A hydrated ethyl­ene­di­ammonium salt of a new polymeric polyoxoanion: (H2en)4[Co(H2O)2(OH)2(VO)6(HPO4)4(PO4)4]·3H2O

The title compound, tetrakis­(ethyl­enedi­ammonium) tetra‐μ‐hydrogenphosphato‐di‐μ‐hydro­xo‐ tetra‐μ‐phosphato‐bis­(aqua­cobalt)­hexakis­(oxovanadium) trihydrate, was synthesized hydro­thermally at moderate temperature. The structure consists of diprotonated ethyl­enedi­ammonium cations and layers of the polyanions. The polyanion contains four PO₄ tetrahedra and three VO₅ square pyramids that are linked through corner‐sharing by alternating P—O—V, which gives rise to a chain. The chains, connected by CoO₄(H₂O)₂ octahedra, form layers, resulting in a two‐dimensional layered structure. The Co—O distances are in the range 1.984 (3)–2.038 (4) Å, the P—O distances 1.508 (3)–1.575 (3) Å and the V—O distances 1.585 (3)–2.010 (3) Å.     

Barium vanadium(III) hydrogen ­phosphate,Ba3V2(HPO4)6

Hydro­thermally prepared Ba₃V₂(HPO₄)₆ contains a three‐dimensional network of V^IIIO₆ octahedra [d_av(V—O) = 2.014 (2) Å] and HPO₄ [d_av(P—O) = 1.537 (3) Å] tetrahedra, sharing vertices. 12‐coordinate Ba²⁺ cations [d_av(Ba—O) = 2.944 (4) Å] complete the structure.     

Synthetic mansfieldite,AlAsO4·2H2O

Hydro­thermally prepared mansfieldite, AlAsO₄·2H₂O (aluminium arsenate dihydrate), contains a vertex‐sharing three‐dimensional network of cis‐AlO₄(H₂O)₂ octahedra and AsO₄ tetrahedra [d_av(Al—O) = 1.907 (2) Å, d_av(As—O) = 1.685 (2) Å and θ_av(Al—O—As) = 134.5 (1)°].     

Bimetallic assemblies, [Ni(en)2]3[M(CN)6]2·3H2O (en = H2NCH2CH2NH2; M = Fe,Co)

The reaction between tris(ethyl­enedi­amine)­nickel(II) cations and hexa­cyanometallate(III) anions (M = Fe, Co) yields ordered bimetallic assemblies, catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­iron‐N,N′)] trihydrate] and catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­cobalt‐N,N′)] trihydrate], [{Ni(C₂H₈N₂)₂}₃{M(CN)₆}₂]·3H₂O, in which both cis and trans [Ni(en)₂] and [M(CN)₆] moieties are linked to give S‐shaped Ni–NC–M–CN–Ni–NC–M–CN–Ni units which are cross­linked to give ribbons parallel to the b axis. The two compounds are isomorphous with mean metal–ligand distances Fe—C = 1.940 (3), Co—C = 1.844 (3) and Ni—N = 2.102 (2) Å for the iron, and 2.105 (3) Å for the cobalt compound. These compounds appear to be identical with those formulated as [Ni(en)₂]₃[M(CN)₆]₂·2H₂O [Ohba, Maruona, Okawa, Enoki & Latour (1994). J. Am. Chem. Soc. 116 , 11566–11567; Ohba, Fukita & Okawa (1997). J. Chem. Soc. Dalton Trans. pp. 1733–1737] which were indexed on a smaller unit cell and described as disordered.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Molecular building blocks for solid‐state chalcogenides: solvothermal synthesis of [Mn(en)3]Te4 and [Fe(en)3]2(Sb2Se5)

Two new molecular metal chalcogenides, tris­(ethyl­enedi­amine‐N,N′)­manganese(II) tetratelluride, [Mn(C₂H₈N₂)₃]Te₄, (I), and bis­[tris­(ethyl­enedi­amine‐N,N′)­iron(II)] penta­seleno­diantimonate(III), [Fe(C₂H₈N₂)₃]₂(Sb₂Se₅), (II), containing the isolated molecular building blocks Te₄^2? and Sb₂Se₅^4?, have been synthesized by solvothermal reactions in an ethyl­enedi­amine solution at 433 K. The anion Te₄^2? in (I) is a zigzag oligometric chain with Te—Te bond lengths in the range 2.709–2.751 Å. There is a very short contact [3.329 (1) Å] between a pair of neighboring Te₄^2? anions. In (II), each Sb atom is surrounded by three Se atoms to give a tripodal coordination. One of the three independent Se atoms is a μ₂‐bridging ligand between two Sb atoms; the other two are terminal.     

