Some Substituent Effects in the Formation of Binuclear Metalladienes and 1,2-Dimetallacycloheptadienones From Reactions Between (η-C5H5)2Rh2(μ-CO)(CF3C2CF3) and Alkynes

1986 ◽  
Vol 39 (8) ◽  
pp. 1187 ◽  
Author(s):  
CW Baimbridge ◽  
RS Dickson ◽  
GD Fallon ◽  
I Grayson ◽  
RJ Nesbit ◽  
...  
Keyword(s):  
Heavy Atom ◽  
Substituent Effects ◽  
Unit Cell ◽  
The Other ◽  
Orthorhombic Space Group ◽  
Methyl Group ◽  
Space Group ◽  
X Ray ◽  
Alternative Pathways ◽  
X Ray Crystallography

The reaction between (η-C5H5)2Rh2(CO)(CF3C2CF3)(1) and alkynes, RC=CR′, can proceed by two alternative pathways. One gives the complexes (η- C5H5)2Rh2{C4(CF3)2RR′CO} (2) in which a pentadienone unit bridges the Rh - Rh bond. The other produces the binuclear metalladiene complexes (η-C5H5)2Rh2{C4(CF3)2RR?} (3) plus the dicarbonyl complex (η-C5H5)2Rh2(CO)2(CF3C2CF3) (4). The formation of (2) is strongly favoured with the dialkylacetylenes BuC≡CBu and MeC =CR (R = Et, Pri, But). With the unsymmetrical acetylenes, two isomers of (2) are isolated. The tendency to form (3) + (4) increases when there are electron-withdrawing substituents such as CN on the alkyne, and becomes dominant when the alkyne is polar (e.g. MeC≡CR with R = Ph, CF3 or CO2Me). The reactions with MeC≡CR are highly regioselective, with only one of the two possible regioisomers being isolated in each case. This has the methyl group in the 3-position of the metalladiene ring. Unexpected products formed in the reactions with MeC≡Cet and MeC≡CPri have been characterized by X-ray crystallography. One is a 1,2- dimetallacycloheptadienone complex, (η-C5H5)2Rh2{C4(CF3)2Me(CMe2OH)CO}. The compound crystallizes with 16 molecules in the orthorhombic space group Fdd2 in a unit cell of dimensions a 31.728(15), b 27.923(14), c 9.275(5) Ǻ. The structure was solved by heavy atom methods and refined to R 0.037 based on 2644 observed reflections. The CMe2(OH) group is adjacent to the carbonyl in the bridging group. The other is a binuclear metalladiene complex (η-C5H5)2Rh2{C4(CF3)2Me( COMe )}. It crystallizes with eight molecules in the orthorhombic space group P bca in a unit cell of dimensions a 17.349(8), b 15.819(8), c 13.720(7) Ǻ. The structure was solved by heavy atom methods and refined to R 0.053 based on 3045 observed reflections above background. The acyl group is adjacent to the metal in the metalladiene ring. These two complexes are formed from (1) and impurities present in the alkynes.

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

Structural and vibrational studies of 1,1,3,3-tetracyanopropane and 2,2,4,4,6-pentacyanocyclohexenamine

1987 ◽  
Vol 65 (2) ◽  
pp. 261-270 ◽  
Author(s):  
R. A. Bell ◽  
B. E. Brown ◽  
M. Duarte ◽  
H. E. Howard-Lock ◽  
C. J. L. Lock
Keyword(s):  
Unit Cell ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
New Methods ◽  
Cell Dimensions ◽  
Cell Data ◽  
Unit Cell Data ◽  
Monoclinic Cell ◽  
C Nmr

