NH4MSO4F (Mu202f=u202fMn, Fe, Co, Ni): A series of thermally stable transition metal fluorosulfates with KTP-type structure

Article abstract of DOI:10.1016/j.poly.2018.06.017

Four new transition metal fluorosulfates NH₄MSO₄F (M = Mn, 1; Fe, 2; Co, 3; Ni, 4) were solvothermally synthesized in the solvent of N,N-dimethylacetamide (DMA) with HF as the mineralization agent. The X-ray single crystal diffraction analyses revealed that 1–4 are isomorphous, and possess a three-dimensional framework with the same structural topology as the known nonlinear optical material KTiOPO₄ (KTP). The four compounds were constructed from MO₄F₂ octahedra and SO₄ tetrahedra to form two kinds of intersecting 6-membered ring channels along the a and c axes, respectively. Within the channels locate the NH₄⁺ cations from the decomposition of DMA molecules. All the compounds are thermally stable up to 330 °C. The magnetic studies of 1–4 revealed the antiferromagnetic interaction behaviors in the range of 1.8–300 K.

Full text of DOI:10.1016/j.poly.2018.06.017

Polyhedron 152 (2018) 55–60
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Polyhedron
journal homepage: www.elsevier.com/locate/poly
NH4MSO4F (M = Mn, Fe, Co, Ni): A series of thermally stable transition
metal fluorosulfates with KTP-type structure
a
a
a
b,
Gen-wu Ge a, , Wen Luo , Xin-lei Zhang , Xiao-di Du , Li-li Liang
⇑
⇑
a Henan Key Laboratory of Rare Earth Functional Materials, The Key Laboratory of Rare Earth Functional Materials and Applications, Zhoukou Normal University, Zhoukou 466001,
PR China
b Department of Chemistry, Bengbu Medical College, Bengbu 233030, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Four new transition metal fluorosulfates NH4MSO4F (M = Mn, 1; Fe, 2; Co, 3; Ni, 4) were solvothermally
synthesized in the solvent of N,N-dimethylacetamide (DMA) with HF as the mineralization agent. The
X-ray single crystal diffraction analyses revealed that 1–4 are isomorphous, and possess a three-
dimensional framework with the same structural topology as the known nonlinear optical material
KTiOPO4 (KTP). The four compounds were constructed from MO4F2 octahedra and SO4 tetrahedra to form
two kinds of intersecting 6-membered ring channels along the a and c axes, respectively. Within the
channels locate the NHþ4 cations from the decomposition of DMA molecules. All the compounds are
thermally stable up to 330 °C. The magnetic studies of 1–4 revealed the antiferromagnetic interaction
behaviors in the range of 1.8–300 K.
Received 23 March 2018
Accepted 5 June 2018
Available online 14 June 2018
Keywords:
Metal fluorosufates
Solvothermal synthesis
Crystal structures
Thermal stability
Magnetic property
Ó 2018 Elsevier Ltd. All rights reserved.
1. Introduction
or MO2F4 units through vertex, edge, or face sharing to form addi-
tional M–F–M linkages, this allows the control of the structural
Porous solid materials based on TO4 (T = Si, Al, P, etc.) tetrahedra
have been extensively studied due to their potential applications in
the fields of catalysis, separation and ion-exchange [1]. The similar-
ities of coordination chemistry and geometry between SO4 and PO4
tetrahedra suggest the possibility to prepare a large family of open-
framework metal sulfates with diverse structures. Compared to the
abundance and diversity of metal phosphates reported in the litera-
ture [2], however, the metal sulfates constructed from SO4 tetrahe-
dra have not been paid much attention until a few transition metal
sulfates and rare earth sulfates with interesting framework struc-
tures and properties were reported in the past decades [3]. Recently,
alkali ion containing metal fluorosulfates LiMSO4F (M = Mn, Fe, Co,
Ni, Zn, etc.) with olivine, tavorite and sillimanite structures have
been of particular interests because these materials exhibit excel-
lent electrochemical properties with promising applications in
lithium-ion based batteries [4]. By using the methods of preparation
of zeolites and aluminophosphates, i.e., hydrothermal synthesis
with the presence of structure-directing agents and/or mineralizer
Fꢀ ion, a number of metal sulfates have been reported [5], which
exhibit rich structural chemistry. The incorporation of fluoride into
the transition metal sulfate frameworks results in linkage of MO4F2
dimensionality and linking fashion of the polyhedra [6], while most
known 3D framework sulfates are formed by strict alternation of
MO6 or MO4 and SO4 units without any direct connection between
two MO6 octahedra or MO4 tetrahedra.
