Structural study of the coordination behavior of a tetradentate NO3-donor amino alcohol ligand toward a CdII:HgII mixture

Article abstract of DOI:10.1515/znb-2016-0222

In this work, the reaction of 2,2′,2″-nitrilotriethanol (NTE) with a 1:1 mixture of CdI₂ and HgI₂ is investigated. The complex [Cd(NTE)₂][Hg₂(μ-I)₂I₄] was synthesized and identified by elemental analysis, FT-IR, ¹H NMR spectroscopy and single-crystal X-ray diffraction. The structure of the [HNTE]Cl salt is also presented. In the crystal structure of the complex, the cadmium atom has a CdN₂O₆ environment in a slightly distorted cube geometry. This geometry is one of the rare cube geometries with a minimum distortion among the Cambridge Structural Database structures for cadmium complexes. The anionic moiety has a binuclear structure with the mercury atoms being in tetrahedral environments. In the network of the complex, in addition to O-H ? I hydrogen bonds, there are I ? I interactions which lead to ten-membered rings.

Full text of DOI:10.1515/znb-2016-0222

Z. Naturforsch. 2017; aop
Zahra Mardani*, Vali Golsanamlou, Saba Khodavandegar, Keyvan Moeini,
Alexandra M.Z. Slawin and J. Derek Woollins
Structural study of the coordination behavior
of a tetradentate NO -donor amino alcohol ligand
3
II
II
toward a Cd :Hg mixture
DOI 10.1515/znb-2016-0222
Database (CSD) data [4]] can act as NO -, NO -, NO-,
3 2
Received October 2, 2016; accepted December 16, 2016
O - and O -donor; the NO -donor form is the most com-
3
2
3
monly observed. Complexes containing both cadmium
and mercury atoms are rare and only 14 structures have
been reported [5–18]. These structural motifs are present
in a variety of compounds including the heterobimetallic
RHg/Cd species [15], heteronuclear complexes of cyano-
metallates [14], coordination polymers [8, 9, 11, 12, 16],
clathrates [ML M′(CN) .2G] [7, 13] and noncentrosymmet-
Abstract: In this work, the reaction of 2,2′,2″-nitrilot-
riethanol (NTE) with a 1:1 mixture of CdI and HgI is
2
2
investigated. The complex [Cd(NTE) ][Hg (μ-I) I ] was
2
2
2 4
synthesized and identified by elemental analysis, FT-IR,
1
H NMR spectroscopy and single-crystal X-ray diffraction.
The structure of the [HNTE]Cl salt is also presented. In the
crystal structure of the complex, the cadmium atom has
a CdN O environment in a slightly distorted cube geom-
n
4
ric materials [18]. Cadmium-mercury thiocyanates exhibit
good second-order nonlinear optical effects, a wide trans-
parency wavelength region [11, 17, 18] and piezoelectricity
properties [18]. In this paper, the preparation, characteri-
zation and crystal structure of [Cd(NTE) ][Hg (μ-I) I ] are
2
6
etry. This geometry is one of the rare cube geometries with
a minimum distortion among the Cambridge Structural
Database structures for cadmium complexes. The anionic
moiety has a binuclear structure with the mercury atoms
being in tetrahedral environments. In the network of the
complex, in addition to O−Hꢀ·ꢀ·ꢀ·ꢀI hydrogen bonds, there
are Iꢀ·ꢀ·ꢀ·ꢀI interactions which lead to ten-membered rings.
2
2
2 4
presented.
2
Results and discussion
Keywords: amino alcohol; Cd/Hg mixed-metal complex;
coordination behavior; cube geometry; X-ray crystal
structure.
