V. Yukhno, D. Charkin, A. Banaru, L. Manelis, A. Gosteva, S. Volkov, S. Aksenov, R. Bubnova
Abstract Crystals of the first new organo–inorganic hybrid borate based on potassium crown ether complex, [K(C12H24O6)B5O6(OH)4](H2O) (1), have been produced from aqueous solutions and characterized by single-crystal X-ray diffraction. 1 crystalizes is orthorhombic system, Pnma, a = 10.1684(3) Å, b = 11.6289(3) Å, c = 21.2247(6) Å, V = 2509.76(12) Å3, Robs = 0.059. The structure of 1 consists of molecular [K(C12H24O6)B5O6(OH)4]0 complexes, common for crown ether complexes but yet not among borates, with a very rare monodentate coordination of the common pentaborate anion(1-). The molecular complexes are linked into weak chains via hydrogen bonding to outer-sphere water molecules. Hirshfeld surfaces analysis and complexity measurement of 1 were performed. Perspectives of borate structures containing crown ether complexes as templates are briefly outlined.
{"title":"Crown ether complexes as a possible template for hybrid organic–inorganic borates","authors":"V. Yukhno, D. Charkin, A. Banaru, L. Manelis, A. Gosteva, S. Volkov, S. Aksenov, R. Bubnova","doi":"10.1515/zkri-2023-0020","DOIUrl":"https://doi.org/10.1515/zkri-2023-0020","url":null,"abstract":"Abstract Crystals of the first new organo–inorganic hybrid borate based on potassium crown ether complex, [K(C12H24O6)B5O6(OH)4](H2O) (1), have been produced from aqueous solutions and characterized by single-crystal X-ray diffraction. 1 crystalizes is orthorhombic system, Pnma, a = 10.1684(3) Å, b = 11.6289(3) Å, c = 21.2247(6) Å, V = 2509.76(12) Å3, Robs = 0.059. The structure of 1 consists of molecular [K(C12H24O6)B5O6(OH)4]0 complexes, common for crown ether complexes but yet not among borates, with a very rare monodentate coordination of the common pentaborate anion(1-). The molecular complexes are linked into weak chains via hydrogen bonding to outer-sphere water molecules. Hirshfeld surfaces analysis and complexity measurement of 1 were performed. Perspectives of borate structures containing crown ether complexes as templates are briefly outlined.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49015084","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 2-(methylthio)benzoic acid (1) is an ortho-substituted benzoic acid derivative, whereas 4-(methylthio)benzoic acid (2) is a para-substituted benzoic acid derivative. The structural analysis of both compounds was carried out using PXRD data. 2-(methylthio)benzoic acid shows a triclinic system with the P 1 ‾ $Poverline{1}$ space group, whereas 4-(methylthio)benzoic acid shows a monoclinic system and crystallizes in the P21/a space group. The strength, as well as relative contributions of intermolecular hydrogen bonds, have been examined through Hirshfeld surfaces as well as 2D fingerprint plots. A weak intramolecular hydrogen bond was found only in the case of ortho-substituted 2-(methylthio)benzoic acid. Supramolecular frameworks for 1 are formed by the interplay of intramolecular and intermolecular interactions, whereas for 2, intermolecular contacts form supramolecular assemblies. Intermolecular O–H⋯O interactions involving carboxyl groups form the R22(8) graph-set motif for both compounds. Theoretical DFT calculations using the B3LYP correlation functional reveal that the energy gap of HOMO–LUMO orbitals in compound 1, with the methylthio moiety in the ortho position relative to the carboxyl group, is lower than that of compound 2, with the methylthio moiety in the para position. Vertical and adiabatic ionization energies are also calculated for both compounds.
