Sulfur-rich nickel(II) complex: Synthesis, characterization, and X-ray crystal structure

Article abstract of DOI:10.1080/15533174.2016.1186034

A sulfur-rich nickel complex has been synthesized by the reaction between 2,4-bis(4-methoxyphenyl)- 1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson’s reagent) and Ni(NO₃)₂·6H₂O in 2-propanol. The complex has been characterized by elemental analysis, IR,¹H NMR,¹³C NMR, and³¹P NMR spectroscopies and molar conductivity. Also, the crystal structure of the complex has been investigated by X-ray diffraction, which illustrates a slightly distorted square planar environment around Ni(II) ion in solid. Furthermore, the crystal structure of the complex shows 3D network through intermolecular C-H…Ni, CH O, and C-H S hydrogen bonds and C–H π interaction.

Full text of DOI:10.1080/15533174.2016.1186034

Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry
ISSN: 1553-3174 (Print) 1553-3182 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt20
Sulfur-rich Nickel(II) Complex: Synthesis,
Characterization and X-ray Crystal Structure
Hadi Jaefari & Seyed Amir Zarei
To cite this article: Hadi Jaefari & Seyed Amir Zarei (2016): Sulfur-rich Nickel(II) Complex:
Synthesis, Characterization and X-ray Crystal Structure, Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry, DOI: 10.1080/15533174.2016.1186034
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Sulfur-rich Nickel(II) Complex: Synthesis, Characterization and X-ray Crystal Structure
*
*
Hadi Jaefari and Seyed Amir Zarei
Department of Chemistry, Faculty of Science, Sanandaj Branch, Islamic Azad University,
Sanandaj, Iran
*
Corresponding author. E-mail: hjs292@yahoo.com; Seyedamirzarei@yahoo.com
Abstract
The sulfur-rich nickel complex has been synthesized by the reaction between 2,4-bis(4-
methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson’s Reagent, LR) and
Ni(NO
3
)
2
·6H
2
O in 2-propanol. The complex has been characterized by elemental analysis, IR,
1
13
31
H NMR, C NMR, and P NMR spectroscopies, and molar conductivity. Also the crystal
structure of the complex has been investigated by X-ray diffraction which illustrates slightly
distorted square planar environment around Ni(II) ion in solid. Furthermore, the crystal structure
of the complex shows 3D network through intermolecular C-H···Ni, C-H···O and C-H···S
hydrogen bonds and C–H···π interaction.
Key words
Sulfur-rich Complex, Nickel(II), Crystal Structure, NMR, hydrogen bond
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Introduction
Transition metal complexes of thio ligands (as thiolate and thioether) have been extensively
investigated for their potential applications in various fields such as: catalysis [1-5], magnetic
materials [6-8] and bioinorganic chemistry [9, 10]. One of the exciting goals in nickel complexes
incorporating thio ligands to a large extent in modern coordination chemistry arises from the
nickel-sulfur moieties that construct the active sites of the enzymes such as hydrogenases [11,
1
2]. Therefore, the investigations for determining the function of the enzymes bearing nickel
ions by simulation of adequate models have resulted in a considerable number of new ligands
and complexes [13, 14]. The relationship between structure and function of the synthesized
complexes has been corroborated and is driving force for preparing new complexes to obtaining
the complexes with high performance in the different fields [14, 15]. 2,4-bis(4-methoxyphenyl)-
1
,3,2,4-dithiadiphosphetane-2,4-disulfide has been found as a convenient candidate for offering
the thiolate ligand that can easily be cleaved in alcohol solvents. Hence, the coordinating ability
of LR derivatives in methanol and ethanol in the presence of nickel(II) and cobalt(II) salts has
been reported by Zhang et. al. [16].We report here the synthesis and spectral properties of
synthesized sulfur-rich nickel complex by using LR in 2-propanol. The crystal structure of this
complex is also reported that shows the intermolecular interaction effects on the stabilization of
the crystal.
Experimental
Materials and Physical measurements
All reagents were purchased from Merck or Fluka and were used without further purification.
CHNS analysis was carried out using a EuroVector, CHNS-O EA3000 elemental analyzer.
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Infrared spectrum was obtained on a Shimadzu-60 instrument as KBr pellets. NMR spectra were
recorded on a Bruker Avance 500 spectrometer in CDCl
3
using Me
85% as the internal reference for P NMR. H:
00 MHz, C{ H}: 125 MHz, P{ H}: 202 MHz. Conductance measurement was performed
4
Si as the internal reference
1
13
31
1
for H and C NMR and in D
2
O using H
3
PO
4
1
3
1
31
1
5
using a Metrohm 712 conductometer.
Synthesis of 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (LR)
LR was synthesized in a way similar to the previously reported procedure [17] using anisole and
diphosphorus pentasulfide. Yield: 54.1%. M.p. 227-230 °C. Elemental analysis found: C, 41.49;
H, 3.56; S, 31.67%, C14
H
14
O
2
S
4
P
2
calcd: C, 41.57; H, 3.49; S, 31.71%. IR (KBr): 3025w,
2
952w, 1597s, 1498s, 1297m, 1261s, 1180m, 767s (υP=S), 662m (υasym P-S), 558m (υsym P-S)
-
1 1
cm . H NMR (CD
Synthesis of sulfur-rich nickel complex
LR (0.8080 g, 2 mmol) was added to 50 mL of 2-propanol and refluxed for 2 h. The mixture was
cooled to room temperature. Ni(NO ·6H O (0.5840 g, 2 mmol) in 2-propanol (20 mL) was
3
CN): δ 7.10-8.20 (m, 8H, aromatics), 3.57 (s, 6H, CH
3
-methoxy).
3
)
2
2
slowly added to this solution. The resulting mixture refluxed for 2 h, and then the volume of the
resulting solution was reduced using a rotary evaporator. After two days, suitable blue crystals
for X-ray analysis were obtained and dried in vacuum desiccators over P
77.5%). M.p. > 210 °C (dec). Elemental analysis found: C, 41.27; H, 4.81; S, 22.11%,
calcd: C, 41.32; H, 4.86; S, 22.02%. IR (KBr): 3052w, 2927w, 1590s, 1490s,
4
O10. Yield: 0.901 g
(
C
20
H28NiO
4
S
P
4 2
-1 1
1
290s, 1270s, 1120s, 973m (P-O-C), 653m (υasym P-S), 562m (υsym P-S) cm . H NMR (CDCl
3
):
δ 7.02-8.02 (m, 8H, aromatics), 5.24 (h, 2H, CH-isopropoxy), 3.86 (s, 6H, CH
3
-methoxy), 1.43
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1
3
1
(
d, 12H, CH
3
-isopropoxy). C{ H} NMR (CDCl ): δ 162.02, 131.61, 128.14, 113.94, 72.14,
3
31
1
