Article

Lutetium(III) cyclotetraphosphate

Acta Crystallographica Section E Structure Reports Online (Impact Factor: 0.35). 06/2010; 66(Pt 6):i46. DOI: 10.1107/S1600536810016363
Source: PubMed
ABSTRACT
Single crystals of the title compound, tetra-lutetium(III) tris-(cyclo-tetra-phosphate), Lu(4)(P(4)O(12))(3), were obtained by solid-state reaction. The cubic structure is isotypic with its Al(III) and Sc(III) analogues and is built up from four-membered (P(4)O(12))(4-) phosphate ring anions ( symmetry), isolated from each other and further linked through isolated LuO(6) octa-hedra (.3. symmetry) via corner sharing. Each LuO(6) octa-hedron is linked to six (P(4)O(12))(4-) rings, while each (P(4)O(12))(4-) ring is linked to eight LuO(6) octa-hedra.

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Available from: Aïcha Mbarek
Lutetium(III) cyclotetraphosphate
¨
cha Mbarek,
a
Mohieddine Fourati,
a
Daniel Zambon
b
and Daniel Avignant
b
*
a
Laboratoire de Chimie Industrielle, De
´
partement de Ge
´
nie des Mate
´
riaux, Ecole
Nationale d’Inge
´
nieurs de Sfax, Universite
´
de Sfax, BP W 3038, Sfax, Tunisia, and
b
Laboratoire des Mate
´
riaux Inorganiques, UMR CNRS 6002, Universite
´
Blaise Pascal,
24 Avenue des Landais, 63177 Aubie
`
re, France
Correspondence e-mail: daniel.avignant@univ-bpclermont.fr
Received 28 April 2010; accepted 4 May 2010
Key indicators: single-crystal X-ray study; T = 296 K; mean (Lu–O) = 0.003 A
˚
;
R factor = 0.020; wR factor = 0.038; data-to-parameter ratio = 17.5.
Single crystals of the title compound, tetralutetium(III)
tris(cyclotetraphosphate), Lu
4
(P
4
O
12
)
3
, were obtained by
solid-state reaction. The cubic structure is isotypic with its
Al
III
and Sc
III
analogues and is built up from four-membered
(P
4
O
12
)
4
phosphate ring anions (4 symmetry), isolated from
each other and further linked through isolated LuO
6
octa-
hedra (.3. symmetry) via corner sha ring. Each LuO
6
octa-
hedron is linked to six (P
4
O
12
)
4
rings, while each (P
4
O
12
)
4
ring is linked to eight LuO
6
octahedra.
Related literature
The title compound belongs to a structural type discovered a
long time ago through the Al
4
(P
4
O
12
)
3
member, the structure
of which was first investigated by Hendricks & Wyckoff (1927)
and then described by Pauling & Sherman (1937). Since then,
five isotypic compounds have been characterized: Cr
4
(P
4
O
12
)
3
(Re
´
my & Boulle
´
, 1964); Ti
4
(P
4
O
12
)
3
(Liebau & Williams,
1964); Fe
4
(P
4
O
12
)
3
(d’Yvoire et al., 1962); Sc
4
(P
4
O
12
)
3
(Bagieu-
Beucher, 1976; Mezentseva et al., 1977; Bagieu-Beucher &
Guitel, 1978; Smolin et al. 1978) and Yb
4
(P
4
O
12
)
3
(Chudinova,
1979). For a review of the crystal chemistry of cyclotetra-
phosphates, see: Durif (1995). For other polymorphs of
composition Lu(PO
3
)
3
, see: Ho
¨
ppe & Sedlmaier (2007); Yuan
et al. (2008); Bejaoui et al. (2008).
