C.-Y. Chang et al.
Journal of Solid State Chemistry 298 (2021) 122129
Table 1
Crystallographic data for 1.
Empirical formula
C26H17N3O6Zn
Mw
532.79
Crystal system
Space group
a/Å
Monoclinic
C2/c
15.6419(8)
20.7242(8)
22.0140(16)
110.727(6)
6674.3(7)
8
b/Å
c/Å
β/ꢀ
V/Å3
Z
Scheme 1. Molecular structure of H2In-4-ba.
T/K
150(2)
λ/Å
0.71073
3264
σ
(I))
0.0645, 0.1633
0.0969, 0.1709
1.107
0.789, ꢁ0.902
2. Experimental section
GOF on F2
2.1. Materials and instruments
Δ
ρmax, Δρmin/e Åꢁ3
P
P
a
R1
¼
jjFoj ꢁ jFcjj = jFoj.
Chemical reagents were purchased commercially and were used as
received without further purification. 1H NMR spectrum was recorded on
a Bruker AMX-300 Solution-NMR spectrometer. All chemical shifts are
reported in δ unit with reference to the residual protons of the deuterated
solvent. Coupling constants are given in Hertz. Mass spectra were
recorded on a JEOL JMS-700 double focusing mass spectrometer. Ther-
mogravimetric (TG) analyses were recorded on a Thermo Cahn Versa-
Therm HS TG analyzer under nitrogen atmosphere. X-ray powder
diffraction (XRPD) measurements were recorded on a Shimadzu XRD-
P
P
2
2
2
1=2
b
2
2
wR2 ¼ f ½wðFo ꢁ Fc Þ ꢃ = ½wðFo Þ ꢃg
.
2.4. X-ray crystallography
X-ray diffraction intensity data for 1 were collected on an Oxford
Diffraction Gemini S diffractometer equipped with a graphite mono-
chromated Mo Kα radiation at 150(2) K. Starting models for structure
refinement were found by direct methods using SHELXS-97 [41] and
refined anisotropically on F2 by the full-matrix least-squares technique
using the SHELXL-2014/7 [42] and WINGX [43] program packages.
Experimental details for X-ray data collection and the refinements are
summarized in Table 1. CCDC 2060260 contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre via www.ccdc.c
7000 diffractometer with a graphite monochromatized Cu Kα radiation
(λ ¼ 1.5406 Å) at 40 kV and 30 mA. Infrared (IR) spectra were recorded
on a Perkin-Elmer RX1 FT-IR spectrometer in the 4000ꢁ500 cmꢁ1 region
using KBr discs. Solid-state excitation and emission spectra were recor-
ded on a Hitachi F7000 fluorescence spectrophotometer at ambient
temperature. CHN elemental microanalyses were performed on an Ele-
mentar Vario EL III analytical instrument.
3. Results and discussion
2.2. Synthesis of 4-carboxyphenyl-1,3-dioxoisoindoline-5-carboxylic acid
(H2In-4-ba)
3.1. Synthesis and crystal structure of [Zn(In-4-ba)(py)2] (1)
In a round bottle, 4-aminobenzoic acid (0.69 g, 5.0 mmol) in glacial
acetic acid (10 mL) was slowly added into a solution of trimellitic an-
hydride (0.96 g, 5.0 mmol) in glacial acetic acid (30 mL), and then the
solution was heated to 180 ꢀC with stirring for 8 h (Scheme S1). After
cooling to room temperature, the solution was stirred for further 6 h and
then the reaction solvents were removed under reduced pressure. The
crude residue was washed with deionized water (100 mL) to give H2In-4-
ba as white powders. Yield 84% (1.32 g, 4.2 mmol). 1H NMR (300 MHz,
DMSO‑d6): δ 8.42 (dd, J ¼ 7.5, 1.2 Hz, 1H), 8.32 (d, J ¼ 0.6 Hz, 1H), 8.09
(dd, J ¼ 6.8, 2.1 Hz, 3H), 7.61 (dd, J ¼ 6.9, 1.8 Hz, 2H) ppm. MS (EIþ):
m/z 311.1 [M]þ (calcd for C16H9NO6: m/z 311.25). Anal. calcd for
Coordination polymer 1 was synthesized from the hydro(solvo)ther-
mal reactions of Zn(OAc)2 and H2In-4-ba using pyridine (py) as solvent at
90 ꢀC for 36 h. As a well-known fact that the hydro(solvo)thermal syn-
thesis gives a unique combination of pressure and temperature condi-
tions for crystallization of such products [44–47]. Single-crystal X-ray
diffraction analysis reveals that 1 crystallized in the monoclinic space
group C2/c. In the asymmetric unit, there are two crystallographic
distinct Zn(II) centers, where Zn(1) located at a special position
symmetry-related by a 2-fold rotation axis while Zn(2) located at a
general position, and two crystallographic distinct In-4-ba2ꢁ ligands,
where one is general case with fully occupation and the other is disor-
C
16H9NO6: C, 61.74; H, 2.91; N, 4.50%. Found: C, 61.93; H, 3.03; N,
dered over
a 2-fold rotation axis with half-occupation. For the
4.59%. IR (KBr pellet):
ν 1782, 1734, 1708, 1605, 1510, 1483, 1429,
fully-occupied In-4-ba2ꢁ ligand, one of the two carboxylate groups is
disordered over two statistical positions with site-of-occupancy of
approximately 0.55 for O(3) and O(4) and 0.45 for O(3’) and (O4’).
Selected bond lengths and bond angles are listed in Table S1. In
considering the coordination environments around the Zn(II) centers,
Zn(1) is coordinated by two py ligands (N(3) and N(3)#1, #1 ¼ –x, y, –z
þ 1/2), with a uniform Zn(1)ꢁN bond length of 2.059(4) Å, and four
carboxylate O atoms (O(3), O(4), O(3)#1, and O(4)#1, #1 ¼ –x, y, –z þ
1/2) of two In-4-ba2ꢁ ligands, with the Zn(1)ꢁO bond lengths of
1.991(8)ꢁ2.304(7) Å, to form a distorted octahedral {ZnN2O4} coordi-
nation geometry (or alternatively, Zn(1) is coordinated by two py ligands
(N(3) and N(3)#1, #1 ¼ –x, y, –z þ 1/2), with a uniform Zn(1)ꢁN bond
1375, 1300, 1218, 1090, 927, 771, 724, 547 cmꢁ1
.
2.3. Synthesis of [Zn(In-4-ba)(py)2]n (1)
H2In-4-ba (31.1 mg, 1.0 ꢂ 10ꢁ1 mmol), Zn(OAc)2 (9.2 mg, 5.0 ꢂ
10ꢁ2 mmol), and pyridine (py, 5 mL) were conducted in an acid digestion
bomb at 90 ꢀC for 36 h. After cooling to room temperature, the solvents
were filtered off. Colorless prismatic crystals were collected in a yield of
96% (25.8 mg, 4.8 ꢂ 10ꢁ2 mmol). Anal. calcd for C26H17N3O6Zn: C,
58.61; H, 3.22; N, 7.89%. Found: C, 59.24; H, 3.36; N, 7.81%. IR (KBr
pellet):
ν 1780, 1720, 1622, 1606, 1508, 1448, 1360, 1220, 1068, 1046,
836, 780, 730, 698 cmꢁ1
.
2