Synthesis, characterization and crystal structure of N,N0-di[(E)-1-(2- hydoxyphenyl)methylidene]-2,6-naphthalenedicarbohydrazide

Article abstract of DOI:10.1007/s10870-011-0238-9

A new bishydrazone compound, N,N0-di[(E)-1- (2-hydoxyphenyl)methylidene]-2, 6-naphthalenedicarbohydrazide (1), has been prepared by condensation reaction of 2,6-naphthalenedicarbohydrazide with salicylaldehyde in ethanol, and characterized by elemental analysis, FT-IR, ¹H- and ¹³C-NMR, ESI-MS and single-crystal X-ray diffraction analysis. The crystal of 1.2DMF belongs to monoclinic, space group P2(1)/n with a = 10.454(1), b = 7.711(1), c = 18.801(2) A° , β = 93.364(1)°, V = 1512.9(3) A° ³, Z = 2, Dc = 1.314 g cm^-3, μ = 0.093 mm ^-1, F(000) = 632, Mr = 598.65, the final R1 = 0.0861 and wR2 = 0.2279 for 7243 observed reflections with I>2σ(I). The structural analysis reveals that compound 1.2DMF contains one N,N0-di[(E)-1-(2-hydoxyphenyl) methylidene]-2,6-naphthalenedicarbohydrazide molecule and two N,N-dimethylformamide solvent molecules. A 2D supramolecular structure of 1.2DMF was constructed by multiple intermolecular N-H...O and C-H...O hydrogen bonds. The Author(s) 2011.

Full text of DOI:10.1007/s10870-011-0238-9

J Chem Crystallogr (2012) 42:271–275
DOI 10.1007/s10870-011-0238-9
ORIGINAL PAPER
Synthesis, Characterization and Crystal Structure
of N,N0-di[(E)-1-(2-hydoxyphenyl)methylidene]-2,6-
naphthalenedicarbohydrazide
•
Qingfu Zhang Jiandong Pang Suyuan Zeng
•
•
•
Caihua Liu Dezhi Sun
Received: 7 January 2011 / Accepted: 3 December 2011 / Published online: 14 December 2011
Ó Springer Science+Business Media, LLC 2011
Abstract A new bishydrazone compound, N,N0-di[(E)-1-
(2-hydoxyphenyl)methylidene]-2,6-naphthalenedicarbohy-
drazide (1), has been prepared by condensation reaction of
2,6-naphthalenedicarbohydrazide with salicylaldehyde in
ethanol, and characterized by elemental analysis, FT-IR,
1H- and 13C-NMR, ESI–MS and single-crystal X-ray dif-
fraction analysis. The crystal of 1ꢀ2DMF belongs to
monoclinic, space group P2(1)/n with a = 10.454(1), b =
antiplatelet and antitumoral activities [1–3], and also
because some of them have been successfully employed in
the self-assembly of several intriguing molecular archi-
tectures, such as metallacrown, macrocycle, nanocage,
inorganic [2]-catenane and [n 9 n] grid etc. [4–10].
Thompson and coworkers [5, 6] have carried out a series of
wonderful work on the construction of functional mole-
cules using hydrazone ligands. He and coworkers have also
reported some interesting artificial chemosensors with
multidentate hydrazone ligands [7, 8]. In our previous
article, we also successfully prepared enneanuclear nano-
cage and trinuclear macrocycle using asymmetric tritopic
hydrazone ligands [9, 10]. To continue our research in this
area, we designed and successfully prepared a new func-
tional aroyl hydrazone compound, N,N’-di[(E)-1-(2-hy-
doxyphenyl)methylidene]-2,6-naphthalenedicarbohydrazide
(1), which was completely characterized by elemental
˚
7.711(1), c = 18.801(2) A, b = 93.364(1)°, V = 1512.9(3)
3
A , Z = 2, Dc = 1.314 g cm-3, l = 0.093 mm-1, F(000) =
˚
632, Mr = 598.65, the final R1 = 0.0861 and wR2 =
0.2279 for 7243 observed reflections with I [ 2r(I). The
structural analysis reveals that compound 1ꢀ2DMF contains
one N,N0-di[(E)-1-(2-hydoxyphenyl)methylidene]-2,6-naph-
thalenedicarbohydrazide molecule and two N,N-dimethyl-
formamide solvent molecules. A 2D supramolecular
structure of 1ꢀ2DMF was constructed by multiple inter-
molecular N–HꢀꢀꢀO and C–HꢀꢀꢀO hydrogen bonds.
