A protected tripeptide Boc-l-Leu-5-AIA-Aib-OMe was synthesized where 5-aminoisophthalic acid (5-AIA), a rigid non-coded aromatic γ-amino acid is incorporated as central residue. The single crystal X-ray diffraction study indicates that the peptide self-assembles into supramolecular sheet through intermolecular hydrogen bonding interaction N–H⋯O and π ··· π interaction.
{"title":"Synthesis and crystal structure of a tripeptide comprising a centrally placed non-coded aromatic γ-amino acid","authors":"Purak Das, Suven Das, Arpita Dutta","doi":"10.1515/zkri-2024-0095","DOIUrl":"https://doi.org/10.1515/zkri-2024-0095","url":null,"abstract":"A protected tripeptide Boc-<jats:sc>l</jats:sc>-Leu-5-AIA-Aib-OMe was synthesized where <jats:italic>5</jats:italic>-aminoisophthalic acid (5-AIA), a rigid non-coded aromatic γ-amino acid is incorporated as central residue. The single crystal X-ray diffraction study indicates that the peptide self-assembles into supramolecular sheet through intermolecular hydrogen bonding interaction N–H⋯O and <jats:italic>π</jats:italic> ··· <jats:italic>π</jats:italic> interaction.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142257128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Crystals of 1-nitronaphthalene were grown by evaporation of a methanol solution. The structure [P21/c, a = 13.2780(13) Å, b = 3.8131(3)° Å, c = 31.851(3) Å, β = 91.173(8), V = 1,612.3 Å3] was solved from a crystal twinned by twofold rotation about [100]. Twinning is explained by the polytype character: layers with (idealized) p2111 symmetry can connect via either 1‾ or 21 operations, leading to geometrically distinct pairs of layers. In the twin individuals, the two kinds of contacts alternate, at the composition plane two subsequent contacts of the same type are realized.
1-nitronaphthalene 晶体是通过甲醇溶液的蒸发作用生长出来的。结构[P21/c, a = 13.2780(13) Å, b = 3.8131(3)° Å, c = 31.851(3) Å, β = 91.173(8), V = 1,612.3 Å3]是由围绕[100]旋转两圈的孪晶求解的。孪晶是由多型特征解释的：具有（理想化的）p2111 对称性的层可以通过 1‾ 或 21 次操作连接起来，从而形成几何上不同的层对。在孪生个体中，两种接触交替进行，在组成平面上实现了两个相同类型的后续接触。
{"title":"1-Nitronaphthalene, a non-OD, non-MDO polytype","authors":"Matthias Schöbinger, Berthold Stöger","doi":"10.1515/zkri-2024-0089","DOIUrl":"https://doi.org/10.1515/zkri-2024-0089","url":null,"abstract":"Crystals of 1-nitronaphthalene were grown by evaporation of a methanol solution. The structure [<jats:italic>P</jats:italic>2<jats:sub>1</jats:sub>/<jats:italic>c</jats:italic>, <jats:italic>a</jats:italic> = 13.2780(13) Å, <jats:italic>b</jats:italic> = 3.8131(3)° Å, <jats:italic>c</jats:italic> = 31.851(3) Å, <jats:italic>β</jats:italic> = 91.173(8), <jats:italic>V</jats:italic> = 1,612.3 Å<jats:sup>3</jats:sup>] was solved from a crystal twinned by twofold rotation about [100]. Twinning is explained by the polytype character: layers with (idealized) <jats:italic>p</jats:italic>2<jats:sub>1</jats:sub>11 symmetry can connect via either 1‾ or 2<jats:sub>1</jats:sub> operations, leading to geometrically distinct pairs of layers. In the twin individuals, the two kinds of contacts alternate, at the composition plane two subsequent contacts of the same type are realized.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"69 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142257129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Federica Bravetti, Robert Hühn, Simone Bordignon, Sylvia Reibeling, Martin U. Schmidt
Pigment Red 48:2 is an industrially important hydrazone pigment, used for the colouration of plastics and printing inks. The crystal structure of the commercial phase was solved and refined from X-ray powder diffraction data. The phase (P.R.48:2, α-phase) was found to be a monohydrate with a chemical composition of Ca[C18H11ClN2O6S]·H2O. Its tautomeric state was investigated by multinuclear solid-state NMR. The 15N CPMAS unambiguously revealed the compound to adopt the hydrazone tautomeric form in the solid state. In an unrestrained Rietveld refinement, the crystal structure did not significantly change. The crystal structure was confirmed by dispersion-corrected DFT optimisation, which also included the calculation of solid-state NMR chemical shifts. Heating the monohydrate to about 200 °C results in an anhydrate (P.R.48:2, β-phase), which has not been described before. Its crystal structure was determined by X-ray powder diffraction, and confirmed by DFT-D, too. Solid-state NMR spectra confirmed that the crystal structure of P.R.48:2 remains mostly unchanged upon dehydration and that also the hydrazone tautomeric form is maintained. Both crystal structures are similar and present a double-layer structure. The non-polar layer contains the phenyl and naphthalene moieties, whereas the polar/ionic layer comprehends the calcium ions, carboxylate, sulfonate, carbonyl groups and water molecules. The calcium ions have a coordination number of 8 and 7 in the monohydrate and anhydrate phases, respectively. For the corresponding Mn salt (Pigment Red 48:4), at least two phases were found, but the quality of the powder patterns did not allow determining their crystal structures.
