Pub Date : 2022-02-17DOI: 10.1107/s2052520622000804
Ginga Kitahara, A. Yoshiasa, M. Tokuda, M. Nespolo, H. Hongu, Koichi Momma, R. Miyawaki, K. Sugiyama
The structure refinement and XANES study of two gold-silver-tellurides [Au1+xAgxTe2, krennerite (x = 0.11-0.13) and sylvanite (x = 0.29-0.31)] are presented and the structures are compared with the prototype structure of calaverite (x = 0.08-0.10). Whereas the latter is well known for being incommensurately modulated at ambient conditions, neither krennerite nor sylvanite present any modulation. This is attributed to the presence of relatively strong Te-Te bonds (bond distances < 2.9 Å) in the two minerals, which are absent in calaverite (bond distances > 3.2 Å). In both tellurides, trivalent gold occurs in slightly distorted square planar coordination, whereas monovalent gold, partly substituted by monovalent silver, presents a 2+2+2 coordination, corresponding to distorted rhombic bipyramids. The differentiation between bonding and non-bonding contacts is obtained by computation of the Effective Coordination Number (ECoN). The CHARge DIstribution (CHARDI) analysis is satisfactory for both tellurides but suggests that the Te-Te bond in the [Te3]2- anion is not entirely homopolar. Both tellurides can therefore be described as Madelung-type compounds, despite the presence of Te-Te in both structures.
{"title":"Crystal structure, XANES and charge distribution investigation of krennerite and sylvanite: analysis of Au-Te and Te-Te bonds in Au1-xAgxTe2 group minerals.","authors":"Ginga Kitahara, A. Yoshiasa, M. Tokuda, M. Nespolo, H. Hongu, Koichi Momma, R. Miyawaki, K. Sugiyama","doi":"10.1107/s2052520622000804","DOIUrl":"https://doi.org/10.1107/s2052520622000804","url":null,"abstract":"The structure refinement and XANES study of two gold-silver-tellurides [Au1+xAgxTe2, krennerite (x = 0.11-0.13) and sylvanite (x = 0.29-0.31)] are presented and the structures are compared with the prototype structure of calaverite (x = 0.08-0.10). Whereas the latter is well known for being incommensurately modulated at ambient conditions, neither krennerite nor sylvanite present any modulation. This is attributed to the presence of relatively strong Te-Te bonds (bond distances < 2.9 Å) in the two minerals, which are absent in calaverite (bond distances > 3.2 Å). In both tellurides, trivalent gold occurs in slightly distorted square planar coordination, whereas monovalent gold, partly substituted by monovalent silver, presents a 2+2+2 coordination, corresponding to distorted rhombic bipyramids. The differentiation between bonding and non-bonding contacts is obtained by computation of the Effective Coordination Number (ECoN). The CHARge DIstribution (CHARDI) analysis is satisfactory for both tellurides but suggests that the Te-Te bond in the [Te3]2- anion is not entirely homopolar. Both tellurides can therefore be described as Madelung-type compounds, despite the presence of Te-Te in both structures.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"168 1","pages":"117-132"},"PeriodicalIF":0.0,"publicationDate":"2022-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72825924","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}
Pub Date : 2022-02-16DOI: 10.1107/s2052520622000191
E. Broadhurst, C. G. Wilson, Georgia A. Zissimou, F. Nudelman, Christos P. Constantinides, P. Koutentis, S. Parsons
The crystal structure of Blatter's radical (1,3-diphenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl) has been investigated between ambient pressure and 6.07 GPa. The sample remains in a compressed form of the ambient-pressure phase up to 5.34 GPa, the largest direction of strain being parallel to the direction of π-stacking interactions. The bulk modulus is 7.4 (6) GPa, with a pressure derivative equal to 9.33 (11). As pressure increases, the phenyl groups attached to the N1 and C3 positions of the triazinyl moieties of neighbouring pairs of molecules approach each other, causing the former to begin to rotate between 3.42 to 5.34 GPa. The onset of this phenyl rotation may be interpreted as a second-order phase transition which introduces a new mode for accommodating pressure. It is premonitory to a first-order isosymmetric phase transition which occurs on increasing pressure from 5.34 to 5.54 GPa. Although the phase transition is driven by volume minimization, rather than relief of unfavourable contacts, it is accompanied by a sharp jump in the orientation of the rotation angle of the phenyl group. DFT calculations suggest that the adoption of a more planar conformation by the triazinyl moiety at the phase transition can be attributed to relief of intramolecular H...H contacts at the transition. Although no dimerization of the radicals occurs, the π-stacking interactions are compressed by 0.341 (3) Å between ambient pressure and 6.07 GPa.
