Complexes of Ni(II) and Pd(II) ions with 15- and 17-membered macrocycles containing O2N2- and O2N3-donors and the crystal structures of Ni(II) and Pd(II) complexes of 2,5-dioxa-13,16,19-triazatricyclo[19.4.0.06,11]-pentacosa-6,8,10,21, 23,25(1)-hexaene

Article abstract of DOI:10.1016/j.molstruc.2003.11.035

The interactions of O₂N₂- and O₂N ₃-donor macrocycles with Ni(II) and Pd(II) have been investigated and four new complexes (L¹a, L²a, L²b and L²c) were synthesized. In rigid 15-membered macrocyclic complex (L¹a), the etheric oxygens are coordinated to the metal ion, while in the more flexible 17-membered macrocyclic complexes (L²a, L ²b and L²c) the etheric oxygens are not bonded to the metal ions. Comparative FTIR, FAB, TGA, DSC, ¹H- and ¹³C-NMR, elemental analyses, magnetic measurements as well as X-ray structure analysis (on two complexes, L²a and L²b) have been used to elucidate the nature of the species formed. The Ni(II) complexes (L¹a and L²a) were found to be octahedral geometry while the Pd(II) complexes (L²b and L²c) were square planar structure. The 1,4,7-triazaheptane macrocyclic fragment in L²a was co-ordinated to Ni(II) ion in a facial manner as supported by the X-ray structural analysis. Two types of Pd(II) complexes have been isolated with acetate ligand, the more insoluble form contains three water molecules without bonding to Pd(II) ion, the other one has not contained any water molecule as proven by TGA and DSC data. L²a crystallizes in the monoclinic space group P2₁/n with a=15.820(1), b=8.237(2), c=17.529(1)?, β=93.17(1)°, V=2280.7(5)?³, Z=4 and D _x=1.527gcm^-3. The complex has a distorted octahedral structure, incorporating the three nitrogen donors of the macrocyclic ring, two oxygen atoms of the bidentate and one oxygen atom of the monodentate nitrate ions. L²b crystallizes in the orthorhombic space group P cab with a=13.791(2), b=14.620(1), c=28.295(2)?, V=5705.0(9)?³, Z=8 and D_x=1.444gcm^-3. The complex contains a mononuclear Pd(II) ion in which there are three water molecules, together with one acetate ion and one acetate ligand bonded to Pd(II). The hydrogen bonds are highly effective between the water molecules, acetate ions and the macroring for stabilizing the molecule as a whole. The coordination around Pd(II) is a distorted square planar. But the close contact of the second O atom of the acetate ligand may cause to a distorted square pyramidal coordination geometry around Pd(II).

Full text of DOI:10.1016/j.molstruc.2003.11.035

Journal of Molecular Structure 691 (2004) 85–96
www.elsevier.com/locate/molstruc
Complexes of Ni(II) and Pd(II) ions with 15- and 17-membered
macrocycles containing O N - and O N -donors and the crystal structures
2
2
2 3
of Ni(II) and Pd(II) complexes of 2,5-dioxa-13,16,19-triazatricyclo
[
6,11
19.4.0.0 ]-pentacosa-6,8,10,21,23,25(1)-hexaene
a
Selen Bilge , Zeynel Kılı c¸ , Tuncer H o¨ kelek , Baki Erdogan
a,
b
c
*
˘
a
Department of Chemistry, Ankara University, 06100 Tando g˘ an-Ankara, Turkey
b
Department of Physics, Hacettepe University, 06532 Beytepe-Ankara, Turkey
c
Department of Chemistry, Gazi University, 06500 Be s¸ evler-Ankara, Turkey
Received 18 August 2003; accepted 17 November 2003
Abstract
The interactions of O
1
2
2
N
2
- and O
L b and L c) were synthesized. In rigid 15-membered macrocyclic complex (L a), the etheric oxygens are coordinated to the metal ion,
2 3
N -donor macrocycles with Ni(II) and Pd(II) have been investigated and four new complexes (L a, L a,
2
2
1
2
while in the more flexible 17-membered macrocyclic complexes (L a, L b and L c) the etheric oxygens are not bonded to the metal ions.
2
2
1
Comparative FTIR, FAB, TGA, DSC, H- and C-NMR, elemental analyses, magnetic measurements as well as X-ray structure analysis (on
13
2
2
1
2
two complexes, L a and L b) have been used to elucidate the nature of the species formed. The Ni(II) complexes (L a and L a) were found
2
to be octahedral geometry while the Pd(II) complexes (L b and L c) were square planar structure. The 1,4,7-triazaheptane macrocyclic
2
2
fragment in L a was co-ordinated to Ni(II) ion in a facial manner as supported by the X-ray structural analysis. Two types of Pd(II)
complexes have been isolated with acetate ligand, the more insoluble form contains three water molecules without bonding to Pd(II) ion, the
2
other one has not contained any water molecule as proven by TGA and DSC data. L a crystallizes in the monoclinic space group P2 =n with
1
3
23
˚
˚
a ¼ 15:820ð1Þ; b ¼ 8:237ð2Þ; c ¼ 17:529ð1Þ A, b ¼ 93:17ð1Þ8; V ¼ 2280:7ð5Þ A , Z ¼ 4 and D ¼ 1:527 g cm . The complex has a
x
distorted octahedral structure, incorporating the three nitrogen donors of the macrocyclic ring, two oxygen atoms of the bidentate and one
2
oxygen atom of the monodentate nitrate ions. L b crystallizes in the orthorhombic space group P cab with a ¼ 13:791ð2Þ; b ¼ 14:620ð1Þ;
3
23
˚
˚
c ¼ 28:295ð2Þ A, V ¼ 5705:0ð9Þ A , Z ¼ 8 and D ¼ 1:444 g cm . The complex contains a mononuclear Pd(II) ion in which there are three
x
water molecules, together with one acetate ion and one acetate ligand bonded to Pd(II). The hydrogen bonds are highly effective between the
water molecules, acetate ions and the macroring for stabilizing the molecule as a whole. The coordination around Pd(II) is a distorted square
planar. But the close contact of the second O atom of the acetate ligand may cause to a distorted square pyramidal coordination geometry
around Pd(II).
q 2003 Elsevier B.V. All rights reserved.
Keywords: Dibenzo-bis-imino crown ether; Dibenzo-triaza crown ether; Dibenzo-bis-imino crown ether complex; Dibenzo-triaza crown ether complex; TGA
and DSC data of Ni(II) and Pd(II) complexes
1
. Introduction
[1–3]. On the other hand, the transition metal ion
recognition with particular metal-ion binding applications
are of fundamental importance to broad areas of coordi-
nation- and bio-chemistry [4]. A large number of open-
chain and macrocyclic multidentate ligand complexes have
been investigated extensively, in order to understand their
synthetic, thermodynamic and/or structural properties of
complex formation [2,5–8]. Our research group have also
been investigated the structures of a series of free
macrocyclic multidentate O N donor-type ligands [9–15].
Macrocyclic multidentate O N ðx; y ¼ 2; 3; · · ·Þ donor-
x
y
type ligands lie at the focal point formed from different
fields of research, including the potential transition metal
ion selective reagents, coordination complexes and catalysts
*
Corresponding author. Tel.: þ90-312-212-67-20; fax: þ90-312-223-
3-95.
E-mail address: zkilic@science.ankara.edu.tr (Z. Kılı c¸ ).
2
x
y
0022-2860/$ - see front matter q 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2003.11.035

