Kryptoracemic compounds
In Chemistry, a kryptoracemic compound or kryptoracemate (sometimes false conglomerate) is a racemic compound crystallizing in a Sohncke space group.
In most of the cases, racemic compounds crystallize in centrosymmetric crystal structures. In a kryptoracemic compound the chemical composition of the crystal is racemic although the crystal belongs to space groups in which all enantiomerically pure molecules have to crystallize.
Crystallographically, in kryptoracemic compounds, the number of independent molecules in the asymmetric unit (Z′) is necessarily greater than 1 and should take an even value (to respect the racemic composition). By extension, the scalemic compounds (or unbalanced compounds), i.e. crystal with non-stoichiometric ratio of enantiomer, crystallizing in Sohncke space group are sometimes included in kryptoracemic compounds although they are not strito-sensu kryptoracemic.
Etymology
The term (kryptoracemate) was coined by Ivan Bernal who employed this term during a meeting of the American Crystallographic Association in 1995.[1]
The name is made of krypto (from Ancient Greek: κρυπτός, romanized: kryptos "the hidden one") and racemic. It comes from the fact that the racemic composition is "hidden" in a Sohncke space group (usually enantiomerically pure).
Frequency of kryptoracemic compounds in organic crystals
There is no space group restriction for the crystallization of racemic compound crystallizing either in centrosymmetric or in non-centrosymmetric space group (SG). The frequency of organic racemic compounds in the Cambridge Structural Database is summarized in the following table:[2]
| Centrosymmetric SGs | Non-centrosymmetric Achiral SGs | Kryptoracemic Compounds
(Non-centrosymmetric Chiral SGs or Sohncke SGs) | |
|---|---|---|---|
| Structure | Permitted | Permitted | Permitted |
| Frequency | 92.75% | 6.25% | 1% |
| Top SG | P21/c, C2/c, Pbca, P-1 | Pna21, Pca21, Cc | P21, P212121 |
Kryptoracemic compounds are thus very rare and represent circa 1% of the racemic compounds.[2] The frequency of kryptoracemic compounds in the whole organic Cambridge Structural Database was estimated to circa 0.4% to 0.8%.[2][3][4][5]
A review covering organometallic compounds with a stereogenic metal atom sorted a list of 26 possible kryptoracemic compounds.[6]
References
- ^ Bernal, Ivan (1995). "Abstract 4a.I.e.". ACA Annual Meeting, Montreal, Quebec, Canada.
- ^ a b c Clevers, Simon; Coquerel, Gérard (2020). "Kryptoracemic compound hunting and frequency in the Cambridge Structural Database". CrystEngComm. 22 (43): 7407–7419. doi:10.1039/D0CE00303D. ISSN 1466-8033. S2CID 225652171.
- ^ Fábián, László; Brock, Carolyn Pratt (2010-02-01). "A list of organic kryptoracemates". Acta Crystallographica Section B. 66 (1): 94–103. doi:10.1107/S0108768109053610. ISSN 0108-7681. PMID 20101089.
- ^ Grothe, E.; Meekes, H.; de Gelder, R. (2017-06-01). "Searching for stereoisomerism in crystallographic databases: algorithm, analysis and chiral curiosities". Acta Crystallographica Section B. 73 (3): 453–465. doi:10.1107/S2052520617001962. ISSN 2052-5206. PMID 28572555.
- ^ Rekis, Toms (2020-06-01). "Crystallization of chiral molecular compounds: what can be learned from the Cambridge Structural Database?". Acta Crystallographica Section B. 76 (3): 307–315. doi:10.1107/S2052520620003601. ISSN 2052-5206. PMID 32831251. S2CID 216451209.
- ^ Bernal, Ivan; Watkins, Steven (2015-03-01). "A list of organometallic kryptoracemates". Acta Crystallographica Section C. 71 (3): 216–221. doi:10.1107/S2053229615002636. ISSN 2053-2296. PMID 25734853.
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