Structural Characterization of a Cage Ligand Fragmentation Reaction

1994 ◽  
Vol 47 (1) ◽  
pp. 181 ◽  
Author(s):  
JM Harrowfield ◽  
AM Sargeson ◽  
BW Skelton ◽  
AH White

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.

1994 ◽  
Vol 47 (2) ◽  
pp. 391 ◽  
Author(s):  
CJ Kepert ◽  
BW Skeleton ◽  
AH White

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.


1994 ◽  
Vol 47 (2) ◽  
pp. 405 ◽  
Author(s):  
PK Bharadwaj ◽  
AM Lee ◽  
BW Skelton ◽  
BR Srinivasan ◽  
AH White

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.


1997 ◽  
Vol 50 (6) ◽  
pp. 587 ◽  
Author(s):  
Effendy ◽  
John D. Kildea ◽  
Allan H. White

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)


2018 ◽  
Vol 30 (3) ◽  
pp. 485-489 ◽  
Author(s):  
Ekaterina A. Sirotkina ◽  
Luca Bindi ◽  
Andrey V. Bobrov ◽  
Anastasia Tamarova ◽  
Dmitry Yu. Pushcharovsky ◽  
...  

1994 ◽  
Vol 47 (4) ◽  
pp. 757 ◽  
Author(s):  
Z Asfari ◽  
JM Harrowfield ◽  
AN Sobolev ◽  
J Vicens

Despite evidence of coordinative interactions with alkali metal picrates in solution, attempts to crystallize Li+, Na+, K+, Rb+ or Cs+ complexes of a 'doubly crowned' calix [4] arene (obtained by reaction of tetraethylene glycol ditosylate with p-t- butylcalix [4] arene ) have resulted only in the deposition of crystals of the free ligand . A room-temperature single-crystal X-ray study has shown the crystals to be hexagonal, space group P6422, a (= b) 17.092(5), c 20.147(7) Ǻ, V 5097(5) Ǻ3, Z 3, conventional R (on |F|) 0.082 for 1397 'observed' reflections [I > 3σ(I)]. The highly symmetrical oblate-globular shape of this doublecrowncalix allows the enclosure of an extended narrow cavity possibly better suited to the binding of two small metal ions rather than one large.


1997 ◽  
Vol 50 (6) ◽  
pp. 675 ◽  
Author(s):  
Effendy ◽  
Warren J. Grigsby ◽  
Robert D. Hart ◽  
Colin L. Raston ◽  
Brian W. Skelton ◽  
...  

Room-temperature single-crystal X-ray structural characterizations of two oxidation products of triphenylstibine of the form XPh3SbOSbPh3X are recorded for X = Cl, NO3. ClPh3SbOSbPh3Cl is monoclinic, P 21/c, Z = 4 f.u., a 9·109(4), b 19·809(8), c 19·30(2) Å, β 109·27(5)°, conventional R on F being 0·038 for No 4431 ‘observe’ (I > 3σ(I)) independent reflections. In this complex, Sb-O-Sb is quasi-linear, 173·1(3)°, in contrast to the previously recorded benzene solvate, in which it is 139·0(3)°; in the nitrate, [(O2NO)Ph3SbOSbPh3(ONO2)], triclinic, P-1, Z = 2 f.u., a 15·609(5), b 13·238(4), c 10·140(2) Å, α 87·11(2), β 88·46(7), γ 72·93(2)°, R 0·036 for No 5275, it is also bent (137·0(2)°). The anionic substituent is opposed to the oxo bridge in the trigonal bipyramidal five-coordinate array about the metal in both complexes. A redetermination of the structure of Ph8Sb4O6 is recorded, presenting a non-disordered model in a triclinic P-1 cell, a 19·98(3), b 11·635(2), c 9·739(2) Å, α 92·28(1), β 98·98(1), γ 99·74(1)°, Z = 2 f.u., R 0·046 for No 3578. A new (‘β’) phase of triphenylstibine, crystallized from hexane/toluene is also recorded: monoclinic, P 21/c, a 15·386(8), b 11·304(5), c 19·078(8) Å, β11·64(4)°, Z = 8, R 0·045 for No 3393.


