Synthesis and spectroscopic characterization of Ni(II) complexes involving functionalised dithiocarbamates and triphenylphosphine: Anagostic interaction in (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S′) (thiocyanato-N)(triphenylphosphine)nickel(II)

Article abstract of DOI:10.1016/j.molstruc.2015.08.053

Twelve new nickel(II) complexes namely [Ni(S₂CNRR′)₂](1-6) and [Ni(S₂CNRR′)(NCS)(PPh₃)](7-12) [where R = cyclopropyl (^cPr); R′ = 2HO-C₆H₄-CH₂- (1,7), 3HO-C₆H₄-CH₂- (2,8), 4HO-C₆H₄-CH₂- (3,9), 4CH₃O-C₆H₄-CH₂- (4,10), 4F-C₆H₄-CH₂- (5,11), 4Cl-C₆H₄-CH₂- (6,12)] have been prepared and characterized by elemental analysis, IR, UV-Vis and NMR (¹H and ¹³C) spectroscopy. A single crystal X-ray structural analysis was carried out for (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S′)(thiocyanato-N)- (triphenylphosphine)nickel(II). The increase in wavenumber of ν_C-N thioureide and decrease in chemical shift values of heteroleptic complexes 7-12 compared to that of homoleptic complexes 1-6 are due to the mesomeric drift of electron density from the dithiocarbamate moiety towards the metal centre, increasing the carbon-nitrogen double bond character. The increased strength of C-N bond is due to the presence of the π-accepting triphenylphosphine. Electronic spectral studies indicated square planar geometry around the nickel(II) central atom for all the complexes. Single crystal X-ray structural analysis of 11 confirms that the coordination geometry about the Ni is distorted square planar. The C-H^...F interactions lead to a polymeric structure and a rare intramolecular anagostic interaction [M^…H = 2.929 ?] is observed. The molecular geometry, HOMO-LUMO in the ground state and MEP have been calculated for 11 using the Hartree-Fock (HF) method with the LANL2DZ basic set. The optimized bond lengths and bond angles agree well with the experimental results. The asymmetry in the Ni-S bonds reveal the greater trans influence of triphenylphosphine compared to that of the isothiocyanate ion.

Full text of DOI:10.1016/j.molstruc.2015.08.053

Accepted Manuscript
Synthesis and spectroscopic characterization of Ni(II) complexes involving
functionalised dithiocarbamates and triphenylphosphine: anagostic interaction
in (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S’)- (thiocyanato-N)
(triphenylphosphine)nickel(II)
E. Sathiyaraj, T. Srinivasan, Dr. S. Thirumaran, D. Velmurugan
PII:
S0022-2860(15)30241-6
10.1016/j.molstruc.2015.08.053
MOLSTR 21785
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 3 April 2015
Revised Date: 19 August 2015
Accepted Date: 25 August 2015
Please cite this article as: E. Sathiyaraj, T. Srinivasan, S. Thirumaran, D. Velmurugan, Synthesis
and spectroscopic characterization of Ni(II) complexes involving functionalised dithiocarbamates and
triphenylphosphine: anagostic interaction in (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S’)-
(thiocyanato-N)(triphenylphosphine)nickel(II), Journal of Molecular Structure (2015), doi: 10.1016/
j.molstruc.2015.08.053.
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ACCEPTED MANUSCRIPT
GRAPHICAL ABSTRACT
MEP
Crystal structure

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Synthesis and spectroscopic characterization of Ni(II) complexes involving
functionalised dithiocarbamates and triphenylphosphine: anagostic
interaction in (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S′)-
(thiocyanato-N)(triphenylphosphine)nickel(II)
E. Sathiyaraja, T. Srinivasanb, S. Thirumarana* and D. Velmuruganb
aDepartment of Chemistry, Annamalai University, Annamalinagar 608 002, Tamilnadu, India.
bCentre of Advanced Study in Crystallography and Biophysics, University of Madras,
Maraimalai Campus (Guindy Campus), Chennai 600 025, India
*Address for correspondence
Dr. S. Thirumaran
Department of Chemistry
Annamalai University
Annamalainagar 608 002
Tamilnadu, INDIA
Tel: +91 9842897597
E-mail: sthirumaran@yahoo.com

