Crystal structure solid-state cross polarization magic angle spinning 13C NMR correlation in luminescent d10 metal-organic frameworks constructed with the 1,2-bis(1,2,4-triazol-4-yl)ethane ligand

Article abstract of DOI:10.1021/ic802069k

Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(ll), zinc(ll), and cadmium(ll) salts have yielded the dinuclear complexes [Zn₂CI₄(μ₂-btre)₂] (1) and [Zn₂Br₄(μ

Full text of DOI:10.1021/ic802069k

Inorg. Chem. 2009, 48, 2166-2180
Crystal Structure Solid-State Cross Polarization Magic Angle Spinning
10
13
C NMR Correlation in Luminescent d Metal-Organic Frameworks
Constructed with the 1,2-Bis(1,2,4-triazol-4-yl)ethane Ligand
†
Hesham A. Habib, Anke Hoffmann,* Henning A. H o¨ ppe, Gunther Steinfeld,
and Christoph Janiak*
,‡
†
†
,†
Institut f u¨ r Anorganische und Analytische Chemie, UniVersit a¨ t Freiburg, Albertstr. 21,
D-79104 Freiburg, Germany, and Institut f u¨ r Makromolekulare Chemie, UniVersit a¨ t Freiburg,
Stefan-Meier-Str. 31, D-79104 Freiburg, Germany
Received October 29, 2008
Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(II), zinc(II), and cadmium(II) salts have
yielded the dinuclear complexes [Zn
2
Cl
-btre)] (3), the two-dimensional networks
(µ -SO (µ -btre) (H O) ](SO O} (6), and the three-dimensional frameworks
)·∼6H
O} (7), {[Zn(µ -btre)(µ -btre)](ClO } (8),
-btre)] (10, 2-fold 3D interpenetrated framework). The copper-containing products 4, 5, 7, and 10 contain
4
(µ
2
-btre)
2
] (1) and [Zn
2
Br
2
∞
4
(µ
2
-btre)
2
] (2), the one-dimensional coordination
1
2
polymer
∞
[Zn(NCS)
2
(µ
-OH)
·∼0.25H
2
[Cu (µ -Cl)
2
2
2 4
(µ -btre)] (4),
∞
[Cu
2
(µ
2
-Br)
2
(µ
4
-btre)]
2
∞
3
(
5), and
btre)]ClO
CN) (µ
{[Cd
(µ
6 3
2
3
)
4 4
4
3
2
6
4
2
∞
{[Cu(µ -
4
3
∞
3
∞
3
4
2
4
2
)
4 2
{[Cd(µ
4
-btre)(µ
2 4 2
-btre)](ClO ) } (9), and
∞
2 2
[Cu (µ -
2
4
the metal in the +1 oxidation state, from a simultaneous redox and self-assembly reaction of the Cu(II) starting
materials. The cyanide-containing framework 10 has captured the CN ions from the oxidative btre decomposition.
-
4+
6-
6-
The perchlorate frameworks 7, 8, or 9 react in an aqueous NH PF solution with formation of the related PF
-
containing frameworks. The differences in the metal-btre bridging mode (µ -κN1:N1′, µ -κN1:N2 or µ -κN1:N2:
2
2
4
13
N1′:N2′) and the btre ligand symmetry can be correlated with different signal patterns in the C cross polarization
magic angle spinning (CPMAS) NMR spectra. Compounds 2, 4, 5 and 7 to 10 exhibit fluorescence at 403-481
nm upon excitation at 270-373 nm which is not seen in the free btre ligand.
Introduction
Scheme 1. Common 1,2,4-Triazole Derivatives for the Construction of
a
Metal Coordination Networks
Coordination polymers, metal coordination networks, or
metal-organic frameworks (MOFs) are of contemporary
interest because of their structural topologies and potential
applications in the areas of catalysis, adsorption, lumines-
1
-4
cence, nonlinear optics, magnetism, and ion exchange.
Coordination compounds containing derivatives of 1,2,4-
triazole have been of increasing interest during the past
1
decade. The 1,2,4-triazole ligand and its 4-substituted
derivatives (Scheme 1) can be used to obtain a wide variety
5
of polynuclear molecules and linear coordination polymers
2
+
6
based on its bridging function, for example, with Cu ,
a
The gray underlined ligand btre is synthetically used in this work.
2+
7
2+
8
Zn , and Cd . The N1:N2-bridging mode of 1,2,4-triazole
or triazolate constitutes a short ligand bridge between metal
atoms which is a prerequisite for stronger magnetic coupling
between paramagnetic metal centers. Surprisingly, with the
*
To whom correspondence should be addressed. E-mail: anke.hoffmann@
1
makro.uni-freiburg.de (A.H.), janiak@uni-freiburg.de (C.J.). Fax: +49 761
2
4
036306 (A.H.), 49 761 2036147 (C.J.). Phone: +49 761 203631 (A.H.),
related 4,4′-bis(1,2,4-triazol-4-yl) ligand (abbreviated as btr,
Scheme 1) this N1:N2 bridging coordination mode has only
9 761 2036127 (C.J.).
†
Institut f u¨ r Anorganische und Analytische Chemie.
Institut f u¨ r Makromolekulare Chemie.
‡
9
been observed recently with Cu(II). Typically the btr ligand
2166 Inorganic Chemistry, Vol. 48, No. 5, 2009
10.1021/ic802069k CCC: $40.75  2009 American Chemical Society
Published on Web 01/29/2009

Luminescent d10 Metal-Organic Frameworks
links transition metal(II) ions using only one nitrogen atom
N2 bridge. At the same time, the btre ligand has been scarcely
10,11
18
from each 1,2,4-triazole ring resulting in one-,
three-dimensional (1D, 2D, 3D) networks.
two-, and
When spac-
used in metal-complex or MOF synthesis. A CSD search gave
12-14
2
19
∞
{M(NCS)
2
(µ
2
-btre-κN1:N1′)
2
(NCS)
2
} (M ) Fe, Co) and
(µ -btre-κN1:N2:
2
O} as the only examples. We
3
ers, like methylene groups, are introduced between the two
,2,4-triazole rings, the resulting ligand acquires more flexibility.
Therefore, we selected 1,2-bis(1,2,4-triazol-4-yl)ethane (ab-
∞
{[Cu
(H
3
(µ
O)
4
-btre-κN1:N2:N1′:N2′)
2
3
20
1
N1′)
4
2
2
]
2
(ClO
4
)12 ·2H
have recently added mixed-ligand 1D to 3D coordination
networks of btre with benzene-1,3,5-tricarboxylate or
15
21
breviated as btre). This btre ligand must not be mistaken with
1
6
the more widely employed 1,2-bis(1,2,4-triazol-1-yl)ethane
benzene-1,4- and -1,3-dicarboxylate and Ni(II), Cu(II), Zn(II)
or Cd(II) as metal atoms which feature solid-state crystal-
17
and other ∼alkane ligands (Scheme 1). These related 1,2-
bis(1,2,4-triazol-1-yl) ligands do only bridge between two metal
atoms in a κN4:N4′ mode. Hence, they cannot bring two metal
atoms closely together as the btre ligand can through its κN1:
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Inorganic Chemistry, Vol. 48, No. 5, 2009 2167

Habib et al.
a
Scheme 2. Schematic Metal-Ligand Connectivity in 1-10
a
The metal-btre bonds are depicted as bold lines.
to-crystal transitions upon drying (Ni, Zn), luminescence (Zn,
Cd), or ferro- (Cu) and antiferromagnetic (Ni) coupling. The
hitherto most often observed btre coordination mode is µ -
4
Results and Discussion
Syntheses. Hydrothermal treatment of copper(II) chloride
or bromide, zinc(II) chloride or bromide, zinc(II) sulfate in
btre-κN1:N2:N1′:N2′ where the bis-triazole-type ligand bridges
the presence of NH
,2-bis(1,2,4-triazol-4-yl)ethane (btre) yields the dinuclear
complexes [Zn Cl (µ -btre) ] (1) and [Zn Br (µ -btre) ] (2),
the 1D coordination polymer (µ -btre)] (3) and
-btre)] (4),
-OH) (µ -SO
4
SCN, and cadmium(II) sulfate with
2
between four metal atoms occupying all of its sp -hybridized
1
2
2
nitrogen atoms (cf. Scheme 2).
2
4
2
2
2
4
2
2
In this work, we report the syntheses, structures, structure-
Cross Polarization Magic Angle Spinning (CPMAS)-NMR
correlations and luminescence of metal-btre complexes,
1
∞
[Zn(NCS)
2
2
2
2
the 2D networks
Br) (µ -btre)] (5), and
O) ](SO
)· ∼6H
D metal-btre frameworks metal salts with less coordinating
∞
[Cu
2
(µ
2
-Cl)
2
(µ
3
4
∞
[Cu
(µ -btre)
2
(µ
2
-
2
2
4
∞
{[Cd (µ
6
2
3
4
)
4
4
3
-
1
0
coordination polymers, and networks with the d metal
(H
2
6
4
2
O} (6) (Scheme 2). For the synthesis of
+
2+
2+
atoms Cu , Zn , and Cd .
3
anions, that is, the perchlorates of copper(II), zinc(II), or
(
13) [Mn(µ-N
M.; Su, G.; Gao, S. Chem. Mater. 2005, 17, 6369.
14) [Fe(NCS) ]: Vreugdenhil, W.; van Diemen, J. H.; de
3 2 2
-κN1,N3) (btr-kN1) ]: Wang, X.-Y.; Wang, L.; Wang, Z.-
cadmium(II) were reacted under hydrothermal conditions
3
(
2
(µ-btr-κN1,N1′)
2
with btre to yield
∞
{[Cu(µ
4
-btre)]ClO
4
· ∼0.25H
{[Cd(µ -btre)(µ
-CN) (µ -btre)] (10)
and btre to contain
2
O} (7),
Graaff, R. A. G.; Haasnoot, J. G.; Reedijk, J.; van der Kraan, A. M.;
Kahn, O.; Zarembowitch, J. Polyhedron 1990, 9, 2971.
