Kristallstrukturen der Fluorochloroplatinate(IV) cis-[(C5H5N)2CH2][PtF4Cl2], trans-[(C5H5N)2CH2][PtF4Cl2] · H2O und [(C5H5N)2CH2][PtF5Cl]

Crystal Structures of the Fluorochloroplatinates(IV) cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂], trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O, and [(C₅H₅N)₂CH₂][PtF₅Cl] The complex ions cis-[PtF₄Cl₂]^2?, trans-[PtF₄Cl₂]^2? and [PtF₅Cl]^2? have been synthesized by stereoselective ligand exchange reactions utilizing the trans effect and are separated by ion exchange chromatography on diethylaminoethyl cellulose. These anions form stable AB-type salts with the doubly charged cation dipyridiniomethane, [(C₅H₅N)₂CH₂]²⁺. X-ray structure determinations on single crystals of cis-[(C₅H₅N)₂CH₂][PtF₄Cl₂] ( 1 ) (monoclinic, space group P2₁/n with a = 10.379(10), b = 9.635(2), c = 13.738(2) Å, β = 99.142(10)°, Z = 4), trans-[(C₅H₅N)₂CH₂][PtF₄Cl₂] · H₂O ( 2 ) (triclinic, space group P1 with a = 7.757(4), b = 10.059(7), c = 10.408(6) Å, α = 82.49(5), β = 68.92(4), γ = 75.46(4)°, Z = 2) and [(C₅H₅N)₂CH₂][PtF₅Cl] ( 3 ) (orthorhombic, space group Pnma with a = 10.394(3), b = 13.320(2), c = 9.2694(10) Å, Z = 4), reveal the perfect ordering of the anion sublattice. The stronger trans influence of Cl compared with F is observed in asymmetric axes $ {\rm F}^ \bullet $? Pt? Cl′. The bond lengths Pt? $ {\rm F}^ \bullet $ are 0.026 Å (1.4%) longer and the Pt? Cl′ distances are 0.078 Å (3,3%) shorter in comparison with those of symmetrically coordinated axes. The weakening of the Pt? $ {\rm F}^ \bullet $ bond and the strengthening of the Pt? Cl′ bond is better recognizable from shifts of the stretching vibrations by 8% to lower and by 13% to higher frequencies, respectively. Correspondingly, the valence force constants are found to be 15% lower and 22% higher. The trans influence is observed most distinctly in the ¹⁹F-nmr spectra exhibiting the coupling constant ¹J($ {\rm F}^ \bullet $Pt) to be 29% smaller than ¹J(FPt).     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalysen der stereoisomeren Trifluorotrichloroplatinate(IV), fac-[(C5H5N)2CH2][PtF3Cl3] · 0,5(CH3)2CO und mer-[(C5H5N)2CH2][PtF3Cl3]

Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Stereoisomeric Trifluorotrichloroplatinates(IV), fac-[(C₅H₅N)₂CH₂][PtF₃Cl₃] · 0.5(CH₃)₂CO and mer-[(C₅H₅N)₂CH₂][PtF₃Cl₃] The geometric isomers fac- und mer-[PtF₃Cl₃]^2? have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The doubly charged complex anions form stable AB-type salts with the dication dipyridiniomethane, [(C₅H₅N)₂CH₂]²⁺. The X-ray structure determination on single crystals of fac-[(C₅H₅N)₂CH₂][PtF₃Cl₃] · 0,5(CH₃)₂CO ( 1 ) (triclinic, space group P1 with a = 8.468(3), b = 8.847(2), c = 12.1260(10) Å, α = 79.986(12), β = 79.009(12), γ = 69.20(3)°, Z = 2) and mer-[(C₅H₅N)₂CH₂][PtF₃Cl₃] ( 2 ) (monoclinic, space group P2₁/n with a = 9.620(2), b = 14.031(4), c = 10.435(3) Å, β = 97.54(2)°, Z = 4) reveals the perfect ordering of the anion sublattice. Due to the stronger trans influence of Cl compared to F in asymmetric axes $ {\rm F}^. $? Pt? Cl′ the Pt? $ {\rm F}^. $ distance is lengthened by 1.8%, the Pt? Cl′ distance is shortened by 1.2% in comparison with symmetrically coordinated axes. Correspondingly, the vibrational spectra exhibit shifts of the Pt$ {\rm F}^. $ streching vibrations by 8% to lower, and of the PtCl′ streching vibrations by 12% to higher frequencies. Normal coordinate analyses performed on the basis of the X-ray data result in valence force constants for weakened Pt? $ {\rm F}^. $ bonds to be 14% lower, for the strengthened Pt? Cl′ bonds to be 20% higher than in symmetric axes, respectively. Generally the trans influence in fluorochloroplatinates(IV) on the bond lengths is very low with 1–2%, it results in considerable shifts of the stretching vibrations by 8–12% and reveals the strongest effect on the valence force constants with 14–20%.     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.     

Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von [(C5H5N)2CH2][1-(O2N)B10H9]

Preparation, ¹¹B NMR, Vibrational Spectra, and Crystal Structure of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] By reaction of [B₁₀H₁₀]^2? in aqueous acetonitrile with a saturated solution of NO₂ in dichloromethane [1-(O₂N) · B₁₀H₉]^2? and [B₁₀H₉(NO)B₁₀H₉]^3? are formed which can be separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound. The X-ray structure determination of [(C₅H₅N)₂CH₂][1-(O₂N)B₁₀H₉] (triclinic, space group P1 , a = 7.1530(9), b = 8.3753(8), c = 15.198(2) Å, α = 96.00(1), β = 95.48(1), γ = 95.60(1)°, Z = 2) reveals the coordination of the NO₂ group via N with a B1? N distance of 1.535(5) Å and an O2? N? O1 angle of 119.3(3)°. The ¹¹B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of an apical monosubstituted B₁₀ cluster with a strong downfield shift of the ipso-B atom at +13.4 ppm. The IR and Raman spectra show strong NO stretching vibrations at 1381 und 1420 cm^?1.     

Synthese und Charakterisierung von Aquapentachloroplatinaten(IV) – Struktur von [K(18-Krone-6)][PtCl5(H2O)]

Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl₅(H₂O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H₁₃O₆][PtCl₅(H₄O₂)] · 2(18-cr-6) ( 2 ) reacts with K₂CO₃ and [NⁿBu₄]OH in aqueous solution to give [K(18-cr-6)][PtCl₅(H₂O)] ( 5 a ) and [NⁿBu₄][PtCl₅(H₂O)] · ¹/₂ (18-cr-6) · H₂O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (¹H, ¹³C, ¹⁹⁵Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl₅(H₂O)]^? and [K(18-cr-6)]⁺ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and O_W? H? O_cr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl₅O] has approximately C_4v symmetry.     

Synthese und Struktur der Nitrido‐Komplexe [(n‐Bu)4N]2[{(L)Cl4Re≡N}2PtCl2] (L = THF und H2O) und [(n‐Bu)4N]2[(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]2

Synthesis and Crystal Structure of the Nitrido Complexes [(n‐Bu)₄N]₂[{(L)Cl₄Re≡N}₂PtCl₂] (L = THF und H₂O) and [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}_2—PtCl₂] ( 1a ) is obtained by the reaction of [(n‐Bu)₄N][ReNCl₄] with [PtCl₂(C₆H₅CN)₂] in THF/CH₂Cl₂. It forms red crystals with the composition 1a · 2 CH₂Cl₂ crystallizing in the tetragonal space group I4₁/a with a = 3186.7(2); c = 1311.2(1) pm and Z = 8. If the reaction of the educts is carried out without THF, however under exposure to air the compound [(n‐Bu)₄N]₂[{(H₂O)Cl₄Re≡N}₂PtCl₂] ( 1b ) is obtained as red trigonal crystals with the space group R3 and a = 3628.3(3), c = 1231.4(1) pm and Z = 9. In the centrosymmetric complex anions [{(L)Cl₄Re≡N}₂PtCl₂]^2— a linear PtCl₂moiety is connected in a trans arrangement with two complex fragments [(L)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡dqN‐Pt. For Pt^II such results a square‐planar coordination PtCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 169.5 pm and Pt‐N = 188.8 pm ( 1a ), respectively, Re‐N = 165.6 pm and Pt‐N = 194.1 pm ( 1b ). By the reaction of [(n‐Bu)₄N][ReNCl₄] with PtCl₄ in CH₂Cl₂ platinum is reduced forming the heterometallic Re^VI/Pt^II complex, [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 2012.9(1); b = 1109.0(2); c = 2687.4(4) pm; β = 111.65(1)° and Z = 4. In the central unit ClPt(μ‐Cl)₂PtCl of the anionic complex [(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂^2— with the symmetry C₂ the coordination of the Pt atoms is completed by two nitrido bridges Re≡N‐Pt to nitrido complex fragments [(H₂O)Cl₄Re≡N] ^— forming a square‐planar arrangement for the Pt atoms. The distances in the linear nitrido bridges are Re‐N = 165.9 pm and Pt‐N = 190.1 pm.     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

