Synthesis and crystal structure of 1,3-bis(p-nitrophenoxy)propane

Article abstract of DOI:10.1007/s10870-008-9471-2

The title compound 1,3-bis(p-nitrophenoxy)propane was synthesized by nucleophilic substitution of p-nitrophenol and 1,3-dibromopropane. Single crystal X-ray diffraction analysis reveals that the molecule in the solid state packs in the monoclinic P2/n spa

Full text of DOI:10.1007/s10870-008-9471-2

J Chem Crystallogr (2009) 39:83–86
DOI 10.1007/s10870-008-9471-2
COMMUNICATION
Synthesis and Crystal Structure of 1,3-Bis
(
p-nitrophenoxy)propane
Muhammad Rafique Æ Sonia Zulfiqar Æ
Glenn P. A. Yap Æ Syed Ismat Shah Æ
Muhammad Ilyas Sarwar
Received: 3 March 2008 / Accepted: 12 September 2008 / Published online: 1 October 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The title compound 1,3-bis(p-nitrophen-
oxy)propane was synthesized by nucleophilic substitution of
p-nitrophenol and 1,3-dibromopropane. Single crystal X-ray
diffraction analysis reveals that the molecule in the solid
state packs in the monoclinic P2/n space group with crystal
oligomer liquid crystals [1]. Several aryl halide, alde-
hyde, ether, nitrile, and amino derivatives of the parent
diphenoxyproprane have also been reported [2–12]. In
particular, the reported amino derivative displays a
rudimentary dendrimeric form [2]. The nitrile derivative,
by coordination to bridging Cu(I) ions, forms a polymer
[3]. The phosphine oxide derivative forms a similar
polymer via bridging coordination to Cd(II) ions [4].
These suggest that diphenoxypropane derivatives have
potential as monomeric synthons for new polymeric
materials.
˚
cell parameters a = 17.465(5) A, b = 4.8433(13) A, c =
˚
3
˚
-
˚
1
7.610(5) A, b = 100.290(6)8, V = 1465.6(7) A , D
=
calc
3
.442 g/cm . Two half-molecules are located in the
1
asymmetric unit which are each completed by twofold
0
symmetry making Z = 4, Z = 1.
Keywords Nitrophenoxypropane ꢀ Crystal structure ꢀ
Aryl-nitro compounds are common precursors for
amines after reduction [13–17]. Diamino compounds when
condensed with diacid chlorides give the corresponding
polyamides [18–25]. In order to overcome insolubility of
aromatic polyamides in organic solvents, flexible groups
can be introduced by incorporating alkyl/ether linkages in
the monomer that persist into the final polymer. In addition
to enhanced solubility, the incorporation of alkyl/ether
linkages generally imparts other desirable physical prop-
erties such as improved processability and increased
toughness of the polymers without decreasing thermal
stability. Soluble polyamides have the added advantage of
being more amenable to physical and chemical character-
ization by common solution-based techniques such as
NMR [22, 23, 26–29] and laser light scattering [30–35].
Such soluble polymers can also be utilized for nanocom-
posite preparation using sol–gel and solution intercalation
techniques [24, 25, 36–39].
Monomer synthon
Introduction
There has been interest in diphenoxypropane and struc-
turally similar compounds as model compounds for
M. Rafique ꢀ S. Zulfiqar ꢀ M. I. Sarwar
Department of Chemistry, Quaid-i-Azam University,
4
5320 Islamabad, Pakistan
G. P. A. Yap (&)
Department of Chemistry and Biochemistry,
University of Delaware, Newark, DE 19716, USA
e-mail: gpyap@udel.edu
The title compound, 1,3-bis(p-nitrophenoxy)propane, 1,
has the prerequisite alkyl/aryl ether linkages and therefore
an attractive synthon, after reduction into the amino
derivative, for the preparation of polyamides and
polyimides.
S. I. Shah
Department of Physics and Astronomy, University of Delaware,
Newark, DE 19716, USA
S. I. Shah ꢀ M. I. Sarwar
Department of Materials Science and Engineering,
University of Delaware, Newark, DE 19716, USA
123

