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Synthesis and structures of morpholine substituted new vic-dioxime ligand and its Ni(II) complexes
Inorganica Chimica Acta 357 (2004) 588–594 www.elsevier.com/locate/ica
Synthesis and structures of morpholine substituted new vic-dioxime ligand and its Ni(II) complexes Mahmut Durmusß a, Vefa Ahsen
a,b,*
, Dominique Luneau
c,*,1
, Jacques Pecaut
c
a
Department of Chemistry, Gebze Institute of Technology, P.O. Box 141, Gebze, Kocaeli 41400, Turkey TUBITAK-Marmara Research Center, Materials and Chemical Technologies Research Institute, P.O. Box 21, Gebze, Kocaeli 41470, Turkey Laboratoire de Chimie Inorganique et Biologique (UMR 5046), DRFMC, CEA-Grenoble, 17 rue des Martyrs, Grenoble Cedex 09, 38054, France b
c
Received 21 October 2002; accepted 23 May 2003
Abstract N; N 0 -bis[4-(2-aminoethyl)morpholino]glyoxime (H2 L) (Fig. 1), has been prepared in various yields using three different methods. The most efficient of these methods is the technique of microwave irradiation. The crystal structures of H2 L, and of two nickel(II) complexes 1 and 2 have been determined by single crystal X-ray diffraction. Both nickel(II) complexes have a metal–ligand ratio of 1:2 in which the ligand coordinates through the two nitrogen atoms as do most vic-dioximes. The nickel(II) complexes are either hydrogen (1) or boron diphenyl bridged (2). Complex 1 was synthesized by reacting H2 L with nickel(II) chloride in refluxing ethanol. Complex 2 was prepared at room temperature in an ethanol solution containing excess NaBPh4 . Elemental analyses, NMR(1 H, 13 C), IR and mass data are also presented. Ó 2003 Published by Elsevier B.V. Keywords: vic-Dioximes; Nickel(II) complexes; Glyoximes
1. Introduction vic-Dioximes and their complexes constitute an important class of compounds having versatile reactivities [1]. Since the pioneering work of Schrauzer [2] cobaloximes have been widely studied as the model for coenzyme B12 . These are bis complexes of dimethylglyoximate. Discoveries on B12 models made since 1989 are assessed in the light of the advances in structural and spectroscopic methodologies. Further studies emanating in part from these advances have confirmed previously identified principles describing the properties of the classic simple models(cobaloximes and iminocobaloximes) and have established some new principles defining the properties of the axial Co–C and Co–N bonds [3]. * Corresponding authors. Tel.: +90-262-641-2300; fax: +90-262-6412309 (V. Ahsen). E-mail addresses: [email protected] (V. Ahsen), [email protected] (D. Luneau). 1 Present address: Universite Claude Bernard Lyon 1, B^at 305, 43 Avenue du 11 Novembre 1918, 69622 Villeurbanne Cedex, France.
0020-1693/$ - see front matter Ó 2003 Published by Elsevier B.V. doi:10.1016/j.ica.2003.05.004
The exceptional stability and unique electronic properties of the vic-dioximes complexes can be attributed to their planar structure which is stabilized by hydrogen bridges. Moreover, in the last decade, polymetallic complexes were synthesized with various vic-dioxime [4], after removal of the hydrogen bridge. This has demonstrated that the oximate group may also act as a bridging ligand to mediate strong antiferromagnetic exchange interactions between the bridged metal ions. This was successfully used to synthesize extended bimetallic compounds with magnet behaviors [5]. Furthermore, vic-dioximes are easily modified by substitution with various groups. The reaction of amines or thiols with (E; E)-dichloroglyoxime or cyanogendi-N-oxide yielded various symmetrically substituted diaminoglyoxime or dithioglyoxime derivatives [6]. In previous papers the synthesis of vic-dioxime ligands and their transition metal complexes containing crown ethers [7], monoaza crown ethers [8], ferrocene groups [9], tetrathiamacrocycles [10], or N2 O2 macrocycles [11] and dendritic groups [12] have also been reported. Other investigated fields for these compounds concern liquid
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crystals [13], gas sensors [14] and inhibitors for chemical warfare agents [15]. Herein, we present the synthesis of a morpholine substituted diaminodioxime ligand (H2 L), together with two nickel(II) complexes. The ligand was obtained using both conventional methods and in solvent-free conditions using the microwave irradiation technique in presence of silica gel. In all cases we obtained the anti ðE; EÞ isomer of H2 L. The structure of the ligand (Figs. 1 and 2) and its complexes (Figs. 3 and 4) have been identified by a combination of elemental analysis, 1 H and 13 C NMR, IR
Fig. 4. View of the molecular structure for complex 2 (E; E)-NiL2 BPh2 . Ellipsoids are drawn at the 30% probability level. Fig. 1. Chemical structure of H2 L.
and mass spectral data and X-ray crystal structure (see Fig. 1).
2. Results and discussion 2.1. Ligand (H2 L)
Fig. 2. View of the molecular structure of the ligand H2 L. Ellipsoids are drawn at the 30% probability level.
Fig. 3. View of the molecular structure for complex 1 (E; E)-Ni(HL)2 (molecule 1A). Ellipsoids are drawn at the 30% probability level.
