V. Grishaev, O. Siidra, Mishel R. Markovski, D. Charkin, Timofey A. Omelchenko, Evgenii V. Nazarchuk
Abstract Crystals of two new polymorphic forms of the known compound (NaCl)[Cu(HSeO3)2], which we term polymorphs II and III, were formed after a ca. one-year dwelling of a crystalline precipitate under mother liquor and upon crystallization in the presence of K+, respectively. Both structures belong to the “layered copper hydroselenite” family. The polymorph II is a structural analog of (KCl)[Cu(HSeO3)2] with a fully ordered Na+ site; the main difference concerns the environment of Cu2+ which is more regular in (NaCl)[Cu(HSeO3)2]-II. In contrast to some expectations, crystallization from solutions containing KCl. NaCl, CuCl2, and H2SeO3 upon evaporation does not result in formation of mixed (Na1−xK x Cl)[Cu(HSeO3)2] crystals, but rather in a separate crystallization of (KCl)[Cu(HSeO3)2] and (NaCl)[Cu(HSeO3)2]-III which exhibits a complex structure with four ordered and one disordered Na+ sites. It is possible that longer crystallization times enhance formation of ordered structures.
摘要:已知化合物(NaCl)[Cu(HSeO3)2]的两种新的多晶型晶体，我们称之为多晶型II和III，分别在母液下和K+存在下结晶沉淀约一年后形成。这两种结构都属于“层状亚硒酸铜”族。晶型II是(KCl)[Cu(HSeO3)2]的结构类似物，具有完全有序的Na+位点;主要区别在于Cu2+在(NaCl)[Cu(HSeO3)2]-II中的环境更为规则。与一些预期相反，含KCl的溶液结晶。NaCl、CuCl2和H2SeO3蒸发后不会形成混合的(Na1−xK x Cl)[Cu(HSeO3)2]晶体，而是形成(KCl)[Cu(HSeO3)2]和(NaCl)[Cu(HSeO3)2]-III的独立结晶，呈现出4个有序和1个无序Na+位的复杂结构。较长的结晶时间可能促进有序结构的形成。
{"title":"Synthesis and crystal structure of two novel polymorphs of (NaCl)[Cu(HSeO3)2]: a further contribution to the family of layered copper hydrogen selenites","authors":"V. Grishaev, O. Siidra, Mishel R. Markovski, D. Charkin, Timofey A. Omelchenko, Evgenii V. Nazarchuk","doi":"10.1515/zkri-2023-0004","DOIUrl":"https://doi.org/10.1515/zkri-2023-0004","url":null,"abstract":"Abstract Crystals of two new polymorphic forms of the known compound (NaCl)[Cu(HSeO3)2], which we term polymorphs II and III, were formed after a ca. one-year dwelling of a crystalline precipitate under mother liquor and upon crystallization in the presence of K+, respectively. Both structures belong to the “layered copper hydroselenite” family. The polymorph II is a structural analog of (KCl)[Cu(HSeO3)2] with a fully ordered Na+ site; the main difference concerns the environment of Cu2+ which is more regular in (NaCl)[Cu(HSeO3)2]-II. In contrast to some expectations, crystallization from solutions containing KCl. NaCl, CuCl2, and H2SeO3 upon evaporation does not result in formation of mixed (Na1−xK x Cl)[Cu(HSeO3)2] crystals, but rather in a separate crystallization of (KCl)[Cu(HSeO3)2] and (NaCl)[Cu(HSeO3)2]-III which exhibits a complex structure with four ordered and one disordered Na+ sites. It is possible that longer crystallization times enhance formation of ordered structures.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"177 - 185"},"PeriodicalIF":1.2,"publicationDate":"2023-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47179143","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 Dolomite-type MSn(BO3)2 phases for M = Mn, Fe, Co and Ni have been synthesized using solid-state synthesis carried out in sealed quartz tubes. X-ray powder diffraction data Rietveld refinements confirm the rhombohedral space group R 3 ‾ $Roverline{3}$ for all compositions. The change in unit-cell parameters follows the increasing nature of the radius of the M-cations. Both the MO6 and SnO6 octahedra are found to be quite regular. 119Sn Mössbauer spectroscopy investigations complement the almost undistorted nature of the SnO6 octahedra and the tetra-valent charge of the tin-atoms. Detailed vibrational features are described from the Raman and the FTIR spectral data collected at ambient conditions. The frequency shifts of some selective Raman and IR bands are explained in terms of the change of cationic sizes and the respective M–O bond distances. The UV/Vis diffuse reflectance data are analyzed using the RATD method, leading to direct bandgaps for all the investigated samples. The wide bandgap semiconductors (3 – 4 eV) show increasing transition energies with increasing cation sizes of the high-spin M-cations in the dolomite types.
