Pillaring role of 4,4′-azobis(pyridine) in substituted malonate-containing manganese(II) complexes: Syntheses, crystal structures, and magnetic properties

Article abstract of DOI:10.1021/cg300670a

Six new manganese(II) complexes of formulas [Mn₂(Rmal) ₂(H₂O)₂(azpy)]_n (1-3), [Mn(Phmal)(H₂O)(azpy)]_n (4), [Mn₂(Et ₂mal)₂(H₂O)₄(azpy)₂] _n (5), and [Mn(Bzmal)(H₂O)₃(azpy)] (6) [azpy = 4,4′-azobispyridine (1-6), Rmal = methylmalonate (Memal) (1), dimethylmalonate (Me₂mal) (2), and butylmalonate (Butmal) (3), Phmal = phenylmalonate (4), Et₂mal = diethylmalonate (5), and Bzmal = benzylmalonate (6)] were synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1-3 are three-dimensional compounds whose structure consists of corrugated layers of manganese(II) linked through syn-anti carboxylate (Rmal) bridges, which are pillared through the bis-monodentate azpy molecule. Complex 4 has a layered structure of manganese(II) ions connected by carboxylate (Phmal) bridges in the syn-anti coordination mode as in 1-3, the azpy group acting here as a terminally bound monodentate ligand. The structure of 5 consists of Et₂mal-Mn(II) neutral chains linked through the azpy ligand, giving rise to a complex three-dimensional network. Complex 6 is constituted by neutral [Mn(Bzmal)(H ₂O)₃(azpy)] mononuclear units, which are interlinked through O-H???O, O-H???N, and π-π type intermolecular interactions to afford a three-dimensional supramolecular structure. The topological analysis of these crystallographic structures shows the occurrence of four different nets: a (3,4)-connected InS-type (1-3), a binodal layered hcb (4), a uninodal CdS-type (5), and a (4,5)-connected tcs topology (6). The magnetic properties of 1-5 were investigated in the 2.0-300 K temperature range. Overall antiferromagnetic behavior occurs in 1-4 with susceptibility maxima in the range 2.8-5.5 K, the exchange pathway being provided by the syn-anti carboxylate (substituted malonate) bridge [manganese-manganese separation in the range 5.4365(3)-5.5274(1) A]. Very weak antiferromagnetic interactions are observed in 5 through the trans-bis-monodentate Et₂mal ligand, the intrachain manganese-manganese separation being 7.328(3) A. The much larger manganese-manganese separation through the bis-monodentate azpy ligand in 1-5 (values greater than 13.5 A) accounts for the lack of any significant magnetic interaction though this extended bridge.

Full text of DOI:10.1021/cg300670a

Article
pubs.acs.org/crystal
Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-
Containing Manganese(II) Complexes: Syntheses, Crystal Structures,
and Magnetic Properties
Mariadel Deniz,† Irene Hernandez-Rodríguez,† Jorge Pasan,*,† Oscar Fabelo,†,§,∥
́
́
́
Laura Canadillas-Delgado,†,§,‡ Consuelo Yuste,⊥,∇ Miguel Julve,∇ Francesc Lloret,∇
̃
and Catalina Ruiz-Perez*,†
†Laboratorio de Rayos X y Materiales Moleculares (MATMOL), Departamento de Física Fundamental II, Facultad de Física,
́
Universidad de La Laguna, Avenida Astrofísico Francisco San
́
chez s/n, E-38204 La Laguna (Tenerife), Spain
§Instituto de Ciencia de Materiales de Aragon
́
, CSIC-Universidad de Zaragoza, C/Pedro Cerbuna 12, E-50009 Zaragoza, Spain
∥Institut Laue-Langevin, Grenoble, 6 rue Jules Horowitz, B.P. 156, 38042 Grenoble Cedex 9, France
⊥Physics Department, CEMDRX Rua Larga, Universidade de Coimbra, P-3004-516 Coimbra, Portugal
∇Departament de Química Inorgan
̀ ́ ́ ́
ica, Instituto de Ciencia Molecular (ICMol), C/Catedratico Jose Beltran no. 2, 46980 Paterna
(Valencia), Spain
S
* Supporting Information
ABSTRACT: Six new manganese(II) complexes of formulas
[Mn2(Rmal)2(H2O)2(azpy)]n (1−3), [Mn(Phmal)(H2O)-
(azpy)]n (4), [Mn2(Et2mal)2(H2O)4(azpy)2]n (5), and [Mn-
(Bzmal)(H2O)3(azpy)] (6) [azpy = 4,4′-azobispyridine (1−6),
Rmal = methylmalonate (Memal) (1), dimethylmalonate
(Me2mal) (2), and butylmalonate (Butmal) (3), Phmal =
phenylmalonate (4), Et2mal = diethylmalonate (5), and Bzmal =
benzylmalonate (6)] were synthesized and structurally charac-
terized by single-crystal X-ray diffraction. Complexes 1−3 are
three-dimensional compounds whose structure consists of
corrugated layers of manganese(II) linked through syn−anti carboxylate (Rmal) bridges, which are pillared through the bis-
monodentate azpy molecule. Complex 4 has a layered structure of manganese(II) ions connected by carboxylate (Phmal) bridges
in the syn−anti coordination mode as in 1−3, the azpy group acting here as a terminally bound monodentate ligand. The
structure of 5 consists of Et2mal−Mn(II) neutral chains linked through the azpy ligand, giving rise to a complex three-
dimensional network. Complex 6 is constituted by neutral [Mn(Bzmal)(H2O)3(azpy)] mononuclear units, which are interlinked
through O−H···O, O−H···N, and π−π type intermolecular interactions to afford a three-dimensional supramolecular structure.
The topological analysis of these crystallographic structures shows the occurrence of four different nets: a (3,4)-connected InS-
type (1−3), a binodal layered hcb (4), a uninodal CdS-type (5), and a (4,5)-connected tcs topology (6). The magnetic
properties of 1−5 were investigated in the 2.0−300 K temperature range. Overall antiferromagnetic behavior occurs in 1−4 with
susceptibility maxima in the range 2.8−5.5 K, the exchange pathway being provided by the syn−anti carboxylate (substituted
malonate) bridge [manganese−manganese separation in the range 5.4365(3)−5.5274(1) Å]. Very weak antiferromagnetic
interactions are observed in 5 through the trans-bis-monodentate Et2mal ligand, the intrachain manganese−manganese
separation being 7.328(3) Å. The much larger manganese−manganese separation through the bis-monodentate azpy ligand in
1−5 (values greater than 13.5 Å) accounts for the lack of any significant magnetic interaction though this extended bridge.
synthetic chemist with some degree of control over the
resultant architecture and properties.
In this sense, carboxylate ligands such as oxalate or malonate
(dianion of propanedioic acid, H2mal) have been frequently
used as linkers of metal ions3 because of their good complexing
ability and also the capability of the carboxylate bridges to
INTRODUCTION
■
Design and synthesis of new coordination polymers, or metal−
organic frameworks (MOFs), have been developing greatly in
the past decade.1 These kinds of complexes, which are
constructed from a metal ion and polynuclear motifs assembled
by organic linkers, are of special relevance due to the variety of
new topologies that they can give rise and also to their potential
applications as multifunctional materials in catalysis, optoelec-
tronics, and luminescent or magnetic devices.2 An appropriate
choice of the suitable molecular building blocks can provide the
Received: May 16, 2012
Revised: July 30, 2012
Published: July 30, 2012
© 2012 American Chemical Society
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Article
Elemental analyses (C, H, and N) were performed on an EA 1108
CHNS-O microanalytical analyzer of the SEGAI service of the
University of Laguna (Tenerife).
mediate magnetic interactions whose magnitude and nature are
dependent on the anti−anti, syn−anti, or syn−syn coordination
modes that they can adopt.4 The number and symmetry of the
magnetic orbitals of the spin carriers together with their
possible overlap through this bridging ligand account for the
ferro- or antiferromagnetic nature of the magnetic coupling
observed in them.5,6
Synthesis of [Mn2(Rmal)2(H2O)2(azpy)]n [Rmal = Memal (1),
Me2mal (2) and Butmal (3)], [Mn(Phmal)(H2O)(azpy)]n (4),
[Mn2(Et2mal)2(H2O)4(azpy)2]n (5) and [Mn(Bzmal)(H2O)3(azpy)]
(6). Complexes 1−6 were obtained by slow diffusion in a test tube
through the following procedure: An aqueous solution (9 cm3)
containing the substituted-malonic acid [0.5 mmol, 59 (1), 66 (2), 80
(3), 90 (4), 80 (5), and 97 mg (6)], manganese(II) chloride
tetrahydrate (0.5 mmol, 99 mg), and sodium carbonate (0.5 mmol, 53
mg) was placed at the bottom of a test tube, and an interface of water/
ethanol (50%, 7 cm3) was added dropwise. Then an ethanolic solution
of azpy (0.5 mmol, 92 mg) was dropped slowly on the interface. The
tube was covered with parafilm and left at room temperature. X-ray
quality crystals as orange prisms were grown at the interface after a few
days. Yield ca. 78 (1), 75 (2), 73 (3), 68 (4), 72 (5), and 64% (6).
