 ± 0.03, c = 18.21 ± 0.03 Å, β = 102.4 ± 0.1°, and V = 4917 Å3. An experimental density of 1.57 (4) g/cm3 is in good agreement with a calculated value of 1.60 g/cm3 for eight molecules in the unit cell. The Ni(TSP)Cl+ complex possesses a nearly regular trigonal-bipyramidal structure with the three S atoms located in the equatorial positions and the P and Cl atoms at the apices. The Ni-P and Ni-Cl distances are 2.113 (7) and 2.227 (7) Å, respectively. The Ni ion is displaced slightly but significantly out of the plane of the equatorial S atoms toward the apical halogen. The magnitude of this displacement is 0.061 (2) Å. The average Ni-S equatorial distance of 2.267 (7) Å is indicative of only slight metal-sulfur bonding in the five-coordinate complex. © 1969, American Chemical Society. All rights reserved.