1,1,3,3-Tetracyanopropane, 1, was prepared in low yields by a literature method with 2,2,4,4,6-pentacyanocyclohexenamine, 2, as a major by-product. The products were examined by X-ray crystallography. 1 has an orthorhombic space group, Pbcn (No. 60) with cell dimensions, a = 7.158(2), b = 10.510(3), c = 9.733(2) Å and has four formula units in the unit cell. 2 has a monoclinic cell, P21/c (No. 14) with cell dimensions a = 14.368(3), b = 6.626(1), c = 12.300(2) Å, β = 115.60(1)° and has 4 formula units in the unit cell. Data were collected with use of MoKα radiation and a Nicolet P3 diffractometer. The crystal structures were determined by standard methods and refined to Rw = 0.037 (1) and Rw = 0.040 (2) on the basis of 782 and 2108 unique reflections. Bond lengths and angles in the two compounds are normal. 2 has what has been considered to be the less likely tautomeric structure. Both compounds were examined by 1H, 13C nmr, vibrational spectroscopy, and mass spectroscopy. For 2 there was no evidence of the alternative tautomeric structure. New methods were developed for the preparation of both compounds and the mechanism of the original reaction rationalized.

X-ray powder diffraction data for 2-[((3R)-5-oxo-4-phenyltetrahy drofuran-3-yl)methyl]isoindoline-1,3-dione, C19H15NO4

2016 ◽  
Vol 31 (2) ◽  
pp. 155-158
Author(s):  
Shoujun Zheng ◽  
Kailin Xu ◽  
Qing Wang ◽  
XiaoLin Tang ◽  
Yanmei Huang ◽  
...  
Keyword(s):  
Cell Volume ◽  
Powder Diffraction ◽  
Unit Cell Volume ◽  
Unit Cell ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Element Analysis ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters

2-[((3R)-5-oxo-4-phenyltetrahydrofuran-3-yl)methyl]isoindoline-1,3-dione, C19H15NO4, was synthesized for the first time. Its structure was characterized by element analysis, ultraviolet spectrometry, nuclear magnetic resonance, and single X-ray diffraction (SXRD). X-ray powder diffraction (XRPD) data of title compound were collected and calculated. The result of SXRD shows that its crystal system is orthorhombic, space group is Pbca, and unit-cell parameters are a = 8.861 57(7), b = 14.6666(10), c = 24.4247(19) Å, α =β =γ =90°, unit-cell volume V = 3174.4 Å3, and Z = 8. All XRPD measured lines were indexed and consistent with the Pbca space group [a = 14.639(7), b = 24.378(3), c = 8.918(1) Å, α = β = γ = 90°, unit-cell volume V = 3182.7(9) Å3, Z = 8]. No detectable impurities were observed.

Synthesis, spectroscopic characterization, and structural studies of new Cu(I) and Cu(II) complexes containing organophosphorus ligands, and crystal structures of (Ph3P)2Cu[S2PMe2], (Ph3P)2Cu[(OPPh2)2N], Cu[(OPPh2)2N]2, and Cu[(OPPh2)(SPPh2)N]2

2001 ◽  
Vol 79 (5-6) ◽  
pp. 983-991 ◽  
Author(s):  
Anca Silvestru ◽  
Adina Rotar ◽  
John E Drake ◽  
Michael B Hursthouse ◽  
Mark E Light ◽  
...  
Keyword(s):  
Spectroscopic Characterization ◽  
Molecular Structures ◽  
Orthorhombic Space Group ◽  
Phosphorus Ligands ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
Multinuclear Nmr Spectroscopy

The Cu(I) complexes, (Ph3P)2CuL (L = [S2PMe2]-, [OSPR2]- (R = Me, Ph), [(XPR2)(YPR'2)N]- (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL2 (L = [(XPR2)(YPR'2)N]- (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear NMR spectroscopy and in two cases by X-ray crystallography. (Ph3P)2Cu[S2PMe2] (1) crystallizes in the orthorhombic space group P212121 (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) Å, V = 3521(6) Å3 and Z = 4, and (Ph3P)2Cu[(OPPh2)2N] (4) in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 9.8079(2), b = 12.9141(3), c = 22.5666(5) Å, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) Å3 and Z = 2. In both cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP2S2 and CuP2O2 cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh2)2N]2 (8) and Cu[(OPPh2)(SPPh2)N]2 (9) crystallize in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 8.887(2), b = 10.739(2), c = 12.477(3) Å, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) Å3 and Z = 1 for 8, and a = 9.626(2), b = 14.151(3), c = 24.752(5) Å, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) Å3 and Z = 3 for 9. The molecule of Cu[(OPPh2)2N]2 (8) has a planar CuO4 core, while in Cu[(OPPh2)(SPPh2)N]2 (9) both planar and tetrahedral copper cores are observed in a ratio of 1:2.Key words: structure, copper, thiophosphinates, oxo- and thio-imidodiphosphinates