86
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
Scheme 1.
1
In this study, the macrocyclic multidentate ligands (L
were obtained on a Bruker DPX FT-NMR (400 MHz)
spectrometer (SiMe , as internal standard and 85% H PO
4
2
and L ) [16,17] and their Ni(II) and Pd(II) complexes (L a,
1
4
3
2
L a–L c) have been synthesized (Scheme 1).
2
as an external standard). IR spectra were recorded on a
Mattson 1000 FTIR spectrometer in KBr discs and were
1
13
The FTIR, H-, C-NMR and MS spectroscopic data,
TGA and DSC results of the newly synthesized products
2
with the crystal structures of complexes (L a and L b) are
2
reported in cm units. Microanalyses were carried out by
1
2
¨
˙
the microanalytical service of TUBITAK (Turkey), electron
impact (EI) and fast atomic bombardment (FAB) spectra
were obtained on the PLATFORM II LC-MS and VG-
ZAPSPEC spectrometers. Thermogravimetric curves of
recently dried samples were recorded using a Du Pont
reported.
2
. Experimental
2
Instruments, using ca. 5 mg sample mass and a platinum
050 thermogravimetric analyser (TGA) system. TA
2
.1. Reagents and techniques
21
sample holder. Heating rate of 5 8C min under dry N2
2
1
Melting points were measured on a Gallenkamp
atmosphere (60 mL min ) was investigated. DSC curves
of samples were recorded on Du Pont 2010 DSC thermal
1
13
apparatus using a capillary tube H-, C-, P-NMR spectra
31

S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
87
analyser, TA Instruments, in a covered aluminium sample
holder with a central pinhole and a sample mass of ca. 4 mg
dppm, 61.0 (N–CH –CH ); 67.3 (N–C H ); 72.2 (Ar–
2 2 2
C H –N); 78.9 (Ar–O–C H ); 109.4, 118.1, 128.5, 132.6,
2
2
2
1
3
21
under a 10 8C min
dynamic air flow. Magnetic moments were determined at
3 8C using a Faraday balance calibrated against
Hg[Co(NCS)4].
heating rate and 100 cm min
141.0, 168.9 (aromatic-C).
6
,11
{2,5-Dioxa-13,16,19-triazatricyclo[19.4.0.0 ]-penta-
cosa-6,8,10,21,23,25(1)-hexaene diacetato} palladium(II).
2
2
trihydrate, [Pd(L )(CH COO)]CH COO.3H O, (L b) and
2
3
3
2
6
,11
{
2,5-Dioxa-13,16,19-triazatricyclo[19.4.0.0 ]-penta-
cosa-6,8,10,21,23,25(1)-hexaene diacetato} palladium(II),
2
.2. Synthetic procedures
,5-Dioxa-13,17-diazatricyclo[17.4.0.0 ]-tricosa-
2
Pd(L )(CH COO)]CH COO, (L c): To a solution of (L )
2
2
[
3 3
6
,11
2
,8,10,12,17,19,21,23(1)-octaene, (L ): Ligand (L ) was
(0.11 g, 0.32 mmol) in dichloromethane (50 ml) was added
dropwise a solution of Pd(CH COO) (0.07 g, 0.32 mmol)
1
1
6
prepared according to the literature method [16], H NMR
3
2
1
in dichloromethane (30 ml). The mixture was refluxed for
5 h and then cooled and filtered. The residue was dissolved
in trichloromethane (30 ml) and set aside for crystallization
3
(
CDCl ): d , 2.32 (m, 2H, N–CH –CH ), J ¼ 5.3 Hz;
3
ppm
2
2
HH
3
3
CH ); 6.98–8.02 (m, 8H, aromatic-H); 8.74 (s, 2H, HCyN);
.63 (t, 4H, N–CH ), J ¼ 5.3 Hz; 4.42 (s, 4H, Ar–O–
2
HH
2
of (L b) at an ambient temperature, yield 0.13 g (33%), m.p.
2
1
3
1
C NMR (CDCl ): d , 29.0 (N–CH –C H ); 58.2 (N–
3
174 8C, H NMR (CDCl
3
): dppm, 1.32 (b, 3H, CH
–C(O)–O); 2.72 (m, 4H, N–CH
CH ); 2.86 (m, 4H, N–CH ); 3.10 (b, 3H, N–H); 3.68
3
–C(O)–
ppm
2
2
C H ); 68.2 (Ar–O–CH ); 113.9, 122.2, 126.0, 127.6,
2
O), 1.90 (b, 3H, CH
3
–
2
2
1
32.2, 159.0 (aromatic-C); 159.2 (HCyN).
,5-Dioxa-13,16,19-triazatricyclo[19.4.0.0 ]-penta-
2
2
6
,11
2
cosa-6,8,10,21,23,25(1)-hexaene, (L ): Ligand (L ) was
1
obtained by the published procedure [17], H NMR
(m, 2H, Ar–O–CH ), 3.92 (m, 2H, Ar–O–CH ); 4.39 (m,
2 2
2
2
2H, Ar–CH –N), 4.82 (m, 2H, Ar–CH –N); 6.92–7.41 (b,
2 2
13
8H, aromatic-H), 9.68 (b, 1H, CH –C(O)O· · ·H),
3
C
(
CDCl ): d , 2.33 (s, 3H, N–H); 2.73 (t, 4H, N–CH –
2
NMR (CDCl ): d , 22.8, 25.0 (C H –C(O)O); 52.1 (N–
3 ppm 3
CH –C H ); 53.2 (N–C H ); 55.8 (Ar–C H –N); 67.3
2 2 2 2
3
3
ppm
3
CH ), J ¼ 5.0 Hz; 2.85 (t, 4H, N–CH ), J ¼ 5.0 Hz;
2
HH
2
HH
3
7
.96 (s, 4H, Ar–CH –N); 4.54 (s, 4H, Ar–O–CH ); 7.06–
2
(Ar–O–C H ); 111.8, 120.7, 121.7, 131.0, 133.9, 158.6
2
2
1
3
.43 (m, 8H, aromatic-H), C NMR (CDCl ): dppm; 49.0
(aromatic-C); 178.0, 180.1 (CH –C(O)O). The mother
3
3
(
(
(
N–CH –C H ); 49.4 (N–CH ); 51.2 (Ar–CH –N); 67.4
2
liquor was evaporated and the residue was redissolved in
dichloromethane (25 ml). The mixture was filtered off and
2
2
2
Ar–O–C H ); 111.3, 121.0, 128.8, 129.1, 131.5, 157.6
2
2
set aside for crystallization of (L c), yield 0.09 g (47%),
aromatic-C).
6
,11
1
{
2,5-Dioxa-13,17-diazatricyclo[17.4.0.0 ]-tricosa-
,8,10,12,17,19,21,23(1)-octaene dinitrato} nickel(II) dihy-
m.p. 181 8C, H NMR (CDCl
3
): dppm, 1.28 (b, 3H, CH
–C(O)–O); 2.71 (m, 4H, N–
); 2.87 (m, 4H, N–CH ); 3.00 (b, 3H, N–H); 3.63
(m, 2H, Ar–O–CH ), 3.86 (m, 2H, Ar–O–CH ); 4.34 (m,
3
–
6
drate, [Ni(L )(NO ) ]·2H O, (L a): To a solution of (L )
(0.50 g, 1.51 mmol) in butanol (50 ml) was added dropwise
a solution of Ni(NO ) ·6H O (0.44 g, 1.51 mmol) in
C(O)–O), 1.85 (b, 3H, CH
CH –CH
3
1
1
1
3
2
2
2
2
2
2
2
2H, Ar–CH –N), 4.77 (m, 2H, Ar–CH –N); 6.89–7.37 (b,
2
3
2
2
2
1
3
8H, aromatic-H), 9.51 (b, 1H, CH –C(O)O· · ·H), C NMR
n-butanol (10 ml). The mixture was refluxed for 7 h and
then the solvent was removed under reduced pressure. The
crude dark blue powder product was crystallized from n-
3
(CDCl þ CH Cl ): d , 22.9, 25.0 (C H –C(O)O); 67.3
3
2
2
ppm
3
(Ar–O–C H ); 111.8, 120.7, 121.8, 131.0, 132.0, 158.6
2
butanol/H O mixture (100:1), yield 0.71 g (89%), 240 8C
2
(aromatic-C); 178.0, 180.1 (CH –C(O)O).
3
1
decompose), H NMR (DMSO): dppm, 2.69 (b, 2H, N–
(
CH –CH ); 3.59 (b, 4H, N–CH ); 4.54 (b, 4H, Ar–O–
2.3. Crystallography
2
2
2
CH ); 7.14–7.98 (b, 8H, aromatic-H); 8.71 (b, 2H, HCyN),
2
1
3
2
The suitable crystals of L a and L b for X-ray analysis
2
C NMR [D –(CH ) CO þ D O]: dppm, 29.1 (N–CH2–
6
3 2
2
C H ); 60.2 (N–C H ); 70.6 (Ar–O–CH ); 116.9, 124.4,
2
were obtained by recrystallization from n-butanol/THF/H O
2
2
2
1
29.7, 131.0, 140.0, 161.9 (aromatic-C); 164.4 (HCyN).
6
(79:29:1) mixture and trichloromethane, respectively.
Experimental data, methods and the procedure used to
elucidate the structure and other related parameters are
,11
{
2,5-Dioxa-13,16,19-triazatricyclo[19.4.0.0 ]-penta-
cosa-6,8,10,21,23,25(1)-hexaene dinitrato} nickel(II),
2
2
2
Ni(L )(NO ) ], (L a): To a solution of (L ) (0.50 g,
2
2
[
given in Table 1. For L a and L b, empirical absorption
corrections based on a series of psi-scans were applied to
the data. The structures of the complexes were solved by
3
2
1.47 mmol) in n-butanol (35 ml) was added dropwise a
solution of Ni(NO ) ·6H O (0.43 g, 1.47 mmol) in n-
3
2
2
2
butanol (15 ml). The mixture was refluxed for 7 h, and the
solvent was evaporated under reduced pressure. The crude
purple powder product was crystallized from n-
direct methods, SHELXS-97 [18]. For L a, atoms H2 and
H3 were located in a difference synthesis and refined
isotropically. The remaining H atoms were positioned
˚
˚
geometrically at distances of 0.97 A (CH ), 0.93 A (CH)
butanol/THF/H O mixture (70:29:1), yield 0.65 g (85%),
2
2
1
˚
and 0.91 A (NH) from the parent C and N atoms; a riding
2
dppm, 3.32 (b, 4H, N–CH –CH ); 3.41 (b, 4H, N–CH );
79 8C (decompose), H NMR [D –(CH ) CO þ D O]:
6
3 2
2
2
model was used during the refinement process. For L b,
2
2
2
0
00
0
00
0
00
5
.11 (b, 4H, Ar–CH –N); 5.49 (b, 4H, Ar–O–CH ); 7.83–
2
atoms H7 , H7 , H8 , H8 , H9 , H9 , H21 and H31 were
located in a difference synthesis and refined isotropically.
2
1
3
9
.79 (b, 8H, aromatic-H), C NMR [D –(CH ) CO þ D O]:
6
3 2
2