{"title":"A first-order phase transition in Blatter's radical at high pressure.","authors":"E. Broadhurst, C. G. Wilson, Georgia A. Zissimou, F. Nudelman, Christos P. Constantinides, P. Koutentis, S. Parsons","doi":"10.1107/s2052520622000191","DOIUrl":"https://doi.org/10.1107/s2052520622000191","url":null,"abstract":"The crystal structure of Blatter's radical (1,3-diphenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl) has been investigated between ambient pressure and 6.07 GPa. The sample remains in a compressed form of the ambient-pressure phase up to 5.34 GPa, the largest direction of strain being parallel to the direction of π-stacking interactions. The bulk modulus is 7.4 (6) GPa, with a pressure derivative equal to 9.33 (11). As pressure increases, the phenyl groups attached to the N1 and C3 positions of the triazinyl moieties of neighbouring pairs of molecules approach each other, causing the former to begin to rotate between 3.42 to 5.34 GPa. The onset of this phenyl rotation may be interpreted as a second-order phase transition which introduces a new mode for accommodating pressure. It is premonitory to a first-order isosymmetric phase transition which occurs on increasing pressure from 5.34 to 5.54 GPa. Although the phase transition is driven by volume minimization, rather than relief of unfavourable contacts, it is accompanied by a sharp jump in the orientation of the rotation angle of the phenyl group. DFT calculations suggest that the adoption of a more planar conformation by the triazinyl moiety at the phase transition can be attributed to relief of intramolecular H...H contacts at the transition. Although no dimerization of the radicals occurs, the π-stacking interactions are compressed by 0.341 (3) Å between ambient pressure and 6.07 GPa.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"42 1","pages":"107-116"},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87267040","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}
Pub Date : 2021-11-30DOI: 10.1107/s2052520621012336
J. Gillet, P. Macchi
In the past few issues of Acta Crystallographica Section B, including the current one, several articles have reported research work on quantum crystallography. Collectively they comprise a virtual special issue on the subject, the first on such an extended concept in the IUCr journals. Previously, a special issue, dedicated to Philip Coppens (1930–2017), was published in Acta Crystallographica Section B (August 2017). It contained many contributions in the field of charge density (as well as photo-crystallography). Originally intended to celebrate his retirement with contributions on two of the main topics developed during his career, the issue appeared just a few weeks after Professor Coppens passed away and became a kind of memorial issue. The occasion of the present special issue is the principal authors’ participation in the first online quantum crystallography meeting (QCrOM2020) held in August 2020. It was organized (and mostly improvised) to replace the sessions on this subject initially programmed for the IUCr Congress in Prague, which, as we know, was postponed to 2021. Its virtual modality (and its subsequent free of charge registration) made it possible to attract attendees from a wider range of expertise. It was the opportunity to present the latest results and reviews on the field and share opinions during fruitful discussion sessions that normally do not take place at large scale and tightly scheduled meetings like those of the IUCr Congress. Despite all the difficulties caused by the pandemic the field is currently blooming, and the community is undergoing a generational turnover with many new young researchers involved and new groups established. The field’s momentum is testified by the rather broad spectrum of studies published in this special issue, with a variety of research themes and many topics analyzed or reviewed in detail. Quantum crystallography is a modern name for a field that started when quantum mechanics itself was put forward, coinciding with the early days of X-ray crystallography. In keeping with Peter Debye’s early intuition (Debye, 1915), the discovery of X-ray diffraction offered a whole new possibility ‘to establish by experiment the particular arrangement of the electrons in the atoms’. Many studies became possible thanks to the interplay between crystallographic techniques and quantum physics. For example, experimental crystallography was used to unveil the nature of electrons (waves and corpuscles; see De Broglie, 1929), to investigate the electronic structures of metals (Weiss & Demarco, 1958), to map the charge density around atoms to form bonds and molecules or solids (Coppens, 1967), and the electron polarization upon application of external stimuli (such as the electric field, see Hansen et al., 2004) or upon temperature changes. Quite remarkably, these kinds of studies are those that originally attracted the interest of quantum physicists for the emerging field of X-ray crystallography in the 1920s.
