Steric Influences on the Ground State of Iron(II) in the Tris(3,3'-dimethyl-2,2'-bipyridine)Iron(II) Ion

1988 ◽  
Vol 41 (8) ◽  
pp. 1157 ◽  
Author(s):  
DC Craig ◽  
HA Goodwin ◽  
D Onggo
Keyword(s):  
Spin Transition ◽  
Spectroscopic Properties ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Complex Ions ◽  
Temperature Dependent ◽  
Ligand Complex ◽  
Metal Atoms ◽  
Donor Nitrogen ◽  
Complex Salts

The tris ( ligand ) complex ions of iron(II) and nickel(II) with 3,3′-dimethyl-2,2′-bipyridine (L) are described. Salts of [FeL3]2+ display anomalously temperature-dependent magnetic and spectroscopic properties which arise from a temperature-induced singlet (1A1) ↔ quintet (5T2) spin transition. The structures of [ML3][ClO4]2(M = Fe, Ni) have been determined and these reveal a strong twist (c. 37°) of the pyridine rings about the C-C bridge. This forces the metal atoms out of the bonding planes of the donor nitrogen atoms and effectively reduces the interaction between L and the metal atoms. The average M-N distances are 2.064 Ǻ (M = Fe) and 2.102 Ǻ (M = Ni). Crystal data: the two complex salts are isostructural in monoclinic space group C2/c. [FeL3][ClO4]2: a 12.252(8), b 15.568(5), c 19.288(11) Ǻ, β 93.62(3)°; Z 4; [NiL3][ClO4]2: a 12.255(5), b 15.619(4), c 19.419(9) Ǻ, β 93.23(2); Z 4.

Coordination of Hydrazone Derivatives of 2,2'-Bipyridine-6-carbaldehyde. Electronic and Structural Aspects of the Iron(II), Cobalt(II) and Nickel(II) Complexes

1991 ◽  
Vol 44 (3) ◽  
pp. 331 ◽  
Author(s):  
D Onggo ◽  
DC Craig ◽  
AD Rae ◽  
HA Goodwin
Keyword(s):  
Metal Atom ◽  
Magnetic Moments ◽  
Spin Transition ◽  
Azomethine Nitrogen ◽  
Ligand Molecule ◽  
Monoclinic Space Group ◽  
Temperature Dependent ◽  
Thermally Induced ◽  
Derivatives Of ◽  
Structural Aspects

Iron(II), cobalt(II) and nickel(II) [MN6]2+ type complexes of the tridentate terimine ligands 2,2′-bipyridine-6-carbaldehyde phenylhydrazone ( bph ) and 2,2′-bipyridine-6-carbaldehyde 2-pyridylhydrazone ( bpyh ) have been prepared. The electronic spectrum of the [NiN6]2+ species indicates that the field strength of these ligands is near that at the iron(II) singlet/quintet crossover. Magnetic and Mossbauer spectral data reveal that salts of [Fe( bph )2]2+ are essentially low spin, while those of [Fe( bpyh )2]2+ are high spin. Salts of [Co( bph )2]2+ have strongly temperature-dependent magnetic moments which indicate a thermally induced doublet ↔ quartet spin transition in the metal atom. The structure of [Ni( bph )2][ClO4]2 reveals meridional coordination of the tridentate units, the azomethine nitrogen of the hydrazone moiety being bound to the metal atom. There is significant twisting (8.3°) of the two pyridyl rings in each ligand molecule about the interring bridge. The [NiN6]2+ fragment is tetragonally compressed and the mean Ni-N distance is 2.09 Ǻ. [Ni( bph )2][ClO4]2 is monoclinic, space group C2/c, Z = 4, a 23.949(3), b 7.868(1), c 21.303(3)Ǻ, β 117.95(2)°.

[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

1992 ◽  
Vol 47 (11) ◽  
pp. 1580-1592 ◽  
Author(s):  
Wolfgang Tremel ◽  
Bernt Krebs ◽  
Klaus Greiwe ◽  
Wolfgang Simon ◽  
Hans-Oscar Stephan ◽  
...  
Keyword(s):  
Type Species ◽  
Nmr Spectra ◽  
Molar Ratio ◽  
Monoclinic Space Group ◽  
Tetrahedral Coordination ◽  
Crystal Data ◽  
Space Group ◽  
H Nmr ◽  
Metal Atoms ◽  
Distorted Tetrahedral Coordination

