Two novel flexible multidentate ligands for crystal engineering: Syntheses, structures, and properties of CuII, MnII complexes with N-[(3-carboxyphenyl)-sulfonyl]glycine and N,N′-(1,3-phenylenedisulfonyl) bis(glycine)

Article abstract of DOI:10.1002/ejic.200700847

One novel N-[(3-carboxyphenyl)sulfonyl]glycine (H₃L¹) ligand (1) was prepared in high yield, and its structure was determined by single-crystal X-ray diffraction. Reaction of H₃L¹ with Mn(ClO₄)₂·6H₂O at different pH values gave two new dinuclear complexes: [Mn₂(HL¹) ₂(phen)₄]·16H₂O (2) and [Mn ₂L¹(phen)₄(H₂O)]ClO ₄·3H₂O (3) (phen = 1,10-phenanthroline). Additionally, two copper(II) complexes, [K₂Cu(L²) ₂-(H₂O)₂]_n (4) and [CuL ²(H₂O)]₂·2H₂O (5), involving another novel ligand, N,N′-(1,3-phenylenedisulfonyl)bis(glycine) (H ₂L²), were prepared by a one-pot reaction of 1,3-phenylenebis(sulfonyl chloride), glycine, and KOH or triethylamine in the presence of Cu^II ions. A self-assembled (H₂O)₃₀ cluster containing a puckered (H₂O)₁₂ ring core was found in 2, which presents a new mode of association of water molecules not predicted theoretically or previously observed experimentally. Furthermore, 2 forms a 2-D supramolecular structure through hydrogen bonding and unique π-π stacking interactions. In 3, there also exist discrete trimeric water clusters. The identity of the base determines the specific structural characteristics of 4 and 5. When potassium hydroxide was used for the synthesis of 4, it led to a 3-D copper(II)-potassium(I) coordination polymer; when triethylamine was used, paddle-wheel dinuclear units of copper(II) carboxylate were produced. Magnetic measurements show that there are weak antiferromagnetic interactions in 2-4. In 5 the χ_MT vs. T curve shows a minimum at 110 K and a climb from 110 K to 5 K, then a long-range antiferromagnetic ordering occurs, as revealed by a decrease in χ_MT with T. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200700847

FULL PAPER
DOI: 10.1002/ejic.200700847
Two Novel Flexible Multidentate Ligands for Crystal Engineering: Syntheses,
Structures, and Properties of CuII, MnII Complexes with N-[(3-Carboxyphenyl)-
sulfonyl]glycine and N,NЈ-(1,3-Phenylenedisulfonyl)bis(glycine)
Lu-Fang Ma,[a,b] Yao-Yu Wang,*[a] Li-Ya Wang,*[b] Jian-Qiang Liu,[a] Ya-Pan Wu,[a]
Jian-Ge Wang,[b] Qi-Zhen Shi,[a] and Shie-Ming Peng[c]
Keywords: N-[(3-Carboxyphenyl)sulfonyl]glycine / N,NЈ-(1,3-Phenylenedisulfonyl)bis(glycine) / Magnetic properties / Com-
plexes / Crystal engineering
One novel N-[(3-carboxyphenyl)sulfonyl]glycine (H3L1) li-
gand (1) was prepared in high yield, and its structure was
determined by single-crystal X-ray diffraction. Reaction of
H3L1 with Mn(ClO4)2·6H2O at different pH values gave two
new dinuclear complexes: [Mn2(HL1)2(phen)4]·16H2O (2) and
mentally. Furthermore, 2 forms a 2-D supramolecular struc-
ture through hydrogen bonding and unique π–π stacking in-
teractions. In 3, there also exist discrete trimeric water clus-
ters. The identity of the base determines the specific struc-
tural characteristics of 4 and 5. When potassium hydroxide
[Mn2L1(phen)4(H2O)]ClO4·3H2O (3) (phen = 1,10-phenan- was used for the synthesis of 4, it led to a 3-D copper(II)–
throline). Additionally, two copper(II) complexes, [K2Cu(L2)2-
(H2O)2]n (4) and [CuL2(H2O)]2·2H2O (5), involving another
novel ligand, N,NЈ-(1,3-phenylenedisulfonyl)bis(glycine)
(H2L2), were prepared by a one-pot reaction of 1,3-phenyl-
enebis(sulfonyl chloride), glycine, and KOH or triethylamine
in the presence of CuII ions. A self-assembled (H2O)30 cluster
containing a puckered (H2O)12 ring core was found in 2,
which presents a new mode of association of water molecules
not predicted theoretically or previously observed experi-
potassium(I) coordination polymer; when triethylamine was
used, paddle-wheel dinuclear units of copper(II) carboxylate
were produced. Magnetic measurements show that there are
weak antiferromagnetic interactions in 2–4. In 5 the χMT vs.
T curve shows a minimum at 110 K and a climb from 110 K
to 5 K, then a long-range antiferromagnetic ordering occurs,
as revealed by a decrease in χMT with T.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
properties.[3] In these reports, most of the bridging ligands
used in the construction of the frameworks are rigid, be-
cause the carboxylate groups in these ligands are attached
to the central aromatic ring directly. However, significantly
fewer studies on the coordination chemistry of flexible car-
boxylate-containing ligands have been carried out, possibly
because of the difficulties in predicting the structures of the
resulting complexes.[4] Now, searching for this kind of ver-
satile polycarboxylato ligands is very important and de-
serves attention in the investigation of new topologies and
various functional materials.
