Synthesis and characterization of cadmium and mercury saccharinate complexes with 2-dimethylaminoethanol: cis-[Cd(sac)2(dmea) 2] and [Hg(sac)2(dmea)(H2O)]

Article abstract of DOI:10.1515/znb-2006-0508

The new cadmium and mercury saccharinate (sac) complexes, cis-[Cd(sac) ₂(dmea)₂] (1) and [Hg(sac)₂(dmea)(H ₂O)] (2) (dmea = 2-dimethylaminoethanol), have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. In complex 1, the cadmium(II) ion is coordinated by two neutral dmea ligands and two sac anions in a distorted octahedral CdN₃O₃ coordination geometry. The dmea ligand acts as a bidentate N, O chelate, while the sac ligands behave as an ambidentate ligands. One of them coordinates to the cadmium(II) ion through the carbonyl oxygen atom, while the other is N-bonded. In complex 2, the mercury(II) ion is coordinated by an aqua ligand, a chelating dmea ligand and two N-bonded sac ligands, forming a distorted trigonal bipyramidal coordination HgN ₃O₂. The molecules interact with each other through O-H?O hydrogen bonds and aromatic π(sac)?π(sac) stacking interactions, leading to a three-dimensional supramolecular network.

Full text of DOI:10.1515/znb-2006-0508

Synthesis and Characterization of Cadmium and Mercury
Saccharinate Complexes with 2-Dimethylaminoethanol:
cis-[Cd(sac)2(dmea)2] and [Hg(sac)2(dmea)(H2O)]
Veysel T. Yilmaza, Vecdi Karsa, and Canan Kazakb
a Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University,
55139 Kurupelit, Samsun, Turkey
b Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University,
55139 Kurupelit, Samsun, Turkey
Reprint requests to Prof. Dr. V. T. Yilmaz. E-mail: vtyilmaz@omu.edu.tr
Z. Naturforsch. 61b, 555 – 559 (2006); received January 20, 2006
The new cadmium and mercury saccharinate (sac) complexes, cis-[Cd(sac)2(dmea)2] (1) and
[Hg(sac)2(dmea)(H2O)] (2) (dmea = 2-dimethylaminoethanol), have been prepared and character-
ized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction.
In complex 1, the cadmium(II) ion is coordinated by two neutral dmea ligands and two sac anions
in a distorted octahedral CdN3O3 coordination geometry. The dmea ligand acts as a bidentate N,
O chelate, while the sac ligands behave as an ambidentate ligands. One of them coordinates to the
cadmium(II) ion through the carbonyl oxygen atom, while the other is N-bonded. In complex 2, the
mercury(II) ion is coordinated by an aqua ligand, a chelating dmea ligand and two N-bonded sac
ligands, forming a distorted trigonal bipyramidal coordination HgN3O2. The molecules interact with
each other through O–H···O hydrogen bonds and aromatic π(sac)···π(sac) stacking interactions,
leading to a three-dimensional supramolecular network.
Key words: Saccharinate, 2-Dimethylaminoethanol, Cadmium, Mercury, Crystal Structure
Introduction
Saccharin (C7H5NO3S; also named 1,2-benzisothi-
azoline-3-(2H)one 1,1-dioxide or o-benzosulfimide)
and its water soluble alkali and earth-alkali salts are
widely used as non-caloric artificial sweeteners [1].
The presence of several potential donor atoms such as
the imino nitrogen, one carbonyl and two sulfonyl oxy-
gen atoms makes sac an interesting polyfunctional lig-
and in coordination chemistry. While metal complexes
of neutral saccharin are not known, its deprotonated
anion, saccharinate (sac), readily coordinates to vari-
ous metal ions [2, 3]. Sac exhibits different coordina-
tion modes using these donor atoms, behaving as a N-
or O-monodentate, bidentate (N,O), tridentate (N,O,O)
chelating and/or bridging ligand, forming complexes
from monomers to coordination polymers [3]. A less-
common coordination characteristic of the ligand is the
ambidentate coordination behavior, or the formation of
M–N and M–O bonds with two different sac ligands in
the same complex [3].
sac with N- and O-donor ligands, we reported a he-
lical polymeric complex of copper(II)-sac with 2-di-
methylaminoethanol (dmea), [Cu2(sac)2(µ-dmea)2(µ-
H2O)]n [4], and in this paper, we describe the syn-
thesis, spectral, thermal and structural characterization
of new bis(saccharinato)cadmium and mercury com-
plexes with the same co-ligand, namely cis-[Cd(sac)2-
(dmea)2] (1) and [Hg(sac)2(dmea)(H2O)] (2).
