Crystal structure of N-(2-pyridylmethylene)benzene-1,4-diamine

Article abstract of DOI:10.1007/s10870-011-0120-9

The crystal structure of amino containing Schiff base, N-(2- pyridylmethylene)benzene-1,4-diamine, was determined via X-ray diffraction analysis. The title compound crystallizes in orthorhombic system, space group Pc2 ₁ n, with unit cell dimens

Full text of DOI:10.1007/s10870-011-0120-9

J Chem Crystallogr (2011) 41:1451–1455
DOI 10.1007/s10870-011-0120-9
ORIGINAL PAPER
Crystal Structure of N-(2-Pyridylmethylene)benzene-1,4-diamine
•
Katayoun Marjani Mohsen Mousavi
•
Fatemeh Namazian
Received: 21 November 2008 / Accepted: 30 April 2011 / Published online: 13 May 2011
Ó Springer Science+Business Media, LLC 2011
Abstract The crystal structure of amino containing Schiff
base, N-(2-pyridylmethylene)benzene-1,4-diamine, was
determined via X-ray diffraction analysis. The title com-
pound crystallizes in orthorhombic system, space group
para substituents may not participate in binding to metal
centers, they affect the coordination behavior of ligands and
the stability of their complexes via their electronic effects or
by formation of hydrogen bonds.
Though some ReI, RuII, ZnII, CdII and HgII complexes of
pmbd have been reported earlier [1–3], they have not been
prepared by direct reactions of pmbd with metal ions.
Instead, they have been resulted from partial hydrolysis of
Pc21n, with unit cell dimensions a = 5.8945(6), b =
3
˚
˚
11.9233 (10), c = 14.5356 (16) A, V = 1021.59 (18) A ,
Z = 4. The molecules are linked by intermolecular
N–HꢀꢀꢀN hydrogen bonds to form supramolecular sheets
along with the bc crystallographic plane. The crystal struc-
ture is further stabilized by C–Hꢀꢀꢀp stacking interactions.
0
N,N -bis(2-pyridylmethylene)benzene-1,4-diamine to pmbd,
in the presence of metal ions (Scheme1). Here we report
the direct synthesis, spectral properties and X-ray dif-
fraction analysis of pmbd.
Keywords Crystal structure ꢀ Hydrogen bonding ꢀ
Supramolecular sheets ꢀ N-(2-pyridylmethylene)benzene-1 ꢀ
4-diamine
Experimental
Introduction
Chemicals were obtained from commercial sources.
1,4-diaminobenzene was used after recrystalization from
toluene. Other chemicals and solvents were used without
further purification. Melting point was measured on an
Electrothermal 9100 apparatus. IR spectrum was recorded
with a Perkin-Elmer 843 spectrometer. NMR spectra were
obtained from Bruker-Avance 300 MHz instrument using
TMS as internal standard. Elemental analysis (CHN) was
obtained from a Perkin-Elmer 2400 series II Analyzer.
N-(2-pyridylmethylene)benzene-1,4-diamine, pmbd (Scheme 1),
is a pyridine derived Schiff base, which acts as bidentate
chelating ligand towards metal centers [1–3]. In this usual
binding mod, free amino group forms two hydrogen bonds to
neighboring molecules to form supramolecular structures
[3]. Several complexes of structurally related Schiff bases
are reported, which have other para substituents such as OH
[4–6], OMe [7–9], Me [10–12], Ph [13–15], Cl [16–18],
COOH [19] and NO2 [20, 21], instead of NH2. Though these
Preparation of pmbd
To a solution of 1,4-diaminobenzene (1.08 g, 10 mmol) in
ethanol (10 ml) was added 2-pyridinecarbaldehyde (1.07 g,
10 mmol) and stirred at room temperature for 90 min. A
yellow precipitate was gradually formed. The mixture was
then filtered, washed with small portion of ethanol, dried in
vacuo, gave yellow precipitate of pmbd (1.5 g, 76%). By
slow cooling of a hot solution of pmbd in benzene, crystals
K. Marjani ꢀ F. Namazian
Faculty of Chemistry, Tarbiat Moalem University,
49 Mofateh Avenue, 15614 Tehran, Iran
M. Mousavi (&)
Department of Chemistry, Saveh Branch, Islamic Azad
University, P.O.Box 39187/366, Saveh, Iran
e-mail: drmousavi@hotmail.com
123

