A New Hydroxo‐bridged Chromium(III) Dimer [Cr(saltn)OH]2·4H2O: Synthesis, Crystal Structure and Magnetic Properties

A new hydroxo-bridged dimeric Cr(III) complex [Cr(saltn)OH]2·4H2O [H2saltn=N,N′-bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P-1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six-coordinate, distorted-octahedral. The bridging Cr2O2 unit is strictly planar, as required by the crystallographic symmetry. The CrOCr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2-300 K. By using the spin-spin coupled model for an S1=S2=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=-0.85(2) cm-1, and zJ' =0.18(3)cm-1, indicating the presence of a weak antiferromagnetic spin-exchange interaction between the Cr(III) ions in the binuclear complex.

[1]  B. Twamley,et al.  Structure of two azide salts of a copper(II) macrocycle and magnetic properties of Cu(14ane)Cu(N3)4. , 2004, Inorganic chemistry.

[2]  J. Long,et al.  Raising the spin-reversal barrier in cyano-bridged single-molecule magnets: linear Mn(III)(2)M(III)(CN)(6) (M = Cr, Fe) species incorporating [(5-Brsalen)Mn](+) units. , 2004, Inorganic chemistry.

[3]  Xiaoping Shen,et al.  Syntheses, crystal structures and magnetic properties of two cyano-bridged two-dimensional assemblies [Fe(salpn)]2 [Fe(CN)5NO] and [Fe(salpn)]2[Ni(CN)4] , 2004 .

[4]  Chunhua Yan,et al.  From achiral ligands to chiral coordination polymers: spontaneous resolution, weak ferromagnetism, and topological ferrimagnetism. , 2004, Journal of the American Chemical Society.

[5]  J. Reedijk,et al.  A unique methoxo- and fluoro-bridged triangular trinuclear Cu(ii) species linked in a lattice via mononuclear Cu(ii) units. Synthesis, X-ray structure and magnetism of [Cu4(2-aminopyrimidine)6(3-OCH3)2(-F)3(F)2](BF4)Electronic supplementary information (ESI) available: fitting of the magnetic coupli , 2003 .

[6]  E. Coronado,et al.  Synthesis, crystal structure and magnetic properties of [Cr2Cu2(bpy)4(ox)5] · 2H2O. An oxalato-bridged heterometallic tetramer , 2003 .

[7]  N. Andersen,et al.  Synthesis, crystal structure, and magnetic properties of mu-hydroxo-bis[pentakis(acetonitrile)chromium(III)] tetrafluoroborate: an acetonitrile analogue to "acid rhodo". , 2003, Inorganic chemistry.

[8]  P. Cheng,et al.  A pentanuclear complex derived from manganese(III) Schiff-based complex and hexacyanoferrate(III): synthesis, structure and magnetic properties , 2003 .

[9]  K. Wieghardt,et al.  The methanol-methanolate CH(3)OH...OCH3(-) bridging ligand: tuning of exchange coupling by hydrogen bonds in dimethoxo-bridged dichromium(III) complexes. , 2002, Inorganic chemistry.

[10]  Yadong Li,et al.  From one-dimensional chain to pentanuclear molecule. Magnetism of cyano-bridged Fe(III)-Ni(II) complexes. , 2002, Inorganic chemistry.

[11]  B. Nair,et al.  Effect of molecular association and reactivity on substitution in chromium(III)–salprn complexes , 2002 .

[12]  M. El-shahat,et al.  SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR AND BINUCLEAR CHROMIUM(III) COMPLEXES OF α-BENZOIN OXIME , 2002 .

[13]  D. Liao,et al.  Synthesis and crystal structure of oxo-bridged dimanganese(III) complex [Mn III (salpn)OH] 2 (CH 3 OH)(CH 3 CN) 2 , 2002 .

[14]  Wei‐Yin Sun,et al.  Synthesis, Crystal Structure and Magnetic Property of Copper(II) Complex with 4′-Cyanobenzyl-1-imidazol , 2002 .

[15]  Xiao‐Ming Chen,et al.  Synthesis, Crystal Structures and Magnetic Properties of Two Methoxo-Bridged Dimeric Copper(II) Complexes [Cu 2(APMD)4(μ2-OMe) 2 ]X 2(APMD = 2-aminopyrimidine; X = BF4 or CIO4) , 2002 .