{"title":"Synthesis, structural and spectroscopic investigations of dolomite-type MSn(BO3)2 with M = Mn, Fe, Co and Ni","authors":"S. Wittmann, M. Murshed, V. Bilovol, T. Gesing","doi":"10.1515/zkri-2023-0002","DOIUrl":"https://doi.org/10.1515/zkri-2023-0002","url":null,"abstract":"Abstract Dolomite-type MSn(BO3)2 phases for M = Mn, Fe, Co and Ni have been synthesized using solid-state synthesis carried out in sealed quartz tubes. X-ray powder diffraction data Rietveld refinements confirm the rhombohedral space group R 3 ‾ $Roverline{3}$ for all compositions. The change in unit-cell parameters follows the increasing nature of the radius of the M-cations. Both the MO6 and SnO6 octahedra are found to be quite regular. 119Sn Mössbauer spectroscopy investigations complement the almost undistorted nature of the SnO6 octahedra and the tetra-valent charge of the tin-atoms. Detailed vibrational features are described from the Raman and the FTIR spectral data collected at ambient conditions. The frequency shifts of some selective Raman and IR bands are explained in terms of the change of cationic sizes and the respective M–O bond distances. The UV/Vis diffuse reflectance data are analyzed using the RATD method, leading to direct bandgaps for all the investigated samples. The wide bandgap semiconductors (3 – 4 eV) show increasing transition energies with increasing cation sizes of the high-spin M-cations in the dolomite types.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"167 - 175"},"PeriodicalIF":1.2,"publicationDate":"2023-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46892672","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 β-phase of Pigment Yellow 110 was determined from X-ray Powder Diffraction (XRPD) data. The crystal structure of the α-phase (Erk et al., CrystEngComm 2004, 6, 474) is re-refined against the original XRPD data to modern-day standards. Dispersion-corrected density functional theory calculations are used to complement the powder data. The α- and β-form crystallise in P 1 ‾ $Poverline{1}$ and P21/c, respectively, with the P.Y. 110 molecule occupying a centre of symmetry in both forms. Both polymorphs are layered structures consisting of infinite chains of hydrogen-bonded molecules.
