Molecular networks based on CN coordination bonds

Article abstract of DOI:10.1002/ejic.201200427

This study examines the use of tetrahedral [E(O-C₆X ₄-CN)₄]^- anions (E = B, Al; X = H, F), which can be synthesized from the reaction of tetrahedral NaBH₄/LiAlH ₄ and HO-C₆X₄-CN, as anionic linkers for the generation of 2D and 3D crystalline coordination polymer networks. Such polymer networks were obtained by the connection of tetrahedral p-cyanophenoxy aluminate or borate linkers with monocationic metal centers such as Li⁺, Na⁺, Ag⁺, and Cu⁺. These studies are specifically focused on the synthesis, structure, and stability of such polymers. Additionally, the perfluorinated O-C₆F₄-CN linker was used to study electronic influences. Salts bearing the perfluorinated [E(O-C₆F₄-CN)₄]^- anion decompose into E(O-C₆F₄-CN)₃ and [O-C₆F ₄-CN]^-, which is also observed when a Lewis acid such as B(C₆F₅)₃ is added. Moreover, addition of B(C₆F₅)₃ leads to the formation of molecular-ion pairs because the cyano groups are now either completely or partly blocked. The structures of M[Al(O-C₆H₄-CN)₄] (M = Li, Ag, Cu), Na[B(O-C₆H₄-CN)₄], and Li[Al(O-C₆F₄-CN)₄] as well as of the decomposition products Na(O-C₆F₄-CN), (THF)Al[O-C ₆H₄-CN·B(C₆F₅) ₃]₃ (THF = tetrahydrofuran), Na[(F₅C ₆)₃B·O-C₆H₄- CN·B(C₆F₅)₃], and Li[NC-C ₆F₄-O-Al{O-C₆F₄-CN·B(C ₆F₅)₃}₃] are discussed. Copyright

Full text of DOI:10.1002/ejic.201200427

Job/Unit: I20427
/KAP1
Date: 24-09-12 16:34:27
Pages: 13
FULL PAPER
DOI: 10.1002/ejic.201200427
Molecular Networks Based on CN Coordination Bonds
Markus Karsch,[a] Henrik Lund,[a] Axel Schulz,*[a,b] Alexander Villinger,[a] and
Karsten Voss[a]
Keywords: Coordination polymers / Aluminates / Borates / Silver / Copper / Bridging ligands
This study examines the use of tetrahedral [E(O–C6X4–CN)4]– bearing the perfluorinated [E(O–C6F4–CN)4]– anion decom-
anions (E = B, Al; X = H, F), which can be synthesized from
the reaction of tetrahedral NaBH4/LiAlH4 and HO–C6X4–CN,
as anionic linkers for the generation of 2D and 3D crystalline
coordination polymer networks. Such polymer networks
were obtained by the connection of tetrahedral p-cyano-
phenoxy aluminate or borate linkers with monocationic
pose into E(O–C6F4–CN)3 and [O–C6F4–CN]–, which is also
observed when a Lewis acid such as B(C6F5)3 is added. More-
over, addition of B(C6F5)3 leads to the formation of molecular-
ion pairs because the cyano groups are now either com-
pletely or partly blocked. The structures of M[Al(O–C6H4–
CN)4] (M = Li, Ag, Cu), Na[B(O–C6H4–CN)4], and Li[Al(O–
metal centers such as Li+, Na+, Ag+, and Cu+. These studies C6F4–CN)4] as well as of the decomposition products Na(O–
are specifically focused on the synthesis, structure, and sta-
bility of such polymers. Additionally, the perfluorinated O–
C6F4–CN linker was used to study electronic influences. Salts
C6F4–CN), (THF)Al[O–C6H4–CN·B(C6F5)3]3 (THF = tetra-
hydrofuran), Na[(F5C6)3B·O–C6H4–CN·B(C6F5)3], and Li[NC–
C6F4–O–Al{O–C6F4–CN·B(C6F5)3}3] are discussed.
their fluorinated analogs[11] have been studied and widely
applied, for example, in catalysis, however, to the best of
our knowledge the cyano-substituted anions are not known
yet. The only known cyanoborates and aluminates are of
the type [B(C6H4–CN)4]– [12] and [B(CN)4]–.[13] In addition,
there is a great wealth of compounds based on polycyano-
metallates,[4b,14] [C(CN)3]–,[15] or Si(p-C6H4–CN)4.[16]
Herein, we describe crystalline coordination polymer net-
works that were obtained through the connection of tetra-
hedral p-cyanophenoxy aluminate or borate linkers with
monocationic transition metal center such as Ag+ and Cu+.
A common feature of these supramolecular polymers is the
presence of dative M–NC bonds (M = Ag, Cu), which are
crucial structure-directing elements in addition to the tetra-
hedral [E(O–C6X4–CN)4]– building block.
Introduction
The directed synthesis of coordination polymers[1] with
two- or three-dimensional framework structures can be
achieved through the connection of molecular building
blocks through hydrogen bonds,[2,3] donor–acceptor
bonds,[4] halogen bonds,[5] metal–metal,[6] CH–π,[7] and π–π
interactions.[8] The synthesis and characterization of infinite
two- and three-dimensional networks has been an area of
rapid growth, because many applications of their useful
electronic, magnetic, optical, and catalytic properties are ex-
pected.
Coordination polymers are composed of connectors and
linkers.[1] We decided to study tetraphenoxyaluminates and
borates of the type [E(O–C6X4–CN)4]– (E = B, Al; X = H,
F) with one cyano group as binding site per phenoxy group
as linker. Transition-metal ions such as silver or copper ions
are often utilized as versatile connectors in the construction
of coordination polymers. Depending on the metal and its
oxidation state, different coordination numbers and geome-
tries, such as linear, tetrahedral, square planar, square pyr-
amidal, trigonal bipyramidal, octahedral, etc. are ob-
tained.[1] Tetraphenoxyaluminates and borates[9,10] and also
Results and Discussion
Ligands, such as p-cyanophenoxy linkers, with the poten-
tial for supplemental Lewis base interactions are finding in-
creasing utility for the stabilization of electrophilic metal
centers (metal = alkali, Cu, Ag, etc.).[17] For the synthesis
of salts bearing the aluminate and borate anions, [E(O–
C6H4–CN)4]– (E = Al, B), LiAlH4 and NaBH4 were treated
with four equivalents of 4-hydroxybenzonitrile, HO–C6H4–
CN, at low temperatures in tetrahydrofuran (THF,
Scheme 1). The resulting solution was heated to reflux for
two hours. After filtration and removal of the solvent in
vacuo, a colorless solid was obtained, which was washed
with Et2O to remove the excess 4-hydroxybenzonitrile. In
both cases, the pure Li[Al(O–C6H4–CN)4] (1) or Na[B(O–
[a] Institut für Chemie, Universität Rostock,
Albert-Einstein-Str. 3a, 18059 Rostock, Germany
Fax: +49-381-498-6381
E-mail: axel.schulz@uni-rostock.de
Homepage: http://www.schulz.chemie.uni-rostock.de/
[b] Leibniz Institut für Katalyse,
Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Fax: +49-381-498-6381
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200427.
Eur. J. Inorg. Chem. 0000, 0–0
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M. Karsch, H. Lund, A. Schulz, A. Villinger, K. Voss
FULL PAPER
Scheme 1. Synthesis of Li[Al(O–C6H4–CN)4] (1) and Na[B(O–C6H4–CN)4] (2).
