Article
5,11,17,23,29,35-Hexa(dihydroxyphosphoryl)-37,38,39,40,41,42-
Crystal Growth & Design, Vol. 10, No. 7, 2010 3217
˚
a = 14.0340(4), b = 16.2130(5), c = 19.4062(6) A,R = 110.878(3),
3
-3
˚
hexamethoxycalix[6]arene (5). 2.89 mL (21.87 mmol) of bromotri-
methylsilane was added to 1.40 g (0.91 mmol) of 4 in 50 mL of dry
acetonitrile and the solution was refluxed for 16 h. The volatiles
were removed under reduced pressure and the resulting residue was
triturated with 30 mL of acetonitrile and 1 mL of water. The
precipitate formed was filtered off, washed with acetonitrile (3 ꢀ
10 mL), and recrystallized from methanol to yield 1.04 g (95%) of 5
as a white solid. Recrystallization from methanol/6 M HNO3/
CsNO3 yielded X-ray quality crystals, 5a, which were also sub-
mitted for microanalysis. mp>280 °C (dec); IR (KBr) 3180 (br),
2937 (m), 2834 (m), 2300 (br), 1641 (w), 1595 (w), 1472 (m), 1272
(m), 1118 (s), 1003 (s), 965 (s), 516 (m) cm-1; 1H NMR (DMSO-d6,
25 °C, 500 MHz) δ7.28 (d, 12H, ArH, JP-H=13.2 Hz), 6.60 (br s,
POH, shifts downfield with increasing [H]þ), 3.96 (s, 12H, ArCH2-
Ar), 3.13 (s, 18H, OCH3); 13C NMR (DMSO-d6, 25 °C, 126 MHz)
β = 95.287(2),γ=99.200(2)°, V=4019.0(2) A , Dc = 1.503 g cm
sin θ/λmax = 0.5981, N(unique) = 14088 (merged from 42363, Rint
,
=
0.0499, Rsig = 0.0770), No (I > 2σ(I)) = 8081, R = 0.0362, wR2 =
-3
˚
0.0704 (A,B = 0.024, 0), GOF = 1.004, |ΔFmax| = 0.55(6) e A
.
Crystal/refinement details for complex 5c: C48H99Ca4O50.5P6, M =
1830.41, F(000) = 961 e, triclinic, P1 (No. 2), Z = 1, T = 100(2) K,
˚
a = 11.4113(7), b = 12.9903(9), c = 15.4684(11) A, R = 112.047(7),
3
-3
˚
β = 95.814(5), γ = 108.467(6 °, V = 1951.6(2) A , Dc = 1.557 g cm
,
=
sin θ/λmax = 0.5984, N(unique) = 6828 (merged from 22732, Rint
0.0977, Rsig = 0.1485), No (I > 2σ(I)) = 3372, R = 0.0495, wR2 =
-3
˚
0.0942 (A,B = 0.025, 0), GOF = 1.008, |ΔFmax| = 1.30(8) e A
.
Acknowledgment. We thank the ARC, NSF, and NIH
(Grant P41RR000954) for financial support of this work
and the University of Western Australia for SIRF, GRST,
and PRT awards to TEC.
3
1
δ158.12, 133.93 (d, JP-C =15.5 Hz), 131.38, 128.47 (d, JP-C
=
186.0 Hz), 59.92, 29.92; 31P NMR (DMSO-d6, 25 °C, 202 MHz)
δ15.17; HRMS (FAB) m/z calcd for (C48H54O24P6)þ 1200.1431,
Supporting Information Available: Crystallographic information
file (cif). This material is available free of charge via the Internet at
found 1200.1491; Anal. Calcd for C48H54O24P6 þ 0.55HNO3
þ
0.1H2O: C 46.60, H 4.46, found: C 46.61, H 4.44.
X-ray Crystallography. Suitable crystals of 5a and 5b for diffrac-
tion studies were prepared by dissolving 4.2 mmol of 5 and 11.4 (for
5a) or 17.0 (for 5b) mmol of Ca(acetate)2 H2O in 2 mL of water
References
3
close to reflux, followed by filtration, cooling to room temperature,
followed by slow evaporation over several days. Uniformity of the
samples was checked by cell determinations of several crystals for
each sample. The X-ray diffracted intensities were measured from
single crystals on one of two machines. The first machine was an
Oxford Diffraction Gemini-R Ultra CCD diffractometer at about
(1) Diamond, D.; McKervey, M. A. Chem. Soc. Rev. 1996, 25, 15–24.
(2) (a) Atwood, J. L.; Barbour, L. J.; Jerga, A. Science 2002, 296, 2367–
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368, 229–231.
(4) Kotek, J.; Lukes, I.; Plutnar, J.; Rohovec, J.; Zak, Z. Inorg. Chim.
˚
100 K using monochromatized Cu-KR (λ=1.54178 A). The second
machine was a Bruker ASX SMART CCD diffractometer at about
Acta 2002, 335, 9.
(5) (a) Atwood, J. L.; Bott, S. G.; Hamada, F.; Means, C.; Orr, G. W.;
Robinson, K. D.; Zhang, H. Inorg. Chem. 1992, 31, 603–607.
