Volume 238, Issue 7-8

Crystals of the first new organo–inorganic hybrid borate based on potassium crown ether complex, [K(C 12 H 24 O 6 )B 5 O 6 (OH) 4 ](H 2 O) ( 1 ), have been produced from aqueous solutions and characterized by single-crystal X-ray diffraction. 1 crystalizes is orthorhombic system, Pnma , a  = 10.1684(3) Å, b  = 11.6289(3) Å, c  = 21.2247(6) Å, V  = 2509.76(12) Å 3 , R obs  = 0.059. The structure of 1 consists of molecular [K(C 12 H 24 O 6 )B 5 O 6 (OH) 4 ] 0 complexes, common for crown ether complexes but yet not among borates, with a very rare monodentate coordination of the common pentaborate anion(1-). The molecular complexes are linked into weak chains via hydrogen bonding to outer-sphere water molecules. Hirshfeld surfaces analysis and complexity measurement of 1 were performed. Perspectives of borate structures containing crown ether complexes as templates are briefly outlined.

Pottery excavated from the archeological UNESCO world heritage site Ban Chiang in Thailand stem from distinct periods. Black vessels with cord-mark design from Pre-metal Age (ca. 3000–1000 BC), Bronze Age pottery (ca 1000–300 BC) with yellow-brown surface and Iron Age samples (ca. 300 BC–200 AD) with red pictorial surface patterns. In a previous work [Bismayer U., Srilomsak S., Treekamol Y., Tanthanuch W., Suriyatham K. Artefacts from Ban Chiang, Thailand: pottery with hematite-red geometric patterns. Z. Kristallogr. 2020, 235 , 559–568] we studied the mineralogical composition and their surface colour materials of shards from Bronze and Iron Age. In this work we focus on bulk features of the dark Pre-metal Age cord-marked ceramic shard PSN2-S10E13 and compare its elemental and mineralogical composition with bulk composition of sample 5412-S6E15 from Bronze Age. Experimental techniques are electron microprobe, X-ray powder diffraction, FTIR spectroscopy, optical microscopy and X-ray tomographic microscopy (XTM). Sample PSN2-S10E13 contains more quartz than 5412-S6E15. In the bulk of the Pre-metal Age shard, diffraction signals of mullite occur, indicating higher firing temperatures compared to the younger sample. Phyllosilicate signals are seen in FTIR spectra of both shards. E-modes of quartz dominate FTIR spectra of both samples. Optical thin sections show voids around micro-particles in PSN2-S10E13 and XTM indicates that the pore volume percentage of sample PSN2-S10E13 is higher than in 5412-S6E15. Because of the large age gap to younger samples from Ban Chiang, the proper age of our oldest sample PSN2-S10E13 was determined using an accelerator mass spectrometer (AMS) by simultaneous 14 C/ 12 C and 13 C/ 12 C isotope ratio measurements which yielded a radiocarbon age of 3609 ± 29 BP (resp. 1659 ± 29 BC).

Herein we report the results of preparing metal compounds (where the metal ions are Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ ) with the cyclic ligand 1,4,8,11-tetraazacyclotetradecane [cyclam] under a variety of conditions of metal-ligand ratios and solvent media. In all cases, we used metal Cl 2 ·nH 2 O salts (except for anhydrous CoCl 2 ), as specified. Outcome: we isolated species with a four-coordinate metal in the N4 cavity of the ligand alone, and also with either one or two additional axial ligands. Those axial ligands can be (a) a single chloride, leading to penta-coordinated moncationic products; (b) two chlorides, leading to octahedral-neutral compounds; (c) two waters, giving rise to hexa-coordinated [(cyclam)metal(H 2 O) 2 ] 2+ species. Finally, in the case of HCl added to the reaction medium, the cyclam can be di-protonated and appears as [(cyclam)H 2 ] 2+ in the crystals. With such a variety of products, it is not surprising that since the metal coordination numbers vary, the cyclam ligand stereochemistries are thereby affected. Interestingly, the [(cyclam)metal] species are invariably hydrogen-bonded to one another in infinite strings of two kinds: (1) those for which the crystal’s Z′ = 1 have single strings; (2) when Z′ = 2, there is a pair of homogeneous strings attached to one another by a variety of hydrogen-bonding linkages. Finally, we observed an interesting pair of hydroxonium cations: the first is hydoxonium cations in a pleated 2-D sheet consisting of fused pentagons located between sheets of [(cyclam)metal] moieties; the second one is an infinite string of composition {(H 3 O + )-(H 2 O)-(H 3 O + )-(H 2 O)-(H 3 O + )-(H 2 O)-(H 3 O + )} ∞ .

