Polymorphism of H2SeO3, NaHSeO4 and Na5H3(SeO4)4(H2O) 2, and re-refinement of the crystal structure of Te2O 4(OH)2

Article abstract of DOI:10.1002/zaac.201400068

New modifications (denoted as β-) of the compounds H ₂SeO₃, NaHSeO₄, and Na₅H ₃(SeO₄)₄(H₂O)₂ were isolated from aqueous solutions and their crystal structures determined from single crystal data. β-H₂SeO₃ crystallizes in the space group P1 with lattice parameters of a = 4.6794(4) A, b = 5.0988(4) A, c = 5.7743(5) A, α = 102.252(6)°, β = 91.594(6)°, γ = 98.054(6)°, and consists of two unique trigonal-pyramidal SeO(OH)₂ units that are held together by O-H...O hydrogen bonds. β-NaHSeO₄ crystallizes in the space group P1 with lattice parameters of a = 5.0814(2) A, b = 5.6345(3) A, c = 6.5125(3) A, α = 88.352(3)°, β = 73.163(3)°, γ = 82.027(3)°, and is made up of distorted NaO ₆ octahedra and tetrahedral SeO₃(OH)^- anions, with the hydrogen atom statistically disordered between two positions. β-Na₅H₃(SeO₄)₄(H ₂O)₂ crystallizes in the space group I2/c with lattice parameters of a = 7.0472(15) A, b = 13.194(3) A, c = 17.845(4) A, β = 101.345(9)°. The asymmetric unit contains three Na ⁺ sites (one situated on a twofold rotation axis and each with a distorted octahedral coordination by oxygen atoms), one water molecule, one SeO₃(OH)^- anion, and half of an [SeO ₄...H...O₄Se] unit with a very short interpolyhedral O...O distance of 2.447 (4) A. The crystal structures of the β-modifications are comparatively discussed with those of the corresponding known α-modifications. Moreover, the crystal structure of Te₂O₄(OH)₂ was reinvestigated [Pna2 ₁, a = 12.0512(8) A, b = 8.0267(5) A, c = 4.7268(3) A], allowing the localization of the hydrogen atoms and hence a more detailed view of the hydrogen bonding system. Copyright

Full text of DOI:10.1002/zaac.201400068

Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
ARTICLE
DOI: 10.1002/zaac.201400068
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O) , and
2
3
4
5 3
4 4
2
2
Re-refinement of the Crystal Structure of Te O (OH)
2
4
2
[a]
[a]
Stephan Pollitt and Matthias Weil*
Keywords: Tellurium; Selenium; Polymorphism; Crystal structure; Hydrogen bonding
Abstract. New modifications (denoted as β-) of the compounds
SeO , NaHSeO , and Na (SeO (H O) were isolated from
aqueous solutions and their crystal structures determined from single
crystal data. β-H SeO crystallizes in the space group P1 with lattice
parameters of a = 4.6794(4) Å, b = 5.0988(4) Å, c = 5.7743(5) Å, α =
02.252(6)°, β = 91.594(6)°, γ = 98.054(6)°, and consists of two
positions. β-Na
5 3 4 4 2 2
H (SeO ) (H O) crystallizes in the space group I2/c
H
2
3
4
5
H
3
4
)
4
2
2
with lattice parameters of a = 7.0472(15) Å, b = 13.194(3) Å, c =
+
17.845(4) Å, β = 101.345(9)°. The asymmetric unit contains three Na
sites (one situated on a twofold rotation axis and each with a distorted
2
3
octahedral coordination by oxygen atoms), one water molecule, one
–
SeO
3
(OH) anion, and half of an [SeO
4
···H···O
4
Se] unit with a very
1
short interpolyhedral O···O distance of 2.447 (4) Å. The crystal struc-
tures of the β-modifications are comparatively discussed with those of
the corresponding known α-modifications. Moreover, the crystal struc-
unique trigonal-pyramidal SeO(OH)
O–H···O hydrogen bonds. β-NaHSeO
2
units that are held together by
crystallizes in the space group
4
¯
P1 with lattice parameters of a = 5.0814(2) Å, b = 5.6345(3) Å, c =
.5125(3) Å, α = 88.352(3)°, β = 73.163(3)°, γ = 82.027(3)°, and is
ture of Te
2 4 2 1
O (OH) was reinvestigated [Pna2 , a = 12.0512(8) Å, b =
6
8.0267(5) Å, c = 4.7268(3) Å], allowing the localization of the hydro-
–
made up of distorted NaO
6
octahedra and tetrahedral SeO
3
(OH)
gen atoms and hence a more detailed view of the hydrogen bonding
system.
anions, with the hydrogen atom statistically disordered between two
Introduction
Experimental Section
The title compounds were serendipitously obtained during Synthetic Conditions for Isolation of β-H
was prepared by heating telluric acid at 350 °C for 1 d. TeO
0.58 mmol) and SeO (127 mg, 1.14 mmol) were mixed and heated
together with HgCl (30 mg) in a sealed and evacuated silica ampoule
2
SeO
3
: Amorphous TeO
3
experiments intended on single crystal growth of the phase
3
(102 mg,
IV
VI
2
Te O (Se O ). Polycrystalline Te O (SeO ) has been origi-
2
3
4
2
3
4
2
nally prepared by combining TeO and H SeO at 160 °C for
2
2
4
in a temperature gradient of 590 °C Ǟ 560 °C for 6 d. In the sink
region of the ampoule, colorless, hygroscopic needles with a maximum
length of 10 mm were obtained as the main product besides few light-
yellow crystals with a block-like form and 0.3 mm in length. Using
single-crystal X-ray diffraction, the needles were determined as tetra-
[1]
4
h. The obtained product exhibited a powder second-har-
monic-generating (SHG) effect with an efficiency of about
00 times that of α-SiO which makes Te O (SeO ) a very
2
2
2
3
4
interesting material. The non-centrosymmetric crystal structure
[
3]
of Te O (SeO ) has originally been determined from powder gonal SeO2 after immediate measurement and if embedded in perflu-
2
3
4
X-ray diffraction (PXRD) data.[1] For a more detailed insight orinated polyether, and the block-like crystals as paratellurite (α-
[
4]
2
into its structure-property relations we made attempts for sin- TeO ). The fraction of the needles that has not been embedded in
perfluorinated polyether was surrounded by a liquid after one night.
