Synthesis and structure of manganese(ii) coordination polymers with 1,4-diazabicyclo[2.2.2]octane N, N′-dioxide: solvent and template effects

Article abstract of DOI:10.1007/s11172-020-2930-4

New metal-organic frameworks [Mn(DMF)₂(odabco)₂](ClO₄)₂ · H₂O (1), [Mn(H₂O)_2? (HCOO)₂] · odabco (2), and [Mn(Hodabco)₂(odabco)₃](NO₃)₄ (3) were synthesized by the reaction of manganese Perchlorate with 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) in N, N-dimethylformamide (DMF) under varying reaction conditions. The reaction in N-methylpyrrolidone afforded the metal-organic framework [Mn(odabco)₃](NO₃)₂ (4). The structures of compounds [Mn(DMF)₂(odabco)₂](ClO₄)₂ · DMF · H₂O (1 · DMF · H₂O), [Mn(DMF)₂(odabco)₂](ClO₄)₂ · THF (1 · THF), 2, 3, and 4 were determined by single-crystal X-ray diffraction analysis. In compounds 1 · DMF · H₂O, 1 · THF, 3, and 4, odabco acts as a bridging ligand; in 2, as a guest template. Compound 1 · DMF · H₂O has a layered structure and contains a system of intersecting channels occupied by perchlorate anions and disordered solvent molecules. The framework of 1 proved to be stable during the post-synthetic exchange of DMF by THF. The coordination framework of the adduct 1 · THF containing localized THF molecules has a similar structure. The layered (2) and chain-like (3) compounds are stabilized by extensive hydrogen-bonding systems, giving rise to pseudo-three-dimensional close-packed structures. The replacement of DMF by N-methylpyrrolidone under conditions similar to the synthesis of 3 affects the coordination ability of odabco and affords compound 4 having a three-dimensional framework with pcu topology.

