Structure and magnetic exchange in poly-bis((μ-dialkylphosphinato)copper(II) compounds

1984 ◽  
Vol 62 (5) ◽  
pp. 891-898 ◽  
Author(s):  
John S. Haynes ◽  
Katherine W. Oliver ◽  
Steven J. Rettig ◽  
Robert C. Thompson ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Magnetic Properties ◽  
Heisenberg Model ◽  
Magnetic Exchange ◽  
Magnetic Susceptibilities ◽  
Full Matrix ◽  
Linear Chains ◽  
Ferromagnetic Exchange ◽  
Structural Details

The preparation, magnetic and thermal properties, electronic and infrared spectra, and molecular structure of poly-bis(μ-di-n-hexylphosphinato)copper(II) are described. Crystals of the compound are triclinic, a = 9.800(3), b = 12.336(6), c = 13.352(8) Å, α = 88.53(3), β = 74.02(4), γ = 82.33(3)°, Z = 2, space group [Formula: see text]. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to R = 0.045 and Rw = 0.056 for 3095 reflections with I ≥ 3σ(I). The crystal structure of Cu[(n-C6H13)2PO2]2 consists of well-separated infinite chains of centro-symmetric spiro-fused eight-membered rings propagating along the crystallographic a axis.The magnetic susceptibility of Cu[(n-C6H13)2PO2]2 was studied over the temperature range 4.2 to 300 K. The compound shows ferromagnetic behaviour and the data have been successfully analyzed according to the isotropic Heisenberg model for linear chains with g = 2.16 and J = 2.58 cm−1. For comparison, the magnetic susceptibilities of Cu[(C2H5)2PO2]2 and Cu[(n-C4H9)2PO2]2 have also been measured over the range 4.2 to 300 K. The butyl derivative shows ferromagnetic exchange with g = 2.16 and J = 2.22 cm−1 while the ethyl derivative is antiferromagnetic with g = 2.19 and −J = 1.27 cm−1. The structural details of all three compounds are examined in the light of the differing magnetic properties.

Nd7,33Ta8O28CI6 — ein Zwischenprodukt des thermischen Abbaus von Nd2Ta2O7Cl2: Präparation, Struktur und magnetische Eigenschaften / Nd7,33Ta8O28Cl6 — an Intermediate Product of the Thermal Decomposition of Nd2Ta2O7Cl2: Preparation, Crystal Structure and Magnetic Properties

1988 ◽  
Vol 43 (12) ◽  
pp. 1567-1574 ◽  
Author(s):  
U. Schaffrath ◽  
R. Gruehn
Keyword(s):  
Crystal Structure ◽  
Thermal Decomposition ◽  
Magnetic Properties ◽  
Calculated Data ◽  
Chemical Transport ◽  
Structure Type ◽  
Magnetic Susceptibilities ◽  
Relationship Of ◽  
The Relationship ◽  
Preparative Route

Abstract Single crystals of the new oxochlorotantalate Nd7.33Ta8O28Cl6, could be obtained only by chemical transport reactions (T2 → T1; T2 - 1000 °C, T, = 900 °C) with mixtures of Cl2/TaCl5 as transport agent. NdTaO4 was chosen as the starting material. A direct preparative route to Nd7.33Ta8O28Cl6 from binary and ternary components, however, was not successful. Nd7.33Ta8O28Cl6 , crystallizes in the space group Cmmm with a = 10.3381(8) Å, b = 18.865(1) Å, c - 3.9152(3) A; Z = 1. The structure was refined to R - 4.42%, R w = 2.76%. Main building units are pairs of edge-sharing TaO6 -octahedra which are connected with threefold capped trigonal prisms around Nd. Especially remarkable is one Nd position with an occupation factor of 0.833. The relationship of this new structure type with Nd2Ta2O7Cl2 is considered. Furthermore, we have measured the magnetic susceptibilities of both Nd-compounds in a temperature range from 3,6 to 251,3 K. The results are compared with calculated data.

Synthetic plant growth regulators. V. The synthesis and crystal structure of a hybrid gibberellin-helminthosporic acid

1980 ◽  
Vol 33 (5) ◽  
pp. 1061 ◽  
Author(s):  
JV Turner ◽  
BF Anderson ◽  
LN Mander
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Carboxylic Acid ◽  
Standard Procedure ◽  
Direct Methods ◽  
Detailed Comparison ◽  
Synthesis And Crystal Structure ◽  
Full Matrix ◽  
Cyclopropyl Ketone ◽  
R Value

(3aRS,4RS,6RS,8aSR)-5-Methyleneoctahydro-4H-3a,6-methanoazulene-4-carboxylic acid (7) has been synthesized and a detailed comparison made between its molecular structure and that of gibberellic acid (4). Indane-5-carboxylic acid (8) was converted by an alternating sequence of reduction and isomerization into the hydrindene acid (11). The diazomethyl ketone derived from (11) was transformed to cyclopropyl ketone (12) which was reduced by Li/NH3 with stereochemical inversion at the β-carbon to give a 1:3 mixture of ketones (13) and (14) respectively. Ketone (14) was then converted into the title acid (7) by a standard procedure. ��� Molecules of (7) crystallize in space group P2/c with a 7.782(1), b 11.055(1), c 14.559(3) Ǻ, β 116.05(1)°. The structure was solved by direct methods and refined by full-matrix least squares to a final R value of 0.053.