The reaction between NTE and an ethanol solution of a
CdI /HgI mixture afforded crystals of a complex which is
2
2
air-stable and soluble in DMF and DMSO. In the IR spec-
trum of the complex, the ν (O–H) band is shifted by about
−1
1
Introduction
100 cm to higher frequency than that of the free ligand
[
19], indicating coordination through the oxygen atoms. In
1
Amino alcohol functional groups are often found in bio- the H NMR spectra of NTE [19] and of the complex, there
logically active molecules, ligands and chiral auxiliaries are two groups of signals in the region of 2.5–3.5 and above
[
1–3]. These types of ligands contain several coordination 4.5 ppm. The broad singlet above 4.5 ppm is assigned
sites, which may interact with a metal center in differ- to protons of the alcoholic moiety and the multiplet is
ent ways. An example of such ligands is 2,2′,2″-nitrilot- assigned to protons of the aliphatic hydrogen atoms. After
riethanol (NTE), which [based on Cambridge Structural coordination of NTE, the OH signal is shifted by about
1
ppm to a lower field, consistent with coordination of all
alcoholic groups toward the metal atom. No significant
shift was observed for the aliphatic hydrogen atoms.
The crystal structure of the complex has been deter-
mined. In addition to the complex, the structure of the
*
Corresponding author: Zahra Mardani, Chemistry Department,
Urmia University, 57561-51818 Urmia, I.R. Iran,
e-mail: mardani_zahra@yahoo.com
Vali Golsanamlou and Saba Khodavandegar: Chemistry Department,
Urmia University, 57561-51818 Urmia, I.R. Iran
[
HNTE]Cl salt is presented in this work (Fig. 1). Owing to
the previous reports on similar structures [20, 21], details
about this structure will only briefly be discussed here.
It should be mentioned that the collection of the data for
this salt was carried out of a different temperature (93 K)
Keyvan Moeini: Chemistry Department, Payame Noor University,
1
9395-4697 Tehran, I.R. Iran
Alexandra M.Z. Slawin and J. Derek Woollins: EaStCHEM School of
Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

ꢁꢁꢁꢂ
ꢀ ꢀZ. Mardani et al.: Coordination behavior of a tetradentate NO -donor amino alcohol ligand
2
3
2
+
The compound consists of [Cd(NTE) ] cations and
2
2−
binuclear [I Hg(μ-I ) HgI ] anions (Fig. 2). The cadmium
2
2
2
2
atom has a slightly distorted cube coordination geometry
of six oxygen and two nitrogen atoms of two NTE ligands
(
Fig. 3). The averages of the six Cd−O (2.4460 Å) and two
Cd−N bond lengths (2.4345 Å) are shorter than the CSD
average [4] for compounds with a Cd(Ntert-amine)(Oalcohol)3
environment (2.4615 and 2.4671 Å, respectively). Each
ligand forms three five-membered non-planar chelate
rings. Similar donor atoms of the two coordinated NTE
ligands lie in trans positions to each other. The three
alcoholic arms of the free ligand (Fig. 1) and its complex
(
Fig. 2) are co-orientated. In the structural network of the
Fig. 1:ꢁOꢍꢎꢏꢐ-III diagram of the molecular structure of the [HNTE]Cl
ligand salt, there are O–Hꢀ·ꢀ·ꢀ·ꢀCl, C–Hꢀ·ꢀ·ꢀ·ꢀO and C–Hꢀ·ꢀ·ꢀ·ꢀCl
interactions. Among them, the O–Hꢀ·ꢀ·ꢀ·ꢀCl hydrogen bonds
salt.
3
participate in the formation of one R (30) hydrogen bond
motif (three acceptors, six donors with degree of 30) [1, 22]
6
+
than before (100 and 283–303 K). A structural compari- between three [HNTE] units (Fig. 4). If the distortion of
son of [HNTE]Cl with the previous results revealed that alcoholic groups in the cationic unit of the [HNTE]Cl salt
bond lengths and angles of them are slightly different is disregarded, with a C axis on the nitrogen atom, it has
as well as the properties of hydrogen bonds. Crystal- C3 symmetry.
3
lographic data and details of the data collection and
A study of the angles at cadmium atoms with coordi-
structure refinement are listed in Table 1, selected bond nation number eight in the CSD reveals that coordination
lengths and angles in Table 2 and hydrogen bond geom- of two ligands including 4,7,13,16,21,24-hexaoxa-l,10-diaz-
etries in Table 3.
abicyclo-[8.8.8]hexacosan [23] and tris(2-pyridylmethyl)
Table 1:ꢁCrystal data and structure refinement for [Cd(NTE) ][Hg (μ-I) I ] and [HNTE]Cl.
