A new intermediate intercalate in superconducting sodium-doped hafnium nitride chloride.

A new phase has been observed during the sodium intercalation of hafnium nitride chloride as intermediate between the host beta-HfNCl and the already reported Na(0.29)HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K.

Anion ordering and defect structure in Ruddlesden-Popper strontium niobium oxynitrides.

The crystal structure of the n = 1 member of the Ruddlesden-Popper family (SrO)(SrNbO(2)N)(n) was refined by the Rietveld method using neutron powder diffraction data. This complex crystallizes in the I4/mmm space group with cell parameters a = 4.0506(2) and c = 12.5936(9) angstroms. The refined composition was Sr(2)NbO(3.28)N(0.72), which corresponds to a formal oxidation state for Nb of +4.72, meaning 72% Nb(V) and 28% Nb(IV). The nitrogen atoms order in the equatorial sites of the niobium octahedra according to Pauling's second crystal rule as the more charged anion occupies the site showing the larger bond strength sums. Pauling's second crystal rule is shown to be able to predict the distribution of anions in the available crystallographic sites in other mixed anion systems such as oxyhalides with K(2)NiF(4) structures and other oxynitrides. The defect structure of the n = 1 and n = 2 members of the same family was investigated by high-resolution electron microscopy. Recurrent intergrowth along the c axis with other Ruddlesden-Popper members (n = 3, 4, and perovskite) is observed, resulting in streaking along this direction in the corresponding electron diffraction patterns.

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides.

The layered nitrides beta-MNX (M = Zr, Hf; X = Cl, Br) crystallize in the space group R&thremacr;m with a hexagonal cell of dimensions a = 3.6031(6) Å, c = 27.672(2) Å for beta-ZrNCl, a = 3.5744(3) Å, c = 27.7075(9) Å for beta-HfNCl, and a = 3.6379(5) Å, c = 29.263(2) Å for beta-ZrNBr. Lithium intercalation using n-buthyllithium in hexane solutions leads to solvent free superconductors of formula Li(0.20)ZrNCl, Li(0.42)HfNCl, Li(0.67)HfNCl, and Li(0.17)ZrNBr showing critical temperatures of 12, 18, 24, and 13.5 K, respectively. Whereas several samples of beta-ZrNBr and beta-ZrNCl showed reproducibility in the lithium uptake and in the corresponding critical temperatures, different samples of beta-HfNCl subjected to the same treatment in n-buthyllithium showed lithium uptakes ranging from 0.07 to 0.67, and corresponding critical temperatures between 0 and 24 K. A linear dependence of T(c) versus the lithium content is observed when all the superconducting samples are considered. The results obtained from electrochemical lithiation are consistent with those obtained with chemical methods, as samples with larger capacity on discharge are also those found to have larger lithium contents after chemical lithiation. Most samples present a reduction step around 1.8 V vs Li(0)-Li(+) whose origin is still unclear. The electrochemical capacity on discharge for beta-HfNCl and beta-ZrNBr depends on the milling time spent in the preparation of the electrodes, with long milling times resulting in lower intercalation degree. Possible causes for this effect are either the creation of structural defects (e.g., stacking faults) or some sample decomposition induced by local heating. The same phenomena are proposed to account for the different behavior of beta-HfNCl samples, although additional aspects such as the presence of hydrogen, oxygen, or extra hafnium atoms in the structure have to be considered. Tight-binding band structure calculations for beta-MNX (M = Zr, X = Cl, Br; M = Hf, X = Cl), ZrCl, and Y(2)C(2)Br(2) are reported. The density of states and Fermi surfaces of the beta-MNX phases as well as the relationship between the electronic structure of the beta-ZrNCl and ZrCl are discussed. Despite the structural relationships, the electronic structures near the Fermi level of the beta-MNX and Y(2)Br(2)C(2) phases are found to be very different.

Synthesis and Crystal Structure of a Novel Lamellar Barium Derivative: Ba(VOPO(4))(2).4H(2)O. Synthetic Pathways for Layered Oxovanadium Phosphate Hydrates M(VOPO(4))(2).nH(2)O.

A unified synthetic strategy has allowed us to rationalize the preparative chemistry of the layered oxovanadium phosphates M(VOPO(4))(2).nH(2)O. Thus, we have been able to isolate as single phases with reasonable yields both all the previously characterized phosphates and a new solid containing Ba(2+) cations as guest species as well as to prepare new related derivatives involving arsenate anions. In order to organize the experimental results, we have used two complementary models: a simple restatement of the partial charge model (PCM), and the valence matching principle (VMP) (derived from the bond valence method). The crystal structure of the new barium lamellar derivative, Ba(VOPO(4))(2).4H(2)O, has been solved from X-ray single crystal data. The cell is monoclinic (space group Pn; Z = 1) with a = 6.3860(3) Å, b = 12.7796(9) Å, c = 6.3870(5) Å, and beta = 90.172(6) degrees. Its structure, like it occurs with the other members of the M(VOPO(4))(2).nH(2)O family, can be thought of as derived from that of the well-known lamellar solid VOPO(4)(.)2H(2)O. Ba(2+) cations are located in the interlamellar space with an environment defined by 12 oxygen atoms. A comparative study of this family shows significant crystallochemical correlations with the radius of the guest cations.

Synthetic Strategies To Obtain V-P-O Open Frameworks Containing Organic Species as Structural Directing Agents. Crystal Structure of the V(IV)-Fe(III) Bimetallic Phosphate [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)][Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O.

A general synthetic approach to rationalize the solution preparative chemistry of oxovanadium phosphates containing organic species as structural directing agents is presented. Careful attention is payed to the hydrolysis and condensation processes involving the ionic species in solution, and a simple restatement of the partial charge model (PCM) has been used in order to organize the experimental results. The structure of a new V(IV)-Fe(III) bimetallic oxovanadium phosphate, [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)] [Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O, has been determined by X-ray single crystal diffraction methods. This compound crystallizes in the monoclinic system, space group P2(1)/n and the cell dimensions are as follows: a = 14.383(3) Å, b = 10.150(2) Å, c = 18.355(4) Å, and beta = 90.39(3) degrees (Z = 2). The existence of a complex intercrossing channel system, including a very large channel of 18.4 Å of diameter (in which both water molecules and ethylenediamine species are located), is the more interesting feature of this structure. Thermal decomposition, including the dehydration/rehydration process, has been studied by thermal analysis and variable temperature X-ray powder diffraction techniques. A complementary SEM study of the different intermediate decomposition products is presented.