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Extra virgin olive oil (EVOO) is a key component of the Mediterranean diet, with several health benefits derived from its consumption. Moreover, due to its eminent market position, EVOO has been thoroughly studied over the last several years, aiming at its authentication, but also to reveal the chemical profile inherent to its beneficial properties. In the present work, a comparative study was conducted to assess Greek EVOOs’ quality and authentication utilizing different analytical approaches, both targeted and untargeted. 173 monovarietal EVOOs from three emblematic Greek cultivars (Koroneiki, Kolovi and Adramytiani), obtained during the harvesting years of 2018– 2020, were analyzed and quantified as per their fatty acids methyl esters (FAMEs) composition via the official method (EEC) No 2568/91, as well as their bioactive content through liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) methodology. In addition to FAMEs analysis, EVOO samples were also analyzed via HRMS-untargeted metabolomics and optical spectroscopy techniques (visible absorption, fluorescence and Raman). The data retrieved from all applied techniques were analyzed with Machine Learning methods for the authentication of the EVOOs’ variety. The models’ predictive performance was calculated through test samples, while for further evaluation 30 commercially available EVOO samples were also examined in terms of variety. To the best of our knowledge, this is the first study where different techniques from the fields of standard analysis, spectrometry and optical spectroscopy are applied to the same EVOO samples, providing strong insight into EVOOs chemical profile and a comparative evaluation through the different platforms. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

The already known Ag(I)-Sb(III) compound of the formula {Ag(Ph3Sb)3(NO3)} (1) and two novel mixed metal Ag(I)-Sb(III) metallotherapeutics of the formulae {Ag(Ph3Sb)3(SalH)}(2) and {Ag(Ph3Sb)3(Asp)}(3) (SalH2 = salicylic acid, AspH = aspirin or 2-acetylsalicylic acid and Ph3Sb = triphenyl antimony(III)) have been synthesised and characterised by m.p., vibrational spectroscopy (mid-FT-IR), 13C-,1H-NMR, UV-visible (UV-vis) spectroscopic techniques, high resolution mass spectroscopy (HRMS) and X-ray crystallography. Compounds 1,- 3 were treated with the surfactant cetyltrimethylammonium bromide (CTAB) in order to enhance their solubility and as a consequence their bioactivity. The resulting micelles a-c were characterised with X-ray powder diffraction (XRPD) analysis, X-ray fluorescence (XRF) spectroscopy, Energy-dispersive X-ray spectroscopy (EDX), conductivity, Thermal gravimetry-differential thermal analysis (TG-DTA), and atomic absorption. Compounds 1-3 and the relevant micelles a-c were evaluated for their in vitro cytotoxic activity against human cancer cell lines: MCF-7 (breast, estrogen receptor (ER) positive), MDA-MB-231 (breast, ER negative) and MRC-5 (normal human fetal lung fibroblast cells) with sulforhodamine B (SRB) colorimetric assay. The results show significant increase in the activity of micelles compared to that of the initial compounds. Moreover, micelles exhibited lower activity against normal cells than tumor cells. The binding affinity of a-c towards the calf thymus (CT)-DNA, lipoxygenase (LOX) and glutathione (GSH) was studied by the fluorescent emission light and UV-vis spectroscopy. © 2015 Elsevier Inc. 150 108 119 Manufacturers: Sigma Aldrich Cited By :4

The reaction of Ξ²-dicarbonyl phenyliodonium ylides with diphenylketene at room temperature affords mixtures of lactone and aurone derivatives. The initial electrophilic attack of the iodonium ylide on the CΞ² position of the diphenylketene, followed by cyclization of the zwitterionic species, and subsequent ejection of iodobenzene, affords the lactone and aurone cycloadducts. Treatment of Ξ²-dicarbonyl iodonium ylides with acyl chlorides yields Ξ±-chloroenones with good to excellent yields. Journal of Organic Chemistry

