A Direct Route to closo-SB n Cl n Thiaboranes from Simple Electron-Precise Synthons: The Different Role of Chalcogen Bonding in SB5Cl5 and SB11Cl11 Crystals.

Six-vertex closo-SB5Cl5 (1) and ten-vertex closo-1-SB9Cl9 (2) thiaboranes have been prepared, besides the already known 12-vertex closo-SB11Cl11 (3), from the co-pyrolysis reaction of B2Cl4 with S2Cl2 at 280 ºC in vacuo. The compounds are sublimable, off-white solids. Their elemental composition has been determined by high-resolution mass spectrometry. They were further characterized by one- and two-dimensional 11B-spectroscopy and X-ray structure determination for 1 and 3. Ab initio/GIAO/NMR computations support octahedral, bicapped square-antiprismatic, and icosahedral geometries for 1, 2 and 3, respectively, as expected based on their closo-electron counts. 1 is the first isolated example of a neutral polyhedral closo-thiaborane with a cluster size smaller than ten vertices. The solid-state structure of 3 is one of the rare examples of a single-crystal X-ray structure determination of an icosahedral heteroborane reported. The corresponding crystal-packing forces show the different role of chalcogen bonding in these octahedral and icosahedral crystals. In addition, there is a mass-spectroscopy evidence for the recurrent formation of further thiaborane homologs of closo-SBnCln with n = 4, 6, 10, and supra-icosahedral 12.

Synthesis, Crystal Structure, and Optical and Magnetic Properties of the New Quaternary Erbium Telluride EuErCuTe3: Experiment and Calculation.

This paper reports for the first time on a new layered magnetic heterometallic erbium telluride EuErCuTe3. Single crystals of the compound were obtained from the elements at 1120 K using CsI as a flux. The crystal structure of EuErCuTe3 was solved in the space group Cmcm (a = 4.3086(3) Å, b = 14.3093(9) Å, and c = 11.1957(7) Å) with the KZrCuS3 structure type. In the orthorhombic structure of erbium telluride, distorted octahedra ([ErTe6]9-) form two-dimensional layers (Er(Te1)2/2e(Te2)4/2k-)∞2, while distorted tetrahedra ([CuTe4]7-) form one-dimensionally connected substructures (Cu(Te1)2/2e(Te2)2/1t5-∞1) along the [100] direction. The distorted octahedra and tetrahedra form parallel two-dimensional layers (CuErTe32-∞2) between which Eu2+ ions are located in a trigonal-prismatic coordination environment (EuTe610-). The trigonal prisms are connected by faces, forming chains (Eu(Te1)2/2(Te2)4/22-∞1) along the [100] direction. Regularities in the variations in structural parameters were established in the series of erbium chalcogenides (EuErCuCh3 with Ch = S, Se, and Te) and tellurides (EuLnCuTe3 with Ln = Gd, Er, and Lu). Ab-initio calculations of the crystal structure, phonon spectrum, and elastic properties of the compound EuErCuTe3 were performed. The types and wavenumbers of fundamental modes were determined, and the involvement of ions in the IR and Raman modes was assessed. The experimental Raman spectra were interpreted. The telluride EuErCuTe3 at temperatures below 4.2 K was ferrimagnetic, as were the sulfide and selenide derivatives (EuErCuCh3 with Ch = S and Se). Its experimental magnetic characteristics were close to the calculated ones. The decrease in the magnetic phase transition temperature in the series of the erbium chalcogenides was discovered.

Experimental and Theoretical Insights on the Structural, Electronic, and Magnetic Properties of the Quaternary Selenides EuPrCuSe3 and EuNdCuSe3.

Magnetic semiconductors EuPrCuSe3 and EuNdCuSe3 were obtained by using the halide flux method. Their crystal structures and magnetic properties were studied and discussed. Optical properties of the obtained selenides were studied by the means of diffuse reflectance spectroscopy, which revealed the values of 1.92/1.97 and 0.90/0.94 eV for the direct and indirect band gaps of Ln = Nd/Pr, respectively. The structural, electronic, and magnetic properties of the obtained compounds were additionally studied with spin-polarized density functional theory calculations, wherein both systems were found to be two new examples of semiconducting quaternary selenides with disperse conduction bands of Nd/Pr 5d character. The modeling showed that various magnetic orderings in the systems have subtle influences on the alignments/overlaps between the Se/Cu, Eu, and Pr/Nd bands, and that the spin-state energetics are very dependent upon the treatment of electron correlation, but a distinguishing feature in the case of ferromagnetic coupling is that the spin density on the Se atoms is maximized. Overall, the calculations are in good agreement with the experimental characterization of ferromagnetism in the bulk crystals, wherein the ferromagnetic transition occurs at temperatures of about 2.5 K for EuPrCuSe3 and about 3 K for EuNdCuSe3.

