The preparation and the crystal and molecular structure of S3N2NH2+BF4−; a molecular orbital study of the protonation of the trisulphur trinitride anion

1984 ◽  
Vol 62 (9) ◽  
pp. 1822-1827 ◽  
Author(s):  
Clifford G. Marcellus ◽  
Richard T. Oakley ◽  
A. Wallace Cordes ◽  
William T. Pennington
Keyword(s):  
Molecular Structure ◽  
Molecular Orbital ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Membered Ring ◽  
Molecular Orbital Calculations ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Molecular Orbital Study

Protonation of the trisulphur trinitride ion, S3N3−, with tetrafluoroboric acid yields the ring-contracted S-amino thiodithiazyl salt, S3N2NH2+BF4−. The crystal and molecular structure of this salt has been determined by X-ray diffraction. The crystals are triclinic, space group P1, with a = 5.445(2), b = 7.346(3), c = 9.473(5) Å, α = 85.89(4), β = 83.92(3), γ = 82.13(3)°, V = 372.6(4) Å3, Dc = 2.02 g cm−3, and Z = 2. The structure was solved by direct methods and refined by full-matrix least-squares procedures to give a final R = 0.060. The structure of the five-membered ring with a single exocyclic NH2 group bonded to sulphur is discussed in relation to other S3N2NR derivatives. The reasons for the instability of six-membered rings of the type S3N3R are discussed in the light of MNDO molecular orbital calculations on an S3N3H model.

Synthese und Molekülgeometrie von Dichloro[η2-bis(di-r-butylphosphino)methan]pIatin(II), Pt(dtbpm)Cl2. Die Elektronenstruktur von 1,3-Diphosphaplatinacyclobutan-Fragmenten / Synthesis and Molecular Structure of Dichloro[η2-bis(di-t-butylphosphino)methane]platinum(II), Pt(dtbpm)Cl2. The Electronic Structure of 1,3-Diphosphaplatinacyclobutane Fragments

1987 ◽  
Vol 42 (4) ◽  
pp. 395-409 ◽  
Author(s):  
Peter Hofmann ◽  
Helmut Heiß ◽  
Gerhard Müller
Keyword(s):  
Molecular Structure ◽  
Electronic Structure ◽  
Crystal And Molecular Structure ◽  
Cone Angle ◽  
Membered Ring ◽  
Experimental Investigations ◽  
Molecular Orbital Calculations ◽  
X Ray Diffraction ◽  
X Ray ◽  
Potential Precursor

Based upon the experimentally known but yet unexplained very different reactivities of the two isoelectronic and isolobal intermediates Pt(PMe3)2 and Pt(PEt3)2, the electronic structure and bonding capability of such 14 electron fragments as a function of their geometry (P-Pt-P angle α, determined by the phosphane cone angle) are investigated using molecular orbital calculations. A decrease of the P-Pt -P angle leads to an exceptionally pronounced energy ascent of the b2-HOMO of Pt(PR3)2 species, which, as a consequence, might lead to unusual reactivity patterns and bonding capabilities of 1,3-diphosphaplatinacyclobutane fragments, for which an extreme electronic situation is enforced by steric constraints. Dichloro[η2-bis(di-r-butylphosphino) methane]platinum(II), Pt(dtbpm)Cl2, is synthesized as a potential precursor of Pt(dtbpm), in order to allow experimental investigations of this taylor made four-membered ring chelate complex of Pt(0). The crystal and molecular structure of Pt(dtbpm)Cl2 · 2 CHCl3 has been determined by X-ray diffraction.

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.

The crystal and molecular structure of tetrabenzocyclodecan-1,6-dione

1980 ◽  
Vol 58 (8) ◽  
pp. 777-779 ◽  
Author(s):  
T. Stanley Cameron ◽  
Christine Chan ◽  
David G. Morris ◽  
Alistair G. Shepherd
Keyword(s):  
Molecular Structure ◽  
Diffraction Analysis ◽  
Title Compound ◽  
Crystal And Molecular Structure ◽  
Membered Ring ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Nmr Spectrum ◽  
X Ray ◽  
C Nmr

The crystals belong to the orthorhombic space group C222, with a = 9.226, b = 12.092, c = 16.513 Å, Z = 4. A single crystal X-ray diffraction analysis has shown that the title compound, in which all carbon atoms are sp2 hybridized, exists with the ten membered ring in a slightly twisted tub conformation. The 13C nmr spectrum is also reported.