{"title":"Crystal structures of two phases of Pigment Yellow 110 from X-ray powder diffraction data","authors":"J. van de Streek, S. N. Ivashevskaya, M. Schmidt","doi":"10.1515/zkri-2023-0003","DOIUrl":"https://doi.org/10.1515/zkri-2023-0003","url":null,"abstract":"Abstract The crystal structure of the β-phase of Pigment Yellow 110 was determined from X-ray Powder Diffraction (XRPD) data. The crystal structure of the α-phase (Erk et al., CrystEngComm 2004, 6, 474) is re-refined against the original XRPD data to modern-day standards. Dispersion-corrected density functional theory calculations are used to complement the powder data. The α- and β-form crystallise in P 1 ‾ $Poverline{1}$ and P21/c, respectively, with the P.Y. 110 molecule occupying a centre of symmetry in both forms. Both polymorphs are layered structures consisting of infinite chains of hydrogen-bonded molecules.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"217 - 223"},"PeriodicalIF":1.2,"publicationDate":"2023-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43975642","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}
A. Topnikova, E. Belokoneva, A. Volkov, O. Dimitrova, S. Stefanovich
Abstract New silicate-germanates (K2.9Cs0.1)(Sc0.7In0.3)[(Si2.95Ge0.05)O9]·H2O and (K2.16Cs0.84)Bi[(Si0.5Ge0.5)3O9]·H2O have been synthesized in multi-component systems under mild hydrothermal conditions. The new compounds are classified as new representatives of close related K3ScSi3O9·H2O parent structure, sp. gr. Pmn21. Their structural and isomorphic peculiarities are compared with it as well as with earlier investigated K1.46Pb1.54Сa[(Ge0.23Si0.77)3O9](ОН)0.54·0.46Н2О. Together with other known compounds, silicate-germanates form the extensive family A3M[T3O9]·H2O, A = K, Cs, Ca, Pb; M = Ho, Sc, Lu, Tb, Er, Y, Bi, Pb, In; T = Si, Ge, with a mixed microporous framework combined of M-octahedra and T-tetrahedra. Large alkali metal or/and Ca, Pb cations fill broad framework channels with cross-section up to 7.3 Å. Because of wide isomorphic substitution in the channels, and in tetrahedra and octahedra, ion exchange properties in the family are expected. Due to polar symmetry, all the crystals possess second-order nonlinearity which was confirmed with positive SHG tests for four compositions. Powder SHG experiments demonstrated moderate second harmonic intensities of order of α-quartz standard signals.
{"title":"Microporous framework polar silicate-germanates with a wide isomorphic substitution: (K2.9Cs0.1)(Sc0.7In0.3)[(Si2.95Ge0.05)O9]·H2O and (K2.16Cs0.84)Bi[(Si1.5Ge1.5)O9]·H2O","authors":"A. Topnikova, E. Belokoneva, A. Volkov, O. Dimitrova, S. Stefanovich","doi":"10.1515/zkri-2022-0056","DOIUrl":"https://doi.org/10.1515/zkri-2022-0056","url":null,"abstract":"Abstract New silicate-germanates (K2.9Cs0.1)(Sc0.7In0.3)[(Si2.95Ge0.05)O9]·H2O and (K2.16Cs0.84)Bi[(Si0.5Ge0.5)3O9]·H2O have been synthesized in multi-component systems under mild hydrothermal conditions. The new compounds are classified as new representatives of close related K3ScSi3O9·H2O parent structure, sp. gr. Pmn21. Their structural and isomorphic peculiarities are compared with it as well as with earlier investigated K1.46Pb1.54Сa[(Ge0.23Si0.77)3O9](ОН)0.54·0.46Н2О. Together with other known compounds, silicate-germanates form the extensive family A3M[T3O9]·H2O, A = K, Cs, Ca, Pb; M = Ho, Sc, Lu, Tb, Er, Y, Bi, Pb, In; T = Si, Ge, with a mixed microporous framework combined of M-octahedra and T-tetrahedra. Large alkali metal or/and Ca, Pb cations fill broad framework channels with cross-section up to 7.3 Å. Because of wide isomorphic substitution in the channels, and in tetrahedra and octahedra, ion exchange properties in the family are expected. Due to polar symmetry, all the crystals possess second-order nonlinearity which was confirmed with positive SHG tests for four compositions. Powder SHG experiments demonstrated moderate second harmonic intensities of order of α-quartz standard signals.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"119 - 127"},"PeriodicalIF":1.2,"publicationDate":"2023-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49663519","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 new cobalt(II) compound with the formula [Co(5-Br-pyc)(2,2′-bipy)(H2O)(Cl)]·2H2O (1·H2O) (5-Br-Hpyc = 5-bromo-pyridine-2-carboxylic acid, 2,2′-bipy = 2,2′-bipyridine) has been hydrothermally synthesized and well characterized. The X-ray single-crystal diffraction analysis showed that 1⋅2H2O has crystallizes in the monoclinic system, space group P21/c (no. 14). The Co(II) center was octahedrally bonded by one bidentate chelate 5-Br-pyc anion and one 2,2′-bipy, one water molecule as well as one chloride anion to form the mononuclear structure of 1⋅2H2O. Complex 1⋅2H2O forms a 3D network through abundant O–H⋅⋅⋅O hydrogen bonds and π⋅⋅⋅π stacking interactions. Notably, the 5-Br-Hpyc ligand was in situ generated by decarboxylation of the 3-bromo-pyridine-2,6-dicarboxylic acid (3-Br-H2pydc) precursor selectively on 2-position under hydrothermal conditions. The magnetic properties, the Hirshfeld surface structure and the synthetic process for 1⋅2H2O have been carefully described and discussed.
