Article

Copper(II) Halide Complexes with 1-tert-Butyl-1H-1,2,4-triazole and 1-tert-Butyl-1H-tetrazole

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Abstract

1-tert-Butyl-1H-1,2,4-triazole (tbtr) was found to react with copper(II) chloride or bromide to give the complexes [Cu(tbtr)2X2]n and [Cu(tbtr)4X2], where X = Cl, Br. 1-tert-Butyl-1H-tetrazole (tbtt) reacts with copper(II) bromide resulting in the formation of the complex [Cu3(tbtt)6Br6]. The obtained crystalline complexes as well as free ligand tbtr were characterized by elemental analysis, IR spectroscopy, thermal and X-ray analyses. For free ligand tbtr, 1H NMR and 13C NMR spectra were also recorded. In all the complexes, tbtr and tbtt act as monodentate ligands coordinated by CuII cations via the heteroring N4 atoms. The triazole complexes [Cu(tbtr)2Cl2]n and [Cu(tbtr)2Br2]n are isotypic, being 1D coordination polymers, formed at the expense of single halide bridges between neighbouring copper(II) cations. The isotypic complexes [Cu(tbtr)4Cl2] and [Cu(tbtr)4Br2] reveal mononuclear centrosymmetric structure, with octahedral coordination of CuII cations. The tetrazole compound [Cu3(tbtt)6Br6] is a linear trinuclear complex, in which neighbouring copper(II) cations are linked by single bromide bridges.

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The title polymeric compound, [CuCl2(C5H10N4)2]n, is the first structurally characterized complex with a bulky 1-alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N-4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry-related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl2(C5H10N4)2] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.
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The crystallographic problem: The production, and the visibility in the published literature, of thermal ellipsoid plots for small-molecule crystallographic studies remains an important method for assessing the quality of reported results. Since the mid 1960s, the program ORTEP (Johnson, 1965) has been perhaps the most popular computer program for generating thermal ellipsoid drawings for publication. The recently released update of ORTEP-III (Johnson & Burnett, 1996) has some additional features over the earlier versions, but still relies on fixed-format input files. Many users will find this very inconvenient, and will prefer to obtain drawings directly from their crystallographic coordinate files. This new version of ORTEP-3 for Windows provides all the facilities of ORTEP-III, but with a modern Graphical User Interface (GUI). Method of solution: A Microsoft-Windows GUI has been added to ORTEP-III. All the facilities of ORTEP-III are retained, and a number of extra features have been added. The GUI is effectively an editor that writes ORTEP-III input files, but the user need not have any knowledge of the inner workings of ORTEP. The main features of this program are: (i) ORTEP-3 for Windows can directly read many of the common crystallographic ASCII file formats. Currently supported formats are SHELX (Sheldrick, 1993), GX (Mallinson & Muir, 1985), GIF (Hall, Allen & Brown, 1991), SPF (Spek, 1990), CRYSTALS (Watkin, Prout, Carruthers & Betteridge, 1996), CSD-XR and CSD-FDAT. In addition, ORTEP-3 for Windows will accept any legal ORTEP-III instruction file. (ii) Covalent radii for the first 94 elements are stored internally, and may be modified by the user. All bonds are calculated automatically, and any individual bonds may be selected for removal, or for a special representation. (iii) The graphical representations of thermal ellipsoids for any element or selected sets of atoms can be individually set. All the possible graphical representations of thermal ellipsoids in ORTEP-III are also available in ORTEP-3 for Windows. (iv) A mouse labelling routine is provided by the GUI. Any number of selected atoms may be labelled, and any available Windows font may be used for the labels. The font attributes, e.g. italic, bold, colour, point size etc. can also be selected via a standard Windows dialog box. (v) As well as HPGL and PostScript Graphics graphic metafiles, it is also possible to get high quality graphics output by printing directly to an attached printer. The screen display may be saved as BMP or PCX format metafiles, and may also be copied to the clip-board for subsequent use by other Windows programs, e.g. word processing or graphics processing programs. Colour is available for all these output modes. (vi) A simple text editor is provided, so that input files may be modified without leaving the program. (vii) Symmetry expansion of the asymmetric unit to give complete connected fragments may be carried out automatically. (viii) Unit-cell packing diagrams are produced automatically. (ix) A number of options are provided to control the view direction. The molecular view may be rotated or translated by button commands from the tool bar, and views normal to crystallographic planes may also be obtained. Software environment and program specification: The program will read several common crystallographic file formats which hold information on the anisotropic displacement parameters. The operation of the program is carried out via standard self-explanatory MS-Windows menu items and dialog boxes. Hard-copy output is either by HPGL or Encapsulated PostScript metafiles, or by directly printing the graphics screen. Hardware environment: The program is implemented for IBM PC compatible computers running MS-Windows versions 3.1x, Windows 95 or Windows NT. At least a 486-66 machine is recommended with 8 Mbytes of RAM, and at least 5 Mbytes of disk space. Documentation and availability: The executable program, together with full documentation, is available free for academic users from http://www.chem. gla.ac.uk/̃louis/ortep3. Although the program is written in Fortran77, a large number of nonstandard FTN77 calls are used to create the GUI. For this reason, the source code is not available.
