Complex Three-dimensional Framework Research Articles

Attempted syntheses of new mixed-cation hexafluoridoarsenates(V) in liquid anhydrous HF acidified with AsF5; the crystal structures of A3M(HF)Mn(AsF6)7 (A = H3O, K/H3O; M = Ca, Sr, Ba)

A study of the reactions between the various starting molar ratios of H3OAsF6, and in situ prepared M(AsF6)2 (M = Mg, Ca, Sr, Ba) and Mn(AsF6)2 in liquid anhydrous hydrogen fluoride (aHF) acidified with AsF5 resulted in three novel oxonium salts, i.e. (H3O)3M(HF)Mn(AsF6)7 (M = Ca, Sr) and (H3O)5BaMn(AsF6)9. Reactions between in situ prepared AAsF6 (A = K, NH4), M(AsF6)2 (M = Ca, Sr, Ba) and M’(AsF6)2 (M’ = Mn, Mg, Ni, Co, Zn) in aHF acidified with AsF5 gave mixtures of various products upon crystallization. An attempt to grow single crystals of K3Ba(HF)Mn(AsF6)7 resulted in (H3O/K)3Ba(HF)Mn(AsF6)7 instead, due to moisture penetrating through the reaction vessel walls during long lasting crystallization. The crystal structures of A3M(HF)Mn(AsF6)7 (A = H3O for M = Ca and Sr; A = H3O/K for M = Ba) salts are isotypical and crystallize in the monoclinic space group P21/n (No. 14). The crystal structures consist of a complex three-dimensional framework formed from M2+ (M = Ca, Sr, Ba) and Mn2+ cations interconnected with [AsF6]– anions. The HF molecules are bound directly to alkaline earth metals via the fluorine atom. Single charged cations are located within the cavities. The Mn atoms are found in an octahedral coordination of six fluorine atoms. The Ca atoms are coordinated by eight fluorine atoms, while this number increases to nine for the Sr and Ba atoms.

Synthesis, crystal structure, and non-covalent interactions in 4-hydrazinobenzoic acid hydrochloride

The compound 4-hydrazinobenzoic acid hydrochloride (4-HBA), C7H9O2·Cl, has been synthesized and characterized by FT-IR spectroscopy and X-ray diffraction. The compound crystallizes as colourless needles in a triclinic system, space group Pˉ1 (Z = 2), and cell parameters a = 3.7176 (4) Å, b = 5.9133 (4) Å, c = 19.3631 (13) Å, α = 87.841 (6), β = 88.924 (6), γ = 80.203 (6), V = 419.13 (6) Å3. The component ions are linked by a combination of O–H⋯O, N–H⋯N and N–H⋯Cl hydrogen bonds to form a complex three-dimensional framework structure in which each cation is linked to two other cations, by O–H⋯O and N–H⋯N hydrogen bonds, and to five different anions, while each anion accepts hydrogen bonds from five different cations. Calculations on the Non-Covalent Interactions (NCI) amplify the crystallographic conclusions concerning the interionic hydrogen bonds.

Synthesis, crystal structure and spectroscopic characterization of a new cadmium phosphate, Na2Cd5(PO4)4

A novel cadmium phosphate compound Na2Cd5(PO4)4 was synthesized in single crystal and in powder forms using flux and Pechini methods, respectively. It was then characterized by single crystal X-ray diffraction, vibrational spectroscopy and photoluminescence measurements. This compound crystallizes in the monoclinic system with space group P21/a, lattice parameters a = 8.276(1) Å, b = 9.301(3) Å, c = 9.455(2) Å, β = 111.82 (1)° and Z = 2. The structure consists of (Na3/4,Cd1/4)O7, (Cd3/4,Na1/4)O6 and CdOx (x = 6, 7), polyhedra and PO4 tetrahedra linked through common corners or edges giving rise to a novel type of complex three-dimensional framework. This structure could be described in terms of [(Na3/4,Cd1/4)2(Cd3/4,Na1/4)2Cd3O16]∞ layers stacked parallel to the (2 0–3) plane and interconnected both directly and via PO4 tetrahedra by sharing common corners and edges. Vibrational spectroscopy and cadmium photoluminescence were analyzed according to the structural results.