{"title":"Crystal structure and tautomeric state of Pigment Red 48:2 from X-ray powder diffraction and solid-state NMR","authors":"Federica Bravetti, Robert Hühn, Simone Bordignon, Sylvia Reibeling, Martin U. Schmidt","doi":"10.1515/zkri-2023-0042","DOIUrl":"https://doi.org/10.1515/zkri-2023-0042","url":null,"abstract":"Pigment Red 48:2 is an industrially important hydrazone pigment, used for the colouration of plastics and printing inks. The crystal structure of the commercial phase was solved and refined from X-ray powder diffraction data. The phase (P.R.48:2, α-phase) was found to be a monohydrate with a chemical composition of Ca[C<jats:sub>18</jats:sub>H<jats:sub>11</jats:sub>ClN<jats:sub>2</jats:sub>O<jats:sub>6</jats:sub>S]·H<jats:sub>2</jats:sub>O. Its tautomeric state was investigated by multinuclear solid-state NMR. The <jats:sup>15</jats:sup>N CPMAS unambiguously revealed the compound to adopt the hydrazone tautomeric form in the solid state. In an unrestrained Rietveld refinement, the crystal structure did not significantly change. The crystal structure was confirmed by dispersion-corrected DFT optimisation, which also included the calculation of solid-state NMR chemical shifts. Heating the monohydrate to about 200 °C results in an anhydrate (P.R.48:2, β-phase), which has not been described before. Its crystal structure was determined by X-ray powder diffraction, and confirmed by DFT-D, too. Solid-state NMR spectra confirmed that the crystal structure of P.R.48:2 remains mostly unchanged upon dehydration and that also the hydrazone tautomeric form is maintained. Both crystal structures are similar and present a double-layer structure. The non-polar layer contains the phenyl and naphthalene moieties, whereas the polar/ionic layer comprehends the calcium ions, carboxylate, sulfonate, carbonyl groups and water molecules. The calcium ions have a coordination number of 8 and 7 in the monohydrate and anhydrate phases, respectively. For the corresponding Mn salt (Pigment Red 48:4), at least two phases were found, but the quality of the powder patterns did not allow determining their crystal structures.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142223447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Md. Izzuddin Jundullah Hanafi, M. Mangir Murshed, Lars Robben, Thorsten M. Gesing
To fabricate metals from the base materials for future Mars exploration, synthesis of representative olivine phases and their structural and spectroscopic characterizations are of crucial importance. Using mechanochemical technique that mimics the mechanical weathering, a complete solid solution of (Mg1−xFex)2SiO4 has been synthesized to investigate the associated crystal chemical properties. X-ray powder diffraction data Rietveld analysis confirms that each polycrystalline sample crystallizes in space group Pbnm. The average crystallite size ranges between 80(1) nm and 223(4) nm. Each lattice parameter increases with increasing Fe-content due to the larger Fe2+ radius than that of Mg2+, following Vegard’s rule. For a given nominal chemical composition, substitution of Mg with Fe at the M1-site (4a: 0,0,0) is preferred to the M2-site (4c: x,y,¼). As a consequence, the average Fe-content lies slightly below the equivalence line for x = 0.2–0.8, indicating that the Fe/Mg ratio in the amorphous scattering content is most likely greater than unity. Characteristic Raman spectral features of the olivines have been explained in terms of the chemical composition (x). Simple regression models are demonstrated based on both X-ray diffraction and Raman spectroscopic data for the calculation of Mg/Fe in olivines. Diffuse reflectance UV/Vis spectra RATD analysis shows each olivine phase possesses direct band-gap between 3.38(3) eV and 4.90(3) eV. This study could keep valuable information to relevant databases for future human missions on Mars, in particular, for precise estimation of the representative olivines from the remote X-ray diffraction and spectroscopic data.
