Bridging Iodine Research Articles

Synthesis and Characterization of Bismuth Complexes [BiI2(4,4′-bpy)(S2CNR2)]∞ and [BiI(S2CNR2)2]∞ and Crystal Structure of [BiI2(4,4′-bpy)(S2CNC4H8O)]∞ and [BiI(S2CNC5H10)2

The six new bismuth(III) complexes [BiI2(4,4′-bpy)(S2CNR2)]∞ (NR2=NC4H8O 1, NC4H82, N(C2H4OH)23) and [BiI(S2CNR2)2]∞ (NR2= NC5H104, NC4H85, NEt26) have been synthesized by the reactions of BiI3 with 4,4′-bipyridine and dithiocarbamate, and their structures have been characterized by elemental analysis and IR spectroscopy. The crystal structures of complexes 1 and 4 have been determined by X-ray diffraction. In the complex 1, the structure shows a distorted pentagonal bipyramid geometry with seven-coordination for the central Bi atom and the bridging 4,4′-bipyridines links the Bi atoms to form one-dimensional chain polymer. The structure of complex 4 shows a distorted octahedral configuration with six-coordination for the central Bi atom and the bridging iodine atom link the Bi atoms to form one-dimensional chain polymer.

Synthesis and Characterization of Bismuth Complexes [BiI2(4,4′-bpy)(S2CNR2)]∞ and [BiI(S2CNR2)2]∞ and Crystal Structure of [BiI2(4,4′-bpy)(S2CNC4H8O)]∞ and [BiI(S2CNC5H10)2

The six new bismuth(III) complexes [BiI2(4,4′-bpy)(S2CNR2)]∞ (NR2=NC4H8O 1, NC4H8 2, N(C2H4OH)2 3) and [BiI(S2CNR2)2]∞ (NR2= NC5H10 4, NC4H8 5, NEt2 6) have been synthesized by the reactions of BiI3 with 4,4′-bipyridine and dithiocarbamate, and their structures have been characterized by elemental analysis and IR spectroscopy. The crystal structures of complexes 1 and 4 have been determined by X-ray diffraction. In the complex 1, the structure shows a distorted pentagonal bipyramid geometry with seven-coordination for the central Bi atom and the bridging 4,4′-bipyridines links the Bi atoms to form one-dimensional chain polymer. The structure of complex 4 shows a distorted octahedral configuration with six-coordination for the central Bi atom and the bridging iodine atom link the Bi atoms to form one-dimensional chain polymer.

Crystal structure of diiodo-bis[(4R,5R)-trans-4,5-bis[(diphenylphosphinomethyl)- 2,2-dimethyl-1,3-dioxalane]dicopper(I), Cu2I2(C31H32O2P2)2

