Journal of Molecular Structure 797 (2006) 49–55
www.elsevier.com/locate/molstruc
Second-sphere coordination complex via hydrogen bonding:
Synthesis, characterization, X-ray crystal structure determination
and packing of hexaamminecobalt(III) chloride di(para-nitrobenzoate)
Raj Pal Sharma a,*, Ritu Bala a, Rajni Sharma a, Julio Perez b,*, Daniel Miguel c
b
a
Department of Chemistry, Panjab University, Chandigarh-160014, India
Departamento de Quı́mica Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, Oviedo 33006, Spain
c
Departamento de Quı́mica Inorgánica, Universidad de Valladolid, Valladolid 47071, Spain
Received 27 January 2006; received in revised form 27 February 2006; accepted 4 March 2006
Available online 24 April 2006
Abstract
A reddish orange coloured crystalline solid of hexaamminecobalt(III) chloride di(para-nitrobenzoate) was obtained when
hexaamminecobalt(III) chloride was reacted with the sodium salt of para-nitrobenzoic acid (1:3 molar ratio) in hot aqueous medium.
This cobalt(III) complex salt has been characterized by elemental analyses and spectroscopic techniques (e.g. UV/visible, IR and
NMR). Single-crystal X-ray structure determination of the title complex salt revealed that it contains the cationic cobaltammine
([Co(NH3)6]3+) and mixed anions (Cl , NO2C6H4COO ), which are held together by electrostatic forces attractions through secondsphere coordination, i.e. N–H O (carboxylate and nitro) and N–H Cl hydrogen bonds, resulting in a three-dimensional network.
2006 Elsevier B.V. All rights reserved.
Keywords: Cobalt(III); Para-nitrobenzoate; Second-sphere coordination; Supramolecular chemistry; Spectroscopy; X-ray crystallography
1. Introduction
In the recent years there has been an enormous increase
of interest in using supramolecular interactions as the basis
of the attempted design of solid state structures, a process
commonly referred to as crystal engineering [1]. The successes of crystal engineering have largely come about
through the use of ‘supramolecular synthons’ [2]. A number of rational design and methodologies towards this goal
have emerged [3]. Reliable supramolecular synthons based
on complementarity of intermolecular interactions have
also been identified. Especially much attention has been
focused on the self-assembly of supramolecular architectures by exploiting non-covalent forces including coordina*
Corresponding authors. Tel.: +91 0172 2544433; fax: +91 0172 2545074
(R.P. Sharma), tel.: +34 985103465; fax: +34985 103446 (J. Perez).
E-mail addresses: rpsharma@pu.ac.in (R.P. Sharma), japm@uniovi.es
(J. Perez).
0022-2860/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2006.03.046
tion bonding, aromatic p–p stacking interactions, and
electronic and charge transfer attractions [4]. Supramolecular assembly is a central theme in the design of new solid
materials with intriguing structures such as brick walls, [5]
square grid [6], honeycomb, and other geometries [7–9].
One of the strategies for the construction of such supramolecular architecture is by second-sphere coordination –
the interaction between already coordinatively saturated
metal complexes and external ligands e.g., through hydrogen bonding. A variety of biological systems utilize secondsphere coordination for modification of the chemistry
around metal ions [10]. In order to enact supramolecular
second-coordination sphere systems, some functional
groups must be appended to the first-sphere ligand. These
groups should not only coordinate to a metal center in
the formation of first-sphere complex, but also bind the
external ions (i.e., second-sphere ion) to build the
supramolecular system. The ammonia, NH3, group
possesses such dual function, the nitrogen atom of NH3
50
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
group being capable of coordinating a cobalt(III), yielding
primary complex e.g., [Co(NH3)6]3+. In addition, this complex cation can serve as a building block for the formation
of larger supramolecular assemblies because the coordinated ammonia groups are good hydrogen bond donors. The
hexaamminecobalt(III) cation in which these hydrogens are
almost spread around the central metal in a spherical manner should be a proper choice in particular if the counteranion is equipped with multiple hydrogen bond acceptor
groups. Regarding the anion, carboxylate groups were considered appropriate as there are four oxygen atoms per
molecule that can act as efficient proton acceptors. In the
solid state, these two ions can be anticipated to form an
intricate network of hydrogen bonds stabilizing the entire
lattice. The understanding of such network interactions
of judiciously chosen cations and anions would be rewarding as it can provide means of constructing intricate and
novel molecular entities based on second-sphere coordination. Thus in continuation [11] of our interest in hexaamminecobalt(III) complexes, we report here the synthesis,
characterization and single crystal X-ray structure determination of hexaamminecobalt(III) chloride di(paranitrobenzoate).
