Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

2018 ◽  
Vol 74 (11) ◽  
pp. 1403-1412 ◽  
Author(s):  
Tao Qin ◽  
Zhe Feng ◽  
Jie Yang ◽  
Xuan Shen ◽  
Dunru Zhu
Keyword(s):  
Solid State ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
X Ray Crystallography ◽  
Circularly Polarized Luminescence ◽  
Metal Organic ◽  
First Time ◽  
Green Photoluminescence ◽  
Hydrogen Bonded

The design and preparation of chiral metal–organic frameworks (CMOFs) from achiral ligands are a big challenge. Using 3-nitro-4-(pyridin-4-yl)benzoic acid (HL) as a new linker, a total of eight chiral lanthanide–organic frameworks (LOFs), namely poly[diaquatris[μ2-3-nitro-4-(pyridin-4-yl)benzoato-κ2 O:O′]lanthanide(III)], L- and D-[Ln(C12H7N2O4)3(H2O)2] n [(1), Ln = Eu; (2), Ln = Gd; (3), Ln = Dy; (4), Ln = Tb], were hydrothermally synthesized without chiral reagents and determined by X-ray crystallography. Crystal structure analyses show that L-(1)–(4) crystallize in the hexagonal P65 space group and are isomorphous and isostructural, while the enantiomers D-(1)–(4) crystallize in the hexagonal P61 space group. All LnIII ions are octacoordinated by six carboxyl O atoms of six 3-nitro-4-(pyridin-4-yl)benzoate ligands and two water molecules in a dodecahedral geometry. A one-dimensional neutral helical [Ln2(CO2)3] n chain is observed in (1)–(4) as a chiral origin. These helical chains are further interconnected via directional hydrogen-bonding interactions between pyridyl groups and water molecules to construct a three-dimensional (3D) homochiral network with hex topology. The present CMOF structure is the first chiral 3D hydrogen-bonded hex-net and shows good water stability. Solid-state circular dichroism (CD) signals revealed that (1)–(4) crystallized through spontaneous resolution. Furthermore, (1) and (4) display a strong red and green photoluminescence at room temperature, respectively, but their intensities reduce to almost half at 200 °C. Notably, upon excitation under visible light (463 nm), a circularly polarized luminescence (CPL) of (1) in the solid state is observed for the first time, with a g lum value of 2.61 × 10−2.

Inclusion Compounds of Thiourea and Peralkylated Ammonium Salts. VI. Hydrogen-Bonded Host Lattices Constructed From Thiourea and Anions of Oxalic Acid and Fumaric Acid

1997 ◽  
Vol 53 (2) ◽  
pp. 252-261 ◽  
Author(s):  
Q. Li ◽  
T. C. W. Mak
Keyword(s):  
Crystal Structure ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Single Column ◽  
Host Lattices ◽  
Type Crystal ◽  
Hydrogen Bonded