C62H64C112I2O4P4, triclinic, PI (no. 1), a = 10.0989(2) A, b = 12.8084(1) A, c = 12.8423(2) A, a = 65.074(l)) β = 84.31°, γ = 87.854(1)°, V= 1499.0 A, Ζ = 1, R&(F) = 0.036, wRreffF) = 0.098, Τ = 293 Κ. Source of material The title compound was synthesized following a published procedure for the silver(I) analogs [1]. To a solution of optically pure DIOP (50.0 mg, 0.10 mmol; DIOP = (4fl,5A)-irans-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyl-l,3-dioxalane) in CH2CI2 (5 mL) was added an excess of Cul (40.0 mg, 0.21 mmol). After refluxing the mixture for 0.5 h, a precipitate was removed by filtration and the filtrate treated with dried diethyl ether (10 mL) to give a white powder (yield 76 %). Colorless crystals suitable for X-ray studies were obtained by slow evaporation of its solution in CH2Cl2/n-heptane (1:1). Elemental analysis found: C, 53.58 %; H, 4.82% (VarioEL); calc. for C62H64CU2I2O4P4: C, 54.04 %; H, 4.68%. Experimental details The absolute configuration of the chiral complex was confirmed by a value of the Flack parameter of 0.02(3) [2]. Discussion The chiral diphosphine DIOP is an important bidentate ligand for transition metal complexes that can be used for asymmetric catalytic reactions [3-5]. In the search for such complexes we have obtained a dimeric Cu(I) compound, [CuI(A,A-DIOP)]2, which features a novel Ο12 core quadruply bridged by all the four ligands. Each copper atom resides at a slightly distorted tetrahedral environment composed of two iodine atoms and two phosphorous atoms each from a DIOP ligand. The four bridging ligands and the two copper atoms form a rhombic four-membered G12I2 ring (I-Cu-1,109.11(6) and 110.42(6)°; Cu-I-Cu, 70.22(5)° and 70.24(5)°, respectively) and an outer 14-membered ring, CuDIOP-Cu-DIOP. Both of the Cul-Il-Cu2-I2 and Cul-Pl-P3Cu2-P4-P2 cores are coplanar (largest deviation 0.0069 A and 0.0317 A, respectively), intersecting at Cul—Cu2 with a dihedral angle of 97.4(6)°. The coordination parameters around the two Cu(I) centers are slightly different. The Cul—PI and Cul—P2 distances (2.252(4) A and 2.254(4) A) are shorter than the Cu2—P3 and Cu2—P4 distances (2.305(4) A and 2.320(4) A), while the Pl-Cul-P2 angle (122.5(2)°) is slightly wider than P3-Cu2-P4 (120.2(2)°). The bond angles about the two bridging iodine atoms are nearly identical (ZCu2-Il-Cul = 70.22(5)°; Z.Cu2-I2-Cul = 70.24(5)°). The Cu-Cu separation of 3.141 A indicates no significant interaction of the metals (the sum of the covalent radii is 2.76 A). Similar coordination mode has been reported for some Ag(I)-DIOP compounds [1] and ((4R,5R)-trans4,5-bis(((3-methylphenyl)phosphino)-methyl)-2,2-dimeth:yll,3-dioxalane)copper(I) chloride [5]. Table 1. Data collection and handling.

Novel 1D and 2D heterometallic Cu/Cd complexes comprising unique mixed-anion Cd(μ-Cl)(μ-O 2CMe)Cl(O 2CMe) 2−, Cd(μ-O 2CMe) 2I(O 2CMe) 2−, Cd(μ-I)(μ-O 2CMe)I(O 2CMe) 2− and [formula omitted] building blocks: Synthesis from elemental copper, structure and magnetism

Three new Cu/Cd mixed-anion solid-state coordination polymers [Cu(en) 2Cd(μ-Cl)(μ-O 2CMe)Cl(O 2CMe)] n ( 1), [Cu(en) 2CdI 1.64(O 2CMe) 2.36] n ( 2) and [Cu 2(en) 4Cd 2(NCS) 6(O 2CMe) 2] n ( 3) have been prepared using unactivated copper powder, cadmium acetate, NH 4X (X = Cl, I, NCS) and ethylenediamine in non-aqueous solvents, namely dmso, dmf and CH 3OH, in the open air. Depending on the nature of the selected counter-anion in the initial ammonium salt, a facile approach to the controlled assembly of 1D or 2D extended networks has been offered. X-ray studies show that 1 and 2 possess 1D helical chain crystal structures, constituting cationic Cu ( en ) 2 2 + and mixed-ligand anionic Cd(μ-Cl)(μ-O 2CMe)Cl(O 2CMe) 2−, Cd(μ-O 2CMe) 2I(O 2CMe) 2− or Cd(μ-I)(μ-O 2CMe)I(O 2CMe) 2− building blocks, conjoining together through the oxygen atoms of chelating bidentate and simultaneously bridging unidentate acetate ligands and also by a bridging chlorine atom (for 1) and by a bridging iodine or oxygen atom of a weakly bidentate acetate group (for 2). In both complexes, distinct hydrogen bonds are present and serve to increase the dimensionality of the compound from one to two. The 2D polymeric sheet of complex 3 consists of a 1D mixed-anion polymer –NCS–Cd(NCS) 2(O 2CMe)–SCN–Cd(NCS) 2(O 2CMe)–NCS– and Cu(en) 2 units. Each of two crystallographically independent cadmium atoms has six coordination, consisting of CdN 4O 2 or CdS 2N 2O 2 distorted octahedral geometries. The copper atom of Cu(en) 2 also exhibits a distorted octahedral arrangement. Apical bonds between the Cu(II) and S atoms from terminal NCS–groups [3.1113(12) and 3.1467(14) Å] link the anionic chains forming a 2D network. Variable-temperature magnetic susceptibility measurements of 1– 3 show weak antiferromagnetic coupling between the copper centres.