2
2
2 4
Complex
[HNTE]Cl
Empirical formula
Formula weight, g mol
Crystal size, mmꢅ
Temperature, K
Crystal system
Space group
Unit cell dimensions
a, Å
C H CdHg I N O
C H ClNO
ꢅ
ꢃꢄ ꢅꢆ
ꢃꢈꢉꢅ.ꢊꢆ
ꢄ
ꢇ
ꢄ
ꢇ
ꢇ
ꢃꢇ
−ꢃ
ꢃꢋꢈ.ꢇꢈ
ꢆ.ꢃꢄꢂ×ꢂꢆ.ꢃꢆꢂ×ꢂꢆ.ꢃꢆ
ꢌꢅ
Monoclinic
Pꢄ/c
ꢆ.ꢄꢆꢂ×ꢂꢆ.ꢄꢆꢂ×ꢂꢆ.ꢄꢆ
ꢌꢅ
Trigonal
Rꢅc
ꢃꢉ.ꢆꢅꢃ(ꢄ)
ꢋ.ꢄꢄꢇ(ꢅ)
b, Å
ꢋ.ꢇꢄꢃꢅ(ꢌ)
ꢋ.ꢄꢄꢇ(ꢅ)
c, Å
ꢄꢃ.ꢅꢉꢉ(ꢅ)
ꢄꢄ.ꢉꢇꢅ(ꢉ)
β, deg
ꢃꢆꢈ.ꢉꢋꢉ(ꢅ)
ꢌꢆ
Volume, Åꢅ
Z
ꢅꢆꢄꢆ.ꢊ(ꢇ)
ꢃꢅꢅꢅ.ꢌ(ꢋ)
ꢊ
ꢇ
Calculated density, g cm−
ꢅ
ꢅ.ꢊꢇ
ꢃ.ꢅꢌ
Absorption coefficient, mm−
ꢃ
ꢃꢉ.ꢆ
ꢆ.ꢊ
F(ꢆꢆꢆ), e
ꢄꢉꢇꢆ
ꢇꢆꢆ
θ range for data collection (deg)
h, k, l ranges
ꢄ.ꢊ–ꢄꢉ.ꢊ
ꢅ.ꢊ–ꢄꢉ.ꢅ
−ꢄꢆꢂ≤ꢂhꢀ≤ꢀꢄꢆ, −ꢃꢆꢂ≤ꢂkꢀ≤ꢀꢃꢆ, −ꢃꢉꢂ≤ꢂlꢀ≤ꢀꢄꢈ
−ꢌꢂ≤ꢂhꢀ≤ꢀꢌ, −ꢌꢂ≤ꢂkꢀ≤ꢀꢌ, −ꢄꢇꢂ≤ꢂlꢀ≤ꢀꢄꢇ
ꢊꢊꢊꢆ/ꢈꢊꢌ/ꢆ.ꢆꢈꢊ
ꢈꢊꢌ/ꢊꢆ
Reflections collected/independent/Rint
Data/ref. parameters
ꢃꢈꢂꢈꢇꢌ/ꢈꢊꢉꢃ/ꢆ.ꢆꢊꢈ
ꢈꢊꢉꢃ/ꢄꢋꢇ
ꢆ.ꢌꢇꢆ
ꢄ
Goodness-of-fit on F
ꢃ.ꢃꢆ
Rꢃ/wRꢄ (Iꢂ>ꢂꢄσ(I))
ꢆ.ꢆꢄꢊꢌ/ꢆ.ꢆꢈꢄꢃ
ꢆ.ꢆꢄꢋꢌ/ꢆ.ꢆꢈꢅꢃ
–
ꢆ.ꢆꢅꢃꢈ/ꢆ.ꢆꢇꢉꢅ
ꢆ.ꢆꢅꢃꢉ/ꢆ.ꢆꢇꢉꢊ
−ꢆ.ꢆꢊ(ꢊ)
Rꢃ/wRꢄ (all data)
Flack parameter
Largest diff. peak/hole, e Å−
ꢅ
ꢃ.ꢇꢆ/−ꢄ.ꢅꢈ
ꢆ.ꢄꢆ/−ꢆ.ꢃꢌ
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

Z. Mardani et al.: Coordination behavior of a tetradentate NO -donor amino alcohol ligandꢀꢂꢁꢁꢁꢀ3
3
2
−
Table 2:ꢁSelected bond lengths (Å) and angles (deg) for [Cd(NTE) ]
The [I Hg(μ-I ) HgI ] anion is a binuclear complex
2 2 2 2
2
a
[
Hg (μ-I) I ] with estimated standard deviations in parentheses .