Results and Discussion
Complexes 1 and 2 are obtained by the direct re-
action of the dmea ligand with the starting complexes
[Cd(sac)2(H2O)4] · 2H2O and [Hg(sac)2], respectively,
As a part of our continuing research on the synthe- in reasonable yields. Complex 1 is soluble in water,
sis and characterization of mixed-ligand complexes of methanol, ethanol, and n-butanol, but sparingly solu-
c
0932–0776 / 06 / 0500–0555 $ 06.00 ꢀ 2006 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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V. T. Yilmaz et al. · Cadmium and Mercury Saccharinate Complexes
Table 1. Selected bond lengths and angles, and hydrogen
bonding geometry of 1.
◦
˚
Bond lengths (A) and angles ( ):
Cd1–N2
Cd1–N3
Cd1–N4
Cd1–O3
Cd1–O7
Cd1–O8
N2–Cd1–N3
N2–Cd1–N4
N3–Cd1–N4
N2–Cd1–O3
N2–Cd1–O7
Hydrogen bonds:
2.299(7)
2.323(8)
2.351(7)
2.262(5)
2.400(6)
2.331(7)
97.9(3)
97.9(3)
162.4(3)
96.5(2)
N2–Cd1–O8
N3–Cd1–O3
N3–Cd1–O7
N3–Cd1–O8
N4–Cd1–O3
N4–Cd1–O7
N4–Cd1–O8
O3–Cd1–O7
O3–Cd1–O8
O7–Cd1–O8
92.4(2)
93.7(3)
78.4(3)
98.3(3)
92.2(3)
85.1(3)
73.4(3)
89.3(2)
163.9(2
82.6(3)
173.3(2)
D–H (A) H···A (A) D···A (A) D–H···A (◦)
˚
˚
˚
D–H···A
O8–H8···O6 0.93
2.62
2.848(11) 95
Fig. 2. Packing diagram of 1, showing π(sac)···π(sac) stack-
ing interactions. All C–H hydrogen atoms are omitted for
clarity.
coordinated at trans positions. During complex forma-
tion, the sac coordination geometry was switched from
trans to cis. Furthermore, complex 1 exhibits a less-
common coordination characteristic of the sac ligand:
both sac ligands are monodentate, but one is N-bonded,
while the other one is coordinated through the carbonyl
O atom behaving as an ambidentate ligand as observed
only in the following complexes: [Cu(sac)2(py)3]
(py = pyridine) [5], [Cu(sac)2(dipy)(H2O)] (dipy =
dipyridylamine) [6], ApyH[Cu(H2O)2(sac)3] (ApyH =
2-aminopyridinium) [7], and [M(sac)2(pym)2], where
pym = 2-pyridylmethanol, M = CoII [8], NiII [12],
ZnII [9], and CdII [9].
Fig. 1. A view of the molecular structure of complex 1, show-
ing 30% displacement ellipsoids (arbitrary spheres for the
H atoms). Intramolecular hydrogen bonds are indicated by
dashed lines.
ble in isopropanol, while complex 2 is slightly soluble
in water and ethanol, but highly soluble in methanol.
Both complexes are non-hygroscopic and stable in air.
Complexes 1 and 2 do not melt, but decompose at 86
and 28 ◦C, respectively.
The Cd–Nsac and Cd–Osac bond distances are simi-
lar to those reported for [Cd(sac)2(pym)2]: 2.2612(14)
and 2.2755(17) A [9]. The M–Ndmea and M–Odmea
bond distances in complex 1 are slightly longer than
the Cd–Nsac and Cd–Osac bond distances. Significant
distortions are evident from the angles in the coordi-
nation octahedron as seen from Table 1. The largest
deviations from the ideal values were observed in the
bite angles of the dmea ligands.
Description of the crystal structures
˚
The molecular structure of complex 1 with the
atom labeling scheme is shown in Fig. 1 and se-
lected bond distances and angles are listed in Table 1.