X-ray structures of adducts of 1,2,5-triphenylphosphole with dimethyl acetylenedicarboxylate: a confirmation, a revision, and a new structure

1993 ◽  
Vol 71 (11) ◽  
pp. 1873-1889 ◽  
Author(s):  
Martin B. Hocking ◽  
Francies W. Van Der Voort Maarschalk
Keyword(s):  
Amorphous Material ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
Dimethyl Acetylenedicarboxylate ◽  
Orthorhombic Space Group ◽  
Polymeric Product ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Refinement

Dimethyl acetylenedicarboxylate was reacted with 1,2,5-triphenylphosphole under mild conditions, and four products isolated. Regardless of conditions used, every preparation gave low yields of dimethyl 3,6-diphenylphthalate coincident with loss of the phosphorus bridge. NMR data and X-ray crystal structures are provided for a yellow, and a red, 2:1 adduct. The yellow adduct, tetramethyl 1,6,7-triphenyl-6-phospha(V)-tricyclo[7.3.1.01,9]nona-3,5,7-triene-2,3,4,5-tetracarboxylate 6, crystallized in the triclinic space group [Formula: see text] (No. 2) with two molecules in the unit cell. Refinement (a = 11.259(1) Å, b = 12.947(3) Å, c = 13.784(3) Å, α = 112.25(2)°, β = 103.44(1)°, and γ = 101.80(1)°) converged at R = 0.0453 (Rw = 0.0453) for 537 parameters using 2880 reflections with I > 2σ(I). The red adduct, trimethyl 1,2,5-triphenylphosphoranylidene-4-methoxycyclopent-2-ene-5-one-2,3,4-tricarboxylate, an exocyclic phosphorane 8, crystallized in the monoclinic space group P21/c (No. 14) with four molecules in the unit cell. Refinement of this structure (a = 13.233(5) Å, b = 15.712(5) Å, c = 17.191(7) Å, α = 90°, β = 110.35(4)°, and γ = 90°) converged at R = 0.0916 (Rw = 0.0937) for 400 parameters using 2052 reflections with I > 2.5σ(I). Small amounts of a white or buff amorphous material, which could represent a polymeric product from the lost phosphorus bridge, were also obtained. Thermal rearrangement of the yellow adduct gave a colourless 6,5,3 tricyclic isomer 11, possibly via the isomeric cyclopropyl derivative 15 or the nine-membered phosphonin 7. The structure of 11 was confirmed by mild oxidation of the colourless rearrangement product to its P-oxide. This product, tetramethyl 2,3,6-triphenyl-2-phosphatricyclo[6.1.01,8.05,9]-2-oxonona-3,6-diene-1,7,8,9-tetracarboxylate 12, was also colourless. It crystallized in the orthorhombic space group Pbc21 (No. 29) with four pairs of molecules in the unit cell. Refinement of this structure (a = 8.918(1) Å, b = 22.605(4) Å, and c = 30.169(6) Å) converged at R = 0.0747 (Rw = 0.0757) for 321 parameters using 3255 reflections with I > 3σ(I). Unequivocal structures for these adducts and derivatives finally confirms, and establishes further understanding of, the complex reactions of the triphenylphosphole with dimethyl acetylenedicarboxylate.

Preparations, X-ray crystal structures, and spectral studies of seleninyl bis(trifluoromethanesulfonate) and seleninyl bis(acetate)

1988 ◽  
Vol 66 (9) ◽  
pp. 2367-2374 ◽  
Author(s):  
Ramesh Kapoor ◽  
Poonam Wadhawan ◽  
Pratibha Kapoor ◽  
Jeffery F. Sawyer
Keyword(s):  
Crystal Packing ◽  
Spectral Studies ◽  
Monoclinic Space Group ◽  
Coordination Geometry ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Intermolecular Contacts ◽  
Ir And Raman