A series of co-crystals of trans-1,2-bis(4-pyridyl) ethylene (bpe) with aliphatic saturated or unsaturated dicarboxylic acids, of the type [(bpe)(L)] (L = dicarboxylic acid), were prepared and characterized by single crystal X-ray crystallography. In all cases chains of the type acid···bpe···acid were formed via strong O-H···N hydrogen bonds. The chains were further linked between them by weak C-H···O hydrogen bonds, π-π and herringbone interactions to form three-dimensional structures. Thermal analysis showed considerable elevation of the melting/decomposition point of the co-crystals with respect either to both components or to bpe, ascribed to the formation of multiple complementary C-H···O bonds as well as to π-π interactions between the two conformer molecules. When L = fumaric acid, the two components stack separately with their C�C bonds strictly parallel between them at 3.83 Å from one another. However, photodimerization reaction takes place only between the olefin bonds of bpe. Photodimerization reaction between one C�C bond of the acid and that of bpe was also induced when L = trans,trans-muconic acid. Crystal Growth Des

The reaction of Fe(III) with the substituted salicylaldehydes [X-saloH, where X = 3-OCH(3) (L (1) ), 5-CH(3) (L (2) ), 5-Cl (L (3) ), 5-NO(2) (L (4) )] led to the formation of four new iron(III) hetero-heptanuclear complexes (Fe-Na) under the general formula [Fe(2)(X-salo)(8)Na(5)] center dot A 3OH center dot A zH(2)I. The two different coordination modes of the ligand, as well as the geometry around the metal ions were deduced by X-ray structure analysis of compound 1, [Fe(2)(3-OCH(3)-salo)(8)Na(5)] center dot A 3OH center dot A 8H(2)I. The complexes have also been characterized by physicochemical and spectroscopic (IR, UV-Vis, Mossbauer) methods. Structural Chemistry

The reactions of tetrachloroauric(III) acid (HAuCl(4)) with the thioamides; 2-mercapto-benzothiazole (mbztH) and 5-ethoxy-2-mercapto-benzimidazole (EtmbzimH) lead to the desulfuration of the ligands and the formation of the ionic complexes {[AuCl(4)](-)[bztH(2)](+)} (1), and {[AuCl(4)](-)[EtbzimH(2)](+)(H(2)O)} (2) (where bztH(2)(+) and EtbzimH(2)(+) are the desulfurated cations of the starting ligands). The reaction of HAuCl(4) with 2-mercapto-nicotinic acid (mnaH(2)), however results in the formation of 2-sulfonate-nicotininc acid (C(6)H(5)NO(5)S) (3) with the simultaneous oxidation of the sulfur atom. On the other hand, the reactions of the gold(I) complex [Au(tpp)Cl] (4) (tpp = triphenylphosphine (Ph(3)P)) with the thioamides; 2-mercapto-thiazolidine (mtzdH), 2-mercapto-benzothiazole (mbztH) and 5-chloro-2-mercapto-benzothiazole (ClmbztH) in the presence of potassium hydroxide resulted in the formation of the gold(I) complexes of formulae [Au(tpp)(mtzd)] (5), [Au(tpp)(mbzt)] (6) and [Au(tpp)(Clmbzt)] (7) without ligand desulfuration. All complexes have been characterized by elemental analysis, FT-IR, far-FT-IR, (1)H-NMR, spectroscopic techniques and X-Ray crystallography. The electrochemical behavior of 1, 2 and 4-7 complexes and the ligands EtmbzimH, mbztH and mnaH(2) was also studied in acetonitrile and DMF using cyclic voltammetry. The results are in support of a mechanism of desulfuration of the ligands by Au(III), involving a first oxidation of S to -SO(3)(-), followed by a C-S bond cleavage. This is also supported by PM6 calculations of bond dissociation energies of the various compounds involved. Complexes 1, 2 and 4-7 were tested for in vitro cytotoxicity against leiomyosarcoma cells and the results are discussed in relation with the geometry of the complexes and compared with those of cisplatin and other metals. Complexes 1 and 5 showed higher activity than that of cisplatin, while HAuCl(4) was inactive against sarcoma cells. Dalton Transactions

