{"id":8898,"date":"2013-01-04T11:01:12","date_gmt":"2013-01-04T11:01:12","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=8898"},"modified":"2023-09-16T19:47:09","modified_gmt":"2023-09-16T18:47:09","slug":"the-gauche-effect-seeking-evidence-by-a-survey-of-crystal-structures","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8898","title":{"rendered":"The gauche effect: seeking evidence by a survey of crystal structures."},"content":{"rendered":"
\n

\n\tI previously blogged about anomeric effects involving π electrons as donors<\/a>, and my post on the conformation of 1,2-difluorethane<\/a> turned out one of the most popular. Here I thought I would present the results of searching the Cambridge crystal database for examples of the gauche effect<\/strong><\/em>. The basic search is defined below\"CCDC-search\"\n<\/p>\n

\n\tHere, we define a four-atom torsion (TOR1), the two central carbon atoms having two groups R which can be only H or C. These two carbons are also defined as acyclic<\/em><\/strong>. The restrictions of the search as defined above also include R-factor < 0.05, not disordered and no errors. These combine to reduce the number of hits significantly (although not dissimilar distributions are obtained for less restricted searches). Each search takes only a few seconds, and one can rattle through many permutations very quickly.\n<\/p>\n

\n\tSo here come the results. First, QA=4M=F. All but one of the examples has a torsion in the region of 60°, the classic gauche effect!\n<\/p>\n

\"F-C-C-F\"

F-C-C-F<\/p><\/div>\n

\n\tNext, QA=O, 4M=F. Rather more hits, and the effect is almost as clear-cut. I should point out that the apparent "exceptions" to the gauche conformation may arise from structural restrictions, and each really would have to be inspected individually for the reasons (which I do not attempt here). \n<\/p>\n

\"OCCF\"

OCCF<\/p><\/div>\n

\n\tWith QA=4M=O,  one has many more instances. The effect is pretty convincing (it may be that hydrogen bonding may also control the conformation).\n<\/p>\n

\"O-C-C-O\"

O-C-C-O<\/p><\/div>\n

\n\tNow for QA=4M=Cl. The distribution is slanted more to the anti conformation, but there are still quite a few gauche.\n<\/p>\n

\"Cl-CC-Cl\"

Cl-CC-Cl<\/p><\/div>\n

\n\tWith QA=4M=S, the conformations are now almost all anti; the gauche effect is no more! \n<\/p>\n

\"S-C-C-S\"

S-C-C-S<\/p><\/div>\n

\n\tAnd for QA=4M=Br, it has also almost vanished (there is only one instance for I, and that too is antiperiplanar).\n<\/p>\n

\"Br-C-C-Br\"

Br-C-C-Br<\/p><\/div>\n

\n\tI now return to an earlier post in which I speculated that a cyano group might participate in the anomeric effect. Well here it is in the gauche effect; QA=CN, 4M = any of N,O,F,Cl,S. Quite a few gauche orientations for this pseudo-halogen!\n<\/p>\n

\"Neg-C-C-CN\"

Neg-C-C-CN<\/p><\/div>\n

\n\tAnother group that can act as a powerful acceptor of electrons from a donor is QA=N(Me)3<\/sub>+.<\/sup>. With 4M= N, O, F, Cl, here  the population of gauche conformers is large. QA=CF3<\/sub> is a similar group.\n<\/p>\n

\"Neg-C-C-NMe3\"

Neg-C-C-NMe3<\/p><\/div>\n

\"Neg-C-C-CF3\"

Neg-C-C-CF3<\/p><\/div>\n

\n\tOne can envisage other combinations. Thus QA= C=C, 4M = any of  N, O, F, Cl. An alkene seems one of the more powerful gauche effect participants!\n<\/p>\n

\"alkene-C-C-Neg\"

alkene-C-C-Neg<\/p><\/div>\n

\n\tAnd alkynes, perhaps slightly less so.\n<\/p>\n

\"Alkyne-C-C-Neg\"

Alkyne-C-C-Neg<\/p><\/div>\n

\n\tWhat about metals (QA = any metal, 4M = any of N, O, F, Cl, S). Well, not particularly biased either way, but clearly one in which the identity of the metal may matter.\n<\/p>\n

\"Metal-C-C-electronegative\"

Metal-C-C-electronegative<\/p><\/div>\n

\n\tI should end with inverting the model. If QA is electropositive (any group to the left of carbon, or below it in the periodic table) and 4M is electronegative, than they align almost exclusively anti-periplanar and not gauche. But notice how relatively few examples there are.  Synthetic chemists, please make more such molecules!\n<\/p>\n