2
2
4
of mercury(II), containing two types of iodide ligands
bridging and terminal) and two mercury atoms with coor-
dination number four in tetrahedral environment. The
averages of the four Hg−Iterminal and two Hg−Ibridging bond
lengths are 2.6910 and 2.9540 Å, respectively, which are
comparable with the CSD averages (2.6931 and 2.9230
Å, respectively). The tetracoordinate geometry of the
(
Bond lengths
Angles
Cd(ꢃ)–N(ꢃ)
Cd(ꢃ)–N(ꢄ)
Cd(ꢃ)–O(ꢄ)
Cd(ꢃ)–O(ꢊ)
Cd(ꢃ)–O(ꢇ)
Cd(ꢃ)–O(ꢋ)
Cd(ꢃ)–O(ꢃꢆ)
Cd(ꢃ)–O(ꢃꢄ)
Hg(ꢃ)–I(ꢃ)
Hg(ꢃ)–I(ꢄ)
Hg(ꢃ)–I(ꢅ)
Hg(ꢄ)–I(ꢊ)
Hg(ꢄ)–I(ꢈ)
Hg(ꢄ)–I(ꢇ)
ꢄ.ꢊꢊꢆ(ꢈ)
ꢄ.ꢊꢄꢊ(ꢈ)
ꢄ.ꢊꢌꢌ(ꢈ)
ꢄ.ꢊꢄꢊ(ꢊ)
ꢄ.ꢊꢃꢌ(ꢈ)
ꢄ.ꢊꢄꢈ(ꢈ)
ꢄ.ꢊꢌꢃ(ꢊ)
ꢄ.ꢊꢄꢉ(ꢈ)
ꢄ.ꢋꢋꢅꢈ(ꢈ)
ꢄ.ꢇꢋꢇꢅ(ꢈ)
ꢄ.ꢉꢄꢄꢆ(ꢇ)
ꢄ.ꢋꢌꢌꢇ(ꢇ)
ꢄ.ꢇꢉꢋꢃ(ꢈ)
ꢄ.ꢇꢉꢇꢋ(ꢈ)
Hg(ꢃ)–I(ꢃ)–Hg(ꢃ)i
ꢋꢆ.ꢋꢇꢃ(ꢃꢊ)
ꢌꢆ.ꢇꢆꢉ(ꢃꢉ)
ꢌꢌ.ꢃꢅꢋ(ꢃꢊ)
ꢃꢄꢊ.ꢌꢃꢉ(ꢃꢉ)
ꢋꢌ.ꢄꢉꢃ(ꢃꢋ)
ii
Hg(ꢄ)–I(ꢊ)–Hg(ꢄ)
i
I(ꢃ)–Hg(ꢃ)–I(ꢃ)
I(ꢄ)–Hg(ꢃ)–I(ꢅ)
ii
I(ꢊ)–Hg(ꢄ)–I(ꢊ)
I(ꢇ)–Hg(ꢄ)–I(ꢈ)
ꢃꢄꢋ.ꢈꢌꢈ(ꢃꢌ) mercury atom can adopt either a tetrahedral or a square
ꢃꢉꢅ.ꢊꢄ(ꢃꢇ) planar configuration. To determine the geometry of such
N(ꢄ)–Cd(ꢃ)–N(ꢃ)
O(ꢊ)–Cd(ꢃ)–O(ꢃꢄ)
O(ꢃꢆ)–Cd(ꢃ)–O(ꢄ)
O(ꢋ)–Cd(ꢃ)–O(ꢇ)
O(ꢊ)–Cd(ꢃ)–O(ꢄ)
N(ꢄ)–Cd(ꢃ)–O(ꢄ)
O(ꢃꢄ)–Cd(ꢃ)–O(ꢄ)
N(ꢃ)–Cd(ꢃ)–O(ꢄ)
ꢃꢉꢅ.ꢅꢈ(ꢃꢇ)
structures, the formula of Hakimi et al. [25] was applied
ꢃꢉꢊ.ꢃꢉ(ꢃꢉ)
in which the angular structural parameter (τ ) is rep-
sq
ꢃꢉꢃ.ꢆꢆ(ꢃꢇ)
resented as the index of tetragonality. The parameter
ꢃꢆꢉ.ꢈꢉ(ꢃꢇ)
τsqꢀ=ꢀ(θ
max
– θmin)/90, where θmax and θmin are the maximum
ꢃꢆꢋ.ꢊꢃ(ꢃꢈ)
ꢇꢌ.ꢌꢃ(ꢃꢋ) and minimum bond angles, respectively. An ideal square