1
analysis, FT-IR, H- and 13C-NMR, ESI–MS and single-
crystal X-ray diffraction analysis.
Keywords Hydrazone compound ꢀ Synthesis ꢀ
Characterization ꢀ Crystal structure
Experimental Section
Introduction
Materials and Method
Currently, hydrazone compounds have been intensively
investigated because they possess widely antimicrobial,
anticonvulsant, antitubercular, analgesic, antiinflammatory,
All chemicals were of reagent grade obtained from com-
mercial sources and used without further purification. The
elemental analyses of C, H and N were performed on a
PE-2400 II elemental analyzer. The melting point was
obtained with SRS OptiMelt-100 melting point apparatus
and is uncorrected. IR spectra were recorded on a Nicolet-
460 spectrophotometer using KBr discs. 1H- and 13C-NMR
spectra were measured on a Bruker AVANCE III 400 MHz
FT-NMR spectrometer using tetramethylsilane (TMS) as
the internal reference. ESI–MS spectra were recorded on a
Q. Zhang (&) ꢀ J. Pang ꢀ S. Zeng ꢀ C. Liu ꢀ D. Sun
Shandong Provincial Key Laboratory of Chemical Energy
Storage and Novel Cell Technology, College of Chemistry
and Chemical Engineering, Liaocheng University, Liaocheng
252059, China
e-mail: zhangqingfu@lcu.edu.cn
123

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J Chem Crystallogr (2012) 42:271–275
Finnigan DE-CAX-30000 LCQ Deca XP ion trap mass
spectrometer.
Table 1 Crystal data and structure refinement for 1ꢀ2DMF
Empirical formula
Formula weight
Temperature (K)
C32H34N6O6
598.65
Preparation of Compound 1
298(2)
˚
Wavelength (A)
0.71073
Monoclinic
P2(1)/n
2,6-naphthalene-dicarbohydrazide (3 mmol, 0.732 g) was
added to EtOH solution (60 mL) containing salicylaldehyde
(6 mmol, 0.732 g). After 3 drops of acetic acid were added,
the yellow mixture was heated at boiling temperature under
magnetic stirring for 24 h. During the reaction, a yellow
precipitate was formed, which was collected by filtration.
Yield: 1.085 g, 80%. M.p.: 326–328 °C. Anal. calc. For
C26H20N4O4 (%): C, 69.02; H, 4.46; N, 12.38. Found (%):
C, 68.95; H, 4.50; N, 12.30. IR (KBr, cm-1): 3450, 3208,
Crystal system
Space group
˚
a = 10.454(1) A
Unit cell dimensions
˚
b = 7.711(9) A
˚
c = 18.801(2) A
b = 93.364(1)°
1512.9(3)
3
˚
Volume (A )
Z
2
1
Calculated density (Mg/m3)
Absorption coefficient (mm-1
F(000)
1.314
1665, 1608, 1445, 1410, 1285, 1028, 875, 465. H-NMR
)
0.093
(400 MHz, DMSO-d6, ppm): 12.365 (s, 2H, –NH), 11.264
(s, 2H, –OH), 8.717 (s, 2H, –CH=N–), 8.649 (s, 2H, Ar–H),
8.250 (d, 2H, J = 8.4 Hz, Ar–H), 8.101 (d, 2H, J = 8.4 Hz,
Ar–H), 7.605 (d, 2H, J = 6.8 Hz, Ar–H), 7.349 (m, 2H,
Ar–H), 6.954 (m, 4H, Ar–H). 13C-NMR (100 MHz,
DMSO-d6, ppm): 183.76 (–C(O)NH–), 168.11 (Ph-C–OH),
162.91 (–CH=N–), 153.85 (Ar–C), 138.98(Ar–C), 137.43
(Ar–C), 136.95(Ar–C), 134.86(Ar–C), 133.34(Ar–C),
130.67(Ar–C), 124.84(Ar–C), 124.18(Ar–C), 121.88(Ar–
C). ESI–MS: m/z 453.4 [M ? H?]. The high-quality yellow
single crystals of 1ꢀ2DMF suitable for X-ray diffraction
were obtained by recrystallization from N,N-dimethyl-
formamide (DMF).
