A novel copper complex [Cu2（L）（DMF）2]（1, H4L =（1 Z,N？Z）-3,5-dibromo-N？-（（3,5-dibromo-2-hydroxyphenyl）（hydroxy）methylene）-2-hydroxybenzohydrazonic acid which was synthesized by in-situ oxidation reaction...A novel copper complex [Cu2（L）（DMF）2]（1, H4L =（1 Z,N？Z）-3,5-dibromo-N？-（（3,5-dibromo-2-hydroxyphenyl）（hydroxy）methylene）-2-hydroxybenzohydrazonic acid which was synthesized by in-situ oxidation reaction derived from H2hdb（H2hdb = 6,6′-（（1 E,1？E）-hydrazine-1,2-diylidenebis（methanylylidene）） bis（2,4-dibromophenol）） has been synthesized and characterized by IR, elemental analysis（CHN）, TG and single-crystal X-ray diffraction. The single crystal belongs to monoclinic system, space group P21/c with a = 13.538（1）, b = 3.912（1）, c = 23.778（1）A°, β = 105.232（5）o, Mr = 857.08, V = 1214.9（1） A°^3, Z = 2, Dc = 2.343 g/cm^3, F（000） = 824, μ = 8.375 mm^–1, R = 0.0566, and w R = 0.1610. Compound 1 displays weak anti-ferromagnetic interactions through a η^1：η^1：η^1：η^1：η^1：η^1：μ2-L^4- bridging mode. Hirshfeld surface analysis revealed that complex 1 was supported mainly by Br···H and H···H intermolecular interactions.展开更多
A highly efficient fluorescence material dinuclear zinc polymer [Zn2（mhbd）2（dca）2]n （1, Hmhbd is 3-methoxy-2-hydroxybenzaldehyde, dca is N（CN）2？） has been synthesized under room temperature and structurally c...A highly efficient fluorescence material dinuclear zinc polymer [Zn2（mhbd）2（dca）2]n （1, Hmhbd is 3-methoxy-2-hydroxybenzaldehyde, dca is N（CN）2？） has been synthesized under room temperature and structurally characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The structure belongs to the triclinic system, space group P with a = 8.475（1）, b = 9.595（1）, c = 15.001（1） A, α = 86.84（1）, β = 81.10（1）, γ = 68.78（1）°, Mr = 565.15, V = 1123.5（1） ？3, Dc = 1.671 g？cm–3, F（000） = 568, μ = 2.185 mm–1, R = 0.0451, and wR = 0.1297. 1 is a dinuclear zinc complex which further constructs a 1D chain through double μ1,5-dca bridge. Luminescent property and Hirshfeld surface analysis of 1 have been studied. The result indicates that the fluorescence intensity of complex 1 is forty-one times the fluorescence intensity of Hmhbd ligand.展开更多
A cocrystal based on 1,3-di（4-pyridyl）propane and 3-（（4′-carboxybenzyl）oxy）benzoic acid,C13H14N2·C15H12O5,has been synthesized and characterized by single-crystal X-ray diffraction.The compound crystallize...A cocrystal based on 1,3-di（4-pyridyl）propane and 3-（（4′-carboxybenzyl）oxy）benzoic acid,C13H14N2·C15H12O5,has been synthesized and characterized by single-crystal X-ray diffraction.The compound crystallizes in monoclinic,space group P21 /c with a = 11.639（4）,b = 9.808（3）,c = 20.854（6）,β = 91.242（7）°,V = 2380.0（13）3,C28H26N2O5,Mr = 470.51,Dc = 1.313 g/cm3,μ（MoKα） = 0.091 mm-1,F（000） = 992,Z = 4,the final R = 0.0677 and wR = 0.1477 for 4175 observed reflections（I 2σ（I））.Intermolecular N H···O hydrogen bonds link two kinds of components into a one-dimensional chain in [10-1] direction and adjacent chains are further arranged into a two-dimensional network by π···π and C H···π interactions.Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the close contacts are mainly focused on weak interactions.The theoretical investigations with HF/6-31G（d） method were performed,and its stability,frontier molecular orbital composition and Mulliken charge distribution were also discussed.展开更多
One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,...One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.展开更多
The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric ...The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.展开更多
Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-am...Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-aminonicotinic acid：perchloric acid：H2O and salt 2 with 2：1：3 stoichiometry of 2-aminonicotinic acid：sulfuric acid：H2O. Their crystal structures were characterized by single-crystal X-ray diffraction,differential scanning calorimetry（DSC） and thermogravimetric analyses（TGA）. The structure determination shows that two salts are both primarily stabilized by the strong N–H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice,a three-dimensional hydrogen-bonded network is observed,including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H,O–H…O and C–O…π intermolecular interactions.展开更多