{"title":"An asymmetric mononuclear cobalt(II) compound derived from 3-bromo-pyridine-2,6-dicarboxylic acid involving in-situ hydrothermal decarboxylation: structure, magnetic property and Hirshfeld surface analysis","authors":"Jun-Xia Li, Shuai Ge, Yi-Jing Lu, Xiao-Jie Xu, Chan-Hua Liu, Shihui Li","doi":"10.1515/zkri-2023-0001","DOIUrl":"https://doi.org/10.1515/zkri-2023-0001","url":null,"abstract":"Abstract A new cobalt(II) compound with the formula [Co(5-Br-pyc)(2,2′-bipy)(H2O)(Cl)]·2H2O (1·H2O) (5-Br-Hpyc = 5-bromo-pyridine-2-carboxylic acid, 2,2′-bipy = 2,2′-bipyridine) has been hydrothermally synthesized and well characterized. The X-ray single-crystal diffraction analysis showed that 1⋅2H2O has crystallizes in the monoclinic system, space group P21/c (no. 14). The Co(II) center was octahedrally bonded by one bidentate chelate 5-Br-pyc anion and one 2,2′-bipy, one water molecule as well as one chloride anion to form the mononuclear structure of 1⋅2H2O. Complex 1⋅2H2O forms a 3D network through abundant O–H⋅⋅⋅O hydrogen bonds and π⋅⋅⋅π stacking interactions. Notably, the 5-Br-Hpyc ligand was in situ generated by decarboxylation of the 3-bromo-pyridine-2,6-dicarboxylic acid (3-Br-H2pydc) precursor selectively on 2-position under hydrothermal conditions. The magnetic properties, the Hirshfeld surface structure and the synthetic process for 1⋅2H2O have been carefully described and discussed.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"139 - 149"},"PeriodicalIF":1.2,"publicationDate":"2023-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45812866","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 new copper(II) complex [Cu(3,5,6-tcpa)(2,2′-bipy)Cl] (1) has been obtained through the one-pot hydrothermal reaction of copper chloride dihydrate with triclopyr (systematic name 2-((3,5,6-trichloropyridin-2-yl)oxy)acetic acid, abbreviation 3,5,6-Htcpa) and 2,2′-bipyridine (2,2′-bipy) coligands. 1 has crystallized in triclinic crystal system, P 1 ‾ $overline{1}$ space group. The central copper(II) ion displayed a distorted square–pyramidal geometry and was connected by one chlorido co-ligand (Clˉ), one 3,5,6-tcpa anionic chelator and one chelating 2,2’-bipy ligand to afford a mononuclear structure. 1 is further extended into a 3D network by the non-covalent interactions of H⋯Cl, H⋯O hydrogen bonds, aromatic π⋯π stacking together with Cl⋯Cl halogen bond interactions. The co-crystallization process, the crystal structure of 1 as well as the Hirshfeld surface analysis for 1 have been analyzed and described. In addition, the flexible conformation of phenoxy methylene group among 1, triclopyr acid and its previously reported co-crystallized compound also have been carefully compared and discussed.
