Syntheses, X-ray crystal structures and intermolecular interaction patterns of hydrazone derivatives with 1,2,3-triazole entity at 100 K

Article abstract of DOI:10.1007/s10870-014-0504-8

Five new hydrazone derivatives, (E)-N-(4-fluorobenzylidene)-5-methyl-1-(4- nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide, (E)-N-(4-chlorobenzylidene)-5- methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide, (E)-N-(4-bromobenzylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2, 3-triazole-4-carbohydrazide, (E)-N-(4-hydroxy-3-methoxybenzylidene)-5-methyl-1- (4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide and (E)-N-(1-(4-bromophenyl) ethylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide (denoted as A-E), were prepared and their molecular structures were characterized by single crystal X-ray diffraction. Compound A crystallizes in monoclinic P2₁/c, a = 6.8057(1) A, b = 12.7447(3) A, c = 18.6936(3) A, β = 105.356(1)°, B crystallizes in monoclinic P2₁/c, a = 8.3815(2) A, b = 20.8298(4) A, c = 9.5932(2) A, β = 99.612(1)°, C crystallizes in monoclinic P2₁/c, a = 8.4213(8) A, b = 21.077(2) A, c = 9.5899(10) A, β = 99.979(2)°, D crystallizes in monoclinic P2₁/c, a = 11.1644(10) A, b = 16.3508(15) A, c = 9.7313(9) A, β = 105.757(1)° and E crystallizes in triclinic P 1 , a = 8.7415(7) A, b = 10.1032(8) A, c = 11.6852(9) A, α = 68.306(1)°, β = 84.894(1)°, γ = 68.289(1)°. All of the five compounds with close molecular conformations adopt a trans configuration with respect to the hydrazone C = N double bond and weak non-classical intermolecular C-H···O hydrogen bonds are observed in the crystal. Isomorphous substitution between compounds B and C with simple replacement of chlorine atom to bromine atom is giving rise to similar molecular geometries, unit cell parameters and intermolecular interaction pattern of three-dimensional network. Graphical Abstract: Five new hydrazone derivatives possessing 5-methyl-1-(4-nitrophenyl)-1,2,3-triazole moiety (denoted as A to E) are characterized by single crystal X-ray structure determination method. The intermolecular interaction pattern of D is strongly influenced by strong O-H···O hydrogen bond, whereas only non-classical C-H···O hydrogen bonds are observed in the rest. Compounds B and C with isomorphous chlorine-bromine substitution are crystallized under same space group and similar unit cell parameters.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-014-0504-8

J Chem Crystallogr (2014) 44:220–228
DOI 10.1007/s10870-014-0504-8
ORIGINAL PAPER
Syntheses, X-ray Crystal Structures and Intermolecular
Interaction Patterns of Hydrazone Derivatives with 1,2,3-Triazole
Entity at 100 K
•
Tze Shyang Chia Ching Kheng Quah
•
•
Wan-Sin Loh Nithin Chandra
•
•
Balakrishna Kalluraya Hoong-Kun Fun
Received: 28 January 2014 / Accepted: 28 February 2014 / Published online: 13 March 2014
Ó Springer Science+Business Media New York 2014
Abstract Five new hydrazone derivatives, (E)-N0-(4-fluo-
robenzylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-
4-carbohydrazide, (E)-N0-(4-chlorobenzylidene)-5-methyl-1-
(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide, (E)-N0-
(4-bromobenzylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,
3-triazole-4-carbohydrazide, (E)-N0-(4-hydroxy-3-methox-
ybenzylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-
4-carbohydrazide and (E)-N0-(1-(4-bromophenyl)ethylidene)-
5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohy-
drazide (denoted as A-E), were prepared and their molecular
structures were characterized by single crystal X-ray dif-
fraction. Compound A crystallizes in monoclinic P21/c,
respect to the hydrazone C = N double bond and weak non-
classical intermolecular C–HꢀꢀꢀO hydrogen bonds are observed
in the crystal. Isomorphous substitution between compounds
B and C with simple replacement of chlorine atom to bromine
atom is giving rise to similar molecular geometries, unit cell
parameters and intermolecular interaction pattern of three-
dimensional network.
Keywords Hydrazone ꢀ Triazole ꢀ Crystal structure ꢀ
Hydrogen bond ꢀ Isomorphous substitution
˚
˚
˚
a = 6.8057(1) A, b = 12.7447(3) A, c = 18.6936(3) A,
b = 105.356(1)°, B crystallizes in monoclinic P21/c, a =
Introduction
˚
˚
˚
8.3815(2) A, b = 20.8298(4) A, c = 9.5932(2) A, b =
Hydrazones, a class of organic compounds which con-
taining an azomethine –NHN=CH– group are formed by
the condensation of substituted hydrazines with aldehydes
or ketones. Hydrazones can also be synthesized through
the coupling of aryldiazonium salts with active hydrogen
compounds [1] and this is also one of the oldest methods
for the synthesis of arylhydrazones as mentioned by
Belskaya et al. [2]. These compounds exhibit efficient non-
linear optical property in their crystalline states [3], com-
plex formation with metal ions and pharmacological
properties like antimicrobial, anticonvulsant, analgesic,
anti-inflammatory, antiplatelet, antitubercular, anticancer
and antitumor activities [4–11].
99.612(1)°, C crystallizes in monoclinic P21/c, a = 8.4213(8)
˚
˚
˚
A, b = 21.077(2) A, c = 9.5899(10) A, b = 99.979(2)°, D
˚
crystallizes in monoclinic P21/c, a = 11.1644(10) A, b =
˚
˚
16.3508(15) A, c = 9.7313(9) A, b = 105.757(1)° and E
ꢀ
˚
crystallizes in triclinic P1, a = 8.7415(7) A, b =
˚
˚
10.1032(8) A, c = 11.6852(9) A, a = 68.306(1)°, b =
84.894(1)°, c = 68.289(1)°. All of the five compounds with
close molecular conformations adopt a trans configuration with
T. S. Chia ꢀ C. K. Quah ꢀ W.-S. Loh ꢀ H.-K. Fun (&)
X- ray Crystallography Unit, School of Physics, Universiti Sains
Malaysia, 11800 Minden, Penang, Malaysia
1,2,3-Triazoles have occupied an important role both in
organic and pharmaceutical chemistry [12]. These 1,2,3-
traizoles are obtained by the 1,3-dipolar cycloaddition
reaction of organoazide with appropriate dipolarophile.
1,2,3-Triazoles with high aromatic stabilization remain
stable under basic and acid hydrolysis and reductive and
oxidative conditions [13, 14]. Moreover, this heterocycle
has a high dipole moment and made it favorable in the
e-mail: hkfun@usm.my; hfun.c@ksu.edu.sa
N. Chandra ꢀ B. Kalluraya
Department of Studies in Chemistry, Mangalore University,
Mangalagangothri, Karnataka 574199, India
H.-K. Fun
Department of Pharmaceutical Chemistry, College of Pharmacy,
King Saud University, Riyadh 11451, Saudi Arabia
123

J Chem Crystallogr (2014) 44:220–228
221
Preparation of (E)-N0-(4-Chlorobenzylidene)-5-methyl-1-
binding of biomolecular targets through hydrogen bonding
[15].
(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide (B)
Prompted by these observations, a new series of
hydrazone derivatives were synthesized and subjected to
single crystal X-ray structure determination studies.
Reflux time: 1–2 h. Solvent used for slow evaporation:
ethanol. Yield: 87 %. Elemental analyses test for C17H13-
ClN6O3: Anal. Calcd.: C, 53.07; H, 3.41; N, 21.84 %.
Found: C, 53.12; H, 3.42; N, 21.82 %. IR (KBr, cm-1):
3321.42 (N–H), 1693.50 (C=O), 1573.91 (C=N stretch),
1548.5 (Asym. N=O), 1329.7 (Sym. N=O).
Experimental
General Procedure for Synthesis
Preparation of (E)-N0-(4-Bromobenzylidene)-5-methyl-1-
(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide (C)
A series of five hydrazone derivatives possessing 5-methyl-
1-(4-nitrophenyl)-1,2,3-triazole moiety were prepared by
the reaction of 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-tria-
zole-4-carbohydrazide with suitably substituted aryl alde-
hydes. To a solution of 5-methyl-1-(4-nitrophenyl)-1H-
1,2,3-triazole-4-carbohydrazide (0.01 mol) in a 1:1 mixture
of DMF and ethanol (10 mL), 0.01 mol of 4-flurobenzal-
dehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde,
4-hydroxy-3-methoxybenzaldehyde or 4-bromoacetophe-
none was added. Concentrated sulphuric acid (0.5 mL) was
added to this reaction mixture and the contents were
refluxed. The solid product separated was collected by
filtration, dried and recrystallized from ethanol. Single
crystals suitable for X-ray analysis were obtained by slow
evaporation method (Scheme 1).