Since the original needle-like crystal form had changed overnight into
a more lath-like form with a smaller maximum length of 2 mm, a
repeated unit cell determination using single crystal diffraction (after
embedding the selected crystals in perfluorinated polyether) showed a
gle crystal growth of Te O (SeO ) for a more precise crystal
2
3
4
structure analysis and for measuring the SHG properties on
directed single crystals. For this purpose we have both modi-
fied the original synthesis conditions[ and have alternatively
applied chemical vapor transport reactions.[ However, these
experiments proved unsuccessful. Instead, single crystals of
1]
2]
triclinic cell in comparison with that of tetragonal SeO
2
. The corre-
sponding lattice parameters showed no match with any other phase
Te O (OH) and new modifications (denoted as β-) of H SeO ,
[5]
2
4
2
2
3
deposited in the Inorganic Crystal Structure Database (ICSD). Sub-
NaHSeO , and Na H (SeO ) (H O) could be isolated in the sequent structure determination revealed a polymorph of H SeO .
4
5
3
4 4
2
2
2
3
course of these studies. Their crystal structures were deter- Phase analysis of the remaining light-yellow solid in the source region
mined and are comparatively discussed in this report.
of the ampoule, prepared for X-ray powder diffraction likewise after
opening of the ampoule after one night, showed the presence of
[
6]
[4]
[7]
TeSeO
4
,
α-TeO
2
,
and TeO
2
·xSeO
2
·zH
2
O
in approximate equal
*
Prof. Dr. M. Weil
Fax: +43-1-58801-17199
E-Mail: mweil@mail.zserv.tuwien.ac.at
proportions.
[
a] Institute for Chemical Technologies and Analytics
Division of Structural Chemistry
Vienna University of Technology
Getreidemarkt 9/164-SC
2 3
Targeted Synthesis to obtain β-H SeO : Various attempts to crys-
tallize β-H SeO from hot or cold saturated aqueous solutions of SeO
2
3
2
or from ethanol/water mixtures thereof did not yield this polymorph.
For some experiments (in particular for those starting from hot solu-
1060 Vienna, Austria
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

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Date: 01-04-14 17:03:34
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S. Pollitt, M. Weil
ARTICLE
tions) a partial reduction of SeIV to elementary selenium, noticeable glass slide was put under a polarizing microscope where needle-like
by precipitation of a red-orange solid, was observed. The other batches crystals up to 5 mm in length could be separated from the mother
resulted exclusively in the formation of the known orthorhombic α- liquor in a while. Selected crystals were immediately immersed in per-
[8]
form of H
2
SeO
3
.
fluorinated polyether. Unit cell determination revealed an I-centered
monoclinic cell with unknown lattice parameters. The composition of
Synthetic Conditions for Isolation of β-NaHSeO
4
:
Na
CO
in an argon atmosphere at 750 °C, were reacted with H
2
TeO
and modification by subsequent structure analysis.
SeO
3
5 3 4 4 2 2
the crystals was determined as Na H (SeO ) (H O) in form of a new
(
204 mg), prepared by heating stoichiometric amounts of Na
2
3
[
9]
TeO
2
2
4
Targeted Synthesis to obtain β-Na
5 3 4 4 2 2
H (SeO ) (H O) : Crystallization
(1.39 g 96%wt) in a Teflon-lined autoclave at 230 °C for 6 d. The
of β-Na (SeO (H O) was tested for similar stoichiometric ratios
5
H
3
4
)
4
2
2
yellow powder obtained was separated from the remaining mother
and concentrations of aqueous solutions of the reactants as described
liquor by suction filtration through a glass frit. PXRD revealed α-
above. Fast crystallization from hot solutions yielded the triclinic α-
[10]
TeO
3
for the solid. Few colorless, lath-shaped crystals had formed
[
11–13]
polymorph of Na
5
H
3
(SeO
4
)
4
(H
2
O)
2
,
whereas the needle-like
after a couple of days in the remaining mother liquor that has been
kept under ambient conditions. Structure analysis showed a new poly-
crystals of the monoclinic β-form could be obtained by slow evapora-
tion of water from concentrated solutions at room temperature. PXRD
measurements of β-Na H (SeO ) (H O) crystals showed the α-poly-
5 3 4 4 2 2
¯
morph of NaHSeO , crystallizing in space group P1.
4
morph as the main and the β-polymorph as the minority phase although
all investigated single crystals of the freshly crystallized material had
Synthetic Conditions for Isolation of β-Na
new monoclinic modification of Na (SeO
during targeted syntheses for crystallization of the new β-NaHSeO
modification. Na SeO (190 mg, 0,87 mmol) and SeO (400 mg,
2 2
,45 mmol) were dissolved in a few drops of water. Afterwards, H O
5
H
3
(SeO
4
)
4
(H
2 2
O) : The
5
H
3
4
)
4
2
(H O)
2
had formed
previously been identified as β-Na
tained crystals without preceding grinding revealed in fact nearly single-
phase β-Na (SeO (H O) . On standing for some hours in the mother
liquor, the needle-like β-Na (SeO (H O) crystals had transformed
into smaller lath-shaped crystals of α-Na (SeO (H O)
5 3 4 4 2 2
H (SeO ) (H O) . PXRD of the ob-
4
2
3
2
5
H
3
4
)
4
2
2
0
5
H
3
4
)
4
2
2
IV
VI
(16 g, 30%wt) was added to oxidize Se to Se . By heating, the
5
H
3
4
)
4
2
2
.
resulting solution was concentrated until the first crystals appeared. A
part of the cold saturated solution was then dropped on a glass slide
and put on a warm surface until the solution became turbid. Then the 70%wt) and TeO
Synthetic Conditions for Isolation of Te O (OH) : H SeO (530 mg
2
4
2
2
4
2
(150 mg, 0.94 mmol) were reacted in a Teflon-lined
Table 1. Details of data collections and structure refinements.
