Synthesis and structure of chiral coordination polymers of CoII, CuII, and MgII saccharates

Article abstract of DOI:10.1007/s11172-013-0098-x

Chiral metal-organic coordination polymers [Co₂(sacch) ₂]·1/₂H₂O·CH₃OH (1), [Cu(sacch)(H₂O)₂]·3H₂O (2), and [Mg(H₂O)₃(sacch)] (3) (H₂sacch is d-saccharic acid) were synthesized from aqueous or water-methanol solutions of potassium hydrogen saccharate and a salt of the corresponding metal. The compositions and structures of the resulting compounds were determined by single-crystal X-ray diffraction and confirmed by X-ray powder diffraction, IR spectroscopy, thermogravimetry, and elemental analysis.

Full text of DOI:10.1007/s11172-013-0098-x

Russian Chemical Bulletin, International Edition, Vol. 62, No. 3, pp. 716—721, March, 2013
716
Synthesis and structure of chiral coordination polymers
of CoII, CuII, and MgII saccharates*
M. S. Zavakhina,a D. G. Samsonenko,a,b D. N. Dybtsev,a,b M. P. Yutkin,a A. V. Virovets,a and V. P. Fedina,b
aA. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences,
3 prosp. Akad. Lavrentieva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9489. Eꢀmail: cluster@niic.nsc.ru
bNovosibirsk State University,
2 ul. Pirogova, 630090 Novosibirsk, Russian Federation
Chiral metalꢀorganic coordination polymers [Co2(sacch)2]•1/2H2O•CH3OH (1),
[Cu(sacch)(H2O)2]•3H2O (2), and [Mg(H2O)3(sacch)] (3) (H2sacch is Dꢀsaccharic acid) were
synthesized from aqueous or waterꢀmethanol solutions of potassium hydrogen saccharate and
a salt of the corresponding metal. The compositions and structures of the resulting compounds
were determined by singleꢀcrystal Xꢀray diffraction and confirmed by Xꢀray powder diffraction,
IR spectroscopy, thermogravimetry, and elemental analysis.
Key words: coordination polymers, chiral complexes, saccharic acid, magnesium comꢀ
plexes, copper(II) complexes, cobalt(II) complexes, Xꢀray diffraction.
The chemistry of enantiomerically pure (homochiral)
have a porous nature.12—15 We characterized a series of
new homochiral porous frameworks based on aspartic,16
malic,17 lactic,18 mandelic,19 camphoric,20,21 and tartaric
acids.22 Nevertheless, a search for new biocompatible and
(or) biodegradable porous coordination structures remains
a topical and important problem.
porous coordination polymers has attracted great interest
since these compounds show promise for applications in
stereoselective processes.1—3 A number of interesting studꢀ
ies on the stereoselective catalysis,4,5 adsorption,6,7 and
enantiomeric separation8 with the use of homochiral poꢀ
rous coordination frameworks were published in recent
years. The recently shown9 possibility of the synthesis
of cyclodextrinꢀbased homochiral porous coordination
frameworks gave a new impetus to the development of the
chemistry of such important compounds. Due to high bioꢀ
compatibility of such "edible" homochiral porous coordiꢀ
nation structures, these compounds can be considered as
new promising drug carriers. The possibility of applying
porous coordination polymers based on abiogenic tereꢀ
phthalates for the drug storage and delivery was examined
in the recent past.10 However, the problem of the toxicity
of the drug carrier or its biodegradation products can be
eliminated only with the use of porous compounds based
on biocompatible compounds. Sugars, amino acids, and
their simplest derivatives that are present in living systems
are the most convenient and evident reagents for the synꢀ
thesis of homochiral coordination polymers with high bioꢀ
compatibility. Due to the availability of such biomoleꢀ
cules, numerous biomoleculeꢀbased coordination comꢀ
pounds were synthesized.11 However, only a few of them
DꢀSaccharic acid (H2sacch) is a product of the partial
oxidation of glucose and a promising ligand for the prepaꢀ
ration of biocompatible homochiral porous frameworks.
