Thulium(III) trifluoroacetates Tm(CF3COO)3 ? 3H2O and Tm2(CF3COO)6 ? 2CF3COOH ? 3H2O: Synthesis and crystal structure

Article abstract of DOI:10.1134/S0036023606040061

Thulium trifluoroacetate compounds have been synthesized, Tm(CF ₃COO)₃ ? 3H₂O (I) and Tm ₂(CF₃COO)₆ ? 2CF₃COOH ? 3H₂O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF₃COO) ₃ ? 3H₂O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for I a = 9.062(2) ?, b = 18.678(3) ?, c = 9.687(2) ?, β = 113.93(1)°, Z = 2, space group P2₁/c, R ₁ = 0.062; for II a = 8.560(4) ?, b = 19.866(5) ?, c = 20.813(7) ?, β = 101.69(4)°, Z = 8, space group C2/c, R ₁ = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)-2.85(2) ?. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds. Pleiades Publishing, Inc., 2006.

Full text of DOI:10.1134/S0036023606040061

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2006, Vol. 51, No. 4, pp. 541–548. © Pleiades Publishing, Inc., 2006.
Original Russian Text © S.I. Gutnikov, E.V. Karpova, M.A. Zakharov, A.I. Boltalin, 2006, published in Zhurnal Neorganicheskoi Khimii, 2006, Vol. 51, No. 4, pp. 593–600.
COORDINATION
COMPOUNDS
Thulium(III) Trifluoroacetates Tm(CF COO) · 3H O
3
3
2
and Tm (CF COO) · 2CF COOH · 3H O:
2
3
6
3
2
Synthesis and Crystal Structure
S. I. Gutnikov, E. V. Karpova, M. A. Zakharov, and A. I. Boltalin
Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
Received June 20, 2005
Abstract—Thulium trifluoroacetate compounds have been synthesized, Tm(CF COO) · 3H O (I) and
3
3
2
Tm (CF COO) · 2CF COOH · 3H O (II). The structure of I has been refined by the Rietveld method on the
2
3
6
3
2
basis of the structural data for Cd(CF COO) · 3H O. The structure of II has been solved in a single-crystal
3
3
2
X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic:
for I a = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P2 /c, R = 0.062;
1
1
for II a = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R = 0.0392.
1
In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions
to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water
molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium
atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with
coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted mono-
capped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm–O bond lengths are in
the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These
chains are linked into layers through hydrogen bonds.
DOI: 10.1134/S0036023606040061
Carboxylates of rare-earth elements form various
The crystals were recrystallized from a mixture of
types of crystal structures owing to their ability to coor- acetonitrile and carbon tetrachloride. X-ray powder dif-
dinate a great number of atoms [1]. Trifluoroacetates fraction data showed that the compound obtained upon
retain this ability of the carboxylates, but at the same fast crystallization from trifluoroacetic acid and the one
time they manifest supplementary properties owing to recrystallized from acetonitrile and carbon tetrachlo-
a higher ionicity of their M–O bonds. A great number ride had identical compositions.
of trifluoroacetates are used as precursors for the prep-
Compound I was dissolved in trifluoroacetic acid.
aration of oxide and fluoride coatings and materials
The solution was allowed to evaporate from a weighing
with various physicochemical properties [2, 3].
bottle with a small opening placed in a desiccator with
Many lanthanide trifluoroacetates have been studied
structurally [4–9]. However, the structure of thulium
trifluoroacetate is not known. We studied the structures
of two thulium trifluoroacetates.
P O as a desiccant. Within 1 week, crystals of a new
4
10
compound appeared.
2
Tm(CF COO) · 3H O + 2CF COOH
3
3
2
3
=
Tm (CF COO) · 2CF COOH · 3H O (II) + 3H O.
2 3 6 3 2 2
EXPERIMENTAL
Synthesis. Thulium(III) acetate tetrahydrate was
dissolved in 99% trifluoroacetic acid taken in 20%
excess. The solution was boiled; its volume was kept
constant until the precipitate dissolved completely. The
solution was cooled; then, an open weighing bottle con-
taining the solution was placed into a desiccator with
P O as a desiccant. Within 24 h, colorless crystals of
The sample was characterized using powder X-ray
powder diffraction, thermal analysis, and single-crystal
X-ray diffraction.
Powder X-ray powder diffraction study was per-
formed on a STADI/P (Stoe) instrument (CuK radia-
α
tion) with a plane detector (Ge monochromator). The
4
10
structure of Tm(CF COO) · 3H O was refined by the
3
3
2
thulium(III) trifluoroacetate trihydrate appeared. The
crystals were stable in air.
Rietveld method using the RIETAN97 program pack-
age [10]. The structural data for Gd(CF COOO) ·
3
3
Tm(CH COO) · 4H O + 3CF COOH
3
3
2
3
3H O were used as the starting model for the refine-
2
3
+
2–
3+
–
=
Tm(CF COO) · 3H O (I) + 3CH COOH + H O.
ment [7]. f-Curves for Tm , O , C , and F were used
3
3
2
3
2
5
41

