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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry

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Synthesis, Characterization, and Crystal Structures of Two Oxidomolybdenum(VI) Complexes With Hydrazones Derived from 3-Hydroxy-2-naphthoic Hydrazide
Jian-Ying Miao
a a

Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji, P. R. China Accepted author version posted online: 27 Jul 2012.Version of record first published: 05 Oct 2012.

To cite this article: Jian-Ying Miao (2012): Synthesis, Characterization, and Crystal Structures of Two Oxidomolybdenum(VI) Complexes With Hydrazones Derived from 3-Hydroxy-2-naphthoic Hydrazide, Synthesis and Reactivity in Inorganic, MetalOrganic, and Nano-Metal Chemistry, 42:10, 1463-1466 To link to this article: http://dx.doi.org/10.1080/15533174.2012.684229

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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:14631466, 2012 Copyright C Taylor & Francis Group, LLC ISSN: 1553-3174 print / 1553-3182 online DOI: 10.1080/15533174.2012.684229

Synthesis, Characterization, and Crystal Structures of Two Oxidomolybdenum(VI) Complexes With Hydrazones Derived from 3-Hydroxy-2-naphthoic Hydrazide
Jian-Ying Miao
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji, P. R. China

Downloaded by [Universiti Putra Malaysia] at 17:32 06 November 2012

Two mononuclear oxidomolybdenum(VI) complexes, [MoO2 (L1)(CH3 OH)]CH3 OH (1) and [MoO2 (L2)(CH3 OH)] (2) (H2 L1 = 3-hydroxynaphthalene-2-carboxylic acid (1-methyl-3-oxobutylidene)hydrazide, H2 L2 = 3-hydroxynaphthalene-2-carboxylic acid [1-(5-chloro-2-hydroxyphenyl)methylidene]hydrazide), were synthesized and characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. The Mo atom in each of the complexes is six-coordinated by the NNO donor atoms of the hydrazone ligand, one methanol O atom, and two oxo O atoms, forming an octahedral geometry. Keywords crystal structure, hydrazone, molybdenum complex, synthesis

2-carboxylic acid (1-methyl-3-oxo-butylidene)hydrazide, H2 L2 = 3-hydroxynaphthalene-2-carboxylic acid [1-(5-chloro2-hydroxyphenyl)methylidene]hydrazide).

OH H N O
H2L
1

OH

N O
H2L
2

H N O

N HO

Cl

EXPERIMENTAL Materials and Measurements 3-Hydroxy-2-naphthoic hydrazide, 5-chlorosalicylaldehyde, and MoO2 (acac)2 with AR grade were purchased from Lancaster (Britain) and used as obtained. C, H, and N elemental analyses were performed with a Perkin-Elmer 240C elemental analyzer (Shanghai, China). The IR spectra were recorded with a Nicolet FT-IR 170-SX spectrophotometer (Japan). Synthesis of [MoO2 (L1)(CH3 OH)]CH3 OH (1) A 5 mL methanol solution of 3-hydroxy-2-naphthoic hydrazide (0.1 mmol, 20.2 mg) was stirred to a 5 mL methanol solution of MoO2 (acac)2 (0.1 mmol, 33.1 mg). The mixture was stirred at reux for 1 h to give a clear yellow solution. The solution was cooled to room temperature, and kept still in air. Yellow block-shaped crystals of the complex, suitable for X-ray single crystal determination, were formed after slow evaporation of the solvents for a few days. The crystals were isolated by ltration and washed with methanol. Yield, 27.2 mg (57.4% based on H2 L1). Anal. Calcd. for C18 H22 MoN2 O7 (FW 474.3): C, 45.58; H, 4.68; N, 5.91. Found (%): C, 45.37; H, 4.75; N, 5.82. Synthesis of [MoO2 (L2)(CH3 OH)] (2) A 5 mL methanol solution of 3-hydroxy-2-naphthoic hydrazide (0.1 mmol, 20.2 mg) and 5-chlorosalicylaldehyde (0.1 mmol, 15.7 mg) was stirred to a 5 mL methanol solution of MoO2 (acac)2 (0.1 mmol, 33.1 mg). The mixture was stirred at reux for 1 h to give a clear yellow solution. The solution was cooled to room temperature, and kept still in air. Yellow

INTRODUCTION The coordination chemistry of molybdenum complexes at high oxidation numbers with dinegative tridentate ligands has attracted much attention in the last few years. These complexes are potential catalysts, because the labile coordination site is favorable for uptake and activation of substrates.[1] Numerous chemical reactions are catalyzed by the complexes with the dioxidomolybdenum(VI) unit O MoVI O.[24] Moreover, Schiff base compounds containing molybdenum play a significant role in the chemistry of molybdoenzymes.[5,6] It is well known that hydrazone compounds are a kind of special Schiff bases, which possess versatile biological activities.[79] In order to investigate the aggregation of the hydrazone compounds with the molybdenum, in this article, I report the synthesis and crystal structures of two new mononuclear oxidomolybdenum(VI) complexes, [MoO2 (L1)(CH3 OH)]CH3 OH (1) and [MoO2 (L2)(CH3 OH)] (2) (H2 L1 = 3-hydroxynaphthalene-

