Syntheses and structural researches of nine-coordinated (NH 4)[EuIII(Edta)(H2O)3]·H 2O and (NH4)3[EuIII(Ttha)] ·5H2O1

Article abstract of DOI:10.1023/B:RUCO.0000015085.35282.af

The crystal and molecular structures of the (NH₄)[Eu ^III(Edta)(H₂O)₃]·H₂O (I); Edta^4- is an ethylenediaminetetraacetate anion) and (NH ₄)₃[Eu^III(Ttha)]·5H₂O (II); Ttha^6- is a triethylenetetraminehexaacetate anion) complexes have been determined by single-crystal X-ray structure analysis. The crystal of complex I is orthorhombic with Fdd2 space group. The crystal data are as follows: a = 1.9505(8) nm, b = 3.5445(14) nm, c = 1.2442(5) nm, V = 8.602(6) nm³, Z = 16, M = 531.29, p = 1.579 g cm^-3, μ = 2.970 mm^-1, and F(OOO) = 3924. The final R and wR values are 0.0378 and 0.1030 for 2799 (I > 2.0σ(I)) unique reflections, and 0.0495 and 0.1072 for all 6237 reflections, respectively. The nine-coordinated [Eu ^III(Edta)(H₂O)₃]^- complex anion has a pseudo-monocapped square antiprismatic structure in which the nine coordinated atoms, two N and four O are from one Edta ligand and three O atoms from water molecules. The crystal of complex II is monoclinic with P2₁/c space group. The crystal data are as follows: a = 1.0387(3) nm, b = 1.2737(4) nm, c = 2.3031(7) nm, β = 90.870(5)°, V = 3.047(2) nm³, Z = 4, M = 784.58, C 51.83, H 4.32, N 115.12. ρ = 1.710 g cm^-3, μ = 2.143 mm^-1 and F(000) = 1608. The final R and wR are 0.0400 and 0.0720 for 5909 (I > 2.0σ(I)) unique reflections, and 0.0747 and 0.0799 for all 13825 reflections, respectively. The nine-coordinated [Eu^III(Ttha)] ^3- complex anion has a pseudo-monocapped square antiprismatic structure in which the Ttha acts as an ninedentate ligand with four N atoms of amino groups and five O atoms of carboxylic groups actually, in addition, there is a non-coordinated free carboxylic group in the structure.

Full text of DOI:10.1023/B:RUCO.0000015085.35282.af

Russian Journal of Coordination Chemistry, Vol. 30, No. 2, 2004, pp. 130–136. From Koordinatsionnaya Khimiya, Vol. 30, No. 2, 2004, pp. 141–147.
Original English Text Copyright © 2004 by Wang, Zhang, Jia, Zhang, Liu.
Syntheses and Structural Researches of Nine-Coordinated
(NH4)[EuIII(Edta)(H2O)3] · H2O and (NH4)3[EuIII(Ttha)] · 5H2O1
J. Wang, X. D. Zhang, W. G. Jia, Y. Zhang, and Z. R. Liu
Department of Chemistry, Liaoning University, Shenyang, 110036 P. R. China
Received January 10, 2003
Abstract—The crystal and molecular structures of the (NH4)[EuIII(Edta)(H2O)3] · H2O (I); Edta4– is an ethyl-
enediaminetetraacetate anion) and (NH4)3[EuIII(Ttha)] · 5H2O (II); Ttha6– is a triethylenetetraminehexaacetate
anion) complexes have been determined by single-crystal X-ray structure analysis. The crystal of complex I is
orthorhombic with Fdd2 space group. The crystal data are as follows: a = 1.9505(8) nm, b = 3.5445(14) nm,
c = 1.2442(5) nm, V = 8.602(6) nm3, Z = 16, M = 531.29, p = 1.579 g cm–3, µ = 2.970 mm–1, and F(OOO) =
3924. The final R and wR values are 0.0378 and 0.1030 for 2799 (I > 2.0σ(I)) unique reflections, and 0.0495
and 0.1072 for all 6237 reflections, respectively. The nine-coordinated [EuIII(Edta)(H2O)3]– complex anion has
a pseudo-monocapped square antiprismatic structure in which the nine coordinated atoms, two N and four O
are from one Edta ligand and three O atoms from water molecules. The crystal of complex II is monoclinic with
P21/c space group. The crystal data are as follows: a = 1.0387(3) nm, b = 1.2737(4) nm, c = 2.3031(7) nm, β =
90.870(5)°, V = 3.047(2) nm3, Z = 4, M = 784.58, C 51.83, H 4.32, N 115.12. ρ = 1.710 g cm–3, µ = 2.143 mm–1
and F(000) = 1608. The final R and wR are 0.0400 and 0.0720 for 5909 (I > 2.0σ(I)) unique reflections, and
0.0747 and 0.0799 for all 13825 reflections, respectively. The nine-coordinated [EuIII(Ttha)]3– complex anion
has a pseudo-monocapped square antiprismatic structure in which the Ttha acts as an ninedentate ligand with
four N atoms of amino groups and five O atoms of carboxylic groups actually, in addition, there is a non-coor-
dinated free carboxylic group in the structure.
