Eight Zn(ii) coordination networks based on flexible 1,4-di(1H-imidazol-1- yl)butane and different dicarboxylates: Crystal structures, water clusters, and topologies

Article abstract of DOI:10.1039/c3dt51114f

Eight new Zn(ii) coordination polymers based on flexible 1,4-di(1H-imidazol-1-yl)butane and different dicarboxylates, [Zn(dimb)(suc)·2DMF]_n (1), [Zn(dimb)(mbda)·3H ₂O]_n (2), [Zn(dimb)(adip)·DMF·2H ₂O]_n (3), [Zn(dimb)(pma)·2.5H₂O] _n (4), [Zn₂(dimb)(tha)₂(H₂O)] _n (5), [Zn(dimb)(chda)·2H₂O]_n (6), [Zn(dimb)(obda)·DMF]_n (7), [Zn(dimb)(tdga)·CH ₃OH]_n (8) (dimb = 1,4-di(1H-imidazol-1-yl)butane, H ₂suc = succinic acid, H₂mbda = m-benzenediacetic acid, H₂adip = adipic acid, H₂pma = pimelic acid, H ₂tha = thiophene-2,5-dicarboxylic acid, H₂chda = 1,4-cyclohexanedicarboxylic acid, H₂obda = o-benzenediacetic acid, H₂tdga = thiodiglycolic acid; DMF = N,N′-dimethylformamide), have been synthesized and structurally characterized by single-crystal X-ray diffraction analyses, and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffractions (PXRD) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analysis reveals that 1, 2, 4, 7 and 8 are 2D wavy 4⁴-sql networks with different dimensions of quadrilateral window units, depending on the conformation and length of dimb and dicarboxylates. Complex 3 is a 2D a 6³-hcb network incorporating a [Zn₂(dimb)₂] cyclic subunit. In complex 5, Zn(ii) centers as 3-connected node are linked by dimb and tha to form a 3D 8-fold interpenetrating ThSi₂ network. Complex 6 is a 4-connected noninterpenetrating cds network. Interestingly, an infinite T4(2)6(2) water tape and a D_2h cyclic water tetramer are also found in complexes 2 and 3, respectively. In 1-8, all Zn(ii) centers are located in a four-coordinated environment, and dimb and dicarboxylates are 2-connected linkers, but networks with diverse topologies are built, which indicates the linkage of central metal ion, the conformation of dimb and dicarboxylate have important influences on the resulting structures. Furthermore, the solid-state photoluminescence properties of the 1-8 were investigated at 298 and 77 K.

Full text of DOI:10.1039/c3dt51114f

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Eight Zn(II) coordination networks based on flexible
1,4-di(1H-imidazol-1-yl)butane and different
dicarboxylates: crystal structures, water clusters,
and topologies†
Cite this: Dalton Trans., 2013, 42, 12324
Di Sun,* Meng-Zhen Xu, Shan-Shan Liu, Shuai Yuan, Hai-Feng Lu, Sheng-Yu Feng
and Dao-Feng Sun
Eight new Zn(II) coordination polymers based on flexible 1,4-di(1H-imidazol-1-yl)butane and different
dicarboxylates, [Zn(dimb)(suc)·2DMF]n (1), [Zn(dimb)(mbda)·3H2O]n (2), [Zn(dimb)(adip)·DMF·2H2O]n (3),
[Zn(dimb)(pma)·2.5H2O]n (4), [Zn2(dimb)(tha)2(H2O)]n (5), [Zn(dimb)(chda)·2H2O]n (6), [Zn(dimb)(obda)·
DMF]n (7), [Zn(dimb)(tdga)·CH3OH]n (8) (dimb = 1,4-di(1H-imidazol-1-yl)butane, H2suc = succinic acid,
H2mbda = m-benzenediacetic acid, H2adip = adipic acid, H2pma = pimelic acid, H2tha = thiophene-2,5-
dicarboxylic acid, H2chda = 1,4-cyclohexanedicarboxylic acid, H2obda = o-benzenediacetic acid, H2tdga =
thiodiglycolic acid; DMF = N,N’-dimethylformamide), have been synthesized and structurally character-
ized by single-crystal X-ray diffraction analyses, and further characterized by infrared spectra (IR), elemen-
tal analyses, powder X-ray diffractions (PXRD) and thermogravimetric analyses (TGA). Single-crystal X-ray
diffraction analysis reveals that 1, 2, 4, 7 and 8 are 2D wavy 44-sql networks with different dimensions of
quadrilateral window units, depending on the conformation and length of dimb and dicarboxylates.