The compounds seleninyl bis(trifluoromethanesulphonate) (1) and seleninyl bis(acetate) (2) have been prepared and characterized by elemental analysis, ir and Raman spectroscopy, and X-ray crystallography. Crystals of 1 are monoclinic, space group P21/n with a = 12.735(1) Å, b = 5.163(4) Å, c = 16.133(2) Å, β = 96.426(8)°, U = 1054 Å3, Dx = 2.48 g cm−3 for Z = 4, R = 0.038 for 1745 observed reflections with I > 2.5σ(I). Those of 2 are orthorhombic, space group Pcab with a = 6,845(3) Å, b = 8.992(2) Å, c = 23.560(9) Å, U = 1450 Å3Dx = 1.95 g cm−3 for Z = 8, R = 0.074 for 1073 observed reflections with I > 3.0σ(I). The primary geometry of the Se atom in SeO(O3SCF3)2 is AX3E with a Se=O distance of 1.571(3) Å and Se—O bond lengths to the CF3SO3 ligands of 1.902(3) and 1.922(3) Å. Completing the overall coordination geometry of the Se atom are 2 intramolecular and 4 intermolecular Se … O contacts which are less than van der Waals limits. The overall coordination geometry is somewhat irregular since the two triflate anions are significantly differently arranged with respect to the SeO3E tetrahedron. The crystal packing consists of layers of interacting molecules. In 2 there is some disorder. However, the major arrangement of the molecule has Se=O and Se—O(1), Se—O(3) distances to the acetate ligands of lengths 1.575(9), 1.847(7), and 1.831(8) Å respectively. The overall geometry of the Se atom in this compound is completed by two intramolecular secondary Se … O contacts involving the second O atoms of both acetates and two intermolecular contacts involving the seleninyl oxygen atom and atom O(2) of an acetate group in two different symmetry related molecules. Overall, the crystal packing consists of essentially centrosymmetric dimeric units linked together through Se=O—Se bridges. A 1:2 adduct of 1 with pyridine has also been prepared and characterised.

Crystal Structure of an Ammonium Dithiocyanatocuprate(I) Complex with 18-Crown-6, [NH4(18-Crown-6){Cu(NCS)2}] Obtained from Zero Valent Metal

1997 ◽  
Vol 52 (11) ◽  
pp. 1311-1314 ◽  
Author(s):  
Julia A. Manskaya ◽  
Volodimir N. Kokozay ◽  
Konstantin V. Domasevitch
Keyword(s):  
Crystal Structure ◽  
Direct Method ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
One Dimensional ◽  
X Ray ◽  
X Ray Crystallography ◽  
A Direct Method

The new macrocyclic dithiocyanatocuprate(I) complex [NH4(18-crown-6){Cu(NCS)2}] has been prepared using a direct method of interaction and characterized by X-ray crystallography (orthorhombic, space group Cmc21, with a = 12.453(2), b = 21.650(4), c = 8.151(2) Å, V = 2197.6(8) Å3, Z = 4 , R1 (F) = 0.054; wR2(F2) = 0.141 for 972 unique reflections with I > 2σ(I) and R1(F) = 0.082; w/?2(F2) = 0.210 for all 1098 unique reflections). The lattice comprises complex cations [NH4(18-crown-6)]+ and infinite polymeric anions [Cu(NCS)2]- of a one-dimensional zig-zag structure. The copper atoms adopt three-fold coordination [CuN2S] (Cu-N 1,89( 1), 1,90( 1) Å; Cu-S 2.278(4) Å).

Synthesis and Spectroscopic Characterization of Mixed Diamidophosphoric Acid Esters: X-Ray Crystal Structure of [(CH3)2N]-[p-H3C-C6H4-O]P(O)X (X = NHC(CH3)3 and p-H3C-C6H4-NH)

2009 ◽  
Vol 64 (5) ◽  
pp. 565-569 ◽  
Author(s):  
Saied Ghadimi ◽  
Mehrdad Pourayoubi ◽  
Ali Asghar Ebrahimi Valmoozi
Keyword(s):  
Spectroscopic Characterization ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
Unit Cell Parameters ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
R Value ◽  
Acid Esters

