Christian Radek

Template self-assembly of polyiodide networks

A range of metal thioether macrocyclic complexes has been used as templating agents in the preparation of extended multi-dimensional polyiodide arrays. A selection of unusual and intriguing polyiodides is described, and the role played by the size, shape and charge of the metal macrocyclic complex discussed.

The synthesis and low-temperature single crystal X-ray structure of the charge-transfer complex ([9]aneS3)2(l2) 4([9]aneS3 = 1,4,7-trithiacyclononane)

Reaction of [9]aneS3(1,4,7-trithiacyclononane) and I2 in cold CH2Cl2 results in the formation of 1 :1 and 1 : 2 adducts; the single crystal X-ray structure of the 1 :2 adduct ([9]aneS3)3(I2d2)4 shows an unusual polymeric structure with I2 bridging [9]aneS3 thioether units.

The synthesis and single-crystal X-ray structure of the tetranuclear silver(I) complex {[Ag2([18]aneS2O4)2]2}(PF6)4([18]aneS2O4= 1,4,7, 10-tetraoxa-13, 16-dithiacyclooctadecane)

Reaction of AgNO3 with [18]aneS2O4([18]aneS2O4= 1,4,7,10-tetraoxa-13, 16-dithiacyclooctadecane) affords a 1 : 1 complex, the single-crystal X-ray structure of which confirms the formation of binuclear [Ag2([18]aneS2O4)2]2+ dications; these dications are linked in pairs by a long S ⋯ S interaction to give an overall tetranuclear structure.

Templatorganisation von Polyiodid-Netzwerken an komplexierten Metallkationen: Synthese und Kristallstruktur von [Pd2Cl2([18]anN2S4)]1.5I5(I3)2 und [K([15]anO5)2]I9

Mit den Kationen [Pd2Cl2L]2+ und [KL]+ (L[18]anN2S4, L′ = [15]anO5) als Templaten sind neuartige dreidimensionale Polyiodid-Netzwerke zuganglich. Die Metallkationen in [Pd2Cl2L]1.5I5(I3)2 sind durch paarweise Wasserstoffbruckenbindung zu unendlichen Ketten verknupft, wobei die resultierenden kationischen Polymere in Kanalen eines ausgedehnten Polyiodid-Netzwerks liegen. [KL]I9 hat ein dreidimensionales Netzwerk aus deformierten wurfelformigen Kafigen aus I9−-Ionen, deren Hohlraume durch die Metallkationen besetzt sind (Ausschnitt aus der Struktur rechts gezeigt).

Potassium Dibenzo-18-crown-6 Triiodide

In (1,4,7,10,13,16-hexaoxa-2,3:11,12-dibenzocyclooctadeca-2,11-diene)potassium triiodide, [K(C 20 H 24 O 6 )]I 3 , the K + ion is coordinated to the six ether O donors of the macrocycle [K-O 2.716(4)-2.779(4) A] and to atom I3 at a distance of 3.6002(13)A ; I1-I2 is 2.8741(7) and I2-I3 2.9838 (7)A. Pairs of symmetry-related [K(dibenzo-18-crown-6)]I 3 molecules aggregate, with an unusually short distance of 3.184 (3) A between the K + ion and the centroid of one of the benzo groups.

Synthesis and characterisation of palladium(II) complexes of mixed thioether/oxa ionophores. Crystal structures of [PdCl2([18]aneS2O4)], [Pd([18]aneS2O4)2][PF6]2([18]aneS2O4= 1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane) and [Pd([18]aneS3O3)2][PF6]2([18]aneS3O3= 1,4,7-trioxa-10,13,16-trithiacyclooctadecane)