Complex 3 is a 2D a 63-hcb network incorporating a [Zn2(dimb)2] cyclic subunit. In complex 5, Zn(II)
centers as 3-connected node are linked by dimb and tha to form a 3D 8-fold interpenetrating ThSi2
network. Complex 6 is a 4-connected noninterpenetrating cds network. Interestingly, an infinite T4(2)6
(2) water tape and a D2h cyclic water tetramer are also found in complexes 2 and 3, respectively. In 1–8,
all Zn(II) centers are located in a four-coordinated environment, and dimb and dicarboxylates are 2-con-
nected linkers, but networks with diverse topologies are built, which indicates the linkage of central
metal ion, the conformation of dimb and dicarboxylate have important influences on the resulting struc-
tures. Furthermore, the solid-state photoluminescence properties of the 1–8 were investigated at 298
and 77 K.
Received 1st May 2013,
Accepted 5th June 2013
DOI: 10.1039/c3dt51114f
www.rsc.org/dalton
new CP structure, especially that based on flexible ligands,
with a specific net topology.3 In general, the assembly of CPs
Introduction
Recently, coordination polymers (CPs) have attracted consider- depends on several factors, such as coordination geometry of
able attention because of their aesthetic appeal of molecular the central metal and the nature of organic ligand, solvent,
connectivities and topologies as well as potential applications temperature, concentration and ratio of reactants, reaction
as functional materials in luminescence, magnetism, sensors, time, and pH, and so on.4 In contrast to the widely studied
gas adsorption, ion exchange and catalysis.1,2 Despite the rigid and aromatic ligands, flexible ligands have not been well
impressive progress, it is still difficult to design and predict a investigated. To achieve the flexibility, ligands built from mul-
tiple functional groups linked by aliphatic chains have been
widely investigated. For example, the flexible ligand 1,3-bis(4-
pyridyl)propane5 can adopt different conformations such as
Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of
anti–anti, gauche–anti, and two kinds of gauche–gauche forms,
which may thus result in diverse fascinating networks with
novel topologies or entanglements.
In terms of crystal engineering, an effective route for the
synthesis of novel CPs with attractive topological structures is
employment of mixed ligands.6 Mixed N- and O-donor ligands
Chemistry and Chemical Engineering, Shandong University, Jinan, 250100,
P. R. China. E-mail: dsun@sdu.edu.cn; Fax: +86-531-88364218
†Electronic supplementary information (ESI) available: Powder X-ray diffraction
(PXRD) patterns for 1–8, solid-state photoluminescent spectra for 1–8, structural
graphics for 2, 4,
7 and 8, additional tables. CCDC reference numbers
932564–932571. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c3dt51114f
12324 | Dalton Trans., 2013, 42, 12324–12333
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Spectrophotometer equipped with a Dewar flask with a
Suprasil quartz cold finger. Powder-XRD measurements were
recorded on a D/Max-2500 X-ray diffractometer using Cu-Kα
radiation. Thermogravimetric analyses (TGA) were performed
on a Netzsch STA 449C thermal analyzer from room tempera-
ture to 800 °C under a nitrogen atmosphere at a heating rate of
10 °C min−1
.
