Novel polymeric heteropolytungstates and -molybdates

C. R. Acad. Sci. Chimie de Petat

Paris, solide

t. 1, SCrie II c, p. 351-360, et cristallochimie/Solid

Novel polymeric and -molybdates

1998 state chemistry

(Received

14 February

Institut.

1997, accepted

Abstract with

- .\ review polvmeric netiorlc

europiutn coInpounds

Lniversidt

crystal

chemistry

heteropolytungstates

Bernt KREBS*, Ina LOOSE, Michael B&ING, Anorganisch-Chemisches

and

Miinster.

27 October

Andreas NOH, Elisabeth DROSTE

1Yiilhelm-I
8, D-481

49 Miinstrr-.

Germany

1997)

is Cgiwn on the wntheGs ot‘ :L se&s of nt>vel heteropolytuIlgst:1Ic!: structures ccmta;uing hisn~uth. chromium, copper, ruthenium,

as heteroatoms:. ‘l’heir ct.\-stal structure3 \vere reported are: Na(,lRh,((!l I,(:(~~O),\~~,,O,,(C)I-1),].3.~11~(

dc~en~~~ed

1,~

1 (li.

single crystal I<,S\‘a,Iliu(l

ant1 -mol$xlates rhocliuin, ceriutn and N-la\methods. l,C.)),~l\Y’,,O,,,(OII),I

‘l’he

IO 1{2O (2:. I<,,Na, [((:u (t I,(.lj,\X~,,( ),,, (Of IjJ)- C\Y,,( ).~,,(OI~I))3]~.31 I I,() (3). (;e(I 1,C))7~(:rlZlo,0,s~(~l I),] .4f110 (4), and S:~,l-I,~l~u,(l-i~~~~l~~(~~i~~~‘~~~~~-~~~~~3?1I,0 (5). :\: \ :I ctrtnmon feature they all contaio oligomcric isopolcmetalatc or heteropol\imct:llatc ‘$-roups of kno\\an st ruciure and size which are linked 1)~ \,arious transition metal or rare earth metal centers to form :I numhcr (If no\ el estendcd polvmeric h~tcropr)l\.rnctnl:llc neturorks.

A polymeric 1aFr structure 1s formed in 1 1)~ ta-o-climensionnl linking .<,f dirhoclium tc;r:uicc.t:ltc units and [W1,O,,(OI Jjd isopolvanious. 111 2 p:u.;~t~mgst:lte-D units :we linked l)\- cjctahedral RuO ,!I I”( )jr: polvhedr:t to form polymwic nnionic chains. Similar chains arc present in 3, howewr with (1~ hcing in a quare plan;tr (:uO.(I_ I,(y), and additlr,nnl molccul:u tiotl-coordiii:ltecl prnhmgstnte anit ~1s art present in the _ - coordination. crystal. In 4 nuie-cooccliIi~~te (:e( ):(I I,( 1): ptrlyheclra share comers with two neighbounrig ;uiions of campsition [Crl\lo,018(( )I&]‘~ tc) f arm p~A\mcric - _I chain mc~lecules 01‘ alternating cerium Ix~lvh~tlra and hesamol~l~dochromate(II1) units. In 5 structurally rcmarlwblc (13i3\Y2~C )7C,11J groulx share edges \vith eight-coordiil:ltc ftuO,(H,( ))(, polyhedra. :igain 10 form three-tliln~nsit,n:il lwlvmcric hcteropol\- nct\vc)rks. ‘(‘8 \cadtmic tics Scicnccs/I
/ heteropolymolybdate

/ polymeric

heteropolymetalate

RCsumC- Nouveaux composCshCtCropolytungstates et -molybdates polymCrisCs.Ce travail decrit la d’une serie de nouveaux hCt&opolytungstates et -molybdates polymeris& en reseau avec du bismuth, du chrome, du cuivre, du rhodium, du ckrium et de l’europium. Leur structure cristalline a et6 d&term&e aux rayons X sur des monocristaux. Ces compose? ont pour formule brute : Na,[Rh,(CH&OO)8W1z038(0H)2] synch&se

,25H20

(1). K,Na,~Ru(H,0),(Vli,30,i,~(OH~~l~10HL0(21,&,Na,, ~~Cu~H,0~,W,104,~~OH~~~,~W,~0,,,(OH~~~l