Synthetic and Theoretical Study of the Incorporation of Metal Halides in [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)

The capacity of the imido-nitrido organometallic ligand [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) to entrap main group metal halides MXn has been investigated. Treatment of 1 with metal halides in toluene or dichloromethane afforded several soluble adducts [MXn(L)] (L=1) in good yields. The reaction of 1 with one equivalent of Group 1 and 13 monohalides MX afforded single cube-type complexes [XM{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (M=Li, X=Br (2), I (3); M=Na, X=I (4); M=In, X=I (5); M=Tl, X=I (6)). Analogous treatment of 1 with Group 2 and 14 dihalides MX(2) gave the corresponding adducts [I2M{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (M=Mg (7), Ca (8), Sr (9)) and [Cl(2)M{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (M=Sn (10), Pb (11)). The treatment of 1 with SnI2 or the reaction of 10 with MeI at 60 degrees C afforded two azametallocubane units linked by two bridging iodine atoms [{ISn(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}2(mu-I)2] (12). Indium triiodide reacted with 1 in toluene to form the adduct [I3In(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)] (13). Density functional theory calculations have been carried out to study these processes and evaluate the influence of the solvent. X-ray crystal structure determinations have been performed for complexes 10, 12, and 13.

A stable dimeric mono-coordinated NHC-Pd(II) complex: synthesis, characterization, and reactivity in Suzuki-Miyaura cross-coupling reaction

A stable dimeric mono-coordinated NHC–Pd(II) complex with bridging iodine atoms was synthesized and characterized by single-crystal X-ray diffraction. It has been successfully applied to the Suzuki–Miyaura cross-coupling reaction under aerobic conditions. Good to excellent yields were obtained in most cases with the addition of H2O. Copyright © 2005 John Wiley & Sons, Ltd.

Synthesis and structure of the heterobimetallic Yb(II) complex of composition L2Yb2LiI3 supported with the β-diketiminato ligand [L=Et2NCH2CH2NC(Me)CHC(Me)NCH2CH2NEt2

The heterobimetallic Yb(II) mixed ligand complex L2Yb2LiI31 has been prepared by the reaction of the lithium salt of the ligand L with the ytterbium diiodide. Compound 1 is characterized by single crystal X-ray structural analysis, multinuclear NMR and mass spectrometry. Complex 1 consists of LYbI and LLi units connected with the central Yb(1) atom. The latter is surrounded by the LYbI and LLi moieties in a sandwich like structure including two bridging iodine atoms. The NCCCN unsaturated system of the ligand in each of the units is almost planar and π coordinated to the Yb(1) atom. These two planar units are tilted to each other and the pendant arms of the β-diketiminato ligand in each moiety are bent. The metal atoms are located out of the NCCCN plane of the ligands and the three metal atoms in complex 1 form almost a straight line.

Metallochain cluster complexes and metallomacrocyclic triangles based on coordination bonds between palladium or platinum and diphosphinoacetylene ligands.

