Journal of Molecular Structure 784 (2006) 117–123

www.elsevier.com/locate/molstruc

Second-sphere coordination in anion binding: Synthesis

and characterization of hexaamminecobalt(III) salts
[Co(NH3)6](L)3$3H2O and [Co(NH3)6]Cl(L)2, LZ(CH3)3C6H2SO3
and X-ray structure determination of [Co(NH3)6]Cl(L)2
Raj Pal Sharmaa,*, Ritu Balaa, Rajni Sharmaa, Kamal Nain Singha, Valeria Ferrettib,*
a
Department of Chemistry, Panjab University, Chandigarh-160014, India
b
Centro di Strutturistica Diffrattometrica and Dipartimento di Chimica, University of Ferrara via L.Borsari 46, I-44100 Ferrara, Italy

Received 16 July 2005; revised 5 August 2005; accepted 5 August 2005

Available online 27 October 2005

Abstract
The reaction of hexaamminecobalt(III) chloride with sodium salt of mesitylenesulphonic acid in aqueous medium (1:3 molar ratio) leads to
formation of two products of hexaamminecobalt(III) salts [Co(NH3)6](L)3$3H2O and [Co(NH3)6]Cl(L)2, LZ(CH3)3C6H2SO3. These
cobalt(III) complexes have been characterized by elemental analyses and spectroscopic techniques (e.g. UV/Visible, IR and NMR). Single
crystal X-ray structure determination of title complex salt revealed supramolecular hydrogen bonding network between ionic groups (i.e.
oxygen atoms of C9H11SOK 3 and Cl ) and NH groups of coordinated NH3 molecules, i.e. N–H/O and N–H/Cl interactions resulting in
K K K

bilayer formation, the bilayers being anchored by Cl ions. The formation of definite salts of composition [Co(NH3)6](L)3$3H2O and
K

[Co(NH3)6]Cl(L)2 and measurement of solubility products suggests that [Co(NH3)6]3C present in [Co(NH3)6]Cl3 is a promising purely
inorganic anion binding agent for the weakly coordinating sulphonate anion.
q 2005 Published by Elsevier B.V.

Keywords: Anion binding agent; Cobalt(III); mesitylenesulphonate; Second-sphere coordination; Supramolecular chemistry; Spectroscopy; X-ray
crystallography

1. Introduction feature that makes the electrostatic binding of anions to the

receptors less effective [2–3], (ii) anions have a wide range
Anions play important role in chemical, biological and of geometries and are often present in delocalized forms,
environmental processes. An important aspect of modern which results in higher complexity in design and synthesis
chemistry is the utilization of hydrogen bonding in the of receptors and (iii) pH sensitivity. Therefore, to achieve
development of receptors for recognition of anions [1]. the desired selectivity, the combination of electrostatic
Although cation receptors have been studied for more than attraction, hydrogen bonding and a suitable framework onto
four decades but the development of anion receptors which these structural components can be assembled needs
received less attention. Several reasons why reliable sensing to be taken into consideration when designing artificial
of anions is a particularly challenging area of research are: anionic host [4,5].
(i) anions are larger than isoelectronic cations and, A successful approach for preparing molecules that binds
therefore, have lower charge-to-radius (surface) ratio, a with anions has been to add hydrogen bond donor groups,
N–H to coordinating ligand to yield receptors that interact
* Corresponding authors. Tel.: c91 0172 2534433; fax: c91 0172 2545074 with anions through hydrogen bonding. Host containing a
(RPS), Tel.: c39 01532 291132; fax: c39 0532 240709 (VF). variety of N–H groups have been investigated. During last
E-mail addresses: [email protected] (R.P. Sharma), [email protected] thirty years, many organic based anion receptors have been
(V. Ferretti). reported, e.g. cationic cyclic polyamines [6–8], tripodal
0022-2860/$ - see front matter q 2005 Published by Elsevier B.V. amines [9], calixarenes [10], sapphyrins [11], azacryptands
doi:10.1016/j.molstruc.2005.08.009 [12] and azacages or open chain counterparts [13], but
118 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123

