Preparation and structure of nickel complex Ni(dppe)Cl2

Article abstract of DOI:10.14233/ajchem.2013.14667

Mononuclear nickel complex Ni(dppe)Cl₂ (dppe = Ph ₂PCH₂CH₂PPh₂) was prepared by reaction of NiCl₂·6H₂O and dppe in CH ₂Cl₂/methanol solution and its structure was determined by single crystal X-ray diffraction analysis. The crystals are monoclinic, space group P2₁/c with a = 12.228(3), b = 15.235(4), c = 15.294(4) A?, α = 90.00, β = 105.933(4), γ= 90.00°, V = 2739.7(13) A?³, Z = 4, F₍₀₀₀₎ = 1256, D_c = 1.486 g/cm³, μ = 1.231 cm^-1, the final R = 0.0543 and wR = 0.1297. A total of 28157 reflections were collected, of which 6516 were independent (R_int = 0.0620).

Full text of DOI:10.14233/ajchem.2013.14667

Asian Journal of Chemistry; Vol. 25, No. 14 (2013), 7876-7878
http://dx.doi.org/10.14233/ajchem.2013.14667
Preparation and Structure of Nickel Complex Ni(dppe)Cl
2
*
WEI GAO , KAI LI and XIN-LING WANG
School of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450046, P.R. China
*
Corresponding author: E-mail: gaowei222@yahoo.cn; weigao415@yahoo.cn
Received: 11 October 2012; Accepted: 22 July 2013)
(
AJC-13831
Mononuclear nickel complex Ni(dppe)Cl
2
(dppe = Ph
2
2
PCH CH
2
PPh
2
) was prepared by reaction of NiCl
2
·6H
2
O and dppe in CH
2
2
Cl /
methanol solution and its structure was determined by single crystal X-ray diffraction analysis. The crystals are monoclinic, space group
3
P2 /c with a = 12.228(3), b = 15.235(4), c = 15.294(4) Å, α = 90.00, β = 105.933(4), γ = 90.00°, V = 2739.7(13) Å , Z = 4, F(000) = 1256,
1
3
-
1
D = 1.486 g/cm , µ = 1.231 cm , the final R = 0.0543 and wR = 0.1297. A total of 28157 reflections were collected, of which 6516 were
c
independent (Rint = 0.0620).
Key Words: Synthesis, Crystal Structure, Nickel complex, Diphosphine.
restraint Uiso(H) = 1.2 Ueq(N). Other H atoms were posi-
INTRODUCTION
tioned geometrically and refined using a riding model, with
d(C---H) = 0.93-0.97 Å and Uiso(H) = 1.2 Ueq(C) or 1.5
Ueq(Cmethyl). The final full-matrix least squares refinement
gave R = 0.0543 and wR = 0.1297.
In past decades, nickel complexes with diphosphine
ligands have been received considerable attention due to their
1
potential application in catalytic reactions . Among these
numerous nickel complexes with diphosphine ligands,
Synthesis: To a methanolic solution of NiCl
mmol) was added a solution of dppe (1 mmol) in CH
2
·6H
Cl
2
O (1
. The
2
Ni(dppe)Cl
2
have been used in the carbon dioxide reaction .
2
2
As we know, dppe is a common diphosphine ligand and easy
to obtain. In order to develop the coordination chemistry of
nickel complexes and novel structures, we carried out study
on nickel complex with a bidentate ligand dppe. In this paper,
we report the preparation and crystal structure of complex
mixture was stirred at room temperature for 1 h and then the
solvent was reduced in vacuo. The residue was crystallized in
CH
2
2
Cl /hexane at room temperature and the red crystals were
obtained after several days.
Ni(dppe)Cl
2
.
RESULTS AND DISCUSSION
Treatment of methanolic solution of NiCl
solution of dppe in CH Cl afforded the Ni(dppe)Cl
2
·6H
2
O with a
complex.
/hexane gave
EXPERIMENTAL
2
2
2
Crystal structure determination: The crystal of
Ni(dppe)Cl with dimensions of 0.20 mm × 0.16 mm × 0.12
mm was mounted on a Rigaku Saturn CCD area-detector
diffractometer with a graphite-monochromated MoK radia-
Slow evaporation of the this complex in CH
red crystals.
Cl
2 2
2
Structure of the Ni(dppe)Cl : The complex was confir-
2
α
med by single crystal X-ray diffraction analysis. Crystallo-
graphic and refinement parameters are given in Table-1. The
selected bond lengths and bond angles listed in Tables 2-4,
respectively. The structure was solved by direct methods.
Anisotropic displacement parameters were applied to all
nonhydrogen atoms in full-matrix least-square refinements
tion (λ = 0.71073 Å) by using a phi and scan modes at 113(2)
K in the range of 1.73º ≤ θ ≤ 27.87º. The crystal belongs to
Monoclinic system with space group P2
1
/c and crystal para-
meters of a = 12.228(3) Å, b = 15.235(4) Å, c = 15.294(4) Å,
3
α = 90º, β = 105.933(4)º, γ = 90°, V = 2739.7(13) Å , D =
c
3
-1
2
1
=
9
.486 g/cm . The absorption coefficient µ = 1.231 mm and Z
4. The structure was solved by direct methods with SHELXS-
based on F . The hydrogen atoms were set in calculated posi-
tions with a common fixed isotropic thermal parameter.
The molecular structure and the packing view of the title
complex are shown in Figs. 1 and 2, respectively.
3
2
7 and refined by the full-matrix least squares method on F
4
data using SHELXL-97 . The empirical absorption corrections
were applied to all intensity data. H atom of N-H was initially
located in a difference Fourier map and were refined with the
The complex Ni(dppe)Cl
2
crystallizes in the monoclinic
space group P2 /c. The unit cell contains one molecule
1

