#### Zeitschrift für Kristallographie - Crystalline Materials

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ISSN / EISSN : 2194-4946 / 2196-7105
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Jun-Xia Li, Lin-Yuan Xiong, Xiao-Jie Xu, Chang Liu, Zheng-Guo Wang
Published: 5 October 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0047

Abstract:
Triclopyr ethyl ester (1) has been co-synthesized through one-pot solvothermal reaction and the crystal structure has been determined by single crystal X-ray structure analysis. The compound C18H16Cl6N2O6 crystallizes in the monoclinic crystal system, P21/c space group with unit-cell parameters: a = 4.9615(2) Å, b = 30.9297(14) Å, c = 15.9155(10) Å, β = 91.466(4)° and Z = 4. Each unit cell is composed of two discrete, similar but reversely arranged triclopyr ethyl ester organic molecules. In the 3D packing plot, 1 is further assembled into a network structure via rich Cl⋯Cl halogen bond interactions. In addition, the crystal structure, the flexible conformation of phenoxy methylene group of 1 has been carefully compared and discussed with those of triclopyr acid.
, Lyna Torzuoli, Assil Bouzid, Philippe Thomas, Olivier Masson
Published: 19 September 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0042

Abstract:
New and refined bond valence parameters related to ion pairs constituted of the tellurium Te4+ cation and non-oxide Xn anions (X = F, S or Se) are proposed. After a selection of specific crystalline structures, the optimization of the bond valence parameters R and b with a cutoff distance is carried out by minimizing the root mean square deviation of the Te4+ cation valence. The results are R = 1.728 Å and b = 0.622 Å with cutoff = 5.3 Å for the Te4+–F pair and R = 2.444 Å and b = 0.387 Å with cutoff = 4.5 Å for the Te4+–S2− pair. These parameters lead to a lower dispersion of the calculated valences around the formal valence compared to that obtained with the parameters available in the literature. As for the new set related to the Te4+–Se2− pair, we find R = 2.578 Å and b = 0.296 Å with cutoff = 3.7 Å.
Maximilian Kai Reimann, Steffen Klenner, Josef Maximilian Gerdes, Michael Ryan Hansen,
Published: 16 September 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0048

Abstract:
The magnesium-rich intermetallic compounds RE3Ag4Mg12 (RE = Y, La–Nd, Sm–Dy, Yb) and AE3Ag4Mg12 (AE = Ca, Sr) were synthesized from the elements in sealed tantalum ampoules through heat treatment in an induction furnace. X-ray powder diffraction studies confirm the hexagonal Gd3Ru4Al12 type structure, space group P63/mmc. Three structures were refined from single crystal X-ray diffractometer data: a = 973.47(5), c = 1037.19(5) pm, wR2 = 0.0296, 660 F2 values, 30 variables for Gd3Ag3.82(1)Mg12.18(1), a = 985.27(9), c = 1047.34(9) pm, wR2 = 0.0367, 716 F2 values, 29 variables for Yb3Ag3.73(1)Mg12.27(1) and a = 992.41(8), c = 1050.41(8) pm, wR2 = 0.0373, 347 F2 values, 28 variables for Ca3Ag3.63(1)Mg12.37(1). Refinements of the occupancy parameters revealed substantial Ag/Mg mixing within the silver-magnesium substructure, a consequence of the [email protected]8 coordination. The alkaline earth and rare earth atoms build Kagome networks. Temperature dependent magnetic susceptibility measurements indicate diamagnetism/Pauli paramagnetism for the compounds with Ca, Sr, Y and YbII, while the others with the trivalent rare earth elements are Curie-Weiss paramagnets. Most compounds order antiferromagnetically at TN = 4.4(1) K (RE = Pr), 34.6(1) K (RE = Gd) and 23.5(1) K (RE = Tb) while Eu3Ag4Mg12 is a ferromagnet (TC = 19.1(1) K). 151Eu Mössbauer spectra confirm divalent europium (δ = −9.88(1) mm s−1). Full magnetic hyperfine field splitting (18.4(1) T) is observed at 6 K. Yb3Ag4Mg12 shows a single resonance in its 171Yb solid state NMR spectrum at 6991 ppm at 300 K indicating a strong, positive Knight shift.
Khurshid Sohail, , , Xiaoyu Guo,
Published: 5 September 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0044