sporadic reports are available with cationic transition metal 2.2. Synthesis of [Co(NH3)6](C9H11SO3)3$3H2O
complexes based anion receptors, i.e. alkoxide-bridged
dinuclear Zn(II) complex [4], urea based Pt(II) receptor [14] Hexaamminecobalt(III) chloride (0.50 g, 0.0018 mol)
and bipyridine Ru(II) complexes [15]. These anion was dissolved in 10 ml hot water taken in a beaker by
receptors are rather difficult to synthesize or are expensive. mechanical stirring. In another beaker 0.22 g (0.0055 mol)
Taking this dilemma into consideration we have undertaken of sodium hydroxide was dissolved in 20 ml of water in
an extensive research program to explore hexaammineco- which 1.12 g (0.0056 mol) of mesitylenesulphonic acid was
balt(III) cation present in hxaamminecobalt(III) chloride as added with stirring. Both the solutions were mixed and
anion receptor (binding agent) because it is relatively easy allowed to cool slowly, first crop of peach coloured solid
to synthesize from readily available materials and could be precipitated immediately, which was filtered and dried in air.
stored for months without any noticeable decomposition. The salt decomposes at 510 K. Solubility: 3.325 g/100 ml in
The cation hxaamminecobalt(III) is tripositively charged, water at 25 (C: Elemental Anal. Calc. for [Co(NH3)6]
possesses eighteen N–H hydrogen bond donor groups and a (C9H11SO3)3$3H2O, (812.90): C, 39.85; H, 7.01; N, 10.33;
stable structural framework onto which anionic components Co, 7.24, Found: C, 39.82; H, 7.00; N, 10.31, Co, 7.10%. IR
can be assembled. In hexaamminecobalt(III) cation, N–H (%), nas 3266b (–NH3), dd 1618m (–NH3), n 1606m (–CC–),
groups are almost spread around the central metal in a n 1565m (–CC–), nas 1463m (–SO3), ds 1326 vs (–NH3), ns
spherical manner should be a proper choice if the counter 1168 vs (–SO3), b 1090 vs, 1019 vs (–CH), vs 873 vs (–CS–),
ion is equipped with multiple hydrogen-acceptors like – rr 840m (–NH3), a 683 vs (–CCC–), 583s nbending (–SO3),
SOK 3 . Understanding of such network interactions of nrocking 548m (–SO3) cmK1. UV/Vis (solution): lmaxZ474
judicially chosen cations and anions would be rewarding (3Z83.36 Mol K1 LK1 cmK1), 338 (3Z77.15 Mol K1
as it can provide means of constructing intricate and novel LK1 cmK1), 280 (3Z2642.29 MolK1 LK1 cmK1), 272
molecular entities based on second-sphere coordination. (3Z2607.68 MolK1 LK1 cmK1). NMR (solution) (D2O):
1
This paper reports the utility of cationic hexaammineco- H NMR, dZ6.9 (s, 6H, aromatic –CH), 2.6 (s,18H,
balt(III) as anion receptor for mesitylenesulphonate ion in (–CH3)2), 2.2 (s, 9H, –CH3), 13C NMR, dZ141.6 (1C),
continuation [16] of our interest in cobalt(III) complexes. 137.7 (2,6C), 131.5 (3,5C), 27.8 (–CH3)2, 25.4 (–CH3) ppm.
We have synthesized and characterized hexaamminecobal-
t(III) mesitylenesulphonate trihydrate, [Co(NH3)6](C9H11- 2.3. Synthesis of [Co(NH3)6]Cl(C9H11SO3)2
SO 3) 3$3H 2O and hexaamminecobalt(III) chloride
mesitylenesulphonate, [Co(NH3)6]Cl(C9H11SO3)2, whose The remaining filtrate of above reaction mixture gave
single crystal X-ray structure determination is also reported. second crop of orange coloured shining crystals after two
We have recently reported the potential use of cationic hours, which were also filtered and dried in air. The overall
hexaamminecobalt(III) as anion receptor for weakly yield is nearly quantitative and salt decomposes at 496 K.
coordinating halate ions [16]. Solubility 4.74 g/100 ml in water at 25 (C: 4.74 g /100 ml.
Elemental Anal. Calc. for [Co(NH3)6]Cl(C9H11SO3)2,
(613.212): C, 35.22; H, 6.52; N, 13.69; Co, 9.60. Found:
2. Experimental C, 35.12; H, 6.49; N, 13.53, Co, 8.9%. IR, nas 3201b (–NH3),
dd 1652m (–NH3), n 1602m (–CC–), n 1565m (–CC–), nas
2.1. General remarks 1453m (–SO3), ds 1337s (–NH3), vs 1168 vs (–SO3), b 1088
vs, 1010 vs (–CH), vs 877 vs (–CS–), rr 840m (–NH3), a
Analytical grade reagents were used without any further 683 vs (–CCC–), 583s nbending (–SO3), nrocking 548m (–SO3)
purification. [Co(NH3)6]Cl3 has been prepared by air cmK1. UV/Vis (solution): lmaxZ474 (3Z59.29 MolK1
oxidation of Co(II) salt in ammonical solution in the LK1 cmK1), 338 (3Z50.31 MolK1 LK1 cmK1), 280 (3Z
presence of activated charcoal as a catalyst according to 1912.52 Mol K1 L K1 cm K1), 272 (3Z1888.77 Mol K1
method described by Bjerrum and McReynold [17]. Cobalt LK1 cmK1). NMR (solution) (D2O): 1H NMR dZ6.91(s,
was determined by standard gravimetric method of 4H, aromatic –CH), 2.4 (s,12H, (–CH3)2), 2.1 (s, 6H, –CH3),
13
estimation [18] and C, H, N were estimated microanalyti- C NMR, dZ141.6 (1C), 137.7 (2,6C), 131.5 (3,5C), 22.5
cally by automatic PERKIN–ELMER 2400CHN elemental (–CH3)2, 20.4 (–CH3) ppm.
analyzer. UV/Visible spectra were recorded using HITA-
CHI 330 spectrometer in water as solvent. Infrared spectra 2.4. Crystal structure determination
of the title complex salts were recorded using PERKIN–
ELMER spectrum RX FT-IR system using Nujol mull in The X-ray diffraction data for the title compound was
KBr plates. 1H NMR and 13C NMR spectra of title complex collected on a Nonius Kappa CCD diffractometer at room
salts were run in the solvent D2O at 25 8C by using JEOL temperature using graphite-monochromated Mo Ka radi-
AL 300 MHz FT NMR spectrometer. The chemical shift ation (lZ0.71073 Å) with a f scan followed by u scan to
values are expressed as d value (ppm) down field from fill the sphere. All intensities were corrected for Lorentz,
tetramethylsilane as an internal standard. polarization and absorption [19] effects. The structure was
 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123 119