Darstellung, 11B-, 13C-, 1H-NMR- und Schwingungsspektren von Monoethoxyhydro-closo-Dodecaborat(2–) sowie Kristallstruktur von [(C5H5N)2CH2][B12H11(OC2H5)]

Preparation, ¹¹B, ¹³C, ¹H NMR and Vibrational Spectra of Monoethoxyhydro-closo-dodecaborate(2–), and the Crystal Structure of [(C₅H₅N)₂CH₂][B₁₂H₁₁(OC₂H₅)] By treatment of Na₂[B₁₂H₁₂] with dry HF in ethanol Na₂[B₁₂H₁₁(OC₂H₅)] is formed which has been separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and by-products. The X-ray structure determination of [(C₅H₅N)₂CH₂][B₁₂H₁₁(OC₂H₅)] (monoclinic, space group P2₁/m, a = 9.1906(3), b = 12.6612(8), c = 9.3640(12) Å, β = 112.947(6)°, Z = 2) reveals the complete ordering of the anion sublattice. The ¹¹B nmr spectrum exhibits the characteristic feature (1:5:5:1) of a mono substituted B₁₂ cage with a strong down-field shift of ipso-B at +6.5 ppm. In the ¹³C nmr spectrum a triplet at 67.9 ppm of the methylene group and a quartet at 19.5 ppm of the methyl group is observed. Correspondingly, the ¹H nmr spectrum shows two multiplets at 3.7 and 1.3 as expected for an ethoxy substituent, and a multiplet at 2.1 ppm due to the protons of the boron cluster. The i.r. and Raman spectra exhibit strong CH stretching vibrations between 2 963 and 2 863 cm^?1, and in the i.r. spectrum the CO and BO stretching frequencies of the B? O? C bridge are observed at 1 175 and 1 140 cm^?1.     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][PrCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][PrCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][PrCl₄(H₂O)₂] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl₆(H₂O)₂]^3– according to [PrCl_4/2Cl₂(H₂O)₂]^–, which are held together by dimethylammonium cations ([(CH₃)₂NH₂]⁺). In order to study the interactions between the praseodymium cation (Pr³⁺) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Zur solvensfreien Darstellung von Tetramethylammoniumsalzen: Synthese und Charakterisierung von [N(CH3)4]2[C2O4], [N(CH3)4][CO3(CH3)], [N(CH3)4][NO2], [N(CH3)4][CO2H] und [N(CH3)4][O2C(CH2)2CO2(CH3)]

Solvent-free Synthesis of Tetramethylammonium Salts: Synthesis and Characterization of [N(CH₃)₄]₂[C₂O₄], [N(CH₃)₄][CO₃CH₃], [N(CH₃)₄][NO₂], [N(CH₃)₄][CO₂H], and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] A general procedure to synthesize tetramethylammonium salts is presented. Several tetramethylammonium salts were prepared in a crystalline state by solvent-free reaction of trimethylamine and different methyl compounds at mild conditions: [N(CH₃)₄]₂[C₂O₄] (cubic; a = 1 114.8(3) pm), [N(CH₃)₄][CO₃CH₃] (P2₁/n; a = 813.64(3), b = 953.36(3), c = 1 131.3(4) pm, β = 90.03(1)°), [N(CH₃)₄][NO₂] (Pmmn; a = 821.2(4), b = 746.5(3), c = 551.5(2) pm), [N(CH₃)₄][CO₂H] (Pmmn; a = 792.8(7), b = 791.7(3), c = 563.3(4) pm) and [N(CH₃)₄][O₂C(CH₂)₂CO₂CH₃] (P2₁; a = 731.1(2), b = 826.4(3), c = 1 025.2(3) pm, β = 110.1(1)°). The tetramethylammonium salts were characterized by IR-spectroscopy and X-ray diffraction. The crystal structures of the methylcarbonate and the nitrite are described.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalysen der Chloro-Iodo-Rhenate(IV) (CH2Py2)[ReCl5I], cis-(CH2Py2)[ReCl4I2] · 2 DMSO,trans-(CH2Py2)[ReCl4I2] · 2 DMSO und fac-(EtPh3P)2[ReCl3I3]

Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Chloro-Iodo-Rhenates(IV) (CH₂Py₂)[ReCl₅I], cis -(CH₂Py₂)[ReCl₄I₂] · 2 DMSO, trans -(CH₂Py₂)[ReCl₄I₂] · 2 DMSO, and fac -(EtPh₃P)₂[ReCl₃I₃] [ReCl₅I]^2–, cis-[ReCl₄I₂]^2–, trans-[ReCl₄I₂]^2–, and fac-[ReCl₃I₃]^2– have been synthesized by ligand exchange reactions of [ReI₆]^2– with HCl and are separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations have been performed on single crystals of (CH₂Py₂)[ReCl₅I] ( 1 ) (triclinic, space group P1 with a = 7.685(2), b = 9.253(2), c = 12.090(4) Å, α = 90.06(2), β = 101.11(2), γ = 95.07(2)°, Z = 2), cis-(CH₂Py₂)[ReCl₄I₂] · 2 DMSO ( 2 ) (triclinic, space group P1 with a = 8.662(2), b = 12.109(2), c = 12.9510(12) Å, a = 97.533(11), β = 96.82(2), γ = 89.90(2)°, Z = 2) , trans-(CH₂Py₂)[ReCl₄I₂] · 2 DMSO ( 3 ) (triclinic, space group P1 with a = 9.315(7), b = 9.663(3), c = 15.232(3) Å, α = 80.09(2), β = 81.79(4), γ = 83.99(5)°, Z = 2) and fac-(EtPh₃P)₂[ReCl₃I₃] ( 4 ) (monoclinic, space group P2₁/a with a = 17.453(2), b = 13.366(1), c = 19.420(1) Å, β = 112.132(8)°, Z = 4). The crystal structure of ( 1 ) reveals a positional disorder of the anion sublattice along the asymmetric axis. Due to the stronger trans influence of I compared with Cl on asymmetric axes Cl˙–Re–I′ is caused a mean lenghthening of the Re–Cl˙ distances of 0.020 Å (0.8%) and a shortening of the Re–I′ distances of 0.035 Å (1.3%) with regard to symmetrically coordinated axes Cl–Re–Cl and I–Re–I, respectively. Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four chloro-iodo-rhenates(IV) are assigned by normal coordinate analyses. The weakening of the Re–Cl˙ bonds and the strengthening of the Re–I′ bonds is indicated by a decrease or increase of the valence force constants each by 9%.     

Synthese,Kristallstruktur und Magnetismus von [(CH3)2NH2][NdCl4(H2O)2]

Preparation, Crystal Structure, and Magnetism of [(CH₃)₂NH₂][NdCl₄(H₂O)₂] The complex water containing chloride [(CH₃)₂NH₂][NdCl₄(H₂O)₂] was prepared for the first time and the crystal structure was determined by X‐ray methods from single crystals. The compound crystallizes in the orthorhombic space group Cmca (Z = 8) with a = 1793.5(2) pm, b = 936.6(2) pm and c = 1232.8(2) pm. The anionic part of the structure is built up by chains of edge connected [NdCl_4/2Cl₂(H₂O)₂]^– trigondodecahedra. In order to study the interactions between the neodymium cation and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.     

New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C3H10N)][Sb8S13], [(C2H8NO)(C2H8N)(CH5N)][Sb8S13], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]

Four new thioantimonates(III) with compositions [(C₃H₁₀NO)(C₃H₁₀N)][Sb₈S₁₃] ( 1 ) (C₃H₉NO = 1‐amino‐3‐propanol, C₃H₉N = propylamine), [(C₂H₈NO)(C₂H₈N)(CH₅N)][Sb₈S₁₃] ( 2 ) (C₂H₇NO = ethanolamine, C₂H₇N = ethylamine, CH₅N = methylamine), [(C₆H₁₆N₂)(C₆H₁₄N₂)][Sb₆S₁₀] ( 3 ) (C₆H₁₄N₂ = 1,2‐diaminocyclohexane) and [C₈H₂₂N₂][Sb₄S₇] ( 4 ) (C₈H₂₀N₂ = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P2₁/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P2₁/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb₈S₁₃]^2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb₈S₁₃]^2– chain anion with Sb₁₂S₁₂ pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb₆S₁₀]^2– in compound 3 is unique and is constructed by corner‐sharing SbS₃ pyramids. Two symmetry‐related single chains consisting of alternating SbS₃ units and Sb₃S₃ rings are bound to Sb₄S₄ rings in chair conformation. Finally, in the structure of 4 the SbS₃ and SbS₄ moieties are joined corner‐linked to form a chain of alternating SbS₄ units and (SbS₃)₃ blocks. Neighboring chains are connected into sheets that contain relatively large Sb₁₀S₁₀ heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.