Racemic and Enantiopure Camphene and Pinene Studied by the Crystalline Sponge Method

Abstract

The use of an achiral metal–organic framework for structure determination of chiral compounds is demonstrated for camphene and pinene. The structure of enantiopure β-pinene can be resolved using the crystalline sponge method. However, α-pinene cannot be resolved using enantiopure material alone because no ordering of guest molecules takes place in that case. Interestingly, enantiomeric pairs order inside the channels of the host framework when impure (+)-camphene is offered to the host, which is also the case when a racemic mixture of α-pinene is used. A mixture of (+)-α-pinene and (−)-β-pinene also leads to ordered incorporation in the host, showing the influence of the presence of an inversion center in the host framework. We further show that powder X-ray diffraction provides a direct view on incorporation of ordered guest molecules. This technique, therefore, provides a way to determine the optimal and/or minimal soaking time. In contrast, color change of the crystal only demonstrates guest uptake, not ordering. Moreover, we show that color change can also be caused by guest-induced host degradation.

The Crystalline Sponge Method in Water

“…Therefore, soaking these crystals with the 99 % pure (−)‐carvone solution would allow for enhancing the enantiomeric excess of the remaining solution. We previously observed the same phenomenon, the ordering of enantiomeric pairs for α‐pinene and camphene, in the ZnI 2 ‐tpt host, which also has a centrosymmetric space group. Finally, RUM‐3 was used to resolve the structures of ϵ ‐caprolactam (Figure ), and N ‐methylcaprolactam (SI‐3).…”

Applying the Crystalline Sponge Method to Agrochemicals: Obtaining X-ray Structures of the Fungicide Metalaxyl-M and Herbicide S-Metolachlor

“… 38 The host’s C2/ c symmetry was retained with four molecules of (+)-camphene and four molecules of (−)-camphene reported within the unit cell; this is comparable to that observed for guests D and E . 38 Another example is the encapsulation of 99% pure (−)-carvone into the host framework RUM-2. 31 Despite the very high enantiopurity of the guest, the host–guest complex was observed to crystallize in the space group C 2/ c .…”

The Crystalline Sponge Method in Water

“…Therefore, soaking these crystals with the 99% pure (-)-carvone solution would allow for enhancing the enantiomeric excess of the remaining solution. We previously observed the same phenomenon, the ordering of enantiomeric pairs for α-pinene and camphene, in the ZnI2-tpt host, 12 which also has a centrosymmetric space group.…”