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HoAl3Cl12 in Crystalline Form.

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Fig. I . Molecular structure of 2 Selected bond distances [A] and angles [ 1:
M o l - N l 1.75(1), N I - 0 1 1.22(1), Mol-010 2.122(5). Mo2-010 2.343(5), M03010 2.363(5). Mo4-010 2.319(5), Mo5-010 2.348(5), Na-010 3 191(7); M o l N 1 - 0 1 178(1). ASymmetrical OCH, bridges with averaged distances: M o l O(12-15) 1.995(6), M0(2-5)-0 2.279(7); Mol-0-Mo 106.8(3). Na-0(21-24)
2.379(9) (averaged).
tion states may be inferred from the polyanion charge; this
polymolybdate contains localized Mo" and Mo"' atoms.
When 2 is dissolved in dichloromethane or acetonitrile, it
spontaneously transforms into another polymolybdate, 3.
The X-ray study"'] revealed another Lindqvist structure
type and confirmed the formula obtained by chemical analysis. The unit cell contains two independent [Mo,(NO)O,,]~~
anions located on inversion centers. The disorder of both
anions influences the observed interatomic distances. Since
this disorder might also result from a statistical distribution
of [Mo,(NO),O,,]~~and [ M O , ~ , , ] ~an
~ ,electrochemical
study was undertaken; cyclic voltammetry in CH,Cl, on a Pt
electrode in the range - 1.0 to + 1.O V vs. SCE reveals only
one quasi-reversible one-electron oxidation process at
+ 0.87 V; pure [ M o , ~ , , ] shows
~ ~ a reversible reduction
process at - 0.29 V. Therefore, the occurrence of
[ M O , ~ , , ]is~ ~ruled out and the species is a mononitrosylhexamolybdate derived from [ M o , ~ , , ] ' ~by replacing one MOO group by one MONO)^@ group. Compound 3
is another member of the family [Mo,01,L]"@.[21
Compounds 2 and 3 are the first examples of polyoxomolybdates containing an MONO)^@ unit. Moreover, 2 is
the first example of a lacunar Lindqvist structure.
2 : In a typical experiment. 1 191 (32 g, 25 mmol) in 20 mL of methanol was
mixed with 8 0 m L of 1 M NH,OH in methanol (the hydroxylamine was prepared from NH,OH . HCI. which was poured into a methanolic solution of
sodium methoxide: NaCl was then removed by filtration). The suspension was
refluxed for 3 h. After standing ca. 12 h at room temperature, the solution
afforded 5 g of violet crystals (yield: 18 %).
3 : Compound 2 (5 g, 3.7 mmol) was dissolved in hot acetonitrile (30 mL) and
the solution was refluxed for 5 h. Cooling the solution gave 2.3 g of brown
crystals (yield: 38%). IR(KBr): !(NO): 2, 1630: 3, 1575cm-'
Received: April 28, 1989;
supplemented: July 3, 1989 [Z 3310 IE]
German version: Angew. Chem. 101 (1989) 1377
$;: VCH Veriu~~~esr/l.scli~/frft
m h H , 0-6940 Wemherm, l 9 K Y
HoAl,Cl,, in Crystalline Form **
By Dietmar Hake and Werner Urland*
The chemical transport of metal halides is only possible
through the formation of gas-phase complexes with, for example, AICI,. GaCI,, or FeCl,.['] Thus, the relatively nonvolatile trichlorides of the lanthanoids (LnCl,) can be transported with AICI,;[2, 31 spectroscopic studies reveal the
formation of gaseous complexes of empirical formulas
LnA1,Cll2 and LnAI,CI,, ,l4I in which the lanthanoid ion,
depending on its size, is probably nona- or hexacoordinated.['] Here we report, for the first time, the synthesis and
crystal structure of HoAI,CI,,.
HoA1,CI was synthesized by reaction of commercially
available holmium oxide with aluminum trichloride followed by chemical transport;['] the analytical composition
was determined by ICP analysis and argentometric titration
with potentiometric indication.['] The salmon-colored compound is sensitive to moisture and decomposes within a few
minutes upon exposure to air.
