Coordination compounds containing a novel tridentate pyrazolylgallate ligand. X-ray structures of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz and [Me2Ga(pz)(OCH2pz)]2Ni (pz = N2C3H3)

1988 ◽  
Vol 66 (1) ◽  
pp. 101-108 ◽  
Author(s):  
Arthur Mar ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal Complexes ◽  
Heavy Atom ◽  
Direct Reaction ◽  
Coordination Geometry ◽  
The Novel ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Normal Bond ◽  
Cis Isomer

The syntheses of the novel anionic tridentate dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallate ligand and representative transition metal complexes thereof are reported. The direct reaction of Me3Ga with 1-hydroxymethyl-3,5-dimethylpyrazole leads to the isolation of Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz. Crystals of (μ-hydroxy)(μ-3,5-dimethylpyrazolyl)bis(dimethylgallium) 1-hydroxymethyl-3,5-dimethylpyrazole solvate are monoclinic, a = 33.105(2), b = 7.3048(7), c = 8.8336(6) Å, β = 97.474(7)°, Z = 4, space group P21/n, and those of bis[dimethyl(pyrazol-1-yl)(1-oxymethylpyrazolyl)gallato-N2,N2′,O]nickel(II) are monoclinic, a = 9.6345(3), b = 14.2731(6), c = 18.6356(7) Å, β = 99,660(3)°, Z = 4, space group P21/c. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.044 and 0.037 for 2660 and 3904 reflections with I ≥ 3σ(I), respectively. Mean bond lengths in Me2Ga(μ-OH)(μ-Me2pz)GaMe2•HOCH2Me2pz are Ga—O = 1.918(11), Ga—N = 2.001(5), and Ga—C = 1.955(5) Å. Fac-[Me2Ga(pz)(OCH2pz)]2Ni crystallizes as an all-cis isomer with normal bond lengths and angles at Ga and Ni—O = 1.918(3) and 1.927(3), Ni—N = 2.030(4)–2.111(4) Å. The coordination geometry about Ni is irregular pseudo-octahedral with evidence of both steric and structural trans effects.

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

Crystal and molecular structure of [dimethyl(1-pyrazolyl)(2-pyridyl-methoxy)gallato-N2,O,N3](η3-allyl)dicarbonylinolybdenum(II)

1988 ◽  
Vol 66 (3) ◽  
pp. 355-358 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Nitrogen Atom ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
Pyridyl Nitrogen ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Crystals of [dimethyl(1-pyrazolyl)(2-pyridylmethoxy)gallato-N2,O,N3](η3-allyl)dicarbonylmolybdenum(II) are triclinic, a = 9.632(2), b = 9.798(2), c = 10.255(2) Å, α = 80.16(1), β = 87.38(1), γ = 81.75(1)°, Z = 2, space group [Formula: see text]. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.033 and Rw = 0.037 for 3000 reflections with I ≥ 3σ(I). The molecule has pseudo-octahedral coordination geometry with the tridentate [Me2Ga(N2C3H3)(OCH2(C5H4N))]− ligand facially coordinated and the η3-allyl ligand occupying one coordination site trans to the pyridyl nitrogen atom. Important bond lengths are Mo—O = 2.219(2), Mo—N(py) = 2.212(3), Mo—N(pz) = 2.232(2), Mo—C(allyl) = 2.290(4), 2.189(4), 2.341(4), Mo—CO (trans to O) = 1.928(4), and Mo—CO (trans to N) = 1.952(4) Å.

The Crystal Structure of (2,2′-Bipyridine)(pyrazine)(2,2′:6′,2″-terpyridine)ruthenium(II) Hexafluorophosphate

1996 ◽  
Vol 49 (4) ◽  
pp. 527 ◽  
Author(s):  
PT Gulyas ◽  
TW Hambley ◽  
PA Lay
Keyword(s):  
Crystal Structure ◽  
Monoclinic Space Group ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Steric Strain ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Distorted Octahedral ◽  
Back Bonding

The crystal structure of [ Ru ( terpy )( bpy )( pz )] (PF6)2 has been determined by X-ray diffraction methods and refined to a residual of 0.046 for 1855 independent observed reflections. The crystals are monoclinic, space group P 21/a, a 16.836(7), b 10.778(5), c l9.342(5) Ǻ, β 115.11(3)°. The coordination geometry around the ruthenium(II) ion is distorted octahedral, with the various Ru -N bond lengths indicative of considerable interligand steric strain. The Ru -N pyrazine bond is the longest within the structure, consistent with other evidence that n back-bonding to pyrazine is weak in the complex.

