Two new non‐centrosymmetric lithium salts of glycine: bis(glycine) lithium chromate monohydrate and bis(glycine) lithium molybdate

In bis­(glycine) lithium chromate monohydrate {systematic name: poly[aquadi‐μ‐glycinato‐μ‐tetra­oxochromato(VI)‐dilithium(I)]}, [CrLi₂(C₂H₅NO₂)₂O₄(H₂O)]_n, (I) (space group P2₁2₁2₁), and bis­(glycine) lithium molybdate {systematic name: poly[di‐μ‐glycinato‐μ‐tetra­oxomolybdato(VI)‐dilithium(I)]}, [Li₂Mo(C₂H₅NO₂)₂O₄]_n, (II) (space group P2₁), all atoms are located on general positions. The crystal structure of (I) is characterized by infinite chains of corner‐sharing [LiO₄] tetra­hedra, which are connected by glycine mol­ecules to form layers. [CrO₄] tetra­hedra are attached to the [LiO₄] tetra­hedra. Compound (II) contains dimers of [LiO₄] tetra­hedra which are connected by [MoO₄] tetra­hedra to form chains, which are in turn connected by glycine mol­ecules to form double layers.     

Na6(H2O)20(V10O28)·4H2O,a novel polyvanadate(V) with a three‐dimensional framework

The novel title polyvanadate(V), poly[[octa‐μ‐aqua‐dodecaaqua‐μ₄‐octacosaoxidodecavanadato‐hexasodium] tetrahydrate], [Na₆(H₂O)₂₀(V₁₀O₂₈)·4H₂O]_n, contains [V₁₀O₂₈]⁶⁻ anions which lie about inversion centres and have approximate 2/m symmetry and which are linked to [Na₃(H₂O)₁₀]³⁺ cations through two terminal and two μ₂‐bridging O atoms. The structure contains three inequivalent Na⁺ cations, two of which form [Na₂(H₂O)₈]_n chains, which are linked via NaO₆ octahedra involving the third Na⁺ ion, thus forming a three‐dimensional framework.     

A lithium complex of pyridine‐2,6‐dicarboxylic acid

The crystal structure of catena‐poly­[[(6‐carboxy­pyridine‐2‐carb­oxyl­ato‐κ³O,N,O′)­lithium(I)]‐μ‐aqua‐κ²O:O], [Li(C₇H₄NO₄)­(H₂O)]_n, contains the Li⁺ ion coordinated to two O atoms and the N atom of the 6‐carboxy­pyridine‐2‐carboxyl­ate ligand, and to two water O atoms, forming a pentavalent coordination geometry. The molecule resides on a mirror plane which contains the Li and N atoms, the para‐CH unit, and the O atom of the coordinated water mol­ecule. The O atom of the water mol­ecule is coordinated to two Li atoms, forming an infinite polymeric chain.     

A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.     

Calcium(II) meso‐2,3‐di­phenyl­succinate heptahydrate

The title compound, [Ca(C₁₆H₁₂O₄)(H₂O)₆]·H₂O, adopts a conformation about the central C—C bond that places the two carboxylate groups in an anti orientation. The crystal consists of layers of two‐dimensional arrays of 2,3‐di­phenyl­succinate dianions which are linked by bridging Ca²⁺ cations. The unit cell contains two Ca²⁺ cations in an unusual four‐membered Ca—O—Ca—O ring in which the bridging O atoms belong to water mol­ecules rather than carboxyl­ates, i.e. poly­[[[di‐μ‐aqua‐bis­[penta­aqua­calcium(II)]]‐μ‐(meso‐2,3‐di­phenyl­succinato‐O:O′)] succinate dihydrate].     

