Three Mn(ii) coordination polymers with a bispyridyl-based quinolinate ligand: The anion-controlled tunable structural and magnetic properties

Article abstract of DOI:10.1039/c4dt00877d

Three new Mn(ii) coordination polymers, namely [Mn₃L ₆·2H₂O] (1), [MnL₂] (2), and [MnL ₂·2H₂O] (3), were prepared by solvothermal reactions of Mn(ii) salts with a bispyridyl-based quinolinate ligand. All complexes were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray crystallography. Single crystal X-ray studies show that these coordination polymers exhibit a structural diversification due to the different counteranions (OAc^-, Cl^-, and NO ₃^-). Complex 1 has a 2D supramolecular structure with a cyclic tetramer Mn₃L₆ secondary building unit. Complex 2 possesses a rhombohedral grid network containing a type of meso-helical chain (P + M) constructed via the metal-ligand coordination interaction. Complex 3 features a 3D non-porous structure based on the arrangement of 2D grids. Magnetic susceptibility measurements indicate that the three Mn(ii) polymers 1-3 show disparate magnetic properties due to their different supramolecular structures.

Full text of DOI:10.1039/c4dt00877d

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Three Mn(II) coordination polymers with a
bispyridyl-based quinolinate ligand: the
anion-controlled tunable structural and
magnetic properties†
Cite this: Dalton Trans., 2014, 43,
9777
a
a
a
a
b
b
Guozan Yuan,* Weilong Shan, Bin Liu, Lulu Rong, Liyan Zhang, Hui Zhang and
Xianwen Wei*
a
3 6 2 2 2 2
Three new Mn(II) coordination polymers, namely [Mn L ·2H O] (1), [MnL ] (2), and [MnL ·2H O] (3), were
prepared by solvothermal reactions of Mn(II) salts with a bispyridyl-based quinolinate ligand. All complexes
were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray crystallography.
Single crystal X-ray studies show that these coordination polymers exhibit a structural diversification due
−
−
−). Complex 1 has a 2D supramolecular structure with
to the different counteranions (OAc , Cl , and NO
a cyclic tetramer Mn secondary building unit. Complex 2 possesses a rhombohedral grid network con-
3
3 6
L
Received 25th March 2014,
Accepted 31st March 2014
taining a type of meso-helical chain (P + M) constructed via the metal–ligand coordination interaction.
Complex 3 features a 3D non-porous structure based on the arrangement of 2D grids. Magnetic suscepti-
bility measurements indicate that the three Mn(II) polymers 1–3 show disparate magnetic properties due
to their different supramolecular structures.
DOI: 10.1039/c4dt00877d
www.rsc.org/dalton
1
4
as appropriate building blocks to be incorporated in ligands.
Especially 2,2′-bipyridine (bipy) is frequently found in forming
Introduction
The design and construction of coordination polymers based functional complexes, because it can form highly stable enti-
1
5
on organic functional ligands are of significance not only for ties with metal ions. In contrast to the neutral 2,2′-bipyri-
their intriguing variety of architectures and topologies but also dine, catecholate ligands possess a charge of 2−, and therefore
for their tremendous potential applications in nonlinear address another kind of metal ion. The latter ligand unit
1
6
optics, catalysis, gas adsorption, luminescence, magnetism, recently has, in particular, attracted a lot of attention. Inter-
1
–4
and medicine.
Numerous reports in this field have mainly estingly, 8-hydroxyquinolinate (in its deprotonated form) is
focused on the design and preparation, as well as the struc- monoanionic and bridges the gap between the neutral bipyri-
ture–property relationships. Significant development has been dine and the dianionic catecholate because it possesses one
5
–7
achieved;
however, it is still a great challenge to rationally pyridine donor of bipy and one phenolate unit of catecholate.
prepare and predict the desired products with exact structures On the other hand, the geometry and chelating size of 8-hydro-
and predefined properties. The resulting structures are deter- xyquinolinate are the same as found for bipy and catecho-
8
17
mined by several factors, including the central metal ion, the late. It has been demonstrated that the 8-hydroxyquinoline
9
10
11
predesigned organic ligands, solvents, metal–ligand ratio,
unit is an ideal building block in coordination and supramole-
cular chemistry. With few notable exceptions, 8-hydroxyqui-
12
13
18
pH value of solution, counterions, and so on.
