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Linarite from Cap Garonne

  • Christian Paulsen , Christopher Benndorf , Daniel Günther , Oliver Oeckler , Helena Osthues , Nikos L. Doltsinis , Valérie Galéa-Clolus , Pierre Clolus and Rainer Pöttgen EMAIL logo
Published/Copyright: May 24, 2021
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 76 Issue 10-12

Abstract

Linarite, PbCuSO4(OH)2, crystallizes as secondary mineral in form of clusters of crystals in Mine du Pradet at Cap Garonne in France. A tiny single crystal was isolated and its structure was refined from synchrotron diffraction data (λ = 0.049592 nm): P121/m1, a = 467.75(2), b = 563.48(4), c = 967.64(5) pm, β = 102.647(5)°, wR = 0.0544, 819 F 2 values and 56 variables. The proton positions were also refined. The Cu2+ cations are located within Cu(OH)2 ribbons and exhibit pronounced Jahn-Teller distortion (d(Cu–O): 2 × 191.9, 2 × 197.3 and 2 × 252.8 pm). The Cu(OH)2 ribbons are condensed with the sulfate tetrahedra and the lead cations. The latter are coordinated to eight oxygen atoms in a slightly anisotropic manner. Calculations of the electron localization function (ELF) of PbO (litharge), PbSO4 (anglesite) and PbCuSO4(OH)2 (linarite) show pronounced lone-pair character for PbO but rather isotropic ELF values around the lead cations in PbSO4 and PbCuSO4(OH)2.

Keywords: crystal structure; lead; linarite; lone pair; Mine du Pradet

1 Introduction

Linarite, PbCuSO4(OH)2 [1], [2] is a typical secondary mineral which occurs in oxidized areas of copper and lead-containing zones. Its occurrence was first reported in 1822 and was named after the locality Linares in Spain. Meanwhile several hundred locations have been reported. Actually, linarite would be a reasonable mineral for copper and lead production; however, its abundance is too low for an economic use. Linarite usually occurs in the form of tufted aggregates of small crystals (on the µm scale). Larger single-crystal specimens (even cm-size) have been collected in the Mammoth Mine and the Grand Reef Mine in Graham County, Arizona. Such crystals allow for property studies. A single crystal approximately 1 cm in size from Grand Reef Mine was used for a neutron diffraction study [3].

Diffraction data was recorded for linarite samples from different locations [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], including powder and single-crystal work with laboratory and synchrotron X-ray data as well as neutron scattering experiments. The hydrogen bonding in linarite was studied on the basis of neutron time-of-flight data [14]. Besides the basic crystallographic characterization, linarite has been investigated with respect to its optical properties [15], [16], [17], [18], [19]. Optical absorption spectroscopic studies confirmed the presence of divalent copper in D 4h site symmetry [16]. Since 2006 PbCuSO4(OH)2 has attracted considerable interest from solid state physicists and chemists [20], [21], [22], [23], [24], [25], [26], [27], [28], [29], [30] with respect to its copper-oxygen substructure which behaves as a quasi-one-dimensional S = 1/2 frustrated-spin chain. The magnetic and transport properties and the multiferroic behaviour [31], [32], [33] of linarite have been studied in depth.

The present contribution focuses on linarite from Cap Garonne [34]. Its existence was first mentioned by Mumme et al. [35] during their study of schulenbergite. Herein we report on synchtrotron single-crystal X-ray data and a study of the electronic structure of linarite with respect to the lead lone-pair of electrons.

2 Experimental

2.1 Sample selection

The linarite sample originates from Cap Garonne (Département du Var, Région Provence-Alpes-Côte d’Azur), Mine du Pradet [34]. It was localized in the northern part of the mine (Mine Nord) in the so-called rift mirror gallery (Galerie du Miroir de Faille) within a rock face. The vertical cut (Figure 1) revealed (from bottom to top) a zinc-containing zone (adamite) followed by a copper-containing one (olivenite, azurite, malachite), a copper/zinc zone (rosasite), a lead zone (galena, linarite, dundasite, caledonite, cerussite) and finally a lead-copper zone (bayldonite, gartrellite). The linarite crystals grew in form of tufted aggregates (Figure 2) on a quartz/covellite/galena matrix. The habit of our linarite microcrystals agrees with the many entries in the RRUFF data base [2].

