Sulfate anion helices formed by the assistance of a flip-flop water chain

Raghavaiah, Pallepogu; Supriya, Sabbani; Das, Samar K.

doi:10.1039/b605899j

Cited by 36 publications

(23 citation statements)

References 30 publications

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“…13 A polymeric chain structure having cyclic tetramers as its basic units has recently been discovered in organic crystalline hosts. 14,15 Herein we report a corner-sharing highly ordered tetrameric water chain with additional water forming a dimeric crown (Figure 1). The chains act as sidewalls, supporting 2D metal-carboxylate sheets, to generate a 3D supramolecular host having rectangular channels ( Figure 2).…”

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confidence: 96%

Crowned Tetrameric Spirocyclic Water Chain: An Unusual Building Block of a Supramolecular Metal−Organic Host

Choudhury

Jana

Colacio

et al. 2007

Crystal Growth & Design

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A 3D supramolecular metal-organic host could be realized in solid in which the water assembly as a whole acted as a building block of the 3D framework with rectangular channels where guest molecules reside, adding a new dimension to water cluster research where the role of water has been shifted from its usual behavior of guest to that of a host. The crystal structure of the compound, {[Cu(mal) 2 ](picH) 2 ‚5H 2 O} n , 1 [mal ) malonate dianion, picH ) protonated 2-amino-4-picoline], synthesized from purely aqueous media, shows that the Cu(II)-malonate 2D coordination polymeric sheets are locked together by the water assembly that lines up perpendicular to the Cu(II)-malonate sheets constituting a 3D infinite supramolecular host where within the channels protonated 2-amino-4-picoline auxiliary ligands are accommodated. A spirocyclic tetrameric water chain having a dimeric crown on it describes the composition of the water assembly that runs down the c-axis.Water, an elixir of life on our planet, is ubiquitous and covers two-thirds of the globe. However, a complete understanding of water's behavior is still lacking, and the quest to understand water's anomalous behavior continues. 1 The realization that condensedphase behavior must be explained in terms of water clusters 2 led to the recent upsurge in water cluster research. Information on small water clusters in the gas phase was obtained through laser spectroscopic experiments, 3 supported by ab initio calculations. 4 Water's ability to form flexible hydrogen bonds with its neighboring molecules has led to the detection of various ordered water assemblies 5-10 in various deformed geometries. 11 The key to understanding the behavior of water is the precise structural data of various hydrogen-bonded networks. One can now even think of engineering the water assembly inside organic and metal-organic frameworks (MOFs) in a systematic way by gradually tuning its environment and studying its effect on the hydrogen-bonded networks. 8b,12 An understanding of this mutual interaction, especially when the components of the framework resemble molecular building blocks in biology, can possibly unravel the role of ordered water in bio-environments.The water tetramer, one of the main cluster components incorporated in models to simulate anomalous behavior 1 of water, has been predicted to be cyclic and planar 2b and has been structurally characterized within MOFs by a number of groups. 13 A polymeric chain structure having cyclic tetramers as its basic units has recently been discovered in organic crystalline hosts. 14,15 Herein we report a corner-sharing highly ordered tetrameric water chain with additional water forming a dimeric crown (Figure 1). The chains act as sidewalls, supporting 2D metal-carboxylate sheets, to generate a 3D supramolecular host having rectangular channels ( Figure 2). This unique host accommodates guest 2-amino-4-picoline ligands in their protonated forms within the channels. 16 The presence of a cyclic dimeric crown of the tetrameric water chain is u...

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confidence: 96%

Crowned Tetrameric Spirocyclic Water Chain: An Unusual Building Block of a Supramolecular Metal−Organic Host

Choudhury

Jana

Colacio

et al. 2007

Crystal Growth & Design

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“…The average N-O bond length of the nitrate groups (1.245(8) Å ) corresponds to that found in many simple ionic nitrate salts [60] and the two pyridyl rings in complex 1 are coplanar with a dihedral angle of 0°, which is rare [61].…”

Section: Discussionmentioning

confidence: 98%

Two new lead(II) coordination polymer and discrete complex containing bipyridine ligands with different positioned methyl substituents: synthesis, characterization, crystal structure determination, and luminescent properties

Alizadeh

Amani

2011

Struct Chem

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Lead(II) coordination polymer [Pb(5,5 0 -dmbpy) (l-NO 3 ) 2 ] n (1) and mononuclear complex [Pb(6,6 0 -dmbpy) (NO 3 ) 2 ] (2) (where 5,5 0 -dmbpy is 5,5 0 -dimethyl-2,2 0 -bipyridine and 6,6 0 -dmbpy is 6,6 0 -dimethyl-2,2 0 -bipyridine) were synthesized from reaction of lead(II) nitrate with 5,5 0 -dmbpy and 6,6 0 -dmbpy, respectively. Both complexes were thoroughly characterized by elemental analysis, infrared, 1 H and 13 C NMR, UV-Vis, emission spectroscopy, as well as single-crystal X-ray diffraction. Polymer 1 possesses one-dimensional (1D) chain structure, whilst complex 2 exhibits a discrete complex which provide an extended chain parallel to the [001] direction, via weak intermolecular C-HÁÁÁO hydrogen bonding. Coordination number of Pb 2? in 1 and 2 are 8 and 6, respectively, with the stereochemically active lone pair, resulting in the hemidirected geometry for both complexes. The nitrate anions exhibit a tridentate chelating/bridging mode in 1, and a bi-chelating mode in 2. The supramolecular features in these complexes are guided/influenced by weak directional intermolecular C-HÁÁÁO hydrogen bonding (1 and 2) together with p-p and C-HÁÁÁp (1) interactions. The luminescence studies of 1 and 2 confirmed that the position of methyl substituent on 2,2 0 -bipyridine rings has a profound effect on the fluorescence emissions.

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“…7 O⋅⋅⋅O non-covalent interactions are also known to be responsible for the sulfate anion helices. 8 However, inter-POM cluster O⋅⋅⋅O contacts were not surveyed prior to this work. 9 We describe here a new type of three-dimensional supramolecular structure of an organic-inorganic hybrid compound (1 g, 4⋅13 mmol) was dissolved in 20 mL of water, in which 10 mL of acetic acid was added.…”

Section: Introductionmentioning

confidence: 99%

Non-covalent O···O interactions among isopolyanions using a cis-{MoO2} moiety by the assistance of N-H···O hydrogen bonds

2008

Self Cite

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An inorganic-organic hybrid material, [2-AmpH] 4 [Mo 8 O 26 ](1) has been isolated by the reaction of Na 2 MoO 4 ·2H 2 O with 2-aminopyrimidine (2-Amp) from an acidic aqueous medium. In this low pH synthesis, the organic molecule (2-Amp) gets mono-protonated (2-AmpH + ) and acts as the cation in stabilizing the octamolybdate anion in 1. Compound 1 crystallizes in the triclinic space group P-1 with a = 9⋅925 (3) (4), β = 64⋅907(4), γ = 89⋅506(4)°, Z = 1. An interesting three-dimensional supramolecular structure, having well-defined channels, is formed through N-H⋅⋅⋅O and C-H⋅⋅⋅O hydrogen bonds, in which the protonated organic cation plays a significant role. The crystal structure also reveals an unusual cluster-cluster (non-covalent O⋅⋅⋅O) interaction using cis-(MoO 2 } moieties of the isopolyanion. N-H⋅⋅⋅O hydrogen bonds, originated from pyridimidinium cation and isopolyanion, are found to influence to attain such non-covalent O⋅⋅⋅O interactions among polyoxometalate anions. An interesting helical arrangement, formed from isopolyanion and organic cation, is observed.

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Sulfate anion helices formed by the assistance of a flip-flop water chain

Abstract: A flip-flop extended water structure assists the formation of sulfate anion helices (both left- and right-handed) in a crystalline hydrate of a simple organic-inorganic compound [C6H10N2]SO4. 1.5H2O (1).

Cited by 36 publications

References 30 publications

Crowned Tetrameric Spirocyclic Water Chain: An Unusual Building Block of a Supramolecular Metal−Organic Host

Crowned Tetrameric Spirocyclic Water Chain: An Unusual Building Block of a Supramolecular Metal−Organic Host

Two new lead(II) coordination polymer and discrete complex containing bipyridine ligands with different positioned methyl substituents: synthesis, characterization, crystal structure determination, and luminescent properties

Non-covalent O···O interactions among isopolyanions using a cis-{MoO2} moiety by the assistance of N-H···O hydrogen bonds

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