Table 1
Crystal data, data collection and refinement parameters of [Co(NH3)6]Cl(C9H11SO3)2

Chemical formula [Co(NH3)6]3CClK$2(C9H11SO3)K

Mr 595.08
Cell setting, space group Monoclinic, C2/m
a, b, c (Å) 22.6294(6), 7.4152(2), 8.1206(2)
b (8) 95.5320(15)
V (Å3) 1356.30(6)
Z 2
Dx(mg mK3) 1.457
m (Mo Ka) (mmK1) 0.928
Crystal form, colour and size (mm3) Plate, orange, 0.38!0.21!0.17
Absorption correction Empirical (SORTAV)
q range (8) 3.8–30.0
No. of measured, independent and observed reflections 6180, 2110, 1845
Criterion for observed reflections IO2s(I)
Rint 0.029
Refinement on F2
R[F2O2s(F2)], wR(F2), goodness of fit 0.030, 0.081, 1.122
No. of observed reflections/No. of parameters 1845/145
Weighting scheme wZ1/[s2(Fo2)C(0.0435P)2C0.3680P], where PZ(Fo2C2Fc2)/3

solved by direct method with the SIR97 program [20] and recrystallization from dilute solution as given in Eq. (1)
refined on F2 by full-matrix least-squares methods with but all the efforts were unsuccessful. The chemical
anisotropic non-H atoms. All H atoms were found in the compositions of newly synthesized complex salts were
difference Fourier map and refined isotropically. All other initially indicated by elemental analyses. These complex
calculations were accomplished using SHELX97 [21], and salts are soluble in hot water but insoluble in any other
PARST [22]. Crystal data and structural refinement commonly used organic solvents (chloroform, ethanol,
parameters are given in Table 1. ORTEPIII [23] view of acetone).
the structure is as shown in Fig. 2.
3.2. Measurement of solubility products

