Synthesis and crystal structure of aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)-(tetrachlorocuprato(II)-Cl)potassium

New mixed complex compound aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(tetrachlorocuprato(II)-Cl)potassium, [K(CuCl₄)(Db18C6)]^? · [K(Db18C6)(H₂O)]⁺, is synthesized and its crystal structure is studied by the method of x-ray structural analysis. The structure includes two independent complex ions, both of guest-host type: two cations K⁺ are located in the respective cavities of the Db18C6 crown-ligand (one in each) and each is coordinated by all its six O atoms and one Cl atom of the anion-ligand [CuCl₄]^2? or O atom of the ligand water molecule. Coordination of these two K⁺ cations is completed to hexagonal pyramidal one by formation by each of unusually weak coordination bond K⁺ → π(\(C\dddot - C\)) with two C atoms of respective benzene ring in the neighboring Db18C6 ligand. In this crystal structure the complex anions and cations form dual infinite chains via these coordination bonds and interionic O-H?Cl hydrogen bonds.     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐(dihydrogen benzene‐1,2,4,5‐tetracarboxylato)‐κ2O1:O4]

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂)]_n, the Cu^II cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H₂TCB²⁻). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB²⁻ anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.     

The structure and thermal behaviour of sodium and potassium multinuclear compounds with hexamethylenetetramine

Sodium and potassium thiocyanate complex compounds of formulae [Na(hmta)(H₂O)₄]₂²⁺·2SCN⁻ (1) and [K₂(hmta)(SCN)₂] _n (2) have been synthesized and characterised by IR spectroscopy, thermogravimetry coupled with differential thermal analysis, elemental analysis and X-ray crystallography. Each sodium and potassium cation is six co-ordinated, the sodium by one monofunctional hmta molecule, three terminal water molecules and two bridging water molecules, and the potassium by two bridging tetrafunctional hmta molecules and four bridging tetrafunctional thiocyanate ions. The coordination polyhedra of the central atoms can be described as distorted tetragonal bipyramids. The complex cations and anions of (1) are interconnected by multiple intramolecular O(water)—H···N(hmta/NCS) and O(water)—H···S hydrogen bonds to the three dimensional net. In each complex cation the intramolecular O–H···O hydrogen bonds link two terminal water molecules bonded to two metal cations. The compound (2) forms the three dimensional hybrid network in which the classical two-dimensional coordination polymers are linked by inorganic SCN⁻ spacers to the third-dimension. Thermal analyses show that the compounds decompose gradually in three (for 1) and two (for 2) steps with formation of Na₂SO₄ and K₂S as the final products, respectively, for 1 and 2.     

A Potassium Diboryllithate: Synthesis,Bonding Properties,and the Deprotonation of Benzene

A potassium diboryllithate (B₂LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B₂LiK, revealed ionic interactions between the two bridging boryl anions and Li⁺ and K⁺. Upon standing in benzene, B₂LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K⁺.     

A Potassium Diboryllithate: Synthesis,Bonding Properties,and the Deprotonation of Benzene

A potassium diboryllithate (B₂LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B₂LiK, revealed ionic interactions between the two bridging boryl anions and Li⁺ and K⁺. Upon standing in benzene, B₂LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K⁺.     

A novel parallel interpenetrating two‐dimensional (4,4) network: poly[[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene](μ2‐naphthalene‐1,4‐dicarboxylato)zinc(II)]

In the title coordination compound, [Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]_n, the two Zn^II centers exhibit different coordination environments. One Zn^II center is four‐coordinated in a distorted tetrahedral environment surrounded by two carboxylate O atoms from two different naphthalene‐1,4‐dicarboxylate (1,4‐ndc) anions and two N atoms from two distinct 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4‐bix) ligands. The coordination of the second Zn^II center comprises two N atoms from two different 1,4‐bix ligands and three carboxylate O atoms from two different 1,4‐ndc ligands in a highly distorted square‐pyramidal environment. The 1,4‐bix ligand and the 1,4‐ndc anion link adjacent Zn^II centers into a two‐dimensional four‐connected (4,4) network. The two (4,4) networks are interpenetrated in a parallel mode.     

