Interaction between chiral ions: Synthesis and characterization of tartratovanadates(V) with tris(2,2'-bipyridine) complexes of iron(II) and nickel(II) as cations

Article abstract of DOI:10.1007/s11243-014-9873-2

Four new compounds composed of chiral complex cations and anions: Δ-[Fe(bpy)₃] Λ-[Fe(bpy)₃][V₄O₈((2R,3R)-tart)₂]·12H₂O (1), Δ-[Fe(bpy)₃]₂Λ-[Fe(bpy)₃]_2<

Full text of DOI:10.1007/s11243-014-9873-2

Transition Met Chem (2014) 39:893–900
DOI 10.1007/s11243-014-9873-2
Interaction between chiral ions: synthesis and characterization
of tartratovanadates(V) with tris(2,20-bipyridine) complexes
of iron(II) and nickel(II) as cations
•
Peter Antal Peter Schwendt Jozef Tatiersky
•
•
•
Robert Gyepes Milan Drabik
´
´
Received: 26 June 2014 / Accepted: 16 August 2014 / Published online: 26 August 2014
Ó Springer International Publishing Switzerland 2014
Abstract Four new compounds composed of chiral complex
cations and anions: D-[Fe(bpy)3] K-[Fe(bpy)3][V4O8((2R,3R)-
tart)2]ꢀ12H2O (1), D-[Fe(bpy)3]2K-[Fe(bpy)3]2[V4O8((2R,3R)-
tart)2][V4O8((2S,3S)-tart)2]ꢀ24H2O (2), D-[Ni(bpy)3]K-[Ni-
(bpy)3][V4O8((2R,3R)-tart)2]ꢀ12H2O (3) and D-[Ni(bpy)3]2K-
[Ni(bpy)3]2[V4O8((2R,3R)-tart)2][V4O8((2S,3S)-tart)2]ꢀ24H2O
(4) have been prepared. The compounds have been character-
ized by spectral methods, and their thermal decomposition was
studied by simultaneous DTA, TG measurements. The final
products after dynamic decomposition and additional heating
were Fe2V4O13 for 1 and 2 and Ni(VO3)2 for 3 and 4. The
crystal structures determined for 1, 2 and 4 have evidenced that
1 is ‘‘hemiracemic’’ and 2 and 4 are ‘‘fully racemic’’
compounds.
may lead to crystallization of a conglomerate, racemic
compound or eventually to concomitant crystallization of
both compound types [1–7]. The kind of products obtained
depends on the type of forces operating in the crystal
structure. Besides electrostatic interactions, various weak
interactions (H-bonds, p–p, cation–p, anion–p interactions)
can influence the results of crystallization; the interplay of
very fine effects often determines the kind of crystals [1–6].
Even in the case of crystallization of racemic compounds,
some homochiral parts of crystals (chains, layers) can be
formed, and preferred interactions between the chiral ions
can be observed. Thus, in the case of [M(bpy)3][-
VO(O2)(ox)(bpy)]2 compounds (M = Fe, Ni; ox = C2-
O42-), we observed the preference of D-[M(bpy)3]2?–A-
[VO(O2)(ox)(bpy)]- and K-[M(bpy)3]2?–B-[VO(O2)(-
ox)(bpy)]- interactions (A and B denote different enanti-
omers of the anion), which resulted in formation of
homochiral layers [7].
Introduction
The interaction of chiral cations with chiral anions or chiral
cations (anions) with achiral anions (cations) in solution
Tartaric acid and its derivatives are often used as
resolving agents, and to continue our previous studies on
interaction of chiral [M(bpy)3]2? cations with various chi-
ral anions, we decided to study their interaction with
anionic vanadium tartrato complexes. Here we present the
characterization of products crystallizing from solutions
containing rac-[M(bpy)3]2? and chiral tartrato complexes
of vanadium(V). In all cases, racemic or hemiracemic
compounds were obtained.