\"Electropositive-C-C-Electronegative\"

Electropositive-C-C-Electronegative<\/p><\/div>\n

\n\tIf you thought the gauche effect was restricted to just a few molecules, think again!\n<\/p>\n

\n

Acknowledgments<\/h4>\n

This post has been cross-posted in PDF format at Authorea<\/a>.<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

I previously blogged about anomeric effects involving π electrons as donors, and my post on the conformation of 1,2-difluorethane turned out one of the most popular. Here I thought I would present the results of searching the Cambridge crystal database for examples of the gauche effect. The basic search is defined below Here, we define a four-atom […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[1745,4],"tags":[976,144,978,17,974,157,977,975,373],"ppma_author":[2661],"class_list":["post-8898","post","type-post","status-publish","format-standard","hentry","category-crystal_structure_mining","category-interesting-chemistry","tag-basic-search","tag-cambridge","tag-cf-3","tag-conformational-analysis","tag-gauche","tag-metal","tag-search-takes","tag-similar","tag-tutorial-material"],"yoast_head":"\nThe gauche effect: seeking evidence by a survey of crystal structures. - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=8898\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"The gauche effect: seeking evidence by a survey of crystal structures. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"I previously blogged about anomeric effects involving π electrons as donors, and my post on the conformation of 1,2-difluorethane turned out one of the most popular. Here I thought I would present the results of searching the Cambridge crystal database for examples of the gauche effect. 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This conjugation is more subtle in\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"C-H\/alkene interaction. Click for 3D.","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/02\/cis-butene-orbitals.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":12276,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12276","url_meta":{"origin":8898,"position":1},"title":"Artemisinin: are stereo-electronics at the core of its (re)activity?","author":"Henry Rzepa","date":"April 13, 2014","format":false,"excerpt":"Around 100 tons of the potent antimalarial artemisinin is produced annually; a remarkable quantity given its very unusual and fragile looking molecular structure (below). When I looked at this, I was immediately struck by a thought: surely this is a classic molecule for analyzing stereoelectronic effects (anomeric and gauche). Here\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"artemisinin1","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/04\/artemisinin1.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":17992,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17992","url_meta":{"origin":8898,"position":2},"title":"The conformation of enols: revealed and explained.","author":"Henry Rzepa","date":"April 6, 2017","format":false,"excerpt":"Enols are simple compounds with an OH group as a substituent on a C=C double bond and with a very distinct conformational preference for the OH group. Here I take a look at this preference as revealed by crystal structures, with the theoretical explanation. First, a search of the Cambridge\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/04\/All-1024x948.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":14485,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14485","url_meta":{"origin":8898,"position":3},"title":"A visualisation of the effects of conjugation; dienes and biaryls.","author":"Henry Rzepa","date":"August 25, 2015","format":false,"excerpt":"Here is another exploration of simple chemical concepts using crystal structures. Consider a simple diene: how does the central C-C bond length respond to the torsion angle between the two C=C bonds? The search of the CSD (Cambridge structure database) is constrained to R < 5%, no errors and no\u2026","rel":"","context":"In "Chemical IT"","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":24483,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=24483","url_meta":{"origin":8898,"position":4},"title":"Protein-Biotin complexes. Crystal structure mining.","author":"Henry Rzepa","date":"December 12, 2021","format":false,"excerpt":"In the previous post, I showed some of the diverse \"non-classical\"interactions between Biotin and a protein where it binds very strongly. Here I take a look at two of these interactions to discover how common they are in small molecule structures. The first search is of a CH hydrogen bond\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/12\/Screenshot-983-1024x893.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":10883,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10883","url_meta":{"origin":8898,"position":5},"title":"The butterfly effect in chemistry: Bimodal M~S bonds?","author":"Henry Rzepa","date":"July 14, 2013","format":false,"excerpt":"I noted previously that some 8-ring cyclic compounds could exist in either a planar-aromatic or a non-planar-non-aromatic mode, the mode being determined by apparently quite small changes in a ring substituent. Hunting for other examples of such chemistry on the edge, I did a search of the Cambridge crystal database\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/8898","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=8898"}],"version-history":[{"count":19,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/8898\/revisions"}],"predecessor-version":[{"id":26481,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/8898\/revisions\/26481"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=8898"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=8898"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=8898"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=8898"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}