Synthesis, Crystallographic Structure, Hirshfeld Surface Analysis, and DFT Calculations of Two Salen-Type Hetero-Halogenated Schiff Base Mn(IV)/(III) Complexes

Article abstract of DOI:10.1134/S1070328420020086

Abstract: Two new supramolecular compounds [Mn^IV(μ-3-Br-5-Cl-Salpn)(μ-O)]₂ · 2[DMF] (I) and [Mn^III(3-Br-5Cl-Salmen)(3-bromo-5-chlorosalicylaldehyde)]₂ (II) (3-Br-5Cl-Salpn = N,N'-bis(3-bromo-5-chlorosalicylidene)-1,3-diamine and 3-Br-5Cl-Salmen = N,N'-bis(3-bromo-5-chlorosalicylidene)-1,2-diamine) have been synthesized via conventional solution method and characterized by single crystal (CIF files CCDC nos. 1855961 (I), 1900154 (II) and powder X-ray diffraction, IR spectroscopy and elemental analysis. The unconventional C–H···X (X = Cl and Br) supramolecular interaction within the compounds were qualitatively and quantitatively studied by Hirshfeld surface analysis. Additionally, in order to gain a deep insight into the electronic features of I, density functional theory was used for the calculations of the HOMO and LUMO energies and molecular electrostatic potential surface.

Full text of DOI:10.1134/S1070328420020086

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2020, Vol. 46, No. 2, pp. 137–144. © Pleiades Publishing, Ltd., 2020.
Synthesis, Crystallographic Structure, Hirshfeld Surface Analysis,
and DFT Calculations of Two Salen-Type Hetero-Halogenated Schiff
Base Mn(IV)/(III) Complexes
Q. Wua, b, *, J. D. Lia, F. X. Liua, J. C. Xiaoa, Y. F. Tanga, and Q. L. Zia
aDepartment of Chemical Science and Technology, Kunming University, Yunnan, Kunming, 65200 P.R. China
bYunnan Engineering Technology Research Center for Plastic Films, Kunming, 65200 P.R. China
*e-mail: wuqiongkm@163.com
Received April 30, 2019; revised July 10, 2019; accepted August 14, 2019
Abstract—Two new supramolecular compounds [MnIV(μ-3-Br-5-Cl-Salpn)(μ-O)]2 · 2[DMF] (I) and
[MnIII(3-Br-5Cl-Salmen)(3-bromo-5-chlorosalicylaldehyde)]2 (II) (3-Br-5Cl-Salpn = N,N'-bis(3-bromo-
5-chlorosalicylidene)-1,3-diamine and 3-Br-5Cl-Salmen = N,N'-bis(3-bromo-5-chlorosalicylidene)-1,2-
diamine) have been synthesized via conventional solution method and characterized by single crystal (CIF
files CCDC nos. 1855961 (I), 1900154 (II) and powder X-ray diffraction, IR spectroscopy and elemental
analysis. The unconventional C–H···X (X = Cl and Br) supramolecular interaction within the compounds
were qualitatively and quantitatively studied by Hirshfeld surface analysis. Additionally, in order to gain a deep
insight into the electronic features of I, density functional theory was used for the calculations of the HOMO
and LUMO energies and molecular electrostatic potential surface.
Кeуwords: halogenated Schiff-base, crystal structure, weak molecular interactions, Hirshfeld surface analy-
sis, density functional theory calculations
DOI: 10.1134/S1070328420020086
INTRODUCTION
and composition is a fundamental way for detailed
exploration of the halogen atom conducted intermo-
lecular interactions [7, 8]. In this aspect, tetradentate
Schiff base (Salen) complex is an ideal candidate, not
only because their diverse structures and tunable con-
stitution [9, 10], but also because salen-type com-
pound is a well researched subject, subtle difference
between analogs can be easily detected and more
deeply studied [11, 12].
