Structural and magnetic properties of bis(ethanolammonium)hexahalodicuprate(II) salts: Copper(II) halide dimers with a square-pyramidal type distortion

Scott, Brian L.; Willett, Roger D.

doi:10.1016/s0020-1693(00)83909-2

Cited by 22 publications

(8 citation statements)

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“…A number of penta-coordinate chloride bibridged copper chains exhibit ferromagnetic behavior. This family of compounds includes catena -(piperazinediium hexachlorodicuprate), polymorphs of catena -(bis(dimethylammonium)hexachlorodicuprate), catena -((cyclopentylammonium)trichlorocuprate), catena -((ethanolammonium)hexachlorodicuprate), catena -((isopropyl- ammonium)hexachlorodicuprate), catena -(bis(2-amino-4-chloro-6-methylpyrimidinium)-hexachlorodicuprate), catena -(tetramethylethylenediium)hexachlorodicuprate, and catena -(bis(pyrrolidinium) hexachlorodicuprate . The strength and sign of the NN magnetic exchange in these compounds has been tied to two structural parameters: the Cu–Cl–Cu bridging angle (φ) and the bifold angle (σ) at each Cu-center …”

Section: Discussionmentioning

confidence: 99%

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Herringer¹,

Landee²,

Turnbull³

et al. 2017

Inorg. Chem.

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The synthesis, structure, magnetic properties, and theoretical analysis of a new phase of dichloro(2-chloro-3-methylpyridine)copper(II) (2) and its isomorphous analogue dichloro(2-bromo-3-methylpyridine)copper(II) (3) are reported. Both complexes crystallize in the orthorhombic space group Pbca and present square pyramidal Cu(II) ions bridged into chains by chloride ions with each copper(II) bearing a single pyridine ligand. Variable temperature magnetic susceptibility measurements were well fit by a uniform one-dimensional ferromagnetic chain model with 2, J = 69.0(7) K, C = 0.487 emu-K/mol-Oe; 3, J = 73.9(4) K, C = 0.463 emu-K/mol-Oe (H = -JΣS·S Hamiltonian). The experimental J-values were confirmed via theoretical calculations. Comparison to a known disordered polymorph of dichloro(2-chloro-3-methylpyridine)copper(II), 1, shows marked differences as there are significant antiferromagnetic next-nearest neighbor interactions in 1 in addition to randomness induced by the disorder which provide a distinctly different magnetic response. The differences in magnetic behavior are attributed principally to the structural difference in the Cu(II) coordination sphere, 1 being significantly closer to trigonal-bipyramidal, whose difference changes both the nearest and next-nearest neighbor interactions.

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Section: Discussionmentioning

confidence: 99%

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Herringer¹,

Landee²,

Turnbull³

et al. 2017

Inorg. Chem.

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“…Correlation of the exchange coupling with structural parameters in Cu 2 Cl 6 2Ϫ dimers has received considerable attention in the past. [19] The coupling is antiferromagnetic, with J/k ഠ 50 K for the planar conformation (based on the interaction Hamiltonian H ϭ ϪJ S 1 ·S 2 ), with the coupling becoming ferromagnetic as distortion from planarity occurs. In particular, for the type of bifold distortion observed in this structure, the crossover is estimated to occur at a bifold angle near 20°.…”

Section: Magneto-structural Correlationsmentioning

confidence: 99%

Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate(II): (Hpy)₂[Cu₃Cl₈(H₂O)₂]

et al. 2003

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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) Å, 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 intermediate on thermal analysis. Magnetic studies reveal ferromagnetic coupling within the chains with an intradimer exchange coupling of 12.1 cm−1 and a dimer‐monomer exchange coupling of 1.34 cm−1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…For instance, chain or layer structures are found for salts of the [cuc1,12-ion (18,19). Various salts of composition A'CUCI, consist of [CuCl,]-units or chlorine-bridged [cu2c1612-dimers connected into a linear chain (20)(21)(22)(23)(24). Salts of [CuCl,(H,O)]-are also known (25).…”

Section: {Cu(3)-cu(2)-cu(l)-cu(l)-cu(2)-cu(3))cu(3)~~~mentioning

confidence: 99%

Preparation and structure of 7-azaindolium salts containing unusual chloro-copper(II) anionic units

Poitras¹,

Leduc²,

Beauchamp³

1993

Can. J. Chem.

