Y.-F. Kang et al.
Journal of Solid State Chemistry 291 (2020) 121620
Scheme 2. The synthetic method of N-oxide functionalized of INO and
NNO ligands.
2. Experimental
Scheme 3. The synthetic route for CPs 1–3.
2
.1. Materials and methods
II CCD diffractometer equipped with a graphite-monochromatic Mo-K
α
All solvents and raw materials were commercially purchased and
radiation (λ ¼ 0.71073 Å) by using a φ/ scan technique at 296(2) K. The
ω
used without further purification. Elemental analyses (carbon, hydrogen,
and nitrogen) were carried on a PerkinElmer 2400C Elemental Analyzer.
The INO/NNO ligand was synthesized in light of the literature reported
previously [17,18] (Scheme 2). Powder X-ray diffraction (PXRD) data
were obtained by the use of a Bruker D8 ADVANCE X-ray powder
structures were solved with direct methods and modified with full-matrix
least-squares method using the program SHELXS-2014 [19]. All the in-
tensity data were corrected for Lorentz and polarization effects as well as
for empirical absorption based on multiscan. Absorption corrections
were applied to the intensities by using SADABS. The non-hydrogen
atoms were refined with anisotropic thermal parameters. The H atoms
attached to C atoms were obtained through theoretical hydrogenation.
The hydrogen atoms of water molecules were placed from diverse Fourier
maps, and after that constraint at settled positions and refined with
ꢀ1
diffractometer (Cu-K
were recorded with KBr pellets on a Nicolet Avatar 360 FTIR spectrom-
eter. Thermogravimetric analyses (TGA) were performed under N
α, 1.5418 Å). The FT-IR spectra (4000-400 cm )
2
stream using a Netzsch TG209F3 equipment at a heating rate of 10
C/min. Variable-temperature magnetic susceptibilities were measured
on a Quantum Design MPMS-XL-7 SQUID magnetometer. Diamagnetic
correction was applied using Pascal’s constant.
ꢁ
isotropic displacement parameters. The methyl of coordinated CH
3
OH in
3
were treated by dividing into two parts automatically with different
occupancy ratio. Crystallographic data of 1–3 are shown in Table S1.
Selected bond lengths and bond angles of 1–3 are given in Table S2.
Hydrogen bond geometries of 1 and 2 are given in Table S3. CCDC
number: 1989899–1989901.
2
.1.1. Synthesis of [Cu
NNO ligand (0.10 mmol, 13.9 mg) and Cu(OAc) O (0.10 mmol,
2
9.9 mg) were dispersed in mixed solvennt CH OH/H O (2:1, 12 mL).
3 4 2 2 2 n
(NNO) (OH) (H O) ] (1)
2
⋅H
2
1
3
The mixture was stirred for 30 min and sealed in a 25 mL Teflon-lined
ꢁ
3. Results and discussion
reactor, and then heated at 100 C for 72 h. After cooling to room tem-
ꢁ
ꢀ1
perature at a rate of 0.1 C min , the blue block crystals of 1 were ac-
3.1. The structural diversities and analysis of [Cu
3
(NNO)
4 2 2 2 n
(OH) (H O) ]
quired. Yield: 68% based on Cu. Elemental analysis (%): Calcd for
(
1), [Cu(INO)(OH)] (2) and [Cu(INO)(CH O)]
n
3
n
(3)
24 3 4
C H22Cu N O16: C, 35.45; H, 2.73; N, 6.89. Found: C, 35.68; H, 2.81; N,
ꢀ
1
7
1
.02. IR(KBr, cm ): 3359 m, 3067 m, 2391 m, 2338 m, 1605 s, 1566 s,
446 m, 1409 m, 1379 m, 1225 m, 1161 m, 1049 w, 1014 w, 854 s, 588 m.