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J Chem Crystallogr (2011) 41:1451–1455
Scheme 1
N
N
NH2
CHO
NH2
Partial hydrolysis
pmbd
+
N
H2N
N
N
N
N
˚
Table 1 Crystal data and structure refinement for pmbd
Table 2 Selected bond lengths [A] and angles [°] for pmbd
Empirical formula
Formula weight
Wave length
C12 H11N3
197.24
C(5)–N(1)
1.344 (3)
1.340 (4)
1.472 (4)
115.0 (2)
123.8 (3)
C(6)–N(2)
1.263 (4)
1.423 (3)
1.378 (4)
119.8 (2)
28.5 (4)
C(1)–N(1)
C(7)–N(2)
˚
0.71073 A
C(5)–C(6)
C(10)–N(3)
Crystal size
0.20 9 0.2 9 0.15 mm
298 (2) K
N(1)–C(5)–C(6)
N(2)–C(6)–C(5)
C(6)–N(2)–C(7)
C(12)–C(7)–N(2)–C(6)
Temperature
Crystal system
Space group
Orthorhombic
Pc21n
˚
a = 5.8945 (6) A
Unit cell dimensions
Volume
1
˚
b = 11.9233 (10) A
(C=N), 1168 (N–H). H NMR (DMSO-d6, ppm): d 5.4 (s,
2H, NH2), 6.61 (d, 2H, ph), 7.22 (d, 2H, ph), 7.42 (t, 1H,
py), 7.87 (t,1H, py), 8.07 (d, 1H, py), 8.58 (s, 1H, CH=N),
8.64 (d, 1H, py). 13C NMR (DMSO-d6, ppm): d 114, 121.3,
123.1, 124.6, 136.8, 138.2, 149, 149.5, 153.7, 155.
˚
c = 14.5356 (16) A
Z
3
˚
1021.59 (18) A
Density (calculated)
Absorption coefficient
F(000)
4
1.282 Mg m-3
0.08 mm-1
416
h range for data collection (°)
Index ranges
X-ray Crystallography
Reflections collected
Independent reflections
2.8–29.3
-8 B h B 8, -16 B k B 14,
-19 B l B 19
Crystals suitable for X-ray diffraction analysis were
obtained from a solution of pmbd in benzene. Diffraction
data were collected on a STOE IPDS II diffractometer with
graphite monochromated Mo-Ka radiation. An orange
prism crystal was mounted on a glass fiber and used for
data collection. Data were collected at a temperature of 298
(2) K. The structure was solved by direct methods, and
refined on F2 using all data by Full-matrix least-square
procedures using SHELXTL-97 programs [22]. All of
hydrogen atoms were located in a difference Fourier map
and then after refined isotropically. Crystal data and
refinement details are given in Table 1.
Reflections with I [ 2r(I)
Number of parameters
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices (all data)
11559
1436 (Rint = 0.082)
1295
148
1.193
-3
)
˚
Largest diff. peak and hole (eA
R1 = 0.052, wR2 = 0.104
R1 = 0.0601, wR2 = 0.107
0.14 and -0.16
Structural Analysis
Figure 1 shows an ORTEP view and atom numbering of
pmbd. The compound crystallizes in orthorhombic system
and belongs to Pc21n space group. The asymmetric unit of
the title compound contains a molecule of pmbd, which has
a trans configuration around C=N double bond and adopt
an anti conformation in conjugated iminopyridyl moiety.
The selected bond geometries are presented in Table 2.
Fig. 1 ORTEP view of pmbd with displacement ellipsoids drown at
50% probability
suitable for X-ray diffraction analysis were obtained. Mp
161–165 °C. Anal. Calc. for C12H11N3 (197.24 g.mol-1):
C 73.07, H 5.62, N 21.30. Found: C 72.32, H 5.51, N 20.93.
IR (KBr, cm-1): 3395, 3323 and 3210 (N–H), 1640, 1621