Synthesis and X-ray crystal structure of the novel Mo—Cu complex, (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu−(where pz″ = 3,5-dimethylpyrazolyl, N2C5H7)

1988 ◽  
Vol 66 (9) ◽  
pp. 2194-2199 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
The Novel ◽  
Tetrahedral Coordination ◽  
X Ray ◽  
Carbonyl Ligands ◽  
Cu Complex ◽  
Anionic Ligand ◽  
Average Bond

The novel complex, (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu− (where pz″ = 3,5-dimethylpyrazolyl), has been synthesized by reacting the (HBpz″3)Mo(CO)3− anionic ligand with CuI in the presence of a stoichiometric amount of Ph2PCH2CH2PPh2. Crystals of (Ph2PCH2CH2PPh2)2Cu+[(HBpz″3)Mo(CO)3]2Cu−•3.5C6H6•CH2Cl2 are triclinic, a = 13.421(1), b = 14.931(3), c = 28.523(5) Å, α = 90.41(2), β = 90.19(1), γ = 104.65(1)°, Z = 2, space group [Formula: see text] The structure was solved by heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.047 and Rw = 0.049 for 8779 reflections with I ≥ 3σ(I). The crystal structure consists of (Ph2PCH2CH2PPh2)2Cu+ cations having irregular tetrahedral coordination geometry about the copper atom (Cu—P = 2.263(2)–2.304(2) Å and P—Cu—P = 88.30(7)–134.62(8)°) and novel [(HBpz″3)Mo(CO)3]2Cu− anions having exact Ci and approximate D3d symmetry. The central Cu atom of the anion is bonded to two Mo atoms in a linear fashion and also interacts with six semi-bridging carbonyl ligands, three from each (HBpz″3)Mo(CO)3− ligand. Average bond lengths and angles for the anion are Mo–Cu = 2.565, Mo—C = 1.955, Mo—N = 2.256, Cu—C = 2.309, C—O = 1.174 Å, Mo—C—O = 171.7° and Cu—C—O = 114.7°.

Synthesis, characterization, and X-ray structures of Rh(I) monocarbonyl complexes containing unsymmetric tridentate pyrazolylgallate ligands

1986 ◽  
Vol 64 (3) ◽  
pp. 566-574 ◽  
Author(s):  
David A. Cooper ◽  
Steven J. Rettig ◽  
Alan Storr
Keyword(s):  
Addition Reaction ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
Space Group ◽  
X Ray ◽  
Square Planar ◽  
Text Interaction ◽  
Cl Atom ◽  
Centrosymmetric Dimers ◽  
Oxidative Addition Reaction

The reaction of the [Rh(CO)2Cl]2 dimer with the Na+[Me2Ga(N2C3H3)(OCH2(C5H4N))]− ligand has yielded the planar four-coordinate species [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO), (LRh(CO)), displaying the tridentate gallate ligand in a meridional coordination mode. In addition, a second product, of similar geometry but with one of the Me groups on the Ga replaced by a Cl atom, viz, [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO), has also been isolated and characterized. The former complex undergoes a facile oxidative addition reaction with MeI, the transient six-coordinate Rh(III) species produced being rapidly converted, in a methyl migration step, to the five-coordinate Rh(III) acetyl complex, LRh(COMe)I. Crystals of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) are monoclinic, a = 13.139(2), b = 13.324(2), c = 17.352(2) Å, β = 103.251(7)°, Z = 8, space group I2/a, and those of [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO) are triclinic, a = 8.846(2), b = 12.714(3), c = 7.631(2) Å, α = 93.82(1), β = 113.94(1), γ = 107.99(1)°, Z = 2, space group [Formula: see text] Both structures were solved by conventional heavy-atom methods and were refined by full-matrix least-squares procedures to final R values of 0.029 and 0.048 for 1890 and 1939 reflections with I ≥ 3σ(I), respectively. Both molecules display irregular square planar coordination geometry about Rh with Rh—O = 2.038(3) and 2.048(3), Rh—N(pyrazolyl) = 2.022(4) and 2.025(7), Rh—N(pyridyl) = 2.038(3) and 2.020(6), Rh—CO = 1.778(5) and 1.808(9) Å, respectively, for the two compounds. Molecules of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) form weakly associated, centrosymmetric dimers via an intermolecular [Formula: see text] interaction of 3.5445(7) Å.

