(Pyrazole)silver(I) and -gold(I) complexes with strong and weak hydrogen-bonding interactions as the basis of one- or two-dimensional structures

Article abstract of DOI:10.1002/ejic.200300947

New Au^I/Ag^I complexes containing one or two substituted pyrazole ligands [Au(Hpz^bp2)(PPh₃)](p-CH ₃C₆H₄SO₃) [Hpz^bp2 = 3,5-bis(4-n-butoxyphenyl)pyrazole] (1) and [M(Hpz^R2) ₂]_nX [Hpz^bp2 M = Au, n = 1, X = p-CH ₃C₆H₄SO₃ (2), NO₃ ^- (3); n = 2, X = 1,5-naphthalenedisulfonate (1,5nds) (4); Hpz ^R2 = Hpz^bp2, M = Ag, n = 1, X = BF₄^- (5), CF₃SO₃^- (6); Hpz^R2 = Hpz ^N02 (3,5-dimethyl-4-nitropyrazole), M = Ag, n = 1, X = BF ₄^- (7), CF₃SO₃^- (8)], have been prepared and characterized. Compounds 1, 2, 5 and 8 have been proved to be useful for supramolecular assembly from their single X-ray diffraction analysis. In all cases strong hydrogen bonds maintain the cationic units bonded to their corresponding counterions. The crystal packing arrangement of 1, 2 and 5 is, however, determined by weak C-H...O/F hydrogen-bonding interactions involving the remaining O/F atoms of the counterion. By contrast, for 8 a two-dimensional layer-type polymeric network is formed by π-π (NO ₂...NO₂) and coordinative Ag...O interactions in which the NO₂ substituent on the pyrazole is implicated. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300947

FULL PAPER
(Pyrazole)silver(
I
) and -gold(
I
) Complexes with Strong and Weak Hydrogen-
Bonding Interactions as the Basis of One- or Two-Dimensional Structures
[a]
[a]
[a]
[a]
[a]
´
´
M. Luz Gallego, Paloma Ovejero, Mercedes Cano,* Jose V. Heras, Jose A. Campo,
Elena Pinilla,[a,b] and M. Rosario Torres[b]
´
Dedicated to Professor Jose Vicente on the occasion of his 60th birthday
Keywords: : Gold / Hydrogen bonds / N ligands / Silver / Supramolecular chemistry
New AuI/AgI complexes containing one or two substituted
hydrogen bonds maintain the cationic units bonded to their
corresponding counterions. The crystal packing arrangement
pyrazole
ligands
[Au(Hpzbp2)(PPh3)](p-CH3C6H4SO3)
[Hpzbp2
=
3,5-bis(4-n-butoxyphenyl)pyrazole] (1) and of 1, 2 and 5 is, however, determined by weak C−H···O/F
[M(HpzR2)2]nX [HpzR2 = Hpzbp2, M = Au, n = 1, X =
hydrogen-bonding interactions involving the remaining O/F
atoms of the counterion. By contrast, for 8 a two-dimensional
layer-type polymeric network is formed by π···π (NO2···NO2)
and coordinative Ag···O interactions in which the NO2 sub-
stituent on the pyrazole is implicated.
−
p-CH3C6H4SO3 (2), NO3 (3); n = 2, X = 1,5-naphthalenedi-
sulfonate (1,5nds) (4); HpzR2 = Hpzbp2, M = Ag, n = 1, X =
BF4− (5), CF3SO3 (6); HpzR2 = HpzNO2 (3,5-dimethyl-4-nitro-
−
−
−
pyrazole), M = Ag, n = 1, X = BF4 (7), CF3SO3 (8)], have
been prepared and characterized. Compounds 1, 2, 5 and 8
have been proved to be useful for supramolecular assembly
from their single X-ray diffraction analysis. In all cases strong
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
the construction of supramolecular structures based on the
aurophilic nature of gold.[6b,7] Furthermore, experimental
Supramolecular architectures derived from metallic com- evidence from structures of Au/Ag-containing cationic com-
plexes as building blocks are an attractive focus of current plexes indicates the relevant role of the counterion in the
research. In this context coordinative interactions and/or molecular architecture.[2b,6c,8]
hydrogen bonds have been extensively used to produce
It has been postulated that the control and manipulation
supramolecular one-, two- or three-dimensional polymeric of weak interactions could be used as the key to tune the
structures.[1] However, although self-assembly has been well properties of the bulk materials. In addition to the classical
documented,[2] much work remains to extend the knowl- O/NϪH···X (X ϭ O, N or F atoms) hydrogen-bonding in-
edge of relevant structures. The nature of the metal, coun- teractions, other weaker CϪH···X (X ϭ O, N or F atoms)
terions or ligands are factors that can be modulated to de- interactions have been shown to control the molecular
termine the molecular assembly.
packing in the solid.[1g,9]
The silver() ion is a favourable building block because of
In previous work from our lab we have made use of hy-
its various potential coordination modes such as linear,[3] drogen-bonding interactions produced between cationic
trigonal[4] or tetrahedral,[5] and its affinity for hard donor metal complexes containing pyrazole ligands and the corre-
atoms such as nitrogen or oxygen. In addition, some sil- sponding counterions. Although the strong NH···X (X ϭ O
Ϫ
Ϫ
ver() derivatives have also been determined to present ex- or F atoms from NO3 or BF4 counterions) hydrogen
perimental evidence for an argentophilic attraction[6] and bonds are the predominant force driving the structure,
therefore with potential applications for self-assembled nets. other different intermolecular interactions, such as
In the same context, gold() complexes are promising for CϪH···O/F, are also considered to be important for the mo-
lecular assembly.[10]
[a]
´
´
Departamento de Quımica Inorganica I, Facultad de Ciencias
We have now extended these results to the use of new
silver() and gold() pyrazole derivatives of the type
[M(HpzR2)2]ϩ [HpzR2 ϭ 3,5-bis(4-n-butoxyphenyl)pyrazole,
Hpzbp2; 3,5-dimethyl-4-nitropyrazole, HpzNO2) containing
different counterions, as well as different substituents on
the pyrazole rings. The related complex containing only one
´
Quımicas, Universidad Complutense,
28040 Madrid, Spain
Fax: (internat.) ϩ 34-91-3944352
E-mail: mmcano@quim.ucm.es
[b]
´
Laboratorio de Difraccion de Rayos-X, Facultad de Ciencias
´
Quımicas, Universidad Complutense,
28040 Madrid, Spain
Eur. J. Inorg. Chem. 2004, 3089Ϫ3098
DOI: 10.1002/ejic.200300947
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M. Cano et al.