Complex 1 consists of individual neutral molecules
of [Cd(sac)2(dmea)2], in which cadmium(II) is oc-
tahedrally coordinated by two neutral dmea lig-
ands and two sac anions, constituting a distorted
meridional CdN3O3 chromophore. Each dmea lig-
Both sac ligands in complex 1 are essentially pla-
and acts as a bidentate N, O-ligand, forming a five- nar. The planes of the two sac ligands are nearly co-
membered metallocyclic chelate ring. The sac lig- planar with a dihedral angle of 8.84(34)◦. The pack-
and is usually involved in the formation of N- or O- ing diagram of complex 1 is presented in Fig. 2. Com-
bonded mononuclear complexes. In the starting com- plex 1 exhibits an intra-molecular O–H···O hydrogen
plex [Cd(sac)2(H2O)4]·2H2O, both sac ligands are N- bond, and packing of the molecules of 1 is achieved
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V. T. Yilmaz et al. · Cadmium and Mercury Saccharinate Complexes
557
Table 2. Selected bond lengths and angles, and hydrogen Table 3. Selected IR spectral dataa for 1 and 2.
bonding geometry of 2.
Assignments
ν(OH)
1
2
◦
˚
3336s,br
3440s,br
3060vw, 2953vw
1624vs
1458m
1384vs
1285vs, 1250vs
1153vs
965s
Bond lengths (A) and angles ( ):
ν(CH)
3106vw, 2978vw, 2802w
1651vs, 1600vs
1472s
1344m
1268vs
Hg1–N1
Hg1–N2
Hg1–N3
Hg1–O1W
Hg1–O7
2.154(9)
2.108(9)
2.349(12)
2.820(9)
2.541(9)
N1–Hg1–O1W
N1–Hg1–O7
N2–Hg1–O1W
N2–Hg1–O7
N3–Hg1–O1W
N3–Hg1–O7
O1W–Hg1–O7
94.9(4)
95.8(3)
90.9(4)
96.6(4)
82.5(4)
72.2(4)
154.1(4)
ν(CO)
ν(CC)
νs(CNS)
νas(SO2)
νs(SO2)
νas(CNS)
a
1165vs
961vs
N1–Hg1–N2
N1–Hg1–N3
N2–Hg1–N3
Hydrogen bonds:
138.4(4)
101.8(4)
119.8(4)
Frequencies in cm−1; b = broad; w = weak; vs = very strong;
s = strong; m = medium; sh = shoulder.
◦
˚
˚
˚
D–H···A
D–H (A) H···A (A) D···A (A) D–H···A ( )
O1W–H1W···O1 0.84(9) 2.39(11)
2.898(13) 119(10)
2.761(13) 135
O7–H7···O1i
0.93
2.02
i
Symmetry operation x, y−1, z.
Fig. 4. Packing diagram of 2, showing hydrogen bonds
and π(sac)···π(sac) stacking interactions. All C–H hydrogen
atoms are omitted for clarity. Hydrogen bonds are indicated
by dashed lines.
(sac)4(mpy)2] [15] and [Hg(sac)2(aepy)] 2.151(4) and
2.233(3) A [16], but much shorter than 2.739(3) A
Fig. 3. A view of the molecular structure of complex 2, show-
ing 30% displacement ellipsoids (arbitrary spheres for the
˚
˚
H atoms). Intramolecular hydrogen bonds are indicated by in [Hg(ea)2(sac)2] [17] and trans-[Hg(sac)2(ampy)2]
dashed lines.
˚
2.7955(16) A [16], where bipy, py, pyet, mpy, ea,
aepy and ampy are 2,2’-bipyridyl, pyridine, 2-pyrid-
ylethanol, 2-pyridylethanol, ethanolamine, 2-amino-
ethylpyridine and 2-aminomethylpyridinerespectively.
The Hg–Ndmea bond distance of 2.349(12) A is sig-
nificantly longer than The Hg–Nsac bond distances.
by an aromatic π(sac)–π(sac) stacking interaction be-
tween the phenyl rings of the neighboring sac units
i
with a Cg ··· Cg (Cg = centroid of atoms) distance of
˚
i
˚
3.693(4) A [ : x, 1/2−y, −1/2+z].
Fig. 3 shows the molecular structure of complex 2
with the atom labeling. Selected interatomic distances
and angles are listed in Table 2, together with the
hydrogen bonding geometry. In complex 2, the mer-
cury(II) cation exhibits a distorted trigonal bipyramidal
coordination geometry with a neutral bidendate (N,O)
dmea ligand and two N-bonded sac ligands, thus form-
ing a HgN3O2 chromophore. The N atoms form the
trigonal plane, while the O atoms occupy the apical
positions. The Hg–Nsac bond distances are similar to
the corresponding values found in previously reported
mercury(II) complexes with sac: 2.037, 2.049, 2.029
Among the five coordination bonds in complex 2, the
Hg–OW bond distance of 2.820(9) A is much longer,
indicating a weak interaction of the water molecule
with mercury(II).
