A two-dimensional copper(I) polymer containing both molecular rod and anionic bridges: synthesis and crystal structure of (µ-chloro)-(µ-pyrazine)copper(I)

Moreno, José María; Suárez‐Varela, José; Colacio, Enrique; Avila-Rosón, J. C.; Hidalgo, M. A.; Martín-Ramos, Daniel

doi:10.1139/v95-197

Cited by 47 publications

(34 citation statements)

References 26 publications

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“…Thermogravimetric mass loss profiles of selected type 2 complexes. -1,3-SCN, µ-1,3-N 3 , µ-1,1-OCN) 18,22,24 and for [CuBr-(cnge)]. 17 Presumably, it is the size differential in B that is responsible for the formation of type 1b structures for Pyz and type 1a for Bpy.…”

Section: Discussionmentioning

confidence: 99%

Coordination Polymers of Copper(I) Halides

Graham¹,

Pike²,

et al. 2000

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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.

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Section: Discussionmentioning

confidence: 99%

Coordination Polymers of Copper(I) Halides

Graham¹,

Pike²,

et al. 2000

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“…The ligand-rich 1:2 coordination polymers with pyrazine have an identical topology of the coordination network to the present pyrimidine compounds. CuX single chains (X ϭ Cl, [39] Br [15] ) are observed as the CuX substructure, and these are connected into layers by the pyrazine ligands. If the N-donor atoms are located in the 1-and 2-positions, like in pyridazine, the topology of the coordination network in the 1:1 compounds is completely different.…”

Section: Crystal Structuresmentioning

confidence: 99%

Synthesis, Crystal Structure and Thermal Reactivity of New Copper(I) Halide Pyrimidine‐Containing Coordination Polymers

Näther

Jeß

2004

Eur J Inorg Chem

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Reaction of copper(I) chloride with pyrimidine in acetonitrile leads to the formation of the ligand‐rich 1:1 compound poly[CuCl(μ2‐pyrimidine‐N,N′)] (1). “Zig‐zag”‐like CuCl chains are found in the crystal structure that are connected by the pyrimidine ligands to form layers. This compound loses half of its ligands upon heating and transforms into the new l2:1 coordination polymer poly[(CuCl)2(μ2‐pyrimidine‐N,N′)] (2). In this structure, ladder‐like CuCl double chains occur which are connected by the pyrimidine ligands to form layers. If copper(I) iodide is used in the synthesis, the new 1:1 coordination polymer poly[CuI(μ2‐pyrimidine‐N,N′)] (3) forms. In contrast to compound 1, CuI single chains and (CuI)2 dimers are found as the CuX substructure, and these are connected by the ligands to form sheets. On heating this compound a similar behaviour as for compound 1 is observed, and a transformation into the new 2:1 compound poly[(CuI)2(μ2‐pyrimidine‐N,N′)] (4) occurs. This compound is not isotypic to 2 even though the topology of the coordination network is identical (CuI double chains are connected into layers by the pyrimidine ligands). The thermal behaviour of the known compounds poly[CuBr(μ2‐pyrimidine‐N,N′)] (5) and poly[(CuBr)2(μ2‐pyrimidine‐N,N′)] (6) was also investigated. A transformation of the ligand‐rich 1:1 compound 5 into the 2:1 compound 6 is also observed in the thermal decomposition reaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…We ourselves have shown that copper(I) halides can also be employed to gether with flexible alkylcycloarsoxanes (RAsO)4 (R = Me, Et) to construct neutral or anionic porous lamellar and three-dimensional coordination poly mers capable of hosting alkali cations or polar guest molecules [ 1 0 -1 2 ], Although a number of copper(I) halide based neutral coordination polymers with linear bidentate bridging N-donor ligands have recently been re ported, their structural motifs are restricted to chains or layers [8 , 13 -16]. For instance the pyrazine ligands in ^ [CuCl(jU-pyz)] link single ^ [CuCl] strings into sheets [14], whereas in ^ [(CuCl^O^-pyz)] they adopt a similar function for ^ [(CuCl)2] staircase double chains [16]. In contrast, the solid state structure of ^[CuC1(/j-4, 4'-bpy)] consists of interwoven honeycomb-like sheets, in which (CuCl) 2 rhomboid dimers are joined by 4, 4'-bipyridine bridges [15], As framework integrity of such coordination polymers at higher temperatures or during guest molecule exchange could play an important role in any envisaged practical appli cation, we considered it to be of interest to de vise general approaches towards the construction of three-dimensional copper(I) halide based coor dination polymers with bridging N-donor ligands.…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional Copper(I) Halide Based Coordination Networks with Asymmetrically Substituted Bridging N-Donor Ligands

Roßenbeck

Sheldrick

1999

Zeitschrift Für Naturforschung B

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The discrete complex [(Cul)2 (pyzCN)4] (1) and the coordination polymers ^ [CuI(pyzCN)] (2) and 3 [(CuX)3 (pyzCN)2] (3, 4; X = Br, Cl) may be prepared from the respective copper(I) halide CuX and 2-cyanopyrazine (pyzCN) by self-assembly in acetonitrile solution at 100-120°C. Whereas 2 exhibits 1 [Cul] staircase double chains as its characteristic substructure, the three-dimensional netwo'rks of 3 and 4 contain single zigzag CuX strings. The influence of the copper(I) halide on both the connectivity pattern and the dimensionality of a resulting coordination network is particularly apparent for the 1:1 complexes ^ [CuI(pymMe)] (5), 3 [(CuBr)3(pymMe)_3] (6) and ^ [CuCl(pymMe)] (7), which were generated by reaction of öaX with 4-methylpyrimidine (pymMe) under reaction conditions similar to those above.

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A two-dimensional copper(I) polymer containing both molecular rod and anionic bridges: synthesis and crystal structure of (µ-chloro)-(µ-pyrazine)copper(I)

Cited by 47 publications

References 26 publications

Coordination Polymers of Copper(I) Halides

Coordination Polymers of Copper(I) Halides

Synthesis, Crystal Structure and Thermal Reactivity of New Copper(I) Halide Pyrimidine‐Containing Coordination Polymers

Three-dimensional Copper(I) Halide Based Coordination Networks with Asymmetrically Substituted Bridging N-Donor Ligands

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