Correlation of Infrared Stretching Frequencies and Hydrogen Bond Distances in Crystals

Abstract

Empirical correlations between X–H≡Y distance R and frequency shift of the X–H stretching motion Δv are presented for O–H≡O, N–H≡O, and N–H≡N hydrogen bonds. A linear correlation is possible provided a distinct straight line is assumed for each hydrogen bond type. The equations of the best straight lines and standard deviations are: O−H···O Δν(cm−1)=4.43·103(2.84−R) σ(Δν)=199cm−1N−H···O Δν(cm−1)=0.548·103(3.21−R)σ(Δν)=24cm−1N−H···N Δν(cm−1)=1.05·103(3.38−R) ?

The crystal structure of HCrO2

“…-1. If this broad band be attributed to O-H vibration in OHO groups this absorption frequency indicates, using the plot of Pimentel & Sederholm (1956), an oxygen-oxygen distance across the hydrogen bond of approximately 2.45 A. An additional fairly strong band appeared at 1190 em.-~; this could be a hydrogen bonding frequency but more likely it arises from chromiumoxygen vibration.…”

“…-~, which very likely is due to O-H vibration in an OHO group. This frequency indicates, using the plot of Pimentel & Sederholm (1956), an oxygen-oxygen distance across the hydrogen bond of about 2.66-2.72 /~. The spectrum of HAIO~ bore no resemblance to that of HCrO~.…”

Microstructure Properties and Cellulase Hydrolysis Efficiency of Hybrid Pennisetum with [Amim]Cl Pretreatment

“…As shown in Fig. 1(b), the intra-molecular H-bonds for O(2)H … O(6) and O(3)H … O(5), and the inter-molecular H-bonds for O(6)H…O(3') appeared at wavenumbers of 3455 to 3410 cm -1 , 3375 to 3340cm -1 , and 3310 to 3230 cm -1 , respectively (Pimentel and Sederholm 1956). The peak-fitting parameters of different H-bonds are shown in Table 1.…”

Relationship between Infrared Peak Maximum Position and Molecular Interactions

“…Let us consider the case of two closely overlapped bands, both with Lorentzian band shape, comprising an apparent single composite peak, (1) where A 1 and A 2 are the maximum intensities of the two bands, ν 1 and ν 2 are the corresponding frequency positions of the two peak maxima, and w 1 and w 2 represent the one half of the full band widths measured at the half height of the maximum intensity. For convenience, we assume ν 1 > ν 2 .…”

“…Pimentel and Sederholm published a classical paper on the "empirical correlation" between shift of stretching frequencies and hydrogen bond distances in solid crystals. 1 Similarly, the energy of hydrogen bonds has been estimated with the equation developed by Struszczyk based on the extent of peak position shift. 2 The success of such empirical correlation provided the support for the so-called single band position shift model, where the position of the vibrational frequency of a single absorption band associated with a specific species under the influence of molecular interaction gradually changes as temperature or concentration of a mixture is changed.…”