A Novel Zn(Ⅱ) Complex with 1D Supramolecular Water Tape Formed by Cyclic Tetrameric Water Clusters

29卷7期结构化学(JIEGOUHUAXUE)Vol. 29, No.72010.7Chinese J. Struct. Chem.1103~1107A Novel Zn(I) Complex with 1D Supramolecular WaterTape Formed by Cyclic Tetrameric Water Clusters①LIU Kai-ShengYANG You-LiZHAO Xiao-JunYANG En-Cui2(College of Chemistry, Tianjin Key Laboratory of Structure andPerformance. for Functional Molecule, TIanjin Normal University, Tianjin 300387, China)ABSTRACT A new mixed-ligand Zn(T) complex, [Zn(4,4'-bipy)2(H2O)4].2ANS-6H2O (1, 4,4'-bipy = 4,4'-bipyridine, HANS = 2-aminonaphtbalene-1-sulfonic acid), has been isolated andstructurally characterized by single-crystal X-ray diffraction, FT-IR spectrum, TG and elementalanalysis. It crystallizes in the monoclinic system, space group P21c with a = 12.4852(8), b =18.3163(12), c = 10.9707(7) A, β= 114.2600(10)*, V = 2287.3(3) A, D。= 1.455 g/cm', M, =1002.37, Z= 2, F(000) = 1048,μ= 0.704 mm*', the final R = 0.0408 and wR = 0.962 for 4029observed reflections with I> 2o(D). Interestingly, an unusual one dimensional (1D) water tape withcyclic tetrameric water clusters can be observed in 1, which are further trapped via Zn-Ocoordination bonds exhibiting a 2D Zn(I)-water layer. These 2D Zn(I)-water layers are stackedtogether into a 3D interdigitated supramolecular architecture via weak n.. interactions, in which freeANS anions are tightly flled by bydrogen-bonding interactions. Thus, T.. and classicalhydrogen-bonding interactions are found as main driving forces to stabilize the 2D Zn(I)-waterlayers.Keywords: water tape, tetrameric water cluster, π.m interaction, bydrogen bond1 INTRODUCTIONpresented in liquid water and explain many physicalproperties, including the anomalous heat capacity ofAs one of the most abundant and cheapest speciesliquid water6. On the other hand, one-dimensionalon the earth, water plays quite important roles not(1D) aggregated water tapes lying between a 2Donly in our common life but also in most biologicalsheet and OD cluster are of much importance resul-self-assembly proceses'. Thus, intense researchesting from their crucial roles in proton translocationhave been devoted to fully understanding its unusualthrough protein membranes', 8. Recently, a fewproperties as well as structur-property correlations.T4(1) water tapes with vertex. sharing cyclic tetra-Up to now, a number of small water clusters inmeric water clusters as building blocks have beendiverse surroundings have been widely investigatedreported and are accommodated in different hosttheoretically and experimentally to recognize theframeworks, which are believed to reveal the naturebehaviors of water'~ 9. Especially, tetrameric waterof water clusters and simulate various biologicalclusters have drawn considerable interest becauseprocesses to some different extents1o. As a con-they could be considered as the principal speciestinuo中国煤化工his work, a novetl:IYHCNMHGReccived 13 Augut 20; ncepled 8 October 20009 (CCDC 645670)①Supportod by h Advanced Prjcat for Young Teachers in Tinji Normsl University②Coresponding autbr Yang EnCui, bom in 1974, pofisor, mjoring im upraolocular cemisty. B mail: cmui. yang@yabo.com.cnoLIU K. s. et al: A Novel Zn(I) Complex with ID Supramolecular1104Water Tape Formed by Cyelic Tetrameric Water ClustersNo.7Zn(I) complex, [Zn(4,4'-bipy)2(H2O)4].2ANS-6H2Omonth, pink block -shaped crystals suitable for X-ray(1), has been synthesized and fully stnucturallyanalysis were obtained by slow evaporation of thecharacterized, in which a novel water tape based onfiltrate in 20% yield (based on 4,4'-bipy). Anal.non-coplanar tetrameric water cluster can be obser-Calcd. for C4oHs2NeO16S2Zn: C, 47.93; H, 5.23; N,ved, which is different from the T4(1) water tapes.8.38%. Found: C, 48.01; H, 5.31; N, 8.59%。