要从基础材料中制造出用于未来火星探测的金属，合成具有代表性的橄榄石相并研究其结构和光谱特性至关重要。利用模拟机械风化的机械化学技术，合成了 (Mg1-x Fe x )2SiO4 的完整固溶体，以研究相关的晶体化学特性。X 射线粉末衍射数据里特维尔德分析证实，每个多晶样品都在 Pbnm 空间群中结晶。平均晶粒大小介于 80(1) nm 和 223(4) nm 之间。由于 Fe2+ 的半径比 Mg2+ 的半径大，因此根据 Vegard 规则，每个晶格参数都会随着铁含量的增加而增加。对于给定的标称化学成分，在 M1 位点（4a：0,0,0）用铁取代镁比在 M2 位点（4c：x,y,¼）优先。因此，在 x = 0.2-0.8 时，平均铁含量略低于等值线，这表明非晶散射含量中的铁/镁比很可能大于一。橄榄石的拉曼光谱特征可以用化学成分（x）来解释。根据 X 射线衍射和拉曼光谱数据建立了简单的回归模型，用于计算橄榄石中的镁/铁含量。漫反射紫外/可见光谱 RATD 分析表明，每种橄榄石相都具有介于 3.38(3) eV 和 4.90(3) eV 之间的直接带隙。这项研究可以为未来人类火星任务的相关数据库提供有价值的信息，特别是可以从远程 X 射线衍射和光谱数据中精确地估算出具有代表性的橄榄石。
{"title":"Mechanochemical synthesis of (Mg1−x Fe x )2SiO4 olivine phases relevant to Martian regolith: structural and spectroscopic characterizations","authors":"Md. Izzuddin Jundullah Hanafi, M. Mangir Murshed, Lars Robben, Thorsten M. Gesing","doi":"10.1515/zkri-2024-0078","DOIUrl":"https://doi.org/10.1515/zkri-2024-0078","url":null,"abstract":"To fabricate metals from the base materials for future Mars exploration, synthesis of representative olivine phases and their structural and spectroscopic characterizations are of crucial importance. Using mechanochemical technique that mimics the mechanical weathering, a complete solid solution of (Mg<jats:sub>1−<jats:italic>x</jats:italic> </jats:sub>Fe<jats:sub> <jats:italic>x</jats:italic> </jats:sub>)<jats:sub>2</jats:sub>SiO<jats:sub>4</jats:sub> has been synthesized to investigate the associated crystal chemical properties. X-ray powder diffraction data Rietveld analysis confirms that each polycrystalline sample crystallizes in space group <jats:italic>Pbnm</jats:italic>. The average crystallite size ranges between 80(1) nm and 223(4) nm. Each lattice parameter increases with increasing Fe-content due to the larger Fe<jats:sup>2+</jats:sup> radius than that of Mg<jats:sup>2+</jats:sup>, following Vegard’s rule. For a given nominal chemical composition, substitution of Mg with Fe at the <jats:italic>M</jats:italic>1-site (4<jats:italic>a</jats:italic>: 0,0,0) is preferred to the <jats:italic>M</jats:italic>2-site (4<jats:italic>c</jats:italic>: <jats:italic>x</jats:italic>,<jats:italic>y</jats:italic>,¼). As a consequence, the average Fe-content lies slightly below the equivalence line for <jats:italic>x</jats:italic> = 0.2–0.8, indicating that the Fe/Mg ratio in the amorphous scattering content is most likely greater than unity. Characteristic Raman spectral features of the olivines have been explained in terms of the chemical composition (<jats:italic>x</jats:italic>). Simple regression models are demonstrated based on both X-ray diffraction and Raman spectroscopic data for the calculation of Mg/Fe in olivines. Diffuse reflectance UV/Vis spectra RATD analysis shows each olivine phase possesses direct band-gap between 3.38(3) eV and 4.90(3) eV. This study could keep valuable information to relevant databases for future human missions on Mars, in particular, for precise estimation of the representative olivines from the remote X-ray diffraction and spectroscopic data.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141864886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ivan Bernal, Roger A. Lalancette, Ahmad Hudaihed, Pavel Kucheryavy
Sirtinol is a known inhibitor of sirtuin proteins – a family of deacetylases involved in the physiology of aging. Its crystalline structure has never been determined except when bound to Fe(III) where it participates in the seven-fold coordination of the metal or to Cu(II) where it acts as a bidentate or tridentate ligand. Herein, we describe the structure of this important molecule, as follows: (a) the prevalent form of the keto-enol tautomerism in the solid state, and (b) in solution. Do they match? If not, how? The crystals of (R)-sirtinol are characterized by a large number of π–π bonded interactions linking molecules in infinite ribbons, which, in turn, are linked by additional π–π interactions of a variety of types, and by hydrogen bonds. In the latter case, we confirm by NMR that the X-ray determined position of an important H atom is on a N atom rather than on an O, which is how the molecule is usually depicted.