A novel zirconium polyoxometalate compound: (NH4)9[Zr2(μ‐OH)(H2O)2(AsOH)2(AsW7O28)(AsW10O36)]·26H2O

The crystal structure of the title compound, nona­ammonium (arsenic decatungstido)(arsenic heptatungstido)­di­aqua‐μ‐hydroxo‐(hydroxy­arsenido)­di­zir­conium hexa­cosa­hydrate, which was ob­tained from the reaction of [NaAs₄W₄₀O₁₄₀]²⁷⁻ with Zr^IV, has been determined. The anionic complex consists of two hydroxyl‐bridged seven‐coordinate capped trigonal‐prismatic zirconium ions, which are bonded to an [AsW₁₀O₃₆]⁹⁻ anion and to an [AsW₇O₂₈]¹¹⁻ anion that has two {AsOH}²⁺ capping units. The asymmetric unit contains half of the complex, with one crystallographically independent Zr atom. Crystallographic m symmetry imposed by the monoclinic C2/m space group gives rise to the asymmetric unit comprising half of the complex with one crystallographically independent Zr atom.     

[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.     

Strontium diibuprofenate dihydrate,strontium malonate sesquihydrate,strontium diascorbate dihydrate and strontium 2‐oxidobenzoate hydrate at 120 K

Four strontium(II) salts with organic acids have been studied. Poly[diaquadi‐μ‐ibuprofenato‐strontium(II)] or poly­[diaqua­bis[μ‐2‐(4‐isobutyl­phen­yl)­propionato]­strontium(II)], [Sr(C₁₃H₁₇O₂)₂(H₂O)₂]_n, crystallizes with eight‐coordinated Sr atoms. The coordination polyhedra are inter­connected by edge‐sharing to form chains. The Sr coordination chains are packed into layers, which are stacked by van der Waals inter­actions. Poly[μ‐aqua‐diaquadi‐μ‐malonato‐distrontium(II)], [Sr₂(C₃H₂O₄)₂(H₂O)₃]_n, crystallizes with nine‐coordinated Sr atoms three‐dimensionally inter­connected into a framework structure. One of the two crystallographically independent water mol­ecules is located on a twofold axial site. catena‐Poly[[diaqua­(ascorbato)strontium(II)]‐μ‐ascorbato], [Sr(C₆H₇O₆)₂(H₂O)₂]_n, crystallizes with isolated eight‐coordinated Sr polyhedra. One of the ascorbate ligands bridges two Sr atoms, forming zigzag polyhedral ascorbate chains. These chains are tied together by a three‐dimensional hydrogen‐bonding network. Poly[aqua‐μ‐2‐oxidobenzoato‐strontium(II)], [Sr(C₇H₄O₃)(H₂O)]_n, crystallizes with eight‐coordinated Sr atoms. The polyhedra are inter­connected by face‐ and edge‐sharing into layers. These layers are stacked by van der Waals forces between the protruding 2‐oxidobenzoate ligands.     

[Cd{C2(COO)2}(H2O)3]·H2O,the first cadmium salt of acetylenedicarboxylic acid

In catena‐poly­[[[tri­aqua­cadmium(II)]‐μ‐acetyl­enedi­carboxyl­ato‐κ⁴O,O′:O′′,O′′′] hydrate], {[Cd(C₄O₄)(H₂O)₃]·­H₂O}_n, the Cd^II atom is coordinated by two bidentate carboxyl­ate groups and three water mol­ecules, thus forming a sevenfold coordination polyhedron with all atoms located on general sites. These polyhedra are connected by the bifunctional acetyl­enedi­carboxyl­ate ligands, forming zigzag chains running parallel to [120]. Hydro­gen bonds, which involve the non‐coordinated water mol­ecule, connect these chains to form a three‐dimensional framework.     

Mixed‐ligand MnII and CuII complexes with alternating 2,2′‐bipyrimidine and terephthalate bridges

