Structures and trends of one-dimensional halide-bridged polymers of five-coordinate cadmium(II) and mercury(II) with benzopyridine and -pyrazine-type N-donor ligands

Cadmium and mercury dihalides were reacted with benzopyridine- and benzopyrazine-type N-donor ligands as Lewis bases. The solid-state structures of 13 novel reaction products were studied by X-ray diffraction. Eleven of the structures can be classified as one-dimensional halide-bridged polymers of composition [MIJμ-X)2IJL)]∞, in which the metal ion displays a coordination number of five, while the remaining two structures exhibit one-dimensional dimers that are linked by long, semi-coordinate M– X⋯M–X interactions to form pseudo-halide-bridged polymers. Four of the structures contain Cd2+ as the metal ion, while the remaining nine have Hg2+ as the metal ion. Although all the halide-bridged polymers show a coordination number of five, two different metal cation geometries are displayed. A detailed comparison of all structural results, which includes related compounds from the literature and allows for the study of the effect of an increase in the width of the N-donor ligand on the halide-bridged chain geometries and other structural features, concludes the discussion.CS gratefully acknowledges the National Research Foundation for financial support through an Innovation Scholarship (SFH20100706000011827). MR acknowledges financial support from the University of Pretoria and the National Research Foundation (Grant No. 87659).http://www.rsc.org/crystengcomm2016-10-19am201

Structures and trends of neutral MXxsolvent4−x tetrahedra and anionic [MX4]2− tetrahalometallates of zinc(II), cadmium(II) and mercury(II) with benzopyridine- and benzopyrazine-type N-donor ligands or cations

Zinc, cadmium and mercury dihalides were reacted with benzopyridine- and benzopyrazinetype N-donor molecules acridine (acr), phenazine (phe), quinoline (quin) and quinoxaline (quinox) as ligands or cations. The solid-state structures of 16 novel, zero-dimensional reaction products were studied by X-ray diffraction. Seven of the compounds were prepared in the presence of an inorganic acid, HX, which resulted in the formation of anionic tetrahalometallates, [MX4]2−, with either Cd2+ or Hg2+ as the cationic metal center and quinolinium (quin-H), quinoxalinium (quinox-H), acridinium (acr-H) or phenazinium (phe- H) as the counter cation. The other nine compounds contain Zn2+ as the tetrahedral cationic node. Five of the nine Zn2+ compounds are neutral, and four are ionic. Three of the four ionic Zn2+ compounds contain an anionic tetrahalometallate inorganic moiety, [ZnX4]2−, while the inorganic component of the fourth ionic Zn2+ compound is coordinated by three halido ligands and one aqua ligand, [ZnX3(H2O)]−. Structural trends, hydrogen bonding interactions and aromatic interactions are identified. In addition, it is observed that in the case of the neutral phenazine or acridine compounds, the size of the organic molecule prevents coordination of the molecule to the metal ion.National Research Foundation financial support through an Innovation Scholarship (SFH20100706000011827). University of Pretoria and the National Research Foundation (Grant No. 87659).http://www.rsc.org/journals-books-databases/about-journals/crystengcomm2017-04-30hb2016Chemistr

Bis(4-amino­benzoic acid-κN)dichloridozinc(II)

Mol­ecules of the title compound [ZnCl2(C7H7NO2)2], are located on a twofold rotation axis. Two 4-amino­benzoic acid moieties, and two chloride ligands are coordinated to a Zn atom in a tetra­hedral fashion, forming an isolated mol­ecule. Neighbouring mol­ecules are linked through hydrogen-bonded carboxyl groups, as well as N—H⋯Cl hydrogen-bonding inter­actions between amine groups and the chloride ligands of neighbouring mol­ecules, forming a three-dimensional network

3-Methyl­anilinium nitrate

In the title compound, C7H10N+·NO3 −, the 3-methyl­anilinium cations inter­act with the nitrate anions through strong bifurcated N+—H⋯(O,O) hydrogen bonds, forming a two-dimensional hydrogen-bonded network

Bis(2-methyl-4-nitro­anilinium) tetra­chloridomercurate(II)

The title compound, (C7H9N2O2)2[HgCl4], self-assembles into cationic organic bilayers containing the 2-methyl-4-nitro­anilinium cations, sandwiched between anionic inorganic layers built up by the distorted tetra­hedral [HgCl4]2− groups. The organic sheets are inter­linked through weak C—H⋯O hydrogen bonds, while they inter­act with the anionic part via strong charge-assisted N+—H⋯Cl—Hg hydrogen bonds. The [HgCl4]2− anions are bis­ected by a mirror plane passing through the metal and two of the chloride ions