The reactions of 1:1:1 molar ratio mixtures of NaSPh/MnCl2/Et4NBr and NaSPh/CoCl2/ Et4NCl in methanol afford the compounds [Et4N]4[Mn(SPh)3Br][Mn(SPh)3Cl] (1) and [Et4N]2[Co4(SPh)6Cl4] · MeCN (2), respectively, with the following crystal data: a = 14.408(5), b = 13.788(4), c = 17.984(5) Å, β = 90.16(2)°, space group P21/c and Ζ = 4 for 1, and a = 21.976(4), b = 13.081(2), c = 22.012(4) Å, β = 105.48(1)°, space group P 21/c for 2. The structures were refined to R values of 0.049 and 0.037, respectively. Crystals of 1 contain both of the paramagnetic (S = 5/2) mononuclear anions [Mn(SPh)3Br]2- (3 a) and [Mn(SPh)3Cl]2- (3b). The anions 3 a and 3 b are superimposed in an averaged unit cell and thus occupy crystallographically equivalent sites, the positions of the chlorine and bromine atoms being unresolved. The monohalide species are distributed statistically over 93% of the total anion positions. The remaining 7% are occupied by the dihalide species [Mn(SPh)2Br2]2- (4a) and [Mn(SPh)2BrCl]2- (4b) in equal amounts. In all these cases the metal atoms exhibit a distorted tetrahedral stereochemistry. In crystals of 2 [Co4(SPh)6Cl4]2- anions (5) are observed which feature a {Co4S6Cl4} core consisting of a distorted (D2d) Co4 tetrahedron inscribed in a moderately irregular S6 octahedron defined by bridging S atoms of an adamantane type cage. The four chlorine atoms each bind to different Co atoms and define an outer Cl4 tetrahedron, such that the overall symmetry of the {Co4S6Cl4} core comes close to Td. The results presented show that [M3(SPh)3Hal6]3- type species reported for M = Fe are not as readily formed for M = Mn and Co in methanolic solution, where other species are found instead. Physical properties such as solid state susceptibilities and 1H NMR spectra confirm the identity of 1 and 2. Reactions of 4:1:2 molar ratio mixtures of NaSePh/MnCl2/Et4NCl and NaTePh/MnCl2/Et4NCl in methanol lead to [Et4N]2[Mn(SePh)4] (6) and [Et4N]2[Mn(TePh)4] (7). Both compounds crystallize in the monoclinic space group P21/n with a = 16.162(4), b = 15.323(4), c = 16.949(4) Å, β = 91.28(2)°, Z = 4 for 6, and a = 16.367(6), b = 15.641(7), c = 17.220(7) Å, β = 92.00(3)°, Z = 4 for 7. Their structures were refined to R = 0.077 and 0.026, respectively. Four benzeneselenolate and benzenetellurolate ligands provide a slightly distorted tetrahedral coordination about the Mn(II) center for 6 and 7, respectively. The Mn–Se and Mn–Te distances average 2.567 and 2.742 Å, the Se– Mn– Se and Te–Mn–Te angles range from 99.1(1) to 124.2(1) and from 94.7(1) to 127.0(1)°, respectively.

scholarly journals Characterization of the mixed axial ligand complex (4-cyanopyridine)(imidazole)(tetramesitylporphinato)iron(iii) perchlorate. Stabilization by synergic bonding

2016 ◽  
Vol 20 (01n04) ◽  
pp. 254-264 ◽  
Author(s):  
Judith A. Serth-Guzzo ◽  
Ilona Turowska-Tyrk ◽  
Martin K. Safo ◽  
F. Ann Walker ◽  
Peter G. Debrunner ◽  
...  
Keyword(s):  
Quadrupole Doublet ◽  
Axial Ligand ◽  
Mixed Ligand ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Ligand Complex ◽  
Epr Spectrum ◽  
Space Group ◽  
Axial Ligands