The great attention has been paid to the rare earth 1 complexes are thought to be typical for all trivalent
metal complexes all along because these metal ions
show biological activities [1–3]. For example, some
Nd(III) complexes exhibit good antiinflammation
activity; the most high-spin (seven unpair-single elec-
trons) Gd(III) complexes were often used as contrast
agent in magnetic resonance imaging diagnoses [4]; the
Tb(III) and Eu(III) complexes have been used to diag-
nose some diseases qua the ionic probes for their char-
acter fluorescence [5]. Recently, we are cooperating
with Dr. J. Kang and studying the luminescence prop-
erties and fluorescence spectra of the Eu(III) complexes
with aminopolycarboxylic acids at low temperature [6].
rare earth metal ions with Edta ligand, but these com-
plexes have different coordination structures or coordi-
nation numbers [9]. For example, the La(III) (having
ionic radius of 0.1172 nm and electronic configuration
of f 0) with Edta ligand forms the ten-coordinated com-
plex having a slightly distorted bicapped square anti-
prismatic structure [10], the Y(III) (0.1040 nm and f 0),
and Gd(III) (0.1078 nm and high-spin f 7) form with
Edta ligand the nine-coordinated complexes having a
slightly distorted monocapped square antiprismatic
structure [11, 12]. However, the Dy(III) (0.1052 nm and
high-spin f 9), Ho(III) (0.1041 nm and high-spin f 10),
and Er(III) (0.1030 nm and high-spin f 11) form with
Edta ligand the eight-coordinated complexes having a
slightly distorted square antiprismatic structure. In
these complexes, the Edta ligand is coordinated to var-
ious rare earth metal ions and acts as a hexadentate
ligand. Because the Eu3+ ion has the ionic radius of
0.1087 nm and electronic configuration of high-spin f 6
which are similar to ones of Y3+ (0.1040 nm and f 0) and
Gd3+ (0.1078 nm and high-spin f 7) ions, it should also
form the nine-coordinated complexes with Edta ligand
like the Y3+ and Gd3+ ions in principle. The nine-coor-
dinated (NH4)[EuIII(Edta)(H2O)3] · H2O (I) complex
has been produced inefficiently. In order to verify this
forecast, the ((NH4)3[EuIII(Ttha)] · 5H2O (II); Ttha6– is a
triethylenetetraminehexaacetate anion) complex was
We know that the electronic configuration of the rare
earth metal ions determines the luminescence proper-
ties and fluorescence spectra of the complexes, but the
electronic configuration rests with the coordinate struc-
tures of the complexes. In order to explain the lumines-
cence properties and fluorescence spectra of the Eu(III)
complexes with aminopolycarboxylic acids particu-
larly and explore the relationships among coordinate
structure, electronic configuration and fluorescence
spectrum, it is very important to determine their molec-
ular and crystal structures. The Edta (H4Edta = ethyl-
enediaminetetraacetic acid) is a simple and useful
ligand in all aminopolycarboxylic acids [7, 8]. The 1 :
1
This article was submitted by the authors in English.
1070-3284/04/3002-0130 © 2004 åÄIä “Nauka /Interperiodica”

SYNTHESES AND STRUCTURAL RESEARCHES
131
O(10)
also prepared and the determined result indicated that
the Eu3+ ion still takes the nine-coordinated structure
with Ttha ligand. Besides, the [EuIII(Ttha)]3– part has an
interesting molecular structure in which there is a non-
coordinated free carboxylic group and the Ttha ligand
gives only nine donor atoms (four amino N and five car-
boxylic O atoms) although it is a decadentate ligand.