Reflux time: 1–2 h. Solvent used for slow evaporation:
ethanol-N,N-dimethylformamide (DMF) (3:1) solution.
Yield: 87 %. Elemental analyses test for C17H13BrN6O3:
Anal. Calcd.: C, 47.57; H, 3.05; N, 19.58 %. Found: C,
47.59; H, 3.10; N, 19.46 %. IR (KBr, cm-1): 3321.42
(N–H), 1685.79 (C=O), 1588 (C=N stretch), 1544.98
(Asym. N=O), 1371.39 (Sym. N=O).
Preparation of (E)-N0-(4-Hydroxy-3-methoxybenzylidene)-
5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carbohydrazide (D)
Reflux time: 1–2 h. Solvent used for slow evaporation:
ethanol. Yield: 87 %. Elemental analyses test for
C18H16N6O5: Anal. Calcd: C, 54.54; H, 4.07; N, 21.20 %.
Found: C, 54.56; H, 4.02; N, 21.20 %. IR (KBr, cm-1):
3356.14 (N–H), 1670.35 (C=O), 1593.20 (C=N stretch),
1544.12 (Asym. N=O), 1384.89 (Sym. N=O).
Preparation of (E)-N0-(4-Fluorobenzylidene)-5-methyl-1-
(4-nitrophenyl)-1H-1,2,3-triazole-4-carbohydrazide (A)
Reflux time: 1–2 h. Solvent used for slow evaporation:
ethanol-N,N-dimethylformamide (DMF) (3:1) solution.
Yield: 90 %. Elemental analyses test for C17H13FN6O3:
Anal. Calcd.: C, 55.44; H, 3.56; N, 22.82 %. Found: C,
55.48; H, 3.80; N, 22.60 %. IR (KBr, cm-1): 3352.28
(N–H), 1683.86 (C=O), 1584 (C=N stretch), 1554.63
(Asym. N=O), 1324.7 (Sym. N=O).
Preparation of (E)-N0-(1-(4-Bromophenyl)ethylidene)-5-
methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carbohydrazide (E)
Refluxed time: 3–4 h. Solvent used for slow evaporation:
ethanol-N,N-dimethylformamide (DMF) (3:1) solution.
Yield: 87 %. Elemental analyses test for C18H15BrN6O3:
Anal. Calcd.: C, 48.77; H, 3.41; N, 18.96 %. Found: C,
48.72; H, 3.46; N, 18.98 %. IR (KBr, cm-1): 3309.6
(N–H), 1682.9 (C=O), 1577.5 (C=N stretch), 1560.4
(Asym. N=O), 1343.6 (Sym. N=O).
Y
N
N
N
H
-O
N
Z
N+
NH2
O
+
O
O
X
N
N
-O
Y
H
N
(
)
mixture
:
DMF/ethanol 1 1
N
N+
Z
X
N
X-ray Data Collection
concentrated sulphuric acid
O
O
(
A
-
E
)
Single crystals suitable for X-ray analysis were performed
on Bruker SMART APEXII CCD and Bruker APEX Duo
CCD area-detector diffractometers using Mo Ka radiation
X = F
X = Cl
X = Br
; Y = H
; Y = H
; Y = H
; Z = H
; Z = H
; Z = H
A
B
C
D
E
X = OH ; Y = H
X = Br ; Y = CH3 ; Z = H
; Z = OCH3
˚
(k = 0.71073 A). Data collection was performed by using
the APEX2 software [16], whereas the cell refinement and
data reduction were performed under the SAINT software
[16]. All five complete crystallographic data were collected
Scheme 1 The chemical syntheses of five compounds (A–E)
described in this paper
123

222
J Chem Crystallogr (2014) 44:220–228
Table 1 Crystal data, data collection and structure refinement details
Compound
A
B
C
D
E
Crystal data
CCDC no.