Supramolecular chemistry is a multidisciplinary
research domain that ranges from pharmaceutics to
materials science [1, 2]. It is now well known that,
although the magnitude is very small, weak interac-
tions are significant influence in the structural solid
geometry and even physicochemical properties, such
as activities of pharmaceutical ingredients (APIs),
magnetic behavior, et al., therefore, in the past
decade, great efforts have been devoted to the explora-
tion regulating effects of physicochemical properties
of different weak interactions [3, 4].
Based on the aforementioned considerations,
recently, we have initiated exploitation of the relation-
ship between the composition of Salen-type haloge-
nated Schiff-base ligands and their special supramolecu-
lar interactions. Herein, we specifically introduced het-
ero-halogenated Salen-type Schiff-base ligands: N,N'-
bis(3-bromo-5-chlorosalicylidene)-1,3-diamine (3-Br-
5Cl-Salpn) and N,N'-bis(3-bromo-5-chlorosalicy-
lidene)-1,2-diamine (3-Br-5Cl-Salmen) and manganate
as starting materials, and isolated two new manganese
In recent years, halogen atoms have been recog-
nized as an important factor in mediation of the supra-
molecular networks of crystalline materials. However,
compared with the classical hydrogen bond interac-
tions, the contact form by halogen atoms are
much weaker, therefore, it is difficult to carry out
qualitative and quantitative research, especially for the
N- and O-rich ligands involved supramolecular com-
plex [5, 6], hence, related work is still at a very early
stage.
complexes
[MnIV(μ-3-Br-5-Cl-Salpn)(μ-O)]2
·
2[DMF] (I) and [MnIII(3-Br-5Cl-Salmen)(3-bromo-5-
chlorosalicylaldehyde)]2 (II). Theoretical analysis result
reveal that, although the interactions formed by halogen
Therefore establishing a series of halogenated atom are weak, halogen atoms play a key role in stabling
ligands constructed complexes with similar structure the solid structure of title compounds.
137

138
WU et al.
hyde (0.1 mmol, 0.0235 g) was added to the above
EXPERIMENTAL
mixture and kept stirring for 2 h, then filtered. The fil-
trate was sealed in a beaker and kept undisturbed at
room temperature. The black block crystals of title
compound were afforded after one week. The crystals
were collected by suction filtration washed with meth-
anol, and dried in air (yield of 41% based on manga-
nese(III) acetate).
Materials and measurements. All chemicals were
also commercially available and used without further
purification. Elemental analyses (C, H, and N) were
carried out on a Perkin-Elmer 240C instrument. The
infrared (IR) spectrum was recorded from 400 to
4000 cm—1 on an Alpha Centaurt FT (Fourier trans-
form) IR spectrophotometer using KBr pellets. Pow-
der X-ray diffraction (PXRD) patterns were recorded
with a Bruker D8 ADVANCE X-ray diffractometer at
the room temperature.
For C48H26N4O8Cl4Br4Mn2 (II)
Anal. calcd., %
Found, %
C, 35.45
C, 34.14
H, 1.75
H, 1.62
N, 4.86
N, 4.42
Synthesis of halogenated Schiff base ligand. The
ligands 3-Br-5Cl-Salpn and 3-Br-5Cl-Salmen were
prepared by mixing 3-bromo-5-chlorosalicylaldehyde
(0.047 g, 0.2 mmol) and 1,3-diaminopropane or 1,2-
diaminopropane for 3-Br-5Cl-Salpn or 3-Br-5Cl-
Salmen, respectively (0.0085 mL, 0.1 mmol) in meth-
anol (30 mL). The obtained solution was stirred and
refluxed at 80°C for 3 h. Then, the solvent was
removed by rotary evaporator to give yellow powder
product (Scheme 1).
IR (KBr; ν, cm–1): 2925 ν(ArC–H), 2826 ν(MeC–
H), 1626, 1590 ν(C=N), 1430 ν(CH2), 1115 ν(C–O),
758 ν(C–Cl), 603 ν(C–Br).