Received 19 October 2011; accepted 8 April 2012. The author acknowledges the project supported by the Key Research Item of the Baoji University of Arts and Sciences (Grant No. ZK1034) and by the Natural Science Foundation of the Education Ofce of Shanxi Province (Grant No. 2010JK409). Address correspondence to Prof. Jian-Ying Miao, Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721007, P. R. China. E-mail: jianying miao@126.com

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TABLE 1 Crystallographic and experimental data for complexes (1) and (2) Complex Formula FW Crystal shape/color Crystal size /mm Crystal system Space group a / b / c / / / / V /3 Z (MoK ) / T /K /mm1 (Mo-K ) T min T max Reections/ parameters Independent reections F (000) Goodness of t on F 2 R1 , wR2 [I 2 (I)]a R1 , wR2 (all data)a
a

TABLE 2 Selected bond lengths () and bond angles ( ) for complexes (1) and (2) (1) Mo1O1 Mo1O5 Mo1N2 O5Mo1O4 O4Mo1O7 O4Mo1O1 O5Mo1N2 O7Mo1N2 O5Mo1O3 O7Mo1O3 N2Mo1O3 (2) 0pt4,251.99997pt Mo1O1 Mo1O4 Mo1O6 O6Mo1O5 O5Mo1O1 O5Mo1O2 O6Mo1N1 O1Mo1N1 O6Mo1O4 O1Mo1O4 N1Mo1O4 1.9973(19) 1.693(2) 2.235(2) 105.91(12) 100.65(10) 97.17(9) 96.76(10) 82.16(9) 171.54(10) 80.15(10) 74.83(8) 1.9186(19) 2.363(2) 1.691(2) 106.21(12) 101.58(9) 98.16(9) 94.66(10) 81.14(8) 170.13(9) 81.32(9) 75.78(7) Mo1O4 Mo1O7 O5Mo1O7 O5Mo1O1 O7Mo1O1 O4Mo1N2 O1Mo1N2 O4Mo1O3 O1Mo1O3 1.714(2) 1.952(2) 98.05(11) 98.84(10) 150.99(9) 156.43(10) 72.57(8) 82.55(10) 79.69(9)

(1) C18 H22 MoN2 O7 474.32 Block/yellow

(2) C19 H15 ClMoN2 O6 498.72 Block/yellow

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0.20 0.18 0.17 0.18 0.17 0.15 monoclinic Triclinic P-1 P21 /n 11.183(3) 7.682(2) 13.061(3) 11.223(3) 14.549(3) 11.689(3) 90 90.253(2) 106.279(3) 103.992(2) 90 101.041(2) 2039.9(8) 958.4(4) 4 2 0.71073 0.71073 298(2) 298(2) 0.684 0.864 0.8754 0.8600 0.8926 0.8813 3657/262 4073/267 2986 968 1.053 0.0326, 0.0777 0.0441, 0.0854
|Fo|, wR2 = [

3438 500 1.031 0.0327, 0.0736 0.0425, 0.0784

w(Fo2)2]1/2.

Mo1O2 Mo1O5 Mo1N1 O6Mo1O1 O6Mo1O2 O1Mo1O2 O5Mo1N1 O2Mo1N1 O5Mo1O4 O2Mo1O4

2.0101(19) 1.696(2) 2.245(2) 99.84(11) 96.66(11) 149.50(9) 158.01(10) 72.07(8) 83.03(10) 78.25(9)

R1 =

||Fo|-|Fc||/

w(Fo2-Fc2)2/

block-shaped crystals of the complex, suitable for X-ray single crystal determination, were formed after slow evaporation of the solvents for a few days. The crystals were isolated by ltration and washed with methanol. Yield, 21.3 mg (42.7% based on H2 L2). Anal. Calcd. for C19 H15 ClMoN2 O6 (FW 498.7): C, 45.76; H, 3.03; N, 5.62. Found (%): C, 45.53; H, 3.16; N, 5.70. Crystal Structure Determination The diffraction intensities for the complexes were collected on a Bruker Smart Apex CCD diffractometer (MoK , = 0.71073 ) at 298 K. Absorption corrections were applied using SADABS (Bruker, Madison, WI, USA).[10] The crystal structures of the complexes were solved with direct methods and rened with a full-matrix least-squares technique using SHELXTL program package (Bruker, Madison, WI, USA).[11] Anisotropic thermal parameters were applied to all non-

hydrogen atoms. The methanol H atoms in the complexes were located from difference Fourier maps and rened with isotropic temperature factors. All other hydrogen atoms on carbon and oxygen atoms were generated geometrically (CH = 0.93 0.96 , OH = 0.82 . The crystallographic data as well as details of data collection and renement for the complexes are summarized in Table 1. Selected bond lengths and angles are given in Table 2. Hydrogen bonds are listed in Table 3.

