Crystal engineering with oxo- and cyanocarbon anions: Synthesis and structural characterization of triorganotin(IV) pentacyanopropenides and hexacyanoazapentadienides

Article abstract of DOI:10.1002/zaac.201000392

The first triorganotin(IV) pentacyanopropenides, [R₃Sn(H ₂O)₂][C₃(CN)₅] (R = Me (2), nBu (3), Ph (4) were prepared by treatment of Ag[C₃(CN)₅] (1) with equimolar amounts of R₃SnCl in reagent grade THF. In a similar manner, dark red [R₃Sn(H₂O)₂][N{C(CN)C(CN) ₂}₂] (6) containing the hexacyanoazapentadienyl anion was prepared in 55 % yield. The molecular structure of [Ph₃Sn(H ₂O)₂][C₃(CN)₅] (4) was determined by X-ray diffraction. The crystal structure consists of separated trigonal-bipyramidal [Ph₃Sn(H₂O)₂]⁺ cations and nearly planar [C₃(CN)₅]^- anions which are linked through O-H...N hydrogen bonds to give a three-dimensional network.

Full text of DOI:10.1002/zaac.201000392

SHORT COMMUNICATION
DOI: 10.1002/zaac.201000392
Crystal Engineering with Oxo- and Cyanocarbon Anions: Synthesis and
Structural Characterization of Triorganotin(IV) Pentacyanopropenides and
Hexacyanoazapentadienides
Asrial,[a] Falk Olbrich,[b] Marlies Spoida,[a] Axel Fischer,[a] and Frank T. Edelmann*[a]
Keywords: Tin; Organotin compounds; Cyanocarbon anions; Pentacyanopropenides; Structure elucidation
Abstract. The
first
triorganotin(IV)
pentacyanopropenides, of [Ph3Sn(H2O)2][C3(CN)5] (4) was determined by X-ray diffraction.
[R3Sn(H2O)2][C3(CN)5] (R = Me (2), nBu (3), Ph (4) were prepared The crystal structure consists of separated trigonal-bipyramidal
by treatment of Ag[C3(CN)5] (1) with equimolar amounts of R3SnCl [Ph3Sn(H2O)2]+ cations and nearly planar [C3(CN)5]– anions which are
in reagent grade THF. In
[R3Sn(H2O)2][N{C(CN)C(CN)2}2] (6) containing the hexacyanoaza- network.
pentadienyl anion was prepared in 55 % yield. The molecular structure
a
similar manner, dark red linked through O–H···N hydrogen bonds to give a three-dimensional
eton is almost planar, allowing for extensive electronic delocal-
Introduction
ization. The discovery of these fascinating materials dates back
to the pioneering work of Middleton and Webster et al. at
DuPont.[6] Although they are frequently found as unbound
counterions or monodentate ligands, they often act as bridging
Triorganotin compounds are of current interest for various
reasons. Among the commercial applications is the extensive
use of tributyltin derivatives (e.g. halides, oxides, and acetates)
as wood preservatives and marine antifouling paints. However,
these uses have caused considerable environmental concerns
in recent years.[1] Triphenyltin derivatives such as triphenyltin
acetate are commercially used as agricultural fungicides.[2]
Many other organotin derivatives are currently being investi-
gated due to their promising antitumor properties.[3] In most
cases it was found that triorganotin compounds display a
higher biomedical activity than their mono- or diorganotin
counterparts.[4] Last, but not least, it is well established that
numerous organotin derivatives have a highly diverse struc-
tural chemistry and give rise to a variety of supramolecular
structures.[5] Thus, these species are excellent targets for stud-
ies in the area of crystal engineering. It was the latter aspect
that prompted us to investigate the preparation and structural
characterization of a series of triorganotin pentacyanopropen-
ides. The pentacyanopropenide anion, [C3(CN)5]–, belongs to
a series of cyanocarbon anions comprising a plurality of cyano
groups juxtaposed in such a way that they cannot all coordinate
to the same metal atom. Typically, the entire cyanocarbon skel-
ligands affording polymeric coordination compounds.[7] Like
2– [8]
the oxocarbon anions CnOn
,
the cyanocarbon anions are
ideal multiform building blocks for crystal engineering.[9] We
report here the synthesis and structural characterization of the
first triorganotin(IV) derivatives of cyanocarbon anions.