Satellite ligand effects on magnetic exchange in dimers. A structural, magnetic and theoretical investigation of Cu2L2X4 (L = methylisothiazolinone and X = Cl−, Br−)

Halide-bridged polymers have gained significant interest due to their diverse properties and potential applications. Stacked Cu2L2X4 dimers, where L is an organic ligand and X can be Cl− or Br−, are of interest because a chloride analogue where L = 2-pyridone, had previously been reported to exhibit bulk ferromagnetism, which augured great potentiality for this class of compounds. The synthesis, structural characterization, magnetic susceptibility measurements, and computational studies of two isostructural CuClMI (MI = methylisothiazolinone) and CuBrMI polymers of Cu(ii), along with a related CuClPYR (PYR = 2-pyridone) is reported. CuClMI and CuBrMI were found to exhibit AFM bulk properties, due to FM/AFM alternating chains along the halide-bridged polymer axis, while FM bulk properties were confirmed for CuClPYR exhibiting a FM spin ladder. In combination with a benzamide analogue, CuClBA, three O-donor amides, CuClMI, CuClBA and CuClPYR were analyzed and revealed that the kinetic exchange is affected by the identity, but more importantly, the orientation of the satellite ligands. The torsional angle of the ligand with the dimer plane is shown to significantly affect the magnetic exchange in the dimer, and between dimers, explaining the reported FM bulk properties of CuClPYR. This finding is exceedingly important, as it suggests that a spin device can be constructed to flip between singlet/triplet states by manipulating the orientation of the satellite/terminal ligand. © 2023 The Royal Society of Chemistry. This article includes supplementary data, also available for download

Robust motifs in 2-phenylethylammonium and related tetrahalometallates

The novel crystal structures of seven compounds which combine 2-phenylethylammonium cations and perhalometallate anions, all with the general formula (C8H9NH3 +)2 MX4 2 , were determined to establish the effect of metal atom and halogen ligand substitution on the structures and hydrogen bonding interactions. Five of the structures, bis(2-phenylethylammonium) tetrachlorozincate, (C8H9NH3 +)2 ZnCl4 2 , bis(2-phenylethylammonium) tetraiodozincate, (C8H9NH3 +)2 ZnI4 2 , bis(2- phenylethylammonium) tetrabromodichloroiodozincate, (C8H9NH3 +)2 ZnCl2BrI2 , bis(2- phenylethylammonium) tetrabromocadmate, (C8H9NH3 +)2 CdBr4 2 , and bis(2- phenylethylammonium) tetrabromomercurate, (C8H9NH3 +)2 HgBr4 2 , were found to be isostructural, while two of the compounds containing iodo ligands, bis(2-phenylethylammonium) tetraiodocadmate, (C8H9NH3 +)2 CdI4 2 , and bis(2-phenylethylammonium) tetraiodomercurate, (C8H9NH3 +)2 HgI4 2 , crystallize in a different, but related disordered structure. Strong N+–H/X –M hydrogen bonding interactions, as well as weaker C–H/p aromatic interactions occur in all seven structures, and two robust tetrameric hydrogen bonded zero-dimensional motifs are present in all seven structures. C–H/ Cl–M hydrogen bonding interactions are present in the structure of bis(2-phenylethylammonium) tetrachlorozincate, and result in the distortion of the geometry of the 2-phenylethylammonium cation. Comparison of the identified zero-dimensional hydrogen bonding motifs with those occurring in related structures reported in the literature shows that the motifs are robust and can tolerate changes in cation, metal and ligand to a large extent.www.rsc.org/crystengcom

2-Chloro-3-fluoropyridine copper(II) complexes and the effect of structural changes on magnetic behavior

Please read abstract in the article.http://www.tandfonline.com/loi/gcoo202019-10-17hj2019Chemistr

The magnetic-structural relationship of [CuX6]4- [X = Cl-or Br-] perovskites containing ncarboxyalkylammonium cations of various chain lengths

Please read abstract in the article.https://onlinelibrary.wiley.com/journal/s20532733am2022Chemistr

Cobalt and zinc halide complexes of 4-chloro and 4-methylaniline : syntheses, structures and magnetic behavior

Please read abstract in the article.The Carlson School of Chemistry and Biochemistry, Clark University and the Department of Chemistry, Brandeis University. F. X. would like to acknowledge the funding from the European Union's Horizon 2020 research and innovation program under the Marie Skodowska-Curie grant agreement No 701647.http://www.elsevier.com/locate/poly2020-08-01hj2019Chemistr