Structural and spectroscopic characterization of a new luminescent NiII complex: bis{2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolato-k3O,N,O′}nickel(II)

Article abstract of DOI:10.1107/S2053229618009166

The design and preparation of transition-metal complexes with Schiff base ligands are of interest due to their potential applications in the fields of molecular magnetism, nonlinear optics, dye-sensitized solar cells (DSSCs), sensing and photoluminescence. Luminescent metal complexes have been suggested as potential phosphors in electroluminescent devices. A new luminescent nickel(II) complex, [Ni(C₁₀H₁₀C_l2NO₂)₂], has been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis, UV–Vis, FT–IR, ¹H NMR, ¹³C NMR and photoluminescence spectroscopies, and LC–MS/MS. Molecules of the complex in the crystals lie on special positions, on crystallographic binary rotation axes. The Ni^II atoms are six-coordinated by two phenolate O, two imine N and two hydroxy O atoms from two tridentate Schiff base 2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolate ligands, forming an elongated octahedral geometry. Furthermore, the complex exhibits a strong green luminescence emission in the solid state at room temperature, as can be seen from the (CIE) chromaticity diagram, and hence the complex may be a promising green OLED (organic light-emitting diode) in the development of electroluminescent materials for flat-panel-display applications.

Full text of DOI:10.1107/S2053229618009166

research papers
Structural and spectroscopic characterization of a
new luminescent NiII complex: bis{2,4-dichloro-
6-[(2-hydroxypropyl)iminomethyl]phenolato-
j3O,N,O0}nickel(II)
ISSN 2053-2296
Duygu Akin Kara,a Adem Donmez,a,b Hulya Karaa,c* and M. Burak Cobanc,d
*
Received 13 February 2018
Accepted 25 June 2018
aDepartment of Physics, Molecular Nano-Materials Laboratory, Mugla Sitki Kocman University, Mugla, Turkey, bScientific
Research Projects Coordination Unit, Mugla Sitki Kocman University, Mugla, Turkey, cDepartment of Physics, Balikesir
University, Balikesir, Turkey, and dCenter of Sci and Tech App and Research, Balikesir University, Balikesir, Turkey.
*Correspondence e-mail: karahulya04@gmail.com, burakcoban@balikesir.edu.tr
Edited by T.-B. Lu, Sun Yat-Sen University,
People’s Republic of China
Keywords: nickel(II) complex; Schiff base;
crystal structure; photoluminescence; green light
emitting devices.
The design and preparation of transition-metal complexes with Schiff base
ligands are of interest due to their potential applications in the fields of
molecular magnetism, nonlinear optics, dye-sensitized solar cells (DSSCs),
sensing and photoluminescence. Luminescent metal complexes have been
suggested as potential phosphors in electroluminescent devices. A new
luminescent nickel(II) complex, [Ni(C10H10Cl2NO2)2], has been synthesized
and characterized by single-crystal X-ray diffraction and elemental analysis,
CCDC reference: 1589491
Supporting information: this article has
supporting information at journals.iucr.org/c
1
UV–Vis, FT–IR, H NMR, 13C NMR and photoluminescence spectroscopies,
and LC–MS/MS. Molecules of the complex in the crystals lie on special positions,
on crystallographic binary rotation axes. The NiII atoms are six-coordinated by
two phenolate O, two imine N and two hydroxy O atoms from two tridentate
Schiff base 2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolate ligands,
forming an elongated octahedral geometry. Furthermore, the complex exhibits a
strong green luminescence emission in the solid state at room temperature, as
can be seen from the (CIE) chromaticity diagram, and hence the complex may
be a promising green OLED (organic light-emitting diode) in the development
of electroluminescent materials for flat-panel-display applications.
1. Introduction
During the last decade, transition-metal complexes have been
of great interest since they have potential applications in
coordination chemistry, catalysis and sensors, and display
biological and magnetic properties (Sherino et al., 2018; Bang
et al., 2016; Vittaya et al., 2017; Hajikhanmirzaei et al., 2015;
Vamja & Surati, 2017; Keypour et al., 2017). Recently, Schiff
base ligands and their metal complexes have attracted atten-
tion as organic photovoltaic materials since their use as
potential substitutes for dye-sensitized solar cells (DSSCs)
(Zhang et al., 2018; Yang et al., 2010; Wesley Jeevadason et al.,
2014; Dinc¸alp et al., 2010). In addition, impressive progress has
been made in the photophysical and optoelectronic applica-
tions of these complexes, because they exhibit photo-
luminescence (PL), as well as electroluminescence (EL), and
these qualities point to potential applications in the develop-
ment of energy-efficient low-cost full-colour and flat-panel
OLED (organic light-emitting diode) displays (Nishal et al.,
2014, 2015; Taghi Sharbati et al., 2011; Yan et al., 2018; Bizzarri
et al., 2017). ZnII, PdII, PtII, IrIII and ReI complexes have been
much more studied as luminescence emitters in comparison
with NiII complexes (Li et al., 2013; Lepeltier et al., 2015; Singh
et al., 2016; Nishal et al., 2015; Bizzarri et al., 2017). Therefore,
# 2018 International Union of Crystallography
Acta Cryst. (2018). C74
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research papers
NiII complexes do not appear as numerously in the literature
as emitter materials for OLEDs. However, some recent arti-
cles have evidenced an increasing interest for emitting NiII
complexes (Srinivas et al., 2016; Cerezo et al., 2017; More et al.,
2017b). In the last decade, our research group and others have
reported the synthesis, structural, spectroscopic, NLO and
magnetic properties of some nickel(II) Schiff base complexes
Elemental analyses (C, H and N) were carried out by standard
methods. The solid-state UV–Vis spectra were determined
with an Ocean Optics Maya 2000 Pro Spectrometer (250–
600 nm). The FT–IR spectra were measured with a Perkin-
Elmer Spectrum 65 instrument in the range 4000–600 cmꢀ1
.
