Article
Crystal Growth & Design, Vol. 11, No. 2, 2011 563
linear, zigzag, and helical chains are obtained. The phospho-
nium cations containing carboxylate anions are prepared by
two routes: by anion exchange reactions with phosphonium
chlorides and by protonation of neutral phosphine(amine)-
imine, P(NPh)(NHPh)3. While the phosphonium cations con-
taining monocarboxylate anions show solvent-assisted supra-
molecular structures, the corresponding phosphonium di- and
tricarboxylate salts display intricate charge-assisted hydrogen-
bonding interactions forming tightly knit 3D structures. All
these compounds were characterized by IR, NMR, and X-ray
crystallographic techniques. Thermogravimetric studies per-
formed on the phosphonium carboxylates show good thermal
stabilities for their supramolecular assemblies. Currently,
work is in progress toward utilizing these phosphonium scaf-
folds as multimodal ligands for obtaining polynuclear clusters,
coordination cages, and porous coordination polymers. Pos-
sible synthesis of such porous coordination polymers based on
phosphonium building blocks may pave way for the quanti-
tative entrapment of gaseous molecules.24
Supporting Information Available: Synthetic procedures for
7-17, crystallographic data in table format as well as in CIF format,
table of bond lengths and bond angles for 1-17, crystal structure of
figures for 17, additional figures for 6 2H2O, 8, 12, and 16 and TGA
3
data. This material is available free of charge via the Internet at
References
(1) (a) Bernstein, J.; Davis, R. E.; Shimoni, L.; Chang, N.-L. Angew.
€
Chem., Int. Ed. Engl. 1995, 34, 1555. (b) Aakeroy, C. B.; Seddon, K. R.
Chem. Soc. Rev. 1993, 397. (c) Desiraju, G. R. Crystal Engineering. The
Design of Organic Solids; Elsevier: Amsterdam, 1989. (d) David, J.;
Wolstenholme, D. J.; Weigand, J. J.; Cameron, E. M.; Cameron, T. S. Cryst.
€
Growth Des. 2009, 9, 282. (e) Aakeroy, C. B.; Nieuwenhuyzen, M. J. Am.
ꢀ
Chem. Soc. 1994, 116, 10983. (f) Katrusiak, A; Szafranski, M. T. J. Am.
Chem. Soc. 2006, 128, 15775. (g) Desiraju, G. R. Acc. Chem. Res. 2002,
35, 565. (h) Desiraju, G. R. Angew. Chem., Int. Ed. 2007, 46, 565.
(2) (a) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629. (b)
Braga, D.; Desiraju, G. R.; Miller, J. S.; Orpen, A. G.; Price, S. L.
CrystEngComm 2002, 4, 500. (c) Hosseini, M. W. Coord. Chem. Rev.
2003, 240, 157. (d) Braga, D.; Brammer, L.; Champness, N. R.
CrystEngComm 2005, 7, 1. (e) Adams, C. J.; Crawford, P. C.; Orpen,
A. G.; Podesta, T. J.; Salt, B. Chem. Commun. 2005, 2457.
(3) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460.
(b) Ockwig, N. W.; Delgado-Friedrichs, O.; O'Keeffe, M.; Yaghi, O. M.
Acc. Chem. Res. 2005, 38, 176. (c) Delgado-Friedrichs, O.; O'Keeffe,
Experimental Section
General Remarks. All manipulations involving phosphorus pen-
tachloride were performed under drynitrogen atmosphere instandard
Schlenk glassware. Solvents were dried over potassium (thf, hexane)
and sodium (toluene). The precursor compounds, phosphonium
chlorides 1-6 and phosphonium bromide 17 were prepared as
described previously.15 PCl5 and primary amines were purchased
from Aldrich and used as received. The carboxylate precursors were
locally procured (SPECTROCHEM, India) and used as received.
NMR spectra were recorded on a 400 MHz Varian FT spectrometer
(1H NMR 400.13 MHz, 13C{1H} NMR 100.62 MHz, 31P{1H} NMR
161.97 MHz) at room temperature using SiMe4 (1H, 13C) and 85%
H3PO4 (31P) as external standards. FT-IR spectra were taken on a
Perkin-Elmer spectrophotometer with samples prepared as KBr
pellets. Melting points were obtained using an Electrothermal melting
point apparatus and are uncorrected. Detailed experimental proce-
dures for the compounds 7-16 and 19 are described in the Supporting
Information.
ꢀ
M.; Yaghi, O. M. Phys. Chem. Chem. Phys. 2007, 9, 1035. (d) Ferey,
G. Chem. Soc. Rev. 2008, 37, 191. (e) Huang, B. L.; Ni, Z.; Millward,
A.; McGaughey, A. J. H.; Kaviany, M.; Yaghi, O. M. Int. J. Heat Mass
Transfer 2007, 50, 405.
(4) (a) Collins, D. J.; Zhou, H.-C. J. Mater. Chem. 2007, 17, 3154. (b)
Klontzas, E.; Emmanuel Tylianakis, E.; Froudakis, G. E. Nano Lett.
2010, 10, 452. (c) Rowsell, J. L. C.; Spencer, E. C.; Eckert, J.; Howard,
J. A. K.; Yaghi, O. M. Science 2005, 309, 1350. (d) Wong-Foy, A. G.;
Matzger, A. J.; Yaghi, O. M. J. Am. Chem. Soc. 2006, 128, 3494.
(5) (a) Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chem., Int. Ed.
