两种基于硫醇配体的银(Ⅱ)配合物的合成、表征和晶体结构

李中峰　张振伟　崔洋哲　刘敏　杨玉平　金琼花＊,(首都师范大学化学系，北京0008)(首都师范大学物理系，北京0008)(北京工业大学材料科学与工程学院，北京00)(中央民族大学理学院，北京0008)

两种基于硫醇配体的银(Ⅱ)配合物的合成、表征和晶体结构

李中峰1张振伟2崔洋哲1刘敏3杨玉平4金琼花＊,1
(1首都师范大学化学系，北京100048)
(2首都师范大学物理系，北京100048)
(3北京工业大学材料科学与工程学院，北京100124)
(4中央民族大学理学院，北京100081)

通过AgCl、PPh3和MBT以1∶2∶1的物质的量之比反应得到2种不同的配合物[AgCl(PPh3)2(BTZT)]·CH3OH(1)和[AgCl(PPh3)2(BTZT)]2(2)(PPh3=三苯基膦；MBT=2-巯基苯并噻唑；BTZT=苯并噻唑-2-硫酮)(其中2已报道)。配合物[AgBr(PPh3)2(BTZT)]·CH3OH (3)和[AgBr(PPh3)2(BTZT)]2(4)改用AgBr以相似的反应获得(其中4已报道)。通过红外光谱、元素分析、核磁共振氢谱、X射线单晶衍射、荧光光谱对配合物1和3进行了分析和表征。我们发现在不同的化学环境中，MBT配体可以转化为BTZT配体，原因是其具有化学活性基团。荧光光谱表明1和3的发射峰均源于配体中的π-π*跃迁。

三苯基膦；2-巯基苯并噻唑；苯并噻唑-2-硫酮；配合物

0　Introduction

Currently,quite a few novel coordination complexes are reported[1-2].With the rapid development of coordination complexes,complexes with closed-shell d10metals have attracted considerable attention due to important applications in catalysis[3-4]and biochemistry[5-6].In particular,complexes bearing the Ag-S bond have raised continuously increasing interest,owing to their use in pharmacology[7]and thin films[8],as well as glass and ceramic technology[9].In coordination chemistry,it is one of the most interesting phenomena that two or more stable products are synthesized by the same reactions.The success of designed synthesis and separation of materials still look upon as something of challenge[10-11].

Herein,we set out to design,prepare,and characterize silver(Ⅱ)complexes of silver halides AgX (X=Cl,Br),using same phosphine moieties and taking into account the coordination versatility of the thiol ligand(Scheme 1),namely[AgCl(PPh3)2(BTZT)]· CH3OH(1),[AgCl(PPh3)2(BTZT)]2(2)[12],and[AgBr (PPh3)2(BTZT)]·CH3OH(3),[AgBr(PPh3)2(BTZT)]2(4)[13](PPh3=triphenylphosphine;BTZT=benzothiazoline-2-thione).The BTZT ligand was transformed from MBT ligand in different chemical environment because of chemically active groups of MBT(MBT=2-mercaptobenzothiazole)[14].Complexes 1 and 3 have been synthesized and characterized by IR,elemental analysis,1H NMR spectroscopyand single-crystalX-raydiffraction.

Scheme 1 Routine of synthesis for complexes 1～4

1　Experimental

1.1Materials 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 ElementarVario MICRO CUBE(Germany)elemental analyzer.1H NMR was recorded at room temperature with a Bruker DPX 600 spectrometer.

1.2Synthesis of[AgCl(PPh3)2(BTZT)]·CH3OH (1)

A mixture of AgCl(0.2 mmol,0.0291g),PPh3(0.4 mmol,0.104 9 g)and MBT(0.2 mmol,0.033 3 g) were dissolved in a mixture of CH3OH(5 mL)and CH2Cl2(5 mL),stirred for 6 h and filtered.Colorless crystal 1 was obtained from the filtrate after standing at the room temperature for several days.Yield:56%. Element analysis Calcd.for C44H39AgClNOP2S2(%):C, 60.89;H,4.50;N,1.61;Found(%):C,61.08;H,4.39; N,1.52.IR data(KBr pellets,cm-1):3 418w,3 049w, 2937w,2815w,1598w,1583w,1495m,1478m,1432 s,1 328m,1 092m,1 077w,1 028m,1 012w,743s, 693s,604w,512m.1H NMR(600 MHz,CDCl3,298 K):δ 7.51～7.23(m,CHbenzene).

