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Methylene Blue Interactions: Complexation and Metallate Formation

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Methylene Blue Interactions: Complexation and Metallate Formation Inorganica Chimica Acta 360 (2007) 1799–1808 www.elsevier.com/locate/ica Mercury(II)–methylene blue interactions: Complexation and metallate formation Mani Mohan Raj a, Allimuthu Dharmaraja a, Savaridasson Jose Kavitha a, Krishnaswamy Panchanatheswaran a,*, Daniel E. Lynch b a School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, Tamil Nadu, India b Faculty of Health and Life Sciences, Coventry University, Coventry CV1 5FB, UK Received 28 March 2006; received in revised form 4 September 2006; accepted 12 September 2006 Available online 19 October 2006 Abstract Reactions of HgX2 (X = Cl, Br, I) with methylene blue (MB) chloride dihydrate and the reaction of HgCl2 with MB nitrate dihydrate have been undertaken in an attempt to prepare metal derivatives of MB. The products were characterized by elemental analysis, UV–Vis, 1 IR, H NMR spectroscopy and X-ray crystallography. The reaction of HgCl2 with MB chloride dihydrate and subsequent crystallization in a DMF/H2O mixture yielded the products (1 and 2) with different crystal morphologies. The structure of complex 1 represents the first structural report of a complex of MB with any metal ion. The efficacy of MB to act as a ligand in spite of its cationic nature is thus demonstrated. The structure of 1 comprises a distorted tetrahedral geometry around Hg(II); the coordination valencies being provided 2À by three chloride ions and a MB cation. The structure of 2 is a salt consisting of an HgCl4 anion and two MB cations. The reaction of 2À HgI2 and HgBr2 with MB chloride dihydrate yielded salts 3 and 4 with Hg2X6 (X = Br or I) anions and MB cations. A mixed salt 5, whose anions comprise mercury(II), chloride and nitrate species resulted from the reaction between HgCl2 with MB nitrate dihydrate. The reaction of Hg2F2 with MB chloride dihydrate and the crystallization of the resulting product 6 in aqueous DMF yielded crystals of (MB)2HgCl4 Æ H2O. Ó 2006 Elsevier B.V. All rights reserved. Keywords: Methylene blue; Metal–dye interaction; Metallate; Mercury(II) 1. Introduction interacting with Hg(II), Cd(II), Ag(I) has been postulated for the removal of these ions from waste water [9], while Methylene blue (MB), which is a ‘‘dyestuff that made the preparation and properties of the gallium chloride– medical history’’ [1], is used as a stain and an agent for MB complex has been reported [10]. However, no struc- blood product decontamination [2,3]. It had been used to tural report of the metal complex of MB is at present treat urinary tract infections, to distinguish between can- known. Therefore, the study of interactions of MB with cerous and normal tissues [4], an antidote for cyanide poi- metal ions will be helpful to understand its applications. soning in humans, and an antiseptic in veterinary medicine The Cambridge Structural Database (version 5.25) [11] [5]. It is also used in photodynamic therapy [6], which is an includes four MB crystal structures containing the pheno- antineoplastic therapy, aided by the absorption of light. It thiazinium moiety, which are the chloride pentahydrate is also one of the most frequently used counter ions for ion- [12], triiodide [13], thiocyanate [14], bis(malenonitriledi- pair formation [7] with salicylic acid [8]. The idea of MB thiolato)cuprate(II) [15]. Additionally the structures of urate hexahydrate [16] and nitrate dihydrate [17] salts are reported. This investigation has been undertaken to under- * Corresponding author. Tel.: +91 431 2351352. E-mail address: [email protected] (K. Panchanatheswaran). stand the interactions between MB salts and different mer- cury halides. 