兩個基于苯并噻唑-2-硫酮的銀（Ⅱ）配合物的合成、晶體結構和光譜性質

李中峰 張彥茹 崔洋哲 耿文筱 劉敏 金瓊花＊,

(1首都師范大學化學系，北京100048)

(2北京工業(yè)大學材料科學與工程學院，北京100124)

兩個基于苯并噻唑-2-硫酮的銀（Ⅱ）配合物的合成、晶體結構和光譜性質

李中峰1張彥茹1崔洋哲1耿文筱1劉敏2金瓊花＊,1

(1首都師范大學化學系，北京100048)

(2北京工業(yè)大學材料科學與工程學院，北京100124)

合成了2個含有雜環(huán)硫酮的銀（Ⅱ）配合物，[AgCl(PPh3)2(BTZT)]2(1)，[Ag(PPh3)2(BTZT)2](NO3)CH3OH(2)(PPh3=三苯基膦; BTZT=苯并噻唑-2-硫酮)，并通過紅外光譜、X射線單晶衍射、熒光光譜和核磁共振氫譜進行表征和分析。雜環(huán)硫酮存在化學活性基團-N(H)-C(=S)-，在平衡中與其硫醇形式可以相互轉化。2個配合物是在含有2-巰基苯并噻唑(MBT)的甲醇與二氯甲烷混合溶液中，AgCl或AgNO3與三苯基膦反應得到的。配合物1的每個不對稱單元中包含2個相同的分子結構，但是它們具有不同的鍵長和鍵角。配合物2是一個簡單的單核雜配配合物，它的主體結構通過氫鍵作用連接游離的CH3OH和NO3-離子。配合物1和2發(fā)射峰的紅移源于配體中的π-π*躍遷。

銀；三苯基膦；2-巰基苯并噻唑；苯并噻唑-2-硫酮

0Introduction

Current interest in the field of coordination chemistry stems from rapid developments in complexes′structuraldiversity[1-2]andintriguingopticalproperties[3-4]. Mono-and multinuclear complexes with closed-shell d10metals have attracted considerable attention because of the potential applications in antibacterialagents[5], nanomaterials[6]and catalysis[7].

Silver（Ⅱ）complexes based on heterocyclic thione or thiolate are reported in the early 1990[8].Heterocyclic thiones have been drawn much attention due to possesschemicallyactivegroups-N(H)-C(=S)-in equilibrium with its thiol form[9].A kind of heterocyclic thiolate,2-mercaptobenzothiazole(MBT),is bonded to metals in the unique fashion,such asand

In previous literature,the similar complex{[AgCl (TPP)2(MBZT)]·(MBZT)·2(toluene)}isreported[13]. Differently,we synthesize a complex whose each asymmetric unit contains two same structures in the mixed solution of CH3OH and CH2Cl2.The complex [Ag(PPh3)2(BTZT)2](NO3)is mentioned in 1998[14],but the spectroscopic properties have not been researched. Maybe the single crystal of[Ag(PPh3)2(BTZT)2](NO3)is inexistent,so crystallographic data doesn′t be acquired by single-crystal X-ray diffraction in previous literature.

We are interested in silver（Ⅱ）complexes with phosphorus and heterocyclic NS ligand.We report our successful syntheses of two novel complexes,[AgCl (PPh3)2(BTZT)]2(1)(PPh3=triphenylphosphine;BTZT= benzothiazoline-2-thione)and[Ag(PPh3)2(BTZT)2](NO3) ·CH3OH(2).The complexes 1～2 have been characterized by IR,single-crystal X-ray diffraction,fluorescence spectrum and1H NMR spectroscopy.Last year, we prepared two new complexes[AgBr(PPh3)2(BTZT)]2(3)and[Ag2Cl2(PPh3)2(BTZT)2]·CH3OH(4).Different structures of 1～4 are formed due to different proportion of martials and different anions(Scheme 1).

