Synthesis, characterization, crystal structure and fluorescence property of tetramethyl 5,5′-(terephthaloylbis(azanediyl))-diisophthalate

Article abstract of DOI:10.1007/s10870-012-0367-9

An aroyl acylamide compound, tetramethyl 5,5′- (terephthaloylbis(azanediyl))-diisophthalate (1), has been prepared by nucleophilic substitution reaction of dimethyl 5-aminoisophthalate and terephthaloyl chloride, and characterized by elemental analysis, F

Full text of DOI:10.1007/s10870-012-0367-9

J Chem Crystallogr (2012) 42:1124–1128
DOI 10.1007/s10870-012-0367-9
ORIGINAL PAPER
Synthesis, Characterization, Crystal Structure and Fluorescence
Property of Tetramethyl 5,50-(Terephthaloylbis(azanediyl))-
Diisophthalate
•
Qingfu Zhang Aijing Geng Zhipeng Liu
•
•
•
Yang Shi Dezhi Sun
Received: 21 April 2012 / Accepted: 20 September 2012 / Published online: 30 September 2012
Ó Springer Science+Business Media New York 2012
Abstract An aroyl acylamide compound, tetramethyl
5,50-(terephthaloylbis(azanediyl))-diisophthalate (1), has
been prepared by nucleophilic substitution reaction of
dimethyl 5-aminoisophthalate and terephthaloyl chloride,
Introduction
Acylamide compounds have attracted considerable
attention due to their wide applications in chemistry,
biology, medicine and materials science along with their
fascinating molecular and supramolecular structures [1–
4]. Acylamides are particularly of high interest because
some of them have been successfully employed in the
self-assembly of several intriguing molecular architec-
tures, such as nanotube, macrocycle and porous metal–
organic frameworks, etc. [5–10]. Sun and coworkers
have carried out a series of wonderful work on the
construction of MOFs using acylamide ligands [6, 8].
Bai et al. [10] have also reported some interesting
luminescent complexes assembled from acylamide
ligands. To explore in this area, we designed and suc-
cessfully prepared a novel aroyl acylamide compound,
tetramethyl 5,50-(terephthaloylbis(azanediyl))-diisophtha-
late (1). Herein, we reported the detailed synthesis,
characterization and crystal structure of compound 1,
which exhibits a strong blue emission at 413 nm in the
solid state at room temperature.
1
and characterized by elemental analysis, FT-IR, H-NMR,
ESI–MS and single-crystal X-ray diffraction. The crystal of
1ꢀ2DMF belongs to monoclinic space group P2/c with
˚
a = 21.609(2) A, b = 4.060(1) A, c = 21.606(2) A,
˚
˚
3
˚
b = 112.805(1)°, V = 1747.4(3) A , Z = 2, Dc = 1.320
Mg m-3, l = 0.101 mm-1, F(000) = 732, Mr = 694.68,
the final R1 = 0.0879 and wR2 = 0.1872 for 8091
observed reflections with I [ 2r(I). The structural analysis
reveals that compound 1ꢀ2DMF contains one tetramethyl
5,50-(terephthaloylbis-(azanediyl))-diisophthalate and two
N,N-dimethylformamide solvent molecules. A 3D supra-
molecular structure of 1ꢀ2DMF is constructed by multiply
intermolecular C–HꢀꢀꢀO H-bonds and p–p stacking inter-
actions. In addition, compound 1 exhibits a strong blue
fluorescence at 413 nm in the solid state at room
temperature.
Keywords Acylamide compound ꢀ Synthesis ꢀ
Crystal structure ꢀ Fluorescence
Experimental Section
Materials and Method
All chemicals and solvents used for synthesis were
obtained from commercial sources. Elemental analyses
for C, H and N were carried out with a Perkin-Elmer
2400 II elemental analyzer. The 1H-NMR spectra were
recorded on a Mercury Plus 400 MHz FT-NMR spec-
trometer using tetramethylsilane (TMS) as an internal
reference. IR spectra were measured on a Nicolet-5700
Q. Zhang (&) ꢀ A. Geng ꢀ Z. Liu ꢀ Y. Shi ꢀ D. Sun (&)
Shandong Provincial Key Laboratory of Chemical Energy
Storage and Novel Cell Technology, College of Chemistry
and Chemical Engineering, Liaocheng University, Liaocheng
252059, China
e-mail: zhangqingfu@lcu.edu.cn
D. Sun
e-mail: sundezhi@lcu.edu.cn
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J Chem Crystallogr (2012) 42:1124–1128
1125
FT-IR spectrophotometer using KBr discs. ESI–MS spectra
were performed on a Finnigan DE-CAX-30000 LCQ Deca
XP ion trap mass spectrometer. Fluorescence spectra of the
solid samples were recorded on a Hitachi F-7000FL fluo-
rescence spectrophotometer.
