X-ray Structure Analysis Online 2012, VOL. 28
2012 © The Japan Society for Analytical Chemistry
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X-ray Structure Analysis Online
Crystal Structure of Bis(O-Propyldithiocarbonato-k2S,S¢)(2,2¢-bipyridinek2N,N¢)nickel(II)
Kuldeep SINGH,* Sanjay KAPOOR,** Renu SACHAR,** Vivek K. GUPTA,* and Rajnikant*†
*X-ray Crystallography Laboratory, Post-Graduate Department of Physics, University of Jammu,
Jammu Tawi – 180 006, India
**Department of Chemistry, University of Jammu, Jammu Tawi–180 006, India
The title complex, bis(O-propyldithiocarbonato-k2S,S¢)(2,2¢-bipyridine-k2N,N¢)nickel(II) [Ni(S2COCH2CH2CH3)2(C10H8N2)],
was synthesized by the reaction of bis(O-propyldithiocarbonato)nickel(II) with the bidentate ligand 2,2¢-bipyridine in
acetone. It crystallized in the tetragonal space group I42d with the following unit-cell parameters: a = 22.071(4), c =
9.189(3)Å and Z = 8. The crystal structure was solved by direct methods, and refined by full-matrix least-squares
procedures to a final R-value of 0.0311 for 1779 observed reflections. The pyridine ring makes a dihedral angle of
86.21(1)˚ with the dithiocarbonato ring. The Ni2+ ion is in a strongly distorted octahedral coordination environment
formed by an N2S4 donor set, defined by two chelating dithicarbonate anions as well as a 2,2¢-bipyridine ligand with the
Ni2+ ion located at the crystallographic two-fold axis of rotation (Wyckoff letter : d).
(Received March 14, 2012; Accepted April 23, 2012; Published on web June 10, 2012)
Xanthates are used in curing and vulcanization of rubber, as
collectors of sulphide ores or minerals in the froth floatation
process, as fungicides and pesticides in agriculture, and in the
manufacture of synthetic textiles.1–3 Metal xanthate complexes
and their reaction products with a variety of Lewis bases have
been extensively studied.4,5 To the best of our knowledge, the
reaction products of nickel(II) propylxanthate with bidentate
heterocyclic imines, such as 2,2¢-bipyridine, have not been very
extensively studied, especially their crystallographic aspects.
Therefore, the synthesis and X-ray crystal structure of bis(Opropyldithiocarbonato)(2,2¢-bipyridine)nickel(II) is reported here.
The complex bis(O-propyldithiocarbonato)nickel(II) was
prepared by mixing of an aqueous solution of nickel(II) chloride
and potassium propylxanthate.6
The addition complex of bis(O-propyldithiocarbonato)nickel(II) with 2,2¢-bipyridine (Fig. 1) was prepared by stirring
green precipitates of the parent complex, [Ni(S2COC3H7)2], in
acetone with 2,2¢-bipyridine. Shining dark green crystals of the
adduct were isolated by slow evaporation of the resulting
solution of the complex. The details are found in Supporting
Information.
Fig. 1 Chemical structure of Bis(O-Propyldithiocarbonato-k2S,S¢)
(2,2¢-bipyridine-k2N,N¢)nickel(II).
† To whom correspondence should be addressed.
E-mail: [email protected]
A dark-green blocked-shaped single crystal of the title
compound was picked up for X-ray intensity data collection.
All hydrogen atoms were located from a difference electron
density map, and their positional and isotropic thermal
parameters were included in the refinement.
The final
refinement cycle yielded an R-factor of 0.0311 [wR(F2) =
0.0717] for the observed data. The crystallographic data are
summarized in Table 1. Selected bond lengths, bond angles and
torsion angles are given in Table 2S. A general view of the
Table 1
Crystal data and other experimental details
Chemical formula: C18H22N2NiO2S4
Formula weight = 970.65
T = 293 K
Crystal system: tetragonal
Space group: I42d (No.122)
a = 22.071(4)Å
Z=8
c = 9.189(3)Å
V = 4476.1(2)Å3
Dx = 1.440 g/cm3
Dm (floatation) = not measured
Radiation: Mo Ka (l = 0.71073 Å)
F(0 0 0) = 2016
m(Mo Ka) = 1.255 mm–1
Crystal size = 0.30 ¥ 0.20 ¥ 0.20 mm3
No. of reflections collected = 15923
No. of independent reflections = 1953
q range for data collection: 3.55 to 25˚
Data/Restraints/Parameters = 1953/0/123
Goodness-of-fit on F2 = 1.037
R indices [I > 2s(I)]: R1 = 0.0311, wR2 = 0.0694
R indices (all data): R1 = 0.0368, wR2 = 0.0717
(D/s)max = –0.001 for y H5
(Dr)max = 0.212 eÅ–3
(Dr)max = –0.175 eÅ–3
Measurement: X’calibur system—Oxford diffraction make, U.K.
Programs system: SHELXL-97, CrysAlis RED
Structure determination: SHELXS-97
CCDC deposition number: 870008
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X-ray Structure Analysis Online 2012, VOL. 28
Fig. 2 ORTEP view of the molecule with displacement ellipsoids
drawn at the 50% probability level. H atoms are shown as small
spheres of arbitrary radii.
molecule indicating atom numbering scheme is shown in Fig. 2.
The molecule is on a two-fold axis and the asymmetric unit
comprises of a half molecule. The bond lengths and bond
angles in bis(O-propyldithiocarbonato-k2S,S¢)(2,2¢-bipyridinek2N,N¢)nickel(II) are in good agreement with some analogous
structures.7,8 The C–S bond lengths involving the xanthate
ligands are: C7–S1 = 1.678(3)Å and C7–S2 = 1.683(3)Å. These
values show a double-bond character due to delocalization over
the two C–S bonds.9 The bond angles in the pyridine ring vary
from 118.1(3) to 122.6(6)˚, the average value being 119.9(3)˚.
The dihedral angle between the dithio-group and the pyridine
ring is 86.21(1)˚, which shows that the pyridine ring is held
almost perpendicular to the dithiocarbonato group. The O1–C7
bond distance [1.322(4)Å] is shorter than O1–C8 [1.457(5)Å] as
a consequence of hybridization of the carbon atom. The short
value of bond distance for the O1–C7 is consistent with a
significant contribution of the resonance form of the xanthate
anion, which features a formal C=O and a negative charge on
each S atom.10 Molecules are arranged in layers (Fig. 3).
Acknowledgements
One of the authors (Rajnikant) acknowledges the Department of
Science & Technology for single crystal X-ray diffractometer as
a National Facility under Project No. SR/S2/CMP-47/2003.
Fig. 3 Packing diagram viewed down the c-axis.
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