C6H4–CN)4] salt (2) was obtained in yields between 60– CN)4] (5) is easily generated in good yields (51%) by utiliz-
70%. Li[Al(O–C6H4–CN)4] (1) is highly soluble in THF ing 4-cyano-2,3,5,6-tetrafluorophenol, HO–C6F4–CN, as
and acetonitrile, whereas Na[B(O–C6H4–CN)4] (2) is shown in Scheme 4, in the reaction of NaBH4 with HO–
slightly less soluble. Both salts are almost insoluble in C6F4–CN in acetonitrile only the formation of Na(O–
CH2Cl2 and aromatic solvents such as benzene or toluene.
C6F4–CN) (6), the free acid B(O–C6F4–CN)3, and molecu-
By utilizing salt metathesis reactions with different silver lar hydrogen (Scheme 5) is observed. If the Na+ ion is not
–
–
salts AgX (X = NO3 , CF3COO–, CF3SO3 ), the exchange stabilized by significant donor–acceptor interactions as in
of the Li+ ions by Ag+ ions was achieved (Scheme 2) to compounds 1–5, the “naked” Na+ ion seems to be the
afford Ag[Al(O–C6H4–CN)4] (3) in yields between 40–50%. stronger Lewis acid, which results in the abstraction of O–
The copper salt Cu[Al(O–C6H4–CN)4] (4) was obtained in C6F4–CN– from the [B(O–C6F4–CN)4]– ion and yields
the reaction of Ag[Al(O–C6H4–CN)4] with CuI, which, un- Na(O–C6F4–CN) and B(O–C6F4–CN)3. Obviously, the
like AgI, is soluble in acetonitrile (50% yield, Scheme 3). In driving force for the formation of 6 is the instability of the
comparison to the lithium salt, the M[Al(O–C6H4–CN)4] [B(O–C6F4–CN)4]– anion towards strong electrophilic ions.
salts (M = Ag, Cu) are also very good soluble in acetonitrile The whole process can formally be regarded as a Lewis
but considerably less soluble in THF. Whereas the silver acid/Lewis base reaction. A similar Lewis acid/Lewis base
and lithium salt can be crystallized as solvent-free species, reaction is assumed to occur for weakly coordinating
solvent molecules occupy the voids in the copper species.
anions of the type [Al(ORF)4]– or [B(C6F5)4]– in the pres-
In a second series of experiments, we tried to synthesize ence of very electrophilic cations, in which the decomposi-
– [20]
the analogous perfluorinated salts Li[E(O–C6F4–CN)4] (E tion is initiated either by ligand (RFO–,[18,19] C6F5 )
= B, Al). Although the aluminate salt Li[Al(O–C6F4– fluoride ion abstraction.[21]
or
Scheme 2. Synthesis of Ag[Al(O–C6H4–CN)4] (3).
Scheme 3. Synthesis of Cu[Al(O–C6H4–CN)4] (4).
Scheme 4. Synthesis of Li[Al(O–C6F4–CN)4] (5).
Scheme 5. Synthesis of Na(O–C6F4–CN) (6).
2
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Molecular Networks Based on CN Coordination Bonds
Finally, we studied the stability of salts bearing the Spectroscopic Studies
[E(O–C6X4–CN)4]– anion towards strong Lewis acids such
The 13C NMR spectroscopic data along with the IR/Ra-
as B(C6F5)3. The idea was to see if either the very bulky
adduct anions[22–25] of the type [E(O–C6X4–CN·
B(C6F5)3)4]– are formed or if Lewis acid assisted degrada-
tion occurs leading to the formation of M[O–C6X4–
CN·B(C6F5)3]. The reaction of Li[Al(O–C6H4–CN)4] with
an excess of B(C6F5)3 led to the isolation of the solvent-
stabilized Lewis acids (THF)2Al[O–C6H4–CN·B(C6F5)3]3
(7) and Li[(F5C6)3B·O–C6H4–CN·B(C6F5)3] [Equation (1)];
and the addition of B(C6F5)3 to a solution of Na[B(O–
C6H4–CN)4] gave Na[(F5C6)3B·O–C6H4–CN·B(C6F5)3] (8a)
as confirmed by X-ray structure analysis. In the latter case,
it can be assumed that the free acid (Et2O)2B[O–C6H4–
CN·B(C6F5)3]3 is also formed; however, this could not be
isolated [Equation (1)]. Only when Li[Al(O–C6F4–CN)4]
was treated with B(C6F5)3, was no decomposition observed,
however, the tri-adduct Li[(NC–C6F4–O)Al{O–C6F4–
CN·B(C6F5)3}3] (9) and not the tetra-adduct was obtained
as shown by X-ray structure analysis.
man data for the compounds described in this work are
listed in Table 1. The IR and Raman data of all considered
CN-group-containing anions in Table 1 show sharp bands
in the expected 2220–2320 cm–1 region, which can be as-
signed to the νCN stretching frequencies. Interestingly, there
is almost no difference between free HO–C6X4–CN (X =
H: 2231; X = F: 2252 cm–1) and the metal salts containing
the [E(O–C6X4–CN)4]– ion (shift Ͻ 10 cm–1; X = H: 2223–
2236; X = F: 2252–2256 cm–1). On the contrary, the coordi-
nation of a Lewis acid such as B(C6F5)3 to a NC–R species
causes a significant band shift to higher wave numbers (Δν
˜
= 76 in 7, 78 in 8a, and 66 cm–1 in 9).[27] For the B(C6F5)3
adducts, 11B spectroscopy is also particularly well suited to
distinguish between three-coordinate borane and the four-
coordinate boron found in the Lewis acid–base adducts for
which the 11B resonance (7: –11.8, 8: –10.1, and 9:
–8.5 ppm) is shifted to lower frequency with respect to free
B(C6F5)3 by more than 65 ppm [cf. B(C6F5)3 in CD2Cl2:
59.1 ppm].[28–33]
2 solvent + [E{O–C6H4–CN·B(C6F5)3}4]– + B(C6F5)3 i
(solvent)2E[O–C6H4–CN·B(C6F5)3]3 +
[(F5C6)3B·O–C6H4–CN·B(C6F5)3]– (1)
X-ray Structure Analysis
Properties
The structures of compounds 1–9 have been determined.
Tables 2 and 3 present the X-ray crystallographic data of
species 1–5, 7, and 8a. X-ray quality crystals of all consid-
ered species were selected in Kel-F-oil (Riedel-de Haën) or
Fomblin YR-1800 (Alfa Aesar) at ambient temperature. All
samples were cooled to –100(2) °C during the measurement.
More details are found in the Supporting Information.
Salts bearing the [E(O–C6X4–CN)4]– anion (E = B, Al;
X = H, F) are neither air- nor considerably moisture-sensi-
tive. They dissolve in solvents such as CH3CN or THF but
not in CH2Cl2 or benzene. They slowly decompose in water
with the formation of the free alcohol HO–C6X4–CN and
B2O3·nH2O and Al2O3·nH2O as shown by H, 19F, and 11B
1
NMR studies. All mentioned [E(O–C6X4–CN)4]– salts are
easily prepared in bulk and are indefinitely stable when
stored in a sealed tube in the dark (silver salts). All consid-
Li[Al(O–C6H4–CN)4] (1)
Crystals suitable for X-ray crystallographic analysis were
ered salts bearing the [E(O–C6X4–CN)4]– ion are thermally obtained by adding three drops of CH2Cl2 to a saturated
stable up to at least 270 °C (Table 1). The thermal stabilities THF solution of 1 and storing it at 7 °C for 2 d. Complex
nicely correlate with the trends found for M[B(CN)4] (M = 1 crystallized as colorless blocks in the tetragonal space
Li 500, Cu 470, Ag 440 °C).[26] The decomposition products group I4 with two formula units per unit cell. Both metal
¯
were analyzed by powder XRD (PXRD) measurements and ions have a tetrahedral coordination environment and all p-
were identified as LiAlO2 (for 1), NaBO2 (for 2), Ag (for cyanophenoxy linker molecules (tetrahedrally attached to
3), and a mixture of Cu2O, CuO, and Cu (for 4).
