Crystal structure of a one-dimensional coordination polymer of gadolinium dibromoacetate with 4,4'-bipyridine European Journal of Chemistry 9 (3) (2018) 178-181 European Journal of Chemistry View Journal Online View Article Online Crystal structure of a one-dimensional coordination polymer of gadolinium dibromoacetate with 4,4'-bipyridine Lesław Sieroń *, Agnieszka Czylkowska and Bartłomiej Rogalewicz Institute of General and Ecological Chemistry, Department of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland. leslaw.sieron@p.lodz.pl (L.S.), agnieszka.czylkowska@p.lodz.pl (A.C.), 211150@edu.p.lodz.pl (B.R.) * Corresponding author at: Institute of General and Ecological Chemistry, Department of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924 Lodz, Poland. Tel: +48.42.6313111 Fax: +48.42.6313103 e-mail: leslaw.sieron@p.lodz.pl (L. Sieroń). 10.5155/eurjchem.9.3.178-181.1742 Received: 28 May 2018 Received in revised form: 17 June 2018 Accepted: 18 June 2018 Published online: 30 September 2018 Printed: 30 September 2018 A new gadolinium(III) complex with 4,4’-bipyridine (4-bpy) and dibromoacetate ligand of general formula [Gd(4-bpy)(CBr2HCOO)3(H2O)]n, has been synthesized, crystallized and characterized by a single-crystal X-ray diffraction analysis. The gadolinium atom has an unsymmetrical eight-coordinate geometry, being coordinated by six oxygen atoms of dibromoacetate anions, one nitrogen atom of 4-bpy and one water molecule. The complex is a one-dimensional polymer as a result of dibromoacetate ligand bridging with the repeating monomeric units. There are π⋅⋅⋅π stacking interactions between the 4-bpy rings as well as O– H⋅⋅⋅O and O–H⋅⋅⋅N hydrogen bonds. Crystal Data for C16H13Br6GdN2O7 (Mw = 981.99 g/mol): triclinic, space group P-1 (no. 2), a = 9.7368(4) Å, b = 11.5416(4) Å, c = 11.7634(4) Å, α = 104.2750(10)°, β = 94.060(2)°, γ = 92.6900(10)°, V = 1275.08(8) Å3, Z = 2, T = 90 K, μ(CuKα) = 28.190 mm-1, Dcalc = 2.558 g/cm3, 8399 reflections measured (7.782° ≤ 2Θ ≤ 133.18°), 4006 unique (Rint = 0.0409, Rsigma = 0.0639) which were used in all calculations. The final R1 was 0.0527 (I > 2σ(I)) and wR2 was 0.1396 (all data). Gd complex 4,4’-Bipyridine Carboxylate ligands Octahedral geometry Coordination polymer Single crystal structure Cite this: Eur. J. Chem. 2018, 9(3), 178-181 Journal website: www.eurjchem.com 1. Introduction Nowadays, coordination polymers gain more and more interest due to their unique and interesting properties. A number of papers have recently been released proofing, that this field of study is especially attractive. Coordination polymers may be exploited in various areas of life and science [1]. They find application in catalysis and absorption [2-6]. Some of coordination polymers are gas absorbents [7,8]. The polymers are used also as sensors [9]. In our research as ligands we used 4,4’-bipyridine (4-bpy) and dibromoacetates. Both of them are interesting because of their structure. 4,4’-Bipyridine may be one or two donor ligand, which gives different possibilities of coordination. Two nitrogen atoms opposing themselves and two independent pyridine rings with ability to rotation along C–C bond give chance to create coordination polymers [10-14]. The structure will depend on the size and coordination number of metal ion as well as the presence of other ligands. In the case of carboxylate ligands, the possibility of various coordination with the central ion also gives the possibility of forming polymeric