The Nature of the Hexahydrates of Divalent Transition Metal Cations: The Structures of the Hexafluorogermanate Hexahydrates of Iron(II), Cobalt(II) and Nickel(II)

1987 ◽  
Vol 40 (3) ◽  
pp. 565 ◽  
Author(s):  
BF Hoskins ◽  
A Linden
Keyword(s):  
Hydrogen Bonding ◽  
Transition Metal ◽  
Room Temperature ◽  
Unit Cell ◽  
Molecular Structures ◽  
Symmetry Element ◽  
Mirror Plane ◽  
Crystal And Molecular Structures ◽  
Cscl Type ◽  
Rhombohedral Symmetry

The crystal and molecular structures of the room temperature phases of MII(H2O)6GeF6 (M = Fe, Co, Ni) are reported. In each structure the M(H2O62+ and GeF62- octahedra are in approximate CsCl -type packing with hydrogen bonding between the ions. Differences in the structures arise from disorder in the orientations of the octahedra . Fe(H2O)6GeF6 crystallizes in the spate group R3M, with three molecules in the unit cell of dimensions ahex , 9.728(2), Chex 9.796(2) �. Refinement converged with R 0.0135 and Rw 0.0137, 286 independent observed reflections being used. There is disorder of both fluorine and oxygen atoms between two positions related by a mirror plane, which raises the 3 symmetry within each octahedron to overall 3m symmetry. Ni(H2O)6GeF6 crystallizes in the spate group R3 with three molecules in the unit cell of dimensions ahex 9.443(1), chex 9 .77O(l) �. Refinement converged with R 0.016 and R, 0.018 for 444 independent observed reflections. There is disorder only of the fluorine atoms between two positions unrelated by any symmetry element. CO(H2O)6GeF6 crystallizes in the space group P21/c with two molecules in the unit cell of dimensions a 6.552(2), b 9.577(2), c 8.520(1) �, ,β 99.74(2)�. Refinement converged with R 0.042 and R, 0.054 for 1232 independent observed reflections. The structure is not disordered and deviates only slightly from rhombohedral symmetry.

Structural and spectroscopic studies of transition metal nitrite complexes. V. Crystal structures and spectra of trans-Tetrakis(pyridine)dinitritonickel(II)-pyridine (1/2), trans-Tetrakis(4-methylpyridine)dinitritonickel(II) and trans-Tetrakis(pyrazole)-dinitritonickel(II)

1981 ◽  
Vol 34 (10) ◽  
pp. 2095 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
BW Skelton ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Transition Metal ◽  
Crystal Structures ◽  
Electronic Spectra ◽  
Spectroscopic Studies ◽  
Molecular Structures ◽  
Aromatic Rings ◽  
Paddle Wheel ◽  
Crystal And Molecular Structures ◽  
Infrared Frequencies

The crystal and molecular structures of the compounds [Ni(py)4(ONO)2],2py, [Ni(γmpy),(ONO)2] and [Ni(prz)4(ONO)2] are reported.�All three are trans nitrito complexes, the pyridine (py) compound containing two pyridine molecules of solvation. The aromatic rings in the first two complexes adopt 'paddle wheel' conformations with pitch angles varying between 40 and 70�. The nitrite ions are positioned so as to minimize repulsive interactions with the amines, and it seems likely that these groups bond through oxygen rather than nitrogen because this allows a lesser degree of interligand steric interference. The amine rings in [Ni(prz)4(ONO)2] are orthogonal to the plane containing the nickel and coordinated pyrazole nitrogen atoms; the nitrito groups are disordered between two inequivalent positions, each of which involves hydrogen bonding with the pyrazole NH groups. The nitrite infrared frequencies are similar to those observed for other nickel(II) nitrito complexes except that the antisymmetric NO stretching mode of one of the groups in the pyrazole complex is much lower in energy than expected, being in the range normally associated with a nitrogen-bonded or chelated nitrite group. It is suggested that this deviation may be caused by the hydrogen bonding in the complex. The electronic spectra of the compounds yield 10Dq values of 9100 and 8500 cm-1 for the nitrite ligands in [Ni(py)4(ONO)2] and Ni(prz)4(ONO)2], respectively, placing the nitrito group towards the weaker end of the spectro-chemical series.

Structural and spectroscopic studies of transition metal nitrite complexes. VIII. Crystal structures and spectra of three pentanuclear species with stoichiometry [Ni5(N-substituted ethane-1,2-diamine)4(OH)2(NO2)8]

1981 ◽  
Vol 34 (10) ◽  
pp. 2139 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
General Formula ◽  
Infrared Spectra ◽  
Spectroscopic Studies ◽  
Molecular Structures ◽  
Structural Variations ◽  
Crystal And Molecular Structures

The preparation of a series of novel compounds of general formula [Ni5L4(NO2)8(OH)2] formed by ethane-1,2-diamine or one of five N-substituted ethane-1,2-diamines (L) is described. The crystal and molecular structures of the ethane-1,2-diamine, N,N'-diethylethane-1,2-diamine and N,N-dimethylethane-1,2-diamine complexes are reported. Each compound contains a planar, pentameric arrangement of nickel(II) ions, linked by bridging hydroxide and nitrite ligands. The details of the nitrite bridges differ among the complexes, causing differences in their electronic and infrared spectra. The structural variations are probably caused by the differing steric requirements of the amine substituents.

