Metal pyrazolate polymers. Part 1. Synthesis, structure, and magnetic properties of the [Cu(pz)2]x polymer

1989 ◽  
Vol 67 (11) ◽  
pp. 1970-1974 ◽  
Author(s):  
M. K. Ehlert ◽  
S. J. Rettig ◽  
A. Storr ◽  
R. C. Thompson ◽  
J. Trotter
Keyword(s):  
Crystal Structure ◽  
Direct Methods ◽  
Magnetic Data ◽  
Coordination Geometry ◽  
Antiferromagnetic Exchange ◽  
Chain Polymer ◽  
X Ray ◽  
Linear Chains ◽  
Polymeric Chains ◽  
Distorted Tetrahedral Coordination

A novel and reliable method for the synthesis of polybis(μ-pyrazolato-N,N′)copper(II), [Cu(pz)2]x(where pz = N2C3H3), is presented. Single crystals of the polymer suitable for X-ray study have been grown under carefully controlled conditions. Crystals of polybis(μ-pyrazolato-N,N′)copper(II) are orthorhombic, a = 7.917(1), b = 11.491(2), c = 7.778(1) Å, Z = 4, space group Ibam. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.029 and Rw = 0.038 for 507 reflections with I ≥ 3σ(I). The crystal structure consists of infinite double-bridged polymeric chains. The Cu atom has a D2 distorted tetrahedral coordination geometry with Cu—N = 1.957(2) Å and N—Cu—N = 94.3(1)–139.5(1)°. Magnetic susceptibility studies (4.2 to 299 K) on this material reveal very strong antiferromagnetic exchange between copper(II) centres in the extended linear chains. The magnetic data have been successfully analyzed according to the isotropic Heisenberg model for linear chains with −J = 78 cm−1 and g = 2.12. Keywords: crystal structure, copper(II) pyrazolate chain polymer, antiferromagnetic exchange.

The methylgallium-2-carboxylatobenzimidazolato hexamer, [MeGa·C8H4N2O2]6·C6H6·(Me2C6H4)2; synthesis and X-ray crystal structure

1999 ◽  
Vol 77 (4) ◽  
pp. 434-438 ◽  
Author(s):  
Steven J Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Carboxylic Acid ◽  
Room Temperature ◽  
Direct Methods ◽  
Membered Ring ◽  
Coordination Geometry ◽  
Temperature Reaction ◽  
Full Matrix ◽  
X Ray ◽  
Solvent Molecules

The room-temperature reaction of Me3Ga with benzimidazole 2-carboxylic acid in xylene solvent has yielded a novel crystalline hexameric gallium compound with "MeGa" moieties bridged by the doubly depronotated ligand precursor. Crystals of [MeGa(4,5-benzimidazolato-2-carboxylato)]6·(C6H6)·(m-Me2C6H4)2 are monoclinic, a = 18.091(2), b = 17.094(2), c = 13.2215(5) Å, Z = 2, space group C2/m. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R (F, I [Formula: see text] 3σ(I)) = 0.064 (Rw (F2, all data) = 0.134). The hexameric Ga complex contains a six-membered ring of Ga atoms, bridged by the benzimidazolate ligands with the benzo rings projecting alternately above and below the Ga plane, thus forming a ball-shaped molecule. The complex could have ideal D3d symmetry, but it contains an encapsulated molecule of benzene, which distorts the regularity of the Ga6 hexagon, and reduces the symmetry of the complex to the crystallographically observed C2h. The coordination geometry at each of the two independent GaO2N2C centres approximates a trigonal bipyramid, with a N2C trigonal plane, and the O atoms above and below; average dimensions are Ga-O = 2.176(2), Ga-N = 1.973(3), Ga-C = 1.927(5) Å, O-Ga-O = 165°. The unit cell also contains four m-xylene solvent molecules (outside the molecular cage).Key words: gallium, crystal structure, benzene intercalate, benzimidazolecarboxylic acid.

