[CuCN·Me₃SnCN·0.5bpy] (bpy = 4,4‘-Bipyridine):  A Novel Supramolecular Assembly Involving the No Longer Unusual {Cu₂(μ-CN)₂(CN)₂} Motif

Abstract

Reaction of K(3)[Cu(CN)(4)] with Me(3)SnCl and 4,4'-bipyridine (bpy) affords the novel ternary adduct [CuCN.Me(3)SnCN.0.5bpy], 2, as yellow, cubelike crystals. The supramolecular architecture of 2 consists, according to a single-crystal X-ray study, of remarkably porous, approximately planar sheets held together by almost perpendicular bpy pillars. Basic building blocks of the sheets are {Cu(2)(&mgr;-CN)(2)(CN)(2)} fragments whose N atoms are connected, via Me(3)Sn bridges, with the N atoms of adjacent fragments. 2 crystallizes in space group P2(1)/c with (at 20 degrees C) a = 10.035(4) Å, b = 11.980(3) Å, c = 12.425(5) Å, beta = 110.94(3) degrees, and Z = 4. The dinuclear building blocks resemble strongly those of the long known, but chemically more labile, layered coordination polymer [CuCN.NH(3)], 1. Although the lattice of 2 consists of two equivalent, ideally interpenetrating 3D frameworks, spacious, straight channels of a cross section of ca. 10 Å x 5 Å persist in this unprecedented structure. The likewise polymeric new adduct [CuCN.Me(3)SnCN.H(2)O] (3) obtained from K(3)[Cu(CN)(4)] and Me(3)SnCl in the absence of bpy may be considered as a formal precursor of 2.

Funktionale poröse Koordinationspolymere

“…[54][55][56][57] CN À -und SCN À -Ionen haben ähnliche Verbrückungseigenschaften wie Halogenide. [58][59][60][61] Cyanometallat-Anionen können vielfältige Geometrien einnehmen: z. B. lineare wie bei [M(CN) 2 ] À (M = Au, [62,63] Ag [64][65][66] ), trigonale wie bei [Cu(CN) 3 ] 2À , [67] tetraedrische wie bei [Cd(CN) 4 ] 2À , [68][69][70][71] quadratisch-planare wie bei [M(CN) 4 ] 2À (M = Ni, [41] Pd, [72][73][74] Pt [72,75] ), oktaedrische wie bei [M(CN) 6 ] 3À (M = Fe, [76][77][78][79][80] Co, [76,81,82] Cr, [83][84][85] Mn [86,87] ) und pentagonal-bipyramidale wie bei [Mo (CN) 7 ] 4À .…”

3D-Interpenetrating Frameworks of 3∞[Cu2(CN)4(Me3Pb)2(bpy)] Containing the Rhombic [Cu2(µ3-CN)2] Motifs

“…The [Cu 2 (l 3 -CN) 2 ] motifs seem to display the essential role as the main building block in the structure of 1. It is worth mentioned that the number of the SCP containing the rhombic [Cu 2 (l 3 -CN) 2 ] motifs is now growing up [7,9,[18][19][20][21][22][23][24][25][26] presenting a rich collection of structural data on cyanide groups point towards the copper ions producing l 3 -CN units. The previously described 3D-framework of the coordination polymer [Cu 2 (CN) 2 (pip)] (pip = piprazine) even seems to involve l 4 -CN units, i.e.…”

“…groups on the topology of the SCP. However, the structure features of these SCP are the formation of 3D-networks which contain the rhombic [Cu 2 (l 3 -CN) 2 ] motif or strong Cu…Cu interaction, even shorter than in elemental copper, via interwoven of the sheets [7][8][9]. Such porous networks have potential applications in areas such as separations, gas storage, antitumor, luminescence and catalysis [5,[10][11][12].…”

Organometallic Polymers of Germanium, Tin and Lead

“…A detailed description of all these compounds is beyond the scope of this article and only the structures of two representatives are discussed in more detail. The copper-containing derivative [CuCN·Me 3 SnCN·0.5 bipy] n (bipy = 4, 4 -bipyridine) (164) forms planar sheets held together by almost perpendicular bipyridine pillars 382 . The sheets consist of [Cu 2 (µ-CN) 2 (CN) 2 ] fragments which are connected via CN−SnMe 3 −NC sequences with the nitrogens in the axial positions of a trigonal-bipyramidal configurated tin to give 24-membered rings.…”