Crystal and molecular structure of [dimethyl(3,5-dimethyl-1-pyrazolyl)(ethanol-amino)gallato (N(2),O,N(3))](η3-cycloheptatrienyl)dicarbonylmolybdenum

1981 ◽  
Vol 59 (11) ◽  
pp. 1665-1670 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Amino Nitrogen ◽  
Full Matrix ◽  
Octahedral Environment ◽  
Distorted Octahedral ◽  
Unusual Type

Crystals of [dimethyl(3,5-dimethyl-l-pyrazolyl)(ethanolamino)gallato(N(2),O,N(3))](η3-cycloheptatrienyl)dicarbonylmolybdenum are monoclinic, a = 10.511(1), b = 8.335(1), c = 24.138(3) Å, β = 102.22(1)°, Z = 4, space group P21/c. The structure was solved by Patterson and Fourier syntheses and was reflned by full-matrix least-squares procedures to R = 0.028 and Rw = 0.046 for 3708 reflections with I ≥ 3σ(I). The crystal structure consists of discrete molecules linked by N—H … O hydrogen bonds (N … O = 2.929(5) Å). The Mo atom is in a distorted octahedral environment with the η3-C7H7 ligand occupying one coordination site, trans to the amino nitrogen, as a π-donating ligand. Important bond distances (corrected for libration) are: Mo—O, 2.245(2), Mo—N(amino), 2.249(3), Mo—N(pyrazolyl), 2.270(3), Mo—C(O), 1.950(4) and 1.947(4), Mo—C(C7H7), 2.176(4), 2.364(4), and 2.380(4), Ga—O, 1.919(3), Ga—N, 1.984(3), and Ga—C, 1.982(5) and 1.983(5) Å. An unusual type of disorder is present in which a second image of the molecule, approximately mirrored by the plane y = 1/4, is in evidence at low occupancy.

Reaction of N,N′-dihydroxy-.N,N′-dimethylmethanediamine with phenylboronic acid and the crystal and molecular structure of N,N′-dihydroxy-N,N′-dimethylmethanediamine

1989 ◽  
Vol 67 (11) ◽  
pp. 1959-1963 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Exact Formula ◽  
Full Matrix ◽  
Space Group ◽  
Hydrogen Bonded

The reaction of N,N′-dihydroxy-N,N′-dimethylmethanediamine with phenylboronic acid leads to the product 1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane rather than the expected product 1,5-dimethyl-3-phenyl-1,5-diaza-2,4-dioxa-3-boracyclohexane. The structure of N,N′-dihydroxy-N,N′-dimethylmethanediamine has been determined and is discussed in terms of its reaction with PhB(OH)2. Crystals of N,N′-dihydroxy-N,N′-dimethylmethanediamine are tetragonal, a = 8.5346(3), c = 8.4178(7) Å, Z = 4, space group P421c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.036 and Rw of 0.038 for 333 reflections with I ≥ 3σ(I). The structure consists of hydrogen-bonded dimers having exact [Formula: see text] symmetry. Keywords: N,N′-dihydroxy-N,N′-dimethylmethanediamine, crystal structure.

Crystal and molecular structure of L-prolinatodiphenylboron

1977 ◽  
Vol 55 (6) ◽  
pp. 958-965 ◽  
Author(s):  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Conformational Disorder ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Crystals of L-prolinatodiphenylboron are monoclinic, a = 5.9427(5), b = 14.4633(7), c = 8.9654(4) Å, β = 98.423(8)°, Z = 2, space group P21. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.037 and Rw of 0.053 for 1477 reflections with I ≥ 3σ(I). The proline ring exhibits conformational disorder. The crystal structure consists of discrete molecules linked by N—H … O hydrogen bonds (N … O = 2.893(3) Å) along the short a axis. Intramolecular N—B coordination occurs to form a system of two fused five-membered rings. Bond lengths (corrected for libration) are: N—B, 1.630(3), O—B, 1.529(3), O—C, 1.219(3) and 1.300(3), N—C, 1.506(3) and 1.507(3), C(sp3)–C(sp3), 1.525(4), C(sp2)—C(sp3), 1.517(3), and mean C—C(phenyl), 1.394 Å.