3
3
∞
{[Zn(µ
btre)](ClO
is special as it originated from CuSO
4
-btre)(µ
2
-btre)](ClO
4
)
2
} (8), and
∞
4
2
-
3
(
(
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)
4 2
} (9). The product
[Cu (µ
∞ 2 2
2
4
4
5
2
13. (b) Zhu, X.; Li, B.; Zhou, J.; Li, B.; Zhang, Y. Acta Crystallogr.
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below, Scheme 2).
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CrystEngComm 2007, 9, 199–292. (c) Chen, Z.-F.; Zhang, S.-F.; Luo,
H.-S.; Abrahams, B. F.; Liang, H. CrystEngComm 2007, 9, 27–29.
(d) Pichon, A.; Fierro, C. M.; Nieuwenhuyzen, M.; James, S.
CrystEngComm 2007, 9, 449–451. (e) Pas a´ n, J.; Sanchiz, J.; Lloret,
F.; Julve, M.; Ruiz-P e´ rez, C. CrystEngComm 2007, 9, 478–487. (f)
Carballo, R.; Covelo, B.; V a´ zquez-L o´ pez, E. M.; Garc ´ı a-Mart ´ı nez,
E.; Casti n˜ eiras, A.; Janiak, C. Z. Anorg. Allg. Chem. 2005, 631, 2006–
2010.
(
(
(
18) Cambridge Structure Database search, CSD Version 5.28 (November
2
006) with 2 updates (Januar 2007, May 2007).
19) Garcia, Y.; Bravic, G.; Gieck, C.; Chasseau, D.; Tremel, W.; G u¨ tlich,
P. Inorg. Chem. 2005, 44, 9723.
20) Garcia, Y.; van Koningsbruggen, P. J.; Kooijman, H.; Spek, A. L.;
Haasnoot, J. G.; Kahn, O. Eur. J. Inorg. Chem. 2000, 307.
(22) Habib, H. A.; Sanchiz, J.; Janiak, C. Dalton Trans. 2008, 1734–1744.
2168 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
Hydrothermal synthesis has been widely employed to
construct assemblies of metal complexes in recent years.
Noteworthy, all of the above copper-containing products 4,
anion in the structures. The products 7′, 8′, and 9′ are still
in a crystalline state and isostructural for 7′ and 8′ to their
starting materials as evidenced by their very similar X-ray
powder diffractograms, although the crystal transparency was
lost (Figures S4-S6, Supporting Information). However,
during the ion-exchange reaction, the crystals do not retain
their shape but disappear and reform (see sequence of
5
, 7, and 10 contain the metal in the +1 oxidation state,
from a simultaneous redox and self-assembly reaction of the
2
+
Cu(II) starting materials. It is known that Cu ions can be
+
reduced to Cu by N-, O-, and S-containing ligands, such
as 4,4′-bipyridine, pyridine-4-thiol, quinoxaline, and py-
photographs in Figure S7, Supporting Information). Thus,
2
3-25
ridinedicarboxylate under hydrothermal conditions.
-
the ClO
4
-containing 3D-frameworks 7-9 do not undergo
Also, under hydro(solvo)thermal conditions, the simultaneous
an ion-exchange in a (topotactic) solid-state crystal-to-crystal
2+
redox and self-assembly reaction of Cu with organonitro-
gen species was observed where the organonitrogen species
behave not only as ligands but also as reducing agents toward
Cu(II). This reduction then results in a decomposition of part
transformation but recrystallize to the apparently less soluble
-
PF
6
-containing frameworks.
Thermal Stability. All of the isolated compounds are
stable up to 270-300 °C without decomposition, except 6.
Compounds 1, 2, 4, and 5 show a rather steady weight loss
starting at ∼300 °C and continuing to over 600 °C because
of the removal of the btre ligands (see Figures S8-S11,
Supporting Information). A continuous weight loss for 3 from
275 to 600 °C is assigned to the removal of the organic ligand
(obs. 45.4, calcd 47.5%, see Figure S12, Supporting Infor-
mation) with 54.4% of the original mass retained as
2
6-28
3
of the organonitrogen species.
CN) (µ
The product
∞
[Cu
2 2
(µ -
2
4
-btre)] (10) captures the cyanide ions from such a
btre decompositon under hydrothermal conditions in the
presence of Cu(II).
The vibrational modes for the triazole rings in the
fingerprint region confirm the presence of btre ligand in the
compounds 1-10. A strong band at 2069 cm- in the IR
spectrum of 3 indicates the metal-isothiocyanate, M-NCS
coordination. The perchlorate anion was observed as a strong
band in the spectra of 7, 8, and 9 at 1071, 1076, and 1073
1
Zn(NCS) (calcd 52.5%). Compound 6 shows the first weight
2
loss in the temperature range 70-130 °C which corresponds
to the removal of the crystal water molecules (obs. 4.2, calcd
-1
cm (cf. Figures S1-S3, Supporting Information,), respec-
2
9,30
tively.
1
Sulfate bands in the IR spectrum of 6 occur at
5
.7% for six or 3.9% for four remaining crystal water in the
-1
-1
270 cm (terminal S-O) and at 1112, 1062, and 960 cm
air-dried sample). From 150 to 280 °C a second weight loss
of 6.1% occurs which is assigned to the six coordinated aqua
ligands (calcd 5.7). A continuing weight loss from 290 to
over 600 °C includes the loss of the btre ligands (Figure
S13, Supporting Information). Noteworthy, in 10 only about
half of the btre ligand is lost from 320-560 °C (obs. 24.0,
calcd 47.8% btre fraction in 10, Figure S14, Supporting
Information). At 650 °C the remaining mass of 73.3% for
(
4
coordinated S-O) which agree with the tridentate SO -
3
1,32
coordination to three Cd atoms.
showed a strong peak at 2094 cm which is assigned to the
bridging cyanide groups.
vibration bands are observed in the range of 632-405 cm .
To check the possibility of ion exchange, freshly prepared
crystals of the perchlorate containing 3D-frameworks 7, 8,
The IR spectrum of 10
-
1
33,34
The M-N, M-Cl, and M-Br
-1
4 6
or 9 were immersed in an aqueous solution of NH PF (3
mol/L) for 24 h, then filtered off, washed thoroughly with
water, and air-dried to give crystalline materials 7′, 8′, or
1
0 probably still includes some of the btre ligand. The
perchlorate compounds 7, 8, and 9 explode at 310 °C under
the thermogravimetric conditions.
9
′, respectively. The infrared spectra of 7′-9′ show the
-
Crystal Structures. The representative nature of the single
crystals investigated by X-ray diffactometry was in all cases
verified by positively matching the measured X-ray powder
diffractogram of a larger crystal selection with the diffrac-
togram simulated from the data of the single-crystal X-ray
refinement (see Figures S15-S23, Supporting Information).
disappearance or absence of the intense ClO
4
peaks
-1
(1071-1076 cm , see above) and the appearance of equally
-
-1
intense PF
6
peaks (822-823 and 554-556 cm ) (Figures
31,32 19
31
S1-S3, Supporting Information).
Also, the P and
) show signals
in the range -143 to -145 ppm for P and in the range of
F
NMR of 7′, 8′, and 9′ (dissolved in DMSO-d
6
3
1
19
-
-
71 to -75 ppm for F indicating the presence of the PF
6
2 4 2 2
[Zn Cl (µ -btre) ] 1 and [Zn
2 4 2 2
Br (µ -btre) ] 2. The iso-
morphous zinc compounds 1 and 2 feature a dinuclear
complex molecule in which two cis-bent btre ligands bridge
between two zinc atoms. Only one nitrogen atom on each
(
(
23) Yaghi, O. M.; Li, H. J. Am. Chem. Soc. 1995, 117, 10401.
24) Wu, C. D.; Lu, C. Z.; Zhuang, H. H.; Huang, J. S. Inorg. Chem. 2002,
1, 5636.
25) Lu, J. Y.; Babb, A. M. Inorg. Chem. 2002, 41, 1339.
26) Cheng, J. K.; Yao, Y. G.; Zhang, J.; Li, Z. J.; Cai, Z. W.; Zhang,
X. Y.; Chen, Z. N.; Chen, Y. B.; Kang, Y.; Qin, Y. Y.; Wen, Y. H.
J. Am. Chem. Soc. 2004, 126, 7796.
27) Kang, Y.; Yao, Y. G.; Qin, Y. Y.; Zhang, J.; Chen, Y. B.; Li, Z. J.;
Wen, Y. H.; Cheng, J. K.; Hu, R. F. Chem. Commun. 2004, 1046.
28) Wen, Y. H.; Cheng, J. K.; Zhang, J.; Li, Z. J.; Kang, Y.; Yao, Y. G.
Inorg. Chem. Commun. 2004, 7, 1120.
4
(
(
triazole ring is used for metal coordination in a µ
2
-btre-κN1:
N1′ mode, different from the µ -btre-κN1:N2:N1′:N2′ mode
4
(
in the complexes 4-10 (see below). The tetrahedral coor-
dination sphere of each Zn atom is concluded by two halide
ligands (Figure 1). The intermolecular packing in 1 and 2 is
(
(
(
(
29) Yaghi, O. M.; Li, H.; Groy, T. L. Inorg. Chem. 1997, 36, 4292.
30) Min, K. S.; Suh, M. P. J. Am. Chem. Soc. 2000, 122, 6834–6840.
31) Clegg, W.; Errington, R. J.; Hockless, D. C. R.; Glen, A. D.; Richards,
D. G. J. Chem. Soc., Chem. Commun. 1990, 1565.
(33) Xia, J.; Shi, W.; Chen, X.-Y.; Wang, H.-S.; Cheng, P.; Liao, D.-Z.;
Yan, S.-P. Dalton Trans. 2007, 2373–2375.
(34) Zhang, W.-H.; Song, Y.-L.; Zhang, Y.; Lang, J.-P. Cryst. Growth Des.
2008, 8, 253.
(
32) Du, M.; Guo, Y.-M.; Chen, S.-T.; Bu, X.-H. Inorg. Chem. 2004, 43,
1
287.
Inorganic Chemistry, Vol. 48, No. 5, 2009 2169

Habib et al.
