One Porous Supramolecular Complex Assembled from Ionic and Neutral Hydrogen-bonds of N–H···O and C–H···O

Abstract  

The imidazolyl derived complex N,N′-butylenebis(imidazole):(oxalic acid)_0.5 was prepared and structurally characterized by X-ray crystallography. The title compound crystallizes in the triclinic, space group P-1, with a = 4.4373(9) ?, b = 12.882(3) ?, c = 15.319(3) ?, α = 99.91(3)°, β = 94.53(3)°, γ = 98.72(3)°, V = 847.7(3) ?³, Z = 2. Two N,N′-butylenebis(imidazole) and two oxalic acid molecules form an annulus via intermolecular hydrogen bonds, with internal dimensions of about 7.1 × 11.1 ?. Neighboring annuluses were connected by N–H···O and C–H···O interactions to form 1D double chain structure. Adjacent double chains stacked just above each other along the a-axis direction, this arrangement of the double chains leads the extended supramolecular architecture to show a three-dimensional porous network.     

Crystal Structure of 2-Thiophenecarboxamide: A One-dimensional Tubular Structure Formed by N–H···O Hydrogen Bonds

Abstract  The crystal structure of 2-thoiphenecarboxamide is described. The compound crystallizes in the orthorhombic Pna2₁ space group with unit cell parameters a = 10.044 (3) ?, b = 14.203 (4) ? and c = 15.941 (3) ?; V = 2,274.1 (10) ?³. The asymmetric unit contains four independent molecules which are linked by N–H···O hydrogen bonds. The asymmetric unit at (x, y, z) is connected with another one, produced by the a-glide plane at 0.75 along the b-axis, that lies at (x + 0.5, −y + 1.5, z) by two N–H···O hydrogen bonds and by a C–H···O weak hydrogen bond to form a one-dimensional tube. Adjacent tubes are linked by C–H···pi interactions to form a three-dimensional framework. Graphical Abstract  The crystal structure of 2-thiophenecarboxamide, contains four crystallographically independent molecular components in the asymmetric unit linked by four N–H···O hydrogen bonds and a weak C–H···O hydrogen bond and form a one-dimensional tube. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Short H· · ·H distances in norbornene derivatives

A short H···H intramolecular interaction was reported previously for an anhydride of syn-sesquinorbornene. The synthesis and structure of a such an anhydride with an additional five-membered dithiole ring has been investigated. While hydrogen atom positions are not accurately located, the 1.62 Å separation indicates this molecule is a candidate for the shortest H···H interaction. Two cycloadducts of norbornadiene, which literature suggests might exhibit additional short interactions, are reported also; however, the isomers with minimal intramolecular interactions are the isolated products. C₂₂H₂₀O₃S₂, 3, crystallizes in P with a = 10.881(4), b = 13.712(8), C = 6.548(8) Å, = 101.32(6), = 107.49(5), = 90.49(4)°, D _calc = 1.445 g cm^–3, and Z = 2, C₂₁H₂₀O₄Cl₈, 5, in P2₁/n with a = 8.168(2), b = 13.488(4), c = 23.500(6) Å, = 94.72(2)°, D _calc = 1.597 g cm^–3, and Z = 4, C₂₁H₂₈O₄, 6, in P> with a = 12.667(2), b = 12.792(2), c = 12.540(2) Å, = 113.51(1), = 98.18(1), = 74.39(1)°, D _calc = 1.276 g cm^–3, and Z = 4.     