On the other hand, it is known that KTiOPO4 (KTP) is an out-
standing nonlinear optical material for second harmonic genera-
tion (SHG) due to its high power conversion efficiencies [7]. The
Ti and P atoms in the KTP framework can be replaced by other
transition or main-group metals, and other group V elements,
respectively, while the K+ ions can also be substituted with other
alkali, ammonium ions, and organic amines etc. [8]. There have
been a number of metal phosphates [9] and arsenates [10] with
KTP-type structure reported in the literature. However, the metal
sulfates with KTP-type structure have not been reported so far.
We herein report the synthesis and characterization of four new
transition metal fluorosulfates NH4MSO4F (M = Mn, 1; Fe, 2; Co,
3; Ni, 4) possessing KTP-type structure.
2. Experimental
2.1. Synthesis
⇑
All reagents were of analytical grade and used as received
without any further purification. The four compounds were
Corresponding authors.
E-mail addresses: gegenwu@163.com (G.-w. Ge), liangjyt@163.com (L.-l. Liang).
https://doi.org/10.1016/j.poly.2018.06.017
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.

56
G.-w. Ge et al. / Polyhedron 152 (2018) 55–60
solvothermally prepared by using nearly identical methods from a
mixture of metal nitrate, concentrated H2SO4 and aqueous HF. A
typical procedure is as follows: 0.5 mmol of metal nitrates
(0.375 g of 50% Mn(NO3)2 solution for 1, 0.202 g of Fe(NO3)3ꢁ9H2O
for 2, 0.146 g of Co(NO3)2ꢁ6H2O for 3 and 0.375 g of 33% Ni(NO3)2
solution for 4) were first dissolved in 6 ml of N,N-dimethylac-
etamide (DMA), followed by dropwise addition of 2 mmol of
concentrated H2SO4 (98%, 0.11 ml) under stirring. To the above
solution was added 2 mmol of 40% HF solution (be cautious!) with
a syringe. The clear solution after stirring for 30 min was trans-
ferred into a 15 ml Teflon-lined stainless steel autoclave, and
heated at 180 °C for 5 days. After cooling to room temperature
naturally, colourless diamond crystals (1 and 2), red (3) or light
green (4) bipyramid crystals were obtained by filtration, and
washed with ethanol and acetone, then dried in air.
SHELXL-97 program [12]. Anisotropic thermal parameters were
refined for all non-hydrogen atoms. Details of the crystal parame-
ters, data collection and refinement results are summarized in the
Table 1. Selected interatomic bond lengths and angles with their
estimated standard deviations and further details can also be
obtained from the Supplementary information.