The reaction of [Fe(TMP)(OClO[Formula: see text]], where TMP is the dianion of tetramesitylporphyrin, with a combination of a strong [Formula: see text]-acceptor ligand and a [Formula: see text]-donating imidazole can lead to the preparation of mixed-ligand complexes [Fe(Porph)(4-CNPy)(L)][Formula: see text] where L is imidazole itself or 1-acetylimidazole and 4-cyanopyridine is the strong [Formula: see text] acceptor ligand. The stability of the new mixed-ligand pair is the presumed result of synergic bonding between the two axial ligands. The molecular structure and other characterization of the new mixed axial ligand complex, [Fe(TMP)(4-CNPy)(HIm)]ClO4 is described. The axial ligands have a relative perpendicular arrangement with Fe–N(imidazole) = 1.945 Å and Fe–N(pyridine) = 2.021 Å. The average equatorial Fe–N[Formula: see text] distance is 1.963 Å, which is consistent with the S4-ruffled TMP core. Despite the relative perpendicular arrangement of axial ligands, the EPR spectrum of the complex is a rhombic signal and not a large gmax signal. The EPR g-values are [Formula: see text] 3.05, [Formula: see text] 2.07, and [Formula: see text] 1.22. A quadrupole doublet was seen in the Mössbauer spectrum with an isomer shift of 0.197 mm/s and quadrupole splitting of 1.935 mm/s. Two crystalline forms of [Fe(TMP)(4-CNPy)(HIm)]ClO4 have been characterized; the two forms differ only in the solvent content of the lattice. Crystal data for form A: [Formula: see text] 15.432 (12) Å, [Formula: see text] 20.696 (2) Å, [Formula: see text] 19.970 (5) Å, and [Formula: see text] 99.256 (14)[Formula: see text], monoclinic, space group P21/n, V [Formula: see text] 6295 (2) Å3, Z [Formula: see text] 4, formula FeCl3O4N8C[Formula: see text]H[Formula: see text], 8397 observed data, [Formula: see text] 0.086, [Formula: see text] 0.210, refinement on [Formula: see text]. Crystal data for form B: [Formula: see text]15.267 (3) Å, [Formula: see text]20.377 (6) Å, [Formula: see text] 19.670 (4) Å, and [Formula: see text] 98.14 (1)[Formula: see text], monoclinic, space group P[Formula: see text]/n, V = 6058 (4) Å3, Z = 4, formula C[Formula: see text]H[Formula: see text]Cl[Formula: see text]FeN8O4, 5464 observed data, [Formula: see text] 0.096, [Formula: see text] 0.112, refinement on F.

scholarly journals Molekül- und Kristallstruktur von 1.1-Dimethylsilylentitanocendichlorid, (CH3)2Si(C5H4)2TiCl2 / Molecular and Crystal Structure of l,r-Dimethylsilylene Titanocene Dichloride, (CH3)2Si(C5H4)2TiCl2

1981 ◽  
Vol 36 (10) ◽  
pp. 1208-1210 ◽  
Author(s):  
Hartmut Köpf ◽  
Joachim Pickardt
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Structure Determination ◽  
Titanocene Dichloride ◽  
Molecular And Crystal Structure ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Space Group ◽  
X Ray ◽  
Structural Dimensions

Abstract The molecular structure of the bridged [1]-titanocenophane 1,1'-dimethylsilylene titanocene dichloride, (CH3)2Si(C5H4)2TiCl2, has been investigated by an X-ray structure determination. Crystal data: monoclinic, space group C2/c, Z = 4, a = 1332.9(3), 6 = 988.7(3), c = 1068.9(3) pm, β = 113.43(2)°. The results are compared with the structural dimensions of similar compounds: 1,1'-methylene titanocene dichloride, CH2(C5H4)TiCl2, with the unbridged titanocene dichloride, (C5H5)2TiCl2 and the ethylene-bridged compound (CH2)2(C5H4)2TiCl2

Strukturuntersuchungen an Diaryldichalkogeniden: Die Molekülstrukturen von [2,4,6-(CF3)3C6H2S]2,[2,4,6-Me3C6H2Te]2 und [2-Me2N-4,6-(CF3)2C6H2Te]2 / Structural Investigations of Diaryl Dichalcogenides: The Molecular Structures of [2,4,6-(CF3)3C6H2S]2, [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2

1992 ◽  
Vol 47 (3) ◽  
pp. 305-309 ◽  
Author(s):  
Anja Edelmann ◽  
Sally Brooker ◽  
Norbert Bertel ◽  
Mathias Noltemeyer ◽  
Herbert W. Roesky ◽  
...  
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Structural Investigations ◽  
Space Group ◽  
X Ray

Abstract The Molecular Structures of [2,4,6-(CF3)3C6H2S]2 (1) [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2 (3) have been determined by X-ray diffraction. Crystal data: 1: orthorhombic, space group P212121, Z = 4, a = 822.3(2), b = 1029.2(2), c = 2526.6(5) pm (2343 observed independent reflexions, R = 0.042); 2: orthorhombic, space group Iba 2, Z = 8, a = 1546.5(2), b = 1578.4(2), c = 1483.9(1) pm (2051 observed independent reflexions, R = 0.030); 3: monoclinic, space group P 21/c, Z = 4, a = 1118.7(1), b = 1536.5(2), c = 1492.6(2) pm, β = 98.97(1)° (3033 observed independent reflexions, R = 0.025).