Meloxicam(MLX) is an anti-inflammatory drug susceptible to variations and crystalline transitions. In compounding pharmacies, the complete crystallographic evaluation of the raw material is not a routine procedure. We...Meloxicam(MLX) is an anti-inflammatory drug susceptible to variations and crystalline transitions. In compounding pharmacies, the complete crystallographic evaluation of the raw material is not a routine procedure. We performed a complete crystallographic characterization of aleatory raw MLX samples from compounding pharmacies. X-ray diffraction indicated the presence of two crystalline forms in one sample. DSC experiments suggested that crystallization, or a crystal transition, occurred differently between samples. The FTIR and ~1H NMR spectra showed characteristic assignments.^(13)C solid-state NMR spectroscopy indicated the presence of more than one phase in a sample from pharmacy B. The Hirshfeld surface analysis, with electrostatic potential projection, allowed complete assignment of the UV spectra in ethanol solution. The polymorph I of meloxicam was more active than polymorph III in an experimental model of acute inflammation in mice. Our results highlighted the need for complete crystallographic characterization and the separation of freely used raw materials in compounding pharmacies,as a routine procedure, to ensure the desired dose/effect.展开更多
One novel adduct based on aminopyridinium and biphenyl-2,4′-dicarboxylate, C5H7N2＋·C14H9O4-, has been synthesized and characterized by X-ray structural study. The compound crystallizes in trigonal, space group ...One novel adduct based on aminopyridinium and biphenyl-2,4′-dicarboxylate, C5H7N2＋·C14H9O4-, has been synthesized and characterized by X-ray structural study. The compound crystallizes in trigonal, space group P32 with a = 9.2886（16）, b = 9.2886（16）, c = 16.746（6） , γ = 120°, V = 1251.2（5） 3, C19H16N2O4, Mr = 336.34, Dc = 1.339 g/cm3, μ（MoKα） = 0.095 mm-1, F（000） = 528, Z = 3, the final R = 0.0438 and wR = 0.1119 for 3097 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Its electronic structure was calculated at the RHF/6-31G（d） level and a detailed analysis of intermolecular interactions was used by Hirshfeld surface and fingerprint plot. Intermolecular N-H…O hydrogen bonds link two components generating R22（8） rings which are linked into three one-dimensional chains in the [100], [010] and [110] directions, and these chains are finally arranged into a three-dimensional framework by hydrogen bonds. Investigation of intermolecular interactions via Hirshfeld surface analysis reveals that the close contacts are mainly associated with the classical hydrogen bonding interactions. The HOMO-LUMO energy gap of the compound indicates a higher kinetic stability.展开更多
Reaction of zinc acetate, potassium thiocyanate and the ligand 3-ampy gave the discrete tetrahedral complex [Zn(NCS)<sub>2</sub>(3-ampy)<sub>2</sub>] in which 3-ampy chelates in a monodentate f...Reaction of zinc acetate, potassium thiocyanate and the ligand 3-ampy gave the discrete tetrahedral complex [Zn(NCS)<sub>2</sub>(3-ampy)<sub>2</sub>] in which 3-ampy chelates in a monodentate fashion through its pyridine-N atom. It was characterized by single crystal X-ray diffraction, infrared, and elemental analysis. Density Functional Theory calculations were performed in order to gain insights into the role of weak molecular interactions in the complex that influence the self-assembly process and crystal packing. X---H (X = H, C, N and S) inter-actions. S-H interactions (30.2%) were found to be the main interactions that hold the molecules in the crystal structure. Furthermore, the thermolysis of the complex was studied in order to evaluate whether it was suitable as a precursor for zinc sulphide.展开更多
Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular in...Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular interactions discussed with Hirshfeld surface analysis and 2D fingerprint plots. In addition, using CIF files obtained from our previous results, Hirshfeld surface analysis was newly performed, and the resulting 3DHirshfeld surfaces, 2D print plots, molecular structural features, and crystal structure relationships were described. Classification of their intermolecular interactions, statistical discussion focused on crystalline water and perspective on ligand-protein docking are also mentioned.展开更多
Two compounds,[Zn2（Hcppp）2（cppp）2（H2O）2]·2 NO3·6 H2O（1） and [Cd（Hcppp）2Cl2]· 3H2O（2）（Hcppp = 1-（2-carboxyl-phenyl）-3-（pyridin-2-yl）pyrazole）,are synthesized and characterized by IR,TGA...Two compounds,[Zn2（Hcppp）2（cppp）2（H2O）2]·2 NO3·6 H2O（1） and [Cd（Hcppp）2Cl2]· 3H2O（2）（Hcppp = 1-（2-carboxyl-phenyl）-3-（pyridin-2-yl）pyrazole）,are synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group P21/c with a = 9.894（2）,b = 15.856（3）,c = 20.430（4） A,β = 101.70（3）°,V = 3138.5（11） A3,Z = 2,Mr = 1457.94,Dc = 1.543 g/cm^3,F（000） = 1504,R = 0.0278 and wR = 0.0749 for 6157 observed reflections（I 〉 2σ（I））.Compound 2 crystallizes in triclinic system,space group P1 with a = 9.1424（4）,b = 11.6427（5）,c = 16.1345（7） A,α = 102.6430（10）°,β = 95.4530（10）°,γ = 104.0060（10）°,V = 1605.94（12） A3,Z = 2,Mr = 767.88,Dc = 1.588 g/cm^3,F（000） = 776,R = 0.0307 and wR = 0.0764 for 6275 observed reflections（I 〉 2σ（I））.Compound 1 exhibits a binuclear structure while compound 2 shows a mononuclear structure.In compound 1,two cppp-ligands display the μ2-kN,N′：k O and two Hcppp ligands show the μ1-kN,N′ coordination modes.However,two Hcppp ligands connect one Cd（Ⅱ） cation and exhibit the μ1-kN,N′ binding mode in compound 2.The compounds are both studied using Hirshfeld surface analyses and 2D fingerprint plots.The luminescent properties are also discussed.展开更多
Three new vortioxexine （VOT） salts with salicylic acid （SA）, 5-fluorouracil （FU） and （p-nitrophenyl）-acetic acid （PA） have been synthesized and characterized in detail. In VOT-SA（1：1）, the protonated VOT ...Three new vortioxexine （VOT） salts with salicylic acid （SA）, 5-fluorouracil （FU） and （p-nitrophenyl）-acetic acid （PA） have been synthesized and characterized in detail. In VOT-SA（1：1）, the protonated VOT and deprotonated salicylic anion form a tetrameric unit with the R4 4（12） synthon via N（1）–H（1）…O（1）^a （a： x–1, y, z） and N（1）–H（2）…O（2）^b （b： –x, –y, –z＋1） hydrogen bonds. However, in VOT–FU（1：2）, the protonated VOT and deprotonated 5-fluorouracil anion feature an R4 4（16） ring motif via N（1）–H（1）…O（2）^c （c： –x＋1, –y＋1, –z＋1） and N（1）– H（2）…O（1）^d （d： x, y–1, z） hydrogen bonds. The neutral FU extends the R4 4（16） ring to form a two-dimensional structure through R2 2（8） N–H…O and N（6）–H（4）…N（4）……e （e： –x＋1, y–1/2, –z＋1/2） hydrogen bonds. In VOT-PA（1：1）, PA molecules are linked through N（1）–H（1）…O（1）f （f： –x＋1, y＋1/2, –z＋1） and N（1）–H（2）…O（2）, which forms a right-handed helical structure. Furthermore, components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface, and the salification improves the equilibrium solubilities and dissolution rates of VOT in three salts at 25 ℃ in water.展开更多
Understanding phase transitions in multi-component crystals is of importance for regulating specified functional materials.Herein,we present two new organic-inorganic hybrid crystals,(Me_(3)NCH_(2)CH_(2)X)_(4)[Ni(NCS)...Understanding phase transitions in multi-component crystals is of importance for regulating specified functional materials.Herein,we present two new organic-inorganic hybrid crystals,(Me_(3)NCH_(2)CH_(2)X)_(4)[Ni(NCS)_6](X=Cl and Br),revealing distinct phase transitions.Specifically,the Clsubstituted cations weakly interact with discrete inorganic part hence reveal step-wise dynamic changes upon heating,which result in multi-step solid-solid phase transitions (P1-P2_1/n-A2/a-Cmce) including a ferroelastic one with a spontaneous strain of 0.0475.Whereas the Br-substituted cations with larger steric effect prevent the solid-solid phase transition but give a solid-liquid phase transition at above 419 K.The present instances well demonstrate the complicity for multi-component crystals arising from the delicate balance established by abundant weak intermolecular interactions,and inspire the design of novel phase-transition materials by judiciously assembling multi-component crystals.展开更多