ꢇꢌ.ꢉꢅ(ꢃꢈ)
plane will have θmaxꢀ=ꢀ180° and θminꢀ=90°, and therefore
ꢀ
aSymmetry codes: i −x, −y+1, −z+1; ii –x+1, y, −z+0.5.
τsqꢀ=ꢀ1, but an ideal tetrahedron will have θmaxꢀ=ꢀ109.28°,
θminꢀ=109.28° and therefore τ ꢀ=ꢀ0. The τ value is calcu-
ꢀ
sq
sq
lated to be 0.29 and 0.44 for Hg1 and Hg2, respectively,
amine [24], to the cadmium atom produces the cube thus indicating an inclination to a tetrahedral geometry
2−
geometry with the lowest distortion, and our complex [25]. In the structure of the complex, two [I Hg(μ-I ) HgI ]
2
2
2
2
with the NTE ligand is now the third example to show this anions have different point group symmetries. The anion
geometry.
containing an Hg1 atom has one center of inversion on the
Table 3:ꢁHydrogen bond geometries (Å, deg) for [Cd(NTE) ][Hg (μ-I) I ].
2
2
2 4
D–Hꢁ·ꢁ·ꢁ·ꢁA
d(D–H)
d(Hꢁ·ꢁ·ꢁ·ꢁA)
ꢁ<(DHA)
d(Dꢁ·ꢁ·ꢁ·ꢁA)
Symmetry code
O(ꢄ)–H(ꢄ)ꢂ·ꢂ·ꢂ·ꢂI(ꢊ)
O(ꢊ)–H(ꢊ)ꢂ·ꢂ·ꢂ·ꢂI(ꢇ)
O(ꢇ)–H(ꢇ)ꢂ·ꢂ·ꢂ·ꢂI(ꢅ)
O(ꢋ)–H(ꢋ)ꢂ·ꢂ·ꢂ·ꢂI(ꢈ)
O(ꢃꢆ)–H(ꢃꢆ)ꢂ·ꢂ·ꢂ·ꢂI(ꢊ)
O(ꢃꢄ)–H(ꢃꢄ)ꢂ·ꢂ·ꢂ·ꢂI(ꢅ)
ꢆ.ꢌꢋ
ꢆ.ꢌꢋ
ꢆ.ꢌꢋ
ꢃ.ꢆ
ꢆ.ꢌꢋ
ꢃ.ꢆ
ꢄ.ꢋꢃ
ꢄ.ꢇꢈ
ꢄ.ꢉꢃ
ꢄ.ꢉ
ꢄ.ꢉꢊ
ꢄ.ꢋ
ꢃꢈꢊ
ꢃꢈꢉ
ꢃꢇꢅ
ꢃꢈꢃ
ꢃꢊꢉ
ꢃꢈꢌ
ꢅ.ꢉꢃꢈ(ꢈ)
ꢅ.ꢈꢉꢋ(ꢇ)
ꢅ.ꢇꢇꢄ(ꢊ)
ꢅ.ꢈꢉꢊ(ꢊ)
ꢅ.ꢇꢆꢊ(ꢈ)
ꢅ.ꢉꢊꢋ(ꢈ)
ꢃ−ꢂx, y, ꢆ.ꢈ−ꢂz
x, −ꢃ+y, z
x, −ꢃ+y, z
x, y, z
ꢃ−x, −ꢃ+y, ꢆ.ꢈ−z
x, y, z
Fig. 2:ꢁOꢍꢎꢏꢐ-III diagram of the molecular structure of [Cd(NTE) ][Hg (μ-I) I ]. The displacement ellipsoids are drawn at the 35% probability
2
2
2 4
level. The hydrogen atoms of the ligand were omitted for clarity.