Table 1. Ranges of Bonds Lengths (Å) and Angles (deg) in 1-10
1
(X ) Cl)
2 (X ) Br)
Zn-N
2.007-2.015
2.214-2.241
103.76(5)
108.14-113.48
113.38(2)
2.005-2.012
2.352-2.371
104.26(11)
107.77-113.04
112.36(2)
Zn-X
N-Zn-N
N-Zn-X
X-Zn-X
3
Zn-N
N-C (NCS)
C-S
N-Zn-N
Zn-N-C(S)
1.922-2.005
1.164-1.166
1.614-1.615
101.0-113.7
167.7-170.6
4
(X ) Cl)
5 (X ) Br)
Figure 1. Dinuclear molecular structure in 1 and 2 (Br instead of Cl in 2).
Selected distances and angles in Table S4, Supporting Information, ranges
in Table 1. Symmetry code in 1 and 2: 7 ) 0.5 - x, 1.5 - y, 1 - z.
Cu-N
Cu-X
2.007-2.038
2.343-2.439
3.027-3.616(1)
112.4(1)
105.6-120.9
101.48(4)
2.009-2.024
2.4616-2.5620
3.176-3.611(4)
112.25(7)
103.61-114.62
101.59(1)
Cu· · ·Cu
N-Cu-N
N-Cu-X
X-Cu-X
Cu-X-Cu
78.52(4)
78.41(1)
6
Cd-O
2.257-2.354
Cd-N
2.299-2.347
169.1-177.0
85.1-97.8
N-Cd-N
N-Cd-O
O-Cd-O
cis: 75.7-122.8
Figure 2. Coordination environment of the zinc atom in 3. Selected
distances and angles in Table S5, Supporting Information, ranges in Table
7
1
. Symmetry codes: 3 ) 0.5 + x, 0.5 + y, z; 3′ ) -0.5 + x, -0.5 + y, z.
Cu-N
N-Cu-N
1.996-2.075
94.95-117.52
3
5,36
35,37
organized by C-H· · ·N
and C-H · · ·X (X ) Cl,
3
8
8 (M ) Zn)
9 (M ) Cd)
Br ) hydrogen bonds (Table S1, Supporting Information).
1
M-N
2.159-2.210
86.4-93.2
2.327-2.353
87.9-91.8
∞
[Zn(NCS)
2
2
(µ -btre)] 3. The tetrahedral zinc atom in 3
cis N-M-N
is coordinated by two nitrogen atoms from two cis-bent
bridging btre ligands and two nitrogen atoms from two
terminal isothiocyanato groups (Figure 2). As in 1 and 2 only
one nitrogen atom on each triazole ring is used for metal
coordination in a µ -btre-κN1:N1′ mode. Each btre ligand
bridges between two zinc atoms. The resulting corrugated
trans N-M-N
179.0-179.8
178.2-178.7
1
0
Cu-C
Cu-N
1.906(3)
1.998-2.084
1.145(4)
101.0-106.4
110.3-119.6
173.6(3)
2
C-N (cyanide)
N-Cu-N
N-Cu-C
strands are interconnected through C-H · · ·N hydrogen
bonds (Figure 3, Table S1, Supporting Information).
Cu-C-N(CN)
Cu-N-C(CN)
3
5,36
165.7(2)
2
-btre)] 4 and 2
∞
2 2
[Cu (µ -Cl)
(µ
2 4
∞
[Cu
2
(µ
2
-Br)
2 4
(µ -btre)]
Cu atoms are bridged by two halogen anions or two triazolyl
rings. Thus, two halogen and two nitrogen atoms coordinate
the copper(I) atom in a tetrahedral fashion. Each trans-bent
btre ligand connects four copper atoms in κN1:N2:N1′:N2′
mode and each halide ligand bridges between two Cu atoms
to give 2D nets (Figure 4 and 5).
5
. The isomorphous copper(I) compounds 4 and 5 feature a
dinuclear metal unit in which inversion symmetry related
(
35) (a) Desiraju, G. R.; Steiner, T. The weak hydrogen bond. In IUCr
Monograph on Crystallography; Oxford Science: Oxford, 1999; Vol.
9
. (b) Desiraju, G. R. Acc. Chem. Res. 2002, 35, 565. (c) Mascal, M.
Chem. Commun. 1998, 303.
Neighboring layers are connected through C-H· · ·X (X
(
(
36) Janiak, C.; Scharmann, T. G. Polyhedron 2003, 22, 1123.
37) (a) Wisser, B.; Janiak, C. Z. Anorg. Allg. Chem. 2007, 633, 1796–
3
5,37
35,38
) Cl,
Br
) hydrogen bonds (Figure 6, Table S2,
1
800. (b) Fun, H. K.; Chantrapromma, S.; Lu, Z. L.; Neverov, A. A.;
39
Supporting Information,) and strong π-π interactions
between the triazolyl rings (Figure 6, Table S3, Supporting
Information).
Brown, R. S. Acta Crystallogr. 2006, E62, m3225-m3227. (c) Gunay,
M. E.; Aygun, M.; Kartal, A.; Cetinkaya, B.; Kendi, E. Cryst. Res.
Technol. 2006, 41, 615–621. (d) Wang, X. F.; Deng, S. L.; Long,
L. S.; Huang, R. B.; Zheng, L. S. J. Incl. Phenom. Macrocycl. Chem.
2
2
006, 54, 295–298. (e) Ban, S. R.; Yang, X.; Chen, W. B.; Cheng,
{[Cd
3
(µ -OH)
(µ
-SO
)
4
(µ
-btre)
3
(H
O)
](SO
)·∼6H
2
O} 6.
∞
6
2
3
4
4
2
6
4
X. F.; Song, H. B. Acta Crystallogr. 2006, E62, o1713-o1714. (f)
Lorono-Gonzalez, D. Acta Crystallogr. 2006, E62, o1735-o1737. (g)
Balamurugan, V.; Mukheriee, R. Inorg. Chim. Acta 2006, 359, 1376–
The cadmium compound 6 features a trinuclear and triangular
metal unit with three crystallographically different cadmium
sites (Figure 7). Each Cd atom has an octahedral environment
of four oxygen atoms and two trans nitrogen atoms. The three
Cd atoms are bridged by a µ -hydroxo and a µ -sulfato group
below and above the Cd -plane (cf. Scheme 2). Along the
edges of the Cd triangle three crystallographically different
1
382. (h) Xu, H.; Song, Y.-L.; Mi, L.-W.; Hou, H-W.; Tang, M.-S.;
Sang, Y.-L.; Fan, Y.-T.; Pan, Y. Dalton Trans. 2006, 838–845. (i)
Ravikumar, K.; Sridhar, B.; Mahesh, M.; Reddy, V. V. N. Acta
Crystallogr. 2006, E62, o318-o320.
40
3
3
(
38) (a) Zhang, W.; Tang, X.; Ma, H.; Sun, W.-H.; Janiak, C. Eur. J. Inorg.
Chem. 2008, 2830–2836. (b) Neve, F.; Crispini, A. Cryst. Growth
Des. 2001, 1, 287–393.
41
3
3
2170 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
Figure 6. Packing diagram of 4 and 5 (Br instead of Cl in 5) showing two
neighboring layers (the one in the rear is depicted semi-transparent)
connected through C-H· · ·X (X ) Cl, Br) hydrogen bonds as dashed lines
and π-π interactions between triazolyl rings. Note the almost perfect face-
to-face stacking of the symmetry related parallel triazolyl rings in the middle
of the picture (for details see Tables S2 and S3, Supporting Information).
2 2
Figure 3. Packing diagram for 3 showing four [Zn(NCS) (µ -btre)] strands
with C-H· · ·N bonding as dashed lines. The C5-H· · ·N2 bonding connects
two adjacent strands (the two middle ones) along their full length (see Table
S1, Supporting Information, for details).
Figure 4. Coordination environment of the copper atom in 4 and 5 (Br
instead of Cl in 5). Selected distances and angles in Table S6, Supporting
Information, ranges in Table 1. Symmetry codes in 4 and 5: 1 ) x, -1 +
y, z; 1′ ) x, -1 + y, z; 1′′ ) -1 + x, y, -1 + z; 2 ) -x, -y, 1 - z; 2′
)
1 - x, -y, 1 - z; 2′′ ) 1 - x, 1 - y, 2 - z.
Figure 7. Trinuclear cadmium unit in 6; hydrogen atoms not shown for
clarity. Selected distances and angles in Table S7, Supporting Information,
ranges in Table 1. Symmetry codes: 1 ) x, -1 + y, z; 2 ) 1 - x, y, 0.5
-
z; 4 ) 0.5 - x, 0.5 + y, 0.5 - z; 4′ ) 0.5 - x, -0.5 + y, 0.5 - z.
(Figure 7). The structure contains two symmetrically different
btre ligands, one of them with symmetry related triazolyl halves.
Each btre ligand is cis-bent and connects four cadmium atoms
in κN1:N2:N1′:N2′ mode (cf. Figure 8b).
The trinuclear and triangular Cd
sulfato groups into 1D strands (Figure 8a). The 2D network in
arises solely through the bridging action of the btre ligands
between the Cd units (Figure 8b). In between adjacent layers
lie water molecules of crystallization and, for charge balance,
a half-occupied and disordered, non-coordinated sulfate anion
(near an inversion center, Figure 9).
3
units are bridged by µ
3
-
6
3
Figure 5. 2D network in 4 and 5 (Br instead of Cl in 5).
triazolyl rings bridge between adjacent Cd atoms in κN1:N2
mode. The coordination sphere of Cd1 is concluded by two
3
oxygen atoms from two other symmetry-related µ
groups which connect three different Cd units (cf. Figure 8a).
The environment of Cd2 is concluded by an oxygen atom of
one of these µ -sulfato groups and an aqua ligand. The
coordination sphere Cd3 is concluded by two aqua ligands
3
-sulfato
∞
{[Cu(µ
4
-btre)]ClO
4
· ∼0.25H
2
O} 7. The copper(I) atom
3
in 7 is tetrahedrally coordinated by four nitrogen atoms from
(
40) (a) Banerjee, S.; Ghosh, A.; Wu, B.; Lassahn, P.-G.; Janiak, C.
Polyhedron 2005, 24, 593–599. (b) Banerjee, S.; Lassahn, P.-G.;
Janiak, C.; Ghosh, A. Polyhedron 2005, 24, 2963–2971.