Only four frameworks of metal saccharates were deꢀ
scribed in the literature,23—26 whereas 13 coordination
polymers are known for sterically isomeric galactaric acid
(a product of the partial oxidation of galactose). However,
since all galactarates are achiral diastereomers, they have
attracted little interest. In the present study, we report the
synthesis and structural characterization of three new
homochiral coordination polymers, cobalt(II) saccharate
[Co2(sacch)2]•1/2H2O•MeOH (1), copper(II) saccharate
[Cu(sacch)(H2O)2]•3H2O (2), and magnesium(II) sacꢀ
charate [Mg(H2O)3(sacch)] (3). Compound 3 is particuꢀ
larly interesting from the point of view of biocompatiꢀ
bility, because the magnesium cation is virtually safe for
the body and is a component of many drugs and food
additives.
* Dedicated to Academician of the Russian Academy of Sciences
I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0716—0721, March, 2013.
1066ꢀ5285/13/6203ꢀ716 © 2013 Springer Science+Business Media, Inc.

Chiral metalꢀorganic frameworks
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
717
Results and Discussion
indicative of hydrogen bonding. Besides, there are empty
hydrophobic channels of a diameter of 5.2 Å, where diꢀ
sordered methanol molecules are located. Compound 1 is
isostructural to the earlier described23 zinc saccharate
[Zn2(sacch)2]•2H2O (Fig. 3). The thermogravimetric
analysis of compound 1 revealed a 5% weight loss in the
temperature range of 20—220 C. This fact can be asꢀ
signed to the removal of guest water and methanol moleꢀ
cules (calculated 7% for 1/2 H2O + MeOH).
The coordination polymer complexes [Co2(sacch)2]•
•1/2H2O•MeOH (1), [Cu(sacch)(H2O)2]•3H2O (2), and
[Mg(H2O)3(sacch)] (3) were prepared by the precipitaꢀ
tion of crystalline products from aqueous or waterꢀmethaꢀ
nol solutions of the corresponding metal salt and potassiꢀ
um hydrogen saccharate KHsacch. The compositions and
structures of the compounds were determined by singleꢀ
crystal Xꢀray diffraction and confirmed by elemental analꢀ
ysis (C, H, N), thermogravimetry (TG), and IR spectroscopy.
The structural model of compound 1 was established
by Xꢀray diffraction study. The crystal structure contains
two crystallographically independent cobalt(II) cations.
Both cations are in an octahedral environment formed by
four ꢀcarboxylate oxygen atoms and two ꢀhydroxyl
oxygen atoms of the saccharate anion in cis positions. The
Co(1) and Co(2) atoms are nonequivalent because they
are surrounded by groups with different configurations
(Fig. 1). The oxygen atoms of the OH groups are coordiꢀ
nated in a monodentate fashion, whereas the carboxylate
oxygen atoms act as 2ꢀbridges between the adjacent coꢀ
balt cations to form chains running along the crystalloꢀ
graphic axis c. The chains are linked via the saccharate
bridges in the perpendicular directions а and b to form
a chiral framework containing two types of channels arꢀ
ranged in the staggered order (Fig. 2). Thus, there are
small hydrophilic zigzag channels of variable diameter
(1.8—2.6 Å), with the uncoordinated ꢀhydroxyl groups of
the saccharate anions pointing inside the channels. These
channels are occupied by disordered methanol and H2O
molecules. The distance between the hydroxyl groups of
the adjacent anions along the channel is 2.74 Å, which is
In the crystal structure of compound 2, the copper(II)
cations are in an octahedral environment formed by oxyꢀ
gen atoms of two different carboxylate groups, two nonꢀ
equivalent ꢀhydroxyl groups (related by a mirror plane),
and two water molecules in trans positions with respect to
each other (Fig. 4). The Cu—OH2 distances (2.303(2) and
2.548(2) Å) are much longer than the Cu—OH (1.989(2) Å)
and Cu—OCO distances (1.929(3) Å). This is typical of
the Cu2+ (d9) cation and results from the JahnꢀTeller disꢀ
tortion. The copper(II) cations and saccharate anions form
chains running along the body diagonal of the unit cell
(Fig. 5). Cystallization water molecules are located beꢀ
tween the chains. The distance between the oxygen atoms
of the crystallization and coordinated water molecules corꢀ
responds to standard hydrogen bonds (2.71—2.86 Å).
