Crystal Growth & Design
Article
and 0.6 g of hydrazine hydrate aqueous solution (1:1 w/w) were
dissolved in 15 mL of glacial acetic acid. The mixture was then stirred
for 8 h at 118 °C resulting in a brown solution. The solution was
cooled to room temperature and slowly poured into a beaker
containing ice water. The crude product was collected by filtration and
recrystallized from ethanol/ethyl acetate (1:1 v/v) mixed solvent as
follows: Yield: 74%; mp: 234−236 °C; colorless; FT-IR (KBr, cm−1):
3449, 2925, 1652, 1602, 1513, 1424, 1251, 1178, 1117, 883, 835, 730.
1H NMR (500 MHz, CDCl3, TMS, δ): 8.50−8.52 (d, J = 9.5 Hz, 1H),
8.40 (s, 1H), 7.99−8.00 (d, J = 8.5 Hz, 2H), 7.81−7.99 (d, J = 8.5 Hz,
1H), 7.74−7.76 (d, J = 9.0 Hz, 2H), 7.52−7.56 (m, 1H), 7.44−7.47 (t,
1H), 7.36−7.39 (t, 1H), 7.31−7.34 (m, 1H), 6.95−6.98 (m, 2H),
6.82−6.86 (dd, 1H), 3.84−3.90 (dd, 1H), 3.85 (s, 3H), 3.44−3.49 (dd,
1H), 2.34 (s, 3H). 13C NMR (500 MHz, CDCl3, TMS, δ): 161.45,
153.67, 131.66, 129.38, 128.27, 126.50, 124.84, 123.17, 114.26, 55.41,
41.95, 21.84. MS (ESI, m/z): calcd. for AMPE [M + H]+, 395.5;
found, 395.1. Elementary analysis calcd. for C26H22N2O2 (394.17): C
79.16, H 5.62, N 7.10; found: C 78.87, H 5.62, N 6.93.
ASSOCIATED CONTENT
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S
* Supporting Information
Determination methods, simulated XRD patterns of the
crystals, optical properties of AMPE in solutions, fluorescence
spectra of solid-state APPE and ANPE, solution-state
fluorescence spectra of crystals II and III, fluorescence decay
curves, excitation spectra, and X-ray crystallographic informa-
tion files (CIF) for crystals I, II, and III. This material is
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
Preparation and X-ray Diffraction Measurements of the
Three Crystals. Crystal I was obtained by slow evaporation of AMPE
ethyl acetate solution. In the above-mentioned synthesis process of
AMPE, the yellow resulting solid was obtained after reaction when the
usage of glacial acetic acid was reduced to 5 mL. The resulting solid
was filtered and dried. Then 0.30 g of solid was dissolved in 25 mL of
acetonitrile/acetic acid (v:v = 4:1) mixed solvent. The solution was
evaporated to yield crystal II. A mixture of AMPE (0.40 g, 1 mmol)
and malonic acid (4.05 g, 39 mmol) in 20 mL of dichloromethane/
ethanol (v:v = 1:1) mixed solvent was stirred at 50 °C for 6 h. Then,
the mixture was cooled to room temperature and filtered to provide a
clear solution. Crystal III was obtained by the slow evaporation of this
clear solution.
The PXRD patterns for the three crystals were recorded using a 18
KW advance X-ray diffractometer with Cu Kα radiation (λ = 1.54056
Å). Single X-ray diffraction data for the three crystals were collected on
a Rigaku SCXmini diffractometer (crystals I and III) with a Mercury2
CCD area-detector or a BRUKER APEX II diffractometer (crystal II)
with an APEX II CCD detector by using graphite-monochromatized
Cu Kα radiation (λ = 0.71073 Å). Direct methods were used to solve
the structure. The structure is solved with direct methods using the
SHELXS-97 program and refine anisotropically with SHELXTL-97
using full-matrix least-squares procedure.29 All non-hydrogen atoms
were refined with anisotropic displacement parameters, and they were
placed in idealized positions and refined as rigid atoms with the
relative isotropic displacement parameters.
ACKNOWLEDGMENTS
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This project gets the supports of the National Basic Research
Program of China (2011CB302004) and Open Project of
Southeast University Key Laboratory of Environmental
Medicine Engineering of Ministry of Education
(2010EME009).
REFERENCES
■
(1) Braga, D. Chem. Commun. 2003, 22, 2751−2754.
(2) Hollingsworth, M. D. Science 2002, 295, 2410−2413.
(3) Desiraju, G. R. CrystEngComm 2003, 5, 466−467.
(4) Bernstein, J. Cryst. Growth Des. 2011, 11, 632−650.
(5) Zaworotko, M. J. Nat. Chem. 2011, 3, 653.
(6) Strassert, C. A.; Chien, C.; Lopez, M. D. G.; Kourkoulos, D.;
Hertel, D.; Meerholz, K.; Cola, De L. Angew. Chem., Int. Ed. 2011, 50,
946−950.
(7) Gao, F.; Liao, Q.; Xu, Z.; Yue, Y.; Wang, Q.; Zhang, H.; Fu, H.