41) Deng, H.; Qiu, Y.-C.; Li, Y.-H.; Liu, Z.-H.; Zeng, R.-H.; Zeller, M.;
Batten, S. R. Chem. Commun. 2008, 2239–2241.
3
(
(
39) Janiak, C. J. Chem. Soc., Dalton Trans. 2000, 3885.
Inorganic Chemistry, Vol. 48, No. 5, 2009 2171

Habib et al.
Figure 10. Coordination environment of the copper atom in 7. Selected
distances and angles in Table S8, Supporting Information, ranges in Table
1
-
. Symmetry codes: 3 ) 0.5 + x, 0.5 + y, z; 2 ) -x, y, 0.5 - z; 5 ) -x,
y, -z; 6 ) x, -y, 0.5 + z; 7 ) 0.5 - x, 0.5 - y, -z.
Figure 11. 3D framework in 7. Disordered perchlorate ions and crystal
water in channels are not shown for clarity (filled network in Figure S24,
Supporting Information).
Figure 8. Packing analysis for 6 by differentiation in individual (a) {Cd-
SO }-strands and (b) {Cd-btre}-nets; hydrogen atoms not shown. The
connecting lines between the Cd atoms in a Cd unit are topological aids.
4
3
Figure 12. Coordination environment of the metal atom in 8 and 9 (Zn
instead of Cd in 8). Selected distances and angles in Table S9, Supporting
Information, ranges in Table 1. Symmetry codes: 2 ) 0.5 - x, 1 - y, 0.5
+
z; 3 ) -x, 0.5 + y, 1 - z; 4 ) 0.5 + x, 0.5 - y, 0.5 - z; 4′ ) -0.5 +
x, 0.5 - y, 0.5 - z; 5 ) -x, 1 - y, 1 - z; 6 ) 0.5 + x, y, 0.5 - z; 6′ )
0.5 + x, y, 0.5 - z; 7 ) x, 0.5 - y, z.
-
bridged by three triazolyl rings to give metal strands along a
(Figure 12). There are two crystallographically different btre
ligands in these structures. The trans-bent ligand with triazol
ring N6-N8 and inversion-symmetry related triazolyl moieties
connects four metal atoms in the typical κN1:N2:N1′:N2′ mode,
as seen before, and gives rise to a 3D framework (Figure 13).
The trans-bent ligand with rings N1-N3 and N4-N5 connects
only between two metal atoms in the novel κN1:N2 mode and
has a non-coordinating triazole ring (N4-N5). Ring N1-N3
lies on a special position within a symmetry plane, and the
triazole ring N4-N5 is bisected by this plane of symmetry.
Both triazol rings of this special btre ligand are, thus, rotated
90° to each other. This dangling btre ligand reaches into the
rhombic channels of the 3D framework (Figure 13). Dangling
btre ligands from opposite corners interdigitate with C-H· · ·N
bonding (Table S1, Supporting Information), thereby separating
the rhombic channels into two trigonal halves which contain
Figure 9. Packing diagram for 6 viewed along 2D layers, parallel to the
0 0 4) planes (indicated in red) to show the disordered, non-coordinated
sulfate anions between the layers.
(
four bridging btre ligands (Figure 10). Neighboring, inver-
sion-symmetry related Cu atoms are bridged by two triazolyl
rings to give metal strands along c (Figure 11). The trans-
bent btre ligand with C -symmetry related triazolyl moieties
2
connects four copper atoms in κN1:N2:N1′:N2′ mode to
create an open 3D framework with rhombic channels (Figure
1
1) which contains the rotationally disordered perchlorate
ions and some crystal water.
3
} 8 and 3
∞
{[Zn(µ
4
-btre)(µ
2
-btre)](ClO
4
)
2
∞
{[Cd(µ
4 2
-btre)(µ -
4 2
btre)](ClO ) } 9. In the isomorphous compounds 8 and 9 the
zinc or cadmium metal atom, respectively, is octahedrally
coordinated by six nitrogen atoms from six bridging btre ligands
(Figure 12). Symmetry related neighboring metal atoms are
2172 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
Figure 15. 2D subnet in 10 from the bridging action of the cyano groups
and the triazolyl rings between the copper atoms; the remainder to each
triazolyl ring is not shown for clarity.
Figure 13. 3D framework in in 8 and 9 (Zn instead of Cd in 8). Perchlorate
ions in the trigonal channels are ordered but are not shown for clarity (filled
network in Figure S25, Supporting Information).
Figure 16. One of the interpenetrating 3D frameworks in 10 (cf. Figure
1
2 4
7). Centroids of the six-membered Cu N rings are shown as green balls
and with connecting lines (semitransparent) to better visualize the open 3D
framework.
Figure 14. Coordination environment of the copper atom in 10. Selected
distances and angles in Table S10, Supporting Information, ranges in Table
1
-
0
. Symmetry codes: 1 ) 1 + x, y, -1 + z; 3 ) -x, 1 - y, 1 - z; 3′ ) 1
x, 1 - y, -z; 4 ) -0.5 + x, 1.5 - y, -0.5 + z; 4′ ) 0.5 + x, 1.5 - y,
.5 + z.
the ordered perchlorate ions (C-H· · ·O bonding, Table S1,
Supporting Information).
3
∞
2 2 2 4
[Cu (µ -CN) (µ -btre)] 10. The copper(I) atom in 10 is
coordinated by two nitrogen atoms from two btre ligands,
one cyano nitrogen, and one cyano carbon atom (Figure 14).
The cyano groups are a decomposition product from the btre
ligand in the hydrothermal synthesis, concomitant with the
reduction from Cu(II) to Cu(I). Each cyano ligand bridges
between two Cu atoms. Adjacent copper(I) atoms are either
connected by a close to linear cyanide bridge or by two
Figure 17. Schematic drawing of the two interpenetrating 3D frameworks
in 10 (one in green and the other in red). Centroids of the six-membered
Cu N rings are given as green or red balls and with connecting lines.
2 4
typical π-stacking interaction (Figure 18, Table S3, Sup-
3
9,42
porting Information).
Solid-State CPMAS NMR. The number of crystallo-
graphically (symmetry) independent (unique) atoms of the
asymmetric unit in (diamagnetic) compounds and coordina-
tion networks should be reflected in the solid-state NMR
2 4
triazolyl rings to a six-membered Cu N ring with inversion
symmetry. These bridging actions create a 2D subnet with
larger openings (Figure 15). Furthermore, each trans-bent
btre ligand has inversion-symmetry related triazolyl moieties
and connects four copper atoms (cf. Figure 14) from adjacent
43,44
spectra of active nuclei.
A collection of solid-state NMR
(
42) Wu, H.-P.; Janiak, C.; Uehlin, L.; Kl u¨ fers, P.; Mayer, P. Chem.
Commun. 1998, 2637–2638.
2
D subnets in κN1:N2:N1′:N2′ mode to give an open 3D
framework (Figure 16).
(43) Chierotti, M. R.; Gobetto, R. Chem. Commun. 2008, 1621–1634.
(
44) (a) Ruiz, J.; Rodr ´ı guez, V.; Cutillas, N.; Hoffmann, A.; Chamayou,
A.-C.; Kazmierczak, K.; Janiak, C. CrystEngComm 2008, 10, 1928–
1938. (b) Habib, H. A.; Hoffmann, A.; H o¨ ppe, H. A.; Janiak, C. Dalton
Trans 2009, DOI: 10.1039/b812670d. (c) Althoff, G.; Ruiz, J.;
Rodr ´ı guez, V.; L o´ pez, G.; P e´ rez, J.; Janiak, C. CrystEngComm 2006,
8, 662–665.
The wide openings in the single 3D framework shown in
Figure 16 lead to the 2-fold intepenetration of two symmetry-
1
related 3D networks to give a densely packed structure. The
interpenetration or internetwork packing is controlled by a
Inorganic Chemistry, Vol. 48, No. 5, 2009 2173

Habib et al.
Figure 19. 13C CPMAS NMR spectrum for 2 (as an example also for 1)
and schematic drawing of the building unit with the unique C atoms given
as atom symbols. The four symmetry different triazolyl-CH carbon atoms
are not resolved. Peak positions: 144.8, 48.2, and 46.4 ppm.
Figure 18. Interpenetration of the two 3D frameworks (differentiated by
the green and red bonds) through the grid windows in 10 with indication
of the controlling π-π stacking interaction (dashed lines) of the (by symmetry
relation 1 - x, 1 - y, 1 - z) parallel triazolyl rings: Centroid-centroid
distance 3.505(2) Å, interplanar separation 3.25 Å, slippage 1.32 Å ()
parallel displacement between ring centroids from a perfect face-to-face
alignment, cf. Table S3, Supporting Information).
spectra for a certain ligand or ligand combination could
eventually serve as a tool to elucidate, without single-crystal
X-ray crystallography, the network topology, the nature and
stereochemistry of hitherto structurally uncharacterized sol-
45
ids, amorphous or poorly crystalline coordination polymers.
Figure 20. 13C CPMAS NMR spectrum for 3 and schematic drawing of
Also, solid-state NMR can be a structurally informative
technique for materials containing stoichiometric paramag-
the building unit with the unique C atoms as atom symbols. Peak positions:
1
50.7, 149.8, 146.4, 142.3, 138.3, 48.3, and 44.2 ppm.
46
netic Cu(I)/Cu(II)/Zn(II) constituents. Structural studies in
1
3
15
the solid state by C and N CPMAS NMR spectroscopy
carried out on a series of 2-aminotroponimine derivatives
have allowed to establish the existence of hydrogen bonding
4
7
and to determine the most stable tautomer. So far, we are
not aware of many in-depth solid-state NMR investigations
of metal-organic coordination networks.
Generally, the 13C CPMAS spectra of the diamagnetic
metal-btre complexes 1-10 exhibit CH resonances between
1
42-149 ppm (btre ligand 145.6 ppm, cf. Figure S26,
Supporting Information) and CH
2
resonances usually between
4
4-49 ppm (btre ligand 44.1 ppm). The dihalozinc com-
pounds 1 and 2 (0D) with a µ
2
-btre-κN1:N1′ coordination
13
mode (cf. Figure 1, Figure 19) give C CPMAS spectra with
a notably lower signal-to-noise ratio. Such an increased noise
could also be seen in the halocopper nets 4 and 5 and is
ascribed to the presence of the halogen quadrupolar nuclei
Figure 21. 13C CPMAS NMR spectrum for 7 (example also for 4 and 5)
and schematic drawing of the building unit with the unique C atoms as
atom symbols. Peak positions: 145.8, 142.2, and 44.9 ppm.
