Thiophenophane metal complexes. II. Preparation, structure, and properties of binuclear copper(II) complexes and of 2,5,9,12-tetrathia[13](2,5) thiophenophane. Evidence for S-coordinated thiophene

1989 ◽  
Vol 67 (4) ◽  
pp. 639-647 ◽  
Author(s):  
C. Robert Lucas ◽  
Shuang Liu ◽  
Michael J. Newlands ◽  
Jean-Pierre Charland ◽  
Eric J. Gabe
Keyword(s):  
Electronic Spectra ◽  
Molecular Structures ◽  
Structure And Properties ◽  
Binuclear Copper ◽  
Space Group ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral ◽  
Group A

Preparations of the thiophenophane C13H20S5, (L2), its binuclear copper(II) complex, (CuCl2•L2)2 and the related thiophenophane complex (CuCl2•L1)2 (L1 = C10H14S4) are described. The 13C and 1H nmr spectra of L2 and the ir and electronic spectra of the complexes are reported. The molecular structures of L2, (CuCl2•L1)2, and (CuCl2•L2)2 have been determined. For L2: space groupP21/a,a = 14.658(1), b = 5.9800(3), c = 19.772(2) Å, β = 111.00(1)°, Z = 4, Rf = 0.050,Rw = 0.046. For (CuCl2•L1)2: space group Pbca, a = 15.383(6), b = 11.409(3), c = 17.423(4) Å, Z = 4, Rf = 0.057, Rw = 0.036. For (CuCl2•L2)2: space group A2/a, a = 12.616(1), b = 10.0542(6), c = 29.180(2) Å, β = 95.81(1)°, Z = 4, Rf = 0.055, Rw = 0.038. The complex (CuCl2•L1)2 has distorted octahedral coordination geometry about each copper. The copper atoms are linked by two bridging chlorines and each copper also bears one terminal chlorine, two thioether-sulfurs and a thiophene-sulfur. In contrast, (CuCl2•L2)2 does not involve coordination by thiophene-sulfur and the remaining coordination sphere has undergone distortion from square pyramidal towards trigonal bipyramidal. Differences in the electronic spectra are interpreted in terms of the structures of the complexes. Keywords: binuclear copper(II) thiophenophane complex.

Copper complexes of Picloram: The crystal and molecular structures of Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate and Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)bis(pyrimidin-2-amine)copper(II)

1983 ◽  
Vol 36 (1) ◽  
pp. 183 ◽  
Author(s):  
EJ O'Reilly ◽  
G Smith ◽  
CHL Kennard ◽  
AH White
Keyword(s):  
Copper Complexes ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral ◽  
A Cell ◽  
Amine Ligands

The crystal structures of two copper(II) complexes of the herbicide Picloram (4-amino-3,5,6-trichloro- pyridine-2-carboxylic acid) have been determined by single-crystal X-ray diffractometry. Bis(4-amino- 3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate (1) is monoclinic, space group C2/c, with Z 4 in a cell of dimensions a 15.593(6), b 7.940(6), c 16.983(6) �, β 107.58(3)�. The structure was refined to a residual R 0.046 for 905 'observed' reflections. Complex (1) is trigonal bipyramidal with the trigonal plane consisting of oxygens from two picolinate ligands [Cu-O 1.995(5) �] and a water molecule [Cu-O 2.080(5) �]. The apical positions are occupied by pyridine ring nitrogens from the Picloram ligands [Cu-N 2.021(5) �]. Bis(4-amino-3,5,6-trichloropyridine- 2-carboxylato)bis(pyrimidin-2-amine)copper(II) (2) is monoclinic, space group P2,/c, with Z 4 in a cell of dimensions a 12.3 11(5), b 15.435(5), c 15.320(6) �, β 115.95(3)�, and gave a final R 0.059 for 2429 'observed' reflections. In complex (2), the copper(II) atom has a tetragonally distorted octahedral stereochemistry with the Picloram ring nitrogens once again occupying the two axial positions [Cu-N 2.586(7) and 2.611(7) �]. The square plane consists of two carboxylato oxygens [Cu-O 1.941(6) and 1.960(7) �] and two hetero-nitrogens from pyrimidin-2-amine ligands [Cu-N 2.048(6) and 2.054(6) �].

