Thermal decomposition of (NH4)2MoS4 and (NH4)2WS4heat of formation of (NH4)2MoS4

The reactions (NH₄)₂MeS₄ = 2 NH₃ + H₂S + MeS₃ (Me = Mo, W) were investigated by measuring the decomposition vapour pressures. Thermochemical data were obtained from these measurements: ΔH = 52 kcal/mole and ΔS = 105 cal/deg.mole for the decomposition of the tetrathiomolybdate. Similarly, ΔH = 69 kcal/mole and ΔS = 106 cal/deg.mole were obtained for the decomposition of the tetrathiotungstate. The normal heat of formation of (NH₄)₂MoS₄ was found to be ΔH = ?140 kcal/mole. The kinetics of thermal decomposition of the above reactions were also measured.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

BONDING CHARACTERISTICS OF COMPLEXES[MoS4（CuCN）n]2—（n=1,2）

<正> The electronic structures and bonding properties of the Mo-Cu-S complexes with a general formula [MoS4(CuCN)n]2-(n=1,2)have been investigated by using CNDO/2 method,and the effect of electron transfer on the formation of the Mo-Cu-S complexes has been discussed based on the bonding properties and the energy of the frontier orbitals.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Rearrangement of molybdocene tetraoxotetrasulfide Cp2MoS4O4 to Give [(Cp2MoS2H)2](HSO4)2: a novel proton-stabilized molybdocene disulfide dimer

Cp(2)MoS(4), 1, in CH(2)Cl(2) undergoes extensive oxidation by m-CPBA at -78 degrees C to give a 1,1,4,4-tetroxide, 2 (59%). Tetraoxide 2 rearranges at room temperature to give an unusual sulfur-atom protonated molybdocene disulfide dimer [(Cp(2)MoS(2)H)(2)](HSO(4))(2), 3. Crystal data for 3 are P, a = 6.751(2) Angstroms, b = 9.865(4) Angstroms, c = 11.549(5) Angstroms, alpha = 109.95(3) degrees, beta = 96.11(3) degrees, gamma = 108.22(3) degrees, V = 666.9(4) Angstroms(3), and Z = 1. The dimer was also obtained directly when the oxidation was conducted at 0 degree C in DMF. Under basic conditions, the dimer is cleaved to give molybdocene disulfide Cp(2)MoS(2), while treatment of the latter with acid converts it to the dimer 3.     

Herstellung und Eigenschaften der Verbindungen Sr2(MnO4)OH und Sr2(MnO4)OH·2H2O

Zusammenfassung Es wird die Herstellung der Verbindungen Sr₂(MnO₄)OH und Sr₂(MnO₄)OH·2H₂O beschrieben. Die Gitterkonstanten wurden aus den entsprechenden Pulverdiagrammen berechnet. Die Infrarotabsorptions-und die Reflexionsspektren im Sichtbaren sowie das magnetische und thermische Verhalten wurden untersucht und kurz besprochen.

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Preparation and properties of the compounds Sr₂(MnO₄)OH and Sr₂(MnO₄)OH·2H₂O

Methods for preparation of the anhydrous compound formulated as Sr₂(MnO₄)OH and of its dihydrate are described. Unit cell parameters, which are the same for both substances, have been calculated from X-ray powder diagramms. Infrared absorption and visible reflectance spectra as well as the magnetic and thermal properties are also reported and briefly discussed.

