A three‐dimensional framework of bis­[tris­(ethyl­enediamine)zinc] tetra­iodo­cadmate diiodide assisted by N—H⋯I hydrogen bonds

The title salt, [Zn(C₂N₂H₈)₃]₂[CdI₄]I₂, conventionally abbreviated [Zn(en)₃]₂[CdI₄]I₂, where en is ethyl­enediamine, contains discrete [Zn(en)₃]²⁺ cations and [CdI₄]²⁻ anions with distorted octa­hedral and nearly tetra­hedral geometries, respectively, as well as uncoordinated I⁻ ions. The cation and the free I⁻ anion lie on twofold rotation axes and the [CdI₄]²⁻ anion lies on a axis in the space group I2d. The structure exhibits numerous weak inter‐ionic hydrogen bonds of two types, viz. N—H⋯I⁻(free ion) and N—H⋯I([CdI₄]²⁻), which support the resulting three‐dimensional framework.     

Second‐sphere coordination in anion binding: sodium hexa­ammine­cobalt(III) tetra­kis­(4‐fluoro­benzoate) monohydrate

In sodium hexa­amminecobalt(III) tetra­kis­(4‐fluoro­benzoate) monohydrate, Na[Co(NH₃)₆](C₇H₄FO₂)₄·H₂O, determined at 180 K, [Co(NH₃)₆]³⁺ cations lie on centres of inversion and form layers in which their C₄ axes lie perpendicular to the layer planes. 4‐Fluoro­benzoate anions lie on twofold axes and general positions and adopt near‐planar geometries. Na⁺ cations and water mol­ecules lie on twofold axes, forming [NaO₅] square pyramids that lie between the [Co(NH₃)₆]³⁺ cations. The second‐sphere inter­actions between [Co(NH₃)₆]³⁺ cations and 4‐fluorobenzoate anions comprise edge‐to‐face and vertex‐to‐face arrangements. The structure is closely comparable with that of the benzoic acid salt, demonstrating that fluorination of the anion in the para position has no significant influence on the second‐sphere inter­actions and minimal influence on the gross crystal structure.     

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).     

Tris­[(R)‐lact­amide‐κ2O,O′]­zinc(II) tetra­bromo­zincate

The title compound, tris­[(R)‐2‐hydroxy­propan­amide‐κ²O,O′]­zinc(II) tetra­bromo­zincate, [Zn(C₃H₇NO₂)₃][ZnBr₄], contains one monomeric six‐coordinate zinc complex cation and one tetrahedral [ZnBr₄]²⁻ anion. Both Zn^II atoms lie on threefold axes. Coordination in the cation occurs via the amide and hydroxy O atoms [Zn—O = 2.074 (5) and 2.073 (6) Å] and has a distorted octahedral geometry, with cis‐O—Zn—O angles in the range 76.2 (2)–109.2 (2)°. In the crystal structure, the cations and anions are linked by N—H⋯Br and O—H⋯O hydrogen bonds, generating a three‐dimensional network.     

Bis­[tris­(ethyl­enedi­amine)­cobalt(III)] di­chloro­bis­[μ‐(1‐hydroxy­ethyl­idene)­di­phospho­nato(4–)]­di­ruthenium(II,­III)­(Ru–Ru) chloride trihydrate

In the title compound, [Co(C₂H₈N₂)₃]₂[Ru₂(C₂H₄O₇P₂)₂Cl₂]Cl·3H₂O, the building unit contains two crystallographically independent dinuclear [Ru₂(hedp)₂Cl₂]⁵⁻ anions, where hedp [viz. (1‐hydroxy­ethyl­idene)­di­phospho­nate] serves as a bis‐chelating bridging ligand, two types of [Co(en)₃]³⁺ cations, one uncoordinated Cl⁻ anion and five water mol­ecules of crystallization. The [Ru₂(hedp)₂Cl₂]⁵⁻ anions are connected to one another, forming one‐dimensional chains along the a axis. The [Co(en)₃]³⁺ cations are located between these chains and lie across inversion centres. An extensive series of hydrogen bonds lead to the formation of a three‐dimensional supramol­ecular network structure, with channels generated along the [100] direction. The uncoordinated water mol­ecules and Cl⁻ anions reside in these channels.     

