Inorganica Chimica Acta 360 (2007) 3448–3451

www.elsevier.com/locate/ica

Note

Square planar mononuclear Pd(II) complexes of substituted

2-(pyrazole-1-yl)phenylamines with a helical twist
Michael G.B. Drew a, Anuradha Mukherjee b, Senjuti De c, Samik Nag c, Dipankar Datta c,*

a
School of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK
b
UMR 6510 SESO, Universite de Rennes 1, 35042 Rennes Cedex, France
c
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Calcutta 700 032, India

Received 12 February 2007; received in revised form 9 April 2007; accepted 9 April 2007
Available online 20 April 2007

Abstract

X-ray crystal structure shows that 3,5-dimethyl-1-(2-nitrophenyl)-1H-pyrazole (DNP) belongs to the rare class of helically twisted
synthetic organic molecules. Hydrogenation of DNP gives 2-(3,5-dimethylpyrazole-1-yl)phenylamine (L) which on methylation yields
[2-(3,5-dimethylpyrazole-1-yl)phenyl]dimethylamine (L 0 ). Two Pd(II) complexes, PdLCl2 (1) and PdL 0 Cl2 (2), are synthesized and char-
acterized by NMR. X-ray crystallography reveals that 1 and 2 are unprecedented square planar complexes which possess well discernible
helical twists.
Ó 2007 Elsevier B.V. All rights reserved.

Keywords: Palladium; Helical; Pyrazole; N ligands; Crystal structures

1. Introduction dination. So much so, that Pd(II), which has a marked

The word ‘‘helix’’ in Greek means winding. Structures
having windings are now amply recognized in biochemis-
try. But these are not so common in organic chemistry.
In fact, only a handful of synthetic organic molecules
(e.g. [n]helicenes) are known to have spiral morphology
[1–4]. The reason is that these can be obtained only
through deliberate, designed syntheses. In contrast, there
are many helical metallo-organic molecules. In these cases,
non-helical organic molecules containing suitable hetero-
donor atoms are wrapped around in a manner directed
by the coordination properties of the metal ions. The metal
ions in the known helicates, with a few exceptions, are four-,
six- or eight-coordinate [5–8]. In the four coordinate heli-
cates, the metal ions are invariably tetrahedral which tends
to suggest that such a geometry is a prerequisite for gener-
ating a helicate of the metal ions which can have four coor-
*
Corresponding author. Tel.: +91 33 24735374; fax: +91 33 24732805.
E-mail address: icdd@mahendra.iacs.res.in (D. Datta).
preference for square planar disposition of the coordinat-
ing atoms, has been found to be distorted penta-coordinate
in its only known helicate, which is dinuclear [9]. To-date
there is no example of a structurally characterized helical
complex where the metal ion is square planar. Herein, we
describe two mononuclear square planar Pd(II) complexes
which possess distinct helical twist.
2. Results and discussion
Our ligands are pyrazole tethered bidentate N donors:
2-(3,5-dimethylpyrazole-1-yl)phenylamine (L) and [2-(3,5-
dimethylpyrazole-1-yl)phenyl]dimethylamine (L 0 ). Their
syntheses are reported in the literature [10]. But, their metal
binding abilities are yet to be explored. Further, their X-ray
crystal structures are also not known. Though it has not
been possible to grow single crystals of L and L 0 , we have
succeeded in getting single crystals of one of their precur-
sors and structural congeners – 3,5-dimethyl-1-(2-nitro-
phenyl)-1H-pyrazole (DNP). Hydrogenation of DNP gives
L which on subsequent methylation yields L 0 . DNP is a red

0020-1693/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.04.013
 M.G.B. Drew et al. / Inorganica Chimica Acta 360 (2007) 3448–3451 3449

solid. While the ligand L is a dirty white solid, L 0 is a vis-

cous pale yellow liquid. The X-ray crystal structure of
DNP is shown in Fig. 1 together with the atomic number-
ing scheme used throughout. The angle between the two
rings is 56.8(1)° and that between the nitro group and the
phenyl ring is 45.8(1)°.
Me

