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. 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. 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.

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 Group 11 Metal(I) Compounds. LXVIII Synthesis and Structural Systematics of Some 1 : 3 Adducts of Silver(I) Compounds with Triphenylstibine, [(Ph3Sb)3AgX], X = Cl, I, SCN, NCS, CN, ONO2

1997 ◽  
Vol 50 (6) ◽  
pp. 587 ◽  
Author(s):  
Effendy ◽  
John D. Kildea ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Room Temperature ◽  
Lewis Base ◽  
Nitrate Complex ◽  
X Ray ◽  
Ethanol Solvate ◽  
New Form ◽  
Pseudo Halides

The syntheses and room-temperature single-crystal X-ray structural characterization of 1 : 3 adducts formed between silver(I) (pseudo-) halides, AgX, and triphenylstibine, SbPh3, are described for X = Cl, I, SCN, NCS, CN, NO3 (1)-(6). The chloride, as its methanol solvate (1a), is isomorphous with the arsine analogue: triclinic, P-1, a 13·373(4), b 14·48(6), c 14·702(3) Å, α 83·49(3), β 87·76(2), γ 76·45(3)°; Z = 2, conventional R on F being 0·046 for No 5514 independent ‘observed’ reflections (I > 3σ(I )). A new form (1b) of the chloride has also been authenticated: monoclinic, P 21/c, a 12·832(2), b 54·24(1), c 18·519(8) Å, β 129·68(3)°; Z = 8 (R 0·065 for No 5672). No bromide has been obtained; the iodide (2) is described as monoclinic, P 21/n, a 19·611(4), b 14·473(6), c 17·74(1) Å, β 98·28(3)°; Z = 4 (R 0·036 for No 6769). The thiocyanate crystallizes from acetonitrile or pyridine as an S-bonded form (3) isomorphous with the arsine analogue: monoclinic, P 21/n, a 19·143(7), b 14·288(5), c 18·694(6) Å, β 98·81(2)°; Z = 4 (R 0·037 for No 4482). From 2-methylpyridine, remarkably, a solvate is obtained in which the thiocyanate is N-bonded (4): triclinic, P-1, a 27·261(5), b 14·767(3), c 13·319(1) Å, α 91·53(1), β 101·58(1), γ 92·29(2)°; Z = 4 (R 0·045 for No 6900). The cyanide is also monoclinic, P 21/n, a 19·442(7), b 14·267(3), c 17·741(6) Å, β 97·63(3)°, z = 4; R 0·057 for No 2487. The unsolvated 1 : 3 nitrate complex (6a) is monoclinic, P 21/n, a 19·602(5), b 14·455(1), c 17·727(2) Å, β 97·19(2)°, Z = 4; R was 0·034 for No 6522. The complex is isomorphous with the arsenic and phosphorus analogues, being mononuclear [(Ph3Sb)3Ag(O2NO)]. The ethanol solvate (6b) is triclinic, P-1, a 13·352(5), b 14·548(9), c 14·701(4) Å, α 81·64(4), β 84·45(3), γ 75·32(4)°, Z = 2; R was 0·058 for No 4702. Ag-Sb range between 2·6980(8) and 2·843(3) Å in the precise determinations; Ag-X are 2·481(4) and 2·52(1) Å (the two chlorides), 2·757(1) (I), 2·533(3) (SCN), 2·21(1) (NCS), 2· 09(3) (CN), 2·377(7) Å (unidentate ONO2)

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

1996 ◽  
Vol 49 (10) ◽  
pp. 1147 ◽  
Author(s):  
JM Harrowfield ◽  
DL Kepert ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
...  
Keyword(s):  
Single Crystal ◽  
Polymer Chain ◽  
Room Temperature ◽  
Lewis Base ◽  
Lead Atom ◽  
Structural Studies ◽  
Complex Species ◽  
X Ray ◽  
The Third ◽  
Metal Ligand