FULL PAPER
pyrazole ligand, [Au(Hpzbp2)(PPh3)](p-CH3C6H4SO3),
All compounds are air-stable white solids and they were
1
has also been prepared and studied (Scheme 1). We report characterized by elemental analysis and IR and H NMR
herein how the presence of strong or weak NϪH···O/F and spectroscopy. In addition, 31P NMR spectroscopy was also
CϪH···O/F inter- and intramolecular hydrogen-bonding in- used for 1. All data are listed in the Exp. Sect. The IR spec-
teractions, supported by the different counterions, are re- tra show, amongst others, the characteristic bands of the
sponsible for the molecular arrangement in the solid for pyrazole ligands, ν(CϭN) ϩ ν(CϭC) at ca. 1600 cmϪ1 and
complexes containing the Hpzbp2 ligand. In contrast, the ν(NϪH) in the range 3112Ϫ3308 cmϪ1, as well as those
molecular packing of those complexes with HpzNO2 is from the corresponding counterions.[8d,12]
dominated by interactions through the NO2 substituents on
the ligands.
1
The H NMR spectra in CDCl3 solution at room tem-
perature show the expected signals of the ligands. It is inter-
1
esting to note that the H NMR spectra of 5Ϫ8 at room
temperature are consistent with the presence of two equiva-
lent coordinated pyrazole ligands, each of them having two
equivalent substituents at the 3- and 5-positions. A related
equivalence of the substituents has also been observed for
1. Thus, it is possible to suggest a metallotropic equilibrium
to explain the above behaviour similar to that previously
found for related complexes.[13] Lowering the temperature
slows down the dynamic process, resulting in the non-equiv-
alence of the substituents, as observed for 5 and 6 at Ϫ40
°C by the well-defined signals for the aromatic and alkyl-
Scheme 1
Results and Discussion
Synthetic and Characterization Studies
Complex 1, containing triphenylphosphane, was ob-
tained from the reaction of [Au(p-CH3C6H4SO3)(PPh3)]
(prepared by a literature procedure)[8d] and one equivalent
of Hpzbp2 in dry THF (Scheme 2). Compounds 2Ϫ4 were
prepared by reaction of [AuCl(THT)] (THT ϭ tetrahydro-
thiophene)[11] with two equivalents of Hpzbp2 and one
equivalent of the corresponding silver salt in dry THF
(Scheme 3). The related silver() derivatives 5Ϫ8 were syn-
thesized by treatment of two equivalents of the correspond-
ing pyrazole ligand with one equivalent of the silver salt in
dry THF or acetonitrile (Scheme 4).
Scheme 2
Scheme 3
Figure 1. a) ORTEP plot of 1 at the 30% probability level; hydrogen
atoms, except H2, and the labelling of some atoms have been omit-
ted for clarity; b) view of the packing along the a axis (the phenyl
groups of the phosphane ligands have been omitted)
Scheme 4
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(Pyrazole)silver(I) and -gold(I) Complexes
FULL PAPER
˚
Table 1. Bond lengths (A) and angles (°) for 1, 2, 5 and 8
[Au(Hpzbp2)(PPh3)](p-CH3C6H4SO3) (1)
[Au(Hpzbp2)2](p-CH3C6H4SO3) (2)
Au1ϪN1
Au1ϪP1
N1ϪN2
S1ϪO3
S1ϪO4
S1ϪO5
S1ϪC44
2.069(5)
2.243(2)
1.396(7)
1.449(5)
1.451(6)
1.433(6)
1.775(7)
N1ϪAu1ϪP1
O3ϪS1ϪO4
O3ϪS1ϪO5
O4ϪS1ϪO5
O3ϪS1ϪC44
O4ϪS1ϪC44
O5ϪS1ϪC44
177.1(2)
111.2(4)
113.5(4)
113.6(4)
107.1(3)
104.7(3)
106.0(3)
Au1ϪN1
Au1ϪN3
N1ϪN2
N3ϪN4
S1ϪO5
S1ϪO6
S1ϪO7
2.019(7)
2.022(7)
1.36(1)
N1ϪAu1ϪN3
O5ϪS1ϪO6
O5ϪS1ϪO7
O6ϪS1ϪO7
O5ϪS1ϪC49
O6ϪS1ϪC49
O7ϪS1ϪC49
176.3(4)
111.7(5)
114.5(5)
112.4(5)
105.0(4)
105.7(4)
106.8(5)
1.36(1)
1.426(6)
1.447(6)
1.416(8)
1.77(1)
S1ϪC49
[Ag(Hpzbp2)2]BF4 (5)
[Ag(HpzNO2)2](CF3SO3) (8)
Ag1ϪN1
Ag1ϪN3
N1ϪN2
N3ϪN4
B1ϪF1
B1ϪF2
B1ϪF3
B1ϪF4
2.129(3)
2.118(3)
1.355(4)
1.359(4)
1.378(4)
1.360(4)
1.354(3)
1.375(4)
N1ϪAg1ϪN3
F1ϪB1ϪF2
F1ϪB1ϪF3
F1ϪB1ϪF4
F2ϪB1ϪF3
F2ϪB1ϪF4
F3ϪB1ϪF4
170.1(1)
108.5(3)
108.9(3)
109.7(3)
111.5(3)
108.8(3)
109.5(3)
Ag1ϪN1
Ag1ϪN4
N1ϪN2
N4ϪN5
N3ϪO1
N3ϪO2
N6ϪO3
N6ϪO4
S1ϪO5
S1ϪO6
S1ϪO7
2.171(2)
2.161(2)
1.363(3)
1.357(3)
1.223(3)
1.223(3)
1.224(5)
1.215(5)
1.427(2)
1.435(3)
1.443(3)
N1ϪAg1ϪN4
O1ϪN3ϪO2
O3ϪN6ϪO4
O5ϪS1ϪO6
O5ϪS1ϪO7
O6ϪS1ϪO7
O5ϪS1ϪC11
O6ϪS1ϪC11
O7ϪS1ϪC11
163.67(9)
123.3(3)
124.5(4)
114.0(2)
114.6(2)
115.1(2)
105.3(2)
103.0(2)
102.9(2)
˚
chain protons of the butoxyphenyl substituents. A similar
feature is also present in the gold derivatives 2Ϫ4, which
exhibit the non-equivalence of the butoxyphenyl substitu-
ents at room temperature. The protons at the 4-positions of
the pyrazole rings of 2 and 3 show an unusual coupling
with the NH proton, which was confirmed by homonuclear
decoupling techniques. This situation has also been ob-
served in some metal complexes containing related pyrazole
ligands.[14] The 31P NMR spectrum of 1 at room tempera-
