Chain caesium borophosphates with B:P ratio 1:2: synthesis, structure relationships and low-temperature thermodynamic properties

2019 ◽  
Vol 75 (6) ◽  
pp. 1174-1185
Author(s):  
Larisa Shvanskaya ◽  
Olga Yakubovich ◽  
Polina Krikunova ◽  
Evgeny Ovchenkov ◽  
Alexander Vasiliev
Keyword(s):  
Magnetic Field ◽  
Hydrogen Bond ◽  
Thermodynamic Properties ◽  
Membered Ring ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Common Edge ◽  
X Ray ◽  
Hydrogen Bond Interactions ◽  
3D Framework

Three caesium-bearing borophosphates, Cs[BP2O6(OH)2] (I), Cs0.51Mn1.17(H2O)2[BP2O8]·0.45H2O (II) and CsMn[BP2O8(OH)] (III), were synthesized by a hydrothermal method at 473–523 K. Their crystal structures have been studied by means of single-crystal X-ray diffraction; all three structures comprise borophosphate chain anions with a B:P ratio of 1:2. The unique construction of (I) is based on four-membered-ring chains running parallel to the [010] direction. These protonated borophosphate chains are linked via hydrogen-bond interactions to form a 3D framework with caesium cations incorporated. (II) is the first Cs and Mn2+,Mn3+ member of a known family characterized by [BP2O8]∞ helical chains running along [001]. These chains are connected through MnO4(H2O)2 octahedra to form a 3D framework. The caesium cations are disordered over two independent positions in the channels, which they occupy together with water molecules. An additional MnO2(H2O)3 bipyramid statistically shares a common edge and two corners with three main Mn octahedra to form tetrameric clusters. The topological relation between the chain anionic fragments of (I) and (II) as well as the structural relation between (I) and previously studied boro- and berillophosphates are discussed. Compound (III) presents the first Mn member of the A I M III[BP2O8(OH)] family and is characterized by a 3D framework built by open-branched borophosphate chains and MnO5 semi-octahedra sharing vertices. The measurements of thermodynamic properties, i.e. magnetization M and specific heat C p, to 2 K and 30 T, provide evidence that (II) orders antiferromagnetically at the Néel temperature T N = 4.6 K and exhibits a plateau-like feature under the action of an external magnetic field accompanied by a pronounced magnetocaloric effect.

scholarly journals Synthesis and Complexation Properties of 2-Hydroxy-5-methoxyphenylphosphonic Acid (H3L1). Crystal Structure of the [Cu(H2L1)2(Н2О)2] Complex

2021 ◽  
Vol 91 (11) ◽  
pp. 2176-2186
Author(s):  
G. S. Tsebrikova ◽  
Yu. I. Rogacheva ◽  
I. S. Ivanova ◽  
A. B. Ilyukhin ◽  
V. P. Soloviev ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Methoxy Group ◽  
Protonation Constants ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Stability ◽  
Intramolecular Hydrogen ◽  
Oxygen Atoms

Abstract 2-Hydroxy-5-methoxyphenylphosphonic acid (H3L1) and the complex [Cu(H2L1)2(H2O)2] were synthesized and characterized by IR spectroscopy, thermogravimetry, and X-ray diffraction analysis. The polyhedron of the copper atom is an axially elongated square bipyramid with oxygen atoms of phenolic and of monodeprotonated phosphonic groups at the base and oxygen atoms of water molecules at the vertices. The protonation constants of the H3L1 acid and the stability constants of its Cu2+ complexes in water were determined by potentiometric titration. The protonation constants of the acid in water are significantly influenced by the intramolecular hydrogen bond and the methoxy group. The H3L1 acid forms complexes CuL‒ and CuL24‒ with Cu2+ in water.

Synthesis and characterization of the new tin borate SnB8O11(OH)4

2018 ◽  
Vol 73 (5) ◽  
pp. 337-348 ◽  
Author(s):  
Sandra Schönegger ◽  
Klaus Wurst ◽  
Gunter Heymann ◽  
Andreas Schaur ◽  
Andreas Saxer ◽  
...  
Keyword(s):  
Hydrothermal Process ◽  
Building Blocks ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Thermoanalytical Investigations ◽  
Hydrogen Bond Interactions ◽  
Simple Hydrothermal Process

