The synthesis and Crystal Structures of di-μ-dichloro-bis{[N,N- dimethylaminobenzyl-C1,N]dipalladium(II)} and of the Cocrystals of {chloro-(triphenylphosphino)-bis[N,N-dimethylaminobenzyl-C1,N] palladium(II)} and {trans-bis(triphenyl

Article abstract of DOI:10.1016/j.molstruc.2004.03.010

The X-ray crystal structures of cyclopalladated complexes are reported. Reaction of {[Pd(dmba)(μ-Cl)]₂}, (1), (dmba=N(CH₃) ₂CH₂C₆H₅) with triphenylphosphine gave crystals containing {chloro

Full text of DOI:10.1016/j.molstruc.2004.03.010

Journal of Molecular Structure 693 (2004) 241–246
www.elsevier.com/locate/molstruc
The synthesis and Crystal Structures of di-m-dichloro-
bis{[N,N-dimethylaminobenzyl-C1,N ]dipalladium(II)}
and of the Cocrystals of {chloro-(triphenylphosphino)-
bis[N,N-dimethylaminobenzyl-C1,N]palladium(II)}
and {trans-bis(triphenylphosphino)-chloro-
[N,N-dimethylaminobenzyl-C]palladium(II)}
a,
Ayfer Mentes , Raymond D.W. Kemmitt , John Fawcett , David R. Russell
b
c
c
*
aDepartment of Chemistry, Faculty of Arts and Sciences, Zonguldak Karaelmas University, Zonguldak,Turkey
bInorganic Research Laboratories Department of Chemistry, The University of Leicester, Leicester, LE1 7RH, UK
cX-Ray Crystallography Laboratory, Department of Chemistry, The University of Leicester, Leicester, LE1 7RH, UK
Received 10 November 2003; revised 8 March 2004; accepted 10 March 2004
Abstract
The X-ray crystal structures of cyclopalladated complexes are reported. Reaction of {[Pd(dmba)(m-Cl)]2}, (1), (dmba ¼ N(CH3)2-
CH2C6H5) with triphenylphosphine gave crystals containing {chloro–(triphenylphosphino)-bis[N,N-dimethylaminobenzyl-C1,N ]
palladium(II)} (2a) and {trans-bis(triphenylphosphino)-chloro-[N,N-dimethylaminozyl-C]palladium(II)} (2b). Complex (1) crystallises
in the space group P2ð1Þ=c with a ¼ 7:849ð1Þ A, b ¼ 15.635(3) A, c ¼ 8:352ð1Þ A, b ¼ 109:298, and Dcalc ¼ 1:895 g cm 23 for Z ¼ 2:
˚
˚
˚
˚
˚
˚
Complexes (2a) and (2b) crystallize together in the space group P2(1)/n with a ¼ 9:964ð2Þ A, b ¼ 34:228ð5Þ A, c ¼ 18:127ð3Þ A,
b ¼ 91:91 8, and Dcalc ¼ 1:439 g cm23
.
q 2004 Elsevier B.V. All rights reserved.
Keywords: X-ray structure; Cyclopalladated; Palladium(II); N,N-dimethylbenzylamine; Triphenylphosphine; Triphenylstibine
1. Introduction
Our interest in investigation of carbon-antimony bond
fission in reactions of triphenylstibine with palladium(II)
complex [14], led us to react dimeric complexes with
triphenylstibine and triphenylphosphines. Treatment of the
dimeric complex [Pd(dmba)(m–Cl)]2 (1) with triphenyl-
phosphine in a 1:4 molar ratio gives a mixture of cyclome-
tallated mononuclear complex [Pd(dmba)(Cl)(PPh3)], (2a),
and the mononuclear complex [Pd(dmba)(Cl)(PPh3)2], (2b),
in a typical bridge splitting reaction. Crystals isolated from
this mixture proved to be cocrystals of (2a) and (2b). The
reactions of triphenylstibine with dimeric complex (1) give
cyclometallated complex [Pd(dmba)(Cl)(SbPh3)], (3a), and
[Pd(dmba)(Cl)(SbPh3)2], (3b).
