5776
Inorg. Chem. 1998, 37, 5776-5780
Cyanoisocyanoarene Metal Complexes as Building Blocks for Coordination Polymers:
Structural Nonrigidity of a Metal-Nitrile Linkage1
Andreas Mayr*,2 and Li-Feng Mao
Department of Chemistry, State University of New York at Stony Brook,
Stony Brook, New York 11794-3400, and Department of Chemistry,
The University of Hong Kong, Pokfulam Road, Hong Kong
ReceiVed January 7, 1998
The complexes trans-[PdI2(CNR)2], 1a-1e, (CNR ) 3-CN-C6H4-CN (1a), 4-CN-3-C2H5-C6H3-CN (1b),
c: 4-CN-3-Cl-C6H3-CN (1c), 4-CN-1,2-(NC)2-C6H3 (1d), 4-CN-C6H4-CH2CN (1e)), have been prepared.
Complex 2a forms a coordination polymer, 3, with copperbis(hexafluoroacetylacetonate) in the ratio of 1:2. The
crystal structures of compounds 2b, 2c, 2e, and 3 have been determined by X-ray crystallography. 2b: C20H16I2N4-
Pd, monoclinic space group, P1 (no. 2), a ) 4.630(2) Å, b ) 8.365(4) Å, c ) 14.835(5) Å, â ) 98.03(2)°, Z )
1 1964 unique reflections, R ) 0.038, Rw ) 0.036. 2c: C16H6Cl2I2N4Pd, monoclinic space group, P1 (no. 2), a
) 7.569(1) Å, b ) 8.229(1) Å, c ) 9.114(2) Å, â ) 77.21(1)°, Z ) 1, 1633 unique reflections, R ) 0.030, Rw
) 0.028. 2e: C18H12I2N4Pd, monoclinic space group, C2/c (no. 15), a ) 14.171(3) Å, b ) 8.3781(7) Å, c )
18.096(4) Å, â ) 103.41(1)°, Z ) 4, 2198 unique reflections, R ) 0.036, Rw ) 0.023. 3: C36H12Cu2F24I2N4O8-
Pd, monoclinic space group, P1 (no. 2), a ) 10.946(2) Å, b ) 11.315(3) Å, c ) 12.261(3) Å, â ) 99.39(1)°, Z
) 1, 2698 unique reflections, R ) 0.049, Rw ) 0.057.
Introduction
assembly of coordination polymers and supramolecular metal
complexes.4 We have recently demonstrated that transition
metal complexes of arylisocyanides bearing nitrile groups in
peripheral locations can be employed in a similar fashion.5 The
presence of the isocyanide transition metal complex cores6 offers
special opportunities concerning the control of the structural
and electronic properties of coordination polymers and molecular
aggregates,7 via independent variation of the metal center and
the isocyanide ligands.8 In the previous study, we have
developed metal complexes of 4-isocyanobenzonitriles with
linear, square planar, and octahedral dispositions of the iso-
cyanide ligands and demonstrated the formation of coordination
polymers with these building blocks.5 The solid formed from
trans-diiodobis(4-isocyanobenzonitrile)palladium and 2 equiv
of bis(hexafluoroacetylacetonate)copper, compound 4, was
found to possess a one-dimensional structure, which can be
described as a string of 20-membered rings, each consisting of
two I-Pd-CN-C6H4-CN subunits that are joined by copper
bridges, whereby the palladium atoms are shared by adjacent
rings. As a consequence of the linear nature of the Pd-CN-
C6H4-CN-4 portion within the rings, the copper-nitrile linkages
are strongly bent. The small C-N-Cu bond angle of only 105°
indicates that the nitrile π electrons are involved in the nitrile-
Organic and organometallic polynitriles3 are representatives
of a growing class of polytopic organic ligands for the self-
(1) Dedicated to Prof. Herbert D. Kaesz on the occasion of his 65th
birthday.
(2) On leave at The University of Hong Kong.
(3) (a) Konnert, J.; Britton, D. Inorg. Chem. 1966, 5, 1191. (b) Chow, Y.
M.; Britton, D. Acta Crystallogr. B 1975, 31, 1934. (c) Hu¨nig, S.;
Meixner, H.; Metzenthin, T.; Langohr, U.; von Schu¨tz, J. U.; Wolf,
H.-C.; Tillmanns, E. AdV. Mater. 1990, 2, 361. (d) Hoskins, B. F.;
Robson, R. J. Am. Chem. Soc. 1990, 112, 1546. (e) Batten, S. R.;
Hoskins, B. F.; Robson, R. J. Chem. Soc., Chem. Commun. 1991, 445.
(f) Bartley, S. L.; Dunbar, K. R. Angew. Chem. 1991, 103, 447; Angew.
Chem., Int. Ed. Engl. 1991, 30, 448. (g) Manriquez, J. M.; Yee, G.
T.; McLean, R.; Epstein, A. J.; Miller, J. S. Science 1991, 252, 1415.