Full text of DOI:10.1007/s11172-020-2930-4

Russian Chemical Bulletin, International Edition, Vol. 69, No. 8, pp. 1511—1519, August, 2020
1511
Synthesis and structure of manganese(II) coordination polymers with
,4-diazabicyclo[2.2.2]octane N,N´-dioxide: solvent and template effects*
1
P. A. Demakov,a,b A. S. Romanov, D. G. Samsonenko, D. N. Dybtsev,a,b and V. P. Fedina,b
b
a,b
aNikolaev 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. E-mail: cluster@niic.nsc.ru
b
Novosibirsk State University,
2
ul. Pirogova, 630090 Novosibirsk, Russian Federation
New metal-organic frameworks [Mn(DMF) (odabco) ](ClO ) •H O (1), [Mn(H O) -
2
2
4 2
2
2
2
(
HCOO) ]•odabco (2), and [Mn(Hodabco) (odabco) ](NO ) (3) were synthesized by the
2 2 3 3 4
reaction of manganese perchlorate with 1,4-diazabicyclo[2.2.2]octane N,N´-dioxide (odabco)
in N,N-dimethylformamide (DMF) under varying reaction conditions. The reaction in
N-methylpyrrolidone afforded the metal-organic framework [Mn(odabco) ](NO ) (4). The
3
3 2
structures of compounds [Mn(DMF) (odabco) ](ClO ) •DMF•H O (1•DMF•H O),
2
2
4 2
2
2
[
Mn(DMF) (odabco) ](ClO ) •THF (1•THF), 2, 3, and 4 were determined by single-crystal
2 2 4 2
X-ray diffraction analysis. In compounds 1•DMF•H O, 1•THF, 3, and 4, odabco acts as a
2
bridging ligand; in 2, as a guest template. Compound 1•DMF•H O has a layered structure and
2
contains a system of intersecting channels occupied by perchlorate anions and disordered solvent
molecules. The framework of 1 proved to be stable during the post-synthetic exchange of DMF
by THF. The coordination framework of the adduct 1•THF containing localized THF molecules
has a similar structure. The layered (2) and chain-like (3) compounds are stabilized by extensive
hydrogen-bonding systems, giving rise to pseudo-three-dimensional close-packed structures.
The replacement of DMF by N-methylpyrrolidone under conditions similar to the synthesis of
3
affects the coordination ability of odabco and affords compound 4 having a three-dimension-
al framework with pcu topology.
Key words: metal-organic frameworks, N-oxides, manganese(II), X-ray diffraction, template
effect.
The past two decades have witnessed considerable prog-
ress in the chemistry of metal-organic frameworks (MOFs).
Due to the structural diversity and a broad range of func-
tional properties, these materials are the subject of great
interest in fundamental physics and inorganic chemistry
tive adsorption and separation of anionic substrates13 and
1
4
also for the post-synthetic modification via ion exchange.
Classical works on the chemistry of MOFs deal with per-
manently porous cationic frameworks containing solely
1
5,16
4,4-bipyridyl as the bridge.
However, the formation
1
—4
research as well as in applied materials science.
Most
of commonly occurring coordination polyhedra (octa-
hedron, tetrahedron, square) solely by N-donor ligands is
often not possible because of steric factors, and the com-
of the available MOFs are based on carboxylate ligands
due to structural rigidity and predictability of the linker
5
geometry and the availability of polycarboxylic acids.
pounds are generally stable only with non-oxophilic cat-
6
—8
17,18
Such N-donor molecules as imidazole derivatives,
ions.
Thus, there are serious obstacles to the use of
4
,4´-bipyridine, and 1,4-diazabicyclo[2.2.2]octane
bridging N-donor ligands for the construction of cationic
MOFs, resulting in scarce publications on such MOFs.
Compared to N-donor analogs, N-oxides are sterically
less hindered ligands and, due to the presence of donor
oxygen atoms, a wider range of metal centers can be
utilized for the framework assembly. For MOFs with
9
—12
(
dabco)
The utilization of electroneutral ligands in the synthe-
sis of MOFs allows the targeted preparation of charged
are also commonly used as bridges in MOFs.
(
cationic) frameworks, which are of interest for the selec-
1
9,20
N,N´-dioxides, examples of unusual topologies,
incorporation of large anions into a porous structure,
the
*
Dedicated to Academician of the Russian Academy of Sciences
2
1,22
A. M. Muzafarov on the occasion of his 70th birthday.
Based on the materials of the International Conference
2
3
and the breathing behavior induced by external stimuli
"
(
Chemistry of Organoelement Compounds and Polymers 2019"
November 18—22, 2019, Moscow, Russia).
were reported. Nevertheless, MOFs with such bridging
ligands are rare. For instance, a search of the Cambridge
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1511—1519, August, 2020.
066-5285/20/6908-1511 © 2020 Springer Science+Business Media LLC
1