{"title":"A new copper(II) complex containing triclopyr: one-pot crystallization, structure, conformation and Hirshfeld surface analyses","authors":"Jun-Xia Li, Shuai Ge, Yi-Jing Lu, Ke-Ying Quan, Li-Bing Wu, Ai-Rong Wang","doi":"10.1515/zkri-2022-0063","DOIUrl":"https://doi.org/10.1515/zkri-2022-0063","url":null,"abstract":"Abstract A new copper(II) complex [Cu(3,5,6-tcpa)(2,2′-bipy)Cl] (1) has been obtained through the one-pot hydrothermal reaction of copper chloride dihydrate with triclopyr (systematic name 2-((3,5,6-trichloropyridin-2-yl)oxy)acetic acid, abbreviation 3,5,6-Htcpa) and 2,2′-bipyridine (2,2′-bipy) coligands. 1 has crystallized in triclinic crystal system, P 1 ‾ $overline{1}$ space group. The central copper(II) ion displayed a distorted square–pyramidal geometry and was connected by one chlorido co-ligand (Clˉ), one 3,5,6-tcpa anionic chelator and one chelating 2,2’-bipy ligand to afford a mononuclear structure. 1 is further extended into a 3D network by the non-covalent interactions of H⋯Cl, H⋯O hydrogen bonds, aromatic π⋯π stacking together with Cl⋯Cl halogen bond interactions. The co-crystallization process, the crystal structure of 1 as well as the Hirshfeld surface analysis for 1 have been analyzed and described. In addition, the flexible conformation of phenoxy methylene group among 1, triclopyr acid and its previously reported co-crystallized compound also have been carefully compared and discussed.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"129 - 137"},"PeriodicalIF":1.2,"publicationDate":"2023-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48395194","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}
C. Paulsen, Josef Maximilian Gerdes, V. Svitlyk, M. Reimann, Alfred Rabenbauer, T. Nilges, M. Hansen, R. Pöttgen
Abstract The metal-rich phosphide TaCrP forms from the elements by step-wise solid state reaction in an alumina crucible (maximum annealing temperature 1180 K). TaCrP is trimorphic. The structural data of the hexagonal ZrNiAl high-temperature phase (space group P 6 ‾ 2 m $Poverline{6}2m$ ) was deduced from a Rietveld refinement. At room temperature TaCrP crystallizes with the TiNiSi type (Pnma, a = 623.86(5), b = 349.12(3), c = 736.78(6) pm, wR = 0.0419, 401 F2 values, 20 variables) and shows a Peierls type transition below ca. 280 K to the monoclinic low-temperature modification (P121/c1, a = 630.09(3), b = 740.3(4), c = 928.94(4) pm, β = 132.589(5)°, wR = 0.0580, 1378 F2 values, 57 variables). The latter phase transition is driven by pairwise Cr–Cr bond formation out of an equidistant chain in o-TaCrP. The phase transition was monitored via different analytical tools: differential scanning calorimetry, powder synchrotron X-ray diffraction, magnetic susceptibility measurements and 31P solid state NMR spectroscopy.
