Synthesis and crystal structure of bis(4-methylpiperidine-dithiocarbamato-S,S′)-palladium(II)

Article abstract of DOI:10.1007/s10870-006-9101-9

The complex bis(4-methylpiperidine-dithiocarbamato-S,)-palladium(II) was synthesized by the reaction of 4-methyl-1-piperidine dithiocarbamic acid with palladium(II) chloride. Its structure was determined by X-ray crystal diffraction analysis. It crystalli

Full text of DOI:10.1007/s10870-006-9101-9

Journal of Chemical Crystallography, Vol. 36, No. 9, September 2006 (ꢀC 2006)
DOI: 10.1007/s10870-006-9101-9
Synthesis and crystal structure of bis(4-methylpiperidine-
ꢀ
dithiocarbamato-S,S )-palladium(II)
(
1)
(1)
(1)
(1)
Saira Shahzadi, Saqib Ali, Amin Badshah, Farkhanda Shaheen,
(2)
(3)∗
Fiaz Ahmed, and Mohammed Fettouhi
Received February 4, 2006; accepted April 18, 2006
Published Online August 9, 2006
ꢁ
The complex bis(4-methylpiperidine-dithiocarbamato-S,S )-palladium(II) was synthesized
by the reaction of 4-methyl-1-piperidine dithiocarbamic acid with palladium(II) chlo-
ride. Its structure was determined by X-ray crystal diffraction analysis. It crystallizes
˚
in the monoclinic P21/c space group with the crystal cell parameters a = 8.6491(8) A,
˚
˚
◦
˚3
b = 18.7305(16) A, c = 11.9933(10) A, β = 107.074(1) , V = 1857.3(3) A and Z = 4. The
palladium (II) ion is bonded to four sulfur atoms, belonging to two dithiocarbamate lig-
ands, in a distorted square planar geometry. The X-ray data suggest a pronounced electronic
delocalization in the two NCS2 moieties.
KEY WORDS: Dithiocarbamate; Palladium(II) complex; Crystal structure.
work,6
−8
we report here the crystal structure
Introduction
Dithiocarbamate ligands are known for their
ꢁ
of bis(4-methylpiperidine-dithiocarbamato-S,S )-
palladium(II).
1
antifungal, antibacterial and biocide activity.
They form complexes with transition metals, lead-
ing to the stabilization of a wide range of oxidation
states. These complexes have found applications
Experimental
2
Synthesis of 4-methyl-1-piperidine
dithiocarbamic acid
in diverse areas such as materials science and
3
,4
medicine. Some dithiocarbamate Pd(II) com-
plexes have been recently reported to have very
close cytotoxicity activity to that of cisplatin.5
Understanding bonding in these complexes will
allow the design of new effective drugs having
reduced toxicity with respect to the currently
used systems. In continuation of our previous
To a solution of CS (6 mL, 1 mmol)
in methanol (15 mL) was added dropwise an
equimolar amount of 4-methylpiperidine (10 mL,
2
1
mmol) in methanol (15 mL). The reaction mix-
ture was stirred for 4 h at room temperature. The
light yellow precipitate was filtered, washed with
1
50 mL diethyl ether and air-dried.
(
1)
Department of Chemistry, Quaid-i-Azam University, Islamabad
◦
Yield 70%, m.p. 178–180 C. Analysis: Cal-
45320 Pakistan.
(
2)
3)
NESCOM, P. O. Box 2216, Islamabad Pakistan.
Department of Chemistry, King Fahd University of Petroleum
and Minerals, Dhahran 31261 Saudi Arabia.
To whom correspondence should be addressed; e-mail: fet-
touhi@kfupm.edu.sa.
culated for C H NS : C, 48.00; H, 7.42; N, 8.00;
S, 36.57. Found: C, 48.12; H, 7.45; N, 7.98; S,
36.52. H NMR (DMSO-d6, ppm), J( H, H),
2.80 (m, 4H), 1.56 (m, 4H), 1.74 (m, 1H), 1.27
7 13 2
(
1
n
1
1
∗
5
67
1
074-1542/06/0900-0567/0 ꢀC 2006 Springer Science+Business Media, Inc.