{"title":"Quo vadis, quantum crystallography?","authors":"J. Gillet, P. Macchi","doi":"10.1107/s2052520621012336","DOIUrl":"https://doi.org/10.1107/s2052520621012336","url":null,"abstract":"In the past few issues of Acta Crystallographica Section B, including the current one, several articles have reported research work on quantum crystallography. Collectively they comprise a virtual special issue on the subject, the first on such an extended concept in the IUCr journals. Previously, a special issue, dedicated to Philip Coppens (1930–2017), was published in Acta Crystallographica Section B (August 2017). It contained many contributions in the field of charge density (as well as photo-crystallography). Originally intended to celebrate his retirement with contributions on two of the main topics developed during his career, the issue appeared just a few weeks after Professor Coppens passed away and became a kind of memorial issue. The occasion of the present special issue is the principal authors’ participation in the first online quantum crystallography meeting (QCrOM2020) held in August 2020. It was organized (and mostly improvised) to replace the sessions on this subject initially programmed for the IUCr Congress in Prague, which, as we know, was postponed to 2021. Its virtual modality (and its subsequent free of charge registration) made it possible to attract attendees from a wider range of expertise. It was the opportunity to present the latest results and reviews on the field and share opinions during fruitful discussion sessions that normally do not take place at large scale and tightly scheduled meetings like those of the IUCr Congress. Despite all the difficulties caused by the pandemic the field is currently blooming, and the community is undergoing a generational turnover with many new young researchers involved and new groups established. The field’s momentum is testified by the rather broad spectrum of studies published in this special issue, with a variety of research themes and many topics analyzed or reviewed in detail. Quantum crystallography is a modern name for a field that started when quantum mechanics itself was put forward, coinciding with the early days of X-ray crystallography. In keeping with Peter Debye’s early intuition (Debye, 1915), the discovery of X-ray diffraction offered a whole new possibility ‘to establish by experiment the particular arrangement of the electrons in the atoms’. Many studies became possible thanks to the interplay between crystallographic techniques and quantum physics. For example, experimental crystallography was used to unveil the nature of electrons (waves and corpuscles; see De Broglie, 1929), to investigate the electronic structures of metals (Weiss & Demarco, 1958), to map the charge density around atoms to form bonds and molecules or solids (Coppens, 1967), and the electron polarization upon application of external stimuli (such as the electric field, see Hansen et al., 2004) or upon temperature changes. Quite remarkably, these kinds of studies are those that originally attracted the interest of quantum physicists for the emerging field of X-ray crystallography in the 1920s. ","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"53 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89295590","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}
Pub Date : 2021-11-26DOI: 10.1107/s2052520621010866
Y. Biryukov, A. Zinnatullin, M. Cherosov, A. Shablinskii, R. Yusupov, R. Bubnova, F. Vagizov, S. Filatov, M. Avdontceva, I. Pekov
This work is devoted to an investigation of the magnetic properties and thermal behaviour of the natural oxoborates vonsenite and hulsite in the temperature range 5–500 K. The local environment, the oxidation states of the Fe and Sn atoms, and the charge distribution were determined using Mössbauer spectroscopy and are in accordance with a refinement of the crystal structure of hulsite from single-crystal X-ray diffraction data (SCXRD) in anisotropic approximation for the first time. The magnetic properties were studied by vibrating sample magnetometry (VSM) (5 ≤ T ≤ 400 K) and are reported for the first time for iron-rich hulsite. Both oxoborates show a very complex magnetic behaviour. Cascades of magnetic transitions are revealed and the critical temperatures were determined. The sequences of magnetic transitions in both vonsenite and hulsite with increasing temperature were found to be as follows: magnetically ordered state → partial magnetic ordering → paramagnetic state. According to X-ray diffraction data (93 ≤ T ≤ 500 K), these processes are accompanied by anomalies in the unit-cell parameters and thermal expansion of the oxoborates at critical temperatures. A strong negative volume thermal expansion is observed for both oxoborates at temperatures below ∼120 K.
