The crystal and molecular structure of the molybdenum tetracarbonyl complex of 1,4-diphenyl-2,2′,3,3′5,5′,6,6′-octamethylcyclo-1,4- diphospha-2,3,5,6-tetrasilahexane

1979 ◽  
Vol 57 (15) ◽  
pp. 1909-1914 ◽  
Author(s):  
Joseph C. Calabrese ◽  
Richard T. Oakley ◽  
Robert West
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Free Ligand ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Distorted Octahedral ◽  
Silyl Groups ◽  
Back Bonding ◽  
The Mean

The crystal and molecular structure of the molybdenum tetracarbonyl complex of 1,4-diphenyl-2,2′,3,3′,5,5′,6,6′-octamethylcyclo-1,4-diphosph a-2,3,5,6-tetrasilahexane, (PhPSi2Me4)2Mo(CO)4, has been determined by single crystal X-ray diffraction. The crystals are monoclinic, space group P21/n, with a = 15.983(5), b = 19.316(6), c = 10.580(3) Å, β = 99.99(2)° V = 3217(2) Å3, Z = 4, and ρcalcd = 1.356 g/cm3. The structure was solved by Patterson heavy atom methods and was refined by full-matrix least-squares procedures to a final R1 of 3.3% and R2 of 4.3%, for 6342 reflections with intensities greater than 2σ. The coordination of the boat-shaped (PhPSi2Me4)2 ligand to molybdenum tetracarbonyl produces a distorted octahedral environment about the metal. The mean Si—Si (2.358(14) Å) and P—Si (2.275(19) Å) distances are not greatly altered from the values found for them in the free ligand. The structural consequences of P → Si π-bonding in the latter are therefore minimal. The relatively long P—Mo (mean length 2.592(13) Å) distances are interpreted as the result of reduced back-bonding from the metal, caused by the presence of the relatively electropositive silyl groups on phosphorus. Consistently, the equatorial Mo—C bonds, which are trans to the diphosphine ligand, are shorter (mean length 1.968(19) Å) than the corresponding bonds to the axial carbonyl groups (mean length 2.021(15) Å).

Group 6 metal carbonyl complexes of tridentate olefinic tertiary diphosphines. Crystal and molecular structure of {(E)-1,3-Bis[2-(diphenylphosphino)phenyl]-propene}tricarbonyltungsten(0),W(CO)3 {(E)-o-Ph2PC6H4CH=CHC6H4PPh2-o}

1980 ◽  
Vol 33 (6) ◽  
pp. 1261 ◽  
Author(s):  
MA Bennett ◽  
S Corlett ◽  
GB Robertson ◽  
WL Steffen
Keyword(s):  
Molecular Structure ◽  
Double Bond ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Metal Carbonyl ◽  
Free Ligand ◽  
Spectroscopic Studies ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
Olefinic Double Bond

The ligands (L) (E)-2,2'-bis(diphenylphosphino)stilbene, (E)-o-Ph2PC6H4CH=CHC6H4PPh2-o (bdps), (E)-1,3-bis[2-(diphenylphosphino)phenyl]propene, (E)-o-Ph2PC6H4CH=CHCH2C6H4PPh2-o (bdpp), and (E)-1,3-bis[2-(diphenylphosphino)phenyl]but-1-ene,( E)-o-Ph2PC6H4CH=CHCHMeC6- H4PPh2-o (bdpb), form complexes of general formula M(CO)3L (M = Cr, Mo, W). N.m.r. (1H, 13C and 31P) and i.r. data indicate that the metal atoms are octahedrally coordinated by mutually trans phosphorus atoms and the double bond of the olefinic tertiary diphosphines and by meridionally disposed carbonyl groups. Conformational isomers of the complexes of bdpb can be detected by n.m.r, spectroscopy, but there is no evidence for similar conformers in the corresponding complexes of bdps and bdpp. The crystal and molecular structure of W(CO)3(bdpp),0.5CH2C12 has been determined by single-crystal X-ray diffraction analysis. The crystals are triclinic, space group PI, with a 10.1 13(Z), b 13.820(2), c 14.512(3) A, α 76.24(1), β 88.08(1), γ 76.31(1)°. The structure, solved by the heavy-atom method and refined to a conventional R of 0.049 for 8418 diffractometer data, confirms the conclusions drawn from spectroscopic studies. The olefinic double bond of bdpp is attached symmetrically to the metal atom [W-C(olefin) 2.403(8), 2.387(9) Ǻ] and is roughly parallel to the P-W-P axis. The C=C bond length of 1.359(11) Ǻ is only slightly longer than that expected for the free ligand and is indicative of relatively weak metal-olefin back-bonding. Other important bond lengths are: W-P 2.450(2), 2.462(2) Ǻ and W-C(C0) 2.020(7), 2.024(7) Ǻ (CO trans to CO) and 1.971(7) Ǻ (CO trans to olefin).