Pyridine derivatives, either as the parent units or as higher nolinate-based coordination polymers with desirable structure
1
9
oligomers (bipyridine, terpyridine, etc.), are very often utilized and functionality have not yet been developed.
Of particular interest to us are studies on the elegant
design and synthesis of novel quinolinate-based coordination
polymers whose structures can be tuned by a careful selection
of appropriate ligand and metal. Our goal is to achieve control
over the molecular or supramolecular structures and thereby
the physical properties of the new materials. In this study, we
have synthesized a bispyridyl-based quinolinate ligand from
the commercially available 8-hydroxyquinaldine to form Mn(II)
coordination polymers and characterized the resulting poly-
a
School of Chemistry and Chemical Engineering, Anhui University of Technology,
Maanshan 243002, China. Fax: +86 555 2311552; Tel: +86 555 2311807
b
School of Chemistry and Chemical Engineering, Huangshan University, Huangshan
2
45041, China. E-mail: yuanguozan@163.com, xwwei@ahut.edu.cn;
Tel: +86 13955996865
Electronic supplementary information (ESI) available: Additional structural
†
figures, the selected bond distances and angles for L-MOM, 1, 2 and 3 were
included. CCDC 972562–972565. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c4dt00877d
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mers by microanalysis, IR, and powder and single-crystal X-ray shown in Fig. 1a, there are intramolecular hydrogen bonds
diffraction. The polymer skeletons exhibit a structural diversifi- between the C–H groups of pyridine (or MOM) and the quino-
cation and fabricate one 2D supramolecular structures with a line N (or O) atoms [C(2)⋯N(1) = 2.962(6) Å, C(24)⋯N(4) =
cyclic tetramer Mn
3 6
L secondary building units, one rhombo- 3.092(5) Å and C(14)⋯O(2) = 2.915(5) Å], and intermolecular
hedral grid network, and one 3D non-porous structure in hydrogen bonds between the MOM C–H group and pyridine
−
−
3−
response to the counteranions OAc , Cl , and NO , respect- nitrogen atoms [C(24)⋯N(3) = 3.514(5) Å]. It is notable that
ively. As a result, the three Mn(II) polymers exhibit disparate two independent molecules are held together by two intermo-
magnetic properties due to their different supramolecular lecular C–H⋯π interactions between C–H groups of quinoline
structures.
(or MOM) and the pyridine ring of the adjacent ligand
C–H⋯π: 3.707(6)–3.922(6) Å). By the coactions of above inter-
molecular noncovalent interactions, the structure extends to a
D supramolecular structure in the bc plane (Fig. 1b).
Mn ·2H O] (1). Single crystals of complex 1 were readily
obtained in good yield by heating Mn(OAc)2 and HL in a
(
2
Results and discussion
Synthetic chemistry
[
3
L
6
2
The ligand L-MOM (MOM: methoxymethyl) was synthesized in mixture of MeOH and water. Complex 1 crystallizes in the
6% yield by Suzuki coupling reaction between 4-pyridylboro- monoclinic space group P2 /n with Z = 2. The asymmetry unit
9
1
nic acid and 5,7-dibromo-2-methyl-8-methoxymethoxyquino- contains one half of a formula unit, that is, 1.5 Mn(II) atoms,
line, which was obtained in two steps in excellent overall yield three ligands HL, and one water molecule. As shown in
from the cheap commercially available 8-hydroxyquinaldine Fig. 2a, the Mn1 atom is six-coordinated by four nitrogen and
1
(
Scheme 1). The L-MOM ligand was fully characterized by H two oxygen atoms provided by four ligands L, forming an octa-
13
and C NMR, ESI-MS, and single-crystal X-ray diffraction. hedral geometry. The equatorial plane is occupied by two NO
Single crystals of [Mn ·2H O] (1), [MnL (2) and donors set of two L ligands around the Mn1 atom and the
MnL ·2H O] (3) were readily obtained in good yield by heating apical position by two pyridyl atoms of two other ligands. Mn2
3
L
6
2
2
]
[
2
2
the corresponding manganese(II) salts and L-MOM in water atom is surrounded by three N and two O atoms provided by
and methanol (or isopropanol). The –MOM group was comple- three different L ligands, resulting in a distorted trigonal
tely removed from the starting ligands upon complexation bipyramidal geometry with the equatorial plane occupied by
with the metal ions. Complexes 1–3 are stable in air and in- the three atoms of three ligands and the apical position by two
soluble in water and organic solvents, and were formulated on phenol oxygen atoms. The bond lengths and angles around
the basis of microanalysis, IR, and single-crystal X-ray diffrac- Mn are 2.090(9)–2.260(6) Å for Mn–N, 1.940(6) and 2.039(5) Å
tion. The reaction was originally accomplished in a 1 : 2 molar for Mn–O, 136.3(3)° and 180.0(3)° for O–Mn–O, 77.7(3)–
ratio of Mn(II) and L-MOM, but the products were not signifi- 116.5(3)° for O–Mn–N, and 86.2(2)–180.0(1)° for N–Mn–N,
cantly affected by a change of the molar ratio. Moreover, when respectively.
