Structure Topology and Graphical Representation of Decorated and Undecorated Chains of Edge-Sharing Octahedra

ABSTRACT Infinite chains of edge-sharing octahedra occur as fundamental building blocks (FBBs) in the structures of several hundred mineral species. Such chains consist of a backbone of octahedra to which decorating polyhedra may be attached. The general, stoichiometric formula of such chains may be written as c[MATxФz] where M is any octahedrally coordinated cation, T is any cation coordinated by a decoration polyhedron (regardless of coordination geometry), Ф is any possible ligand [O2–, (OH)–, (H2O), Cl–, or F–], and c indicates the configuration of backbone octahedra. In the minerals in which they occur, these types of chains will commonly (though not exclusively) form part of the structural unit (i.e., the strongly bonded part) of a mineral. Hence, investigating the topology, configuration, and arrangement of such chains may yield fundamental insights into the stability of minerals in which they occur. A discussion of the topological variability of chains is presented here, along with the formulae necessary for their characterization. It is shown that many aspects of chain topology can be efficiently communicated by a pair of values with the form ([x], [Bopqrst]), where [x] summarizes the symmetry operations necessary to characterize the configuration of backbone octahedra, B indicates the length of the topological repeat, and o through t indicate the number of individual decorations (related to B). A methodology for developing finite graphical representations for infinite chains is presented in detail, showing that for any given chain, a single, irreducible finite graph exists that contains all topological information. Such a graph, however, can correspond to multiple chain topologies, highlighting the importance of geometrical isomerism. The utility of the graphical approach in facilitating the development of a hierarchy of chains and chain-bearing structures is also discussed.

Synthesis, crystal structure determination of a novel phosphate Ag1.64Zn1.64Fe1.36(PO4)3 with an alluaudite-like structure

Single crystals of Ag1.64Zn1.64Fe1.36(PO4)3 [silver zinc iron phosphate (1.64/1.64/1.36/3)] have been synthesized by a conventional solid-state reaction and structurally characterized by single-crystal X-ray diffraction. The title compound crystallizes with an alluaudite-like structure. All atoms of the structure are in general positions except for four, which reside on special positions of the space group, C2/c. The Ag+ cations reside at full occupancy on inversion centre sites and at partial occupancy (64%) on a twofold rotation axis. In this structure, the unique Fe3+ ion with one of the two Zn2+ cations are substitutionally disordered on the same general position (Wyckoff site 8f), with a respective ratio of 0.68/0.32 (occupancies were fixed so as to ensure electrical neutrality for the whole structure). The remaining O and P atoms are located in general positions. The three-dimensional framework of this structure consists of kinked chains of edge-sharing octahedra stacked parallel to [10\overline{1}]. These chains are built up by a succession of [MO6] (M = Zn/Fe or Zn) units. Adjacent chains are connected by the PO4 anions, forming sheets oriented perpendicular to [010]. These interconnected sheets generate two types of channels parallel to the c axis, in which the Ag+ cations are located. The validity and adequacy of the proposed structural model of Ag1.64Zn1.64Fe1.36(PO4)3 was established by means of bond-valence-sum (BVS) and charge-distribution (CHARDI) analysis tools.

dz2 orbital character of polyhedra in complex solid-state transition-metal compounds

dz2 orbitals of the transition metals make major contributions to electronic structures near the Fermi levels in d0-, d1-complex transition-metal compounds containing face-sharing, edge-sharing octahedra, or edge-sharing trigonal prismatic layers.

Folvikite, Sb5+Mn3+(Mg,Mn2+)10O8(BO3)4, a new oxyborate mineral from the Kitteln mine, Nordmark ore district, Värmland, Sweden: description and crystal structure

