Antimonato polyoxovanadates with structure directing transition metal complexes: Pseudopolymorphic{Ni(dien)2}3[V 15Sb6O42(H2O)]·nH 2O compounds and {Ni(dien)2}4[V 16Sb4O42(H2O)]

Article abstract of DOI:10.1039/c1dt11635e

Three new poloxovanadates were synthesized under solvothermal conditions and were structurally characterized. The two compounds with composition {Ni(dien)₂}₃[V₁₅Sb₆O ₄₂(H₂O)]·nH₂O (n = 12 and 8; dien = bis(2-aminoethyl)amine or diethylenetriamine) are pseudopolymorphs crystallizing in different space groups. The compounds were obtained by applying identical reaction slurries but using different reaction temperatures. Both compounds feature the [V₁₅Sb₆O₄₂(H₂O)] ^6- anion which is the antimony analogue to the single molecule magnet [V₁₅As₆O₄₂(H₂O)]^6-. Crystal data: 1 tetragonal space group P4, a = 46.9378(3), c = 16.51300(10) A and V = 36380.7(4) A³. 2 rhombohedral space group R3c with a = 23.0517(4), c = 28.6216(5) A and V = 13171.3(4) A³. In 1 several unusual short inter-cluster Sb...O contacts lead to the formation of three different super-clusters with composition V₆₀Sb₂₄O₁₆₈. The 12 unique {Ni(dien)₂}²⁺ complexes adopt all three possible configurations. In 2 the special arrangement of the {Ni(dien)₂} ²⁺ complexes around the cluster anion prevents inter-cluster Sb...O contacts. The main structural motif of the third compound {Ni(dien)₂}₄[V₁₆Sb₄O ₄₂(H₂O)] (3) is the [V₁₆Sb₄O ₄₂(H₂O)]^8- cluster anion consisting of two perpendicular eight-membered rings of VO₅ pyramids. Two additional VO₅ polyhedra are located on opposite sides. Crystal data: 3 triclinic space group P1, a = 13.5159(4), b = 14.2497(5), c = 14.9419(4) A, α = 98.322(2), β = 114.080(2), γ = 110.130(2)°and V = 2326.35(12) A³.

Full text of DOI:10.1039/c1dt11635e

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PAPER
Antimonato polyoxovanadates with structure directing transition metal
complexes: pseudopolymorphic {Ni(dien)2}3[V15Sb6O42(H2O)]·nH2O
compounds and {Ni(dien)2}4[V16Sb4O42(H2O)]†
Elena Antonova, Christian Na¨ther and Wolfgang Bensch*
Received 30th August 2011, Accepted 26th October 2011
DOI: 10.1039/c1dt11635e
Three new poloxovanadates were synthesized under solvothermal conditions and were structurally
characterized. The two compounds with composition {Ni(dien)2}3[V15Sb6O42(H2O)]·nH2O (n = 12 and
8; dien = bis(2-aminoethyl)amine or diethylenetriamine) are pseudopolymorphs crystallizing in different
space groups. The compounds were obtained by applying identical reaction slurries but using different
reaction temperatures. Both compounds feature the [V15Sb6O42(H2O)]6- anion which is the antimony
6-
¯
analogue to the single molecule magnet [V15As6O42(H2O)] . Crystal data: 1 tetragonal space group P4,
3
˚
˚
a = 46.9378(3), c = 16.51300(10) A and V = 36380.7(4) A . 2 rhombohedral space group R3c with a =
3
˚
˚
23.0517(4), c = 28.6216(5) A and V = 13171.3(4) A . In 1 several unusual short inter-cluster Sb ◊ ◊ ◊ O
contacts lead to the formation of three different super-clusters with composition V60Sb24O168. The 12
2+
unique {Ni(dien)2} complexes adopt all three possible configurations. In 2 the special arrangement of
2+
the {Ni(dien)2} complexes around the cluster anion prevents inter-cluster Sb ◊ ◊ ◊ O contacts. The main
structural motif of the third compound {Ni(dien)2}4[V16Sb4O42(H2O)] (3) is the [V16Sb4O42(H2O)]8-
cluster anion consisting of two perpendicular eight-membered rings of VO5 pyramids. Two additional
¯
VO5 polyhedra are located on opposite sides. Crystal data: 3 triclinic space group P1, a = 13.5159(4),
◦
3
˚
˚
b = 14.2497(5), c = 14.9419(4) A, a = 98.322(2), b = 114.080(2), g = 110.130(2) and V = 2326.35(12) A .
