Poly­[[aqua­neodymium(III)]‐μ3‐decane‐1,10‐di­carboxyl­ato‐μ3‐9‐carboxy­nonane­carboxyl­ato]

The title compound, [Nd(C₁₀H₁₆O₄)(C₁₀H₁₇O₄)(H₂O)]_n, has a novel Nd–organic framework constructed from sebacic acid (C₁₀H₁₈O₄) linkers, the longest aliphatic ligand used to date in lanthanide metal–organic framework compounds. The structure contains edge‐shared chains of NdO₈(H₂O) tricapped trigonal prisms that propagate in the [100] direction, with Nd—O distances in the range 2.414 (4)–2.643 (4) Å.     

[TMPA]4[Si8O20] · 34 H2O and [DDBO]4[Si8O20] · 32 H2O are heteronetwork clathrates with 1,1,4,4-tetramethylpiperazinium (TMPA) and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (DDBO) guest cations

[TMPA]₄[Si₈O₂₀] · 34 H₂O ( 1 ) and [DDBO]₄[Si₈O₂₀] · 32 H₂O ( 2 ) have been prepared by crystallization from aqueous solutions of the respective quaternary alkylammonium hydroxide and SiO₂. The crystal structures have been determined by single-crystal X-ray diffraction. 1 : Monoclinic, a = 16.056(2), b = 22.086(6), c = 22.701(2) Å, β = 90.57(1)° (T = 210 K), space group C2/c, Z = 4. 2 : Monoclinic, a = 14.828(9), b = 20.201(7), c = 15.519(5) Å, β = 124.13(4)° (T = 255 K), space group P2₁/c, Z = 2. The polyhydrates are structurally related host-guest compounds with three-dimensional host frameworks composed of oligomeric [Si₈O₂₀]^8? anions and H₂O molecules which are linked via hydrogen bonds. The silicate anions possess a cube-shaped double four-ring structure and a characteristic local environment formed by 24 H₂O molecules and six cations (TMPA, [C₈H₂₀N₂]²⁺, or DDBO, [C₈H₁₈N₂]²⁺). The cations themselves reside as guest species in large, irregular, cage-like voids. Studies employing ²⁹Si NMR spectroscopy and the trimethylsilylation method have revealed that the saturated aqueous solutions of 1 and 2 contain high proportions of double four-ring silicate anions. Such anions are also abundant species in the saturated solution of the heteronetwork clathrate [DMPI]₆[Si₈O₁₈(OH)₂] · 48.5 H₂O ( 3 ) with 1,1-dimethylpiperidinium (DMPI, [C₇H₁₆N]⁺) guest cations.     

Structural and Physicochemical Studies of [4-ClC6H4CH2NH3]4Li2P6O18·4H2O

The crystal structure of a new organic cation cyclohexaphosphate, [4-ClC ₆ H ₄ CH ₂ NH ₃ ] ₄ Li ₂ P ₆ O ₁₈ .4H ₂ O, is reported. It crystallizes in the triclinic system (space group P-1) with the following unit-cell parameters: a = 9.628(8), b = 12.801(9), c = 19.528(6) Å, α = 78.60(4)°, β = 83.00(5)°, β = 89.98(4)°, Z = 2, and V = 2341(3)Å ³ . The structure has been solved using direct methods and refined by least-squares analysis [R ₁ = 0.043, wR ₂ = 0.108]. The structure can be described as infinite anionic layers with composition of [Li ₂ (P ₆ O ₁₈ )(H ₂ O) ₄ ] ^{4 ?} and parallel to the ac plane. The organic groups are located in the accessible voids. The molecules are stabilized by O─H…O and N─H…O types of intermolecular hydrogen bonds in the unit cell in addition to Van der Waals forces.     

Synthesis,structure and magnetic properties of a two-dimensional polymer based on sandwich-type tetra-cobalt(II)-substituted polyoxotungstate anions and 1-D potassium-chains

A 2-D coordination polymer, (C₇N₄H₁₆)₂{NH(CH₃)₃}[{K(H₂O)}₄Na(H₂O)₅{Co₄(H₂O)₂(B-α-PW₉O₃₄)₂}]·2H₂O (1), was hydrothermally synthesized and structurally characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and X-ray single-crystal crystallography. Crystal structure analysis shows a triclinic space group Pī with a?=?12.4677(8)?Å, b?=?12.5054(8)?Å, c?=?18.5745(1)?Å, α?=?73.3220(1)°, β?=?87.1890(1)°, γ?=?62.2710(1)°, and V?=?2443.4(3)?ų. Sandwich-type tetra-cobalt(II)-substituted [Co₄(H₂O)₂(B-α-PW₉O₃₄)₂]^10? of 1 consists of two trivacant Keggin [B-α-PW₉O₃₄]^9? moieties and a rhomb-like Co₄O₁₆ unit. Each sandwich-type polyoxotungstate subunit connects 12 K(1) and K(2) centers from two adjacent 1-D K-chain units resulting in an interesting 2-D layer framework. Magnetic properties of 1 have been investigated.     

