Metal coordination architectures of N-acyl-salicylhydrazides: The effect of metal ions and steric repulsion of ligands to their structures of polynuclear metal complexes

Polyhedron 28 (2009) 300–306

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Metal coordination architectures of N-acyl-salicylhydrazides: The effect of metal ions and steric repulsion of ligands to their structures of polynuclear metal complexes Wei Luo a,*, Xiu-Teng Wang b, Xiang-Gao Meng c, Gong-Zhen Cheng a,*, Zhen-Ping Ji a a

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, PR China Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China c Key Laboratory of Pesticide and Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China b

a r t i c l e

i n f o

Article history: Received 10 July 2008 Accepted 22 October 2008 Available online 4 December 2008 Keywords: Polynuclear Mn and Cu complexes N-Acyl-salicylhydrazides Steric effect Metallacrown Trinuclear

a b s t r a c t Three polynuclear transition metal complexes [Mn8(DMF)8(L1)8]  4DMF (1), [Mn6(DMF)6(L2)6]  [Mn6(DMF)4(H2O)2(L2)6]  2DMF (2), [Cu3(L3)2(py)2] (3) of the pentadentate ligands N-acyl-salicylhydrazides were synthesized and characterized, their crystal structures were investigated. The oxidation state and properties of the central metal ions are important in crystal structure formation, trivalent Mn(III) ion which easily form stable octahedral coordination metallamacrocycle complexes, metallacrowns 1 and 2 were obtained; while bivalent Cu(II) ion is easier to form square planar, trinuclear complexes 3 was obtained. The steric effect of the N-acyl side chains also plays an important role in the structures of these polynuclear complexes. The magnetic property of 1 was also investigated. Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction Polynuclear transition metal complexes containing nitrogen and phenolic oxygen donor atoms are of considerable interest in inorganic and biomimetic chemistry due to their potential application in catalysis, their biological relevance, and potentially interesting magnetic properties [1]. To prepare such polynuclear complexes with desired structures and properties, it becomes important to understand the delicate factors influencing the formation of those systems [2,3]. The trianionic pentadentate Nacyl-salicylhydrazide ligands, a good example of these ligands, have been utilized to construct many interesting polynuclear complexes. Trivalent metal ions such as Ga, Co, Fe and Mn that can generally form stable octahedral coordination are found to yield hexanuclear, octanuclear, decanuclear and dodecanuclear metallamacrocycles with these ligands, known as metallacrowns [4–7], where the ring size and nuclearity of the metallacrowns could be modulated by controlling the steric repulsion of the N-acyl side chains. The ligands with flexible linear or b-branched N-alkyl groups that have sterically flexible Ca methylene groups tend to yield 18-membered hexanuclear metallacrowns; while for the ligands of a-branched N-alkyl groups, metallacrowns with extended

nuclearity have been prepared [8]. When the central atoms are bivalent metal ions that can easily form planar square coordination, several trinuclear nickel(II), copper(II) and zinc(II) compounds and one hexanuclear nickel(II) compound with these types of ligands have been reported [9]. Regardless of the ring size, metal ions, nuclearity or stereochemistry of these polynuclear complexes, the binding mode of the ligands around the metal centers are the same, it is the different connectivities of the ligands between the two kinds of metal ions that lead to the formation of metallacrowns and trinuclear complexes. With the aim of understanding the coordination chemistry of the N-acyl-salicylhydrazide with metal ions, and side effect of the N-acyl on the formation and structures of these polynuclear complexes, we report three pentadentate ligands N-2-methylacryloyl-5-bromosalicylhydrazide (H3L1), N-(phenylacetyl)-5-bromosalicylhydrazide (H3L2) and N-(3-t-butylbenzoyl)-5-bromosalicylhydrazide (H3L3) (Scheme 1) and three polynuclear complexes [Mn8(DMF)8(L1)8]  4DMF (1), [Mn6(DMF)6(L2)6]  [Mn6(DMF)4 (H2O)2(L2)6]  2DMF (2), [Cu3(L3)2(py)2] (3) from these ligands. 2. Experiment 2.1. General