Synthesis and characterization of [MII(bqb)] (M = Co, Ni, Cu), [N(n-Bu)4][CoIII(bqb)(CN)2], and [N(n-Bu)4][CoIII(bqb)(N3)2] containing deprotonated N,N'-bis(2-quinolinecarboxamide)-1,2-benzene (bqb) – X-ray crystal structures of [NiII(bqb)] and [N(n-Bu)4][CoIII(bqb)(N3)2]

2006 ◽  
Vol 84 (7) ◽  
pp. 971-978 ◽  
Author(s):  
Soria Meghdadi ◽  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Alison Zamanpoor
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Elemental Analyses

Cobalt(II), nickel(II), copper(II), and two cobalt(III) complexes of a new dianionic ligand, bqb, [H2bqb = N,N'-bis(2-quinolinecarboxamide)-1,2-benzene] have been synthesized and characterized by elemental analyses, IR, and 1H NMR spectroscopy. The crystal and molecular structures of the [Ni(bqb)] (2) and [N(n-Bu)4][CoIII(bqb)(N3)2] (5) complexes were determined by X-ray crystallography. Complex 2 crystallizes in the monoclinic space group C2/c with a distorted square-planar structure including two short Ni–N (1.848 Å) and two long Ni–N (1.958 Å) bonds. The structure consists of sheets formed in the plane parallel to the b axis and diagonal to vectors a and c by intermolecular hydrogen bonds. Complex 5 crystallizes in the monoclinic space group C2 with a distorted octahedral structure. The [N(n-Bu)4]+ ion is disordered at the C3A and C4A atoms of one Bu. The IR and 1H NMR spectra of the complexes are also discussed.Key words: N4-dianionic amido ligand (bqb), (bqb) complexes of Co(II), Ni(II), Cu(II), and Co(III), azide, cyanide, X-ray crystal structures.

Manganese, molybdenum, and tungsten carbonyl derivatives incorporating the dimethylbis(1-pyrazolyl)gallate ligand, [Me2Ga(N2C3H3)2]−

1981 ◽  
Vol 59 (22) ◽  
pp. 3123-3135 ◽  
Author(s):  
Sharon E. Anslow ◽  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Mirror Symmetry ◽  
Variable Temperature ◽  
Nmr Studies ◽  
Space Group ◽  
H Nmr ◽  
Carbonyl Derivatives ◽  
Distorted Octahedral Coordination Geometry ◽  
Distorted Octahedral ◽  
Tungsten Carbonyl ◽  
And Tungsten

The synthesis of a number of six-coordinate manganese, molybdenum, and tungsten carbonyl compounds incorporating both the bidentate bispyrazolyl gallate ligand, [Me2Ga(N2C3H3)2]−, and a neutral pyrazole ligand in a facial coordination arrangement are described. Variable temperature 1H nmr studies have revealed interestingly different behaviours in solution for the valence isoelectronic species [Me2Ga(N2C3H3)2](N2C3H4)Mn(CO)3 and [Me2Ga(N2C3H3)2](N2C3H4)Mo(CO)3−. X-ray structural analyses of crystalline samples of the two compounds have been carried out in an effort to shed light on these behavioural differences. Crystals of [Me2Ga(N2C3H3)2](N2C3H4)Mn(CO)3 are monoclinic, a = 31.053(2), b = 8.0503(4), c = 15.8629(8) Å, β = 108.164(2)°, Z = 8, space group C2/c and crystals of [(C2H5)4N]+{[Me2Ga(N2C3H3)2](N2C3H4)Mo(CO)3}− are monoclinic, a = 10.058(1), b = 20.6488(5), c = 13.533(1) Å, β = 93.800(5)°, Z = 4, space group P21/n. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to final R values of 0.028 and 0.023 for 2613 and 4388 observed reflections for the Mn and Mo complexes, respectively. The neutral Mn complex and the complex Mo anion both have approximate mirror symmetry and both metal atoms have trigonally distorted octahedral coordination geometry. Important bond distances (corrected for thermal vibration) are: Mn—N, 2.074(3)–2.086(3), Mn—C, 1.795(4)–1.809(5), Mo—N, 2.291(2)–2.295(2), and Mo—C, 1.918(3)–1.936(3) Å. Although structural differences between these two species do offer plausible explanations for the differences observed in solution, it appears that other factors are more important.

Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinat]-THF (1/2) - Synthese, spektroskopische Charakterisierung und Struktur/Calcium-bis[N,N'-bis(trimethylsilyl)benzamidinate]-THF (1/2) - Syntheses, Spectroscopic Characterization and Structure

1992 ◽  
Vol 47 (4) ◽  
pp. 453-459 ◽  
Author(s):  
Matthias Westerhausen ◽  
Wolfgang Schwarz
Keyword(s):  
Title Compound ◽  
High Field ◽  
Spectroscopic Characterization ◽  
Calcium Atom ◽  
Space Group ◽  
Bond Lengths ◽  
H Nmr ◽  
Distorted Octahedral ◽  
Anionic Charge ◽  
Field Shift

The reaction of calcium-bis[bis(trimethylsilyl)amide]-THF (1/2) with benzonitrile in THF nearly quantitatively yields the title compound calcium-bis[N,N'-bis(trimethylsilyl)- benzamidinate]-THF (1/2). Under similar conditions pivalonitrile substitutes an ether ligand of calcium-bis[bis(trimethylsilyl)amide]-DME (1/2) without the formation of the corresponding amidinate derivative. The calcium-di(benzamidinate) [H5C6-C(NSiMe3)2]2Ca · 2THF crystallizes in the space group Pbcn with {a = 188.8(6); b = 1286.0(3); c = 1802.5(5) pm; Z = 4}. The calcium atom is hexa-coordinate with a distorted octahedral trans-configuration and with Ca - O and Ca - N bond distances of 238 and 243 pm, respectively. The bond lengths within the NCN moiety with values of 132 pm are characteristic of a diazaallylic system. The short N - Si bond lengths of about 170.5 pm as well as the high field shift of the 29Si{1H} NMR signal are evidence for an effective backdonation of the anionic charge from the nitrogen to the silicon atoms.

Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids

1993 ◽  
Vol 48 (4) ◽  
pp. 409-417 ◽  
Author(s):  
Rostislav D. Lampeka ◽  
Zamira D. Uzakbergenova ◽  
Victor V. Skopenko
Keyword(s):  
Electronic Absorption Spectra ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
R Factors

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.

Synthesis, characterization, and crystal and molecular structures of the coordination compounds, [Me2Ga•O(C5H3N)CH2NMe2] and [Me2Ga•O(C9H6N)]2

1987 ◽  
Vol 65 (4) ◽  
pp. 782-788 ◽  
Author(s):  
Emmanuel C. Onyiriuka ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Heavy Atom ◽  
Amino Nitrogen ◽  
Molecular Structures ◽  
Geometrical Parameters ◽  
Planar System ◽  
Gallium Atom ◽  
Space Group ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal Coordination ◽  
Centrosymmetric Dimers

Crystals of (2-dimethylaminomethyl-3-pyridolato)dimethylgallium are monoclinic, a = 13.443(3), b = 6.7563(3), c = 13.046(2) Å, β = 100.38(1)°, Z = 4, space group I2/m, and those of bis[(8-quinolinolato)dimethylgallium] are monoclinic, a = 9.7340(4), b = 12.7135(5), c = 9.6843(4) Å, β = 117.014(3)°, Z = 2, 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 0.032 for 1485 and 1567 reflections with I ≥ 3σ(I), respectively. The structure of [Me2Ga•O(C5H3N)CH2NMe2] consists of discrete monomeric molecules which contain tetrahedrally coordinated gallium atoms. The bidentate anionic 2-dimethylaminomethyl-3-pyridolate ligand coordinates Ga via the oxygen and amino nitrogen atoms (Ga—O = 1.892(3), Ga—N = 2.127(4), Ga—C = 1.950(5) and 1.939(6) Å). The structure of [Me2Ga•O(C9H6N)]2 consists of centrosymmetric dimers which contain a nearly planar system of seven fused rings. The Ga atoms are five-coordinate, having distorted trigonal bipyramidal coordination geometry. The dimerization occurs via the formation of a central, planar, four-membered (Ga—O)2 ring in which each asymmetrically bridging oxygen atom occupies an equatorial coordination site on one gallium atom and an axial site on the other. Important geometrical parameters for [Me2Ga•O(C9H6N)]2 are Ga—O(eq) = 1.937(3), Ga—O(ax) = 2.297(3), Ga—N(ax) = 2.211(3), Ga—C(eq) = 1.948(6) and 1.945(5) Å, O(ax)—Ga—N(ax) = 149.7(1)°.