Induction of steady-state glomeruloid sphere by self-assembly from human embryonic kidney cells

The glomerulus is a network of capillaries known as a tuft, located at the beginning of a nephron in the kidney. Here we describe a novel method for the induction of a macroscopically visible three-dimensional glomerulus-like sphere (GLS). This procedure did not require any additional cytokines and completed the formation of spheres within 24 h. After the formation was complete, GLS maintained a steady state for at least five days without proliferation and without a decrease in viability. Therefore, this procedure assists various assays for a prolong period of time. Overall, our protocol allows for a very simple mixing of cells from different sources to obtain fine-grained and highly dispersed GLSs. The kidney filtration barrier is a unique structure characterized by a complex three-dimensional framework of podocytes and endothelial cells. GLS exhibited the induction of many podocyte-specific gene profiles similar to those in adult human kidneys, suggesting that the sphere formation process is important for the maturation of podocytes. Focal segmental glomerulosclerosis (FSGS) is one of the major causes of steroid-resistant nephrotic syndrome, and some circulating permeability factors in the patient's serum FSGS have been implicated in the pathogenesis of the disease. Serum from patients with FSGS induced the collapse of GLS, which imitates the appearance of glomerulosclerosis in patients. In conclusion, the investigation and use of GLS may provide a novel method to elucidate the molecular mechanisms underlying complicated and unexplained events in glomeruli in a similar condition in adult kidneys.

Site-selective As–P substitution and hydrogen bonding in the crystal structure of philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O

Philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O, from the Middle Pit, Gold Hill Mine, Tooele Co., Utah, USA, was studied by single-crystal X-ray diffraction and scanning electron microscopy. The empirical formula of the studied sample is (Cu4.69Zn1.23)(As0.86P0.18O4)2(OH)5.61·H2O, which agrees well with the previous reports on the mineral. Philipsburgite is monoclinic, P21/c, a = 12.385(6), b = 9.261(4), c = 10.770(5) A, β = 97.10(1)o, V = 1225.7(9) A3 (at 100 K), and Z = 4. The crystal structure was refined to R1 = 0.046 for 2563 unique observed reflections with |Fo| ≥ 4σF. The crystal structure of philipsburgite is isotypic to that of kipushite and can be considered as a complex three-dimensional framework consisting of two types of layers stacked parallel to the a-axis. The A-type layer is formed by the edge-sharing Jahn–Teller-distorted Cuφ6 octahedra [φ = O2−, (OH)−, H2O]. Two adjacent octahedral layers are linked via (As2O4) tetrahedra. The B-type layer is built by corner-sharing (ZnO4) and (As1O4) tetrahedra and is formed by the four- and eight-membered tetrahedral rings. The A:B ratio of the A and B layers is equal to 2:1. The hydrogen bonding network in philipsburgite is rather complex and consists of two- and three-center hydrogen bonds. The As1 site accommodates ca. 18% of P and is a preferable position for the P substitution in philipsburgite. The observed selectivity of the As1 site for P may indicate that, for the intermediate compositions with the P:As ratios close to 1:1, there is a fully ordered species with P prevalent at the As1 site and As prevalent at the As2 site. The intermediate composition would, therefore, be Cu5Zn(AsO4)(PO4)(OH)6·H2O and such a mineral can be considered as a separate species, according to the rules of the International Mineralogical Association (IMA). Philipsburgite should be considered as structurally complex with the Shannon information contents of 4.954 bits/atom and 614.320 bits/cell. The obvious reason for the structural complexity of the mineral is its modularity, i.e., the presence of two structurally distinct modules, the octahedral–tetrahedral (A) and tetrahedral (B) layers.

Redetermination of the crystal structure of bis-(tri-2-pyridyl-amine)-iron(II) bis-(perchlorate), and a new refinement of the isotypic nickel(II) analogue: treatment of the perchlorate anion disorder.

The redetermination of the structure of the title compound, [Fe(C15H12N4)2](ClO4)2, (I), confirms the structure previously reported [Kucharski et al. (1978a ▸). Aust. J. Chem. 31, 53-56], but models the perchlorate over four sets of atomic sites, rather than using just one set of sites as in the original report. The supra-molecular assembly, not reported previously, takes the form of a complex three-dimensional framework built from C-H⋯O hydrogen bonds. The isotypic nickel(II) analogue, [Ni(C15H12N4)2](ClO4)2, (III), has been refined using the original data set [Wang et al. (2011 ▸). Acta Cryst. E67, m78], again using a four-component disorder model for the anion, rather than a two-component model as in the original report, leading to more satisfactory Cl-O distances and O-Cl-O angles.

