The [Sn5]2± Cluster Compound [K-(2,2,2-crypt)]2Sn5 ± Synthesis, Crystal
Structure, Raman Spectrum, and Hierarchical Relationship to CaIn2
Mehmet Somer
Istanbul/Turkey, KocË University, Chemistry Department
Wilder Carrillo-Cabrera, Eva-Maria Peters, Karl Peters, Martin Kaupp and Hans Georg von Schnering*
Stuttgart, Max-Planck-Institut fuÈr FestkoÈrperforschung
Received August 19th, 1998.
Professor Klaus-JuÈrgen Range zum 60. Geburtstag gewidmet
Abstract. Dark red crystals of [K-(2,2,2)-crypt)]2Sn5 precipi-
tate after the reaction of (2,2,2)-crypt with a solution of
K1.33Sn in liquid ammonia at room temperature. The com-
pound is sensitive to oxidation and hydrolysis. The sequence
of Raman bands (104, 120, 133 and 180 cm±1) is characteris-
tic for the trigonal bipyramidal closo-[Sn5]2± cluster anion.
The wave numbers correspond with the data from Hartree-
Fock calculations (114, 128, 142 and 187 cm±1). The com-
pound crystallizes trigonally (a = 11.736 A Ê , c = 22.117 A
Ê,
Z = 2, space group P3c1 (No. 165); Pearson code hP262), iso-
typic with [Na-(2,2,2)-crypt)]2Pb5. The atoms of the cluster
show strange anisotropic displacements, which are perfectly
Die [Sn5]2±-Clusterverbindung [K-(2,2,2-crypt)]2Sn5 ± Synthese, Kristallstruktur,
Ramanspektrum und hierarchische Relationen zu CaIn2
InhaltsuÈbersicht. Dunkelrote Kristalle von [K-(2,2,2)-
crypt)]2Sn5 bilden sich bei 20 °C nach Umsetzung einer LoÈ-
sung von K1.33Sn in fluÈssigem Ammoniak mit (2,2,2)-crypt.
Die Verbindung ist empfindlich gegen Oxidation und Hydro-
lyse. Das Ramanspektrum zeigt ein Bandenmuster (104, 120,
133 und 180 cm±1), welches fuÈr das trigonal-bipyramidale
Clusteranion closo-[Sn5]2± charakteristisch ist. Die Wellen-
zahlen stimmen mit den Daten aus Hartree-Fock-Rechnun-
gen uÈberein (114, 128, 142 und 187 cm±1). [K-(2,2,2)-
crypt)]2Sn5 kristallisiert trigonal (a = 11.736(1) A Ê, c=
Ê
22.117(3) A, Z = 2, Raumgruppe P3c1 (Nr. 165); Pearson
code hP262), isotyp mit [Na-(2,2,2)-crypt)]2Pb5. Die Atome
* Prof. Dr. Dr. h. c. H. G. von Schnering
Max-Planck-Institut fuÈr FestkoÈrperforschung
Heisenbergstraûe 1
D-70569 Stuttgart
* Prof. Dr. M. Somer
KocË University, Chemistry Department
Cayir Cad. 5
TR-80860 Istinye-Istanbul/Turkey
Z. anorg. allg. Chem. 1999, 625, 37±42  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
reducible to a helical rigid-body motion around and along
Ê ). The structure
[001] (libration: ± 9.5°; translation ± 0.29 A
can be described as a hierarchical derivative of the initiator
CaIn2 (P63/mmc, hP6), generated by an atom-to-aggregate
replacement: [Ca][In]2 = [Sn5][K @ C36H72N4O12]2. Thus, the
distribution of the [Sn5]2± Zintl anions is hexagonal primi-
tive, and the cation complexes are located close to the cen-
ters of trigonal superprisms formed by Sn5 clusters.
Keywords: Clusters; Tin; [K-(2,2,2-crypt)]2Sn5; Zintl phases;
[Sn5]2± cluster anion; vibrational spectra; rigid-body motion;
hierarchical structure
des Clusters zeigen seltsame anisotrope Auslenkungen,
welche sich aber vollstaÈndig auf eine helicale Bewegung
eines starren KoÈrpers um und entlang [001] zuruÈckfuÈhren
Ê ). Die Struktur
lassen (Libration: ± 9.5°; Translation ± 0.29 A
laÈût sich als eine hierarchische Variante des Basistyps CaIn2
(P63/mmc, hP6) beschreiben, erzeugt durch die Substitu-
tion einzelner Atome durch Aggregate: [Ca][In]2 =
[Sn5][K @ C36H72N4O12]2. Das Verteilungsmuster der Zintl-
Anionen [Sn5]2± entspricht dem einer hexagonal primitiven
Zelle mit den KomplexmolekuÈlen K @ C36H72N4O12 nahe
den Zentren von trigonalen Superprismen, die durch Sn5-
Cluster gebildet werden.
1 Introduction
In 1977, Edwards and Corbett [1] characterized the
first compounds [Na-(2,2,2)-crypt)]2Sn5 and [Na-
(2,2,2)-crypt)]2Pb5 with the trigonal bipyramidal closo-
[E5]2 cluster anions (E = Sn, Pb). They obtained these
compounds from solutions of the corresponding NaEx
precursors in en in the presence of crypt. The Zintl
phase derivative [K-(2,2,2)-crypt)]2Pb5 was prepared
in a similar way, but it was not structurally character-
0044±2313/99/62537±42 $ 17.50+.50/0 37
 M. Somer et al.