Sirtinol 是一种已知的 sirtuin 蛋白抑制剂，sirtuin 蛋白是参与衰老生理过程的脱乙酰酶家族。除了与 Fe（III）结合时参与金属的七重配位，或与 Cu（II）结合时作为双齿或三齿配体外，它的晶体结构尚未确定。在此，我们将对这一重要分子的结构进行如下描述：(a) 酮烯醇同分异构体在固态下的普遍形式，以及 (b) 在溶液中的形式。它们是否吻合？如果不吻合，如何吻合？(R)-松脂醇晶体的特点是有大量的 π-π 键相互作用将分子连接成无限的带状，而这些带状又通过各种类型的附加 π-π 作用和氢键连接起来。在后一种情况下，我们通过核磁共振证实，X 射线确定的一个重要氢原子的位置是在一个 N 原子上，而不是通常描述的分子的 O 原子上。
{"title":"The crystal and molecular structure of (R)-sirtinol – C26H22N2O2 – a chemo-sensitive enhancer and ligand in metal complexes with important bio-inorganic applications","authors":"Ivan Bernal, Roger A. Lalancette, Ahmad Hudaihed, Pavel Kucheryavy","doi":"10.1515/zkri-2024-0073","DOIUrl":"https://doi.org/10.1515/zkri-2024-0073","url":null,"abstract":"Sirtinol is a known inhibitor of sirtuin proteins – a family of deacetylases involved in the physiology of aging. Its crystalline structure has never been determined except when bound to Fe(III) where it participates in the seven-fold coordination of the metal or to Cu(II) where it acts as a bidentate or tridentate ligand. Herein, we describe the structure of this important molecule, as follows: (a) the prevalent form of the keto-enol tautomerism in the solid state, and (b) in solution. Do they match? If not, how? The crystals of (<jats:italic>R</jats:italic>)-sirtinol are characterized by a large number of <jats:italic>π–π</jats:italic> bonded interactions linking molecules in infinite ribbons, which, in turn, are linked by additional <jats:italic>π–π</jats:italic> interactions of a variety of types, and by hydrogen bonds. In the latter case, we confirm by NMR that the X-ray determined position of an important H atom is on a N atom rather than on an O, which is how the molecule is usually depicted.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"69 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141778380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Christopher S. Reuter, M. M. Murshed, Michael Fischer, T. Gesing
The crystal structures of both Pb2PbO4 (Pb3O4) and Pb2SnO4 at room temperature can be described using mullite-type setting in the space groups P42/mbc and Pbam, respectively. At what chemical extend the crystal structure prefers either of the space groups would be an excellent playground in the Pb2(Pb1−x Sn x )O4 solid solution. Members of the solid solutions have been prepared by solid-state reactions carried out in sealed quartz tubes. Each sample has been found to be phase pure confirmed by X-ray powder diffraction data Rietveld refinement. Samples with higher tin content require higher synthesis temperatures, and controlled decomposition of Pb3O4 serves as the source for both Pb2+ and Pb4+ cations. Since the Pb4+ cation is larger than Sn4+, the MO6 polyhedral volume decreases with increasing Sn-content. As such, each metric parameter shows a linear trend following Vegard’s rule. The concomitant contraction of the MO6 octahedra and the high stereo-chemical activity of the 6s 2 lone electron pairs of lead in the Pb2+O4 distorted pyramid results in symmetry reduction. DFT suggests dynamical instability of the tetragonal Pb3O4 while Pb2SnO4 keeps orthorhombic symmetry at low temperatures, which agrees well with the experimental findings. The global blue shift of the vibrational mode frequencies is explained by the quasi-harmonic approach. The indirect band-gap linearly increases from 2.1(1) eV (x = 0) to a maximum value of 2.5(1) eV for x = 0.8 followed by a sharp drop towards Pb2SnO4. Thermogravimetric analysis demonstrates higher thermal stability with increasing Sn-content, which is explained in terms of higher bond strength of Sn–O than that of Pb–O in the MO6 octahedra.
