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(2-Deoxy-2-{[2-(2-pyridinyl-κN)-4-thiazolecarbonyl-κN3]amino}-α-d-glucopyranose)dichloropalladium(II) Methanol Solvate

(2-Deoxy-2-{[2-(2-pyridinyl-κN)-4-thiazolecarbonyl-κN3]amino}-α-d-glucopyranose)dichloropalladium... molbank Short Note (2-Deoxy-2-{[2-(2-pyridinyl-N)- 4-thiazolecarbonyl-N ]amino}- -D-glucopyranose) dichloropalladium(II) Methanol Solvate 1 ID 1 , 1 2 2 Shintaro Kodama , Akihiro Nomoto *, Yuta Sakai , Shouhei Katao , Kiyomi Kakiuchi , 2 1 , Shigenobu Yano and Akiya Ogawa * Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan; s-kodama@chem.osakafu-u.ac.jp (S.K.); nomotoakihiro@yahoo.co.jp (Y.S.) Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0192, Japan; katao@ms.naist.jp (S.K.); kakiuchi@ms.naist.jp (K.K.); yano-shigenobu@ms.naist.jp (S.Y.) * Correspondence: nomoto@chem.osakafu-u.ac.jp (A.N.); ogawa@chem.osakafu-u.ac.jp (A.O.) Received: 21 August 2017; Accepted: 22 September 2017; Published: 25 September 2017 Abstract: A novel palladium(II) complex with a glycoconjugated 2-(2-pyridyl)thiazole ligand was synthesized. Single-crystal X-ray analysis revealed a packing structure that may be stabilized by hydrogen bonding between sugar moieties and between methanol (crystal solvent) and a sugar moiety. Keywords: palladium complex; sugar; pyridylthiazole; X-ray structure analysis; hydrogen bonding 1. Introduction Glycoconjugated transition-metal complexes have played an important role in bioinorganic and biomedicinal chemistry [1–4]. In the context of our recent research on complexes of group 10 metals with sugar-conjugated ligands as antitumor metallo-drugs [5,6], we have synthesized a novel glycoconjugated palladium complex and have successfully determined its crystal structure. 2. Results and Discussion Glycoconjugated 2-(2-pyridyl)thiazole ligand 1 was synthesized by the condensation of 2-(2-pyridinyl)-4-thiazolecarboxylic acid [7] with glucosamine in the presence of 1-[3-dimethylaminopropyl]-3-ethylcarbodiimide (EDC) and 1-hydroxybenzotriazole (HOBT). Then, the reaction of 1 with sodium tetrachloropalladate(II) (Na PdCl ) in a mixed MeOH/H O 2 4 2 solvent afforded the desired glycoconjugated palladium(II) complex 2 in an 86% yield (Scheme 1). The structure of complex 2 has been determined unambiguously by single-crystal X-ray analysis (Figure 1) to show a distorted square planar geometry about the Pd(II) atom. The Pd–N (2.024(10) and 2.028(9) Å) and Pd–Cl (2.283(3) and 2.288(3) Å) bond distances are within the range reported for the structurally related palladium(II) bipyridine complexes [8,9]. In addition, a hydrogen bond was observed between the hydroxyl proton (H2) of the D-glucopyranose moiety and methanol (crystal solvent), and the O2O7 distance is 2.737(12) Å. Molbank 2017, 2017, M959; doi:10.3390/M959 www.mdpi.com/journal/molbank Molbank 2017, 2017, M959 2 of 5 Molbank 2017, 2017, M959 2 of 5 Molbank 2017, 2017, M959 2 of 5 Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Figure 1. Crystal structure of 2·MeOH with numbered atoms. Ellipsoids are shown at the 50% probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. Figure 1. Crystal structure of 2·MeOH with numbered atoms. Ellipsoids are shown at the 50% Figure 1. Crystal structure of 2MeOH with numbered atoms. Ellipsoids are shown at the 50% The absolute configuration of complex 2 were established by the structure determination of the probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion The absolute configuration of complex 2 were established