The crystal structures of the low‐temperature (LT) and high‐temperature (HT) modifications of silver pyrophosphate, Ag 4 P 2 O 7 , were determined from single‐crystal X‐ray data. Thermal analysis, vibrational and 31 P‐MAS‐NMR spectroscopy studies, and density functional theory calculations complement the results. The crystal structure of HT‐Ag 4 P 2 O 7 ( T = 487 °C, , Z = 2, a = 5.5734(5) Å, c = 13.7613(18) Å) is very similar to that of the aristotype, γ ‐K 4 P 2 O 7 , whereas the crystal structure of LT‐Ag 4 P 2 O 7 ( T = 25 °C, P 3 1 21/ P 3 2 21, Z = 6, a = 5.5128(1) Å, c = 40.8723(11) Å) differs significantly from LT‐K 4 P 2 O 7 . The experimental results and those of DFT structure optimization yield bent pyrophosphate groups (bridging angle ∠(P−O b −P) ≈ 129°) for both LT‐ and HT‐Ag 4 P 2 O 7 , while their conformations change from eclipsed (HT) to staggered (LT). For one half of the Ag + cations in the HT modification, the unusual ninefold coordination in a truncated hexagonal pyramid changes to a distorted tetrahedral coordination in the LT form. Structural/dynamic instability expresses itself by formation of multinary compounds in the systems A 4 P 2 O 7 /Ag 4 P 2 O 7 ( A = Li, Na). Thus, the crystal structures of Li 3 AgP 2 O 7 and LiAg 3 P 2 O 7 show no similarity at all to that of Ag 4 P 2 O 7 , while the closely related crystal structure of Na 2 Ag 2 P 2 O 7 shows distinct ordering of Na + /Ag + despite similar ionic radii.

As part of crystal growth experiments on transition metal oxidotellurates using chemical vapor transport reactions or hydrothermal conditions, single crystals of NiIITeVIO4 and CuIITeIV2O5 were obtained for the first time in the form of new modifications, as revealed by crystal structure determinations from X-ray data. In the course of these investigations, the crystal structure model of the only phase of NiIITeVIO4 reported so far (from now on named α-) was corrected. Both α-(space group P21/c, Z = 2) and the new β-polymorph of NiIITeVIO4 (space group I41/a, Z = 8) can be considered derivatives (hettotypes) of the rutile structure (aristotype), as shown by detailed symmetry relationships. For CuTe2O5 also, only one crystalline phase has been described so far (from now on named α-) that corresponds to the mineral rajite (space group P21/c, Z = 2). Its anion comprises two different trigonal-pyramidal TeO3 groups linked through corner-sharing into a ditellurite unit. The anion part of the new β-CuTe2O5 modification (space group P21/c, Z = 2), likewise, comprises two TeIV atoms but is more complex. Here, one TeIV atom exhibits a coordination number of 4 and is part of a [∝1TeO2/2O2/1] chain, and the other has a coordination number of 5 and is part of a [∝1TeO2/2O3/1]2 dimer. The two types of anions are linked into a tri-periodic framework where both TeIV atoms are stereochemically active. The α- and β-CuTe2O5 modifications show no closer structural relationship, which is also reflected in their clearly different Raman spectra. Data mining for knowledge discovery in a structure database reveals that polymorphism is a rather common phenomenon for the family of inorganic oxidotellurates.

Fe-57-M & ouml;ssbauer spectra of double MM'(C2O4)(2)& sdot;4H(2)O (M = Fe, M' = Mg, Co, Zn) and triple metal oxalates MM'M"(C2O4)(3)& sdot;6H(2)O (M = Fe, M' = Mg, Mn, Co; M" = Zn) were recorded at room temperature and briefly discussed on the basis of their structural characteristics. No changes in the hyperfine interactions at the Fe-57 site were detected because of the presence of the other metal ions.

The most important aspects of the chemistry and structure of l-ascorbic acid (vitamin C) will be presented.

Different aspects of the chemistry and biochemistry of vanadium are analyzed in this review. The preparation and characterization of oxovanadates and polyoxovanadates, including simple orthovanadates, vanadates with the apatite structure, materials belonging to the CrVO4 structural type, as well as divanadates, metavanadates and decavanadates were initially discussed. The second part is devoted to vanadium compounds and systems related to vanadium biochemistry. The coordination chemistry involved in vanadium metabolism is discussed in great detail, followed by the investigation of vanadium complexes of nucleotides, carbohydrates, amino acids, and related systems. Complexes of oxo-diacetic acid and of 8-hydroxyquinoline and related ligands were also investigated. The biological activity of some of these complexes is also analyzed. Besides, systems involved in enzymatic reactions and in the activity of vanadium-dependent-haloperoxidases as well as in vanadium toxicology and detoxification are discussed. In these studies different physicochemical characterization methodologies were used, usually including vibrational (IR and Raman) and electronic absorption spectroscopy. Crystallographic studies were performed in some cases as well as the investigation of the thermal, electrochemical and magnetic behaviour. Resonance-Raman, ESR and photoelectron spectroscopy were also used in certain cases.