´
P. Antal ꢀ P. Schwendt ꢀ J. Tatiersky (&) ꢀ M. Drabik
Department of Inorganic Chemistry, Faculty of Natural Sciences,
´
Comenius University, Mlynska dolina, 842 15 Bratislava,
Slovak Republic
e-mail: tatiersky@fns.uniba.sk
R. Gyepes
Faculty of Education, J. Selye University, Bratislavska cesta
´
3322, 945 01 Komarno, Slovak Republic
´
Experimental
R. Gyepes
J. Heyrovsky Institute of Physical Chemistry of the AS CR,
ˇ
v.v.i., Dolejskova 3, 182 23 Prague 8, Czech Republic
´
Chemicals
´
M. Drabik
Institute of Inorganic Chemistry, Slovak Academy of Sciences,
´
´
Dubravska cesta 9, 845 36 Bratislava 45, Slovak Republic
KVO3 was prepared by reaction of an aqueous solution
of KOH with V2O5 [7]. V2O5 was prepared as follows.
123

894
Transition Met Chem (2014) 39:893–900
All other chemicals used were of reagent grade and used
without further purification.
(119 mg, 0.50 mmol) and 2,20-bipyridine (234 mg,
1.50 mmol) in ethanol (u = 48 %, 10.0 mL) was added.
The obtained solution was filtered and allowed to crystal-
lize at 5 °C. Orange crystals were isolated after 12 h and
dried at 5 °C. The obtained crystals were not suitable for
structural analysis. Anal. Calc. for C68H76N12O32V4Ni2: C,
43.1; H, 4.0; N, 8.9. Found: C, 42.1; H, 3.8; N, 8.6.
Preparation of V2O5
Ammonium vanadate (50.0 g) was purified by dissolving
in an aqueous solution of ammonia (w = 26 %, 60.0 mL)
and water (1.50 L). The obtained solution was heated to
60 °C, filtered and cooled in air to ambient temperature.
Ammonium nitrate (70.0 g) was then added. A white pre-
cipitate was obtained (NH4VO3), which was filtered off and
washed with cold water (20.0 mL) and then ethanol
(20.0 mL). V2O5 was prepared by thermal decomposition
(2 h at 500 °C) of purified ammonium vanadate. The purity
of vanadium pentoxide was verified by powder XRD and
reductometric determination of vanadium [8].
Synthesis of D-[Ni(bpy)3]2K-
[Ni(bpy)3]2[V4O8((2R,3R)-tart)2][V4O8((2S,3S)-
tart)2]ꢀ24H2O (4)
Potassium vanadate (276 mg; 2.00 mmol) was dissolved in
water (15.0 mL). After the addition of solid racemic tar-
taric acid (300 mg, 2.00 mmol), a red solution was
obtained. To this solution, another solution of nickel(II)
chloride hexahydrate (237 mg, 1.00 mmol) and 2,20-
bipyridine (469 mg, 3.00 mmol) in ethanol (u = 48 %,
10.0 mL) was added. The solution obtained was filtered
and allowed to crystallize at 5 °C. Orange crystals were
isolated after 12 h and dried at 5 °C. Anal. Calc. for C68-
H76N12O32V4Ni2: C, 43.1; H, 4.0; N, 8.9. Found: C, 43.1;
H, 4.0; N, 8.7.
Synthesis of D-[Fe(bpy)3]K-[Fe(bpy)3][V4O8((2R,3R)-
tart)2]ꢀ12H2O (1)
Potassium vanadate (138 mg; 1.00 mmol) was dissolved in
water (10.0 mL). After the addition of solid (2R,3R)-tartaric
acid (76.6 mg, 0.50 mmol), a red solution was obtained. To
this solution, another solution of iron(II) sulfate heptahydrate
(139 mg, 0.50 mmol) and 2,20-bipyridine (234 mg,
1.5 mmol) in aqueous ethanol (u = 24 %, 20.0 mL) was
added. The solution obtained was allowed to crystallize at
5 °C. Dark red crystals were isolated after 2 weeks and dried
at 5 °C. Anal. Calc. for C68H76N12O32V4Fe2: C, 43.2; H, 4.1;
N, 8.9. Found: C, 42.8; H, 3.9; N, 8.6.
