Poly[[tetra-aqua-tris(μ3-2,2-dimethyl-malonato) dilanthanum(III)] mono-hydrate]

Article abstract of DOI:10.1107/S0108270109012931

In the title complex, {[La2(C5H6O4)3(H2O)4]·H2O} n , the La atoms are connected by bridging O atoms from carboxyl-ate groups to build, through centres of inversion, two-dimensional layers parallel to the ac plane containing deca-nuclear 20-membered rings.

Full text of DOI:10.1107/S0108270109012931

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
molecules and one solvent water molecule. Selected geometric
parameters are given in Table 1. Fig. 1 shows a symmetry-
expanded view, which displays the full coordination of the two
La atoms and gives details of the symmetry codes used below.
ISSN 0108-2701
Poly[[tetraaquatris(l3-2,2-dimethyl-
malonato)dilanthanum(III)] mono-
hydrate]
Ming-Lin Guo* and Chen-Hu Guo
School of Materials and Chemical Engineering, and Key Laboratory of Hollow Fiber
Membrane Materials and Membrane Processes, Tianjin Polytechnic University,
Tianjin 300160, People’s Republic of China
Correspondence e-mail: guomlin@yahoo.com
Received 24 January 2009
Accepted 6 April 2009
Online 10 April 2009
All the symmetry-related La atoms of (I) are related by
inversion centres. Thus, the L1 dianion is coordinated to
centrosymmetrically related atoms La1 and La1i via bis-
bidentate 1,2-chelating and six-membered ring modes. The L2
dianion binds to atoms La1, La2 and La2iii, with the two
carboxylate groups using two bis-bidentate 1,2-chelating
modes and one six-membered ring mode. The L3 ligand also
adopts two bis-bidentate 1,2-chelating modes and one six-
membered chelating mode to connect to atoms La2, La1ii and
La2ii, but it differs from the L2 ligand with the bond angle at
C12 being smaller than the normal value (Table 1), indicating
that there is greater distortion in this six-membered ring. This
smaller angle was observed in polymeric tetraaquatrimalon-
atodilanthanum(III) monohydrate complexes (Benmerad et
al., 2000).
In the title complex, {[La2(C5H6O4)3(H2O)4]ꢀH2O}n, the La
atoms are connected by bridging O atoms from carboxylate
groups to build, through centres of inversion, two-dimensional
layers parallel to the ac plane containing decanuclear 20-
membered rings. The coordinated water molecules are
involved in intralayer hydrogen-bond interactions. Adjacent
layers are linked via hydrogen bonding to the solvent water
molecules. This work represents the first example of a new
substituted malonate–lanthanide complex.
Comment
Recently, the design and preparation of novel lanthanide
dicarboxylate metal–organic frameworks have received
considerable attention because of the interesting properties
that they exhibit, such as porosity, luminescence, magnetism
and catalytic activity (Shi et al., 2008; Luo et al., 2008; Ghosh &
Bharadwaj, 2005; Mahata & Natarajan, 2007; Wang et al.,
2007). Of these, malonate has been used as the ligand of
choice for the design of such metal–organic frameworks/
molecular assemblies because of its manifold coordination
modes and the variety of the resulting architectures (Hansson,
1973a,b; Canadillas-Delgado et al., 2006). Two complexes with
lanthanum have been reported to date, one containing the
malonate dianion (Marrot & Trombe, 1993; Benmerad et al.,
2000) and the other both the malonate dianion and the
hydrogen malonate monoanion as ligands (Marrot & Trombe,
1994). However, in spite of this wealth of possibilities, no
complexes of a lanthanide with dimethylmalonate have been
reported to date. Using the 2,2-dimethylmalonate dianion as a
ligand, we have obtained the novel title ten-coordinate
dimethylmalonate–La complex, (I), which is described here.
The asymmetric unit of (I) contains two independent ten-
coordinate La atoms, three independent dimethylmalonate
dianions, denoted L1, L2 and L3 (containing O atoms O1–O4,
O5–O8 and O9–O12, respectively), four coordinated water
The La—O distances in (I) (Table 1) are comparable with
the values reported for polymeric tetraaquatrimalonatodi-
lanthanum(III) monohydrate (Benmerad et al., 2000), but with
three La—O bonds being considerably longer. These longer
distances seem to be rather typical of the chelating carboxyl-
Figure 1
A view of part of the structure of (I), showing the atom-numbering
scheme and the coordination for atoms La1 and La2. Displacement
ellipsoids are drawn at the 30% probability level. The H atoms of the
methyl groups have been omitted for clarity and the remaining H atoms
are shown as small spheres of arbitrary radii. [Symmetry codes: (i) ꢁx + 2,
ꢁy + 2, ꢁz + 2; (ii) ꢁx + 2, ꢁy + 2, ꢁz + 1; (iii) ꢁx + 1, ꢁy + 2, ꢁz + 1.]
Acta Cryst. (2009). C65, m195–m197
doi:10.1107/S0108270109012931
# 2009 International Union of Crystallography m195