1
512
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
Demakov et al.
Structural Database (CSD) revealed only four MOFs
Mn
containing 1,4-diazabicyclo[2.2.]octane N,N´-dioxide
2
3—25
N
O
N
(
odabco).
The combination of odabco and transition
metal cations in MOFs provides the framework porosity
along with such functional properties as breathing behav-
O
2
6—28
29
ior
and UV transparency of the aliphatic framework
Mn(1)
or a combination of magnetism and catalytic activity of
the metal center.
3
0—32
Therefore, the development of
O
N
facile methods for the synthesis of MOFs with odabco is
of great importance.
N
O
b
c
Here we report the synthesis of new metal-organic
frameworks based on manganese(II) and 1,4-diazabi-
cyclo[2.2.2]octane N,N´-dioxide (odabco) and the results
a
of single-crystal X-ray diffraction study of [Mn(DMF)2-
Fig. 1. Coordination environment of the Mn(1) atom in com-
(
(
(
(
odabco) ](ClO ) •DMF•H O (1•DMF•H O), [Mn-
pound 1•DMF•H O. Hydrogen atoms are omitted for clarity.
2
4 2
2
2
2
DMF) (odabco) ](ClO ) •THF (1•THF), [Mn(H O) -
The Mn(2) atom has a similar coordination environment.
2
2
4 2
2
2
HCOO) ]•odabco (2), [Mn(Hodabco) (odabco) ]-
2
2
3
NO ) (3), and [Mn(odabco) ](NO ) (4).
3
4
3
3 2
The bridging odabco ligands connect MnII ions to form
distorted tetragonal polymer layers with windows of ca.
Results and Discussion
2
4
×6 Å . The Mn—Oodabco—Oodabco—Mn torsion angles
are 167.2 and 116.5. The polymer layers in 1•DMF•H O
2
We developed a convenient procedure for the synthe-
alternate along the c axis to form a two-layer packing. The
shortest interlayer Mn—Mn distance is 13.147 Å. In the
interlayer space, there are intersecting channels running
in two directions with dimensions of about 6×7 and
sis of 1,4-diazabicyclo[2.2.2]octane N,N´-dioxide in gram
quantities in order to efficiently elaborate the synthesis of
MOFs based on odabco. 1,4-Diazabicyclo[2.2.2]octane
N,N´-dioxide was synthesized under mild conditions by
the oxidation of 1,4-diazabicyclo[2.2.2]octane with hy-
drogen peroxide and was crystallized as an adduct with
2
9×11 Å . The smaller channels are occupied by perchlorate
anions, while the larger channels (Fig. 2) contain disor-
dered DMF and water molecules, the presence of which
3
3
34
H O , the structure of which was reported previously.
was confirmed by the SQUEEZE routine. The solvent-
2
2
The optimization of the procedure allowed us to rapidly
prepare large amounts of the ligand in quantitative yield
as a finely crystalline substance convenient for further
processing and use. The elemental and phase purity of the
accessible volume of 1•DMF•H O, calculated with the
2
PLATON software, is 22%. According to the SQUEEZE
routine (102 e– in 366 Å ), the formula [Mn(DMF) -
3
2
(odabco) ](ClO ) •DMF•H O can be assigned to the
2
4 2
2
solvate odabco•3H O was confirmed.
crystals of 1•DMF•H O. The crystals of 1•DMF•H O
2
2
2
2
Compound 1 was synthesized in high yield from
easily lose dimethylformamide solvent molecules on stor-
age in air. According to the elemental analysis data, the
Mn(ClO ) •6H O, odabco•3H O , and HClO on heat-
4
2
2
2
2
4
ing in N,N-dimethylformamide at 80 C for 18 h. The
resulting product is [Mn(DMF) (odabco) ](ClO ) •H O
2 2 4 2 2
2
+
–
Mn : ClO4 molar ratio in the reaction mixture was ca.
: 4. The reaction with HNO or HCl instead of HClO ,
(1). The easy loss of guest solvent molecules is apparently
attributed to high lability of the coordination layers and
conformational flexibility of the bridging odabco ligands.
The replacement of the solvent guest molecules in the
1
3
4
as well as using manganese chloride instead of its perchlor-
ate did not afford compound 1. Apparently, the perchlor-
ate anion is a template for the formation of a porous
metal-organic framework of compound 1. According to
the single-crystal X-ray diffraction data for the triclinic
crystals taken directly from the reaction mixture, there are
two Mn atoms, two coordinated odabco molecules, two
coordinated DMF molecules, and two perchlorate an-
ions per asymmetric unit of the crystal structure of
channels of 1•DMF•H O by tetrahydrofuran resulted in
2
the formation of compound 1•THF with a monoclinic
crystal structure. The Mn—Oodabco distances vary in
a narrow range of 2.127(3)—2.198(3) Å. The Mn—ODMF
distances are 2.202(4) and 2.212(4) Å. The metal centers
are linked by bridging odabco ligands to form layers struc-
turally similar to the layers in 1•DMF•H O. The polymer
2
1
•DMF•H O. The Mn(1) and Mn(2) atoms have a sim-
layers alternate along the b axis, also forming a two-layer
packing. The Mn—Oodabco—Oodabco—Mn torsion angles
are 168.9° and 104.9°, which attests to a slight contrac-
tion of the two-dimensional network compared to
2
ilar octahedral coordination environment formed by four
oxygen atoms of four bridging odabco ligands and two
DMF oxygen atoms (Fig. 1). The Mn—Oodabco distances
are in the range of 2.137(3)—2.144(3) Å. The Mn—ODMF
distances are somewhat larger (2.252(3) and 2.239(3) Å).
1•DMF•H O. The interlayer distances are somewhat
shorter; the shortest interlayer Mn—Mn distance in
2

