Bis(μ2-1-carboxybenzene-2-carboxylato)diaqua(monohydrogen phthalato)-(1,10-phenanthroline)samarium(III): Hydrothermal synthesis and crystal structure

Article abstract of DOI:10.1134/S1070328409110128

A new lanthanide complex [{Sm(HPht)(Phen)(H₂O)₂} ₂(μ-Pht)₂] (I), where Pht^2- is dianion of o-phthalic acid; HPht^- is monoanion of o-phthalic acid; Phen is 1,10-phenanthroline, has been synt

Full text of DOI:10.1134/S1070328409110128

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2009, Vol. 35, No. 11, pp. 864–867. © Pleiades Publishing, Ltd., 2009.
Bis(m2-1-Carboxybenzene-2-
Carboxylato)diaqua(monohydrogen Phthalato)-
(1,10-Phenanthroline)samarium(III):
Hydrothermal Synthesis and Crystal Structure1
L. C. Yu*, L. Lai, S. L. Liu, and Y. Xia
College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangta 411201, P.R. China
*E-mail: ylcphd@163.com
Received December 8, 2008
Abstract—A new lanthanide complex [{Sm(HPht)(Phen)(H2O)2}2(μ-Pht)2] (I), where Pht2– is dianion of o-
phthalic acid; HPht– is monoanion of o-phthalic acid; Phen is 1,10-phenanthroline, has been synthesized, and its crys-
tal structure was determined by X-ray crystallography. Complex I crystallizes in the triclinic system, space group
P1, with lattice parameters a = 10.1126(3), b = 10.7029(3), c = 11.9360(3) Å, α = 90.2260(10)°, β = 99.526(2)°,
γ =100.9810(10)°, V = 1249.87(6) Å3, Z = 2, ρc = 1.849 mg/m3, final R indices I > 2σ(I): R1 = 0.0202, wR2 = 0.0493;
R indices (all data): R1 = 0.0220, wR2 = 0.0504.
DOI: 10.1134/S1070328409110128
1
INTRODUCTION
In
this
paper,
a
dimeric
complex
[{Sm(HPht)(Phen)(H2O)2}2(μ-Pht)2] (I), where Pht2– is
dianion of o-phthalic acid; HPht– is monoanion of o-
phthalic acid; Phen is 1,10-phenanthroline has been
synthesized through the hydrothermal reaction, and its
Lanthanide ions are known for their luminescence
properties, which make them interesting candidates for
luminescence applications, such as bioactive probes for
magnetic resonance and luminescence [1–7]. Since the crystal structure has been investigated.
emission mechanism is based on f–f transitions with
consequent narrow bandwidth and no theoretical cap on
EXPERIMENTAL
the quantum efficiency, they are especially interesting
candidates for LED (liquid electronic display) applica-
tions. The f–f transitions are spin and parity forbidden,
and to exploit the luminescent properties, ligands that
function as sensitizers are used. Benzoic acid and its
derivatives have been described as efficient sensitizers
for lanthanide emission [8–11]. Of the numerous lan-
thanide complexes with carboxylate ligands widely
studied, most possess a variety of dimeric or infinite
chain structures in which the carboxylate groups act as
bridges between metal atoms, and the number of bridg-
ing carboxylate groups varies in different complexes
[12]. Aromatic polycarboxylic acids, such as 2,6-naph-
thalenedicarboxylic acid [13], 1,4-benzenedicarboxylic
acid [14], and 1,3-benzenedicarboxylic acid [15, 16]
were used extensively in the synthesis of coordination
polymers, whereas the utilization of 1,2-benzenedicar-
boxylic acid, monobenzoate and derivatives to con-
struct polymeric Ln(III) complexes is much less well
known, although several examples have been reported
recently [17, 18].
Synthesis of I. Sm(NO3)3 · 6H2O (0.1370 g,
0.3 mmol), KHPhth (potassium biphthalate, 0.0920 g,
0.45 mmol), and Phen (0.0590 g, 0.3 mmol) were
mixed in 10 ml of deionized water. After being stirred
half an hour, the mixture was placed in a 25-ml teflon-
lined reactor, heated at 160°C in an oven for 3 days, and
cooled slowly to room temperature, and the pink block
crystals of complex I suitable to X-ray diffraction anal-
ysis were obtained. IR spectrum exhibits a complicated
pattern of bands in the range 4000–400 cm–1: 1417 cm–1
(νsCOO–), 1545 cm–1 (νasCOO–).
The X-ray single crystal data collections for com-
plex I was performed on a Bruker Smart CCD diffrac-
tometer equipped with a graphite monochromator
MoKα radiation (λ = 0.71073 Å). Multiscan absorption
correction was applied using the SADABS program
[19]. The structure was solved by a direct method using
the SHELXS-97 program [20]. Refinement on F2 was
performed using SHELXL-97 [21] by a full-matrix
least-squares method with anisotropic parameters for
all non-hydrogen atoms. The hydrogen atoms of the
ligands were generated geometrically, while the H
1
The article is published in the original.
864