{"title":"Synthesis, characterization and structure-property relations in mullite-type Pb2(Pb1−x\u0000 Sn\u0000 x\u0000 )O4 solid solution","authors":"Christopher S. Reuter, M. M. Murshed, Michael Fischer, T. Gesing","doi":"10.1515/zkri-2024-0088","DOIUrl":"https://doi.org/10.1515/zkri-2024-0088","url":null,"abstract":"\u0000 The crystal structures of both Pb2PbO4 (Pb3O4) and Pb2SnO4 at room temperature can be described using mullite-type setting in the space groups P42/mbc and Pbam, respectively. At what chemical extend the crystal structure prefers either of the space groups would be an excellent playground in the Pb2(Pb1−x\u0000 Sn\u0000 x\u0000 )O4 solid solution. Members of the solid solutions have been prepared by solid-state reactions carried out in sealed quartz tubes. Each sample has been found to be phase pure confirmed by X-ray powder diffraction data Rietveld refinement. Samples with higher tin content require higher synthesis temperatures, and controlled decomposition of Pb3O4 serves as the source for both Pb2+ and Pb4+ cations. Since the Pb4+ cation is larger than Sn4+, the MO6 polyhedral volume decreases with increasing Sn-content. As such, each metric parameter shows a linear trend following Vegard’s rule. The concomitant contraction of the MO6 octahedra and the high stereo-chemical activity of the 6s\u0000 2 lone electron pairs of lead in the Pb2+O4 distorted pyramid results in symmetry reduction. DFT suggests dynamical instability of the tetragonal Pb3O4 while Pb2SnO4 keeps orthorhombic symmetry at low temperatures, which agrees well with the experimental findings. The global blue shift of the vibrational mode frequencies is explained by the quasi-harmonic approach. The indirect band-gap linearly increases from 2.1(1) eV (x = 0) to a maximum value of 2.5(1) eV for x = 0.8 followed by a sharp drop towards Pb2SnO4. Thermogravimetric analysis demonstrates higher thermal stability with increasing Sn-content, which is explained in terms of higher bond strength of Sn–O than that of Pb–O in the MO6 octahedra.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"22 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141648057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Block, Jutta Kösters, Samir F. Matar, Valentin Antoine Chamard, Rainer Pöttgen
The zinc-rich intermetallic phases CaRu2Zn10, SrRu2Zn10 and EuRu2Zn10 were synthesized by induction-melting of the elements in sealed tantalum ampoules followed by annealing to increase the crystallinity. The samples were characterized by powder X-ray diffraction and the structures were refined from single crystal X-ray diffractometer data: new type, P42/nnm, a = 894.68(14), c = 518.44(9) pm, wR2 = 0.0830, 432 F 2 values, 22 variables for CaRu2Zn10, a = 907.01(10), c = 516.35(6), wR2 = 0.0469, 445 F 2 values, 22 variables for SrRu2Zn10 and a = 902.84(9), c = 515.91(5) pm, wR2 = 0.0469, 434 F 2 values, 22 variables for EuRu2Zn10. The three structures are new ordering variants of the aristotype ThMn12. They are discussed on the basis of a group-subgroup scheme and compared to the known superstructures CaCr2Al10, ErNi10Si2 and ScFe6Ga6. The calcium atoms within the Ca@Ru4Zn16 polyhedra have flattened tetrahedral ruthenium coordination, reducing the calcium site symmetry to 4 ‾ $bar{4}$ 2m (instead of 4/mmm in the aristotype). Electronic structure calculations show a substantial charge transfer from calcium to ruthenium and an almost neutral zinc substructure.
