- Email: [email protected]
[CoI2(C6H4N3CH2CO2C4H2SCO2CH2C6H4N3)], a coordination polymer containing the thiophene-2,5-di(carboxylatomethylenebenzotriazole) bridging ligand: synthesis, structure, redox properties
Inorganic Chemistry Communications 5 (2002) 264–266 www.elsevier.com/locate/inoche
[CoI2(C6H4N3CH2CO2C4H2SCO2CH2C6H4N3)], a coordination polymer containing the thiophene-2,5-di(carboxylatomethylenebenzotriazole) bridging ligand: synthesis, structure, redox properties Christophe M. Thomas, Antonia Neels, Helen Stoeckli-Evans, Georg S€ uss-Fink
*
Institut de Chimie, Universit e de Neuch^ atel, Case Postale 2, Avenue de Bellevaux 51, CH-2007 Neuch^ atel, Switzerland Received 16 November 2001; accepted 6 February 2002
Abstract The title complex was obtained by reacting CoI2 with thiophene-2,5-di(carboxylatomethylenebenzotriazole) in dichloromethane. The single-crystal X-ray structure analysis of the green material reveals a polymeric chain of CoI2 units, tetrahedrally coordinated and connected by the 3-nitrogen atoms of the two benzotriazole groups of the multifunctional ligand. The paramagnetic cobalt(II) polymer can be oxidised by hexachloroethane to give the corresponding cationic cobalt(III) complex [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )(H2 O)2 ]þ which is diamagnetic and precipitates as the green–yellow chloride salt. Ó 2002 Elsevier Science B.V. All rights reserved. Keywords: Cobalt; Polymer; Nitrogen ligand
Coordination polymers have received much attention in recent years due to their potential use as materials with electronic and magnetic properties [1–4]. The multifunctional ligands used in this area are nitrogencontaining heterocycles, mainly pyrazine [5,6], 4; 40 -bipyridine [7] and 2; 20 :60 ; 200 -terpyridine [8,9] derivatives. Benzotriazole derivatives have not been encountered so far in coordination polymers. Recently we reported the synthesis of thiophene2,5-di(carboxylatomethylenebenzotriazole) (1) as a new multifunctional ligand for the rhodium-catalysed carbonylation of methanol [10]. From the reaction of 1 with [RhCl(CO)2 ]2 , the macrocyclic rhodium [Rh(CO)Cl(C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )]2 was isolated and characterised [10] (see Figs. 1 and 2). In this communication we report the reaction of 1 with cobalt(II) iodide to give the polymeric complex
*
(2). [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )] The reaction of CoI2 with 1 in dichloromethane at room temperature yields 2 quantitatively; 2 can be recrystal-
Corresponding author. Tel.: +41-32-7182405; fax: +41-32-7182511. E-mail address: georg.suess-fi[email protected] (G. S€ uss-Fink).
1387-7003/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 7 - 7 0 0 3 ( 0 2 ) 0 0 3 7 6 - 3
Fig. 1. Molecular structure of the asymmetric unit of 1.
C.M. Thomas et al. / Inorganic Chemistry Communications 5 (2002) 264–266
265
Fig. 2. Molecular structure of 1.