The [EuIII(Ttha)]3– complex anion is likely to be used as
the targeting fluorescent diagnostic reagent with direc-
tional function through embellishing this non-coordi-
nated free carboxylic group.
O(11)
O(9)
O(7)
O(8)
O(3)
C(9)
O(4)
Eu(1)
O(5)
C(3)
O(1)
C(4)
N(2)
C(10)
C(7)
O(6)
C(8)
N(1)
C(1)
C(2)
O(2)
C(6)
EXPERIMENTAL
C(5)
Synthesis of (NH4)[EuIII(Edta)(H2O)3] · H2O (I).
1.46 g (5.0 mmol) H4Edta was added to 100 ml water,
and then 0.87 g (2.5 mmol) Eu2O3 powder was added in
batches. The mixture was stirred and refluxed for
15.5 h, the pH was adjusted to 6.5 with aqueous NH3
after the solution became transparent and then the solu-
tion was concentrated to 25 ml. The colorless crystals
appeared after two weeks at room temperature.
III
–
Fig. 1. Molecular structure of [Eu (Edta)(H O) ] .
2
3
c
For C10H20EuN3O12
anal. cacld (%):
Eu, 28.60;C, 22.61; H, 4.74; N, 7.91.
Eu, 28.68;C, 22.60; H, 4.76; N, 7.90.
b
0
Found (%):
This formula is approximately consistent with the
result of X-ray diffraction analysis.
Synthesis of (NH4)3[EuIII(Ttha)] · 5H2O (II).
2.47g (5.0 mmol) H6Ttha was added to 100 ml water,
and then 0.87 g (2.5 mmol) Eu2O3 powder was added to
above solution slowly. The mixture was stirred and
refluxed for 10 h at the same time, the pH was adjusted
to 5 by aqueous NH3 after the solution became transpar-
ent and then the solution was concentrated to 25 ml.
The colorless crystals appeared after three weeks at
room temperature.
a
For C18H46EuN7O17
anal. cacld (%):
Eu, 19.37; C, 27.55; H, 5.91; N, 12.50.
Eu, 19.30; C, 27.56; H, 5.90; N, 12.52.
Found (%):
III
Fig. 2. Packing of (NH )[Eu (Edta)(H O) ] · H O mole-
4
2
3
2
This formula is approximately consistent with the
result of X-ray diffraction analysis.
cules in unit cell.
IR analysis. H4Edta, H6Ttha, complexes I and II
mull and press slice with KBr, respectively. Their IR
spectra were recorded on a Shimadzu-IR 408 spec-
trograph.
X-ray diffraction analysis. The details of crystal
data collection and refinement parameters for com-
plexes I and II are listed in Table 1. Data were collected
with a Bruker SMART CCD type X-ray diffractometer
using graphite-monochromated MoKα radiation (λ =
0.071073 nm). The structures were solved by direct
methods. All non-hydrogen atoms were refined with
anisotropic thermal parameters by full-matrix method.
gram on PDP11/44 and Pentium MMX/166 computers.
The structures of the complex anions and the molecular
packing of the complexes in unit cell are shown in Figs.
1 and 2 for I, Figs. 3 and 4 for II, respectively. The
coordination polyhedrons around Eu3+ ions in
[EuIII(Edta)(H2O)3]– and [EuIII(Ttha)]3– complex anions
are shown in Figs. 5 and 6, respectively. All the non-
hydrogen fractional atomic coordinates and equivalent
isotropic temperature factors of these two complexes
are listed in Table 2 and Table 3, respectively. The
selected bond distances and bond angles of these two
All calculations were carried with SHELXTL97 pro- complexes are listed in Tables 4 and 5, respectively.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004

132
WANG et al.