Benzylamines are prone to cyclometallation by
appropriate palladium(II) compounds. The usual
products are cyclopalladated dimers of general formula
{[Pd(L)(m-X)]2}, where X ¼ halide or OAc, L ¼
benzylamines [1–5]. Carbon-to-metal s-bonds also occur
with reaction of Pd(II) and differently substituted Schiff
bases ligands [6–13].
The insertion of an alkyne in the metal-carbon bond has
proved to be attractive for the selective syntheses of both
carbo- and heterocycles [8].
The synthesis of polynuclear cyclometallated palla-
dium(II) complexes and their reactivity towards mono-
and ditertiary phosphine have been studied [9,13].
2. Results and discussion
*
Corresponding author. Tel.: þ90-372-257-7225 fax: þ90-372-
The compounds described in this paper were character-
ized by elemental analysis (C, H, N), IR, 1H NMR,
2574181.
E-mail address: ayfermentes@yahoo.com (A. Mentes).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.03.010

242
A. Mentes et al. / Journal of Molecular Structure 693 (2004) 241–246
13C{1H}-NMR and 31P{1H} NMR spectroscopy and by
FAB-MS spectroscopy. The IR spectra of (1)–(3) showed
the nðC ¼ CÞ stretching at region 1576–1568 cm21. The
reaction of (1) and PPh3 in dichloromethane in 1:2 molar
ratio gave a mononuclear cyclometallated complex
[Pd(dmba)(PPh3)Cl], (2a). In the 1H NMR spectrum of
triplets at 6.87 and 6.40 ppm. which can be assigned to
aromatic protons of the benzyl group. The aromatic protons
of the SbPh3 ligands appeared as a multiplets in the range
7.65–7.35 ppm. Integration of these signals indicated that
a sample of (3a) has proved the formulation of mono-
nuclear cyclometallated complex [Pd(dmba)(SbPh3)Cl],
(3a), carbon-antimony bond fission was not observed.
The methyl groups bonded to nitrogen showed a singlet at
2.93 ppm. The 13C{1H}-NMR spectrum of the complex
(3a) proved the assignments of these aromatic groups.
FAB mass spectrum showed peak at m=z ¼ 630 for
[Pd(dmba)(SbPh3)Cl]þ and 594 for [Pd(dmba)(SbPh3)]þ.
The molecular structure of the complex (1) is shown in
Fig. 1 which also gives the crystallographic numbering
scheme. Selected bond distances and angles are given in
Table 1. In the complex (1) each dmba ligand is bonded to
the di-m-chloro-bridged unit through a nitrogen atom and an
aromatic carbon atom, providing two equivalent five-
membered N–C–Pd–C-chelate rings. The geometry at
the palladium in (1) is square planar with the two
cyclometallated ligands in a trans arrangement with respect
to the Pd…Pd axis.
(2a), the –CH2 –N resonance was
a
doublet
ðJðPHÞ ¼ 1:4 . Hz), showing coupling to the phosphorus
nucleus and the CH3–N resonance was also a doublet
ðJðPHÞ ¼ 2:4 Hz), showing coupling to the phosphorus
nucleus [4]. In the 31P{1H} spectrum the resonance of the
coordinated phosphine trans to the N atom in (2a) was a
singlet at d ¼ 42:49: FAB mass spectrum showed peak at
m=z ¼ 537 for [Pd(dmba)(PPh3)Cl]þ, and 502 for due to loss
of chlorine [Pd(dmba)(PPh3)]þ.
The reaction of (1) with PPh3 in dichloromethane in
1:4 molar ratio gave a mixture of mononuclear
cyclometallated complex [Pd(dmba)(PPh3)Cl], (2a), and
non-cyclometallated complex [Pd(dmba)(PPh3)2Cl], (2b).