lised from acetone/hexane to give green, air-stable crystals. 1 The single-crystal X-ray structure analysis 2 reveals 2 to be a coordination polymer, each cobalt(II) centre being tetrahedrally coordinated to two iodine atoms and to the 3-N nitrogen atoms of two triazole ligands. The angles N(6)–Co(1)–N(2), N(6)–Co(1)–I(1), N(6)–Co(1)– I(2), N(1)–Co(1)–I(1), N(1)–Co(1)–I(2), I(1)–Co(1)–I(2) (103.55(14)°, 106.20(10)°, 116.79(10)°, 112.04(10)°, 106.51(10)°, 111.57(2)°, respectively) are not far from
1
Synthesis of 1: A solution of CoI2 (100 mg, 0.31 mmol) in dichloromethane (10 ml) was added dropwise to a solution of thiophene-2,5-di(carboxylato-methylenebenzotriazole) (140 mg, 0.32 mmol) in the same solvent (10 ml). The resulting solution was stirred at room temperature for 1 h. The product precipitated as green solid, which was filtered off, washed with hexane (20 ml) and dried in vacuo (174 mg, 75%). Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a 1:3 acetone/hexane solution. C20 H14 CoI2 N6 O4 S (747.17): calcd. C, 32.2; H, 1.9; N, 11.25. Found C, 32.6; H, 1.6; N, 11.3. IR (4000–400 cm1 ): 3029vw, 2979w, 1727vs, 1532m, 1452m, 1280s, 1240s, 1159m, 1069s, 989m, 743s, 543m, 493m cm1 . 2 Crystal data for 1: 0.5 C6 H12 , crystal dimensions 0:30 0:25 0:20 mm, Stoe Imaging Plate Diffractometer System, triclinic, space group , P 1, a ¼ 8:7294ð7Þ, b ¼ 12:8364ð11Þ, c ¼ 14:2166ð12Þ A a ¼ 90:648ð10Þ, b ¼ 91:198ð10Þ, c ¼ 95:957ð10Þ°, volume ¼ 1583:9ð2Þ 3 3 , Z ¼ 2, q A calcd ¼ 1:657 g/cm , F ð0 0 0Þ ¼ 764, kðMoKa Þ ¼ 0:71073 A, hrange ¼ 2:13–25:84°, 153(2) K, 12 460 measured reflections, 5713 independent reflections (Rint ¼ 0:0311) with I > 2rðIÞ, 363 refined parameters with R1 ¼ 0:0381 and xR2 ¼ 0:1020, max./min. residual 3 . The structure was solved by direct electron density 0.833/)0.514 eA methods using the program SHELXL-97 [12] and refined by full matrix least squares on F 2 with SHELXL-97 [13]. The hydrogen atoms were included in calculated positions and treated as riding atoms using SHELXL-97 default parameters. The compound crystallises with 1/2 molecule of hexane per asymmetric unit, all carbon atoms having occupancies of 0.5 or 0.25 are refined isotropically. An absorption correction using MULTISCAN in PLATON99 was applied (Tmin ¼ 0:385, Tmax ¼ 0:415). The figures were drawn with ORTEP32 [14]. Data collection was performed at )120 °C using Mo-Ka radiation ). 200 exposures (3 min per exposure) were obtained at (k ¼ 0:71073 A an image plate distance of 70 mm with 0 < / < 200° and with the crystal oscillating through 1° in u. The resolution was Dmin Dmax . 12.45–0.81 A
the ideal tetrahedral angle. The two cobalt–nitrogen , Co(1)–N(2) 2.020(3) A ] bonds [Co(1)–N(1) 2.035(4) A and the two cobalt–iodine bonds [Co(1)–I(1) 2.5563(7) , Co(1)–I(2) 2.5714(7) A ] are almost equal in length A (see Scheme 1). The paramagnetic cobalt(II) polymer can be oxidised to give the cobalt(III) complex [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )(H2 O)2 ]þ 3, which is probably also polymeric and precipitates as the chloride salt. The oxidation is achieved by a smooth anaerobic oxidation method developed by Herberich and Greiss [11] using hexachloroethane as the oxidant. Micro-analytical and NMR data 3 are consistent with the composition proposed.
Supplementary material Full crystallographic data for compound 2 may be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, quoting the CIF deposition number CCDC 173832 (Email: [email protected]).