Table 1. Crystal data and refinement of structure I and II
I
II
Formula weight
Temperature, K
Crystal system
Space group
Unit cell dimensions
a, nm
531.29
293(2)
784.58
293(2)
Orthorhombic
Fdd2
Monoclinic
P21/c
1.9505(8)
3.5445(14)
1.2442(5)
1.0387(3)
1.2737(4)
2.3031(7)
90.870(5)
3.0468(17)
4
b, nm
c, nm
β, deg
Volume, nm3
8.602(6)
16
Z
Calculated density, mg m–3
Absorption coefficient, mm–1
F(000)
1.579
1.710
2.970
2.143
3924
1608
Crystal size, mm
θ range, deg
Index ranges
0.25 × 0.20 × 0.15
2.02–23.30
0.30 × 0.20 × 0.16
1.77–26.40
–21 ≤ h ≤ 17
–22 ≤ k ≤ 39
–13 ≤ l ≤ 13
–12 ≤ h ≤ 12
–15 ≤ k ≤ 5
–28 ≤ l ≤ 26
Reflections collected
Independent reflections
Final R indices (I > 2σ(I))
R indices (all data)
6237
13825
2799 (Rint = 0.0376)
R = 0.0378, wR = 0.1030
R = 0.0495, wR = 0.1072
5909 (Rint = 0.0538)
R = 0.0400, wR = 0.0720
R = 0.0747, wR = 0.0799
Absorption correction
Refinement method
Semi-empirical from equivalents
Full-matrix least-squares on F2
RESULTS AND DISCUSSION
spectrum of II. The νas(COO) at 1642 cm–1 of H6Ttha
red-shifts to 1603 cm–1 partly and νs(COO) at 1389 cm–1
of H6Ttha blue-shifts to 1415 cm–1 partly for II, which
not only confirms that the O atoms of some –COO–
groups coordinate with central Eu3+ ion, but also shows
that there is a non-coordinated free carboxylic group in
the complex II. There is a wide ν(OH) band of H2O
near 3455 cm–1 showing the existence of H2O in the
complex.
It can be seen in Fig. 1 that the central Eu3+ ion of
the structure I is coordinated with two N atoms and four
O atoms from an Edta ligand, and the other three O
atoms from three coordinated H2O molecules in the
[EuIII(Edta)(H2O)3]– complex anion. The set of O(3),
O(7), O(9) and O(11) atoms and the set of O(1), O(5),
It can be seen that ν(C–N) of I is at 1085 cm–1 and
red-shifts 43 cm–1 comparing with that of H4Edta
(1128 cm–1) which indicates that the two N atoms from
an Edta ligand are coordinated to the central Eu3+ ion.
For the vibration related -COOH group, it was found
that the νas(COOH) in Edta at 1690 cm–1 disappeared in
the IR spectrum of I, and νas(COO) at 1610 cm–1 of
Edta red-shifts to 1578 cm–1 and νs(COO) at 1390 cm–1 of
Edta violet-shifts to 1404 cm–1 for I, which confirms
that the O atoms of all four –COO– groups are also
coordinated with Eu3+ ion. There is a wide ν(OH) band
of H2O near 3440 cm–1 showing the existence of H2O in
the complex.
It can be observed that the ν(C–N) of II is at N(1) and N(2) atoms form two approximate squares,
1075 cm–1 and red-shifts 50 cm–1 comparing with that respectively, which make a square antiprism, so the
of H6Ttha (1125 cm–1) which indicates that the N atom EuIIIN2O7
part
in
the
nine-coordinated
from Ttha ligand coordinates with central Eu3+ ion. The [EuIII(Edta)(H2O)3]– complex anion has a pseudo-mono-
νas(COOH) in Ttha at 1736 cm–1 disappeared in the IR capped square antiprismatic structure (Fig. 5). The
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004

SYNTHESES AND STRUCTURAL RESEARCHES
133
O(3)
O(4)
C(3)
O(12)
O(6)
a
C(4)
c
0
C(17)
O(5)
C(7)
C(8)
C(5)
N(1)
O(11)
C(2)
O(18)
C(1)
C(6)
O(1)
Eu(1)
O(2)
N(4)
N(2)
C(14)
C(16)
b
O(9)
C(9)
C(15)
O(7)
C(10)
N(3)
C(13)
C(11)
O(10)
C(12)
O(8)
III
Fig. 4. Packing of (NH ) [Eu (Ttha)] · 5H O molecules in
4 3
2
III
3–
unit cell.
Fig. 3. Molecular structure of [Eu (Ttha)] .
O(10)
O(1)
O(3)
N(1)
O(7)
O(7)
O(11)
O(11)
O(9)
O(9)
Eu(1)
Eu(1)
O(1)
N(1)
O(5)
N(2)
N(2)
N(4)
O(5)
N(3)
Fig. 5. Coordination polyhedrons around Eu(III) in
Fig. 6. Coordination polyhedrons around Eu(III) in
[Eu (Ttha)] .