894705
894704
894703
894706
C18H16N6O5
396.37
894707
Chemical formula
Formula weight
Temperature (K)
C
17H13FN6O3
C17H13ClN6O3
384.78
C17H13BrN6O3
429.24
C18H15BrN6O3
443.27
368.33
100
100
100
100
100
˚
Wavelength (A)
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
Triclinic
Crystal system
Space group
ꢀ
P1
Unit cell dimensions
˚
a (A)
6.8057(1)
12.7447(3)
18.6936(3)
90
8.3815(2)
20.8298(4)
9.5932(2)
90
8.4213(8)
21.077(2)
9.5899(10)
90
11.1644(10)
16.3508(15)
9.7313(9)
90
8.7415(7)
10.1032(8)
11.6852(9)
68.306(1)
84.894(1)
68.289(1)
889.52(12)
2, 1.655
2.35
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
Volume (A )
Z, Dx (Mg/m3)
105.356(1)
90
99.612(1)
90
99.979(2)
90
105.757(1)
90
3
˚
1563.53(5)
4, 1.565
0.12
1651.32(6)
4, 1.548
0.27
1676.4(3)
4, 1.701
2.49
1709.7(3)
4, 1.540
0.12
l (mm-1
)
F(000)
Crystal size, mm3
Color, shape
760
792
864
824
448
0.28 9 0.11 9 0.08 0.49 9 0.14 9 0.08 0.37 9 0.21 9 0.05 0.42 9 0.23 9 0.08 0.39 9 0.11 9 0.06
Yellow, block
Colorless, plate
Colorless, plate
Yellow, plate
Yellow, plate
Data collection
hmax, hmin (°)
27.5, 2.0
27.5, 2.0
27.5, 2.4
27.5, 1.9
27.5, 1.9
Method
u and x scans
-8 B h B 8
-14 B k B 16
-24 B l B 24
15,319
u and x scans
-10 B h B 10
-26 B k B 27
-12 B l B 12
27,361
u and x scans
-10 B h B 10
-27 B k B 22
-12 B l B 12
15,733
u and x scans
-14 B h B 14
-21 B k B 20
-12 B l B 12
16,130
u and x scans
-11 B h B 10
-13 B k B 12
-15 B l B 15
15,542
hkl range
Measured reflections
Independent reflections
3,590
3,790
3,819
3,914
4,055
Reflections with I [ 2r(I) 2,578
3,152
3,361
3,327
3,721
Rint
0.048
0.048
0.029
0.026
0.028
Completeness (%)
99.9
100
99.5
99.4
99.1
Tmin, Tmax
0.968, 0.991
0.881, 0.979
0.460, 0.886
0.953, 0.991
0.465, 0.864
Refinement
Parameters/restraints
R[F2 [ 2r(F2)]
wR(F2)
296/0
296/0
296/0
326/0
313/0
0.052
0.039
0.027
0.034
0.024
0.122
0.093
0.066
0.090
0.060
Goodness of fit
w: A, B
1.04
1.03
1.05
1.04
1.07
0.0578, 0.3767
0.26, -0.39
0.0375, 0.834
0.24, -0.27
0.0293, 1.2374
0.38, -0.42
0.0393, 0.7467
0.32, -0.25
0.0286, 0.3466
0.40, -0.34
-3
)
˚
Dqmax, Dqmin (e A
Weighting scheme, w = 1/[r2(Fo2) ? (AP)2 ? BP] where P = (Fo2 ? 2F2c)/3
at 100 (1) K using the Oxford Cryosystem Cobra low
temperature attachment [17] and these crystallographic
data are showed in Table 1. The crystal structures were
solved by direct method and refined against F2 by full-
matrix least-squares refinement using SHELXTL package
[18]. The non-hydrogen atoms were refined anisotropically,
whereby the hydrogen atoms were located in differ-
˚
ence Fourier maps [O–H = 0.84(2) A, N–H = 0.83(2)–
123

J Chem Crystallogr (2014) 44:220–228
223
Fig. 1 The molecular structures of compounds A to E, (a–e) with atom numbering schemes and 50 % probability displacement ellipsoids. The
dashed lines represent the intramolecular hydrogen bond interactions (Color figure online)
˚
˚
0.883(16) A and C–H = 0.92(3)–1.006(17) A]. The final
refinement converged well. Absorption correction was
applied to the final crystal data by using the SADABS
software [16]. PLATON [19] was used to prepare material
for publication. The overlay diagrams were drawn using
Olex2 software [20].