Scheme 1Routine of synthesis for complexes 1～4

1Experimental

1.1 Materials and measurements

All chemical reagents are commercially available and used without furthermore treatment.FT-IR spectra (KBr pellets)were measured on a Perkin-Elmer Infrared spectrometer.C,H and N elemental analysis were carried out on an Elementar Vario MICRO CUBE (Germany)elementalanalyzer.Room-temperature fluorescence spectra were measured on F-4500 FL Spectrophotometer.1H NMR was recorded at room temperature with VARIAN VNMRS 600 MHz NMR.

1.2 Synthesis of[AgCl(PPh3)2(BTZT)]2(1)

2-mercaptobenzothiazole(MBT,0.2 mmol,0.033 0 g)was added to a stirred solution of triphenylphosphine(0.4 mmol,0.105 1 g)and AgCl(0.2 mmol, 0.028 9 g)in CH3OH(5 mL)and CH2Cl2(5 mL).After stirred for 6 h,the solution was filtered at room temperature.After slow evaporation of the filtrate at ambient temperature for 6 days,colorless and transparent crystals of the title complex were obtained. Yield:64%.Element analysis Calcd.(%)for C43H35Ag ClNP2S2:C,61.79;H,4.19;N,1.68.Found(%):C, 62.26;H,4.59;N,1.47.IR data(KBr pellets,cm-1): 3429w,3054w,3000w,2936w,1596w,1497s,1478s, 1 460m,1 432s,1 324s,1 292w,1 254m,1 093m,1 077 m,1 031s,1 021m,997m,744s,695s,664m,606w, 513s,503s,492s,439w.1H NMR(600 MHz,CDCl3, 298 K):δ 7.51～7.23(m,CHbenzene),7.26(s,CHCDCl3).

1.3 Synthesis of[Ag(PPh3)2(BTZT)2](NO3)· CH3OH(2)

2-mercaptobenzothiazole(MBT,0.4 mmol,0.066 9 g)was added to a stirred solution of triphenylphosphine(0.4 mmol,0.104 9 g)and AgNO3(0.2 mmol, 0.034 0 g)in CH3OH(5 mL)and CH2Cl2(5 mL).After stirred for 6 h,the solution was filtered at room temperature.After slow evaporation of the filtrate at ambienttemperaturefor6days,colorlessandtransparent crystals of the title complex were obtained. Yield:47%.Element analysis Calcd.(%)for C51H44Ag N3O4P2S4:C,57.68;H,4.15;N,3.96.Found(%):C, 57.75;H,4.16;N,3.94.IR data(KBr pellets,cm-1): 3 449m,3 068m,2959w,2821w,1 637w,1 597m,1 583 w,1 494s,1 478m,1 433s,1 384s,1 326s,1 293s,1 093 m,1 077m,1 029s,1 012s,849w,744s,721w,692s, 670m,514s,497s,425w.1H NMR(600 MHz,CDCl3, 298 K):δ 7.56～7.22(m,CHbenzene),7.26(s,CHCDCl3),3.49 (s,CH3).

1.4 Structure determination

Singlecrystalsofthetitlecomplexeswere mounted on a Bruker Smart 1000 CCD diffractometer equipped with a graphite-monochromated Mo Kα(λ= 0.071 073 nm)radiation at 298 K.Semi-empirical absorption corrections were applied using SABABS program[15].All the structures were solved by direct methods using SHELXS program of the SHELXTL-97 package and refined with SHELXL-97[16].Metal atom centers were located from the E-maps and other nonhydrogen atoms were located in successive difference Fourier syntheses.The final refinements were performed by full matrix least-squares methods with anisotropic thermal parameters for non-hydrogen atoms on F2.The hydrogen atoms were generated geometrically and refined with displacement parameters riding on the concerned atoms.

Crystallographic data and experimental details for structural analysis are summarized in Table1 ,and selected bond lengths and angles of complexes 1～2 are summarized in Table2 .The hydrogen bonds of complexes 1～2 are observed in Table3 .

CCDC:1059719,1;1059720,2.

