Cation-anion interactions via hydrogen bonding; Synthesis, characterization and single crystal X-ray structure of [Cu(phen)3](1,3- benzenedisulphonate)η7H2O

Article abstract of DOI:10.1016/j.molstruc.2014.04.046

A new copper(II) complex, [Cu(phen)₃](1,3-benzenedisulphonate) η7H₂O, has been synthesized by reacting hydrated cupric chloride with phenanthroline (phen) and disodium salt of 1,3-benzenedisulphonate in ethanol-water mixture. It has been characterized on the basis of elemental analysis, spectroscopic techniques (FT-IR, UV-visible, EPR), thermogravimetric analyses and single crystal X-ray structure determination. A detailed packing analysis has revealed the existence of non-covalent interactions which stabilize the crystal lattice.

Full text of DOI:10.1016/j.molstruc.2014.04.046

Journal of Molecular Structure xxx (2014) xxx–xxx
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Cation–anion interactions via hydrogen bonding; synthesis,
characterization and single crystal X-ray structure
of [Cu(phen)3](1,3-benzenedisulphonate)ꢀ7H2O
a
a
a
b
b,
R.P. Sharma a, , S. Kumar , A. Saini , P. Venugopalan , A. Rodríguez-Diéguez , J.M. Salas
⇑
⇑
a Department of Chemistry, Panjab University, Chandigarh, India
b Departmento de Quimica Inorganica, Universidad de Granada, Campus Fuenteneva, s/n, E-18071, Granada, Spain
g r a p h i c a l a b s t r a c t
h i g h l i g h t s
Cation–anion interactions via hydrogen bonding.
ꢁ
ꢁ
ꢁ
Synthesis of a new copper(II)
complex, [Cu(phen)3](1,3-
C6H4(SO3)2)ꢀ7H2O.
Complex has been characterized by
X-ray crystallography and
spectroscopic techniques.
Non-covalent interactions like
hydrogen bonding, p–p, anion–p, etc.
stabilize the crystal lattice of this
inorganic salt.
a r t i c l e i n f o
a b s t r a c t
Article history:
A new copper(II) complex, [Cu(phen)3](1,3-benzenedisulphonate)ꢀ7H2O, has been synthesized by reacting
hydrated cupric chloride with phenanthroline (phen) and disodium salt of 1,3-benzenedisulphonate in
ethanol–water mixture. It has been characterized on the basis of elemental analysis, spectroscopic
techniques (FT-IR, UV-visible, EPR), thermogravimetric analyses and single crystal X-ray structure
determination. A detailed packing analysis has revealed the existence of non-covalent interactions which
stabilize the crystal lattice.
Received 10 February 2014
Received in revised form 14 April 2014
Accepted 14 April 2014
Available online xxxx
Keywords:
Phenanthroline
Ó 2014 Elsevier B.V. All rights reserved.
Non-covalent interactions
Spectroscopic techniques
Single crystal X-ray
Introduction
activation, oxygen transport and catalysis [1–6]. Non-covalent
interactions involving p-systems play crucial role in different areas
It is well recognized that non-covalent interactions play a very
important role in our daily life through their involvement in
interactions of metal complexes with DNA, chemical sensors, gene
of modern chemistry, from materials design to molecular biology
[7]. Structural investigations, mostly fortuitously, can lead to
unexpected supramolecular structures due to the cooperative
effect of multiple non-covalent interactions, in addition to metal
coordination.
⇑
Corresponding authors. Tel.: +91 0172 2534433; fax: +91 0172 2545074.
E-mail addresses: rpsharma@pu.ac.in (R.P. Sharma), jsalas@ugr.es (J.M. Salas).
http://dx.doi.org/10.1016/j.molstruc.2014.04.046
0022-2860/Ó 2014 Elsevier B.V. All rights reserved.
