Iodoplumbate mit vier‐ und fünffach koordinierten Pb2+‐Ionen

Iodoplumbates with Tetra‐ and Penta‐coordinated Pb²⁺ Ions In contrast to all known iodoplumbates with octahedrally coordinated Pb²⁺ ions, square pyramidal geometry is observed in the iodoplumbate chains of (Pr₄N)[PbI₃] ( 1 ) and [Mg(dmf)₆][PbI₃]₂ ( 2 ), whereas the isolated anions in (Ph₄P)₂[Pb₂I₆] ( 3 ) and [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ) contain tetra‐coordinated lead atoms. (Pr₄N)[PbI₃] ( 1 ): a = 910.86(6), b = 1221.46(7), c = 1907.7(1) pm, V = 2122.5(2) · 10⁶ pm³, space group P2₁2₁2₁; [Mg(dmf)₆][PbI₃]₂ ( 2 ): a = 891.24(9), b = 1025.34(7), c = 1234.82(9) pm, α = 92.938(8), β = 106.457(8), γ = 98.100(7)°, V = 1066.4(2) · 10⁶ pm³, space group P1; (Ph₄P)₂[Pb₂I₆] ( 3 ): a = 1174.5(1), b = 722.29(7), c = 3104.8(4) pm, β = 100.50(1)°, V = 2589.8(5) · 10⁶ pm³, space group P2₁/n; [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ): a = 2178.3(1), b = 1008.63(5), c = 1888.3(1) pm, β = 110.003(5)°, V = 3898.6(4) · 10⁶ pm³, space group P2/c.     

Modified Tellurium Subhalides in the New Structure Type [Te15X4]n[MOX4]2n (M = Mo,W; X = Cl,Br)

The reactions of Te₂Br with MoOBr₃, TeCl₄ with MoNCl₂/MoOCl₃, and Te with WBr₅/WOBr₃ yield black, needle-like crystals of [Te₁₅X₄][MOX₄]₂ (M = Mo, W; X = Cl, Br). The crystal structure determinations [Te₁₅Br₄][MoOBr₄]₂: monoclinic, Z = 1, C2/m, a = 1595.9(4) pm, b = 403.6(1) pm, c = 1600.4(4) pm, β = 112.02(2)°; [Te₁₅Cl₄][MoOCl₄]₂: C2/m, a = 1535.3(5) pm, b = 402.8(2) pm, c = 1569.6(5) pm, β = 112.02(2)°; [Te₁₅Br₄][WOBr₄]₂: C2, a = 1592.4(4) pm, b = 397.5(1) pm, c = 1593.4(5) pm, β = 111.76(2)° show that all three compounds are isotypic and consist of one-dimensional ([Te₁₅X₄]²⁺)_n and ([MOX₄]^?)_n strands. The structures of the cationic strands are closely related to the tellurium subhalides Te₂X (X = Br, I). One of the two rows of halogen atoms that bridges the band of condensed Te₆ rings is stripped off, and additionally one Te position has only 75% occupancy which leads to the formula ([Te₁₅X₄]²⁺)_n (X = Cl, Br) for the cation. The anionic substructures consist of tetrahalogenooxometalate ions [MOX₄]^? that are linked by linear oxygen bridges to polymeric strands. The compounds are paramagnetic with one unpaired electron per metal atom indicating oxidation state M^v, and are weak semiconductors.     

Pentaazadienido-Komplexe von Zink,Cadmium und Quecksilber Die Kristallstruktur von [Cd(EtOC6H4-N5-C6H4OEt)2(py)2] und [Hg(tol-N5-tol)2(py)]

Pentaazadienido Complexes of Zinc, Cadmium, and Mercury. The Crystal Structure of [Cd(EtOC₆H₄-N₅-C₆H₄OEt)₂(py)₂] and [Hg(tol-N₅-tol)₂(py)] The pentaazadienido complexes [M(EtOC₆H₄N₅C₆H₄OEt)₂] (M = Zn ( 1 ), Cd ( 2 )) are formed by the reaction of [M(NH₃)₄]²⁺ with [EtOC₆H₄N₅C₆H₄OEt]^? in aqueous ammonia. 2 crystallizes from pyridine as [Cd(EtOC₆H₄N₅C₆H₄OEt)₂py₂] ( 3 ) with the triclinic space group P1 and a = 937.2(2); b = 1422.7(2); c = 2085.5(2) pm; α = 75.28(1)°; β = 94.74(1)°; γ = 99.75(1)°; Z = 2. The central Cd²⁺ ion of 3 exhibits an octahedral coordination by two pyridine ligands in cis arrangement and two (N1, N3)-²⁺ chelating pentaazadienide ions. The reaction of [HgI₄]² with the 1,5-di(tolyl)pentaazadienide anion in aqueous ammonia affords [Hg(p-tol-N₅-tol)₂] ( 4 ), which crystallizes from pyridine in form of [Hg(tol-N₅-tol)₂py] ( 5 ) with the space group P1 and a = 1176.2(4); b = 1203.1(3); c = 1295.6(5) pm; α = 100.77(3)°; β = 110.08(3)°; γ = 94.29(2)°; Z = 2. In 5 the Hg²⁺ cation is threefold coordinated by two monodentate (N3)-η¹ pentaazadienid anions and one pyridine ligand. Within the N₅ chains of the pentaazadienid anions of 3 and 5 localized N? N double bonds are found in the positions N1? N2 and N4? N5 with distances between 125 and 129 pm.     

Einkristall-Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall—Metall-Bindung. II. Die Molekül- und Kristallstruktur von X2Sn[Mn(CO)5]2 (XCl,Br) Verbindungen

Single Crystal X-Ray Analysis of Compounds with Covalent Metal–Metal Bonds. II. Molecular and Crystal Structure of X₂Sn[Mn(CO)₅]₂ (X?Cl, Br) Both X₂Sn[Mn(CO)₅]₂ compounds (X?Cl, Br) crystallize in the monoclinic crystal system with at times different values in the lattice parameters. They belong to the space group C_2h⁵. The structures have been solved using 2 107 symmetrical independent reflection for Cl₂Sn[Mn(CO)₅]₂ and 1 470 reflections for Br₂Sn[Mn(CO)₅)₂] by applying the heavy atom method. The following interatomic distances have been found: Cl₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.635(1) Å, Sn? Cl = 2.385(2) Å, Mn? C = 1.852(8) Å, C? O = 1.128(10) Å; Br₂Sn[Mn(CO)₅]₂, Sn? Mn = 2.642(3) Å, Sn? Br = 2.548(2) Å, Mn? C = 1.851(21) Å, C? O = 1.124(25) Å. In addition, bond angles of X? Sn? X and Mn? Sn? Mn of these compounds have also been estimated in the case of X = Cl: 95.80(7)° and 126.25(4)° and for X?Br: 98.44(8)° and 125.88(9)°. The individual molecules of the X₂Sn[Mn(CO)₅]₂ solids are surrounded by ligands showing distorted tetrahedral configuration at the Sn atom and distorted octahedral configuration at the Mn atom.     

Über „Orthoindate”︁ der Alkalimetalle: Zur Kenntnis von K5[InO4]

A New ?Orthoindate”? of an Alkali Metal: K₅[InO₄] Hitherto unknown K₅[InO₄] was prepared by heating intimate mixtures of K₂O, In₂O₃ and elementar In (molar ratio 10.0 : 1.0 : 4.0) in closed Ni-cylinders (30 days, 500°C) in form of pale red, nearly colourless, transparent, single crystals. Same crystals were obtained by heating mixtures of K₂O, CdO and elementar In (molar ratio 3.1 : 1.0 : 1.0) in closed Ag-cylinders (30 days, 450°C), too. In this case we also found yellow-brown crystals of K₁₄[In₄O₁₃] [1]. Structure determination by four circle diffractometer data (MoKα, 15279 out 17454 I_o(hkl), R = 5.60%, R_w = 5.25%). Space group P1 with a = 1827.9 pm; b = 1694.4 pm; c = 1329.4 pm; α = 113.3°; β = 111.4°; γ = 105.2°; Z = 16. Characteristic feature of the structure are isolated [InO₄]^5?-tetraeder. The Madelung Part of Lattice Energy, MAPLE, the Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, and Charge Distribution, VADI, are calculated.     

Bi4RuBr2 und Bi4RuI2: Zwei Varianten einer Kolumnarstruktur mit flächenverknüpften quadratischen [RuBi8/2]-Antiprismen

Bi₄RuBr₂ and Bi₄RuI₂: Two Varieties of a Column Structure with Face-Sharing [RuBi_8/2] Square Antiprisms Reaction of the elements yields black, lustrous, air insensitive crystals of the subhalides Bi₄RuI₂ (tetragonal, I4/m, a = 1183.9(2) pm, c = 669.7(2) pm, V = 938.66 · 10⁶ pm³) and Bi₄RuBr₂ (monoclinic, I112/m, a = 1211.9(2) pm, b = 1072.6(2) pm, c = 663.9(2) pm, γ = 91.63(1)°, V = 862.64 · 10⁶ pm³). The structures of the homöotypic compounds contain [RuBi_8/2] strands of face-sharing square antiprisms. Halogen atoms lie above the edges of alternate Bi₄ squares. Thereby chemical bonding differs significantly within the two types of Bi₄ squares. Though the Ru atoms on the central axis of the strand of antiprisms form pairs, extended Hückel calculations give no evidence of Ru? Ru bonds.     

Synthese und Kristallstrukturen von Bromid—Thiosilicaten Ln3Br[SiS4]2 der Lanthanide (Ln = La,Ce, Pr,Nd, Sm,Gd)

Synthesis and Crystal Structures of Lanthanide Bromide Thiosilicates Ln₃Br[SiS₄]₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) Single crystals of the bromide—thiosilicates Ln₃Br[SiS₄]₂ were prepared by reaction of lanthanide metal (Ln = La, Ce, Pr, Nd, Sm, Gd), sulfur, silicon and bromine in quartz glass tubes. The thiosilicates crystallize in the monoclinic spacegroup C2/c (Z = 4) isotypically to the iodide analogues Ln₃I(SiS₄)₂ and the A—type chloride—oxosilicates Ln₃Cl[SiO₄]₂ with the following lattice constants: La₃Br[SiS₄]₂: a = 1583.3(4) pm, b = 783.0(1) pm, c = 1098.2(3) pm, β = 97.33(3)° Ce₃Br[SiS₄]₂: a = 1570.4(3) pm, b = 776.5(2) pm, c = 1092.2(2) pm, β = 97.28(2)° Pr₃Br[SiS₄]₂: a = 1562.6(3) pm, b = 770.1(2) pm, c = 1088.9(2) pm, β = 97.50(2)° Nd₃Br[SiS₄]₂: a = 1561.4(4) pm, b = 766.0(1) pm, c = 1085.3(2) pm, β = 97.66(3)° Sm₃Br[SiS₄]₂: a = 1555.4(3) pm, b = 758.5(2) pm, c = 1079.9(2) pm, β = 98.28(2)° Gd₃Br[SiS₄]₂: a = 1556.5(3) pm, b = 750.8(1) pm, c = 1074.5(2) pm, β = 99.26(2)° In the crystal structures the bromide ions form chains along [001] with trigonal planar coordination by lanthanide cations, while the [SiS₄]^4‐—building units display isolated distorted tetrahedra.     

Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh₃)₂Pt(P^tBu)₃], [(PPh₃)₂Pd(P^tBu)₂], [(CO)₄Cr{(PⁱPr)₃}₂], [RhCl(PPh₃)(P^tBu)₃], [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂], and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh₃)₂Pt(P^tBu)₃] ( 1 ), [(PPh₃)₂Pd(P^tBu)₂] ( 2 ), [(CO)₄Cr{(PⁱPr)₃}₂] ( 3 ), [RhCl(PPh₃)(P^tBu)₃] ( 4 ), [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂] ( 5 ) and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P2₁/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P2₁/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P2₁/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.     