3. Results and discussion
3.1. Synthesis
The four title compounds were solvothermally synthesized
from the DMA solution of metal nitrates, concentrated H2SO4 and
aqueous HF. Even though the DMA molecules were not incorpo-
rated into the final products, part of the DMA molecules may
decompose to NHþ4 ion in the acidic solution under high tempera-
ture and press. It is noted that although Fe(III) nitrate was used
during the synthesis, the valence of iron in the final product turned
to be divalent while ammonia decomposed from the solvent of
DMA may act as the reducing agent in the reduction procedure
2.2. Characterization
Powder X-ray diffraction (PXRD) data were obtained using
Bruker D8 Advance diffractometer with Cu
Ka radiation
(k = 1.54056 Å), with a step speed of 0.2° per second. FT-IR spectra
were recorded on a Nicolet Impact 410 spectrometer between 400
and 4000 cmꢀ1 using the KBr pellet method. Thermogravimetric
analyses (TGA) were conducted on a Perkin-Elmer Pyris I thermo-
gravimetric analyzer with a heating rate of 20 °C minꢀ1 in an N2
atmosphere. The temperature-dependent magnetic susceptibility
measurements of compounds 1–4 were performed on the
powdered samples in the temperature range of 1.8–300 K at a
2000 Oe external field with a Quantum Design MPMS-XL7 SQUID
magnetometer.
2.3. Crystal structure determinations
Suitable single crystals of 1–4 were selected for single-crystal
X-ray diffraction analyses. The measurements were carried out
on a Bruker SMART APEX CCD diffractometer operating at room
temperature. Intensities were collected with graphite monochrom-
atized Mo-Ka radiation (k = 0.71073 Å) operating at 50 kV and 30
mA. Data reductions and absorption corrections were performed
using the SAINT and SADABS programs [11], respectively. The struc-
tures were solved by direct methods using the SHELXS-97 program
and refined with full-matrix least squares on F2 using the
Fig. 1. PXRD patterns of 1: (a) calculated, (b) as-synthesized.
Table 1
Crystallographic and structural data for 1–4.
Compound reference
1
2
3
4
CCDC No.
843552
843553
843554
843555
Chemical formula
Formula mass
NH4MnSO4F
188.04
NH4FeSO4F
188.95
NH4CoSO4F
192.03
NH4NiSO4F
191.81
Crystal system
orthorhombic
orthorhombic
orthorhombic
orthorhombic
Unit cell dimensions
a (Å)
b (Å)
13.4004(12)
11.0933(10)
6.7101(6)
997.49(15)
291(2)
Pnna
13.2721(9)
10.8809(7)
6.6449(4)
959.61(11)
291(2)
Pnna
13.1861(7)
10.6969(5)
6.6201(3)
933.77(8)
291(2)
Pnna
13.0229(16)
10.6215(13)
6.5487(8)
905.83(19)
291(2)
Pnna
c (Å)
V (Å3)
T (K)
Space group
Number of formula units per unit cell, Z
Number of reflections measured
Number of independent reflections
Rint
8
8
4766
947
0.0606
0.0567
0.1249
0.0724
0.1291
1.066
8
4561
921
0.0607
0.0505
0.1079
0.0700
0.1131
1.089
8
4918
986
4529
893
0.0689
0.0542
0.0974
0.0809
0.1032
1.014
0.0602
0.0515
0.0927
0.0763
0.0969
1.022
Final R1 values (I > 2
r
(I))a
Final wR(F2) values (I > 2
r
(I))a
Final R1 values (all data)a
Final wR (F2) values (all data)a
Goodness of fit (GOF) on F2
a
R1
=
R
||Fo| ꢀ |Fc||/
R
|Fo|, wR = [
R
w(F2o ꢀ F2c)2/
R .
w(F2o)2]1/2

G.-w. Ge et al. / Polyhedron 152 (2018) 55–60
57
for the powder samples. Elemental analysis for 1, H, 2.3%; N, 7.3%
(calculated as H, 2.2%; N, 7.5%), for 2, H, 2.2%; N, 7.1% (calculated
as H, 2.1%; N, 7.4%); for 3, H, 2.2%; N, 7.1% (calculated as H, 2.1%;
N, 7.3%); for 4, H, 2.1%; N, 7.0% (calculated as H, 2.1%; N, 7.3%).