Al atoms through O atoms and to Li atoms through N
Table 1. Thermal analysis: melting and decomposition points (from DSC measurements); spectroscopic data: IR, Raman, and 13C NMR
spectroscopic data of HO–C6X4–CN(X = H, F) based species along with the data of free p-cyanophenols.
M.p. [°C] 13C NMR δ(CN) [ppm] IR υCN [cm–1]
Raman υCN [cm–1]
HO–C6H4–CN
HO–C6F4–CN
Li[Al(O–C6H4–CN)4] (1)
Na[B(O–C6H4–CN)4] (2)
113
268
119.6
107.8
120.8
119.4
120.7
120.9
109.7
113.0
115.6
114.7
114.8
2231 (s)
2252 (s)
2236 (s)
2226 (m)
2223 (s)
2231 (m)
2256 (m)
2253 (s)
2307 (s)
2309 (s)
2239(10)
2267(1), 2252(10)
2244(2), 2235(10), 2217(4)
2230(10)
2244(10)
2235(10), 2181(1)
2266(10)
2252(10)
2312(10)
2312(10)
349[a]
362[a]
243[a]
281[a]
271
Ag[Al(O–C6H4–CN)4] (3)
Cu[Al(O–C6H4–CN)4] (4)
Li[Al(O–C6F4–CN)4] (5)
Na(O–C6F4–CN) (6)
367
(thf)2Al[O–C6H4–CN·B(C6F5)3]3 (7)
Na[(F5C6)3B·O–C6H4–CN·B(C6F5)3] (8a)
Li[(NC–C6F4–O)Al{O–C6F4–CN·B(C6F5)3}3] (9)
137[a]
155
319[a]
2318 (m), 2263 (w) 2324(10)
[a] Decomposition temperature.
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M. Karsch, H. Lund, A. Schulz, A. Villinger, K. Voss
Table 2. Crystallographic details of Li[Al(O–C6H4–CN)4] (1), Na[B(O–C6H4–CN)4] (2), Ag[Al(O–C6H4–CN)4] (3).
FULL PAPER
1
2
3
Empirical formula
C28H16AlLiN4O4
506.37
colorless
C46H52BN4NaO8.5
830.72
colorless
triclinic
P1
C28H16AgAlN4O4
607.3
colorless
Formula weight. [gmol–1]
Color
Crystal system
Space group
tetragonal
tetragonal
¯
I4
¯
I4
a [Å]
b [Å]
c [Å]
α [°]
6.9524(8)
6.95424(8)
25.457(7)
90
90
90
1230.5(4)
2
0.13
11.3778(4)
14.5700(6)
14.8545(6)
83.928(2)
76.016(2)
70.325(2)
2249.2(2)
2
6.9541(3)
6.9541(3)
26.2002(15)
90
90
90
1267.0(1)
2
0.87
β [°]
γ [°]
V [Å3]
Z
μ [mm–1]
0.09
λ Mo-Kα [Å]
T [K]
Measured reflections
Independent reflections
Reflections with IϾ2σ(I)
Rint
0.71073
173
4206
2153
2053
0.03
0.71073
173
38231
11158
7149
0.044
880
0.71073
173
5766
2274
2167
0.022
1480
F(000)
520
R1 {R[F2 Ͼ 2σ(F2)]}
wR2 (all data)
GooF
0.036
0.091
1.08
0.067
0.204
0.99
644
0.026
0.048
1.002
87
Parameters
87
Table 3. Crystallographic details of Cu[Al(O–C6H4–CN)4]·2CH2Cl2 (4), Li[Al(O–C6F4–CN)4] (5), and (THF)2Al[O–C6H4–CN·B(C6F5)3]
(7).
3
4
5
7
Empirical formula
C30H20AlCl4CuN4O4
732.82
colorless
monoclinic
P21/c
C48H40.8AlF16LiN4O9
1155.55
colorless
monoclinic
C2/c
C83.5H29AlClB3F45N3O5
2103.96
colorless
Formula weight [gmol–1]
Color
Cryst. system
Space group
triclinic
¯
P1
a [Å]
b [Å]
c [Å]
α [°]
12.4486(6)
15.0360(6)
16.5961(7)
90
92.074(2)
90
3104.4 (2)
4
1.12
23.49(2)
13.024(9)
33.99(2)
90
98.59(2)
90
10280(12)
8
0.16
16.921(9)
17.643(9)
18.37(1)
62.08(2)
62.87(2)
83.93(2)
4271(4)
2
β [°]
γ [°]
V [Å3]
Z
μ [mm–1]
0.21
λ Mo-Kα [Å]
T [K]
Measured reflections
Independent reflections
Reflections with IϾ2σ(I)
Rint
0.71073
173
36748
7508
4900
0.71073
173
43873
11625
6878
0.71073
173
71398
20425
11411
0.041
0.058
0.032
F(000)
1480
0.043
0.110
1.06
4710
0.051
0.138
1.05
2082
0.055
0.174
0.99
R1 {R[F2 Ͼ 2σ(F2)]}
wR2 (all data)
GooF
Parameters
442
846
1365
atoms) bridge the two metal ions to form a 3D framework and the LiN4 moiety are slightly distorted with one smaller
structure as shown in Figures 1 and 2. Each nitrile group [N1–Li1–N1Ј 106.78(3) and O1Ј–Al1–O1 107.43(3)°] and
in the structure is coordinated to a lithium atom with a Li– one larger angle [N1Ј–Li1–N1ЈЈ 115.00(6) and O1Ј–Al1–
N length of 2.054(1) Å (cf. Σrcov = 2.05 Å) and an Al–O O1ЈЈ 113.63(7)°]. Whereas the LiN4 tetrahedra are almost
bond length of 1.7329(9) (cf. Σrcov = 1.89 Å).[34] These val- linearly attached to the phenoxy linker [C7–N1–Li1
ues are similar to those observed for phenoxyaluminates 160.0(1)°], the AlO4 tetrahedra display a bent structure
and lithium nitrile complexes.[35] Both the AlO4 tetrahedron [C1–O1–Al1 134.20(8)°].
4
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Molecular Networks Based on CN Coordination Bonds
Figure 2. Five interpenetrating diamond-like frameworks in the
structure of 1 showing the translational relationship between inde-
pendent nets.
An inherent feature of such entangled interpenetrated
structures is that they can be disentangled only by breaking
internal connections.[1a] Furthermore, N2 sorption measure-
ments with compound 1 did not show significant perma-
nent porosity (approximately 4 m2 g–1 of BET surface). The
structural collapse seems to occur in one step at 349 °C
upon thermal treatment and results in the formation of Li-
AlO2.
Ag[Al(O–C6H4–CN)4] (3)
Compound 3 crystallizes isostructurally to compound 1
with very similar cell parameters [cf. Li: 6.9524(8),
6.9524(8), 25.457(7) vs. Ag: 6.9541(3), 6.9541(3),
26.200(2) Å; Table 2]. Only the c axis is slightly elongated.
All the structural features discussed before for compound 1
Figure 1. Top: Ball-and-stick drawing of the local environment
about the tetrahedral centers in 1 (hydrogen atoms omitted for clar-
ity). Selected bond lengths [Å] and angles [°]: Al1–O1 1.7329(9),
O1–C1 1.338(1), C7–N1 1.149(2), N1–Li1 2.054(1); O1Ј–Al1–O1
107.43(3), O1Ј–Al1–O1ЈЈ 113.63(7), N1–Li1–N1Ј 106.78(3), N1Ј–
Li1–N1ЈЈ 115.00(6), C1–O1–Al1 134.20(8), C7–N1–Li1 160.0(1).