Experimen fa1 Procedure
[l] 0. Nagano, Y. Sazaki, Acru C r w u h g r . Sect. 835 (1979) 2387.
[2] a ) T. C. Hsieh, J. Zubieta. Po/yhedron 5 (1986) 1655; b) S. Bank, S. Liu,
S. N. Shaikh. X. Sun, J. Zubieta, P. D. Ellis. Inotx. Chem. 27 (1988) 3535;
c) H. Kang, J. Zubieta, J. Chem. Soc. Clzem. Commwz. 1988, 1192.
[3] a ) D. Carrillo. P. Gouzerh. Y. Jeannin, Noin,.J. Cliim. 9 (1985) 749; b) V.
Chilou, P. Gouzerh, Y. Jeannin, G. Olivares, F. Robert, T. C. Hsieh. J.
Zubieta, Po/diurlron 8 (2989) 29.
[4] a) T. C. Hsieh. J. Zubieta, Po(rhrriron 5 (1986) 305; b) S. N . Shalkh. J.
Zubieta, lnorg Clzini. Acru f2f (1986) L43.
[5] T. C. Hsieh. J. Zubieta. J. Chem. Soc. Clzem. Conimun. 1985. 1749.
[6] a) A. P. Gaughan. B. L. Haymore, J. A. Ibers. W. H. Myers. T. E. Nappier,
D. W. Meek. J A m C h n . Soc. 95 (1973) 6859: b) D. Sutton, Chem. Soc.
R w . 4 (1975) 443.
[7] a) A. Miiller. S. Sarkar, N. Mohan. R. G. Bhattacharyya, Inorg. Chrm.
Actu 45 (1980) L245: b) R. Bhattacharyya. G. P. Bhattacharjee. J. C/zwn.
Soc. Dulton Guns. I983, 1593; c) K. Wieghardt. W. Holzbach, J. Weiss. B.
Nuber. B. Prikner. Angew. C'hrm. 91 (1979) 582; Anpew. Chmi. Inr. Ed.
Engl. 18 (1979) 548: d) K . Wieghardt, V. Holzbdch. ibid. 91 (1979) 583 and
I8 (1979) 549. e) K. Wieghardt. V. Holzbach, B. Nuber, J. Weiss, Chem.
Bc,r. I 1 3 (19x0) 629: f , K. Wieghardt. G. Backes-Dahmann. W. Swiridoff.
J. Weiss, Inorg. Clicm. 23 (1983) 1221.
[XI a) A. Miiller. W Eltzner. N. Mohan, Angen.. Chrm. 91 (1979) 158; A n g w .
Clirm. Inr. Ed EngI. f8 (1979) 168: b) A. Mdller. W. Eltzner, H. Bogge, S.
Sarkar, ibrri. Y4(19X2) 555 and 21 (1982) 535; Angew. Cliem. Suppl. 1982.
1167; c) A. Miiller. W. Eltzner. H. Bogge. E. Krickemeyer. Angew. Chcm.
95 (1983) 905; Angeir. Climf. h r . Ed. Engi. 22 (1983) 884.
[9] This compound was prepared as described for acetdmidoxime. V. Chilou,
P. Gouzerh. Y. Jeannin, F. Robert, J Clreni. Soc. Chm. Commun. fY87,
[lo] 2 : monoclinic. P2,,u, M , = 1477.93 g, Z = 4. ir = 23.325(7), h =
15 917(5), c = 18.433(7) A, /I = 105.82(6).. V = 6584(8) A'. Q , , , ~ , , =
2 i O i 2 3 i(Mo,,)=0.71069A. p = 9 . 7 3 c m - ' . R =
0.059, R, = 0.063. 7286 unique reflections collected; direct methods; 5281
reflections ( 1 > 3u(1)) were used for least-squares refinement; 642 refined
parameters. 3: monoclinic, P2,ju. M , = 1621.04 g, Z = 4. u = 16.688(3).
b = 17.210(3). c = 24.267(4) A. fl = 97.44(1) , V = 6910(4) A3, Q - , ? ~ =
1 < f ) < 2 3 , . i.(MoK,)=0.7I069A, p = 10.9cm-'. R =
0.055. R, = 0.063.9575 unique reflections collected; direct methods; 3436
( I> 3 4 0 ) were used for least-squares refinement; 707 refined parameters.