Analysis of C–H···O Intermolecular Interactions in 4-Androstene-3,17-dione

Abstract  4-Androstene-3,17-dione was synthesized for its crystallographic analysis and to investigate the role of intra- and intermolecular interactions in steroids. It crystallizes in the orthorhombic space group P2₁2₁2₁ with unit cell parameters, a = 7.330(2) ?, b = 13.095(11) ?, c = 16.856(17) ?, V = 1,618(5) ?³ and Z = 4. The structure has been solved by direct methods using X-ray diffraction techniques and the refined final reliability index for the computed structure is 0.033 for 1,655 observed reflections. Two six-membered rings B and C exist in chair conformation while ring A occupies a sofa conformation. The five-membered ring D depicts envelope conformation. The C–H···O intermolecular hydrogen interaction results into a ring like configuration which makes the dimers. Index Abstract   Androgen is the generic term for any natural or synthetic compound, usually a steroid hormone, that stimulates or controls the development and maintenance of masculine characteristics in vertebrates by binding to androgen receptors [1]. Androgens have been used in breast cancer when excision or radiotherapy have failed to control the progress of local recurrent disease. They are also used in case where the primary tumour is inoperable or is unsuited for, or resistant to, radiotherapy. Androgens are also believed to be responsible for linear bone growth in both males and females, probably in conjunction with somatotrophin [2]. In continuation to our work on the single crystal growth of X-ray diffraction quality crystals and crystallographic analysis of steroidal molecules, [3-7] synthesis and crystallographic study 4-androstene-3,17-dione is reported in this paper.     

Crystal Structure of 2′,3′-Di-<Emphasis Type="Italic">O</Emphasis>-Acetyl-5′-Deoxy-5-Fluorocytidine with N–H···(O,F) Proton Donor Bifurcated and (C,N)–H···O Bifurcated Acceptor Dual Three-Center Hydrogen Bond Configurations

Abstract  The title compound, C₁₃H₁₆O₆N₃F, features a central furan ring containing four carbon atom chiral centers with a 4-amino-5-fluoro-2-oxopyrimidine group, two acetyl groups and a methyl group bonded at the 2,3,4,5 positions, each in an absolute R configuration (2R,3R,4R,5R). It crystallizes in the monoclinic space group C2 with unit cell parameters a = 14.5341(3), b = 7.26230(10), c = 16.2197(3) ?, β = 116.607(2)°, Z = 4. An extensive array of intra and intermolecular hydrogen bond interactions dominate crystal packing in the unit cell highlighted by a relatively rare three-center proton-bifurcated donor N–H···(O,F) hydrogen bond interaction in cooperation with a second, (C,N)–H···O bifurcated acceptor three-center hydrogen bond in a supportive fashion. Additional weak Cg π-ring intermolecular interactions between a fluorine atom and the 4-amino-5-fluoro-2-oxopyrimidine ring in concert with multiple donor and acceptor hydrogen bonds significantly influence the bond distances, bond angles and torsion angles of the deoxy-5-fluorocytidine group. Comparison to a MOPAC computational calculation provides support to these observations. Index Abstract  Crystal structure of (2R,3R,4R,5R)-2-(4-amino-5-fluoro-2-oxopyrimidin-1(2H)-yl)-5-methyl-tetrahydrofuran-3,4-diyl diacetate with dual N–H···(O,F) proton donor bifurcated and (C,N)–H···O bifurcated acceptor three-center hydrogen bond configurations is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

C–H···π and C=O···π Intermolecular Interactions in Dibenzyl-3,6-dimethylpyrazine-2,5-dicarboxylate

Abstract A new pyrazine compound, has been synthesised and characterised by single-crystal X-ray diffraction: monoclinic, P2₁/c with a = 11.0707(3) ?, b = 5.23700(10) ?, c = 16.6997(5) ?, β = 103.5385(16)°, Mr = 376.40, V = 941.30(4) ?³, Z = 2. Each molecule possesses C _i symmetry with the two halves of the molecule related by an inversion centre. C–H···π and C=O···π interactions held the molecules together. Index Abstract C–H···π and C=O···π intermolecular interactions in dibenzyl-3,6-dimethylpyrazine-2,5-dicarboxylate Joana A. Silva, Ana C. Santos, Ana T. Marques, Manuela Ramos Silva, Ana Matos Beja, Abílio J. F. N. Sobrala In dibenzyl-3,6-dimethylpyrazine-2,5-dicarboxylate, each molecule possesses C _i symmetry. The molecules are assembled in chains via carbonyl···π interactions. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