Abstract:
As described in the Introduction, we became interested in the existing literature for the crystallization behavior of (±)-[Co(en)3]I3·H2O and the absolute configuration of its enantiomers because of our project on the historical sequence of chemical studies leading Werner to formulate his Theory of Coordination Chemistry. In so doing, we discovered a number of interesting facts, including the possibility that the published “Pbca” structure of the (±)-[Co(en)3]I3·H2O was incorrect, and that it really crystallizes as a kryptoracemate in space group P212121. Other equally interesting facts concerning the crystallization behavior of [Co(en)3]I3·H2O are detailed below, together with an explanation why Platon incorrectly selects, in this case, the space group Pbca instead of the correct choice, P212121. As for the Flack parameter, (±)-[Co(en)3]I3·H2O provides an example long sought by Flack himself – a challenging case, differing from the norm. For that purpose, data sets (for the pure enantiomer and for the racemate) were collected at 100 K with R-factors of 4.24 and 2.82%, respectively, which are ideal for such a test. The fact that Pbca is unacceptable in this case is documented by the results of Second-Harmonic Generation experiments. CCDC nos: 1562401 for compound (I) and 1562403 for compound (II).
Reinhard K. Kremer, Sebastian Bette, Eva Brücher, Jürgen Nuss, Armin Schulz, Myung-Hwan Whangbo, Hyun-Joo Koo
Published: 2 September 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0040

Abstract:
We report on the magneto-structural properties of the rare copper aluminum hydroxo-arsenate mineral liroconite with chemical composition Cu2AlAs1−xPxO4(OH)4·4H2O (x ≈ 0.2). In order to characterize the natural mineral sample chemical analyses, X-ray single crystal and powder diffraction, heat capacity and crystal water desorption, anisotropic thermal expansion and Raman scattering and magnetic susceptibility investigations have been carried out. The magnetic properties are well described by two discrete oxygen bridged Cu2+ spin S = 1/2 dimers with antiferromagnetic spin exchange ranging between −320 K and −136 K, depending on to which group-15 five-valent cation, As5+ or P5+, the dimer bridging oxygen atoms coordinate to. Accordingly the temperature dependence of the magnetic susceptibilities can be well fitted to a sum of two Bleaney–Bowers type spin S = 1/2 dimer susceptibilities suggesting that the dimers show negligible mixed coordination to (AsO4)3−/(PO4)3− tetrahedra. DFT + U calculation confirm the ratio of the spin exchange parameters of the (AsO4)3− or (PO4)3− coordinated Cu2+ – Cu2+ dimers. Inter dimer spin exchange is about two orders of magnitude smaller than intra dimer exchange.
, Irina I. Buchinskaya, Nikolay I. Sorokin
Published: 26 August 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0032

Abstract:
The temperature dependences of the ionic electrical conductivity of fluorite-type (sp. gr. F m 3 ‾ m $Fm\overline{3}m$ , Z = 8) KDy3F10 and KHo3F10 single crystals grown by the Bridgman technique have been studied by impedance spectroscopy for the first time. The correlation between the conductometric and structural characteristics of KR3F10 (R = Tb, Dy, Ho, Y) crystal family from the point of view of the observed size effect in the ionic conductivity is discussed. With decrease in the unit-cell volume V1F per fluorine atom in a series of crystals with R = Tb, Dy, Ho and Y, the activation energy Eσ of ion transfer decreases from 1.57 to 1.16 eV respectively and the fluorine-ion conductivity value increases from 3.0 × 10−5 to 4.4 × 10−4 S cm at 773 K, i.e. the nature of the conductivity change is linearly antibatic. This phenomenon can be useful for developing approaches and search strategies for new ionic conductors.
, Stanislav Savvin, Siân E. Dutton
Published: 22 August 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0029

Abstract:
Calcium lanthanide oxyborates Ca4LnO(BO3)3 are of interest for their optical and electromechanical properties. Their crystal structure has been well characterised using powder and single-crystal X-ray diffraction but there remains some disagreement regarding cation ordering in these compounds. In this study, combined X-ray and neutron powder diffraction was employed to study the cation distribution and obtain accurate boron and oxygen atomic coordinates for six Ca4LnO(BO3)3 compounds (Ln = Pr, Nd, Tb, Ho, Er, Yb) at room temperature and one (Ln = Tb) at 50 and 1.5 K. All compounds adopt the previously reported monoclinic structure with space group Cm. The Ln3+ ions are disordered over two of the three metal sites, with the extent of disorder increasing across the lanthanide series with decreasing ionic radius. Low-temperature neutron data for Ca4TbO(BO3)3 showed a decrease in paramagnetic scattering on cooling but no obvious magnetic Bragg or diffuse scattering at the lowest temperature of 1.5 K. We report specific heat data at cryogenic temperatures for eight Ca4LnO(BO3)3 compounds and relate the magnetic properties of these compounds to their structural behaviour.
Feodor F. Chausov, Nikita E. Suksin, Aleksandr V. Kholzakov, Natalya V. Lomova, Irina S. Kazantseva, Dmitry S. Rybin
Published: 19 August 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0034

