{"id":24380,"date":"2021-10-17T10:09:12","date_gmt":"2021-10-17T09:09:12","guid":{"rendered":"https:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=24380"},"modified":"2021-10-17T12:10:01","modified_gmt":"2021-10-17T11:10:01","slug":"more-examples-of-crystal-structures-containing-embedded-linear-chains-of-iodines","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=24380","title":{"rendered":"More examples of crystal structures containing embedded linear chains of iodines."},"content":{"rendered":"
\n

The previous post<\/a> described the fascinating 170-year history of a crystalline compound known as Herapathite and its connection to the mechanism of the Finkelstein reaction via<\/em> the complex of Na+<\/sup>I2<\/sub>–<\/sup> (or Na2<\/sub>2+<\/sup>I4<\/sub>2-<\/sup>). Both compounds exhibit (approximately) linear chains of iodine atoms in their crystal structures, a connection which was discovered serendipitously. Here I pursue a rather more systematic way of tracking down similar compounds.<\/p>\n

Here is one search query which can be used in the CSD database of crystal structures. A chain of eight iodine atoms is defined, and the six angles subtended at iodine restricted to the range 150-180\u00b0 (i.e. linear). The inner six iodines are also defined as having only two bonded atoms.‡<\/sup><\/p>\n

\"\"<\/a><\/p>\n

This results in four hits (October 2021), three of which are shown below (the fourth, JOPLEH, contains chains of I8<\/sub>2-<\/sup> anions which do not appear to be infinitely repeating).<\/p>\n

    \n
  1. IQIVIP, containing the heterocyclic unit pyrroloperylene and connected chains of I29<\/sub>.[1]<\/a><\/span> See also DOI: 10.5517\/ccdc.csd.cc1m1tj0<\/a>
    \n
    \"\"

    Click to load 3D model of IQIVIP<\/p><\/div>
    \n
    \nThe truly remarkable feature is that the iodine chain appears to adopt a gentle right-handed helix in this isomer. One has to wonder how this might respond to light!<\/li>\n

  2. IQIVOV, closely related to IQIVIP, this time containing connected chains of gently spiralling I10<\/sub> groups.[1]<\/a><\/span> See also DOI: 10.5517\/ccdc.csd.cc1m1tk1<\/a>
    \n
    \"\"

    Click to load 3D model of IQIVOV<\/p><\/div>\n<\/li>\n

  3. WEVFAE, containing a tetramethyl stilbonium cation (an analogue of a tetramethylammonium cation) and this time infinite chains of I8<\/sub>3-<\/sup> anions.[2]<\/a><\/span>
    \n
    \"\"

    Click to load 3D model of WEVFAE<\/p><\/div>\n<\/li>\n<\/ol>\n

    The list is not long, but contains some fascinating examples of how iodine can catenate into infinitely long chains, sometimes linear (on the time averaged scale at the temperature of the data recording), sometimes gently helical and as with Herapathite, a rather more undulating motif. Again how the crystals of these compounds respond to light remains to be established. However it may be that since these three molecules are reported variously as being black-green, black and golden, some may be opaque to light in any orientation. I also note that linear chains of Ag, Ga In and Tl have also been reported in inorganic metal nitrides.[3]<\/a><\/span><\/p>\n

    \n

    ‡<\/sup> The same result is obtained if the specification of iodine in this search is replaced by “any” element. This post has DOI: 10.14469\/hpc\/9540. See also DOI: 10.1016\/j.hm.2005.11.005<\/a> for a connection between coiled chains of iodine atoms and Einstein’s theory of teleparallel spacetime, invoking torsional geometries.<\/p>\n