Table1 Crystallographic data for complexes 1～2

Table2 Selected bond distances(nm)and bond angles(°)for complexes 1～2

Table3 Hydrogen bond angles(°)and bond distances(nm)for complexes 1～2

2Results and discussion

2.1 Synthesis of the single crystals

Different proportions of the metal and ligand influencethestructuresofthecompounds.The complex 1 is synthesized by AgCl,PPh3,and BTZT in 1∶2∶1 molar ratio generating a complex whose each asymmetric unit contains two same structures.Also the complex 3 is similar with 1,because of the same proportion.While,the complex 4 is synthesized by AgCl,PPh3and BTZT in 1∶1∶1 molar ratio generating inversion symmetric dimers with a diamond-shaped Ag2Cl2group at the center.And two adjacent[AgCl (PPh3)(BTZT)]units are bridged by two Cl atoms. Different anions also influence the structures of the compounds.As is well-known,NO3-is an uncoordinated anion in the most of cases and halide atoms usually have the ability to connect Ag cations.Complex 2 is a mononuclear compound.

2.2 Description of the crystal structure

The complex 1 contains two same structures in each asymmetric unit,but there are different bond lengths and bond angles.Each asymmetric unit is comprised of AgCl,PPh3,and BTZT in 1∶2∶1 molar ratio.The Ag（Ⅱ）metal adopts four-coordinated mode, which is bonded to two P atoms from two PPh3ligands,a chlorine atom and a S atom from the C=S fragment of the BTZT ligand peripherally establishing a distorted tetrahedral geometry about the metal(Fig. 1).The geometry around each metal center is distorted tetrahedral as is evident from the angles in the range of 98.26(4)°～121.27(4)°.The angles around one Agatom are in the range of 99.05(5)°～120.76(4)°.The angles around the other Ag atom are in the range of 98.26(4)°～121.27(4)°.Geometrical distortionfrom idealanglescanbederivedfromtheneedto accommodate the bulky PPh3ligand and BTZT ligand.

Fig.1 Molecular structure of complex 1

Fig.2 Molecular structure of complex 2

The Ag-Cl bond distances(0.259 37(12)nm and 0.258 27(12)nm)are shorter than that observed in [AgCl(η1-S-H2stsc-NHEt)(PPh3)2](0.265 91(12)nm)[17]. But the Ag-Cl bond distances are close to those found in:[AgCl(κ1-S-C3H5NS(NeMe))(PPh3)2](0.257 0(1)nm)[18]and[AgCl(κ1-S-C3H5NS(NePrn)(PPh3)2)](0.257 51(5) nm)[18].The Ag-P bond distance is similar with that inpreviousliterature.TheAg-Sbonddistances (0.273 94(14)nmand 0.278 13(13)nm)inthe complex 1 is longer than that observed in[AgCl(TPP)2(MTZD)](0.268 61(10)nm)and{[AgCl(TPP)2(MBZT)]· (MBZT)·2(toluene)}(0.270 37(13)nm)[13].

Moreover,intramolecular N-H…Cl hydrogen bonds are observed(N…Cl 0.310 3 nm and 0.308 5 nm,∠N-H…Cl 169.18°,162.59°)in the complex 1.The Cl-Ag-S bond angles(100.47(4)°and 101.03(4)°)are smaller than[AgCl(TPP)2(MTZD)](102.68(3)°)and {[AgCl(TPP)2(MBZT)]·(MBZT)·2(toluene)}(104.91(4)°)[13]. The P-Ag-P bond angles(120.76(4)°and 121.27(4)°) are smaller than that in(Ph3P)2AgO3SCH3(132.4(4)°)[19].

Complex 2 is a simple mono-nuclear heteroleptic complex formed with distinctly soft Ag（Ⅱ）and PPh3, BTZT andanion.Each Ag is four-coordinated, surrounded by two P atoms from two PPh3ligands and two S atoms from two BTZT ligands(Fig.2 ).The angles around Ag（Ⅱ）ranging from 96.41(5)°to 126.89(4)° indicate that the geometry around Ag atom is distortedly tetrahedral.The Ag-P bond distances(0.244 59(12) nm and 0.246 31(11)nm)are longer than those in the complex[(Ph3P)2Ag(thione)]NO3(0.240 29(10)nm and0.241 57(10)nm)[20].The Ag-S bond distances (0.257 75(13)nmand 0.275 36(14)nm)are longer than those in the complex[Ag(DPEphos)(py2SH)2]NO3(0.254 37(6)nm and 0.259 49(6)nm)[21].

