Hydrogen Bonding Network Assembled with 2-Amino-3-hydroxypyridium and Isonicotinate-N-oxide

The crystal structure of the compound (C₅H₇N₂O)·(C₆H₄NO₃)·H₂O (1) consisting of 2-amino-3-hydroxypyridium, isoniconate-N-oxide and lattice water was characterized by single-crystal X-ray diffraction analysis: monoclinic, P2₁/c, a = 9.6905(8), b = 6.0040(4), c = 21.039(2) Å, β = 101.062(8)°, V = 1201.34(18) Å³, Z = 4. In 1, the deprotonated isoniconate-N-oxide, the protonated 2-amino-3-hydroxypyridium and the lattice water are linked by a series of classical hydrogen bonds to form 2-D layer. Then, these 2-D sheets assemble to a 3-D network via weak hydrogen bonds.     

Synthesis and Crystal Structure of [2-(4-chlorobenzoyloxy)-5-methylphenyl]-(4-methylphenyl)methanone

[2-(4-Chlorobenzoyloxy)-5-methylphenyl]-(4-methylphenyl)methanone was synthesized and characterized by spectroscopic and X-ray diffraction methods. The molecule crystallizes in the monoclinic space group P2₁/c with cell parameters a = 13.7530(19) Å, b = 10.0560(19) Å, c = 13.469(3) Å, β = 100.630(7)° and Z = 4. There is a large discrepancy between the carbonyl group bond lengths of ketone and the ester. The structure exhibits intermolecular hydrogen bonds of the type C–H···O.     

含酯基吡啶类离子液体的晶体结构及酯基链长微变对其性质的影响

基于酯基链长的微小变化,采用两步法设计合成两个含酯基吡啶类离子液体1-乙酸甲酯基-3-甲基吡啶六氟磷酸盐[MeMPy][PF6](记IL1)和1-乙酸乙酯基-3-甲基吡啶六氟磷酸盐[EAMPy][PF6](记IL2).采用溶剂挥发法在混合溶剂体系中获得6.5 mm IL1和8.0 mm IL2大单晶体,酯基链由乙酸甲酯基微变为乙酸乙酯基,其晶体结构及超分子结构的形成具有显著的变化.晶体学数据研究表明,IL1属于三斜晶系,空间群为P1,其晶胞参数为a=0.8754(3) nm,b =0.8780(3) nm,c=1.0551(6) nm,z=2等.IL2属于正交晶系,空间群为P2(1)2(1)2(1),其晶胞参数为a=0.7127(17) nm,b=1.2792(3) nm,c=1.5327(3) nm,z=4等.随着酯基链的增长,分子结构空间位阻发生了变化,IL2中亚甲基和吡啶环上的甲基均参与超分子空间网络形成,改变了晶体堆积的空间点阵和性质.进一步实验验证表明,酯基链较长的IL2熔点较高,热稳定性较差,然而阳离子结构的微小变化对其离子导电活性的影响相对较小.     

Synthesis and Crystal Structure of the Hydrated Nickel(II) Complex of Tartrate

Abstract  A new dinuclear hydrated nickel(II) tartrate has been isolated and structurally characterized by single-crystal X-ray diffraction. The title compound formulated as [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 (C₁₇H_55.5Ni₄O_42.75) crystallizes in monoclinic system, space group P2(1)/c with a = 13.684(5), b = 17.143(6), c = 18.586(6) ?, β = 96.638(6)°, V = 4331(3) ?³, Z = 4. The unit cell contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference, half of menthol molecule and ten and a quarter packing water molecules. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way. Each Ni(II) atom is six-coordinated by six O atoms from two tartrate units and two water molecules. Index Abstract  The crystal structure of complex [Ni₄(C₄H₄O₆)₄(H₂O)₈](EtOH)_0.5(H₂O)_10.25 contains two crystallographic independent dimeric units of [Ni₂(C₄H₄O₆)₂(H₂O)₄] without significant structural difference. In each dimeric unit, one (R,R)-tartrato dianion chelates two Ni(II) ions by the use of two hydroxy oxygen and two carboxyl oxygen atoms as donor atoms, and another tartrato dianion chelates the same pair of Ni(II) cations in the same way.      