* Corresponding authors. Tel.: +86 2787218274 (W. Luo). E-mail addresses: [email protected] (W. Luo), [email protected] (G.-Z. Cheng). 0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2008.10.055

All reagents for the syntheses were obtained commercially with analytical grade and were used without further purification. 1H and

W. Luo et al. / Polyhedron 28 (2009) 300–306

O

R1

R1

O

H3L1: R1 = 2-methyl-acryloyl, R2 = Br

M NH OH

HN

N O

301

H3L2: R1 = phenylacetyl, R2 = Br

N

M O

H3L3: R1 = 3-t-butylbenzoyl, R2 = Br

O

R2

R2 Scheme 1. The ligands and their same binding modes.

13 C NMR spectra were recorded on a Varian Inova 600 MHz NMR spectrometer at 25 °C. Chemical shifts were referenced to the residual solvent peak. IR spectra were recorded on AVATAR 360 FT-IR spectrophotometer in the range 4000–400 cm1 (KBr pellets). Element analyses were performed on a Perkin–Elmer 2400 CHN elemental analytical instrument. Temperature-dependent magnetic susceptibility measurements were carried out on powdered samples between 2 and 300 K using a Quantum Design (SQUID) magnetometer MPMS-XL-5 in a field of 1 kOe.

2.2. Synthesis of the ligands and metal complexes 2.2.1. N-2-Methyl-acryloyl-5-bromosalicylhydrazide (H3L1) 2-Methyl-acryloyl chloride (1.9 ml, 19.7 mmol) was added to a solution of chloroform (100 ml) containing water (0.36 ml, 20.0 mmol) and triethylamine (5.7 ml, 40.0 mmol) at 0 °C. The reaction mixture was slowly warmed to ambient temperature. Then a further amount of 2-methyl-acryloyl chloride (1.9 ml, 19.7 mmol) was added to the mixture and stirred for a further 1 h. At the completion of the above reaction, 5-bromosalicylhydrazide (3.7 g, 16.4 mmol) was added to the reaction mixture. The resulting mixture was stirred at ambient temperature for 1 day. The solution was diluted with hexane (90 ml), kept under refrigeration overnight, filtered, and washed with ether (30 ml  3), dried in vacuo over P2O5. Yield: 2.50 g, 83.5%. Anal. Calc. for C11H11N2O3Br: C, 44.17; H, 3.71; N, 9.37. Found: C, 44.06; H, 3.68; N, 9.41%. IR (KBr pellet, cm1): 3440 (s, broad); 3330 (s); 3130 (s, broad); 2760 (m); 2670 (m); 1670 (s); 1620 (s); 1590 (s); 1530 (m); 1480 (s); 1390 (s). 1H NMR (300 MHz, DMSO-d6), d ppm: 12.03 (s, 1H, Ar-OH); 10.52 (s, 1H), 10.27 (s, 1H) (both amide NH’s); 8.05 (s, 1H, Ar); 7.59 (s, 1H, Ar); 7.01 (s, 1H, Ar); 5.83 (s, 1H, –C@CH); 5.51 (s, 1H, –C@CH); 1.92 (s, 3H, –CH3). 13C NMR(150.9 MHz, DMSO-d6), d ppm: 168.40 (C7); 167.49 (C8); 159.71 (C2); 139.67 (C9); 138.22 (C4); 132.79 (C6); 122.93 (C1); 121.60 (C10); 119.99 (C3); 111.11 (C5); 20.39 (C11). 2.2.2. N-(Phenylacetyl)-5-bromosalicylhydrazide (H3L2) The ligand H3L2 was prepared in a manner analogous to that used for H3L1, except that phenylacetyl chloride was used instead of 2-methyl-acryloyl chloride. Yield: 4.98 g, 87.4%. Anal. Calc. for C15H13N2O3Br: C, 51.60; H, 3.75; N, 8.02. Found: C, 51.48; H, 3.75; N, 8.09%. IR (KBr pellet, cm1): 3440 (s); 3170 (s, broad); 2980 (s); 2670 (s); 1640 (s); 1610 (s); 1590 (vs); 1480 (s); 1390 (s); 1220 (s). 1H NMR (300 MHz, DMSO-d6), d ppm: 12.02 (s, 1H), 11.80 (s, 1H) (both amide NH’s); 10.68 (b, 1H, Ar-OH); 8.02 (s, 1H, Ar); 7.59 (m, 1H, Ar); 7.32 (d, 2H, Bz); 7.25 (dd, 2H, Bz); 7.03 (d, 1H, Ar); 3.57 (s, 2H, –CH2–). 13C NMR(150.9 MHz, DMSO-d6), d ppm: 169.15 (C8); 165.15 (C7); 158.24 (C6); 136.85 (C4); 136.27 (C10); 131.74 (C2); 129.77 (C11, C15); 128.95 (C12, C14); 127.23 (C13); 120.32 (C1); 118.08 (C5); 110.78 (C3); 45.97 (C9).