{"title":"Structure determination through powder X-ray diffraction, Hirshfeld surface analysis, and DFT studies of 2- and 4-(methylthio)benzoic acid","authors":"P. Chatterjee","doi":"10.1515/zkri-2022-0069","DOIUrl":"https://doi.org/10.1515/zkri-2022-0069","url":null,"abstract":"Abstract 2-(methylthio)benzoic acid (1) is an ortho-substituted benzoic acid derivative, whereas 4-(methylthio)benzoic acid (2) is a para-substituted benzoic acid derivative. The structural analysis of both compounds was carried out using PXRD data. 2-(methylthio)benzoic acid shows a triclinic system with the P 1 ‾ $Poverline{1}$ space group, whereas 4-(methylthio)benzoic acid shows a monoclinic system and crystallizes in the P21/a space group. The strength, as well as relative contributions of intermolecular hydrogen bonds, have been examined through Hirshfeld surfaces as well as 2D fingerprint plots. A weak intramolecular hydrogen bond was found only in the case of ortho-substituted 2-(methylthio)benzoic acid. Supramolecular frameworks for 1 are formed by the interplay of intramolecular and intermolecular interactions, whereas for 2, intermolecular contacts form supramolecular assemblies. Intermolecular O–H⋯O interactions involving carboxyl groups form the R22(8) graph-set motif for both compounds. Theoretical DFT calculations using the B3LYP correlation functional reveal that the energy gap of HOMO–LUMO orbitals in compound 1, with the methylthio moiety in the ortho position relative to the carboxyl group, is lower than that of compound 2, with the methylthio moiety in the para position. Vertical and adiabatic ionization energies are also calculated for both compounds.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46373201","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 crystal structure of the title compound was determined using electron diffraction data collected in continuous rotation mode. The structure was successfully solved and refined kinematically in the monoclinic space group P21/c, with a Z value of 2 and Z′ value of 0.5. Within the crystal structure, the entire molecule is predominantly flat. The molecular packing exhibits a herringbone pattern, distinct from that of the unchlorinated analogue molecule. The largest facet of the crystals, which faces the supporting carbon film, is designated as (01‾1‾$bar{1}bar{1}$).
{"title":"Crystal structure of 9,10-bis-((perchloro-phenyl)-ethynyl)anthracene determined from three-dimensional electron diffraction data","authors":"T. Gorelik, Andreas Ulmer, A. Schleper, A. Kuehne","doi":"10.1515/zkri-2023-0009","DOIUrl":"https://doi.org/10.1515/zkri-2023-0009","url":null,"abstract":"Abstract The crystal structure of the title compound was determined using electron diffraction data collected in continuous rotation mode. The structure was successfully solved and refined kinematically in the monoclinic space group P21/c, with a Z value of 2 and Z′ value of 0.5. Within the crystal structure, the entire molecule is predominantly flat. The molecular packing exhibits a herringbone pattern, distinct from that of the unchlorinated analogue molecule. The largest facet of the crystals, which faces the supporting carbon film, is designated as (01‾1‾$bar{1}bar{1}$).","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47514916","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}
L. Sallum, L. Silva, J. E. Queiroz, Vitor Duarte, Wesley F. Vaz, M. Hernandes, G. Aquino, A. Camargo, H. Napolitano
Abstract Fluorinated chalcones are organic compounds with diverse biological activities and are of interest for drug development due to their improved properties, such as lipophilicity, bioavailability, and metabolic stability. Therefore, the correlation between structure and properties is fundamental to discover the potential use on pharmaceutical and technological applications. In this sense, we synthesized and characterized a novel fluorinated chalcone (E)-1-(4-fluorophenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (FCH), and compared its supramolecular arrangement and topological analysis with a chalcone (E)-1-(4-hydroxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (HCH). The molecular electrostatic potential, QTAIM, and frontier molecular orbitals of both chalcones were investigated using the M06-2X/6-311++G(d,p) level of theory. Our findings show that the FCH exhibits a herringbone packing with intermolecular interactions of C–H⋯F and C–H⋯π, while the HCH assumes a staircase packing coordinated by O–H⋯O and π⋯π intermolecular interactions. Furthermore, the electrostatic potential analysis shows that FCH is susceptible to electrophilic attack, while HCH is susceptible to nucleophilic attack. Finally, the structural basis analysis for both chalcones indicated that FCH has a higher lipophilicity than HCH due to the stronger hydrogen bond of HCH with water.
