Angewandte
Chemie
CH protons being refined in riding geometries (SHELXTL)
against F2. In most cases, amide protons were refined isotropi-
cally subject to a distant constraint. Any other restraints or
additional features of the refinement are detailed for each
structure below. The structure determination for H21 proved
particularly problematic; we collected full datasets using a
variety of collection routines on more than 15 different crystals
from several different crystallization experiments. The data were
always poor, principally because of disorder arising from the
alkyl chain and solvated molecules. The structure was refined
isotropically with no protons included in the refinement. H21:
C112H130N4O6, Mr = 1628, crystal size = 0.2 0.1 0.03 mm3,
orthorhombic, Pbca, a = 18.338(4), b = 23.545(5), c =
44.922(9) , V= 19396(7) 3, Z = 8, 1calcd = 1.115 MgmÀ3; m =
0.068 mmÀ1, 18573 data (17303 unique), R = 0.3339 for F
[1] For reviews, see: a) Molecular Catenanes, Rotaxanes, and Knots:
A Journey Through the World of Molecular Topology (Eds.: J.-P.
Sauvage, C. Dietrich-Buchecker), Wiley-VCH, Weinheim, 1999;
b) V. Balzani, A Credi, F. M. Raymo, J. F. Stoddart, Angew.
Chem. 2000, 112, 3484 – 3530; Angew. Chem. Int. Ed. 2000, 39,
3348 – 3391; c) V. Balzani, M. Venturi, A. Credi, Molecular
Devices and Machines—A Journey into the Nanoworld, Wiley-
VCH, Weinheim, 2003; d) A. H. Flood, R. J. A. Ramirez, W.-Q.
Deng, R. P. Muller, W. A. Goddard, J. F. Stoddart, Aust. J. Chem.
2004, 57, 301 – 322; e) “Synthetic Molecular Machines”: E. R.
Kay, D. A. Leigh in Functional Artificial Receptors (Eds.: T.
Schrader, A. D. Hamilton), Wiley-VCH, Weinheim, 2005, 333 –
406.
[2] For examples in which encapsulation and/or preorganization of
the coordinating ligand geometry in a mechanically interlocked
architecture can bring about significant property effects, see:
(stabilization of oxidation state/complex geometry) a) C. O.
Dietrich-Buchecker, J.-P. Sauvage, J. Am. Chem. Soc. 1984,
106, 3043 – 3045; b) N. Armaroli, L. De Cola, V. Balzani, J.-P.
Sauvage, C. O. Dietrich-Buchecker, J.-M. Kern, A. Bailal, J.
Chem. Soc. Dalton Trans. 1993, 3241 – 3247; (protection of
functional groups) c) D. Leigh, A. Murphy, J. P. Smart, A. M. Z.
Slawin, Angew. Chem. 1997, 109, 752 – 756; Angew. Chem. Int.
Ed. Engl. 1997, 36, 728 – 731; d) M. R. Craig, M. G. Hutchings,
T. D. W. Claridge, H. L. Anderson, Angew. Chem. 2001, 113,
1105 – 1108; Angew. Chem. Int. Ed. 2001, 40, 1071 – 1074;
e) J. E. H. Buston, F. Marken, H. L. Anderson, Chem.
Commun. 2001, 1046 – 1047; f) T. Oku, Y. Furusho, T. Takata,
Org. Lett. 2003, 5, 4923 – 4925; g) D. A. Leigh, E. M. PØrez,
Chem. Commun. 2004, 2262 – 2263; (solubility) h) H. W. Gibson,
S Liu, P. Lecavalier, C. Wu, Y. X. Shen, J. Am. Chem. Soc. 1995,
117, 852 – 874; i) A. G. Johnston, D. A. Leigh, A. Murphy, J. P.
Smart, M. D. Deegan, J. Am. Chem. Soc. 1996, 118, 10662 –
10663; j) S. Anderson, H. L. Anderson, Angew. Chem. 1996,
108, 2075 – 2078; Angew. Chem. Int. Ed. Engl. 1996, 35, 1956 –
1959; (conformation of a component) k) W. Clegg, C. Gimenez-
Saiz, D. A. Leigh, A. Murphy, A. M. Z. Slawin, S. J. Teat, J. Am.
Chem. Soc. 1999, 121, 4124 – 4129; (electroluminescence) l) F.
Cacialli, J. S. Wilson, J. J. Michels, C. Daniel, C. Silva, R. H.
Friend, N. Severin, P. Samori, J. P. Rabe, M. J. OꢀConnell, P. N.
Taylor, H. L. Anderson, Nat. Mater. 2002, 1, 160 – 164; (mem-
brane transport) m) V. Dvornikovs, B. E. House, M. Kaetzel,
J. R. Dedman, D. B. Smithrud, J. Am. Chem. Soc. 2003, 125,
8290 – 8301.
values of reflections with Fo > 4sFo), S = 4.90 for 463 parameters.
À3
Residual electron density extremes were 1.665 and À4.557 e
.
H22: C62H76N4O8, Mr = 1005.27, colorless prism, crystal size =
0.2 0.2 0.2 mm3, triclinic, P-1, a = 11.3539(11), b =
12.0635(11), c = 20.445(2) , a = 82.323(6), b = 88.351(7), g =
80.397(7)8, V= 2736.2(5) 3, Z = 2, 1calcd = 1.220 MgmÀ3; m =
0.080 mmÀ1
, 15494 data (8824 unique, Rint = 0.0176), R =
0.0499, S = 0.987 for 677 parameters. Residual electron density
À3
extremes were 0.759 and À0.336 e
.