Li1.52Na4.48Cd8(PO4)2(P2O7)4: A new mixed-anion diphosphate containing four types of dimensions groups

A new mixed-anion diphosphate, Li1.52Na4.48Cd8(PO4)2(P2O7)4, was synthesized by standard high-temperature solid state technique for the first time. It crystallizes in triclinic space group P-1, with unit cell parameters a=6.7330(3) Å, b=9.5603 (4) Å, c=11.3838 (5) Å, α=98.5630(10) °, β=92.3460(10) °, γ=90.4500(10) °. The crystal structure contains four types of dimensions, that is zero-dimensional (0D) Cd4O16 groups, one-dimensional (1D) [M2P5O20]∞ (M=Li/Na, Na) chains, two-dimensional (2D) Na/CdO6 layers and the complex three-dimensional (3D) framework. After careful structural analysis, it is found that the number of cations has an effect on the degree of polymerization of the [PO4] groups. Thermal behaviors indicate that the title compound melts congruently and infrared (IR) spectrum shows the existences of PO4 and P2O7 groups. The ultraviolet-visible light-near infrared (UV/Vis/NIR) diffuse reflectance spectra are also performed on this compound.

Hidden impacts of ocean acidification to live and dead coral framework.

Cold-water corals, such as Lophelia pertusa, are key habitat-forming organisms found throughout the world's oceans to 3000 m deep. The complex three-dimensional framework made by these vulnerable marine ecosystems support high biodiversity and commercially important species. Given their importance, a key question is how both the living and the dead framework will fare under projected climate change. Here, we demonstrate that over 12 months L. pertusa can physiologically acclimate to increased CO2, showing sustained net calcification. However, their new skeletal structure changes and exhibits decreased crystallographic and molecular-scale bonding organization. Although physiological acclimatization was evident, we also demonstrate that there is a negative correlation between increasing CO2 levels and breaking strength of exposed framework (approx. 20–30% weaker after 12 months), meaning the exposed bases of reefs will be less effective ‘load-bearers’, and will become more susceptible to bioerosion and mechanical damage by 2100.

Ternary Arsenides A2Zn5As4 (A = K, Rb): Zintl Phases Built from Stellae Quadrangulae

Stoichiometric reaction of the elements at high temperature yields the ternary arsenides K(2)Zn(5)As(4) (650 °C) and Rb(2)Zn(5)As(4) (600 °C). They adopt a new structure type (Pearson symbol oC44, space group Cmcm, Z = 4; a = 11.5758(5) Å, b = 7.0476(3) Å, c = 11.6352(5) Å for K(2)Zn(5)As(4); a = 11.6649(5) Å, b = 7.0953(3) Å, c = 11.7585(5) Å for Rb(2)Zn(5)As(4)) with a complex three-dimensional framework of linked ZnAs(4) tetrahedra generating large channels that are occupied by the alkali-metal cations. An alternative and useful way of describing the structure is through the use of stellae quadrangulae each consisting of four ZnAs(4) tetrahedra capping an empty central tetrahedron. These compounds are Zintl phases; band structure calculations on K(2)Zn(5)As(4) and Rb(2)Zn(5)As(4) indicate semiconducting behavior with a direct band gap of 0.4 eV.

Na7Mg13Nd(PO4)12

Investigations of the quasi-ternary system Na3PO4–Mg3(PO4)2–NdPO4 allowed us to obtain the new phosphate hepta­sodium trideca­magnesium neodymium dodeca­kis­phosphate, Na7Mg13Nd(PO4)12, by applying a flux method. The crystal structure is isotypic with that of the previously reported Na7Mg13 Ln(PO4)12 (Ln = Eu, La) compounds. It consists of a complex three-dimensional framework built up from an NdO8 polyhedron (m symmetry), an MO6 octa­hedron statistically occupied by M = Mg and Na, and eight MgOx (x = 5, 6) polyhedra (four with site symmetry m), linked either directely by sharing corners, edges and faces, or by one of the eight unique PO4 tetra­hedra through common corners. Two of the PO4 tetra­hedra are statisticaly disordered over a mirror plane. The whole structure can be described as resutling from an assembly of two types of structural units, viz [Mg4 MP4O22]∞ 2 layers extending parallel to (100) and stacked along [100], and [Mg4NdP4O36]∞ 1 undulating chains running along the [010] direction. The six different Na+ cations (five with site symmetry m and one with 0.5 occupancy) are situated in six distinct cavities delimited by the framework. The structure was refined from data of a racemic twin.

