The novel magnetism and crystal structure of the complex di-µ-hydroxybis(bipyridyl)dicopper(<scp>II</scp>) sulphate pentahydrate

Casey, A. T.; Hoskins, Bernard F.; Whillans, Francis D.

doi:10.1039/c29700000904

Cited by 54 publications

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“…Hatfield Jeter, Lewis, Hempel, Hodgson & Hatfield, 1972) and similar studies on the analogous systems [Cu(bipy)OH] 2+, where bipy is 2,2'-bipyridine (Casey, Hoskins & Whillans, 1970;Majeste & Meyers, 1970;Barnes, Hodgson & Hatfield, 1972) and [Cu(tmen)OH] 2+, where tmen = tetramethylethylenediamine (Mitchell, Bernard & Wasson, 1970;Cole & Brumage, 1970) we were able to deduce that the value of 2J, the singlet-triplet energy separation, decreases as the Cu-O-Cu bridging angle ~0 increases, and that 2J changes from positive to negative in the region 97 to 99 ° .…”

Section: Introductionmentioning

confidence: 99%

The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

Veal¹,

Hatfield²,

Hodgson³

1973

Acta Crystallogr Sect B

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THE STRUCTURES OF FLUORIDES. Iresult of decreasing stability of the octahedral structure with decreasing cation size, with a consequent tendency to form fivefold and, finally, tetrahedral coordination. In the alkali metal niobates (Megaw, 1968b) The Crystal and Molecular Structure of Di-~t-hydroxobisldi(1,10-phenanthroline)chromium(III)l Chloride Hexahydrate BY JACK T. VEAL,* WILLIAM E. HATFIELD AND DEREK J. HODGSONt Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27514, U.S.A. (Received 17 May 1972; accepted 14 September 1972)The crystal and molecular structure of di-/t-hydroxobis[di(1,10-phenanthroline)chromium(IlI)] chloride hexahydrate, [Cr(phen)2OH]2Cla.6H20, has been determined from three-dimensional counter X-ray data. The material crystallizes in the triclinic space group PI with two dimeric formula units in a cell whose dimensions are a= 14.056 (7), b= 11.296 (6), c= 18.990 (9) A, ~=87.15 (3), fl= 107-63 (2), and ),=74.68 (3) °. The observed and calculated densities are 1.39 (4) and 1.342 g cm -3 respectively. The structure has been refined by full-matrix least-squares techniques to a conventional R value of 0.077 for 3392 independent intensities greater than three times their estimated standard deviations. The complex consists of pairs of chromium atoms which are linked by two hydroxo bridges, with two 1,10-phenanthroline groups coordinated to each metal; the coordination geometry around each chromium is roughly octahedral. The average Cr-N and Cr-O bond lengths are 2-052 (6) and 1.927 (6) .~, respectively, while the Cr-Cr separation is 3.008 (3) ,& and the average Cr-O-Cr angle is 102-7 (4) °. The geometry of this complex is compared with that of [Cr(gly)2OH]2 and with those of complexes of the type [CuLOH]~. +, and the magnetic properties of the complex are discussed in terms of the bridging geometry.

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Section: Introductionmentioning

confidence: 99%

The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

Veal¹,

Hatfield²,

Hodgson³

1973

Acta Crystallogr Sect B

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“…The copper(II) environment found here is similar to those found in di-^-hydroxo-bis(Ar,7V',7V,,7V'/-tetramethylethylenediamine)dicopper(II) bromide (hereafter the ligand is abbreviated as tmen)18 and di-µhydroxo-bis(bipyridyl)dicopper(II) sulfate pentahydrate. 4 The main differences among these complexes are found in the geometric arrangement at the bridging oxygen atoms, In these three complexes, the Cu-O-Cu bridge angles are 97 (bipyridyl), 99 (EAEP), and 104°( tmen). Another structural difference is in the angle between the two basal planes.…”

Section: Resultsmentioning

confidence: 99%

Magnetic properties of the complex di-.mu.-hydroxo-bis[2-(2-ethylaminoethyl)pyridine]dicopper(II) perchlorate

Jeter¹,

Lewis²,

Hempel³

et al. 1972

Inorg. Chem.