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Mit 4 Abbildung     

Synthese und Strukturbestimmung von (i-Pr)2NB(t-BuP)3 und (i-Pr)2NB(t-BuP)4

Synthesis and Structure Analysis of (i-Pr)₂NB(t-BuP)₃ and (i-Pr)₂NB(t-BuP)₄ The diphosphide K(t-Bu)P-(t-BuP)₂-P(t-Bu)K obtained by the cleavage reaction of the 3-membered ring system (i-Pr)₂BN(t-BuP)₂ with potassium reacts with t-BuPCl₂ at ?78°C under ring expansion to form the P₃B ring system (i-Pr)₂NB(t-BuP)₃ – 1,2,3-tri-t-butyl-tri-phospha-4-diisopropyl-aminoboretane ( 1 ). – The 5-membered P₄B ring system (i-Pr)₂NB(t-BuP)₄ – 1,2,3,4-tetra-t-butyl-tetraphospha-5-diisopropylaminoborolidine, ( 2 ) – is formed from K(t-Bu)P? (t-BuP)₂? P(t-Bu)K and (i-Pr)₂NBCl₂ analogous to the above reaction. 1 and 2 could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analysis. 1 shows at 200 K two conformation isomers; for 2 ³¹P-^10,11B-isotopic shifts could be identified.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Darstellung und Kristallstruktur von Ba(en)4(SbSe2)2

Preparation and Crystal Structure of Ba(en)₄(SbSe₂)₂ The new compound Ba(en)₄(SbSe₂)₂ can be synthesized by dissolving of Ba₄Sb₄Se₁₁ in ethylenediamine. It crystallizes in the monoclinic system, space group P2₁/c, with lattice constants see “Inhaltsübersicht”. Characteristic elements of the structure are [SbSe₂^?]_n chains, which are formed by distorted trigonal SbSe₃ pyramids connected by common corners.     

Synthese der Silatetraphospholane (tBuP)4SiMe2, (tBuP)4SiCl2 und (tBuP)4Si(Cl)SiCl3 Molekül- und Kristallstruktur von (tBuP)4SiCl2

Synthesis of the Silatetraphospholanes (tBuP)₄SiMe₂, (tBuP)₄SiCl₂, and (tBuP)₄Si(Cl)SiCl₃ Molecular and Crystal Structure of (tBuP)₄SiCl₂ The reaction of the diphosphide K₂[(tBuP)₄] 7 with the halogenosilanes Me₂SiCl₂, SiCl₄ or Si₂Cl₆ in a molar ratio of 1:1 leads via a [4 + 1]-cyclocondensation reaction to the silatetraphospholanes (tBuP)₄SiMe₂ 1,1-dimethyl-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 1 , (tBuP)₄SiCl₂, 1,1-dichloro-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 2 , and (tBuP)₄Si(Cl)SiCl₃, 1-chloro-1-trichlorsilyl-1-sila-2,3,4,5-tetra-t-butyl-2,3,4,5-tetraphospholane, 3 , respectively, with the 5-membered P₄Si ring system. The reaction leading to 1 is accompanied with the formation of the by-product Me₂(Cl)-Si–(tBuP)₄–Si(Cl)Me₂ 1a (5:1), which has a chain structure. On warming to 100°C 1a decomposes to 1 and Me₂SiCl₂. The compounds 2 and 3 do not react further with an excess of 7 due to strong steric shielding of the ring Si atoms by the t-butyl groups. 1, 2 and 3 could be obtained in a pure form and characterized NMR spectroscopically; 2 was also characterized by a single crystal structure analysis. 1a was identified by NMR spectroscopy only.     

Synthese und Kristallstrukturen von (PPh4)2[As2Se4Cl12] und (PPh4)2[As2Se4Br12]

Synthesis and Crystal Structures of (PPh₄)₂[As₂Se₄Cl₁₂] and (PPh₄)₂[As₂Se₄Br₁₂] The reaction of PPh₄Cl and As₂Se₃ with SOCl₂ or with chlorine in dichloromethane affords (PPh₄)₂[As₂Se₄Cl₁₂] with good yields. From PPh₄Br, As₂Se₃ and bromine the corresponding bromo compound was obtained. According to the X-ray crystal structure determinations both compounds are isotypic, crystallizing in the space group of P1 . In the anions two Se₂X₂ molecules are linked with two X^? ions forming an Se₄X₂ ring in chair conformation. Each X^?-ion is associated with an additional AsX₃ molecule (X = Cl, Br).     