ture in CDCl3 shows a single resonance at δ ϭ 31.06 ppm in
the characteristic region of gold-phosphane complexes.[15]
Table 2. Hydrogen bond geometries for 1, 2, 5 and 8 (lengths in A
and angles in degrees)
DϪH···A
d(DϪH) d(H···A) d(D···A) Є(DϪH···A)
[Au(Hpzbp2)(PPh3)](p-CH3C6H4SO3) (1)
N2ϪH2···O4
1.02
1.79
2.55
2.48
2.84
2.701(7) 147.2
C29ϪH29···O3[a] 0.93
C31ϪH31···O2[b] 0.93
C34ϪH34···O5[c] 0.93
3.39(1)
3.35(1)
3.43(1)
149.8
156.2
122.0
[Au(Hpzbp2)2](p-CH3C6H4SO3) (2)
N2ϪH2···O5
N4ϪH4···O6
0.99(9)
0.9(1)
1.72(9)
1.7(1)
2.51
2.70(1)
2.71(1)
3.39(2)
3.42(2)
174(8)
175(8)
158.4
146.9
The photoluminescence study of 1Ϫ3 in the solid state C4ϪH4A···O7[d] 0.93
C34ϪH34···O7[e] 0.93
2.61
shows that, under 325Ϫ330 nm UV irradiation, all of them
emit luminescence in the 440Ϫ510 nm range. For 1 this em-
ission occurs both at room temperature and 77 K, while for
2 and 3 this behaviour is only observed at low temperature.
The maximum-emission wavelengths are red-shifted by ca.
100 nm relative to the free pyrazole ligands.
[Ag(Hpzbp2)2]BF4 (5)
N2ϪH2···F1
N4ϪH4···F4
C7ϪH7···F3[f]
0.97
0.95
0.93
1.88
1.85
2.69
[Ag(HpzNO2)2](CF3SO3) (8)
N2ϪH2···O6
N5ϪH5···O7
0.93
0.92
1.85
1.95
2.771(3) 176.0
2.852(4) 165.9
Crystal Structure of 1
[a]
[b]
[c]
[d]
Ϫx, Ϫy ϩ 1, Ϫz ϩ 1. Ϫx, Ϫy ϩ 1, Ϫz ϩ 2. x ϩ 1, y, z.
[e]
[f]
The molecular structure of [Au(Hpzbp2)(PPh3)](p-
CH3C6H4SO3) (1) is depicted in Figure 1a, which also
shows the numbering scheme. Selected bond lengths and
angles and the hydrogen-bond parameters for all com- 177.1(2)° in 1, and 2.239(2), 2.077(5) A and 178.1(2)° in A].
pounds crystallographically characterized in this work are In addition, the cationic unit in both 1 and A is bonded to
Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 1. x Ϫ 1/2, Ϫy ϩ 1/2, z Ϫ 1/2. Ϫx,
Ϫy ϩ 1, Ϫz.
˚
collected in Table 1 and 2, respectively.
The structure of 1 consists of p-toluenesulfonate anions with N···O distances of 2.701(7) A (Table 2) and 2.764(9)
and cationic units where the gold() atom is two-coordinate. A, respectively.
the corresponding counterion by a strong hydrogen bond,
˚
˚
The coordinative environment (shape, AuϪP and AuϪN
However, when considering the packing arrangement in
distances, and PϪAuϪN angles) are, as expected, similar to the solid several differences are observed. A two-dimen-
those of the complex [Au(Hpzbp2)(PPh3)](NO3) (A), pre- sional structure was envisaged for A from weak intermolec-
viously reported by us,[10b] which contains the same cationic ular CϪH···O interactions of 3.31Ϫ3.38 A involving two of
˚
fragment and NO3Ϫ as counterion [Au1ϪP1, Au1ϪN1 and the oxygen atoms of the counterion, which were not impli-
P1ϪAu1ϪN1 bond parameters are 2.243(2), 2.069(5) A and cated in the previous hydrogen bond.[10b] In contrast, in 1
˚
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M. Cano et al.
FULL PAPER
the p-toluenesulfonate counterion forms a weak CϪH···O
˚
interaction at 3.39(1) A (Table 2) to produce a columnar
one-dimensional arrangement along the a axis (see b in Fig-
ure 1). These columns are also reinforced by the presence
of a new CϪH···O interaction between the O2 atom of the
substituent on the pyrazole ligand and the C31 atom of the
PPh3 ligand of
a neighbouring molecule (Table 2).
Throughout this one-dimensional distribution the gold
atoms are in a zig-zag disposition at a distance of 5.58(1)
˚
A, which excludes the presence of intermetallic interactions.
The above differences in the supramolecular architectures
are clearly dependent on the counterions. It can therefore
be suggested that the driving force of the reorientation of
cationic entities when the planar NO3Ϫ is substituted by the
bulkier p-toluenesulfonate could be related to the pseudo-
tetrahedral geometry of the SO3 group; interactions
through this group appear to preclude a layer-like distri-
bution.
However, this result does not exclude the possibility of
new contacts involving the remaining free oxygen atom of
the SO3 group (which was not used in the previous interac-
tions). In fact, the columns in 1 are connected to each other
˚
by very weak CϪH···O interactions at 3.43(1) A (Table 2).
At this point, it is important to mention that similar
weak CϪH···O contacts observed in a large variety of com-
pounds have been considered as support of the supramol-
ecular network.[9,16] On these basis, we propose for 1 that
the strong NϪH···O hydrogen bonds as well as the weak
CϪH···O inter- and intramolecular contacts through the
SO3 group of the counterion stabilize the crystal structure
in the solid state forming a two-dimensional network.