{"title":"Structural basis for fluorine substitution on a new naphthalene–chalcone analog","authors":"L. Sallum, L. Silva, J. E. Queiroz, Vitor Duarte, Wesley F. Vaz, M. Hernandes, G. Aquino, A. Camargo, H. Napolitano","doi":"10.1515/zkri-2022-0066","DOIUrl":"https://doi.org/10.1515/zkri-2022-0066","url":null,"abstract":"Abstract Fluorinated chalcones are organic compounds with diverse biological activities and are of interest for drug development due to their improved properties, such as lipophilicity, bioavailability, and metabolic stability. Therefore, the correlation between structure and properties is fundamental to discover the potential use on pharmaceutical and technological applications. In this sense, we synthesized and characterized a novel fluorinated chalcone (E)-1-(4-fluorophenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (FCH), and compared its supramolecular arrangement and topological analysis with a chalcone (E)-1-(4-hydroxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (HCH). The molecular electrostatic potential, QTAIM, and frontier molecular orbitals of both chalcones were investigated using the M06-2X/6-311++G(d,p) level of theory. Our findings show that the FCH exhibits a herringbone packing with intermolecular interactions of C–H⋯F and C–H⋯π, while the HCH assumes a staircase packing coordinated by O–H⋯O and π⋯π intermolecular interactions. Furthermore, the electrostatic potential analysis shows that FCH is susceptible to electrophilic attack, while HCH is susceptible to nucleophilic attack. Finally, the structural basis analysis for both chalcones indicated that FCH has a higher lipophilicity than HCH due to the stronger hydrogen bond of HCH with water.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43670307","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}
H. Ben Yahia, K. Motohashi, S. Mori, Atsushi Sakuda, A. Hayashi
Abstract Yellow needles-like single crystals of Li4P2S6 were obtained serendipitously during the preparation of Li7P3S10O. The twinned crystal structure of Li4P2S6 was determined from single-crystal X-ray diffraction data [wR(F2) = 0.069, 716 reflections, 40 variables]. Li4P2S6 crystallizes in the trigonal system, space group P 3 ‾ m 1 $Poverline{3}m1$ (N° 164), a = 10.5042(8) Å, c = 6.5837(6) Å, V = 629.11(9) Å3 and Z = 2. The lithium octahedra form a [Li4S6]8− honeycomb-like structure within which diphosphate units are located. The comparison of our crystal structure to those of P63/mcm-, P 3 ‾ 1 m $Poverline{3}1m$ -, and P321-Li4P2S6 demonstrated group-subgroup relationships and associated the disorder or order of the phosphorus atoms within the identical [Li4S6]8− 3d-frameworks to the choice of the unit cell (the subcell with a ∼ 6.07 Å vs. the supercell with a ∼ 10.5 Å).
{"title":"Twinned single crystal structure of Li4P2S6","authors":"H. Ben Yahia, K. Motohashi, S. Mori, Atsushi Sakuda, A. Hayashi","doi":"10.1515/zkri-2023-0013","DOIUrl":"https://doi.org/10.1515/zkri-2023-0013","url":null,"abstract":"Abstract Yellow needles-like single crystals of Li4P2S6 were obtained serendipitously during the preparation of Li7P3S10O. The twinned crystal structure of Li4P2S6 was determined from single-crystal X-ray diffraction data [wR(F2) = 0.069, 716 reflections, 40 variables]. Li4P2S6 crystallizes in the trigonal system, space group P 3 ‾ m 1 $Poverline{3}m1$ (N° 164), a = 10.5042(8) Å, c = 6.5837(6) Å, V = 629.11(9) Å3 and Z = 2. The lithium octahedra form a [Li4S6]8− honeycomb-like structure within which diphosphate units are located. The comparison of our crystal structure to those of P63/mcm-, P 3 ‾ 1 m $Poverline{3}1m$ -, and P321-Li4P2S6 demonstrated group-subgroup relationships and associated the disorder or order of the phosphorus atoms within the identical [Li4S6]8− 3d-frameworks to the choice of the unit cell (the subcell with a ∼ 6.07 Å vs. the supercell with a ∼ 10.5 Å).","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"209 - 216"},"PeriodicalIF":1.2,"publicationDate":"2023-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42678311","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 We present the crystallographic program Jana2020, the successor of Jana2006. Jana2020 has new, technically different graphics and structure plot-driven intuitive control. Tools known from Jana2006 were revised and inserted into a new logical scheme, and their control connected with the structure plot. Some of the tools were considerably improved. We focus on the details of the most dynamically developing parts, namely twinned structures, magnetic structures, and structure analysis based on electron diffraction data.