The main structure of 2 links free CH3OH and NO3-anion by hydrogen bonding interactions.The OH…O hydrogen bond linking free CH3OH and NO3-anion is observed(O…O 0.301 9 nm,O-H…O 175.75°) in the complex 2.The main structure and NO3-anion are sustained by hydrogen bonding interactions(N1-H1…O1,N1-H1…O2,N1-H1…N3,N2-H2…O1). The N2-H2…S2 hydrogen bonding interaction can be ignored,because the N2-H2…S2 angle(111.59°) deviates from 180°so much.The S-Ag-S angle (96.41(5)°)is smaller than those in the complex[(Ph3P)2Ag(thione)]NO3(112.18(5)°and 113.64(3)°)[20].The PAg-P angle(126.89(4)°)is larger than that in the[Ag (DPEphos)(py2SH)2]NO3(112.20(2)°)[21].

2.3 Infrared spectroscopy

The infrared spectra of complexes 1～2 shows the absorption around 1 460～1 497 cm-1due to C-C stretch vibration of the phenyl rings.The middle absorption around 3 054 cm-1for 1 and 3 068 cm-1for 2 is caused by C-H vibration of the phenyl rings.The C-H out-of-plane bending vibrations of the phenyl rings are found around 744 and 695 cm-1for 1,while 744 and 692 cm-1for 2.The absorption of the N-H stretch vibration is in 3 429 cm-1for 1 and 3 449 cm-1for 2. The C=S bond vibration is found in 1 077 cm-1.

2.4 Fluorescence spectrum

The luminescent excitation and emission spectra of complexes 1～2 and MBT ligand in the solid state at room temperature are obtained.The emission peak of PPh3is at 402 nm(λex=372 nm)[22].In the fluorescence emission spectra of MBT ligand,the emission peaks are found at 419 nm(λex=342 nm).When excited at 361 nm,a fluorescence emission peak of complex 1 is found at 432 nm.The complex 2 exhibits fluorescence signal centered at 435 nm with an excitation maximum at 353 nm.The red-shift of emission peak of 1～2 is derived from ligand-centered π-π*transition.

Fig.3 Solid-state excitation and emission spectra of 1～2 at 298 K

3Conclusions

In summary,we have successfully synthesized and characterized two novel thione complexes,[AgCl (PPh3)2(BTZT)]2and[Ag(PPh3)2(BTZT)2](NO3)·CH3OH, using IR,single-crystal X-ray diffraction,fluorescencespectrum and1H NMR spectroscopy.The complex 1 contains two same structures in each asymmetric unit, but there are different bond lengths and bond angles. Complex 2 is a simple mono-nuclear heteroleptic complex whose main structure links free CH3OH and NO3-anion by hydrogen bonding interactions.The red -shift of emission peak of 1～2 is derived from ligandcentered π-π*transition.The research plays an important role in designing and synthesizing sulfur/ phosphine ligand-based Ag（Ⅱ）complexes.

[1]Katagiri K,Sakai T,Hishikawa M,et al.Cryst.Growth Des., 2014,14:199-206

[2]Kim E,Lee H,Noh T H,et al.Cryst.Growth Des.,2014,14: 1888-1894

[3]Nitsch J,Kleeberg C,Frhlichc R,et al.Dalton Trans.,2015, 44:6944-6960

[4]Rajput G,Yadav M K,Drew M G B,et al.Inorg.Chem., 2015,54:2572-2579

[5]Pallavicini P,Dacarroa G,Diaz-Fernandezb Y A,et al.Coord. Chem.Rev.,2014,275:37-53