.31H,O (3),Ce(HZO),(CrMo,0,,(OH-I),]~4H,0(4) et Na,H,[(Bi,W,10,,)].29H2C) (5). Cei; composes contiennent tous des groupements oligomCriqucs isopolym6tall& ou h~tPropolym~tallCs de taille et de structure connues relits entre eux par des metaux dc transition ou des cerres rares pour former de nouveaux rbseaux plus itetldus. Lc composC 1 forme une couche par associarion bidimensionnelle du t&a&ate de dirhodium avec les isopolyanions [W,z0,,(OH),]6-. Les unit& de paratungstate B du compose 2 sont reliies aux poly$dres octogonaux de Ru04(H,O), pour former des chaines anioniques polym&rist-es, Les chai’nes similaires de 3 respectent la structure en plan carrg du cuivre mais des anions de paratungstatc non coordonn& apparaissent aussi dans le cristal. Les polykdres de Ce(H,O)? partagent des sommets avec deux anions [Cr~,~o,O,,(OH),]‘voisins pour former des chaines oh les polyPdres de &urn alternent avec les hexatnolybdochromate(III). Les groupes BizWz107, du compose 5, remarquables par leurs structure, partagent des catis avec des polytdres de Eu,(HzO),, pour former B nouveau des reseaux en trois dimensions. (R&umC: redig6 par la r6daction). 0 Academic d~.s Sciences/Elsevier, Paris hCt&opolytungstate

/ hCtCropolymolybdate

I polymkre

h&&opolym&allate -

Communicated * Correspondence

by Fraqois and reprints

MATHJX

B. Krebs

Version

et al.

franqaise

abrkghe

La chimie des polyoxometallates est principalement dominee par le molybdtne, le tungstene et le vanadium dans leur plus haut &at d’oxydation. Le d&eioppement le plus speceaculaire est observe, de composition [X$I,O,]7(M = W, MO, outre pour la famille [M,,O,]p- p our les heteropolyanions Nb, V, . . ; X = Si, P, B, Co, Fe, Cu, .. .). La plupart de ces clusters ont des structures discretes formtes d’arrangements t&s symetriques d’octatdres Mo(, mettant en commun des a&es, des sommets ou des faces. En revanche, des structures polyoanioniques plus &endues telles que des chaines ou des structures en couches sont trb rares. I.es polyanions peuvent aussi jouer le role de ligands pour former des structures lacunaires ou saturbes. Dam ces structures associant le polyanion a un cation, l’augmentation de la nuclParitC peut conduire h des structures polymeriques comme dans [UMor204J8et Th”’ oh le polyanion peut erre consider+ comme un ligand hexadentate, develop ant des chaines P+ oh deux unites d’unitts UMo,, liees par des ions Th”‘. Un autre exemple est constitue par [MO,&] adjacentes sont likes par deux Eu’+. D’autes exemples, a base de cobalt en particulier, sont disponibles dans la litttrature. Dans ce travail, cinq nouveaux hettropolytungstates polymerists sont dtcrits, illustrant la plus grande varietal! structurale.

1. ComposCs contenant

un seul type d’h&tCroatome

forNa~[Rh~(OOCCH~)8](W120~s((->H)~)]~25H~0 (I) p ossede une structure bidimensionnelle mte d’unites metatungstatiques [W,,O,,,(OH),]“1ites par des groupes Rh,(OOCCHJ,. L’ion metatungstate derive de la structure Keggin-CY. par abstraction du tttraedre central X0,. Le rhodium est dans un environnement octaedrique form& par quatre groupes OOCCH,. K,Na2[Ru(H10),(W, ,O,,,,(OH)L)]. 1OHlO (2) represente le premier polyoxometallate polymerist contenant du ruthenium comme heterotlbment. Sa structure en chaine peut etre d&rite comme des assemblages de groupes paratungstace-B connect& par des ponts Ru04(H,0),. K,,Na,[Cu(H,0),(W,20,,,(OH),)1.31H,0 (3) : comme (2), ce compose contient des unites paraB connect&es les unes aux autres par des ponrs Cu02(H2C>), pour former des chai’nes avec en plus, des groupes pant-B isoles distribues alternativement de part et d’autre des chaines.

2. ComposCs contenant

deux types d’hCtCroatomes

Ce(HzO),[CrMob0,,(OH),]~4H,0 (4) : la structure de ce compost monodimensionnel peut @tre d&rite a partir d’unites a structure d’Anderson [CrMo60,s(OH)G]3-, &es entre elles par des ions Ce3+. Celui-ci est au centre d’un octatdre d’atomes d’oxygkne. La structure de Na3H,[Eu,(H20),X(Bi2W1?C)7(,].29Hr0 (5) consiste en un arrangement tridimensionnel d’anions [Bi,Wzz07(,]‘4-lits par des ions Eu”‘. (Version frangaise abrtgte redigee par la redaction).