Methods and instrumentation
Elemental analyses (C, H, N) were performed on a Vario
MIKRO cube (Elementar). IR spectra were recorded on an
FTIR Nicolet 6700 spectrometer in Nujol mulls and KBr
discs. The 51V NMR spectra of aqueous solutions were
registered at 278 K on a Varian Mercury Plus 300 MHz
spectrometer operating at 78.94 MHz (51V) in 5-mm tubes
without locking on D2O and 30 min after dissolution.
Chemical shifts are related to VOCl3 as an external standard.
Electronic spectra of aqueous solutions were measured in
range 200–1,000 nm on a Jasco V-530 (Shimadzu) appara-
tus in 1-cm quartz cuvettes at room temperature. The spectra
were measured 10 min after dissolution. Powder X-ray dif-
fraction patterns were obtained on a PANalytical Empyrean
Synthesis of D-[Fe(bpy)3]2K-
[Fe(bpy)3]2[V4O8((2R,3R)-tart)2][V4O8((2S,3S)-
tart)2]ꢀ24H2O (2)
Potassium vanadate (139 mg; 1.00 mmol) was dissolved in
water (10.0 mL), and racemic tartaric acid (76.5 mg;
0.50 mmol) was added. To the red solution obtained,
another solution of iron(II) sulfate heptahydrate (139 mg;
0.50 mmol) and 2,20-bipyridine (234 mg, 1.5 mmol) in
ethanol (5.0 mL), water (20.0 mL) and acetonitrile (5 mL)
was added. The solution was allowed to crystallize at 5 °C.
Dark red crystals were isolated after 3 weeks. Anal. Calc.
for C68H76N12O32V4Fe2: C, 43.2; H, 4.1; N, 8.9. Found: C,
42.2; H, 3.6; N, 9.2.
˚
diffractometer using CuKa radiation (k = 1.5406 A) with
Bragg–Brentano arrangement. DTA and TG curves were
measured on SDT 2960 (TA Instruments) apparatus in air
in the temperature range 20–500 °C with the heating rate
10 °C min-1
.
X-ray data collection and structure refinement
Synthesis of D-[Ni(bpy)3]K-[Ni(bpy)3][V4O8((2R,3R)-
tart)2]ꢀ12H2O (3)
Diffraction data were collected at 150(2) K on a Nonius
KappaCCD diffractometer (MoKa radiation, k =
˚
0.71073 A) equipped with a Bruker APEX-II CCD detector
Potassium vanadate (138 mg; 1.00 mmol) was dissolved in
water (10.0 mL), and solid (2R,3R)-tartaric acid (75 mg;
0.50 mmol) was added. To the red solution obtained,
another solution of nickel(II) chloride hexahydrate
and processed using the software package delivered with
the diffractometer. Diffraction data were corrected
employing a symmetry-related (multi-scan) absorption
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Transition Met Chem (2014) 39:893–900
895
Table 1 Crystal data and
Compound
1
2
4
structure refinement for 1, 2 and
4 (formulas of compounds are
normalized as crystallographic
formula units)
Formula
C68H76N12O32V4Fe2
1,888.87
Monoclinic
P21 (no. 4)
23.4634(6)
13.6462(3)
24.5395(7)
90.422(1)
7,857.0(3)
4
C68H76N12O32V4Fe2
1,888.87
Monoclinic
P21/c (no. 14)
24.2609(10)
13.9399(5)
23.382(1)
99.023(2)
7,809.8(5)
4
C68H76N12O32V4Ni2
1,894.59
Mr
Crystal system
Space group
Monoclinic
P21/c (no. 14)
24.3341(8)
14.5312(5)
23.3803(9)
99.611(1)
8,151.3(5)
4
˚
a (A)
˚
b (A)
˚
c (A)
b (°)
Volume (A )
a
I [ 2r(I)
3
˚
b
R1 = 100R(||F0| - |Fc||)/R|F0|
wR2 = 100[R[w(F20 - Fc2)2]/
Z
c
a,b
R[w(F20)2]]1/2, w = 1/
R1
0.0478
0.0399
0.0393
[r2(F20) ? [(ap)2 ? bp]], where
p = [max (F20, O) ? 2F2c]/3,
a and b are constants
c
wR2
0.1072
0.0943
0.0991
R1 (all data)
0.0672
0.0518
0.0533
correction. All non-hydrogen atoms were refined aniso-
tropically; hydrogen atoms were included in their ideal
positions and refined isotropically. Solvent molecules
could not be refined satisfactorily in either case and have
been removed from the final model using the SQUEEZE
procedure as implemented in Platon [9]. A disorder of one
tart ligand in 2 and 4 was treated by constraining the sum
of site occupancy factors of the two moieties located on
difference Fourier maps. An analogous approach was used
to resolve the other disorder of 2, which had one of its bpy
ligands struck by a similar division into two positions.
