Synthesis, characterization and crystal structures of 3-hydroxy-N'- [methyl(2-pyridyl)methylene]-2-naphthohydrazide monohydrate and 3-hydroxy-N'-(3,5-dibromo-2-hydroxybenzylidene)-2-naphthohydrazide dimethylformamide solvate

Article abstract of DOI:10.1007/s10870-012-0297-6

Two hydrazone compounds, 3-hydroxy-N'-[methyl (2-pyridyl)methylene]-2- naphthohydrazide monohydrate (1), and 3-hydroxy-N'-(3,5-dibromo-2- hydroxybenzylidene)-2-naphthohydrazide dimethylformamide solvate (2), have been prepared and characterized by elemental analysis, IR spectra, ¹HNMR spectra, and X-ray single crystal structural determination. Compound (1) crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 11.072(2) A, b = 12.017(2) A, c = 23.753(3) A, β = 95.710(2)°, V = 3144.7(9) A³, Z = 8, R₁ = 0.0780, and wR₂ = 0.1465. Compound (2) crystallizes in the triclinic space group P-1 with unit cell dimensions a = 7.601(2) A, b = 16.522(4) A, c = 17.048(3) A, α = 92.516(11)°, β = 96.726(12)°, γ = 94.117(12)°, V = 2117.8(8) A³, Z = 4, R₁ = 0.0490, and wR₂ = 0.1012. The hydrazone molecules in the compounds adopt trans configurations about the C=N double bonds. The crystal structures of the compounds are stabilized by intermolecular hydrogen bonds and π ... π stacking interactions. Springer Science+Business Media, LLC 2012.

Full text of DOI:10.1007/s10870-012-0297-6

J Chem Crystallogr (2012) 42:668–672
DOI 10.1007/s10870-012-0297-6
ORIGINAL PAPER
Synthesis, Characterization and Crystal Structures of 3-Hydroxy-
N0-[methyl(2-pyridyl)methylene]-2-naphthohydrazide
monohydrate and 3-Hydroxy-N0-(3,5-dibromo-2-
hydroxybenzylidene)-2-naphthohydrazide dimethylformamide
solvate
•
Guo-Ping Cheng Ling-Wei Xue Wei-Chun Yang
•
Received: 22 October 2011 / Accepted: 14 February 2012 / Published online: 28 February 2012
Ó Springer Science+Business Media, LLC 2012
Abstract Two hydrazone compounds, 3-hydroxy-N0-[methyl
(2-pyridyl)methylene]-2-naphthohydrazide monohydrate (1),
and 3-hydroxy-N0-(3,5-dibromo-2-hydroxybenzylidene)-2-naph-
thohydrazide dimethylformamide solvate (2), have been
prepared and characterized by elemental analysis, IR spec-
tra, 1HNMR spectra, and X-ray single crystal structural
determination. Compound (1) crystallizes in the monoc-
linic space group C2/c with unit cell dimensions a =
have been proved to have interesting biological activities
such as antibacterial, antifungal, and antitumor [1–5].
Hydrazone compounds bearing NNO donor atoms have
also been introduced to coordination chemistry [6–8].
Detailed study on the preparation and structures of such
compounds seems important to understand their biologi-
cal activities and coordination capabilities. Ibrahim and
coworkers reported a series of complexes with 3-hydroxy-
N0-[methyl(2-pyridyl)methylene]-2-naphthohydrazide [9].
In addition, a few references have mentioned 3-hydroxy-
N’-(3,5-dibromo-2-hydroxybenzylidene)-2-naphthohydraz-
ide [10, 11]. However, no single-crystal X-ray diffraction
has been characterized for the compounds. In this paper,
two hydrazone compounds, 3-hydroxy-N0-[methyl(2-pyri-
dyl)methylene]-2-naphthohydrazide monohydrate (1) and
3-hydroxy-N0-(3,5-dibromo-2-hydroxybenzylidene)-2-
naphthohydrazide dimethylformamide solvate (2), have
been prepared and structurally characterized (Chart 1).
