Two hydrogen-bonded supramolecular frameworks of the 4,4′-diazido-2, 2′-stilbene disulfonate anion

Article abstract of DOI:10.1002/zaac.200500235

Two novel supramolecular frameworks, [Co(en)₃](dasb)(ClO ₄)·H₂O (1) and [Ni(en)₂(H ₂O)₂](dasb) (2), constructed by 4,4′-diazido-2, 2′-stilbenedisulfonate anion (dasb)^2- through w

Full text of DOI:10.1002/zaac.200500235

Two Hydrogen-bonded Supramolecular Frameworks of the
4,4Ј-Diazido-2,2Ј-stilbene Disulfonate Anion
Yanqin Wang, Rong Cao*, Wenhua Bi, Xing Li, Xiaoju Li, and Yuling Wang
Fuzhou, Fujian/China, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences
Received May 20th, 2005.
Abstract.
Two
novel
supramolecular
frameworks,
with the coordinated en and water molecules as H-bond acceptor
and the components were connected by the hydrogen bonds into
3D networks.
[Co(en)3](dasb)(ClO4)·H2O (1) and [Ni(en)2(H2O)2](dasb) (2), con-
structed by 4,4Ј-diazido-2,2Ј-stilbenedisulfonate anion (dasb)2Ϫ
through weak interactions, have been synthesized and characterized
by single crystal X-ray diffraction. As expected, in the two struc-
tures sulfonate groups of the anion form strong hydrogen bonds
Keywords: Hydrogen bond; Supramolecule; Sulfonate anion
˚
Hydrogen-bonded supramolecular frameworks have attracted ex-
treme interests for their significance in chemistry and biology [1].
In chemistry, knowledge of hydrogen bond is extremely important
in the fields of crystal engineering [2]. Much work has been done in
identifying commonly occurring H-bonding motifs [3], often called
synthons, which could be used to construct desired crystal assembl-
ies [4]. Among the supramolecular synthons, sulfonate hydrogen-
bonding synthon is important one. Because of the weak coordi-
nation ability of sulfonate toward transition metal ions, most of the
reported transition metal-sulfonate complexes prepared in aqueous
solution were formed by segregation of aquametal complex cations
and sulfonate anions [5]. Previous research has shown that the
(RSO3)Ϫ anions are good hydrogen-bond acceptors and can form
strong hydrogen bonds and even hydrogen-bonded networks with
H-donors [6]. Even though much work has been done for the coor-
dination polymers of sulfonate ligands [7], the study for weak inter-
actions attracts much less attention of chemists [8]. Recently, Shim-
izu and co-workers [9] synthesized two complexes which form pil-
lared layered structures and include guest molecules. The networks
are sustained by charge-assisted hydrogen bonding and show two
different assembly motifs, one based on the complementarity of the
edges of the triangular triamine faces with sulfonate groups, and
the other on hydrogen-bond complementarity with the centroids of
the triangular faces.
Table 1 Selected bond lengths /A and angles /° for 1
Co(1)-N(16)
Co(1)-N(17)
Co(1)-N(9)
Co(1)-N(14)
Co(1)-N(11)
Co(1)-N(7)
N(16)-Co(1)-N(17)
N(16)-Co(1)-N(9)
N(17)-Co(1)-N(9)
N(16)-Co(1)-N(14)
N(17)-Co(1)-N(14)
1.903(9)
1.914(9)
1.959(9)
1.981(10)
1.987(9)
2.002(9)
88.0(4)
92.6(4)
93.2(4)
93.5(4)
N(9)-Co(1)-N(14)
N(16)-Co(1)-N(11)
N(17)-Co(1)-N(11)
N(9)-Co(1)-N(11)
N(14)-Co(1)-N(11)
N(16)-Co(1)-N(7)
N(17)-Co(1)-N(7)
N(9)-Co(1)-N(7)
N(14)-Co(1)-N(7)
N(11)-Co(1)-N(7)
172.9(4)
90.8(4)
174.7(4)
91.9(4)
84.4(4)
175.7(4)
93.0(4)
83.2(4)
90.6(4)
88.6(4)
90.6(4)
guanidinium cation and could possibly form highly complementary
hydrogen-bond pairs with sulfonate anions [10, 11]. So, we adopt
ethylenediamine coordination complexes as building blocks to as-
semble with (dasb)2Ϫ anion. As expected, two supramolecular
frameworks, [Co(en)3](dasb)(ClO4)·H2O (1) and [Ni(en)2(H2O)2](d-
asb) (2), were isolated. To the best of our knowledge, they are the
first two supramolecular compounds constructed from (dasb)2Ϫ
anion.