Synthesis under high pressure: crystal structure and properties of cubic Dy36O11F50[AsO3]12 ∙ H2O.

The multi-anionic compound with the composition Dy36O11F50[AsO3]12 ∙ H2O, which can be described in the non-centrosymmetric cubic space group F 4¯3 c, already shows an unusually large unit cell with an axis of a = 2587.59(14) pm. Its crystal structure exhibits isolated ψ1-tetrahedral [AsO3]3- anions, but both the coordination numbers and the linking schemes of the Dy3+-centered polyhedra differ significantly from the mostly layered structures described so far in literature. (Dy1)3+ is sevenfold coordinated by oxygen atoms and F- anions, forming a capped trigonal prism [(Dy1)O4.333F2.667]8.333-, and the remaining two cations (Dy2)3+ and (Dy3)3+ both reside in an eightfold coordination of anions. In both cases they form slightly distorted square antiprisms, which have the compositions of [(Dy2)O3.667F4.333]8.667- and [(Dy3)O4.667F3.333]9.667-, respectively. Some of the oxygen atoms are not part of ψ1-[AsO3]3- tetrahedra, but occur as O2- anions and one of these even shares a common crystallographic position with fluoride (F-). It is also worth mentioning that the single crystals were obtained as comparatively large cubes with an edge length of several 100 µm providing very good data with regard to single-crystal X-ray diffraction. To verify the simultaneous presence of oxygen and fluorine, electron-beam microprobe analysis was carried out, and a single-crystal Raman spectrum ruled out the presence of hydroxide anions or protonated [AsO3]3- groups, but proved the interstitial crystal-water molecules, which could not be determined precisely by the crystal-structure refinement.

Synthesis and Characterization of High-Energy Anti-Perovskite Compounds Cs3X[B12H12] Based on Cesium Dodecahydro-Closo-Borate with Molecular Oxoanions (X- = [NO3]-, [ClO3]- and [ClO4]-).

Three novel anti-perovskite compounds, formulated as Cs3X[B12H12] (X- = [NO3]-, [ClO3]-, and [ClO4]-), were successfully synthesized through the direct mixing of aqueous solutions containing Cs2[B12H12] and CsX (X-: [NO3]-, [ClO3]-, [ClO4]-), followed by isothermal evaporation. All three compounds crystallize in the orthorhombic space group Pnma, exhibiting relatively similar unit-cell parameters (e.g., Cs3[ClO3][B12H12]: a = 841.25(5) pm, b = 1070.31(6) pm, c = 1776.84(9) pm). The crystal structures were determined using single-crystal X-ray diffraction, revealing a distorted hexagonal anti-perovskite order for each. Thermal analysis indicated that the placing oxidizing anions X- into the 3 Cs+ + [B12H12]2- blend leads to a reduction in the thermal stability of the resulting anti-perovskites Cs3X[B12H12] as compared to pure Cs2[B12H12], so thermal decomposition commences at lower temperatures, ranging from 320 to 440 °C. Remarkably, the examination of the energy release through DSC studies revealed that these compounds are capable of setting free a substantial amount of energy, up to 2000 J/g, upon their structural collapse under an inert-gas atmosphere (N2). These three compounds represent pioneering members of the first ever anti-perovskite high-energy compounds based on hydro-closo-borates.

H-type Ce2[Si2O7].

The title compound, dicerium(III) oxidodisilicate, Ce2[Si2O7], was obtained as a by-product in its H-type structure after attempts to synthesize CeSb2O4Cl from fused silica ampoules. It crystallizes isotypically with H-La2[Si2O7]. The four crystallographically distinct CeIII cations form distorted square anti-prisms, capped square anti-prisms, and bicapped square anti-prisms as coordination polyhedra consisting of oxygen atoms. Four crystallographically different silicon atoms recruit the centers of two different isolated [Si2O7]6- units.

Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

M-type Gd2[Si2O7].