TABLE 3 Hydrogn-bond geometry (, ) for the complexes (1) and (2) DHA (1) O6H6O3 O3H3AO6 O2H2N1 (2) O3H3N2 O4H4AO3i DH 0.82 0.85(1) 0.82 0.82 0.85(1) HA 2.22 1.89(2) 1.92 1.87 1.88(2) DA 2.732(5) 2.732(5) 2.635(3) 2.595(3) 2.718(3) DHA 120 170(7) 146 147 170(4)

Symmetry code for (i): 1 x, 1 y, 1 z.

OXIDOMOLYBDENUM(VI) COMPLEXES WITH HYDRAZONES

1465

O N H OH NH2 O MeOH

O HOMe Mo O O N OH (1 ) N

MoO2(acac)2

MeOH

O N H NH2 Cl CHO

O HOMe

+
OH

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OH

MoO2(acac)2

MeOH

O O

Mo O N N Cl

OH (2)
SCH. 1.

Drawings were produced with SHELXTL and the gures showed 30% probability of ellipsoids. RESULTS AND DISCUSSION Synthesis The reactions of MoO2 (acac)2 with tridentate Schiff bases in appropriate solvent usually results in the formation of oxidomolybdenum(VI) complexes.[1214] The synthesis of the complexes (1) and (2) is shown in Scheme 1. The 3hydroxy-2-naphthoic hydrazide reacts with the acetylacetone group of MoO2 (acac)2 give the tridentate hydrazone ligand H2 L1. The 3-hydroxy-2-naphthoic hydrazide reacts with 5chlorosalicylaldehyde give the tridentate hydrazone ligand H2 L2. The hydrazone ligands react with the MoO2 units form the nal structures of the complexes. Each hydrazone ligand coordinates to the Mo atom through the ethanolic O, imine N, and phenolic O atoms. IR Spectra The middle and broad absorptions in the range 33103450 cm1 for the spectra of the complexes are assigned to the vibrations of OH groups of the methanol and phenol. The Mo O stretching modes occur as a pair of sharp and middle bands at 935 and 903 cm1 for (1) and 932 and 898 cm1 for (2), assigned to the antisymmetric and symmetric stretching modes of the dioxomolybdenum(VI) units. The bands due to the C O and NH were absent in the complexes, and new CO stretches appear in the range 12601285 cm1. This suggests occurrence of keto-imine tautomerization of the hydrazone ligands during the coordination. The strong bands indicative of the C NN C groups in the two complexes are shifted to 1601 cm1 for (1) and 1604 cm1 for (2). The weak peaks observed in the range

830670 cm1 may be attributed to the MoO streching vibrations for the complexes. Structure Description of the Complexes The molecular structures of the complexes (1) and (2) are respectively shown in Figures 1 and 2, respectively. The complexes are similar mononuclear oxidomolybdenum(VI) compounds. Complex (1) contains a methanol molecule of crystallization. The hydrazone ligands possess intramolecular OHN hydrogen bonds in the complexes are approximately coplanar. For (1), the dihedral angle between the naphthyl ring and the C12-C16/N2/O7 plane is 2.8(3) . For (2), the dihedral angle between the benzene ring and the naphthyl ring is 5.9(3) . The hydrazone ligands coordinate to the Mo atoms through the dianionic mode, generating one ve- and one sixmembered chelate rings. The bond lengths of C11N1 (1.306(3) ) and C11O1 (1.326(3) ) in (1), and C8N2 (1.303(3) ) and C8O2 (1.313(3) ) in (2), suggest the presence of the

