Z. Kristallogr.
2021; aop
Oleg I. Siidra* and Mishel R. Markovski
KCu(SeO4)Cl(H2O)2, a first copper chloride
selenate
https://doi.org/10.1515/zkri-2021-2020
Received March 30, 2021; accepted June 14, 2021;
published online June 24, 2021
Abstract: A first copper chloride selenate was obtained
upon attempted preparation of a selenate analog of chlor-
othionite. The new compound is monoclinic, P21/c,
a = 7.1833(5) Å, b = 11.7784(8) Å, c = 8.2419(6) Å, β = 91.083(2)°,
V = 697.20(8) Å3, R1 = 0.033. KCu(SeO4)Cl(H2O)2 has no
structural analogs and adds to the small family of transition
metal selenate halides. The CuO3(H2O)2Cl strongly distorted
octahedra share common O–O edges thus forming dimeric
units with a Cu–Cu distance of 3.49 Å. Dimeric units and SeO4
tetrahedra in KCu(SeO4)Cl(H2O)2 share common O atoms to
produce unique [Cu(SeO4)Cl(H2O)2]− chains. We discuss
further perspectives of the selenate halide family and ex-
pected differences in crystal chemistry of sulfate and selenate
halides.
Keywords: chlorides; chlorothionite; copper; crystal
structure; selenates.
1 Introduction
Multinary copper sulfate halides form a unique class of
compounds, mostly minerals, which exhibit unique crys-
tal chemistry [1]. The presence of magnetically active Cu2+
cations (S = ½) at relatively low distances makes many of
them promising novel magnetic materials [2–4]. Chlor-
othionite, K2Cu(SO4)Cl2 [5], can be readily prepared syn-
thetically from aqueous solutions containing KCl and
Cu(SO4) [3]; this also permitted to study magnetic prop-
erties of several analogs, e.g., K2Cu(SO4)Br2 [3] and
Na2Cu(SO4)Cl2 [4]. While there exist enough examples of
isostructural compounds among multinary copper sul-
fates and selenates (e.g., [6–8]), no copper selenate ha-
lides have been reported to date. This might be caused by
*Corresponding author: Oleg I. Siidra, Department of
Crystallography, St. Petersburg State University, University Emb. 7/9,
199034, St. Petersburg, Russia; and Kola Science Center, Russian
Academy of Sciences, Apatity, 184200, Murmansk Region, Russia,
E-mail: o.siidra@spbu.ru
Mishel R. Markovski, Department of Crystallography, St. Petersburg
State University, University Emb. 7/9, 199034, St. Petersburg, Russia
relatively low thermal and redox stability of selenates
compared to sulfates. In order to fill this gap and to look
for possible selenate analogs of chlorothionite, we have
undertaken this study.
2 Experimental
2.1 Synthesis
Caution! 96% selenic acid is toxic and can vigorously react with
reducing agents and water.
The initial synthetic approach was similar to that described in
[3, 4]. Copper selenate pentahydrate was prepared by heating excess
CuO (Aldrich, 99.9%) with 20% selenic acid (prepared from analyti-
cally pure 98% reagent) at 50–60 °C until no more CuO dissolved. The
pH of the deep blue solution was about six. The unreacted CuO was
filtered and the solution evaporated slowly at room temperature to
yield large blue crystals which were air-dried for a short time and kept
in a closed vial to prevent efflorescence. Solutions containing 10 mmol
Cu(SeO4) and 20 mmol KCl in 25 ml of distilled water were then pre-
pared and heated slowly on a steam bath or a hot (80 °C) plate. Upon
evaporation to ca. 50% of the initial volume, the solution turned green
and turbid with subsequent precipitation of green crystals identified
as the selenate analog of kaliochalcite, KCu2(SeO4)2(OH)·H2O [7].
Adding one drop of 50% CF3COOH led to their dissolution. At the final
evaporation stages, the deep green solutions produced relatively large
blue crystals of Tutton’s salt, K2Cu(SeO4)2·6H2O [8], with small
aggregates of bluish-green crystals (Figure 1) which were found to
belong to a new compound, KCu(SeO4)Cl(H2O)2. The crystals readily
deteriorate when taken out of the mother liquor which did not permit
to study other properties. The estimated yield was below 10%.
Attempts to increase it were not successful due to competing forma-
tion of K2Cu(SeO4)2·6H2O. When Cu(SeO4) was replaced by Cu(SO4) in
a test run aimed to check the correctness of synthetic procedure,
K2Cu(SO4)Cl2 was obtained.
2.2 Single-crystal X-ray studies
A prismatic crystal of KCu(SeO4)Cl(H2O)2 was mounted on a glass fiber
and studied on a Bruker APEX II DUO X-ray diffractometer equipped
with a micro-focus X-ray tube operating with MoKα radiation at 50 kV
and 0.6 mA. The data were integrated and corrected for absorption
using a multi-scan type model implemented in the Bruker programs
APEX and SADABS [9]. More than a hemisphere of X-ray diffraction data
was collected. The structure was solved by direct methods and refined
using SHELX software package [10]. The structure solution revealed
positions for all atoms except of hydrogens; those were ascertained
from the difference Fourier maps. The new compound is monoclinic,
2 O.I. Siidra and M.R. Markovski: Crystal structure of KCu(SeO4)Cl(H2O)2