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JACQUES POITRAS, MARTIN LEDUC, and ANDRE L. BEAUCHAMP. Can. J. Chem. 71, 549 (1993).Dark-red crystals of (H,a~a)~[Cu~Cl,,(H,0)~]Cl were obtained by addition of HC1 to equimola~ amounts of 7-azaindole (Haza) and CuC12. 2H,O in methanol. They were shown by X-ray diffraction (triclinic, P1, a = 9.396(1), b = 9.894(1), c = 15.958(1), A, a = 106.10(1)", (3 = 98.25(1)', y = 105.56(1)0,' Z = 1, R = 0.031) to contain infinite chains in which the basic [ C U~C~, , ( H~O )~] ' pattern is built up from ti-an~-CuCl~(H,O)~, [CuC13(H,0)]-, and dichlorobridged [cu,c~,]' species. In the idealized chain, these units occur in the 1 :2: 1 ratio, but disorder is present and some of the C U C~~( H~O )~ units are randomly replaced by [CuC13(H,0)]-. The Cu atoms have a roughly square-planar primary coordination, and connection along the chain is achieved by weaker apical Cu-CI bridging interactions. All azaindole molecules are present as uncoordinated N7-protonated monocations. A related (H2aza)3[Cu3Cl,(H20)3]Cl salt was obtained as a side-product of the reaction of 7-azaindole with excess CuCl,. 2H20 in methanol without acid. In these brown crystals (triclinic, P I , a = 9.308(1), b = 9.964(1), c = 19.212(4) A, a = 76.67(1)", P = 79.35(1)", y = 75.27(1)", Z = 2, R = 0.046), the [Cu6~1,,(H20)6]'-pattern of the chain contains the same three building units as above, but in the 2:2: 1 ratio. In both salts, the polymeric chloro-copper chains are parallel and separated by azaindolium cations stacked along the same direction. The structures are stabilized by networks of hydrogen bonds involving the azaindolium cations, the chlorine atoms, and water molecules in the chloro-copper chain, and a noncoordinated C1-ion. Most of the azaindolium cations are disordered. The influence of N7-protonation on the infrared spectrum of azaindole is discussed. La plupart des cations azaindolium sont dCsordonnCs. L'influence de la protonation en N7 sur le spectre infrarouge de l'azaindole est discutCe. IntroductionIn many of the complexes of 7-azaindole (Haza, Scheme 1) reported so far, the ligand monoanion plays a bridging role rn "7 PI similar to that of carboxylates in stabilizing dinuclear units. HFor instance, copper(I1) azaindolate has been found to con-SCHEME 1 tain discrete Cu,(aza), dimeric units with the "windmill" tetra(azaindolate)dimetal structure of cop~er(II) acetate (1).azaindole with copper(I1) chloride in methanol, under con-A similar bridging role has been observed in compounds with ditions that favored ligand binding in the neutral form. To several other metals (2-4). As Yet, midentate binding of the complete our survey of the CuC1,-azaindole system, some anionic form has been observed only in the [CH,Hg(aza)l experiments were run in slightly acidic solution, conditions molecule, which was recently s h~w n to exist as an N lthat were known to lead to N7-protonated azaindolium salts bonded monomer (4-6). Because azaindole is a much weaker with ZnC1, (7). This was intended to yield salts of simple acid, adduct formation with the neutral mol...

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Structural and magnetic properties of bis(ethanolammonium)hexahalodicuprate(II) salts: Copper(II) halide dimers with a square-pyramidal type distortion

Cited by 22 publications

References 9 publications

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate(II): (Hpy)₂[Cu₃Cl₈(H₂O)₂]

Preparation and structure of 7-azaindolium salts containing unusual chloro-copper(II) anionic units

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Structural and magnetic properties of bis(ethanolammonium)hexahalodicuprate(II) salts: Copper(II) halide dimers with a square-pyramidal type distortion

Cited by 22 publications

References 9 publications

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Ferromagnetic Exchange in Bichloride Bridged Cu(II) Chains: Magnetostructural Correlations between Ordered and Disordered Systems

Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate(II): (Hpy)2[Cu3Cl8(H2O)2]

Preparation and structure of 7-azaindolium salts containing unusual chloro-copper(II) anionic units

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Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate(II): (Hpy)₂[Cu₃Cl₈(H₂O)₂]