ized. In the course of our studies of binary alkali me-
tal compounds containing the cluster anions [E4]4±
and [E9]4± with E = Si, Ge, Sn, Pb [2, 3] we tried again
to prepare crystalline solvates of those compounds,
and we found by the way [K-(2,2,2)-crypt)]2Sn5. The
results of the X-ray single crystal structure analysis,
the Raman spectra of the potassium and sodium com-
pounds, and the ab initio calculations of the [Sn5]2±
Raman spectrum are presented here.
2 Synthesis
Crystals of [K-(2,2,2-crypt)]2Sn5 were obtained as a
precipitation byproduct after the reaction of 2,2,2-
crypt with a solution of K1.33Sn in liquid ammonia,
which was carried out to prepare [Sn4]4± containing
solutions for Raman spectra measurements. The ex-
cess of potassium is necessary in order to reduce the
formation of the competitive [Sn9]4± anions. After two
weeks at room temperature, a very small quantity of
long dark red trigonal crystals of [K-crypt]2Sn5 were
formed on the glass wall close to the glass/liquid/gas
phase boundary together with some shiny black pris-
matic `crystals'. The powder of the black product
turned out to be amorphous to X-rays, but the Raman
spectrum was surprisingly identical with that of deri-
vatives with [Sn4]4± tetrahedranide anions. After the
soxhlet extraction in the absence of 2,2,2-crypt, the
tetrahedranide derivative was the only precipitation
product. This indicates that the formation of at least
this cluster compound is not affected by the cryptand,
which is in good agreement with the results reported
for NaSn in liquid ammonia [4].
The synthesis of [Na-(2,2,2-crypt)]2Sn5 was carried
out by using the route described by Edwards and Cor-
bett [1].
3 Properties
Crystalline [K-(2,2,2-crypt)]2Sn5 is transparent dark
red. The compound is sensitive to oxidation and hy-
drolysis and has to be handled under inert conditions
(i. e. glove box; Ar, O2, and H2O ≤ 1 ppm).
4 Structure Determination
The X-ray diffraction data of a single crystal of [K-
(2,2,2-crypt)]2Sn5 mounted in a capillary were recorded
using a Siemens P4 four-circle diffractometer. The unit
cell dimensions were determined from the least-
square refinement of the 2h values of 29 reflections
(15.5° ≤ 2h ≤ 24.8°). The Laue symmetry, the systema-
tic reflection absences and the |E| distribution lead to
the trigonal space group P3c1 (No. 165). These data
indicated that the compound is isotypic with [Na-
(2,2,2-crypt)]2Pb5 [1]. The positional parameters of
[Na-(2,2,2-crypt)]2Pb5 were used as starting set for the
structure refinement. The refinement on the whole F2
data converged rapidly (Table 1). The refined posi-
tions were then rotated by 60° around the c-axis in or-
der to have a direct comparison with the structure of
the hierarchical initiator CaIn2. The idealized posi-
tions of all hydrogen atoms were calculated, and in
the final refinement their positions `ride' on those of
the atoms to which they are attached. The displace-
ment parameter of all H atoms was refined as a
common overall parameter. The results are given in
Table 2 and 3.
Table 1 Crystallographic data for [K-(2,2,2)-crypt)]2Sn5a)
Crystal dark red trigonal prism
(0.25 × 0.25 × 0.14 mm)
Space group; formula units P3c1 (No. 165); Z = 2
Structure type; Pearson code [Na-(2,2,2)-crypt)]2Pb5, hP262
Unit cell (297 K) a = 11.736(1) A Ê , c = 22.117(3) AÊ
Ê3
V = 2638.1(5) A
dcalc 1.793 g ´ cm±3
Measurement, refinement Siemens-Nicolet four-circle diffractometer,
Mo-Kα (k = 0.71073 A Ê ); x-scan mode;
2h ≤ 55°. Empirical absorption correction
(w-scan method), l = 25.5 cm±1, min.
and max. transmission: 0.46, 0.59.
SHELXTL [5] (91 variable parameters)
N(hkl) measured/unique 4710/2035
N'(hkl) with I > 2 ´ r(I) 904
RN'(F); Rw(F2) 0.070; 0.138 (all data)
a)
Further details of the crystal structure determination can be ordered
from Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopolds-
hafen under the depository number CSD-410240.