New inclusion complexes tetra-n-butylammonium hydrogen oxalate–thiourea (1/2), (n-C4H9)4N+.HC2O4 −.2[(NH2)2CS] (1), tetramethylammonium hydrogen fumarate–thiourea (1/1), (CH3)4N+.HC4H2O4 −.(NH2)2CS (2), di(tetraethylammonium) fumarate–thiourea (1/2), [(C2H5)4N+]2.C4H2O4 2−.2[(NH2)2CS] (3) and tetra-n-propylammonium hydrogen fumarate–thiourea–water (1/1/2), (n-C3H7)4N+.HC4H2 O4 −.(NH2)2CS.2H2O (4) have been prepared and characterized by X-ray crystallography. Crystal data, Mo Kα radiation: (1), space group P21/n, a = 8.854 (6), b = 9.992 (3), c = 32.04 (2) Å, β = 97.34 (3), Z = 4, R F = 0.055 for 2261 observed data; (2), space group P\overline 1, a = 6.269 (2), b = 8.118 (4), c = 14.562 (8) Å, α = 104.79 (4), β= 91.72 (4), γ = 101.30 (4)°, Z = 2, R F = 0.078 for 1543 observed data; (3), space group P21/n, a = 11.340 (2), b = 9.293 (6), c = 14.619 (2) Å, β = 102.41 (2)°, Z = 2, R F = 0.050 for 1856 observed data; (4), space group P2/n, a = 16.866 (4), b = 8.311  (1), c = 17.603 (2) Å, β = 104.94 (1)°, Z = 4, R F = 0.048 for 2785 observed data. In the crystal structure of (1) the tetra-n-butylammonium ions are sandwiched between puckered layers, which are constructed from thiourea-hydrogen oxalate ribbons. In the crystal structure of (2), zigzag O--H...O and C--H...O hydrogen-bonded hydrogen fumarate ribbons are linked by thiourea dimers to form a wide puckered ribbon and the crystal structure is built of a packing of these thiourea–anion composite ribbons and the cationic columns. In the layer-type crystal structure of (3) a series of thiourea–fumarate layers match the (002) planes and the (C2H5)4N+ cations occupy the intervening space. In the crystal structure of (4) the thiourea, hydrogen fumarate ions and water molecules are connected by hydrogen bonds to form wide puckered ribbons, which are crosslinked to generate a three-dimensional host framework containing open channels aligned parallel to the a axis, with the tetra-n-propylammonium cations accommodated in a single column within each channel.

scholarly journals Molecular Recognition in Proton-Transfer Compounds of Brucine with Achiral Substituted Salicylic Acid Analogues

2006 ◽  
Vol 59 (5) ◽  
pp. 320 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White
Keyword(s):  
Proton Transfer ◽  
Three Dimensional ◽  
Water Molecules ◽  
Sulfosalicylic Acid ◽  
X Ray ◽  
X Ray Crystallography ◽  
Guest Species ◽  
Substituted Benzoic Acids ◽  
Proton Transfer Compounds ◽  
Hydrogen Bonded

The 1:1 proton-transfer brucinium compounds from the reaction of the alkaloid brucine with 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 5-sulfosalicylic acid, namely anhydrous brucinium 5-nitrosalicylate (1), brucinium 3,5-dinitrosalicylate monohydrate (2), and brucinium 5-sulfosalicylate trihydrate (3) have been prepared and their crystal structures determined by X-ray crystallography. All structures further demonstrate the selectivity of brucine for meta-substituted benzoic acids and comprise three-dimensional hydrogen-bonded framework polymers. Two of the compounds (1 and 3) have the previously described undulating brucine sheet host-substructures which incorporate interstitially hydrogen-bonded salicylate anion guest species and additionally in 3 the water molecules of solvation. The structure of 2 differs in having a three-centre brucinium–salicylate anion bidentate N+–H···O(carboxyl) hydrogen-bonding association linking the species through interstitial associations involving also the water molecules of solvation. A review of the crystallographic structural literature on strychnine and brucine is also given.

Phosphonopropionic acid as a building block in supramolecular chemistry: salts with organic diamines

2003 ◽  
Vol 59 (2) ◽  
pp. 248-262 ◽  
Author(s):  
Katharine F. Bowes ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Chemistry ◽  
Three Dimensional ◽  
Supramolecular Structures ◽  
Water Molecules ◽  
Two Dimensional ◽  
Phosphonoacetic Acid ◽  
Space Group ◽  
Hydrated Salt ◽  
Hydrogen Bonded