Figure 1: Location of linarite in the north mine, rift mirror gallery (Mine Nord, Galerie du Miroir de Faille) of Cap Garonne (Photo: E. Magnan). The source of discovery (red arrow) has a width of ca. 60 × 70 cm.
Figure 1:

Location of linarite in the north mine, rift mirror gallery (Mine Nord, Galerie du Miroir de Faille) of Cap Garonne (Photo: E. Magnan). The source of discovery (red arrow) has a width of ca. 60 × 70 cm.

Figure 2: Agglomerated linarite crystals of the north mine (Mine Nord, Galerie du Miroir de Faille) of Cap Garonne; FoV 2.1 mm (Photo: P. Clolus).
Figure 2:

Agglomerated linarite crystals of the north mine (Mine Nord, Galerie du Miroir de Faille) of Cap Garonne; FoV 2.1 mm (Photo: P. Clolus).

2.2 X-ray diffraction

Part of the linarite surface was scraped off with a spatula, powdered and filled into a 0.1 mm Lindemann capillary. A powder pattern was recorded at room temperature on a STOE Stadi P diffractometer with CuKα 1 radiation in the 2θ range 5–80°. Eight ranges of 2 h each were added up. The refined lattice parameters of a = 467.78(6), b = 563.73(4), c = 967.64(9) pm, β = 102.66(1)° and V = 0.2490 nm3 compare well with the single-crystal data (Table 1).

Table 1:

Crystal data and structure refinement parameters for PbCu(OH)2SO4, space group P121/m1, Z = 2 and 400.81 g mol−1. Standard deviations are given in parentheses.

Temperature, K 295(2)
Lattice parameters (single-crystal data)
a, pm 467.75(2)
b, pm 563.48(4)
c, pm 967.64(5)
β, deg 102.647(5)
Unit cell volume V, nm3 0.2489
Calculated density, g cm−3 5.35
Crystal size, µm3 40 × 40 × 40
Beamline DESY PETRA III P24
Diffractometer type Kappa diffractometer
Wavelength λ, Å 0.49592 (synchrotron)
Transmission (min/max) 0.620/0.746
Detector distance, mm 111.08
Exposure time, s 2.5
ω range/increment, deg. 360/0.5
Absorption coefficient, mm−1 15.1
Absorption correction Multi-scan
F(000), e 354
θ range, deg 1.51–20.74
Range in hkl ±6; −7 → +6, ±13
Total no. reflections 3069
Independent reflections/R int 819/0.0446
Reflections with I > 2 σ(I)/R σ 774/0.0398
Data/parameters 819/56
Goodness-of-fit on F 2 for all data 1.05
R/wR for I > 2 σ(I) 0.0222/0.0539
R/wR for all data 0.0230/0.0544
Largest diff. peak/hole, e Å−3 1.94/−1.04

Small fragments of the lath-shaped overgrown tufts were selected after careful mechanical fragmentation. The tiny crystal splinters were glued to glass fibres using varnish and their quality was checked using a Buerger precession camera with white Mo radiation and an image plate technique. Intensity data of a suitable crystal was collected at beamline P24 (EH1) of the Deutsches Elektronen-Synchrotron (room temperature, Huber Kappa-diffractometer, Pilatus 1M CdTe detector, λ = 0.49592 Å). Data integration and absorption correction were performed with the CrysAlis [36] and Sadabs [37] routines.

2.3 Structure refinement

The data set showed a primitive monoclinic lattice and the systematic extinctions were in agreement with space group P21/m. The standardized atomic parameters (entry 1,223,862 in the Pearson data base [38]) of the time-of-flight neutron diffraction study [14] were taken as starting values and the structure was refined on F 2 values with the Shelxl software package [39] with anisotropic atomic displacement parameters for the non-hydrogen atoms. The latter were refined with isotropic displacement parameters which were set to values of 1.2 U eq of the neighbouring oxygen atoms [40]. The final difference Fourier syntheses revealed no significant residual electron density. The refined atomic positions, displacement parameters, and interatomic distances are given in Tables 2 and 3.