Table 2 Positional and displacement parameters (in pm2) for [K-(2,2,2)-crypt)]2Sn5. Displacement factor:
exp[±2p2(U11h2a*2 + . . . + 2 U23klb*c*)]. Standard deviations are given in parentheses

Atom Site x y z U11 U22 U33 U12 U13 U23

Sn1 6f 0.15112(8) 0 1/4 699(5) 1342(11) 1108(9) 671(6) 213(4) 426(8)

Sn2 4c 0 0 0.14823(6) 912(6) U11 790(8) 456(3) 0 0
K 4d 1/3 2/3 0.4533(1) 424(9) U11 363(13) 212(4) 0 0
N1 4d 1/3 2/3 0.3204(5) 565(43) U11 367(54) 283(22) 0 0
C2 12 g 0.3232(11) 0.5425(9) 0.2980(3) 1179(86) 948(76) 400(43) 659(70) ±30(52) ±48(49)
C3 12 g 0.3988(12) 0.4968(10) 0.3307(3) 1276(90) 947(76) 402(52) 694(72) ±24(56) ±166(49)
O4 12 g 0.3744(6) 0.4786(5) 0.3944(2) 746(42) 555(36) 438(31) 333(39) ±76(29) ±95(28)
C5 12 g 0.2633(9) 0.3640(10) 0.4113(4) 705(65) 850(69) 635(59) 473(60) ±144(50) ±313(53)
C6 12 g 0.2671(9) 0.3397(8) 0.4773(4) 706(59) 470(48) 825(65) 361(45) 128(54) 59(48)
O7 12 g 0.2573(5) 0.4369(5) 0.5108(2) 574(31) 423(28) 464(30) 317(25) 52(26) 26(25)
C8 12 g 0.2870(8) 0.4356(8) 0.5729(3) 564(53) 489(47) 524(49) 257(43) ±30(42) 28(39)
C9 12 g 0.2579(8) 0.5303(7) 0.6065(3) 601(51) 613(53) 387(38) 281(46) 32(41) 37(38)
N10 4d 1/3 2/3 0.5862(4) 453(39) U11 482(67) 226(20) 0 0