To explore the potential of the coordination chemistry of Pd and Pt halides with phosphinoacetylene ligands for the generation of novel, highly metallated organometallic coordination polymers, investigations on model compounds [MX2(PPh2 C identical to CPh)2] that exhibit trans-configured Pd centers and cis-configured Pt centers have been performed. The molecular structure of the trans-Pd complexes 2 (M = Pd, X = Br) and 5 (M = Pd, X = I) appeared suitable for the generation of linear materials, whereas the cis-Pt complex 6 (M = Pt, X = I) suggested the prospective formation of ring systems. The presence of acetylene moieties allowed for further increase of metal concentration by cluster formation with [Co2(CO)8]. Two novel bimetal cluster complexes 7 and 8 were obtained from 5 and 6, respectively, and these exhibit a bridging iodine ligand as an interesting structural motif leading to heterocyclic systems with M-I-Co-C-P skeletons (M = Pd or Pt). A similar approach with [Fe2(CO)9] led to the formation of several products, including an unusual Pd-Fe cluster-containing compound 10. The extension of the coordination strategy to rigid bis(phosphinoacetylene) ligands gave rise to strained ring systems. Surprisingly, for the cis-configured PtCl2 center, a rarely observed triangular structure 12 was obtained exclusively. The corresponding PtI2 analog, 13a rearranged over time to form a "ring-fused" system 13b with an extended BINAP-like ligand.

Kristallstrukturen der Komplexe Von Quecksilber(Ii)Iodid und -Thiocyanat mit L,13-Bis(8-Chinolyl)-L,4,7,10,13-Pentaoxatridecan („Kryptand 5“)

Abstract Reactions of 1,13-bis(8-chinolyl)-1,4,7,10,13-pentaoxatridecane (“Cryptand 5”) with HgX2 (X = I, SCN) yield crystals of [(cryptand 5)(HgI2)2] (1) and [(cryptand 5 )2{Hg(SCN)2}4] (2), resp. In both complexes two molecules of HgX2 are bound to one ligand molecule. 1 has symmetry Ci with the oxygen atom O(3 ) of the ether chain on a center of symmetry of the unit cell, each Hg atom is bound to the two I atoms, the N atom of the chinolyl residue, and one oxygen atom, O(1) and O(l)i, resp. of the ligand; neighbouring complex units are connected via iodine bridges thus forming chains. In 2 also two formula units of HgX2 are bound to one ligand molecule, but contrary to 1 the complex is not centrosymmetric. The Hg atoms of the two Hg(SCN)2 groups are co-ordinated differently: both are bound via sulphur atoms to two SCN-groups, one being a terminal SCN group, the other acting as a bridge to the Hg atom of a neighbouring complex unit. The first Hg atom is connected to a chinolyl N atom and too oxygen atoms, the second to a chinolyl N atom and three oxygen atoms. There are two independent complex units per asymmetric unit which are related by a non-crystallographic twofold axis, and which are connected via two SCN bridges. These “double molecules” are also interconnected by thiocyanate bridges, thus forming a chain structure

Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions

Reactions of CsI and HgI2 with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)2]2[Hg2I6] (1) and {[Cs(15C5)]2[Hg2I6]}n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs+ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5)2+ cations and a Hg2I62- anion. Cs+ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5)2+ and anionic Hg2I62- are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]2[Hg2I6] units. Each structural unit contains two Cs(15C5)+ cations and a Hg2I62- anion. Cs+ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg2I62-, and an iodine atom of Hg2I62- in an adjacent structural unit. The interactions between the Cs+ of Cs(15C5)+ and an I− in Hg2I62- from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg2I62- in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P21/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) A, β = 111.0(1)°, V = 3860 A3, Z = 4, R = 0.082 (Rw = 0.089). Crystal data for 2: space group P21/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) A, β = 91.54(3)°, V = 2146 A3, Z = 4, R = 0.034 (Rw = 0.048).

Untersuchungen an Polyhalogeniden, XXXVI. Zur Kenntnis des Oktaiodid-Ions I8 2-: Darstellung und Kristallstruktur des [(Crypt-2.2.2)H2]l8, des [Ni(phen)3]I8 · 2CHCl3 und der Bis(N-alkylurotropinium) oktaiodide (UrR)2I8 mit R = Methyl und Ethyl / Studies on Polyhalides, XXXVI. On the Octaiodide Ion I8 2-: Preparation and Crystal Structure of [(Crypt-2.2.2)H2]I8, of [Ni(phen)3]I8-2CHCl3 and of the Bis(N-alkylurotropinium)octaiodides (UrR)2I8 with R = methyl and ethyl

Abstract The new compound [(Crypt-2.2.2)H2]I8 has been prepared by the reaction of [(Crypt-2.2.2)H2](I3)2 with iodine in methanol. It crystallizes in the orthorhombic space group Pbcn with a = 11.476 (2), b = 13.589 (2), c = 22.888 (2) Å and Z = 4. The crystal structure has been refined to RF = 0.031 for 1618 reflections. It may be described as a layerlike packing of octaiodide anions I8 2-and diprotonated 2.2.2-Crypt as cations. The non planar octaiodide anion is built up from two triiodide groups and a bridging iodine molecule. Tris(1, 10-phenanthroline)nickel(II) octaiodide bis(chloroform) crystallizes in the monoclinic space group P21/n with a = 11.683 (8), b = 21.717 (8), c = 20.752 (5) Å, β = 95.03 (5)° and Z = 4 formula units. The crystal structure has been refined to RF = 0.058 for 3894 reflections. The structure consists of two chloroform molecules, octahedrally coordinated complex cations [Ni(phen)3]2+ and nonplanar octaiodide anions I8 2- each composed of two asymmetric triiodide units I3 - weakly associated with an elongated bridging iodine molecule I2. The already known structure of bis(N-methylurotropinium) octaiodide, (UrMe)2I8, has been verified and more accurate crystal data have been collected. The crystal structure has been refined to RF = 0.045 for 1908 reflections. The compound crystallizes in the monoclinic space group P21/c with a = 11.302 (2), b = 9.850 (2), c = 14.188 (2) Å , β = 92.59 (1)° and Z = 2. The anion has the shape of a stretched Z. The structure of bis(N-ethylurotropinium) octaiodide (UrEt)2I8 has been determined and a new configuration (I3 -, I5 -) for octaiodide ions between Z (I3 - · I2 ·I3 -) and a “broken” configuration (I3 -, I5 -) has been observed. The compound crystallizes in the triclinic space group P1̄ with a = 9.741 (3), b = 11.815 (3), c = 15.426 (3) Å, α = 91.80 (2), β = 107.14 (2), γ = 90.04 (2)° and Z = 2. The crystal structure has been refined to RF = 0.037 for 3657 reflections.

Novel Bonding of Iodine: Crystal Structure of HIS2 O8.

Iodine bridges two sulfate tetrahedra in the title compound and therefore participates in unusual and novel bonding. The structure of the compound (section shown on the right) can be regarded as the result of a condensation reaction between the protonated form of the hypothetical iodic(III) acid, sulfuric acid, and hydrogensulfate.

Crystal and molecular structure of tris( N-methylaminoethanoldithiocarbamato)antimony(III), bismuth(III) and bis(iodobis( N-methylaminoethanoldithiocarbamato)antimony(III) and VBS calculations

Syntheses, crystal strucutres and VBS calculations for Sb(nmedtc) 3 ( 1), Bi(nmedtc) 3 ( 2) and Sb 2(nmedtc) 4I 2 ( 3) complexes (where nmedtc= N-methylaminoethanoldithiocarbamate) are reported. Crystallographic data: 1: C 12H 24N 3O 3S 6Sb, monoclinic, P2 1/ c, a=11.352(2), b=17.674(3), c=11.272(2) Å, β=101.53(4)°, Z=4; 2: C 12H 24N 3O 3S 6Bi, monoclinic, P2 1/ c, a=11.225(2), b=17.953(1), c=11.346(2) Å, β=102.28(3)°, Z=4; 3: C 10H 20I 2N 2O 4Sb, triclinic, P1, a=10.356(3), b=11.047(2), c=10.009(3) Å, α=80.12(4), β=51.49(3), γ=67.41(3)°, Z=2. The present study has conclusively proved the presence of intermolecular hydrogen bonding in complexes 1 and 2 and ruled out the intramolecular hydrogen bonding predicted on the basis of an IR study. The anisobidenticity associated with the dithiocarbamate ligand is due to the presence of a lone pair of electrons on the central ion and the stereochemical requirements. Complex 3 exists as a dimer (Sb–I=3.359(5), Sb–I′=3.280(5) Å) unlike its diethyl analogue which is a single polymeric strand with iodine bridges (Sb–I=3.516(2) Å)). The valence bond sums (VBS) for all the complexes have been calculated and were found to be equivalent to 3.0±0.2 indicating the compromise between the steric and electronic requirements of the ligand and the central ion.

Two Closely Related Structure Types with Unprecedented Bioctahedral Rare-Earth-Metal Clusters Centered by Transition Metals: A2R10I17Z2(A = Rb, Cs; R = La, Ce, Pr; Z = Co, Ni, Ru, Os) and La10I15Os2

A family of compounds has been discovered in which pairs of octahedral rare-earth-metal clusters, each centered by a late transition metal Z, share a common edge. This R{sub 10}Z{sub 2} units, sheathed and interbridged by iodine atoms, occur in the quaternary phases Rb{sub 2}La{sub 10}I{sub 17}Co{sub 2}, Cs{sub 2}La{sub 10}I{sub 17}Z{sub 2} (Z = Co, Ni, Ru, Os), Cs{sub 2}Ce{sub 10}I{sub 17}Os{sub 2}, and Cs{sub 2}Pr{sub 10}I{sub 17}Z{sub 2}(Z = Co, Ru, Os) and in the ternary La{sub 10} I{sub 15}Os{sub 2}. All are obtained as black, air-sensitive crystals from reactions of RI{sub 3}, R, Z, and RbI or CsI as appropriate in welded Nb containers at 800-850{degree}C. The structure of Cs{sub 2} Ce{sub 10}I{sub 17}Os{sub 2} has been refined by single-crystal X-ray diffraction methods for comparison with the isotypic Cs{sub 2}La{sub 10}I{sub 17}Co{sub 2}, and the structure of a unique ternary La{sub 10}I{sub 15}Os{sub 2} has been defined. These new bioctahedral clusters may be regarded as the missing links between discrete clusters and infinite chains of condensed octahedral clusters among rare-earth-metal cluster halides that are stabilized by interstitial transition metals. The biclusters in both structures are extensively interconnected into three-dimensional arrays through bridging iodine atoms. The structural interconversion betweenmore » Cs{sub 2}La{sub 10}I{sub 17}Os{sub 2} and La{sub 10}I{sub 15}Os{sub 2} + 2CsI may be easily visualized in terms of changes in iodide bridging modes and accommodation of cesium cations. 29 refs., 7 figs., 7 tabs.« less

Synthesis and Stereochemistry of the First Chiral (Imidazolinylidene)‐ and (Triazolinylidene)palladium(ii) Complexes

AbstractThe reaction of three equiv. of a chiral imidazolium or triazolium perchlorate with one equiv. of Pd(OAc)2, an excess of NaI and a base leads to the corresponding chiral dicarbenediiodopalladium(II) complexes in chemical yields up to 98% and with the trans isomer as the major product (1, 2). If only one equiv. of the imidazolium or triazolium perchlorate is used, then dinuclear complexes with bridging iodine atoms are formed (3, 4, chemical yield 92—94%). The latter can add Lewis basic ligands, e.g. amines, phosphanes or other carbenes, to give mononuclear complexes with one carbene ligand coordinated to the PdI2 fragment (5, 6). Preliminary test experiments with these Pd(II) complexes as catalysts for an enantioselective Heck‐type reaction have been carried out.