88
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
Table 1
Experimental data
2
L a)
2
(L b)
(
Compound
C
20
H
29
N
5
O
9
Ni
24 39 3 9
C H N O Pd
Color/shape
Purple/prism
524.18
Dark yellow/plate
619.98
Formula weight
Space group
P2 =n
1
P cab
Temperature (K)
Cell constants
293
293
˚
˚
˚
˚
a ¼ 15:820ð1Þ A, b ¼ 8:237ð2Þ A,
a ¼ 13:791ð2Þ A, b ¼ 14:620ð1Þ A,
˚
˚
c ¼ 17:529ð1Þ A, b ¼ 93:17ð1Þ8
c ¼ 28:295ð2Þ A
3
Cell volume (A )
˚
2280.7(5)
5705.0(9)
Formula units/unit cell
2
4
8
3
)
Dcalc (Mg m
2
1.527
1.444
1
)
mcalc (mm
Diffractometer/scan
0.908
0.703
Enraf-nonius CAD-4/v-2u
ꢀ
Enraf-nonius CAD-4/v-2u
ꢀ
Radiation used, graphite monochromator
3
Maximum crystal dimension (mm )
Mo Ka ðl ¼ 0:71073 AÞ
Mo Ka ðl ¼ 0:71073 AÞ
0.15 £ 0.25 £ 0.35
0.15 £ 0.25 £ 0.35
Standard reflections
Decay of standard (%)
Reflections measured
3
3
,1
3610
,1
5459
2
u(max)(8)
Range of h; k; l
26.30
26.29
0 , h , 19; 210 , k , 0; 217 , l , 21
2456
0 , h , 17; 218 , k , 0; 235 , l , 0
3069
Number of reflections with I . 2sðIÞ
Corrections applied
Lorentz-polarization and absorption
SHELX-97 [18], ORTEP-3 [19]
Int. Table for X-ray Cryst. vol. IV, 1976 [20]
Direct methods
Lorentz-polarization and absorption
SHELX-97 [18], ORTEP-3 [19]
Int. Table for X-ray Cryst. vol. IV, 1976 [20]
Direct methods
Computer programs
Source of atomic scattering factors
Structure solution
Treatment of hydrogen atoms
No. of parameters var.
Weight
Geometric calculation and difference map
315
Geometric calculation and difference map
361
2
2
2
2
2
2
w ¼ 1=½s ðF Þ þ ð0:0778PÞ þ 0:7618Pꢀ
w ¼ 1=½s ðF Þ þ ð0:0482PÞ þ 0:04Sinu=lꢀ
o
o
2
o
2
c
2
o
2
c
where P ¼ ðF þ 2F Þ=3
where P ¼ 0:33333F þ 0:66667F
GOF
1.096
0.935
R ¼ SðlF l 2 lF lÞ=SlF l
0.0396
0.1101
0.521
0.0384
0.0982
0.521
o
c
o
2
2
1=2
R
w
¼ ½SðwlF l 2 lF lÞ =wlF l ꢀ
23
˚
max
o
c
o
ðDrÞ
(eA )
2
3
˚
ðDrÞ (eA
min
)
20.627
20.338
2
L a) of (L and L ) were obtained from the reaction of
1
2
The remaining H atoms were positioned geometrically at
1
2
˚
˚
˚
distances of 0.97 A (CH ), 0.96 A (CH ), 0.93 A (CH) and
(L ) and (L ) with Ni(NO ) ·6H O in n-butanol, respect-
3 2 2
2
3
1
ively. In the (L a) and (L a) complexes, two NO ligands
2
˚
0.91 A (NH) from the parent C and N atoms; a riding
model was used during the refinement process.
3
1
are coordinated to Ni(II) ions as monodentate in (L a) and
2
as monodentate and bidentate in (L a) which was
supported by X-ray crystallography. These complexes
1
(L a and L a) have less solubilities in most of the organic
2
3
. Result and discussion
1
solvents, but L a is soluble in DMSO and acetone/H O
2
2
mixture and L a is soluble in acetone/H
3
.1. Synthesis and reactions
2
O mixture. The
reaction of (L ) with Pd(CH COO) in dichloromethane
2
3
2
1
Dibenzo-bis-imino-crown ether (L ) and dibenzo-triaza
2
yield a mixture of complexes (L b and L c). Both
2
2
2
complexes (L b and L c) are suggested to be monomeric
2
crown ether (L ) have been synthesized from the reaction
of 1,4-bis(formylphenyl)-1,4-dioxabutane with 1,3-diami-
nopropane and 1,3-diamino-3-azapentane, respectively,
according to the literature method [16,17]. The syntheses
structure containing two acetate ions, one of the acetate ion
2
bonded to Pd(II) as a ligand. On the other hand, in (L a),
2
(L b) and (L c), the etheric oxygens are not bonded to the
2
1
1
1
metal ions, although; in (L a), the etheric oxygens are
of [Ni(L )X ] (X ¼ Cl; Br, I, NCS), [Cu(L )](ClO ) ,
2
4 2
1
1
[
(
[
Cu(L )(X)]ClO (X ¼ Cl; Br, NCS), [Cu(L )(Br)]Y
bonded to Ni(II) ion, which are in accordance with the
observations reported in the literature [16,22,23,25,26].
4
1
2
Y ¼ BF ; PF ), [Cd(L ) ](ClO ) ·H O, [Ni(L )(Cl)]ClO ,
4
6
2
4 2
2
4
2
Ni(L )(NCS) ]·H O, {[Ni(L )(NCS) ]} and [Cu(L )(X)]
2
2
1
The analytical and experimental details of the ligands (L
2
2
2
2
2
1
2
2
ClO (X ¼ Cl; Br) and the crystal structures of some of
and L ) and their complexes (L a and L b–L c) are given
in Table 2, which are in accordance with the proposed
structures.
4
them have been previously reported in the literature [2,16,
1
1
7,21–24]. However, the new Ni(II) complexes (L a and