Synthesis and Crystal Structure of a New Mo(V) Complex of Cyano Ligands

Abstract  A new complex, [H₃teta][Mo(CN)₈] · H₂O, (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene), has been synthesized and characterized by IR spectrum, element analysis and single crystal X-ray diffraction: monoclinic, space group P2(1)/c with a = 10.8553(8) ?, b = 12.4854(8) ?, c = 22.6348(15) ?, α = 90.00°, β = 97.3080(10)°, γ = 90.00°, Mr = 609.63, v = 3042.8(4), Z = 4. There are one [H₃teta]³⁺, one [Mo(CN)₈]³⁻ and one water molecule in the asymmetric unit. The complex is interconnected through hydrogen bond and formed into a 3D porous network. Graphical Abstract  A new complex, [H₃teta][Mo(CN)₈] · H₂O, has been synthesized and characterized by IR spectrum, element analysis and single crystal X-ray diffraction. And it shows a 3D porous network through hydrogen bonds.      

Crystal Structure of the Tunnel-like Supramolecular Complex: Methylviologen(2+) Octaaquaoxalatodiiron(II) Disulfate

Abstract  The 3D supramolecular complex, (C₁₂H₁₄N₂)[Fe(II)₂(C₂O₄)(OH₂)₈] · 2(SO₄)²⁻, is monoclinic, P2₁/n, with the following cell parameters: a = 8.0413(16) ?, b = 17.272(4) ?, c = 9.806(2) ?, β = 106.25(3)°, V = 1307.6(5) ?³, Z = 2, R ₁ = 0.0344, and wR ₂ = 0.0763. X-ray crystallography revealed that the structure can be regarded as a hydrogen-bonded tunnel-like supramolecule with the methylviologen lying in the tunnel as the charge compensating cation. The multiple intermolecular hydrogen bonds between the octaaquaoxalatodiiron cations and the isolated sulfate ions link the supramolecular complex into a quasi-three-dimensional open-framework structure. Graphical Abstract  Crystal Structure of the Tunnel-like Supramolecular Complex: Methylviologen(2+) Octaaquaoxalatodiiron(II) Disulfate Xin Yang, Jiang Li, Shenyi Shi, Yawei Hou and Yongkui Shan A hydrogen-bonded tunnel-like supramolecular structure with the methylviologen lying in the tunnel as the charge compensating cation has been synthesized for the first time.      

Cu(II) Compounds with Pyrimidine-Based Chelating Ligands,Bridged by a Flexible Alkyl Spacer: Synthesis,Characterisation and X-Ray Structures of Methoxide-Bridged Dinuclear-Based Species

Abstract  The synthesis and full structural characterisation is described of 3 dinuclear-based Cu(II) compounds bridged by methoxide anions, and flexible linear bis(pyrimidine)-α,ω-diaminoalkane ligands. The structures are dinuclear based in all cases, in which the bis(pyrimidine)diaminoalkane ligand chelates to 2 Cu(II) ions in the same dinuclear unit (N–C–C–C–C–C–N linker), or to two different dinuclear units (with the short N–C–C–N linker), thereby generating a polymeric chain. The magnetic exchange in the compounds is dominated by the alkoxido-bridged ligands, which generate a very strong antiferromagnetic coupling between the Cu(II) ions, resulting in diamagnetism at room temperature and below, and EPR silent behaviour. Index Abstract  Dinuclear-based Cu(II) compounds with pyrimidine-based chelating ligands flexible linear bis(pyrimidine)-α,ω-diaminoalkane ligands are described, bridged by methoxide anions. The structures are dinuclear based in all cases, with the ligand chelating to 2 Cu(II) ions in the same dinuclear unit (N–C–C–C–C–C–N linker), or to 2 different dinuclear units (with short N–C–C–N linkers). The very strong antiferromagnetic magnetic exchange in all compounds is caused by the alkoxido-bridged ligands. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal and Molecular Structure of Songorine from the Root of Aconitum szechenyianum Gay

Songorine was isolated from the root of Aconitum szechenyianum Gay and its crystal structure was determined by X-ray single crystal diffraction. The compound compactly packs in an orthorhombic unit cell in the P2₁2₁2₁ space group with unit cell dimensions a = 9.7733(7) Å, b = 13.4892(9) Å, c = 14.8097(10) Å, V = 1952.4(2) Å³ and Z = 4. A series of intricate hydrogen bonds assemble the title compound into a three-dimensional networking structure.     