The crystal structure of the title compound was determined using electron diffraction data collected in continuous rotation mode. The structure was successfully solved and refined kinematically in the monoclinic space group P 2 1 / c , with a Z value of 2 and Z′ value of 0.5. Within the crystal structure, the entire molecule is predominantly flat. The molecular packing exhibits a herringbone pattern, distinct from that of the unchlorinated analogue molecule. The largest facet of the crystals, which faces the supporting carbon film, is designated as (0 1 ‾ 1 ‾ $\bar{1}\bar{1}$ ).

2-(methylthio)benzoic acid ( 1 ) is an ortho-substituted benzoic acid derivative, whereas 4-(methylthio)benzoic acid ( 2 ) is a para-substituted benzoic acid derivative. The structural analysis of both compounds was carried out using PXRD data. 2-(methylthio)benzoic acid shows a triclinic system with the P 1 ‾ $P\overline{1}$ space group, whereas 4-(methylthio)benzoic acid shows a monoclinic system and crystallizes in the P 2 1 / a space group. The strength, as well as relative contributions of intermolecular hydrogen bonds, have been examined through Hirshfeld surfaces as well as 2D fingerprint plots. A weak intramolecular hydrogen bond was found only in the case of ortho-substituted 2-(methylthio)benzoic acid. Supramolecular frameworks for 1 are formed by the interplay of intramolecular and intermolecular interactions, whereas for 2 , intermolecular contacts form supramolecular assemblies. Intermolecular O–H⋯O interactions involving carboxyl groups form the R 2 2 (8) graph-set motif for both compounds. Theoretical DFT calculations using the B3LYP correlation functional reveal that the energy gap of HOMO–LUMO orbitals in compound 1 , with the methylthio moiety in the ortho position relative to the carboxyl group, is lower than that of compound 2 , with the methylthio moiety in the para position. Vertical and adiabatic ionization energies are also calculated for both compounds.

We present the crystallographic program J ana 2020, the successor of J ana 2006. J ana 2020 has new, technically different graphics and structure plot-driven intuitive control. Tools known from J ana 2006 were revised and inserted into a new logical scheme, and their control connected with the structure plot. Some of the tools were considerably improved. We focus on the details of the most dynamically developing parts, namely twinned structures, magnetic structures, and structure analysis based on electron diffraction data.

Fluorinated chalcones are organic compounds with diverse biological activities and are of interest for drug development due to their improved properties, such as lipophilicity, bioavailability, and metabolic stability. Therefore, the correlation between structure and properties is fundamental to discover the potential use on pharmaceutical and technological applications. In this sense, we synthesized and characterized a novel fluorinated chalcone (E)-1-(4-fluorophenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (FCH), and compared its supramolecular arrangement and topological analysis with a chalcone (E)-1-(4-hydroxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (HCH). The molecular electrostatic potential, QTAIM, and frontier molecular orbitals of both chalcones were investigated using the M06-2X/6-311++G(d,p) level of theory. Our findings show that the FCH exhibits a herringbone packing with intermolecular interactions of C–H⋯F and C–H⋯π, while the HCH assumes a staircase packing coordinated by O–H⋯O and π⋯π intermolecular interactions. Furthermore, the electrostatic potential analysis shows that FCH is susceptible to electrophilic attack, while HCH is susceptible to nucleophilic attack. Finally, the structural basis analysis for both chalcones indicated that FCH has a higher lipophilicity than HCH due to the stronger hydrogen bond of HCH with water.