ethanol was used as a solvent instead of methanol or isopro-
panol, the same products were obtained. The complexes 1–3
are thus favorable species irrespective of the reactant molar
ratios as well as the organic solvents used.
Structural description
Ligand (L-MOM). Neutral ligand L-MOM was crystallographi-
cally characterized. The dihedral angle (ca. 37.1–55.3°)
between the quinoline and pyridine moieties indicates that the
molecule is noncoplanar. In the crystal structure of L-MOM, as
Fig. 1 (a) Perspective views of hydrogen-bonding interactions in
L-MOM. (b) Perspective views of the 2D supramolecular structure fabri-
Scheme 1 Synthesis of ligand L-MOM and polymers 1–3.
cated by intermolecular noncovalent forces in L-MOM.
9778 | Dalton Trans., 2014, 43, 9777–9785
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Fig. 3 (a) View of 1D helical chains fabricated via C–H⋯π interactions
in 1 along the b-axis. (b) Perspective views of intermolecular C–H⋯π
interaction in 1.
Fig. 2 (a) Views of the coordination geometries of Mn(II) atoms in 1. (b)
One 1D infinite chain in 1 along the a-axis; (c) 3-fold interpenetrated
architecture in 1.
In complex 1, six L ligands with eight uncoordinated
pyridyl groups connect four Mn cations to form a cyclic tetra-
mer Mn L , which is further linked into a 2D supramolecular
4
6
structure in the ac plane (Fig. 2b). Because of the spacious
nature of the 2D supramolecular structure, it allows another
two independent identical structures to penetrate it in a
normal mode, thus giving a 3-fold interpenetrated architecture
(
Fig. 2c and S3†). Interestingly, a helical chain is alternately
arranged through the intermolecular C–H⋯π interactions
between the C–H group of quinoline units and the pyridine
(
ring of the adjacent ligand, 3.875(17) Å) in complex 1. The
helical chain is thus generated around the crystallographic
Fig. 4 (a) Views of the coordination geometries of Mn(II) atoms in 2;
2
(1) axis with a pitch of 23.721(15) Å, which is equal to the
b axis length (Fig. 3).
MnL ] (2). When the ligand L-MOM reacted with MnCl2
(b) the rhombohedral grid structure of 2 in the bc plane.
[
2
under the same reaction conditions, complex 2 was obtained phically independent Mn(II) atom and one ligand L. The
2
+
as yellow block-like crystals. A single-crystal X-ray diffraction coordination environment of Mn ion in complex 2 is shown
study of 2 reveals an infinite square grid consisting of six- in Fig. 4a, and it can be seen that Mn1 is six-coordinated to
coordinate Mn centers and bridging ligands (Fig. 4a). 2 crys- two phenolato oxygen atoms and four nitrogen atoms from
tallizes in the monoclinic space group P2
1
/c, with one half of a four ligands L. The Mn(II) center adopts an octahedral geome-
formula unit in the asymmetric unit, that is, 1/2 crystallogra- try with the equatorial plane occupied by two chelating NO
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donor sets from two ligands L and the apical position by two cated by the dihedral angles between the terminal pyridyl ring
nitrogen atoms of two other ligands. in the 7-position and phenolato ring decreasing from 42.26° in
In the bc plane, each Mn1 atom is linked to four adjacent 2 to 38.89° and 37.42° in 3. Similar to 2, the terminal pyridyl
Mn1 atoms through the chelating NO donors and pyridyl groups in the 7-position and chelating NO donors of ligands
groups of ligands L to form a rhombohedral grid structure link the Mn(II) centers into a 2D grid structure in the ab plane,
(
(
Fig. 4b). These grids are further linked by the C–H⋯π and the distances between Mn centers exhibit a subtle distinc-
between the C–H group of pyridine and the phenolato ring of tion (2, 8.8332(25) Å; 3, 8.7862(11) Å and 8.8517(12) Å). A type
the adjacent ligand, 3.586(8) Å) interactions along the a axis to of meso-helical chain (P + M) is alternately arranged in the ab
form a 3D porous framework structure (Fig. 5a and S6†). It is plane (Fig. 6). Note that complex 3 avoids extremely large void
notable that a kind of meso-helical chain (P + M) constructed spaces by the arrangement of the 2D grids (Fig. 7 and S9†).