Introduction
Crystal engineering of coordination polymers and supra-
molecules have attracted a lot of attention because of their
potential as functional materials, as well as their intriguing
compositions and topologies.[1] A successful strategy in
building such networks is to employ appropriate bridging
ligands that can bind metal ions in different modes and pro-
vide a possible way to achieve more robust polymeric struc-
tures.[2] In this context, benzenedicarboxylic acid and its
derivatives (such as 1,3-benzenedicarboxylic acid, 1,4-
benzenedicarboxylic acid, 5-hydroxyisophthalic acid) are
widely used as building blocks to link metal ions to produce
metal–organic frameworks with interesting structures and
Recently, we introduced a versatile ligand, N-(phenylsul-
fonyl)--glutamic acid, to construct various coordination
polymers in which N-(phenylsulfonyl)--glutamic acid op-
ens up the possibility to obtain structures with different
[a] Key Laboratory of Synthetic and Natural Functional Molecule kinds of carboxylato bridges.[5] The interesting results in-
Chemistry of the Ministry of Education (Shaanxi Key Labora-
spired us to investigate its analogues, N-[(3-carboxyphenyl)-
tory of Physico-Inorganic Chemistry), Department of Chemis-
sulfonyl]glycine and N,NЈ-(1,3-phenylenedisulfonyl)bis(gly-
cine) (Scheme 1), for the following reasons: (1) both of the
ligands contain two bridging carboxylato moieties, which
can lead to a variety of connection modes with metal cen-
ters and provide abundant structural motifs; (2) they can
act as not only hydrogen-bond acceptors but also hydrogen-
bond donors, which make them excellent candidates for the
try, Northwest University,
Xi’an, Shaanxi 710069, P. R. China
E-mail: wyaoyu@nwu.edu.cn
[b] Department of Chemistry, Luoyang Normal University,
Luoyang, Henan 471022, P. R. China
[c] Department of Chemistry, National Taiwan University,
Taipei, Taiwan
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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Scheme 1.
construction of supramolecular networks; (3) they possess
With the aim of understanding the coordination chemis-
two other potential groups in addition to benzenedicarbox- try of N,NЈ-(1,3-phenylenedisulfonyl)bis(glycine) and N-[(3-
ylic acids, i.e., the nitrogen atoms and oxygen atoms of sul- carboxyphenyl)sulfonyl]glycine and preparing new materi-
fonyl groups, which are good candidates to produce unique als with interesting structures and excellent physical proper-
structural motifs with aesthetics and useful functional prop- ties, we have recently engaged in the research of metal com-
erties; (4) they are flexible: N,NЈ-(1,3-phenylenedisulfonyl)- plexes with these two ligands. The two ligands can be
bis(glycine) can freely rotate with certain spacers to meet viewed either as sulfonamide derivatives or as N-substituted
the requirement of coordination geometries of metal ions in amino acids, and were expected to stabilize water clusters
the assembly process. In addition, the N-[(3-carboxyphen- with their biologically relevant functional moieties. Herein,
yl)sulfonyl]glycine ligand not only has one rigid carboxy we report the syntheses, structures, and properties of
group affixed to the aromatic ring but also extends one flex- H3L1·H2O (1) and its two dinuclear MnII complexes,
ible carboxy group from its glycine moiety. This asymmetric [Mn2(HL1)2(phen)4]·16H2O (2) and [Mn2L1(phen)4(H2O)]-
geometry may lead to acentric crystal structures.
ClO4·3H2O (3), and two new copper(II) complexes,
Recently, intense experimental and theoretical studies [K2Cu(L2)2(H2O)2]n (4) and [CuL2(H2O)]2·2H2O (5). Inter-
have focused on unraveling structural morphologies of estingly, an unprecedented (H2O)30 cluster consisting of a
water clusters to understand the nature of water–water in- basic puckered 12-membered ring fused with six dangling
teractions in bulk water or ice, probing its possible roles in trimeric water clusters was stabilized by 2.
the stabilization and functioning of biomolecules and in the
design of new materials.[6] Structural studies on discrete
water clusters within the lattice of a crystal host have signif-
icantly advanced our knowledge toward the first step of un-
Results and Discussion
derstanding the behavior of bulk water. Until now, a
Syntheses
number of different discrete water clusters, namely tetra-
meric,[7] hexameric,[8] octameric,[9] decameric,[10] undeca-
(Phenylsulfonyl)amino acids were usually prepared in
meric,[11] dodecameric,[12] tetradecameric,[6f] hexadeca- two steps: reaction of starting materials and then acidifica-
meric,[13] and heptadecameric[14] clusters have been struc- tion.[19] The ligand N-[(3-carboxyphenyl)sulfonyl]glycine
turally characterized and assigned different conformations. was synthesized in aqueous solution, and the reaction could
However, the units in these clusters are all small water clus- be accomplished within 2 h. The product could be handled
ters. The investigation of larger water aggregates is still a easily by using hydrochloric acid, and the yield was above
challenge in this field, although several examples of larger 60%. A reaction of Mn(ClO4)2·6H2O, H3L1, and phen at
water clusters have been reported in crystal hosts very re- 70 °C at different pH values produced yellow crystals of 2
cently. Notable examples are a discrete large protonated and 3. In 2, (HL1)2– behaves just as a simple carboxylato
water cluster, H+(H2O)27, in a 3-D metal–organic frame- group coordinated to the metal ions, and the sulfonamide
work, and the formation of an infinite 2-D layer of a nitrogen atom is free from coordination, whereas in 3, as
(H2O)45 cluster in a cryptand–water supramolecular com- the pH value increases, it switches to an N,O-bidentate che-
pound.[15] Chen and co-workers also reported an unprece- lating ligand because of the environment of the deproton-
dented (H2O)32 water cluster containing a central cyclic ated amide nitrogen atom as an additional donor site.