Kristallstrukturen von Kalium- und Silbercyanamidonitrat

Pseudoelement Compounds. XV Crystal Structure Analysis of Potassium and Silver Cyanamidonitrate The crystal structures of potassium and silver cyanamidonitrate are reported. In both the potassium and the silver salt metal anion contacts via the atoms cyano-N, amide-N and oxygen are observed. The structural parameters of the ion [NO₂NCN]^– are only slightly influenced by the different environments (potassium, silver). K[NO₂NCN] forms a coordination lattice in which the nearest neighbours of the potassium ion are nine N and O atoms belonging to seven different anions. Ag[NO₂NCN] has a layer structure; the silver atoms are arranged in zickzack chains running perpendicular to the layers with an Ag–Ag distance of 3.169(1) Å.     

Polymeric aqua­(μ4‐di­hydrogen benzene‐1,2,4,5‐tetra­carboxylato)(1,10‐phen­anthroline)cobalt(II)

In the title compound, poly[[aqua(1,10‐phenanthroline)­cobalt(II)]‐μ₄‐di­hydrogen benzene‐1,2,4,5‐tetra­carboxyl­ato], [Co(C₁₀H₄O₈)(C₁₂H₈N₂)(H₂O)]_n, each cobalt(II) cation has an octahedral geometry completed by one aqua O atom, three carboxy O atoms belonging to three H₂TCB²⁻ anions (H₂TCB²⁻ is di­hydrogen ­benzene‐1,2,4,5‐tetra­carboxyl­ate) and two N atoms from a 1,10‐phenanthroline mol­ecule. In the asymmetric unit, there are two half H₂TCB²⁻ anions lying about independent inversion centres. The bridging H₂TCB²⁻ anions have two coordination modes, viz.μ₂‐H₂TCB²⁻ and μ₄‐H₂TCB²⁻, resulting in a two‐dimensional coordination polymer. Furthermore, a three‐dimensional network is formed by O_carboxy⋯O_carboxy hydrogen‐bond interactions, with H⋯A distances in the range 1.69–1.82 Å, and O_carboxy⋯O_water interactions, with H⋯A distances in the range 1.91–1.94 Å.     

Poly[(μ4‐biphenyl‐3,3′,4,4′‐tetracarboxylato)bis[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene]dicobalt(II)]

The asymmetric unit of the title two‐dimensional coordination polymer, [Co₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]_n, contains one Co²⁺ ion, half of a biphenyl‐3,3′,4,4′‐tetracarboxylate (bptc) anion lying about an inversion centre and one 1,4‐bis(imidazol‐1‐ylmethyl)benzene (bix) ligand. The Co^II atom is coordinated by three carboxylate O atoms from two different bptc ligands and two N atoms from two bix ligands constructing a distorted square pyramid. Each Co²⁺ ion is interlinked by two bptc anions, while each bptc anion coordinates to four Co atoms as a hexadentate ligand so that four Co^II atoms and four bptc anions afford a larger 38‐membered ring. These inorganic rings are further extended into a two‐dimensional undulated network in the (10) plane. Two Co^II atoms in adjacent 38‐membered rings are joined together by pairs of bix ligands forming a 26‐membered [Co₂(bix)₂] ring that is penetrated by a bptc anion; these components share a common inversion centre.     

