Neutral pyrazolyl-bridged nickel nitrosyl complexes. Synthesis, structure, and reactivity

1979 ◽  
Vol 57 (23) ◽  
pp. 3090-3098 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Nucleophilic Attack ◽  
Donor Ligands ◽  
Nickel Compound ◽  
Neutral Donor ◽  
Full Matrix ◽  
Space Group ◽  
Nitrosyl Complexes ◽  
Square Planar

A series of neutral pyrazolyl-bridged nickel nitrosyl complexes, [LNi(NO)]2 (where L = pyrazolyl, N2C3H3; 3,5-dimethylpyrazolyl, N2C5H7; or 3,5-di-tert-butylpyrazolyl, N2C11H19), is described. The nickel atoms are susceptible to nucleophilic attack and the reactivity of the dimers with neutral donor ligands is reported. In addition to the dimeric molecules a novel trimetallic nickel compound [(ON)Ni(N2C5H7)2]2Ni has also been isolated. Crystals of [Ni(NO)(N2C5H7)]2 are monoclinic, a = 18.925(2), b = 11.012(1), c = 7.037(2) Å, β = 100.93(1)°, Z = 4, space group C2/c and crystals of [(ON)Ni(N2C5H7)2]2Ni are triclinic, a = 7.4041(7), b = 9.6331(7), c = 9.7595(8) Å, α = 85.698(9), β = 73.174(8), γ = 76.109(8)°, Z = 1, space group [Formula: see text]. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.035 and 0.028 for 832 and 2128 reflections with I ≥ 3σ(I) respectively. Nearly planar centrosymmetric molecules of [Ni(NO)(N2C5H7)]2 contain trigonal planar nickel atoms with Ni—N(pyrazolyl) = 1.880(3) and 1.922(3), Ni—NO = 1.616(4), and N—O = 1.158(4) Å, Ni—N—O = 178.9(4)°. This structure also contains an unusually long N—N bond in the pyrazolyl ring (1.463(4) Å). Centrosymmetric molecules of [(ON)Ni(N2C5H7)2]2Ni contain a central square-planar Ni(II) atom bonded to four pyrazolyl nitrogen atoms (mean Ni—N = 1.905(1) Å) and two trigonal planar outer nickel atoms coordinated to two pyrazolyl nitrogen atoms (mean Ni—N = 1.922(3) Å) and to a somewhat bent nitrosyl group (Ni—N = 1.625(3), N—O = 1.153(4) Å, Ni—N—O = 168.9(3)°).

Synthesis and characterization of [Me2Ga(3,5-Me2pz)2]Rh(CO)PPh3 and the X-ray structure of its toluene solvate

1985 ◽  
Vol 63 (2) ◽  
pp. 503-508 ◽  
Author(s):  
Brenda M. Louie ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Physical Properties ◽  
Least Squares ◽  
Heavy Atom ◽  
Synthesis And Characterization ◽  
Boat Conformation ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Square Planar

Details of the synthesis and physical properties of [Me2Ga(3,5-Me2pz)2]Rh(CO)PPh3 are given. Crystals of [dimethylbis(3,5-dimethyl-1-pyrazolyl)gallato-N,N′](triphenylphosphine)carbonylrhodium(I) – toluene (1:1) are triclinic, a = 10.690(2), b = 12.928(2), c = 13.998(2) Å, α = 77.44(1), β = 83.50(1), γ = 72.70(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 = 0.039 and Rw = 0.048 for 5987 reflections with I ≥ 3σ(I). The Rh(I) is in a distorted square planar environment with Rh—N = 2.090(3) and 2.097(2), Rh—CO = 1.815(4), and Rh—P = 2.2700(8) Å. The central six-membered RhGaN4 ring has a steep boat conformation with a [Formula: see text] separation of 3.3819(4) Å.