{"title":"Jana2020 – a new version of the crystallographic computing system Jana","authors":"V. Petříček, L. Palatinus, J. Plášil, M. Dušek","doi":"10.1515/zkri-2023-0005","DOIUrl":"https://doi.org/10.1515/zkri-2023-0005","url":null,"abstract":"Abstract We present the crystallographic program Jana2020, the successor of Jana2006. Jana2020 has new, technically different graphics and structure plot-driven intuitive control. Tools known from Jana2006 were revised and inserted into a new logical scheme, and their control connected with the structure plot. Some of the tools were considerably improved. We focus on the details of the most dynamically developing parts, namely twinned structures, magnetic structures, and structure analysis based on electron diffraction data.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"0 1","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42945626","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}
Samuel Abdelmaseh, M. Burianek, J. Birkenstock, L. Fischer, H. Schneider, R. Fischer
Abstract Single crystals of five (Al,Ge)-mullites incorporating Pb, and four of which also incorporating foreign cations (Fe,Cr,Nd,Sm) were grown by flux techniques in a PbO-MoO3 flux. They were characterized by scanning electron microscopy, electron microprobe analyses, single-crystal X-ray diffraction. In addition, the refractive indices of mullite containing Nd were determined by spindle-stage optical investigations. Careful inspection of the single-crystal X-ray diffraction data revealed that weak superstructure reflections observed in all doped crystals violating the reflection conditions can be attributed to λ/2 contributions in the primary X-ray beam. Consequently, all crystal structures were refined in space group Pbam, thus avoiding a symmetry lowering to a noncentrosymmetric subgroup as done in earlier work on a (Al,Ge)-mullite doped with Pb and Nd (Saalfeld & Klaska, Z. Kristallogr. 1985, 172, 129–133). The following phases with chemical compositions used in the refinements were obtained: undoped mullite (Al4.50Ge1.50O9.75; a = 7.6559(4) Å, b = 7.7763(4) Å, c = 2.9233(2) Å, V = 174.04(2) Å3); (Pb,Fe)-doped mullite (Pb0.02Fe0.68Al3.95Ge1.37O9.70; a = 7.7125(7) Å, b = 7.8527(7) Å, c = 2.9528(2) Å, V = 178.83(3) Å3); (Pb,Cr)-doped mullite (Pb0.01Cr0.63Al3.90Ge1.47O9.75; a = 7.6917(6) Å, b = 7.8168(6) Å, c = 2.9522(2) Å, V = 177.50(2) Å3); (Pb,Nd)-doped mullite (Pb0.06Nd0.02Al4.82Ge1.18O9.69; a = 7.6585(7) Å, b = 7.7666(7) Å, c = 2.9164(3) Å, V = 173.47(3) Å3); (Pb,Sm)-doped mullite (Pb0.06Sm0.02Al4.55Ge1.45O9.79; a = 7.6563(3) Å, b = 7.7873(3) Å, c = 2.9236(1) Å, V = 174.31(1) Å3); Pb is only incorporated into the crystal structure when a co-dopant element is present. Then it resides together with Nd or Sm in the oxygen-vacancy sites created by the formation of triclusters of AlO4 and GeO4 tetrahedra. In the case of (Pb,Fe)-doped mullite, Fe shares the same position as Al and Ge. In contrast to the (Al,Si)-mullites, Ge is located in both tetrahedral sites T and T*. The occupancies follow a substitution scheme according to Pb q (Nd,Sm) r (Cr,Fe) z Al4+2v−zGe2−2vO10−v+q+3/2r. With v = number of vacancies, such a mullite can be understood as a “stuffed mullite” derived from a related “open mullite” (no vacancies filled with large cations) of composition (Cr,Fe) z Al4+2v−zGe2−2vO10−v and then “stuffed” with qPb2+ + r(Nd3+,Sm3+) formula units where concurrently the number of available O3-vacancies is reduced by q + 3/2r units of extra oxygen. Thus, charge compensation upon incorporation of Pb2+ and (Nd,Sm)3+ is achieved by adding the amount of oxygen corresponding to the oxidation state of divalent Pb2+ and trivalent rare-earth elements. Based on this description, the maximum number of large cations which can be stuffed into the mullite structure can directly be calculated from the v-value of the related “open mullite”. In contrast, the smaller cations Fe3+ and Cr3+ are directly substituting Al3+. In the stuffed mullites, Pb and (Nd,Sm) could