Table 1 Crystal data and structure refinement for 1ꢀ2DMF
Empirical formula
Formula weight
Crystal system
C34H38N4O12
694.68
Monoclinic
P2/c
Space group
˚
a = 21.609(2) A
Unit cell dimensions
˚
b = 4.060(1) A
Synthesis of Compound 1
˚
c = 21.606(2) A
Dimethyl 5-aminoisophthalate (1.32 g, 6.33 mmol) and
triethylamine (1.50 ml, 9.50 mmol) were reacted with te-
rephthaloyl chloride (0.58 g, 2.86 mmol) in anhydrous
dichloromethane (20 mL) for 10 h at room temperature.
The solvent was removed by rotary evaporation, and the
solid was washed three times with dichloromethane. The
white product was dried under vacuum overnight. Yield:
1.43 g, 91.30 %. Anal. Calcd. for C28H24N2O10 (548.50):
C, 61.31; H, 4.41; N, 5.11. Found: C, 61.27; H, 4.35; N,
5.14 %. 1H-NMR (DMSO-d6, ppm): d 10.82 (s, 2H,
–CONH–), 8.75 (s, 4H, Ar–H), 8.23 (s, 2H, Ar–H), 8.16 (s,
4H, Ar–H), 3.91 (s, 12H, –CH3). 13C-NMR could not be
done because of the insolubility of the compound. Selected
IR spectrum (KBr, cm-1): 3346, 2955, 1720, 1555, 1263,
865, 758, 671. ESI–MS: m/z 549.3 [M ? H?]. The color-
less crystals of 1ꢀ2DMF suitable for X-ray diffraction were
obtained by recrystallization from N,N-dimethylformamide
(DMF).
b = 112.805(1)°
1747.4(3)
3
˚
Volume(A )
Z
2
Calculated density(Mg m-3
Absorption coefficient(mm-1
)
1.320
)
0.101
F(000)
Crystal size(mm3)
732
0.44 9 0.11 9 0.09
2.26 to 25.01
Theta range for data collection(°)
Limiting indices
-17 B h B 25, -4 B k B 4,
-25 B l B 25
Reflections collected/Unique
Completeness to h = 25.01°
Max. and min. transmission
Data/Restraints/Parameters
Goodness-of-fit on F2
8091/3061 [Rint = 0.0837]
99.6 %
0.9910 and 0.9569
3061/0/230
1.065
Final R indices [I [ 2r(I)]
R indices (all data)
R1 = 0.0879, wR2 = 0.1872
R1 = 0.1641, wR2 = 0.2115
0.687 and -0.243
-3
)
˚
Largest diff. peak and hole(e.A
X-Ray Crystallography
Results and Discussion
A colorless needle single-crystal with dimensions of
0.44 9 0.11 9 0.09 mm3 was selected for indexing and
intensity data collection on a Bruker smart-1000 CCD
diffractometer at 298(2) K using graphite monochromated
Synthesis and Spectral Characterization of Compound 1
As shown in Scheme 1, compound 1 was obtained from the
nucleophilic substitution reaction of dimethyl 5-amin-
oisophthalate and terephthaloyl chloride in dichloromethane
with triethylamine. The molecular formula of compound 1 is
determined to be C28H24N2O10 according to elemental
analysis and ESI–MS spectrum.
The number of hydrogen atoms observed in the 1H-
NMR spectrum is in agreement with the molecular for-
mula. The downfield signal at 10.82 is ascribed to –
C(O)NH and the signal at 3.91 is assigned to the –CH3. The
other three signals at 8.75, 8.23 and 8.16 are ascribed to the
hydrogen atoms on the phenyl ring.
