∞1[M(μ-O2C-C6H 4-CO2)(NH3)2] (M = Cu, Cd; O 2C-C6H4-CO2 = benzene-1,4- dicarboxylate, terephthalate): ID coordination polymers with strong inter-chain hydrogen bonding

Article abstract of DOI:10.1002/zaac.200400240

Compounds _∞¹[M(μ-O₂C-C ₆H₄-CO₂)(NH₃)₂] crystallize as straight- (M = Cu) and kinked-chain (M = Cd) coordination polymers through the bridging action of the bis-mono (Cu) and bisbidentate (Cd) benzene-1,4-dicarboxylate (terephthalate) ligand. N-H...O hydrogen bonding connects the chains to a three-dimensional supramolecular network. Thermogravimetry shows the compounds to be stable up to 255°C (M = Cu) and 70°C (M = Cd) where decomposition starts with the loss of one ammin ligand. _∞¹[(Cd(μ-O₂C-C₆H ₄-CO₂)(NH₃)₂] exhibits a luminescence with λ_em,max = 392 nm (λ_ex = 240 nm) on the same order of magnitude as Na₂(O₂C-C ₆H₄-CO₂).

Full text of DOI:10.1002/zaac.200400240

1
[
M(µ-O C-C H -CO )(NH ) ] (M ؍ Cu, Cd; O C-C H -CO ؍
ؕ
2
6
4
2
3 2
2
6
4
2
benzene-1,4-dicarboxylate, terephthalate): 1D Coordination Polymers with
Strong Inter-Chain Hydrogen Bonding
a
b
c
a,*
Barbara Paul , Boris Zimmermann , Katharina M. Fromm and Christoph Janiak
Freiburg, a Institut für Anorganische und Analytische Chemie und b Institut für Physikalische Chemie der Universität
c
Basel/Schweiz, Department of Chemistry, University of Basel
Received June 17th, 2004.
Abstract. Compounds 1
[M(µ-O
C-C
H
4
-CO
)(NH
)
2
] crystallize as
decomposition starts with the loss of one ammin ligand. 1
C-C -CO )(NH ] exhibits a luminescence with λem,max
392 nm (λex ϭ 240 nm) on the same order of magnitude as
Na (O C-C -CO ).
ϱ
2
6
2
3
ϱ
[Cd(µ-
straight- (M ϭ Cu) and kinked-chain (M ϭ Cd) coordination poly-
mers through the bridging action of the bis-mono (Cu) and bis-
bidentate (Cd) benzene-1,4-dicarboxylate (terephthalate) ligand. N-
H···O hydrogen bonding connects the chains to a three-dimensional
supramolecular network. Thermogravimetry shows the compounds
to be stable up to 255 °C (M ϭ Cu) and 70 °C (M ϭ Cd) where
O
2
6
H
4
2
3
)
2
ϭ
2
2
6
H
4
2
Keywords: Coordination polymers; Terephthalate; Benzene-1,4-di-
carboxylate; Thermogravimetry; Luminescence
1
[
M(µ-O C-C H -CO )(NH ) ] (M ؍ Cu, Cd; O C-C H -CO ؍ Benzol-1,4-
ؕ
2
6
4
2
3 2
2
6
4
2
dicarboxylat, Terephthalat): 1D-Koordinationspolymere mit starken H-Brücken
zwischen den Ketten
Inhaltsübersicht. Die Verbindungen 1
[M(µ-O
C-C
H
4
-CO
)(NH
)
2
]
Verbindungen bis zu einer Temperatur von 255 °C (M ϭ Cu) oder
ϱ
2
6
2
3
kristallisieren als Koordinationspolymere mit geraden (M ϭ Cu)
oder gewinkelten Ketten (M ϭ Cd) durch die Verbrückung des
bis-ein- (Cu) oder bis-zweizähnigen (Cd) Benzol-1,4-dicarboxylat-
70 °C (M ϭ Cd) wo Zersetzung mit dem Verlust eines Ammin-
1
Liganden
CO )(NH
nm) und einer Intensität in der gleichen Größenordnung wie
Na (O C-C -CO ).
beginnt.