The crystal structure and packing of a series of six nearly tetrahedral organic compounds 1-6, of general formula PhNH-(CArArAr3)-Ar-1-Ar-2 [1(Ph, Ph, Ph), 2(Ph, Ph, 2-Py), 3(Ph, Ph, 3-Py), 4(Ph, Ph, 4-Py), 5(Ph, 2-Py, 2-Py), and 6(2-Py, 2-Py, 2-Py)] were investigated by X-ray crystallography and supported, in some cases, by ab initio calculations, IR spectroscopy, and H-1 NMR. All molecules have in common an aniline group, but they differ in the number of phenyl groups that are replaced by pyridyl ones (1, 2, 5, 6) or the position of the nitrogen heteroatom at the pyridyl ring (2-4). Purely van der Waals solids are obtained when the molecule can form an intramolecular N-H center dot center dot center dot N hydrogen bond (2, 5, 6), and, in this case, a correlation between melting point and structure was attempted. However, when intermolecular N-H center dot center dot center dot N bonds were established, helices (4) or tetrameric (two organic molecules + two solvent molecules) molecular complexes (3) were obtained. Crystal Growth & Design

A 2D layered structure composed of Cd dimers, linked by fumarate anions to form a rectangular grid network, was pillared, via metal coordination, to afford a 3D photoreactive metal-organic framework. Crystengcomm

Organotin(IV) complexes with the formulas [(C6H5)3Sn(mbzt)] (1), [(C6H5)3Sn(cmbzt)] (3), and [(C6H5)2Sn(cmbzt)2] (4) (Hmbzt ) 2-mercaptobenzothiazole and Hcmbzt ) 5-chloro-2-mercaptobenzothiazole) have been synthesized and characterized by elemental analysis; FT-IR, Raman, 1H, 13C, and 119Sn NMR, and Mo¨ssbauer spectroscopic techniques; and X-ray crystallography at various temperatures. The crystal structures of complexes 1, 3, and 4 were determined by X-ray diffraction at room temperature [295(1) or 293(2) K]. The complexes [(C6H5)3Sn(mbzo)] (2) and [(n-C4H9)2Sn(cmbzt)2] (5) (Hmbzo ) 2-mercaptobenzoxazole) were synthesized by new improved methods, and their structures were determined at low temperature [100(1) K] and compared to those solved at room temperature. Comparison with {(CH3)2Sn(cmbzt)2]} (6), already reported, was also attempted. The influence of temperature on the geometry of the complexes is discussed. In the cases of complexes 1-3, three carbon atoms from phenyl groups and one sulfur atom and one nitrogen atom from thione ligands form a tetrahedrally distorted trigonal-bipyramidal geometry around the five-coordinate tin(IV) ion. In complexes 4-6, two carbon atoms from aryl groups and two sulfur atoms and two nitrogen atoms from thione ligands form a distorted tetrahedral geometry, tending toward octahedral, around the six-coordinate tin(IV) ions, with trans-C2, cis-N2, and cis-S2 configurations. Although the C-Sn and S-Sn bond distances are found to be constant in compounds 1-6, their N-Sn bond lengths vary significantly (from 2.635 to 3.078 Å), with the longer distances found in the cases of five-coordinate complexes 1-3. Inorg. Chem.

Crystals of a water soluble, potassium(I) complex with the heterocyclic thioamide; 2-mercapto-nicotinic acid (H2mna), of formula {[K(H2mna)2]+.[K(ΞΌ-OH)2]-.4H2O}n (1) were grown from the filtrate of the reaction between 2-mercapto-nicotinic acid with KOH in a molar ratio 1:1.5 in water. The complex has been characterized by elemental analysis, TG-DTA, 1H NMR and FT-IR spectroscopic techniques and X-ray powder diffraction. The single crystal structure of complex (1) has been determined by X-ray diffraction at ambient conditions. The polymeric structure of the complex is microporous, where water molecules are retained. The water molecules can be reversibly removed. The complex is ionic, containing [S-K+-S] linkages and an infinite ribbon of {[K(ΞΌ-OH)2]-}n as a counter anion. Strong hydrogen bonds and Ο€-Ο€ interactions stabilize the supramolecular architecture of the inorganic/metal-organic hybrid formed. Heating of (1) at 100 Β°C for 4 h forms the {[K(H2mna)2]+ .[K(ΞΌ-OH)2]-}n (2), which retains the framework structure although the coordinated water molecules were evacuated. Inorg. Chim. Acta