Experimental
Crystal data
Lu
4
(P
4
O
12
)
3
M
r
= 1647.52
Cubic, I
43d
a = 14.6920 (6) A
˚
V = 3171.3 (2) A
˚
3
Z =4
Mo K radiation
= 13.08 mm
1
T = 296 K
0.18 0.10 0.08 mm
Data collection
Bruker APEXII CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
T
min
= 0.534, T
max
= 0.746
3088 measured reflections
717 independent reflections
659 reflections with I >2(I)
R
int
= 0.034
Refinement
R[F
2
>2(F
2
)] = 0.020
wR(F
2
) = 0.038
S = 1.03
717 reflections
41 parameters
max
= 0.90 e A
˚
3
min
= 0.67 e A
˚
3
Absolute structure: Flack (1983),
272 Friedel pairs
Flack parameter: 0.000 (15)
Table 1
Selected bond lengths (A
˚
).
Lu—O3
i
2.182 (3)
Lu—O3
ii
2.182 (3)
Lu—O3 2.182 (3)
Lu—O2
i
2.185 (4)
Lu—O2
ii
2.185 (4)
Lu—O2 2.185 (4)
P—O2
iii
1.464 (4)
P—O3 1.481 (4)
P—O1
iv
1.583 (3)
P—O1 1.594 (3)
Symmetry codes: (i) z þ 1; x
1
2
; y þ
1
2
; (ii) y þ
1
2
; z þ
1
2
; x þ 1; (iii)
z þ 1; x þ
3
2
; y; (iv) y þ
5
4
; x
3
4
; z þ
3
4
.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT
(Bruker, 2008); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CaRine
(Boudias & Monceau, 1998) and ORTEP-3 (Farrugia, 1997); software
used to prepare material for publication: SHELXTL (Sheldrick,
2008).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: WM2342).
References
Bagieu-Beucher, M. (1976). J. Appl. Cryst. 9, 368–369.
Bagieu-Beucher, M. & Guitel, J. C. (1978). Acta Cryst. B34, 1439–1442.
Bejaoui, A., Horchani-Naifer, K. & Fe
´
rid, M. (2008). Acta Cryst. E64, i48.
Boudias, C. & Monceau, D. (1998). CaRine. CaRine Crystallography,
DIVERGENT S.A., Compie
`
gne, France.
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Chudinova, N. N. (1979). Izv. Akad. Nauk SSSR Neorg. Mater. 15, 833–837.
Durif, A. (1995). In Crystal Chemistry of Condensed Phosphates. New York
and London: Plenum Press.
d’Yvoire, F. (1962). Bull. Soc. Chim. pp. 1237–1243.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Hendricks, S. B. & Wyckoff, R. W. G. (1927). Am. J. Sci. 13, 491–496.
Ho
¨
ppe, H. A. & Sedlmaier, S. J. (2007). Inorg. Chem. 46, 3467–3474.
Liebau, F. & Williams, H. P. (1964). Angew. Chem. 76, 303–304.
Mezentseva, L. P., Domanskii, A. I. & Bondar, I. A. (1977). Russ. J. Inorg.
Chem. 22, 43–45.
Pauling, L. & Sherman, J. S. (1937). Z. Kristallogr. 96, 481–487.
Re
´
my, P. & Boulle
´
, A. (1964). C. R. Acad. Sci. 258, 927–929.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Smolin, Y. I., Shepelev, Y. F., Domanskii, A. I. & Belov, N. V. (1978).
Kristallografiya, 23, 187–188.
Yuan, J. L., Zhang, H., Zhao, J. T., Chen, H. H., Yang, X. X. & Zhang, G. B.
(2008). Opt. Mater.