5
42
GUTNIKOV et al.
Table 1. Experimental details and refined parameters for the Table 2. Atomic coordinates in the structure of I
structure of Tm(CF COO) · 3H O (I)
3
3
2
Atom
x
y
z
Crystal system
Space group
Monoclinic
P21/c
5–71
Tm(1)
0.213(3)
0.335(4)
0.261(7)
0.262(3)
–0.027(9)
–0.008(2)
0.231(5)
0.092(2)
0.335(9)
0.470(2)
0.442(1)
0.331(1)
0.159(5)
0.140(6)
–0.218(3)
–0.149(1)
0.542(9)
0.467(1)
0.369(1)
0.136(7)
0.297(5)
0.057(5)
–0.138(1)
–0.189(6)
–0.360(7)
0.068(7)
0.112(8)
0.223(3)
–0.036(1)
0.090(4)
0.062(1)
–0.011(3)
0.182(3)
0.140(6)
0.024(3)
0.162(4)
0.165(9)
–0.166(7)
–0.089(4)
0.072(4)
0.044(1)
0.131(2)
0.215(3)
0.109(4)
–0.212(2)
–0.164(9)
–0.170(9)
0.060(8)
0.127(1)
0.065(1)
0.029(1)
–0.123(5)
–0.209(2)
–0.065(5)
0.059(6)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
F(1)
F(2)
F(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
2
θ range, deg
θ step, deg
0.03
Imax (pulses)
3164
–0.208(1)
0.221(7)
Unit cell parameters
a, Å
9.062(2)
18.678(3)
9.687(2)
113.93(1)
1498.8(5)
2
0.151(1)
b, Å
0.247(1)
c, Å
0.116(2)
β, deg
V, Å3
Z
–0.283(8)
–0.200(7)
–0.204(6)
–0.102(5)
–0.445(6)
–0.272(4)
–0.212(1)
–0.313(1)
–0.386(7)
–0.105(4)
–0.180(4)
–0.300(4)
–0.522(2)
–0.443(6)
–0.519(1)
ρcalc, g/cm3
1498.6
713
Number of collected reflections
Number of refined parameters
structural
79
17
other
Discrepancies
R , %
0.1234
0.062
2.54
wp
RI, %
S
D-Wd
0.38
for the refinement. The peak profiles were described
Single-crystal X-ray diffraction study of II was
using a modified pseudo-Voigt function (Mod-TCH performed on a CAD4 Enraf-Nonius diffractometer
pseudo-Voigt). The background profiles were described (MoK radiation, graphite monochromator, ω scan
α
by a tenth-order polynomial.
mode). The unit cell parameters were determined from
the positions of 20 centered reflections in a θ range of
The refinement of the positional parameters of
atoms and all other parameters (background, profile,
unit-cell parameters, scale parameters, origin shift
parameters) showed a good agreement of the calculated
and experimental X-ray powder diffraction patterns.
Thermal parameters were not refined. Selected experi-
mental details and refined parameters for the structure
of I are listed in Table 1. Tables 2 and 3 display the
refined position parameters and selected interatomic
distances for I. Figure 1 shows fragments of the exper-
imental, simulated, and difference X-ray powder dif-
fraction patterns.
2
0°–25°. The structure was solved by the direct method
(SHELXS97) [11]. The crystal parameters of II are
listed in Table 4; atomic coordinates and thermal
parameters, in Table 5; selected interatomic distances,
in Table 6.
RESULTS AND DISCUSSION
Compound I is a member of the series of isostruc-
tural
lanthanide
trifluoroacetate
trihydrates
Ln(CF COO) · 3H O (Ln = La, Ce, Pr, Nd, Sm, Eu,
3
3
2
Thermal analysis was performed on a D-2 deri- Gd, Tb, Dy, Ho, Er, Tm, orY). The existence of this iso-
vatograph (heating rate 5 K/min, a 75-mg sample, an structural series was hypothesized in [12]. In [12] the
alumina crucible). The measurements were carried out composition of the compounds was determined from
in nitrogen or air.
the results of elemental analysis. The X-ray diffraction
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