2. Experimental
2.1. General remarks
Analytical grade reagents were used without any further
purification. [Co(NH3)6]Cl3 has been prepared by air oxidation of Co(II) salt in ammoniacal solution in the presence of activated charcoal as a catalyst according to the
method described by Bjerrum and McReynold [12]. Cobalt
was determined by a standard gravimetric method of estimation [13] and C, H, N were estimated microanalytically
by an automatic Perkin Elmer 2400CHN elemental analyzer. UV/visible spectra were recorded using a HITACHI 330
spectrometer in water as solvent. The infrared spectrum of
the title complex salt was recorded using a Perkin Elmer
spectrum RX FT-IR system using Nujol mull in KBr
plates. 1H NMR and 13C NMR spectra of title complex salt
were run in the solvent D2O at 25 C by using a JEOL AL
300 MHz FT NMR spectrometer. The chemical shift values are expressed as d value (ppm) downfield from tetramethylsilane as an internal standard.
2.2. X-ray structure determination
A suitable crystal was attached to a glass fiber and transferred to a Bruker AXS SMART 1000 diffractometer with
graphite monochromatized Mo Ka X-radiation and a
CCD area detector. Raw frame data were integrated with
the SAINT [14] program. The structures were solved by
direct methods with SHELXTL [15]. An empirical absorption correction was applied with the program SADABS
[16]. All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were set in calculated positions and
refined as riding atoms. Calculations were made with
SHELXTL and PARST [17] under WINGX [18]. Drawings were made with SHELXTL. All other information
regarding the refinement is also recorded in Table 1.
2.3. Synthesis of [Co(NH3)6]Cl(O2NC6H4COO)2
Hexaamminecobalt(III) chloride (1.00 g, 0.0037 mol)
was dissolved in 25 ml hot water in a beaker by mechanical
stirring. In another beaker, a sodium salt of para-nitrobenzoate was prepared by dissolving 0.452 g (0.0112 mol)
of sodium hydroxide and para-nitrobenzoic acid (1.88 g
0.0112 mol) in 20 ml of hot water. Both solutions were
mixed and allowed to cool slowly. A yellow solid that precipitated immediately was washed with ice-cold water and
air-dried. Orange-yellowish coloured shining crystals were
obtained from the hot aqueous medium, which were filtered and dried in air. The overall yield is nearly quantitative, and the salt decomposes at 478 K. Solubility (25 C) in
water: 0.512 g/100 ml. Elemental Anal. Calcd for
C14H26ClCoN8O8, (528.81): C, 31.76; H, 4.91; N, 21.17;
Co, 11.13. Found: C, 31.74; H, 4.85; N, 21.14, Co,
11.01%. IR m = 3174 (b), 1615 (m), 1566 (s), 1507 (s),
1346 (vs), 1318 (s), 1168 (m), 1103 (m), 1010 (m), 882
(m), 819 (m) cm 1. UV/visible (solution): kmax = 474,
273. NMR (solution): 1H NMR (D2O), d = 7.8 (d, 4H),
8.1 (d, 4H), 13C NMR, d = 174, 149, 143, 130, 124 ppm.