For both structures. final refinement was carried out with anisotropic
thermal parameters for all atoms: hydrogen atoms not introduced. Further details of the crystal structure investigations may be obtained from the
Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlichtechnische Information mhH. D-7514 Eggenstein-Leopoidshafen 2
(FRG). on quoting the depository number CSD-53953. the names of the
authors. m d the journal citation.
Prof. Dr. W. Urland. Dipl-Chem. D. Hake
lnstitut I'ur Anorgdnische Chemie der Universitdt
Cdllinstrasse 9, D-3000 Hannover 1 (FRG)
This work was supported by the Fonds der Chemischen Industrie
S. 02.50;O
Angew. Cliem. Inr. Ed. EngI. 28 (I 989) No. I 0
The result of the X-ray structure analysisI'l is shown in
Figure 1 . The structure type presented here is, to our knowledge. the first in which a cation is surrounded by chlorine
181 HoAI,Cl,,:P3,12, u = 1050.04(7), c = 1562.24(9) pm (25 C), V =
1491.73 x 10' pm', Z = 3; Siemens AED-2 diffractometer, Mo,, radiation, graphite monochromator. measuring range 3 ' 5 20 I SO . 0-20
scan, 5915 measured reflections, 1770 unique reflections, absorption correction with II, scan. anisotropic refinement, R = 0.035 for 74 refined
parameters. R, = 0.025. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe.
Gesellschaft fur wissenschaftlich-technische Information mbH, D-7514
Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number
CSD-53974, the names of the authors, and the journal citation.
[9] H. Gunsilius, H. Borrmann, A. Simon, W. Urland. 2. Nufrrrforsch. 5 4 3
(1988) 1023.
(lo] D. Hake, W. Urland, 2. Krirtdlugr. I86 (1989), in press.
[ l l ] W Lenhard, H. Schifer, H.-U. Hurter. B. Krebs. Z. Anorg. Allg. Chem.
4x2 (1981) 19.
[12] C. Hirdyamd. P. M. Castle. C. S.Liu, R. J. Zollweg. J. Ilium. /?fig. Sot. 6
(1 977) 209.
Synthesis, Structure and Magnetic Properties
of a Dinuclear Manganese(r1) Complex
with One p-Aqua and Two p-Carboxylato Bridges **
Fig. 1. ORTEP view of HoAI,CI,, with the coordination polyhedron for
HoJe. Selected bond lengths [pm]: Ho-CIl 281.7(2), Ho-CI2 273.4(2). Ho-CI3
270.8(2), Ho-CI4 287.7(2). All-C11 212.4(2). All-C14 213.6(3), A12-CI2
218.9(3). A12-CI3 220.0(3), A12-Cl5 206.9(3), A12-CI6 206.7(4), Ho-All
368.2( 1). Ho-A12 366.8(2).
atoms in such a way as to form a square antiprism. Usually,
a trigonal bicapped prism is formed for octacoordinated lan'I The square antiprism found here is
thanoid trichl~rides.'~.
edge-linked with four AICI, tetrahedra, two of which are
linked to the next HoCI, polyhedron. This linkage leads to
a screw-shaped chain along [OOI]. The Ho-C1 distances within the antiprism vary from 270.8 to 287.7 pm. The antiprism
is slightly distorted; this is especially revealed in the slightly
bent faces, which, ideally, are square planar (Fig. 1). The
terminal AI-CI distances (206.7 and 206.9 pm) are significantly shorter than the AI-CI bridging distances, in agreement with the results of a crystal structure analysis of
PdAI,CI, .I1
The synthesis and X-ray structure analysis of HoAI,Cl,,
and of analogous compounds is of particular interest in connection with the determination of thermodynamic data for a
better understanding of chemical transport and with respect
to the role of these substances in high-pressure discharge
lamps." 2l
Received: June 7, 1989 [Z 3383 IE]
German version: Angew. Chem. 101 (1989) 1416
H Schifer, .4ngrk.. Chem. X8 (1976) 775; AnRcw. Chem. Int. Ed. Engi. 15
(1976) 713.