Bottom: adamantane structural motif in 1.
A closer look at the 3D network of 1 revealed a highly
interpenetrated structure, which does not possess large free
channels or pores. It consists of five independent infinite
frameworks, each with diamond-like topology (Figure 2).
The interpenetrated framework of 1 is related to some clas-
sic inorganic frameworks, as it features the adamantane
structural motif known from diamondlike frameworks such
as that of zinc cyanide, which consists of two independent
infinite frameworks, each with diamondlike topology.[36] In-
terpenetrating diamond-related nets with n = 5 (n = number
of nets) have been describe for adamantane-1,3,5,7-tetra-
carboxylic acid,[37] [Cu(L)2](BF4) (L = 1,4-dicyanobenz-
ene)[38] and [Cu(bpe)2](BF4) [with CH3CN or CH2Cl2 as
guest molecules, bpe = 1,4-bis(4-pyridyl)butadiyne].[39]
Figure 3. Ball-and-stick drawing of the local environment about the
tetrahedral centers in 3 (hydrogen atoms omitted for clarity). Se-
lected bond lengths [Å] and angles [°]: Ag1–N1 2.286(2), Al1–O1
1.736(1), N1–C7 1.144(3); N1Ј–Ag1–N1 117.76(7), N1Ј–Ag1–N1ЈЈ
105.49(3), O1ЈЈ–Al1–O1 112.7(1), O1Ј–Al1–O1 107.89(5), C7–N1–
Ag1 154.0(2), C1–O1–Al1 131.4(1).
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FULL PAPER
(Figure 1) are similarly found in the silver salt (Figure 3). average Cu–N distance of 1.995 Å {cf. 1.979 Å in [Cu2-
Only slight differences arise from the longer Ag–N bond (1,2,4,5-tetracyanobenzene)3](PF6)2(Me2CO)4 or 1.977 Å in
length of 2.286(2) compared to 2.054(1) Å for Li–N in 1; Cu[B(CN)4]}[26] and 1.732 Å for the Al–O bond lengths [cf.
the Al–O distances are essentially identical and the angles 1.733 and 1.736(1) Å in compounds 1 and 3, respectively].
are also very similar.
The solid-state structure possesses relatively large cavities
despite fourfold interpenetration (see Supporting Infor-
mation Figure S2), and the cavities are filled by two solvent
molecules per formula unit. As illustrated in Figure 4 (bot-
tom), the major difference in the solid-state structure of 4
compared to the those of compounds 1 and 2 arises from
the smaller degree of interpenetration in 4 leading to larger
voids, which are filled with disordered CH2Cl2 solvent mo-
lecules. Thermogravimetric analysis (TGA) indicates that
the solvent can be fully removed at 90 °C. However, re-
moval of the solvent leads to a loss of crystallinity (single-
crystal integrity is not maintained), as evidenced by powder
X-ray diffraction analysis (see Supporting Information). No
specific surface could be found by nitrogen sorption experi-
ments of the desolvated compound.
Cu[Al(O–C6H4–CN)4]·2CH2Cl2 (4)
Single crystals of 4 were grown by slow vapor diffusion
of CH2Cl2 into a saturated acetonitrile solution of the com-
pound overnight at ambient temperature. In contrast to the
isostructural complexes 1 and 3, the copper salt crystallizes
in the monoclinic space group P21/c with four formula units
per unit cell. Again, both metal centers sit in a slightly dis-
torted tetrahedral environment (Figure 4, top) with an
Na[B(O–C6H4–CN)4]·8THF (2)
Crystals suitable for X-ray crystallographic analysis were
obtained by adding three drops of CH2Cl2 to a saturated
THF solution and storing it at ambient temperature. Com-
¯
plex 2 crystallizes in the triclinic space group P1 with two
formula units per unit cell. As the Na+ ions prefer an octa-
hedral rather than a tetrahedral coordination sphere (in
contrast to Li+ or Cu+, see above), the coordination sphere
around the sodium ions is either composed of four square
planar arranged N atoms of the p-cyanophenoxy linker and
two O atoms of THF molecules (Na1) with a linear O5–
Na1–O5Ј moiety (180.0°) or two N atoms of the p-cyano-
phenoxy linker (N4–Na2–N4Ј 180.0°) and four square
planar arranged O atoms of THF molecules as observed
for Na2 (Figure 5, top). The boron atom is in a distorted
tetrahedral environment with an average O–B–O angle of
108.8°. Interestingly, only three of the p-cyanophenoxy link-
ers act as bridging ligands between both metal ions and the
fourth remains uncoordinated (N1 in Figure 5). Obviously,
no stable network can be composed with octahedral Na+
ions and a tetrahedral BO4 building block in the presence
of a donating solvent such as THF. Thus a 2D network
with three different parallel layers is formed as depicted in
Figure 5 (bottom). In addition to the six coordinated THF
molecules, two further uncoordinated THF molecules per
unit cell are found between these layers. The average B–O
distance is 1.466 Å, which is slightly longer than the sum
of the covalent radii (1.38 Å).[34] The C–N distance of the
Figure 4. Top: Ball-and-stick drawing of the local environment uncoordinated CN group is slightly shorter than those that
are attached to Na+ ions [1.137(3) vs. 1.143(3), 1.141(2),
and 1.148(2) Å].
about the tetrahedral centers in 4 (hydrogen atoms omitted for clar-
ity). Selected bond lengths [Å] and angles [°]: Al1–O2 1.735(2),
Al1–O4 1.735(2), Al1–O1 1.739(2), Al1–O3 1.722(2), Cu1–N1
1.975(2), Cu1–N2 2.018(2), Cu1–N3 1.992(2), Cu1–N4 1.996(2);
[Li(THF)3.6(Et2O)0.4][(THF)Al(O–C6F4–CN)4] (5)
N1–Cu1–N3 110.1(1), N1–Cu1–N4 118.07(9), N3–Cu1–N4
101.55(9), N1–Cu1–N2 105.10(9), N3–Cu1–N2 111.68(9), N4–
Cu1–N2 110.53(9), O3–Al1–O2 115.55(9), O3–Al1–O4 107.38(9),
O2–Al1–O4 108.39(9), O3–Al1–O1 105.25(9), O2–Al1–O1
108.42(9), O4–Al1–O1 111.90(9). Bottom: space filling model of a
section of 4, view along a axis, disordered solvent molecules
(CH2Cl2) inside the pores are omitted for clarity.
Crystals of 5 were obtained by a slow diffusion method.
Et2O was layered above a saturated THF solution of 5,
stored at –30 °C, and after one day crystals had formed
near the original solvent interface. Complex 5 crystallized
as colorless prisms in the monoclinic space group C2/c with
6
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Molecular Networks Based on CN Coordination Bonds
teractions since all CN groups remain uncoordinated. The
Li+ ion is tetrahedrally surrounded exclusively by either
THF or Et2O molecules. Hence, no network is formed. Ob-
viously, perfluorination at the phenyl rings results in a dra-
matic decrease of the basicity of the CN groups; therefore,
the Li+ ions favor coordination by solvent molecules. The
positions of four THF molecules in 5 were found to be dis-
ordered and were split in two parts. The occupancy of each
part was refined freely (for details see Supporting Infor-
mation). The position of the fifth THF molecule in 5 was
found to be partially displaced by Et2O and was split in two
parts. The occupancy of each part was refined freely (THF/
Et2O: 0.606(7)/0.394(7)).