1. Introduction The chemistry of polynuclear oxometalate anions is dominated by molybdenum, tungsten, and vanadium in their highest oxidation states or in certain reduced states. The most spectacular development is observed, besides the class of isopolyanions [M,,O,]“, for the even more variable heteropolymetalates with the general formula [X,M,rJO,,Iq- (M = W, MO, Nb, V ,...; X = Si, R B, Co, Fe, Cu ,...) [l-5]. Most of them have discrete cluster-like srructures of definite sizes and shapes formed by highly symmetrical networks of MO, octahe-

352

dra sharing edges, corners, or faces. Extended heteropolyanions showing chain- or layer-like networks have been observed very rarely [G-l 01. Polyoxometalates can act as ligands forming either plenary or lacunary structures [3]. These cation-polyanion complexes of increasing nuclearities may exhibit polymeric structures: This is the case for the complex formed from the heteropolyanion [ UMo , 204L] sand Th4+, in which the polyanion acts as a hexadentate ligand forming chains of UMO,~ units [6] linked by Th”‘. A second example is provided by the corn lex formed from the isopolyanion [Mos02,] P‘- and ELI". In this case,

Novel polymeric

rwo adjacent MO&& units are linked by two Eu3+ ions to give an infinite chain [7]. Another two structures, (ET)s[PMnW, t03J.2Hz0 [8] (ET = bis(ethylenedithio)-tetrathiafulvalene) and [NEt3H]5[XCoW,,03J~3H20 [91 have to be mentioned, which both consist of chains of Keggin-type molecules joined by W-O-M links (M = Co, Mn). Further recently reported examples of extended heteropolyanions showing polymeric structures are the cobalt-containing compounds KCOW,Q~)~(H,W,,[ 101, @k+Q2Na2[Na2C02W&4,,0*2)1,? Na, [NaCo3(OH)2(H20)121~16H20and

W,,O,,,O-U,W,O),,l

.22&O [Ill.

In this review we report five novel polymeric heteropolytungstates which show chain-, layerlike and three-dimensional framework structures, respectively.

2. Polymeric heteroatom

complexes with one

1 can be obtained by reacting Na,W04 .2H,O with NaOOCCH3 and RhC1,.3H,O in acidic aqueous solution: 12[W0,12+ 4Rh3+ + lO[CH:,COO]-+

16H30’ -+ [~4(00CCH3),(W,,Q3,(OH),)1+ 2CH,OH

t 2C0,

Figure

la. View

Figure

la.

t 22H,O

on the unit

Vue de la maille

cell of 1 (anionic ClCmentaire

part

de 1 (partie

heteropolytungstates

and -molybdates

The interesting novel heteropolytungstate

Na,[~4(00CCH3)8(W,2038(0H)2)1.25H20 [ 121 is the first rhodium-containing polymeric polyoxometalate. It shows a layer-like structure. Metatungstate units are linked by four [Rh2(00CCH,)J groups in a two-dimensional way. A view of the unit cell of 1 in the c-direction is shown injgure la. Figure lb representsa part of an anionic layer of 1. The metatungstate unit W,,O,,KW,l G consistsof twelve WO, octahedra arranged in four groups of three edgeshared octahedra, W,0t3. These triplet W30,, groups are linked by shared corners to each other. lF/o protons are located inside the anion framework at triply bridged oxygen atoms [ 131. The metatungstate anion hasbeen characterized severaltimes and can be derived from the wellknown a-Keggin structure by removing a central X0, tetrahedron [ 141. Bond distancesand angles inside these metatungstate anions are comparable to those in 1. The bridging [Rh,(OOCCH,),] unit consistsof two rhodium atoms which are bonded to each other with an intermetallic bond length of 2.383(4) A. Besides,the Rhz4’ ion is capped with four [OOCCHJgroups with Rh-O(acetate) bond distances of 1.98(2) A and 2.05(3) A. The distorted octahedral coordination of each rhodium atom is completed by a terminal oxygen atom of a metatungstate unit which suppliesalso the connection between the poly-

of the structure). anionique

de la structure).

353

6. Krebs

et al.

Figure

lb.

Part of an anionic

Figure

lb.

