Multi odd-even effects on cell parameters, melting points, and optical properties of chiral crystal solids based on S-naproxen

Article abstract of DOI:10.1039/c5ce01345c

A set of chiral crystal solids with odd and even numbers of carbon atoms based on S-naproxen, ester S-naproxen-R₁ (R₁ = H, methyl, ethyl, n-propyl, n-butyl, and n-amyl), has been prepared, alternatively crystallizing in the space groups P2₁ and P2₁2₁2₁, respectively, which shows the multi odd-even effects on cell parameters, melting points, and optical properties.

Full text of DOI:10.1039/c5ce01345c

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Multi odd-even effects on cell parameters, melting points, and optical
properties of chiral crystal solids based on S-naproxen
Gui-Mei Tang,a Jin-Hua Wang,a Chao Zhao,a Yong-Tao Wang,*a Yue-Zhi Cui,a Fei-Yue Cheng,a Seik
Weng Ngb
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
to dominate the intermolecular packing interactions. Herein, we
50 report the syntheses, crystal structures, melting points, solid
circular dichroism (CD), NLO, and photoluminescence properties
of Sꢀnaproxene (1) and its ester derivatives 2ꢀ6 (Sꢀnaproxen-R1,
R1 = methyl, ethyl, nꢀpropanyl, nꢀbutanly, and nꢀamyl for 2ꢀ6,
respectively), which were prepared by different alcohol solution
55 reaction of naproxen under H2SO4 at refluxing temperature,
respectively (Scheme 1, ESI).†
A set of chiral crystal solids with odd and even number of
carbon atoms based on S-naproxen have been prepared, ester
S-naproxen-R1 (R1 = H, methyl, ethyl, n-propanyl, n-butanly,
10 and n-amyl), alternatively crystallizing in the space group P21
and P212121, respectively, which show multi odd-even effects
on cell parameters, melting points, and optical properties.
Chiral crystal solids (CCSs) have received considerable attention
in the field of material chemistry owing to a variety of
15 technologically important properties such as second harmonic
Interestingly, naproxen 1 and its derivatives 2ꢀ6 crystallize in
two sets of different chiral space group, P212121 and P21,
repectively, though only the difference number of carbon chain
60 exist in this set of naproxene derivatives (Table S1).† More
notably, the type of chiral space group alternatively change upon
the number of carbon atoms, which illustrates that there exists
oddꢀeven effects on space group for naproxen and its derivatives.
It is predicted that the present study will provide us useful
65 information for developing and designing some specific CCSs.
Single crystal Xꢀray crystallographic analysis of 1 reveals that
compound 1 crystallizes in P21 space group, and an asymmetric
unit of 1 contains one naproxen molecule (Fig. S1a). The
hydrogen bondings are formed between two oxygen atoms from
70 carboxylic group, which results in the formation of a 1D helix
chain along the crystallographic b axis (Fig. 1a). Additionally,
there exist the weak CꢀH···π packing interactions formed by
CH3Oꢀ group and naphthene rings. As a result, a supramolecular
layer is generated through the interchain CꢀH···π packing
75 interactions between carbon atoms of naphthene groups and
naphthene rings, which further results in a 3D supramolecular
framework by means of OꢀH···O hydrogen bonds (Table S2, Fig.
S1).
XꢀRay crystal structural determination of 2 reveals that it
80 crystallizes in P212121 space group and consists of one methyl Sꢀ
naproxen ester molecule in asymmetric unit (Fig. S2a). There are
two types of weak CꢀH···π packing interactions, which are found
between CH3Oꢀ groups and naphthene rings, and between C
atoms of naphthene rings, which result in the chiral 2D layer
85 along the crystallographic ab plane (Fig. 1b). There exist weak Cꢀ
H···O interactions formed by C atoms of ester groups and O
atoms of carboxylic ones. The 2D supramolecular layers are
further constructed to a 3D supramolecular architecture through
these weak interlayer interactions (Fig. S2, Table S3).
generation
(SHG)
nonlinear
optical
(NLO),
and
ferroelectricity.1,2,3 Among of them, NLOꢀactive and behaviors
have widely been applied in NLO devices, signal processing,
optical communication, and information storage.4 So far, crystal
20 engineering has extensively been provided insight into the
preparation of the desired functional materials. Though there
exist some progressive advances based on crystal engineering in
5,6
the fabrication of CCSs,2a,2e,
it remains the strenuous
challenges in the design and syntheses of chiral and packing
25 arrangement.
Oddꢀeven effect has been observed in many homologues such
as nꢀalkanes,7 diols,8 diamines,8 diamides,9 dicarboxylate esters,10
dithiols,11 diselenides,12 and dicarboxylic acids,13 which affects
some physical properties such as melting temperature, density,
30 solubility, wettability, tribological behavior, electrochemistry,
and electron transfer.14 Interestingly, most of them display
symmetrical features of these structures. To date, the
development and investigation of the compounds based on
asymmetrical structure with singleꢀside substitutes remains a
35 great challenge, especially, chiral features with oddꢀeven effects
motifs. On the other hand, there exist one or two kinds of oddꢀ
even alternation for physical properties in the reported homologs.