˚
˚
˚
11.072(2) A, b = 12.017(2) A, c = 23.753(3) A, b =
´
3
˚
95.710(2)°, V = 3144.7(9) A , Z = 8, R1 = 0.0780, and
wR2 = 0.1465. Compound (2) crystallizes in the triclinic
space group P-1 with unit cell dimensions a =
˚
˚
˚
7.601(2) A, b = 16.522(4) A, c = 17.048(3) A, a = 92.516(11)°,
´
3
˚
b = 96.726(12)°, c = 94.117(12)°, V = 2117.8(8) A , Z =
4, R1 = 0.0490, and wR2 = 0.1012. The hydrazone mole-
cules in the compounds adopt trans configurations about the
C=N double bonds. The crystal structures of the compounds
are stabilized by intermolecular hydrogen bonds and pꢀꢀꢀp
stacking interactions.
Keywords Synthesis ꢀ Crystal structure ꢀ X-ray
diffraction ꢀ Hydrazone
Experimental
Materials and Methods
Introduction
3-Hydroxy-2-naphthoic acid hydrazide, 2-acetylpyridine,
and 3,5-dibromo-2-hydroxybenzaldehyde with AR grade
were purchased from Fluka. Other reagents and solvents
were used without further purification. Elemental (C, H and
N) analyses were made on a Perkin-Elmer Model 240B
automatic analyser. IR spectra were recorded on an IR-408
Shimadzu 568 spectrophotometer. The [1]HNMR spectra
were recorded on Bruker AVANCE 400 MHz spectrome-
ter with tetramethylsilane as the internal reference. X-ray
diffraction was carried out on a Bruker SMART 1000 CCD
area diffractometer.
Hydrazone compounds are readily prepared by the reaction
of aldehydes with hydrazines, with quantitative yields and
high purity. In the last few years, hydrazone derivatives
G.-P. Cheng ꢀ L.-W. Xue (&) ꢀ W.-C. Yang
College of Chemistry and Chemical Engineering,
Pingdingshan University, Pingdingshan 467000, Henan,
People’s Republic of China
e-mail: pdsuchemistry@163.com
123

J Chem Crystallogr (2012) 42:668–672
669
Br
HO
O
O
N
N
N
N
H
Br
N
H
OH
H2O
DMF
OH
(1)
(2)
Chart 1 The hydrazone compounds
Preparation of 3-hydroxy-N0-[methyl(2-pyridyl)
calculated for C18H15N3O2: C, 70.8; H, 5.0; N, 13.8%;
found: C, 70.6; H, 5.0; N, 13.7%. IR data (KBr, cm-1):
3432 (br, w), 3207 (w, sh), 1655 (vs), 1608 (m), 1547 (s),
1511 (s), 1453 (s), 1382 (w), 1346 (s), 1312 (m), 1259 (s),
1172 (m), 1116 (w), 932 (m), 851 (w), 807 (m), 691 (w),
627 (m), 572 (w), 475 (w). 1H NMR (CDCl3): d (ppm) 1.80
(s, 3H), 7.45–7.61 (m, 3H), 7.64 (t, 1H), 7.77–7.96 (m, 4H),
8.38 (s, 1H), 8.62 (d, 1H), 10.27 (s, 1H), 13.35 (s, 1H).