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Synthesis and spectroscopic characterization of Ni(II) complexes involving
functionalised dithiocarbamates and triphenylphosphine: anagostic
interaction in (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S′)-
(thiocyanato-N)(triphenylphosphine)nickel(II)
E. Sathiyaraja, T. Srinivasanb, S. Thirumarana* and D. Velmuruganb
ABSTRACT
Twelve
new
nickel(II)
complexes
namely
[Ni(S2CNRR')2](1-6)
and
[Ni(S2CNRR')(NCS)(PPh3)](7-12) [where R=cyclopropyl (cPr); R'=2HO–C6H4–CH2– (1,7),
3HO–C6H4–CH2– (2,8), 4HO–C6H4–CH2– (3,9), 4CH3O–C6H4–CH2– (4,10), 4F–C6H4–CH2–
(5,11), 4Cl–C6H4–CH2– (6,12)] have been prepared and characterized by elemental analysis, IR,
UV-Vis and NMR (1H and 13C) spectroscopy. A single crystal X-ray structural analysis was
carried out for (N-cyclopropyl-N-(4-fluorobenzyl)dithiocarbamato-S,S′)(thiocyanato-N)-
(triphenylphosphine)nickel(II).
The
increase
in
wavenumber
of
νC-N thioureide and decrease in chemical shift values of heteroleptic complexes 7-12 compared
to that of homoleptic complexes 1-6 are due to the mesomeric drift of electron density from the
dithiocarbamate moiety towards the metal centre, increasing the carbon-nitrogen double bond
character. The increased strength of C−N bond is due to the presence of the π-accepting
triphenylphosphine. Electronic spectral studies indicated square planar geometry around the
nickel(II) central atom for all the complexes. Single crystal X-ray structural analysis of 11
confirms that the coordination geometry about the Ni is distorted square planar. The C−H F
interactions lead to a polymeric structure and a rare intramolecular anagostic interaction [M H=
2.929 Å] is observed. The molecular geometry, HOMO-LUMO in the ground state and MEP
have been calculated for 11 using the Hartree-Fock (HF) method with the LANL2DZ basic set.
The optimized bond lengths and bond angles agree well with the experimental results. The
asymmetry in the Ni−S bonds reveal the greater trans influence of triphenylphosphine compared
to that of the isothiocyanate ion.
Keywords: Nickel(II) dithiocarbamate; FT-IR; UV-Vis; NMR; Anagostic interaction

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INDRODUCTION
The current interest in the study of the chemistry of transition metal dithiocarbamate
complexes is motivated by their utility in a diverse applications, such as in medicine [1-4],
agriculture [5-7], organic synthesis [8] and even as synthetic precursor for metal sulfide
nanoparticles [9-15]. In addition to this, considerable interest was also for the X-ray
crystallographic studies of transition metal complexes, and there is a wealth of structural data
available for these complexes, with some notable studies motivated by crystal engineering [16-
18]. Many metal dithiocarbamate complexes are stabilized by C−H S, C−H O, C−H N,
C−H π and π−π interactions providing 3D, 2D and 1D supramolecular structures [19, 20]. The
functionalizaton of N-bound organic moiety in the dithiocarbamate ligand may generate a variety
of molecular architectures and potentially gives rise to tunable physical properties [21]. One
commonly
known
functionalized
dithiocarbamate
ligand
is
N,N-di(2-
hydroxyethyl)dithiocarbamate which exhibits different supramolecular aggregation in its
complexes [22, 23].
In addition to these interactions, some homoleptic and heteroleptic dithiocarbamate
complexes of group 10 metal ions exhibited the rare C−H M intramolecular anagostic
…
interactions [24-29]. Recently, C−H Ni intermolecular anagostic interactions in some nickel-bis
dithiocarbamate complexes have been reported [30, 31]. This anagostic interactions (H Ni
distance between ≈2.3-2.9 Å) are believed to be important for catalytic applications [32]. In
recent years, scientists used computational methods to characterize the complexes because of
their good efficiency and great precision in the prediction of a number of molecular properties
[33]. Computational studies also help to evaluate compound properties economically and to
clarify some experimental phenomena insightfully [34, 35]. Due to the applications of metal