H. Schifer, M. Binnewies, W Domke, J. Karhinski, Z. Anorg. Allg. Chew.
403 (1974) 116
H. Gunsilius. W. Urland, R. Kremer. 2'. Anorg. A[%. Chem. 550 (1987) 35.
H. A. Oye, D. M. Gruen. 1 Am. Chem. Soc. 91 (1969) 2229.
G. N . Papatheodorou, G. M. Kucera, Inurg. Chem. IX (1979) 385.
Ho,O, (378 mg, 1 mmol) and AICI, (475 mg. 3.5 mmol) were placed in a
cylindrical transport ampoule made of Duran glass. The ampoule was
sealed under inert gas and the reaction was initiated with a burner. Transport was then carried out in a two-zone oven with a temperature gradient
from 250 C to 160 'C (transport time: three days). The salmon-colored
product was deposited on thecooler side in the form of trigonal trapezoids.
Determination of the analytical composition (Ho and A1 by inductively
coupled plasma (ICP) analysis, CI by argentometry): H o 25.5% (calcd
24.6'Yo). AI 12.2% (calcd 12.0%). CI 60.4% (Cdlcd 63.4%).
A n p w Chiwi. Int. Ed. EngI. 28 (1989) N o . 10
By Andrea Caneschi, Fabrizio Ferraro, Dante Calfexhi,*
Maria Chiara Melandri, Paul Rey, and Roberta Sessoli
Polynuclear manganese complexes are currently of great
interest owing to their relevance to many important naturally occurring processes. In particular, a cluster of four manganese ions is known to be involved in the photosynthetic
water-oxidizing complex,['] and two manganese ions per
protein subunit are present in the pseudo-catalase from Lactobacillus plantarum .I2]
During our efforts to synthesize magnetic materials by
using manganese(r1) and stable organic radicals comprising
two equivalent NO groups,[31we isolated the dinuclear complex 1, L = 2-ethy1-4,4,5,5-tetramethyl-3-0~0-4,5-dihydro[Mn,(F,C,COO),(H,O),Lzl
1H-imadazolyl-I-oxyl (see Table
Complex 1 contains
one p-H,O and two p-carboxylato bridges with a structure
of the Mn,(p-H,O)(p-O,CR), core analogous to that observed in hemer~thrin,'~]
the marine invertebrate oxygen
transport protein, and in various metal complexes.[']
O Z e , OH',
Scheme 1. Framework of complexes 1-7 (Table 1).
Complex 1 is the first such manganese compound in which
X is water (see Scheme I), although similar structures are
known for ruthenium, cobalt, and nickel compounds[71(an
iron analogue does not exist). This provides the opportunity
the efficiency of the three X groups in transmitto
ting exchange interactions between the two d5 ions.
[*] Prof. Dr. D. Gatteschi, Dr. A. Caneschi, F. Ferraro, M. C. Melandri,
u r . K.sessoii..
Universita degli Studi di Firenze
Dipartimento di Chimica
Via Maragliano 77, 1-50144 Firenze (Italy)
Dr. P. Rey
Lahordtoire de Chemie, U A 1194 CNRS
Departement de Recherche Fondamentale, C.E.N.G.
F-38041 Grenoble (France)
[*'I This work was supported by the Italian Ministry of Public Education and
by CNR.
VCH Verlugsgesellschufi m h H , 0-6940 Weinhcim, 1989
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