Partie

d’une

couche

layer of 1. anionique

de 1

oxotungstate and rhodate part of the whole layer-like anion framework. The Rh-O(metatungstate) bond distance amounts to 2.25(2) A and the W-O(rhodium) bond length is 1.72(2) A. Another previously reported two-dimensional heteropolytungstate has the formula (Me4N),.Naz[Na,Co,W,2040(0H)2 (H,O),,].lGH,O which can best be described as an anionic polymer [Na,Co,W,,O,+,(OH), (Hz0),J4~[ 111. The layers are formed here by connection of paratungstate-B units through four COO,, octahedra and two NaO, pentagonal bipyramids. An interesting recently reported non-polymeric rhodium-substituted anion of formula [(PO,)W, ,Oj,(Rhz(OAc),(dmso)z)]iis related to the structure of 1. Compared to 1, this lacunary Keggin-like anion incorporates a Rh14’ group into the surface of the molecular unit. The Rh-Rh bond is stretched, apparently to accommodate the size of the lacunary Keggin anion vacancy [ 151,

with Reaction of RuC1JCH3CN), Na,W04+2H,0 in an aqueous acidic solution gives polymeric anions of 2: 12[WO,]‘-- + Ru2+ + 14H,O’ (W,7040(OH)JlX+ 18H,O

354

--+ [Ru(H,O),.

The [Ru(H,O),(H,W,~O~~)]‘anion [12] represents the first polymeric polyoxometalate structure with ruthenium as a heteroelement. In contrast to [Rh4(00CCH3),(W,,04,~(OH),)]‘-, 2 showsa chain-like structure with paratungstate-B units connected to each other by Ru04(H,0), bridges. In fl’gurc 2 the unit cell of 2 is presented illustrating chains of [Ru(H20),(W,,0,,(OH),)]srunning parallel to the u-axis. The well-known paratungstate-B unit [W, 2040(OH)2] lo- shows structural details similar to those reported previously [ 16, 171 with almost the samebond distancesand angles inside the anion. It consists of twelve WO, octahedra which can be separatedinto four corner-sharing groups. The upper and lower groups consist of three edge-sharingWO6 octahedra with one common oxygen; each W atom has one terminal oxygen atom. In contrast, the two other groups are linearly connected; thus the structure does not involve u?, oxygen bridges, and each W atom is bonded to two unshared oxygen atoms. The two protons are bonded in the sameway asin 1 inside the anion framework to triply bridging oxygen atoms. These isopolyanions are bridged through distorted RuOj(H,O), octahedra with Ru-O(paratungstate) bond distances of 2.01(4) A and 2.47(3) A. Th e coordination of the ruthenium atom is completed by two aquo ligands

Novel

Figure

2. The

unit

Figure

2. Maille

cell of 2 (anionic

&mentaire

polymeric

heteropolytungstates

and

-molybdates

part oE the structure).

de 2 (partie

anionique

de la structure).

with a Ku-O(water) distance of 1.99(4) A. The W-O(ruthenium) bond length amounts to 1.72(4) A. Another recent example of an extended heteropolyanion showing a chain-like structure is the cobalt-containing heteropolyanion

[(CO(H~O),),(W,~O~~(OH)~)I~-

[ 101. The

structure of this anion is formed by paradodecatungstate jons F’,2040(OH)21 “ions to yield chains in linked by two Co almost the same way as in 2.

If NazW04.2H,0 and CU(N~~),.~H,O are reacted in water (acidic pH) according to 36[WO,]‘+ 2Cu” + 42H,O+ -+ 2[Cu-

(H20)2(W,2040((~H)L)18-

the structure to give a layer-like anion framework. Figure.3 shows the unit cell of 3 projected in the direction of the crystallographic a-axis. As expected, the paratungstate-B anions are structurally similar to the ones in 2 with almost the same bond lengths and angles inside the cluster. Being typical for Cul’ complexes, the coordination of the cop er ion is a square plane. Spec&ally, the Cu P+ ion is surrounded by two terminal oxygen atoms of the paratungstate-B anions with Cu-O(paratun state) bond lengths of 1.35(3) A and 1.37(3) 1 and by two water molecules with Cu-O(water) bond distances of 1.92(3) A and I .97(3) A. The average W’O(copper) bond distance amounts to 1.72 A. Until now there is no corresponding heteropolytungstate structure published with two different types of anions (polymeric chains and individual units) within one crystal structure.