H21·TfOH:
C113H131F3N4O9S, Mr = 1778.28, colorless prism, crystal size =
0.15 0.1 0.1 mm3, monoclinic, P21/c, a = 20.555(2), b =
18.7503(19),
c = 27.853(3) ,
b = 109.574(2)8,
V=
10114.6(17) 3, Z = 4, 1calcd = 1.168 MgmÀ3
;
m = 0.096 mmÀ1
,
59606 data (18472 unique, Rint = 0.0449), R = 0.1058, S = 1.028
for 1149 parameters. Residual electron density extremes were
1.366 and À0.649 eÀ3. Cu1: C117H135.5CuN6.5O6, Mr = 1792.36,
violet platelet, crystal size = 0.2 0.1 0.01 mm3, triclinic, P-1,
a = 16.404(3), b = 17.516(3), c = 20.046(4) , a = 100.573(3), b =
106.016(3), g = 96.178(3)8, V= 5365.3(17) 3, Z = 2, 1calcd
1.109 MgmÀ3 m = 0.258 mmÀ1
41166 data (17787 unique,
int = 0.0318), R = 0.1507, S = 1.812 for 1163 parameters. Resid-
=
;
,
R
ual electron density extremes were 2.325 and À1.107 eÀ3. The
half-weight acetonitrile solvent molecules were refined isotropi-
cally. Ni1: C117H137.5N6.5NiO7, Mr = 1805.54, orange needle,
crystal size = 0.15 0.015 0.015 mm3, triclinic, P-1 a =
16.423(3), b = 17.582(3), c = 20.056(3) , a = 100.0161(19), b =
106.234(3), g = 96.2695(18)8, V= 5398.6(15) 3, Z = 2, 1calcd
1.111 MgmÀ3 m = 0.235 mmÀ1
40853 data (17841 unique,
int = 0.0506), R = 0.1302, S = 1.465 for 1184 parameters. Resid-
=
;
,
R
ual electron density extremes were 1.874 and À0.891. The half-
weight acetonitrile and quarter-weight water solvent molecules
were refined isotropically. The protons on all solvated molecules
were discounted in the refinement. [Pd(H21)Cl2(MeCN)]:
[3] A.-M. Fuller, D. A. Leigh, P. J. Lusby, I. D. H. Oswald, S.
Parsons, D. B. Walker, Angew. Chem. 2004, 116, 4004 – 4008;
Angew. Chem. Int. Ed. 2004, 43, 3914 – 3918.
[4] For a recent example of a [2]rotaxane that utilizes square-planar
PdII coordination, see: I. Yoon, M. Narita, T. Shimizu, M.
Asakawa, J. Am. Chem. Soc. 2004, 126, 16740 – 16741.
C
122H145N9O6Cl2Pd, Mr = 2010.77, yellow platelet, crystal size =
0.2 0.1 0.01 mm3, monoclinic, C2/c, a = 29.6525(12), b =
23.2314(10), c = 32.6559(14) , b = 99.071(3)8, V=
22214.3(16) 3, Z = 8, 1calcd = 1.202 MgmÀ3 m = 0.273 mmÀ1
[5] S. L. Jain, P. Bhattacharyya, H. L. Milton, A. M. Z. Slawin, J. A.
Crayston, J. D. Woollins, Dalton Trans. 2004, 862 – 871.
;
,
58779 data (19158 unique, Rint = 0.1733), R = 0.1416, S = 1.090
for 1253 parameters. Residual electron density extremes were
0.946 and À0.925 eÀ3. The half-weight acetonitrile solvent
molecules were refined isotropically. The protons on solvated
molecules were discounted in the refinement. CCDC 259162–
259166 contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from the
ac.uk/data_request/cif.
[6] F. Biscarini, M. Cavallini, D. A. Leigh, S. León, S. J. Teat, J. K. Y.
Wong, F. Zerbetto, J. Am. Chem. Soc. 2002, 124, 225 – 233.
[7] Structural data for H21, Cu1, and Ni1 were collected at 93 K
using a Rigaku Saturn diffractometer (MM007 high-flux RA/
MoKa radiation, confocal optic); for H22 and [Pd(H21)Cl2-
(MeCN)] at 93 K using a Rigaku Mercury diffractometer
(MM007 high-flux RA/MoKa radiation, confocal optic); and for
H21·TfOH at 125 K using a Bruker SMART diffractometer
(sealed tube MoKa radiation, graphite monochromator, l =
0.71073 ). All data collections employed narrow frames (0.3–
1.08) to obtain at least a full hemisphere of data. Intensities were
corrected for Lorentzpolarization and absorption effects (multi-
ple equivalent reflections). Structures were solved by direct
methods, non-hydrogen atoms were refined anisotropically with
[8] F. G. Gatti, D. A. Leigh, S. A. Nepogodiev, A. M. Z. Slawin, S. J.
Teat, J. K. Y. Wong, J. Am. Chem. Soc. 2001, 123, 5983 – 5989.
[9] J. S. Hannam, S. M. Lacy, D. A. Leigh, C. G. Saiz, A. M. Z.
Slawin, S. G. Stitchell, Angew. Chem. 2004, 116, 3322 – 3326;
Angew. Chem. Int. Ed. 2004, 43, 3260 – 3264.
Angew. Chem. Int. Ed. 2005, 44, 4557 –4564
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4563