Crystal structure, quantum chemical investigation, and thermal behavior of acyl hydrazones C10H10N2O4 · 2H2O

Article abstract of DOI:10.1080/15533174.2013.809741

N-(2-(propionic acid)-salicyloyl hydrazone C₁₀H ₁₀N₂O₄ · 2H₂O (H ₃L) was synthesized by refluxing the aroylhydrazine and pyruvic acid in nonaqueous ethanol. Single crystals of H₃L suitable for X-ray measurement were obtained by methanol-water (V/V = 1:1). The theoretical studies on the title compound were carried out at HF/6-31+G(d) and B3LYP/6-31+G(d) levels. The results indicated that HF/6-31+G(d) gave better structural optimization datathan B3LYP/6-31+G(d) method. In addition, the thermal stabilityhad been tested by TG-DTG under a nitrogen atmosphere. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2013.809741

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Crystal Structure, Quantum Chemical Investigation, and
Thermal Behavior of Acyl Hydrazones C10H10N2O4·2H2O
Feng-Ying Chenab, Wang-Ting Wuac, Shui-Yang Hea & Zhen-Yi Wena
a College of Chemistry and Material Science, Northwest University and Key Laboratory of
Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Xi’an, P. R.
China
b Department of Chemistry & Chemical Engineering, Shangluo University, Shangluo, P. R.
China
c Capital Museum, Beijing, P. R. China
Accepted author version posted online: 11 Oct 2013.Published online: 17 Apr 2014.
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To cite this article: Feng-Ying Chen, Wang-Ting Wu, Shui-Yang He & Zhen-Yi Wen (2014) Crystal Structure, Quantum Chemical
Investigation, and Thermal Behavior of Acyl Hydrazones C10H10N2O4·2H2O, Synthesis and Reactivity in Inorganic, Metal-
Organic, and Nano-Metal Chemistry, 44:9, 1345-1348, DOI: 10.1080/15533174.2013.809741
To link to this article: http://dx.doi.org/10.1080/15533174.2013.809741
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:1345–1348, 2014
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.809741
Crystal Structure, Quantum Chemical Investigation,
and Thermal Behavior of Acyl Hydrazones
C10H10N2O4·2H2O
Feng-Ying Chen,1,2 Wang-Ting Wu,1,3 Shui-Yang He,1 and Zhen-Yi Wen1
1College of Chemistry and Material Science, Northwest University and Key Laboratory of Synthetic and
Natural Functional Molecule Chemistry of Ministry of Education, Xi’an, P. R. China
2Department of Chemistry & Chemical Engineering, Shangluo University, Shangluo, P. R. China
3Capital Museum, Beijing, P. R. China
EXPERIMENTAL
N-(2-(propionic acid)-salicyloyl hydrazone C10H10N2O4·2H2O
Material and Physical Measurements
(H3L) was synthesized by refluxing the aroylhydrazine and pyru-
All reagents were commercial grade and were used as re-
vic acid in nonaqueous ethanol. Single crystals of H3L suitable
for X-ray measurement were obtained by methanol-water (V/V =
1:1). The theoretical studies on the title compound were carried out
at HF/6–31+G(d) and B3LYP/6–31+G(d) levels. The res-ults indi-
cated that HF/6–31+G(d) gave better structural optimization data
than B3LYP/6–31+G(d) method. In addition, the thermal stability
had been tested by TG-DTG under a nitrogen atmosphere.
ceived. The elemental analysis was measured on a PE-2400
Element Analytical instrument (Perkin Elmer, USA) and the X-
ray data for the crystals were collected on a Bruker Smart-1000
CCD X-ray single-crystal diffractometer.
Synthesis of H3L
The synthesis route about H3L was according to literature.[8]
But the crystal structure had never obtained. H3L was dissolved
in the mixed solvent of methanol and water (v/v = 1:1) and
stirred 5 h, then filtrated. After two weeks at the room tempera-
ture, the colorless virgulate crystal suitable for X-ray measure-
ment was obtained.
Keywords aroylhydrazone, crystal structure, quantum chemistry
INTRODUCTION
Owing to their biological activity, especially as effective in-
hibitors for many enzymes, hydrazones, especially acyl and
aroyl hydrazones, have been intensively investigated for many
years.[1–3] They are widely used in analytical chemistry as a se-
lective metal extracting agent as well as in spectroscopic deter-
mination of certain transition metals.[4,5] Acyl hydrazone ligands
bearing both nitrogen and oxygen donors that exhibit both hard
and soft base character could form more stable complexes than
polyoxa or polyaza ligands.[6] The theoretical studies on cop-
per complex with H3L have been reported.[7] However, to our
knowledge, no detailed theoretical studies on H3L have been
published. So here we report the theoretical studies and thermal
behavior of this compound.
Determination of the Single-Crystal Structure
Single-crystal X-ray diffraction measurements of H3L were
carried out with Bruker Smart 1000 CCD X-ray diffractometer.
Intensities of reflections were measured at 298 K using graphite
monochromatized Mo Kα radiation (λ = 0.71073Å) with ω scan
mode in the range of 1.88 ≤ θ ≤ 25.09. The structure was solved
by direct methods, and refined by full-matrix least-squares on
F2 with the SHELXTL-97 program.[9] Data processing was per-
formed via the SAINT processing program.[10] Crystallographic
information is summarized in Table 1.
The Quantum Chemical Investigation
The geometry optimization was performed by GAUS-
SIAN 03 program package using HF/6–31+G(d) and
B3LYP/6–31+G(d) methods. All calculations were carried out
on a Dell P4 computer with 2.0 GHz and 256 MB memories.
Received 10 March 2013; accepted 27 May 2013.
Address correspondence to Shui-Yang He, College of Chemistry
and Material Science, Northwest University and Key Laboratory of
Synthetic and Natural Functional Molecule Chemistry of Ministry of
Education, Xi’an, P. R. China. E-mail: xdchemistry411@126.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
Thermal Decomposition
The TG-DTG experiment for the title compound was per-
formed using a model Q600SDT under a nitrogen atmosphere,
1345

