Zeitschrift für Kristallographie 183, 51 - 6 1 (1988)

f by R. Oldenbourg Verlag, München 1988 - 0044 -2968/88 $3.00 + 0.00

Crystal and molecular structure

of a mixed alkali-tetraborate trihydrate
Ki 6 7 Na 0 33B 4 0 5 (OH) 4 · 3 H 2 0
Cornelia Smykalla and Helmut Behm
Crystallography Laboratory, University of Nijmegen, Toemooiveld, 6525 ED Nijmegen,
The Netherlands

Dedicated to Professor Dr. Theo Hahn on the occasion of his 60th birthday
Received: October 14,1987

Crystal structure / Soro borate / Mixed alkali-tetraborate trihydrate

Abstract. The structure of the title compound, K1.67Na0.33B4O5(OH)4

• 3H 2 0, was determined by X-ray structure analysis at T = 293 K. M, =
159.07, hexagonal, space group PT>2c, cell dimensions a = 11.278(8), c =
15.806(10) Ä; V = 1741.07(9) A 3 , Ζ = 6, Dx = 1.821 Mg/m 3 , Dm = 1.83
Mg/m 3 (floation method). F(000) = 968, MoXix radiation (graphite crystal
monochromator, λ = 0.71073 Α), μ(ΜοΑΓα) = 7.537 cm" 1 . Final conven-
tional fl-factor = 0.043, Rw = 0.063 for 1394 'observed' reflections and
120 variables.
The structure belongs to the class of soro borates and contains isolated
tetraborate [Β 4 0 5 (0Η) 4 ] groups. It is the first known hydrated mixed
alkali-borate. The structure is built up by layers perpendicular to the
hexagonal axis, each layer containing the borate molecules and adjacent
cations with the schicht-group symbol 3p21 (Niggli, 1959). The structure
is strongly related to that of tincalconite (Giacovazzo et al., 1973), both
structures have almost equal layers, but the stacking sequence is of a
different kind.

Introduction
The first samples of the title compound were found fortuitously during an
experiment to investigate mixed — potassium — sodium — copper —
borates. Colourless, hexagonal-shaped crystals have been observed, grown

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52 Cornelia Smykalla and Helmut Behm

from a Κ, Na-tetraborate (molar ratio 1:1) solution, saturated with

CU(OH)2. These crystals seem to be metastable at room temperature,
several of them decompose after days or weeks.
The IR-spectra (Fig. 1) of this new compound as well as the X-ray
powder diagram show much similarity to those of the already known
tincalconite, but they are not identical. A chemical analysis of the alkali
ratio in one picked single crystal gave a Na —Κ ratio of 1:4.8. Further
attempts to crystallize this compound from a Na:K = l : 5 tetraborate
solution failed.
Since hydrated, mixed-alkali borates have not been reported earlier, it
seemed desirable to investigate the structure and the relation with
tincalconite.
After solving and understanding the new structure, a method has been
developed to crystallize the new compound. A solution of alkali-
tetraborate, molar ratio for Na: Κ = 1:5, is concentrated carefully, to avoid
crystallization of K-pentaborate. The concentrated solution is than seeded
with powder of tincalconite or the new compound. By this method crystals
up to several mm can be obtained.

Experimental
A colourless crystal with hexagonal columnar shape of approximately
0.3 χ 0.3 χ 0.5 mm, crystallized from the solution of K, Na — Cu-borate was
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κ , 67Na 0 3 3 Β 4 0 5 ( 0 Η ) 4 · 3 Η 2 0 53

used for the measurements using MoAfa radiation with a graphite crystal
monochromator on a Picker single crystal diffractometer. The unit-cell
dimensions were determined from the angular settings of 14 reflections
with 8 < 0 < 31 The space group was determined to be P62c from
systematic absences.
The intensity data of 10545 reflections (half a sphere up to 0 = 58°)
were measured, using the ω-2θ scan technique, scan speed 2° per min, scan
range from 0.9 below KOLX to 0.8 above KA2, background 2 χ 20 s. The
intensity of the primary beam was checked throughout the data collection
by monitoring three standard reflections every 100 reflections. The final
drift correction factors were less than 3%. Lorentz and polarization correc-
tions with a program written by Holub (1982) were applied and the data
were reduced to |Fo|-values. Laue-symmetry-equivalent reflections were
averaged, RFo = E(F-(F»/EF= 0.026, resulting in 920 reflections.
The structure was solved using Patterson methods and was refined by
full-matrix least-squares on |F| values using SHELX (Sheldrick, 1976).
Scattering factors were taken from International Tables (1974).
Three atoms were found to be disordered: individual positional
parameters for K(1A) and 0(7AW), but not for H(7A), were found in the
difference Fourier map. At the first stages of the refinement the individual
occupancy factors were refined as independent parameters and were found

Table 1. Fractional positional and thermal parameters (with e.s.d.'s).