Preparation of complexes 1–8
[Zn(dimb)(suc)·2DMF]n (1). A mixture of Zn(NO3)2·6H2O
(29.7 mg, 0.10 mmol), dimb (19.0 mg, 0.10 mmol) and H2suc
(11.8 mg, 0.10 mmol) in DMF–CH3OH–H2O (6.0 mL, v : v : v =
2 : 1 : 1) was treated by ultrasound (160 W, 40 kHz, 50 °C). The
resultant solution was allowed to evaporate slowly at room
temperature for several days to afford the product as crystals of
1. The pale-yellow crystals were collected and washed with
EtOH and dried in the air (yield: 62%). Elemental analysis:
calc. (%) for 1 (C10H16N3O3Zn0.5): C 46.38, H 6.23, N 16.23;
found: C 46.18, H 6.36, N 16.45. Selected IR peaks (cm−1):
3438 (s), 1612 (s), 1561 (s), 1492 (s), 1396 (m), 1350 (m), 765
(m), 633 (m).
[Zn(dimb)(mbda)·3H2O]n (2). The synthesis of 2 was similar
to that of 1, but using H2mbda (19.4 mg, 0.10 mmol) instead
of H2suc. Ammonia (25%, 15 drops) was added to dissolve the
mixture. The yellow crystals were collected and washed with
EtOH and dried in the air (yield: 69%). Elemental analysis:
calc. (%) for 2 (C20H28N4O7Zn): C 47.87, H 5.62, N 11.16;
found: C 47.21, H 5.85, N 11.45. Selected IR peaks (cm−1):
3441 (s), 1632 (s), 1566 (s), 1500 (s), 1387 (m), 1357 (m), 766
(m), 639 (m).
[Zn(dimb)(adip)·DMF·2H2O]n (3). The synthesis of complex
3 was similar to that of 1 but using H2adip (14.6 mg,
0.10 mmol) instead of H2suc. Pale-yellow crystals of 3 were col-
lected and washed with EtOH and dried in the air (yield: 61%).
Elemental analysis: calc. (%) for 3 (C19H33N5O7Zn): C 44.84,
H 6.54, N 13.72; found: C 44.99, H 6.64, N 13.41. Selected
IR peaks (cm−1): 3399 (s), 1621 (s), 1588 (s), 1502 (s), 1392 (m),
1357 (m), 806 (m), 680 (m).
[Zn(dimb)(pma)·2.5H2O]n (4). The synthesis of complex 4
was similar to that of 1 but using H2pma (16.0 mg, 0.10 mmol)
instead of H2suc. Ammonia (25%, 15 drops) was added to dis-
solve the mixture. Pale-yellow crystals of 4 were collected and
washed with EtOH and dried in the air (yield: 55%). Elemental
analysis: calc. (%) for 4 (C17H29N4O6.5Zn): C 44.50, H 6.37,
N 12.21; found: C 44.25, H 6.23, N 12.17. Selected IR peaks
(cm−1): 3455 (s), 1630 (s), 1545 (s), 1501 (s), 1381 (m), 1355
(m), 780 (m), 662 (m).
Scheme 1 Structures of dimb and dicarboxylate ligands used in this work.
