Manganese(II) 9-Molybdomanganate(IV), [Mn(H2O)4] 3 ? [MnMo9O32] ? 2H2O: Synthesis, thermal analysis, IR spectra, and crystal structure

Article abstract of DOI:10.1134/S1070328407110061

The [Mn(H₂O)₄]₃ ? [MnMo ₉O₃₂] ? 2H₂O complex was synthesized and studied by X-ray diffraction, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32, a = 14.811(2) A, c = 14.232(2) A, V = 2703.7(8) A³, M = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm³.

Full text of DOI:10.1134/S1070328407110061

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2007, Vol. 33, No. 11, pp. 826–830. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © G.Z. Kaziev, A.V. Oreshkina, S. Holguin Quinones, V.E. Zavodnik, A. de Ita, T.A. Tripol’skaya, 2007, published in Koordinatsionnaya Khimiya, 2007,
Vol. 33, No. 11, pp. 840–844.
Manganese(II) 9-Molybdomanganate(IV), [Mn(H O) ] ·
2
4 3
[
MnMo O ] · 2H O: Synthesis, Thermal Analysis, IR Spectra,
9
32
2
and Crystal Structure
a
a
b
c
G. Z. Kaziev , A. V. Oreshkina , S. Holguin Quinones , V. E. Zavodnik ,
b
d
A. de Ita , and T. A. Tripol’skaya
a
Moscow State Pedagogical University, ul. Malaya Pirogovskaya 1, Moscow 119882 Russia
b
Universidad Autonoma Metropolitana, Azcapotzalco, Mexico
c
Karpov Research Institute of Physical Chemistry, ul. Vorontsovo pole 10, Moscow, 103064 Russia
d
Kurnakov Institute of General and Inorganic Chemistry, Rusian Academy of Sciences,
Leninskii pr., 31, Moscow 119991 Russia
Received December 27, 2006
Abstract—The [Mn(H O) ] · [MnMo O ] · 2H O complex was synthesized and studied by X-ray diffraction,
2
4 3
9
32
2
thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are trigonal: space group R32,
3
3
a = 14.811(2) Å, c = 14.232(2) Å, V = 2703.7(8) Å , å = 1848.5, Z = 3, ρ(calcd.) = 3.419 g/cm .
DOI: 10.1134/S1070328407110061
Heteropoly compounds (HPC) constitute a large ammonium molybdate solution acidified to pH 3 with
class of polyoxo compounds coordination compounds nitric acid, a 30% solution of hydrogen peroxide
composed of metal–oxygen octahedra åé , which (20 ml) was added with stirring and then, the Mn(II)
6
share vertices and edges to form a strong framework, sulfate solution. The mixture was heated on a water
i.e., heteropolyanion (HPA). Heteropoly compounds bath for 3.5 h. In 3 days, red-brown crystals were
are widely used as homogeneous and heterogeneous, formed that were recrystallized from hot water and
acid, and oxidating catalysts [1–4] and as model sys- washed with an alcohol.
tems in studying fundamental catalysis problems [5, 6].
The elemental analysis for Mo, Mn was performed
Today, heteropoly compounds are known with p-,
d-, and f complex-forming elements; hydrogen, alkali,
by a known procedure [14]. The composition of the
synthesized compound I was confirmed by the mass
and alkaline earth metal and ammonium ions can serve
spectrometry method.
as the cations [7, 8].
The first data on molybdomanganates (red crystals
For [Mn(H O) ] · [MnMo O ] · 2H O
2
4 3
9
32
2
of the potassium and ammonium salts of the composi-
anal. calcd., %: Mn 12.03; Mo 46.71; O 27.58; H O 13.67
2
tion 5å é · Mn O · 16MoO · 12H O) were reported
2
2
3
3
2
in [9]. Later, ruby-red crystals of Na é · MnO · Found, %:
Mn 11.90; Mo 46.74; O 27.69; H2O 13.63
2
2
1
2MoO · nH O and K é · MnO · 12MoO · nH O
2 2 3 2
(NH ) O · K é · Mn O · 10MoO · 5H O [11] were
4 2 2 2 3 3 2
3 2 2 2 3 2
10] and the salts 3K é · MnO · 8MoO · 5H O and
[
The powder X-ray diffraction analysis was per-
formed on a STOE IP autodiffractometer, 2θ = 5°–80°.