MOFs with 1,4-diazabicyclooctane N,N´-dioxide Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1513
Cl(1)
Cl(2)
Mn(2)
Mn(1)
Cl(1)
Cl(2)
Mn
O
N
Cl
c
b
Fig. 2. Layered structure of 1•DMF•H O projected along the a axis. Hydrogen atoms are omitted for clarity.
2
1
•THF is 12.877 Å. The interlayer space is occupied by
incorporates a guest odabco molecule linked via hy-
perchlorate anions and localized guest THF molecules.
The solvent-accessible volume of 1•THF, calculated
with the PLATON software, is 16%. Therefore, the coor-
dination network of 1 proved to be stable, and the chan-
nels were shown to have a size sufficient for the guest
exchange.
drogen bonds to coordinated water; the corresponding
…
Oodabco OH2O distances are 2.659 and 2.684 Å. The geo-
metric complementarity between the cavity and the odabco
molecule and the absence of other examples of layered
formates containing guest molecules suggest that the
odabco molecule acts as a template in the synthesis of 2.
The elemental analysis data for compound 2 are consistent
Compound 2 was synthesized from Mn(ClO ) •6H O,
4
2
2
odabco•3H O , and HClO on heating in DMF at 80 C
with the formula [Mn(H O) (HCOO) ]∙odabco, which
2
2
4
2 2 2
for 3 days. The asymmetric unit of the crystal structure of
was determined from the X-ray diffraction data. The ab-
sence of solvent-accessible voids in 2 was confirmed by
calculations with the PLATON software.
II
2
contains one Mn cation in an octahedral coordination
environment formed by four oxygen atoms of four bridg-
ing carboxyl groups and two oxygen atoms of aqua ligands.
The Mn—OCOO distances are 2.1929(11) and 2.1967(12) Å,
Compound 3 was synthesized from Mn(ClO ) •6H O,
4
2
2
odabco•3H O , and HNO on heating in DMF at 80 C
2
2
3
and the Mn—O
distance is 2.1519(15) Å. The for-
for 7 days. The asymmetric unit of the crystal structure of
H O
2
II
II
mate anions link Mn ions to form distorted tetrahedral
3 involves three Mn cations. All cations have a similar
2
layers (Fig. 3) with windows of ca. 3×5 Å . The polymer
octahedral coordination environment formed by two
oxygen atoms of the bridging odabco ligands and four
layers alternate along the b axis. Adjacent layers are mirror
+
images of each other. A similar layer motif is characteris-
oxygen atoms of the terminal odabco and Hodabco li-
tic of the manganese formates with no guest molecules
gands. The Mn—O distances are 2.151(5)—2.246(6) Å.
prepared previously.3
5,36
In the structure of 2, the inter-
The Mn ions are linked by two bridging odabco li-
II
3
layer space has cavities with a size of about 3×6×6 Å
enclosed by water oxygen atoms (Fig. 4). Each cavity
gands to form one-dimensional chains (Fig. 5). The
Mn—Oodabco—Oodabco—Mn torsion angles in the chains

1
514
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
Demakov et al.
Mn
O
N
a
c
Fig. 3. Layer in the structure of compound 2 projected along the b axis. Hydrogen atoms are omitted for clarity.
Mn
O
H
N
b
a
c
Fig. 4. Tetragonal cavity in the interlayer space of compound 2. Hydrogen atoms of formate anions are omitted for clarity. The
…
O(odabco) H(H O) hydrogen bonds are indicated by dashed lines.
2

MOFs with 1,4-diazabicyclooctane N,N´-dioxide Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1515
Mn
O
Mn(1)
N
c
b
a
Fig. 5. Coordination environment of the Mn(1) atom in compound 3. Hydrogen atoms are omitted for clarity. The interchain
O(odabco)—O(odabco) contacts are indicated by dashed lines. The Mn(2) and Mn(3) atoms have a similar coordination environment.
Mn
O
N
c
a
Fig. 6. Packing of chains in the three-dimensional structure of 3 projected along the b axis. Hydrogen atoms and nitrate anions are
omitted for clarity.