Insertion of SO(2) into the S-S bond of Cp(2)MoS(2) and Cp(2)MoS(2)O to give molybdocene dithiosulfate and bis(O-alkylthiosulfates)

Cp(2)MoS(2), 3, reacts with SO(2) in CH(2)Cl(2)/EtOH mixtures to give Cp(2)MoS(3)O(2), 4, wherein the SO(2) has inserted into the S-S bond to give a dithiosulfate ligand. Crystal data for 4: P2(1)/n, a = 7.6782(6) A, b = 14.580(3) A, c = 10.2730(10) A, beta = 92.04(1) degrees, V = 1149(3) A(3), Z = 4. Cp(2)MoS(2)O, 5, reacts with SO(2) in CH(2)Cl(2) to give low yields of 4 plus other identified products. 5 reacts with SO(2) in MeOH and EtOH to give the corresponding bis(O-alkylthiosulfate), 6a and 6b, respectively. Crystal data for 6a: P 1 macro, a = 8.3226(13) A, b = 8.4736(11) A, c = 12.382(2) A, alpha = 87.803(11) degrees, beta = 77.758(11) degrees, gamma = 86.383(12) degrees, V = 851.4(2) A(3), Z = 2.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Darstellung,Ramanspektren und Kristallstrukturen von V2O3(SO4)2, K[VO(SO4)2] und NH4[VO(SO4)2]

Preparation, Raman Spectra, and Crystal Structures of V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] The oxo-sulfato-vanadates(V) V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V₂O₃(SO₄)₂ consists of a threedimensional network of pairs of cornershared VO₆ octahedra with one terminal oxygen atom each, and SO₄ tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH₄[VO(SO₄)₂] and K[VO(SO₄)₂] are isostructural. VO₆ octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO₃ molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO₄)₂] ? K[VO₂(SO₄)] + SO₃ at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V₂O₃(SO₄)₂, monoclinic, space group P2₁/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(R_w) = 0.039(0,033); K[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(R_w) = 0,11(0,10); NH₄[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(R_w) = 0.088(0.083).     

Darstellung,Kristallstrukturen und Eigenschaften der Chrom(II)-phosphat-halogenide Cr2(PO4)Br und Cr2(PO4)I

Synthesis, Crystal Structures, and Properties of the Chromium(II) Phosphate Halides Cr₂(PO₄)Br and Cr₂(PO₄)I The new compounds Cr₂(PO₄)Br and Cr₂(PO₄)I have been obtained by reaction of CrPO₄, Cr and Br₂ or I₂ in evacuated silica tubes at elevated temperatures (Cr₂(PO₄)Br: 900 °C, Cr₂(PO₄)I: 700 °C). Single crystals of deep blue Cr₂(PO₄)Br and turquoise Cr₂(PO₄)I with edge-lengths up to 2 mm and 0.3 mm, respectively, have been grown in experiments involving the gaseous phase. Single crystal data have been used for structure determination and refinement. Though being not isotypic, the two crystal structures are closely related. Two crystallographically independent Cr²⁺, in polyhedra [Cr1O₃X₃] and [Cr2O₅X], form dimers [Cr1₂O₂O_2/2X₄] and [Cr2₂O₈X₂]. Distances are 1.978 Å ≤ d(Cr–O) ≤ 2.096 Å (for the iodide: 1.959 Å ≤ d(Cr–O) ≤ 2.105 Å), 2.587 Å ≤ d(Cr–Br) ≤ 3.158 Å and 2.867 Å ≤ d(Cr–I) ≤ 3.327 Å. The structures of bromide and iodide can be distinguished by the different way of connection of the Cr1 containing dimers. The phosphate group shows slightly distorted tetrahedral geometry with 1.491 Å ≤ d(P–O) ≤ 1.559 Å (1.486 Å ≤ d(P–O) ≤ 1.567 Å) and angles of 106.48° ≤ ∠(O–P–O) ≤ 111.69° (106.57° ≤ ∠(O–P–O) ≤ 111.72°. IR-spectra of Cr₂(PO₄)Br and Cr₂(PO₄)I, the Raman-spectrum of Cr₂(PO₄)Br and electronic spectra of the two compounds in the UV/vis region at low temperature are reported and discussed.     