The two compounds were obtained as crystals by the reaction of
disodium salt of 4,4Ј-diazido-2,2Ј-stilbenedisulfonate (dasb)2Ϫ
,
ethylenediamine (en) and metal chlorides in H2O/CH3CH2OH at
room temperature. They were prepared in almost the same con-
ditions, but HClO4 was used in the preparation of 1 and the ratio
of metal salt and en is 1:3 in 1 and 1:2 in 2.
In the present work, we choose 4,4Ј-diazido-2,2Ј-stilbenedisulfon-
ate anion (dasb)2Ϫ as research object based on the following con-
siderations: (1) the anion contains two sulfonate groups and can be
good hydrogen-bond acceptors; (2) the benzene rings can form π-
π stacking and C-H···π interactions to stabilize the resulted struc-
tures, and (3) the diazido groups can be weak hydrogen-bond ac-
ceptors since its resonance is electronegative. On the other hand,
ethylenediamine metal complex can provide divergent N-H bonds
to act as hydrogen-bond donors. Thus, it would be similar to a
X-ray diffraction analyses show that in the two compounds,
(dasb)2Ϫ anion does not coordinate to metal atoms but connects
metal centers to form supramolecular frameworks through weak
interactions as a building block. Selected bond lengths and angles
of 1 and 2 are listed in table1 and 2, respectively.
In compound 1, with the presence of (ClO4)Ϫ, CoII in the starting
material was oxidated to CoIII. Compound 1 consists of five inde-
pendent subunits: [Co(en)3]3ϩ cation, two (dasb)2Ϫ anions, (ClO4)Ϫ
and a free water molecule. Each Co3ϩ ion is coordinated by three
en molecules in octahedral coordination. In an asymmetry unit of
1, there are two (dasb)2Ϫ ligands, and they are packed together to
be a sheet through edge-to-face aromatic C-H···π and face-to-face
π-π stacking interactions. The distance between the aromatic ring
* Prof. Rong Cao
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences
Fuzhou, Fujian 350002 / China
Tel.: ϩ86-591-83796710; Fax: ϩ86-591-83714946
E-mail: rcao@ms.fjirsm.ac.cn
center in (dasb)2Ϫ and H6 is 3.35(3) A (Figure 1). The vertical dis-
˚
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DOI: 10.1002/zaac.200500235
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Y. Wang, R. Cao, W. Bi, X. Li, X. Li, Y. Wang
˚
Table 2 Selected bond lengths /A and angles /° for 2
Ni(1)-N(2)
2.078(4)
2.078(4)
2.090(3)
2.090(3)
2.112(3)
2.112(3)
1.455(3)
1.457(3)
1.457(3)
180.00(13)
96.32(14)
83.68(14)
N(2)-Ni(1)-N(1)
83.68(14)
96.32(14)
180.000(1)
93.44(14)
86.56(14)
88.37(13)
91.63(13)
86.56(14)
93.44(14)
91.63(13)
88.37(13)
180.000(1)
Ni(1)-N(2)#1
Ni(1)-N(1)#1
Ni(1)-N(1)
Ni(1)-O(5)#1
Ni(1)-O(5)
S(2)-O(1)
S(2)-O(2)
S(2)-O(3)
N(2)#1-Ni(1)-N(1)
N(1)#1-Ni(1)-N(1)
N(2)-Ni(1)-O(5)#1
N(2)#1-Ni(1)-O(5)#1
N(1)#1-Ni(1)-O(5)#1
N(1)-Ni(1)-O(5)#1
N(2)-Ni(1)-O(5)
N(2)#1-Ni(1)-O(5)
N(1)#1-Ni(1)-O(5)
N(1)-Ni(1)-O(5)
N(2)-Ni(1)-N(2)#1
N(2)-Ni(1)-N(1)#1
N(2)#1-Ni(1)-N(1)#1
Figure 1 CH-π and π-π stacking interactions in complex 1
O(5)#1-Ni(1)-O(5)
Symmetry transformations used to generate equivalent atoms:
#1: Ϫxϩ1,Ϫyϩ1,Ϫzϩ1.