Synthese und Kristallstruktur von Tetramethylammonium-Sodalith

Tetramethylammonium sodalite, a synthetic species of composition (CH₃)₄NAlSi₅O₁₂, has been obtained in good yield under hydrothermal conditions in the absence of metal cations. Its crystal structure has been determined using accurate powder data since single crystals could not be grown. The structure seems to be body-centered cubic with a = 8.975 Å but the true symmetry is non-cubic (probable space group I4 ). Each cage of the aluminosilicate framework contains one tetramethylammonium ion. The organic cation does not conform to the cubic symmetry of the ideal framework. The methyl groups point to oxygen atoms of the framework, and the short methyl-oxygen distances of 3.06 Å indicate strong C? H … O interaction. The present results indicate beyond doubt that C? H … O hydrogen bonding involving methyl groups can occur in silicates. This is of particular significance in zeolite chemistry and in the interpretation of interlayer distances in organic clay complexes.     

Geometric and topological analysis of zeolite crystal structures by the tiling method: The model of structure of Na,K-paulingite (PAU) Na82K72[Al154Si518O1344] · wH2O

Cluster analysis of the crystal structures of paulingite zeolites (Na,Ca_0.5,K,K,Ba_0.5)₁₀[Al₁₀Si₃₂O₈₄] · 30H₂O (PAU, space group Im [`3]\bar 3 m) has been performed by the tiling method with the TOPOS program package. The tetrahedral T framework of PAU with 672 tetrahedra in the translated unit cell with a = 35.1 ? and V = 43 217 ?³ has been completely decomposed into tiles, complementarily connected polycyclic (polyhedral) T clusters. The zeolite structure is represented by an ensemble consisting of nine geometrically different nanoclusters containing 16 to 48 T tetrahedra (the linear dimensions of the nanoclusters are 12 to 18 ?, respectively). The nanoclusters correspond to seven topologically different types of tiles: 48T-grc (2a), 32T-pau (12e), 30T-plg (16f), 24T-phi (24h), 20T-gsm (12d), 16T-opr (6b, 12e), and 16T-oto (24h, 48k). In the tiles, the positions occupied by extraframework cations A = Na⁺/Ca²⁺ and B = K⁺/Ba²⁺ have been determined. The characteristic arrangement of the Na⁺/Ca²⁺ cations only at the centers of the 8T rings has been revealed, and for them a new equivalent position in the 16T-opr (6b) tile has been determined. A common crystal-chemical formula of paulingite family zeolites has been obtained: (A,B_0.5)₁₅₄[T₆₇₂O₁₃₄₄]·wH₂O; for the two outermost members, this formula takes the form A₁₅₄[T₆₇₂O₁₃₄₄]·wH₂O and B₇₇[T₆₇₂O₁₃₄₄]·wH₂O. The composition of the alkaline Na,K-paulingite A₁₅₄T₆₇₂O₁₃₄₄·wH₂O = Na₈₂K₇₂[Al₁₅₄Si₅₁₈O₁₃₄₄] ·wH₂O corresponds to the model of a structure with a maximal (100%) and ordered filling of the A cation positions: in the 16T-oto (24h, 48k) tiles for K⁺ and in the 20T-gsm (12d), 30T-plg (16f), and 16T-opr (6b, 12e) tiles for Na⁺. Such a distribution and the overall number of Na and K atoms are in good agreement with the data for synthetic paulingite analogues the (Na₈₇K₇₂TEA₁₅)[Al₁₆₄Si₅₀₈O₁₃₄₄]·wH₂O aluminosilicate and (Na_84.5K_70.5TEA_24.7)[Ga_179.7Si_492.3O₁₃₄₄]·wH₂O gallosilicate.     

Non-empirical SCF molecular orbital studies on simple zeolite model systems

Non-empirical molecular orbital studies on the relative stabilities of topologically closed ring clusters H₈Si₄O₄, [H₈Si₃AlO₄]^? and [H₈Si₂Al₂O₄]^? modelling building units of zeolite frameworks, have been carried out. According to the calculations, AlOAl type bridges are unstable in doubly negative charged species, but can be stabilized in the presence of cations. This stabilization effect increases with increasing cation charge. Several hypothetical bimolecular cluster equilibria are also discussed.     