Article
In the title compound, [CuCl2(C3H5N7)(2)], the coordination polyhedron of the Cu atom is an elongated square bipyramid with (1) over bar site symmetry. The equatorial positions are occupied by the two Cl atoms with Cu-Cl distances of 2.288 (1) Angstrom and two azidoethyltetrazole ligands with Cu-N distances of 1.999 (2) Angstrom. Two Cl atoms in axial positions are 2.956 (1) Angstrom distant from the Cu atom. The Cl atoms play the role of nonsymmetrical bridges responsible for formation of layers parallel to the bc plane.
Article
Complexes CuL3Cl2, PdL2Cl2 and PtL2Cl2, where L is a novel ligand from the series of 2-substituted 5-aminotetrazoles, namely 5-amino-2-tert-butyltetrazole (1), have been synthesized by the reaction of metal(II) chlorides with 1 and characterized by IR spectroscopy, thermal and X-ray analyses. The crystallographic structural analysis of these complexes revealed that 1 acts as a monodentate ligand coordinated to the metal via endocyclic N4 atom. Platinum complex demonstrates promising cytotoxicity against human cervical carcinoma cells with IC50 value average between those of cisplatin and carboplatin.
Article
The current great interest in preparing functional metal-organic materials is inevitably associated with tremendous research efforts dedicated to the design and synthesis of new families of sophisticated multi-nucleating ligands. In this context, the N-donor triazole and tetrazole rings represent two categories of ligands that are increasingly used, most likely as the result of the recent dramatic development of “click chemistry” and Zeolitic Imidazolate Frameworks (ZIFs). Thus, azole-based complexes have found numerous applications in coordination chemistry.In the present review, we focus on the utilization of 1,2,3-triazole, 1,2,4-triazole and tetrazole ligands to create coordination polymers, metal complexes and spin-crossover compounds, reported to the end of 2009. In the first instance, we present a compendium of all the relevant ligands that have been employed to generate coordination polymers and Metal-Organic Frameworks (MOFs). Due to the huge amount of reported MOFs and coordination polymers bearing these azole rings, three representative examples for each category (therefore nine in total) are described in detail. The second section is devoted to the use of the bridging abilities of these azole ligands to prepare metal complexes (containing at least two metal centers). Given the large number and the great structural diversity of the polynuclear compounds found in the literature, these have been grouped according to their nuclearity. Finally, in the last section, the triazole- and tetrazole-containing coordination compounds exhibiting spin-crossover properties are presented.
Article
In the title compound, [CUCl2(C3H6N4)(2)], the tetrazole ligand is coordinated terminally by the N4 ring atom. The coordination polyhedron of the Cu atom takes the form of an elongated square bipyramid with 1 site symmetry. The equatorial positions are occupied by two Cl atoms [Cu-Cl 2.290(1) Angstrom] and two ethyltetrazole ligands [Cu-N 1.990(4) Angstrom]. In addition, there are two Cl atoms in axial positions [Cu-Cl 2.993(1) Angstrom]. Hence, the Cl atoms play the role of non-symmetrical bridges and connect the molecules into infinite layers located in the yz plane.
Article
The linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH2)][ClO4]2, in the monoclinic space group P21/n, with Z= 4, a= 18.459(3), b= 10.362(2), c= 16.365(3)Å, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to R= 0.047 and R′= 0.075 for 3 343 independent reflections with l > 2σ(l). The compound consists of [Cu(bmdhp)(OH2)]2+ ions and ClO4– counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu–N distances of 1.950(4) and 1.997(4)Å, Cu–O(water) 2.225(4)Å, and Cu–S 2.328(1) and 2.337(1)Å. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH2)]2+ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO4). E.s.r. and ligand-field spectra show that the copper(II) compounds adopt a tetragonal structure in donor solvents.