+ [W,,O,,(OH)$“+ 56H,O a novel copper-containing heteropolytungstate is formed. The single crystal X-ray structure analysis of 3 reveals the first polymeric heteropolymetalate with copper as the heteroelement. Compared to K~Na,[Ru(HzO),(W,,O~,(OH)~)l~lOH,O, 3 contains paratungstate-B units connected to each other by Cu0,(H20), bridges which leads to a chain-like anion [Cu(H20), (W,,04,(OH)2)]8[12]. In addition to this, 3 contains also individual paratungstate-B units

4 can be obtained from acidic aqueous solutions containing Na,Mo04.2H20, CeCl, .7H,O, and Cr(N03),.6H,0 in stoichiometric amounts: GHMoO*+ Ce3’ + Cr3+ + 7H,O +

alternating

Ce(HL0)7[CrMo601x(OH),l

with

the chain-like

polymeric

part

of

3. Polymeric complexes with two heteroatoms 3.1. Ce(H,O),[CrMoJl,,(OH)~~4H,O (4)

355

EL Krebs

et al.

b A 7

Figure

3. View

of the unit

Figure

3. Vue de la maille

cell of 3 ( anionic &mentaire

part of the structure).

de 3 (partie

anionique

The polymeric cerium- and chromium-containing heteropolymolybdate Ce(H,0)7[CrMoG0,,(OH),J.4H,0 4 [18] shows a chainlike structure. As depicted injqre 4a hexamolybdate subunits containing Cr +, known as the Anderson anion, [19] [CrMo$O,,(OH),l’, are linked to each other by Ce + cations in a one-dimensional way. The well-known Anderson anion consists of six edge-sharing WO, octahedra arranged in a planar ring-like arrangement, Likewise, the heteroatom (i.e. Cr3+) in the centre is coordinated octahedrally by six oxygen atoms. The Anderson subunit of 4 reveals W-O and Cr-0 bond distances and reported for Na,angles as previously [CrMoG0,,(OH),J.8Hz0 [ 191. Each Ce(III)

Figure . Rgure

356

4a. Section

of the polymeric

4a. Section

d’une

chaine

chain polym&re

de la structure).

cation is coordinated by seven water molecules and two oxygen ligand atoms of two different anions forming a distorted three-capped trigonal prism. The Ce-0 bond distances in the range of 2.446 to 2.638 A are in good agreement with comparable Ce-0 bond distances found in the literature. A view of the unit cell of Ce(Hz0)7[CrMo~0,8(OH),]~4H,0 along the crystallographic c-direction is given in figure 46. The one-dimensional chains of alternating [CrMobO,,(OH),]‘units and Ce3+ run along the &axis of the orthorhombic unit cell. The Ce3+ cations link subunits of the same orientation relative to the b-axis. The direction of the chains alternates in each layer.

in Ce(H20),[CrMo,0,,(OH)6].4H20. dans Ce(HZO),[CrMo,0,,(OH),,].4H,0.

Novel polymeric

Figure

4b. The unit cell of 4; view along c-axis.

Figure

4b. Maille

kltmentaire

de 4 ; we

suivant

I’axe c,

5 is obtained by reacting stoichiometric amounts of Eu(N0,),.5H,O and NaGIBiWll. 03,H]~xH,0 [20] in aqueous solution: 3Eu3+ +2[BiW,,O,,H]“-

+ 20H,O

heteropolytungstates

and -molybdates

(H20)6]G-, has recently been reported by our group [4]. As expected, the Bi-0 bond distances and angles of both compounds are in good agreement [Bi-O,, = 2.15 A (5), 2.10 A (Bi2W’20Fe2); 0-Bi-O,,, = 87.9” (5), 86.03” (Bi2Wz0Fe,)]. A special feature of the [Bi,W,,0,G]‘4anion is the presence of WO, octahedra with one, two, and without any terminal oxygen ligand atoms. The two antiLipscomb octahedra at the periphery of the anion with the unusual number of three terminal oxy en atoms are stabilisedby coordinating 5+-cations each. Obviously, these octatwo ELI. hedra can be understood to be crypto-antiLipscomb octahedra showing a strongly lessened tranr-effect. Beside this feature the structure of the [Bi2W2207J14- anion is closely related to the antimony compound [Sb,W,,0,4(0H)J 12- [4,2 11. The corresponding peripheral octahedra of the latter differ from those of 5 by the presence of two terminal hydroxo groups. Further heteropolytungstates containing antimony [22,23] and selenium [24,25] provide related structure types and have been previously published. . . The coordmatron of [BI~W~~O,~] ‘*- by the four Eu-‘+ cations described above is completed by another two Eu”’ ions each linked to one quasi-terminal oxygen atom of both P-BBiW, units. The resulting three-dimensional network structure is depicted in figure 56.

-+ [Euj.

