Comparative Structural Studies on Three-Coordinate Copper(I) Halide Complexes With Tertiary Phosphines. Crystal Structures of [(PPh2Mes)CuX]2 and [(PPhMes2)CuX]2 (Mes = Mesityl X = Cl, Br, I)

1992 ◽  
Vol 45 (7) ◽  
pp. 1155 ◽  
Author(s):  
GA Bowmaker ◽  
D Camp ◽  
RD Hart ◽  
PC Healy ◽  
BW Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Copper Atom ◽  
Structural Studies ◽  
Coordination Environment ◽  
X Ray ◽  
Tertiary Phosphines ◽  
Structure Determinations ◽  
Halide Complexes ◽  
The Subject

The 1 : 1 complexes of the substituted triphenylphosphine ligands mesityldiphenylphosphine and dimesitylphenylphosphine with copper(1) chloride, bromide and iodide have been the subject of single-crystal X-ray structure determinations at 295 K. All six complexes crystallize as air-stable dimeric molecules, [(PPh2Mes)CuX]2 and [ (PPhMes2)CUX]2 with each copper atom in a distorted trigonal PCuX2. coordination environment. Crystals of [(PPh2Mes)CuCl]2 (1) are monoclinic, P21/n, a 9.961(3), b 18.687(6), c 11.009(7) Ǻ, β 114.63(4)°; R was 0.049 for 2450 'observed' reflections. [(PPh2Mes)CuBrI2 (2) is monoclinic, P21/n, a 9.939(2), b 18.832(6), c 11.238(6) Ǻ, β 115.36(3)°; R was 0.046 for 1803 'observed' reflections. [(PPh2Mes)CuI]2.4/3 C6H6 (3) is rhornbohedral, R3, a 36.877(8), c 9.047(5) A; R was 0.039 for 2537 'observed' reflections. Crystals of [(PPhMes2)CuCl]2.2MeCN (4) are triclinic, Pi, a 15.783(7), b 9.570(4), c 8.914(4) Ǻ, α 72.43(3), β 76.37(3), γ 74.03(3)°; R was 0.045 for 3341 'observed' reflections. [(PPhMes2)CuBr]2.3C6H6 (5) is monoclinic, C2/c, a 9.694(6), b 30.15(2), c 20.66(2) Ǻ, β 98.00(7)°; R was 0.047 for 2117 'observed' reflections. [(PPhMes2)CuI]2.2MeCN (6) is orthorhombic, PP1nb, a 11.694(8), b 14.77(1), c 29.76(3) Ǻ; R was 0.049 for 3447 'observed' reflections. Cu-P bond lengths are: 2.196(2) A (1); 2.198(3) Ǻ (2); 2.222(5) and 2.226(5) Ǻ (3); 2.202(1) Ǻ (4); 2.197(3) A (5); 2.201(4) and 2.264(5) Ǻ (6). The geometries of the LCuX2 and CuX2Cu units are compared with data reported for other monomeric and dimeric compounds for both phosphorus- and nitrogen-based ligands L.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LIX. Crystal Structure Determinations of Tetrakis(trimethylphosphine)copper(I) Halides and Tetrakis(triphenylphosphine)-copper(I) and -silver(I) Hexafluorophosphates

1990 ◽  
Vol 43 (10) ◽  
pp. 1697 ◽  
Author(s):  
GA Bowmaker ◽  
PC Healy ◽  
LM Engelhardt ◽  
JD Kildea ◽  
BW Skelton ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Crystal Structures ◽  
Lewis Base ◽  
X Ray Diffraction ◽  
Coordination Environment ◽  
X Ray ◽  
Bond Lengths ◽  
Cu Complex ◽  
Structure Determinations

The crystal structures of [Cu(Pme3)4]X (X = Cl , Br, I) and of [M(PPh3)4] [PF6] (M = Cu, Ag) have been determined by single-crystal X-ray diffraction methods at 295 K. The former compounds contain nearly tetrahedral [Cu(PMe3)4]+ ions on sites of m symmetry with mean Cu-P bond lengths of 2.270, 2.271 and 2.278 Ǻ for X = Cl , Br and I respectively. The latter compounds contain [M(PPh3)4]+ ions on sites of 3 symmetry. In the M =Ag complex the coordination environment is close to tetrahedral, but in the M =Cu complex the length of the axial Cu-P bond [2.465(2)Ǻ] is significantly shorter than that of the off-axis bonds [2.566(2)Ǻ]. Possible reasons for this are discussed.