摘要:在PbO-MoO3助熔剂中，采用助熔剂法制备了5个含Pb的(Al,Ge)莫来石单晶和4个含外源阳离子(Fe,Cr,Nd,Sm)莫来石单晶。通过扫描电镜、电子探针分析、单晶x射线衍射等方法对其进行了表征。此外，用轴级光学法测定了含Nd莫来石的折射率。对单晶x射线衍射数据的仔细检查表明，在所有违反反射条件的掺杂晶体中观察到的弱上层结构反射可归因于主x射线束中的λ/2贡献。因此，所有的晶体结构都在pam空间群中进行了改进，从而避免了像早期在(Al,Ge)-莫来石中掺杂Pb和Nd的研究那样，对称性降低到非中心对称亚群(Saalfeld & Klaska, Z. Kristallogr. 1985, 172,129 - 133)。得到的化学成分为:未掺杂莫来石(Al4.50Ge1.50O9.75;= 7.6559 (4) a、b = 7.7763 (4) a, c = 2.9233 (2), V = 174.04 (2) A3);(Pb,Fe)掺杂莫来石(Pb0.02Fe0.68Al3.95Ge1.37O9.70;= 7.7125 (7), b = 7.8527 (7) a, c = 2.9528 (2), V = 178.83 (3) A3);(Pb,Cr)掺杂莫来石(Pb0.01Cr0.63Al3.90Ge1.47O9.75;= 7.6917 (6), b = 7.8168 (6) a, c = 2.9522 (2), V = 177.50 (2) A3);(Pb,Nd)掺杂莫来石(Pb0.06Nd0.02Al4.82Ge1.18O9.69;= 7.6585 (7), b = 7.7666 (7) a, c = 2.9164 (3), V = 173.47 (3) A3);(Pb,Sm)掺杂莫来石(Pb0.06Sm0.02Al4.55Ge1.45O9.79;= 7.6563 (3) a、b = 7.7873 (3) a, c = 2.9236 (1), V = 174.31 (1) A3);只有当共掺杂元素存在时，铅才被并入晶体结构中。然后，它与Nd或Sm一起存在于由AlO4和GeO4四面体形成的三簇形成的氧空位上。在(Pb,Fe)掺杂莫来石的情况下，Fe与Al和Ge占据相同的位置。与(Al,Si)莫来石不同，Ge同时位于四面体T和T*上。占位遵循Pb q (Nd,Sm) r (Cr,Fe) z Al4+2v−zGe2−2vO10−v+q+3/2r的取代方案。当v =空位数时，这样的莫来石可以理解为由相关的(Cr,Fe) z Al4+2v−zGe2−2vO10−v组成的“开放莫来石”(没有空位被大阳离子填充)衍生而来的“填充莫来石”，然后用qPb2+ + r(Nd3+，Sm3+)公式单元“填充”，同时可用的o3空位数减少了q + 3/2r个额外的氧单位。因此，通过添加与二价Pb2+和三价稀土元素氧化态相对应的氧量，可以实现Pb2+和(Nd,Sm)3+掺入后的电荷补偿。在此基础上，可直接从相关“开口莫来石”的v值计算莫来石结构中可塞进的大阳离子的最大数目。而较小的阳离子Fe3+和Cr3+则直接取代了Al3+。在填入的莫来石中，Pb和(Nd,Sm)无法区分，在同一地点混合使用。除结构分析外，采用浸没法测定了(Pb,Nd)莫来石的折射率，采用微折射计主轴台，n x = 1.697(3)， n y = 1.708(3)， n z = 1.710(3)， 2V z = 122(4)°。平均折射率与化学成分计算的相应参数非常接近，而如果忽略额外的阳离子，平均折射率将显著偏离，因此代表了Pb和Nd掺入晶体结构的独立证据。
{"title":"Incorporation of Pb in (Al,Ge)-mullites in the presence of Fe, Cr, Nd, and Sm","authors":"Samuel Abdelmaseh, M. Burianek, J. Birkenstock, L. Fischer, H. Schneider, R. Fischer","doi":"10.1515/zkri-2022-0026","DOIUrl":"https://doi.org/10.1515/zkri-2022-0026","url":null,"abstract":"Abstract Single crystals of five (Al,Ge)-mullites incorporating Pb, and four of which also incorporating foreign cations (Fe,Cr,Nd,Sm) were grown by flux techniques in a PbO-MoO3 flux. They were characterized by scanning electron microscopy, electron microprobe analyses, single-crystal X-ray diffraction. In addition, the refractive indices of mullite containing Nd were determined by spindle-stage optical investigations. Careful inspection of the single-crystal X-ray diffraction data revealed that weak superstructure reflections observed in all doped crystals violating the reflection conditions can be attributed to λ/2 contributions in the primary X-ray beam. Consequently, all crystal structures were refined in space group Pbam, thus avoiding a symmetry lowering to a noncentrosymmetric subgroup as done in earlier work on a (Al,Ge)-mullite doped with Pb and Nd (Saalfeld & Klaska, Z. Kristallogr. 