Results and Discussion
General Molecular Structure Descriptions
In all of the five compounds (A–E; Fig. 1), each molecule
consists of a 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole
123

224
J Chem Crystallogr (2014) 44:220–228
Table 2 Dihedral angle
between two moeities
Moeities
Dihedral angle, °
Molecule A
Molecule B
Molecule C
Molecule D
Molecule E
I, II
34.53(10)
13.72(10)
25.03(9)
18.50(12)
6.77(6)
25.16(9)
11.11(8)
15.90(8)
15.4(3)
24.63(9)
10.67(9)
15.93(8)
14.3(3)
22.55(6)
13.16(6)
33.41(6)
18.77(1)
6.54(11)
6.67(9)
33.49(9)
7.57(9)
I, III
II, III
IV, II
I, V
27.52(8)
11.8(3)
Moeties I–V are N1-N3/C7/C8,
C1-C6, C11-C16 rings, N1/O1/
O2 nitro-group and O3/N5/N6/
C9/C10 bridge, respectively
9.59(11)
4.01(11)
9.29(13)
3.66(13)
6.43(10)
7.59(10)
III, V
6.96(4)
Crystal Structure of (E)-N0-(4-Chlorobenzylidene)-5-
methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carbohydrazide (B)
In the crystal, simple replacement of fluorine atom by chlorine
atom in the molecule changes the crystal packing from two-
dimensional networks in compound A to a three dimensional
network with an additional C–HꢀꢀꢀCl interaction (Table 3).
Fig. 4a shows that atom O3Baccepts two hydrogen from atoms
C13B and C17B to link the molecules into two molecular-thick
chains with R22(12) and R22(18) ring motifs [22], running along
the c axis. The [001] two molecular-thick chains are cross-
linked by intermolecular C16B–H16BꢀꢀꢀCl1B hydrogen bonds
into two-dimensional planes (Fig. 4b) parallel to (100) and
the adjacent planes are further connected into a three-dimen-
sional network (Fig. 4c) via weak intermolecular C15B–
H15BꢀꢀꢀO1B interactions. The crystal packing is further stabi-
lized by p-p interactions, involving the centroids of triazole
ring and chloro-substituted benzene ring [centroid to centroid
Fig. 2 The overlay diagram of compounds A to E shows close
similarity in their molecular geometries. Only non-H atoms common
to all five compounds are shown (Color figure online)
group connected to a substituted benzene ring through
C9(=O3)–N5–N6=C10 connecting bridge. The 1,2,3-tria-
zole ring is essentially planar with r.m.s. deviations from
˚
0.003 to 0.005 A. The least squares planes formed by
C(=O)–NH–N=C bridge in compounds A to E are nearly
planar as indicated by the r.m.s. deviations of 0.026, 0.04,
˚
0.038, 0.04 and 0.088 A. The hydrazone N6=C10 double
bond with lengths of 1.285(2), 1.279(2), 1.279(3), 1.284(2)
˚
and 1.291(2) A, respectively in A to E are in agreement
˚
with the typical Csp2=N double bond length of 1.279(8) A
˚
distance = 3.5972(9) A; symmetry code = x, y, 1 ? z].
[21]. The dihedral angles between the least squares planes
formed by two moieties are summarized in Table 2. Fig. 2
shows the overlay diagram of all five compounds with
similarities in their molecular conformations. A weak
intramolecular C17–H17BꢀꢀꢀO3 hydrogen bond (Table 3)
was observed in all compounds and it features an S(6) ring
motif [22] as shown in Fig. 1.
Crystal Structure of (E)-N0-(4-Bromobenzylidene)-5-
methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carbohydrazide (C)
The space group and unit cell parameters of the crystal
structure of C are similar to those found in compound
B (Table 1) after the simple substitution of chlorine atom
with bromine atom, which is also known as isomorphous
substitution. In the crystal, three intermolecular C–HꢀꢀꢀO
hydrogen bonds and one C–HꢀꢀꢀBr hydrogen bonds
(Table 3) were observed, involving the atoms C13, C15,
C16, C17, O1 and O3 which are equivalent to those atoms
involved in the hydrogen bonding in compound B. This
interesting observation is due to the uniqueness of space
group (both are in space group P21/c) and also the simi-
larity in the unit cell parameters and molecular geometries
between compounds B and C as shown in Fig. 5. The
torsion angles formed between two moieties (nitro group,
Crystal Structure of (E)-N0-(4-Fluorobenzylidene)-5-
methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-4-
carbohydrazide (A)
In the crystal, molecules are linked by intermolecular C13A–
H13AꢀꢀꢀO1A(nitro) hydrogen bond into head-to-tail chains
running along the c axis. The [001] chains are then connected
by C10A–H10AꢀꢀꢀO3A and C16A–H16AꢀꢀꢀO3A hydrogen
bonds, with atom O3A as the same acceptor, into sheets
parallel to (010) plane with R12(6) ring motifs [22] as shown in
Fig. 3.