{"title":"Trimorphic TaCrP – A diffraction and 31P solid state NMR spectroscopic study","authors":"C. Paulsen, Josef Maximilian Gerdes, V. Svitlyk, M. Reimann, Alfred Rabenbauer, T. Nilges, M. Hansen, R. Pöttgen","doi":"10.1515/zkri-2022-0070","DOIUrl":"https://doi.org/10.1515/zkri-2022-0070","url":null,"abstract":"Abstract The metal-rich phosphide TaCrP forms from the elements by step-wise solid state reaction in an alumina crucible (maximum annealing temperature 1180 K). TaCrP is trimorphic. The structural data of the hexagonal ZrNiAl high-temperature phase (space group P 6 ‾ 2 m $Poverline{6}2m$ ) was deduced from a Rietveld refinement. At room temperature TaCrP crystallizes with the TiNiSi type (Pnma, a = 623.86(5), b = 349.12(3), c = 736.78(6) pm, wR = 0.0419, 401 F2 values, 20 variables) and shows a Peierls type transition below ca. 280 K to the monoclinic low-temperature modification (P121/c1, a = 630.09(3), b = 740.3(4), c = 928.94(4) pm, β = 132.589(5)°, wR = 0.0580, 1378 F2 values, 57 variables). The latter phase transition is driven by pairwise Cr–Cr bond formation out of an equidistant chain in o-TaCrP. The phase transition was monitored via different analytical tools: differential scanning calorimetry, powder synchrotron X-ray diffraction, magnetic susceptibility measurements and 31P solid state NMR spectroscopy.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"105 - 117"},"PeriodicalIF":1.2,"publicationDate":"2023-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41726185","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 cyanamide and carbodiimide anions are complex nitrogen-derived one-dimensional species of the type NCN2− (hence, resembling O2− but more covalently bonding) that form a huge number of salt-like phases with a variety of metal cations stemming from the whole Periodic Table. Depending on the coloring (binary, ternary and quaternary salts are known), the cationic size and charge as well as covalent contributions, different distortion (tilting in particular) and/or vacancy ordering variants of cyanamides/carbodiimides occur. Herein we summarize those cyanamide/carbodiimide structures that derive from the aristotype NiAs. The crystal chemistry is discussed on the basis of group-subgroup schemes (Bärnighausen trees).
{"title":"NiAs-derived cyanamide (carbodiimide) structures – a group-theoretical view","authors":"R. Pöttgen, Alex J. Corkett, R. Dronskowski","doi":"10.1515/zkri-2022-0062","DOIUrl":"https://doi.org/10.1515/zkri-2022-0062","url":null,"abstract":"Abstract The cyanamide and carbodiimide anions are complex nitrogen-derived one-dimensional species of the type NCN2− (hence, resembling O2− but more covalently bonding) that form a huge number of salt-like phases with a variety of metal cations stemming from the whole Periodic Table. Depending on the coloring (binary, ternary and quaternary salts are known), the cationic size and charge as well as covalent contributions, different distortion (tilting in particular) and/or vacancy ordering variants of cyanamides/carbodiimides occur. Herein we summarize those cyanamide/carbodiimide structures that derive from the aristotype NiAs. The crystal chemistry is discussed on the basis of group-subgroup schemes (Bärnighausen trees).","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"95 - 103"},"PeriodicalIF":1.2,"publicationDate":"2023-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48109895","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 magnesium-rich intermetallic compounds Gd5Cu5Mg13 and Tb5Cu5Mg13 were obtained from direct reactions of the elements (induction melting) in sealed tantalum ampoules. Both compounds crystallize with the orthorhombic Y5Cu5Mg13 type structure, space group Cmcm and Z = 4. The polycrystalline samples were characterized by powder X-ray diffraction. The structure of the gadolinium compound was refined from single crystal X-ray diffraction data: a = 414.78(2), b = 1921.87(12), c = 2573.89(16) pm, wR2 = 0.0492, 1611 F2 values and 77 variables. Refinement of the occupancy parameters revealed a small degree of Gd/Mg mixing for the Gd3 site, leading to the composition Gd4.93(1)Cu5Mg13.07(1) for the studied crystal. The Gd5Cu5Mg13 structure contains slabs of equiatomic GdCuMg, which are embedded in a magnesium matrix. From a geometrical point of view, one can describe the Gd5Cu5Mg13 and Tb5Cu5Mg13 structures as intergrowth variants of distorted W/CsCl and AlB2 related slabs. The most remarkable crystal chemical feature concerns the bcc like magnesium slabs with short Mg–Mg distances ranging from 300 to 342 pm. Temperature dependent magnetic susceptibility measurements show Curie-Weiss paramagnetism for Tb5Cu5Mg13 (10.5(1) μ B Tb atom−1 and Θ P = −11.6(1) K). Antiferromagnetic ordering was detected below the Néel temperatures of T N = 30.5(3) K.