Synthesis, characterization, and X-ray structural studies of octahedral transition metal complexes incorporating the novel anionic tridentate ligand, dimethyl(ethanolamino)(1-pyrazolyl)- gallate, [Me2Ga(OCH2CH2NH2)(N2C3H3)]−

1978 ◽  
Vol 56 (9) ◽  
pp. 1212-1221 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Tridentate Ligand ◽  
The Novel ◽  
Structural Studies ◽  
Space Group ◽  
X Ray ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral

Details of the synthesis and physical properties of octahedral transition metal complexes of the tridentate tris chelating ligand [Me2Ga(OCH2CH2NH2)(N2C3H3)]− are given. Crystals of sym-fac-bis[dimethyl(ethanolamino)(1-pyrazolyl)gallato(N(2),O,N]nickel(II) are monoclinic, a = 11.7908(6), b = 7.3158(6), c = 12.5797(8), β = 97.035(7)°, Z = 2, space group P21/n and crystals of the mer isomer are monoclinic, a = 18.6617(7), b = 8.7941(4), c = 13.5670(8), β = 91,766(4)°, Z = 4, space group P21/c. The structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to final R values of 0.048 and 0.052 for 1881 and 2573 reflections with I ≥ 3σ(I) for the fac and mer isomers respectively. The nickel atoms in both structures were found to have distorted octahedral coordination geometry. Bond lengths (corrected for libration) are: Ni—O, 2.090(3); Ni—N, 2.085(3) and 2.112(3); Ga—O, 1.908(3); Ga—N, 2.010(3); and Ga—C, 1.979(5) and 1.981(6) Å for the fac isomer, and Ni—O, 2.045(4) and 2.049(4); Ni—N, 2.091 (4)-2.156(5); Ga—O, 1.898(4) and 1.899(4); Ga—N, two at 1.991 (5); and Ga—C, 1.948(8)-1.971 (7) Å for the mer isomer.

Crystal and molecular structures of three transition metal complexes incorporating the anionic tridentate chelating ligands [Me2Ga(N2C5H7)OCH2CH2SR]− where R = Et or Ph

1981 ◽  
Vol 59 (15) ◽  
pp. 2391-2401 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
Distorted Octahedral Geometry ◽  
The Novel ◽  
Space Group ◽  
Bond Lengths ◽  
Tetrahedral Environment ◽  
Distorted Octahedral

X-ray crystallographic studies of three transition metal complexes incorporating the novel anionic tridentate chelating ligand [Me2Ga(N2C5H7)OCH2CH2SR]− (R = Et or Ph) show that the ligand is facially coordinated in each case. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thioethoxyethoxy)gallato(N(2), O,S)]nitrosylnickel(I) are monoclinic, a = 8.8313(4), b = 7.2402(2), c = 26.539(1) Å, β = 94.390(3)°, Z = 4, space group P21/c, R = 0.040 and Rw = 0.050 for 2489 reflections. The Ni atom is in a distorted tetrahedral environment with bond angles about Ni ranging from 87.90(7) to 127.9(1)°. The nitrosyl coordination is slightly non-linear with Ni—N—O = 170.1(4)°. Important bond lengths (corrected for libration) are: Ni—S, 2.326(1), Ni—O, 2.019(2), Ni—N(pyrazolyl), 1.980(3), Ni—N(O), 1.633(3) and N—O, 1.156(4) Å. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thiophenoxyethoxy)gallato(N(2),O,S)]tricarbonylmanganese(I) are triclinic, a = 9.4911(5), b = 10.4323(6), c = 11.7618(7) Å, α = 86.17(1), β = 69.547(5), γ = 81.402(4)°, Z = 2, space group [Formula: see text]R = 0.029 and Rw = 0.035 for 2496 reflections. The Mn atom is coordinated to the fac-tridentate gallate ligand and to three carbonyl ligands resulting in a slightly distorted octahedral geometry. Important corrected bond lengths are: Mn—S, 2.397(1), Mn—O, 2.055(2), Mn—N, 2.082(3), and Mn—C, 1.794(4), 1.807(4), and 1.807(4) Å. Crystals of [dimethyl(3,5-dimethyl-1-pyrazolyl) (2-thioethoxyethoxy)gallato(N(2),O,S)](η3-cycloheptatrienyl)dicarbonylmolybdenum are monoclinic, a = 17.030(3), b = 19.097(2), c = 15.908(3) Å, β = 115.99(1)°, Z = 8, space group P21/n R =0.036 and Rw = 0.043 for 4477 reflections. The two crystallographically independent molecules differ primarily in the orientation of the S-ethyl moiety and each contains an η3-C7H7 ligand which occupies one coordination site of a distorted octahedron as a %-donating ligand. Important corrected bond distances are: Mo—S, 2.527(2) and 2.541(2), Mo—O, 2.241(5) and 2.237(4), Mo—N, 2.277(5) and 2.254(5), Mo—C(O), 1.940(7)–1.960(7), and Mo—C(C7H7), 2.198(6)−2.391(7) Å.