Poly[(μ4‐2,5‐dimethoxybenzene‐1,4‐dicarboxylato)manganese(II)] and its zinc(II) analogue: three‐dimensional coordination polymers containing unusually coordinated metal centres

The title compounds, [Mn(C₁₀H₈O₆)]_n and [Zn(C₁₀H₈O₆)]_n, are isomorphous coordination polymers prepared from 2,5‐dimethoxyterephthalic acid (H₂dmt) and the respective metal(II) salts. Both complexes form three‐dimensional metal–organic frameworks with each M^II centre bridged by four 2,5‐dimethoxyterephthalate (dmt²⁻) anions, resulting in the same type of network topology. The asymmetric unit consists of one M^II cation on a twofold axis and one half of a dmt²⁻ anion (located on a centre of inversion). In the crystal structure, the M^II centres are coordinated in a rather unusual way, as there is a distorted tetrahedral inner coordination sphere formed by four carboxylate O atoms of four different dmt²⁻ anions, and an additional outer coordination sphere formed by two methoxy and two carboxylate O atoms, with each of the O atoms belonging to one of the four different dmt²⁻ anions forming the inner coordination sphere. Consideration of both coordination spheres results in a super‐dodecahedral coordination geometry for the M^II centres. Besides the numerous M^II...O interactions, both structures are further stabilized by weak C—H...O contacts.     

Cerous sodium nitrate monohydrate,Na2Ce(NO3)5·H2O

The title compound, disodium cerium pentanitrate monohydrate, was synthesized from a nitric acid solution of Ce(NO₃)₃·6H₂O and NaNO₃, and its structure has been determined from single‐crystal X‐ray diffraction data. The structure is built from isolated chains of irregular icosahedral [Ce(NO₃)₆]^3? anions. Na atoms and water mol­ecules are located between the chains. The Na coordination polyhedra, in the form of a square antiprism or a monocapped square antiprism, share common vertices and contribute to the formation of a three‐dimensional network. Ten nitrate groups act as bridging ligands.     

以方酸及咪唑基配体构筑的二维层状镉(Ⅱ)配位聚合物的合成和表征

水热条件下,以1,4-双(咪唑基-1-甲基)苯(bix)及方酸阴离子(C4O42-)为配体,合成了新的镉的配位聚合物[Cd(C4O4)(bix)(H2O)2]n(1)。单晶结构分析表明,该配合物为二维层状结构,镉中心为六配位八面体结构,赤道平面上4个配位原子分别来自方酸和bix配体,轴向2个配位原子来自配位水分子,镉原子通过双配体桥连形成四连接的二维(4,4)网络。同时,测定了配合物的热稳定性和荧光性质。     

catena‐Poly[[aqua(11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline‐κ2N4,N5)cadmium(II)]‐μ‐benzene‐1,4‐dicarboxylato‐κ3O1,O1′:O4]: an inclined interpenetrating (6,3) network

The asymmetric unit of the title compound, [Cd(C₈H₄O₄)(C₁₇H₈ClN₅)(H₂O)]_n, contains one Cd^II atom, two half benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, one 11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline (L) ligand and one coordination water molecule. The 1,4‐bdc ligands are on inversion centers at the centroids of the arene rings. The Cd^II atom is six‐coordinated by two N atoms from one L ligand, three carboxylate O atoms from two different 1,4‐bdc ligands and one water O atom in a distorted octahedral coordination sphere. Each Cd^II center is bridged by the 1,4‐bdc dianions to give a one‐dimensional chain. π–π stacking interactions between L ligands of neighboring chains extend adjacent chains into a two‐dimensional supramolecular (6,3) network. Neighboring (6,3) networks are interpenetrated in an unusual inclined mode, resulting in a three‐dimensional framework. Additionally, the water–carboxylate O—H...O hydrogen bonds observed in the network consolidate the interpenetrating nets.     

Synthesis and crystal structure of [Ag2(μ4-hmt)(NO2)2]n. A two-dimensional network with square cavities self-assembled by hmt (hmt = Hexamethylenetetramine)

AgNO₂ (1 mol) reacts with hexamethylenetetramine (hmt) (1 mol) in MeCN–H₂O to yield a two-dimensional coordination polymer [Ag₂( ₄-hmt)(NO₂)₂]_n with square cavities. The Ag2 atom is located in a linear structure coordination environment with two nitrogen atoms from two hmt molecules respectively. The Ag1 atom is coordinated in a triangular prism surrounded by two nitrogen atoms from two hmt molecules respectively and four oxygen atoms from two NO^– ₂ ions respectively. The four nitrogen atoms of each hmt unit are all connected to Ag^I to form a two-dimensional network.     

