Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1. Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, Saïbatou Yague, Florence Le Dret To cite this version: Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, et al.. Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1.. Journal de la Société Ouest-Africaine de Chimie, Société Ouest-Africaine de Chimie, 2013, 035, pp.57-63. hal-01074624 HAL Id: hal-01074624 https://hal.archives-ouvertes.fr/hal-01074624 Submitted on 15 Oct 2014 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Journal de la Société Ouest-Africaine de Chimie J. Soc. Ouest-Afr. Chim. Code Chemical Abstracts : JSOCF2 Cote INIST (CNRS France) : <27680> ISSN 0796-6687 18èmeAnnée, Juin 2013, N° 035 Site Web: http://www.soachim.org J. Soc. Ouest-Afr. Chim. (2013) 035 ; 57 - 63 Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]∞. Magatte Camaraa*, Carole Daiguebonneb,c, Olivier Guilloub,c, Albert Manga Badianea, Insa Badianea, Saïbatou Yaguea, Florence Le Dretb,c. aUniversité Assane Seck de Ziguinchor, LCPM – Groupe "Matériaux Inorganiques : Chimie Douce et Cristallographie", BP. 523 Ziguinchor – Sénégal bUniversité européenne de Bretagne, France. c INSA, UMR 6226 "Institut des Sciences Chimiques de Rennes", F-35708 Rennes. (Reçu le 10/04/2013 – Accepté après corrections le 30 /06/2013) Abstract : Reaction in gel between the sodium salt of 1,3,5-benzenetricarboxylic acid or trimesic (Na3[C6H3(COO)3] hereafter referenced as Na3btc) and calcium chloride has afforded single crystals of a bidimensional coordination polymer with chemical formula [Ca3(btc)2(H2O)12]∞. This compound crystallizes in the monoclinic system, space group C2/c (n° 15) with a = 19.3028 (16) Å, b = 11.4850 (9) Å, c = 13.0435 (12) Å, β = 106.394 (10)° and Z = 4. The crystal structure consists of a superposition of molecular planes that spread parallel to the, plane. Keywords : Ca(II); Crystal structure; Trimesate coordination polymers. Synthèse et caractérisation structurale d’un nouveau polymère de coordination à base de calcium et du ligand trimésate: [Ca3(btc)2(H2O)12]∞. Résumé : La réaction en milieu gel entre le sel de sodium de l'acide 1,3,5-benzènetricarboxylique ou trimésique (Na3 [C6H3 (COO)3] noté par la suite Na3btc) et le chlorure de calcium a donné des monocristaux d'un polymère de coordination bidimensionnel de formule chimique [Ca3(btc)2(H2O)12]∞. Ce composé cristallise dans le système monoclinique, groupe d'espace C2/c (n°15) avec a = 19,3028 (16) Å, b = 11,4850 (9) Å, c = 13,0435 (12) Å, β = 106,394 (10) ° et Z = 4. La structure cristalline consiste en une superposition de plans moléculaires se propageant parallèlement au plan, . Mots-clés : Ca(II); Structure cristalline; Polymères de coordination à base de l’acide trimésique. * Corresponding author: [email protected] , tel. (+221) 33938 85 86. fax: (+221) 33991 68 09 M. Camara et al 57 J. Soc. Ouest-Afr. Chim. (2013) 035 ; 57 - 63 1. Introduction. possible to obtain diffeifferent crystal structure by replacing an alkaline eartarth metal ion by another. Over the past few decaecades, a number of In order to initnitiate this study, we have coordination polymers have beenen published for their chosen to use Ca2+ as memetal ions because it is non- fascinating topologies coupled wwith their potential toxic and abundant in eearth crust and because its application in gas storageage[1-3], catalysis[4], ionic radius (1.00 Å) is similar to the one of the separation[5], luminescent devices[6,7] or lightest lanthanide ionions. Trimesate or 1,3,5- magnetism[8].For more than a dececade some of us are benzenetricarboxylate ligligand (hereafter symbolized engaged in that research field wiwith the objective of by btc2-) has been chosensen because it is a non-toxic designing new lanthanide-babased coordination and commercially availabilable ligand (See Scheme 1). polymers exhibiting interestesting luminescent Moreover, this ligand ppresents a great ability to properties[9,10] and/or porosity[11-13]. As far as this form infinite connectiontions with lanthanide metal second objective is targeted lalanthanide ions are ions[18-21] and a remarkakable versatility in adopting mainly used because of their abilibility to adopt various several different coordindination modes ranging from coordination modes. Actually,ly, it is generally unidentate to chelating aand bridging. At last, to the admitted that, due to the innennerness