Three-dimensional Supramolecular Architecture Research Articles

Synthesis, crystal structure and fluorescent sensing property of metal–organic frameworks with 1,3-di(1H-imidazol-4-yl)benzene and 1,4-phenylenediacetate

In this work, two new metal–organic frameworks (MOFs) based on 1,3-di(1H-imidazol-4-yl)benzene (L) and 1,4-phenylenediacetic acid (H2pda), namely [Ni(L)(pda)(H2O)] (1) and [Cd(L)(pda)] (2), have been achieved. MOFs 1 and 2 have distinct infinite one-dimensional (1D) chain structures, which are further linked together by hydrogen bonding interactions to give the eventual three-dimensional (3D) supramolecular architectures. Photoluminescence studies revealed that the Cd(II) MOF 2 shows strong emission at 346 nm upon excitation at 308 nm at room temperature. Furthermore, 2 can efficiently detecting acetone molecules, and Fe3+ and Cr2O72− ions via fluorescent quenching.

Metal-organic structures with formate and sulfate anions: Synthesis, crystallographic studies and hydrogen storage by PM7 and ONIOM

Six coordination complexes: {[H2NMe2][Co(CHO2)3]}n (1), [Co(bpy)(CHO2)2]n (2), [Cu(dmf)(CHO2)2]2 (3), {[H2NMe2][Cu(CHO2)3]}n (4), [H2NMe2]4[Fe4O2(dmf)4(SO4)6] (5) and [Co3(bpy)(SO4)3]n (6) have been efficaciously synthesized using solvothermal techniques and slow evaporation. Two compounds (5 and 6) containing the sulfate anion (SO42−) with iron (III) and cobalt (II) had never been described in the Cambridge Structural Database. In all complexes, the transition metal is hexacoordinated with a distorted octahedral geometry and displays a three-dimensional supramolecular architecture through hydrogen bonding interactions [NH⋯O]. Formate (CHO2−) and sulfate (SO42−) anions were very important to the assembly of the three-dimensional MOFs and can be regarded as the template for all structures. All metal-organic complexes were identified by single-crystal X-ray diffraction, elemental composition and Fourier-transform infrared spectroscopy. In this paper, we propose the PM7 and ONIOM calculations as two effective methods in the determination of hydrogen storage. The weight percentage (wt %) of the hydrogen stored in the small cavities of the PCPs studied were: (1) 1.03 wt %, (4) 1.01 wt %, (6) 0.28 wt %.

Crystal structure of (1,3-thia-zole-2-carboxyl-ato-κN)(1,3-thia-zole-2-carb-oxy-lic acid-κN)silver(I).

The linear two-coordinate silver (I) complex [Ag(C4H2NO2S)(C4H3NO2S)] or [Ag(2-Htza)(2-tza)] is reported (2-Htza = 1,3-thia-zole-2-carb-oxy-lic acid). The AgI ion is coordinated by two heterocyclic N atoms from two ligands in a linear configuration, forming a discrete coordination complex. There is an O-H⋯O hydrogen bond between 2-tza- and 2tzaH of adjacent complexes. The hydrogen atom is shared between the two oxygen atoms. This inter-action produces a hydrogen-bonded tape parallel to the [110] direction, which is augmented through inter-molecular C-H⋯O hydrogen-bonding inter-actions between the bound thia-zole groups. There is a further rather long Ag⋯O inter-action [2.8401 (13) Å, compared with a mean of 2.54 (11) Å for 23 structures in the CSD] that assembles these tapes into columns, between which there are C-H⋯π inter-actions, leading to the formation of a three-dimensional supra-molecular architecture.

Crystal structure of 4-[(3-meth-oxy-2-oxidobenzyl-idene)azaniumyl]-benzoic acid methanol monosolvate.

In the crystal of the title compound, C15H13NO4·CH3OH, the Schiff base mol-ecule exists in the zwitterionic form; an intra-molecular N-H⋯O hydrogen bond stabilizes the mol-ecular structure. The benzene rings are nearly co-planar, subtending a dihedral angle of 5.34 (2)°. In the crystal, classical O-H⋯O and weak C-H⋯O hydrogen bonds link the Schiff base mol-ecules and methanol solvent mol-ecules into a three-dimensional supra-molecular architecture. The crystal studied was refined as an inversion twin.

