Nitrosonium nitratometallates NO[M(NO3)3] (M = Co, Ni): new synthetic approach and crystal structures

Article abstract of DOI:10.1016/j.mencom.2016.09.019

Monoclinic and triclinic modifications of nitrosonium nitratonickelate NO[Ni(NO₃)₃] as well as triclinic modification of nitrosonium nitratocobaltate NO[Co(NO₃)₃] (isostructural to triclinic NO[Ni(NO₃)₃]) have been synthesized by a new synthetic approach. Single crystal XRD studies revealed the similarity of all these structures in which octahedrally coordinated metal atoms are connected through NO₃^? bridges forming three-dimensional distorted cubic framework with NO⁺ cations located in the framework cavities.

Full text of DOI:10.1016/j.mencom.2016.09.019

Mendeleev
Communications
Mendeleev Commun., 2016, 26, 421–422
Nitrosonium nitratometallates NO[M(NO3)3] (M = Co, Ni):
new synthetic approach and crystal structures
Evgeniya B. Deeva, Anna V. Merkulova, Sergey I. Troyanov, Maxim A. Zakharov,
Viktor A. Tafeenko, Vadim F. Kozlovskii and Igor V. Morozov*
Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation.
Fax: +7 495 939 0998; e-mail: morozov@inorg.chem.msu.ru
DOI: 10.1016/j.mencom.2016.09.019
Monoclinic and triclinic modifications of nitrosonium nitrato-
nickelate NO[Ni(NO3)3] as well as triclinic modification of
nitrosonium nitratocobaltate NO[Co(NO3)3] (isostructural
to triclinic NO[Ni(NO3)3]) have been synthesized by a new
synthetic approach. Single crystal XRD studies revealed
the similarity of all these structures in which octahedrally
coordinated metal atoms are connected through NO3− bridges
forming three-dimensional distorted cubic framework with
NO+ cations located in the framework cavities.
Ni(NO3)2·xH2O
+ N2O5, HNO3, N2O4
(NO)[Ni(NO3)3]
Nitrate complexes of d-elements adopt the range of unusual
extended crystal structures, where metal atoms are linked in
chains, ribbons, layers or frameworks by nitrate bridges. Such
complexes often exhibit new types of magnetic ordering or
frustrated states as a result of the exchange interaction bet-
ween the metal atoms via nitrate bridges {e.g., Cu(NO3)2(H2O),
NO[Cu(NO3)3], Ni(NO3)21–3}. Formationoftheextended structures
is typical of the trinitratometallates A[M(NO3)3]: compounds
NO[M(NO3)3] (M = Cu,4 Mn5) possess layered structures,
whereas Ag[Co(NO3)3] contains infinite anionic chains.6 Nitrate
complexes NO[M(NO3)3] (M = Co, Ni), formulated earlier as
M(NO3)2·N2O4, have the same stoichiometry but their crystal
structures are unknown.7–9
of new compounds in all three cases. The crystal structures of the
compounds were determined by a single crystal XRD study.†
A comparison of the powder X-ray data with the calculated XRD
patterns based on single crystal data showed that the obtained
samples are practically single-phase compounds 1, 2, and 3. All
compounds were unstable in air due to their high hygroscopicity.
The reactions of 1−3 with water were accompanied by the evolu-
tion of nitrogen oxides, which indicates the presence of NO+
cations in their crystal structures.
An application of the mixtures of N2O5, N2O4, and HNO3 in
different proportions allowed us to precisely control the compo-
sition of the final products. That contradict previously published
synthetic procedures, which use only dinitrogen pentoxide.11–13
Usually N2O5 acts as a dehydrating and oxidizing agent producing
HNO3 and N2O4, respectively. The excess of N2O5 decomposes
to N2O4 and O2 within few days, which leads to the pressure
increase in the sealed ampoule; therefore, large excess of N2O5
should be avoided. According to our studies, if the consumption
of N2O5 results in the N2O4/HNO3 molar ratio close to 0.37, the
crystallization of NO[Ni(NO3)3] occurs. Deviations from this
condition lead to the formation of other nitrate species: Ni(NO3)2
for low N2O4/HNO3 ratios (ca. 0.1) and (NO)6[Ni4(NO3)12]
(NO3)2·HNO3 for N2O4/HNO3 ratio of ca. 0.66.
Herein we report the synthesis and structural characterization
of three nitrosonium nitratometallates: monoclinic (1) and triclinic
(2) modifications of NO[Ni(NO3)3] as well as triclinic modifica-
tion of NO[Co(NO3)3] (3) which is isostructural to 2.
For the synthesis of 1–3 the calculated amounts of anhydrous
nitric acid HNO3 and liquid N2O4 were added to the freshly
prepared N2O5 followed by a slow addition (~20 min) of partially
dehydrated nickel nitrate hydrate Ni(NO3)2·2.6H2O or Co powder
at 0°C with stirring. Anhydrous HNO3 and liquid N2O4 were
obtained by published procedure.10 Nitric anhydride, N2O5, was
prepared by the reaction of the anhydrous HNO3 with P2O5
according to ref. 10. In a typical experiment, 5–8 mmol of the
metal or nitrate were used; the total scale of the reaction mixture
was 6–9 g. Molar ratio of the reagents was Ni(NO3)2·2.6H2O:
N2O5 :N2O4 :HNO3 = 1:3:4:5.5 for the synthesis of 1 and 2, and