In this work we prepared vic-dioxime ligand (H2 L) in various yields following three different synthesis methods. Along the first method (A), H2 L was synthesized from the reaction of a solution of 4-(2-aminoethyl)morpholine in diethylether with a solution of cyanogen di-N-oxide in diethylether. In a second method (B), 4-(2-aminoethyl) morpholine was reacted with ethanolic (E; E)-dichloroglyoxime in the presence of NaHCO3 as a buffer to neutralize HCl formed during the reaction. In the third method (C), H2 L was obtained by microwave irradiation in solvent-free conditions in the presence of silica gel. In the 1 H NMR spectrum of H2 L in DMSO-d6 , the deuterium exchangeable protons of the @N–OH groups show only one chemical shifts at d ¼ 9:49 ppm as a singlet which indicates an (E; E)-structure for the vicinal dioxime [16]. The chemical shifts which belong to –NH protons were observed at d ¼ 5:64 ppm as a triplet and disappeared with D2 O exchange. The chemical shifts which belong to –CH2 protons were observed at d ¼ 3:55 ppm (CH2 –O), 3.12 ppm (CH2 –NH) and 2.38 ppm (CH2 –N). The chemical shifts of CH2 –N protons at d ¼ 3:12 ppm were observed as quartet, but they converted to a triplet after D2 O exchange. More detailed information about the structure of H2 L is provided by
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C NMR spectral data. The chemical shifts for the amide carbon atoms are found at d ¼ 146:9 ppm [17]. These equivalent carbon atoms, especially belonging to hydroxyimino carbon atoms, also confirm the anti structure of H2 L [18]. The mass spectrum (LSIMS) of H2 L exhibits a molecular ion peak at m=z 345 ½M þ 1þ . The peak 327 indicates the loss of water ([M–OH2 ]þ ). In the IR spectrum of H2 L, the O–H stretching vibration is observed at 3463 cm1 . Bands due to N–H, C@N and N–O stretches are at 3346, 1639, 1021 cm1 . The stretching vibration for –NH2 disappears after the condensation reaction of 4-(2-aminoethyl)morpholine with (E; E)-dichloroglyoxime. These results indicate that the formation of vic-dioxime ligand was completed. The molecular structure of the ligand H2 L is shown on Fig. 2. The asymmetric unit comprises one half molecule of the ligand. The whole molecule is deduced by symmetry operation (x; y; y 1=2) and has a butterfly shape. The two symmetry related moieties make an angle of 80.0°. The oxime groups have the anti (E; E) conformation in agreement with the 1 H NMR spectrum. The bond lengths and angles are found to be normal (Table 2). Intermolecular hydrogen bonds involve the oxime groups with the morpholine nitrogen atoms (N3) and with the amido nitrogen atoms (N2) (O1–N3 ¼ 2.760(2) and O1–N2 ¼ 2.925(2) A). This affords chains which A are parallel to the c axis direction (Fig. 1S, in supplementary material). 2.2. Nickel(II) complex [(E,E)-Ni(HL)2 ] H2 O (1) This was obtained by refluxing the ligand and NiCl2 6H2 O (ratio 2:1) together in ethanol. The complex is soluble in common organic solvents, which allowed full characterization. In the 1 H NMR spectrum of 1, the resonances of intramolecular bonding OH–O protons shifted to d ¼ 16.84 ppm, which disappear by D2 O exchange. The other chemical shifts (1 H- and 13 C NMR) observed for complex 1 are very similar to those found for the ligand H2 L. In the IR spectrum the usual hydrogen bridges of the square-planar vic-dioxime complexes were also characterized by the weak deformation bands [19] around 1730 cm1 . The C@N vibrations are at lower wave numbers, as expected for N ; N 0 -chelated vicinal dioxime complexes. The crystal structure of complex 1 consists of two crystallographically independent complex molecules, which are denoted molecule 1A and molecule 1B, and crystallize with water molecules. A view of the complex molecules is shown on Fig. 3 (molecule 1A). Some methylene groups (C10A, C9B, C10B) were found to be disordered and were refined on two positions with a half occupancy. The complex molecules are centrosymmetrical. The nickel(II) ion is in a square planar environment and is bound by the four oxime nitrogens atoms.
The Ni–N(oxime) bond lengths [1.863(2)–1.868(2) A] (Table 2) are in the previously observed range for nickel(II)-dioxime complexes [20]. The N1A–NiA–N4A and N1B–NiB–N4B are 82.48(7)° and 82.71(7)°, respectively. The complexation leads to a shortening of as the N–O oxime bond length [1.345(2)–1.393(2) A] compared to that found for the free ligand [1.434(1) A]. In each of the molecule 1A and 1B, the oximic oxygen atoms are hydrogen bonded as normally observed for the anti isomer complex of dioxime [O1A–O3A ¼ and O1B–O3B ¼ 2.485(2) A] [21]. The dif2.482(3) A ferences found between the N1–O1 and N4–O3 bond lengths [N1A–O1A ¼ 1.391(2), N1B–O1B ¼ 1.393(2), N4A–O3A ¼ 1.356(2) and N4B–O3B ¼ 1.345(2)] are due to the fact that the hydrogen atoms are not symmetrically located between the oximic oxygen atoms (O1 and O3) as previously observed [21]. The water molecules are found to be hydrogen bonded to the oximic oxygen at and O9w–O3B ¼ 3.015(3) oms [O9w–O3A ¼ 2.855(3) A A]. 2.3. Nickel(II) complex (E,E)-NiL2 (BPh2 )2 (2) The boron diphenyl bridged Ni(II) complex (2) was prepared at room temperature from the solution of H2 L and NiCl2 6H2 O in ethanol, with an excess NaBPh4 . The bridging protons (O–H–O) that are involved in intramolecular hydrogen bonding in complex 1, were replaced with BPh2þ groups to synthesize the O–B–O bridged Ni(II) complex 2. Also, the BPh2 -bridging dioxime complexes are known from previous studies [22], they are usually synthesized with diphenyl borinic anhydride to replace hydrogen atoms with boron ones on the dioxime complexes. In our study, replacements of the hydrogen atoms were carried out by using NaBPh4 instead of diphenyl borinic anhydride. In the 1 H NMR spectrum of 2, the deuterium exchangeable hydrogen-bridged protons, which were evident in 1, disappear after the formation of the BPh2þ -bridged complex. Indeed, the chemical shifts of the aromatic protons are obtained at d ¼ 7:19 ppm as multiplets, which proves that the O–H–O bridges between the molecules are replaced by BPh2þ . The chemical shifts of the aromatic C atoms are obtained at d ¼ 132:01, 127.11 and 125.78 ppm. The other chemical shifts (1 H- and 13 C NMR) belonging to BPh2þ -capped Ni(II) complex 2 are very similar to those for the hydrogen bonded Ni(II) complex 1. The IR spectra of BPh2þ -bridged Ni(II) complex is very similar to the hydrogen-bridged Ni(II) complex 1. A downward shift of the C@N stretching vibrations in the hydrogen-bridged complex indicates coordination through the N-atoms. In contrast to this downward shift, the BPh2þ macrocyles exhibit upward shifts of about 20–30 cm1 due to the strong electron withdrawing influence of BPh2þ groups incorporated in
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macrocycles. The stretching vibration of O–H–O bond at 3346 cm1 disappeared upon encapsulation of the Hbonded complex with the appearance of peaks due to the BPh2þ contaminant around 1190 and 860 cm1 for B–O and B–Ph groups, respectively [23]. The molecular structure of complex 2 is shown on Fig. 4. The complex molecule is centrosymmetrical. One methylene group (C3) was found to be disordered and was refined on two positions with half occupancy. As in complex 1 the nickel(II) ion is bound by the four oxime nitrogen atoms. The Ni–N(oxime) bond lengths Ni–N1 respectively, and and Ni–N4, 1.844(2) and 1.850(2) A, the N1–Ni–N4 of 82.8(1)° are similar to those observed for 1 (Table 2). In 2 the oximic oxygen atoms (O1, O3) are bound by the two BPh2 groups [O1–B ¼ 1.523(4) A and O3–B ¼ 1.521(4) A]. The distance between the oximic oxygen atoms bound by the boron atom [O1– is close to those found in 1 and in O3 ¼ 2.484(3) A] bis(diphenylboron-dimethylglyoximato)nickel(II) [22a]. As found for 1, there is a shortening of the N–O oxime as compared to that bond length [1.380(3)–1.390(3) A] However, as the found for the free ligand [1.434(1) A]. boron atoms are symmetrically bonded to the oximic oxygen atoms (O1, O3) the N–O bond lengths are closer in complex 2 [N1–O1 ¼ 1.380(3) and O3–N4 ¼ 1.390(3)] than in complex 1 (see above).