38 Z. anorg. allg. Chem. 1999, 625, 37±42

The [Sn5]2± Cluster Compound [K-(2,2,2-crypt)]2Sn5

Ê ). Standard de-
Table 3 Selected interatomic distances (in A 5.2 Quantum Chemical Calculations
viations are given in parentheses.
The structure of the bare Sn52± anion has been opti-
Sn1±Sn2 2.866(1) N1±C2 1.486(9) mized at the Hartree-Fock level, using a DZVP all-elec-
(2.901)* C2±C3 1.440(12)
±Sn1 3.072(2) (2 × ) O4±C5 1.377(10)
tron basis set [6] for tin. Harmonic vibrational frequen-
(3.128)* C5±C6 1.494(11) cies and Raman intensities have been calculated from
Sn2±Sn1 2.866(1) (3 × ) C6±O7 1.413(8) analytical second derivatives. All calculations have
(2.901)* O7±C8 1.419(8)
K±O7 2.698(5) (3 × ) C8±C9 1.511(10) been carried out with the Gaussian94 program [7].
±O4 2.805(5) (3 × ) C9±N10 1.459(8)
±N1 2.939(11)
±N10 2.940(10) 6 Results and Discussion
* Distance corrected for libration 6.1 Crystal Structure
(K-(2,2,2-crypt)]2Sn5 is isostructural with [Na-(2,2,2-
5 Raman Spectrum crypt)]2Pb5 and [Na-(2,2,2-crypt)]2Sn5 (hP282), the lat-
ter structure, however, was described in the non-cen-
5.1 Measurement tric space group P3c1 (No. 158) [1]. The structure is
characterized by isolated [Sn5]2± Zintl anions, which
The room temperature Raman spectrum was recorded are well separated from each other by the [K+-(2,2,2-
from single crystals (sealed in silica tubes) with a crypt)] inclusion complexes. Fig. 1 shows the perfect
module FRA 106 (Nd: YAG-Laser, 1.064 nm, 200 mW) self-accommodation of the K+-(2,2,2-crypt) inclusion
attached to a Bruker IFS 66v spectrometer. The re- complexes (3-C3 symmetry) to form puckered hexago-
sults are illustrated in Fig. 4 and are discussed in sec-
tion 6.3.

Fig. 1 Section of the [K-(2,2,2-crypt)]2Sn5 structure pro-

jected along the c-axis, showing the distribution of [Sn5]2±
and [K+-(2,2,2-crypt)] units. Notice the perfect accommoda-
tion of the [K+-(2,2,2-crypt)] inclusion complexes in the hex-
agonal primitive Sn5 cluster pattern to form puckered
hexagonal nets.
Fig. 2 The structures of (a) CaIn2 and (b) [K-(2,2,2-
crypt)]2Sn5 demonstrate the hierarchical relationship be-
tween the initiator (a) and its derivative by atom-to aggre-
gate replacement: CaIn2 = [Sn5] [K @ crypt]2.

