twin-ligands (Fig. S7, ESIw), and interestingly, the helical
chains in the three independent nets have equal helical pitches,
˚
which are 50.865(2) A, corresponding to 2 ꢂ a. 1 relates to a
recently published compound with helical chains around the
1
I-strands however this had much longer distances between
9
ꢀ
˚
the I atoms [12.287(1) A].
In summary, we have described the first 8-fold non-
equivalent interpenetrated architecture. Large nanotubes
formed in such a highly interpenetrated system should be
ascribed to the unique interpenetration mode and the unusual
cationic and anionic frameworks interpenetration.
We thank the Natural Science Foundation of China (Nos.
ꢀ
Fig. 2 Left: Nanotubular structure of 1 (the free I ions are omitted
9
1022011; 20971065; 21021062) and National Basic Research
for clarity). Right: Space filling mode showing the close packing of the
SBUs of the eight frameworks (W pink, S yellow, Cu light blue).
Program of China (2010CB923303; 2007CB925103) for
financial support.
retained. As the anionic and cationic networks are packed
alternatively as aforementioned, the SBUs of adjacent frame-
works take opposite charges, coulombic interactions lead to a
close packing of SBUs (Fig. 2, right), the separations of the
Notes and references
1
Recent reviews: (a) L. Ma, C. Abney and W. Lin, Chem. Soc. Rev.,
2009, 38, 1248; (b) S. Ma and H.-C. Zhou, Chem. Commun., 2010,
46, 44; (c) S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem.,
Int. Ed., 2004, 43, 2334; (d) G. Fe
´
rey, Chem. Soc. Rev., 2008, 37,
91; (e) L. J. Murray, M. Dinc and J. R. Long, Chem. Soc. Rev.,
009, 38, 1294; (f) R. E. Morris and P. S. Wheatley, Angew. Chem.,
centers of the SBUs of adjacent nets are just 6.261(1) and
˚
1
2
6
.646(1) A. Single and twined dpbp ligands also packed
1
8
compactly by C–Hꢁ ꢁ ꢁp hydrogen bonding interactions and
Int. Ed., 2008, 47, 4966; (g) A. U. Czaja, N. Trukhan and
U. Muller, Chem. Soc. Rev., 2009, 38, 1284; (h) C. Janiak and
J. K. Vieth, New J. Chem., 2010, 34, 2366.
form the ‘walls’ of the nanotubes along the [100] direction
¨
(
Fig. S5 ESI,w the Hꢁ ꢁ ꢁp
distances are in the range
angles are in the range
centroid
2
3
(a) M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke,
M. O’Keeffe and O. M. Yaghi, Acc. Chem. Res., 2001, 34, 319;
(b) N. W. Ockwig, O. Delgado-Friedrichs, M. O’Keeffe and
O. M. Yaghi, Acc. Chem. Res., 2005, 38, 176.
J. L. C. Rowsell, E. C. Spencer, J. Eckert, J. A. K. Howard and
O. M. Yaghi, Science, 2005, 309, 1350.
4 S. Y. Stephen, C. Samuel, M. F. Lo, P. H. Jonathan, A. Charmant,
˚
2
.797(1) B 3.220(1) A, C–Hꢁ ꢁ ꢁp
centroid
1
36.0 B 160.51). Therefore, both the extraordinary inter-
penetrating mode and the unusual cationic and anionic
frameworks interpenetration account for the formation of
large tubes in this highly interpenetrating system.
It is noticeable that the individual nanotube is chiral which
is formed by eight helical chains in the same chirality, and
adjacent tubes are formed by helical chains with opposite
handedness as shown in Fig. 2 and Fig. S6 (ESIw). To
demonstrate the formation of meso-nanotubes, we simplify a
dia net as two adamantane cages sharing one vertex
G. Orpen and I. D. Williams, Science, 1999, 283, 1148.
5
(a) Y. Niu, H.-G. Zheng, H.-W. Hou and X.-Q. Xin, Coord. Chem.
