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).

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).

Structure cristalline et moléculaire d'un composé tricyclique contenant le cycle à dix chaînons dioxo diaza diphosphécine

1992 ◽  
Vol 70 (3) ◽  
pp. 809-816 ◽  
Author(s):  
Brigitte Duthu ◽  
Karim El Abed ◽  
Douraid Houalla ◽  
Robert Wolf ◽  
Joël Jaud
Keyword(s):  
Molecular Structure ◽  
Comparative Analysis ◽  
Double Bond ◽  
Mass Spectroscopy ◽  
Crystal And Molecular Structure ◽  
Accurate Information ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nmr Parameters ◽  
C Nmr

The sulfuration of the tricyclic organophosphorous dimer 2 leads easily to the dithiotricyclic derivative 3, which has been characterized by 31P, 1H, and 13C NMR, elemental analysis, and mass spectroscopy. Its crystal and molecular structure has been established by X-ray diffraction and compared to that of 2, which was previously determined. The comparative analysis of X-ray diffraction and NMR parameters gives accurate information about the molecular structure of both compounds. A numerical value of the anistropy cone of the P=S double bond is proposed. Keywords: phosphecine, NMR, X-ray, tricycle.

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.

Crystal and molecular structure of carbonylcyanide-4-chlorophenylhydrazone(4-chlorophenylhydrazonopropanedinitrile)

1984 ◽  
Vol 49 (10) ◽  
pp. 2363-2370
Author(s):  
Viktor Vrábel ◽  
Ernest Šturdík ◽  
Michal Dunaj-Jurčo ◽  
Jan Lokaj ◽  
Ján Garaj
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Structural Analysis ◽  
Least Squares Method ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Diffraction Method ◽  
X Ray Diffraction ◽  
X Ray ◽  
Heavy Atom Method

The crystal structure of carbonylcyanide-4-chlorophenylhydrazone was solved by the single crystal X-ray diffraction method and interpreted by the heavy atom method. The compound crystallizes in the P21/c monoclinic group with 4 molecules per unit cell and with lattice parameters: a = 1.1843(3), b = 0.5944(1), c = 1.4922(3) nm and β = 117.92(2)°. The structure was refined by the least squares method for 1 078 observed reflections to a final value of R = 4.9%. The crystal structure consists of monomeric units, where hydrogen bonds were observed between atoms N3...H5 0.2193 nm and N3...H3 0.2404 nm between two molecules transformable through centre of symmetry -x, -y, -z. The name 4-chlorophenylhydrazonopropanedinitrile is recommended for the studied compound on the basis of this X-ray structural analysis.

Synthesis and Spectroscopic Studies of Triorganotin(IV) Complexes Involving Diorganophosphino and Diorganophosphino-N-Phenyl(Thioformamido) Ligands - the Crystal and Molecular-Structure of Dicyclohexylphosphino-N-Phenyl(Thioformamido)-Triphenyltin, Ph3Sn[(c-C6H11)2PC(S)NPh]

1986 ◽  
Vol 39 (8) ◽  
pp. 1221 ◽  
Author(s):  
D Dakternieks ◽  
BF Hoskins ◽  
CL Rolls
Keyword(s):  
Molecular Structure ◽  
Sulfur Atom ◽  
Crystal And Molecular Structure ◽  
Spectroscopic Studies ◽  
X Ray Diffraction ◽  
Dichloromethane Solution ◽  
Triclinic Space Group ◽  
X Ray ◽  
Tetrahedral Environment ◽  
Tin Complexes

Phosphorus-31 and tin-119 n.m.r . data imply that the tin complexes R3Sn[R1,PC(S) NPh ] (where R = Ph, Me, Bu; R′ = Ph) exist in solution as both sulfur-bonded and nitrogen-bonded isomers. When R′ = c-C6H11, only one isomer is observed. n.m.r . data are also reported for the series R3SnPR′2. Both series of complexes contain four-coordinate tin in dichloromethane solution. The crystal and molecular structure of the tin(IV) complex Ph3Sn[(c-C6H11)2PC(S) NPh ] has been determined by single-crystal X-ray diffraction techniques. The crystals are triclinic, space group Pī , a 10.689(2), b 11.066(1), c 16.315(3) Ǻ, α 101.94(1), β 104.85(1) and γ 105.72(1)° with Z 2; R and Rw were 0.032 and 0.030 respectively for 5169 unique reflections with I ≥ 2σ(I). The structure has two independent centrosymmetrically related mononuclear molecules within the unit cell. The tin atom is in a tetrahedral environment formed by three phenylic carbon atoms and a sulfur atom from the [(c- C6H11)2PC(S) NPh ]- ligand.