3，5-二羟基-2，4，6-三硝基苯酚铷的晶体结构和热行为

0IntroductionSom e nitrogen鄄rich alkaline and alkali鄄earth m et鄄als com pounds of polynitro hydroxybenzenes can beused environm entally friendly prim ary explosives[1￣5].2,4,6鄄Trinitro鄄1,3,5鄄trihydroxybenzene(trinitrophloroglu鄄cinol,TNPG)belongs to a polynitro hydroxybenzeneand has been used in chem icalindustry as an ingredi鄄entfor prim ing com position,percussion caps and deto鄄nator form ulations[6].Therefore,in recent years,ithasbeen exploited to prepare a num ber of salts of ba…     

Poly[[aqua(4,4′‐diazenediyldibenzoato‐κ4O,O′:O′′,O′′′)cadmium(II)]: a twofold interpenetrated three‐dimensional coordination polymer of PtS topology

In the title coordination compound, [Cd(C₁₄H₈N₂O₄)(H₂O)]_n, the Cd^II cation and the coordinated water molecule lie on a twofold axis, whereas the ligand lies on an inversion center. The Cd^II center is five‐coordinated in a distorted square‐pyramidal geometry by four carboxylate O atoms from four different 4,4′‐diazenediyldibenzoate (ddb) anions and one water O atom. The three‐dimensional frameworks thus formed by the bridging ddb anions interpenetrate to generate a three‐dimensional PtS‐type network. Additionally, the coordination water molecule and the carboxylate O atom form a hydrogen‐bonding interaction, stabilizing the three‐dimensional framework structure.     

Synthesis,Crystal Structure,Thermal, Spectroscopic and Magnetic Properties of a 2D Grid‐like Copper(II) μ‐1,1 Isocyanato Coordination Polymer with Pyrazine Bridges

Reaction of copper(II) cyanate with pyrazine leads to the formation of [Cu(NCO)₂(pyrazine)]_n ( 1 ), in which the Cu²⁺ cations are coordinated by two nitrogen atoms of the pyrazine ligands, as well as by four nitrogen atoms of the cyanate anions within a slightly distorted octahedral coordination. In the crystal structure the Cu²⁺ cations are connected by the pyrazine ligands into chains which are further linked by the cyanate anions through asymmetric μ‐1,1‐NCO coordination into layers. On heating compound 1 transforms quantitatively to copper(II) cyanate which decompose to elemental copper on further heating. No ligand deficent intermediates are observed. Magnetic measurements reval an antiferromagnetic ordering at lower temperatures mediated by the π‐system of the aromatic pyrazine ligand as well as net ferromagnetic interactions mediated by the μ‐1,1‐NCO bridging cyanato anions. A search in the Cambridge Crystal Structure Database shows that the terminal coordination mode in cyanato complexes as well as their azido and thiocyanato analogs is obviously energetically favored. In addition, a comparison of their symmetric and asymmetric end‐on (μ‐1,1) as well as end‐to‐end (μ‐1,3) bridging modes reveal interesting correlations.     

A new two‐dimensional CdII coordination polymer based on 2‐(1H‐imidazol‐1‐ylmethyl)‐6‐methyl‐1H‐benzimidazole and benzene‐1,2‐dicarboxylate: synthesis,crystal structure and characterization