III
–
III
3–
[Eu (Edta)(H O) ] .
2
3
the repulsion of these four coordinated O atoms, the
EuIII–O(10) distance (0.2539(8) nm) is the longest
among all the EuIII–O distances, while the EuIII–O(9)
and EuIII–O(11) distances (O(9) and O(11) atoms also
come from coordinated water molecules) are only
0.2458(8) and 0.2474(8) nm, respectively. The results
in this paper and the ones reported previously indicate
atom O(10) from a coordinated H2O molecule is above
the plane formed by O(3), O(7), O(9) and O(11) atoms
and the average value of the angles O(3)Eu(1)O(10),
O(7)Eu(1)O(10), O(9)Eu(1)O(10) and O(11)Eu(1)O(10)
is 71.73° close to 70° that most complexes with nine-
coordinate pseudo-monocapped square antiprismatic
structure adopt, in which the biggest and smallest
angles are 74.13° and 69.13°, respectively. Because of that the Eu3+ ion having the ionic radius of 0.1087 nm
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004

134
WANG et al.
Table 2. Coordinates of atoms (×104) and their equivalent isotropic thermal parameters Ueq (×103) in the crystal structure I
Atom
Eu(1)
x
y
z
Ueq, nm2
Atom
x
y
z
Ueq, nm2
1683(1)
1957(5)
1038(5)
1536(5)
1412(8)
2797(5)
3534(7)
468(4)
9044(1)
9784(2)
9441(3)
9315(3)
9800(3)
9181(3)
9576(4)
9182(2)
9255(3)
9156(2)
9246(3)
8591(2)
8479(2)
8538(3)
10082(1)
10200(10)
8518(8)
34(1)
42(2)
40(3)
53(2)
92(5)
57(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
N(3)
O(12)
O(13)
1502(8)
9661(4) 12061(12)
58(4)
66(5)
68(4)
58(4)
57(5)
53(4)
42(3)
46(3)
40(3)
38(3)
66(4)
78(7)
N(1)
N(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
1591(10) 9934(5) 11096(14)
3010(9)
2671(8)
1752(8)
1063(8)
43(7)
9521(5) 10964(12)
9826(4) 10383(11)
11858(7)
12981(8)
10829(8)
9973(5)
9846(4)
9252(3)
9318(4)
9362(3)
9252(3)
352(3)
9154(14)
8798(12)
9638(10)
8518(10)
7455(11)
7591(12)
3604(10)
3569(16)
11603(11) 102(4)
10364(7)
9761(7)
8510(7)
6732(8)
8827(7)
9908(7)
11252(7)
43(2)
64(3)
41(2)
59(3)
42(2)
50(2)
50(3)
315(7)
–598(5)
2361(5)
2467(5)
1163(5)
2475(5)
1230(5)
1371(5)
2129(6)
557(7)
1354(13) 8853(6)
8470(20) 9041(6)
8310(30) 137(15)
Table 3. Coordinates of atoms (×104) and their equivalent isotropic thermal parameters Ueq (×103) in the crystal structure II
Atom
x
y
z
Ueq, nm2
Atom
x
y
z
Ueq, nm2
Eu(1)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(12)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
2443(1)
1588(3)
–61(3)
2311(1)
2214(3)
8670(1)
9616(1)
21(1)
27(1)
33(1)
50(1)
45(1)
33(1)
51(1)
29(1)
46(1)
30(1)
52(1)
29(1)
41(1)
23(1)
26(1)
26(1)
26(1)
23(1)
26(1)
29(1)
28(1)
30(1)
C(6)
–354(4)
1992(5)
1288(5)
1239(5)
2665(5)
1672(5)
2904(5)
4702(5)
5159(5)
4980(5)
5673(5)
4443(5)
5191(5)
1369(5)
4120(5)
2080(4)
3389(4)
6780(4)
1553(4)
3026(4)
6391(6)
2312(4)
4071(4)
3205(4)
1320(4)
1101(4)
–122(4)
–125(4)
997(4)
7856(2)
7632(2)
7311(2)
7342(2)
7309(2)
8449(2)
8100(2)
7823(2)
7887(2)
9178(2)
8917(2)
8995(2)
8515(2)
9081(2)