Crystal and Molecular Structure of Dithiocyanato(triphenylarsine)mercury(II)

1975 ◽  
Vol 53 (22) ◽  
pp. 3383-3387 ◽  
Author(s):  
Joseph Hubert ◽  
André L. Beauchamp ◽  
Roland Rivest
Keyword(s):  
Molecular Structure ◽  
Least Squares ◽  
Coordination Number ◽  
Diffraction Data ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Heavy Atom Method

The crystal and molecular structure of dithiocyanato(triphenylarsine)mercury(II) has been determined from X-ray diffraction data. The crystals are monoclinic, space group P21/c, with a = 10.290(7), b = 21.199(23), c = 10.719(7) Å, β = 112.00(2)°, and Z = 4. The structure has been solved by the heavy-atom method and refined by block-diagonal least-squares calculations. The agreement factor R obtained for 2607 'observed' reflections is 0.030. The crystal consists of single molecules. The 'characteristic' coordination number of mercury is three, with two sulfur and one arsenic atoms at the apexes of a triangle. The nitrogen atoms of the thiocyanate groups are at 2.67 and 2.74 Å from the adjoining mercury atoms and therefore link the different molecules together.

An Intermediate in the Conversion of an Acetylene to a Vinyl Derivative: The Crystal and Molecular Structure of trans-Chloromethylbis(trimethylarsine)-platinum(II) Hexafluorobut-2-yne

1972 ◽  
Vol 50 (14) ◽  
pp. 2276-2284 ◽  
Author(s):  
Brian W. Davies ◽  
Richard J. Puddephatt ◽  
Nicholas C. Payne
Keyword(s):  
Molecular Structure ◽  
Bond Length ◽  
Crystal And Molecular Structure ◽  
Three Dimensional ◽  
Free Ligand ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Monodentate Ligand ◽  
X Ray ◽  
Trigonal Bipyramidal

The crystal and molecular structure of trans-chloromethylbis(trimethylarsine)platinum(II) hexafluorobut-2-yne has been determined from three dimensional X-ray diffraction data recorded by diffractometric methods. The structure has been refined by full-matrix least-squares methods on F using 1156 reflections to an agreement factor R = 0.077. The crystals are monoclinic, space group [Formula: see text] with a = 6.803(8), b = 14.93(2), c = 20.20(2) Å, β = 104.9(1)°, and Z = 4. The coordination of the platinum atom is trigonal bipyramidal, with the acetylene considered a monodentate ligand, and the two trimethylarsine ligands occupying the equatorial plane. The chlorine atom and the methyl ligand occupy the apical positions, with Pt—Cl and Pt—C distances of 2.47(1) Å and 2.10(4) Å, respectively. The long Pt—Cl bond length indicates the strong trans-influence of the methyl ligand. The observed C—C bond length of 1.32(4) Å in the acetylene ligand is lengthened from the value of 1.22(9) Å measured in the free ligand. The geometry of the coordinated ligand is discussed in terms of the bonding scheme proposed by Greaves etal.