Figure 2 Packing diagram of compound 1 along the b axis (Hydro-
gen bonding was omitted because of the disorder of N atoms in en.)
Figure 3 The sheet in complex 2 vertical to the b axis
tance between two neighboring benzene rings of (dasb)2Ϫ is
˚
˚
2.003(4) A and the centroid-centroid distance is 4.368(2) A. The
dihedral angle of the two rings is 11.9(3)°. Between two sheets, the
[Co(en)3]3ϩ cations and the perchlorate anions are included and
extend the structure into a three-dimensional framework through
hydrogen bonding (figure 2). However, because of the disorder of
the nitrogen atoms of en, the positions of hydrogen atoms on them
are uncertain, so detailed discussion on the hydrogen-bonding from
en will not be made here.
The results of TGA illustrate that compound 1 loses the free water
molecule (found 2.13 %, calc. 2.32 %) first at 71 °C and loses the
coordinated en molecules (found 22.12 %, calc. 23.16 %) later at
177 °C. However, compound 2 loses the en molecules (found
17.73 %, calc. 18.89 %) first at 126 °C and then loses the water
molecules (found 5.41 %, calc. 5.67 %) at 211.7 °C. This may be
attribute to the structure difference of the two compounds. In 2,
water molecules not only coordinate to metal center but also form
strong hydrogen bonding with (dasb)2Ϫ ligand; however, en mol-
ecules only form very weak hydrogen bonding with the (dasb)2Ϫ
anions. The backbone of 1 and 2 collapsed at 306 °C and 332 °C,
respectively.
Compound
2 is made up of two building blocks: the
[Ni(en)2(H2O)2]2ϩ cation and the (dasb)2Ϫ anion. In this com-
pound, NiII is coordinated by two en molecules and two water mol-
ecules in a distorted octahedron. The [Ni(en)2(H2O)2]2ϩ cation lo-
cates on the two-fold axis. As expected, there are intramolecular
hydrogen bonds between the cation and the sulfonate anion. The
sulfonate group forms three kinds of hydrogen bonds accepting
three protons, two from the coordinated water molecules and one
from en N-H group, respectively. The average donor-acceptor dis-
In conclusion, two novel supramolecular frameworks of 4,4Ј-diaz-
ido-2,2Ј-stilbenedisulfonate anion were rationally designed and
synthesized. Single crystal X-ray diffraction indicates that the two
compounds are 3D networks constructed through weak interac-
tions. They are the first two supramolecular compounds of the
(dasb)2Ϫ anion so far and have some interest as additional ex-
amples of crystal engineering of supramolecular structures.
˚
tance of the three H-bonds is 2.870(4) A and the average angle of
donor-H···acceptor is 173.2°. The three hydrogen bonds connect
the two building blocks into a sheet vertical to the b axis, as shown
in Figure 3. Furthermore, the sulfonate O3 forms an accepting hy-
drogen bond with C-H from another [Ni(en)2(H2O)2]2ϩ cation and
the diazido N3 atom forms an accepting hydrogen bond with N-H
from the next sheet. The O3···C8 and N3···N2 distances of 3.430(3)
Experimental Section
˚
and 3.205(5) A, are comparatively long and the C8-H8B···O3 and
N2-H2B···N3 angles of 143.3 and 133.3° are much more acute than
the usual range of 160-180° for strong hydrogen bonds [12], indicat-
ing that the two hydrogen bonds are very weak. Just through the
two weak hydrogen bonds, the sheets are packed together to be a
3D framework.
Synthesis of 1 and 2: Compound 1 was prepared as following.
