Lewis Base Adducts of Lead(II) Compounds. I. Polymer Isomerism in Some 1-2 Adducts of Lead(II) Halides With Pyridine Bases

1987 ◽  
Vol 40 (12) ◽  
pp. 2107 ◽  
Author(s):  
LM Engelhardt ◽  
JM Patrick ◽  
CR Whitaker ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Coordination Sphere ◽  
Structure Determination ◽  
Lone Pair ◽  
Lewis Base ◽  
The Other ◽  
X Ray ◽  
Coordination Sites ◽  
Pyridine Bases ◽  
Orthogonal Geometry

Recrystallization of lead(II) halides, PbX2 (X = C1, Br, I), from n- methylpyridine, n = 3, 4, yields crystalline 1 : 2 adducts; these have all been shown by single-crystal X-ray structure determination to contain the lead in an essentially octahedral six-coordinate environment, two of the coordination sites being occupied by monodentate pyridine base moieties and four by bridging halogen, yielding infinite polymeric arrays. For X = Cl, Br, n = 3, the nitrogen atoms lie cis in the coordination sphere; for the other complexes, they are trans. In the two cis complexes, distortion from ideal orthogonal geometry is more substantial than in the trans, possibly indicative of the presence of a sterically active 'lone pair'.

Lewis-Base Adducts of Lead(II) Compounds. III. Synthesis and Structural Characterization of Mononuclear (Nitrato-O,O′)bis(1,10-phenanthroline)-(thiocyanato-N)lead(II)

1989 ◽  
Vol 42 (2) ◽  
pp. 335 ◽  
Author(s):  
LM Engelhardt ◽  
JM Patrick ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Structure Determination ◽  
Title Compound ◽  
Lone Pair ◽  
Lewis Base ◽  
Lead Atom ◽  
X Ray

The isolation and single-crystal X-ray structure determination of the title compound, [(phen)2Pb(NCS)(O2NO)] is described; crystals are triclinic, P1, a 15.554(7), b 9-670(4), c 8.429(3) α 72.53(3), β 81.90(3), γ 72.88(3)� Z = 2, yielding R 0.052 for 3405 independent 'observed' reflections. The lead atom is seven-coordinate [Pb-N 2.49(1)-2.60(1) (phen), 2.89(1) (NCS); Pb-O 2.75(1), 2.89(1) �] with a large vacancy in the coordination sphere, possibly indicative of a stereochemically active lone pair.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXI. The 1 : 1 Adducts of the Copper(I) Halides (Cl, Br, I) With Bis(2-diphenylphosphinoethyl)phenylphosphine, 'triphos'

1991 ◽  
Vol 44 (7) ◽  
pp. 919 ◽  
Author(s):  
RD Hart ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structure Determination ◽  
Copper Atom ◽  
Phosphorus Atom ◽  
Lewis Base ◽  
The Other ◽  
Asymmetric Unit ◽  
X Ray

The 1 : 1 adducts between the copper(I) halides, CuX , X = Cl , Br, I, and the title ligand, 'triphos', Ph2P(CH2)2P(Ph)(CH2)2PPh2, have been synthesized and characterized by single-crystal X-ray structure determination. The three complexes are isomorphous : monoclinic P21/c, a ≈ 14.5, b ≈ 20.5, c ≈ 24.5 Ǻ, β ≈ 118.5°; the asymmetric unit of each structure is the binuclear [Cu2X2( triphos )2] unit (with one acetonitrile solvate). Residuals were 0.047, 0.049 and 0.065 for 6006, 4832 and 5108 'observed', independent reflections respectively. About each copper atom, the four-coordinate environment comprises a terminal halogen [Cu- Cl,Br,I , 2.305(3), 2.311(2); 2.441(2), 2.443(2); 2.614(2), 2.614(2)Ǻ], two phosphorus atoms (central and distal) from the same ligand , and one distal phosphorus atom from the other ligand.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. XXXVII. A Novel Isomerism in the Heterobimetallic 1:1 Adducts of Copper(I) Halides With Tris(dithiocarbamato)cobalt(III)

1988 ◽  
Vol 41 (6) ◽  
pp. 839 ◽  
Author(s):  
LM Engelhardt ◽  
PC Healy ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structure Determination ◽  
Lewis Base ◽  
X Ray

Reaction of copper(I) iodide with tris (N,N- dipropyl -and N, N- diisopropyl-dithiocarbamato )cobalt(III), [Co(S2CNR2)3 ≡ Co( dtc )3](R = Pr or Pri ), yields 1:1 adducts which have been characterized by single-crystal X-ray structure determination. Crystals of the propyl species are monoclinic, P21/c, a 13.722(7), b 16.854(7), c 16.787(8)Ǻ, β 121.66(3)°, R was 0.056 for No 2834 'observed' reflections. The isopropyl derivative is orthorhombic, Ccca , a 33.93 (1), b 13.616(8), c 14.574(5)Ǻ; R was 0.075 for No 726. Each adduct is dimeric [Co( dtc )3](CuI2Cu)[Co( dtc )3]; the propyl derivative has crystallographically imposed i symmetry, whereas the isopropyl adduct has quasi-222 symmetry. Thus, the chiralities of the pair of Co( dtc )3 moieties in the dipropyl adduct are opposite, whereas in the isopropyl adduct they are the same.