THULIUM(III) TRIFLUOROACETATES Tm(CF COO) · 3H O
543
3
3
2
Intensities, pulses
3
3
2
2
1
1
500
000
500
000
500
000
5
00
0
a
b
c
1
0
15
20
25
30
35
2
θ, deg
Fig. 1. Fragments of (a) experimental, (b) simulated, and (c) difference X-ray powder diffraction patterns for Tm(CF COO) ·
3
3
3
H O (I).
2
study of single-crystal was carried out only for Pr [6], error of structure determination by the X-ray powder
Eu [4], Gd [7], Tb [9], and Dy [5] compounds.
diffraction method. In I, dimeric molecules are linked
into chains through hydrogen bonds.
The molecular structure of I consists of dimeric
structural units (symmetry C ). The metal atoms are
2
Table 3. Selected bond lengths (d) in the structure of I
bound together by four bidentate bridging carboxylate
groups (Fig. 2). The coordination polyhedron of the
thulium atom also includes the three oxygen atoms of
water molecules and an oxygen atom of the monoden-
tate trifluoroacetate group. The coordination number of
thulium atom is eight. The Tm–O distances vary in the Tm(1)–O(4)
range 2.28(1)–2.85(2) Å. The shortest distance corre-
sponds to the Tm–O(1) bond with the monodentate tri-
Bond
d, Å
Bond
d, Å
Tm(1)–O(1)
Tm(1)–O(3)
2.33(1)
2.28(1)
2.35(5)
2.36(4)
2.34(1)
2.85(2)
2.36(2)
2.28(6)
1.23(3)
1.52(3)
1.22(8)
1.42(1)
1.79(8)
O(6)–C(6)
O(6)–C(5)
O(5)–C(6)
O(4)–C(4)
C(1)–F(1)
C(1)–F(2)
C(1)–F(3)
C(3)–F(6)
C(3)–F(5)
C(3)–F(4)
C(5)–F(8)
C(5)–F(9)
C(5)–F(7)
1.21(2)
1.62(3)
1.21(9)
1.24(9)
1.06(9)
1.07(7)
1.37(1)
1.01(3)
1.17(6)
1.35(9)
1.05(1)
1.20(2)
1.25(1)
Tm(1)–O(5)
Tm(1)–O(6)
Tm(1)–O(7)
Tm(1)–O(8)
Tm(1)–O(9)
O(1)–C(2)
fluoroacetate group. The Tm–O(7)
distance
H O
2
(2.85(2) Å) is significantly longer than the distances to
the O atoms of the other two water molecules, which
are comparable to the Tm–O distances (bidentate triflu-
oroacetate groups) and are in the range 2.28(1)–
2
.36(4) Å. For the single-crystal X-ray structures of C(1)–C(2)
lanthanide trifluoroacetates, the spread of bond length
values is not so significant; in the structure of dyspro-
sium trifluoroacetate, the Dy–O distances vary within
O(2)–C(2)
O(3)–C(4)
C(3)–C(4)
2
.33(3)–2.42(3) Å. This fact may be due to a greater
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

