Red and orange 1: 1 adducts of copper(1) hydride with triphenylphosphine have been isolated from tetrahydrofuran as hexameric and pentameric cluster species that have been characterized crystallographically. The red hexameric species [ (PPh3)CuH],.0.5thf crystallizes in the monoclinic space group P2, with a = 14.464 (IO) A, b = 16.252 (9) A, c = 21.487 ( 5 ) A, 0 = 91.38 (3)O, Z = 2, and R = 0.052 for 5932 observed (I 1 30(1)) reflections. Cu-P distances are 2.200 (3)-2.246 (3) A. Hydrogen atoms have been located by refinement at the centers of six triangular faces equatorial about a quasi-6 axis of the octahedral copper skelton. A crystalline "hydrolysis" product of this compound, tentatively formulated as [(PPh,),CU&O]*thf, has also been structurally characterized, crystallizing in the orthorhombic space group Pbca with a = 40.19 (2) A, b = 22.78 (2) A, c = 21.72 (2) A, Z = 8, and R = 0.071 for 5041 observed reflections in a lattice isomorphous with the previously recorded [(PPh3)CuHI6.dmf compound. An orange pentameric species, formulated as [(PPh,)CuH],.thf, crystallizes in the monoclinic space group P21/c with a = 12.827 (6) A, b = 12.952 (8) A, c = 54.226 (14) A, @ = 95.96 (4)", Z = 4, and R = 0.095 for 2393 observed reflections. The copper atoms are disposed in a distorted-trigonal-bipyramidal array with Cu,,-.Cu, distances ranging between 2.431 (7) and 2.582 (7) 8, and Cu,--Cu, distances between 2.493 (8) and 2.608 (7) A. The Cu-P distances range between 2.16 (1) and 2.21 ( I ) A. Hydride positions were not found