1
516
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
Demakov et al.
vary from 169.7 to 177.7. In the interchain space (Fig. 6),
in the range of 24.0—28.9. The framework has narrow
2
2
there are channels with a cross-section of about 7×7 Å
channels with a cross-section of 3×4 Å (Fig. 7) that con-
3
occupied by nitrate anions. The closest interchain Oodabco
—
nect larger voids with a size of 6×6×8 Å . The voids are
Oodabco contacts are in the range of 2.362—2.441 Å, which
attests to the presence of hydrogen bonds between oxygen
atoms. In this case, half of the terminal odabco ligands
should be protonated, thereby compensating the excessive
negative charge of the nitrate anions that present in
the structure. The resulting formula [Mn(Hodabco)2-
occupied by partially disordered nitrate anions. The frame-
work structure of 4 exhibits chain motifs similar to those
in 3; however, the structure of 4 does not contain coordi-
nated odabco molecules, and all N,N´-dioxide ligands are
bridging. This results in the cross-linking of {—Mn—
odabco—}∞ chains to form a closer-packed three-dimen-
sional framework with a primitive cubic (pcu) topology.
Therefore, the nature of the solvent affects the dimension-
ality of the resulting polymer structure.
(
odabco) ](NO ) is electroneutral. The hydrogen bond
3 3 4
network links the cationic chains {[Mn(Hodabco) -
2
(
odabco)3]2+}∞ to form a doubly interpenetrated supra-
molecular framework. The elemental analysis data for
compound 3 are consistent with the formula determined
from the X-ray diffraction data.
An analysis of the synthesis conditions and the struc-
tural features of compounds 1—4 suggests that the crystal-
lization of a particular product in systems containing Mn2
and odabco is affected by several factors. The template
effect of the perchlorate anion, which occupies a cavity of
suitable size, was revealed in the synthesis of 1. At lower
concentrations of the reagents and longer reaction times,
the hydrolysis of DMF gives formate anions that displace
the neutral ligand. In this case, the odabco molecules oc-
+
The synthesis with the use of NMP instead of DMF
resulted in the crystallization of single crystals of com-
pound 4 upon keeping at 80 C for 10 days. The asym-
II
metric unit of the crystal structure of 4 contains two Mn
cations, four coordinated odabco molecules, and four
nitrate anions. The Mn(1) and Mn(2) atoms have a simi-
lar octahedral coordination environment formed by
six oxygen atoms of six bridging odabco ligands. The
Mn—Oodabco distances are in the range of 2.191(10)—
cupy positions between the {Mn(H O) (HCOO) } lay-
2
2
2 ∞
ers in the cavities complementary in size and chemical
environment. Therefore, the hydrolysis of DMF upon
prolonged heating of the reaction mixture and the template
effect of the odabco molecule lead to a change in the reac-
tion pathway and result in the crystallization of 2. The
2
.234(10) Å. The metal centers are linked by bridging li-
gands to form a three-dimensional metal-organic frame-
work. The Mn—Oodabco—Oodabco—Mn torsion angles are
Mn
O
N
b
a
c
Fig. 7. Fragment of the crystal structure of compound 4. Hydrogen atoms and nitrate anions are omitted for clarity.

