Nickel(II) thiolate complexes with a flexible cyclo-{Ni10S 20} framework

Article abstract of DOI:10.1002/anie.200600319

A tale of two toroids: New cyclic nickel(II) thiolate complexes (see structures; Ni green, S red, C purple) were synthesized by stepwise introduction of two kinds of thiolates to a nickel(II) center. The flexible {Ni ₁₀S₂₀} core configuration crystallizes in different forms, either circular or ellipsoidal, depending on the presence or absence of an encapsulated guest molecule. (Figure Presented)

Full text of DOI:10.1002/anie.200600319

Angewandte
Chemie
DOI: 10.1002/anie.200600319
Communications
The flexible configuration of the new cyclo-Ni10S20 toroid was revealed
by X-ray structural analysis to be circular or ellipsoidal, depending on
the presence or absence of an encapsulated benzene molecule. For a
more detailed discussion on the synthesis and structure, see the
Communication by K. Tatsumi and co-workers on the following pages.
3768
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3768 – 3772

Angewandte
Chemie
Nickel Thiolates
the ring configuration of the decanuclear nickel cluster is
flexible and exhibits either a circular or ellipsoidal form which
is dependent on the presence or absence of an encapsulated
guest molecule.
DOI: 10.1002/anie.200600319
Nickel(ii) Thiolate Complexes with a Flexible
cyclo-{Ni10S20} Framework**
The reaction of NiCl2·6H2O with one equivalent of [K-
(mtet)] at room temperature led to an immediate color
change from light green to deep red, and the thiolate-bridged
dinuclear nickel complex[{NiCl( m-mtet)}2] (1) was isolated in
70% yield as brown-red block-shaped crystals.[17,18] In the
structure of 1, the two mtet ligands link the Ni atoms through
the thiolate sulfur atoms, and the thioether sulfur atoms and
chloride atoms occupy the terminal positions. Thus, two
square {NiClS3} units are conjoined at an edge, and the Ni2S2
rhombus is puckered (dihedral angle: 117.88). This complex
was found to be a suitable precursor for the synthesis of a
series of mixed-thiolato complexes of nickel. Thus, 1 was
treated with two equivalents of K(SiPr) in MeOH for
sixhours, and subsequent crystallization from a mixture of
benzene/hexane generated deep-red hexagonal plates of
[{Ni(m-SiPr)(m-mtet)}6]·C6H6 (2) in 35% yield (Scheme 1).
The X-ray crystal analysis revealed a hexagonal {Ni6S12}
framework (Figure 1), as was observed for the previously
reported complexes [{Ni(m-SR)2}6].[10,18] The cocrystallized
benzene molecule is located outside the Ni6 ring. The
transannular Ni···Ni separations are in the range 5.757(2)–
5.915(1) Š, and the dihedral angles between two adjacent
NiS2 planes (121.6–125.68) are close in value to the interior
angle of the ideal hexagon. The two kinds of thiolate ligands,
mtet and SiPr, are situated alternately above and below the
Ni6 plane. The iPr groups are oriented away from the ring, and
each thioether substituent of the mtet ligands extends above
or below the Ni6 plane.