Bis(μ2-1-CARBOXYBENZENE-2-CARBOXYLATO)
Table 1. Selected bond distances and bond angles for compound I*
865
Bond
d, Å
Bond
d, Å
Bond
d, Å
Sm(1)–N(1)
Sm(1)–O(5)
Sm(1)–O(8A)
2.563(2)
2.3819(18)
2.448(2)
Sm(1)–N(2)
Sm(1)–O(6)
Sm(1)–O(9)
2.527(2)
2.4886(19)
2.409(2)
Sm(1)–O(1)
Sm(1)–O(7A)
Sm(1)–O(10)
2.332(2)
2.4043(19)
2.3098(18)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
N(2)Sm(1)N(1)
O(10)Sm(1)O(1)
O(10)Sm(1)O(7A)
O(10)Sm(1)O(9)
O(7A)Sm(1)O(9)
O(5)Sm(1)O(8A)
O(1)Sm(1)O(6)
O(8A)Sm(1)O(6)
O(5)Sm(1)N(2)
O(8A)Sm(1)N(2)
O(1)Sm(1)N(1)
64.66(7)
83.78(8)
131.71(7)
74.97(7)
71.28(7)
127.79(7)
68.88(7)
143.07(8)
80.92(7)
94.77(8)
71.26(7)
O(5)Sm(1)O(6)
O(10)Sm(1)O(5)
O(1)Sm(1)O(7A)
O(1)Sm(1)O(9)
O(10)Sm(1)O(8A)
O(9)Sm(1)O(8A)
O(7A)Sm(1)O(6)
O(10)Sm(1)N(2)
O(7A)Sm(1)N(2)
O(6)Sm(1)N(2)
O(5)Sm(1)N(1)
53.42(6)
130.33(7)
143.44(7)
137.67(8)
84.05(8)
O(7A)Sm(1)O(8A)
O(1)Sm(1)O(5)
O(5)Sm(1)O(7A)
O(5)Sm(1)O(9)
O(1)Sm(1)O(8A)
O(10)Sm(1)O(6)
O(9)Sm(1)O(6)
O(1)Sm(1)N(2)
O(9)Sm(1)N(2)
O(10)Sm(1)N(1)
O(8A)Sm(1)N(1)
53.81(7)
87.36(7)
75.61(7)
79.67(7)
140.91(7)
77.99(7)
71.09(7)
72.16(7)
142.82(7)
77.70(8)
69.88(7)
73.20(8)
120.37(6)
140.02(7)
73.33(7)
119.58(7)
143.46(7)
* Coordinates of atoms A: –x + 1, –y, –z + 1.
atoms of the coordination water molecules were located
Selected bond distances and bond angles for com-
from Fourier difference synthesis and refined with pounds I are listed in Table 1. The ORTEP drawing of
restraints.
I is shown in Fig. 1. Crystallographic data for com-
O(6)
O(8)
O(10)
O(7)
O(5)
O(1)
N(2A)
N(1A)
O(2)
Sm(1)
O(9)
O(4A)
O(3A)
O(3)
Sm(1A)
O(9A)
O(4)
N(2)
O(2A)
O(1A)
N(1)
O(5A)
O(7A)
O(8A)
O(10A)
O(6A)
Fig. 1. Dimeric structure of complex I. Atomic displacement ellipsoids are shown at the 30% probability level.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 35 No. 11 2009