5
68
Shahzadi, Ali, Badshah, Shaheen, Ahmed, and Fettouhi
Table 1. Crystal Data and Structure Refinement
(
(
3
s, 1H), 0.99 (d, 3H, CH , (7.8)). 13C NMR
3
DMSO-d , ppm), 212.1 (CSS), 51.91 (C–2,6),
6
CCDC deposit no
Empirical formula
Formula weight
Temperature (K)
295231
C14H24N PdS
454.99
297
1.78 (C–3,5), 30.1 (C–4), 21.52 (CH ). IR (KBr,
3
2
4
−
1
cm ), 962 v (C=S), 1003 v (C–S), 2754 v (S–H),
1
410 v (C–N).
˚
Wavelength (A)
0.71073
Monoclinic
P21/c
Crystal system
Space group
S
Unit cell dimensions
1
N
˚
3
a (A)
8.6491(8)
18.7305(16)
11.9933(10)
107.074(1)
1857.3(3)
4
2
C
SH
˚
b (A)
4
c ( A˚ )
β ( )
Volume (A )
◦
CH3
˚
3
Z
Calculated density (g cm 3)
−
1.627
Absorption coefficient (mm 1) 1.444
−
F(000)
Crystal size (mm)
θ range for data collection ( )
Limiting indices
928
Synthesis of bis(4-methylpiperidine-
dithiocarbamato-S,S )-palladium(II)
0.36 × 0.26 × 0.07
ꢁ
◦
2.08–28.38
−
−
−
11 ≤ h ≤ 11
25 ≤ k ≤ 24
16 ≤ l ≤ 15
To a solution of 4-methyl-1-piperidine
dithiocarbamic acid (0.350 g, 2.00 mmol) in
acetone was added an aqueous solution of
palladium(II) chloride (0.175 g, 1.00 mmol)
dropwise with constant stirring at room tem-
perature in 100 mL round bottom flask. Af-
ter 0.5 h the yellow precipitates were filtered
and dried in air. The crystals suitable for X-ray
diffraction were grown by recrystallization from
chloroform.
Max and min transmission
Data/restraints/parameters
Goodness-of-fit on F
Final R indices [I>2σ(I)]
R indices (all data)
Tmin = 0.6245, Tmax = 0.9057
4497/0/192
1.078
2
R1 = 0.0414, wR2 = 0.0944
R = 0.0535, wR = 0.0994
1
2
Largest diff. Peak and hole
1.255 and -0.298
˚
−3
eA )
(
◦
Yield 80%, m.p. 282–284 C. Analysis: Cal-
culated for C H N S Pd: C, 36.79; H, 5.73; N,
14
26
2 4
6
.13; S, 28.06. Found: C, 36.83; H, 5.78; N, 6.18;
−
1
refined by full matrix least square methods based
S, 28.12. IR (KBr, cm ), 982 ν(C=S), 1195 v
2
on F , using the structure determination and
(
C–S), 1490 v (C–N), 445 v (Pd–S).
12
graphics package SHELXTL based on SHELX
13
9
7. Hydrogen atoms were included at calcu-
lated positions using a riding model. The final
refinement gave a ratio of maximum/minimum
residual density of 4.21 due to a positive resid-
X-ray data collection and structure
determination
−
3
˚
ual density maximum of 1.255 eA located at
A crystal of the complex was mounted on
glass fiber. Diffraction data were recorded on a
Bruker-AXS Smart Apex system equipped with
˚
0
.918 A from Pd1. The crystallographic data
are given in Table 1. Selected bond lengths and
angles are given in Table 2. Complete bond
lengths and bond angles, anisotropic thermal pa-
rameters and calculated hydrogen coordinates
are deposited as supplementary materials. The
ORTEP atomic labeling Scheme is given in
Fig. 1.
a graphite monochromatized Mo Kα radiation
˚
(
λ = 0.71073 A). The data were collected using
9
SMART. The data integration was performed
1
0
using SAINT. An empirical absorption cor-
11
rection was carried out using SADABS. The
structure was solved with the direct methods and

