Cation-π Interactions in the Solid State: Crystal Structures of M+(benzene)2CB11Me12- (M = Tl, Cs, Rb, K, Na) and Li+(toluene)CB11Me12-

1999 ◽  
Vol 64 (6) ◽  
pp. 1001-1012 ◽  
Author(s):  
Benjamin T. King ◽  
Bruce C. Noll ◽  
Josef Michl
Keyword(s):  
Solid State ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Electrostatic Interactions ◽  
Van Der Waals ◽  
X Ray Diffraction ◽  
X Ray ◽  
Π Interactions ◽  
Toluene Molecule ◽  
Polymeric Chains

In these crystal structures, the relatively weak electrostatic interactions between the bulky CB11Me12- anion and the title cations permit cation-π interactions in the solid state. In all cases, single-crystal X-ray diffraction analysis reveals η6-arene-cation interactions within 10% of the expected van der Waals distance. The Tl+, Cs+, Rb+, and K+ structures are isomorphous, with the benzene molecules sandwiching the cation and four anions equatorially disposed in a nearly square arrangement. Both the cation and the near-square of closest anions are positioned to interact favorably with the local dipoles of benzene. The smaller Na+ crystallizes in polymeric chains with a nearly tetrahedrally coordinated cation in van der Waals contact with two anions and two benzene molecules in a tilted-sandwich arrangement. The Li+ structure possesses two motifs, a simple van der Waals sandwich of a toluene molecule and an anion, and chains of half-occupied toluene-Li complexes on inversion centers between anions. The simple van der Waals model is reasonably accurate for the cation-arene distances, only slightly underestimating the separation (2-10% deviation), with worse agreement for the smaller cations.

Polymorphism of Trimeric Perfluoro-ortho-phenylene Mercury, [Hg(o-C6F4)]3

2004 ◽  
Vol 59 (11-12) ◽  
pp. 1483-1487 ◽  
Author(s):  
Mason R. Haneline ◽  
François P. Gabbaï
Keyword(s):  
Single Crystal ◽  
Electrostatic Interactions ◽  
Van Der Waals ◽  
Relativistic Effects ◽  
Van Der Waals Interactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Π Interactions

Three new modifications of trimeric perfluoro-ortho-phenylene mercury (2) have been investigated by single crystal X-ray diffraction. In each of these modifications, the molecules of 2 form extended stacks. Within each stack, the successive molecules are parallel and separated by approximately 3.3 - 3.4 Å. The packing observed in the different structures is rationalized on the basis of secondary mercury-π interactions, mercuriophilic interactions and electrostatic interactions. Altogether, little preference is given for one particular type of interaction. The packing appears to be dominated by non-directional van der Waals interactions between molecules of 2 which are largely aromatic and whose overall polarizability is magnified by relativistic effects at the mercury(II) centers.

Dimethyl-, Disilyl- and Digermylsulfide: Different Intermolecular Contacts in the Solid State

2004 ◽  
Vol 59 (6) ◽  
pp. 635-638 ◽  
Author(s):  
Norbert W. Mitzel ◽  
Udo Losehand
Keyword(s):  
Solid State ◽  
Low Temperature ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Intermolecular Contacts

The compounds (H3C)2S, (H3Si)2S and (H3Ge)2S have been crystallised in situ on a diffractometer and their crystal structures determined by low-temperature X-ray diffraction. The molecules are present as monomers in the crystals. The aggregation of the molecules through secondary intermolecular contacts in the crystal is different: (H3C)2S is weakly associated into dimers by S···S contacts, whereas (H3Si)2S and (H3Ge)2S form Si···S and Ge···S contacts in an ice-analogous aggregation motif. Important geometry parameters are (H3C)2S: C-S 1.794(av) Å , C-S-C 99.2(1)°; (H3Si)2S: Si- S 2.143(1) Å , Si-S-Si 98.4°; (H3Ge)2S Ge-S 2.223(2) and 2.230(2) Å , Ge-S-Ge 98.2(1)◦.