Lewis-Base Adducts of Lead(II) Compounds. XVI. Synthetic and Structural Studies of Some Adducts of 2-Aminomethylpyridine With Lead(II) Compounds

1996 ◽  
Vol 49 (10) ◽  
pp. 1127 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Lewis Base ◽  
Structural Studies ◽  
Problem Structure ◽  
Coordination Environment ◽  
X Ray ◽  
The Third ◽  
Structure Determinations ◽  
Centrosymmetric Dimers

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 2:1 adducts of 2-aminomethylpyridine ('amp') with lead(II) nitrate and thiocyanate . [(amp)2Pb(NO3)2]2 is triclinic, Pī, a 11.616(4), b 11.145(6), c 7.341(3) Ǻ, α 83.87(4), β 89.17(3), γ 64.12(3)°, Z = 1 dimer ; R was 0.043 for No 3529 independent 'observed' (I > 3σ(I)) reflections. [(amp)2Pb(SCN)2]2 is also triclinic, Pī , a 12.121(9), b 9.301(14), c 8.615(8) Ǻ, α 70.11(10), β 84.00(7), γ 79.38(10)°, Z = 1 dimer (R 0.033 for No 3467). Both complexes are centrosymmetric dimers ; the coordination environment is made up in each case of a pair of N,N°-bidentate bases, one terminally bound anion (O,O°-chelating nitrate or S-bonded thiocyanate ) and bridging anions. In the case of the thiocyanates, these bridge end-on, so that the lead(II) environment is seven-coordinate PbN5S2; in the nitrate, the anion chelates through two of its oxygen atoms, bridging via the third, so that the lead(II) environment is nine-coordinate PbN4O5. A 'problem structure', [(amp)2Pb(ClO4)2], monoclinic, C2/c (?), a 14.528(3), b 8.203(3), c 15.495(6) Ǻ, β 91.14(3)°, Z = 4 f.u ., R 0.044 for No 1775, is also recorded, the crystal seemingly a disordered aggregate of [(N, N′-amp)2Pb(OClO3)2] moieties.

Structural studies in the iron(III)/chloride/α,α'-diimine system. II. Ionic derivatives of stoichiometry FeCl3(phen,bpy)1,1.5

1983 ◽  
Vol 36 (10) ◽  
pp. 2043 ◽  
Author(s):  
BN Figgis ◽  
JM Patrick ◽  
PA Reynolds ◽  
BW Skelton ◽  
AH White ◽  
...  
Keyword(s):  
Single Crystal ◽  
Least Squares ◽  
Crystal Structures ◽  
Acetonitrile Solution ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structure Determinations ◽  
Derivatives Of

The crystal structures of the 1 : 1 adducts of FeCl3 with 2,2'-bipyridine (bpy) (1) and 1,10-phenanthroline (phen) (2), as recrystallized from nitromethane, have been determined by single-crystal X-ray diffraction methods at 295 K, being refined by least squares to residuals of 0.038 and 0.032 for 1341 and 3968 'observed' reflections; the result for (2) is a redetermination. Crystals of (1) are orthorhombic, Pbnb, a 15.013(4), b 13.510(5), c 12.471(3) Ǻ, Z 4. Crystals of (2) are triclinic, P1, a 15.823(5), b 11.021(5), c 8.200(3) Ǻ, α 80.27(3), β 76.78(3), γ 89.64(3)°, Z 2. Both complexes haw the stoichiometry (FeCl3)1(bpy,phen)1, but are formulated as cis-[Fe(bpy,phen)2Cl2] [FeCl4]; in both compounds, the Fe-N distance is c. 2.20, (trans to Cl), 2.1, Ǻ(cis to Cl), while Fe-Cl, c. 2.2, Ǻ, is short. The structure determinations of Fe2Cl6(phen,bpy)3 as [Fe(phen)2Cl2]+ [Fe(phen)Cl4]- (3) and [Fe(bpy)2Cl2]+ [Fe(bpy)Cl4]- (4) are also reported. Compound (3) (from acetonitrile solution) is triclinic, P1, a 16.502(5), b 11.857(3), c 10.653(3) Ǻ, α 84.92(2), β 72.66(2), γ 74.80(2)°, Z 2, and was refined to a residual of 0.034 for 5540 'observed' reflections. The cation geometry is similar to that of (2); in the anion, the two Fe-CI bonds trans to each other are long [2.377(1) and 2.365(1) Ǻ] while those trans to the Fe-N bonds are short [2.287(1) and 2.318(1) Ǻ]. Fe-N distances are 2.216(3) and 2.220(3) A. Compound (4) (as its nitromethane solvate) is also triclinic, P1, a 14.480(7), b 12.645(5), c 10.678(4) Ǻ, α 95.68(3), β 109.21(3), γ 9258(3)°, Z 2; a residual of 0.042 was obtained for 4962 'observed' reflections. Cation and anion metal geometries are similar to those of (3).