富锌金属间相 CaRu2Zn10、SrRu2Zn10 和 EuRu2Zn10 是通过在密封的钽安瓿瓶中感应熔化元素，然后退火以提高结晶度而合成的。样品采用粉末 X 射线衍射法进行表征，并根据单晶 X 射线衍射仪数据完善了结构：新型，P42/nnm，a = 894.68(14)，c = 518.44(9) pm，wR2 = 0.0830, 432 F 2 values, 22 variables for CaRu2Zn10, a = 907.01(10), c = 516.35(6), wR2 = 0.0469, 445 F 2 values, 22 variables for SrRu2Zn10 and a = 902.84(9), c = 515.91(5) pm, wR2 = 0.0469, 434 F 2 values, 22 variables for EuRu2Zn10.这三种结构是原型 ThMn12 的新排序变体。我们根据基团-子群方案对它们进行了讨论，并与已知的超结构 CaCr2Al10、ErNi10Si2 和 ScFe6Ga6 进行了比较。Ca@Ru4Zn16 多面体中的钙原子具有扁平的四面体钌配位，将钙位点对称性降低到 4 ‾ $bar{4}$ 2m（而不是原型中的 4/mmm）。电子结构计算显示，钙向钌转移了大量电荷，锌的亚结构几乎呈中性。
{"title":"CaRu2Zn10, SrRu2Zn10 and EuRu2Zn10 – new superstructure variants of ThMn12","authors":"T. Block, Jutta Kösters, Samir F. Matar, Valentin Antoine Chamard, Rainer Pöttgen","doi":"10.1515/zkri-2024-0084","DOIUrl":"https://doi.org/10.1515/zkri-2024-0084","url":null,"abstract":"\u0000 The zinc-rich intermetallic phases CaRu2Zn10, SrRu2Zn10 and EuRu2Zn10 were synthesized by induction-melting of the elements in sealed tantalum ampoules followed by annealing to increase the crystallinity. The samples were characterized by powder X-ray diffraction and the structures were refined from single crystal X-ray diffractometer data: new type, P42/nnm, a = 894.68(14), c = 518.44(9) pm, wR2 = 0.0830, 432 F\u0000 2 values, 22 variables for CaRu2Zn10, a = 907.01(10), c = 516.35(6), wR2 = 0.0469, 445 F\u0000 2 values, 22 variables for SrRu2Zn10 and a = 902.84(9), c = 515.91(5) pm, wR2 = 0.0469, 434 F\u0000 2 values, 22 variables for EuRu2Zn10. The three structures are new ordering variants of the aristotype ThMn12. They are discussed on the basis of a group-subgroup scheme and compared to the known superstructures CaCr2Al10, ErNi10Si2 and ScFe6Ga6. The calcium atoms within the Ca@Ru4Zn16 polyhedra have flattened tetrahedral ruthenium coordination, reducing the calcium site symmetry to \u0000 \u0000 \u0000 \u0000 \u0000 4\u0000 ‾\u0000 \u0000 \u0000 \u0000 \u0000$bar{4}$\u0000\u0000 \u0000 \u0000 2m (instead of 4/mmm in the aristotype). Electronic structure calculations show a substantial charge transfer from calcium to ruthenium and an almost neutral zinc substructure.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"120 20","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141646979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Venkataraman Balasubramanian, Sukumar Kalpana, Aziz Ibragimov, Chellakarungu Balakrishnan
This study focuses on synthesizing and characterizing supramolecular cocrystals derived from 4-cyano-1-methylpyridinium iodide and 18-crown-6. The synthesis employed a solvent evaporation technique, followed by a thorough structural analysis utilizing XRD methods. The compound’s purity is confirmed by powder XRD analysis, while single-crystal XRD confirms its triclinic system packing with a centrosymmetric space group (P1‾$Poverline{1}$). The findings unveiled the emergence of unique cocrystals characterized by distinct molecular configurations supported by hydrogen bonding and ion-dipole interactions. Through diffuse reflectance spectral measurements, the direct band gap energy was assessed at 2.36 eV. Thermogravimetric analysis was utilized to evaluate the thermal properties of the compound across varying temperatures. The compound’s elemental composition and surface morphology were analyzed through investigations using EDS and SEM.