˚
Mo-Ka radiation (k = 0.71073 A). Multi-scan absorption
corrections based on symmetry equivalents were applied
to the 8091 reflections collected (2hmax = 50.02), 3061
unique reflections were observed [Rint = 0.0837] after
data reduction. The structure was solved by direct meth-
ods and refined on F2 by full-matrix least-squares meth-
ods using the SHELX-97 program package [11]. All non-
hydrogen atoms were refined anisotropically, and hydro-
gen atoms were located at calculated positions and refined
isotropically. The refinement converged to
a final
R1 = 0.0879, and wR2 = 0.1872 of I [ 2r(I), S = 1.065,
(D/r)max = 0.000. The largest peak in the final difference
-3
Fourier map is 0.687 e A and the minimum peak is -
In the IR spectrum, the broad adsorption band at
3346 cm-1 characterizes the –NH– stretching vibration of
the acylamide group in compound 1. The peak at
2955 cm-1 is assigned to the Ar–H stretching vibration
adsorption, and the peak at 1720 cm-1 is ascribed to the
–C=O adsorption of –Ar(C=O)OCH3 group. The absorp-
tion peaks at 1555 cm-1 and 1263 cm-1 are ascribed to the
˚
0.243 e A-3. The details of the crystal parameters, data
˚
collection and refinements for the 1ꢀ2DMF are summa-
rized in Table 1, selected bond lengths and angles are
listed in Table 2, the geometric parameters of H-bonds
and p–p stacking interactions for 1ꢀ2DMF are given in
Table 3.
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J Chem Crystallogr (2012) 42:1124–1128
˚
Structural Description of Compound 1ꢀ2DMF
Table 2 Selected bond lengths [A] and angles [°] for 1ꢀ2DMF
˚
Lengths(A)
Single-crystal X-ray diffraction analysis reveals that com-
pound 1ꢀ2DMF crystallizes in monoclinic space group P2/
c and consists of one tetramethyl 5,50-(terephthaloyl-
bis(azanediyl))-diisophthalate molecule and two DMF
solvent molecules. As shown in Fig. 1, the –CH group of
terminal phenyl ring and amide O atom are linked by
intramolecular C–HꢀꢀꢀO (Table 3, C10–H10ꢀꢀꢀO1) H-bonds
to form a six-member-ring structure, thus the plane con-
taining terminal phenyl ring group and C1, N1, O1 atoms is
almost coplanar. However, the whole tetramethyl 5,50-(te-
O1–C1
1.229(4)
1.346(5)
1.437(5)
1.221(4)
1.355(5)
1.459(5)
1.212(5)
1.242(6)
1.383(5)
N1–C5
1.433(5)
1.335(6)
1.446(6)
1.440(7)
1.505(6)
1.400(6)
1.400(6)
1.515(6)
1.508(5)
O2–C11
N2–C15
N2–C16
N2–C17
C1–C2
C3–C4a
C4–C3a
C7–C11
C9–C13
O2–C12
O3–C11
O4–C13
O4–C14
O5–C13
O6–C15
N1–C1
Angles(°)
rephthaloylbis(azanediyl))-diisophthalate
in
1ꢀ2DMF
O1–C1–N1
O1–C1–C2
O2–C11–O3
O2–C11–C7
O3–C11–C7
O4–C13–O5
O4–C13–C9
O5–C13–C9
O6–C15–N2
N1–C1–C2
N1–C5–C6
N1–C5–C10
123.0(4)
121.7(4)
123.4(4)
112.1(4)
124.4(4)
124.1(4)
112.5(4)
123.4(4)
127.3(5)
115.2(4)
117.7(4)
122.1(4)
C1–N1–C5
127.2(3)
117.2(4)
124.4(4)
120.2(4)
121.6(4)
118.2(4)
116.8(3)
115.0(3)
122.0(5)
120.5(5)
117.5(5)
adopts a non-planar conformation, and the dihedral angle
between the central phenyl ring and the above mentioned
plane containing C1, N1, O1 atoms and phenyl ring group
is about 34.91(14)°. This non-planar conformation of tet-
ramethyl 5,50-(terephthaloylbis(azanediyl))-diisophthalate
should root from the C–C (C1–C2) single bond rotation
between the central phenyl ring and acylamide group, and
be stabilized by the N–HꢀꢀꢀO (Table 3, N1–H1ꢀꢀꢀO6) and
C–HꢀꢀꢀO (Table 3, C4–H4ꢀꢀꢀO6 and C6–H6ꢀꢀꢀO6) H-bonds.