AbstractA new tin(II) borate with the composition SnB8O11(OH)4 was synthesized by a simple hydrothermal process. It crystallizes in the centrosymmetric monoclinic space group P21/n (no. 14) with the lattice parameters a=790.1(1), b=1402.2(2), c=994.8(1) pm, and β=90.40(5)° (Z=4). The new compound SnB8O11(OH)4 is isotypic to PbB8O11(OH)4 and isostructural to BaB8O11(OH)4. The borate layers are built up from fundamental building blocks (FBBs) with the composition [B8O11(OH)4]2−. Four of these FBBs form a nine-membered ring wherein the Sn2+ cations are located. These boron-oxygen layers are further connected by O–H···O hydrogen bond interactions. The characterization of SnB8O11(OH)4 is based on single-crystal X-ray diffraction data, vibrational spectroscopy, DFT calculations, and thermoanalytical investigations including high temperature powder XRD.

Synthesis of ReItricarbonyl complexes with various sulfur- and oxygen-donating ligands: crystal structures of two ReIdinuclear structures bridged by S atoms

2018 ◽  
Vol 74 (10) ◽  
pp. 1116-1122
Author(s):  
Pheello I. Nkoe ◽  
Hendrik G. Visser ◽  
Chantel Swart ◽  
Alice Brink ◽  
Marietjie Schutte-Smith
Keyword(s):  
Hydrogen Bond ◽  
Intermolecular Hydrogen Bond ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
Pyridine Ligand ◽  
X Ray ◽  
Hydrogen Bond Interactions ◽  
Mononuclear Complexes

The synthesis and characterization of two dinuclear complexes, namelyfac-hexacarbonyl-1κ3C,2κ3C-(pyridine-1κN)[μ-2,2′-sulfanediyldi(ethanethiolato)-1κ2S1,S3:2κ3S1,S2,S3]dirhenium(I), [Re2(C4H8S3)(C5H5N)(CO)6], (1), and tetraethylammoniumfac-tris(μ-2-methoxybenzenethiolato-κ2S:S)bis[tricarbonylrhenium(I)], (C8H20N)[Re2(C7H7OS)3(CO)6], (2), together with two mononuclear complexes, namely (2,2′-bithiophene-5-carboxylic acid-κ2S,S′)bromidotricarbonylrhenium(I), (3), and bromidotricarbonyl(methyl benzo[b]thiophene-2-carboxylate-κ2O,S)rhenium(I), (4), are reported. Crystals of (1) and (2) were characterized by X-ray diffraction. The crystal structure of (1) revealed two Re—S—Re bridges. The thioether S atom only bonds to one of the ReImetal centres, while the geometry of the second ReImetal centre is completed by a pyridine ligand. The structure of (2) is characterized by three S-atom bridges and an Re...Re nonbonding distance of 3.4879 (5) Å, which is shorter than the distance found for (1) [3.7996 (6)/3.7963 (6) Å], but still clearly a nonbonding distance. Complex (1) is stabilized by six intermolecular hydrogen-bond interactions and an O...O interaction, while (2) is stabilized by two intermolecular hydrogen-bond interactions and two O...π interactions.

A two-dimensional copper(II) coordination polymer based on 2-propyl-1H-imidazole-4,5-dicarboxylic acid

2015 ◽  
Vol 71 (2) ◽  
pp. 152-154 ◽  
Author(s):  
Di-Chang Zhong ◽  
Hua-Bin Guo ◽  
Ji-Hua Deng ◽  
Ping Lian ◽  
Xu-Zhong Luo
Keyword(s):  
Hydrogen Bond ◽  
Carboxylic Acid ◽  
Dicarboxylic Acid ◽  
Three Dimensional ◽  
Acid Group ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
Carboxylic Acid Group ◽  
X Ray ◽  
Hydrogen Bond Interactions

Single-crystal X-ray diffraction analysis of poly[bis(μ2-5-carboxy-2-propyl-1H-imidazole-4-carboxylato-κ3N3,O4:O5)copper(II)], [Cu(C8H9N2O4)2)]n, indicates that one carboxylic acid group of the 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PDI) ligand is deprotonated. The resulting H2PDI−anion, acting as a bridge, connects the CuIIcations to form a two-dimensional (4,4)-connected layer. Adjacent layers are further linked through interlayer hydrogen-bond interactions, resulting in a three-dimensional supramolecular structure.