ABSTRACTFolvikite, Sb5+Mn3+(Mg,Mn2+)10O8(BO3)4, is a new oxyborate mineral from the Kitteln mine, Värmland, Sweden, where it occurs as a primary skarn mineral embedded in calcite. It forms striated prismatic crystals up to 0.3 mm, and is black to dark reddish-brown with submetallic lustre and a reddish-brown streak. It is brittle, has a Mohs hardness of 6, and the calculated density is 4.14 g/cm3. Folvikite is biaxial with indeterminate optic sign due to pervasive twinning. The optic axial angle is 68.9(4)°. Refractive indices were not measured; the calculated mean refractive index is 1.85. Strong pleochroism was observed in plane-polarized light: AB = brown (intermediate), OB = dark brown (maximum) and ON = honey brown (minimum). Folvikite is monoclinic, space group P2, a = 5.3767(10), b = 6.2108(10), c = 10.9389(18) Å, β = 94.399(9)°, V = 364.22(16) Å3 and Z = 1. Chemical analysis by electron microprobe gave Sb2O5 18.15, MgO 24.11, MnO 29.73, Mn2O3 11.62, Al2O3 0.27, Fe2O3 0.45, B2O3 15.27, sum 99.60 wt.%. The B2O3 content was assigned as B = 4 apfu and the Mn2O3 / (MnO + Mn2O3) ratio was determined from the crystal structure. The empirical formula was normalized on the basis of 20 anions pfu: (Sb5+1.02Mn3+1.34Al0.05Fe3+0.05Mg5.46Mn2+3.82□0.26)Σ12O8(BO3)4. A simplified formula may be written as Sb5+Mn3+(Mg,Mn2+)10O8(BO3)4 with Z = 1. The crystal structure was solved by direct methods and refined to an R1 index of 4.1%. Folvikite is a member of the (3 Å) zigzag wallpaper-borate structures in which chains of edge-sharing octahedra extend along the c axis and are cross-linked by BO3 groups. There are five X sites partly occupied by Mn2+ > Mg, one octahedrally coordinated M-site occupied by Sb5+ > Mg, two M sites occupied by Mg ≥ Mn > Sb5+, two M sites occupied by Mn3+ > Mn2+, two M sites occupied by Mg > Mn2+, and one M-site occupied by Mg > □; plus two [3]-coordinated B sites occupied by B. As with the other zigzag borates, the polyhedra are arranged in F-walls, C-walls and S-columns.

Flurlite, Zn3Mn2+Fe3+(PO4)3(OH)2·9H2O, a new mineral from the Hagendorf Süd pegmatite, Bavaria, with a schoonerite-related structure

Flurlite, ideally Zn3Mn2+Fe3+(PO4)3(OH)2·9H2O, is a new mineral from the Hagendorf-Süd pegmatite, Hagendorf, Oberpfalz, Bavaria, Germany. Flurlite occurs as ultrathin (<1 μm) translucent platelets that form characteristic twisted accordion-like aggregates. The colour varies from bright orange red to dark maroon red. Cleavage is perfect parallel to (001). The mineral occurs on mitridatite and is closely associated with plimerite. Other associated minerals are beraunite, schoonerite, parascholzite, robertsite and altered phosphophyllite. The calculated density of flurlite is 2.84 g cm–3. It is optically biaxial (–), α = 1.60(1), β= 1.65(1) and γ = 1.68(1), with weak dispersion and parallel extinction, X ≈ c, Y ≈ a, Z ≈ b. Pleochroism is weak, with colours: X = pale yellow, Y = pale orange, Z = orange brown. Electron microprobe analyses (average of seven) with FeO and Fe2O3 apportioned and H2O calculated on structural grounds, gave ZnO 25.4, MnO 5.28, MgO 0.52, FeO 7.40, Fe2O3 10.3, P2O5 27.2, H2O 23.1, total 99.2 wt.%. The empirical formula, based on 3 P a.p.f.u. is Zn2.5Mn2+0.6Fe2+0.8Mg0.1Fe3+(PO4)3(OH)2·9H2O. Flurlite is monoclinic, P21/m, with the unit-cell parameters (at 100 K) of a = 6.3710(13), b = 11.020(2), c = 13.016(3) Å, β = 99.34 (3)°. The strongest lines in the X-ray powder diffraction pattern are [dobs in Å(I) (hkl)] 12.900(100)(001); 8.375(10)(011); 6.072(14)(101); 5.567(8)(012); 4.297(21)(003); 2.763(35)(040). Flurlite (R1 = 0.057 for 995 F > 4σ(F)) has a heteropolyhedral layer structure, with layers parallel to (001) and with water molecules packing between the layers. The slab-like layers contain two types of polyhedral chains running parallel to [100]: (a) chains of edge-sharing octahedra containing predominantly Zn and (b) chains in which Fe3+-centred octahedra share their apices with dimers comprising Zn-centred trigonal bipyramids sharing an edge with PO4 tetrahedra. The two types of chains are interconnected by corner-sharing along [010]. A second type of PO4 tetrahedron connects the chains to MnO2(H2O)4 octahedra along [010] to complete the structure of the (001) slabs. Flurlite has the same stoichiometry as schoonerite, but with dominant Zn rather than Fe2+ in the edge-shared chains. Schoonerite has a similar heteropolyhedral layer structure with the same layer dimensions 6.4 × 11.1 Å. The different symmetry (orthorhombic, Pmab) for schoonerite reflects a different topology of the layers.