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2
R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
In addition, a number of other supramolecular interactions
involving aromatic moieties i.e. CAH. . . (stacking), cation-
, anion- and lone pair- [8–10] interactions can lead to strong
solution of phen 3.96 g (0.02 mol)) with stirring. To the above
p,
p
–p
warm solution, an aqueous solution of disodium salt of 1,3-ben-
zenedisulphonic acid, 2.82 g (0.01 mol) was added. The resulting
solution was refluxed for 30 min. After cooling the mixture to
ambient temperature a light green product was obtained. It was
filtered through a fine filter paper to obtain a bluish green clear
filtrate and it was put aside at room temperature for evaporation.
After two days we obtained mixture of bluish green crystals along
with light green microcrystalline product. After drying in air,
bluish green crystals (Fig. S1) were separated manually from the
mixture of crystals. The newly synthesized 1 is freely soluble in
methanol, partially soluble in water and decomposes at 303 °C.
Anal. Calcd. (%): C, 52.17; H, 4.34; N, 8.69; S, 6.62; Cu, 6.57. Found
(%): C, 52.37; H, 4.18; N, 8.92; S, 6.78; Cu, 6.66.
p
p
p
cooperativity effects [11] to build solid state networks [12,13].
Great attention has been paid to organosulphonates as a conse-
quence of their longstanding applications as surfactants, dyes, fuels,
lubricant detergents, antioxidants, potential liquid crystalline and
non-linear optical materials [14–17]. The activity of these organ-
osulphonates is enhanced if we made coordination of these organo-
sulphates with metal centers. Such coordination can impart useful
properties like optical, electrical, catalytic and second sphere
interactions to the receptor molecule which are quite helpful in
determining the receptor molecule–anion association [18–21]. In
this work, we explored the supramolecular chemistry of copper
phen based coordination complexes i.e. [Cu(phen)3]2+ or
[Cu(phen)2(H2O)2]2+ (analogus to [Cu(en)2(H2O)2]2+ [22]) in contin-
uation of our research interest in metal-phen based supramolecular
assemblies [23–28]. Complex cation [Cu(phen)3]2+ fulfills all the
requirements to be a good binding agent [29] i.e. (i) it has doubly
positive charged cation for electrostatic interactions, (ii) coordi-
nated phen contains 8 CAH groups, that can act as hydrogen-bond
donor groups, and (iii) it has a stable structural framework. All these
donor groups (8 per ligand) can facilitate interactions with properly
oriented negatively charged oxygen atoms of organosulphonate
groups and hence can result in a donor–acceptor complex involving
second sphere coordination via CAHꢀ ꢀ ꢀO hydrogen bonds [30]. Such
structural studies can be very interesting in the context of their for-
mation, thermodynamic stability, association patterns involving
different coordination mode(s) and packing patterns that can result
in the crystalline phase.
Single crystal X-ray diffraction
A suitable single crystal of 1 was mounted on glass fiber and
used for data collection. Data were collected with a Bruker AXS
APEX CCD area detector equipped with graphite monochromated
Mo-Ka radiation (k = 0.71073 Å) by applying the x-scan method.
The data were processed with APEX2 [32] and corrected for
absorption using SADABS [33]. The structure was solved by direct
methods using SIR97 [34] revealing positions of all non-hydrogen
atoms. These atoms were refined on F2 by a full matrix least-
squares procedure using anisotropic displacement parameters
[35], except for O7W and O8W for solvent disordered patterns.
All hydrogen atoms were located in difference Fourier maps and
included as fixed contributions riding on attached atoms with iso-
tropic thermal displacement parameters 1.5 times those of the
respective atom. Final R(F), wR(F2) and goodness of fit agreement
factors, details on the data collection and analysis can be found
in Table 1.
Thus in this paper, synthesis, characterization and single
crystal X-ray structure of newly synthesized copper(II) complex,
[Cu(phen)3](1,3-benzenedisulphonate)ꢀ7H2O is reported. To the
best of our knowledge, this is first crystal structure of a compound
containing [Cu(phen)3]2+ and arene-disulphonate anion.
