Krystalová struktura anorganických fosforečnanů

½ž ËÙÑÑ ÖÝ Ó ×× ÖØ Ø ÓÒ ½ž½ž Ñ Ó ×× ÖØ Ø ÓÒ The aim of this thesis was to solve and describe the crystal struc- ture of selected inorganic phosphates. Nine different compounds have been studied, including the NASICON type phosphates Co0.5Ti2(PO4)3, Mn0.5Ti2(PO4)3, Na3.215Fe2(PO4)3, the iron(II) diphosphate Fe2P2O7 and hydrates of rare-earth hydrogen diphosphates LnHP2O7·3H2O (Ln = Y, Tb, Dy, Yb) and TbHP2O7·4H2O. While NASICON type phos- phates and rare-earth hydrogen diphosphates have a conventional three- dimensional crystal structure, the structure of α-Fe2P2O7 is incommen- surately modulated and has been described in (3+1)-dimensional super- space. ½ž¾ž ÇÚ ÖÚ Û Ó Ø ÓÒØ ÒØ Ó ×× ÖØ Ø ÓÒ Dissertation is divided in six parts. Part 1 introduce the crystal struc- ture analysis, the concept of aperiodic crystals and the superspace ap- proach. Part 2 describes course of X-ray diffraction experiment and used experimental equipment. The next three parts, Part 3, Part 4 and Part 5, in which the structures of NASICON-type phospates, iron(II) diphos- phate, and rare-earth hydrogen diphosphates are discussed, are the main parts of this work. Part 1. Introduction and Initiation Chapter 2, "Basic principles of crystal structure analysis" con- cerns by fundamentals of crystal structure analysis, i.e. behaviour of X-...¾ž ÙØÓÖ Ö Ø Þ ÖØ ¾ž½ž Ð Þ ÖØ Cílem této práce bylo vyřešit a popsat krystalové struktury vybra- ných anorganických fosforečnanů. Bylo prozkoumáno devět různých lá- tek, a to: fosforečnany typu NASICON: Mn0,5Ti2(PO4)3 Co0,5Ti2(PO4)3, Na3,215Fe2(PO4)3, difosforečnan železnatý Fe2P2O7 a hydráty hydrogen- difosforečnanů prvků vzácných zemin LnHP2O7·3H2O (Ln = Y, Tb, Dy, Yb) a TbHP2O7·4H2O. Zatímco fosforečnany typu NASICON a hydráty hydrogendifosforečnanů prvků vzácných zemin mají konvenční třídimen- zionální krystalové struktury, struktura α-Fe2P2O7 je nesouměřitelně mo- dulovaná a byla popsána v (3 +1)-rozměrném superprostoru. ¾ž¾ž È Ð Ó × Ù Þ ÖØ Práce je rozdělena do šesti částí. Část 1 přibližuje základy strukturní analýzy krystalů, koncepci aperiodických krystalů a superprostorový pří- stup. Část 2 popisuje průběh rentgenového difrakčního experimentu a použité přístroje. Další tři části, část 3, část 4 a část 5, ve kterých jsou diskutovány struktury fosforečnanů typu NASICON, difosforečnanu že- leznatého a hydrátů hydrogendifosforečnanů prvků vzácných zemin, jsou hlavními částmi této práce. Část 1. Úvod a obeznámení s problematikou Kapitola 2, "Základní principy krystalové strukturní analýzy se zabývá základy strukturní analýzy krystalů, tj. chováním rentgenového záření, základní buňkou, symetrií,...Department of Inorganic ChemistryKatedra anorganické chemieFaculty of SciencePřírodovědecká fakult

(E)-4-Bromo-N-(2,3-dimeth­oxy­benzyl­idene)aniline

The title Schiff base compound, C15H14BrNO2, was prepared by the condensation of 2,3-dimeth­oxy­benzaldehyde with 4-bromo­aniline. It adopts an E configuration with respect to the C=N bond. The dihedral angle between the two aromatic rings is 56.79 (8)°. Weak C—H⋯O and C—-H⋯π bonds can be found in the crystal structure

N,N′-Bis(2,3-dimethoxy­benzyl­idene)propane-1,3-diamine

The title compound, C21H26N2O4, adopts an E configuration with respect to the azomethine C=N bonds. The dihedral angle between the two rings is 8.16 (8)°. The crystal structure is stabilized by weak inter­molecular C—H⋯O inter­actions

