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. 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 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 Group 11 Metal(I) Compounds. LIII. Synthesis and Structural Characterization of Binuclear μ,μ'-Dichloro-, Dibromo and Diiodo-bis[(pyridine)(triphenylphosphine)copper(I)] Complexes, and Their Pyridine-4-carbonitrile Analogues

1989 ◽  
Vol 42 (6) ◽  
pp. 913 ◽  
Author(s):  
LM Engelhardt ◽  
PC Healy ◽  
JD Kildea ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Lewis Base ◽  
The Other ◽  
X Ray ◽  
Structure Determinations ◽  
M Phase ◽  
And Inversion ◽  
Iodide Single Crystal

Mixed base pyridine (py)/triphenylphosphine adducts of the copper(1) halides, CuX, have been synthesized for 1 : 1 : 1 stoichiometry for X = chloride and iodide; single-crystal X-ray structure determinations of these show them to be isomorphous and isostructural with that of the bromide recorded elsewhere, being �,�′- dihalo-bridged dimers , [(PPh3)( py )CuX2Cu( py )(PPh3)], monoclinic, C2/c, a ≈ 26.2, b ≈ 14.3, c ≈ 11 .2 � , β ≈ 95, Z = 4 dimers. The bromide has been isolated as a new monoclinic C 2/m polymorph, a 11 .279(8), b 14.268(6), c 13.858(4) �, β 109.33(6)�, Z=4 dimers, and details of its structure are also recorded. The structures of their pyridine-4-carbonitrile (pycn) analogues have also been determined and found to be also binuclear, with no cyano-copper interactions; these also are an isomorphous, isostructural series, monoclinic P21/n, a ≈ 15.4, b ≈ 8.1, c ≈ 17.9 � , β ≈ 101 �, Z = 2 dimers. In each series of dimers, one half of the dimer is crystallographically independent, the generators of the other half being twofold rotor (C2/c phase), mirror (C2/m phase) and inversion centre (P21/n phase) respectively.

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.

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.

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. XIV. Synthetic and Structural Studies of Some 2:1 Adducts of 2,2'-Bipyridine With Lead(II) Oxoanion Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1111 ◽  
Author(s):  
LM Engelhardt ◽  
JM Harrowfield ◽  
H Miyamae ◽  
JM Patrick ◽  
BW Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Chloride Ions ◽  
Lewis Base ◽  
The Other ◽  
Coordination Environment ◽  
X Ray ◽  
Structure Determinations ◽  
Chloride Adduct ◽  
Species Being

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 2: 1 adducts of the N,N′-bidentate aromatic base 2,2′-bipyridine (' bpy ') with lead(II) nitrate and perchlorate. [( bpy )2Pb(NO3)2]2 is triclinic, Pī , a 14.609(6), b 9.400(4), c 8.396(4) Ǻ, α 71.10(3), β 83.53(3), γ 81.72(3)°, Z = 1 dimer; R was 0.037 for No = 3001 independent, 'observed' (I > 3σ(I)) reflections. [( bpy )2Pb(ClO4)2] is monoclinic, P21/c, a 9.8806(6), b 12.198(6), c 19.924(2) Ǻ, β 106.80(1)°, Z = 4, R 0.040 for No 4456. Unlike the two 1,10-phenanthroline (' phen ') systems which are mononuclear with eight-coordinate PbN4O4 environments incorporating a pair of O,O′;- bidentate anions, the bpy systems are centrosymmetric dimers; in each case the coordination environment incorporates a pair of N,N′- bidentate aromatic bases and an O,O′- bidentate anion, but the other anion is not only O,O′- bidentate, but also bridges by a third oxygen atom to the other lead atom so that it is nine-coordinate PbN4O5. Syntheses and room-temperature single-crystal X-ray structure determinations are also recorded for a pair of 2:1 adducts of 2,2?-bipyridine with lead(II) salts of mixed anion stoichiometry , viz. ( bpy )2PbX(ClO4), X = acetate ('ac'), chloride. [( bpy )2Pb(ac)(ClO4)] is triclinic, Pī , a 15.910(6), b 9.067(5), c 8.588(3) Ǻ, α 102.91(4), β 93.64(3), γ 103.41(4)°, Z = 2, R 0.039 for No 5283. [( bpy )2PbCl(ClO4)2 is monoclinic, P 21/c, a 12.923(2), b 8.759(2), c 19.650(2) Ǻ, β 94.776(9)°, Z = 2 dimers (R 0.037 for No 4433). Like the 1:2 oxoanion/phen adducts, the acetate is a discrete molecular species with an eight-coordinate PbN4O4 lead environment, the oxygen array comprising a pair of O,O′- bidentate perchlorate and acetate ligands. The chloride adduct, however, is like the 1:2 oxoanion/bpy adducts, being centrosymmetric binuclear, a pair of μ-chloride ions linking the two lead atoms which have seven-coordinate PbN4(μ- Cl )2O lead environments, the perchlorate species being O-unidentate.

Sign in / Sign up

Export Citation Format

Share Document