The solid-state luminescence spectra in the visible region were
measured at room temperature with an ANDOR SR500i-BL
photoluminescence spectrometer equipped with a triple
grating and using an air-cooled CCD camera as the detector.
The measurements were carried out using the excitation
source (349 nm) of a Spectra-physics Nd:YLF laser with a 5 ns
pulse width and 1.3 mJ of energy per pulse as the source. Mass
spectra were determined with an LC–MS/MS AB Sciex Qtrap
¨
(Elerman et al., 2001; Kara et al., 2003; Unver et al., 2006;
Shawish et al., 2016; Elmehdawi et al., 2017). According to the
Cambridge Structural Database (CSD, Version 5.38,
November 2016 updates; Groom et al., 2016), there are few
reports on investigations of the emission spectra of salen-type
ligands [salen is 2,20-ethylenebis(nitrilomethylidene)diphenol]
and their NiII complexes (More et al., 2017a,b; Donmez et al.,
2017a,b). Green emitting materials provide one of the prime
colours in the development of full-colour display technology
and there is still a big challenge in developing emission
materials to display green light. In this context, in view of the
importance of luminescent NiII complexes and in an effort to
enlarge the library of such complexes, a new luminescent
nickel(II) complex, namely bis{2,4-dichloro-6-[(2-hydroxy-
propyl)iminomethyl]phenolato-ꢀ3O,N,O0}nickel(II), (1), has
been synthesized and characterized by single-crystal X-ray
diffraction and elemental analysis, solid-state UV–Vis, FT–IR,
1H NMR, 13C NMR and solid-state photoluminescence spec-
troscopies, and LC–MS/MS.
1
5500 instrument. The H and 13C NMR spectra of the free
Schiff base ligand were recorded [in dimethyl sulfoxide
(DMSO)] using a Bruker Ultrashield Plus Biospin (400 MHz)
instrument. Powder X-ray diffraction (PXRD) patterns were
recorded on a Bruker D8 Advance diffractometer using Cu
ꢁ
˚
Kꢁ radiation (ꢂ = 1.5418 A) in the range 5 < 2ꢃ < 50 in ꢃ–ꢃ
mode with a step of n s (5 < n < 10 s) and a step width of 0.03ꢁ.
A comparison between the experimental and calculated (from
the CIF) PXRD patterns was performed with the Mercury
program (Macrae et al., 2008).
2.1. Synthesis and crystallization
A solution of 3-aminopropan-1-ol (1 mmol, 0.075 g) in
methanol (10 ml) was added slowly to a solution of 3,5-di-
chlorosalicylaldehyde (1 mmol, 0.191 g) in methanol (20 ml).
The mixture was stirred for 1 h at 330 K. The yellow product
of 2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenol (H2L)
precipitated from the solution on cooling (yield 82%).
Elemental analysis calculated for C10H11Cl2NO2 (%): C 48.41,
H 4.47, N 5.65; found: C 48.36, H 4.49, N 5.63. LS–MS/MS m/z
found 248.0, requires 248.1 (see Fig. S3 in the supporting
1
information). H NMR (400 MHz, DMSO-d6, Me4Si, ppm): ꢄ
8.56 (s, 1H, HC N), 7.55 (d, J = 2.8 Hz, 1H, aromatic), 7.40 (d,
J = 2.4 Hz, 1H, aromatic), 4.68 (brs, 1H, OH), 3.72 (t, J =
6.8 Hz, 2H, H2C—N), 3.51 (t, J = 6.0 Hz, 2H, H2C—OH), 1.82
(quint, J = 6.4, 10.4 Hz, 2H, aliphatic methylene). 13C NMR
(100 MHz, DMSO-d6, Me4Si, ppm): ꢄ 165.33 (C N), 163.54
(C
C
O), 132.72 (aromatic), 130.22 (aromatic), 124.57
(C C—Cl), 116.76 (C C—O), 57.83 (methylene), 50.94
(H2C—OH), 32.61 (H2C—N). See Figs. S1 and S2 in the
supporting information for the NMR spectra.
Complex (1) was prepared by the addition of a solution of
nickel(II) acetate tetrahydrate (0.249 g, 1 mmol) in methanol
(30 ml) to a solution of H2L (1 mmol, 0.248 g) in methanol
(30 ml). The resulting solution was stirred for 2 h at 333 K and
then filtered. The filtrate was left to stand at room tempera-
ture. After two weeks, single crystals were obtained (yield
44%). The synthetic route for the preparation of H2L and (1)
is outlined in Scheme 1. Analysis calculated for C20H20Cl4-
N2NiO4 (%): C 43.45, H 3.65, N 5.07; found: C 43.11, H 3.67, N
5.08. LS–MS/MS m/z found 553.3, requires 552.9 (see Fig. S4 in
the supporting information).
2. Experimental
All chemicals and solvents used for the synthesis were of
reagent grade and were used without further purification.
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Table 1
Experimental details.
Table 2
Selected geometric parameters (A, ).