(E)-N-(2,4-Dimeth­oxy­benzyl­idene)-4-ethoxyaniline

In the title compound, C17H19NO3, the mol­ecule has an E configuration with respect to the C=N bond and the dihedral angle between the aromatic rings is 56.07 (5)°. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds occur. The dimers are linked by weak C—H⋯π inter­actions, forming a three-dimensional network

Hydro­nium perchlorate–dibenzo-18-crown-6 (1/1): monoclinic polymorph

The asymmetric unit of the title compound, H3O+·ClO4 −·C20H24O6, contains two mol­ecules/ions of each species. Both dibenzo-18-crown-6 mol­ecules have a complexed hydro­nium ion inside their cavity with O—H⋯O and O—H⋯(O,O) links between the two species. The associated perchlorate anions also accept O—H⋯O hydrogen bonds from the hydro­nium ion. Both crown ether mol­ecules are present in a butterfly conformation with approximate C 2v symmetry and their cavities are closed by the benzene ring of a neighbouring mol­ecule. The packing is consolidated by C—H⋯O and C—H⋯π inter­actions

Low-temperature superstructure of [(N,N-diisobutyl­carbamo­yl)meth­yl]oct­yl(phen­yl)phosphine oxide (CMPO)

At 120 K, the title compound, C24H42NO2P, crystallizes in a unit cell with a doubled a parameter compared with the room-temperature structure. There are four mol­ecules in the asymmetric unit, one of which shows extensive disorder in a 0.588 (3):0.412 (3) ratio. In the crystal, numerous C—H⋯O inter­actions link the mol­ecules

1,4,8,11-Tetra­azoniacyclo­tetradecane diaqua­tetra­chloridomanganese(II) dichloride dihydrate

The title compound, (C10H28N4)[MnCl4(H2O)2]Cl2·2H2O, consists of isolated octa­hedral [MnCl4(H2O)2]2− anions, tetra­protonated 1,4,8,11-tetra­azoniacyclo­tetradecane cations, chloride anions and water mol­ecules connected by a network of hydrogen bonds. The MnII atom is situated on an inversion centre, and the 1,4,8,11-tetra­azoniacyclo­tetradecane cation is located on a mirror plane

4,4′-Dichloro-3,3′,5,5′-tetra­methyl-2,2′-[(3aR,7aR/3aS,7aS)-2,3,3a,4,5,6,7,7a-octa­hydro-1H-1,3-benzimidazole-1,3-di­yl)bis­(methyl­ene)]diphenol

In the title compound, C25H32Cl2N2O2, there are two intra­molecular O—H⋯ N hydrogen-bonding inter­actions between the hy­droxy groups on the aromatic rings and the two N atoms of the heterocyclic group. The cyclo­hexane ring adopts a chair conformation and the imidazolidine unit to which it is fused has a twisted envelope conformation. The asymmetric unit comprises one half-mol­ecule which is completed by a twofold rotation axis. A C—H⋯O inter­action is observed in the crystal structure

2-(2-Hydroxy­ethyl)-3-[(2-hydroxy­ethyl)imino]isoindolin-1-one

In the crystal structure of the title compound, C12H14N2O3, mol­ecules are packed into layers parallel to (100). Each layer contains centrosymmetric dimers formed by a pair of strong O—H⋯N hydrogen bonds with an R 2 2(10) motif, while strong O—H⋯O hydrogen bonds forming C(10) chains connect mol­ecules into a two-dimensional network. Additional stabilization is supplied by weak C—H⋯O hydrogen bonds and weak π–π stacking inter­actions with centroid–centroid distances in the range 3.4220 (7)–3.9616 (7) Å

1-Hexyl-1,3,6,8-tetra­aza­tricyclo­[4.3.1.13,8]undecan-1-ium iodide

In the title compound, C13H27N4 +·I−, the ethyl­ene bridge is distorted from the ideal D 2d symmetry wherein an N—C—C—N planar bridge, around whose C—C bond the C—N and C—H bonds are exactly eclipsed, is disordered over two sites with equal occupancies. In both disorder components, the hexyl chain adopts an ideal all-trans conformation. In the crystal, adjacent ions are connected by C—H⋯I hydrogen bonds, forming ionic pairs that are further linked into chains along [101] via a second C—H⋯I inter­action