Crystal structure of strontium dinickel iron orthophosphate

The title compound, SrNi2Fe(PO4)3, synthesized by solid-state reaction, crystallizes in an ordered variant of the α-CrPO4structure. In the asymmetric unit, two O atoms are in general positions, whereas all others atoms are in special positions of the space groupImma: the Sr cation and one P atom occupy the Wyckoff position 4e(mm2), Fe is on 4b(2/m), Ni and the other P atom are on 8g(2), one O atom is on 8h(m) and the other on 8i(m). The three-dimensional framework of the crystal structure is built up by [PO4] tetrahedra, [FeO6] octahedra and [Ni2O10] dimers of edge-sharing octahedra, linked through common corners or edges. This structure comprises two types of layers stacked alternately along the [100] direction. The first layer is formed by edge-sharing octahedra ([Ni2O10] dimer) linked to [PO4] tetrahedraviacommon edges while the second layer is built up from a strontium row followed by infinite chains of alternating [PO4] tetrahedra and FeO6octahedra sharing apices. The layers are held together through vertices of [PO4] tetrahedra and [FeO6] octahedra, leading to the appearance of two types of tunnels parallel to thea- andb-axis directions in which the Sr cations are located. Each Sr cation is surrounded by eight O atoms.

Crystal structure of a sodium, zinc and iron(III)-based non-stoichiometric phosphate with an alluaudite-like structure: Na1.67Zn1.67Fe1.33(PO4)3

The new title compound, disodium dizinc iron(III) tris(phosphate), Na1.67Zn1.67Fe1.33(PO4)3, which belongs to the alluaudite family, has been synthesized by solid-state reactions. In this structure, all atoms are in general positions except for four, which are located on special positions of theC2/cspace group. This structure is characterized by cation substitutional disorder at two sites, one situated on the special position 4e(2) and the other on the general position 8f. The 4esite is partially occupied by Na+[0.332 (3)], whereas the 8fsite is entirely filled by a mixture of Fe and Zn. The full-occupancy sodium and zinc atoms are located at the Wyckoff positions on the inversion center 4a(-1) and on the twofold rotation axis 4e, respectively. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The three-dimensional framework of this structure consists of kinked chains of edge-sharing octahedra stacked parallel to [10-1]. The chains are formed by a succession of trimers based on [ZnO6] octahedra and the mixed-cation FeIII/ZnII[(Fe/Zn)O6] octahedra [FeIII:ZnIIIratio 0.668 (3)/0.332 (3)]. Continuous chains are held together by PO4phosphate groups, forming polyhedral sheets perpendicular to [010]. The stacked sheets delimit two types of tunnels parallel to thecaxis in which the sodium cations are located. Each Na+cation is coordinated by eight O atoms. The disorder of Na in the tunnel might presage ionic mobility for this material.

Crystal structure of dichloridobis(methyl isonicotinate-κN)copper(II)

In the title compound, [CuCl2(C7H7NO2)2], the square-planar-coordinated CuIIion lies on a centre of symmetry and is bonded to two monodentate methylisonicotinate ligands through their N atoms and by two chloride ligands. The molecules pack in a herringbone pattern. Perpendicular to [100] there are weak intermolecular C—H...Cl and C—H...O contacts. Along [100] there are infinite chains of edge-sharing octahedra linked through the chlorido ligands