Crystal structure and Hirshfeld surface analysis of (succinato-κO)[N,N,N',N'-tetra-kis-(2-hy-droxy-eth-yl)ethyl-enedi-amine-κ5 O,N,N',O',O'']nickel(II) tetra-hydrate.

In the title compound, [Ni(C10H24N2O4)(C4H4O4)]·4H2O, the NiII cation is octa-hedrally coordinated by one O atom of the succinate anion and three O atoms and two N atoms from an N,N,N',N'-tetra-kis-(2-hy-droxy-eth-yl)ethyl-enedi-amine mol-ecule. In the crystal, mol-ecules are linked by O-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular architecture. Hirshfeld surface analyses and two-dimensional fingerprint plots were used to analyse the inter-molecular inter-actions present in the crystal, indicating that the most important contributions for the crystal packing are from H⋯H (63.3%) and H⋯O/O⋯H (34.5%) inter-actions.

2-Amino-5-chlorobenzophenone

The asymmetric unit of the title compound (systematic name: 2-benzoyl-4-chloroaniline), C13H10ClNO, contains four independent molecules with similar dihedral angles between the benzene rings [ranging from 53.7 (2) to 59.8 (2)°]. In the crystal, the molecules are linked by N—H...O hydrogen bonds into a three-dimensional supramolecular architecture.

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW12O40]4-: a synthetic, structural and computational investigation.

As an extension of our continued interest in the preparation of inorganic-organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ-1,10-phenanthroline-2,9-dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(C14H6N2O4)3(H2O)9(SiW12O40)]·12H2O}n or Na[Dy(PDA)(H2O)3]3[SiW12O40]·12H2O (1), and sodium aqua tris[tetraaqua(μ-4-hydroxypyridine-2,6-dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(C7H3NO5)3(H2O)13(SiW12O40)]·12H2O}n or Na(H2O)[Pr(pydc-OH)(H2O)4]3[SiW12O40]·12H2O (2) (in which H2PDA is 1,10-phenanthroline-2,9-dicarboxylic acid and H2pydc-OH is 4-hydroxypyridine-2,6-dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X-ray diffraction methods. Structural characterization by single-crystal X-ray diffraction reveals that these compounds consist of [SiW12O40]4- Keggin-type polyoxometalates (POMs), where a single {W3O13} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion-π interactions, resulting in three-dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both 1 and 2, and have been rationalized using molecular electrostatic potential (MEP) surface calculations.

Crystal structure and Hirshfeld surface analysis of tetra-aqua-bis-(isonicotinamide-κN 1)nickel(II) fumarate.

The reaction of NiCl2 with fumaric acid and isonicotinamide in a basic solution produces the title complex, [Ni(C6H6N2O)2(H2O)4](C4H2O4). The nickel(II) ion of the complex cation and the fumarate anion are each located on an inversion centre. The NiII ion is coordinated octa-hedrally by four water O atoms and two N atoms of isonicotinamide mol-ecules. The fumarate anion is linked to neighbouring complex cations via Owater-H⋯Ofumarate hydrogen bonds. In the crystal, the complex cations are further linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular architecture. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyse the inter-molecular inter-actions present in the crystal and indicate that the most important contributions for the crystal packing are from H⋯O/O⋯H (41.8%), H⋯H (35.3%) and H⋯C/C⋯H (10.2%) inter-actions.

Crystal structure and Hirshfeld surface analysis and of 2-ammoniumylmeth-yl-1H-benzimidazol-3-ium chloride monohydrate.

The asymmetric unit of the title compound, C8H11N3 2+·2Cl-·H2O, contains three organic cations, six chloride anions and three water mol-ecules of crystallization, which are connected by extensive hydrogen-bonding inter-actions into a three-dimensional supra-molecular architecture. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (37.4%), Cl⋯H/H⋯Cl (35.5%), C⋯H/H⋯C (9.5%) and C⋯C (6.9%) inter-actions.

Sponge-Like Water De-/Ad-Sorption versus Solid-State Structural Transformation and Colour-Changing Behavior of an Entangled 3D Composite Supramolecuar Architecture, [Ni₄(dpe)₄(btc)₂(Hbtc)(H₂O)₉]·3H₂O.

