Two new monoprotonated products of macrocyclic polyamine 1,4,7 trimethyl 1,4,7 triazacyclononane(Me 3〔9〕aneN 3), (Me 3〔9〕aneN 3H)(SO 3CF 3) 1 (C 10 H 22 N 3O 3SF 3, M r =321.36) and (Me 3〔9〕aneN 3H)I 2 (C 9H 22 N 3I, M r =299.20) were obtained by the reactions of Me 3〔9〕aneN 3 and yttrium triflate or ytterbium diiodide as the unexpected products. The crystal structures of compounds 1 and 2 have been determined. Crystal 1 is orthorhombic, space group P2 12 12 1(#19), a =12.609(3), b=13.531(1), c=9.225(3) , V=1573.9(7)  3, Z=4, D c= 1.356 g/cm 3, μ =2.47 cm -1 , F (000)=680 and R=0.052, R w =0.052 for 807 unique reflections with I>2σ(I) . Crystal 2 belongs to the orthorhombic system with space group P2 12 12 1(#19), a=11.417(2), b=13.099(3), c=8.762(2) , V=1310.5(4)  3, Z=4, D c =1^516 g/cm 3, μ =24.14 cm -1 , F (000)=600 and R=0.035, R w =0.042 for 1427 unique reflections with I>3σ(I) . The two structures contain the same cyclic framework in which the acid proton is bonded to an amine nitrogen. This proton exhibits strong intramolecular hydrogen bonds with the other two nitrogen atoms. The methyl groups are directed away from the ring cavity. The bond distance between acid proton and an amine nitrogen in compound 2 is extremely short. The bond angles for 1 and 2 also exhibit obvious diversity inside of triazacyclononae. Two new monoprotonated products of macrocyclic polyamine 1,4,7 trimethyl 1,4,7 triazacyclononane (Me 3 [9] aneN 3), (Me 3 [9] aneN 3H) (SO 3CF 3) 1 (C 10 H 22 N 3O 3SF 3, M r = 321.36) and (Me 3 [9] aneN 3H) I 2 (C 9H 22 N 3I, M r = 299.20) were obtained by the reactions of Me 3 [9] aneN 3 and yttrium triflate or Crystal 1 is orthorhombic, space group P2 12 12 1 (# 19), a = 12.609 (3), b = 13.531 (1), c = 9.225 (3)  V = 1573.9  3 Z = 4 D c = 1.356 g / cm 3 μ = 2.47 cm -1 F (000) = 680 and R = 0.052 R w = 0.052 for 807 unique reflections with I> 2σ (I). Crystal 2 belongs to the orthorhombic system with space group P2 12 12 1 (# 19), a = 11.417 (2), b = 13.099 (3), c = 8.762 2) , V = 1310.5 (4)  3, Z = 4, D c = 1 ^ 516 g / cm 3, μ = 24.14 cm -1, F (000) = 600 and R = = 0.042 for 1427 uniqu The two structures contain the same cyclic framework in which the acid proton is bonded to an amine nitrogen. This proton presents presents the intramolecular hydrogen bonds with the other two nitrogen atoms. The methyl groups are directed away The bond distance between acid proton and an amine nitrogen in compound 2 is extremely short. The bond angles for 1 and 2 also exhibit obvious obvious inside of triazacyclononae.