JCPDS-ICDD Research Associateship (Cooperative Program with NBS/NIST).

The Research Associateship program of the Joint Committee on Powder Diffraction-International Centre for Diffraction Data (JCPDS-ICDD, now known as the ICDD) at NBS/NIST was a long standing (over 35 years) successful industry-government cooperation. The main mission of the Associateship was to publish high quality x-ray reference patterns to be included in the Powder Diffraction File (PDF). The PDF is a continuing compilation of patterns gathered from many sources, compiled and published by the ICDD. As a result of this collaboration, more than 1500 high quality powder diffraction patterns, which have had a significant impact on the scientific community, were reported. In addition, various research collaborations with NBS/NIST also led to the development of several standard reference materials (SRMs) for instrument calibration and quantitative analyses, and computer software for data collection, calibration, reduction, for the editorial process of powder pattern publication, analysis of powder data, and for quantitative analyses. This article summarizes information concerning the JCPDS-ICDD organization, the Powder Diffraction File (PDF), history and accomplishments of the JCPDS-ICDD Research Associateship.

Lattice Symmetry and Identification-The Fundamental Role of Reduced Cells in Materials Characterization.

In theory, physical crystals can be represented by idealized mathematical lattices. Under appropriate conditions, these representations can be used for a variety of purposes such as identifying, classifying, and understanding the physical properties of materials. Critical to these applications is the ability to construct a unique representation of the lattice. The vital link that enabled this theory to be realized in practice was provided by the 1970 paper on the determination of reduced cells. This seminal paper led to a mathematical approach to lattice analysis initially based on systematic reduction procedures and the use of standard cells. Subsequently, the process evolved to a matrix approach based on group theory and linear algebra that offered a more abstract and powerful way to look at lattices and their properties. Application of the reduced cell to both database work and laboratory research at NIST was immediately successful. Currently, this cell and/or procedures based on reduction are widely and routinely used by the general scientific community: (i) for calculating standard cells for the reporting of crystalline materials, (ii) for classifying materials, (iii) in crystallographic database work (iv) in routine x-ray and neutron diffractometry, and (v) in general crystallographic research. Especially important is its use in symmetry determination and in identification. The focus herein is on the role of the reduced cell in lattice symmetry determination.

A new method for phase identification for electron diffractionists.

An accurate analytical procedure for phase identification for electron diffractionists has been developed. The method opens new frontiers in the identification of solid-state materials, as crystalline samples in the size range 10 microns to 10 A can be accurately characterized. Research with NIST CRYSTAL DATA (a large database with chemical, physical, and crystallographic data on solid-state materials) has proved that a material can be uniquely characterized on the basis of its lattice and chemical composition. To characterize a material, it is sufficient to determine any primitive cell of the lattice and the element types present. Using a modern analytical electron microscope (AEM), the experimentalist can collect the required data on an unknown sample. The lattice information is obtained by rotation of the sample to obtain two or more planes of data. From these planes, a unit cell defining the lattice can be deduced. The chemical data are determined by energy-dispersive spectroscopy (EDS). Once the experimental data are measured, the unknown is identified against the database of knows using lattice/element-type matching techniques. The basic strategy consists of three conceptual steps. First, the unknown lattice is searched against the database to find all lattices that are the same or related; the results are kept in set 1. Second, the unknown is searched against the database to find all materials with the same or similar element types; the results are kept in set 2. Finally, the results in sets 1 and 2 are combined to obtain the answer set. Experience has proved that the procedure is highly selective and reliable.

NIST/Sandia/ICDD Electron Diffraction Database: A Database for Phase Identification by Electron Diffraction.

A new database containing crystallographic and chemical information designed especially for application to electron diffraction search/match and related problems has been developed. The new database was derived from two well-established x-ray diffraction databases, the JCPDS Powder Diffraction File and NBS CRYSTAL DATA, and incorporates 2 years of experience with an earlier version. It contains 71,142 entries, with space group and unit cell data for 59,612 of those. Unit cell and space group information were used, where available, to calculate patterns consisting of all allowed reflections with d-spacings greater than 0.8 A for ~ 59,000 of the entries. Calculated patterns are used in the database in preference to experimental x-ray data when both are available, since experimental x-ray data sometimes omits high d-spacing data which falls at low diffraction angles. Intensity data are not given when calculated spacings are used. A search scheme using chemistry and r-spacing (reciprocal d-spacing) has been developed. Other potentially searchable data in this new database include space group, Pearson symbol, unit cell edge lengths, reduced cell edge length, and reduced cell volume. Compound and/or mineral names, formulas, and journal references are included in the output, as well as pointers to corresponding entries in NBS CRYSTAL DATA and the Powder Diffraction File where more complete information may be obtained. Atom positions are not given. Rudimentary search software has been written to implement a chemistry and r-spacing bit map search. With typical data, a full search through ~ 71,000 compounds takes 10~20 seconds on a PDP 11/23-RL02 system.