However, coꢀexistence of multiꢀproperties with oddꢀeven
alternation in homologs is still not documented so far. The multi
40 oddꢀeven alternation phenomena will help us understand the
structureꢀproperty relationships and finely tune physical
properties. Thus, the design and studies of these homologues with
multi oddꢀeven effect remain an unprecedented challenge.
During the investigation on CCSs with interesting NLO
45 properties,15 we have realized that chiral Sꢀnaproxen compounds
easily construct CCSs with SHG responses.16 Sꢀnaproxen and its
derivatives possess some specific features: chiral, single ester,
singleꢀside substitutes and naphthene rings, which are propitious
90
XꢀRay structural analysis of 3 reveals that it shows P21 space
group. An asymmetric unit contains one ethyl Sꢀnaproxen ester
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molecule (Fig. S3a). There exist weak CꢀH···π interactions
respectively, which may be affiliated to πꢀπ* transition band.
between carbon atoms of CH3Oꢀ groups and naphthene rings, 60 Interestingly, compounds 1, 3, 5 and 2, 4, 6 display the positive
resulting into forming a 1D chain (Fig. 1c). The weak π···π
packing interactions were observed. Through these packing
interactions, a 2D layer supramolecular layer was generated along
the crystallographic ab plane. Notably, there do not exist obvious
interlayer packing interactions (Fig. S3).
The singleꢀcrystal structure analysis reveals that compound 4
crystallizes in P212121 space group. An asymmetric unit is
10 composed of one nꢀpropanol Sꢀnaproxen ester molecule (Fig.
S4a). It is observed that there exist weak CꢀH···π interactions
and the negative CE, respectively, which illustrate the oddꢀeffect
alternation.
5
Given
naphthene
derivatives
displaying
interesting
photoluminescence properties,17 the solution photoluminescent
65 spectra of compounds 1–6 at room temperature have been
examined (Fig. S11). It is found that compound 1 exhibit an
emission upon excitation at 230 nm with maxima at 351.8 nm,
which might be assigned to the intraligand πꢀπ* transition.18
Esters 2ꢀ6 exhibit blue photoluminescence with emission peaks at
between carbon aotms of CH3Oꢀ group and naphthene rings of 70 approximately 349.4 nm, 350.6 nm, 351.4 nm, 351.0 nm, 351.0
CH3Oꢀterminaed group, constructing a 1D chain (Fig. 1d).
Notably, it is not found that the interchain interactions evidently
15 occur. The nearest distance is 5.19 Å among CH3Oꢀterminaed
naphthene rings (Fig. S4).
nm (λex = 230 nm), respectively, which may be attributed to the
emission of the intraligands.18
To further investigate the packing interactions effects on
photoluminescent properties, the solid state luminescence spectra
75 of compounds 1ꢀ6 at room temperature have been carried on. As
illustrated in Fig. S12, the luminescent spectra of naproxen 1
display two emission peaks located at 353.8 nm and 357.0 nm
(λex = 230 nm), respectively, being assigned to the intraligand πꢀ
π* transition.18 Esters 2ꢀ6 also show blue luminescence with
Xꢀray determine anaylsis indicates that compound
5
crystallizes in P21 space group. In an asymmetric unit, it is
consisted of one nꢀbutyl Sꢀnaproxen ester molecule (Fig. S5a).
20 There exist weak CꢀH···π interactions between carbon atoms of
CH3Oꢀ group and CH3Oꢀterminaed naphthene rings, resulting
into a 1D chain along the crystallographic b axis (Fig. 1e). It is 80 emission peaks at 357.8 nm, 356.6 nm, 359.2 nm, 356 nm, and
observed that there exist weak CꢀH···π interactions between
methyl carbon atoms of butyl group and carboxylic groupꢀ
25 terminated naphthene rings, which consequently form a 2D
supramolecular layer (Fig. S5). The weak CꢀH···O hydrogen
359.4 nm, respectively, upon the excitation at 230 nm, which can
be attributed to the intraligand πꢀπ* transition.18 Notably, it is
found that the maximal peaks of these compounds display oddꢀ
even effects on photoluminescent properties (Fig. 3a). Compared
bonds occur between chiral methyl carbon atoms and oxygen 85 to the photoluminescent spectra in solution, those of the solid
atoms from carboxylic group, resulting into a 3D architecture.
Singleꢀcrystal structure analysis reveal that compound 6
30 crystallizes in P212121 space group. It is made of one nꢀamyl Sꢀ
naproxen ester molecule in an asymmetric unit (Fig. S6a). It is
state compounds 1ꢀ6 are similar. The presence of redꢀshifted
phenomena occurs about 5.2 nm, 8.4 nm, 6.0 nm, 7.8 nm, 5.0 nm,
and 8.4 nm, which can be ascribed to intermolecular πꢀπ packing
interactions at solid state. More importantly, it is observed that
observed that the weak CꢀH···π interactions formed by C atoms 90 the redꢀshifted values also display the alternation trend in
of CH3Oꢀ groups and naphthene rings, forming a 1D chain (Fig.