Shorter contacts are observed between the crystallization
water molecules and the carboxyl oxygen atom (2.55 Å),
which is attributed to stronger hydrogenꢀacceptor properꢀ
ties of the COO group. In addition, there are hydrogen
bonds (2.75 and 2.77 Å) between the adjacent chiral chains.
An extensive hydrogen bond network in the crystal strucꢀ
ture of 2 can serve as a proton transport channel and proꢀ
mote the proton conductivity of the compound. The
thermogravimetric analysis of compound 2 showed that
a 18% weight loss occurs in the temperature range of
20—150 C. This can be assigned to the removal of two
guest crystallization water molecules and two coordinated
water molecules (calculated 20% for 4 H2O).
R
Compound 3 also has a chain structure. The magneꢀ
sium cations are in a distorted octahedral environment
formed by three meridional water molecules, two carboxꢀ
ylate oxygen atoms of the saccharate anions in cis posiꢀ
tions with respect to each other, and one hydroxyl group
(Fig. 6). In compound 3, only three donor groups of the
saccharate anions (2 + ) are involved in the formation
of coordination bonds, as opposed to compounds 1 and 2
possessing four such groups (2 + 2). Therefore, the carbꢀ
oxylate groups of the saccharate anion in compound 3 are
coordinated to different metal cations in different fashion
to form chelating coordination ( + ) with one Mg cation
and monodentate coordination () with another Mg cation.
The coordination chains [Mg(sacch)] are arranged along
the b axis of the unit cell, the saccharate anions being
oriented in the same direction in a headꢀtoꢀtail manner.
In the crystal packing of 3, the chains are in an antiparalꢀ
lel arrangement (Fig. 7). There are short hydrogen bonds
Co(1)
Co(2)
S
Fig. 1. Coordination environment of the cobalt cations in comꢀ
pound 1. The carbon atoms in the R and S configurations are
presented in lilac and violet, respectively. The hydrogen atoms
are not shown.
Note. Figures 1, 4, and 6 are available in full color in the onꢀline
version of the journal (http://www.springerlink.com).

718
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
Zavakhina et al.
b
a
Fig. 2. Structure of the framework of compound 1. The hydrogen atoms are not shown.
(2.66 and 2.70 Å) and several longer bonds (2.90—3.06 Å)
between the chains. The chains form a close packing, where
the solvent molecules of solvation are absent.
A comparison of our data and the earlier results shows
that the bridging mode of coordination is typical of the
saccharate ligand. The carboxylate groups of saccharic
acid are always coordinated to different metal cations,
resulting in the formation of homochiral coordination
polymers. The ꢀhydroxyl groups adjacent to the carboxyl
groups are usually also involved in the coordination to the
1
2
R
Cu
S
5
10
15
20
25
30
2/deg
Fig. 4. Coordination environment of the copper cation in comꢀ
pound 2. The carbon atoms in the R and S configurations are
presented in lilac and violet, respectively. The hydrogen atoms
are not shown.
Fig. 3. Comparison of the experimental Xꢀray powder diffracꢀ
tion pattern of compound 1 (1) and the calculated pattern for
[Zn2(sacch)2]•2H2O (2).