Acknowledgements This work was supported by the Fonds National Suisse de la Recherche Scientifique (grant no 20 61227.00). 3
Synthesis of 3: To a solution of 1 (80 mg, 0.11 mmol) in THF (100 ml) was added 25 mg (0.11 mmol) of C2 Cl6 . The resulting solution was stirred at room temperature for 30 min. After evaporation of all volatile substances in vacuo, the residue was washed with ether to give 50 mg (55%) of 3. C20 H18 ClCoI2 N6 O6 S (818.6): calcd. C, 29.3; H, 2.2; N, 10.3. Found C, 29.6; H, 2.4; N, 10.0. IR (4000–400 cm1 ): 3035vw, 2975w, 1727vs, 1529m, 1455m, 1237s, 1159m, 1070s, 984m, 746s, 493m cm1 . 1 H NMR (CDCl3 ): d ¼ 8:12 (d, 2H), d ¼ 7:85 (d, 2H), d ¼ 7:64 (s, 2H), d ¼ 7:57 (t, 2H), d ¼ 7:46 (t, 2H), d ¼ 6:82 (s, 4H); d ¼ 1:60 (s, 2H), 13 C NMR (CDCl3 ): d ¼ 160:46, 146.31, 138.28, 134.73, 132.95, 128.94, 124.97, 120.44, 110.17, 68.82.
266
C.M. Thomas et al. / Inorganic Chemistry Communications 5 (2002) 264–266
Scheme 1.
References [1] [2] [3] [4]
J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 29 (1990) 1304. S.R. Batten, R. Robson, Angew. Chem. Int. Ed. 37 (1998) 1460. H.J. Choi, M.P. Suh, J. Am. Chem. Soc. 120 (1998) 10622. S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853. [5] M. Inoue, M. Kubo, Coord. Chem. Rev. 21 (1976) 1. [6] J. Steel, Coord. Chem. Rev. 106 (1990) 227. [7] E.C. Constable, P. Harverson, M. Oberholzer, Chem. Commun. (1996) 1821.
[8] E.C. Constable, A.M.W. Cargill Thompson, J. Chem. Soc., Dalton Trans. (1995) 1615. [9] E.C. Constable, P. Harverson, C.E. Housecroft, J. Chem. Soc., Dalton Trans. (1999) 3693. [10] C.M. Thomas, A. Neels, H. Stoeckli-Evans, G. S€ uss-Fink, Eur. J. Inorg. Chem. 12 (2001) 3005. [11] G.E. Herberich, G.J. Greiss, J. Organomet. Chem. 27 (1971) 113. [12] G.M. Sheldrick, Acta Cryst. A 46 (1990) 467. [13] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement, University of G€ ottingen, Germany, 1997. [14] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565.
[CoI2(C6H4N3CH2CO2C4H2SCO2CH2C6H4N3)], a coordination polymer containing the thiophene-2,5-di(carboxylatomethylenebenzotriazole) bridging ligand: synthesis, structure, redox properties Christophe M. Thomas, Antonia Neels, Helen Stoeckli-Evans, Georg S€ uss-Fink
*
Institut de Chimie, Universit e de Neuch^ atel, Case Postale 2, Avenue de Bellevaux 51, CH-2007 Neuch^ atel, Switzerland Received 16 November 2001; accepted 6 February 2002
Abstract The title complex was obtained by reacting CoI2 with thiophene-2,5-di(carboxylatomethylenebenzotriazole) in dichloromethane. The single-crystal X-ray structure analysis of the green material reveals a polymeric chain of CoI2 units, tetrahedrally coordinated and connected by the 3-nitrogen atoms of the two benzotriazole groups of the multifunctional ligand. The paramagnetic cobalt(II) polymer can be oxidised by hexachloroethane to give the corresponding cationic cobalt(III) complex [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )(H2 O)2 ]þ which is diamagnetic and precipitates as the green–yellow chloride salt. Ó 2002 Elsevier Science B.V. All rights reserved. Keywords: Cobalt; Polymer; Nitrogen ligand
Coordination polymers have received much attention in recent years due to their potential use as materials with electronic and magnetic properties [1–4]. The multifunctional ligands used in this area are nitrogencontaining heterocycles, mainly pyrazine [5,6], 4; 40 -bipyridine [7] and 2; 20 :60 ; 200 -terpyridine [8,9] derivatives. Benzotriazole derivatives have not been encountered so far in coordination polymers. Recently we reported the synthesis of thiophene2,5-di(carboxylatomethylenebenzotriazole) (1) as a new multifunctional ligand for the rhodium-catalysed carbonylation of methanol [10]. From the reaction of 1 with [RhCl(CO)2 ]2 , the macrocyclic rhodium [Rh(CO)Cl(C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )]2 was isolated and characterised [10] (see Figs. 1 and 2). In this communication we report the reaction of 1 with cobalt(II) iodide to give the polymeric complex
*
(2). [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )] The reaction of CoI2 with 1 in dichloromethane at room temperature yields 2 quantitatively; 2 can be recrystal-
Corresponding author. Tel.: +41-32-7182405; fax: +41-32-7182511. E-mail address: georg.suess-fi[email protected] (G. S€ uss-Fink).