(H2O)4 in a Cd complex containing succinic acid (H2adi)
Unfortunately, when the reaction solution of 1,3-phenyl-
and N,NЈ-bis(picolinamide)azine (bpa) ligands: {[Cd2(bpa)2- enebis(sulfonyl chloride), glycine, and KOH was acidified
(adi)2]·11H2O}n.[16] These studies provide novel structural to pH = 4 with 6  hydrochloric acid, no precipitates were
aspects of and new insights into water with implications in obtained. In attempts to seek an efficient synthesis, we
the biological environment. Moreover, organic compounds found that a one-pot method with 1,3-phenylenebis(sulfonyl
with functional groups similar to those present in biological chloride), glycine, Cu(OAc)2·2H2O, and KOH or triethyl-
molecules can stabilize water clusters of different sizes and amine in water could produce complexes 4 and 5 of this
shapes in environments resembling those in living sys- ligand. In addition, the same reaction was carried out with
tems.[17] The glycine–water complex provides the simplest different salts of Ni, Mn, Co, Zn, and Cd. However, no
molecular model of biologically important amino acid– complexes in crystalline form suitable for an X-ray study
water interactions and represents the initial step of the hy- were obtained, which indicates that the copper(II) ion is an
dration process.[18]
effective template for synthesizing this ligand.
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Two Novel Flexible Multidentate Ligands for Crystal Engineering
Crystal Structures
and oxygen atoms from the N-protected amino acid motif
to afford a 3-D supramolecular structure (O···O distance:
2.573 Å).
Crystal Structure of 1
The structure of H3L1·H2O was determined by IR spec-
troscopy, elemental analysis, and single-crystal X-ray struc-
ture analysis. The IR spectra of H3L1·H2O exhibit several
Crystal Structure of 2
The structure analysis shows that the two MnII ions in 2
characteristic strong bands. The band observed at are both six-coordinate with a distorted octahedral geome-
3285 cm–1 is attributed to the N–H stretching vibration, try, as shown in Figure 3. The six atoms coordinated to
while those at 1337 and 1171 cm–1 are due to νas(–SO2–) each MnII ion come from four nitrogen atoms of two chelat-
and νs(–SO2–) in H3L1·H2O, respectively. The strong ab- ing phenyl groups and one oxygen atom of the COO– group
sorptions at 1709 and 1441 cm–1 are attributed to the asym- of benzoic acid, as well as one oxygen atom of the N-sul-
metric stretching vibration νas(COO–) and the symmetric fonylglycine group. The Mn–O bond lengths are both
νs(COO–) vibration, respectively. The structure of 2.124(3) Å, and the Mn–N bond lengths are in the range
H3L1·H2O, which was further confirmed by X-ray diffrac- 2.266(4)–2.342(3) Å, which are in the normal range of
tion techniques, is shown in Figure 1. Both of the carboxyl- lengths observed in manganese(II) carboxylate complexes
ate groups are protonated. There are intermolecular hydro- containing 2,2Ј-bipy or 1,10-phen. The Mn1 and Mn1A
gen bonds between carboxylate oxygen atoms from the ions are linked together to form a dinuclear unit where
C6H5COO– motif (O···O distance: 2.630 Å) and hydrogen (HL1)2– acts as the bridging ligand. The two phen molecules
bonds between carboxylate oxygen atoms from the amino are almost perpendicular with an intersecting angle of
acid motif and the lattice water molecules (O···O distances: 99.7°.
2.837 and 2.823 Å, respectively), forming 1-D hydrogen-
Eight crystallographically unique free water molecules
bonding chains in which six-membered-ring and eight- are observed in the unit of 2, in which five water molecules
membered-ring units are alternately arranged along the c form a (H2O)30 cluster associated by O–H···O hydrogen
axis. These chains are assembled by hydrogen bonds be- bonds as shown in Figure 4a. The (H2O)30 cluster consists
tween sulfonamide nitrogen atoms and sulfonamide oxygen of one (H2O)12 subunit and six (H2O)3 subunits. The lattice
atoms from adjacent chains to give rise to a 2-D layered water molecules (O8 and O12) are associated by hydrogen
supramolecular structure (N···O distance: 2.881 Å), as bonds to form a puckered 12-membered ring (Figure 4b).
shown in Figure 2. Furthermore, the adjacent layers are Six dangling trimeric water clusters (O10, O4, and O7) at
connected by hydrogen bonds between the water molecules the periphery are attached to the 12-membered-ring core to
Figure 1. ORTEP representation (30% thermal probability ellipsoids) of the crystal structure of compound 1. Hydrogen atoms and lattice
water have been omitted for clarity.