Mehrkernige Kobaltkomplexe. II. Herstellung und Struktur von [(tren) (NH3)Co(O2)Co(NH3) (tren)](SCN)4 · 2H2O

Polynuclear Cobalt Complexes. II. Preparation and Structure of [(tren) (NH₃)Co(O₂)Co(NH₃) (tren)](SCN)₄ · 2H₂O The title compound is obtained on oxygenation of [Co(tren)(H₂O)₂]²⁺ in 6M aqueous ammonia or by ligand exchange starting from [(NH₃)₅Co(O₂)Co(NH₃)₅]-(NO₃)₄. An X-ray structure determination was made. The substance forms monoclinic crystals, space group P2₁/c, lattice constants a=10,135, b=8,473, c=19,484 Å, β=108,58°, with two formula units in the cell. The final R is 0,066. The binuclear cation has a center of symmetry, so the Co? O? O? Co unit is planar; the Co? O? O angle is 111,5°. The tertiary nitrogen atoms of both chelate groups are cis to the O₂ bridge, as found in doubly bridged [(tren)Co(O₂,OH)Co(tren)](ClO₄)₃ · 3H₂O. On acidification in solution, the singly bridged cation [(tren) (NH₃)CoO₂Co(NH₃)(tren)]⁴⁺ (a) loses the bound O₂ completely. But unlike the doubly bridged cation b , the rate of dissociation of a is independent of pH (Fig. 5). At higher pH (8–10) bridging a→b (Fig. 2) occurs. Both reactions must have the same rate determining step, the first order rate constants being of the order of 2 · 10^?3 s^?1 (25°, 0,35M KCl).     

A new three‐dimensional cobalt(II) coordination polymer with a 4‐connected CdSO4‐like topology

The title cobalt(II) coordination polymer, poly[[diaquacobalt(II)]‐μ₄‐3,3′‐(p‐phenylene)diacrylato], [Co(C₁₂H₈O₄)(H₂O)₂]_n, was obtained by reaction of Co(NO₃)₂·6H₂O and 3,3′‐(p‐phenylene)diacrylic acid (H₂L) under hydrothermal conditions. Each Co^II cation sits on a centre of inversion and is hexacoordinated by six O‐atom donors in an octahedral geometry. The Co^II centres are connected by four centrosymmetric L²⁻ anions, resulting in a three‐dimensional framework structure. The coordinated water molecules and carboxylate O atoms form hydrogen‐bond interactions, stabilizing the structure of the three‐dimensional framework. Topologically, the framework represents a rare example of the three‐dimensional 4‐connected CdSO₄ network type. The metal cations and the organic ligand both show in‐plane coordination with respect to the extended structure.     

Synthesis,crystal structure and properties of a novel 1D chain organic–inorganic rare earth coordination polymer: Gd0.5H0.5{[Gd(H2O)6] [Gd(H2O)2(DMSO)] [α-SiW11O39]}·7H2O

A 1D chain organic–inorganic rare earth coordination polymer Gd_0.5H_0.5{[Gd(H₂O)₆] [Gd(H₂O)₂(DMSO)][α-SiW₁₁O₃₉]}·7H₂O has been synthesized by reaction of α-K₈SiW₁₁O₃₉·13H₂O, HClO₄, Gd₂O₃ with dimethyl sulfoxide (DMSO) and characterized by elemental analysis, IR, UV, ESR spectra and X-ray diffraction. The title compound crystallizes in a monoclinic lattice, P2₁/c space group, with a?=?23.544(5), b?=?11.527(2), c?=?23.297(5)?Å, β?=?109.05(3)°, V?=?35976(2)?ų, Z?=?4, R ₁?=?0.0838, wR ₂?=?0.1300. The neighboring polyanion units {[Gd(H₂O)₆][Gd(H₂O)₂(DMSO)][α-SiW₁₁O₃₉]}^2? are bridged together forming a 1D chain structure by means of [Gd(H₂O)₂(DMSO)]³⁺ ions. The ESR spectra of the title compound at room temperature are composed of eight lines, indicating the strong effect of the crystal field generated by the nearest surrounding ligands of the Gd^III cation.     