The title compound, digadolinium(III) oxidodisilicate, Gd2[Si2O7], was obtained in its M-type crystal structure after attempts to synthesize Gd5Br3[AsO3]4 as a by-product from fused silica ampoules. It crystallizes isotypically with M-type Eu2[Si2O7]. This structure consists of layers of ecliptically arranged oxidodisilicate [Si2O7]6- units separated from each other by bilayers consisting of GdIII cations.

Single Crystals of EuScCuSe3: Synthesis, Experimental and DFT Investigations.

EuScCuSe3 was synthesized from the elements for the first time by the method of cesium-iodide flux. The crystal belongs to the orthorhombic system (Cmcm) with the unit cell parameters a = 3.9883(3) Å, b = 13.2776(9) Å, c = 10.1728(7) Å, V = 538.70(7) Å3. Density functional (DFT) methods were used to study the crystal structure stability of EuScCuSe3 in the experimentally obtained Cmcm and the previously proposed Pnma space groups. It was shown that analysis of elastic properties as Raman and infrared spectroscopy are powerless for this particular task. The instability of EuScCuSe3 in space group Pnma space group is shown on the basis of phonon dispersion curve simulation. The EuScCuSe3 can be assigned to indirect wide-band gap semiconductors. It exhibits the properties of a soft ferromagnet at temperatures below 2 K.

A Challenge toward Novel Quaternary Sulfides SrLnCuS3 (Ln = La, Nd, Tm): Unraveling Synthetic Pathways, Structures and Properties.

We report on the novel heterometallic quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm), obtained as both single crystals and powdered samples. The structures of both the single crystal and powdered samples of SrLaCuS3 and SrNdCuS3 belong to the orthorhombic space group Pnma but are of different structural types, while both samples of SrTmCuS3 crystallize in the orthorhombic space group Cmcm with the structural type KZrCuS3. Three-dimensional crystal structures of SrLaCuS3 and SrNdCuS3 are formed from the (Sr/Ln)S7 capped trigonal prisms and CuS4 tetrahedra. In SrLaCuS3, alternating 2D layers are stacked, while the main backbone of the structure of SrNdCuS3 is a polymeric 3D framework [(Sr/Ln)S7]n, strengthened by 1D polymeric chains (CuS4)n with 1D channels, filled by the other Sr2+/Ln3+ cations, which, in turn, form 1D dimeric ribbons. A 3D crystal structure of SrTmCuS3 is constructed from the SrS6 trigonal prisms, TmS6 octahedra and CuS4 tetrahedra. The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS6)n and 1D free channels. In both crystal structures of SrLaCuS3 obtained in this work, the crystallographic positions of strontium and lanthanum were partially mixed, while only in the structure of SrNdCuS3, solved from the powder X-ray diffraction data, were the crystallographic positions of strontium and neodymium partially mixed. Band gaps of SrLnCuS3 (Ln = La, Nd, Tm) were found to be 1.86, 1.94 and 2.57 eV, respectively. Both SrNdCuS3 and SrTmCuS3 were found to be paramagnetic at 20-300 K, with the experimental magnetic characteristics being in good agreement with the corresponding calculated parameters.

Extraordinary intense blue Tl+ lone-pair photoluminescence from thallium(I) chloride hydroborate Tl3Cl[B12H12].

Microcrystalline powder of previously unknown thallium(I) chloride hydroborate Tl3Cl[B12H12] was obtained through the reaction of thallium(I) oxocarbonate Tl2[CO3] with an aqueous solution of (H3O)2[B12H12] in the presence of chloride anions. Tl3Cl[B12H12] crystallises in a primitive, orthorhombic lattice with the space group Pnma (a = 835.189(7) pm, b = 970.132(8) pm and c = 1597.912(12) pm for Z = 4) showing a distorted hexagonal anti-perovskite type arrangement of the ions. The structure features two thallium sites with mixed coordination spheres consisting of borate related hydrogen atoms and chloride anions with coordination numbers of eleven and thirteen. Tl3Cl[B12H12] shows strong excitation bands at 240 and 260 nm attributed to the 1S0 → 3P2 and 1S0 → 3P1 interconfigurational transitions of the Tl+ 6s2 cations, respectively. The emission spectrum at 300 K upon VUV excitation exhibits a broad band at 440 nm with a quantum efficiency of 41%. In addition, temperature-dependent emission spectra, colour points, reflectance, decay time, thermal quenching curve and radioluminescence spectra for Tl3Cl[B12H12] were determined.