Vol. 25, No. 14 (2013)
Preparation and Structure of Nickel Complex Ni(dppe)Cl 7877
2
TABLE-1
CRYSTAL DATA AND STRUCTURE
REFINEMENT OF Ni(dppe)Cl2
Items
Values
Empirical formula
Formula weight
Crystal system
C H Cl NiP
2
612.93
Monoclinic
27
26
4
Unit cell dimensions
a (Å)
b (Å)
c (Å)
12.228(3)
15.235(4)
15.294(4)
Unit cell angles (º)
α
β
γ
90
105.933(4)
90
2739.7(13)
4
3
Volume (Å )
Z
Fig. 1. Molecular structure of Ni(dppe)Cl
2
Temperature (K)
Space group
Wavelength (Å)
113(2)
P2 /c
1
0.71073
1.486
1.231
1256
3
Calculated density (g/cm )
Absorption coefficient (mm )
F(000)
-1
Crystal size (mm)
0.20 × 0.16 × 0.12
1.73 – 27.87
28157
6516 [R(int) = 0.0620]
Theta range for data collection (º)
Reflections collected
Independent reflections
Final R indices [I > 2σ(I)]
R = 0.0543, wR = 0.1297
1 2
TABLE-2
SELECTED BOND LENGTHS [Å] OF Ni(dppe)Cl2
Bond lengths
Ni(1)-P(1)
Ni(1)-P(2)
Ni(1)-Cl(2)
Ni(1)-Cl(1)
P(1)-C(7)
X-Ray crystal
2.1306(11)
2.1551(10)
2.2021(10)
2.2100(9)
Bond lengths
P(1)-C(1)
P(1)-C(13)
P(2)-C(15)
P(2)-C(21)
P(2)-C(14)
X-Ray crystal
1.826(4)
1.867(4)
1.816(3)
1.818(3)
1.804(4)
1.829(3)
TABLE-3
SELECTED BOND ANGLES [º] OF Ni(dppe)Cl2
Bond angles
X-Ray crystal
87.46(4)
175.21(4)
88.59(4)
Bond angles
P(2)-Ni(1)-Cl(1)
Cl(2)-Ni(1)-Cl(1)
C(1)-P(1)-Ni(1)
C(15)-P(2)-Ni(1)
X-Ray crystal
175.56(4)
95.50(4)
119.38(12)
118.01(11)
P(1)-Ni(1)-P(2)
P(1)-Ni(1)-Cl(2)
P(2)-Ni(1)-Cl(2)
P(1)-Ni(1)-Cl(1)
88.54(4)
TABLE-4
SELECTED BOND ANGLES [º] TORSIONAL
ANGELS (º) OF Ni(dppe)Cl2
Fig. 2. Two-dimensional network of hydrogen bonds (dashed lines)
Bond angles
X-Ray crystal
103.37(13)
137.7(4)
-74.71(13)
-132.52(16)
-98.2(5)
49.40(16)
-12.78(13)
21.6(5)
P(2)-Ni(1)-P(1)-C(7)
Cl(2)-Ni(1)-P(1)-C(7)
Cl(1)-Ni(1)-P(1)-C(7)
P(2)-Ni(1)-P(1)-C(1)
Cl(2)-Ni(1)-P(1)-C(1)
Cl(1)-Ni(1)-P(1)-C(1)
P(2)-Ni(1)-P(1)-C(13)
Cl(2)-Ni(1)-P(1)-C(13)
5
complex . The P1-Ni1-P2 bond angle [87.46(4)º] are shorter
than the corresponding angle in the crystal structure of
Ni(dppe)Cl [131.0(4)º]. The phenyl rings (C1, C2, C3, C4,
2
C5, C6), (C7, C8, C9, C10, C11, C12), (C15, C16, C17, C18,
C19, C20) and (C21, C22, C23, C24, C25, C26) are fairly
planar with plane equation 4.902x + 11.020y + 7.477z =
11.2291, -8.274x + 9.506y + 8.589z = 2.3887, -3.285x +
5
.131y + 14.400z = 1.3027 and 9.755x + 0.860y + 5.480z =
of Ni(dppe)Cl
2
and one molecule of CH
2
Cl
2
.As can be seen in
9.1137, respectively. The largest deviation from the least
squares plane is 0.0103 Å .
As shown in Fig. 2, there are intermolecular C-H···Cl
hydrogen bonds in the crystal packing. These interactions can
help to stabilize the crystal structure.
6
Fig. 1, the molecular structure of the title complex consists of
a nickel atom coordinated by a dppe ligand and two chloride
anions. The Ni-Cl bond lengths [2.2021(10) and 2.2100(9) Å]
are close to the values found in the related nickel diphosphine