Figure 1: Crystals of KCu(SeO4)Cl(H2O)2

under optical microscope (left) and BSE
image (right). Cavities on the surfaces on
the right image are likely due to starting
deterioration (efflorescence in vacuo).

Table : Crystallographic data and refinement parameters for Table : Selected interatomic distances (Å) in the structure of
KCu(SeO)Cl(HO). Experiments were carried out at  K with KCu(SeO)Cl(HO).
MoKα radiation on Bruker Smart DUO, CCD.
K–O .() Cu–O .() Se–O .()
Space group P/c K–O .() Cu–Ow .() Se–O .()
a(Å) .() K–O .() Cu–Ow .() Se–O .()
b(Å) .() K–O .() Cu–O .() Se–O .()
c(Å) .() K–Ow .() Cu–Cl .() <Se–O> .
β(°) .() K–O .() Cu–O .()
V(Å) .() K–Ow .()
Dx (g/cm) .
Crystal size, mm . × . × .
θ max (°) . described to date. The potassium cation is coordinated by
h, k, l range −– two chlorine and seven oxygen atoms, two from water mol-
−– ecules. The H2O molecules donate hydrogen bonds to chlo-
−–
rine atoms (d(H1···Cl1) = 2.56(3) Å, d(H2···Cl1) = 2.41(3) Å) and
Total reflections collected 
Unique reflections (Rint) (.) oxygen atoms of selenate anions (d(H1···O4) = 2.59(3) Å,
Unique reflections F > σ(F)  d(H3···O1) = 1.84(3) Å, d(H4···O1) = 1.89(2) Å) (Table 3). H···Cl
R . bonds are weaker compared to those observed in the [HCl2]−
wR . anions [11].
S .
The CuO3(H2O)2Cl strongly distorted octahedra share
ρmax, min/e·Å− ./−.
common O–O edges thus forming dimeric units with a Cu–
CCDC 
Cu distance of 3.49 Å. Dimeric units and SeO4 tetrahedra in
KCu(SeO4)Cl(H2O)2 share common O atoms to produce
P21/c, a = 7.1833(5) Å, b = 11.7784(8) Å, c = 8.2419(6) Å, β = 91.083(2)°, [Cu(SeO4)Cl(H2O)2]− chains elongated along the a axis and
V = 697.20(8) Å3, R1 = 0.033 (Table 1). All non-hydrogen atoms were depicted in Figure 3a. Figure 3b shows a black-and-white
refined anisotropically. The positions of the H atoms were constrained
connectivity graph of the [Cu(SeO4)Cl(H2O)2]− chain with
to H-O distances of 0.90(3) Å. The isotropic displacement parameters
for H3 and H4 atoms were held constant at 0.05 Å, but were refined for
the edges linking adjacent Cu (black) and Se (white)
H1 and H2 sites. Selected interatomic distances are given in Table 2. vertices. The single and double edges correspond to mono
and bidentate linkage modes between the cation poly-
hedra, respectively. Nodal representation of the [Cu(SeO4)
Cl(H2O)2]− chain in the structure of KCu(SeO4)Cl(H2O)2 al-
3 Crystal structure lows to identify its uniqueness among minerals and