X-ray crystal structure determination. The data
set of reflections were collected at 296(2) K on a Xcal-
ibur Eos automated diffractometer with MoKα radia-
tion (λ = 0.71073 Å) and a low-temperature device
Cryostream cooler (Oxford Cryosystem). Integration
of the intensities and correction for Lorentz and polar-
ization effects were performed using the CrysAlisPro
software [13, 14]. The central manganese atom was
located by direct methods, and successive Fourier syn-
theses revealed the remaining atoms. Refinements
were achieved by the full-matrix method on F2 using
the Olex2 software package [15]. In the final refine-
ment, all the non-H atoms were anisotropically
refined. All H atoms were placed in calculated posi-
tions and refined using the riding model approxima-
tion. For compound I, C–H bonds of methyl and
methylene group were fixed at 0.98 and 0.99 Å,
respectively; for compound II, C–H bonds of methyl
group were fixed at 0.96 Å. The detailed crystal data
and structure refinement for I and II were given in
Table 1. Selective bond lengths and angles of I and II
were listed in Table 2.
R
N
N
Cl
OH HO
Cl
Br
Br
R = 1,3-diaminopropane for 3-Br-5Cl-Salpn
R = 1,2-diaminopropane for 3-Br-5Cl-Salmen
Scheme 1.
Synthesis of [MnIV(µ-3-Br-5-Cl-Salpn)(µ-O)]2 ·
2DMF (I). Mn(AC)2 · 4H2O (0.03675 g, 0.15 mmol)
was added in a mixture solution of methanol (20 mL)
and DMF (10 mL) of 3-Br-5Cl-Salpn (0.0310 g,
0.1 mmol). The black solution was stirred for 2 h. The
black filtrate was sealed in a beaker and kept undis-
turbed at room temperature. The black block crystals
of title compound were afforded after one week. The
crystals were filtrated, washed with methanol, and
dried in air (the yield I was 32%).
The crystal data can be obtained free of charge
from Cambridge Crystallographic Data Centre
(CCDC nos. 1855961 (I), 1900154 (II); www.ccdc.
cam.ac.uk/data_request/cif).
RESULTS AND DISCUSSION
For C40H38N6O8Cl4Br4Mn2 (I)
As shown in Fig. 1a, the basic unit of compound I
consists of a Mn(IV) dimer structure in which two het-
ero-halogenated Salen-type Schiff-base ligands ride
both Mn4+ ions via two nitrogen atoms in the stereo-
scopic mode, then, two μ-2 oxygen atoms further
bridge the metal atoms yield a planar Mn2O2 center
core, this kind of bridging mode is similar to that of
previously reported structure [16], noteworthy that
these two oxygen atoms are assigned as bridging atoms
μ-2 O2– rather than H2O nor to OH– is based on the
bond valence sum (BVS) calculations and symmetry
Anal. calcd., %
Found, %
C, 36.89
C, 37.53
H, 2.94
H, 3.14
N, 6.45
N, 6.73
IR (KBr; ν, cm–1): 2930 ν(ArC–H), 2816 ν(MeC–
H), 1584 ν(C=N), 1421 ν(CH2), 1125 ν(C–O), 756
ν(C–Cl), 598 ν(C–Br).