Die
Verbindung
ϱ
[Cd(µ-O
2
C-C
6
H
4
-
2
3 2
) ] zeigt Lumineszenz mit λem,max ϭ 392 nm (λex ϭ 240
(Terephthalat-)Liganden. NϪH···O-Wasserstoffbrücken verknüp-
fen die Ketten zu einem dreidimensionalen supramolekularen Netz-
werk. Thermogravimetrische Messungen zeigen die Stabilität der
2
2
6
H
4
2
1
II
Introduction
In [Cu(µ-bdc)(NH ) ] (1, Fig. 1) the Cu ion is coordi-
3 2
ϱ
nated square-planar in a trans configuration by two ammin
and two bis-monodentate terephthalato ligands. The Jahn-
Teller distortion manifests itself towards additional long
contacts to the second oxygen atom of each pseudo-chelat-
ing carboxyl group. The trans-arranged terephthalato li-
gands bridge between the metal ions to a straight-chain
polymer. Other 1D Cu-terephthalate structures have biden-
tate chelating nitrogen ligands so that the benzene-1,4-di-
Metal-organic networks or coordination polymers recently
attract much attention because of topology design and po-
tential properties in adsorption, catalysis, luminescence,
magnetism etc. [1Ϫ3]. In particular aromatic dicarboxylate
ligands, with terephthalate (benzene-1,4-dicarboxylate, bdc)
being one of the simplest member of this series, feature
prominently as bridging ligands in the construction of
highly porous and robust metal-organic (carboxylate)
frameworks [4, 5]. We describe here the structures and ther-
mal stabilities of two one-dimensional (1D) metal-tereph-
thalate coordination polymers with strong N-H···O in-
terchain bonding leading to three-dimensional supramole-
cular networks.
*
Prof. Dr. Chr. Janiak
Institut für Anorganische und Analytische Chemie
Universität Freiburg
Fig. 1 Straight-chain structure of 1
[Cu(µ-bdc)(NH ) ] in 1.
ϱ 3 2
Albertstr. 21
D-79104 Freiburg
E-Mail: janiak@uni-freiburg.de
˚
Selected distances/A and angles/°: Cu-O1 1.961(2), Cu-N 1.989(2), Cu-O2
2
2.738(2), O1-Cu-N 87.99(9), O1-C-N 92.01(9), symmetry operation:
ϭ Ϫxϩ1, Ϫyϩ1, Ϫz; ϭ Ϫxϩ2, Ϫyϩ2, Ϫzϩ1.
2
2Ј
1650
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
DOI: 10.1002/zaac.200400240
Z. Anorg. Allg. Chem. 2004, 630, 1650Ϫ1654

1D Coordination Polymers with Strong Inter-Chain Hydrogen Bonding
Fig. 2 Hydrogen bonding between the 1
{[Cu(µ-bdc)(NH ) ]-chains in 1 (a) along b, that is within the bc plane, and (b) along a and b; see
ϱ 3 2
Table 1 for details; symmetry operations 1 ϭ x, yϪ1, z; ϭ xϪ1, y, z; ϭ x, yϩ1, z; ϭ Ϫx, Ϫyϩ1, Ϫz.
1Ј
1Љ
2Љ
Table 1 Hydrogen-bonding interactions in 1.
D-H···A a)
D-H /A
˚
H···A /A
˚
D···A /A
˚
D-H···A /°
N-H1A···O21 0.90(3)
2.08(3)
2.42(3)
2.38(3)
2.966(3)
3.191(3)
3.066(3)
170(3)
171(3)
151(3)
2Љ
N-H1B···O2
0.78(3)
N-H1C···O11 0.76(3)
Ј
a)
Symmetry operations: 1 ϭ x, yϪ1, z; 1Ј ϭ xϪ1, y, z; 2Љ ϭ Ϫx, Ϫyϩ1, Ϫz.
carboxylate (bdc) bridges are forced into a cis-position to
each other, thereby resulting in zig-zag chain (cf. compound
2) [6, 7, 8].