X-ray pictures were indexed with the Powder-2 pro-
gram package. The comparison of X-ray picture
obtained with the PCPDFWIN database showed that
2
synthesized. The preparation of potassium and ammo-
nium molybdomanganates with different Mn : Mo ratio
was described in [12].
Previously, we synthesized and studied ammonium compound I is individual and does not contain impuri-
9
-molybdomanganate [13]. It was of interest to synthe- ties. The powder X-ray diffraction data are available
size and study by X-ray diffraction, powder X-ray dif- from the authors (e-mail: gkaziev@mail.ru.).
fraction, IR spectroscopy, and thermogravimetry
TGA of I was carried out on a Paulik–Paulik–Erdey
[
Mn(H O) ] · [MnMo O ] · 2H O (I).
2 4 3 9 32 2
setup in the temperature range of 20–1000°ë (heating
rate 10 K/min, a 100 g sample) using calcined alumina
as the reference.
EXPERIMENTAL
Compound I was synthesized using a known proce-
IR spectra were recorded on a Perkin Elmer spectro-
dure [7] that was slightly modified. To a saturated photometer at 400–4000 cm (as KBr pellets).
–
1
8
26

MANGANESE(II) 9-MOLYBDOMANGANATE(IV)
827
Table 1. Selected bond lengths and bond angles in [Mn(H O) ] · [MnMo O ] · 2H O*
2
4 3
9
32
2
Bond
d, Å
Bond
Mo(2)–O(1d)
d, Å
Mo(1)–O(4)
1.707(2)
1.967(2)
2.229(2)
1.700(2)
1.715(2)
1.881(2)
2.076(1)
2.206(2)
2.240(2)
1.889(2)
1.931(2)
1.999(4)
2.232(2)
2.060(2)
Mo(1)–O(3b)
Mo(1)–O(1b)
Mo(2)–O(5)
Mo(2)–O(6)
Mo(2)–O(3)
Mo(2)–O(2)
Mo(2)–O(1a)
Mo(2)–O(1a)
Mn(2)–O(1wa)
Mn(2)–O(2w)
Mn(2)–O(6)
Mn(2)–O(1wb)
Angle
ω, deg
Angle
ω, deg
O(4a)Mo(1)O(4)
O(4a)Mo(1)O(3b)
O(4)Mo(1)O(3b)
O(3b)Mo(1)O(3c)
O(4a)Mo(1)O(1b)
O(4)Mo(1)O(1b)
O(3b)Mo(1)O(1b)
O(3c)Mo(1)O(1b)
O(1b)Mo(1)O(1c)
O(5)Mo(2)O(6)
O(5)Mo(2)O(3)
O(6)Mo(2)O(3)
O(5)Mo(2)O(2)
O(6)Mo(2)O(2)
O(3)Mo(2)O(2)
O(5)Mo(2)O(1d)
O(6)Mo(2)O(1d)
O(3)Mo(2)O(1d)
O(2)Mo(2)O(1d)
O(5)Mo(2)O(1d)
O(6)Mo(2)O(1a)
O(3)Mo(2)O(1a)
O(2)Mo(2)O(1a)
O(1d)Mo(2)O(1a)
Mo(2d)O(1)Mo(2a)
Mo(1e)O(1)Mo(2a)
106.19(1)
96.67(1)
100.17(1)