Angew. Chem., Int. Ed. 2010, 49, 732−735.
(8) Yan, D.; Lu, J.; Ma, J.; Wei, M.; Evans, D. G.; Duan, X. Angew.
Chem., Int. Ed. 2011, 50, 720−723.
(9) Denk, W. Proc. Natl. Acad. Sci. U.S.A. 1994, 91, 6629−6633.
̌ ̌ ́
(10) Yan, D.; Delori, A.; Lloyd, G. O.; Friscic, T.; Day, G. M.; Jones,
W.; Lu, J.; Wei, M.; Evans, D. G.; Duan, X. Angew. Chem., Int. Ed.
2011, 50, 12483−12486.
(11) Mizobe, Y.; Tohnai, N.; Miyata, M.; Hasegawa, Y. Chem.
Commun. 2005, 14, 1839−1841.
Crystal data for crystal I: C26H22N2O2, M = 394.46, orthorhombic,
space group P212121, a = 10.856(2), b = 11.111(2), c = 17.560(4) Å, V
= 2118.0(7) Å3, Z = 4, T = 293(2) K, Dc =1.237 g·cm−3, μ(Mo−Kα) =
0.079 mm−1, F(000) = 832, λ = 0.71073 Å, 22 090 reflections
measured, 4843 unique (Rint = 0.054), which were used in all
calculations. The final R1 and wR2 were 0.0528 (observed data) and
0.1111 (observed data), respectively. GOF = 1.055. CCDC 842 081.
Crystal data for crystal II: C26H22N2O2·C2H4O2, M = 454.51,
(12) Zhang, G.; Lu, J.; Sabat, M.; Fraser, C. L. J. Am. Chem. Soc. 2010,
132, 2160−2162.
(13) Davis, R.; Rath, N. P.; Das, S. Chem. Commun. 2004, 1, 74−75.
(14) Hisaki, I.; Kometani, E.; Shigemitsu, H.; Saeki, A.; Seki, S.;
Tohnai, N.; Miyata, M. Cryst. Growth Des. 2011, 11, 5488−5497.
(15) Zhou, T.; Jia, T.; Zhao, S.; Guo, J.; Zhang, H.; Wang, Y. Cryst.
Growth Des. 2012, 12, 179−184.
triclinic, space group P1, a = 8.2824(19), b = 11.048(3), c = 14.035(3)
̅
(16) Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.;
Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.; Bred
Å, α = 86.649(3)°, β = 76.491(3)°, γ = 70.242(3)°, V = 1174.9(5) Å3,
Z = 2, T = 296(2) K, Dc = 1.285 g·cm−3, μ(Mo−Kα) = 0.086 mm−1,
F(000) = 480, λ = 0.71073 Å, 8216 reflections measured, 4003 unique
(Rint = 0.031), which were used in all calculations. The final R1 and
wR2 were 0.0470 (observed data) and 0.1424 (observed data),
respectively. GOF = 1.075. CCDC 860 387.
́
as,
J. L.; Lodlund, M.; Salaneck, W. R. Nature 1999, 397, 121−128.
̈
(17) Moorthy, J. N.; Venkatakrishnan, P.; Natarajan, P.; Huang, D.
F.; Chow, T. J. J. Am. Chem. Soc. 2008, 130, 17320−17333.
(18) An, B. K.; Kwon, S. K.; Jung, S.; Park, S. Y. J. Am. Chem. Soc.
2002, 124, 14410−14415.
Crystal data for crystal III: C26H22N2O2·C3H4O4, M = 498.52,
(19) Chen, J.; Law, C.; Lam, J.; Dong, Y.; Lo, S.; Williams, D. I.; Zhu,
D.; Tang, B. Chem. Mater. 2003, 15, 1535−1546.
(20) Hong, Y.; Lam, J.; Tang, B. Chem. Soc. Rev. 2011, 40, 5361−
5388.
triclinic, space group P1, a = 10.343(2), b = 10.623(2), c = 12.106(2)
̅
Å, α = 93.00(3)°, β = 91.2(3)°, γ = 113.69(3)°, V = 1214.2(5) Å3, Z =
2, T = 293(2) K, Dc = 1.364 g·cm−3, μ(Mo−Kα) = 0.096 mm−1,
F(000) = 524, λ = 0.71073 Å, 10 254 reflections measured, 4183
unique (Rint = 0.041), which were used in all calculations. The final R1
and wR2 were 0.0559 (observed data) and 0.1394 (observed data),
respectively. GOF = 1.009. CCDC 876 362.
(21) Wu, C. H.; Chien, C. H.; Hsu, F. M.; Shih, P. I.; Shu, C. F. J.
Mater. Chem. 2009, 19, 1464−1470.
(22) Fahrni, C. J.; Yang, L.; VanDerveer, D. G. J. Am. Chem. Soc.
2003, 125, 3799−3812.
5992
dx.doi.org/10.1021/cg301055j | Cryst. Growth Des. 2012, 12, 5986−5993