30, 1369–1374.
inorganic compounds
i46 Mbarek et al. doi:10.1107/S1600536810016363 Acta Cryst. (2010). E66, i46
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
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supplementary materials
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supplementary materials
sup-1
Acta Cryst. (2010). E66, i46 [ doi:10.1107/S1600536810016363 ]
Lutetium(III) cyclotetraphosphate
A. Mbarek, M. Fourati, D. Zambon and D. Avignant
Comment
The title compound is the third polymorph of composition Lu(PO
3
)
3
besides the monoclinic form described by Höppe &
Sedlmaier (2007) and Yuan et al. (2008) and the trigonal form more recently reported by Bejaoui et al. (2008). The title
compound is also the less dense polymorph with a calculated density of 3.451 Mg
.
m
3
versus 3.587 Mg
.
m
3
for the trigonal
and 3.708 Mg
.
m
3
for the monoclinic form and is probably the highest temperature form. This cyclotetraphosphate belongs
to a structural type (cubic, with space group I43d) known since 1927 through the archetype Al
4
(P
4
O
12
)
3
determined by
Hendricks & Wyckoff (1927). Then Pauling & Sherman (1937) gave the first description of the structure and reported
roughly estimated atomic coordinates deduced from geometrical considerations. Since this time only five members of this
family, viz. Cr
4
III
(P
4
O
12
)
3
(Rémy & Boullé, 1964), Ti
4
III
(P
4
O
12
)
3
(Liebau & Williams, 1964), Fe
4
III
(P
4
O
12
)
3
(d'Yvoire
et al., 1962), Sc
4
III
(P
4
O
12
)
3
(Bagieu-Beucher, 1976; Mezentseva et al.,1977 and Smolin et al., 1978) and Yb
4
III
(P
4
O
12
)
3
(Chudinova, 1979), have been identified. Corresponding unit cell parameters are listed in Durif (1995). Among these iso-
typic compounds only the structure of the Sc
4
(P
4
O
12
)
3
cyclotetraphosphate has almost simultaneously been refined from
single-crystal data by Bagieu-Beucher & Guittel (1978) and Smolin et al. (1978). Their refinements confirmed the descrip-
tion of Pauling & Sherman (1937) according to which all the crystallographically independent atoms except the A
III
element
(.3. symmetry) are in general positions. The structure is built of four-membered phosphate ring anions (P
4
O
12
)
4-
(Fig. 1),
isolated from each other and further linked by LuO
6
octahedra by sharing corners. Each LuO
6
octahedron is linked to six
(P
4
O
12
)
4-
rings (Fig. 2a) while each (P
4
O
12
)
4-
ring is linked to eight LuO
6
octahedra (Fig. 2b) through oxygen atoms with
shorter P—O distances (1.464 (4) and 1.481 (4) Å). The (P
4
O
12
)
4-
ring anions are located around the 12a Wyckoff positions
of space group I43d and exhibit 4 symmetry. Comparison of the (P
4
O
12
)
4-
ring anions in both Sc
4
(P
4
O
12
)
3
and Lu
4
(P
4
O
12
)
3
structures shows these two ring anions being geometrically quite identical with alternating upward- and downward-pointing
tetrahedra and P—O—P angles of 137.1° and 136.9 (2)°, respectively. The P—O distances in the PO
4
groups are identical
within their e.s.d.. The four bridging oxygen atoms of these ring anions are located at the apices of a flattened tetrahedron
with characteristic angles of 148.22° and 94.30° for Sc and 147.95° and 94.37° for the Lu cyclotetraphosphate. The LuO
6
octahedron is very slightly distorted along a threefold axis, resulting in two sets of Lu—O distances equal to 2.182 (3) and
2.185 (4) Å, respectively.
Experimental
Single crystals of the title compound were obtained by solid state reaction while attempting to synthesized a long chain
polyphosphate by reacting Lu
2
O
3
with (NH
4
)H
2
PO
4
and Rb
2
CO
3
in an alumina boat. A mixture of these reagents in the
molar ratio 27 : 85.5 : 8.7 was used for the synthesis. The mixture was successively heated at 473 K for 24 hours, then at 573
K for 24 additional hours and finally at 813 K for 24 hours. Then the sample was cooled down to 683 K at the rate of 3 K h
-1
and maintained at this temperature for 36 hours. Finally, the sample was cooled down to room temperature by shutting the
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muffle furnace off. Single crystals were extracted from the batch by washing with hot water and filtering. The crystals were
dried at 353 K in an oven. A translucent octahedral crystal of the title compound was selected for the structure refinement.