A new compound, [Ni（Hdctrz）（H2O）4]（1, H3dctrz = 1-H-1,2,4-triazole-3,5-dicarboxylic acid）, has been successfully synthesized via slow evaporation. The structure of 1 was characterized by FT-IR, elemental analysi...A new compound, [Ni（Hdctrz）（H2O）4]（1, H3dctrz = 1-H-1,2,4-triazole-3,5-dicarboxylic acid）, has been successfully synthesized via slow evaporation. The structure of 1 was characterized by FT-IR, elemental analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 6.871（1）, b = 11.468（1）, c = 12.178（1） A, b = 101.291（1）o, V = 941.01（16） A3, Z = 4, C4H9N3O8Ni, Mr = 285.85, Dc = 2.018 g·cm–3, m = 2.10 mm–1, F（000） = 584, GOOF = 1.025, the final R = 0.0515 and wR = 0.2125 for 1404 observed reflections（I 〉 2s（I））. The crystal structure is assembled by a slightly distorted {NiNO5} octahedral geometry and hydrogen bonds viz. N–H…O, O–H…O, C–O…π and π···π weak interactions. A rare π···π interaction from triazolate and carboxylate is affirmed through the molecular orbitals（MO） of three adjacent Ni CN molecules. The 3D Hirshfeld surface analysis was employed to gain additional insight into the interactions responsible for the packing of compound 1. Quantitative examination of 2D fingerprint plots revealed, amongst others, the dominating participation of O···H, N···H and π···π interactions in the molecular packing.展开更多
Dexmedetomidine and its novel salt have been synthesized and characterized by single-crystal XRD and TGA/DSG. Components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld s...Dexmedetomidine and its novel salt have been synthesized and characterized by single-crystal XRD and TGA/DSG. Components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed. In this work, the salt strategy has been applied successfully to dexmedetomidine. One important parameter, i.e. stability, has also been significantly improved, which proves to be an important factor for solid dosage formulation. Furthermore, DSC/TGA analysis indicates that the salt maintains its crystallinity up to 300℃, suggesting a higher stability of the salt compared to pure dexmedetomidine.展开更多
1-（3-Fluorobenzoyl）-3-（4-trifluoromethylphenyl）thiourea, C15H10F4N2OS, has been synthesized firstly and determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system...1-（3-Fluorobenzoyl）-3-（4-trifluoromethylphenyl）thiourea, C15H10F4N2OS, has been synthesized firstly and determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group C2/c with a = 31.87（3）, b = 7.705（9）, c = 12.591（14） A°, b = 106.06（2）°, V = 2971（6） A°^3, Z = 8, Dc=1.530 g·cm^-1, F（000） = 1392, m = 0.266 mm^–1, S = 1.06, the final R = 0.070 and w R（I 〉 2s（I）） = 0.249. The crystal structure revealed that the carbonyl thiourea unit in the determined compound was mostly planar due in part to the formation of intramolecular N–H···O=C and C–H···S=C hydrogen bonds that form two S（6） rings. The intermolecular contacts of the crystal structure have been preformed based on the Hirshfeld surface and their associated 2D fingerprint plots. In the packing diagram of the synthesized compound, the C=S group formed two types of intermolecular hydrogen bonds by the H–N（C=O） group and the H–C of the phenyl ring, respectively, and they formed R2^2（8） and R2^2（14） ring motifs, respectively. The crystal packing form was also stabilized by the intermolecular hydrogen bonds C–H···O（1–x, y, 0.5–z） with the R2^2（10） ring motifs. In addition, supramolecular layers sustained by π-π stacking interactions（between the C（2）～C（7） rings with the C（10）～C（15） rings） are formed in the crystal structure of the title compound. The electronic and reactivity were assessed by the natural bond orbital（NBO） analysis in this study.展开更多
An organic-inorganic hybrid based on a-Keggin-typed [BWI2040]5- anionic cluster, [Co（BIIM）3]2H[BWx2040]＇7H20 （BIIM = 2,2＂-biimidazole）, was hydrothermally synthesized and structurally characterized by thermograv...An organic-inorganic hybrid based on a-Keggin-typed [BWI2040]5- anionic cluster, [Co（BIIM）3]2H[BWx2040]＇7H20 （BIIM = 2,2＂-biimidazole）, was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490（10）, b = 33.270（3）, c = 18.9660（16） A, β = 105.9950（10）°, V= 7490.5（11） A3, C36HsoBCo2N24047W12, Mr = 3905.80, Dc = 3.45 l g/cm3, μ（MoKa） = 18.886 rnm-1, F（000） = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections （1 〉 2tr（/））. The compound consists of two isolated [Co（BIIM）3]2＋ cations and one [BW12040]5 anion, in which each Co2＋ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H...O（polyoxometalate and wate） hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W--Oterminal···πimidazole ring interactions which cooperate with the classical N-H···O hydrogen bonds to stabilize the structural packing.展开更多