151.80(1)
91.76(1)
161.22(1)
82.77(9)
74.29(8)
71.03(1)
105.74(1)
102.10(1)
102.42(1)
90.10(1)
101.48(1)
148.97(1)
95.70(1)
158.16(1)
76.48(8)
73.96(8)
160.98(1)
86.90(1)
88.60(9)
73.22(9)
71.30(1)
98.13(7)
153.96(1)
Mo(2e)O(2)Mo(2)
Mo(2)O(3)Mo(1e)
O(1a)Mn(1)O(1)
O(1a)Mn(1)O(1)
O(1b)Mn(1)O(1)
107.99(9)
112.34(1)
101.29(1)
86.61(9)
169.23(1)
73.60(1)
170.10(5)
98.50(7)
90.00(3)
91.80(8)
80.40(6)
167.90(7)
110.00(3)
85.50(5)
89.90(5)
88.63(1)
95.44(4)
84.90(6)
91.80(6)
174.26(1)
101.31(1)
101.20(8)
92.26(7)
100.06(8)
158.16(1)
O(1wae)Mn(2)O(1wa)
O(1wae)Mn(2)O(2w)
O(1wa)Mn(2)O(2w)
O(2w)Mn(2)O(2we)
O(1wae)Mn(2)O(1wb)
O(2w)Mn(2)O(1wb)
O(2we)Mn(2)O(1wb)
O(1wbe)Mn(2)O(1wb)
O(1waf)Mn(2)O(6)
O(1wa)Mn(2)O(6)
O(2w)Mn(2)O(6)
O(2wf)Mn(2)O(6)
O(1wbf)Mn(2)O(6)
O(1wb)Mn(2)O(6)
O(6f)Mn(2)O(6)
Mn(1)O(1)Mo(2d)
Mn(1)O(1)Mo(1e)
Mo(2d)O(1)Mo(1e)
Mn(1)O(1)Mo(2a)
Mo(2)O(6)Mn(2)
*
The coordinates of symmetrically equivalent atoms: (a) –x, –x + y, –z + 1; (b) y, x, –z + 1; (c) –y, –y, z; (d) –y, –y, –z + 1; (e) –x + y, –x, z;
(f) –y – 1/3, –y – 2/3, –z + 1/3.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 11 2007

8
28
KAZIEV et al.
4
Table 2. The coordinates of atoms (×10 ) and their equivalent
Symmetrically equivalent octahedral with the atoms
Mo(2), Mo(2a), Mo(2b), Mo(2c), Mo(2d), Mo(2e) each
contain two terminal atoms O(5) and O(6) of the
3
thermal parameters (×10 ) for [Mn(H O) ] · [MnMo O ] ·
2
4 3
9
32
2
H O
2
cis-åÓé groups (Mo=O
1.700 and 1.715 Å,
2
2
term
Atom
x
y
z
U , Å
eq
respectively), the bridging atom µ -é(3) (åÓ(2)–é(3)
2
Mo(1)
Mo(2)
Mn(1)
Mn(2)
O(1)
0
2154(1)
–887(1)
0
5000
18(1)
17(1)
12(1)
31(1)
15(1)
17(1)
19(1)
29(1)
30(1)
29(1)
77(6)
1.881 Å), the bridging atom µ -é(2), linking three Mo
3
atoms in the triplet åÓ é (åÓ(2)–é(2) 2.076 Å), and
617(1)
0
3235(1)
3
13
two atoms µ -é(1‡) and µ -é(1b), linking three Mo
4
4
50000
atoms in the triplet åÓ é with the central heteroatom
3
13
–912(1) –3333
1667
Mn(1) (Mo(2)–O(1d) 2.206, Mo(2)–O(1a) 2.240 Å).