Results and Discussion
As a logical synthetic pathway to triorganotin(IV) pentacyano-
propenides the reaction of triorganotin halides with the readily
available silver pentacyanopropenide, Ag[C3(CN)5] (1),[6b,10]
was chosen. These reactions were carried out in suitable sol-
vents such as THF, dichloromethane or acetonitrile. It soon be-
came clear that under strictly anhydrous conditions the heteroge-
neous reactions were very sluggish and incomplete. Even after
prolonged reaction times no well-defined crystalline reaction
* Prof. Dr. F. T. Edelmann
Fax: +49-391-67-18327
E-Mail: frank.edelmann@ovgu.de
[a] Chemisches Institut
Otto-von-Guericke-Universität Magdeburg
Universitätsplatz 2
39106 Magdeburg, Germany
[b] Institut für Anorganische und Angewandte Chemie
Martin-Luther-King-Platz 6
20146 Hamburg, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201000392 or from the
author.
Scheme 1. Synthesis of the triorganotin(IV) pentacyanopropenides 2–4.
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2011, 637, 190–194
190

Triorganotin(IV) Pentacyanopropenides and Hexacyanoazapentadienides
products could be isolated. However, it was found that the con- which are found in the narrow range of 112.9–117.2 ppm. The
versions were greatly accelerated by the presence of small resonances of the carbon atoms of the propenide unit are ob-
amounts of water, i.e. when the solvents were not specially dried served at ca. 136 ppm (central carbon atom C-3) and ca.
and used as received. The best results were obtained in THF as 57 ppm (outer carbon atoms C-2,4) (cf. Figure 1a). These val-
reaction medium. X-ray structure analyses carried out on the ues are in excellent agreement with those reported in the
products (vide infra) revealed, that this leads to the formation literature.[7]
of [R3Sn(H2O)2]+ cations. Thus, the overall reactions can be for-
The molecular structure of 4 was determined by X-ray diffrac-
mulated as illustrated in Scheme 1.
tion (Figure 1, Table 1). The crystal structure comprises sepa-
All three new compounds 2–4 were isolated in the form of rated [Ph3Sn(H2O)2]+ cations and nearly planar pentacyano-
light yellow crystals, which are readily soluble in polar organic propenide anions. The coordination geometry around tin in the
solvents such as THF, diethyl ether, and dichloromethane, but [Ph3Sn(H2O)2]+ cation[11] is nearly perfect trigonal-bipyramidal
virtually insoluble in hydrocarbon solvents. The compounds with the phenyl substituents occupying the equatorial positions
were characterized by elemental analyses as well as the usual (O1–Sn–O2: 177.85(5)°). With 212.19(17), 212.50(16), and
spectroscopic methods (IR, 1H NMR, 13C NMR). The IR spec- 212.52(17) pm, the three Sn–C bond lengths are virtually identi-
tra display a very strong band slightly above 2200 cm–1, which cal (Table 2).
can be readily assigned to the ν(C≡N) vibration. It has been
Table 1. Crystallographic Data for [Ph3Sn(H2O)2][C3(CN)5] (4).
noted earlier that these bands are not significantly influenced
by the coordination mode of the pentacyanopropenide ion and
differ only in their intensity ratios.[7a] The same effect was
found for the bands of the ν(C=C) vibrations. As expected, the
13C NMR spectra display three signals for the CN groups
4
Identification code
Empirical formula
Formula weight
Temperature
15_00md
C26H19N5O2Sn
552.18
173(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Unit cell dimensions
monoclinic
P21/n
a = 8.2537(1) Å, α = 90°
b = 20.9291(3) Å, β = 103.843(1)°
c = 14.8407(1) Å, γ = 90°
5387.1(3) Å3
4
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
1.251 Mg·m–3
1.058 mm–1
1104
Crystal size
0.6 × 0.6 × 0.4 mm
Theta range for data collection 1.72 to 28.00°
Reflections collected
Index ranges
16185
–10 ≤ h ≤ 10
–27 ≤ k ≤ 21
–19 ≤ l ≤ 19
Independent reflections
Completeness to θ = 29.23°
Absorption correction
Refinement method
Max./ min. transmission
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
Extinction coefficient
Largest diff. peak and hole
5969 [R(int) = 0.0267]
99.5 %
Semi-empirical from equivalents
Full-matrix least-squares on F2
0.6769 and 0.5693
5969 / 6 / 325
1.017
R1 = 0.0239, wR2 = 0.0573
R1 = 0.0291, wR2 = 0.0594
0.0071(3)
1.041 and –0.805 e·Å–3
The structural parameters within the [C3(CN)5]– anion closely
resemble those reported in the literature for other pentacyano-
propenide salts and coordination compounds.[7,12] With C–C
bond lengths of 140.0(2) Å (C2–C3) and 139.7(2) pm (C3–
C4) the central allylic unit clearly shows evidence for multiple
bonding between the three carbon atoms with an almost ideal
symmetrical electronic delocalization. The C–CN distances
amount to 145.6(2) pm (C3–C7) for the central carbon atom
and are slightly shorter for the outer carbon atoms (142.2(2) to
142.8(2) pm). These values are favorably similar to those re-
ported earlier, e.g. for [Et4N][W(CO)5{C3(CN)5}].[12f] The
Figure 1. Molecular (a) and crystal (b) structure of
[Ph3Sn(H2O)2][C3(CN)5] (4).
