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 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.

Structural Systematics of Rare Earth Complexes. VII. Crystal Structure of Bis(2,2'/6',2␛-Terpyridinium) Octaaquaterbium(III) Heptachloride Hydrate

1994 ◽  
Vol 47 (2) ◽  
pp. 391 ◽  
Author(s):  
CJ Kepert ◽  
BW Skeleton ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Rare Earth ◽  
Single Crystal ◽  
Structural Characterization ◽  
Title Compound ◽  
Room Temperature ◽  
Chloride Ions ◽  
Full Matrix ◽  
X Ray

The room-temperature single-crystal X-ray structural characterization of the title compound (tpyH2)2[Tb(OH2)8]Cl7.~2⅓H2O is recorded. Crystals are triclinic, Pī , a 17.063(5), b 16.243(3), c 7.878(3) Ǻ, α 84.78(2), β 84.39(3), γ 87.81(2)°, Z = 2 formula units; 3167 'observed' diffractometer reflections were refined by full-matrix least-squares procedures to a residual of 0.057. Notable features of interest of the compound are the 'chelation' of chloride ions by the terpyridinium cations , and the existence of a free [Tb(OH2)8]2+ cation in the presence of an abundance of chloride ions.

Structural Characterization of a Cage Ligand Fragmentation Reaction

1994 ◽  
Vol 47 (1) ◽  
pp. 181 ◽  
Author(s):  
JM Harrowfield ◽  
AM Sargeson ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Room Temperature ◽  
Fragmentation Reaction ◽  
X Ray ◽  
Nitrogen Donor ◽  
Crystal Structural

The room temperature X-ray single-crystal structural characterization of a protonated copper(II) complex of a ligand artefact, L′, of L = N-Me6sar (described in an accompanying paper) is recorded, the new ligand L′ being generated formally by elimination of a CH2CH2 bridge between a pair of nitrogen donor atoms of L. The complex, [ ClCu (H2L′) (ClO4)3.2H2O, is orthorhombic, Pccn , a 22.528(7), b 10.544(3), c 13.748(6) Ǻ, Z = 4 formula units, R being 0.053 for 1133 independent 'observed' [I > 3σ(I)] reflections. The cation, containing five-coordinate square-pyramidal ClCuN4 copper, is disposed with the Cu- Cl bond [2.458(3)Ǻ] lying on a crystallographic 2 axis; Cu-N distances are 2.094(8) and 2.093(8)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.

Single Crystal X-Ray Structural Characterization of [BiX2(S2CNEt2)]Infinity∞, X=Cl, Br

1994 ◽  
Vol 47 (2) ◽  
pp. 405 ◽  
Author(s):  
PK Bharadwaj ◽  
AM Lee ◽  
BW Skelton ◽  
BR Srinivasan ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Sulfur Atom ◽  
Structural Characterization ◽  
Structure Determination ◽  
Room Temperature ◽  
X Ray ◽  
Structure Determinations

Single-crystal room-temperature X-ray structure determinations of the title compounds have been carried out. The two compounds are isomorphous, and isomorphous with the previously determined iodide analogue, being monoclinic, P 21/c, a ≈ 10.0, b ≈ 14.9, c ≈ 7.8 Ǻ, β ≈ 92°, Z = 4 formula units; residuals were 0.037, 0.036 for 2197, 1654 'observed' reflections for X = Cl , Br respectively. As in the iodide, the complexes are infinite polymers, with successive bismuth atoms bridged by the two halides and one sulfur atom of the ligand , which also chelates each bismuth. The structure determination of C5H5NCONEt2]2 [Cl5Bi(NC5H5)], isostructural with its thiocarbamoyl analogue, is also recorded.

Lewis-Base Adducts of Group 11 Metal-Compounds. XXXIII. Structural Characterization of Two Novel 'Trigonal Planar' Halobis(N-Base)Copper(I) Complexes

1988 ◽  
Vol 41 (3) ◽  
pp. 335 ◽  
Author(s):  
JC Dyason ◽  
LM Engelhardt ◽  
PC Healy ◽  
JD Kildea ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Lewis Base ◽  
Metal Compounds ◽  
Base Complex ◽  
X Ray ◽  
Structure Determinations

Single-crystal X-ray structure determinations are recorded for two unusual trigonal planar XCuL2 species, X = halogen, L = monodentate N- base. For iodobis (2-methylquinoline)copper(I) (1) crystals are orthorhombic, P212121, a 15.079(7), b 12.592(7), c 9.585(4)Ǻ, Z 4. R was 0.028 for 1285 independent 'observed' reflections; the copper(I) environment is trigonal planar [I-Cu, 2.533(2); Cu-N, 2.034(6), 2.0l5(7)Ǻ; I-Cu-N are 119.1(2), 120.4(2) and N-Cu-N, 120.4(2)°]. For the mixed base complex bromo (3,5-dimethylpyridine)(2,4,6-trimethylpyridine )copper(I) (2), crystals are triclinic, pī , a 13.643(5), b 8.434(5), c 8.163(4)Ǻ, α 59.65(4), β 79.76(4), γ 89.68(4)°, Z 2; R was 0.046 for 1551 'observed' reflections. Br-Cu is 2.418(2); Cu-N, 1.971(5), 1.963(6)Ǻ; Br-Cu-N are 113.5(2), 110.0(2) and N-Cu-N, 136.4(3)°.

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 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 Group-11 Metal(I) Compounds. XXXI. Reaction of 2,6-Bis[1-phenyl-1-(pyridin-2-Yl)ethyl]pyridine (L), and Copper(I) Halides in Acetonitrile: Structural Characterization of Salts of the [(MeCN)Cu(meso-L)]+ Cation

1987 ◽  
Vol 40 (11) ◽  
pp. 1881 ◽  
Author(s):  
AJ Canty ◽  
LM Engelhardt ◽  
PC Healy ◽  
JD Kildea ◽  
NJ Minchin ◽  
...  
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Lewis Base ◽  
Tridentate Ligand ◽  
Acetonitrile Solution ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ligand Conformation

Reaction of 2,6-bis[l-phenyl-1-(pyridin-2-yl)ethyl]pyridine, L, with copper(1) chloride, bromide, and iodide in acetonitrile solution has been shown to yield salts, structurally characterized by single-crystal X-ray diffraction methods as [( MeCN ) CuL ]+ [ ClCuCl ]-, (1), [( MeCN ) CuL ]+2 [XCuX2CuX]2-, X = Br (2), I (3) (both isomorphous ), all as yellow needles, and a form of (3), orange blocks, as the hemiacetonitrile solvate, (4), [( MeCN ) CuL ]+2 [IcuI2Cul]2-. MeCN . The same cation is common to all four species, containing four-coordinate copper(r), with L as meso -tridentate ligand; in (4), the most precisely defined example, Cu-N( MeCN ) is 1.919(5) �, the shortest copper(1) acetonitrile distance known, while Cu-N(L) are 2.065(5)-2.073(5) �. The reason for non-formation of species of the type [ LCuX ] appears to lie in the tridentate ligand conformation which permits coordination of acetonitrile but not larger halide species.

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