Crystal data and final refinement parameters are given in
Table 1.
was [250 cm-1, indicating that the carboxylate groups in
the tartrate ligand are coordinated to vanadium in a
monodentate fashion [12]. The infrared spectra of 1–4
exhibit a mutual similarity—only small differences can be
observed for ms(COO-) and m(V–Oh) vibrations (Table 2).
The 51V NMR spectra of all compounds exhibit two dom-
inant signals (Fig. 1): a signal at approximately -523 ppm
corresponding to [V4O8(tart)2]4- (-524 ppm, Irel = 72 % for
1; -521 ppm, Irel = 67 % for 2; -524 ppm, Irel = 77 % for
3; -523 ppm, Irel = 68 % for 4) and another at -539 ppm
corresponding to [V2O4(H2tart)2]2- (-540 ppm, Irel = 28 %
for 1; -536 ppm, Irel = 33 % for 2; -539 ppm, Irel = 23 %
for 3; -539 ppm, Irel = 32 % for 4) [11].
The UV–Vis spectra of 1–4 are dominated by the absorp-
tion bands of the cations. Therefore, we discuss here only the
spectra of 1 and 4 (Figs. 2, 3). Electronic spectra of 1 and 4
exhibit in the UV-region below 320 nm bands corresponding
to the intraligand (bpy) p ? p* transitions [13, 14]. In the
spectrum of 1, the characteristic MLCT [13, 15] bands were
observed at 347, 491 and 522 nm, which account for the
typical red color of the Fe(II)-tris(diimine) complexes
(Table 3). The d–d transitions give rise to three bands in the
spectrum of 4. The lowest energy band is in agreement with
literature data [14, 16] assigned to the spin forbidden transi-
Results and discussion
Syntheses and spectroscopic studies
Compounds 1–4 were prepared by crystallization from
the KVO3–tartaric acid–FeSO4ꢀ7H2O (NiCl2ꢀ6H2O)–2,20-
bipyridine–H2O–ethanol–(acetonitrile) systems. The com-
pounds are moderately soluble in water under partial
decomposition (vide infra). The solid complexes are rela-
tively stable, as they can be stored at 5 °C at least for
1 week without decomposition. Compounds 1–4 are mod-
erately soluble in water and insoluble in acetonitrile.
The infrared spectra of 1–4 (Table 2) exhibit charac-
teristic bands of the [M(bpy)3]2? cations and tetranuclear
[V4O8(tart)2]4- anions. The strong bands corresponding to
stretching vibrations, in plane and out of plane bending
vibrations of the 2,20-bipyridine rings, can be observed in
expected positions [10]. For the [V4O8(tart)2]4- anions
especially the bands which can be assigned to mas(COO-),
ms(COO-), m(V=Ot) and m(VOV) vibrations are character-
istic [11]. For all of the complexes studied here, the dif-
ference between the asymmetric and symmetric stretches
3
1
tion A2g ? Eg. The third spin allowed d–d band
3
[3A2g ? T1g(P)]inthespectrumof1 issupposedtobebelow
330 nm and is hidden behind the very strong p ? p* bands.