N–H···π Interactions in Two Isomers of an Amino Group Containing <Emphasis Type="Italic">bis</Emphasis>-Phenol

Abstract  

Crystal structures of two bis-phenols namely bis-(3,5-dimethyl-2-hydroxyphenyl)(3-amino phenyl)methane 1 and bis-(3,5-dimethyl-4-hydroxyphenyl)(3-aminophenyl) methane 2 are determined. The compound 1 crystallises in monoclinic P2₁/c with a = 12.2579(16) ?, b = 16.0906(19) ?, c = 10.6664(13) ?, β = 115.417(7)°, V = 1900.2(4) ?³ whereas 2 crystallizes in monoclinic C2/c, a = 9.2538(2) ?, b = 18.6579(4) ?, c = 23.2725(5) ?, β = 98.796(2)°, V = 3970.89(15) ?³. The crystal lattice of both the compounds shows presence of N–H···π interactions but no O–H···π interactions.     

Crystal Packing of Potentially Mesomorphic Azobenezene Derivatives R1–C6H4–N=N–C6H4–R2 (R1, R2 = CH3COO,C2H5O; CH2=C(CH3)COO,C2H5; C6H13COO,C2H5O)

Crystallography Reports - The structure and thermal properties of azobenzene derivatives R1–C6H4–N=N–C6H4–R2, where R1/R2 = CH3COO/C2H5O (I), CH2=C(CH3)COO/C2H5 (II), or...     

Self-Assembly of N-1, 3-Dithiolan-2-ylidene-N′-[1-furan-2-yl-meth-(E)-ylidene]-hydrazine via Left-Handed Helical Chains of S···O Short Contacts and C–H···N Inter-Molecular Hydrogen-Bonds

Abstract  The title compound, N-1, 3-Dithiolan-2-ylidene-N′-[1-furan-2-yl-meth-(E)-ylidene]-hydrazine was synthesized via furfural with 2-hydrazono-1, 3-dithiolane and characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR, UV–Vis and single crystal XRD. The crystal belongs to orthorhombic, space group F2 ₁ 2 ₁ 2 ₁ with unit cell parameters a = 6.4035(9) ?, b = 11.8835(16) ?, c = 12.3809(17) ?, V = 942.1(2) ?³, Z = 4, Dc = 1.497, Mr = 212.28, μ = 0.523 mm⁻¹, F(000) = 440, R ₁  = 0.0243, and wR ₂  = 0.0602. The molecule is the anti-rotamer of the trans-isomer and every molecule forms zig-zag C(7) chains via C–H···N inter-molecular hydrogen-bond [H···N = 2.74 ?, C···N = 3.354(3) ? and C–H···N = 142°] running parallel to the [010] direction. At the same time many molecules self-assemble the left-handed spiral C(7) chains and inverse ones via the S···O short contacts [S···O = 3.1867(13) ?] along a axis. Index Abstract  The title compound was synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR, UV–Vis and single crystal XRD.      

Possibility of AlN growth using Li–Al–N solvent

The possibility of AlN growth using Li–Al–N solvent was investigated. Based on theoretical prediction, we selected Li₃N as a suitable nitrogen source for AlN growth. First, vapor phase epitaxy using Li₃N and Al as source materials was performed to confirm the following reaction on the growth surface: Li₃N+Al=AlN+3Li. The results suggest that the reaction proceeds to form AlN on the substrate under appropriate conditions. Next, AlN growth using Li–Al–N solvent was carried out. The Li–Al–N solvent was prepared by annealing of mixtures composed of Li₃N and Al. The results imply that AlN was formed under an Al-rich condition. Moreover, it was found that Li was swept out from AlN grains during growth. The results suggest that AlN growth using Li–Al–N solvent might be a key technology to obtain an AlN crystal boule.     

