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. LXX Synthesis, Spectroscopy and Structural Systematics of 1 : 2 Binuclear Adducts of Copper(I) Halides with Triphenylstibine, [(Ph3Sb)2Cu(-X)2Cu(SbPh3)2], X = Cl, Br, I

1997 ◽  
Vol 50 (6) ◽  
pp. 621 ◽  
Author(s):  
Robert D. Hart ◽  
Graham A. Bowmaker ◽  
Eban N. de Silva ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Related Species ◽  
Far Infrared ◽  
Lewis Base ◽  
The Other ◽  
X Ray ◽  
Structure Determinations ◽  
Far Infrared Spectra

Crystallization of 1 : 2 mixtures of the copper(I) halides CuX, X = Cl, Br, I, with triphenylstibine from acetonitrile yields adducts of 1 : 2 CuX/SbPh3 stoichiometry, confirmed by single-crystal X-ray structure determinations. The three complexes are isomorphous, monoclinic, P 21/c, a ≈ 24·3, b ≈ 14·2, c ≈ 20 Å, β 110°, Z = 4 dimers; conventional R on F were 0·047, 0·044 and 0·045 for No 11247, 4673 and 10418 independent ‘observe’ (I > 3σ(I)) reflections respectively. The complexes, also isomorphous with some related species, e.g. 1 : 2 AgBr,I/AsPh3, are dimers: [(Ph3Sb)2Cu(µ-X)2Cu(SbPh3)2]. The chloride is also recorded as a chloroform disolvate, isomorphous with its arsine analogue, being monoclinic, C 2/c, a 21·486(9), b 17· 925(9), c 19·972(7) Å, β 91·31(3)°, Z = 4 dimers, R 0·057 for No 3756. The far-infrared spectra of [(Ph3Sb)2Cu(µ-X)2Cu(SbPh3)2] (X = Br, I) showed no clear v(CuX) bands, in contrast to the situation reported previously for the corresponding Ph3As compounds. A possible v(CuCl) band is observed in the X = Cl complex at 219 cm-1 , but this occurs in a region where there is also significant absorption in the other two compounds. The absence of strong v(CuX) bands in these complexes is consistent with the situation observed previously for the 3 : 1 compounds [(Ph3Sb)3CuX].

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXI Synthesis, Spectroscopy and Structural Systematics of Some 1 : 2 Binuclear Adducts of Silver(I) Compounds with Triphenylarsine, [(Ph3As)2Ag(µ-X)2Ag(AsPh3)2], X = Cl, Br, I, SCN

1997 ◽  
Vol 50 (6) ◽  
pp. 627 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Effendy ◽  
John D. Kildea ◽  
Eban N. de Silva ◽  
Allan H. White
Keyword(s):  
Infrared Spectra ◽  
Structural Characterization ◽  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
X Ray ◽  
C 23 ◽  
Pseudo Halides ◽  
Far Infrared Spectra

