Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N ′-Aromatic Bidentate Base Systems. III Some Novel Bismuth(III) Halide/N,N ′-Bidentate Ligand (1 : 1)

1998 ◽  
Vol 51 (4) ◽  
pp. 317 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Peter C. Junk ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Room Temperature ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Bidentate Ligand ◽  
Mononuclear Complex ◽  
Infrared And Raman Spectra ◽  
Dmso Solution ◽  
Coordination Environment ◽  
X Ray ◽  
Structure Determinations

Syntheses and single-crystal room-temperature X-ray structure determinations are recorded for a number of adducts obtained by the crystallization of bismuth(III) halides with 2,2′-bipyridine (bpy) or 1,10- phenanthroline (phen) from dimethyl sulfoxide (dmso) solution. [(phen)BiX3(O-dmso)2].dmso, X = Cl, Br, are triclinic, P-1,a ≈ 14·6, b ≈ 9·7, c ≈ 9·5 Å, α ≈ 96, β ≈ 96, γ ≈ 98°, Z = 2; conventional R on | F| were 0·057, 0·037 for No 5775, 4847 independent ‘observed’ (I > 3σ(I)) reflections respectively. The metal atom coordination environments are seven-coordinate pentagonal bipyramidal with axial halides and the two O-dmso ligands cis in the equatorial plane. BiI3/phen/dmso (1 : 1 : 1 ) is orthorhombic, Pmc21, a 12·745(3), b 9·697(3), c 18·335(5) Å, Z = 4, R 0·049 for No 2012. The complex is ionic [(phen)BiI2(O-dmso)3]+[(phen)BiI4]-, the halide atoms being axial in a pentagonal bipyramidal array about the metal in the cation, with a quasi-octahedral coordination environment in the anion. With bpy, by contrast, BiI3/bpy/dmso (1 : 1 : 1) is obtained, orthorhombic, Pnma, a 17·86(2), b 12·87(1), c 8·47(1) Å, Z = 4, R 0·058 for No 1194, a neutral mononuclear complex [(bpy)BiI3(O-dmso)] with a six-coordinate array about the metal, O-dmso trans to an iodine atom. Bands in the far-infrared and Raman spectra due to the vibrations of the O2N2BiX3 cores in [(phen)BiX3(O-dmso)2] (X = Cl, Br) are assigned, and discussed in relation to the structures of the complexes.

Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. II Bipyridinium (2,2' Bipyridine) tetraholobismuthate (III) (Halogen = Chloride or Bromide)

1998 ◽  
Vol 51 (4) ◽  
pp. 311 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Jack M. Harrowfield ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Raman Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Infrared And Raman Spectra ◽  
X Ray ◽  
Structure Determinations ◽  
Anionic Species

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for the title compounds, [bpyH]+[(bpy)BiX4]-, X = Cl, Br, the chloride being obtained in a second acetonitrile- sesquisolvated form. [bpyH]+[(bpy)BiX4]-, X = Cl, Br, are isomorphous, monoclinic C2/c, a ≈ 15·3, b ≈ 9·6, c ≈ 16·8 Å, β 109°, Z = 4, conventional R on |F| being 0·056, 0·059 for No 1456, 769 independent ‘observed’ (I > 3σ(I)) reflections respectively. [bpyH] [(bpy)BiCl4].1½MeCN is monoclinic, P21/m, a 9·572(2), b 34·521(8) c 8·218(2) Å, β 102·13(2)°, Z = 4, R 0·043 for No 2635. All anionic species are mononuclear, the bismuth being quasi-octahedral. Bands in the far-infrared and Raman spectra due to the vibrations of the N2BiCl4 core in [(bpy)BiCl4]- are assigned, and their relationship to the vibrations of [BiCl6]3- is discussed.

Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. V Bismuth(III) Halide/N,N′-Bidentate Ligand (1 : 2) Systems

1998 ◽  
Vol 51 (4) ◽  
pp. 331 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Frances M. M. Hannaway ◽  
Peter C. Junk ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Bidentate Ligand ◽  
X Ray ◽  
B 31 ◽  
Far Infrared Spectra

Syntheses and room-temperature single-crystal X-ray determinations are recorded for a number of adducts of BiX3/N,N′-bidentate 1 : 2 stoichiometry (N,N′-bidentate = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen)). BiX3/bpy (1 : 2), X = Br, I, are isomorphous, monoclinic, P21/c, a ≈ 7·5, b ≈ 31, c ≈ 10·3 Å, β ≈ 113°, Z = 4; conventional R on |F| were 0·058, 0·055 for No 1744, 2068 independent ‘observed’ (I > 3σ(I)) reflections. BiCl3/phen (1 : 2) is monoclinic, P21/C, a 9·675(3), b 31·845(7), c 7·756(2) Å, β 109·94(2), Z = 4, R 0·071 for No 2537, while BiBr3/phen (1 : 2), also monoclinic, P21/c, has a 17·590(5), b 8·812(2), c 17·537(7) Å, β 117·58(3)°, Z = 4; R 0·083 for No 890. BiX3/phen (1 : 2).S, X/S = Br/MeCN, I/CH2Cl2, are isomorphous, orthorhombic, Pna21, a ≈ 20·7, b ≈ 14·2, c ≈ 8·9 Å, Z = 4, R 0·060, 0·046 for No 1553, 2423 respectively. All complexes are mononuclear with seven-coordinate (N2)2BiX3 bismuth environments. Bands in the far-infrared spectra due to the v(BiX) vibrations in [(phen)2BiCl3] and [(bpy)2BiX3] (X = Br, I) are assigned and discussed in relation to the structures of the complexes.

Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. IV Bismuth(III) Halide/N,N′-Bidentate Ligand (1 : 1) Systems

1998 ◽  
Vol 51 (4) ◽  
pp. 325 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Frances M. M. Hannaway ◽  
Peter C. Junk ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Bidentate Ligand ◽  
X Ray ◽  
Far Infrared Spectra

Room-temperature single-crystal X-ray studies are recorded for a number of adducts of BiX3 and N,N′-bidentate ligand (2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen)), devoid of coordinated solvent. BiBr3/bpy/MeCN (1 : 1 : 1) is triclinic P-1, a 12·129(2), b 9·955(4), c 7·748(1) Å, α 73·14(2), β 77·34(1), γ 69·79(2)°, Z = 2; conventional R on |F| was 0·036 for No 2252 independent ‘observed’ (I > 3σ(I)) reflections. The phen analogue is isomorphous, a 11·586(3), b 10·839(6), c 7·769(10) Å, α 73·70(7), β 76·67(7), γ 70·34(4)°, Z = 2, R 0·042 for No 800. BiI3/bpy (1 : 1) is triclinic, P-1, a 11·742(4), b 9·261(1), c 8·261(3) Å, α 86·46(2), β 71·48(3), γ 67·25(2)°, Z = 2, R 0·043 for No 1164. All complexes are centrosymmetric binuclear [(N,N′-bidentate)X2Bi(µ-X)2BiX2(N,N′-bidentate)] with six-coordinate pseudo-octahedral bismuth(III). Attempts to produce a chloride analogue have resulted, in the case of N,N′-bidentate = bpy, in a novel adduct of BiCl3/bpy 1 : 1·5 stoichiometry, monoclinic, P21/c, a 9·377(8), b 17·699(5), c 21·58(1) Å, β 107·82(6)°, Z = 8, R 0·055 for No 1804. The complex is [(bpy)2Cl2Bi(µ-Cl)BiCl3(bpy)], containing seven- and six-coordinate bismuth. Bands in the far-infrared spectra due to the v(BiX) vibrations in [(bpy)2Cl2Bi(µ-Cl)BiCl3(bpy)] and [(bpy)I2Bi(µ-I2)BiI2(bpy)] are assigned and discussed in relation to the structures of the complexes.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXIV Syntheses, Spectroscopy and Structures of Some 1 : 4 Adducts of Copper(I) and Silver(I) Perchlorates with Triphenylarsine and Triphenylstibine

1997 ◽  
Vol 50 (6) ◽  
pp. 539 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Effendy ◽  
Robert D. Hart ◽  
John D. Kildea ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
X Ray ◽  
Cation Disorder ◽  
Structure Determinations ◽  
Consistent Picture ◽  
Far Infrared Spectra