˚
The C=Npyridyl bond length is 0.081 A longer than
C=Nimine bond length. The C(7)–N(2) and C(5)–C(6) bonds
which are connecting p system moieties, mainly present
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J Chem Crystallogr (2011) 41:1451–1455
1453
Fig. 2 The rotation of
p-aminophenyl moiety from
the main plane of molecule; and
the C–Hꢀꢀꢀp stacking interaction
between two adjacent molecules
single bond character. These values are comparable with
related bond lengths in pmbd complexes [1–3].
The crystal packing in pmbd is dominated by N–HꢀꢀꢀN
hydrogen bonding interactions, with donor–acceptor dis-
˚
tances of 2.35 (4) and 2.50 (3) A (Table 3). Each molecule
In the structure of title compound, the conjugated imi-
nopyridyl moiety is planar, but the p-aminophenyl ring is
rotated 24.69° from the main plane (Fig. 2).
is connected to four of its neighbors via intermolecular
hydrogen bonds, to form a two-dimensional supramolecu-
lar structure along with the bc crystallographic plane
(Fig. 3). The structure of pmbd is further stabilized by
C–Hꢀꢀꢀp stacking interactions (Fig. 2 and Table 3). Propa-
gation of C–Hꢀꢀꢀp stacking interactions results in the for-
mation of zig-zag chains along c-axis (Fig. 4 and Table 4).
Table 3 Hydrogen bonds and C–Hꢀꢀꢀp stacking interactions at the
˚
solid state of pmbd [A and °]
D–HꢀꢀꢀA
d(D–H)
d(HꢀꢀꢀA) d(DꢀꢀꢀA)
\(DHA)
N(3)–H(3A)ꢀꢀꢀN(2)#1 0.86 (3) 2.35 (4)
N(3)–H(3B)ꢀꢀꢀN(1)#2 0.80 (4) 2.50 (3)
3.200 (3) 169 (3)
3.235 (4) 155 (4)
3.473 (3) 151
C(1)–H(1)ꢀꢀꢀCg(2)
0.93
2.63
Supplementary Data
Symmetry transformations: #1: -1/2 ? x, -1/2 ? y, -1/2-z; #2:
-1/2-x, y,1/2 ? z; #3: 1/2-x, y, -1/2 ? z
CCDC 709687 contains the supplementary crystallographic
data for pmbd. These data can be obtained, free of charge,
Cg(2) refers to the gravity centre of the ring C(7)–C(12)
Fig. 3 Two-dimensional
supramolecular structure
formed by intermolecular
N–HꢀꢀꢀN hydrogen bonds
123

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J Chem Crystallogr (2011) 41:1451–1455
Fig. 4 The packing diagram of
pmbd, the hydrogen atoms are
omitted for clarity
via www.ccdc.cam.ac.uk/data_request/cif (or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK. (Fax: 44-1223-336033 or
e-mail: data_request@ccdc.com.ac.uk)).
Table 4 Fractional atomic coordinates and isotropic or equivalent
2
isotropic displacement parameters (A )
˚
x
y
z
Uiso*/Ueq
C1
H1
C2
H2
C3
H3
C4
H4
C5
C6
H6
C7
C8
H8
C9
H9
0.5764 (5) -0.0114 (3)
-0.5839 (2)
-0.6164
0.0555 (7)
0.067*
Acknowledgments The financial support from Tarbiat Moalem
University is gratefully acknowledged.
0.6764
-0.0569
0.1021 (3)
0.1324
0.6117 (6)
0.7344
-0.5850 (2)
-0.6166
0.0592 (8)
0.071*
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0.4634 (6)
0.4820
0.1705 (3)
0.2480
-0.5386 (2)
-0.5394
0.0585 (8)
0.070*
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123

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