Li+ cation coordination in [Li2(CF3SO3)2(diglyme)] and [Li3(C2F3O2)3(diglyme)]

The title compounds, poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­methanesulfonato‐lithium(I)], [Li₂(CF₃SO₃)₂(C₆H₁₄O₃)]_n, and poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­acetato‐dilithium(I)‐μ₃‐tri­fluoro­acetato], [Li₃(C₂F₃O₂)₃(C₆H₁₄O₃)]_n, consist of one‐dimensional polymer chains. Both structures contain five‐coordinate Li⁺ cations coordinated by a tridentate diglyme [bis(2‐methoxy­ethyl) ether] mol­ecule and two O atoms, each from separate anions. In both structures, the [Li(diglyme)X₂]^? (X is CF₃SO₃ or CF₃CO₂) fragments are further connected by other Li⁺ cations and anions, creating one‐dimensional chains. These connecting Li⁺ cations are coordinated by four separate anions in both compounds. The CF₃SO₃^? and CF₃CO₂^? anions, however, adopt different forms of cation coordination, resulting in differences in the connectivity of the structures and solvate stoichiometries.     

A new rubidium beryllium borate,RbBe4(BO3)3

Single crystals of a new rubdidium beryllium borate, RbBe₄(BO₃)₃, have been obtained by spontaneous nucleation from a high‐temperature melt. This new ortho­rhom­bic (Pnma) structure type contains [Be₂BO₄]⁻ rings, made of two BeO₄ tetra­hedra and one BO₃ triangle, which constitute the basic structural units. The m plane runs through the B and one of the O atoms and intersects the ring. These rings form chains in the a direction, which are connected in the b and c directions to form zeolite‐type cages in which the Rb⁺ cations are located, at sites of m symmetry.     

Lithium zincopyrophosphate,Li2Zn3(P2O7)2

The title compound, dilithium(I) trizinc(II) bis[diphosphate(4−)], is the first quaternary lithium zincopyrophosphate in the Li–Zn–P–O system. It features zigzag chains running along c, which are built up from edge‐sharing [ZnO₅] trigonal bipyramids. One of the two independent Zn sites is fully occupied, whereas the other is statistically disordered by Zn²⁺ and Li⁺ cations, although the two Zn sites have similar coordination environments. Li⁺ cations occupy a four‐coordinated independent site with an occupancy factor of 0.5, as well as being disordered on the partially occupied five‐coordinated Zn site with a Zn²⁺/Li⁺ ratio of 1:1.     

RbLi2Ga2(BO3)3

The structure of rubidium dilithium digallium tris­(borate), RbLi₂Ga₂(BO₃)₃, contains two‐dimensional sheets of open‐branched rings of GaO₄ tetrahedra and planar BO₃ triangles that are joined by LiO₄ tetrahedra to form a three‐dimensional framework. Ten‐coordinate Rb atoms lie on twofold axes and occupy channels within the framework that extend along the b axis.     

Synthesis and Crystal Structure of the two Lithium Hypersilylcuprates LiCu2[Si(SiMe3)3]3 and [Li7(OtBu)6][Cu2{Si(SiMe3)3}3]

The two hypersilylcuprates LiCu₂Hyp₃ ( 2 ) and [Li₇(O^tBu)₆][Cu₂Hyp₃] ( 3 ) (Hyp = Si(SiMe₃)₃) were synthesized by reactions of unsolvated lithium hypersilanide, LiHyp with hypersilylcopper and CuO^tBu, respectively. Both contain the novel A‐frame trihypersilyldicuprate anion [Cu₂Hyp₃]^–. In the former case a molecular compound is produced containing intimate ion pairs. In the latter case the cuprate anion and the unique large [Li₇(O^tBu)₆]⁺ cation form a salt‐like compound, only sparingly soluble in unpolar solvents. According to NBO analyses the bonding within the trihypersilyldicuprate moiety is best described by interaction of a bridging lewis‐basic hypersilanide anion with two lewis‐acidic hypersilyl copper fragments.     

