Factors Affecting the Solid-State Structure and Dimensionality of Mercury Cyanide/Chloride Double Salts, and NMR Characterization of Coordination Geometries Neil D. Draper, † Raymond J. Batchelor, † Pedro M. Aguiar, ‡ Scott Kroeker,* ,‡ and Daniel B. Leznoff* ,† Departments of Chemistry, Simon Fraser UniVersity, 8888 UniVersity DriVe, Burnaby, British Columbia V5A 1S6, Canada, and UniVersity of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada Received February 16, 2004 In the reaction of organic monocationic chlorides or coordinatively saturated metal-ligand complex chlorides with linear, neutral Hg(CN) 2 building blocks, the Lewis-acidic Hg(CN) 2 moieties accept the chloride ligands to form mercury cyanide/chloride double salt anions that in several cases form infinite 1-D and 2-D arrays. Thus, [PPN][Hg(CN) 2 Cl]‚H 2 O(1), [ n Bu 4 N][Hg(CN) 2 Cl]‚0.5 H 2 O(2), and [Ni(terpy) 2 ][Hg(CN) 2 Cl] 2 (4) contain [Hg(CN) 2 Cl] 2 2- anionic dimers ([PPN]Cl ) bis(triphenylphosphoranylidene)ammonium chloride, [ n Bu 4 N]Cl ) tetrabutylammonium chloride, terpy ) 2,2′:6′,6′′-terpyridine). [Cu(en) 2 ][Hg(CN) 2 Cl] 2 (5) is composed of alternating 1-D chloride-bridged [Hg(CN) 2 Cl] n n- ladders and cationic columns of [Cu(en) 2 ] 2+ (en ) ethylenediamine). When [Co(en) 3 ]Cl 3 is reacted with 3 equiv of Hg(CN) 2 , 1-D {[Hg(CN) 2 ] 2 Cl} n n- ribbons and [Hg(CN) 2 Cl 2 ] 2- moieties are formed; both form hydrogen bonds to [Co(en) 3 ] 3+ cations, yielding [Co(en) 3 ][Hg(CN) 2 Cl 2 ]{[Hg(CN) 2 ] 2 Cl} (6). In [Co(NH 3 ) 6 ] 2 [Hg(CN) 2 ] 5 Cl 6 ‚2H 2 O (7), [Co(NH 3 ) 6 ] 3+ cations and water molecules are sandwiched between chloride-bridged 2-D anionic {[Hg(CN) 2 ] 5 Cl 6 } n 6n- layers, which contain square cavities. The presence (or absence), number, and profile of hydrogen bond donor sites of the transition metal amine ligands were observed to strongly influence the structural motif and dimensionality adopted by the anionic double salt complex anions, while cation shape and cation charge had little effect. 199 Hg chemical shift tensors and 1 J( 13 C, 199 Hg) values measured in selected compounds reveal that the NMR properties are dominated by the Hg(CN) 2 moiety, with little influence from the chloride bonding characteristics. δ iso ( 13 CN) values in the isolated dimers are remarkably sensitive to the local geometry. Introduction Research into the chemistry of supramolecular coordina- tion polymers has rapidly grown in recent years due to an increased demand for functional materials with tunable properties. 1-7 The self-assembly of simple molecular building blocks containing organic ligands and inorganic metal ions provides an efficient and reliable approach for the design and synthesis of such organic/inorganic hybrid materials. 8-10 The characteristics of both the inorganic and organic moieties, such as available coordination sites, coordination geometry preference, ligand flexibility, and hydrogen bond interactions, ideally control the extended structure, thereby creating enormous potential for complexity and functionality of these modular materials. 11-18 Thus, with a careful selection * Corresponding authors. E-mail: dleznoff@sfu.ca (D.B.L.); Scott_Kroeker@UManitoba.ca (S.K.). Phone: 1-604-291-4887 (D.B.L.); 1-204-474-9335 (S.K.). Fax: 1-604-291-3765 (D.B.L.); 1-204-474-7608 (S.K.). † Simon Fraser University. ‡ University of Manitoba. (1) Caulder, D. L.; Raymond, K. N. Acc. Chem . Res. 1999, 32, 975- 982. (2) Fujita, M. Chem. Soc. ReV. 1998, 27, 417-425. (3) Jones, C. J. Chem. Soc. ReV. 1998, 27, 289-299. (4) Janiak, C. J. Chem. Soc., Dalton Trans. 2003, 2781-2804. (5) Chen, C. T.; Suslick, K. S. Coord. Chem. ReV. 1993, 128, 293-322. (6) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705-714. (7) Mitzi, D. B. J. Chem. Soc., Dalton Trans. 2001,1-12. (8) Moulton, B.; Zaworotko, M. J. Chem. ReV. 2001, 101, 1629-1658. (9) Eddaoudi, M.; Moler, D. B.; Li, H. L.; Chen, B. L.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem . Res. 2001, 34, 319-330. (10) Holliday, B. J.; Mirkin, C. A. Angew. Chem., Int. Ed. 2001, 40, 2022- 2043. (11) Ciurtin, D. M.; Smith, M. D.; zur Loye, H. C. J. Chem. Soc., Dalton Trans. 2003, 1245-1250. (12) Hoskins, B. F.; Robson, R. J. Am. Chem. Soc. 1990, 112, 1546-1554. (13) Gardner, G. B.; Venkataraman, D.; Moore, J. S.; Lee, S. Nature 1995, 374, 792-795. (14) Keller, S. W. Angew. Chem., Int. Ed. 1997, 36, 247-248. (15) Xu, Z. M.; White, S.; Thompson, L. K.; Miller, D. O.; Ohba, M.; O h kawa, H.; Wilson, C.; Howard, J. A. K. J. Chem. Soc., Dalton Trans. 2000, 11, 1751-1757. Inorg. Chem. 2004, 43, 6557-6567 10.1021/ic049792e CCC: $27.50 © 2004 American Chemical Society Inorganic Chemistry, Vol. 43, No. 21, 2004 6557 Published on Web 09/18/2004