Phosphaniminato‐Komplexe des Hafniums. Die Kristallstrukturen von [Hf(NPPh3)4] · 3 THF und [Hf(NPPh3)2Cl2(HNPPh3)2]

Phosphoraneiminato Complexes of Hafnium. Crystal Structures of [Hf(NPPh₃)₄] · 3 THF and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] The phosphoraneiminato complexes [Hf(NPPh₃)₄] · 3 THF ( 1 · 3 THF) and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] ( 2 ) have been prepared as colourless, moisture sensitive single crystals by reactions of hafnium tetrachloride with [CsNPPh₃]₄ · 2 toluene in tetrahydrofurane solutions by application of different ratios of the educts. Both complexes are characterized by IR spectroscopy and X‐ray crystal structure determinations. 1 · 3 THF: space group P 1, Z = 4, lattice dimensions at 193 K: a = 2007.6(1); b = 2064.2(1); c = 2115.9(1) pm; α = 109.193(4)°; β = 111.285(4)°; γ = 96.879(4)°; R₁ = 0.0506. 1 forms monomeric molecules with tetrahedral coordination of the nitrogen‐atoms of the (NPPh₃^–)‐groups towards the Hafnium atom. The HfN distances of 200.9 pm in average correspond with double bonds. 2 : space group P 1, Z = 4, lattice dimensions at 193 K: a = 1444.0(1); b = 1928.1(1); c = 2455.8(2) pm; α = 67.273(8)°; β = 87.445(8)°; γ = 87.082(8)°; R₁ = 0.0312. 2 has a monomeric molecular structure with octahedral coordination of the hafnium atom. The chlorine atoms are in trans position to one another, whereas the nitrogen atoms of the phosphoraneiminato groups (NPPh₃^–) are in trans position towards the nitrogen atoms ot the phosphorane imine molecules (HNPPh₃). The HfN bond lengths of the (NPPh₃^–) groups of 199.7 pm in average correspond with double bonds, whereas the HfN distances of the HNPPh₃ molecules with bond lengths of 230.2 pm in average are of donor‐acceptor type.     

Schwache Sn…I‐Wechselwirkungen in den Kristallstrukturen der Iodostannate [SnI4]2– und [SnI3]–

Weak Sn…I Interactions in the Crystal Structures of the Iodostannates [SnI₄]^2– and [SnI₃]^– Iodostannate complexes can be crystallized from SnI₂ solutions in polar organic solvents by precipitation with large counterions. Thereby isolated anions as well as one, two or three‐dimensional polymeric anionic substructures are established, in which SnI₃^– and SnI₄^2– groups are linked by weak Sn…I interactions. Examples are the iodostannates [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ), (Ph₄P)₂[Sn₂I₆] ( 2 ), [Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ), [Fe(dmf)₆][SnI₃]₂ ( 4 ) and (Pr₄N)[SnI₃] ( 5 ), which have been characterized by single crystal X‐ray diffraction. [Me₃N–(CH₂)₂–NMe₃][SnI₄] ( 1 ): a = 671.6(2), b = 1373.3(4), c = 2046.6(9) pm, V = 1887.7(11) · 10⁶ pm³, space group Pbcm;(Ph₄P)₂[Sn₂I₆] ( 2 ): a = 1168.05(6), b = 717.06(4), c = 3093.40(10) pm, β = 101.202(4)°, V = 2541.6(2) · 10⁶ pm³, space group P2₁/n;[Me₃N–(CH₂)₂–NMe₃][Sn₂I₆] ( 3 ): a = 695.58(4), b = 1748.30(8), c = 987.12(5) pm, β = 92.789(6)°, V = 1199.00(11) · 10⁶ pm³, space group P2₁/c;[Fe(dmf)₆][SnI₃]₂ ( 4 ): a = 884.99(8), b = 1019.04(8), c = 1218.20(8) pm, α = 92.715(7), β = 105.826(7), γ = 98.241(7), V = 1041.7(1) · 10⁶ pm³, space group P1;(Pr₄N)[SnI₃] ( 5 ): a = 912.6(2), b = 1205.1(2), c = 1885.4(3) pm, V = 2073.5(7) · 10⁶ pm³, space group P2₁2₁2₁.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