Lewis-Base Adducts of Groups 11 Metal(I) Compounds. LXII. The Crystal Structures of the 1 : 1 Adducts of Copper(I) Chloride, Bromide and Thiocyanate With Quinoline

1991 ◽  
Vol 44 (8) ◽  
pp. 1049 ◽  
Author(s):  
PC Healy ◽  
BW Skelton ◽  
AF Waters ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Lewis Base ◽  
X Ray ◽  
Structure Determinations ◽  
The Subject ◽  
The Common

Adducts (1 : 1) of copper(I) chloride, bromide and thiocyanate with quinoline have been synthesized and have been the subject of single-crystal X-ray structure determinations at 295 K. Crystals of the chloride are orthorhombic, P 212121, a 15.358(7), b 14.309(6), c 3.801(2)Ǻ, Z 4; R was 0.055 for 541 'observed' reflections. Crystals of the bromide are monoclinic, C2/c, a 19.417(5), b 14.048(4), c 15.753(6) Ǻ, β 125.31(2)°, Z 4 tetramers; R was 0.049 for 1138 'observed' reflections. Crystals of the thiocyanate are monoclinic, P 21/c, a 5.682(1), b 10.412(2), c 16.838(5)Ǻ, β 97.48(2)°, Z 4 f.u .; R was 0.045 for 914 'observed' reflections. The chloride takes the form of the common 'stair' polymer, unexpectedly, while the thiocyanate is an expanded version of the same. The bromide provides a second example of a novel tetrameric 'basket' structure exemplified previously by the iodide analogue.

Crystal structures of some eriostyl/nitrobenzoate derivatives

1980 ◽  
Vol 33 (2) ◽  
pp. 313 ◽  
Author(s):  
PR Jefferies ◽  
BW Skelton ◽  
B Walter ◽  
AH White
Keyword(s):  
Charge Transfer ◽  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structure Determinations

Following the suggestion made earlier, on the basis of solution spectroscopy, that a number of eriostyl/nitrobenzoate compounds form charge-transfer self-complexes, a number of these have been investigated structurally by single-crystal X-ray diffraction methods in order to ascertain the presence or otherwise of such interactions in the solid state. The substances thus studied were eriostyl 3,5-dinitrobenzoate (1), eriostyl p-nitrobenzoate (2), tetrahydroeriostyl 3,5-dinitrobenzoate (3), and eriostemyl 3,5-dinitrobenzoate (4);* structure determinations in all cases, although displaying the presence of strong charge-transfer interactions from the two moieties of each molecule, show that the interactions in the solid state are intermolecular in nature.

Crystal-Structures of 2 3-Substituted 10,11-Dimethoxy-1,2,3,4,5,6-Hexahydro-7,9-etheno-3-benzazecine Derivatives

1989 ◽  
Vol 42 (2) ◽  
pp. 321
Author(s):  
XY Jia ◽  
JB Bremner ◽  
BW Skelton ◽  
AH White ◽  
KN Winzenberg
Keyword(s):  
Hydrogen Atom ◽  
Chemical Shift ◽  
Single Crystal ◽  
Crystal Structures ◽  
Naphthalene Ring ◽  
Methyl Derivative ◽  
X Ray ◽  
Structure Determinations