The structures of seven salts formed by phosphonopropionic acid with organic diamines are reported; in these salts, the hydrogen-bonded substructures formed by the anions can be zero-, one- or two-dimensional, while the overall hydrogen-bonded supramolecular structures are three-dimensional. The 1:1 adduct, compound (1), formed between 1,2-bis(4′-pyridyl)ethene and phosphonopropionic acid is a salt, [{(C12H10N2)H2}2+]·[(C12H10N2)]·[(C3H6O5P)−]2, in which both diamine components lie across centres of inversion in space group P21/c. The anions form hydrogen-bonded head-to-head dimers, and these are linked by the two diamine units into sheets, which are themselves linked by C—H...O hydrogen bonds. With 2,2′-dipyridylamine the acid forms the hydrated salt [{(C10H9N3)H}+]·[(C3H6O5P)−]·H2O (2), in which all components are disordered with occupancy 0.5 in space group Fmm2. The anions form head-to-tail dimers, which are linked into sheets by the cations, and the sheets are linked into a three-dimensional framework by the water molecules. The piperazine salt [{(C4H10N2)H2}2+]·[(C3H5O5P)2−] (3) contains simple anion chains linked into a three-dimensional framework by the two independent cations, both of which are centrosymmetric. In the hydrated salt formed by N,N′-dimethylpiperazine, [{(MeNC4H8NMe)H2}2+]·[(C3H6O5P)−]2·(H2O)2 (4), head-to-tail anion chains combine with the water molecules to form a three-dimensional framework, which encloses voids that contain the cations. In the 4,4′-bipyridyl adduct [{(C10H8N2)H0.72}0.72+]·[{(H0.5O)3PCH2CH2COOH0.78}0.72−] (5), there is extensive disorder of the H atoms that are bonded to N and O atoms, and the anion chains are linked by the cations into sheets, which are themselves linked by C—H...O hydrogen bonds. In the 1:2 adduct formed with 1,2-bis(4′-pyridyl)ethane, [{(C12H12N2)H2}2+]·[(C3H6O5P)−]2 (6), where the cation lies across an inversion centre, the anions form molecular ladders. These ladders are linked into sheets by the cations, which are themselves linked by C—H...O hydrogen bonds. In the methanol-solvated salt formed with 2,6-dimethylpiperazine, [{(C6H14N2)H2}2+]·[(C3H6O5P)−]2· (CH4O)0.34 (7), the anions form sheets that are linked into a three-dimensional framework by the cations. The supramolecular structures are compared with those of analogous salts formed by phosphonoacetic acid.

scholarly journals Hydrogen-bonding patterns in 2,2-bis(4-methylphenyl)hexafluoropropane pyridinium and ethylenediammonium salt crystals

2020 ◽  
Vol 76 (5) ◽  
pp. 742-746 ◽  
Author(s):  
Haruki Sugiyama
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
One Dimensional ◽  
Salt Crystals ◽  
Bonding Patterns ◽  
Hydrogen Bonded

The crystal structures of two salt crystals of 2,2-bis(4-methylphenyl)hexafluoropropane (Bmphfp) with amines, namely, dipyridinium 4,4′-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)dibenzoate 4,4′-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)dibenzoic acid, 2C5H6N+·C17H8F6O4 2−·C17H10F6O4, (1), and a monohydrated ethylenediammonium salt ethane-1,2-diaminium 4,4′-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)dibenzoate monohydrate, C2H10N2 2+·C17H8F6O4 2−·H2O, (2), are reported. Compounds 1 and 2 crystallize, respectively, in space group P21/c with Z′ = 2 and in space group Pbca with Z′ = 1. The crystals of compound 1 contain neutral and anionic Bmphfp molecules, and form a one-dimensional hydrogen-bonded chain motif. The crystals of compound 2 contain anionic Bmphfp molecules, which form a complex three-dimensional hydrogen-bonded network with the ethylenediamine and water molecules.

scholarly journals Tris(2,2′-bipyridine)iron(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) dihydrate: chiral hydrogen-bonded frameworks interpenetrate in three dimensions

2014 ◽  
Vol 70 (5) ◽  
pp. 465-469 ◽  
Author(s):  
Zouaoui Setifi ◽  
Fatima Setifi ◽  
Habib Boughzala ◽  
Adel Beghidja ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Three Dimensional ◽  
Three Dimensions ◽  
Water Molecules ◽  
Space Group ◽  
Rotation Axes ◽  
Hydrogen Bonded

In the title compound, [Fe(C10H8N2)3](C9H5N4O)2·2H2O, the chiral cations lie across twofold rotation axes in the space group C2/c. The anions and the water molecules are linked by two independent O—H...N hydrogen bonds to form C 2 2(8) chains, and these chains are linked by the cations via C—H...N and C—H...O hydrogen bonds to form two interpenetrating three-dimensional frameworks, each of which contains only one enantiomeric form of the chiral cation.