β-H
2
SeO
3
β-NaHSeO
4
β-Na
725.85
0.50ϫ0.05ϫ0.01
–173
Mo-K , 0.71073
APEXII CCD (Bruker)
5
H
3
(SeO
4
)
4
(H
2
O)
2
Te
2 4 2
O (OH)
M
128.97
0.09ϫ0.05ϫ0.02
166.96
0.08ϫ0.07ϫ0.01
353.22
0.25ϫ0.04ϫ0.04
Crystal size /mm3
Temperature /°C
Radiation, λ /Å
Diffractometer
α
Crystal color; form
Space group, No.
colorless; fragment
P1, 1
colorless; fragment
P1, 2
colorless; needle
I2/c, 15
colorless; lath
Pna2 , 33
1
¯
Formula units Z
2
2
4
4
a /Å
b /Å
c /Å
α /°
4.6794(4)
5.0988(4)
5.7743(5)
102.252(6)
91.594(6)
98.054(6)
133.069(19)
13.841
5.0814(2)
5.6345(3)
6.5125(3)
88.352(3)
73.163(3)
82.027(3)
176.729(14)
10.589
7.0472(15)
13.194(3)
17.845(4)
12.0512(8)
8.0267(5)
4.7268(3)
β /°
101.345(9)
γ /°
V /Å3
1626.8(6)
9.248
2.964
1.93 – 31.00
–10 Ǟ 10
–19 Ǟ 19
–25 Ǟ 25
27476
457.23(5)
12.699
5.131
4.23 – 45.95
–24 Ǟ 24
–16 Ǟ 16
–9 Ǟ 9
63865
μ /mm–1
X-ray density /g·cm–3
Range θmin – θmax
Range h
3.219
3.137
3.62 – 34.99
–7 Ǟ 7
–8 Ǟ 8
–9 Ǟ 9
12500
3.27 – 46.19
–10 Ǟ 10
–11 Ǟ 11
–13 Ǟ 13
24869
k
l
Measured reflections
Independent reflections
Obs.reflections [I Ͼ 2σ(I)]
2332
2005
3087
2736
2584
2059
3973
3941
R
i
0.0740
0.0656
0.0821
0.0380
Absorption correction
Trans. coef. Tmin; Tmax
Number of parameters
Ext. coef. (SHELXL97)
Flack parameter; no. of Friedel pairs 0.016(14); 1163
Diff. elec. dens. max / e ·Å
SADABS (Bruker)
0.5284; 0.7491
87
0.034(4)
0.4586; 0.7491
63
0.026(3)
–
0.0905; 0.9132
124
0.00040(6)
–
0.4074; 0.7491
82
0.00699(18)
0.009(13); 1828
1.29
–
–3
0.80
1.63
0.97
(
dist. /Å, atom)
Diff. elec. dens. min / e ·Å
dist. /Å, atom)
(0.95, Se1);
–0.82
(0.90, H3)
0.0279
0.0473
1.004
(0.84, O2);
–1.57
(0.57, Se1)
0.0303
0.0648
1.126
(0.87, Se1);
–0.96
(0.80, Se2)
0.0255
0.0538
1.035
(0.52, Te1);
–1.26
(1.52, H1)
0.0117
0.0247
1.164
–
–3
(
2
2
R [F Ͼ 2σ(F )]
wR
Goof
2
2
(F all)
2
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Job/Unit: Z14068
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Date: 01-04-14 17:03:34
Pages: 11
2 3 4 5 3 4 4 2 2
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O)
steel autoclave for 24 h at 220 °C, yielding a yellow microcrystalline
were optimized with the APEX2[15] program, resulting in highly re-
reaction product. The reaction was prolonged for another 4 d under dundant data sets covering the complete reciprocal sphere up to high-
the same conditions. Besides the yellow microcrystalline solid (deter-
diffraction angles. After integration of the data with the program
), colorless SAINT,[15] for each of the data sets an absorption correction based on
the semi-empirical “multi-scan” approach was applied with the pro-
[
10]
[14]
mined by PXRD as a mixture of α-TeO
3
2 4
and H TeO
single crystals of Te (OH) were isolated.
2
O
4
2
[
15]
gram SADABS.
Single Crystal Diffraction and Structure Analysis: All selected methods and were refined using the SHELXTL program package.
crystals were embedded in perfluorinated polyether. Unit cell determi-
For all structures atoms (except hydrogen atoms) were refined with
nations were performed at room temperature; final intensity data were anisotropic displacement parameters. All hydrogen atoms were located
recorded at –173 °C with a Bruker Kappa APEXII CCD diffractometer
from difference Fourier maps and their positions were refined with an
Mo-K radiation) using ω- and φ-scans. The data collection strategies O–H distance restraint of 0.98(1) Å for Se/Te–OH groups and of
The crystal structures were solved by using direct
[
16]
(
α
i j ij i j
Table 2. Atomic coordinates and equivalent isotropic displacement parameters Ueq = (1/3)Σ Σ U a ·a
/Å2.