Anal. Calcd for C9H10MnN2O5 (1): C, 38.43; H, 3.59; N, 9.97. Found:
C, 38.44; H, 3.24; N 9.93%. Anal. Calcd for C10H12MnN2O5 (2): C,
40.68; H, 4.10; N, 9.49. Found: C, 40.39; H, 4.16; N, 9.41%. Anal.
Calcd for C12H12MnN2O5 (3): C, 45.14; H, 3.79; N, 8.78. Found: C,
45.39; H, 3.65; N, 8.62%. Anal. Calcd for C19H16MnN4O5 (4): C,
52.41; H, 3.71; N, 12.87. Found: C, 52.15; H, 3.67; N, 12.63%. Anal.
Calcd for C34H44Mn2N8O5 (5): C, 54.10; H, 5.88; N, 14.85. Found: C,
54.64; H, 5.36; N, 14.54%. Anal. Calcd for C20H22MnN4O7 (6): C,
49.48; H, 4.57; N, 11.55. Found: C, 49.44; H, 4.32; N, 11.81%.
Selected IR peaks (KBr, cm−1): 3205w, 1562vs, 1443 m, 1335s, 840 m,
694s (1); 3236w, 1547vs, 1434 m, 1327s, 841 m, 667s (2); 3248w,
1551vs, 1443 m, 1339s, 837 m, 667s (3); 3217w, 1566s, 1412 m, 1315
m, 837 m, 706s (4); 3302w, 1539 m, 1416 m, 1312 m, 841 m, 667 m
(5); 3368w, 1601vs, 1420 m, 1327s, 841 m, 698s (6).
Physical Techniques. IR spectra were recorded on a Bruker IF
S66 spectrophotometer with an ATR module for solid samples over
the range 4000−500 cm−1. The thermogravimetric analyses were
performed on a Perkin-Elmer Pyris Diamond, TGA/DTA equipment.
Samples were heated in Al2O3 crucibles from 25 to 500 °C in flowing
N2 atmosphere with a heating rate of 5 °C min−1. Magnetic
susceptibility measurements on polycrystalline samples of compounds
1−5 were carried out in the temperature range 2.0−300 K with a
Quantum Design SQUID magnetometer under applied dc magnetic
field of 1 T (15 ≤ T ≤ 300 K) and 1000 G (2 ≤ T ≤ 15 K) (1), 1 T
(15 ≤ T ≤ 300 K) and 250 G (2 ≤ T ≤ 15 K) (2), 1 T (30 ≤ T ≤ 300
K), 3000 G (15 ≤ T ≤ 30 K), and 100 G (2 ≤ T ≤ 15 K) (3), 1 T (15
≤ T ≤ 300 K) and 250 G (2 ≤ T ≤ 15 K) (4), and 1 T (50 ≤ T ≤ 300
K) and 1000 G (2 ≤ T ≤ 50 K) (5). Diamagnetic corrections of the
constituent atoms were estimated from Pascal’s constants:14 −135 ×
10−6 (1), −146 × 10−6 (2), −171 × 10−6 (3), −223 × 10−6 (4), and
−234 × 10−6 cm3 mol−1 (5) [per one manganese(II) ion].
Experimental susceptibilities were also corrected for the magnetization
of the sample holder (a plastic bag).
Rigid carboxylate type ligands such as oxalate or benzene-1,4-
dicarboxylate have been extensively used since they allow a
priori a quite good prediction of the resulting crystal structure
and spin topology. However, MOFs based on more flexible
spacers have been less developed due to their greater versatility
as ligands. An example of this more complex situation is
represented by the malonate dianion, which can not only act as
a terminally bound monodentate or bidentate ligand but also
adopt several bridging modes through its carboxylate groups.5j,7
At first sight, subtle modifications at the methylene carbon of
the malonate group could be a suitable strategy to exert some
control over the coordination modes of the modified malonate
and also on the intermolecular interactions.8 In this respect, the
influence that the alkyl or aryl substituents would exert on the
solubility in polar and nonpolar solvents of the resulting
modified malonate, the electron donor or acceptor effects, the
hydrophobic character and, finally, the possibility of additional
intermolecular interactions and new coordination modes
deserves to be outlined.
The introduction of a coligand in the metal assembling with
substituted malonate would contribute to the interconnection
or isolation of the spin carriers as a function of its bridging or
blocking character. A rod-like spacer such as the 4,4′-
azobispyridine (azpy) seems a good choice aimed at designing
high-dimensional structures with substituted malonate-contain-
ing complexes. This rigid N-donor ligand has two coordination
sites involving the pyridyl-nitrogen atoms, and it can act as a
bridging ligand either in trans or in cis modes. The possibility of
π···π9 and C−H/π10 type intermolecular interactions between
the azpy ligand and the alkyl or aryl groups of the substituted
malonate could play a significant structural role and even
modify the final network.11 Only one complex combining the
malonate and the azpy ligand of formula [Cu(mal)(H2O)-
(azpy)1/2]·H2O has been previously reported.12 Its structure
consists of syn−anti malonate-bridged copper(II) chains, which
are linked through azpy to build a two-dimensional network
where ferro- (intrachain) and antiferromagnetic (interchain)
interactions coexist.
X-ray Data Collection and Structure Determination. Data
collection of 1 and 4 were carried out on a Bruker-Nonius KappaCCD
diffractometer, and the crystallographic data were collected at 293(2)
K using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å),
while data for complex 3 were measured on an Agilent SuperNova X-
ray source at the same temperature using Cu Kα radiation (λ =
1.54184 Å). Single crystals of 2, 5, and 6 were measured at the BM16
beamline in the ESRF synchrotron facilities (Grenoble, France) with λ
= 0.7380 Å at 100(2) K. The data were indexed, integrated, and scaled
with the EVALCCD15 software (1−4), CrysAlis PRO16 (3), and
HKL200017 (2, 5, and 6) programs. The crystal structures of 1, 5, and
6 were solved by direct methods by using the SHELXS-97 package,18
while those of 2−4 were solved using the SIR92 software.19 The
structures were refined with the full-matrix least-squares technique on
F2 with SHELXL-97 programs18 included in the WINGX20 software
package. All non-hydrogen atoms were refined anisotropically. The
hydrogen atoms of the organic ligands in 1−6 were set on geometrical
positions and refined with a riding model. Those of the coordinated
water molecules were located from Fourier differences and refined
with isotropic thermal factors, except for 5 where the hydrogen atoms
In the present work, we present a magnetostructural study of
six new manganese(II) complexes of different dimensionality
with formulas [Mn2(R-mal)2(H2O)2(azpy)]n (1−3), [Mn-
(Phmal)(H2O)(azpy)]n (4), [Mn2(Et2mal)2(H2O)4(azpy)2]n
(5), and [Mn(Bzmal)(H2O)3(azpy)] (6) [Rmal = methyl-
malonate (Memal) (1), dimethylmalonate (Me2mal) (2), and
butylmalonate (Butmal) (3), Phmal = phenylmalonate (4),
Et2mal = diethylmalonate (5), and Bzmal = benzylmalonate
(6)], which result from the metal assembling with alkyl/aryl-
substituted malonate and azpy as ligands.