via the metal–ligand coordination interactions is observed in
the solid state of this compound (Fig. 5b). These meso-helical
PXRD and fluorescent properties
chains with a pitch of 10.2952(14) Å are alternately arranged
To prove that the crystal structures of complexes 1–3 are truly
along the b axis, which is identical to the b axis length. To the
representative of their bulk materials, powder X-ray diffraction
best of our knowledge, such a supramolecular layer containing
(
PXRD) experiments (Fig. 8) were carried out on the as-syn-
meso-helical chains is very rare.
MnL ·2H O] (3). In order to further investigate the influ-
thesized samples. The peak positions of experimental and
simulated PXRD patterns are in good agreement, which
[
2
2
ence of counterions on the formation and structure of the
complexes, ligand L-MOM was reacted with Mn(NO under
the same conditions, complex 3 (MnL ·2H O) was obtained.
3 2
)
2
2
Single-crystal X-ray diffraction analysis reveals that the
complex 3 crystallizes in the orthorhombic system, space
group Pca2 . As shown in Fig. S6,† there is one crystallographi-
1
cally independent Mn(II) atom, two L ligands, and two water
molecules in the asymmetric unit. As compared with the struc-
ture of 2, the linkage of MnL remains intact, but L ligands in 3
undergo significant twists around the metal centers, as indi-
Fig. 6 The meso-helical chains in 3 are alternately arranged in the
ab plane.
Fig. 5 (a) The 3D framework structure of 2 mediated by C–H⋯π inter-
actions; (b) 2D layer structure of 2 containing meso-helical chains
(
P + M).
Fig. 7 The twofold interpenetrated architecture in 3.
9780 | Dalton Trans., 2014, 43, 9777–9785
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Fig. 10 Temperature dependence of magnetic susceptibility in the
Fig. 8 PXRD patterns of complexes 1–3.
−1
form of χ
M
T vs. T for 1, inset: χ
M
vs. T plot for 1 (open circles and red
line represent the experimental data and fit).
confirm their phase purity. The difference in intensity of some
diffraction peaks may be attributed to the preferred orientation
of the crystalline samples.
decrease with a very slow speed and attain a minimum of
3
−1
4
.74 cm K mol at ca. 47 K. Then the χ T values start to
M
The fluorescent properties of complexes 1–3 and their
corresponding free L-MOM ligand were investigated in the
solid state at room temperature (Fig. 9). 1–3 exhibit intense
photoluminescence with the emission maxima at 523, 527,
and 527 nm, respectively, upon excitation at 365 nm. Com-
pared with the bond at 402 nm of the L-MOM ligand, the com-
plexes exhibit a remarkable red shift. However, the green
emissions of complexes 1–3 show no significant difference,
and may originate from metal-to-ligand charge transfer
increase with a high speed and reach the highest peak with
the value of 8.47 cm K mol at 31 K, strongly suggesting the
3
−1
presence of global antiferromagnetic interactions and three-
21
M
dimensional magnetic ordering. After that, the χ T values
3
−1
decrease abruptly to the minimum value 4.11 cm K mol , at
K, probably due to the interlayer antiferromagnetic inter-
2
action. The magnetic susceptibility conforms to the Curie–
Weiss law in a range of 30–300 K and gives the negative con-
3
−1
stant θ = −16.54 K, Curie constant C = 6.08 cm K mol
,
(MLCT) transition.
further confirming the antiferromagnetic coupling nature
between the Mn(II) ions.
