Lewis-Base Adducts of Lead(II) Compounds. XIII. Synthetic, Structural and Theoretical Studies of Some 2:1 Adducts of 1,10-Phenanthroline With Lead(II) Oxoanion Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1099 ◽  
Author(s):  
I Bytheway ◽  
LM Engelhardt ◽  
JM Harrowfield ◽  
DL Kepert ◽  
H Miyamae ◽  
...  
Keyword(s):  
Room Temperature ◽  
Electron Pair ◽  
Lone Pair ◽  
Coordination Complexes ◽  
Lewis Base ◽  
Theoretical Studies ◽  
Hydrogen Atoms ◽  
X Ray ◽  
Structure Determinations ◽  
Good Agreement

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 2 : 1 adducts of the N,N′- bidentate aromatic base 1,10-phenanthroline (' phen ') with lead(II) nitrate and perchlorate . [( phen )2Pb(NO3)2] is monoclinic, P21/n, a 18.104(4), b 7.733(2), c 16.688(3) Ǻ, β 98.17(2)′, Z = 4, R being 0.036 for No = 3381 independent 'observed' reflections, while [( phen )2Pb(ClO4)2] is triclinic, Pī , a 13.134(4), b 12.342(4), c 7.771(3) Ǻ, α 94.34(3), β 101.49(3), γ 93.91(2)′, Z = 2, R being 0.056 for No 3473. The two systems are mononuclear with eight-coordinate PbN4O4 coordination environments incorporating a pair of O,O'- bidentate anions. Stereochemical calculations, based on valence shell electron pair repulsion (VSEPR) theory, have been performed for coordination complexes of the general type [M( bidentate A)n( bidentate B)4-n] (n = 1 or 2) and for several types of lead(II) complex thought to contain sterically active lone pairs of electrons. Expected deviations from ideal stereochemistry have been successfully predicted and for many of the complexes studied there is good agreement between the observed and calculated stereochemistry. In the particular case of these lead(II)/ phen complexes it appears to be necessary to invoke steric interactions of the a-hydrogen atoms in addition to a sterically active lone pair.

Lewis-Base Adducts of Lead(II) Compounds. X. Synthetic and Structural Studies of Some 1:1 Adducts of 'tet-b' With Lead(II) (Pseudo-)Halides

1996 ◽  
Vol 49 (10) ◽  
pp. 1067 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Hydrogen Bonding ◽  
Room Temperature ◽  
Lewis Base ◽  
Double Salt ◽  
Rear Side ◽  
Hydrogen Atoms ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Structure Determinations ◽  
Pseudo Halides

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of (7R*,14R*)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (' tet -b') with a variety of lead(II) salts. [( tet -b)PbCl2] is monoclinic, P 21/c, a 7.183(3), b 12.425(2), c 24.418(2) Ǻ, β 95.32(3)°, Z = 4; conventional R on |F| was 0.044 for 3188 independent, 'observed' (I > 3σ(I)) reflections. [( tet -b)PbI2] is monoclinic, P 21/c, a 19.920(5), b 7.772(5), c 15.605(6) Ǻ, β 108.39(2)°, Z = 4; R 0.051 for No 2507. [( tet -b) Pb (NCS)2] is orthorhombic, P 212121, a 36.99(1), b 8.996(5), c 6.964(3) Ǻ, Z = 4; R 0.043 for No 2100. All are discrete mononuclear [( tet -b)PbX2] entities in which the macrocyclic N4 ligand occupies one 'face' of the N4PbX2 coordination sphere, the thiocyanate ligands being N-bonded, with Pb -N-C angles of 116(2) and 118(1)°; interesting hydrogen-bonding interactions are found, columns of molecules being formed by way of hydrogen bonding between the coordinated (pseudo-)halides and the NH hydrogen atoms which project to the 'rear' face of the ligand of the next molecule, opposite the metal. In contrast to these, the bromide analogue, monoclinic, P21, a 9.342(3), b 12.720(5), c 18.845(5) Ǻ, β 103.17(2)°, Z = 4, R 0.035 for No 3593, is best formulated as [( tet -b) PbBr ] Br, one only of the bromide entities being bound to the lead, the other being fully dissociated by hydrogen bonding/ion pairing to the 'rear' side of adjacent ligands , forming hydrogen-bonded sheets rather than columns. This formulation has been extended to provide a description of an analogous mixed chloride- perchlorate 'double salt', [( tet -b) PbCl ] (ClO4).CH3OH, which is orthorhombic, P 212121, a 19.475(2), b 18.73(1), c 6.820(2) Ǻ, Z = 4, R 0.054 for No 3075. However, another double salt, modelled in refinement as Pb ( tet -b)Cl0.5(ClO4)1.5.H2O, orthorhombic Pnma , a 20.640(5), b 26.16(1), c 8.937(4) Ǻ, Z = 4 dimers , R 0.074 for No 1769, is in this case more appropriately described as [( tet -b) Pb (OClO2O)2Pb( tet -b)] (ClO4) Cl.H2O with perchlorate rather than halide coordinated, and an incipiently dimeric cation, as in the parent [( tet -b) Pb (OClO3)]2 (ClO4)2.2H2O.