Figure 6. Ball-and-stick drawing of the asymmetric unit in 5 (hy-
drogen atoms omitted for clarity, disorder not shown). Selected
bond lengths [Å] and angles [°]: Al1–O2 1.765(2), Al1–O1 1.766(2),
Al1–O3 1.771(2), Al1–O4 1.821(2), Al1–O5 1.966(2), N1–C7
1.138(3), N2–C14 1.136(3), N3–C21 1.135(3), N4–C28 1.137(3);
O2–Al1–O1 122.46(9), O2–Al1–O3 116.49(9), O1–Al1–O3
120.17(9), O2–Al1–O4 92.55(8), O1–Al1–O4 95.97(8), O3–Al1–O4
90.63(9), O2–Al1–O5 90.15(8), O1–Al1–O5 84.84(7), O3–Al1–O5
85.76(9), O4–Al1–O5 176.19(8), C1–O1–Al1 132.3(2), C8–O2–Al1
141.3(2), C15–O3–Al1 129.2(2), C22–O4–Al1 147.3(2).
Figure 5. Top: Ball-and-stick drawing of the local environment
about the tetrahedral centers in 2 (hydrogen atoms omitted for clar-
ity, only the O atoms of the coordinated THF molecules are
shown). Selected bond lengths [Å] and angles [°]: B–O1 1.463(2),
B–O4 1.467(2), B–O2 1.467(2), B–O3 1.468(2), N2–Na1 2.443(2),
N3–Na1 2.572(2), N4–Na2 2.541(2), Na1–O5 2.375(1), Na2–O6
2.419(5), N1–C7 1.137(3), N2–C14 1.143(3), N3–C21 1.141(2), N4–
C28 1.148(2), Na2–O7 2.44(1); O1–B–O4 114.7(1), O1–B–O2
113.9(2), O4–B–O2 100.5(1), O1–B–O3 101.0(1), O4–B–O3
113.6(2), O2–B–O3 113.7(1), O5Ј–Na1–O5 180.00(9), O5–Na1–N2
86.50(6), O5–Na1–N2Ј 93.50(6), O5–Na1–N2 93.50(6), O5–Na1–
N2 86.50(6), N2Ј–Na1–N2 180.0(1), O5–Na1–N3 93.86(5), O5–
Na1–N3 86.14(5), N2–Na1–N3 83.34(6), N2–Na1–N3 96.66(6),
O5–Na1–N3 86.14(5), N2–Na1–N3 96.66(6), N3–Na1–N3Ј
180.0(1), O6–Na2–O6Ј 180.0(1), O6–Na2–O7 92.7(4), O6–Na2–O7
87.3(4), O7–Na2–O7Ј 180.000(2). Bottom: view along c axis dis-
playing parallel layers (A, B, C) of the 2D network (hydrogen atoms
and all uncoordinated THF molecules omitted for clarity, only O
atoms of coordinating THF molecules are shown).
Probably the most interesting feature of the molecular
structure of 5 is the pentacoordination of the Al3+ in the
complex anion, which displays a distorted trigonal bipy-
ramidal arrangement of the O atoms around the Al3+ cen-
ter. The one coordinating THF molecule adopts an apical
position with an O4–Al1–O5 angle of 176.19(8)°. As ex-
pected the Al–Oax bond lengths [Al1–O4 1.821(2) and Al1–
O5 1.966(2) Å] are considerably elongated compared to the
Al–Oeq bond lengths [Al1–O2 1.765(2), Al1–O1 1.766(2),
and Al1–O3 1.771(2) Å]. In contrast to compounds 1–4, the
perfluorinated p-cyanophenoxy linker, –O–C6F4–CN, is
considerably less basic and thus allows pentacoordination
at the Al3+ center and prevents the cyano groups from coor-
dinating to the Li+ ion. Moreover, the perfluorinated p-
cyanophenoxy linker does not provide sufficient steric hin-
drance to prevent solvent coordination. The oxygen-penta-
eight crystallographically equivalent [Li(THF)3.6(Et2O)0.4]- coordinate aluminate is well known and can be found in
[(THF)Al(O–C6F4–CN)4] asymmetric units per unit cell. As aluminium containing alcoholates[40] or can be achieved by
illustrated in Figure 6, the asymmetric unit consists of the additional solvent coordination.[41] Furthermore, penta-
+
separated complex ion pair [Li(THF)3.6(Et2O)0.4
]
and coordination by nitrogen and oxygen containing ligands is
[(THF)Al(O–C6F4–CN)4]–, which display no significant in- known.[42]
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M. Karsch, H. Lund, A. Schulz, A. Villinger, K. Voss
FULL PAPER
Na(O–C6F4–CN)·3THF and Na(O–C6F4–CN)·nCH3CN
ions thus forming chains of planar Na2O2 rings connected
by two perfluorinated p-cyanophenoxy linkers. In 6b, the
oxygen of the perfluorinated p-cyanophenoxy coordinates
in a μ3 coordination mode to three adjacent Na+ ions re-
sulting in the formation of a distorted Na4O4 cube (Fig-
ure 8 bottom). These cubes are linked by the nitrogen and
oxygen atoms of the p-cyanophenoxy linker leading to the
formation of 3D network with channels and voids as illus-
trated in Figure 8 (top). Moreover, one CH3CN solvent mo-
lecules is attached to each Na+ center.
Crystals of Na(O–C6F4–CN) were obtained from THF
(6a) and CH3CN (6b) solutions. As the X-ray data sets for
both species were rather poor, the structural details cannot
be discussed in detail, but the data allowed us to establish
the connectivity as displayed in Figures 7 and 8. In 6a the
oxygen atom of the –O–C6F4–CN linker bridges two Na+
(THF)2Al{O–C6H4–CN·B(C6F5)3}3 (7)
¯
Compound 7 crystallizes in the triclinic space group P1
with two formula units per unit cell. There are no signifi-
cant interactions between adjacent (THF)2Al[O–C6H4–
CN·B(C6F5)3]3 molecules. As shown in Figure 9, species 7
can be considered as a solvent-stabilized Al[O–C6H4–
CN·B(C6F5)3]3 Lewis acid with a trigonal pyramidal coor-
dinated Al center with Oeq–Al–Oeq angles close to 120°
[O1–Al1–O3 118.85(9), O1–Al1–O2 121.53(9), O3–Al1–O2
119.58(9)°] and an almost linear Oax–Al–Oax unit [O5–Al1–
O4 177.70(8)°]. Both THF solvent molecules occupy axial
positions, and the B(C6F5)3 molecules are attached to the
N atom of the cyano group thus preventing the formation
of 2D or 3D networks. The average Al–Oeq bond length is
1.742 Å (cf. Al–Oax 1.976 Å).
Figure 7. Drawing of the chains in 6a (hydrogen atoms omitted for
clarity, disorder not shown).
Figure 9. Drawing of the molecular structure of 7 (hydrogen atoms
omitted for clarity). Selected bond lengths [Å] and angles [°]: Al1–
O1 1.722(2), Al1–O3 1.748(2), Al1–O2 1.755(2), Al1–O4 1.986(2),
Al1–O5 1.965(2), N1–C7 1.137(3), N2–C14 1.142(3), N3–C21
1.139(3), N1–B1 1.588(4), N2–B2 1.581(3), N3–B3 1.574(3); O1–
Al1–O3 118.85(9), O1–Al1–O2 121.53(9), O3–Al1–O2 119.58(9),
O1–Al1–O5 92.1(1), O3–Al1–O5 88.30(9), O2–Al1–O5 91.63(9),
O1–Al1–O4 88.5(1), O3–Al1–O4 89.47(8), O2–Al1–O4 89.94(8),
O5–Al1–O4 177.70(8), C7–N1–B1 176.7(2), C14–N2–B2 177.3(2),
C21–N3–B3 175.5(2).
