Template Syntheses and Crystal Structures of Hexaaza Macrocyclic Complexes with C-Methyl Substituent

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Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL](ClO4)2 (L = 5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetrade- cane) 1 and [NiL](ClO4)2 2, have been synthesized and structurally characterized through X-ray diffraction analysis. Also, crystal structure of [CuL1](ClO4)2 (L1 = 1,8-dimethyl-1,3,6,8,10,13- he- xaazacyclotetradecane) 3 has been determined. Crystal data for 1: C14H32Cl2CuN6O10, Mr = 578.90, monoclinic, P21/n, a = 8.3529(11), b = 10.8105(17), c = 13.3709(17) ?, β = 105.189(10)°, V = 1165.2(3) ?3, Z = 2, Dc = 1.650 g/cm3, F(000) = 602, λ(MoKα) = 0.71073 ?, μ = 1.229 mm-1, R = 0.0474 and wR = 0.0895 for 2771 observed reflections (I > 2σ(I)). Crystal data for 2: C14H32Cl2N6NiO10, Mr = 574.07, monoclinic, P21/c, a = 8.3636(12), b = 12.997(2), c = 10.764(2) ?, β = 99.31(2)°, V = 1154.7(3) ?3, Z = 2, Dc = 1.651 g/cm3, F(000) = 600, λ(MoKα) = 0.71073 ?, μ = 1.134 mm-1, R = 0.0380 and wR = 0.0796 for 2670 observed reflections (I > 2σ(I)). Crystal data for 3: C10H26Cl2CuN6O8, Mr = 492.81, monoclinic, P21/n, a = 8.4860(17), b = 8.6320(17), c = 12.662(3) ?, β = 103.40(3)°, V = 902.2(3) ?3, Z = 2, Dc = 1.814 g/cm3, F(000) = 510, λ(MoKα) = 0.71073 ?, μ = 1.562 mm-1, R = 0.0505 and wR = 0.1061 for 1967 observed reflections (I > 2σ(I)). Complexes 1 and 2 are isostructural with the metal ions situated at the inversion center. Hydrogen bonds be- tween O atoms of pendant and perchlorate anion give rise to a two-dimensional supramolecular layer. The Cu(II) ions of compounds 1 and 3 adopt distorted axially-elongated octahedral coordinate geometry, and the nickel(II) ion in complex 2 is four-coordinated with a square-planar configuration. Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL] (ClO4) 2 (L = 5,12-dimethyl- 1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetrade --Cane) 1 and [NiL] (ClO4) 2 2, have been synthesized and structurally characterized by X-ray diffraction analysis. Also, crystal structure of [CuL1] (ClO4) 2 Crystal data for 1: C14H32Cl2CuN6O10, Mr = 578.90, monoclinic, P21 / n, a = 8.3529 (11), b = 10.8105 (17), 3,6,8,10,13-heaxaazacyclotetradecane (10), V = 1165.2 (3)? 3, Z = 2, Dc = 1.650 g / cm3, F (000) = 602 and λ (MoKα) = 0.71073? , μ = 1.229 mm -1, R = 0.0474 and wR = 0.0895 for 2771 observed reflections (I> 2σ (I)). Crystal data for 2: C14H32Cl2N6NiO10, Mr = 574.07, monoclinic, P21 / c, a = 8.3636 , b = 12.997 (2), c = 10.764 (2) ?, β = 99.31 (2) °, V = 1154.7 (3)? 3, Z = 2 and Dc = 1.651 g / cm3 600, λ (MoKα) = 0.71073 μ, μ = 1.134 mm-1, R = 0.0380 and wR = 0.0796 for 2670 observed re flections (I> 2σ (I)). Crystal data for 3: C10H26Cl2CuN6O8, Mr = 492.81, monoclinic, P21 / n, a = 8.4860 (17), b = 8.6320 (17), c = 12.662 = 103.40 (3) °, V = 902.2 (3) 3 3, Z = 2, Dc = 1.814 g / cm3, F (000) = 510, λ (MoKα) = 0.71073?, Μ = 1.562 mm-1, R = 0.0505 and wR = 0.1061 for 1967 observed reflections (I> 2σ (I)). Complexes 1 and 2 are isostructural with the metal ions situated at the inversion center. Hydrogen bonds be- tween O atoms of pendant and perchlorate anion give rise to The Cu (II) ions of compounds 1 and 3 adopt distorted axially-elongated octahedral coordinate geometry, and the nickel (II) ion in complex 2 is four-coordinated with a square-planar configuration.
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