by the structure determination of the The absolute configuration of complex 2 were established by the structure determination of the effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles N3–C9, 1.327(14); O2···O7, 2.737(12); N1–Pd1–N2, 81.1(4); N1–Pd1–Cl1, 92.8(3); N2–Pd1–Cl1, (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); 173.9(3); N1–Pd1–Cl2, 177.6(3); N2–Pd1–Cl2, 96.6(3); Cl1–Pd1–Cl2, 89.53(12); O1–C9–N3, 125.3(11); N3–C9, N3–C9, 1 1.327(14); .327(14); O2 O2O7, ···O7 2.737(12); , 2.737(12); N1– N1–Pd1–N2, Pd1–N2 81.1(4); , 81.1( N1–Pd1–Cl1, 4); N1–Pd1–C 92.8(3); l1, 92.8(3) N2–Pd1–Cl1, ; N2–Pd1–Cl1, 173.9(3); O1–C9–C8, 118.9(11); N3–C9–C8, 115.6(11). N1–Pd1–Cl2, 173.9(3); N1–P 177.6(3); d1–Cl2, 177.6(3 N2–Pd1–Cl2, ); N2–Pd1–Cl2 96.6(3); Cl1–Pd1–Cl2, , 96.6(3); Cl1–Pd1–Cl2, 89.53(1 89.53(12); O1–C9–N3, 2); O1–C9–N3 125.3(11); O1–C9–C8, , 125.3(11); 118.9(11); O1–C9–C8, 118.9(11); N3–C9– N3–C9–C8, 115.6(11). C8, 115.6(11). Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the formation of two-dimensional (2D) molecular networks. The selected interatomic distances and D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) formation of two-dimensional (2D) molecular networks. The selected interatomic distances and formation of two-dimensional (2D) molecular networks. The selected interatomic distances and Å (O2–H2···O7), 2.737(12) Å, and 171(15)° (O2–H2···O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3···O3 ), angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) Å i i i i i 2.848(7) Å, and 151(12)° (O3–H3 ··· O3 ); 0.84(3) Å (O4 –H4 ), 1.89(5) Å (O4 –H4 ···O1 = C9), 2.691(11) i Å (O2–H2···O7), 2.737(12) Å, and 171(15)° (O2–H2···O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3···O3 ), (O2–H2O7), 2.737(12) Å, and 171(15) (O2–H2O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3O3 ), i i ii i i i i i Å, and 161(14)° (O4 –H4 ···O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6···O4 ), 2.659(13) Å, and 140(14)° 2.848(7) Å, and 151(12)° (O3–H3 ··· O3i); 0.84(3) Å (O4 i –H4i), 1.89(5) Å (O4 i –H4i···O1 = C9), 2.691(11) 2.848(7) Å, and 151(12) (O3–H3  O3 ); 0.84(3) Å (O4 –H4 ), 1.89(5) Å (O4 –H4 O1 = C9), 2.691(11) ii (O6–H6···O4 ). Symmetry operators: i i (i) −1/2 + X, 3/2 − Y, 1 − Z; (ii) −1 + X, iiY, Z. Å, and 161(14)° (O4 –H4 ···O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6···O4 ), 2.659(13) Å, and 140(14)° i i ii Å, and 161(14) (O4 –H4 O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6O4 ), 2.659(13) Å, and 140(14) ii (O6–H6···O4 ). Symmetry operators: (i) −1/2 + X, 3/2 − Y, 1 − Z; (ii) −1 + X, Y, Z. ii (O6–H6O4 ). Symmetry operators: (i) 1/2 + X, 3/2 Y, 1 Z; (ii) 1 + X, Y, Z. Molbank 2017, 2017, M959 3 of 5 Molbank 2017, 2017, M959 3 of 5 Figure 2. Crystal packing of 2·MeOH viewed along the a-axis (top) and b-axis (bottom). Hydrogen Figure 2. Crystal packing of 2MeOH viewed along the a-axis (top) and b-axis (bottom). Hydrogen bonds bonds are represented by the dotted blue lines. are represented by the dotted blue lines. 3. Materials and Methods 3. Materials and Methods 3.1. General 3.1. General All reagents and solvents were purchased from chemical companies and used without further All reagents and solvents were purchased from chemical companies and used without further 1 13 1 purification. 