An entangled composite compound, [Ni4(dpe)4(btc)2(Hbtc)(H2O)9]·3H2O (1), where H3btc = 1,3,5-benzenetricarboxylic acid and dpe = 1,2-bis(4-pyridyl)ethane, has been synthesized and structurally characterized. Single-crystal structural determination reveals that compound 1 consists of four coordination polymers (CPs), with two two-dimensional (2D) (4,4) layered metal-organic frameworks (MOFs) of [Ni(dpe)(Hbtc)(H2O)] and [Ni(dpe)(btc)(H2O)]− anion, and two one-dimensional (1D) polymeric chains of [Ni(dpe)(btc)(H2O)3]− anion and [Ni(dpe)(H2O)4]2+ cation, respectively. The three-dimensional (3D) supramolecular architecture of 1 is constructed via the inter-penetration of inter-digited, double-layered, 2D rectangle-grid MOFs by two 1D coordination polymeric chains, and tightly entangled together via the combination of inter-CPs π–π stacking and hydrogen bonding interactions. The ad-/de-sorption isotherms of 1 for water displays a hysteresis profile with a maximum adsorption of 17.66 water molecules of per molecule unit at relative P/P0 < 0.89. The reversible de-/re-hydration processes in 1 monitored by cyclic water de-/ad-sorption TG analysis and PXRD measurements evidence a sponge-like water de-/ad-sorption property associated with a thermal-induced solid-state structural transformation. The magnetic property of 1 suggests that the ferromagnetic coupling might refer to a stronger inter-Ni(II) interaction, which could be along the btc3− or Hbtc2− ligands; the antiferromagnetic coupling corresponding to the weaker inter-Ni(II) interactions, which could be the dpe ligands for the 2D framework.

Synthesis, crystal structure and Hirshfeld surface analysis of a 1D coordination polymer catena-poly[[di-aqua-bis-(nicotinamide-κN1)nickel(II)]-μ-fumarato-κ2O1:O4

The reaction of NiCl2 with fumaric acid and nicotinamide in basic solution produces the title polymeric complex, [Ni(C4H2O4)(C6H6N2O)2(H2O)2] n . The NiII cation, located on an inversion centre, is coordinated by two O atoms of the fumarate dianions, two N atoms from nicotinamide ligands and two water mol-ecules in a distorted octa-hedral fashion. In the crystal, the fumarate dianions bridge the NiII cations, forming polymeric chains propagating along the [101] direction; the polymeric chains are further linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular architecture. Hirshfeld surface analyses and two-dimensional fingerprint plots were used to analyse the inter-molecular inter-actions present in the crystal, indicating that the most important contributions for the crystal packing are from H⋯O/O⋯H (35.9%), H⋯H (31.7%) and C⋯C (10.4%) inter-actions.

A supramolecular uranyl phosphonate [BTEA]2[(UO2)2(1,3-pbpH2)2F2]: Synthesis, structure, and spectroscopic characterization

In this work, a uranyl phosphonate [BTEA]2[(UO2)2(1,3-pbpH2)2F2] (1) (1,3-pbp = 1,3-phenylenebis(phosphonic acid), BTEA = benzyltriethylammonium cation) has been synthesized hydrothermally and characterized by single crystal X-ray diffraction, showing one-dimensional chain structure of uranium phosphonate which is isolated by BTEA cations and achieve three-dimensional supramolecular architecture by non-covalent interactions. In addition, powder X-ray diffraction, thermal stability, UV absorption, temperature dependent fluorescence, Infrared, and Raman spectroscopies have been performed.