O-imino esters of N,N-bis(2-chloroethyl)phosphorodiamidic acid. Synthesis, X-ray structure determination, and anticancer evaluation.

Nine representatives of the title series of compounds [(ClCH2CH2)2NP(O)(NH2)ON = CRR'] were synthesized as potential anticancer prodrugs, based on the possibility of enzymatic reduction of the N-O bond to release the known cytotoxic agent phosphoramide mustard [1, (ClCH2CH2)2NP(O)(NH2)OH]. The dimethyl derivative (2, R = R' = CH3) exhibited a statistically significant, albeit low, level of anti-L1210 activity in mice. Derivative 2, which was shown by 31P NMR measurements to be very stable toward hydrolysis at 37 degrees C over a pH range of 5.7-7.4 (T1/2 congruent to 7-8 weeks), gave colorimetrically detectable amounts of alkylating material upon incubation with mouse liver slices: approximately 3-5% conversion after 20 min at 37 degrees C. A single-crystal X-ray study of 2 revealed an unusual hydrogen-bonded "ladder" and a very similar steric relationship for the NCH2CH2Cl and ON = CCH3 moieties.

Synthesis and antitumor activity of cyclophosphamide analogues. 3. Preparation, molecular structure determination and anticancer screening of racemic cis- and trans-4-phenylcyclophosphamide.

Cyclization of racemic 3-amino-3-phenyl-1-propranol with bis(2-chloroethyl)phosphoramidic dichloride gave a diastereomeric mixture of 4-phenylcyclophosphamide (3), which was chromatographically separated into the faster and slower eluting components. A combination of 1H/31PNMR and IR spectral data indicated that the faster and slower racemates correspond to cis-3 (mp 129-130 degrees C) and trans-3 (mp 112-114.5 degrees C), respectively. The molecular structure of the former compound was determined by X-ray crystallography and thereby unambiguously established the cis relationship between equatorially disposed phenyl and P = O substituents in a chair conformation. These results confirm the stereochemical assignments for cis- and trans-3 which have been independently deduced by Y. E. Shih, J. S. Wang, and C. T. Chen [Heterocycles, 9, 1277 (1978)]. Anticancer screening tests against L1210 lymphoid leukemia in mice have revealed that, while both diastereomers of 3 afford toxic metabolites, trans-3 led to therapeutic activity and cis-3 did not. The relevance of these findings to results reported for 4-methylcyclophosphamide and cyclophosphamide is briefly discussed.

Dixanthylurea (N, N'-di-9H-Xanthen-9-ylurea).

C27H20N2O3, MW = 420, orthorhombic, Pbc21, a = 4.686(2), b = 16.784(8), c = 25.924(10)Å, V = 2039Å3, d obs = 1.37 g cm-3 (flotation), d calc = 1.369g cm-3, Z = 4. The structure has been determined by direct methods and refined to R = 0.045 based on 1419 independent reflections. No crystallographic symmetry element is present in the dixanthylurea molecule. In fact, the molecule is considerably distorted from any possible mirror symmetry. The molecules are hydrogen bonded in an infinite chain along the a-axis. The compound is of interest because of its role in the analytical determination of urea.

Crystal Structure of Benzene II at 25 Kilobars.

Crystals of a high-pressure form of benzene (benzene 11) were grown in the diamond-anvil pressure cell at elevated temperature and pressure from the transition of solid I to solid II. X-ray precession data were obtained from a single-crystal in the high-pressure cell. At 21 degrees C and about 25 kilobars, benzene II crystallizes in the monoclinic system with a = 5.417 +/- 0.005 angstroms (S.D.), b = 5.376 +/- 0.019 angstroms, c = 7.532 +/- 0.007 angstroms, beta = 110.00 degrees +/- 0.08 degrees , space group P2(1)/ c, Pc= 1.26 grams per cubic centimeter. The crystal structure was solved by generating all possible molecular packing configurations and calculating structure factors, reliability factors, and packing energies for each configuration. This procedure produced a unique solution for the molecular packing of benzene II.