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dithiocarbamate complexes and their diverse supramolecular aggregation patterns, we thought it
is worth to study the synthesis and characterization of some new homoleptic and heteroleptic
Ni(II) complexes involving functionalized dithiocarbamate ligands.
Experimental
All materials and solvents were obtained from commercial suppliers and used
without further purification. Melting points were determined on an electro thermal melting point
apparatus and were reported uncorrected. Elemental analysis was performed in a varioMICRO
V2.2.0 apparatus. Infrared spectra were recorded on a SHIMADZU FT-IR spectrophotometer in
the frequency range 4000–400 cm–1. 1H NMR spectra were recorded on Bruker 400 MHz and the
13C NMR spectra on a Bruker 100 MHz spectrometer using CDCl3 and DMSO-d6 as solvents and
tetramethylsilane (TMS) as internal standard. Single-crystal X-ray structural studies were
performed on a bruker SMART APEXII Diffractometer. The intensity data were collected at
293(2) K using graphite monochromated Mo Kα radiation (λ = 0.71073 Å). The structure was
solved by the direct method and refined using the SHELX-97 [36, 37] suite of programs. Figures
were drawn using ORTEP-3.2 and MERCURY-2.3. The hydrogen atoms were included at
geometrically calculated positions in the final stages of the refinement and were refined
according to the ‘‘riding model”. All non-hydrogen atoms were refined anisotropically. All
calculations were performed with GAUSSIAN09 program package [38] with the aid of the
GaussView visualization program. All the characterization data are given in supplementary
material.
EXPERIMENTAL
Preparation of amines

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4.6 mmol of cyclopropylamine and 5.1 mmol of substituted benzaldehydes (2-OH, 3-OH,
4-OH, 4-OCH3, 4-F and 4-Cl) were dissolved in methanol (30 mL) and the solution was stirred for 2 h
at room temperature. The solvent was removed by evaporation. The resulting colourless oil was
dissolved in methanol-dichloromethane solvent mixture (1:1, 20 mL) and sodium borohydride
(13.8 mmol) was added slowly at 5°C and stirred for 2 h before removal of ice bath. The
reaction mixture was stirred at room temperature for 20 h. After evaporation of the solvent, the
resulting viscous liquid was washed with water, and dichloromethane was added in order to
extract the product. Evaporation of the organic layer gave N-cyclopropyl-N-substituted
benzylamine as a pale yellow oil
Preparation of complexes (1-6)
N-cyclopropyl-N-substituted benzylamine (4.0 mmol) in ethanol was mixed with carbon
disulfide (4.0 mmol) under ice cold condition. To the resultant yellow dithiocarbamic acid solution,
aqueous solution of NiCl2 6H2O (2.0 mmol) was added with constant stirring. The solid
which precipitated was washed several times with cold water and then dried. (Fig. 1)
Preparation of complexes (7-12)
A mixture of complex (1-6) (1.0 mmol, 0.624 g), PPh3 (2.0 mmol, 0.524 g), NiCl2 6H2O
(1.0 mmol, 0.237 g) and NH4SCN (2.0 mmol, 0.152 g) was refluxed for 3 h in acetonitrile-
methanol solvent mixture (1:1, 50 mL). The purple-red solution obtained was filtered and left for
evaporation. After 2 days, a purple-red solid separated out which was recrystallized from
dichloromethane. (Fig. 1)
Results and discussion
IR spectral studies

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Important absorptions in the dithiocarbamate complexes are due to νC–N and νC–S
stretching modes [39-42]. For the homoleptic complexes (1–6), strong bands appeared in the
1470-1474 cm−1 region that are due to νC–N (thioureide). For the heteroleptic complexes (7-12),
νC-N (thioureide) bands were observed in the 1474-1491 cm-1 region. The increase in
wavenumber for complexes (7-12), compared to that of the parent complexes (1-6), is attributed
to the mesomeric drift of electron density from dithiocarbamate ligand to nickel through the
thioureide C-N bond [43]. The νC−S stretching vibrations are observed around 1000 cm-1 without
,
any splitting, supporting the bidentate coordination of the dithiocarbamate ligand [44]. The
observed stretching frequencies around 2088 cm-1 are due to the ‘N’-coordinated isothiocyanate
anion.
Electronic spectral studies
Electronic spectra of the prepared complexes 1-12 support the assumption of the
square planar coordination of nickel(II) central atom [45, 46]. In all the complexes, the bands
observed below 350 nm are due to the intraligand π-π* transitions. In addition to the charge
transfer bands, the bands observed in the range of 425-650 nm are due to the d-d transitions. In
Complexes 1-6, two bands are observed around 620 and 460 nm. These bands correspond to
dxy→ dx2–y2 and dz2→ dx2–y2 transitions, respectively. A band observed around 483 nm for the
heteroleptic complexes (7-12) are due to d-d transitions. These bands are assigned to
dz2/dxy→ dx2–y2 transitions.
NMR spectral studies
1H NMR spectral studies
In the complexes 1-6, the methylene protons of benzyl and methyne protons of
cyclopropyl group give signals around 4.66 and 2.60 ppm, respectively. The remaining signals in

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the aliphatic region are assigned to the methylene protons of cyclopropyl group. The methylene
protons and methyne proton adjacent to nitrogen atom are greatly deshielded and are observed in
the downfield region due to complexation. For all the complexes, the signals observed in the
downfield region, 6.64-7.71 ppm, are due to the aromatic protons in the dithiocarbamate and
triphenylphosphine ligands. Aliphatic proton signals in heteroleptic complexes 7-12 appeared as
broad signals. The fast isothiocyanate ligand exchange process is responsible for the broadening
of the aliphatic proton signals [47]. A singlet observed around 9.80 ppm in complexes
1-3 is assigned to OH protons. A signal is expected for OH proton in complexes 7-9. But this
signal is merged with aromatic proton signals of dithiocarbamate and triphenylphosphine
ligands. Complexes 4 and 10 exhibit a singlet around 3.8 ppm due to methyl protons of the
methoxy group.
13C NMR spectral studies
All the complexes show a single downfield resonance characteristic of NCS2
carbon of dithiocarbamate ligands in the range 206.1-213.1 ppm [48]. The upfield shift in the
NCS2 chemical shift values of heteroleptic complexes (10-12) compared to that of homoleptic
complexes (4-6) is due to the mesomeric drift of electron density from the dithiocarbamate
moiety towards the metal centre, increase the carbon nitrogen double bond character. This
observation reveals that the increased strength of the thioureide bond is due to the presence of
π-accepting phosphine. In all the complexes 1-12, the signals for methylene carbon of benzyl
group and methyne carbon of cyclopropyl group appear around 51.8 and 31.6 ppm, respectively.
The remaining signals in the aliphatic region are assigned to the methylene carbon of
cyclopropyl group. In all the cases, aromatic carbon signals appear in the region 113.8-163.9
ppm. A weak signal observed in the downfield region 154.8-159.6 ppm for complexes 1-4 and

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7-10 is due to the ipso carbon of the dithiocarbamate ligand. In the case of complexes 9 and 10,
the thiocyanate (NCS) carbon resonates around 143 ppm. In the fluoro-substituted complexes 5
and 11, two signals appeared around 161 and 164 ppm that are due to the ipso carbon [49].
Crystal structure
We prepared Ni(II) complexes containing functionalized dithiocarbamate ligands to
study the intra-and intermolecular interactions due to the presence of a functional group on the
phenyl ring. Most of the samples gave rise to the plates upon recrystalisation, and these crystals
proved to be unsuitable for single crystal X-ray structural analysis. Crystals suitable for single
crystal X-ray structure determination were obtained only for complex 11.
The ORTEP diagram of complex 11 is given in Fig. 2. Details of the crystal data
and structure refinement parameters are summarized in Table 1. Selected bond lengths and
angles are given in Table 2. Single crystals of complex 11 suitable for X-ray crystallography
were obtained from dichloromethane: acetonitrile (2:1) solution. In this complex, the nickel(II) ion
is coordinated to three ligands, two sulfur atoms from dithiocarbamate, one nitrogen from
thiocyanate and one phosphorus from triphenylphosphine in a distorted square planar. The bond
angles P1-Ni-S2= 92.73(4)°, N2-Ni-S1=93.45(10)°, and N2-Ni-P1=93.45(3)° are less distorted
from 90° than S2-Ni-S1 angle, which is 78.55(4)°. The large deviation of the S2-Ni-S1 bond
angle from 90° is due to the chelation of dithiocarbamate ligand. The structure adopted by this
complex is characterized using τ4–descriptor for four coordinated ions [50]. The distortion index
is defind as τ4 = (360–(α+β))/141. The τ4 values for perfect tetrahedral, trigonal pyramid,
seesaw structure and perfect square planar are 1.00, 0.85, 0.64-0.07 and 0.00, respectively. The
τ4 value of this complex (0.1249) indicates that the coordination geometry around Ni(II) is best

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described as being 12% along the pathway of distortion from the square planar toward seesaw
structure (τ4=0.64-0.07) .
The average Ni-S bond lengths, 2.2026(12) Å, are similar to those observed in
other nickel dithiocarbamate complexes [51]. The Ni-S distance trans to the phosphorus is longer
2.2234(12) Å than those found in case of the trans to the NCS [Ni-S=2.1819 (11) Å]. This
reflects the greater trans influence of triphenylphosphine compared to that due to the thiocyanate
group. The short Ni-N2 [1.859(3) Å] and Ni-P1 [2.1991(12) Å] distances confirm the effective
bonding of nickel to the thiocyanate and triphenylphosphine moieties. The N-C-S angle (178.6°)
indicates a slight deviation from linearity. This is due to the both steric effect of the bulky
triphenylphosphine and weak S H-C (S H=2.619 Å) interaction. A significant delocalization of
the π-electron density over the S2CN moiety in complex 11 is typical for bidentate coordination
of any dithiocarbamate anion to a transition metal and is evident from the C-N and C-S bond
length values (Table 2).
For complex 11, in addition to the van der Waals interactions, the molecular structure is
influenced by the intramolecular C-H S hydrogen bond involving S1 (Fig. 3.). The complex
molecules are bonded to an neighbouring molecule through C3-H3 F and C1-H1 F
interactions, resulting in a polymeric structure (Fig. 4.). Three forms of C-H M interactions,
namely: (i) hydrogen bond (ii) agostic and (iii) anagostic were reported [52, 53]. Hydrogen
bonds are 3-centre-4-electron interactions with an almost linear geometry. Agostic interactions
are 3-centre-2-electron interactions and characterized by the short M…H distance (ꢀ1.8-2.2 Å)
and C-H M bond angles (90-130°). Anagostic interactions are largely electrostatic in nature and
characterized by long M…H distance (ꢀ2.3–2.9 Å) and large M H-C bond angles (ꢀ110-170°).
The anagostic interactions are typically formed with group 10 metal ions with d8 configurations

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[54]. The packing, steric and electronic effects of both bulky ligands and diamagnetic nickel(II)
d8, forces the ortho proton of one of the phenyl ring of PPh3 ligand to be in close proximity to
one of the axial positions around the nickel. This creates an unusual anagostic interaction (Fig. 5)
and is observed in 11 (M H=2.929 Å and <M H-C=117.13°). Anagostic and C-H F
(polymeric structure) interactions are absent in (N-cyclopropyl-N-benzyldithiocarbamato-S,S′)
(thiocyanato-N)(triphenylphosphine)nickel(II)[55].
This results show that the interactions observed in the complex 11 are mainly due to the
presence of fluorine on the para position of phenyl ring in the dithiocarbamate ligand, and also
confirms that the functionalizaton of the N-bound organic moiety in dithiocarbamate ligand
influences the properties of the complexes.
Optimized structure
The geometry of complex 11 is fully optimized by the HF/LANL2DZ method using the
Gaussian09 software. Some important experimental and theoretical geometric parameters are
listed in Table 4 and are in accordance with the atom numbering scheme given in the ORTEP
view of the compound (Fig. 6). Bond lengths and bond angles obtained from the single crystal
X-ray structure determination are compared with their optimized counterparts. It can be seen that
the calculated structural parameters for complex in the gas phase are in good agreement with the
structure determined by X-ray crystallography in the solid state except Ni-S and Ni-P distances.
Comparison of the experimental bond parameters with the calculated values shows that the bond
length difference is 0.079 Å and 0.020 Å for C-S and C-N distances and bond angle difference is
3.84° (C12-N2-Ni1). The difference in Ni-S and Ni-P bond distances is 0.222 Å (Ni-S1) and
0.331 (Ni-P1), respectively. This indicates the absence of trans influence and back bonding
interaction between Ni and P in gaseous state.