3. Experimental 3.1. Materials and methods Elemental analyses were obtained from Carlo Erba 1106 Instrument and FT-IR spectra were recorded on a Bio-Rad FTS 175C FTIR spectrophotometer as KBr pellets. Mass spectra were recorded on a VG Zab Spec GC-MS spectrometer using the liquid secondary ion mass spectrometer (LSIMS) method (35 kV) with mnitrobenzyl alcohol as the matrix. 1 H and 13 C NMR spectra were recorded in CDCl3 or in DMSO-d6 solutions on a Bruker 200 MHz spectrometer using TMS as an internal reference. 3.2. Crystallography Data were collected at room temperature (298 K) with a Bruker S M A R T CCD diffractometer equipped with a normal monochromatized focus X-ray tube having a molybdenum target. The data were processed through the S A I N T reduction software [24]. Empirical absorption corrections were carried out by SADABS (G. B. Sheldricks, 1994). The structures were solved and refined on F 2 using the S H E L X T L software [25]. All nonhydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms were included in the final refinement model in calculated positions with iso-
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tropic thermal parameters. Crystal structure and refinement data for the H2 L and its complexes 1 and 2 are summarized in Table 1. 3.3. Synthesis ðE; EÞ-dichloroglyoxime [26] and cyanogen di-Noxide [27] were prepared according to a described procedures. Other reagents and solvents were obtained from commercial suppliers and were dried as described in the literature [28] before use.
Table 1 Summary of data collection and refinement for compounds H2 L and its complexes 1 (molecule 1A and 1B) and 2
Formula Fw T (K) Crystal system Space group a (A) b (A) c (A) a (°) b (°) c (°) 3 ) V (A Z l (mm1 ) d (g cm3 ) k (A) R ðF Þa Rw (F 2 )b a b
H2 L
1
2
C14 H28 N6 O4 344.42 298(2) monoclinic C2=c 22.274(6) 6.130(2) 13.834(4) 90 113.07(1) 90 1737.9(8) 4 0.098 1.316 0.71073 0.0530 0.1589
C28 H56 N12 O9 Ni 763.56 298(2) triclinic P1 11.2413(7) 12.5612(8) 14.2781(9) 114.037(1) 90.707(1) 98.543(1) 1814.9(2) 2 0.601 1.397 0.71073 0.0385 0.1132
C52 H72 N12 O8 B2 Ni 1073.55 298(2) triclinic P1 9.136(1) 11.858(2) 13.259(2) 82.319(3) 73.906(3) 81.611(3) 1358.7(3) 1 0.421 1.312 0.71073 0.0567 0.1086
I > 2rðIÞ, RðF Þ ¼ RkFoj jFcj=RjFoj. All data, RwðF 2 Þ ¼ ½RwðFo2 Fc2 Þ2 =RwðFo2 Þ2 1=2 .
Table 2 and angles (°) for the ligand H2 L and its Selected bond lengths (A) complexes 1 and 2 H2 L O1–N1 N1–C1 N2–C1 C1–C1# C1–C8 O3–N4 N4–C8 N5–C8 Ni–N1 Ni–N4 B–O1 B–O3 N1–Ni–N4 N1–Ni–N4# O1–B–O3# O1–O3#
1.434(1) 1.283(2) 1.356(2) 1.497(2)
1A
1B
2
1.391(2) 1.305(3) 1.337(3)
1.393(2) 1.301(3) 1.337(3)
1.380(3) 1.291(3) 1.346(4)
1.490(3) 1.356(2) 1.296(3) 1.366(3) 1.868(2) 1.864(2)
1.485(3) 1.345(2) 1.301(3) 1.370(3) 1.867(2) 1.863(2)
1.509(4) 1.390(3) 1.300(3) 1.328(3) 1.844(2) 1.850(2) 1.523(4) 1.521(4) 82.8(1) 97.3(1) 109.4(2) 2.484(3)
82.48(7) 97.52(7) 2.48(3)
82.71(7) 97.29(7) 2.485(3)
(# symmetry related position: H2 L, x; y; z 1=2; x; y þ 1; z; 1B, x; y; z; 2, x; y; z).