The crystal and molecular structure of di-μ-phenylthiolatobis[trichloro(dimethyl sulfide) tungsten(IV) (W—W)]

1983 ◽  
Vol 61 (12) ◽  
pp. 2809-2812 ◽  
Author(s):  
P. Michael Boorman ◽  
Joanne M. Ball ◽  
Kelly J. Moynihan ◽  
Vikram D. Patel ◽  
John F. Richardson
Keyword(s):  
Molecular Structure ◽  
Bond Length ◽  
Dimethyl Sulfide ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sulfide Ligands ◽  
Heavy Atom Method

The complex (Me2S)Cl3W(μ-SPh)2WCl3(SMe2), 1, has been isolated as one product of the 1:1 reaction between WCl4(Me2S)2 and SiMe3(SPh) in CH2Cl2 solution. A single crystal X-ray diffraction study shows that the molecule has the relatively unusual edge-shared bioctahedral structure, with a W—W bond length of 2.759(1) Å. The dimethyl sulfide ligands occupy positions trans to one another in the equatorial mean plane of the molecule, which has two-fold symmetry imposed on it. The structure was solved by the heavy atom method and refined to R = 0.044 and Rw = 0.058 for 2001 reflections. Crystals of 1 are monoclinic, space group C2/c, with a = 17.445(4), b = 12.594(2), c = 11.509(3) Å, β = 91.22(1)°, and Z = 4.

Determination of the structure of bis(propyldithiocarbamate)nickel(II)

1990 ◽  
Vol 55 (4) ◽  
pp. 1010-1014 ◽  
Author(s):  
Jiří Kameníček ◽  
Richard Pastorek ◽  
František Březina ◽  
Bohumil Kratochvíl ◽  
Zdeněk Trávníček
Keyword(s):  
Molecular Structure ◽  
Title Compound ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
Planar Configuration ◽  
Compound C ◽  
Heavy Atom Method

The crystal and molecular structure of the title compound (C8H16N2NiS4) was solved by the heavy atom method and the structure was refined anisotropically to a final R factor of R = 0.029 (wR = 0.037) for 715 observed reflections. The crystal is monoclinic, space group P21/c with a = 948.3(2), b = 776.9(2), c = 1 167.4(2) pm, β = 125.14(2)°, Z = 2. The molecule contains two four-membered NiSCS rings of approximately planar configuration with the Ni atom situated at a centre of symmetry. The molecules are arranged in chains along the c-axis of the unit cell.

The crystal structure of dibutyl-bis(pentamethylenedithiocarbamato)tin(IV)

1986 ◽  
Vol 51 (11) ◽  
pp. 2521-2527 ◽  
Author(s):  
Jan Lokaj ◽  
Eleonóra Kellö ◽  
Viktor Kettmann ◽  
Viktor Vrábel ◽  
Vladimír Rattay
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Coordination Polyhedron ◽  
Crystal And Molecular Structure ◽  
Distorted Octahedron ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The crystal and molecular structure of SnBu2(pmdtc)2 has been solved by X-ray diffraction methods and refined by a block-diagonal least-squares procedure to R = 0.083 for 895 observed reflections. Monoclinic, space group C2, a = 19.893(6), b = 7.773(8), c = 12.947(8) . 10-10 m, β = 129.07(5)°, Z = 2, C20H38N2S4Sn. Measured and calculated densities are Dm = 1.38(2), Dc = 1.36 Mg m-3. Sn atom, placed on the twofold axes, is coordinated with four S atoms in the distances Sn-S 2.966(6) and 2.476(3) . 10-10 m. Coordination polyhedron is a strongly distorted octahedron. Ligand S2CN is planar.