3. Results and discussion Solubility of ionic salts in water differs to a great extent
and on the basis of solubility criterion, the salts are classified
3.1. Synthesis into three categories (a) solubility O0.1 M (soluble), (b)
solubility between 0.01 and 0.1 M (slightly soluble) and (c)
Hexaamminecobalt(III) chloride can react with sodium solubility !0.01 M (sparingly soluble). The solubility
salt of mesitylenesulphonate in number of ways depending measurement at room temperature (Table 1) show that
upon the stoichiometric ratios of reactants as given in Eqs. both [Co(NH3)6](C9H11SO3)3$3H2O and [Co(NH3)6]Cl(C9-
(1)–(3). But in the present work, when hexaamminecobal- H11SO3)2 are sparingly soluble in water but [Co(NH3)6]Cl3
t(III) chloride and sodium salt of mesitylenesulphonate were is soluble. It is observed that the binding (association) of
reacted in 1:3 molar ratio in aqueous medium, not only the mesitylenesulphonate with [Co(NH3)6]3C is much more as
peach coloured precipitate of expected complex salt, compared to chloride ions as Ksp are in the order
[Co(NH3)6](C9H11SO3)3 (as shown in Eq. (1)) formed but [Co(NH 3) 6](C 9H 11SO 3) 3$3H 2 O![Co(NH 3) 6 ]Cl(C 9H 11-
surprisingly orange coloured crystals of complex salt, SO3)2/[Co(NH3)6]Cl3. As reported in the experimental
[Co(NH3)6]Cl(C9H11SO3)2, (as shown in Eq. (2)) were section, when the appropriate amounts of the reactants were
obtained from the filtrate. The overall yield is almost mixed in minimum amount of water the precipitation
quantitative. occurred immediately resulting in the formation of complex
H2 O
½CoðNH3 Þ6 Cl3 C3C9 H11 SO3 Na/½CoðNH3 Þ6 ðC9 H11 SO3 Þ3 C3NaCl
salt, [Co(NH3)6](C9H11SO3)3$3H2O. But complex salt
(1)
[Co(NH3)6]Cl(C9H11SO3)2 crystallized after an hour, at
that crystallization point ionic product is greater than
H2 O
½CoðNH3 Þ6 Cl3 C2C9 H11 SO3 Na/½CoðNH3 Þ6 ClðC9 H11 SO3 Þ2 C2NaCl solubility product, Ksp (Table 2).
(2)

H2 O 3.3. Spectroscopy
½CoðNH3 Þ6 Cl3 CC9 H11 SO3 Na/½CoðNH3 Þ6 Cl2 ðC9 H11 SO3 ÞCNaCl
(3) The infrared spectra of the title complex salts were
We have also attempted to obtain single crystals of measured over the range 600–4000 cmK1. Previous studies
composition [Co(NH3) 6](C 9H 11SO3 ) 3$3H 2O by on the vibrational spectra have provided a considerable
120 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123