1346
F.-Y. CHEN ET AL.
TABLE 1
Crystallographic data and structure refinement summary
for H3L
Empirical formula
C10H14N2O6
258.23
Formula weight
Crystal system, space group
Unit cell dimensions
Orthorhombic, Fdd2
a = 28.887(9) Å α = 90◦
b = 32.733(10) Å β = 90◦
c = 4.9281(14) Å γ = 90◦
4660(2) Å3
Volume
Z, Calculated density
Absorption coefficient
12, 1.592 Mg/m3
0.127
(mm−1
F(000)
R, wR2
)
2304
0.0439, 0.1317
–34 ꢀ h ꢀ33, –36 ꢀ k ꢀ 38,
–5 ꢀ l ꢀ 5
FIG. 1. Crystal structure of H3L.
Limiting indices
Figure 1, the packing of the molecular in the crystal lattice were
shown in Figure 2. The structure of title compound was quasi
coplanarity of the whole molecule skeleton (see Figure 1). The
crystal formed a two-dimensional reticulation along the a axis
(see Figure 2). The lattice waters liked inlaid diamonds between
two rows linking by hydrogen bonds with the compound. The in-
tramolecular hydrogen bond existed between O1 and N1 to form
a five-numbered ring sharing the same edge with phenol ring
(O1. . .H-N1 = 2.609 Å, ∠NHO = 136.12◦). The intermolec-
ular hydrogen bonds (O4. . .H-O5 = 2.931 Å N2. . .H-O5 =
2.997 Å O2. . .H-O5 = 2.736 Å) determined a molecular con-
formation corresponding to a potential ONO chelating behavior,
which was confirmed by its complex.[11]
Reflections collected / unique
5890 / 1957
Goodness-of-fit on F2
1.113
at a flow rate of 150 mL min−1. The sample mass was about
2 mg. The heating rate used was 10.0◦C·min−1 from ambient
temperature to 1000◦C. The temperature and heat were cali-
brated using pure indium and tin particles.
RESULTS AND DISCUSSION
Crystal Structure
The bond lengths and bond angles of H3L are summarized in
Table 2. The molecular structure and atom labeling are shown in
Atomic Net Charges of the Compounds
Optimized structure of H3L by HF/6–31+G(d) method is
displayed in Figure 3. Table 3 shows the calculated bond lengths
and bond angles for H3L.
Comparing Tables 2 and 3, it can be seen that the results
obtained from two different methods were in conformity with
TABLE 2
Selected bond lengths (Å) and bond angles (◦)
Bond lengths
Bond angles
C(7)-N(1)-N(2)
N(2)-C(8)
1.281(4)
1.406(4)
1.375(4)
1.368(5)
1.396(5)
1.410(4)
1.498(5)
1.491(4)
120.0(2)
122.2(3)
120.0(3)
120.2(3)
120.9(3)
119.3(3)
117.2(3)
116.8(2)
127.0(3)
118.3(3)
123.4(3)
122.1(3)
114.5(3)
C(1)-C(6)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(8)-C(9)
C(8)-C(10)
C(2)-C(1)-C(6)
C(1)-C(2)-C(3)
C(4)-C(3)-C(2)
C(3)-C(4)-C(5)
O(1)-C(5)-C(6)
C(5)-C(6)-C(1)
N(1)-C(7)-C(6)
N(2)-C(8)-C(10)
C(10)-C(8)-C(9)
O(3)-C(9)-O(4)
O(3)-C(9)-C(8)
O(4)-C(9)-C(8)
FIG. 2. The packing of the molecule in the crystal lattice.

