Structure and electrons in mayenite electrides.

One major goal in materials chemistry is to find inexpensive compounds with improved capabilities. Stable inorganic electrides, derived from nanoporous mayenite [Ca12Al14O32]O, are a new family that has very interesting properties such as electronic conductivity combined with transparency. However, an intriguing fundamental problem is to understand the structures of these cubic materials and to characterize their free-electron loadings. Here we report an accurate structural study for three members of the series [Ca12Al14O32]O(1-delta)e(2delta) (delta = 0, 0.15, and 0.45), from single-crystal low-temperature synchrotron X-ray diffraction. The complex structural disorder imposed by the presence of the oxide anions into the mayenite cages has been unravelled. Furthermore, the final electron density map for delta = 0.45 black mayenite has shown electron density localized into the center of the cages, which is the first experimental proof of their electride nature. The reported structural findings challenge theorists to improve predictive models in this new family of materials.

Crystal structures and in-situ formation study of mayenite electrides.

Mayenite inorganic electrides are antizeolite nanoporous materials with variable electron concentration [Ca12Al14O32]2+ square5-deltaO1-delta2-e2delta- (0 < delta < or = 1), where square stands for empty sites. The oxymayenite crystal structure contains positively charged cages where loosely bounded oxide anions are located. These oxygens can be removed to yield electron-loaded materials in which the electrons behave like anions (electrides). Here, a new preparation method, which allows synthesizing powder mayenite electrides easily, is reported. Accurate structural data for the white (delta = 0) and green electride (delta approximately 0.5) are reported from joint Rietveld refinements of neutron and synchrotron X-ray powder diffraction data and also from single-crystal diffraction. The electride formation at high temperature under vacuum has been followed in-situ by neutron powder diffraction. The evolution of mayenite crystal structure, including the changes in the key occupation factor of the intracage oxide anions, is reported. Furthermore, the stability of mayenite framework in very low oxygen partial pressure conditions is also studied. It has been found that C12A7 decomposes, at 1373 K in reducing conditions, to give Ca5Al6O14 (C5A3) and Ca3Al2O6 (C3A). The kinetics of this transformation has also been studied. The fit of the transformed fraction to the classic Avrami-Erofe'ev equation gave an "Avrami exponent", n = 2, which indicates that nucleation is fast and the two-dimensional linear growth of the new phases is likely to be the limiting factor.

Complexes formed between nitrilotris(methylenephosphonic acid) and M(2+) transition metals: isostructural organic-inorganic hybrids.

Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation.

Simultaneous Antiferromagnetic Order and Spin-Glass-like Behavior in MnAsO(4).

A low-temperature time-of-flight neutron powder diffraction study of a simple new solid, MnAsO(4), in a sample also containing 20% Mn(2)As(2)O(7) has been performed. MnAsO(4) orders magnetically at 14.5(5) K, and the unusual antiferromagnetic structure below this temperature has been determined. Only half of the Mn(3+) spins are ordered, and the remaining "idle" spins show some spin-glass behavior evidenced by susceptibility measurements. The ordered moment is reduced to a value of 2.6 &mgr;(B) by frustration. It is not possible to determine which of the two crystallographically inequivalent Mn sublattices is magnetically ordered and which is idle. The antiferromagnetic structure of the minority phase Mn(2)As(2)O(7) which orders at 10.5(5) K has also been determined.

Aluminum Phenylphosphonates: A Fertile Family of Compounds.

Six aluminum phenylphosphonates have been synthesized depending upon the synthetic conditions: Al(2)(O(3)PC(6)H(5))(3).2H(2)O (I), Al(2)(O(3)PC(6)H(5))(3) (II), alpha-Al(HO(3)PC(6)H(5))(O(3)PC(6)H(5)).H(2)O (III), beta-Al(HO(3)PC(6)H(5))(O(3)PC(6)H(5)).H(2)O (IV), Al(HO(3)PC(6)H(5))(3).H(2)O (V), and Al(OH)(O(3)PC(6)H(5)) (VI). Thermal analysis, X-ray powder thermodiffractometry, IR spectroscopy, and (27)Al and (31)P MAS NMR data have been obtained to study the structure and thermal stability of these materials. III crystallizes in the orthorhombic system, space group Pbca, with a = 9.7952(1) Å, b = 29.3878(4) Å, c = 9.3537(3) Å, and Z = 8. The structure was solved ab initio, from synchrotron data (lambda approximately 0.4 Å), using direct methods, and refined by Rietveld methods. The final agreement factors were R(wP) = 6.73%, R(P) = 5.24%, and R(F)() = 6.8%. The compound is layered with the aluminum atoms in an octahedral environment of oxygens and two crystallographically independent phosphonate groups, one being protonated. The powder patterns of V and VI have been indexed, and the experimental observations are consistent with layered structures. The unit cell of V contains one octahedral site for Al and three tetrahedral sites for P. Phosphonate I seems to have a three-dimensional tubular structure with aluminum atoms in both octahedral and tetrahedral environments and phosphorus atoms in three different types of sites.

Structure Determination of a Complex Tubular Uranyl Phenylphosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, from Conventional X-ray Powder Diffraction Data.

The three-dimensional structure of a complex tubular uranyl phosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2(1)2(1)2(1), with a = 17.1966(2) Å, b = 7.2125(2) Å, c = 27.8282(4) Å, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure solution of complex inorganic compounds, including organometallic compounds.