Mater. Res. Express 4 (2017) 105036 https://doi.org/10.

1088/2053-1591/aa9194

PAPER

Growth and structural analysis of ammonium nickel cobalt sulfate

hexahydrate crystals
RECEIVED
23 August 2017
RE VISED
3 October 2017
ACCEP TED FOR PUBLICATION
Michelle de Oliveira1, Santunu Ghosh2 , Tiago S Pacheco1,2, Genivaldo J Perpétuo1 and Carlos J Franco1
1
6 October 2017 Departamento de física, Universidade Federal de Ouro Preto, Ouro Preto 35400-000, Brasil
2
PUBLISHED
Departamento de física, Universidade Federal de Juiz de fora, Juiz de Fora 36036-330, Brasil
24 October 2017 E-mail: [email protected] (S Ghosh)

Keywords: x-ray diffraction, growth from solutions, crystal structure, Tutton’s salt

Abstract
We have obtained a set of crystals of the empirical formula (NH4)2NixCo(1−x)(SO4)2 · 6H2O with
the different concentrations of Ni and Co, by employing the growth from the solution technique.
We have chosen the monocrystal (NH4)2Ni0.3Co0.7(SO4)2 · 6H2O for the structural analysis. The
structure was resolved by x-ray diffraction method and refined by the full-matrix least-squares
method with the help of SHELXS software. This crystal belongs to a monoclinic space group P21/c
with crystal parameters, a  =  6.2455 (2) Å, b  =  12.5065 (3) Å, c  =  9.2303 (2) Å, α  =  γ  =  90°,
β  =  106.995 (3)°, V  =  689.49 (3) Å3, Z  =  2. We have shown the configuration of the unit cell of the
above monocrystal, along with that we have also reported the length, angles between the bonds and
the geometry of the hydrogen bonds of the monocrystal.

1. Introduction

From few decades, the study on the growth and characterization of Tutton’s salts are becoming very popular due
to its important applications [1] in the area of UV light filters, UV made sensors, spaceships and modern missile
approach warning systems. Tutton salts are the hydrated complexes with the molecular formula M2M′(XO4)2 ·
6H2O where M is a univalent cation, which may be the alkali metals K+, NH+ + +
4 , Rb or Cs . The M’ symbol is a
2+ 2+ 2+ 2+ 2+
bivalent cation: Ni , Co , Mg , Zn , Fe , one of the first transition metals in the periodic table and X being
S or Se. The similarity between the bivalent ions of the first transition series [2–4] encouraged several researchers
to grow crystals of this type. The Tutton’s salts crystallize in a monoclinic space group P21/c [Z  =  2] [5, 6], with
two chemical formulas per unit cell. The XO2− 2+
4 group is tetrahedral while [M′(H2O)6] has octahedral structure
formed by a bivalent ion at its center and six molecules of water at its apex. The octahedral groups are distorted
by the Jahn–Teller effect [7–9]. Studies show that, most of these salts have the same crystallographic arrangement
and in certain crystallographic families, the mixed systems usually have properties that are not present in the pure
systems.
The most commonly used method for growing crystals of this family is the preparation of an aqueous solu-
tion containing the appropriate compounds taken in a molar ratio which is left to evaporate slowly to obtain good
quality samples. Nickel sulfate hexahydrate (NSH) crystals are good to use in UV light filters and UV made sen-
sors, but the main drawback is, these crystals lacks the temperature stability for the use in high temperature appli-
cations. There are some recent studies on the growth, structural analysis, characterization, optical transmittance
spectra of very good NSH crystals for UV light filters, for example, rubidium nickel sulfate hexahydrate (RNSH)
[10, 11], guanidine carbonate doped nickel sulfate hexahydrate [12], α-nickel sulfate hexahydrate (α-NSH)
[13–15], cesium nickel sulfate hexahydrate [16], potassium manganese nickel sulfate hexahydrate (KMNSH)
[17, 18], iron nickel sulfate twelvehydrate (FNSH) [19], potassium nickel sulfate hexahydrate (KNSH) [20],
potassium cobalt nickel sulfate hexahydrate (KCNSH) [21–24].
Ammonium nickel sulfate hexahydrate crystals (ANSH) [25–27] shows same type of optical transmission
spectra as that of NSHs, but with better thermal stability and higher dehydration temperature. To obtain more
sophisticated UV light filters, the addition of transition metal (such as Co) in ANSH crystals improve their opti-
cal performance, as well as it also helps us to acquire more pure UV light signal from white spectra. Ammo-
nium nickel cobalt sulfate hexahydrate (ACNSH) crystals shows higher thermal stability and superior UV light

© 2017 IOP Publishing Ltd

Mater. Res. Express 4 (2017) 105036 M de Oliveira et al

Table 1. Mass of the salts (NH4)2SO4, NiSO4 · 6H2O and CoSO4 · 7H2O used for the preparations of the solutions.