2.2.3. N-(3-t-Butylbenzoyl)-5-bromosalicylhydrazide (H3L3) The ligand H3L3 was prepared in a manner analogous to that used for H3L1, except that 3-t-butylbenzoyl chloride was used instead of 2-methyl-acryloyl chloride. Yield: 4.18 g, 65.2%. Anal. Calc. for C18H19N2O3Br: C, 55.24; H, 4.86; N, 7.16. Found: C, 55.18; H, 4.79; N, 7.21%. IR (KBr pellet, cm1): 3440 (s); 3190 (s, br); 2970 (s), 2680 (s); 2490 (m); 1750 (s); 1650 (s); 1610 (s); 1480 (s); 1400 (s). 1H NMR (300 MHz, DMSO-d6), d ppm: 12.09 (s, Ar-OH); 10.72 (s, 1H), 10.66 (s, 1H) (both amide NH’s); 8.04 (m, 1H, Ar); 7.85 (m, 1H, Ar); 7.56(m, 1H, Ar); 7.39 (d, 2H, Bz); 7.04 (d, 2H, Bz); 1.21 (s, 9H, –C(CH3)3. 13C NMR (150.9 MHz, DMSOd6), d ppm: 169.56 (C8); 162.63 (C7); 160.28 (C4); 153.33 (C12); 141.74 (C2); 140.13 (C6); 136.40 (C9); 135.49 (C10, C14); 134.86 (C11, C13); 132.47 (C5); 131.03 (C3); 125.17 (C1); 50.68 (C15); 36.34 (C16, C17, C18). 2.2.4. [Mn8(DMF)8(L1)8]  4DMF (1) H3L1 (29.9 mg, 0.1 mmol) was dissolved in 30 ml of 2:1 methanol + DMF, and manganese acetate tetrahydrate (24.5 mg, 0.1 mmol) was added to it, stirred for 2 h with the color of the solution changing to dark brown, then the mixture was filtered. After slow evaporation of the mother liquor over several weeks, dark brown block crystals suitable for X-ray diffraction were obtained. Yield: 65.3%. IR (KBr pellet, cm1): 3430 (s, br); 1650 (s); 1600 (m); 1560 (m); 1510 (s); 1430 (m); 715 (m); 629 (m). 2.2.5. [Mn6(DMF)6(L2)6][Mn6(DMF)4(H2O)2(L2)6]  2DMF (2) Complex 2 was prepared in a manner analogous to that of 1, use H3L2 as the ligand. Yield: 72.7%. IR (KBr pellet, cm1): 3440 (s, br); 1650 (s); 1600 (s); 1550 (s); 1500 (s); 1430 (s); 1380 (s); 729 (m); 633 (m). 2.2.6. [Cu3(L3)2(py)2] (3) H3L3 (39.0 mg, 0.1 mmol) was dissolved in 30 ml of 1:1 methanol/DMF, and then copper acetate monohydrate (19.9 mg, 0.1 mmol) was added, followed by four drops of pyridine. The mixture was stirred for 1 h, the resulting solution was filtered. After slow evaporation of the mother liquor for several days, blue block crystals suitable for X-ray diffraction were obtained. Yield: 67.5%. Anal. Calc. for C46H42Cu3N6O6Br2: C, 49.10; H, 3.76; N, 7.47. Found: C, 49.01; H, 3.71; N, 7.51%. IR (KBr pellet, cm1): 1610 (m); 1590 (m); 1500 (s); 1410 (s); 634 (w); 559 (w). 2.3. Crystallographic data collection and refinement of the structures X-ray single-crystal diffraction data for compounds 1–3 were collected on a Bruker Smart APEX diffractometer at 293 (2) K with Mo Ka radiation (k = 0.71073 Å). There was no evidence of crystal decay during data collection of complex 3. In the data collection of complexes 1 and 2, suitable crystal was mounted in glass