Synthesis of [MnIII(3-Br-5Cl-Salmen)(3-bromo-
5-chlorosalicylaldehyde)]2 (II). Mn(AC)2 · 4H2O
(0.03675 g, 0.15 mmol) was added to 3-Br-5Cl-
Salmen (0.0504 g, 0.1 mmol) were dissolved in meth-
anol (30 mL), after this 3-bromo-5-chlorosalicylalde- about the central core [17]. Therefore, each Mn4+ ions
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 46
No. 2
2020

SYNTHESIS, CRYSTALLOGRAPHIC STRUCTURE, HIRSHFELD SURFACE ANALYSIS
139
Table 1. Crystallographic data and structure refinement for compounds I and II
Value
Parameter
I
II
Mr
1302.08
173(2)
0.71073
Triclinic
P1
1588.71
293(2)
0.71073
Monoclinic
P21/c
Temperature, K
Wavelength, Å
Crystal system
Space group
a, Å
b, Å
c, Å
α, deg
β, deg
10.207(2)
10.9368(14)
11.9899(11)
102.911(9)
95.437(13)
116.110(17)
1142.6(3)
13.4540(11)
15.4193(9)
14.479(2)
90
118.297(8)
90
γ, deg
Volume, Å3
2644.8(5)
Z
1
2
Calculated density, mg/m3
1.892
1.995
Absorption coefficient, mm–1
4.342
5.370
F(000)
642
1536
θ Range for data, deg
collection, deg
3.57–25.00
3.57–25.00
Limiting indices
–10 ≤ h ≤ 12,
–12 ≤ k ≤ 12,
–14 ≤ l ≤ 14
–15 ≤ h ≤ 15,
–18 ≤ k ≤ 18,
–17 ≤ l ≤ 14
Reflections collected/unique (Rint
Completeness to θ = 25.00, %
Refinement method
)
7650/4006 (0.0668)
15692/4637 (0.0885)
99.7
99.6
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Data/restraints/parameters
4006/0/289
0.975
4637/21/345
1.026
Goodness-of-fit on F2
Final R indices (I > 2σ(I))
R indices (all data)
R1 = 0.0591, wR2 = 0.0758
R1 = 0.1008, wR2 = 0.0910
0.652 and –0.642
R1 = 0.0735, wR2 = 0.1533
R1 = 0.1453, wR2 = 0.1943
0.919 and –0.939
Largest diff. peak and hole, e Å–3
is in a distorted octahedral coordination environment formed C–H···O hydrogen bonds and chlorine atom
[MnO4N2]. Specifically, the equatorial plane of
Mn(IV) center is occupied by two phenol oxygen
atoms (O(1) and O(2)) from two different 3-Br-5Cl-
Salpn ligands and two bridging oxo atoms (O(3) and
O(3)1 (1 3 – x, 1 – y, 1 – z)). The axial sites are defined
by also two imine nitrogen atoms derived from two dif-
ferent Schiff bases ligands, the distance of Mn(1)–
N(1) and Mn(1)–N(2) is 2.012(5) and 1.991(5) Å. The
distance of Mn–Ophenol is 1.935(4) and 1.929(4) Å, the
observed value of I is in accordance with previously
reported di-μ-oxo-bridged Mn(IV) dimer structures
[18, 19].
formed C–H···Cl hydrogen bonds play a key role in
stabilizing the crystal structure, which result is consist
with the Hirshfeld surface analysis. As illustrated in
Fig. 1b, the adjacent dimers are connected by inter-
molecular C–H···O and C–H···Cl hydrogen bonding
interactions C(7)–H(7A)···O(4) (D···A 3.230(8) Å,
D–H···A 137°) and C(17)–H(17B)···Cl(1) (D···A
3.680(9) Å, D–H···A 145°) to generate one-dimen-
sional chain structure along the crystallographic
b-axis.
The asymmetric unit of compound II contains one
3-Br-5Cl-Salmen salen-type ligand, one manga-
nese(III) ion and one 3-bromo-5-chlorosalicylalde-
According to the analysis of result of PLATON
software [20], phenoxy oxygen atom from DMF hyde anion (Fig. 1c). The basal plane of Mn(III) cen-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

140
WU et al.
Table 2. Selected bond distances (Å) and angles (deg) for the complexes I and II*
Bond
Mn(1)–O(3)1
Mn(1)–O(3)
Mn(1)–O(2)
Cl(1)–C(3)
Cl(2)–C(11)
d, Å
Bond
Mn(1)–O(1)
d, Å
I
1.801(4)
1.810(4)
1.929(4)
1.739(6)
1.741(6)
1.935(4)
1.991(5)
2.012(5)
1.894(6)
1.896(6)
Mn(1)–N(1)
Mn(1)–N(2)
Br(1)–C(5)
Br(2)–C(13)
1
* Symmetry codes for complex I: –x + 3, –y + 1, –z + 1.
II
Mn(1)–O(2)
Mn(1)–O(1)
Mn(1)–N(1)
Cl(1)–C(4)
Cl(2)–C(13)
Cl(3)–C(21)
1.731(10) ?