FT-IRParicularly, these neighboring ID water tapes are (cm"', KBr): 3429(), 3328(8), 3045(w), 1618(6),trapped by Zn~0 coordination bonds forming 2D1506(w), 1475(w)， 1416(m), 1252(w), 1200(vs),Zn()-water layers, revealing that coordination1045(s), 813(m), 625(m), 554(v), 508(m).bonds can be cooperative with water cluster hydro-2.3 Structure determinationgen bonds and thus afford an interesting waterThe structure measurement of a selected crystalassembly mannerf"!.with dimensions of 0.15mm x 0.13mm x 0.1 1mmwas performed on a computer contolled Bruker2 EXPERIMENTALAPEX-II CCD iffractometer equipped with agraphite- monochromated Mo-Ka radiation ( =2.1 Reagents and instruments0.71073 A) by using an (w-P scan mode at 294(2) KReagents were purchased commercially (HANSA total of 12332 reflections with 4029 unique oneswas from Acros and other analytical-grade reagents(Rmt = 0.0293) were measured in the range of 1.79≤were from Tianjin Chemical Reagent Factory) and0≤25.01°, of which 4029 were observed with I >used without further purification. Elemental analyses20(). The program SAINT(2] was used for integra-of carbon, hydrogen and nitrogen were carried outtion of the diffraction profles. Semi empiricalwith a CE 440 (Leeman-Labs) analyzer. FT-IRabsorption corrections were applied using thespectra (KBr pellets) were taken on an Avatar-370SADABS program. The structure was solved by(Nicolet) spectrometer in a range of 4000~400 cm^'. direct methods and refined with fll-matrix least-Thermogravimetric analysis (TGA) experiment wassquares technique using the SHELXS-97 andcarried out on a Shimadzu simultaneous DTG-60ASHELXL-97 programsl3, 49. Anisotropic thermalthermal analysis instrument from room temperatureparameters were assigned to all non-hydrogen atoms.to 800 C under N2 atmosphere at a heating rate of7The organic bydrogen atoms were generated geome-C-min*'.trically. A full-matrix least squares refinement gave22 Synthesis of[Zn(4,4' bipy)(H2O)4].2ANS-6H2Othe final R = 0.0408 and wR = 0.0962 (w = 1[(F3)The tite complex was synthesized by dissolving+ (0.0484P)2 + 1.5598P], where P= (F2+ 2F)3).the reaction mixture of HANS (89.3 mg, 0.4 mmol),The godnessof-ft indicator is 1.009. The maxi-4,4'-bipy (38.44 mg, 0.2 mmol), ZnAc2:2H2O (87.8mum peak in the final difference Fourier map ismg, 0.4 mmol), NaOH (24 mg, 0.6 mmol) and H2O0.449 e/A3 and the minimum peak- -0.290 e/A'. In(15 mL) in a 23 mL Teflon-lined autoclave at 140 Cthe final circle of refinement the largest parameterfor 2 days under autogenous pressure. After slowlyshift (No)mx = 0.001.cooling to room temperature at a rate of5"C.h", theThe selected bond lengths and bond angles arereaction mixture was filtered. Within about onelisted in Table 1.Table 1. Selected Bond Lengths (A) and Bond Angles (0)BondZ(1)-0(4)2.0875(19)2Zn(1)- N(1)中国煤化工54(19)2Z0(0)-0(5)2.1254(19)20()-04"AngleYHCNMHG0(4)- Zn(1)- 0(5)87.61(8)0(4)- Zn(1)-N(1)*89.37(8)0(4)- Zn(1)-N(I)90.63(8)04)"-Zn()-0(5)_ 92.398)0(5)-Zn()-N0)"_ 89.85(8)0(S)-2(0-N0)90.15(8)__Symmety transfomation;#l: -x+1,-y+1,-+12010 Vol. 29结构化学(JIEGOUHUAXUE) Chinese J. Struct. Chem.1105_3 RESULTS AND DISCUSSIONmetry, and the dihedral angle between the planes of0(5), 0(6), 0(7) and 0(6), 0(7). 0(8) is 21.182. In3.1 Crystal structure of 1the tetramer, the 0(5) and 0(8) atoms are trigonallyThe asymmetric unit of 1 contains half of a Zn(ID)planar with three bonds of water molecules for 0(8)center, one monodentate 4,4'-bipy ligand, one freeand two bonds of water molecules and one coor-ANS anion, two coordinated water molecules (O(4) dination bond with Zn(I) ion for 0(5). Differentand 0(5)), and three lattice water molecules (0(6),from 0(5) and 0(8), both 0(6) and 0(7) have a0(7), and 0(8)). As shown in Fig. 1, the Zn(I) cen-four-coordinated configuration with two hydrogenter located at an inversion center is six. coordinatedatoms and two lone pairs. Furthermore, the neigh-to four oxygen atoms from four coordinated waterboring tetrameric water clusters are linked viamolecules and two nitrogen atoms from two 4,4'-0(8)-H()A)-.0(6) interactions forming the 1Dbipy ligands, exhibiting a nearly ideal octahedralwater tape. All the O-H..O hydrogen bond distan-coordination geometry with all Zn-0 and Zn- Nces and bond angles within the ID water tape arebond distances flling in the normal ranges!ls!.gathered in Table 2. The average O -H.. bonddistance is 2.875 A, comparable with that of liquidwater (2.854 A)16Q.