have been selected as the best combination in the crystal
engineering field.7 Inspired by this strategy, a great number of
CPs have been reported by the utilization of pyridyl or imid-
azolyl based bridging ligands and aliphatic or aromatic polycar-
boxylic acids.8 Among the flexible N-donor bridging ligands,
the 1,4-di(1H-imidazol-1-yl)butane (dimb) ligand with a long
alkyl (–CH2–)4 spacer allows it to bend and rotate freely so as
to satisfy the demand of coordination environments of metal
ions in the assembly process to produce favored arrangements
with beautiful architectures and useful functional properties.9
Taking inspiration from the aforementioned points and
our previous work,10 we successfully applied a mixed ligand
strategy (Scheme 1) and obtained eight new CPs, namely,
[Zn(dimb)(suc)·2DMF]n (1), [Zn(dimb)(mbda)·3H2O]n (2),
[Zn(dimb)(adip)·DMF·2H2O]n (3), [Zn(dimb)(pma)·2.5H2O]n
(4), [Zn2(dimb)(tha)2(H2O)]n (5), [Zn(dimb)(chda)·2H2O]n (6),
[Zn(dimb)(obda)·DMF]n (7), [Zn(dimb)(tdga)·CH3OH]n (8)
(dimb = 1,4-di(1H-imidazol-1-yl)butane, H2suc = succinic acid,
H2mbda = m-benzenediacetic acid, H2adip = adipic acid,
H2pma = pimelic acid, H2tha = thiophene-2,5-dicarboxylic
acid, H2chda = 1,4-cyclohexanedicarboxylic acid, H2obda =
o-benzenediacetic acid, H2tdga = thiodiglycolic acid; DMF =
N,N′-dimethylformamide). These CPs vary their structures from
2D 44-sql and 63-hcb networks to 3D 8-fold interpenetrating
ThSi2 network and non-interpenetrating cds network. Their
syntheses, crystal structures, topologies, thermal stabilities
and photoluminescent properties are reported in this paper.
Experimental section
Materials and general methods
[Zn2(dimb)(tha)2(H2O)]n (5). A mixture of Zn(NO3)2·6H2O
(29.7 mg, 0.10 mmol), dimb (9.5 mg, 0.05 mmol), H2tha
All chemicals and solvents used in the syntheses were of (8.6 mg, 0.05 mmol) and 1.0 mL DMF–CH3OH–H2O (v : v : v =
analytical grade and used without further purification. C, 2 : 1 : 1) was sealed in a glass tube and heated to 130 °C for
N and H analyses were performed on an EA1110 CHNS-0 CE 10 h, kept 130 °C for 50 h then slowly cooled to 30 °C for 15 h.
65 elemental analyzer. IR (KBr pellet) spectra were recorded on Yellow crystals of 5 were collected and washed with EtOH and
a Nicolet Magna 750FT-IR spectrometer. Photoluminescence dried in the air (yield: 75%). Elemental analysis: calc. (%) for
spectra were measured on a Hitachi F-7000 Fluorescence 5 (C44H44N8O20S4Zn4): C 37.89, H 3.18, N 8.03; found: C 37.64,
This journal is © The Royal Society of Chemistry 2013
Dalton Trans., 2013, 42, 12324–12333 | 12325

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H 3.25, N 8.47. Selected IR peaks (cm−1): 3405 (s), 1655 (s), no additional symmetry could be applied to the models. Perti-
1582 (s), 1487 (s), 1388 (m), 1354 (m), 761 (m), 655 (m). nent crystallographic data collection and refinement para-
[Zn(dimb)(chda)·2H2O]n (6). Synthesis of complex 6 was meters are collated in Table 1. Selected bond lengths and
similar to that of 5 but using H2chda (8.6 mg, 0.050 mmol) angles are collated in Table S1, ESI.† Topological analysis of
instead of H2tha. Pale-yellow crystals of 6 were collected and coordination networks in all complexes was performed with
washed with EtOH and dried in the air (yield: 74%). Elemental the program package TOPOS.15
analysis: calc. (%) for 6 (C36H56N8O12Zn2): C 46.81, H 6.11, N
12.13; found: C 46.92, H 6.68, N 12.59. Selected IR peaks
(cm−1): 3456 (s), 1622 (s), 1588 (s), 1499 (s), 1385 (m), 1353
(m), 762 (m), 652 (m).