5
44
GUTNIKOV et al.
Table 4. Crystallographic parameters and experimental details Table 5. Atomic coordinates, isotropic equivalent thermal
for the structure of Tm (CF COO) · 2CF COOH · 3H O (II)
parameters of non-hydrogen atoms, and isotropic thermal pa-
2
3
6
3
2
rameter of the hydrogen atoms (U ) in the structure of II
H
Formula unit
FW
Tm (CF COO) · 2CF COOH · 3H O
2 3 6 3 2
2
Atom
x
y
z
U , Å
eq
822
Crystal system
Space group
a, Å
Monoclinic
C2/c
Tm(1)
Tm(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
H(1)
O(9)
O(10)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
0.5
1
0.16305(2) 0.75
0.07052(2) 0.75
0.0283(2)
0.0278(2)
8.560(4)
19.866(5)
20.813(7)
101.69(4)
3466(2)
8
0.7395(5) 0.1093(3) 0.6952(2) 0.037(1)
0.5743(6) 0.1869(3) 0.6478(3) 0.038(1)
0.2703(6) 0.2042(3) 0.6877(3) 0.055(2)
1.0312(7) 0.1612(3) 0.6882(3) 0.054(2)
1.1687(6) 0.0278(3) 0.6877(3) 0.046(1)
0.4069(6) 0.0727(3) 0.6874(3) 0.043(1)
0.9421(9) –0.1449(3) 0.6331(3) 0.055(2)
b, Å
c, Å
β, deg
V, Å3
Z
ρcalc, g/cm3
2.522
–
1
µ(MoK ), cm
5.295
α
θmax, deg
25.97
0.449(1)
0.49(1)
0.2782(4) 0.5545(4) 0.076(2)
0.258(4) 0.581(4) 0.05(2)
Number of collected
reflections
3400
0.8695(7) –0.0216(3) 0.6899(3) 0.058(2)
0.5 0.2804(4) 0.75 0.087(4)
0.6759(8) 0.1421(4) 0.6470(4) 0.035(2)
0.706(1) 0.1230(5) 0.5785(5) 0.058(2)
1.1233(8) 0.2047(4) 0.6769(4) 0.041(2)
0.046(1) 0.2698(6) 0.6470(7) 0.075(3)
Numberofreflections
2825
282
2
2
with F > 2σ(F )
Number of refined
parameters
R1/WR2
0.0392/0.0994
293
Temperature, K
GOOF
1.084
0.3022(8) 0.0291(4) 0.6744(4) 0.035(2)
0.346(1) –0.0322(5) 0.6374(6) 0.065(3)
The results of the thermal analysis for I are given in
Table 7. The composition of the compound calculated
from the thermoanalytical data coincides with
0.419(1)
1.155(1)
0.3365(4) 0.5768(5) 0.049(2)
0.1158(5) 0.4777(5) 0.065(3)
Tm(CH COO) · 3H O. The decomposition of this C(8)
3
3
2
complex proceeds in two stages. At the first stage, crys-
tal water molecules are eliminated. At the second stage,
anhydrous thulium trifluoroacetate decomposes to thu-
lium fluoride, which is confirmed by the X-ray powder
diffraction study of the product of thermal decomposi-
tion. The temperature range and the final decomposi-
tion product of I coincide with the results for
Nd(CF COO) · 3H O [13].
F(1)
F(2)
F(3)
F(4)
F(5)
0.8373(9) 0.0874(4) 0.5825(4) 0.103(3)
0.596(1)
0.718(1)
0.0846(7) 0.5499(4) 0.174(6)
0.1736(5) 0.5433(4) 0.164(5)
–0.1010(8) 0.2746(4) 0.6480(6) 0.153(5)
3
3
2
0.119(1)
0.073(1)
0.3228(3) 0.6770(6) 0.137(4)
0.2790(5) 0.5885(5) 0.153(4)
Compound Tm (CF COO) · 2CF COOH · 3H O F(6)
2
3
6
3
2
(
II) belongs to the family of chain structures with tri-
F(7)
0.4935(9) –0.0420(5) 0.6455(6) 0.158(5)
0.281(1) –0.0848(4) 0.6490(8) 0.176(6)
0.295(2) –0.0257(7) 0.5772(5) 0.240(9)
0.745(1) –0.0763(5) 0.5405(4) 0.151(5)
ple carboxylate bridges (the scandium acetate family),
according to the classification in [1]. The structure F(8)
includes two crystallographically independent thu-
lium atoms linked into a chain through the tridentate
chelate bridging
F(9)
(32)
trifluoroacetate group
F(10)
F(11)
F(12)
(
O(1)O(2)C(1)C(2)) and two bidentate trifluoroacetate
0.219(2)
1.059(1)
0.1422(5) 0.5295(5) 0.209(8)
0.0763(7) 0.4910(8) 0.227(8)
groups (O(3)O(4)C(3)C(4) and O(5)O(6)C(5)C(6)).
The coordination polyhedron of each thulium atom
consists of four oxygen atoms of bridging bidentate tri-
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