Syntheses and room-temperature single crystal X-ray structure determinations are recorded for adducts [M(EPh3)4] (ClO4), M = Cu, E = As (1), Sb (2); M = Ag, E = As (3), Sb (4), enabling comparison with analogous, previously studied MP4 and MN4 environments. The four complexes so characterized all crystallize in the familiar rhombohedral R-3 array (a ≈ 14·4, c ≈ 52 Å, hexagonal setting) with the metal and chlorine atoms located on crystallographic threefold axes. In these arrays Cu–E (axial, off axis) are 2·493(2), 2·533(1) for (1), and 2·572(1), 2·577(1) Å for (2), the disparity in the two independent M-E distances being diminished relative to those of previously studied phosphorus analogues, perhaps in consequence of increasing E size. In (3) and (4), some cation disorder is evident in respect of the ligand pnictide atom (E); for the major components Ag-E are 2·652(3), 2·680(2) in (3); 2·732(2), 2·7295(8) Å in (4). Problems associated in defining the metal atom environment geometries in the latter are, nevertheless, more satisfactorily overcome in two further determinations of nitrate salts: [Ag(SbPh3)4] (NO3) (5) is of the rhombohedral family with no cation core disorder, Ag–E (axial, off axis) being 2·720(4), 2·725(2) Å, while the structural characterization of a 1 : 4 triphenylarsine adduct of silver nitrate is recorded as its tetraethanol solvate, namely [Ag(AsPh3)4] (NO3).~ 4C2H5OH(6), monoclinic, C2/c, a 18·373(4), b 20·786(5), c 21·070(8) Å, β 108·18(3)°, Z = 4 f.u. The silver atom of the [Ag(AsPh3)4]+cation unusually lies on a crystallographic 2 (rather than a 3 ) axis of the incipiently23 (T) array, with Ag-As 2·649(2), 2·650(2) Å and As-Ag-As ranging from 108·22(4) to 111·41(6)°. The structure determination of a chloroform solvate of (2), denoted (2a), of low precision, is noted, together with the structure of an interesting artefact, isomorphous with the rhombohedral oxoanion array, modelled as [Ag(PPh3)4]2 (SiF6).py (7). Bands in the far-infrared spectra of [M(AsPh3)4] (ClO4) are assigned to v(MAs) vibrations at 119 (M = Cu) and 103 cm¯1 (M = Ag); this produces a more consistent picture of the variation in the wavenumbers of the v(ME) modes in [M(EPh3)4]+ compounds than was available previously.

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.

Syntheses, Structures and Vibrational Spectra of Some Dimethyl Sulfoxide Solvates of Bismuth(III) Bromide and Iodide

1998 ◽  
Vol 51 (4) ◽  
pp. 285 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Jack M. Harrowfield ◽  
Peter C. Junk ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Dimethyl Sulfoxide ◽  
Raman Spectra ◽  
Vibrational Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Infrared And Raman Spectra ◽  
X Ray

Room-temperature single-crystal X-ray studies are recorded for some dimethyl sulfoxide (dmso) solvates of bismuth(III) bromide and iodide. Colourless BiBr3.3dmso is triclinic, P-1, a 8·467(4), b 9·109(4), c 13·901(4) Å, α 76·34(4), β 76·95(4), γ 64·56(4)°, Z = 2; conventional R on |F| was 0·050 for No 2306 independent ‘observed’ (I > 3σ(I)) reflections. The complex is mononuclear with a quasi-octahedral fac-bismuth environment, [(dmso-O)3BiBr3], isomorphous with the previously determined chloride. Orange BiI3-2dmso is triclinic, P-1, a 12·558(2), b 8·962(2), c 8·342(1) Å, α 61·85(1), β 78·27(1), γ 76·89(2)°, Z = 2 f.u., R 0·048 for No 1953. The complex is binuclear, a pair of iodide atoms bridging the two bismuth atoms, [(dmso-O)2I2Bi(µ-I)2BiI2(O-dmso)2]; the two O-dmso ligands about each six-coordinate bismuth lie trans. Red BiI3.2 ⅔ dmso is triclinic, P-1, a 16·435(6), b 14·926(2), c 12·396(3) Å, α 74·89(2), β 73·24(2), γ 79·18(2)°, Z = 6, R 0·059 for No 5858. The complex is [Bi(O-dmso)8] [Bi2I9], the eight-coordinate metal environment of the cation being, unusually, dodecahedral; in the anion a pair of quasi-octahedral six-coordinate bismuth atoms are bridged by three iodides, [I3Bi(µ-I)3BiI3]3-. Bands in the far-infrared and Raman spectra due to the v(BiX) modes are assigned and discussed in relation to the structures of the complexes. The assignment of the v(BiO) modes is discussed.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXVI Synthesis, Spectroscopy and Structural Systematics of Some 1 : 3 Adducts of Copper(I) Compounds with Triphenylstibine, [(Ph3Sb)3CuX], X = Br, I, ONO2