Caesium vanadium selenite,Cs(VO2)3(SeO3)2

Caesium vanadium(V) selenite contains infinite sheets of distorted vertex‐sharing VO₆ octahedra, capped by selenite groups [d_av(V—O) = 1.927 (4) Å and d_av(Se—O) = 1.709 (3) Å]. Interlayer caesium cations complete the structure [d_av(Cs—O) = 3.365 (4) Å].     

Hexagonal ammonium zinc ­phosphate, (NH4)ZnPO4, at 10 K

The title compound, (NH₄)ZnPO₄–HEX, is built up from a three‐dimensional network of ZnO₄ and PO₄ tetrahedra [d_av(Zn—O) = 1.9400 (7) Å and d_av(P—O) = 1.5396 (7) Å], fused together via Zn—O—P links [θ_av = 133.47 (4)°]. An undisordered linear Zn—O—P bond occurs (all three atoms lie on a threefold axis). Extra‐framework NH₄⁺ cations, which interact with the [ZnPO₄]^? framework by hydrogen bonds, complete the crystal structure.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.     

Lanthanum selenite,La2(SeO3)3

Hydro­thermally prepared La₂(SeO₃)₃ contains a three‐dimensional network of LaO₁₀ polyhedra [d_av(La—O) = 2.622 (3) Å] and SeO₃ pyramids [d_av(Se—O) = 1.691 (3) Å]. One of the SeO₃ pyramids is in a general position and the other has crystallographic m symmetry. There are pseudo‐channels in the [010] direction which are probably associated with the Se^IV lone pairs.     

The three‐dimensional coordination polymer tetra­ethyl­ammonium (ethyl­ene­di­amine)­cadmium(II) hexa­cyano­ferrate(III), (Et4N){[Cd(en)]4[Fe(CN)6]3}

The title compound, tetra­ethyl­ammonium dodeca‐μ‐cyano‐hexa­cyano­tetrakis­(ethyl­ene­di­amine)­tetra­cadmium(II)­tri­fer­rate(III), (C₈H₂₀N)[Cd₄Fe₃(CN)₁₈(C₂H₈N₂)₄], was pre­pared from a reaction mixture containing CdCl₂, K₃[Fe(CN)₆], ethyl­ene­di­amine (en) and [Et₄N]Br in a 1:1:3:1 molar ratio. The crystal structure consists of a negatively charged three‐dimensional framework of {[Cd(en)]₄[Fe(CN)₆]₃} anions, with [Et₄N]⁺ cations located in the cavities of the framework. The Cd atom is octahedrally coordinated by one disordered chelating en mol­ecule [mean Cd—N = 2.35 (3) Å] and four N‐­bonded bridging cyano groups [Cd—N distances are in the range 2.283 (2)–2.441 (2) Å]. There are two crystallographically independent [Fe(CN)₆]³⁻ anions in the structure and in each the Fe atom lies on a twofold axis. In the first [mean Fe—C = 1.941 (5) Å], all the cyano groups are bridging ligands, while in the second [mean Fe—C = 1.945 (2) Å], there are two terminal cyano ligands in trans positions. The Cd—N—C angles range from 128.6 (2) to 172.8 (2)°.     