1A,
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3.3.1. N ; N 0 -bis[4-(2-aminoethyl)morpholino]glyoxime (H2 L) 3.3.1.1. Procedure A. A solution of cyanogen di-N-oxide, obtained by treating (E; E)-dichloroglyoxime (4.08 g, 25.9 mmol) in diethylether (50 ml) with 1 M Na2 CO3 (300 ml), was added at )20 °C to a stirring solution of 4(2-aminoethyl)morpholine (4.6 g, 35.3 mmol) in diethylether (50 ml). The reaction mixture was stirred at )20 °C for 2 h, then allowed to warm to room temperature. The white solid product which precipitated was filtered, washed with cold ethanol and then with cold diethylether. Recrystallization from water (50 ml) afforded a white crystalline solid. The product was soluble in water, acetonitrile, DMF, DMSO and hot ethanol. Yield: 2.45 g (%40). m.p.: 227–229 °C (dec.). Found C, 48.63; H, 8.04; N, 24.15%, C14 H28 N6 O4 ; requires C, 48.82; H, 8.19; N, 24.40%; IR (mmax /cm1 ) 3463 (OH), 3346 (NH), 2965–2823 (CH), 1639 (C@N), 1461 and 1353 (CH), 1113 (C–O), 1021 (N–O); MS (LSIMS), m=z (%): þ 345(100) ½M þ 1 , 327(15) [M–OH2 ]þ , 307(10), 289(8); 1 H NMR (DMSO-d6 ) d ppm: 9.49 (s, 2H, O–H), 5.64 (t, 2H, C–NH), 3.55 (t, 8H, CH2 –O), 3.12 (q, 4H, CH2 – NH), 2.38 (m, 12H, CH2 –N); 13 C NMR (DMSO-d6 ) d ppm: 146.9 (C@N–O), 66.40 (CH2 –O), 58.70 (CH2 –N), 53.45 (CH2 –N), 39.58 (CH2 –NH). 3.3.1.2. Procedure B. An excess of solid NaHCO3 (5 g) was added to a solution of 4-(2-aminoethyl)morpholine (3 g, 23 mmol) in 100 ml of ethanol. This mixture was stirred at room temperature for 2 h. To this mixture a solution of (E; E)-dichloroglyoxime (1.8 g, 11.5 mmol) in 100 ml of ethanol was added dropwise. The mixture was stirred at room temperature. After 24 h a white solid product was filtered and washed with cold ethanol and cold diethylether. Recrystallization from ethanol (200 ml) afforded a white crystalline solid. Yield: 0.85 g (%21). m.p.: 227–229 °C (dec.). 3.3.1.3. Procedure C. A mixture of 4-(2-aminoethyl)morpholine (3.28 g, 25.2 mmol) and (E; E)-dichloroglyoxime (1 g, 6.3 mmol) was ground thoroughly in a mortar and mixed with silica gel (7 g) (silica gel 60, 230-400mesh. Merck). The mixture, in a watch glass, was put inside a Beko Microwave (2450 MHz, 1330 W). The compounds were irradiated for 4 min and the progress of the reaction was monitored by TLC. After the completion of the reaction the mixture was cooled to room temperature. Then, 50 ml water was added to this mixture then stirred and filtered. The water was removed under reduced pressure. The white solid residue was dissolved in hot ethanol (100 ml) and cooled to room temperature. White crystals were filtered off, washed with cold diethylether and dried. Yield: 1.76 g (%81). m.p.: 227–229 °C (dec.).
3.3.2. Ni(II) complex [(E,E)-Ni(HL)2 ] H2 O (1) To a solution of H2 L (0.5 g, 1.45 mmol) in 150 ml of hot ethanol (60 °C) was added a solution of NiCl2 6H2 O (0.172 g, 0.724 mmol) in 10 ml of hot ethanol (60 °C). After 15 minute of stirring at 60 °C an orange colored solution was obtained. Removal of ethanol under reduced pressure gave an orange solid residue that was dissolved in CH2 Cl2 (100 ml). The solution was filtered, extracted with water and then dried with Na2 SO4 . The CH2 Cl2 was removed after filtration of the solution to give an orange product. Recrystallization from CH2 Cl2 /n-heptane (1:10) gave orange single crystals which were filtered, washed with n-heptane and dried. Yield: 0.254 g (%47). m.p.: 182–183 °C. Found C, 44.97; H, 7.19; N, 22.63%, C28 H56 N12 O9 Ni; requires C, 44.05, H, 7.39 N, 22.01%; IR (mmax /cm1 ) 3346 (OH), 3329 (NH), 2959–2820 (CH), 1588 (C@N), 1454 and 1338 (CH), 1118 (C–O), 1025 (N–O); MS (LSIMS), m=z (%): 745(100) ½M þ 1þ , 242(5); 1 H NMR (DMSO-d6 ) d ppm: 16.84 (s, 2H, O–H–O), 6.00 (t, 4H, C–NH), 3.61 (t, 16H, CH2 –O), 3.24 (q, 8H, CH2 –NH), 2.38 (m, 24H, CH2 –N); 13 C NMR (DMSO-d6 ) d ppm: 144.85 (C@N– O), 66.08 (CH2 –O), 58.73 (CH2 –N), 53.17 (CH2 –N), 40.88 (CH2 –NH). 3.3.3. Ni(II) complex (E,E)-NiL2 (BPh2 )2 (2) To a solution of H2 L (0.5 g, 1.45 mmol) in 150 ml of warm ethanol (60 °C) was added a solution of NiCl2 6H2 O (0.172 g, 0.724 mmol) in 10 ml of warm ethanol (60 °C) with stirring. The color of the solution turned to orange and then the ethanol solution was cooled to room temperature. A solution of excess NaBPh4 (3.97 g, 11.6 mmol) in 50 ml ethanol was added dropwise to this clear orange solution. The ethanol was removed under reduced pressure. The orange solid residue was dissolved with CH2 Cl2 (100 ml). The solution was filtered, extracted with water, dried with Na2 SO4 and then filtered. Removal of CH2 Cl2 gave an orange solid which was recrystallized from CH2 Cl2 /EtOH (1:10) to give orange single crystals which were filtered, washed with EtOH, n-heptane, diethylether and dried. Yield: 0.435 g (%47). m.p.: 291 °C(dec.). Found C, 58.01; H, 6.39; N, 15.72%, C52 H72 N12 O8 B2 Ni; requires C, 58.18; H, 6.76; N, 15.66%; IR (mmax /cm1 ) 3341 (NH), 3067 (Ar–CH), 2856–2819 (CH2 ), 1612 (C@N), 1508 and 1430 (C–H), 1190 (B–O), 1119 (C–O), 1010 (N–O), 860 (B–Ph), 738 and 704 (Ar–CH).
4. Supplementary material View of the crystal packing of the ligand H2 L along the b axis in Fig. 1S. Tables of atomic coordinates, anisotropic thermal parameters, bond lengths and angles have been deposited with the Cambridge Crystallographic Data Center as CCDC deposition number 193792–
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[7] [8] [9] [10]
Fig. 1S. View of the crystal packing of the ligand H2 L along the b axis.
193794 for H2 L, 1 and 2. Copies of the data may be obtained free of charge on application from The Director, CCDC, 12 Union Road, Cambridge CB2 1 EZ, UK (fax: +44-1223-336-033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).
[11] [12] [13]
[14] [15]
Acknowledgements This work was supported in France by the Centre National de la Recherche Scientifique (CNRS), the Commissariat a lÕEnergie Atomique (CEA) and Grenoble University (UJF). Grants for travelling between France and Turkey were sponsored through the CNRSTUBITAK collaboration program.
