Pub Date : 2021-10-10DOI: 10.2116/xraystruct.37.59
V. Sabirov, M. Jumaev, Djumanali Irkabaev, J. Ashurov
The isomorphism and isodimorphism of the d metal sulfates are of particular importance for the crystal chemistry of minerals, materials science, solid solutions physics and processing of the ores. The thermodynamic theory of solid-solution aqueoussolution interactions and available the effects of ionic substitutions on the thermodynamic properties of binary sulfate solid solutions were discussed before in detail.1 Chalcanthite is paramagnetic compound, and doping another paramagnetic atom, Fe2+, to it allow to modify it’s magnetic susceptibility.2 Crystals of chalcanthite have an optical band pass with a transmission band of 0.280 – 0.570 nm with a maximal transmission of 75%; they can be successfully used as an optical bandpass in higher resolution spectral devices.3 Some Fe-containing chalcanthite crystals were studied by the single crystal X-ray diffraction method and the distribution of the Cu and Fe atoms over the crystallographic sites are determined by using of the results of analytical chemistry or according to the degree of the distortion of the coordination polyhedrons around sites.4,5 Site occupations of the Cu and Fe atoms are not possible because of the similar scattering-factors of these elements. To except the problems of non-distinguishability of Cu and Fe during an X-ray diffraction study, we have synthesized the solid solutions of chalcanthite with a priory known chemical compositions, (Cu0.90Fe0.10)SO4·5H2O (I) and (Cu0.80Fe0.20) SO4·5H2O (II), and have studied (Fig. 1). The influence of substituting Cu for Fe ion on the structural disorders of the subunits in the crystal of chalcanthite was not performed. For this reason, this work is aimed at an X-ray diffraction study of the crystal structure of these compounds. Single crystals of (I) and (II) were synthesized by stirring 0.01 M sulfuric acid solution of CuSO4·5H2O and FeSO4·7H2O in molar of ratios of 9:1 and 8:2 at a temperature of ∼45°C, respectively. The X-ray diffraction data were collected on a Xcalibur, Ruby diffractometer using graphite-monochromated Cu-Kα radiation. Crystal and experimental data details are given in the Table 1. The values of the |E2 – 1| statistical parameters show that both crystals are centrosymmetric, and because it’s crystal structures were solved in the space group P1 and refined by a full-matrix least-squares method.6 The hydrogen atoms were found from difference maps, though not refined. Disorder manifests itself as a splitting of the O atoms sites and trigonal planar configuration of the O atoms of aqua ligands. The perceptible residual electron density remain around the M2 site on the distance 0.52 Å. Both crystal structures are composed of the square-planar [Cu(H2O)4] located at the M1(0,0,0) site and [(Cu,Fe)(H2O)4] at the M2(0,1/2,–1/2) site. The SO4 tetrahedra acts as a μ2-bridging ligand between these cations, which lead to a chain structure (Figs. 2 and 3). The water of crystallization takes place in the hydrogen bonds. Selected Cu–O
{"title":"Disorder of the Water Molecules and Sulfate Anion in the Crystal Structure of Fe-substituted Synthetic Chalcanthite Crystals (Cu1–xFex)SO4·5H2O (x = 0.1 and 0.20)","authors":"V. Sabirov, M. Jumaev, Djumanali Irkabaev, J. Ashurov","doi":"10.2116/xraystruct.37.59","DOIUrl":"https://doi.org/10.2116/xraystruct.37.59","url":null,"abstract":"The isomorphism and isodimorphism of the d metal sulfates are of particular importance for the crystal chemistry of minerals, materials science, solid solutions physics and processing of the ores. The thermodynamic theory of solid-solution aqueoussolution interactions and available the effects of ionic substitutions on the thermodynamic properties of binary sulfate solid solutions were discussed before in detail.1 Chalcanthite is paramagnetic compound, and doping another paramagnetic atom, Fe2+, to it allow to modify it’s magnetic susceptibility.2 Crystals of chalcanthite have an optical band pass with a transmission band of 0.280 – 0.570 nm with a maximal transmission of 75%; they can be successfully used as an optical bandpass in higher resolution spectral devices.3 Some Fe-containing chalcanthite crystals were studied by the single crystal X-ray diffraction method and the distribution of the Cu and Fe atoms over the crystallographic sites are determined by using of the results of analytical chemistry or according to the degree of the distortion of the coordination polyhedrons around sites.4,5 Site occupations of the Cu and Fe atoms are not possible because of the similar scattering-factors of these elements. To except the problems of non-distinguishability of Cu and Fe during an X-ray diffraction study, we have synthesized the solid solutions of chalcanthite with a priory known chemical compositions, (Cu0.90Fe0.10)SO4·5H2O (I) and (Cu0.80Fe0.20) SO4·5H2O (II), and have studied (Fig. 1). The influence of substituting Cu for Fe ion on the structural disorders of the subunits in the crystal of chalcanthite was not performed. For this reason, this work is aimed at an X-ray diffraction study of the crystal structure of these compounds. Single crystals of (I) and (II) were synthesized by stirring 0.01 M sulfuric acid solution of CuSO4·5H2O and FeSO4·7H2O in molar of ratios of 9:1 and 8:2 at a temperature of ∼45°C, respectively. The X-ray diffraction data were collected on a Xcalibur, Ruby diffractometer using graphite-monochromated Cu-Kα radiation. Crystal and experimental data details are given in the Table 1. The values of the |E2 – 1| statistical parameters show that both crystals are centrosymmetric, and because it’s crystal structures were solved in the space group P1 and refined by a full-matrix least-squares method.6 The hydrogen atoms were found from difference maps, though not refined. Disorder manifests itself as a splitting of the O atoms sites and trigonal planar configuration of the O atoms of aqua ligands. The perceptible residual electron density remain around the M2 site on the distance 0.52 Å. Both crystal structures are composed of the square-planar [Cu(H2O)4] located at the M1(0,0,0) site and [(Cu,Fe)(H2O)4] at the M2(0,1/2,–1/2) site. The SO4 tetrahedra acts as a μ2-bridging ligand between these cations, which lead to a chain structure (Figs. 2 and 3). The water of crystallization takes place in the hydrogen bonds. Selected Cu–O ","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.2,"publicationDate":"2021-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45421064","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 : 2021-10-10DOI: 10.2116/xraystruct.37.65
J. Guillon, N. Pinaud, Solène Savrimoutou, M. Marchivie, S. Moreau, Sandra Albenque-Rubio, P. Sonnet
The X-ray crystal structure of the antimalarial 1-(3-ferrocenyl-2-methylpyrrolo[1,2- a ]quinoxalin-4-yl)piperazin-4-ium chloride has been established. It crystallizes in the tetragonal space group P -42 1 c with cell parameters a = 24.6705(19)Å, b = 24.6705(19)Å, c = 7.4533(6)Å, α = 90 ° , β = 90 ° , γ = 90 ° V = 4536.3(8)Å 3 and Z = 8. The crystal structure was refined to final values of R 1 = 0.0354 and wR 2 = 0.0837. An X-ray crystal structure analysis revealed that each molecule features intermolecular N–H···Cl hydrogen bonds interactions between the ammonium group and the chloride anion to form tetramers.