When the reaction of 1 was carried out with K(StBu)
instead of K(SiPr), a decanuclear cluster [{Ni(m-StBu)(m-
mtet)}10] (3) was obtained in 62–66% yield as dark-red block-
shaped crystals after recrystallization from benzene/HMDSO
or toluene/HMDSO (HMDSO = hexamethyldisiloxane). The
toroidal {Ni10S20} core geometry of 3 was determined by X-ray
analysis, and analogously to the ligand conformation in 2, the
mtet and StBu ligands bridge the Ni atoms alternately above
and below the Ni10 plane. Interestingly, 3 was found to
crystallize in different forms depending on the solvent used
for crystallization. In the X-ray structure of crystals obtained
from a mixture of benzene/HMDSO, one of the three
benzene molecules is encapsulated in the cavity formed by
the {Ni10S20} toroid. Thus, the compound is formulated as
[C6H6ꢀ{Ni(m-StBu)(m-mtet)}10]·2C6H6 (3a), and the toroidal
{Ni10S20} core assumes a circular shape.[18] However, no
solvent molecule was incorporated inside the ring when
compound 3 was crystallized from a mixture of toluene/
HMDSO. In this case, the {Ni10S20} core displays an ellipsoidal
shape, and the compound is formulated as [{Ni(m-StBu)(m-
mtet)}10]·CH3C6H5 (3b).[18]
Chi Zhang, Satoshi Takada, Michael Kölzer,
Tsuyoshi Matsumoto, and Kazuyuki Tatsumi*
First-row transition-metal toroidal architectures are impor-
tant motifs for potential applications in molecular recognition
and magnetic materials.[1,2] In contrast to the ubiquitous O- or
N-bridged metal rings, which exhibit fascinating cluster
configurations,[3–9] the study of the S-bridged variants remains
limited. Homoleptic nickel(ii) thiolates [{Ni(m-SR)2}n] occa-
sionally generate cyclic structures by forming shared edges of
the square NiS4 coordination planes, and several hexanuclear
ring clusters [{Ni(m-SR)2}6] have been reported.[10] Tetranu-
clear[11] and pentanuclear cyclic complexes have also been
isolated,[11c,12] but reports of the synthesis of larger cyclic
complexes are still limited. The structure of [{Ni(m-
SCH2CO2Et)2}8] was reported by Dance et al. in which the
substituent of one thiolate bridge is tilted inward to fill the
cavity of the octanuclear ring.[13] Recently, the intriguing
cyclic structures of nona- and undecanuclear complexes
[{Ni(m-SPh)2}n] (n = 9, 11) were determined by Dahl and co-
workers, although in low yield.[14] Each of the cyclic nickel
thiolates described above is composed of one kind of thiolate
ligand. In contrast, Wolczanski and co-workers synthesized a
dodecanuclear cyclic complex[{Ni( m-SSitBu3)(m-Br)}12], in
which the nickel atoms, in a tetrahedral geometry, are linked
by a sterically demanding thiolate ligand and a bromine atom;
however, the complexwas obtained as a mixture with by-
products.[15] As an extension of our study on transition-metal
thiolates,[16] we became interested in thioether–thiolate
hybrid ligands. Reported herein is a new synthetic route to
cyclic nickel thiolate complexes with two different thiolate
bridges, namely an alkylthiolate ligand (SiPr or StBu) and 2-
methylthioethanethiolate (mtet), and the use of these ligands
resulted in the selective formation of cyclo-[{Ni(m-SiPr)(m-
mtet)}6] and cyclo-[{Ni(m-StBu)(m-mtet)}10]. We found that
[*] Dr. C. Zhang, S. Takada, M. Kölzer, Dr. T. Matsumoto,
Prof. Dr. K. Tatsumi
Research Center for Materials Science and
Department of Chemistry
Graduate School of Science
Nagoya University
Furo-cho, Chikusa-ku, Nagoya 464-8602 (Japan)
Fax: (+81)52-789-2943
E-mail: i45100a@nucc.cc.nagoya-u.ac.jp
[**] This research was financially supported by Grants-in-Aid for
Scientific Research (Nos. 14078211, 16350031, and 17036020) from
the Ministry of Education, Culture, Sports, Science, and Technology,
Japan. C.Z. is grateful to the Japan Society for the Promotion of
Science (JSPS) for a fellowship.
In the crystal structure of 3a (Figure 2), the benzene
molecule inside the cavity lies approximately in the Ni10 plane
but is tilted by 16.68. As was the case for [{Ni(m-SiPr)(m-
mtet)}6]·C6H6 (2), the tBu groups are each oriented outward
from the {Ni10S20} toroid. The mtet substituents are oriented
above and below the Ni10 plane, except for two of the mtet
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2006, 45, 3768 –3772
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3769

Communications
dihedral angles between two adjoining NiS2 planes (138.4
to 152.48) and the varied transannular Ni···Ni separations
(9.496(2) to 11.113(3) Š, Figure 4). Thus, the geometry of
the {Ni10S20} toroid is flexible.
Expansion of the ring size from the hexanuclear
cluster 2 to the decanuclear cluster 3a or 3b appears to be
promoted by the change of bridging thiolate ligand, from
SiPr to StBu. A close inspection of the X-ray structures
reveals that the averaged sum of the bond angles at the
S atoms of the m-StBu ligands is 3108 (3a) or 3118 (3b),
while the corresponding sum for the m-SiPr ligands in
hexanuclear 2 is distinctively smaller (2948). Although the
difference is not large, we speculate that the bulkier
tBu group, relative to iPr, would have caused the decrease
in pyramidality at the thiolate sulfur atoms to minimize
steric repulsion between the tBu groups and the {Ni2(m-
S)2} core atoms. The steric hindrance is revealed in the
short contacts between protons of the tBu groups and
both the S atoms of each m-mtet ligand and Ni atoms
within each {Ni2S2} quadrangular unit;[19] these separa-
tions are close to the sums of the van der Waals radii of
the individual atoms.[20] Dance et al.[13] pointed out that
the Ni-S(R)-Ni bond angles of doubly bridged {Ni(m-
Scheme 1. The synthesis of 2 and 3.