Z. Anorg. Allg. Chem. 2011, 190–194
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
191

Asrial, F. Olbrich, M. Spoida, A. Fischer, F. T. Edelmann
SHORT COMMUNICATION
Table 2. Selected bond lengths /pm and angles /° for [Ph3Sn(H2O)2]-
[C3(CN)5] (4).
for recrystallization. The IR spectrum showed a very strong
band at 2205 cm–1, which could be readily assigned to the
ν(C≡N) vibration.
Sn–C(11)
Sn–C(31)
Sn–C(21)
Sn–O(2)
212.19(17)
212.50(16)
212.52(17)
227.21(13)
231.82(13)
114.2(2)
142.6(2)
140.0(2)
142.8(2)
139.7(2)
145.6(2)
142.2(2)
142.5(2)
115.0(2)
114.5(2)
113.9(2)
115.3(3)
Sn–O(1)
C(1)–N(1)
C(1)–C(2)
C(2)–C(3)
C(2)–C(6)
C(3)–C(4)
C(3)–C(7)
C(4)–C(8)
C(4)–C(5)
C(5)–N(5)
C(6)–N(2)
C(7)–N(3)
C(8)–N(4)
Scheme 2. Synthesis of [Ph3Sn(H2O)2][N{C(CN)C(CN)2}2] (6).
Conclusions
C(31)–Sn–O(2)
C(21)–Sn–O(2)
C(11)–Sn–O(1)
C(31)–Sn–O(1)
C(21)–Sn–O(1)
O(2)–Sn–O(1)
88.25(6)
The first triorganotin(IV) derivatives of cyanocarbon anions
were synthesized and characterized. Surprisingly, the reactions
according to Scheme 1 and Scheme 2 worked well only in the
presence of minor amounts of water to give the salt-like spe-
cies [R3Sn(H2O)2][C3(CN)5] (R = Me (2), nBu (3), Ph (4) and
[R3Sn(H2O)2] [N{C(CN)C(CN)2}2] (6) in moderate to good
yields. The molecular and crystal structure of
[Ph3Sn(H2O)2][C3(CN)5] (4) was determined by X-ray diffrac-
tion. The crystal structure consists of separated trigonal-bipy-
ramidal [Ph3Sn(H2O)2]+ cations and nearly planar [C3(CN)5]–
anions which are linked through O–H···N hydrogen bonds to
give a three-dimensional network.
95.72(6)
89.67(6)
93.87(6)
83.55(6)
177.85(5)
120.36(7)
120.21(7)
119.34(7)
88.96(5)
C(11)–Sn–C(31)
C(11)–Sn–C(21)
C(31)–Sn–C(21)
C(11)–Sn–O(2)
N(1)–C(1)–C(2)
C(3)–C(2)–C(1)
C(3)–C(2)–C(6)
C(1)–C(2)–C(6)
C(4)–C(3)–C(2)
C(4)–C(3)–C(7)
C(2)–C(3)–C(7)
C(3)–C(4)–C(8)
C(3)–C(4)–C(5)
C(8)–C(4)–C(5)
N(5)–C(5)–C(4)
N(2)–C(6)–C(2)
N(3)–C(7)–C(3)
N(4)–C(8)–C(4)
177.3(2)
121.24(15)
121.36(15)
117.25(15)
128.81(15)
115.17(14)
116.00(14)
119.56(15)
124.48(15)
115.91(16)
176.7(2)
Experimental Section
The reactions were carried out under ambient conditions without any
special precautions to exclude air or moisture. Reagent grade THF was
used as received without drying. IR spectra were recorded with a Per-
kin–Elmer FT-IR spectrometer System 2000. NMR spectra were re-
corded in DMSO-d6 with a Bruker DPX 400 NMR spectrometer (1H:
400 MHz, 13C: 101 MHz). Microanalyses were performed at the
Chemistry Department, Otto-von-Guericke-Universität Magdeburg.
