Synthesis and structure of catena((μ2-4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione-O,O′)dichloro-zinc)

Abstract

The coordination polymer, catena-((μ₂-4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione-O,O′)dichloro-zinc) {[Zn(C₁₁H₂₀N₄O₂)Cl₂]}_n (I), is prepared for the first time from zinc chloride and bicyclic bis(urea), 4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione, and investigated by X-ray diffraction (CIF file CCDC no. 877812). The crystals of I are monoclinic: space group P2₁, a = 6.2121(17), b = 11.276(3), c = 11.387(3) Å, β = 94.99(3)°, V = 794.6(3) ų, ρ(calcd.) = 1.574 g/cm³, Z = 2. The singe-phase nature of the powder sample of I is confirmed by Rietveld refinement of the powder X-ray diffraction pattern; at 293 K, a = 6.20369(11), b = 11.23336(18), c = 11.36013(16) Å, β = 95.3001(11)°, V = 788.28(2) ų. The content of the major phase I in the sample is 100 ± 1%, no impurity lines are found. The zinc coordination polyhedron in the coordination polymer chain is a tetrahedron with vertices being occupied by two chlorine atoms and carbonyl O(1) and O(2) atoms of two TTSU molecules related by the symmetry code (2 − x, 1/2 + y, 2–z). The zinc bond angles are 101.05(12)°–122.13(9)°. The Zn···Zn distance in the polymer is 9.480(2) Å. The chains in the coordination polymers are additionally combined by intermolecular hydrogen bonds, N(2)–H(2)···O(2)ⁱ (ⁱ 2–x, 1/2 + y, 2 − z) (H···O 2.17 Å, N−H···O 147°) and N(4)–H(4)···Cl(2)ⁱⁱ (ⁱⁱ 1–x, −1/2 + y, 2–z) (H···Cl 2.48 Å, N−H···Cl 159°). The chains are joined into layers along the (0 0 1) plane by intermolecular hydrogen bonds, N(1)−H(1)···Cl(1)ⁱⁱⁱ (ⁱⁱⁱ 1 − x, −1/2 + y, 2–z) (H···Cl 2.78 Å, N−H···Cl 148°).