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN Part I: ionic conductivity and defect chemistry.

This work reports on the ion transport properties and defect chemistry in anhydrous lithium thiocyanate Li(SCN), which is a pseudo-halide Li+ cation conductor. An extensive doping study was conducted, employing magnesium, zinc and cobalt thiocyanate as donor dopants to systematically vary the conductivity and derive a defect model. The investigations are based on impedance measurements and supported by other analytical techniques such as X-ray powder diffraction (XRPD), infrared (IR) spectroscopy, and density functional theory (DFT) calculations. The material was identified as Schottky disordered with lithium vacancies being the majority mobile charge carriers. In the case of Mg2+ as dopant, defect association with lithium vacancies was observed at low temperatures. Despite a comparably low Schottky defect formation enthalpy of (0.6 ± 0.3) eV, the unexpectedly high lithium vacancy migration enthalpy of (0.89 ± 0.08) eV distinguishes Li(SCN) from the chemically related lithium halides. A detailed defect model of Li(SCN) is presented and respective thermodynamic and kinetic data are given. The thiocyanate anion (SCN)- has a significant impact on ion mobility due to its anisotropic structure and bifunctionality in forming both Li-N and Li-S bonds. More details about the impact on ion dynamics at local and global scale, and on the defect chemical analysis of the premelting regime at high temperatures are given in separate publications (Part II and Part III).

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN part III: charge carrier interactions in the premelting regime.

In lithium thiocyanate Li(SCN), the temperature regime below the melting point (274 °C) is characterized by excess conductivities over the usual Arrhenius behavior (premelting regime). Here, the Schottky defect pair concentration is high, and the point defect chemistry can no longer be considered as dilute. Coulomb interactions of Schottky pairs are expected to occur lowering the formation energy of new carriers and hence leading avalanche-like to a transition into a fully defective superionic state. The respective non-linear behavior is investigated using the cube-root law approach characterized by a defect interaction parameter J, which is a measure of the effective defect-lattice energy. In the case of Li(SCN), the rather pronounced volume expansion is to be included in the model. A literature comparison with other materials emphasizes to what degree defect formation as well as defect interactions depend not only on the dominant mobile defect, but also on the respective sublattice. Overall, a quantitative description of the defect chemistry of Li(SCN) in the premelting regime is derived.

Ion transport mechanism in anhydrous lithium thiocyanate LiSCN part II: frequency dependence and slow jump relaxation.

Specific aspects of the Li+ cation conductivity of anhydrous Li(SCN) are investigated, in particular the high migration enthalpy of lithium vacancies. Close inspection of impedance spectra and conductivity data reveals two bulk relaxation processes, with comparatively fast ion transport at high frequencies and slow ion migration at low frequencies. The impedance results are supported by solid state nuclear magnetic resonance (ssNMR), and pair distribution function (PDF) analysis. This behavior reflects a frequency dependent conductivity, which is related to the extremely slow thiocyanate (SCN)- anion lattice relaxation that occurs when a Li+ cation jumps to the next available site. Two possible migration models are proposed: the first model considers an asymmetric energy landscape for Li+ cation hopping, while the second model is connected to the jump relaxation model and allows for 180° rotational disorder of the (SCN)- anion. A complete kinetic analysis for the hopping of Li+ cations is presented, which reveals new fundamental insights into the ion transport mechanism of materials with complex anions.

Quaternary Selenides EuLnCuSe3: Synthesis, Structures, Properties and In Silico Studies.

In this work, we report on the synthesis, in-depth crystal structure studies as well as optical and magnetic properties of newly synthesized heterometallic quaternary selenides of the Eu+2Ln+3Cu+1Se3 composition. Crystal structures of the obtained compounds were refined by the derivative difference minimization (DDM) method from the powder X-ray diffraction data. The structures are found to belong to orthorhombic space groups Pnma (structure type Ba2MnS3 for EuLaCuSe3 and structure type Eu2CuS3 for EuLnCuSe3, where Ln = Sm, Gd, Tb, Dy, Ho and Y) and Cmcm (structure type KZrCuS3 for EuLnCuSe3, where Ln = Tm, Yb and Lu). Space groups Pnma and Cmcm were delimited based on the tolerance factor t', and vibrational spectroscopy additionally confirmed the formation of three structural types. With a decrease in the ionic radius of Ln3+ in the reported structures, the distortion of the (LnCuSe3) layers decreases, and a gradual formation of the more symmetric structure occurs in the sequence Ba2MnS3 → Eu2CuS3 → KZrCuS3. According to magnetic studies, compounds EuLnCuSe3 (Ln = Tb, Dy, Ho and Tm) each exhibit ferrimagnetic properties with transition temperatures ranging from 4.7 to 6.3 K. A negative magnetization effect is observed for compound EuHoCuSe3 at temperatures below 4.8 K. The magnetic properties of the discussed selenides and isostructural sulfides were compared. The direct optical band gaps for EuLnCuSe3, subtracted from the corresponding diffuse reflectance spectra, were found to be 1.87-2.09 eV. Deviation between experimental and calculated band gaps is ascribed to lower d states of Eu2+ in the crystal field of EuLnCuSe3, while anomalous narrowing of the band gap of EuYbCuSe3 is explained by the low-lying charge-transfer state. Ab initio calculations of the crystal structures, elastic properties and phonon spectra of the reported compounds were performed.