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. 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.

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.

Lewis-Base Adducts of Lead(II) Compounds. XIX. Synthetic and Structural Studies of Some 1:1 Adducts of 2,4,6-Tris (2-pyridyl)-1,3,5-triazine With Lead(II) (Pseudo-)Halides

1996 ◽  
Vol 49 (10) ◽  
pp. 1157 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Lewis Base ◽  
Structural Studies ◽  
Adjacent Pair ◽  
X Ray ◽  
Structure Determinations ◽  
Pseudo Halides

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1:1 adducts of 2,4,6-tris(2-pyridyl) 1,3,5-triazine (' trz ') with lead(II) chloride, bromide, iodide and thiocyanate, the chloride and bromide being methanol monosolvates. [( trz )PbCl2](∞|∞). MeOH is monoclinic, P 2/c, a 9.178(2), b 14.833(3), c 7.347(8) Ǻ, β 93.89(2)°, Z = 2 f.u .; R was 0.042 for No = 1451 'observed' (I > 3σ(I)) reflections; the bromide is related, having a derivative triclinic cell, Pī, a 9.259(3), b 15.153(6), c 7.428(2) Ǻ, α 90.28(3), β 94.62(2), γ 91.15(3)°, Z = 2 f.u .; R was 0.047 for No 2729. [( trz )PbI2](∞|∞), also solvated, is triclinic, Pī , a 15.266(9), b 8.9448(8), c 8.148(11) Ǻ, α 80.60(6), β 77.05(7), γ 83.45(3)°, Z = 2; R was 0.032 for No 3222. In all three compounds an infinite PbX2PbX2Pb polymer is found with the plane of the tridentate trz lying quasi normal to the polymer axis. Pb -N distances lie between 2.63(1) and 2.803(8) Ǻ; Pb-Cl are 2.848(3) and 3.074(3), Pb -Br 2.963(2)-3.257(2) and Pb-I 3.192(3)-3.466(2) Ǻ. The thiocyanate, monoclinic, C 2/c, a 16.974(6), b 6.410(2), c 39.49(2) Ǻ, β 96.33(4)°, Z = 8, R 0.13 for No 2465, is a column of dimeric units stacked up b, successive lead atoms being bridged by thiocyanate sulfur atoms packed in between them, and quasi-parallel to a, and by thiocyanates parallel to b which link pairs of lead atoms in each dimer with the same b coordinate by pairs of bridging nitrogens and bridging sulfurs from the adjacent pair.