Figure 2. Perspective view of the 2-D structure through hydrogen bonds in compound 1. Hydrogen atoms have been omitted for clarity.
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Figure 3. Molecular structure of 2 (30% thermal probability ellipsoids). Symmetry operations: i: x, y, z – 1; ii: –x + 1, –y, –z.
form an overall (H2O)30 cluster. The trimeric water clusters six large dinuclear molecules. Apart from the interactions
at the periphery are situated alternately above and below with the surrounding water molecules, O7 and O8 also act
the puckered 12-membered ring so as to accommodate the as hydrogen-bond donors to the uncoordinated oxygen
atom (O2) of the N-protected amino acid with O···O dis-
tances of 2.779(9) and 2.728(9) Å, respectively. In the
(H2O)30 cluster, the O···O distances range from 2.697(2) to
3.04(2) Å with an average distance of 2.80 Å, which is
shorter than those observed in liquid water (2.85 Å)[20] and
comparable to the corresponding value in the ice II phase
(2.77–2.84 Å).[21] Furthermore, the inter-(H2O)12 ring
water–water connections have an average O···O distance of
2.743 Å, which is close to the corresponding value of
2.759 Å in hexagonal ice (Ih)[22] but 0.033 Å shorter than
2.776 Å in the 2-D supramolecular ice-like layer containing
(H2O)12 rings in the organic compound bpedo·5H2O
[bpedo = (E)-1,2-bis(4-pyridyl)ethene dioxide].[23] This may
be attributed to its different modes of connectivity with the
surrounding water molecules and the interaction with the
host molecule. The O···O distance between the water mole-
cule at the core and the one connected to it at the periphery
is 2.697(2) Å, which is the strongest hydrogen bonding in
the (H2O)30 cluster. The O···O···O angles vary widely (ca.
95.12–132.83°) with an average of 109.54°, which is close to
the corresponding value of 109.3° in hexagonal ice. Each O
atom of the 12-membered ring shows tricoordination, just
like water molecules at the surface of ice or liquid water
where hydrogen-bond-deficient water molecules are pres-
ent.[24] It is interesting to note that the other two types of
water molecules, O9 and O13, form the water dimer as
acceptor and donor, respectively. The dimers attach to the
dinuclear unit by hydrogen bonds between O13 and O5 as
well as hydrogen bonds between O9 and N5. The O···O and
O···N distances are 2.688(2) and 2.959(9) Å, respectively.
Moreover, there exist orderly aromatic-ring-stacking in-
teractions between phen ligands. The hexaatomic ring of
the phen ligand forms strong π–π stacking with the same
part of a phen ligand in another molecule with the distance
of 3.468 Å. Interestingly, these hydrogen-bonding and π–π
stacking interactions lead to a giant supramolecular unit
Figure 4. Perspective view of the discrete (H2O)30 cluster (a) with
the puckered 12-membered-water-ring core (b) in 2 (H14W of O8
and H11W of O12 are omitted for clarity).
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Two Novel Flexible Multidentate Ligands for Crystal Engineering
consisting of six dinuclear molecules surrounding the
(H2O)30 cluster (Figure 5). Each of these units acts as a sec-
ondary building unit and further form the 2-D supramolec-
ular structure through π–π stacking and hydrogen-bonding
interactions (Figure 6). It can be seen that more hydrophilic
cavities are likely to be formed by choosing appropriate li-
gands containing hydrophilic groups, which prefer to inter-
act with water molecules filled in the cavities through hy-
drogen bonding in the aqueous system.
Figure 6. View of the 2-D supramolecular system of 2 showing hy-
drophilic cavities [green balls represent the hydrophilic oxygen
atoms, (H2O)30 clusters are omitted for clarity].
the discrete (H2O)12 ring core and the additional six dan-
gling trimeric water clusters in compound 2 is rather un-
usual.
Crystal Structure of 3
The perchlorate ions display disorder in the crystal. Fig-
ure 7 only shows the structure of the coordinated cation.
The structural unit of 3 contains two independent MnII
ions: the Mn1 ion has a slightly distorted octahedral ar-
rangement (MnON5) with four nitrogen atoms from the
phen ligand as well as one nitrogen atom and one carboxyl-
ate oxygen atom from the coordinated N-(phenylsulfonyl)-
glycine dianion motif. The Mn(2) ion also has a slightly
distorted octahedral environment (MnO2N4): four nitrogen
atoms from two different phen molecules and one oxygen
atom from the C6H5COO– motif as well as one water mole-
cule. The Mn–O bond lengths are in the range 2.126(4)–
2.148(4) Å, and the Mn–N bond lengths are in the range
2.153(4)–2.288(4) Å. The H3L1 ligand displays different co-
Figure 5. View showing the hydrogen bonding and π–π stacking
interactions in the supramolecular unit in 2.
A search of the latest version of the Cambridge Struc- ordination modes in 2 and 3. In 3, the (L1)3– group acts as
tural Database (CSD)[25] reveals rare examples of water a trianion in a mono(bidentate) mode (O and N,O) and
(H2O)12 rings. Moreover, the reported water (H2O)12 rings bridges two Mn atoms resulting in a dinuclear structure,
are often planar or form 2-D water layers by inter-hydro- whereas in 2, each (HL1)2– group acts as a bis(monodent-
gen-bonding interactions.[22,26] Here, the present mode of ate) (O,O) ligand to bridge two MnII ions. Overall, the li-
Figure 7. View of the coordination environment of MnII in compound 3. Hydrogen atoms and perchlorate anions have been omitted for
clarity.