The palladium(II) complexes cis-[PdCl2([18]aneS2O4)], [Pd([18]aneS2O4)2][PF6]2([18]aneS2O4= 1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane), [Pd([18]aneS3O3)2][PF6]2([18]aneS3O3= 1,4,7-trioxa-10,13,16-trithiacyclooctadecane) and [PdCl([20]aneS3O3)]BPh4([20]aneS3O3= 1,4,7-trioxa-10,14,18-trithiacycloicosane) have been synthesised and characterised. Reaction of PdCl2 with 1 molar equivalent of [18]aneS2O4 afforded cis-[PdCl2([18]aneS2O4)]; addition of a second equivalent gave the bis complex cation [Pd([18]aneS2O4)2]2+. The crystal structure of cis-[PdCl2([18]aneS2O4)] showed the PdII in a square-planar co-ordination geometry with mutually cis Cl– ligands, Pd–S(1) 2.276(2), Pd–S(4) 2.2786(14), Pd–Cl(1) 2.307(2), Pd–Cl(2) 2.3100(14)A, Cl(1)–Pd–Cl(2) 92.12(5), Cl(1)–Pd–S(1) 176.33(5), Cl(1)–Pd–S(4) 87.76(5), Cl(2)–Pd–S(1) 91.19(4) Cl(2)–Pd–S(4) 179.24(4) and S(1)–Pd–S(4) 88.96(4)°. The near-planar macrocycle co-ordinates as a bidentate chelating ligand via the exo oriented S-donor atoms leaving the endo oriented O atoms free. The SCH2CH2S moiety adopts a gauche conformation [S(1)–C(2)–C(3)–S(4)–58.3(4)°] with the ethylene bridge occupying part of the macrocyclic cavity. The crystal structure of [Pd([18]aneS2O4)2][PF6]2 showed the PdII occupying a crystallographic inversion centre, with square-planar co-ordination by the [18]aneS2O4 ionophores through the thioether S donors, Pd–S(1) 2.3217(14), Pd–S(4) 2.3102(13)A and S(1)–Pd–S(4) 88.71(5)°. The conformation of the macrocycle is very similar to that found in cis-[PdCl2([18]aneS2O4)], with the O atoms in endo orientations. Reaction of PdCl2 with 2 equivalents of [18]aneS3O3 afforded [Pd([18]aneS3O3)2][PF6]2 which has the PdII occupying a crystallographic inversion centre, with square-planar co-ordination by the [18]aneS3O3 ligands via two of their three thioether S-donor atoms, Pd–S(1) 2.308(2), Pd–S(4) 2.319(2)A, S(1)–Pd–S(4) 88.33(8)°. The structure exhibits some disorder in the polyether/thioether chain which was modelled in terms of two half-occupied orientations. In one component of the disorder the third S-donor atom of each ligand exhibits a long-range apical interaction with the PdII, Pd ⋯ S(16) 3.290(2)A. Reaction of PdCl2 with 1 equivalent of [20]aneS3O3 afforded the monocation [PdCl([20]aneS3O3)]+.

Structural and solution studies of diiodine charge-transfer complexes of thioether crowns

The charge-transfer complexes 2[9]aneS 3 ·4I 2 ([9]aneS 3 = 1,4,7-trithiacyclononane), [12]aneS 4 ·I 2 ([12]aneS 4 = 1,4,7,10-tetrathiacyclododecane), [14]aneS 4 ·I 2 , [14]aneS 4 ·2I 2 ([14]aneS 4 = 1,4,8,11-tetrathiacyclotetradecane), [16]aneS 4 ·I 2 and [16]aneS 4 ·4I 2 ([16]aneS 4 = 1,5,9,13-tetrathiacyclohexadecane) have been prepared by slow evaporation of solutions containing I 2 and the appropriate thioether macrocycle in CH 2 Cl 2 . The structure of 2[9]aneS 3 ·4I 2 shows two independent macrocycles in the asymmetric unit which are linked by a diiodine bridge. Asymmetric units are linked by I · · · I and S · · · I interactions to form an extended array of linked macrocycles. The single-crystal structure of [12]aneS 4 ·I 2 features an infinite chain structure formed by alternating [12]aneS 4 and I 2 molecules. The structure contains both symmetric and asymmetric diiodine bridges. Although the 1∶1 adduct [14]aneS 4 ·I 2 can also be described as a one-dimensional infinite chain structure with asymmetric diiodine bridging, the structure is better visualised as alternating layers of macrocycle and iodine spanned by short contacts of 3.335(4) A. The adduct [14]aneS 4 ·2I 2 shows two independent macrocycles each co-ordinated to two I 2 molecules. The charge-transfer network consists of chains of molecules with alternating orientations. The single-crystal structure of a third 1∶1 adduct [16]aneS 4 ·I 2 contains only symmetrical diiodine bridges between neighbouring macrocycles leading to an infinite chain structure. The compound [16]aneS 4 ·4I 2 is the first example of a tetradentate macrocycle which incorporates I 2 bound to all four S atoms. The single-crystal structure shows four terminal I 2 molecules co-ordinated to the four S donors of the macrocycle. Molecules are linked into interwoven sheets by I · · · I interactions of 3.639(2) A. The formation enthalpies (ΔH) and constants (K) of 1∶1 adducts obtained by treating various thioether macrocycles with I 2 in CH 2 Cl 2 have been determined by electronic spectroscopy. The Fourier-transform Raman spectra for all the charge-transfer adducts have been recorded in CH 2 Cl 2 solutions at different concentrations. The Raman frequencies of the ν(I–I) vibrations show good correlation with the measured formation enthalpies ΔH.

