SYNTHESIS, CHARACTERIZATION, AND X-RAY CRYSTAL-STRUCTURES OF CYCLAM DERIVATIVES .2. HEPTAHYDRATE TETRAPROTONATED -2-CARBOXYETHYL)-1,4,8,11-TETRAAZACYCLOTETRADECANE H(4)TETP-CENTER-DOT-7H(2)0, THE PERCHLORATE PENTAPROTONATED FORM (H(5)TETP)(-)CENTER-DOT-2H(2)0()CL0(4), AND THE TETRACHLORIDE DIHYDRATE OCTAPROTONATED FORM (H(8)TETP)(4+),4CL()

The synthesis, characterization, and X-ray diffraction study of the te traprotonated, pentaprotonated, and octaprotonated forms of 1,4,8,11-( tetra-2-carboxyethyl) 1,4,8,11 -tetraazacyclotetradecane acid are repo rted. Crystal data for (H(4)TETP). 7H(2)O: (C22N4O8H40). 7H(2)O, Mr = 614.7, triclinic, P ($) over bar 1, a = 7.497(2) Angstrom, b = 9.348(1 ) Angstrom, c = 11.911(2) Angstrom, alpha = 71.92(1)degrees, beta = 73 .24(1)degrees, gamma = 81.15(1)degrees, V = 757.9(2) Angstrom(3), Z = 1, D-x = 1.35 g.cm(-3) F(000) = 334 e(-), mu = D.96 mm(-1) for lambda( CU K alpha) = 1.5418 Angstrom, R(\F\) = 0.082 for 1451 data (parallel to sigma(\)greater than or equal to 3). Crystal data for (H(5)TETP)(+) , ClO ($) over bar(4): (C22N4O8H41)(+), ClO4, Mr = 589.0, monoclinic, C2/c, a = 17.797(8) Angstrom, b = 12.611(3) Angstrom, c = 13.577(3) An gstrom, beta = 111.08(3)degrees, V = 2843(2) Angstrom(3), Z = 4, D-x = 1.38 g.cm(-3), F(000) = 1256 e(-), mu = 0.20mm(-1) for lambda(MoK alp ha) = 0.7107 Angstrom, R(\F\) = 0.050 for 1726 data (parallel to sigma (\)greater than or equal to 3). Crystal data for (H(8)TETP)(4+) 4Cl(-) . 2H(2)0: (C22N4O8H44)(4+) 4Cl(-)2H(2)O, Mr = 670.5, triclinic, P ($) over bar 1, a = 8.119(5) Angstrom, b = 9.704(6) Angstrom, c = 10.172(5 ) Angstrom, alpha = 95.87(5)degrees, beta = 97.41(4)degrees, gamma = 1 06.06(5)degrees, V = 755.7(8) Angstrom(3), Z = 1, D-x = 1.47 g.cm(-3), F(000) = 356 e(-), mu = 0.45 mm(-1) for lambda(MoK alpha) = 0.7107 An gstrom, R(\F\) = 0.077 for 1493 data (parallel to sigma(\)greater than or equal to 3). Each macrocycle has a [3434] conformation. In the tet ra-and pentaprotonated forms, two propionate groups are extended out o f the cycle whereas the other two are folded and linked to the nitroge n atoms of the macrocycle via hydrogen bonds. In the octaprotonated fo rm the four propionate groups are extended out of the cycle. These res ults reinforce a theoretical investigation based on density functional calculations.