Hydrothermal synthesis and structural characterization of three novel lanthanide coordination polymers with fumarate and 1,10-phenanthroline

Article abstract of DOI:10.1016/j.molstruc.2004.02.012

Three novel lanthanide complexes, [Ln₂(fum)₃(phen) ₂(H₂O)₂]_n (Ln=La, 1; Pr, 2. fum=fumarate dianion; phen=1,10-phenanthroline) and [Er₂(fum) ₃(phen)₂]_n

Full text of DOI:10.1016/j.molstruc.2004.02.012

Journal of Molecular Structure 692 (2004) 249–253
www.elsevier.com/locate/molstruc
Hydrothermal synthesis and structural characterization of three novel
lanthanide coordination polymers with fumarate and 1,10-phenanthroline
*
Liang Huang, Li-Ping Zhang
Department of Chemistry, Anyang Teachers College, Anyang 455000, China
Received 25 December 2003; revised 7 February 2004; accepted 11 February 2004
Abstract
Three novel lanthanide complexes, [Ln
and [Er (fum) (phen) ] (3), were synthesized hydrothermally and characterized by X-ray crystallography. Single crystal X-ray diffraction
2
(fum)
3
(phen)
(H
2 2
O)
2
]
n
(Ln ¼ La, 1; Pr, 2. fum ¼ fumarate dianion; phen ¼ 1,10-phenanthroline)
2
3
2 n
analysis shows that complex 1 is isostructural with 2. Ln(III) centers are nine-coordinated in 1 and 2 but eight-coordinated in 3 duo to
lanthanide contraction. The coordination modes of fumarate and phen ligands are identical in three complexes. So structures of three
complexes are very similar. In three structures, Ln(III) ions are bridged by fumarate anions in two modes, forming polymeric sheets. These
sheets are further assembled into 3D supramolecular network by different intermolecular hydrogen bonding and p–p stacking interactions
duo to the lack of coordinated water in 3. IR spectra are assigned based on the molecular structures.
q 2004 Elsevier B.V. All rights reserved.
Keywords: Lanthanide; Complex; Hydrothermal synthesis; Crystal structure; IR
1
. Introduction
and [Er (fum) (phen) ] (3), which were characterized by
2 3 2 n
single crystal X-ray diffraction.
Research on metal-directed supramolecular compounds
has rapidly been expanding duo to their interesting
topologies and potential applications as functional materials
2. Experimental
[
1–3]. Though the use of various saturated aliphatic a,v-
2.1. Materials and apparatus
dicarboxylic acid to form bridges between metal centers has
been extensively studied [4], the use of unsaturated aliphatic
a,v-dicarboxylic acid is scanty in the literature [5]. Fumaric
acid is the simplest compound of unsaturated aliphatic
diacids, and 1,10-phenanthroline (phen) is a good ligand for
lanthanide ions and can construct supramolecular structure
via C–H· · ·O hydrogen bonding and p–p stacking
interactions. Therefore, we selected the two compounds as
mixed ligands and hope to construct novel lanthanide
complexes with fascinating structures. Several structural
studies have been published on lanthanide fumarates [6].
But the lanthanide complexes containing both the ligands
of fumarate and phen have not been synthesized so far.
Herein, we report three novel lanthanide fumarate com-
plexes, [Ln (fum) (phen) (H O) ] (Ln ¼ La, 1; Pr, 2)
LnCl ·nH O (Ln ¼ La and Pr, n ¼ 7; Ln ¼ Er, n ¼ 6)
3
2
were prepared by dissolving their oxides in dilute
hydrochloric acid, respectively and then dried. All other
chemicals were purchased and used as received without
further purification. C, H and N data were obtained using the
PE 2400 II CHNS/O elemental analyzer. Infrared spectra
were recorded with the Nicolet Avatar 360 FT-IR
spectrometer.
2
.2. Preparation of complexes
LnCl ·nH O (0.3 mmol; La, n ¼ 7; 0.1114 g; Pr, n ¼ 7;
3
2
0
0
.1120 g; Er, n ¼ 6; 0.1145 g) and H fum (0.3 mmol,
2
2
3
2
2
2 n
.0348 g) were dissolved in 10 ml deionized water,
respectively, to which phen·H O (0.3 mmol, 0.0595 g) was
2
*
Corresponding author. Tel.: þ86-30-6443-3577; fax: þ86-37-2290-
048.
E-mail address: lpzhang@aytc.edu.cn (L.-P. Zhang).
added and the pH value was adjusted to about four with
NaOH aqueous solution. The mixture was placed in
2
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.02.012