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HOMO-LUMO
The HOMO–LUMO gap energy is an important parameter which characterizes the
electronic structure of molecules and is also used to determine their kinetic stability (reactivity)
and electrical conductivity [56]. From the MO’s plot (Fig.7), it can be seen that the HOMO is
mainly centered on the P atom of the triphenylphosphine and on the metal coordinated sulfur
atom (which act as donor atoms) whereas the LUMO is mainly located over the N and S atoms
of the thiocyanate fragment (which function as acceptor atoms).
HOMO energy = -8.1110 eV
LUMO energy = 1.8206 eV
HOMO-LUMO energy gap = -6.2904 eV
The energy gap between the HOMO and LUMO are related to the hardness of a
molecule, η, which is defined as: η = (I-A)/2. Where I and A are the ionization potential and the
electron affinity of the system, respectively. The hardness of complex 11 is then calculated as
-3.452 eV.
Molecular Electrostatic Potential (MEP) surface
The MEP surface was obtained at the HF/LANL2DZ optimized geometry to predict
reactive sites for electrophilic attack and nucleophilic reaction processes for the complex.
Molecular electrostatic potential surface map of complex 11 is given in Fig. 8. The negative and
positive regions of the MEP are related to electrophilic and nucleophilic regions of the
compound, respectively. The negative regions are indicated by red and yellow and positive
regions
are
represented
in
blue
colour

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(Fig. 8). From the figures, it can be concluded that this molecule has several possible sites for
electrophilic attack. The negative regions are mainly over the thiocyanate sulfur (-6.669). Thus,
it is predicted that an electrophile would preferentially attack the thiocyanate sulfur atom [57,
58]. The positive charge (dark blue) on the nitrogen atom N1, and the negative charge (light
yellow) on the C1, S1 and S2 atoms of dithiocarbamate group, indicate a partial the double bond
character of the formally single N-C bond (Fig. 9) in the dithiocarbmate moiety.
Conclusion
Complexes 1-12 were prepared and characterized by IR, UV-Vis, and NMR
spectroscopy. IR and 13C NMR spectral studies showed the increase in the double bond character
of the thioureide C-N bond in heteroleptic complexes, due to the presence of the
…
triphenylphosphine group. Anagostic and C-H F (polymeric structure) interactions are
observed in complex 11. These interactions are totally absent in (N-cyclopropyl-N-
benzyldithiocarbamato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II).
This
confirms that functionalization of the dithiocarbamate ligand might increases the inter- and
intramolecular interactions. The molecular geometry, HOMO-LUMO and MEP have been
calculated, the latter also supporting the partial double bond character of the C-N thioureide bond
in the dithiocarbamate fragment.
Supplementary data
Crystallographic data for the structure reported in this paper have been deposited in the
Cambridge Crystallographic Data Centre, as supplementary publication CCDC No.-1057195
(complex 11). Copies of the data can be obtained free of charge from the CCDC, 12 Union Road,

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Cambridge CB1 1EZ, UK (Tel: (+44) 1223-336-408; Fax: (+44) 1223-336-003; E-mail:
deposit@ccdc.cam.ac.uk).
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Figure captions
Fig. 1. Structure of complexes
Fig. 2. ORTEP of complex 11
Fig. 3. Intramolecular S H–C interaction in complex 11
Fig. 4 Polymeric chain through intermolecular C-H F interactions
Fig. 5. Intramolecular Ni H-C anagostic interaction in complex 11
Fig. 6. Optimized structure of complex 11
Fig. 7. The frontier molecular orbital (HOMO-LUMO) pictures of the optimized complex 11
Fig. 8. Molecular electrostatic potential surface map of complex 11
Fig. 9. Resonance forms of dithiocarbamate

