Structural and spectroscopic studies of transition metal nitrite complexes. I. Crystal structures and spectra of trans-Bis(ethane- 1,2 diamine)dinitronickel(II), trans-Bis[N, N-dimethyl(ethane- 1,2-diamine)]dinitritonickel(II) and trans-bis[N,N'-dimethyl(ethane-1,2 diamine)]dinitronickel(II) monohydrate

1981 ◽  
Vol 34 (10) ◽  
pp. 2047 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
Spectroscopic Properties ◽  
Spectroscopic Studies ◽  
Chelate Rings

The crystal structures of the trans complexes bis(ethane-1,2-diamine)dinitronickel(II) (1), bis[N,N-dimethyl(ethane-1,2-diarnine)]dinitritonickel(II) (2) and bis[N,N'-dimethyl(ethane-1,2-diamine)]dinitronickel(II) monohydrate (3) are described, (1) and (2) being redeterminations of previously reported structures. The complexes formed by the substituted amines have significantly different geometries, both in the manner of coordination of the nitrite ligands, and in the conformations adopted by the diamine chelate rings. These differences can be explained in terms of the particular steric requirements of the amine substituents. The changes in nitrite geometry which occur upon coordination, and the spectroscopic properties of the complexes are discussed.

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.

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. VI. Crystal structures and spectra of Hexakis(imidazole)nickel(II) dinitrate, trans-Tetrakis(2-methylimidazole)dinitritonickel(II) and cis-Tetrakis(2-methylimidazole)-(nitrito-O,O')nickel(II) nitrate-methanol (2/1)

1981 ◽  
Vol 34 (10) ◽  
pp. 2113 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Crystal Structures ◽  
Symmetry Axis ◽  
Spectroscopic Properties ◽  
Spectroscopic Studies ◽  
Ligand Field ◽  
Coordination Geometry ◽  
Distorted Octahedral ◽  
Relative Field ◽  
Ligand Coordination ◽  
Fourfold Symmetry

The crystal structures and spectroscopic properties of the complexes cis-tetrakis(2-methy1imidazole)-(nitrito-O,O')nickel(II) nitrate-methanol (2/1) and trans-tetrakis(2-methylimidazole)dinitritonickel(II) are reported. The nitrite group in the former compound chelates, giving a distorted octahedral ligand coordination geometry. The ligand stereochemistry in the second complex is also a distorted octahedron, with both anions coordinating as trans nitrito groups though with significantly different Ni-O bond lengths and the nickel(II) ion being raised out of the plane of the four imidazole ligand nitrogen atoms towards the closer nitrite group. The Ni-O bond directions also deviate substantially from the fourfold symmetry axis in this latter complex. These distortions apparently occur in order to minimize ligand-ligand repulsions, particularly those associated with the amine methyl substituents. The electronic spectra of both complexes show significant band splittings due to the departure of the ligand field from regular octahedral symmetry and these are discussed in terms of the relative field strengths of the imidazole and nitrito ligands. The structure of hexakis(imidazole)nickel(II) nitrate (redetermination) is also reported.

Synthesis, Crystal Structures, and Thermal and Spectroscopic Properties of Thiocyanato Coordination Compounds with 3-Acetylpyridine as a Ligand

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1419-1428
Author(s):  
Julia Werner ◽  
Inke Jeß ◽  
Christian Näther
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
Coordination Polymers ◽  
Coordination Compounds ◽  
Spectroscopic Properties ◽  
Second Step ◽  
Crystalline Phases ◽  
Thermogravimetric Investigations ◽  
New Compounds ◽  
Ir Spectroscopic

Abstract The reaction of transition metal thiocyanates with 3-acetylpyridine (3-Acpy) leads to the formation of compounds of compositions M(NCS)2(3-Acpy)4 (M1; M = Mn, Fe, Ni) and M(NCS)2(3- Acpy)2(H2O)2 (M2; M = Mn, Fe, Ni). Thermogravimetric investigations show that in the first step some of these compounds transform into the new coordination polymers M(NCS)2(3-Acpy)2 (M3 with M = Mn, Fe and Ni), that decompose into the new compounds M(NCS)2(3-Acpy) (M4 with M = Mn and Ni) in the second step. Unfortunately, the powder patterns of compounds M3 and M4 cannot be indexed, and there are strong indications that these compounds are contaminated with a small amount of the precursor or unknown crystalline phases. IR spectroscopic investigations indicate that in compounds M3 the metal cations are linked by μ-1,3-bridging thiocyanato anions into 1D or 2D coordination polymers that are further linked by the 3-Acpy ligands in compounds M4.