Z. anorg. allg. Chem. 1999, 625, 37±42 39


Fig. 3 Configuration of the [Sn5]2± cluster anion with dis-
placement ellipsoids (50% probability) and bond lengths
corrected for the librational motion (Table 3).
nal layers. The topological analysis of the structure
shows that [K-(2,2,2-crypt)]2Sn5 forms a hierarchical
structure generated from the initiator CaIn2 (P63/
mmc, hP6) by an atom-to-aggregate replacement
(Fig. 2): [Ca][In]2 = [Sn5][K @ C36H72N4O12]2. Thus,
the distribution of the [Sn5]2± Zintl anions is hexago-
nal primitive, and each [K+ @ C36H72N4O12] inclusion
complex is close to the center of a trigonal superprism
Ê along
formed by six Sn5 clusters, being shifted 1 A
[001] to the position (1/3, 2/3, 0.453).
The [Sn5]2± clusters are centered at a crystallo-
graphic position with 32-D3 symmetry but they have
the higher internal symmetry 6m2-D3h (trigonal bipy-
Ê instead of the published position (±0.0054, 0.151,
ramidal). The bond lengths are d(Sn1±Sn2) = 2.866 A
Ê 0.3145).
and d(Sn2±Sn2) = 3.072 A (Table 3; Fig. 3) almost
identical to those in [Na-(2,2,2-crypt)]2Sn5 [3] (2.865
(average) and 3.10 A Ê , respectively). The structure of
the sodium compound was described by Edwards and
Corbett [1] in the non-centric space group P3c1
mainly because of the presence of a rotational disor-
der (14%) in the Sn5 clusters, which obviously results
in a non-centric Na+ position in the 2,2,2-crypt ligand
cavity (but not in the Na/Pb compound).
6.2 Rigid-body motion of the Sn5 cluster
The Sn atoms of the potassium compound exhibit
large displacement ellipsoids (Fig. 3; Table 2), which
are very similar to those in the cluster anions of [Na-
(2,2,2-crypt)]2Pb5 and [Na-(2,2,2-crypt)]2Sn5 [1]. The
apical atoms have almost spherical shape, but the
equatorial atoms exhibit strange displacements ellip-
soids both in size and orientation. In order to explain
this peculiar feature, a disorder model was postulated
by Edwards and Corbett [1], involving `up' and `down'
oriented distorted cluster anions with the lower 3m-
C3v symmetry.
However, a rigid-body motion analysis of the Uij of
[K-(2,2,2-crypt)]2Sn5 (Table 2) now shows that the dis-
40
M. Somer et al.
placement ellipsoids definitively result from a com-
bined LST motion of a rigid [Sn5]2± anion with full
6m2-D3h symmetry. A libration of ± 9.5° around the
c-axis combined with a translation of ± 0.29 A Ê along
the c-axis leads to a helical up and down motion. This
feature is correlated to the somewhat larger displace-
ment parameters of the upper part of the cation com-
plexes (i. e. nearest neighbors to Sn5, namely N1, C2,
C3 and O4; Table 2). The parameters for libration,
screwing and translation were determined from the
orthogonalized Uij using the least-squares refinement
program of Schomaker and Trueblood [8] included
in the program package SHELXTL-plus [5]. The
value Rg = 0.013 obtained represents a perfect agree-
ment. The bond lengths corrected for the libration
are d1 = d(Sn1±Sn2) = 2.901 A Ê and d2 = d(Sn1±Sn1) =
3.128 AÊ (Fig. 3). They are somewhat shorter than the
calculated ones by quantum chemical methods:
3.202 AÊ and 2.913 A Ê [9]; and 3.229 AÊ and 2.941 A Ê [this
work].
We have then analyzed the data of Edwards and
Corbett [1] as well. The result is also an excellent
agreement of observed Uij and calculated ones: Pb
Ê ); Sn
(Rg = 0.011; libration ± 10.1°; translation ± 0.32 A
Ê
(Rg = 0.088; libration ± 9.3°; translation ± 0.31 A). The
Ê
bond lengths corrected for the libration are d1 = 3.041 A
Ê
and d2 = 3.301 A for [Na-(2,2,2-crypt)]2Pb5, and d1 =
Ê and d2 = 3.153 A Ê for [Na-(2,2,2-crypt)]2Sn5. In
2.906 A
the latter compound, in order to match the published
bond lengths and ellipsoid orientation for Sn1, we had
to used the Sn1 position (0.151, ±0.0054, 0.3155)
6.3 Vibrational Spectrum
The spectroscopical relevant unit is the discrete
[Sn5]2± anion with 6m2-D3h symmetry, for which
9 fundamentals are expected:
Cvib(D3h) = 2 A'1(R) + A@2(IR) + 2 E'(R, IR) + E@(R).
The modes A'1 (m1, m2) and E@ (m6) are only Raman ac-
tive, A@2 (m3) is only IR active. E' (m4, m5) is both Ra-
