Synthesis, crystal structure determination of two-dimensional supramolecular co-ordination polymer of silver(I) with 1,2-Bis(phenylthio)ethane and its Hirshfeld surface analysis (original) (raw)
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Acta crystallographica. Section E, Structure reports online, 2014
The asymmetric unit of the title compound, {[Ag(C11H11N3)]NO3·2(CH3)2SO} n , comprises one Ag(I) atom, one N-(pyridine-4-ylmeth-yl)pyridine-3-amine ligand, one nitrate anion and two dimethyl sulfoxide mol-ecules. The Ag(I) atoms are bridged by two pyridine N atoms from two symmetry-related ligands, forming a helical chain and adopting a slightly distorted linear coordination geometry [N-Ag-N = 175.37 (8)°]. The helical chain, with a pitch length of 16.7871 (8) Å, propagates along the b-axis direction. In the crystal, symmetry-related right- and left-handed helical chains are alternately arranged via Ag⋯Ag inter-actions [3.4145 (4) Å] and π-π stacking inter-actions [centroid-centroid distance = 3.650 (2) Å], resulting in the formation of a two-dimensional supra-molecular network extending parallel to (100). Weak Ag⋯O [2.775 (2), 3.169 (4) and 2.690 (2) Å] inter-actions, as well as several N-H⋯O and C-H⋯O hydrogen-bonding inter-actions, contribute to the stabilization of the crystal s...
Hierarchy of Hydrogen Bonding versus Anion Binding in Self-Assembled Network Structures of Silver(I)
Crystal Growth & Design, 2006
Reaction of the ligands 1,2-C 6 H 4 {NHC(dO)-4-C 5 H 4 N} 2 (1) and 1,2-C 6 H 4 {NHC(dO)-3-C 5 H 4 N} 2 (2) with silver(I) salts AgX, X ) CF 3 CO 2 , NO 3 , CF 3 SO 3 , and PF 6 , gave the corresponding complexes [(AgX)(µ-LL)] n , 3a-4d (3a-3d: LL ) 1; 4a-4d: LL ) 2; a, X ) CF 3 CO 2 ; b, X ) NO 3 ; c, X ) CF 3 SO 3 ; d, X ) PF 6 ). The complexes probably exist in solution primarily as the disilver(I) macrocyclic complexes [{AgX(µ-LL)} 2 ] or [Ag 2 (µ-LL) 2 ]X 2 , but in the solid state they may exist as either macrocycles or polymers [{AgX(µ-LL)} n ] or [Ag n (µ-LL) n ]X n . The silver(I) centers have distorted tetrahedral stereochemistry when X ) CF 3 CO 2 or NO 3 but roughly linear stereochemistry when X ) CF 3 SO 3 or PF 6 , and it is argued that the hierarchy of control in the selfassembly process is by the bonds Ag-N > Ag-O > NH‚‚‚OdC when X ) CF 3 CO 2 or NO 3 , but Ag-N > NH‚‚‚OdC > Ag‚‚‚O or Ag‚‚‚F when X ) CF 3 SO 3 or PF 6 . In complexes 3a and 3b, macrocyclic complexes are connected to form polymers or sheets, respectively, through bridging anions, whereas polymers of 4a are connected through bridging anions to form a double-stranded polymer. In all these cases, network structures are formed through formation of intermolecular hydrogen bonds NH‚‚‚OdC, and these porous networks contain large solvent-filled channels. In the molecular materials assembled using the more weakly bonding anions (X ) CF 3 SO 3 or PF 6 ), the network structures are more compact, and they do not contain solvent molecules. Complexes 3c and 4d exist as polymers, whereas 4c exists as a macrocycle. These complexes are further connected through hydrogen bonding and through weak Ag‚‚‚O or Ag‚‚‚F interactions to form network structures. Complexes 3a-3c and 4a adopt the polar anti conformation of the two amidopyridyl units of the bidentate ligands, and 4d adopts a similar conformation with an intramolecular NH‚‚‚OdC bond, but complex 4c adopts the nonpolar syn conformation. Complex 4d is unusual because it undergoes spontaneous resolution to give crystals in which chiral polymers are self-assembled to give a chiral network.
Inorganic Chemistry, 2008
New coordination polymers have been obtained by the self-assembly of silver salts AgX (X ) BF 4 , PF 6 , CF 3 SO 3 ) and 2,4-diamino-6-R-1,3,5-triazines L (R ) phenyl and p-tolyl) of formulas AgLX (1-6). A complex of different stoichiometry, [Ag 3 L 2 (H 2 O)(acetone) 2 ](BF 4 ) 3 , 7 (R ) phenyl), has also been synthesized. The three-dimensional structures of five compounds have been determined by X-ray diffraction studies. For the AgLX complexes, when X ) BF 4 and R ) phenyl or p-tolyl, chiral chains with alternating Ag and L are formed. The chains are cross-linked by the counteranions in a three-dimensional fashion through hydrogen bonds and weak Ag · · · F interactions giving rise to a structure with solvent-filled channels. Different and more compact structures have been found when the counteranion is CF 3 SO 3 (OTf). When R ) phenyl, sheets are formed which consist of [Ag 2 (OTf) 2 L 2 ] units with double triflate bridges and which contain columns of π-π stacked arenes. Hydrogen bonds connect the sheets. When AgOTf is used and R is p-tolyl, a different and unusual ladderlike structure is obtained in which the rungs are double asymmetric bridges consisting of the triflate groups bonded to Ag in κ 2 O,µ 2 -O and κ 1 O,µ 2 -O fashion. The ladders are parallel to each other and are mutually linked by N-H · · · N hydrogen bonds to give a 3D architecture. A very similar ladderlike structure has been found for 7 but with a water molecule and a BF 4group acting as bridges. The role played by the hydrogen bonds in complex 6 to form the 3-D structure is played in 7 by [Ag(acetone) 2 ] fragments. The noncovalent interactions play an important role in the different solid-state 3D structures. The behavior of the new derivatives in solution has also been analyzed. A new species has been detected at low temperatures, and this exhibits restricted rotation of the phenyl ring. Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O'Keeffe, M.; Yagi, O. M. Acc. Chem. Res. 2001, 34, 319-330. (d) Ockwig, N. W.; Delgado-Friedrichs, O.; O'Keeffe, M.; Yagi, O. M.
After deprotonation, the acetylacetonate moiety of the ditopic ligand 3-cyanoacetylacetone (HacacCN) acts as a chelating ligand towards PdIJII). The resulting square-planar complex PdIJacacCN) 2 represents a suitable building unit for extended structures via coordination of AgIJI) cations to the peripheral nitrile groups. These target compounds have been structurally characterized: with silver salts of the anions BF 4 − , ClO 4 − , PF 6 − and CF 3 SO 3 − , chain polymers with an alternating sequence of PdIJII) and AgIJI) are obtained. Solvent molecules and counter anions fill voids close to the silver cations; more weakly coordinating anions are engaged in longer, the triflate anion in a shorter interaction to AgIJI). In contrast to powder samples, larger crystals of these one-dimensional polymers are rather stable with respect to desolvation. Two isomorphous 1D structures undergo a fully reversible k 2 phase transition which can be monitored by single crystal diffraction. The phase transition temperature depends on the nature of the counter anion and may therefore be tuned as a function of chemical composition. The formation of chain polymers by linking PdIJacacCN) 2 building blocks with AgIJI) salts of BF 4 − , ClO 4 − , PF 6 − and CF 3 SO 3 − follows chemical intuition whereas its reaction with silver nitrate leads to an unexpected and close-packed 3D structure in which layers of composition AgIJNO 3 ) are connected by PdIJacacCN) 2 linkers. ; Tel: +1 612 8021080 † Electronic supplementary information (ESI) available: Crystallographic information in CIF format, displacement ellipsoid plots for 1-7, powder patterns for 2, 3, 5 and 7, intensity ratio IIJ f/t) for 2 and 3 over larger temperature ranges, intensity of single reflections in 2, 3 and 4, 19 F NMR result of 4 and sequence of slides visualizing the phase transition in 2.
A Triple-Stranded Ladder-Type Coordination Polymer
Crystal Growth & Design, 2012
The IR spectra were recorded on a VERTEX 80v FT-IR spectrometer. Elemental analysis was carried out on a CHNS-932 elemental analyzer. Thermogravimetric analysis (TGA) was performed under nitrogen on a SDT Q600 thermogravimetric analyzer. In TGA measurements, the samples were heated using a 10 o C/min heating rate from 20 to 900 o C.
Chemical Data Collections
N,N,N 0 ,N 0-tetrakis-[(2-benzimidazolyl)methyl]-1,2-ethanediamine (EDTB), a multidentate ligand, was synthesized by refluxing of EDTA and o-phenylenediamine in glycol with a molar ratio of 1:4. Reaction of the 2:1:1 stoichiometric proportion of EDTB with cadmium(II) bromide and copper(II) bromide in methanol and distilled water affords a mononuclear copper(II) complex, [Cu(EDTB)] [CdBr 4 ]ÁH 2 O (1), which crystallizes in the monoclinic space group P2 1 /c with a = 12.226(3), b = 20.948(5), c = 19.330(3) Å , b = 116.597(11)°, V = 4426.7(17) Å 3 and Z = 4. [Cu(EDTB)] 2? cations are linked to the [CdBr 4 ] 2anions and water molecules by N-HÁÁÁBr and N-HÁÁÁO hydrogen bonds. Furthermore, C-HÁÁÁBr, C-HÁÁÁp and pÁÁÁp weak interactions also connect these units into a 2D structure. A detailed investigation of the crystal packing and intermolecular interactions has been examined using the Hirshfeld surface analysis. Hirshfeld surfaces and fingerprint plots showed the presence of intermolecular interactions.
Inorganic Chemistry, 1987
By the use of a novel series of sterically hindered thiolate ligands, (RR'R"Si),CH,-,SH, the colorless silver-thiolate complexes [AgSC(SiMe,Ph),], (5a) and [AgSC(SiMe3),14 (4a) and the yellow species [AgSCH(SiMe3),18 (3a) and [Ag,(SCH,-(SiMe3)]3(OCH3)], (2a) have been synthesized and structurally characterized. The structure of Sa consists of a discrete nonplanar six-membered cycle of alternating silver and sulfur atoms, Ag,S,, exhibiting no secondary A g S interactions between trinuclear units. In contrast, the structure of 4a consists of a planar eight-membered cycle, Ag&, and exhibits unstrained digonal Ag-S coordination, unperturbed by secondary A g S interactions. The results suggest that a degree of control of aggregation may be introduced by employing ligands possessing sufficient steric bulk. Furthermore, the reduction of ligand steric hindrance in-SCH(SiMe3)2 has profound structural consequences as illustrated by the structure of 3a, which consists of two weakly interacting [AgSCH(SiMe,),], cycles, facing each other and connected by secondary A g. S interactions, producing a T-shaped geometry about the Ag centers. Further reduction in the steric bulk of the ligand results in the polymeric structure of 2a. The complex three-dimensional polymer may be described in terms of kinked chains of fused octanuclear Ag4S4 cyclic links cross-linked through bridging Ag,S, monocycles. Crystal data: for 5a, triclinic Pi, a = 11.236 (2) A, b = 16.445 (3) A, c = 25.686 (4) A, CY = 92.79 (1)". /3 = 97.52 (l)", y = 108.77 (I)O, V = 4434.2 (9) A', Da,d = 1.34 g cm-, for Z = 2, R = 0.061 for 9537 reflections; for 4a, orthorhombic Pbca, a = 17.478 (3) A, b = 28.314 (4) A, c = 29.706 (4) A, V = 14700.6 (12) A3, DmId = 1.28 g cm-' for Z = 8, R = 0.069 for 2759 reflections; for 3a, monoclinic C2/c, a = 18.339 (4) A, b = 24.623 (4) A, c = 24.473 (4) A, @ = 96.74 (I)', V = 10974.6 (1 1) A', Dald = 1.45 g cm-, for 2 = 4, R = 0.063 for 3919 reflections; for 2b, monoclinic C2/c, a = 17.023 (3) A, b = 29.470 (5) A, c = 23.372 (4) A, /3 = 104.21 (l)", V = 11366.2 (14) A', Dald = 1.92 g cm-, for 2 = 16, R = 0.069 for 1366 reflections.