N
N
NR2 Me

R = H: L; R = Me: L'

Reaction of Na2[PdCl4] with L and L 0 in methanol in

equimolar proportions gives PdLCl2 (1) and PdL 0 Cl2 (2)
respectively in moderate yield. These are yellow in colour.
In single crystal X-ray crystallography, two molecules are
found in the asymmetric unit of 1 with equivalent geom- Fig. 2. The structure of PdLCl2 (1) with ellipsoids at 25% probability.
There are two molecules in the asymmetric unit with equivalent geom-
etries (Fig. 2). The metal forms a four-coordinate square etries. Selected bond distances (Å) and angles (°): Pd(1)–Cl(1) 2.291(2),
environment although it is significantly distorted from 2.289(2), Pd(1)–Cl(2) 2.289(2), 2.309(2), Pd(1)–N(11) 2.038(4), 2.044(4),
planarity. In the two molecules, the r.m.s. deviations of Pd(1)–N(22) 2.014(4), 2.025(5), Cl(1)–Pd(1)–Cl(2) 90.8(1), 91.7(1),
the atoms in the PdN2Cl2 plane are both 0.16 Å. The phe- Cl(1)–Pd(1)–N(11) 92.0(1), 90.7(1), Cl(1)–Pd(1)–N(22) 174.9(1), 174.9(1),
nyl ring of L intersects the equatorial plane at angles of Cl(2)–Pd(1)–N(11) 175.6(1), 175.6(1), Cl(2)–Pd(1)–N(22) 94.3(1), 94.3(1),
N(11)–Pd(1)–N(22) 83.0(2), 83.0(2).
60.2(1)°, 60.3(1)° and the pyrazole ring at 50.4(1)°,
47.2(1)°. The two rings of L intersects at 38.5(1)°,
38.7(1)°. Thus, coordinated L is slightly more planar than
DNP. The two hydrogen atoms on the donor nitrogen Table 1
atom N(11) [and N(51)] form intermolecular hydrogen Hydrogen bonds in 1 (distances, Å; angles, °)
bonds to the chlorine atoms of the other molecule in H  Cl N–H  Cl N  Cl
the asymmetric unit as shown in Table 1. The X-ray crys- N(11)–H(11A) 2.64 135 3.34(1) Cl(4) [x, y + 1,
tal structure of 2 is shown in Fig. 3 [12]. The bond lengths z + 1]
are equivalent to those in 1 apart from Pd(1) to N(11) N(11)–H(11A) 2.98 152 3.79(1) Cl(3) [x, y + 1,
z + 1]
which is 2.131(3) Å compared to 2.038(4), 2.044(4) Å in
N(11)–H(11B) 2.79 166 3.67(1) Cl(4) [x, y  1, z + 1]
1. The increase may be caused by the methyl groups on N(51)–H(51A) 2.49 152 3.31(1) Cl(1) [x + 1, y + 1,
N(11) in 2. The presence of the methyl groups on N11 z + 1]
in 2 also affects the overall shape of the molecule when N(51)–H(51A) 2.70 130 3.35(1) Cl(2) [x + 1, y + 1,
compared to 1. The atoms in the equatorial plane are z + 1]
much closer to being coplanar with a r.m.s. deviation of