Crystals of a water soluble, potassium(I) complex with the heterocyclic thioamide; 2-mercapto-nicotinic acid (H(2)mna), of formula {[K(H2mna)(2)](+) center dot [K(mu-OH)(2)](-) center dot 4H(2)O}(n) (1) were grown from the filtrate of the reaction between 2-mercapto-nicotinic acid with KOH in a molar ratio 1: 1.5 in water. The complex has been characterized by elemental analysis, TG-DTA, H-1 NMR and FT-IR spectroscopic techniques and X-ray powder diffraction. The single crystal structure of complex (1) has been determined by X-ray diffraction at ambient conditions. The polymeric structure of the complex is microporous, where water molecules are retained. The water molecules can be reversibly removed. The complex is ionic, containing [S-K+-S] linkages and an infinite ribbon of { [K(mu-OH)(2)](-)}(n) as a counter anion. Strong hydrogen bonds and pi-pi interactions stabilize the supramolecular architecture of the inorganic/metal-organic hybrid formed. Heating of (1) at 100 degrees C for 4 h forms the {[K(H2mna)(2)](+) center dot [K(V-OH)(2)](-)}(n) (2), which retains the framework structure although the coordinated water molecules were evacuated. (c) 2005 Elsevier B.V. All rights reserved. Inorganica Chimica Acta

Thermal rearrangement of (±)-spiro{naphthalene-1(2H),4′- (naphtho-[2′,1′:2,3]pyrano[4,5-c]furazan)}-2-one-11′-oxides in DMF or acetic anhydride at 140°C gave an isomeric mixture of (±)-spiro{naphthalene-1(2H),1′-(5′-hydroxyphenalene[1,2-c] furazan)}-2-one-2′-oxides and 4′-oxides. The rearranged structure was confirmed from X-ray analysis and was consistent with the through space NOE data. The rearrangement is suggested to be an overall tandem isomerization process. Using variable temperature 1H NMR spectroscopy the lower limit for the isomerisation barrier for a pair of tautomers was calculated to be 22 kcal mol-1 at 423 K. The isomerisation equilibrium for a pair of isomers was studied by variable temperature 1H NMR. The lower limit for the isomerisation barrier was calculated to be 22 kcal mol-1 at 423 K. This low value may be indicative of the difficulty encountered in separating the isomers by chromatography. Semi-empirical AM1 and molecular mechanics calculations suggest that the (±)-spiro{naphthalene-1(2H), 1′-(5′-hydroxyphenalene[1,2-c]furazan)}-2-one-2′-oxides are more stable than their 4′-oxide counterparts, in accordance to the X-ray structure. The lower population of the 4′-oxide isomers relative to that of the 2′-oxide isomers was explained in terms of an unfavourable intramolecular steric interaction found in the low energy structure of the former. © 2005 Elsevier Ltd. All rights reserved.

