A novel aggregation of (4-nitrophenoxy)acetic acid [1-(2-hydroxyphenyl) methylidene]hydrazide and its dioxomolybdenum(VI) complex: Synthesis and structure

Article abstract of DOI:10.1080/15533174.2012.762676

A novel aggregation of (4-nitrophenoxy)acetic acid [1-(2-hydroxyphenyl) methylidene]hydrazide and its dioxomolybdenum(VI) complex has been prepared by the reaction of salicylaldehyde, (4-nitrophenoxy)acetic acid hydrazide, and MoO₂(acac)₂ in methanol. The compound was characterized by elemental analysis and single-crystal X-ray diffraction method. The asymmetric unit of the compound contains a free hydrazone molecule and a dioxomolybdenum(VI) complex molecule. The Mo atom in the complex molecule is coordinated by one phenolate O, one imino N, and one enolic O atoms of the hydrazone ligand, two oxo O atoms, and one water O atom, forming an octahedral coordination. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2012.762676

This article was downloaded by: [New York University]
On: 13 May 2015, At: 03:33
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
A Novel Aggregation of (4-Nitrophenoxy)acetic Acid
[1-(2-Hydroxyphenyl)methylidene]hydrazide and
Its Dioxomolybdenum(VI) Complex: Synthesis and
Structure
Xiao-Qiang He a
a College of Chemical Engineering and Pharmacy , Jingchu University of Technology ,
Jingmen Hubei , P. R. China
Accepted author version posted online: 13 May 2013.Published online: 25 Aug 2013.
To cite this article: Xiao-Qiang He (2013) A Novel Aggregation of (4-Nitrophenoxy)acetic Acid [1-(2-
Hydroxyphenyl)methylidene]hydrazide and Its Dioxomolybdenum(VI) Complex: Synthesis and Structure, Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:10, 1402-1405, DOI: 10.1080/15533174.2012.762676
To link to this article: http://dx.doi.org/10.1080/15533174.2012.762676
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1402–1405, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.762676
A Novel Aggregation of (4-Nitrophenoxy)acetic Acid
[1-(2-Hydroxyphenyl)methylidene]hydrazide and Its
Dioxomolybdenum(VI) Complex: Synthesis and Structure
Xiao-Qiang He
College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen Hubei,
P. R. China
A novel aggregation of (4-nitrophenoxy)acetic acid [1-(2-
hydroxyphenyl)methylidene]hydrazide and its dioxomolybde-
num(VI) complex has been prepared by the reaction of salicylalde-
hyde, (4-nitrophenoxy)acetic acid hydrazide, and MoO2(acac)2 in
methanol. The compound was characterized by elemental analysis
and single-crystal X-ray diffraction method. The asymmetric unit
of the compound contains a free hydrazone molecule and a dioxo-
molybdenum(VI) complex molecule. The Mo atom in the complex
SCH. 1. H2L.
molecule is coordinated by one phenolate O, one imino N, and one
enolic O atoms of the hydrazone ligand, two oxo O atoms, and one
water O atom, forming an octahedral coordination.
hydroxyphenyl)methylidene]hydrazide (H2L) and its dioxo-
molybdenum(VI) complex [MoO2L(OH2)] was reported.
Keywords crystal structure, hydrazone, hydrogen bonding, molyb-
denum complex, synthesis
INTRODUCTION
EXPERIMENTAL
Hydrazone compounds derived from the reaction of
carbonyl-containing compounds with hydrazides have attracted
much attention for their effective biological activities[1–3] and
interesting coordinate capabilities.[4–7] In the last few years,
a large number of complexes of copper, vanadium, molyb-
denum, palladium, zinc, nickel, cobalt, ruthenium, organic
tin, rhodium, cadmium, manganese, uranium, and germanium
with hydrazone ligands have been reported,[8–16] among which
there are 40 molybdenum complexes. Some of the molyb-
denum complexes have been reported to have versatile cat-
alytic properties.[17–19] The construction of novel structures
of molybdenum complexes with hydrazone ligands is im-
Salicylaldehyde and (4-nitrophenoxy)acetic acid hydrazide
were obtained from Aldrich (Jingchu University of Technology,
China). The remaining chemicals and solvents were of analyt-
ical reagent grade, and were purchased from Beijing Chemical
Reagent Company (China). Microanalyses (C, H, N) were per-
formed using a Perkin-Elmer 2400 elemental analyzer (Jingchu
University of Technology, China). X-ray measurement was per-
formed using a Bruker Smart 1000 CCD diffractometer (Wuhan
University, China) with graphite monochromated Mo-Kα radi-
ation (λ = 0.71073 Å).