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Table 1. Data Refinement Parameters for complex
Empirical formula
C30 H26 F N2 Ni P S3
619.39
FW
Crystal dimensions (mm)
0.30 × 0.25 × 0.20
Monoclinic
P 21/n
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
14.227(5)
9.947(5)
21.271(5)
90.000
102.721(5)
90.000
β/°
γ/°
V/Å3
Z
2936.3(19)
4
Dc/g cm–3
µ/cm–1
F(000)
λ/Å
1.388
0.957
1280
MoKα (0.71073)
1.58-28.37
θ Range/°
Index ranges
-19≤ h ≤ 18, -13 ≤ k ≤ 13, -26≤ l ≤ 28
Reflections collected
Observed reflections I > 2σ(I)
Weighting scheme
28037
4839
Calc. W = 1/(σ2(Fo2) + (0.0791p)2 + 2.4944p)
2
2
where p = (Fo + 2Fc )/3
343
Number of parameters refined
R[F2 > 2σ(F2)], wR(F2)
GOOF
0.0527, 0.1380
1.061

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Table 2. Selected bond distances (Å) and angles (°) for complex 11
Bond distances (Å)
XRD
XRD
Bond angles (°)
C1-N1
C1-S1
C1-S2
C12-N2
C12-S3
N2-Ni1
P1-Ni1
S1-Ni1
S2-Ni1
1.314(4)
1.709(3)
N1-C1-S1
N1-C1-S2
S1-C1-S2
N2-C12-S3
C12-N2-Ni1
N2-Ni1-P1
N2-Ni1-S1
S2-Ni1-S1
S1-Ni1-P1
126.8(3)
124.5(3)
108.63(19)
178.6(4)
170.3(4)
95.13(10)
93.45(10)
78.55(4)
92.73(4)
1.725(3)
1.147(5)
1.609(4)
1.859(3)
2.1991(12)
2.2234(12)
2.1819(11)
Table 3. Distances (Å) and angles (°) of the hydrogen bond interactions in complex 11
Interactions
C4-H4B...S1a
D-H
H…A
2.619
2.441
2.352
2.929
D…A
3.078
3.345
3.311
3.455
D-H…A
109.23
154.81
165.85
117.13
0.970
0.970
0.986
0.931
C3-H3B...F1b
C1-H1...F1b
C24-H24...Nia
aIntramolecular contacts.
bIntermolecular contacts.

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Table 4. Selected bond distances (Å) and angles (°) for complex 11
HF/LAN2DZ
HF/LAN2DZ
Bond distances (Å)
XRD
Bond angles (°)
XRD
C1-N1
C1-S1
C1-S2
C12-N2
C12-S3
N2-Ni1
P1-Ni1
S1-Ni1
S2-Ni1
1.314(4)
1.709(3)
1.320
1.788
1.782
1.167
1.676
1.893
2.531
2.379
2.404
N1-C1-S1
N1-C1-S2
S1-C1-S2
N2-C12-S3
C12-N2-Ni1
N2-Ni1-P1
N2-Ni1-S1
S2-Ni1-S1
S1-Ni1-P1
126.8(3)
124.5(3)
108.63(19)
178.6(4)
170.3(4)
95.13(10)
93.45(10)
78.55(4)
92.73(4)
123.12
124.40
112.46
178.20
174.14
92.57
1.725(3)
1.147(5)
1.609(4)
1.859(3)
2.1991(12)
2.2234(12)
2.1819(11)
95.50
76.68
95.15

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(a)
1-6
(b)
7-12
Fig. 1.
Complex
1, 7
Substituent (R)
2-OH
2, 8
3-OH
3, 9
4-OH
4, 10
5, 11
6, 12
4-OCH3
4-F
4-Cl

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Fig. 2.

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Fig. 3.

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Fig. 4.

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Fig. 5.

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Fig. 6.

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(a)
(b)
Fig. 7.

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Fig. 8.