2
-1
-1
5
5.50, 24.31. P{ H} NMR (D
2
O): δ 105.01. Λ = 15 cm Ω mol in DMF.
m
X-ray crystallography
Single crystals of synthesized sulfur-rich nickel complex were obtained from 2-propanol solution
of the complex by slow evaporation. Single crystal X-ray diffraction data for the complex were
collected with use of the program SMART [18] on a Bruker Smart 1000 CCD diffractometer.
Monochromatized Mo Kα radiation was employed. Cell refinement and data reduction were
carried out with the use of the program SAINT-PLUS [19]. An absorption correction was applied
using SADABS [20]. The structures were solved using direct methods and refined by full-matrix
least squares procedures using SHELXTL [21]. Crystal data and experimental details of the
complex are listed in Table 1.
Results and discussion
Synthesis and characterization
The sulfur-rich nickel complex prepared in a two-step one-pot reaction that summarized in
1
13
31
Scheme 1. Elemental analysis, IR, H NMR, C NMR, and P NMR spectroscopies, and
conductance measurement have been used for complex characterization. The elemental analysis
data are agreement with the proposed molecular formula (i.e. C20
H28NiO
4
S
4
P
2
) that showed a
1
:1:2 ratios of nickel, LR and 2-propanol. The measured molar conductance value of the nickel
-3
complex for ca. 10 M solution in DMF at 25 °C is very low and indicates the non-electrolyte
behavior for this complex [22]. Thus the LR must act as two negatively charged moieties in the
complexation process. This hypothesis is supported by the presence of P-O-C stretch [23] in the
IR spectrum of the nickel complex, reflecting the cleavage of LR by alcohol attack to phosphorus
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atoms in the presence of nickel ion that leads to the formation of two negatively charged moieties
1
13
31
and their complexation with nickel. The H NMR, C NMR and P NMR spectra of the
complex can signify that the complex structure contains the symmetry element of inversion
center. So, it is expected that nickel ion has been surrounded by S-donors in a square planar
molecular geometry.
X-ray structure
X-ray crystallographic investigation shows that the unit cell of the synthesized sulfur-rich nickel
complex consists of one molecule. Figure 1 shows the atomic labeling Scheme of the complex.
The arrangement around the nickel ion in the complex is slightly distorted square planar, with
four S-donors from two formed negatively moieties of LR. The selected bond lengths and angles
of the complex are listed in Table 2. In the complex structure the Ni–S distances and
semiperpendicular S-Ni-S angles are in the range 2.225(6) to 2.231(6) Å and 88.63 to 91.37°
respectively, which are accordance with the values of corresponding bonds at the similar
reported complexes [16].
In the crystal structure of the synthesized sulfur-rich nickel complex (Figure 2), along a axis an
i
intermolecular C2-H2C···Ni1 hydrogen bond (2.786 Å, 173.27°, symmetry code: (i) –1+x, y, z)
exists between the CH
3
-isopropoxy group of one molecule and the nickel atom of adjacent
ii
molecule. Also, along a axis the doubly C10–H10B···π interactions (2.919 Å, 144.76°,
symmetry code: (ii) -x, -1-y, 1-z) between benzene rings Cg(3) [C6, C7, C8, C9, C4 and C5]
from MeOPh moiety of one molecule and aliphatic hydrogen of MeOPh moiety from contiguous
molecule stabilize further the crystal (Figure 2). Along bc plane of the crystal an intermolecular
iii
C10-H10D···O1 hydrogen bond (2.634 Å, 134.64°, symmetry code: (iii) -x, -1-y, 1-z) creates
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between the CH -methoxy group of one molecule and the oxygen atom of propoxy of the
3
neighboring molecule (Figure 2). Cooperative intermolecular C-H···Ni and C-H···O hydrogen
bonds and C–H···π interactions result in 2D sheet structure (Figure 2).
Furthermore, in the crystal structure of the synthesized sulfur-rich nickel complex (Figure 3)
iv
along bc plane an intermolecular C10-H10A···S2 hydrogen bonds (2.956 Å, 140.55°, symmetry
code: (iv) -x, -y, 1-z) exist between the methoxy group of one molecule from a sheet structure
and the sulfur atom of adjacent molecule from a neighboring sheet structure that construct a 3D
network in this complex.
Conclusion
The NMR spectra of the synthesized sulfur-rich nickel(II) complex signify the symmetry element
of inversion center in the complex structure that reflects the square planar environment around
Ni(II) ion in solution. Also the crystal structure evolution of the complex by X-ray diffraction
method illustrates slightly distorted square planar environment around Ni(II) ion in solid.
Hydrogen bonding in the form of fourteen-membered {…HCCNi}2 synthons leads to the
formation of one-dimensional aggregation pattern. Furthermore, 3D network in the crystal
structure of the complex is stabilized by intermolecular C-H···Ni, C-H···O and C-H···S
hydrogen bonds and C–H···π interaction.
ACKNOWLEDGEMENT
We are grateful to Sanandaj Branch, Islamic Azad University Council for the financial support of
this research.
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Appendix A. Supplementary data
CCDC 955683, contain the supplementary crystallographic data for synthesized sulfur-rich
nickel
complex.
These
data
can
be
obtained
free
of
charge
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
1
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Table 1. Crystal data and structure refinement of the complex.
Parameter
Value
Crystal shape/color
Empirical formula
Formula weight
Temperature (K)
Crystal system
Plate/blue
C
20
H28NiO
4
P
S
2 4
581.31
120(2)
Triclinic
Pī
Space group
Unit cell dimensions (Å, °)
a = 7.8126(7)
b = 8.7183(8)
c = 10.8460(10)
α = 99.274(2)
β = 96.977(2)
γ = 112.451(2)
3
V (Å )
660.13(10)
Z
1
-3
ρ (calcd) (g cm )
1.462
-
1
μ (mm )
1.196
F (000)
302
Crystal size (mm)
θ range for data collection (°)
0.45 × 0.36 × 0.26
1.94-26.00
1
2
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Limiting indices
-9≤h≤9, -10≤k≤10, -13≤l≤13
0.732 and 0.601
5786l2584
Max. and min. transmission
Reflections collected/unique
R
int
0.0175
-
1
Absorption coefficient (mm )
1.196
a
R
R
1
1
/wR
/wR
2
2
[I > 2σ(I)]
0.0333/0.0824
0.0362/0.0844
2584/0/145
(all data)
Data/restraints/parameters
2
Goodness-of-fit on F
1.017
-3
Largest difference peak and hole (e Å )
0.706, -0.408
2
2