Table 1
Crystal data and structure refinement for hexaamminecobalt(III) chloride
di(para-nitrobenzoate)
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
Unit cell dimensions
Volume
Z
Density (calculated)
Absorption coefficient
F (0 0 0)
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 23.29
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r (I)]
R indices (all data)
Largest diff. peak and hole
C14H26ClCoN8O8
528.81
293(2) K
0.71073 Å
Triclinic
P-1
a = 6.9976(14) Å, a = 64.778(3)
b = 12.886(3) Å, b = 86.202(4)
c = 13.622(3) Å, c = 80.691(4)
1096.6(4) Å3
2
1.602 Mg/m3
0.963 mm 1
548
0.23 · 0.20 · 0.12 mm3
1.77–23.29
7 6 h 6 7, 9 6 k 6 14,
15 6 l 6 15
4858
3105 [R (int) = 0.0174]
98.2%
SADABS
1.000000 and 0.729010
Full-matrix least-squares on F2
3105/0/298
1.076
R1 = 0.0358, wR2 = 0.1002
R1 = 0.0416, wR2 = 0.1037
0.301 and 0.597e Å 3
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
3. Results and discussion
3.1. Synthesis
The new hexaamminecobalt(III) complex salt [Co(NH3)6]Cl(O2NC6H4COO)2 has been synthesized by reacting
sodium para-nitrobenzoate with [Co(NH3)6]Cl3 in a 3:1
molar ratio in hot aqueous medium. Single crystals of
[Co(NH3)6]Cl(O2NC6H4COO)2 were obtained from hot
aqueous medium by allowing it to evaporate at room temperature. However, all efforts to obtain a complex salt of
composition [Co(NH3)6](O2NC6H4COO)3 were unsuccessful. The chemical composition of the newly synthesized
complex salt was initially indicated by elemental analyses.
The title complex salt is highly soluble in DMSO, soluble
in hot water, but insoluble in other organic solvents (e.g.,
chloroform, ethanol, acetone).
3.2. Measurement of solubility products
Solubility of ionic salts in water differs to a great extent
and on the basis of solubility criterion, the salts are classified into three categories [11]. The solubility measurements
at room temperature (Table 2) show that [Co(NH3)6](4nitrophenolate)3 Æ 4H2O is slightly soluble in water whereas
[Co(NH3)6]Cl(para-nitrobenzoate)2 is sparingly soluble. It
is observed that the binding (association) of 2,4,6-trinitrophenolate and 2,4-dinitrophenolate ions with [Co(NH3)6]3+
is much larger than that of para-nitrobenzoate and 4-nitrophenolate ion, i.e. the binding affinities are in the
order [Co(NH3)6](2,4,6-trinitrophenolate)3 > [Co(NH3)6](2,4dinitrophenolate)3 [Co(NH3)6]Cl(para-nitrobenzoate) >
[Co(NH3)6](4-nitrophenolate)3 Æ 4H2O. This may be ascribed to the increase in the number of nitro groups on
the phenolate ion. As reported in the experimental section,
when the appropriate amounts of the reactants were mixed
in a minimum amount of water, the precipitation occurred
immediately, resulting in the formation of title complex
salt, a fact which indicates that ionic product is larger than
solubility product, Ksp (Table 2).
3.3. Spectroscopy
The vibrational spectrum of newly synthesized
hexaamminecobalt(III) complex salt show that the stretching vibrations of the coordinated NH3 molecule are lower
Table 2
Solubility products (Ksp) of hexaamminecobalt(III) salts
Complex salts
Solubility (M)
Ksp
[Co(NH3)6]Cl3
[Co(NH3)6](4-nitrophenolate)3 Æ 4H2O
[Co(NH3)6](2,4-dinitrophenolate)3
[Co(NH3)6](2,4,6-trinitrophenolate)3
[Co(NH3)6]Cl(4-nitrobenzoate)2
0.26052
0.01352
0.00079
0.00046
0.00969
0.123
9.0 · 10 7
1.0 · 10 11
1.2 · 10 12
3.4 · 10 8
51
than those of the free NH3 molecules for two reasons:
the effect of coordination and the effect of the counterion,
i.e. para-nitrobenzoate. This is attributed to the weakening
of the N-H bond due to the formation of N–H O, N–
O H type of hydrogen bond. It is seen that the antisymmetric stretch and symmetric NH3 stretch, NH3 degenerate
deformation, NH3 symmetric deformation and NH3 vibrations appear in the regions of 3400–3000, 1650–1550, 1370–
1200 and 800–900 cm 1, respectively, for [Co(NH3)6]Cl3[19], values comparable with those for the newly synthesized hexaamminecobalt(III) complex salts. For the paranitrobenzoate anionic group,the hydrogen bonding weakens the N@O bond, resulting in a shift of the absorption
to lower frequency and (the sharp peaks are observed at
1507 and 1346 cm 1 for NO2 (ms) and NO2 (mas), respectively). However, in the case of carboxylate group, the hydrogen bonding and resonance weaken the C@O bond,
resulting in absorption at lower frequency and the sharp
peak at 1566 for C@O (mas). The peaks have been assigned
by comparison with the reported [20,21] values.
