Archive for the ‘crystal_structure_mining’ Category

Molecule of the year (month/week)?

Monday, December 12th, 2016

Chemical and engineering news (C&EN) is asking people to vote for their molecule of the year from six highlighted candidates. This reminded me of the history of internet-based “molecules of the moment“. It is thought that the concept originated in December 1995 here at Imperial and in January 1996 at Bristol University by Paul May and we were joined by Karl Harrison at Oxford shortly thereafter. Quite a few more such sites followed this concept, differentiated by their time intervals of weeks, months or years. The genre is well suited for internet display because of plugins or “helpers” such as Rasmol, Chime, Jmol and now JSmol which allow the three dimensions of molecular structures to be explored by the reader. Here I discuss a second candidate from the C&EN list; a ferrocene-based Ferris wheel[1],[2] (DOI for 3D model: 10.5517/CCDC.CSD.CC1JPKYQ) originating from research carried out at Imperial by Tim Albrecht, Nick Long and colleagues.

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References

  1. M.S. Inkpen, S. Scheerer, M. Linseis, A.J.P. White, R.F. Winter, T. Albrecht, and N.J. Long, "Oligomeric ferrocene rings", Nature Chemistry, vol. 8, pp. 825-830, 2016. https://doi.org/10.1038/nchem.2553
  2. Inkpen, Michael S.., Scheerer, Stefan., Linseis, Michael., White, Andrew J.P.., Winter, Rainer F.., Albrecht, Tim., and Long, Nicholas J.., "CCDC 1420914: Experimental Crystal Structure Determination", 2016. https://doi.org/10.5517/ccdc.csd.cc1jpkyq

Long C=C bonds.

Thursday, December 1st, 2016

Following on from a search for long C-C bonds, here is the same repeated for C=C double bonds.

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Long C-C bonds.

Wednesday, November 30th, 2016

In an earlier post, I searched for small C-C-C angles, finding one example that was also accompanied by an apparently exceptionally long C-C bond (2.18Å). But this arose from highly unusual bonding giving rise not to a single bond order but one closer to one half! How long can a “normal” (i.e single) C-C bond get, a question which has long fascinated chemists.

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Hydrogen bonding to chloroform.

Monday, November 14th, 2016

Chloroform, often in the deuterated form CDCl3, is a very common solvent for NMR and other types of spectroscopy. Quantum mechanics is increasingly used to calculate such spectra to aid assignment and the solvent is here normally simulated as a continuum rather than by explicit inclusion of one or more chloroform molecules. But what are the features of the hydrogen bonds that form from chloroform to other acceptors? Here I do a quick search for the common characteristics of such interactions.

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The largest C-C-C angle?

Tuesday, November 1st, 2016

I am now inverting the previous question by asking what is the largest angle subtended at a chain of three connected 4-coordinate carbon atoms? Let’s see if further interesting chemistry can be unearthed.

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The smallest C-C-C angle?

Monday, October 31st, 2016

Is asking a question such as “what is the smallest angle subtended at a chain of three connected 4-coordinate carbon atoms” just seeking another chemical record, or could it unearth interesting chemistry?

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An inorganic double helix: SnIP.

Sunday, October 16th, 2016
After sixty years of searching, the first non-templated double helical carbon-free inorganic molecular structure has been reported.[1] That is so neat that I thought to load the 3D coordinates here for you to interact with and then to explore the prospect of using these coordinates to add some value with e.g. some chiroptical calculations.

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References

  1. D. Pfister, K. Schäfer, C. Ott, B. Gerke, R. Pöttgen, O. Janka, M. Baumgartner, A. Efimova, A. Hohmann, P. Schmidt, S. Venkatachalam, L. van Wüllen, U. Schürmann, L. Kienle, V. Duppel, E. Parzinger, B. Miller, J. Becker, A. Holleitner, R. Weihrich, and T. Nilges, "Inorganic Double Helices in Semiconducting SnIP", Advanced Materials, vol. 28, pp. 9783-9791, 2016. https://doi.org/10.1002/adma.201603135

Catenated atoms and groups.

Thursday, October 13th, 2016

Chemists are as fond of records as any, although I doubt you will find many chemical ones in the Guinness world records list. Polytriangulanes chase how many cyclopropyl 3-rings can be joined via a vertex. Steve Bachrach on his blog reports some recent work by Peter Schreiner and colleagues[1] and the record for catenation of such rings appears to be 15. This led me to think about some other common atoms and groups. Here I have searched for crystal structures only; there may be examples of course for which no such data has been reported.

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References

  1. W.D. Allen, H. Quanz, and P.R. Schreiner, "Polytriangulane", Journal of Chemical Theory and Computation, vol. 12, pp. 4707-4716, 2016. https://doi.org/10.1021/acs.jctc.6b00669

σ or π? The ambident nucleophilic reactivity of imines: crystallographic and computational reality checks.

Wednesday, September 21st, 2016

Nucleophiles are species that seek to react with an electron deficient centre by donating a lone or a π-bond pair of electrons. The ambident variety has two or more such possible sources in the same molecule, an example of which might be hydroxylamine or H2NOH. I previously discussed how for this example, the energetics allow the nitrogen lone pair (Lp) to win out over the O Lp. Here, I play a similar game, but this time setting an NLp up against a π-pair.

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What’s in a name? Stabilised “nitrenes”.

Monday, September 19th, 2016

I previously explored stabilized “carbenes” with the formal structures (R2N)2C:, concluding that perhaps the alternative ionic representation R2N+=CNR2 might reflect their structures better. Here I take a broader look at the “carbene” landscape before asking the question “what about nitrenes?”

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