Strukturen der mehrkernigen nickelthiolato-komplexe [(μ-SMe)2(Ni(MeNHCS2))2] und cyclo-[(μ-SMe)2Ni]6 / Structures of Two Polynuclear Nickel-Thiolato-Complexes [(μ-SMe)2(Ni(MeNHCS2))2] and cyclo-[(μ-SMe)2Ni]6

1994 ◽  
Vol 49 (6) ◽  
pp. 770-772 ◽  
Author(s):  
Klaus Schulbert ◽  
Rainer Mattes
Keyword(s):  
Crystal Structures ◽  
Nickel Acetate ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Dithiocarbamic Acid ◽  
Coordination Spheres ◽  
Partial Degradation ◽  
Acid Esters

The reactions of N-substituted dithiocarbamic acid esters and nickel acetate yield, by partial degradation of the esters, the polynuclear nickel thiolato complexes cyclo-[(μ-SMe)2Ni]6, 1 and [(μ-SMe)2(Ni(MeNHCS2))2, 2. Their crystal structures have been determined. The Ni coordination spheres are comprised of four sulfur atoms in a planar arrangement. 1 is a second, highly symmetrical modification of the already known cyclic hexamer Ni6(SMe)12. In 2 two Ni(PhNHCS2) moieties are bridged to dimers by thiolato groups. Two of these dimers are connected to a tetramer by weak axial Ni-S interactions. Crystal data for 1: monoclinic, space group P21/n, a = 986.1(2), b = 1308.1(3), c = 1228.6(2) pm, β = 96.07(3)°, Z = 2, R = 0.072, Rw = 0.062, 3797 reflections. 2: orthorhombic, space group Pnma, a = 1790.0(4), b = 1806.7(4), c = 934.4(2) pm. Z = 4, R = 0.061, Rw = 0.051, 2079 reflections

Structural and Electronic Properties of the Iron(II) and Nickel(II) Bis(ligand) Complexes of 6-(5-Methyl-1,2,4-oxadiazol-3-yl)-2,2′-bipyridine— a Terpyridine-Based Tridentate

1999 ◽  
Vol 52 (7) ◽  
pp. 673 ◽  
Author(s):  
Bradley J. Childs ◽  
Marcia L. Scudder ◽  
Donald C. Craig ◽  
Harold A. Goodwin
Keyword(s):  
Electronic Properties ◽  
Spectroscopic Data ◽  
Room Temperature ◽  
Spin Transition ◽  
Iron Complex ◽  
Ligand Field ◽  
Monoclinic Space Group ◽  
Space Group ◽  
C 23 ◽  
Structural And Electronic Properties

Iron(II) and nickel(II) bis(ligand) complexes of 6-(5-methyl-1,2,4-oxadiazol-3-yl)-2,2′-bipyridine (L) are described. The ligand field in the iron complex is close to that at the singlet ( 1 A1) ? quintet ( 5 T2) crossover and magnetic and Mössbauer spectral evidence indicates that a spin transition occurs in salts of the iron complex but is centred above room temperature. The structures of [FeL2] [CF3SO3]2.CH3CN and [NiL2] [BF4]2.CH3CN were determined and both are very similar to the structures of the corresponding terpyridine complexes. Spectroscopic data indicate that for the iron complex π-interaction between the metal and the ligand is less than that in the terpyridine system. [FeL2] [CF3SO3]2.CH3CN is monoclinic, space group P 21/c; a 8 . 232(5), b 25 . 273(10), c 17 . 306(10) Å, β 92 . 37(3)°, Z 4; [NiL2] [BF4]2.CH3CN is monoclinic, space group P 21/c; a 8 . 136(2), b 17 . 558(2), c 23 . 783(7) Å, β 109 . 32(1)°, Z 4.

scholarly journals The Isomorphous Structures of Ammonium trans-Diiodobis(ethanedial-dioximato-(1–)-N,N′)cobaltate(III) and Ammonium trans-Diiodobis(ethanedial-dioximato-(1–)-N,N′)rhodate(III): Extended Metaloximate Chains with a Novel ···I–M–I···I–M–I··· Zigzagged Structure