EXPERIMENTAL SECTION
■
Materials. The malonic acid derivatives, H2Memal, H2Me2mal,
H2Butmal, H2Phmal, H2Et2mal, and H2Bzmal, MnCl2·4H2O, Na2CO3,
and ethanol were purchased from commercial sources and used
without further purification. The azpy molecule was synthesized by
following the previously reported procedure, which consists of the
oxidation of 4-aminopyridine with a solution of sodium hypochlorite.13
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Table 1. Crystallographic Data for Complexes 1−6
1
2
3
4
5
6
formula
FW
C9H10MnN2O5
281.13
C10H12MnN2O5
295.16
C12H12MnN2O5
319.18
C19H16MnN4O5
435.30
C34H40Mn2N8O12
862.62
C20H22MnN4O7
485.36
cryst syst
space group
a (Å)
monoclinic
P21/n
monoclinic
P21/n
orthorhombic
Pnnm
orthorhombic
Pnma
triclinic
triclinic
P1
̅
P1
̅
7.300(3)
7.4740(15)
21.371(4)
7.5710(15)
7.2570(3)
25.9657(10)
7.5506(3)
37.055(2)
7.3447(6)
7.3447(5)
12.947(3)
13.527(3)
14.019(3)
92.85(3)
114.30(3)
112.22(3)
2009.2(7)
2
5.9390(12)
10.612(2)
16.723(3)
80.24(3)
89.46(3)
84.87(3)
1034.5(4)
2
b (Å)
20.927(10)
7.5480(7)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
91.40(2)
90.12(3)
1152.8(8)
4
1209.3(4)
4
1422.78(10)
4
1998.9(2)
4
μ(Mo Kα) (cm−1
)
1.156
1.218
7.746
0.698
0.697
0.759
T (K)
293(2)
100(2)
293(2)
293(2)
100(2)
100(2)
ρcalc (g cm−3
λ (Å)
)
1.620
1.621
1.490
1.446
1.426
1.558
0.71073
−9 ≤ h ≤ 6
−27 ≤ k ≤ 26
−9 ≤ l ≤ 9
2610 (0.0381)
1960
0.73800
−9 ≤ h ≤ 9
−27 ≤ k ≤ 27
−9 ≤ l ≤ 9
2632 (0.0676)
2238
1.54184
−8 ≤ h ≤ 9
−32 ≤ k ≤ 28
−8 ≤ l ≤ 9
1563 (0.0438)
1370
0.71073
−47 ≤ h ≤ 47
−9 ≤ k ≤ 9
−9 ≤ l ≤ 6
2464 (0.0580)
1824
0.73800
−16 ≤ h ≤ 16
−17 ≤ k ≤ 17
−17 ≤ l ≤ 17
7749 (0.0464)
5416
0.73800
−7 ≤ h ≤ 7
−12 ≤ k ≤ 13
−21 ≤ l ≤ 21
4244 (0.0690)
4049
index ranges
indep reflns (Rint)
obsd reflns [I > 2σ(I)]
params
162
209
117
173
511
314
GOF
1.110
1.085
1.142
1.125
1.258
1.047
R [I > 2σ(I)]
Rw [I > 2σ(I)]
R (all data)
0.0566
0.0583
0.0793
0.0797
0.1072
0.0670
0.0943
0.1622
0.2326
0.2268
0.2967
0.1840
0.0854
0.0653
0.0863
0.1068
0.1291
0.0683
Rw (all data)
0.1025
0.1702
0.2403
0.2418
0.3212
0.1855
could not be found. The refinement indices in 5 are slightly high, and
large values for the anisotropic displacement parameters of the diethyl
groups of the Et2mal ligand are observed although 5 was measured in a
synchrotron beamline at 100 K. The final geometrical calculations and
the graphical manipulations were carried out with the PLATON21 and
DIAMOND22 programs. The topology of these complexes has been
determined by using the TOPOS software package.23 A summary of
the crystallographic data and structure refinement is given in Table 1.
Selected bond distances and angles together with the hydrogen bonds
are listed in Tables 2 (1−3), 3 (4), 4 (5), and 5 (6), while the C−
H···π (complexes 2−4) and π−π interactions (complexes 5 and 6) are
shown in Tables 6 (2−4) and 7 (5 and 6). Crystallographic data
(excluding structure factors) for the compounds 1−6 have been
deposited at the Cambridge Crystallographic Data Centre with CCDC
reference numbers 878821 (1), 878822 (2), 878823 (3), 878824 (4),
878825 (5), and 878826 (6).
Å (3), whereas the shortest interlayer metal−metal distances
are 9.409(4) (1), 9.724(2) (2), and 11.337(2) Å (3). Two
features are responsible for this intermetallic shortening: (i) the
corrugation of the layers [the values of the dihedral angle
between the involved equatorial planes being 88.69(4) (1),
83.79(2) (2), and 82.77(5)° (3)], and (ii) the angle subtended
by the azpy ligand and the normal to the planes [48.017(5) (1),
45.459(2) (2), and 34.673(5)° (3)]. These two parameters are
correlated: the smaller the corrugation angle is, the lower the
angle between the azpy ligand and the normal to the plane, and
the greater the interlayer distance. The interlayer distance in
complex 3 is limited by the butyl group, not by the azpy ligand
as in 1 and 2, and this accounts for the greater interlayer Mn−
Mn distance exhibited in 3.
There are no π−π interactions in 2 and 3 since the shortest
centroid−centroid distances between adjacent aromatic rings
are much longer than those expected between the pyridyl rings
for this type of interaction [values in the range 5.223(3)−
8.075(2) Å for 2 and a value of 7.551(3) Å for 3], but they
occur in 1 [centroid−centroid distance of 4.472(2) Å with an
offset angle of 32.15(13)°].10 C−H/π type intermolecular
interactions are discarded in 1 since the shortest hydrogen−
centroid distance is 3.9124(6) Å, a value that is longer than the
average one for this type of interaction between C−H and
C(π).11 However, these interactions occur in 2 and 3, where
the shortest hydrogen−centroid distances are 3.18(4) and
3.17(3) Å (2) and 3.12(2) Å (3) (Table 6). Moreover, there
are several intralayer hydrogen bonds in these three complexes
between the coordinated water molecule and the oxygen atoms
of the carboxylate bridges (Table 2).
RESULTS AND DISCUSSION
■
Description of the Structures. [Mn2(Rmal)2(H2O)2-
(azpy)]n [Rmal = Memal (1), Me2mal (2), and Butmal (3)].