The novel polymeric complexes catena‐poly[[diaquamanganese(II)]‐μ‐2,2′‐bipyrimidine‐κ⁴N¹,N^1′:N³,N^3′‐[diaquamanganese(II)]‐bis(μ‐terephthalato‐κ²O¹:O⁴)], [Mn₂(C₈H₄O₄)₂(C₈H₆N₄)(H₂O)₄]_n, (I), and catena‐poly[[[aquacopper(II)]‐μ‐aqua‐μ‐hydroxido‐μ‐terephthalato‐κ²O¹:O^1′‐copper(II)‐μ‐aqua‐μ‐hydroxido‐μ‐terephthalato‐κ²O¹:O^1′‐[aquacopper(II)]‐μ‐2,2′‐bipyrimidine‐κ⁴N¹,N^1′:N³,N^3′] tetrahydrate], {[Cu₃(C₈H₄O₄)₂(OH)₂(C₈H₆N₄)(H₂O)₄]·4H₂O}_n, (II), containing bridging 2,2′‐bipyrimidine (bpym) ligands coordinated as bis‐chelates, have been prepared via a ligand‐exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht²⁻) anions were found. In (I), two tpht²⁻ anions acting as bis‐monodentate ligands bridge the Mn^II centres in a parallel fashion. In (II), the tpht²⁻ anions act as endo‐bridges and connect two Cu^II centres in combination with additional aqua and hydroxide bridges. In this way, the binuclear [Mn₂(tpht)₂(bpym)(H₂O)₄] entity in (I) and the trinuclear [Cu₃(tpht)₂(OH)₂(bpym)(H₂O)₄]·4H₂O coordination entity in (II) build up one‐dimensional polymeric chains along the b axis. In (I), the Mn^II cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu^II cation is also on a special position (site symmetry ). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face‐to‐face π–π interactions [in (I)], forming three‐dimensional metal–organic frameworks. The Mn^II cation in (I) has a trigonally deformed octahedral geometry, whereas the Cu^II cations in (II) are in distorted octahedral environments. The Cu^II polyhedra are inclined relative to each other and share common edges.     

(Et4N)4[V4O12]·2H2O

The title compound, tetrakis(tetraethylammonium) cyclo‐tetra‐μ‐oxo‐tetrakis[dioxovanadium(V)] dihydrate, (C₈H₂₀N)₄[V₄O₁₂]·2H₂O, was obtained by reacting V₂O₅ with (C₂H₅)₄NOH. It consists of a discrete centrosymmetric molecular anion, [V₄O₁₂]^4?, where four tetrahedral VO₄ units share two vertices with each other to form a ring. A water mol­ecule is attached on each side of the ring through hydrogen bonds.     

Three yttrium crotonate complexes with diimines

The synthesis and crystal structures of three new yttrium crotonate (crot) compounds, associated with three different nitro­genous bases, namely 1,10‐phenanthroline (phen), 4‐­methyl‐1,10‐phenanthroline (mphen) and 2,2′‐bipyridyl­amine (bpa), are presented. All three compounds organize as centrosymmetric dimers, to give tetra‐μ‐crotonato‐bis[croto­nato(1,10‐phenanthroline)yttrium(III)] dihydrate, [Y₂(C₄H₅O₂)₆(C₁₂H₈N₂)₂]·2H₂O or [Y(crot)₃(phen)]₂·2H₂O, (I), tetra‐μ‐crotonato‐bis­[crotonato(4‐methyl‐1,10‐phenan­throline)­yttrium(III)] dihydrate, [Y₂(C₄H₅O₂)₆(C₁₃H₁₀N₂)₂]·2H₂O or [Y(crot)₃(mphen)]₂·2H₂O, (II), and tetra‐μ‐crot­onato‐bis­[di­aqua(crotonato)yttrium(III)] 2,2′‐bipyridyl­amine tetrasolvate, [Y₂(C₄H₅O₂)₆(H₂O)₄]·4C₁₀H₉N₃ or [Y(crot)₃(aq)₂]₂·4(bpa), (III). Complexes (I) and (II) are isomorphous, with the bases acting as chelating ligands. In complex (III), the coordination sphere is built up of carboxyl­ate and aqua ligands, with the non‐coordinated di­imine acting as included solvent.     

catena‐Poly­[[di­aqua­lithium(I)]‐μ‐[9H‐purine‐2,6(1H,3H)‐dionato‐O2:N7]]

In the title compound, [Li(C₅H₃N₄O₂)(H₂O)₂]_n, the coordinate geometry about the Li⁺ ion is distorted tetrahedral and the Li⁺ ion is bonded to N and O atoms of adjacent ligand mol­ecules forming an infinite polymeric chain with Li—O and Li—N bond lengths of 1.901 (5) and 2.043 (6) Å, respectively. Tetrahedral coordination at the Li⁺ ion is completed by two cis water mol­ecules [Li—O 1.985 (6) and 1.946 (6) Å]. The crystal structure is stabilized both by the polymeric structure and by a hydrogen‐bond network involving N—H?O, O—H?O and O—H?N hydrogen bonds.     

[Cu{C2(COO)2}(H2O)3]·H2O,the first copper complex of acetyl­ene­dicarboxyl­ic acid

In the title compound, catena‐poly­[[[tri­aqua­copper(II)]‐μ‐acetyl­enedi­carboxyl­ato‐κ²O:O′′] hydrate], {[Cu(C₄O₄)(H₂O)₃]·H₂O}_n, the Cu^II ion is coordinated by two monodentate carboxyl­ate groups in trans positions and three water mol­ecules, thus forming a fivefold coordination polyhedron that can be described as a distorted square pyramid. All atoms are located on general sites. The polyhedra are connected by bifunctional acetyl­ene­di­carboxyl­ate ligands, to form almost linear chains parallel to [001]. Hydro­gen bonds involving the non‐coordinated water mol­ecule connect these chains to form a three‐dimensional framework.     

Ba3Li2V2O7Cl4, a new vanadate with a channel structure

The tribarium dilithium divanadate tetrachloride Ba₃Li₂V₂O₇Cl₄ is a new vanadate with a channel structure and the first known vanadate containing both Ba and Li atoms. The structure contains four non‐equivalent Ba²⁺ sites (two with m and two with 2/m site symmetry), two Li⁺ sites, two nonmagnetic V⁵⁺ sites, five O²⁻ sites (three with m site symmetry) and four Cl⁻ sites (m site symmetry). One type of Li atom lies in LiO₄ tetrahedra (m site symmetry) and shares corners with VO₄ tetrahedra to form eight‐tetrahedron Li₃V₅O₂₄ rings and six‐tetrahedron Li₂V₄O₁₈ rings; these rings are linked within porous layers parallel to the ab plane and contain Ba²⁺ and Cl⁻ ions. The other Li atoms are located on inversion centres and form isolated chains of face‐sharing LiCl₆ octahedra.     

Three novel non‐centrosymmetric compounds of glycine: glycine lithium sulfate,glycine nickel dichloride dihydrate and glycine zinc sulfate trihydrate

The crystal structures of three compounds of glycine and inorganic materials are presented and discussed. The ortho­rhombic structure of glycinesulfatodilithium(I), [Li₂(SO₄)(C₂H₅NO₂)]_n, consists of corrugated sheets of [LiO₄] and [SO₄] tetrahedra. The glycine mol­ecules are located between these sheets. The main features of the monoclinic structure of di­aqua­di­chloro­glycinenickel(II), [NiCl₂(C₂H₅NO₂)(H₂O)₂]_n, are helical chains of [NiO₄Cl₂] octahedra connected by glycine mol­ecules. The orthorhombic structure of tri­aqua­glycinesulfatozinc(II), [Zn(SO₄)(C₂H₅NO₂)(H₂O)₃]_n, is made up of [O₃SOZnO₅] clusters. These clusters are linked by glycine mol­ecules into zigzag chains. All three compounds are examples of non‐centrosymmetric glycine compounds.     

The lithium chloride complex of the anti isomer of the bridged spherand C50H48O6

The structure of (11,12,24,25‐tetra­hydro‐28,34‐di­methoxy‐3,6,16,19,31,37‐hexa­methyl‐1,21[1′,3′]:8,14[1′′,3′′]‐di­benzeno‐10H,23H‐tetrabenzo­[f,h,o,z][1,5,10,14]­tetraoxa­cyclo­octa­decane)­lithium chloride monohydrate, anti‐[Li(C₅₀H₄₈O₆)]Cl·H₂O, at 100 K reveals that the host is less strained than that of the syn‐bridged isomer. There are two independent complex cations, each lying on a center of symmetry. Four short [1.944 (2)–1.998 (2) Å] and two long [2.381 (2) and 2.455 (2) Å] Li⁺?O distances provide six‐coordination in a distorted octahedral environment.     