Atom
x
y
z
U
eq
β-H
Se1
Se2
O4
O5
O6
O1
O2
O3
H1
H2
H3
H4
2 3
SeO
0.81213(6)
0.31227(6)
0.1231(5)
0.1014(5)
0.1638(5)
0.6050(5)
0.6495(5)
0.6427(6)
0.741(10)
0.806(8)
0.17630(5)
0.79570(5)
0.5430(5)
1.0402(5)
0.7320(5)
–0.1191(5)
0.2956(5)
0.3529(5)
0.535(4)
0.33403(5)
0.77787(5)
0.8659(5)
0.8967(5)
0.4830(4)
0.2403(5)
0.5996(5)
0.1573(5)
0.155(9)
0.00726(14)
0.00718(14)
0.0102(5)
0.0122(5)
0.0127(5)
0.0098(4)
0.0126(5)
0.0114(5)
0.023(7)
0.395(10)
1.2378(14)
0.785(11)
0.714(7)
0.918(10)
0.385(7)
0.023(7)
0.023(7)
0.023(7)
0.145(12)
0.320(7)
β-NaHSeO
Na1
Se1
O1
O2
4
–0.02829(16)
0.63005(3)
0.6850(3)
0.7730(3)
0.7868(3)
0.3043(3)
0.510(8)
0.25005(14)
0.28735(3)
0.1368(2)
0.1266(2)
0.5304(3)
0.3754(2)
0.080(12)
0.516(19)
0.15372(13)
0.73849(3)
0.5078(2)
0.8961(2)
0.6621(2)
0.8433(2)
0.511(15)
0.565(10)
0.01011(12)
0.00496(4)
0.01000(18)
0.0112(2)
0.0117(2)
0.0121(2)
0.040(18)
0.040(18)
O3
O4
H1
H2
a)
a)
0.976(8)
β-Na
Na1
Na2
Na3
Se1
Se2
O1
O2
O3
O4
O5
5
H
3
(SeO
4
)
4
(H
2
O)
2
0.58966(14)
0
0.59356(8)
0.25471(12)
0.07831(8)
0.622531(19)
0.361473(19)
0.65489(14)
0.54960(14)
0.73315(14)
0.57183(14)
0.25567(14)
0.43089(14)
0.42818(14)
0.33204(14)
0.13248(14)
0.7212
0.15484(6)
¼
0.04767(6)
0.0105(2)
0.0139(3)
0.0112(2)
0.00657(7)
0.00723(7)
0.0110(4)
0.0105(4)
0.0107(4)
0.0101(4)
0.0116(4)
0.0100(4)
0.0122(4)
0.0130(4)
0.0135(4)
0.016
0.36013(14)
0.10934(3)
0.38524(3)
0.1685(3)
–0.0788(2)
0.0551(3)
0.2974(2)
0.3741(3)
0.5715(2)
0.1905(3)
0.4325(3)
0.2440(3)
0.0820
0.152429(13)
0.059518(13)
0.07151(10)
0.14276(10)
0.18910(10)
0.20737(10)
0.10439(10)
0.09692(10)
0.04600(11)
–0.02837(10)
0.24390(11)
0.2445
O6
O7
O8
O9
a)
H1
H2
H3
H4
0.3799
0.2736
0.2184
0.2644
0.0802
0.1138
–0.0425
0.2668
0.1992
0.019
0.020
0.020
2 4 2
Te O (OH)
Te1
Te2
O1
O2
O3
O4
O5
O6
H1
H2
0.109802(5)
0.440729(5)
0.23069(8)
0.45100(7)
0.85353(8)
0.98466(8)
0.07605(8)
0.20758(8)
0.251(3)
0.033683(8)
0.141330(8)
0.00409(12)
0.04573(11)
0.16266(12)
0.09108(12)
0.23442(12)
0.16718(12)
–0.1132(12)
0.116(4)
0.999340(19)
0.863651(18)
0.7354(2)
0.5047(3)
0.6874(2)
0.2388(2)
0.7992(2)
0.2247(2)
0.708(8)
0.00213(1)
0.00263(1)
0.00495(12)
0.00501(11)
0.00457(13)
0.00464(12)
0.00425(12)
0.00523(13)
0.027(6)
0.219(3)
0.411(3)
0.027(6)
a) Occupancy 0.5.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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S. Pollitt, M. Weil
ARTICLE
0
.82(1) Å for water molecules. The difference Fourier maps of the final Drawings of structural details were produced using the program
[
17]
models showed no significant residual electron density attributable to
any additional atoms.
ATOMS.
Results and Discussion
Numerical details of data collections and structure refinements are
listed in Table 1. Atomic coordinates and equivalent isotropic displace-
ment parameters are summarized in Table 2. Selected bond lengths and
angles are gathered in Table 3.
Formation
In a closed silica ampoule using a temperature gradient
VI
IV
IV
5
90 °C Ǟ 560 °C, the redox reaction Te + Se Ǟ Te
+
Further details of the crystal structures investigations may be
obtained from the Fachinformationszentrum Karlsruhe, 76344 Egg-
enstein-Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail:
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for
deposited data.html) on quoting the depository numbers CSD-427359
VI
Se does not occur; all identified (solid) products originating
from this reaction exhibited selenium and tellurium in oxi-
dation state +IV. Above 400 °C, the employed TeO decom-
3
[
9]
poses into TeO and elementary oxygen, the oxidizing power
2
IV
VI
(
β-H
2
SeO
3
), CSD-427360 (for β-NaHSeO
(H O) ] and CSD-427362 [for Te
4
), CSD-427361 [for of which evidently is not strong enough to oxidize Se to Se
β-Na
5
H
3
(SeO
4
)
4
2
2
2
O
4
(OH) ]. under these conditions.
2
Table 3. Selected bond lengths /Å and angles /° with estimated standard deviations in parentheses.
5 3 4 4 2 2
SeO β-Na (SeO (H O) β-Na H (SeO ) (H O)
H
2
3
5
H
3
4
)
4
2
2
Se1–O1
Se1–O3
Se1–O2
Se2–O4
Se2–O5
Se2–O6
1.648(2)
1.739(3)
1.760(3)
1.639(2)
1.737(3)
1.767(3)
Na1–O6
Na1–O3
Na1–O8
Na1–O4
Na1–O4
Na1–O2
Na2–O9
Na2–O9
Na2–O9
Na2–O9
Na2–O5
Na2–O5
Na3–O1
Na3–O7
2.375(2)
2.392(2)
2.438(2)
2.442(2)
2.448(2)
2.457(2)
2.325(2)
2.325(2)
2.375(2)
2.375(2)
2.5788(19)
2.5788(19)
2.327(2)
2.336(2)
Se1–O2
Se1–O4
Se1–O1
Se1–O3
Se2–O7
Se2–O5
Se2–O6
Se2–O8
1.6200(18)
1.6290(17)
1.6365(18)
1.6743(18)
1.6079(18)
1.6188(18)
1.6316(17)
1.7110(18)
O1–Se1–O3
O1–Se1–O2
O3–Se1–O2
O4–Se2–O5
O4–Se2–O6
O5–Se2–O6
96.86(12)
99.86(12)
97.50(13)
96.53(12)
99.15(12)
96.48(13)
O2–Se1–O4
O2–Se1–O1
O4–Se1–O1
O2–Se1–O3
O4–Se1–O3
111.85(9)
113.98(9)
108.66(9)
108.31(9)
110.13(9)
NaHSeO
4
Na3–O6
2.372(2)
O1–Se1–O3
103.59(9)
Na1–O2
Na1–O2
Na1–O4
Na1–O4
Na1–O3
Na1–O1
Se1–O4
Se1–O2
Se1–O3
Se1–O1
2.3072(15)
2.3587(16)
2.3635(15)
2.3899(15)
2.4156(16)
2.4645(15)
1.6092(12)
1.6115(12)
1.6706(13)
1.6791(13)
Na3–O2
Na3–O5
Na3–O7
2.372(2)
2.544(2)
2.571(2)
O7–Se2–O5
O7–Se2–O6
O5–Se2–O6
O7–Se2–O8