The starting materials Ag[C3(CN)5] (1)[6b] and Ag[N{C(CN)C(CN)2}2]
(5)[13] were prepared according to the literature procedure whereas the
178.6(2)
178.21(19)
179.2(2)
same is true for the C–N bond lengths (113.9(2) to 115.3(3)
pm). In the crystal structure (Figure 1b), the two ionic moieties triorganotin halides R3SnCl (R = Me, nBu, Ph) were commercially
available (Aldrich). The Mass spectrum (EI, 70 eV) was measured
with a MAT 95 apparatus. Microanalysis was performed using a Leco
CHNS 923 or a VARIO EL cube apparatus. The intensity data of 4
were collected using a Stoe IPDS 2T diffractometer with Mo-Kα radia-
tion. The data were collected with the Stoe XAREA[14] program using
ω-scans. Space groups were determined with XRED32[14] program.
The structures were solved by direct methods (SHELXS-97) and re-
fined by full-matrix least-squares methods on F2 using SHELXL-
97.[15]
are connected through O–H···N hydrogen bonds. Each hydro-
gen atom of the coordinated water molecules [Ph3Sn(H2O)2]+
cation interacts in this way with a cyano group of the
[C3(CN)5]– anion to give a three-dimensional network in the
solid state.
In a similar manner, the hitherto unknown [Ph3Sn(H2O)2]+-
salt of the more extended hexacyanoazapentadienyl anion
[N{C(CN)C(CN)2}2]–[6b] was prepared according to Scheme 2.
Treatment of the readily accessible silver salt
Ag[N{C(CN)C(CN)2}2],[6b,13] suspended in reagent grade
THF, with an equimolar amount of Ph3SnCl afforded the dark
red hydrated triphenyltin(IV) derivative [Ph3Sn(H2O)2]
[N{C(CN)C(CN)2}2] (6) in 55 % yield. Compound 6 was
characterized by elemental analysis as well as by IR and NMR
spectroscopy, but failed to produce X-ray quality single-crys-
Preparation of Compounds 2–4 (General Procedure)
To a suspension of Ag[C3(CN)5] (1, 0.55 g, 2 mmol) in reagent grade
THF (20 mL) was added a solution of R3SnCl (2 mmol, R = Me:
0.40 g; R = nBu: 0.65 g; R = Ph: 0.77 g) in THF (20 mL) and the
mixture was stirred at room temp. for 24 h. AgCl was removed by
tals despite several attempts using different solvent mixtures filtration and the clear filtrate was concentrated in vacuo to a total
192 www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 190–194

Triorganotin(IV) Pentacyanopropenides and Hexacyanoazapentadienides
volume of ca. 20 mL. The resulting yellow solution was carefully lay-
ered with n-pentane and left to stand undisturbed for a few days to
give pale yellow crystals of the product. Further purification could be
achieved by recrystallization from diethyl ether.
References
[1] a) S. J. de Mora, in: Tributyltin: Case Study of an Environmental
Contaminant (Ed.: S. J. de Mora), Cambridge University Press,
London, 1996, p. 1–20 ; b) P. E. Gibbs, G. W. Bryan, in: Tributyl-
tin: Case Study of an Environmental Contaminant (Ed.: S. J.
de Mora), Cambridge University Press, London, 1996, p. 212–
236 ; c) I. Omae, Chem. Rev. 2003, 103, 3431.
[2] a) S. J. Blunden, P. A. Cusack, R. Hill, The Industrial Uses of Tin
Chemicals, Royal Society of Chemistry, London, 1985; b) A. K.