The photochemistry of three structurally very similar triphenylmethylsilanes 1, 2, 3 [p-X - C6H4 - CPh2- SiMe3: X = PhCO, 1; H, 2; Ph(OCH2CH2O) C, 3] is described by means of 248 and 308 nm nanosecond laser. ash photolysis (ns-LFP), femtosecond LFP, EPR spectroscopy, emission spectroscopy (fluorescence, phosphorescence), ns-pulse radiolysis (ns-PR), photoproduct analysis studies in MeCN, and X-ray crystallographic analysis of the two key-compounds 1 and 2. The photochemical behavior of 1, 2 and 3 is discussed and compared with that of a fourth one, 4, bearing on the p-position an amino group ( X = Me2N) and whose detailed photochemistry we reported earlier (J. Org. Chem., 2000, 65, 4274 - 4280). Silane 1 undergoes on irradiation with 248 and 308 nm laser light a fast photodissociation of the C - Si bond giving the p-(benzoyl) triphenylmethyl radical ( 1(center dot)) with a rate constant of k(diss) = 3 x 10(7) s(-1). The formation of 1(center dot) is a one-quantum process and takes place via the carbonyl triplet excited state with high quantum yield (Phi(rad) = 0.9); the intervention of the triplet state is clearly demonstrated through the phosphorescence spectrum and quenching experiments with ferrocene (k(q) = 9.3 x 10(9) M-1 s(-1)), Et3N ( 1.1 x 10(9) M-1 s(-1)), and styrene (3.1 x 10(9) M-1 s(-1)) giving quenching rate constants very similar to those of benzophenone. For comparative reasons radical 1(center dot) was generated independently from p-( benzoyl) triphenylmethyl bromide via pulse radiolysis in THF and its absorption coefficient at lambda(max) = 340 nm was determined (epsilon = 27770 M-1 cm(-1)). We found thus that the p-PhCO-derivative 1 behaves similar to the p- Me2N one 4 ( the latter giving the p-( dimethylamino) triphenylmethyl radical with Phi(rad) = 0.9), irrespective of their completely different ground state electronic properties. In contrast, compounds 2, 3 that bear only the aromatic chromophore give by laser or lamp irradiation both, (i) radical products [ Ph3Ccenter dot and p-Ph(OCH2CH2O)C-C6H4 -C((center dot)) Ph-2, respectively] after dissociation of the central C - Si bond ( Phi(rad) = 0.16), and ( ii) persistent photo-Fries rearrangement products ( of the type of 5-methylidene-6-trimethylsilyl-1,3-cyclohexadiene) absorbing at 300 - 450 nm and arising from a 1,3-shift of the SiMe3 group from the benzylic to the ortho-position of the aromatic ring (Phi approximate to 0.85 for 2). Using fs-LFP on 2 we showed that the S-1 state recorded at 100 fs after the pulse decays on a time scale of 500 fs giving Ph3C center dot through C - Si bond dissociation. In a second step and within the next 10 ps trityl radicals either escape from the solvent cage ( the quantum yield of Ph3C center dot formation Phi(rad) = 0.16 was measured with ns- LFP), or undergo in-cage recombination to photo-Fries products. Thus, singlet excited states (S-1) of the aromatic organosilanes ( 2, 3) prefer photo-Fries rearrangement products, while triplet excited states ( 1, 4) favor free radicals. Both reactions proceed via a common primary photodissociation step ( C - Si bond homolysis) and differentiate obviously in the multipliciy of the resulting geminate radical pairs; singlet radical pairs give preferably photo-Fries products following an in-cage recombination, while triplet radical pairs escape the solvent cage ( MeCN). The results demonstrate the crucial role which is played by the chromophore which prescribes in a sense, ( i) the multiplicity of the intervening excited state and consequently that of the resulting geminate radical pair, and ( ii) the dominant reaction path to be followed: the benzophenone-and anilino-chromophore present in silanes 1 and 4, respectively, impose effective intersystem crossing transitions (k(isc) = 10(11) s(-1) and 6 x 10(8) s(-1), respectively) leading to triplet states and finally to free radical products, while the phenyl chromophore in 2 and 3, possessing ineffective isc (k(isc) = 6 x 10(6) s(-1)) leads to photo-Fries product formation via the energetic high lying S-1 state [approximate to 443 kJ mol(-1) (106 kcal mol(-1))]. Photochemical & Photobiological Sciences