The layered structure of poly­[[di‐μ‐chloro‐bis­[chloro(2‐ethyl­tetrazole‐κN4)copper(II)]]‐di‐μ‐2‐ethyl­tetrazole‐κ2N1:N4]

In the polymeric title complex, [CuCl₂(C₃H₆N₄)₂]_n, there are two ligands in the asymmetric unit. The Cu atom adopts an elongated octahedral geometry, with two 2‐ethyl­tetrazole ligands [Cu—N = 2.0037 (16) and 2.0136 (16) Å] and two Cl atoms [Cu—Cl = 2.2595 (6) and 2.2796 (6) Å] in equatorial positions. A Cl atom and a symmetry‐related 2‐ethyl­tetrazole mol­ecule [Cu—Cl = 2.8845 (8) Å and Cu—N = 2.851 (2) Å] lie in the axial positions of the octahedron. One of the two 2‐­ethyltetrazole ligands of the asymmetric unit exhibits bidentate binding to two Cu atoms through two N atoms of the tetrazole ring, whereas the other ligand is coordinated in a monodentate fashion via one tetrazole N atom. The Cu‐atom octahedra form dimer entities by sharing edges with equatorial and axial Cl atoms. The dimers are linked together through the 2‐ethyl­tetrazole ligands to form one‐dimensional polymeric zigzag chains extending along the b axis. The chains are connected into infinite layers parallel to the (10) plane via the 2‐ethyl­tetrazole ligands.     

Hydro­gen bonding in ethyl­ene­di­ammonium bis­(hydrogen malonate) mono­hydrate

In the title compound, C₂H₁₀N₂²⁺·2C₃H₃O₄^?·H₂O, the hydrogen malonate anion has an intramolecular O—H?O hydrogen bond of 2.430 (2) Å. The water mol­ecule lies on a twofold axis and connects the anions into pairs through hydrogen bonds of 2.734 (1) Å. The ethyl­enedi­ammonium cation lies across an inversion centre. Each of the ammonium protons is involved in hydrogen bonding to an anion or a water mol­ecule [N?O 2.815 (2)–2.875 (2) Å].     

Layered zincoarsenate templated by N,N,N′,N′‐tetra­methyl­ethyl­ene‐di­amine mol­ecules

The title compound, N,N,N′,N′‐tetra­methyl­ethyl­enedi­ammon­ium di­aqua­(arsenate)­(hydrogen arsenate)­dizinc(II), (C₆H₁₈N₂)_0.5[Zn₂(AsO₄)(HAsO₄)(H₂O)₂], is a new zincoarsenate obtained by hydro­thermal synthesis. The structure consists of infinite two‐dimensional anionic layers alternating with planes containing centrosymmetric organic diprotonated template N,N,N′,N′‐tetra­methyl­ethyl­enedi­ammonium cations, [H₃N­C₆H₁₂NH₃]²⁺. The latter are interconnected to the framework through hydrogen bonds.     

Hexa‐μ2‐chloro‐μ4‐oxo‐tetrakis[(2‐ethyl­tetrazole‐κN4)copper(II)]

In the title molecular complex, [Cu₄Cl₆O(2‐EtTz)₄], where 2‐EtTz is 2‐ethyl­tetrazole (C₃H₆N₄), the central O atom is located on the symmetry site and is tetrahedrally coordinated to four Cu atoms, with Cu—O distances of 1.8966 (4) Å. A very slight distortion of Cu₄O from a regular tetrahedron is observed [two Cu—O—Cu angles are 108.76 (3)° and four others are 109.828 (13)°]. Each Cu atom is connected to three others via the Cl atoms, forming a slightly distorted Cl octahedron around the O atom, with O⋯Cl distances of 2.9265 (7) Å for Cl atoms lying on the twofold axis and 2.9441 (13) Å for those in general positions. The Cu atom has a distorted trigonal–bipyramidal environment, with three Cl atoms in the equatorial plane, and with the N atom of the 2‐ethyl­tetrazole ligand and the μ₄‐O atom in axial positions. The Cu atom is displaced out of the equatorial plane by ca 0.91 Å towards the coordinated N atom of the 2‐­ethyl­tetrazole ligand.     