O5–Se2–O8
O6–Se2–O8
115.05(9)
110.37(10)
113.26(9)
107.52(9)
107.15(9)
102.49(9)
O4–Se1–O2
O4–Se1–O3
O2–Se1–O3
O4–Se1–O1
O2–Se1–O1
O3–Se1–O1
113.77(7)
107.82(7)
110.65(7)
110.74(7)
109.64(7)
103.73(7)
2 4 2
Te O (OH)
Te1–O3
Te1–O5
Te1–O6
Te1–O1
Te1–O4
Te1–O4
Te2–O2
Te2–O5
Te2–O3
Te2–O2
1.8625(9)
1.9121(9)
1.9160(9)
1.9326(10)
1.9412(9)
1.9532(9)
1.8664(12)
1.9357(9)
2.0673(9)
2.0979(9)
O3–Te1–O5
O3–Te1–O6
O5–Te1–O6
O3–Te1–O1
O5–Te1–O1
O6–Te1–O1
O3–Te1–O4
O5–Te1–O4
O6–Te1–O4
O1–Te1–O4
O3–Te1–O4
178.26(4)
93.56(4)
86.25(4)
91.44(4)
86.83(4)
87.93(4)
96.13(4)
85.60(4)
91.21(4)
172.41(4)
90.31(4)
O5–Te1–O4
O6–Te1–O4
O1–Te1–O4
O4–Te1–O4
O2–Te2–O5
O2–Te2–O3
O5–Te2–O3
O2–Te2–O2
O5–Te2–O2
O3–Te2–O2
89.78(4)
174.63(4)
88.25(4)
92.09(2)
90.74(4)
88.87(4)
88.44(4)
87.33(3)
83.96(4)
171.45(4)
4
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Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
2 3 4 5 3 4 4 2 2
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O)
In the course of crystallization experiments for structure with preceding grinding revealed mainly the α-form and the β-
analysis of selenous acid, Wells and Bailey have already re- form as a minority phase. These findings and the results of the
ported that “on rapid cooling, a supersaturated solution (of phase formation studies in the system Na SeO /H SeO /H O
2
4
2
4
2
aqueous selenous acid) deposits lath-shaped crystals belonging at 25 °C under equilibrium conditions[ should provide an
to the triclinic system”.[ However, lattice parameters of the indication that the α-form is the thermodynamically stable
triclinic form of H SeO or any further details have not been phase of Na H (SeO ) (H O) .
18]
8]
2
3
5
3
4 4
2
2
given in the original report or afterwards. In our crystallization
experiments we were not able to reproduce these results when
working with hot- or cold-saturated aqueous solutions of
Structures
H SeO and different crystallization times. In all cases we ex-
2
3
All title compounds belong to the family of oxidochalco-
genates containing E–O bonds (E = S, Se, Te). General fea-
clusively received the orthorhombic α-H SeO modification.
2
3
Few β-H SeO crystals had only formed by chance if the as-
2
3
tures (occurrence, preparation, structures) of this family of
2
compounds have been reviewed recently[
19]
and now are
grown SeO crystals (obtained from the chemical transport re-
action experiment) were left under ambient conditions over-
night. The hygroscopic character of these crystals apparently
led to the formation of a solution of selenous acid. It seems
plausible that a local supersaturation of the resulting solution
expanded by the new polymorphic β-forms of H SeO ,
2
3
NaHSeO , and Na H (SeO ) (H O) .
4
5
3
4 4
2
2
For all crystals, the unit cell determination at room tempera-
ture and at –173 °C showed the same symmetry and similar
lattice parameters, indicating no phase transitions within this
temperature range.
could be the reason for crystallization of β-H SeO , as de-
2
3
scribed by Wells and Bailey. Such conditions make a targeted
crystallization of β-H SeO difficult or even unreproducible.
2
3
The fact that the triclinic form of H SeO has not been struc-
2
3
2
α- and β-H SeO3
turally characterized more than 60 years after the first report
of its existence clearly supports this assumption.
The crystal structure of the orthorhombic α-form of selenous
acid has been determined in 1949 by Wells and Bailey based
on X-ray data from oscillation and Weissenberg photographs
and was later re-investigated on basis of single-crystal neutron
data, allowing the localization of hydrogen atoms.
Two SeO(OH) molecules are present in the asymmetric unit
of the triclinic β-polymorph of H SeO . Both molecules have a
very similar trigonal-pyramidal configuration about the central
Se atom, with the two Se–OH bonds (O atoms of the OH
Concentrated selenic acid oxidizes TeIV to Te under the
VI
given hydrothermal conditions at 220 °C. A partial oxidation
[8]
IV/VI
of the employed TeO to the mixed-valent Te
compound
2
Te O (OH) was achieved in 70 %wt selenic acid, whereas a
[20]
2
4
2
IV
complete oxidation of Te (employed as Na TeO ) to TeO
2
3
3
2
resulted in 96 %wt selenic acid. The triclinic β-NaHSeO4
2
3
phase then spontaneously crystallized from the remaining solu-
tion. Monoclinic α-NaHSeO has been obtained during phase
IV
4
formation studies in the system Na SeO /H SeO /H O at
2
4
2
4
2
functions are O2, O3, O5, O6; mean bond length for the two
molecules 1.750 Å) significantly longer than the Se–O bond
O1, O6; 1.644 Å). The O–Se–O angles vary from 96.48(13)°
2
5 °C under isothermal equilibrium conditions and was re-
[18]
ported to be incongruently soluble.
Since no polymorphism
(
was reported for NaHSeO under these conditions (equilibra-
4
to 99.86(12)° and are typical for trigonal-pyramidal SeO3
tion time was 3 d), it appears likely that the α-modification is
the thermodynamically stable modification. Our targeted
[21,22]
units.