A novel supramolecular structure, [C8H11N2S](2)center dot(C6Cl2O4), based on hydrogen bonding of the organic S-benzylthiuronium (SBT) cation and the chloranilate dianion, is presented. Chloranilic acid or 2,5-dichlro-3.6-dihydroxy-1,4-benzoquinone, is a strong quinoidal diphenic acid (pK(1) = 1.09 and pK(2) = 2.42), with molecular formula C6Cl2O4H2 (H(2)CA). The CA-dianions and the aromatic rings of the SBT-cation; form columns along the c-axis giving an ordered pattern of dianions surrounded by densely populated areas of SBT-cations. Each CA-dianion forms eight hydrogen bonds with the amine protons of six SBT-cations, through its oxygen atoms. In this way, an extended H-bond network, containing infinite chains of alternative R-4(2)(8) and R-2(2)(9) cyclic patterns, is obtained. The whole arrangement leads to a C2/c space group crystal structure, with unit cell dimensions a = 15.109 angstrom, b = 11.606 angstrom, and c = 14.390 angstrom and with unit cell angles of alpha = gamma = 90 degrees, and beta = 97.01 degrees, and average density of 1.43 g/cm(3). Dissolution of the crystalline material in DMSO leads to the formation of associated organic ions or charge-transfer complexes as evidenced from the bathochromic shift of the absorption band of chloranilic acid from 420 to 520 nm. Chemistry of Materials

Tetrahedron

Eur. J. Inorg. Chem.

[Cd(phen)(2)(CA)](n) (I, where phen is 1,10-phenanthroline and CA(2-) is the dianion of 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) has been synthesized and its crystal structure has been determined by single-crystal X-ray diffraction at room temperature. The crystal of I is built from infinite chains of chloranilate-bridged cadmium(II) leading to a zig-zag structure, with the phenanthroline ligands being stacked between the chains. These interactions assist the formation of a closely packed 3D structure. The coordination environment of cadmium(II) - very scarce in its chemistry - is square antiprismatic. The polymer was also characterized with spectroscopic (IR, Raman, DRS) and thermogravimetric (TG, DTA) techniques. (C) 2004 Elsevier Ltd. All rights reserved. Polyhedron

Silver(I) bromide reacts with 2-mercapto-3,4,5,6-tetrahydropyrimidine (StpmH(2), C4H8N2S) in DMSO with an excess of triethylamine to give a water-insoluble complex of formula [Ag-6(mu(2)-Br)(6)(mu(2)-StpmH(2))(4)(mu(3)-StpmH(2))(2)](n) (1), while the reaction of silver(I) nitrate with StpmH(2) under the same conditions gives a water-insoluble complex of formula [{Ag-4(mu(2)-StpmH(2))(6)}(NO3)(4)](n) (2). The products were characterized by elemental analyses, and FT-IR far-IR, UV/Vis, H-1 and C-13 NMR spectroscopy. Crystal structures of complexes 1 and 2 were determined by X-ray diffraction. Complex 1, C24H48Ag6N12S6, crystallizes in the triclinic system space group P (1) over bar, a = 8.041(1) Angstrom, b = 12.838(4) Angstrom, c = 13.281(2) Angstrom, alpha = 68.40(1)degrees, = 72.97(1)degrees, gamma = 87.80(2), Z = 2, forming a one-dimensional infinite ribbon structure by strong interatomic interactions of two mu(2)-Br bonds with Ag(1). Complex 2, C24H48Ag4N16O12S6, crystallizes in the orthorhombic system, space group Cmc2(1), and a = 32.148(3) Angstrom, b = 9.461(2) Angstrom, c = 7.234(1) Angstrom, alpha = beta = gamma = 90degrees, Z = 8, forming infinite Ag-S-Ag chains which are bridged to each other by a sulfur atom of mu(2)-StpmH(2) ligands. Complexes 1 and 2 were studied for their cytostatic activity against murine leukemia (L1210) and human T-lymphocyte (Molt4/C8 and CEM) cells and for their antiviral activity against a wide variety of viruses. They are markedly cytostatic at 50% inhibitory concentration (IC50) values ranging from 3 to 17 mug/mL. None of the compounds showed appreciable antiviral activity at subtoxic concentrations. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004. European Journal of Inorganic Chemistry

Reaction of 4-formylantipyrine with thiosemicarbazide, N(3)-methylthiosemicarbazide and N(3)-ethylthiosemicarbazide produced the expected thiosemicarbazones, 1, 2 and 3. The three thiosemicarbazones were then reacted with K2PdCl4 to produce [Pd(NS)(2)] complexes, 4, 5, and 6, respectively, with coordination by the imine nitrogen and thiolate sulfur of the anionic thiosemicarbazone moiety. The thiosemicarbazones and their palladium complexes have been characterized by spectral IR, UV-Vis and H-1, C-13 NMR and electrochemical techniques. The crystal structure of 6 has been obtained and found to be highly symmetrical with a trans arrangement of the two bidentate ligands. (K) (C) 2003 Elsevier Science B.V. All rights reserved. Inorganica Chimica Acta