Saxena, Appl. Organomet. Chem. 1987, 1, 39; c) A. J. Crowe,
Appl. Organomet. Chem. 1987, 1, 143; d) S. Nicklin, M. W. Rob-
son, Appl. Organomet. Chem. 1988, 2, 487.
[Me3Sn(H2O)2][C3(CN)5] (2): Yield: 0.53 g (72 %), m.p. 121 °C.
C11H13N5O2Sn (365.97): C 36.10, H 3.58, N 19.14; found: C 36.23, H
3.73, N 19.60 %. IR (KBr): ν = 2997 (m), 2206 (vs, C≡N)), 1507 (vs,
˜
C=C), 1487 (m), 1386 (m), 794 (m), 557 (s) cm–1. 1H NMR
(400.13 MHz, [D6]DMSO, 25 °C): δ = 0.54 (s, 9 H, CH3). 13C NMR
(100.62 MHz, [D6]DMSO, 25 °C): δ = 135.7 (C-3); 117.2, 113.9,
113.3 (C≡N); 57.0 (C-2,4); 0.68 (CH3).
[3] a) R. C. Poller, The Chemistry of Organotin Compounds, Aca-
demic Press, New York, 1970; b) M. Gielen, Main Group Met.
Chem. 1994, 17, 1; c) M. Gielen, Metal-Based Drugs 1995, 2,
99; d) E. Lukevics, O. Pudova, Chem. Org. Germanium Tin Lead
Compd. 2002, 2, 1685; e) S. K. Hadjikakou, N. Hadjiliadis, Co-
ord. Chem. Rev. 2009, 253, 235.
[4] a) W. N. Aldrigde, Organotin Compounds. New Chemistry and
Applications. in: Advances in Chemistry Series (Ed.: J. J. Zucker-
man), vol. 168, American Chemical Society, Washington, DC,
1976.p. 157; b) B. M. Elliot, W. N. Aldridge, J. M. Bridges, Bio-
chemistry J. 1979, 177, 461; c) A. G. Davies, P. J. Smith, Adv.
Inorg. Chem. Radiochem. 1980, 23, 1; d) A. K. Saxena, Appl.
Organomet. Chem. 1987, 1, 39; e) Z.-Q. Yang, X.-Q. Song, Q.-
L. Xie, Youji Huaxue 1996, 16, 111.
[5] a) R. G. Swisher, J. F. Vallano, V. Chandrasekhar, R. O. Day,
R. R. Holmes, Inorg. Chem. 1984, 23, 3147; b) J. F. Vallano,
R. O. Day, D. N. Rau, V. Chandrasekhar, R. R. Holmes, Inorg.
Chem. 1984, 23, 3153; c) M. Gielen, R. Willem, M. Biesemans,
M. Boualam, A. El Khloufi, D. de Vos, Appl. Organomet. Chem.
1992, 6, 287; d) E. R. T. Tiekink, Appl. Organomet. Chem. 1991,
5, 1; e) E. R. T. Tiekink, Trends Organomet. Chem. 1994, 1, 71;
f) V. Chandrasekhar, R. Boomishankar, A. Steiner, J. F. Bickley,
Organometallics 2003, 22, 3342; g) C. Ma, Y. Han, R. Zhang, D.
Wang, Eur. J. Inorg. Chem. 2005, 1649; h) V. Chandrasekhar, P.
Thilagar, T. Senapati, Eur. J. Inorg. Chem. 2007, 1004; i) M.
Moya-Cabrear, V. Jancik, R. Cea-Olivares, Tin Chem. 2008, 231;
j) I. Haiduc, E. R. T. Tiekink, J. Zuckerman-Schpector, Tin Chem.
2008, 392; k) M. Zia-ur-Rehman, S. Niaz, S. Shuja, S. Ali, I. S.
Butler, A. Meetsma, M. Khan, Polyhedron 2009, 28, 3439.
[6] a) T. L. Cairns, R. A. Carboni, D. D. Coffman, V. A. Engelhardt,
R. E. Heckert, E. L. Little, E. G. McGeer, B. C. McKusick, W. J.
Middleton, R. M. Scribner, C. W. Theobald, H. E. Winberg, J.
Am. Chem. Soc. 1958, 80, 2775; b) W. J. Middleton, E. L. Little,
D. D. Coffman, V. A. Engelhardt, J. Am. Chem. Soc. 1958, 80,
2795; c) O. W. Webster, J. Am. Chem. Soc. 1964, 86, 2898; d) Re-
view: O. W. Webster, J. Polym. Sci.: Part A: Polymer Chem.