1 mol/L aqueous solution HClO4 was added dropwise into the mix-
ture of dehydrated CoCl2 0.130 g (1.0 mmol) and 3.0 mmol ethylen-
ediamine (en) in 10 mL ethanol, deposition was observed and dis-
appeared gradually. To the resulted brown solution, 10 mL aqueous
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zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2309Ϫ2311

Supramolecular Frameworks of the 4,4Ј-Diazido-2,2Ј-stilbene Disulfonate Anion
0.447 g (1.0 mmol) Na2dasb was added with stirring. The resulted
solution was allowed to evaporate at room temperature. A few days
later, deep red prism crystals were obtained in yield of 67.5 %. El-
emental analysis for C20H33CoN12O7S2·ClO4 (776.06): Calcd: C ϭ
30.91, H ϭ 4.41, N ϭ 21.63. Found: C ϭ 31.55, H ϭ 4.46, N ϭ
21.57 %. IR (KBr, cmϪ1): 3508-3400(m), 3255-3099(s), 2114(vs),
1597(m), 1487(m), 1296(s), 1209(s), 1157(s), 1078(s), 1022(s),
827(w), 627(s), 544(m).
Province (B982003), and the “One Hundred Talent” project from
CAS.
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Compound 2 was prepared with the same procedure except that
HClO4 was not used and the ratio of NiCl2 and en was changed
to 1:2. Orange prism crystals of 2 were collected in yield of 76.4 %.
Elemental analysis for C18H28N10NiO8S2 (635.29): Calcd: C ϭ
34.03, H ϭ 4.44, N ϭ 22.05. Found: C ϭ 33.88, H ϭ 4.64, N ϭ
21.11 %. IR (KBr, cmϪ1): 3357-3277(s), 2114(vs), 1599(s), 1485(s),
1298(s), 1192(vs), 1080(s), 1020(s), 901(w), 820(w), 625(s), 544(m).
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Thermogravimetric analyses (TGA) were performed from 30 to
1000 °C in N2 using a Netzsch STA449C analyzer at a heating rate
of 15 °C/min. IR spectra were recorded on a Magna 750 FT-IR
spectrophotometer as KBr pallets.
The intensity data of 1 and 2 were collected on a Rigaku CCD
diffractometer with graphite-monochromatized Mo-KͰ radiation
˚
(λ ϭ 0.71073 A) at 173 K. The absorption correction was per-
formed using the CrystalClear [13] program. The structures were
solved by direct methods and refined on F2 by full-matrix least-
squares using the SHELXTL-97 program package [14]. CCDC
numbers: 261634 for 1 and 261635 for 2. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB21EZ (FAX: [ϩ44]1223-336-033; E-mail: deposit@-
ccdc.cam.ac.uk).
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Crystal data for C20H34CoN12O7S2ClO4 (1), monoclinic, P21/c, a ϭ
˚
16.737(14), b ϭ 7.479(6), c ϭ 28.175(17) A, β ϭ 122.87(3)°, V ϭ
3
3
˚
2962(4) A , Z ϭ 4, Dc ϭ 1.740 g/cm , 17691 reflections collected,
5204 unique (Rint ϭ 0.0447). Final GooF ϭ 1.106, R1 ϭ 0.0738,
wR2 ϭ 0.1895 with I > 2σ(I). C18H28N10NiO8S2 (2), monoclinic,
˚
[12] J. D. Crane, D. J. Moreton, E. Rogerson, Eur. J. Inorg. Chem.
P21/c, a ϭ 6.7818(8), b ϭ 15.3370(17), c ϭ 12.5266(15) A, β ϭ
3
3
˚
2004, 4237.
104.739(5)°, V ϭ 1260.0(3) A , Z ϭ 4, Dc ϭ 1.675 g/cm , 7880 re-
flections collected, 2215 unique (Rint ϭ 0.0534). Final GooF ϭ
1.097, R1 ϭ 0.0485, wR2 ϭ 0.0996 with I > 2σ(I).
[13] Molecular Structure Corporation Rigaku, 2000. CrystalClear.
Version 1.36. MSC, 9009 New Trails Drive, The Woodlands,
TX 77381-5209, USA, and Rigaku Corporation, 3-9-12 Aki-
shima, Tokyo, Japan.
Acknowledgments. We are grateful to the financial support from
NNSF of China (90206040, 20325106, 20333070), NSF of Fujian
[14] G. M. Sheldrick, SHELXS-97, University of Göttingen, 1997.
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