1997 ◽  
Vol 50 (6) ◽  
pp. 567 ◽  
Author(s):  
Robert D. Hart ◽  
Graham A. Bowmaker ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
X Ray ◽  
Strong Band ◽  
C 23 ◽  
Structure Determinations ◽  
Far Infrared Spectra

The syntheses of adducts, [(Ph3Sb)3CuX], X = Br, I, NO3, obtained by crystallization of 1 : 3 CuX/SbPh3 mixtures from appropriate solvents are described, together with their room-temperature single-crystal X-ray structure determinations. The bromide, obtained as a chloroform monosolvate from that solvent, is triclinic, P-1, a 13·861(4), b 14·306(4), c 14·347(4) Å, α 84·40(2), β 86·93(2), γ 75·56(2)°, Z = 2 f.u., conventional R on F being 0·053 for No = 4136 independent ‘observed’ (I > 3σ(I)) reflections; this solvate is isomorphous with its previously recorded chloride counterpart. The iodide is triclinic, P-1, a 14·55(1), b 14·385(2), c 23·626(6) Å, α 91·78(1), β 90·77(4), γ 92·54(5)°; Z= 4, R 0·050 for No 6917, and isomorphous with its phosphorus counterpart. The nitrate, although a methanol sesquisolvate, is also isomorphous with the chloride and bromide, a 13·369(9), b 14·398(3), c 14· 504(12) Å, α 82·29(5), β 84·39(6), γ 75·11(4)°, R 0·052 for No 5672. Cu-X are (2·235(5) (Cl)), 2·366(3) (Br), 2· 556(2) ( 2 ) (I), 1·98(1) Å (ONO2), appreciably shorter than in their previously recorded EPh3, E = P, As counterparts. The far-infrared spectra of [(Ph3Sb)3CuX] showed no clear v(CuX) bands, in contrast to the situation reported previously for the corresponding Ph3P and Ph3As compounds. It is likely that v(CuCl) is masked by a strong band at 270 cm-1 due to the Ph3Sb ligand. However, the region below 250 cm-1 in which the v(CuX) bands are expected for the X = Br, I complexes contains no strong ligand bands. Possible reasons for the absence of v(CuX) bands in these complexes are considered.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXV Synthesis, Spectroscopy and Structural Systematics of Some 1 : 3 Adducts of Copper(I) Compounds with Triphenylarsine, [(Ph3As)3CuX], X = Cl, Br, I, ONO2

1997 ◽  
Vol 50 (6) ◽  
pp. 553 ◽  
Author(s):  
Robert D. Hart ◽  
Graham A. Bowmaker ◽  
Eban N. de Silva ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Bond Strength ◽  
Infrared Spectra ◽  
Copper Atom ◽  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
X Ray ◽  
Α Phase ◽  
Structure Determinations ◽  
Far Infrared Spectra

Crystallization of some copper(I) salts, CuX, with triphenylarsine in 1 : 3 stoichiometry from acetonitrile has yielded an array of adducts, [(Ph3As)3CuX], characterized by room-temperature single crystal X-ray structure determinations. [(Ph3As)3CuCl] (1) has been characterized in two unsolvated phases, α and β, the second form previously recorded as monoclinic, P21/n, Z = 8. The ‘α’ phase, like the bromide (2) and iodide (3), adopts the trigonal P3 array, widespread among many [(Ph3E)3MX] adducts with a ≈ 19, c ≈ 11 Å; conventional R on F was 0·037, 0·041, 0·056 for No 3458, 3259, 3434 independent ‘observed’ (I > 3σ(I)) reflections for these three adducts respectively. A further form, γ, is a toluene hemisolvate, monoclinic, P21/c, a 21·490(5), b 10·218(7), c 24·901(6) Å, β 117·53(2)°, Z = 4, R 0·057 for No 7207. The nitrate (4), obtained as a monosolvate from methanol, is monoclinic, P21/n, a 15 ·115(9), b 23·201(9), c 14·170(14) Å, β 92·56(7)°, Z = 4, R 0·049 for No 5476. In all compounds, the copper atom is four-coordinate, E3CuX, the nitrate in (4) being -ONO2 unidentate. The CuX bond lengthsr(CuX) in [(Ph3E)3CuX] (X = Cl, Br, I) show a decrease from the Ph3P to the corre3sponding Ph3As compound, and this is consistent with the observed increase in the v(CuX) wavenumbers in the far-infrared spectra. These trends are both consistent with an increase in the CuX bond strength from the Ph3P to the Ph3As complexes, and possible reasons for this are discussed.