Bis(2-hydroxyethanaminium) tetrachloridopalladate(II)

In the title compound, (C2H8NO)2[PdCl4], 2-hy­droxy­ethanaminium cations and tetra­chloridopalladate(II) dianions crystallize in a 2:1 ratio with the anion residing on a crystallographic inversion center. The cations and anions are linked in a complex three-dimensional framework by three types of strong hydrogen bonds (N—H⋯O, N—H⋯Cl, and O—H⋯Cl), which form various ring and chain patterns of up to the ternary graph-set level.

Synthesis and structural characterization of a new yttrium phosphate: Na 2.5Y 0.5Mg 7(PO 4) 6 with fillowite-type structure

A new phosphate, Na 2.5Y 0.5Mg 7(PO 4) 6 was synthesized as single crystals by the flux method and as a powdered sample by the Pechini technique, and investigated by single crystal X-ray diffraction, charge distribution (CD) and 31P NMR spectroscopy. This compound crystallized in the rhombohedral space group R ▪ and its equivalent hexagonal cell had the following parameters: a=1.4976(6) nm, c= 4.2599(7) nm, Z= 18. The structure consisted of MgO 5, MgO 6, YO 6, (Na,Y)O 8 and NaO x ( x=6, 7 and 9) polyhedra which were linked either directly through common corners, edges and faces and by means of the PO 4 tetrahedra via common corners and edges, giving rise to a complex three-dimensional framework, similar to that of the fillowite-like structure. The cation distribution was confirmed by charge distribution (CD) calculations and 31P NMR spectroscopy study.

Anomeric effect and hydrogen-bonded supramolecular motif in 5-(3-fluoro-4-methoxyphenyl)-1-[(3-fluoro-4-methoxyphenyl)aminomethyl]-1,3,5-triazinane-2-thione

In the title compound, C(18)H(20)F(2)N(4)O(2)S, the triazinane-2-thione ring adopts an envelope conformation, the ring substituents lie on the same side of the mean plane of the heterocyclic ring and the exo lp-N-C-N(triaz) unit (lp is a lone pair and triaz is the triazinane ring) exhibits an antiperiplanar orientation, which is shown to be governed by strong anomeric effects. Molecules are linked into a complex three-dimensional framework by a combination of two N-H...S hydrogen bonds, three C-H...F hydrogen bonds and a pi-pi stacking interaction.

Ba 5Ti 12Sb 19+x, a polar intermetallic compound with a stuffed γ-brass structure

The polar intermetallic compound Ba 5Ti 12Sb 19+ x ( x⩽0.2) has been synthesized by reaction of the elements. Single-crystal X-ray diffraction analysis revealed that it adopts a new structure type (Ba 5Ti 12Sb 19.102(6), space group P 4 3 ¯ m , Z=2, a=12.4223(11) Å, V=1916.9(3) Å 3). The set of Ba and Sb sites corresponds to the structure of Cu 9Al 4, a γ-brass type with a primitive cell. A complex three-dimensional framework of Ti atoms, in the form of linked planar Ti 9 clusters, is stuffed within the γ-brass-type Ba–Sb substructure. Notwithstanding its relationship to the γ-brass structure, the compound does not appear to conform to the Hume–Rothery electron concentration rules. Band structure calculations on an idealized Ba 5Ti 12Sb 19 model suggest that the availability of bonding states above the Fermi level is responsible for the partial occupation, but only to a limited degree, of an additional Sb site within the structure. Magnetic measurements indicated Pauli paramagnetic behaviour.