Figure 1. Molecular structure of 2 (Ni green, S red, C purple). All
protons and the solvent molecule are omitted for clarity. Neighboring
interatomic distances [Š]: Ni–S 2.188(2)–2.207(2) (av: 2.20), Ni–Ni
2.893(1)–2.951(1) (av: 2.92).
Figure 2. Molecular structure of 3a (Ni green, S red, C purple). All
protons and the solvent molecules are omitted for clarity. Neighboring
interatomic distances [Š]: Ni–S 2.190(1)–2.214(1) (av: 2.20), Ni–Ni
3.1307(8)–3.172(1) (av: 3.16).
ligands which are extended toward the center of the toroid
cavity such that the thioether groups clamp the encapsulated
benzene molecule from above and below. The transannular
Ni···Ni separations are nearly constant (10.075(2)–
10.336(2) Š), thus consistent with the round shape of the
{Ni10S20} toroid. The dihedral angles between adjacent NiS2
planes also do not vary significantly (144.1–147.88) and are
understandably larger than those of the hexanuclear core of 2.
In the case of 3b (Figure 3), the thioether substituents of
four of the mtet ligands are extended toward the center of the
{Ni10S20} toroid, and two of these penetrate into the central
cavity where the benzene molecule is incorporated for 3a. In
addition, the {Ni10S20} toroid in 3b possesses an ellipsoidal
shape, and the consequences of this shape are the varied
SR)2Ni} units tend to increase as the pyramidality of the m-
S atoms decreases.[10–13,21] The averaged Ni-S(tBu)-Ni bond
angle of 928 for 3a (and for 3b) is evidently larger than that of
2 (838) and those of the related complexes [{Ni(m-SR)2}n] (n =
4, 5, 6, 8).[10–13] The larger Ni-S(tBu)-Ni bond angles, in turn,
bring about the larger dihedral angles between the adjacent
NiS2 planes of 3a and 3b, and the larger decanuclear ring is
the consequence.
In conclusion, the decanuclear nickel(ii) thiolato cluster
[{Ni(m-StBu)(m-mtet)}10] with a flexible core was synthesized
by the reaction of the preformed complex[{NiCl( m-mtet)}2]
with KStBu. This approach using stepwise introduction of two
3770
www.angewandte.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3768 –3772

Angewandte
Chemie
dissolved in benzene and layered with HMDSO to afford 3a as black-
red block-shaped crystals (yield: 0.173 g, 62%). Alternatively,
analogous crystallization using toluene and HMDSO gave 3b as
black-red block-shaped crystals (yield: 0.174 g, 66%).
Received: January 25, 2006
Published online: April 19, 2006
Keywords: cluster compounds · nickel · S ligands ·
.
structure elucidation · supramolecular chemistry
[1] a) V. L. Pecoraro, A. J. Stemmler, B. R. Gibney, J. J. Bodwin, H.
Wang, J. W. Kampf, A. Barwinski, Prog. Inorg. Chem. 1997, 45,
83 – 177; b) G. Mezei, P. Baran, R. G. Raptis, Angew. Chem.
2004, 116, 584 – 587; Angew. Chem. Int. Ed. 2004, 43, 574 – 577.
[2] a) D. Foguet-Albiol, T. A. OꢀBrien, W. Wernsdorfer, B. Moulton,
M. J. Zaworotko, K. A. Abboud, G. Christou, Angew. Chem.
2005, 117, 919 – 923; Angew. Chem. Int. Ed. 2005, 44, 897 – 901;
b) O. Cador, D. Gatteschi, R. Sessoli, F. K. Larsen, J. Overgaard,
A. L. Barra, S. J. Teat, G. A. Timco, R. E. P. Winpenny, Angew.
Chem. 2004, 116, 5308 – 5312; Angew. Chem. Int. Ed. 2004, 43,
5196 – 5200; c) C. Dendrinou-Samara, M. Alexiou, C. M. Zale-
ski, J. W. Kampf, M. L. Kirk, D. P. Kessissoglou, V. L. Pecoraro,
Angew. Chem. 2003, 115, 3893 – 3896; Angew. Chem. Int. Ed.