9407(2)
4992(2)
9896(2)
9524(2)
6222(2)
8246(2)
8733(3)
31(1)
31(1)
31(1)
36(1)
35(1)
28(1)
34(1)
35(1)
37(1)
33(1)
33(1)
27(1)
32(1)
43(1)
68(2)
33(1)
50(1)
59(1)
59(1)
59(1)
114(2)
C(7)
1535(3) 10096(2)
C(8)
–715(4)
–1987(3)
2543(3)
1994(4)
1287(3)
1125(4)
3753(3)
5613(3)
3599(3)
4682(4)
101(4)
5795(3)
4438(3)
3834(3)
4957(3)
736(3)
9289(2)
9184(2)
8103(2)
7416(2)
8646(2)
8522(2)
9168(2)
9390(2)
9244(2)
9106(2)
8809(2)
7675(2)
7882(2)
8474(2)
9681(2)
9214(2)
9188(2)
9072(2)
8253(2)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
N(5)
–972(3)
1078(3)
321(3)
2121(4)
1043(4)
1965(4)
4182(4)
3667(4)
7076(4)
8419(4)
5005(4)
6366(3)
6469(3)
4849(4)
6302(3)
8251(4)
3633(3)
5114(3)
3155(3)
2287(3)
913(3)
1004(4)
3273(4)
4912(4)
389(5)
N(6)
N(7)
2533(3)
2035(3)
2423(4)
4860(4)
4193(4)
3218(4)
O(13)
O(14)
O(15)
O(16)
O(17)
–519(4)
–918(5)
270(5)
–634(5)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004

SYNTHESES AND STRUCTURAL RESEARCHES
Table 4. Bond lengths and angles in the crystal structure I
135
Bond
d, nm
Bond
d, nm
Bond
d, nm
Eu(1)–O(1)
Eu(1)–O(7)
Eu(1)–O(11)
0.2427(9)
0.2394(9)
0.2474(8)
Eu(1)–O(3)
Eu(1)–O(9)
Eu(1)–N(1)
0.241(1)
0.2458(8)
0.2679(9)
Eu(1)–O(5)
Eu(1)–O(10)
Eu(1)–N(2)
0.2446(8)
0.2539(8)
0.271(1)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O(1)Eu(1)O(3)
O(1)Eu(1)O(9)
O(1)Eu(1)N(1)
O(3)Eu(1)O(7)
O(3)Eu(1)O(11)
O(5)Eu(1)O(7)
O(5)Eu(1)O(11)
O(7)Eu(1)O(9)
O(7)Eu(1)N(1)
O(9)Eu(1)O(11)
O(10)Eu(1)O(11)
O(11)Eu(1)N(1)
71.1(3)
142.0(3)
65.6(3)
77.5(3)
103.9(3)
128.3(3)
73.4(3)
79.5(3)
76.8(3)
75.7(3)
72.2(3)
138.5(3)
O(1)Eu(1)O(5)
O(1)Eu(1)O(10)
O(1)Eu(1)N(2)
O(3)Eu(1)O(9)
O(3)Eu(1)N(1)
O(5)Eu(1)O(9)
O(5)Eu(1)N(1)
O(7)Eu(1)O(10)
O(7)Eu(1)N(2)
O(9)Eu(1)N(1)
O(10)Eu(1)N(1)
O(11)Eu(1)N(2)
71.1(3)
117.5(3)
113.2(3)
138.4(3)
66.5(3)
O(1)Eu(1)O(7)
O(1)Eu(1)O(11)
O(3)Eu(1)O(5)
O(3)Eu(1)O(10)
O(3)Eu(1)N(2)
O(5)Eu(1)O(10)
O(5)Eu(1)N(2)
O(7)Eu(1)O(11)
O(9)Eu(1)O(10)
O(9)Eu(1)N(2)
O(10)Eu(1)N(2)
N(1)Eu(1)N(2)
138.0(3)
73.1(3)
141.0(3)
69.1(3)
126.2(3)
139.5(3)
63.2(3)
143.0(3)
71.4(3)
72.1(3)
129.1(3)
67.9(3)
79.8(3)
89.4(3)
74.1(3)
65.4(3)
139.2(3)
130.9(3)
129.3(3)
Table 5. Bond lengths and angles in the crystal structure II
Bond
d, nm
Bond
d, nm
Bond
d, nm
Eu(1)–O(1)
Eu(1)–O(9)
Eu(1)–N(2)
0.2369(3)
0.2363(3)
0.2718(4)
Eu(1)–O(5)
Eu(1)–O(11)
Eu(1)–N(3)
0.2342(3)
0.2445(3)
0.2694(4)
Eu(1)–O(7)
Eu(1)–N(1)
Eu(1)–N(4)
0.2338(3)
0.2683(4)
0.2626(4)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O(1)Eu(1)O(5)
O(1)Eu(1)O(11)
O(1)Eu(1)N(3)
O(5)Eu(1)O(9)
O(5)Eu(1)N(2)
O(7)Eu(1)O(9)
O(7)Eu(1)N(2)
O(9)Eu(1)O(11)
O(9)Eu(1)N(3)
O(11)Eu(1)N(2)
N(1)Eu(1)N(2)
N(2)Eu(1)N(3)
125.2(2)
74.2(1)
135.5(1)
142.3(1)
64.4(1)
74.5(1)
72.2(1)
85.5(1)
72.5(1)
136.3(1)
67.5(1)
66.5(1)
O(1)Eu(1)O(7)
O(1)Eu(1)N(1)
O(1)Eu(1)N(4)
O(5)Eu(1)O(11)
O(5)Eu(1)N(3)
O(7)Eu(1)O(11)
O(7)Eu(1)N(3)
O(9)Eu(1)N(1)
O(9)Eu(1)N(4)
O(11)Eu(1)N(3)
N(1)Eu(1)N(3)
N(2)Eu(1)N(4)
77.2(1)