The chains in 1 are interconnected through N-H···O
Fig. 3 TGA curve of 1
[Cu(µ-bdc)(NH ) ] (1).
ϱ 3 2
hydrogen bonds from the ammin to the terephthalato li-
gands to yield an overall three-dimensional network based
on a 1D coordination polymer and extended by supramole-
cular hydrogen bonding (Fig. 2). Related hydrogen-bonded
networks are formed between the Cu-ligand chains in
1
{
[Cu(µ-bdc)(1,10-phen)(H O)]·(H O)(dmf)} [6] and in
ϱ
2 2
1
{[Cu(µ-btecH )(H O) ]·(H O) } (btec ϭ benzene-1,2,4,5-
ϱ
2
2
3
2
3
tetracarboxylate) [9] and the Cu-ligand nets in
2
{
[Cu(µ-bdc)(µ-H O)(H O)] [10]. The latter three structures
ϱ
2 2
feature square-pyramidal coordinated metal ions.
A thermogravimetric analysis (TGA) of 1 (Fig. 3) shows
the first weight loss at 255 °C (6.5 %) corresponding to the
removal of one ammonia molecule per formula unit (6.5 %
calc.). The second weight loss at 280 °C (6.5 %) matches the
removal of the second ammin ligand (6.5 % theor.). The
third mass loss at 375 °C (41.0 %) is due to the decompo-
sition of the terephthalato ligand into carbon dioxide
Fig. 4 Zig-zag-chain structure of 1
[Cd(µ-bdc)(NH ) ] in 2.
ϱ 3 2
˚
11
10
Selected distances/A and angles/°: Cd-O 2.385(2), Cd -N 2.251(3), N-Cd-N
1
1
11
9
9.6(2), N-Cd-O 91.37(9), N-Cd-O 136.25(6), O-Cd-O 54.4(1), O-Cd-O
4 2
8
5.05(11), O-Cd-O 109.4(1), symmetry operations ϭ Ϫx, Ϫy, zϩ1/2;
4 10 11
3
ϭ x, Ϫy, Ϫz; ϭ Ϫx, y, Ϫzϩ1/2; ϭ x, y, Ϫzϩ1/2; ϭ Ϫx, y, z.
(30.6 % theor.), carbon monoxide, hydrocarbons and car-
bonous material [11]. The residue appears to consist of the
metal and a noticeable amount of carbonous material.
The zig-zag chains in 2 are interconnected through
NϪH···O hydrogen bonds between the ammin and the
terephthalato ligands to again yield an overall 3D network
based on the 1D coordination polymer which is extended
by supramolecular hydrogen bonding (Fig. 5).
1
In [Cd(µ-bdc)(NH ) ] (2) the Cd(II) ion is trigonal-pris-
ϱ
3 2
matic coordinated in a cis-configuration by two ammin and
two bis-bidentate terephthalato ligands (Fig. 4).
Z. Anorg. Allg. Chem. 2004, 630, 1650Ϫ1654
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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1651

B. Paul, B. Zimmermann, K. Fromm, C. Janiak
Fig. 5 Hydrogen bonding between the 1
[Cd(µ-bdc)(NH
)
]-chains in 2 (a) along a and (b) along b; see Table 1 for details, symmetry
ϱ
3
2
operations: 1 ϭ x, yϩ1, z; 5 ϭ xϩ1/2, yϩ1/2, z; 8 ϭ Ϫxϩ1/2, yϩ1/2, Ϫzϩ1/2; ϭ x, y, Ϫzϩ1/2;
10
10’
ϭ x, yϩ1, Ϫzϩ1/2; ϭ Ϫxϩ1/2,
15
yϩ1/2, z.
Table 2 Hydrogen-bonding interactions in 2.