ꢁ
˚
Crystal data
Chemical formula
Mr
Ni1—O1
Ni1—O2
Ni1—N1
2.096 (3)
2.029 (3)
2.060 (3)
Ni2—O3
Ni2—O4
Ni2—N2
2.041 (3)
2.106 (3)
2.053 (3)
[Ni(C10H10Cl2NO2)2]
552.89
Crystal system, space group
Temperature (K)
Monoclinic, C2/c
292
20.5375 (19), 10.7332 (6),
22.4073 (19)
108.073 (10)
4695.6 (7)
O1i—Ni1—O1
O2—Ni1—O1
O2i—Ni1—O1
O2i—Ni1—O2
O2—Ni1—N1i
O2—Ni1—N1
N1—Ni1—O1i
N1—Ni1—O1
N1i—Ni1—N1
86.70 (16)
175.92 (11)
89.59 (11)
94.17 (15)
94.59 (12)
87.55 (12)
87.15 (13)
90.57 (13)
176.86 (19)
O3—Ni2—O3i
O3—Ni2—O4i
O3—Ni2—O4
O3—Ni2—N2i
O3—Ni2—N2
O4—Ni2—O4i
N2—Ni2—O4i
N2—Ni2—O4
N2i—Ni2—N2
94.75 (15)
90.54 (11)
173.47 (11)
96.02 (12)
86.57 (12)
84.44 (16)
88.10 (13)
89.08 (13)
176.19 (19)
˚
a, b, c (A)
ꢅ (ꢁ)
3
˚
V (A )
Z
Radiation type
8
Mo Kꢁ
1.31
0.32 ꢄ 0.21 ꢄ 0.17
ꢆ (mmꢀ1
Crystal size (mm)
)
3
2
Symmetry code: (i) ꢀx þ 1; y; ꢀz þ .
Data collection
Diffractometer
Absorption correction
Agilent Xcalibur Eos
Analytical [CrysAlis PRO (Rigaku
OD, 2015), based on expressions
derived by Clark & Reid (1995)]
0.521, 0.685
with those observed in nickel(II) Schiff base complexes (Wang
´
et al., 2011; Zhou et al., 2009; Ayikoe et al., 2011). In the crystal
Tmin, Tmax
structure of (1), the aliphatic –OH group of the tridentate
Schiff base ligand actively participates in intermolecular O—
Hꢃ ꢃ ꢃO hydrogen bonds, connecting to one other unit and
resulting in a one-dimensional chain along the b axis (Fig. 2
and Table 3). The intramolecular Ni1ꢃ ꢃ ꢃNi2 distance is
No. of measured, independent and
observed [I > 2ꢇ(I)] reflections
Rint
7742, 4420, 3127
0.032
0.610
ꢀ1
˚
(sin ꢃ/ꢂ)max (A
)
Refinement
R[F2 > 2ꢇ(F2)], wR(F2), S
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
ii
0.051, 0.129, 1.09
4420
287
2
H atoms treated by a mixture of
independent and constrained
refinement
˚
5.346 (3) A and the intermolecular Ni2ꢃ ꢃ ꢃNi1 [symmetry
˚
code: (ii) x, y ꢀ 1, z] distance is 5.388 (3) A in the chain
structure (Fig. 2). The shortest intermolecular Clꢃ ꢃ ꢃCl contact
iii
1
3
˚
is Cl2ꢃ ꢃ ꢃCl4 of 3.443 (3) A [symmetry code: (iii) x + 2, ꢀy + 2,
1
2
z ꢀ ], which connects the molecules into a two-dimensional
ꢀ3
˚
Áꢈmax, Áꢈmin (e A
)
0.96, ꢀ0.48
Computer programs: CrysAlis PRO (Rigaku OD, 2015), SHELXT (Sheldrick, 2015a),
structure in the bc plane (Fig. 3).
SHELXL2016 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).
2.2. Refinement
Crystal data, data collection and structure refinement
details for complex (1) are summarized in Table 1. H-atom
positions were calculated geometrically and refined using a
riding model, except for the hydroxy H atoms, for which their
˚
positional parameters were refined with restraints [0.84 (2) A]
applied to the O—H distances.
3. Results and discussion
3.1. Crystal structure
Molecules of complex (1) in the crystal lie on special posi-
tions, on crystallographic binary rotation axes, and have
crystallographic C2 point symmetry (Fig. 1). The crystal-
lographically independent unit contains two independent half
molecules. The NiII atom is six-coordinated by two phenolate
O, two imine N and two hydroxy O atoms from two tridentate
Schiff base ligands, forming a slightly elongated octahedral
geometry. The Ni—O bond lengths range from 2.029 (3) to
˚
˚
2.106 (3) A and the Ni—N distances are 2.060 (3) and
2.053 (3) A. The trans angles at the Ni atom are in the range
173.47 (11)–176.86 (19)ꢁ, while the other angles are close to
90ꢁ, ranging from 84.44 (16) to 96.02 (12)ꢁ, indicating a slightly
distorted octahedral coordination. Selected bond lengths and
angles are listed in Table 2, and are typical and comparable
Figure 1
The molecular structure of (1), showing the atom-labelling scheme and
drawn with 50% probability displacement ellipsoids. [Symmetry code: (i)
ꢀx, ꢀy + 1, ꢀz + 1.]
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Figure 2
The one-dimensional hydrogen-bonded chain structure in (1). Dotted
lines indicate O—Hꢃ ꢃ ꢃO hydrogen bonds. Generic atom labels without
symmetry codes have been used. See Table 3 for hydrogen-bond details.
Figure 4
Powder X-ray diffraction pattern of (1). The black line represents the
pattern simulated from the CIF and the red line represents the
experimental pattern.
3.2. Powder X-ray diffraction pattern
Before proceeding to the spectroscopic and photolumin-
escence studies, we also carried out a powder X-ray diffraction
(PXRD) experiment to investigate the purity of (1). The
PXRD results showed that the peak positions match well with
those from the simulated PXRD patterns on the basis of
single-crystal structure data, indicating reasonable crystalline
phase purity (Fig. 4).