Results and discussion
Experimental
Synthesis
Materials and physical measurements
Complex 1 was obtained by refluxing (30 min) a mixture of eth-
anolic solution made out of cupric chloride dihydrate and phen
with aqueous solution of disodium1,3-benzenedisulphonate in
appropriate stoichiometric ratio as shown in Scheme 1. When
the solution reached to ambient temperature after stopping the
Analytical grade reagents were used throughout this work with-
out any further purification. Carbon, hydrogen and nitrogen were
measured micro-analytically by an automatic Perkin Elmer 2400
CHN elemental analyzer and copper was determined gravimetri-
cally [31]. FT-IR spectra were recorded as KBr pellets with PERKIN
ELMERSPECTRUM RXFT-IR system. Electronic spectrum was
recorded in water using a HITACHI 330 SPECTROPHOTOMETER.
The thermogravimetric analysis (TGA) was conducted with a SDT
Q600 instrument. The sample contained in alumina pan was heated
from 33 to 1000 °C at a constant rate of 10 °C minꢂ1 under nitrogen
atmosphere with flow rate of 10 mL/min. X-band EPR measure-
ments were carried out on a Bruker ELEXSYS 500 spectrometer with
a maximum available microwave power of 200 mW and equipped
with a super-high-Q resonator ER-4123-SHQ. For Q-band studies,
EPR spectra were recorded on a Bruker EMX system equipped with
an ER-510-QT resonator and a ER-4112-HV liquid helium cryostat.
The magnetic field was calibrated by a NMR probe and the fre-
quency inside the cavity was determined with a Hewlett-Packard
5352B microwave frequency counter. Computer simulation: WIN-
EPR-Simfonia, version 1.5, Bruker Analytische Messtechnik GmbH).
Table 1
Crystal data, data collection and refinement details of 1.
Chemical formula
C42H42N6O13S2Cu
966.48
100
M/g molꢂ1
T (K)
k (Å)
0.71073
Monoclinic
P21/n
12.930(2)
16.057(3)
20.483(3)
90.224(2)
4252.3(12)
4
Cryst. system
Space group
a/Å
b/Å
c/Å
b (deg)
V (Å3)
Z
q
l
(g cmꢂ3
)
)
1.510
0.686
(mmꢂ1
Unique reflections
R (int)
26,337
0.038
1.033
0.056
GOF on F2
aR1 [I > 2
r(I)]
Synthesis of [Cu(phen)3](1,3-benzenedisulphonate 2)ꢀ7H2O; 1
bwR2 [I > 2
r(I)]
0.140
a
1.71 g (0.01 mol) CuCl2.2H2O was dissolved in 20 mL of ethanol
taken in 100 mL round bottom flask. Added to it, a warm ethanolic
R(F) =
R
||Fo| ꢂ |Fc||
R||Fo|.
b
wR(F2) = [
R
w(F2o ꢂ Fc2)2/
R .
wF4]1/2
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R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
3
Scheme 1. Schematic representation of the synthetic procedure.
refluxing, a light green precipitate was settled at the bottom of the
round bottom flask.
there is no direct CuAO bond [39]. This means that phen forms
an octahedral type arrangement around copper atom and 1,3-ben-
zenedisulphonate links to primary coordination sphere via weak
hydrogen bonding. FT-IR spectrum of 1 is shown in supplementary
material (Fig. S2).
The precipitated product so obtained was filtered and the
resulting clear filtrate was allowed to stand at room temperature.
After two days, a mixture of bluish-green crystals (B) and light
green microcrystalline (A) product was formed. The product
mixture was filtered and dried in air. Bluish-green crystals
(Fig. S1) were manually separated from the mixture of products
obtained. Repeated attempts to grow single crystals of light green
precipitated product (A) were not successful. Elemental analysis of
bluish-green crystals indicated the formation of [Cu(phen)3](1,
3-benzenedisulphonate)ꢀ7H2O which was further fully character-
ized by spectroscopic and single crystal X-ray structure determina-
tion as reported below.
Electronic spectroscopy
An octahedral copper(II) complex is expected to show one
broad absorption band in the electronic spectrum due to d-d (t2g
to eg) transition in visible region [40]. The electronic spectrum of
1 recorded in methanol showed an absorption band at 679 nm
(e
max = 42.80 L molꢂ1 cmꢂ1) corresponding to d–d transition [41].