Two new C–N bonds in 1ꢀ2DMF formed by the nucleo-
philic substitution reaction represent the typical acylamide
C1–C2–C3
C1–C2–C4
C2–C3–C4a
C2–C4–C3a
C3–C2–C4
C11–O2–C12
C13–O4–C14
C15–N2–C16
C15–N2–C17
C16–N2–C17
˚
bonds. The bond lengths of C–N (C1–N1 1.383(5) A) and
˚
C=O (C1–O1 1.229(4) A) suggest the C(O)NH group
a
Symmetry code: -x,-y-1,-z
adopts usually ketonic form in 1ꢀ2DMF, which are in the
normal range of acylamide compounds [12–14].
As shown in Fig. 2, the non-planar molecules of tetra-
5,50-(terephthaloylbis(azanediyl))-diisophthalate
vibrations of acylamide II band and acylamide III band,
respectively. In addition, the adsorption bands at 865, 758
and 671 cm-1 are ascribed to the Ar–H out-of-plane ring
deformation vibrations in compound 1. All the above IR
attribution is consistent with structural determination.
methyl
are linked by intermolecular C–HꢀꢀꢀO (Table 3, C14–
H14BꢀꢀꢀO3b) H-bonds to form a 1D double chain structure
along the c-axis. The resulting chains are further connected
through intermolecular p-p stacking interactions (Table 3)
Table 3 The geometric
H-bonds
parameters of H-bonds and p-p
stacking interactions for
1ꢀ2DMF
˚
D–H (A)
˚
˚
HꢀꢀꢀA (A)
DꢀꢀꢀA (A)
D–HꢀꢀꢀA (°)
N1–H1ꢀꢀꢀO6
0.86
0.93
0.93
0.93
0.96
0.96
0.93
2.18
2.62
2.62
2.30
2.78
2.57
2.63
3.019(5)
3.354(6)
3.351(7)
2.875(5)
3.168(5)
3.467(5)
3.406(8)
163.9(3)
136.7(3)
136.5(3)
119.5(3)
105.1(3)
154.9(3)
141.9(4)
C4–H4ꢀꢀꢀO6
C6–H6ꢀꢀꢀO6
C10–H10ꢀꢀꢀO1
C12–H12BꢀꢀꢀO5a
C14–H14BꢀꢀꢀO3b
C15–H15ꢀꢀꢀO3c
p–p stacking interactions
Cg1 and Cg2 are the centroids
of the rings defined by C5–C6–
C7–C8–C9–C10, C2–C3–C4–
C2d–C3d–C4d, respectively
Centroid–Centroid
˚
(A)
Interplanar
separation (A)
Dihedral
angle (°)
Slip angle
(°)
˚
a
Symmetry codes: 1 - x,
Cg1ꢀꢀꢀCg1c
Cg2ꢀꢀꢀCg2c
Cg1dꢀꢀꢀCg1e
4.060
4.060
4.060
3.491
3.623
3.491
0.00
0.00
0.00
30.7
26.8
30.7
b
1 ? y, ‘ - z; x, -y, z - 1/2;
d
cx, y-1, z; -x, -y - 1, -z;
e-x, -y - 2, -z
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J Chem Crystallogr (2012) 42:1124–1128
1127
Scheme 1 Synthesis of
compound 1
Fig. 1 Molecular structure of 1ꢀ2DMF. Dotted lines indicate the N–HꢀꢀꢀO and C–HꢀꢀꢀO H-bonds
Fig. 2 A 1D double chain
structure of 1ꢀ2DMF linked by
intermolecular C–HꢀꢀꢀO
H-bonds along c-axis (solvent
DMF molecules and H atoms
except for H14B are omitted for
clarity). Symmetry codes: (b) x,
-y, z - 1/2; (d) -x, -y - 1,
-z; (f) -x, y - 1, -z-1/2
Fluorescence Property of 1
and another intermolecular C–HꢀꢀꢀO H-bonds (Table 3,
C12–H12BꢀꢀꢀO5a) along two different directions, yielding a
3D supramolecular framework with large rectangle chan-
nels. Interestingly, the guest DMF molecules are found in
these 1D channels (Fig. 3). In consideration of the H-bonds
(Table 3, N1–H1ꢀꢀꢀO6, C4–H4ꢀꢀꢀO6, C6–H6ꢀꢀꢀO6 and C15–
H15ꢀꢀꢀO3c) between the host framework and guest mole-
cules, the DMF molecules can be considered as supramo-
lecular templates and are beneficial to the stability of this
3D framework.