D-H···A a)
N-H1···O8
D-H /A
˚
H···A /A
˚
D···A /A
˚
D-H···A /°
0.88(3)
0.70(5)
0.70(5)
2.32(3)
2.65(4)
2.65(4)
3.107(4)
3.235(4)
3.235(4)
148(3)
142(9)
142(9)
N-H2···O1
N-H2···O1
0Ј
a)
Symmetry operations: 1 ϭ x, yϩ1, z; 8 ϭ Ϫxϩ1/2, yϩ1/2, Ϫzϩ1/2; 10Ј
ϭ
x, y, Ϫzϩ1/2.
With respect to the zig-zag chain structure in 2 similar
1
chains are found in {[Cd(µ-bdc)(H O) ]·(H O) } albeit
ϱ
2
3
2
4
with a more complicated hydrogen-bonding network [12]
3
or in {[Ph PCH Ph][Cd(µ-bdc)Cl]·(H O) } as part of a
3
Fig. 6 TGA curve of 1
ϱ
3
2
2
2
ϱ
3 2
[Cd(µ-bdc)(NH ) ] (2).
D framework with the bridging chloro ligands [13].
Other terephthalato-bridged cadmium coordination
polymers
contain
tetrakis-monodentate
(in
3
1
[
Cd(µ -bdc) Cl(1,10-phen)] [14]) or bis-tridentate tereph-
Compound [Cd(µ-bdc)(NH ) ] (2) but not the Cu analog
3 2
ϱ
4
1/2
ϱ
3
thalato ligands (in [Cd(µ -bdc)(pyridine)] [15]) bridging
1 exhibits luminescence in the same wavelength region and
on at least the same order of magnitude if not stronger than
free terephthalic acid or its disodium salt. The absorption
spectrum of 2 in diffuse reflectance mode shows two max-
ima at 237 and 288 nm (Fig. 7a). The luminescence spec-
trum of 2 exhibits an emission maximum at 392 nm and a
shoulder at 420 nm upon excitation at 240 nm (Fig. 7b),
essentially unshifted from the maximum for free tereph-
thalic acid (λem,max ϭ 389 nm) or its disodium salt (λem,-
ϱ
4
between four cadmium ions as part of a 3D framework.
Noteworthy, the last two structures have been obtained
through hydrothermal reactions from 1,4-dicyanobenzene
by its slow hydrolysis into terephthalic acid [14, 15].
A thermogravimetric analysis of 2 (Fig. 6) shows the first
weight loss at 70 °C (6.5 %) corresponding to the removal
of one ammonia molecule per formula unit (5.5 % calc.).
The second weight loss at 240 °C (6 %) matches the removal
of the second ammin ligand (5.5 % theor.). The third mass
loss at 440 °C (34.0 %) is due to the decomposition of the
terephthalato ligand (CO theor. 25.8 %) [11]. The residue
appears to consist of the metal and a noticeable amount of
carbonous material.
Coordination polymers are studied for luminescence
properties owing to their often higher thermal stability than
the pure organic ligand and the ability of affecting the emis-
sion wavelength of the ligand by metal coordination [1].
ϭ 385 nm). Because of the unchanged emission wave-
max
length the luminescence is assigned to intraligand tran-
sitions. The concomitant excitation spectrum (Fig. 7c, col-
lected at the emission wavelength of 420 nm) reveals a
mirror-image like absorption at 342 nm with a shoulder at
330 nm. The luminescence intensity of 2 seems somewhat
stronger than in disodium terephthalate and even more so
2
3
than in the free acid. Still in the complex [Cd(µ -bdc)(pyri-
dine)] [15] the emission intensity was enhanced about 100
ϱ
4
1652
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1650Ϫ1654

1D Coordination Polymers with Strong Inter-Chain Hydrogen Bonding
for the NMR study means disintegration into the metal and ligand
building blocks. Thermogravimetric analyses were carried out on a
simultaneous thermoanalysis apparatus STA 409 from Netzsch un-
Ϫ1
der nitrogen (heating rate 5 K min ). The diffuse reflectance spec-
trum was measured on a Perkin-Elmer Lambda 900 spectrophoto-
meter with an integrating sphere against a white standard. Emis-
sion spectra were measured on a Perkin-Elmer LS-50B (λex
2
ϭ
40 nm, split widths (em, ex) 5.0 nm, scan speed 2 nm sϪ1, sample
in quartz capillary) or together with the excitation spectrum on an
Ϫ1
SLM-Aminco 8100 (split widths 16 nm, scan speed 0.5 nm s ). All
optical spectra were collected with powders at room temperature.