Three new amidophosphoric acid esters with a P(O)[OCH2C(CH3)2CH2O] segment: X-ray diffraction, DFT, AIM and Hirshfeld surface investigations of bi- and tri-furcated (three and four-center) hydrogen bond interactions

2020 ◽  
Vol 235 (3) ◽  
pp. 69-84 ◽  
Author(s):  
Marjan Sadat Bozorgvar ◽  
Atekeh Tarahhomi ◽  
Arie van der Lee
Keyword(s):  
Hydrogen Bond ◽  
Crystal Packing ◽  
Closed Shell ◽  
Hirshfeld Surface ◽  
Asymmetric Unit ◽  
X Ray Diffraction ◽  
X Ray ◽  
Hydrogen Bond Interactions ◽  
Amidophosphoric Acid ◽  
Acid Esters

AbstractStructural and packing features of three new amidophosphoric acid esters having a common part XP(O)[OCH2C(CH3)2CH2O], with X = [(CH3)3CNH] (1), [(CH3)2HCNH] (2) and [C6H11(CH3)N] (3), are investigated by single crystal X-ray diffraction. The results illustrate that the compounds 1 and 3 crystallize with one independent molecule in the asymmetric unit; whereas, for 2, the compound crystallizes with three independent molecules in the asymmetric unit. The crystal structures are mostly stabilized via tri-furcated hydrogen bond interactions (C–H · · ·)2(N–H · · ·)O=P in 1 and (C–H · · ·)3O=P in 3, while the stability is given by bi-furcated hydrogen bond interactions (C–H · · ·)(N–H · · ·)O=P in 2. For a better understanding of the nature, strength and energetics associated with the formation of the quoted multi-center hydrogen bond interactions, the Natural Bond Order (NBO) method from Density Functional Theory (DFT) and a topological analysis by means of Atoms In Molecules (AIM) and Hirshfeld surface procedures were performed. These studies reveal that the studied multi-center hydrogen bond interactions of the type O · · · H are favoured in the crystal packing displaying enrichment ratios larger than unity. The detailed nature of the different interactions in these multi-center interactions is studied for the first time in such compounds. It is shown that the N–H · · · O interaction is rather non-covalent closed-shell whereas the C–H · · · O interaction is more van der Waals closed-shell. Stronger hydrogen bond interactions are observed for a lower multiple H-atom acceptor oxygen in three-center hydrogen bond interactions (C–H · · ·)(N–H · · ·)O=P of 2 than for four-center interactions in 1 [i.e. (C–H · · ·)2(N–H · · ·)O=P] and 3 [i.e. (C–H · · ·)3O=P]. The better H-atom acceptability of the O atom of P=O compared with the esteric O atom is explained by the richer s-character of the hybrid orbital of the O atom acceptor of P=O coupled with enhance of the polarization and charge. The obtained results are also confirmed by Molecular Electrostatic Potential (MEP).

Synthesis and Crystal Structure of the Bimetallic Complex [Fe(phen)3]2[phen][V4O12]·19H2O

2008 ◽  
Vol 63 (12) ◽  
pp. 1352-1356 ◽  
Author(s):  
Xiuhong Xua ◽  
Qilin Caob ◽  
Fang Luo ◽  
Guang Wang
Keyword(s):  
Electrostatic Interactions ◽  
Water Molecules ◽  
Supramolecular Framework ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Bimetallic Complex ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Hydrogen Bond Interactions ◽  
1D Chains

A new bimetallic complex, [Fe(phen)3]2[phen][V4O12]·19H2O (1) has been obtained under nonhydrothermal conditions and characterized by single-crystal X-ray diffraction, IR and TG analysis. Crystal data: Fe2V4O31N14C84H94, triclinic, P1̄̄, a = 12.920(5), b = 17.833(5), c = 23.420(5) Å , α = 107.119(5)°, β = 90.643(5)°, γ = 107.643(5)°, Z = 2. In compound 1, water molecules build up 1D chains and decameric rings by hydrogen bonds. The hydrogen bond interactions between decameric rings and 1D chains form a 2D supramolecular sheet with large holes. The [V4O12]4− anions fill these holes. The [Fe(phen)3]2+ cations play a role as charge-compensating and space-filling units. Hydrogen bonding and electrostatic interactions lead to a new 3D supramolecular framework.