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

ꢁꢁꢁꢂ
ꢀ ꢀZ. Mardani et al.: Coordination behavior of a tetradentate NO -donor amino alcohol ligand
4
3
3
Conclusion
In this work, a new complex of NTE, [Cd(NTE) ][Hg (μ-I) I ],
2
2
2 4
1
was synthesized and its spectral (IR, H NMR) and structural
properties were investigated. The structure of the [HNTE]
Cl salt was also then determined by X-ray diffraction analy-
sis and reported. The NTE ligand acts as an NO -donor in
3
this complex by forming three five-membered non-planar
chelate rings. X-ray analysis of the complex revealed a
cadmium atom with a slightly distorted cube geometry
(
CdN O ) and mercury atoms in a binuclear structure [I Hg(μ-
2 6 2
I ) HgI ] with a tetrahedral geometry. On the basis of CSD
2−
2
2
2
studies, we observe that the coordination geometry around
the cadmium atom is a cube with only modest distortion.
4
Experimental section
Fig. 3:ꢁPacking of complex, showing the hydrogen bonds in the ac
plane. Only the hydrogen atoms involved in hydrogen bonding are
shown. Each CdN O unit is shown as a cube.
2
6
4.1 Materials and instrumentation
All chemicals and solvents were reagent or analytical grade
and used as received. The carbon, hydrogen and nitrogen
contents were determined in a Thermo Finnigan Flash Ele-
mental Analyzer 1112 EA. The infrared spectra of KBr pellets
were recorded in the range of 400–4000 cm− using an
FT-IR 8400-Shimadzu spectrometer. The melting point was
determined using Barnstead Electrothermal 9200 electri-
1
1
cally heated apparatus. The H NMR spectrum was recorded
on a Bruker Aspect 3000 instrument operating at 250 MHz;
chemical shifts are given in parts per million, with values
in reference to an internal standard of tetra methyl silane.
4
.2 [HNTE]Cl
NTE (0.15 g, 1 mmol) dissolved in EtOH (10 mL) was added
with stirring to a solution containing 0.27 g (1 mmol)
of HgCl in ethanol (10 mL). The reaction mixture was
2
refluxed for 6 h and then filtered. The colorless crystals
Fig. 4:ꢁPacking in crystals of [HNTE]Cl, showing the hydrogen bonds suitable for X-ray diffraction were obtained from the solu-
3
and R (30) motifs.
6
tion after standing for a week. Yield: 0.01 g, 5%; m.p.:
68°C. –C H ClNO (185.65): calcd. C 38.82, H 8.69, N 7.54;
1
6
16
3
found C 38.47, H 8.66, N 7.68. – IR (KBr disk): νꢀ=ꢀ3314 (OH),
158 (NH), 2938 (CH), δ ꢀ=ꢀ1459 (CH ), δ ꢀ=ꢀ1404 (CH ),
i
i
center of the Hg1/I1/Hg1 /I1 plane and C symmetry, while
i
3
as
−1
2
s
2
another anion has a C axis perpendicular to the Hg2/I4/
Hg2 /I4 plane and C symmetry.
2
νꢀ=ꢀ1253 (CO), 1095 (CN) cm .
i
i
2
In the structural network of the complex (Fig. 3),
there are intermolecular O–Hꢀ·ꢀ·ꢀ·ꢀI and Iꢀ·ꢀ·ꢀ·ꢀI interactions.