[Na(Et2O)4][(C6F5)3B–NC–C6H4–O–B(C6F5)3] (8a),
[Na(Et2O)4][(C6F5)3B–NC–C6F4–O–B(C6F5)3] (8b),[43]
and Li[(NC–C6F4–O)Al{O–C6F4–CN·B(C6F5)3}3] (9)
Compounds 8a, 8b, and 9 crystallize as ion pairs. As the
X-ray data sets for 8b and 9 were rather poor, structural
details cannot be discussed in detail. The connectivity of all
Figure 8. Top: view along the a axis of the 3D network in 6b; bot-
tom: Na4O4 cube in 6b, each Na+ center is attached to one N atom
of the phenoxy linker and one of the CH3CN molecule.
8
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Molecular Networks Based on CN Coordination Bonds
three species is displayed in Figures 10 (anions of 8a and hedrally attached to either aluminium or boron, with
8b) and 11 (ion pair in 9). Whereas no significant monocationic metal centers (M) such as Li+, Na+, Ag+, and
cation···anion interactions are observed for 8, in 9 the Cu+. An interesting common feature of these supramolec-
[Li(Et2O)3]+ ion is strongly coordinated to one unblocked ular polymers is the presence of dative metal–nitrogen
cyano group of the [(NC–C6F4–O)Al{O–C6F4–CN· bonds as crucial structure-directing elements besides the
B(C6F5)3}3] anion. However, there are no interactions be- tetrahedral [E(O–C6H4–CN)4]– (E = Al, B) anion. Utilizing
tween the ion pairs of 9 worthy of discussion. For both the perfluorinated O–C6F4–CN linker leads to a decrease
species, the metal ions as well as the Al and B centers are in the stability of the [E(O–C6H4–CN)4]– anion with respect
tetrahedrally coordinated. (Figure 11).
to decomposition into E(O–C6H4–CN)3 and (O–C6H4–
CN)–, which is also observed when a Lewis acid such as
B(C6F5)3 is added. Moreover, addition of B(C6F5) leads to
the formation of molecular ion pairs because now the cyano
groups are either completely or partly blocked.
Experimental Section
General Information: All manipulations were carried out under
oxygen- and moisture-free conditions under argon using standard
Schlenk or drybox techniques.
Dichloromethane and acetonitrile were heated to reflux over CaH2;
tetrahydrofuran and Et2O were dried with Na/benzophenone and
freshly distilled prior to use. Lithium aluminium hydride (Alfa
Aeser) was purified by recrystallization from Et2O prior to use. 4-
Hydroxybenzonitrile (Merck) was sublimated in vacuo at 60 °C
prior use. AgNO3 (VEB Arzneimittelwerk, Dresden) was recrys-
tallized from water, powdered, and dried in vacuo for 10 h. NaBH4
1
(Merck) and KOH (VWR) were used as received. H, 11B and 13C
NMR spectra were obtained with Bruker Avance 250 (250 MHz)
and Avance 300 (300 MHz) spectrometers and were referenced ex-
ternally. CD2Cl2 and CDCl3 were dried with P4O10, [D6]DMSO
and CD3CN were dried with CaH2, and C6D6 was dried with so-
dium. FTIR spectra were obtained with a Nicolet 380 FTIR spec-
trometer with a Smart Orbit attenuated total reflectance (ATR)
device. Raman spectra were obtained with a Bruker Vertex 70
FTIR spectrometer with a RAM II FT-Raman module equipped
with a Nd:YAG laser (1064 nm) or Kaiser Optical Systems RXN1–
785 nm microprobe. CHN analyses were conducted with an Ana-
lysator Flash EA 1112 instrument from Thermo Quest or C/H/N/
S-Mikronalysator TruSpec-932 instrument from Leco. Differential
scanning calorimetry (DSC) measurements were obtained with a
Mettler-Toledo 823e instrument (heating rate 5 °C/min). Thermo-
gravimetric analysis (TGA) measurements were performed with a
Setaram LapSys 1600 TGA-DSC under an argon atmosphere
(heating rate 5 °C/min). Nitrogen sorption experiments were per-
formed at –192 °C with a Thermo Sorptomatic 1990 instrument.
Figure 10. Drawing of the molecular structures of the anion in 8a
(top) and 8b (bottom).
X-ray Structure Determination: X-ray quality crystals were selected
in Fomblin YR-1800 perfluoroether (Alfa Aesar) at ambient tem-
peratures. The samples were cooled to 173(2) K during measure-
ment. The data were collected with a Bruker Apex Kappa-II CCD
diffractometer using graphite monochromated Mo-Kα radiation (λ
= 0.71073 Å). The structures were solved by direct methods
(SHELXS-97) and refined by full-matrix least-squares procedures
(SHELXL-97). Semi-empirical absorption corrections were applied
(SADABS). All non-hydrogen atoms were refined anisotropically,
hydrogen atoms were included in the refinement at calculated posi-
tions using a riding model.
Figure 11. Drawing of the molecular structure of 9.
XRD: Powder XRD patterns were collected with a Stoe Stadi P
diffractometer using a position sensitive detector and germanium-
monochromatized Cu-Kα1 radiation (λ = 1.5406 Å) at ambient tem-
Conclusions
Crystalline coordination polymer networks were ob-
tained by connection of p-cyanophenoxy linker units, tetra- perature.
Eur. J. Inorg. Chem. 0000, 0–0
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Syntheses[44]
1
C 58.84, H 3.44, N 9.65. H NMR (CD3CN, 250 MHz, 25 °C): δ
= 7.50–7.41 (m, 8 H, CH–C–CN), 6.90–6.82 (m, 8 H, CH–C–O)
ppm. 13C NMR (CD3CN, 250 MHz, 25 °C): δ = 164.9 (s, 1 C, CO),
135.0 (s, 1 C, C–C–CN), 121.1 (s, 1 C, CN), 120.7 (s, 1 C, C–C–
O), 101.4 (s, 1 C, C–CN) ppm.
Li[Al(O–C6H4–CN)4] (1): 4-Hydroxybenzonitrile (2 g, 17 mmol,
4.25 equiv.) dissolved in THF (18 mL) was added slowly to a stirred
solution of activated LiAlH4 (0.152 g, 4 mmol, 1 equiv.) in THF
(24 mL) at 0 °C. The resulting solution was heated to reflux for two
hours. The solution was filtered, and the solvent was removed in
vacuo to yield a colorless solid. This crude product was washed
two times with Et2O (10 mL) to remove the excess 4-hydroxybenzo-
nitrile. The pure product was dried for three hours in vacuo at
70 °C; yield 1.32 g (65%). M.p. (DSC): (onset) 349.4 °C, (peak)
353.9 °C. C28H16AlLiN4O4 (506.37): calcd. C 66.41, H 3.18, N
11.06; found C 65.35, H 3.54, N 10.68. 1H NMR (CD3CN,
300 MHz, 25 °C): δ = 7.49–7.42 (m, 8 H, CH–C–CN), 6.90–8.84
(m, 8 H, CH–C–O) ppm. 13C NMR (CD3CN, 300 MHz, 25 °C): δ
= 164.9 (s, 1 C, CO), 135.0 (s, 1 C, C–C–CN), 121.1 (s, 1 C, CN),
120.8 (s, 1C, C–C–O), 101.4 (s, 1 C, C–CN) ppm.