[16]  S. Ohba,et al.  Synthesis and Magnetic Properties of a Polymeric Nitridochromium(V) Complex with a Tetradentate Schiff Base Ligand , 2001 .

[17]  T. Rojo,et al.  Polynuclear NiII and MnII azido bridging complexes. Structural trends and magnetic behavior , 1999 .

[18]  R. Caballol,et al.  AB INITIO CONFIGURATION INTERACTION CALCULATION OF THE EXCHANGE COUPLING CONSTANT IN HYDROXO DOUBLY BRIDGED CR(III) DIMERS , 1999 .

[19]  C. Olsen,et al.  Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Difluoro-Bridged Dinuclear Chromium(III) Complex with a Substituted Tetrahydrosalen Derivative as Ligand† , 1996 .

[20]  W. Reiff,et al.  Synthesis and characterization of a hydroxyl-bridged iron(III) dimer of N,N'-ethylenebis(salicylamine) , 1983 .

[21]  K. Wieghardt,et al.  Exchange coupling in tris(.mu.-hydroxo)bis[(1,4,7-trimethyl-1,4,7-triazacyclononane)chromium(III)] triperchlorate trihydrate , 1983 .

[22]  E. Pedersen,et al.  A Novel Correlation between Magnetism and Structural Parameters in Superexchange Coupled Chromium(III) Dimers. , 1983 .

[23]  K. Wieghardt,et al.  New triply hydroxo-bridged complexes of chromium(III), cobalt(III), and rhodium(III): crystal structure of tris(.mu.-hydroxo)bis[(1,4,7-trimethyl-1,4,7-triazacyclononane)chromium(III)] triiodide trihydrate , 1982 .

[24]  S. Larsen,et al.  The Crystal Structure of Di-mu-hydroxobis[bis{(S)-1-(2-pyridyl)ethylamine}chromium(III)] Dithionate Dihydrate and the Absolute Configuration of the Cation. , 1981 .

[25]  S. J. Cline,et al.  Structural and magnetic characterization of the chromium(III) dimers di-.mu.-hydroxo-bis[(4-hydroxo-2,6-dicarboxylatopyridine)aquachromium(III)] tetrahydrate, [Cr(chel)(OH2)OH]2.4H2O, and di-.mu.-hydroxo-bis[(4-chloro-2,6-dicarboxylatopyridine)aquachromium(III)] dihydrate, [Cr(Cl-dipic)(OH2)OH]2.2H2 , 1979 .

[26]  D. Hodgson,et al.  A ferromagnetically coupled chromium(III) dimer: synthesis, structure, and magnetic properties of sodium di-.mu.-hydroxo-bis[bis(malonato)chromate(III)] pentahydrate , 1977 .

[27]  D. Hodgson,et al.  Magnetic and structural characterization of the chromium(III) dimer sodium diμ-hydroxobis[bis(oxalato)chromate(III)] hexahydrate, Na4[Cr(C2O4)2OH]2·6H2O , 1977 .

[28]  S. J. Cline,et al.  Structural and magnetic properties of di-µ-hydroxo-bis[bis(ethylenediamine)chromium(III)] dithionate , 1977 .

[29]  D. Hodgson,et al.  Structural and magnetic characterization of di-.mu.-hydroxo-bis[bis(1,10-phenanthroline(chromium(III)] iodide tetrahydrate , 1975 .

[30]  E. D. Estes,et al.  Structural characterization of di-.mu.-hydroxo-bis(N,N,N',N'-tetraethylethylenediamine)dicopper(II) perchlorate, [Cu(teen)OH]2(ClO4)2 , 1974 .

[31]  D. Hodgson,et al.  Structural and magnetic properties of di-.mu.-hydroxo-tetraglycinatodichromium(III) , 1973 .

[32]  D. Hodgson,et al.  The crystal and molecular structure of di‐μ‐hydroxobis[di(1,10‐phenanthroline)chromium(III)] chloride hexahydrate , 1973 .

[33]  J. A. Stanko,et al.  Structures of the oxo- and hydroxo-bridged, binuclear chromium(III)-ammine complexes. Rhodo and erythro series , 1971 .

[34]  A. McPhail,et al.  Preparation, magnetic, and electronic spectral properties of some chromium(III)–NN′-ethylenebis(salicylideneiminato) complexes: crystal and molecular structure of NN′-ethylenebis(salicylideneiminato)diaquochromium(III) chloride , 1970 .