Allylic derivatives of nickel and palladium

1981 ◽  
Vol 59 (6) ◽  
pp. 996-1006 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Trinuclear Complex ◽  
Boat Conformation ◽  
Coordination Geometry ◽  
Orientational Disorder ◽  
Full Matrix ◽  
Space Group ◽  
Coordination Sites ◽  
Square Planar ◽  
Derivatives Of

The synthesis of novel allylic derivatives of Ni and Pd incorporating the bispyrazolylgallate ligand Me2Ga(N2C5H7)2− is described. Pyrazolyl-bridged homobinuclear and trinuclear nickel allyl systems are also presented. Crystal structures of [Me2Ga(N2C5H7)2]Ni(η3-C3H5) and [(η3-C3H5)Ni(N2C5H7)2]2Ni are described. Crystals of the former are triclinic, a = 8.265(1), b = 10.487(1), c = 11.755(2) Å, α = 72.60(1), β = 87.28(1), γ = 67.58(1)°, Z = 2, space group [Formula: see text] and crystals of the latter are monoclinic, a = 7.9172(3), b = 10.6929(1), c = 16.9118(6) Å, β = 102.887(2)°, Z = 2, space group P21/c. Both structures were solved by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to R = 0.026 and 0.025 for 3329 and 2914 reflections with I ≥ 3σ(I) respectively. In both structures the M—(N—N)2—M rings are in the boat conformation and the allyl groups display twofold orientational disorder. In [Me2Ga(N2C5H7)2]Ni(η3-C3H5) the nickel coordination may be regarded as square-planar with the allyl ligand occupying two coordination sites and the coordination about the gallium is distorted tetrahedral. Important bond lengths (corrected for libration) are: Ni—N, 1.926(2) and 1.929(2), Ni—C, 1.971(5)–2.025(3), Ga—N, 1.994(2) and 1.996(2), Ga—C, 1.966(3) and 1.988(3) Å. The trinuclear complex [(η3-C3H5)Ni(N2C5H7)2]2Ni is centrosymmetric with the central Ni(1) atom bonded to four pyrazolyl nitrogen atoms in square-planar fashion. The outer Ni(2) atom is bonded to two pyrazolyl nitrogens and to an allyl group and also has square-planar coordination geometry. Important bond distances in this complex are: Ni(1)—N, 1.897(1) and 1.901(1), Ni(2)—N, 1.908(2) and 1.912(2), Ni(2)—C, 1.97(l)–2.022(3) Å.

Studies in aryltin chemistry. Part 6. Crystal and molecular structures of tetra(p-methylsulphonylphenyl)tin(IV) and tetra(p-methylsulphinylphenyl)tin(IV) monohydrate

1990 ◽  
Vol 68 (8) ◽  
pp. 1277-1282 ◽  
Author(s):  
Ivor Wharf ◽  
Michel G. Simard ◽  
Henry Lamparski
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Direct Method ◽  
Molecular Structures ◽  
Water Molecules ◽  
Monoclinic Space Group ◽  
Molecular Symmetry ◽  
Asymmetric Unit ◽  
Full Matrix ◽  
Space Group

Tetrakis(p-methylsulphonylphenyl)tin(IV) and tetrakis(p-methylsulphinylphenyl)tin(IV) n-hydrate have been prepared and their spectra (ir 1350–400 cm−1; nmr, 1H, 13C, 119Sn) and X-ray crystal structures are reported. The first compound is monoclinic, space group C2/c, Z = 4, with a = 21.589(6), b = 6.207(3), c = 22.861(11) Å, β = 93.80(3)° (22 °C); the structure was solved by the direct method and refined by full-matrix least squares calculations to R = 0.043 for 2755 observed reflections. It has 2 molecular symmetry with the methyl group and one oxygen atom completely disordered in both CH3S(O2) groups in the asymmetric unit. The second compound is tetragonal, space group P42/n, Z = 2, with a = b = 15.408(6), c = 6.379(2) Å (−100 °C); the structure was solved by the Patterson method and refined by full-matrix least squares calculations to R = 0.060 for 1209 observed reflections. It has [Formula: see text] molecular symmetry with the whole asymmetric unit disordered. Water molecules occupy positions on parallel 42 axes but molecular packing requirements prevent all sites having 100% occupancy giving n ~ 1 for the hydrate. Keywords: Tetra-aryltins, crystal structures, sulphone, sulphoxide, hydrogen-bonding.