3.3. Spectroscopy
The FT–IR spectrum of (1) is consistent with the structural
characteristics determined by single-crystal X-ray diffraction
(Fig. 5). By comparing the IR spectra of H2L and its complex
(1), the coordination modes and the parts of the ligand bound
to the metal ion were explored. On coordination, the
stretching vibrations for the ꢉ(C N) and ꢉ(C—O) bonds
show a significant shift from 1648 to 1633 cmꢀ1 and from 1204
to 1167 cmꢀ1 for H2L and (1), respectively (Coban et al., 2018;
Donmez et al., 2017a). The absorptions between 2964 and
2855 cmꢀ1 are characteristic of the C—H aromatic and
aliphatic stretching vibrations for both structures (Kocak et al.,
2017). The broad band attributed to the existence of a
ꢉ(O—H) stretching vibration at 3231 cmꢀ1 of H2L was
Figure 5
The IR spectra of H2L (black line) and (1) (red line).
Table 3
Hydrogen-bond geometry (A, ).
ꢁ
˚
D—Hꢃ ꢃ ꢃA
D—H
Hꢃ ꢃ ꢃA
Dꢃ ꢃ ꢃA
D—Hꢃ ꢃ ꢃA
O1—H1ꢃ ꢃ ꢃO3
0.84 (3)
0.84 (2)
1.87 (3)
1.91 (2)
2.702 (4)
2.736 (4)
172 (4)
168 (4)
O4—H4Aꢃ ꢃ ꢃO2ii
Symmetry code: (ii) x; y ꢀ 1; z.
Figure 3
A crystal packing view of the polymeric networks in the bc plane showing the intermolecular Clꢃ ꢃ ꢃCl interactions (dotted lines). Generic atom labels
without symmetry codes have been used.
4 of 6 Kara et al. A new luminescent NiII complex
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trum of (1) is characterized by a broad band (ꢂmax = 381 nm),
which shifts towards lower energy upon complexation.
The solid-state photoluminescence spectra of free H2L and
(1) were investigated at room temperature upon excitation at
ꢂ
ex = 349 nm. As shown in Fig. 7, H2L displays a broad yellow
emission band at ꢂmax = 592 nm, with CIE coordinates of 0.55
and 0.41, which can be attributed to ꢊ!ꢊ* electronic transi-
tions in the molecular orbital manifolds of the aromatic ring
systems of the ligand, suggesting that there may be intraligand
charge transfer (ILCT) (Coban et al., 2016, 2018; Oylumluoglu
et al., 2017). The occurrence of a photo-induced electron
transfer (PET) process may be responsible for quenching the
luminescence of the ligand, depending on the presence of a
lone pair of electrons on the N- and O-donor atoms in the
ligand (Shafaatian et al., 2015; Basak et al., 2007). Complex (1)
displays an intense green broad emission band occurring at
ꢂmax = 526 nm, with CIE coordinates of 0.22 and 0.62 in the
visible region. The intensity of the emission in (1) is greater
than that of the free ligand (H2L). The main reason for this is
that the PET process was prevented by the complexation of
the ligand to the metal ion. Therefore, the luminescence
intensity may be greatly increased by the coordination of the
NiII atom (Hopa & Cokay, 2016). In addition, chelation of H2L
to the NiII atom increases the rigidity of the HLꢀ ligand and
thus reduces energy loss through thermal vibration decay (Das
et al., 2006). However, the increase of luminescence by
complexation is very interesting because it creates opportu-
nities for the photochemical applications of these complexes
(Majumder et al., 2006). Upon coordinating to the NiII atom,
the observed blue shift (66 nm) of the emission maximum
between free H2L and its complex (1) may be denoted as
CHEF (chelation-enhanced fluorescence) (Song et al., 2015;
Erkarslan et al., 2016).
Figure 6
The solid-state UV–Vis spectra of H2L (black line) and (1) (red line).
replaced by the weaker broad band at 3085 cmꢀ1 after metal
and ligand complexation (Yahsi et al., 2016a). The shift of the
peak position of the hydroxy groups and the broadening of the
band could be attributed to the formation of the metal
complex. The ꢉ(C—Cl) stretching vibrations from the 3,5-
chlorobenzene rings are observed between 858 and 824 cmꢀ1
in H2L and (1), respectively (Donmez et al., 2017b).
The photophysical properties of H2L and (1) have been
reported through solid-state UV–Vis absorption (Fig. 6) and
solid-state photoluminescence spectroscopy (Fig. 7). The
similarity in the shapes of the absorption and emission bands
suggests that the bands result from ligand-centred transitions.
As shown in the solid-state UV–Vis spectrum in Fig. 6, H2L
displays an essential broad band in the UV region (ꢂmax
=
263 nm), which may be attributed to ligand-centred ꢊ!ꢊ*
and n!ꢊ* transitions (Gliemann, 1985; Celen et al., 2013;
Yahsi et al., 2016b). On the other hand, the absorption spec-
4. Conclusion
The compound characterized in this study is a new example of
a nickel(II) Schiff base complex which shows luminescence in
the green region of the spectrum. Our results show that the
emission band in the complex displays a blue shift and a
greater intensity than that of the free organic ligand (H2L)
when excited at 349 nm. The blue shift and enhanced lumi-
nescence intensity for the complex may be due to the chela-
tion of the ligand to the metal centre. Such chelation enhances
the rigidity of the ligand and thus reduces the loss of energy by
radiationless decay of the intraligand emission excited state.
The CIE graph indicated that this phosphor might be very
useful for green-light-emitting diodes and solid-state lighting
applications.