1985, 172, 129–133). The following phases with chemical compositions used in the refinements were obtained: undoped mullite (Al4.50Ge1.50O9.75; a = 7.6559(4) Å, b = 7.7763(4) Å, c = 2.9233(2) Å, V = 174.04(2) Å3); (Pb,Fe)-doped mullite (Pb0.02Fe0.68Al3.95Ge1.37O9.70; a = 7.7125(7) Å, b = 7.8527(7) Å, c = 2.9528(2) Å, V = 178.83(3) Å3); (Pb,Cr)-doped mullite (Pb0.01Cr0.63Al3.90Ge1.47O9.75; a = 7.6917(6) Å, b = 7.8168(6) Å, c = 2.9522(2) Å, V = 177.50(2) Å3); (Pb,Nd)-doped mullite (Pb0.06Nd0.02Al4.82Ge1.18O9.69; a = 7.6585(7) Å, b = 7.7666(7) Å, c = 2.9164(3) Å, V = 173.47(3) Å3); (Pb,Sm)-doped mullite (Pb0.06Sm0.02Al4.55Ge1.45O9.79; a = 7.6563(3) Å, b = 7.7873(3) Å, c = 2.9236(1) Å, V = 174.31(1) Å3); Pb is only incorporated into the crystal structure when a co-dopant element is present. Then it resides together with Nd or Sm in the oxygen-vacancy sites created by the formation of triclusters of AlO4 and GeO4 tetrahedra. In the case of (Pb,Fe)-doped mullite, Fe shares the same position as Al and Ge. In contrast to the (Al,Si)-mullites, Ge is located in both tetrahedral sites T and T*. The occupancies follow a substitution scheme according to Pb q (Nd,Sm) r (Cr,Fe) z Al4+2v−zGe2−2vO10−v+q+3/2r. With v = number of vacancies, such a mullite can be understood as a “stuffed mullite” derived from a related “open mullite” (no vacancies filled with large cations) of composition (Cr,Fe) z Al4+2v−zGe2−2vO10−v and then “stuffed” with qPb2+ + r(Nd3+,Sm3+) formula units where concurrently the number of available O3-vacancies is reduced by q + 3/2r units of extra oxygen. Thus, charge compensation upon incorporation of Pb2+ and (Nd,Sm)3+ is achieved by adding the amount of oxygen corresponding to the oxidation state of divalent Pb2+ and trivalent rare-earth elements. Based on this description, the maximum number of large cations which can be stuffed into the mullite structure can directly be calculated from the v-value of the related “open mullite”. In contrast, the smaller cations Fe3+ and Cr3+ are directly substituting Al3+. In the stuffed mullites, Pb and (Nd,Sm) could ","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"151 - 166"},"PeriodicalIF":1.2,"publicationDate":"2023-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48708466","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 In intermetallic chemistry, the Gd14Ag51 structure type is rather common and has many amalgam representatives. Up to today, binary amalgams of this type have been described for M = Na, Ca, Sr, Eu, Yb, and the structure family still is growing. Yb11Hg54 is the only representative with a fully ordered crystal structure, and all other representatives exhibit individual disorder phenomena or patterns. The diversity of disorder phenomena in this structural family is unique. In order to shed a light on the underlying reasons for this unexpected structural complexity, we compare the available literature structure models with three new ternary variants, Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54 and Ca6.9Na4.1Hg54 (all in space group type P 6 ‾ $Poverline{6}$ , a = 13.5379(12), 13.5406(8) and 13.564(5) Å, c = 9.7488(14), 9.7149 and 9.810(7) Å for Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54 and Ca6.9Na4.1Hg54, respectively). Their crystal structures have been examined in detail on the basis of both single crystal and powder X-ray diffraction data. Each of the three new amalgams exhibits its own set of disorder phenomena that is again different from those of the respective binary variants. The synopsis of the crystal structures and their individual disorder phenomena indicates that the reason for the disorder phenomena cannot be found only by analyzing geometric details such as atomic radii quotients or coordination polyhedral volumina, and additional electronic reasons must be assumed.