Influence of different metal ions on the assembly, structures, and properties of two complexes based on the semi-rigid bis(pyridyl)-bis(amide) ligand and 4,4′-oxybis(benzoic acid)

Abstract Two transitional metal complexes, [Zn(oba)(3-bpcd)] n (1) and [Cd(oba)(3-bpcd)0.5] n (2) [H2oba= 4,4′-oxybis(benzoic acid), 3-bpcd=N,N′-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide], have been hydrothermally synthesized and structurally characterized by elemental analyses, infrared spectra, powder X-ray diffraction, thermogravimetric and single-crystal X-ray diffraction. Complex 1 possesses a three-fold interpenetrating network based on layers with a 4-connected sql topology. Complex 2 is a layered framework constructed by the oba anions and 3-bpcd ligands, which represents a binodal (3,4)-connected {62.10}{6} topology. The adjacent layers of complex 2 are further linked by hydrogen bonding interactions to build a three-dimensional supramolecular architecture. The differences of metal ions in coordination modes show a significant effect on the final structures of the Zn(II)/Cd(II) complexes. The photocatalytic activities and the fluorescence sensing properties of complexes 1 and 2 were investigated.

Synthesis of 1,1′-(2,6-dihydroxy-2,6-dimethyl-3,7-dioxabicyclo [3.3.1]nonane-1,5-diyl)diethanone dihydrate: crystal structure and quantitative analysis of molecular interaction via molecular electrostatic potential and Hirshfeld surface analysis

ABSTRACTA new bicyclononane derivative, 1,1′-(2,6-dihydroxy-2,6-dimethyl-3,7-dioxa-bicyclo[3.3.1]nonane-1,5-diyl) diethanone dihydrate (1), has been synthesized and structurally characterized by the single-crystal X-ray diffraction technique. In the solid-state structure of the compound, molecular units are interlinked via strong hydrogen bonds as well as non-classical weak hydrogen bonds leading to a three-dimensional supramolecular architecture. Solid-state DFT optimized geometry in (1) agrees closely with that obtained from the crystallographic analysis. The C(dioxa-bicyclononane)–H … O(hydroxy) hydrogen bond generates cyclic (10) ring in (1) which are further connected through C–H … O and O–H … O hydrogen bonds into a three-dimensional framework in the title compound. Hirshfeld surface analysis of the title compound along with some related nonane derivatives retrieved from the Cambridge Structural Database shows that the most of the Hirshfeld surface area in this class of compounds is due to H … H and O … H interactions.

Synthesis, structural characterization and luminescence properties of 1-carboxymethyl-3-ethylimidazolium chloride.

A microcrystalline carboxyl-functionalized imidazolium chloride, namely 1-carboxymethyl-3-ethylimidazolium chloride, C7H11N2O2+·Cl-, has been synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform IR spectroscopy (ATR-FT-IR), single-crystal X-ray diffraction, thermal analysis (TGA/DSC), and photoluminescence spectroscopy. In the crystal structure, cations and anions are linked by C-H...Cl and C-H...O hydrogen bonds to create a helix along the [010] direction. Adjacent helical chains are further interconnected through O-H...Cl and C-H...O hydrogen bonds to form a (10-1) layer. Finally, neighboring layers are joined together via C-H...Cl contacts to generate a three-dimensional supramolecular architecture. Thermal analyses reveal that the compound melts at 449.7 K and is stable up to 560.0 K under a dynamic air atmosphere. Photoluminescence measurements show that the compound exhibits a blue fluorescence and a green phosphorescence associated with spin-allowed (1π←1π*) and spin-forbidden (1π←3π*) transitions, respectively. The average luminescence lifetime was determined to be 1.40 ns for the short-lived (1π←1π*) transition and 105 ms for the long-lived (1π←3π*) transition.

Synthesis, Structure, and Band Gap of a Novel Inorganic–Organic Hybrid Material Based on Antimony Halide and Organoamine

Using an organoamine, 2,5-bis (1-imidazoly) pyridine (L), a novel inorganic-organic hybrid material based on antimony halide formulated as {(CH3)2L}2+{(Sb4Cl8I8)0.5}2–(1) was synthesized in situ via solvothermal technique and characterized by the single-crystal X-ray diffraction. During the synthesis, the organoamine L was transformed in situ into the imidazolium ion, {(CH3)2L}2+. In the compound 1, four Sb(III) ions are linked by two $${u_{{3^ - }}}$$ I– and four u $${u_{{2^ - }}}$$ I– ligands into a (Sb4I8Cl8)4–unit, in which eight Cl–ions and two I–ions act as the terminal ligands. The uncoordinated {(CH3)2L}2+ organoamine moieties are linked with the (Sb4I8Cl8)4– clusters via H bonds into three-dimensional (3D) supramolecular architecture. The band structure calculation shows that the compound has an indirect band gap of 2.253 eV.