Table 2 1010 cmK1. Other ring modes for aromatic ring gave very
Solubility products (Ksp) of hexaamminecobalt(III) salts strong sharp peak at 683 (CCC) cmK1.
Complex salts Solubility (M) Ksp The two transitions in the electronic spectra of hexaammi-
[Co(NH3)6](C9H11SO3)3 0.0040 7.3!10K9 necobalt(III) complexes are observed around 470 and 340 nm
[Co(NH3)6]Cl(C9H11SO3)2 0.0079 1.6!10K8 (d–d transitions typical for low spin Co(III) d6 octahedral
[Co(NH3)6]Cl3 0.26052 0.123 complex) assigned to 1A1g/T1g and 1A1g/1T2g, respect-
ively as reported in the literature [26]. The UV/visible
spectrum of the aqueous solution of complex salt,
amount of information with regard to the fundamental [Co(NH3)6](C9H11SO3)3 shows two ligand field absorption
modes of vibration of this cation. And the present work has at lmaxZ474 (3Z83.36 MlK1cmK1) and 338 nm (3Z
made identification of those bands arising primarily from 77.15 MolK1cmK1). However, two new electronic transitions
the antisymmetric stretch and symmetric NH3 stretch, NH3 were observed in the UV region at 280 and 272 nm having
degenerate deformation, NH3 symmetric deformation and absorption coefficients 2642.29 and 2607.68 MK1cmK1,
NH3 vibrations appear in the regions of 3400–3000, 1650– respectively, which may be assigned to symmetry allowed
1550, 1370–1000 and 950–590 cmK1, respectively for charged transfer bands [27]. Similar pattern was observed for
[Co(NH3)6]Cl3 [24] which are comparable with those in complex salt [Co(NH3)6]Cl(C9H11SO3)2, having lmaxZ474
the title complex salts. The assignments of anionic group of (3Z50.31 MolK1cmK1), 338 (3Z59.29 MolK1cmK1), 280
the title complex salt were made, based on the literature data (3Z1912.52 MolK1cmK1), 272 (3Z1888.77 MolK1cmK1).
[25]. All the bands of the anionic group are divided into two Strong absorption maxima observed for the title complex salts
groups: (a) bands connected to sulphonate anion and (b) are also in agreement with those of related salts such as
bands connected with aromatic rings. The bands due to the hexaamminecobalt(III) chloride selenate trihydrate (lmax 470;
asymmetric vibration (nas) and symmetric vibration (ns) 340 nm) [16] and hexaamminecobalt(III) chloride dichromate
stretches of sulphonate anion occur at 1460–1350 and 1130– monohydrate (lmax 360; 260 nm) [22]. However, in the case of
1200 cmK1, respectively. A very strong band for defor- hexaamminecobalt(III) chloride dimethanesulfonate [22]
mation vibrations of the CSO3 group was observed at there are appreciable shifts of absorption bands (lmax 430;
877 cmK1. The strong and medium bands at 578 and 373 nm).
532 cmK1 are assigned for bending and rocking modes of In the title complex salts, 1H and 13C NMR chemical shift
sulphonate ion. The assignments for the aromatic part of the values are in good agreement with the mesitylenesulphonic
anionic groups are: stretching vibrations for CC bond acid. The 1H NMR spectra of both complex salts show sharp
appeared at 1602, 1565 cmK1, strong and sharp peaks due to peaks in the range 6.7–7.2 and 2.0–2.7 ppm which were
in plane deformation for CH group appeared at 1088, assigned to aromatic protons and substituted methyl groups in

Fig. 1. NMR spectra of [Co(NH3)6]Cl(C9H11SO3)2 (A) and (CH3)3C6H2SO3H (B).

 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123 121

Table 3 agreement with those found in other hexaamminecobalt(III)