1.864(5)
1.883(5)
1.973(6)
1.711(7)
1.713(8)
Mn(1)–N(2)
Mn(1)–O(3)
2.000(6)
2.027(5)
Br(1)–C(2)
Br(2)–C(15)
1.863(7)
1.884(9)
1.731(10)
Br(3)–C(19)
1.894(8)
Angle
ω, deg
Angle
ω, deg
I
O(3)1Mn(1)O(3)
O(3)1Mn(1)O(2)
O(3)Mn(1)N(1)
O(2)Mn(1)N(1)
O(1)Mn(1)N(1)
O(3)1Mn(1)N(2)
O(3)Mn(1)N(2)
O(2)Mn(1)N(2)
O(1)Mn(1)N(2)
80.8(2)
92.1(2)
172.40(19)
91.9(2)
92.28(19)
173.0(2)
95.07(19)
94.07(19)
84.1(2)
O(3)Mn(1)O(2)
89.16(19)
93.8(2)
O(3)1Mn(1)O(1)
O(3)Mn(1)O(1)
O(2)Mn(1)O(1)
94.35(18)
88.8(2)
O(3)1Mn(1)N(1)
85.29(19)
1
* Symmetry codes for complex (I): –x + 3, –y + 1, –z + 1.
II
O(2)Mn(1)O(1)
O(2)Mn(1)N(1)
O(1)Mn(1)N(1)
O(2)Mn(1)N(2)
O(1)Mn(1)N(2)
94.1(2)
163.7(2)
89.7(2)
90.5(2)
164.7(3)
N(1)Mn(1)N(2)
O(2)Mn(1)O(3)
O(1)Mn(1)O(3)
N(1)Mn(1)O(3)
N(2)Mn(1)O(3)
82.1(3)
100.9(2)
96.1(2)
94.5(2)
97.4(3)
ter of II is chelated by O(1), O(2), N(1), and N(2) formed intermolecular hydrogen bonding C(10)–
from 3-Br-5Cl-Salmen, the bond lengths of Mn–
O(N) are in the range of 1.864(5)–2.027(5) Å, while
bond angles of O(N)MnO vary from 80.8(2)° to
173.0(2)°. The dihedral angle calculated between the
planes of two benzene rings for II is 13.807(235)°.
Thus, the moiety overall exhibit Z-type distortion. The
apical positions of II are occupied by one oxygen atom
O(3) from 3-bromo-5-chlorosalicylaldehyde anion
and one oxygen atom O(1)1 (1 1 – x, –1 – y, 1 – z ))
from phenolate group of other halve of 3-Br-5Cl-Sal-
H(10)···O(4) (D···A 3.403(10) Å, D–H···A 156°) play
an important part in linking the neighbouring mole-
cules to form two-dimensional lay structure (Fig. 1d).
In order to check the phase purities of complexes I
and II, the XRD patterns have been checked at ambi-
ent temperature. As shown in Fig. 2, for both com-
pounds, the simulated patterns agreed well with those
of the experimental patterns, indicating phase purities
of the as-synthesized samples. The slight differences
men ligand, the bond length of Mn(1)–O(3) and in reflection intensity between the simulated and
experimental patterns are due to the variation in crys-
ther analysis shows that aldehyde oxygen atoms tal orientation of the powder samples.