Synthese und Kristallstrukturen von (PPh4)2[In(S4)(S6)Cl] und (PPh4)2[In(S4)Cl3]

Synthesis and Crystal Structures of (PPh₄)₂[In(S₄)(S₆)Cl] and (PPh₄)₂[In(S₄)Cl₃] InCl and PPh₄Cl yield (PPh₄)₂[In₂Cl₆] in acetonitrile. This reacts with Na₂S₄ in presence of PPh₄Cl, forming (PPh₄)₂[In(S₄)(S₆)Cl]. Its crystal structure was determined by X-ray diffraction (R = 0.075, 2 282 observed reflexions). It is isotypic with (PPh₄)₂[In(S₄)(S₆)Br] and contains anions with trigonal-bipyramidal coordination of In, Cl occupying an axial position, and the S₄ and S₆ groups being bonded in a chelate manner. The reaction of (PPh₄)₂[In₂Cl₆] and sulfur in acetonitrile yielded (PPh₄)₂[InCl₅] and (PPh₄)₂[In(S₄)Cl₃]. The crystal structure analysis of the latter (R = 0.072, 4 080 reflexions) revealed an anion with distorted trigonal-bipyramidal coordination of In, the S₄ group occupying one axial and one equatorial position; the S₄ group shows positional disorder.     

Synthese und Kristallstruktur von Hydrogensulfaten einwertiger Metalle – Ag(H3O)(HSO4)2, Ag2(HSO4)2(H2SO4), AgHSO4 und Hg2(HSO4)2

Synthesis and Crystal Structure of Metal(I) Hydrogen Sulfates – Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂(H₂SO₄), AgHSO₄, and Hg₂(HSO₄)₂ Hydrogen sulfates Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂ · (H₂SO₄), and AgHSO₄ have been synthesized from Ag₂SO₄ and sulfuric acid. Hg₂(HSO₄)₂ was obtained from metallic mercury and 96% sulfuric acid as starting materials. The compounds were characterized by X‐ray single crystal structure determination. Ag(H₃O)(HSO₄)₂ belongs to the structure type of Na(H₃O)(HSO₄). The silver atom is coordinated by 6 + 2 oxygen atoms. In the structure, there are dimers and chains of hydrogen bonded HSO₄^– tetrahedra. Dimers and chains are connected by the H₃O⁺ ion to form a three dimensional hydrogen network. Ag₂(HSO₄)₂(H₂SO₄) crystallizes isotypic to Na₂(HSO₄)₂(H₂SO₄). The coordination number of silver is 6 + 1. The structure of Ag₂(HSO₄)₂(H₂SO₄) is characterized by hydrogen bonded trimers of HSO₄^– tetrahedra, which are further connected to chains. For the recently published structure of AgHSO₄ the hydrogen bonding system was discussed. There are tetrameres and chains, connected by bifurcated hydrogen bonds. The structure of Hg₂(HSO₄)₂ contains Hg₂²⁺ cations with Hg–Hg distance of 2.509 Å. Every mercury atom is coordinated by one oxygen atom at shorter distance (2.18 Å) and three ones at longer distances (2.57 to 3.08 Å). The HSO₄^– tetrahedra form zigzag chains by hydrogen bonds.     

Acetic acid induced self-assembly of supramolecular compounds [Et4N]3[(WS4Cu2)2(mu-CN)3].2MeCN and [PPh4][WS4Cu3(mu-CN)2].MeCN from preformed clusters [A]2[WS4(CuCN)2] (A = Et4N, PPh4)

Reactions of two preformed trinuclear W/Cu/S clusters, [A](2)[WS(4)(CuCN)(2)] (1: A = Et(4)N; 2: A = PPh(4)), with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et(4)N](3)[(WS(4)Cu(2))(2)(mu-CN)(3)].2MeCN (3), and [PPh(4)][WS(4)Cu(3)(mu-CN)(2)].MeCN (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)(4)]PF(6) in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS(4)Cu(2) cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS(4)Cu(3) core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].