[6]Saira N,Stefano A S,Anita T,et al.Inorg.Chem.,2014,53: 2404-2416

[7]Qin L,Xiao S L,Ma P J,et al.Transition Met.Chem.,2013, 38:627-633

[8]Karagiannidis P,Aslanidis P.Inorg.Chim.Acta,1990,172: 241-251

[9]Lobana T S,Sultana R,Butcher R J,et al.Z.Anorg.Allg. Chem.,2014,640:1688-1695

[10]Chen S C,Yu R M,Zhao Z G,et al.Cryst.Growth Des., 2010,10:1155-1160

[11]Yue C Y,Yan C F,Feng R,et al.Inorg.Chem.,2009,48: 2873-2879

[12]Jin Q H,Zhou L L,Xu L J,et al.J.Chem.Crystallogr., 2010,40:432-436

[13]Kyros L,Banti C N,Kourkoumelis N,et al.J.Biol.Inorg. Chem.,2014,19:449-464

[14]McFarlane W,Akrivos P D,Aslanidis P,et al.Inorg.Chim. Acta,1998,281:121-125

[15]SMART and SAINT,Siemens Analytical X-ray Instrument Inc.,Madison:WI,1996.

[16]Sheldrick G M.SHELXS-97 and SHELXL-97,Program for the Refinement of Crystal Structure,University of G?ttingen, Germany,1997.

[17]Lobana T S,Kumari P,Kaur I,et al.J.Coord.Chem.,2012, 65:1750-1764

[18]Lobana T S,Sultana R,Butcher R J,et al.J.Organomet. Chem.,2013,745-746:460-469

[19]Zhang Y Y,Wang Y,Tao X,et al.Polyhedron,2008,27: 2501-2505

[20]Isab A A,Nawaz S,Saleem M,et al.Polyhedron,2010,29: 1251-1256

[21]Christofidis G,Cox P J,Aslanidis P.Polyhedron,2012,31: 502-505

[22]Huang X,Li Z F,Qiu Q M.et al.Polyhedron,2013,65:129-135

Syntheses,Crystal Structures and Spectroscopic Properties of Two Benzothiazoline-2-thione-Based Complexes for Silver（Ⅱ）

LI Zhong-Feng1ZHANG Yan-Ru1CUI Yang-Zhe1GENG Wen-Xiao1LIU Min2JIN Qiong-Hua＊,1
(1Department of Chemistry,Capital Normal University,Beijing 100048,China)
(2The College of Materials Science and Engineering,Beijing University of Technology,Beijing 100124,China)

Two silver（Ⅱ）complexes with heterocyclic thione,[AgCl(PPh3)2(BTZT)]2(1)and[Ag(PPh3)2(BTZT)2](NO3) ·CH3OH(2)(PPh3=triphenylphosphine;BTZT=benzothiazoline-2-thione)have been synthesized and characterized by IR,single-crystal X-ray diffraction,fluorescence spectrum and1H NMR spectroscopy.Heterocyclic thiones possess chemically active groups-N(H)-C(=S)-in equilibrium with its thiol form.1 and 2 are obtained by the reactions of AgCl or AgNO3with PPh3in the presence of 2-mercaptobenzothiazole(MBT)in mixed solvent(CH3OH/ CH2Cl2).The complex 1 contains two same structures in each asymmetric unit,but there are different bond lengths and bond angles.Complex 2 is a simple mono-nuclear heteroleptic complex whose main structure links free CH3OH and NO3-anion by hydrogen bonding interactions.The red-shift of emission peak of 1～2 is derived from ligand-centered π-π*transition.CCDC:1059719,1;1059720,2.

silver;triphenylphosphine;2-mercaptobenzothiazole;benzothiazoline-2-thione

O614.122

A

1001-4861(2015)08-1637-07

10.11862/CJIC.2015.195

2015-04-21。收修改稿日期：2015-05-13。

國家自然科學基金(No.21171119)，863國家高技術研究發(fā)展計劃(No.2012AA063201)，北京教育委員會基金(No.KM201210028020)，北京市優(yōu)秀人才項目(No.2010D005016000002)，北京市自然科學基金(No.7122015)資助項目。

＊通訊聯(lián)系人。E-mail：jinqh@cnu.edu.cn；會員登記號：S06N3669M1105。