Untersuchungen an Polyhalogeniden, XIX [1] Bis(methyltriphenylphosphonium)oktaiodid (MePh3P)2I8, Cäsium(18-Krone-6)triiodid [Cs(C12H24O6)]I3, Iodoblei(18-Krone-6)triiodid [Pb(C12H24O6I]I3 und Diiodothallium(18-Krone-6)tetraiodothallat [Tl(C12H24O6)I2](TlI4) / Studies of Polyhalides, XIX [1] Bis(methyltriphenylphosphonium) Octaiodide (MePh3P)2I8, Cesium(18-crown-6) Triiodide [Cs(C12H24O6)]I3, Iodolead(18-crown-6) Triiodide [Pb(C12H24O6)I]I3 and Diiodothallium(18-crown-6) Tetraiodothallate [Tl(C12H24O6)I2](TlI4)

(MePh3P)2l8 has been prepared by the reaction of methyltriphenylphosphonium iodide with iodine in ethanol. It crystallizes in the monoclinic space group P21/n with a = 985.2(2), b = 1260.0(1), c = 1872.6(4) pm, β = 91.50(2)° and Z = 4. The crystal structure has been refined to R = 0.030 for 2882 reflections. It may be described as a layerlike packing of cations and anions. The anion with point symmetry 1̅ consists of two triiodide groups and a bridging iodine molecule forming a rather common nearly planar Z-shaped octaiodide ion I8 2-. [Cs(18-crown-6)]I3 has been prepared by the reaction of cesium iodide and 18-crown-6 with iodine in ethanol. It crystallizes in the triclinic space group P1̅ with a = 921.4(1), b = 1175.4(7), c = 1178.0(4) pm, a = 112.82(4), β = 94.24(7), γ = 98.60(3)° and Z = 2. The crystal structure has been refined to R = 0.038 for 3302 reflections. The geometry of the cation [Cs(18-crown-6)]+ and of the anion I3 - is quite normal. [Pb(18-crown-6)I]I3 has been prepared by the reaction of lead iodide and 18-crown-6 with iodine in dichloromethane. It crystallizes in the monoclinic space group P 21/n with a = 833.6(3), b = 1721.0(6), c = 1730.6(6) pm, β = 99.61(3)° and Z = 4. The crystal structure has been refined to R = 0.047 for 2772 reflections. It consists of complex cations [Pb(18-crown-6)I]+ and triiodide anions I3- forming weakly bonded ion pairs. [Tl(18-crown-6)I2](TlI4) has been prepared by the reaction of thallium(I)iodide and 18-crown-6 with iodine in dichloromethane. It crystallizes in the monoclinic space group P21/n with a = 1236.8(3), b = 1382.6(3), c = 1710.2(2) pm, β = 90.76(1)° and Z = 4. The crystal structure has been refined to R = 0.044 for 2916 reflections. It is composed of complex cations [Tl(18-crown-6)I2] + nd complex anions TlI4 - with their usual and expected geometry.

Untersuchungen an Polyhalogeniden, XX [1] Darstellung und Kristallstruktur von Tetra(methyltriphenylphosphonium)docosaiodid (MePh3P)4I22 / Studies of Polyhalides, XX [1] Preparation and Crystal Structure of Tetra(methyltriphenylphosphonium)docosaiodide (MePh3P)4I22

The new compound (MePh3P)4I22 has been prepared by the reaction of Ph3MePI with iodine in a mixture of methanol and dichloromethane. It crystallizes in the triclinic space group P1̅ with a = 1018.4(3), b = 1333.0(4), c = 2042.9(6) pm, a = 88.56(2), β = 78.05(2), γ = 76.03(2)° and Z = 1. The crystal structure has been refined to RF = 0.0487 for 5525 reflections. It may be described as a layer-like packing of cations [CH3(C6H3)3P]+ and anions I22 4- divided in one I12 2- and two I5 - groups. The central I12 2- anion with point symmetry Q consisting of two L-shaped pentaiodide groups and a bridging iodine molecule is completed by two further end-on bonded pentaiodide ions with a rather short distance of 366.7(2) pm to the weakly bonded and nearly isolated docosaiodide ion.