2002, 40, 210.
[nBu3Sn(H2O)2][C3(CN)5] (3): Yield: 0.50 g (51 %), m.p. 112 °C.
C20H31N5O2Sn (492.21): C 48.80, H 6.35, N 14.23; found: C 48.28, H
5.95, N 14.11 %. IR (KBr): ν = 2208 (vs, C≡N), 1548 (vs), 1506 (vs,
˜
C=C), 1484 (m), 1417 (m), 1378 (m), 1259 (m), 535 (s) cm–1. 1H
NMR (400.13 MHz, [D6]DMSO, 25 °C): δ = 1.22 (m, 6 H, CH2), 1.29
(m, 6 H, CH2), 0.93 (m, 6 H, CH2), 0.06 (s, 9 H, CH3). 13C NMR
(100.62 MHz, [D6]DMSO, 25 °C): δ = 135.1 (C-3); 116.0, 114.3,
113.1 (C≡N); 57.2 (C-2,4); 27.9, 26.8, 17.8 (CH2); 13.6 (CH3).
[Ph3Sn(H2O)2][C3(CN)5] (4): Yield: 0.83 g (75 %), m.p. 127 °C.
C26H19N5O2Sn (552.18): C 56.56, H 3.47, N 12.68; found: C 55.65, H
3.38, N 12.82 %. IR (KBr): ν = 3068 (m), 2208 (vs, C≡N), 1578 (m),
˜
1503 (vs, C=C), 1430 (s), 1385 (m), 1195 (m), 1076 (m), 997 (w), 731
(s), 669 (s) cm–1. 1H NMR (400.13 MHz, [D6]DMSO, 25 °C): δ =
7.81, 7.79, 7.55 (m, Ph). 13C NMR (100.62 MHz, [D6]DMSO, 25 °C):
δ = 135.9 (C-3); 134.0, 133.1, 130.2, 129.2 (Ph); 116.4, 114.0, 112.9
(C≡N); 57.1 (C-2,4).
Preparation of [Ph3Sn(H2O)2][N{C(CN)C(CN)2}2] (6)
Solid Ph3SnCl (0.39 g, 1.0 mmol) was added in one portion to a stirred
suspension of Ag[N{C(CN)C(CN)2}2] (5, 0.33 g, 1.0 mmol) in THF
(20 mL) and the reaction mixture was stirred at room temp. for 24 h.
After removal of the solvent in vacuo, the residue was extracted with
diethyl ether (30 mL). Insoluble material was filtered off, and the fil-
trate was again evaporated to dryness. The crude product was redis-
solved in a THF/toluene mixture (1:2, 20 mL) and carefully layered
with n-pentane to produce dark red crystals of 6 after standing undis-
turbed for
a few days. Yield: 0.83 g (55 %), m.p. 127 °C.
C28H19N7O2Sn (604.21): C 55.66, H 3.17, N 16.23; found: C 54.97, H
2.95, N 15.82 %. IR (KBr): ν = 3060 (m), 2205 (vs, CN), 1588 (m),
˜
1500 (vs, C=C), 1428 (s), 1411 (s), 1383 (m), 1188 (m), 1067 (m),
1
1002 (w), 735 (s), 658 (s) cm–1. H NMR (400.13 MHz, [D6]DMSO,
25 °C): δ = 7.48, 7.25 (m, Ph). 13C NMR (100.62 MHz, [D6]DMSO,
25 °C): δ = 135.7 (C(CN)); 133.2, 130.7, 129.3, 128.8 (Ph); 57.1
(C(CN)2).
[7] a) L. Jäger, C. Tretner, K. Sünkel, J. Košížek, Z. Anorg. Allg.
Chem. 1998, 624, 1381; b) E. Lefebvre, F. Conan, N. Cosquer, J.-
M. Kerbaol, M. Marchivie, J. S. Pala, M. M. Kubicki, E. Vigier,
C. J. G. Garcia, New J. Chem. 2006, 30, 1197
[8] a) G. Gilli, V. Bertolasi, P. Gilli, V. Ferretti, Acta Crystallogr.,
Sect. B 2001, 57, 859; b) Y. Liu, A. H. W. Lam, F. W. Fowler,
J. W. Lauher, Mol. Cryst. Liquid. Cryst. Sci. Technol. A 2002,
389, 39; c) C. Borel, K. Larsson, M. Håkansson, B. E. Olsson,
A. D. Bond, L. Öhrström, Crystal Groth Des. 2009, 9, 2821;
d) V. E. de Oliveira, R. Diniz, L. F. C. de Oliveira, Quimica
Nova 2009, 32, 1917.