The syntheses and room-temperature single-crystal X-ray structural characterization of binuclear 1 : 2 adducts formed between silver(I) (pseudo-)halides, AgX, and triphenylarsine, AsPh3, for X = Cl, Br, I, SCN (1)–(4), are described. The chloride (1), obtained from 2-methylpyridine, is triclinic, P-1, a 10·410(2), b 12·716(2), c 14·196(6) Å, α 113·38(2), β 109·41(2), γ 75·08(1)°, Z = 1 (dimer); conventional R on F was 0·037 for No 3979 independent ‘observed’ (I > 3σ(I)) reflections. The bromide (2a), obtained from 2,6-dimethylpyridine, and iodide (3), obtained from a mixture of AgI/saturated KI in MeOH solutions, are isomorphous, monoclinic, P 21/c a≈ 24·2, b ≈ 13·9, c ≈ 20·2 Å, β ≈ 109·5°, Z = 4 dimers; R was 0·046 and 0·044 for No 5670 and 6039 respectively. The thiocyanate (4) has a similar cell, a 24·12(1), b 12·558(8), c 23·244(4) Å, β 110·11(3)°, Z = 4 dimers, R being 0·044 for No 7956; one of the thiocyanate ligands (which bridge in Ag-SCN-Ag mode) is disordered. A second polymorph of the bromide (2b) (from a mixture of AgBr/saturated KBr in H2O) is also monoclinic, P 21/c, a 14·121(8), b 25·577(3), c 21·968(2) Å, β 125·54(3)°, Z = 4 dimers (R was 0·047 for No 5715). Ag–As range between 2·568(1) and 2·633(1) Å throughout the series; in the isomorphous bromide and iodide, values increase slightly: 2·578(1)–2·611(1), cf. 2·601(2)-2·633(1) Å respectively. Ag–X are 2·568(2)-2·670(2) (Cl); 2·688(2)–2·715(2) (Br); 2·828(2)–2·856(1) Å (I); Ag-S, N for the ordered SCN group are 2·646(3), 2·255(6) Å. A redetermination of improved precision (R 0·035, No 6030) is reported for the triphenylphosphine/thiocyanate analogue. The far-infrared spectra of [(Ph3As)2Ag(µ-X)2Ag (AsPh3)2] show v(AgX) bands at 185, 145 (X = Cl), 145, 130, 106 (X = Br) and 121 cm-1 (X = I). The splittings and band widths reflect a decrease in the degree of distortion of the Ag(µ-X)2Ag units from a symmetrically bridged structure from X = Cl to I.

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 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.

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. LXXII Synthesis, Spectroscopy and Structural Systematics of Some 1 : 2 Binuclear Complexes of Silver(I) Halides with Triphenylstibine, [(Ph3Sb)2Ag(μ-X)2Ag(SbPh3)2], X = Cl, Br, I

1997 ◽  
Vol 50 (6) ◽  
pp. 641 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Effendy ◽  
Eban N. de Silva ◽  
Allan H. White
Keyword(s):  
Infrared Spectra ◽  
Structural Characterization ◽  
Room Temperature ◽  
Far Infrared ◽  
Lewis Base ◽  
Binuclear Complexes ◽  
X Ray ◽  
Centrosymmetric Dimers ◽  
Far Infrared Spectra

Syntheses and room-temperature single-crystal X-ray structural characterization of binuclear 1 : 2 adducts formed between silver(I) halides, AgX (X = Cl, Br, I), and triphenylstibine, SbPh3, are described. The three complexes are isomorphous, being triclinic, P-1, a ≈ 18·5, b ≈ 14·6, c ≈ 14·5 Å, α ≈ 62·5, β ≈ 74, γ ≈ 77°, Z = 2 centrosymmetric dimers. Conventional R on F were 0·043, 0·038 and 0·046 for 4984, 8479 and 4166 independent, ‘observed’ (I > 3σ(I)) reflections respectively. In [(Ph3b)2Ag(µ-X)2Ag(SbPh3)2], Ag–Sb range between 2·702(1) and 2·744(2) Å, lengthening slightly from chloride to iodide; Ag–X are 2·567(5)–2·628(4) (Cl), 2·684(1)–2·737(1) (Br) and 2·826(3)–2·869(3) Å (I). The far-infrared spectra of [(Ph3Sb)2Ag(µ-X)2Ag(SbPh3)2] show v(AgX) bands at 178, 158 (X = Cl), 121 (X = Br) and 110 cm-1 (X = I). The splittings and band widths reflect a decrease in the degree of distortion of the Ag(µ-X)2Ag units from a symmetrically bridged structure from X = Cl to I.

Lewis-Base Adducts of Lead(II) Compounds. XVII. Synthetic and Structural Studies of Some 1:1 Adducts of 2,2':6,2'-Terpyridine With Lead(II) Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1135 ◽  
Author(s):  
LM Engelhardt ◽  
JM Harrowfield ◽  
H Miyamae ◽  
JM Patrick ◽  
BW Skelton ◽  
...  
Keyword(s):  
Water Molecule ◽  
Single Crystal ◽  
Room Temperature ◽  
Lewis Base ◽  
Polymeric Chain ◽  
Lead Atom ◽  
X Ray ◽  
Structure Determinations ◽  
Pass Through ◽  
Nitrate And Nitrite