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Table 1 Crystal data and structure refinement parameters for complexes 1–3.

Formula Fw Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z D (g cm3) l (mm1) T (K) Ra/wRb Total/unique/Rint F(0 0 0) a b

1

2

3

C115H131Br8Mn8N25O36 3518.25 triclinic  P1

C222H222Br12Mn12N38O52 5872.58 triclinic  P1

18.1638(12) 19.7532(13) 23.0902(15) 75.017(5) 69.077(5) 79.164(5) 7433.1(8) 2 1.572 2.885 294(2) 0.0953/0.2394 71 638/25 997/0.1594 3528

16.2373(14) 16.7448(14) 26.53(2) 80.082(2) 76.886(2) 68.216(2) 6492(5) 1 1.502 2.486 292(2) 0.0838/0.2019 63 076/22 736/0.1518 2956

C46H42Br2Cu3N6O6 1125.30 monoclinic Cc 11.0820(10) 32.210(3) 13.5920(12) 90 108.305(2) 90 4606.2(7) 4 1.623 3.162 295(2) 0.0369/0.0666 14 853/8637/0.0323 2260

P P R = (||Fo|  |Fc||)/ |Fo|. P P wR ¼ ½ wðjF o j2  jF c j2 Þ2 = wðF 2o Þ1=2 .

capillaries with mother liquor to prevent the loss of the structure solvent molecules. In the complexes 1 and 2, the crystals diffracted poorly, with a relatively low percentage of observed intensities above the threshold of 2r(I) within the 1.73–25.00° (1) and 0.97–25.00° (2) h ranges. In complex 2, the non-coordinated solvent molecules are severely disordered which could not be modeled by discrete atoms in the complexes. Correspondingly, the contribution of the solvent to the diffraction pattern was subtracted using SQUEEZE procedure of the PLATON [10]. These voids consist of about 11.8% of the crystal volume (6492(5) per unit cell). Conventional least-squares refinement of the same solvent-exclude structure model against the original data set converged only at R1 = 0.22. Refinement calculations with the modified data converged at R1 = 0.0831 for 7965 reflections with intensities above the threshold of 2r(I). In the three complexes, the structures were solved by direct methods and all non-hydrogen atoms were refined

with anisotropic thermal parameters. All hydrogen atoms were located in calculated positions and/or in the position from difference Fourier map. The positions and anisotropy from difference of nonhydrogen atoms were refined on F2 by full-matrix least-squares techniques with the SHELXTL program package [11,12]. Crystal data of complexes 1–3 are listed in Table 1. 3. Results and discussion 3.1. Spectral characterization In the IR spectra, the ligands H3L1, H3L2 and H3L3 show stretching bands attributed to C@O, PhO–H (phenolic, including intramolecular and intermolecular hydrogen bond) and N–H at 1620, 1670, 2670–3130, 3440 cm1; 1610, 1640, 2670–3170, 3440 cm1 and 1610, 1650, 2490–3190, 3440 cm1, respectively [13]. The infrared

Fig. 1. Ortep plot of complex 1, H-atoms have been omitted for clarity.