Many attempts to chromatographic separation of the
reaction mixture on silica gel using variety of solvents
were unsuccessful. In the 1H NMR spectrum of (2b),
neither the (H6) nor the -CH2–N protons showed
coupling to the 31P-nucleus of the phosphine due to
opening of the cyclometallated ring. In the 31P{1H}
spectrum the resonance of the two trans phosphorus
atoms was a singlet 27.5 and broad singlet at d ¼ 43:37
for coordinated phosphine trans to the N atom [2,5].
FAB mass spectrum showed peak at m=z ¼ 800 for
[Pd(dmba)(PPh3)2Cl]þ, 538 for [Pd(dmba)(PPh3)2]þ.
13C{1H}-NMR spectra for (2a) and (2b) showed
resonances at d149:7; 147.4 (C1, C6) and 136.8 (C2) shifted
to higher frequency, confirming metallation of the organic
ligand.
˚
Pd(1)–C(1) bond, [1.961(3) A] is shorter than the
˚
expected value of 2.081 A based on the sum of the covalent
radii of carbon and palladium. This is consistent with those
found for related complexes where partial multiple-bond
character of the Pd–C was assumed [4,7].
˚
Pd(1)–N(1) bond distance [2.073(3) A] is in agreement
with the value based on the sum of covalent radii for
nitrogen and palladium [17] and similar to values reported
previously [4,7].
The lengths of the Pd–Cl bonds trans to C
˚
[2.4658(1) A], and the Pd–Cl bonds trans to N [2.327(1)
˚
A], parallel the different trans influences exerted by the
The reaction of (1) and SbPh3 in dichloromethane gave
the mononuclear cyclometallated complex [Pd(dmba)
1
(SbPh3)Cl], (3a). The H NMR spectrum of the complex
(3a) contained two doublets at 7.03 and 6.68 ppm and two
phenyl carbon and the nitrogen atoms. In the five-
membered chelate rings four atoms (Pd1, C1, C6 and
˚
C7) are essentially planar [0.0113 A maximum deviation]
˚
with the N1 atom 0.5494 A out of this plane. The bite angle
Fig. 1. Molecular structure of (1) showing the atom numbering scheme. Displacement parameters are shown at the 50% level. Hydrogen atoms are omitted for
clarity. The molecule is located on a centre of symmetry, the primed atoms are generated by symmetry (2x, 1 2 y, 2z).

A. Mentes et al. / Journal of Molecular Structure 693 (2004) 241–246
243
Table 1
˚
Selected bond distances (A) and bond angles (8) with estimated standard deviations in parenthesis for (1) and (2)
Complexes (1)
Complexes (2)
Bond distances
Pd(1)–Cl(1)
Pd(1)–C(1)
Pd(1)–N(1)
C(7)–N(1)
N(1)–C(8)
Pd(1)–Cl(1)
2.327(1)
1.961(3)
2.073(3)
1.502(4)
1.475(4)
2.4658(1)#1
Pd(1)–Cl(1)
Pd(2)–Cl(1a)
Pd(1)–N(1)
Pd(1)–P(1)
Pd(2)–P(1a)
Pd(2)–P(2a)
Pd(1)–C(4)
Pd(1)–C(4a)
2.3808(10)
2.402(1)
2.150(3)
2.246(1)
2.327(1)
2.321(1)
2.012(4)
2.009(4)
Bond angles
C(1)–Pd(1)–N(1)
C(1)–Pd(1)–Cl(1)
N(1)–Pd(1)–Cl(1)
N(1)–Pd(1)–Cl(1)#2
82.63(13)
94.98(10)
177.61(8)
96.59(8)
Cl(1)–Pd(1)–N(1)
N(1)–Pd(1)–P(1)
C(4)–Pd(1)–N(1)
C(4)–Pd(1)–Cl(1)
C(4a)–Pd(2)–Cl(1a)
P(1a)–Pd(2)–P(2a)
C(4a)–Pd(2)–P(1a)
C(4a)–Pd(2)–P(2a)
90.96(9)
175.45(9)
81.80(13)
170.29(11)
175.25(11)
164.23(4)
90.37(11)
89.58(11)
symmetry transformation used to generate equivalent atoms:#1 (2x, 1 2 y, 2 2 z) #2 (2x, 2 y þ 1, 2 z).
value [C(1)–Pd(1)–N(1) ¼ 82.63(13)8] is in good agree-
ment with these found in structurally related m–Cl
dimer [7].
trans phosphine donors and substituted phenyl group trans
to chlorine.