Mn(1)–O(1)1 is 2.028 and 2.954 Å, respectively. Fur-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 46
No. 2
2020

SYNTHESIS, CRYSTALLOGRAPHIC STRUCTURE, HIRSHFELD SURFACE ANALYSIS
(а) (b)
141
Br(2)
Сl(2)
Br(1)
С(12)
С(4)
С(13)
С(5)
С(3)
С(2)
O(2) O(1)
С(10)
Cl(1)
H(17B)
Cl(1)
H(17B)
Сl(1)
С(11)
С(8)
С(14)
С(6)
С(1)
С(7)
С(9)
O(4)
O(4)
Mn(1)
С(15)
С(16)
С(17)
H(7)
H(7)
O(4)
H(7)
H(7)
H(17B)
O(3)
O(4)
H(17B)
(c)
(d)
Br(3)
С(19)
O(3)
С(9)
С(8)
С(25)
С(24)
С(17)
С(10)
С(11)
С(20)
С(12)
H(10)
O(4)
H(10)
O(4)
С(21)
С(22)
N(2)
С(13)
С(14)
С(23)
O(4)
С(7)
Mn(1)
N(1)
С(1)
С(15)
С(5)
С(4)
O(2)
Br(2)
O(4)
O(4)
H(10)
H(10)
С(6)
С(2)
O(1)
H(10)
O(4)
H(10)
С(3)
O(4)
Br(1)
O(4)
H(10)
O(4)
H(10)
Fig. 1. Molecular structure of complex I (a), supramolecular interactions of complex I showing the intermolecular hydrogen
bonding formed one-dimensional chain structure (b), ball-and-stick representation of complex II (c), the intermolecular hydro-
gen bonding formed two-dimensional layer structure of complex II (d).
It is noteworthy that according to the analysis of
result of PLATON software [18], seemingly that
except aldehyde oxygen from 3-bromo-5-chlorosalic-
ylaldehyde formed C–H···O interactions (Table 3),
there is no other intermolecular hydrogen bond exist
in the crystal structure. By comparison, Hirshfeld sur-
face analysis give us a more specific qualitative and
quantitative contributions of the interactions in the
crystal packing. Detailed discussion is addressed in
Hirshfeld surface analysis section.
Hirshfeld surface in the 2D fingerprint for com-
pound II is similar with that of I (Fig. 3b), the major
intermolecular interaction is also contribute by halo-
gen atoms, and the Cl···H/H···Cl and Br···H/H···Br
interaction covers the highest proportion (42.5%) of
the total plots, whereas, the C–H···C and C–H···O
contacts only cover less than a half proportion of
Cl···H/H···Cl and Br···H/H···Br interaction, merely
comprising 19.2% of the total Hirshfeld surface. These
results indicate that albeit halogen formed hydrogen
bond interaction is weak, halogen atoms in I and II
play the most important part in stabilizing the solid
stature.
The frontier molecular orbitals (FMOs) is an
important theoretical method in providing informa-
tion about kinetic stability, energy levels and molecu-
lar reactivity. All of the calculations were done by
Gaussian 09 software. Density functional theory
(DFT) with the B3LYP functional levels for the
6-311G (d, p) basis set was used for complete calcula-
tions [23]. Figure 4a shows the distributions and
energy levels of the HOMO−LUMO orbitals com-
puted at the B3LYP level for I. The value of the energy
separation between the HOMO and LUMO is ‒2.97
and –6.12 eV, respectively. The magnitude of the
energy separation between the HOMO and LUMO is
The bundle of inter-related weak molecular inter-
actions is difficult to be unraveled by traditional meth-
ods [21]. Hirshfeld surface analysis offer us a new per-
spective on the issue. This analysis method can pro-
vide detailed explanation about the nearby
environment of the molecules in a crystal, and the
comparison between similar structures can give a
more specific description of the difference [22].
Hirshfeld surface in the 2D fingerprint plots show that
(Fig. 3a), for compound I, the Cl···H/H···Cl and
Br···H/H···Br interaction covers the highest propor-
tion (33.4%) of the total plots, whereas, the proportion
C–H···C and C–H···O contacts only cover 25.5%,
which is much smaller than the halogen atom involved
contacts.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

142
WU et al.
potential (MEP) surface map of the compounds was
(I)
investigated with theoretical calculations at the
B3LYP/6-311G (d,p) level. In Fig. 4b, MEP is shown.
As expected, the most negative electrostatic potential
corresponds to the region between the phenolic oxy-
gen atom, also influenced by the halogen atoms. This
nucleophile site (negative potential value of –26.2 kcal
mol–1) is distributed around the oxygen atom due to
the intermolecular C–H···O and C–H···Cl interac-
tions. The most positive region is observed in the
region of the 1,3-diaminopropane group at the molec-
ular plane (29.9 kcal mol–1). This result is in accor-
dance with the single-crystal structure analysis.