In the crystal structure, the molecules are arranged
in layers parallel to (100) with the apices of the trigonal-pyra-
mids all pointing in the same direction, which reflects the non-
centrosymmetric space group symmetry (Figure 1). Strong
O–H···O hydrogen bonding is observed between the OH func-
tions and the terminal oxygen atoms of molecules in an adja-
cent layer (O5···O4; O2···O4; O6···O1) and leads to the cohe-
crystallization procedures to obtain β-NaHSeO proved unsuc-
4
cessful, and we obtained a new modification of the acid salt
Na H (SeO ) (H O) instead. This phase (in the original re-
5
3
18]
4 4
2
2
port[
,
the composition of this salt was given as
Na SeO ·2H SeO ·4H O) has also been reported to occur in
2
4
2
4
2
the system Na SeO /H SeO /H O in a phase region very sion of the structure. There is also a bifurcated O–H···O hydro-
2
4
2
4
2
close to that of NaHSeO4.[
18]
Recrystallization of gen bond present. One part of this bond is a strong intra-layer
[18]
Na H (SeO ) (H O) , a congruently soluble salt,
from hot hydrogen bond (O3···O1) and the other part (O3···O4) defines
5
3
4 4
2
2
water was unproblematic. However, different nucleation condi- another inter-layer hydrogen bond, significantly weaker in na-
tions led to crystallization of one of the two modifications. ture (Table 4).
Whereas crystallization from hot solutions yielded exclusively
The known α-polymorph of selenous acid crystallizes with
α-Na H (SeO ) (H O) , crystallization from saturated room- orthorhombic symmetry in space group P2 2 2 with one mo-
5
3
4 4
2
2
1 1 1
temperature solutions yielded β-Na H (SeO ) (H O) that was lecule in the asymmetric unit.[
8,20]
5
3
4 4
2
2
The configuration of the
stable only in freshly crystallized form. After 1 d, the mono- molecular entity is the same as in the β-polymorph, i.e. a
clinic β-form had completely transformed into the triclinic α- SeO(OH)2 trigonal-pyramid with one short Se–O bond of
form in the remaining mother liquor. This β Ǟ α transforma- 1.643(2) Å and two longer Se–OH bonds of 1.735(2) and
[
20]
tion seems to be accelerated or even induced by applying pres- 1.743(2) Å, as determined from neutron single crystal data.
sure. PXRD measurements of as-crystallized material without The arrangement and the hydrogen-bonding scheme of the
preceding grinding and performed immediately after drying of SeO(OH) molecules differ in the crystal structures of the two
2
the crystals revealed the β-form, whereas PXRD measurements polymorphs. In the α-polymorph individual molecules are ar-
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
S. Pollitt, M. Weil
ARTICLE
2.621(2) Å] and lead to the formation of a layered structure
parallel to (100) (Figure 2).
Figure 2. The crystal structure of α-H
2
SeO
3
in a projection along
¯
[
010]. Displacement elliposoid are drawn at the 90% probability level;
hydrogen bonding is indicated by dashed lines. Structure data were
[
20]
taken from the literature.
α- and β-NaHSeO4
NaHSeO was also obtained as a phase appearing in the
4
phase diagram of the Na SeO /H SeO /H O system at
2
4
2
4
2
18]
2
5 °C.[ Its crystal structure was later determined to belong
[23]
¯
to the monoclinic system (space group P2 /n).
Polymor-
Figure 1. The crystal structure of β-H
2
SeO
3
in a projection along [100]
1
(
top) and along [021] (bottom). Displacement ellipsoids are drawn at phism has not been reported to occur for this phase.
the 90% probability level; hydrogen atoms are given as spheres of
arbitrary radius. Hydrogen bonding is indicated by dashed lines (strong
interactions) and dotted lines (medium-strength interactions).
The basic structure units of β-NaHSeO are NaO octahedra
4
6
and SeO (OH) tetrahedra. The NaO octahedra share edges
3
6
(
[
O2···O2; O4···O4) to form zigzag chains running parallel to
010]. These chains are linked through SeO (OH) tetrahedra
3
ranged alternately in an “up and down” fashion with respect via common oxygen atoms into a three-dimensional frame-
to the apices of the trigonal pyramids. Two hydrogen bonds work structure (Figure 3), in which each NaO octahedron is
6
are of medium-strength [O···O distances 2.667(2) and linked to six SeO (OH) tetrahedra and each SeO (OH) tetrahe-
3
3
Table 4. Details of the hydrogen bonding arrangement /Å,° in the crystal structures of the title compounds.
D
H
A
D–H
H···A
D···A
D–H···A
β-H
O3
O3
O5
O2
O6
2 3
SeO
H1
H1
H3
H2
H4
O1
O4
O4
O4
O1
0.98
0.98
0.98
0.98
0.98
1.93(4)
2.48(5)
1.66(2)
1.693(12)
1.664(6)
2.665(3)
3.019(4)
2.595(3)
2.659(4)
2.641(3)
130(4)
114(4)
158(5)
168(5)
175(5)
β-NaHSeO
4
O1
O3
H1
H2
O1
O3
0.98
0.98
1.71(3)
1.61(3)
2.616(3)
2.540(3)
153(6)
156(7)
β-Na
O3
O8
O9
O9
5 4 18 7
Se O H
H1
H2
H3
H4
O3
O1
O4
O6
0.98
0.98
0.81
0.82
1.68
1.55
2.14
2.00
2.447(4)
2.519(3)
2.865(3)
2.793(3)
133
169
150
162
2 4 2
Te O (OH)
O6
O1
H2
H1
O1
O6
0.98
0.98
1.784(4)
1.836(7)
2.7604(15)
2.8052(14)
174(3)
170(4)
6
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
2 3 4 5 3 4 4 2 2
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O)
dron to four NaO octahedra. The Na–O distances in the dis- drogen bond between two SeO (OH) tetrahedra in the α-form
6
3
torted NaO6 octahedron range from 2.3072(15) to is characterized by a donor···acceptor distance of 2.655(3) Å
.4645(15) Å, with the two longest bonds to those oxygen and passes through adjacent layers (Figure 4). It is interesting
atoms that are also part of SeO (OH) tetrahedra. In contrast to to note that the homologous compound NaHSO is likewise
2
3
4
[
25]
the majority of tetrahedral hydrogenselenate(IV) anions with dimorphic. The monoclinic β-polymorph of NaHSO4
is iso-
one significantly longer Se–OH bond and three shorter Se–O typic with α-NaHSeO ; the triclinic α-polymorph of NaHSO
4
4
bonds with similar length,[
11–13,24]
there are two pairs of (Z = 4)
[26,27]
crystallizes in a different structure than the tri-
Se–O bonds in the SeO (OH) tetrahedron, one with two longer clinic β-polymorph of NaHSeO (Z = 2).