The TG curves of 1–4 show several overlapping
decomposition steps without any distinct plateaus. The first
step on the TG curves of 1 and 2 (Fig. 4, because of sim-
ilarity of both TG curves only the curve of 2 is depicted)
accompanied by an endothermic peak on the DTA curve at
about 100 °C was assigned predominantly to the release of
crystal water (calc. weight loss 11.45 %, found 13.02 %
and 9.22 % for 1 and 2, respectively). The next step on the
TG curves with a corresponding exothermic maximum on
the DTA curve at &190 °C was attributed mostly to the
123

896
Transition Met Chem (2014) 39:893–900
Table 2 Infrared spectra of 1–4 (1,700–400 cm-1
)
1
2
3
4
Assignment
1,624 vs
1,603 vs
1,624 vs
1,602 vs
1,631 s
1,628 vs
mas(COO-)
m(ring)
1,605 vs
1,598 vs
1,575 m
1,568 sh
1,493 w
1,473 m
1,443 vs
1,597 vs
1,574 w
1,566 sh
1,492 m
1,472 m
1,442 vs
m(ring)
m(ring)
1,568 sh
1,467 s
1,568 sh
1,466 m
m(ring)
m(ring)
m(ring)
Fig. 1 51V NMR spectra of aqueous solution of
(c = 1 9 10-4 mol/L)
3
1,443 s
1,443 s
m(ring)
1,427 m
1,358 m
1,313 m
1,271 w
1,242 w
1,229 w
1,173 w
1,161 w
1,092 m
1,067 w
1,426 m
1,363 m
1,314 m
1,271 w
1,241 w
1,226 w
1,172 w
1,160 w
1,091 m
1,065 m
1,045 w
m(ring)
ms(COO-)
nearly pure Fe2V4O13 [18]. The whole process of the
thermal decomposition of 1 and 2 is described by Sche-
mes I and II (calc. total weight loss 71.61 %, found
72.76 % for 1 and 72.30 % for 2.
1,369 w
1,314 m
1,283 w
1,247 w
1,226 w
1,176 w
1,160 m
1,090 m
1,064 w
1,045 w
1,021 s
963 s
1,347 m
1,314 m
m(ring)
m(ring)
1,247 m
1,224 w
1,175 m
1,158 m
1,092 m
1,063 w
1,045 w
1,022 m
962 vs
a(C–H)
m(ring)
Â
à Â
Ã
FeðbpyÞ3 V4O8ðð2R; 3RÞ-tartÞ2 ꢀ12H2O
2
a(C–H)
a(C–H)
m(C–Oh)
m(C–Oh)
m(ring)
! 2FeVO4 þ V2O5 þ gaseous products
ðIÞ
ðIIÞ
2FeVO4 þ V2O5 ! Fe2V4O13
The TG curves of 3 and 4 (Fig. 5; because of the sim-
ilarity of both TG curves only that of 4 is depicted) exhibit
some similarities with the TG curves of 1 and 2. We can
propose the release of crystal water (endothermic peak at
&100 °C, calc. weight loss 11.43 %, found 11.56 % for 3
and 8.58 % for 4). Three exothermic effects on the DTA
curves at &197, &260 and &395 °C correspond to the
decomposition of organic ligands.
m(ring)
963 s
960 s
m(V=Ot)
918 sh
850 m
822 m
775 vs
752 sh
735 s
920 w
849 m
822 m
775 vs
754 sh
734 s
916 w
918 w
m(Ctart–Ctart
d(COO)
d(COO)
c(ring)
)
848 m
849 m
819 sh
823 w
778 vs
775 vs
The whole decomposition process is expressed by
Schemes III and IV (calc. total weight loss 72.86 %, found
73.24 % for 3 and 72.11 % for 4).
mas(VOV)
c(C–H)
m(ring)
738 s
737 vs
663 sh
653 m
552 s
659 m
648 w
551 s
660 m
649 m
547 s
Â
à Â
Ã
653 m
548 m
530 sh
497 w
439 m
420 w
m(ring)
NiðbpyÞ3 V4O8ðð2R; 3RÞ-tartÞ2 ꢀ12H2O
2
ms(VOV)
m(V–Oh)
m(V–Oh)
c(ring)
! Ni2V2O7 þ V2O5 þ gaseous products
ðIIIÞ
ðIVÞ
515 sh
513 w
514 m
486 w
436 m
417 w
Ni2V2O7 þ V2O5 ! 2Ni(VO3Þ2
435 m
409 w
434 m
409 w
The products of decomposition given in Schemes III
and IV were confirmed by X-ray powder patterns and IR
spectra [19, 20]. The final product of dynamic decompo-
sition was Ni(VO3)2 including a small admixture of V2O5
and Ni2V2O7. After additional heating of this mixture
(580 °C, 3 h), pure Ni(VO3)2 was obtained.