基金financially supported by the Natural Science Foundation of Guangxi Province(No.2015GXNSFAA139031)the Program for the scientific research,technology development plan of Guilin(No.20150133-5)Program of the Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials in Guangxi(No.gxysxtzx 2017-II-3)
文摘A novel copper complex [Cu2（L）（DMF）2]（1, H4L =（1 Z,N？Z）-3,5-dibromo-N？-（（3,5-dibromo-2-hydroxyphenyl）（hydroxy）methylene）-2-hydroxybenzohydrazonic acid which was synthesized by in-situ oxidation reaction derived from H2hdb（H2hdb = 6,6′-（（1 E,1？E）-hydrazine-1,2-diylidenebis（methanylylidene）） bis（2,4-dibromophenol）） has been synthesized and characterized by IR, elemental analysis（CHN）, TG and single-crystal X-ray diffraction. The single crystal belongs to monoclinic system, space group P21/c with a = 13.538（1）, b = 3.912（1）, c = 23.778（1）A°, β = 105.232（5）o, Mr = 857.08, V = 1214.9（1） A°^3, Z = 2, Dc = 2.343 g/cm^3, F（000） = 824, μ = 8.375 mm^–1, R = 0.0566, and w R = 0.1610. Compound 1 displays weak anti-ferromagnetic interactions through a η^1：η^1：η^1：η^1：η^1：η^1：μ2-L^4- bridging mode. Hirshfeld surface analysis revealed that complex 1 was supported mainly by Br···H and H···H intermolecular interactions.
基金financially supported by the National Natural Science Foundation of China(Nos.51638006 and 51569008)the Natural Science Foundation of Guangxi Province(No.2015GXNSFAA139240)
文摘A highly efficient fluorescence material dinuclear zinc polymer [Zn2（mhbd）2（dca）2]n （1, Hmhbd is 3-methoxy-2-hydroxybenzaldehyde, dca is N（CN）2？） has been synthesized under room temperature and structurally characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The structure belongs to the triclinic system, space group P with a = 8.475（1）, b = 9.595（1）, c = 15.001（1） A, α = 86.84（1）, β = 81.10（1）, γ = 68.78（1）°, Mr = 565.15, V = 1123.5（1） ？3, Dc = 1.671 g？cm–3, F（000） = 568, μ = 2.185 mm–1, R = 0.0451, and wR = 0.1297. 1 is a dinuclear zinc complex which further constructs a 1D chain through double μ1,5-dca bridge. Luminescent property and Hirshfeld surface analysis of 1 have been studied. The result indicates that the fluorescence intensity of complex 1 is forty-one times the fluorescence intensity of Hmhbd ligand.
基金Supported by the Natural Science Foundation of Henan Province(No.102300410021)
文摘A cocrystal based on 1,3-di（4-pyridyl）propane and 3-（（4′-carboxybenzyl）oxy）benzoic acid,C13H14N2·C15H12O5,has been synthesized and characterized by single-crystal X-ray diffraction.The compound crystallizes in monoclinic,space group P21 /c with a = 11.639（4）,b = 9.808（3）,c = 20.854（6）,β = 91.242（7）°,V = 2380.0（13）3,C28H26N2O5,Mr = 470.51,Dc = 1.313 g/cm3,μ（MoKα） = 0.091 mm-1,F（000） = 992,Z = 4,the final R = 0.0677 and wR = 0.1477 for 4175 observed reflections（I 2σ（I））.Intermolecular N H···O hydrogen bonds link two kinds of components into a one-dimensional chain in [10-1] direction and adjacent chains are further arranged into a two-dimensional network by π···π and C H···π interactions.Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the close contacts are mainly focused on weak interactions.The theoretical investigations with HF/6-31G（d） method were performed,and its stability,frontier molecular orbital composition and Mulliken charge distribution were also discussed.
基金Supported by the financial support of Fundamental Research Funds for the Central Universities(3207045420)Jiangsu Ainaji Neoenergy Science&Technology Co.,Ltd.(8507040091)
文摘One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.
基金supported by the National Natural Science Foundation of China(No.20801012)New Energy Technology Co.Ltd.of Ai Naji of Jiangsu Province(No.8507040091)
文摘The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.