3.2. Descriptions of crystal structures
All the four title compounds crystallize in the orthorhombic
system with Pnna space group. In comparison, most of other
known KTP-type structures crystallize in the space group of
Pna21, with the exception of NH4VPO4F [9c], which preclude the
possibility of nonlinear optics at room temperature like other
KTP-type materials. In fact, the space group of Pna21 was initially
considered in solving these structures, however, the structural
model cannot be refined properly in this acentric space group,
while it can only be well solved in the centric space group of
Pnna. It can be seen from Table 1 that the cell volume of 1 to 4
decreases from 997.49(15) to 905.83(19) Å3, which was
correlated with the reduced ionic radii of Mn2+, Fe2+, Co2+ and
Ni2+ ions and consistent with the Vegard’s law [13]. Similar obser-
vations have been obtained in the KTP-type metal fluorophos-
phates NH4MPO4F (M = Ga, V, Fe) [9], as shown in Fig. 2.
Compared to the metal phosphates or arsenates with KTP-typed
structures, the metal sulfates show slightly larger changes in cell
volumes.
Fig. 2. Plots of the unit-cell volume vs. ionic radius for the KTP-type compounds.
Since four compounds are isomorphous, compound 1 is chosen
as an example for structural description. As shown in Fig. 3, the
asymmetric unit of compound 1 consists of ten crystallographically
unique non-hydrogen atoms, including two Mn, two S, four O and
one F framework atoms, and one N atom from extra-framework
ammonium ion. Both Mn sites are six-coordinated by four O and
two F atoms in MnO4F2 octahedron geometry. However, the Mn1
adopt a cis-configuration with the F–Mn1ꢀF angles of 87.37°, while
the Mn2 is in a trans-configuration with the F–Mn2–F angles of
180°. The two Mn atoms are linked by an F bridge with the
Mn1–F–Mn2 angle of 122.52°. The Mn–O bond distances are in
the range of 2.145(4) to 2.211(4) Å, while the Mn–F lengths is
2.083(3) Å. Both sulfur atoms are in a tetrahedral coordination
geometry with the S–O lengths in the range of 1.465(4)–1.479(4) Å
and O–S–O angles in the range of 106.5(4)–111.1(2)°, which are
consistent with those of the other transition metal sulfates in
the literature [6]. The calculated bond valence sums [14] for the
metal sites in 1–4 are within the expected values, as listed in
the Table 2.
The 3-dimensional framework of compound 1 is constructed by
linkages of MnO4F2 octahedra and SO4 tetrahedra. As shown in
Fig. 4, the alternative connections of cis- and trans-MnO4F2
octahedra via F atoms form two identical sets of infinite zig-zag
Mn–F–Mn chains, running along the [011] and [01ꢀ1] directions,
respectively. The adjacent parallel chains within each set are linked
by S1O4 tetrahedra to form a pair of two-dimensional sheets with
3- and 6-membered rings along the a axis. The sheets are then
stacked alternatively along the c axis and further linked by S2O4
tetradedra to form a three-dimensional framework of 1 (Fig. 5).
Fig. 3. ORTEP drawing of the asymmetric unit of 1 with ellipsoids drawn at the 50%
probability.
of Fe(III) to Fe(II). The use of Fe(II) chloride also resulted in the for-
mation of the title compound NH4FeSO4F. The ion exchange of NHþ
4
have been carried out by mixing and boiling the title compound
with lithium salts (LiI, LiBr, LiCl) in the solvent of anhydrous
C2H5OH or CH3CN for several hours. However, the results showed
to be unsuccessful that almost no Li+ ions can penetrate into the
structures.
The PXRD patterns for all the products are identical. As exempli-
fied in Fig. 1 (see Fig. S2 for the PXRD patterns of 4 in Supplemen-
tary information), the PXRD peaks of 1 are consistent with those
calculated on the basis of the single-crystal structures, indicating
the pure phase of the as-synthesized samples. Slight differences
in reflection intensities between the calculated and experimental
patterns may be attributed to the variation in crystal orientation
Table 2
Average bond lengths (Å) of M–O and M–F, and bond valences (BV) for M2+ ions in 1–4.