{"title":"Low-temperature investigation of natural iron-rich oxoborates vonsenite and hulsite: thermal deformations of crystal structure, strong negative thermal expansion and cascades of magnetic transitions","authors":"Y. Biryukov, A. Zinnatullin, M. Cherosov, A. Shablinskii, R. Yusupov, R. Bubnova, F. Vagizov, S. Filatov, M. Avdontceva, I. Pekov","doi":"10.1107/s2052520621010866","DOIUrl":"https://doi.org/10.1107/s2052520621010866","url":null,"abstract":"This work is devoted to an investigation of the magnetic properties and thermal behaviour of the natural oxoborates vonsenite and hulsite in the temperature range 5–500 K. The local environment, the oxidation states of the Fe and Sn atoms, and the charge distribution were determined using Mössbauer spectroscopy and are in accordance with a refinement of the crystal structure of hulsite from single-crystal X-ray diffraction data (SCXRD) in anisotropic approximation for the first time. The magnetic properties were studied by vibrating sample magnetometry (VSM) (5 ≤ T ≤ 400 K) and are reported for the first time for iron-rich hulsite. Both oxoborates show a very complex magnetic behaviour. Cascades of magnetic transitions are revealed and the critical temperatures were determined. The sequences of magnetic transitions in both vonsenite and hulsite with increasing temperature were found to be as follows: magnetically ordered state → partial magnetic ordering → paramagnetic state. According to X-ray diffraction data (93 ≤ T ≤ 500 K), these processes are accompanied by anomalies in the unit-cell parameters and thermal expansion of the oxoborates at critical temperatures. A strong negative volume thermal expansion is observed for both oxoborates at temperatures below ∼120 K.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74952391","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}
Pub Date : 2021-11-26DOI: 10.1107/s2052520621011495
Júlia Adamko KoŽíšková, Yu‐Sheng Chen, Sudan Grass, Y. Chuang, I. Hsu, Yu Wang, M. Lutz, A. Volkov, Peter Herich, Barbora Vénosová, Ingrid Jelemenská, L. Bučinský, M. Breza, J. Kožíšek
High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO [complex (1)] and (MePh3P)[NiIII(bdtCl2)2] [complex (2)]. Combining the techniques of nickel K- and sulfur K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally NiII; that of complex (2) should be formally NiIII, yet it is best described as a combination of Ni2+ and Ni3+, due to the involvement of the non-innocent ligand in the Ni—L bond. A detailed description of Ni—S bond character (σ,π) is presented.
{"title":"Electronic structure of (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO and (MePh3P)[NiIII(bdtCl2)2] (bdtCl2 = 3,6-dichlorobenzene-1,2-dithiolate)","authors":"Júlia Adamko KoŽíšková, Yu‐Sheng Chen, Sudan Grass, Y. Chuang, I. Hsu, Yu Wang, M. Lutz, A. Volkov, Peter Herich, Barbora Vénosová, Ingrid Jelemenská, L. Bučinský, M. Breza, J. Kožíšek","doi":"10.1107/s2052520621011495","DOIUrl":"https://doi.org/10.1107/s2052520621011495","url":null,"abstract":"High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO [complex (1)] and (MePh3P)[NiIII(bdtCl2)2] [complex (2)]. Combining the techniques of nickel K- and sulfur K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally NiII; that of complex (2) should be formally NiIII, yet it is best described as a combination of Ni2+ and Ni3+, due to the involvement of the non-innocent ligand in the Ni—L bond. A detailed description of Ni—S bond character (σ,π) is presented.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72741491","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}
Pub Date : 2021-11-24DOI: 10.1107/s205252062101115x
I. Garkul, A. Zadesenets, E. Filatov, I. Baidina, S. Tkachev, D. Samsonenko, S. Korenev
New coordination compounds trans-bis(oxalato)diaquarhodiate sodium dihydrate Na[Rh(H2O)2Ox2]·2H2O (crystallizes in two polymorphic forms NaRh-1 and NaRh-2), trans-bis(oxalato)hydroxoaquarhodiate sodium tetrahydrate Na2[Rh(H2O)(OH)Ox2]·4H2O (Na2Rh) and trans-bis(oxalato)diaquarhodic acid tetrahydrate (H3O)[Rh(H2O)2Ox2]·4H2O (HRh) are synthesized. The compounds are characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. NaRh-1, NaRh-2 and Na2Rh crystallize in space group P 1. Trans-bis(oxalato)diaquarhodic acid exists not only in solution, but can also crystallize as a tetrahydrate (space group C2/c). The formation of various species in solution of rhodium hydroxide in oxalic acid and their redistribution were studied using 103Rh NMR spectroscopy.
