Cyanocomplexes with one-dimensional structures: preparations, crystal structures and magnetic properties

A total of 21 complexes of CuX (X = Cl, Br, I) with bridging ligand (B = 4,4'-dipyridyl (Bpy), pyrazine (Pyz), quinoxaline (Quin), phenazine (Phz), 1,4-diazabicyclo[2.2.2]octane (DABCO), and hexamethylenetetramine (HMTA)) have been synthesized. The products show two stoichiometries: [CuXB] (type 1) and [(CuX)2B] (type 2). Both types can be obtained for B = Bpy, depending on the conditions of preparation. In these cases, the type 2 stoichiometry is the kinetic product. Type 2 complexes only are found for B = Pyz (X = I), Quin, Phz, DABCO, and HMTA. Type 1 complexes form for Pyz (X = Cl, Br). Thermogravimetic analyses of the complexes reveal the general decomposition trend: 1 --> 2 --> [(CuX)2B(1/2)] --> CuX. The X-ray crystal structure of [CuBr(Pyz)] (type 1) features copper atoms bridged by Br and Pyz, forming 2D sheets of fused rectangular Cu4Br2(Pyz)2 units. The X-ray structure of [(CuI)2(Quin)] (type 2) shows 2D layers composed of [Cu2I2]infinity "stair step" chains which are cross-linked by Quin ligands. A total of 16 complexes of CuXL (L = P(OPh)3) with bridging ligand (B = those above and 1,4-dimethylpiperazine (DMP)) have also been prepared. All of these products, except those of HMTA, are of type 3 formulation, [(CuXL)2B]. The HMTA products have the formula [CuX(HMTA)], type 4. Thermal decomposition of the type 3 and 4 complexes occurs with initial loss of B, L, or both. The X-ray structures of [(CuBrL)2(Bpy)] and [(CuBrL)2(Pyz)] (type 3) reveal 1D chains formed from rhomboidal (LCu)2Br2 units linked by the B ligand. The type 4 structure of [CuBrL(HMTA)] is shown by X-ray to be a simple halide-bridged dimer.

Coordination Polymers of Copper(I) Halides

Hexamethylenetetramine: An old new building block for design of coordination polymers

A series of composite inorganic–organic materials from the copper/cyanide/organoimine system have been isolated and structurally characterized The structural consequences of introducing sterically demanding substituents and of expanding the donor to donor distance in linear dipodal organodiimine ligands has been addressed, exploiting the bridging bidentate ligands pyrazine (pyr), 2-methylpyrazine (mpyr), 2-ethylpyrazine (etpyr), 2,3-dimethylpyrazine (2,3-dmp), 2,5-dimethylpyrazine (2,5-dmp), 2,6-dimethylpyrazine (2,6-dmp), quinoxaline (qox), phenazine (phenz), 4,4′-bipyridine (4,4′-bpy) and trans-4,4′-bipyridylethylene (dpe) Hydrothermal reactions of CuCN and KCN with the appropriate ligand yielded two general subclasses of materials: two-dimensional networks and three-dimensional frameworks The 2-D phases include [Cu3(CN)3(pyr)] (1), [Cu2(CN)2(etpyr)]
(2), [Cu2(CN)2(tmp)] (3), [Cu2(CN)2(qox)] (4), [Cu2(CN)2(phenz)] (5) and [Cu7(CN)7(4,4′-bpy)2] (6) The 3-D materials are represented by [Cu3(CN)3(pyr)2] (7), [Cu2(CN)2(mpyr)] (8), [Cu2(CN)2(2,3-dmp)] (9), [Cu2(CN)2(2,5-dmp)] (10), [Cu2(CN)2(2,6-dmp)] (11), [Cu2(CN)2(4,4′-bpy)](12)
and [Cu2(CN)2(dpe)] (13) The materials characteristically exhibit {Cu(CN)}n chains and/or {Cux(CN)x} rings as structural motifs The detailed connectivity between such substructures is influenced by the identity of the organodiimine ligand and the associated steric demands and spatial extension The syntheses and structural characterization by X-ray diffraction of 1–13 are discussed in relation to the supramolecular chemistry of other copper cyanide solid state materials

Solid state coordination chemistry of the copper(I)–cyano–organodiimine system. Two- and three-dimensional copper cyanide phases incorporating linear dipodal ligands

This review focuses on topological features of three-periodic (framework) p, d, and f metal cyano complexes or cyanometallates, i.e. coordination compounds, where CN– ligands play the main structure-forming role. In addition, molecular, one-periodic (chain), and two-periodic (layer) cyanometallates are considered as possible building blocks of the three-periodic cyanometallates. All cyanometallates are treated as systems of nodes (mononuclear, polynuclear, or transitional metal cluster complexes) joined together via CN-containing spacers. The most typical nodes and spacers as well as methods of their connection are described and systematized. Particular attention is paid to the overall structural motifs in the three-periodic cyanometallates, especially to the relations between the local coordination (coordination figure) of structural units and the entire framework topology. The chemical factors are discussed that influence the cyanometallate topological properties due to modification of nodes, spacers, o...