Regiospecificity of nucleotide–amino acid mating vs. water dynamics: a key to protein–nucleic acid assemblies: structure of unidecahydrated inosine-5′-monophosphate and L–glutamic acid (2C10H13N4O8P·C5H11NO4·11H2O) cocrystal at atomic resolution

The crystal structure of a unidecahydrated cocomplex between two Inosine-5-monophosphates (IMP) and one L-glutamic acid has been determined by X-ray crystallographic methods. The crystal belongs to the monoclinic space group P2₁ with cell dimensions a = 8.650(1), b = 21.900(1), c = 12.370(1) Å, and = 110.4°(9). This structure reveals extensive hydrogen bonding of glutamic acid to the nucleotide through direct and water-mediated interactions. The phosphate oxygens (O3B and O1B) seem to prefer nonspecific interaction with the functional sites of glutamic acid (OE2 ······O1B = 1.78 Å, NA······O3B = 2.73 Å, OH······O3B = 3.06 Å), whereas the bases prefer specific (O······N3B = 2.88 Å) binding. A solvent mediated N7A···W5···N7B hydrogen bond used for stabilization of the stacked purine bases has been observed as in other amino acid–nucleotide cocrystals. Glutamic acid occupies the same hydrophilic region in the nucleotide cocrystal as was found in glutamine–inosine monophosphate (Gln–IMP) and in serine–inosine monophosphate (Ser–IMP) complexes through substantial replacement of free and bound water molecules. This points to the dynamic hydrogen bonding nature of the water molecules and their stereochemical cooperation for the placement of amino acid through the polycoordination within the crystal.     

C–H···F Hydrogen-Bonded Assembly of Ni(II) and Cu(II) Complexes Generate 3D Supramolecular Frameworks

Abstract  Syntheses and X-ray structural characterizations of two new complexes [Ni(imi)₆](pfbz)₂ (1) and Cu(imi)₂(pfbz)₂ (2) (imi = imidazole, pfbz = pentafluorobenzoate) are reported. The first complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 9.180(2) ?, b = 9.742(3) ?, c = 11.466(3) ?, α = 76.947(18)°, β = 80.629(18)°, γ = 78.043(19)°, V = 970.0(4) ?³ and Z = 1. The second complex crystallizes in the triclinic space group P-1 with the crystal cell parameters a = 7.3250(12) ?, b = 7.6685(10) ?, c = 10.888(4) ?, α = 92.80(2)°, β = 101.92(2)°, γ = 115.038(12)°, V = 535.7(2) ?³ and Z = 1. Examination of the structures shows that both complexes form three-dimensional hydrogen bonded networks in which C–H···F hydrogen bonds play significant roles. Index Abstract   C–H···F Hydrogen-Bonded Assembly of Ni(II) and Cu(II) Complexes Generate 3D Supramolecular Frameworks Chun-Hua Ge, Xiao-Yan Zhang, Fang Yu, Ya-Nan Guo, Xiang-Dong Zhang* and Qi-Tao Liu C–H···F interactions link simple complexes to form intricate three-dimensional supramolecular networks.      

New Crystals in the CsHSO4–CsH2PO4–NH4H2PO4–H2O System

Crystallography Reports - The phase equilibria in the CsHSO4–CsH2PO4–NH4H2PO4–H2O four-component aqueous salt system have been studied. The crystallization ranges and solubilities...     