THULIUM(III) TRIFLUOROACETATES Tm(CF COO) · 3H O
545
3
3
2
Table 6. Selected bond lengths (d) in the structure of II
Tm–O distances are within 2.26(5)–2.76(5) Å. This
wide range of bond lengths can be explained by the
variety of structural functions of oxygen atoms in the
coordination polyhedron of thulium atoms.
Bond
d, Å
Bond
d, Å
Tm(1)–O(6)
Tm(1)–O(3)
Tm(1)–O(10)
Tm(1)–O(2)
Tm(1)–O(1)
Tm(2)–O(4)
Tm(2)–O(5)
Tm(2)–O(9)
Tm(2)–O(1)
O(1)–C(1)
O(2)–C(1)
O(3)–C(3)
O(4)–C(3)
O(5)–C(5)
O(6)–C(5)
O(7)–C(7)
O(8)–C(7)
2.266(5)
2.276(5)
2.331(9)
2.388(5)
2.756(5)
2.260(5)
2.290(5)
2.364(5)
2.416(5)
1.227(9)
1.246(8)
1.233(9)
1.224(9)
1.230(8)
1.237(8)
1.20(1)
C(1)–C(2)
C(2)–F(3)
C(2)–F(2)
C(2)–F(1)
C(3)–C(4)
C(4)–F(4)
C(4)–F(6)
C(4)–F(5)
C(5)–C(6)
C(6)–F(8)
C(6)–F(9)
C(6)–F(7)
C(7)–O(7)
C(7)–C(8)
C(8)–F(12)
C(8)–F(11)
C(8)–F(10)
1.54(1)
1.26(1)
1.26(1)
1.31(1)
1.52(1)
1.26(1)
1.29(1)
1.31(1)
1.527(1)
1.23(1)
1.24(1)
1.25(1)
1.20(1)
1.51(3)
1.21(1)
1.22(1)
1.26(1)
The Tm–O distances for the oxygen atoms of the
bidentate bridging trifluoroacetate groups (O(3)–O(6))
are similar (2.26(5)–2.29(1) Å). The increased Tm–O
distances for water molecules (2.33(9) and 2.36(5) Å)
are due to the participation of the water molecules in
hydrogen bonds. The atoms O(1) and O(2), belonging
to the tridentate chelate bridging trifluoroacetate group,
are the most remote from the thulium atoms (2.38(5),
2
.41(5), and 2.75(6) Å).
The acid molecules in II are hydrogen-bonded
(
Table 8). An acid molecule acts as the donor of the
hydrogen bond O(8)–H(1)···O(2); in the other two
hydrogen bonds, the acid molecule acts as the acceptor
(
O(7)···O(10) and O(7)···O(9)). The atoms O(2) and
O(10) belong to the coordination polyhedron of the
Tm(1) atom; atom O(9), to the coordination polyhedron
of the Tm(2) atom of the neighboring chain (Fig. 4).
Thus, the chains of Tm atoms bound by carboxylate
groups are linked into layers through hydrogen bonds
(Fig. 5).
Tris-glycyl neodymium chloride (III) [14] and
cerium acetate monohydrate (IV) [15] are structures
with triple carboxylate bridges. In contrast to II, these
structures include only one type of metal atom linked
through three carboxylate groups into chains, but, as
in II, they contain tridentate carboxylate groups. The
1.29(1)
fluoroacetate groups. In addition, each Tm(1) coordi- structure of III includes one tridentate carboxylate
nates two oxygen atoms from two tridentate chelate group, whereas there are two tridentate carboxylate
bridging (3 ) trifluoroacetate groups. The oxygen atoms groups in the structure of cerium acetate monohydrate.
2
of water molecules complete the coordination number Water molecules complete the coordination number of
of atoms Tm(1) and Tm(2) to nine and eight, respec- the metal atoms in the structures of III and IV to nine;
tively (Fig. 3).
the coordination polyhedra are close to monocapped
antiprisms.
The coordination polyhedra of atoms Tm(1) and
Tm(2) are a distorted monocapped tetragonal antiprism
and a distorted tetragonal antiprism, respectively. The belong to the series of isostructural trifluoroacetate tri-
Among the lanthanide trifluoroacetates that do not
Table 7. Thermoanalytical data for Tm (CF COO) · 3H O
2
3
6
2
∆
T
Tmax
Weight loss, %
Decomposition
product
Compound
°C
exp.
theor.
Tm (CF COO) · 3H O
50–100
75
10.8
55.5
9.6
56
Tm (CF COO)
2
3
3
2
2
3
3
Tm (CF COO)
170–200
190
TmF3
2
3
3
Table 8. Parameters of hydrogen bonds in the structure of II
D–H···A, Å
D–H, Å
0.721
H···A, Å
2.007
D···A, Å
Angle D–H···A, deg
167.25
O(2)–H(1)···O(8)
O(7)···O(9)
2.714
2.845
2.807
O(7)···O(10)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