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Synthesis and structures of morpholine substituted new vic-dioxime ligand and its Ni(II) complexes Mahmut Durmusß a, Vefa Ahsen
a,b,*
, Dominique Luneau
c,*,1
, Jacques Pecaut
c
a
Department of Chemistry, Gebze Institute of Technology, P.O. Box 141, Gebze, Kocaeli 41400, Turkey TUBITAK-Marmara Research Center, Materials and Chemical Technologies Research Institute, P.O. Box 21, Gebze, Kocaeli 41470, Turkey Laboratoire de Chimie Inorganique et Biologique (UMR 5046), DRFMC, CEA-Grenoble, 17 rue des Martyrs, Grenoble Cedex 09, 38054, France b
c
Received 21 October 2002; accepted 23 May 2003
Abstract N; N 0 -bis[4-(2-aminoethyl)morpholino]glyoxime (H2 L) (Fig. 1), has been prepared in various yields using three different methods. The most efficient of these methods is the technique of microwave irradiation. The crystal structures of H2 L, and of two nickel(II) complexes 1 and 2 have been determined by single crystal X-ray diffraction. Both nickel(II) complexes have a metal–ligand ratio of 1:2 in which the ligand coordinates through the two nitrogen atoms as do most vic-dioximes. The nickel(II) complexes are either hydrogen (1) or boron diphenyl bridged (2). Complex 1 was synthesized by reacting H2 L with nickel(II) chloride in refluxing ethanol. Complex 2 was prepared at room temperature in an ethanol solution containing excess NaBPh4 . Elemental analyses, NMR(1 H, 13 C), IR and mass data are also presented. Ó 2003 Published by Elsevier B.V. Keywords: vic-Dioximes; Nickel(II) complexes; Glyoximes
1. Introduction vic-Dioximes and their complexes constitute an important class of compounds having versatile reactivities [1]. Since the pioneering work of Schrauzer [2] cobaloximes have been widely studied as the model for coenzyme B12 . These are bis complexes of dimethylglyoximate. Discoveries on B12 models made since 1989 are assessed in the light of the advances in structural and spectroscopic methodologies. Further studies emanating in part from these advances have confirmed previously identified principles describing the properties of the classic simple models(cobaloximes and iminocobaloximes) and have established some new principles defining the properties of the axial Co–C and Co–N bonds [3]. * Corresponding authors. Tel.: +90-262-641-2300; fax: +90-262-6412309 (V. Ahsen). E-mail addresses: [email protected] (V. Ahsen), [email protected] (D. Luneau). 1 Present address: Universite Claude Bernard Lyon 1, B^at 305, 43 Avenue du 11 Novembre 1918, 69622 Villeurbanne Cedex, France.
0020-1693/$ - see front matter Ó 2003 Published by Elsevier B.V. doi:10.1016/j.ica.2003.05.004
The exceptional stability and unique electronic properties of the vic-dioximes complexes can be attributed to their planar structure which is stabilized by hydrogen bridges. Moreover, in the last decade, polymetallic complexes were synthesized with various vic-dioxime [4], after removal of the hydrogen bridge. This has demonstrated that the oximate group may also act as a bridging ligand to mediate strong antiferromagnetic exchange interactions between the bridged metal ions. This was successfully used to synthesize extended bimetallic compounds with magnet behaviors [5]. Furthermore, vic-dioximes are easily modified by substitution with various groups. The reaction of amines or thiols with (E; E)-dichloroglyoxime or cyanogendi-N-oxide yielded various symmetrically substituted diaminoglyoxime or dithioglyoxime derivatives [6]. In previous papers the synthesis of vic-dioxime ligands and their transition metal complexes containing crown ethers [7], monoaza crown ethers [8], ferrocene groups [9], tetrathiamacrocycles [10], or N2 O2 macrocycles [11] and dendritic groups [12] have also been reported. Other investigated fields for these compounds concern liquid
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crystals [13], gas sensors [14] and inhibitors for chemical warfare agents [15]. Herein, we present the synthesis of a morpholine substituted diaminodioxime ligand (H2 L), together with two nickel(II) complexes. The ligand was obtained using both conventional methods and in solvent-free conditions using the microwave irradiation technique in presence of silica gel. In all cases we obtained the anti ðE; EÞ isomer of H2 L. The structure of the ligand (Figs. 1 and 2) and its complexes (Figs. 3 and 4) have been identified by a combination of elemental analysis, 1 H and 13 C NMR, IR
Fig. 4. View of the molecular structure for complex 2 (E; E)-NiL2 BPh2 . Ellipsoids are drawn at the 30% probability level. Fig. 1. Chemical structure of H2 L.
and mass spectral data and X-ray crystal structure (see Fig. 1).
2. Results and discussion 2.1. Ligand (H2 L)
Fig. 2. View of the molecular structure of the ligand H2 L. Ellipsoids are drawn at the 30% probability level.
Fig. 3. View of the molecular structure for complex 1 (E; E)-Ni(HL)2 (molecule 1A). Ellipsoids are drawn at the 30% probability level.