[Zn(dimb)(obda)·DMF]n (7). The synthesis of complex 7 was
similar to that of 1 but using H2obda (19.4 mg, 0.10 mmol)
Results and discussion
Structure descriptions. [Zn(dimb)(suc)·2DMF]n (1), [Zn(dimb)-
(mbda)·3H2O]n (2), [Zn(dimb)(pma)·2.5H2O]n (4), [Zn(dimb)-
(obda)·DMF]n (7) and [Zn(dimb)(tdga)·CH3OH]n (8)
instead of H2suc. Ammonia (25%, 23 drops) was added to dis-
solve the mixture. Yellow crystals of 7 were collected and Complexes 1, 2, 4, 7 and 8 have similar 2D wavy nets. In them,
washed with EtOH and dried in the air (yield: 53%). Elemental all Zn(II) atoms are located in tetrahedral four-coordinated
analysis: calc. (%) for 7 (C23H29N5O5Zn): C 53.03, H 5.61, N environments, and both dimb and different dicarboxylates are
13.44; found: C 53.23, H 5.66, N 13.82. Selected IR peaks uniformly 2-connected linkers, so that 44-sql nets were
(cm−1): 3440 (s), 1617 (s), 1565 (s), 1491 (s), 1389 (m), 1355 obtained. Herein, we only describe the structure of 1 and the
(m), 746 (m), 652 (m).
interesting infinite T4(2)6(2) water tape in 2 in detail. The
[Zn(dimb)(tdga)·CH3OH]n (8). Synthesis of complex 8 was structural graphics for the other four structures are shown
similar to that of 1 but using H2tdga (15.0 mg, 0.10 mmol) in ESI.†
instead of H2suc. Ammonia (25%, 6 drops) was added to dis-
X-Ray single-crystal diffraction analysis reveals that 1 is a 2D
solve the mixture. The yellow crystals were collected and 44-sql net. It crystallizes in the monoclinic crystal system with
washed with EtOH and dried in the air (yield: 64%). Elemental space group of C2/c. The asymmetric unit contains one Zn(II)
analysis: calc. (%) for 8 (C15H22N4O5SZn): C 41.34, H 5.09, N ion passed by one C2 axis, half of one dimb ligand, half of one
12.86; found: C 41.79, H 5.21, N 12.58. Selected IR peaks suc dianion and one lattice DMF molecule. A C2 axis also
(cm−1): 3440 (s), 1615 (s), 1573 (s), 1499 (s), 1393 (m), 1351 passes the midpoint of C5–C5 of a dimb ligand, whereas the
(m), 762 (m), 657 (m).
suc dianion is disordered, imposed by a crystallographic inver-
sion center. As shown in Fig. 1a, the Zn1 atom is in a ZnN2O2
tetrahedral geometry (Zn1–N1 = 2.0012(17) and Zn1–O2A =
X-Ray crystallography
Single crystals of the complexes 1–8 with appropriate dimen- 1.849(9) Å). The distortion of the tetrahedron can be indicated
sions were chosen under an optical microscope and quickly by the calculated value of the τ4 parameter introduced by
coated with high vacuum grease (Dow Corning Corporation) Houser16 to describe the geometry of a four-coordinate metal
before being mounted on a glass fiber for data collection. Data system, which is 0.87 for Zn1 (for an ideal tetrahedron τ4 = 1).
for them were collected on a Bruker Apex II CCD diffracto- Both Zn–N and Zn–O bond lengths are well-matched to those
meter with
a
graphite-monochromated Mo-Kα radiation observed in similar complexes.17 The dimb ligand adopts an
source (λ = 0.71073 Å). A preliminary orientation matrix and anti–gauche–anti conformation18 with torsion angles along the
unit cell parameters were determined from 3 runs of 12 frames C chain of 175.2(2), −87.4(3) and 175.2(2)°. The suc shows a
each, each frame corresponds to a 0.5° scan in 5 s, followed by perfect anti conformation due to the torsion angle of 180°,
spot integration and least-squares refinement. For 1–8, data imposed by an inversion center. The dimb and suc ligands
were measured using ω scans of 0.5° per frame for 5 s until a adopt a bidentate bridging mode to extend the Zn(II) atoms to
complete hemisphere had been collected. Cell parameters the resulting 2D 44-sql network (Fig. 1b), in which the quadri-
were retrieved using SMART software and refined with SAINT lateral window has a dimension of 9.15 × 13.45 Å. Although
on all observed reflections.11 Data reduction was performed this 2D sheet has large windows and also exhibits an undulat-
with the SAINT software and corrected for Lorentz and polariza- ing character with a thickness of about 3.94 Å, interpenetration
tion effects. Absorption corrections were applied with the between adjacent sheets is not observed, which may be due to
program SADABS.11 In all cases, the highest possible space the occupancy of a pair of opposite arranged DMF molecules
group was chosen. All structures were solved by direct methods in each window. The adjacent 2D sheets are packed into
using SHELXS-9712 and refined on F2 by full-matrix least- the resulting 3D supramolecular framework by non-classical
squares procedures with SHELXL-97.13 Atoms were located C–H⋯O hydrogen bonds ranging from 3.074(8) to 3.325(8) Å.