250
L. Huang, L.-P. Zhang / Journal of Molecular Structure 692 (2004) 249–253
a Teflon-lined stainless steel vessel (23 ml). The vessel was
sealed and heated at 140 8C for 3d under autogenous
pressure and then cooled to room temperature. After filtered,
the product was washed with ethanol and then dried under
ambient. Columnlike crystals of the complexes 1–3 were
collected (yields: 0.0465 g, 30.5% for 1; 0.0554 g, 36.2%
for 2; 0.0638 g, 41.0% for 3).
Table 1
Crystallographic data for complexes 1–3
1
2
3
Formula
LaC18
H
13
N
2
O
7
PrC18
510.21
Triclinic
H
13
N
2
O
7
11 2 6
ErC18H N O
Formula weight
Crystal system
Space group
˚
a (A)
˚
b (A)
508.21
Triclinic
ꢀ
P1
518.55
Triclinic
ꢀ
P1
ꢀ
P1
[La (fum) (phen) (H O) ] 1. Found (Calcd., %): C,
2.28(42.54); H, 2.42(2.58); N, 5.53(5.51). IR(KBr pellet,
2 3 2 2 2 n
9.0567(18)
10.072(2)
10.610(2)
72.54(3)
77.83(3)
70.02(3)
2
9.013(3)
9.999(3)
8.842(3)
9.352(4)
4
cm ): 3601(m), 3078(w), 2933(w), 1575(vs), 1366(vs),
2
1
˚
c (A)
10.546(3)
72.551(5)
77.538(5)
70.006(5)
2
10.686(4)
80.278(6)
76.543(6)
73.357(5)
2
1
8
199(s), 1138(m), 1103(m), 1011(m), 989(m), 966(w),
50(s), 802(s), 731(s), 685(s), 658(s), 576(m), 562(m).
a (deg)
b (deg)
g (deg)
Z
[Pr (fum) (phen) (H O) ] 2. Found (Calcd., %): C,
2.01(42.37); H, 2.41(2.57); N, 5.48(5.49). IR(KBr pellet,
2 3 2 2 2 n
4
cm ): 3603(m), 3386(m, br), 3082(w), 2926(w), 2855(w),
3
˚
V (A )
861.4(3)
1.959
845.2(5)
2.005
818.4(5)
2.104
2
1
3
dcalcd (g/cm )
Temperature (K)
Fð000Þ
1
1
6
578(vs), 1397(vs), 1365(vs), 1200(s), 1140(m), 1104(m),
009(m), 991(m), 981(w), 850(s), 802(s), 731(s), 686(s),
58(s), 577(m), 562(m).
291(2)
496
293(2)
500
293(2)
498
2
1
)
m (mm
2.527
2.930
5.168
R½I . 2sðIÞꢀR
0.0309
0.0790
0.0297
0.0623
0.0257
0.0580
1
[
1.46(41.69); H, 1.95(2.14); N, 5.58(5.40). IR(KBr pellet,
Er (fum) (phen) ] 3. Found (Calcd., %): C,
2 3 2 n
wR
2
4
cm ): 3448(m, br), 3059(w), 2925(w), 2854(w), 1597(vs),
2
1
environment by virtue of two N atoms from a phen ligand
and six oxygen from five fumarate ligands. Two types of
coordination modes of fumarate ligands exist in complex 1:
1
1
7
421(vs), 1407(vs), 1340(s), 1262(m), 1196(s), 1145(m),
106(m), 1017(m), 1000(m), 987(w), 848(s), 806(s), 730(s),
02(s), 661(s), 583(m), 421(m).
(i) bridging bidentate and monodentate [Scheme 1 (a)], the
fumarate anions are bonded in this mode to La(III) cations
along b-axis; (ii) two chelating/bridging tridentate [Scheme
2
.3. Single-crystal X-ray diffraction
1 (b)], the fumarate anions are centrosymmetric and bonded
in this mode to La(III) cations along a-axis. Thus a 2D
Single-crystal X-ray data were collected on a Bruker
SMART 1000 CCD diffractometer equipped with graphite
˚
polymeric sheet is formed via bridging fumarate ligands
(
monochromatized Mo Ka radiation ðl ¼ 0:71073 A).
Fig. 2). The 2D sheet is parallel to the ab plane and has
˚
Semiempirical absorption corrections were applied using
the SADABS program. All calculations were carried out
with use of SHELXS 97 and SHELXL 97 programs [7]. The
structures were solved by the direct methods. All structures
rhombus grids with a cavity of ca. 9.1 £ 10.1 A. All the
La(III) ions in a 2D sheet are not coplanar but distributed in
2
Table 2
˚
Selected bond lengths (A) for complexes 1, 2 and 3
were refined on F by full-matrix least-squares methods.
The crystallographic data of the complexes are summarized
in Table 1 and the selected bond lengths in Table 2.
Bond lengths in 1
La(1)–O(1)
La(1)–O(3A)
La(1)–O(4B)
La(1)–O(6C)
La(1)–O(6)
2.417(3)
2.471(3)
2.491(3)
2.498(3)
2.820(3)
La(1)–O(5)
La(1)–O(7)
La(1)–N(1)
La(1)–N(2)
2.598(3)
2.605(4)
2.746(4)
2.697(4)
3
. Results and discussion
3
.1. Structural description of [Ln (fum) (phen) (H O) ]
2 n
2
3
2
2
Bond lengths in 2
Pr(1)–O(4A)
Pr(1)–O(2B)
Pr(1)–O(5)
(
Ln ¼ La, 1; Pr, 2) and [Er (fum) (phen) ] (3)
2
3
2 n
2.380(4)
2.427(3)
2.450(3)
2.452(3)
2.798(4)
Pr(1)–O(6B)
Pr(1)–O(7)
Pr(1)–N(1)
Pr(1)–N(2)
2.555(4)
2.583(4)
2.702(4)
2.635(4)
Single-crystal X-ray diffraction studies reveal that
Pr(1)–O(1)
complexes 1 and 2 are isostructural and the complexes 1
and 3 will be described in detail. As shown in Fig. 1, there is
only one type of Ln(III) ion environment in the asymmetric
units of 1 and 3. The coordination modes of fumarate and
phen ligands are identical in both complexes. The obvious
difference between 1 and 3 is that there is a coordinated
water molecule in 1. So La(1) is nine-coordinated and
surrounded by two nitrogen atoms from a phen molecule,
six carboxylate oxygen atoms from five fumarate ligands
and one oxygen atom from coordinated water molecule.
While Er(1) is eight-coordinated and possesses an N O
Pr(1)–O(5B)
Bond lengths in 3
Er(1)–O(3A)
Er(1)–O(1)
2.170(3)
2.279(3)
2.294(3)
2.311(3)
Er(1)–O(5B)
Er(1)–O(6B)
Er(1)–N(1)
Er(1)–N(2)
2.578(3)
2.403(3)
2.529(4)
2.485(4)
Er(1)–O(2B)
Er(1)–O(5)
Symmetry transformations used to generate equivalent atoms for 1: A
x þ 1; 2y þ 1; 2z; B x; y 2 1; z; C 2x þ 1; 2y; 2z: Symmetry trans-
2
formations used to generate equivalent atoms for 2: A x; y 2 1; z; B 2x þ 1;
2
y þ 1; 2z þ 1: Symmetry transformations used to generate equivalent
atoms for 3: A 2x; 2y; 2z þ 1; B 2x; 2y þ 1; 2z þ 1:
2
6