As reported in the literature [22] the two transitions
1
A1g fi T1g and 1A1g fi 1T2g for hexaamminecobalt(III)
complexes are observed around 470 and 340 nm, respectively, producing the familiar orange yellow colour for
number of classical coordination compounds containing
cobalt(III). For the title complex salt the kmax for lower
energy was observed at 470 nm but the kmax for higher
energy was not observed but shifted to left i.e. 273 nm this
might be due to outer-sphere charge transfer from nitro
substituted phenolate ion to central metal cation. These
values of kmax in the newly synthesized complex salts are
also in agreement with those of the earlier reported complex salts [11 (l)], but quite different from our earlier reported hexaamminecobalt(III) salts [11 (a–k)].
In the title complex salt, 1H and 13C NMR chemical
shift values are close with the literature values reported
for para-nitrobenzene and benzoic acid [23]. In 13C
NMR, chemical shift values for carbon atoms of the
groups COO , C–NO2 and C–COO are 174, 149 and
143 ppm, respectively. These 1H and 13C NMR chemical
shift values are in good agreement with sodium salt of
para-nitrobenzoic acid (d = 7.8 (d, 2H), 7.6 (d, 2H), 13C
NMR, d = 172, 148, 142, 129, 123 ppm) shown in Fig. 1.
4. X-ray
X-ray crystal structure of the hexaamminecobalt(III)
chloride di(para-nitrobenzoate) has been unambiguously
determined by single crystal X-ray crystallography. The
crystal structure not only conclusively establishes the existence of the single salt of composition [Co(NH3)6]Cl(O2NC6H4COO)2 but also rules out the possibility
of a mixture of salts or a double salt. Furthermore, this
revealed for the first time that it is a first ionic salt which
contains discrete ions [Co(NH3)6]3+, Cl
and two
O2NC6H4COO in the solid state. The ORTEP diagram
of title complex salt is shown in Fig. 2.
52
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
Fig. 1. (A) 1H NMR of sodium para-nitrobenzoate, (B) 13C NMR of sodium para-nitrobenzoate.
Fig. 2. ORTEP diagram of hexaamminecobalt(III) chloride di(para-nitrobenzoate).
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
In [Co(NH3)6]3+, the cobalt(III) metal ion is surrounded
by six nitrogen atoms originating from six coordinated
ammonia molecules resulting in a octahedral geometry.
The Co–N bond distances are in the range 1.960(2)–
1.970(2) Å, while cis N–Co–N bond angles are in the range
86.68(10)–93.32(10) and trans N–Co–N bond angles are in
the range 180.00(0)–180.00(13). In the hexaamminecobalt(III) chloride [24], the average Co–N distance is
1.964 Å and the maximum deviation of cis N–Co–N bond
angles from their ideal values is 2.1 with a standard deviation of 0.7. These values of the [Co(NH3)6]Cl(O2NC6H4COO)2 salt are also in agreement with the earlier reported
hexaamminecobalt(III) complex salts [11]. The selected
bond angles and bond lengths are listed in Table 3.