Rev., 2004, 248, 169; (b) H.-W. Hou, X.-Q. Xin and S. Shi, Coord.
Chem. Rev., 1996, 153, 25.
6 (a) Y.-J. Huang, Y.-L. Song, Y. Chen, H.-X. Li, Y. Zhang and
J.-P. Lang, Dalton Trans., 2009, 1411; (b) L. Song, J.-R. Li, P. Lin,
Z.-H. Li, T. Li, S.-W. Du and X.-T. Wu, Inorg. Chem., 2006, 45,
1
0155.
(
Scheme 2). Four helical chains can be derived with adjacent
7
8
9
J.-P. Lang, Q.-F. Xu, W.-H. Zhang, H.-X. Li, Z.-G. Ren,
J.-X. Chen and Y. Zhang, Inorg. Chem., 2006, 45, 10487.
Z.-R. Pan, J. Xu, H.-G. Zheng, K.-X. Huang, Y.-Z. Li, Z.-J. Guo
and S. R. Batten, Inorg. Chem., 2009, 48, 5772.
Y. Cai, Y. Wang, Y.-Z. Li, X.-S. Wang, X.-Q. Xin, C.-M. Liu and
H.-G. Zheng, Inorg. Chem., 2005, 44, 9128.
0 J.-P. Lang, Q.-F. Xu, R.-X. Yuan and B. F. Abrahams, Angew.
Chem., Int. Ed., 2004, 43, 4741.
1 K. Liang, H.-G. Zheng, Y.-L. Song, M. F. Lappert, Y.-Z. Li,
X.-Q. Xin, Z.-X. Huang, J.-T. Chen and S.-F. Lu, Angew. Chem.,
Int. Ed., 2004, 43, 5776.
helical chains sharing edges. The dia network is not chiral and
the four helical chains are two P and two M. One of the
P helical chains was emphasized in red in Scheme 2. The
interpenetration with the vector parallel to the helical axis can
make the two P helical chains interweave together. The
tubular structure can be formed on the basis that the helices
1
1
are packed close enough to form the walls of the tube. In 1, the
ꢀ
4 3 2
helical chains in NET A are constructed by the [WS Cu I ]
1
2 (a) V. A. Blatov, L. Carlucci, G. Ciani and D. M. Proserpio,
CrystEngComm, 2004, 6, 378 (and references therein);
(b) I. A. Baburin, V. A. Blatov, L. Carlucci, G. Ciani and
D. M. Proserpio, J. Solid State Chem., 2005, 178, 2452.
SBU and dpbp single-ligands, and helical chains within
2+
net B or C are constructed by the [WS Cu ] SBU and dpbp
4
4
1
1
3 X.-L. Wang, C. Qin, S.-X. Wu, K.-Z. Shao, Y.-Q. Lan, S. Wang,
D.-X. Zhu, Z.-M. Su and E.-B. Wang, Angew. Chem., Int. Ed.,
2
009, 48, 5291.
4 S. R. Batten and R. Robson, Angew. Chem., Int. Ed., 1998, 37,
460.
1
1
1
1
1
5 S. R. Batten, CrystEngComm, 2001, 3, 67.
6 O. R. Evans and W. Lin, Chem. Mater., 2001, 13, 2705.
7 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7.
¨
8 (a) H. A. Habib, A. Hoffmann, H. A. Hoppe, G. Steinfeld and
C. Janiak, Inorg. Chem., 2009, 48, 2166; (b) C. Janiak, J. Chem.
Soc., Dalton Trans., 2000, 3885.
19 E. Redel, C. Rohr and C. Janiak, Chem. Commun., 2009, 2103.
¨
Scheme 2 A presentation demonstrates the assembly of helical chains
derived from dia nets into meso-tubes.
This journal is c The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 2919–2921 2921