Chiral metalꢀorganic frameworks
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
719
b
a
c
Fig. 5. Structure of the chains in compound 2. The hydrogen atoms are not shown.
cation to form strong chelate complexes. The ꢀhydroxyl
groups are not involved in the coordination. However,
they can serve as potential active sites for the stereospecifꢀ
ic recognition or catalytic activation. The conformational
flexibility of the saccharate ligand decreases the possibility
of the formation of porous structures and hinders the diꢀ
rected design of coordination frameworks with a specified
topology. In our opinion, the conformational lability can
be partially compensated by means of additional bridging
ligands having rigid geometry in the synthesis of heteroꢀ
ligand coordination polymers.
Experimental
Potassium hydrogen saccharate, magnesium(II) chloride,
magnesium(II) perchlorate, copper(II) nitrate, cobalt(II) chloride,
and methanol used as the starting compounds were at least of
reagent grade. The IR spectra were recorded on a Scimitar FTS
2000 instrument in KBr pellets. The thermogravimetric analysis
was performed on a TG 209 F1 thermobalance (Natzsch); samꢀ
ples were decomposed under an argon atmosphere at a heating
rate of 10 deg min–1. The elemental analysis for C, H, and N was
carried out on an EURO EA 3000 instrument (EuroVector) in
S
Mg
R
Fig. 6. Coordination environment of the magnesium cation in
molecule 3. The carbon atoms in the R and S configurations are
presented in lilac and violet, respectively. The hydrogen atoms
are not shown.
b
a
c
Fig. 7. Arrangement of the chains in the structure of compound 3. The hydrogen atoms are not shown.

720
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
Zavakhina et al.
Table 1. Crystallographic characteristics and the Xꢀray data collection and structure refinement statistics for compounds 1—3
Parameter
1
2
3
Molecular formula
C13H21Co2O17.5
575.16
C6H18CuO13
361.74
Triclinic
P1
6.6359(2)
7.1541(2)
7.4077(2)
100.120(1)
103.445(1)
108.058(1)
313.294(15)
1
C6H14MgO11
286.48
M/g mol–1
Crystal system
Space group
a/Å
Tetragonal
P41212
18.968(1)
18.968(1)
5.773(1)
90
Orthorhombic
P212121
5.8180(2)
10.4281(3)
17.9763(6)
90
b/Å
c/Å
/deg
/deg
90
90
90
90
/deg
V/Å3
2077.0(4)
4
1.839
1090.63(6)
4
1.745
Z

calc/g cm–3
1.917
1.814
/mm–1
4.245
0.220
F(000)
1172
187
600
Crystal size/mm
ꢀAngle scan range/deg
hkl range
0.10×0.06×0.02
2.14—35.41
–21  h  21,
–21  k  21,
–6  l  6
10036/1681
1672
0.50×0.29×0.21
2.93—30.96
–8  h  8,
–10  k  6,
–9  l  9
3947/2636
2628
0.30×0.22×0.08
2.26—28.33
–7  h  7,
–8  k  13,
–23  l  23
8956/2706
2655
Nhkl of measured/unique
Nhkl with I > 2(I)
Rint
0.1126
1.199
0.0141
1.225
0.0285
1.088
Goodness of fit on F2
R factors [I > 2(I)]
R1
wR2
0.1862
0.3972
0.0191
0.0610
0.0215
R factors (based on all reflections)
R1
wR2
0.1867
0.3975
0.0194
0.0686
0.0220
0.0603
Absolute structure parameter
Residual electron density (max/min), e Å–3
0.23(10)
3.025/–2.875
0.016(8)
0.381/–0.315
0.09(16)
0.329/–0.246
the Analytical Laboratory of the A. V. Nikolaev Institute of Inꢀ
organic Chemistry of the Siberian Branch of the Russian Acadeꢀ
my of Sciences. The Xꢀray powder diffraction data were obꢀ
tained on a Philips PW 1820/PW 1710 powder diffractometer
(CuꢀK,  = 1.54056 Å).
dried in air. The yield was 0.029 g (40%). Found (%): C, 21.3;
H, 4.8. C6H16CuO12 ([Cu(sacch)(H2O)2]•2H2O). Calculated:
C, 21.0; H, 4.7. IR (KBr), /cm–1: 400 (m), 512 (m), 589 (s), 687 (w),
716 (w), 807 (m), 835 (m), 962 (w), 1067 (m), 1123 (m), 1235 (m),
1291 (s), 1347 (s, sh), 2634 (w), 2612 (w), 2922 (m), 3413 (s, sh).