1 H (400 MHz) and 13 C{ H} (100 MH 1 z) NMR spectra were recorded on a JEOL ECX-400 purification. H (400 MHz) and C{ H} (100 MHz) NMR spectra were recorded on a JEOL ECX-400 spectrometer (JEOL, Tokyo, Japan). Chemical shifts are reported in δ, referenced to residual 1H and spectrometer (JEOL, Tokyo, Japan). Chemical shifts are reported in , referenced to residual H and 13 C signals of N,N-dimethylformamide-d7 (DMF-d7) as an internal standard. The IR spectrum was C signals of N,N-dimethylformamide-d (DMF-d ) as an internal standard. The IR spectrum was 7 7 recorded on a JASCO FT/TR-8900 spectrometer (JASCO, Tokyo, Japan). recorded on a JASCO FT/TR-8900 spectrometer (JASCO, Tokyo, Japan). 3.2. Synthesis of Glycoconjugated Palladium(II) Complex 2 3.2. Synthesis of Glycoconjugated Palladium(II) Complex 2 A mixture of 2-(2-pyridinyl)-4-thiazolecarboxylic acid (430 mg, 2.0 mmol), D-(+)-glucosamine A mixture of 2-(2-pyridinyl)-4-thiazolecarboxylic acid (430 mg, 2.0 mmol), D-(+)-glucosamine hydrochloride (481 mg, 2.2 mmol), EDC (448 mg, 2.9 mmol) and HOBT (324 mg, 2.4 mmol) in DMF hydrochloride (481 mg, 2.2 mmol), EDC (448 mg, 2.9 mmol) and HOBT (324 mg, 2.4 mmol) in DMF (16 mL) was stirred at room temperature for 1 h. The resulting mixture was evaporated in vacuo, and the residue was washed with Et2O and then dissolved in EtOH. The solution was filtered, and Molbank 2017, 2017, M959 4 of 5 (16 mL) was stirred at room temperature for 1 h. The resulting mixture was evaporated in vacuo, and the residue was washed with Et O and then dissolved in EtOH. The solution was filtered, and the filtrate was evaporated in vacuo to afford glycoconjugated 2-(2-pyridyl)thiazole ligand 1 (163 mg, 21% yield) as yellow solid. Then, Na PdCl (58.9 mg, 0.2 mmol) and 1 (75.8 mg, 0.2 mmol) were stirred in 2 4 a mixed MeOH/H O (1:1) solvent (30 mL) at room temperature for 10 h. The resulting suspension was filtered to obtain 2 (93.0 mg, 86% yield) as pale yellow powder. Mp 247–250 C (decomp.); H NMR (DMF-d , 400 MHz)  9.15 (d, J = 4.8 Hz, 1H), 8.51 (d, J = 7.2 Hz, 1H), 8.43 (td, J = 8.0, 1.2 Hz, 1H), 8.36 (s, 1H), 8.34 (s, 1H), 7.90 (ddd, J = 7.6, 5.6, 1.6 Hz, 1H), 6.75 (d, J = 3.6 Hz, 1H), 5.46 (t, J = 3.8 Hz, 1H), 5.06 (d, J = 3.6 Hz, 1H), 4.73 (br, 1H), 4.46 (br, 1H), 4.00 (td, J = 10, 2.5 Hz, 1H), 3.88–3.78 (m, 3H), 13 1 3.73–3.59 (m, 1H), 3.46–3.38 (m, 1H); C{ H} (DMF-d , 100 MHz)  169.9, 161.6, 153.4, 152.5, 150.8, 142.6, 128.3, 125.7, 125.3, 92.1, 73.5, 72.9, 72.8, 63.1, 56.6; IR (cm ) 3245, 3117, 2924, 1647, 1539, 1506, 1309, 1095, 1037, 779; Anal. Calcd for C H Cl N O Pd: C, 33.32; H, 3.67; N, 7.29. Found: C, 33.01; H, 16 21 2 3 7 3.58; N, 7.63. 3.3. X-ray Diffraction Studies An X-ray crystallographic measurement was carried out on a Rigaku RAXIS-RAPID diffractometer (Rigaku, Tokyo, Japan) with Mo K radiation at 123 K. Of 28,532 reflections collected, 3712 were unique (R = 0.1634). An empirical absorption correction was applied, which resulted in transmission int factors ranging from 0.283 to 0.987. The data were corrected for Lorentz and polarization effects. The structure of 2MeOH was solved by direct methods and expanded using Fourier techniques. The non-hydrogen atoms were refined anisotropically, and hydrogen atoms were refined using the riding model. All calculations were performed with the CrystalStructure [10] crystallographic software package except for refinements, which was performed using SHELXL Version 2016/6 [11]. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. The hydrogen atom of hydroxyl group of methanol was not included in the refinements. The absolute configuration of complex 2 were established by the structure determination of the D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion effects in diffraction measurements on the crystal. Although the present results provide a marginal dataset, the acceptable structure model has been achieved. Crystallographic data: formula weight = 575.71; orthorhombic; space group P2 2 2 ; a = 4.9453(3) 1 1 1 3 3 Å, b = 12.1389(8) Å, c = 34.058(2) Å; V = 2044.5(2) Å ; Z = 4;  = 1.870 gcm ; total reflections calcd collected = 28,532; GOF = 1.050; R = 0.0657; wR = 0.1224. Crystallographic data have been deposited 1 2 with Cambridge Crystallographic Data Centre (CCDC-1567381). These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44-1223-336033; E-mail: deposit@ccdc.cam.ac.uk). Supplementary Materials: The following are available online: http://www.mdpi.com/1422-8599/2017/4/M959 1 13 1 Figure S1: H-NMR spectrum (DMF-d , 400 MHz) of 2; Figure S2: C{ H}-NMR spectrum (DMF-d , 400 MHz) 7 7 of 2. Acknowledgments: This work was supported by JSPS KAKENHI Grant Number JP16H04138 (Scientific Research B). This work was partly supported by the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. Author Contributions: S.K., A.N., Y.S., and A.O. performed research; S.K., K.K., and S.Y. analyzed X-ray data. All authors read and approved the final manuscript. Conflicts of Interest: The authors declare no conflict of interest. References 1. Yano, S.; Mikata, Y. Recent progress of functional glycoconjugated metal complexes. Bull. Chem. Soc. Jpn. 2002, 75, 2097–2113. [CrossRef] 2. Storr, T.; Thompson, K.H.; Orvig, C. Design of targeting ligands in medicinal inorganic chemistry. Chem. Soc. Rev. 2006, 35, 534–544. [CrossRef] [PubMed] Molbank 2017, 2017, M959 5 of 5 3. Gottschaldt, M.; Schubert, U.S. Prospects of metal complexes peripherally substituted with sugars in biomedicinal applications. Chem. Eur. J. 2009, 15, 1548–1557. [CrossRef] [PubMed] 4. Singh, S.; Aggarwal, A.; Bhupathiraju, N.V.S.D.K.; Arianna, G.; Tiwari, K.; Drain, C.M. Glycosylated porphyrins, phthalocyanines, and other porphyrinoids for diagnostics and therapeutics. Chem. Rev. 2015, 115, 10261–10306. [CrossRef] [PubMed] 5. Yano, S.; Ohi, H.; Ashizaki, M.; Obata, M.; Mikata, Y.; Tanaka, R.; Nishioka, T.; Kinoshita, I.; Sugai, Y.; Okura, I.; et al. Syntheses, characterization, and antitumor activities of platinum(II) and palladium(II) complexes with sugar-conjugated triazole ligands. Chem. Biodivers. 2012, 9, 1903–1915. [CrossRef] [PubMed] 6. Hayashi, N.; Kataoka, H.; Yano, S.; Kikuchi, J.-I.; Tanaka, M.; Nishie, H.; Kinoshita, Y.; Hatano, M.; Nomoto, A.; Ogawa, A.; et al. Anticancer effects of a new aminosugar-conjugated platinum complex agent against cisplatin-resistant gastric cancer. Anticancer Res. 2016, 36, 6005–6010. [CrossRef] [PubMed] 7. Credico, B.D.; Reginato, G.; Gonsalvi, L.; Peruzzini, M.; Rossin, A. Selective synthesis of 2-substituted 4-carboxy oxazoles, thiazoles and thiazolidines from serine or cysteine amino acids. Tetrahedron 2011, 67, 267–274. [CrossRef] 8. Newkome, G.R.; Fronczek, F.R.; Gupta, V.K.; Puckett, W.E.; Pantaleo, D.C.; Kiefer, G.E. Acute bonding deviation in square-planar d palladium(II) complexes. J. Am. Chem. Soc. 1982, 104, 1782–1783. [CrossRef] 9. Beer, P.D.; Fletcher, N.C.; Drew, M.G.B.; Wear, T.J. Chloride anion recognition by neutral platinum(II) and palladium(II) 5,5 -bis-amide substituted bipyridyl receptor molecules. Polyhedron 1997, 16, 815–823. [CrossRef] 10. Crystal Structure 4.2.4: Crystal Structure Analysis Package; Rigaku Corporation: Tokyo, Japan, 2000–2016. 11. Sheldrick, G.M. A short history of SHELX. Acta Cryst. Sect. A 2008, 64, 112–122. [CrossRef] [PubMed] © 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Molbank Multidisciplinary Digital Publishing Institute