5
46
GUTNIKOV et al.
hydrates, lanthanum and cerium trifluoroacetates [16]
are noticeable. These compounds are isostructural.
Their structures are layered: three crystallographically
independent metal atoms are linked by two carboxylate
groups; two of the six carboxylate groups are tridentate.
The oxygen atoms of water molecules complete the
coordination number of the metal atoms to nine. The
increased coordination number of the metal and the
elongated M–O bonds in lanthanum and cerium trifluo-
roacetates compared to the thulium complex can be
explained by lanthanide contraction. For example, the
La–O distances in lanthanum trifluoroacetate are
slightly longer than the Tm–O distances in the structure
of I and are within 2.42(2)–3.04(4) Å for carboxylate
groups and 2.49(1)–2.56(7) Å for water molecules. In
the structure of cerium trifluoroacetate the spread of
M–O bond lengths is more significant (2.39(2)–
2.54(4) Å for carboxylate groups and 2.46(2)–
C(6)
C(3)
C(4)
C(5)
O(4)
O(6)
O(3)
O(5)
O(7)
Tm(1)
2
.53(4) Å for water molecules).
In summary, we have shown that compounds with
O(1)
O(8)
O(9)
different structures can form in the lanthanide–trifluo-
roacetic acid systems. This is made possible by the vari-
ety of coordination modes of carboxylate groups, as
well as the high coordination number of metal atoms.
Further studies of the structure as dependent on the syn-
thesis conditions will allow one to synthesize com-
pounds with designed properties, which will extend
their use in practice.
C(2)
O(2)
C(1)
Fig. 2. Fragments of the structure of Tm(CF COO)
·
3
3
3
H O (I).
2
C(8)
O(8)
H(1)
C(7)
O(7)
C(2)
C(6)
C(5)
O(2)
C(1)
O(6)
O(9)
O(1)
O(5)
O(10)
Tm(1)
Tm(2)
O(3)
O(4)
C(3)
C(4)
a
c
Fig. 3. Fragments of the structure of Tm (CF COO) · 2CF COOH · 3H O (II).
2
3
6
3
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

THULIUM(III) TRIFLUOROACETATES Tm(CF COO) · 3H O
547
3
3
2
Tm(2)
O(9)
b
c
a
C(8)
C(7)
O(7)
O(10)
O(8)
H(1)
O(2)
Tm(1)
Fig. 4. Packing of structural units in the crystal of II.
b
O(9) O(9)
O(7)
O(7)
O(8)
O(10)
O(2)
a
c
Fig. 5. Hydrogen bonds in the structure of Tm (CF COO) · 2CF COOH · 3H O (II).
2
3
6
3
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 51 No. 4 2006

5
48
GUTNIKOV et al.
ACKNOWLEDGMENTS
This study was supported by the Russian Founda-
7. J. Zhang, S. Zhang, X. Miao, G. Wei, N. Hu, and Z. Jin,
Chin. J. Chem. 5, 30 (1988).
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. S. R. Drake, A. Lyons, D. J. Otway, and D. J. Williams,
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Inorg. Chem. 33, 1230 (1994).
. A. A. Rastorguev, A. A. Remova, G. V. Romanenko,
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