As a result of Paul Pfeiffers suggestion of applying Werners coordination

theory to crystals (Paper Five) and the advent of new experimental techniques
(Max von Laues X-ray diffraction method (1912), William Lawrence Bragg and
William Henry Braggs method for obtaining the distances between crystal
planes (1912), and Peter Debye and Paul Scherrers powder method (1916), a
number of scientist in various countries simultaneously began to investigate
the crystal structures of coordination compunds by means of X-rays. In the
words of Ralph W.G. Wyckoff (1897-), one of the pioneers in crystallography
and the co-author of Paper Six:
Werners theory of coordination must be counted one of the great steps
forward in our understanding of chemical combination. Concerned with
the distribution of atoms in molecular complexes and coming not long
before the discovery of X-ray diffraction, it was particularly important for
those of us who were then beginning crystal analysis. This analysis, in
establishing of the first time exactly where the atoms are in a solid,
offered the most direct check imaginable of how correct Wernerns
notions about valence were, and, conversely, the ideas about
coordination arising from this theory could suggest many compounds
that it would be profitable to examine with X-rays.
According to Wyckoff, the X-ray diffraction method also provided an
unexpectedly direct way to ascertain the measure of reality behind the Werner
theory and its implied equivalence of some primary and secondary bonds.
Shortly after receiving his doctorate, Wyckoff chose ammonium
chloroplatinate as a crystal that should provide a clear-cut test of Werner
coordination. The results of his investigation, published in 1921 together with
Eugen Posnjak (1888-1949) as co-author (paper six), constitute the first
published experimental crystallographic study of a coordination compound. In
Wyckoffs own words:

All six chlorine atoms in (NH4)2PtCl6 were crystallographically identical,

They were equally distant from the metal atom, and hence there was no
difference3 in the bonds they formed with it.
Furthermore, chlorines were found to be at the corners of a regular octahedron
having the platinum atom at its center. A more complete agreement with the
predictions of the Werner theory could scarcely have been imagined.
Others quickly applied the X-ray diffraction technique and confirmed the
octahedral configuration of the six halogen atoms or ammonia molecules in
similar hexacoordinate complexes, e.g., K2(PtCl6), [Co(NH3)6 ]Cl2, Rb2[PdBr6],
(NH4)2[SnCl6], and (NH4)2[SiF6]. Wyckoff also confirmed Werners view that

the molecules of water and of ammonia in most crystalline hydrates and

ammines are associated with the metallic atom in the same wqay as the
coordinated atoms and radicals in a complex anion. Thus he showed that
[Ni(NH3)6]Cl2 has the same crystal structure as (NH4)2[PtCl6] with
[Ni(NH3)6]2+ ions in place of [PtCl6]2- ions. He found the structures of
[Ni(NH3)6](NO3)2 and NiSO4-6H2O to be similar. In the case of NiSO4-7H2O,
Beevers and Schwartz confirmed Werners prediction of octahedral coordination
of six water molecules around the metal ion, with the seventh water molecule
situated elsewhere in the structure, unattached ot the metal. Since the early
1920s the structures of numerous coordination compounds of various
coordination numbers (see Paper Five) have been determined by the X-ray
diffraction method. To quote Wyckoff once more:
Results such as these have put the basic correctness of the coordination theory
beyond dispute; its formulation will remain permanently useful even though
crystal structure methods have advanced until we no longer need rely on its
predictions.
RALPH W. G. WYCKOFF, currently Professor of Physics and Bacteriology at the
University of Arizona, was born in Geneva, New York, on August 9, 1897. In
1916 he received his Bachelor of Science degree from Hobart College in
Geneva and his doctorate in chemistry from Cornell University in 1919. During
his long and varied career, he has held many positions, of which the following
may be mentioned: Instructor in Analytical Chemistry, Cornell University, 19171919; Physical Chemist, Geophysical Laboratory, Carnegie Institution of
Washington, 1919-1927 during which time Paper Six was written; Research
Associate, California Institute of Technology, 1921-1922; Associate Member in
charge of the subdivision of biophysics, Rockefeller Institute, 1927-1938;
Associate Director of Research, Lederle Laboratories , 1942-1943; Lecturer,
University of Michigan 1943-1945; Scientific Director and Biophysicist, National
Institutes of Health, 1945-1959; Science Attach, American Embassy, ondon,
1952-1954; and Director of Research, Centre National de la Recherche
Scientifique of France, 1958-1962. The holder of two honorary degrees, he has
been editor of a number of journals, president of several scientific societies,
and honorary member of various foreign scientific societies.
His research interest include the structure of crystals, effects of radiation on
cells, the ultracentrifuge, purification of viruses and macromolecules, electron
microscopy, applied electron optics, and the physics of soft X-rays and
application of these and other physical techniques to the microstructure of hard
tissues, both fossil and modern. His scientific publications include sixteen
books and about three hundred fifty technical papers, of which eighty-five deal
with crystallography, thirty with other phases of pure physics, and the rest with
various aspects of biophysical research.

EUGEN WALDEMAR POSNJAK was born in Moscow, Russia on Jun 23, 1888. After
receiving his doctorate from the University of Leipzig in 1912, he became
Research Associate in Physical Chemistry at the Massachusetts Institute of
Technology. The following year he became a chemist at the Geophysical
Laboratory of the Carnegie Institution of Washington where he remained for the
rest of his career. His first experience with X-ray techniques was obtained
working with Dr. Wyckoff on Paper Six. During World War II he was a consultant
for the National Defense Research Center. He died in Santa Barbara, California,
in July of 1949. In addition to his studies on the structure of crystals, he worked
on problems in colloid chemistry, geochemistry, salt solution equillibria, and
ferromagnetism.---G.B.K.