Structural and spectroscopic studies of transition metal nitrite complexes. X. Crystal structures of cis-Bis(2,2'-bipyridine)(nitrito-O,O')nickel(II) nitrate and hydrated Tris(2,2'-bipyridine)nickel(II) nitrite/nitrate and sulfate. Stereochemistry of the [M(bidentate ligand)2(bidentate ligand')1] system

1981 ◽  
Vol 34 (10) ◽  
pp. 2177 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
DL Kepert ◽  
CL Raston ◽  
GL Rowbottom ◽  
...  
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
Coordination Sphere ◽  
Nickel Atom ◽  
Spectroscopic Studies ◽  
Bidentate Ligand ◽  
The Other ◽  
Bidentate Ligands ◽  
Nitrite Nitrate ◽  
Oxygen Atoms

The crystal structures of the title compounds are reported. In all cases, the coordination sphere of the nickel atom comprises three bidentate ligands. In (1), [Ni(bpy)2(O2N)] NO3, (Ni-N) is 2.M2 � although there are small differences between those nitrogen atoms trans to the nitrite oxygen atoms and the other two. (Ni-O) is 2.12 �. In (2), [Ni(bpy)3] NO2/NO3,xH2O, and (3), [Ni(bpy)3]- SO4,7.5H2O, a redetermination, Ni-N is shown to be c. 2.09 �; serious disorder is present among the non-cationic components of (2), precluding a definite assignment of stoichiometry.

155Gd Mössbauer Spectroscopic Study of GdM(CN)6 · 4H2O (M = CrIII, FeIII and CoIII) and KGdM(CN)6 · 3H2O (M = FeII and RuII)

2002 ◽  
Vol 57 (6-7) ◽  
pp. 581-585 ◽  
Author(s):  
Junhu Wang ◽  
Junko Abe ◽  
Takafumi Kitazawa ◽  
Masashi Takahashi ◽  
Masuo Takeda
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Spectroscopic Study ◽  
Crystal Structures ◽  
Transition Metal Ions ◽  
Spectroscopic Studies ◽  
Coupling Constants ◽  
Orthorhombic Distortion ◽  
Ionic Radii ◽  
Quadrupole Coupling

155Gd Mössbauer spectroscopic studies of the title complexes have been performed. Although the 155Gd isomer shifts (d) varied scarcely, the quadrupole coupling constants (e2qQ) changed in the range 4.07-4.81 mm s-1. The e2qQ values of KGdM(CN)6 · 3H2O (M = FeII and RuII) are larger than those of GdM(CN)6 · 4H2O (M = CrIII, FeIII, and CoIII), these values increasing with increasing orthorhombic distortion of the crystal structures. A relationship between the e2qQ values and the ionic radii of the transition metal ions has also been recognized

Structural and spectroscopic studies of transition metal nitrite complexes. II. Crystal structures of cis-Bis(ethane-1,2-diamine)(nitrito-O,O')zinc(II) nitrite and trans-Bis[N,N-dimethyl(ethane-1,2-diamine)]dinitritozinc(II)

1981 ◽  
Vol 34 (10) ◽  
pp. 2061 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Crystal Structures ◽  
Coordination Polyhedron ◽  
Metal Ion ◽  
Spectroscopic Studies ◽  
Bond Lengths ◽  
Coordination Sites ◽  
Metal Ligand ◽  
Ligand Bond

The crystal structures of the complexes cis-bis(ethane-1,2-diamine)(nitrito-O,O')zinc(II) nitrite and trans-bis[N,N-dimethyl(ethane-l,2-diamine)]dinitritozinc(II) are described. The former compound contains one chelating nitrite, the second group being present as a counter ion. In this complex the coordination polyhedron about the metal ion may be described either as a distorted trigonal bi-pyramid or an octahedron, depending upon whether the chelated nitrite is considered to occupy one or two coordination sites. The second compound is a trans nitrito complex, having an octahedral ligand geometry, though with three markedly different metal-ligand bond lengths. The structures of the complexes are compared with those of analogous nickel(II) nitrite complexes, and the differences are discussed in terms of the electron configurations of the two metal ions.

Sign in / Sign up

Export Citation Format

Share Document