c(ring)
m Stretching, d bending, a in plane bending, c out of plane bending, Ot
terminal oxygen atom, Oh oxygen atom from deprotonated hydroxyl
group of tartrate ligand, Ctart carbon atom from tartrate ligand
decomposition of the tartrate ligand. The following steps
on the TG curves accompanied by several exothermic
peaks on the DTA curves were assigned to the decompo-
sition of [Fe(bpy)3]2? cation, which exhibits a considerable
thermal stability [17] while undergoing a simultaneous
oxidation of FeII–FeIII.
A nicely differentiated IR spectrum of Ni(VO3)2, to the
best of our knowledge unpublished so far, is presented in
Fig. 6. The rich spectrum in the range of V–O stretching
vibrations corresponds to variability of the V–O bond
lengths found in the structure [21].
The final product of dynamic decomposition, according
to the IR spectra and powder X-ray diffraction patterns, is a
mixture of V2O5 and FeVO4 including a small admixture of
Fe2V4O13. According to IR and X-ray diffraction, the
prolonged heating of 1 and 2 (24 h) at 620 °C afforded
Description of the crystal structures
Crystallization from solution containing both enantiomers
of the cation and anion can lead to different types of pro-
ducts (Fig. 7). The most common crystallization product
123

Transition Met Chem (2014) 39:893–900
897
Fig. 2 Electronic spectrum of
aqueous solution of 1
(c = 1 9 10-5 mol/L)
Fig. 3 Electronic spectra of
aqueous solutions of 4 measured
at various concentrations:
7.4 9 10-6 mol/L (a) and
4.7 9 10-4 mol/L (b, c) (the
concentrations are based on
chemical formula given in
Table 1)
Table 3 Electronic spectral data of aqueous solutions of 1 and 4
k (nm)
e (L mol-1 cm-1
)
Assignment
[Fe(bpy)3]2[V4O8((2R,3R)-tart)2]ꢀ12H2O (1) (c = 1 9 10-5 mol/L)
247
289
298
348
491
522
4.8 9 104
9.7 9 104
1.1 9 105
1.2 9 104
1.4 9 104
1.5 9 104
p ? p*
p ? p*
p ? p*
MLCT
MLCT
MLCT
[Ni(bpy)3]4[V4O8((2R,3R)-tart)2][V4O8((2R,3R)-tart)2]ꢀ24H2O (4)a
245
295
307
485
783
854
5.7 9 104
7.0 9 104
6.4 9 104
sh
p ? p*
p ? p*
p ? p*
3
3A2g ? T1g (F)
Fig. 4 TG and DTA curves of 2
3
35
3A2g ? T2g
3A2g ? Eg
1
sh
(approximately 90 % of products) is a racemic compound
containing both enantiomers of cations and anions in equal
amount in its crystal structure. The other type is a racemic
conglomerate (approximately 10 % of products). Some-
times (generally very rarely), racemic compound and
Values of e were calculated using chemical formulas given in Table 1
a
Electronic spectra of compound 4 were measured at different
concentrations: 7.4 9 10-6 mol/L (bands: 245, 295, 307 nm) and
4.7 9 10-4 mol/L (bands 485 sh, 783, 854 sh nm)
123

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Transition Met Chem (2014) 39:893–900
Fig. 7 The types of crystallization products from racemic solution
containing both enantiomers of cation (D, K) and anion (A, B)
Fig. 5 TG and DTA curves of 4
racemic conglomerate crystallize concomitantly [7, 22].
Racemic conglomerates can be divided into two types:
Crystals of the first type contain only one enantiomer both
of cations and anions, while crystals of the second type are
composed of one enantiomer of cation (anion) and both
enantiomers of anion (cation) (‘‘hemiracemic’’ compound).