(2-Deoxy-2-{[2-(2-pyridinyl-κN)-4-thiazolecarbonyl-κN3]amino}-α-d-glucopyranose)dichloropalladium(II) Methanol Solvate

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Abstract

molbank Short Note (2-Deoxy-2-{[2-(2-pyridinyl-N)- 4-thiazolecarbonyl-N ]amino}- -D-glucopyranose) dichloropalladium(II) Methanol Solvate 1 ID 1 , 1 2 2 Shintaro Kodama , Akihiro Nomoto *, Yuta Sakai , Shouhei Katao , Kiyomi Kakiuchi , 2 1 , Shigenobu Yano and Akiya Ogawa * Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan; s-kodama@chem.osakafu-u.ac.jp (S.K.); nomotoakihiro@yahoo.co.jp (Y.S.) Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0192, Japan; katao@ms.naist.jp (S.K.); kakiuchi@ms.naist.jp (K.K.); yano-shigenobu@ms.naist.jp (S.Y.) * Correspondence: nomoto@chem.osakafu-u.ac.jp (A.N.); ogawa@chem.osakafu-u.ac.jp (A.O.) Received: 21 August 2017; Accepted: 22 September 2017; Published: 25 September 2017 Abstract: A novel palladium(II) complex with a glycoconjugated 2-(2-pyridyl)thiazole ligand was synthesized. Single-crystal X-ray analysis revealed a packing structure that may be stabilized by hydrogen bonding between sugar moieties and between methanol (crystal solvent) and a sugar moiety. Keywords: palladium complex; sugar; pyridylthiazole; X-ray structure analysis; hydrogen bonding 1. Introduction Glycoconjugated transition-metal complexes have played an important role in bioinorganic and biomedicinal chemistry [1–4]. In the context of our recent research on complexes of group 10 metals with sugar-conjugated ligands as antitumor metallo-drugs [5,6], we have synthesized a novel glycoconjugated palladium complex and have successfully determined its crystal structure. 2. Results and Discussion Glycoconjugated 2-(2-pyridyl)thiazole ligand 1 was synthesized by the condensation of 2-(2-pyridinyl)-4-thiazolecarboxylic acid [7] with glucosamine in the presence of 1-[3-dimethylaminopropyl]-3-ethylcarbodiimide (EDC) and 1-hydroxybenzotriazole (HOBT). Then, the reaction of 1 with sodium tetrachloropalladate(II) (Na PdCl ) in a mixed MeOH/H O 2 4 2 solvent afforded the desired glycoconjugated palladium(II) complex 2 in an 86% yield (Scheme 1). The structure of complex 2 has been determined unambiguously by single-crystal X-ray analysis (Figure 1) to show a distorted square planar geometry about the Pd(II) atom. The Pd–N (2.024(10) and 2.028(9) Å) and Pd–Cl (2.283(3) and 2.288(3) Å) bond distances are within the range reported for the structurally related palladium(II) bipyridine complexes [8,9]. In addition, a hydrogen bond was observed between the hydroxyl proton (H2) of the D-glucopyranose moiety and methanol (crystal solvent), and the O2O7 distance is 2.737(12) Å. Molbank 2017, 2017, M959; doi:10.3390/M959 www.mdpi.com/journal/molbank Molbank 2017, 2017, M959 2 of 5 Molbank 2017, 2017, M959 2 of 5 Molbank 2017, 2017, M959 2 of 5 Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Scheme 1. Synthesis of the glycoconjugated palladium(II) complex 2. Figure 1. Crystal structure of 2·MeOH with numbered atoms. Ellipsoids are shown at the 50% probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. Figure 1. Crystal structure of 2·MeOH with numbered atoms. Ellipsoids are shown at the 50% Figure 1. Crystal structure of 2MeOH with numbered atoms. Ellipsoids are shown at the 50% The absolute configuration of complex 2 were established by the structure determination of the probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. probability level. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion The absolute configuration of complex 2 were established by the structure determination of the The absolute configuration of complex 2 were established by the structure determination of the effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles effects in diffraction measurements on the crystal. Selected interatomic distances (Å) and angles N3–C9, 1.327(14); O2···O7, 2.737(12); N1–Pd1–N2, 81.1(4); N1–Pd1–Cl1, 92.8(3); N2–Pd1–Cl1, (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); (deg): Pd1–N1, 2.028(9); Pd1–N2, 2.024(10); Pd1–Cl1, 2.283(3); Pd1–Cl2, 2.288(3); O1–C9, 1.238(13); 173.9(3); N1–Pd1–Cl2, 177.6(3); N2–Pd1–Cl2, 96.6(3); Cl1–Pd1–Cl2, 89.53(12); O1–C9–N3, 125.3(11); N3–C9, N3–C9, 1 1.327(14); .327(14); O2 O2O7, ···O7 2.737(12); , 2.737(12); N1– N1–Pd1–N2, Pd1–N2 81.1(4); , 81.1( N1–Pd1–Cl1, 4); N1–Pd1–C 92.8(3); l1, 92.8(3) N2–Pd1–Cl1, ; N2–Pd1–Cl1, 173.9(3); O1–C9–C8, 118.9(11); N3–C9–C8, 115.6(11). N1–Pd1–Cl2, 173.9(3); N1–P 177.6(3); d1–Cl2, 177.6(3 N2–Pd1–Cl2, ); N2–Pd1–Cl2 96.6(3); Cl1–Pd1–Cl2, , 96.6(3); Cl1–Pd1–Cl2, 89.53(1 89.53(12); O1–C9–N3, 2); O1–C9–N3 125.3(11); O1–C9–C8, , 125.3(11); 118.9(11); O1–C9–C8, 118.9(11); N3–C9– N3–C9–C8, 115.6(11). C8, 115.6(11). Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the Figure 2 shows that intermolecular hydrogen-bonding interactions were present between the formation of two-dimensional (2D) molecular networks. The selected interatomic distances and D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the D-glucopyranose moieties and between methanol and the D-glucopyranose moiety, resulting in the angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) formation of two-dimensional (2D) molecular networks. The selected interatomic distances and formation of two-dimensional (2D) molecular networks. The selected interatomic distances and Å (O2–H2···O7), 2.737(12) Å, and 171(15)° (O2–H2···O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3···O3 ), angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) angles for hydrogen bonds found in the molecules are shown as follows: 0.85(3) Å (O2–H2), 1.89(4) Å i i i i i 2.848(7) Å, and 151(12)° (O3–H3 ··· O3 ); 0.84(3) Å (O4 –H4 ), 1.89(5) Å (O4 –H4 ···O1 = C9), 2.691(11) i Å (O2–H2···O7), 2.737(12) Å, and 171(15)° (O2–H2···O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3···O3 ), (O2–H2O7), 2.737(12) Å, and 171(15) (O2–H2O7); 0.83(3) Å (O3–H3), 2.09(7) Å (O3–H3O3 ), i i ii i i i i i Å, and 161(14)° (O4 –H4 ···O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6···O4 ), 2.659(13) Å, and 140(14)° 2.848(7) Å, and 151(12)° (O3–H3 ··· O3i); 0.84(3) Å (O4 i –H4i), 1.89(5) Å (O4 i –H4i···O1 = C9), 2.691(11) 2.848(7) Å, and 151(12) (O3–H3  O3 ); 0.84(3) Å (O4 –H4 ), 1.89(5) Å (O4 –H4 O1 = C9), 2.691(11) ii (O6–H6···O4 ). Symmetry operators: i i (i) −1/2 + X, 3/2 − Y, 1 − Z; (ii) −1 + X, iiY, Z. Å, and 161(14)° (O4 –H4 ···O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6···O4 ), 2.659(13) Å, and 140(14)° i i ii Å, and 161(14) (O4 –H4 O1); 0.84(3) Å (O6–H6), 1.96(10) Å (O6–H6O4 ), 2.659(13) Å, and 140(14) ii (O6–H6···O4 ). Symmetry operators: (i) −1/2 + X, 3/2 − Y, 1 − Z; (ii) −1 + X, Y, Z. ii (O6–H6O4 ). Symmetry operators: (i) 1/2 + X, 3/2 Y, 1 Z; (ii) 1 + X, Y, Z. Molbank 2017, 2017, M959 3 of 5 Molbank 2017, 2017, M959 3 of 5 Figure 2. Crystal packing of 2·MeOH viewed along the a-axis (top) and b-axis (bottom). Hydrogen Figure 2. Crystal packing of 2MeOH viewed along the a-axis (top) and b-axis (bottom). Hydrogen bonds bonds are represented by the dotted blue lines. are represented by the dotted blue lines. 