K5.76Ga5.76Si10.24O32·3.4H2O,a gallosilicate with the zeolite gismondine topology

The title compound, K–GaSi–GIS, potassium gallium silicon oxide hydrate, was synthesized hydro­thermally and its crystal structure was determined from data collected on a single crystal of dimensions 10 × 10 × 8 µm at a synchrotron X‐ray source. The compound, which has the aluminosilicate (AlSi) zeolite gismondine (GIS) topology, Ca₄[Al₈Si₈O₃₂]·16H₂O, crystallizes in the tetragonal space group I4₁/a. A disordered distribution of the framework Si/Ga sites leads to higher symmetry of the GIS‐type network compared with the usual monoclinic symmetry in AlSi–GIS. Framework Ga substitution for Al in AlSi–GIS leads to substantial distortion of the crankshaft chains, reducing the effective pore dimensions and suggesting the possibility of pore‐dimension control via partial framework‐cation substitution.     

Formation of Silicon-Containing Polyoxoniobates from Hexaniobate Under High Temperature Conditions

Hydrothermal reaction of K₇H[Nb₆O₁₉]·13H₂O with Na₂SiO₃·9H₂O (220 °C, 24 h) produces a lacunary siliconiobate [Si₄Nb₁₆O₅₆]^16?, which was isolated as mixed salt NaK₈H₆[Na@Si₄Nb₁₆O₅₆]·26H₂O (1). Changing the silicon source to Ph₂Si(OH)₂ under the same conditions slightly improves the yield of [Si₄Nb₁₆O₅₆]^16?, which was isolated as K₁₄H[K@Si₄Nb₁₆O₅₆]·26H₂O (2). Extending the reaction time leads to rearrangement of [Si₄Nb₁₆O₅₆]^16? into Keggin-type silicododecaniobate [SiNb₁₂O₄₀]^16?, which was isolated and characterized as K₈H₂(Nb₂O₂)[SiNb₁₂O₄₀]·20H₂O (3). The complexes were characterized by X-ray single crystal analysis, elemental analysis, thermogravimetry, ²⁹Si NMR.     

Synthesis and Crystal Structure of the Coordination Polymer of Ni-Mo8-Pyrazinecarboxylic Acid

An inorganic–organic hybrid compound [Ni₄(pzac)₄(H₂O)₈(β-Mo₈O₂₆)]·2H₂O (1), pzac = 2- pyrazinecarboxylic acid, was synthesized hydrothermally and characterized by IR spectrum, TGA, X-ray single-crystal diffraction. Photoluminescence property has been investigated. In 1 pzac coordinates to Ni1 with a chelating mode and bridges Ni2 forming a one-dimensional undulate chain structure. Ni atom accepts a terminal oxygen atom of [β-Mo₈O₂₆]^4? anion with a little longer Ni–O distances of 2.685 Å and 2.767 Å. [β-Mo₈O₂₆]^4? anion links four Ni atoms of four chains, forming a three-dimensional covalent framework. Lattice water molecules fill the vacancies of the framework.     

β‐Y2Si2O7, a new thortveitite‐type compound,determined at 100 and 280 K

A new form of Y₂Si₂O₇ (diyttrium heptaoxodisilicate) has been synthesized which is isotypic with thortveitite, Sc₂Si₂O₇, and crystallizes in the centrosymmetric space group C2/m, both at 100 and 280 K. The Y³⁺ cation occupies a distorted octahedral site, with Y—O bond lengths in the range 2.239 (2)–2.309 (2) Å. The SiO₄ tetrahedron is remarkably regular, with Si—O bond lengths in the range 1.619 (2)–1.630 (2) Å. The bridging O atom of the Si₂O₇ pyrosilicate group shows a large anisotropic displacement perpendicular to the Si—O bond. Changes in lattice and structural parameters upon cooling are small with, however, a distinct decrease of the anisotropic displacement of the briding O atom. Structure solution and refinement in the non‐centrosymmetric space group C2 are possible but do not yield a significantly different structure model. The Si—O—Si bond angle of the isolated Si₂O₇ groups is 179.2 (1)° at 280 K in C2 and 180° per symmetry in C2/m. The C2/m structure model is favoured.     

A polyoxoniobate constructed from Lindqvist-type hexaniobates and copper coordinated cations

A new organic–inorganic hybrid polyoxoniobate [Cu(1,3-dap)₂(H₂O)][(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]?·?4(1,3-dap)·20H₂O (1) (1,3-dap?=?1,3-diaminopropane) has been synthesized by the diffusion method and structurally characterized by elemental analyses, infrared spectrum, ultraviolet spectroscopy, and single crystal X-ray diffraction. Crystal structure analysis reveals that 1 consists of a dimeric dumbbell anion [(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]^2?, a copper coordinated cation, four 1,3-dap ligands and 20 crystal water molecules. Neighboring units are combined via hydrogen bonds forming a 3-D supramolecular framework.     