Mixed diamidophosphoric acid esters [(CH3)2N][p-H3C-C6H4-O]P(O)X, where X = NH(CH3) (1), NHCH(CH3)2 (2), NHC(CH3)3 (3) and p-H3C-C6H4-NH (4) were synthesized and characterized by 31P, 31P{1H}, 13C, 1H NMR, and IR spectroscopy and mass spectrometry, and single crystal X-ray diffraction analysis for the compounds 3 and 4. Compound 3 crystallizes in the monoclinic, space group P21/c with unit cell parameters a = 9.006(3), b = 16.286(5), c = 10.319(3) A° , β = 99.633(6)◦, V = 1492.2(8) °A3, Z = 4. The final R value is 0.0622 for 2074 reflections [I ≥ 2σ (I)]. Compound 4 crystallizes in the orthorhombic, space group Pna21 with unit cell parameters a = 7.0459(14), b = 20.934(4), c = 10.436(2) ° A, V = 1539.3(5) °A3, Z = 4. The final R value is 0.0530 for 3025 reflections [I ≥ 2σ (I)].

scholarly journals Formation of an unexpected 3,3-diphenyl-3H-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate

2019 ◽  
Vol 15 ◽  
pp. 1347-1354
Author(s):  
Andrew T King ◽  
Hugh G Hiscocks ◽  
Lidia Matesic ◽  
Mohan Bhadbhade ◽  
Roger Bishop ◽  
...  
Keyword(s):  
Single Crystal ◽  
Unit Cell ◽  
Unit Cell Parameters ◽  
One Pot ◽  
Space Group ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
The One ◽  
Close Contacts

The one-pot reaction of 2,6-bis(diphenylmethyl)-4-methoxyaniline with tert-butylnitrite, BTEAC and DABSO in the presence of CuCl2 provided an unexpected 3H-indazole product 8. The structure of the compound was determined by HRMS, IR, NMR and further confirmed by single crystal X-ray crystallography. The compound crystallises in the triclinic P-1 space group, with unit cell parameters a = 9.2107 (4), b = 10.0413 (5), c = 14.4363 (6) Å, α = 78.183 (2), β = 87.625 (2), γ = 71.975 (2)°. The formation of 8 proceeded through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate 9. The molecules of 8 are organised by edge–face Ar–H···π, face–face π···π, and bifurcated OCH2–H···N interactions. In addition to these, there are Ar–H···H–Ar close contacts, (edge–edge and surrounding inversion centres) arranged as infinite tapes along the a direction.

A comparison of the molecular structures of Dicyclohexyl(N-phenylthiocarbamoyl)-phosphine and Diphenyl(N-phenylthiocarbamoy1)phosphine as determined by X-ray crystallography

1984 ◽  
Vol 37 (10) ◽  
pp. 1991 ◽  
Author(s):  
SW Cowan ◽  
BF Hoskins ◽  
ERT Tiekink
Keyword(s):  
Three Dimensional ◽  
Unit Cell ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hydrogen Atoms ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Conformational Effects

The crystal and molecular structures of the title compounds, (C6H11)2PC(S)N(H)C6H5(1) and (C6H5)2PC(S)N(H)C6H5(2) have been determined by single-crystal three-dimensional X-ray diffraction techniques. Crystals of (1) are monoclinic, space group P21/c, with eight molecules in the unit cell of dimensions a 20.541(4), b 17.784(2), c 10.2564(9) � and β 94.54(1)�; (2) crystallizes in the triclinic space group P1 with two molecules in the unit cell which has the dimensions a 9.242(2), b 9.994(3), c 10.373(3) �, α 68.56(2), β 71.21(2) and γ 86.00(2)�. Both structures were refined by a least-squares procedure, applying anisotropic thermal parameters to all non-hydrogen atoms, with the use of 3119 and 2971 statistically significant reflections for (1) and (2) respectively; final R 0.055 for (1) and R 0.061 (Rw 0.062) for (2). The N, C(l), S moieties of both (1) and (2) display features consistent with the delocalization of π-electrons. There are notable differences in some of the bond angles between (I) and (2) which have been attributed to conformational effects arising from variations in steric pressures; this may account for the observed differences in reactivity between the two compounds.

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