Crystal structure of (S)-5-chloro-N-({2-oxo-3-[4-(3-oxomorpholin-4-yl)phen-yl]oxazolidin-5-yl}meth-yl)thio-phene-2-carboxamide.

The asymmetric unit of the crystal of the title compound (common name rivaroxaban), C19H18ClN3O5, contains two rivaroxaban mol-ecules with different conformations; the C-C-N-C torsion angles between the oxazolidine and thio-phene rings are -171.1 (7) and -106.8 (9)° in the two independent mol-ecules. In the crystal, classical N-H⋯O hydrogen bonds and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular architecture.

Copper-based metal coordination complexes with Voriconazole ligand: Syntheses, structures and antimicrobial properties

Three new chiral metal coordination complexes, namely, [Cu(FZ)2(CH3COO)2(H2O)]·2H2O (1), [Cu(FZ)2(NO3)2] (2), and [Cu2(FZ)2 (H2O)8](SO4)2·4H2O (3) [FZ = (2R,3S)-2-(2,4-difluorophenyl)-3-(5-fluoro-4-pyrimidiny)-1-(1H-1,2,4-triazol-1-yl)-2-butanol) (Voriconazole)] have been obtained by the reaction of Cu(II) salts and the free ligand FZ at room temperature. Complexes 1–3 were structurally characterized by X-ray single-crystal diffraction, IR, UV–vis, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). Complex 1 crystallizes in the chiral space group C2, which exhibits a mono-nuclear structure. Both complexes 2 and 3 display a one-dimensional (1D) tape structure, which crystallize in chiral space group P21212 and P212121, respectively. Among these complexes, there exist a variety of hydrogen bonds and stacking interactions, through which a three-dimensional supramolecular architecture will be generated. Compared with the standard (Voriconazole), these Cu-based complexes show the more potent inhibiting efficiency against the species of Candida and Aspergillus. Moreover, among these complexes, complex 1 shows the most excellent efficiency.

Crystal structure of a zigzag CoII coordination polymer: catena-poly[[di-chlorido-bis-(methanol-κO)cobalt(II)]-μ-bis-(pyridin-3-ylmeth-yl)sulfane-κ2N:N'

Reaction of bis-(pyridin-3-ylmeth-yl)sulfane (L) with cobalt(II) chloride in methanol led to the formation of the title coordination polymer, [CoCl2(C12H12N2S)(CH3OH)2] n , in which the CoII cation lies on a crystallographic inversion centre and the S atom of the L ligand lies on a twofold rotation axis. Each CoII ion is coordinated by two pyridine N atoms from two bridging L ligands, two O atoms from methanol mol-ecules and two chloride anions, all inversion-related. The complex unit has an elongated octa-hedral geometry, in which N2O2 donor atoms occupy the equatorial positions and two chloride anions occupy the axial positions. Each L ligand links two CoII ions, forming an infinite zigzag chain propagating along the c-axis direction and further stabilized by O-H⋯Cl hydrogen bonds between the methanol mol-ecules and the chloride anions. Adjacent chains in the structure are connected by inter-molecular C-H⋯Cl hydrogen bonds, resulting in the formation of a three-dimensional supra-molecular architecture.

Sonochemical synthesis of a new nano-sized barium coordination polymer and its application as a heterogeneous catalyst towards sono-synthesis of biodiesel

A new nano-sized barium coordination polymer, {(bipyH)[Ba2(pydc)2(Hpydc)(H2O)2]}n·nH2O (1), (bipy = 4,4′-bipyridine and H2pydc = pyridine-2,6-dicarboxylic acid), has been sonochemically synthesized and fully characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy, thermogravimetric analysis (TGA) and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction and it was shown that this compound consists of 1D anionic coordination polymers and bipyH+ cationic species that construct a three-dimensional supramolecular architecture via non-covalent interactions i.e. ion-pairing and hydrogen bonding. The role of compound 1 as a heterogeneous catalyst in the production of biodiesel was also investigated. A full conversion of soybean oil to biodiesel was accomplished in an exceptionally short timeframe through an ultrasonic-assisted transesterification process in the presence of compound 1.