(NH4)2SO4 (g) x NiSO4 · 6H2O (g) (1  −  x) CoSO4 · 7H2O (g)

5.000 1.00 9.940 0.00 0.000

5.000 0.90 8.952 0.10 1.064
5.000 0.80 7.957 0.20 2.127
5.000 0.70 6.962 0.30 3.215
5.000 0.60 5.967 0.40 4.255
5.000 0.50 4.972 0.50 5.318
5.000 0.40 3.978 0.60 6.381
5.000 0.35 3.481 0.65 6.913
5.000 0.30 2.983 0.70 7.445
5.000 0.25 2.486 0.75 7.977
5.000 0.20 1.989 0.80 8.509
5.000 0.10 0.994 0.90 9.572
5.000 0.00 0.000 1.00 10.630

transmission spectra than ANSH crystals. Su et al [28] reported the growth, structural analysis by x-ray diffrac-
tion and optical transmission spectra of a ACNSH single crystal. The dehydration temperature of their crystal
was 97 °C and they compared UV transmittance of ACNSH crystal with ANSH crystal. In this paper, we have
obtained a series of ACNSH crystal with the different concentrations of cobalt and nickel by the growth from the
solution method at 40 °C. There was a recrystallization peak observed that appears only for the 70% cobalt con-
centration. As a result, we have analyzed the structure of this interesting ACNSH monocrystal with 30% Ni and
70% Co by using x-ray diffraction method.

2. Materials and method

For the preparation of the solutions, we used the reagents ammonium sulfate (NH4)2SO4, nickel sulfate NiSO4
· 6H2O and the cobalt sulfate CoSO4 · 7H2O from the stoichiometric ratio given by the compositional form
(NH4)2NixCo(1−x)(SO4)2 · 6H2O
(NH4 )2 SO4 + NiSO4 · 6H2 O + CoSO4 · 7H2 O  (NH4 )2 Nix Co(1−x) (SO4 )2 · 6H2 O + H2 O.
The apparatus used for the preparation of the solutions were analytical balance, water purification system,
greenhouse, glassware and magnetic stirrer.
The amount of ammonium sulfate (NH4)2SO4 was set at 5 g. By stoichiometric calculations, the amounts of
the other reactants were determined respecting the ratio NixCo(1−x), i.e. for each fraction x of nickel was added
the fraction of cobalt was (1  −  x). The table 1 shows the quantities of reagents used.
In a beaker, calculated masses of reagents were placed by adding approximately 100 ml of deionized water,
with resistivity of 18.2 MΩ. The beaker was then brought to a magnetic stirrer with heating so that the solution
was completely diluted. The dilution in the magnetic stirrer began with a temperature of 60 °C for all solutions,
but in some case, it was necessary to increase this temperature, but it did not exceed 80 °C. After dilution, the solu-
tion was passed through the filtration process using a funnel and paper filters. Then the solutions was placed in
a new beaker that was covered with plastic film where some holes were made so that the slow evaporation of the
solution could occur. The solutions were then brought to a greenhouse where the temperature was maintained
at 40 °C.
To analyze the crystalline structure of the samples, x-ray diffraction measurements were performed for
monocrystals using the GEMINI A Oxford diffractometer equipped with a CCD detector. The radiation used
was MoKα with wavelength, λ  =  0.710 73 Å, at room temperature. Samples selected for these measurements
needed to be ~0.1 mm in size, so that they can be attached to the goniometer of the equipment and completely
bathed by the x-ray beam. For this purpose, some crystals were diluted in water to reduce size or cut with a stylet,
satisfying the requirement of being free of imperfections such as cracking.

