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Variations in Catenation Behavior in Aromatic Guest Clathrates Containing Rigid Host Entities p-Xylylenediamine (p-xda) and Tetracyanonickelate(II) Linking Octahedral Cadmium(II) in [Cd(p-xda)nNi(CN)4] Host (n = 1, 1.5, or 2) and the Related Complex [Cd(C6H5NH2)2(p-xda)Ni(CN)4]

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journal contribution
posted on 27.03.1996, 00:00 by Hidetaka Yuge, Yohsuke Noda, Toschitake Iwamoto
A number of catena-μ-linkage modes have been observed for the p-xylylenediamine (p-xda) and Ni(CN)4 linking octahedral Cd atoms in the X-ray single crystal structures of five inclusion compounds with aromatic guests and a three-dimensional (3D) complex salt:  [Cd(p-xda)Ni(CN)4o-CH3C6H4NH2 (1), [Cd(p-xda)2Ni(CN)4m-CH3C6H4NH2 (2), [Cd(p-xda)2Ni(CN)4]·C6H5OH·H2O (3a), [Cd(p-xda)2Ni(CN)4]·C9H7N (3b), [Cd2(p-xda)3{Ni(CN)4}2]·2C4H5N (4), and [Cd(C6H5NH2)2(p-xda)Ni(CN)4] (5). Clathrate 1 crystallizes in the triclinic system, space group P1̄, with a = 6.960(2) Å, b = 7.718(2) Å, c = 9.693(2) Å, α = 90.61(2)°, β = 91.72(2)°, γ = 90.17(2)°, Z = 1, and R = 0.0298 for 2751 reflections; clathrate 2 crystallizes in the triclinic system, P1̄, with a = 8.149(2) Å, b = 9.577(1) Å, c = 9.865(2) Å, α = 81.03(1)°, β = 94.08(2)°, γ = 106.08(1)°, Z = 1, and R = 0.0490 for 3285 reflections; clathrate 3a crystallizes in the monoclinic system, P21/m, with a = 8.615(3) Å, b = 17.568(2) Å, c = 9.950(2) Å, β = 105.30(2)°, Z = 2, and R = 0.0519 for 2792 reflections; clathrate 3b crystallizes in the monoclinic system, P21/m, with a = 8.505(1) Å, b = 17.737(1) Å, c = 10.106(1) Å, β = 102.64(1)°, Z = 2, and R = 0.0422 for 3480 reflections; clathrate 4 crystallize in the monoclinic system, C2/c, with a = 19.820(2) Å, b = 7.738(2) Å, c = 31.213(1) Å, β = 109.138(5), Z = 4, and R = 0.0480 for 4092 reflections; complex 5 crystallize in the monoclinic system, C2/c, with a = 22.240(1) Å, b = 9.254(1) Å, c = 16.241(1) Å, β = 130.668(3)°, Z = 4, and R = 0.0389 for 2810 reflections. The puckered two-dimensional (2D) network of [CdNi(CN)4] in 1 is successively spanned by p-xda at every Cd atom to form a 3D host for the o-toluidine. The 2D network in 2 is broken at a couple of CN groups in trans positions of each Ni(CN)4; instead, the bridge of p-xda is doubled to span the Cd atoms in the host accommodating m-toluidine. The breaking is at cis positions in the hosts of 3a and 3b, enclathrating hydrated phenol and quinoline, respectively. The complicated 3D host structure of pyrrole clathrate 4 is constructed of three single spans of p-xda from one Cd to three other Cd atoms, the respective Cd atoms being interconnected by cis-[−NC−Ni(CN)2−CN−] and four-handed Ni(CN)4 moieties. The bis(aniline)-ligated Cd complex 5 has a 3D structure built from the −[Cd−p-xda−] and −[(cis-)NC−Ni(CN)2−CN−Cd−] catenations. These structural variations are interpreted in terms of rigidity of p-xda and Ni(CN)4 skeletons, partial flexibility of the −CH2NH2 substituents in p-xda, flexible utilization of N-ends of Ni(CN)4 in the catenation, hydrogen bond interactions among the host entities, and host−guest interactions through hydrogen bonds; no strong π−π interactions were observed between the guest and the π-rich host entities.

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