0.05 Å. The two rings of L 0 intersect the equatorial plane

Fig. 1. The structure of DNP with ellipsoids at 25% probability.
at 70.7(1)°, 50.4(1)° for the 6- and 5- membered rings,
respectively and these rings intersect each other at an
angle of 48.9(1)°.
Our ligands L and L 0 are two new examples of bidentate
chelating ligands which have an anilino N as a binding site.
The molecule DNP has a helical twist. The two rings in it
are twisted with respect to each other and the nitro group
provides the third plane needed to define a helix. Thus, it
belongs to the rare class of synthetic organic molecules
which have a helical sense. This inherent twist is preserved
in its structural congeners L and L 0 in their metal-coordi-
nated mode. In fact, the helical twists can be discerned bet-
ter in their complexes (Fig. 4). Thus, the complexes 1 and 2
described here are examples of rare square planar com-
pounds having helical twists.
3450 M.G.B. Drew et al. / Inorganica Chimica Acta 360 (2007) 3448–3451
Fig. 3. The structure of PdL 0 Cl2 (2) with ellipsoids at 25% probability.
Selected bond distances (Å) and angles (°): Pd(1)–Cl(1) 2.286(1), Pd(1)–
Cl(2) 2.286(1), Pd(1)–N(11) 2.131(3), Pd(1)–N(22) 2.031(7), Cl(1)–Pd(1)–
Cl(2) 87.8(1), Cl(1)–Pd(1)–N(11) 95.7(1), Cl(1)–Pd(1)–N(22) 178.9(1),
Cl(2)–Pd(1)–N(11) 174.6(1), Cl(2)–Pd(1)–N(22) 91.7(1), N(11)–Pd(1)–
N(22) 84.8(1).
Fig. 4. Views of the helical twists in the Pd(II) complexes: (a), 1 and (b), 2.
3. Experimental
3.1. Materials and physical measurements
L and L 0 were prepared according to a reported proce-
dure [10]. Microanalyses were performed by a Perkin–
Elmer 2400II elemental analyzer. UV–Vis spectra in meth-
anol were recorded on a Perkin–Elmer Lambda 950 spec-
trophotometer and NMR spectra in CDCl3 (reference:
TMS) on a Brucker AMX 300 spectrometer.
3.2. Preparation of DNP
A reported procedure [10] was followed. Red single crys-
tals were obtained by slow aerial evaporation of an acetone
solution of it. UV–Vis kmax/nm (e/dm3 mol1 cm1): 330
(320), 422 (1460).
3.3. Preparation of PdLCl2 (1)
59 mg (0.2 mmol) of Na2[PdCl4] dissolved in 5 ml of
methanol was added dropwise to 37 mg (0.2 mmol) of
ligand L dissolved in 15 ml of methanol with stirring.
The resulting yellow solution was then left for slow aerial
evaporation. After several days, the deposited orange crys-
talline compound was filtered off, washed with a few drops
of cold methanol and dried in air. Yellow single crystals
were obtained from acetonitrile–toluene mixture. Yield:
45 mg (62%). UV–Vis kmax/nm (e/dm3 mol1 cm1): 216
(21 900), 252 (140), 394 (920). 1H NMR d/ppm: 1.26,
2.10, 2.18, 2.37, 2.53, 6.18 (s, 1H, pyrazole), 6.25 (br.),
7.34–7.54 (d + m, 4H, aryl protons). Anal. Calc. for
C11H13Cl2PdN3: C, 36.21; H, 3.60; N, 11.52. Found: C,
36.07; H, 3.44; N, 11.29%.
3.4. Preparation of PdL 0 Cl2 (2)
29 mg (0.1 mmol) of Na2[PdCl4] dissolved in 5 ml of
methanol was added dropwise to 21 mg (0.1 mmol) of
ligand L 0 dissolved in 10 ml of methanol and stirred for
30 min. Within 10 min of stirring, a yellow crystalline com-
pound started appearing. The yellow compound was fil-
tered, washed with few drops of methanol and dried in
air. Yellow single crystals were obtained from acetoni-
trile–toluene mixture Yield: 15 mg (40%). UV–Vis kmax/
nm (e/dm3 mol1 cm1): 218 (26 200), 398 (520). 1H
NMR d/ppm: 2.03 (s, 3H, methyl), 2.41 (s, 3H, methyl),
2.76 (s, 3H, methyl), 3.12 (s, 3H, methyl), 6.34 (s, 1H, pyr-
azole), 7.54–7.62 (t + m, 4H, aryl protons). Anal. Calc. for
C13H17Cl2PdN3: C, 39.74; H, 4.36; N, 10.69. Found: C,
39.74; H, 4.10; N, 10.56%.
3.5. X-ray crystallography
Crystal data for DNP, 1 and 2 are given in Table 2.
These were measured at 150 K using the Oxford X-Calibur
CCD System with Mo Ka radiation. The crystals were
positioned at 50 mm from the CCD. 321 frames were mea-
sured with a counting time of 3 s. Data analyses were car-
ried out with the CRYSALIS program [11]. The structures
were solved using direct methods with the SHELXS97 pro-
gram [12]. The hydrogen atoms bonded to carbon and
nitrogen were included in geometric positions and given
 M.G.B. Drew et al. / Inorganica Chimica Acta 360 (2007) 3448–3451 3451

