NaZn(H2O)2[BP2O8].H2O: a novel open-framework borophosphate and its reversible dehydration to microporous sodium zincoborophosphate N

Crystals of NaZn(H2O)2[BP2O8].H2O were grown under mild hydrothermal conditions at 170 degrees C. The crystal structure (solved by X-ray single-crystal methods: hexagonal, P6(1)22 (no. 178), a = 946.2(2), c= 1583.5(1) pm, V= 1227.8(4).10(6) pm3, Z = 6) exhibits a chiral octahedral-tetrahedral framework related to the CZP topology and contains helical ribbons of corner-linked borate and phosphate tetrahedra. Investigation of the thermal behavior up to 180 degrees C shows a (reversible) dehydration process; this leads to the microporous compound Na[ZnBP2O8].H2O, which has the CZP topology. The crystal structure of Na[ZnBP2O8].H2O was determined by X-ray powder diffraction by using a combination of simulated annealing, lattice-energy minimization, and Rietveld refinement procedures (hexagonal, P6(1)22 (no. 178), a = 954.04(2), c = 1477.80(3) pm, V= 164.88(5).10(6) pm3, Z = 6). The essential structural difference caused by the dehydration concerns the coordination of Zn2- changing from octahedral to tetrahedral arrangement.     

Synthesis,Magnetism, and Crystal Structure of Li2Fe[(PO4)(HPO4)] and its Hydrogen Position Refinement

Lithium iron(III) monophosphate-monohydrogen-monophosphate, Li₂Fe[(PO₄)(HPO₄)], was synthesized under mild hydrothermal conditions and its crystal structure was determined by single crystal X-ray diffraction methods. Crystallographic data: monoclinic, P12₁/n1 (no. 14), a = 4.8142(2) Å, b = 7.9898(4) Å, c = 7.4868(4) Å, β = 104.398(3)°, V = 278.93(2) ų, Z = 2, D_x = 3.104 g · cm^-3. The structure is characterized by FeO₆ octahedra sharing common O-corners with six neighbouring PO₄ tetrahedra to form a three-dimensional framework. Lithium cations are located within channels running along [100]. The channels are formed by eight-membered rings resulting from the connection of alternating FeO₆ octahedra (4×) and phosphate tetrahedra (4×). High-resolution diffraction data allowed to refine a split model for the position of the hydrogen atom. Magnetization data confirm the valence state 3+ for iron and detect an antiferromagnetic ordering of the iron moments below 23.6 K. Thermal decomposition of the compound was investigated by DTA/TG methods.     

Li24[MnN3]3N2 and Li5[(Li1-xMnx)N]3, two intermediates in the decomposition path of Li7[MnN4] to Li2[(Li1-xMnx)N]: an experimental and theoretical study

The crystal structure of Li7[Mn(V)N4] was re-determined. Isolated tetrahedral [Mn(V)N4](7-) ions are arranged with lithium cations to form a superstructure of the CaF2 anti-type (P4bar3n, No. 218, a = 956.0(1) pm, Z = 8). According to measurements of the magnetic susceptibility, the manganese (tetrahedral coordination) is in a d(2) S = 1 state. Thermal treatment of Li7[Mn(V)N4] under argon in the presence of elemental lithium at various temperatures leads to Li24[Mn(III)N3]3N2, Li5[(Li1-xMnx)N]3, and Li2[(Li1-xMn(I)x)N], respectively. Li24[Mn(III)N3]3N2 (P3bar1c, No. 163, a = 582.58(6) pm, c = 1784.1(3) pm, Z = 4/3) crystallizes in a trigonal unit cell, containing slightly, but significantly nonplanar trigonal [MnN3](6-) units with C3v symmetry. Measurements of the magnetic susceptibility reveal a d(4) S = 1 spin-state for the manganese (trigonal coordination). Nonrelativistic spin-polarized DFT calculations with different molecular models lead to the conclusion that restrictions in the Li-N substructure are responsible for the distortion from planarity of the [Mn(III)N3](6-). Li5[(Li1-xMnx)N]3 (x = 0.59(1), P6bar2m, No. 189, a = 635.9(3) pm, c = 381.7(2) pm, Z = 1) is an isotype of Li5[(Li1-xNix)N]3 with manganese in an average oxidation state of about +1.6. The crystal structure is a defect variant of the alpha-Li3N structure type with the transition metal in linear coordination by nitrogen. Li2[(Li1-xMn(I)x)N] (x = 0.67(1), P6/mmm, No. 191, a = 371.25(4) pm, c = 382.12(6) pm, Z = 1) crystallizes in the alpha-Li3N = Li2[LiN] structure with partial substitution of the linearly nitrogen-coordinated Li-species by manganese(I). Measurements of the magnetic susceptibility are consistent with manganese (linear coordination) in a low-spin d(6) S = 1 state.     

Ba[CoN]: Ein niedervalentes Nitridocobaltat mit gewinkelten Ketten [CoN2/22−]

Ba[CoN]: A Low-Valency Nitridocobaltate with Angled Chains [CoN_2/2^2?] Ba[CoN] is prepared by reaction of barium and cobalt (molar ratio Ba : Co = 1 : 2.5) in tantalum crucibles at 870°C with flowing nitrogen (1 atm) within a period of 96 h. After cooling down to room temperature (24°C/h) black single crystals of the ternary phase with a platy habit are obtained (orthorhombic, Pnma; a = 959.9(2) pm, b = 2 351.0(3) pm, c = 547.6(2) pm; Z = 20). The crystal structure of Ba[CoN] contains angled (planar) chains [CoN_2/2^2?] which run along the [010]-direction (N? Co? N[°]: 178.5(5), 179.6(6), 180.0; Co? N? Co[°]: 82.9(6), 84.2(5), 177.1(8); Co? N[pm]: 174.6(12), 177.2(12), 181.9(13), 184.3(13), 187.1(12)). Nitrogen is in an octahedral coordination (N Ba₄Co₂) and is arranged in a distorted cubic close packing. Barium occupies one half of the tetrahedral holes (Ba? N[pm]: 274.8(16) ? 308.2(12)). The cis-positions of the Co-atoms at the nitrogen coordination-octahedra cause short Co? Co contacts within the chains [CoN_2/2^2?]. Through this, Co₂-units (Co? Co[pm]: 247.8(4); bridged by nitrogen) and linear Co₃-groups (Co? Co [pm]: 245.5(2); Co? Co? Co[°]: 180.0; bridged by nitrogen) alternate along the chains. The crystal structure of Ba[CoN] is closely related to the Ba[NiN] type structure.     

Control of Oxidation States of Transition Elements (Cr,Mn) in Nitridometalates and the Solid Solution Series Li6(Ca1‐xSrx)2[Mn2N6]

The formation of ternary nitridometalates from the elements in the case of the systems Li—Cr, V, Mn—N leads to compounds which contain the transition metals in the highest (V^V, Cr^VI) or a comparably high (Mn^V) oxidation state. In the corresponding calcium and strontium systems, the transition metals show a lower oxidation state (V^III, Cr^III, Mn^III). Transition metals with intermediate oxidation states (Cr^V, Mn^IV) are present in the quaternary (mixed cation) compounds Li₄Sr₂[CrN₆], Li₆Ca₂[MnN₆], and Li₆Sr₂[MnN₆] (R3¯(#148), a = 585.9(3) pm, c = 1908.6(4) pm, Z = 3), as well as in the solid solution series Li₆(Ca_1—xSr_x)₂[MnN₆].