The tetranuclear anions [V4O8(tart)2]4- in 1, 2 and 4
(Fig. 8) consist of one {V4O8} group and two (2R,3R)-tart or
(2S,3S)-tart ligands. In accordance with previous results, the
tetranuclear anions incorporate the same enantiomers of the
tart ligand [11]. The {V4O8} group is composed of four V=Ot
groups that are bridged by four Ob atoms. The central {V4O4}
ring acquires an approximate boat conformation. All vana-
dium atoms are penta-coordinated, and the geometry of the
coordination polyhedra can be described as square pyramids
distorted toward trigonal bipyramids. The s value (s = 0 for
ideal square pyramid; s = 1 for ideal trigonal bipyramid [23])
is 0.3483 for V1, 0.3124 and 0.1972 for V2, 0.0863 for V3 and
0.1998 for V4. Each of the {VO5} pyramids contains one
terminal oxygen atom (Ot), two bridging oxygen atoms (Ob),
and two oxygen atoms from the tartrato ligand (Oh—from
hydroxyl group and Oc—from carboxylate group). The bond
lengths in the anion are within the expected ranges:
1.5782(34)–1.6053(32) (1), 1.5925(18)–1.6094(19) (2),
˚
1.5937(19)–1.6081(19) (4) A for V=Ot bonds; 1.7671(31)–
1.8701(32) (1), 1.7599(16)–1.8747(16) (2), 1.7696(17)–
˚
1.8813(16)(4) A for V–Ob bonds;1.8535(39)–1.9506(33) (1),
˚
1.8655(160)–1.9678(104) (2), 1.7932(53)–2.0052(104) (4) A
for V–Oh; 2.0288(33)–2.0719(33) (1), 2.0190(84)–
˚
2.0981(221) (2), 2.0154(98)–2.0742(44) (4) A for V–Oc. The
weak interactions between V and O atoms from the opposite
pyramids [d(Vꢀ ꢀ ꢀO) = 2.6407(31) and 2.5154(36),
2.7231(32) and 2.6602(36), 2.4684(30) and 2.4719(38),
2.5987(30) and 2.5903(30) (1), 2.5567(15), 2.4538(18),
2.6373(142), 2.7035(17) (2), 2.6131(15), 2.4576(15),
˚
2.4535(114), 2.6371(16) (4) A] complete the coordination
polyhedra of the central atoms to strongly distorted octahedra.
The tartrate anions are bonded as bis(bidentate) ligands and
possess a trans conformation. The [Fe(bpy)3]2? and
[Ni(bpy)3]2? cations have slightly distorted octahedral
˚
geometry with average bond lengths Fe–N 1.90–1.98 A in 1
˚
and 2 and Ni–N 2.07–2.10 A in 4.
Fig. 6 IR spectrum of
Ni(VO3)2 in a KBr pellet
123

Transition Met Chem (2014) 39:893–900
899
Fig. 8 Structure of the [V4O8((2R,3R)-tart)2]4- anion in 4. Selected
˚
bond lengths (A) [V1–O13, 1.6054(17); V1–O4, 1.9271(15); V1–O6,
Fig. 9 Presentation of homochiral layers in structure of 1 (D-Fe = D-
[Fe(bpy)3]2?
,
K-Fe = K-[Fe(bpy)3]2?
,
RR = [V4O8((2R,3R)-
tart)2]4-
)
2.0510(19); V1–O17, 1.7765(17); V1–O18, 1.9271(15); V2–O14,
1.5957(15); V2–O1, 2.0263(17); V2–O3, 1.8666(17); V2–O19,
1.8813(16); V2–O20, 1.8241(16); V3–O15, 1.5937(19); V3–O7,
2.0742(44); V3–O9, 1.7932(5); V3–O17, 1.8690(17); V3–O20,
1.8164(16); V4–O16, 1.6081(19); V4–O10, 2.0052(1); V4–O12,
2.0154(9); V4–O18, 1.8172(16); V4–O19, 1.7696(17)] and angles
(°) [O13–V1–O4, 109.587(8); O13–V1–O6, 93.302(8); O13–
V1–O17, 106.985(9); O13–V1–O18, 101.629(8); O14–V2–O1,
100.451(8); O14–V2–O3, 99.706(8); O14–V2–O19, 103.306(8);
O14–V2–O20, 102.62(8); O15–V3–O7, 99.117(1); O15–V3–O9,
99.010(2); O15–V3–O17, 103.699(9); O15–V3–O20, 102.934(8);
O16–V4–O10, 109.524(3); O16–V4–O12, 97.087(3); O16–V4–O18,
101.017(8); O16–V4–O19, 107.526(9); V1–O17–V3, 112.044(9);
V1–O18–V4, 128.029(9); V2–O20–V3, 170.972(9); V2–O19–V4,
112.589(9)]
The crystal structure of 1 is composed of three types of
homochiral layers parallel to (100): (i) the layer consisting
of D-[Fe(bpy)3]2? cations; (ii) the layer consisting of
[V4O8((2R,3R)-tart)2]4- anions, and (iii) the layer con-
sisting of K-[Fe(bpy)3]2? cations (Fig. 9). The layers
alternate in the order i–ii–iii–ii. The water molecules are
distributed between the layers. In all presented structures,
the layers consisting of [M(bpy)3]2? cations are homochiral
irrespective of the configuration of the anions.