建立了抗疟药1-(3-二茂铁基-2-甲基吡咯[1,2- a]喹诺沙林-4-基)哌嗪-4-氯化铵的x射线晶体结构。晶胞参数为a = 24.6705(19)Å， b = 24.6705(19)Å， c = 7.4533(6)Å， α = 90°，β = 90°，γ = 90°V = 4536.3(8)Å 3, Z = 8。晶体结构细化到最终值r1 = 0.0354, wr2 = 0.0837。x射线晶体结构分析表明，每个分子都具有分子间N-H···Cl氢键，在铵基和氯阴离子之间相互作用形成四聚体。
{"title":"Crystal Structure of 1-(3-Ferrocenyl-2-methylpyrrolo[1,2-a]quinoxalin-4-yl)piperazin-4-ium Chloride","authors":"J. Guillon, N. Pinaud, Solène Savrimoutou, M. Marchivie, S. Moreau, Sandra Albenque-Rubio, P. Sonnet","doi":"10.2116/xraystruct.37.65","DOIUrl":"https://doi.org/10.2116/xraystruct.37.65","url":null,"abstract":"The X-ray crystal structure of the antimalarial 1-(3-ferrocenyl-2-methylpyrrolo[1,2- a ]quinoxalin-4-yl)piperazin-4-ium chloride has been established. It crystallizes in the tetragonal space group P -42 1 c with cell parameters a = 24.6705(19)Å, b = 24.6705(19)Å, c = 7.4533(6)Å, α = 90 ° , β = 90 ° , γ = 90 ° V = 4536.3(8)Å 3 and Z = 8. The crystal structure was refined to final values of R 1 = 0.0354 and wR 2 = 0.0837. An X-ray crystal structure analysis revealed that each molecule features intermolecular N–H···Cl hydrogen bonds interactions between the ammonium group and the chloride anion to form tetramers.","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.2,"publicationDate":"2021-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42489179","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 : 2021-10-10DOI: 10.2116/xraystruct.37.61
Shusaku Wada, D. Yoshioka, M. Tsuboi, M. Mikuriya
Dinuclear zinc(II) complex with 1,4,8,11-tetrakis(salicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane (H 4 tsaec), [Zn 2 (tsaec)]·2CHCl 3 , was synthesized. The crystal structure was determined by the single-crystal X-ray diffraction method at 293 K. The complex crystallizes in the monoclinic space group P 2 1 / c with a = 9.496(3), b = 11.568(3), c = 23.338(7)Å, β = 96.270(4) ° , V = 2548.3(12)Å 3 , D calcd = 1.505 g/cm 3 , Z = 2. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0407 and 0.1034, respectively, for all 6119 independent reflections. The two zinc(II) atoms are bound to the tsaec ligand outside the central teraazacyclotetradecane ring with an intramolecular Zn···Zn distance of 9.426(2)Å, where each zinc(II) atom is coordinated by two Schiff-base pendant arms with two phenolato-oxygen and two imino-nitrogen atoms to form a distorted tetrahedral geometry.
合成了双核锌(II)与1,4,8,11-四(水杨基氨基乙基)-1,4,8,11-四氮杂环十四烷(h4 tsaec)配合物[zn2 (tsaec)]·2CHCl 3。在293 K下用单晶x射线衍射法测定了晶体结构。配合物在单斜空间群p1 /c中结晶，a = 9.496(3)， b = 11.568(3)， c = 23.338(7)Å， β = 96.270(4)°，V = 2548.3(12)Å 3, D calcd = 1.505 g/cm 3, Z = 2。所有6119个独立反射的R 1 [I > 2 σ (I)]和wR 2(所有数据)值分别为0.0407和0.1034。两个锌(II)原子与中心三氮杂环十四烷环外的tsaec配体结合，分子内Zn··Zn距离为9.426(2)Å，其中每个锌(II)原子由两个希夫碱垂臂与两个酚氧和两个亚胺氮原子配位，形成扭曲的四面体几何形状。
{"title":"Dinuclear Zinc(II) Complex with a Cyclam-based Ligand with Four Schiff-base Pendant Arms","authors":"Shusaku Wada, D. Yoshioka, M. Tsuboi, M. Mikuriya","doi":"10.2116/xraystruct.37.61","DOIUrl":"https://doi.org/10.2116/xraystruct.37.61","url":null,"abstract":"Dinuclear zinc(II) complex with 1,4,8,11-tetrakis(salicylideneaminoethyl)-1,4,8,11-tetraazacyclotetradecane (H 4 tsaec), [Zn 2 (tsaec)]·2CHCl 3 , was synthesized. The crystal structure was determined by the single-crystal X-ray diffraction method at 293 K. The complex crystallizes in the monoclinic space group P 2 1 / c with a = 9.496(3), b = 11.568(3), c = 23.338(7)Å, β = 96.270(4) ° , V = 2548.3(12)Å 3 , D calcd = 1.505 g/cm 3 , Z = 2. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0407 and 0.1034, respectively, for all 6119 independent reflections. The two zinc(II) atoms are bound to the tsaec ligand outside the central teraazacyclotetradecane ring with an intramolecular Zn···Zn distance of 9.426(2)Å, where each zinc(II) atom is coordinated by two Schiff-base pendant arms with two phenolato-oxygen and two imino-nitrogen atoms to form a distorted tetrahedral geometry.","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.2,"publicationDate":"2021-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48361562","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 : 2021-09-10DOI: 10.2116/xraystruct.37.49
M. Mikuriya, C. Yamakawa, Kensuke Tanabe, Raigo Nukita, D. Yoshioka, R. Mitsuhashi, M. Handa, M. Tsuboi
X-ray for the crystal Bruker X-ray diffractometer (SMART APEX) α radiation. Crystal data The structure intrinsic with SHELXT-2014, methods Hydrogen atoms at their calculated the A dinuclear copper(II) carboxylate with 2,3,6-trimethoxybenzoic acid (H236-tmbz), tetrakis( μ -2,3,6-trimethoxybenzoato-κ O : κ O ′ )bis[(methanol)copper(II)], [Cu 2 (236-tmbz) 4 (CH 3 OH) 2 ], was prepared, and the crystal structure was determined by a single-crystal X-ray structure analysis at 90 K. It crystallizes in the triclinic space group P 1 with a = 7.4282(11)Å, b = 12.2389(18)Å, c = 13.3158(19)Å, α = 115.128(2) ° , β = 95.396(3) ° , γ = 91.086(2) ° , V = 1088.8(3)Å 3 , D x = 1.580 g/cm 3 , and Z = 1. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0513 and 0.1207, respectively, for all 4894 independent reflections. The two copper atoms are bridged by four 2,3,6-trimethoxybenzoato ligands in a syn - syn mode to form a dinuclear cluster (Cu···Cu 2.6071(8)Å) with the apical methanol molecules. The benzoate phenyl rings are largely rotated to the bridging OCO moieties with a rotation angle ( f rot ) of 74.9(2) and 44.6(3) ° .
{"title":"Crystal Structure of Tetrakis(μ-2,3,6-trimethoxybenzoato-κO:κO′)bis[(methanol)copper(II)]: Largely Rotated Benzoate Ring to the Carboxylato Bridge","authors":"M. Mikuriya, C. Yamakawa, Kensuke Tanabe, Raigo Nukita, D. Yoshioka, R. Mitsuhashi, M. Handa, M. Tsuboi","doi":"10.2116/xraystruct.37.49","DOIUrl":"https://doi.org/10.2116/xraystruct.37.49","url":null,"abstract":"X-ray for the crystal Bruker X-ray diffractometer (SMART APEX) α radiation. Crystal data The structure intrinsic with SHELXT-2014, methods Hydrogen atoms at their calculated the A dinuclear copper(II) carboxylate with 2,3,6-trimethoxybenzoic acid (H236-tmbz), tetrakis( μ -2,3,6-trimethoxybenzoato-κ O : κ O ′ )bis[(methanol)copper(II)], [Cu 2 (236-tmbz) 4 (CH 3 OH) 2 ], was prepared, and the crystal structure was determined by a single-crystal X-ray structure analysis at 90 K. It crystallizes in the triclinic space group P 1 with a = 7.4282(11)Å, b = 12.2389(18)Å, c = 13.3158(19)Å, α = 115.128(2) ° , β = 95.396(3) ° , γ = 91.086(2) ° , V = 1088.8(3)Å 3 , D x = 1.580 g/cm 3 , and Z = 1. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0513 and 0.1207, respectively, for all 4894 independent reflections. The two copper atoms are bridged by four 2,3,6-trimethoxybenzoato ligands in a syn - syn mode to form a dinuclear cluster (Cu···Cu 2.6071(8)Å) with the apical methanol molecules. The benzoate phenyl rings are largely rotated to the bridging OCO moieties with a rotation angle ( f rot ) of 74.9(2) and 44.6(3) ° .","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.2,"publicationDate":"2021-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47916747","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 : 2021-08-10DOI: 10.2116/xraystruct.37.41