7
878 Gao et al.
Asian J. Chem.
3
4
5
.
.
.
G.M. Sheldrick, SHELXS97, A Program for Crystal Structure Solu-
tion; University of Göttingen: Germany (1997).
G.M. Sheldrick, SHELXL97, A Program for Crystal Structure Refine-
ment; University of Göttingen: Germany (1997).
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M.R. Foreman, R.A. Howie, M.J. Plater and J.M.S. Stakle, Acta
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Supplementary material
CCDC 901592 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/ retrieving.html or from
the Cambridge CrystallographicData Centre (CCDC), 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-
3
36033; email: deposit@ccdc.cam.ac.uk or www: http://
6. (a) X.H. Liu, C.X. Tan and J.Q. Weng, Phosphorus Sulfur Silicon Rel.
Elem., 186, 552 (2011); (b) X.H. Liu, C.X. Tan and J.Q. Weng, Phos-
phorus Sulfur Silicon Rel. Elem., 186, 558 (2011); (c) P.Q. Chen, C.X.
Tan, J.Q. Weng and X.H. Liu, Asian J. Chem., 24, 2808 (2012); (d)
Y.L. Xue, Y.G. Zhang and X.H. Liu, Asian J. Chem., 24, 3016 (2012);
www.ccdc.cam.ac.uk).
ACKNOWLEDGEMENTS
(
(
e)Y.L. Xue,Y.G. Zhang and X.H. Liu, Asian J. Chem., 24, 1571 (2012);
f) X.F. Liu and X.H. Liu, Acta Cryst., E67, o202 (2011); (g) X.H. Liu,
The authors gratefully acknowledged the financial support
from the Doctoral Research Fund of Henan University of
Traditional Chinese Medicine.
L. Pan, C.X. Tan, J.Q. Weng, B.L. Wang and Z.M. Li, Pestic. Biochem.
Physiol., 101, 143 (2011); (h) X.H. Liu, J.Q. Weng, C.X. Tan and H.J.
Liu, Acta Cryst., E67, o1940 (2011); (i) X.H. Liu, J.Q. Weng, C.X.
Tan, L. Pan, B.L. Wang and Z.M. Li, Asian J. Chem., 23, 4031 (2011);
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