63.8(1)
O(1)Eu(1)O(9)
O(1)Eu(1)N(2)
O(5)Eu(1)O(7)
O(5)Eu(1)N(1)
O(5)Eu(1)N(4)
O(7)Eu(1)N(1)
O(7)Eu(1)N(4)
O(9)Eu(1)N(2)
O(11)Eu(1)N(1)
O(11)Eu(1)N(4)
N(1)Eu(1)N(4)
N(3)Eu(1)N(4)
75.0(1)
124.5(1)
136.4(1)
77.4(1)
76.3(1)
83.1(1)
126.2(1)
135.0(1)
95.6(1)
63.0(1)
150.1(1)
68.4(1)
123.0(1)
72.8(1)
98.9(1)
148.5(1)
65.6(1)
136.5(1)
66.3(1)
131.3(1)
130.2(1)
112.4(1)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004

136
WANG et al.
and high-spin f 6 electronic configuration should form nium cation. A net structure is formed in a unit cell
nine-coordinated complexes with aminopolycarboxylic through the hydrogen bonds and static electricities.
acids if all chelate rings are five-membered cycles in the
structure.
Thus, the Eu(III) complexes with Edta and Ttha
ligands are prepared and their compositions and struc-
tures are determined as (NH4)[EuIII(Edta)(H2O)3] · H2O
and (NH4)3[EuIII(Ttha)] · 5H2O, respectively, by single-
crystal X-ray diffraction analyses and elemental analy-
ses. In the nine-coordinated [EuIII(Edta)(H2O)3]– com-
plex anion, the EuIIIN2O7 part forms a mono-capped
square antiprism. In the nine-coordinate [EuIII(Ttha)]3–
complex anion, the EuIIIN4O5 part forms a mono-
capped square antiprism. In addition, the [EuIII(Ttha)]3–
complex anion supplies a non-coordinated free carbox-
ylic group.
In one unit cell, there are sixteen complex mole-
cules. The hydrogen bonds contact among crystal water
and crystal water, crystal water and O atom of Edta
ligand as well as crystal water and coordinated water. A
net structure is formed among complex molecules in a
unit cell through the hydrogen bonds and static electric-
ities.
It can be seen in Fig. 3 that the central Eu3+ ion of
the II structure is coordinated with four N atoms and
five O atoms from one Ttha ligand. The EuIIIN4O5 part
in nine-coordinated [EuIII(Ttha)]3– complex anion
forms a pseudo-monocapped square antiprismatic
structure in which the set of O(7), O(9), O(11), and
N(1) atoms and the set of N(2), N(3), N(4), and O(5)
atoms form two approximate squares (Fig. 6), respec-
tively. The ninth coordinated atom O(1) is above the
plane formed by O(7), O(9), O(11), and N(1) atoms. In
general, the EuIII–O(1) distance (0.2369(3) nm) should
originally be the longest among all the EuIII–O dis-
tances for the repulsion of other four coordinate atoms
in plane, but O(11) atom not only coordinates with cen-
ter Eu3+ ion but also forms hydrogen bond with one
crystal water molecule which results in the longest
EuIII–O(11) distance (0.2445(3) nm) among all the
EuIII–O distances in the structure II. Through compar-
ing the coordination bonds in complexes I and II, it can
be found that the coordination bonds of [EuIII(Ttha)]3–
complex anion are all shorter than those of
[EuIII(Edta)(H2O)3]– complex anion, which indicates
that the coordination capacity of Ttha ligand is stronger
than that of Edta ligand.