Complexes 1−3 are three-dimensional isostructural compounds
whose structure consists of [63] corrugated layers of
manganese(II) ions with substituted malonate groups growing
in the ac plane, which are pillared by bis-monodentate azpy
ligands (Figures 1−4) leading to a topology of a 3,4-binodal net
with a Schlafli symbol [63][658] ins net24,25 (Figure 5). The
̈
manganese atoms within each layer are connected by syn−anti
carboxylate (from the substituted malonate) bridges. The same
net has been reported in previous studies with other rod-like N-
donor coligands.8b,26 The aliphatic skeleton of the substituted
malonate ligand is located alternatively above and below these
layers, inversely to the position of the azpy molecule. The
values of the manganese−manganese separation across the
bridging azpy are 13.562(4) (1), 13.583(2) (2), and 13.588(2)
Each manganese atom in 1−3 is six-coordinated in a
somewhat distorted octahedral environment (Figure 4) with
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Article
a
Table 2. Selected Bond Lengths (Å) and Angles (deg) and Hydrogen Bonds in 1−3
1
Mn(1)−O(2)
Mn(1)−O(4)
Mn(1)−O(1a1)
Mn(1)−O(3b1)
Mn(1)−O(1W)
Mn(1)−N(1)
2.175(2)
2.147(2)
2.174(2)
2.150(2)
2.226(3)
2.290(3)
82.49(9)
O(2)−Mn(1)−O(1a1)
O(2)−Mn(1)−O(3b1)
O(4)−Mn(1)−O(1a1)
O(4)−Mn(1)−O(3b1)
O(1a1)−Mn(1)−O(3b1)
O(2)−Mn(1)−O(1W)
O(2)−Mn(1)−N(1)
170.32(10)
85.19(10)
88.17(10)
167.34(9)
104.00(10)
94.01(10)
91.45(11)
O(4)−Mn(1)−O(1W)
O(4)−Mn(1)−N(1)
92.15(10)
88.56(11)
88.84(10)
85.77(10)
91.57(10)
88.89(11)
174.54(11)
O(1a1)−Mn(1)−O(1W)
O(1a1)−Mn(1)−N(1)
O(3b1)−Mn(1)−O(1W)
O(3b1)−Mn(1)−N(1)
O(1W)−Mn(1)−N(1)
O(2)−Mn(1)−O(4)
2
Mn(1)−O(2)
Mn(1)−O(4)
Mn(1)−O(1c1)
Mn(1)−O(3a1)
Mn(1)−O(1W)
Mn(1)−N(1)
2.160(2)
2.162(2)
2.171(2)
2.166(2)
2.216(2)
2.279(3)
82.05(9)
O(2)−Mn(1)−O(1c1)
O(2)−Mn(1)−O(3a1)
O(4)−Mn(1)−O(1c1)
O(4)−Mn(1)−O(3a1)
O(1c1)−Mn(1)−O(3a1)
O(2)−Mn(1)−O(1W)
O(2)−Mn(1)−N(1)
169.60(10)
88.71(9)
O(4)−Mn(1)−O(1W)
O(4)−Mn(1)−N(1)
97.92(10)
89.79(12)
88.06(9)
88.53(9)
O(1c1)−Mn(1)−O(1W)
O(1c1)−Mn(1)−N(1)
O(3a1)−Mn(1)−O(1W)
O(3a1)−Mn(1)−N(1)
O(1W)−Mn(1)−N(1)
169.77(10)
100.31(10)
97.54(10)
89.61(11)
85.95(12)
87.61(9)
85.74(12)
170.12(11)
O(2)−Mn(1)−O(4)
3
Mn(1)−O(2)
Mn(1)−O(1g1)
Mn(1)−O(1W)
Mn(1)−N(1)
O(2)−Mn(1)−O(1g1)
D−H···A
2.150(4)
2.157(4)
2.218(5)
2.288(6)
171.6(2)
O(2)−Mn(1)−O(1d1)
O(2)−Mn(1)−O(2f1)
O(1g1)−Mn(1)−O(1d1)
O(2)−Mn(1)−O(1W)
90.3 (2)
81.6(2)
97.8(2)
92.1(2)
O(2)−Mn(1)−N(1)
O(1g1)−Mn(1)−O(1W)
O(1g1)−Mn(1)−N(1)
O(1W)−Mn(1)−N(1)
91.4(2)
90.33(14)
86.6(2)
175.4(2)
D−H (Å)
H···A (Å)
D···A (Å)
D−H···A (deg)
1
2
3
O(1W)−H(1WB)···O(2a1)
O(1W)−H(1WA)···O(4b1)
0.87(2)
0.88(2)
1.91(3)
1.86(2)
2.730(3)
2.711(3)
157(5)
161(4)
O(1W)−H(1WB)···O(2c1)
O(1W)−H(1WA)···O(4a1)
0.90(2)
0.90(2)
1.88(2)
1.89(3)
2.743(3)
2.735(3)
161(4)
156(4)
O(1W)−H(1WB)···O(2d1)
0.89(2)
1.91(4)
2.730(4)
152(7)
a
Symmetry code: (a1) = x + 1/2, −y + 1/2, z − 1/2; (b1) = x + 1/2, −y + 1/2, z + 1/2; (c1) = x − 1/2, −y + 1/2, z − 1/2; (d1) = x + 1/2, −y + 3/2,
−z + 3/2; (f1) = x, y, −z + 2; (g1) = x + 1/2, −y + 3/2, z + 1/2.
a
Table 3. Selected Bond Lengths (Å) and Angles (deg) and Hydrogen Bonds for 4
4
Mn(1)−O(2)
2.153(3)
2.153(3)
2.153(3)
2.153(3)
2.248(5)
Mn(1)−N(1)
2.276(6)
O(1d4)−Mn(1)−O(2c4)
O(1d4)−Mn(1)−O(1a4)
O(1d4)−Mn(1)−O(1W)
O(1d4)−Mn(1)−N(1)
O(1W)−Mn(1)−N(1)
D···A (Å)
89.99(14)
98.1(2)
Mn(1)−O(2c4)
Mn(1)−O(1a4)
Mn(1)−O(1d4)
Mn(1)−O(1W)
O(2)−Mn(1)−O(1a4)
O(2)−Mn(1)−O(1W)
O(2)−Mn(1)−N(1)
O(2)−Mn(1)−O(2c4)
D−H (Å)
89.99(14)
90.25(14)
91.71(16)
81.87(19)
91.68(13)
86.63(14)
177.4(2)
D−H···A
O(1W)−H(1WA)···O(2a4)
H···A (Å)
1.83(2)
D−H···A (deg)
165(5)
0.89(2)
2.703(4)
a
Symmetry code: (a4) = −x + 3/2, −y, z + 1/2; (b4) = −x + 2, y − 1/2, −z; (c4) = x, −y + 1/2, z; (d4) = −x + 3/2, y + 1/2, z + 1/2.
distortion parameters s/h and ϕ of 1.194 and 51.96° (1), 1.221
and 50.62° (2), and 1.234 and 53.39° (3) (the values for an
ideal octahedron being s/h = 1.22 and ϕ = 60°).27 The
equatorial plane is built by four carboxylate-oxygen atoms
[O(1), O(2), O(3), and O(4) for 1 and 2 and O(1), O(2), and
the symmetry-related atoms for 3], with average values for the
Mn−O bond distance of 2.162(2) (1), 2.165(2) (2), and
2.153(4) (3) Å. The axial positions are filled by a nitrogen atom
of the azpy ligand [N(1)] and a coordinated water molecule
[O(1W)], the Mn−O1W bond length being shorter [values
covering the narrow range 2.216(2)−2.226(3) Å] than the
Mn−N bond distance [2.279(3)−2.290(3) Å].
and through O(2) and O(2f1) (3) [values of the bite angle of
82.48(9)° (1), 82.051(3)° (2), and 81.58(13)° (3); symmetry
code (f1) = x, y, −z + 2] and as bis-monodentate through O(1)
toward Mn(1h1) (1), Mn(1b1) (2), or Mn(1e1) (3) and
through O(3) toward Mn(1c1) (1) and Mn(1h1) (2)
[symmetry codes (b1) = x + 1/2, −y + 1/2, z + 1/2; (c1) =
x − 1/2, −y + 1/2, z − 1/2; (e1) = x − 1/2, −y + 3/2, −z + 3/
2; (h1) = x − 1/2, −y + 1/2, z + 1/2]. The metal−metal
separation across the syn−anti carboxylate bridges [through
O(1) and O(3) toward two adjacent equatorial positions] are
5.5274(15) and 5.4047(14) Å (1), 5.4486(15) and 5.4592(15)
Å (2), and 5.4898(11) Å (3).