Abstract:
The cluster structure, thermochemical behavior, and some mechanisms of thermal decomposition of the crystalline products in the isodimorphic substitution series CuxNi(1−x)NTP (x = 0 … 1) have been studied by simultaneous the thermal gravimetric analysis and differential thermal analysis (TGA/DTA) and X-ray photoelectron spectroscopy (XPS). The complexes NiNTP and Cu1/8Ni7/8NTP with a monoclinic crystal structure are the most thermo-stable and characterized by one-step decomposition at 400–440 °C with the formation of metal phosphides and phosphates. The complexes Cu3/8Ni5/8NTP–Cu3/4Ni1/4NTP with the triclinic crystal lattice and the trigonal-bipyramidal coordination of metal atoms decompose in two steps. Firstly, the formation of a heteroligand complex with imino-bis-methylenephosphonic and methylphosphonic acids takes place at 245 °C. Secondly, the complex decomposes at 270–380 °C. The monometallic complex CuNTP decomposes almost completely at 280–300 °C.
, Erika Samolová, Michal Dušek
Published: 17 August 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2021-2074

Abstract:
There are reported two related structures of Ba5Mg4C54O48H114 (dodeca(aqua-6κ3O,7κ3O,8κ3O,9κ3O)-tris(μ2-propanoato-1:6κ2O,1κO′)-tris(μ-propanoato-2:7κ2O,2κO′-tris(μ-propanoato-3:8κ2O,3κO′)-tris(μ-propanoato-4:9κ2O,4κO′)-hexakis(μ3-propanoato-1:5κ2O,2:5κ2O′;1:5κ2O,3:5κ2O′;1:5κ2O,4:5κ2O′;2:5κ2O,3:5κ2O′;2:5κ2O,4:5κ2O′;3:5κ2O,4:5κ2O′)-pentabarium tetramagnesium), (I), and Pb5Mg4C54O48H114 (dodeca(aqua-1κ3O,2κ3O,3κ3O,4κ3O)-hexakis(μ3-propanoato-1:5κ2O,2:5κ2O′;1:5κ2O,3:5κ2O′;1:5 κ2O,4:5κ2O′;2:5κ2O,3:5κ2O′;2:5κ2O,4:5κ2O′;3:5κ2O,4:5κ2O′)tetramagnesium lead(II) tris(propanoato-κ2O,O′)plumbate(II)), (II). The title structures are compositional isomers which crystallize in the same space group type. The structure of (I) comprises molecules with symmetry 4 ‾ 3 m $\overline{4}3m$ . The structure (II) comprises the complex cation {Pb(C3H5O2)6[Mg(H2O)3]4}4+ with the symmetry 4 ‾ 3 m $\overline{4}3m$ and four anions [tris(propanoato-κ2O,O′)plumbate(II)], [Pb(C3H5O2)3] , with 3m symmetry. The central cations Ba12+ and Pb12+ in (I) and in the cation {Pb(C3H5O2)6[Mg(H2O)3]4}4+ of the structure (II), respectively, have similar structural features which are comparable to the environment of the Ba2+ cation in BaCa2(C3H5O2)6 [Stadnicka, K. & Glazer, A. M. (1980). Acta Cryst. B36, 2977–2985]. The molecules in (I) and the ions in (II) are interconnected by Owater‒H⋯Opropanoate hydrogen bonds of a moderate strength. The ethyl chains are disordered which is common in propanoates. However, there are unprecedented features in the title structures: 1) The central atom Pb12+ is the first known example of a Pb2+ cation which is surrounded by six carboxylates in a bidentate bridging mode, i.e. by 12 oxygens. 2) The anion [tris(propanoato-κ2O,O′)plumbate(II)] has a constitution with unusually prominent stereochemical activity of the 6s2 electron pair of the cation Pb2+ completing the coordination to the tetrahedral one. Thus, its formula can be expressed as [Pb[ψ−4t](C3H5O2)3]. 3) In both title structures, there are propanoate molecules with disordered carboxylate oxygens.
Ilya V. Kornyakov, Sergey V. Krivovichev
Published: 12 August 2022
Zeitschrift für Kristallographie - Crystalline Materials; https://doi.org/10.1515/zkri-2022-0046

Abstract:
Single crystals of Na2Cu+[Cu2+3O](AsO4)2Cl (1) and Cu3[Cu3O]2(PO4)4Cl2 (2) were prepared by chemical vapor transport reactions. Both crystal structures are based upon the same [O2Cu6]8+ chains formed by corner-sharing (OCu4)6+ tetrahedra and interconnected by (TO4)3− (T = P, As) tetrahedra into porous {[OCu3](TO4)2Cl}3− frameworks. The channels within the frameworks are occupied by Na+, Cu+ and Cl ions in the crystal structure of 1, whereas the channels in the structure of 2 contain edge-sharing CuO4Cl tetragonal pyramids. Both compounds are structurally related to the previously described synthetic Na2Cu+[Cu2+3O](PO4)2Cl and NaCu2+[Cu2+3O](PO4)2Cl. The compound 2 is structurally and chemically related to yaroshevskite, Cu3[Cu3O]2(VO4)4Cl2, a mineral discovered in volcanic fumaroles, but the two structure types are drastically different. The crystal chemical analysis of the title and related compounds allows to recognize a family of at least four compounds based upon {[OCu3](TO4)2Cl}3− frameworks with channels occupied by different chemical constituents.