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Scheme 2. Coordination modes of H3L1and H2L2.
gand H3L1 can be used as a polydentate ligand to coordi- Four oxygen atoms from four different (L2)2– ligands de-
nate transition-metal ions into coordination polymers in scribe an approximately square coordination environment
different modes (Scheme 2). Further investigation of this around the copper atom. The Cu–O bond lengths are
structure suggests that discrete trimeric water clusters exist. 1.9260(13) and 1.9654(10) Å. Both of the potassium atoms
Interestingly, the dinuclear structure is connected into a are seven-coordinate by four carboxylate oxygen atoms (O7,
high-dimensional structure by the water trimer through hy- O8, O3, O8A) from three (L2)2– groups, two sulfonamide
drogen bonding between the water trimer and coordinated oxygen atoms (O2, O5) from the other two (L2)2– groups,
water molecules, sulfonamide oxygen atoms, carboxylate as well as one water molecule (O9) (Figure 9). The K–O
oxygen atoms, and perchlorate anions (Figure 8). It is obvi- bond lengths are in the range 2.6141(13)–3.1346(17) Å,
ous that the water trimer plays a crucial role in contributing which are in agreement with those reported for carboxylate
to the stability of the host of 3.
and potassium heterometallic complexes.[27]
For every N,NЈ-(1,3-phenylenedisulfonyl)bis(glycine) li-
gand there are six oxygen atoms participating in coordina-
tion; the other two sulfonamide oxygen atoms (O1, O6) are
free. One sulfonamide oxygen atom (O2 or O5) of every
N-sulfonylglycine motif coordinates a potassium atom in a
monodentate mode. The two flexible carboxylate groups of
(L2)2– exhibit different coordinating modes. One adopts a
bis(monodentate) bridging mode, while the other displays
an unusual µ3-η2:η2 coordinating mode (each oxygen atom
coordinates to two metal atoms, and the carboxylate group
coordinates to three metal atoms). To the best of our
knowledge, this type of coordinating mode of the amino
acid ligand has not been observed in previously reported
amino acid or N-protected amino acid complexes. Overall,
the (L2)2– group acts in a nonadentate coordination to link
seven metal centers, as shown in Scheme 2.
Figure 8. High-dimensional structure of 3 formed by the water tri-
mer, perchlorate ions, and dinuclear units through hydrogen bond-
ing.
It is worth noting that pairs of K atoms and a single Cu
atom are arrayed alternately where the (L2)2– group acts as
a bridging ligand. The dimetallic K2Cu units grow along
the 101 direction to lead to the formation of the 1-D regular
alternating chain (Figure 10). These chains are linked by K–
Crystal Structure of 4
The crystal structure of [K2Cu(L2)2(H2O)2]n consists of O (sulfonamide oxygen atom) bonds to build 2-D planes,
an asymmetric polynuclear [K2Cu(L2)2(H2O)2] structural which constitute further a complicated 3-D structure owing
unit. The copper atom is four-coordinate (CuO4) (Figure 9). to the K–O (carboxylate oxygen atom) bonds (Figure S1,
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Two Novel Flexible Multidentate Ligands for Crystal Engineering
Figure 9. View of the CuII and KI coordination environments in 4. Symmetry operations: (a) x + 1, y, z; (b) –x + 1, –y, –z + 1; (c) –x +
2, –y, –z + 1; (d) –x + 1, –y + 1, –z + 1; (e) x, y, z + 1; (f) –x + 2, –y + 1, –z + 1; (g) x, y, z – 1; (h) x – 1, y, z.
Figure 10. View of the K2Cu dimetallic chain arrangement growing along the [101] direction in 4. Unnecessary atoms are omitted for
clarity.
Supporting Information). Obviously, the K–O bonds tures. Some 500 X-ray crystal structures containing the
formed between the neighboring structural units play an Cu2(OOCR)4 core can be found in the Cambridge Struc-
important role in constructing the high-dimensional coordi- tural Database. In most structures, four different ligands are
nation polymer.
involved in coordination. Our results are different from
those reported coordination polymers, because the second
carboxylate group of (L2)2– is also included in a paddle-
wheel unit. Only one crystal structure of this type involving
two ligands has been reported in the literature.[28] The
ligand 2,9-bis(methoxymethyl)-2,9-dimethyl-4,7-dioxade-
canedioic acid in the literature and our reported ligand are
both flexible, and the distances between the two carboxylate
groups are so long that they can rotate to embrace two cop-
per ions in the opposite direction.
Crystal Structure of 5
The structure of 5 consists of a centrosymmetric dinu-
clear paddle-wheel unit in which four carboxylate groups
bridge two copper atoms in a syn-syn disposition (Fig-
ure 11). Each copper atom has a square-pyramidal coordi-
nation environment in which four oxygen atoms of two
(L2)2– groups form an equatorial plane and one water
molecule occupies an axial position. The axial Cu–Owater
Several kinds of hydrogen bonding are observed in the
distance is longer than the Cu–Ocarboxylate bond. Thus, the structure: (a) hydrogen bonding between lattice water and
coordination geometry around the copper(II) atom can be coordinated water [the O···O distance is 3.001(8) Å.]; (b) hy-
regarded as a distorted square-pyramidal one, and the drogen bonding between lattice water and sulfonamide ni-
Jahn–Teller effect in the polymer manifests itself as an trogen atom [the N···O distance is 2.929(6) Å]; (c) hydrogen
asymmetric elongation along the axial direction. The Cu– bonding between lattice water and coordinated carboxylate
Cu distance is 2.643(2) Å. In general, copper(II) carboxyl- oxygen atom [the O···O distances are 2.965(6) and
ate complexes exhibit dinuclear paddle-wheel cage struc- 3.001(8) Å, respectively]; (d) hydrogen bonding between sul-
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Figure 11. Representation of the dinuclear unit in 5. Symmetry operation: –x + 2, –y + 1, –z + 2.
fonamide nitrogen atom and sulfonamide oxygen atom [the T plots in Figures 13 and 14. The experimental χMT values
N···O distance is 2.962(5)]. Interestingly, the paddle-wheel of and at room temperature are 9.22 and
2
3
units are associated by the above hydrogen bonds to form 9.66 cm3 Kmol–1, respectively, both of which are larger than
a one-dimensional chain (Figure 12). These chains are as-
sembled by hydrogen bonds between sulfonamide oxygen
atoms and water molecules from adjacent chains (the O···O
distance is 2.797 Å) to give rise to a 2-D layer supramolec-
ular structure.
Figure 12. H-bond system providing a one-dimensional array in 5.
Thermogravimetric Analysis
The TG analysis of 2 shows the onset of water loss at
30 °C. Water removal takes place without showing any dis-
tinct plateau in the curve, giving a total loss of 17.87% at
about 165 °C, which corresponds to loss of all water mole-
cules (calcd. 17.63%). Complete decomposition of the com-
pound is achieved above 700 °C. The TG analysis of 3
shows that the first weight loss of 5.36% (calcd. 5.73%)
observed from 30 to 225 °C corresponds to the loss of three
lattice water molecules and one coordinated water per for-
mula unit. The second process might include two steps from
225 to 720 °C. This represents the decomposition of the ma-
terial. The final residue of 11.41% is close to the 11.28%
calculated on the basis of MnO (Figure S2, Supporting In-
formation, shows the TG curves for 2 and 3).
Magnetic Properties
Figure 13. Temperature dependence of χMT and χM for 2 (a) and
The magnetic susceptibilities of 2–5 were measured in the
2–300 K temperature range and shown as χMT and χM vs. Equation (1) described in the text.
3 (b). The solid line represents the theoretical values based on
700 Eur. J. Inorg. Chem. 2008, 693–703
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Two Novel Flexible Multidentate Ligands for Crystal Engineering
that expected for five independent coupled spins 3. The J values indicate a weakly antiferromagnetic interac-
(8.75 cm3 Kmol–1, S = 5/2) of MnII. As the temperature is tion between the two MnII ions bridged by N-[(3-car-
lowered to 2 K, the χMT products decrease first slowly and boxyphenyl)sulfonyl]glycine. Their low magnitude can be
then rapidly. This behavior suggests that antiferromagnetic associated with the excessive span of the H3L1 bridge.
interactions are operative in 2 and 3.
The experimental χMT value of 4 at room temperature is
0.38 cm3 Kmol–1 per CuII ion, close to the spin value ex-
pected for an uncoupled CuII ion (0.375 cm3 Kmol–1). As
the temperature is lowered to 2 K, the χMT value decreases.
This behavior suggests that an antiferromagnetic interac-
tion is operative in 4. The temperature dependence of the
reciprocal susceptibilities (1/χM) obeys the Curie–Weiss law
above 5 K with θ = –6.113 K. The negative θ value further
supports the presence of overall antiferromagnetic interac-
tions in 4.
Although 4 leads to a three-dimensional network, mag-
netic interactions are operative between the shortest Cu–Cu
distances, and no magnetic coupling could be taking place
through the K atoms. The magnetic susceptibility data were
fitted by assuming that the (L2)2– bridges between the CuII
ions form a uniform chain with a Cu–Cu separation of
8.662 Å (Figure S3, Supporting Information). To simulate
the experimental magnetic behavior, we used the analytical
expression for a one-dimensional Heisenberg chain of clas-
sical spins (S = 1/2), which is similar to 4.[30]
χM = (Ng2β2/KT)[(A + BX + CX2)/(1 + DX + EX2 + FX3)]
where χM denotes the susceptibility per CuII complex, X =
|J |/KT, A = 0.25, B = 0.14995, C = 0.30094, D = 1.9862,
E = 0.68854, and F = 6.0626.
The least-squares analysis of the magnetic susceptibility
data led to J = –0.15 cm–1, g = 2.17, and R = 3.92ϫ10–4.
The J value indicates a weakly antiferromagnetic interac-
tion between the two CuII ions bridged by (L2)2–.
The χMT value of
5
at room temperature is
0.71 cm3 Kmol–1, which falls in the normal range of two
non-coupled CuII ions. Upon cooling, χMT decreases
continuously down to
a
minimum of χMT
=
0.58055 cm3 Kmol–1 about 110 K before rapidly reaching a
sharp maximum of χMT = 0.71654 cm3 Kmol–1 at 5 K. This
behavior is characteristic of a ferrimagnet. Below 5 K, χMT
quickly decreases. This is a classical behavior with antiferro-
magnetic order.[31] Further studies probing this phenome-
non are currently in progress.