Atom X y ζ t/eqC X 100)

K(l) 0.52492(27) -0.07839(23) 0.75000 4.12(10)1

K(2) 0.00000 0.00000 0.75000 4.36(7)
K(3) 0.33333 0.66667 0.25000 1.82(4)
Na(l) 0.00000 0.00000 0.50000 3.30(10)
K(1A) 0.66553(39) 0.00980(37) 0.25000 4.00(12)2
O(l) 0.53275(23) 0.00000 0.00000 0.97(8)
0(2) 0.36639(23) -0.04758(20) 0.60868(11) 1.62(7)
0(3) 0.29458(21) -0.16002(22) 0.47419(13) 1.64(7)
0(4H) 0.86835(23) 0.46417(23) 0.87038(12) 1.55(8)
0(5H) 0.59233(27) -0.15621(24) 0.90375(15) 2.56(10)
0(6W) 0.18935(35) 0.12337(36) 0.90264(24) 4.15(13)
0(7W) 0.26937(76) 0.06644(96) 0.25000 4.27(40)'
0(7AW) 0.6765(26) -0.2304(16) 0.25000 9.2(12)2
B(l) 0.93730(29) 0.42809(31) 0.93394(19) 1.07(10)
B(2) 0.27458(33) -0.15223(32) 0.55914(20) 1.49(11)
H(4) 0.189(6) -0.335(6) 0.119(3) 4.8(16)
H(5) 0.412 0.311 0.058 12.6(33)
H(6) 0.821(6) 0.034(6) 0.084(4) 6.5(16)
H(6A) 1.082(11) -0.116(12) 0.057(5) 13.4(42)
H(7) 0.916(8) 0.241(7) 0.205(4) 3.1(19)'

Occupancy factors: 1 0.634(2), 2 0.366(2).

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54 Cornelia Smykalla and Helmut Behm

to be equal (range 0.638—0.625 and 0.344,0.391). Therefore the occupancy

factors were restrained to o n e parameter. Isotropic refinement converged
to R = 0.113. At this stage an absorption correction was applied (Walker
and Stuart, 1983), resulting in a further decrease of R to 0.092 (correction
factors were in the range of 0.876 —1.167). After completion of the isotropic

Table 2. Bond and polyhedra lengths A (with e.s.d.'s).

B(l)-0(1) 1.466(3) K(3)-< 3(4H) 2.760(4) 6 χ

B(l)-0(2) 1.491(4) 0(4H)-- 0 ( 4 H ) 3.462(4) 2 · 3
B(l)-0(3) 1.491(3) 0(4H)-- 0 ( 4 H ) 3.805(4)'
B(1)-0(4H) 1.448(3)
B(2)-0(2) 1.362(4) NA(1)-- 0(6W) 2.428(4) 6 χ
B(2)-0(3) 1.372(4) 0(6W) —0(6W) 3.252(6)2·3
B(2)-0(5H) 1.373(4) 0(6W) —0(6W) 3.337(7)4
0(6W) —0(6W) 3.909(8)5
K(l)-0(2) 2.988(2) 2 χ
K(1)-0(4H) 2.824(3) 2 χ K(1A)-- 0 ( 4 H ) 2.775(6) 2 χ
K(1)-0(5H) 2.814(3) 2 χ K(1A)-- 0 ( 5 H ) 2.822(6) 2 χ
0(2)-0(4H) 2.378(5) K(1A)--0(6W) 3.260(6) 2 χ
0(2)-0(5H) 3.340(5) K(1A)-- 0(7W) 2.701(7)
0(4H)-0(5H) 3.270(5) K(1A)--0(7AW) 2.77(2)
0(2)-0(2) 4.467(4)' 0(4H)-- 0 ( 4 H ) 3.805(4)'
0(4H)-0(4H) 3.805(4)' 0(4H) -- 0(5H) 3.270(5)
0(5H)-0(5H) 4.860(5)' 0(4H)-- 0 ( 6 W ) 3.631(4)
0(5H)-- 0 ( 5 H ) 4.860(5)'
K(2)-0(6W) 3.057(4) 6 χ 0(5H)-- 0(6W) 2.920(6)
K(2)-0(7W) 2.741(5) 3 χ 0(5H) - 0(7W) 3.072(6)
0(6W)-0(6W) 3.252(6)2· 3 0(6W) —0(7W) 3.569(6)
0(6W)-0(7W) 3.279(5) 0(6W) —0(7AW) 2.96(1)
0(6W)-0(7W) 3.569(5)2
0(7W)-0(7W) 4.748(6)'
1
Symmetry operations: x,y,l/2 — z; 2—y,x—y,z; 3
y—x, — x,z; *y,x,—z; 5
x—y,—y,
— z.