In this work we prepared vic-dioxime ligand (H2 L) in various yields following three different synthesis methods. Along the first method (A), H2 L was synthesized from the reaction of a solution of 4-(2-aminoethyl)morpholine in diethylether with a solution of cyanogen di-N-oxide in diethylether. In a second method (B), 4-(2-aminoethyl) morpholine was reacted with ethanolic (E; E)-dichloroglyoxime in the presence of NaHCO3 as a buffer to neutralize HCl formed during the reaction. In the third method (C), H2 L was obtained by microwave irradiation in solvent-free conditions in the presence of silica gel. In the 1 H NMR spectrum of H2 L in DMSO-d6 , the deuterium exchangeable protons of the @N–OH groups show only one chemical shifts at d ¼ 9:49 ppm as a singlet which indicates an (E; E)-structure for the vicinal dioxime [16]. The chemical shifts which belong to –NH protons were observed at d ¼ 5:64 ppm as a triplet and disappeared with D2 O exchange. The chemical shifts which belong to –CH2 protons were observed at d ¼ 3:55 ppm (CH2 –O), 3.12 ppm (CH2 –NH) and 2.38 ppm (CH2 –N). The chemical shifts of CH2 –N protons at d ¼ 3:12 ppm were observed as quartet, but they converted to a triplet after D2 O exchange. More detailed information about the structure of H2 L is provided by
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13
C NMR spectral data. The chemical shifts for the amide carbon atoms are found at d ¼ 146:9 ppm [17]. These equivalent carbon atoms, especially belonging to hydroxyimino carbon atoms, also confirm the anti structure of H2 L [18]. The mass spectrum (LSIMS) of H2 L exhibits a molecular ion peak at m=z 345 ½M þ 1þ . The peak 327 indicates the loss of water ([M–OH2 ]þ ). In the IR spectrum of H2 L, the O–H stretching vibration is observed at 3463 cm1 . Bands due to N–H, C@N and N–O stretches are at 3346, 1639, 1021 cm1 . The stretching vibration for –NH2 disappears after the condensation reaction of 4-(2-aminoethyl)morpholine with (E; E)-dichloroglyoxime. These results indicate that the formation of vic-dioxime ligand was completed. The molecular structure of the ligand H2 L is shown on Fig. 2. The asymmetric unit comprises one half molecule of the ligand. The whole molecule is deduced by symmetry operation (x; y; y 1=2) and has a butterfly shape. The two symmetry related moieties make an angle of 80.0°. The oxime groups have the anti (E; E) conformation in agreement with the 1 H NMR spectrum. The bond lengths and angles are found to be normal (Table 2). Intermolecular hydrogen bonds involve the oxime groups with the morpholine nitrogen atoms (N3) and with the amido nitrogen atoms (N2) (O1–N3 ¼ 2.760(2) and O1–N2 ¼ 2.925(2) A). This affords chains which A are parallel to the c axis direction (Fig. 1S, in supplementary material). 2.2. Nickel(II) complex [(E,E)-Ni(HL)2 ] H2 O (1) This was obtained by refluxing the ligand and NiCl2 6H2 O (ratio 2:1) together in ethanol. The complex is soluble in common organic solvents, which allowed full characterization. In the 1 H NMR spectrum of 1, the resonances of intramolecular bonding OH–O protons shifted to d ¼ 16.84 ppm, which disappear by D2 O exchange. The other chemical shifts (1 H- and 13 C NMR) observed for complex 1 are very similar to those found for the ligand H2 L. In the IR spectrum the usual hydrogen bridges of the square-planar vic-dioxime complexes were also characterized by the weak deformation bands [19] around 1730 cm1 . The C@N vibrations are at lower wave numbers, as expected for N ; N 0 -chelated vicinal dioxime complexes. The crystal structure of complex 1 consists of two crystallographically independent complex molecules, which are denoted molecule 1A and molecule 1B, and crystallize with water molecules. A view of the complex molecules is shown on Fig. 3 (molecule 1A). Some methylene groups (C10A, C9B, C10B) were found to be disordered and were refined on two positions with a half occupancy. The complex molecules are centrosymmetrical. The nickel(II) ion is in a square planar environment and is bound by the four oxime nitrogens atoms.
The Ni–N(oxime) bond lengths [1.863(2)–1.868(2) A] (Table 2) are in the previously observed range for nickel(II)-dioxime complexes [20]. The N1A–NiA–N4A and N1B–NiB–N4B are 82.48(7)° and 82.71(7)°, respectively. The complexation leads to a shortening of as the N–O oxime bond length [1.345(2)–1.393(2) A] compared to that found for the free ligand [1.434(1) A]. In each of the molecule 1A and 1B, the oximic oxygen atoms are hydrogen bonded as normally observed for the anti isomer complex of dioxime [O1A–O3A ¼ and O1B–O3B ¼ 2.485(2) A] [21]. The dif2.482(3) A ferences found between the N1–O1 and N4–O3 bond lengths [N1A–O1A ¼ 1.391(2), N1B–O1B ¼ 1.393(2), N4A–O3A ¼ 1.356(2) and N4B–O3B ¼ 1.345(2)] are due to the fact that the hydrogen atoms are not symmetrically located between the oximic oxygen atoms (O1 and O3) as previously observed [21]. The water molecules are found to be hydrogen bonded to the oximic oxygen at and O9w–O3B ¼ 3.015(3) oms [O9w–O3A ¼ 2.855(3) A A]. 2.3. Nickel(II) complex (E,E)-NiL2 (BPh2 )2 (2) The boron diphenyl bridged Ni(II) complex (2) was prepared at room temperature from the solution of H2 L and NiCl2 6H2 O in ethanol, with an excess NaBPh4 . The bridging protons (O–H–O) that are involved in intramolecular hydrogen bonding in complex 1, were replaced with BPh2þ groups to synthesize the O–B–O bridged Ni(II) complex 2. Also, the BPh2 -bridging dioxime complexes are known from previous studies [22], they are usually synthesized with diphenyl borinic anhydride to replace hydrogen atoms with boron ones on the dioxime complexes. In our study, replacements of the hydrogen atoms were carried out by using NaBPh4 instead of diphenyl borinic anhydride. In the 1 H NMR spectrum of 2, the deuterium exchangeable hydrogen-bridged protons, which were evident in 1, disappear after the formation of the BPh2þ -bridged complex. Indeed, the chemical shifts of the aromatic protons are obtained at d ¼ 7:19 ppm as multiplets, which proves that the O–H–O bridges between the molecules are replaced by BPh2þ . The chemical shifts of the aromatic C atoms are obtained at d ¼ 132:01, 127.11 and 125.78 ppm. The other chemical shifts (1 H- and 13 C NMR) belonging to BPh2þ -capped Ni(II) complex 2 are very similar to those for the hydrogen bonded Ni(II) complex 1. The IR spectra of BPh2þ -bridged Ni(II) complex is very similar to the hydrogen-bridged Ni(II) complex 1. A downward shift of the C@N stretching vibrations in the hydrogen-bridged complex indicates coordination through the N-atoms. In contrast to this downward shift, the BPh2þ macrocyles exhibit upward shifts of about 20–30 cm1 due to the strong electron withdrawing influence of BPh2þ groups incorporated in
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macrocycles. The stretching vibration of O–H–O bond at 3346 cm1 disappeared upon encapsulation of the Hbonded complex with the appearance of peaks due to the BPh2þ contaminant around 1190 and 860 cm1 for B–O and B–Ph groups, respectively [23]. The molecular structure of complex 2 is shown on Fig. 4. The complex molecule is centrosymmetrical. One methylene group (C3) was found to be disordered and was refined on two positions with half occupancy. As in complex 1 the nickel(II) ion is bound by the four oxime nitrogen atoms. The Ni–N(oxime) bond lengths Ni–N1 respectively, and and Ni–N4, 1.844(2) and 1.850(2) A, the N1–Ni–N4 of 82.8(1)° are similar to those observed for 1 (Table 2). In 2 the oximic oxygen atoms (O1, O3) are bound by the two BPh2 groups [O1–B ¼ 1.523(4) A and O3–B ¼ 1.521(4) A]. The distance between the oximic oxygen atoms bound by the boron atom [O1– is close to those found in 1 and in O3 ¼ 2.484(3) A] bis(diphenylboron-dimethylglyoximato)nickel(II) [22a]. As found for 1, there is a shortening of the N–O oxime as compared to that bond length [1.380(3)–1.390(3) A] However, as the found for the free ligand [1.434(1) A]. boron atoms are symmetrically bonded to the oximic oxygen atoms (O1, O3) the N–O bond lengths are closer in complex 2 [N1–O1 ¼ 1.380(3) and O3–N4 ¼ 1.390(3)] than in complex 1 (see above).