Lewis-Base Adducts of Lead(II) Compounds. XV. Synthesis and Structure of Some Adducts of Bis(2-pyridyl)amine With Lead(II) Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1121 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Room Temperature ◽  
Bidentate Ligand ◽  
Lewis Base ◽  
Linear Polymers ◽  
Lead Atom ◽  
Coordination Environment ◽  
One Dimensional ◽  
X Ray ◽  
Unit Cells ◽  
Similar Unit

Several complexes of bis(2-pyridyl)amine ('dpa') with lead(II) salts have been synthesized and subjected to room-temperature single-crystal X-ray studies. 1:1 Adducts have been obtained with lead(II) bromide and iodide. They have similar unit cells, also similar to those of a variety of other N,N′-heteroaromatic bidentate ligand adducts with metal(II) halides, and the C2/c cell described elsewhere in this series may be regarded as archetypical. [(dpa)PbBr2](∞|∞) is monoclinic, P21/a, a 9.791(4), b 9.720(4), c 16.498(4) Ǻ, β 95.96(4)′, Z = 4 f.u.; conventional R on |F| at convergence was 0.066 for No = 2717 'observed' (I > 3σ(I)) reflections. [(dpa)PbI2](∞|∞) is monoclinic, P21/c, a 8.299(2), b 10.229(3), c 16.905(5) Ǻ, β 101.47(2)°, Z = 4 f.u.; R was 0.044 for No 2140. Both complexes, like their 2,2'-bipyridine and 1,10-phenanthroline analogues, are linear polymers with six-coordinate (cis-N2)Pb(μ-X)4 environments linked in infinite ... (μ-X)2Pb(μ-X)2… one-dimensional chains, and with dpa being bidentate. A 2:1 adduct of bis(2-pyridyl)amine with lead(II) acetate ('Pb(ac)2') is also described. [(dpa)2Pb(ac)2](∞|∞) is monoclinic, C 2/c, a 28.835(5), b 10.868(3), c 7.665(2) Ǻ, β 94.21(2)°, Z = 4; R was 0.029 for No 1854. The complex is a linear polymer along c; the lead atom lies on a crystallographic twofold axis with a coordination environment comprising a pair of symmetry-related dpa ligands, in this case unidentate (Pb-N 3.092(6) Ǻ), and a pair of symmetry-related bidentate acetate ligands (Pb-O 2.465(4) and 2.568(5) Ǻ) with the first oxygen atom performing an additional bridging function to adjacent symmetry-related lead atoms (Pb-O 2.663(4)Ǻ).

Structural Systematics of Rare Earth Complexes. XIX (Hydrated) 1 : 2 Mononuclear Adducts of Lanthanoid(III) Chlorides with 2,2′-Bipyridine and 1,10-Phenanthroline

1999 ◽  
Vol 52 (6) ◽  
pp. 571 ◽  
Author(s):  
Lioubov I. Semenova ◽  
Allan H. White
Keyword(s):  
Rare Earth ◽  
Single Crystal ◽  
Metal Atom ◽  
Room Temperature ◽  
Rare Earth Complexes ◽  
Coordination Environment ◽  
X Ray ◽  
Structure Determinations