Two I5ꢀ·ꢀ·ꢀ·ꢀI6 interactions are evident between adjacent
2 2 2 2
extend the network in the bc plane (Fig. 5).
4
.3 [Cd(NTE) ][Hg (μ-I) I ]
2
2
2 4
2−
[
I Hg(μ-I ) HgI ] units to form a ten-membered ring and NTE (0.30 g, 2 mmol) dissolved in EtOH (15 mL) was added
with stirring to a solution containing 0.37 g (1 mmol) of
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

Z. Mardani et al.: Coordination behavior of a tetradentate NO -donor amino alcohol ligandꢀꢂꢁꢁꢁꢀ5
3
Fig. 5:ꢁParticipation of Iꢂ·ꢂ·ꢂ·ꢂI interactions in forming ten-membered rings. Each HgI unit is shown as a tetrahedron.
4
[
[
[
5] M. Zhou, W. T. Yu, D. Xu, S. Y. Guo, M. K. Lu, D. R. Yuan, Z.
Kristallogr. New Cryst. Struct. 2000, 215, 425.
6] N. A. Bell, M. Goldstein, L. A. March, I. W. Nowell, Inorg. Chim.
Acta 1984, 83, 75.
CdI and 0.45 g (1 mmol) of HgI in ethanol (25 mL). The
2
2
reaction mixture was refluxed for 6 h and then filtered. The
yellow crystals suitable for X-ray diffraction were obtained
from the solution after standing for 5 days. Yield: 0.64 g,
7] R. Kuroda, Inorg. Nucl. Chem. Lett. 1973, 9, 13.
8
2%; m.p.: 160°C. –C H CdHg I N O (1573.40): calcd. C
[8] X. Q. Wang, W. T. Yu, D. Xu, H. Q. Sun, Acta Crystallogr. 2005,
E61, m548.
[
1
2
30
2
6
2
6
9
.13, H 1.92, N 1.78; found C 8.12, H 2.01, N 1.85. – IR (KBr
9] X. Q. Wang, W. T. Yu, D. Xu, G. H. Zhang, Acta Crystallogr. 2005,
E61, m1147.
disk): νꢀ=ꢀ3442 (OH), 2953 (CH), δ ꢀ=ꢀ1446 (CH ), δ ꢀ=ꢀ1369
as
2
s
−
1
1
(
CH ), νꢀ=ꢀ1251 (CO), 1060 (CN) cm . – H NMR (250 MHz,
2
[
10] J. J. Vittal, P. A. W. Dean, Polyhedron 1998, 17, 1937.
[11] S.-L. Li, J.-Y. Wu, Y.-P. Tian, H. Ming, P. Wang, M.-H. Jiang, H.-K.
[
D ]DMSO): δꢀ=ꢀ5.56 (s, 3H, OH), 3.50 (m, 6H, OCH), 2.68
6
(
m, 6H, NCH) ppm.
Fun, Eur. J. Inorg. Chem. 2006, 2006, 2900.
[
12] X.-Q. Wang, W.-T. Yu, X.-Q. Hou, D. Xu, Y.-L. Geng, Acta Crystal-
logr. 2006, E62, m2333.
[
13] T. Iwamoto, D. F. Shriver, Inorg. Chem. 1972, 11, 2570.
4
.4 X-ray structure determinations
[14] S. Chattopadhyay, K. Bhar, S. Das, S. Khan, P. Mitra, J. Ribas, B.
K. Ghosh, Polyhedron 2012, 39, 48.
[
[
[
[
[
15] T. S. Basu Baul, I. Longkumer, A. Linden, J. Organomet. Chem.
Data were collected at 93.0 K using a Rigaku FRX (Mo-K,
confocal optic) and Dectris P200. The structures were
solved and refined with Sꢁꢂꢃꢄ [26]. Diagrams of the mole-
cular structure and unit cell were created using Oꢅꢆꢂꢇ-III
2
014, 761, 156.
16] I.-H. Park, J.-Y. Kim, K. Kim, S. S. Lee, Cryst. Growth Des. 2014,
4, 6012.
1
17] X. Q. Wang, L. Y. Zhu, J. D. Fan, W. T. Yu, G. Yu, D. Xu, J. Chem.