Structural studies of organoboron compounds. XX.(Salicylaldoximato-O,N)diphenylboron

1984 ◽  
Vol 62 (7) ◽  
pp. 1363-1368 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bonds ◽  
Least Squares ◽  
Chelate Ring ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Phenolic Oxygen

Crystals of (salicylaldoximato-O,N)diphenylboron are triclinic, a = 10.125(2), b = 10.797(1), c = 14.760(2) Å, α = 89.05(1), β = 86.98(1), γ = 83.18(1)°, Z = 4, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.040 and Rw = 0.048 for4145 reflections with I ≥ 3σ(I). The structure consists of two crystallographically independent, but essentially identical, molecules linked by strong [Formula: see text] hydrogen bonds to form continuous spirals along the a axis. The Ph2B moiety is chelated by the phenolic oxygen and oxime nitrogen atoms of the ligand resulting in the formation of a non-planar six-membered chelate ring. Important libration-corrected mean bond lengths are O—B = 1.516(1), N—B = 1.609(2), and C—B = 1.613(2) Å.

Coordinated fluoride in rhenium(I) carbonyl complexes

1984 ◽  
Vol 37 (1) ◽  
pp. 35 ◽  
Author(s):  
E Horn ◽  
MR Snow
Keyword(s):  
Hydrogen Bonding ◽  
Least Squares ◽  
Mass Spectra ◽  
Structural Data ◽  
Monoclinic Space Group ◽  
Carbonyl Complexes ◽  
Full Matrix ◽  
Space Group ◽  
Corrected Data ◽  
R Value

Bromide abstraction from the complexes Re(CO)3L2Br (where L = SbPh3 and L2 = bpy, dpe, tmen)* by AgF2H gives the corresponding fluoro compounds Re(CO)3L2F. Mass spectra and structural data show that the fluoride in these complexes is coordinated to the metal. The structures of Re(CO)3(tmen)F and [Re(CO)3(tmen)F]2H.HOBF3 are reported here. Crystals of Re(CO)3(tmen)F are monoclinic, space group P21/c, with a 8.202(2), b 13.115(9), c 12.048(4) � and β 102 24(3)�. A full-matrix least-squares refinement by using the absorption corrected data gave a conventional R value of 0.041. [Re(CO)3(tmen)F]2H.HOBF3 also crystallizes in the space group P21/c. The lattice parameters are: a 17.495(2), b 10.772(2), c 15.447(1) � and β ( 101.409(8)�. The final R value of a blocked least-squares calculation converged at 0.061. In these two complexes the simple Re-F distance is 2.040(4) �, in Re(CO)3(tmen)F. The Re-F distance is increased to 2.236(10)�, as a result of hydrogen bonding between the fluoride and HOBF3 in the latter compound.

The crystal structure and vibrational spectra of cis-dichlorobis(cyclopropylamine)-platinum(II), PtCl2(C3H5NH2)2

1981 ◽  
Vol 59 (18) ◽  
pp. 2737-2745 ◽  
Author(s):  
Helen Elaine Howard-Lock ◽  
Colin James Lyne Lock ◽  
Graham Turner ◽  
Maruta Zvagulis
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Vibrational Spectra ◽  
Vibrational Analysis ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Deuterated Analogue

Crystals of cis-dichlorobis(cyclopropylamine)platinum(II), PtCl2(C3H5NH2)2, are monoclinic, a = 12.770(5), b = 5.838(2), c = 15.113(6) Å, β = 104.46(3)°, Z = 4, space group P21/c. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares to R = 0.057, Rw = 0.055 for 1577 reflections with I > 3σ(I). Bond lengths and angles are normal. A vibrational analysis of the compound and its d2-deuterated analogue was performed.

Reaction of N,N′-dihydroxy-.N,N′-dimethylmethanediamine with phenylboronic acid and the crystal and molecular structure of N,N′-dihydroxy-N,N′-dimethylmethanediamine

1989 ◽  
Vol 67 (11) ◽  
pp. 1959-1963 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Exact Formula ◽  
Full Matrix ◽  
Space Group ◽  
Hydrogen Bonded

The reaction of N,N′-dihydroxy-N,N′-dimethylmethanediamine with phenylboronic acid leads to the product 1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane rather than the expected product 1,5-dimethyl-3-phenyl-1,5-diaza-2,4-dioxa-3-boracyclohexane. The structure of N,N′-dihydroxy-N,N′-dimethylmethanediamine has been determined and is discussed in terms of its reaction with PhB(OH)2. Crystals of N,N′-dihydroxy-N,N′-dimethylmethanediamine are tetragonal, a = 8.5346(3), c = 8.4178(7) Å, Z = 4, space group P421c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.036 and Rw of 0.038 for 333 reflections with I ≥ 3σ(I). The structure consists of hydrogen-bonded dimers having exact [Formula: see text] symmetry. Keywords: N,N′-dihydroxy-N,N′-dimethylmethanediamine, crystal structure.