基金supported by the prospective joint research project of Jiangsu province(BY20122193)the Fundamental Research Funds for the Central Universities(CXZZ12_0119)
文摘Since 2-aminonicotinic acid is a zwitterionic molecule,the salt or co-crystal strategy was used for the precipitation under identical conditions and obtained two novel salts： salt 1 with 2：1：2 stoichiometry of 2-aminonicotinic acid：perchloric acid：H2O and salt 2 with 2：1：3 stoichiometry of 2-aminonicotinic acid：sulfuric acid：H2O. Their crystal structures were characterized by single-crystal X-ray diffraction,differential scanning calorimetry（DSC） and thermogravimetric analyses（TGA）. The structure determination shows that two salts are both primarily stabilized by the strong N–H…O hydrogen bonding interaction between 2-aminonicotinic acid and its corresponding acids. Constituents of the salt-crystalline phase were also investigated in terms of Hirshfeld surfaces. In the crystal lattice,a three-dimensional hydrogen-bonded network is observed,including the formation of a two-dimensional molecular scaffolding motif. Hirshfeld surfaces and fingerprint plots of two salts show that the structures are stabilized by H…H,O–H…O and C–O…π intermolecular interactions.
基金Fundacao de Amparo a Pesquisa do Estado de Minas Gerais project APQ-01083-11Conselho Nacional de Desenvolvimento Cientifico e Tecnologico grant 245914/2012-9+1 种基金Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior grant PNPD 1648694Pro-Reitoria de Pesquisa/UFMG IE 27/2010 for financial support
文摘Meloxicam(MLX) is an anti-inflammatory drug susceptible to variations and crystalline transitions. In compounding pharmacies, the complete crystallographic evaluation of the raw material is not a routine procedure. We performed a complete crystallographic characterization of aleatory raw MLX samples from compounding pharmacies. X-ray diffraction indicated the presence of two crystalline forms in one sample. DSC experiments suggested that crystallization, or a crystal transition, occurred differently between samples. The FTIR and ~1H NMR spectra showed characteristic assignments.^(13)C solid-state NMR spectroscopy indicated the presence of more than one phase in a sample from pharmacy B. The Hirshfeld surface analysis, with electrostatic potential projection, allowed complete assignment of the UV spectra in ethanol solution. The polymorph I of meloxicam was more active than polymorph III in an experimental model of acute inflammation in mice. Our results highlighted the need for complete crystallographic characterization and the separation of freely used raw materials in compounding pharmacies,as a routine procedure, to ensure the desired dose/effect.
基金Supported by the Natural Science Foundation of Henan Province (No. 102300410021)
文摘One novel adduct based on aminopyridinium and biphenyl-2,4′-dicarboxylate, C5H7N2＋·C14H9O4-, has been synthesized and characterized by X-ray structural study. The compound crystallizes in trigonal, space group P32 with a = 9.2886（16）, b = 9.2886（16）, c = 16.746（6） , γ = 120°, V = 1251.2（5） 3, C19H16N2O4, Mr = 336.34, Dc = 1.339 g/cm3, μ（MoKα） = 0.095 mm-1, F（000） = 528, Z = 3, the final R = 0.0438 and wR = 0.1119 for 3097 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Its electronic structure was calculated at the RHF/6-31G（d） level and a detailed analysis of intermolecular interactions was used by Hirshfeld surface and fingerprint plot. Intermolecular N-H…O hydrogen bonds link two components generating R22（8） rings which are linked into three one-dimensional chains in the [100], [010] and [110] directions, and these chains are finally arranged into a three-dimensional framework by hydrogen bonds. Investigation of intermolecular interactions via Hirshfeld surface analysis reveals that the close contacts are mainly associated with the classical hydrogen bonding interactions. The HOMO-LUMO energy gap of the compound indicates a higher kinetic stability.
文摘Reaction of zinc acetate, potassium thiocyanate and the ligand 3-ampy gave the discrete tetrahedral complex [Zn(NCS)<sub>2</sub>(3-ampy)<sub>2</sub>] in which 3-ampy chelates in a monodentate fashion through its pyridine-N atom. It was characterized by single crystal X-ray diffraction, infrared, and elemental analysis. Density Functional Theory calculations were performed in order to gain insights into the role of weak molecular interactions in the complex that influence the self-assembly process and crystal packing. X---H (X = H, C, N and S) inter-actions. S-H interactions (30.2%) were found to be the main interactions that hold the molecules in the crystal structure. Furthermore, the thermolysis of the complex was studied in order to evaluate whether it was suitable as a precursor for zinc sulphide.
文摘Hirshfeld surface analysis has been widely used in recent years as a means to quantify and visualize various types of intermolecular interactions in molecular crystals. This review article introduces intermolecular interactions discussed with Hirshfeld surface analysis and 2D fingerprint plots. In addition, using CIF files obtained from our previous results, Hirshfeld surface analysis was newly performed, and the resulting 3DHirshfeld surfaces, 2D print plots, molecular structural features, and crystal structure relationships were described. Classification of their intermolecular interactions, statistical discussion focused on crystalline water and perspective on ligand-protein docking are also mentioned.