3. Materials and Methods 3. Materials and Methods 3.1. General 3.1. General All reagents and solvents were purchased from chemical companies and used without further All reagents and solvents were purchased from chemical companies and used without further 1 13 1 purification. 1 H (400 MHz) and 13 C{ H} (100 MH 1 z) NMR spectra were recorded on a JEOL ECX-400 purification. H (400 MHz) and C{ H} (100 MHz) NMR spectra were recorded on a JEOL ECX-400 spectrometer (JEOL, Tokyo, Japan). Chemical shifts are reported in δ, referenced to residual 1H and spectrometer (JEOL, Tokyo, Japan). Chemical shifts are reported in , referenced to residual H and 13 C signals of N,N-dimethylformamide-d7 (DMF-d7) as an internal standard. The IR spectrum was C signals of N,N-dimethylformamide-d (DMF-d ) as an internal standard. The IR spectrum was 7 7 recorded on a JASCO FT/TR-8900 spectrometer (JASCO, Tokyo, Japan). recorded on a JASCO FT/TR-8900 spectrometer (JASCO, Tokyo, Japan). 3.2. Synthesis of Glycoconjugated Palladium(II) Complex 2 3.2. Synthesis of Glycoconjugated Palladium(II) Complex 2 A mixture of 2-(2-pyridinyl)-4-thiazolecarboxylic acid (430 mg, 2.0 mmol), D-(+)-glucosamine A mixture of 2-(2-pyridinyl)-4-thiazolecarboxylic acid (430 mg, 2.0 mmol), D-(+)-glucosamine hydrochloride (481 mg, 2.2 mmol), EDC (448 mg, 2.9 mmol) and HOBT (324 mg, 2.4 mmol) in DMF hydrochloride (481 mg, 2.2 mmol), EDC (448 mg, 2.9 mmol) and HOBT (324 mg, 2.4 mmol) in DMF (16 mL) was stirred at room temperature for 1 h. The resulting mixture was evaporated in vacuo, and the residue was washed with Et2O and then dissolved in EtOH. The solution was filtered, and Molbank 2017, 2017, M959 4 of 5 (16 mL) was stirred at room temperature for 1 h. The resulting mixture was evaporated in vacuo, and the residue was washed with Et O and then dissolved in EtOH. The solution was filtered, and the filtrate was evaporated in vacuo to afford glycoconjugated 2-(2-pyridyl)thiazole ligand 1 (163 mg, 21% yield) as yellow solid. Then, Na PdCl (58.9 mg, 0.2 mmol) and 1 (75.8 mg, 0.2 mmol) were stirred in 2 4 a mixed MeOH/H O (1:1) solvent (30 mL) at room temperature for 10 h. The resulting suspension was filtered to obtain 2 (93.0 mg, 86% yield) as pale yellow powder. Mp 247–250 C (decomp.); H NMR (DMF-d , 400 MHz)  9.15 (d, J = 4.8 Hz, 1H), 8.51 (d, J = 7.2 Hz, 1H), 8.43 (td, J = 8.0, 1.2 Hz, 1H), 8.36 (s, 1H), 8.34 (s, 1H), 7.90 (ddd, J = 7.6, 5.6, 1.6 Hz, 1H), 6.75 (d, J = 3.6 Hz, 1H), 5.46 (t, J = 3.8 Hz, 1H), 5.06 (d, J = 3.6 Hz, 1H), 4.73 (br, 1H), 4.46 (br, 1H), 4.00 (td, J = 10, 2.5 Hz, 1H), 3.88–3.78 (m, 3H), 13 1 3.73–3.59 (m, 1H), 3.46–3.38 (m, 1H); C{ H} (DMF-d , 100 MHz)  169.9, 161.6, 153.4, 152.5, 150.8, 142.6, 128.3, 125.7, 125.3, 92.1, 73.5, 72.9, 72.8, 63.1, 56.6; IR (cm ) 3245, 3117, 2924, 1647, 1539, 1506, 1309, 1095, 1037, 779; Anal. Calcd for C H Cl N O Pd: C, 33.32; H, 3.67; N, 7.29. Found: C, 33.01; H, 16 21 2 3 7 3.58; N, 7.63. 