Ruthenium complexes of thioether/oxa ionophores: the synthesis and single-crystal X-ray structures of [RuCl2(PPh3)2([15]aneS2O3)], [RuCl(PPh3)([18]aneS2O4)2]PF6, [RuCl(p-MeC6H4i-Pr)([15]-aneS2O3)]PF6, [RuCl(C6H6)([18]aneS2O4)]X (X = PF6 or BPh4) and [Ru(C5H5)(PPh3)([18]aneS2O4)PF6, ([15]aneS2O3 = 1,4,7-trioxa-10,13-dithiacyclopentadecane; [18]aneS2O4 = 1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane)

SummaryReaction of [RuCl2(PPh3)3] with one molar equivalent of [15]aneS2O3 yields the complex [RuCl2(PPh3)2 ([15]aneS2O3)]. Reaction of two equivalents of [15]-aneS2O3 or [18]aneS2O4 with [RuCl2(PPh3)3] yields the complex cations [RuCl(PPh3) ([15]aneS2O3)2]+ and [RuCl(PPh3)([18]aneS2O4)2]+, respectively. The complex [RuCl2(PPh3)2([15]aneS2O3)]·1/2Et2O shows RuII in an octahedral Cl2S2P2 environment: 600-01(1), 2.4447(15); 600-02(2), 2.4154(15); 600-03(1), 2.4085(15); 600-04(4), 2.4215(16); 600-05(1), 2.3775(6); and 600-06(2), 2.3640(15) Å. The phosphine ligands are mutually cis and in common with the thioether S-donors of the macrocycle occupy equatorial binding sites; the Cl− ligands are in apical positions. The complex [RuCl(PPh3)([18]aneS2O4)] PF6·1/2EtOH shows the RuII in an octahedral ClS4P environment: 600-07, 2.441(6); 600-08, 2.340(5); 600-09(1), 2.387(5); 600-10(4), 2.389(6); 600-11(1′), 2.348(6); and 600-12(4′), 2.438(6) Å. The Cl− and PPh3 ligands adopt a cis configuration in contrast to the reported analogous [15]aneS2O3 complex which shows a trans configuration. 31P-n.m.r. spectroscopic studies show the presence of two geometric isomers in both cases. Reactions of [18]aneS2O4 with [Ru2Cl4(C6H6)2] and [Ru(Cp)Cl(PPh3)2] yields the complexes [RuCl(C6H6)-([18]aneS2O4)]+ and [RuCp(PPh3)([18]aneS2O4)]+, respectively. The complex [RuCl(C6H6)([18]aneS2O4)]-PF6 shows the Cl− ligand and the two thioether S-donors of [18]aneS2O4 coordinated to the [Ru(C6H6)] fragment: 600-13, 2.416(2); 600-14(1), 2.382(5); and 600-15(4), 2.377(5) Å. The single crystal structure of [RuCl(C6H6)-([18]aneS2O4)]BPh4 shows a similar geometry around the RuII ion: 600-16, 2.411(6); 600-17(1), 2.384(6); and 600-18(4), 2.369(6) Å. [Ru(C5H5)(PPh3)([18]ane-S2O4)]PF6 shows the PPh3 ligand and [18]aneS2O4 coordinated to the pseudo-octahedral RuII fragment: 600-19, 2.3126(17); 600-20(1), 2.3793(17); and 600-21(4), 2.3587(19) Å.

Tetra(n-butyl)ammonium trifluoromethanesulfonate

The title structure comprises two ion pairs in each asymmetric unit. There are no close contacts between any of the ions. Although the structure determination was carried out at reduced temperature there are large vibration amplitudes for some F atoms and disorder in one of the n-butyl chains

catena-{[HgCl2([18]aneS2O4)]HgCl2} at 150K: a Redetermination and Reinterpretation

The structure of the title compound {[HgCl2([18]aneS2O4)]HgCl2}n ([18]aneS2O4 = 1,4,7,10-tetraoxa-13,16-dithiacyclooctadecane), [Hg2Cl4(C12H24O4S2)], has been redetermined, and reinterpreted as a one-dimensional polymeric thread comprising linked Hg4Cl4 macrocyclic moieties with pendant macrocyclic ligands. {the compound may be named catena-poly[(chloromercury)-di-μ-chloro-bis[(1,4,7,10-tetraoxa-13,16-di-thiacyclooctadecane-S,S)mercury]-di-μ-chloro-(chloromercury)-di-μ-chloro]}.