Li2Eu3Br2[BO3]2: A New Europium(II) Halide Oxoborate with Yellow Luminescence

The europium(II) oxoborate Li₂Eu₃Br₂[BO₃]₂ featuring lithium and bromide ions was synthesized by the reaction of Eu₂O₃ with Li[BH₄] as lithium- and boron- as well as EuBr₃ as bromide-source at 750 °C for 24 h in silica-jacketed sealed niobium capsules. The yellow, air-stable and yellow fluorescent compound crystallizes in the trigonal space group R3 m (a = 1049.06(7) pm, c = 2993.1(3) pm, c/a = 2.853, Z = 12). The two crystallographically distinguishable Eu²⁺ cations show either an eightfold coordination as bicapped trigonal prism ([EuO₆Br₂]^12–) or a ninefold coordination as monocapped square antiprism ([EuO₅Br₄]^12–). All oxygen atoms stem from isolated triangular [BO₃]^3– anions and the Li⁺ cations reside in octahedral voids provided by both oxygen atoms and Br^– anions.     

Mixed cobalt(III) complexes with aromatic amino acids and di­amines. III.

The title compound, [Co(C₉H₁₀NO₃)₂(C₂H₈N₂)]Cl·4H₂O, is one of six possible diastereomers of the (1,2‐di­amino­ethane)­bis(S‐tyrosinato)­cobalt(III) complex. The cobalt(III) ion has an octahedral coordination, with three five‐membered chelate rings which have deformed coordination angles and coordinated O atoms in trans positions. In comparison with the previously reported crystal structure of the Δ‐C₁‐cis(O) diastereomer [Miodragovi?et al. (2001). Enantiomer, 6 , 299–308], the compound presented in this paper has more planar five‐membered amino­carboxyl­ate rings. Complex cations, chloride anions and water mol­ecules of crystallization are linked together by a network of hydrogen bonds. The chloride anions lie approximately between two Co atoms and form hydrogen bonds with all coordinated NH₂ groups. In the crystal structure, there is a weak intermolecular π?π interaction between the phenyl rings.     

Reaktionen von tBuPLi2 mit Carbodiimiden

Reaction of ^tBuPLi₂ with Carbodiimides The reaction of bis(cyclohexyl)carbodiimide with ^tBuPLi₂ in THF at 20 °C leads to the tetranuclear Li‐complex [Li₄(THF)₂{^tBuP([^cHexN]₂C)₂}₂] ( 1 ). No addition on the carbodiimide but a silyl transfer was observed under similar conditions during the treatment of bis(trimethylsilyl)carbodiimide with ^tBuPLi₂ to give the lithium salts ^tBuP(SiMe₃)Li and [Li(THF)(Me₃SiN‐C≡N)]_n ( 2 ). 1 was characterized by NMR, IR and RE spectroscopy, mass spectrometry and X‐ray analyses. Theoretical calculations were performed for 1 . According to the structural investigations 1 consists ofa central centrosymmetrical twelve‐membered Li₂N₄C₄P₂ ring adjacent by two six‐membered LiN₂C₂P rings. The peripheric Li⁺ cations posssess coordination number (cn) 3 buildt‐up by two N atoms and a THF ligand, while the two central Li⁺ cations possess only cn 2. However, the theoretical calculations have shown no relevant bonding Li···Li or Li···P interaction.     

(C4N2H12)[(GeO2)3(BO1.5F)2], a layered borogermanate containing three‐ and nine‐membered rings

A new borogermanate, viz. piperazine‐1,4‐di­ium di­fluoro­nona­oxo­tri­germanium­di­boron, (C₄H₁₂N₂)[(GeO₂)₃(BO_1.5F)₂], was solvo/hydro­thermally synthesized. The crystal structure consists of layers composed of three‐membered‐ring Ge₃O₉ subunits and nine‐membered‐ring channels formed by six GeO₄ tetrahedra and three BO₃F tetrahedral pairs. The diprotonated piperazine cations, which lie about inversion centres, are located between adjacent layers and connect the layers via hydrogen bonds.     

catena‐Poly­[[tri‐n‐butyl­tin]‐μ‐N‐(1‐naphthyl)­maleamato]