866
YU et al.
Table 2. Intra- and intermolecular hydrogen bond geometry for structure I*
Distance, Å
Contect D–H···A
Angle DHA, deg
D–H
H···A
D···A
O(3)–H(3A)···O(2)
O(9)–H(9A)···O(5)#1
O(9)–H(9B)···O(3)#2
O(10)–H(10A)···O(4)#2
O(10)–H(10B)···O(6)#1
C(1)–H(1)···O(10)
0.82(5)
0.86(2)
0.86(2)
0.87(2)
0.86(4)
0.93
1.58(5)
2.07(2)
2.02(3)
1.80(3)
1.95(3)
2.46
2.388(3)
2.904(3)
2.881(3)
2.661(3)
2.806(3)
3.065(4)
3.354(4)
3.116(4)
2.687(4)
3.342(4)
169(7)
164(5)
176(5)
169(5)
175(5)
123
C(11)–H(11)···O(2)#3
C(12)–H(12)···O(5)
C(15)–H(15)···O(1)
C(15)–H(15)···O(6)#4
C(18)–H(18)···O(4)
0.93
2.47
158
0.93
2.48
125
0.93
2.33
102
0.93
2.53
147
0.93
2.29
2.663(4)
103
#1
#2
#3
#4
* Symmetry transformations used to generate equivalent atoms: 1 – x, –y, 1 – z; –x, –y, 1 – z; 1 – x, 1 – y, 1 – z; x, –1 + y, z.
the Sm3+ ion, whose bond distances are 2.563(2) and
2.527(2) Å. The bond angles consisting of Sm(III) and
the oxygen atoms from the Pht2– ions range from
53.42(6)° to 53.81(7)°; the bond angle consisting of
Sm(III) and the two nitrogen atoms is 64.66(7)°. The
distance of Sm(1)–Sm(1A) in the dimeric unit was
determined to be 5.855 Å.
pound I was deposited with the Cambridge Crystallo-
graphic Data Center (no. 707666; deposit@ccdc.
cam.ac.uk).
RESULTS AND DISCUSSION
The title complex I crystallizes in the triclinic sys-
Two types of coordination modes of the Pht2– and
HPht– ligands exist in the molecular structure of the
binuclear complex: (1) tetradentate bis(chelating) bridg-
ing, the Pht2– anions are completely deprotonated and
all four oxygen atoms take part in the coordination to
the two central metal ions and the Sm3+ ions are con-
nected into dinuclear structure by this coordination
mode, and (2) monodentate coordination, the HPht–
anions merely lose one proton and the deprotonated
carboxylic acid group provides one carbonyl oxygen
atom coordinated with the Sm3+ ion. There are rich
tem, with space group P1. The two Sm3+ ions are both
equivalent in the same coordination environment and so
there is only one type of metal configuration. Each cen-
tral Sm3+ ion is nine-coordinated, whose coordination
geometry can be described as a distorted square
monoantiprism. Among the nine coordinations, four
oxygen atoms are from the two bridging Pht2– groups
(for Sm(1) ion, O(5), O(6) from one chelate-bridging
Pht2– and O(7A), O(8A) from the symmetric Pht2– with
the bond distances of 2.3819(18)–2.4886(19) Å for
Sm(1)–O, and one oxygen atom is from the HPht– intramolecular hydrogen bonds (Table 2). The unit cell
group (O(1) for Sm(1)), whose bond distance is shorter (Fig. 2) diagram indicates that there are four types of
(2.332(2) Å). Besides this, there are other two coordi- intermolecular hydrogen bonds. The first type is
nated oxygen atoms from the two water molecules formed between the oxygen atom of the bridging Pht2–
(O(9) and O(10)) with bond distances of 2.409(2) Å for ligand and the oxygen atom of the coordinated water
Sm(1)–O(9) and 2.3098(18) Å for Sm(1)–O(10). One molecules in the adjacent molecular unit, such as O(9)–
bidentate Phen provides two nitrogen atoms chelated to H(9A)···O(5)#1 and O(10)–H(10B)···O(6)#1. The second
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 35 No. 11 2009

Bis(μ2-1-CARBOXYBENZENE-2-CARBOXYLATO)
867
x
z
0
y
Fig. 2. Crystal packing perspective view of I showing supramolecular weak interaction of hydrogen bonds.
7. Dickins, R.S., Aime, S., Batsanov, A.S., et al., J. Am.
Chem. Soc., 2002, vol. 124, p. 12697.
8. Barja, B., Baggio, R., Garland, M.T., et al., Inorg. Chim.
Acta, 2003, vol. 346, p. 187.
9. Wang, Z., Strobele, M., Zhang, K.L., et al., Inorg. Chem.
Commun., 2002, vol. 5, p. 230.
10. Wan, Y., Zhang, L., Jin, L., et al., Inorg. Chem., 2003,
vol. 42, p. 4985.
11. Wan, Y., Jin, L., Wang, K., et al., New J. Chem., 2002,
vol. 26, p. 1590.
12. Serre, C., Millange, F., Thouvenot, C., et al., J. Mater.
Chem., 2004, vol. 14, p. 1540.
type is formed between the oxygen atom of the coordi-
nated water molecule and the oxygen atom of the HPht–
group from an adjacent molecule, such as O(9)–
H(9B)···O(3)#2 and O(10)–H(10A)···O(4)#2. The third one
is formed between the O atom of the Pht2– group and the
C atom of HPht– C(15)–H(15)···O(6)#4 from adjacent
molecular units. The forth one is formed between the O
atom of HPht– and the C atom of the Phen molecule
C(11)–H(11)···O(2)#3 from an adjacent molecule
(Table 2). The intermolecular hydrogen bonds link up
the complex to form a 3D network.
13. Wei, P.R., Wu, D.D., Zhou, Z.Y., et al., Polyhedron.,
1997, vol. 16, p. 749.
ACKNOWLEDGMENTS
14. Rosi, N.L., Eddaoudi, M., Kim, J., et al., Angew. Chem.
Int. Ed., 2002, vol. 41, p. 284.
15. Bourne, S.A., Lu, J.J., Mondal, A., et al., Angew. Chem.
Int. Ed., 2001, vol. 40, p. 2111.
16. Zheng, C.G., Zhang, J., Chen, Z.F., et al., J. Coord.
Chem., 2002, vol. 55, p. 835.
This work was supported by the Scientific Research
Fund of the Hunan Provincial Education Department
(08c340) and the Foundation of the Hunan University
of Science and Technology (E55106).
17. Zhang, L.P., Wan, Y.H., and Jin, L.P., Polyhedron.,
2003, vol. 22, p, 981.
18. Roh, S.G., Nah, M.K., Oh, J.B., et al., Polyhedron.,
2005, vol. 24, p. 137.
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