2003, 42, 3763 – 3766.
Figure 3. Molecular structure of 3b (Ni green, S red, C purple). All
protons and the solvent molecule are omitted for clarity. Neighboring
interatomic distances (Š): Ni–S 2.196(1)–2.224(1) (av: 2.21), Ni–Ni
3.098(1)–3.224(1) (av: 3.17).
[3] S. P. Watton, P. Fuhrmann, L. E. Pence, A. Caneschi, A. Cornia,
G. L. Abbati, S. J. Lippard, Angew. Chem. 1997, 109, 2917 – 2919;
Angew. Chem. Int. Ed. Engl. 1997, 36, 2774 – 2776.
[4] L. F. Jones, A. Batsanov, E. K. Brechin, D. Collison, M.
Helliwell, T. Mallah, E. J. L. McInnes, S. Piligkos, Angew.
Chem. 2002, 114, 4494 – 4497; Angew. Chem. Int. Ed. 2002, 41,
4318 – 4321.
[5] a) M. Murugesu, W. Wernsdorfer, K. A. Abboud, G. Christou,
Angew. Chem. 2005, 117, 914 – 918; Angew. Chem. Int. Ed. 2005,
44, 892 – 896; b) A. J. Tasiopoulos, A. Vinslava, W. Wernsdorfer,
K. A. Abboud, G. Christou, Angew. Chem. 2004, 116, 2169 –
2173; Angew. Chem. Int. Ed. 2004, 43, 2117 – 2121.
[6] C. M. Zaleski, E. C. Depperman, J. W. Kampf, M. L. Kirk, V. L.
Pecoraro, Angew. Chem. 2004, 116, 4002 – 4004; Angew. Chem.
Int. Ed. 2004, 43, 3912 – 3914.
Figure 4. Top view of the {Ni10S20} core configurations of 3a and 3b.
[7] a) F. K. Larsen, J. Overgaard, S. Parsons, E. Rentschler, A. A.
Smith, G. A. Timco, R. E. P. Winpenny, Angew. Chem. 2003, 115,
6160 – 6163; Angew. Chem. Int. Ed. 2003, 42, 5978 – 5981;
b) A. L. Dearden, S. Parsons, R. E. P. Winpenny, Angew.
Chem. 2001, 113, 155 – 158; Angew. Chem. Int. Ed. 2001, 40,
151 – 154.
kinds of thiolate ligands to a nickel(ii) center expands the
scope of synthetic routes to cyclic polynuclear nickel(ii)
thiolates with various sizes and functions.
[8] S. Piligkos, G. Rajaraman, M. Soler, N. Kirchner, J. van Slageren,
R. Bircher, S. Parsons, H. U. Gudel, J. Kortus, W. Wernsdorfer,
G. Christou, E. K. Brechin, J. Am. Chem. Soc. 2005, 127, 5572 –
5580.
[9] S. X. Liu, S. Lin, B. Z. Lin, C. C. Lin, J. Q. Huang, Angew. Chem.
2001, 113, 1118 – 1121; Angew. Chem. Int. Ed. 2001, 40, 1084 –
1087.
[10] a) P. Woodward, L. F. Dahl, E. W. Abel, B. C. Crosse, J. Am.
Chem. Soc. 1965, 87, 5251 – 5253; b) E. W. Abel, B. C. Crosse, J.
Chem. Soc. A 1966, 1377 – 1378; c) T. A. Wark, D. W. Stephan,
Organometallics 1989, 8, 2836 – 2843; d) K. Schulbert, R. Mattes,
Z. Naturforsch. B 1994, 49, 770 – 772; e) H. Feld, A. Leute, D.
Rading, A. Benninghoven, G. Henkel, T. Krüger, B. Krebs, Z.
Naturforsch. B 1992, 47, 929 – 936; f) R. O. Gould, M. M.
Harding, J. Chem. Soc. A 1970, 875 – 881; g) A. H. Mahmoud-
khani, V. Langer, Polyhedron 1989, 8, 3407 – 3410; h) M.
Capdevila, P. Ginzales-Duarte, J. Soda, C. Focces-Foces, F. H.
Cano, M. Martines-Ripoll, Polyhedron 1989, 8, 1253 – 1259; i) H.