metal-organic compounds
Figure 2
A partial packing diagram for (I), showing the two-dimensional
polymeric layer and hydrogen-bonding interactions (as dashed lines) in
the direction of the ac plane, viewed down the b axis. The H atoms of the
methyl groups have been omitted for clarity.
ate group (Hansson, 1973a,b). The La geometries do not
approximate to an idealized polyhedron, a bicapped square
antiprism or a bicapped dodecahedron. This is not surprising
in view of the steric requirements of the dimethylmalonate
ligands in the structure and the large distortions imposed by
the bite angles, which are considerably small (Table 1) (see
Benmerad et al., 2000). Through the centres of inversion, each
group of six La2 atoms and four La1 atoms builds up a
decanuclear 20-membered ring. These decanuclear rings are
further joined into a two-dimensional layer structure parallel
to the ac plane (Fig. 2).
Figure 3
A partial packing diagram for (I), showing the connection between
neighbouring layers generated by the twofold screw axis. Interlayer
hydrogen-bond interactions are shown as dashed lines. The H atoms of
the methyl groups have been omitted for clarity.
Experimental
Within these layers, strong intra- and intermolecular
hydrogen-bond interactions (entries 6 and 7 in Table 2; Brown,
1976) are responsible for the formation of two six-membered
hydrogen-bonded S(6) and R(6) ring graph sets (Bernstein et
al., 1995). The two coordinated water molecules, O13 and O14,
are involved in a hydrogen bond (entry 9 in Table 2) which
crosslinks two La1 atoms together within the decanuclear 20-
membered ring via an R22(8) motif (Fig. 2), thus enhancing the
stability of the decanuclear 20-membered ring. These two-
dimensional dianionic (dimethylmalonato)lanthanum metal–
La2O3 (0.4 g, 1.2 mmol) was dissolved in dilute hydrochloric acid and
the solvent evaporated to dryness. The resulting LaCl3ꢀnH2O was
dissolved in distilled water (20 ml) at room temperature, and then
dimethylmalonic acid (0.3 g, 2.3 mmol) and sodium dimethyl-
malonate (0.6 g, 3.4 mmol) were added under continuous stirring.
After filtration, slow evaporation over a period of two weeks at room
temperature provided colourless needle-shaped crystals of (I).
Crystal data
3
˚
[La2(C5H6O4)3(H2O)4]ꢀH2O
V = 2388.2 (8) A
Z = 4
Mr = 758.19
Monoclinic, P21=n
1
organic layers occur near y = 0 and y = by way of the crys-
Mo Kꢁ radiation
ꢂ = 3.61 mmꢁ1
T = 133 K
0.12 ꢃ 0.08 ꢃ 0.06 mm
2
˚
a = 8.3835 (17) A
tallographic twofold screw axis. The solvent water molecule
(O17), acting as both proton donor and acceptor, provides
strong interlayer binding along the b axis through further
hydrogen bonds (entries 1–3 and 10 in Table 2; Fig. 3).
A comparison with the two previously reported lanthanum
malonate compounds (Marrot & Trombe, 1993; Benmerad et
al., 2000) reveals that all these structures contain the same
number of water molecules. However, the two crystal-
lographically independent La atoms of the former are nine-
and eight-coordinate, respectively, while in the latter there is
only one crystallographically independent La atom and two
independent malonate dianions. The present work therefore
represents a new example of the substituted malonate series of
lanthanide complexes.
˚
b = 20.229 (4) A
˚
c = 14.101 (3) A
ꢀ = 92.989 (3)ꢂ
Data collection
Rigaku Saturn diffractometer
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC,
2005)
13664 measured reflections
4177 independent reflections
3140 reflections with I > 2ꢃ(I)
Rint = 0.061
Tmin = 0.715, Tmax = 0.802
Refinement
R[F2 > 2ꢃ(F2)] = 0.035
wR(F2) = 0.088
S = 0.94
313 parameters
H-atom parameteꢁrs3 constrained
˚
Áꢄmax = 1.04 e A
ꢁ3
˚
4177 reflections
Áꢄmin = ꢁ0.81 e A
ꢄ
m196 Guo and Guo [La2(C5H6O4)3(H2O)4]ꢀH2O
Acta Cryst. (2009). C65, m195–m197