Refinement
The highest residual peak in the final difference Fourier map was located 0.87 Å from atom Lu and the deepest hole was
located 0.99 Å from atom Lu.
Figures
Fig. 1. ORTEP-3 view of the four-membered phosphate (P
4
O
12
)
4-
ring anion. Displacement
ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) 1-z, 3/2-x, y ; (ii) 3/
4+y, 5/4-x, 3/4-z ; (iii) 5/4-y, -3/4+x,3/4-z ; (iv) -1/4+x, 1/4-z, 3/4-y ; (v) 9/4-x, 1/4+z, 3/4-y
;(vi) 2-x, 1/2-y, z ; (vii) 1+z, -1+x, y.
Fig. 2. Partial view of the Lu
4
(P
4
O
12
)
3
structure showing: (a) the connections between the
LuO
6
octahedron and the (P
4
O
12
)
4-
ring anions, (b) the connections between the (P
4
O
12
)
4-
ring anion and the LuO
6
octahedra.
Tetralutetium(III) tris(cyclotetraphosphate)
Crystal data
Lu
4
(P
4
O
12
)
3
D
x
= 3.451 Mg m
−3
M
r
= 1647.52
Mo Kα radiation, λ = 0.71073 Å
Cubic, I43d
Cell parameters from 1548 reflections
Hall symbol: I -4bd 2c 3 θ = 3.4–30.3°
a = 14.6920 (6) Å
µ = 13.08 mm
−1
V = 3171.3 (2) Å
3
T = 296 K
Z = 4
Truncated octahedron, colourless
F(000) = 3008
0.18 × 0.10 × 0.08 mm
Data collection
Bruker APEXII CCD
diffractometer
717 independent reflections
Radiation source: fine-focus sealed tube
659 reflections with I > 2σ(I)
graphite
R
int
= 0.034
Detector resolution: 8.3333 pixels mm
-1
θ
max
= 30.4°, θ
min
= 3.9°
φ and ω scans
h = −16→11
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
k = −6→20
T
min
= 0.534, T
max
= 0.746
l = −19→9
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supplementary materials
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3088 measured reflections
Refinement
Refinement on F
2
Primary atom site location: structure-invariant direct
methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F
2
> 2σ(F
2
)] = 0.020
w = 1/[σ
2
(F
o
2
) + (0.0088P)
2
]
where P = (F
o
2
+ 2F
c
2
)/3
wR(F
2
) = 0.038
(Δ/σ)
max
< 0.001
S = 1.03
Δρ
max
= 0.90 e Å
−3
717 reflections
Δρ
min
= −0.67 e Å
−3
41 parameters Absolute structure: Flack (1983), 272 Friedel pairs
0 restraints Flack parameter: 0.000 (15)
0 constraints
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds
in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used
for estimating esds involving l.s. planes.