The unique crystal structure of KCu(SeO4)Cl(H2O)2 contains

each one K, Se, and Cu site, six O sites, and four H sites Table : Hydrogen bonds (D = donor, A = acceptor) in the structure
corresponding to the water molecules (Figure 2). Se(VI) forms of KCu(SeO)Cl(HO).
a typical SeO4 tetrahedron with d(Se–O) = 1.617(2)–1.661(2) Å. D–H···A d(D–H) d(H···A) <DHA d(D···A)
Cu(II) cations reside in strongly distorted CuO3(H2O)2Cl Ow–H···Cl .() .() () .()
octahedra. CuO3(H2O)2Cl octahedron is rather unusual with Ow–H···O .() .() () .()
the longest Cu–O distance formed with O2− but not with Cl− or Ow–H···Cl .() .() () .()
Ow–H···O .() .() () .()
oxygen atom of water molecule. This type of Cu-centered
Ow–H···O .() .() () .()
octahedron, to the best of our knowledge, has not been
 O.I. Siidra and M.R. Markovski: Crystal structure of KCu(SeO4)Cl(H2O)2 3

Figure 2: Coordination of atoms in the structure of KCu(SeO4)Cl(H2O)2. Thermal ellipsoids are drawn at the 50% probability level.

Figure 3: [Cu(SeO4)Cl(H2O)2]− chain in the structure of KCu(SeO4)Cl(H2O)2 (a). Thermal ellipsoids are drawn at the 50% probability level. Graph
representation of the [Cu(SeO4)Cl(H2O)2]− chain with the edges linking adjacent Cu (black) and Se (white) vertices (b). The single and double
edges correspond to mono and bidentate linkage modes between the cation polyhedra, respectively.
4 O.I. Siidra and M.R. Markovski: Crystal structure of KCu(SeO4)Cl(H2O)2

Figure 4: General projections of the structure of KCu(SeO4)Cl(H2O)2 (a, b). Hydrogen bonding between [Cu(SeO4)Cl(H2O)2]− chains (c). Blue
dashed lines highlight hydrogen bonds (b, c). K atoms are omitted for clarity in c.