The fluorescence emission spectrum of tetramethyl 5,50-
(terephthaloylbis(azanediyl))-diisophthalate was investi-
gated in the solid state at room temperature, with the result
shown in Fig. 4. Upon excitation at 270 nm, compound 1
exhibits a strong blue emission with the main peak (kmax
)
appearing at 413 nm, indicating that 1 is a good molecule-
based solid fluorescent material. Besides, considering that
compound 1 could easily form H-bonds with guest
123

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J Chem Crystallogr (2012) 42:1124–1128
prepared and characterized by elemental analysis, FT-IR,
1H-NMR, ESI–MS and single-crystal X-ray diffraction
analysis. The structural analysis reveals that the tetra-
methyl
5,50-(terephthaloylbis(azanediyl))-diisophthalate
molecule adopts a non-planar conformation by the solvent-
assisted C–C single bond rotation, and a 3D supramolec-
ular framework structure is constructed by multiply inter-
molecular C–HꢀꢀꢀO H-bonds and p–p stacking interactions.
Moreover, compound 1 exhibits a strong blue fluorescence
at 413 nm in the solid state at room temperature.
Supplementary Material
CCDC 857994 contains the supplementary crystallographic
data for the compound. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.
html, or from the Cambridge Crystallographic Data Centre,
12 Union Road, Cambridge CB2 1EZ, UK; fax: (?44)
1223-336-033; or e-mail:deposit@ccdc.cam.ac.uk.
Fig. 3 A 3D supramolecular framework structure of 1ꢀ2DMF con-
structed by intermolecular C–HꢀꢀꢀO H-bonds and p–p stacking
interactions, the guest DMF molecules (space-filling mode) occupy
in the 1D channels. Symmetry codes: (c) x, y - 1, z; (d) -x, -y - 1,
-z; (e) -x, -y - 2, -z
Acknowledgments This study was supported by the National Nat-
ure Science Foundation of China (Grant No. 21001061) and the
Nature Science Foundation of Shandong Province (Grant No.
ZR2010BL020).
References
1. Garima G, Vijayakumar R, Adam RU, Werner MN (2011) J Am
Chem Soc 133:7528
2. Liu DH, William FDG (2001) J Am Chem Soc 123:7553
3. Mileni M, Garfunkle J, Ezzili C, Cravatt BF, Stevens RC, Dale
LB (2011) J Am Chem Soc 133:4092
´
4. Vazquez ME, Blanco JB, Imperiali B (2005) J Am Chem Soc
127:1300
5. Chen MS, Fan J, Okamura TA, Lv GC, Sun WY (2011) Inorg
Chim Acta 366:268
6. Chen MS, Chen Y, Takamizawa S, Okamura TA, Fan J, Sun WY
(2011) Chem Commun 47:3787
7. Prasad TK, Hong DH, Suh MP (2010) Chem Eur J 16:14043
8. Chen MS, Bai ZS, Okamura TA, Su Z, Chen SS, Sun WY,
Ueyama N (2010) CrystEngComm 12:1935
9. Zheng BS, Bai JF, Duan JG, Wojtas L, Michael JZ (2011) J Am
Chem Soc 133(4):748
10. Duan JG, Zheng BS, Bai JF, Zhang Q, Zuo KY (2010) Inorg
Chim Acta 363:3172
11. Sheldrick GM (2008) Acta Crystallogr A64:112
12. Zhang QF, Xiong KC, Yang M, Jiang FL, Hong MC (2009) Chin
J Struct Chem 28:1625
Fig. 4 Solid-state emission spectrum of compound 1 (kex = 270 nm)
at room temperature
molecules, it may be further used as a prospected photo-
sensor in detecting small organic molecules or biologic
macromolecules [15].
13. Xu HM, Liu SX (2006) Acta Crystallogr E62:o3026
14. Yang DS (2007) J Chem Crystallogr 37:343
15. Cui YJ, Yue YF, Qian GD, Chen BL (2012) Chem Rev 112(2):
1126
Conclusions
In summary, an acylamide compound, tetramethyl 5,50-
(terephthaloylbis(azanediyl))-diisophthalate (1), has been
123