Crystals suitable for X-ray diffaction were obtained by
methylene]-2-naphthohydrazide monohydrate (1)
A methanol solution (30 ml) of 3-hydroxy-2-naphthoic
acid hydrazide (0.20 g, 1 mmol) and 2-acetylpyridine
(0.12 g, 1 mmol) was refluxed for 1 h. The solution was
then cooled to room temperature and the solid product
formed was filtered off, washed with cold methanol, and
dried over silica gel. Yield 0.23 g (75%). Analysis
Table 1 Crystal and structure
Compound
(1)
(2)
refinement data for (1) and (2)
CCDC
849709
849710
Molecular formula
Molecular weight
Crystal system
Space group
C
18H17N3O3
C21H19Br2N3O4
537.2
323.3
Monoclinic
Triclinic
C2/c
P-1
´
˚
a/A
11.072(2)
7.601(2)
´
˚
b/A
12.017(2)
16.522(4)
17.048(3)
92.516(11)
96.726(12)
94.117(12)
2117.8(8)
4
´
˚
c/A
23.753(3)
a/°
b/°
c/°
90
95.710(2)
90
´
3
˚
V/A
3144.7(9)
Z
8
Dcalc (g cm-3
)
1.353
1.685
Crystal dimensions (mm)
0.13 9 0.10 9 0.10
0.095
0.23 9 0.20 9 0.20
3.861
l/mm
´
˚
Radiation k (A)
Mo Ka (0.71073)
0.9878/0.9906
13173
Mo Ka (0.71073)
0.4704/0.5123
13028
Tmin/Tmax
Reflections measured
Range/indices (h, k, l)
h limit (°)
Unique reflections
Observed reflections (I [ 2r(I))
Parameters
-13, 14; -15, 15; -29, 30
1.72–27.00
3391 [Rint = 0.0858]
1666
-9, 9; -18, 21; -19, 21
1.20–27.00
9033 [Rint = 0.0291]
4762
229
559
Restraints
5
4
Goodness of fit on F2
R1, wR2 [I C 2r(I)]a
R1, wR2 (all data)a
1.020
1.007
P
P
a
R1 = ||Fo|-|Fc||/ |Fo|,
wR2 = [ w(F2o-Fc2)2/
0.0779, 0.1471
0.1667, 0.1819
0.0490, 0.1012
0.1196, 0.1235
P
P
w(F2o)2]1/2
123

670
J Chem Crystallogr (2012) 42:668–672
slow evaporation of a methanol solution of the compound
at room temperature.
Table 3 Hydrogen geometries for (1) and (2)
˚
d(D–H) (A)
D–HꢀꢀꢀA
d(HꢀꢀꢀA)
d(DꢀꢀꢀA)
Angle(D–
HꢀꢀꢀA) (°)
˚
(A)
˚
(A)
Preparation of 3-hydroxy-N0-(3,5-dibromo-2-
hydroxybenzylidene)-2-naphthohydrazide
dimethylformamide solvate (2)
(1)
O1–H1AꢀꢀꢀO3i
N1–H1ꢀꢀꢀO1
O3–H3AꢀꢀꢀN3ii
O3–H3BꢀꢀꢀO2iii
(2)
0.82(1)
0.82(1)
0.90(1)
0.90(1)
1.83(2)
1.93(2)
1.96(1)
1.92(1)
2.626(4)
2.642(3)
2.853(4)
2.810(3)
163(4)
144(4)
172(3)
166(4)
A methanol solution (30 ml) of 3-hydroxy-2-naphthoic acid
hydrazide (0.20 g, 1 mmol) and 3,5-dibromo-2-hydro-
xybenzaldehyde (0.28 g, 1 mmol) was refluxed for 1 h. The
solution was then cooled to room temperature and the solid
product formed was filtered off, washed with cold methanol, and
dried over silica gel. Yield 0.37 g (80%). Analysis calculated for
C18H12Br2N2O3: C, 46.6; H, 2.6; N, 6.0%; found: C, 46.5; H,
2.7; N, 6.1%. IR data (KBr, cm-1): 3410 (br, w), 3222 (w, sh),
1658 (vs), 1601 (m), 1559 (s), 1518 (m), 1443 (s), 1386 (m),
1357 (m), 1320 (s), 1305 (s), 1228 (s), 1171 (m), 1151 (m), 1105
(w), 945 (w), 904 (w), 879 (w), 794 (m), 761 (w), 739 (w), 687
(w), 666 (w), 636 (w), 470 (w), 418 (w). 1H NMR (DMSO-d6): d
(ppm) 7.45–7.59 (m, 3H), 7.73–7.95 (m, 4H), 8.40 (s, 1H), 8.77
(s, 1H), 10.45 (s, 1H), 13.27–13.45 (b, 2H). Crystals suitable for
X-ray diffaction were obtained by slow diffusion of diethyl ether
to DMF solution of the compound at room temperature.