Crystal Structures of 2 and 5
The molecular structures of complexes 2 and 5 are rep-
resented in parts a of Figure 2 and 3, respectively. The
structures of the mononuclear cations [M(Hpzbp2)2]ϩ [M ϭ
Au (2), Ag (5)] show similar features. In both cases an angu-
lar molecular shape is formed by the two 3,5-disubstituted
pyrazole groups bonded through the pyridinic nitrogen to
the metal centre. In addition, each cationic unit has both
heterocycles in a cis-orientation and is bonded to its corre-
sponding counterion by two strong hydrogen bonds using
both NH groups and two of the oxygen or fluorine atoms
of the counterion, forming an eight-membered metallacycle
(OϪNϪNϪAuϪNϪNϪOϪS and FϪNϪNϪAgϪNϪNϪ
FϪB in 2 and 5, respectively). The molecules have a quasi-
linear NϪMϪN atomic sequence [176.3(4) in 2 and
˚
170.1(1)° in 5] and the average AuϪN (2.02 A) and AgϪN
˚
(2.12 A) lengths (Table 1) in 2 and 5, respectively, are simi-
lar to those found for related complexes containing pyra-
zole-type ligands.[10b,15b,15d,17Ϫ19] The main difference in
the molecular structure of 2 and 5 is related to the orien-
tation of the two pyrazole rings; they are almost parallel in
2 [dihedral angle of 4.5(5)°] but slightly tilted in 5 [dihedral
angle of 24.6(1)°]. Other dihedral angles are collected in
Table 3.
Figure 2. a) ORTEP plot of 2 at the 30% probability level; hydrogen
atoms, except H2 and H4, and the labelling of some atoms have
been omitted for clarity; b) view of the packing along the b axis
¯
showing the layer-like arrangement in the (1 0 2) direction; c) view
of the distribution in a layer
The crystal packing of 2 can be defined as layer-like (see razole)gold units bonded to its corresponding counterion.
¯
b in Figure 2), with the sheet containing the cationic bis(py- The layers are situated in the (1 0 2) direction. The cationic
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(Pyrazole)silver(I) and -gold(I) Complexes
FULL PAPER
Table 3. Dihedral angles (°) between selected planes[a] for 2 and 5
[Au(Hpzbp2)2](p-CH3C6H4SO3) (2) [Ag(Hpzbp2)2]BF4 (5)
1Ϫ2
1Ϫ3 35.8(4)
1Ϫ4 6.1(4)
3Ϫ4 35.8(4)
2Ϫ5 12.7(5)
2Ϫ6 20.1(5)
5Ϫ6 12.9(4)
4.5(5)
24.6(2)
39.9(2)
21.8(2)
61.5(2)
27.1(2)
3.6(2)
29.1(2)
[a] Plane 1: N1ϪN2ϪC3ϪC4ϪC5; plane 2: N3ϪN4ϪC6ϪC7ϪC8;
plane 3: C9ϪC10ϪC11ϪC12ϪC13ϪC14; plane 4: C19ϪC20Ϫ
C21ϪC22ϪC23ϪC24; plane 5: C29ϪC30ϪC31ϪC32ϪC33ϪC34;
plane 6: C39ϪC40ϪC41ϪC42ϪC43ϪC44.
entities in the layer adopt a head-to-tail alignment with no
short contacts between them (see c in Figure 2). However,
weak CϪH···O interactions between the layers are observed
which involve the free O7 atom of the counterion in a bifur-
cated form [C4···O7 (Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 1) of 3.39(2)
˚
˚
A; C34···O7 (x Ϫ 1/2, Ϫy ϩ 1/2, z Ϫ 1/2) of 3.42(2) A]
(Table 2). These weak intermolecular contacts form a one-
dimensional framework.
The crystal packing of 5 also presents similar character-
¯
istics, the layers being oriented in the (1 1 4) direction (see
b and c in Figure 3). Weak inter-layer interactions involving
Ϫ
the BF4 counterion are also observed for this complex.
These CϪH···F interactions [C7···F3 (Ϫx, Ϫy ϩ 1, Ϫz) of
˚
3.40(1) A] (Table 2) also form a one-dimensional frame-
work.
Crystal Structure of 8
The most relevant structure of complexes of the type
[M(HpzR)2]X is that of complex 8, where the pyrazole li-
gand is 3,5-dimethyl-4-nitropyrazole (HpzNO2) and X is
CF3SO3Ϫ. The structure of the cation [Ag(HpzNO2)2]ϩ is
shown in Figure 4 (see part a). The silver atom is coordi-
nated to the two pyridinic nitrogen atoms of the hetero-
˚
cyclic ligands at ca. 2.17 A (Table 1). The geometry around
the metal is distorted lineal with an N1ϪAg1ϪN4 angle of
163.67(9)°. Both pyrazole rings are almost parallel [angle of
4.8(1)°]. They show a cis orientation and are bonded
through strong hydrogen bonds to the counterion [N2···O6:
˚
˚
2.771(3) A; N5···O7: 2.852(4) A] (Table 2). The nitro groups
at the 4-position of the heterocyclic rings are almost co-
planar with their own pyrazole planes [dihedral angles of
5.1(2) °and 6.3(4)°]; as a consequence the molecule shows a
high planarity.
Figure 3. a) ORTEP plot of 5 at the 30% probability level; hydrogen
atoms, except H2 and H4, and the labelling of some atoms have
been omitted for clarity; b) view of the layer-like packing in the
¯
(1 1 4) direction; c) view of the distribution in a layer
The structure built by the strongest interactions can be
considered as that formed by dimers involving coordinative
interactions Ag1···O5(Ϫx ϩ 1, Ϫy ϩ 1, Ϫz ϩ 1) of 2.821(3) atoms of the nitro groups from two neighbouring mol-
˚
A between the oxygen atom of the counterion (not impli- ecules, which are not implicated in the same dimer, are
˚
˚
cated in the above hydrogen bond) and the silver centre of 3.268(4) A [N6···N6(Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 2)] and
each molecule, giving rise to a closest distance of the met- 3.168(6) A [O3···O3(Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 2)]. These are
˚
allic centres in the dimer of 3.7841(4) A (b in Figure 4).
remarkably short distances and show the existence of a π···π
The next step in the packing is due to π···π contacts be- interaction between those NO2 groups,[16eϪ16g] which are
tween dimers to form columns. The distances between situated in an alternating fashion. This mode of interaction
Eur. J. Inorg. Chem. 2004, 3089Ϫ3098
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3093

M. Cano et al.
FULL PAPER
Figure 4. a) ORTEP plot of 8 at the 30% probability level; hydrogen atoms, except H2 and H4, and the labelling of some atoms have
been omitted for clarity. b) View of the ‘‘dimeric unit’’ showing the close intermetallic approach. c) View of the two-dimensional network.