A photodimer of a 4-phenyl-4H-pyran

2006 ◽  
Vol 62 (5) ◽  
pp. o1951-o1953 ◽  
Author(s):  
Hong Yan ◽  
Hui-Qin Wang ◽  
Cheng-Liang Ni ◽  
Xiu-Qing Song
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Hydrogen Bond ◽  
Solid State ◽  
Mass Spectroscopy ◽  
Elemental Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Hydrogen Bond Interactions

A new cage photodimer, tetraethyl 2,4,8,10-tetramethyl-6,12-diphenyl-3,9-dioxapentacyclo[6.4.0.02,7.04,11.05,10]dodecane-1,5,7,11-tetracarboxylate, C38H44O10, was prepared through [2+2]-photocycloaddition of diethyl 2,6-dimethyl-4-phenyl-4H-pyran-3,5-dicarboxylate in the solid state. The molecular structure was elucidated by X-ray diffraction analysis, 1H NMR, IR and mass spectroscopy, and elemental analysis. The molecule possesses a crystallographically imposed centre of symmetry. The crystal structure is stabilized by weak C—H...O hydrogen-bond interactions.

scholarly journals Crystal Structure and Electrochemical Property of Tetrazole Complex of Copper [Cu(pta)2(NO3)2(H2O)2] (pta = 1-Phenyl-1H-tetrazole)

2019 ◽  
Vol 31 (10) ◽  
pp. 2370-2374
Author(s):  
E. Liu ◽  
Fangfang Jian
Keyword(s):  
Crystal Structure ◽  
Irreversible Process ◽  
Membered Ring ◽  
Water Molecules ◽  
Stacking Interactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Electrode Cell ◽  
2D Network ◽  
3D Framework

A new compound, [Cu(pta)2(NO3)2(H2O)2] (pta = 1-phenyl-1H-tetrazole) has been synthesized and characterized by IR, elemental analysis and single-crystal X-ray diffractions. X-ray structural analysis reveals that each Cu atom is coordinated by two pta molecules, two nitrate ions and two water molecules to form octahedral coordination geometry. O(1w) atoms of the water molecules serve as H-donor to interact with the nitrate oxygen atoms O(2), O(3) (H-acceptor) and form 1D hydrogen-bond ladder chains. These chains then, construct a 2D network layer via π-π stacking interactions between the five-membered ring of tetrazole and the six-membered ring of benzene. The 3D framework was constructed through the hydrogen bonds of C(7)-H(7A)····O(3). The behaviour of cyclic voltammetry of the compound on three-electrode cell showed an irreversible process.

A New One-Dimensional Coordination Polymer [Co(CCl3COO)2(CH3OH)2(μ-4,4’-bipy)]n: Synthesis and Structural Aspects

2005 ◽  
Vol 60 (1) ◽  
pp. 33-36 ◽  
Author(s):  
Pritha Talukder ◽  
Amitabha Datta ◽  
Samiran Mitra ◽  
Georgina Rosair
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Coordination Polymer ◽  
Linear Chain ◽  
Membered Ring ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Intramolecular Hydrogen ◽  
Structural Aspects

A new one-dimensional coordination polymer [Co(CCl3COO)2(CH3OH)2(μ-4,4’-bipy)]n (1), has been synthesised and its crystal structure determined by single-crystal X-ray diffraction. The structure consists of a one-dimensional linear chain of cobalt(II) centres linked by bridging 4,4’-bipyridine units. The Co(II) ion lies at an inversion centre forming an elongated octahedral coordination sphere. There is an intramolecular hydrogen bond [2.02(5) Å ] between a trichloroacetate oxygen and a methanolic hydrogen forming a planar six-membered ring.

Infrared Studies of Water in Crystalline Hydrates: LiI.3H2O

1971 ◽  
Vol 49 (3) ◽  
pp. 347-351 ◽  
Author(s):  
George Brink ◽  
Michael Falk
Keyword(s):  
Hydrogen Bond ◽  
Water Molecule ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Infrared Studies ◽  
Librational Motion ◽  
Increasing Temperature ◽  
Crystalline Hydrates

The infrared spectra of undeuterated and partially deuterated LiI.3H2O were recorded between 4000 and 1000 cm−1. The splitting of the fundamentals of isotopically dilute HDO indicates that the water molecules are distorted and form one strong, linear OH … I− hydrogen bond and one weak, non-linear hydrogen bond. The non-equivalence of the two hydrogens of the water molecule disagrees with the space group P63mc − C6υ4 for this hydrate, proposed on the basis of X-ray diffraction studies. It is concluded that the space group, including hydrogens, is one of lower symmetry, P63 − C66. The gradual broadening and convergence of the HDO fundamentals at increasing temperature is explained by increasing librational motion of the water molecules.

Sign in / Sign up

Export Citation Format

Share Document