The experimental charge distribution in sulfur-containing molecules. Structure determination and electron density study of NaSCN at reduced temperatures

Bats, Jan W.; Coppens, P.; Kvick,

doi:10.1107/s0567740877006451

Cited by 38 publications

(22 citation statements)

References 14 publications

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“…This fact suggests some neutralization of the Na + ion. In fact the net charge on the Na atom obtained by charge integration is +0.6 (1) e, being independent of radius r for the range of 1.25 <_ r < 1.50 A. Neutralization of the Na atom is observed to a greater extent in the crystals of NaSCN, NaCN.2H20 and Na sulfanilate.2H20 (Bats, Coppens & Kvick, 1977). In fact, the Na...O distance of 2.7619 (7) ,A, is longer than those observed in NaCN.2H20 (about 2.4 A).…”

Section: Residual Electron Densitymentioning

confidence: 95%

Electron-densoty distribution in crystals of K₂Na[Co(NO₂)₆]

Ohba¹,

Toriumi²,

Sato³

et al. 1978

Acta Crystallogr Sect B

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The electron-density distribution in crystals of K2Na[Co(NO2) 6] has been determined by the single-crystal Xray diffraction method. The residual electron density around the Co atom in the octahedral complex ion, [Co(NO2)6] 3-, comprises the eight positive peaks arranged at the corners of a cube [1.69 (14) e A -3 at 0.43 A from Co] and the six negative peaks on the Co-N bond [-0.79 (13) e A -3 at 0.62 A from Co]. The central Co atom is largely neutralized, the number of electrons within a sphere of radius 1.22 A (octahedral covalent radius of Co) being 26.3 (l). The valence-electron populations of the atoms were refined and the net charges of Co, N and O atoms were estimated to be +0.06 (6), -0.07 and -0.22 (2) e, respectively. A bonding peak with height 0.32 (10) e A -3 is observed between the N and O atoms. The bonding electron in the N-O bond is largely extended perpendicularly to the plane of the nitro group, showing some ~z-bond character.

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Section: Residual Electron Densitymentioning

confidence: 95%

Electron-densoty distribution in crystals of K₂Na[Co(NO₂)₆]

Ohba¹,

Toriumi²,

Sato³

et al. 1978

Acta Crystallogr Sect B

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“…This set of information is consistent with that obtained from the NaSCN crystals. [43][44][45] However, in the NaSCN crystal, each sodium atom was surrounded by three S and three N atoms. According to this coordination criterion for the Na atoms in the bulk, there has no obvious crystal structure formed yet for the sodium thiocyanate clusters that are investigated here, which is in accord with a recent theoretical study that illustrated striking differences between its gas-phase and crystal-phase structure.…”

Section: Summary Of Calculationsmentioning

confidence: 99%

Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

2015

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Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged Mx(SCN)x+1(-), doubly charged My(SCN)y+2(2-) (M = Na, K), and triply charged Kz(SCN)z+3(3-) anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions Mx(SCN)x+1(-) (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions My(SCN)y+2(2-) (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions Kz(SCN)z+3(3-) (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of Mx(SCN)x+1(-) with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged clusters were suppressed. The series of anion clusters investigated here range from molecular-like M1(SCN)2(-) to nano-sized K22(SCN)25(3-), providing a vivid molecular-level growth pattern reflecting the initial salt nucleation process.

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“…A relatively distinct single peak, compared to those at S(3) and S(5), was observed in the vicinity of S(1) in the axial direction. Recently, the electron density distributions around S atoms have been observed in low-temperature studies of several sulfur-containing compounds: sodium thiocyanate (Bats, Coppens & Kvick, 1977), 2,5-dimercaptothiadiazole (Bats, 1976), sulfamic acid (Bats, Coppens & Koetzle, 1977), sodium sulfanilate (Bats, 1977a) and dicyanotrisulfane (Bats, 1977b). The lone-pair peaks that they observed were at about 0.6-0.8 /k from the S nuclei, with peak heights of 0.15-0.45 e/k -3.…”

Section: Description Of the Structure And Discussionmentioning

confidence: 99%