1990 ◽  
Vol 45 (11) ◽  
pp. 1508-1512 ◽  
Author(s):  
Michel Mégnamisi-Bélombé ◽  
Bernhard Nuber
Keyword(s):  
Room Temperature ◽  
Ammonium Salts ◽  
Monoclinic Space Group ◽  
Hydroxyl Groups ◽  
Coordination Geometry ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
X Ray ◽  
Anionic Complexes ◽  
Complex Anions

The ammonium salts of the complex anions trans-diiodobis(ethanedial-dioximato)-cobaltate(III), [Col2(GH)2]-, and trans-diiodobis(ethanedial-dioximato)rhodate(III), [RhI2(GH)2]- (GH- = ethanedial dioximate or glyoximate), have been synthesized and their structures determined from single crystal X-ray diffraction data at room temperature. The crystals of the two salts are monoclinic, space group C2/c. NH4[CoI2(GH)2] (I) crystallizes as dark-brown prisms with a greenish reflectance; its crystal data are: C4H10Col2N5O4, Mr = 504.90; a = 8.910(6), b = 11.700(9), c = 11.691(6) Å; β = 93.55(5)°; V = 1216.4 Å3; Z = 4; Dc = 2.78 Mg m-3. NH4[RhI2(GH)2] (II) crystallizes as yellow-brown blocks with crystal data: C4H10I2N5O4Rh, Mr = 548.88; a = 9.038(4), b = 11.949(5), c = 11.770(3) Å; β = 95.54(3)°; V = 1265.16 A3; Z = 4; Dc = 2.87 Mg m-3. The two structures were refined to a final RW = 0.045 for 1209 observed independent reflections and 95 parameters for I, and to a final RW = 0.040 for 1922 observed independent reflections and 87 parameters for II. The coordination geometry around Co or Rh in the anionic complexes is a distorted (4 + 2) octahedron of four equatorial chelating N atoms and two apical iodides. The H atoms of the hydroxyl groups are involved, as usual, in intramolecular O—H—O bridges with uniform Ο···Ο separations of 2.582 Å for I, and 2.713 Å for II. The rectilinear I—Co—I or I—Rh—I triads form “infinite” zigzag chains extending parallel to the ab plane, with a weak I—I contact of 3.988 Å for I, and 4.010 Å for II.

Magneto-structural correlation of cyano-substituted 3-tert-butyl-1-phenyl-1,2,4-benzotriazin-4-yl: spin transition behaviour observed in a 6-cyano derivative

2018 ◽  
Vol 42 (12) ◽  
pp. 9949-9955 ◽  
Author(s):  
Yusuke Takahashi ◽  
Naoya Tsuchiya ◽  
Youhei Miura ◽  
Naoki Yoshioka
Keyword(s):  
Spin Transition ◽  
Spectroscopic Properties ◽  
Tert Butyl ◽  
Structural Correlation ◽  
Transition Behaviour

New cyano-substituted 3-tert-butylbenzotriazinyls, 7CN and 6CN, were synthesized and their spectroscopic properties and magneto-structural correlation were investigated.

Structure and Fluorescence Properties of a Novel Supramolecular Zinc Complex

2008 ◽  
Vol 63 (12) ◽  
pp. 1357-1360 ◽  
Author(s):  
Gang Chen
Keyword(s):  
Hydrothermal Reaction ◽  
Three Dimensional ◽  
Free Ligand ◽  
Distorted Octahedral Geometry ◽  
Monoclinic Space Group ◽  
Ligand Complex ◽  
Complex Molecules ◽  
Hydrogen Bonding Interactions ◽  
Distorted Octahedral ◽  
Cell Dimensions

Hydrothermal reaction of Zn(NO3)2 · 6H2O and 2-hydroxypyridine-3-carboxylic acid afforded a novel supramolecular complex, [Zn(C6H4NO3)2(H2O)2] (1). The complex has been characterized by macroanalysis, IR spectra, and thermogravimetric and differential thermal analysis (TG/DTA). Single crystal X-ray analysis shows that complex 1 crystallizes in the monoclinic space group P21/c with the cell dimensions a = 7.534(6), b = 12.289(1), c = 7.534(6) Å, β = 100.51°, V = 685.85(1) Å3, and Z = 2. The six-coordinated Zn atom is in a severely distorted octahedral geometry. The complex molecules are assembled via strong O-H· · ·O and N-H· · ·O hydrogen bonding interactions into a three-dimensional supramolecular framework. Compared with the free ligand, complex 1 exhibits strong fluorescence in the solid state at room temperature.

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