Table 2:

Wyckoff sites, atomic coordinates, equivalent isotropic and anisotropic displacement parameters in pm2 for PbCu(OH)2SO4 measured at 295 K. The anisotropic displacement factor exponent takes the form: −2π 2[(ha*)2 U 11 + … + 2hka*b*U 12]. Standard deviations are given in parentheses.

Atom Wyckoff x y z U 11 U 22 U 33 U 12 U 13 U 23 U eq/U iso
Pb 2e 0.32863(4) 1/4 0.84188(2) 208(1) 261(2) 150(1) 0 −11(1) 0 214(1)
Cu 2c 0 0 1/2 117(3) 107(3) 160(3) 5(2) 21(2) −11(2) 129(1)
S 2e 0.1160(3) 1/4 0.16792(13) 121(5) 158(6) 136(6) 0 33(5) 0 138(2)
O1 2e 0.9344(9) 1/4 0.0243(4) 200(20) 251(19) 154(18) 0 1(16) 0 207(8)
O2 2e 0.4291(10) 1/4 0.1640(5) 130(20) 400(20) 270(20) 0 67(17) 0 266(9)
O3 4f 0.0572(7) 0.0374(4) 0.2471(3) 287(16) 169(12) 155(13) −25(11) 37(11) 15(10) 206(6)
O4 2e 0.7146(8) 1/4 0.4658(4) 107(16) 127(16) 157(17) 0 21(14) 0 131(7)
O5 2e 0.2678(8) 1/4 0.5950(4) 114(16) 152(16) 148(17) 0 35(13) 0 137(7)
H1 2e 0.628(14) 1/4 0.373(2) 160a
H2 2e 0.428(10) 1/4 0.558(7) 160a

  1. aFixed parameter.

Table 3:

Interatomic distances (pm) for PbCu(OH)2SO4. All distances of the first coordination spheres are listed. Standard deviations are given in parentheses.

Pb: 1 O5 234.3(4)
2 O3 243.7(3)
1 O1 281.8(3)
1 O1 299.2(3)
2 O2 304.2(3)
1 O2 304.9(3)
Cu: 2 O4 191.9(3)
2 O5 197.3(2)
2 O3 252.8(3)
S: 1 O1 146.2(4)
1 O2 147.3(5)
2 O3 148.0(3)
O4: 1 H1 90(2)
O5: 1 H2 90(6)

CCDC 2071334 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

2.4 EDX data

A clump of linarite crystals from the sample shown in Figure 2 was broken off the matrix and studied by energy-dispersive X-ray spectroscopy (EDX) using a Zeiss EVO® MA10 scanning electron microscope in variable pressure mode (60 Pa) with PbF2, Cu, FeS2 and SiO2 as standards. The EDX analyses on several lath-shaped crystals showed a Pb:Cu:S:O ratio of 1.0(1):0.9(1):1.1(1):6.2(2), close to the ideal composition. No impurity elements were detected.

2.5 Electronic structure calculations

All density-functional theory (DFT) single-point calculations were performed using the periodic Amsterdam density functional (ADF-BAND) package [41], [42] within generalized gradient approximation using the Perdew–Burke–Ernzerhof (PBE) [43] functional and a double zeta with polarization functions (DZP)-type basis set. The Brillouin zone was sampled by a 5 × 3 × 3 k-grid. Relativistic effects are treated with the scalar relativistic zero order regular approximation (ZORA) [44], [45]. The experimentally determined structure of linarite was employed without further optimization. Optimized structures of PbO and PbSO4 were taken from the literature [46]. Chemical bonding was analysed using the electron localization function (ELF) [47], [48] as included in ADF-BAND, providing a measure of electron pairing (a value of unity indicates perfect localization).