2
2


2
1/2
]]
a
R    F  F || /  Fo ;wR2 
w

| F  F |

/
w

Fo

1
o
c
o
c









1
3
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Table 2. Selected bond lengths (Å) and bond angles (°) for the synthesized sulfur-rich nickel
complex.
Bond lengths
Bond angles
Ni(1)-S(1)
Ni(1)-S(1)#1 2.225(6) S(2)-Ni-S(1)#1
Ni(1)-S(2)
2.225(6) S(1)-Ni-S(2)
88.63(2)
91.37(2)
2.231(6) S(1)#1-Ni-S(2)#2 88.63(2)
Ni(1)-S(2)#2 2.231(6) S(2)#2-Ni-S(1)
S(1)-Ni-S(1)#1
91.37(2)
180
S(2)-Ni-S(2)#2
180
Symmetry codes:#1 – x,  y,  z; #2 – x,  y,  z.
1
4
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Fig. 1. ORTEP representation of the synthesized sulfur-rich nickel complex.
1
5
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Fig. 2. Hydrogen bonds and C–H···π interaction of the crystal which lead to 2D sheet structure.
1
6
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Fig. 3. Hydrogen bonds of the crystal between neighboring sheet structures
which lead to 3D network.
1
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+
OH
O H
S
S
S
S
S
+
P
+
P
MeO
P
P
OMe
MeO
OMe
S
Reflux
S
+
S
O H
LR
O
S
S
Ni
MeO
P
P
OMe
S
S
Ni(NO3)2
O
Scheme 1
1
8
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