portant for the exploration of new functional materials. In Syntheses of the Compound [MoO2L(OH2)]·H2L
the present paper, the synthesis and structure of a novel ag-
gregation (Scheme 1) of (4-nitrophenoxy)acetic acid [1-(2-
Salicylaldehyde (0.25 g, 2 mmol) and (4-nitrophenoxy)acetic
acid hydrazide (0.43 g, 2 mmol) were mixed in methanol
(30 mL). The mixture was stirred for 30 min at room tem-
perature. To the above solution, a methanolic solution (20 mL)
of MoO2(acac)2 (0.33 g, 1 mmol) was added. The final mixture
was further stirred for 30 min to give a brown solution. Sin-
gle crystals suitable for X-ray diffraction were formed by slow
evaporation of the solution of the compound in air for a few
days. Yield: 53%. Anal. Calcd. for C30H26MoN6O13: C, 46.5;
H, 3.4; N, 10.9. Found: C, 46.7; H, 3.5; N, 10.8%.
Received 9 January 2012; accepted 23 December 2012.
The author acknowledges the Jingchu University of Technology for
financial support.
Address correspondence to Xiao-Qiang He, College of Chemical
Engineering and Pharmacy, Jingchu University of Technology, Jing-
men Hubei 448000, P. R. China. E-mail: hexq2012@163.com
1402

HYDRAZONE ITS DIOXOMOLYBDENUM(VI) COMPLEX
1403
TABLE 1
Crystal data for the compound
X-Ray Structure Determination
X-ray measurement was performed by using the ω-scan tech-
nique. Determination of the Laue class, orientation matrix, and
cell dimensions were performed according to the established
procedures where Lorentz polarization and absorption correc-
tions were applied. Absorption corrections were applied by fit-
ting a pseudoellipsoid to the ψ-scan data of selected strong
reflections over a wide range of 2 θ angles. The positions of
non-hydrogen atoms were located with direct methods. Sub-
sequent Fourier syntheses were used to locate the remaining
non-hydrogen atoms. All non-hydrogen atoms were refined
anisotropically. The water H atoms in [MoO2L(OH2)] and the
amino and hydroxyl H atoms in H2L were located from a differ-
ence Fourier map and refined isotropically, with O H, N H,
and H···H distances restrained to 0.85(1), 0.90(1), and 1.37(2) Å,
respectively. The remaining hydrogen atoms were placed in cal-
culated positions and constrained to ride on their parent atoms.
The analysis was performed with the aid of the SHELXS-97 and
SHELXL-97 suite of codes.[20, 21] The crystallographic data for
the complex are summarized in Table 1. Selected bond lengths
and angles are given in Table 2. Hydrogen bonding information
is given in Table 3.
Chemical formula C30H26MoN6O13
Moiety formula
Fw
C15H13MoN3O8·C15H13N3O5
774.5
Crystal shape/color
Crystal size (mm)
T (K)
Block/yellow
0.27 × 0.23 × 0.23
298(2)
λ (MoKα) (Å)
Crystal system
Space group
a (Å)
0.71073
Triclinic
P–1
8.087(1)
13.681(2)
16.035(2)
113.362(2)
91.857(2)
100.691(2)
1589.2(4)
2
b (Å)
c (Å)
α (◦)
β (◦)
γ (◦)
V (Å3)
Z
μ (MoKα) (mm−1
)
0.491
Tmin
Tmax
0.879
0.895
1.619
Dc (g cm−3
)
RESULTS AND DISCUSSION
Measured reflections
Reflections/parameters
Unique reflections
Restraints
9068
6491/463
4881
The compound was prepared by the reaction of MoO2(acac)2
with H2L in methanol in a 1:2 mole proportion at room temper-
ature (Scheme 2). The excess of the ligand was aggregate to the
dioxomolybdenum(VI) complex molecule during the crystal-
lization. The chemical formula of the compound was confirmed
by elemental analyses and single-crystal X-ray diffraction.