Untersuchungen am Chlordiphenyl‐ und Tribenzylstiban sowie am Tribenzyldibromstiboran – Molekülstrukturen und Isotypie

Element–Element Bonds. X. Studies of Chloro(diphenyl)stibane, Tribenzylstibane and Tribenzyldibromostiborane – Molecular Structures and Isotypism Chlorodiphenylstibane ( 1 d ) {P2₁/c; Z = 4; a = 1191.8(1); b = 853.4(1); c = 1112.0(1) pm; β = 93.60(1)°; –100 ± 2 °C} crystallizes isotypically with a series of homologous (H₅C₆)₂E–X compounds (E = As, X = Cl, Br, I; E = Sb, X = Br, I); the structure type of tribenzylstibane ( 5 d ) {Pbca; Z = 8; a = 832.1(2); b = 2681.3(5) pm; c = 1600.9(3); –100 ± 3 °C} is already known from tribenzylmethanol, ‐silanol and ‐silane. Tribenzyldibromostiborane ( 6 ) {P2₁/n; Z = 4; a = 938.4(2); b = 2292.4(5); c = 1019.7(2) pm; β = 112.71(1)°; –100 ± 3 °C} does not show an analogous relationship to known structure types. Characteristic mean bond lengths and angles are { 1 d , Sb–Cl 240.9(1), Sb–C 214.0 pm, Cl–Sb–C 93.8°, C–Sb–C 98.6(1)°; 5 d , Sb–C 217.5(3) pm, C–Sb–C 94.9(6)°; 6 , Sb–Br 264.6; Sb–C 217.0(8) pm, Br–Sb–Br 179.4(1)°; C–Sb–C 120°; Br–Sb–C 84.8(2)° to 94.7(2)°}. Stiborane 6 exhibits very weak intermolecular Sb‥Br interactions of 417 pm which, however, affect the molecular conformation in a striking way.     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Darstellung und Kristallstrukturen der ersten Alkalimetall‐hexacarbonatooxotetraberyllate: K6[Be4O(CO3)6] · 7 H2O und K6[Be4O(CO3)6]

Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K₆[Be₄O(CO₃)₆] · 7 H₂O and K₆[Be₄O(CO₃)₆] K₆[Be₄O(CO₃)₆] · 7 H₂O has been prepared by dissolving freshly precipitated Be(OH)₂ in an aqueous KHCO₃ solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, V_EZ = 1290, 6(3)·10⁶ pm³, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, V_EZ = 2961, 4(3)·10⁶ pm³, Z = 6).     

Bifunktionalisierte 1 H‐Phosphiren‐ und g1‐1‐Phosphaallen‐Wolframkomplexe

Bifunctionalized 1 H‐Phosphirene and g¹‐1‐Phosphaallene Tungsten Complexes The tungsten(0) complex [{(Me₃Si)₂HCPC(Ph)=N}W(CO)₅] 1 reacts upon heating with acetylene derivatives 2 a–d in toluene to form benzonitrile and the complexes [{(Me₃Si)₂HCPC(R)=COEt} · W(CO)₅] 5 a–d ( 5 a : R = SiMe₃; 5 b : R = SiPh₃; 5 c : R = SnMe₃; 5 d : R = SnPh₃) and [{(Me₃Si)₂HCP=C=C(OEt)R} · W(CO)₅] 6 a, b ( 6 a : R = SnMe₃; 6 b : R = SnPh₃), which have been isolated by chromatography; complexes 5 c and 6 a have been characterized as mixtures. Spectroscopic and mass spectrometric data are discussed. The crystal structure of the compound 5 a was determined by X‐ray single crystal structure analysis ( 5 a : space group P2₁/n, Z = 4, a = 977.6(2) pm, b = 1814.6(4) pm, c = 1628.0(4) pm, β = 93.95(2)°).     