基金supported by the National Natural Science Foundation of China(Nos.21571118 and 21671124)the Natural Science Foundation of Shanxi Province(2015021031)A portion of this work was performed on the Scientific Instrument Center of Shanxi University of China
文摘Two compounds,[Zn2（Hcppp）2（cppp）2（H2O）2]·2 NO3·6 H2O（1） and [Cd（Hcppp）2Cl2]· 3H2O（2）（Hcppp = 1-（2-carboxyl-phenyl）-3-（pyridin-2-yl）pyrazole）,are synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group P21/c with a = 9.894（2）,b = 15.856（3）,c = 20.430（4） A,β = 101.70（3）°,V = 3138.5（11） A3,Z = 2,Mr = 1457.94,Dc = 1.543 g/cm^3,F（000） = 1504,R = 0.0278 and wR = 0.0749 for 6157 observed reflections（I 〉 2σ（I））.Compound 2 crystallizes in triclinic system,space group P1 with a = 9.1424（4）,b = 11.6427（5）,c = 16.1345（7） A,α = 102.6430（10）°,β = 95.4530（10）°,γ = 104.0060（10）°,V = 1605.94（12） A3,Z = 2,Mr = 767.88,Dc = 1.588 g/cm^3,F（000） = 776,R = 0.0307 and wR = 0.0764 for 6275 observed reflections（I 〉 2σ（I））.Compound 1 exhibits a binuclear structure while compound 2 shows a mononuclear structure.In compound 1,two cppp-ligands display the μ2-kN,N′：k O and two Hcppp ligands show the μ1-kN,N′ coordination modes.However,two Hcppp ligands connect one Cd（Ⅱ） cation and exhibit the μ1-kN,N′ binding mode in compound 2.The compounds are both studied using Hirshfeld surface analyses and 2D fingerprint plots.The luminescent properties are also discussed.
基金supported by the Guangdong Department of Science and Technology(2012A080800002 and 2015A020211005)
文摘Three new vortioxexine （VOT） salts with salicylic acid （SA）, 5-fluorouracil （FU） and （p-nitrophenyl）-acetic acid （PA） have been synthesized and characterized in detail. In VOT-SA（1：1）, the protonated VOT and deprotonated salicylic anion form a tetrameric unit with the R4 4（12） synthon via N（1）–H（1）…O（1）^a （a： x–1, y, z） and N（1）–H（2）…O（2）^b （b： –x, –y, –z＋1） hydrogen bonds. However, in VOT–FU（1：2）, the protonated VOT and deprotonated 5-fluorouracil anion feature an R4 4（16） ring motif via N（1）–H（1）…O（2）^c （c： –x＋1, –y＋1, –z＋1） and N（1）– H（2）…O（1）^d （d： x, y–1, z） hydrogen bonds. The neutral FU extends the R4 4（16） ring to form a two-dimensional structure through R2 2（8） N–H…O and N（6）–H（4）…N（4）……e （e： –x＋1, y–1/2, –z＋1/2） hydrogen bonds. In VOT-PA（1：1）, PA molecules are linked through N（1）–H（1）…O（1）f （f： –x＋1, y＋1/2, –z＋1） and N（1）–H（2）…O（2）, which forms a right-handed helical structure. Furthermore, components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface, and the salification improves the equilibrium solubilities and dissolution rates of VOT in three salts at 25 ℃ in water.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22071273 and 21821003)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01C161)。
文摘Understanding phase transitions in multi-component crystals is of importance for regulating specified functional materials.Herein,we present two new organic-inorganic hybrid crystals,(Me_(3)NCH_(2)CH_(2)X)_(4)[Ni(NCS)_6](X=Cl and Br),revealing distinct phase transitions.Specifically,the Clsubstituted cations weakly interact with discrete inorganic part hence reveal step-wise dynamic changes upon heating,which result in multi-step solid-solid phase transitions (P1-P2_1/n-A2/a-Cmce) including a ferroelastic one with a spontaneous strain of 0.0475.Whereas the Br-substituted cations with larger steric effect prevent the solid-solid phase transition but give a solid-liquid phase transition at above 419 K.The present instances well demonstrate the complicity for multi-component crystals arising from the delicate balance established by abundant weak intermolecular interactions,and inspire the design of novel phase-transition materials by judiciously assembling multi-component crystals.