Bis(4‐nitro­phenyl) di­sulfide at 150 K,a three‐dimensional framework built from C—H⋯O hydrogen bonds and aromatic π⋯π stacking interactions

In the title compound, (4‐O₂NC₆H₄)₂S₂ or C₁₂H₈N₂O₄S₂, the mol­ecules lie across twofold rotation axes. A single type of C—H?O hydrogen bond, with C?O = 3.394 (3) Å and C—H?O = 158°, links the mol­ecules into continuous two‐dimensional sheets built from a single type of R⁴₄(44) ring. These sheets are linked by aromatic π?π stacking interactions to form a continuous three‐dimensional framework.     

Tetrameric triphenylsilanol, (Ph3SiOH)4, and the adduct (Ph3SiOH)2–di­methyl sulfoxide,both at 120 K,and the adduct (Ph3SiOH)4–1,4‐dioxan at 150 K: interplay of O—H⋯O and C—H⋯π(arene) interactions

The structure of tetrameric tri­phenyl­silanol, C₁₈H₁₆OSi, (I), has been re‐investigated at 120 (2) K. The hydroxyl H atoms were readily located and one of the arene rings is disordered over two closely positioned sets of sites. The mol­ecules are linked into cyclic tetramers, having approximate (S₄) symmetry, via O—H?O hydrogen bonds [H?O 1.81–1.85 Å, O?O 2.634 (3)–2.693 (3) Å and O—H?O 156–166°]. At ambient temperature, there are indications of multiple disorder of the phenyl‐ring sites. In bis­(tri­phenyl­silanol) di­methyl sulfoxide solvate, 2C₁₈H₁₆OSi·C₂H₆OS, (II), the di­methyl sulfoxide component is disordered across a twofold rotation axis in C2/c, and the molecular components are linked by a single O—H?O hydrogen bond [H?O 1.85 Å, O?O 2.732 (2) Å and O—H?O 172°] into three‐mol­ecule aggregates, which are themselves linked into a single three‐dimensional framework by two C—H?π(arene) interactions. In tetrakis­(tri­phenyl­silanol) 1,4‐dioxan solvate, 4C₁₈H₁₆OSi·C₄H₈O₂, (III), the 1,4‐dioxan component lies across an inversion centre in space group P and centrosymmetric five‐mol­ecule aggregates are linked by paired C—H?π(arene) interactions to form molecular ladders.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

catena‐Poly[[[(di‐2‐pyridylamine‐κ2N2,N2′)copper(II)]‐μ‐benzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], a zigzag coordination polymer with strong π–π interactions

The novel title coordination polymer, {[Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O}_n, synthesized by the slow‐diffusion method, takes the form of one‐dimensional zigzag chains built up of Cu^II cations linked by benzene‐1,3‐dicarboxylate (ipht) anions. An exceptional characteristic of this structure is that it belongs to a small group of metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate coordination of individual carboxylate groups. The Cu^II cation has a highly distorted square‐pyramidal geometry formed by three O atoms from two ipht anions and two N atoms from a di‐2‐pyridylamine (dipya) ligand. The zigzag chains, which run along the b axis, further construct a three‐dimensional metal–organic framework via strong face‐to‐face π–π interactions and hydrogen bonds. A solvent water molecule is linked to the different carboxylate groups via hydrogen bonds. Thermogravimetric and differential scanning calorimetric analyses confirm the strong hydrogen bonding.     

Hydrogen‐bonded bilayers in ­piperazinium(2+) bis(mandelate) bis(methanol) solvate

In the title compound, C₄H₁₂N₂²⁺·2C₈H₇O₃^?·2CH₄O, the cations lie across centres of inversion and are disordered over two orientations with equal occupancy; there are equal numbers of (R)‐ and (S)‐mandelate anions present (mandelate is α‐hydroxy­benzene­acetate). The anions and the neutral water mol­ecules are linked by O—H?O hydrogen bonds [O?O 2.658 (3) and 2.682 (3) Å, and O—H?O 176 and 166°] into deeply folded zigzag chains. Each orientation of the cation forms two symmetry‐related two‐centre N—H?O hydrogen bonds [N?O 2.588 (4) and 2.678 (4) Å, and N—H?O 177 and 171°] and two asymmetric, but planar, three‐centre N—H?(O)₂ hydrogen bonds [N?O 2.686 (4)–3.137 (4) Å and N—H?O 137–147°], and by means of these the cations link the anion/water chains into bilayers.