4
Compound 4, 5, and 7 with a µ -btre coordination mode
(
vide infra).
The 13C CPMAS NMR spectrum of the 1D di(isothiocy-
and half a ligand unique, that is, one symmetry-independent
triazolyl-methylene group (cf. Figure 4 and 10), display the
three signals expected for the three symmetry-different
carbon atom (Figure 21).
anato)zinc chain 3 with µ
the expected number of different C atoms resolved, with the
zinc-bound NCS signals in the expected region (Figure 20).
2
-btre-κN1:N1′ mode has almost
48
The 13C CPMAS spectrum of 6 (Figure 22) displays 5
out of 9 signals expected for the symmetry-independent
carbon atoms of a full and half a unique btre ligand, with
(
(
(
45) Masciocchi, N.; Galli, S.; Alberti, E.; Sironi, A.; Di Nicola, C.;
Pettinari, C.; Pandolfo, L. Inorg. Chem. 2006, 45, 9064–9074.
46) Ouyang, L.; Aguiar, P. M.; Batchelor, R. J.; Kroeker, S.; Leznoff,
D. B. Chem. Commun. 2006, 744–746.
47) Claramunt, R. M.; Sanz, D.; P e´ rez-Torralba, M.; Pinilla, E.; Torres,
M. R.; Elguero, J. Eur. J. Org. Chem. 2004, 4452–4466.
both of them in µ
Compound 8 and 9 contain in 1:1 ratio a µ
as well as a µ -κN1:N2-bridging (dangling) btre ligand
4
-bridging mode (cf. Figure 7).
4
- (half-unique)
2
2174 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
Figure 22. 13C CPMAS NMR spectrum for 6 and schematic drawing of
Figure 25. Fluorescence excitation and emission spectra of 2, 4, and 5;
the building unit with the unique C atoms as atom symbols. Peak positions:
the respective excitation (emission spectra) and monitored wavelengths
1
46.7, 145.4, 143.3, 142.2, and 47.7 ppm.
(
excitation spectra) are indicated.
integral ratio of this upfield-shifted CH
other signal groups matches the expected ratio of 8 (CH) to
(remaining three CH ) to 1 (CH ). Noteworthy, a chemical
shift difference of 8-9 ppm between the CH resonances is
unusually large for otherwise chemically very similar groups.
We assign this CH resonance below 40 ppm to the CH
2
resonance to the
3
2
2
2
2
2
group bound to the uncoordinated triazolyl ring (C4, cf.
Figure 12) as the bonding angle (C3-C4-N4) at this carbon
atom is only 106.9(4)°. Its neighboring methylene group (C3)
has a bonding angle of 113.8(4)°. The other btre-methylene
groups in 1-10 and in the benzene-1,3,5-tricarboxylate
1
5
adduct of btre lie between 109.6(4)° and 113.8(3)°,
typically being somewhat widened relative to the tetrahedral
Figure 23. 13C CPMAS NMR spectrum for 8 (example also for 9) and
schematic drawing of the building unit with the unique C atoms as atom
symbols. All atoms of the µ
2
-κN1:N2-bridging, dangling btre ligand have
angle. Angular distortions can affect the MAS chemical
shift. Also, the CH group bound to the uncoordinated
2
triazolyl ring may come close to the shielding region of a
nearby triazolyl group from an interdigitated dangling btre
ligand (cf. Figure 13).
half-occupancy (indicated by plain font style). Integral of CH
2
resonance
49
around 37 ppm set to 1. Peak positions: 148.8, 148.1, 146.6, 144.2, 45.7,
and 36.5 ppm (148.4, 147.6, 146.3, 144.3, 45.6, and 37.2 ppm for 9, cf.
Figure S27, Supporting Information).
4
The cyanide framework 10 features again a µ -coordination
1
3
mode with half a btre ligand being unique. Its C CPMAS
spectrum (Figure 24) shows 2 out of 3 signals expected for
the three symmetry-independent triazolyl-methylene carbon
atoms, plus the signal for the cyano carbon atom.
1
The H MAS NMR spectra feature broader peaks and
hence are less susceptible to a direct interpretation. Yet, they
1
3
follow in resolution and differing patterns the C spectra
(cf. Figures S28-S38, Supporting Information).
It is obvious that different metal-btre coordination modes
13
give rise to different signal patterns in the C CPMAS NMR
spectra from which, in turn, the metal-ligand substructure
can be deduced. The ligand symmetry is clearly visible
through the number of peaks. Furthermore increased split-
tings (cf. Figure 20) or enhanced chemical shifts (cf. Figure
Figure 24. 13C CPMAS NMR spectrum for 10 and schematic drawing of
the building unit with the unique C atoms as atom symbols. Peak positions:
1
43.3 (broad but not spiked), 88.6, and 45.4 ppm.
2
3) in comparison to similar spectra are evidence for packing
(
within and bisected by a mirror plane, cf. Figure 12) and
show 6 out of 8 signals expected for the symmetry-different
unique) carbon atoms (Figure 23). The special case of the
-κN1:N2-btre ligand gives rise to a new signal at high field,
effects. The latter cannot yet be traced to a simple origin.
To understand and quantify the different effects possible in
the solid state a more thorough analysis of the chemical shifts
(
µ
2
1
3
around 37 ppm, which is not seen in any other C CPMAS
NMR spectra of the metal-btre complexes or the free btre
ligand (cf. Figure S26). Repeated NMR experiments on
different batches (Figure S27, Supporting Information) ruled
out that it originates from any impurities. Furthermore, the
(
48) Fratiello, A.; Kubo-Anderson, V.; Lee, D. J.; Mao, T.; Ng, K.;
Nickolaisen, S.; Perrigan, R. D.; San Lucas, V.; Tikkanen, W.; Wong,
A.; Wong, K. J. Solution Chem. 1998, 27, 331–359.
49) Sebastini, D. Int. J. Quantum Chem. 2005, 101, 849–853. Alam, T. M.;
Friedmann, T. A.; Schultz, P. A.; Sebastiani, D. Phys. ReV.B 2003,
67, 245309.
(
Inorganic Chemistry, Vol. 48, No. 5, 2009 2175

Habib et al.
Figure 26. Fluorescence excitation and emission spectra of 7, 8, 9, and 10; the respective excitation (emission spectra) and monitored wavelengths (excitation
spectra) are indicated.
Table 2. Crystal Data and Structure Refinement for 1-3
compound
1
2
3
empirical formula
C
12
H
16Cl
4
Zn
2
N
12
C
12
H
16Br
4
Zn
2
N
12
C
8
H
8
ZnN
8 2
S
-
1
M/g mol
crystal size/mm
θ range/deg
600.91
778.75
345.71
0.41 × 0.29 × 0.04
6.42-72.64
-32, 29; -11, 10; -24, 27
monoclinic
C2/c
19.7337(4)
6.71120(10)
16.7151(3)
90.00
97.4060(10)
90.00
2195.23(7)
4
0.32 × 0.18 × 0.03
4.12-58.02
(26; ( 9; -22, 23
monoclinic
C2/c
19.9430(6)
6.9223(2)
16.9212(5)
90.00
97.101(3)
90.00
2318.08(12)
4
0.23 × 0.12 × 0.05
4.34 - 51.70
(18; -11, 10; ( 23
monoclinic
C2/c
14.898(2)
9.514(1)
19.584(2)
90.00
106.316(2)
90.00
2664.2(6)
8
2
h; k; l range
crystal system
space group
a/Å
b/Å
c/Å
R/deg
ꢀ/deg
γ/deg
V/Å3
Z
3
D
calc/g cm-
1.818
2.231
1.724
F (000)
µ/mm
1200
2.700
1488
8.991
1392
2.155
-
1
max/min transmission
reflections collected (Rint
independent reflections
obs. reflect. [I > 2σ(I)]
parameters refined
0.8997/0.4041
14437 (0.0255)
4979
3877
136
0.476/-0.576
0.0303/0.0676
0.0460/0.0727
1.020
0.7742/0.1610
23706 (0.0753)
3081
2180
136
0.647/-0.751
0.0335/0.0573
0.0634/0.0652
0.999
0.8999/0.6370
11194 (0.0634)
2441
1824
172
0.427/-0.379
0.0367/0.0690
0.0577/0.0774
1.040
)
a
-3
max./min. ∆F /e Å
b
R
R
1
/wR
/wR
2
[I > 2σ(I)]
b
1
2
(all reflect.)
2
c
Goodness-of-fit on F
d
weight. scheme w; a/b
0.0351/0.4069
0.0242/1.7857
0.0268/2.6630
a
b
2
2
2
2)2]]1/2
c
2
2 2
Largest difference peak and hole.
R
1
) [∑(|F
o
| - |F
c
|)/∑|F
o
|]; wR
2
) [∑[w(F
o
- F
c
) ]/∑[w(F
o
.
Goodness-of-fit ) [∑ [w(F
o
- F ) ]/(n -
c
p)]1/2
.
d
w ) 1/[σ (F
2
2
) + (aP) + bP] where P ) (max(F
2
2
or 0) + 2F
2
o
o
c
)/3.
by quantum chemical calculations or the systematic inves-
tigation of many more systems is needed.
Luminescence Properties. The compounds 2, 4, 5, 7, 8,
The relative intensity of the chloride containing 4 is weaker
compared with that of the bromide one (5). No luminescence
was found for the cadmium sulfate network 6 probably
mainly because of quenching as a consequence of high-
frequency oscillations of OH-groups directly coordinated to
cadmium. This observation is made frequently in the case
of rare earth ions when multiples of the oscillation strength
9
, and 10 exhibit broadband luminescence under UV
excitation (Figures 25 and 26). The free ligand btre did not
show fluorescence probably because of a photoinduced
5
0
electron transfer.
The dinuclear molecular zinc complex exhibits only
luminescence if coordinated to bromide (compound 2). Under
excitation at 270 nm an emission at 411 nm was observed.
The chloride compound 1 did not show any measurable
luminescence. Both copper(I) halide centered 2D coordina-
tion polymers 4 and 5 show strong blue luminescence
peaking around 470 nm upon excitation at 282 and 284 nm.
of the OH group approximately match the energy of the
51,52
radiative emission.
Additionally, one rather often ob-
serves a significant decrease of fluorescence intensity caused
by the coordination of complex ions to heavier atoms like
cadmium(II) because of the heavy-atom effect. With increas-
ing atom number these ions promote intersystem crossings
leading to quenching of fluorescence and in some cases
53
increasing phosphorescence. This fits very nicely with our
results which show more intense fluorescence of the copper(I)
(
50) Ji, H. F.; Dabestani, R.; Brown, G. M.; Hettich, R. L. Photochem.
Photobiol. 1999, 69, 513.
2176 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
Table 3. Crystal Data and Structure Refinement for 4-7
compound
4
5
6
7
e
e
e,f
2.5
g
empirical formula
C
3
H
4
ClCuN
3
C
3
H
4
BrCuN
3
C
9
H
25Cdf
3
N
9
17
O S
C
6
H
6 4.25
8.5CelCuN O
-
1
M/g mol
crystal size/mm
θ range/deg
181.08
225.54
948.73
331.67
0.38 × 0.24 × 0.04
0.22 × 0.07 × 0.02
0.44 × 0.24 × 0.05
3.96-53.8
(35; ( 11; ( 27
monoclinic
C2/c
0.45 × 0.28 × 0.03
4.74 - 52.96
(13; ( 23; ( 9
monoclinic
C2/c
2
6.26-53.88
5.90-56.78
h; k; l range
crystal system
space group
a/Å
b/Å
c/Å
(8; ( 8; ( 8
(8; ( 8; ( 9
triclinic
P1j
triclinic
P1j
6.4000(5)
6.5778(6)
7.0244(5)
81.555(5)
69.126(6)
86.387(6)
273.29(4)
2
6.3012(4)
6.7360(4)
7.3182(5)
83.084(4)
71.846(3)
86.448(2)
292.91(3)
2
28.0573(7)
9.0053(2)
21.2997(5)
90.00
101.5040(10)
90.00
5273.6(2)
8
2.367
11.0004(4)
18.6159(7)
7.2158(2)
90.00
118.241(2)
90.00
1301.77(8)
4
1.690
R/deg
ꢀ/deg
γ/deg
V/Å3
Z
3
D
calc/g cm-
2.201
2.557
F(000)
µ/mm
178
4.357
214
10.430
3624
2.687
664
1.901
-
1
max/min transmission
reflections collected (Rint
independent reflections
obs. reflect. [I > 2σ(I)]
parameters refined
0.8450/0.2883
5307 (0.0329)
1184
1093
73
2.134 /-0.636
0.0504/0.1605
0.0527/0.1648
1.123
0.8185/0.2075
6186 (0.0265)
1471
1366
73
0.538/-0.653
0.0202/0.0454
0.0223/0.0461
1.076
0.8774/0.3843
27302 (0.0340)
5648
5531
405
1.162/-0.735
0.0433/0.1030
0.0441/0.1033
1.360
0.9452/0.4816
12268 (0.0351)
1353
1250
118
0.257/- 0.335
0.0249/0.0638
0.0276/0.0649
1.087
)
a
-3
max./min. ∆F /e Å
b
R
R
1
/wR
/wR
2
[I > 2σ(I)]
b
1
2
(all reflect.)
2
c
Goodness-of-fit on F
d
weight. scheme w; a/b
0.1323/0.0512
0.0126/0.3592
0.0000/115.7791
0.0351/0.8630
a
b
c
d
e
See footnote a to Table 2. See footnote b to Table 2. See footnote c to Table 2. See footnote d to Table 2. Throughout the text the doubled formula
f
of the asymmetric unit was used to have full ligand numbers. H atoms on some aqua ligands and crystal water not located but included in formula and
g
formula mass. H atoms on partly occupied crystal water not located but included in formula and formula mass.
Table 4. Crystal Data and Structure Refinement for 8-10
compound
8
9
10
e
Empirical formula
C
12
H
16Cl
2
ZnN12
O
8
C
12
H
16Cl
2
CdN12
O
8
C
4
H
4
CuN
4
-
1
M/g mol
crystal size/mm
θ range/deg
592.64
639.67
171.65
0.30 × 0.25 × 0.10
3.74-56.28
(10; -22, 23; -18, 17
orthorhombic
Pnma
8.0135(3)
17.6580(7)
13.8841(6)
90.00
90.00
90.00
1964.63(14)
4
2.004
0.12 × 0.08 × 0.01
3.66-63.22
-12, 11; -15, 26; -20, 17
orthorhombic
Pnma
8.23350(10)
17.8751(4)
14.2061(3)
90.00
90.00
90.00
2090.78(7)
4
2.032
0.24 × 0.15 × 0.03
6.28-51.82
(7; ( 15; -9, 8
monoclinic
2
h; k; l range
crystal system
space group
a/Å
b/Å
c/Å
1
P2 /n
6.1253(3)
12.9739(9)
7.6245(5)
90.00
103.989(2)
90.00
R/deg
ꢀ/deg
γ/deg
V/Å3
Z
587.94(6)
4
1.939
3
D
calc/g cm-
F(000)
µ/mm
1200
1.600
1272
1.373
340
3.610
-
1
max/min transmission
reflections collected (Rint
independent reflections
obs. reflect. [I > 2σ(I)]
parameters refined
0.8564/0.6453
14000 (0.0631)
2473
1917
172
0.848/-0.600
0.0483/0.1277
0.0639/0.1369
1.108
0.9864/0.8525
16400 (0.0599)
3598
2302
172
0.752/-0.590
0.0358/0.0652
0.0734/0.0757
1.004
0.8994/0.4778
4871 (0.0385)
1140
1019
82
0.424/-0.460
0.0280/0.0611
0.0331/0.0651
1.080
)
a
-3
max./min. ∆F /e Å
1
b
R
R
/wR2 [I > 2σ(I)]
b
1 2
/wR (all reflect.)
2
c
Goodness-of-fit on F
d
weight. scheme w; a/b
0.0668/2.4355
0.0284/0.0799
d
0.0222/1.2033
a
b
c
e
See footnote a to Table 2. See footnote b to Table 2. See footnote c to Table 2. See footnote d to Table 2. Throughout the text the doubled formula
of the asymmetric unit was used to have full ligand numbers.
and zinc species compared with the cadmium ones. This also
holds for the 3D coordination polymers. Those of copper(I)
26) and emit around 480 nm under excitation around 280
nm. In the isomorphous zinc and cadmium compounds (8
(7 and 10) show a very similar luminescent behavior (Figure
(
52) Stein, O.; W u¨ rzberg, E. J. Chem. Phys. 1975, 62, 208.
(
51) Heller, A. J. Am. Chem. Soc. 1966, 88, 2058.
(53) Minaev, B.; Ågren, H. Chem. Phys. 2005, 315, 215.
Inorganic Chemistry, Vol. 48, No. 5, 2009 2177

Habib et al.
and 9) an emission peaking at 429 nm (8) and 403 nm (9)
was observed when excited around 370 nm. Both of them
also show an analogous emission at the same wavelengths
if excited at 280 nm, that is, the same excitation wavelength
as found in the copper compounds.
mL) was stirred for 30 min at room temperature, transferred
to a Teflon-lined stainless-steel autoclave, and heated at 180
°C for 3 d. Then the autoclave was cooled to room
temperature at a rate of 2.8 °C h . A colorless crystalline
product, which was suitable for X-ray single crystal analysis
was filtered off, washed with distilled water, and dried in
air (Yield 140 mg, 36% based on Zn). Elemental analysis
-
1
Experimental Section
12 2 4
C H16Zn N12Br (778.72) calcd C 18.51, H 2.07, N 21.58;
Commercially available solvents, monoformylhydrazine, triethyl
found: C 18.22, H 2.09, N 20.92%; IR (KBr) 3102(w),
3060(w), 2998(w), 2951(w), 1543(s), 1470(m), 1391(m),
1363(w), 1241(w), 1194(s), 1072(s), 1028(s), 974(w), 943(w),
orthoformate, ethylenediamine, NH
CuSO ·5H O, Cu(ClO ·6H O, ZnCl
O, CdSO ·8/3H O and Cd(ClO
4
SCN, NH
, ZnBr , ZnSO
·6H O were used without
4
PF
6
, CuCl
2 2
, CuBr ,
4
2
)
4 2
2
2
2
4
, Zn(ClO
4 2
) ·
6
H
2
4
2
4
)
2
2
-
1
further purification. Caution! Perchlorate salts of metal complexes
are potentially explosiVe and should be handled with extreme
caution and only in Very small quantities. The ligand 1,2-bis(1,2,4-
triazol-4-yl)ethane (btre) was prepared according to the method from
868(s), 681(w), 638(s), 485(m), 417(w) cm .
catena-[{µ
isothiocyanato-KN)-zinc(II)],
mixture of ZnSO · 7H
98 mg, 1.30 mmol), btre (233 mg, 1.42 mmol), and water
20 mL) was stirred for 30 min under reflux. The clear
2
-1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN1′}-bis-
1
(
∞
[Zn(NCS)
2
(µ
2
-btre)] (3). A
SCN
O (164 mg, 0.57 mmol), NH
4
5
4
4
2
Bayer. Dried methanol was used for the preparation of the btre
ligand. All Cu(I) products were collected under argon atmosphere
to avoid oxidative decomposition of the colorless Cu(I) crystals to
green colored Cu(II) containing powders in air. Elemental analyses
were performed on a VarioEL from Elementaranalysensysteme
GmbH. Infrared spectra were recorded in the range 400-4000 cm-
on a Nicolet Magna 760 Spectrometer using a diamond orbit ATR
unit. Thermogravimetric analyses were carried out in a simultaneous
thermoanalysis apparatus STA 409C from Netzsch under nitrogen
with a heating rate of 10 °C min- in the range 50 to 600 °C. The
filled sample container was conditioned by first applying oil pump
vacuum down to 1 bar for 5 min, then flushing with nitrogen.
