M. Reimann, Steffen Klenner, Josef Maximilian Gerdes, M. Hansen, R. Pöttgen
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 Ag@Mg8 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 T N = 4.4(1) K (RE = Pr), 34.6(1) K (RE = Gd) and 23.5(1) K (RE = Tb) while Eu3Ag4Mg12 is a ferromagnet (T C = 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.
{"title":"Magnesium-rich intermetallic compounds RE3Ag4Mg12 (RE = Y, La–Nd, Sm–Dy, Yb) and AE3Ag4Mg12 (AE = Ca, Sr)","authors":"M. Reimann, Steffen Klenner, Josef Maximilian Gerdes, M. Hansen, R. Pöttgen","doi":"10.1515/zkri-2022-0048","DOIUrl":"https://doi.org/10.1515/zkri-2022-0048","url":null,"abstract":"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 Ag@Mg8 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 T N = 4.4(1) K (RE = Pr), 34.6(1) K (RE = Gd) and 23.5(1) K (RE = Tb) while Eu3Ag4Mg12 is a ferromagnet (T C = 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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"417 - 427"},"PeriodicalIF":1.2,"publicationDate":"2022-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42598533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Khurshid Sohail, R. Lalancette, I. Bernal, Xiao-Ling Guo, Liuyan Zhao
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).
{"title":"Revisiting the structure of (±)-[Co(en)3]I3·H2O – X-ray crystallographic and second-Harmonic results","authors":"Khurshid Sohail, R. Lalancette, I. Bernal, Xiao-Ling Guo, Liuyan Zhao","doi":"10.1515/zkri-2022-0044","DOIUrl":"https://doi.org/10.1515/zkri-2022-0044","url":null,"abstract":"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).","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"393 - 402"},"PeriodicalIF":1.2,"publicationDate":"2022-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46780182","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
R. Kremer, S. Bette, E. Brücher, J. Nuss, A. Schulz, M. Whangbo, H. Koo
Abstract We report on the magneto-structural properties of the rare copper aluminum hydroxo-arsenate mineral liroconite with chemical composition Cu2AlAs1−x P x O4(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.
摘要研究了化学成分为Cu2AlAs1−x P x O4(OH)4·4H2O (x≈0.2)的稀有铜铝羟基砷酸盐矿物lioconite的磁结构性质。为了表征天然矿物样品的化学性质，进行了x射线单晶和粉末衍射、热容和结晶水解吸、各向异性热膨胀和拉曼散射以及磁化率研究。两个氧桥接的Cu2+自旋S = 1/2二聚体的反铁磁自旋交换范围在- 320 K和- 136 K之间，这取决于桥接氧原子与哪个基团-15五价阳离子As5+或P5+的配位。因此，磁化率的温度依赖性可以很好地拟合为两个Bleaney-Bowers型自旋S = 1/2二聚体磁化率的总和，表明二聚体与(AsO4)3−/(PO4)3−四面体的混合配位可以忽略不计。DFT + U计算证实了(AsO4)3−或(PO4)3−配位Cu2+ - Cu2+二聚体自旋交换参数的比值。二聚体间的自旋交换比二聚体内的交换约小两个数量级。
{"title":"Multiple strongly coupled antiferromagnetic spin S = 1/2 dimers in liroconite Cu2Al(As,P)O4(OH)4·4H2O","authors":"R. Kremer, S. Bette, E. Brücher, J. Nuss, A. Schulz, M. Whangbo, H. Koo","doi":"10.1515/zkri-2022-0040","DOIUrl":"https://doi.org/10.1515/zkri-2022-0040","url":null,"abstract":"Abstract We report on the magneto-structural properties of the rare copper aluminum hydroxo-arsenate mineral liroconite with chemical composition Cu2AlAs1−x P x O4(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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"403 - 415"},"PeriodicalIF":1.2,"publicationDate":"2022-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42199457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract The temperature dependences of the ionic electrical conductivity of fluorite-type (sp. gr. F m 3 ‾ m $Fmoverline{3}m$ , 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.