632
Crystal size (mm3)
0.30 9 0.20 9 0.15
Theta range for data collection (°) 2.17–25.02
Limiting indices
-12 B h B 8, -9 B k B 9,
-22 B l B 22
Reflections collected/unique
Completeness to h = 25.02°
Absorption correction
7243/2675 (Rint = 0.0496)
99.9%
Multi-scan
Max. and min. transmission
Refinement method
0.9862 and 0.9727
Full-matrix least-squares on F2
2675/0/201
Data/restraints/parameters
Goodness-of-fit on F2
1.025
Final R indices [I [ 2r(I)]
R indices (all data)
R1 = 0.0861, wR2 = 0.2279
R1 = 0.1620, wR2 = 0.2980
0.847 and -0.333
X-Ray Crystallography
-3
)
˚
Largest diff. peak and hole (eA
A suitable yellow single-crystal with dimensions of
0.30 9 0.20 9 0.15 mm was selected for indexing and
intensity data collection on a Bruker smart-1000 CCD
diffractometer at 298(2) K using MoKa radiations (0.71073
parameters are given in Table 3. The molecular structure of
compound 1ꢀ2DMF is shown in Fig. 1, and the supramo-
lecular structure including the H-bonding interactions is
illustrated in Fig. 2.
˚
A). Multi-scan absorption corrections based on symmetry
equivalents were applied to the 7243 reflections collected
(2hmax = 50.04), 2675 unique reflections were observed
(Rint = 0.0496) after data reduction. The structure was
solved by direct methods and refined by full-matrix least-
squares on F2 using SHELXL-97 program [11]. All non-
hydrogen atoms were refined anisotropically. Hydrogen
atoms were located at calculated positions and refined
isotropically. The final refinement by full-matrix least
squares method was converged at R1 = 0.0861, and
wR2 = 0.2279 (R = R||Fo|-|Fc||/R|Fo|, wR = [Rw(F2o-
F2c)/Rw(F2o)2]1/2), S = 1.025, (D/r)max = 0.000. The larg-
Results and Discussion
Synthesis and Spectral Characterization of Compound 1
As shown in Scheme 1, compound 1 was prepared by
Schiff base reaction of 2,6-naphthalene-dicarbohydrazide
and salicylaldehyde in ethanol with 3 drops of acetic acid.
The molecular formula of 1 is determined to be
C26H20N4O4 according to elementary analysis and ESI–MS
spectrum.
-3
˚
est peak in the final difference Fourier map is 0.847 eA
-3
The number of hydrogen atoms observed in the 1H-
˚
and the minimum peak is -0.333 eA
.