The visible spectrum of 1 is shown in Fig. S3. The other absorption
bands at 267 nm (
e
max = 34522 L molꢂ1 cmꢂ1) correspond to
p–
pꢃ
transitions which are characteristic of phen moiety as reported in
the literature [42].
Infrared spectroscopy
Infrared spectrum of the newly synthesized complex has been
recorded in the region of 4000–400 cmꢂ1. Tentative assignments
have been made on the basis of earlier reports in literature
[36,37]. The broad band at 3381 cmꢂ1 was assigned to OAH
stretching frequency of water molecule. The stretching band at
3068 cmꢂ1 corresponds to aromatic HAC@C group stretch. The
peaks at 721 cmꢂ1; d(CAH) out of plane, 846 cmꢂ1; d(C@C), 1623,
1652cm–1(C@C/C@N stretch) were characteristics of phen. In the
aromatic compounds containing sulphonate groups, the anti-
symmetric stretching vibrations of the ASO3 groups were expected
in the region 1202 40 cmꢂ1 and symmetric ASO3 group were
expected in the region 1112 40 cmꢂ1 [38]. The mas (ASO3) and
ms (ASO3) bands for 1 appeared at 1190 cmꢂ1 and 1089 cmꢂ1
respectively. The peaks in the region 1000–1100 cmꢂ1 appeared
due to internal vibrations in 1,3-benzenedisulphonate. A weak
band at 694 cmꢂ1 was assigned to m(CAS) stretching. The peak due
to m(CuAO) was absent in the region 500–540 cmꢂ1 indicating that
EPR spectroscopy
The X-band EPR spectra for 1 exhibit near axial symmetry for
the g tensor in the DMs = 1 region, but an appreciable extent of
rhombicity can be detected operating at Q-band (Fig. 1). The main
components of the g tensors obtained from the fit of the experi-
mental room temperature spectrum are: g1 = 2.261, g2 = 2.091
and g3 = 2.075. These values are typical of Cu(II) ions in distorted
octahedral environments which is in good agreement with the
structural characteristics of the CuN6 chromophore [43,44]. More-
over, the lowest g deviates appreciably from the free electron value
(g0 = 2.0023) indicating a dX2 ꢂ y2 ground state, that corresponds
to an axially elongated octahedral environment for Cu(II) ions.
The absence of well resolved hyperfine lines contrast with the
structurally monomeric nature of the compound. The collapse of
the hyperfine structure usually indicates the presence of long
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R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
Fig. 1. Q-band EPR powder spectrum of 1 registered at room temperature. Dotted
line is the best fit; see text for the fitting parameters.
Fig. 3. TG curve of 1.
range exchange coupling. In this sense, the calculated G parameter
is 3.1 [44,45], which indicates that the g values obtained from
experiment are not equal to the molecular ones. This fact implies
the averaging by exchange coupling of the signal corresponding
to magnetically non-equivalent copper sites. Moreover, when the
temperature is lowered down to 5 K, a weak displacement of the
perpendicular component was observed on the X-band spectra
simultaneously to the expected signal narrowing (Fig. 2). This
behavior can be attributed to a small change in the magnitude of
the superexchange coupling because of the thermal expansion of
the crystal structure [46]. Thus, in spite of the large distances
between copper atoms (shorter distance, 10.762) and the absence
of a covalent skeleton connecting them, it can be concluded that
weak magnetic interactions are operative in this compound. The
from 575 °C to 1000 °C (calcd. = 10.83, found = 9.20%) corresponds
to formation of CuO.
Single crystal X-ray structure determination
The compound crystallizes in the P21/n space group pertaining
to monoclinic crystal system. The asymmetric unit is formed by
one tris(phen)copper(II) cation, one 1,3-benzenedisulphonate
anion and seven water molecules of crystallization (Fig. 4).