Crystal Structures of Hexameric and Dimeric Complexes of Lithioisobutyrophenone

Abstract The crystal structures of two unsolvated hexameric complexes and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated dimeric complex of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported. The unsolvated LiIBP complexes crystallize from benzene-d ₆ to yield two different types of crystals that have similar structures: one in the triclinic space group P-1 with a = 10.7944(7), b = 11.9350(8), c = 12.0956(8) ?; α = 117.5560(10), β = 100.8090(10), γ = 92.3030(10)° and Z = 1 and a second in the monoclinic space group C2/c with a = 17.6011(11), b = 14.7389(9), c = 21.0943(13) ?; β = 105.2510(10)° and Z = 4. The two LiIBP hexamers differ slightly in the conformations of the enolate moieties around the Li₆O₆ core. The hexamer in both the triclinic as well as the monoclinic polymorph is located on a crystallographic inversion center that each generates the other half of the cluster. The TMEDA-solvated LiIBP dimer crystallizes from hexanes in the monoclinic space group C2/c with a = 11.8472(6), b = 14.8268(7), c = 19.2719(9) ?; β = 98.8480(10)° and Z = 4. The center of the dimer is located on a crystallographic C2 axis. These complexes represent only the second reported crystal structures of either an unsolvated hexamer or a solvated dimer of a lithium enolate of a simple monocarbonyl ketone. Graphical Abstract The X-ray crystal structures of two unsolvated hexameric and one N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)-solvated complexes of the lithium enolate of 2-methyl-1-phenyl-1-propanone (lithioisobutyrophenone, LiIBP) are reported. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

The Syntheses and Crystal Structures of Metronidazole-derived Compounds

Abstract Metronidazole (MET-OH), widely used as an antibacterial agent, is found to have some side effects on human bodies. Due to these disadvantages, people have been looking for its modification compounds for substituents. In this article, four MET-OH derivatives were designed, prepared, and structurally characterized by single crystal X-ray diffraction. These compounds are MET-OTs (1), MET-Br (2), MET-Cl (3), and MET-I (4). X-ray structure analyses revealed that, 1 crystallized in the monoclinic system with space group P2 ₁ /c, with a = 16.1178, b = 7.5473, c = 13.4161 ?, V = 1520.3 ?³, β = 111.3210^o and Z = 4. 2 crystallized in the monoclinic system with space group P2 ₁ /c, with a = 12.079, b = 11.089, c = 6.380 ?, V = 847.1 ?³, β = 97.57^o and Z = 4. 3 crystallized in the monoclinic system with space group P2 ₁ /c, with a = 12.098, b = 11.007, c = 6.295 ?, V = 830.3 ?³, β = 97.886^o and Z = 4. 4 crystallized in the triclinic system with space group P1, with a = 6.192, b = 7.740, c = 10.001 ?, V = 457.9 ?³, α = 89.073, β = 86.903, γ = 73.097^o and Z = 2. Index Abstract In this article, metronidazole-derived compounds were prepared and structurally characterized by single crystal X-ray diffraction      

The Simultaneous Presence of Different Varieties of Intermolecular Hydrogen Bonds in a New Layer-Type Anionic Host Lattice Built of Thiourea,Fumaric Acid and Fumarate Anion

A new inclusion complex (n-C₄H₉)₄N⁺C₄H₃O ₄ ^?  · C₄H₄O₄ · (NH₂)₂CS has been prepared and characterized by X-ray crystallography. Crystal data: space group P \( \overline 1 \), a = 8.799(2) Å, b = 9.590(1) Å, c = 18.684(4) Å, α = 89.63(1)°, β = 79.56(1)°, γ = 79.74(1)°, V = 1525.2(5) ų, Z = 2, R ₁ = 0.0562 and wR = 0.1033. In the title compound, thiourea molecules, fumaric acid and fumarate anions are joined together by typical O–H···O, N–H···O and N–H···S, plus weak C–H···O and C–H···S, hydrogen bonds to generate a hydrogen-bonded layer corresponding to the (100) family of planes. The tetra-n-butylammonium cations are orderly arranged in a sandwich-like packing mode between the stacked layers. The simultaneous presence of different varieties of intermolecular hydrogen bonds is an interesting feature of the title compound.     