Reaktionen von Oxo-Rhenium(VII und V)-Verbindungen mit Thiobenzoylhydrazin. Kristall- und Molekülstrukturen von Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 und [Re(NHNC(S)Ph)(NHNHC(S)Ph)2]Cl · 1/3 C2H5OH · 1/3 H2O / Reactions of Oxorhenium(VII and V) Complexes with Thiobenzoylhydrazine. Crystal and Molecular Structures of Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 and [Re(NHNC(S)Ph)(NHNHC(S)Ph)2]Cl · 1/3 C2H5OH · 1/3 H2O

1990 ◽  
Vol 45 (8) ◽  
pp. 1167-1176 ◽  
Author(s):  
Alfons Möhlenkamp ◽  
Rainer Mattes
Keyword(s):  
Unit Cell ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Chelating Ligands ◽  
Rhenium Atom ◽  
Coordination Polyhedra ◽  
Space Group ◽  
Crystal And Molecular Structures ◽  
Ligand Structure

The reaction of NaReO4 with thiobenzoylhydrazine yields Re(NHNC(S)Ph)3- DMF (1). With ReOCl3(PPh3)2 thiobenzoylhydrazine reacts to give Re(NHNC(S)Ph)3 · OPPh3 (2) and in the presence of HCl to yield [Re(NHNC(S)Ph)(NHNHC(S)Ph),]Cl · 1/3 C2H5OH -1 /3 H2O (3). The structures of 1-3 have been determined. 1: monoclinic, space group P2,/c, a = 1150.1(9), b = 2050.0(9), c = 1181.0(8) pm, β = 109.62(5)°, Z = 4, 2980 reflections, R = 0.055; 2: trigonal, space group R 3, a = 1399.8(1), c = 1684.0(1) pm, Z = 3, 1419 reflections, R = 0.033; 3: monoclinic, space group P2,/c, a = 1446.8(3), b = 3220.7(5), c = 1727.1(4) pm, β = 108.42(2)°, Z = 12, 6112 reflections, R = 0.062. In 1 and 2 three N,S-chelating ligands NHNR (R = C(S)Ph) are coordinated to the central rhenium atom. The ligand structure is intermediate between a diazene and a hydrazido(2–) structure. In 3 each rhenium atom is coordinated by one NHNR and two NHNHR ligands, all N,S-chelating. The latter can be considered as protonated diazene ligands. The unit cell contains three isomeric coordination polyhedra.

Isopoly- und Heteropoly-Thioanionen. Kristall- und Molekülstrukturen von (PPh4)2[(WS4)WS(WS4)],CS2[(WS4)WO(WS4)H2O]·2H2O und (AsPh4)2[(WS4)Ni(WS4)]/Isopoly- and Heteropoly-Thioanions. Crystal and Molecular Structures of (PPh4)2[(WS4)WS(WS4)], Cs2[(WS4)WO(WS4)H2O] · 2 H2O and (AsPh4)2[(WS4)Ni(WS4)]

1982 ◽  
Vol 37 (8) ◽  
pp. 1014-1019 ◽  
Author(s):  
Achim Müller ◽  
Hartmut Bögge ◽  
Erich Krickemeyer ◽  
Gerald Henkel ◽  
Bernt Krebs
Keyword(s):  
Transition Metal ◽  
Coordination Compounds ◽  
Molecular Structures ◽  
Crystal And Molecular Structures

The crystal and molecular structures of (PPh4)2[(WS4)WS(WS4)] (1a) and CS2[(WS4)WO(WS4)H2O] · 2 H2O (2a), which contain the first reported isopoly-thioanion of a transition metal have been determined: 1a: (P1̅, a = 913.0(1), b = 1060.1(2), c = 1333.9(2) pm, α = 87.11(1), β = 85.18(1), γ = 83.07(1)°, V = 1277.6 · 106 pm3, Z = 1); 2a: (P21/n, a = 671.6(2), b = 2018.5(4), c = 714.4(2) pm, β = 101.42(2)°, V = 949,3 · 106 pm3, Z = 2) and compared with that of the trimetallic heteropoly-thioanion of(AsPh4)2[(WS4)Ni(WS4)] (3a). 3a: (P1̄, a = 1255.2(3), b = 1277.1(3), c = 939.0(2) pm, α = 113.19(2), β = 96.28(2), γ = 108.72(2)°, V = 1261.5 · 106 pm3, Z = 1). Though there are delocalized orbitals in the isopoly-thioanions they can be regarded as coordination compounds of WIVX2+ containing two WVIS42- ligands.

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