1387-7003/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 7 - 7 0 0 3 ( 0 2 ) 0 0 3 7 6 - 3
Fig. 1. Molecular structure of the asymmetric unit of 1.
C.M. Thomas et al. / Inorganic Chemistry Communications 5 (2002) 264–266
265
Fig. 2. Molecular structure of 1.
lised from acetone/hexane to give green, air-stable crystals. 1 The single-crystal X-ray structure analysis 2 reveals 2 to be a coordination polymer, each cobalt(II) centre being tetrahedrally coordinated to two iodine atoms and to the 3-N nitrogen atoms of two triazole ligands. The angles N(6)–Co(1)–N(2), N(6)–Co(1)–I(1), N(6)–Co(1)– I(2), N(1)–Co(1)–I(1), N(1)–Co(1)–I(2), I(1)–Co(1)–I(2) (103.55(14)°, 106.20(10)°, 116.79(10)°, 112.04(10)°, 106.51(10)°, 111.57(2)°, respectively) are not far from
1
Synthesis of 1: A solution of CoI2 (100 mg, 0.31 mmol) in dichloromethane (10 ml) was added dropwise to a solution of thiophene-2,5-di(carboxylato-methylenebenzotriazole) (140 mg, 0.32 mmol) in the same solvent (10 ml). The resulting solution was stirred at room temperature for 1 h. The product precipitated as green solid, which was filtered off, washed with hexane (20 ml) and dried in vacuo (174 mg, 75%). Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a 1:3 acetone/hexane solution. C20 H14 CoI2 N6 O4 S (747.17): calcd. C, 32.2; H, 1.9; N, 11.25. Found C, 32.6; H, 1.6; N, 11.3. IR (4000–400 cm1 ): 3029vw, 2979w, 1727vs, 1532m, 1452m, 1280s, 1240s, 1159m, 1069s, 989m, 743s, 543m, 493m cm1 . 2 Crystal data for 1: 0.5 C6 H12 , crystal dimensions 0:30 0:25 0:20 mm, Stoe Imaging Plate Diffractometer System, triclinic, space group , P 1, a ¼ 8:7294ð7Þ, b ¼ 12:8364ð11Þ, c ¼ 14:2166ð12Þ A a ¼ 90:648ð10Þ, b ¼ 91:198ð10Þ, c ¼ 95:957ð10Þ°, volume ¼ 1583:9ð2Þ 3 3 , Z ¼ 2, q A calcd ¼ 1:657 g/cm , F ð0 0 0Þ ¼ 764, kðMoKa Þ ¼ 0:71073 A, hrange ¼ 2:13–25:84°, 153(2) K, 12 460 measured reflections, 5713 independent reflections (Rint ¼ 0:0311) with I > 2rðIÞ, 363 refined parameters with R1 ¼ 0:0381 and xR2 ¼ 0:1020, max./min. residual 3 . The structure was solved by direct electron density 0.833/)0.514 eA methods using the program SHELXL-97 [12] and refined by full matrix least squares on F 2 with SHELXL-97 [13]. The hydrogen atoms were included in calculated positions and treated as riding atoms using SHELXL-97 default parameters. The compound crystallises with 1/2 molecule of hexane per asymmetric unit, all carbon atoms having occupancies of 0.5 or 0.25 are refined isotropically. An absorption correction using MULTISCAN in PLATON99 was applied (Tmin ¼ 0:385, Tmax ¼ 0:415). The figures were drawn with ORTEP32 [14]. Data collection was performed at )120 °C using Mo-Ka radiation ). 200 exposures (3 min per exposure) were obtained at (k ¼ 0:71073 A an image plate distance of 70 mm with 0 < / < 200° and with the crystal oscillating through 1° in u. The resolution was Dmin Dmax . 12.45–0.81 A
the ideal tetrahedral angle. The two cobalt–nitrogen , Co(1)–N(2) 2.020(3) A ] bonds [Co(1)–N(1) 2.035(4) A and the two cobalt–iodine bonds [Co(1)–I(1) 2.5563(7) , Co(1)–I(2) 2.5714(7) A ] are almost equal in length A (see Scheme 1). The paramagnetic cobalt(II) polymer can be oxidised to give the cobalt(III) complex [CoI2 (C6 H4 N3 CH2 CO2 C4 H2 SCO2 CH2 C6 H4 N3 )(H2 O)2 ]þ 3, which is probably also polymeric and precipitates as the chloride salt. The oxidation is achieved by a smooth anaerobic oxidation method developed by Herberich and Greiss [11] using hexachloroethane as the oxidant. Micro-analytical and NMR data 3 are consistent with the composition proposed.