catalysis,17 selective oxidation reactions,18 sorption applications19
or as deNOx catalysts.2
Introduction
The chemistry of polyoxometalates (POMs) is a fast growing
field of active research due to the fascinating diversity of crystal
structures and interesting properties. Many applications are
envisaged in areas like catalysis, supramolecular, analytical and
clinical chemistry, medicine, electronic and protonic conductors,
batteries and sorption.1–5 Although the interest in POM chemistry
is enormous, the number of publications on antimony substituted
polyoxovanadates (POVs) is comparably small. On the other hand,
arsenato POVs with the general formula [V18-xAs2xO42]·nH2O (x =
2–4)6–10 have been intensively studied owing to their attractive
magnetic properties11,12 like e.g. spin frustration,13,14 and their
potential applications in nanoscale magnetism.15 In contrast to
arsenato POVs, the antimony based POVs are less explored
although the antimony cations have a stabilizing effect on poly-
oxometalates at high temperatures.16 Therefore, antimony POVs
may find applications in many areas like heterogeneous oxidation
While the arsenic substituted polyoxovanadates can be chemi-
cally modified by other elements like Cd or Zn,20,21 there are only
three known types of antimony substituted clusters with shell
structures ([V14Sb8O42]4-, [V15Sb6O42]6-, and [V16Sb4O42]8- 22–26),
which are either extended by the transition metal complexes17,19
or being functionalized by Sb–N bonding to amine molecules.27
Very recently we successfully modified the shells of anti-
monato polyoxovanadate clusters with Co2+ and Ni2+ com-
plexes ((Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O
and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)])28 and with
1-(2-aminoethyl)piperazine ([V14Sb8(C6H15N3)4O42(H2O)]·4H2O
and (C6H17N3)2[V15Sb6(C6H15N3)2O42(H2O)]·2.5H2O).27
Here we report the syntheses and X-ray crystal structures of
new antimonato polyoxovanadates with the isolated spherical
[V15Sb6O42(H2O)]6- and [V16Sb4O42(H2O)]8- cluster anions and
2+
additional {Ni(dien)2} complexes, which were obtained under
solvothermal conditions by variation of temperature and reac-
tants.
Christian-Albrechts-Universita¨t zu Kiel, Institut fu¨r Anorganische Chemie,
D-24098, Kiel, Germany. E-mail: wbensch@ac.uni-kiel.de; Fax: +49 431
880 1520; Tel: +49 431 880 2091
Results and discussion
† Electronic supplementary information (ESI) available. CCDC reference
numbers 841371–841373. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c1dt11635e
¯
Compound 1 crystallizes in the tetragonal space group P4 with
16 formula units per unit cell, compound 2 crystallizes in
1338 | Dalton Trans., 2012, 41, 1338–1344
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Table 1 Selected crystal data and details of the structure determination
of the new compounds
Compound 1
Compound 2
Compound 3
Crystal system
Sum formula
Tetragonal
C24H104N18Ni3-
O55Sb6V15
Hexagonal
C24H96N18Ni3-
O51Sb6V15
3123.8087
R3c
23.0517(4)
23.0517(4)
28.6216(5)
90
90
120
13171.3(4)
6
2.357
Triclinic
C32H106N24Ni4-
O43Sb4V16
Formula weight
Space group
3195.8699
3052.1526
¯
¯
P4
P1
˚
a (A)
46.9378(3)
46.9378(3)
16.5130(10)
90
13.5159(4)
14.2497(5
14.9419(4)
98.322(2)
114.080(2)
110.130(2)
2326.35(12)
2
˚
b (A)
˚
c (A)
a (◦)
b (◦)
g (◦)
Fig. 1 The [V15Sb6O42(H2O)]6- cluster anion in compounds 1 and 2.