The substituted malonate ligand in 1−3 adopts the μ3-
κO:κO′:κO″:κO‴ coordination mode acting simultaneously as
bidentate through O(2) and O(4) toward Mn(1) (1 and 2)
The azpy ligand in 1−3 exhibits the bis-monodentate
coordination mode acting as linker of adjacent parallel neutral
layers. The aromatic rings of the N-donor ligand are coplanar
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a
Table 4. Selected Bond Lengths (Å) and Angles (deg) and Hydrogen Bonds for 5
5
Mn(1)−O(2)
Mn(1)−O(1W)
Mn(1)−N(1)
2.148(3)
2.155(3)
2.303(4)
89.47(12)
Mn(2)−O(3)
Mn(2)−O(2W)
Mn(2)−N(3)
2.163(3)
2.150(4)
2.314(4)
89.39(14)
Mn(3)−O(6)
Mn(3)−O(3W)
Mn(3)−N(5)
2.192(3)
2.183(3)
2.309(3)
Mn(4)−O(8)
Mn(4)−O(4W)
Mn(4)−N(7)
2.197(3)
2.168(3)
2.297(4)
O(2)−Mn(1)−
O(3)−Mn(2)−O(2W)
O(6)−Mn(3)−O(3W) 92.98(13)
O(8)−Mn(4)−O(4W) 92.16(12)
O(1W)
O(2)−Mn(1)−N(1)
O(2)−Mn(1)−O(2l5)
92.11(13)
180.00(9)
90.53(12)
O(3)−Mn(2)−N(3)
O(3)−Mn(2)−O(3m5)
92.59(14)
180.0
O(6)−Mn(3)−N(5)
O(6)−Mn(3)−O(6c5)
90.15(13)
O(8)−Mn(4)−N(7)
90.74(14)
180.000(1)
87.84(12)
180.00(17) O(8)−Mn(4)−O(8e5)
87.02(13)
O(2)−Mn(1)−
O(3)−Mn(2)−
90.61(14)
O(6)−Mn(3)−
O(8)−Mn(4)−
O(4We5)
O(1Wl5)
O(2Wm5)
O(3Wc5)
O(1W)−Mn(1)−
O(1Wl5)
180.0
O(2W)−Mn(2)−
O(2Wm5)
180.000(1) O(3W)−Mn(3)−
O(3Wc5)
180.000(1) O(4W)−Mn(4)−
O(4We5)
180.000(1)
O(1W)−Mn(1)−
90.88(16)
O(2W)−Mn(2)−N(3)
91.32(18)
O(3W)−Mn(3)−N(5) 91.35(13)
O(4W)−Mn(4)−N(7) 91.02(14)
N(1)
O(2l5)−Mn(1)−N(1)
87.89(13)
89.12(16)
O(3m5)−Mn(2)−N(3)
87.41(14)
88.68(18)
O(6c5)−Mn(3)−N(5)
89.85(13)
88.65(13)
O(8e5)−Mn(4)−N(7)
89.26(14)
88.98(14)
O(1Wl5)−Mn(1)−
O(2Wm5)−Mn(2)−
O(3Wc5)−Mn(3)−
O(4We5)−Mn(4)−
N(1)
N(3)
N(5)
N(7)
N(1)−Mn(1)−N(1l5)
180.000(1) N(3)−Mn(2)−N(3m5)
180.000(1) N(5)−Mn(3)−N(5c5)
D···A
180.000(1) N(7)−Mn(4)−N(7e5)
180.000(1)
D···A
D···A (Å)
D···A (Å)
O(1W)···O(1)
O(1W)···O(5a5)
O(2W)···O(4)
O(2W)···O(7b5)
2.600(8)
2.646(8)
2.620(5)
2.630(6)
O(3W)···O(5c5)
O(3W)···O(4d5)
O(4W)···O(7e5)
O(4W)···O(1f5)
2.635(5)
2.701(7)
2.638(7)
2.665(6)
a
Symmetry code: (a5) = x − 1, y − 1, z; (b5) = x, y − 1, z; (c5) = −x + 1, −y + 3, −z; (d5) = x, y + 1, z; (e5) = −x + 2, −y + 3, −z + 1; (f5) = x + 1, y
+ 1, z; (l5) = −x, −y + 1, −z; (m5) = −x + 1, −y + 1, −z + 1.
a
Table 5. Selected Bond Lengths (Å) and Angles (deg) and Hydrogen Bonds for 6
6
Mn(1)−O(2)
Mn(1)−O(4)
Mn(1)−O(2W)
Mn(1)−O(1W)
Mn(1)−O(3W)
Mn(1)−N(1)
O(2)−Mn(1)−O(4)
D−H···A
2.119(2)
2.154(2)
2.166(2)
2.189(2)
2.189(2)
2.296(2)
84.43(8)
O(2)−Mn(1)−N(1)
O(2)−Mn(1)−O(1W)
O(2)−Mn(1)−O(2W)
O(2)−Mn(1)−O(3W)
O(4)−Mn(1)−N(1)
O(4)−Mn(1)−O(1W)
O(4)−Mn(1)−O(2W)
D−H (Å)
174.53(8)
94.44(9)
92.22(9)
92.36(8)
90.41(9)
93.13(9)
94.39(9)
O(4)−Mn(1)−O(3W)
O(1W)−Mn(1)−N(1)
O(1W)−Mn(1)−O(2W)
O(1W)−Mn(1)−O(3W)
O(2W)−Mn(1)−N(1)
O(2W)−Mn(1)−O(3W)
O(3W)−Mn(1)−N(1)
D···A (Å)
176.24(7)
83.98(9)
170.40(8)
85.14(9)
90.00(9)
87.69(9)
92.72(9)
H···A (Å)
D−H···A (deg)
O(1W)−H(1WA)···O(3a6)
O(1W)−H(1WB)···O(3b6)
O(2W)−H(2WA)···O(2c6)
O(3W)−H(3WA)···O(1c6)
O(3W)−H(3WB)···O(4a6)
O(2W)−H(2WB)···N(4d6)
0.88(2)
0.89(2)
0.89(4)
0.90(2)
0.89(2)
0.89(2)
1.80(2)
1.87(2)
1.85(4)
1.78(2)
1.93(3)
1.97(2)
2.667(3)
2.746(3)
2.729(3)
2.682(3)
2.799(3)
2.847(3)
168(4)
170(4)
170(4)
173(6)
165(6)
166(4)
a
Symmetry code: (a6) = x − 1, y, z; (b6) = −x + 1, −y, −z + 1; (c6) = −x, −y + 1, −z + 1; (d6) = −x + 1, −y + 1, −z.
a
a
Table 6. C−H···π-type Interactions in 2−4
Table 7. π−π-type Interactions Present in 5 and 6
C−H
H···π
(Å)
C−H···π
centroid−centroid
offset angle
(deg)
dihedral angle
(deg)
C−H···π
(Å)
C···π (Å)
(deg)
distance (Å)
2
5
C(5)−H(5B)···π(2a1)
C(19)−H(19)···π(1a1)
0.98(3)
0.98(3)
3.18(4)
3.17(3)
3.883(2)
3.874(2)
130(3)
130(2)
π(1)···π(2)
π(3)···π(4)
π(4)···π(2g5)
π(1)···π(3h5)
4.039(2)
28.96(11)
30.51(11)
34.69(10)
35.63(12)
6.6(2)
5.3(2)
6.1(2)
6.2(2)
4.092(2)
3
4
4.2636(10)
4.2763(10)
C(6)−H(6)···π(1e1)
0.96(2)
0.93(1)
3.12(2)
3.20(2)
3.953(9)
3.883(2)
146(2)
132(2)
6
C(18)−
π···π(d6)
3.5967(9)
18.86(2)
6.12(3)
H(18)···π(azpyb4)
a
Symmetry code: (g5) = −x + 1, −y + 2, −z + 1; (h3) = −x + 1, −y +
2, −z; (d6) = −x + 1, −y + 1, −z.
a
Symmetry code: (a1) = x + 1/2, −y + 1/2, z − 1/2; (e1) = x − 1/2,
−y + 3/2, −z + 3/2; (b4) = −x + 2, y − 1/2, −z.
positions in complex 2, with occupancy factors of 0.54 and 0.46
and an angle of 40.112(9)° between the aromatic rings.
[Mn(Phmal)(H2O)(azpy)]n (4). The structure of 4 consists of
[63] corrugated layers of manganese(II) ions with phenyl-
since the whole molecule is centrosymmetric due to the
presence of an inversion center located at the middle of the
inner NN bond. The azpy ligand is disordered between two
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Figure 2. Perspective views of the crystal packing of 1 along the
crystallographic a axis.