of their 4f best of our knowledge,, tthere are only few reported valence orbitals, lanthanide ions,s, in contrast with 3d trimesate coordination ppolymers that involve this metal ions, present only littlee ppreference in bond metallic cation[22,23]. direction[14]. However, shortagee oof these metals is a In lanthanide coordinatioion polymers three bonding global concern [15,16] and rationalalization of their use modes have been obsobserved according to the is mandatory. Therefore, we hhave undertaken a coordination environmenent of the COO− group [18,24] study in which alkaline earthh metal ions would as shown in Schemee 2: Mode I, acting as a replace lanthanide ions in coordordination polymers. unidentate ligand to bindind one metal ion; Mode II, Indeed, alkaline earth metall ions as well as acting as a bidentate ligangand to chelate one metal ion; lanthanide ions present little ppreference in bond Mode III, acting as a brbridging group between two direction and their coordination mmode is essentially metal ions. governed by steric hindrancee aand intermolecular In this paper wee wwish to report the synthesis interaction between ligands. MMoreover, alkaline and the crystal structurture of a new coordination earth ionic radii vary from 0.722 Å (Mg2+) to 1.35 Å polymer, [Ca (btc) (H OO) ] , that constitutes our (Ba2+) while lanthanide ionic radiadii vary from 0.86 Å 3 2 2 12 ∞ (Lu3+) to 1.03 Å (La3+)[17]. Therefrefore, it must be first result in this project. Scheme 1. 11,3,5-benzenetricarboxylate (or trimesate) ligandd ((btc3-). Modee I Mode II Modee IIIII Scheme 2. Bondingg mmodes in lanthanide-containing trimesate coordinaination polymers. M. Camara et al 58 J. Soc. Ouest-Afr. Chim. (2013) 035 ; 57 - 63 2. Experimental section hydrogen atoms. All non-hydrogen atoms were refined anisotropically using the SHELXL program 2.1 Synthesis [30]. Hydrogen atoms bound to the organic ligands Trimesic acid was purchased from Acros were localized at ideal positions. Hydrogen atoms Organics and used without further purification. of water molecules have not been localized. Calcium chloride was purchased from STREM Absorption corrections were performed using the Chemicals and used without further purification. Its facilities [29,31,32] included in the WINGX program sodium salt was prepared by addition of three suite [31].Crystal and final structure refinement data equivalents of sodium hydroxide to a suspension of are listed in Table I. Positional parameters, selected trimesic acid in de-ionized water until complete bond lengths and angles are listed in Tables II to dissolution. Then, the solution was evaporated to IV. dryness. The solid phase was then put in suspension in ethanol, stirred and refluxed during 1 h. After Table I. Crystal and final structure refinement data filtration and drying in a desiccator, a white powder for[Ca3(btc)2(H2O)12]∞. of tri-sodium trimesate was obtained. The yield of Molecular formula Ca3C18 O24H30 this synthesis is 90%. Anal. Calc.(found) for Formula weight 750.66 -1 System monoclinic C9H3O6Na3(MW = 276 g mol ) : C : 39.1%(39.0%) Space-group C2/c (n° 15) ; H : 1.1%(1.1%) ; O : 34.8%(34.5%) ; Na : a/Å 19.3028(16) 25.0%(25.4%). b/Å 11.4850(9) c/Å 13.0435(12) Single crystals of the coordination polymer α/° 90 were obtained by slow diffusions of dilute aqueous β/° 106.394(10) solutions of Ca(II) chloride (0.25 mmol in 20mL) γ/° 90 V/Å3 2774.1(4) and of sodium salt of trimesate (0.25 mmol in Z 4 -3 20mL) through an agar-agar gel bridge in a U- Dcalcd/g·cm 1.797 shaped tube. The gel was purchased from Acros F(000) 1560 µ/mm-1 0,703 Organics and jellified according to established Radiation Monochromated Mo Kα (λ = 0.71073 Å [25-27] procedure . After several weeks, colorless hkl Range -23 ≤ h ≤ 22; 0 ≤ k ≤ 14; 0 ≤ k ≤ 15 single crystals were obtained. θ Range (°) 2.09 ≤ θ ≤ 25.92 Data Collected 2547 Anal. Calc.(found) for [Ca3(btc)2(H2O)12]∞(MW = -1 Observed data (Fobs ≥ 1895 2 750.66 g mol ) : Ca : 16,0% (16,2%); C : 2σ (Fobs )) 28.8%(28.79%) ; H :4.0%(4.0%) ; O : Parameters refined 205 51.2%(51.0%). R (%) 4.14 Rw (%) 8.53 IR spectrum clearly shows vibration bands Goodness-of-fit 0.901 characteristic of the – (O– C – O) – groups around Final shift/error 0 -1 -1 a b 2 2 1/2 R1 = Σ[|Fo|-|Fc|]/Σ|Fo| ; Rw = [Σw(|Fo|-|Fc|) /Σw|Fo| ] 1560 cm and 1490 cm confirming the presence of 2 2 2 2 2 w = 1/[σ (Fo )+(0.0650×P) +42.0485×P] where P = (Fo +2×Fc )/3.