5
Goodness of fit on F2
Rint
1.064
0.0292
R1 [I ≥ 2σ(I)]
wR2 [I ≥ 2σ(I)]
R1 (all data)
0.0468
0.0975
0.0688
0.1084
Structure Description of the Compound
The molecular structure of the compound is shown in
Figure 1. The asymmetric unit of the compound contains a
wR2 (all data)
NO2
NO2
CHO
O
H
N
O
+
H
N
N
OH
H2N
(H2L)
O
OH
O
NO2
NO2
O
O
2 H L
MoO (acac)
2 2
+
2
H
N
N
N
O
N
O
O
O
Mo
OH
O
H2O
SCH. 2. The preparation of the compound.

1404
X.-Q. HE
TABLE 2
Selected bond lengths (Å) and angles (◦) for the compound
[MoO2L(OH2)]
Bond lengths
Mo1-O1
Mo1-O2
Mo1-N1
Mo1-O11
Mo1-O12
1.916(2)
2.002(2)
2.244(3)
1.680(2)
1.702(2)
2.331(2)
C7-N1
N1-N2
N2-C8
O2-C8
C2-O1
1.290(4)
1.403(4)
1.283(4)
1.320(4)
1.359(4)
FIG. 1. Molecular structure of the compound with 30% probability thermal
ellipsoids. Left: H2L; Right: [MoO2L(OH2)]. Intramolecular O–H···N hydrogen
bond is drawn as a dashed line.
Mo1-O13
Bond angles
O11-Mo1-O12
O12-Mo1-O1
O12-Mo1-O2
O11-Mo1-N1
O1-Mo1-N1
O11-Mo1-O13
O1-Mo1-O13
N1-Mo1-O13
104.6(1)
103.1(1)
98.4(1)
94.4(1)
81.3(1)
172.6(1)
82.5(1)
78.3(1)
O11-Mo1-O1
O11-Mo1-O2
O1-Mo1-O2
O12-Mo1-N1
O2-Mo1-N1
O12-Mo1-O13
O2-Mo1-O13
98.1(1)
96.6(1)
149.8(1)
159.5(1)
71.4(1)
82.4(1)
79.7(1)
O12, and N1 atoms toward the apical oxo atom O11 is 0.301(1)
Å. The hydrazone ligand is coordinated to the Mo atom in its
dianionic form, generating five- and six-membered chelate rings
with angles of 71.4(1) and 81.3(1)◦, respectively. The dihedral
angle between the C1-C6 and C10-C15 benzene rings in the
hydrazone ligand of the complex molecule is 7.6(3)◦. The plane
defined by O4, N3, and O5 atoms forms a dihedral angle of
2.4(3)◦ with the C10-C15 benzene ring. The enolate form of
the ligand is evident from the N2–C8 and O2–C8 bond lengths
with values of 1.283(4) and 1.320(4) Å, respectively, which are
much different from the corresponding bonds of the free hydra-
zone molecule [N5–C23 = 1.339(4) Å, O7–C23 = 1.222(4) Å].
The coordinate bond lengths around the Mo atom are compa-
rable to the values observed in similar dioxomolybdenum(VI)
complexes.[22–24]
H2L
Bond lengths
C22-N4
N4-N5
1.276(4)
1.384(4)
1.339(4)
O7-C23
C17-O6
1.222(4)
1.351(5)
N5-C23
free hydrazone molecule and a dioxomolybdenum(VI) complex
molecule. In the hydrazone molecule, there forms an intramolec-
ular O6–H6A···N4 hydrogen bond. The dihedral angle between
the C16-C21 and C25-C30 benzene rings is 3.4(3)◦. The plane
defined by O9, N6, and O10 atoms forms a dihedral angle of
4.8(3)◦ with the C25-C30 benzene ring. The torsion angle of
C22-N4-N5-C23, N4-N5-C23-C24, and N5-C23-C24-O8 are
2.3(3)◦, 0.8(3)◦, and 4.8(3)◦, respectively. In the dioxomolyb-
denum(VI) complex molecule, the Mo atom is coordinated by
one phenolate O, one imino N, and one enolic O atoms of the
hydrazone ligand, two oxo O atoms, and one water O atom,
forming an octahedral coordination. The displacement of the
Mo atom from the equatorial mean plane defined by the O1, O2,
In the crystal structure of the compound, the free hy-
drazone molecules and the dioxomolybdenum(VI) complex
molecules are linked through intermolecular O–H···O, O–H···N,
and N–H···O hydrogen bonds, to form 2D layers parallel to the
ab plane (Figure 2).