In the crystal lattice, there are two independent
[Co(NH3)6]3+ cations and each is placed on a center of
inversion. As a result, they have octahedral coordination
geometry around the central metal ion (Table 3). The packing of the title complex salt shows some interesting structural features. The aromatic rings of the two paranitrobenzoate ions are arranged in an edge-to-face manner
with an angle of 108.04. The average C–O and >C–COO
bond lengths of the benzoate ion, 1.226(4) and 1.483(4) Å,
can be compared with those of the coordinated benzoate in
the complex salt [25] [Co(H2O)4(O2NC6H4COO)2]. 2 H2O,
(C–Ocoord, 1.292(6) and 1.246(8) Å; and >C–COO,
1.513(7) Å) and with benzoic acid [26] where these values
are 1.275 (5) and 1.268(6) Å; and >C–COOH, 1.494(5) Å.
In the crystal lattice of title complex salt, interactions of
the type N–H O (COO and NO2) and N–H Cl are
encountered linking anions and the hexaamminecobalt(III)
cation. The role of the chloride ions is to stabilize the intervening hexaamminecobalt(III) cations by extensive hydrogen bonding (N2–H2A Cl1 = 2.577(.001) Å, N6–
H6A Cl1 = 2.487(.001) Å, Fig. 3). The adjacent paranitrobenzoate ions in the unit cell are arranged in a headto-tail fashion and forming hydrogen bonding from both
ends (using both –COO and –NO2 groups except two –
C(17)OO ) with ammonia molecules of [Co(NH3)6]3+ as
shown in Fig. 4. This type of arrangement was also
observed in complex [Co(NH3)6](4-O2NC6H4O)3 Æ 4H2O,
six linear columns present at the inversion center of the unit
cell forming a tubular cavity in which the 4-nitrophenolate
anions reside, forming hydrogen bonding linkages to adjacent columns from both ends (using both –O and –NO2
groups), i.e. head-to-tail bonding of 4-np ion which we
have observed for the first time.
The parameters describing major types of intermolecular H-bonding interactions within the inorganic and organic layers are listed in Table 4. These include various types of
hydrogen bonds and edge-to-face interactions involving all
benzoate groups. As it can be seen from this Table, the
uncoordinated oxygen atoms of the carboxylate group in
para-nitrobenzoate act as double (O23, O24) acceptors
and oxygen atoms of nitro group in para-nitrobenzoate
act as double (O14, O12) and triple (O13) acceptors, by
interacting with hydrogen atoms of NH3 groups.
53
Table 3
Bond lengths (Å) and angles () for hexaamminecobalt(III) chloride
di(para-nitrobenzoate)
Co(1)–N(2)#1
Co(1)–N(2)
Co(1)–N(3)#1
Co(1)–N(3)
Co(1)–N(1)
Co(1)–N(1)#1