123

J Chem Crystallogr (2014) 44:220–228
225
Table 3 Hydrogen bond
geometries in compounds A–E
˚
D–H/A
˚
˚
D–HꢀꢀꢀA
HꢀꢀꢀA/A
DꢀꢀꢀA/A
\D–HꢀꢀꢀA/°
Symmetry code
A
C10A–H10AꢀꢀꢀO3A
C13A–H13AꢀꢀꢀO1A
C16A–H16AꢀꢀꢀO3A
C17A–H17BꢀꢀꢀO3A
B
0.98(2)
0.98(3)
0.93(2)
0.96(2)
2.42(2)
2.34(2)
2.48(2)
2.54(2)
3.305(3)
3.231(2)
3.298(2)
3.042(2)
149.7(17)
150(2)
x - 1, y, z
x, y, z ? 1
x - 1, y, z
147(2)
112.9(16)
C13B–H13BꢀꢀꢀO3B
C15B–H15BꢀꢀꢀO1B
C16B–H16BꢀꢀꢀCl1B
C17B–H17BꢀꢀꢀO3B
C17B–H17CꢀꢀꢀO3B
C
0.944(18)
0.931(17)
0.96(2)
2.288(18)
2.483(17)
2.78(2)
3.115(2)
3.359(2)
3.6695(17)
3.105(2)
3.350(2)
146.0(14)
156.8(14)
155.0(14)
119.6(13)
143.1(15)
-x ? 1, -y?1, -z
x ? 1, -y?1/2, z - 3/2
x, -y?1/2, z ? 1/2
0.964(19)
0.97(2)
2.513(18)
2.523(17)
-x ? 1, -y?1, -z?1
C13C–H13CꢀꢀꢀO3C
C15C–H15CꢀꢀꢀO1C
C16C–H16CꢀꢀꢀBr1C
C17C–H17BꢀꢀꢀO3C
C17C–H17CꢀꢀꢀO3C
D
0.95(2)
0.94(2)
0.95(2)
0.96(3)
0.99(3)
2.29(2)
2.52(2)
2.86(2)
2.49(3)
2.49(3)
3.132(2)
3.392(3)
3.710(2)
3.098(3)
3.324(3)
148(2)
-x ? 1, -y?1, -z?1
x - 1, -y?1/2, z ? 3/2
x, -y?1/2, z - 1/2
155.9(19)
149.8(17)
121.5(19)
142(2)
-x ? 1, -y?1, -z
O4D–H1ODꢀꢀꢀO3D
C2D–H2DꢀꢀꢀN3D
C17D–H17BꢀꢀꢀO3D
E
0.84(2)
1.93(2)
2.7658(14)
3.1804(16)
3.1087(17)
177.5(19)
128.6(12)
125.7(12)
-x ? 2, -y, -z?1
x, -y?1/2, z - 1/2
0.969(15)
0.990(16)
2.485(16)
2.425(16)
C2E–H2EꢀꢀꢀO3E
C5E–H5EꢀꢀꢀO3E
C17E–H17BꢀꢀꢀO3E
0.94(2)
0.94(2)
0.98(2)
2.45(2)
3.148(2)
3.320(2)
3.120(2)
131.3(15)
141.6(16)
118.4(19)
x, y ? 1, z
2.530(19)
2.53(3)
-x ? 2, -y?1, -z?1
Fig. 3 The crystal packing in
compound A viewed along the
a a and b b axes. The dashed
lines represent the hydrogen
bonds. For clarity sake,
hydrogen atoms not involved in
hydrogen bonding have been
omitted (Color figure online)
benzene rings, triazole ring or connecting bridge) in B and
C are highly similar as tabulated in Table 2. Because of the
above factors, the molecules in compound C are connected
by intermolecular hydrogen bonds into a three-dimensional
network which is similar to the crystal packing in com-
pound B. p-p stacking interactions are also observed with a
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J Chem Crystallogr (2014) 44:220–228
Fig. 4 Development of
hydrogen bond interactions in
the crystal packing of
compound B from a two
molecular thick chain to b two-
dimensional plane and further
established into c three-
dimensional network. Dashed
lines show the intermolecular
hydrogen bonds. H atoms not
involved in hydrogen bonding
are omitted for clarity (Color
figure online)
˚
centroid–centroid distance of 3.5745(11) A, involving the
centroids of triazole ring and bromo-substituted benzene
rings [symmetry code = x, y, -1 ? z]. Since the crystal
packing is similar to that of compound B, (Fig. 4), the
packing diagrams are not shown.