3.3. X-ray Diffraction Studies An X-ray crystallographic measurement was carried out on a Rigaku RAXIS-RAPID diffractometer (Rigaku, Tokyo, Japan) with Mo K radiation at 123 K. Of 28,532 reflections collected, 3712 were unique (R = 0.1634). An empirical absorption correction was applied, which resulted in transmission int factors ranging from 0.283 to 0.987. The data were corrected for Lorentz and polarization effects. The structure of 2MeOH was solved by direct methods and expanded using Fourier techniques. The non-hydrogen atoms were refined anisotropically, and hydrogen atoms were refined using the riding model. All calculations were performed with the CrystalStructure [10] crystallographic software package except for refinements, which was performed using SHELXL Version 2016/6 [11]. Hydrogen atoms were added automatically except for H2, H3, H4, H6, and H3A. The hydrogen atom of hydroxyl group of methanol was not included in the refinements. The absolute configuration of complex 2 were established by the structure determination of the D-glucopyranose moiety of known absolute configuration and confirmed by anomalous-dispersion effects in diffraction measurements on the crystal. Although the present results provide a marginal dataset, the acceptable structure model has been achieved. Crystallographic data: formula weight = 575.71; orthorhombic; space group P2 2 2 ; a = 4.9453(3) 1 1 1 3 3 Å, b = 12.1389(8) Å, c = 34.058(2) Å; V = 2044.5(2) Å ; Z = 4;  = 1.870 gcm ; total reflections calcd collected = 28,532; GOF = 1.050; R = 0.0657; wR = 0.1224. Crystallographic data have been deposited 1 2 with Cambridge Crystallographic Data Centre (CCDC-1567381). These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44-1223-336033; E-mail: deposit@ccdc.cam.ac.uk). Supplementary Materials: The following are available online: http://www.mdpi.com/1422-8599/2017/4/M959 1 13 1 Figure S1: H-NMR spectrum (DMF-d , 400 MHz) of 2; Figure S2: C{ H}-NMR spectrum (DMF-d , 400 MHz) 7 7 of 2. Acknowledgments: This work was supported by JSPS KAKENHI Grant Number JP16H04138 (Scientific Research B). This work was partly supported by the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. Author Contributions: S.K., A.N., Y.S., and A.O. performed research; S.K., K.K., and S.Y. analyzed X-ray data. All authors read and approved the final manuscript. Conflicts of Interest: The authors declare no conflict of interest. References 1. Yano, S.; Mikata, Y. Recent progress of functional glycoconjugated metal complexes. Bull. Chem. Soc. Jpn. 2002, 75, 2097–2113. [CrossRef] 2. Storr, T.; Thompson, K.H.; Orvig, C. Design of targeting ligands in medicinal inorganic chemistry. Chem. Soc. Rev. 2006, 35, 534–544. 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Anticancer effects of a new aminosugar-conjugated platinum complex agent against cisplatin-resistant gastric cancer. Anticancer Res. 2016, 36, 6005–6010. [CrossRef] [PubMed] 7. Credico, B.D.; Reginato, G.; Gonsalvi, L.; Peruzzini, M.; Rossin, A. Selective synthesis of 2-substituted 4-carboxy oxazoles, thiazoles and thiazolidines from serine or cysteine amino acids. Tetrahedron 2011, 67, 267–274. [CrossRef] 8. Newkome, G.R.; Fronczek, F.R.; Gupta, V.K.; Puckett, W.E.; Pantaleo, D.C.; Kiefer, G.E. Acute bonding deviation in square-planar d palladium(II) complexes. J. Am. Chem. Soc. 1982, 104, 1782–1783. [CrossRef] 9. Beer, P.D.; Fletcher, N.C.; Drew, M.G.B.; Wear, T.J. Chloride anion recognition by neutral platinum(II) and palladium(II) 5,5 -bis-amide substituted bipyridyl receptor molecules. Polyhedron 1997, 16, 815–823. [CrossRef] 10. Crystal Structure 4.2.4: Crystal Structure Analysis Package; Rigaku Corporation: Tokyo, Japan, 2000–2016. 11. Sheldrick, G.M. A short history of SHELX. Acta Cryst. Sect. A 2008, 64, 112–122. [CrossRef] [PubMed] © 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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Published: Sep 25, 2017

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