O1–H1ꢀꢀꢀN1
O4–H4ꢀꢀꢀN3
N2–H2ꢀꢀꢀO7iv
O6–H6ꢀꢀꢀO5
O3–H3ꢀꢀꢀO2
0.82
1.90
2.588(5)
2.588(5)
2.810(5)
2.553(5)
2.543(5)
141
0.82
1.87
146
0.90(1)
0.85(1)
0.85(1)
1.97(3)
1.76(3)
1.81(3)
153(5)
154(5)
144(5)
Symmetry codes: (i) -1/2 ? x, ‘ - y, ‘ ? z; (ii) 3/2 - x,-1/2 ? y,
3/2 - z; (iii) 1 - x, y, 3/2 - z; (iv) -1 ? x, y, z
SADABS [13]. The structures of the compounds were
solved by direct method using the program SHELXS-97,
and were refined by full-matrix least-squares technique on
F2 using anisotropic displacement parameters [14]. The N
and O attached hydrogen atoms in both compounds were
located from difference Fourier maps and refined isotrop-
ically. The remaining H atoms were placed at the calcu-
lated positions. Idealized H atoms were refined with
isotropic displacement parameters set to 1.2 (1.5 for methyl
groups) times the equivalent isotropic U values of the
parent carbon atoms. The crystallographic data for the
compounds are listed in Table 1. Selected bond lengths and
angles are in listed in Table 2. Hydrogen bonding inter-
actions are summarized in Table 3.
X-Ray Diffraction
Data were collected from selected crystals mounted on
glass fibres. The data for the two compounds were pro-
cessed with SAINT [12] and corrected for absorption using
´
˚
Table 2 Selected bond lengths (A) and angles (°) for (1) and (2)
(1)
Bond lengths
Results and Discussion
C12–N2
1.282(4)
1.355(4)
1.371(4)
N2–N1
1.369(3)
1.224(3)
N1–C11
C11–O2
The two compounds were first prepared as white solid
products. Compound (1) is soluble in methanol, ethanol,
acetonitrile, and chloroform. The single crystals of (1) were
recrystallized from methanol. Compound (2) is insoluble in
C2–O1
Bond angles
C12–N2–N1
N1–C11–O2
(2)
117.1(3)
122.3(3)
N2–N1–C11
118.8(3)
Bond lengths
C7–N1
1.272(5)
1.356(6)
1.348(5)
1.269(5)
1.347(5)
1.341(5)
118.5(4)
119.8(4)
118.2(4)
N1–N2
1.367(5)
1.241(5)
1.356(5)
1.366(5)
1.229(5)
1.356(5)
117.9(4)
118.6(4)
120.3(4)
N2–C8
C8–O2
C2–O1
C10–O3
C25–N3
N3–N4
N4–C26
C26–O5
C20–O4
C28–O6
C7–N1–N2
N2–C8–O2
N3–N4–C26
N1–N2–C8
C25–N3–N4
N4–C26–O5
Fig. 1 Perspective view of (1) with 30% probability thermal
ellipsoids. Hydrogen bond is drawn as a dashed line
123

J Chem Crystallogr (2012) 42:668–672
671
Fig. 2 Molecular packing of (1). Hydrogen bonds are drawn as
dashed lines
the solvents mentioned above, but soluble in DMF and
DMSO. The single crystals of (2) were obtained by slow
diffusion of the diethyl ether to the DMF solution of the
compound. Both compounds were crystallized as air-stable
colorless crystals. The elemental analyses are in agreement
with the formulae proposed by the X-ray determination.