TG data: m = 18% (150 C), calculated 20% for 4 H2O.
Synthesis of catena{Dꢀsaccharatetriaquamagnesium},
[Mg(H2O)3(sacch)] (3). A mixture of MgCl2•6H2O (0.020 g,
0.10 mmol) and KHsacch (0.025 g, 0.1 mmol) in water (1 mL)
was placed in a sealed glass tube and kept under temperatureꢀ
controlled conditions at 60 C for 24 h. The crystals that formed
were washed several times with water and dried in air. The yield
was 0.002 g (7%). In the synthesis, an equivalent amount of
magnesium perchlorate can be used instead of magnesium
chloride. IR (KBr), /cm–1: 473 (m), 498 (w), 629 (s), 701 (m),
790 (w), 843 (w), 887 (w), 947 (w), 1042 (s), 1097 (s), 1235 (m),
1286 (s), 1327 (s), 1388 (m), 1423 (m), 1474 (w), 1610 (s), 1646
(s), 2687 (w), 2612 (w), 2920 (m), 3179 (s, sh), 3477 (s).
Synthesis of catena{bis(Dꢀsaccharate)dicobaltate(II)} hemihyꢀ
drate methanol solvate, [Co2(sacch)2]•1/2H2O•CH3OH (1). The
compounds CoCl2•6H2O (0.335 g, 1.4 mmol) and KHsacch
(0.252 g, 1.00 mmol) in a mixture of methanol and water (1 : 1,
v/v, 3.00 mL) were placed in a sealed glass tube and kept under
temperatureꢀcontrolled conditions at 60 C for 48 h. After coolꢀ
ing, the pink crystals that formed were separated from the mothꢀ
er liquor by decantation, washed several times with methanol,
and dried in air. The yield was 0.098 g (36%). Found (%):
C, 26.8; H, 3.8. C13H21Co2O17.5. Calculated (%): C, 27.1; H, 3.7.
IR (KBr), /cm–1: 528 (m), 566 (m), 632 (w), 686 (w), 738 (m),
850 (m), 895 (w), 1037 (m), 1120 (s, sh), 1232 (s), 1292 (s), 1352
(s), 1440 (s), 1645 (s), 2612 (w), 2934 (w), 3339 (m, sh). TG data:
m = 5% (220 C), calculated 7% for 1/2H2O + CH3OH.
Synthesis of catena{Dꢀsaccharatediaquacopper(II)} trihydrate,
[Cu(sacch)(H2O)2]•3H2O (2). A mixture of Cu(NO3)2•3H2O
(0.048 g, 0.20 mmol) and KHsacch (0.042 g, 0.17 mmol) in
water (2.00 mL) was kept at room temperature for 48 h. The
crystals that formed were washed several times with water and
Xꢀray diffraction study. Singleꢀcrystal Xꢀray diffraction data
sets for compounds 2 and 3 were collected at 150 K on an autoꢀ
mated Bruker X8Apex fourꢀcircle diffractometer equipped with
an area detector (ꢀ and ꢀscanning technique, (MoꢀK) =
= 0.71073 Å, graphite monochromator). Absorption corrections
were applied based on comparison of redundant and equivalent

Chiral metalꢀorganic frameworks
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
721
Table 2. Selected bond lengths in compounds 1—3
4. K. S. Jeong, Y. B. Go, S. M. Shin, S. J. Lee, J. Kim, O. M.
Yaghi, N. Jeong, Chem. Sci., 2011, 2, 877.