Berrera, J. C. Bayson, J. Suades, C, Germain, J. P. Declerq,
Polyhedron 1984, 3, 969 – 975; j) J. Sletten, J. A. Kovacs, Acta
Experimental Section
1: The reported synthetic method was modified as follows.[17] [K-
(mtet)], prepared from H(mtet) (0.108 g, 1 mmol) and KOtBu
(0.112 g, 1 mmol), was slowly added to a solution of NiCl2·6H2O
(0.237 g, 1 mmol) in MeOH (15 mL), and the mixture was stirred at
room temperature for 4 h. The volatiles were removed, and the
resulting brown residue was extracted with toluene and then dried in a
vacuum. The dark red powder was dissolved in toluene and layered
with hexane to afford brown-red block-shaped crystals of 1 (yield:
0.141 g, 70%).
2: KSiPr, prepared from HSiPr (0.076 g, 1 mmol) and KOtBu
(0.112 g, 1 mmol), was slowly added to a solution of [NiCl(m-mtet)]2
(1; 0.201 g, 0.5 mmol) in MeOH (20 mL) and stirred at room
temperature for 6 h. A work up similar to that for 1 afforded a dark
red powder, which was dissolved in benzene and layered with hexane
to give 2 as deep-red hexagonal plates (yield: 0.089 g, 35%).
3: A similar synthetic procedure to that for 2, except that KStBu
was added instead of KSiPr, gave a dark red powder, which was
Angew. Chem. Int. Ed. 2006, 45, 3768 –3772
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3771

Communications
Chem. Scand. 1994, 48, 929 – 932; k) F. F. Jian, K. Jiao, Y. Li, P. S.
Zhao, L. D. Lu, Angew. Chem. 2003, 115, 5900 – 5902; Angew.
Chem. Int. Ed. 2003, 42, 5722 – 5724.
[19] The mean separations of the closest CtBu···Smtet and CtBu···Ni
contacts at the {Ni2S2} quadrangle units of 3a are 3.34 and
3.55 Š, respectively.
[20] A. Bondi, J. Phys. Chem. 1964, 68, 441 – 451.
[11] a) T. Krüger, B. Krebs, G. Henkel, Angew. Chem. 1989, 101, 54 –
55; Angew. Chem. Int. Ed. Engl. 1989, 28, 61 – 62; b) W. Gaete, J.
Ros, X. Solans, M. Font-Altaba, J. L. Brianso, Inorg. Chem. 1984,
23, 39 – 43; c) M. Kriege, G. Henkel, Z. Naturforsch. B 1987, 42,
1121 – 1128.
[12] a) A. H. Mahmoudkhani, V. Langer, Inorg. Chim. Acta 1999,
294, 83 – 86; b) B. K. Koo, E. Block, H. Kang, S. Liu, J. Zubieta,
Polyhedron 1988, 7, 1397 – 1399.
[21] a) W. Tremel, B. Krebs, G. Henkel, Angew. Chem. 1984, 96, 604 –
605; Angew. Chem. Int. Ed. Engl. 1984, 23, 634 – 635; b) W.
Tremel, B. Krebs, G. Henkel, J. Chem. Soc. Chem. Commun.
1986, 1527 – 1529; c) A. D. Watson, C. P. Rao, J. R. Dorfman,
R. H. Holm, Inorg. Chem. 1985, 24, 2820 – 2826; d) J. P. Fack-
ler, Jr., W. J. Zegarski, J. Am. Chem. Soc. 1973, 95, 8566 – 8574;
e) K. Schulbert, R. Mattes, Z. Naturforsch. B 1994, 49, 770 – 772.
[13] I. G. Dance, M. I. Scudder, R. Secomb, Inorg. Chem. 1985, 24,
1201 – 1208.
[14] S. A. Ivanov, M. A. Kozee, W. A. Merrill, S. Agarwal, L. F. Dahl,
J. Chem. Soc. Dalton Trans. 2002, 4105 – 4115.
[15] a) O. L. Sydora, P. T. Wolczanski, E. B. Lobkovsky, E. Rum-
berger, D. N. Hendrickson, Chem. Commun. 2004, 650 – 651;
b) O. L. Sydora, P. T. Wolczanski, E. B. Lobkovsky, Angew.
Chem. 2003, 115, 2789 – 2791; Angew. Chem. Int. Ed. 2003, 42,
2685 – 2687.
