0000000000225867
AUTHOR
Roger D. Willett
Exchange Coupling Mediated by N–H···Cl Hydrogen Bonds: Experimental and Theoretical Study of the Frustrated Magnetic System in Bis(o-phenylenediamine)nickel(II) Chloride
The title compound crystallizes in the monoclinic P2(1)/c space group with a = 11.2470(3) A, b = 5.9034(2) A, c = 12.0886(3) A, β = 115.143(1)°, and V = 726.58(4) A(3) and consists of discrete monomeric NiCl(2)(o-phenylendiamine)(2) molecules. Each o-phen ligand coordinates in a bidentate mode with the chloride ions occupying trans positions in the resulting tetragonally distorted octahedral coordination sphere. Two discrete sets of N-H···Cl hydrogen bonds link the octahedral molecules into a two-dimensional network, with type 1 interactions linking adjacent monomers along the c axis and type 2 interactions linking monomers along the diagonals in the bc plane. Analysis of the magnetic data …
(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system
Abstract The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2-dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt)2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order–disorder type involving one arm of the NBu 4 + cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) A and β = 115.642(3)° with V = 6020.8(11) A3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) A and β = 115.073(2)° and V = 5652.1(9) A3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction.…
Structure and magnetic properties of [(REDA)Cl]2CuCl4 salts: A new series of ferromagnetic layer perovskites
Abstract The preparation, structure and magnetic properties of two mono- N -substituted ethylenediammonium copper chloride salts are reported. Both [(MEDA)Cl] 2 CuCl 4 and [(EEDA)Cl] 2 CuCl 4 assume monoclinic layered perovskite A 2 CuCl 4 type structures (here MEDA 2+ is the N -methylethylenediammonium dication and EEDA 2+ is the N -ethylethylenediammonium dication). In these structures, planar CuCl 4 2 - ions are linked together into layers of corner-sharing distorted octahedra via semi-coordinate Cu⋯Cl bonds. The magnetic studies reveal the presence of dominant ferromagnetic coupling in both compounds and analysis of the higher temperature data yielded J / k = 19.29(1) K and 19.0(4) K f…
Structure and Magnetic Properties of the Ferromagnetic Cu3Cl126- Trimer in [(NH3C2H4)3NH]2Cu3Cl14
The crystal structure consists of a strongly hydrogen bonded network of tris(N-ethylammonium)ammonium cations, Cu3Cl12(6)- trimeric species, and Cl- anions. The Cu3Cl12(6)- trimers are formed by two distorted tetrahedral CuCl4(2)- anions linked to a central square planar CuCl4(2)- anion via semicoordinate Cu-Cl...Cu mu1 bridges. The central copper ion shows only small deviations from ideal D4h symmetry, while the terminal copper ions show a mild distortion from D2d symmetry with an average trans Cl-Cu-Cl angle of 136.0 degrees. The semicoordinate linkages provide a ferromagnetic exchange pathway between the copper ions with J/k = 6.91(3) K. Short Cl...Cl contacts (3.67-3.90 angstoms) lead t…
Crystal structure and magnetic properties of Cu(TIM)CuBr4: An alternating site-alternating exchange chain system
Abstract The title compound, Cu(TIM)CuBr4 (where TIM is a macrocycle ligand) is a member of the Cu(TIM)MX4 family, which contains linear chain structures with ⋯ Cu ⋯ X – M – X ⋯ Cu ⋯ X – M - ⋯ linkages. This chain structure defines an alternating exchange/alternating site 1d system. For M=Cu, alternating FM/AFM chains are formed with JFM>| JAFM|. Structural and magnetic data are presented, along with an analysis of the exchange pathways.
Synthesis, Structure, and Magnetic Properties of [(S)-[PhCH(CH3)N(CH3)3]][Mn(CH3CN)2/3Cr(ox)3]·(CH3CN)_(solvate), a 2D Chiral Magnet Containing a Quaternary Ammonium Chiral Cation
The synthesis, structure, and magnetic properties of a novel oxalate-based bimetallic magnet obtained by using the chiral (S)-trimethyl-(1-phenyl-ethyl)-ammonium, ((S)-[PhCH(CH3)N(CH3)3](+)), cation as template is reported. This compound can be formulated as [(S)-[PhCH(CH3)N(CH3)3]][Mn(CH3CN)2/3Cr(ox)3] x (CH3CN)_(solvate), and it crystallizes in the chiral trigonal space group P3. It shows a distorted two-dimensional honeycomb structure formed by Mn(II) and Cr(III) ions connected through oxalate anions with [(S)-[PhCH(CH3)N(CH3)3](+) cations and solvent molecules intercalated between the oxalate layers. Two-thirds of the Mn(II) ions of the honeycomb anionic network are heptacoordinated. Th…
Structure and Magnetic Properties of the Ferromagnetic Cu3Cl126- Trimer in [(NH3C2H4)3NH]2Cu3Cl14
The crystal structure consists of a strongly hydrogen bonded network of tris(N-ethylammonium)ammonium cations, Cu3Cl12(6)- trimeric species, and Cl- anions. The Cu3Cl12(6)- trimers are formed by two distorted tetrahedral CuCl4(2)- anions linked to a central square planar CuCl4(2)- anion via semicoordinate Cu-Cl...Cu mu1 bridges. The central copper ion shows only small deviations from ideal D4h symmetry, while the terminal copper ions show a mild distortion from D2d symmetry with an average trans Cl-Cu-Cl angle of 136.0 degrees. The semicoordinate linkages provide a ferromagnetic exchange pathway between the copper ions with J/k = 6.91(3) K. Short Cl...Cl contacts (3.67-3.90 angstoms) lead t…
Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate( II ): (Hpy) 2 [Cu 3 Cl 8 (H 2 O) 2 ]
A one-dimensional polymeric pyridinium chlorocuprate (HPy)2[Cu3Cl8(H2O)2], an intermediate between (HPy)CuCl3 and CuCl2·2H2O, has been synthesized and characterized by X-ray analysis [monoclinic, P21/c, a = 7.8950(10), b = 14.144(2), c = 9.921(10) A, β = 99.20(2)°]. The structure contains [Cu3Cl8(H2O)2]n2n− chains in which both square-pyramidal and octahedral CuII exist. The chains are composed of linked [Cu2Cl6]2− dimers and CuCl2(H2O)2 monomeric units. On being heated in the solid state the compound undergoes dehydration followed by dehydrohalogenation to produce a pyridine complex of CuII: [Cu3Py2Cl6]. Other compounds, (HPy)2[CuCl4], CuPyCl2 and CuPy2Cl2, also produce [Cu3Py2Cl6] as an i…
Long‐Range Order in Layered Perovskite Salts – Structure and Magnetic Properties of [(CH 3 ) 2 CHCH 2 NH 3 ] 2 CuX 4 (X = Cl, Br)
The synthesis, structure, and magnetic properties of two new layered perovskite-type copper halide salts are reported. Dominant ferromagnetic coupling is observed with J/k = 14.58(1) and 21.5(4) K for the Cl and Br salts, respectively. For [(iBA)2CuCl4] (1); (iBA = isobutylammonium): P21/c with a = 13.9481(8) A, b = 7.5061(4) A, c = 7.5133(4) A and β = 102.520(1)° with Z = 4. In this structure, planar CuCl42– ions are linked together into layers of corner-sharing distorted octahedra. Ferromagnetic ordering occurs at Tc = 6.5 K for 1 with spin canting. Hysteresis loops show a coercive field of 2 mT with rapid saturation at 2 K that persists up to T = 9 K. The bromide salt is not isomorphous …