The molecular bilayer motif reported here is formed by trimesic acid and Cd(2+). The ligand acts as a three-connected node while the metal is a simple spacer. The assembly of these motifs into a three-dimensional structure forms cavities into which coordinated and lattice water molecules are located. Chemistry of Materials

Inorg. Chem.

The structure and dehydration behavior of the porous 3D coordination polymer {[La-2(adipate)(3)(H2O)(4)]6H(2)O}(n) are described. Each La3+ is coordinated by nine oxygen atoms belonging to five carboxylate ligands and to two water molecules. Large infinite interconnected channels filled with hydrogen-bonded water molecules are formed in the structure. Upon heating, this compound transforms reversibly into a nonporous lower hydrate. Inorg Chem

Single crystals of [Cd(terephthalate) (H2O)(3)].4H(2)O (1), triaquo(1,4-benzenecarboxylato-kappa O)cadmium tetrahydrate, are grown in a silica gel column. Crystal structure analysis shows that (1) is a polymer with metal-organic chains stacked along the a axis forming layers parallel to the ab plane. These layers are linked by an unusual hydrogen-bonded network formed by the water molecules (both 'free' and coordinated ones) and the carboxylate O atoms. This network comprises tridymite-like O-8 cages which 'propagate' in the direction of the a axis, mimicking the way they 'propagate' along the c axis in hexagonal ice. Acta Crystallographica Section B-Structural Science

Acta Crystallographica Section C

The two title compounds, [Ni(C2H4NO2)(2)(C12H8N2).]-3H(2)O and [Ni(C2H4NO2)(2)(C10H8N2)].3H(2)O, are isostructural. Their structures consist of discrete complex molecules, together with water molecules of crystallization. All ligands are bidentate and the coordination polyhedron is a distorted octahedron. Distinct segregation of hydrophilic and hydrophobic regions appears along the c axis. In the hydrophilic region a three-dimensional network of hydrogen bonds is formed involving principally the water molecules. Aromatic interactions exist in the hydrophobic region. Acta Crystallographica Section C-Crystal Structure Communications

J. Chem. Soc. Chem. Commun.

Silver(i) glutarate is a 2D polynuclear polymer whose repeat unit consists of a tetranuclear silver cluster coordinated by two bridging glutarate anions; these units are organised, through additional metal-oxygen linkages, in layers parallel to the ac plane, in which uncommon metal-metal contacts (3.14-3.43 Angstrom) are observed. Journal of the Chemical Society-Chemical Communications

Angewandte Chemie-International Edition in English

Copper(I) complexes of the general formula [Cu(totp)(L)X], where X = Cl, I; totp = tri-ortho-tolylphosphine; L = pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), 1,3-thiazolidine-2-thione (tzdtH), 1-methyl-1,3-imidazole-2-thione (meimtH), benz-1,3-imidazoline-2-thione (bzimtH2) and quinoline-2-thione (qntH) were prepared and characterized by their IR, UV-Vis and H-1 NMR spectroscopic data. The behaviour of the complexes upon photolysis in chloroform solutions has been investigated. The structures of [Cu(totp)(pymtH)Cl] and [Cu(totp)(tzdtH)I] were determined by X-ray diffraction: [Cu(totp)(pymtH)Cl] crystallizes in the trigonal space group P3BAR with a = 22.433(4), b = 22.433(4), c = 9.526(3) angstrom, gamma = 120-degrees and Z = 6; [Cu(tzdtH)(totp)I] crystallizes in the monoclinic space group P2(1)/n with a = 17.111(2), b = 10.505(1), c = 14.823(1) angstrom, beta = 108.30(1)-degrees, Z = 4. In both complexes the coordination around Cu is approximately trigonal planar. Steric protection at the central metal by the three methyl groups neighbouring the donor phosphorus of the phosphine ligand is likely to explain the preferential formation of three-coordinate complexes. Inorganica Chimica Acta