Copper is an essential element for most aerobic organisms, with an important function as a structural and catalytic cofactor, and in consequence, it is implicated in several biological actions. The relevant aspects of chemistry and biochemistry and the importance of copper compounds in medicine give us a comprehensive knowledge of the multifaceted applications of copper in physiology and physiopathology. In this review, we present an outline of the chemistry, and the antitumor properties of copper complexes on breast, colon, and lung cancer cells focus on the role of copper in cancer, the relationship between structure-activity, molecular targets, and the study of the mechanism of action involved in its anticancer activity. This overview is expected to contribute to understanding the design, synthesis, and uses of copper complexes as antitumor agents in the most common cancers.

Copper is an essential element for most aerobic organisms, with an important function as a structural and catalytic cofactor, and in consequence, it is implicated in several biological actions. The relevant aspects of chemistry and biochemistry and the importance of copper compounds in medicine give us a comprehensive knowledge of the multifaceted applications of copper in physiology and physiopathology. In this review, we present an outline of the chemistry, and the antitumor properties of copper complexes on breast, colon, and lung cancer cells focus on the role of copper in cancer, the relationship between structure-activity, molecular targets, and the study of the mechanism of action involved in its anticancer activity. This overview is expected to contribute to understanding the design, synthesis, and uses of copper complexes as antitumor agents in the most common cancers.

After the presentation of the most relevant characteristics of the chemistry of germanium (IV), the pharmacological effects of some of its organometallic compounds are discussed, in particular those of spirogermanium, the so-called Ge-132, the germatranes and the organogermanium sesquisulfides. Studies with porphyrinic compounds and other macrocyclic ligands, as well as the substitution of Si by Ge in the fungicidal compound flusilazole are also mentioned. Finally, the use of Ge-69 in Nuclear Medicine is analysed, and brief comments on the toxicological effects of germanium are also made.

The goal of this work was to display the anticancer and antimetastatic activity of a copper(II) with tropolone (trp), complex [Cu(trp)(2)] toward human breast cancer cells in monolayer (2D) and spheroids (3D). Cytotoxicity assays against MCF7 (IC50(complex) = 5.2 +/- 1.8 mu M, IC50(CDDP) = 19.3 +/- 2.1 mu M) and MDA-MB-231 (IC50(complex) = 4.0 +/- 0.2 mu M, IC50(CDDP) = 27.0 +/- 1.9 mu M) demonstrate that [Cu(trp)(2)] exert greater antitumor potency than cisplatin (CDDP) on 2D and 3D human breast cancer cell models. Besides, [Cu(trp)(2)] inhibits cell migration by reducing the metalloproteinases activities and the compound undergoes the breast cancer cells to apoptosis at lower concentrations (2.5-10 mu M). Moreover, [Cu(trp)(2)] overcame CDDP presenting an IC50, value 26-fold more lower against breast multicellular spheroids (IC50(complex) = 4.9 mu M, IC50(CDDP) = 130 mu M)). Also, our results showed that [Cu(trp)(2)] inhibited the cell migration and cell invasion of breast multicellular spheroids, showing that [Cu(trp)(2)] exhibited antimetastatic properties. On the other hand, [Cu(trp)(2)] reduced mammosphere forming capacity affecting the size and number of mammospheres. Taken together, [Cu(trp)(2)] exhibited anticancer and antimetastatic properties on monolayer (2D) and spheroids (3D) derived from human breast cancer cells.

The crystal structure of tetraaqua-bis(6-methyl-1,2,3-oxathiazin-4(3H)-onato 2,2-dioxide) copper(II) complex, for short [Cu(ace)(2)(H2O)(4)], was determined by X-ray diffraction methods. The complex crystallizes in the monoclinic C2/c space group with a = 11.9838(4), b = 9.5240(3), c = 15.1686(6) angstrom, beta = 102.975(4)degrees and Z = 4 molecules per unit cell. The structure was determined from 1609 reflections with I > 2 sigma(I) and refined to an agreement R1-factor of 0.0345. [Cu(ace)2(H2O)(4)] is a new member in the family of acesulfamate complexes of first row transition metals, namely [M(ace)(2)(H2O)(4)], M: Co, Ni, Zn. It differs from the other members in the bonding of acesulfamate to metal through one of its sulfoxide oxygen atoms. The new complex was further characterized by its infrared, Raman and electronic absorption spectra, which were discussed in comparison with those of other related species. (C) 2020 Elsevier B.V. All rights reserved.