d) View of the packing along the c axis showing the herringbone-type distribution
gives rise to the formation of columns along the (1 0 1) di- or two-dimensional networks. Complex 1 is formed by self-
rection.
assembly of cationic [Au(Hpzbp2)(PPh3)]ϩ units and p-tolu-
Finally, the columns are bonded each other to give a two- enesulfonate counterions, providing linear polymeric chains
dimensional network which is extended parallel to the plane through NϪH···OϪSϪO···HϪC bridges containing both
¯
(1 0 1) by long-range coordinative Ag1···O1(x ϩ 1/2, Ϫy ϩ strong and weak hydrogen-bonding interactions. The ge-
˚
1/2, z ϩ 1/2) interactions at 2.978(3) A, produced between ometry of the p-toluenesulfonate counterion appears to be
an oxygen atom of a NO2 group, which is not implicated in responsible for the one-dimensional chain, which is differ-
the previously described π···π interactions, and the metal ent to the two-dimensional network produced by related in-
Ϫ
centre of neighbouring columns (c in Figure 4). This layer- teractions with the planar NO3 counterion. Therefore for
like supramolecular structure can also be described as a cationic complexes containing one pyrazole ligand the one-
herringbone-type arrangement of dimers connected dimensional supramolecular arrangement appears to be de-
through coordinative Ag···O interactions (d in Figure 4), termined not only by the hydrogen-bonding interactions
the dimers being almost orthogonal to the layer as deduced but also by the geometry of the counterion.
by the angle defined between the C2ϪC7 line and the a axis
of 77.01(3)°. No short interlayer distances are observed.
For complexes 2, 5 and 8, on the basis of the interactions
between the counterion and the two NH-pyrazolic groups
of each cationic unit, a polymeric chain was expected. How-
ever, the molecular conformation is responsible for a differ-
Concluding Remarks
The present work shows that Au/Ag complexes contain- ent assembly. In fact, in contrast to the observed trans dis-
ing pyrazole-type ligands are efficient in constructing one- position of the pyrazole groups found in the [Ag(HpzR2)2]ϩ
3094
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Eur. J. Inorg. Chem. 2004, 3089Ϫ3098

(Pyrazole)silver(I) and -gold(I) Complexes
FULL PAPER
ν˜ ϭ 3113 cmϪ1 ν(NϪH), 1614 ν(CϭN) ϩ ν(CϭC), 1174, 1162 and
compounds (HpzR2 ϭ pyrazole, 3,5-dimethylpyrazole),[17]
complexes 2, 5 and 8 present a cis orientation, which gives
1
1119 νd(SO3), 1007 νs(SO3). H NMR (300 MHz, CDCl3, 25 °C):
δ ϭ 1.00 (t, 6 H, CH3 Hpzbp2), 1.48Ϫ1.56 (m, 4 H, CH2 Hpzbp2),
1.75Ϫ1.82 (m, 4 H, CH2 Hpzbp2), 2.27 (s, 3 H, p-CH3C6H4SO3),
rise
to
[M(HpzR2)2]X
unities
containing
the
AϪNϪNϪMϪNϪNϪAϪB metallacycle (A ϭ donor
atom of the counterion; B ϭ central atom of the coun-
terion). The molecular assembly in 2 and 5 is therefore de-
termined by new, weak, intermolecular CϪH···O/F contacts
through the remaining O/F atoms of the counterion, its
geometry being responsible for the polymeric one-dimen-
sional network. Alternatively, an embracing effect of the
cations around the anions could also be considered as driv-
ing force for encapsulation.
3
3.97 (t, JH,H ϭ 6.6 Hz, 4 H, OCH2 Hpzbp2) 6.71 (s, 1 H, H4
Hpzbp2), 6.86 (d, 3JH,H ϭ 8.5 Hz, 4 H, Hm Hpzbp2), 6.95 (d, 3JH,H ϭ
7.9 Hz, 2 H, p-CH3C6H4SO3), 7.60Ϫ7.48 (m, 15 H, PPh3), 7.74 (d,
3
3JH,H ϭ 7.9 Hz, 2 H, p-CH3C6H4SO3), 7.79 (d, JH,H ϭ 8.5 Hz, 4
H, Ho Hpzbp2) ppm. 31P NMR (121.49 MHz, CDCl3, 25 °C): δ ϭ
31.06 (s) ppm.
Synthesis of [Au(Hpzbp2)2](p-CH3C6H4SO3) (2): A THF solution
(20 mL) of Hpzbp2 (116 mg, 0.32 mmol) was added to a solution of
[AuCl(THT)] (50 mg, 0.16 mmol) in dry THF (15 mL), and finally
a solution of silver() p-toluenesulfonate (44 mg, 0.16 mmol) in dry
THF (15 mL) was also added. After 24 h of stirring, the resulting
mixture was filtered through a plug of Celite and the obtained
A special behaviour has been found for 8. The presence
of the nitro group on the pyrazoles plays the most relevant
role in the formation of its polymeric architecture, which
adopts a two-dimensional, herringbone-type structure in- colourless clear filtrate was evaporated to dryness. The residue was
dissolved in dichloromethane and precipitated with hexane. X-ray
quality crystals were obtained by slow diffusion of hexane into a
dichloromethane solution of the product. C53H63AuN4O7S
(1097.1): calcd. C 58.02, H 5.79, N 5.11; found C 58.00, H 5.68, N
5.03. IR (KBr): ν˜ ϭ 3112 cmϪ1 ν(NϪH), 1613 ν(CϭN) ϩ ν(Cϭ
C), 1221, 1174 and 1124 νd(SO3), 1037 νs(SO3). 1H NMR
(300 MHz, CDCl3, 25 °C): δ ϭ 1.01 (m, 12 H, CH3 Hpzbp2).
1.46Ϫ1.60 (m, 8 H, CH2 Hpzbp2), 1.75Ϫ1.86 (m, 8 H, CH2 Hpzbp2),
volving both coordinative Ag···O and π···π interactions. The
extensive hydrogen-bonds between the counterions and the
cationic unities only determine the formation of dimers.