Selected bond lengths (Å) and angles (8) of [Co(NH3)6]Cl(C9H11SO3)2 complexes recently reviewed [16]. Selected bond lengths
Co1–N1 1.970(1) C2–C3 1.393(4) and angles are reported in Table 3. ORTEPIII view of the
Co1–N2 1.968(1) C3–C4 1.383(4) structure is shown in Fig. 2. For each hexaamminecobal-
S1–O1 1.459(2) C4–C5 1.378(3) t(III) complex cation, the counter ions are one ClK and two
S1–O2 1.458(1) C5–C6 1.388(3)
S1–C1 1.783(2) C6–C1 1.411(3)
mesytilenesulphonate anions, linked together by N–H/OK
C1–C2 1.410(3) and N–H/ClK hydrogen bonds, whose structural par-
N1–Co1–N2 87.15(4) C2–C1–C6 120.6(2) ameters are reported in Table 4.
O1–S1–O2 111.29(5) C1–C2–C3 117.6(2) The anion, C9H11SOK 3 possesses nearly equal S–O bond
O1–S1–C1 110.07(9) C2–C3–C4 123.0(2)
lengths of 1.459(2) and 1.458(1) Å, while O–S–O bond
O2–S1–C1 105.98(5) C3–C4–C5 117.8(2)
S1–C1–C2 123.9(2) C4–C5–C6 122.8(2) angle is 111.29(5)8 (Table 3). The average bond length of
S1–C1–C6 115.8(1) C1–C6–C5 118.2(2) SO3 group in the mesitylenesulphonate ion of title complex
salt is comparable with those of [(H 2O)4Cr(m-OH2)
Cr(OH2)4)][(H3C)3C6H2SO3]4$4H2O (ionic) [30] and [(n-
mesitylenesulphonate, respectively, as reported in the litera-
C 4H 9) 2Sn{m-OSO 2(C 6H 2(CH 3) 2) 3} 2] n and [(n-
ture [28]. To the best of our knowledge there is no report in the
C4H9)2Sn{(m-OH)(m-OSO2C6H2(CH3)3}]n (coordinated)
literature regarding 13C NMR of mesitylenesulphonic acid or
[29] in which the average S–O bond length is 1.452(2)
its salts. In 13C NMR spectra, chemical shift values for first
(ionic), 1.442(4) and 1.450 Å (coordinated), respectively.
carbon atom (CSOK 3 ) in mesitylenesulphonate group in the
The average O–S–O and O–S–C bond angles in
title complex salts were observed at 141 ppm (Fig. 1). The
[(H 2O) 4Cr(m-OH 2)Cr(OH 2) 4 )][(H 3C) 3C 6H 2SO 3] 4$4H 2O
values for the subsequent carbon atoms in the aromatic rings
are 111.7(1) and (107.13(1)8, respectively [30].
are in good agreement with mesitylenesulphonic acid (138.8
Organic anions and cations form alternate layers linked
and 132,1 ppm) for aromatic carbons, 21.0 (–CH3) and
together by N–H/OK hydrogen bonds, the chloride anion
23.2 ppm ((–CH3)2) as shown in Fig. 1. For the oxygen
coordinated mesitylenesulphonate group [29] the 13C NMR bridging two adjacent cobalt complexes (Fig. 3). Because of
values are 25,6 ((–CH3)2), 27.0 ppm (–CH3) and 141.7, symmetry, the packing architecture is quite complicated
137.05, 136.2 and 130.1 ppm for aromatic ring. and can be described according to the graph-set approach
[31–32]. The layer formed by cobalt complexes is
connected by two equivalent N–H/ClK bonds linking
two N2 atoms with the chloride anion and forming a planar
4. X-ray crystallography R12 ð6Þ (RZring) motif, duplicated by symmetry (we have
taken into account only the strongest N–H/ClK inter-
The composition and structure of [Co(NH3)6]Cl(C9H11- actions). This leads to the formation of two intercrossed Co–
SO3)2 complex salt has been unambiguously established by N2–H/Cl/H–N2–Co. C(4) chains running along the c
single crystal X-ray crystallography. The cobalt(III) metal direction. Along the a direction, the two layers are linked by
ion is coordinated to six ammonia molecules, and the N–H/OK hydrogen bonds, forming a R22 ð8Þ ring on both
geometry of the complex is almost perfectly octahedral, the sides of each Co complex which is one of the simplest and
central Co atom being positioned on an inversion centre: most commonly occurring motifs formed between oxygen
Co–N bond lengths are 1.970(1) and 1.968(1) Å, in atoms of RSOK 3 and the NH donors (bidentate motif)

Fig. 2. ORTEPIII view of [Co(NH3)6]Cl(C9H11SO3)2. The displacement ellipsoids are drawn at 40% probability.
122 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123

Fig. 3. Packing diagram of [Co(NH3)6]Cl(C9H11SO3)2 along the a axis. Hydrogen bonds are drawn as broken lines.

reported in the literature [33]. Along the b direction, N1– [Co(NH3)6](C9H11SO3)3![Co(NH3)6]Cl(C9H11SO3)2/