Polymere Iodoplumbate – Synthese und Kristallstrukturen von (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N–C2H4–NMe3)2[Pb2I7]I

Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF, (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF, and (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ) and (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the Pb^II atoms are coordinated either by six bridging I^– ligands in the two-dimensional [Pb₅I₁₄]^4– network or by six DMF ligands in the [Pb(dmf)₆]²⁺ cations. In contrast, (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ) contains non-coordinating I^– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI₆ octahedra, whereas in 1 PbI₆ and PbI₅(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI₂ structure. (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 10⁶ pm³; (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄]·DMF ( 2 ): Space group P2₁, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 10⁶ pm³; (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 10⁶ pm³.     

Dimers and Chains of Hydrogen bonded [HS2O7]– Anions in the Crystal Structures of M[HS2O7] (M = K, [NH4], [NO], Rb,Cs)

The reactions of KCl, [NH₄]₂[SO₄], Rb₂[CO₃], and Cs₂[CO₃] with fuming sulfuric acid (65 % SO₃) yielded colorless and moisture sensitive crystals of K[HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 716.67(3) pm, b = 1043.57(4) pm, c = 828.78(3) pm, β = 107.884(1)°, V = 589.89(4) × 10⁶ pm³), [NH₄][HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 729.29(1) pm, b = 1079.73(1) pm, c = 843.26(1) pm, β = 106.397(1)°, V = 637.01(1) × 10⁶ pm³), Rb[HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 724.49(2) pm, b = 1073.19(3) pm, c = 852.01(3) pm, β = 106.534(1)°, V = 635.06(3) × 10⁶ pm³), and Cs[HS₂O₇] (triclinic, P$\bar{1}$ (no. 2), Z = 2, a = 537.61(3) pm, b = 784.71(4) pm, c = 867.93(4) pm, α = 94.214(2)°, β = 103.138(2)°, γ = 105.814(2)°, V = 339.47(3) × 10⁶ pm³). Colorless crystals of [NO][HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 739.90(4) pm, b = 1048.00(5) pm, c = 830.97(4) pm, β = 106.985(2)°, V = 106.985(2) × 10⁶ pm³) were obtained as a side product from the reaction of [NH₄]₂[Rh(NO₂)₄] with oleum (65 % SO₃) in the ionic liquid [BMIm][OTf]. The crystal structures of K[HS₂O₇], [NH₄][HS₂O₇], [NO][HS₂O₇], and Rb[HS₂O₇] show the [HS₂O₇]^– ions linked into dimers by strong hydrogen bonds. Contrastingly, in the crystal structure of Cs[HS₂O₇] the [HS₂O₇]^– ions are connected to infinite chains. Raman spectra were recorded for M[HS₂O₇] (M = K, Rb, Cs).     

Zinkselenid- und Zinktelluridcluster mit Phenylselenolat- und Phenyltellurolatliganden. Die Kristallstrukturen von [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr,Ph) und [Zn10Te4(TePh)12(PR3)2] (R = nPr,Ph)

Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt₄]₂[Zn₄Cl₄(SePh)₆], [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂], [Zn₈Se(SePh)₁₄(PⁿPr₃)₂], [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr, Ph), and [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr, Ph) In the prescence of NEt₄Cl ZnCl₂ reacts with PhSeSiMe₃ or a mixture of PhSeSiMe₃/Se(SiMe₃)₂ to form the ionic complexes [NEt₄]₂[Zn₄Cl₄(SePh)₆] 1 or [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂] 2 respectively. The use of PⁿPr₃ instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn₈Se(SePh)₁₄(PⁿPr₃)₂] 3 . Reactions of ZnCl₂ with PhTeSiMe₃ and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr 4 , Ph 5 ) and in THF of the uncharged [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P2₁/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P2₁/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P2₁/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I4₁/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°)     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).