Acknowledgements
The authors are grateful to Dokuz Eylul University for the use
of the Agilent Xcalibur Eos diffractometer (purchased under
University Research grant No. 2010.KB.FEN.13) and Balikesir
University, Science and Technology Application and Research
Center (BUBTAM) for the use of the mass and photo-
Figure 7
The emission spectra of H2L (yellow line) and (1) (green line) in solid
samples at room temperature (ꢂex = 349 nm). The upper left and lower
left photos are luminescence images of (1) and H2L, respectively. The
upper right inset is a CIE colour space chromaticity diagram of the H2L
(yellow circle) and complex (1) (green circle) emissions.
A new luminescent NiII complex 5 of 6
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´
Lepeltier, M., Morlet-Savary, F., Graff, B., Lalevee, J., Gigmes, D. &
Dumur, F. (2015). Synth. Met. 199, 139–146.
Li, K., Cheng, G., Ma, C., Guan, X., Kwok, W.-M., Chen, Y., Lu, W. &
Che, C.-M. (2013). Chem. Sci. 4, 2630–2644.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe,
P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. &
Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
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luminescence spectrometers. The authors also thank Dr
Muhittin Aygun (Dokuz Eylul University) for the X-ray
measurement and Dr Erhan Kaplaner (Mugla Sıtkı Kocman
University) for NMR comments.
Funding information
Funding for this research was provided by: Research Funds of
Mugla Sitki Kocman University (grant No. BAP-2017/029).
More, M. S., Devkule, S. S. & Chavan, S. S. (2017a). J. Fluoresc. 27,
841–851.
More, M. S., Pawal, S. B., Lolage, S. R. & Chavan, S. S. (2017b). J. Mol.
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6 of 6 Kara et al. A new luminescent NiII complex
Acta Cryst. (2018). C74
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supporting information
Acta Cryst. (2018). C74 [https://doi.org/10.1107/S2053229618009166]
Structural and spectroscopic characterization of a new luminescent NiII
complex: bis{2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolato-
3
κ O,N,O′}nickel(II)
Duygu Akin Kara, Adem Donmez, Hulya Kara and M. Burak Coban
Computing details
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction:
CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to
refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used
to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
3
Bis{2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolato-κ O,N,O′}nickel(II)
Crystal data
[Ni(C10H10Cl2NO2)2]
Mr = 552.89
F(000) = 2256
Dx = 1.564 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2317 reflections
θ = 3.7–28.1°
Monoclinic, C2/c
a = 20.5375 (19) Å
b = 10.7332 (6) Å
c = 22.4073 (19) Å
β = 108.073 (10)°
V = 4695.6 (7) Å3
Z = 8
µ = 1.31 mm−1
T = 292 K
Prism, green
0.32 × 0.21 × 0.17 mm
Data collection
Xcalibur, Eos
diffractometer
Detector resolution: 8.0667 pixels mm-1
ω scans
7742 measured reflections
4420 independent reflections
3127 reflections with I > 2σ(I)
Rint = 0.032
Absorption correction: analytical
[CrysAlis PRO (Rigaku OD, 2015), based on
expressions derived by Clark & Reid (1995)]
θmax = 25.7°, θmin = 3.2°
h = −24→22
k = −13→10
l = −27→16
T
min = 0.521, Tmax = 0.685
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.051
wR(F2) = 0.129
S = 1.09
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0441P)2 + 4.9249P]