Table 3. Selected bond angles 0 (with e.s.d.'s).

B(l)-0(1)-B(l) 111.3(4)
B(l)-0(2)-B(2) 117.0(4)
B(l)-0(3)-B(2) 120.6(3)
0(l)-B(l)-0(2) 108.4(4)
0(l)-B(l)-0(3) 108.9(2)
0(1)-B(1)-0(4H) 112.2(5)
0(2)-B(l)-0(3) 108.5(4)
0(2)-B(l)-0(4H) 108.1(4)
0(3) — B( 1)—0(4H) 110.6(5)
0(2)-B(2)-0(3) 122.7(3)
0(2) — B(2)—0(5H) 117.9(4)
0(3)—B(2)—0(5H) 119.3(3)

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Κ 167 Ν30.33Β4θ5(ΟΗ) 4 ·3Η 2 Ο 55

Ο ο
Fig. 2. Projection of the structure viewed along the c axis (the main positions of the
disordered atoms are given only).

refinement the Bijvoet coefficient was calculated (Beurskens et al., 1980),

resulting in a value of 0.75(3), based on 57 Friedel pairs, showed that the
absolute structure is correct.
During the final stages of the refinement the positional parameters and
the anisotropic temperature factors of all nonhydrogen atoms were refined.
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56 Cornelia Smykalla and Helmut Behm

Ο Ο

ο
Fig. 3. Projection of one layer of tincalconite, viewed along the c axis.
ο

The hydrogen atoms were found from difference Fourier syntheses and
were included with isotropic temperature factors in the refinement, H(5)
with fixed positional parameters.
The final conventional agreement factors were R = 0.043 and Rw =
0.063 for 1349 'observed' reflections and 120 variables. The function
minimized was Iw • (Fo - Fc)2 with w = 1 /(<x2(/o) + 0.0002 Fo2) with a(Fo)
from counting statistics. The maximum shift over error ratio in the last
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K167Na0.33B4O5(OH)4-3H2O 57

c
ο
>

Ο Ο C D o ( Χ Χ > C D o Ο s
εο
α

1υ
•ρ

C
ο

aΒ
'3
Ε

ο ο c d o α χ > ( Τ ) ο οο
c
ο
Τ3
'S
υ
?

3
8
Ο ο ( Γ )Ο Χ ) ο ( Ό Ο Ο «

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K,. 6 ,Na 0 33Β 4 0 5 (0Η) 4 3H20 59

06W
06W / 06W 0 21 05H

06W 06W 02 05H

a T&w" b 04H

04H

04H

05H

Fig. 6. Coordination polyhedra of a) Na(l) octahedron; b) K(l) trigonal prism; c) K(2)

tricapped trigonal prism; d) K(3) trigonal prism; e) K(1 A) square antiprism.

full-matrix least-squares cycle was less than 0.03 for the nonhydrogen atoms
and 0.08 for the hydrogen atoms. The final difference Fourier map showed
no peaks higher than 0.6 e/A 3 . Plots were made with PLUTO (Motherwell,
1976).
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60 Cornelia Smykalla and Helmut Behm