Synthesis, characterization, and X-ray structural analysis of the Cu(I) derivative, [Me2Ga(OCH2CH2NMe2)N2C5H7]Cu• PPh3

1981 ◽  
Vol 59 (3) ◽  
pp. 518-523 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Structural Analysis ◽  
Copper Atom ◽  
Direct Methods ◽  
Carbonyl Complex ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
Full Matrix ◽  
X Ray ◽  
Complex Crystals ◽  
Distorted Tetrahedral Coordination

The Cu(I) complex [Me2Ga(OCH2CH2NMe2)N2C5H7]Cu•PPh3 has been synthesized and its fluxional behavior in solution probed. Attempts have been made to isolate the analogous Cu(I) carbonyl complex. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl)(N,N-dimethylethanolamino)gallato (N(2),O,N(3))](triphenylphosphine)copper(I) are monoclinic, a = 18.871(2), b = 9.464(1), c = 18.374(2) Ā, β = 109.62(1)°, Z = 4, space group P21/c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.028 and Rw = 0.035 for 2729 reflections with I ≥ 3σ(I). The copper atom is bonded to the phosphine and to the tridentate Me2Ga(OCH2CH2NMe2)N2C5H7− ligand resulting in a distorted tetrahedral coordination geometry. The Cu—P distance of 2.156(1) Å is unusually short. Other important bond distances (corrected for libration) are: Cu—O, 2.163(2), Cu—N(pyrazolyl), 2.025(3), Cu—N(amino), 2.144(3), Ga—O, 1.896(3), Ga—N, 2.005(3), and Ga—C, 1.972(5) and 1.987(5) Å.

Synthesis and characterization of the mixed valence Cu(l)/Cu(ll) 3,5-bis(trifluoromethyl)-pyrazolate complex, [Cu(ll)2Cu(l)(F6dmpz)5]

1997 ◽  
Vol 75 (5) ◽  
pp. 491-498 ◽  
Author(s):  
Martin K. Ehlert ◽  
Alan Storr ◽  
David A. Summers ◽  
Robert C. Thompson
Keyword(s):  
Exchange Coupling ◽  
Mixed Valence ◽  
Direct Methods ◽  
Magnetic Data ◽  
Antiferromagnetic Exchange ◽  
Coupling Constant ◽  
Copper Metal ◽  
X Ray ◽  
R Value

The reaction of molten 3,5-bis(trifluoromethyl)pyrazole (F6dmpzH) with copper metal shot under an atmosphere of dioxygen yields the green trimetallic mixed valence [Cu(II)2Cu(1)(F6dmpz)5]. Crystals of [Cu(II)2Cu(I)(F6dmpz)5] are triclinic, a = 9.0557(2), b = 9.6164(2), c = 11.8874(3) Å, α= 105.406(1)°, β = 112.317(1)°, γ = 90.662(1)°, Z= 1, space group P͞1. The crystal structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R value of 0.0538 for 2591 reflections with I≥2σ(I). Magnetic susceptibility studies over the range 2–300 K reveal strong antiferromagnetic exchange coupling between the two copper(II) centers. Fits of the magnetic data to the Bleaney-Bowers equation for two interacting S= ½ centers gives the exchange coupling constant J = –235 cm–1. Key words: trimetallic, copper, 3,5-bis(trifluoromethyl)pyrazolates, X-ray structure, antiferromagnetism.

Crystal structure determination of the conformation of two bicyclo[3.3.1]nonan-ones

1985 ◽  
Vol 63 (6) ◽  
pp. 1166-1169 ◽  
Author(s):  
John F. Richardson ◽  
Ted S. Sorensen
Keyword(s):  
Crystal Structure ◽  
Direct Methods ◽  
Chair Conformation ◽  
Molecular Structures ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Final Agreement

The molecular structures of exo-7-methylbicyclo[3.3.1]nonan-3-one, 3, and the endo-7-methyl isomer, 4, have been determined using X-ray-diffraction techniques. Compound 3 crystallizes in the space group [Formula: see text] with a = 15.115(1), c = 7.677(2) Å, and Z = 8 while 4 crystallizes in the space group P21 with a = 6.446(1), b = 7.831(1), c = 8.414(2) Å, β = 94.42(2)°, and Z = 2. The structures were solved by direct methods and refined to final agreement factors of R = 0.041 and R = 0.034 for 3 and 4 respectively. Compound 3 exists in a chair–chair conformation and there is no significant flattening of the chair rings. However, in 4, the non-ketone ring is forced into a boat conformation. These results are significant in interpreting what conformations may be present in the related sp2-hybridized carbocations.