{"title":"Oxonium trans-bis(oxalato)rhodate and related sodium salts: a rare example of crystalline complex acid","authors":"I. Garkul, A. Zadesenets, E. Filatov, I. Baidina, S. Tkachev, D. Samsonenko, S. Korenev","doi":"10.1107/s205252062101115x","DOIUrl":"https://doi.org/10.1107/s205252062101115x","url":null,"abstract":"New coordination compounds trans-bis(oxalato)diaquarhodiate sodium dihydrate Na[Rh(H2O)2Ox2]·2H2O (crystallizes in two polymorphic forms NaRh-1 and NaRh-2), trans-bis(oxalato)hydroxoaquarhodiate sodium tetrahydrate Na2[Rh(H2O)(OH)Ox2]·4H2O (Na2Rh) and trans-bis(oxalato)diaquarhodic acid tetrahydrate (H3O)[Rh(H2O)2Ox2]·4H2O (HRh) are synthesized. The compounds are characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. NaRh-1, NaRh-2 and Na2Rh crystallize in space group P\u0000 1. Trans-bis(oxalato)diaquarhodic acid exists not only in solution, but can also crystallize as a tetrahydrate (space group C2/c). The formation of various species in solution of rhodium hydroxide in oxalic acid and their redistribution were studied using 103Rh NMR spectroscopy.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"58 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85826638","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}
Pub Date : 2021-11-24DOI: 10.1107/s2052520621012440
A. Krawczuk
by quantum mechanical calculations, employs information obtained from high-resolution X-ray diffraction experiments to assess forces and potential in a crystalline state. Electronic forces, observed in a crystal, are expressed by kinetic and DFT potentials and are further defined in terms of experimental electron density and its derivatives.
{"title":"Crystallography meets orbital-free DFT – two-pronged approach towards chemical bonding characteristics in chemical bonding analysis","authors":"A. Krawczuk","doi":"10.1107/s2052520621012440","DOIUrl":"https://doi.org/10.1107/s2052520621012440","url":null,"abstract":"by quantum mechanical calculations, employs information obtained from high-resolution X-ray diffraction experiments to assess forces and potential in a crystalline state. Electronic forces, observed in a crystal, are expressed by kinetic and DFT potentials and are further defined in terms of experimental electron density and its derivatives.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86745591","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}
Pub Date : 2021-11-23DOI: 10.1107/s2052520621012075
D. Allan
In this issue of Acta Crystallographica Section B, Michal Kaźmierczak and Ewa PatykKaźmierczak (2021) provide a comprehensive survey of high-pressure crystal structural depositions in the Cambridge Structural Database (Groom et al., 2016) and offer a valuable perspective on the status of high-pressure research within the field of crystal chemistry. For structural chemists, X-ray crystallographic techniques have been recognized as providing an extremely powerful method for the determination of the structure of matter and, specifically, the arrangement of atoms of a crystalline solid in three-dimensional space. The origin of the field comes from the theoretical work of Paul Ewald who, in collaboration with Max von Laue examined the propagation of X-rays through crystals. Encouraged by Laue, Walter Friedrich and Paul Knipping carried out an experiment where they shone a beam of X-rays at a crystal of zinc blende (ZnS) with a photographic film placed behind it to record the diffraction spots. The interpretation of the diffraction images was determined fully by Lawrence Bragg, who inferred that the diffraction events could be understood in terms of mirror-like reflections from planes within the crystal, which he formulated as the now very familiar ‘Bragg’s law’. For their work on translating the information recorded on diffraction images to crystal structure determination at atomic resolution Max von Laue and Lawrence Bragg (with his father William Bragg) won the Nobel Prize for Physics on consecutive years, 1914 and 1915 respectively (Woolfson, 2018). This brief period unlocked the use of X-ray crystal structure analysis for scientists working in disparate fields and by 1929 the output of the fledgling X-ray crystallography community was of sufficient volume for the founding of Strukturberichte, to provide a regularly published source of recent crystal structure determinations. Strukturberichte eventually became Structure Reports as an official publication of the International Union of Crystallography until the 1990s. The period also marked the evolution of X-ray crystallography and crystal structure analysis away from its origins in inorganic chemistry. Long-standing questions on the nature of chemical bonding and interactions in organic chemistry were addressed and the structures of a wide range of natural and synthesized molecules were determined. The biological and life sciences also embraced X-ray crystallography and went on to address several dauntingly complex challenges which, in turn, have revolutionized our understanding of life at the molecular level (Groom & Allen, 2014). From 1929 to the early 1960s, crystal structure compilations and references were print based, with both Strukturberichte and Structure Reports joined by several other publications, and by the late 1940s there were growing concerns about the plethora of sources for primary scientific material, which was dubbed ‘the information explosion’. In 1964, when computer-based syst