本研究的重点是合成和表征由 4-氰基-1-甲基吡啶鎓碘化物和 18-冠醚-6 衍生的超分子共晶体。合成采用了溶剂蒸发技术，然后利用 XRD 方法进行了全面的结构分析。粉末 X 射线衍射分析证实了该化合物的纯度，而单晶 X 射线衍射分析则证实了其具有中心对称空间群（P 1 ‾ $Poverline{1}$ ）的三菱系填料。这些发现揭示了独特的共晶体的出现，其特点是通过氢键和离子-偶极子相互作用支持独特的分子构型。通过漫反射光谱测量，直接带隙能被评估为 2.36 eV。热重分析用于评估该化合物在不同温度下的热特性。通过使用 EDS 和 SEM 对化合物的元素组成和表面形态进行了分析。
{"title":"Synthesis and structural characterization of supramolecular cocrystals of [(4-cyano-1-methylpyridinium)2-(18-crown-6)] diiodide","authors":"Venkataraman Balasubramanian, Sukumar Kalpana, Aziz Ibragimov, Chellakarungu Balakrishnan","doi":"10.1515/zkri-2024-0085","DOIUrl":"https://doi.org/10.1515/zkri-2024-0085","url":null,"abstract":"This study focuses on synthesizing and characterizing supramolecular cocrystals derived from 4-cyano-1-methylpyridinium iodide and 18-crown-6. The synthesis employed a solvent evaporation technique, followed by a thorough structural analysis utilizing XRD methods. The compound’s purity is confirmed by powder XRD analysis, while single-crystal XRD confirms its triclinic system packing with a centrosymmetric space group (<jats:inline-formula> <jats:alternatives> <m:math xmlns:m=\"http://www.w3.org/1998/Math/MathML\" overflow=\"scroll\"> <m:mrow> <m:mi>P</m:mi> <m:mover accent=\"true\"> <m:mn>1</m:mn> <m:mo>‾</m:mo> </m:mover> </m:mrow> </m:math> <jats:tex-math>$Poverline{1}$</jats:tex-math> <jats:inline-graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" xlink:href=\"graphic/j_zkri-2024-0085_ineq_001.png\"/> </jats:alternatives> </jats:inline-formula>). The findings unveiled the emergence of unique cocrystals characterized by distinct molecular configurations supported by hydrogen bonding and ion-dipole interactions. Through diffuse reflectance spectral measurements, the direct band gap energy was assessed at 2.36 eV. Thermogravimetric analysis was utilized to evaluate the thermal properties of the compound across varying temperatures. The compound’s elemental composition and surface morphology were analyzed through investigations using EDS and SEM.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"221 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141552299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
New triazole-based tridentate ligands were synthesized, and their crystal structures determined. Through comparison with the crystal structures of the starting materials and related published ligands, dependencies of intermolecular interactions based on the substitution patterns of the triazole motif were identified. In addition to π-stacking interactions, hydrogen bonding, and C–H···π interactions emerged as key players in intermolecular interactions. The observed variations in these interactions will aid in the design of platinum(II) complexes with specific properties.
{"title":"Structural influences of the substituents of tridentate triazole-based ligands – more than just a minor role in the solid-state structure","authors":"Simon Kroos, Marian Hebenbrock","doi":"10.1515/zkri-2024-0069","DOIUrl":"https://doi.org/10.1515/zkri-2024-0069","url":null,"abstract":"New triazole-based tridentate ligands were synthesized, and their crystal structures determined. Through comparison with the crystal structures of the starting materials and related published ligands, dependencies of intermolecular interactions based on the substitution patterns of the triazole motif were identified. In addition to π-stacking interactions, hydrogen bonding, and C–H···π interactions emerged as key players in intermolecular interactions. The observed variations in these interactions will aid in the design of platinum(II) complexes with specific properties.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"34 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141552300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Christopher Benndorf, Hellmut Eckert, Rainer Pöttgen
A series of ternary rare earth – transition metal – tetrelides RET2Tt2 (RE = Sc, Y, La, Lu; T = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au; Tt = Si, Ge) was synthesized by arc melting of the elements and subsequent annealing. The samples were characterized by powder X-ray diffraction and in addition, the structures of REOs2Si2 (RE = Y, La, Lu), LaAu2Si2, LaAg2Ge2 and LaAu2Ge2 were refined from single crystal X-ray diffractometer data. The tetrelides crystallize with the ThCr2Si2 type (I4/mmm) except the platinum compounds which adopt the klassengleiche superstructure of the CaBe2Ge2 type (P4/nmm). The transition metal atoms have tetrahedral tetrel coordination and the tetrahedra condense to layers via common edges. The stacking of these layers leads to Tt−Tt bonds in the ThCr2Si2 type phases and heteroatomic T−Tt bonds in the CaBe2Ge2 type phases. The rare earth atoms fill larger cages within these three-dimensional networks (coordination number 16 with RE@T8Tt8) with site symmetries 4/mmm (ThCr2Si2 type) and 4mm (CaBe2Ge2 type). Systematic multinuclear solid state NMR spectroscopic investigations allowed observing the effect of the involved rare-earth metal, transition metal and tetrel group element, respectively. In particular, 29Si isotropic resonance shifts can be predicted from element-specific increments and interatomic Si–Si bonding interactions manifest themselves in axially symmetric magnetic shielding anisotropies.