0020-1693/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2006.09.022 1800 M.M. Raj et al. / Inorganica Chimica Acta 360 (2007) 1799–1808 2. Experimental 1483, 1432, 1388, 1351, 1329, 1240, 1214, 1170, 1133, 1037, 882, 820, 661, 617, 532. UV–Vis (CH3OH) kmax/ 1 2.1. Preparation of 3,7-bis(dimethylamino)phenothiazin-5- nm: 653, 610 (sh), 291. H NMR (200 MHz, DMSO-d6): ium nitrate dihydrate (MB nitrate dihydrate) d 3.14 (s, 12H), 7.19 (s, 4H), 7.62 (s, 2H). The above compound was prepared by adding a solu- 2.4. Preparation of 3,7-bis(dimethylamino)phenothiazin-5- tion of MB chloride trihydrate (0.373g, 1mmol) in water/ ium hexaiododimercurate(II) (4) MeOH to a solution of silver nitrate (0.34g, 2mmol) in water. The solution was filtered. Crystals of MB nitrate The above compound was obtained by the reaction of dihydrate separated as violet crystals when the filtrate HgI2 (0.45 g, 1 mmol) with MB chloride dihydrate was allowed to evaporate. Yield: 0.25g (65%); m.p. (0.35 g, 1 mmol) adopting the same procedure as described >320 °C. Anal. Calc. for C16H22N4O5S: C, 50.25; H, 5.80; in Section 2.3. Yield: 0.53 g (61%); m.p. >320 °C. Anal. N, 14.65; S, 8.38. Found: C, 49.98; H, 5.79; N, 14.41; S, Calc. for C16H18I3HgN3S Æ [(CH3)2NCOH]: C, 24.31; H, 7.98%. IR (cmÀ1): 3418, 1599, 1486, 1443, 1384, 1356, 2.68; N, 5.97; S, 3.42. Found: C, 24.79; H, 2.34; N, 5.45; À1 1252, 1176, 1147, 1082, 961, 884, 612. UV–Vis (CH3OH) S, 3.89%. IR (cm ): 2818, 1593, 1479, 1436, 1384, 1346, 1 kmax/nm: 653, 601 (sh), 292. H NMR (200 MHz, D2O): 1327, 1244, 1168, 1133, 1035, 944, 879, 825, 776, 663. 3 1 d 2.97 (s, 12H), 6.60 (s, 2H), 6.84 (d, J = 10.0, 2H), 7.06 UV–Vis (CH3OH) kmax/nm: 653, 601 (sh), 291. H NMR 3 (d, J = 8.01, 2H). (200 MHz, DMSO-d6): d 3.36 (s, 12H), 7.48 (s, 4H), 7.87 (d, 3J = 9.58, 2H). 2.2. Preparation of 3,7-bis(dimethylamino)phenothiazin-5- ium-jN10-trichloromercury(II) (1) and 3,7- 2.5. Synthesis of 3,7-bis(dimethylamino)phenothiazin-5-ium bis(dimethylamino)phenothiazin-5-ium octachlorodinitratotetramercurate(II) (5) tetrachloromercurate(II) (2) To a solution of HgCl2 (0.07 g, 0.27 mmol) in methanol, To a solution of HgCl2 (0.271 g, 1 mmol) in methanol, MB nitrate dihydrate (0.1 g, 0.26 mmol) also in methanol MB chloride dihydrate (0.355 g, 1 mmol) in the same sol- was added slowly. The blue precipitate was formed slowly vent was added slowly. The blue precipitate was formed and the reaction mixture was stirred for few minutes for immediately and stirred for a few minutes for completion completion of the reaction. The precipitate was filtered of the reaction. The precipitate was filtered and recrystal- and recrystallized in an ethanol/water mixture. Yield: lized in DMF/H2O resulting in two types of crystals viz., 0.15 g (65%); m.p 320 °C. Anal. Calc. for green needles (1) and red brown cubic crystals (2), which C16H18Cl4Hg2N4O3S: C, 21.61; H, 2.04; N, 6.30; S, 3.61. were mechanically separated. Combined yield: 0.42 g Found: C, 21.63; H, 2.23; N, 6.19; S, 3.81%. IR (cmÀ1): (72%). For 1, m.p. chars at 227 °C. Anal. Calc. for 2915, 1738, 1599, 1483, 1435, 1385, 1351, 1336, 1244, C16H18Cl3HgN3S: C, 32.49; H, 3.07; N, 7.11; S, 5.42. 1222, 1174, 1137, 1037, 945, 886, 835, 805, 772, 532. UV– À1 1 Found: C, 32.24; H, 3.21; N, 7.15; S, 5.42%. IR (cm ): Vis (CH3OH) kmax/nm: 652, 608 (sh), 291. H NMR 1597, 1491, 1385, 1353, 1251, 1177, 1142, 1037, 945, 883, (200 MHz, DMSO-d6): d 3.35 (s, 12H merged with residual 3 844, 801, 665, 532, 451. UV–Vis (CH3OH) kmax/nm: 651, H2O), 7.51 (s, 4H), 7.89 (d, J = 10.2, 2H). 1 610 (sh), 291, 244. H NMR (200MHz, DMSO-d6): d 3.36 (s, 12H), 7.48 (s, 4H), 7.88 (s, 2H). For 2, m.p. chars 2.6. Preparation of 3,7-bis(dimethylamino)phenothiazin-5- at 240 °C. Anal. Calc. for C32H36Cl4HgN6S2: C, 42.18; H, ium tetrachloromercurate(II) monohydrate (6) 3.98; N, 9.22; S, 7.04. Found: C, 42.00; H, 4.32; N, 9.51; À1 S, 6.78%. IR (cm ): 1593, 1489, 1436, 1384, 1349, 1317, Reaction of Hg2F2 (0.25 g, 0.57 mmol) with MB chlo- 1241, 1168, 1134, 1028, 941, 876, 789, 665, 536. UV–Vis ride dihydrate (0.2 g, 0.56 mmol) adopting the procedure (CH3OH) kmax/nm: 651, 610 (sh), 291. described in Section 2.3 yielded the above compound. Yield: 0.19 g (70%); m.p. >320 °C. Anal. Calc. for 2.3. Preparation of 3,7-bis(dimethylamino)phenothiazin-5- C32H38Cl4HgN6OS2: C, 41.36; H, 4.09; N, 9.04; S, 6.90. ium hexabromodimercurate(II) (3) Found: C, 41.36; H, 3.98; N, 9.19; S, 6.79%. IR (cmÀ1): 1593, 1488, 1439, 1386, 1324, 1253, 1222, 1170, 1140, To a solution of HgBr2 (0.20 g, 0.56 mmol) in hot meth- 1037, 949, 878, 849, 820, 787, 665 532, 447. UV–Vis anol, MB chloride dihydrate (0.2 g, 0.56 mmol) also in (CH3OH) kmax/nm: 651, 609 (sh), 291. methanol was slowly added. The blue precipitate was formed immediately and stirred for a few minutes for com- 2.7. Instrumentation pletion of the reaction. The precipitate was filtered and recrystallized in a DMF/water mixture. Yield: 0.27 g Elemental analysis was carried out using a model Ele- (68%); m.p. >320 °C. Anal. Calc. for C16H18Br3HgN3S: menter varioEL III at the Sophisticated Test and Instru- C, 26.52; H, 2.50; N, 5.80; S, 4.42.
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