From the above results we can deduce that, in the absence
of coordinative NO2 groups as substituents on the pyrazole
rings, which appear to be determinant for supramolecular
interactions, the conformations of the complexes as well as
intermolecular orientations between them and the coun-
terions are responsible for the hydrogen-bonding contacts
involved in the molecular assembly.
3
2.38 (s, 3 H, p-CH3C6H4SO3), 3.98 (t, JH,H ϭ 6.5 Hz, 8 H, OCH2
3
Hpzbp2), 4.01 (t, JH,H ϭ 6.5 Hz, 8 H, OCH2 Hpzbp2), 6.71 (d,
3
4JH,H ϭ 2.0 Hz, 2 H, H4 Hpzbp2), 6.79 (d, JH,H ϭ 8.7 Hz, 4 H,
3
Hm Hpzbp2), 6.96 (d, JH,H ϭ 8.7 Hz, 4 H, Hm Hpzbp2), 7.21 (d,
3
3JH,H ϭ 7.8 Hz, 2 H, p-CH3C6H4SO3), 7.76 (d, JH,H ϭ 8.7 Hz, 4
3
H, Ho Hpzbp2), 7.79 (d, JH,H ϭ 8.7 Hz, 4 H, Ho Hpzbp2), 7.96
Experimental Section
3
(d, JH,H ϭ 7.8 Hz, 2 H, p-CH3C6H4SO3), 14.54 (br. s, 2 H, NH
Hpzbp2) ppm.
Materials and Instrumentation: All commercial reagents were used
as supplied. The ligands 3,5-bis(4-n-butoxyphenyl)pyrazole
Synthesis of [Au(Hpzbp2)2](NO3) (3): This compound was prepared
by the same method previously described for 2, from [AuCl(THT)]
(50 mg, 0.16 mmol), AgNO3 (27 mg, 0.16 mmol) and Hpzbp2
(116 mg, 0.32 mmol). C46H56AuN5O7 (987.96): calcd. C 55.92, H
5.71, N 7.09; found C 55.97, H 5.56, N 7.10. IR (KBr): ν˜ ϭ 3213
and 3141 cmϪ1 ν(NϪH), 1614 ν(CϭN) ϩ ν(CϭC), 1302 νas(NO3).
1H NMR (300 MHz, CDCl3, 25 °C): δ ϭ 1.02 (m, 12 H, CH3
Hpzbp2), 1.46Ϫ1.60 (m, 8 H, CH2 Hpzbp2), 1.78Ϫ1.83 (m, 8 H,
CH2 Hpzbp2), 3.99 (t, 3JH,H ϭ 6.5 Hz, 4 H, OCH2 Hpzbp2), 4.03 (t,
3JH,H ϭ 6.5 Hz, 4 H, OCH2 Hpzbp2), 6.75 (d, 4JH,H ϭ 1.9 Hz, 2 H,
(Hpzbp2 [20] and 3,5-dimethyl-4-nitropyrazole (HpzNO2 [21]
) as well
)
as the starting gold() derivatives [AuCl(THT))][11] and [Au(p-
CH3C6H4SO3)(PPh3)][8d] were prepared by literature procedures.
Commercial solvents were dried prior to use. Elemental analyses
for carbon, hydrogen and nitrogen were carried out by the Micro-
analytical Service of the Complutense University. IR spectra were
performed on a FTIR Nicolet Magna-550 spectrophotometer with
samples as KBr pellets in the 4000Ϫ400 cmϪ1 region. 1H and
31P{1H} NMR spectra were recorded on Varian VXR-300 or
Bruker DPX-300 spectrophotometers of the NMR Service of the
Complutense University, from solutions in CDCl3. Chemicals shifts
δ(H) are given in ppm relative to SiMe4, with the signal of the
deuterated solvent as reference, and δ(P) in ppm relative to 85%
H3PO4. Coupling constants (J) are in Hz. The 1H and 31P chemical
shifts and coupling constants are accurate to Ϯ0.01 ppm and
Ϯ0.3 Hz, respectively. Excitation and emission spectra of solid
samples placed in capillary tubes were recorded on a PerkinϪElmer
LS-55 luminescence spectrometer equipped with a R928 photomul-
tiplier tube.
3
H4 Hpzbp2), 6.84 (d, JH,H ϭ 8.9 Hz, 4 H, Hm Hpzbp2), 7.02 (d,
3
3JH,H ϭ 8.9 Hz, 4 H, Hm Hpzbp2), 7.77 (d, JH,H ϭ 8.9 Hz, 4 H,
3
Ho Hpzbp2), 7.80 (d, JH,H ϭ 8.9 Hz, 4 H, Ho Hpzbp2), 13.70 (br.
s, 2 H, NH Hpzbp2) ppm.
Synthesis of [Au(Hpzbp2)2]2(1,5nds) (1,5nds ؍ 1,5-naphthalenedisul-
fonate) (4): Ag2O (32 mg, 0.14 mmol) was added to an aqueous
solution (25 mL) of 1,5-naphthalenedisulfonic acid (50 mg,
0.14 mmol) with constant stirring until all the solids had dissolved.
Acetone was then added to this solution and the resulting white
precipitate was filtered off, dried and identified as silver 1,5-naph-
Synthesis of [Au(Hpzbp2)(PPh3)](p-CH3C6H4SO3) (1): Hpzbp2 thalenedisulfonate.
(18 mg, 0.05 mmol) was added to solution of [Au(p- Compound 4 was obtained by the same procedure described for 2,
a
CH3C6H4SO3)(PPh3)] (30 mg, 0.05 mmol) in freshly distilled THF from [AuCl(THT)] (38 mg, 0.12 mmol), silver 1,5-naphthalenedi-
(20 mL) and stirred for 24 h. The solvent was then removed in va-
cuo and the product was precipitated by addition of hexane/diethyl
ether. Slow diffusion of diethyl ether into a dichloromethane/di-
ethyl ether solution of this product gave colourless crystals suitable
sulfonate (60 mg, 0.12 mmol) and Hpzbp2 (87 mg, 0.24 mmol).
C102H118Au2N8O14S2 (2138.2): calcd. C 57.30, H 5.56, N 5.24;
found C 57.29, H 5.39, N 5.19. IR (KBr): ν˜ ϭ 3115 cmϪ1 ν(NϪH),
1612 ν(CϭN) ϩ ν(CϭC), 1178 νd(SO3), 1031 νs(SO3), 607 δs(SO3).