compounds. When coordination polymers are formed, not only ligands, but also central ions play a very important role. The greater coordination number of the metal, the greater possibility of polymer formation. Due to this feature, lanthanides are good central atoms. In the literature there is little information about similar types of compounds we have studied [15-18]. In our earlier papers we described very similar complexes [19,20]. In this paper we present synthesis and structure of new coordination polymer with general formulae [Gd(C10H8N2)(CBr2HCOO)3(H2O)]n. 2. Experimental A solution of gadolinium(III) dibromoacetate as hydrated product was prepared by dissolving freshly precipitated hydroxide in 2 mol/L CBr2HCOOH in stoichiometric quantities (pH ≌ 5.0). The content of Gd(III) ions in obtained solution of dibromoacetate was complexometrically (EDTA) determined. The mixed-ligand complex was prepared by mixing 12.4 mmol of 4-bpy in 96% v:v ethanol (31.25 mL) with the freshly obtained solution of 6.2 mmol metal dibromoacetate in 8.75 mL of water at room temperature. The obtained solid compound was filtered off; washed with 40% ethanol and then with ethanol and diethyl ether mixture (1:1, v:v), air dried at room temperature and described in [21]. ABSTRACT RESEARCH ARTICLE KEYWORDS European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2018 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. http://dx.doi.org/10.5155/eurjchem.9.3.178-181.1742 http://dx.doi.org/10.5155/eurjchem.9.3.178-181.1742 https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.9.3.178-181.1742&domain=pdf&date_stamp=2018-09-30 http://www.eurjchem.com/ http://dx.doi.org/10.5155/eurjchem.9.3.178-181.1742 mailto:leslaw.sieron@p.lodz.pl mailto:agnieszka.czylkowska@p.lodz.pl mailto:211150@edu.p.lodz.pl mailto:leslaw.sieron@p.lodz.pl http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.9.3.178-181.1742&domain=pdf&date_stamp=2018-09-30� Sieroń et al. / European Journal of Chemistry 9 (3) (2018) 178-181 179 Table 1. Crystal data and details of the structure refinement. Empirical formula (C16H13Br6GdN2O7)n Formula weight 981.99 Temperature (K) 90 Crystal system Triclinic Space group P-1 a, (Å) 9.7368(4) b, (Å) 11.5416(4) c, (Å) 11.7634(4) α, (°) 104.2750(10) β, (°) 94.060(2) γ, (°) 92.6900(10) Volume (Å3) 1275.08(8) Z 2 ρcalc (g/cm3) 2.558 μ (mm-1) 28.190 F(000) 906 Crystal size (mm3) 0.08 × 0.10 × 0.10 Radiation CuKα (λ = 1.54178 Å) 2Θ range for data collection (°) 7.78 to 133.18 Index ranges -11 ≤ h ≤ 11, -13 ≤ k ≤ 13, -13 ≤ l ≤ 9 Reflections collected 8399 Independent reflections 4006 [Rint = 0.041, Rsigma = 0.064] Data/restraints/parameters 4006/0/278 Goodness-of-fit on F2 1.096 Final R indexes [I≥2σ (I)] R1 = 0.0527, wR2 = 0.0539 Final R indexes [all data] R1 = 0.1386, wR2 = 0.1396 Largest diff. peak/hole (e Å-3) 0.22/-2.68 Figure 1. ORTEP drawing of independent fragment of the compound with the atom numbering scheme. Atomic displacement ellipsoids are drawn at 50% probability level. A new coordination polymer of gadolinium(III) of general formula [Gd(4-bpy)(CBr2HCOO)3(H2O)]n, has been obtained by slow crystallization from mother solution after separation of the solid complex Gd(4-bpy)(CBr2HCOO)3⋅3H2O [21] and characterized by single-crystal X-ray diffraction. 