S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
89
Table 2
Analytical and experimental details
a
meff B.M.
Compound
Formula
Color
Elemental analyses (%) calculated (found)
C
H
N
1
L
C
19
C
20
C
19
C
20
C
24
C
24
H
20
H
27
H
24
H
27
H
39
H
33
N
2
N
3
N
4
N
5
N
3
N
3
O
O
O
O
O
O
2
2
–
–
74.00 (74.40)
70.35 (70.70)
43.29 (43.26)
45.83 (46.17)
46.49 (46.59)
50.97 (50.49)
6.54 (5.79)
7.97 (8.00)
4.59 (3.66)
5.19 (5.77)
6.34 (6.57)
5.84 (5.58)
9.08(8.69)
2
L
–
–
12.31 (12.31)
10.63 (10.36)
13.36 (13.83)
6.78 (6.57)
1
L a
1
10Ni;[NiL (NO
3
)
2
]·2H
2
O
Dark blue
Purple
Dark yellow
Brown
2.86
2
L a
2
Ni;[NiL (NO
8
9
6
3
)
2
]
3.04
b
2
L b
2
Pd;[PdL (CH
3
COO)]CH
COO)]CH
3
COO·3H
2
O
2
L c
2
Pd;[PdL (CH
b
3
3
COO
7.43 (7.20)
a
223
22
A m .
At 296 K, B.M. ¼ 0.927 £ 10
b
Square planar complex.
3
.2. Spectroscopic studies
signals due to the paramagnetism of the Ni(II) ion while, in
1
the H-NMR spectra of Pd(II) complexes (L b and L c), the
2
2
1
2
Selected IR data for the ligands (L and L ) and their
signals are very sharp upon to diamagnetism of Pd(II) ion.
2
The values of Ar–CH –N and N–CH signals for L b and
1
complexes (L a, L a–L c) are given in Table 3. The free
2
2
2
2
1
1
2
L c are in accordance with the values of Zn(II) and Cd(II)
complexes of similar ligands [27]. The azomethine protons
ligand (L ) and it’s mononuclear Ni(II) complex (L a) show
characteristic imine (CyN) absorption bands at 1632 and
2
1
650 cm , respectively. On the other hand, the obser-
1
give signals at 8.74 and 8.71 ppm (for L and L a,
1
1
1
2
2
respectively) as singlets. The peaks of the complex (L a)
are considerably shifted toward low-fields with respect to
vations of n(Ar–O) and n(C–O–C) bands (for L and L
ligands and also for their metal complexes) between
2
292–1221 and 1137–1066 cm were the evidences for
1
2
the peaks of the free ligand (L ). The H-NMR spectra of
1
1
the existence of etheric groups. In the Ni(II) complexes (L a
2
and L a), two new intense bands are observed at 1344,
1
2
2
the complexes (L b and L c) show two different kinds of
CH COO proton signals at 1.32; 1.90 and 1.28; 1.80 ppm
3
2
30 cm (for L a) and 1310, 829 cm (for L a), which
1
1
21
2
8
they can be assigned to the NO ion stretching bands, which
values, respectively. Besides that, the signals observed at
2
3
2
2
9.68 and 9.51 ppm (for L b and L c) indicate the existence
2
indicate the coordination of the oxygen atom between NO3
and Ni(II) ions. These absorption bands are comparable with
of the CH –C(O)O· · ·H hydrogen bonding as supported by
3
2
the obtained crystallographic results for L b
2
1
i
i
˚
the bands of Ni(NO ) ·6H O at 1384 and 826 cm , values.
3
[H21(N2)· · ·O3 2.14(3) A and N2–H21· · ·O3 160.2(3.7)8;
(i) x þ 0:5; 2y; 2z þ 0:5].
2
2
2
The IR spectrum of the ligand (L ) has characteristic peaks
indicating three different N–H absorption bands at 3332,
1
3
1
The C-NMR spectral data of the ligands (L and L )
2
and their complexes (L a, L a–L c) are given in exper-
2
2
310 and 3231 cm . On the other hand, the IR spectra of
1
1
2
3
the complexes (L a–L c) contain N–H absorption bands at
3
2
2
imental section. As expected, all of the possible carbon
13
peaks are observed in the C-NMR spectra of the ligands
2
305, 3287, 3261; 3199 and 3192, 3154 cm , respectively,
1
2
and their complexes, except of L c because of overlapping
with solvent peaks. The characteristic (CyN) imine carbon
which are assigned to the N atoms coordinated to Ni(II) and
Pd(II) ions. The observations of the broad absorption bands
2
at 3166 and 3439 cm (for L a, L b) are the evidences for
2
1
1
1
peak of L a is shifted (ca. 5 ppm) to higher value with
1
respect to the peak of L . On the other hand, the aliphatic
the existence of H O molecules.
2
1
The H-NMR spectral data of the ligands (L and L ) and
1
2
2
2
carbon signals of L a and L a are shifted (ca. 2–21 ppm) to
1
2
2
their Ni(II) and Pd(II) metal complexes (L a, L a–L c) are
1
2
higher values with respect to the signals of L and L ,
1
given in experimental section. H-NMR spectra of Ni(II)
2
respectively. Especially, for L a the signals of the CH
carbon atoms bonded to the N atoms show higher chemical
2
1
complexes (L a and L a) synthesized, show very broad
2
Table 3
Selected IR bands
Compound
n
CyN
n
C–O–C(arom.)
n
C–O–C(aliph.)
n
C–H(aliph.)
n
CyC
n
N–H
nNO3
2
nCH3COO
2
n
O–H
1
L
1632
1290–1232
1286–1237
1288–1221
1242
1110–1069
1128–1066
1110–1075
1137–1073
1123–1068
1120–1075
2941–2829
2925–2784
2925–2945
2966–2875
2970–2866
2970–2871
1600
1599
1603
1593
1573
1569
–
–
–
–
–
–
–
2
L
–
3332; 3310; 3231
–
–
1
L a
1650
1344; 830
3166
–
2
L a
–
–
–
3305; 3287; 3261
3192; 3154
3199
1310; 829
–
a
2
L b
1292–1246
1292–1250
–
–
3439
–
2
L c
a
a
Overlapping with C ¼ C stretching bands.