{"title":"Magnesium-rich intermetallic compounds Gd5Cu5Mg13 and Tb5Cu5Mg13 – intergrowth variants with CsCl and AlB2 related slabs","authors":"M. Reimann, R. Pöttgen","doi":"10.1515/zkri-2022-0064","DOIUrl":"https://doi.org/10.1515/zkri-2022-0064","url":null,"abstract":"Abstract The magnesium-rich intermetallic compounds Gd5Cu5Mg13 and Tb5Cu5Mg13 were obtained from direct reactions of the elements (induction melting) in sealed tantalum ampoules. Both compounds crystallize with the orthorhombic Y5Cu5Mg13 type structure, space group Cmcm and Z = 4. The polycrystalline samples were characterized by powder X-ray diffraction. The structure of the gadolinium compound was refined from single crystal X-ray diffraction data: a = 414.78(2), b = 1921.87(12), c = 2573.89(16) pm, wR2 = 0.0492, 1611 F2 values and 77 variables. Refinement of the occupancy parameters revealed a small degree of Gd/Mg mixing for the Gd3 site, leading to the composition Gd4.93(1)Cu5Mg13.07(1) for the studied crystal. The Gd5Cu5Mg13 structure contains slabs of equiatomic GdCuMg, which are embedded in a magnesium matrix. From a geometrical point of view, one can describe the Gd5Cu5Mg13 and Tb5Cu5Mg13 structures as intergrowth variants of distorted W/CsCl and AlB2 related slabs. The most remarkable crystal chemical feature concerns the bcc like magnesium slabs with short Mg–Mg distances ranging from 300 to 342 pm. Temperature dependent magnetic susceptibility measurements show Curie-Weiss paramagnetism for Tb5Cu5Mg13 (10.5(1) μ B Tb atom−1 and Θ P = −11.6(1) K). Antiferromagnetic ordering was detected below the Néel temperatures of T N = 30.5(3) K.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"32 47","pages":"87 - 93"},"PeriodicalIF":1.2,"publicationDate":"2023-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41330417","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 This mini-review focuses on up-to-date advances of hybrid materials consisting of organic and inorganic components and their applications in different chemical processes. The purpose of forming such hybrids is mainly to functionalize and stabilize inorganic supports by attaching an organic linker to enhance their performance towards a target application. The interface chemistry is present with the emphasis on the sustainability of their components, chemical changes in substrates during synthesis, improvements of their physical and chemical properties, and, finally, their implementation. The latter is the main sectioning feature of this review, while we present the most prosperous applications ranging from catalysis, through water purification and energy storage. Emphasis was given to materials that can be classified as green to the best in our consideration. As the summary, the current situation on developing hybrid materials as well as directions towards sustainable future using organic-inorganic hybrids are presented.
{"title":"Organic-inorganic interface chemistry for sustainable materials","authors":"J. Pia̧tek, Bruno V. M. Rodrigues, Adam Slabon","doi":"10.1515/zkri-2022-0054","DOIUrl":"https://doi.org/10.1515/zkri-2022-0054","url":null,"abstract":"Abstract This mini-review focuses on up-to-date advances of hybrid materials consisting of organic and inorganic components and their applications in different chemical processes. The purpose of forming such hybrids is mainly to functionalize and stabilize inorganic supports by attaching an organic linker to enhance their performance towards a target application. The interface chemistry is present with the emphasis on the sustainability of their components, chemical changes in substrates during synthesis, improvements of their physical and chemical properties, and, finally, their implementation. The latter is the main sectioning feature of this review, while we present the most prosperous applications ranging from catalysis, through water purification and energy storage. Emphasis was given to materials that can be classified as green to the best in our consideration. As the summary, the current situation on developing hybrid materials as well as directions towards sustainable future using organic-inorganic hybrids are presented.","PeriodicalId":48676,"journal":{"name":"Zeitschrift Fur Kristallographie-Crystalline Materials","volume":"238 1","pages":"73 - 85"},"PeriodicalIF":1.2,"publicationDate":"2022-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41727977","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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