3
for crystallographic studies. C48H50AuN2O5PS (994.90): calcd. C 1H NMR (300 MHz, CDCl3, 25 °C): δ ϭ 0.93 (t, JH,H ϭ 7.3 Hz,
3
57.95, H 5.02, N 2.82; found C 57.90, H 5.05, N 2.79. IR (KBr):
12 H, CH3 Hpzbp2), 1.02 (t, JH,H ϭ 7.3 Hz, 12 H, CH3 Hpzbp2),
Eur. J. Inorg. Chem. 2004, 3089Ϫ3098
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3095

M. Cano et al.
FULL PAPER
1.41Ϫ1.58 (m, 16 H, CH2 Hpzbp2), 1.69Ϫ1.84 (m, 16 H, CH2
Synthesis of [Ag(Hpzbp2)2](CF3SO3) (6): This compound was pre-
pared in a similar way to 5, from AgCF3SO3 (21 mg, 0.08 mmol)
3
Hpzbp2), 3.91 (t, JH,H ϭ 6.5 Hz, 8 H, OCH2 Hpzbp2), 3.97 (t,
3JH,H ϭ 6.5 Hz, 8 H, OCH2 Hpzbp2), 6.70 (s, 4 H, H4 Hpzbp2), 6.79 and Hpzbp2 (60 mg, 0.16 mmol). The resulting white solid was puri-
3
3
(d, JH,H ϭ 8.7 Hz, 8 H, Hm Hpzbp2), 6.82 (d, JH,H ϭ 8.7 Hz, 8
fied by washing with dichloromethane. C47H56AgF3N4O7S
(985.92): calcd. C 57.26, H 5.73, N 5.68; found C 57.58, H 5.73, N
H, Hm Hpzbp2), 7.47 (t, 2 H, 1,5nds), 7.72 (d, 3JH,H ϭ 8.7 Hz, 8 H,
Ho Hpzbp2), 7.77 (d, JH,H ϭ 8.7 Hz, 8 H, Ho Hpzbp2), 8.44 (d, 5.62. IR (KBr): ν˜ ϭ 3227 cmϪ1 ν(NϪH), 1615 ν(CϭN) ϩ ν(Cϭ
3
3JH,H ϭ 6.5 Hz, 2 H, 1,5nds), 9.30 (d, 3JH,H ϭ 8.7 Hz, 2 H, 1,5nds),
C), 1226 νs(CF3), 1028 νs(SO3). 1H NMR (300 MHz, CDCl3, 25
14.53 (s, 4 H, NH Hpzbp2) ppm.
°C): δ ϭ 1.00 (t, JH,H ϭ 7.3 Hz, 12 H, CH3 Hpzbp2), 1.43Ϫ1.61
3
(m, 8 H, CH2 Hpzbp2), 1.73Ϫ1.87 (m, 8 H, CH2 Hpzbp2), 3.98 (br.
s, 8 H, OCH2 Hpzbp2), 6.69 (s, 2 H, H4 Hpzbp2), 6.70Ϫ7.00 (br. s,
Synthesis of [Ag(Hpzbp2)2](BF4) (5): AgBF4 (19 mg, 0.10 mmol) was
added under nitrogen to a solution of Hpzbp2 (71 mg, 0.20 mmol)
in dry THF (10 mL). After 24 h of stirring, the solvent was re-
moved in vacuo, giving rise to an oil from which a white solid
was isolated after addition of dichloromethane and pentane. This
product was crystallized by diffusion of hexane into a dichloro-
methane solution. C46H56AgBF4N4O4 (923.63): calcd. C 59.83, H
6.11, N 6.07; found C 59.64, H 6.10, N 5.94. IR (KBr): ν˜ ϭ 3308
cmϪ1 ν(NϪH), 1614 ν(CϭN) ϩ ν(CϭC), 1067 and 1037 ν(BF). 1H
3
8 H, Hm Hpzbp2), 7.63 (d, JH,H ϭ 8.0 Hz, 8 H, Ho Hpzbp2), 12.66
1
(s, 2 H, NH Hpzbp2) ppm. H NMR (300 MHz, CDCl3, Ϫ40 °C):
3
δ ϭ 0.95 (t, JH,H ϭ 6.9 Hz, 12 H, CH3 Hpzbp2), 1.39Ϫ1.51 (m, 8
H, CH2 Hpzbp2), 1.69Ϫ1.80 (m, 8 H, CH2 Hpzbp2), 3.83 (t, 3JH,H ϭ
3
5.1 Hz, 4 H, OCH2 Hpzbp2), 3.95 (t, JH,H ϭ 5.4 Hz, 4 H, OCH2
3
Hpzbp2), 6.67 (s, 2 H, H4 Hpzbp2), 6.69 (d, JH,H ϭ 8.7 Hz, 4 H,
3
Hm Hpzbp2), 6.95 (d, JH,H ϭ 8.7 Hz, 4 H, Hm Hpzbp2), 7.53 (d,
3JH,H ϭ 8.4 Hz, 4 H, Ho Hpzbp2), 7.61 (d, 3JH,H ϭ 8.4 Hz, 4 H, Ho
3
NMR (300 MHz, CDCl3, 25 °C): δ ϭ 1.00 (t, JH,H ϭ 7.3 Hz, 12
Hpzbp2), 12.54 (s, 2 H, NH Hpzbp2) ppm.