{"title":"Multinuclear solid state NMR spectroscopy of ternary rare-earth silicides RET 2Si2 and germanides LaT 2Ge2 (RE = Sc, Y, La, Lu; T = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au)","authors":"Christopher Benndorf, Hellmut Eckert, Rainer Pöttgen","doi":"10.1515/zkri-2024-0068","DOIUrl":"https://doi.org/10.1515/zkri-2024-0068","url":null,"abstract":"A series of ternary rare earth – transition metal – tetrelides <jats:italic>RET</jats:italic> <jats:sub>2</jats:sub> <jats:italic>Tt</jats:italic> <jats:sub>2</jats:sub> (<jats:italic>RE</jats:italic> = Sc, Y, La, Lu; <jats:italic>T</jats:italic> = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au; <jats:italic>Tt</jats:italic> = Si, Ge) was synthesized by arc melting of the elements and subsequent annealing. The samples were characterized by powder X-ray diffraction and in addition, the structures of <jats:italic>RE</jats:italic>Os<jats:sub>2</jats:sub>Si<jats:sub>2</jats:sub> (<jats:italic>RE</jats:italic> = Y, La, Lu), LaAu<jats:sub>2</jats:sub>Si<jats:sub>2</jats:sub>, LaAg<jats:sub>2</jats:sub>Ge<jats:sub>2</jats:sub> and LaAu<jats:sub>2</jats:sub>Ge<jats:sub>2</jats:sub> were refined from single crystal X-ray diffractometer data. The tetrelides crystallize with the ThCr<jats:sub>2</jats:sub>Si<jats:sub>2</jats:sub> type (<jats:italic>I</jats:italic>4/<jats:italic>mmm</jats:italic>) except the platinum compounds which adopt the <jats:italic>klassengleiche</jats:italic> superstructure of the CaBe<jats:sub>2</jats:sub>Ge<jats:sub>2</jats:sub> type (<jats:italic>P</jats:italic>4/<jats:italic>nmm</jats:italic>). The transition metal atoms have tetrahedral tetrel coordination and the tetrahedra condense to layers via common edges. The stacking of these layers leads to <jats:italic>Tt</jats:italic>−<jats:italic>Tt</jats:italic> bonds in the ThCr<jats:sub>2</jats:sub>Si<jats:sub>2</jats:sub> type phases and heteroatomic <jats:italic>T</jats:italic>−<jats:italic>Tt</jats:italic> bonds in the CaBe<jats:sub>2</jats:sub>Ge<jats:sub>2</jats:sub> type phases. The rare earth atoms fill larger cages within these three-dimensional networks (coordination number 16 with <jats:italic>RE</jats:italic>@<jats:italic>T</jats:italic> <jats:sub>8</jats:sub> <jats:italic>Tt</jats:italic> <jats:sub>8</jats:sub>) with site symmetries 4/<jats:italic>mmm</jats:italic> (ThCr<jats:sub>2</jats:sub>Si<jats:sub>2</jats:sub> type) and 4<jats:italic>mm</jats:italic> (CaBe<jats:sub>2</jats:sub>Ge<jats:sub>2</jats:sub> type). Systematic multinuclear solid state NMR spectroscopic investigations allowed observing the effect of the involved rare-earth metal, transition metal and tetrel group element, respectively. In particular, <jats:sup>29</jats:sup>Si isotropic resonance shifts can be predicted from element-specific increments and interatomic Si–Si bonding interactions manifest themselves in axially symmetric magnetic shielding anisotropies.","PeriodicalId":23855,"journal":{"name":"Zeitschrift für Kristallographie - Crystalline Materials","volume":"52 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141509098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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