metal-organic compounds
˚
with O—H = 0.85 A and their Uiso values were set at 1.2Ueq(O). The
H atoms of the C—H groups were treated as riding, with C—H =
Table 1
Selected geometric parameters (A, ).
ꢂ
˚
˚
0.96 A and Uiso(H) = 1.5Ueq(C).
La1—O3
La1—O1
La1—O13
La1—O5
La1—O1i
La1—O11ii
La1—O12ii
La1—O14
La1—O6
La1—O2i
La2—O15
La2—O16
2.421 (4)
2.490 (4)
2.550 (4)
2.594 (4)
2.604 (4)
2.620 (4)
2.623 (4)
2.625 (4)
2.645 (4)
2.747 (4)
2.466 (4)
2.498 (4)
La2—O7
La2—O9
La2—O5
La2—O10ii
La2—O8iii
La2—O12ii
La2—O7iii
La2—O10
O3—C3
2.544 (4)
2.574 (4)
2.590 (3)
2.599 (4)
2.604 (4)
2.617 (4)
2.712 (4)
2.756 (4)
1.260 (6)
1.222 (6)
1.251 (7)
1.273 (6)
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement:
CrystalClear; data reduction: CrystalClear; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: SHELXTL.
O4—C3
O6—C6
O7—C8
The authors thank Tianjin Polytechnic University for
financial support.
O11ii—La1—O12ii
O13—La1—O14
O5—La1—O6
O15—La2—O16
O8iii—La2—O7iii
49.23 (12)
66.83 (12)
49.18 (11)
140.22 (13)
48.59 (11)
O9—La2—O10
C1—C2—C3
C8—C7—C6
48.49 (11)
114.8 (4)
112.8 (4)
105.7 (4)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GA3119). Services for accessing these data are
described at the back of the journal.
C13—C12—C11
Symmetry codes: (i) ꢁx þ 2; ꢁy þ 2; ꢁz þ 2; (ii) ꢁx þ 2; ꢁy þ 2; ꢁz þ 1; (iii) ꢁx þ 1,
ꢁy þ 2; ꢁz þ 1.
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ꢂ
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O17—H17Bꢀ ꢀ ꢀO4
O17—H17Aꢀ ꢀ ꢀO2iv
O16—H16Bꢀ ꢀ ꢀO17v
O16—H16Aꢀ ꢀ ꢀO9iii
O15—H15Bꢀ ꢀ ꢀO8vi
O15—H15Aꢀ ꢀ ꢀO3
O14—H14Bꢀ ꢀ ꢀO11vii
O14—H14Aꢀ ꢀ ꢀO6viii
O13—H13Bꢀ ꢀ ꢀO14viii
O13—H13Aꢀ ꢀ ꢀO17v
0.85
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0.85
0.85
0.85
0.85
0.85
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1.84
2.06
1.98
1.99
2.00
1.90
1.82
2.01
1.99
1.91
2.681 (5)
2.810 (6)
2.819 (5)
2.773 (5)
2.777 (5)
2.709 (5)
2.667 (6)
2.754 (5)
2.828 (5)
2.707 (5)
171
146
169
153
151
160
176
145
168
155
1
3
1
2
3
2
Symmetry codes: (iii) ꢁx þ 1; ꢁy þ 2; ꢁz þ 1; (iv) x ꢁ ; ꢁy þ ; z ꢁ ; (v) ꢁx þ ,
2
2
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1
3
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2
2
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ꢄ
Acta Cryst. (2009). C65, m195–m197
Guo and Guo
[La2(C5H6O4)3(H2O)4]ꢀH2O m197