Charge-assisted hydrogen bonding in three diaminobenzene salts

2018 ◽  
Vol 74 (12) ◽  
pp. 1725-1731 ◽  
Author(s):  
Patricia L. Zick ◽  
David K. Geiger
Keyword(s):  
Hydrogen Bonding ◽  
Density Functional ◽  
Rational Design ◽  
Three Dimensional ◽  
Water Molecules ◽  
Functional Theory ◽  
Space Group ◽  
Hydrogen Bonding Interactions ◽  
Significant Difference ◽  
Hydrogen Bonded

Hydrogen-bonding interactions play an important role in the rational design of crystal systems with desirable architectures. The crystal structures of benzene-1,2-diaminium sulfate sesquihydrate, C6H20N2 2+·SO4 2−·1.5H2O, (1), benzene-1,3-diaminium tetrachloridozincate(II), (C6H20N2)[ZnCl4], (3), and 3-aminoanilinium perchlorate, C6H9N2 +·ClO4 −, (4), are reported. Hydrated salt (1) is a polymorph (space group C2/c) of a previously reported [Anderson et al. (2011). Cryst. Growth Des. 11, 4904–4919] crystalline modification of salt (2) (space group P21/c). The contents of the asymmetric unit of (2) are twice that of (1). In each, the extended structures exhibit hydrogen bonds, resulting in chains of ions and hydrogen-bonded rings with an R 4 4(8) motif involving water molecules. Hirshfeld surface analysis shows that a significant difference between the two is the degree of C...C interaction. Salt (3) exhibits an extended structure having hydrogen-bonded rings and parallel benzene rings, with a centroid-to-centroid separation of 3.860 (2) Å. Salt (4) displays a three-dimensional superstructure that results from linked planes of ions joined by an extensive hydrogen-bonding network involving N—H...O, N—H...N and C—H...π interactions. The cation–anion and N—H...N interaction energies in (4), determined using density functional theory (DFT), show significantly stronger aminium–perchlorate than amine–perchlorate interactions.

Clathrates with Three-Dimensional Host Structures of Hydrogen-Bonded Pentaborate [B5O6(OH)4]- Ions: Pentaborates with the Cations NMe4+, NEt4+, NPhMe3+ and pipH+ (pipH+ = Piperidinium)

1993 ◽  
Vol 48 (7) ◽  
pp. 978-985 ◽  
Author(s):  
Michael Wiebcke ◽  
Clemens C. Freyhardt ◽  
Jürgen Felsche ◽  
Günter Engelhardt
Keyword(s):  
Rectangular Cross Section ◽  
Three Dimensional ◽  
Organic Cations ◽  
Water Molecules ◽  
Space Group ◽  
X Ray ◽  
Structure Topology ◽  
Guest Species ◽  
Gas Atmosphere ◽  
Hydrogen Bonded

X-ray structure analyses of crystalline [NMe4][B5O6(OH)4] · nH2O with n ≈ 0.25-0.50 (1), [NEt4][B5O6(OH)4] (2), [NPhMe3][B5O6(OH)4] (3), and [pipH][B5O6(OH)4] (4) reveal that these materials are novel clathrates with closely related three-dimensional host structures built up of hydrogen-bonded oligomeric pentaborate [B5O6(OH)4]- ions. The organic cations and water molecules (in 1) occupy as guest species large straight channel-like voids of nearly rectangular cross-section. Compound 1 crystallizes monoclinically with space group P2,/c (Z = 4); the compounds 2,3 and 4, which possess the same host-structure topology, crystallize triclinically with space group P1̄ (Z = 2). 11B-MAS NMR spectra allow the detection of small angular distortions in the pentaborate anions caused by the specific hydrogen bonding in the host frameworks. Upon heating the compounds on a thermobalance in a dynamic inert gas atmosphere dehydration occurs at temperatures of 563 K (1), 543 K (2), 558 K (3) and 523 K (4) before degradation of the organic cations starts at temperatures of 633 K (1), 623 K (2), 623 K (3) and 613 K (4).