Figure 14. Experimental temperature dependence of χMT and χM
for 4 (a) and 5 (b).
In order to quantitatively evaluate these magnetic inter-
actions in the system, for similar dinuclear MnII complexes,
Conclusions
ˆ
Equation (1) is induced from the Hamiltonian H =
–JS1S2.[29]
Ng2β2 A
Two novel versatile glycine derivatives were synthesized
successfully by the reaction of 3-carboxybenzenesulfonyl
chloride or 1,3-phenylenebis(sulfonyl chloride) with glycine.
They will enrich the coordination chemistry of organic aro-
matic polycarboxylates and amino acids. The versatile li-
gands have been introduced to construct four CuII and
MnII complexes simply by changing the pH value or the
base. We have observed a hitherto unknown discrete
(H2O)30 cluster in 2. The present mode of association of a
χM = 2
(1)
kT
B
A = exp[2J/KT] + 5exp[6J/KT] + 14exp[12J/KT] + 30exp[20J/KT]
+ 55exp[30J/KT]
B = 1 + 3exp[2J/KT] + 5exp[6J/KT] + 7exp[12J/KT] + 9exp[20J/
KT] + 11exp[30J/KT]
The least-squares analysis of the magnetic susceptibility puckered 12-membered ring fused with six dangling tri-
data leads to J = –0.09 cm–1, g = 2.21, and R = 2.88ϫ10–4 meric water clusters has not been predicted theoretically
for 2 and J = –0.07 cm–1, g = 2.10, and R = 2.06ϫ10–4 for nor previously reported experimentally. Magnetic proper-
Eur. J. Inorg. Chem. 2008, 693–703
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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701

Y.-Y. Wang, L.-Y. Wang et al.
FULL PAPER
The IR spectrum shows a broad band centered around 3415 cm–1,
which is comparable to the O–H stretching vibrations of water clus-
ters in other complexes.[6d,6f]
Synthesis of [Mn2L1(phen)4(H2O)]ClO4·3H2O (3): Complex 3 was
synthesized in a procedure analogous to that of 2, except that the
ties of the four complexes were also measured. Future stud-
ies will focus on the construction of new metal–organic co-
ordination polymers from these two ligands and their iso-
mers.
pH value was adjusted to around
C57H46ClMn2N9O14S (1258.42): calcd. C 54.40, H 3.68, N 10.01;
7 with NaOH (1 ).
Experimental Section
found C 54.31, H 3.57, N 9.91. IR (KBr): ν = 3452 (s), 1592 (s),
˜
Materials and Instruments: All reagents used in the syntheses were
of analytical grade. Elemental analyses for carbon, hydrogen, and
nitrogen atoms were performed with a Vario EL III elemental ana-
lyzer. Infrared spectra (4000–600 cm–1) were recorded by using KBr
pellets with an AvatarTM 360 ESP IR spectrometer. Crystal deter-
mination was performed with a Bruker SMART APEX II CCD
diffractometer equipped with graphite-monochromatized Mo-Kα
radiation (λ = 0.71073 Å). Variable-temperature magnetic suscep-
tibilities were measured with an MPMS-7 SQUID magnetometer.
Diamagnetic corrections were made with Pascal’s constants for all
constituent atoms. Thermogravimetric (TG) analyses were carried
out with an STA449C integration thermal analyzer.
1423 (s), 1102 (s), 1172 (m), 725 (m), 1385 (s), 849 (m) cm–1.
Synthesis of [K2Cu(L2)2(H2O)2]n (4): To a solution of 1,3-phenyl-
enebis(sulfonyl chloride) (0.289 g, 1 mmol), glycine (0.150 g,
2 mmol), and KOH (0.175 g, 3 mmol) was added a hot water
(30 mL) solution of Cu(OAc)2·2H2O (0.193 g, 1 mmol). The reac-
tion mixture was then heated with a water bath at 70 °C for 8 h
and then filtered. Blue crystals separated from the mother liquor
by slow concentration at room temperature after 2 weeks.
C20H24CuK2N4O18S4 (878.41): calcd. C 27.35, H 2.75, N 6.38;
found C 27.46, H 2.92, N 6.29. IR (KBr): ν = 3257 (s), 1585 (s),
˜
1423 (s), 1161 (m), 709 (m), 1393 (s), 884 (m) cm–1.
Synthesis of H3L1·H2O (1): To a solution of glycine (2.25 g, 0.03
mol) in NaOH (2 , 30 mL), 3-carboxybenzenesulfonyl chloride
(6.78 g, 0.03 mol) was added. The mixture was stirred at room tem-
perature for 2 h. Then the aqueous solution was acidified to pH =
4 with hydrochloric acid (6 ), and a white solid derivative began
to crystallize at once. The crystals were collected on a filter and
recrystallized from alcohol (50%), with a yield of about 65%.
C9H11NO7S (277.25): calcd. C 38.99, H 4.0, N 5.05; found C 38.90,
Synthesis of [Cu(L2)(H2O)]2·2H2O (5): Complex 5 was prepared in
a similar manner to that of 4 by using triethylamine instead of
KOH. C20H28Cu2N4O20S4 (899.78): calcd. C 26.70, H 3.14, N 6.23;
found C 26.79, H 3.25, N 6.15. IR (KBr): ν = 3297 (s), 1651 (s),
˜
1431 (s), 1156 (m), 715 (m), 1383 (s), 872 (m) cm–1.