The coordination geometry around central copper(II) ion is
slightly distorted from octahedron because of the geometrical
restrictions imposed by the phen. The CuAN bond distances are
in agreement with those found in similar compounds of known
structures, which are in the range 2.032(3)–2.349(3) Å. The copper
atom shows Jahn-Teller distortion, due to this, there are two longer
distances in apical positions, 2.313(3) and 2.349(3) Å (see Table 3).
All bond lengths of CuAN(cis) and CuAN(trans) in the title complex
salt fall within the range reported in literature (see Table 2). The
bite angle of phen ligands i.e. <NACuAN in complex salt 1 approx.
76.8° is also closer to that reported in similar compounds (see
Table 2 and Table 3).
hydrogen bonding and/or the p-stacking of the phen rings can pro-
vide the necessary exchange pathway (vide infra).
Thermogravimetric analysis (TGA)
Thermal studies of 1 were performed under nitrogen atmo-
sphere to study the stability of the complex at elevated tempera-
ture. Complex salt when heated from 33 °C to 1000 °C (Fig. 3),
showed that it is stable only up to 70 °C. The first weight loss from
70 °C to 120 °C corresponds to the loss of seven water molecules
(calcd. = 13.04, found = 12.94%). The resulted anhydrous salt at
130 °C was stable up to 230 °C. The second weight loss
(calcd. = 20.52, found = 18.92%) step from 245 °C to 325 °C was
due to loss of one phen moiety. The third weight loss step
(calcd. = 49.06, found = 48.92%) from 325 °C to 575 °C in 1 corre-
sponds to the formation of copper sulphate (loss of two phen,
one benzene and one sulfur dioxide moieties). The final weight loss
The structural parameters of sulphonate group (SAO, CAS,
<CASAO) in 1, amongst other disulphonate salts also do not show
any significant variation (see Table 2).
In crystal lattice, 1,3-benzenedisulphonate and phen groups are
held together by a complex three-dimensional network of hydro-
gen bonds (OAHꢀ ꢀ ꢀO, CAHꢀ ꢀ ꢀO) and
p p stacking interactions as
ꢂ
shown in Fig. 5 (hydrogen bonding parameters are given in
Table 4). Indeed, the packing pattern can be conceived as a com-
plex network of counter ions interspersed by water molecules
and for convenience, it can be described by two types of sheets
in which the first cationic one is made of the mononuclear cop-
per(II) entities united by
pꢂp stacking interactions of 3.385 Å
(phenꢀ ꢀ ꢀphen), 3.380 Å (phenꢀ ꢀ ꢀ1,3-benzenedisulphonate) and the
anionic sheet is constructed through hydrogen bonds involving
the 1,3-benzenedisulphonate anions and the water molecules. It
is noteworthy that all the seven water molecules of crystallization
are extensively OAHꢀ ꢀ ꢀO hydrogen bonded and all of them get
involved in multiple ways (two for each water molecules) as
shown in Table 4 and Fig. 6.
The SO3 groups of 1,3-benzenedisulphonate anion and water
molecules are involved in a complex 2-dimensional hydrogen
bonds network (Fig. 6). In this network, hydrogen bonds are in
the range 2.437–2.931 Å. Along b axis, the structure can be
described by supramolecular sheets generated by hydrogen bonds
among 1,3-benzenedisulphonate anions and water molecules.
Fig. 2. X-band EPR powder spectrum of 1 registered 290 and 5 K.
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R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
5
Fig. 4. A Perspective view of 1. Thermal ellipsoids are drawn at the 50% probability level. Water molecules and hydrogen atoms are omitted for clarity.
Table 2
A comparison of bond lengths (Å) and bond angles (°) of cation and anion in various [Cu(phen)3]2+ disulphonate complexes.
Cation, X = [Cu(phen)3]
CuAN (axial)
CuAN (eq.)
cis-<NACuAN
Trans-<NACuAN
Ref.