A group of mixed ligand copper(I) coordination compounds with the saturated heterocyclic thione 2-thioxohexamethyleneimine (omega-thiocaprolactam, tclH) and tricyclohexylphosphine (Pcy3) is prepared and studied. The concerted steric effects of the two bulky ligands result in the formation of three-coordinate copper(I) complexes. The iodo compound is studied by single crystal X-ray diffraction and is shown to crystallize in the P2(1)/n space group. Four monomer units with no apparent close contacts between them are present in the unit cell, the dimensions of which are a = 10.306(2), b = 15.937(2), c = 16.774(2) angstrom, and beta = 100.06(1)-degrees. The compound is trigonal planar with the Cu-S, Cu-P and Cu-I bonds equal to 2.243(2), 2.241(2) and 2.564(1) angstrom respectively. A computational study is also carried out aiming at the understanding of the factors influencing planar or pyramidal conformation in three-coordinate CuLL'L" compounds. Inorganica Chimica Acta

The conformation of compounds 1 and 2 has been determined in the solid state by X-ray crystallography and in solution by nmr spectroscopy. MM2 and molecular dynamics calculations were used to determine the conformation of compound 2 in vacuo and in solution. Journal of Heterocyclic Chemistry

Copper(I) chloride complexes with various heterocyclic thiones and triphenylphosphine as ligands were prepared and characterized by elemental analysis, IR, UV-Vis and NMR spectroscopies. Crystal structures of the title compounds (complexes A and B, respectively) were determined by X-ray analysis. Crystals of complex A are yellow, monoclinic, space group P2(1)/c with a = 13.147(2), b = 18.592(3), c = 17.259(3) angstrom, beta = 97.45(2)-degrees, Z = 4. The final R value is 0.036 (R(W) = 0.036, gof = 1.8). Crystals of complex B are yellow, triclinic, space group P1BAR with a = 10.815(6), b = 13.109(2), c = 18.211(3) angstrom alpha = 110.87(1), beta = 100.55(4), gamma = 91.97(4)-degrees, Z = 2. The final R value is 0.060 (R(W) = 0.062, gof = 1.7). In both cases the asymmetric units include one complex molecule in which the bzimtH2 or nbzimtH2 act as monodentate ligands through the sulfur atom, as well as one solvent molecule (CH3COCH3) in the case of complex A. Inorganica Chimica Acta

For the understanding of the influence of organic complexing additives on crystal growth, we studied the habit modification of Ni(beta-ala)2.2H2O crystals in the presence of glycine. We show that the mixed complex Ni(beta-ala)(gly).2H2O is formed on the crystal surface and causes disruption of one hydrogen bond in the [11BAR0] direction, accounting for the observed habit modification. Journal of Crystal Growth

A new series of mixed ligand coordination compounds with Cu-As bonds is synthesized by the reaction of Cu(AsPh3)3X, where X=Cl, Br, or [Cu(AsPh,)I], with 2-thioxohexamethyleneimine (o-thiocaprolactam, tclH) in acetone or by the addition of triphenylarsine to Cu(tclH),X in methanol/chloroform. The products of both reactions are formulated as Cu(tclH)(AsPh&X, on the basis of their elemental analyses, IR, "�H NMR and UV-Vis spectral data. The crystal structure of the bromo compound is reported and discussed with respect to that of Cu(tclH),(AsPh,)Br. The compound crystallizes in the monoclinic space group C2/c, with a =41.981(8), b=9.961(2), c=19.087(2) A, ~=101.09(1)0, 8 discrete molecules being present in the unit cell. The copper environment is a distorted tetrahedron, with two inequal Cu-As bonds, which are 2.411(2) and 2.372(2) A, respectively. The Cu-Br and CuS bond lengths are equal to 2.456(3) and 2.313(4) A, respectively, while the bond angles around copper vary from 104.4(O)"� for Asl-Cu-S to 116.1(l)"� for Asl-Cu-As2. Inorganica Chimica Acta