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1:1 adducts of 2,2':6',2"-terpyridine (' tpy ') with the lead(II) oxoanion salts perchlorate, nitrate and nitrite, ( tpy ) Pb ( oxoanion )2. All structures are monoclinic, C2/c, Z = 4, with approximate ranges a from 9 to 11 Ǻ, b from 16 to 20 Ǻ, c from 9.8 to 13.8 Ǻ, β from 113 to 130° and V from 1650 to 1850 Ǻ3. In all cases the lead(II) atoms are disposed on crystallographic 2 axes which also pass through the axis of the central tpy ring; a pair of symmetry related oxoanions link successive lead atoms in a one-dimensional polymeric chain parallel to the ac cell diagonal, one pair of oxygen atoms functioning as an O,O'-bidentate with another oxygen (replaced by the nitrogen in the nitrite) bridging to the adjacent lead atom; the third anionic oxygen atom in the nitrate is replaced by a water molecule in the nitrite, which thus becomes a monohydrate. Residuals were 0.030, 0.034 and 0.040 for 2122, 1564 and 2059 independent 'observed' (I > 3σ(I)) reflections respectively. Also recorded are the syntheses and room-temperature single-crystal X-ray structure determinations for 1:1 aducts of 2,2':6',2"-terpyridine with lead(II) chloride, bromide and iodide, the chloride and bromide being hydrated. ( tpy )PbCl2.H2O is monoclinic, P 21/c, a 8.938(1), b 15,210(7), c 13.414(3) Ǻ, β 115.17(1)°, Z = 4 f.u .; R was 0.036 for No = 3346 independent, 'observed' reflections. The complex is centrosymmetric, binuclear [( tpy ) (H2O)( Cl ) Pb (μ- Cl )2Pb( Cl )(OH2)( tpy )], with the two lead atoms linked by bridging chlorine atoms; the lead atoms are seven-coordinate N3,O,ClPb(μ- Cl )2. The bromide ( tpy )PbBr2.2/3H2O, triclinic, Pī, a 12.360(6), b 12.452(4), c 18.372(6) Ǻ, α 108.31(3), β 109.44(3), γ 90.56(3)°, Z = 6 f.u ., R being 0.046 for No 7282, is in fact trinuclear [Pb3Br6( tpy )6].2H2O, a novel and elegant oligomer with quasi-2 symmetry in which a central lead atom (on the quasi-2 axis) is seven-coordinated [( tpy ) Pb (μ-Br)4] with the associated bromides bridging to a pair of peripheral lead atoms, also seven coordinated, [( tpy )(Br) Pb (μ-Br)3]. Unsolvated ( tpy )PbI2, triclinic, Pī , a 10.834(3), b 9.023(3), c 8.906(2) Ǻ, α 80.34(2), β 89.40(2), γ 79.78(2)°, Z = 2 f.u ., R 0.031 for No 2347 is, like the chloride, centrosymmetric binuclear, [( tpy )(I) Pb (μ-I)2Pb(I)( tpy )], but with the lead(II) now six-coordinate N3(I) Pb (μ-I)2. In both chloride and iodide, the tpy plane is approximately normal to the Pb ... Pb line with the water molecule of the chloride approximately trans to the central tpy nitrogen; in the iodide that site is occupied by the terminal halide.

Structural Systematics of Rare Earth Complexes. XIV Hydrated 1 : 1 Adducts of Lanthanoid(III) Nitrates with 2,2′:6′,2″-Terpyridine

1999 ◽  
Vol 52 (6) ◽  
pp. 507 ◽  
Author(s):  
Lioubov I. Semenova ◽  
Allan H. White
Keyword(s):  
Rare Earth ◽  
Single Crystal ◽  
Room Temperature ◽  
Rare Earth Complexes ◽  
X Ray ◽  
C 23 ◽  
Structure Determinations