(H20),,(Bi,W,,07(;)15- + 2H.P’ The complex structure of Na3H,[Eu3(H2. O),,(Bi 14-2 W 22 0 76 )]*29H,O consistsof [Bi,W$ anions linked by Eu”’ forming a three?%I dimensional polymeric network. Figure 5a represents the [Bi,W,,O,,]‘“anion surrounded by six Eu”’ cations. Each Eu”’ is linked to the anionic network by two oxygen atoms, and another six water molecules complete the distorted coordination sphere. The Eu-0 bond distances(2.394 A) are slightly shorter than the Eu-Ow distances of 2.464 A (0,x) = water). The novel centrosymmetric [BiLW2,0,,] “anion consistsof two identical B-B-BiW, subunits which are connected to each other by four WO6 octahedra. The centre of each unit is formed by a trigonally coordinated BiO, group with the lone pair at the top of the pyramid. The first Bi(II1) heteropolytungstate consisting only of B-B-BiW,, units, lBizW,OFezOGs(OH),

Figure 5a. Polyhedral plot of the [Bi2W,,0,,]‘*and its coordination by six Eu”. The coordination of ELI” is completed by water molecules (empty

anion sphere circles).

Figure 5a. Graphe polytdrique de I‘anion [Bi,W,20,,] 14et sa coordination par six cations .tk”. La sphere de coordination de Eu” est complCtte par des mokcules d’eau (crrcles vides).

357

B. Krebs

et al.

L Figure

5b. The

Figure

a unit

5b. Maille

cell of 5: view

&mentaire

along

the h-direction

de 5 ; vue suivant

4. Conclusion

~Na~lRu(H,0),(W,20~~(OH)~)1.10H~0, K,oNaG[Cu(H,0),(W,2040(0H)2)12[W,2040 (OH),].3 1 H,O, and Ce(H,O),[CrMo,O, (OH),].4H,O form a layer-like structure,

s

Na,[Rh~(00CCH.,),(W,~0.~8(0H)2)1. 25H,O,

(water

l’axe b (I’eau

and sodium et les cations

cations sodium

are omitted sent omis

for clarity). pour

la clam? du dessin).

polyoxometalates We$J),Na2N2C02WtZ 040(OH)2(H20)121~16H2C~ and Na,[NaCo3 W,,04,(0H),(H,0)16]~22H20 have applications in oxidation catalysis [I I]. Therefore, we investigate the properties of the present structures in heterogenous catalysis. These results will be published soon.

and

Na3H,[Eu~(H20),8(Bi~W2207G)1~29H20 a two- and three-dimensfional polymer, respectively. The basic units in all these structures are complete isopolyanions (in 1, 2, and 3) and heteropolyanions (in 3, and 4) acting as multiby transition dentate ligands coordinated metal-oxygen and lanthanoid-oxygen polyhedra. Due to the exclusively inorganic nature of these novel polymeric heteropolyanions, making them inherently stable towards decomposition under extreme conditions, 1, 2, 3,4, and 5 are attractive as robust oxidation catalysts.

Diffraction experiments were performed on Syntex P2, (for 1 and 4), Siemens P3lV diffractometers (for 2 and 3)) and a STOE IPDS (for 5) respectively with MoKtr radiation (h = for 0.71073 A) and with different correction absorption, Lorentz and polarisation effects. The structures were solved by direct methods

We

with

previously

358

reported

that

the

polymeric

5. Experimental

section

5.1. Crystal structure

the program

detertninution

SHELX’I’l.-PLUS

and

refined

Novel

heteropolytungstates

and

-molybdates

CN),: RuC13.3H,0 (2 g, 7.6 mmol) was dissolved in acetonitrile (40 mL) under nitrogen atmosphere and Zn powder (10 g, 152 mmol) was added. The mixture was allowed to react at room temperature for 3 h, after which the solution had changed colour from brown to yellow; it was filtered and 3/4 of the initial volume was evaporated under vacuum; in the resulting volume a yellow precipitate was formed, it was filtered off, washed with diethylether and dried. In a second step Na,WO,, 2H,O (5.08 g, 15.4 mmol) dissolved in boiling water (I 5 mI,) and concentrated HNO, (1 mL) was mixed under nitrogen atmosphere with a solution of RuC12(CH,CN), (0.336 g, 1 mmol) in water (4 mL) and stirred for 1 h at 95 “C. The final pH of the 20 “C reaction mixture was 7.5. After addition of KNO, (2 g, 20 mmol) and repeated filtration of paratungstate-B, brown crystals of 2 were formed after several weeks.