TABLE 3
Distances (Å) and angles (◦) involving hydrogen bonding of
the compound
d
d
d
Angle
D–H···A
(D–H) (H··A)
(D···A) (D–H···A)
O6–H6A···N4
0.84(1) 1.96(3) 2.619(4)
134(4)
173(4)
132(4)
160(4)
161(4)
O13–H13A)···O7#1 0.84(1) 1.93(2) 2.768(3)
O13–H13B···O3#2 0.84(1) 2.64(3) 3.264(3)
O13–H13B···N2#2 0.84(1) 2.05(2) 2.855(4)
N5–H5···O12#3
0.90(1) 2.22(2) 3.082(4)
FIG. 2. Molecular packing of the compound, viewed along the b-axis.
Symmetry codes: #1: 2 – x, 1 – y, 1 – z; #2: 1 – x, – y, – z; #3: x, y, Hydrogen bonds are drawn as dashed lines.
1 + z.

HYDRAZONE ITS DIOXOMOLYBDENUM(VI) COMPLEX
1405
CONCLUSION
mono(mu-pyrazolate) bridged dicopper(II) complexes derived from N-
salicylidenearoylhydrazines. Polyhedron 2001, 20, 2787–2798.
10. Dinda, R.; Sengupta, P.; Ghosh, S.; Sheldrick, W.S. Synthesis, structure, and
reactivity of a new mononuclear molybdenum(VI) complex resembling the
active center of molybdenum oxotransferases. Eur. J. Inorg. Chem. 2003,
363–369.
11. Cariati, F.; Caruso, U.; Centore, R.; Marcolli, W.; De Maria, A.; Panunzi,
B.; Roviello, A.; Tuzi, A. Synthesis, structure, and second-order nonlinear
optical properties of copper(II) and palladium(II) acentric complexes with
N-salicylidene-Nꢁ-aroylhydrazine tridentate ligands. Inorg. Chem. 2002,
41, 6597–6603.
In summary, a novel aggregation of (4-nitrophenoxy)acetic
acid [1-(2-hydroxyphenyl)methylidene]hydrazide and its diox-
omolybdenum(VI) complex has been obtained. The structure
of the compound was characterized by elemental analysis and
single-crystal X-ray diffraction method. The hydrazone ligand
coordinates to the Mo atoms through the phenolic O, imino N,
and enolic O atoms.
12. Pal, S.; Pal, S. Ruthenium(III) complexes with a phenolate-O, imine-N, and
amide-O coordinating ligand: Syntheses, structures, properties, and proto-
nation studies of coordinated amide. Eur. J. Inorg. Chem. 2003, 4244–4252.
13. Dey, D.K.; Samanta, B.; Lycka, A.; Dahlenburg, L. Simple synthesis, char-
acterization and structure of diorganotin(IV) complexes containing the N-
(2-salicylidene)-Nꢁ-benzoylhydrazone ligand. Z. Naturforsch. Teil B 2003,
58, 336–344.
14. Borbone, F.; Caruso, U.; Centore, R.; De Maria, A.; Fort, A.; Fusco, M.; Pa-
nunzi, B.; Roviello, A.; Tuzi, A. Second order optical nonlinearities of cop-
per(II) and palladium(II) complexes with N-salicylidene-Nꢁ-aroylhydrazine
tridentate ligands. Eur. J. Inorg. Chem. 2004, 2467–2476.
SUPPLEMENTARY MATERIALS
CCDC 861282 contains the supplementary crystallographic
data for the complex. These data can be obtained free of
charge via http://www.ccdc.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 email:
deposit@ccdc.cam.ac.uk.
15. Bai, Y.; Dang, D.-B.; Cao, X.; Duan, C.-Y.; Meng, Q.-J. One-dimensional
copper polymers with pentadentate diazine ligands. Inorg. Chem. Commun.
2006, 9, 86–89.
16. Nica, S.; Rudolph, M.; Gorls, H.; Plass, W. Structural characterization
and electrochemical behavior of oxovanadium(V) complexes with N-
salicylidene hydrazide. Inorg. Chim. Acta 2007, 360, 1743–1752.
17. Gupta, S.; Pal, S.; Barik, A.K.; Roy, S.; Hazra, A.; Mandal, T.N.; Butcher,
R.J.; Kar, S.K. Molybdenum(VI) complexes of a few pyrimidine derived
REFERENCES
1. Wang, J.-P.; Fu, Y.-J.; Yin, W.-P.; Wang, J.-G.; Qin, J.-H. Synthesis and
characterization of biological active hydrazone derivatives. Chin. J. Org.
Chem. 2007, 27, 524–527.