from iterative examination of difference F-maps following
For 2, the solvent accessible voids are occupied by free
least-squares refinements of the earlier models. Hydrogen water molecules, which are associated by O–H⋯O hydrogen
atoms were placed in calculated positions and included as bonds, leading to a 1D infinite staircase-like water tape
riding atoms with isotropic displacement parameters 1.2–1.5 (Fig. 2). This water tape can be seen as the combination
times Ueq of the attached C atoms. All structures were exam- of chair-like cyclic hexamer (O1W⋯O2W⋯O3W⋯O1Wiii⋯
ined using the Addsym subroutine of PLATON14 to assure that O2Wiii⋯O3Wiii) and uudd tetramer (O1W⋯O3Wiii⋯O1Wv⋯O3Wii)
12326 | Dalton Trans., 2013, 42, 12324–12333
This journal is © The Royal Society of Chemistry 2013

Table 1 Crystal data for 1–10
Complex
1
2
3
4
5
6
7
8
Empirical formula
Mr
C10H16N3O3Zn0.5
258.94
C20H28N4O7Zn
501.83
C19H33N5O7Zn
508.87
C17H29N4O6.5Zn
458.81
C11H11N2O5SZn
348.68
C18H28N4O6Zn
461.81
C20H22N4O4Zn
447.79
C14H18N4O4SZn
403.75
T/K
298(2)
298(2)
298(2)
298(2)
298(2)
298(2)
298(2)
298(2)
Crystal system
Monoclinic
C2/c
13.453(2)
11.1544(17)
16.508(3)
90.00
99.666(3)
90.00
2442.1(7)
8
1.409
1.052
5901
2140 [R(int) =
0.0225]
1.026
R1 = 0.0307,
wR2 = 0.0797
R1 = 0.0407,
wR2 = 0.0865
Triclinic
Triclinic
Triclinic
Orthorhombic
Pbcn
11.664(5)
11.683(5)
19.847(8)
90.00
90.00
90.00
2704.7(19)
8
1.712
1.990
10 054
2373 [R(int) =
0.0440]
1.017
R1 = 0.0368,
wR2 = 0.1083
R1 = 0.0500,
wR2 = 0.1196
Monoclinic
P21/n
9.8348(10)
15.2564(17)
13.8403(15)
90.00
95.714(2)
90.00
2066.3(4)
4
1.484
1.231
9921
3630 [R(int) =
0.0609]
1.026
R1 = 0.0599,
wR2 = 0.1608
R1 = 0.0933,
wR2 = 0.1840
Triclinic
Monoclinic
C2/c
35.840(3)
9.0465(8)
12.2671(11)
90.00
90.468(2)
90.00
3977.2(6)
8
1.349
1.362
9304
3496 [R(int) =
0.1032]
1.158
R1 = 0.0776,
wR2 = 0.2323
R1 = 0.1018,
wR2 = 0.2452
ˉ
ˉ
ˉ
ˉ
Space group
a/Å
b/Å
c/Å
α/°
P1
P1
P1
P1
7.3767(12)
9.6740(16)
16.395(3)
86.541(3)
84.230(3)
83.400(3)
1154.9(3)
2
9.1919(12)
11.4363(14)
13.0821(16)
66.308(2)
78.744(2)
80.613(2)
1229.6(3)
2
8.2532(11)
9.6073(12)
14.1941(19)
96.513(2)
96.661(2)
104.406(2)
1070.8(2)
2
7.984(2)
8.729(2)
16.898(4)
93.577(4)
95.508(5)
103.030(4)
1137.7(5)
2
β/°
γ/°
V/Å3
Z
Dc/mg mm−3
1.443
1.111
5771
4034 [R(int) =
0.0202]
1.043
R1 = 0.0332,
wR2 = 0.0847
R1 = 0.0381,
wR2 = 0.0879
1.374
1.045
6026
4255 [R(int) =
0.0275]
1.029
R1 = 0.0424,
wR2 = 0.0972
R1 = 0.0561,
wR2 = 0.1048
1.423
1.188
5363
3724 [R(int) =
0.0219]
1.039
R1 = 0.0433,
wR2 = 0.0961
R1 = 0.0602,
wR2 = 0.1055
1.307
1.110
5658
3972 [R(int) =
0.0332]
0.946
R1 = 0.0468,
wR2 = 0.1047
R1 = 0.0659,
wR2 = 0.1113
μ/mm−1
Reflections collected
Independent reflections
Goodness-of-fit on F2
Final R indexes [I ≥ 2σ(I)]a
Final R indexes [all data]
a R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = [∑w(Fo2 − Fc2)2]/∑w(Fo2)2]1/2