Synthesis and characterisation of two lithium-thiocyanate solvates with tetrahydrofuran: Li[SCN]·THF and Li[SCN]·2THF.

Li[SCN]·THF and Li[SCN]·2THF can be obtained from solutions of anhydrous Li[SCN] in tetrahydrofuran (C4H8O, THF). Both compounds are very hygroscopic and slowly decompose even at room temperature. At ambient conditions Li[SCN]·THF crystallizes in the monoclinic space group P21/c with the lattice parameters a = 574.41(2), b = 1643.11(6), c = 830.15(3) pm and ß = 99.009(1)° for Z = 4 as determined by laboratory X-ray powder diffraction. Its crystal structure contains Li+ cations surrounded by one THF molecule and three thiocyanate anions [SCN]- forming {Li[NCS]2[SCN](OC4H8)}2- tetrahedra, which join together as pairs via shared N⋯N edges. CHNS combustion analysis and vibrational spectroscopy confirmed its composition, whereas differential scanning calorimetry and thermogravimetric analysis coupled with a mass spectrometer were applied to record its thermal behaviour. Li[SCN]·2THF crystallises in a primitive monoclinic lattice as well, but in the space group P21/n with the lattice parameters a = 1132.73(3), b = 1637.98(3), c = 1264.88(2) pm and ß = 94.393(2)° for Z = 8 as determined from single-crystal X-ray diffraction data at 100 K. Its structure contains two crystallographically independent Li+-centred tetrahedra {Li[NCS]2(OC4H8)2}-, which form dimers {(C4H8O)2Li[µ2-NCS]2Li(OC4H8)2} via shared N⋯N edges. They are merely stabilised by weak agostic H⋯S interactions between some CH2-groups of the C4H8O molecules and the [NCS]- ligands.

Synthesis, characterization and thermal behaviour of solid phases in the quasi-ternary system Mg(SCN)2-H2O-THF.

Mg(SCN)2·4H2O can be converted into previously unknown compounds Mg(SCN)2·(4 - x) H2O·xTHF with x = 0, 2 and 4 by multiple recrystallization in tetrahydrofuran (THF). The phases were characterized by infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), and their crystal structures were solved from X-ray powder diffraction (XRPD) data. In the crystal structures isolated Mg(NCS)2(H2O)4-x(THF)x units form layered motifs. The thermal behavior of Mg(SCN)2·4H2O and Mg(SCN)2·4THF was investigated by temperature dependent in situ XRPD, where Mg(SCN)2·4THF was found to acquire a room temperature (α-form) and high temperature modification (ß-form). The phase transformation is associated with an order-disorder transition of the THF molecules and with a reversion of the stacking order of the layered motifs. Further heating eventually leads to the formation of Mg(SCN)2·2THF. There thiocyanate related sulfur atoms fill the voids in the coordination sphere of magnesium, which leads to the formation of one dimensional electroneutral ∞[Mg(NCS)2/2(SCN)2/2(THF)2] chains. All investigated Mg(SCN)2·(4 - x) H2O·xTHF phases exhibit a remarkable anisotropic thermal expansion, and Mg(SCN)2·4H2O and Mg(SCN)2·2THF were found to show both positive and negative thermal expansion coefficients.

Synthesis, crystal structures and spectroscopic properties of pure YSb2O4Br and YSb2O4Cl as well as Eu3+- and Tb3+-doped samples.