3 Crystal chemical description

The structural description of linarite so far mainly focused on the hydrogen bonding [14] and the copper-oxygen substructure [3], [22], [26], which is the striking structural motif for the quasi one-dimensional S = 1/2 frustrated-spin chain. A view of the PbCuSO4(OH)2 structure along the monoclinic axis is presented in Figure 3, emphasizing two important building groups, (i) the isolated SO4 2− tetrahedra and (ii) the strongly elongated CuO6 10− octahedra. The SO4 2− tetrahedra show S–O distances in a comparatively small range of 146.2–148.0 pm. These distances are in good agreement with those of previous work [12], [14] as well as in the anglesite structure (PbSO4, d(S–O): 142–148 pm [49]).

Figure 3: (left) Unit cell of PbCuSO4(OH)2. Lead, copper, oxygen and hydrogen atoms are drawn as grey, blue, red, and black circles, respectively. The elongated CuO6 (4 + 2 coordination) octahedra and the SO4 tetrahedra are emphasized. (right) Cutout of a chain of condensed CuO6 octahedra and SO4 tetrahedra. The longer Cu–O3 distances of 252.8 pm are emphasized by dashed lines.
Figure 3:

(left) Unit cell of PbCuSO4(OH)2. Lead, copper, oxygen and hydrogen atoms are drawn as grey, blue, red, and black circles, respectively. The elongated CuO6 (4 + 2 coordination) octahedra and the SO4 tetrahedra are emphasized. (right) Cutout of a chain of condensed CuO6 octahedra and SO4 tetrahedra. The longer Cu–O3 distances of 252.8 pm are emphasized by dashed lines.

The SO4 2− tetrahedra condense with the lead cations and build double-layers which extend in ab direction. These double-layers are further condensed in c direction with the copper-oxygen substructure. The formally very high charge density on the CuO6 10− octahedra is diminished by two different features: (i) the Cu2+ cations show a pronounced Jahn-Teller distortion (d(Cu–O4): 2 × 191.9 pm, d(Cu–O5): 2 × 197.3 pm and d(Cu–O3): 2 × 252.8 pm), and (ii) the O4 and O5 atoms correspond to the hydroxide groups. Neglecting the loosely bound O3 atoms and considering the substantial monoclinic distortion, the copper-oxygen coordination is distorted square-planar. These CuO4 units are trans edge-linked to infinite chains (Figure 4). Adjacent CuO4 units are slightly tilted with respect to each other. The copper atoms (Wyckoff site 2c) have centrosymmetric site symmetry 1 ‾ ; and therefore the hydrogen atoms of the hydroxide groups point alternatingly up and down the CuO4 units.

Figure 4: Cutout of the Cu(OH)2 substructures of Cu(OH)2 [41] (top) and PbCuSO4(OH)2 (bottom). Copper, oxygen and hydrogen atoms are drawn as blue, red, and black circles, respectively. Atom designations and relevant interatomic distances (in pm) are given.
Figure 4:

Cutout of the Cu(OH)2 substructures of Cu(OH)2 [41] (top) and PbCuSO4(OH)2 (bottom). Copper, oxygen and hydrogen atoms are drawn as blue, red, and black circles, respectively. Atom designations and relevant interatomic distances (in pm) are given.

The CuO4 substructure of PbCuSO4(OH)2 is closely related to the structure of Cu(OH)2 (Figure 4) [50]. The striking difference concerns the orientation of the hydroxide groups. Cu(OH)2 is non-centrosymmetric (space group Cmc21) and the copper atoms on Wyckoff position 4a have site symmetry m and two slightly different Cu–O distances. The O1H1 and O2H2 groups point all to one side of each CuO4/2 ribbon. These 1D Cu(OH)2 ribbons are condensed via hydrogen bonding. For a more general overview on copper-oxygen substructures in complex oxides we refer to a detailed review by Eby and Hawthorne [51].

4 Lone-pair character at the lead cations

A final structural issue of linarite not discussed in the literature as yet concerns the coordination of the lead atoms. Each Pb2+ cation has eight oxygen neighbours (Figure 5), O5 from a hydroxide group, five oxygen atoms from end-on and two oxygen atoms from a side-on coordination of sulfate tetrahedra. In view of the similar Cu(OH)2 ribbons (Figure 4), at first sight one might consider PbCuSO4(OH)2 as a 1:1 intergrowth structure of PbSO4 and Cu(OH)2 slabs; however, the lead coordination in the anglesite structure is distinctly different (Figure 6). The coordination number therein is increased to 10, resulting from four end-on and three side-on coordinating sulfate tetrahedra.