Silver(I)-Saccharinato Complexes with 2-(Aminomethyl)pyridine and 2-(2-Aminoethyl)pyridine Ligands: [Ag(sac)(ampy)] and [Ag2(sac)2(μ-aepy)2]

2005 ◽  
Vol 60 (9) ◽  
pp. 978-983 ◽  
Author(s):  
Sevim Hamamci ◽  
Veysel T. Yilmaz ◽  
William T. A. Harrison
Keyword(s):  
Thermal Analysis ◽  
Hydrogen Bonds ◽  
Monoclinic Space Group ◽  
Stacking Interactions ◽  
Coordination Geometry ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Pyridine Ligands

Two new saccharinato-silver(I) (sac) complexes, [Ag(sac)(ampy)] (1), and [Ag2(sac)2(μ-aepy)2] (2), [ampy = 2-(aminomethyl)pyridine, aepy = 2-(2-aminoethyl)pyridine], have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the monoclinic space group P21/c and triclinic space group P1̄, respectively. The silver(I) ions in both complexes 1 and 2 exhibit a distorted T-shaped AgN3 coordination geometry. 1 consists of individual molecules connected into chains by N-H···O hydrogen bonds. There are two crystallographically distinct dimers in the unit cell of 2 and in each dimer, the aepy ligands act as a bridge between two silver(I) centers, resulting in short argentophilic contacts [Ag1···Ag1 = 3.0199(4) Å and Ag2···Ag2 = 2.9894(4) Å ]. Symmetry equivalent dimers of 2 are connected by N-H···O hydrogen bonds into chains, which are further linked by aromatic π(py)···π(py) stacking interactions into sheets.

Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Nickel Complexes ◽  
Addition Reactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Square Planar ◽  
Structure Determinations

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.

scholarly journals Über die Reaktion von Wolframhexachlorid mit Se4N2; Kristallstruktur von PPh4[WCl5(NSeCl)] / On the Reaction of Tungsten Hexachloride with Se4N2; Crystal Structure of PPh4[WCl5(NSeCl)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1625-1628 ◽  
Author(s):  
Stefan Vogler ◽  
Werner Massa ◽  
Kurt Dehnicke
Keyword(s):  
Crystal Structure ◽  
Double Bond ◽  
Structure Determination ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Tetraphenylphosphonium Chloride ◽  
Tungsten Hexachloride

The reaction of tungsten hexachloride with Se4N2 leads to [WCl4(NSeCl)]2, which reacts with pyridine to form [WCl4(NSeCl)Py], and with tetraphenylphosphonium chloride to form PPh4[WCl5(NSeCl)], which was characterized by an X-ray structure determination. Space group P21, Z = 2, 1657 observed unique reflections, R = 0.074, wR = 0.061. Lattice dimensions at —80 C: a = 710.7(1), b = 2217.9(4), c = 953.6(2) pm; β = 111.93(3) . The [WCl5(NSeCl)]- ion possesses an almost linear WNSe group with bond lengths WN = 188 pm, corresponding to a double bond, and NSe = 200 pm.

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