[KCl<Subscript>3</Subscript>{H<Subscript>2</Subscript>dabco}]: A Unique 3-D Charge-Assisted Hydrogen-Bonded Hybrid Network of Anionic KCl<Subscript>3</Subscript> Chains and Organic Cations

Abstract  The 3-D hybrid network [KCl₃{H₂dabco}] resulted from the assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O. The compound crystallizes in the trigonal space group R-3c with a = b = 16.0437(2) Å, and c = 22.3094(2) Å. The structure consists in polymeric chains of anionic {KCl₃}²⁻ linked to {H₂dabco}²⁺ units by hydrogen bonds. Each organic cation establishes such charge-assisted H···Cl interactions with two inorganic arrays leading to a 3-D network. Index Abstract  Assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O resulted in a 3-D hybrid network of inorganic {KCl₃}²⁻ chains H-bonded to bridging organic cations.      

Crystal structure of a salt complex between (<Emphasis Type="Italic">S</Emphasis>)-2-(2′-methylbenzyl)succinic acid and (<Emphasis Type="Italic">R</Emphasis>)-1-phenylethylamine

The optically pure 2-(2′-methylbenzyl)succinic acid were obtained by the optical resolution of the racemates with the chiral host 1-phenylethylamine. The structure of the salt complex between (S)-2-(2′-methylbenzyl)succinic acid and (R)-1-phenylethylamine was first elucidated by X-ray analysis: Monoclinic, Space group P2₁ with a=6.0781(12) ?, b=8.8224(18) ?, c=17.675(4) ?, β=97.64(3)°, V=939.4(3) ?³, Z=2, the absolute structure parameter is 0 (9). The crystal structure indicates that the hydrogen bonds are formed between the acetate anions and the protonated amino group. The intermolecular hydrogen bond links the salt complex into a quasi-two-dimentional netlike structure.     

Crystal structure of the piperazine-1,4-diium (DL-)hydrogen malate (1:2)

The crystalline salt of piperazine-1,4-diium (DL-)hydrogen malate (1:2), (C₄H₁₂N₂)²⁺ (C₄H₅O₅)₂^–, has been prepared and characterized by X-ray crystallography. The title salt crystallizes in monoclinic space group P2₁/n with a = 7.073(1), b = 14.180(2), c = 7.526(1) Å, = 94.66(1), V = 752.33(18) ų and Z = 2. Results indicate that the title salt exists as a racemic compound but a conglomerate. In the structure, axial and equatorial hydrogen atoms of piperiaine-1,4-diium are all involved in different bifurcated hydrogen bonds. The integral structure, formed by the hard hydrogen bonds of N–HsO and O–HsO, is stabilized further by soft hydrogen bond of C–HsO.     

Synthesis and X-ray Crystal Structures of Two Luminescent Imidazopyridinium Derivatives from the Corresponding N-(aryl)-Pyridine-2-aldimines

Syntheses and X-ray structural characterizations of two new luminescent imidazopyridinium derivatives, 2-(phenyl)-N(3)-(4(methyl)phenyl)-imidazo[1,5a] pyridinium perchlorate (1) and 2-(pyridyl)-N(3)-(4-(chloro)phenyl)-imidazo[1,5a] pyridinium perchlorate (2) are reported. The compounds are prepared in one step from N-(4-(methyl)phenyl) pyridine-2-aldimine and N-(4-(chloro)phenyl) pyridine-2-aldimine respectively in a transformation mediated by Mn(OAc)₂-KMnO₄ mixture. It is found that the molecular structures of the two compounds are similar. In the solid state, 1 forms a three-dimensional network through a series of hydrogen bonds between the cations and anions in the lattice while 2 forms a similar but less extensively linked network. The substitution of hydrogen at the 2-position of the imidazopyridinium ring by phenyl or 2-(pyridyl) affects the nature of their first excited states as detected by changes in their emission and absorption spectra.     

结晶生长的化学键合理论

针对一般晶体的生长过程,在测定相应溶液(熔体)组成结构的基础上,我们引入了晶体生长过渡相区的概念,并采用键价模型来衡量生长过程中发生变化的化学键的键强度。过饱和溶液(熔体)中的生长单元经过生长过渡相区时,依据彼此之间弱的化学键合作用来微调其内部强的化学键,并以单个生长单元或者生长单元的简单连接体的形式键合进入晶格。在整个结晶生长过程中,生长单元之间弱的键合作用对整个结晶过程(生长速度、晶相的形成)起着决定性作用;同时,中等强度的化学键在生长过渡相区中的变化情况对晶体的最终形貌具有重要影响。     