8
4
J Chem Crystallogr (2009) 39:83–86
Experimental
Table 1 Crystal data and structure refinement details
CCDC deposit number
Empirical formula
678947
Chemicals
15 14 2 6
C H N O
Formula weight (g/mol)
Temperature (K)
318.28
120(2)
p-Nitrophenol (C99%), anhydrous potassium carbonate
(
99.99%), N,N-dimethylformamide (99.8%), toluene
99.8%), 1,3-dibromopropane (99%), methanol (99.8%),
˚
Wavelength (A)
0.71073
(
Crystal system
Monoclinic
and ethanol (99.5%) were procured from Aldrich and used
as received.
Space group
P2/n
Unit cell dimensions:
˚
a (A)
17.465(5)
4.8433(13)
17.610(5)
Synthesis of 1,3-Bis(p-nitrophenoxy)propane
˚
b (A)
˚
c (A)
p-Nitrophenol 6.26 g (0.045 mol) and anhydrous potas-
sium carbonate 6.22 g (0.045 mol) were placed in the
b (°)
Volume (A )
100.290 (6)
3
˚
0
1465.6(7)
mixture of N,N -dimethylformamide (DMF) 45 mL and
0
Z, Z
4, 1
toluene 23 mL followed by refluxing at 200 °C using a
Dean-Stark trap to remove the water azeotropically. After
the removal of toluene, 1,3-dibromopropane 2.3 mL
3
Density calculated (g/cm )
Absorption coefficient (mm
F(000)
1.442
-
1
)
0.113
664
(
0.0225 mol) was added to the mixture and then refluxed
Crystal size (mm)
0.28 9 0.09 9 0.05
1.51–28.30
for 8 h. The resulting solution was allowed to cool to room
temperature and was then poured into 200 mL methanol/
water (1:1) to give golden yellow precipitate. After being
washed thrice with water, the product was collected by
filtration and was recrystallized from ethanol, yield 80%;
m.p. 122 °C (Scheme 1).
h range for data collection (°)
Limiting indices
-23 B h B 22, -6 B k B 6,
-
23 B l B 23
No. of reflections collected
No. of unique reflections
(Rint = 0.0875)
11,425
3,489
Completeness to h = 25.00°
Absorption correction
99.9%
Determination of Crystal Structure
Multiscan
0.9938 and 0.9693
3489/0/210
1.048
Max. and min. transmission
Data/restraints/parameters
Crystal data and structure refinement details are presented
in Table 1. Crystals suitable for X-ray diffraction studies
were obtained from a slow evaporation of a saturated
solution of the compound in ethanol. A data crystal was
selected and mounted on a plastic mesh using ParatoneÒ
oil flash-cooled to the data collection temperature. Data
were collected on a Br u¨ ker-AXS APEX CCD diffractom-
2
Goodness-of-fit on F
Final R indices [I [ 2r(I)] (R1, wR2) 0.0787, 0.2416
R indices (all data) (R1, wR2)
0.0925, 0.2567
0.007(3)
Extinction coefficient
3
Largest diff. peak and hole (e/A )
˚
0.437 and -0.341
eter with graphite-monochromated Mo-Ka radiation
˚
(
k = 0.71073 A). Unit cell parameters were obtained from
results of refinement. The data-sets were treated with
SADABS absorption corrections based on redundant mul-
tiscan data [40]. The structures were solved using direct
methods and refined with full-matrix, least-square proce-
6
0 data frames, 0.3° x, from three different sections of the
Ewald sphere. The systematic absences in the data and the
unit cell parameters were consistent with Pn and P2/n.
Solution in the centrosymmetric space group option yiel-
ded chemically reasonable and computationally stable
2
dures on F . All non-hydrogen atoms were refined with
anisotropic displacement parameters. All hydrogen atoms
were treated as idealized contributions. Structure factors
are contained in the SHELXTL 6.12 program library [40].
Results and Discussion
The title compound 3-bis(p-nitrophenoxy)propane, 1, was
synthesized in good yield by a facile aromatic nucleophilic
substitution reaction of p-nitrophenol and 1,3-dibromo-
propane in the presence of K CO . Since this compound is
2
Scheme 1 Reaction for the formation of 1,3-bis(p-nitrophenoxy)
propane
3
a precursor and is easily isolated as crystalline material
1
23