90
90
3
˚
Volume (A )
Z
36380.7(4)
16
2.163
200 212
31 512
˚
for 2) and short V O (1.586(8)–1.642(8) A for 1 and 1.599(6)–
Density (g cm-3)
Refl. collected
Independ.
reflections
Rint
2.269
31 328
12 535
1.610(5) for 2) distances (Tables S1 and S2†). The shortest V–V
˚
˚
64 789
6231
distances are between 2.839(3) and 3.068(2) A (average: 2.95 A)
˚
for 1 and 2.8303(15) to 3.0728(15) (average: 2.98 A) for 2. All
geometric parameters agree with those reported in literature for
structurally related POVs.22–24,27 In the well characterized arsenato
POV cluster [V15As6O42(H2O)]6- slightly smaller V–O and V–V
0.0560
0.0306
1.039
0.0500
0.0396
1.146
0.0403
0.0483
1.141
R1 for [I > 2s(I)]
GOOF
wR2 for all
reflections
T (K)
0.0768
0.085
0.0866
distances (V-m-O: 1.912(5) to 2.006(5), V O: 1.610(5) to 1.618(5)
29
˚
and V–V: 2.870(1) to 3.049(1) A) are observed, which may be
293
293
293
due to the presence of the smaller As(III).
In 1 several unusual short Sb–O distances of only 2.678,
˚
˚
˚
the rhombohedral space group R3c with 6 formula units, and
compound 3 crystallizes in the triclinic space group P1 with 2
2.691 A and 2.704 A (sum of van der Waals radii: 3.52 A)
¯
are found between the cluster anions besides longer Sb–O
distances from 2.817 to 2.969 A (Table 2) which are either
˚
formula units per unit cell. Selected crystal data and details of
the structure determination of the compounds are summarized in
Table 1.
As mentioned above, the composition of compounds 1 and 2 is
identical but the crystal structures are different.
between Sb2O5 moieties (short) or between Sb2O5 and a ter-
minal O atom of the neighboured cluster (long). The former
distances are significantly shorter than those observed in dif-
ferent antimony modified POVs like (C6H17N3)4[V16Sb4O42]·2H2O
˚
While the asymmetric unit of 2 comprises only a third of the
cluster anion and one Ni2+ complex, the asymmetric unit of
1 consists of four crystallographically independent [V15Sb6O42]6-
(2.85 A), [trenH3]2[tren]0.33[V15Sb6O42]·H2O (x: 3–5) (tren = tris(2-
˚
aminoethyl)amine) (2.88 A), [(C2N2H10)2-b-{V14Sb8O42(H2O)}]-
˚
(C2N2H8)·4H2O (2.79 A) and [V14Sb8(C6H15N3)4O42(H2O)]·4H2O
2+
22,23,25,27
˚
clusters and 12 unique {Ni(dien)2} complexes.
(2.73 A) indicating weak bonding interactions.
The central structural motif of 1 and 2 is a spherical [V15Sb6O42]6-
cluster anion. The centre of the cluster anion is occupied by one
H2O molecule and the diameter of the clusters in both compounds
Taking the inter-cluster Sb–O interactions into account three
super-clusters of composition V60Sb24O168 are formed consisting
of four [V15Sb6O42]6- anions (Fig. 2 right). Two of the three super-
clusters consist of only one crystallographically independent anion
(type A: Sb1–Sb6; type B: Sb31–Sb36) and one is formed by two
crystallographically independent cluster shells (type C: Sb11–Sb16
and Sb21–Sb26 atoms).