˚
The sac ligands are planar and the dihedral an-
gle between them is 70.56(20)◦. The individual
molecules of 2 are linked by O–H···O hydrogen bonds
i
and π(sac)–π(sac) stacking interactions [Cg ··· Cg
=
i
˚
3.589(8) A; 1 − x, 2 − y, −z], leading to a three-
dimensional network as shown in Fig. 4.
IR spectra
˚
˚
and 2.058 A in [Hg(sac)2] [10], 2.019 A in [Hg(Cl)-
˚
(sac)] [11], 2.120 and 2.140 A in [Hg(sac)2(bipy)] [12],
Selected FTIR data of both complexes 1 and 2
˚
2.106(7) and 2.209(7) A in [Hg2(Cl)2(sac)2(py)] [13], are presented in Table 3. The strong and relatively
2.087(2), 2.117(2), 2.182(2) and 2.193(2) A in [Hg- broad bands centered at around 3340 cm−1 are at-
˚
˚
(sac)2(pyet)] [14], 2.094(2) and 2.106(2) A in [Hg2- tributed to the ν(O–H) vibration of the hydrogen-
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558
V. T. Yilmaz et al. · Cadmium and Mercury Saccharinate Complexes
Table 4. Crystallographic data for 1 and 2.
bonded hydroxyl groups of the dmea ligand and the
aqua ligand in complex 2. The relatively weak absorp-
tion bands between 2960– 3100 cm−1 are assigned
to the ν(CH) vibrations. The stretching vibration of
the carbonyl group of sac appears as two separate
sharp bands at 1651 and 1600 cm−1 for complex 1,
and as a single band at 1624 cm−1 for complex 2.
The higher frequency absorption band in the spec-
trum of complex 1 is characteristics for the N-bond-
ed sac ligand, whereas the lower frequency band is
assigned to the sac O-bonded via the carbonyl group,
due to the expected weakening of the C=O bond upon
coordination. The single carbonyl band in the spec-
trum of complex 2 clearly indicates that both sac lig-
ands are N-coordinated. The strong absorption bands at
around 1460 cm−1 correspond to the ν(CC) vibrations
of the aromatic ring of sac. The νas(SO2) vibrations
appear as a sharp band centered at 1268 cm−1 in com-
plex 1, but as two split bands at 1285 and 1250 cm−1
in complex 2, while the νs(SO2) mode of sac appears
1
2
Empirical formula
Mr
C22H30N4O8S2Cd C18H21N3O8S2Hg
655.05
monoclinic
P21/c
14.3890(7)
12.7790(5)
15.5260(8)
90
109.786(4)
90
2686.3(2)
4
672.11
triclinic
P1
Crystal system
Space group
¯
˚
a [A]
7.6376(9)
7.8699(9)
20.563(2)
94.741(9)
92.967(9)
116.765(18)
1094.3(3)
2
˚
b [A]
˚
c [A]
α [◦]
β [◦]
γ [◦]
3
˚
V [A ]
Z
Dc [g/cm3]
1.620
1.021
1336
2.040
7.275
652
µ [mm−1
F(000)
]
Crystal size [mm3]
θ Range [◦]
0.52×0.35×0.22 0.37×0.33×0.28
2.12 – 27.87
−18/17,
2.00 – 26.00
−9/9,
Index range (h,k,l)
−16/16,
−9/9,
−20/20
−25/25
Reflections collected
Independent refls (Rint
Absorption correction
28192
14012
)
6368 (0.0828)
Numerical
4305 (0.0768)
Numerical
0.082 and 0.127
4305 / 278
1.056
0.0603
0.1592
1.5 and −3.2
as a very strong band at ca. 1160 cm−1
.