FIG. 1. The structure of (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

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J.-Y. MIAO

REFERENCES
1. Sobczak, J.M.; Glowiak, T.; Ziolkowski, J.J. The structure of binuclear molybdenum(VI) oxocomplexes with dianionic tridentate Schiff bases. Transition Met. Chem. 1990, 15, 208211. 2. Gomez, M.; Jansat, S.; Muller, G.; Noguera, G.; Teruel, H.; Moliner, V.; Cerrada, E.; Hursthouse, M. First dioxomolybdenum(VI) complexes containing chiral oxazoline ligands: synthesis, characterization and catalytic activity. Eur. J. Inorg. Chem. 2001, 4, 10711076. 3. Arnaiz, F.J.; Aguado, R.; Pedrosa, M.R.; De Cian, A.; Fischer, A. Synthesis, characterization and catalytic activity of addition compounds of dioxomolybdenum(VI) pyridine-2,6-dicarboxylate. Crystal structure of MoO2 (dipic)(L) (L = DMF, DMSO, OPPh3 ). Polyhedron 2000, 19, 2141 2147. 4. Zhang, C.; Rheinwald, G.; Lozan, V.; Wu, B.; Lassahn, P.-G.; Lang, H.; Janiak, C. Structural study and solution integrity of dioxomolybdenum(VI) complexes with tridentate Schiff base and azole ligands. Z. Anorg. Allg. Chem. 2002, 628, 12591268. 5. Howard, J.B.; Rees, D.C. Structural basis of biological nitrogen xation. Chem. Rev. 1996, 96, 29652982. 6. Holm, R.H.; Kennepoh, P.; Solomon, E.I. Structural and functional aspects of metal sites in biology. Chem. Rev. 1996, 96, 22392314. 7. Bernhardt, P.V.; Chin, P.; Sharpe, P.C.; Richardson, D.R. Hydrazone chelators for the treatment of iorn overload disorders: iron coordination chemistry and biological activity. Dalton Trans. 2007, 30, 32323244. 8. El-Dissouky, A.; Al-Fulaij, O.; Awad, M.K.; Rizk, S. Synthesis, characterization, and biological activity studies of copper(II)-metal(II) binuclear complexes of dipyridylglyoxal bis(2-hydroxybenzoyl hydrazone). J. Coord. Chem. 2010, 63, 330345. 9. El-Sayed, M.A. A.; Abdel-Aziz, N.I.; Abdel-Aziz, A.A. M.; El-Azab, A.S.; Asiri, Y.A.; ElTahir, K.E. H. Design, synthesis, and biological evaluation of substituted hydrazone and pyrazole derivatives as selective COX-2 inhibitors: molecular docking study. Bioorg. Med. Chem. 2011, 19, 3416 3424. 10. Sheldrick, G.M. SADABS. Program for Empirical Absorption Correction of Area Detector; University of G ottingen, Germany, 1996. 11. Sheldrick, G.M. SHELXTL, Version 6.10, Software Reference Manual; Madison, WI: Bruker Instrumentation, 2000. 12. Cindric, M.; Strukan, N.; Vrdoljak, V.; Kajfez, T.; Kamenar, B. A series of molybdenum(VI) complexes with tridentate Schiff base ligands. Z. Anorg. Allg. Chem. 2002, 628, 21132117. 13. Sah, A.K.; Rao, C.P.; Saarenketo, P.K.; Wegelius, E.K.; Kolehmainen, E.; Rissanen, K. First crystallographic investigation of complexes of cisVO2 +, cis-MoO2 +, and trans-UO2 2+ species with Schiff-base molecules derived from 4,6-o-ethylidene- -D-glucopyranosylamine. Eur. J. Inorg. Chem. 2001, 27732781. 14. Cindric, M.; Strukan, N.; Vrdoljak, V.; Kamenar, B. Synthesis, characterization, and crystal structure of mononuclear and dinuclear dioxomolybdenum(VI) complexes with tridentate Schiff-base ligands. Z. Anorg. Allg. Chem. 2004, 630, 585590.

FIG. 2. The structure of (2), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

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enolate form of the amide groups in the ligands. In (1), the Mo atom is coordinated by O1, N2, and O7 atoms of L1, two oxo O atoms, and one methanol O atom, forming a highly distorted octahedral geometry. In (2), the Mo atom is coordinated by O1, N1, and O2 atoms of L2, two oxo O atoms, and one methanol O atom, forming a highly distorted octahedral geometry. The Mo atoms are displaced by 0.346(1) for (1) and 0.333(1) for (2) toward the axial oxo O atoms from the least-squares planes dened by the four equatorial donor atoms. The MoO and MoN bonds in the complexes are comparable to each other, and are within the usual values observed for the similar oxidomolybdenum(VI) complexes.[1214] The longest bonds in the molybdenum coordination sphere are those related to the solvent molecules, with Mo-Osolv distances ranging from 2.36 to 2.38 . The trans angles range from 151.0(1) to 171.5(1) for (1) and from 149.5(1) to 170.1(1) for (2), and all the other angles from 72.6(1) to 105.9(1) for (1) and from 72.1(1) to 106.2(1) for (2). The crystal structures of the complexes are stabilized by intermolecular OHO and OHN hydrogen bonds.

SUPPLEMENTARY MATERIALS Crystallographic data for the two complexes have been deposited with the Cambridge Crystallographic Data Centre (CCDC 848895 and 848896).