˚
is approximately 11 A.
The spherical [V15Sb6O42]6- cluster shell is easily derived from
the {V18O42} archetype cluster by substituting three VO5 square
pyramids by three Sb2O5 moieties. The resulting cluster shell
is identical with that of the most studied arsenato analogue
[V15As6O42]6- consisting of 15 VO5 square pyramids and 3 Sb2O5
The super-clusters show two alternating orientations in the ab
plane yielding a layer-like arrangement (Fig. 2 left).
˚
handle-like moieties (Sb–O bond lengths: 1.912(7)–1.988(7) A for
The formation of super-clusters has been reported before.
˚
1 and 1.935(5)–1.945(5) for 2) (Tables S1 and S2;† Fig. 1). A central
{V3} triangle is capped above and below by {V6} rings. The V–O
bonds in the VO5 polyhedra exhibit the typical pattern of relatively
However, the inter-cluster Sb–O separation of 2.884(8) A
in [trenH3]2[tren]0.33[V15Sb6O42] interconnects the anions into
[V45Sb18O126] super-clusters forming Sb3O3 rings displaying a
pattern being different to that in 1.23
˚
long V-m-O (1.867(7) to 2.040(7) A for 1 and 1.897(6)–2.032(6)
˚
Table 2 Sb–O distances (A) between the neighbouring clusters in compound 1. Ot = terminal O atoms of the cluster anions
Super-cluster A
Bond
Super-cluster B
Bond
Super-cluster C
Bond
˚
˚
˚
Distance/A
Distance/A
Distance/A
Sb1–O5t
Sb4–O15
2.912
2.691
Sb31–O178t
Sb36–O154
2.931
2.704
Sb16–O115t
Sb24–O72
Sb22–O60
Sb12–O103t
2.678
2.948
2.817
2.969
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Fig.
3
Representation of the transition metal complexes: s-fac-
2+
2+
2+
{Ni(dien)2} (left), mer-{Ni(dien)2} (middle) and u-fac-{Ni(dien)2}
complex (right).
2+
Fig. 4 shows the arrangement of the {Ni(dien)2} complexes
in the unit cell. In the center of the cell, symmetry related Ni6
centred complexes occupy the corners of a square. The Ni1, Ni10,
Ni2, and Ni7 containing complexes are arranged in a ring-like
fashion (denoted as ring 2) separating the super-cluster B from
the other clusters. Another ring-like arrangement is observed for
the complexes centered by Ni3, Ni5, Ni8, Ni11, Ni12 (ring 3). The
remaining complexes (Ni4 and Ni9) are located at the corners of
unit cell.
Fig. 2 Arrangement of the super-clusters A, B, and C in compound 1 in
the ab plane. The red lines (left) clarify the different orientations of these
structural motifs.
The values of the bond-valence sums (BVS) yield values for
the Sb atoms in the range from 3.09 (Sb31) to 3.38 (Sb4, Sb16)
(average: 3.26) (Table 3).30 In tendency, the values for the Sb atoms
involved in inter-cluster Sb–O interactions (Sb4, Sb16 and Sb36)
are larger than for the remaining Sb atoms. However, one should
keep in mind that the BVS method is not very accurate for “soft”
atoms and those with a lone electron pair like Sb(III).
The water molecules and the Ni2+ centred complexes occupy
the free voids between these cluster quartets. In compounds 1
and 2 Ni2+ is coordinated by six N atoms from two dien ligands.