where P = (Fo2 + 2Fc2)/3
4420 reflections
287 parameters
2 restraints
(Δ/σ)max = 0.001
Δρmax = 0.96 e Å−3
Δρmin = −0.48 e Å−3
Acta Cryst. (2018). C74
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supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Ni1
Cl1
Cl2
O1
O2
N1
0.500000
0.94958 (7)
1.15988 (12)
1.0281 (2)
0.8076 (3)
1.0783 (2)
0.9443 (3)
0.7924 (4)
0.717088
0.862248
0.7847 (4)
0.721245
0.758498
0.9072 (5)
0.972646
0.898814
0.750000
0.0279 (2)
0.0517 (3)
0.1007 (7)
0.0367 (7)
0.0313 (7)
0.0320 (8)
0.0428 (12)
0.051*
0.051*
0.0428 (12)
0.051*
0.051*
0.0456 (12)
0.055*
0.055*
0.0376 (10)
0.045*
0.0346 (10)
0.0488 (13)
0.059*
0.54771 (7)
0.30179 (8)
0.50449 (16)
0.49229 (14)
0.39456 (18)
0.4526 (2)
0.461837
0.454575
0.3824 (2)
0.382276
0.350644
0.3569 (2)
0.361152
0.308672
0.3588 (2)
0.312089
0.94460 (5)
0.96063 (7)
0.68720 (13)
0.81378 (12)
0.71840 (15)
0.62759 (19)
0.607678
0.600710
0.6339 (2)
0.664696
0.594005
0.6535 (2)
0.625136
0.649568
0.7555 (2)
0.739480
C1
H1A
H1B
C2
H2A
H2B
C3
H3A
H3B
C4
H4
C5
C6
H6
0.9615 (4)
0.945846
1.0033 (4)
0.9951 (5)
0.960868
0.3846 (2)
0.3394 (2)
0.296078
0.82048 (19)
0.8565 (2)
0.838905
C7
C8
H8
0.3588 (3)
0.4222 (3)
0.435033
1.0369 (5)
1.0881 (5)
1.115878
0.9168 (2)
0.9440 (2)
0.985345
0.0542 (14)
0.0487 (13)
0.058*
C9
0.4666 (2)
0.4498 (2)
0.500000
0.70002 (6)
0.67063 (8)
0.55891 (14)
0.44015 (15)
0.44185 (18)
0.3686 (2)
0.343523
0.352385
0.3541 (2)
0.306440
0.381921
0.3682 (2)
0.350323
1.0977 (4)
1.0594 (4)
0.45155 (7)
0.66331 (13)
0.42402 (18)
0.5803 (2)
0.3063 (3)
0.4452 (3)
0.2922 (4)
0.360106
0.214891
0.2912 (4)
0.269108
0.90923 (19)
0.84608 (18)
0.750000
0.74089 (7)
0.52341 (7)
0.72366 (13)
0.76858 (14)
0.65718 (16)
0.7356 (2)
0.746926
0.748466
0.6655 (2)
0.645841
0.654872
0.6385 (2)
0.593009
0.0362 (10)
0.0311 (10)
0.0275 (2)
0.0579 (4)
0.0819 (6)
0.0326 (7)
0.0375 (7)
0.0330 (8)
0.0405 (11)
0.049*
0.049*
0.0454 (12)
0.054*
0.054*
0.0432 (12)
0.052*
C10
Ni2
Cl3
Cl4
O3
O4
N2
C11
H11A
H11B
C12
H12A
H12B
C13
H13A
0.227162
0.4154 (4)
0.412019
Acta Cryst. (2018). C74
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supporting information
H13B
C14
H14
C15
C16
H16
C17
C18
H18
C19
C20
H4A
H1
0.344280
0.4702 (2)
0.442685
0.5413 (2)
0.5688 (2)
0.541716
0.6345 (3)
0.6749 (2)
0.719243
0.6479 (2)
0.5815 (2)
0.459 (2)
0.519 (2)
0.481296
0.4524 (4)
0.436358
0.4833 (4)
0.4496 (5)
0.407314
0.4778 (5)
0.5468 (5)
0.569347
0.5818 (4)
0.5497 (4)
0.237 (3)
0.737 (2)
0.652679
0.6140 (2)
0.573133
0.6228 (2)
0.5754 (2)
0.540169
0.5800 (2)
0.6297 (2)
0.631525
0.6768 (2)
0.6766 (2)
0.779 (2)
0.701 (2)
0.052*
0.0368 (10)
0.044*
0.0361 (10)
0.0454 (12)
0.054*
0.0481 (13)
0.0476 (13)
0.057*
0.0404 (11)
0.0330 (10)
0.050*
0.050*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Ni1
Cl1
Cl2
O1
O2
N1
C1
C2
C3
C4
0.0350 (4)
0.0576 (8)
0.0610 (10)
0.048 (2)
0.0381 (17)
0.039 (2)
0.058 (3)
0.048 (3)
0.045 (3)
0.033 (2)
0.037 (3)
0.036 (3)
0.050 (3)
0.051 (3)
0.042 (3)
0.043 (3)
0.0255 (4)
0.0381 (7)
0.0729 (10)
0.0335 (17)
0.0310 (17)
0.034 (2)
0.026 (2)
0.028 (2)
0.033 (3)
0.035 (3)
0.034 (3)
0.051 (3)
0.053 (3)
0.038 (3)
0.036 (3)
0.0194 (4)
0.0540 (8)
0.197 (2)
0.0244 (16)
0.0251 (16)
0.0244 (18)
0.035 (3)
0.035 (3)
0.048 (3)
0.030 (2)
0.035 (2)
0.065 (3)
0.080 (4)
0.062 (3)
0.031 (2)
0.021 (2)
0.0198 (4)
0.0510 (8)
0.1293 (16)
0.0225 (15)
0.0235 (16)
0.0240 (18)