Topological Motifs in Cyanometallates: From Building Units to Three-Periodic Frameworks

A new synthetic procedure developed recently in our laboratories has made possible the synthesis of variety of new complexes of CuCN with diamines. Synthesis was effected by adding the ligand to a ...

Crystal Structures of a Series of Complexes Produced by Reaction of Copper(I) Cyanide with Diamines.

The syntheses and crystal structures of a family of silver cyanide complexes of thiourea and substituted thioureas are reported. The sulfur ligands include thiourea (tu), 1-methyl-2-thiourea (mtu), 1,3-dimethyl-2-thiourea (dmtu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N‘-ethylenethiourea, etu). Synthesis was effected by dissolving AgCN in an aqueous solution of ligand. Two different complexes were obtained by the reaction of AgCN with tu. Complex 1a:  (AgCN)(tu), monoclinic, P21/c, a = 9.3851 (6) A, b = 8.2782 (5) A, c = 7.1178 (5) A, β = 94.591 (1)°, and Z = 4. Complex 1b:  (AgCN)(tu)2, triclinic, P1, a = 7.9485 (14) A, b = 9.431 (2) A, c = 12.771 (2) A, α = 85.695 (3)°, β = 81.210 (4)°, γ = 77.987 (2)°, and Z = 4. Complex 2:  (AgCN)(mtu), triclinic, P1, a = 4.113 (2) A, b = 9.472 (4) A, c = 9.679 (4) A, α = 113.918 (5)°, β = 98.188 (6)°, γ = 97.725 (6)°, and Z = 2. Complex 3 (AgCN)2(dmtu)2, monoclinic, P21/m, a = 7.1482 (7) A, b = 14.776 (2) A, c = 7.3366 (7) A, β = 92.418...

Crystal Structures of a Family of New Copper(I) Cyanide Complexes of Thiourea and Substituted Thioureas.

The crystal structure of (CuCN) 3 (C 6 H 12 N 4 ) 2 consists of infinite chains of alternating copper(I) and CN which are bound into infinite sheets by hexamethylenetetramine. The CN groups appear to be totally end-for-end disordered. The preparation of the complex is unusual by the fact that none of the final constituent species is present in the starting material; i.e. the copper(I) ion, the cyanide ion, and the hexamethylenetetramine are all created in situ. The crystal is monoclinic, space group C2/c

Crystal structure of a novel copper(I) cyanide complex with hexamethylenetetramine, (CuCn)3(C6H12N4)2

The reaction of both histamine (hista) and cysteine (cys) with aqueous CuCN/S2O32- produced Cu(II) ion. In the histamine case thiocyanate ion was also created leading to the production of Cu(SCN)2(hista)2. With cysteine, the 2-amino-2-thiazoline-4-carboxylic acid (atca) ligand was created leading to the production of Cu(atca)2(H2O). The crystal structures of the two complexes are discussed, and pathways for the production of thiocyanate and the atca ligand are proposed.

Copper(II) Complexes of Histamine and Cysteine Produced by Thiosulfate-Assisted Synthesis Using Copper(I) Cyanide. The in Situ Formation of the Thiocyanate Anion and the 2-Amino-2-thiazoline-4-carboxylic Acid Ligand

Fred B. Stocker

Papers

Crystal Structures of a Series of Complexes Produced by Reaction of Copper(I) Cyanide with Diamines.

Crystal Structures of a Family of New Copper(I) Cyanide Complexes of Thiourea and Substituted Thioureas.

Crystal structure of a novel copper(I) cyanide complex with hexamethylenetetramine, (CuCn)3(C6H12N4)2

Copper(II) Complexes of Histamine and Cysteine Produced by Thiosulfate-Assisted Synthesis Using Copper(I) Cyanide. The in Situ Formation of the Thiocyanate Anion and the 2-Amino-2-thiazoline-4-carboxylic Acid Ligand