Lewis-Base Adducts of Lead(II) Compounds. VIII. Synthetic and Structural Studies of Some Adducts of Linear Polyamines With Lead(II) Bromide

1996 ◽  
Vol 49 (10) ◽  
pp. 1043 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
TM Shand ◽  
BW Skelton ◽  
AA Soudi ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Room Temperature ◽  
Lewis Base ◽  
Lead Atom ◽  
Two Dimensional ◽  
Structural Studies ◽  
Atom Type ◽  
X Ray ◽  
Structure Determinations ◽  
A Chain

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for adducts of lead(II) bromide with some linear polyamines. Adducts with ethane-1,2-diamine ('en') and propane- 1,2-diamine (' pn ') are of 2:1 and 1:1 stoichiometry respectively. [(en)2PbBr2](∞|∞) is monoclinic, C2/c, a 13,076(4), b 7.586(2),c 13.248(4) Ǻ, β 117.88(2)°, Z = 4 f.u .; R was 0.029 for No = 1832 'observed' (I > 3σ(I)) reflections (a redetermination ). [( pn )PbBr2](∞|∞) is orthorhombic, Pbca , a 23.457(3), b 9.567(2), c 7.714(3) Ǻ, Z = 8; R 0.051 for No 1297. [(en)2PbBr2](∞|∞) is a single stranded linear polymer parallel to c; the lead atom, lying on a crystallographic twofold axis, is six-coordinate PbN4Br2, with the bromine atoms cis in the coordination sphere and lying opposed to a bidentate en ligand. The trans sites are linked into a chain by bridging en ligands . [( pn )PbBr2](∞|∞) is a more complex two-dimensional polymer; the pn is bidentate , but the lead atoms are now eight coordinate with doubly and quadruply bridging bromines linking them into the polymeric sheet. The adduct with '323tet' (4,7-diazadecane 1,10-diamine) is of a novel (323tet)2(PbBr2)3 stoichiometry , best represented (simplistically) as {[ Pb (323tet)]2[PbBr6]}(∞|∞); crystals are triclinic, Pī , a 11.892(4), b 9.306(3), c 9.016(6) Ǻ, α 60.74(4), β 86.04(4), γ 74.43(3)°, Z = 1 f.u ., with R 0.061 for No 2071. About one lead atom type, the ligand is quadridentate , lying on one face of the coordination sphere; the region opposite is occupied by four triply bridging bromine atoms from the [PbBr6] anionic units (which contain quasi-octahedral, centrosymmetric lead. with a pair of trans-bromine atoms terminal and the others bridging) linking the array into a two dimensional polymer.

Lewis-Base Adducts of Lead(II) Compounds. IX. Synthetic and Structural Studies of Some 1:1 Adducts of 'cyclam' and Its Hexamethylated Derivative 'tet-b' With Lead(II) Oxoanion Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1051 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
TM Shand ◽  
BW Skelton ◽  
AA Soudi ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Room Temperature ◽  
Lewis Base ◽  
The Other ◽  
Lead Atom ◽  
Structural Studies ◽  
Centrosymmetric Dimer ◽  
X Ray ◽  
Structure Determinations ◽  
Perchlorate Complex