Crystal and molecular structure of difluoroboron N-methylacethydroxamate (2,2-difluoro-4,5-dimethyl-1,3-dioxa-4-azonia-2-boranatacyclopent-4-ene)

1977 ◽  
Vol 55 (1) ◽  
pp. 1-7 ◽  
Author(s):  
Steven J. Rettig ◽  
James Trotter ◽  
W. Kliegel ◽  
D. Nanninga
Keyword(s):  
Molecular Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Crystals of difluoroboron N-methylacethydroxamate are monoclinic, a = 5.097(1), b = 10.653(2), c = 11.520(2) Å, β = 103.57(2)°, Z = 4, space group P21/c. The structure was solved by direct methods and was refined by full-matrix least squares procedures to a final R of 0.056 and Rw of 0.077 for 988 reflections with I ≥ 3σ(I). The structure features a planar five-membered BO2CN ring. Bond lengths (corrected for libration) are: B—F, 1.374(3) and 1.381(3), O—B, 1.496(3) and 1.497(3), O—N, 1.349(2), O—C, 1.346(2), C—N, 1.298(3) and 1.458(3), and C—C, 1.468(3) Å.

The Crystal Structure of Dimedone

1975 ◽  
Vol 53 (7) ◽  
pp. 1046-1050 ◽  
Author(s):  
Ishwar Singh ◽  
Crispin Calvo
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Least Squares ◽  
Direct Methods ◽  
Monoclinic Symmetry ◽  
Enolic Form ◽  
Full Matrix ◽  
Space Group ◽  
Least Squares Techniques

Dimedone, C8H12O2, crystallizes with monoclinic symmetry, a = 10.079(7), b = 6.835(3), c = 12.438(4) Å, β = 110.24(5)°, space group P21/n and Z = 4. The structure of this compound was solved by direct methods and refined by full-matrix least-squares techniques using 1205 unique reflections to a final R of 0.047. In the solid state it exists in the enolic form and these molecules pack in the crystal in systems of infinite chains linked together by hydrogen bonds in the y direction. These results are virtually the same as recently reported by Semmingsen.

A crystallographic and spectroscopic study of mercury(II) dithiocarbamate

1981 ◽  
Vol 59 (18) ◽  
pp. 2746-2749 ◽  
Author(s):  
Chung Chieh ◽  
Sing Kwen Cheung
Keyword(s):  
Mass Spectrum ◽  
Spectroscopic Study ◽  
Least Squares ◽  
Least Squares Method ◽  
Two Dimensional ◽  
Polymeric Compound ◽  
Full Matrix ◽  
Space Group ◽  
Polymeric Networks ◽  
Ir Bands

Ammonium dithiocarbamate, H2NCS2NH4, decomposes easily but the anion forms a stable mercury(II) complex, the crystals of which are orthorhombic with a = 7.851(3), b = 17.565(7), c = 12.051(3) Å, and space group Pbca. The structure was solved by the Patterson method and refined by the full-matrix least-squares method to an R of 0.038 for 781 reflections. The structure consists of layers of two-dimensional polymeric networks. The dimeric subunits in the layer containing two each of mutually connected Hg atoms and dithiocarbamates are further linked by other bridging dithiocarbamates forming a sheet-like structure. Each Hg atom bonds to four S atoms from four separate dithiocarbamates with Hg—S distances of 2.499(4), 2.508(4), 2.533(4), and 2.629(4) Å. The ir bands observed were: ν(NH2), 3320, 3220, 3125; δ(NH2), 1600; ν(C—N), 1395; ρr(NH2), 1172; and v(C—S), 840 cm−1. The mass spectrum of this polymeric compound gave peaks corresponding to Hg, S2, CNH2, HNCS, S, CS2, S5, S4, S3, and S8 in the order of their intensities.

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