90
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
Table 4
1
EI (for L and L ) and FAB (for the complexes) mass spectral data
2
a
Fragments (m/z)
Compound
1
L )
1 þ
1
1
[L ] (308), [L -C
þ
1
)] (280), [L -OPhCN] (189),
þ
(
(
2
H
4
þb
[
L -{OPhCN þ C
2
H
4
}] (161)
2
L )
2 þ
2
[L ] (341), [L -CH
þ
2
N] (310), [L -C
þb
2
þ
2
N ]
5
2
H
6
N
2
]
(283), [L -C
þ
3
N ] (238)
3
H
8
2
267), [L -C
þ
2
(253), [L -C
(
4
þb
H
10
N
2
]
4
H
11
1
1
L a) [NiL (NO
1
[NiL (NO
1 2þ
1 þ
(
(
3
)
)
2
]·2H
]
2
O
3
)] (428), [NiL ] (366), [L ] (308)
2
L a) [NiL (NO
2
2
[NiL (NO
þ
2 2þb
2
(399), [{NiL }-CH
þ
3
2
3
)] (461), [NiL ]
þ
2
O] (369),
2
{NiL }-C
[
2
H
4
O] (355)
þ
2
L b) [PdL (CH
2
2
[PdL (CH
2 2þb
2 2þb
(
(
3
COO)]CH
COO)]CH
3
COO·3H
COO
2
O
3
COO)] (506), [PdL ]
þ
(447)
(447)
2
2
L c) [PdL (CH
2
[PdL (CH
3
3
3
COO)] (506), [PdL ]
a
Based on the mass of the most abundance isotope.
Parent ion peak.
b
shift values than the other carbon signals, probably due to
the coordination of the N atoms to Ni(II) ion. The signals of
methyl and carbonyl carbons of C H COO were observed at
in Figs. 1 and 2, respectively. Mass loss (TGA and
calculated), temperature ranges and a description of thermal
events observed in the studies are summarised in Table 5.
The initial weight loss occurring in the 26–135 8C
3
2
2
1
2.8; 25.0 and 178.0; 180.1 ppm for L b and 22.9; 24.9 and
2
78.0; 181.3 ppm for L c, respectively. These data support
1
2
temperature range for (L a) and (L b) is attributed as a
loss of the lattice water molecules. The dehydration
processes are interpreted by endothermic peaks in DSC
1
the results obtained in H-NMR spectra, indicating that one
of the acetate ion is bonded to the Pd(II) ion as a ligand
while, the other one is non-bonded.
1
curves. DSC curves presented a melting process for (L a),
2
(L a), (L b) and (L c), at 252, 279, 172 and 179 8C,
2
2
The prominent fragments in the EI and FAB mass spectra
of all the compounds are given in Table 4. The molecular
respectively, followed by decomposition represented by
þ
1
ion peaks (M ) of the free ligands (L and L ) are observed
2
1
exothermic process for octahedral complexes (L a and L a)
2
2
and endothermic process for square planar complexes (L b
in the EI mass spectra. In the FAB mass spectra of the
1
2
2
2
and L c). All the complexes decomposed completely
complexes (L a and L a–L c), the molecular ion peaks
could not been determined, although the complexes are
found to be consistent with the presence of 1:1 (metal to
macrocycle) stoichiometries (see Table 4). Both of the
1
between 167 and 787 8C. The Ni(II) complexes (L a) and
2
(L a) decomposed in two steps for (L a) and three steps for
1
2
(L a), resulting in Ni and NiO as the final residue,
2
1
2
2
respectively. On the other hand, the Pd(II) complex (L b)
also decomposed in three steps, resulting in Pd as the final
complexes (L a and L a) have two nitrate ions. As
1
mentioned before, in L a, two nitrate ions were bonded to
the Ni(II) ion as monodentate ligands. On the other hand, in
2
residue as observed in the Pd(II) complex (L c). The
2
L a, one nitrate ion is bonded to the Ni(II) ion as a
decomposition of PdO in the thermal process
2
monodentate ligand, while the other one as bidentate. In
þ
PdO ! Pd þ 1/2O for (L b) is easily distinguished in the
2
2þ
each case, [M(macrocycle)(X)] and [M(macrocycle)]
M: Ni, Pd; X: NO , CH COO) ion peaks were observed.
The FAB mass data are in good agreement with the reported
TGA curve. The process may be used for obtaining very
pure metallic Pd. The presence of metallic Ni and Pd
(
3
3
1
2
2
residues for (L a), (L b) and (L c) indicate the presence of
carbonaceous material as decomposition intermediate.
Consequently, the order for thermal stability found is
2
values for nickel(II) thiocyanate complexes of L and other
N O macrocycles [22]. In nickel thiocyanate complexes,
3
2
2
1
2
2
any molecular ion peaks are not observed, but the FAB mass
spectra of the monomeric thiocyanate complexes include
(L a) . (L a) . (L b) . (L c). It is understood that the
1
octahedral complexes (L a) and (L a) are more stable than
2
the square planar complexes (L b) and (L c).
2
2
þ
þ
2
the [Ni(macrocycle)(NCS)] and [Ni(macrocycle)] ion
peaks.
1
2
Both of the Ni(II) complexes (L a and L a) have
3.4. Crystal study
magnetic moments which are typical of the Ni(II) ion in the
2
high spin state. On the other hand, Pd(II) complexes (L b
2
Single crystal X-ray structures of the complexes (L a and
2
and L c) have not gotten any magnetic moment values due
to the their square planar structure (see Table 2 and Fig. 4).
2
L b) are reported to further corroborate the structure
assignments. The final coordinates and equivalent isotropic
displacement parameters are given in Table 6. The
molecular structures with the atom-numbering schemes
are shown in Figs. 3 and 4. The molecular packings are
shown in Figs. 5 and 6. The packings of the molecules in the
unit cells are purely due to dipole–dipole, hydrogen
3
.3. TGA and DSC
The thermogravimetric (TGA) and differential scanning
calorimetric (DSC) curves for the complexes are illustrated

S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
91
1
Fig. 1. TGA curves for the complexes (L a and L a–L c).
2
2
1
Fig. 2. DSC curves for the complexes (L a and L a–L c).
2
2

92
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
Table 5
TGA mass losses, temperature range and DSC peaks related to the thermal decomposition processes of the Ni(II) and Pd(II) complexes
Complex
Process
TGA data
DSC Peaks
a
(
8C)
Temperature range Mass loss a or
(
8C)
residue b
%)
(
TGA
Calculated
1
L a)
1
[Ni(L )(NO
1
(
3
)
)
2
2
]·2H
2
O ! [Ni(L )(NO
3
)
2
] þ 2H
2
O
78–135
6.40 a 6.84
44.80 a 46.39
10.40 b 11.03
132.20 (endo)
252.23 (exo)
1
Ni(L )(NO
[
3
] ! [Ni(B)] þ A þ 2(NO þ O
2
)
230–248
239–787
[
Ni(B)] ! Ni þ B
2
2
[
Ni(L )(NO
3
)
2
] ! [Ni(L )O
] ! [Ni(B)O ] þ A
] ! NiO þ B
2
] þ 2NO
2
265–283
285–423
423–661
20.00 a 17.59
12.00 a 11.02
17.60 b 17.29
279.38 (exo)
2
Ni(L )O
[
2
2
2
L a)
(
[Ni(B)O
2
2
2
PdL (AcO)]AcO·3H
2
[
2
O ! [PdL (AcO)]AcO þ 3H
2
O
26–87
9.33 a
8.81
95.66 (endo)
171.45 (endo)
172.16 (endo)
2
[
PdL (AcO)]AcO ! [Pd(B)O] þ A þ AcO þ Ac
170–330
330–467
640–670
54.00 a 55.79
15.33 a 16.48
16.00 b 17.29
2
L b)
(
(
[Pd(B)O] ! PdO þ B
2
PdO ! Pd þ 1/2O
2
L c)
2
2
[PdL (AcO)]AcO ! Pd þ L þ 2AcO
167–610
18.58 b 19.17
178.31 (endo)
1
78.64 (endo)
AcO: CH
3
COO; Ac: CH
3
CO.
a
Exo: exothermic process; endo: endothermic process.
bonding and van der Waals forces of interaction. The
molecules are elongated through the c-axes of the unit cells.
The bond lengths and angles with some selected torsion
angles are given in Tables 7 and 8. The co-ordination
ion in a facial configuration. The Ni–N bond lengths vary
˚
from 2.047(3) to 2.158(3) A and hence, fall within the
˚
literature range (2.04–2.33 A) which is typical of nickel to
3
sp -nitrogen bonds [29]. The nickel to monodentate and
2
2
geometry of the nickel in [Ni(L )(NO ) ], (L a) is distorted
3
bidentate nitrates oxygens bond lengths are in the range
˚
2.096(3)–2.197(3) A. On the other hand, there are intra-
2
octahedral involving three nitrogen donors of the macro-
cyclic ring, two oxygen atoms of the bidentate and one
oxygen atom of the monodentate nitrate ions. The etheric
oxygens are not bound to the nickel, non-co-ordination of
the ether oxygens has been previously confirmed for several
complexes by X-ray diffraction [16,17,22,23,25,26,28]. The
main distortion from octahedral symmetry is arisen with
molecular hydrogen bonds between etheric oxygen and aza-
nitrogen atoms [N2· · ·O1 2.846(4), O1· · ·H2(N2)
˚
2.370(4) A, N2–H2· · ·O1 120.3(3.4)8] and also between
monodentate nitrate oxygen and aza-nitrogen atoms
˚
[N1· · ·O7 2.902(5), O7· · ·H1(N1) 2.178(4) A, N1–
2
H1· · ·O7 135.9(2)8]. The complex L b contains a mono-
the small bite of the bidentately co-ordinated nitrate ion
˚
nuclear Pd(II) ion in which there are three water molecules
and two acetate anions. The one acetate anion in the
complex does not act as a ligand but is incorporated into the
[
Ni–O5 2.197(3) A]. The angles around the Ni(II) ion in the
four- and five-membered chelate rings are as usual, less than
i
the ideal value of 908 [60.0(1), 85.9(1) and 82.8(1)8]. In this
2
structure, the three nitrogens of (L ) co-ordinate to Ni(II)
crystal lattice by hydrogen bonding [N2· · ·O3 2.751(6),
i
i
˚
H21(N2)· · ·O3 2.14(3) A and N2–H21· · ·O3 160.2(3.7)8;