1
2
10
20
30
2θ, deg
40
50
(II)
In summary, two new salen-type halogenated
Schiff-base Mn(IV)/Mn(III) complexes have been
synthesized by conventional method. The structures
have been determined by the single crystal X-ray dif-
fraction, IR and XRD techniques. Hirshfeld surface
analysis and DFT calculations have been employed to
further analyze the inter/intramolecular interactions,
all the results agree well with the single-crystal struc-
ture analyses. The detailed comparison of Hirshfeld
surface analysis result indicates that Cl···H/H···Cl and
Br···H/H···Br interaction cover a quite high propor-
tion in solid structures. That is to say, although the
interactions formed by halogen atom are weak, halo-
gen atoms can play an important role in directing and
stabilizing the solid structures of Schiff-base com-
plexes. As different supramolecular interaction can
lead a totally different physicochemical properties,
further work will continue focusing on the synthesis of
halogenate ligands constructed complexes to system-
1
2
10
20
30
2θ, deg
40
50
Fig. 2. Experimental (1) and simulated (2) XRPD patterns
of I and II at room temperature.
3.15 eV. This relatively high value indicates the good
stability of the title structure.
To further compare the weak interactions and
chemical reactivity of I, the molecular electrostatic atically explore the regulating effect of halogen atoms.
Table 3. Geometric parameters of hydrogen bond distances (Å) and angles (deg) for the complexes I and II
Distance, Å
Angle
DHA, deg
D–H···A
H···A
2.47
D···A
I
C(7)–H(7A)···O(4)1
C(15)–H(15A)···O(3)
C(15)–H(15A)···O(1)1
3.230(8)
137
2.58
2.56
3.027(8)
3.041(8)
108
109
C(16)–H(16A)···O(3)
C(16)–H(16A)···O(2)1
2.52
2.55
2.980(9)
2.993(8)
108
107
C(17)–H(17B)···Cl(1)2
C(18)–H(18A)···O(4)
2.83
2.37
3.680(9)
145
105
2.786(11)
1
2
* Symmetry codes for complex I: 1 – x, 1 – y, 1 – z, 1 – x, –y, 1 – z.
II
C(8)–H(8)···Br(1)1
C(10)–H(10)···O(4)2
2.81
3.676(11)
3.403(10)
147
156
2.53
1
2
* Symmetry codes for complex II: 1 – x, –y , –z, –x, –1/2 + y, 1/2 – z.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 46
No. 2
2020

SYNTHESIS, CRYSTALLOGRAPHIC STRUCTURE, HIRSHFELD SURFACE ANALYSIS
(a)
143
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
17.2
17.2
27.2
33.4
H···Cl/Cl···H 17.5%
H···Br/Br···H 15.9%
H···O/O···H 8.3%
8.3
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
X...H 33.4%
O...H 8.3%
H...H 27.2%
C...H 17.2%
H···H 27.2%
H···C/C···H 17.2%
N···H 0.2%
(b)
7.7
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
20.6
41.5
11.5
H···Cl/Cl···H 28.8%
H···Br/Br···H 12.7%
H···O/O···H 11.5%
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
2.2
1.8
1.4
1.0
0.6
X...H 41.5%
O...H 11.5%
H...H 20.6%
C...H 7.7%
H···H 20.6%
H···C/C···H 7.7%
N···H 0.2%
0.6 1.0 1.4 1.8 2.2
0.6 1.0 1.4 1.8 2.2
0.6 1.0 1.4 1.8 2.2
Fig. 3. Two dimensional fingerprint plots of the complex I (a) and II (b): resolved contacts showing the percentages of the weak
contacts contributed to the total Hirshfeld Surface area of the title compounds (left), columns highlight the relevant surface
patches associated with the specific contacts in the total Hirshfeld Surface area of the title compounds (right).