Synthesis and crystal structure
569
˚
◦
Table 2. Selected Bond Lengths (A) and Bond Angles ( )
˚
Bond lengths (A)
Pd(1)–S(1)
Pd(1)–S(4)
Pd(1)–S(3)
Pd(1)–S(2)
S(1)–C(1)
2.3096(9)
2.3131(9)
2.3179(9)
2.3187(9)
1.714(3)
S(2)–C(1)
S(3)–C(8)
S(4)–C(8)
N(1)–C(1)
N(2)–C(8)
1.718(3)
1.713(3)
1.715(3)
1.310(4)
1.314(4)
◦
Bond angles ( )
S(1)–Pd(1)–S(4)
S(1)–Pd(1)–S(3)
S(4)–Pd(1)–S(3)
S(1)–Pd(1)–S(2)
S(4)–Pd(1)–S(2)
S(3)–Pd(1)–S(2)
103.77(3)
176.53(4)
75.40(3)
75.28(3)
174.18(4)
105.19(3)
C(1)–S(1)–Pd(1) 86.84(11)
C(1)–S(2)–Pd(1) 86.47(11)
C(8)–S(3)–Pd(1) 86.37(11)
C(8)–S(4)–Pd(1) 86.47(11)
S(1)–C(1)–S(2)
S(3)–C(8)–S(4)
110.91(19)
111.40(19)
◦
Results and discussion
and 103.77(3) respectively. These values are
in agreement with those reported for other
bis(N,N-dialkyldithiocarbamato)-palladium(II)
The reaction of 4-methyl-1-piperidine
dithiocarbamic acid with palladium(II) chloride
resulted in the deprotonation of the former by
Pd(II) to afford the title complex. The palladium
1
4–15
complexes.
The N–C bonds of the two
NCS moieties, N1–C1 1.310(4) A˚ and N2–C8
1.314(4) A˚ , are shorter than a single N–C bond
2
(
II) ion is bonded to four sulfur atoms belonging
hence suggesting a partial double bond character.
The four S–C bond distances show no significant
difference and average to 1.715(3) A˚ , indicating
also a partial double bond character. These data
suggest a pronounced electronic delocalization in
to two dithiocarbamate ligands and the PdS core
exhibits a distorted square planar geometry. The
Pd(II) ion is displaced from the least square plane
4
˚
defined by the four sulfur atoms by 0.0926(5) A.
The four Pd–S bond distances are not equal and
are in the range 2.3096(9)–2.3187(9) A. The
the NCS moiety. The two piperidyl rings adopt a
2
˚
chair conformation with the methyl groups taking
equatorial positions. The two methyl substituents
are anti and the torsional angle for C5 C4 C11
S–Pd–S bond angles in the two strained four-
◦
membered chelate rings average to 75.34(3) . The
◦
◦
remaining S–Pd–S bond angles are 105.19(3)
and C12 is −169.1(7) . The shortest Pd. . .Pd
ꢁ
Fig. 1. Molecular structure of bis(4-methylpiperidine-dithiocarbamato-S,S )-palladium(II). Thermal
ellipsoids have been drawn with 30% probability. Hydrogen atoms have been omitted for clarity.

5
70
Shahzadi, Ali, Badshah, Shaheen, Ahmed, and Fettouhi
Fig. 2. Side view of the molecular structure of bis(4-methylpiperidine-dithioc-
ꢁ
arbamato-S,S )-palladium(II). Thermal ellipsoids have been drawn with 30% proba-
bility. Hydrogen atoms have been omitted for clarity.
˚
2. Hogarth, G. Prog. Inorg. Chem. 2005, 53, 71.
. Regulacio, M.D.; Tomson, N.; Stoll, S.L. Chem. Mater. 2005,
7, 3114, and references therein.
4. Giovagnini, L.; Marzano, C.; Bettio, F.; Fregona, D. J. Inorg.
Biochem. 2005, 99, 2139 and references therein.
distance is 6.244 A, ruling out any metal-metal
3
ꢁꢁ
interaction. One intermolecular S3–S3 distance
˚
3.566 A) is significantly less than the some of
the Van der Waals radii, indicating intermolecular
interactions through sulfur atoms.
1
(
5. Alverdi, V.; Giovagnini, L.; Marzano, C.; Seraglia, R.; Bettio,
F.; Sitran, S.; Graziani, R.; Fregona, D. J. Inorg. Biochem. 2004,
9
8, 1117.
6
7
8
9
. Ali, S.; Ahmad, S.U.; Shahzadi, S.; Rehman, S.; Parvez, M.;
Mazhar, M. Appl. Organomet. Chem. 2005, 19, 201.
. Ali, S.; Ahmad, S.U.; Rehman, S.; Shahzadi, S.; Parvez, M.;
Mazhar, M. Appl. Organomet. Chem. 2005, 19, 200.
. Parvez, M.; Badshah, A.; Asma, M.; Ali, S.; Ahmad, S.; Malik,
A.; Ahmed, F. Acta. Cryst. 2004, E60, m1602.
Supplementary materials The supplementary X-ray data are avail-
able from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK on
request, quoting the deposition No 295231.
Acknowledgements
. SMART APEX software (5.05) for SMART APEX detector,
Bruker Axs Inc. Madison. Wisconsin, USA.
This work was partly supported by King
Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia. SA is thankful to Quaid-
i-Azam University, Islamabad, Pakistan for finan-
cial support.
10. SAINT software (5.0) for SMART APEX detector, Bruker Axs
Inc. Madison. Wisconsin, USA.
1
1. Sheldrick, G.M. SADABS. Program for Empirical Absorption
correction of Area detector Data. University of gottingen,
Germany, 1996.
12. Sheldrick, G.M. SHELXTL V5.1 Software, Bruker AXS, Inc.,
Madison, Wisconsin, USA, 1997.
13. Sheldrick, G.M. University of Gottingen: Germany, 1997.
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