S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
93
Table 6
Atomic coordinates and isotropic displacement parameters with e.s.d’s in parentheses for (L a and L b)
2
2
2
L a)
2
(L b)
(
Atom
x
y
z
Uiso
Atom
x
y
z
Uiso
Ni
0.77371(3)
0.8826(3)
0.7937(3)
0.7357(2)
0.6966(3)
0.7401(3)
0.7020(3)
0.6209(4)
0.5752(3)
0.6130(3)
0.4942(2)
0.4678(2)
0.5240(2)
0.4574(3)
0.4540(3)
0.5152(3)
0.5805(2)
0.5867(2)
0.6588(2)
0.8119(2)
0.8937(2)
0.57355(16)
0.53149(16)
0.66695(16)
0.6621(2)
0.76715(17)
0.81896(18)
0.9409(2)
0.9104(2)
0.88437(19)
0.7377(2)
0.74200(18)
0.6975(2)
0.8909(3)
0.13941(5)
0.3265(4)
0.3631(4)
0.1015(4)
0.1627(4)
0.1647(4)
0.2217(5)
0.2783(5)
0.2785(5)
0.2182(4)
0.2808(4)
0.2404(4)
0.2715(4)
0.1845(4)
0.1577(4)
0.2201(5)
0.3091(4)
0.3359(4)
0.4356(4)
0.4716(4)
0.3847(5)
0.2029(3)
0.3022(3)
0.93393(2)
1.0357(2)
1.0579(2)
1.1017(2)
1.1721(2)
1.2430(2)
1.3073(2)
1.3007(2)
1.2308(2)
1.1678(2)
1.0811(2)
1.0003(2)
0.8762(2)
0.8417(2)
0.7640(2)
0.7203(2)
0.7553(2)
0.8330(2)
0.8676(2)
0.8784(2)
0.8968(2)
1.09660(14)
0.95364(14)
0.90086(14)
0.79688(16)
0.82284(15)
0.98198(17)
0.9320(2)
1.00595(19)
0.95730(17)
1.03863(17)
0.86684(17)
0.83902(18)
0.9751(2)
0.03110(19)
0.0463(10)
0.0424(10)
0.0383(9)
0.0372(9)
0.0489(11)
0.0589(13)
0.0620(13)
0.0521(11)
0.0390(9)
0.0422(9)
0.0425(9)
0.0322(8)
0.0426(9)
0.0491(11)
0.0496(1
Pd1
C1
0.36528(2)
0.6260(3)
0.7197(3)
0.7909(4)
0.7718(4)
0.6796(4)
0.6075(3)
0.5003(3)
0.4006(4)
0.2383(3)
0.1949(4)
0.0993(5)
0.0420(4)
0.0835(3)
0.1831(3)
0.2254(3)
0.2599(3)
0.3139(3)
0.4615(3)
0.5355(3)
0.5496(3)
0.0550(4)
0.02897(2)
0.0426(3)
0.0608(4)
0.349818(10)
0.39618(15)
0.38010(17)
0.38116(18)
0.39653(18)
0.41327(18)
0.41309(15)
0.45853(16)
0.47747(16)
0.44667(16)
0.49105(17)
0.4953(2)
0.04268(11)
0.0593(12)
0.0774(15)
0.0861(17)
0.0886(18)
0.0751(14)
0.0583(12)
0.0663(13)
0.0638(12)
0.0557(11)
0.0722(14)
0.0826(16)
0.0842(16)
0.0643(12)
0.0545(11)
0.0550(11)
0.0664(13)
0.0660(12)
0.0572(11)
0.0623(12)
0.0568(11)
0.0671(13)
0.0935(18)
0.0595(12)
0.0818(16)
0.0627(8)
C1
C2
C2
C3
C3
20.0039(5)
20.0896(5)
20.1119(4)
20.0455(3)
20.1397(3)
20.1320(3)
20.1307(3)
20.1235(3)
20.1068(4)
20.0963(3)
20.1041(3)
20.1231(3)
20.1374(3)
20.0750(3)
0.0000(4)
C4
C4
C5
C5
C6
C6
C7
C7
C8
C8
C9
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
O1
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
O1
0.4551(2)
0.41116(17)
0.40617(16)
0.35845(14)
0.27960(15)
0.25523(15)
0.26955(14)
0.30803(14)
0.39629(15)
0.21816(17)
0.17463(18)
0.42053(17)
0.47036(17)
0.43977(11)
0.42990(11)
0.24382(13)
0.22900(13)
0.38662(14)
0.41675(9)
0.3251(2)
0.0417(9)
0.0318(8)
0.0318(8)
0.0382(9)
0.0458(10)
0.0440(6)
0.0413(6)
0.0374(6)
0.0616(9)
0.0469(7)
0.0584(8)
0.0911(12)
0.0783(10)
0.0401(7)
0.0336(7)
0.0306(7)
0.0407(8)
0.0572(10)
0.0970(3)
0.1084(3)
0.1151(3)
0.1889(3)
O2
20.0020(5)
0.2445(3)
0.2123(4)
0.3346(2)
0.5161(2)
0.0229(3)
0.1224(3)
0.1965(3)
0.3208(2)
0.0578(5)
0.9078(4)
0.7451(3)
0.2475(2)
0.4033(3)
0.4828(2)
0.2090(4)
O3
20.0023(3)
20.1491(3)
0.0151(3)
0.1075(3)
O4
0.1271(4)
O5
20.1506(2)
20.0600(2)
0.1257(3)
O6
20.0790(3)
20.0668(5)
20.2679(3)
0.2630(3)
O2
0.0661(8)
O7
O3
0.1201(17)
0.0922(12)
0.0881(11)
0.0527(7)
O8
O4
0.2379(3)
N1
O5
0.1380(3)
N2
0.2241(3)
O6
0.05939(19)
0.0516(5)
N3
0.3527(3)
O7
0.1358(19)
0.151(2)
N4
20.0485(3)
20.1398(4)
O8
0.2053(4)
0.3374(3)
N5
O9
0.2724(3)
0.30169(16)
0.33105(11)
0.28223(13)
0.35371(12)
0.1007(12)
0.0508(8)
N1
20.0523(2)
0.0162(3)
N2
0.0533(11)
0.0499(8)
N3
0.1143(2)
2
Fig. 3. An ORTEP [19] drawing of (L a) with the atom-numbering scheme.
2
Fig. 4. An ORTEP [19] drawing of (L b) with the atom-numbering scheme.
The thermal ellipsoids are drawn at the 50% probability level.
The thermal ellipsoids are drawn at the 50% probability level.

94
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
2
Fig. 5. The molecular packing diagram for (L a).
(
i) x þ 0:5; 2y; 2z þ 0:5]. There are also intramolecular
2y þ 0:5; z] hydrogen bonds between three water molecules
and also between the water molecules and the macroring.
The macrorings are elongated along the c-axis of the unit
cell (Fig. 6) and there are cavities between the macroring
lines. One of the acetate ion and the three water molecules
fill in the cavities by forming the hydrogen bonds. Pd(II) ion
0
0
˚
O8· · ·O9 2.849(8), H9 (O9)· · ·O8 2.22(9) A, O9–H9 · · ·O8
[
0
˚
08.2(5.3)8; O7· · ·N1 3.029(7), H7 (O7)· · ·N1 2.45(9) A,
1
O7–H7 · · ·N1 130.0(7.2)8; N1· · ·O7 3.029(7), H1(N1)· · ·O7
2
0
˚
ii
.134(6) A, N1–H1· · ·O7 167.4(3)8] and intermolecular
ii
˚
N3· · ·O8 2.871(7), H31(N3)· · ·O8 1.94(5) A, N3–
[
ii
˚
is at a distance of 20.1060(3) A to the best plane of N1, N2,
H31· · ·O8 156.5(4.1)8; (ii) x 2 0:5; 2y þ 0:5; z;
iii
00
iii
O7· · ·O8 3.074(9), H7 (O7)· · ·O8 2.31(10) A, O7–
˚
N3, O6 atoms, and the coordination around Pd(II) ion is a
distorted square planar (Table 8). Although the Pd(II) ion
has four coordination, the close contact of the O5 atom
0
0
iv
H7 · · ·O8 140.9(7.5)8; (iii) x 2 1; y; z; O9· · ·O5 2.818(6),
00
iv
H9 (O9)· · ·O5 2.20(7) A, O9–H9 · · ·O5 134.4(5.7)8; (iv)
00
iv
˚
v
00
v
˚
x þ 0:5; 2y þ 0:5; z; O8· · ·N3 2.871(7), H8 (O8)· · ·N3
[Pd· · ·O5 ¼ 3.007(3) A] may cause the Pd(II) ion to have
00
v
˚
2
.09(15) A, O8–H8 · · ·N3 163.6(5.8)8; (v) x þ 0:5;
five coordination. The five coordination around Pd(II) can
2
Fig. 6. The molecular packing diagram for (L b).

S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
95
Table 7
The selected bond lengths (A) and angles (8) with the torsion angles (8) for
Table 8
˚
The selected bond lengths (A) and angles (8) with the torsion angles (8) for
2
(L b)
˚
2
L a)
(
Ni–N1
2.047(3) C2–C1
2.072(3) C17–C18
2.158(3) C3–C4
2.096(3) C3–N2
2.108(2) N1–C1
2.197(3) O1–C9
1.379(4) O1–C10
1.426(4) C4–C9
1.493(5) O4–N4
1.386(5) O3–N4
1.473(5) O5–N4
1.499(5) O6–N5
1.482(4) O8–N5
1.483(4) N5–O7
1.476(4)
1.509(6)
1.506(4)
1.497(5)
1.499(4)
1.471(5)
1.370(4)
1.423(4)
1.397(5)
1.226(4)
1.269(4)
1.266(4)
1.256(4)
1.218(4)
1.273(5)
C24–C23
Pd1–N2
Pd1–O6
Pd1–N3
Pd1–N1
O6–C23
N3–C19
N3–C20
N2–C17
N2–C18
N1–C15
N1–C16
O1–C9
1.505(6) C20–C1
1.991(4) O5–C23
2.040(3) C14–C9
2.048(3) C14–C15
2.081(3) C19–C18
1.270(5) C1–C6
1.485(5) O2–C6
1.516(5) O2–C7
1.469(6) C7–C8
1.473(6) C16–C17
1.498(5) O4–C21
1.503(5) C21–O3
1.373(5) C21–C22
1.429(5)
1.496(6)
1.248(6)
1.380(6)
1.485(6)
1.501(6)
1.397(6)
1.364(5)
1.435(5)
1.479(7)
1.495(7)
1.213(5)
1.255(5)
1.490(7)
Ni–N2
Ni–N3
Ni–O6
Ni–O3
Ni–O5
O2–C12
O2–C11
C11–C10
C12–C17
C20–N1
C20–C19
N3–C19
N3–C18
C2–N2
O1–C8
N2–Pd1–O6
N2–Pd1–N3
O6–Pd1–N3
N2–Pd1–N1
O6–Pd1–N1
N3–Pd1–N1
C23–O6–Pd1
C19–N3–C20
C19–N3–Pd1
C20–N3–Pd1
C17–N2–C18
C17–N2–Pd1
C18–N2–Pd1
C15–N1–C16
C15–N1–Pd1
C16–N1–Pd1
C9–O1–C8
172.34(15) C9–C14–C15
84.30(15) O5–C23–O6
93.18(12) O5–C23–C24
84.65(15) O6–C23–C24
97.26(12) N3–C19–C18
168.22(13) C6–C1–C20
121.8(4)
N1–Ni–N2
N1–Ni–O6
N2–Ni–O6
N1–Ni–O3
N2–Ni–O3
O6–Ni–O3
N1–Ni–N3
N2–Ni–N3
O6–Ni–N3
O3–Ni–N3
N1–Ni–O5
N2–Ni–O5
O6–Ni–O5
O3–Ni–O5
N3–Ni–O5
C12–O2–C11
O2–C11–C10
O2–C12–C17
N1–C20–C19
C19–N3–C18
C19–N3–Ni
C18–N3–Ni
N2–C2–C1
C12–C17–C18
85.94(12) C4–C3–N2
94.44(12) C2–N2–C3
92.15(11) C2–N2–Ni
173.68(11) C3–N2–Ni
100.06(11) C1–N1–C20
83.44(11) C1–N1–Ni
82.79(11) C20–N1–Ni
98.14(11) N1–C1–C2
169.10(12) N3–C18–C17
98.19(10) C9–O1–C10
114.02(11) O1–C10–C11
160.02(12) C9–C4–C3
87.39(11) O1–C9–C4
114.1(3)
124.9(4)
119.7(4)
115.4(5)
107.8(3)
121.6(4)
117.7(3)
106.4(3)
115.7(3)
115.6(4)
106.6(4)
107.9(4)
110.0(4)
107.2(4)
115.6(4)
123.9(5)
119.8(5)
116.0(5)
113.0(3)
105.8(2)
116.4(2)
116.0(3)
107.6(2)
108.2(2)
112.3(3)
113.5(3)
119.0(3)
106.1(3)
119.9(3)
113.6(3)
110.0(3)
93.64(19)
89.6(2)
116.6(3)
113.3(3)
107.8(3)
121.9(2)
117.4(4)
107.1(3)
107.6(3)
109.9(3)
120.1(2)
106.5(3)
118.0(3)
114.9(4)
C6–O2–C7
N2–C18–C19
C14–C15–N1
O1–C9–C14
O2–C7–C8
O1–C8–C7
C17–C16–N1
N2–C17–C16
O2–C6–C1
60.03(9)
N3–C19–C20
84.16(10) N4–O3–Ni
O4–C21–O3
O4–C21–C22
O3–C21–C22
118.3(3)
107.2(3)
116.3(3)
111.1(3)
110.5(3)
108.3(2)
123.3(2)
110.0(3)
122.5(3)
N4–O5–Ni
N5–O6–Ni
O8–N5–O6
O8–N5–O7
O6–N5–O7
O4–N4–O5
O4–N4–O3
O5–N4–O3
126.5(3)
120.7(4)
121.5(4)
117.7(4)
121.3(3)
122.3(3)
116.4(3)
C1–C20–N3
C19–N3–C20–C1
C20–N3–C19–C18
N3–20–C1–C6
248.4(5)
173.4(3)
285.1(5)
168.6(4)
255.4(5)
C6–O2–C7–C8
C9–O1–C8–C7
O2–C7–C8–O1
172.1(4)
2167.9(4)
73.6(4)
C17–N2–C18–C19
N3–C19–C18–N2
C15–N1–C16–C17 2160.7(4)
C18–N2–C17–C16 2170.6(4)
C9–C14–C15–N1 2101.8(5)
C16–N1–C15–C14 2162.6(4)
N1–C16–C17–N2
C7–O2–C6–C1
C20–C1–C6–O2
52.6(5)
2164.1(4)
20.6(6)
C12–O2–C11–C10
C11–O2–C12–C17
O2–C12–C17–C18
C1–C2–N2–C3
176.2(3)
179.1(3)
20.6(4)
88.7(4)
C12–C17–C18–N3
C9–O1–C10–C11
O2–C11–C10–O1
N2–C3–C4–C9
110.9(4)
2179.5(3)
260.2(4)
59.3(4)
C8–O1–C9–C14
C15–C14–C9–O1
161.1(4)
1.2(6)
the Pd(II) ion is, therefore, best described as a distorted
square pyramid.
C4–C3–N2–C2
66.2(4)
C10–O1–C9–C4
C3–C4–C9–O1
2168.9(3)
2.7(4)
C19–C20–N1–C1
C20–N1–C1–C2
N2–C2–C1–N1
277.0(4)
91.1(4)
C18–N3–C19–C20
N1–C20–C19–N3
166.1(3)
248.7(4)
48.5(4)
C19–N3–C18–C17
162.3(3)
Acknowledgements
The authors wish to acknowledge the Scientific and
Technical Research Council of Turkey (grant number:
TBAG-1693) and Hacettepe University Scientific Research
Unit (grant number: 02 02 602 002) for financial support.
be described as a distorted square pyramid or trigonal
bipyramid. Further information can be obtained by estimat-
ing the structural index, t [30], which represents the relative
amount of trigonality (square pyramid, t ¼ 0; trigonal
pyramid, t ¼ 1; t ¼ ðb 2 aÞ=608; where a and b being the
two largest angles [bðN2–Pd1–O6Þ ¼ 172:34ð15Þ8 and
aðN3–Pd1–N1Þ ¼ 168:22ð13Þ8] around the central atom.
The value of t is 0.07(14). The co-ordination geometry of
References
[
1] L.F. Lindoy, B.W. Skelton, S.V. Smith, A.H. White, Aust. J. Chem.
46 (1993) 363.

