{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T00:56:53Z","timestamp":1760144213652,"version":"build-2065373602"},"reference-count":57,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2024,3,27]],"date-time":"2024-03-27T00:00:00Z","timestamp":1711497600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["GR\/J85974\/01","EP\/D07746X\/1","44076"],"award-info":[{"award-number":["GR\/J85974\/01","EP\/D07746X\/1","44076"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000271","name":"Science and Technology Facilities Council","doi-asserted-by":"publisher","award":["GR\/J85974\/01","EP\/D07746X\/1","44076"],"award-info":[{"award-number":["GR\/J85974\/01","EP\/D07746X\/1","44076"]}],"id":[{"id":"10.13039\/501100000271","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A systematic study has been conducted on barbiturate complexes of all five alkali metals, Li\u2013Cs, prepared from metal carbonates or hydroxides in an aqueous solution without other potential ligands present, varying the stoichiometric ratio of metal ion to barbituric acid (BAH). Eight polymeric coordination compounds (two each for Na, K, and Rb and one each for Li and Cs) have been characterised by single-crystal X-ray diffraction. All contain some combination of barbiturate anion BA\u2212 (necessarily in a 1:1 ratio with the metal cation M+), barbituric acid, and water. All organic species and water molecules are coordinated to the metal centres via oxygen atoms as either terminal or bridging ligands. Coordination numbers range from 4 (for the Li complex) to 8 (for the Cs complex). Extensive hydrogen bonding plays a significant role in all the crystal structures, almost all of which include pairs of N\u2013H\u00b7\u00b7\u00b7O hydrogen bonds linking BA\u2212 and\/or BAH components into ribbons extending in one dimension. Factors influencing the structure adopted by each compound include cation size and reaction stoichiometry as well as hydrogen bonding.<\/jats:p>","DOI":"10.3390\/molecules29071495","type":"journal-article","created":{"date-parts":[[2024,3,27]],"date-time":"2024-03-27T12:41:57Z","timestamp":1711543317000},"page":"1495","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["The Sensitivity of Structure to Ionic Radius and Reaction Stoichiometry: A Crystallographic Study of Metal Coordination and Hydrogen Bonding in Barbiturate Complexes of All Five Alkali Metals Li\u2013Cs"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1643-5298","authenticated-orcid":false,"given":"William","family":"Clegg","sequence":"first","affiliation":[{"name":"Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gary S.","family":"Nichol","sequence":"additional","affiliation":[{"name":"Chemistry, School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, UK"},{"name":"School of Chemistry, Joseph Black Building, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,3,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1978","DOI":"10.1107\/S056774086900505X","article-title":"The crystal structure of two polymorphs of 5,5\u2032-diethylbarbituric acid (barbital)","volume":"25","author":"Craven","year":"1969","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1917","DOI":"10.1107\/S0567740871005090","article-title":"The crystal structure of polymorph IV of 5,5-diethylbarbituric acid (barbital)","volume":"27","author":"Craven","year":"1971","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"3719","DOI":"10.1107\/S0567740878011954","article-title":"The neutron crystal structure at \u221275 \u00b0C of polymorph II of 5,5-diethylbarbituric acid (barbital)","volume":"34","author":"McMullen","year":"1978","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1942","DOI":"10.1107\/S056774088200764X","article-title":"The charge density in polymorph II of 5,5-diethylbarbituric acid (barbital) at 198 K","volume":"38","author":"Craven","year":"1982","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"817","DOI":"10.1002\/crat.2170300619","article-title":"Crystal and molecular structure of 3,3-diethyl-2,4,6-[1H,3H,5H]pyrimidine trione","volume":"30","author":"Sambyal","year":"1995","journal-title":"Cryst. Res. Technol."