5. A. M. Shultz, O. K. Farha, D. Adhikari, A. A. Sarjeant, J. T.
Hupp, S. T. Nguyen, Inorg. Chem., 2011, 50, 3174.
6. X. Y. Bao, L. J. Broadbelt, R. Q. Snurr, Mol. Simul., 2009,
35, 50.
7. S. C. Xiang, Z. Zhang, C.ꢀG. Zhao, K. Hong, X. Zhao,
D. R. Ding, M. H. Xie, C. D. Wu, M. C. Das, R. Gill, K. M.
Thomas, B. Chen, Nature Commun., 2011, 2, 204.
8. A. L. Nuzhdin, D. N. Dybtsev, K. P. Bryliakov, E. P. Talsi,
V. P. Fedin, J. Am. Chem. Soc., 2007, 129, 12958.
9. R. A. Smaldone, R. S. Forgan, H. Furukawa, J. J. Gassenꢀ
smith, A. M. Z. Slawin, O. M. Yaghi, J. F. Stoddart, Angew.
Chem. Int. Ed., 2010, 49, 8630.
Bond
d/Å
1
2
3
M—O(OH)
2.016(16),
2.069(17)
2.058(17),
2.077(17),
2.060(17),
2.128(18)
—
1.980(2),
1.989(2)
1.925(2),
1.929(3)
2.0924(8)
M—O(COO)
1.9963(9),
2.0421(9),
2.0832(9)
M—O(OH2)
2.303(2),
2.548(2)
2.0476(9),
2.0783(10)
10. P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin,
P. Couvreur, G. Férey, R.E. Morris, C. Serre, Chem. Rev.,
2012, 112, 1232.
11. I. Imaz, M. RubioꢀMartínez, J. An, I. SoléꢀFont, N. L. Rosi,
D. Maspoch, Chem. Commun., 2011, 7287.
12. J. P. Barrio, J.ꢀN. Rebilly, B. Carter, D. Bradshaw, J. Bacsa,
A. Y. Ganin, H. Park, A. Trewin, R. Vaidhyanathan, A. I.
Cooper, J. E. Warren, M. J. Rosseinsky, Chem. Eur. J., 2008,
14, 4521.
13. E. V. Anokhina, Y. B. Go, Y. Lee, T. Vogt, A. J. Jacobson,
J. Am. Chem. Soc., 2006, 128, 9957.
reflections using the SADABS software.27 The singleꢀcrystal
Xꢀray diffraction data for compound 1 were recorded at 90 K using
a synchrotron source at the 2D Supramolecular Crystallography
beamline of the Pohang Accelerator Laboratory equipped with
a oneꢀcircle goniometer and the ADSC Quantum 210 area deꢀ
tector ( = 1.00000 Å, silicon monochromator, ꢀscanning techꢀ
nique). The Xꢀray data were collected, the frames were integratꢀ
ed, the data set was processed, and the absorption correction for
the crystal of 1 was applied using the HKL2000 program packꢀ
age.28 Structures 1—3 were solved by direct methods and refined
anisotropically (except for the H atoms) by the fullꢀmatrix leastꢀ
squares method using the SHELXꢀ97 program package.29 The
hydrogen atoms were positioned geometrically and refined using
a riding model. The positions of the hydrogen atoms of the water
molecules in structures 2 and 3 were refined with constraints
imposed on O—H bonds and atomic displacement parameters.
Unfortunately, the low quality of the Xꢀray diffraction data
for compound 1 did not allow us to perform the complete reꢀ
finement of the crystal structure. According to the singleꢀcrystal
Xꢀray diffraction data and the powder diffraction data (see
Fig. 3), compound 1 is isostructural to the earlier described23
[Zn2(sacch)2]•2H2O. Crystallographic parameters and the Xꢀray
diffraction data collection and refinement statistics are given in
Table 1. Selected interatomic distances are listed in Table 2. The
complete tables of interatomic distances, bond angles, atomic
coordinates, and displacement parameters were deposited to the
Cambridge Crystallographic Data Centre (CCDC 926289 (1),
917000 (2), 917001 (3); deposit@ccdc.cam.ac.uk or http://
www.ccdc.cam.ac.uk/data_request/cif), and can be obtained
from the authors.