Figure 1. (a) A view of the Rmal−Mn(II) layers in 1−4, along the b
axis. (b) Detail of the [63] layer built through the syn−anti carboxylate
bridges where the yellow and black spheres represent the Mn(II) ions
and the Rmal ligand, respectively.
malonate groups growing in the ac plane as in 1−3 (Figure 1),
giving rise to a hcb-type Shubnikov hexagonal net.24,25e,28 The
manganese atoms within each layer are linked through
carboxylate (phenylmalonate) groups exhibiting the syn−anti
bridging. In contrast to what occurs in 1−3, the azpy molecule
in 4 acts as a terminally bound monodentate ligand and is
located alternatively above and below the layers, inversely to
the position of the phenyl group. No π−π type interactions
occur in 4 [the shortest centroid−centroid distance between
adjacent pyridyl rings being 5.8117(3) Å and minimum offset
angle 18.8(2)°]10 because the presence of intra- and interlayer
C−H/π interactions (Table 6) with values of hydrogen−
centroid distances of 3.20(2) Å11 precludes the parallel facing
between the aromatic rings and indeed leads to a three-
dimensional supramolecular network (Figure 6). Intralayer
hydrogen bonds between the axially bound water molecule
[O(1W)] and a carboxylate (phenylmalonate) oxygen [O-
(2a4)] also contribute to the stabilization of the structure (see
end of Table 3).
Figure 3. A view of the 3D structure of compound 1 along the
crystallographic c axis showing the corrugated layers of the carboxylate-
bridged manganese(II) ions linked through the bis-monodentate azpy
ligand.
equatorial bonds being shorter [average value for the Mn−O
bond length of 2.153(3) Å] than the axial ones [2.248(5) and
2.276(6) Å for Mn(1)−O(1W) and Mn(1)−N(1), respec-
tively].
The phenylmalonate ligand in 4 adopts the same μ3-
κO:κO′:κO″:κO‴ coordination mode than the Rmal ligands in
1−3: bidentate through O(2) and O(4) toward Mn(1) [the
Each manganese in 4 is six-coordinated in a distorted
octahedral environment (Figure 7) with values for s/h and ϕ of
1.231 and 54.20°.27 The equatorial plane is built by four
carboxylate-oxygen atoms [O(1), O(2), O(3), and O(4)],
while the axial positions are filled by a water molecule [O(1W)]
and a nitrogen atom from the azpy ligand [N(1)], the
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Figure 4. A view of a fragment of 1 (a), 2 (b), and 3 (c) showing the numbering scheme and the symmetry codes of each atom. The disorder of the
azpy ligand in 2 has been removed for clarity.
Figure 5. Topological representation of the three-dimensional ins
topology in 1−3 (the black and yellow spheres represent the Rmal
nodes and the Mn(II) ions, respectively).
Figure 7. A view of a fragment of the structure of 4 with the atom
numbering. The disorder of the azpy ligand has been removed for
clarity.
Figure 6. Views of the packing 4 along the crystallographic a axis
showing the C−H···π type interactions (blue dashed lines).
angle subtended at the manganese atom being 81.9(2)°] and
bis-monodentate through O(1) and O(1c4) toward Mn(1e4)
and Mn(1f4), respectively [symmetry codes (e4) = −x + 3/2,
−y, z − 1/2; (f4) = −x + 3/2, −y + 1, z − 1/2]. The Mn−Mn
separation through the syn−anti carboxylate bridges is
5.4365(3) Å, these bridges connecting equatorial positions
from adjacent metal ions. The value of the dihedral angle
between the neighboring equatorial planes is 87.86(5)°.
between two positions with the same probability of occupation
and an angle of 49.066(9)° between the aromatic rings.
The shortest interlayer manganese−manganese distance is
19.4231(9) Å, a value much greater than those observed for
complexes 1−3. The different coordination mode of the azpy
ligand in 4 together with the C−H/π intermolecular
interactions, which lead to the opposition between the free
pyridyl ring from the azpy ligand and the aromatic ring from
the phenylmalonate group, cause a larger separation between
the neutral layers. Finally, the corrugation of these layers gives
The aromatic rings of the monodentate azpy ligand in 4 are
planar, and the free pyridyl ring is found to be disordered
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rise to a compact structure, the angle between the azpy ligand
[a vector defined by the uncoordinated from the plane] and the
normal to its corresponding layer being 38.55(8)°.
[Mn2(Et2mal)2(H2O)4(azpy)2]n (5). The three-dimensional
structure of 5 consists of chains of manganese(II) ions, which
grow along the normal of the (101) plane where the
diethylmalonate ligand acts as a linear connector through two
carboxylate-oxygen atoms from its two carboxylate groups
(Figure 8). Each chain is linked to other four chains through
Figure 9. Topological representation of the three-dimensional cds
topology of 5. The yellow nodes and the black and yellow bonds
correspond to the Mn(II) ions, the Rmal, and the connection through
the azpy ligand, respectively.
Both π−π type interactions [the range of the centroid−
centroid distances being 4.039(2)−4.2763(10) Å, with offset
angles between 28.96(11)° and 35.63(12)°, respectively]
(Table 7) and intra- and interchain hydrogen bonds occur in
5, and they contribute to the stabilization of the resulting
supramolecular three-dimensional structure (Table 4).
Four crystallographically independent manganese(II) ions
are present in the structure of 5 (Figure 10), all of them with an
almost ideal octahedral environment (values for s/h of 1.253
[Mn(1)], 1.263 [Mn(2)], 1.244 [Mn(3)], and 1.231 for
[Mn(4)], with a parameter ϕ of 60.0° for all of them).27 The
equatorial plane is built by two diethylmalonate-oxygen atoms
and two water molecules with each manganese(II) ion located
at an inversion center [O(2) and O(1W) at Mn(1), O(3) and
O(2W) at Mn(2), O(6) and O(3W) at Mn(3), and O(8) and
O(4W) at Mn(4)], the average values for the Mn−Oeq bonds
being 2.185(5) Å. Two nitrogen atoms from two azpy ligands
[N(1) and N(1l5) at Mn(1), N(3) and N(3m5) at Mn(2), N(5)
and N(5c5) at Mn(3), and N(7) and N(7e5) at Mn(4)] occupy
the axial positions with the mean value for the Mn−Nazpy bond
lengths of 2.306(5) Å.
Figure 8. Views of 5 along the normal of the (101) plane (a) and the
crystallographic c axis (b) showing the chain interlinking through the
bridging azpy.
The diethylmalonate ligand shows an unusual trans-bis-
monodentate coordination mode (μ-κO:κO‴), the manga-
nese−manganese linking corresponding to the Mn(1)−O(2)−
C(1)−C(2)−C(3)−O(3)−Mn(2) and Mn(3)−O(6)−C(19)−
C(20)−C(21)−O(8) pathways. This coordination mode has
been previously observed in Cd(II),31 Zn(II),31a,32 and
Cu(II)33 chain compounds. The manganese−manganese intra-
chain separation in 5 is 7.328(3) Å, a value that is in the upper
limit of the range observed for the previously reported
complexes [5.958−7.629 Å].
the azpy ligand, which occupies the two axial positions in the
distorted octahedral metal environment, giving rise to a
complex topology corresponding to a (65.8)-cds-type net-
work24,29,30 (Figure 9). There are several examples of this type
of network in MOFs, most of them being constructed by means
of flexible linear spacers and exhibiting highly distorted and
even interpenetrated nets.30
The azpy molecule in 5 acts as bis-monodentate ligand
linking a chain with four other ones, giving rise to a complex
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Figure 10. View of the asymmetric unit of 5 together with the
numbering scheme.
Figure 11. View of 6 along the crystallographic a axis, showing the
π−π type interactions plus the hydrogen bonds.
network with interchain metal−metal separations of 13.527(3)
[Mn(2)···Mn(2d5) and Mn(3)···Mn(3b5)] and 13.534(8) Å
[Mn(1)···Mn(4)] (symmetry codes (b5) = x, y − 1, z; (d5) = x,
y + 1, z). The azpy molecule is coplanar and centrosymmetric
since there is an inversion center at the middle of the inner
NN bond.
