Layered copper hydrogen selenites: a family of decorated perovskite derivatives

D.O. Charkin,1* V.Yu. Grishaev,1 M.R. Markovski,2 D.O. Nekrasova,2 O.I. Siidra2,3
1
Moscow State University, Leninskie Gory 1, Moscow 119992 Russia
2
St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
3
Kola Science Center, Russian Acad. Sci., Apatity, 184200, Murmansk Region, Russia

* charkin@inorg.chem.msu.ru

While “normal” and basic selenties and selenite halides of transition metals are in the focus of
extensive studies due to natural occurrence and excellent and non-trivial magnetic properties (Verma 1999),
their analogs containing protonated selenite ions received essentially less attention. A small but interesting
family involves a set of 2D structures based on neutral [M(HSeO3)2] layers (M = commonly CuII, a handful
of CoII and ZnII representatives are also known). These layers interleave with sheets of water molecules of
various metal-halide or metal-nitrate slabs of varied complexity leading, in most cases, to decorated
perovskite-like structures, the decorating ions being HSeO3- and NO3-, respectively (Kovrugin et al. 2015).
Evaporation of strongly acidic aqueous solutions containing H2SeO3, CuX2, AX (A = univalent
cation, X = Cl, Br, or NO3), and HNO3 or CF3COOH produced single crystals of new copper hydrogen
selenite nitrates and halides. The latter contain a series of (AX)[Cu(HSeO3)2] compounds demonstrating
various distorted versions of decorated (AX)(BX2) 3D perovskite structures. In all cases, chlorides and
bromides are complete analogs and the structural details depend on the relative size of the A+ cation. The
smallest Na+ produces a unique monoclinic motif (Kovrugin et al. 2015 and references therein); larger K +
results in a less distorted monoclinic arrangement previously observed for (RbX)[Zn(HSeO3)2]. The largest
NH4+, Rb+, and Cs+ gives rise to the orthorhombic structure first observed for (NH4Cl)[Cu(HSeO3)2]. The
dependence of the structure motif vs. the relative size of A+ and M2+ suggests that, akin to non-decorated
perovskites, an analog of Goldschmidt tolerance factor can be suggested.
On the contrary, related nitrates were found only for the largest NH4+, Rb+, Tl+, and Cs+. This comes
due to the less symmetrical bonding mode of the nitrate ion compared to halide. This family hosts structures
exhibiting decorated versions of Ruddlesden – Popper series closely related to cuprate superconductors.
While Cs+ and Tl+ contribute to decorated perovskites (ANO3)[Cu(HSeO3)2], intermediate Rb+ gives rise
to (RbNO3)2[Cu(HSeO3)2] (decorated K2NiF4). The smallest NH4+, which actively partakes in hydrogen
bonding, yields the most complex structure of (NH4NO3)3[Cu(HSeO3)2], a decorated version of TlBa2CuO5.
The structure of the ammonium compound was re-determined for more accurate analysis of hydrogen
bonding.
Our studies of the halide compounds have also produced some curious side results. While Li+ is too
small to contribute to the perovskite-like structure, it serendipitously evokes formation of
Li2Cu(Se2O5)Cl2.2H2O with an unprecedented 2D structure which has no bromide analogue. We have also
isolated two isostructural compounds KXH2SeO3 (X = Cl and Br) which may be considered as simplest
representatives of salt-inclusion structures. We also observed formation of a new 3D compound
CaCl(HSeO3)H2O which also has no bromide analogue.
This study was financially supported by the Russian President grant MD-5229.2018.5. Technical
support by the X-Ray Diffraction Resource Centre of Saint-Petersburg State University is gratefully
acknowledged.

Kovrugin V.M., Krivovichev S.V., Mentré O., Colmont M. [NaCl][Cu(HSeO3)2], NaCl-

intercalated Cu(HSeO3)2: synthesis, crystal structure and comparison with related compounds. Z.
Kristallogr. 2015, 230, 573-578.
Verma V.P. A review of synthetic, thermoanalytical, IR, Raman, and X-ray studies on metal
selenites, Thermochimica Acta 1999, 327, 63-102

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