3
4
(O1, O3) and one with two shorter (O2, O4) bonds. This un-
usual bond length distribution in the SeO (OH) tetrahedron is
3
caused by the disorder of the proton. Two hydrogen atom posi-
tions could be clearly located in difference Fourier maps, with
bonds to O1 and O3. Both oxygen atoms are simultaneously
the donator and acceptor atoms of two strong hydrogen bonds
[O3···O3 = 2.540(3) Å; O1···O1 = 2.616(3) Å]. Since the corre-
sponding hydrogen atoms are related by inversion symmetry
and directly point to each other, both hydrogen atoms cannot
show full occupation and consequently are half-occupied (Fig-
ure 3, Table 4).
4
Figure 4. The crystal structure of α-NaHSeO in polyhedral represen-
¯
tation in a projection along [010]. Hydrogen bonding is indicated by
dashed lines; color code as in Figure 3. Structure data were taken from
[
23]
the literature.
α- and β-Na H (SeO ) (H O)
2
5
3
4 4
2
Another phase occurring in the Na SeO /H SeO /H O sys-
2
4
2
4
2
tem at 25 °C[ is Na H (SeO ) (H O) (α-modification). Its
18]
5
3
4 4
2
2
[
11]
crystal structure was independently determined in 1989
and
12]
[13]
1
990,[ and was later re-investigated and has triclinic sym-
Figure 3. The crystal structure of β-NaHSeO
4
in polyhedral represen-
octahedra are light-grey, SeO
tetrahedra are dark-grey. Hydrogen bonding is indicated by dashed
¯
¯
tation in a projection along [010]. NaO
6
4
metry (space group P1). Polymorphism has not been reported
for Na H (SeO ) (H O) .
5
3
4 4
2
2
lines; the hydrogen atom of the SeO
and half-occupied.
3
(OH) tetrahedron is disordered
The structure of β-Na H (SeO ) (H O) is characterized by
5
3
4 4
2
2
the presence of two NaO6 octahedra (Na1, Na3), one
The main structural units of the monoclinic α-polymorph of NaO (H O) octahedron (Na2) situated on a twofold rotation
2
2
4
NaHSeO are likewise NaO octahedra, with Na–O distances axis, one SeO (OH) tetrahedron (Se2) with three similar
4
6
3
in the range 2.374(3) to 2.499(3) Å, and SeO (OH) tetrahedra Se–O and one longer Se–O(H) bond (Table 3), and one
3
with three short Se–O distances 1.604(2), 1.620(2), and hydrogen-bis[monoselenate(VI)] [SeO ···H···O Se] unit (Se1)
4
4
1.627(2) Å and one long Se–O distance of 1.726(2) Å, the lat- that has a very short interpolyhedral O3···O3 distance of
ter corresponding to the Se–OH bond. 2.447(4) Å. The linkage of these building blocks leads to a
In the crystal structures of the two polymorphs, the arrange- rather complex framework structure for which the following
ment of the NaO octahedra is markedly different. In the α- structural motifs are highlighted: The Na2O (H O) octahedra
6
2
2
4
polymorph, two NaO6 polyhedra share an edge to form a share edges (each defined by the water molecule O9) to build
Na O unit. Adjacent Na O units are linked to another by up infinitive chains running parallel to [100]. Other oxygen
2
10
2 10
sharing a corner atom, resulting in the formation of a layered atoms (O5) of these chains each are part of another NaO octa-
6
arrangement parallel to (101). The SeO (OH) tetrahedra are hedron (Na3) and of one SeO (OH) tetrahedron (Se2). These
3
3
attached above and below such a layer and connect adjacent two types of polyhedra are in turn linked to NaO octahedra
6
layers into a three-dimensional framework. The O–H···O hy- (Na1) to make up the three-dimensional framework structure
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7

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/KAP1
Date: 01-04-14 17:03:34
Pages: 11
S. Pollitt, M. Weil
ARTICLE
(
Figure 5). The [Se1O ···H···O Se1] unit is connected to this additional neutron diffraction measurements will eventually
4 4
framework, thereby filling the voids. Hydrogen bonding in- give experimental evidence whether our model with a disor-
cluding the Se2O (OH) tetrahedron (strong interactions) as dered proton is correct or not. Unfortunately, the necessity to
3
well as the water molecule (medium interactions) as donor grow large and stable single crystals of β-Na H (SeO ) (H O)
2
5
3
4 4
2
groups with the framework oxygen atoms as acceptor groups complicate matters to perform this kind of experiment.
enhances the stability of the structure (Table 4). In comparison with the monoclinic β-polymorph of
[13]
Na H (SeO ) (H O) , in the triclinic α-polymorph
very
5
3
4 4
2
2
similar building blocks are present, but the structural arrange-
ment is markedly different. Two NaO octahedra (one of which
6
is located about an inversion center), one NaO (H O) polyhe-
6
2
dron and two SeO tetrahedra make up the crystal structure.
4
One of the two tetrahedral selenate units can be considered
as a hydrogenselenate(VI) anion with three short Se–O bonds
[
[
1.604(2), 1.611(2) and 1.625(2) Å] and with one long Se–O
1.719(2) Å] bond. The second SeO tetrahedron, with Se–O
4
bond lengths of 1.619(2), 1.624(2), 1.629(2), and 1.680(2) Å,
likewise forms a centrosymmetric [SeO ···H···O Se] unit with
4
4
a similar short interpolyhedral O···O distance of 2.472(4) just
as observed in the β-polymorph. In the first structure refine-
[11]
ment of α-Na H (SeO ) (H O)
2
the corresponding proton
5
3
4 4
2
was refined (X-ray data) on the inversion center located about
this hydrogen bond, resulting in a symmetrical O···H···O hy-
drogen bond, whereas subsequent refinements (X-ray data)
used a disorder model with one short O–H and one long H···O
contact.[
12,13]
Again, only neutron diffraction studies will give
clear evidence about the nature of the hydrogen bonding situa-
tion within the [SeO ···H···O Se] unit in the structure of α-
(SeO (H O) . The three kinds of NaO polyhedra are
Figure 5. The crystal structure of β-Na
dral representation in a projection along [100]. The proton of the
Se1O ···H···O
Se1] unit is disordered and half-occupied. Hydrogen Na
bonds are omitted for clarity; color code as in Figure 3.