Article
For the first time, a representative of the 2,5-disubstituted tetrazoles, namely, 2-tert-butyl-5-(2-pyridyl)-2H-tetrazole (), has been found to participate in oxidative dissolution of copper powder in homometalic systems Cu(0)-L-NH(4)X-DMSO (X = Cl, SCN, ClO(4)) and heterobimetallic ones Cu(0)-Mn(OAc)(2)-L-NH(4)OAc-Solv (Solv = DMSO, DMF), providing the formation of molecular homometallic complexes [CuL(2)Cl(2)] (), [CuL(2)(SCN)(2)] (), and [CuL(2)(H(2)O)](ClO(4))(2) (), heterobimetallic complex [Cu(2)MnL(2)(OAc)(6)] () from DMF solution and its mixture with complex [Cu(2)MnL(2)(OAc)(6)]·2DMSO () from DMSO solution. Free ligand and complexes were characterized by elemental analysis, IR spectroscopy, thermal and X-ray single crystal analyses, whereas complex was characterized by X-ray analysis only. Compounds are mononuclear complexes, with chelating coordination mode of L via the tetrazole ring N4 and pyridine ring N7 atoms. Heterobimetallic complexes and possess trinuclear structures, with a linear Cu-Mn-Cu arrangement of the metal atoms, linked by the acetate anions; each copper(ii) atom is decorated by a chelating unit of L via the tetrazole ring N1 and pyridine ring N7 atoms in complex , and via the N4, N7 atoms in complex . Temperature-dependent magnetic susceptibility measurements of complex revealed a weak antiferromagnetic coupling between the paramagnetic copper(ii) and manganese(ii) ions (J = -2.5 cm(-1), g(Cu) = 2.25 and g(Mn) = 2.01), with magnetic exchange through the acetato bridges.
Article
Published data on the synthesis, structure, properties and applications of metal derivatives of tetrazoles are generalised and described systematically. Compounds based on the anionic and neutral tetrazole forms, C- and N-mono- and C,N-disubstituted tetrazoles are considered.
Article
Two new isostructural complexes, dibromobis(1-ethyltetrazole)copper(II) (1) and dibromobis(1-hexyltetrazole)copper(II) (2), have been synthesised. Each bromine atom in the crystal structure of 1 and 2 is bonded to two copper atoms to give rise to a polymeric corrugated network. The polymeric layers are distinctly separated by tetrazole ligands. Both solids exhibit a phase transition to the ferromagnetic state with Curie temperatures of 8.5 K and 8.9 K for 1 and 2, respectively, and a strong anisotropy of the magnetic susceptibility below the ordering temperature. The easy magnetisation axis lies along the monoclinic axis, and the hard magnetisation axis is orthogonal to the polymeric layers. Effective anisotropy fields were estimated as (720–3020 Oe). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Article
It is now over 60 years since the Jahn–Teller theorem was put forward and shown to account for the distorted stereochemistry of copper(II) complexes. Numerous accounts have been written describing the origin of the distortion. However, recent work, involving the emerging field in structural chemistry of comparative X-ray crystallography, has shown that the vibronic coupling mechanism can now be applied to low symmetry systems, suggesting that the original static stereochemistries are all connected and continuously variable. This review of copper(II) stereochemistry involving structural pathways is presented here in an attempt to describe and rationalise these variable stereochemistries. Some recent perspectives and new interpretations linking the Jahn–Teller effect (JTE), vibronic coupling, structure correlation analysis, structural pathways and comparative X-ray crystallography are reported.
Article
1,2,4-Triazole and its derivatives have gained great attention as ligands to transition metals by the fact that they unite the coordination geometry of both pyrazoles and imidazoles, and in addition exhibit a strong and typical property of acting as bridging ligands between two metal centres. In this bridging capacity, the 1,2,4-triazole ligands show a great coordination diversity, especially when the triazole nucleus is substituted with additional donor groups. This property together with their strong σ donor properties and the relative ease of synthesis make them very appealing for the design of new polynuclear metal complexes with interesting properties. A number of X-ray structures have been evaluated in some detail in the present paper.
Article
The title polymeric compound, [CuCl(2)(C(5)H(10)N(4))(2)](n), is the first structurally characterized complex with a bulky 1-alkyltetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu-Cl distances of 2.2920 (8) and 2.2796 (9) A, and by the two N-4 atoms of the tetrazole ligands, with Cu-N distances of 2.023 (2) and 2.039 (2) A. Two symmetry-related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) A from the Cu atom. The [CuCl(2)(C(5)H(10)N(4))(2)] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.
Article
Tetrazole compounds have been studied for more than one hundred years and applied in various areas. Several years ago Sharpless and his co-workers reported an environmentally friendly process for the preparation of 5-substituted 1H-tetrazoles in water with zinc salt as catalysts. To reveal the exact role of the zinc salt in this reaction, a series of hydrothermal reactions aimed at trapping and characterizing the solid intermediates were investigated. This study allowed us to obtain a myriad interesting metal-organic coordination polymers that not only partially showed the role of the metal species in the synthesis of tetrazole compounds but also provided a class of complexes displaying interesting chemical and physical properties such as second harmonic generation (SHG), fluorescence, ferroelectric and dielectric behaviors. In this tutorial review, we will mainly focus on tetrazole coordination compounds synthesized by in situ hydrothermal methods. First, we will discuss the synthesis and crystal structures of these compounds. Their various properties will be mentioned and we will show the applications of tetrazole coordination compounds in organic synthesis. Finally, we will outline some expectations in this area of chemistry. The direct coordination chemistry of tetrazoles to metal ions and in situ synthesis of tetrazole through cycloaddition between organotin azide and organic cyano group will be not discussed in this review.
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