(on F2) with SHELXL 93 by full matrix leastsquares. Oxygen atoms were refined isotropitally; all other atoms were refined anisotropitally. Crystal data for 1: tetragonal, space group 14 m2, d = 17.275(2), c = 12.960(2) A. Crystal data for 2: monoclinic, space group P2,/n, a = 13.066(10), 6 = 14.945(8), c = 13.507(13) A, B = 116.28(Z): Crystal data for 3: triclinic, space group Pl , a = 11.860(5), 6 = 13.087(4), c = 25.026(7)&a = 76.54(10), p = 87.67(10), y= 88.13(10)". Crystal data for 4: orthorhombic, space group Pca2, a = 11.808(2), b = 10.958(2), c = 22.545(4) A. Crystal data for 5: monoclinic, space group 12/a, a = 35.806(6), 6 = 19.084(3), c = 35.888(6)A, p = 92.20(2)". Details of the data collection and processing, structure analysis and refinement for 1, 2, 3, 4, and 5 are summarised in [ 12, 181 and the supplementary material cited therein.

5.2. Preparation

polymeric

of the compounds

5 2.1. Na~~Rb4(00CC~~,(W,,q,,(OH),)/ .25H,O (1) Na,W0,.2Hz0 (2.6 g, 7.9 mmol), Cu(NOJ,.3H,O (0.75 g, 3.1 mmol) and RuCl,.3H,O (0.25 g, 1 mmol) were dissolved in a solution of HOOCCH3/Na00CCHj (1 M, 30 mL) and refluxed for 1 h at 80 “C. This solution was mixed with a KC1 solution (1 M, 10 ml,) and allowed to cool slowly. After partial evaporation of the solvent at room temperature, brown crystals of 2 were obtained in several days. The role of RuC13.3H,0 in the synthesis of 2 is not yet clearly understood; the brown colour of the product may result from RuClj sticking on the surface of the crystals.

Na,W04.2H,0 (1.98 g, 6 mmol) and NaOOCCH, (0.328 g, 4 mmol) were dissolved in a HOOCCH,/NaOOCCH, solution (1 M, 25 mL) and stirred. To this mixture RhCl,.3H,O (0.543 g, 2 mmol) in a solution of HOOCCH,/NaOOCCH, (1 M, 5 ml,) was dropwise added and refluxed 8 h at 80 “C. During the reaction the solution changed colour from dark red to deep green. ‘I-he mixture was allowed to cool slowly and green crystalline needles were formed after several hours.

5.2.2. K~Na2[R~fi”lT20~,CW,,040fOH)~)/ .IOHzO

(2)

5.2.4. Ce(H,0),fCrMo601,(OH)~~4H,0

The first step in the synthesis of 2 is the preparation of the Ru(II)-Complex RuC12(CH,

Table

Selected

I.

average

K,Na,lRu(HLO),(W,ZO,o(OH)~)l,lO Tableau

bond H,O

I. Une st!lection

de longueurs

K,Na2lRu(H~0)2(W,,04o(oH)~~l.lO

lengths

NazMoOh.2Hz0 (4.2 g, 17.4 mmol) was dissolved in water (60 mL) and heated at 60 “C.

of

Na,LRh.,(<)O(:CHI)8(W/,Z0,,(C)H),)125H~~~

(2) and ~~,,Na,[~~u(H110)L(W,LOiiO(OH)~)]L[W1~O4,~~OH)Zj.3lHZO

de liaisons Hz0

(A)

moyennes

(4)

(en A) dans Na,,[Rh,,([)C)CCHj)x(\\X’,,0,,((~H),)].25Hz0

(2) et KL,,n‘a,[Cu(H2C)),(W,zo,,,(oH)~)].~l

HLO

(l), (3). (I),

(3).

M-O(W) IL-O(Ac) &O(H,C)) W-O(M) “M

= Rh “M

= Ru ‘M

= Cu.

359

B. Krebs et al.

A solution of CeC13.7H,0 (0.924 g, 2.48 mmol) and Cr(N0J36H,0 (0.992 g, 2.48 mmol) in water (30 mL) was then added to this mixture. By dropwise addition of HCl (1 M) the pH of the solution was set to 1.5. The reaction mixture was stirred and heated for 2 h at 80 “C, hot filtered and allowed to cool slowly. Pink single crystals of 4 were formed over several hours. 5.2.5.

Na..3H2rEu~(H20)lR(BiZW220,(Sj

.29H*O (5) The polymeric compound 5 can be obtained in a two-step synthesis. First step is the preparation of Na(,[BiW, 1038H] .xH,O. Na,WO,, .2H,O (32.1 g, 100 mmol) was dissolved in a mixture of boiling water (I 00 mL) and a HOOCCHj/Na00CCH3 solution (4 M, 40 ml.). Then BiO(NO,,)SH,O (2.77 g, 9.1 mmol) dissolved in concentrated HNO, (IO.4 mL) was added dropwise to the tung-

References [l]

Pope M.T., Hereropoly Springer-Verlag, Berlin. 1983.

and lsopoly Oxometalaces, Heidelberg, New York, Tokyo,

[2] Pope M.l:, in: Wilkinson G. (Ed.), Comprehensive ordination Chemistry, l’ergamon Press, Oxford, vol. 3, pp. 1023-105X. [3]

Co1987.