1.3Synthesis of[AgBr(PPh3)2(BTZT)]CH3OH(3)

Complex 3 was prepared in a manner similar to that described for 1,using AgBr(0.2 mmol,0.037 0 g),PPh3(0.4 mmol,0.104 8 g)and MBT(0.2 mmol, 0.033 2 g)as starting materials.Yield:51%.Element analysis Calcd.for C44H39AgBrNOP2S2(%):C,57.92;H, 4.27;N,1.53.Found(%):C,57.81;H,4.02;N,1.46. IR data(KBr pellets,cm-1):3 434w,3 052w,3 001w, 2 935w,2 875w,2 825w,1 596w,1 492m,1 478m, 1 432s,1 323m,1 093m,1 076w,1 030m,1 012w, 996w,743s,694s,606w,513m.1H NMR(600 MHz, CDCl3,298 K):δ 7.51～7.23(m,CHbenzene).

1.4Structure determ ination

Single crystals of the title complexes were 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 SADABS program[15a].All the structures were solved by direct methods using SHELXS program of the SHELXTL-97 package and refined with SHELXL-97[15b].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 withanisotropic 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 Table 1,and selected bond lengths and angles of complexes 1 and 3 are summarized in Table 2.The bond lengths and angles of hydrogen bonds of complexes 1 and 3 are listed in Table 3.

CCDC:1407305,1;1407306,3.

Table 1 Crystallographic data for com p lexes 1 and 3

Table 2 Selected bond distances(nm)and bond angles(°)for complexes 1 and 3

Table 3 Hydrogen bonds of com p lexes 1 and 3

2　Results and discussion

2.1Synthesis of comp lexes

As is known to all,many factors can influence the structures of the compounds,such as temperature, solvent and molar ratio of the starting materials.We obtain two kinds of complexes 1 and 2 by the reactions of AgCl,PPh3,and BTZT in 1∶2∶1 molar ratio in mixed solvent(CH3OH/CH2Cl2).Complex 1 crystallizes in the monoclinic system with space group P21/n,while 2[12]crystallizes in the triclinic system with space group P1.

3 and 4 were obtained by the reactions of AgBr with PPh3in the presence of 2-mercaptobenzothiazole (MBT)in 1∶2∶1 molar ratio in mixed solvent(CH3OH/ CH2Cl2).3 crystallizes in the monoclinic system with space group P21/n,while 4[13]crystallizes in the triclinic system with space group P1.

Complexes 2 and 4 were synthesized in winter, but 1 and 3 were obtained in summer.So we think that the temperature of volatilization may influence the structures of the compounds.

2.2Infrared spectroscopy

The infrared spectra of complexes 1 and 3 show the absorption around 1 459～1 495 cm-1due to C-C stretch vibration of the phenyl rings and the middle absorption around 3 049 or 3 052 cm-1is caused by C-H vibration of the phenyl rings.The C-H out-ofplane bending vibrations of the phenyl rings are found around 743 and 694 cm-1.The absorption of the N-H stretch vibration is in the range of 3 418～3 434 cm-1. The C=N bond vibration is found in 1 432 cm-1.

2.3Description of the crystal structure

Single-crystal X-ray diffraction analysis of 1 reveals the Ag(Ⅱ)metal adopts four-coordinated mode, which is bonded to two P atoms from two PPh3ligands,one chlorine atom and one S atom from the C=S fragment of the BTZT ligand peripherally establishing a distorted tetrahedral geometry about the metal.In particular,the complex 2 contains two same moieties in each asymmetric unit[12].