Ethylenediammonium bis{bis[N‐(2‐aminoethyl)glycinato‐κ3N,N′,O]chromium(III)} tetrachloride dihydrate at 293 and 100 K

The crystal structure of the title compound, (C₂H₁₀N₂)[Cr(C₄H₉N₂O₂)₂]₂Cl₄·2H₂O, has been determined by single‐crystal X‐ray diffraction studies at 293 and 100 K. The analyses demonstrated that the crystal consists of ethyl­enedi­ammonium dications (which lie about inversion centres), bis­[N‐(2‐amino­ethyl)­glycin­ato]­chromium(III) monocations, Cl^? anions and hydrate water mol­ecules, in a molecular ratio of 1:2:4:2. The complex cation unit has a slightly distorted octahedrally coordinated Cr atom, with two Cr—O and four Cr—N bonds in the ranges 1.951 (1)–1.953 (1) and 2.054 (1)–2.089 (2) Å, respectively, at 293 K. The geometry of the bis­[N‐(2‐amino­ethyl)­glycinato]­chromium(III) moiety was found to be trans,cis,cis with respect to the carboxyl­ate O atom and the primary and secondary amine N atoms. The two analyses, at 293 and 100 K, exhibited no remarkable structural differences, although the colour of the crystals did differ, being red at 293 K and orange at 100 K.     

μ‐Acetato‐O:O′‐bis{[bis­(salicyl­idene)­ethyl­ene­diamin­ato]manganese(III)} per­chlorate

In the title complex, [Mn₂(C₁₆H₁₄N₂O₂)₂(C₂H₃O₂)]ClO₄, two [Mn(salen)] moieties [salen is bis­(salicyl­idene)­ethyl­enedi­amine] are connected through a μ‐acetate bridge in a syn–anti fashion. The Mn?Mn distance is 5.365 (1) Å.     

Sodium scandium arsenate,Na3Sc2(AsO4)3

Nasicon-type trisodium discandium tris­(arsenate), Na₃Sc₂(AsO₄)₃, contains a polyhedral network of vertex-sharing octahedral ScO₆ and tetrahedral AsO₄ units [d_av(Sc—O) = 2.089 (2) Å and d_av(As—O) = 1.672 (2) Å] encapsulating two types of Na⁺ species. The sodium site occupancies are similar to those of the equivalent species in β-Na₃Sc₂(PO₄)₃.     

π‐Stacked hydrogen‐bonded dimers in 2‐(2‐nitro­phenyl­amino­carbonyl)­benzoic acid,and hydrogen‐bonded sheets in orthorhombic and monoclinic polymorphs of 2‐(4‐nitro­phenyl­amino­carbonyl)­benzoic acid

Molecules of 2‐(2‐nitrophenylaminocarbonyl)benzoic acid, C₁₄H₁₀N₂O₅, are linked into centrosymmetric R(8) dimers by a single O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.623 (2) Å and O—H⋯O = 178°] and these dimers are linked into sheets by a single aromatic π–π stacking interaction. The isomeric compound 2‐(4‐nitrophenylaminocarbonyl)benzoic acid crystallizes in two polymorphic forms. In the orthorhombic form (space group P2₁2₁2₁ with Z′ = 1, crystallized from ethanol), the mol­ecules are linked into sheets of R(22) rings by a combination of one N—H⋯O hydrogen bond [H⋯O = 1.96 Å, N⋯O = 2.833 (3) Å and N—H⋯O = 171°] and one O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.614 (3) Å and O—H⋯O = 173°]. In the monoclinic form (space group P2₁/n with Z′ = 2, crystallized from acetone), the mol­ecules are linked by a combination of two N—H⋯O hydrogen bonds [H⋯O = 2.09 and 2.16 Å, N⋯O = 2.873 (4) and 2.902 (3) Å, and N—H⋯O = 147 and 141°] and two O—H⋯O hydrogen bonds [H⋯O = 1.84 and 1.83 Å, O⋯O = 2.664 (3) and 2.666 (3) Å, and O—H⋯O = 166 and 174°] into sheets of some complexity. These sheets are linked into a three‐dimensional framework by a single C—H⋯O hydrogen bond [H⋯O = 2.45 Å, C⋯O = 3.355 (4) Å and C—­H⋯O = 160°].