3. Experimental 3.1. Materials and methods Elemental analyses were obtained from Carlo Erba 1106 Instrument and FT-IR spectra were recorded on a Bio-Rad FTS 175C FTIR spectrophotometer as KBr pellets. Mass spectra were recorded on a VG Zab Spec GC-MS spectrometer using the liquid secondary ion mass spectrometer (LSIMS) method (35 kV) with mnitrobenzyl alcohol as the matrix. 1 H and 13 C NMR spectra were recorded in CDCl3 or in DMSO-d6 solutions on a Bruker 200 MHz spectrometer using TMS as an internal reference. 3.2. Crystallography Data were collected at room temperature (298 K) with a Bruker S M A R T CCD diffractometer equipped with a normal monochromatized focus X-ray tube having a molybdenum target. The data were processed through the S A I N T reduction software [24]. Empirical absorption corrections were carried out by SADABS (G. B. Sheldricks, 1994). The structures were solved and refined on F 2 using the S H E L X T L software [25]. All nonhydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms were included in the final refinement model in calculated positions with iso-
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tropic thermal parameters. Crystal structure and refinement data for the H2 L and its complexes 1 and 2 are summarized in Table 1. 3.3. Synthesis ðE; EÞ-dichloroglyoxime [26] and cyanogen di-Noxide [27] were prepared according to a described procedures. Other reagents and solvents were obtained from commercial suppliers and were dried as described in the literature [28] before use.
Table 1 Summary of data collection and refinement for compounds H2 L and its complexes 1 (molecule 1A and 1B) and 2
Formula Fw T (K) Crystal system Space group a (A) b (A) c (A) a (°) b (°) c (°) 3 ) V (A Z l (mm1 ) d (g cm3 ) k (A) R ðF Þa Rw (F 2 )b a b
H2 L
1
2
C14 H28 N6 O4 344.42 298(2) monoclinic C2=c 22.274(6) 6.130(2) 13.834(4) 90 113.07(1) 90 1737.9(8) 4 0.098 1.316 0.71073 0.0530 0.1589
C28 H56 N12 O9 Ni 763.56 298(2) triclinic P1 11.2413(7) 12.5612(8) 14.2781(9) 114.037(1) 90.707(1) 98.543(1) 1814.9(2) 2 0.601 1.397 0.71073 0.0385 0.1132
C52 H72 N12 O8 B2 Ni 1073.55 298(2) triclinic P1 9.136(1) 11.858(2) 13.259(2) 82.319(3) 73.906(3) 81.611(3) 1358.7(3) 1 0.421 1.312 0.71073 0.0567 0.1086
I > 2rðIÞ, RðF Þ ¼ RkFoj jFcj=RjFoj. All data, RwðF 2 Þ ¼ ½RwðFo2 Fc2 Þ2 =RwðFo2 Þ2 1=2 .
Table 2 and angles (°) for the ligand H2 L and its Selected bond lengths (A) complexes 1 and 2 H2 L O1–N1 N1–C1 N2–C1 C1–C1# C1–C8 O3–N4 N4–C8 N5–C8 Ni–N1 Ni–N4 B–O1 B–O3 N1–Ni–N4 N1–Ni–N4# O1–B–O3# O1–O3#
1.434(1) 1.283(2) 1.356(2) 1.497(2)
1A
1B
2
1.391(2) 1.305(3) 1.337(3)
1.393(2) 1.301(3) 1.337(3)
1.380(3) 1.291(3) 1.346(4)
1.490(3) 1.356(2) 1.296(3) 1.366(3) 1.868(2) 1.864(2)
1.485(3) 1.345(2) 1.301(3) 1.370(3) 1.867(2) 1.863(2)
1.509(4) 1.390(3) 1.300(3) 1.328(3) 1.844(2) 1.850(2) 1.523(4) 1.521(4) 82.8(1) 97.3(1) 109.4(2) 2.484(3)
82.48(7) 97.52(7) 2.48(3)
82.71(7) 97.29(7) 2.485(3)
(# symmetry related position: H2 L, x; y; z 1=2; x; y þ 1; z; 1B, x; y; z; 2, x; y; z).
