Michael Berkei

Darstellung, spektroskopische Charakterisierung und Kristallstrukturen von Quecksilber(II)-bis(tetracyanoborat) Hg[B(CN)4]2 und Diquecksilber(I)-bis(tetracyanoborat) Hg2[B(CN)4]2†

Die Reaktion von Hg(NO3)2 mit K[B(CN)4] fuhrt zu Hg[B(CN)4]2 (1). Eine Komproportionierungsreaktion von 1 mit elementaren Quecksilber liefert das entsprechende Quecksilber(I)-Salz Hg2[B(CN)4]2 (2). Die Charakterisierung von 1 und 2 erfolgt anhand von Schwingungsspektren, 13C- und 11B-NMR-Spektren sowie der Auswertung von Kristallstrukturanalysen. Hg[B(CN)4]2 kristallisiert trigonal in der Raumgruppe P3¯m1 mit a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)A3 und einer Formeleinheit in der Elementarzelle. Fur Hg2[B(CN)4]2 wird eine orthorhombische Elementarzelle der Raumgruppe Pbcm mit a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)A3 und Z = 4 gefunden. n n n nPreparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)-bis(tetracyanoborate) Hg[B(CN)4]2 and Dimercury(I)-bis(tetracyanoborate) Hg2[B(CN)4]2 n n n nHg[B(CN)4]2 (1) is synthesised by the reaction between Hg(NO3)2 and K[B(CN)4]2. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg2[B(CN)4]2 (2) is obtained. The compounds were characterised by vibrational- and NMR-spectroscopy, and their crystal structures were determined. Hg[B(CN)4]2 crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)A3, and one formula unit per unit cell. For Hg2[B(CN)4]2 an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)A, and Z = 4 is observed.

Polymeric anionic networks using dibromine as a crosslinker; the preparation and crystal structure of [(C4H9)4N]2[Pt2Br10]·(Br2)7 and [(C4H9)4N]2[PtBr4Cl2]·(Br2)6

The reaction of M[PtX3(CO)] (M+ = [(C4H9)4N]+, X = Br, Cl) with an excess of Br2 gives the new platinum(IV) salts, [(C4H9)4N]2[Pt2Br10].(Br2)7, 1, and [(C4H9)4N]2[PtBr4Cl2].(Br2)6, 2, which, in the solid state, contain strong Br Br interactions resulting in the formation of polymeric networks; they could provide useful solid storage reservoirs for elemental bromine.

Spektroskopische Charakterisierung und Kristallstruktur von Trifluormethyliod(III)-bis(trifluoracetat) CF3I(OCOCF3)2 / Spectroscopic Characterisation and Crystal Structure of Trifluoromethyliodine(III) Bis-trifluoroacetate, CF3I(OCOCF3)2

Abstract Trifluoromethyliodine(III) bis-trifluoracetate [CF3I(OCOCF3)2] was obtained by reaction between CF3IF2 and (CH3)3SiOCOCF3 at -50 °C. It crystallises in the triclinic space group P1̄ with a = 520.8(1), b = 1042.9(1), c = 1087.5(1) pm, α = 65.22(0)°, β = 81.18(0)°, γ = 80.09(0)°, and two formula units per unit cell. The compound has also been characterised by its Raman and IR spectra.

Crystal Structure of LiOiPr · 5iPrOH — a Hydrogen-Bonded Chain Structure

The title compound was obtained as thin needles from a complex reaction mixture at low temperature. According to the single crystal X-ray structure analysis it crystallizes in the triclinic space group P1¯ and consists of solvent separated cations and anions. As a result of hydrogen-bonding a one-dimensional polymer is formed with short O···O distances in the range 2.458(4)—2.709(3)A. n n n nDie Kristallstruktur von LiOiPr · 5iPrOH — eine wasserstoffverbruckte Kettenstruktur n n n nLiOiPr · 5iPrOH wurde als dunne Nadeln aus einer komplexen Reaktionsmischung bei tiefen Temperaturen erhalten. Nach der Kristallstrukturanalyse kristallisiert es in der triklinen Raumgruppe P1¯, und es besteht aus solvensisolierten Kationen und Anionen. Als Ergebnis von Wasserstoffbrucken-Bindungen wird ein eindimensionales Polymer mit kurzen O···O-Abstanden im Bereich von 2, 458(4)-2, 709(3)A gebildet.

Kristallstruktur von Tetraphenylphosphonium Dichloroiodat(I) [PPh4][ICl2] / Crystal Structure of Tetraphenylphosphonium Dichloroiodate(I) [PPh4][ICl2]

Abstract Dichloroiodate Tetraphenylphosphonium dichloroiodate(I) [PPh4] [ICl2] crystallises in the monoclinic system in the space group P2/n with a = 1025.7(1), b = 770.2(1), c = 1446.4(1) pm, ß = 90.11(1)° and two formula units per unit cell. The ICl2- anion is symmetrical (C2v) and almost linear with I-Cl bond lengths of 257.1(2) pm and a bond angle of 178.10(6)°.

Crystal Structure of Tetrabutylammonium Carbonyltribromoplatinate(II) [(C4H9)4N][PtBr3(CO)]

Abstract Tetrabutylammonium carbonyltribromoplatinate(II) [(C4H9)4N][PtBr3(CO)] crystallises in the monoclinic system in the space group P21/n with a = 1487.84(13), b = 897.41(8), c = 1849.6(2) pm, β = 106.558(2)° and four formula units per unit cell. The [PtBr3 (CO)]- anion is symmetrical (C2v) and almost planar with Pt-Br bond lengths of 242.40(12) pm (trans to CO), 243.25(10) pm and 242.99(9) pm (trans to Br), and a Pt-C bond length of 185.6(11) pm.