(a)
(b)
LUMO
3.15 eV
HOMO
Fig. 4. Molecular orbital surfaces for the HOMO and LUMO of I computed at B3LYP/6-311G (d, p) level (a); the molecular elec-
trostatic potential surface of I (b).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 46 No. 2 2020

144
WU et al.
FUNDING
9. Egekenze, R., Gultneh, Y., and Butcher, R., Polyhe-
dron, 2018, vol. 144, p. 198.
This work was supported by Fund for Less Developed
10. Hazari, A., Gomez-Garcia, C.J., Drew, M.G.B., and
Regions of the National Natural Science Foundation of
China (no. 31760257); Joint Basic Research Program (par-
tial) of Yunnan Local Undergraduate Universities
(2017FH001-002); The the reserve academic and technical
leaders of Yunnan Province (2019HB098); The Kunming
University Chemistry and Chemical Engineering Students’
Science and Technology Innovation Project HXHG1808.
Ghosh, A., Polyhedron, 2017, vol. 138, p. 145.
11. Shao, L., Chen, Q., and Qi, C., Kinet. Catal., 2017,
vol. 58, no. 6, p. 758.
12. Xue, C., Zhang, H., and Zhang, D.P.R., J. Coord.
Chem., 2017, vol. 43, no. 4, p. 260.
13. CrysAlisPro, Version 1.171.35.19, Santa Clara: Agilent
Technologies Inc., 2011.
14. CrysAlisPRO, Software System, Version 1.171.39.9g, Ox-
ford: Agilent Technologies, 2015.
REFERENCES
15. Dolomanov, O.V., Bourhis, L.J., Gildea, R., et al., J.
1. Huang, F. and Anslyn, E.V., Chem. Rev., 2015, vol. 115,
Appl. Crystallogr., 2010, vol. 42, no. 2, p. 339.
no. 15, p. 6999.
16. Bermejo, M.R., Castineiras, A., Garcia-Monteagudo, J.C.,
et al., Dalton Trans., 1996, no. 14, p. 2935.
2. Slater, A.G., Perdigao, L.M., Beton, P.H., and
Champness, N.R., Accounts Chem. Res., 2014, vol. 47,
no. 12, p. 3417.
17. Brown, I.D. and Altermatt, D., Acta Crystallogr., Sect.
B: Struct. Sci., 1985, vol. 41, no. 4, p. 244.
18. Maneiro, M., Bermejo, M., Fondo, M., et al., Polyhe-
dron, 2001, vol. 20, no. 7, p. 711.
3. Wu, Q., Tang, Y., and Zi, Q., Polyhedron, 2019,
vol. 166, p. 123.
19. Law, N.A., Kampf, J.W., and Pecoraro, V.L., Inorg.
4. Lecren, L., Wernsdorfer, W., Li, Y.G., et al., J. Am.
Chem. Soc., 2007, vol. 129, no. 16, p. 50451.
Chim. Acta, 2000, vol. 297, no. 1, p. 252.
20. Spek, A.L.J., J. Appl. Crystallogr., 2003, vol. 36, no. 1,
5. Ma, C., Tian, G., and Zhang, R., J. Organomet. Chem.,
p. 7.
2006, vol. 691, no. 9, p. 2014.
21. Spackman, M.A. and Jayatilaka, D., CrystEngComm,
6. d’Arová, M., Sivák, M., Kuchta, L., et al., Dalton
Trans., 2004, vol. 2004, no. 20, p. 3313.
2009, vol. 11, no. 1, p. 19.
22. McKinnon, J., Spackman, M.A., and Mitchell, A.S.,
Acta. Crystallogr. Sect. B: Struct. Sci., 2004, vol. 60,
no. 6, p. 627.
7. Phonsri, W., Macedo, D.S., Vignesh, K.R., et al.,
Chem. Eur. J., 2017, vol. 23, no. 29.
8. Armentano, D., Barquero, M.A., Rojasdotti, C., et al., 23. Andersson, M.P. and Uvdal, P., J. Phys. Chem., A,
Cryst. Growth Des., 2017, vol. 17, no. 10. 2005, vol. 109, no. 12, p. 2937.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
Vol. 46
No. 2
2020