scholarly journals Protonation sites and hydrogen bonding in mono-hydrobromide salts of two N,4-diheteroaryl 2-aminothiazoles

2021 ◽  
Author(s):  
Denise Böck ◽  
Andreas Beuchel ◽  
Richard Goddard ◽  
Adrian Richter ◽  
Peter Imming ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Water Molecules ◽  
Monoclinic Space Group ◽  
Intermolecular Hydrogen Bonding ◽  
Molecular Conformations ◽  
Space Group ◽  
Hydrogen Bonded

AbstractThe synthesis and structural characterization of N-(6-methoxypyridin-3-yl)-4-(pyridin-2-yl)thiazol-2-amine mono-hydrobromide monohydrate (3) and N-(6-methoxypyridin-3-yl)-4-(pyrazin-2-yl)thiazol-2-amine mono-hydrobromide 0.35 methanol solvate (4) are reported. The crystal structures of 3 (monoclinic, space group P21/n, Z = 4) and 4 (monoclinic, space group, C2/c, Z = 8) feature N,4-diheteroaryl 2-aminothiazoles showing similar molecular conformations but different sites of protonation and thus distinctly different intermolecular hydrogen bonding patterns. In 3, Namine–H⋯Br−, N+pyridine–H⋯Owater, and Owater–H⋯Br− hydrogen bonds link protonated N-(6-methoxypyridin-3-yl)-4-(pyridin-2-yl)thiazol-2-amine and water molecules and bromide anions into a three-dimensional hydrogen-bonded network, whereas intermolecular N+methoxypyridine–H⋯Npyrazine hydrogen bonds result in hydrogen-bonded zigzag chains of protonated N-(6-methoxypyridin-3-yl)-4-(pyrazin-2-yl)thiazol-2-amine molecules in 4.

Bis(1-phenyl-1-propyne) complexes of tungsten(II): crystal structures of [WI2(CO)(NCR)(η2-MeC2Ph)2] (R = Me, Et, or Ph)

2001 ◽  
Vol 79 (3) ◽  
pp. 263-271
Author(s):  
Paul K Baker ◽  
Michael GB Drew ◽  
Deborah S Evans
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Crystal Structures ◽  
Octahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Alkyne Complexes ◽  
First Time

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

Gold(I) Complexes Bearing P∩N-Ligands: An Unprecedented Twelve-membered Ring Structure Stabilized by Aurophilic Interactions

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1513-1524 ◽  
Author(s):  
Uwe Monkowius ◽  
Manfred Zabel ◽  
Michel Fleck ◽  
Hartmut Yersin
Keyword(s):  
Solid State ◽  
Ring Structure ◽  
Phosphine Ligands ◽  
X Ray Crystallography ◽  
Aggregation Pattern ◽  
Elemental Analyses ◽  
High Yields ◽  
First Time ◽  
Solid State Structures ◽  
Aurophilic Interactions

The P∩N-ligands Ph2Pqn, 1, Ph2 Piqn, 2, Ph2 Ppym, 3, and the As∩N-ligands Ph2Asqn, 4, Ph2Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have been synthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesis of gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chlorogold complexes Ph2RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph2RAs-Au-Cl (R = qn, 9; iqn, 10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF4 provided the complexes [(Ph2Piqn)Au]BF4, 11, [(Ph2Ppym)Au]BF4, 12, and [(Ph2Piqn)Au(tht)]BF4, 14. For comparison, the previously reported complex [(Ph2Ppy)Au]BF4 (py = pyridine), 13, was re-investigated. The compounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. In addition, the solid-state structures of 2, 3, 6, 7, 9 - 14 have been determined by X-ray crystallography. The chloro-gold compounds crystallize in the common rod-like structure known from R3EAuCl (R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all cases the phosphine acts as a monodentate ligand. In the solid state compounds 11 - 13 feature an unprecedented cyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinated by the bridging phosphine ligands forming a cyclic (P-Au-N)3 arrangement. The resulting twelvemembered ring is further stabilized by Au · · · Au interactions. Due to the presence of these Au · · · Au contacts, 11 - 13 are emissive in the solid state but not in solution

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