[16] a) Z. Li, Y. Ohki, K. Tatsumi, J. Am. Chem. Soc. 2005, 127, 8950 –
8951; b) Y. Ohki, H. Sadohara, Y. Takikawa, K. Tatsumi, Angew.
Chem. 2004, 116, 2340 – 2343; Angew. Chem. Int. Ed. 2004, 43,
2290 – 2293; c) Y. Ohki, Y. Sunada, M. Honda, M. Katada, K.
Tatsumi, J. Am. Chem. Soc. 2003, 125, 4052 – 4053; d) T. Komuro,
T. Matsuo, H. Kawaguchi, K. Tatsumi, Angew. Chem. 2003, 115,
481 – 484; Angew. Chem. Int. Ed. 2003, 42, 465 – 468; e) T.
Komuro, T. Matsuo, H. Kawaguchi, K. Tatsumi, J. Am. Chem.
Soc. 2003, 125, 2070 – 2071; f) H. Kawaguchi, K. Yamada, S.
Ohnishi, K. Tatsumi, J. Am. Chem. Soc. 1997, 119, 10871 –
10872; g) H. Kawaguchi, K. Yamada, J. Lang, K. Tatsumi, J.
Am. Chem. Soc. 1997, 119, 10346 – 10358; h) H. Kawaguchi, K.
Tatsumi, J. Am. Chem. Soc. 1995, 117, 3885 – 3886.
[17] B. C. Bloodworth, B. Demetriou, R. Grzeskowiak, Transition
Met. Chem. 1979, 4, 187 – 190.
[18] Crystal data for 1: C6H14Ni2S4Cl2, monoclinic, space group C2/c
(No. 15), a = 13.343(5), b = 6.632(2), c = 15.258(4) Š, b =
91.00(2)8, V= 1350.0(7) Š3, Z = 4, T= 173 K, l = 0.71073 Š,
F(000) = 816, m = 37.63 cmÀ1, 1calcd = 1.981 gcmÀ3, 7778 reflec-
tions (2q < 55.208), 1824 independent (Rint = 0.036), R1 = 0.029
(I > 2s(I)), Rw = 0.073 (all data). Crystal data for 2:
¯
C42H90Ni6S18, triclinic, space group P1 (No. 2), a = 12.733(2),
b = 12.940(2), c = 12.953(3) Š, a = 66.44(1), b = 66.19(1), g =
60.92(1)8, V= 1650.2(5) Š3, Z = 1, T= 113 K, l = 0.71073 Š,
F(000) = 798, m = 22.75 cmÀ1, 1calcd = 1.534 gcmÀ3, 12961 reflec-
tions (2q < 54.968), 7211 independent (Rint = 0.036), R1 = 0.080
(I > 2s(I)), Rw = 0.216 (all data). Crystal data for 3a:
¯
C88H178Ni10S30, triclinic, space group P1 (No. 2), a = 15.337(4),
b = 15.542(4), c = 16.396(4) Š, a = 104.5377(5), b = 112.387(3),
g = 107.078(2)8, V= 3149(1) Š3, Z = 1, T= 113 K, l = 0.71073 Š,
F(000) = 1466, m = 19.93 cmÀ1, 1calcd = 1.468 gcmÀ3, 24747 reflec-
tions (2q < 54.978), 13759 independent (Rint = 0.017), R1 = 0.059
(I > 2s(I)), Rw = 0.162 (all data). Crystal data for 3b:
¯
C77H168Ni10S30, triclinic, space group P1 (No. 2), a = 14.130(4),
b = 14.925(5), c = 16.708(6) Š, a = 109.871(3), b = 111.328(3),
g = 98.234(2)8, V= 2940(1) Š3, Z = 1, T= 113 K, l = 0.71073 Š,
F(000) = 1390, m = 21.31 cmÀ1, 1calcd = 1.493 gcmÀ3, 22982 reflec-
tions (2q < 54.978), 12826 independent (Rint = 0.020), R1 = 0.065
(I > 2s(I)), Rw = 0.184 (all data). All calculations were per-
formed with the TEXSAN program package, and structures
were solved by Patterson methods (DIRDIF94 PATTY) and
refined by full-matrixleast squares against F2. The protons were
À
placed at calculated positions (d(C H): 0.97 Š). CCDC-295875
(1) and CCDC-294804–294806 (2, 3a, 3b) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
3772
www.angewandte.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3768 –3772