0.030 (2)
0.044 (3)
0.047 (3)
0.035 (2)
0.034 (3)
0.051 (3)
0.055 (3)
0.048 (3)
0.026 (2)
0.0314 (4)
0.000
0.0134 (3)
0.0157 (6)
0.0411 (8)
0.0094 (14)
0.0205 (13)
0.0125 (16)
0.015 (2)
0.011 (2)
0.006 (2)
0.012 (2)
0.0146 (19)
0.017 (2)
0.028 (2)
0.023 (2)
0.015 (2)
0.018 (2)
0.0148 (3)
0.0265 (7)
0.0454 (8)
0.0217 (14)
0.0162 (15)
0.0153 (17)
0.015 (2)
0.010 (2)
0.011 (2)
0.009 (2)
0.018 (2)
0.018 (2)
0.031 (3)
0.034 (3)
0.021 (2)
0.000
0.0434 (6)
0.0597 (9)
0.0356 (16)
0.0369 (15)
0.0339 (19)
0.035 (2)
0.043 (3)
0.039 (3)
0.048 (3)
0.035 (2)
0.048 (3)
0.042 (3)
0.039 (3)
0.038 (2)
0.034 (2)
0.0404 (4)
0.0892 (10)
0.0606 (9)
0.0479 (17)
0.059 (2)
0.043 (2)
0.067 (3)
0.061 (3)
0.049 (3)
0.038 (2)
0.044 (3)
0.037 (2)
0.047 (3)
0.069 (3)
0.063 (3)
−0.0137 (7)
−0.0077 (12)
0.0037 (15)
−0.0040 (13)
0.0011 (17)
0.004 (2)
−0.004 (2)
0.006 (2)
−0.001 (2)
0.003 (2)
−0.002 (3)
0.004 (3)
0.006 (3)
−0.001 (2)
0.005 (2)
0.000
−0.0115 (6)
0.0225 (10)
−0.0019 (13)
−0.0014 (14)
0.0013 (16)
−0.001 (2)
−0.011 (2)
−0.003 (2)
0.002 (2)
0.007 (2)
0.010 (3)
0.012 (3)
0.009 (2)
−0.0060 (6)
−0.0009 (11)
−0.0045 (14)
−0.0028 (12)
0.0013 (16)
−0.004 (2)
−0.009 (2)
−0.006 (2)
0.001 (2)
0.007 (2)
0.009 (3)
0.010 (3)
0.004 (2)
0.003 (2)
0.0039 (19)
0.000
−0.0143 (7)
0.0049 (9)
−0.0011 (13)
0.0056 (15)
0.0028 (17)
0.002 (2)
−0.004 (3)
0.001 (2)
0.000 (2)
0.007 (2)
0.004 (2)
C5
C6
C7
C8
C9
C10
Ni2
Cl3
Cl4
O3
O4
N2
C11
C12
C13
C14
C15
C16
C17
C18
C19
0.008 (3)
0.016 (3)
0.006 (2)
0.003 (2)
Acta Cryst. (2018). C74
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supporting information
C20
0.033 (2)
0.024 (2)
0.048 (3)
0.006 (2)
0.022 (2)
0.008 (2)
Geometric parameters (Å, º)
Ni1—O1
Ni1—O1i
Ni1—O2i
Ni1—O2
Ni1—N1
Ni1—N1i
Cl1—C9
Cl2—C7
O1—C1
O1—H1
O2—C10
N1—C3
N1—C4
C1—H1A
C1—H1B
C1—C2
C2—H2A
C2—H2B
C2—C3
C3—H3A
C3—H3B
C4—H4
C4—C5
C5—C6
C5—C10
C6—H6
C6—C7
C7—C8
C8—H8
C8—C9
C9—C10
2.096 (3)
Ni2—O3
2.041 (3)
2.096 (3)
2.029 (3)
2.029 (3)
2.060 (3)
2.060 (3)
1.741 (5)
1.749 (4)
1.436 (5)
0.831 (19)
1.312 (4)
1.474 (5)
1.282 (5)
0.9700
0.9700
1.495 (6)
0.9700
0.9700
1.530 (6)
0.9700
Ni2—O3i
2.041 (3)
2.106 (3)
2.106 (3)
2.053 (3)
2.053 (3)
1.737 (5)
1.754 (4)
1.319 (4)
1.434 (5)
0.836 (19)
1.474 (5)
1.277 (5)
0.9700
0.9700
1.505 (6)
0.9700
0.9700
1.529 (6)
0.9700
Ni2—O4
Ni2—O4i
Ni2—N2
Ni2—N2i
Cl3—C19
Cl4—C17
O3—C20
O4—C11
O4—H4A
N2—C13
N2—C14
C11—H11A
C11—H11B
C11—C12
C12—H12A
C12—H12B
C12—C13
C13—H13A
C13—H13B
C14—H14
C14—C15
C15—C16
C15—C20
C16—H16
C16—C17
C17—C18
C18—H18
C18—C19
C19—C20
0.9700
0.9300
0.9700
0.9300
1.457 (6)
1.408 (6)
1.416 (6)
0.9300
1.362 (6)
1.370 (7)
0.9300
1.450 (6)
1.398 (5)
1.422 (6)
0.9300
1.355 (6)
1.379 (7)
0.9300
1.374 (6)
1.410 (5)
1.389 (6)
1.405 (6)
O1i—Ni1—O1
O2—Ni1—O1
O2i—Ni1—O1i
O2i—Ni1—O1
O2—Ni1—O1i
O2i—Ni1—O2
O2—Ni1—N1i
O2i—Ni1—N1
O2i—Ni1—N1i
O2—Ni1—N1
N1i—Ni1—O1
N1i—Ni1—O1i
86.70 (16)
O3—Ni2—O3i
O3—Ni2—O4i
O3i—Ni2—O4i
O3—Ni2—O4
O3i—Ni2—O4
O3—Ni2—N2i
O3—Ni2—N2
O3i—Ni2—N2i
O3i—Ni2—N2
O4—Ni2—O4i
N2i—Ni2—O4i
N2—Ni2—O4i
94.75 (15)
90.54 (11)
173.47 (11)
173.47 (11)
90.54 (11)
96.02 (12)
86.57 (12)
86.57 (12)
96.02 (12)
84.44 (16)
89.08 (13)
88.10 (13)
175.92 (11)
175.92 (11)
89.59 (11)
89.59 (11)
94.17 (15)
94.59 (12)
94.59 (12)
87.55 (12)
87.55 (12)
87.15 (13)
90.57 (13)
Acta Cryst. (2018). C74
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supporting information
N1—Ni1—O1i
N1—Ni1—O1
N1i—Ni1—N1
Ni1—O1—H1
C1—O1—Ni1