Structure of 3α,4α:5β,6β-Diepoxyandrostan-17-one

1983 ◽  
Vol 36 (11) ◽  
pp. 2333 ◽  
Author(s):  
B Kamenar ◽  
RA Pauptit ◽  
JM Waters
Keyword(s):  
Crystal Structure ◽  
Title Compound ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray

The X-ray crystal structure of 3α,4α:5β,6β-diepoxyandrostan-17-one has been determined. Crystals of the title compound (C19H26O3)are monoclinic, space group P21, with a 9.208(2), b 9.620(4), c 9.312(3) �, β 99.14(2)�, V 814.5 Ǻ3 and Z 2. The structure was solved by direct methods and refined to R 0.039 for 887 observed reflexions. The 3α,4α:5β,6β configuration of the epoxide rings confirms the assignment based on proton n.m.r. studies.

scholarly journals Synthesis, Crystal Structure and Magnetic Behaviour of Dimeric and Polymeric Gadolinium Trifluoroacetate Complexes

2006 ◽  
Vol 61 (6) ◽  
pp. 699-707 ◽  
Author(s):  
Daniela John ◽  
Alexander Rohde ◽  
Werner Urland
Keyword(s):  
Crystal Structure ◽  
Magnetic Behaviour ◽  
Magnetic Data ◽  
Space Group ◽  
X Ray ◽  
Lattice Constants ◽  
Temperature Range ◽  
X Ray Crystallography ◽  
Carboxylate Groups

The gadolinium(III) trifluoroacetates ((CH3)2NH2)[Gd(CF3COO)4] (1), ((CH3)3NH)[Gd(CF3 COO)4(H2O)] (2), Gd(CF3COO)3(H2O)3 (3) as well as Gd2(CF3COO)6(H2O)2(phen)3 · C2H5OH (4) (phen = 1,10-phenanthroline) were synthesized and structurally characterized by X-ray crystallography. These compounds crystallize in the space group P1̅ (No. 2, Z = 2) (1, 2 and 4) and P 21/c (No. 14, Z = 4) (3), respectively, with the following lattice constants 1: a = 884.9(2), b = 1024.9(2), c = 1173.1(2) pm, α = 105.77(2), β = 99.51(2), γ = 107.93(2)°; 2: a = 965.1(1), b = 1028.6(1), c = 1271.3(2) pm, α = 111.83(2), β = 111.33(2), γ = 90.44(2)°; 3: a = 919.6(2), b = 1890.6(4), c = 978.7(2) pm, β = 113.94(2)°; 4: a = 1286.7(8), b = 1639.3(8), c = 1712.2(9) pm, α = 62.57(6), β = 84.13(5), γ = 68.28(5)°. The compounds consist of Gd3+ ions which are bridged by carboxylate groups either to chains (1 and 2) or to dimers (3 and 4). In addition to the Gd3+ dimers, compound (4) also contains monomeric Gd3+ units. The magnetic behaviour of 2 and 3 was investigated in a temperature range of 1.77 to 300 K. The magnetic data for these compounds indicate weak antiferromagnetic interactions

The crystal structure of gatehouseite

2011 ◽  
Vol 75 (6) ◽  
pp. 2823-2832
Author(s):  
P. Elliott ◽  
A. Pring
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Three Dimensional ◽  
Direct Methods ◽  
Chemical Analyses ◽  
X Ray Diffraction ◽  
X Ray ◽  
Manganese Phosphate ◽  
Phosphate Mineral ◽  
Unit Formula