3. Results and discussion

Good monocrystals with natural and well-developed faces were obtained throughout the composition range.
Dimensions of our sample crystals was almost in the order of 0.5  ×  0.7  ×  0.3 cm3, whereas, dimension of the
crystal with 10% cobalt was 1  ×  0.5  ×  0.8 cm3, higher than that of other crystals. The concentration varied
with steps of 0.05 between 0.60 and 0.80, region of interest, because there was a recrystallization peak observed
that appears only for the 70% cobalt concentration near to 280 °C in the differential scanning calorimetry

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Mater. Res. Express 4 (2017) 105036 M de Oliveira et al

Figure 1. Crystals with (A) 0% Co (B) 10% Co (C) 20% Co (D) 30% Co (E) 40% Co (F) 50% Co (G) 60% Co (H) 65% Co (I) 70%
Co (J) 75% Co (K) 80% Co (L) 90% Co (M) 100%.

measurements, as shown in the figure 3. The crystal growth period varied between days and weeks, and for some
solutions the first crystalline nuclei appeared in few minutes after being placed in the greenhouse. This fact
indicates that it reached the supersaturation curve described in the Ostwald–Miers diagram [29] rapidly.
The time taken for each solution to reach supersaturation can be considered an unresolved problem and still
difficult to control. The amount of crystals formed within the beaker varied from solution to solution. The color-
ation of the crystals changes through the green to those with low concentration of cobalt to a reddish coloration
to wine red to those with high concentration of cobalt. In figure 1 we have shown the photographs of some of the
crystals obtained. For all the solutions, there were withdrawals containing a single crystal and, for later withdraw-
als of the same solution, there were also withdrawals with a large number of small crystals of different sizes and
shapes (shown in the figure 2), but with well-defined faces and characteristic morphology of the Tutton salts.
After obtaining the crystals, we have done structural analysis of some of the crystals. At first, we have per-
formed the x-ray diffraction measurements of the monocrystals. The data collection for the determination of
the unit cell of the samples and the data reduction was performed through the CrysAlisPro package [30]. The
structures were solved from the positions of the heavy atoms (nickel, cobalt, sulfur, potassium and oxygen)
of pure compounds, as mentioned in the literature [31, 32]. The hydrogen atoms were located by the Fourier

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Mater. Res. Express 4 (2017) 105036 M de Oliveira et al

Figure 2. Smaller crystals with (i) 10% Co (ii) 75% Co (iii) 90% Co.

Figure 3. Results of differential scanning calorimetry (DSC) measurements.

synthesis procedure implemented in the SHELXS software [33]. The refinement of the structures was performed
by using the least squares method implemented in the SHELXL program. These software are composed of the
WinGX package [34], which also includes the ORTEP3 program [35], used for graphical representation of the
asymmetric unit and other illustrations of the crystallographic structures of the samples.
For the structural analysis of monocrystals, the following strategy was adopted. Initially a pure crystalline
sample was chosen, that is, it contained only one of the metals (Ni). It serves as a learning technique to see that
whether it can corroborate or not to the formation of the method of obtaining the samples of Tutton salt. Next, we
proceed to the measurement of unpublished compounds of samples containing different percentages of Ni (30%)
and Co (70%). The reason behind the analysis of the structure of the crystal (NH4 )2 Ni0.30 Co0.70 (SO4 )2 · (6H2 O),
because in the crystal growth process, this specific crystal shows recyclization peak near about 280 °C, as shown in
the figure 3 in the DSC measurement.
The monocrystal of the chemical formula (NH4 )2 Ni0.30 Co0.70 (SO4 )2 · (6H2 O) with weight 395.12 was cho-
sen for structural analysis and mounted on the goniometer of diffractometer. Table 2 lists the parameters for
the samples and the measurement conditions. The structure was resolved by direct method and refined by the
full-matrix least-squares method with SHELXS software [33]. (NH4 )2 Ni0.30 Co0.70 (SO4 )2 · (6H2 O) belongs to
a monoclinic space group P21/c with crystal parameters, a  =  6.2455 (2) Å, b  =  12.5065 (3) Å, c  =  9.2303 (2) Å,
α  =  γ  =  90°, β  =  106.995 (3)°, V  =  689.49 (3) Å3, Z  =  2, D  =  1.903 mg m−3. In this crystal, Ni2+ or Co2+ con-
nected with six H2O molecules forming distorted octahedral Ni (H2 O)2+ 2+ 2−
6 and Co (H2 O)6 units. The SO4 ions
2+ 2+
have tetrahedral geometry connected with Ni (H2 O)6 or Co (H2 O)6 through O–H…O bonds, and NH+ 4 ions
2−
are bonded with O of SO4 with N–H…O hydrogen bonds. The whole structure has alternative octahedral and
tetrahedral layered packing arrangement.
The positions of the hydrogen atoms were refined, and their thermal vibration was treated isotropically and
kept fixed at 1.2 times the value corresponding to the oxygen atom to which it is attached. This makes a total of

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Table 2. Crystallographic data and the refinement of the structure.