H, CH3 Hpzbp2), 1.40Ϫ1.60 (m, 8 H, CH2 Hpzbp2), 1.70Ϫ1.90 (m,
3
8 H, CH2 Hpzbp2), 3.99 (t, JH,H ϭ 6.6 Hz, 8 H, OCH2 Hpzbp2),
6.69 (s, 2 H, H4 Hpzbp2), 6.70Ϫ7.00 (br. s, 8 H, Hm Hpzbp2), 7.62
Synthesis of [Ag(HpzNO2)2](BF4) (7): AgBF4 (35 mg, 0.18 mmol)
was added under nitrogen to a solution of HpzNO2 (131 mg,
0.36 mmol) in dry acetonitrile (25 mL). After stirring for 24 h, the
3
(d, JH,H ϭ 8.8 Hz, 8 H, Ho Hpzbp2), 11.95 (s, 2 H, NH Hpzbp2
)
ppm. 1H NMR (300 MHz, CDCl3, Ϫ40 °C): δ ϭ 0.95 ppm (t,
3JH,H ϭ 7.2 Hz, 6 H, CH3 Hpzbp2), 0.96 (t, JH,H ϭ 7.2 Hz, 6 H, solvent was removed under vacuum to give an oil from which a
3
CH3 Hpzbp2), 1.40Ϫ1.51 (m, 8 H, CH2 Hpzbp2), 1.68Ϫ1.80 (m, 8 white solid was isolated after addition of dichloromethane and pen-
H, CH2 Hpzbp2), 3.86 (t, 3JH,H ϭ 6.6 Hz, 4 H, OCH2 Hpzbp2), 3.94 tane. C10H14AgBF4N6O4 (476.93): calcd. C 25.18, H 2.96, N 17.62;
3
(t, JH,H ϭ 6.6 Hz, 4 H, OCH2 Hpzbp2), 6.67 (s, 2 H, H4 Hpzbp2),
found C 25.34, H 2.97, N 17.72. IR (KBr): ν˜ ϭ 3175 cmϪ1
6.72 (d, 3JH,H ϭ 8.4 Hz, 4 H, Hm Hpzbp2), 6.95 (d, 3JH,H ϭ 8.7 Hz, ν(NϪH), 1595 ν(CϭN) ϩ ν(CϭC), 1506 νas(NO), 1363 νs(NO),
4 H, Hm Hpzbp2), 7.53 (d, 3JH,H ϭ 8.7 Hz, 4 H, Ho Hpzbp2), 7.60 (d,
1034 ν(BF). H NMR (300 MHz, CDCl3, 25 °C): δ ϭ 2.71 (s, 12
1
3JH,H ϭ 8.4 Hz, 4 H, Ho Hpzbp2), 11.86 (s, 2 H, NH Hpzbp2) ppm. H, CH3 HpzNO2), 11.67 (s, 2 H, NH HpzNO2) ppm.
Table 4. Crystal and refinement data for 1, 2, 5 and 8
1
2
5
8
Formula
C48AuH50N2O5PS
994.90
triclinic
¯
P1
11.264(1)
13.808(1)
14.633(1)
95.161(1)
101.889(1)
100.809(1)
2167.8(3)
2
C53H63AuN4O7S
1097.10
monoclinic
P21/n
11.518(1)
28.170(2)
16.315(1)
C46H56AgBF4N4O4
923.63
triclinic
¯
P1
9.1023(6)
14.576(1)
19.180(1)
111.201(1)
92.791(1)
105.387(1)
2257.7(3)
2
C11H14AgF3N6O7S
539.21
monoclinic
P21/n
8.8207(6)
18.165(1)
Mol. mass
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
12.3303(8)
α (°)
β (°)
γ (°)
106.830(2)
106.143(1)
3
˚
V (A )
5066.9(7)
4
1897.7(2)
4
Z
F(000)
1004
1.524
296(2)
3.527
2240
1.438
296(2)
2.999
960
1.359
296(2)
0.509
1072
1.887
296(2)
1.249
Dc (g cmϪ3
T (K)
)
µ(Mo-Kα) (mmϪ1
)
Crystal size (mm)
Scan technique
Data collected
θ (°)
0.35 ϫ 0.12 ϫ 0.04
ϕ and ω
0.32 ϫ 0.26 ϫ 0.12
ϕ and ω
0.37 ϫ 0.20 ϫ 0.15
ϕ and ω
0.38 ϫ 0.18 ϫ 0.12
ϕ and ω
(Ϫ14,Ϫ14,Ϫ19) to (14,18,19) (Ϫ12,Ϫ33,Ϫ14) to (13,33,19) (Ϫ10,Ϫ15,Ϫ22) to (10,17,17) (Ϫ8,Ϫ22,Ϫ15) to (11,20,13)
1.44Ϫ28.72
13974
1.45Ϫ25.00
26518
1.15Ϫ25.00
11769
2.05Ϫ26.37
10664
Refls. collected
Refls. indep.
9846 (Rint ϭ 0.072)
9846/0/527
5854
0.862
0.054
8933 (Rint ϭ 0.084)
8933/13/601
3716
0.856
0.048
7845 (Rint ϭ 0.030)
7845/16/545
4737
0.903
0.043
3870 (Rint ϭ 0.037)
3870/0/216
3068
1.031
0.033
Data, restraints, parameters
Refls. observed [(I) Ͼ 2σ(I)]
GOF (F2)
R(F)[a]
wR(F2) (all data)[b]
0.118
1.321
0.133
1.359
0.111
0.472
0.087
0.775
Ϫ3
˚
Largest residual peak (e·A
)
[a]
[b]
2
2 2
2 2
Σ(|Fo| Ϫ |Fc|)/Σ|Fo|. {Σ[w(Fo Ϫ Fc ) ]/Σ[w(Fo ) ]}1/2
.
3096
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 3089Ϫ3098

(Pyrazole)silver(I) and -gold(I) Complexes
FULL PAPER
Synthesis of [Ag(HpzNO2)2](CF3SO3) (8): The synthetic procedure
for 8 was analogous to that used for 5 from AgCF3SO3 (46 mg,
0.18 mmol) and HpzNO2 (51 mg, 0.36 mmol). Crystals were ob-
tained by the slow diffusion of hexane into a dichloromethane solu-
tion of the compound. C11H14AgF3N6O7S (539.21): calcd. C 24.50,
H 2.62, N 15.59; found C 24.57, H 2.59, N 15.57. IR (KBr): ν˜ ϭ
3205 and 3128 cmϪ1 ν(NϪH), 1600 ν(CϭN) ϩ ν(CϭC), 1509
νas(NO), 1366 νs(NO), 1252 νd(SO3), 1230 νs(CF3), 1040 νs(SO3).
1H NMR (300 MHz, CDCl3, 25 °C): δ ϭ 2.70 (s, 12 H, CH3
HpzNO2), 12.50 (s, 2 H, NH HpzNO2) ppm.
Angew. Chem. 1997, 109, 2421Ϫ2423; Angew. Chem. Int. Ed.
[1g]
Engl. 1997, 36, 2327Ϫ2329.
D. Braga, F. Grepioni, G. R.
[1h]
Desiraju, Chem. Rev. 1998, 98, 1375Ϫ1406.
D. Braga, F.
J. C. Mac-
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