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3031","DOI":"10.1021\/acs.jpca.7b11674","article-title":"Exploring the binding of barbital to a synthetic macrocyclic receptor. A charge density study","volume":"122","author":"Du","year":"2018","journal-title":"J. Phys. Chem. A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"249","DOI":"10.1107\/S0108270197013899","article-title":"5,5-Dihydroxyethylbarbituric acid","volume":"54","author":"Irles","year":"1998","journal-title":"Acta Crystallogr. Sect. C"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1107\/S205698901402619X","article-title":"Crystal structure of 5,5-bis(4-methylbenzyl)pyrimidine-2,4,6(1H,3H,5H)-trione monohydrate","volume":"71","author":"Suchetan","year":"2015","journal-title":"Acta Crystallogr. Sect. E"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"3583","DOI":"10.1021\/jp910778j","article-title":"Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid","volume":"114","author":"Roux","year":"2010","journal-title":"J. Phys. Chem. A"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Gelbrich, T., Braun, D.E., Oberparleiter, S., Schottenberger, H., and Griesser, U.J. (2016). The hydrogen bonded structures of two 5-bromobarbituric acids and analysis of unequal C5\u2013X and C5\u2013X\u2032 bond lengths (X = X\u2032 = F, Cl, Br or Me) in 5,5-disbustituted barbituric acids. Crystals, 6.","DOI":"10.3390\/cryst6040047"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"o771","DOI":"10.1107\/S1600536806056546","article-title":"5,5-Dibenzylbarbituric acid monohydrate","volume":"63","author":"Bhatt","year":"2007","journal-title":"Acta Crystallogr. Sect. E"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/S0040-4020(01)93197-7","article-title":"Polymorphism in substituted barbituric acids","volume":"7","author":"Cleverley","year":"1959","journal-title":"Tetrahedron"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2641","DOI":"10.1107\/S0567740880009594","article-title":"On the polymorphism of barbituric acid derivatives","volume":"36","author":"Caillet","year":"1980","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"979","DOI":"10.1021\/cg034209a","article-title":"An experimental and theoretical search for polymorphs of barbituric acid: The challenges of even limited conformational flexibility","volume":"4","author":"Lewis","year":"2004","journal-title":"Cryst. Growth Des."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"983","DOI":"10.1021\/cg049661o","article-title":"Investigating unused hydrogen bond acceptors using known and hypothetical crystal polymorphism","volume":"5","author":"Lewis","year":"2005","journal-title":"Cryst. Growth Des."},{"key":"ref_17","first-page":"166","article-title":"The crystal structure of anhydrous barbituric acid","volume":"16","author":"Bolton","year":"1963","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3046","DOI":"10.1039\/c2ce06636j","article-title":"On the high-temperature phase of barbituric acid","volume":"14","author":"Glinneman","year":"2012","journal-title":"CrystEngComm"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"881","DOI":"10.1107\/S0365110X61002539","article-title":"The crystal structure of barbituric acid dihydrate","volume":"14","author":"Jeffrey","year":"1961","journal-title":"Acta Crystallogr."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1655","DOI":"10.1107\/S0567740877006839","article-title":"A neutron diffraction study of barbituric acid dihydrate","volume":"33","author":"Ajaj","year":"1977","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2821","DOI":"10.1007\/s11696-019-00835-5","article-title":"Noncentrosymmetric organic crystals of barbiturates as potential nonlinear optical phores: Experimental and theoretical analyses","volume":"73","author":"Ivanova","year":"2019","journal-title":"Chem. Pap."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"464","DOI":"10.1107\/S0108768105017258","article-title":"A variable-temperature study of a phase transition in barbituric acid dihydrate","volume":"61","author":"Nichol","year":"2005","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4745","DOI":"10.1021\/acs.cgd.9b00633","article-title":"True polymorphic phase transition or dynamic crystal disorder? An investigation into the unusual phase behavior of barbituric acid dihydrate","volume":"19","author":"Paul","year":"2019","journal-title":"Cryst. Growth Des."