The title compounds are 3-aza[6](1,7)-naphthalenophanes with 3-Me and 3-CO2Me substituents, C18H23NO2 and C19H23NO4; in the former the chemical shift of the naphthalene hydrogen enclosed by the medium nitrogen-containing ring is the highest yet observed in a derivative of this type ( σ 9.33). In order to examine the environment of this hydrogen atom and the expected associated naphthalene ring distortions in both compounds, single-crystal X-ray structure determinations have been carried out at 295 K showing the transannular H…N distance in the methyl derivative to be remarkably short at 2.08(2) � . Crystals are triclinic, P1, a 11.683(3), b 10.846(3), c 6.729(2) �, α 90.08(2), β 93.33(2), γ 112.88 Z 2; R was 0.041 for 1378 'observed' reflections. Crystals of the 3-CO2Me derivative are also triclinic, P1, a 12.587(9), b 10.650(4), c 6.758(3) � , a 91.91(3), β 100.51(4), γ 104.74(5)° Z 2; R 0.067 for 1267 'observed' reflections.

A simple synthetic route to the formation of tetracopper(I) 2-mercaptothiazoline compounds — The crystal structures of [Cu4(S-thiaz)4(PEt2Ph)2], [Cu4(S-thiaz)4(PEt3)2], [Cu4(S-thiaz)4]2, and [Cu4(S-thiaz)4]4

2006 ◽  
Vol 84 (2) ◽  
pp. 251-256 ◽  
Author(s):  
Olaf Fuhr ◽  
Lucia Fernandez-Recio ◽  
Dieter Fenske
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Copper Complexes ◽  
Synthetic Route ◽  
Reaction Conditions ◽  
One Dimensional ◽  
X Ray ◽  
Tertiary Phosphines ◽  
Oligomeric Compounds

Reactions of copper(I) acetate with 2-mercaptothiazoline (HS-thiaz) in the presence of tertiary phosphines lead to the formation of tetranuclear sulphur-bridged copper complexes. Depending on the reaction conditions, isolated clusters ([Cu4(S-thiaz)4(PR3)2] (PR3 = PPh3 (1), PEt2Ph (2), PEt3 (3)), oligomeric compounds ([Cu4(S-thiaz)4]2 (4) and [Cu4(S-thiaz)4]4 (5)), or a one-dimensional polymer ([Cu4(S-thiaz)4]∞ (6)) are formed. The structures of the compounds 2–5 have been determined by single crystal X-ray analysis.Key words: copper, 2-mercaptothiazoline, single crystal X-ray analysis.

scholarly journals Crystal structures of cristobalite-type and coesite-type PON redetermined on the basis of single-crystal X-ray diffraction data

2015 ◽  
Vol 71 (11) ◽  
pp. 1325-1327 ◽  
Author(s):  
Maxim Bykov ◽  
Elena Bykova ◽  
Vadim Dyadkin ◽  
Dominik Baumann ◽  
Wolfgang Schnick ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Single Crystals ◽  
Crystal Structures ◽  
Rotation Axis ◽  
Asymmetric Unit ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structure Determinations ◽  
Anisotropic Displacement Parameters

Hitherto, phosphorus oxonitride (PON) could not be obtained in the form of single crystals and only powder diffraction experiments were feasible for structure studies. In the present work we have synthesized two polymorphs of phosphorus oxonitride, cristobalite-type (cri-PON) and coesite-type (coe-PON), in the form of single crystals and reinvestigated their crystal structures by means of in house and synchrotron single-crystal X-ray diffraction. The crystal structures ofcri-PON andcoe-PON are built from PO2N2tetrahedral units, each with a statistical distribution of oxygen and nitrogen atoms. The crystal structure of thecoe-PON phase has the space groupC2/cwith seven atomic sites in the asymmetric unit [two P and three (N,O) sites on general positions, one (N,O) site on an inversion centre and one (N,O) site on a twofold rotation axis], while thecri-PON phase possesses tetragonalI-42dsymmetry with two independent atoms in the asymmetric unit [the P atom on a fourfold inversion axis and the (N,O) site on a twofold rotation axis]. In comparison with previous structure determinations from powder data, all atoms were refined with anisotropic displacement parameters, leading to higher precision in terms of bond lengths and angles.

Sign in / Sign up

Export Citation Format

Share Document