{"title":"Mapping high-pressure crystallography in a structural chemistry landscape","authors":"D. Allan","doi":"10.1107/s2052520621012075","DOIUrl":"https://doi.org/10.1107/s2052520621012075","url":null,"abstract":"In this issue of Acta Crystallographica Section B, Michal Kaźmierczak and Ewa PatykKaźmierczak (2021) provide a comprehensive survey of high-pressure crystal structural depositions in the Cambridge Structural Database (Groom et al., 2016) and offer a valuable perspective on the status of high-pressure research within the field of crystal chemistry. For structural chemists, X-ray crystallographic techniques have been recognized as providing an extremely powerful method for the determination of the structure of matter and, specifically, the arrangement of atoms of a crystalline solid in three-dimensional space. The origin of the field comes from the theoretical work of Paul Ewald who, in collaboration with Max von Laue examined the propagation of X-rays through crystals. Encouraged by Laue, Walter Friedrich and Paul Knipping carried out an experiment where they shone a beam of X-rays at a crystal of zinc blende (ZnS) with a photographic film placed behind it to record the diffraction spots. The interpretation of the diffraction images was determined fully by Lawrence Bragg, who inferred that the diffraction events could be understood in terms of mirror-like reflections from planes within the crystal, which he formulated as the now very familiar ‘Bragg’s law’. For their work on translating the information recorded on diffraction images to crystal structure determination at atomic resolution Max von Laue and Lawrence Bragg (with his father William Bragg) won the Nobel Prize for Physics on consecutive years, 1914 and 1915 respectively (Woolfson, 2018). This brief period unlocked the use of X-ray crystal structure analysis for scientists working in disparate fields and by 1929 the output of the fledgling X-ray crystallography community was of sufficient volume for the founding of Strukturberichte, to provide a regularly published source of recent crystal structure determinations. Strukturberichte eventually became Structure Reports as an official publication of the International Union of Crystallography until the 1990s. The period also marked the evolution of X-ray crystallography and crystal structure analysis away from its origins in inorganic chemistry. Long-standing questions on the nature of chemical bonding and interactions in organic chemistry were addressed and the structures of a wide range of natural and synthesized molecules were determined. The biological and life sciences also embraced X-ray crystallography and went on to address several dauntingly complex challenges which, in turn, have revolutionized our understanding of life at the molecular level (Groom & Allen, 2014). From 1929 to the early 1960s, crystal structure compilations and references were print based, with both Strukturberichte and Structure Reports joined by several other publications, and by the late 1940s there were growing concerns about the plethora of sources for primary scientific material, which was dubbed ‘the information explosion’. In 1964, when computer-based syst","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"142 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86238565","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}
Pub Date : 2021-11-23DOI: 10.1107/s2052520621011458
M. Kaźmierczak, E. Patyk-Kaźmierczak
The Cambridge Structural Database (CSD) is the largest repository of crystal structures of organic and metal–organic compounds, containing over 1.1 million entries. Over 3300 of the deposits are structures determined under high pressure, with the number being strongly affected by the experimental requirements of the high-pressure techniques. Nevertheless, it still presents a population sufficiently representative for statistical data mining. In this work, an in-depth analysis of this population is presented, showing where contributors of high-pressure depositions come from, which journals high-pressure structures are published in, and also providing information on some trends in high-pressure crystallography and how they have changed over the years elucidated from data collected in the CSD. The ultimate goal of this article is to bring the high-pressure crystallography content in the CSD to a wider audience of scientists.