The crystal structure of catena‐poly­[[tri‐n‐butyl­tin]‐μ‐3‐(1‐naph­thyl­amino­carbonyl)­acrylato‐κ²O¹:O³], [Sn(C₄H₉)₃(C₁₄H₁₀NO₃)]_n, is composed of polymeric chains wherein the metal center exhibits a distorted trigonal‐bipyramidal geometry, with three n‐butyl groups defining the trigonal plane [mean Sn—C 2.133 (7) Å] and the axial positions being occupied by the carboxyl­ate O atoms of two different N‐(1‐naphthyl)­maleamate ligands with inequivalent Sn—O distances [2.167 (4) and 2.457 (4) Å]. The N‐(1‐naphthyl)­maleamate fragment forms an essentially planar seven‐membered ring involving an intramolecular N—H?O hydrogen bond.     

Poly[(acetone)tetraaqua[μ6‐ethyl (dichloromethylene)diphosphonato][μ5‐ethyl (dichloromethylene)diphosphonato]tribarium(II)]

The novel title compound, [Ba₃(C₃H₅Cl₂O₆P₂)₂(C₃H₆O)(H₂O)₄]_n, has a polymeric two‐dimensional network structure which lies parallel to the (10) plane. The asymmetric unit consists of three independent Ba²⁺ ions, two of them eight‐coordinated and the third nine‐coordinated, and two independent ethyl (dichloromethylene)diphosphonate(3−) ligands, one acetone ligand and four aqua ligands. The coordination environments around the BaO₈ polyhedra are best described as bicapped trigonal prismatic, while the BaO₉ polyhedron is in a distorted tricapped trigonal prismatic geometry. The two diphosphonate ligands adopt different coordination modes. Both ligands chelate three metal cations, but one is coordinated to six metal cations in total and forms two six‐membered and one four‐membered chelate ring, while the other is coordinated to five metal cations in total and forms one six‐membered and two four‐membered chelate rings, the fifth unsubstituted O atom remaining uncoordinated.     

Li2B12 and Li3B12: Prediction of the Smallest Tubular and Cage‐like Boron Structures

An intriguing structural transition from the quasi‐planar form of B₁₂ cluster upon the interaction with lithium atoms is reported. High‐level computations show that the lowest energy structures of LiB₁₂, Li₂B₁₂, and Li₃B₁₂ have quasi‐planar (C_s), tubular (D_6d), and cage‐like (C_s) geometries, respectively. The energetic cost of distorting the B₁₂ quasi‐planar fragment is overcompensated by an enhanced electrostatic interaction between the Li cations and the tubular or cage‐like B₁₂ fragments, which is the main reason of such drastic structural changes, resulting in the smallest tubular (Li₂B₁₂) and cage‐like (Li₃B₁₂) boron structures reported to date.     

Pr(BO2)3 und PrCl(BO2)2: Zwei meta‐Borate des Praseodyms im Vergleich

Pr(BO₂)₃ and PrCl(BO₂)₂: Two Praseodymium meta‐Borates in Comparison Single‐crystalline PrCl(BO₂)₂ can be obtained by the reaction of praseodymium, Pr₆O₁₁ and PrCl₃ with a small excess of B₂O₃ in evacuated silica tubes after seven days at 850 °C. If NaCl is additionally used as flux, single crystals of Pr(BO₂)₃ dominate the main product. Both praseodymium(III) meta‐borates are air and water stable. The crystals of PrCl(BO₂)₂ emerge as long, thin, pale green needles which tend to severe twinning due to their fibrous habit. The crystal structure (triclinic, P1¯; a = 420.56(4), b = 655.42(7), c = 808.34(8) pm, α = 82.361(8), β = 89.173(9), γ = 71.980(7)°, Z = 2) exhibits zigzag chains {[(B1)o^t_1/1O^e_2/2(B2)O^t_1/1O^e_2/2]²⁻} (≡ {[BO₂]⁻}) of corner‐linked [BO₃]³⁻ triangles with syndiotactic orientation of the terminal oxygen atoms which are running parallel to the [100] direction. The Pr³⁺ cations are surrounded by three Cl⁻ and seven O²⁻ anions with the shape of a tetracapped trigonal prism. The green, transparent crystals of Pr(BO₂)₃ (monoclinic, C2/c; a= 984.98(9), b = 809.57(8), c = 641.02(6) pm, β = 126.783(9)°, Z = 4) appear either lath‐shaped or rather spherical. In the crystal structure the B³⁺ cations reside both in trigonal planar as well as in tetrahedral coordination of oxygen atoms. Both types of borate polyhedra ([BO₃]³⁻ and [BO₄]⁵⁻) are linked via corners to form chains of the composition {[(B2)‐O^t_1/1O^e_2/2(B1)O^e_4/2(B2)O^t_1/1O^e_2/2]³⁻} (≡ {[BO₂]⁻}) which run parallel [101]. The coordination sphere of the Pr³⁺ cations consists of ten oxide anions which build up a bicapped square antiprism.     