ACKNOWLEDGMENTS
The authors thank Prof. K. Miyoshi and T. Mizuta
(Faculty of Science, Hiroshima University, Japan) for
teaching and Dr. H.G. Wang (Central Laboratory, Nan-
kai University) for the X-ray structure determination.
REFERENCES
1. Zhou, J., Wang, L.F., Wang, J.Y., et al., J. Inorg. Bio-
chem., 2001, vol. 8, no. 1, p. 41.
2. Akaboshia, M., Suminoa, T., Tanakaa,Y., et al., J. Radio.
Nucl. Chem., 1997, vol. 217, no. 2, p. 179.
3. Banaszka, J.E., Rittmann, B.E., and Reed, D.T., Nucl.
Chem., 1999, vol. 41, p. 385.
4. Lauffer, R.B., Chem. Rev., 1988, vol. 87, p. 901.
5. Richardson, F.R., Chem. Rev., 1982, vol. 82, p. 541.
6. Kang, J.G., Hong, J.P., Yoon, S.K., et al., J. Alloys
Compd., 2002, vol. 339, p. 248.
7. Miyoshi, K., Wang, J., and Mizuta, T., Bull. Chem. Soc.
Jpn., 1993, vol. 66, p. 2547.
The results mentioned above show again that the
Eu(III) can form a nine-coordinated complex with
Ttha ligand like (NH4)3[DyIII(Ttha)] · 5H2O [13],
(NH4)2[GdIII(HTtha)] · 9H2O [14] and (NH4)3[YIII(Ttha)] ·
5H2O [15] complexes since it has the ionic radius of
0.1087 nm being similar to ones of Dy(III) (0.1052 nm),
Gd(III) (0.1078 nm) andY(III) (0.1040 nm) and high-spin
f 6 electronic configuration. These structures prove that
the theoretical inferences about the coordination num-
ber or structure were accurate [16, 17]. In addition, it
can also be seen that this nine-coordinated complex II
contains a non-coordinated free carboxyl group
(−CH2COOH). The –CH2COOH group can be modified
by chemical method using some biological molecules
and make the complex form targeting ionic fluores-
cence probe having directional function to some abnor-
mal tissues.
8. Mizuta, T., Wang, J., and Miyoshi, K., Inorg. Chim. Acta,
1993, vol. 230, p. 249.
9. Sakagami, N., Homma, J., Konno, T., et al., Inorg. Chim.
Acta, 1999, vol. 288, p. 1376.
10. Hoard, J.L., Lee, B., and Lind, M.D., J. Am. Chem. Soc.,
1965, vol. 87, p. 1612.
11. Wang, J., Zhang, X.D., and Zhang, W.Q., Chin. Rare
Metal, 2001, vol. 20, p. 267.
12. Wang, J., Zhao, J., and Zhang, X.D., Chin. Rare Metal,
2002, vol. 21, p. 106.
13. Wang, J., Zhang, X.D., and Jia, W.G., Chin. Rare Earth,
2002, vol. 8, p. 765.
14. Wang, R.Y., Zhang, H.J., and Jin, T.Z. Chem. J. Chin.
Univ., 1999, vol. 20, p. 176.
15. Wang, J., Zhang, X.D., and Ma, R., Acta Chim. Sinica,
1998, vol. 61, p. 536.
In one unit cell, there are four complex molecules
shown in Fig. 4. The hydrogen bonds contact among
crystal water and crystal water, crystal water and O
atom of Ttha ligand as well as crystal water and ammo-
16. Mizuta, T., Wang, J., and Miyoshi, K., Bull. Chem. Soc.
Jpn., 1993, vol. 66, p. 3662.
17. Wang, J., Zhang, X.D., and Ma, R., Chin. Inorg. Chem.,
2001, vol. 17, no. 1, p. 119.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 2 2004