14. M. J. Ingleson, J. Bacsa, M. J. Rosseinsky, Chem. Commun.,
2007, 3036.
15. J. Zhang, R. Liu, P. Feng, X. Bu, Angew. Chem., Int. Ed.,
2007, 46, 8388.
16. M. P. Yutkin, M. S. Zavakhina, D. G. Samsonenko, D. N.
Dybtsev, V. P. Fedin, Russ. Chem. Bull. (Int. Ed.), 2010, 59, 733.
17. M. P. Yutkin, M. S. Zavakhina, D. G. Samsonenko, D. N.
Dybtsev, V. P. Fedin, Inorg. Chim. Acta, 2013, 394, 367.
18. D. N. Dybtsev, A. L. Nuzhdin, H. Chun, K. P. Bryliakov,
E. P. Talsi, V. P. Fedin, K. Kim, Angew. Chem., Int. Ed.,
2006, 45, 916.
19. D. N. Dybtsev, M. P. Yutkin, D. G. Samsonenko, V. P.
Fedin, A. L. Nuzhdin, A. A. Bezrukov, K. P. Bryliakov, E. P.
Talsi, R. V. Belosludov, H. Mizuseki, Y. Kawazoe, O. S.
Subbotin, V. R. Belosludov, Chem. Eur. J., 2010, 16, 10348.
20. D. N. Dybtsev, M. P. Yutkin, V. P. Fedin, Russ. Chem. Bull.
(Int. Ed.), 2009, 58, 2246 [Izv. AN. Ser. Khim., 2009, 2179].
21. D. N. Dybtsev, M. P. Yutkin, E. V. Peresypkina, A. V. Virovets,
C. Serre, G. Férey, V. P. Fedin, Inorg. Chem., 2007, 46, 6843.
22. M. S. Zavakhina, M. P. Yutkin, D. G. Samsonenko, D. N. Dybꢀ
tsev, V. P. Fedin, Russ. Chem. Bull. (Int. Ed.), 2011, 60, 2425
[Izv. AN. Ser. Khim., 2011, 2378].
M. S. Zavakhina thanks the Haldor Topsøe A/S for
financial support.
23. B. F. Abrahams, M. Moylan, S. D. Orchard, R. Robson,
Angew. Chem. Int. Ed., 2003, 42, 1848.
This study was financially supported by the Russian
Academy of Sciences (Program of the Division of Chemꢀ
istry and Materials Science of the Russian Academy of
Sciences 5.6.3) and by the Russian Foundation for Basic
Research (Project No. 11ꢀ03ꢀ00112).
24. Y.ꢀK. Lv, Y.ꢀL. Feng, J.ꢀW. Liu, Zh.ꢀG. Jiang, J. Solid State
Chem., 2011, 184, 1339.
25. Y.ꢀK. Lv, C.ꢀH. Zhan, Zh.ꢀG. Jiang, Y.ꢀL. Feng, Inorg.
Chem. Commun., 2010, 13, 440.
26. F. Ferrier, A. Avezou, G. Terzian, D. Benlian, J. Mol. Struct.,
1998, 442, 281.
27. Bruker Advanced Xꢀray Solutions, Madison (WI, USA): Bruker
AXS Inc., 2004.
References
28. Z. Otwinowski, W. Minor, Methods Enzimol., 1997, 276, 307.
29. G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112.
1. W. Lin, MRS Bull., 2007, 32, 544.
2. M. P. Yutkin, D. N. Dybtsev, V. P. Fedin, Russ. Chem. Rev.
(Engl. Transl.), 2011, 80, 1061.
3. M. Yoon, R. Srirambalaji, K. Kim, Chem. Rev., 2012,
112, 1196.
Received December 26, 2012;
in revised form February 27, 2013