Fig. 10 Presentation of homochiral layers of cations (D and K) and
heterochiral layers od anions (RR ? SS) in the crystal structure of 4
(D-Ni = D-[Ni(bpy)3]2?, K-Ni = K-[Ni(bpy)3]2?, RR = [V4O8((2-
R,3R)-tart)2]4-, SS = [V4O8((2S,3S)-tart)2]4-
)
Compounds 2 and 4 are isostructural. The crystal
structure of 4 is composed from the following layers: (i) the
layer consisting of both enantiomeric forms of anions
[V4O8((2R,3R)-tart)2]4- and [V4O8((2S,3S)-tart)2]4-; (ii)
layer consisting of D-[Ni(bpy)3]2? cations; and (iii) layer
consisting of K-[Ni(bpy)3]2? cations. The layers alternate
in the order i–ii–i–iii (Fig. 10). The water molecules are
distributed between the layers.
interactions are present: (1) between bipyridine ligands of
cations with the same configuration and (2) between
bipyridine ligands of cations with different configuration
(Fig. 11). The centroid to centroid distance between
˚
interacting bipyridine ligands are 3.83 and 3.77 A in 4. The
angles between planes of interacting pyridine rings are
Some noteworthy p–p interactions are present between
the complex cations in the crystal structures of 2 and 4. In
the crystal structure of 2, p–p interactions between cations
having different configurations are present. The interacting
bipyridine planes are parallel, and the centroid to centroid
9.59° and 0.0° for 4.
Supporting information
˚
distance is 3.77 A. The second centroid to centroid dis-
˚
tance (3.92 A) is exceeding the limit suggested by Janiak
CCDC no. 1010531 (1) 1010532 (2) and 1010530 (4)
contain supplementary crystallographic data. These data
can be obtained free of charge from The Cambridge
[24]. In the crystal structure of 4, two types of p–p
123

900
Transition Met Chem (2014) 39:893–900
Fig. 11 Presentation of p–p
interactions in the crystal
structure of 4. Centroids are
defined by following atoms:
Ct1: N13, C19, C25, C26, C27,
C28; Ct2: N22, C40, C41, C42,
C43, C44; Ct3: N21, C39, C45,
C46, C47, C48; Ct4: N21, C39,
C45, C46, C47, C48
ˇ
´
´
´
11. Schwendt P, Tracey AS, Tatiersky J, Galikova J, Zak Z (2007)
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Inorg Chem 46:3971–3983
12. Nakamoto K (1986) Infrared and Raman spectra of inorganic and
coordination compounds. Wiley, New York
13. Braterman PS, Song JI, Peacock RD (1992) Inorg Chem
31:555–559
14. Hadadzadeh H, Mansouri G, Rezvani A, Khavasi HR, Skelton
BW, Makha M, Charati FR (2011) Polyhedron 30:2535–2543
15. Palmer RA, Piper TS (1966) Inorg Chem 5:864–878
Acknowledgments This work was supported by the Ministry of
Education, Science, Research and Sport of the Slovak Republic
(Grant No. VEGA 1/0336/13).
´
16. Gonzalez E, Rodrigue-Witchel A, Rebel C (2007) Coord Chem
Rev 251:351–363
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