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Fig. 2. Ortep plot of complex 2a, H-atoms have been omitted for clarity.

stretching bands for compounds 1–3 are quite similar. The absence of the N–H band and the weakness of the C@O stretching bands are consistent with the deprotonation of the CONH groups and coordination to the Mn(III) and Cu(II) ions, which indicate the same chelating mode of the ligands to metal ions. The deprotonation and coordination are also confirmed in complexes 1–3 by the bands at 715, 729 and 634 cm1, attributed to M–O linkages; bands at 629, 633 and 559 cm1, attributed to M–N linkages [14]. The

C@N–C@N framework bands are found at 1430 and 1410 cm1, respectively [15].

Fig. 3. Ortep plot of complex 2b, H-atoms have been omitted for clarity.

Fig. 4. Ortep plot of complex 3, H-atoms have been omitted for clarity.

3.2. Description of the structures of 1–3 The structure of complex 1 is illustrated in Fig. 1. The neighboring Mn  Mn interatomic distance are 4.886–4.935 Å. The Mn  Mn  Mn interatomic angles in the 24-membered core ring are in the range of 124.37–130.96°. These values are very close to the value of the interior angle in an n-octagon (135°). The flex-

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O

M

O

N R2

M

N O O

3+

S O

metallacrown

R1 R

1

M N N

M O

R2

R2 O

S1 O OH HN

R1

M

R1

N

NH

O

S2

Ni

trinuclear unit O

Ni

O

N

O

2+

R2

N

O

N S2

M

R1

S1

O

R2

R2 O

S

R1

M

O

N O

N

Cu trinuclear unit

N

O

N

O

M

Cu2+

S R1

O

R2 Scheme 2. Connective modes of metallacrown and trinuclear complex.

ibility around the N–N single bond and the conformational adaptability of the deprotonated pentadentate ligand (L1)3 assist the formation of the complex 1 and its propeller configuration of the Mn(III) ions. The chiralities of the manganese ions alternate between the K and D forms. The four DMF molecules coordinated to Mn centers with K configuration are on one face of the metallacrown, while the remaining four DMF molecules coordinated to the other Mn centers with D configuration on the other face of the metallacrown. The two faces of each metallacrown molecule have opposite chiralities. All manganese ions in 1 are in a distorted octahedral MnN2O4 geometry. In each octahedral environment around Mn(III), the mean axial distance of Mn–O/N is approximately 0.36 Å longer than the mean value of the basal distances due to the Jahn–Teller elongation of the octahedrons. The X-ray structure analysis results shown in Figs. 2 and 3 reveal that complex 2 is a hexanuclear Mn(III) metallacrown with a [Mn–N–N]6 unit, it has two independent molecules(2a and 2b) in each crystallographic asymmetric unit. All manganese ions of 2 are in an octahedral MnN2O4 environment, with the rest axial sites occupied by O atoms from six DMF molecules in 2b, and four DMF molecules, two H2O molecules in 2a. The mean axial distances are about 0.33 Å longer than the average basal bond lengths for each Mn(III) center, which indicates that the elongation of the octahedrons takes place in the axial direction due to the Jahn–Teller distortion of the high-spin d4 electronic configuration of Mn(III) ion. The pentadentate ligand (L2)3 not only bridge the adjacent man-