Lewis-Base Adducts of Main Group 1 Metal Compounds. V. Diaquabis(quinoline)lithium(I) Bromide Bis(quinoline)

1988 ◽  
Vol 41 (3) ◽  
pp. 409 ◽  
Author(s):  
CL Raston ◽  
BW Skelton ◽  
CR Whitaker ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structure Determination ◽  
Title Compound ◽  
Lithium Bromide ◽  
Main Group ◽  
Lewis Base ◽  
Metal Compounds ◽  
X Ray ◽  
Group 1

The title compound, an artefact of recrystallization of lithium bromide from improperly dried quinoline, has been characterized by a single- crystal X-ray structure determination. Crystals are triclinic, Pī , a 16.608(9), b 12.27(1), c 7.962(8)Ǻ, α 101.98(8),β 91.79(7),γ 92.27(6), Z 2; R was 0.058 for 2404 'observed' reflections. The cation is the first to be structurally defined for a [Li(OH2)2 (N-base)2]+ system; Li-O are 1.92(2), 1.93(2)Ǻ and Li-N 2.12(2), 2.14(2)Ǻ.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LI. Synthesis and Structural Characterization of Mononuclear Chloro-, Bromo- and Iodo-pyridinebis(triphenylphosphine)copper(I) Complexes

1989 ◽  
Vol 42 (6) ◽  
pp. 895 ◽  
Author(s):  
LM Engelhardt ◽  
PC Healy ◽  
JD Kildea ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Structure Determination ◽  
Copper Atom ◽  
Lewis Base ◽  
X Ray

Complexes [ XCu ( py )(PPh3)2], X = Cl, Br, I, py = pyridine, have been synthesized and characterized by single-crystal X-ray structure determination. Chloride and iodide derivatives have similar cells [ isomorphous (?) but not isostructural ], triclinic, pi, a = 19.5 A, b = 10.5, c = 9.6 � , α ≈ 66, β ≈ 86, γ ≈ 83�, Z = 2; the bromide is monoclinic, Cc, a 13.568(9), b 15.760(12), c 16.545(8) � , β 95.65(5)�, Z = 4. Cl, Br, I structures were refined to residuals of 0.042, 0.055, 0.039 for 4288, 2241, 4808 'observed' reflections. In all cases, the copper atom is four-coordinate; for such an array, Cu-X lengths are unusually short [2.318(2), 2.459(2), 2.636(1) � (Cl, Br, I) and Cu-N unusually long (2.14(1) � ], while (Cu-P) increase from 2.264 to 2.288 � across the series. The dominant aspect of the complexes is thus that of XCu (PPh3)2 solvated by pyridine.

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.

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXIV Synthesis and Structure of the 1 : 1 Adduct of Silver(I) Nitrate with Triphenylstibine

1997 ◽  
Vol 50 (6) ◽  
pp. 671 ◽  
Author(s):  
Effendy ◽  
John D. Kildea ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Structure Determination ◽  
Related Species ◽  
Room Temperature ◽  
Structural Data ◽  
Lewis Base ◽  
One Dimensional ◽  
X Ray ◽  
The One

The synthesis and room-temperature single-crystal X-ray structure determination of the 1 : 1 adduct of silver(I) nitrate with triphenylstibine, AgNO3/SbPh3 (1 : 1), is recorded, being monoclinic, Cc,a 12·824(2), b 15·794(4),c 9·796(2) Å, β 117·50(1)°, Z= 4; conventional R on F was 0·030 for 2881 independent ‘observed’ (I > 3σ(I)) reflections. The complex is a one-dimensional polymer with bridging nitrate groups, resembling in this respect its phosphine and arsine analogues. The completion of this study, along with related species recorded in accompanying papers, means that full structural data are now available for the complete array AgNO3/EPh3 (1 : n), E = P, As, Sb, n = 1–4, with the one exception of E = Sb, n = 2.

Lewis-Base Adducts of Main Group 1 Metal Compounds. IV. Synthesis and Structure of the XLiL3 System (X = Cl, Br, I, L = 4-t-Butylpyridine, and X = I, L = Quinoline)

1988 ◽  
Vol 41 (3) ◽  
pp. 341 ◽  
Author(s):  
CL Raston ◽  
BW Skelton ◽  
CR Whitaker ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structure Determination ◽  
Main Group ◽  
Lewis Base ◽  
Similar Data ◽  
Metal Compounds ◽  
X Ray ◽  
Close Parallel ◽  
Group 1

Complexes [XLiL3], X = Cl , Br, I; L = 4-t-butylpyridine, (1)-(3) have been synthesized by recrystallization of the anhydrous lithium halide from the parent base, and characterized structurally by single-crystal X-ray structure determination. (1) and (2) are isomorphous (monoclinic, P21), a ≈ 11.8, b ≈ 12.1, c ≈ 11.8 Ǻ, β 120°, Z 2 (R 0.051, 0.040 for No 1491, 1499 'observed' reflections); (3) is orthorhombic, Pbca, a 22.119(10), b 21.108(10), c 12.845(10) Ǻ, Z 8, R 0.067 for No 967. (1)- (3) are all pseudo- trigonal and contain four-coordinate XLiN3 arrays [Li-X, 2.33(1); 2.53(1); 2.76(4) Ǻ; Li-N, 2.03(1)-2.11(1); 2.04(1)-2.09(2); 2.03(4)-2.07(4)Ǻ]. Similar data are also recorded for X = I, L = quinoline (4)[monoclinic, P21/c, a 15.684(6), b 7.693(4), c 26.758(12) Ǻ,β 107.71(3)°, Z 4; R 0.072, No 3096; Li-I, 2.78(2); Li-N, 2.08(2)- 2.13(2)Ǻ]. While a close parallel may be drawn between the similarity of the chemistry of lithium(I) and copper(I) in respect of (1)-(3), (4) is unusual being the first XML3 derivative for a quinoline -type ligand; it is a monoquinoline solvate.

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 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].

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