H₂S⋯Cl₂characterised in a pre-reactive gas mixture of hydrogen sulfide and chlorine through rotational spectroscopy: the nature of the interaction

Abstract

The ground-state rotational spectra of five isotopomers (H,S. . .35CI,, H, S. . .35C137CI, H, S. --37C135CI, HDS. . s ~~C I , and D,S-. .35C12) of a complex formed by hydrogen sulfide and chlorine have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The reaction of H , S and CI, was precluded by employing a fast-mixing nozzle. The rotational constant i ( B o + Co), the centrifugal distortion constant D, and the CI-nuclear quadrupole coupling constants xaa(Cli) and xaa(CI0) (i = inner CI atom, o = outer CI atom) were determined in each case. The rotational constants were interpreted, under the assumption of unperturbed monomer geometries, to establish that H, S. . CI, has a geometry in which the SClCl nuclei are collinear or almost collinear, with the CI, subunit nearly perpendicular to the plane of the H, S nuclei. The observed angular geometry is rationalised in terms of a set of rules previously used to discuss hydrogen-bonded complexes B.. -HX. The strength of the interaction, as measured by the force constant k, (determined from D,), and the electric charge redistribution within CI, on formation of H,S -CI, [determined from the xaa(Clx)] both indicate that the complex is of the weak, outer type described by Mulliken. A comparison of the properties of H,S-. CI, and H,S-.-HCI reveals that the complexes are similar in several respects and explanations for these similarities are given in terms of the electric charge distributions of CI, and HCI. In particular, the reason why the angular geometries of both can be predicted by some electrostatically based rules is discussed.

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

“…2. From Table 2, the calculated halogen-bond length d SÁÁÁX (the distance between sulfur and halogen atoms) at the MP2(full)/aug-cc-pVDZ level is in good agreement with the experimental data [45][46][47][48][49]. The halogen-bond length d SÁÁÁX for all the complexes studied are within a range from 2.529 to 3.297 Å , all of which are less than the sums of van der Waals (vdW) radii of sulfur atom and corresponding X atoms (vdW radii for S, Cl and Br are 1.80, 1.75, and 1.85 Å , respectively).…”

Comparison between standard and counterpoise-corrected optimization using some hydrogen and halogen bonded systems

“…The B Á Á Á X bond lengths have previously been determined by experimental techniques for some dimers [20][21][22][23][24][25][26][27][28][29][30][31][32] Some optimized structures are minimum stationary points at the standard level whereas they are maximum stationary points at the CP-corrected level, and vice versa. For example, linear structures of N 2 Á Á Á HCl and N 2 Á Á Á HBr are ground states by the CP-corrected method and, with negative vibrational frequencies, are transition states by the standard method.…”

Präreaktive Komplexe der Dihalogene XY mit Lewis-Basen B in der Gasphase: eine systematische Studie der Halogen-Analoga B⋅⋅⋅XY der Wasserstoffbrückenbindungen B⋅⋅⋅HX

“…Die B-HX-Wechselwirkungen sind im allgemeinen vom schwachen elektrostatischen Typ, [67,68] und die k s -Werte lassen sich bei einer groûen Zahl von Komplexen über die empirische Gleichung (10) berechnen. [61,62] [32] (3.6) 5.1 [40] (6.3) 6.3 [45] (6.3) 7.0 [53] (6.9) C 2 H 2 ± (2.0) 5.6 [36] (5.4) ± (7.8) 9.4 [47] (9.5) 10.0 [54] (10.3) C 2 H 4 ± (2.2) 5.9 [27] (6.0) ± (8.7) 10.5 [46] (10.6) 11.0 [55] (11.5) HCN 2.6 [63] (2.3) 6.6 [37] (6.2) ± (9.1) 11.1 [49] (11.0) 12.3 [56] (12.0) H 2 S 2.4 [64] (2.6) 6.3 [35] (6.9) ± (10.0) 12.2 [48] (11.0) 13.3 [57] (13.2) NH 3 4.7 [65] (4.7) 12.7 [38] (12.6) 18.5 [39] ± (11.8) 5.9 (5.9) 5.2 [118] (4.9) H 2 S 12.0 (12.0) 6.8 (6.0) 5.9 (5.0) HCN 18.2 (18.2) 9.1 (9.1) 7.3 (7.7) NH 3 32.8 (30.0) [b] 17.6 (14.9) [76] 13.4 (12.5) [77] [a] Die experimentellen Werte sind aus Lit. [61] oder [62], falls nicht anders angegeben.…”

“…Gemäû Regel (1) sollte in der Gleichgewichtsgeometrie der H 2 S´´´XY-Komplexe die Achse des XY-Moleküls senkrecht zur H 2 S-Ebene stehen. Tatsächlich erlauben detaillierte Interpretationen der Halogen-Kernquadrupolkopplungskonstanten der Komplexe H 2 S´´´Cl 2 , [35] H 2 S´´´BrCl [48] und H 2 S´´´ClF [57] den Schluû, daû die Atomkerne S, X und Y in diesen drei Komplexen bis auf ca. 18 kollinear sind.…”