CRYSTAL, QUANTUM CHEMICAL, AND THERMAL BEHAVIOR
1347
TABLE 3
TABLE 4
The calculated non-hydrogen bond lengths (Å) and bond
Mulliken net charges on atoms of H3L
angles (◦)
Atoms
Charge
B3LYP/6–31 +
HF/6–31 + G(d) B3LYP/6–31 + G(d)
HF/6–31 + G(d)
G(d)
O(1)
O(2)
O(3)
O(4)
H(4)
N(1)
H(1)
N(2)
H(1A)
C(5)
C(6)
C(7)
C(8)
C(9)
–0.913862
–0.575522
–0.402353
–0.392372
–0.444172
0.339594
–0.549299
0.334827
–0.109867
0.341381
0.180839
0.787451
0.484001
0.139836
0.412128
N(2)-C(8)
C(1)-C(6)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(8)-C(9)
C(8)-C(10)
Largest deviation
C(7)-N(1)-N(2)
C(2)-C(1)-C(6)
C(1)-C(2)-C(3)
C(4)-C(3)-C(2)
C(3)-C(4)-C(5)
O(1)-C(5)-C(6)
C(5)-C(6)-C(1)
N(1)-C(7)-C(6)
N(2)-C(8)-C(10)
C(10)-C(8)-C(9)
O(3)-C(9)-O(4)
O(3)-C(9)-C(8)
O(4)-C(9)-C(8)
Largest deviation
1.2600
1.3964
1.3867
1.3823
1.3889
1.3970
1.4987
1.5081
0.021
119.48
122.17
119.11
120.11
120.35
119.77
117.59
117.01
126.19
117.53
122.77
122.43
114.80
0.89
1.3030
1.4075
1.4002
1.3960
1.3985
1.4097
1.4790
1.5066
0.028
–0.587924
–0.577933
–0.706832
0.579213
–0.954180
0.564980
0.322892
0.601121
0.403165
0.765291
0.233402
0.286445
0.743160
120.08
121.86
119.57
119.89
120.03
118.824
117.44
116.09
125.56
117.09
121.77
123.14
115.08
1.63
and coordination bonds can be formed easily on them, which
had been conformed by experiment. The charge sequence in
H3L was O1>O4>O2>O3, which was in agreement with the
numbers of the hydrogen bonds formed on them.
Table 5 shows the uncalibrated IR frequencies by
HF/6–31+G(d). The largest deviation between the theoretical
and the experimental values was 33 cm−1. The theoretical values
were in agreement with the experimental ones.
those observed from X-ray analysis. The largest deviations of
the bond lengths and bond angles were in the range of the error.
The differences between two calculated results were very small.
Compared with B3LYP/6–31+G(d), the structural data given
by HF/6–31+G(d) was better.
Thermal Behavior
Typical TG-DTG curves for H3L were shown in Figure 4.
It decomposed completely and had nearly no remainder. The
thermal decomposition process of H3L can be divided into three
stages: The first stage was connected with the loss of crystal wa-
ter and the peak of the temperature is 91.0◦ (β = 10◦C·min−1) on
the DTG curve. The second stage was the further decomposition
of H3L except the benzene ring. The peak of the temperature was
216.0◦C. The third stage was the benzene ring decomposition,
and the peak of the temperature was 531.0◦C.
Mulliken net charges on atoms are listed in Table 4, and it
can be seen that most of the negative charge obtained by each
method was located on O and N atoms. It also shows that O1,
N1 had relative large negative charges, and the hydrogen bonds
TABLE 5
The IR frequencies (cm−1) of H3L
Compound υC = O
υC-N
υN-H
υC = N
υOH
Cal.
Exp.
1765
1755
1286
1279
3244
3277
1667
1642
3471
3492
FIG. 3. Optimized structure of H3L by HF/6–31+G(d).

1348
F.-Y. CHEN ET AL.
FUNDING
The study was supported by the Project of Education Com-
mittee of Shaanxi Province (No. 2011JG04), the Shaanxi
Provincial Science and Technology Project (No. 08ZDKG-268),
and the National Science Foundation of China (No. 21273171).
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FIG. 4. TG-DTG curves for the compound H3L at a heating rate of 10◦C
min−1
.
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CONCLUSIONS
The crystal structure of H3L was confirmed by X-ray single-
crystal diffraction. The theoretical study on the title compound
was carried out at HF/6–31+G(d) and B3LYP/6–31+G(d) lev-
els by G03 program. Compared with the experiment data,
HF/6–31+G(d) gave better structural optimization data than
B3LYP/6–31+G(d) method.