基金Supported by the National Natural Science Foundation of China(No.21571118)Shanxi Scholarship Council of China(2013-026)
文摘A new compound, [Ni（Hdctrz）（H2O）4]（1, H3dctrz = 1-H-1,2,4-triazole-3,5-dicarboxylic acid）, has been successfully synthesized via slow evaporation. The structure of 1 was characterized by FT-IR, elemental analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 6.871（1）, b = 11.468（1）, c = 12.178（1） A, b = 101.291（1）o, V = 941.01（16） A3, Z = 4, C4H9N3O8Ni, Mr = 285.85, Dc = 2.018 g·cm–3, m = 2.10 mm–1, F（000） = 584, GOOF = 1.025, the final R = 0.0515 and wR = 0.2125 for 1404 observed reflections（I 〉 2s（I））. The crystal structure is assembled by a slightly distorted {NiNO5} octahedral geometry and hydrogen bonds viz. N–H…O, O–H…O, C–O…π and π···π weak interactions. A rare π···π interaction from triazolate and carboxylate is affirmed through the molecular orbitals（MO） of three adjacent Ni CN molecules. The 3D Hirshfeld surface analysis was employed to gain additional insight into the interactions responsible for the packing of compound 1. Quantitative examination of 2D fingerprint plots revealed, amongst others, the dominating participation of O···H, N···H and π···π interactions in the molecular packing.
基金supported by the prospective joint research project of Jiangsu province(BY20122193)the Fundamental Research Funds for the Central Universities(CXZZ12_0119)
文摘Dexmedetomidine and its novel salt have been synthesized and characterized by single-crystal XRD and TGA/DSG. Components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed. In this work, the salt strategy has been applied successfully to dexmedetomidine. One important parameter, i.e. stability, has also been significantly improved, which proves to be an important factor for solid dosage formulation. Furthermore, DSC/TGA analysis indicates that the salt maintains its crystallinity up to 300℃, suggesting a higher stability of the salt compared to pure dexmedetomidine.
基金supported by the Science and Technology Program of Shaanxi Province,China(No.2013K02-25)the Science and Technology Program of Xi’an,China(No.NC1404)+1 种基金the Science and Technology Research and Development Program of Shaanxi Province,China(No.14JF025)the college students innovative training program of Northwest University,China(No.2017214)
文摘1-（3-Fluorobenzoyl）-3-（4-trifluoromethylphenyl）thiourea, C15H10F4N2OS, has been synthesized firstly and determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group C2/c with a = 31.87（3）, b = 7.705（9）, c = 12.591（14） A°, b = 106.06（2）°, V = 2971（6） A°^3, Z = 8, Dc=1.530 g·cm^-1, F（000） = 1392, m = 0.266 mm^–1, S = 1.06, the final R = 0.070 and w R（I 〉 2s（I）） = 0.249. The crystal structure revealed that the carbonyl thiourea unit in the determined compound was mostly planar due in part to the formation of intramolecular N–H···O=C and C–H···S=C hydrogen bonds that form two S（6） rings. The intermolecular contacts of the crystal structure have been preformed based on the Hirshfeld surface and their associated 2D fingerprint plots. In the packing diagram of the synthesized compound, the C=S group formed two types of intermolecular hydrogen bonds by the H–N（C=O） group and the H–C of the phenyl ring, respectively, and they formed R2^2（8） and R2^2（14） ring motifs, respectively. The crystal packing form was also stabilized by the intermolecular hydrogen bonds C–H···O（1–x, y, 0.5–z） with the R2^2（10） ring motifs. In addition, supramolecular layers sustained by π-π stacking interactions（between the C（2）～C（7） rings with the C（10）～C（15） rings） are formed in the crystal structure of the title compound. The electronic and reactivity were assessed by the natural bond orbital（NBO） analysis in this study.
基金Supported by the Natural Science Foundation of Henan Province(No.102300410021)
文摘An organic-inorganic hybrid based on a-Keggin-typed [BWI2040]5- anionic cluster, [Co（BIIM）3]2H[BWx2040]＇7H20 （BIIM = 2,2＂-biimidazole）, was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490（10）, b = 33.270（3）, c = 18.9660（16） A, β = 105.9950（10）°, V= 7490.5（11） A3, C36HsoBCo2N24047W12, Mr = 3905.80, Dc = 3.45 l g/cm3, μ（MoKa） = 18.886 rnm-1, F（000） = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections （1 〉 2tr（/））. The compound consists of two isolated [Co（BIIM）3]2＋ cations and one [BW12040]5 anion, in which each Co2＋ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H...O（polyoxometalate and wate） hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W--Oterminal···πimidazole ring interactions which cooperate with the classical N-H···O hydrogen bonds to stabilize the structural packing.