Crystallographic data for the crystal structure reported in this paper
can be obtained from the Cambridge Crystallographic Data Center, 12
Union Road, Cambridge CB21EZ, UK (Fax: +44-1223-336-033; E-
Mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/) by re-
ferring to the CIF deposition code CCDC-233441.
Supporting Information (see footnote on the first page of this article):
ORTEP drawings and X-ray structural data as well as complete CIF
file for 4.
[9] a) D. Braga, F. Grepioni, Coord. Chem. Rev. 1999, 183, 19; b) D.
Braga, G. R. Desiraju, J. S. Miller, S. G. Orpen, S. L. Proce,
CrystEngComm 2002, 4, 500; c) G. R. Desiraju, J. Ind. Chem.
Soc. 2003, 80, 151; d) D. Braga, Chem. Commun. 2003, 2751;
e) L. Brammer, Chem. Soc. Rev. 2004, 33, 476; f) K. Biradha,
CrystEngComm 2003, 5, 374; g) G. R. Desiraju, Angew. Chem.
Int. Ed. 2007, 46, 8342; h) C. B. Aakeroy, N. R. Champness, C.
Janiak, CrystEngComm 2010, 12, 22.
Acknowledgement
F. O. thanks the Government of Sachsen-Anhalt for a Habilitation
scholarship (Graduiertenförderung). Financial support by the Otto-von-
Guericke-Universität Magdeburg is also gratefully acknowledged.
[10] L. Jäger, C. Wagner, W. Hanke, J. Mol. Struct. 2000, 525, 107.
Z. Anorg. Allg. Chem. 2011, 190–194
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
193

Asrial, F. Olbrich, M. Spoida, A. Fischer, F. T. Edelmann
SHORT COMMUNICATION
[11] A. Azadmehr, M. Jabbari, F. Gharib, M. M. Mostafa, Can. J.
Chem. 2008, 86, 751.
Miller, J. Mol. Struct. 2008, 890, 41; i) D. V. Poltorak, A. V.
Gutov, E. B. Rusanov, A. N. Chernega, Ukrainskii Khim. Zh.
2009, 75, 114.
[12] a) M. F. Retting, R. M. Wing, Inorg. Chem. 1978, 17, 2685;
b) G. A. Sim, D. I. Woodhouse, G. R. Knox, J. Chem. Soc., Dal- [13] M. Decoster, J. E. Guerchais, Y. Le Mest, J. S. Pala, S. Triki, L.
ton Trans. 1979, 629; c) W. D. Jensen, R. A. Jacobson, Inorg.
Chim. Acta 1981, 50, 189; d) J. S. Miller, J. C. Calabrese, H. [14] Stoe, XAREA Program for X-ray Crystal Data Collection
Rommelmann, S. R. Chittipeddie, J. H. Zhang, W. M. Reiff, A. J. (XRED32 included in XAREA), Stoe, 2002.
Toupet, Polyhedron 1996, 15, 195.
Epstein, J. Am. Chem. Soc. 1987, 109, 769; e) M. L. Yates, A. A. [15] a) G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Arif, J. L. Manson, B. A. Kalm, B. M. Burkhart, J. S. Miller, In-
org. Chem. 1998, 37, 840; f) S. Duclos, F. Conan, S. Triki, Y.
Le Mest, M. L. Gonzalez, J. S. Pala, Polyhedron 1999, 18, 1935;
g) M. I. Bruce, M. A. Buntine, K. Costuas, B. G. Ellis, J.-F.
Halet, P. J. Low, B. W. Skelton, A. H. White, J. Organomet.
Chem. 2004, 689, 3308; h) Q. Zhu, A. M. Arif, L. Öhrström, J. S.
Refinement, Universität Göttingen, Germany, 1997; b) G. M.
Sheldrick, SHELXS-97, Program for Crystal Structure Solution,
Universität Göttingen, Germany, 1997.
Received: October 29, 2010
Published Online: December 29, 2010
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