Synthesis,crystal structure and spectral studies of the complex [Ni(C3H4N2)4(H2O)2]·(C6H4COSO2N)2

The title compound has been synthesized and its crystal structure determined at room temperature.M _r =731.39, triclinic, space groupP¯1,a=9.020(3),b=11.280(7),c=7.784(2)Å,=97.05(4),=97.08(2), =105.32(4)°, U=748(1)ų,Z=1,D _calc.=1.624 g/cm³. The finalR is 0.030 for 3095 independent observed reflections withI3(I). The crystal structure consists of repeated [Ni(im)₄(H₂O)₂]²⁺ cations and noncoordinated saccharin anions. In the complex cation [Ni(im)₄(H₂O)₂]²⁺, Ni² is bonded to four N atoms from four imidazole molecules and two O atoms from two water molecules forming an approximately square octahedral stereochemistry. The d-d transition spectrum of the title compound is also reported and is explained perfectly with the scaling radial theory which was proposed by us.     

Altering Hydrophilic and Hydrophobic Region via O–H···O and C–H···O Hydrogen Bonds and van der Waals Forces in Solagenin 6- O -( β -d -quinovopyranoside) Methanol Solvate Monohydrate

Abstract  The title compound, C₃₃H₅₂O₈·CH₃OH·H₂O, isolated from Solanum torvum, consisted of a solagenin 6-O-(β-d-quinovopyranoside) molecule, a methanol solvate and a hydrate. The six-membered rings A, B, C, F and G have chair conformations. The five-membered ring D adopts a half-chair conformation and the ring E adopts an envelope conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis. The molecular packing appeared to be established by alternation of a hydrophilic region involving methanol molecules, water molecules and the β-d-quinovopyranoside of the steroid nucleus via the classic O–H···O hydrogen bonds and a hydrophobic region consisted by the other part of the steroid nucleus via weak C–H···O hydrogen bonds and van der Waals forces. Graphical Abstract  The molecular packing of the title compound appeared to be established by alternation of a hydrophilic region involving methanol molecules, water molecules and the β-d-quinovopyranoside of the steroid nucleus via the classic O–H···O hydrogen bonds and a hydrophobic region consisted by the other part of the steroid nucleus via weak C–H···O hydrogen bonds and van der Waals forces.      

Ni(C6H12N4)2SO4·4H2O晶体的生长、热学和光谱性质

六次甲基四胺(C6H12N4,HMTA)部分取代六水合硫酸镍(NSH)晶体结构中的配位水,合成Ni(C6H12N4)2SO4·4H2O(NSH-HMTA)晶体材料.采用称量法测定了NSH-HMTA晶体的溶解度曲线,应用水溶液降温法在温度区间56 ～44℃之间生长出6 mm×6 mm×2 mm尺寸的晶体,生长速度约为0.5 mm/d.通过等离子发射光谱分析所生长晶体中镍离子含量,X射线单晶衍射用于验证晶体的结构.采用热重法(TGA)和差热分析法(DTA)测定晶体脱水温度和分解温度分别为93℃、1 14℃.测量晶体的紫外-可见光谱特性,其紫外波段透过峰位于波长为307 nm处,比NSH晶体(287 nm)红移了约20 nm,HMTA与Ni2+配位提高了Ni2+的3A2g光谱项的能级,3A2g→3T1g(P)所需能量更低,导致吸收谱红移.     

Zn(II) and Cd(II) Complexes Extended Structures Sustained by Hydrogen Bonding, π–π and C–H···π Interactions

Abstract  

Two new complexes [Zn(sal)₂(tpt)]·H₂O(1), [Cd(sal)₂(tpt)(H₂O)]·H₂O(2), have been obtained through ligands tpt and Hsal, where Hsal is salicylic acid and tpt is 2,4,6-tripyridyl-1,3,5-triazine, reacting with Zn(II) and Cd(II) salts. Their structures are fully characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction. In complex 1, Zn(II) is coordinated by three N atoms and two O atom with a distorted square pyramidal coordination geometry. In 2, Each Cd(II) atom is seven-coordinated with a distorted pentagonal bipyramidal coordination geometry. The structural differences between two complexes show the influence of the coordinating orientation of metal ions. These two mononuclear complexes are further extended into three-dimensional structure via π–π, C–H···π and hydrogen bonding interactions. The solid state luminescent properties of complex 1, 2 are also reported.