Bond lengths in organic and metal-organic compounds revisited:X—H bond lengths from neutron diffraction data

Abstract

The number of structures in the Cambridge Structural Database (CSD) has increased by an order of magnitude since the preparation of two major compilations of standard bond lengths in mid-1985. It is now of interest to examine whether this huge increase in data availability has implications for the mean bond-length values published in the late 1980s. Those compilations reported meanX—H bond lengths derived from rather sparse information and for rather few chemical environments. During the intervening years, the number of neutron studies has also increased, although only by a factor of around 2.25, permitting a new analysis ofX—H bond-length distributions for (a) organicX= C, N, O, B, and (b) a variety of terminal and homometallic bridging transition metal hydrides. New mean values are reported here and are compared with earlier results. These new overall means are also complemented by an analysis ofX—H distances at lower temperatures (T≤ 140 K), which indicates the general level of librational effects inX—H systems. The study also extends the range of chemical environments for which statistically acceptable meanX—H bond lengths can be obtained, although values from individual structures are also collated to further extend the chemical range of this compilation. Updated default `neutron-normalization' distances for use in hydrogen-bond and deformation-density studies are also proposed for C—H, N—H and O—H, and the low-temperature analysis provides specific values for certain chemical environments and hybridization states ofX.