The resulting octahedra are strongly distorted with Ni–N bonds
˚
from 2.025(19) to 2.33(3) A for 1 and from 2.059(9) to 2.169(6)
for 2 (Table S1, S2†) which are in agreement with data reported
in literature.31–40 Around Ni12 the Ni–N bonds are significantly
˚
longer (from 2.13 to 2.33 A) than in the other complexes. This
elongation is caused by a slight positional disorder which could not
2+
be resolved during structure refinement. Two of 12 {Ni(dien)2}
complexes (Ni12, Ni11) adopt the mer-, Ni1, Ni7 the s-fac,
and the remaining complexes (Ni2–Ni6, Ni8–Ni10) the u-fac-
configuration (Fig. 3). The maximum diameter of the complexes
Fig. 4 Arrangement of the cluster shells (red balls) and Ni2+ centred
complexes in the unit cell of compound 1. H atoms and H2O molecules
are not shown.
˚
is in the range of 5.468 to 5.947 A (Table 4).
The cluster shells in 2 alternate in an . . . ABC . . . fashion along
the b-axis and in an . . . ABAB . . . manner along the c-axis (Fig.
5). Neighboring clusters being directed along the c-axis are rotated
by about 20 degrees against each other (Fig. 6). In contrast to 1 no
short inter-cluster Sb–O separations are observed and the shortest
Table 3 Bond valence sums of the antimony atoms in 1
Sb1 3.31
Sb2 3.22
Sb3 3.19
Sb4 3.38
Sb5 3.16
Sb6 3.29
Sb11 3.17
Sb12 3.25
Sb13 3.22
Sb14 3.27
Sb15 3.28
Sb16 3.38
Sb21 3.22
Sb22 3.16
Sb23 3.29
Sb24 3.21
Sb25 3.30
Sb26 3.23
Sb31 3.09
Sb32 3.37
Sb33 3.31
Sb34 3.24
Sb35 3.36
Sb36 3.24
˚
distance is 5.21 A. However, one relatively short Sb–O distance
˚
is found to the O atom of a water molecule (2.9524(0) A). In the
(001) plane the Ni2+ complexes are located between the anions
Table 4 The diameter (A) of the {Ni(dien)2}2+ complexes in compound 1
˚
˚
˚
Complex
Min. diameter/A
Max. diameter/A
Ni1 - s-fac
Ni2 - u-fac
Ni3 - u-fac
Ni4 - u-fac
Ni5 - u-fac
Ni6 - u-fac
Ni7 - s-fac
Ni8 - u-fac
Ni9 - u-fac
Ni10 - u-fac
Ni11 - mer
Ni12 - mer
4.153
4.185
4.199
4.218
4.207
4.215
4.140
4.182
4.178
4.169
4.066
4.262
5.891
5.875
5.947
5.750
5.821
5.854
5.908
5.924
5.783
5.811
5.730
5.468
Fig. 5 Arrangement of the constituent in the structure of 2 in the bc
plane. Atoms of the complexes are not displayed.
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centre of the cluster a H2O molecule is encapsulated. All geometric
parameters match well with those of compounds 1 and 2 and with
literature data.14–16,27 Bond-valence sum calculations reveal that
the oxidation state of the Sb atoms is close to III (Sb1: 3.19; Sb2:
3.27).
There are 3 crystallographically independent Ni2+ ions in 3. One
is located on a general position and two on special positions. Like
Fig. 6 View of two clusters along c-axis in the structure of 2.
2+
in compounds 1 and 2 the {Ni(dien)2} octahedron is strongly
forming a triangular-like arrangement around the cluster shells
thus isolating the [V15Sb6O42]6- anions preventing inter-cluster Sb–
distorted. The Ni–N bonds (Table S3†) and N–Ni–N angles are
comparable with those in 1 and 2 and agree with literature data.32–41
2+
2+
O interactions (Fig. 7). The {Ni(dien)2} cation in 2 adopts the
Two of three {Ni(dien)2} complexes adopt the s-fac- and one
mer-configuration (see Fig. 3 and 7). In contrast to compound
1 the complex in compound 2 exhibits a smaller diameter (max.
occurs in the u-fac-configuration (see Fig. 3). The minimum
˚
diameter of the complexes varies from 4.196 A (Ni2) to 4.246
˚
˚
˚
5.585 A).
A (Ni1) and the maximum extension varies from 5.865 A (Ni2) to
˚
5.928 (Ni1) A. The anionic clusters in compound 3 are arranged
in layers in the (100) plane with intervening water molecules and
complex cations (Fig. 9).