[Mn(Bzmal)(H2O)3(azpy)]n (6). The structure of 6 consists of
neutral [Mn(Bzmal)(H2O)3(azpy)] mononuclear units where
the Bzmal and azpy groups act as bidentate and monodentate
blocking ligands, respectively, three coordinated water mole-
cules in a mer arrangement completing the six-coordination
around the manganese(II) ion. The neutral units are
interconnected through an extensive network of hydrogen
bonds involving all the carboxylate-oxygen atoms from the
Bzmal ligand and the coordinated water molecules (Table 5)
leading to layers where the N-donor ligand is alternatively
located above and below, inversely to the position of the benzyl
group. These layers grow in the ab plane and are pillared
through O−H···N and π−π type interactions [values of the
shortest centroid−centroid distance and offset angle of
3.5967(9) Å and 18.86(2)°, respectively] (Tables 5 and 7;
Figure 11), affording a supramolecular three-dimensional tcs-
type topology34 (Figure 13).
Each manganese atom exhibits a somewhat distorted
octahedral environment (Figure 12) [values for s/h and ϕ of
1.263 and 53.75°, respectively].27 The equatorial plane is built
by two carboxylate-oxygen atoms [O(2) and O(4)], one
nitrogen atom from the azpy ligand [N(1)], and a water
molecule [O(3W)], while the axial positions are filled by two
other water molecules [O1W) and O(2W)]. The shortest and
longest bond lengths at the manganese atom are 2.119(2)
[Mn(1)−O(1)] and 2.296(2) Å [Mn(1)−N(1)], the Mn(1)−
Ow bond distances [2.166(2) and 2.189(2) Å] lying within this
range.
Figure 12. View of a fragment of the structure of 6 showing the atom
numbering.
The benzylmalonate group in 6 acts only as a bidentate
ligand through O(2) and O(4) toward Mn(1) [bite angle of
84.435(15)°]. The hydrogen bonds involving all the carbox-
ylate-oxygen atoms and the coordinated water molecules lead
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to corrugated layers with values of the intralayer metal−metal
distance of 5.2212(15) [through O(2W)···O(2) toward
Mn(1c6)], 5.9390(12) [across O(3W)···O(4) toward Mn-
(1e6)], and 7.781(3) Å [through O(1W)···O(3) toward
Mn(1b6); symmetry codes (b6) = −x + 1, −y, −z + 1; (c6) =
−x, −y + 1, −z + 1; (e6) = x + 1, y, z].
The azpy molecule in 6 adopts a monodentate coodination
mode as in 4, but in the present case there is an O−H···N
intermolecular interaction [O(2W)−H(2W)···N(4d6) with a
hydrogen−nitrogen distance of 1.97(2) Å; symmetry code (d6)
= −x + 1, −y + 1, −z] that connects the adjacent layers giving
rise to a three-dimensional supramolecular structure. The
shortest interlayer manganese−manganese separation is
13.908(3) Å [Mn(1)···Mn(1f4); symmetry code (f6) = −x,
−y + 1, −z], a value that is longer than those distances found in
1−3. As in previously studied complexes, the corrugation of the
layers in 6 leads to a more compact structure, with an angle
between the azpy ligand and the normal to its respective plane
of 18.005(5)°. However, in this case the pyridyl rings of the N-
donor ligand are not coplanar [the dihedral angle between their
mean planes is 6.12(3)°].
Structural Discussion. The substituted malonate ligand in
complexes 1−4 shows the usual bidentate and bis-monodentate
coordination mode leading to [63] layers,8g where the Rmal acts
as a 3-fold connector and the metal ion acts as a 3-fold node.
These layers can be pillared through a N-donor coligand like
the azpy molecule to achieve a [63][658] ins-net, if the
substituent of the Rmal is small enough. The honeycomb layers
are usually corrugated, and this situation influences the
interlayer distance, the stacking being directly dependent on
the angle between the bridging coligand and the normal to
these layers. For example, the Butmal ligand in 3 forces the
azpy molecule to adopt a more perpendicular position with
respect to the Rmal−Mn(II) layers, leading to a larger
separation between them than in 1 and 2, where smaller
substituents occur in the Rmal. The aliphatic (3) and aromatic
(4) character of the bulky groups causes the butyl group to
allow enough space for the azpy to bridge the layers whereas
the phenyl precludes the pillaring. Since the structure of 4 is
two-dimensional, the layers are engaged to ensure the
maximum packing. In order to reduce the interlayer space,
the phenyl group is faced with the azpy of the adjacent layer, a
situation previously observed in a Cu(II)−Phmal compound
where a monodentate 2,4′-bipyridine coligand was used.8h
The structures of complexes 5 and 6 have a lower symmetry,
observed in Bzmal-containing complexes only in one first-row
transition metal complex [with copper(II)]37 although other
coordination modes have been observed with alkaline-earth and
second-row transition metal ions.38 Remarkably, the azpy acts
as a terminal ligand despite the fact that three easy leaving
groups (the three coordinated water molecules) build part of
the metal environment. The constraints introduced by the
bulky benzyl group of the Bzmal could be responsible for this
situation.
Thermogravimetric Studies. The curve of the thermal
decomposition of 1 can be described as a plateau, and its
structure is thermally stable until 210 °C. Then, the
degradation process starts with a great weight loss on the TG
curve (∼65%) in two overlapped steps [(DTG)peaks at 267 and
293 °C] and a strong endothermic effect on the DTA curve
with a minimum at 255 °C, which are consistent with the loss
of the coordinated water molecules and the final collapse of the
lattice structure (vide supra). Further, the degradation
continued without formation of any thermally stable
intermediate up to 334 °C. Weak exothermic effects with
maxima at 330 °C accompanied this part of the thermal
decomposition, and it corresponds to the release and pyrolysis
of the organic part of the complex. The thermal decay is
finished at 334 °C when a solid residue (most likely ZnO) is
formed. Complexes 2−5 show very similar thermogravimetric
behaviors, which are comparable to that of 1 (Figure 13 and
Figure 13. TG curves represented as mass loss (%) of 1 (red), 2
(blue), 3 (dark yellow), 4 (green), 5 (pink), and 6 (purple).
Figure S8, Supporting Information). The thermal behavior of
2−5 showed substantially less stability than 1, being thermally
stable up to 170 °C, followed by some complicated overlapped
weight losses (Figure 13 and Figure S8, Supporting
Information). One endothermic effect with minimum at 207
°C, which might be associated with melting of unstable
intermediates, and various exothermic effects with maxima at
250, 317, and 827 °C accompany this part of the
decomposition. These latter sharp exothermic effects can be
connected with the release and pyrolysis of the organic parts of
the complexes.
Magnetic Properties of 1−6. The magnetic properties of
1−5 under the form of χM against T plot [χM is the magnetic
susceptibility per one manganese(II) ion] are shown in Figures
14 (1−4) and 15 (5). At room temperature, the values of the
χMT product for 1−5 vary in the narrow range 4.3−4.40 cm3
mol−1 K in agreement with the presence of a magnetically
isolated spin sextet (χMT = 4.375 cm3 mol−1 K for SMn = 5/2
with g = 2.0). Upon cooling, a Curie law is obeyed in a wide
range of temperature and a decrease of χMT occurs only at low
temperatures reaching 0.819 (1), 0.231 (2), 0.801 (3), 0.785
(4), and 3.566 cm3 mol−1 K (5) at 2.0 K. The shape of these
crystallizing in the P1 space group. The diethyl group of the
̅
Et2mal in 5 is bulky enough to preclude the usual bidentate and
bis-monodentate coordination mode of the malonate. In this
case, the Rmal behaves as bis-monodentate through its two
carboxylate groups, and it acts as a linear connector. This
coordination mode for the Et2mal is rarely observed in
complexes with other substituted malonates, although it has
been previously observed in a Memal complex of formula
[Cu(4,4′-bpy)2(Memal)(H2O)]n·nH2O (4,4′-bpy = 4,4′-bipir-
idine).8b However, seven of the eight diethylmalonate-
containing metal complexes found in the CCDC present this
type of bis-monodentate coordination mode,35 and only one of
them exhibits a bidentate one36 (a polynuclear manganese
complex with the participation of other carboxylate ligands).