The quaternary halide-containing yttrium(iii) oxidoantimonates(iii) YSb2O4Cl and YSb2O4Br were synthesised through solid-state reactions from the binary components (Y2O3, Sb2O3 and YX3, X = Cl and Br) at 750 °C in evacuated fused silica ampoules with eutectic mixtures of NaX and CsX (X = Cl and Br) as fluxing agents. YSb2O4Cl crystallizes tetragonally in the non-centrosymmetric space group P4212 with unit-cell parameters of a = 773.56(4) pm and c = 878.91(6) pm, whereas YSb2O4Br is monoclinic (space group: P21/c) with a = 896.54(6) pm, b = 780.23(5) pm, c = 779.61(5) pm and ß = 91.398(3)°, both for Z = 4. The two new YSb2O4X compounds contain [YO8]13- polyhedra, which are connected via four common edges to form layers (d(Y3+-O2-) = 225-254 pm) without any Y3+⋯X- bonds (d(Y3+⋯X-) > 400 pm). Moreover, all oxygen atoms belong to ψ1-tetrahedral [SbO3]3- units, which are either connected to four-membered rings [Sb4O8]4- in the chloride (Y2[Sb4O8]Cl2 for Z = 2) or endless chains in the bromide (Y1/2(SbO2)Br1/2 for Z = 8) by common vertices. With distances of 307 pm in YSb2O4Cl and 326 pm in YSb2O4Br there are not even substantial bonding Sb3+⋯X- (X = Cl and Br) interactions at work. Luminescence spectroscopy on samples doped with trivalent europium and terbium showed an energy transfer from the oxidoantimonate(iii) moieties as the sensitizer in the host structure onto the lanthanoid activators.

Corrosion of Heritage Objects: Collagen-Like Triple Helix Found in the Calcium Acetate Hemihydrate Crystal Structure.

Helical motifs are common in nature, for example, the DNA double or the collagen triple helix. In the latter proteins, the helical motif originates from glycine, the smallest amino acid, whose molecular confirmation is closely related to acetic acid. The combination of acetic acid with calcium and water, which are also omnipresent in nature, materializing as calcium acetate hemihydrate, was now revealed to exhibit a collagen-like triple helix structure. This calcium salt is observed as efflorescence phase on calcareous heritage objects, like historic Mollusca shells, pottery or marble reliefs. In a model experiment pure calcium acetate hemihydrate was crystallized on the surface of a terracotta vessel. Calcium acetate hemihydrate crystallizes in a surprisingly large unit cell with a volume of 11,794.5(3) Å3 at ambient conditions. Acetate ions bridge neighboring calcium cations forming spiral chains, which are arranged in a triple helix motif.

Efflorescence on calcareous objects in museums: crystallisation, phase characterisation and crystal structures of calcium acetate formate phases.

During the systematic investigation of the ternary system Ca(CH3COO)2-Ca(HCOO)2-H2O at room temperature, the congruent crystallisation of two solid calcium acetate formates was observed: the hitherto unknown Ca3(CH3COO)4(HCOO)2·4H2O and the poorly characterised Ca(CH3COO)(HCOO)·H2O. The latter is a frequently observed efflorescence phase found on calcareous objects and it could be also identified as a corrosion phase in a natural history collection of birds' eggs. Elemental and thermal analyses were employed to determine the phase compositions and by Raman and IR spectroscopy the presence of acetate and formate anions in both solids was confirmed. Laboratory X-ray powder diffraction data were used to solve the crystal structures. Ca3(CH3COO)4(HCOO)2·4H2O crystallises in a primitive tetragonal unit cell with space group P41212 and lattice parameters of a = 6.8655(1) Å and c = 45.5454(6) Å, while Ca(CH3COO)(HCOO)·H2O crystallises in a primitive monoclinic unit cell with space group P21/c and lattice parameters of a = 9.2729(1) Å, b = 6.8002(1) Å, c = 11.2219(2) Å and ß = 121.232(1)°. Calcium carboxylate zig-zag chains [Ca(µ2-RCOO)+]n (R = CH3 or H) are the main motif of both crystal structures. In Ca3(CH3COO)4(HCOO)2·4H2O these chains are exclusively composed of acetate anions, whereas in Ca(CH3COO)(HCOO)·H2O only formate anions are situated in the chains. The remaining places in the 7-8 fold coordination sphere of the calcium cations are filled by water molecules and additional carboxylate anions that interconnect neighbouring chains, which eventually leads to layered motifs in both structures.