In complex1(Fig.1),theAg-Pbond distance issimilar to that in previous literature.The Ag-Cl bond distance is comparable with those observed in related complexes[AgCl(κ1-S-C3H5NS(NeMe))(PPh3)2](0.257 0(1) nm)[16]and[AgCl(κ1-S-C3H5NS(NePrn)(PPh3)2)] (0.257 51(5)nm)[16].The Ag-S bond distance is longer than that found in[Ag(imdt)Cl]n[17](0.248 66(14)nm), but it is shorter than that of complex 2[12].The angles around the Ag atom are in the range of 100.50(3)°～129.27(3)°.The Cl-Ag-S bond angle is smaller than that of[AgCl(TPP)2(MTZD)](102.68(3)°)and{[AgCl (TPP)2(MBZT)]·(MBZT)·2(toluene)}(104.91(4)°)[18].

Fig.1 Perspective view of complex 1 with thermal ellipsoids drawn at the 30%probability level

Moreover,intramolecular N-H…Cl hydrogen bonds are observed(N…Cl 0.311 6(3)nm,N-H…Cl 170.0°)in the complex 1.The main structure of 1 links free CH3OH by hydrogen bonding interactions.

In complex 3(Fig.2),the angles around the Ag atom are in the range of 101.13(4)°～129.04(5)°.The coordination geometry around each Ag atom indicates a distorted tetrahedron.The Ag-P bond length is typical Ag-P distance[19].The Ag-Br distance is found in good agreement with the reported values[16,20],but is longer than those of complex 4.The Ag-S bond length is longer than that observed in[Ag2(μ-S-pySH)2(PPh3)2Br2](0.260 8(1)nm)[14].The P-Ag-P bond angle is all longer than those in another similar complex[21]. Moreover,intramolecular N-H…Br hydrogen bonds are observed(N…Br 0.326 9(5)nm,N-H…Br 169.2°) in the complex 3.The main structure of 3 links free CH3OH by hydrogen bonding interactions.The O-H…Br hydrogen bond to link free CH3OH and NO3-anion is observed(O…Br 0.332 9(7)nm,O-H…Br 171.2°) in the complex 3.

Fig.2 Perspective view of complex 3 with thermal ellipsoids drawn at the 30%probability level

Compared to complex 3,the complex 4 contains two same structures in each asymmetric unit.Each Ag atom adopts four-coordinated mode,which is coordinated with two P atoms from two PPh3,one Br atom and one S atom from benzothiazoline-2-thione ligand (BTZT).

2.4Fluorescence spectra

The luminescent excitation and emission spectra of complexes 1,3 and MBT ligand in the solid state at room temperature are obtained.The emission peak of PPh3is at 402 nm(λex=372 nm)[19].In the fluorescence emission spectrum of MBT ligand,the emission peak is found at 419 nm(λex=342 nm).When excited at 365 nm,a fluorescence emission peak of complex 1 is found at 431 nm.The complex 3 exhibits fluorescencesignal centered at 423 nm with an excitation maximum at 353 nm.The red-shift of emission peaks of 1 and 3 are derived from ligand-centered π-π* transition.

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

3　Conclusions

In summary,two kinds of silver(Ⅱ)halide complexes based on triphenylphosphine and benzothiazoline-2-thione,[AgCl(PPh3)2(BTZT)]·CH3OH(1),and [AgBr(PPh3)2(BTZT)]·CH3OH(3),were synthesized and characterized by IR,elemental analysis,1H NMR spectroscopy,luminescent spectra and single-crystal X-ray diffraction.However,by the same reactions two different products 2(The reaction condition was same as 1)and 4(The reaction condition was same as 3) were synthesized.Single-crystal X-ray diffraction analysis reveals that 1 and 3 crystallize in the monoclinic system with space group P21/n,while 2 and 4 crystallize in the triclinic system with space group P1.The luminescent spectra show that 1 and 3 emission peaks were assigned to the ligand centered π-π*transition.