Crystal Structure of (E)-N0-(4-Hydroxy-3-
methoxybenzylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-
triazole-4-carbohydrazide (D)
Fig. 5 The overlay diagram of compounds B (purple) to C (yellow)
shows high similarity in their molecular structures with good fitting.
Only non-H atoms common to both compounds are shown (Color
figure online)
In the crystal (Fig. 6), the hydroxyl group which is attached
to the benzene ring acts as a good electron donor and a
strong intermolecular O4D–H1ODꢀꢀꢀO3D hydrogen bond is
formed. This OH(hydroxyl)ꢀꢀꢀO=C hydrogen bond links the
molecules into inversion dimers [symmetry code = 2-x,
-y, 1-z], generating R22(22) graph-set motifs [22] and they
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J Chem Crystallogr (2014) 44:220–228
227
Fig. 6 Dashed lines show the
intermolecular hydrogen bond
interactions which linked the
molecules of compound D into
2-dimensional sheets parallel to
bc plane (Color figure online)
Fig. 7 The crystal packing in
compound E showing distorted
ladder-like chains, propagating
along the b-axis, with H atoms
not involved in intermolecular
interactions being omitted. The
simple dashed lines and dashed
lines with double arrows
represent the intermolecular
hydrogen bonds and p-p
stacking interactions,
respectively (Color figure
online)
are further inter-linked by C2D–H2DꢀꢀꢀN3D into sheets
parallel to bc plane.
Crystal Structure of (E)-N0-(1-(4-Bromophenyl)
ethylidene)-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-
4-carbohydrazide (E)
Fig. 8 Overlay diagram of compound E (light green) and reported
compound XEBGAO (red). Only non-H atoms common to both
compounds are shown (Color figure online)
In comparison to compound C (monoclinic P21/c), a sim-
ple substitution of H atom attached to atom C10 with
methyl group results in the crystallization of E in triclinic
R22(16) ring motifs [22]. The crystal packing is further
consolidated by the p-p stacking interactions between the
inversion-related C1E-C6E rings within each [010] dis-
torted ladder-like chain as represented by the dashed lines
with double arrows as shown in Fig. 7 [centroid to centroid
ꢀ
P1. In the crystal, non-classical intermolecular C–HꢀꢀꢀO
hydrogen bonds produce a crystal packing which is dif-
ferent from those observed in compound C. The intermo-
lecular C2E–H2EꢀꢀꢀO3E hydrogen bond links the
molecules into chains, propagating along the b axis. Each
pair of anti-parallel [010] chains is inter-connected by
C5E–H5EꢀꢀꢀO3E hydrogen bond into a [010] distorted
ladder-like chain (Fig. 7) which comprised of R24(14) and
˚
distance = 3.6988(11) A and symmetry code = -x ? 2,
-y ? 2, -z ? 1].
Unlike the isomorphous chlorine-bromine substitution in
compounds B and C which is resulting in similar molecular
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J Chem Crystallogr (2014) 44:220–228
846076) and Research University Cluster Grant (1001/PSKBP/
8630013). TSC thanks the Malaysian government and USM for the
award of Research Fellowship. The authors extend their appreciation
to The Deanship of Scientific Research at King Saud University for
the funding the work through the research group project No. RGP-
VPP-207.
conformation, unit cell parameters and crystal packing,
compound E and its chlorine derivative (ref. code XE-
ꢀ
˚
BGAO [23], space group P1, a = 8.6603 (1) A,
˚
˚
b = 10.2844 (1) A, c = 10.4033 (1) A, a = 83.816 (1)°,
b = 81.402 (1)°, c = 76.373 (1)°) do not exhibit the same
similarity as shown in former after the simple substitution
of bromine atom to chlorine atom. The differences in
between their molecular conformations are displayed in the
overlay diagram (Fig. 8).