N(11)–O(14)
N(11)–O(13)
N(11)–C(14)
C(27)–O(24)
C(27)–O(23)
C(27)–C(24)
C(11)–C(16)
C(11)–C(12)
C(11)–C(17)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
1.960(2)
1.960(2)
1.963(2)
1.963(2)
1.968(2)
1.968(2)
1.253(4)
1.256(4)
1.533(4)
1.246(4)
1.249(4)
1.509(4)
1.372(5)
1.376(5)
1.457(4)
1.372(5)
1.380(4)
1.381(4)
Co(2)–N(5)#2
Co(2)–N(5)
Co(2)–N(4)
Co(2)–N(4)#2
Co(2)–N(6)#2
Co(2)–N(6)
C(15)–C(16)
C(17)–O(11)
C(17)–O(12)
C(21)–C(22)
C(21)–C(26)
C(21)–N(21)
C(22)–C(23)
C(23)–C(24)
C(24)–C(25)
C(25)–C(26)
N(21)–O(21)
N(21)–O(22)
1.961(2)
1.961(2)
1.967(2)
1.967(2)
1.970(2)
1.970(2)
1.379(5)
1.205(5)
1.206(4)
1.376(5)
1.379(5)
1.476(4)
1.365(5)
1.393(5)
1.385(4)
1.380(4)
1.212(4)
1.236(4)
N(2)#1–Co(1)–N(2)
N(2)#1–Co(1)–N(3)#1
N(2)–Co(1)–N(3)#1
N(2)#1–Co(1)–N(3)
N(2)–Co(1)–N(3)
N(3)#1–Co(1)–N(3)
N(2)#1–Co(1)–N(1)
N(2)–Co(1)–N(1)
N(3)#1–Co(1)–N(1)
N(3)–Co(1)–N(1)
N(2)#1–Co(1)–N(1)#1
N(2)–Co(1)–N(1)#1
N(3)#1–Co(1)–N(1)#1
N(3)–Co(1)–N(1)#1
N(1)–Co(1)–N(1)#1
O(14)–N(11)–O(13)
O(14)–N(11)–C(14)
O(13)–N(11)–C(14)
O(24)–C(27)–O(23)
O(24)–C(27)–C(24)
O(23)–C(27)–C(24)
C(16)–C(11)–C(12)
C(16)–C(11)–C(17)
C(12)–C(11)–C(17)
C(13)–C(12)–C(11)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
C(13)–C(14)–N(11)
C(15)–C(14)–N(11)
C(16)–C(15)–C(14)
C(11)–C(16)–C(15)
180.0(2)
91.47(10)
88.53(10)
88.53(10)
91.47(10)
180.0
91.77(10)
88.23(10)
93.32(10)
86.68(10)
88.23(10)
91.77(10)
86.68(10)
93.32(10)
180.00(13)
125.9(3)
116.6(3)
117.5(3)
125.0(3)
117.2(3)
117.8(3)
121.8(3)
119.3(3)
118.9(3)
118.4(3)
121.6(3)
118.5(3)
119.5(3)
122.0(3)
121.1(3)
118.6(3)
N(5)#2–Co(2)–N(5)
N(5)#2–Co(2)–N(4)
N(5)–Co(2)–N(4)
N(5)#2–Co(2)–N(4)#2
N(5)–Co(2)–N(4)#2
N(4)–Co(2)–N(4)#2
N(5)#2–Co(2)–N(6)#2
N(5)–Co(2)–N(6)#2
N(4)–Co(2)–N(6)#2
N(4)#2–Co(2)–N(6)#2
N(5)#2–Co(2)–N(6)
N(5)–Co(2)–N(6)
N(4)–Co(2)–N(6)
N(4)#2–Co(2)–N(6)
N(6)#2–Co(2)–N(6)
O(11)–C(17)–O(12)
O(11)–C(17)–C(11)
O(12)–C(17)–C(11)
C(22)–C(21)–C(26)
C(22)–C(21)–N(21)
C(26)–C(21)–N(21)
C(23)–C(22)–C(21)
C(22)–C(23)–C(24)
C(25)–C(24)–C(23)
C(25)–C(24)–C(27)
C(23)–C(24)–C(27)
C(26)–C(25)–C(24)
C(21)–C(26)–C(25)
O(21)–N(21)–O(22)
O(21)–N(21)–C(21)
O(22)–N(21)–C(21)
180.0
90.53(10)
89.47(10)
89.47(10)
90.53(10)
180.000(1)
91.70(10)
88.30(10)
90.19(10)
89.81(10)
88.30(10)
91.70(10)
89.81(10)
90.19(10)
180.000(1)
122.2(3)
118.7(4)
119.0(4)
122.3(3)
119.0(3)
118.7(3)
118.2(3)
121.2(3)
119.3(3)
121.5(3)
119.2(3)
120.1(3)
118.8(3)
124.1(3)
118.7(3)
117.2(4)
Symmetry transformations used to generate equivalent atoms: #1
x, y + 1, z; #2 x + 1, y, z + 2.