Discussion
Final positional and thermal parameters are given in Table 1. Selected
molecular geometry data are collected in Tables 2 and 3.
The tetraborate molecule lies on the twofold axis. B(l) is surrounded by
four Ο atoms [ B - O 1.448(3)-1.491(4) A], which form a slightly distorted
tetrahedron. The three Ο atoms, bonded to B(2) [1.362(4)-1.373(4) Ä],
form a nearly ideal triangle. The averaged Β —Ο distance in many
compounds is 1.37(2) Ä (Zobetz, 1981). This type of anion is found in
several borates, as in tincalconite (Giacovazzo et al., 1973) or borax
(Morimoto, 1956).
The polyhedra which surround the Na and Κ atoms are shown in
Figure 6 as an arrangement of points on a sphere that maximize their
distances (Gillepsie, 1972). The 0(6W) atoms form a nearly regular
octahedron around Na(l). K(2) is surrounded by nine Ο atoms which form
a tricapped trigonal prism. The edges of the middle triangle, which is built
up from three 0(7W) atoms, are elongated. The Na(l) octahedron shares
two faces with two K(2) polyhedra forming a chain along the c axis. The
K(2) polyhedron shares also one edge, 0 ( 6 W ) - 0 ( 7 W ) , with the K(1A)
square antiprism along the a axis. The two square bases of the K(1A)
polyhedron are irregular (edges 3.805(4) A, 4.806(5) A and 3.569(6) A,
2.957(10) A, respectively). This polyhedron shares one face, built up from
two 0(4H) and two 0(5H), with a K(l) trigonal prism along the a axis.
The trigonal prisms around K(l) and K.(3) are elongated along the c axis.
The K(3) prism shares three edges with three K(l) prisms along the c axis.
The similarity of the new structure and the tincalconite structure is
seen from Figures 2 and 3, projections of one layer along c. Tincalconite,
Na 2 B 4 0 5 (0H)4 · 3 H 2 0 crystallizes in space group Ä32, a = 11.09(3), c =
21.07(4) A. The tetraborate ion lies, as in the new structure, on the twofold
axis.
The difference between the structures is obvious from Figures 4 and 5,
which are projections along the b axis. The new structure is built up from
two layers, related by the mirror plane of the 6 operation. Tincalconite
shows three layers, displaced by the Ä-centering of the space group.
The positional parameters of the cations in projections along c are equal
for the two structures. The position of Na(l) in tincalconite corresponds
to those of K(1A) and K(l), with K(1A) more nearby. The Ο atoms of the
water molecules have different positions, because the cation polyhedra in
the new structure are larger than those in tincalconite, which consist only
of NaO e octahedra.
Acknowledgements. The synthetic work and X-ray data collection was performed at
the Kristallographisches Institut, Universität Karlsruhe, FRG, 4 uring the tenure of a
fellowship (H.B.). The authors are grateful to Prof. Dr. W. E. Klee, for measuring the
IR-spectra. We thank Prof. Dr. Paul T. Beurskens (Nijmegen) for critically reading the
manuscript.

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Κι 67Na0 33B 4 0 5 (0H) 4 · 3 H 2 0 61

References
Beurskens, G., Noordik, J. H., Beurskens, P. T.: 9,9a-dihydro-l,2,9,9-tetramethyl-2,9a-
epitetrathio-3,10-diketopiperaziiio [1,2-a] indole, Ci5Hi6N 2 0 2 S 4 , absolute configu-
ration. Cryst. Struct. Commun. 9 (1980) 2 3 - 2 8 .
Giacovazzo, C.. Menchetti, S., Scordari, F.: The crystal structure of tincalconite. Am.
Mineral. 58 (1973) 523-530.
Gillepsie, R. J.: Molecular Geometry, Van Nostrand Reinhold Series in inorganic
chemistry (1972).
Holub, D.: Dissertation, Röntgenstrukturbestimmung von Tetracyclononan-4-carbon-
säure und Dibenzo-bicyclo-octadien-trans-dicarbonsäure-dimethylesther. Univ.
Karlsruhe (1982).
International Tablesfor X-ray Crystallography. Vol. IV. Birmingham: Kynoch Press 1974.
Morimoto, N.: The crystal structure of borax. Struct. Rep. 20 (1956) 376 - 380.
Motherwell, W. D. S.: PLUTO, A program for plotting molecular and crystal structures.
University Chemical Laboratory, Cambridge, England 1976.
Niggli, A.: Zur Systematik und gruppentheoretischen Ableitung der Symmetrie-, Anti-
Symmetrie- und Entartungssymmetriegruppen. Z. Kristallogr. I I I (1959) 288 — 300.
Sheldrick, G. M.: SHELX, A program for crystal structure determination. University
Chemical Laboratory, Cambridge, England 1976.
Walker, N., Stuart, D.: An empirical method of correcting diffractometer data for
absorption efTects. Acta Crystallogr. A39 (1983) 158 - 1 6 6 .
Zobetz, E.: Über die Gestalt von BOj-Gruppen. Z. Kristallogr. 160 (1981) 81 - 9 2 .

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