Co :N2O5 :N2O4 :HNO3 = 1:3:3.5:5.4 for the synthesis of 3.
The obtained mixture was sealed in a glass ampoule and
placed in a Dewar flask filled with 70°C water for 2 and 3, and
40°C for 1. Crystallization proceeded during gradual cooling of
the ampoule to room temperature for ca. 3 days yielding the
formation of green crystals for 1 and 2 and purple crystals for 3.
Finally, the sealed ampoule was opened, the solution was decanted,
and a crystalline precipitate was dried over P2O5 in a vacuum
desiccator. Powder XRD studies (DRON-3M diffractometer;
CuKa radiation, graphite monochromator) revealed the formation
†
Crystal data. Data collection for single crystals was performed on the
CCD diffractometer STADI–VARI Pilatus–100K, for 1 and 2, and IPDS
(Stoe) for 3.
1: monoclinic, space group P21/c, a = 7.4035(3), b = 10.1944(5) and
c = 9.0757(4) Å, b = 92.605(3)°, V = 684.27(5) Å3, Z = 4. Refinement with
1968 reflections and 137 parameters to wR2 = 0.0969 and R1 = 0.0387 for
1354 reflections with F2–> 2s(F2); ICSD 427984.
2: triclinic, space group P1, a= 6.8622(4), b= 7.1243(4) and c = 8.4433(4)Å,
a = 114.715(4)°, b = 94.889(4)°, g = 109.114(5)°, V = 342.22(3) Å3, Z = 2;
refinement with 2311 reflections and 139 parameters to wR2 = 0.0580 and
R1 = 0.0566 for 1867 reflections with F2 > 2s(F2); ICSD 427894.
3: triclinic, spacegroupP1
–, a=6.8429(6), b=7.0648(7)andc = 8.4100(8)Å,
a = 113.510(7)°, b = 94.909(7)°, g = 109.772(7)°, V = 339.19(5) Å3, Z = 2;
refinement with 1769 reflections and 140 parameters to wR2 = 0.0593 and
R1 = 0.0242 for 1592 reflections with F2 > 2s(F2); ICSD 427909.
© 2016 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
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Mendeleev Commun., 2016, 26, 421–422
O(8)
N(3)
O(7)
Ni(1)
Ni(2)
O(8)
(a)
O(7)
O(7)
N(1)
O(1)
a
(b)
Ni(1)
Ni
Ni(1)
O
N
c
b
O(3)
Ni(1)
Figure 1 Crystal structure of 2. Nickel atoms are located inside of the
octahedra.
N(2)
O(9)
O(9)
N(2)
(c)
(d)
Single crystal XRD data revealed that monoclinic (1) and
triclinic (2) modifications of NO[Ni(NO3)3] have similar crystal
structures. Both compounds display a 3D anionic framework
[Ni(NO3)3]–, which has a structure of a distorted cubic network
with nitrosonium cations located in the cavities (Figure 1). Nickel
atoms are located at the nodes of the framework and are con-
nected with each other by the nitrate bridges. Each Ni atom is
six coordinated which results in a slightly distorted octahedral
environment. The structure of 2 contains two crystallographically
independent Ni atoms, both located in the inversion centers
[Figure 2(a),(d)].
Ni(1)
O(3)
O(2)
N(1)
O(1)
O(1)
Ni(2)
Ni(1)
Ni(2)
N(1)
O(2)
Figure 2 Chains in the crystal structures of 1 and 2. Chains with anti-anti
NO3 groups: (a) type 1 for 2 and (b) type 2 for 1. Chains with sin-anti NO3
groups (type 3) for (c) 1 and (d) 2.
Three types of infinite chains can be discriminated in the
crystal structures of 1 and 2, each chain passes via Ni atom
connecting trans vertices of [NiO6] octahedra (Figure 1). Two of
these chains have similar structures and consist of Ni atoms lying
almost on a straight line [Figure 2(a),(b)] and NO3− bridges of the
anti-anti type.14 Ni···Ni distances are 6.0 Å for the chains of the
first type [Figure 2(a)] and 5.7 Å for the chains of the second
type [Figure 2(b)]. The most significant differences can be seen
between the structures of chains of the third type with the shortest
Ni···Ni distance of 5.25 Å in 1 and 5.20 Å in 2. In these chains Ni
atoms are bound by NO3− groups of the sin-anti type14 and form
a zig-zag chain in case of structure 1 [Figure 2(c)], and have
linear arrangement in the structure 2 [Figure 2(d)].
The chains of the types 2 and 3 with short Ni···Ni distances
can be considered as forming layers in both triclinic and mono-
clinic modifications of NO[Ni(NO3)3]. Ni atoms in these layers
form a rectangular network, which is similar to the network in
the structure of Ni(NO3)2(H2O)2.15,16 The layers are connected
with each other via nitrate bridges of the anti-anti type (type 1
chains, Ni···Ni distance of ca. 6.0 Å), which leads to the forma-
tion of a three-dimensional framework. The N–O bond lengths
in NO+ cations [0.989(6) Å in 1 and 1.031(3) Å in 2] are typical
of NO+ containing compounds.5
properties, as even small structural differences may substantially
affect the nature of magnetic exchange interactions.
This work was supported by the Russian Foundation for Basic
Research (grant no. 16-33-01131-a). The authors are grateful to
the Development program of M. V. Lomonosov Moscow State
University for the purchase of the CCD diffractometer STADI–
VARI Pilatus–100K.
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Received: 16th May 2016; Com. 16/4936
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