AbstractThe crystal structure of the manganese phosphate mineral gatehouseite, ideally Mn52+(PO4)2(OH)4, space group P212121, a = 17.9733(18), b = 5.6916(11), c = 9.130(4) Å, V= 933.9(4) Å3, Z = 4, has been solved by direct methods and refined from single-crystal X-ray diffraction data (T = 293 K) to an R index of 3.76%. Gatehouseite is isostructural with arsenoclasite and with synthetic Mn52+(PO4)2(OH)4. The structure contains five octahedrally coordinated Mn sites, occupied by Mn plus very minor Mg with observed <Mn—O> distances from 2.163 to 2.239 Å. Two tetrahedrally coordinated P sites, occupied by P, Si and As, have <P—O> distances of 1.559 and 1.558 Å. The structure comprises two types of building unit. A strip of edge-sharing Mn(O,OH)6 octahedra, alternately one and two octahedra wide, extends along [010]. Chains of edge- and corner-shared Mn(O,OH)6 octahedra coupled by PO4 tetrahedra extend along [010]. By sharing octahedron and tetrahedron corners, these two units form a dense three-dimensional framework, which is further strengthened by weak hydrogen bonding. Chemical analyses by electron microprobe gave a unit formula of (Mn4.99Mg0.02)Σ5.01(P1.76Si0.07(As0.07)Σ2.03O8(OH)3.97.

Unique thallium mineralization in the fumaroles of Tolbachik volcano, Kamchatka Peninsula, Russia. I. Markhininite, TlBi(SO4)2

2014 ◽  
Vol 78 (7) ◽  
pp. 1687-1698 ◽  
Author(s):  
Oleg I. Siidra ◽  
Lidiya P. Vergasova ◽  
Sergey V. Krivovichev ◽  
Yuri L. Kretser ◽  
Anatoly N. Zaitsev ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Microprobe Analysis ◽  
Cinder Cone ◽  
Direct Methods ◽  
Kamchatka Peninsula ◽  
Single Crystal Diffraction ◽  
X Ray ◽  
The North ◽  
Tolbachik Volcano ◽  
Academy Of Sciences

AbstractMarkhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P1̄ , a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)º, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2]– layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.

scholarly journals Einkristallzüchtung und Röntgenstrukturanalyse polymerer 1:1-Komplexe von CuBr2 und CuCl2 mit Pyrazin aus Gelen / Crystal Growth in Gels and X-Ray Characterization of Polymeric 1:1-Complexes of CuBr2 and CuCl2 with Pyrazine

1989 ◽  
Vol 44 (5) ◽  
pp. 553-556 ◽  
Author(s):  
Th. Fetzer ◽  
A. Lentz ◽  
T. Debaerdemaeker
Keyword(s):  
Crystal Structure ◽  
Thermal Decomposition ◽  
Crystal Growth ◽  
Chloro Complex ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Space Group ◽  
X Ray ◽  
Linear Chains

Single crystals of Cu(pz)Br2 and Cu(pz)Cl2 were grown by using gel methods with tetramethoxysilane as the gel-forming reagent. Thermal decomposition is interpreted. Crystal data for the bromo complex: monoclinic, space group C2/m with a = 1239.2(3) pm, b = 685.9(2) pm, c = 390.7(3) pm, β = 96,23(5)°. Crystal data for the chloro-complex: monoclinic, space group C2/m with a = 1197.1(3) pm, b = 684.9(3) pm, c = 370.1(3) pm, β = 95.96(5)°. Crystal structure analyses reveal that CuHal2 molecules are bonded by pyrazine to form linear chains. These chains are cross-linked by bridging halogen atoms.

Oxofluoro-oxalato-vanadate des vierwertigen Vanadins: Schwingungsspektrum und Struktur von Na3[VOF(C2O4)2] • 6 H2O.

1976 ◽  
Vol 31 (5) ◽  
pp. 537-540 ◽  
Author(s):  
Helmut Rieskamp ◽  
Rainer Mattes
Keyword(s):  
Crystal Structure ◽  
Oxygen Atom ◽  
Fluorine Atom ◽  
Direct Methods ◽  
Terminal Oxygen Atom ◽  
Triclinic Space Group ◽  
Trans Effect ◽  
Space Group ◽  
X Ray ◽  
In Cis

The Na and NH4 salts of the [VOF(C2O4)2]3--ion have been prepared. The crystal structure of the former has been determined from X-ray diffractometer data. The crystals are triclinic, space group P with Z = 2. The structure was solved by `direct methods' and refined to R 0.050 for 1749 reflections. In the anion, vanadium(IV) is octahedrally coordinated by a terminal oxygen atom, a fluorine atom in cis-position to the former, and two bidentate oxalate ligands. The terminal V—O-bond exhibits a strong ‘trans’ effect.

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