5. Conclusion
A complex salt of definite composition [Co(NH3)6]Cl(O2NC6H4COO)2 was synthesized by allowing
hexaamminecobalt(III) chloride to react with sodium
para-nitrobenzoate in a 1:3 molar ratio in hot aqueous
medium. The newly synthesized salt of hexaamminecobalt(III) cation has been characterized by elemental
analyses and spectroscopic studies. X-ray structure determination of the title complex salt revealed that it contains
54
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
Fig. 3. The two adjacent hexaamminecobalt(III) cations are bonded through N–H Cl hydrogen bonds (dotted lines). The other hydrogen bonds are
omitted for clarity.
Fig. 4. The adjacent para-nitrobenzoate ions in head-to-tail fashion and forming hydrogen bonds from both ends (using both –COO and –NO2 groups)
with ammonia molecules of [Co(NH3)6]3+.
Table 4
Hydrogen bonding parameters (Å) and () of the hexaamminecobalt(III) complex salt
D–H. . .A
d (D–H)
d (H. . .A)
<DHA
d (D . . . A)
Symmetry operations
N4–H4C. . .Cl1
N6–H6A. . .Cl1
N2–H2A. . .Cl1
N1–H1B. . .Cl1
N3–H3B. . .Cl1
N3–H3A. . .O14
N2–H2B. . .N11
N2–H2B. . .O14
N1–H1C. . .O13
N2–H2C. . .Cl1
N5–H5C. . .O23
N4–H4A. . .O24
N6–H6C. . .O13
N5–H5A. . .O13
N5–H5B. . .O23
N6–H6B. . .O24
0.890(.003)
0.890(.002)
0.890(.003)
0.890(.003)
0.890(.003)
0.890(.002)
0.890(.002)
0.890(.002)
0.890(.002)
0.890(.003)
0.890(.002)
0.890(.003)
0.890(.003)
0.890(.003)
0.890(.003)
0.890(.002)
2.506(.001)
2.487(.001)
2.577(.001)
2.697(.001)
2.537(.001)
2.071(.002)
2.658(.003)
2.079(.002)
2.110(.002)
2.528(.001)
2.237(.002)
2.104(.003)
2.144(.002)
2.021(.003)
2.038(.002)
1.991(.002)
148.97(0.18)
151.66(0.17)
161.57(0.16)
154.95(0.16)
164.28(0.16)
170.54(0.17)
141.35(0.18)
164.46(0.17)
176.60(0.17)
142.69(0.17)
156.96(0.16)
159.06(0.17)
162.44(0.18)
172.05(0.19)
167.83(0.18)
161.05(0.18)
3.300(.003)
3.298(.002)
3.433(.003)
3.524(.003)
3.402(.003)
2.952(.003)
3.399(.004)
2.946(.003)
2.999(.003)
3.281(.003)
3.075(.003)
2.953(.004)
3.004(.003)
2.905(.004)
2.914(.004)
2.847(.003)
x, y, z
x, y, z
x, +y, +z 1
x 1, +y, +z 1
x 1, +y, +z 1
x, +y 1, +z
x, +y 1, +z
x, +y 1, +z
x, +y 1, +z
x + 1, y + 1, z + 1
x, y + 1, z + 1
x, y + 1, z + 1
x, +y 1, +z + 1
x, +y 1, +z + 1
x, +y 1, +z + 1
x + 1, +y 1, +z + 1
R.P. Sharma et al. / Journal of Molecular Structure 797 (2006) 49–55
cationic cobaltammine and mixed anions chloride and
para-nitobenzoate, which are held together by electrostatic
forces of attractions and intermolecular H-bond interactions, i.e. N–H O (carboxylate and nitro) and N–H Cl
based on second-sphere coordination. Thus, the hexaamminecobalt(III) cation acts as a good anion receptor
donor for such oxo-anions in aqueous medium and forms
a three dimensional network.
6. Supplementary information
Crystallographic data for the structural analysis of the
title compound 1 have been deposited with the Cambridge
Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK, and are available free of charge
from the Director on request quoting the deposition number CCDC 291414 (fax: +44 1223 336033, email:
deposit@ccdc.cam.ac.uk).
Acknowledgement
Ritu Bala thanks the CSIR, New Delhi, India, for the
financial support (Grant No. 01(1768)/02/EMR-II).
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