Crystal and molecular structure of 4α-t-Butylcyclohexane-1β,2β-diol

1972 ◽  
Vol 25 (10) ◽  
pp. 2117 ◽  
Author(s):  
MD Brice ◽  
BR Penfold ◽  
WT Robinson
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Chair Conformation ◽  
Intensity Data ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Full Matrix ◽  
X Ray ◽  
R Factor ◽  
Least Squares Techniques

The crystal and molecular structure of 4α-t-butylcyclohexane-1β,2,β-diol, C10H20O2, has been determined by X-ray diffraction methods. The compound crystallizes in the triclinic space group Pi with 4 molecules in a unit cell of dimensions a = 12.268, b = 15.921, c = 6.322�, α = 82.53, β = 114.45, γ = 111.13�. The intensity data were measured by counter methods using Cu Kα radiation; the structure was solved by means of the tangent formula, and was refined using full matrix least-squares techniques to a final R-factor of 0.063 for 1199 reflections. The crystal structure consists of two sets of crystallographically non-equivalent molecules hydrogen-bonded to form discrete chains parallel to the c axis. The cyclohexane rings are in the chair conformation.

Crystal and molecular structure of Octacarbonylbis(diphenylarsino)-methanedimanganese(0)

1983 ◽  
Vol 36 (4) ◽  
pp. 683 ◽  
Author(s):  
BF Hoskins ◽  
RJ Steen
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Parent Compound ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Fourier Methods ◽  
X Ray

The crystal structure of the complex Mn2(CO)8(dam) (dam = Ph2AsCH2AsPh2) has been determined by three-dimensional X-ray diffraction methods. The crystals are triclinic, space group P1, with a 11.191(1), b 16.498(5), c 9.455(1) �, a 93.64(2), β 109.08(2), γ 89.36(2)� and contain two discrete, binuclear molecules of Mn2(CO)8(dam) per unit cell. The structure, solved by direct and Fourier methods, was refined by a least-squares procedure to R and Rw of 0.065 and 0.082 respectively for 1907 independent, statistically significant reflections collected by counter methods. The feature of particular interest in this compound is the accommodation of the bridging bidentate dam ligand [As.. .As separation 3.242(2) �] across a shorter Mn�-Mn� bond [2.962(3) �] which constrains the molecule so that a much less staggered configuration of the two manganese coordination octahedra is observed relative to the parent compound Mn2(CO)10, the rotation of the two equatorial planes in the former being 30�.

Synthesis, conformational analysis, and molecular structure of 5-ethyl-5,6-dihydro-11H-dibenzo[b,e]azepine-6-thione

1994 ◽  
Vol 72 (2) ◽  
pp. 334-338 ◽  
Author(s):  
J. Irurre ◽  
F. Marquillas ◽  
A. Alvarez-Larena ◽  
J.F. Piniella
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Conformational Analysis ◽  
Activation Barrier ◽  
Direct Methods ◽  
Membered Ring ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
X Ray ◽  
R Value

5-Ethyl-5,6-dihydro-11H-dibenzo[b,e]azepine-6-thione has been synthesized and studied in the solid state and in solution by X-ray diffraction and 1H DNMR, respectively. The crystals are monoclinic, P21/n, a = 9.642(1), b = 13.757(2), c = 9.889((2) Å, β = 98.57(1)°, Z = 4. The structure has been solved by direct methods and refined to an R value of 0.040 for 1771 reflections with I > 2.5σ(I). The seven-membered ring has a slightly deformed boat conformation. The activation barrier associated with the inversion ring has been determined, being ΔG≠ = 21.6 kcal/mol.