[1]Rajput G,Yadav M K,Drew M G B,et al.Inorg.Chem., 2015,54:25722579

[2]Lee E,Park K M,Ikeda M,et al.Inorg.Chem.,2015,54: 5372-5383

[3]Liu H Y,Ji S J,Hao Y H.Z.Anorg.Allg.Chem.,2014,640: 2595-2599

[4]Geng J C,Qin L,Du X,et al.Z.Anorg.A llg.Chem.,2012, 638:1233-1238

[5]Banti C N,Kyros L,Geromichalos G D,et al.Eur.J.Med. Chem.,2014,77:388-399

[6]Tsukihara T,Aoyama H,Yamashita E,et al.Science,1995, 269:1069-1074

[7]Sutton B M,McGusty E,Walz D T,et al.J.Med.Chem., 1972,15:1095-1098

[8]Bain C D,Whitesides G M.Angew.Chem.,Int.Ed.,1989, 28:506-512

[9]Dash K C,Schmidbaur H.Met.Ions Biol.Syst.,1982,14: 179-205

[10]Zeidan T A,Trotta J T,Chiarella R A,et al.Cryst.Growth Des.,2013,13:2036-2046

[11]Kumalah S A,Holman K T.Inorg.Chem.,2009,48:6860-6872

[12]LI Zhong-Feng(李中峰),ZHANG Yan-Ru(张彦茹),CUI Yang-Zhe(崔洋哲),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31(8):1637-1643

[13]CUI Yang-Zhe(崔洋哲),GENG Wen-Xiao(耿文筱),QIU Qi-Ming(仇启明),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31(6):1224-1230

[14]Lobana T S,Sharma R,Butcher R J.Polyhedron,2008,27: 1375-1380

[15](a)Sheldrick GM.SADABS,University of Göttingen,Germany, 1996. (b)Sheldrick G M.SHELXS-97 and SHELXL-97,University of Göttingen,Göttingen,Germany,1997.

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

[17]Zhu Q L,Huang R D,Xu Y Q,et al.J.Coord.Chem.,2009, 62:2656-2664

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

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

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

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

Syntheses,Characterizations and Crystal Structures of Two Kinds of Silver(Ⅱ)Com p lexes Derived from Thiol Ligand

LI Zhong-Feng1ZHANG Zhen-Wei2CUI Yang-Zhe1LIU Min3YANG Yu-Ping4JIN Qiong-Hua＊,1
(1Department of Chemistry,Capital Normal University,Beijing 100048,China)
(2Department of Physics,Capital Normal University,Beijing 100048,China)
(3The College of Materials Scienceand Engineering,Beijing University of Technology,Beijing 100124,China)
(4School of Science,Minzu University of China,Beijing 100081,China)

Two kinds of complexes[AgCl(PPh3)2(BTZT)]·CH3OH(1)and[AgCl(PPh3)2(BTZT)]2(2)were obtained by the reaction of AgCl,PPh3,and MBT in 1∶2∶1 molar ratio(PPh3=triphenylphosphine;MBT=2-mercaptobenzothiazole BTZT=benzothiazoline-2-thione)(2 has been reported).[AgBr(PPh3)2(BTZT)]·CH3OH(3)and[AgBr(PPh3)2(BTZT)]2(4)were prepared in a manner similar to 1 and 2 using AgBr(4 has been reported).Complexes 1 and 3 have been characterized by IR,elemental analysis,1H NMR spectroscopy,fluorescence spectrum and singlecrystal X-ray diffraction.The MBT ligand can transform into the BTZT ligand in different chemical environment because of its chemically active groups.The luminescent spectra show that emission peaks of 1 and 3 are assigned to the ligand centered π-π*transition.CCDC:1407305,1;1407306,3.

triphenylphosphine;2-mercaptobenzothiazole;benzothiazoline-2-thione;complex

O614.122

A

1001-4861(2016)01-0139-06

10.11862/CJIC.2016.023

2015-08-19。收修改稿日期：2015-11-11。

国家自然科学基金(No.21171119，11104360，11204191，81573832)、863国家高技术研究发展计划(No.2012AA063201)、北京教育委员会基金(No.KM201210028020)和北京市优秀人才项目(No.2010D005016000002)资助。

＊通信联系人。

E-mail：jinqh@cnu.edu.cn；会员登记号：S06N3669M1105。