The Pd(1)–P(1), Pd(2)–P(1a), Pd(2)–P(2a) distances
˚
(2.246(1), 2.327(1), and 2.321(1) A, respectively) are
The molecular structure of the complex (2a), (2b) is
shown in Fig. 2 which also gives the crystallographic
numbering scheme. Selected bond distances and angles are
given in Table 1. The geometry at the palladium in (2a)
is square planar with the chlorine (Cl1) trans to the
Pd(1)–C(4) bond of the dimethylaminobenzyl ligand and
the triphenylphosphine group trans to the Pd(2)–N(1) bond.
The geometry at the palladium in (2b) is square planar with
similar to those in the palladium(II) phosphine complexes
[5,6,10,11].
˚
The Pd(1)–N(1) bond length of 2.150(3) A is longer than
those found in literatures [5,11]. The Pd(1)–C(4) and
˚
Pd(1)–C(4a) distances [2.012(4) and 2.009(4) A, respect-
ively] are also longer than that found in the related
complexes but the Pd(1)–Cl(1) distance in (2a)
Fig. 2. Molecular structure of (2a), (2b) showing the atom numbering scheme. Displacement parameters are shown at the 50% level. Hydrogen atoms are
omitted for clarity.

244
A. Mentes et al. / Journal of Molecular Structure 693 (2004) 241–246
˚
2.3808(10) A is similar to that found in (1) 2.327(1) A while
˚
Pd(2)–Cl(1a) (2b) distance 2.402(1) A is longer than that
found in the related complexes and consistent with the trans
influence of a phenyl group [10,11].
˚
3 h under N2. The solution was cooled to room temperature
and diethyl ether was added to precipitate yellow solid of
0.160 g (82% yield based on Pd) of [Pd(dmba)(PPh3)Cl]
(2a). M.p. 175–178 (dec.) 8C. (Found; C, 63.1; H, 5.1; N,
2.3. C27H27ClNPPd calc.; C, 60.2; H, 5.1; N, 2.6, %).
Fab–Mass m=z : 537 [M]þ, 502 [M–Cl]þ (100%.peak). 1H
NMR (Bruker–Avance 500 MHz, CDCl3) d ¼ 7:56–7:52
(m, 6H, PPh3), 7.23–7.06 (m, 9H, PPh3), 6.81 (d, 1H,
J(HH) ¼ 6.7 Hz, H3), 6.63 (t, 1H, J(HH) ¼ 7.2 Hz, H5), 6.16
(m, 2H, H4, H6), 3.88 (d, 2H, J(PH) ¼ 1.4, CH2), 2.66 (d, 6H,
J(PH) ¼ 2.4, N–CH3). 13C{1H}-NMR (Bruker-Avance
125 MHz, CDCl3) d ¼ 138:6; 137.3 (C1, C6); 136.0 (C2),
124.4, 123.2, 121.8 (C3, C4, C5); P-phenyl: 134.7, 129.9,
128.7, 127.4 (Co, Ci, Cp, Cm); 73.2 (N-CH3), 50.05
(–CH2–N). 31P–1{H} NMR (Bruker-Avance 202 MHz,
CDCl3) d ¼ 42:49 (s) ppm and small impurities at 23.44
3. Experimental
3.1. Instruments and reagents
All reactions were performed under a dry, oxygen-free,
nitrogen atmosphere, using solvents which were dried and
distilled under nitrogen prior to use.
Microanalysis were carried out by Butterworth Labora-
tories Ltd., 54–56 Waldegrave Rd., Teddington, Middles-
¨ ˙
sex, TW11 8LG and TUBITAK Marmara Research Center,
Turkey. Melting points were measured on a Reichert hot
stage apparatus and are uncorrected. The FAB mass
spectrum of the solid complexes were obtained on a Kratos
Concept Double Focusing Sector Mass Spectrometer. The
1H NMR spectra were recorded at room temperature in
[2H1] chloroform on a BRUKER ARX 250 spectrometer
operating at 250.13 MHz with SiMe4 (0.0 ppm) as internal
reference, 13C–{1H} NMR spectra were recorded at room
temperature in [2H1]chloroform on a BRUKER ARX 250
spectrometer operating at 62.9 MHz and the 31P–{1H}
NMR spectra were recorded in CDCl3 on a BRUKER ARX
250 spectrometer operating at 25.1 MHz unless otherwise
stated. The quoted IR spectra were recorded on a Perkin–
Elmer 580B spectrophotometer in Nujol mulls between
(s) ppm. (28:1 ratio). IR.: 1568 y(CyC), cm21
.
3.2.2.2. Reaction of (1) with PPh3: (2b). A mixture of
complex (1) (0.1 g, 0.18 mmol) and an excess of PPh3
(0.190 g, 0.72 mmol) was refluxed in 10 cm3 of dichloro-
methane for 3 h under N2. The solution was cooled to room
temperature and diethyl ether was added to precipitate
yellow solid of 0.225 g of [Pd(dmba)(PPh3)2Cl] (2b) and
small impurities of [Pd(dmba)(PPh3)Cl] (2a). M.p.
183–185 8C. (Found; C, 65.4; H, 5.2; N, 1.9. C45H42ClNP2-
Pd calc.; C, 67.5; H, 5.2; N, 1.8, %). Fab-Mass m/z: 800 [M]þ,
630 [M-2L]þ. 1H NMR (300 MHz, CD2Cl2) d ¼ 7.71–7.32
(m, PPh3), 7.00 (d, 1H, J(HH) ¼ 7 Hz, H3), 6.80 (td, 1H,
J(HH) ¼ 7 Hz, H5), 6.34 (m, 2H, H4, H6), 4.07 (s, 2H, CH2),
2.80 (s, 6H, N–CH3). 13C{1H}–NMR, (62.90 MHz, 298 K,
CDCl3,) d ¼ 149.7, 147.4 (C1, C6), 136.8 (C2), 123.9, 122.8,
121.4 (C3, C4, C5); P-phenyl: 134.0, 130.9, 129.5, 127.2 (Co,
Ci, Cp, Cm); 72.1 (N–CH3), 49.43 (–CH2–N). 31P–1{H}
NMR (101.25 MHz, 298 K, CD2Cl2) d ¼ 27:5(s) ppm for
NaCl plates in the range 3000–600 cm21
.
3.2. Synthesis
3.2.1. Preparation of compounds (1)
The synthesis of complex (1) has been previously
reported [1]. A heterogeneous mixture of N,N-dimethyl-
benzylamine, (dmba), (1.35 g, 10 mmol) and palladium(II)
dichloride (0.875 g, 5 mmol) in 50 cm3 of methanol
was stirred at room temperature. After 4 h, all of the
palladium(II) dichloride had dissolved and was replaced by
a yellow-brown crystalline solid of (1). The complex was
recystallized from boiling benzene/n-hexane to obtain 1.2 g
(44% yield based on Pd) of [Pd(dmba)(m–Cl)]2. M.p. 188–
190 8C. (Found; C, 39.5; H, 4.2; N, 5.1. C18H24Cl2N2Pd2
calc.; C, 39.1; H, 4.3; N, 5.0, %). Fab–Mass: 552 [Mþ]. 1H
NMR (250 MHz, CDCl3) d ¼ 7:10 (t, 1H, J(HH) ¼ 7 Hz,
H4), 6.89 (t, 1H, J(HH) ¼ 7 Hz, H5), 6.82 (d, 1H,
J(HH) ¼ 7 Hz, H3, H6), 3.86 (s, 2H, CH2), 2.77 (d, 6H,
(2b) and 43.37 (br s) ppm for (2a). IR.: 1576 y(CyC), cm21
.
3.2.2.3. Reaction of (1) with SbPh3: (3a). Complex (1)
(0.1 g, 0.18 mmol) and SbPh3 (0.130 g, 0.36 mmol) were
refluxed in 10 cm3 of dichloromethane for 5 h under N2. The
solution was cooled to room temperature and diethylether
was added to precipitate yellow solid of 0.100 g (44% based
on Pd) of [Pd(dmba)(SbPh3)Cl], (3a). M.p. 159–160 8C.
(Found; C, 51.4; H, 4.2; N, 2.0. C27H27ClNSbPd calc.; C,
51.5; H, 4.3; N, 2.2, %). Fab-Mass m/z: 630 [M]þ, 594 [M–
1
Cl]þ. H NMR (CDCl3) d ¼ 7:65–7:35 (m, 15H, SbPh3),
7.03 (d, 1H, J(HH) ¼ 7 Hz, H3), 6.87 (t, 1H, J(HH) ¼ 7 Hz,
H4), 6.68 (d, 1H, J(HH) ¼ 8 Hz, H6), 6.40 (t, 1H,
J(HH) ¼ 7 Hz, H5), 4.10 (s, 2H, CH2), 2.93 (s, 6H,
N–CH3). 13C{1H}-NMR, d ¼ 149:7; 145.8, 140.6 (C1,
C6, C2), 125.8, 124.7, 123.2 (C3, C4, C5); Sb-phenyl:
136.9, 131.3, 130.5, 129.5 (Co, Ci, Cp, Cm); 73.8 (N–CH3),
J(HH) ¼ 5 Hz, N–CH3). IR.: 1576 y(CyC), cm21
3.2.2. Reaction of (1) with PPh3 and SbPh3
.
51.3 (–CH2–N). IR.: 1568 y(CyC), cm21
.
3.2.2.1. Reaction of (1) with PPh3: (2a). A mixture of
complex (1) (0.1 g, 0.18 mmol) and PPh3 (0.095 g,
0.36 mmol) was refluxed in 10 cm3 of dichloromethane for
3.2.2.4. Reaction of (1) with SbPh3: (3b). Complex (1)
(0.1 g, 18 mmol) and SbPh3 (0.260 g, 0.72 mmol) were

A. Mentes et al. / Journal of Molecular Structure 693 (2004) 241–246
245
refluxed in 10 cm3 of dichloromethane for 5 h under N2. The
solutionwascooled toroom temperatureanddiethyletherwas
addedtoprecipitateyellowsolidof0.300 g(85%basedonPd)
of [Pd(dmba)(SbPh3)2Cl], (3b). M.p. 138–140 (dec.) 8C.
(Found; C, 55.9; H, 4.4; N, 1.0. C45H42ClNSb2Pd calc.; C,
54.9; H, 4.3; N, 1.4, %). Fab-Mass m/z: 982 [M]þ, 947
[M–Cl]þ. 1H NMR (Bruker–Avance 500 MHz, CDCl3)
d ¼ 7.56 2 7.15 (m, 30H, SbPh3), 6.85 (d, 1H,
J(HH) ¼ 7.3 Hz, H3), 6.70 (t, 1H, J(HH) ¼ 7.3 Hz, H4),
6.51 (d, 1H, J(HH) ¼ 7.7 Hz, H6), 6.24 (t, 1H,
J(HH) ¼ 7.5 Hz, H5), 3.92 (s, 2H, CH2), 2.76 (s, 6H, N–
CH3). 13C{1H}-NMR (Bruker-Avance 500 MHz, CDCl3),
d ¼ 140:9;139.6(C1,C6),126.1,125.0,123.7,122.2(C2,C3,
C4, C5); Sb-phenyl: 137.1, 135.9, 133.8, 129.5 (Co, Ci, Cp,
Cm); 73.5 (N–CH3), 50.3 (CH2). IR.: 1576 y(CyC), cm21
.
3.3. X-ray crystallography
Crystals of (1) and (2a), (2b) suitable for X-ray crystallo-
graphic analysis were grown from hot benzene/ n-hexane
and dichloromethane/diethyl ether at room temperature,
respectively, Scheme 1. The crystal data, a summary of
Scheme 1. (i) PdCl2 (methanol); (ii) PPh3 or SbPh3 (dichloromethane).
Table 2
Crystallographic data and parameters of the complexes (1) and (2)
Compound
(1)
(2)
Empirical formula
Formula weight
Temperature
C18H24Cl2N2Pd2
552.09
C72H69Cl2N2P3Pd2
1338.90
190(2) K
˚
0.71073 A
190(2) K
˚
0.71073 A
Wavelength
Crystal system
Space group
Monoclinic
Monoclinic
P21=c
P21=n
Unit cell dimensions
˚
7.849(1) A
˚
15.635(3) A
˚
8.352(1) A
˚
9.964(2) A
˚
34.228(5) A
˚
18.127(3) A
a
b
c
a
b
g
908
109.298
908
908
91.918
908
3
˚
3
˚
Volume
967.4(3) A
6179(2) A
Z
2
4
Density (calculated)
Absorption coefficient
F(000)
1.895 Mg m23
0.2137 mm21
544
1.439 Mg m23
0.791 mm21
2744
Crystal size
0.66 £ 0.51 £ 0.38 mm
2.61–248
0.74 £ 0.68 £ 0.52 mm
2.54-24.08
Theta range for data collection
Index ranges
21 # h # 8, 21 # k # 17, 29 # l # 9
2023
-1 # h # 11, -1 # k # 39, -20 # l # 20
11986
Reflection collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I . 2sigma(I)]
R indices (all data)
Largest diff. peak and hole
1508 [R(int) ¼ 0.0254]
Full-matrix least-squares on F2
1508/0/111
9696 [R(int) ¼ 0.0251]
Full-matrix least-squares on F2
9696/0/734
1.183
1.070
R1 ¼ 0.0231, wR2 ¼ 0.0614
R1 ¼ 0.0237, wR2 ¼ 0.0617
R1 ¼ 0.0348, wR2 ¼ 0.0731
R1 ¼ 0.0501, wR2 ¼ 0.0794
23
23
˚
0.307 and 20.597 e A
˚
0.556 and 20.545 e A
˚
Details in common: Siemens P4 diffractometer monochromated Mo–Ka radiation ðl ¼ 0:7107 A) omega scans, R1 ¼ SllFo–lFcll=SlFol;
2
2
2
1=2
wR2 ¼ ½wðFo2 –Fc2Þ =ðFo2Þ ꢀ1=2; goodness of fit s ¼ ½SwðFo2 –Fc2Þ =ðn–pÞꢀ where n ¼ number of reflections and p ¼ total number of parameters,
w ¼ 1=½s2ðFo2Þ þ ðaPÞ þ bPꢀ where P ¼ ðFo2 ¼ Fc2Þ=3:
2

246
A. Mentes et al. / Journal of Molecular Structure 693 (2004) 241–246
the data collection and structure refinement parameters are
given in Table 2. Crystals were glued on glass fibers. Unit cell
dimensions were determined by least squares refinement of
optimised setting angles. The data were corrected for Lorentz
and polarisation effects, and empirical absorption corrections
were applied. The structures were solved by Patterson
methods (SHELXTL PC) [15], and refined by full matrix
least squares using SHELXL 96 [16]. H atoms were included in
calculated positions. The Methyl H atoms had isotropic
displacement parameters fixed at 1.5 Ueq of the bonded atom
for all other H atoms the value of 1.2 Ueq of the bonded atom
was used. All non H atoms were refined with anisotropic
displacement parameters.
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We thank to Zonguldak Karaelmas University for
financial support of this project (Project No: 98-111-003-
15). We also thank to University of Leicester, UK, for
laboratory facilities, and Johnson Matthey plc for the supply
of palladium metal salts.
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