Adducts of lead(II) nitrate with 2,4,6-tris(2-pyridyl)-1,3,5-triazine (' trz ') have been synthesized and structurally characterized by room-temperature single-crystal X-ray studies, for 1:1 and 1:2 stoichiometry. Crystals of [( trz ) Pb (NO3)2](∞|∞) are monoclinic, P 21/c, a 10.531 (1), b 12.856(2), c 16.874(3) Ǻ, β 102.83(1)°, Z = 4 f.u .; R was 0.027 for No = 2773 'observed' (I > 3σ(I)) reflections. The complex is an infinite polymer; the plane of the tridentate trz ligand lies normal to the polymer axis ( Pb -N(central; distal) 2.523(5); 2.594(5), 2.568(5) Ǻ) with unsymmetrically bidentate nitrate groups to either side ( Pb -O 2.598(6), 2.928(7); 2.556(6), 2.911(7) Ǻ). The third oxygen of each nitrate group bridges to the next lead atom in the polymer chain ( Pb -O 3.008(5), 3.083(6)Ǻ). [( trz )2Pb(NO3)2] is monoclinic, C 2/c, a 15.723(5), b 10.034(2), c 24.379(15) Ǻ, β 106.84(4)°, Z = 4 f.u .; R was 0.038 for No 3030. The compound is a methanol monosolvate. The complex species is mononuclear, with the lead atom located on a crystallographic 2 axis and 10-coordinated by pairs of symmetry-related tridentate trz ( Pb -N(central; distal) 2.779(4); 2.800(5), 2.818(5) Ǻ) and bidentate nitrate ligands ( Pb -O 2.796(6), 2.689(5)Ǻ). A hexahydrate has also been obtained (triclinic, Pī a 23.580(9), b 10.147(4), c 9.762(4)Ǻ, α 113.14(3), β 92.11(3), γ 101.60(3)°, Z = 2 f.u ; R 0.041 for No 5633); although metal-ligand distances are similar to those found in the methanol solvate, and quasi-2 symmetry is retained, a very different stereochemistry is evident in respect of the relative dispositions of the ligands about the (quasi)-2 axis, involving a substantial twist of the two nitrate ligands relative to the triazines, and a flattening of the latter. The coordination polyhedron is different in the two 1:2 adducts. In the methanol solvate the stereochemistry is pentagonal antiprismatic whereas in the hexahydrate it is bicapped square antiprismatic.

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 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 Lead (II) Compounds. XI. Synthetic and Structural Studies of Some 1:1 Adducts of 2,2'-Bipyridine and 1,10-Phenanthroline With Lead(II) Oxoanion Salts

1996 ◽  
Vol 49 (10) ◽  
pp. 1081 ◽  
Author(s):  
JM Harrowfield ◽  
H Miyamae ◽  
BW Skelton ◽  
AA Soudi ◽  
AH White
Keyword(s):  
Room Temperature ◽  
Lewis Base ◽  
The Other ◽  
Lead Atom ◽  
Structural Studies ◽  
Centrosymmetric Dimer ◽  
One Dimensional ◽  
X Ray ◽  
Structure Determinations ◽  
Oxygen Atoms

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1 : 1 adducts of 1,10-phenanthroline ('phen') with lead(II) nitrate (as a monohydrate; the structure of the isomorphous 2,2'-bipyridine (' bpy ') analogue is also recorded) and of its lead(II) acetate ('ac') analogue (as a dihydrate ). [( bpy ) Pb (NO3)2](∞|∞).H2O is monoclinic, P 21/c; a 7.244(9), b 9.872(2), c 20.395(5) Ǻ, β 109.08(7)°, Z = 4 f.u ., R being 0.048 for No = 3447 independent 'observed' (I > 3σ(I)) reflections. [( phen ) Pb (NO3)2](∞|∞).H2O has a 7.168(2), b 9.972(1), c 21.069(3) Ǻ, β 99.47(1)°, R 0.034 for No 3596. [( phen ) Pb (ac)2]2.4H2O is triclinic, Pī , a 13.932(3), b 12.904(4), c 12.716(5) Ǻ, α 62.37(2), β 71.16(2), γ 60.55(2)°, Z = 2 ( dimers ); R was 0.029 for No 5457. The nitrates are one-dimensional polymers along b, successive lead atoms being linked by one oxygen of one of the nitrate groups, each of the other oxygen atoms completing a chelate to either side; the lead environment is completed as N2PbO7 by the other nitrate (as a chelate ), the bidentate base, and the water molecule. In the acetate which is a centrosymmetric dimer (manifested in two distinct independent dimers ) the two lead atoms are linked by bridging oxygen atoms derived from pairs of chelating acetate moieties about each lead atom. The coordination sphere of each lead atom is completed by the bidentate aromatic base. The two dimers differ significantly in parallel comparison of their geometrical descriptors.

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