Table 2
Crystallographic data
DNP PdLCl2(1) PdL 0 Cl2(2)
Formula C11H11N3O2 PdCl2C11H13N3 PdCl2C13H17N3
M 217.23 364.54 392.60
Space group monoclinic, P21/n monoclinic, P21/n monoclinic, P21/c
Cell dimensions (Å, °)
a 7.931(1) 10.822(1) 9.458(2)
b 12.530(2) 14.937(2) 14.508(5)
c 10.677(14) 16.903(1) 11.776(3)
a (90) (90) (90)
b 95.89(1) 108.03(1) 114.05(1)
c (90) (90) (90)
U (Å3) 1055.5(2) 2598.4(4) 1475.6(7)
Z, dcalc (gm cm3) 4, 1.367 8, 1.864 4, 1.767
Number of reflections
Measured 6886 18 059 11 751
Reflections/constraints/parameters 3072/0/146 7477/0/307 5257/0/176
R1, wR2 (I > 2r(I)) 0.0640, 0.1856 0.0441, 0.0777 0.0481, 0.0877
R1, wR2 (all data) 0.0836, 0.1926 0.0828, 0.1230 0.0916, 0.0964
Largest peak/hole (e Å3) 0.475/0.520 2.509/1.558 1.269/0.676

thermal parameters equivalent to 1.2 times those of the
atom to which they were attached. Empirical absorption
corrections for 1 and 2 were carried out using the ABSPACK
program [13]. The structures were refined on F2 using
SHELXL97 [12].
Acknowledgements
M.G.B.D. thanks EPSRC and the University of Read-
ing for funds for the Oxford Instruments X-Calibur system.
S.N. thanks the Council of Scientific and Industrial Re-
search, Government of India, New Delhi for a fellowship.
Appendix A. Supplementary material
CCDC 617300, 617301 and 617302 contain the supple-
mentary crystallographic data for DNP, 1 and 2. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.ica.2007.04.013.
References
[1] J.C. Nelson, J.G. Saven, J.S. Moore, P.G. Wolynes, Science 277
(1997) 1793.
[2] V. Berl, I. Huc, R.G. Khoury, M.J. Krische, J.-M. Lehn, Nature 407
(2000) 720.
[3] A. Urbano, Angew. Chem., Int. Ed. 42 (2003) 3986.
[4] S. De, S. Chowdhury, D.A. Tocher, D. Datta, CrystEngComm. 8
(2006) 670.
[5] C. Piguet, Chem. Rev. 97 (1997) 2005.
[6] M.A. Albrecht, Chem. Rev. 101 (2001) 3457.
[7] V.G. Machado, P.N.W. Baxter, J.-M. Lehn, J. Braz. Chem. Soc. 12
(2001) 431.
[8] M.G.B. Drew, D. Parui, S. De, J.P. Naskar, D. Datta, Eur. J. Inorg.
Chem. (2006) 4026.
[9] E.C. Constable, S.M. Elder, J. Healy, M.D. Ward, D.A. Tocher, J.
Am. Chem. Soc. 112 (1990) 4590.
[10] A. Mukherjee, U. Subramanyam, V.G. Puranik, T.P. Mohandas, A.
Sarkar, Eur. J. Inorg. Chem. (2005) 1254.
[11] Crysalis, Oxford Diffraction Ltd., Version 1, 2005.
[12] SHELXS97 and SHELXL97 G.M. Sheldrick, Programs for Crystal
Structure Calculations, University of Gottingen, 1997.
[13] Abspack, Oxford Diffraction Ltd, 2005.