Crystal Structure and Spectroscopic Behaviour of a Binuclear Copper(II) Complex of Mefenamic Acid and Dimethylsulfoxide

1998 ◽  
Vol 53 (8) ◽  
pp. 871-874 ◽  
Author(s):  
G. Facchin ◽  
M. H. Torre ◽  
E. Kremer ◽  
O. E. Piro ◽  
E. J. Baran
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Mefenamic Acid ◽  
Electronic Spectra ◽  
Anthranilic Acid ◽  
Binuclear Copper ◽  
Triclinic Space Group ◽  
Spectroscopic Behaviour ◽  
Space Group ◽  
X Ray

Abstract The crystal structure of the binuclear Cu(II) complex [Cu(mef)2DMSO]2 (mef = deprotonated N-2,3-dimethylphenyl-anthranilic acid; DMSO = dimethylsulfoxide) has been determined by single-crystal X-ray diffractometry. It crystallizes in the triclinic space group P1̄ with Z = 1. IR and electronic spectra of the compound are also discussed briefly.

Copper(II) and Nickel(II) Complexes of Pentaaza Macrocyclic Ligands

1987 ◽  
Vol 40 (2) ◽  
pp. 347 ◽  
Author(s):  
P Osvath ◽  
NF Curtis ◽  
DC Weatherburn
Keyword(s):  
Aqueous Solution ◽  
Solid State ◽  
Electronic Spectra ◽  
Macrocyclic Ligands ◽  
Distorted Octahedral Environment ◽  
Trigonal Bipyramidal ◽  
Octahedral Environment ◽  
Distorted Octahedral

The preparations of the pentaazamacrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, cpad , l,4,7,l0,13-pentaazacyclohexadecane, ched , l,4,7,l0,14-pentaazacycloheptadecane, chad , 1,4,7,11,14-pentaazacycloheptadecane, cnad , 1,4,7,11,15-pentaazacyclooctadecane, cnad , 1,4,8,11,15-pentaazacyclooctadecane, cnad , 1,4,8,12,16-pentaazacyclononadecane, cnad , and 1,5,9,13,17-pentaazacycloeicosane, ceic , as well as the new linear pentaamine N-(3-aminopropy1)- N'-[3-[(3-aminopropyl)amino] propyl ]propane-1,3-diamine, tpah , are described. Copper(II) and nickel(II) complexes of the above ligands have been prepared and characterized. The nickel(II) complexes of the smaller macrocycles and the linear pentaamine contain NiII in a tetragonally distorted octahedral environment in the presence of coordinating anions or in aqueous solution but the [Ni( cnad )]2+ and [Ni( ceic )]2+ cations are five-coordinate both in the solid state and in aqueous solution. The copper(II) complexes of the macrocyclic pentaamines appear to be square-pyramidal on the basis of their electronic spectra, whereas the complex [cu( tpah )]2+ is probably trigonal- bipyramidal.

