Cadmium cyanide–ether clathrates: crystal structures of Cd₈(CN)₁₆(H₂O)₆·6G (G = Et₂O or Prⁱ₂O) and Cd₃(CN)₆(H₂O)₂·2Prⁿ₂O

Abstract

The cadmium cyanide host clathrates Cd8(CN),,(H,O),.6G (G = Et,O l a or Pri,O l b ) and Cd,( CN),( H,0),~2Prn,0 2 have been prepared and their structures determined by X-ray crystallography: l a , cubic, space group P43n. a = 15.661 (5) A, Z = 2, R = 0.045 for 565 reflections; 1 b, cubic, space group P43n. a = 15.762(9) A, Z = 2, R = 0.035 for 653; 2, monoclinic, space group C2/c, a = 14.044(6). b = 18.034(6), c = 12.931 (4) A, p = 11 1.47(2)", Z = 4, R = 0.040 for 2003. The novel hosts in l a and 1 b contain tetrahedral and octahedral Cd atoms in a 5:3 ratio. The host in 2 is isostructural to that of the previously reported Cd,( CN),( H,0),*2PriOH 3, containing tetrahedral and octahedral cadmium atoms in a ratio of 2: 1. The guest ether molecules are accommodated in cage-like cavities, and participate in hydrogen bonding between their 0 atoms and those of the co-ordinated water molecules.

Synthesis and Crystal Structures of Cadmium(II) Cyanide with Branched-Butoxyethanol

“…This suggests that the Cd(CN) 2 framework and coordination environment of Cd(II) are strongly affected by not only the number of carbons of the alkyl group of the Rcel molecule but also by the shape of the alkyl group of the Rcel molecule. Because of the differences in their alkyl groups, the Cd(CN) 2 frameworks of cadmium(II) cyanide coordination polymers with alkoxyethanol [22] change more dramatically than the frameworks of complexes with either dialkyl-ether [16,17] or with alkyl-alcohol [8,13,14,18,19]. The effect of the alkyl group of alkoxyethanol compounds was found to be stronger than the effect of either alkyl-alcohol or dialkyl-ether compounds.…”

“…For Cd(CN) 2 clathrates containing a lipophilic guest, the coordination geometries of Cd(II) were Cd T and the Cd(CN) 2 frameworks were cristobalite-like or tridymite-like structures [4][5][6][7][8][9][10][11]21]. In contrast, the Cd(CN) 2 clathrates with the water molecule(s) coordinating to Cd(II) ion contain alcohol or short dialkyl-ether (alkyl group with a carbon number less than 3) as a guest, and the host frameworks function as zeolite-mimetic structures [8,[13][14][15][16][17][18][19]. Incidentally, for Cd(CN) 2 , there was no guest molecule found to facilitate a doubly interpenetrated diamond-like framework.…”

“…The coordination geometry of Cd(II) in Cd(CN) 2 is normally a tetrahedral four-coordination geometry (denoted as Cd T ). However depending on the influence of other ligands (for example, H 2 O [8, [13][14][15][16][17][18][19]), the geometry might also be trigonal-bipyramidal five-coordination geometry (Cd TB ), or octahedral six-coordination geometry (Cd OC ). For Cd(CN) 2 clathrates containing a lipophilic guest, the coordination geometries of Cd(II) were Cd T and the Cd(CN) 2 frameworks were cristobalite-like or tridymite-like structures [4][5][6][7][8][9][10][11]21].…”

“…Cadmium(II) cyanide is a 3D porous coordination polymer clathrating various guest molecules (for example, CCl 4 [4][5][6], C 6 H 6 [9] CH 2 ClCHCl 2 [10], and Bu 2 O [10]) by van der Waals force in its cavity space. Interestingly, the Cd(CN) 2 host structures change according to the guest [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20], and the hosts form a mineralomimetic framework. The coordination geometry of Cd(II) in Cd(CN) 2 is normally a tetrahedral four-coordination geometry (denoted as Cd T ).…”

Three-Dimensional Cadmium(II) Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

“…Cadmium(II) cyanide of formula Cd(CN) 2 and the related compounds have interesting, unique chemical properties [1][2][3][4][5][6][7][8][9][10][11]. Cadmium(II) cyanide is a three-dimensional porous coordination polymer, and is the clathration of various guest molecules (ex.…”