man and IR active. In the crystal, the [Sn5]2± anion
centers positions with 32-D3 symmetry. The selection
rules for A'1, A@2 and E' in 6m2-D3h are the same as
for the 32-D3 symmetry, except for E@ which becomes
also active in the infrared with the lower symmetry.
Four of the predicted five fundamentals are ob-
served in the Raman spectra of [K-(2,2,2-crypt)]2Sn5
and [Na-(2,2,2-crypt)]2Sn5 at: 180, 133, 120, 104 cm±1
and 181, 131, 121 102 cm±1, respectively. The band at
85 cm±1, observed only in the spectrum of [Na-(2,2,2-
crypt)]2Sn5, is probably an external mode, or is due to
an impurity (but not due to symmetry reduction). The
assignment of the fundamental vibrations is based on
Z. anorg. allg. Chem. 1999, 625, 37±42
The [Sn5]2± Cluster Compound [K-(2,2,2-crypt)]2Sn5
quantum chemical calculations of the Raman frequen-
cies and intensities of the [Sn5]2± cluster anion with
the 6m2-D3h symmetry. Calculated and measured fre-
quencies (Fig. 4) agree within 12 cm±1 and may even
be improved to less than 3 cm±1 by applying an overall
scaling factor of 0.96. The agreement between the cal-
culated and measured intensities is also quite satisfac-
tory, except for the pairs mª4 (E') and mª2 (A'1), exhibit-
ing intensities which are in reverse order to the
measured ones. The calculated frequencies correspond
also with those recently reported [9].
The combination of experimental and calculated
Raman data has recently been demonstrated to be a
very powerful method for understanding the spectra
of the [E9]4± cluster anions with E = Si, Ge, Sn [2, 3].
Again, the characteristic breathing mode mª1 (A'1) has
the largest intensity and the wave numbers 180 cm±1
(K) and 181 cm±1 (Na), respectively. The calculated
wave number for the bare [Sn5]2± cluster anion is
187 cm±1. In order of their intensities follow the
modes mª2 (A'1), mª4 (E') and mª6 (E@) with 120, 133, and
104 cm±1 for the potassium compound and 122, 131,
and 102 cm±1 for the sodium compound. According
Fig. 4 Raman spectra of [K-(2,2,2-crypt)]2Sn5 and [Na-
(2,2,2-crypt)]2Sn5, and the calculated spectrum of the bare
[Sn5]2± anion.
Z. anorg. allg. Chem. 1999, 625, 37±42
with the predictions for the crystallographic site-group
symmetry 32-D3, the doubly degenerate E' and E@
modes are not split. The absence of the Raman active
mode mª5 (E') in the measured spectrum (mªcalc. ≈
70 cm±1) is attributed to the low intensity.
The exclusively IR active mª3 (A@2) mode is expected to
be at 185 cm±1 and should give rise to the most intensive
absorption in the infrared spectrum. However, in the
FIR spectra of [K-(2,2,2-crypt)]2Sn5 and [Na-(2,2,2-
crypt)]2Sn5 no absorption is observed in this region
(185 ± 20 cm±1) indicating that the infrared activity of
the skeleton modes for [Sn5]2± in general must be
quite low. Otherwise, the FIR spectra show in the re-
gion of the internal modes four bands with varying
intensities at 224, 149, 127, 75 cm±1 (K) and 213, 154,
131, 80 cm±1 (Na), arising predominantly from the
vibrations of the cation complexes [M+-(2,2,2-crypt)].
These findings agree well with the results of spec-
troscopical investigations on the Wade clusters [Si9]4±,
[Ge9]4± and [Sn9]4± in binary compounds and cryptates
[2, 3, 10, 11]. As for [Sn5]2±, the [E9]4± Raman spectra
are very characteristic, and consequently well suitable
for diagnostic purposes. On the other hand, no speci-
fic absorption bands are observed in the IR spectra of
the respective compounds. The lack of the infrared ac-
tivity of [Sn5]2± and the [E9]4± cluster ions may be cor-
related to a more homogenous charge distribution in
these Wade clusters.
Note that the assigned sequence of the wave num-
bers for [Sn5]2± derived from the quantum chemical
calculations in this work is consistent with the theore-
tical assignment of Ulvenlund et al. [9], but quite dif-
ferent from that reported for the isoelectronic clusters
[Ge5]2± [12] and [Bi5]3+ [13], namely: mª1 (A'1) > mª2 ´
(A'1) > mª6 (E') > mª4 (E@).
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Z. anorg. allg. Chem. 1999, 625, 37±42