Synthesis, structure, and properties of poly-bis(μ-diethylphosphinato)copper(II)

1982 ◽  
Vol 60 (15) ◽  
pp. 2017-2022 ◽  
Author(s):  
Katherine W. Oliver ◽  
Steven J. Rettig ◽  
Robert C. Thompson ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Magnetic Properties ◽  
Magnetic Susceptibility ◽  
Infrared Spectra ◽  
Field Model ◽  
Direct Methods ◽  
Coordination Geometry ◽  
Structure And Properties ◽  
Tetrahedral Coordination ◽  
Full Matrix

The preparation, magnetic properties, electronic and infrared spectra, and molecular structure of poly-bis(μ-diethylphosphinato)copper(II) are described. Crystals of poly-bis(μ-diethylphosphinato)copper(II) are triclinic, a = 7.700(1), b = 9.807(1), c = 10.101(1) Å, α = 90.48(1), β = 104.77(1), γ = 112.21(1)°, Z = 2, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.025 and Rw = 0.032 for 3491 reflections with I ≥ 3σ(I). The polymeric structure consists of Cu atoms with flattened tetrahedral coordination geometry linked by double phosphinate bridges. Mean bond lengths (corrected for libration) are: Cu—O, 1.924(3), P—O, 1.526(4), and P—C, 1.807(4) Å. Assignment of the electronic spectrum using a crystal field model gives Dq = 1665 cm−1 and Cp = 1800 cm−1. Magnetic susceptibility studies give no evidence for magnetic concentration over the temperature range 80 to 300 K.

Structural studies of organoboron compounds. XXII. Preparation and crystal and molecular structure of tetramethylammonium-2,4,6,6-tetraphenyl-1,3,5-trioxa-2,4- dibora-6-boratacyclohexane

1985 ◽  
Vol 63 (12) ◽  
pp. 3516-3520 ◽  
Author(s):  
W. Kliegel ◽  
H.-W. Motzkus ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Physical Properties ◽  
Crystal And Molecular Structure ◽  
Structural Parameters ◽  
Direct Methods ◽  
Maximum Deviation ◽  
Structural Studies ◽  
Full Matrix ◽  
The Mean

Details of the preparation and physical properties of (Me4N)+ (Ph4B3O3)− are given. Crystals of tetramethylammonium 2,4,6,6-tetraphenyl-1,3,5-trioxa-2,4-dibora-6-boratacyclohexane are orthorhombic, a = 18.130(2), b = 11.9745(7), c = 12.5187(5) Å, Z = 4, space group Pna21. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.056 and Rw = 0.064 for 1460 reflections with I ≥ 2σ(I). The crystal structure consists of discrete tetramethylammonium cations and tetraphenylboroxinate anions, the first such anion to be structurally characterized. The six-membered B3O3 ring is significantly non-planar, having a flattened O(1)-envelope conformation (maximum deviation from the mean plane = 0.074(4) Å for O(1)). The boroxine ring in the anion shows significant deviations from the D3h symmetry observed for neutral boroxines. Important mean structural parameters: B(sp3)—O = 1.494(2), B(sp2)—O[B(sp3)] = 1.320(9), B(sp2)—O[B(sp2)] = 1.389(3) Å, O—B(sp3)—O = 110.5(5), O—B(sp2)—O = 121.7(6), B(sp2)—O—B(sp2) = 118.9(5), and B(sp3)—O—B(sp2) = 122.9(1)°.

Complexes of the methyl tris(3,5-dimethylpyrazol-1-yl) gallate ligand, MeGa(N2C5H7)3−, and its hydroxy derivative, MeGa(N2C5H7)2(OH)−. Crystal and molecular structure of [MeGa(N2C5H7)2(OH)]Mo(CO)2(η3-C4H7)

1979 ◽  
Vol 57 (2) ◽  
pp. 139-146 ◽  
Author(s):  
Kenneth R. Breakell ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Structure Determination ◽  
Carbonyl Compounds ◽  
Crystal And Molecular Structure ◽  
Hydroxy Derivative ◽  
Full Matrix ◽  
Sterically Demanding

The synthesis and coordinating properties of the tridentate tris-chelating ligand, methyl tris(3,5-dimethylpyrazol-1-yl)gallate, MeGa(N2C5H7)3−, are described. Carbonyl and nitrosyl carbonyl compounds of manganese, molybdenum, and tungsten incorporating this ligand are detailed. The ready conversion of the above ligand to the less sterically demanding tris-chelating 'hydroxy' ligand [MeGa(N2C5H7)2(OH)]− occurs in attempted syntheses of the 'η3-allyl' complexes, [MeGa(N2C5H7)3]M(CO)2'η3-allyl', (where M = Mo or W, 'η3-allyl' = η3-C3H5, η3-C4H7). The tridentate chelating nature of this 'hydroxy' ligand is conclusively demonstrated in the crystal structure determination of the complex, [MeGa(N2C5H7)2(OH)]-Mo(CO)2(η3-C4H7). Crystals of this complex are monoclinic, a = 14.020(4), b = 10.110(1), c = 15.493(7) Å, β = 111.58(3)°, Z = 4, space group P21/n. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to a final R of 0.40 and Rw of 0.043 for 3374 reflections with I ≥ 3.5σ(I).

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