Min. and max. transmission 0.773 and 0.825
Data / parameters
Goodness-of-fit on F2
R Indices [I > 2σ(I)]
wR2 (all data)
6368 / 322
1.086
0.0771
Thermal analysis
The thermal decomposition processes for com-
plexes 1 and 2 were followed up to 800 ◦C in a
static atmosphere of air. Complex 1 decomposes at two
0.2365
Largest diff. pea−k3
4.2 and −2.0
˚
and hole [e.A
]
◦
stages. The first stage between 86 and 342 C corre-
according to the literature methods reported by Haider et
al. [18] and Kamenar et al. [19], respectively.
sponds to the endothermic removal of two dmea lig-
ands (mass loss: found 27.0%, calcd. 27.2%). Decom-
position of the sac moiety occurs at higher temper-
atures characterized by two highly exothermic peaks
at 471 and 521 ◦C. The decomposition of 1 ends
at 566 ◦C, giving a solid residue of CdO.
Complex 2 shows a three-step decompos◦ition pro-
cess. In the first step between 28 and 58 C, it de-
hydrates with a mass loss of 3.0% (calcd. 2.7%). In
the second step, the elimination of the dmea ligand
takes place in the temperat◦ure range 65 – 212 with an
endothermic peak at 187 C. The experimental mass
loss of 13.4% is in accord with the calculated value
of 13.2%. At higher temperatures, the degradation of
the sac ligands occurs with two extremely exothermic
peaks at 323 and 479 ◦C to give an end product of HgO.
Elemental analyses (C, H, N and S) were carried out
on an Elementar Vario EL elemental analyzer. The FT-IR
spectra were recorded from KBr pellets in the range 4000 –
400 cm−1 by using a JASCO FT/IR-430 spectrophotometer.
Thermal analysis curves (TG and DTA) were obtained using
a Rigaku TG8110 thermal analyzer in a static air atmosphere
at a heating rate of 10 ◦C min−1
.
Synthesis of the complexes
The dmea ligand (0.09 g, 1.0 mmol) was added drop-wise
to a solution of [Cd(sac)2(H2O)4]·2H2O (0.29 g, 0.5 mmol)
dissolved in a methanol and isopropanol mixture (1 : 1, v : v;
20 cm3) with continuous stirring at 60 ◦C. Colorless crystals
of complex 1 suitable for X-ray diffraction were obtained
by slow diffusion of the resulting solution into ether after
◦
two days. Yield: ca. 40%. d. p. 86 C. C22H30N4O8S2Cd
(655.02); calcd. C 40.3, H 4.6, N 8.6, S 9.8; found C 40.5,
H 4.5, N 8.9, S 10.0.
Experimental Section
Materials and measurements
Complex 2 was prepared by a similar synthesis pro-
All reagents were commercially available and used cedure, using [Hg(sac)2] (0.29 g, 0.5 mmol) instead of
without further purification. The starting complexes [Cd(sac)2(H2O)4]·2H2O. Colorless crystals of complex 2
[Cd(sac)2(H2O)4]·2H2O and [Hg(sac)2] were prepared were obtained by slow diffusion of the resulting solution
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V. T. Yilmaz et al. · Cadmium and Mercury Saccharinate Complexes
559
into ether after two days. Yield ca. 35%. d. p. 28 ◦C. positions. The hydrogen atoms of the disordered atoms were
C18H21N3O8S2Hg (672.09): calcd. C 32.2, H 3.1, N 8.6, positioned by applying the HFIX. Attempts to solve the
S 9.8; found C 32.5, H 3.3, N 8.9, S 10.0.
problem failed. Therefore, the disorder phenomena results
in short intra- and intermolecular hydrogen bonds, a short
C15–C16 distance and a high residual electron density. The
details of data collection, refinement and crystallographic
data are summarized in Table 4.
Crystallographic data have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publi-
cation no, CCDC-295608 (1) and CCDC-295609 (2). Copies
of the data can be obtained on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK [Fax: (internat.)
+ 44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
X-ray crystallography
The data collections were performed at 293 K for
both complexes on a Stoe-IPDS-2 diffractometer with
graphite-monochromated Mo-Kα radiation (λ = 0.71073 A).
˚
The structures were solved by Direct Methods using
SHELXS-97 [20] and refined by full-matrix least-squares
methods using SHELXL-97 [20]. All non-hydrogen atoms
were easily found in a difference Fourier map and refined
anisotropically. All hydrogen atoms were refined in the rid-
ing mode on their carrier atoms. Atoms C15, C16 and C18
in complex 1 were found to be highly disordered and an
isotropic refinement of the disordered atoms split over two
Acknowledgement
The authors wish to thank Ondokuz Mayis University for
financial support.
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