Crystal structures of some eriostyl/nitrobenzoate derivatives

1980 ◽  
Vol 33 (2) ◽  
pp. 313 ◽  
Author(s):  
PR Jefferies ◽  
BW Skelton ◽  
B Walter ◽  
AH White
Keyword(s):  
Charge Transfer ◽  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structure Determinations

Following the suggestion made earlier, on the basis of solution spectroscopy, that a number of eriostyl/nitrobenzoate compounds form charge-transfer self-complexes, a number of these have been investigated structurally by single-crystal X-ray diffraction methods in order to ascertain the presence or otherwise of such interactions in the solid state. The substances thus studied were eriostyl 3,5-dinitrobenzoate (1), eriostyl p-nitrobenzoate (2), tetrahydroeriostyl 3,5-dinitrobenzoate (3), and eriostemyl 3,5-dinitrobenzoate (4);* structure determinations in all cases, although displaying the presence of strong charge-transfer interactions from the two moieties of each molecule, show that the interactions in the solid state are intermolecular in nature.

scholarly journals Darstellung und Kristallstrukturen von (PH4P)4Sb8I28 und (Ph4P)Sb3I10(Ph = C6H5) / Synthesis and Crystal Structures of (PH4P)4Sb8I28 and (Ph4P)Sb3I10(Ph = C6H5)

1987 ◽  
Vol 42 (12) ◽  
pp. 1493-1499 ◽  
Author(s):  
Siegfried Pohl ◽  
Wolfgang Saak ◽  
Detlev Haase
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Diffraction Data ◽  
Lone Pair ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Molar Ratios ◽  
Polymeric Chains ◽  
Bond Strengths

AbstractThe compounds (Pn4P)4Sb8I28 (1) and (Ph4P)Sb3I10 (2) were prepared by the reaction of SbI3 and Ph4PI in acetonitrile (molar ratios 2:1 and 3:1 respectively). The structures of 1 and 2 were determined from single crystal X-ray diffraction data.1 crystallizes in the triclinic space group P1̄ with a - 1321.7(5). b = 1346.7(5), c = 2201.8(8) pm, α = 104.18(2). β = 99.92(2), γ = 100.33(2)°; 2: monoclinic, C2/c, a = 2371.1(2), b = 745.0(1), c = 2495.1(2) pm, β = 100.75(1)°.Whereas 1 exhibits isolated Sb8I284- ions, the anions of 2 are built up of polymeric chains [Sb3I10- ]∞. In both compounds the distorted Sbl6 octahedra are linked by common edges. The Sb-I distances are in the range between 277.4 and 354.8 pm (1) and between 277.4 and 342.4 pm (2). The observed structures do not only depend on stoichiometry, the nature of the counter cations, and the possibility of oligomerisation but also on the wide variety of the Sb-I bond strengths and the different bridges formed by iodine.The lone pair of Sb(III) seems to be predominantly 5 s2.

New Cu(II), Co(II), and Ni(II) complexes with thieno[2,3-b]pyridine and 2-methylthieno[2,3-b]pyridine as ligands: Synthesis and crystal structures

2009 ◽  
Vol 63 (3) ◽  
Author(s):  
Ján Halgaš ◽  
Viera Kolenová ◽  
Zuzana Števíková ◽  
Lucia Perašínová ◽  
Jozef Kožíšek
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Elemental Analysis ◽  
Zinc Chloride ◽  
Coordination Compounds ◽  
Biological Activities ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ft Ir

AbstractAlthough thienopyridines attract attention because of their biological activities, they have not been used as ligands in coordination compounds. Thieno[2,3-b]pyridine was prepared by known procedures; by reduction of 2-nitrothiophene, and reaction of the resulting 2-thienyl ammonium salt with malondialdehyde tetramethylacetal in the presence of zinc chloride. The same procedure was used for the preparation of a new derivative, 2-methylthieno[2,3-b]pyridine, starting from 2-methyl-5-nitrothiophene. The thienopyridines were used in the synthesis of coordination compounds. Chlorides, isothiocyanates, acetates, and chloroacetates of copper(II), nickel(II), or cobalt(II) were used as starting salts. The prepared complexes were characterized by elemental analysis and FT IR. Structures of the four complexes were determined by single-crystal X-ray diffraction analysis.

