Review of Tl(I) coordination polyhedra in oxysalt minerals and synthetic compounds

Mishel R. Markovski1,*, Oleg I. Siidra1,2

1
Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034
St. Petersburg, Russia
2
Kola Science Center, Russian Academy of Sciences, Apatity, 184200, Murmansk Region, Russia

* mishelmarkovski@gmail.com

183 unique (i.e. without isostructural duplicates) monovalent thallium oxysalts for which good
refinements exist were reviewed. 303 Tl+-On and 11 Tl+-OnXm (X = F, Cl, Br) polyhedra containing 2449
Tl+-O (≤ 3.55Å) and 74 Tl-X (≤ 3.7 Å) bonds were taken into consideration. Bond-valence calculations and
geometrical parameters proposed by [Balic-Žunic and Makovicky, 1996] were employed in order to
evaluate the influence of the ‘lone pair’ (LP) stereoactivity on the distortion of Tl-centered coordination
polyhedra. In 2/3 of the described complexes, LP is stereochemically active. LP occupies approximately
the volume of O ion and strongly influences on the Tl(I) coordination environments.
5 different types of coordination polyhedra (Fig. 1) were observed:
I-Hemidirected convex geometry of the Tl complexes, typical for low CN from 2 to 6, and strong
stereoactivity of LP, raised above the surrounding O atoms;
II-Hemidirected concave geometry, typical for CN 6-11, and pronounced stereoactivity of LP;
III-Equatorial geometry is very rare and observed in Tl+-Onpolyhedra with CN 5-12;
IV-Bisdirected geometry was earlier described for Pb(II) complexes [Severen et al., 2009]. The
similar geometry was observed also for Tl+-On.
V-Holodirected geometry [Shimoni-Livny et al., 1998] is typical for high CN 8-15 and no indication
LP stereoactivity which in turn resultsin the formation of many relatively weak Tl+-O bonds around the
central thallium atom.

Fig. 1. The 5 different types of Tl(I) coordination polyhedrain oxysalt minerals and synthetic compounds and some
examples of Tl-On coordination environments (left). Bonds > 3.0 Å are shown by dashed lines. Distribution of Tl(I)
coordination polyhedra in reviewed structures (right).

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The Pb(II) 6s6p lone pair can be bisdirected in proteins. Chem. Phys. Lett., 2009, 478, 17-19.
Shimoni-Livny L., Glusker J.P., Bock C.W. Lone pair functionality in divalent lead compounds.
Inorg. Chem. 1998, 37, 1853-1867.

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