Room-temperature single-crystal X-ray structure determinations are recorded for (hydrated) lanthanoid(III) nitrate/2,2′:6′,2″-terpyridine (‘tpy’) (1 : 1) complexes; all are of the form Ln(NO3)3/tpy/H2O(1 : 1 :x), [(tpy)Ln(O2NO)2(OH2)y](NO3)(.z H2O), and form two series of compounds. For Ln = La(-)Gd, the complexes are [(tpy)Ln(O2NO)2(OH2)3](NO3), the lanthanoid atom being ten-coordinate; crystals are triclinic, P 1, a ≈ 11·8, b ≈ 11·3, c ≈ 8·9 Å, α ≈ 75, β 69, γ ≈ 89°, Z = 2 f.u., conventional R on |F| 0·045, 0·062 for No 4513, 2710 independent ‘observed’ (I > 3σ(I)) diffractometer reflections for Ln = La, Gd respectively. For Ln = Tb(-)Lu, a different form is found: monoclinic, P 21/c, a ≈ 8·8, b ≈ 11·5, c ≈ 23·8 Å, β ≈ 111°, Z = 4, R 0·055, 0·037, 0·056 for No 2427, 3079, 1857 for Ln = Tb, Lu, Y respectively, the form of the complex being [(tpy)Ln(O2NO)2(OH2)2](NO3).2H2O, with nine-coordinate lanthanoid. Crystallization of the Ln = La adduct from methanol yields an adduct of La(NO3)3/tpy/MeOH (1 : 1 : 2) [(tpy)La(O2NO)3(HOMe)2] stoichiometry with 11-coordinate lanthanum. Crystals are triclinic, P 1, a 12·361(2), b 12·244(3), c 7·753(2) Å, α 96·56(2), β 103·22(2), γ 91·16(2)°, Z = 2, R 0·037 for No 6597.

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

1997 ◽  
Vol 50 (6) ◽  
pp. 577 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Effendy ◽  
John D. Kildea ◽  
Allan H. White
Keyword(s):  
Room Temperature ◽  
Far Infrared ◽  
Phosphine Ligands ◽  
Lewis Base ◽  
X Ray ◽  
Bonding Parameters ◽  
Pseudo Halides ◽  
The Relationship ◽  
Far Infrared Spectra

The syntheses and room-temperature single-crystal X-ray structure determination of 1 : 3 adducts formed between silver(I) (pseudo-)halides, AgX, and triphenylarsine, AsPh3, are described (X = Cl, Br, I, SCN), [(Ph3As)3AgX], (1)–(4). The chloride (1) has been previously described as its acetone hemisolvate; other solvates (1a–d) (0·75 MeCN, MeOH, 1·5 pyridine, 0·75 2,6-dimethylpyridine) are isomorphous, being triclinic, P-1, a ≈ 13·5, b ≈ 14·0, c ≈ 14·25 Å, α ≈ 83, β ≈ 87, γ ≈ 76°, V ≈ 2600 Å3, Z = 2 f.u. The bromide (2), iodide (3) and thiocyanate (4) are isomorphous with [(Ph3P)3AgI], monoclinic, P21/n, a ≈ 19·1, b ≈ 14·0, c ≈ 17·7 Å, β ≈ 97°, Z = 4 f.u. In the chlorides, Ag–Cl are 2·494(5)–2·525(6) Å, with appreciably different Cl–Ag–As ranges (99·7(1)–114·3(1)° in the acetonitrile solvate; 104·8(2)–110·2(1)° in the 2,6-dimethylpyridine solvate) and more compact As–Ag–As distributions (overall range: 109·93(8)–113·26(3)°). For the bromide and iodide, Ag–X are 2·627(1) and 2·779(1) Å respectively, while for the thiocyanate Ag–S is 2·550(5) Å with Ag–S–C 104·2(3)°; the latter complexes also display wide ranges for many of the associated bonding parameters about the silver atom. The far-infrared spectra of [(Ph3As)3AgX] (X = Cl, Br, I) show v(AgX) bands at 217, 145 and 124 cm-1 respectively. The relationship between the v(AgX) wavenumbers and the Ag–X bond length r (AgX) is found to be the same as that for a range of AgX complexes with phosphine ligands, and is similar to that observed previously for analogous CuX complexes.

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