Molecular structure of sym-fac-[(1,5,9-triazanonane)-(R,S)-aspartato]cobalt(III) perchlorate monohydrate and its relationship to the optically active [Co(dtp)(S)-Asp]+ isomers

1990 ◽  
Vol 55 (9) ◽  
pp. 2216-2225 ◽  
Author(s):  
Jan Ondráček ◽  
Jitka Soldánová ◽  
František Jursík
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Structural Data ◽  
Chair Conformation ◽  
Optically Active ◽  
X Ray Diffraction ◽  
X Ray ◽  
Network Of Hydrogen Bonds ◽  
Heavy Atom Method

The crystal and molecular structure of the title compound was determined by X-ray diffraction. The structure was solved by the heavy-atom method and refined to an R value of 0.118 for 997 observed reflections. The unit cell is monoclinic with a = 11.980(1), b = 12.130(1), c = 12.641(1) Å, β = 108.18(1)°, Z = 4. The space group is P21/c. The crystals are composed of sym-fac-[Co(dtp)(R,S)-Asp]+, ClO4-, and H2O held together probably in a network of hydrogen bonds. The structural data obtained allow an explanation for the sym-fac-[Co(dtp)(S)-Asp]+ isomer optical activity contributions which can arise from the distorted chair conformation of one of the two dpt fused chelate rings, the donor atom distortions from the defined plane, and the (S)-aspartic acid vicinal chirality.

The crystal and molecular structure of 4-phosphonomethyl-2-oxo-1-piperazinylacetic acid

1989 ◽  
Vol 54 (1) ◽  
pp. 160-165 ◽  
Author(s):  
František Pavelčík ◽  
Karol Havetta ◽  
Jaroslav Páterek
Keyword(s):  
Molecular Structure ◽  
Double Bond ◽  
Single Crystals ◽  
Functional Group ◽  
Least Squares Method ◽  
Crystal And Molecular Structure ◽  
Monoclinic Space Group ◽  
Carboxyl Group ◽  
X Ray Diffraction ◽  
X Ray

The structure of the title compound was determined by the method of X-ray diffraction of single crystals. The substance crystallizes in the P21/c monoclinic space group. The structure was refined by the least squares method to R = 0.044 on the basis of 2 076 observed reflections. It was found that this compound is not a dicarboxylic acid but rather an intramolecularly cyclized lactam. The hydrogen phosphonato functional group participates in the betain form, while the carboxyl group is not ionized. The conformation of the six-membered oxopiperazine ring is similar to that of cyclohexane in which the peptidic group plays a similar role to the double bond.

The Crystal and Molecular Structure of sym-fac-(1,4,7-Triazaheptane)-(S)-aspartatocobalt(III) Diperchlorate Dihydrate

1994 ◽  
Vol 59 (5) ◽  
pp. 1052-1058 ◽  
Author(s):  
Jan Ondráček ◽  
Jana Ondráčková ◽  
Jaroslav Maixner ◽  
František Jursík
Keyword(s):  
Molecular Structure ◽  
Aspartic Acid ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Membered Ring ◽  
Boat Conformation ◽  
Hydrogen Atoms ◽  
Orthorhombic System ◽  
Anisotropic Temperature ◽  
Heavy Atom Method

The crystal and molecular structure of s-fac-[Co((S)-Asp)(dien)]ClO4 . HClO4 .2 H2O (dien = 1,4,7-triazaheptane) was solved by the heavy atom method. The position parameters of the non-hydrogen atoms and their anisotropic temperature parameters were refined based on 1 726 observed reflections with a final value of R = 0.073. The substance crystallizes in the orthorhombic system in the space group P212121, Z = 4, a = 8.506(1), b = 17.171(2), c = 13.277(1) Å. The structure involves hydrogen bonds between the O2, O4 and HN2 atoms of aspartic acid and the two molecules of water. The five-membered dien chelate rings take the asymmetric envelope conformations. The five-membered ring of (S)-aspartic acid possesses the symmetric envelope conformation whereas the six-membered ring exhibits the skew boat conformation.

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