{"title":"Kilobytes of kilopascals: high-pressure depositions of the Cambridge Structural Database","authors":"M. Kaźmierczak, E. Patyk-Kaźmierczak","doi":"10.1107/s2052520621011458","DOIUrl":"https://doi.org/10.1107/s2052520621011458","url":null,"abstract":"The Cambridge Structural Database (CSD) is the largest repository of crystal structures of organic and metal–organic compounds, containing over 1.1 million entries. Over 3300 of the deposits are structures determined under high pressure, with the number being strongly affected by the experimental requirements of the high-pressure techniques. Nevertheless, it still presents a population sufficiently representative for statistical data mining. In this work, an in-depth analysis of this population is presented, showing where contributors of high-pressure depositions come from, which journals high-pressure structures are published in, and also providing information on some trends in high-pressure crystallography and how they have changed over the years elucidated from data collected in the CSD. The ultimate goal of this article is to bring the high-pressure crystallography content in the CSD to a wider audience of scientists.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75440173","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}
Pub Date : 2021-11-23DOI: 10.1107/s2052520621010350
O. Siidra, D. Charkin, Vadim M. Kovrugin, Artem S. Borisov
Alkali copper sulfates form a rapidly developing family of inorganics. Herein, we report synthesis and crystal structure, and evaluate possible ion migration pathways for a novel Na-K-Cu anhydrous sulfate, K(Na,K)Na2[Cu2(SO4)4]. The CuO7 and SO4 polyhedra share common vertices and edges to form [Cu2(SO4)4]4− wide ribbons, which link to each other via common oxygen atoms forming the host part of the structure. Four guest alkali sites are occupied by solely K+, mixture of K+ and Na+, and solely Na+, which agrees well with the size of the cavities. The crystal structure of K(Na,K)Na2[Cu2(SO4)4] contains two symmetry-independent Cu sites with [4+1+(2)] coordination environments. The overall coordination polyhedra of Cu2+ can be considered as `octahedra with one split vertex'. A similar coordination mode was observed also in some other multinary copper sulfates, mostly of the mineral world. These coordination modes were reviewed and five types of CuO7 polyhedra are identified. CuO7 polyhedra are almost restricted to copper sulfates and phosphates. It was found that a larger amount of the smaller SO4 2− and PO4 3− anions can cluster around a single Cu2+ cation; in addition, for such relatively small anions, both mono (κ1) and bidentate (κ2) coordination modes to the Cu2+ are possible. The correlation between crystallographic characteristics and bond valence energies showed that the new copper sulfate framework, [Cu2(SO4)4]4−, contains one interconnected path suitable for Na+ mobility at tolerable activation energies and that K(Na,K)Na2[Cu2(SO4)4] can be considered as a potential candidate for novel Na-ion conductors.
{"title":"K(Na,K)Na2[Cu2(SO4)4]: a new highly porous anhydrous sulfate and evaluation of possible ion migration pathways","authors":"O. Siidra, D. Charkin, Vadim M. Kovrugin, Artem S. Borisov","doi":"10.1107/s2052520621010350","DOIUrl":"https://doi.org/10.1107/s2052520621010350","url":null,"abstract":"Alkali copper sulfates form a rapidly developing family of inorganics. Herein, we report synthesis and crystal structure, and evaluate possible ion migration pathways for a novel Na-K-Cu anhydrous sulfate, K(Na,K)Na2[Cu2(SO4)4]. The CuO7 and SO4 polyhedra share common vertices and edges to form [Cu2(SO4)4]4− wide ribbons, which link to each other via common oxygen atoms forming the host part of the structure. Four guest alkali sites are occupied by solely K+, mixture of K+ and Na+, and solely Na+, which agrees well with the size of the cavities. The crystal structure of K(Na,K)Na2[Cu2(SO4)4] contains two symmetry-independent Cu sites with [4+1+(2)] coordination environments. The overall coordination polyhedra of Cu2+ can be considered as `octahedra with one split vertex'. A similar coordination mode was observed also in some other multinary copper sulfates, mostly of the mineral world. These coordination modes were reviewed and five types of CuO7 polyhedra are identified. CuO7 polyhedra are almost restricted to copper sulfates and phosphates. It was found that a larger amount of the smaller SO4\u0000 2− and PO4\u0000 3− anions can cluster around a single Cu2+ cation; in addition, for such relatively small anions, both mono (κ1) and bidentate (κ2) coordination modes to the Cu2+ are possible. The correlation between crystallographic characteristics and bond valence energies showed that the new copper sulfate framework, [Cu2(SO4)4]4−, contains one interconnected path suitable for Na+ mobility at tolerable activation energies and that K(Na,K)Na2[Cu2(SO4)4] can be considered as a potential candidate for novel Na-ion conductors.","PeriodicalId":7080,"journal":{"name":"Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials","volume":"125 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2021-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91116803","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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