M. Mikuriya, Sayuri Ono, Yoshiki Koyama, R. Mitsuhashi, M. Tsuboi
A hexanuclear Mn II2 Mn III4 complex with 2-(5-nitro-2-hydroxyphenyl)-1,3-bis(2-(5-nitro-2-hydroxybenzylideneamino)-ethyl)imidazolidine (H 3 L NO2 ) and its hydrolyzed ligand, 1,10-bis(5-nitrosalicylideneamino)-4,7-azadecane (H 2 L NO2 ′ ), was isolated. The crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The complex crystallized as [{Mn 3 ( μ 3 -O)( μ -CH 3 COO) 2 ( μ -L NO2 )} 2 (L NO2 ′ )]·2.5THF·CH 3 OH in the monoclinic space group C 2/ c with a = 21.253(3), b = 16.630(2), c = 29.508(4)Å, β = 93.147(2) ° , V = 10413(2)Å 3 , D calcd = 1.551 g/cm 3 , Z = 4. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0836 and 0.2500, respectively, for all 11924 independent reflections. The complex is a hexanuclear manganese molecule which has a crystallographic inversion center at the midpoint of the ethylenediamine backbone of L NO2 ′ 2– ligand. In the asymmetric unit, three manganese atoms (Mn1, Mn2, and Mn3) are arranged in a μ 3 -oxido-centered triangle, and the Mn1 and Mn2 atoms are further bridged by a phenolato-oxygen atom of L NO23– , and both of the Mn1 and Mn3 atoms and the Mn2 and Mn3 atoms are further bridged by an acetato ligand in a syn - syn mode. The charge balance and a bond valence sum calculation supported the mixed-valent Mn II2 Mn III4 state with the Mn II state for the Mn1 atom and the Mn III state for the Mn2 and Mn3 atoms, respectively.
{"title":"Crystal Structure of a Mixed-valent Hexanuclear Manganese Complex Made-up from Two Oxido-centered Triangular MnIIMnIII2 Cores","authors":"M. Mikuriya, Sayuri Ono, Yoshiki Koyama, R. Mitsuhashi, M. Tsuboi","doi":"10.2116/xraystruct.37.41","DOIUrl":"https://doi.org/10.2116/xraystruct.37.41","url":null,"abstract":"A hexanuclear Mn II2 Mn III4 complex with 2-(5-nitro-2-hydroxyphenyl)-1,3-bis(2-(5-nitro-2-hydroxybenzylideneamino)-ethyl)imidazolidine (H 3 L NO2 ) and its hydrolyzed ligand, 1,10-bis(5-nitrosalicylideneamino)-4,7-azadecane (H 2 L NO2 ′ ), was isolated. The crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The complex crystallized as [{Mn 3 ( μ 3 -O)( μ -CH 3 COO) 2 ( μ -L NO2 )} 2 (L NO2 ′ )]·2.5THF·CH 3 OH in the monoclinic space group C 2/ c with a = 21.253(3), b = 16.630(2), c = 29.508(4)Å, β = 93.147(2) ° , V = 10413(2)Å 3 , D calcd = 1.551 g/cm 3 , Z = 4. The R 1 [ I > 2 σ ( I )] and wR 2 (all data) values are 0.0836 and 0.2500, respectively, for all 11924 independent reflections. The complex is a hexanuclear manganese molecule which has a crystallographic inversion center at the midpoint of the ethylenediamine backbone of L NO2 ′ 2– ligand. In the asymmetric unit, three manganese atoms (Mn1, Mn2, and Mn3) are arranged in a μ 3 -oxido-centered triangle, and the Mn1 and Mn2 atoms are further bridged by a phenolato-oxygen atom of L NO23– , and both of the Mn1 and Mn3 atoms and the Mn2 and Mn3 atoms are further bridged by an acetato ligand in a syn - syn mode. The charge balance and a bond valence sum calculation supported the mixed-valent Mn II2 Mn III4 state with the Mn II state for the Mn1 atom and the Mn III state for the Mn2 and Mn3 atoms, respectively.","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.2,"publicationDate":"2021-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47440868","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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