For 1 based on NNO ligand, X-ray diffraction shows 1 crystallizes in
the triclinic crystal system of P-1 space group, and the asymmetric unit
consists of one and a half Cu(II), two NNO ligands, one coordinated OH
and one coordinated water molecule. As shown in Fig. 1a, Cu1 is penta-
ꢀ
2
.1.2. Synthesis of [Cu(INO)(OH)]
INO ligand (0.10 mmol, 13.9 mg) and Cu(OAc)
9.9 mg) were dispersed in mixed solvennt CH OH/DMF (2:1, 12 mL).
n
(2)
2
2
⋅H O (0.10 mmol,
coordinated slightly distorted tetragonal pyramid geometry (
(β - )/60, where and β represent for the two largest bond angles
around Cu1;
τ
¼ 0.29,
τ
1
3
¼
α
α
The mixture was stirred for 30 min and sealed in a 25 mL Teflon-lined
ꢁ
τ
¼ 0 on behalf of ideal tetragonal pyramid, and
τ
¼ 1 on
reactor, and then heated at 100 C for 72 h. After cooling to room tem-
ꢁ
ꢀ1
behalf of ideal trigonal bipyramid [20,21]), in which two carboxylic
perature at a rate of 0.1 C min , the green block crystals of 2 were
filtered out. Yield: 67% based on Cu. Elemental analysis (%): Calcd for
ꢀ
oxygen atoms (O3, O6A) from two NNO ligands, one OH (O7) and one
terminal water molecule (O8) occupy the equatorial plane, as well as one
N-Oxide group oxygen atom (O1B) from one NNO ligand occupy the
vertex. Cu2 is hexa-coordinated slightly distorted octahedron geometry
with two carboxylic oxygen atoms (O5, O5A) from two NNO ligands and
6 5 4
C H CuNO : C, 32.96; H, 2.30; N, 6.41. Found: C, 32.79; H, 2.21; N, 6.75.
ꢀ
1
IR(KBr, cm ): 3408 m, 3079 m, 2465 m, 2340 m, 1606 s, 1568 s, 1497 w,
1468 w, 1394 s, 1247 s, 1188 m, 1141 m, 1080 w, 1046 w, 892 s, 583 m.
ꢀ
two OH (O7, O7A) comprising the equatorial plane, and two N-Oxide
2
.1.3. Synthesis of [Cu(INO)(CH
The procedure was similar to the preparation of 1, except that NNO
ligand was changed into INO ligand. The resulting green block crystals of
were obtained. Yield: 74% based on Cu. Elemental analysis (%): Calcd
for C CuNO : C, 36.13; H, 3.03; N, 6.02. Found: C, 36.32; H, 3.18; N,
.89. IR(KBr, cm ): 3410 m, 3094 m, 2926 m, 2814 m, 2473 m, 2388 m,
338 m, 1601 s, 1563 s, 1471 m, 1396 s, 1245 s, 1187 m, 1149 m, 1061 w,
73 s, 588 m (Scheme 3).
3 n
O)] (3)
groups oxygen atom (O1B, O1C) locating at the axial positions. In 1, the
Cu–O bond lengths (ranging from 1.893(4) to 1.987(3) Å) are within the
normal range of reported literature [22,23], except Cu1–O1 and Cu2–O1
bond lengths (2.434(4) Å and 2.699(3) Å, respectively) slightly beyond
the normal ones in virtue of Jahn-Taylor effect [24,25]. Cu1 and Cu2 ions
3
7
H
7
4
ꢀ1
5
2
8
ꢀ
are connected by carboxylate groups, N-Oxide groups and OH to
generate
O)
Fig. 1b and c, NNO ligands in 1 show two types of coordination mode.
a
trinuclear copper building block [Cu
3 4 2
(COO) (OH) (-
H
2
2 2
(ON-Oxide) ] with Cu⋯Cu separation of 3.076(4) Å. As shown in
2
.2. X-ray crystallography
1
0
One’s carboxylate group take
the dihedral angle relative to pyridine ring being 36.4 , and the N-Oxide
1
μ -
η
:
η
mode bridging one Cu(II) ion with
ꢁ
Crystallographic data for 1–3 were collected on a Bruker Smart Apex-
2