The study of novel mechanisms of action of vanadium compounds is critical to elucidating the role and importance of these kinds of compounds as antitumor and antimetastatic agents. This work deals with in silico and in vitro studies of one clioquinol oxidovanadium(iv) complex [VO(clioquinol)2], VO(CQ)2, and its regulation of FAK. In particular, we focus on elucidating the relationship of the FAK inhibition, MMP activity and antimetastatic effects of the complex in human bone cancer cells.

Disodium-oxidovanadium(IV) disulfate, a new and interesting battery electrode material, is prepared by a new very simple, and easy synthetic procedure. Its infrared and Raman spectra were recorded and discussed on the basis of their structural peculiarities with the aid of a factor group analysis of the internal vibrations of the sulfate groups of the compound. The spectra appear strongly dominated by correlation field effects.

The mixed cation diphosphate of composition NH4FeP2O7 has been prepared by heating of adequate mixtures of NH4(H2PO4) and Fe(NO3)3⋅9H2O in concentrated phosphoric acid, and characterized by X-ray powder diffractometry. Its infrared and Raman spectra were recorded and briefly analyzed on the basis of the structural peculiarities of the P2O74− anion and the NH4+ cation, which is demonstrated, do not rotate freely in the lattice. Its 57Fe- Mössbauer spectrum shows that the typical high-spin FeIIIO6 octahedra present in the compound exhibit almost no distortion.

The term organic minerals' means naturally occurring crystalline organic compounds including metal salts of formic, acetic, citric, mellitic, methanesulfonic and oxalic acids. As for the rest of the (inorganic) minerals, the primary tool to disclose their crystal and molecular structure and therefore to understand their mutual relationship with each other and with synthetic analogues and also their physicochemical properties is X-ray diffraction crystallography ever since the dawn of this methodology in 1913. The structure of several synthetic organic minerals was solved well before the discovery of their natural counterpart. On the other hand, complete crystal structure determination of early discovered organic minerals had to await the advent of combined synthetic and advanced X-ray diffraction methods to fully unveil their crystal structures. We review here the crystal chemistry of organic minerals and show the importance of structural studies on their synthetic analogues. This will be highlighted by case studies on the recently reported synthetic novgorodovaite, Ca-2(C2O4)Cl(2)2H(2)O, and its heptahydrate analogue, Ca-2(C2O4)Cl(2)7H(2)O, and the isotypic to each other stepanovite, NaMg[Fe(C2O4)(3)]9H(2)O, and zhemchuzhnikovite, NaMg[AlxFe1-x(C2O4)(3)]9H(2)O.

Synthetic novgorodovaite analog Ca-2(C2O4)Cl-2 center dot 2H(2)O is identical to its natural counterpart. It crystallizes in the monoclinic I2/m space group with a = 6.9352(3), b = 7.3800(4), c = 7.4426(3) , beta = 94.303(4)A degrees, V = 379.85(3) (3) and Z = 2. The heptahydrate analog, Ca-2(C2O4)Cl-2 center dot 7H(2)O, crystallizes as triclinic twins in the P space group with a = 7.3928(8), b = 8.9925(4), c = 10.484(2) , alpha = 84.070(7), beta = 70.95(1), gamma = 88.545(7)A degrees, V = 655.3(1) (3) and Z = 2. The crystal packing of both calcium oxalate-chloride double salts favors the directional bonding of oxalate, C2O4 (2-), ligands to calcium ions as do other related calcium oxalate minerals. The pi-bonding between C and O atoms of the C2O4 (2-) oxalate group leaves sp (2)-hydridised orbitals of the oxygen atoms available for bonding to Ca. Thus, the Ca-O bonds in both calcium oxalate-chloride double salts are directed so as to lie in the plane of the oxalate group. This behavior is reinforced by the short O center dot center dot center dot O distances between the oxygens attached to a given carbon atom, which favors them bonding to a shared Ca atom in bidentate fashion. Strong bonding in the plane of the oxalate anion and wide spacing perpendicular to that plane due to repulsion between oxalate pi-electron clouds gives rise to a polymerized structural units which are common to both hydrates, explaining the nearly equal cell constants similar to 7.4 which are defined by the periodicity of Ca-oxalate chains in the framework (monoclinic b ae triclinic a). When compared with novgorodovaite, the higher water content of Ca-2(C2O4)Cl-2 center dot 7H(2)O leads to some major differences in their structures and ensuing physical properties. While novgorodovaite has a three-dimensional framework structure, in the higher hydrate, the highly polar water molecules displace chloride ions from the calcium coordination sphere and surround them through OwH center dot center dot center dot Cl hydrogen bonds. As a result, polymerization in Ca-2(C2O4)Cl-2 center dot 7H(2)O solid is limited to the formation of two-dimensional Ca-2(C2O4)(H2O)(5) slabs parallel to (001), inter-layered with hydrated chloride anions. This layered structure accounts for (001) being both a perfect cleavage and a twin interface plane. The infrared and Raman spectra of both salts are also briefly discussed.