General Procedure for the Preparation of 1
A solution of M(NO ·(H O)
n
(3.24 mmol, M ϭ Cu2 , n ϭ 3;
Cd , n ϭ 4) in MeOH (5 ml) was combined with a solution of
ammonia (26 %, 15 ml). The solvent was then allowed to evaporate
slowly at room temperature. After several days crystals formed
which were suitable for X-ray single crystal analysis.
ϱ
3 2
[M(µ-bdc)(NH ) ]:
ϩ
3
)
2
2
Fig. 7 Optical spectra of 1
flectance absorption spectrum, (b) emission spectrum with λex
40 nm (the sharp peak at 480 nm is the second harmonic tran-
sition), (c) excitation spectrum collected at λem ϭ 420 nm.
2ϩ
ϱ
3 2
[Cd(µ-bdc)(NH ) ] (2): (a) Diffusion re-
ϭ
2
2
1
4
catena-polydiammin(µ-benzene-1,4-dicarboxylato-κ O :O )copper(II)],
times over that of the free terephthalate ligand, probably
due to a symmetry decrease by serious ligand twisting.
1
ؕ
2 6 4 2 3 2
[Cu(µ-O C-C H -CO )(NH ) ] (1). Blue-violet isometric crystals,
yield 14.0 mg, 53 %. Calc. for C H CuN O (261.73): C 36.71, H
8
10
2
4
3.85, N 10.70. Found C 36.58, H 3.91, N 10.68 %.
IR (cm؊1): 3343m, 3320m, 3265m, 3239m, 3158m, 1946w, 1641m, 1622m,
Experimental
1
569s, 1500m, 1400m, 1380s, 1355s, 1317m, 1300m, 1234m, 1144m, 1103w,
012m, 880w, 837m, 742m, 711m, 584m, 494m.
1
Elemental analyses were obtained on a VarioEL from Elementar-
analysensysteme GmbH. IR spectra (2-4 mg compound/300 mg
KBr pellet) were measured on a Bruker Optik IFS25. NMR spectra
1
6
H-NMR: (DMSO-d /HCl): δ 7.94 (s).
4
1
1Ј
4
4Ј
catena-polydiammin(µ-benzene-1,4-dicarboxylato-κ O ,O :O ,O )-
1
1
were collected on a Bruker ARX200 (200 MHz for H) with cali-
cadmium(II)],
ؕ
[Cd(µ-O
2
C-C
6
H
4
-CO
2
)(NH
3
)
2
] (2). Colorless plates,
bration against the residual protonated solvent signal (DMSO
yield 23.0 mg, 74 %. Calc. for C
8
H10CdN
2
O
4
(310.59): C 30.94, H
2.52 ppm). Dissolution of the coordination polymeric compounds
3.25, N 9.02. Found: C 30.80, H 3.34, N 8.80 %.
Table 3 Crystal data and structure refinement for compounds 1 and 2.