The Crystal and Molecular Structure of a Polymorph and a Pseudo-Polymorph of Droperidol

Abstract Crystals of two crystal modifications of droperidol: a hemihydrate (1) and the z polymorph (2), have been isolated and their structure determined using X-ray diffraction methods. Droperidol hemihydrate crystallized in the triclinic space group P − 1, with unit cell parameters a = 6.2842(15), b = 10.1473(8), c = 16.1850(2) ?; α = 102.554(9); β = 91.917(14); γ = 99.316(12)°; V = 991.6(3) ?³, and Z = 2. The droperidol z polymorph crystallized in the monoclinic space group P2₁/c, with unit cell parameters a = 20.0406(8), b = 7.4955(4), c = 12.9733(5) ?; β = 98.089(2)°; V = 1929.39(15) ?³, and Z = 4. In 1 and 2 two molecules of droperidol are joined by two N–H···O hydrogen bonds. The structure of 1 shows a possible additional hydrogen bond linking the two droperidol molecules via the water molecule. Graphical Abstract The crystal and molecular structure of a polymorph and a pseudo-polymorph of droperidol A. Actins, R. Arajs, S. Belakovs, L. Orola, and M. V. Veidis Crystals of two crystal modifications of droperidol: a hemihydrate and the z polymorph have been isolated and their structure determined using single crystal X-ray diffraction methods. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

一种新型三维包结物的合成和晶体结构

以六氰合钴酸钾,五水硫酸铜和乙二胺为原料,通过采用不同溶剂、不同配比实验对比,合成了一种新的三维夹心配位包结物 [Cu(en)2]2{K[Co(CN)6]}2[en=乙二胺]晶体,对其进行了元素分析、红外光谱表征和单晶结构测定.X射线单晶衍射测定表明,该配位包结物属单斜晶系,C2/c空间群,晶胞参数为a=0.8406(3)nm,b=1.6906(5)nm,c=1.1803(4)nm,β=98.931(5)°,V=0.16570(9)nm3,Z=2,dc=1.755g/cm3,μ=2.549mm-1,F(000)=884, R1=0.0323,wR2=0.0807.这种新的三维的夹心配位包结物由[Co(CN)6]3-与外界的K+离子通过氰根(-CN-)配位形成三维网络格子,在每个网格中镶嵌着二乙胺合铜(II)配合物.     

Crystal Structure of Meso-tetrakis[4-(pentyloxy)phenyl]porphyrin

Abstract  The crystal structure of the title compound, C₆₄H₇₀N₄O₄, has been determined by single crystal X-ray diffraction methods. The title compound crystallizes in the monoclinic space group P2(1)/c with cell dimensions a = 13.8946(3) ?, b = 16.1069(3) ?, c = 12.1974(2) ?, β = 93.4050(10)°, Z = 2. The porphyrin core to be composed of four pyrrole rings linked through methane carbon bridges. Each molecule lies across a crystallographic inversion center. The porphyrin core is planar, which facilitates π-electron delocalization. The inner nitrogen H atoms are found localized on opposite pyrrole rings and these rings differ structurally from the other two pyrrole rings. The imino H atoms form bifurcated intramolecular hydrogen bonds with the adjacent unprotonated N atoms due to the contract porphyrin core. Graphical Abstract  The crystal structure of meso-tetrakis[4-(pentyloxy)phenyl]porphyrin is reported in this paper.      

The Role of Hydrogen Bonding and Halogen Bonding in the Polymorphic Structures of 3,5-Dibromo-2,6-diaminopyridinium Bromide

Abstract  

An analysis is made of the supramolecular interactions in the two polymorphic structures of 3,5-dibromo-2,6-diaminopyridinium bromide, with particular emphasis on the roles of hydrogen and halogen bonding. Because of the extensive hydrogen bonding capabilities, hydrogen bonding interactions dominate in both phases. This causes a competition between C–Br···Br–C and C–Br···Br⁻ halogen bonding interactions, with the former dominating in the orthorhombic Pbca phase and the latter in the monoclinic P2₁/c phase. For Pbca phase a = 5.5197(11) ?, b = 15.040(3) ?, c = 23.2555(5) ?, and for P2₁/c phase a = 8.1143(19) ?, b = 14.226(3) ?, c = 8.9005(18) ?, β = 113.18(2)°.