−
1
Magnetic properties
The χ T and χ
vs. T plots for compound 2 as shown in
M
M
3
Fig. 11. The χ
M
T value per Mn(II) at 300 K is about 6.20 cm K
The magnetic measurements were performed on polycrystal-
line samples of 1, 2 and 3 using a SQUID magnetometer under
an applied field of 1000 Oe over the temperature range
−
1
mol , which is slightly higher than the spin only value of
3
−1
4
.375 cm K mol for uncoupled high spin Mn(II) (g = 2.00
3
−1
−
1
and S = 5/2) and it gradually decreases to 5.58 cm K mol at
1 K. Upon further cooling, χ T increases dramatically and
reaches a maximum of 6.26 cm K mol at 31 K. The Curie–
2
–300 K. Fig. 10 shows the χ
M
T and χ
M
vs. T plots of com-
3
−1
4
M
3
pound 1. The magnitude of χ T at 300 K is 6.02 cm K mol
,
M
−1
3
which is slightly higher than the spin only value of 4.375 cm
K mol− for uncoupled high spin Mn(II) (S = 5/2) based g =
1
2
.00. With the temperature decreasing, the χMT values
Fig. 11 Temperature dependence of magnetic susceptibility in the form
−1
of χ
M
T vs. T for 2, inset: χ
M
vs. T plot for 2 (open circles and red line
Fig. 9 Emission spectra of complexes 1–3 in the solid state.
represent experimental data and fit).
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were carried out on a Quantum Design SQUID MPMS XL-7
instrument (2–300 K) in the magnetic field of 1 kOe, and the
diamagnetic corrections were evaluated using Pascal
constants.
Synthesis of L-MOM and 1–3. 5,7-Dibromo-2-methyl-8-
2
0
hydroxyquinoline.
To a solution of 8-hydroxyquinaldine
3.18 g, 20 mmol) in MeOH (30 mL) was added solid NaHCO
3.18 g, 37.8 mmol). To this suspension was added drop-wise
5 min) at rt a solution of Br (3.2 mL, 62.4 mmol, excess) in
(
(
(
3
2
methanol (10 mL). The reaction mixture was stirred at rt for
0 min to give an orange solution and a white precipitate.
Solid Na SO (23.0 g, 183.0 mmol, excess) was added to this
3
2
3
suspension in small portions over 5 min to quench residual
Br . The reaction was mildly exothermic. A colorless suspen-
2
Fig. 12 Temperature dependence of magnetic susceptibility in the
−1
sion was obtained after final addition and further stirring for
30 min. It was diluted with water (40 mL) to give a thick white
suspension which was stirred for 30 min. The pH of the reac-
tion mixture at that stage was close to neutral (pH test paper).
The product was filtered, thoroughly washed with water and
extracted with CH Cl –water to remove inorganic materials.
form of χ
M
T vs. T for 3, inset: χ
M
vs. T plot for 3 (open circles and red
line represent experimental data and fit).
3
−1
Weiss fit of the data above 30 K gives C = 6.14 cm mol
K
and θ = −3.02 K. The negative value of the Weiss constant
reveals the antiferromagnetic interactions between Mn(II) ions.
2
2
The organic layer was evaporated to give the product as a pale
orange solid (6.0 g, 96%).
Synthesis of 5,7-dibromo-2-methyl-8-methoxymethoxyquino-
line. Under a nitrogen atmosphere, the solution of 5,7-
dibromo-2-methyl-8-hydroxyquinoline (3.15 g, 10.0 mmol) in
THF (30 mL) was added to a suspension of NaH (1.0 g,
Below 30 K, the χ T drops quickly and approaches a value of
M
3
−1
5
.26 cm mol K at 2 K. The further decrease may be due to
the saturation effect.
2
2
As shown in Fig. 12, for compound 3, at room temperature
3
−1
M
the value of the product χ T is 4.44 cm K mol , which is
3
−1
similar to the expected value of 4.375 cm K mol for one iso-
41.7 mol) in anhydrous THF (30 mL) at 0 °C with stirring. The
lated high-spin Mn(II) ion (g = 2.00 and S = 5/2). Upon cooling,
resulting solution was stirred at 0 °C for 30 min, and then
methoxymethyl chloride (2.7 mL, 35.8 mmol) was slowly
added. The mixture was allowed to warm to room temperature
and stirred for 12 h. Then the reaction was quenched by water.