摘要萤石型（sp.gr.Fm3‾m$Fmoverline）离子电导率的温度依赖性{3}m首次用阻抗谱法研究了用Bridgman技术生长的KDy3F10和KHo3F10单晶。从离子电导率中观察到的尺寸效应的角度，讨论了KR3F10（R=Tb，Dy，Ho，Y）晶体族的电导率与结构特征之间的相关性。在一系列R=Tb、Dy、Ho和Y的晶体中，随着每个氟原子的晶胞体积V1F的减小，离子转移的活化能Eσ分别从1.57 eV降低到1.16 eV，氟离子电导率值在773K时从3.0×10−5增加到4.4×10−4 S cm，即电导率变化的性质是线性反极化的。这一现象有助于开发新的离子导体的方法和搜索策略。
{"title":"The relationship between ionic conductivity and structural characteristics of melt-grown KR3F10 (R = Tb, Dy, Ho, Y) single crystals","authors":"D. Karimov, I. I. Buchinskaya, N. Sorokin","doi":"10.1515/zkri-2022-0032","DOIUrl":"https://doi.org/10.1515/zkri-2022-0032","url":null,"abstract":"Abstract The temperature dependences of the ionic electrical conductivity of fluorite-type (sp. gr. F m 3 ‾ m $Fmoverline{3}m$ , 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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"429 - 434"},"PeriodicalIF":1.2,"publicationDate":"2022-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43337108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Crystal structure and specific heat of calcium lanthanide oxyborates Ca4LnO(BO3)3","authors":"Nicola D. Kelly, S. Savvin, S. Dutton","doi":"10.1515/zkri-2022-0029","DOIUrl":"https://doi.org/10.1515/zkri-2022-0029","url":null,"abstract":"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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"255 22","pages":"317 - 327"},"PeriodicalIF":1.2,"publicationDate":"2022-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41272421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
F. Chausov, N. Suksin, A. V. Kholzakov, Natalya V. Lomova, I. Kazantseva, D. Rybin
Abstract The cluster structure, thermochemical behavior, and some mechanisms of thermal decomposition of the crystalline products in the isodimorphic substitution series Cu x Ni(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.
{"title":"The cluster structure of crystalline phases according to TGA/DTA and XPS data in isodimorphic substitution series [Cu x Ni(1−x){N(CH2PO3)3}]Na4·nH2O (x = 0 … 1)","authors":"F. Chausov, N. Suksin, A. V. Kholzakov, Natalya V. Lomova, I. Kazantseva, D. Rybin","doi":"10.1515/zkri-2022-0034","DOIUrl":"https://doi.org/10.1515/zkri-2022-0034","url":null,"abstract":"Abstract The cluster structure, thermochemical behavior, and some mechanisms of thermal decomposition of the crystalline products in the isodimorphic substitution series Cu x Ni(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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"377 - 383"},"PeriodicalIF":1.2,"publicationDate":"2022-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42323032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Na2Cu+[Cu2+3O](AsO4)2Cl and Cu3[Cu3O]2(PO4)4Cl2: two new structure types based upon chains of oxocentered tetrahedra","authors":"I. V. Kornyakov, S. Krivovichev","doi":"10.1515/zkri-2022-0046","DOIUrl":"https://doi.org/10.1515/zkri-2022-0046","url":null,"abstract":"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.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"343 - 350"},"PeriodicalIF":1.2,"publicationDate":"2022-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47370298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract A survey of the crystallographic literature of metal-organic crystal structures for the presence of C–I···π(arene) interactions where the iodide atom occupies a position close to plumb to the ring centroid, corresponding to a delocalised interaction, and is within the assumed sum of the van der Waals radii, i.e. 3.88 Å, has been undertaken. The majority of the 26 identified examples feature supramolecular chains of varying topology whereby C–I···π(arene) contacts are readily identified and apparently operating independently of other obvious supramolecular synthons. The next most prevalent supramolecular aggregate was zero-dimensional, containing up to a maximum of three molecules. While there were three examples of two-dimensional arrays among a series of isostructural crystal structures, no examples of three-dimensional structures largely sustained by C–I···π(arene) interactions were noted. This distribution of supramolecular aggregation patterns matched that noted for all-organic systems. In terms of the overall adoption rate, delocalised C–I···π(arene) interactions were found in 3% of crystals of metal-organic species where they could form, a percentage lower than 4% noted for all-organic crystals.
{"title":"A bibliographic survey of the supramolecular architectures sustained by delocalised C–I⋯π(arene) interactions in metal-organic crystals","authors":"E. Tiekink","doi":"10.1515/zkri-2022-0038","DOIUrl":"https://doi.org/10.1515/zkri-2022-0038","url":null,"abstract":"Abstract A survey of the crystallographic literature of metal-organic crystal structures for the presence of C–I···π(arene) interactions where the iodide atom occupies a position close to plumb to the ring centroid, corresponding to a delocalised interaction, and is within the assumed sum of the van der Waals radii, i.e. 3.88 Å, has been undertaken. The majority of the 26 identified examples feature supramolecular chains of varying topology whereby C–I···π(arene) contacts are readily identified and apparently operating independently of other obvious supramolecular synthons. The next most prevalent supramolecular aggregate was zero-dimensional, containing up to a maximum of three molecules. While there were three examples of two-dimensional arrays among a series of isostructural crystal structures, no examples of three-dimensional structures largely sustained by C–I···π(arene) interactions were noted. This distribution of supramolecular aggregation patterns matched that noted for all-organic systems. In terms of the overall adoption rate, delocalised C–I···π(arene) interactions were found in 3% of crystals of metal-organic species where they could form, a percentage lower than 4% noted for all-organic crystals.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"367 - 376"},"PeriodicalIF":1.2,"publicationDate":"2022-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47803358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Herein we describe materials of composition [Co(NH3)4(X-leucinato)]I2·H2O in which the amino acid ligand is either L or D, and in which (a) while in pure enantiomorphic form (L), crystallizes in a Sohncke space group with Z′ = 2.0; but, whose packing closely resembles that of its racemate. Such substances are labeled a Racemic Mimic; and (b) crystals in which the L:D ratio of the amino acid ligand in the asymmetric unit is (71:29), which interestingly crystallize in the same space group and cell constants as those of the former. Moreover, the packing behavior is essentially the same in both—the difference being that the (1:1) species is fully ordered, while that with L:D (71:29) ratio has a partially disordered propyl chain. The (71:29) species we describe herein as an Unbalanced Racemate.