The crystal and molecular structures of the bispyridine and 1,10-phenanthroline adducts of Bis(ethyl 3-mercaptobut-2-enoato)nickel(II)

1982 ◽  
Vol 35 (2) ◽  
pp. 331 ◽  
Author(s):  
J Sachinidis ◽  
MF Mackay ◽  
MW Grant
Keyword(s):  
Thermodynamic Data ◽  
Molecular Structures ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Crystal And Molecular Structures ◽  
Distorted Octahedral ◽  
In Cis ◽  
Oxygen Atoms

X-ray analyses of monoclinic crystals of the bispyridine and 1,10-phenanthroline adducts of the monothioacetylacetonate complex bis(ethyl 3-mercaptobut-2-enoato)nickel(n), Ni(eosm)2,* have defined their structures. Crystals of the bispyridine adduct Ni(eosm)2,py2, C22H28N2NiO4S2, belong to the space group P21/c with a 8.865(6), b 15.758(4), c 9.136(3)Ǻ, β 109.18(4)°, Z 2. Crystals of the 1,10-phenanthroline adduct Ni(eosm)2,phen, C24H26N2NiO4S2, belong to the space group P21c with a 12.451(2), b 16.949(1), c 15 5921(2) Ǻ, β 130.97(1)°, Z 4. The structures were refined with diffractometer data measured with Cu Ka radiation to R 0.047 (1962 terms) for the bispyridine adduct and R 0.061 (3115 terms) for the phenanthroline adduct. The geometry about the nickel in each complex is distorted octahedral. The molecule of the bispyridine adduct has exact rn symmetry with the two sulfur atoms cis-equatorial and the nitrogen atoms axial. In the phenan- throline adduct, pairs of sulfur, nitrogen and oxygen atoms are in cis configurations. In the bis-pyridine adduct, the Ni-N bond lengths, 2.153(3) and 2.182(4) Ǻ, are significantly longer than those in other bispyridine adducts of nickel(II) species. It is suggested that the long Ni-N distances reflect the relative instability of the bispyridine adduct, and thermodynamic data are presented to support this.

Monomere und dimere Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von [As(C6H5)4]SeOCl3 und [N(C2H5)4]SeOCl3 / Monomerie and Dimeric Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of [As(C6H5)4]SeOCl3 and [N(C2H5)4]SeOCl3

1983 ◽  
Vol 38 (1) ◽  
pp. 20-29 ◽  
Author(s):  
Bernt Krebs ◽  
Marita Hucke ◽  
Michael Hein ◽  
Andreas Schäffer
Keyword(s):  
Polymer Chains ◽  
Monoclinic Space Group ◽  
Structure And Properties ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Centrosymmetric Dimers

Abstract The monomeric SeOCl3- ion, which can be prepared as the tetraphenylarsonium salt from SeOCl2 and As(C6H5)4Cl, was structurally characterized by a low-temperature single crystal X-ray diffraction analysis. [As(C6H5)4]SeOCl3 is monoclinic, space group P21/c, with a = 9,332(3), b = 13,761(4), c = 18,985(6) Å, β = 110,97(3)° (at -135 °C), Z = 4; it contains a novel type of ψ-trigonal bipyramidal oxotrichloroselenate(IV) anion which is not associated to dimers or polymer chains as in known structures. The equatorial positions are occupied by doubly bonded oxygen (Se-O 1,601(3) Å) and by one Cl(Se-Cl 2,234(1) Å), the axial Se-Cl bonds (2,430(1) and 2,475(1) Å) being significantly longer. [N(C2H5)4]SeOCl3, which was obtained as crystals by oxidation of trichloroselenate(II), is triclinic, space group P1̄, with a = 10,607(3), b = 8,950(2), c = 8,862(2) Å, α = 119,79(2)°, β = 101,07(2)°, γ = 96,28(2)°, Z = 2. The X-ray structure analysis shows the anions to be present as centrosymmetric dimers Se2O2Cl62- like in the [P(C6H5)4]+ salt, with two tetragonal SeOCl4 pyramids linked through a Cl···Cl edge and the lone pairs trans to the axial Se-O bonds (1,589(4) Å). Se-Cl bond lengths are 2.270(1) and 2,351(2) Å (terminal); 2,698(1) and 2,920(1) Å (bridging). The results show that the nature of the reaction products of the Lewis acid SeOCl2 with halogenides as bases changes very sensitively with small variations in cations and environment. The vibrational spectra are discussed.

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