(h) Miller, J. S.; Calabrese, J. C.; McLean, R. W.; Epstein, A. J. AdV.
Mater. 1992, 4, 498. (i) Bunn, A. G.; Caroll, P. J.; Wayland, B. B.
Inorg. Chem. 1992, 31, 1297. (j) Li, D. Q.; Huckett, S. C.; Frankcom,
T.; Paffett, M. T.; Farr, J. D.; Hawley, M. E.; Gottesfeld, S.; Thompson,
J. D.; Burns, C. J.; Swanson, B. I. In Supramolecular Architecture;
Bein, T., Ed.; ACS Symposium Series 499; American Chemical
Society: Washington, DC, 1992; p 33. (k) Cotton, F. A.; Kim, Y. J.
Am. Chem. Soc. 1993, 115, 8511. (l) Kaim, W.; Moscherosch, M.
Coord. Chem. ReV. 1994, 129, 157. (m) Carlucci, L.; Ciani, G.;
Proserpio, D. M.; Sironi, A. J. Chem. Soc., Chem. Commun. 1994,
2755. (n) Abrahams, B. F.; Hoskins, B. F.; Michail, D. M.; Robson,
R. Nature 1994, 369, 727. (o) Venkataraman, D.; Gardner, G. B.; Lee,
S.; Moore, J. S. J. Am. Chem. Soc. 1995, 117, 11600. (p) Gardner, G.
B.; Ventakaraman, D.; Moore, J. S.; Lee, S. Nature 1995, 374, 792.
(q) Dunbar, K. R. Angew. Chem. 1996, 108, 1769; Angew. Chem.,
Int. Ed. Engl. 1996, 35, 1659. (r) Gardner, G. B.; Kiang, Y.-H.; Lee,
S.; Asgaonkar, A.; Venkataraman, D. J. Am. Chem. Soc. 1996, 118,
6946. (s) Venkataraman, D.; Lee, S.; Moore, J. S.; Zhang, P.; Hirsch,
K. A.; Gardner, G. B.; Covey, A. C.; Prentice, C. L. Chem. Mater.
1996, 8, 2030. (t) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T.;
Maekawa, M.; Suenaga, Y. Furuichi, K. J. Am. Chem. Soc. 1996, 118,
3305. (u) Zhou, Y.; Arif, A. M.; Miller, J. S. J. Chem. Soc., Chem.
Commun. 1996, 1881. (v) Jacopozzi, P.; Dalcanale, E. Angew. Chem.
1997, 109, 665; Angew. Chem., Int. Ed. Engl. 1997, 36, 613. (w)
Batten, S. R.; Hoskins, B. F.; Robson, R. Angew. Chem. 1997, 109,
652; Angew. Chem., Int. Ed. Engl. 1997, 36, 636. (x) Whiteford, J.
A.; Lu, C. V.; Stang, P. J. J. Am. Chem. Soc. 1997, 119, 2524. (y)
Hirsch, K. A.; Wilson, S. R.; Moore, J. S. J. Am. Chem. Soc. 1997,
119, 10401. (z) Huck, W. T. S.; van Veggel, F. C. J. M.; Reinhoudt,
D. N. J. Mater. Chem. 1997, 7, 1213.
(4) (a) Robson, R.; Abrahams, B. F.; Batten, S. R.; Gable, R. W.; Hoskins,
B. F.; Liu, J. in Supramolecular Architecture; Bein, T., Ed.; ACS
Symposium Series 499; American Chemical Society: Washington,
DC, 1992. (b) Lehn, J.-M. In PerspectiVes in Coordination Chemistry;
Williams, A. F., Floriani, C., Merbach, A. S., Eds.; VCH Publishers:
Weinheim, 1992; p 447. (c) Dunbar, K. R.; Heintz, R. A. Prog. Inorg.
Chem. 1997, 45, 283.
(5) Mao, L.-F.; Mayr, A. Inorg. Chem. 1996, 35, 3183.
(6) (a) Malatesta, L.; Bonati, F. Isocyanide Complexes of Transition
Metals; Wiley: New York, 1969. (b) Treichel, P. M. AdV. Organomet.
Chem. 1973, 11, 21. (c) Lippard, S. J. Prog. Inorg. Chem. 1976, 21,
91. (d) Yamamoto, Y. Coord. Chem. ReV. 1980, 32, 193. (e) Singleton,
E.; Oosthuizen, H. E. AdV. Organomet. Chem. 1983, 22, 209. (f) Hahn,
F. E. Angew. Chem. 1993, 105, 681; Angew. Chem., Int. Ed. Engl.
1993, 32, 650. (g) Lentz, D. Angew. Chem. 1994, 106, 1377; Angew.
Chem., Int. Ed. Engl. 1994, 33, 1315.
10.1021/ic980019r CCC: $15.00 © 1998 American Chemical Society
Published on Web 10/15/1998