L. Huang, L.-P. Zhang / Journal of Molecular Structure 692 (2004) 249–253
251
Fig. 1. The coordination environments of La(III) in 1 and Er(III) in 3 showing 50% thermal ellipsoids.
2
1365–1425 cm for symmetric stretching. The relatively
1
two parallel planes. The distance between the two planes is
˚
ca. 3.3 A. The uncoordinated carboxylate oxygen atoms,
large values of D
ðy
2 yOCOsymÞ calculated for 1
OCO OCOasym
2
1
21
coordinated water molecules and phen ligands are situated
at both sides of the polymeric sheet. The uncoordinated
oxygen atoms form two kinds of C–H· · ·O hydrogen bonds
with C–H of phen molecules and one kind of O–H· · ·O
hydrogen bonds with coordinated water molecules in the
crystal [Fig. 3(a)]. The relevant hydrogen bond parameters
are summarized in Table 3. In addition, weak p–p stacking
interactions exist between the phen molecules of neighbor-
ing sheets, and the average distances between two phen
(209 cm ) and 2 (212 cm ) are close to the value
expected for a monodentate coordination mode of the
carboxylate moiety [8]. The IR spectrum of complex 3
2
1
shows the positions of yOCOasym band at 1597(vs) cm and
2
yOCOsym bands at 1407(vs) and 1340(s) cm . The
1
2
1
symmetric stretching band at 1340 cm
2
is unusual
1
(D ¼ 257 cm ) and maybe it is duo to the marked
˚
planes are 3.1 and 3.3 A, respectively. Such intermolecular
hydrogen bonding and p–p stacking interactions between
sheets result in a 3D supramolecular structure [Fig. 3 (a)].
Fig. 3 (b) shows the packing of the sheets in complex 3.
Similar to 1, the Er(III) ions are bridged by fumarate ligands
in two coordination modes (Scheme 1) into a 2D polymeric
Scheme 1. Coordination modes of fumarate groups in complexes 1–3.
sheet which has rhombus grids with a cavity of ca.
˚
8
.8 £ 9.4 A. Due to the lack of coordinated water, in 3
exist only one kind of weak C–H· · ·O hydrogen bonds
between the uncoordinated carboxylate oxygen atom and
C–H of phen from adjacent sheet (Table 3). Phen ligands
locate at both sides of the sheets. p–p interactions exist
between phen ligands of adjacent sheets with the average
˚
distances of 3.3 and 3.5 A, respectively. Thus a 3D
supramolecular network is formed via C–H· · ·O hydrogen
bonds and p–p interactions between the sheets (Fig. 3(b)).
3
.2. IR spectra
In both spectra of complexes 1 and 2, the characteristic
bands of the carboxylate groups occur within the range
Fig. 2. Projection down the c-axis for complex 1. All the hydrogen atoms
are omitted for clarity.
–
545–1598 cm for asymmetric stretching and the range
1
1