ganese ions by –N–N–, but also forces the stereochemistry of the metal ions into a propeller configuration because of the meridional coordination of the neighboring ligands. As a result, the complex 2 exhibits a combination of DKDK chiral configuration. The Mn  Mn distances fall in the range of 4.899–4.938 Å and the Mn  Mn  Mn angles of 112.63–116.02°. Complex 3 is composed of three Cu(II) ions, two (L3)3 ligands and two pyridine molecules, as shown in Fig. 4. The chelating modes of the ligands to Mn(III) ions and Cu(II) ions are the same, they serve as both bidentate ligand for one metal ions, and at the same time, tridentate ligand for the adjacent metal ions. Central copper ion and two terminal copper ions are connected by two bridging deprotonated (L3)3 ligands, forming a bent trinuclear copper structure unit with a Cu–N–N–Cu–N–N–Cu core. The coordination geometry of the central Cu(1) is distorted square, it is bound to carbonyl oxygen atoms, O(2) and O(4), two hydrazine nitrogen atoms N(1), N(4) from two ligands. For two terminal Cu(II) ions, the square geometry is realized with carbonyl oxygen, hydrazine nitrogen, phenolic oxygen and pyridine nitrogen atoms. The bent angle of Cu(2)  Cu(1)  Cu(3) is 162.7°. 3.3. Coordination architectures From the structures of complexes 1–3 and other trinuclear complexes obtained by us: [Ni3(H2O)2(DMA)2(acbshz)2]  2DMF [9b], [Ni3(pabshz)2(DMF)2(py)2, [Ni3(3-t[Cu3(3,5-dmbzshz)2(py)2,

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change coupling between the Mn(III) centers. This is further confirmed by a negative Weiss constant h = 31.6 K, which is calculated from the data within T > 55 K. The magnetic data were not fitted based on an eight Mn(III) ring model owing to the computing difficulties of dealing with such a large system. In order to evaluate the exchange interaction values of Mn(III) ions, the data were fitted to a one-dimensional chain model [16] since the ring is large and approximates a one-dimensional chain. The magnetic susceptibility of 1 can be written as [17]:

v¼

NSðS þ 1Þ 2 2 1  uðKÞ g b 8 3kT 1 þ uðKÞ

ð1Þ

where u(K) is 1/K  coth(K), K = 2JS(S + 1)/kT, S = 2 for Mn(II) and N, b, K, g and T have their usual meanings. The best fitting was obtained with g = 2.14(2), J = 1.94(4) K. The negative J value indicates the antiferromagnetic couplings between the Mn(III) centers. Fig. 5. Temperature dependence of vMT and W1 M of 1 at H = 1 kOe from 2 to 300 K. The line a represents the best fit to the Curie–Weiss law.

bbzshz)2(py)4  2H2O [9c], [Ni3(H2O)2(DMA)2(acshz)2]  2DMF [4i], [Cu3(mashz)2(py)2], [Ni3(mashz)2(py)4] [9e], [Ni3(3,5-dmbzshz)2 (py)4]  DMF1 [9d]. It is obvious that the N-acyl-salicylhydrazide ligands act as pentadentate ligands to metal ions, with bidentate to one metal ion centre and tridentate to the adjacent metal ion. The chelating modes of the ligands around the metal centers are the same, but the different connectivities of them lead to the formation of metallacrowns or trinuclear complexes. For trivalent metal ions Mn(III), Fe(III), Co(III) and Ga(III) that can easily form stable octahedral coordination, the two adjacent ligands serve as pentadentate to the central metal ion, and the one-by-one connectivity of these units forms a metallamacrocycle, known as metallacrowns. While for bivalent metal ions such as Cu(II), Ni(II) that are easier to form planar square geometry, the two adjacent ligands serve as tetradentate ligands to the central metal ions, but tridentate ligands to the terminal metal ions forming an isolated unit, so it can only form trinuclear complex (Scheme 2). The steric effect of the N-acyl side chains can also effect the formation of these polynuclear complexes. b-branched N-alkyl groups that have sterically flexible Ca methylene groups yield 18-membered hexanuclear metallacrown and linear trinuclear Ni(II) complex; while a-branched N-alkyl groups yield the 24-membered octanuclear Mn(III) metallacrown and bent trinuclear Ni(II) complex. In the trinuclear Cu(II) complexes, Cu(II) ions all take distorted planar square geometry, while in the trinuclear Ni(II) complexes, two terminal Ni(II) are distorted planar square, the central Ni(II) ions are octahedral. This difference reflects the steric requirement of coordination, and the presence of inter- and intra-molecular interactions. Further research on why the significantly bent molecular conformation is formed is still under way. 3.4. Magnetic properties The magnetic behavior of complex 1 is illustrated in Fig. 5. The value of vmT decreases slight with decreasing temperature from 26.07 cm3 mol1 K at 300 K to 18.16 cm3 mol1 K at 55 K. Below 55 K, vmT decreases rapidly and reaches 0.98 cm3 mol1 K at 2 K. The vmT value at 300 K is slightly larger than the sum value (24 cm3 mol1 K) expected for eight spin-only Mn(III) systems with S = 2. This behavior is characteristic of antiferromagnetic ex1 H3acbshz, H33,5-dmbzshz, H3pabshz, H33-t-bbzshz, H3acshz and H3mashz represent N-acyloyl-5-bromosalicylhydrazide, N-(3,5-dimethylbenzoyl)salicylhydrazide, N-(phenylacetyl)-5-bromosalicylhydrazide, N-(3-t-butylbenzoyl)salicylhydrazide, Nacryloyl-salicylhydrazide and N-2-methyl-acryloyl-5-bromosalicylhydrazide, respectively.