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of (1,4,8,11-tetraazacyclotetradecane) ('cyclam') with lead(II) perchlorate and (7R*,14R*)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ('tet -b') with lead(II) nitrate, perchlorate and acetate ('ac'). [( cyclam ) Pb (ClO4)2] is orthorhombic, Pb21a, a 16.024(7), b 13.595(4), c 8.6810(5) Ǻ, Z = 4 f.u .; R was 0.055 for No 1318 independent 'observed' (I > 3σ(I)) reflections. [( tet -b) Pb (NO3)2]2 is monoclinic. P 21/a, a 16.15(2), b 14.550(6), c 19.775(2) Ǻ, β 90.86(5)°, Z = 4 dimers ; R 0.074 for No 3184. [( tet -b) Pb (ClO4)2]2.H2O is monoclinic, P 21/c, a 13.663(9), b 9.031(3). c 20.61(1) Ǻ, β 100.40(3)°, Z = 4 f.u .; R 0.044 for No 2857. [( tet -b) Pb (ac)2].2H2O is triclinic, Pī , a 13.138(5), b 10.924(4), c 10.518(3) Ǻ, α 115.48(3), β 91.95(2), γ 102.38(2)°, Z = 2 f.u .; R 0.031 for No 6485. In all complexes, the macrocycle-N4 ligand occupies one 'side' of the coordination sphere of the lead atom, with anionic oxygens opposed; the cyclam/perchlorate complex is, like the nitrate, mononuclear with seven-coordinate (N4)PbO3 with a bidentate O,O'- and a unidentate O- perchlorate . In the tet-b acetate, the anionic oxygen atoms are surprisingly sparse, comprising simply a bidentate acetate in a mononuclear (N4)PbO2 environment with the other (lattice) acetate bonded to the macrocycle axial NH hydrogens . The nitrate and perchlorate complexes involve bridging anions: in the nitrate. a central centrosymmetric PbO2Pb array is found, the lead atoms being bridged by one oxygen of a bidentate nitrate, the other nitrate being unidentate and the coordination sphere (N4)PbO4: in the perchlorate , again a centrosymmetric dimer is found, the lead atoms being linked by O,O'-bridging perchlorates (again with (N4)PbO2 coordination environments), the complex being essentially [( tet -b) Pb (OClO2O)2Pb( tet -b)](ClO4)2H2O. The structure of [cyclamH4]4+ (NO3-)4.2H2O is also recorded [triclinic, Pī , a 8.626(2), b 8.549(1), c 8.400(2) Ǻ, α 80.60(2), β 76.62(2), γ 65.06(1)°, Z = 1; R 0.044 for No 1539], together with that of the diprotonated hexamethyl derivative [tet-bH2]2+(ClO4-)2.CH3OH [monoclinic, P21/c, a 11.296(3), b 8.834(8), c 26.22(1) Ǻ, β 99.05(3)°, Z = 4 f.u .; R 0.063 for No 2583].

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. VII. Synthetic and Structural Studies of Some 1:1 Adducts of Linear Polyamines With Lead(II) Nitrate

1996 ◽  
Vol 49 (10) ◽  
pp. 1029 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Coordination Sphere ◽  
Room Temperature ◽  
Internal Symmetry ◽  
Lewis Base ◽  
Structural Studies ◽  
One Dimensional ◽  
X Ray ◽  
Structure Determinations

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of lead(II) nitrate with the linear multidentate polyamines ethane-1,2-diamine ('en'(= '2')), H2N(CH2)2NH(CH2)2NH2(' dien ' = '22') and H2N(CH2)xNH(CH2)yNH(CH2)zNH2 ( xyztet = '222tet' (= ' trien '), '232tet', '323tet'). Crystal/refinement data are as follows: [(en) Pb (NO3)2](∞|∞) is monoclinic, P 21/c, a 5.388(2), b 12.440(5), c 13.123(3) Ǻ, β 102.33(3)°, Z = 4 f.u .; R 0.037 for No 2698 'observed' (I > 3σ(I)) reflections. [( dien ) Pb (NO3)2](∞|∞) is orthorhombic, Ccma , a 9.800(2), b 10.840(2), c 20.521(5), Z = 8; R 0.045, No 991. [( trien ) Pb (NO3)2](∞|∞) is orthorhombic, P 212121, a 14.815(3), b 10.975(3), c 8.410(2) Ǻ, Z = 4; R 0.050, No 1360; [(232tet) Pb (NO3)2](∞|∞) is isomorphous, a 14.524(6), b 11.221(1), c 8.860(2) Ǻ, R 0.036, No 2371. [(323tet) Pb (NO3)2](∞|∞) is monoclinic, P21/c, a 8.195(4), b 14.407(7), c 13.312(4) Ǻ, β 91.05(3)°, Z = 4; R 0.049, No 1644. In general, the degree of complexity of the adduct diminishes as the ligand size increases: whereas the en adduct is a compact one-dimensional two stranded polymer with nearly all nitrate oxygens involved in tight bridging interactions, the extent of bridging diminishes in the adducts of the larger amines, until, for the 323tet species, a monomer is obtained involving a lead coordination sphere containing the ligand and a pair of bidentate nitrate groups. The 1 : 2 adduct with en is also recorded, and is a dimer with quasi-i internal symmetry. [(en)2Pb(NO3)2]2 is monoclinic, P21, a 6.661(2), b 14.226(8), C 13.618(4)Ǻ, β 96.51(2)°; R 0.072, No 1713.

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