2009, 48, 7502. (b) Yang, L.; Kinoshita, S.; Yamada, T.; Kanda, S.;
Kitagawa, H.; Tokunaga, M.; Ishimoto, T.; Ogura, T.; Nagumo, R.;
Miyamoto, A.; Koyama, M. Angew. Chem., Int. Ed. 2010, 49, 5348.
(c) Kitagawa, S.; Matsuda, R. Coord. Chem. Rev. 2007, 251, 2490. (d)
Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43,
2334. (e) Bradshaw, D.; Claridge, J. B.; Cussen, E. J.; Rosseinsky, M. J.
Acc. Chem. Res. 2005, 38, 273. (f) Lu, G.; Hupp, J. T. J. Am. Chem.
Soc. 2010, 132, 7832. (g) Lin, W. Top. Catal. 2010, 53, 869.
(6) (a) Desiraju, G. R. Nature 2001, 412, 397. (b) Sharma, C. V. K. Cryst.
Growth Des. 2002, 2, 465. (c) Desiraju, G. R. Angew. Chem., Int. Ed.
2007, 46, 8342. (d) Jeffrey, G. A. An Introduction to Hydrogen
Bonding; Oxford University Press: Oxford, U.K., 1997.
(7) (a) Asymmetric Phase Trnasfer Catalysis; Maruoka, K., Ed.; Wiley-
VCH: Weinheim, Germany, 2008. (b) Kosolapoff, G. M. In Organo-
phosphorus Compounds; John Wiley and Sons: New York, 1950. (c) A
Guide to Organophosphorus Chemistry; Quin, L. D., Ed.; John Wiley
and Sons: New York, 2000. (d) Wittig, G.; Geissler, G. Liebigs Ann.
Chem. 1953, 580, 44. (e) Venkatachalam, T. K.; Samuel, P.; Ucken,
F. M. Bioorg. Med. Chem. 2005, 13, 1763. (f) Nam, N. H.; Kim, Y.;
You, Y. J.; Hong, D. H.; Kim, H. M.; Ahn, B. Z. Bioorg. Med. Chem.
2005, 11, 1021.
Crystallography. Reflections were collected either on a Bruker
Smart Apex II CCD diffractometer at 293 K or on a Bruker Smart
Apex CCD diffractometer at 100 K using Mo KR radiation (λ =
˚
0.71073 A). Structures were refined by full-matrix least-squares
against F2 using all data (SHELX).25 Non-hydrogen atoms were
refined aniostropically. Hydrogen atoms were constrained in
geometric positions to their parent atoms, with the exception of
N-bound H-atoms, which were refined without constraints. Crys-
tallographic data of 2, 3, 4, 5, 6 2H2O, 7, 8, 9, 10 2thf, 12, 13, 16,
3
3
and 17 are listed in Table S1, Supporting Information. The crystal
structure of 4 contains one disordered isobutyl group and one
disordered isobutyl amino group. The solvated molecules of water
and thf in the crystal structures of 6 2H2O and 10 2thf, respec-
3
3
tively, are disordered. One phenyl ring in 7 and three phenyl rings
in 13 are disordered. Atom positions of the disordered groups in 4,
6 2H2O, 10 2thf, and 13 were split over two positions and refined
€
(8) Rexin, O.; Mulhaupt, R. J. Polym. Sci., Part A: Polym. Chem.
2002, 40, 864.
(9) Uraguchi, D.; Ueki., Y.; Ooi, T. J. Am. Chem. Soc. 2008, 130,
14088.
(10) (a) Uraguchi, D.; Sakaki, S.; Ooi, T. J. Am. Chem. Soc. 2007, 129,
12392. (b) Uraguchi, D.; Ito, T.; Ooi, T. J. Am. Chem. Soc. 2009, 131,
3836.
(11) (a) Uraguchi, D.; Ueki, Y.; Ooi, T. Science 2006, 326, 120. (b) Rix,
D.; Lacour, J. Angew. Chem., Int. Ed. 2010, 49, 1918.
(12) (a) Bickley, J. F.; Copsey, M. C.; Jeffery, J. C.; Leedham, A. P.;
Russell, C. A.; Stalke, D.; Steiner, A.; Stey, T.; Zacchini, S. Dalton
Trans. 2004, 989. (b) Steiner, A.; Zacchini, S.; Richards, P. I. Coord.
Chem. Rev. 2002, 227, 193. Other examples of isoelectronic N-analo-
gues of phosphate derivates can be found at (c) Fleischer, R.; Stalke, D.
Coord. Chem. Rev. 1998, 176, 431. (d) Raithby, P. R.; Russell, C. A.;
Steiner, A.; Wright, D. S. Angew. Chem., Int. Ed. Engl. 1997, 36, 649.
(e) Armstrong, A. F.; Chivers, T.; Krahn, M.; Parvez, M.; G. Schatte, G.
Chem. Commun. 2002, 2332. (f) Armstrong, A. F.; Chivers, T.; Krahn,
M.; Parvez, M. Can. J. Chem. 2005, 83, 1768.
3
3
isotropically using similar-distance restraints. The disordered
phenyl group of 7 was split over three positions and isotropically
refined. Crystals of 4 and 13 diffracted weakly lacking observed
reflections at higher angles; thus a cutoff at 2θ = 45ꢀ was
applied. Although the unit cell parameters of 16 show a good
fit for orthorhombic P, both the diffraction pattern and the
crystal structure shows monoclinic P symmetry and no sign of
twinning.
Acknowledgment. This work was supported by the De-
partment of Science and Technology, Fast Track proposal for
young scientists, through Grant No. SR/FT/CS-014/2008
(R.B.) and Engineering and Physical Sciences Research Council,
U.K. (A.S.).