J Chem Crystallogr (2009) 39:83–86
85
with a sharp melting point, characterization by single X-ray
diffraction was the most straightforward technique to
confirm identity (Fig. 1). Compound 1 crystallizes as two
symmetry-unique half-molecules in the asymmetric unit
with each molecule being completed by twofold symmetry:
molecules exhibit intermolecular p–p aromatic interactions
that are absent in bent 1 [42, 43].
It is well known that aromatic polymers that contain aryl
ether or aryl sulfone linkages generally have lower glass
transition temperatures, greater chain flexibility and trac-
tability than their corresponding polymers without these
groups in the chain. Such polymers are amorphous exhib-
iting excellent mechanical properties. The lower glass
transition temperatures and the improved solubility are
attributed to the flexible linkages that provide a polymer
chain with a lower energy of internal rotation. The syn-
thesized monomer precursor has alkyl ether linkage that is
expected to lower the glass transition temperature with
increased flexibility and solubility for ease in further
mechanical processing of the resulting polymer.
-
x ? 3/2, y, -z ? 1/2 and –x ? 3/2, y, -z ? 3/2. Neither
a close inspection of the packing diagram nor the program
ADDSYMM [41] suggests any overlooked symmetry.
The molecules may be thought of packing in an inter-
locked herringbone array. Although it is conceivable that the
molecule may adopt a linear conformation or develop
bend(s) in the dialkoxy chain at the O atom or the 1 C (or 3 C)
atom, consistent with the parent diphenoxypropane solid-
state geometry, the molecules bend at the middle 2 C atom.
Consequently, a molecular twofold symmetry arises from
this bend and the relatively coplanar aryl group with ether O
and the 1 and 2 C atoms. The C–C–C angle at the bend are
1
11.6(3)°, 115.1(3)° which is larger than ideal tetrahedral
Conclusion
3
geometry of an sp hybridized C most likely because of steric
bulk of the aryloxy groups. The angles between the phenyl
planes are 91.6(2)° and 93.5(2)°. Slight differences between
the symmetry-unique molecules can be mostly accounted by
rotation around C–C single bonds or steric relief deforma-
tions perhaps in order to promote better packing.
The synthesis of title compound in good yield allows
access to a synthon with the requisite alkyl/aryl linkages in
the eventual preparation of soluble polyamides with pro-
jected desirable physical properties. The X-ray crystal
structure confirms the structural similarity with the parent,
unmodified diphenoxypropane but with nitro groups
accessible for further chemical modification.
The structures of the even C chain analogs 1,3-bis
(
p-nitrophenoxy)ethane, 2, and 1,3-bis(p-nitrophenoxy)
butane, 3, have been previously reported. In sharp contrast
with the bent 1, both 2 and 3 are relatively flat and linear.
The angles between the mean planes described by the aryl
rings are nil in 2 and 3. In 3 there is some buckling
observed at the butyl chain such that the two aryl rings are
located in different but parallel planes. While the mole-
cules exhibit twofold rotation in 1, the molecules in 2 and 3
are located at inversion centers. The relatively flat 2 and 3
Supplementary Material
CCDC 678947 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/data_request/cif, by
e-mailing data_request@ccdc.cam.ac.uk, or by contacting:
Fig. 1 Molecular diagram of
1
.3-bis(p-nitroxy)propane with
labeling scheme. Atoms are
depicted with 30% probability
ellipsoids. A second symmetry-
unique but chemically
equivalent molecule is omitted
for clarity. Atoms labeled with
A are generated by symmetry
operation (-x ? 3/2, y, -
z ? 1/2)
123

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J Chem Crystallogr (2009) 39:83–86
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