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569. (b) Coleman, A. W.; Kuduva, S. S.; Shahgaldian, P.; Zaworotko,
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˚
100 or 153 K using monochromatized Mo-KR (λ=0.71073 A). Data
were corrected for Lorentz and polarization effects and absorption
correction applied using multiple symmetry equivalent reflections.
The structures were solved by direct method and refined on F2 using
the SHELX-97 crystallographic package17 and X-seed interface.18
A full matrix least-squares refinement procedure was used, mini-
mizing w(Fo2 - Fc ), with w=[σ2(Fo2) þ (AP)2 þ BP]-1, where P=
2
2
2
(Fo þ 2Fc )/3. Agreement factors (R=Σ Fo| - |Fc /Σ|Fo|, wR2 =
{Σ[w(Fo2 - Fc ) ]/Σ[w(Fo2)2]}1/2 and GOF={Σ[w(Fo2 - Fc ) ]/(n -
p)}1/2 are cited, where n is the number of reflections and
p is the total number of parameters refined). All non-hydrogen
atoms were refined anisotropically. The positions of hydrogen
atoms partly were localized from the difference Fourier map, partly
calculated from geometrical consideration, and their atomic para-
meters were constrained to the bonded atoms during the refinement.
CCDC deposition numbers 766115-766116, 766252-766253.
Crystal/refinement details for complex 4a: C72H104O25P6, M=
1555.37, F(000)=6608 e, monoclinic, C2/c (No. 15), Z=8, T=
2 2
2 2
(7) Arduini, A.; Casnati, A. Macrocycle Synthesis, 1st ed.; Oxford
University Press: Oxford, 1996.
(8) (a) Clark, T. E.; Makha, M.; Sobolev, A. N.; Su, D.; Rohrs, H.;
Gross, M. L.; Atwood, J. L.; Raston, C. L. New J. Chem. 2008, 32,
1478–1483. (b) Clark, T. E.; Makha, M.; Sobolev, A. N.; Rohrs, H.;
Atwood, J. L.; Raston, C. L. Chem.;Eur. J. 2008, 14, 3931–3938.
(9) Clark, T. E.; Makha, M.; Sobolev, A. N.; Su, D.; Rohrs, H.; Gross,
M. L.; Raston, C. L. Cryst. Growth Des. 2009, 9, 3575–3580.
(10) Cheng, B.; Mattson, M. P. J. Neurosci. 1992, 12, 1558–1666.
(11) Thackery, E. The Gale Encyclopedia of Cancer, 1st ed.; The Gale
Group: Farmington Hills, MI, 2002.
(12) Martin, A. D.; Raston, C. L.; Sobolev, A. N.; Spackman, M. A.
Cryst. Growth Des. 2009, 9, 3759–3764.
(13) (a) Clark, T. E.; Makha, M.; Sobolev, A. N.; Raston, C. L. Cryst.
Growth Des. 2008, 8, 890–896. (b) Jayatilaka, D.; Spackman, M. A.
Cryst. Eng. Comm. 2009, 11, 19–32.
(14) Jayatilaka, D.; McKinnon, J. J.; Spackman, M. A. Chem. Commun.
2007, 3814–3816.
(15) Parker, D., Ed. Macrocycle Synthesis: A Practical Approach;
Oxford University Press: Oxford, 1996.
(16) Gutsche, C. D; Lin, L. Tetrahedron 1986, 42, 1633.
(17) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 3.
(18) Barbour, L. J. J. Supramol. Chem. 2001, 1, 189.
(19) Dalgarno, S. J.; Hardie, M. J.; Makha, M.; Raston, C. L. Chem.;
Eur. J. 2003, 9, 2384.
˚
153(2) K, a=40.464(5), b=17.430(2), c=27.483(4) A, β=123.113-
(1)°, V=16235(4) A , Dc=1.273 g cm-3, μMo=0.205 mm-1, sin
θ/λmax = 0.5946, N(unique) = 13879 (merged from 49484, Rint
3
˚
=
0.0311, Rsig=0.0339), No (I>2σ(I))=9507, R=0.1489, wR2=0.3559
-3
˚
(A,B=0.15, 190.0), GOF=1.041, |ΔFmax|=2.1(1) e A
.
Crystal/refinement details for complex 5a: C48H70N4O42P6, M=
1560.90, F(000)=812 e, triclinic, P1 (No. 2), Z=1, T=100(2) K, a=
˚
12.182(2), b=12.332(2), c=13.108(2) A, R=113.447(3), β=94.212(3),
γ=108.695(3)°, V=1664.9(5) A , Dc=1.557 g cm-3, μMo =0.270
3
˚
mm-1, sin θ/λmax =0.5946, N(unique)=5816 (merged from 10181,
R
int=0.0251, Rsig=0.0465), No (I > 2σ(I))=4259, R=0.0697, wR2=
-3
˚
0.1849 (A,B=0.10, 3.70), GOF=1.054, |ΔFmax| = 1.1(1) e A
Crystal/refinement details for complex 5b: C48H104Ca3O52P6, M =
1819.37, F(000) = 1916 e, triclinic, P1 (No. 2), Z = 2, T = 100(2) K,
.