Crystallographic Data Collection and Structural Determination: Sin-
gle-crystal X-ray diffraction analyses of the five compounds were
carried out. The single crystals of 1–5 were placed in a Bruker
SMART APEX II CCD diffractometer, and diffraction data were
obtained by using graphite-monochromated Mo-Kα radiation (λ =
0.71073 Å) with an ω-2θ scan technique at room temperature. The
H 3.92, N 4.95. IR (KBr): ν = 3285 (s), 1709 (s), 1441 (s), 1171
˜
(m), 753 (m), 1337 (s), 894 (m) cm–1.
Synthesis of [Mn2(HL1)2(phen)4]·16H2O (2):
A mixture of
Mn(ClO4)2·6H2O (0.18 g, 0.5 mmol) and H3L1 (0.23 g, 1 mmol) in
water (15 mL) was stirred. Then the pH was adjusted to around 5
with NaOH (1 ), and an ethanol solution of phen (0.2 g, 1 mmol,
3 mL) was added. The reaction mixture was heated with a water
bath at 70 °C for 10 h and then filtered. Yellow crystals separated
from the mother liquor by slow concentration at room temperature
after 2 weeks. C66H78Mn2N10O28S2 (1633.39): calcd. C 48.53, H
structures were solved by direct methods with SHELXS-97.[32]
A
full-matrix least-squares refinement on F2 was carried out by using
SHELXL-97.[33] The final agreement factors are R1 = 0.0400, wR2
= 0.1119 for 1, R1 = 0.0775, wR2 = 0.2255 for 2, R1 = 0.0711, wR2
= 0.1612 for 3, R = 0.0330, wR2 = 0.0918 for 4, and R = 0.0448,
wR2 = 0.1049 for 5. Crystallographic data and selected bond
lengths and angles for 1–5 are listed in Table 1 and Tables S1–S2
in the Supporting Information. CCDC-632830, -632586,
4.81, N 8.57; found C 48.64, H 4.69, N 8.50. IR (KBr): ν = 3415
˜
(s), 1599 (s), 1425 (s), 1169 (m), 729 (m), 1383 (s), 847 (m) cm–1. -632588, -632589, and -632590 contain the supplementary crystal-
Table 1. Crystallographic data for 1–5.
Compound
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
C9H11NO7S
277.25
monoclinic
C2/c
C66H78Mn2N10O28S2 C57H46ClMn2N9O14S C20H24CuK2N4O18S4 C20H28Cu2N4O20S4
1633.39
1258.42
triclinic
878.41
899.78
rhombohedral
triclinic
triclinic
¯
¯
¯
¯
Space group
R3
P1
P1
P1
Unit cell dimensions
a = 40.620(6) Å a = 33.9311(7) Å
b = 5.1473(7) Å b = 33.9311(7) Å
a = 8.6762(14) Å
b = 17.202(3) Å
c = 20.879(3) Å
α = 104.806(2)°
β = 91.646(2)°
γ = 104.082(2)°
2908.4(8), 2
1.437
a = 8.6624(10) Å
b = 9.8659(11) Å
c = 10.6864(12) Å
α = 62.9880(10)°
β = 84.0450(10)°
γ = 78.2360(10)°
796.50(16), 1
1.831
a = 8.398(8) Å
b = 9.360(9) Å
c = 10.788(10) Å
α = 88.813(11)°
β = 75.571(11)°
γ = 78.950(11)°
805.7(13), 1
1.854
c = 11.326(2) Å
β = 99.170(2)°
2337.8(6), 8
c = 19.7253(8) Å
γ = 120°
19667.5(10), 9
1.241
Volume [Å3], Z
Calculated density [Mgm–3] 1.575
F(000)
1152
7650
1292
0.25ϫ0.14ϫ0.10
1.013
R1 = 0.0711,
wR2 = 0.1612
R1 = 0.1754,
wR2 = 0.2119
0.955/–0.426
447
458
Crystal size [mm]
Goodness of fit
Final R indices [I Ͼ 2σ (I)]
0.34ϫ0.23ϫ0.07 0.39ϫ0.28ϫ0.22
1.082
R1 = 0.0400,
wR2 = 0.1119
R1 = 0.0470,
wR2 = 0.1171
0.37ϫ0.30ϫ0.25
1.060
R1 = 0.0330,
wR2 = 0.0918
R1 = 0.0357,
wR2 = 0.0940
0.586/–0.893
0.22ϫ0.16ϫ0.11
1.054
R1 = 0.0448,
wR2 = 0.1049
R1 = 0.0644,
wR2 = 0.1165
0.689/–0.706
1.016
R1 = 0.0775,
wR2 = 0.2255
R1 = 0.1322,
wR2 = 0.2839
0.790/–0.516
R indices (all data)
Largest diff. peak/hole [eÅ–3] 0.449/–0.551
702
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Eur. J. Inorg. Chem. 2008, 693–703

Two Novel Flexible Multidentate Ligands for Crystal Engineering
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Published Online: December 17, 2007
Eur. J. Inorg. Chem. 2008, 693–703
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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703