.

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the average distance is 2.863(4) Å, which are all close to the simplified to a 3-connected net with 63-hcb topology in which
distance of O⋯O in ice Ic (2.75 Å) and Ih (2.759 Å) determined the loops become 2-connected linkers.
at −130 and −90 °C.20 Within the water tape, O1W acts as a
In the hydrophilic pores of the 2D network in 3, a rare D2h
double hydrogen bond donor and single hydrogen bond accep- water tetramer is observed. Each water molecule in the D2h
tor, O2W acts as single hydrogen bond donor and single hydro- water tetramer is in a tetrahedral environment and it is
gen bond acceptor, while O3W act as acts as a single hydrogen involved in the formation of four hydrogen bonds, two are
bond donor and double hydrogen bond acceptor. The water tape O2W⋯O1W and O2W⋯O1Wiii and the other two are O1W⋯O2
connects with the host framework with hydrogen-bond inter- and O1W⋯O4ii (Fig. 3c). Geometrical parameters of the water
actions of O2W⋯O2, and O3W⋯O3iv, and penetrates the cluster are listed in Table 2. The average hydrogen bond dis-
windows of 2D network (Fig. S1, ESI†). Up to now, only limited tance within the water tetramer in this case is 2.915(4) Å. O1W
T4(2)6(2) motifs have been reported in the literature,21 and and O2W act as double hydrogen bond acceptor and donor,
Mascal et al. also enumerated some occurrence of T4(2)6(2) respectively, as a result, the hydrogen bond motif for this tetra-
2
water tapes according to the search in Cambridge Structural mer is R4 (8), according to graphset analysis nomenclature.22
Database (CSD).19c
The hydrogen atoms of O1W are 0.72(2) and 0.69(2) Å above
The coordination networks of complexes 2, 4, 7 and 8 are and below the ring, respectively. Such an arrangement
depicted in Fig. S2–S5, ESI.† They possess similar 44-sql nets results in a D2h symmetry.23 As a simple two-structure model
but with different window size and fold amplitude depending for liquid water,24 the cyclic water tetramer is of particular
on the conformation and linkage orientation of dimb and interest. Although theoretical studies on the basis of ab initio
different dicarboxylate ligands.
electronic structure calculations have predicted several con-
figurations of cyclic water tetramers, such as udud, uudd, uuud,
C4 and Cs,25 and some of them have been characterized by far-
infrared vibration-rotation tunneling spectroscopy26 or found
in different crystal hosts,27 crystallographic observation and
analysis of a D2h cyclic water tetramer is very sparse. The
formation of the less stable D2h water tetramer in 3 indicates
that the cooperative association of the water clusters and crystal
host plays an important role in stabilizing the water cluster
(symmetry codes: (ii) x − 1, y, z; (iii) −x + 1, −y + 1, −z + 1).