M.T., Miiller A., Angew. Chetn. 103 (1991) 56; Angew. Chem., lnr. Ed. Engl. 30 (1991) 34. (41 Krebs B., Klein R., in: Pope M.T., Miiller A. (Eds.j Heteropolp and lsopoly Oxom&ates: From Platonic Solids to Anti-Retroviral Activity, Kluwer Academic Publishers. Dordrecht, The Netherlands. 1994, pp. 4l57. [i]

Pope

Krcbs B., Klein

R., Mol.

Engineering

3 (109.3)

[6] Molchanov V.N., Tatjanina l.V., Torchenkova J. Chem. Sot. Chem. Commun. (I 98 I ) 0.3. [7] Yamasc I’., Naruke (1991) 285.

H., J. Chem.

Sot. Dalton

4.3. E.A.. Tram.

[Sj Gal&n-Mascar& J.R., GinGnwSaiz (1.. Triki S., C;&ncz-Garcia J,, Coronado I-.., Ouahab I.., Angew. Chem. 107 (1995) 1601; Anger. Chcm., [nt. Ed. Engl 34 (1395) 1460. [9] Evans Jr. H .T., Weakley T.J.K.. Jameson Sot. Dalton (1996) 2537.

(;.B., J. Chem.

II 01 GimCnez-Saiz C., Gal&n-Mascartis J.R., %iki S., Coronado E., Ouahab L.. Inorg. Chem. 34 (1935) 524.

360

state-containing solution. The resulting reaction mixture was refluxed for 2 h, then evaporated to one-half of its volume and allowed to cool down slowly. After recrystallisation in water the white product was obtained. In a second step of the synthesis Na(,[BiW,,038H].~HZ0 (1.978 g, 0.58 mmol) was dissolved in water (10 mL) and one after another solutions of Na,WO* (0.19 1 g, 0.58 mmol) in water (5 mL) and Eu(NO,),.SH,O (0.124 g, 0.29 mL) in water (5 mL) were dropwise added. The resulting mixture was heated for 30 min at 70 “C and after cooling single colourless crystals of 5 were obtained. Acknowledgements Generous support of our work by the Deutsche Forschungsgemeinschaft,by the Fonds der Chemischen Industrie, by the Bundesminister fi.ir Bildung und Forschung and the Hoechst AG, Corporate Research 8r Technology, is gratefully acknowledged.

[ 1 I] Loose I., Biising M., Klein R., Ktebs B.. Schulz R.I?, Schatbert B., Inorg. Chim. Acca, 263 (1997) 99. [ 121 Biising M., Loose I., Krebs B., Inorg. Chem., submirted for publication. [13] Pope M.T., Varga Jr. G.M., Comm. (1966) 653.

J. Chem.

Sot.

Chem.

[14] Fuchs J., Flint E.I?, Z Naturforsch. 34b (1979) 412. [15] Wei X., Dickman M.H., Pope hd.T., Inorg. Chem. 36 (1997) 130. [16] Allmann R., Acta Cryst. 1327 (1971)1393. 1171 D’Amout 1181 Loose I., submitted [I 91 Perloff A.,

H., Allmann R., %. Kristallogr. 138 (1973) 5. B6sing M., Krebs B.. Eur. J. Inorg. Chem.. for publication. Inorg. Chem. 9 (1970) 2228.

1201 Souchay E, Leray M., He&G., C. R. Acad. Sci. S&ic C. 271 (1970) 1337. [21] Blising M., Loose I., Pohlmann H., Krebs B., Chem. Eur. J. 8 (1997)1232. 1221 Bbsing M., Thiilig C.. Nedcr R.B.. Burghammer M., Gras1 T., Rogel E, Krebs B.. Schulz H., Kvick A., Z. Kristallogr. (Suppl.) 1 I (1996) 76. 1231 Biihner R., I’ohlmann H.. Ktcbs B., Z. Kristallogr. (Suppl.) 8 (1994) 262. 1241 ‘I‘hiilig C., Klein R., Ktebs B., %. Kristallogr. (Suppl.) 0 (1995) 229. [25] Bdhner R., Klein R., Pohlmann t1.. Krebs B., %. Kristallog’. (Suppl.) 7 (1993) 23.