Refinement. Refinement of F
2
against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F
2
, convention-
al R-factors R are based on F, with F set to zero for negative F
2
. The threshold expression of F
2
> σ(F
2
) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å
2
)
x y z
U
iso
*/U
eq
Lu 0.896610 (13) 0.396610 (13) 0.103390 (13) 0.00602 (8)
P 0.95737 (9) 0.37294 (9) 0.33447 (9) 0.0077 (2)
O1 1.0613 (2) 0.3432 (2) 0.3430 (2) 0.0128 (7)
O2 1.0325 (2) 0.3642 (3) 0.0522 (2) 0.0188 (8)
O3 0.9295 (2) 0.3498 (3) 0.2404 (2) 0.0142 (7)
Atomic displacement parameters (Å
2
)
U
11
U
22
U
33
U
12
U
13
U
23
Lu 0.00602 (8) 0.00602 (8) 0.00602 (8) 0.00039 (8) −0.00039 (8) −0.00039 (8)
P 0.0097 (5) 0.0051 (6) 0.0082 (6) 0.0017 (5) −0.0008 (5) 0.0015 (4)
O1 0.0113 (15) 0.0146 (18) 0.0123 (17) 0.0007 (15) −0.0025 (14) 0.0054 (17)
O2 0.0103 (17) 0.024 (2) 0.022 (2) 0.0016 (18) 0.0015 (16) −0.0014 (18)
O3 0.0202 (19) 0.0141 (19) 0.0084 (16) 0.0012 (16) −0.0050 (15) 0.0023 (16)
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supplementary materials
sup-4
Geometric parameters (Å, °)
Lu—O3
i
2.182 (3)
P—O2
iii
1.464 (4)
Lu—O3
ii
2.182 (3) P—O3 1.481 (4)
Lu—O3 2.182 (3)
P—O1
iv
1.583 (3)
Lu—O2
i
2.185 (4) P—O1 1.594 (3)
Lu—O2
ii
2.185 (4)
O1—P
v
1.583 (3)
Lu—O2 2.185 (4)
O2—P
vi
1.464 (4)
O3
i
—Lu—O3
ii
89.06 (14) O3—Lu—O2 92.64 (13)
O3
i
—Lu—O3
89.06 (14)
O2
i
—Lu—O2
87.72 (15)
O3
ii
—Lu—O3
89.06 (14)
O2
ii
—Lu—O2
87.72 (15)
O3
i
—Lu—O2
i
92.64 (13)
O2
iii
—P—O3
118.0 (2)
O3
ii
—Lu—O2
i
178.26 (14)
O2
iii
—P—O1
iv
107.3 (2)
O3—Lu—O2
i
90.59 (14)
O3—P—O1
iv
111.5 (2)
O3
i
—Lu—O2
ii
90.59 (14)
O2
iii
—P—O1
109.2 (2)
O3
ii
—Lu—O2
ii
92.64 (13) O3—P—O1 106.0 (2)
O3—Lu—O2
ii
178.26 (14)
O1
iv
—P—O1
103.9 (2)
O2
i
—Lu—O2
ii
87.72 (15)
P
v
—O1—P
136.9 (2)
O3
i
—Lu—O2
178.26 (14)
P
vi
—O2—Lu
164.9 (2)
O3
ii
—Lu—O2
90.59 (14) P—O3—Lu 148.2 (2)
Symmetry codes: (i) −z+1, x−1/2, −y+1/2; (ii) y+1/2, −z+1/2, −x+1; (iii) −z+1, −x+3/2, y; (iv) −y+5/4, x−3/4, −z+3/4; (v) y+3/4, −x+5/
4, −z+3/4; (vi) −y+3/2, z, −x+1.
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supplementary materials
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Fig. 1
Page 7
supplementary materials
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Fig. 2
Page 8
  • Source
    [Show abstract] [Hide abstract] ABSTRACT: A new compound, thulium cyclotetraphosphate Tm4(P4O12)3, has been synthesized in the system Tm2O3–P2O5–H2O at the temperature of 400 ºC and at the molar ratio Tm : P = 1 : 5. X-ray studies have been performed for powder samples of Tm4(P4O12)3: cubic system, space group I–43d, a = 14,7606(5) Å. Thermal behaviour of the compound has been investigated within the temperature range of 30–1500 ºC. It is found that the compound demonstrates high thermal stability. It decomposes only above the temperature of 1200 ºC. Its melting tempera-ture is 1440 ºC. An additional endothermic peak on the DSC curve in the temperature range of thulium cyclotetraphosphate melting is explained by physical displacement of the sample to the crucible centre under the influence of surface tension forces. (in Russian)
    Full-text · Article · Jan 2013