synthetic compounds. K+ cations are located between
[Cu(SeO4)Cl(H2O)2]− chains in the structure of KCu(SeO4)
Cl(H2O)2 (Figure 4a, b). H3···O1 and H4···O1 bonds sew
[Cu(SeO4)Cl(H2O)2]− chains into pseudolayers depicted in
Figure 4c. In addition to K–O and K–Cl bonds, H1···Cl1 and
H1···O4 bonds (Figure 4b) provide the three-dimensional
integrity of the structure.
4 Discussion
KCu(SeO4)Cl(H2O)2 has no structural analogs and adds to
the small family of transition metal selenate halides. It is
also the first known selenate chloride. It was noted earlier
that “the existence of the large number of selenite chlorides
and almost complete absence of selenate chlorides can be
explained by the tendency of Se4+ cations possessing a
lone electron pair to participate in attractive Se4+–Cl−
interactions, which cannot be realized in Se6+ oxysalts”
[12]. Note that the number of attempts to synthesize such
compounds is very small to date. The relatively high
chemical stability of selenites versus selenates is probably
the true reason why selenite halides are essentially more
numerous. An inverse pattern is observed for sulfur com-
pounds wherein sulfites are essentially less thermally and
chemically stable and sulfite halides are exceptionally rare
[13, 14], not considering the inert complexes of late tran-
sition metals.
The low thermal stability of most selenates essentially
hinders thermal approaches, and an only alkali compound,
K3(SeO4)F anti-perovskite, has been prepared by a solid-
state reaction [15]. The utmost chemical stability of silver
iodide permitted preparation of two complex silver iodide
selenates, Ag4I2(SeO4) [16] and Ag9I3(SeO4)2(IO3)2 [17].
Solution syntheses (including hydrothermal) are an evident
alternative leading readily to hydrated products. The only
 O.I. Siidra and M.R. Markovski: Crystal structure of KCu(SeO4)Cl(H2O)2
compound synthesized earlier in this way, NaCo(SeO4)
F⋅2H2O [18] (a formal chemical analog of KCu(SeO4)Cl(H2O)2)
belongs to the NaMg(SO4)F·2H2O family and exhibits a
totally unrelated structure with hexacoordinated Co2+ and
trans-arrangement of fluoride ions, water molecules, and
oxygens from bridging selenate anions. The relatively low
solubility of fluorides renders them additional stability: we
also note that KCo(SO4)F·2H2O and KCo(SeO4)F·2H2O are
isostructural and can be prepared under similar conditions.
The behavior of KCl–CuSO4–H2O and KCl–CuSeO4–H2O
systems is entirely different. A possible explanation lies
in the structure of chlorothionite itself which features a rare
η2-coordination of SO42− to Cu2+ which corresponds to edge
sharing of CuOnXm and SO4 polyhedra. The other known
example is the structure of majzlanite K2Na3(Zn,Cu)Ca(SO4)4
[19] yet Cu2+ is a minor (18%) substituent for Zn2+. Such
coordination is yet unknown for SeO42− which coordinates to
Cu2+ in a monodentate mode only [7, 20–22].
It needs also to be noted that the solution synthesis of
selenate halides, except probably fluorides, is expected to
meet more restrictions compared to sulfates. In concen-
trated acidic solutions, SeVI readily oxidizes halide anions
[23]; as selenous acid is weaker, its salts (including copper
selenate) undergo easy hydrolysis which in our case was
manifested by the formation of KCu(SeO4)Cl(H2O)2. We
predict existence of more such compounds which are ex-
pected to exhibit its unique crystal chemistry, at least
partially different from that of sulfate halides.
Acknowledgment: We are grateful to two anonymous re-
viewers for valuable comments. Technical support by the
SPbSU Resource Centers is gratefully acknowledged.
Author contributions: All the authors have accepted
responsibility for the entire content of this submitted
manuscript and approved submission.
Research funding: This work was financially supported
by the Russian Foundation for Basic Research, Grant No.
19-05-00413.
Conflict of interest statement: The authors declare no
conflicts of interest regarding this article.
References
1. Pekov I. V., Zubkova N. V., Pushcharovsky D. Y. Copper minerals
from volcanic exhalations – a unique family of natural compounds:
crystal-chemical review. Acta Crystallogr. 2018, B74, 502–518.
2. Kikuchi H., Kunieda K., Fujii Y., Astuti F., Sari D. P., Watanabe I.
Successive magnetic phase transition of the new frustrated
compound KCu3OCl(SO4)2. RIKEN Accel. Prog. Rep. 2017, 50, 236.
5
3. Hälg M., Lorenz W. E. A., Povarov K. Y., Månsson M., Skourski Y.,
Zheludev A. Quantum spin chains with frustration due to
Dzyaloshinskii-Moriya interactions. Phys. Rev. 2014, B90,
174413.
4. Fujihala M., Mitsuda S., Mole R. A., Yu D. H., Watanabe I., Yano S.,
Kuwai T., Sagayama H., Kouchi T., Kamebuchi H., Tadokoro M.
Spin dynamics and magnetic ordering in the quasi-one-
dimensional S=1/2 antiferromagnet Na2CuSO4Cl2. Phys. Rev.
2020, B101, 024410.
5. Giacovazzo C., Scandale E., Scordari F. The crystal
structure of chlorothionite CuK2Cl2SO4. Z. Kristallogr. 1976,
144, 226.
6. Pekov I. V., Siidra O. I., Chukanov N. V., Yapaskurt V. O., Belakovskiy
D. I., Murashko M. N., Sidorov E. G. Kaliochalcite,
KCu2(SO4)2х[(OH)(H2O)], a new tsumcorite-group mineral from the
Tolbachik volcano, Kamchatka, Russia. Eur. J. Mineral 2014, 26, 597.
7. Giester G., Zemann J. The crystal structure of the natrochalcite-
type compounds Me+Cu2(OH)(ZO4)2H2O [Me+= Na, K, Rb; Z= S,
Se], with special reference to the hydrogen bonds. Z. Kristallogr.
1987, 179, 431–442.
8. Simmons C. J., Stratemeier H., Hitchman M. A., Riley M. J.
Influence of lattice interactions on the Jahn-Teller distortion of the
[Cu(H2O)6]2+ ion: dependence of the crystal structure of
K2[Cu(H2O)6](SO4)2x(SeO4)2-2x upon the sulfate/selenate ratio.
Inorg. Chem. 2006, 45, 1021–1031.
9. Bruker. AXS APEX2 (version 2014.11-0): Madison, Wisconsin, USA,
2014.
10. Sheldrick G. M. Crystal structure refinement with SHELXL. Acta
Crystallogr. 2015, A71, 3–8.
11. Tuck D. G., Cotton F. A., Eds. Progress in Inorganic Chemistry;
Wiley, 5, 2009; pp. 161–191.
12. Krivovichev S. V., Gorelova L. A. Se-Cl interactions in selenite
chlorides: a theoretical study. Crystals 2018, 8, 193.
13. Weil M., Breitinger D. K., Liehr G., Zuerbig J. Structural
investigations and thermal behaviour of mercury(II) sulfito
complexes. Z. Anorg. Allg. Chem. 2007, 633, 429–434.
14. Weil M., Baumann S., Breitinger D. K. Structural studies of new
sulfito mercurates(II) with general formula xM[XHgSO3] ·yHgX2·
zMX·nH2O (M = NH4, K; X = Cl, Br). Z. Anorg. Allg. Chem. 2008,
634, 1742–1748.
15. Skakle J. M. S., Fletcher J. G., West A. R. The crystal structures of
the potassium oxyfluorides, K3SeO4F and K3PO3F2. An. Quim.
1996, 92, 358–361.
16. Pitzschke D., Curda J., Cakmak G., Jansen M. Ag4I2SeO4 and
Ag3ITeO4 – two new silver solid electrolytes. Z. Anorg. Allg. Chem.
2008, 634, 1071–1076.
17. Pitzschke D., Curda J., Cakmak G., Jansen M. Ag9I3(SeO4)2(IO3)2 –
synthesis, crystal structure, and ionic conductivity. Z. Anorg. Allg.
Chem. 2008, 634, 1907–1910.
18. Melot B. C., Chotard J.-N., Rousse G., Ati M., Reynaud M.,
Tarascon J-M. Synthesis, structure, and magnetic properties of
the NaCoXO4F·2H2O phases where X = S and Se. Inorg. Chem.
2011, 50, 7662–7668.
19. Siidra O. I., Nazarchuk E. V., Zaitsev A. N., Shilovskikh V.,
Majzlanite V. K2Na(ZnNa)Ca(SO4)4, a new anhydrous sulfate
mineral with complex cation substitutions from Tolbachik
volcano. Miner. Mag. 2020, 84, 153–158.
20. Peytavin S., Philippot E., Maurin M. Etude structurale du sel double
dihydrate: Na2Cu(SeO4)2.2H2O. J. Solid State Chem. 1974, 9, 63–68.
 6 O.I. Siidra and M.R. Markovski: Crystal structure of KCu(SeO4)Cl(H2O)2

21. Fleck M., Giester G. Crystal structures of the new double salts
K2Cd3(SO4)4·5H2O, Rb2Cu3(SO4)3(OH)2 and Cs2Cu(SeO4)2·4H2O.
J. Alloys Compd. 2003, 351, 77–83.
22. Snyman H. C., Pistorius C. W. F. T. Polymorphism in the selenates
of Mg, Mn, Co and Cu at high pressures. Z. Kristallogr. 1964, 120,
317–322.
23. Rich R. L. Inorganic Reactions in Water, 1st ed.; Springer-Verlag:
Berlin – Heidelberg, 2007; p. 438.
Supplementary Material: The online version of this article offers
supplementary material (https://doi.org/10.1515/zkri-2021-2020).

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