Crystallogr. 2010, 40, 93.
[
27–29] and Dꢈꢉꢊꢋꢌꢍ [30, 31]. In all CSD searches which
18] X. Liu, X. Wang, X. Yin, S. Zhang, L. Wang, L. Zhu, G. Zhang,
D. Xu, J. Mater. Chem. 2014, C2, 723.
have been presented, the structures containing any error
or disorder have been omitted.
19] SDBSWeb, National Institute of Advanced Industrial Science
and Technology: http://sdbs.db.aist.go.jp (accessed 13 August
CCDC 1530145 and 1506871 for [Cd(NTE) ][Hg (μ-I) I ]
2
2
2 4
and [HNTE]Cl, respectively, contain the supplemen-
2
016).
tary crystallographic data for this paper. These data [20] D. Mootz, D. Brodalla, M. Wiebcke, Acta Crystallogr. 1990,
can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
C46, 797.
[
21] S. I. Al-Resayes, A. A. Khan, M. Azam, A. Trzesowska-Kruszynska,
R. Kruszynski, M. Oves, Asian J. Chem. 2014, 26, 887.
22] M. Hakimi, K. Moeini, Z. Mardani, F. Mohr, Polyhedron 2014,
[
7
0, 92.
[
[
23] J. Pickardt, B. Kuhn, Z. Naturforsch. 1994, 49b, 1031.
24] N. G. Spiropulos, E. A. Standley, I. R. Shaw, B. L. Ingalls, B.
Diebels, S. V. Krawczyk, B. F. Gherman, A. M. Arif, E. C. Brown,
Inorg. Chim. Acta 2012, 386, 83.
References
[
[
[
[
1] M. Hakimi, Z. Mardani, K. Moeini, F. Mohr, M. A. Fernandes,
[25] M. Hakimi, Z. Mardani, K. Moeini, F. Mohr, Polyhedron 2015,
102, 569.
[26] G. Sheldrick, Acta Crystallogr. 2008, A64, 112.
[27] C. K. Johnson, M. N. Burnett, Oꢍꢎꢏꢐ-III (version 1.0.2), Oak
Ridge Thermal Ellipsoid Plot Program for Crystal Structure
Illustrations, Rep. ORNL-6895, Oak Ridge National Laboratory,
Oak Ridge, TN (USA) 1996.
Polyhedron 2014, 67, 27.
2] M. Hakimi, Z. Mardani, K. Moeini, M. A. Fernandes, J. Coord.
Chem. 2012, 65, 2221.
3] M. Hakimi, Z. Mardani, K. Moeini, E. Schuh, F. Mohr, Z. Natur-
forsch. 2013, 68b, 272.
4] F. H. Allen, Acta Crystallogr. 2002, B58, 380.
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

ꢁꢁꢁꢂ
ꢀ ꢀZ. Mardani et al.: Coordination behavior of a tetradentate NO -donor amino alcohol ligand
6
3
[
[
[
28] L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
29] L. J. Farrugia, J. Appl. Crystallogr. 2012, 45, 849.
30] G. Bergerhof, M. Berndt, K. Brandenburg, J. Res. Natl. Stand.
Technol. 1996, 101, 221.
[31] K. Brandenburg, Dꢑꢒꢓꢔꢕꢖ, Crystal and Molecular Structure
Visualization, Crystal Impact, H. Putz and K. Brandenburg GbR,
Bonn (Germany) 2012. See also: http://www.crystalimpact.
com/diamond/.
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM

Z. Naturforsch. 2017; x(x)b: xxx–xxx
Graphical synopsis
Zahra Mardani, Vali Golsanamlou,
Saba Khodavandegar, Keyvan
Moeini, Alexandra M.Z. Slawin and
J. Derek Woollins
Structural study of the coordination
behavior of a tetradentate
NO -donor amino alcohol ligand
3
II
II
toward a Cd :Hg mixture
DOI 10.1515/znb-2016-0222
Z. Naturforsch. 2017; x(x)b: xxx–xxx
Brought to you by | University of Florida
Authenticated
Download Date | 4/21/17 8:57 PM