Crystal and molecular structure of Bis(4-amino-3,5,6-trichloropicolinato)-manganese(II) dihydrate

1981 ◽  
Vol 34 (4) ◽  
pp. 891 ◽  
Author(s):  
G Smith ◽  
EJ O'Reilly ◽  
CHL Kennard
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Three Dimensional ◽  
Direct Methods ◽  
Polymer Chains ◽  
Monoclinic Space Group ◽  
Carboxylate Oxygen ◽  
Group 12 ◽  
Distorted Octahedral ◽  
A Cell

The manganese(II) complex [Mn(picl)2,2H2O]n of the herbicide picloram has been prepared and the crystal and molecular structure determined from three-dimensional X-ray data collected by counter methods. The crystals of the complex are monoclinic, space group 12/a with two complex units in a cell of dimensions a 23·052(5), b 13·840(2), c 6·441(1) �, β 98·20(1)�. The structure was solved by direct methods and refined by full matrix least squares to unweighted and weighted Rfactors of 0·035 and 0·038 respectively for 887 'observed' reflections. The polymer is best described as having a centrosymmetric two-molecule unit [Mn-O, 2·162(3), 2·246(3) �] with two oxo bridges between manganese centres through two single carboxylate oxygens of the four substituted picolinate ligands. The two molecules are related by a twofold axis. The units form infinite one-dimensional polymer chains in the c direction through oxo bridges involving one oxygen from the other two picolinate ligands [Mn-Mn 3·636(1)�]. The bis(bidentate)picolinate bites are completed by the pyridlne nitrogens [Mn-N, 2·313(4) �] giving a very distorted octahedral MnO4N2 coordination sphere about each manganese [N-Mn-N', 97.0(3)�; O-Mn-O range, 68·9-168.2(3)�; O-Mn-Nrange, 69·9-138·5(3)�]. The lattice waters are involved in hydrogen-bonding interactions which link the polymer in the a crystallographic direction with the uncoordinated carboxylate oxygen ( O···O,2·824, 2·936 �) and the 4-amino groups from the adjacent picolinate ligand (N· ··0, 2·852, 3·030�).

The crystal and molecular structure of 1,4-diphenyl-2,2′,3,3′,5,5′,6,6′-octamethylcyclo-1,4-diphospha-2,3,5,6-tetrasilahexane, a phosphorus–silicon heterocycle

1979 ◽  
Vol 57 (2) ◽  
pp. 174-179 ◽  
Author(s):  
A. Wallace Cordes ◽  
Paul F. Schubert ◽  
Richard T. Oakley
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Chair Conformation ◽  
Monoclinic Space Group ◽  
Single Bond ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
X Ray ◽  
Bond Lengths

The crystal structure of 1,4-diphenyl-2,2′,3,3′,5,5′,6,6′-octamethylcyclo-1,4-diphospha-2,3,5,6-tetrasilahexane, (PhPSi2Me4)2, has been determined by single crystal X-ray diffraction. The crystals are monoclinic, space group P21/c, with a = 9.866(1), b = 11.921(1), and c = 11.324(2) Å, β = 104.31(1)°, Z = 2, and ρcalcd = 1.15 g/cm3. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.060 and Rw of 0.078, for 1173 reflections with intensities greater than 3σ. The (PhPSi2Me4)2 molecule lies on a crystallographic centre of symmetry, and the six-membered P2Si4 ring has a chair conformation with equatorial phenyl groups. The endocyclic angles at P (104.4(1)°) and Si (104.9(2)°) are intermediate between those found in cyclic hexaphosphine and hexasilane molecules, and the Si—Si and P—Si distances of 2.345(3) and 2.252(4) Å, respectively, correspond to single bond lengths, with no appreciable evidence for secondary pπ → dπ bonding between phosphorus and silicon. The Si—C (1.867(8) Å) and P—C (1.828(7) Å) bond lengths are also normal. The variations in the Si—P—C (101.6(2)°, 108.6(2)°), P—Si—C (range 106.2(3)–120.0(3)°), and Si—Si—C (range 105.8(3)–113.7(3)°) angles indicate that the positions of the exocyclic methyl and phenyl groups are influenced by both intra- and intermolecular steric forces.