Present data Present data Su et al [28]

Empirical formula (NH4)2Ni(SO4)2 · 6H2O (NH4)2Ni0.3Co0.7(SO4)2 · 6H2O (NH4)2Co0.17Ni0.83(SO4)2 · 6H2O

Molecular weight (g mol−1) 395.01 395.12 395.05
Crystaline system, space group Monoclinic, P21/c Monoclinic, P21/c Monoclinic, P21/c
a (Å) 6.244 80 (1) 6.2455 (2) 6.2432 (3)
b (Å) 12.4665 (2) 12.5065 (3) 12.4728 (5)
c (Å) 9.1891 (1) 9.2303 (2) 9.1967 (4)
β (°) 106.920 (2) 106.995 (3) 106.9880 (10)
V (Å3) 684.41 (2) 689.49 (3) 684.90 (5)
Z 2 2 2
D (Mg m−3) 1.917 1.903 1.916
Absorption coefficient, μ (mm−1) 1.794 1.700

Mesaurement parameters
Type of radiation Mo Kα Mo Kα
Wavelength. λ (Å) 0.710 73 0.710 73
Temperature (K) 293 K 293 K
Interval of measurements, θ (°) 2.835–37.885 2.824–37.857
Measured reflections 107 853 67 955
Independent reflections 3630 3653
Observed reflections 104 223 64 302
Parameters of refinement

Refinement F2 F2
Rint 0.0703 0.0703
R[F2  >  2σ(F2)] 0.0310 0.0322 0.0295
wR2 (reflections) 0.0866 0.0878 0.0733
Goodness-of-fit (S) 1.151 1.135
Δρmax, Δρmin 0.607, −0.482 0.778, −0.519
    
2 2
wR = w(F02 − Fc2 ) / wF04 ; w = 1/ σ 2 (F02 ) + (0.0542 ∗ P) + 0.00 ∗ P , where P = (F02 + 2Fc ) /3

Figure 4. Representation of the asymmetric unit (M  =  Ni or Co) for the crystal (NH4)2Ni0.3Co0.7(SO4)2 · 6H2O.

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Mater. Res. Express 4 (2017) 105036 M de Oliveira et al

Table 3. Length and angles between the bonds of the sample (NH4)2Ni0.3Co0.7(SO4)2 · 6H2O.

Bond Bond length (Å) Angle Bond angle (°)

M–O7 2.0544 (10) O6–M–O7 89.52 (5)

M–O6 2.0886 (10) O5–M–O7 90.85 (5)
M–O5 2.0901 (11) O5–M–O6 88.83 (4)
H1–N–H2 119 (2)
N–H1 0.73 (3) H1–N–H3 99 (2)
N–H2 0.84 (2) H1–N–H4 106 (2)
N–H3 0.94 (2) H2–N–H3 111 (2)
N–H4 0.84 (2) H2–N–H4 113 (2)
H3–N–H4 108 (2)

O1–S–O3 110.93 (8)

S–O1 1.4793 (11) O3–S–O2 108.93 (7)
S–O2 1.4775 (10) O3–S–O4 109.57 (8)
S–O3 1.4611 (12) O1–S–O2 109.72 (6)
S–O4 1.4824 (12) O1–S–O4 109.62 (7)
O2–S–O4 108.02 (7)

M–O5–H5A 111.3 (15)

O5–H5A 0.82 (2) M–O5–H5B 114.4 (16)
O5–H5B 0.76 (2) H5A–O5–H5B 111 (2)
M–O6–H6A 110.9 (17)
O6–H6A 0.76 (2) M–O6–H6B 115.4 (16)
O6–H6B 0.76 (2) H6B–O6–H6A 115.4 (16)
M–O7–H7A 118.8 (15)
O7–H7A 0.79 (2) M–O7–H7B 121.8 (15)
O7– H7B 0.78 (2) H6B–O7–H7A 102 (2)

Figure 5. Unit cell with the hydrogen bonds shown.