References
1. Rollas S, Ku¨c¸u¨kgu¨zel SG (2007) Molecules 12:1910–1939
2. Belskaya NP, Dehaen W, Bakulev VA (2010) Arkivoc i:275–332
3. Serbutoviez C, Bosshard C, Knoepfle G, Wyss P, Pretre P,
Guenter P, Schenk K, Solari E, Chapuis G (1995) Chem Mater
7:1198–1206
Conclusion
4. Vittorio F, Ronsisvalle G, Marrazzo A, Blandini G (1995) Il
Farmaco 50:265–272
5. Yildir I, Perc¸iner H, Sahin MF, Abbasoglu U (1995) Arch Pharm
328:547–549
6. Dimmock JR, Vashishtha SC, Stables JP (2000) Eur J Med Chem
35:241–248
7. Loncle C, Brunel JM, Vidal N, Dherbomez M, Letourneux Y
(2004) Eur J Med Chem 39:1067–1071
8. Melnyk P, Leroux V, Sergheraert C, Grellier P (2006) Bioorg
Med Chem Lett 16:31–35
9. Nithinchandra, Kalluraya B, Aamir S, Shabaraya AR (2012) Eur
J Med Chem 54:597–604
10. Rollas S, Gulerman N, Erdeniz H (2002) Il Farmaco 57:171–174
11. Bedia KK, Elcin O, Seda U, Fatma K, Nathaly S, Sevim R,
Dimoglo A (2006) Eur J Med Chem 41:1253–1261
12. Duan YC, Ma YC, Zhang E, Shi XJ, Wang MM, Ye XW, Liu
HM (2013) Eur J Med Chem 62:11–19
13. Vatmurge NS, Hazra BG, Pore VS, Shirazi F, Chavan PS,
Deshpande MV (2008) Bioorg Med Chem Lett 18:2043–2047
14. Whiting M, Muldoon J, Lin YC, Silverman SM, Lindstron W,
Olson AJ, Kolb HC, Finn MG, Sharpless KB, Elder JH, Fokin
VV (2006) Angew Chem Int Ed 45:1435–1439
15. Bock VD, Speijer D, Hiemstra H, van Maarseveen JH (2007) Org
Biomol Chem 5:971–975
16. Bruker (2009) SADABS, APEX2 and SAINT. Bruker AXS Inc,
Madison
17. Cosier J, Glazer AM (1986) J Appl Cryst 19:105–107
18. Sheldrick GM (2008) Acta Cryst A64:112–122
19. Spek AL (2009) Acta Cryst D65:148–155
Five new hydrazone derivatives are synthesized with (E)-
N0-benzylidene-5-methyl-1-(4-nitrophenyl)-1H-1,2,3-tria-
zole-4-carbohydrazide moiety as the main body and dif-
ferent functional groups (F, Cl, Br, OH, OCH3) are
substituted at the terminal benzene ring.
A weak
intramolecular C–HꢀꢀꢀO hydrogen bond is observed in each
compounds, featuring an S(6) ring motif. Strong intermo-
lecular O–HꢀꢀꢀO = C hydrogen bond is formed in the
crystal structure of D, whereas for the rest of the com-
pounds, only weak intermolecular C–HꢀꢀꢀCl, C–HꢀꢀꢀBr and
C–HꢀꢀꢀO hydrogen bonds are observed. Isomorphous
chlorine-bromine substitution has taken place in com-
pounds B and C in which they are both crystallize in space
group P21/c with similar unit cell parameters.
Supplementary Materials
The crystallographic data for compounds A-E have been
deposited with the Cambridge Crystallographic Data Cen-
ter No. CCDC 894703–894707. These data can be obtained
free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting
The Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; fax: ?44-1223-336033.
20. Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Pusch-
mann H (2009) J Appl Cryst 42:339–341
21. Allen FH, Kennard O, Watson DG, Brammer L, Orpen AG,
Taylor R (1987) J Chem Soc Perkin Trans 2:S1–S19
22. Bernstein J, Davis RE, Shimoni L, Chang NL (1995) Angew
Chem Int Ed Engl 34:1555–1573
Acknowledgments The authors thank Universiti Sains Malaysia
(USM) for the APEX DE 2012 grant (1002/PFIZIK/910323),
RU-PRGS grant (X-Ray Protein Structure Determination for Glycerol
Kinase, GlpK of Samonella Typhi and other Proteins, 1001/PFIZIK/
23. Fun HK, Quah CK, Nitinchandra, Kalluraya B, Shetty S (2012)
Acta Cryst E68:o2164
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