Xꢀ(S4O6)S8
2.31
2.30
2.26
2.32
2.29
2.34
2.22
2.34
2.06
2.04
2.11
2.03
2.05
2.04
2.10
2.03
93.8
87.0
77.8
96.3
–
96.2
93.4
95.1
164.1
170.2
167.2
169.1
–
167.3
171.1
166.6
[47a]
[47a]
[47b]
[47c]
[47d]
[47e]
Xꢀ(BF4)2
XꢀCl2ꢀCH2Cl2ꢀ9H2O
Xꢀ(ClO4)2
Xꢀ(PF6)
Xꢀ(CF3SO3)2ꢀ2H2O
Xꢀ(C(CN)3)2
[47f]
This work
Xꢀ(1,3C6H4(SO3)2ꢀ7H2O
Anion, Y = aromatic disulphonate
K2ꢀY
CAS
1.79
1.79
1.77
1.57
1.79
1.77
1.78
SAO
1.45
1.42
1.44
1.42
1.45
1.46
1.45
<CASAO
108.6
104.2
105.7
109.3
104.8
106.3
105.4
[48a]
[48a]
[48b]
[48c]
[48d]
[48e]
This work
[Potꢀtetramethyl ammoniumsalt]ꢀY
[Zn(C4H12N2)2(H2O2)]ꢀY
[Ag(4,40-bipy)H2O)]ꢀY
[Ag(NH3)2]4ꢀY
[Mg(H2O)6]ꢀY
[Cu(phen)3]ꢀY
Table 3
Structural parameters in 1.
supramolecular network in 1 and responsible for the stabilization of
the crystal structure of this compound.
A note on the structural stability of a variety metal complexes of
phen based on our experience [23–28] put forwards the impor-
tance of cooperative interplay of weak interactions in these family
Bond lengths (Å)
Cu1AN1C
Cu1AN8A
2.032(3)
2.039(3)
2.047(3)
Cu1AN8B
Cu1AN8C
Cu1AN1B
2.052(3)
2.313(3)
2.349(3)
Cu1AN1A
Bond angles (°)
N1CACu1AN8A
N1CACu1AN1A
N8AACu1AN1A
N1CACu1AN8B
N8AACu1AN8B
N1AACu1AN8B
N1CACu1AN8C
N8AACu1AN8C
of complexes. Though anionꢀ ꢀ ꢀ
p
and
p p interactions lie at the
ꢀ ꢀ ꢀ
167.39(10)
94.09(11)
81.38(11)
92.79(10)
95.13(10)
161.42(10)
76.85(10)
92.42(10)
N1AACu1AN8C
N8BACu1AN8C
N1CACu1AN1B
N8AACu1AN1B
N1AACu1AN1B
N8BACu1AN1B
N8CACu1AN1B
101.25(10)
97.11(10)
98.65(10)
92.71(10)
85.10(10)
76.81(10)
172.38(9)
bottom of the energetics of weak interactions for lattice stabiliza-
tion, their synergistic behavior contribute significantly to the over-
all stability of the observed crystal packing. For example, in lattice
stability of [Co(phen)2CO3]+ complexes, the crystal structure fea-
tures the synergistic directional bonding interactions including
cation to anion CAHꢀ ꢀ ꢀX (X = Cl, Br of the anion) bonds along with
cation Clꢀ ꢀ ꢀ
p
and cation to cation
pꢀ ꢀ ꢀp stacking interactions
[23,24,26]. In the case of phen metal complexes, in which the
counter anion is predominantly organic (such as arylcarboxylates),
the layer formation (as observed here also) is also dictated by
non-covalent interactions of the type OAHꢀ ꢀ ꢀO and CAHꢀ ꢀ ꢀO (car-
These anionic sheets (Fig. 7) are interspersed with cationic layers
formed by mononuclear copper (II) entities united by stacking
and sulphonate anion- interactions. This cationic layer has stack-
ing interactions among the ‘‘phen ligands’’ with a distance of
3.385 Å. The aromatic ring pertaining to 1,3-benzenedisulphonate
anion posseses stacking interaction with the ‘‘ phen’’ pertaining to
the mononuclear copper (II) unit with a distance of 3.380 Å
(Fig. 7). These are the interactions generating the three-dimensional
pꢂp
p
boxylate/water/carbonato) along with subtitle interplay of p p,
ꢀ ꢀ ꢀ
CAHꢀ ꢀ ꢀ
p
and anionꢀ ꢀ ꢀ
p interactions. In nutshell, in this family of
phen metal complexes, though there are lattice stabilizing O/
NAHꢀ ꢀ ꢀO/N hydrogen bonding possibilities (including that from
occluded water).