1
2
3
4
Mn1–O
Mn1–F
2.1909
2.0833
Fe1–O
Fe1–F
2.1535
2.0444
Co1–O
Co1–F
2.1309
2.0043
Ni1–O
Ni1–F
2.1033
1.9673
BVMn1 = 2.06
BVFe1 = 1.98
BVCo1 = 1.98
BVNi1 = 1.98
Mn2–O
Mn2–F
2.1764
2.0833
Fe2–O
Fe2–F
2.1424
1.9974
Co2–O
Co2–F
2.1124
2.0013
Ni2–O
Ni2–F
2.0719
1.9714
BVMn2 = 2.12
BVFe2 = 2.12
BVCo2 = 2.05
BVNi2 = 2.08

58
G.-w. Ge et al. / Polyhedron 152 (2018) 55–60
Fig. 4. Polyhedral view of the zig-zag chain made by alternation of cis- and trans-
MnO4F2 octahedra in 1 along the [011] direction.
The open channels of six-membered rings constructed from four
MnO4F2 octahedra and two SO4 tetrahedra along the a and c axis
are formed, where the ammonium cations locate (Fig. 6). The
NHþ4 cations, formed by the decomposition of DMA molecules dur-
ing the synthesis under high temperature and high pressure, play
important roles not only to balance the anionic charges of the inor-
ganic skeleton, but also to stabilize the framework by forming
hydrogen bonds with the framework O atoms. This may be the rea-
son why the ammonium cation can’t be replaced by the Li+ ion in
the ion-exchange experiments.
In order to further understand the structure of 1, the framework
can be simplified into a topological net by considering the MnO4F2
octahedra and SO4 tetrahedra as a 6- and 4-connected node,
respectively. Therefore, 1 can be reduced into a (4,4,6,6)-connected
net (Fig. 5). The point (Schlafli) symbol for the net is (32ꢁ62ꢁ72)
(32ꢁ63ꢁ7)(34ꢁ42ꢁ63ꢁ76)(34ꢁ42ꢁ64ꢁ74ꢁ8) as calculated by using TOPOS
software [15]. This net is the same as that of known nonlinear opti-
cal material KTiOPO4. As one of the most important structure types
in minerals, a number of metal phosphates [9] and arsenates [10]
Fig. 6. Polyhedral presentation of the 3D framework of 1 along the a axis, showing
the ammonium cations located in the channels.
with KTP-type structure have been prepared so far. However, the
metal sulfates with KTP-type structure have not been reported in
the literature. Compounds 1–4 are new members to this class of
materials.
Fig. 5. Polyhedral and simplified presentation of 1, (a) the 3D framework constructed from the 2D sheets connecting by S2O4 tetrahedra, and (b) the different orientation 1D
zig–zag chain was connected by S1O4 to form the 2D layer along the bc-plane. The teal and yellow balls represent the MnO4F2 octahedra and SO4 tetrahedra, respectively.

G.-w. Ge et al. / Polyhedron 152 (2018) 55–60
59
3.3. FT-IR spectrum and TG analyses
23.8% from 330 to 480 °C for 1 (calculated: 19.7%), 20.0% from
330 to 435 °C for 2 (calculated: 19.6%), 19.5% from 335 to 430 °C
for 3 (calculated: 19.3%) and 20.7% from 405 to 515 °C for 4 (calcu-
lated: 19.3%) can be attributed to the loss of NH4F. The weight
losses above 550 °C in all the four compounds could be attributed
to the loss of SO3 as results of thermal decomposition. It is noted
that although compounds 1–4 are isomorphous, they exhibited
slightly different thermal decomposition behaviors. For example,
compound 2 turned to be FeSO4 after the loss of NH4F, which start
to decompose almost immediately from ca. 450 °C to loss SO2 or
SO3 [16], unlike the others with a relatively long thermally stable
region. Since compound 4 possess the highest thermal stability,
which was chose as an example to examine the thermal stability
by PXRD studies. The as-synthesized samples were calcined in
atmosphere at different temperatures in the range of 200–800 °C.