[Ni(terpy)(H2O)]‐trans‐[Ni‐(μ‐CN)2‐(CN)2]n,a one‐dimensional linear tetra­cyano­nickelate chain

The one‐dimensional chain catena‐poly­[[aqua(2,2′:6′,2′′‐terpyridyl‐κ³N)­nickel(II)]‐μ‐cyano‐κ²N:C‐[bis­(cyano‐κC)nickelate(II)]‐μ‐cyano‐κ²C:N], [Ni(terpy)(H₂O)]‐trans‐[Ni‐μ‐(CN)₂‐(CN)₂]_n or [Ni₂­(CN)₄­(C₁₅H₁₁N₃)(H₂O)], consists of infinite linear chains along the crystallographic [10] direction. The chains are composed of two distinct types of nickel ions, paramagnetic octahedral [Ni(terpy)(H₂O)]²⁺ cations (with twofold crystallographic symmetry) and diamagnetic planar [Ni(CN)₄]^2? anions (with the Ni atom on an inversion center). The [Ni(CN)₄]^2? units act as bidentate ligands bridging through two trans cyano groups thus giving rise to a new example of a trans–trans chain among planar tetra­cyano­nickelate complexes. The coordination geometry of the planar nickel unit is typical of slightly distorted octahedral nickel(II) complexes, but for the [Ni(CN)₄]^2? units, the geometry deviates from a planar configuration due to steric interactions with the ter­pyridine ligands.     

Synthesis,Structure and Thermodynamic Property of a New Lithium Borate: Li4[B8O13(OH)2]·3H2O

A new hydrated lithium borate, Li₄[B₈O₁₃(OH)₂]·3H₂O, has been hydrothermally synthesized and characterized by single crystal X‐ray diffraction, FT‐IR spectroscopy, simultaneous TGA‐DTA and chemical analysis. It crystallizes in the triclinic, space group , a=8.4578(5) Å, b=8.7877(5) Å, c=10.8058(7) Å, α=87.740(3)°, β=71.819(3)°, γ=61.569(3)°, Z=2, V=665.26(7) ų, D_c=2.043 g/cm³. Its crystal structure features polyborate anionic layers with the larger odd 13‐membered boron rings constructed by [B₈O₁₃(OH)₂]^4? FBBs. Through designing the thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be ?(7953.8±6.6) kJ·mol^?1 by using a heat conduction microcalorimeter.     

Synthese und Eigenschaften der Di‐tert‐butylphosphide [M(PtBu2)2]2 (M = Zn,Hg) und [Cu(PtBu2)]4

Syntheses and Properties of Di‐tert‐butylphosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ The phosphides [M(PtBu₂)₂]₂ (M = Zn, Hg) and [Cu(PtBu₂)]₄ are accessible from reaction of LiPtBu₂ with ZnI₂, HgCl₂ and CuCl, respectively. [M(PtBu₂)₂]₂ (M = Zn, Hg) are dimers in the solid state. X‐ray structural analyses of these phosphides reveal that [M(PtBu₂)₂]₂ (M = Zn, Hg) contain four‐membered M₂P₂‐rings whereas [Cu(PtBu₂)]₄ features a planar eight‐membered Cu₄P₄‐ring. Degradation reaction of LiPtBu₂(BH₃) in the presence of HgCl₂ results in the dimeric phosphanylborane BH₃ adduct [tBu₂PBH₂(BH₃)]₂. X‐ray quality crystals of [tBu₂PBH₂(BH₃)]₂ (monoclinic, P2₁/n) are obtained from a pentane solution at 6 °C. According to the result of the X‐ray structural analysis, the O₂‐oxidation product of [Hg(PtBu₂)₂]₂, [Hg{OP(O)(tBu)OPtBu₂}(μ‐OPtBu)]₂, features in the solid state structure two five‐membered HgP₂O₂‐rings and a six‐membered Hg₂P₂O₂‐ring. Herein the spiro‐connected Hg atoms are member of one five‐membered and of the six‐membered ring.     