2.1. Instrumentation Single crystal X-ray diffraction data were collected at 90 K by the ω-scan technique using a Bruker AXS Smart APEX-II CCD [22] diffractometer with MonoCap capillary and 30W Incoatec Microfocus Source IµS with Montel optics and CuKα radiation (λ = 1.54178 Å). Absorption correction was based on symmetry equivalent reflections using the SADABS program [23]. The structure was solved by direct methods with SHELXT-2018/2 [24] and followed by successive Fourier and difference Fourier syntheses and refined by full-matrix least- squares on F2 using the SHELXL-2018/3 program [25]. All non-hydrogen atoms in the complex were refined with anisotropic thermal parameters. The hydrogen atoms were placed in calculated positions and refined isotropically with a riding model except for those bound to water molecules, which were initially located in a difference (Table 1). Software used to molecular graphics: Mercury [26]. Software used to geometry calculations: PLATON [27]. 3. Results and discussion The single crystal X-ray diffraction study at 90 K revealed that the compound crystallizes in the centrosymmetric triclinic space group P-1 as of general formula [Gd(4-bpy) (CBr2HCOO)3(H2O)]n and forms a complex polymer of gadolinium(III) with eight-coordinated GdIII atom by six oxygen atoms from six dibromoacetate anions, one oxygen atom of water molecule and one nitrogen atom from 4-bpy ligand. The crystal structure consists of two crystal- lographically independent formula units in the unit cell. A perspective view of the title compound structure, occupying the asymmetric unit of the unit cell, together with the atom numbering scheme is shown in Figure 1. The selected bond lengths and angles are listed in Table 2. The dibromoacetate groups coordinate the gadolinium ion in only a bridged bidentate mode. The crystal structure is built of chains of alternating bridges formed by two or four carboxylato groups of dibromoacetates that join the two neighboring GdIII centers, with metal separation distances of 5.2762(7) and 4.5366(7) Å, respectively. 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.3.178-181.1742 180 Sieroń et al. / European Journal of Chemistry 9 (3) (2018) 178-181 Table 2. Selected bond distances and bond angles for the title compound. Bond Bond length, Å Gd1–O1 2.353(7) Gd1–O2i 2.383(7) Gd1–O3 2.389(7) Gd1–O4ii 2.349(7) Gd1–O5 2.301(7) Gd1–O6ii 2.374(7) Gd1–O7 2.420(6) Gd1–N1 2.657(7) O1–C1 1.258(11) O2–C1 1.239(11) O3–C3 1.218(11) O4–C3 1.264(11) O5–C5 1.212(13) O6–C5 1.250(12) Bonds Bond angles, ° O1–Gd1–O2 i 86.8(2) O1–Gd1–O3 87.1(2) O1–Gd1–O4 ii 86.0(2) O1–Gd1–O5 70.4(2) O1–Gd1–O6 ii 145.8(2) O1–Gd1–O7 70.4(2) O1–Gd1–N1 69.5(2) O2i–Gd1–O3 145.8(2) O2i–Gd1–O4 ii 82.4(2) O2i–Gd1–O5 86.6(3) O2i–Gd1–O6 ii 142.6(2) O2i–Gd1–O7 77.0(2) O2i–Gd1–N1 73.7(2) O3–Gd1–O4 ii 121.3(2) O3–Gd1–O5 78.7(3) O3–Gd1–O6 ii 70.2(2) O3–Gd1–O7 69.3(2) O3–Gd1–N1 134.2(3) O4 ii–Gd1–O5 73.0(3) O4 ii–Gd1–O6 ii 80.6(3) O4 ii–Gd1–O7 141.1(3) O4 ii–Gd1–N1 71.6(3) O5–Gd1–O6 ii 119.2(3) O5–Gd1–O7 73.2(3) O5–Gd1–N1 141.3(3) O6 ii–Gd1–O7 133.6(2) O6 ii–Gd1–N1 69.4(3) O7–Gd1–N1 130.9(2) Symmetry code: (i) 1-x, 1-y, 1-z; (ii) -x, 1-y, 1-z. Figure 2. A fragment of the polymeric chain of the title compound, extending along the a axis. H-atoms have been omitted for clarity. A resulting polymeric structure extends in a straight line along a axis of the unit cell with the Gd1···Gd1’···Gd1’’ angle of 165.7° (Figure 2). The Gd–Ocarboxyl distances range from 2.301(7) to 2.389(6) Å, with a mean value of 2.358 Å and the Gd–Owater bond length is 2.420(6) Å. The 4-bpy ligand coordinates to Gd3+ ion through one N1 atom at a distance of 2.657(7) Å. The uncoordinated