These features suggest that this coordination mode seems to be
the preferred one for the Et2mal ligand.
The Bzmal in 6 acts as a bidentate ligand leading to isolated
mononuclear entities. This coordination mode has been
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Article
Figure 14. χM vs T plots for complexes 1 (a), 2 (b), 3 (c), and 4 (d). The solid line is the best fit (see text). The inset shows the maximum of χM vs
T in detail for 1, 3, and 4.
to mediate magnetic interactions,39 allow us to conclude that
the magnetic properties of 1−3 would correspond to those of a
square grid system of spin sextets. This is also valid for
compound 4 where the same layers of manganese(II) ions
occur, a water molecule and a terminally bound azpy ligand
filling the axial position at each metal atom. Consequently, the
magnetic data of 1−4 were treated through the Lines approach
for a quadratic layer of local spin sextets that interact across
syn−anti carboxylate bridges [eq 1]:40
−1
6
Nβ2g2
|J|
Cn
Θn−1
⎡
⎢
⎤
⎥
χM
=
3Θ +
∑
⎢
⎣
⎥
⎦
(1)
n=1
where N, β, and k have their usual meaning, Θ = kT/[|J|S(S +
Figure 15. χM vs T plot for 5. The solid line is the best fit (see text).
1)], C1 = 4, C2 = 1.448, C3 = 0.228, C4 = 0.262, C5 = 0.119, and
n
̂
̂
̂
C6 = 0.017, the Hamiltonian being defined as H = −J∑i=1Si·Si+1
n
̂
̂
plots is typical of an overall weak antiferromagnetic interaction,
a feature that is supported by the occurrence of a maximum of
the magnetic susceptibility at 3.0 (1 and 4), 5.5 (2), and 2.8 K
(3). No maximum is observed for 5 down to 2.0 K suggesting a
weaker magnetic interaction in this compound.
Given the structural similarity of complexes of the three-
dimensional compounds 1−3, where square grids of Mn(II)
ions with intralayer carboxylate (Rmal) bridges in the syn−anti
conformation and interlayer connection through bis-mono-
dentate azpy ligands occur, we will analyze first the magnetic
data of this family of complexes. Although two exchange
pathways could be involved in 1−3, the syn−anti carboxylate
bridge and the more extended bis-monodentate azpy ligand, the
much greater manganese−manganese separation through the
latter pathway (values in the range 13.56−13.59 Å) compared
with those across the former one (values from 5.40 to 5.52 Å),
together with the well-known ability of the carboxylate bridge
+ gβH∑i=1Si. Least-squares best-fit parameters for 1−4 are J =
−0.31(1) cm−1 and g = 1.98(1) (1), J = −0.41(1) and g =
2.02(1) (2), J = −0.36(2) cm−1 and g = 2.00(1) (3), and J =
−0.31(1) cm−1 and g = 1.95(1) (4). The calculated curves for
1−4 reproduce the magnetic data in the whole temperature
range investigated.
Dealing with the three-dimensional structure of compound 5,
two exchange pathways could be operative: the bis-mono-
dentate Etmal and azpy ligands with values of the manganese−
manganese separation through them of ca. 7.3 and 13.5 Å,
respectively. By neglecting the more extended pathway, we
would be faced with a uniform chain of interacting spin sextets,
the intrachain magnetic coupling being weak and antiferro-
magnetic. Therefore, its magnetic data can be analyzed by
means of Fisher’s law for a regular chain with classical spin
moments [eq 2]:41
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Crystal Growth & Design
Article
35Nβ2g2
12kT ⎩1 − u(K) ⎭
⎧
⎫
⎬
situation that is also observed for 5 through the uncommon and
more extended Mn−OCCCO−Mn pathway.
1 + u(K)
⎨
χM
=
(2)
ASSOCIATED CONTENT
* Supporting Information
■
where (K) = coth K − 1/K, K = 35J/4kT, and J is the intrachain
magnetic coupling. Least squares analysis of the susceptibility
data led to J = −0.045(1) cm−1 and g = 1.97(1). The calculated
curve matches well the experimental data in the whole
temperature range investigated.
S
Crystallographic information in the form of cif files, views of the
crystal packing and the weak interactions present in the
compounds 1−6, the topological representation of the
supramolecular 3D structure of 6, thermogravimetric analyses
of 1−6, and the magnetic susceptibility curves for 1−4 and 5.
This material is available free of charge via the Internet at
http://pubs.acs.org.
The magnetic couplings in 1−4 are weak and antiferro-
magnetic [values of J in the range −0.26 (1) to 0.41 cm−1 (2)],
and they agree with the expected interactions between
manganese(II) ions separated by ca. 5.4 Å through a single
carboxylate (Rmal) in the syn−anti coordination mode.42
Subtle structural differences in the Mn−OCO−Mn bridging
skeleton would account for the somewhat larger value of the
magnetic coupling for 2. Finally, the weak antiferromagnetic
coupling between the manganese(II) ions in the extended Mn−
OCCCO−Mn pathway is also as expected given the great
metal−metal separation (ca. 7.3 Å). This value could be
compared with that through the same pathway in the
copper(II) complex [Cu(4,4′-bpy)2(Memal)(H2O)]n·nH2O (J
= −1.38 cm−1)8a where only one unpaired electron at the metal
center occurs (versus five at each metal ion in 5).
AUTHOR INFORMATION
Corresponding Author
*E-mail: jpasang@ull.es; caruiz@ull.es.
■
Present Address
‡Centro Universitario para la Defensa, Academia General
Militar, Ctra de Huesca s/n, 50090 Zaragoza, Spain.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support by the Spanish Ministerio de Ciencia e
■
CONCLUSIONS
Innovacion
́
through projects MAT2010-16981, CTQ2010-
■
́
́
15364, DPI2010-21103-C04-03, “Factoria de Crystalizacion”
Although the substituted malonate presents in almost all these
complexes common bidentate (6) or bidentate/bis-mono-
dentate (1−4) coordination modes, an unusual trans-bis-
monodentate coordination mode occurs in compound 5. The
carboxylate (Rmal) bridges lead to corrugated grids (1−4) or
chains (5) of manganese(II) ions with Mn−Mn intralayer (1−
4) or intrachain (5) distances of 5.4047(14)−5.5274(15) Å or
7.328(3) Å. The coordination of the azpy molecule either as a
bis-monodentate (1−3 and 5) or monodentate (4 and 6)
ligand leads to three-dimensional networks in the case of 1, 3,
and 5, where 4 and 6 are two-dimensional and mononuclear
compounds, respectively. One can observe in these structures
how the disposition of N-donor ligand and the alkyl-substituted
malonate ligands used leaves no void space for the formation of
cavities or pores in any case. From a structural point of view,
four different topologies have been observed:
(i) a binodal [63][65.8] ins-type topology (1−3), where the
Rmal ligand and the Mn(II) ion act as 3- and 4-
connected nodes, respectively
(ii) a hcb two-dimensional topology (4), which does not give
rise to an ins topology because the azpy molecule acts as
a blocking ligand
(Consolider Ingenio2010 CSD2006-0015), Molecular Nano-
science (Consolider Ingenio CSD2007-00010), ACIISI Go-
bierno de Canarias (PIL2070901), and Generalitat Valenciana
(PROMETEO/2009/108, and ISIC/2012/002) is gratefully
acknowledged. M. Den
́
iz thanks the Spanish Ministerio de
for a predoctoral fellowship. J.P. also
Ciencia e Innovacion
́
thanks the Universidad de La Laguna as part of the Campus of
Excellence Project ‘CEI Canarias: Campus Atlantico Triconti-
nental’.
́
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