Li[Al(O–C6F4–CN)4] (5): 4-Hydroxy-2,3,5,6-tetrafluorobenzonitrile
(5.52 g, 28.87 mmol, 4.2 equiv.) dissolved in THF (18 mL) was
added slowly to a stirred solution of activated LiAlH4 (0.26 g,
6.87 mmol, 1 equiv.) in THF (24 mL) at 0 °C. The resulting solu-
tion was heated to reflux for two hours. The solution was filtered,
and the solvent was removed in vacuo to yield the desired product
as a colorless solid. This crude product was washed two times with
CH2Cl2 (10 mL) to remove the excess 4-hydroxy-2,3,5,6-tetra-
fluorobenzonitrile. The pure product was dried for ten hours in
vacuo at 80 °C; yield 3.5 g (64.16%). M.p. (DSC): (onset) 271.2 °C,
(peak) 281.4 °C; dec. (onset) 361 °C. C28AlF16LiN4O4 (794.23):
calcd. C 42.34, N 7.05; found C 42.15, N 6.75. 13C NMR (CD3CN,
Na[B(O–C6H4–CN)4]
(2):
4-Hydroxybenzonitrile
(2.728 g,
1
300 MHz, 25 °C): δ = 149.1 (dm, JC,F = 251.7 Hz, 1 C, CF–CO),
23 mmol, 4.25 equiv.) dissolved in THF (18 mL) was rapidly added
to a stirred suspension of NaBH4 (0.205 g, 5.4 mmol, 1 equiv.) in
THF (24 mL) at 0 °C. The resulting suspension was heated to re-
flux for three hours. A colorless solid was obtained after filtration
and removal of the solvent in vacuo. This crude product was
washed two times with Et2O (10 mL) to remove the excess 4-hy-
droxybenzonitrile. The pure product was dried for six hours in
vacuo at 70 °C; yield 1.56 g (67%); decomp. (DSC): (onset)
362.1 °C. C28H16B N4NaO4 (506.26): calcd. C 66.43, H 3.19, N
11.07; found C 66.10, H 3.39, N 10.25. 1H NMR ([d6]DMSO,
300 MHz, 25 °C): δ = 7.55–7.45 (m, 8 H, CH–CCN), 7.12–7.04 (m,
8 H, CH–C–O) ppm. 13C NMR (CD3CN, 250 MHz, 25 °C): δ =
165.3 (s, 1 C, CO), 133.1 (s, 1 C, C–C–CN), 119.4.6 (s, 1 C, CN),
119.1 (s, 1 C, C-C-O), 100.6 (s, 1 C, C–CN) ppm. 11B NMR
(CD3CN, 300 MHz, 25 °C): δ = 2.55 (s) ppm.
1
145.2 (m, 1 C, CO), 141.2 (dm, JC,F = 242.2 Hz, 1 C, CF–CCN),
109.7 (t, JC,F = 3.6 Hz, 1 C, CN), 84.9 (m, 1 C, C–CN) ppm. 19F
3
1
NMR (CD3CN, 282.4 MHz, 25 °C): δ = –139.1 (d, JC,F
11.23 Hz, 8 F), –161.4 (d, JC,F = 14.83 Hz, 8 F) ppm.
=
1
Na(O–C6F4–CN) (6): To a stirred suspension of NaBH4 (0.257 g,
6.75 mmol, 1 equiv.) in THF (24 mL), cooled to 0 °C, 4-hydroxy-
2,3,5,6-tetrafluorobenzonitrile (5.435 g, 28.5 mmol, 4.2 equiv.) dis-
solved in freshly distilled THF (18 mL) was added. The resulting
suspension was heated to reflux for three hours. The suspension
was filtered, and the solvent was removed in vacuo to give a color-
less solid. The solid was washed two times with freshly distilled
Et2O (10 mL) to remove the excess 4-hydroxy-2,3,5,6-tetra-
fluorobenzonitrile; decomp. (DSC): (onset) 366.56 °C, (peak)
371.11 °C. C7F4NNaO (213.07): calcd. C 39.46, N 6.57; found C
39.40 N 6.20. 13C NMR ([D6]DMSO, 75.5 MHz, 25 °C): δ = 153.7
Ag[Al(O–C6H4–CN)4] (3): Lithium tetrakis-(4-cyanophenyl)alumi-
nate (4 mmol, 2.0255 g) and silver triflate (4.5 mmol, 1.1562 g) were
each dissolved in acetonitrile (40 mL). The silver salt solution was
added to the stirred aluminate solution through a dropping funnel
at ambient temperature. The turbid deep red solution was filtered,
and the volume of the solvent was reduced to ca. 40mL and filtered
again. The microcrystalline product was crystallized overnight in a
freezer at –30 °C from the clear red solution. The solvent was re-
moved by decantation and the product was dried in vacuo for 2 h.
After powdering and drying again for 2 h in high vacuum a light
red-gray powder was obtained; yield 1.038 g (42.71% with respect
to Al); decomp. (DSC): (onset) 243 °C. C28H16AlAgN4O4 (607.31):
1
2
3
(d, JC,F = 260.4 Hz, 2 C, C–CO), 146.9 (tt, JC,F = 13.9, JC,F
=
1
4.5 Hz, 1 C, CO), 140.3 (d, JC,F = 247.6 Hz, 2 C, C–CN), 112.7
(t, 3JC,F = 3.77 Hz, 1 C, CN), 63.4 (t, 2JC,F = 18.1 Hz, 1 C, C–CN).
19F NMR ([D6]DMSO, 282.4 MHz, 25 °C, ppm): δ = –144.8 (m, 2
F), –167.7 (m, 2 F) ppm.
(THF)Al[O–C6H4–CN·B(C6F5)3]3 (7): To a stirred solution of
B(C6F5)3 (2.56 g, 5 mmol, 5 equiv.) in THF (50 mL), solid Li[Al-
(O–C6H4–CN)] (0.505 g, 1 mmol, 1 equiv.) was added in one por-
tion and the resulting solution was stirred overnight. Removal of
the solvent yielded a colorless solid, which was washed two times
with n-hexane (50 mL). The residual n-hexane was removed in
vacuo, and the solid was dissolved in Et2O (20 mL). The resulting
solution was filtered and concentrated to 6 mL. Storage over 48 h
at 7 °C resulted in the precipitation of (THF)2Al[O–C6H4–
CN·B(C6F5)3]3; yield 0.6 g (31%). For analytical experiments the
solid was dried in vacuo for six hours at 70 °C and (THF)Al{O–
C6H4–CN·B(C6F5)3}3 was obtained; decomp. (DSC): (onset)
136.8 °C. C79H20AlB3F45N3O4 (1989.37): calcd. C 47.70, H 1.01,
N, 2.11; found C 47.43, H 1.33, N 1.71. 1H NMR (CDCl3,
300 MHz, 25 °C): δ = 7.54–7.48 (m, 6 H, CH–C–CN), 6.77–6.71
(m, 6 H, CH–CO) ppm. 13C NMR (CDCl3, 300 MHz, 25 °C): δ =
166.4 (s, 3 C, CO), 147.2 (m, 6 C, CF–CB), 139.7 (m, 3 C, CF–
CF–CF–CB), 136.3 (m, 6 C, CF–CF–CB), 136.0 (s, 6 C, CH–C–
CN), 120.4 (s, 6 C, CH–CO), 115.6 (s, 3 C, CN), 114.9 (br., 3 C,
1
calcd. C 55.38, H 2.66, N 9.23; found C 54.57, H 2.49, N 8.84. H
NMR (CD3CN, 300 MHz, 25 °C): δ = 7.50–7.42 (m, 8 H, CH–C–
CN), δ = 6.89–6.81 (m, 8 H, CH–C–O) ppm. 13C NMR (CD3CN,
300 MHz, 25 °C): δ = 164.6 (s, 1 C, CO), 135.0 (s, 1 C, C–C–CN),
120.7 (s, 1 C, CN), 119.7 (s, 1 C, C–C–O), 101.6 (s, 1 C, C–CN)
ppm.