699(2)
0
–459(2)
5810(1)
2715(2)
4242(2)
5769(2)
2472(2)
2757(2)
The HPA also contains three Mo(1)O(6) octahedral
that are not bonded with the complex cation
O(2)
0
2+
[
Mn(H O) ] and each contain two terminal O(4) and
2 4
O(3)
1217(2) –1227(2)
O(4a) atoms (Mo(1)=O(4) 1.707 Å), two atoms O(3)
and O(3a) forming the bridging bond with the Mo
atoms of two different triplet groups åÓ é
O(4)
636(2)
3164(2)
–296(2)
O(5)
1632(2)
3
6
O(6)
–213(2) –2086(2)
(åÓ(1)−é(3) 1.967 Å) and two atoms O(1) and O(1b),
bonding three Mo atoms and a central atom Mn(1)
O(1wa)
O(1wb)
O(2w)
O(3w)
–202(14) –4000(20) 2213(10)
(Mo(1)−O(1) 2.229 Å).
–605(18) –4320(20) 2457(14) 102(8)
The Mn(1) heteroatom has a regular octahedral sur-
rounding of the O atoms (Mn(1)–O 1.889 Å).
–2215(3) –4031(4)
364(14) –283(15)
2435(3)
779(10)
73(2)
82(4)
The outer-sphere hydrated complex cation forms an
octahedron containing four O atoms of water molecules
2
+
[
Mn(H O) ] (ån(2)–é(1w) 1.999, ån(2)–é(2w)
2 4
X-ray diffraction analysis was carried out on auto-
mated Enraf-Nonius CAD-4 (MoK radiation, λ =
1
.931 Å), two O(6) atoms (Mn(2)−O(6) 2.232 Å). The
O(6) atoms of dioxo group cis-åÓé act as the bridg-
α
2
0
.71073 Å) at room temperature.
ing bonds between the HPA and the outer-sphere cat-
ions in the HPC.
The crystals are trigonal: a = 14.811(2), c =
3
1
4.232(2) Å, V = 2703.7(8) Å , M = 1855.5, Z = 3,
The coordination of the outer-sphere cation brings
about some changes in the bond lengths of the HPA in
accordance with the regularities discovered in [17–19].
It was found that the complex formation leads to some
elongation of one Mo=Oterm bond in the Mo(2)O(6)
3
ρ(calcd.) = 3.419 g/cm , space group R32.
The red-brown single crystal 0.32 × 0.32 × 0.26 mm
in size was used. Three control reflections measured
every 100 min showed constant intensities to within
octahedron of the triplet group åÓ é from 1.707 to
0
.4%. Altogether 2790 reflections were recorded,
3
13
1
1
.715 Å and shortening of the other bond from 1.707 to
.700 Å (Fig. 2).
including 1751 independent reflections (I > 2σ(I)) in
the θ range of 2.14°–29.98° (R = 0.0191). The struc-
int
ture was solved by the direct method and refined by the
The water molecules in compound I have partially
full-matrix least-squares method in the anisotropic occupied positions.
approximation for non-hydrogen atoms. An absorption
The TGA of the title compound I (Fig. 3) revealed
three endotherms, the first (at 125°ë) corresponding to
dehydration of the compound with removal of two crys-
tallization water molecules. The second endotherm at
330°ë corresponds to removal of 12 water molecules of
the outer-sphere complex cation and decomposition of
the HPC with the formation of the brown mixture
–1
correction was applied (µ = 4.505 mm ) by ψ-scan-
ning, í = 0.326, Tmax = 0.387. The range of indices:
min
0
0
0
≤ h ≤ 20, –20 ≤ k ≤ 18, 0 ≤ l ≤ 19. The value ∆
=
max
–3
–3
.427 e Å , ∆ = –0.474 e Å . The final values R =
min
1
.0168, wR = 0.0422 (for I > 2σ(I)), R = 0.0182,
2
1
wR = 0.0425 (for all), GOOF = 1.136, extinction coef-
2
ficient 0.00238(8). The calculations were carried out
with the SHELX-97 program package [15]. The bond
lengths and bond angles are listed in Table 1, the coor-
dinates of the atoms and the thermal parameters are
given in Table 2.