C1—O1—H1
C10—O2—Ni1
C3—N1—Ni1
C4—N1—Ni1
C4—N1—C3
O1—C1—H1A
O1—C1—H1B
O1—C1—C2
H1A—C1—H1B
C2—C1—H1A
C2—C1—H1B
C1—C2—H2A
C1—C2—H2B
C1—C2—C3
H2A—C2—H2B
C3—C2—H2A
C3—C2—H2B
N1—C3—C2
N1—C3—H3A
N1—C3—H3B
C2—C3—H3A
C2—C3—H3B
H3A—C3—H3B
N1—C4—H4
N1—C4—C5
C5—C4—H4
C6—C5—C4
C6—C5—C10
C10—C5—C4
C5—C6—H6
C7—C6—C5
C7—C6—H6
C6—C7—Cl2
C6—C7—C8
C8—C7—Cl2
C7—C8—H8
C7—C8—C9
C9—C8—H8
C8—C9—Cl1
C8—C9—C10
C10—C9—Cl1
O2—C10—C5
O2—C10—C9
87.15 (13)
90.57 (13)
176.86 (19)
120 (3)
122.2 (3)
108 (3)
119.6 (2)
121.4 (3)
121.7 (3)
116.6 (4)
109.2
109.2
112.2 (4)
107.9
109.2
109.2
108.8
108.8
114.0 (4)
107.7
108.8
108.8
113.2 (4)
108.9
108.9
108.9
108.9
107.7
117.0
126.1 (4)
117.0
116.9 (4)
120.1 (4)
122.7 (4)
119.8
120.4 (5)
119.8
119.9 (4)
121.3 (4)
118.8 (4)
120.5
118.9 (4)
120.5
N2i—Ni2—O4
N2—Ni2—O4
N2i—Ni2—N2
C20—O3—Ni2
Ni2—O4—H4A
C11—O4—Ni2
C11—O4—H4A
C13—N2—Ni2
C14—N2—Ni2
88.10 (13)
89.08 (13)
176.19 (19)
116.7 (2)
118 (3)
123.0 (3)
111 (3)
121.2 (3)
120.5 (3)
117.8 (4)
109.2
109.2
112.2 (3)
107.9
109.2
109.2
108.7
108.7
114.1 (4)
107.6
108.7
108.7
112.4 (4)
109.1
109.1
109.1
109.1
107.9
117.1
125.9 (4)
117.1
117.7 (4)
120.5 (4)
121.8 (4)
119.6
120.8 (5)
119.6
120.3 (4)
121.2 (4)
118.4 (4)
120.8
118.4 (4)
120.8
C14—N2—C13
O4—C11—H11A
O4—C11—H11B
O4—C11—C12
H11A—C11—H11B
C12—C11—H11A
C12—C11—H11B
C11—C12—H12A
C11—C12—H12B
C11—C12—C13
H12A—C12—H12B
C13—C12—H12A
C13—C12—H12B
N2—C13—C12
N2—C13—H13A
N2—C13—H13B
C12—C13—H13A
C12—C13—H13B
H13A—C13—H13B
N2—C14—H14
N2—C14—C15
C15—C14—H14
C16—C15—C14
C16—C15—C20
C20—C15—C14
C15—C16—H16
C17—C16—C15
C17—C16—H16
C16—C17—Cl4
C16—C17—C18
C18—C17—Cl4
C17—C18—H18
C17—C18—C19
C19—C18—H18
C18—C19—Cl3
C18—C19—C20
C20—C19—Cl3
O3—C20—C15
O3—C20—C19
118.7 (4)
123.2 (4)
118.1 (3)
123.3 (4)
120.7 (4)
118.4 (4)
123.2 (4)
118.4 (3)
123.1 (4)
121.2 (4)
Acta Cryst. (2018). C74
sup-5

supporting information
C9—C10—C5
115.9 (4)
C19—C20—C15
115.8 (4)
Ni1—O1—C1—C2
Ni1—O2—C10—C5
Ni1—O2—C10—C9
Ni1—N1—C3—C2
Ni1—N1—C4—C5
Cl1—C9—C10—O2
Cl1—C9—C10—C5
Cl2—C7—C8—C9
O1—C1—C2—C3
N1—C4—C5—C6
N1—C4—C5—C10
C1—C2—C3—N1
C3—N1—C4—C5
C4—N1—C3—C2
C4—C5—C6—C7
C4—C5—C10—O2
C4—C5—C10—C9
C5—C6—C7—Cl2
C5—C6—C7—C8
C6—C5—C10—O2
C6—C5—C10—C9
C6—C7—C8—C9
C7—C8—C9—Cl1
C7—C8—C9—C10
C8—C9—C10—O2
C8—C9—C10—C5
C10—C5—C6—C7
−53.3 (5)
−37.6 (5)
144.0 (3)
50.4 (5)
Ni2—O3—C20—C15
Ni2—O3—C20—C19
Ni2—O4—C11—C12
Ni2—N2—C13—C12
Ni2—N2—C14—C15
Cl3—C19—C20—O3
39.1 (5)
−141.0 (3)
53.0 (4)
−55.5 (5)
−9.6 (6)
0.0 (6)
179.9 (3)
−175.4 (3)
−66.9 (5)
160.3 (4)
−22.0 (7)
68.7 (5)
178.5 (4)
116.4 (4)
178.7 (4)
4.6 (6)
−175.3 (4)
174.7 (4)
−3.9 (8)
−177.8 (4)
2.4 (6)
3.2 (7)
177.5 (4)
0.4 (7)
9.2 (6)
−4.7 (5)
176.7 (3)
−178.6 (4)
69.4 (5)
−169.0 (4)
16.1 (7)
−68.4 (5)
−177.3 (4)
−123.2 (4)
−177.4 (5)
−0.1 (7)
178.4 (4)
179.2 (4)
0.2 (8)
−174.9 (4)
3.6 (6)
0.4 (8)
−178.7 (4)
1.2 (7)
175.4 (4)
−3.2 (6)
−2.3 (7)
Cl3—C19—C20—C15
Cl4—C17—C18—C19
O4—C11—C12—C13
N2—C14—C15—C16
N2—C14—C15—C20
C11—C12—C13—N2
C13—N2—C14—C15
C14—N2—C13—C12
C14—C15—C16—C17
C14—C15—C20—O3
C14—C15—C20—C19
C15—C16—C17—Cl4
C15—C16—C17—C18
C16—C15—C20—O3
C16—C15—C20—C19
C16—C17—C18—C19
C17—C18—C19—Cl3
C17—C18—C19—C20
C18—C19—C20—O3
C18—C19—C20—C15
C20—C15—C16—C17
177.1 (4)
−3.1 (6)
1.0 (7)
Symmetry code: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···O3
O4—H4A···O2ii
0.84 (3)
0.84 (2)
1.87 (3)
1.91 (2)
2.702 (4)
2.736 (4)
172 (4)
168 (4)
Symmetry code: (ii) x, y−1, z.
Acta Cryst. (2018). C74
sup-6