5 3 4 4 2 2
H (SeO ) (H O) in polyhe-
¯
4
4
[
4
4
5
H
3
4
)
4
2
2
x
condensed into slabs running along [001], thereby forming a
¯
layered arrangement parallel to (110). The layers are bridged
by the two kinds of selenate units, and the cohesion of the
In general, two hydrogen-bonding situations are possible in structure is supported by hydrogen bonding between the hy-
such a hydrogen-bis[monoselenate(VI)] anion: (i) an asymmet- drogenselenate groups and between water molecules and oppo-
ric O–H···O hydrogen bond with a disordered proton, or (ii) a site oxygen atoms (Figure 6).
symmetric hydrogen bond with an ordered proton located on
the inversion center. On basis of the present single-crystal X-
ray diffraction data, the proton of the centrosymmetric
[
Se1O ···H···O Se1] unit was discernible from difference Fou-
4 4
rier maps and is located closer to one of the symmetry-related
O3 atoms, hence ruling out possibility (ii). A very similar hy-
drogen-bonding situation is present in the related structure of
Na H (SeO ) with a likewise very close interpolyhedral O···O
3
5
4 4
distance between two SeO tetrahedra of ca. 2.48 Å. According
4
to the Na H (SeO ) structure model derived from single-crys-
3
5
4 4
tal X-ray diffraction data,[ this proton is disordered in the
23]
corresponding [SeO ···H···O Se] unit, whereas refinements
4
4
based on single crystal neutron diffraction data unambiguously
showed the presence of a symmetric and linear hydrogen
bond.[
24]
We certainly are aware that the localization of
the hydrogen position in the [SeO ···H···O Se] unit in
4
4
β-Na H (SeO ) (H O) is connected with a high uncertainty.
5
3
4 4
2
2
Although in many cases high-quality X-ray data allow the de-
termination of protons even in the vicinity of much heavier
elements, in the case of β-Na H (SeO ) (H O) the reliability
of this method is all the more limited due to the disordered
character of the proton. Therefore the real hydrogen-bonding
5
3
4 4
2
2
5 3 4 4 2 2
Figure 6. The crystal structure of α-Na H (SeO ) (H O) in polyhe-
dral representation in a projection along [110]. Hydrogen bonds are
omitted for clarity; color code as in Figure 3. Structure data were taken
[
13]
situation in β-Na H (SeO ) (H O) could be different. Only from the literature.
5
3
4 4
2
2
8
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2 3 4 5 3 4 4 2 2
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O)
Table 5. Bond valence sums (BVS) of individual atoms in the crystal structures of the title compounds. Values are given in valence units (v.u.)
without contribution of H atoms; O atoms bonded to H atoms are marked with an asterisk for OH functions or with two asterisks for a water
molecule.
β-H
Se1 3.91, Se2 3.94, O1 1.55,
O2* 1.15, O3* 1.12, O4 1.59, O1* 1.60, O2 2.19,
2
SeO
3
β-NaHSeO
4
β-Na
Na1 1.12, Na2 1.16, Na3 1.17, Se1 5.98, Se2
5.96, O1 1.85, O2 2.06, O3* 1.65, O4 1.99, O5 2.07, O3 2.15, O4 2.17, O5 2.31,
1.94, O6 2.05, O7 2.09, O8* 1.49, O9** 0.46 O6* 1.18
5
H
3
(SeO
4
)
4
(H
2
O)
2
Te
2 4 2
O (OH)
Na1 1.26 Se1 5.95,
Te1 5.98, Te2 3.97, O1* 1.13, O2
O5* 1.22, O6* 1.13
O3* 1.65, O4 2.15
Te O (OH)
2
cated in the original study, the authors assumed the same type
of hydrogen bonding scheme on basis of O···O distances and
the bonding situation of these two oxygen atoms, with only
one strong bond to the tellurium(VI) atom. The current redeter-
mination shows that this assumption was altogether correct.
Bond valence sum calculations[ were performed for all
2
4
In comparison with the previous structure determination of
the mixed-valent tellurium(IV/VI) compound Te O (OH) ,
the current redetermination reports the localization of hydro-
gen atoms and, as expected, a more precise determination of
lattice parameters and atomic coordinates.
The re-determination of Te O (OH) confirmed the basic
structural features as determined in the original study. In the
structure, [Te O (OH) ] octahedra are linked by sharing cor-
ner oxygen atoms into zigzag chains extending parallel to
[28]
2
4
2
29]
structures using the bond valence parameters of Brese and
2
4
2
[30]
O’Keeffe
(Table 5). The Na sites, the Te or Se sites are rea-
sonably close to the expected values of 1 for Na and 4 or 6
for tetra- or hexavalent Te and Se, respectively. The oxygen
VI
4
2
atoms of OH or H O functions are readily identifiable. The
IV
2
[001]. Similar chains of corner-sharing Te O bisphenoids run
4
underbonded oxygen atoms are, as expected, acceptors of the
hydrogen bonds. This behavior is particularly pronounced in
the structure of β-H SeO with bond valence sums around 1.6
parallel to the first type of chains in an alternating fashion.
Both types of chains are connected by common edges to form
a layer parallel to (100). These layers are held together by
medium-strength hydrogen bonds between the two OH func-
tions [O1···O6 = 2.8052(14) Å]. The acceptor oxygen atom and
the donator oxygen atom of this hydrogen bond are at the same
time the donator oxygen atom and the acceptor oxygen atom,
respectively, of an intra-layer hydrogen bond with a somewhat
shorter donor···acceptor distance of O6···O1 = 2.7604(15) Å
2
3
v.u. for the two acceptor oxygen atoms O1 and O4.
Acknowledgements
The X-ray centre of the Vienna University of Technology is acknow-
ledged for providing access to the powder and single-crystal dif-
(Figure 7). Although the two hydrogen atoms could not be lo- fractometers.
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2
O
4
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(OH)
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Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
9

Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
S. Pollitt, M. Weil
ARTICLE
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[
Received: February 14, 2014
Published Online: ᭿
1
0
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z14068
/KAP1
Date: 01-04-14 17:03:34
Pages: 11
2 3 4 5 3 4 4 2 2
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O)
S. Pollitt, M. Weil* .......................................................... 1–11
Polymorphism of H SeO , NaHSeO and Na H (SeO ) (H O) ,
2
3
4
5
3
4 4
2
2
and Re-refinement of the Crystal Structure of Te O (OH)
2
2
4
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
11