1
1
Compound
ϱ
[Cu(µ-O
2
C-C
6
H
4
-CO
2
)(NH
3
)
2
] (1)
ϱ
[Cd(µ-O
2
C-C
6
H
4
-CO
2
)(NH
3
)
2
] (2)
Empirical formula
C
261.73
8
H
10CuN
2
O
4
C
310.59
8
H
10CdN
2 4
O
Ϫ1
M /(g mol
)
Crystal size /mm
θ Range /°
0.12 ϫ 0.07 ϫ 0.04
2.11 Ϫ 28.46
0.15 ϫ 0.12 ϫ 0.03
2.53 Ϫ 28.82
Ϫ14, 14; Ϫ7, 7; Ϫ20, 20
orthorhombic
Cmcm
10.931(7)
5.565(3)
h; k; l range
Ϫ5, 5; Ϫ7, 8; Ϫ13, 13
triclinic
Crystal system
Space group
¯
P1
˚
a /A
4.090(3)
6.037(4)
9.822(7)
93.57(1)
99.19(1)
100.16(1)
234.6(3)
1
˚
b /A
˚
c /A
16.112(10)
Ͱ /°
β /°
γ /°
˚
3
V /A
980(1)
4
2.105
Z
D
calc /(g cmϪ3
)
1.852
F (000)
µ /mm
133
2.322
608
2.223
Ϫ1
Max/min transmission
Reflections collected
Unique reflections (Rint
0.9129/0.7680
1975
1070 (0.0160)
997
0.9363/0.7315
4210
674 (0.0372)
597
)
Observed reflections [I > 2σ(I)]
Parameters refined
79
46
Max./min. ∆ρ (e AϪ3)
a)
˚
0.478/Ϫ0.547
0.0277/0.0670
0.0297/0.0679
1.018
0.853/Ϫ0.802
0.0245/0.0555
0.0288/0.0568
1.055
b)
R1/wR2 [I > 2σ(I)]
b)
R1/wR2 (all data) 2
c)
Goodness-of-fit on F
d)
Weighting scheme w; a/b
0.0409/0.0000
0.0328/0.0000
a)
b)
2ϪF
2)2]/Σ[w(F
2)2]]1/2 Ϫ c) Goodness-of-fit ϭ [Σ[w(F
2ϪF
2)2]/(nϪp)]1/2
Largest difference peak and hole. Ϫ R1 ϭ [Σ(ʈF
o
ΗϪΗF
c
ʈ)/ΣΗF
c
o
Η]; wR
2
ϭ [Σ [w(F
o
c
0
o
c
Ϫ
d)
2
2
2
2
2
w ϭ 1/[σ (F
o
)ϩ(aP) ϩbP] where P ϭ (max(F
o
or 0)ϩ2F )/3
Z. Anorg. Allg. Chem. 2004, 630, 1650Ϫ1654
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1653

B. Paul, B. Zimmermann, K. Fromm, C. Janiak
IR (cm 1): 3342m, 3260m, 3245m, 1567s, 1503m, 1397s, 1377m, 1299m,
؊
[
[
4] M. Eddaoudi, J. Kim, D. Vodak, A. Sudik, J. Wachter, M.
1
213m, 1110m, 1011m, 887m, 839m, 745m, 573m, 522m.
H-NMR: (DMSO-d /HCl): δ 7.96 (s).
6
O’Keeffe, O. M. Yaghi, Proc. Nat. Acad. Sci. USA (PNAS)
1
2
002, 99, 4900. M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T.
M. Reineke, M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001,
4, 319.
3
Structure determinations
5] Examples of recent work: L.-Y. Zhang, G.-F. Liu, S.-L. Zheng,
B.-H. Ye, X.-M. Zhang, X.-M. Chen, Eur. J. Inorg. Chem.
Data Collection: Bruker AXS with CCD area-detector, tem-
perature 233(2) K, Mo-KͰ radiation (λ ϭ 0.71073 A),
2003, 2965. W. Chen, Q. Yue, C. Chen, H.-M. Yuan, W. Xu,
˚
J.-S. Chen, S.-N. Wang, Dalton Trans. 2003, 28. N. L. Rosi, J.
Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O’Keeffe, O.
M. Yaghi, Science 2003, 300, 1127. C. Serre, F. Millange, C.
Thouvenot, M. Nogu e` s, G. Marsolier, D. Lou e¨ r, G. F e´ rey, J.
Am. Chem. Soc. 2002, 124, 13159. M. Eddaoudi, J. Kim, N.
Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O. M. Yaghi, Science
graphite monochromator, double-pass method φϪω-scan,
Data collection and cell refinement with SMART [16], data
reduction with SAINT [16], experimental absorption cor-
rection with SADABS [17]. Structure Analysis and Refine-
ment: The structure was solved by direct methods
2
002, 295, 469.
{[Cu(µ-bdc)(1,10-phen)(H
(
SHELXS-97) [18]; refinement was done by full-matrix least
1
[
6] 1
ϱ
2
O)]·(H
2
O)(dmf)} and
ϱ
[Cu(µ-
2
squares on F using the SHELXL-97 program suite [18].
All non-hydrogen positions were found and refined with an-
isotropic temperature factors. Hydrogen atoms on the aro-
matic ring were placed at calculated positions with an ap-
propriate riding model (AFIX 43) and an isotropic tem-
2
bdc)(1,10-phen)(H O)]: L.-G. Zhu, H.-P. Xiao, J. Y. Lu, Inorg.
Chem. Commun. 2004, 7, 94.
7] 1
[
ϱ
{[Cu(µ-bdc)(di-2-pyridyl-κN-amine]·(H
2
O)}: L. Karanovi c´ ,
D. Poleti, J. Rogan, G. A. Bogdanovi c´ , A. Spasojevi c´ -de Bir e´ ,
Acta Crystallogr. C 2002, 58, m275.
[8] 1
[Cu(µ-bdc)(1,10-phen)]: D. Sun, R. Cao, Y. Liang, Q. Shi, W.
perature factor of Ueq ϭ 1.2 U (C). The hydrogen atoms
ϱ
eq
Su, M. Hong, Dalton Trans. 2001, 2335.
9] R. Diniz, H. A. de Abreu, W. B. de Almeida, M. T. C. Sansivi-
ero, N. G. Fernandes, Eur. J. Inorg. Chem. 2002, 1115.
10] L. Deakin, A. M. Arif, J. S. Miller, Inorg. Chem. 1999, 35,
of the ammin ligand were found and refined with Ueq
.5 U (N).
ϭ
[
1
eq
Graphics were obtained with DIAMOND [19]. Displace-
ment ellipsoids are drawn at the 70 % (1) and 50 % (2) prob-
ability level and H atoms are shown as spheres of arbitrary
radii. Crystal data and details on the structure refinement
are given in Table 3. The structural data have been de-
posited with the Cambridge Crystallographic Data Center
[
5072.
[
[
11] R. J. Acheson, A. K. Galwey, J. Chem. Soc. (A) 1967, 1174.
12] O. A. Michaelides, D. Tsaousis, S. Skoulika, C. P. Raptopou-
lou and A. Terzis, Acta Crystallogr. 1998, B54, 657.
[13] J.-C. Dai, X.-T. Wu, Z.-Y. Fu, S.-M. Hu, W.-X. Du, C.-P. Cui,
(No. 244887 for 1, CCDC-244886 for 2).
L.-M. Wu, H.-H. Zhang, R.-Q. Sun, Chem. Commun. 2002,
12.
[
[
[
14] D. Sun, R. Cao, Y. Liang, Q. Shi, W. Su, M. Hong, Dalton
Trans. 2001, 2335.
15] H.-K. Fun, S. S. S. Raj, R.-G. Xiong, J.-L. Zuo, Z. Yu, X.-Z.
You, Dalton Trans. 1999, 1915.
16] SMART, Data Collection Program for the CCD Area-Detec-
tor System; SAINT, Data Reduction and Frame Integration
Program for the CCD Area-Detector System. Bruker Analyti-
cal X-ray Systems, Madison, Wisconsin, USA, 1997.
17] G. Sheldrick, Program SADABS: Area-detector absorption
correction, University of Göttingen, Germany, 1996.
Acknowledgements. The work was supported by the Univer-
sity of Freiburg. We thank Mrs. Claudia Leiggener and Prof.
Dr. Gion Calzaferri (University of Bern) for the recording
of the diffuse reflectance spectrum and Prof. Dr. Claude
Piguet (University of Geneva) for helpful discussions.
References
[
[
[
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