Title

Synthesis, Prediction, and Determination of Crystal Structures of (R/S)- and (S)-1,6-Dinitro-3,8-dioxa-1,6-diazaspiro[4.4]nonane-2,7-dione

Document Type

Article

Publication Date

11-1-2012

Department

Polymers and High Performance Materials

Abstract

Spiro-cyclic compounds frequently have screw-type symmetry (C-2) and are therefore optically active even though they do not contain an asymmetric carbon atom. (R/S)-1,6-Dinitro-3,8-dioxa-1,6-diazaspiro[4.4]nonane-2,7-dione is such a molecule. A blind crystal structure prediction study of structures containing one molecule in the asymmetric unit and considering all 230 space groups was undertaken using a dispersion-corrected density functional approach, which found a packing that matched the experimental structure of the (R/S) form as the lowest energy packing alternative. The densities of (R/S); and (S)- or (R)-1,6-dinitro-3,8-dioxa-1,6-diazaspiro[4.4]nonane-2,7-dione calculated for the Optimized experimental crystal structures confirmed that there is a small difference in the densities of the racemate and the optically active compound, with the optically active material being slightly more dense (1.875 versus 1.842 g/cm(3)). (R/S)-1,6-Dinitro-3,8-dioxa-1,6-diazaspiro[4.4]nonane-2,7-dione was synthesized as previously described Synthesis of the pure (S)-stereoisomer was accomplished by resolution of the racemic dithiourethane using a previously described method, followed by reaction of the pure enantiomer with acetyl nitrate. The absolute configuration of the l-3,8-dioxa-1,6-diazaspiro[4.4]nonane-2,7-dithione was established as (S)- by redetermining the crystal structure at 150 K. The racemate crystallizes in space group P2(1)/n with a density of 1.835 g/cm(3) (296 K). The (S)-compound crystallizes in space group P2(1)2(1)2(1) with a density of 1.854 g/cm(3) (296 K). This is the first demonstration of a difference in the density between the racemic mixture and the optically pure stereoisomer of an energetic material. It is also an apparent violation of Wallach's rule, which states that racemic crystals tend to be denser than their optically active counterparts.

Publication Title

Crystal Growth and Design

Volume

12

Issue

11

First Page

5292

Last Page

1346