After separation, the aqueous layer was extracted with CH Cl
the χ
M
T value decreases continuously, reaching a value of
3
−1
2
.64 cm K mol at 2 K. These features indicate an antiferro-
−
1
magnetic coupling. Data fitting of the χM –T curve using the
3
Curie–Weiss law gives the Curie constant (C = 4.41 cm
K
2
2
−
1
mol ) and the Weiss constant (θ = −3.07 K). The negative θ
value suggesting an antiferromagnetic interaction between
Mn(II) ions in compound 3.
(
3 × 60 mL). The combined organic layers were washed with
brine and dried over MgSO . After removal of the solvent, the
residue was purified by column chromatography on silica gel
1 : 1, hexane–CH Cl ) to afford 5,7-dibromo-2-methyl-8-meth-
oxymethoxyquinoline as a white solid (3.09 g, 86%). H NMR
4
(
2
2
1
(
(
400 MHz, CDCl ) δ: 8.32 (d, J = 8.0 Hz, 1H), 7.90 (s, 1H), 7.37
3
Experimental
Materials and characterization methods
1
3
d, J = 8.0 Hz, 1H), 5.65 (s, 2H), 3.74 (s, 3H), 2.75 (s, 3H);
C
NMR (400 MHz, CDCl
3
) δ: 159.9, 150.3, 143.1, 136.2, 132.9,
All of the chemicals are commercially available, and used 126.6, 123.6, 116.4, 116.3, 100.4, 58.5, 25.6; ESI-MS: m/z 360.0
+
+
+
without further purification. Elemental analyses of C, H and N ([M + 1] ), 361.0 ([M + 2] ), 361.9 ([M + 3] ); Elemental analysis
were performed with an EA1110 CHNS-0 CE elemental analy- (%): calcd for (C12
H
11Br
2
NO
C: 39.88, H: 3.16, N: 3.79.
Ligand L-MOM. 5,7-Dipyridyl-2-methyl-8-methoxymethoxy-
2
) C: 39.92, H: 3.07, N: 3.88; found
zer. The IR (KBr pellet) spectrum was recorded (400–4000 cm−
1
region) on a Nicolet Magna 750 FT-IR spectrometer. Powder
X-ray diffraction (PXRD) data were collected on a DMAX2500 quinoline (4.8 g, 13.4 mmol), 4-pyridylboronic acid (4.8 g,
diffractometer using Cu Kα radiation. The calculated PXRD 40.11 mmol), Na CO3 (7.0 g, 66.04 mmol) and
2
patterns were produced using the SHELXTL-XPOW program PdCl
and single crystal reflection data. All fluorescence measure- 250 mL Schlenk flask, which was then pump-purged with N
ments were carried out on a LS 50B Luminescence Spectro- three times. DME (60 mL) and H O (30 mL) were added under
2 2 2
(dppf)·CH Cl (0.41 g, 0.80 mmol) were weighed into a
2
2
1
13
2
meter (Perkin Elmer, Inc., USA). H and C NMR experiments a dry N atmosphere. The mixture was stirred at 95 °C over-
were carried out on a MERCURY plus 400 spectrometer operat- night. The reaction mixture was cooled to room temperature
ing at a resonance frequency of 100.63 MHz. Electrospray and extracted with CH Cl . The organic layers were dried over
2
2
2 4
ionization mass spectra (ES-MS) were recorded on a Finnigan anhydrous Na SO and then concentrated under reduced
LCQ mass spectrometer using dichloromethane–methanol as pressure. The crude product was purified by column chromato-
mobile phase. Variable temperature magnetic measurements graphy on silica gel (8 : 3 : 1 AcOEt–hexane–Et N) to afford
3