Pr12I17Fe2: A Novel Hypostoichiometric Compound with Only Isolated Clusters

Reactions of the elements with PrI[sub 3] in sealed Nb containers at 860-920 [degrees]C yields Pr[sub 12]I[sub 17]Z[sub 2] for Z = Fe and Re. The new structure type was characterized for the former (P[bar 1], Z = 1, a = 11.798 (4) [angstrom], b = 11.791 (2) [angstrom], c = 9.830 (2) [angstrom], [alpha] = 114.87(2)[degrees], [beta] = 104.82(4)[degrees], [gamma] = 93.19(2)[degrees], R/R[sub w] = 3.2/3.8% for 2967 data, 143 variables). The unusually low I:Pr ratio for a phase with isolated clusters is achieved by seven I[sup i-i] bridges per cluster in which iodine simultaneously bridges metal edges in two clusters. The Z-centered Pr[sub 6]I[sub 12]-type clusters are joined into layers by three pairs of centric I[sup i-i] and (I[sup i-a]) bridges. The layers are further joined in the third direction by a unique planar I[sup i-i] plus other types of iodine bridges. The 2.75-[angstrom] Pr-Fe bonds appear to be particularly short.

Metallkomplexe mit 1,4,7-Trithiacyclononan: Kristallstrukturen von [CdI2 · C6H12S3]2 und [Hg(C6H12S3)2](HgI3)2 / Metal Complexes with 1,4,7-Trithiacyclononane: Crystal Structures of [CdI2 · C6H12S3]2 and [Hg(C6H12S3)2](HgI3)2

Crystals of the complexes [CdI2 · C6H12S3]2 (1) and [Hg(C6H12S3)2](HgI3)2 (2) were obtained by diffusion of 1,4,7-trithiacyclononane (9 S 3) in ethanol into aqueous solutions of cadmium iodide and mercuric iodide/potassium iodide, resp. Both compounds crystallize monoclinically,1: space group P21/n, Z = 4, a = 1207.1(5), b = 909.9(2), c = 1240.3(7) pm, β = 92.59(9)°; 2: P21/c, Z = 2, a = 804.7(6), b = 934.0(6), c = 2167.9(4) pm, β = 94.34(7)°. 1 is dimeric, consisting of two [CdI2 · 9S3] units, connected via iodine bridges. Crystals of 2 contain sandwich-like cations [Hg(9S3)2]2+ and [HgI3]- anions, forming chains via Hg ··· S and Hg ··· I bridges.

Untersuchungen an Polyhalogeniden, XII [1] Darstellung und Kristallstruktur von [K(Crypt-2.2.2)]l2I12 / Studies on Polyhalides, XII [1] / Preparation and Crystal Structure of [K(Crypt-2.2.2)]2I12

The new compound [K(Crypt-2.2.2)]2I12 has been prepared by the reaction of [K(Crypt-2.2.2)]I with iodine in a mixture of ethanol and dichloromethane. It crystallizes in the triclinic space group PĪ with a = 1201,5(5), b = 1213,4(5), c = 1432,1(2) pm, α = 69,11(2), β = 72,01(2), γ= 61,93(3) and Z = 1. The crystal structure has been refined to RF = 0.030 for 2882 reflections. The structure may be described as a layerlike packing of I12 2- anions and [K(Crypt-2.2.2)]+ cations. The anion with point symmetry Ci consists of two pentaiodide groups and a bridging iodine molecule.