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NotesScheme I category IV reactions should have similar values for the rate constants, as is observed.The rate constant calculated for reaction 1 in Table III lies well in the diffusion-controlled region and seems prohibitively high. It should be noted, however, that the value given in Table III is only about two or three times greater than the values for Cu(II)-en reactions given in Table II or reported by Kirschenbaum and Kustin13for25°.The high rate constants are the direct result of attributing "normal" relaxation times, such as those given in Table I, to paths involving a species (free en) which is present at very low concentration levels owing to its dibasic nature. A kinetically equivalent path involving the rapidly formed conjugate species of reaction 1 can also be written. The product of the concentrations of kv (hm)Cu(OH)+ + Hen+ (hm)Cu(en)2^+ H20 (V)

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“…The apical Cu-06 bond at 2.205 (5) Á is only 10% longer than basal Cu-O bonds as is also the case for copper complexes of hippurate anion,11 phenoxyacetate,12 and [Cu2(bpy)2-( )28 4( )]•4 2 with a sulfate oxygen coordinated at the apex. 13 The two Cu-Obase bonds are remarkably similar considering that one is to a sulfate oxygen (1.986 Á) and the other to a water molecule (1.974 Á). The four basal donor atoms (01, 05, NI, N2) lie within one standard deviation (±0.08 Á) of the least-squares plane they generate, the plane being defined by the equation 0.040a -0.0155y + 0.0594z = 0.259.…”

Section: Methodsmentioning

confidence: 97%

Preparation, properties, and crystal and molecular structure of diaquosulfato (N,N,N',N'-tetramethylethylenediamine)copper(II) hydrate

Balvich¹,

Fivizzani²,

Pavkovic³

et al. 1976

Inorg. Chem.

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The compound diaquosulfato(A,Ar,Ar',yV'-tetramethylethylenediamine)copper(II) hydrate, [Cu(tmen)S04(0H2)2]'H20, has been prepared and its structure determined crystallographically. This substance crystallizes in space group Pbca with eight molecules per unit cell of dimensions a = 12.543 (1), b = 15.782 (1), and c = 13.862 (1) Á. The observed and calculated densities are 1.59 (2) and 1.597 g/cm3, respectively. From a total of 2189 independent reflections measured with Ni-filtered copper x radiation, 1869 statistically significant reflections (|Fo| > 3 ( 0)) were used to determine the structure and resulted in final values of R = 0.067 and Rw = 0.061 (154 parameters were least-squares refined). Hydrogen atoms were located but not refined. The molecular structure consists of monomeric [Cu(tmen)S04(0H2)2] units in which the coordination polyhedron about copper is a tetragonal pyramid. The Cu-OH2 apical bond length of 2.205 (5) Á is 10% longer than the four remaining bonds to water, 1.974 (5) Á, monodentate sulfate oxygen, 1.986 (5) Á, and chelated diamine nitrogens, 2,024 (5) and 2.025 (5) A. Copper is situated 0.25 A above the basal plane, and chelate ring conformation is gauche. All water molecules participate in an extensive hydrogen-bonding network to noncoordinated sulfate oxygens with an average 0-0 separation of 2.68 A. The room-temperature magnetic moment is 1.87 BM.

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The novel magnetism and crystal structure of the complex di-µ-hydroxybis(bipyridyl)dicopper(II) sulphate pentahydrate

Cited by 54 publications

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The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

The crystal and molecular structure of di-μ-hydroxobis[di(1,10-phenanthroline)chromium(III)] chloride hexahydrate

Magnetic properties of the complex di-.mu.-hydroxo-bis[2-(2-ethylaminoethyl)pyridine]dicopper(II) perchlorate

Preparation, properties, and crystal and molecular structure of diaquosulfato (N,N,N',N'-tetramethylethylenediamine)copper(II) hydrate

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