MOFs with 1,4-diazabicyclooctane N,N´-dioxide Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1517
reaction in a mixture of DMF and nitric acid affords
Experimental
+
compound 3 with protonated Hodabco ligands, which
are involved in one-dimensional chains linked to each
other via short hydrogen bonds. Under similar conditions,
the use of NMP instead of DMF resulted in the formation
of a three-dimensional structure of 4 containing no ter-
minal ligands. Consequently, the variation of the solvent
nature allows the change of the dimensionality of the re-
sulting metal-organic framework.
1,4-Diazabicyclo[2.2.2]octane N,N´-dioxide, solvate with
tris(hydrogen peroxide), odabco•3H O . 1,4-Diazabicyclo[2.2.2]-
2
2
octane (dabco) (2.0 g, 18 mmol) was added portionwise with
stirring to a 30% H O solution (10.0 mL, 97 mmol). The suspen-
2
2
sion was slowly heated with stirring to 50 C until dabco was
completely dissolved. Then the solution was carefully concen-
trated to approximately half of the initial volume. The resulting
solution was salted out by the addition of dioxane (5 mL) and
then cooled to 0 C. The finely crystalline precipitate that formed
was filtered off on a porous paper filter, successively washed with
dioxane (2×10 mL) and benzene (2×10 mL), and dried in air for
Therefore, using odabco•3H O as a convenient source
2
2
of the ligand, we synthesized five new metal-organic
frameworks with 1,4-diazabicyclo[2.2.2]octane N,N´-di-
oxide. The structure of the reaction product was found to
be affected by the anionic composition of the medium and
the nature of the solvent. The possibility of varying the
Mn—Oodabco—Oodabco—Mn torsion angle over a wide
range from 0 to 180 (conformational flexibility of the
linker) provides a great structural diversity of metal-organic
frameworks and allows the control of the dimensionality
and porosity of the framework.
5
min. Yield 4.3 g (98%). Found (%): C, 29.4; H, 7.4; N, 11.5.
C H N O (odabco•3H O ). Calculated (%): C, 29.3; H, 7.4;
6
18
2
8
2
2
N, 11.4.
catena-[Bis( -1,4-diazabicyclo[2.2.2]octane N,N´-dioxide)-
2
bis(N,N-dimethylformamide)manganese(II)] perchlorate mono-
aqua solvate, [Mn(DMF) (odabco) ](ClO ) •H O (1). Man-
2
2
4 2
2
ganese perchlorate hexahydrate (36.2 mg, 0.10 mmol),
odabco•3H O (49.2 mg, 0.20 mmol), N,N-dimethylformamide
2
2
(2.50 mL), and a 65% HClO solution (0.02 mL (0.21 mmol)
4
Table 1. Crystallographic data and the X-ray diffraction data collection and refinement statistics for com-
pounds 1•DMF•H O and 1•THF
2
Parameter
1•DMF•H O
1•THF
2
Molecular formula
M/g mol–
Crystal system
Space group
T/K
C21H47N O Cl Mn
C22H46N O Cl Mn
6 15 2
7
16
2
1
779.49
760.49
Triclinic
Monoclinic
–
P1
P2 /n
1
130(2)
170(2)
a/Å
12.1175(12)
12.4298(9)
13.334(2)
117.665(11)
90.093(11)
92.333(8)
1776.8(4)
2
12.2223(12)
22.723(3)
12.1956(10)
90
b/Å
c/Å
α/deg
β/deg
91.538(8)
90
γ/deg
3
V/Å
Z
3385.8(6)
4
–
3
dcalc/g cm
1.457
1.492
–
1
μ/mm
F(000)
Crystal size/mm
-Scan range/deg
Index ranges hkl
0.597
0.622
818
1596
0.550.470.07
3.37—25.35
−13 < h < 14
0.800.380.35
2.39—25.68
−14 < h < 14
−27 < k < 21
−10 < l < 14

−
−
14 < k < 14
16 < l < 16
Number of reflections
measured
14535
6488
14828
6407
unique
observed (I > 2σ(I))
Rint
4646
3533
0.0623
0.0817
0.2224
0.1038
0.2422
1.111
0.0221
0.0602
0.1193
0.1144
0.1337
1.124
R (I > 2σ(I))
1
wR (I > 2σ(I))
2
R (based on all reflections)
1
wR (based on all reflections)
2
2
Goodness of fit on F
Residual electron density (max/min)/e Å–3
1.098/−0.595
0.423/−0.370