●06To the best of our knowledge, although severalexamples with vertex-sharing T4(1) water tapeshave been recently reported, such a 1D water tapeassembled from tetrameric water clusters is stillscarcely investigated. Moreover, as sbown in Fig. 2b,these 1D tapes are trapped by Zn(I) centers viaZn- 0 coordination bonds forming 2D Zn(I)-waterFig. 1. ORTEP drawing of the structural unit of1layers. Within the 2D layer the Z---Zn distances are10.971(1) and 10.675(1) A, respectively. Such anInterestingly, novel water tapes with tetramericinteresting water assembly manner with thewater clusters can be observed in 1 (Fig. 2a). Withinformation of 2D metal-water by metal and waterthe tetrameric water cluster, 0(5), 0(6), 0(7) andclusters has been unusually reported", indicating0(8) occupy its four corners. Notably, the tetramericcooperative interactions of the coordination bondswater cluster is in a slightly distorted planar geo-and water cluster bydrogen bonds.mety, and the dihedral angle between the planes ofTable 2. Hydrogen Bond Lengths (A) and Bond Angles (°)D-H-AdD-FD) .d-A)dD..A)CDHA0(6) H(6)-0(8)0.852.042.892(5)740(5)-H(5A)-0(7)1.892.707(4)612.052.829/3)520(8)-(1(8)-0(07)2.272.970(4)6806(-6(6)-0(2)"2.212.947(7)40077)-1()-0(2)2.162.783(5)30(3()-H3)-(3)20.862.987(7)6204()-H4()-0(3)*1.962.810(3)730(4)- H()-(2)*中国煤化工|6407)-H(A)-0(1)”1.850(8)- H8)-(6.62.45MHCNMHG18(3)-H3)-0(2)_2.659(9)35Symmety codes:(间#1: 1-x 1/2+x,3/2-z;#2:x-y+ 12,z- 1/2;#3:-x+1,-y+1,-++2;料:鸣-y+ 1,2-z5:.,J,2- 1,#6:x y+ 3/2,z- 1/2LIUK s. et al: A Novel Zn(I) Complex with ID Supramolecular1106Water Tape Formed by Cyelic Tetrameric Water ClustersNo.7a)上。(bFig.2. 1D water tspe wth tetramerde water clusters () and 2D Zm(I)-water layer (b) of1Furthermore, these 2D Zn(ID)-water layers are notan important role in consolidating the overallisolated, which are further cortelative by 4,4'-bipy.packing structure of 1 and 2D Zn"(I)-water layers.As shown in Fig. 3, acting as protruding ligands,More interestingly, the free ANS anions are tightly4,4'-bipys between the adjacent 2D Zn(I)- waterencapsulated in the channels of the 3D packinglayers can be stacked together by weak T"" interac-structure of 1 via N-H..O interactions betweentions into a 3D interdigitated supramoleuclar ar-amino groups of ANS and the lattice and coor-chitecture. The nearest centroid-to-centroid distancedinated water molecules (see Fig. 3 and Table 2).is 3.6613 A. Obviously, these rr interactions play首(ab)Flg.3. () 3D interdigitated architecture o[1 formed by rx tnternctions and(6) Space fllng of ANS in the channels of1 by hydrogen bonding interactions3.2 TGA and FT-IR spectrum of1lose its weight until 214 °C. From 214 to 754°C, theTGA analysis of 1 shows that the first weight losssecor中国煤化工ight loss can beranges from room temperature to 120 。C, whichobserYHCNMHG,.87%), ascribingcorresponds to the removal of three frce and twoto the leICasCUl 4,+ -upy au A anions. And thecoordinated water molcules (calcd: 17.96%, obs.: final product should be ZnO Fig. 4).17.05%). Then the remaining compound does notIn the FT-IR spectrum of 1, the strong and broad2010 VolL. 29结构化学(JIEGOUHUAXUE) Chinese J._ Struct. Chem.1107absorption centered at 3429 and 3328 cm-' can beanalysis. The aromatic C H stretching frequencyassociated to the ID water tape with strong hydro-appeared at 3045 cm^. Characteristic bands corres-gen- bonding interactionst]l and the N-H stretchingponding to the fundamental and split vS 0 stre-frequencies of the amino groups. The result is alsotching modes were observed in the range of 1000~consistent with the crytallograpbic structural1252 crm-1[18).10080-δ60+4020-oL100 200 300 400, .500600 700 800Fig.4. TG curve for1REFERENCES1) Tajkhorshid, B; Nolen, P; Jenscn, M; Micrcke, L.1; oConnell, J; Stroud, R. M; Schuten, K Science 2002, 296, 525 -S30.(2) (@Yoshizown, M; Kusukawn, T; Kawano, M; Ohhan, T; Tanaka, I; Kurihan, K; Nimun, N; Fujia, M J. sm. Chem. Soc. 2005, 127,2798- 2799. (b) Mcng, X 1; Wang, K C; Wu, W. s;Ll, B. H; Wang, D.J. ChinereJ. Sirnet, Chem. 2006, 25, 1078 -1084.(3) Srcivasuhn, B; Vtal,J.J. Angew. Chem. Im. Ed.204,43, 5769 S72.(4) Cuamatzi, P. R; Diaz, G. V; Hopf, H Angew. Chem. Imt. 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