[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.     

Tris{bis­[N-(2-amino­ethyl)-1,2-ethane­di­amine-κ3N]­nickel(II)} bis­(tetra­thio­antimonate)

Yellow crystals of [Ni(deta)₂]₃[SbS₄]₂ (deta is diethyl­enetri­amine, C₄H₁₃N₃) were synthesized under solvothermal conditions by reacting elemental Ni, Sb and S in a solution of diethyl­enetri­amine. The structure is composed of tetrahedral [SbS₄]³⁻ anions in general positions and octahedral [Ni(deta)₂]²⁺ cations located at centres of inversion. In the crystal structure, the anions and cations are stacked in the direction of the a axis in a pseudo-hexagonal arrangement.     

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)°.     

Tris(ethyl­ene­diamine)­nickel(II) bis­[2‐cyano‐2‐(oxidoimino)­acetamidato]­nickelate(II) monohydrate

The title compound, [Ni(C₂H₈N₂)₃][Ni(C₃HN₃O₂)₂]·H₂O, appears to be a modular associate consisting of two complex counter‐ions, containing bivalent nickel as the central atom in both cases, and a solvent water mol­ecule. The Ni^II ion in the complex cation lies on the C₂ crystallographic axis. Its coordination environment is formed by six N atoms of three ethyl­ene­diamine (en) mol­ecules, representing a distorted octa­hedral geometry. The Ni^II ion in the complex anion occupies a position at the center of inversion. It exhibits a distorted square‐planar coordination geometry formed by four N atoms belonging to the deprotonated oxidoimine and amide groups of the two doubly charged 2‐cyano‐2‐(oxidoimino)acetamidate anions, situated in trans positions with respect to each other. In the crystal packing, the complex anions are linked by water mol­ecules via hydrogen bonds between the amide O atoms and water H atoms, forming chains translated along the a direction. The [Ni(en)₃]²⁺ cations fill empty spaces between the translational chains, connecting them by hydrogen bonds between the oxime and amide O atoms of the anions and the amine H atoms of the cations, forming layers along the ac plane. The water mol­ecules provide connection between layers through N atoms of the cations, thus forming a three‐dimensional modular structure.     

Tetrakis­(pyridinium‐2‐thiol­ato)­zinc(II) dinitrate

The crystal structure of the title compound, [Zn(C₅H₅NS)₄](NO₃)₂, consists of a [Zn(C₅H₅NS)₄]²⁺ (C₅H₅NS is pyridinium‐2‐thiol­ate) cation and two nitrate anions. The central Zn^II atom lies at a site with imposed symmetry and is surrounded by four S atoms [Zn—S = 2.3371 (5) Å] from four symmetrical pyridinium‐2‐thiol­ate ligands in a distorted tetrahedral geometry. There are N—H⋯O hydrogen‐bonding interactions between the pyridinium‐2‐thiol­ate ligands and nitrate O atoms. In addition, π–π interactions via aromatic N‐containing ligands are discussed.     

Three different bonding modes of cyano groups in the coordination polymer [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O (en is 1,2‐diaminoethane)

Partial reduction of the Cu^II ions in the aqueous system Cu^II–en–[Ni(CN)₄]^2? (1/1/1) (en is 1,2‐di­amino­ethane) yields a novel heterobimetallic mixed‐valence compound, poly­[[aqua­bis(1,2‐di­amino­ethane)copper(II)] [hexa‐μ‐cyano‐tetra­cyano­bis(1,2‐di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C₂H₈N₂)₂(H₂O)][Ni₂Cu₃(CN)₁₀(C₂H₈N₂)₂]·2H₂O or [Cu(en)₂(H₂O)][Cu(en)₂Ni₂Cu₂(CN)₁₀]·2H₂O. The structure is formed by a negatively charged two‐dimensional array of the cyano complex [Cu(en)₂Ni₂Cu₂(CN)₁₀]_n^2n?, [Cu(en)₂(H₂O)]²⁺ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen‐bonding system. The cyano groups act as terminal, μ₂‐bridging or μ₃‐bridging ligands.     