Figure 5: Coordination of the lead atom (site symmetry m) in PbCuSO4(OH)2. Atom designations and relevant Pb–O distances (in pm) are given.
Figure 5:

Coordination of the lead atom (site symmetry m) in PbCuSO4(OH)2. Atom designations and relevant Pb–O distances (in pm) are given.

Figure 6: Coordination of the lead atom (site symmetry m) in PbSO4 [49]. Atom designations and relevant Pb–O distances (in pm) are given.
Figure 6:

Coordination of the lead atom (site symmetry m) in PbSO4 [49]. Atom designations and relevant Pb–O distances (in pm) are given.

This difference is reflected in the calculated electronic structure, especially in the ELF. Figure 7 shows rather isotropic ELF values around the lead cations in PbSO4. In linarite, the density of spin-paired electrons is less symmetric around the lead cations (Figure 8). Yet, it does not display the typical localization basin pointing towards void space, associated with a lone pair, as is clearly visible for PbO in Figure 9 and in ref. [52], [53].

Figure 7: (a) Electron localization function (ELF) heat map of PbSO4 viewed along the crystallographic a axis. (b) ELF isosurface at a value of 0.4. Lead, sulfur and oxygen atoms are drawn as grey, yellow and red spheres, respectively.
Figure 7:

(a) Electron localization function (ELF) heat map of PbSO4 viewed along the crystallographic a axis. (b) ELF isosurface at a value of 0.4. Lead, sulfur and oxygen atoms are drawn as grey, yellow and red spheres, respectively.

Figure 8: Electron localization function (ELF) of linarite. View along the a axis (a) and the b axis (b) with isosurface value of 0.4. (c) Orientation of the coloured plane shown in (d). (d) ELF heat map viewed along the c axis. Lead, copper, sulfur, oxygen and hydrogen atoms are drawn as grey, orange, yellow, red, and white spheres, respectively.
Figure 8:

Electron localization function (ELF) of linarite. View along the a axis (a) and the b axis (b) with isosurface value of 0.4. (c) Orientation of the coloured plane shown in (d). (d) ELF heat map viewed along the c axis. Lead, copper, sulfur, oxygen and hydrogen atoms are drawn as grey, orange, yellow, red, and white spheres, respectively.

Figure 9: Electron localization function (ELF) of PbO. (a) Isosurface at a value of 0.4. (b) Heat map. Lead and oxygen atoms are drawn as grey and red spheres, respectively.
Figure 9:

Electron localization function (ELF) of PbO. (a) Isosurface at a value of 0.4. (b) Heat map. Lead and oxygen atoms are drawn as grey and red spheres, respectively.

Dedicated to: Professor Richard Dronskowski of the RWTH Aachen on the occasion of his 60th birthday.

Corresponding author: Rainer Pöttgen, Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster, Germany, E-mail:

Acknowledgements

We thank SIMMCG (Syndicat Intercommunal du Musée de la Mine de Cap Garonne) for supporting the scientific work within the mine and Dr. Carsten Paulmann and the beamline staff of P24, DESY, for their support during the diffraction experiments.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-03-25
Accepted: 2021-05-05
Published Online: 2021-05-24
Published in Print: 2021-11-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
  8. Solving the puzzle of the dielectric nature of tantalum oxynitride perovskites
  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. Exploring the frontier between polar intermetallics and Zintl phases for the examples of the prolific ALnTnTe3-type alkali metal (A) lanthanide (Ln) late transition metal (Tn) tellurides
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
https://doi.org/10.1515/znb-2021-0041
Keywords for this article
crystal structure; lead; linarite; lone pair; Mine du Pradet

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
  8. Solving the puzzle of the dielectric nature of tantalum oxynitride perovskites
  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. Exploring the frontier between polar intermetallics and Zintl phases for the examples of the prolific ALnTnTe3-type alkali metal (A) lanthanide (Ln) late transition metal (Tn) tellurides
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
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