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Table 1 Crystal data and structure refinement for ligand L-MOM, complexes 1–3
Identification code
L-MOM
1
2
3
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
C
22
H
19
N
3
O
2
C
120
H
88Mn
N O
3 18 8
C
40
H
28
N
6
O
2
Mn
C
40 32 6 4
H N O Mn
357.40
141(2)
0.71073
Monoclinic
P2 /n
2074.90
173(2)
0.71073
Monoclinic
P2 /n
679.62
141(2) K
0.71073
Monoclinic
P2 /c
711.62
173(2)
1.54178
Orthorhombic
Pca2
Space group
1
1
1
1
Unit cell dimensions
a = 12.619(3) Å
b = 21.772(7) Å
c = 14.394(4) Å
alpha = 90°
beta = 110.5°
gamma = 90°
3705.1(18), 8
1.281
a = 14.623(11) Å
b = 23.721(16) Å
c = 15.965(11) Å
alpha = 90°
beta = 109.0°
gamma = 90°
5238(6), 2
1.316
0.424
2146
a = 13.073(5) Å
b = 10.287(4) Å
c = 14.362(6) Å
alpha = 90°
beta = 114.2°
gamma = 90°
1762.1(12), 2
1.281
a = 14.1579(9) Å
b = 10.5162(7) Å
c = 24.8704(15) Å
alpha = 90°
beta = 90°
gamma = 90°
3703.4(4), 4
1.276
3
Volume (Å ), Z
Density (calculated) (Mg m−
Absorption coefficient (mm−
F(000)
3
)
1
)
0.084
1504
0.418
702
3.291
1468
θ Range for data collection (°)
Reflections collected
Independent reflections
Completeness to theta
1.78 to 27.47
13 780
8295 [R(int) = 0.0483]
27.47/97.6%
829/0/487
1.72 to 27.47
22 778
11 394 [R(int) = 0.1123]
25.24/98.0%
11 394/130/700
0.909
1.71 to 27.56
7503
3964 [R(int) = 0.0528]
27.56/97.3%
3964/0/223
0.950
3.55 to 68.14
10 405
5705 [R(int) = 0.0465]
68.14/97.6%
5705/1/444
1.033
Data/restraints/parameters
2
Goodness-of-fit on F
1.026
Final R indices [I > 2σ(I)]
R indices (all data)
R
R
1
= 0.0683, wR
= 0.1576, wR
2
= 0.1780
= 0.2532
R
R
1
= 0.0965, wR
= 0.2600, wR
2
2
= 0.2299
= 0.3213
R
R
1
= 0.0485, wR
= 0.1243, wR
2
= 0.0945
= 0.1205
R
R
1
= 0.0734, wR
= 0.0869, wR
2
= 0.2064
= 0.2209
1
2
1
1
2
1
2
Largest diff. peak and hole (e Å−
3
)
0.243 and −0.240
0.717 and −0.580
0.396 and −0.575
0.695 and −0.394
1
ligand L-MOM as a white solid. Yield: 4.4 g, 92%. H NMR
2 2
Elemental analysis data and IR of [MnL ·2H O] (3). Anal (%).
(400 MHz, CDCl ) δ: 8.72 (dd, J = 1.6, 4.4 Hz, 2H), 8.69 (dd, J = Calcd for C H N O Mn: C, 67.13; H, 4.51; N, 11.74. Found:
3 40 32 6 4
1
.6, 4.4 Hz, 2H), 8.05 (d, J = 8.8 Hz, 1H), 7.63 (dd, J = 1.6, 4.4 C, 67.05; H, 4.66; N, 13.85. FTIR (KBr pellet): 3443.2(s),
Hz, 2H), 7.42 (s, 1H), 7.38 (dd, J = 1.6, 4.4 Hz, 2H), 7.30 (d, J = 1595.6(s), 1544.2(s), 1513.5(s), 1439.7(s), 1420.8(s), 1384.5(s),
13
8
.8 Hz, 1H), 5.43 (s, 2H), 3.06 (s, 3H), 2.76 (s, 3H); C NMR 1365.8(s), 1332.8(m), 1275.1(s), 1217.8(w), 1184.7(w),
(
400 MHz, CDCl ) δ: 159.4, 150.4, 150.3, 150.0, 147.1, 146.2, 1106.3(m), 1067.9(w), 1006.2(m), 834.0(s), 804.4(w), 758.1 (m),
3
1
1
42.5, 134.1, 133.6, 131.6, 127.7, 125.9, 125.1, 124.9, 123.3, 744.7(w), 721.9(m), 705.2(m), 683.1(m), 655.6(m), 584.4(s),
00.5, 57.5, 25.8; ESI-MS: m/z 358.1 ([M + 1] ), 359.0 ([M + 2] ). 510.9(m), 457.8(m).
+
+
Elemental analysis (%): calcd for (C H N O ) C: 73.93, H:
2
2
19 3 2
X-ray crystallography
5
.36, N: 11.76 (%); found C: 73.82, H: 35.31, N: 11.83.