4
MnO + 9MoO . The third endotherm (at 700°ë) refers
2 3
to removal of nine åÓé molecules. The scheme of the
3
thermal decomposition is as follows:
[
Mn(H O) ] ⋅ [MnMo O ] ⋅ 2H O
4
3
2 9 32 2
–
2H O
2
[
Mn(H O) ] · [MnMo O ]
RESULTS AND DISCUSSION
2 4 3 9 32
1
25°C
6
–
.
The structure of the HPA [MnMo O ] can be rep-
–12H O,
9
32
2
3
/2O
–9MoO3
3700°C
2
resented as a result of removal of three out of the six
4
MnO + 9MoO
4MnO
2
2
3
30°C
octahedra lying in the plane perpendicular to the ë
3
4
–
axis of the hypothetical anion [MnO Mo O ] con-
IR spectra of the HPC are sufficiently characteristic
for the compounds of this class belonging to different
4
12 36
taining twelve åÓé octahedra [16, 17].
6
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 11 2007

MANGANESE(II) 9-MOLYBDOMANGANATE(IV)
829
O(6e)
O(6e)
O(4d)
O(5b)
O(3e)
O(5e)
O(4d)
Mo(2e)
O(5e)
O(5b)
O(3e)
Mo(2e)
O(2w)
O(1d)
Mo(1a)
O(4a)
O(4c)
Mo(6b)
O(3d)
O(4b)
O(1wa)
O(1d)
O(4a)
O(3d)
Mo(1a)
O(6a)
O(4e)
O(3b)
O(4c)
Mo(6b)
O(6a)
O(6d)
Mo(1b)
O(6d)
O(4a)
O(1c)
O(5a)
Mo(1b)
O(6b)
O(3b)
O(1e)
O(1e)
Mo(2d)
O(5d)
O(1c)
Mn(2)
O(4b)
O(5d)
O(6b)
Mn(1)
O(1b) O(5c)
Mo(2a)
O(1)
O(5a)
Mn(1)
O(3c)
Mo(2a)
Mo(2d)
O(1)
O(2wa)
O(5c)
O(1b)
O(3c)
O(1a)
O(1wb)
O(1a)
O(3a)
O(2)
Mo(2c)
O(3a)
O(2)
Mo(2c)
O(6c)
O(6c)
Mo(1)
O(4)
O(4)
Mo(2)
O(6)
O(3)
O(6)
Mo(1)
Mo(2)
O(3)
O(4a)
O(4a)
O(5)
O(5)
6
–
Fig. 1. The structure of HPA [MnMo O ] .
9
32
Mn(2a)
O(5)
.715
O(4)
1
2.232
1
.999
Mo(1)
1
.707
O(6)
Mn(2)
O(4a)
Mo(2)
Mn(1)
Mn(2e)
Mn(2c)
Mn(2b)
Mn(2d)
Fig. 2. The structure of HPC I.
structural types. The IR spectrum of compound I con- terminal (multiple) bonds Mo=O appear as a doublet
term
–
1
tains several sets of the bands due to vibrations of the at 900–1000 cm . However, in addition to two remain-
–
1
terminal and bridging bonds metal–oxygen. As follows ing bonds at 900 (ν ) and 935 (ν ) cm due to the
s
as
from the literature data [19, 20], the vibrations of the vibrations of the cis-åÓé groups and not participation
2
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 11 2007

8
30
KAZIEV et al.
T, °C
∆m, %
2. Maksimov, G.V., Usp. Khim., 1995, vol. 64, no. 5,
p. 480.
DTA
TG
9
7
5
3
1
00
00
00
00
00
3. Pop, M.T., Geteropoli- i izopolioksometallaty (Het-
eropoly- and Isopolyoxometallates), Novosibirsk:
Nauka, 1990.
10
4
5
6
. Kozhevnikov, I.V., Usp. Khim., 1987, vol. 56, no. 9,
p. 1417.
7
00
. Misono, M., Catalysis by Acids and Bases, Imelik, B.,
Ed., Amsterdam: Elsevier, 1985, p. 147.