4. Conclusion Three complexes with the ligands derived from N-acyl-salicylhydrazides were reported. The 3d Metal coordination architectures of these kinds of ligands were also studied. For trivalent Mn(III), Fe(III), Co(III), Ga(III), which can easily form stable octahedral coordination, metallacrowns were obtained. While for bivalent Cu(II), Ni(II), Zn(II) that are easier to form planar square geometry, trinuclear complexes were obtained. The steric effect of the N-acyl side chains can also effect the formation of these polynuclear complexes. Antiferromagnetic couplings were observed between the Mn(III) centers in complex 1. Acknowledgment We greatly thank Prof. Song Gao for his kind help in the magnetic analysis. Appendix A. Supplementary data CCDC 678388, 678405 and 665860 contain the supplementary crystallographic data for 1–3. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.poly.2008.10.055. References [1] (a) A. Messerschmidt, A. Rossi, R. Ladenstein, R. Huber, M. Bolognesi, G. Gatti, A. Marchesini, R. Petruzzelli, A. Finazziagro, J. Mol. Biol. 206 (1989) 513; (b) V. Tangoulis, C.P. Raptopoulou, S. Paschalidou, E.G. Bakalbassis, S.P. Perlepes, A. Terzis, Angew. Chem., Int. Ed. 36 (1997) 1083; (c) V. Tangoulis, C.P. Raptopoulou, S. Paschalidou, A.E. Tsohos, E.G. Bakalbassis, A. Terzis, S.P. Perlepes, Inorg. Chem. 36 (1997) 5270; (d) A. Mukherjee, M. Nethaji, A.R. Chakravarty, Angew. Chem., Int. Ed. 43 (2004) 87; (e) Y. Nishida, S. Kida, J. Chem. Soc., Dalton Trans. (1986) 2633. [2] (a) S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853; (b) K. Severin, Chem. Commun. (2006) 3859; (c) J.J. Bodwin, A.D. Cutland, R.G. Malkani, V.L. Pecoraro, Coord. Chem. Rev. 216–217 (2001) 489; (d) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; (e) B.J. Holliday, C.A. Mirkin, Angew. Chem., Int. Ed. 40 (2001) 2022. [3] (a) P.J. Stang, B. Olenyuk, Acc. Chem. Res. 30 (1997) 502; (b) G. Mezei, P. Baran, R.G. Raptis, Angew. Chem., Int. Ed. 43 (2004) 574; (c) U. Patel, H.B. Singh, G. Wolmershäuser, Angew. Chem., Int. Ed. 44 (2005) 1715; (d) K.L. Taft, S.J. Lippard, J. Am. Chem. Soc. 112 (1990) 9629; (e) R. Wang, M. Hong, J. Luo, R. Cao, J. Weng, Chem. Commun. (2003) 1018; (f) D.T. Puerta, S.M. Cohen, Chem. Commun. (2003) 1278.

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