Fig. 7 Representation of the clusters and Ni2+ complexes in compound 2
in the ab plane. The clusters are shown as red balls.
Fig. 9 Arrangement of the cluster anions and Ni2+ centred complexes in
compound 3. H atoms are not shown.
The mer-configuration of the complex allows denser packing,
but the shielding of the clusters by the complexes leads to larger
distances between the Sb2O5 units (Fig. 7). In total 24 N–H ◊ ◊ ◊ O
bonds in the range from 2.0627(0) A to 2.9213(0) A are identified
leading to a three-dimensional network structure.
The central structural motif of compound 3 can also be derived
from the {V18O42} archetype cluster. Substitution of two of the VO5
square pyramids by two Sb2O5 moieties (Sb–O 1.934(3)–1.955(3)
A) generates the spherical [V16Sb4O42]8- cluster anion consisting of
˚
˚
˚
Bond-valence sum calculations reveal that the oxidation state
of all the vanadium atoms in the studied compound is around +4
(Rs = 4.07–4.33 for 1, Rs = 4.15– 4.22 for 2 and Rs = 4.09– 4.17
for 3), which is consistent with the overall charge balance in the
formula. This is also proven in compounds 1 and 2 by IR spectra,
where the typical vibration of V4+ (V O)s appears as a very strong
band at 968 cm-1 (Fig. 10).
two eight-membered rings of VO5 (V–O: 1.9008(3)–2.000(3) and
˚
V
O: 1.607(4)–1.639(3) A) perpendicular to each other (Fig. 8).
Two additional VO5 pyramids are located on opposite sides and
these polyhedra share two edges with the two rings (Fig. 8). In the
Fig. 10 IR spectra of compounds 1 and 2. Some important absorption
modes are marked.
Fig. 8 [V16Sb4O42]8- cluster as the central fragment in compound 3.
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In the IR spectra of 1 and 2 the n(O–H) = 3431 (s), n(N–H) =
3268 (s) and n(C–H) = 2927, 2871 (m) cm-1 vibrations and also the
asymmetric nas(V–O–V) at 726 cm-1 are observed besides further
absorptions that can be assigned to the organic molecules. The
characteristic terminal ns(V O) stretching vibration occurs at
968 cm-1. The assignment of the vibrational modes are in good
agreement with literature data.41
DTA-TG investigations reveal that compounds 1 and 2 decom-
pose in two steps with a total mass loss of Dmexp = 37.4 wt%.
The first process in the temperature range from 30 to 300 ◦C
corresponds to the loss of water molecules (Dmexp = 5.4 wt %).
After 400 ◦C an almost smooth decrease of the sample mass is
observed with a mass loss of Dmexp = 32 wt %. Crystalline powders
were obtained as the products of the decomposition reaction of
both compounds which were identified as mixtures of NiSb, NiSb2,
Sb and V2O3.
Experimental
Syntheses of the compounds
For compound 1 1.34 mmol NH4VO3, 1.06 mmol Sb2O3 and 0.66
mmol NiCl2·6H2O in a mixture of 1.7 mL bis(2-aminoethyl)amine
(or diethylenetriamine = dien) and 2.3 mL water were sealed in a
30 mL Teflon lined stainless steel autoclave and heated at 150 ◦C
for 7 days. After cooling to room temperature the product was
filtered off and washed with water and acetone. The brown
crystals were dried under vacuum. Yield: 36% based on antimony.
Elemental analysis: C 9.8, H 2.6, N 8.8%, calc. C 9.02, H 3.28, N
7.89%.