摘要在金属间化学中，Gd14Ag51结构类型较为常见，有许多汞合金代表。到目前为止，这种类型的二元汞合金已经被描述为M = Na, Ca, Sr, Eu, Yb，并且结构家族仍在增长。Yb11Hg54是唯一具有完全有序晶体结构的代表，其他代表均表现出个别的无序现象或模式。在这个结构家庭中，紊乱现象的多样性是独一无二的。为了阐明这种意外的结构复杂性的潜在原因，我们将现有的文献结构模型与三个新的三元变体，Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54和Ca6.9Na4.1Hg54进行比较(所有的空间群类型都是P 6形式的$Poverline{6}$， a = 13.5379(12)， 13.5406(8)和13.564(5)Å，对于Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54和Ca6.9Na4.1Hg54, c = 9.7488(14)， 9.7149和9.810(7)Å)。在单晶和粉末x射线衍射数据的基础上，对其晶体结构进行了详细的研究。三种新汞合金中的每一种都表现出自己的一套紊乱现象，这些现象又不同于各自的二元变体。晶体结构及其个别无序现象的概述表明，无序现象的原因不能仅仅通过分析原子半径商或配位多面体体积等几何细节来找到，必须假定额外的电子原因。
{"title":"Ternary amalgams: expanding the structural variety of the Gd14Ag51 family","authors":"T. Hohl, L. Nusser, Jessica Wulfes, C. Hoch","doi":"10.1515/zkri-2023-0007","DOIUrl":"https://doi.org/10.1515/zkri-2023-0007","url":null,"abstract":"Abstract In intermetallic chemistry, the Gd14Ag51 structure type is rather common and has many amalgam representatives. Up to today, binary amalgams of this type have been described for M = Na, Ca, Sr, Eu, Yb, and the structure family still is growing. Yb11Hg54 is the only representative with a fully ordered crystal structure, and all other representatives exhibit individual disorder phenomena or patterns. The diversity of disorder phenomena in this structural family is unique. In order to shed a light on the underlying reasons for this unexpected structural complexity, we compare the available literature structure models with three new ternary variants, Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54 and Ca6.9Na4.1Hg54 (all in space group type P 6 ‾ $Poverline{6}$ , a = 13.5379(12), 13.5406(8) and 13.564(5) Å, c = 9.7488(14), 9.7149 and 9.810(7) Å for Yb10.7Sr0.3Hg54, Ca4.5Eu6.5Hg54 and Ca6.9Na4.1Hg54, respectively). Their crystal structures have been examined in detail on the basis of both single crystal and powder X-ray diffraction data. Each of the three new amalgams exhibits its own set of disorder phenomena that is again different from those of the respective binary variants. The synopsis of the crystal structures and their individual disorder phenomena indicates that the reason for the disorder phenomena cannot be found only by analyzing geometric details such as atomic radii quotients or coordination polyhedral volumina, and additional electronic reasons must be assumed.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"187 - 199"},"PeriodicalIF":1.2,"publicationDate":"2023-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44262041","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}
Joshua Wiethölter, Aylin Koldemir, T. Block, M. Reimann, Steffen Klenner, Rainer Pöttgen
Abstract The ternary Laves phases Sr2Pd3Sn, Eu2Pd3Sn and Eu2Pd3In were synthesized by induction melting of the elements in sealed tantalum ampoules. The polycrystalline products were characterized through their powder X-ray diffraction patterns. The structure of Eu2Pd3Sn was refined from single crystal X-ray diffractometer data: Mg2MnGa3 type, Cmcm, a = 583.36(5), b = 908.31(7), c = 958.06(8) pm, wR2 = 0.0366, 557 F2 values, 23 variables. The palladium and tin atoms show the inverse coloring on the network of condensed tetrahedra of Mg2MnGa3, i.e., MnGa3 versus Pd3Sn. Refinement of the occupancy parameters revealed small defects for the europium site, leading to composition Eu1.962(6)Pd3Sn for the studied crystal. Sr2Pd3Sn is a Pauli paramagnet and Eu2Pd3Sn shows Curie-Weiss paramagnetism (7.86(1) µB Eu atom−1 and ΘP = 48.1(1) K). Ferromagnetic ordering is observed below TC = 46.1(1) K. The 119Sn and 151Eu Mössbauer spectra of Sr2Pd3Sn and Eu2Pd3Sn are discussed with respect to electron density changes as a function of the tin content and the ionicity in the sequence of the stannides Sr2Pd3Sn/Eu2Pd3Sn → Sr2Pd2Sn/Eu2Pd2Sn → EuPdSn → EuPdSn2.
