The structures of five dicopper complexes of binucleating ligand HL-H (N,N,N’,N’-tetrakis[(2-benzimadazolyl)methyl]-2-hydroxy-1,3-diaminopropane) with thiocyanate and some other counterions were investigated by the x-ray diffraction method. In Cu-2(HL-H)(NCS)(2)Cl-2.6H(2)O.CH3OH, 1 (a = 12.524(5) Angstrom, B = 14.429(4) Angstrom, c = 16.343(3) Angstrom, Alpha = 109.01(2)-degrees, Beta = 92.62(2)-degrees, Gamma = 115.27(3)-degrees, Z = 2, triclinic P(1)-over-bar), one chloride is not coordinated. Distorted square pyramidal (SP) geometry is found for both CuN3CIN and CuN3ON coordination sites in which the N-3 tripodal coordination sites come from the two symmetric halves of HL-H and other nitrogen atoms come from thiocyanate ions. In Cu-2(HL-H)(NCS)(2)(ClO4)(2).6H(2)O.2EtOH, 2 (a = 10.955(2) Angstrom, b = 15.366(5) Angstrom, c = 18.465(9) Angstrom, Alpha = 65.57(4)-degrees, Beta = 89.73(3)-degrees, Gamma = 79.81(2)-degrees, Z = 2, triclinic P(1)-over-bar), the coordination environments for the two copper ions are both CuN3ON. However, their geometries are different : one is distorted SP and the other is distorted trigonal bypyramid (TBP). In Cu-2(HL-H)(NCS)(2)(ClO4)(2)Cl.H3O.3.5H(2)O, 3 (a = 11.986(6) Angstrom, b = 12.778(5) Angstrom, c = 17.81(1) Angstrom, Alpha = 82.41(4)-degrees, Beta = 75.44(5)-degrees, Gamma = 78.46(4)-degrees, Z = 2, triclinic, P(1)-overbar), the chloride ion does not coordinate to copper ion, but it is hydrogen bonded to the hydroxy hydrogen. The coordination environments for the two copper ions are both CuN3ON with distorted SP geometries. In Cu-2(HL-H)(NCS)Cl-3.6H(2)O, 4 (a = 12.026(5) Angstrom, b = 14.369(6) Angstrom, c = 16.430(6) Angstrom, Alpha = 111.64(3)-degrees, Beta = 90.51(4)-degrees, Gamma = 113.90(3)-degrees, Z = 2, triclinic, P(1)-over-bar), one chloride does not coordinate. The coordination environments for the two copper ions are CuN3ON in severely distorted TBP geometry and CuN3Cl2 in SP geometry. In Cu-2(HL-H)(NCS)(3)OH.2H(2)O.3CH(3)OH.Et(2)O, 5 (a = 18.322(5) Angstrom, b = 15.543(6) Angstrom, c = 19.428(7) Angstrom, Beta = 102.78(3)-degrees, Z = 4, monoclinic, P2(1)/c), the hydroxide ion does not coordinate. The coordination environments for the two copper ions CuN3N2 with a geometry inbetween SP and TBP geometry but slightly closer to SP and CuN3ON in distorted SP geometry. The distances between the copper ions are in the range 4.45-7.99 Angstrom, indicating negligible interaction between the copper ions. The hydroxy groups of HL-H in 1-5 all coordinate to copper ions either in a terminal mode (in complexes 1, 4, and 5, denoted as OHR(t))or in a bridging mode (in complexes 2 and 3, denoted as OHR(b)). These hydroxy groups do not lose their protons in all cases. All thiocyanate anions coordinate to copper ions through nitrogen atoms. All copper ions in 1-5 are pentacoordinated. The fact that the CuN3 geometries of the tripodal coordination sites in HL-H do not allow the formation of a square planar complex, may be the driving force for the formation of pentacoordinated complexes. From the structurally known dicopper complexes of the HL-H type ligands, the relative coordinating abilities of ligands to CuN3 are OHR(t) greater-than NCS- greater-than Cl--(t) greater-than OHR(b) is-similar-to Cl--(b), where the letters b and t in parentheses denote bridging and terminal coordination modes respectively.<畯