Supplementary material Full crystallographic data for compound 2 may be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, quoting the CIF deposition number CCDC 173832 (Email: [email protected]).
Acknowledgements This work was supported by the Fonds National Suisse de la Recherche Scientifique (grant no 20 61227.00). 3
Synthesis of 3: To a solution of 1 (80 mg, 0.11 mmol) in THF (100 ml) was added 25 mg (0.11 mmol) of C2 Cl6 . The resulting solution was stirred at room temperature for 30 min. After evaporation of all volatile substances in vacuo, the residue was washed with ether to give 50 mg (55%) of 3. C20 H18 ClCoI2 N6 O6 S (818.6): calcd. C, 29.3; H, 2.2; N, 10.3. Found C, 29.6; H, 2.4; N, 10.0. IR (4000–400 cm1 ): 3035vw, 2975w, 1727vs, 1529m, 1455m, 1237s, 1159m, 1070s, 984m, 746s, 493m cm1 . 1 H NMR (CDCl3 ): d ¼ 8:12 (d, 2H), d ¼ 7:85 (d, 2H), d ¼ 7:64 (s, 2H), d ¼ 7:57 (t, 2H), d ¼ 7:46 (t, 2H), d ¼ 6:82 (s, 4H); d ¼ 1:60 (s, 2H), 13 C NMR (CDCl3 ): d ¼ 160:46, 146.31, 138.28, 134.73, 132.95, 128.94, 124.97, 120.44, 110.17, 68.82.
266
C.M. Thomas et al. / Inorganic Chemistry Communications 5 (2002) 264–266
Scheme 1.
References [1] [2] [3] [4]
J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 29 (1990) 1304. S.R. Batten, R. Robson, Angew. Chem. Int. Ed. 37 (1998) 1460. H.J. Choi, M.P. Suh, J. Am. Chem. Soc. 120 (1998) 10622. S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853. [5] M. Inoue, M. Kubo, Coord. Chem. Rev. 21 (1976) 1. [6] J. Steel, Coord. Chem. Rev. 106 (1990) 227. [7] E.C. Constable, P. Harverson, M. Oberholzer, Chem. Commun. (1996) 1821.
[8] E.C. Constable, A.M.W. Cargill Thompson, J. Chem. Soc., Dalton Trans. (1995) 1615. [9] E.C. Constable, P. Harverson, C.E. Housecroft, J. Chem. Soc., Dalton Trans. (1999) 3693. [10] C.M. Thomas, A. Neels, H. Stoeckli-Evans, G. S€ uss-Fink, Eur. J. Inorg. Chem. 12 (2001) 3005. [11] G.E. Herberich, G.J. Greiss, J. Organomet. Chem. 27 (1971) 113. [12] G.M. Sheldrick, Acta Cryst. A 46 (1990) 467. [13] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure Refinement, University of G€ ottingen, Germany, 1997. [14] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565.