96
S. Bilge et al. / Journal of Molecular Structure 691 (2004) 85–96
[
[
2] K.R. Adam, A.J. Leong, L.F. Lindoy, H.C. Lip, B.W. Skelton, A.H. [20] J.A. Ibers, W.C. Hamilton, International Tables for X-Ray Crystal-
White, J. Am. Chem. Soc. 105 (1983) 4645.
lography, vol. IV, Kynoch Press, Birmingham (Present Distributor
Kluwer Academic Publisher, Dordrecht), 1974.
3] D.E. Fenton, B.P. Murphy, A.J. Leong, L.F. Lindoy, A. Bashall, M.
McPartlin, J. Chem.Soc., Dalton Trans. (1987) 2543.
[21] L.F. Lindoy, H.C. Lip, L.P. Power, J.H. Rea, Inorg. Chem. 15 (1976)
1724.
[
[
[
4] L.F. Lindoy, Pure Appl. Chem. 69 (1997) 2179.
5] L.F. Lindoy, Prog. Macrocyclic Chem. 3 (1987) 53.
6] K.R. Adam, C. Clarkson, A.J. Leong, L.F. Lindoy, M. McPartlin, H.R.
Powell, S.V. Smith, J. Chem. Soc., Dalton Trans. (1994) 2791.
7] P.S.K. Chia, A. Ekstrom, I. Liepa, L.F. Lindoy, M. McPartlin, S.V.
Smith, P.A. Tasker, Aust. J. Chem. 44 (1991) 737.
[22] K.R. Adam, A.J. Leong, L.F. Lindoy, B.J. McCool, A. Ekstrom, I.
Liepa, P.A. Harding, K. Henrick, M. McPartlin, P.A. Tasker, J. Chem.
Soc., Dalton Trans. (1987) 2537.
[
[
[23] P.A. Harding, K. Henrick, L.F. Lindoy, M. McPartlin, P.A. Tasker,
J. Cem. Soc., Chem. Commun. (1983) 1300.
8] K.R. Adam, M. Antolovich, D.S. Baldwin, P.A. Duckworth, A.J.
Leong, L.F. Lindoy, M. McPartlin, P.A. Tasker, J. Chem. Soc., Dalton
Trans. (1993) 1013.
[24] K.R. Adam, M. Antolovich, D.S. Baldwin, L.G. Brigden, P.A.
Duckworth, L.F. Lindoy, A. Bashall, M. McPartlin, P.A. Tasker,
J. Chem. Soc., Dalton Trans. (1992) 1869.
[
9] T. H o¨ kelek, Z. Kılı c¸ , S. Bilge, Acta Cryst. C55 (1999) 248.
[25] H.J. Goodwin, K. Henrick, L.F. Lindoy, M. McPartlin, P.A. Tasker,
Inorg. Chem. 21 (1982) 3261.
[
[
[
[
[
[
10] T. H o¨ kelek, Z. Kılı c¸ , S. Bilge, Acta Cryst. C55 (1999) 381.
11] T. H o¨ kelek, N. Akduran, S. Bilge, Z. Kılı c¸ , Anal. Sci. 17 (2001) 465.
12] T. H o¨ kelek, N. Akduran, S. Bilge, Z. Kılı c¸ , Anal. Sci. 17 (2001) 801.
13] T. H o¨ kelek, S. Bilge, Z. Kılı c¸ , Anal. Sci. 18 (2002) 1065.
[26] K.R. Adam, G. Anderegg, K. Henrick, A.J. Leong, M. L, F. Lindoy,
H.C. Lip, M. McPartlin, R.J. Smith, P.A. Tasker, Inorg. Chem. 20
(1981) 4048.
14] T. H o¨ kelek, E.E. Kaya, Z. Kılı c¸ , Acta Cryst. E57 (2001) o309.
15] T. H o¨ kelek, N. Akduran, E.E. Kaya, Z. Kılı c¸ , Anal. Sci. 16 (2000)
[27] L.F. Lindoy, H.C. Lip, J.H. Rea, R.J. Smith, K. Henrick, M.
McPartlin, P.A. Tasker, Inorg. Chem. 19 (1980) 3360.
[28] K.R. Adam, S.P.H. Arshad, M. D, S. Baldwin, P.A. Duckworth, A.J.
Leong, L.F. Lindoy, B.J. McCool, M. McPartlin, B.A. Tailor, P.A.
Tasker, Inorg. Chem. 33 (1994) 1194.
997.
[
[
16] L.G. Armstrong, L.F. Lindoy, Inorg. Chem. 14 (1975) 1322.
17] K.R. Adam, L.F. Lindoy, H.C. Lip, J.H. Rea, B.W. Skelton, A.H.
White, J. Chem. Soc., Dalton Trans. (1981) 74.
[29] N.F. Curtis, in: G.A. Melson (Ed.), Coordination Chemistry of
Macrocyclic Compounds, Plenum, New York, 1979, p. 219.
[30] S. Uhlenbrock, R. Wegner, B. Kebs, J. Chem. Soc., Dalton Trans.
(1996) 3731.
[
[
18] G.M. Sheldrick, SHELXS-97 and SHELXL-97, University of G o¨ ttingen,
Germany, 1997.
19] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565.