NMR spectrum of compound 1 is in agreement with this
1
molecular formula. In the H-NMR spectrum, two down-
The crystallography details for the structure determina-
tion and refinement for 1ꢀ2DMF are summarized in
Table 1, selected bond lengths and bond angles for com-
pound 1ꢀ2DMF are listed in Table 2, and hydrogen bond
field signals at 12.365 and 11.264 are ascribed to
–C(O)NH– and –OH, respectively. The signal at 8.717 is
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J Chem Crystallogr (2012) 42:271–275
273
Table 2 Selected bond lengths
˚
Table 2 continued
˚
Bond lengths (A)
O2–C13–C8
O2–C13–C12
C8–C13–C12
O3–C19–N3
122.7(4)
117.0(5)
120.4(5)
131.6(9)
(A) and angles (°) for 1ꢀ2DMF
O1–C6
1.221(6)
1.353(6)
1.194(8)
1.347(6)
1.371(5)
1.282(6)
1.277(8)
1.410(8)
1.452(9)
1.368(6)
1.407(6)
1.412(6)
1.414(9)
1.367(6)
1.410(7)
1.487(7)
1.368(7)
1.446(6)
1.391(7)
1.395(7)
1.371(7)
1.369(8)
1.367(7)
1.393(7)
Symmetry transformations used
to generate equivalent atoms: #1
-x ? 1, -y ? 1, -z
O2–C13
O3–C19
N1–C6
N1–N2
N2–C7
˚
Table 3 Hydrogen bond lengths (A) and angles (°) for 1ꢀ2DMF
N3–C19
D–H
HꢀꢀꢀA
DꢀꢀꢀA
D–HꢀꢀꢀA
N3–C21
N3–C22
N1–H1AꢀꢀꢀO3
O2–H2AꢀꢀꢀN2
C5–H5ꢀꢀꢀO3
C7–H7ꢀꢀꢀO3
C16–H16AꢀꢀꢀO#1
C16–H16CꢀꢀꢀO2#1
0.79
0.81
0.93
0.93
0.96
0.96
2.09(5)
1.93(6)
2.40
2.835(6)
2.610(5)
3.299(6)
3.291(3)
3.574(2)
3.349(2)
158.8(3)
144.3(2)
161.8(3)
139.1(3)
150.3(1)
125.3(2)
C1–C5#1
C1–C2
C2–C3
2.53
C2–C2#1
2.71
C3–C4
2.70
C4–C5
Symmetry transformations used to generate the equivalent atoms: #1
x - 1/2, 3/2 - y, z - 1/2
C4–C6
C5–C1#1
C7–C8
C8–C13
ascribed to the proton on the –CH=N– group, and the other
signals from 8.649 to 6.954 can be ascribed to the hydrogen
atoms on the phenyl and naphthyl rings. Additional support
for the structure of the compound 1 was provided by 13C-
NMR spectra. The chemical shift values (ppm) at 183.76,
168.11 and 162.91 are tentatively ascribed to the carbon
atoms in –C(O)NH–, Ph-C–OH and –CH=N– groups,
respectively. And the other ten signals from 153.85 to
121.88 could be ascribed to the aromatic carbon atoms on
the phenyl and naphthyl rings.
C8–C9
C9–C10
C10–C11
C11–C12
C12–C13
Bond angles (°)
C6–N1–N2
C7–N2–N1
C19–N3–C21
C19–N3–C22
C21–N3–C22
C5#1–C1–C2
C1–C2–C3
C1–C2–C2#1
C3–C2–C2#1
C4–C3–C2
C3–C4–C5
C3–C4–C6
C5–C4–C6
C1#1–C5–C4
O1–C6–N1
O1–C6–C4
N1–C6–C4
N2–C7–C8
C13–C8–C9
C13–C8–C7
C9–C8–C7
C10–C9–C8
C11–C10–C9
C12–C11–C10
C11–C12–C13
117.8(4)
117.4(4)
123.5(7)
118.8(7)
117.6(7)
120.6(5)
122.1(4)
119.6(5)
118.4(5)
121.4(4)
119.8(4)
116.9(4)
123.3(4)
120.3(4)
121.3(5)
121.7(5)
117.0(5)
120.1(5)
118.2(4)
122.3(4)
119.5(5)
121.3(5)
119.3(5)
121.5(5)
119.3(5)
In the IR spectrum, the absorption bands at 3,450–
3,208 cm-1 characterize the –OH and –NH groups in com-
pound 1. The two strong peaks at 1,665 and 1,410 cm-1 are
assigned to the –C=O and –C=N absorption of the hydrazone
group according to the literature [12]. The absorption peak at
1,285 cm-1 is ascribed to the vibration of amide III band, and
the absorption peak at 1,028 cm-1 is ascribed to the C–O
stretching vibration of Ph-OH group. In addition, the
absorption peak at 875 cm-1 is ascribed to the C–H bending
vibration of E-(–CH=N–) group. And the absorption band at
465 cm-1 is ascribed to the Ar–H out-of-plane ring defor-
mation vibrations in compound 1. All the above IR attribution
is consistent with structural determination.