Powder X-ray diffraction patterns were measured at ambient
temperature using a STOE STADI-P with Debye-Scherrer geom-
etry, Mo KR radiation (λ ) 0.7093 Å), a Ge(111) monochromator
and the samples in glass capillaries on a rotating probe head.
Simulated powder patterns were based on single-crystal data and
(
(
colorless solution was left for slow evaporation at room
temperature while colorless needles crystals were formed
after 1 day, which were suitable for X-ray single crystal
analysis. The product was filtered off, washed with distilled
water, and dried in air (Yield 140 mg, 71% based on Zn).
1
Elemental analysis C
8 8 8 2
H ZnN S (345.71) calcd C 27.79, H
1
2
1
2
1
1
6
.33, N 32.41, S 18.55; found: C 27.80, H 2.34, N 32.74, S
8.50%; IR (KBr) 3119(w), 3084(w), 3052(w), 3008(w),
092(w), 2069(s), 1661(w), 1553(s), 1480(m), 1448(s),
390(m), 1361(m), 1321(w), 1248(w), 1206(s), 1177(w),
073(s), 1035(s), 984(m), 955(w), 909(m), 870(w), 834(m),
-
1
72(m), 651(s), 623(s), 511(m), 481(m) cm .
catena-[{µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
KN1′:KN2′}-dichloro-dicopper(I)],
(4). A mixture of CuCl (134 mg, 1.00 mmol), btre (493
4
5
5
2
calculated using the STOE WinXPOW software package.
∞
2 2 2 4
[Cu (µ -Cl) (µ -btre)]
Emission spectra were measured on a Perkin-Elmer LS-55, λexc
259-285 nm, split widths (em, ex) 5.0 nm, scan speed 2 nm
s , solid sample at room temperature.
2
)
mg, 3.00 mmol), and water (10 mL) was stirred for 30 min
at room temperature, transferred to a Teflon-lined stainless-
steel autoclave, and heated at 180 °C for 3 d. Then the
autoclave was cooled to room temperature at a rate of 2.8
-
1
Syntheses
-
1
°
C h . A colorless crystalline product, which was suitable
[
Bis{{µ
zinc(II)}], [{ZnCl
.00 mmol), btre (493 mg, 3.00 mmol), and water (10 mL)
2
-1,2-bis(1,2,4-triazol-4-yl)ethane-KN1:KN1′}-dichloro-
for X-ray single crystal analysis, was filtered off, washed
with distilled water, dried, and stored under argon (Yield
2
(µ -btre)} ] (1). A mixture of ZnCl (136 mg,
2
2
2
1
1
10 mg, 61% based on Cu). Elemental analysis
Cu Cl (362.19) calcd C 19.90, H 2.23, N 23.20;
found: C 20.17, H 2.21, N 23.26%; IR (KBr) 3134(w),
was stirred for 30 min at room temperature, transferred to a
Teflon-lined stainless-steel autoclave, and heated at 180 °C
for 3 d. Then the autoclave was cooled to room temperature
C
6
H
8
N
2 6
2
-1
3
1
8
107(m), 3065(w), 3002(w), 2958(w), 1536(s), 1474(m),
at a rate of 2.8 °C h . A colorless crystalline product, which
was suitable for X-ray single crystal analysis, was filtered
off, washed with distilled water, and dried in air (Yield 130
445(s), 1393(s), 1361(w), 1322(s), 1184(s), 1076(s), 988(s),
-
1
71(s), 838(s), 774(m), 683(m), 629(s), 405(w) cm .
catena-[{µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
KN1′:KN2′}-dibromo-dicopper(I)],
(5). A mixture of CuBr (223 mg, 1.00 mmol), btre (493
mg, 43% based on Zn). Elemental analysis C12
H16Zn
2
N
12Cl
4
4
2
(
600.91) calcd C 23.99, H 2.68, N 27.97; found: C 23.08, H
∞
2 2 2 4
[Cu (µ -Br) (µ -btre)]
2
2
1
4
.70, N 27.26%; IR (KBr) 3109(w), 3060(w), 3003(w),
957(w), 1544(s), 1473(m), 1392(s), 1244(w), 1197(s),
075(s), 1031(s), 974(w), 871(s), 861(w), 639(s), 488(m),
2
mg, 3.00 mmol), and water (10 mL) was stirred for 30 min
at room temperature, transferred to a Teflon-lined stainless-
steel autoclave, and heated at 180 °C for 3 d. Then the
autoclave was cooled to room temperature at a rate of 2.8
-
1
08(w) cm .
Bis{µ -1,2-bis(1,2,4-triazol-4-yl)ethane-KN1:KN1′}-dibromo-
zinc(II)}], [{ZnBr (µ -btre)} ] (2). A mixture of ZnBr (235
mg, 1.00 mmol), btre (493 mg, 3.00 mmol), and water (10
[
2
-
1
°
C h . A colorless crystalline product, which was suitable
2
2
2
2
for X-ray single crystal analysis, was filtered off, washed
with distilled water, dried, and stored under argon (Yield
125 mg, 55% based on Cu). Elemental analysis
(
(
54) Bayer, H. O.; Cook, R. S.; von Meyer, W. C. U. S. Pat. 1974, 3,
21–376.
55) STOE WinXPOW, Version 1.10; STOE & Cie GmbH: Darmstadt,
8
C
6
H
8
Cu
2 6 2
N Br (451.08) calcd C 15.98, H 1.79, N 18.63;
Germany, 2002.
found: C 16.37, H 1.66, N 17.84%; IR (KBr) 3130(w),
2178 Inorganic Chemistry, Vol. 48, No. 5, 2009

Luminescent d10 Metal-Organic Frameworks
3
1
8
106(m), 3065(w), 2993(w), 2955(w), 1535(s), 1473(m),
catena-[{(µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
4
445(s), 1391(s), 1360(w), 1321(s), 1186(s), 1075(s), 989(s),
KN1′:KN2′)}-{(µ
2
-1,2-bis(1,2,4-triazol-4-yl)ethane-KN1:KN2)}cad-
-
1
3
63(s), 837(s), 773(s), 681(m), 629(s), 405(w) cm .
catena-{Hexaaqua-tris{(µ -1,2-bis(1,2,4-triazol-4-yl)ethane-
KN1:KN2:KN1′:KN2′)}-di(µ -hydroxo)-tetra{(µ -sulfato-
KO,KO′,KO′′)}-hexacadmuim(II)-sulfate-hexahydrate},
mium(II)] diperchlorate,
∞ 4 2 4 2
{[Cd(µ -btre)(µ -btre)](ClO ) }
(
9). A mixture of Cd(ClO
)
4 2
· H O (329 mg, 1.00 mmol),
2
4
btre (493 mg, 3.00 mmol) and water (10 mL) was stirred
for 30 min at room temperature, transferred to a Teflon-
lined stainless-steel autoclave, and heated at 180 °C for 3 d.
Then the autoclave was cooled to room temperature at a rate
3
3
2
∞
{[Cd
6
(µ
3
-OH)
2
(µ
3
-SO
4
)
4
(µ
2
4
-btre)
3
(H
2
O)
6
](SO
4
)·∼6H
2
O} (6).
A mixture of CdSO
4
·8/3H
O (256 mg, 1.00 mmol), btre (493
-1
of 2.8 °C h . A colorless crystalline product, which was
mg, 3.00 mmol), and water (10 mL) was stirred for 30 min
at room temperature, transferred to a Teflon-lined stainless-
steel autoclave, and heated at 180 °C for 3 d. Then the
autoclave was cooled to room temperature at a rate of 2.8
suitable for X-ray single crystal analysis was filtered off,
washed with distilled water, and dried in air (Yield 310 mg,
4
(
2
1
8 2
9% based on Cd). Elemental analysis C12H16CdN12O Cl
639.67) calcd C 22.53, H 2.52, N 26.28; found: C 22.49, H
.48, N 25.78%; IR (KBr) 3105(m), 3024(w), 1554(m),
463(m), 1395(w), 1313(w), 1281(w), 1218(m), 1117(s),
-
1
°
C h . A colorless crystalline product, which was suitable
for X-ray single crystal analysis, was filtered off, washed
with distilled water, and dried in air (Yield 80 mg, 26% based
on Cd). Elemental analysis C18
1073(s), 1027(m), 896(m), 861(m), 795(w), 684(m), 615(s),
-
1
H50Cd N O S
6 18 34 5
(1897.46)
463(w), 423(w) cm .
catena-[{(µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
KN1′:KN2′}-di-µ -cyano-KN:KC-dicopper(I)], [Cu (µ -
calcd C 11.39, H 2.66, N 13.28, S 8.45; found: C 11.45, H
4
3
2
3
1
9
.66, N 13.24, S 8.48%; IR (KBr) 3094(m), 3039(w),
010(w), 2974(w), 1679(m), 1525(s), 1454(s), 1384(m),
270(m), 1223(m), 1222(w), 1187(s), 1112(w), 1062(s),
2
∞
2
2
CN) (µ -btre)] (10). A mixture of CuSO · 5H O (250 mg,
2
4
4
2
1.00 mmol), btre (493 mg, 3.00 mmol), and water (10 mL)
was stirred for 30 min at room temperature, transferred to a
Teflon-lined stainless-steel autoclave, and heated at 180 °C
for 3 d. Then the autoclave was cooled to room temperature
-
1
60(s), 883(s), 783(w), 676(m), 634(s), 419(w) cm .
catena-[{µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
KN1′:KN2′}-copper(I)] perchlorate hydrate,
btre)]ClO O} (7). A mixture of Cu(ClO
4
3
∞
{[Cu(µ
4
-
-1
at a rate of 2.8 °C h . A colorless crystalline product, which
was suitable for X-ray single crystal analysis, was filtered
off, washed with distilled water, dried, and stored under argon
4
·∼0.25H
2
)
4 2
·6H O
2
(
(
370 mg, 1.00 mmol), btre (493 mg, 3.00 mmol), and water
10 mL) was stirred for 30 min at room temperature,
(
C
Yield 135 mg, 79% based on Cu). Elemental analysis
Cu (343.30) calcd C 27.99, H 2.35, N 32.64; found:
C 27.68, H 2.36, N 33.06%; IR (KBr) 3120(m), 3003(w),
transferred to a Teflon-lined stainless-steel autoclave, and
heated at 180 °C for 3 d. Then the autoclave was cooled to
room temperature at a rate of 2.8 °C h . A colorless
crystalline product, which was suitable for X-ray single
crystal analysis, was filtered off, washed with distilled water,
dried, and stored under argon (Yield 290 mg, 89% based on
H
8 8
2 8
N
-1
2
1
6
959(w), 2094(s), 1539(s), 1453(m), 1394(s), 1362(w),
324(s), 1191(s), 1075(s), 1001(m), 863(s), 840(w), 776(s),
-1
79(m), 632(s), 439(w) cm .