Supramolecular architectures in two 1:1 cocrystals of 5-fluorouracil with 5-bromothiophene-2-carboxylic acid and thiophene-2-carboxylic acid

2017 ◽  
Vol 73 (6) ◽  
pp. 481-485 ◽  
Author(s):  
Marimuthu Mohana ◽  
Packianathan Thomas Muthiah ◽  
Colin D. McMillen
Keyword(s):  
Solid State ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
Base Pairs ◽  
X Ray ◽  
Supramolecular Architectures ◽  
Acid Acid ◽  
Carboxylic Acid Dimer

In solid-state engineering, cocrystallization is a strategy actively pursued for pharmaceuticals. Two 1:1 cocrystals of 5-fluorouracil (5FU; systematic name: 5-fluoro-1,3-dihydropyrimidine-2,4-dione), namely 5-fluorouracil–5-bromothiophene-2-carboxylic acid (1/1), C5H3BrO2S·C4H3FN2O2, (I), and 5-fluorouracil–thiophene-2-carboxylic acid (1/1), C4H3FN2O2·C5H4O2S, (II), have been synthesized and characterized by single-crystal X-ray diffraction studies. In both cocrystals, carboxylic acid molecules are linked through an acid–acid R 2 2(8) homosynthon (O—H...O) to form a carboxylic acid dimer and 5FU molecules are connected through two types of base pairs [homosynthon, R 2 2(8) motif] via a pair of N—H...O hydrogen bonds. The crystal structures are further stabilized by C—H...O interactions in (II) and C—Br...O interactions in (I). In both crystal structures, π–π stacking and C—F...π interactions are also observed.

Bindung von Metall-Ionen an Dipeptide: Struktur von Thallium(I)-(3-benzyl-6-carboxylatomethyl-2,5-diketopiperazin) / Binding of Metal Ions by Dipeptides: Structure of Thallium(I) 3-Benzyl-6-carboxylatomethyl-2,5-diketopiperazine

1992 ◽  
Vol 47 (7) ◽  
pp. 952-956
Author(s):  
P. Mikulcik ◽  
P. Bissinger ◽  
J. Riede ◽  
H. Schmidbaur
Keyword(s):  
Solid State ◽  
Nitrogen Atom ◽  
Hydrogen Bonds ◽  
Diffraction Analysis ◽  
Carbonyl Oxygen ◽  
State Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Crystalline Product ◽  
Oxygen Atoms

Ester cleavage of aspartame (L-α-aspartyl-L-phenylalanine methylester) (1), by equimolar quantities of thallium ethoxide is accompanied by intramolecular cyclisation to give thallium 3-benzyl-6-(carboxylatomethyl)-2,5-dioxopiperazine (2). The solid state structure of the crystalline product was determined by single-crystal X-ray diffraction analysis. The cations were found to form four short and four elongated contacts to seven oxygen atoms and one nitrogen atom of a total of six neighbouring 3-benzyl-6-(carboxylatomethyl)-2,5-dioxopiperazine anions. There are inter-anionic hydrogen bonds only between the imino groups and the carbonyl oxygen atoms (O3, O4), featuring a pattern similar to that found for cytosine-guanosine contacts in DNA.

Crystal Structures of New Compounds Na0.5Sm4.5Ti4O15 and Na0.5Eu4.5Ti4O15

2011 ◽  
Vol 415-417 ◽  
pp. 468-471
Author(s):  
Qiao Hong Yu ◽  
Zheng Fa Li ◽  
Yong Xiang Li ◽  
Ping Zhan Si ◽  
Jiang Ying Wang ◽  
...  
Keyword(s):  
Solid State ◽  
Crystal Structures ◽  
Powder Diffraction ◽  
Diffraction Data ◽  
Diffraction Method ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ordinary Temperature ◽  
Europium Titanate ◽  
New Compounds

New compounds of sodium samarium titanate Na0.5Sm4.5Ti4O15and sodium europium titanate Na0.5Eu4.5Ti4O15were synthesized successfully by solid state reaction at 1300 oC and 1200 oC, respectively. The lattice parameters of Na0.5Sm4.5Ti4O15and Na0.5Eu4.5Ti4O15were determined at ordinary temperature by using X-ray powder diffraction method. Their Lattice types were determined, and their patterns were indexed. Polycrystalline X-ray diffraction data of sodium samarium titanate were listed. Differences of their crystal structures were analyzed and discussed.

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