Fig. 3 Perspective view of (2) with 30% probability thermal
ellipsoids. Hydrogen bonds are drawn as dashed lines
Crystal Structure Description of (1)
The molecular structure of (1) is depicted in Fig. 1. The
compound contains a hydrazone molecule and a water
molecule. The hydrazone molecule displays a trans con-
figuration about the C=N double bond. The bond lengths
are within normal ranges [15–17]. The C12=N2 bond
˚
length is 1.282(4) A, confirming it as a double bond. The
˚
C11–N1 bond length of 1.355(4) A and the N1–N2 bond
˚
length of 1.370(3) A in the hydrazone molecule are rela-
tively short, suggesting some degree of delocalization in
the acetohydrazide system. The delocalization of the mol-
ecule, as well as the presence of the intramolecular N1–
H1ꢀꢀꢀO1 hydrogen bond, lead to the planarity of the
Fig. 4 Molecular packing of (2), viewed along the a axis. Hydrogen
bonds are drawn as dashed lines
Table 4 Parameters between the planes for (1) and (2)
Cg
Distance between
˚
ring centroids (A)
Dihedral
angle (°)
Perpendicular distance
˚
of Cg(I) on Cg(J) (A)
Beta
angle (°)
Gamma
angle (°)
Perpendicular
distance of Cg(J) on
˚
Cg(I) (A)
(1)
Cg(1)–Cg(2)b
Cg(1)–Cg(3)b
Cg(2)–Cg(2)c
(2)
4.443
3.881
4.072
8.11
6.34
0.00
3.512
3.532
3.562
40.08
20.56
28.99
37.78
24.49
28.99
3.400
3.634
3.562
Cg(4)–Cg(5)d
Cg(4)–Cg(5)e
Cg(4)–Cg(6)d
Cg(7)–Cg(8)f
Cg(7)–Cg(8)g
3.774
4.802
4.578
4.769
4.716
0.75
0.75
0.38
2.50
2.50
3.514
3.485
3.508
3.518
3.482
21.57
44.07
39.60
44.78
40.31
21.41
43.47
39.97
42.46
42.41
3.510
3.450
3.527
3.385
3.597
Cg(1), Cg(2), and Cg(3) are the centroids of N3–C13–C14–C15–C16–C17, C1–C2–C3–C4–C9–C10, and C4–C5–C6–C7–C8–C9 in (1),
respectively. Cg(4), Cg(5), Cg(6), Cg(7), and Cg(8) are the centroids of C1–C2–C3–C4–C5–C6, C9–C10–C11–C12–C17–C18, C12–C13–C14–
C15–C16–C17, C19–C20–C21–C22–C23–C24, and C27–C28–C29–C30–C35–C36 in (2), respectively. Symmetry codes: (b) ‘ - x, ‘ - y,-z;
(c) -x, 1 - y, -z; (d) -x, -y, 1 - z; (e) 1 - x, -y, 1 - z; (f) -x, 1 - y, -z; (g) 1 - x, 1 - y, -z
123

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J Chem Crystallogr (2012) 42:668–672
hydrazone molecule. The dihedral angle between the
naphthyl ring and the pyridine ring is 6.8(2)°.
In the crystal structure of (1), the hydrazone molecules
are linked by the water molecules through intermolecular
O–HꢀꢀꢀO and O–HꢀꢀꢀN hydrogen bonds, to form 1D chains
(Fig. 2). In addition, there are pꢀꢀꢀp stacking interactions
(Table 4) among the adjacent aromatic systems [15].
ac.uk/const/retrieving.html or from the Cambridge Crys-
tallographic Data Centre (CCDC), 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: ?44(0)1223-336033 or e-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgments This research was supported by the National
Sciences Foundation of China (No. 20676057 and 20877036) and
Top-class foundation of Pingdingshan University (No. 2008010).
Crystal Structure Description of (2)
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lengths are within normal ranges [15–17], and are com-
parable to those observed in (1). The C7=N1 and C25=N3
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Supplementary Material
CCDC-849709 for (1) and 849710 for (2) contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge at http://www.ccdccam.
123