Room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of hydrated lanthanoid(III) trichlorides with 2,2′-bipyridine (‘bpy’) and 1,10-phenanthroline (‘phen’), crystallized from water, methanol or ethanol solutions, containing mononuclear arrays with 1 : 2 Ln/bpy or phen stoichiometry. LaCl3/phen/H2O(1 : 3 : 9), [(phen)2La(OH2)5]Cl3.phen.4H2O, although of overall 1 : 3 LaCl3/phen stoichiometry, has a lattice phen; it is orthorhombic, Pnna, a 19·947(7), b 16·457(5), c 12·213(2) Å, Z = 4; conventional R on |F| was 0·030 for No 2567 ‘observed’ (I >3σ(I)) diffractometer reflections. LaCl3/phen/H2O/MeOH (1 : 2 : 6 : 1), [(phen)2La(OH2)5]Cl3.H2O.MeOH, is triclinic, P 1, a 19·060(3), b 9·252(3), c 8·994(3) Å, α 69·33(3), β 86·81(2), γ 89·66(2)°, Z = 2, R 0·037 for No 5452. LaCl3/bpy/H2O (1 : 2 : 6), [(bpy)2La(OH2)4Cl]Cl2.2H2O, is monoclinic, P 21/c, a 19·389(3), b 9·071(1), c 16·873(2) Å, β 114·10(1)°, Z = 4, R 0·029 for No 4699. All three of these complexes have a nine-coordinate [(N,N′-bidentate)2La(unidentate)5] coordination environment with quasi-2 symmetry; that of the remaining compounds following is eight-coordinate [(N,N′-bidentate)2Ln(unidentate)4]. LuCl3/phen/H2O (1 : 2 : 6), [(phen)2Lu(OH2)4]Cl3.2H2O, is monoclinic, C 2/c, a 11·045(7), b 17·660(6), c 14·474(9) Å, β 92·82(5)°, Z = 4, R 0·042 for No 1695, the Lu lying on a crystallographic 2 -axis. Crystals of LnCl3/phen/H2O(1 : 2 : 4), [(phen)2Ln(OH2)3Cl]Cl2.H2O (Ln = Dy, Er, Y), are triclinic, P 1, a≈ 12·6, b ≈ 10·5, c ≈ 10·4 Å, α ≈ 93·3, β ≈ 109·3, γ ≈ 96·8°, Z = 2, R 0·030, 0·040, 0·052 for No 4221, 5100, 2690 respectively. PrCl3/bpy/H2O/EtOH (1 : 2 : 1 : 0·5), [(bpy)2Pr(OH2)Cl3].½EtOH, is triclinic, P 1, a 13·331(3), b 10·734(2), c 9·758(2) Å, α 63·67(2), β 78·99(2), γ 71·24(2)°, Z = 2, R 0·033 for No 4596, while [(bpy)2Pr(OH2)2Cl2]Cl is monoclinic, C 2/c, a 15·921(15), b 11·314(8), c 14·114(8) Å, β 116·70(6)°, Z = 4, R 0·041 for No 2269. ErCl3/bpy/H2O(1 : 2 : 2 (also)), [(bpy)2Er(OH2)2Cl2]Cl, is cubic, I 23, a 26·032(4) Å, Z = 24, R 0·066 for No 1644. Crystals of LnCl3/phen/H2O/MeOH (1 : 2 : 1 : 1), [(phen)2Ln(OH2)Cl3].MeOH (Ln = La, Pr, Nd, Eu), are monoclinic, P 21/a, a ≈ 13·2, b ≈ 10·7, c ≈ 18·5 Å, β ≈ 102·1°, Z = 4, R 0·054, 0·032, 0·040, 0·054 for No 2872, 4792, 3179, 2847 respectively. LnCl3/bpy/H2O/EtOH (1 : 2 : 1 : 1), [(bpy)2Ln(OH2)Cl3].EtOH (Ln = Nd, Eu), are triclinic, P 1, a ≈ 11·3, b ≈ 10·9, c ≈ 10·4 Å, α ≈ 75·5, β ≈ 89·8, γ ≈ 78·0°, Z = 2, R 0·044, 0·056 for No 4979, 3596 respectively. LaCl3/bpy/EtOH (1 : 2 : 0·5) is binuclear [(bpy)2Cl2La(µ-Cl)2LaCl2(bpy)2].EtOH, monoclinic, P 21/c, a 9·6878(2), b 17·5696(3), c 16·1341(2) Å, β 123·10(1)°, Z = 2, R 0·033 for No 4256. A totally unsolvated array is found for YbCl3/bpy (1 : 2), [(bpy)2YbCl3], monoclinic, P 21/c, a 15·065(8), b 8·598(4), c 16·92(1) Å, β 112·46(5)°, Z = 4, R 0·032 for No 3548, in which, alone, the metal atom is seven-coordinate.

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