As shown in Fig. S2, the framework of 4 was sustainably stable
up to ca. 400 °C, consistent with TG results. Upon losing NH4F
above 400 °C, 4 was converted to an orthorhombic phase NiSO4
(JCPDS no. 13-0435). As the temperature increased to more than
650 °C, it began to transform into the cubic oxide phase NiO
(JCPDS no. 75-197). The residue after calcination at 800 °C under
atmosphere for the other three compounds turned to be metal
The FT-IR spectra of four title compounds are almost identical.
As shown in Fig. S1 (see Supplementary information), FT-IR spec-
trum of 1 exhibits the bands corresponding to the vibrations of
ammonium cation and the SO24ꢀ sulfate. The strong and broad band
at 3235 cmꢀ1 with shoulders at ca. 3000 cmꢀ1 can be attributed to
the stretching modes of the NHþ4 group. The band near 1419 cmꢀ1
can be assigned to the bending vibration of the NHþ4 cation.
The stretching
(m3) and bending (m4) vibrational bands of
the SO24ꢀ group appears as doublets at 1153–1105 cmꢀ1 and
617–603 cmꢀ1, respectively. The presence of two sets of bands is
related to the different local symmetry of the sulfate groups, which
is consistent with the crystal structure analysis results.
The TG analyses of 1–4 are shown in Fig. 7. All the compounds
are thermally stable up to at least 330 °C. The weight losses of
oxides hausmannite Mn3O4 (JCPDS no. 89-4837) for 1, a-hematite
Fe2O3 (JCPDS no. 87-1165) for 2, and cobalt oxide Co3O4 (JCPDS
no. 78-1969) for 3, respectively.
3.4. Magnetic studies of 1–4
The plots of
vMT versus T and 1/vM versus T for 1–4 are shown
in Fig. 8(a–d). All compounds show similar magnetic behaviors.
The
v
MT value at room temperature is 3.68 cm3 K molꢀ1 (for 1),
which is slightly lower than spin-only value of 4.375 cm3 K molꢀ1
of one magnetically isolated Mn2+ ions (for S = 5/2 and g = 2), while
3.21 (for 2), 5.43 (for 3) and 2.47 (for 4) cm3 K molꢀ1, respectively,
which is much higher than the spin-only value of 3.0 cm3 K molꢀ1
for one magnetically isolated Fe2+ ions (for S = 2 and g = 2),
Fig. 7. TG curves of 1–4.
Fig. 8. Temperature dependence of vM T and 1/vM for 1–4 (a–d) at 2000 Oe (open circles and squares, and red line represent experimental data and fits, respectively).

60
G.-w. Ge et al. / Polyhedron 152 (2018) 55–60
3.75 cm3 K molꢀ1 for one Co2+ ions (for S = 3/2 and g = 2), and
2 cm3 K molꢀ1 for one Ni2+ ions (for S = 1 and g = 2), indicating
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4. Conclusions
Four new thermally stable transition metal fluorosulfates
NH4MSO4F (M = Mn, 1; Fe, 2; Co, 3; Ni, 4) were solvothermally
synthesized in DMA with the presence of HF. The four compounds
are isomorphous and adopt a KTP-type structure. Each compound
is constructed from MO4F2 octahedra and SO4 tetrahedra to form
two kinds of intersecting 6-membered ring channels along the a
and c axes, in which the ammonium cations from the decomposi-
tion of the DMA molecules locate to balance the framework
charges. The syntheses of 1–4 further show the rich structural
chemistry of metal sulfates. More new metal sulfates with
interesting structure and properties are expected by using similar
synthetic methods.
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We gratefully appreciate financial support by Program for Inno-
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Henan Province (14IRTSTHN009), Henan Province Higher Educa-
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Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.poly.2018.06.017.