    References<\/h2>\n
    1. S. Madhu, H.A. Evans, V.V.T. Doan\u2010Nguyen, J.G. Labram, G. Wu, M.L. Chabinyc, R. Seshadri, and F. Wudl, \"Infinite Polyiodide Chains in the Pyrroloperylene\u2013Iodine Complex: Insights into the Starch\u2013Iodine and Perylene\u2013Iodine Complexes\", Angewandte Chemie International Edition<\/i>, vol. 55, pp. 8032-8035, 2016. https:\/\/doi.org\/10.1002\/anie.201601585<\/a>\n\n<\/li>\n
    2. U. Behrens, H.J. Breunig, M. Denker, and K.H. Ebert, \"Iodine Chains in (Me<sub>4<\/sub>Sb)<sub>3<\/sub>I<sub>8<\/sub> and Discrete Triiodide Ions in Me<sub>4<\/sub>AsI<sub>3<\/sub>\", Angewandte Chemie International Edition in English<\/i>, vol. 33, pp. 987-989, 1994. https:\/\/doi.org\/10.1002\/anie.199409871<\/a>\n\n<\/li>\n
    3. P. H\u00f6hn, G. Auffermann, R. Ramlau, H. Rosner, W. Schnelle, and R. Kniep, \"(Ca<sub>7<\/sub>N<sub>4<\/sub>)[M<sub><i>x<\/i><\/sub>] (M=Ag, Ga, In, Tl): Linear Metal Chains as Guests in a Subnitride Host\", Angewandte Chemie International Edition<\/i>, vol. 45, pp. 6681-6685, 2006. https:\/\/doi.org\/10.1002\/anie.200601726<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      The previous post described the fascinating 170-year history of a crystalline compound known as Herapathite and its connection to the mechanism of the Finkelstein reaction via the complex of Na+I2– (or Na22+I42-). Both compounds exhibit (approximately) linear chains of iodine atoms in their crystal structures, a connection which was discovered serendipitously. Here I pursue a […]<\/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":[2644,1745],"tags":[],"ppma_author":[2661],"class_list":["post-24380","post","type-post","status-publish","format-standard","hentry","category-chiroptics","category-crystal_structure_mining"],"yoast_head":"\nMore examples of crystal structures containing embedded linear chains of iodines. - 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=24380\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"More examples of crystal structures containing embedded linear chains of iodines. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"The previous post described the fascinating 170-year history of a crystalline compound known as Herapathite and its connection to the mechanism of the Finkelstein reaction via the complex of Na+I2– (or Na22+I42-). Both compounds exhibit (approximately) linear chains of iodine atoms in their crystal structures, a connection which was discovered serendipitously. Here I pursue a […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=24380\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2021-10-17T09:09:12+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2021-10-17T11:10:01+00:00\" \/>\n<meta property=\"og:image\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/10\/Screenshot-925-1024x248.jpg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"2 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"More examples of crystal structures containing embedded linear chains of iodines. - Henry Rzepa's Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=24380","og_locale":"en_GB","og_type":"article","og_title":"More examples of crystal structures containing embedded linear chains of iodines. - Henry Rzepa's Blog","og_description":"The previous post described the fascinating 170-year history of a crystalline compound known as Herapathite and its connection to the mechanism of the Finkelstein reaction via the complex of Na+I2– (or Na22+I42-). Both compounds exhibit (approximately) linear chains of iodine atoms in their crystal structures, a connection which was discovered serendipitously. 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We met for the first time in person for more than 18 months and were treated to a splendid and diverse program about the subject.\u2026","rel":"","context":"In "Chiroptics"","block_context":{"text":"Chiroptics","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2644"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/10\/NAIACE.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":2687,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=2687","url_meta":{"origin":24380,"position":1},"title":"Hypervalency: Third time lucky?","author":"Henry Rzepa","date":"October 23, 2010","format":false,"excerpt":"One approach to reporting science which is perhaps better suited to the medium of a blog than a conventional journal article is the opportunity to follow ideas in unexpected, even unconventional directions. Thus my third attempt, like a dog worrying a bone, to explore hypervalency. I have, somewhat to my\u2026","rel":"","context":"In "Hypervalency"","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2010\/10\/I8.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":13105,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13105","url_meta":{"origin":24380,"position":2},"title":"Halogen bonds 2: The DABCO-Iodine structure.","author":"Henry Rzepa","date":"November 30, 2014","format":false,"excerpt":"Pursuing the topic of halogen bonds, the system DABCO (a tertiary dibase) and iodine form an intriguing complex. Here I explore some unusual features of the structure HEKZOO as published in 2012 and ask whether the bonding between the donor (N) and the acceptor (I-I) really is best described as\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":[]},{"id":3670,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=3670","url_meta":{"origin":24380,"position":3},"title":"From the colour blue to molecular wires","author":"Henry Rzepa","date":"March 9, 2011","format":false,"excerpt":"In the previous post I pondered the colour of Monastral blue (copper phthalocyanine). Something did not quite fit, and so I speculated that perhaps some oxidation of the pigment might give a new species. This species (Cambridge code FEGJOQ) comprises two parts of copper phthalocyanine, 1 part of the corresponding\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":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/03\/FEGJOQ2.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":16497,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=16497","url_meta":{"origin":24380,"position":4},"title":"A wider look at chlorine trifluoride: crystal structures and data mining.","author":"Henry Rzepa","date":"June 10, 2016","format":false,"excerpt":"A while ago, I explored how the 3-coordinate halogen compound ClF3\u00a0is conventionally analyzed using\u00a0VSEPR (valence shell electron pair repulsion theory). Here I (belatedly) look at other such tri-coordinate halogen compounds using known structures gleaned from the\u00a0crystal structure database (CSD). The search query specifies\u00a07A as the central atom, defined with just\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":"","width":0,"height":0},"classes":[]},{"id":13003,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13003","url_meta":{"origin":24380,"position":5},"title":"More simple experiments with crystal data. The pyramidalisation of nitrogen.","author":"Henry Rzepa","date":"November 1, 2014","format":false,"excerpt":"We are approaching 1 million recorded crystal structures (actually, around 716,000 in the CCDC and just over 300,00 in COD). One delight with having this wealth of information is the simple little explorations that can take just a minute or so to do. This one was sparked by my helping\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":"pyramidal","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/11\/pyramidal.jpg?resize=350%2C200","width":350,"height":200},"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\/24380","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=24380"}],"version-history":[{"count":15,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/24380\/revisions"}],"predecessor-version":[{"id":24403,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/24380\/revisions\/24403"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=24380"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=24380"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=24380"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=24380"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}