2. Rollas, S.; Kucukguzel, S.G. Biological activities of hydrazone derivatives.
Molecules 2007, 12, 1910–1939.
3. 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 evalua-
tion of substituted hydrazone and pyrazole derivatives as selective COX-
2 inhibitors: molecular docking study. Bioorg. Med. Chem. 2011, 19,
3416–3424.
4. Bernhardt, P.V.; Chin, P.; Sharpe, P.C.; Richardson, D.R. Hydrazone chela-
tors for the treatment of iron overload disorders: iron coordination chemistry
and biological activity. Dalton Trans. 2007, 30, 3232–3244.
5. Yang, Z.-Y.; Yang, R.-D.; Li, Q.; Li, F.-S. Synthesis, characterization and bi-
ological activity of rare earth complexes of 1-phenyl-3-methyl-5-hydroxy-
4-pyrazolyl phenyl ketone isonicotinoyl hydrazone. Synth. React. Inorg.
Met.-Org. Chem. 1999, 29, 205–214.
6. Zhang, L.; Tang, N.; Wu, J.-C.; Tan, M.-Y.; Wang, Q.; Han, Y. Synthesis,
characterization, and biological activities of 3,5-dibenzyloxybenzoyl hy-
drazone and its complexes with some transition metals. Synth. React. Inorg.
Met.-Org. Chem. 2003, 33, 847–856.
7. El-Sherif, A.A. Synthesis, spectroscopic characterization and biological
activity on newly synthesized copper(II) and nickel(II) complexes incor-
porating bidentate oxygen-nitrogen hydrazone ligands. Inorg. Chim. Acta
2009, 362, 4991–5000.
ligands and the study of metal mediated C
N bond cleavage resulting
in ligand transformation during complex formation. Polyhedron 2009, 28,
711–720.
18. Sheikhsoaie, I.; Rezaeffard, A.; Monadi, N.; Kaafi, S. A novel tridentate
Schiff base dioxo-molybdenum(VI) complex: synthesis, crystal structure
and catalytic performance in green oxidation of sulfides by urea hydrogen
peroxide. Polyhedron 2009, 28, 733–738.
19. Rao, S.N.; Kathale, N.; Rao, N.N.; Munshi, K.N. Catalytic air oxidation
of olefins using molybdenum dioxo complexes with dissymmetric triden-
tate O,N,S-donor Schiff base ligands derived from o-hydroxyacetophenone
and S-benzyldithiocarbazate or S-methyldithiocarbazate. Inorg. Chim. Acta
2007, 360, 4010–4016.
20. Sheldrick, G.M. SHELX-97, Program for Crystal Structure Solution and
Refinement; University of Go¨ttingen, Germany, 1997.
21. Sheldrick, G.M. SHELXTL Version 5; Siemens, Madison, WI, 1995.
22. Zhai, Y.-L.; Xu, X.-X.; Wang, X. Synthesis and characterization of cis-
dioxomolybdenum(VI) complex of the Schiff-base salicylaldehyde son-
coyhydrazone (SAIH) and the crystal-structure of [MoO2(ortho-C6H4CH
NN COC5H4N)CH3OH]. Polyhedron 1992, 11, 415–418.
23. Dinda, R.; Sengupta, S.; Ghosh, S.; Mayer-Figge, H.; Sheldrick, W.S. A
family of mononuclear molybdenum-(VI), and -(IV) oxo complexes with a
tridentate (ONO) ligand. J. Chem. Soc. Dalton Trans. 2002, 23, 4434–4439.
24. Gupta, S.; Barik, A.K.; Pal, S.; Hazra, A.; Roy, S.; Butcher, R.J.; Kar, S.K.
Oxomolybdenum(VI) and (IV) complexes of pyrazole derived ONO donor
ligands – synthesis, crystal structure studies and spectroelectrochemical
correlation. Polyhedron 2007, 26, 133–141.
8. Sangeetha, N.R.; Kavita, V.; Wocadlo, S.; Powell, A.K.; Pal, S. Vana-
dium(V) complexes of O,N,O-donor tridentate ligands containing the
{VvO(OMe)}2+ unit: syntheses, structures and properties. J. Coord. Chem.
2000, 51, 55–66.
9. Iskander, M.F.; Khalil, T.E.; Haase, W.; Werner, R.; Svoboda, I.;
Fuess, H. Synthesis, magnetochemical studies and X-ray molecular
structures of some mononuclear copper(II)-1H-pyrazole adducts and