1A,
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3.3.1. N ; N 0 -bis[4-(2-aminoethyl)morpholino]glyoxime (H2 L) 3.3.1.1. Procedure A. A solution of cyanogen di-N-oxide, obtained by treating (E; E)-dichloroglyoxime (4.08 g, 25.9 mmol) in diethylether (50 ml) with 1 M Na2 CO3 (300 ml), was added at )20 °C to a stirring solution of 4(2-aminoethyl)morpholine (4.6 g, 35.3 mmol) in diethylether (50 ml). The reaction mixture was stirred at )20 °C for 2 h, then allowed to warm to room temperature. The white solid product which precipitated was filtered, washed with cold ethanol and then with cold diethylether. Recrystallization from water (50 ml) afforded a white crystalline solid. The product was soluble in water, acetonitrile, DMF, DMSO and hot ethanol. Yield: 2.45 g (%40). m.p.: 227–229 °C (dec.). Found C, 48.63; H, 8.04; N, 24.15%, C14 H28 N6 O4 ; requires C, 48.82; H, 8.19; N, 24.40%; IR (mmax /cm1 ) 3463 (OH), 3346 (NH), 2965–2823 (CH), 1639 (C@N), 1461 and 1353 (CH), 1113 (C–O), 1021 (N–O); MS (LSIMS), m=z (%): þ 345(100) ½M þ 1 , 327(15) [M–OH2 ]þ , 307(10), 289(8); 1 H NMR (DMSO-d6 ) d ppm: 9.49 (s, 2H, O–H), 5.64 (t, 2H, C–NH), 3.55 (t, 8H, CH2 –O), 3.12 (q, 4H, CH2 – NH), 2.38 (m, 12H, CH2 –N); 13 C NMR (DMSO-d6 ) d ppm: 146.9 (C@N–O), 66.40 (CH2 –O), 58.70 (CH2 –N), 53.45 (CH2 –N), 39.58 (CH2 –NH). 3.3.1.2. Procedure B. An excess of solid NaHCO3 (5 g) was added to a solution of 4-(2-aminoethyl)morpholine (3 g, 23 mmol) in 100 ml of ethanol. This mixture was stirred at room temperature for 2 h. To this mixture a solution of (E; E)-dichloroglyoxime (1.8 g, 11.5 mmol) in 100 ml of ethanol was added dropwise. The mixture was stirred at room temperature. After 24 h a white solid product was filtered and washed with cold ethanol and cold diethylether. Recrystallization from ethanol (200 ml) afforded a white crystalline solid. Yield: 0.85 g (%21). m.p.: 227–229 °C (dec.). 3.3.1.3. Procedure C. A mixture of 4-(2-aminoethyl)morpholine (3.28 g, 25.2 mmol) and (E; E)-dichloroglyoxime (1 g, 6.3 mmol) was ground thoroughly in a mortar and mixed with silica gel (7 g) (silica gel 60, 230-400mesh. Merck). The mixture, in a watch glass, was put inside a Beko Microwave (2450 MHz, 1330 W). The compounds were irradiated for 4 min and the progress of the reaction was monitored by TLC. After the completion of the reaction the mixture was cooled to room temperature. Then, 50 ml water was added to this mixture then stirred and filtered. The water was removed under reduced pressure. The white solid residue was dissolved in hot ethanol (100 ml) and cooled to room temperature. White crystals were filtered off, washed with cold diethylether and dried. Yield: 1.76 g (%81). m.p.: 227–229 °C (dec.).
3.3.2. Ni(II) complex [(E,E)-Ni(HL)2 ] H2 O (1) To a solution of H2 L (0.5 g, 1.45 mmol) in 150 ml of hot ethanol (60 °C) was added a solution of NiCl2 6H2 O (0.172 g, 0.724 mmol) in 10 ml of hot ethanol (60 °C). After 15 minute of stirring at 60 °C an orange colored solution was obtained. Removal of ethanol under reduced pressure gave an orange solid residue that was dissolved in CH2 Cl2 (100 ml). The solution was filtered, extracted with water and then dried with Na2 SO4 . The CH2 Cl2 was removed after filtration of the solution to give an orange product. Recrystallization from CH2 Cl2 /n-heptane (1:10) gave orange single crystals which were filtered, washed with n-heptane and dried. Yield: 0.254 g (%47). m.p.: 182–183 °C. Found C, 44.97; H, 7.19; N, 22.63%, C28 H56 N12 O9 Ni; requires C, 44.05, H, 7.39 N, 22.01%; IR (mmax /cm1 ) 3346 (OH), 3329 (NH), 2959–2820 (CH), 1588 (C@N), 1454 and 1338 (CH), 1118 (C–O), 1025 (N–O); MS (LSIMS), m=z (%): 745(100) ½M þ 1þ , 242(5); 1 H NMR (DMSO-d6 ) d ppm: 16.84 (s, 2H, O–H–O), 6.00 (t, 4H, C–NH), 3.61 (t, 16H, CH2 –O), 3.24 (q, 8H, CH2 –NH), 2.38 (m, 24H, CH2 –N); 13 C NMR (DMSO-d6 ) d ppm: 144.85 (C@N– O), 66.08 (CH2 –O), 58.73 (CH2 –N), 53.17 (CH2 –N), 40.88 (CH2 –NH). 3.3.3. Ni(II) complex (E,E)-NiL2 (BPh2 )2 (2) To a solution of H2 L (0.5 g, 1.45 mmol) in 150 ml of warm ethanol (60 °C) was added a solution of NiCl2 6H2 O (0.172 g, 0.724 mmol) in 10 ml of warm ethanol (60 °C) with stirring. The color of the solution turned to orange and then the ethanol solution was cooled to room temperature. A solution of excess NaBPh4 (3.97 g, 11.6 mmol) in 50 ml ethanol was added dropwise to this clear orange solution. The ethanol was removed under reduced pressure. The orange solid residue was dissolved with CH2 Cl2 (100 ml). The solution was filtered, extracted with water, dried with Na2 SO4 and then filtered. Removal of CH2 Cl2 gave an orange solid which was recrystallized from CH2 Cl2 /EtOH (1:10) to give orange single crystals which were filtered, washed with EtOH, n-heptane, diethylether and dried. Yield: 0.435 g (%47). m.p.: 291 °C(dec.). Found C, 58.01; H, 6.39; N, 15.72%, C52 H72 N12 O8 B2 Ni; requires C, 58.18; H, 6.76; N, 15.66%; IR (mmax /cm1 ) 3341 (NH), 3067 (Ar–CH), 2856–2819 (CH2 ), 1612 (C@N), 1508 and 1430 (C–H), 1190 (B–O), 1119 (C–O), 1010 (N–O), 860 (B–Ph), 738 and 704 (Ar–CH).
4. Supplementary material View of the crystal packing of the ligand H2 L along the b axis in Fig. 1S. Tables of atomic coordinates, anisotropic thermal parameters, bond lengths and angles have been deposited with the Cambridge Crystallographic Data Center as CCDC deposition number 193792–
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[7] [8] [9] [10]
Fig. 1S. View of the crystal packing of the ligand H2 L along the b axis.
193794 for H2 L, 1 and 2. Copies of the data may be obtained free of charge on application from The Director, CCDC, 12 Union Road, Cambridge CB2 1 EZ, UK (fax: +44-1223-336-033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).
[11] [12] [13]
[14] [15]
Acknowledgements This work was supported in France by the Centre National de la Recherche Scientifique (CNRS), the Commissariat a lÕEnergie Atomique (CEA) and Grenoble University (UJF). Grants for travelling between France and Turkey were sponsored through the CNRSTUBITAK collaboration program.
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