125 parameters including scale factor and percentage of metals. After convergence, the R and wR indexes were
0.0322 and 0.0878, respectively. The maxima and minima of the electron density residue, ∆ρmax and ∆ρmin, indi-
cate that all the atoms have been located. The asymmetric unit can be seen in figure 4.
The asymmetric unit of the crystal (NH4)2Ni0.3Co0.7(SO4)2 · 6H2O consists of: an ammonium group, a
sulfate tetrahedron and three water molecules in generic positions; the Ni/Co metals are in special position,
namely in the inversion center. It is observed that, only three water molecules are crystallographically independ-
ent, and through inversion symmetry a coordinating pseudo-octahedron of the metal is formed. This pseudo-
octahedron is slightly spatially distorted, however, of the three axes O–M–Oi, the distance M–O7 is markedly

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Mater. Res. Express 4 (2017) 105036 M de Oliveira et al

Table 4. Geometry of hydrogen bonds.

D–H…A (D–H) (H…A) (D…A) DHA

N–H1…O1i 0.73 (3) 2.21 (3) 2.918 (2) 163 (3)

N–H2…O4ii 0.84 (2) 2.17 (2) 2.959 (2) 156 (2)
N–H3…O2iii 0.94 (2) 1.92 (2) 2.851 (2) 173 (2)
N–H4…O3 0.84 (2) 2.46 (2) 3.151 (2) 140 (2)
N–H4…O4 0.84 (2) 2.19 (2) 2.983 (2) 158 (2)
O5–H5A…O2 ii 0.82 (2) 1.98 (3) 2.790 (2) 169 (2)
O5–H5B…O1iv 0.76 (2) 2.08 (2) 2.831 (2) 169 (2)
O6–H6A…O1 i 0.76 (2) 2.01 (2) 2.763 (2) 169 (2)
O6–H6B…O3v 0.76 (2) 1.96 (2) 2.709 (2) 174 (2)
O7–H7A…O4vi 0.79 (2) 1.93 (2) 2.710 (2) 174 (2)
O7–HBA…O2vii 0.78 (2) 2.01 (2) 2.772 (2) 166 (2)

smaller than M–O6 and M–O5. Table 3 shows the lengths and angles between the bonds. The sulfate ion consists
of four chemically identical oxygen atoms, forming a slightly distorted tetrahedron. The anisotropic displace-
ments of the oxygen atoms indicate a greater deformation of the electron cloud perpendicular to the S–O direc-
tion.
The structure of this salt consists of [M(H2 O)6 ]2+ (M  =  Ni or Co) and NH+ −
4 groups around SO4 , as observed
in figure 5. This interaction between oppositely charged ions is responsible for the packing in the space group
P21/c and the stability of the crystal, because it favors the appearance of hydrogen bonds. Figure 5 shows the unit
cell of the crystal with 70% cobalt
The oxygen atoms of the sulfate are receptors of six hydrogen bonds of the type O–H ··· O, where the water
molecules participate as donors of H. In addition, the oxygen atoms belonging to the sulfate are also receptors of
eight hydrogen bonds of the type N–H ··· O where the molecules of NH4 act as donors of H, all these bonds are
represented in table 4.

4. Conclusions

Good quality single crystals of ammonium nickel cobalt sulfate hexahydrate have been grown by slow evaporation
solution growth technique. In our samples, the ratios of the Ni and Co varies from 0 to 100%. In some cases, we
have varied the concentration of Co by steps of 0.05 to observe the recrystallization peak better, that appears
only for the 70% cobalt concentration at ~280 °C. The structural analysis of the monocrystal (NH4)2Ni0.3Co0.7
(SO4)2 · 6H2O have been performed by x-ray diffraction method refined by the full-matrix least-squares method
with the help of SHELXS software. X-ray diffraction measurement reveals that the crystal belongs to monoclinic
system with centrosymmetric space group P21/c and the cell parameters are a  =  6.2455 (2) Å, b  =  12.5065 (3)
Å, c  =  9.2303 (2) Å, α  =  γ  =  90°, β  =  106.995 (3)°, V  =  689.49 (3) Å3, Z  =  2. Our crystal parameters have been
compared with the parameters of ACNSH crystal reported by Su et al [28]. The asymmetric unit of the crystal
(NH4)2Ni0.3Co0.7(SO4)2 · 6H2O contains an ammonium group, a sulfate tetrahedron and three water molecules
in generic positions, whereas, Ni or Co metals are positioned at the inversion center. The whole structure is
repeated through alternative octahedral and tetrahedral layers. The values of the length and angle between the
bonds and the geometry of the hydrogen bonds for ammonium nickel cobalt sulfate hexahydrate monocrystal
have been reported for the first time in our work.

ORCID iDs

Santunu Ghosh https://orcid.org/0000-0002-2666-9461

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