Synthetic novgorodovaite analog Ca2(C2O4)Cl2·2H2O is identical to its natural counterpart. It crystallizes in the monoclinic I2/m space group with a = 6.9352(3), b = 7.3800(4), c = 7.4426(3) Å, β = 94.303(4)°, V = 379.85(3) Å3 and Z = 2. The heptahydrate analog, Ca2(C2O4)Cl2·7H2O, crystallizes as triclinic twins in the P \(\overline{1}\) space group with a = 7.3928(8), b = 8.9925(4), c = 10.484(2) Å, α = 84.070(7), β = 70.95(1), γ = 88.545(7)°, V = 655.3(1) Å3 and Z = 2. The crystal packing of both calcium oxalate–chloride double salts favors the directional bonding of oxalate, C2O4 2−, ligands to calcium ions as do other related calcium oxalate minerals. The π-bonding between C and O atoms of the C2O4 2− oxalate group leaves sp 2-hydridised orbitals of the oxygen atoms available for bonding to Ca. Thus, the Ca–O bonds in both calcium oxalate–chloride double salts are directed so as to lie in the plane of the oxalate group. This behavior is reinforced by the short O···O distances between the oxygens attached to a given carbon atom, which favors them bonding to a shared Ca atom in bidentate fashion. Strong bonding in the plane of the oxalate anion and wide spacing perpendicular to that plane due to repulsion between oxalate π-electron clouds gives rise to a polymerized structural units which are common to both hydrates, explaining the nearly equal cell constants ~7.4 Å which are defined by the periodicity of Ca-oxalate chains in the framework (monoclinic b ≈ triclinic a). When compared with novgorodovaite, the higher water content of Ca2(C2O4)Cl2·7H2O leads to some major differences in their structures and ensuing physical properties. While novgorodovaite has a three-dimensional framework structure, in the higher hydrate, the highly polar water molecules displace chloride ions from the calcium coordination sphere and surround them through OwH···Cl hydrogen bonds. As a result, polymerization in Ca2(C2O4)Cl2·7H2O solid is limited to the formation of two-dimensional Ca2(C2O4)(H2O)5 slabs parallel to (001), inter-layered with hydrated chloride anions. This layered structure accounts for (001) being both a perfect cleavage and a twin interface plane. The infrared and Raman spectra of both salts are also briefly discussed.

The complex bis (4,7-dimethyl-1,10-phenantroline)sulfatooxidovanadium(IV), commonly known as Metvan, was prepared using a known synthetic procedure. Its optimized molecular structure was obtained by DFT calculations, as it was impossible to grow single crystals adequate for a crystallographic study. The complex was also characterized by a detailed analysis of its infrared spectrum, supported by the theoretical calculations, and also by some data derived from its Raman spectrum. In addition, cytotoxicity studies were performed using human osteosarcoma (MG-63) and human colorectal adenocarcinoma (HT-29) cell lines. The results show that Metvan impaired cell viability of both cancer cell lines in a low concentration range (0.25–5.0 μM).

La palabra bioinorgánica parece encerrar una contradicción profunda ya que el prefijo bio significa vida e inorgánico es todo lo no viviente, una situación que apunta a una temática fuertemente interdisciplinaria. Y así es en efecto, ya que la llamada Química Bioinorgánica es una rama interdisciplinaria de la Química que se ocupa de una amplia gama de problemas ubicados en la interfase entre la Química y las Ciencias Biológicas...

Abstract The crystal structure of pyridinium 6-methyl-1,2,3,-oxathiazine-4(3H)-one-2,2-dioxide [(C5NH6)(C4H4NO4S)], for short, pyH(ace), was determined by X-ray diffraction methods. It crystallizes as a twin in the monoclinic space group P21/c with a=6.9878(9), b=7.2211(7), c=21.740(2) Å, β=91.67(1)° and Z=4 molecules per unit cell. The structure was determined employing 1599 reflections with I>2σ(I) from one of the twin domains and refined employing 2092 reflections from both crystal domains to an agreement R1 factor of 0.0466. Besides electrostatic attractions, intermolecular pyH···O=C(ace) hydrogen bonds stabilize the acesulfamate anion and the pyridinium cation into planar discrete units parallel to the (100) crystal plane. The units form stacks of alternating ace− and pyH+ ions along the a axis that favors inter-ring π–π interactions. The Fourier transform-infrared (FT-IR) spectrum of the compound was recorded and is briefly discussed. Some comparisons with related pyridinium saccharinate salts are also made.