Bis(acesulfamato‐κ2O4,N)bis­(3‐methyl­pyridine)copper(II)

In the crystal structure of the title compound {systematic name: bis­[6‐methyl‐1,2,3‐oxa­thia­zin‐4(3H)‐one 2,2‐dioxide(1−)‐κ²N³,O⁴]bis­(3‐meth­yl­pyridine)copper(II)}, [Cu(C₄H₄NO₄S)₂(C₆H₇N)₂], the Cu^II centre resides on a centre of symmetry and has an octa­hedral geometry that is distorted both by the presence of four‐membered chelate rings and because of the Jahn–Teller effect. The equatorial plane is formed by the N atoms of two methyl­pyridine ligands and by the more basic O atoms of the acesulfamate ligands, while the weakly basic N atoms of these ligands are in elongated axial positions with a misdirected valence. The crystal is stabilized by two inter­molecular C—H⋯O inter­actions involving the methyl and CH groups, and the sulfonyl O atoms of the acesulfamate group.     

Structural,electronic, and magnetoresponsive properties of triangular lanthanide clusters and their free‐standing nitrides

The molecular and electronic structures, stabilities, bonding features, and magnetoresponsive properties of three‐membered [c‐Ln₃]^+/0/? (Ln = La, Ce, Pr, Nd, Gd, Lu) and heterocyclic six‐membered [c‐Ln₃E₃]^q (Ln = La, Ce, Pr, Nd, Gd, Lu; E = C, N; q = 0 or 1) rings have been investigated by means of electronic structure calculation methods at the DFT level. The [c‐Ln₃]^+/0/? clusters are predicted to be bound with respect to dissociation to their constituent atoms, the estimated binding energies ranging from 45.8 to 2056.4 kJ/mol. The [c‐Ln₃] rings capture easily a planar three‐coordinated nitrogen atom at the center or above the center of the ring yielding the lanthanide nitride clusters [c‐Ln₃(μ₃‐N)] adopting a planar geometry, except [c‐La₃(μ₃‐N)] which exhibits pyramidal geometry. The [c‐Ln₃(μ₃‐N)] clusters are predicted to be bound, with respect to dissociation to N (⁴S) atom and [c‐Ln₃] clusters in their ground states, the binding energies ranging from 53.9 to 257.9 kcal/mol. The six‐membered [c‐Ln₃E₃]^q rings are predicted to be bound with respect to dissociation to LnE^q monomers in their ground states with dissociation energies in the range of 173.8 to 318.0 kcal/mol. Calculation of the NICS_zz‐scan curves of the clusters predicted a “hermaphrodic” magnetic response of the [c‐Ln₃]^+/0/? and heterocyclic six‐membered [c‐Ln₃E₃]^q rings, manifested by the coexistence of successive diatropic (aromatic) and paratropic (antiaromatic) zones. The [c‐La₃]^+/0/? and [c‐Lu₃]^? are predicted to be weakly antiaromatic, the [c‐Lu₃]^0/+, [c‐Lu₃C₃]⁺, and [c‐Lu₃N₃] double (σ+π) aromatic, and the [c‐Gd₃C₃] and [c‐Gd₃N₃]⁺ rings (σ+δ)‐aromatic systems. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

catena‐Poly[sodium(I)‐μ‐tetra­ethoxy­borato]

The title compound, [Na(C₈H₂₀BO₄)]_n, has twofold crystallographic symmetry, with the Na⁺ cations bound by four O atoms [Na—O = 2.251 (3) Å]. The tetra­ethoxy­borate anion acts as a bridging ligand to form one‐dimensional polymers running along the twofold crystal axis. The crystal was treated as a racemic twin.