Cu[Al(O–C6H4–CN)4](4):
A solution of Ag[Al(O–C6H4–CN)4]
(607.3 mg, 1 mmol) in acetonitrile (40 mL) was added to a stirred
yellow colored solution of CuI (190.4 mg, 1 mmol) in acetonitrile
(15 mL) at ambient temperature. A white precipitate was formed,
and the solution turned slightly green. The reaction mixture was
allowed to stir for ten minutes, and the precipitate was allowed to
settle out. The solution was filtered and the residue was washed
with acetonitrile (15mL). The solution was filtered again, and the
solvent was removed under reduced pressure. The white solid was
dried for twelve hours at ambient temperature to yield the desired
product (316.6 mg, 51% yield). Dec (DSC): (Onset) 281 °C.
C28H16AlCuN4O4 (562.89): calcd. C 59.74, H 2.86, N 9.95; found
C–B), 92.2 (s, 3 C, C–CN) ppm. 19F NMR (CDCl3, 282 MHz,
3
25 °C): δ = –135.1 to –135.2 (m, 6 F, CF–CB), –157.9 (t, JF,F
=
20.3 Hz, 3 F, CF–CF–CF–CB), –164.7 to –164.8 (m, 6 F, CF–CF–
CB) ppm. 11B NMR (CDCl3, 96 MHz, 25 °C): δ = –11.7 (s, 3 B)
ppm.
10
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Molecular Networks Based on CN Coordination Bonds
Na[(F5C6)3B·O–C6H4–CN·B(C6F5)3] (8a): A Schlenk flask was
loaded with B(C6F5)3 (2.56 g, 5 mmol, 5 equiv.) and Na[B-
(O–C6H4–CN)] (0.505 g, 1 mmol, 1 equiv.). To this mixture Et2O
(50 mL) was added to obtain a suspension. The suspension was
stirred overnight and a colorless solution was obtained. After re-
moval of the solvent in vacuo a solid was obtained, which was
washed three times with n-hexane (20 mL). The residual n-hexane
was removed in vacuo, and the solid was dissolved in Et2O (15 mL).
The resulting solution was filtered and concentrated to 5 mL. Col-
orless crystals of [Na(Et2O)4][(F5C6)3B·O–C6H4–CN·B(C6F5)3]
suitable for X-ray crystallographic analysis were grown by storage
at –30 °C overnight. The crystallized product was dried in vacuo
for six hours at 70 °C to give the solvent-free product Na[(F5C6)3-
B·O–C6H4–CN·B(C6F5)3] for analytical experiments; yield 0.25 g
(21%). M.p. (DSC): (onset) 154.7 °C, (peak) 164.4 °C; dec. (onset)
303.9 °C. C51H28B2F30NNaO5 (1349.3): calcd. C 45.40, H 2.09, N
[1]
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1
1.04; found C 45.22, H 1.46, N 1.04. H NMR (CDCl3, 300 MHz,
25 °C, ppm): δ = 7.71–7.47 (m, CH–C–CN, 2 H), 6.96–7.78 (m, 2
H, CH–CO). 13C NMR (CDCl3, 300 MHz, 25 °C, ppm): δ = 163.5
(s, 1C, C–O), 148.0 (m, 12C, CF–CB), 139.5 (m, CF–CF–CF–CB,
6C), 137.4 (m, 12C, CF–CF–CB), 136.6 (s, 2C, CH–C–CN), 117.8
(s, 2C, CH–CO), 115.0 (br., 6C, C–B), 114.7 (s, 1C, CN), 96.3 (s,
[3]
[4]
[5]
1C, C–CN). 19F NMR (CDCl3, 300 MHz, 25 °C): δ = –134.4 to
3
–134.5 (m, 12 F, CF–CB), –156.2 (t, 6 F, CF–CF–CF–CB, JF,F
=
19.3 Hz), –163.2 to –163.4 (m, 12 F, CF–CF–CB). 11B NMR
(CDCl3, 300 MHz, 25 °C): δ = –11.7 (s, 1B, B·NC), –2.9 (s, 1B,
B·O).
Li[NC–C6F4–O–Al{O–C6F4–CN·B(C6F5)3}3] (9): A Schlenk flask
was loaded with B(C6F5)3 (1.03 g, 2 mmol, 4 equiv.) and Li[Al(O–
C6F4–CN)] (0.4 g, 0.5 mmol, 1 equiv.). To this mixture Et2O
(25 mL) was added to obtain a suspension. The suspension was
stirred overnight and a colorless solution was obtained. The solu-
tion was filtered and the volume of the solvent reduced to 10 mL.
Storage at –40 °C overnight gave colorless crystals of [(Et2O)3Li]-
[(NC–C6F4–O)Al{O–C6F4–CN–B(C6F5)3}3] suitable for X-ray
crystallographic analysis. The crystallized product was dried in
vacuo for six hours at 70 °C to give the solvent-free product
Li[(NC–C6F4–O)Al{O–C6F4–CN–B(C6F5)3}3] for analytical ex-
periments; yield 0.86 g (74%); decomp. (DSC): (onset) 318.7 °C.
C82AlB3F61LiN4O4 (2330.17): calcd. C 42.27, N 2.40; found C
41.92, N 1.81. 13C NMR (CDCl3, 300 MHz, 25 °C, ppm): δ =
151.23 (m, 1C, CF–C–CN), 149.83 (m, CO), 148.24 (dm, CF–C–
B), 145.93 (dm, CF–CF–CF–CB), 142.87 (m, CF–CO), 137.53 (dm,
CF–CF–CB), 107.92 (m, CN). 19F NMR (CDCl3, 300 MHz. 25 °C,
ppm): δ = –130.93 (s), –133.78 (s), –155.82 (s), –156.46 (s), –163.19
(s). 11B NMR (CDCl3, 300 MHz, 25 °C): δ = 2.5 to –41.5 (br).
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CCDC-901962 (for 1), -901963 (for 5), -901964 (for 3), -901965
(for 4), -901966 (for 7), -901967 (for 2) contain the supplementary
crystallographic data for this paper. These data can be obtained
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[12]
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Acknowledgments
Financial support by the Deutsche Forschungsgemeinschaft
(DFG) is gratefully acknowledged. We are indebted to Martin
Ruhmann (University of Rostock) and Johannes Thomas (Univer-
sity of Rostock) for the measurement of Raman spectra.
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Date: 24-09-12 16:34:27
Pages: 13
M. Karsch, H. Lund, A. Schulz, A. Villinger, K. Voss
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Received: April 29, 2012
Published Online: ᭿
12
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 0000, 0–0

Job/Unit: I20427
/KAP1
Date: 24-09-12 16:34:27
Pages: 13
Molecular Networks Based on CN Coordination Bonds
Coordination Polymer Networks
Tetrahedral [E(O–C6X4–CN)4]– anions (E
= B, Al; X = H, F) were synthesized and
used as anionic linkers for the generation
of 2D and 3D crystalline coordination
polymer networks.
M. Karsch, H. Lund, A. Schulz,*
A. Villinger, K. Voss ....................... 1–13
Molecular Networks Based on CN Coordi-
nation Bonds
Keywords: Coordination polymers / Alumi-
nates / Borates / Silver / Copper / Bridging
ligands
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