N2 atom of 4-bpy forms intermolecular hydrogen bond with coordinated water [O7–H72···N2, with d(O7···N2) = 2.792(12) Å and angle of O7–H72···N2 = 169°]. The neighboring polymeric chains are interlinked by these H- bonds leading to the formation of layers extending parallel to the (01-1) plane (Figure 3). The closest distance between adjacent 4-bpy moieties of C8···C111-x,-y,-z = 3.315(4) Å indicates π⋅⋅⋅π stacking interactions. The pyridyl rings in 4-bpy are not coplanar and the dihedral angle between them is 32.4°. The second hydrogen atom of the water molecule participates in the hydrogen bond with the O1 atom of one of the carboxyl groups [O7–H71···O1, with d(O7···O1) = 2.812(9) Å and angle of O7–H71···O1 = 165°]. The crystal is found to be isostructural with catena-(tris(µ2-2-fluorobenzoato-O,O')-(4- bpy)-aqua-terbium(III)) [28]. 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.3.178-181.1742 Sieroń et al. / European Journal of Chemistry 9 (3) (2018) 178-181 181 Figure 3. A part of the crystal packing diagram of [Gd(4-bpy)(CBr2HCOO)3(H2O)]n showing hydrogen bonds joining polymeric chains. 4. Conclusion The polymeric complex of gadolinium(III) with the 4,4’- bipyridine and dibromoacetate ligands was synthesized and characterized as [Gd(C10H8N2)(CBr2HCOO)3(H2O)]n. The structure of the complex was established via single-crystal X-ray diffraction showing eight-coordination geometry of the central Gd3+ ion. The crystal is built of chains of alternating bridges formed by two or four chelating dibromoacetate ligands in a bridged bidentate mode. The bridges join the neighboring Gd3+ centers, resulting in one-dimensional polymeric structure. Supporting information CCDC-1844278 contains the supplementary crystal- lographic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interests: The authors declare that they have no conflict of interest. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. ORCID Lesław Sieroń http://orcid.org/0000-0002-7797-0262 Agnieszka Czylkowska http://orcid.org/0000-0001-7157-5408 Bartłomiej Rogalewicz http://orcid.org/0000-0002-9899-6402 References [1]. Liu, Y.; Li, Z.; Niu, N.; Zou. J.; Liu, F. J. Appl. Polym. Sci. 2018, 135(25), 46400. [2]. Mochizuki, S.; Ogiwara, N.; Takayanagi, M.; Nagaoka, M.; Kitagawa, S.; Uemura, T. Nat. Commun. 2018, 9(1), 329. [3]. Zheng, T. R.; Blatov, V. A.; Zhang, Y. Q.; Yang, Ch. H.; Qian, L. L.; Li, K.; Li, B. L.; Wu, B. J. Lumin. 2018, 199, 126-132. [4]. Etaiw, S. E. -D. H.; El-bendary, M. M. J. Lumin. 2018, 199, 232-239. [5]. Berillo, D.; A. Cundy, A. Carbohydr. Polym. 2018, 192, 166-175. [6]. Zhang, X; Fu, J.; Zhang, D. S.; Geng, L. Polyhedron, 2018, 146, 12-18. [7]. Emerson, A. J.; Chahine, A.; Batten, S. R.; Turner, D. R. Coord. Chem. Rev. 2018, 365, 1-22. [8]. Gayen, S.; Saha, D. , Koner, S. J. Mol. Struct. 2018, 1162, 10-16. [9]. 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Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). 2018 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.9.3.178-181.1742 https://www.ccdc.cam.ac.uk/structures/ mailto:data_request@ccdc.cam.ac.uk http://orcid.org/0000-0002-7797-0262 http://orcid.org/0000-0001-7157-5408 http://orcid.org/0000-0002-9899-6402 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Instrumentation 3. Results and discussion 4. Conclusion Supporting information Disclosure statement ORCID References PrintField10: PrintField11: PrintField12: PrintField13: PrintField20: PrintField21: PrintField22: PrintField23: