Crystal and molecular structure of the 1 : 1 adduct between diphenyl sulphoxide and mercury (II) chloride

Biscarini, P.; Fusina, L.; Nivellini, G.D.; Mangia, A.; Pelizzi, Giancarlo

doi:10.1039/dt9730000159

Cited by 22 publications

(10 citation statements)

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“…naphthalene [46], f 3 = 110.6", (e2QqZ,h-'), = 39.211 MHz, and q = ,088. Substituting in(18) and(19) one obtains uB2 = 0.032 and oB1 = 0.493. Using Eqs.…”

mentioning

confidence: 99%

Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Wulfsberg

Weiß

1980

Ber Bunsenges Phys Chem

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Chemische Bindung i Kernquadrupolresonanz I Kristallstruktur I MolekiilstrukturHalogen atoms bridge metal atoms by forming two M -X bonds of about equal length ("symmetric bridging", as in cadmium halide adducts of oxygen-donor ligands), or by forming two bonds of significantly different lengths ("secondary bridging", as mercuric halide adducts of the same ligands). Halogen (%, "Br, '"I) NQR spectra of the title and related complexes show characteristic differences for the two types of bridging. Bridging halogen atoms (in nontransition metal halides) have lower frequencies than do analogous terminal halogen atoms; if the bridging is symmetric, the lowering depends on the bridging angle and is quite variable; if the bridging is secondary, the lowering is less but relatively constant. Asymmetry parameters for symmetrically-bridging halogens are ofteii large and depend on the bridging angle; those of secondary-bridging halogens are small. The temperature dependence of the NQR frequencies of symmetric bridgng halogens is normal negative; that of secondary bridging halogens is less negative than for analogous terminal halogens, and may even be positive. Two Townes-Dailey treatments of secondary bridging have been developed: one assumes the use of sp hybrid orbitals by the halogen, and the other uses pure p orbitals for the secondary bond. Analysis of the data leads to a picture of the formation of a "typical" secondary bond: 0.03 electrons are polarized or transferred towards the metal atom from the halogen pr orbital, and the halogen acquires an additional 0.01 electron in the original M -X bond.Halogenatome bilden mit Metallatomen Briickenbindungen aus, wobei die beiden Bindungslangen ungefahr gleich sein konnen (,,symmetrische Briickenbindung", wie in Cd-halidaddukten mit Sauerstoff-Donorliganden) oder wesentlich ungleich lang sein konnen (,,sekundare Briickenbindung", wie in Hg-halidaddukten). Halogen ("CI, "Br, '271)-NQR-spektren der genannten und ahnlicher Komplexe zeigen fur die beiden Typen von Briickenbindung charakteristische Unterschiede. Halogenbriickenatome zeigen in Verbindungen mit Hauptgruppenmetallen niedrigere Frequenzen als die endstandigen Halogene. 1st die Briicke symmetrisch, so hangt die Frequenzabsenkung 475 empfindlich vom Bruckenwinkel ab. Sekundare Bruckenbindung ist weniger effektiv. Die Asymmetrieparameter symmetrischer Briickenhalogenatome sind meist hoch und vom Winkel abhangig; bei sekundarer Briickenbindung sind sie niedrig. Die Temperaturabhangigkeit der NQR-frequenzen symmetrischer Briickenhalogenatome ist normal, d. h. negativ: in sekundareren Bruckenbindungen ist sie schwacher negativ als die terminaler Halogenatome, ja manchmal positiv. Zwei verschiedene Berechnungen der sekundiren Bruckenbindung nach Townes und Dailey wurden durchgefiihrt: einmal werden sp-Hybrid-Orbitale am Halogen angenommen, im anderen Fall reine p-Orbitale. Daraus ergibt sich fur eine ,,typische" sekundare Bruckenbindung von Halogenen: 0.03 Elektronen aus dem py-Orbital des Halogens sind in Richtung Metallato...

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“…naphthalene [46], f 3 = 110.6", (e2QqZ,h-'), = 39.211 MHz, and q = ,088. Substituting in(18) and(19) one obtains uB2 = 0.032 and oB1 = 0.493. Using Eqs.…”

mentioning

confidence: 99%

Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Wulfsberg

Weiß

1980

Ber Bunsenges Phys Chem

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“…Normally, for d 10 metal ions, the trigonal-bipyramidal polyhedron with D 3h -symmetry is preferred [14][15][16][17][18][19][20][21][22][23][24][25]. Thus, only a few square-pyramidal structures with C 4v -symmetry are known [26][27][28]. In general, all these structures are distorted due to the presence of different atom types and crystalpacking effects.…”

Section: Discussionmentioning

confidence: 99%

Crystal and molecular structure of [Hg3(H2pdm)2(Hpdm) (?-Cl)2Cl3]

Farfn¹,

Hpfl²

1998

Heteroatom Chem.

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The reaction between mercury(II)‐chloride and 2,6‐pyridinedimethanol provides a molecule with the empirical formula [Hg3(H2pdm)2‐(Hpdm) (μ‐Cl)2Cl3], whose crystal and molecular structure has been studied: a = 10.640(1), b = 10.818(2), c = 13.159(2) Å, α = 88.480(5), β = 75.067(4), γ = 89.736(5)°, V = 1463.0(4) Å3, Z = 2, P‐1. The molecule consists of a central [Hg(Hpdm)Cl] fragment that is connected by chloro bridges to twolateral fragments of identical constitution, [Hg‐(H2pdm)Cl2]. The coordination geometry around the central mercury atom is distorted octahedral, while the lateral metal atoms are located in significantly different, distorted square‐pyramidal polyhedrons. The tridentate ligand induces the formation of the square‐pyramidal environment instead of the trigonal‐bipyramidal one that is normally preferred by d10 systems. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:377–382, 1998

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“…Grafting pyridine groups onto a selected organic fragment is a method generally used by supramolecular chemists to construct various coordination architectures with interesting properties. However, the use of a pyridine-based sulfoxide as a ligand to construct coordination supramolecular architectures remains almost unexplored, except for several well characterized complexes of diphenyl sulfoxide (L), such as HgCl 2 (L) (Biscarini et al, 1973) Almeida et al, 1992) and the metal complexes with dipyrazinyl sulfoxide reported by our group recently (Wan et al, 2010).…”

Section: Commentmentioning

confidence: 99%

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]

Wan

Wang²,

Qiao³

et al. 2012

Acta Crystallogr C

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In the title complex, [Ag(NO(3))(C(9)H(7)N(3)OS)](n), η(1):η(1):η(1):μ(2)-bridging 2-(pyridin-4-ylsulfinyl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag(I) cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [ ̅201] direction. An FT-IR spectroscopic study shows a decreased stretching frequency for the η(1)-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and interconnected via O(S=O)···π(pyridine/pyrimidine) and C-H(pyridine)···O(NO(3)(-)) interactions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO(3)(-))···π(pyrimidine) interactions to form a three-dimensional supramolecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)···π(pyridine/pyrimidine) and anion(NO(3)(-))...π(pyrimidine) interactions in the supramolecular assembly of the title complex are presented.

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Crystal and molecular structure of the 1 : 1 adduct between diphenyl sulphoxide and mercury (II) chloride

Cited by 22 publications

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Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Crystal and molecular structure of [Hg3(H2pdm)2(Hpdm) (?-Cl)2Cl3]

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]

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Crystal and molecular structure of the 1 : 1 adduct between diphenyl sulphoxide and mercury (II) chloride

Cited by 22 publications

References 0 publications

Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Halogen‐Metal Secondary Bonding). An NQR Study in Mercury and Cadmium Halide Adducts of Polyethers

Crystal and molecular structure of [Hg3(H2pdm)2(Hpdm) (?-Cl)2Cl3]

Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ3N,O:N′]

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Supramolecular framework incatena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ³N,O:N′]