Synthesis, Infrared and X-Ray Studies of Diphenyltellurium(IV) Nitrosocarbamylcyanmethanides. X-Ray Evidence for Stability of a Tritelluroxane Fragment -Ph2Te-O-Ph2Te-O-Ph2Te-

1996 ◽  
Vol 51 (6) ◽  
pp. 832-837 ◽  
Author(s):  
Konstantin V. Domasevitch ◽  
Victor V. Skopenko ◽  
Eduard B. Rusanov
Keyword(s):  
Molecular Structure ◽  
Oxygen Atom ◽  
Spectroscopic Data ◽  
Crystal And Molecular Structure ◽  
X Ray Diffraction ◽  
Nitroso Group ◽  
Triclinic Space Group ◽  
X Ray ◽  
Ir Spectroscopic ◽  
Derivatives Of

Abstract Diphenyltellurium(IV) derivatives of the types Ph2Te{ACO}2 (1), Ph4Te2O{ACO}2 (2) and Ph6Te3O2{ACO} (3) (ACO = nitrosocarbamylcyanmethanide -ONC(CN)C(O)NH2) have been prepared. The IR spectroscopic data reveal that the ambidentate ligands are coordinated to the tellurium(IV) atom in a monodentate manner via the nitroso oxygen atom. The crystal and molecular structure of 3 has been determined from X-ray diffraction data (triclinic, space group P1̅ with a = 12.382(2), 6=13.100(2), c = 14.944(3) Å, a = 87.74( 1), β = 85.04(2), 7 = 66.29( 1)°, V = 2211.0 A , Z = 2, R = 0.040). The structure is made up of unsymmetric molecules, in which the tellurium atoms are linked by oxo bridges to form chains Te-O-Te-O-Te (d(Te-O) ca. 1.94-2.09 A). The Te-0 (nitroso group) bond lengths are in the range 2.33 - 2.36 Å

Crystal structures of medium ring compounds. Part III. The crystal and molecular structure of trans-anti-trans-4,5:9,10-biscyclohexano-1,3,6,8-tetraoxecane

1979 ◽  
Vol 57 (16) ◽  
pp. 2154-2158 ◽  
Author(s):  
Aris Terzis ◽  
T. Bruce Grindley
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Chair Conformation ◽  
Membered Ring ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ring Compounds ◽  
R Value ◽  
Medium Ring

The crystal structure of trans-anti-trans-4,5:9,10-biscyclohexano-1,3,6,8-tetraoxecane (3) has been determined by X-ray diffraction. The crystals are monoclinic, a = 11.919(3), b = 17.330(7), c = 7.019(2) Å, β = 98.91(1)°, P21/c, with Z = 4. The structure was solved by application of the tangent formula and refined by large block least squares to a final R value of 0.060 (Rw = 0.058).The ten-membered ring is present in the crystal in a twist-chair-boat-chair conformation — one which has been calculated to be relatively unstable for cyclodecane. Possible reasons why 3 adopts this conformation are discussed.

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.

The conformation of a ten-membered ring: the crystal and molecular structure of trans-syn-trans-4,5:9,10-biscyclohexano-1,3,6,8-tetraoxecane

1977 ◽  
Vol 55 (14) ◽  
pp. 2692-2699 ◽  
Author(s):  
Aris Terzis ◽  
T. Bruce Grindley ◽  
J. Brian Faught
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Membered Ring ◽  
Thermal Parameters ◽  
X Ray Diffraction ◽  
X Ray ◽  
R Value

The crystal structure of trans-sys-trans-4,5:9,10-biscyclohexano-1,3,6,8-tetraoxecane (1) has been determined by X-ray diffraction. The crystals are monoclinic, a = 10.995(2), b = 5.291(1), c = 12.241(2) Å, β = 114.68(1)°, P21/c, with Z = 2. The structure was solved by the application of symbolic addition procedures and refined with anisotropic thermal parameters for all atoms to a final R value of 0.039 (Rw 0.062) for 1135 independent reflections.The ten-membered tetraoxecane ring is present in the crystal in a boat-chair-boat (BCB) conformation, which is somewhat different in geometry than the BCB conformations observed for cyclodecane derivatives. The causes of these differences are discussed. Intramolecular non-bonded interactions cause one CH2 group to be significantly distorted from local C2v symmetry.

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