H2/O2 hydrogen bonds form two symmetric C(4) chains. [Co(NH3)6]Cl3. In the case of [Co(NH3)6]Cl(C9H11SO3)2, the
The combination of these motifs gives the complex packing single crystal X-ray structure determination revealed the
pattern reported in Fig. 3, in a projection along the a axis presence of N–H/OK and N–H/ClK charge assisted
where the layered structure is particularly evident. hydrogen bond interactions apart from coulombic attractions
It is interesting that out of six ammonia ligands in the solid state which may be present in the other title
(coordinated to cobalt(III)), only two hydrogen atoms of complex salt also. Therefore, the present study shows that
two ammonia ligands (in trans geometry), are involved in purely inorganic cationic metal complex, [Co(NH3)6]3C
hydrogen bonding with oxygen atoms of mesitylenesulpho- present in [Co(NH3)6]Cl3 is a promising anion binding agent
nate and out of three hydrogen atoms of remaining four for weakly coordinating mesitylenesulphonate ion in aqueous
ammonia ligands, two are involved in hydrogen bond medium in contrast to other synthetic receptors which are
formation with oxygen atoms of mesitylenesulponate and effective in non-aqueous solvents. An understanding of the
the remaining one is responsible for imparting stability to intricate details of assembly of molecules (crystal engineer-
the bilayers through N–H/ClK hydrogen bond interaction ing) may be useful synthetic strategy to produce new
as shown in Fig. 4. However, its is quite different from our technologically relevant materials.
previously reported complex salt, [Co(NH3)6]Cl(CH3SO3)2
in which out of the three hydrogen atoms of each ammonia
ligands, two are involved in rosette formation and the
remaining one is responsible for imparting stability to these 6. Supplementary data
bilayers though N–H/ClK hydrogen bonds. Around each
chloride ion, there are six such interactions, three of them to Crystallographic data for the structural analysis of the
each side of the bilayer. Overall, an interesting network of complex salt [Co(NH3)6]Cl(C9H11SO3)2 has been deposited
N–H/OK and N–H/ClK hydrogen bonds through at the Cambridge Crystallographic Data Center,12 Union
second-sphere coordination generates and stabilizes rosette Road,Cambridge, CB2 1EZ, UK, and are available free of
layers of the crystal lattice. charge from the Director on request quoting the deposition
Table 4
Hydrogen bonding parameters (Å,8) of [Co(NH3)6]Cl(C9H11SO3)2
5. Conclusion D–H/A D–H D/A H/A !D–H/A
N1–H1/Cl1 0.73(3) 3.436(2) 2.77(3) 152(3)
In the conclusion, we have reported here the utility of N2–H1/O1 0.91(2) 3.051(2) 2.14(2) 175(2)
[Co(NH3)6]3C as anion receptor for mesitylenesulphonate ion. N2–H2/Cl1 0.86(2) 3.251(1) 2.45(2) 156(2)
The measurements of solubility products show that relative N1–H2/O2a 0.92(2) 2.936(1) 2.04(2) 165(2)
affinities of three mesitylenesulphonate ion for hexaammine- N2–H3/O2b 0.91(2) 2.901(2) 2.01(2) 164(2)
cobalt(III) is less as compared to two mesitylenesulphonate a
Sym. Op.: x,KyK1,z.
b
and chloride ions, i.e. the solubility products are in order Sym. Op.: 1Kx,y,Kz.
 R.P. Sharma et al. / Journal of Molecular Structure 784 (2006) 117–123 123

Fig. 4. Packing diagram of [Co(NH3)6]Cl(C9H11SO3)2 along the c axis.

number CCDC 274221. (Fax: C44 1223 336033, email: P. Venugopalan, J. Coord. Chem. 57 (2004) 1563; R.P. Sharma,
[email protected]). R. Bala, R. Sharma, M. Quiros, J.M. Salas, J. Coord. Chem. 58 (2005)
217; R.P. Sharma, R. Bala, R. Sharma, V. Ferretti, Inorg. Chim Acta.
358 (2005) 3457; R.P. Sharma, R. Bala, R. Sharma, P. Venugopalan,
J. Mol. Struct. 694 (2004) 229; R.P. Sharma, R. Bala, R. Sharma,
Acknowledgements B.M. Kariuki, U. Rychlewska, B. Warzajtis, J. Mol. Struct. 748 (2005)
143–151; R.P. Sharma, R. Bala, R. Sharma, A.D. Bond, Acta
Ritu Bala thanks the CSIR, New Delhi, India for the Crystallogr. C61 (2005) m356; R.P. Sharma, R. Bala, R. Sharma,
U. Rychlewska, B. Warzÿajtis, J. Fluorine Chem. 126 (2005) 967; (i)
financial support (Grant No.01(1768)/02 /EMR-II).
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