A three‐dimensional CuII–WIV bimetallic porous assembly containing a zigzag ladder structure

The asymmetric unit of the three‐dimensional Cu^II–W^IV polymeric assembly {[Cu(en)₂][Cu(en)][W(CN)₈]·4H₂O}_n (en is ethyl­enedi­amine, C₂H₈N₂) or {[Cu₂W(CN)₈(C₂H₈N₂)₃]·4H₂O}_n, which can be named as polymeric bis­(ethyl­enedi­amine)copper(II) (ethyl­enedi­amine)copper(II) octa­cyano­tungstate(IV) tetrahydrate or penta‐μ‐cyano‐tri­cyano­tris­(ethyl­enedi­amine)­dicopper(II)­tungsten(IV) tetra­hydrate, consists of two half [Cu(en)₂]²⁺ cations (Cu²⁺ on inversion centres), a [Cu(en)]²⁺ cation and a [W(CN)₈]^4? ion, together with four water mol­ecules. The latter Cu^II site is coordinated by five N atoms from an en ligand and by three cyanides in a distorted square‐pyramidal geometry. The Cu^II atoms of the two [Cu(en)₂]²⁺ cations reside in an elongated octahedral coordination environment, and one of them is localized at a centre of inversion. The W atom is coordinated by eight cyano groups in an irregular square antiprism. Five of these act as bridging units connecting the W and the three Cu atoms, to form an infinite three‐dimensional porous network containing a zigzag ladder structure.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

Synthese und Eigenschaften von Triphenylzinnmolybdaten mit kettenförmigen Anionen des Typs 1∞[(Ph3Sn)MoO4]–. Die Kristallstrukturen von (nPr4N)[(Ph3Sn)MoO4]·CH3CN, (nBu4N)[(Ph3Sn)MoO4], [Zn(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH und [Cu(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH

The reaction of Ph₃SnCl, (R₄N)₂[Mo₆O₁₉] and (R₄N)OH in a molar ratio of 6:1:10 leads to the formation of (R₄N)[(Ph₃Sn)MoO₄] (R = ⁿPr ( 1 ), ⁿBu ( 2 )). Compounds 1· CH₃CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH₃CN forms orthorhombic crystals, space group P2₁2₁2₁ with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P2₁ with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R₄N⁺ cations and polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains with an alternating arrangement of Ph₃Sn⁺ and MoO₄^2– groups. Treatment of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)copper(II) succinate yields [Cu(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 3 ). The zinc derivative [Zn(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 4 ) is obtained similarly by reaction of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P2₁/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains are observed. The [M(en)₂]²⁺ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains to give 2D layer structures with (6, 3) net topology.     

catena‐Poly[tris(ethylenediamine‐κ2N,N′)nickel(II) [[trithiocyanato‐κ3N‐sodium(I)]‐μ‐aqua‐κ2O:O]]

The title complex, {[Ni(C₂H₈N₂)₃][Na(NCS)₃(H₂O)]}_n, con­sists of discrete [Ni(en)₃]²⁺ dications (en is ethyl­enedi­amine) and polymeric [(H₂O)_0.5Na(NCS)₃(H₂O)_0.5]_n^2n? anions. The compound crystallizes in space group Pc1. The Ni^II atom lies on a threefold axis and has a distorted octahedral coordination geometry. The Na⁺ cation also lies on a site with imposed crystallographic threefold symmetry and is coordinated by the thio­cyanate N atoms (the thio­cyanates are in general posi­tions), by one water mol­ecule with crystallographically imposed 32 symmetry and by a second water mol­ecule with crystallographically imposed symmetry. The unique Na atom thus has trigonal–bipyramidal coordination. The O atoms of the water mol­ecules bridge the Na⁺ cations to form one‐dimensional polymeric chains in the crystal structure. The [Ni(en)₃]²⁺ dications are distributed around and between the chains and are linked to them via N—H?S hydrogen bonds.     

Iron(III) dihydrogenphosphate(I)

The structure of rhombohedral (R) iron(III) tris­[di­hydrogen­phosphate(I)] or iron(III) hypophosphite, Fe(H₂PO₂)₃, has been determined by single‐crystal X‐ray diffraction. The structure consists of [001] chains of Fe³⁺ cations in octa­hedral sites with symmetry bridged by bidentate hypophosphite anions.     

[Cu(C8H16N4O2)0.5{N(CN)2}]n,a novel ladder‐like coordination polymer

A new polymeric copper complex, viz.catena‐poly[[[μ‐N,N′‐bis(3‐amino­propyl)oxa­mid­ato‐κ⁶N,N′,O:N′′,N′′′,O′]­dicopper(II)]‐di‐μ‐dicyan­amido‐1:1′κ²N¹:N⁵;2:2′κ²N¹:N⁵], [Cu₂(C₈H₁₆N₄O₂)(C₂N₃)₂]_n or [Cu(oxpn)_0.5{N(CN)₂}]_n [where H₂oxpn is N,N′‐bis(3‐amino­propyl)­ox­amide], has been ­synthesized by the reaction of Cu(oxpn), [Cu(ClO₄)₂]·6H₂O and NaN₃. In the crystal structure, the Cu atom is five‐coordinate and has a square‐pyrimidal (SP) configuration. In the polymer, dicyan­amide (dca⁻) groups link Cu^II cations in a μ‐1,5‐bridging mode, generating novel ladders in which each step is composed of dimeric [Cu₂(oxpn)]²⁺ cations. Abundant hydrogen bonds connect the polymer ladders into a two‐dimensional network structure.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

A one‐dimensional iodine‐bridged PtII/PtIV mixed‐valence complex,catena‐poly[[[bis­(ethyl­ene­diamine)­platinum(II)]‐μ‐iodo‐[bis­(ethyl­ene­di­amine)platinum(IV)]‐μ‐iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

The title compound, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄](HPO₄)(H₂PO₄)I·3H₂O}_n, has a chain structure composed of square‐planar [Pt(en)₂]²⁺ and elongated octa­hedral trans‐[PtI₂(en)₂]²⁺ cations (en is ethyl­ene­diamine) stacked alternately along the c axis and bridged by the I atoms; a three‐dimensionally valence‐ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetra­mer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O⋯O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ⋯I—Pt^IV—I⋯Pt^II⋯ chain, with Pt^IV—I bond distances of 2.6997 (7) and 2.6921 (7) Å, inter­atomic Pt^II⋯I distances of 3.3239 (8) and 3.2902 (7) Å, and Pt^IV—I⋯Pt^II angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed‐valence state of platinum, expressed by δ = (Pt^IV—I)/(Pt^II—I), are 0.812 and 0.818 for the two independent I atoms.     

catena‐Poly[[[tetra­aqua­zinc(II)]‐μ‐4,4′‐bipyridine] bis­(4‐hydroxy­benzene­sulfonate) trihydrate]

In the title compound, {[Zn(C₁₀H₈N₂)(H₂O)₄](C₆H₅O₄S)₂·3H₂O}_n, the Zn atom, the bipyridine ligand and one of water mol­ecules are located on twofold rotation axes. The Zn atom is coordinated by four O atoms from four water mol­ecules and two N atoms from two 4,4′‐bipyridine mol­ecules in a distorted octa­hedral geometry. The Zn²⁺ ions are linked by the 4,4′‐bipyridine mol­ecules to form a one‐dimensional straight chain propagating along the c axis. The 4‐hydroxy­benzene­sulfonate counter‐ions are bridged by the solvent water mol­ecules through hydrogen bonds to generate a two‐dimensional layer featuring large pores. In the crystal packing, the intra­layer pores form one‐dimensional channels along the c axis, in which the one‐dimensional [Zn(C₁₀H₈N₂)(H₂O)₄]²⁺ chains are encapsulated. Electrostatic inter­actions between cations and anions and extensive hydrogen bonds result in a three‐dimensional supra­molecular structure.