Compound 2 was synthesized applying the same starting
materials in identical ratio but the temperature was kept at 130 ◦C
for 7 days. The main product consisted of red–brown needles,
which were washed with water and acetone and dried in vacuum.
Yield: 37% based on antimony. Elemental analysis of the needles:
C 9.4, H 3.1, N 8.1%, calc. C 9.23, H 3.1 N 8.07%. SEM images
of crystals are shown in Fig. 12.
Both, compounds 1 and 2 readily dissolve in methanol and
ethanol. In contrast the solubility of the two compounds in water
is significantly different as becomes apparent by the color of the
solutions (Fig. 11), i.e., compound 1 is significantly less soluble in
H2O than 2.
Fig. 11 Aqueous solutions of compound 1 (left) and compound 2 (right).
The absorption maximum in the UV spectra is at 255 for 1 and
at 265 nm for 2.
Conclusions
Polymorphs or pseudopolymorphs of antimonato polyoxovana-
date compounds have not been reported in literature until
now. Applying identical starting material ratios but varying the
reaction temperature afforded crystallization of compounds 1
and 2. The main difference between the two compounds is the
occurrence of Ni2+ centred complexes adopting three different
configurations in 1 while only one configuration is observed in
2. The special arrangement of the complex cations around the
spherical [V15Sb6O42]6- clusters in 1 allows short intermolecular
Sb ◊ ◊ ◊ O interactions whereas the location of the complexes in
2 prevents such interactions. Currently investigations of the
magnetic properties are under way to probe whether the inter-
cluster interactions in 1 influence the magnetic properties of the
single molecule magnet behaviour. Compound 3 was synthesized
using the bimetallic precursor Sb2VO5 which is a promising source
for further syntheses.
Fig. 12 SEM micrographs and images of crystals.
The product of the synthesis at 130 ◦C (2) contained brown nee-
dles of 2 and black crystals that were identified as [V5O11(dien)3].42
In order to avoid the formation of the byproduct the synthesis
parameters such as temperature, reactants and concentration of
amine were varied, but the variation of temperature and concen-
tration of amine led mainly to the formation of [V5O11(dien)3].
Often the water to amine ratio played a crucial role and further
syntheses were carried out with 5, 10 and 20 mL water keeping
the amount of the other educts constant. The product of these
reactions was a green powder which was identified as Sb2VO5
(Stibivanite). Unfortunately, the variation of the syntheses did not
increase the yield of compound 2.
1342 | Dalton Trans., 2012, 41, 1338–1344
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For compound 3 a mixture of 1 mmol Sb2VO5, 0.66 mmol
NH4VO3, 0.66 mmol NiCl2·6H2O was treated with an amine–water
solution analogous to compound 1. X-ray powder diffractometry
showed reflections of at least two different compounds. Because
the black crystals grow in chunks a manual separation of the
different compounds was not possible (Fig. 12). For this reason
chemical analyses were not possible, and only the X-ray structure
is reported here.
min-1; Al2O3 crucibles) using a Netzsch STA-409CD instrument.
To determine the water content of 1 several TG measurements were
performed using products of different syntheses. For all products
the weight loss corresponded to 12 H2O molecules per formula
unit.
Acknowledgements
The financial support from the State of Schleswig-Holstein is
grateful acknowledged.
Crystal structure determination
The X-ray intensity data of a single crystal of compound 1
with dimensions 0.0542 ¥ 0.1027 ¥ 0.1476 mm3, of a crystal of
compound 2 with dimensions 0.057 ¥ 0.0728 ¥ 0.1325 mm3 and of
a crystal of 3 with dimensions 0.0395 ¥ 0.0588 ¥ 0.0686 mm3,
were collected at room temperature using a STOE-1 Imaging
Plate Diffraction System (IPDS-1) with Mo-Ka radiation (l =
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˚
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