In the construction of coordination polymers, many factors can influence the formation of the final architectures, such as the nature of the metal centres, the organic ligands and the counter‐anions. In the coordination polymer poly[aqua(μ‐benzene‐1,2‐dicarboxylato‐κ⁴O ¹,O ^1′:O ²,O ^2′)[μ‐2‐(1H‐imidazol‐1‐ylmethyl)‐6‐methyl‐1H‐benzimidazole‐κ²N ²:N ³]cadmium(II)], [Cd(C₁₂H₁₂N₄)(C₈H₄O₄)(H₂O)]_n or [Cd(immb)(1,2‐bdic)(H₂O)]_n , each Cd^II ion is seven‐coordinated by two N atoms from two symmetry‐related 2‐(1H‐imidazol‐1‐ylmethyl)‐6‐methyl‐1H‐benzimidazole (immb) ligands, by four O atoms from two symmetry‐related benzene‐1,2‐dicarboxylate (1,2‐bdic²⁻) ligands and by one water molecule, leading to a CdN₂O₅ distorted pentagonal bipyramidal coordination environment. The immb and 1,2‐bdic²⁻ ligands bridge Cd^II ions and form a two‐dimensional network structure. O—H…O and N—H…O hydrogen bonds stabilize the structure. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviour and fluorescence properties of the title polymer have been investigated.     

EPR and electronic spectroscopic studies of Keggin type undecatungstophosphocuprate(II) and undecatungstoborocuprate(II)

The coordination of Cu(II) to the Keggin type anions α-undecatungstophosphocuprate(II) and α-undecatungstoborocuprate(II) was investigated in different environments by EPR and electronic spectroscopy. This study has shown that the coordination geometry around Cu(II) in the tetrabutylammonium (TBA) salts, (TBA)₄H_x[XW₁₁CuO₃₉], with X=P or B, is square pyramidal, with copper bound to the five oxygen donor atoms of the polyoxometalate, whereas for the [XW₁₁Cu(H₂O)O₃₉]ⁿ⁻ anion, on the corresponding potassium salt, a tetragonally elongated pseudo-octahedral geometry was found. For the potassium salts, in aqueous solution, six-coordinated copper is the only form found. For the TBA salts, in nonaqueous solvents, we can observe either the presence of only one form (the six-coordinated Cu(II) species, with a solvent molecule bound to copper), or of two forms: the solvent coordinated copper anions and the five-coordinated copper [XW₁₁CuO₃₉]ⁿ⁻ anions.     

An easy way to achieve three‐dimensional metal–organic coordination polymers: synthesis and crystal structure of dizinc diisophthalate bis‐dimethylsulfoxide monohydrate: [Zn2(ip)4(DMSO)2(H2O)·3 DMSO]n

An easy way of producing three‐dimensional metal–organic coordination polymers involving zinc(II) benzene‐dicarboxylates is reported. The reaction of zinc oxide with benzene dicarboxylic acids in water yielded the expected hydrated zinc dicarboxylates. These zinc compounds were then suspended in dimethylsulfoxide and heated to above 100 °C for a couple of hours; the solutions were allowed after filtration to cool down to eventually deliver crystalline compounds displaying complex zeotype structures. The crystal structure of the title compound, [Zn₂(ip)₄(DMSO)₂(H₂O)·3 DMSO]_n (ipH₂ = isophthalic acid = 1,3‐benzenedicarboxylic acid, DMSO = dimethylsulfoxide), is reported for the first time and shows a three‐dimensional network where octahedrally and tetrahedrally coordinated zinc atoms (present in a 1:1 ratio) are linked by bridging isophthalate ligands. The complex coordination network exhibits a remarkable channel structure along the z‐axis. The related zinc terephthalate–DMSO complex was similarly prepared and the crystal structure determination revealed an already documented zeotypic structure: [{Zn₄(OH)₂(tp)₃(DMSO)₄} 2H₂O]_n (tpH₂ = terephthalic acid = 1,4‐benzenedicarboxylic acid). Weak interactions as well as hydrogen bonds involving water molecules and carboxy groups play a major role in the formation of these complex three‐dimensional networks. In comparison, the zinc 1,2‐benzene‐dicarboxylate–DMSO complex could not be isolated, even under more drastic conditions. The higher symmetry of the coordination network found in the zinc terephthalate–DMSO complexes was incidentally corroborated by ¹³C CP/MAS spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.