Synthesis of complexes 1–3. A mixture of MnX (X = OAc ,
−
2
Single-crystal XRD data for compounds L-MOM, 1, 2 and 3
were all collected on a Bruker APEX area-detector X-ray
diffractometer with Mo-Kα radiation (λ = 0.71073 Å) or Cu-Kα
radiation (λ = 1.54178 Å). The empirical absorption correction
was applied by using the SADABS program (G. M. Sheldrick,
SADABS, program for empirical absorption correction of area
detector data; University of Göttingen, Göttingen, Germany,
−
−
Cl , NO , 0.02 mmol), L-MOM (0.04 mmol), H O (0.2 mL),
3
2
and MeOH (2 mL) in a capped vial was heated at 80 °C for one
day. Yellow block-like crystals of 1–3 suitable for single-crystal
X-ray diffraction were collected, washed with ether and dried
in air. The products were not significantly affected by a change
in the molar ratio of Mn(II) and L-MOM (1 : 1, 2 : 1 or 1 : 2).
Yield: 1, 10.8 mg, 78%; 2, 10.9 mg, 80%; 3, 11.6 mg, 81%.
1996). The structure was solved using direct methods, and
2
Elemental analysis data and IR of [Mn
Calcd for C120 Mn : C, 69.46; H, 4.27; N, 12.15.
Found: C, 69.32; H, 4.36; N, 12.08. FTIR (KBr pellet): 3443.6(s),
3 6 2
L ·2H O] (1). Anal (%).
refined by full-matrix least-squares on F (G. M. Sheldrick,
SHELXTL97, program for crystal structure refinement, University
of Göttingen, Germany, 1997). Crystal data and details of the
data collection are given in Table 1, whereas the selected bond
distances and angles are presented in Tables S1–3.† The CCDC
numbers of L-MOM, 1, 2 and 3 are 972562, 972563, 972564,
and 972565, respectively.
H
88
N
18
O
8
3
1
1
1
7
743.5(w), 1597.0(s), 1550.1(s), 1515.3(s), 1414.5(s), 1384.2(s),
376.2(s), 1335.6(m), 1320.7(m), 1276.0(m), 1218.8(w),
109.3(m), 1027.4(m), 1003.5(w), 833.8(m), 802.8(w), 760.3(w),
46.5(w), 657.6(m), 584.8(m), 513.0(m), 471.7(m).
Elemental analysis data and IR of [MnL
2
] (2). Anal (%). Calcd
for C H N O Mn: C, 70.69; H, 4.15; N, 12.37. Found: C,
4
0
28 6 2
7
1
1
1
7
0.50; H, 4.22; N, 13.32. FTIR (KBr pellet): 3445.2(s), 1595.3(s),
543.9(s), 1513.7(s), 1439.7(s), 1421.0(s), 1384.4(s), 1366.16(s),
332.6(m), 1275.1(m), 1218.6(w), 1184.7(w), 1106.26(m), In summary, three Mn(II) coordination polymers with different
068.1(w), 1006.6(m), 833.8(m), 804.49(w), 758.0(w), 744.9(w), structures were prepared under solvothermal conditions, using
22.5(w), 683.0(w), 655.9(w), 584.4(m), 511.4(w).
Conclusion
−
−
−
Mn(II) salts (different counteranions: OAc , Cl , and NO )
3
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and a bispyridyl-based quinolinate ligand synthesized from
the cheap commercially available 8-hydroxyquinaldine. In the
solid state, the polymers 1–3 show a structural diversification
and fabricate one 2D supramolecular structure, one rhombo-
hedral grid structure, and 3D non-porous structure in response
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−
−
−
3
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Mn(II) polymers exhibit disparate magnetic properties due to
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Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (no. 21201002 and 21271006),
Anhui Provincial Natural Science Foundation (1308085QB22).
Provincial natural science research program of higher edu-
cation institutions of Anhui province (KJ2013Z028), Anhui Pro-
vincial Science Foundation for Outstanding Young Talent
(2012SQRL187), National Training Programs of Innovation and
Entrepreneurship for Undergraduates (201210360087). The
Natural Science Foundation of High Learning Institutions of
Anhui Province (KJ2012ZD11).
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Dalton Trans., 2014, 43, 9777–9785 | 9785