Structural Description of Compound 1ꢀ2DMF
Single-crystal X-ray diffraction analysis reveals that com-
pound 1ꢀ2DMF crystallizes in monoclinic P2(1)/n space
group and consists of one N,N0-di[(E)-1-(2-hydoxyphe-
nyl)methylidene]-2,6-naphthalenedicarbohydrazide mole-
cule and two DMF solvent molecules. As shown in Fig. 1,
the hydroxyl group and imine N atom are linked by
intramolecular O–HꢀꢀꢀN (O2–H2AꢀꢀꢀN2: O2ꢀꢀꢀN2 2.610(5)
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J Chem Crystallogr (2012) 42:271–275
Fig. 1 The molecular structure
of 1ꢀ2DMF. Dotted lines
indicate the O–HꢀꢀꢀN, N–HꢀꢀꢀO
and C–HꢀꢀꢀO H-bonding
interactions
Fig. 2 The suparmolecular
structure of 1ꢀ2DMF linked by
intermolecular O–HꢀꢀꢀN, N–
HꢀꢀꢀO and C–HꢀꢀꢀO H-bonding
interactions: a 1D
supramolecular chain, b 2D
supramolecular network
˚
A, O2–H2AꢀꢀꢀN2 144.3(2)°) H-bonding interactions to
conformation, and the dihedral angle between the central
naphthyl ring and the above mentioned plane containing
C6, N1, O1 atoms and iminosalicylidene group is about
11.94°. This non-planar conformation of N,N0-di[(E)-1-
(2-hydoxyphenyl)methylidene]-2,6-naphthalenedicarbohy-
drazide should root from the C–C (C4–C6) single bond
rotation between the central naphthyl ring and acyl
form a six-member-ring structure, thus the plane containing
iminosalicylidene group and C6, N1, O1 atoms is almost
˚
coplanar with the maximum deviation 0.087 A for O1 atom
in the acyl group. However, to our surprise, the whole
N,N0-di[(E)-1-(2-hydoxyphenyl)methylidene]-2,6-naphtha-
lenedicarbohydrazide in 1ꢀ2DMF adopts a non-planar
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J Chem Crystallogr (2012) 42:271–275
275
Supplementary Material
CCDC 780563 contains the supplementary crystallographic
data for the compound. These data can be obtained free of
charge via http://www.ccdc.cam.ac.Uk/deposit, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambambridge CB2 1EZ, UK; fax: (?44) 1223-336-033;
or e-mail:deposit@ccdc.cam.ac.uk.
Scheme 1 Synthesis of compound 1
group, and be stabilized by the intermolecular N–HꢀꢀꢀO
˚
(N1–H1AꢀꢀꢀO3: N1ꢀꢀꢀO3 2.835 (6) A, N1–H1AꢀꢀꢀO3
Acknowledgments This study was supported by the National Nature
Science Foundation of China (Grant No. 21001061), the Nature Science
Foundation of Shandong Province (Grant No. ZR2010BL020) and the
Liaocheng University Funds for Young Scientist (31805), and also par-
tiallysupportedbyPostgraduateStudents’InovationProjectofShandong
Province (LCUYZ10008).
˚
158.8(3)°) and C–HꢀꢀꢀO (C5–H5ꢀꢀꢀO3: C5ꢀꢀꢀO3 3.299 (6) A,
C5–H5ꢀꢀꢀO3 161.8(3)° and C7–H7ꢀꢀꢀO3: C7ꢀꢀꢀO3 3.291 (3)
˚
A, C7–H7ꢀꢀꢀO3 139.1(3)°) H-bonding interactions. Two new
C=N bonds in 1ꢀ2DMF formed by the condensation reaction
represent the typical double bonds with distances of 1.282(6)
˚
(C7–N2 and C7A–N2A) A. The bond lengths of C=O (C6–
˚
˚
O1 1.221(6) A) and C–N (C6–N1 1.347(6) A) suggest the
C(O)NH group adopts usually ketonic form in 1ꢀ2DMF,
which are in the normal range of carbohydrazone compounds
[12–14].
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