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6
R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
Fig. 5. A view along b axis of supramolecular sheets generated by hydrogen bonds in 1.
Table 4
Hydrogen – bonding parameters in 1 (Å, °).
DAHꢀ ꢀ ꢀA
d(DAH)
d(Hꢀ ꢀ ꢀA)
(<DHA)
d(Dꢀ ꢀ ꢀA)
O1WAH11Wꢀ ꢀ ꢀO31d
O1WAH12Wꢀ ꢀ ꢀO.13D
O2WAH21Wꢀ ꢀ ꢀO1W
O2WAH22Wꢀ ꢀ ꢀO3W
O3WAH31Wꢀ ꢀ ꢀO.13D
O3WAH32Wꢀ ꢀ ꢀO.32D
O4WAH41Wꢀ ꢀ ꢀO.5W
O4WAH42Wꢀ ꢀ ꢀO.6W
O6WAH61Wꢀ ꢀ ꢀO.2W
O6WAH62Wꢀ ꢀ ꢀO5W
O5WAH51Wꢀ ꢀ ꢀO12D
O5WAH52Wꢀ ꢀ ꢀO33D
O7WAH71Wꢀ ꢀ ꢀO4W
O7WAH72Wꢀ ꢀ ꢀO11D
0.885
0.794
0.834
0.753
0.701
0.767
1.009
0.825
0.883
0.684
0.938
0.935
0.842
0.846
2.022
2.066
1.970
2.017
2.174
2.032
2.017
1.948
1.893
2.153
1.933
1.820
2.118
2.078
165.95
169.53
169.88
174.68
169.79
169.43
122.01
164.95
168.12
178.47
167.75
170.63
161.26
154.88
2.888
2.851a
2.794
2.767
2.866
2.790a
2.691
2.753b
2.762c
2.837
2.857
2.746d
2.927e
2.866e
Symmetry transformations used to generate equivalent atoms:
a
Fig. 7. A view to the plane showing p–p stacking and anion-p interactions between
1,3-benzenedisulphonate anion in the cationic sheet in 1 along ‘‘c’’ axis. Hydrogen
atoms are omitted for clarity.
[ꢂx + 5/2, y ꢂ 1/2, ꢂz + 1/2].
b
[ꢂx + 2, ꢂy + 1, ꢂz].
c
[x ꢂ 1/2, ꢂy + 1/2, z ꢂ 1/2].
d
[ꢂx + 2, ꢂy, ꢂz].
e
[x ꢂ 1, y, z].
Conclusion
A new copper(II) complex salt [Cu(phen)3](1,3-benzenedisulph-
onate)ꢀ7H2O has been synthesized and structurally characterized
for the first time. A detailed packing analyses has revealed that
non-covalent interactions like hydrogen bonding,
p–p, anion–p,
etc. stabilize the crystal lattice of this inorganic salt. The involve-
ment of large number of water of crystallization through OAHꢀ ꢀ ꢀO
hydrogen bonding has a profound influence in the layer formation
and overall stability of the crystal lattice.
Acknowledgments
One of us (RPS) acknowledges the financial support of UGC,
New Delhi (India) vide grant no. F. 40-60/2011 (SR) and the Junta
de Andalucía FQM-3705 (Spain). Authors gratefully acknowledge
the help of Prof. L. Lezama, Basque Country University, Bilbao
(Spain) for EPR studies.
Appendix A. Supplementary material
Fig. 6. The 2-D network of hydrogen bonding (OAHꢀ ꢀ ꢀO) interactions involving 1,3-
benzenedisulphonate moiety of the anion and six water molecules that generates a
cyclic arrangement.
Crystallographic data (excluding structure factors) for the
reported structure have been deposited with the Cambridge
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R.P. Sharma et al. / Journal of Molecular Structure xxx (2014) xxx–xxx
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