An inorganic–organic hybrid material with a novel oxometallic framework: Hydrothermal synthesis and characterization of [Zn3O3(C13H14N2)3]V6O15

A new hybrid material [Zn3O3(C13H14N2)3]V6O15 (1) with extended framework structure has been synthesized hydrothermally and characterized by vibrational spectroscopy, thermogravimetry and complete single crystal X-ray diffraction analysis. The compound has a complex three-dimensional covalent framework structure. It exhibits a fully oxidized novel oxometallic framework containing 10-membered {V4ZnO5} oxometalate rings and 4,4′-trimethylene dipyridine ligands (C13H14N2) that connect pairs of crystallographically equivalent zinc atoms. The extended structure of 1 may also be viewed as containing a framework of corner-sharing {VO4} and {ZnO2N2} polyhedra together with 4,4'-trimethylene dipyridine ligands linking zinc centers. The hybrid material is thermally stable up to 323 °C. It contains metal centers and coordination geometry that make it a potentially attractive model compound for investigating the structures of metallo-organic biomolecules by use of solid state NMR spectroscopic techniques. Crystal data for C39H42N6O18V6Zn3: monoclinicic P21, a = 10.9894(9) A, b = 18.1493 (15) A, c = 13.0903 (11) A, β = 109.8880(10)°, V = 2455.1(4) A3, Z = 2, Dcalc. = 1.873 Mg/m3. © 2009 Elsevier B.V. All rights reserved.

Codeine dihydrogen phosphate hemihydrate

The cation of the title structure [systematic name: (5alpha,6alpha)-6-hydroxy-7,8-didehydro-4,5-epoxy-3-methoxy-17-methylmorphinanium dihydrogen phosphate hemihydrate], C18H22NO3+.H2PO4-.0.5H2O, has a T-shaped conformation. The dihydrogen phosphate anions are linked by O-H...O hydrogen bonds to give an extended ribbon chain. The codeine cations are linked together by O-H...O hydrogen bonds into a zigzag chain. There are also N-H...O bonds between the two types of hydrogen-bonded units. Additionally, they are connected to one another via O...H-O-H...O bridging water molecules. The asymmetric unit contains two codeine hydrogen cations, two dihydrogen phosphate anions and one water molecule. This study shows that the water molecules are firmly bound within a complex three-dimensional hydrogen-bonded framework.

Ethyl 4-amino-5-cyano-2-methyl-6-(2-nitrophenoxy)nicotinate

In the title compound, C16H14N4O5, the benzene ring of the nicotinate residue is inclined at an angle of 64.06 (10)° to the benzene ring of the nitrophenoxy group. The molecules are linked by two intermolecular C—H...O and N—H...N hydrogen bonds into a complex three-dimensional framework structure. C—H...π interactions also contribute to the stability of the crystal packing.

Magnesium Borohydride: Synthesis and Crystal Structure

(Figure Presented) Unexpected structural complexity: Well-crystallized Mg(BH4)2 powder is obtained, allowing the structure to be determined from synchrotron X-ray and neutron diffraction data. Mg(BH 4)2 is a novel and remarkably complex three-dimensional framework in which each Mg2+ ion (blue) is tetrahedrally coordinated by four [BH4]- tetrahedra (B red, H gray; see picture). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

Poly[bis(μ3-dihydrogen malonato)calcium(II)

The title compound, [Ca(C3H3O4)2]n, has a polymeric structure, built up from noncentrosymmetric Ca2O12 face-sharing bipolyhedra, linked through the spacers of the ligands and forming a complex three-dimensional framework containing empty channels parallel to the [001] direction. The calcium ion lies on a 2 axis and is coordinated by eight O atoms from six hydrogen malonate ligands in a distorted bicapped dodeca­hedron. The tridentate ligand displays an η5-chelating coordination mode and forms both μ1,1 and μ1,3 bridges. In the extended network, the protonated O atom is involved in a strong hydrogen bond with a deprotonated O atom, forming an infinite array of the ligands. An M—O—M infinite linkage characteristic of metal–organic frameworks is prevented here by cage assembly around the metal.

N-(4-Nitrobenzoyl)-N′-phenylhydrazine: a three-dimensional hydrogen-bonded framework

In the title compound (systematic name: N-anilino-4-nitrobenzamide), C(13)H(11)N(3)O(3), the molecules are linked into a complex three-dimensional framework structure by a combination of two-centre N-H...O and C-H...O hydrogen bonds and a three-centre N-H...(O,N) hydrogen bond.