Variation of hydrogen‐bonded networks in hexa­fluoro­phosphate salts of amidate‐bridged dirhodium(II,III) complexes with axial aqua ligands

In diaqua­tetra‐μ‐acetamidato‐κ⁴N:O;κ⁴O:N‐di­rhodium(II,III) hexa­fluoro­phosphate, [Rh₂(C₂H₄NO)₄(H₂O)₂]PF₆, and diaqua­tetra‐μ‐acetamidato‐κ⁴N:O;κ⁴O:N‐di­rho­dium(II,III)hexa­fluoro­phosphate dihydrate, [Rh₂(C₂H₄NO)₄(H₂O)₂]PF₆·2H₂O, the cations and anions lie on inversion centers. Diaqua­tetra‐μ‐propionamidato‐κ⁴N:O;κ⁴O:N‐dirhodium(II,III) hexa­fluoro­phosphate dihydrate, [Rh₂(C₃H₆NO)₄(H₂O)₂]PF₆·2H₂O, and diaqua­tetra‐μ‐butyramidato‐κ⁴N:O;κ⁴O:N‐dirhodium(II,III) hexa­fluoro­phosphate, [Rh₂(C₄H₈NO)₄(H₂O)₂]PF₆, crystallize with two crystallographically independent complexes that lie on inversion centers. In all of the structures, the dirhodium units are hydrogen bonded to one another. The hydrogen‐bonded networks vary with the alkyl substituents.     

A cyano‐bridged dinuclear 4f–3d array

A cyano‐bridged bimetallic 4f–3d complex, tri­aqua‐1κ³O‐μ‐cyano‐1:2κ²N:C‐penta­cyano‐2κ⁵C‐tetrakis(2‐pyrrolidone‐1κO)­chromium(III)­dysprosium(III) dihydrate, [CrDy(C₄H₇NO)₄(CN)₆(H₂O)₃]·2H₂O, has been prepared and characterized by X‐ray crystallographic analysis. The structure consists of a neutral cyano‐bridged Dy–Cr dimer. A hydrogen‐bonded three‐dimensional architecture is formed through N—H?O, O—H?N and O—H?O hydrogen bonds.     

Cadmium nitrate coordination polymers with substituted pyridazino[4,5‐d]pyridazines

catena‐Poly[[aquabis(nitrato‐κ²O,O′)cadmium(II)]‐μ‐1,2,3,6,7,8‐hexa­hydro­cinnolino[5,4,3‐cde]cinnoline‐κN¹:κN⁶], [Cd(NO₃)₂(C₁₂H₁₂N₄)(H₂O)]_n, (I), and catena‐poly[[[bis(nitrato‐κ²O,O′)cadmium(II)]‐μ‐2,2,7,7‐tetra­methyl‐1,2,3,6,7,8‐hexahydro­cinnolino[5,4,3‐cde]cinnoline‐κN¹:κN⁶] chloro­form solvate], {[Cd(NO₃)₂(C₁₂H₁₂N₄)]·CHCl₃}_n, (II), are the first structurally examined cadmium–pyridazine coordination compounds. They possess one‐dimensional polymeric structures supported by the bidentate bridging function of the cinnolino[5,4,3‐cde]cinnoline ligands, which lie about inversion centres. The Cd atoms are seven‐coordinated in (I) and six‐coordinated in (II), involving two bidentate nitrate groups [Cd—O = 2.229 (2)–2.657 (2) Å], two N atoms of the cinnoline ligands [Cd—N = 2.252 (2)–2.425 (2) Å], and, additionally, a water O atom in (I) [Cd—O = 2.284 (2) Å]. In (I), the coordinated organic and aqua ligands form an intra­molecular O—H⋯N hydrogen bond [O⋯N = 2.730 (3) Å].