Synthesis, IR and X-Ray Studies of Tetra(N,N′-tetraethyl-N″-benzoyl- phosphorictriamide)-tetra(μ-3-methoxo)-tetra(methanol)tetra-NickeI(II)

1998 ◽  
Vol 53 (8) ◽  
pp. 836-840 ◽  
Author(s):  
Vladimir A. Ovchynnikov ◽  
Vladimir M. Amirkhanov ◽  
Anatoliy A. Kapshuk ◽  
Tatyana Yu. Sliva ◽  
Tadeusz Glowiak ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Oxygen Atom ◽  
Metal Ion ◽  
Crystal And Molecular Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Octahedral Environment ◽  
Distorted Octahedral ◽  
Methoxy Groups ◽  
Oxygen Atoms

Abstract A new nickel(II) complex with N,N′-tetraethyl-N″-benzoylphosphortriamide (HL = C6H5C(O)N(H)P(O)(NEt2)2) of composition Ni4L4(OCH3)4·(HOCH3)4 (1) has been synthe­ sized. The crystal and molecular structure of 1 has been determined from the X-Ray diffraction data (tetragonal, space group P4̄21c with a = 17.000(2) Å, c = 15.338(3) Å, Z = 2; R = 0.0399 for 1412 unique reflections). The structure is made up of cubane-like tetramers. In the corners of a cube there are 4 atoms of nickel and 4 atoms of oxygen of methoxy groups. The nickel atoms are characterized by a slightly distorted octahedral environment, which consists of three oxygen atoms of methoxy groups, carbonylic and phosphorylic oxygen atoms of the ligand L-, and an oxygen atom of a methanol molecule. The ligands L- coordinate to the metal ion forming a chelate via the oxygen atoms of carbonylic and phosphorylic groups.

Weak interactions observed in ruthenium and iridium complexes containing hydride, amine, and bulky phospyhine ligands

1997 ◽  
Vol 75 (5) ◽  
pp. 475-482 ◽  
Author(s):  
Wei Xu ◽  
Alan J. Lough ◽  
Robert H. Morris
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Weak Interactions ◽  
Crystal Structure Analysis ◽  
Monoclinic Space Group ◽  
Iridium Complexes ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
X Ray ◽  
Van Der Waals Contacts

New amineruthenium and amineiridium hydride derivatives have been synthesized and characterized with the objective of observing intramolecular [Formula: see text] or [Formula: see text] interactions. These include RuHCl(CO)(L)(PPri3)2 (1a, L = NH2NH2; 1b, L = NH3) and IrCl2(L)(H)(PCy3)2 (2a, L = SC(NH2)2; 2b, L = NH3; 2c, L = NH2NH2; 2d, L = NH2(CH2)3NH2; 2e, L = NH2OH). Instead, weak [Formula: see text] van der Waals contacts have been detected in the solid state by X-ray analysis and in solution by NMR T1 measurements and nOe techniques. Both X-ray crystal structure analysis and minimum T1 measurements indicate that the [Formula: see text] distances in the [Formula: see text] interactions are ca•2.0–2.2 Å. The weak interactions might influence the course of deuteration of these complexes under D2 gas. The crystal and molecular structure of IrCl2(NH3)(H)(PCy3)22a has been determined by X-ray diffraction at 173 K: monoclinic, space group P21/n, a = 14.859(2) Å, b = 18.579(3) Å, c = 18.548(3) Å, β = 97.29(1)°, V = 5079.1(13) Å3, Z = 4, full-matrix least-squares refinement on F2 for 10 953 independent reflections; R[F2 > 4σ(F2)] = 0.0283, wR(F2) = 0.0704. Keywords: ruthenium, iridium, hydride, dihydrogen, complexes, hydrogen bond, NMR, X-ray.

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