1999 ◽  
Vol 52 (6) ◽  
pp. 481 ◽  
Author(s):  
Cameron J. Kepert ◽  
Lioubov I. Semenova ◽  
Lu Wei-Min ◽  
Brian W. Skelton ◽  
Allan H. White

A room-temperature single-crystal X-ray structure determination of the 1 : 1 adduct of 1,10-phenanthroline (`phen") with lutetium(III) acetate (as its dihydrate) is recorded. Crystals are triclinic, P 1, a 12·430(8), b 10·681(4), c 8·134(8) Å, α 74·76(6), β 84·81(7), γ 74·29(4)°, Z = 2 f.u.; conventional R on |F| was 0·031 for No 3939 independent ‘observed’ (I > 3σ(I)) diffractometer reflections. The complex [(N,N′-phen)(O,O′-ac)Lu(O-ac-O′)4Lu(O,O′-ac)(N,N′-phen)].2H2O is binuclear, the lutetium being eight-coordinated by bidentate phen and ac (acetate) ligands and four oxygen atoms from the bridging acetate ligands. Also recorded is the structural characterization of 1 : 1 Lu(ac)2Cl/tpy (tpy = 2,2′:6′,2″-terpyridine) as its pentahydrate; this complex is triclinic, P 1, a 12·410(3), b 11·559(4), c 9·976(4) Å, α 85·19(3), β 70·30(3), γ 65·70(2)°, Z = 2, R 0·049 for No 4717. The complex is shown to be [(tpy)(H2O)2Lu(O2CCH3)2]Cl.3H2O, with the lutetium nine-coordinated by tridentate tpy, a pair of bidentate acetates and two unidentate water molecules, with the chloride uncoordinated. Structural characterizations of a number of 1 : 1 adducts of variously solvated lanthanoid(III) trichloroacetates, Ln(tca)3, with tpy are also recorded. Yb(tca)3/tpy/MeOH (1 : 1 : 1) is triclinic, P 1, a 14·016(4), b 12·951(5), c 9·604(3) Å, α 73·89(3), β 76·56(3), γ 69·20(3)°, Z = 2 f.u., R 0·057 for No 4465. The complex is mononuclear, the eight-coordinate N3YbO5 array containing tridentate tpy, unidentate methanol, and two unidentate and one bidentate chelating anions. 1 : 1 : 1 Ln(tca)3/tpy/OH2 adducts for Ln = La(-)Nd are triclinic, P 1, a ≈ 13·4, b ≈ 12·47, c ≈ 11·5 Å, α ≈ 114·5, β ≈ 89·9, γ ≈ 115·6°, Z = 1 binuclear array, R 0·061, 0·071 for No 3240, 2394. The two Ln atoms are O,O′-bridged by a pair of anions, the N3LnO6 nine-coordinate lanthanoid environment being completed by a tridentate tpy, one water, one unidentate and one bidentate anion. A 1 : 1 : 1 Lu(tca)3/tpy/OH2 array, by contrast, is triclinic, P 1, a 16·569(8), b 14·815(5), c 14·375(6) Å, α 62·05(3), β 81·35(4), γ 77·97(3)°, Z = 4 ‘mononuclear’ f.u., R 0·067 for No 6710. The array, remarkably, contains species of both of the above types in a 1 : 2 binuclear-to-mononuclear ratio, but with water replacing methanol in the mononuclear array.


1996 ◽  
Vol 49 (6) ◽  
pp. 673 ◽  
Author(s):  
LAP Kanemaguire ◽  
SG Pyne ◽  
AFH Siu ◽  
BW Skelton ◽  
AH White

The synthesis and room temperature single-crystal X-ray structural characterization of the title compound [( PhCH =CHCH= NCHMePh )Fe(CO)2(PPh3)] are described, the first optically pure 1-azabuta-1,3-diene adduct of iron(0) to be so recorded. Crystals are orthorhombic, P212121, a 20.197(6), b 14.09(1), c 11.094(5) Ǻ, Z 4; conventional R on |F| was 0.061 for 2217 independent 'observed' (I> 3σ(I)) reflections. This compound has been employed to transfer the Fe(CO)2(PPh3) moiety to cyclic 1,3-dienes to give new complexes, including the first example of optically active dicarbonyl ( triphenyl - phosphine )(η4-1-methoxycyclohexa-1,3-diene)iron.


2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.


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