1
518
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
Demakov et al.
were mixed in a glass flask with a screw cap. The mixture was
coarse-crystalline precipitate was filtered off on a porous paper
filter, washed with DMF (2×3 mL), and dried in air. The struc-
ture of the product was determined by single-crystal X-ray dif-
fraction. Yield 17.0 mg (52%). Found (%): C, 29.8; H, 5.6; N, 8.8.
treated in an ultrasonic bath for 5 min and then kept at 80 C for
1
8 h. The resulting colorless precipitate was filtered off on a porous
paper filter, washed with DMF (2×5 mL), and dried in air. Yield
3.0 mg (81%). Found (%): C, 30.5; H, 5.6; N, 12.4; Cl, 10.6.
C18H40N O Cl Mn ([Mn(DMF) (odabco) ](ClO ) •H O).
6
C H N O Mn ([Mn(H O) (HCOO) ]•odabco). Calculated (%):
8 18 2 8 2 2 2
–
1
C, 29.5; H, 5.6; N, 8.6. IR (KBr), /cm : 3336 (s, br), 3232 (w),
3188 (w), 2922 (w), 2850 (w), 2745 (w), 2391 (m), 2302 (w),
1853 (w), 1765 (m), 1627 (s), 1377 (s, br), 1245 (s), 1046 (m),
819 (m), 691 (s), 425 (m).
6
15
2
2
2
4 2
2
Calculated (%): C, 30.6; H, 5.7; N, 11.9; Cl, 10.0. IR (KBr),
–
1

2
1
1
5
/cm : 3420 (w, br), 3040 (m), 3020 (m), 2933 (m), 2819 (w),
651 (w), 2499 (w), 2320 (w), 2272 (w), 2147 (w), 2017 (w),
664 (s), 1491 (m), 1475 (m), 1442 (m), 1415 (m), 1390 (m),
377 (m), 1253 (m), 1090 (s), 895 (m), 861 (w), 689 (s), 613 (s),
21 (w), 455 (m).
catena-[Mono( -1,4-diazabicyclo[2.2.2]octane N,N´-di-
2
oxide)-bis(1,4-diazabicyclo[2.2.2]octane N,N´-dioxide)-bis(hydro-
1,4-diazabicyclo[2.2.2]octane N,N´-dioxide)manganese(II)] ni-
Single crystals of 1•DMF•H O were taken directly from the
trate, [Mn(Hodabco) (odabco) ](NO ) (3). Manganese perchlor-
2
2 3 3 4
reaction mixture. Single crystals of 1•THF were obtained upon
ate hexahydrate (90.5 mg, 0.25 mmol), odabco•3H O (123.0 mg,
2 2
storage of the crystals of 1•DMF•H O in tetrahydrofuran for
0.50 mmol), N,N-dimethylformamide (5.00 mL), and a 62%
2
2
days using a one-time replacement of the solvent.
HNO solution (1 mL) were mixed in a glass flask with a screw
3
catena-[Bis( -formato)bis(aqua)manganese (II)], solvate
cap. The mixture was treated in an ultrasonic bath for 5 min and
then kept at 80 C for 7 days. The resulting colorless coarse-
crystalline precipitate was filtered off on a porous paper filter,
washed with DMF (2×5 mL), and dried in air. Yield 23.5 mg
(23%). Found (%): C, 34.6; H, 6.1; N, 18.8. C30H62N14O22Mn
2
with mono(1,4-diazabicyclo[2.2.2]octane N,N´-dioxide), [Mn-
(
H O) (HCOO) ]•odabco (2). Manganese perchlorate hexa-
2
2
2
hydrate (36.2 mg, 0.10 mmol), odabco•3H O (24.6 mg,
2
2
0
.10 mmol), N,N-dimethylformamide (4.00 mL), and a 65%
HClO solution (0.08 mL, 0.84 mmol) were mixed in a glass flask
([Mn(Hodabco) (odabco) ](NO ) ). Calculated (%): C, 35.1;
4
2 3 3 4
–1
with a screw cap. The mixture was treated in an ultrasonic bath
for 5 min and then kept at 80 C for 72 h. The resulting colorless
H, 6.1; N, 19.1. IR (KBr), /cm : 3430 (w, br), 3038 (m), 2990 (w),
2931 (w), 2828 (w), 2710 (w), 2495 (w), 2382 (w), 2150 (w),
Table 2. Crystallographic data and the X-ray diffraction data collection and refinement statistics for compounds 2—4
Parameter
2
3
4
Molecular formula
C H N O Mn
C30H62N14O22Mn
1025.87
C18H36N O12Mn
8
18
325.18
2
8
8
–
1
M/g mol
611.49
Trigonal
R3c
Crystal system
Space group
T/K
Orthorhombic
Pnma
Monoclinic
Cc
295(2)
21.7238(7)
26.8436(10)
21.8917(9)
90
90.651(3)
90
130(2)
130(2)
a/Å
8.6099(6)
15.3443(12)
9.0241(6)
90
23.5703(6)
23.5703(6)
30.1114(9)
90
b/Å
c/Å
α/deg
β/deg
90
90
90
120
γ/deg
3
V/Å
Z
1192.20(15)
4
12765.2(8)
12
14487.4(9)
24
–
3
dcalc/g cm
1.812
1.601
1.682
–
1
μ/mm
F(000)
Crystal size/mm
-Scan range/deg
Index ranges hkl
1.148
0.413
0.629
676
6492
7704
0.150.150.09
3.27—29.51
−11 < h < 10
0.510.390.35
3.44—29.55
−21 < h < 29
−36 < k < 26
−29 < l < 30
0.200.200.14
3.36—25.35
−16 < h < 28
−24 < k < 29
−37 < l < 30