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2382","DOI":"10.1021\/ja00085a018","article-title":"Design of organic structures in the solid state: Molecular tapes based on the network of hydrogen bonds present in the cyanuric acid\u00b7melamine complex","volume":"116","author":"Zerkowski","year":"1994","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1250","DOI":"10.1021\/cm00044a024","article-title":"Investigations into the robustness of secondary and tertiary architecture of hydrogen-bonded crystalline tapes","volume":"6","author":"Zerkowski","year":"1994","journal-title":"Chem. Mater."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"4298","DOI":"10.1021\/ja00089a019","article-title":"Steric control of secondary, solid-state architecture in 1:1 complexes of melamines and barbiturates that crystallize as crinkled tapes","volume":"116","author":"Zerkowsi","year":"1994","journal-title":"J. Am. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1021\/ar00049a006","article-title":"Noncovalent synthesis: Using physical-organic chemistry to make aggregates","volume":"28","author":"Whitesides","year":"1995","journal-title":"Acc. Chem. Res."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1016\/j.ica.2017.07.002","article-title":"Hydrated and anhydrous cobalt(II) barbiturates: Crystal structures, spectroscopic and thermal properties","volume":"467","author":"Golovnev","year":"2017","journal-title":"Inorg. Chim. Acta"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"569","DOI":"10.1134\/S1070328419080037","article-title":"Structure of barbituratobis(2,2\u2032-dipyridyl)copper(II) heptahydrate","volume":"45","author":"Golovnev","year":"2019","journal-title":"Russ. J. Coord. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1023\/A:1022592701631","article-title":"An approach to the structure and spectra of copper barbiturate trihydrate","volume":"28","author":"Xiong","year":"2003","journal-title":"Trans. Met. Chem."},{"key":"ref_31","first-page":"270","article-title":"Synthesis and crystal structure of bis(barbiturate)triwater complex of copper(II)","volume":"22","author":"Yang","year":"2003","journal-title":"Chin. J. Struct. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"392","DOI":"10.1107\/S2052520615013505","article-title":"Charge density and optical properties of multicomponent crystals containing active pharmaceutical ingredients or their analogues","volume":"71","author":"Gryl","year":"2015","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"418","DOI":"10.1016\/j.molstruc.2019.02.017","article-title":"Investigation of structural analysis and thermostatic properties of thermal and UV stabilizer as organometallic Sn(II), Cu(II) and Cd(II) barbiturate complexes","volume":"1184","author":"Kavlak","year":"2019","journal-title":"J. Mol. Struct."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"88","DOI":"10.1016\/j.inoche.2018.09.011","article-title":"Crystal structures of [Cu2(2,2\u2032-bipyridine-N,N\u2032)2(H2O)2(\u03bc2-OH)2](barbiturate)2\u00b72H2O and [Cu(2,2\u2032-bipyridine-N,N\u2032)(H2O)(barbiturate-O)Cl]\u00b72H2O","volume":"97","author":"Golovnev","year":"2018","journal-title":"Inorg. Chem. Commun."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"901","DOI":"10.1134\/S1070328410120067","article-title":"The first barbiturate-bridged manganese(II) polymer: Synthesis, crystal structure, and magnetic properties","volume":"36","author":"Chu","year":"2010","journal-title":"Russ. J. Coord. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"m850","DOI":"10.1107\/S1600536807008185","article-title":"(Barbiturato-\u03baO)[hydridotris(5-methyl-3-phenyl-1-pyrazolyl)borato-\u03ba3N2,N2\u2032,N2\u2033]zinc(II) methanol solvate","volume":"63","author":"He","year":"2007","journal-title":"Acta Crystallogr. Sect. E"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"15962","DOI":"10.1021\/acs.inorgchem.0c02433","article-title":"Explorations of second-order nonlinear optical materials in the alkaline earth barbiturate system: Noncentrosymmetric Ca(H3C4N2O3)2\u00b7H2O and centrosymmetric Sr(H5C8N4O5)2\u00b74H2O","volume":"59","author":"Xu","year":"2020","journal-title":"Inorg. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1984","DOI":"10.1080\/00958972.2017.1319943","article-title":"Bis(\u03bc3-barbiturato\u2212O,O,O\u2032)-(\u03bc2-aqua)-aqua-barium(II): Crystal structure, spectroscopic and thermal properties","volume":"70","author":"Solovyov","year":"2017","journal-title":"J. Coord. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"7598","DOI":"10.1039\/c3ce40938d","article-title":"From molecular crystals to salt co-crystals of barbituric acid via the carbonate ion and an improvement of the solid state properties","volume":"15","author":"Chierotti","year":"2013","journal-title":"CrystEngComm"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"746","DOI":"10.1134\/S0036023617060092","article-title":"Polymeric lithium(I) diaquabarbiturate: Crystal structure","volume":"62","author":"Golovnev","year":"2017","journal-title":"Russ. J. Inorg. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"m571","DOI":"10.1107\/S1600536811012657","article-title":"Rubidium 2,4,6-trioxo-1,3-diazinan-5-ide\u20131,3-diazinane-2,4,6-trione\u2013water (1\/1\/1)","volume":"67","author":"Gryl","year":"2011","journal-title":"Acta Crystallogr. Sect. E"},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Yang, L., Powell, D.R., and Houser, R.P. (2007). Structural variation in copper(I) complexes with pyridylmethylamide ligands: Structural analysis with a new four-coordinate geometry index, \u03c44. Dalton Trans., 955\u2013964.","DOI":"10.1039\/B617136B"},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Clegg, W., and Nichol, G.S. (2024). Investigating the competitive factors of metal\u2013anion coordination, coordination by water, and hydrogen bonding in complexes of cyanuric acid with the alkaline earth metals. Crystals, 14.","DOI":"10.20944\/preprints202401.0669.v1"},{"key":"ref_44","unstructured":"Bruker (2001). SMART, Bruker AXS Inc."},{"key":"ref_45","unstructured":"Bruker (2003). APEX2, Bruker AXS Inc."},{"key":"ref_46","unstructured":"Hooft, R.W.W. (1999). COLLECT, Nonius BV."},{"key":"ref_47","unstructured":"Bruker (2001). SAINT, Bruker AXS Inc."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1107\/S0021889891010634","article-title":"Indexing in single-crystal diffractometry with an obstinate list of reflections","volume":"25","author":"Duisenberg","year":"1992","journal-title":"J. Appl. Crystallogr."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"220","DOI":"10.1107\/S0021889802022628","article-title":"An intensity evaluation method: EVAL-14","volume":"36","author":"Duisenberg","year":"2003","journal-title":"J. Appl. Crystallogr."},{"key":"ref_50","unstructured":"Sheldrick, G.M. (2003). SADABS, University of G\u00f6ttingen. Version 2.09."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"1103","DOI":"10.1107\/S0021889803012585","article-title":"SIR2002: The program","volume":"36","author":"Burla","year":"2003","journal-title":"J. Appl. Crystallogr."},{"key":"ref_52","unstructured":"Sheldrick, G.M. (2001). SHELXTL, Bruker AXS Inc.. Version 6."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. C"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"168","DOI":"10.1107\/S0021889802000249","article-title":"The derivation of non-merohedral twin laws during refinement by analysis of poorly fitting intensity data and the refinement of non-merohedrally twinned crystal structures in the program CRYSTALS","volume":"35","author":"Cooper","year":"2002","journal-title":"J. Appl. Crystallogr."},{"key":"ref_55","unstructured":"Pink, M., and Young, J.V.G. (2001). ROTWIN, University of Minnesota."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"389","DOI":"10.1107\/S0108768102003324","article-title":"New software for searching the Cambridge Structural Database and visualizing crystal structures","volume":"58","author":"Bruno","year":"2002","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"1555","DOI":"10.1002\/anie.199515551","article-title":"Patterns in hydrogen bonding: Functionality and graph set analysis in crystals","volume":"34","author":"Bernstein","year":"1995","journal-title":"Angew. Chem. Int. Ed. Engl."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/7\/1495\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:19:32Z","timestamp":1760105972000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/7\/1495"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,3,27]]},"references-count":57,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2024,4]]}},"alternative-id":["molecules29071495"],"URL":"https:\/\/doi.org\/10.3390\/molecules29071495","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2024,3,27]]}}}