Cu). Elemental analysis C
2.03, H 2.46, N 25.69; found: C 21.63, H 2.56, N 24.90%;
IR (KBr) 3137(w), 2962(w), 1534(m), 1468(m), 1446(w),
6
H
8
CuN
6
O
4
Cl (327.17) calcd C
Solid-State NMR
2
All spectra were recorded using 2.5 mm rotors on a Bruker
Avance 500 solid-state NMR spectrometer (11.7 T) operating
at Lamor frequencies of 125.78 MMz for C. RF pulses
were applied at a transverse B1 field of 125 kHz correspond-
ing to a π/2 pulse width of 2 µs. C { H} CPMAS experi-
ments were performed under magic angle spinning at 20 KHz
and 30 kHz with bearing gas at ambient temperature. Cross
polarization was achieved using a ramp with typically 1024
steps applied to the proton channel ranging from 80 to 100%
1
9
5
391(m), 1364(w), 1322(w), 1190(s), 1168(m), 1071(s),
88(m), 961(m), 928(w), 857(s), 738(w), 682(w), 620(s),
1
3
-
1
32(w), 516(w), 485(w), 464(w), 447(w), 409(m) cm .
catena-[{(µ -1,2-Bis(1,2,4-triazol-4-yl)ethane-KN1:KN2:
-1,2-bis(1,2,4-triazol-4-yl)ethane-KN1:KN2)}zinc(II)]
13
1
4
KN1′:KN2′)}-{(µ
diperchlorate,
2
56
3
∞
{[Zn(µ
4
-btre)(µ
2
-btre)](ClO
4
)
2
} (8). A
mixture of Zn(ClO
)
4 2
2
·6H O (372 mg, 1.00 mmol), btre (493
1
3
and a contact time of 2 ms. In all C experiments, TPPM
dipolar decoupling was employed. C spectra were
referenced to the methyne resonance of alanine (51 ppm).
mg, 3.00 mmol), and water (10 mL) was stirred for 30 min
at room temperature, transferred to a Teflon-lined stainless-
steel autoclave, and heated at 180 °C for 3 d. Then the
autoclave was cooled to room temperature at a rate of 2.8
5
7
13
Fluorescence Spectroscopy
-
1
°
C h . A colorless crystalline product, which was suitable
for X-ray single crystal analysis, was filtered off, washed
Photoluminescence analyses for the fluorescing powders
of compounds 2, 4, 5, 7, 8, 9, and 10 were performed at
room temperature on a Perkin-Elmer LS55 fluorescence
with distilled water, and dried in air (Yield 415 mg, 70%
8 2
based on Zn). Elemental analysis C12H16ZnN12O Cl (592.64)
calcd C 24.32, H 2.72, N 28.36; found: C 24.36, H 2.70, N
(
56) (a) Metz, G.; Ziliox, M.; Smith, S. O. Solid State Nucl. Magn. Reson.
996, 7, 155–160. (b) Metz, G.; Wu, X.; Smith, S. O. J. Magn. Reson.
A 1994, 110, 219–227. (c) Metz, G.; Wu, X.; Smith, S. O. Chem.
Phys. Lett. 1994, 173, 461–465.
57) Bennett, A. E.; Rienstra, C. M.; Auger, M.; Lakshmi, K. V.; Griffin,
R. G. J. Chem. Phys. 1995, 103, 6951–6958.
2
1
1
7.98%; IR (KBr) 3107(m), 3026(w), 1551(m), 1464(m),
399(m), 1314(w), 1286(w), 1214(m), 1117(s), 1076(s),
018(w), 903(m), 864(m), 800(w), 681(m), 618(s), 425(w)
1
(
-
1
cm .
Inorganic Chemistry, Vol. 48, No. 5, 2009 2179

Habib et al.
spectrometer equipped with a Xe discharge lamp (equivalent
to 20 kW for 8 µs duration) and a gated photomultiplier with
modified S5 response.
water oxygen atom. The occupation of this crystal water adds
up to 1 crystal water per unit cell. No hydrogen atoms could
be found or refined for this partially occupied O atom. The
structure of 10 could also be refined to identical R-values in
X-ray Crystallography
the monoclinic space group P2
1
/c with the cell constants a
)
6.1253(3), b ) 12.9739(9), c ) 8.5483(4) Å, ꢀ )
Suitable single crystals were carefully selected under a
polarizing microscope. Data Collection: Bruker AXS with
APEXII CCD area-detector, Mo KR radiation (λ ) 0.71073
Å), graphite monochromator, double-pass method ω-scan,
3
120.062(3)°, V ) 587.94(6) Å . Graphics were obtained with
61
DIAMOND. Details of the supramolecular C-H· · ·N/X
X ) Cl, Br, S) and π-π interaction were calculated by the
(
62
5
8
program PLATON. π-Stacking interactions can be viewed
as medium to weak if they exhibit rather long centroid-
centroid distances (Cg · · · Cg > 4.0 Å) together with large
slip angles (ꢀ, γ > 30°) and vertical displacements (d > 2.0
Å). In comparison, strong π-stackings show rather short
centroid-centroid contacts (<3.8 Å), small slip angles (ꢀ, γ
Data collection and cell refinement with APEX2, respec-
5
8
tively, cell refinement and data reduction with SAINT,
59
experimental absorption correction with SADABS. Struc-
ture Analysis and Refinement: The structure was solved by
direct methods (SHELXS-97); refinement was done by full-
60
matrix least-squares on F2 using the SHELXL-97 program
60
<
25°) and vertical displacements (d < 1.5 Å) which
suite. All non-hydrogen positions were refined with aniso-
tropic temperature factors. Hydrogen atoms on carbon were
39,63,64
translate into a sizable overlap of the aromatic planes.
Crystal data and details on the structure refinement are given
in Table 2-4. The structural data has been deposited with
the Cambridge Crystallographic Data Center (CCDC-
numbers. 710669 to 710678 for 1-10, respectively).
positioned geometrically (C-H ) 0.98 Å for CH
for aromatic CH) and refined using a riding model (AFIX
3, 43, respectively), with Uiso(H) ) 1.2Ueq(C). In the
2
, 0.94 Å
2
structure of 6 the hydrogen atom on the hydroxo O atom
was positioned geometrically (O-H ) 0.99 Å) and refined
using a riding model (AFIX 13), with Uiso(H) ) 1.2Ueq(O).
Hydrogen atoms on the aqua ligand O2 and the half-occupied
crystal water O7 were found but had to be kept fixed in
subsequent refinement. Hydrogen atoms on the other aqua
ligands O1 and O3 and the other crystal water O atoms O5
and half-occupied O6, O35, and O36 could not be found.
The non-coordinated sulfate group around S3 is disordered
near an inversion center. It also resides on a split position
with the half-occupied crystal water O atoms O35 and O36.
In the structure of 7 the Cl atom of the perchlorate group
sits on a special position (2-fold rotation axis, Wyckoff
notation 4e, 1/2 y 1/4). The four oxygen atoms of the
perchlorate groups are disordered over 8 positions. Some
residual electron density is assigned to a partially occupied
Acknowledgment. The work is supported by KAAD and
DFG Grant Ja466/14-1.
Supporting Information Available: Crystal reactivity of 7, 8,
or 9 with NH PF /H O, thermogravimetric analyses, X-ray powder
4
6
2
diffractograms, tables of intermolecular interactions, tables of
selected bond distances and angles, additional pictures of networks,
1
3
1
CPMAS C, and H NMR spectra (26 pages). This material is
available free of charge via the Internet at http://pubs.acs.org.
IC802069K
(
(
61) Brandenburg, K. Diamond (Version 3.1e), Crystal and Molecular
Structure Visualization, Crystal Impact; K. Brandenburg & H. Putz
Gbr: Bonn, Germany, 2007.
62) (a) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7–13. (b) Spek, A. L.
PLATON - A Multipurpose Crystallographic Tool; Utrecht University:
Utrecht, The Netherlands, 2008; Windows implementation: L. J.
Farrugia, University of Glasgow, Scotland, Version 40608 (2008).
(
58) APEX2 (Version 2.1-0) Data Collection Program for the CCD Area-
Detector System; SAINT, Data Reduction and Frame Integration
Program for the CCD Area-Detector System; Bruker Analytical X-ray
Systems: Madison, WI, 2006.
(63) (a) Monfared, H. H.; Kalantari, Z.; Kamyabi, M.-A.; Janiak, C. Z.
Anorg. Allg. Chem. 2007, 633, 1945–1948. (b) Wu, B.; Huang, X.;
Xia, Y.; Yang, X.-J.; Janiak, C. CrystEngComm 2007, 9, 676–685.
(c) Wisser, B.; Janiak, C. Acta Crystallogr. 2007, E63, o2871–2872.
(d) Dorn, T.; Janiak, C.; Abu-Shandi, K. CrystEngComm 2005, 7, 633.
(64) Yang, X.-J.; Drepper, F.; Wu, B.; Sun, W.-H.; Haehnel, W.; Janiak,
C. Dalton Trans. 2005, 256–267; and supplementary material therein.
(59) Sheldrick, G. Program SADABS: Area-detector absorption correction;
University of G o¨ ttingen: G o¨ ttingen, Germany, 1996.
(
60) Sheldrick, G. M. SHELXS-97, SHELXL-97, Programs for Crystal
Structure Analysis; University of G o¨ ttingen: G o¨ ttingen, Germany,
1
997.
2180 Inorganic Chemistry, Vol. 48, No. 5, 2009