−
−
21 < k < 14
12 < l < 11
Number of reflections
measured
4388
1474
32917
20902
10415
4367
unique
observed (I > 2σ(I))
Rint
1119
15386
3971
0.0310
0.0295
0.0659
0.0465
0.0712
1.031
0.0310
0.0501
0.1016
0.2543
0.1125
0.2668
1.136
R (I > 2σ(I))
0.0750
1
wR (I > 2σ(I))
0.2160
2
R (based on all reflections)
0.0988
1
wR (based on all reflections)
0.2441
2
2
Goodness of fit on F
1.090
Residual electron density (max/min)/e Å–3
0.304/−0.266
1.613/−0.599
0.871/−1.411

MOFs with 1,4-diazabicyclooctane N,N´-dioxide Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1519
1
1
7
740 (w), 1660 (w), 1585 (m), 1472 (m), 1348 (s), 1165 (w),
096 (w), 1046 (m), 982 (m), 906 (m), 858 (m), 827 (w), 778 (w),
13 (m), 675 (m), 562 (m), 481 (w), 444 (m).
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catena-[Tris( -1,4-diazabicyclo[2.2.2]octane N,N´-dioxide)-
2
manganese(II)] nitrate, [Mn(odabco) ](NO ) (4). Manganese
perchlorate hexahydrate (58.0 mg, 0.16 mmol), odabco•3H O
3
3 2
2
2
(
39.4 mg, 0.16 mmol), N-methylpyrrolidone (5.00 mL), and
a 62% HNO solution (1 mL) were mixed in a glass flask with
3
a screw cap. The mixture was treated in an ultrasonic bath for
5
min and then kept at 80 C for 10 days. The resulting small
prismatic crystals were selected for X-ray diffraction. The struc-
ture and composition of the product were determined by single-
crystal X-ray diffraction.
X-ray diffraction study. Single-crystal X-ray diffraction data
sets for compounds 1—4 were collected on an Agilent Xcalibur
automated diffractometer equipped with an AtlasS2 area detec-
tor (graphite monochromator, (Mo-K) = 0.71073 Å, -scan-
ning technique with a step of 0.5). The intensities were inte-
grated, absorption corrections were applied, and the unit cell
3
7
parameters were determined using the CrysAlisPro software.
The crystal structures were solved with the SHELXT program
3
8
suite and refined by the full-matrix least-squares method with
anisotropic displacement parameters (except for hydrogen atoms)
using the SHELXL program suite.39 The hydrogen atoms of
organic ligands were positioned geometrically and refined using
a riding model. The crystallographic data and the X-ray diffrac-
tion data collection and refinement statistics are given in Tables 1
and 2. Complete tables of interatomic distances, bonds angles,
atomic coordinates, and atomic displacement parameters were
deposited with the Cambridge Crystallographic Data Centre
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(
CCDC 1973653—1973657) and can be obtained from the
authors.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 19-43-
5
2
2
2
7. H. Reinsch, R. S. Pillai, R. Siegel, J. Senker, A. Lieb,
G. Maurin, N. Stock, Dalton Trans., 2016, 45, 4178.
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43016) and the Government of the Novosibirsk Region.
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Received December 26, 2019;
in revised form March 11, 2020;
accepted June 25, 2020