1f). These 1D chains are further extended to a 2D supermolecular
35 layer along the crystallogrpahic ab plane through the weak Cꢀ
H···π packing interactions constructed by C atoms of naphthene
photoluminescent properties (Fig. 3b). The present results show
that the alternation of photoluminescent spectra is in good
agreement with that of packing interactions (Fig. 3 and Fig. S7).
To our best knowledge, it is first example that it is observed oddꢀ
rings and naphthene groups. Interestingly, the absence of strong 95 even effects on not only luminescence but also their accordant
packing interactions between the adjacent layers does occurs (Fig.
S6).
relationships. The present results provide us an excelent model to
explain the nature of oddꢀeven effect.
40
As mentioned above, the existence of oddꢀeven effects on cell
parameters such as axis lengths, beta angles, cell volumes and
Given that compounds 1ꢀ6 crystallize in chiral space group
associated with NLO property, we examine their NLO behaviors.
space group obviously occurs with the length of carbon chain in 100 Preliminary experimental results of compounds 1-6 indicate that
ester groups (Fig. 2aꢀd). For so, we carefully compare the
packing interactions among the crystal structures of these
45 compounds. As illustrated in Fig. S7 and Table S4, the packing
interactions exhibit the oddꢀeven alternation, which may account
for these phenomena and the following physical properties.
To further investigate physical properties of these compounds,
their melting points, UvꢀVis, and solid CD spectra were
50 examined. As illustrated in Fig. S8, it is observed that there exists
the melting point alternation of naproxen and its derivatives,
they are SHGꢀactive. The SHG efficiency of compounds 1-6 are
weaker than that of urea,19 which may be as a consequence of the
absence of classical donorꢀacceptor system in the molecules.
In summary, we have successfully prepared a series of chiral
105 crystal solids based on Sꢀnaproxen and its five derivatives, which
display multi oddꢀeven effects on cell parameters, space group,
melting point, and optical properties, and exhibit moderate
nonlinear optical activities. To our knowledge, it is first example
that multi oddꢀeven effects on cell parameters and optic
which may be attributed to the crystalꢀpacking arrangements and 110 properties occurs, which pave a way for exploring and tuning the
intermolecular hydrogen interactions (Table S5). As shown in Fig.
S9, the maximal adsorption peaks occur at 231.8, 232.1, 232.2,
55 232.0, 232.1, and 232.0 nm for 1ꢀ6, respectively, which can be
attributed to πꢀπ* transition among organic molecules.
organic materials with charming physical properties. Current
studies on developing other chiral organic solids with interesting
optoelectronic properties is under way in our laboratory.
This work was financially supported by the Project of
Interestingly, the CD spectra display the Cotton effect (CE) (Fig. 115 Shandong Province Higher Educational Science and Technology
S10) from 239, 239, 238, 239, 239, 237, and 240 nm for 1ꢀ6,
Program (J09LB03), Shandong Distinguished Middleꢀaged
2
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Scheme 1. A set of naproxen and its esters.
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(c)
(e)
(d)
(f)
Fig. 1 (a)ꢀ(f) Perspective views of the chiral 1D chain in 1ꢀ6,
respectively.
(a)
(b)
40
32
24
16
8
1750
1500
1250
1000
750
a
b
c
500
0
1
2
3
4
5
0
1
2
3
4
5
Number of carbon atoms
Number of carbon atoms
5
(c) 104
(d)
P212121
100
96
β
β
β
β
P21
92
88
0
1
2
3
4
5
0
1
2
3
4
5
Number of carbon atoms
Number of carbon atoms
Fig. 2 The cell parameters alternation upon number of carbon atoms in
ester groups. (a) axis lengths, (b) cell volumes, (c) β angles, and (d) space
group. Note: Number of carbon atoms stands for substituent groups in
10 naproxen and its derivatives.
360
(a)
(b)
8.0
7.2
6.4
5.6
4.8
359
358
357
356
355
0
1
2
3
4
5
0
1
2
3
4
5
Number of carbon atoms
Number of carbon atoms
Fig. 3 (a) The maximal luminescent peaks of compounds 1ꢀ6 at solid state
under room temperature as number of carbon atoms. (b) The redꢀshifted
values of peaks between solid state and solution as number of carbon
15 atoms.
4
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Page 5 of 5
CrystEngComm
View Article Online
DOI: 10.1039/C5CE01345C
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Synopsis
A set of chiral crystal solids with odd and even number of carbon atoms based on S-naproxen have been
prepared, alternatively crystallizing in the space group P21 and P212121, respectively, which show odd-
even effects on cell parameters, melting points, and luminescent properties.
Table of Contents Graphic
360
359
358
357
356
355
40
32
24
16
8
a
b
c
0
1
2
3
4
5
0
1
2
3
4
5
Number of carbon atoms
Number of carbon atoms
1