{"title":"Unbalanced racemates: solid state solutions containing enantiomeric pairs crystallizing in Sohncke space groups with (L:D) ratios other than (1:1) – illustrated with crystals of a Co(III) coordination compound","authors":"I. Bernal, R. Lalancette","doi":"10.1515/zkri-2022-0023","DOIUrl":"https://doi.org/10.1515/zkri-2022-0023","url":null,"abstract":"Abstract Herein we describe materials of composition [Co(NH3)4(X-leucinato)]I2·H2O in which the amino acid ligand is either L or D, and in which (a) while in pure enantiomorphic form (L), crystallizes in a Sohncke space group with Z′ = 2.0; but, whose packing closely resembles that of its racemate. Such substances are labeled a Racemic Mimic; and (b) crystals in which the L:D ratio of the amino acid ligand in the asymmetric unit is (71:29), which interestingly crystallize in the same space group and cell constants as those of the former. Moreover, the packing behavior is essentially the same in both—the difference being that the (1:1) species is fully ordered, while that with L:D (71:29) ratio has a partially disordered propyl chain. The (71:29) species we describe herein as an Unbalanced Racemate.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"311 - 316"},"PeriodicalIF":1.2,"publicationDate":"2022-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44246744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Single crystals of the two alkali metal zinc oxidotellurates(IV), Rb2Zn(TeO3)(CO3)·H2O and Na2Zn2Te4O11, were obtained by reactions of mixtures of ZnO, TeO2, Rb2CO3 (molar ratios 2:3:6) and ZnO, TeO2, Na2CO3 (molar ratios 2:3:10), respectively, with small amounts of water as a mineralizer. Both compounds crystallize as order-disorder (OD) structures of layers and feature a high stacking fault probability. The crystal structure of Rb2Zn(TeO3)(CO3)·H2O is composed of layers extending parallel to (100). The structure is composed of two kinds of non-polar OD layers consisting of trigonal-pyramidal [TeO3]2−, tetrahedral [ZnO4]6−, Rb1+, and CO32−, H2O, Rb2+, respectively. Different centrings of the layer groups lead to an ambiguity in the stacking arrangement. The crystal structure of Na2Zn2Te4O11 is built from layers extending parallel to (001). Trigonal-pyramidal [TeO3]2− and bisphenoidal [TeO4]4− polyhedra form [Te4O11]6− groups, which are connected by longer Te–O-contacts to form 1∞[Te8O22]12− double chains oriented along either [100] or [010]. These chains form non-polar layers, which appear alternatingly in two orientations related by a fourfold rotoinversion. The Zn2+ and Na+ cations are located at the layer interface. The stacking ambiguity is due to different lattices of adjacent layers.
{"title":"Order-disorder (OD) structures of Rb2Zn(TeO3)(CO3)·H2O and Na2Zn2Te4O11","authors":"F. Eder, B. Stöger, M. Weil","doi":"10.1515/zkri-2022-0030","DOIUrl":"https://doi.org/10.1515/zkri-2022-0030","url":null,"abstract":"Abstract Single crystals of the two alkali metal zinc oxidotellurates(IV), Rb2Zn(TeO3)(CO3)·H2O and Na2Zn2Te4O11, were obtained by reactions of mixtures of ZnO, TeO2, Rb2CO3 (molar ratios 2:3:6) and ZnO, TeO2, Na2CO3 (molar ratios 2:3:10), respectively, with small amounts of water as a mineralizer. Both compounds crystallize as order-disorder (OD) structures of layers and feature a high stacking fault probability. The crystal structure of Rb2Zn(TeO3)(CO3)·H2O is composed of layers extending parallel to (100). The structure is composed of two kinds of non-polar OD layers consisting of trigonal-pyramidal [TeO3]2−, tetrahedral [ZnO4]6−, Rb1+, and CO32−, H2O, Rb2+, respectively. Different centrings of the layer groups lead to an ambiguity in the stacking arrangement. The crystal structure of Na2Zn2Te4O11 is built from layers extending parallel to (001). Trigonal-pyramidal [TeO3]2− and bisphenoidal [TeO4]4− polyhedra form [Te4O11]6− groups, which are connected by longer Te–O-contacts to form 1∞[Te8O22]12− double chains oriented along either [100] or [010]. These chains form non-polar layers, which appear alternatingly in two orientations related by a fourfold rotoinversion. The Zn2+ and Na+ cations are located at the layer interface. The stacking ambiguity is due to different lattices of adjacent layers.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"237 1","pages":"329 - 341"},"PeriodicalIF":1.2,"publicationDate":"2022-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44524257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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