252
L. Huang, L.-P. Zhang / Journal of Molecular Structure 692 (2004) 249–253
Fig. 3. Packing of the sheets showing the 3D network ((a) for complex 1 and (b) for 3) via hydrogen bonding and p–p stacking viewed down b-axis. The
hydrogen atoms attached to carbon atoms are omitted for clarity.
Table 3
˚
Hydrogen bonds parameters (A, 8) for complexes 1, 2 and 3
Complex
1
D–H
d(D–H)
d(H· · ·A)
/DHA
d(D· · ·A)
Position of A
O(7)–H(7F)
0.822
0.930
0.930
1.899
2.491
2.500
175.1
148.1
146.2
2.719
3.317
3.314
O(2) ð2x þ 1; 2y; 2z þ 1Þ
O(2) ð2x þ 1; 2y; 2z þ 1Þ
O(2) ð2x; 2y þ 1; 2z þ 1Þ
C(10)–H(10A)
C(11)–H(11A)
2
3
O(7)–H(7A)
C(5)–H(5)
0.850
0.930
0.930
1.896
2.462
2.474
167.7
148.5
143.6
2.733
3.291
3.270
O(3) ð2x þ 1; 2y þ 2; 2zÞ
O(3) ð2x þ 2; 2y þ 1; 2zÞ
O(3) ð2x þ 1; 2y þ 2; 2zÞ
O(4) ðx þ 1; y; z 2 1Þ
C(10)–H(10)
C(5)–H(5)
0.930
2.428
159.0
3.312
˚
difference of 0.084 A between the two C–O distances of the
monodentate coordinated carboxylate group implying a
(E-mail: deposit@ccdc.cam.ac.uk; fax: þ 44-1223-336033;
http://www.ccdc.cam.ac.uk).
partial single bond character of the C(16)–O(3) bond
˚
(1.296 A). Comparing the spectra of three complexes, C–H
stretching vibrations appear above 3000 cm
2
1
[9] and
characteristic C–H out-of-plane bending vibrations are seen
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