摘要:在密封钽安瓿中，通过感应熔融法制备了Sr2Pd3Sn、Eu2Pd3Sn和Eu2Pd3In三元Laves相。通过粉末x射线衍射图对产物进行了表征。利用x射线衍射单晶数据对Eu2Pd3Sn的结构进行了精化:Mg2MnGa3型，Cmcm, a = 583.36(5)， b = 908.31(7)， c = 958.06(8) pm, wR2 = 0.0366, 557 F2值，23个变量。钯和锡原子在Mg2MnGa3的缩合四面体网络上呈现相反的着色，即MnGa3与Pd3Sn。通过对占位参数的改进，发现铕位点存在较小的缺陷，从而得到了Eu1.962(6)Pd3Sn。Sr2Pd3Sn为泡利顺磁体，Eu2Pd3Sn为居里-魏斯顺磁体(7.86(1) µB Eu 原子−1和ΘP = 48.1(1) K)。在TC = 46.1(1) K以下观察到铁磁有序。本文从Sr2Pd3Sn/Eu2Pd3Sn→Sr2Pd2Sn/Eu2Pd2Sn→EuPdSn→EuPdSn2的顺序，讨论了Sr2Pd3Sn和Eu2Pd3Sn的119Sn和151Eu Mössbauer光谱中电子密度随锡含量和离子性的变化规律。
{"title":"Ternary orthorhombic Laves phases Sr2Pd3Sn, Eu2Pd3Sn and Eu2Pd3In","authors":"Joshua Wiethölter, Aylin Koldemir, T. Block, M. Reimann, Steffen Klenner, Rainer Pöttgen","doi":"10.1515/zkri-2023-0014","DOIUrl":"https://doi.org/10.1515/zkri-2023-0014","url":null,"abstract":"Abstract The ternary Laves phases Sr2Pd3Sn, Eu2Pd3Sn and Eu2Pd3In were synthesized by induction melting of the elements in sealed tantalum ampoules. The polycrystalline products were characterized through their powder X-ray diffraction patterns. The structure of Eu2Pd3Sn was refined from single crystal X-ray diffractometer data: Mg2MnGa3 type, Cmcm, a = 583.36(5), b = 908.31(7), c = 958.06(8) pm, wR2 = 0.0366, 557 F2 values, 23 variables. The palladium and tin atoms show the inverse coloring on the network of condensed tetrahedra of Mg2MnGa3, i.e., MnGa3 versus Pd3Sn. Refinement of the occupancy parameters revealed small defects for the europium site, leading to composition Eu1.962(6)Pd3Sn for the studied crystal. Sr2Pd3Sn is a Pauli paramagnet and Eu2Pd3Sn shows Curie-Weiss paramagnetism (7.86(1) µB Eu atom−1 and ΘP = 48.1(1) K). Ferromagnetic ordering is observed below TC = 46.1(1) K. The 119Sn and 151Eu Mössbauer spectra of Sr2Pd3Sn and Eu2Pd3Sn are discussed with respect to electron density changes as a function of the tin content and the ionicity in the sequence of the stannides Sr2Pd3Sn/Eu2Pd3Sn → Sr2Pd2Sn/Eu2Pd2Sn → EuPdSn → EuPdSn2.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"201 - 208"},"PeriodicalIF":1.2,"publicationDate":"2023-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45789869","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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