. Sergienko, V.S. and Porai-Koshits, M.A., Itogi Nauki
Tekh., Ser. Kristallokhimiya, Moscow: VINITI, 1985,
vol. 19, p. 79.
2
3
0
0
3
30
í
1
25
7
. Holguin Quinones, S., Ivanov-Emin, B.N., and
Kaziev, G.Z., Zh. Neorg. Khim., 1979, vol. 24, no. 12,
p. 3279.
0
30
Time, min
60
8
. Maksimova, L.G., Torchenkova, E.A., and Kazanskii, L.P.,
Fig. 3. Thermogravimetric pattern of compound I.
Zh. Neorg. Khim., 1988, vol. 33, no. 9, p. 2278.
9
. Struve, H., J. Prakt. Chem., 1854, vol. 61 P, p. 499.
1
1
0. Pechard, E., Compt. Rend., 1897, vol. 129, p. 29.
in the complex formation, the spectrum also contains a
1. Rosenheim, A. and Itzig, H., Z. Anorg. Allg. Chem.,
–
1
band, at 875 cm , which appears due to a new coordi-
1
898, vol. 16, p. 76.
nation Mo(2)−Oterm−Mn(2).
1
2. Hall, R.D., J. Am. Chem. Soc., 1907, vol. 29, no. 5,
The IR spectrum of compound I also exhibits the
p. 692.
–
1
intense absorption bands at 500−700 cm (493, 592, 13. Holguin Quinones, S., Kaziev, G.Z, Oreshkina, A.V.,
6
56, 692) corresponding to different vibrations of the
et al., Koord. Khim., 2007, vol. 33, no. 6, p. 422 [Russ. J.
Inorg. Chem. (Engl. Transl.), vol. 33, no. 6, p. 412].
bridging bonds Mo–O–Mo. The intense band at
–1
5
42 cm should be assigned to the vibrations of 14. Kaziev, G.Z., Dutov, A.A., Holguin Quinones, S., et al.,
Zh. Neorg. Khim., 2004, vol. 49, no. 5, p. 743 [Russ. J.
Inorg. Chem. (Engl. Transl.), vol. 49, no. 5, p. 678].
Mn(1)–O of a central octahedron of the HPA, whereas
–
1
the band in the form of a doublet at 425, 435 cm cor-
responds to the Mn(2)–O vibrations of the outer-sphere
hydrated cation [Mn(H O) ] .
1
1
1
5. Sheldrick, G.M., SHELX-97, Göttingen (Germany):
2+
Univ. of Göttingen, 1997.
2
4
6. Waugh, T.L.T., Shoemaker, P., and Pauling, L., Acta
Crystallogr., 1954, vol. 7, no. 5, p. 438.
7. Porai-Koshits, M.A. and Atovmyan, L.O., Itogi Nauki
Tekh., Ser. Kristallokhimiya, Moscow: VINITI, 1985,
vol. 19, p. 3.
8. Porai-Koshits, M.A. and Atovmyan, L.O., Kristal-
lokhimiya i stereokhimiya koordinatsionnykh soedinenii
molibdena (Crystal Chemistry and Stereochemistry of
Coordination Compounds of Molybdenum), Moscow:
Nauka, 1975, p. 231.
–1
The bands at 1620 and 3000–3650 cm are due to
vibrations of the crystallization water molecules.
The X-ray diffraction and IR study confirm the
6
–
hexadentate function of a macroligand [MnMo O ]
9
32
1
due to two triplet groups åÓ é with six active termi-
nal O atoms of the cis-åÓé groups capable of coordi-
3
13
2
nating with the central metal atom.
1
9. Gavrilova, L.O. and Molchanov, V.N., Koord. Khim.,
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2
005, vol. 31, no. 6, p. 427.
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. Nikitina, E.N., Geteropolisoedineniya (Heteropoly 20. Davydov, A.A. and Goncharova, O.I., Usp. Khim., 1993,
Compounds), Moscow: Goskhimizdat, 1962. vol. 62, no. 2, p. 118.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 11 2007