[Zn(dimb)(adip)·DMF·2H2O]n (3)
Complex 3 is a 2D 63-hcb network incorporating [Zn2(dimb)2]
cyclic subunits. The asymmetric unit of 3 consists of one Zn(II)
ion, one dimb, two adip dianions lying on the inversion
center, one DMF and two water molecules. As depicted in
Fig. 3a, Zn1 is four-coordinated by two nitrogen atoms from
two dimb ligands and two oxygen atoms from two adip anions
in a distorted tetrahedral coordination environment (τ4
=
0.86). Three torsion angles for dimb are 175.7(3), 169.5(3) and
61.4(4)°, which defines an anti–anti–gauche conformation,
while the conformation of adip is anti–anti–anti (175.4(3), 180,
175.4(3)°). A pair of centrosymmetric dimb ligands bind two
Zn(II) ions to form a 22-membered ring, which is extended by
the adip ligand to generate a 2D honeycomb-like sheet with a
dimension of 24.75 × 21.94 Å (Fig. 3b). Each hexagon has four
edges represented by the adip ligands and two edges replaced
by Zn2(dimb)2 loops. That is to say, each Zn atom is connected
to three others by two single μ2-adip bridges and one pair of
dimb ligands. In this analysis, this 2D sheet could be
[Zn2(dimb)(tha)2(H2O)]n (5)
The single-crystal diffraction analysis indicates that complex 5
crystallized in an orthorhombic manner with space group
Pbcn. There is one Zn(II) ion, one dimb ligand, one tha dianion,
and one coordination water molecule in an asymmetric unit of
5. The coordination environment around the Zn(II) atom is
shown in Fig. 4a. The Zn1 is four-coordinated by two N atoms
from two different dimb, and two O atoms from one tha and
one water molecule, respectively. The τ4 parameter is 0.83 for
Fig. 4 (a) The coordination environment of Zn(II) ion in 5 with thermal ellip-
soids at 50% probability level (symmetry code: (i) x − 1, y − 1, z). (b) Ball-and-
stick view of single 3D network (purple: Zn; blue: N; red: O; gray: C).
(c) Simplified single ThSi2 network. (d) View of simplified 8-fold interpenetrated
ThSi2 network (networks individually colored).
Fig. 3 (a) The coordination environment of Zn(II) ion in 3 with thermal ellip-
soids at 50% probability level (symmetry code: (i) −x + 2, −y, −z + 1; (iii) −x + 1,
−y + 1, −z + 1). (b) Ball-and-stick view of the 2D 63-hcb net (purple: Zn; blue: N;
red: O; gray: C). (c) The D2h water tetramer in 3.
12328 | Dalton Trans., 2013, 42, 12324–12333
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Zn1. The dimb and tha adopt anti–anti–anti and planar confor-
mations, respectively, to extend Zn(II) atom into a complicated
3D network (Fig. 4b).
Better insight of the complicated 3D architecture can be
achieved by topology analysis. Due to the coordination of the
water molecule, the four-coordinated Zn(II) atom just acts as a
3-connected node and both ligands are 2-connected linkers,
then, each node has three angles and each of the angles forms
part of a 10-membered shortest circuit and hence the 3D
network has the Wells point symbol/Schläfli symbol of 103.28
So this 3D net could be simplified to a 3-connected uninodal
net of ThSi2 topology (Fig. 4c) with the vertex symbol of
{102·104·104}. To explain the vertex symbol further, in the ThSi2
network, one angle is associated with two 10-membered funda-
mental rings and the other two angles are associated with four
Fig. 5 (a) The coordination environment of Zn(II) ion in
6
with the
1/2,
thermal ellipsoids at 50% probability level (symmetry code: (i)
x
+
10-membered fundamental rings. The single 3D network con- −y + 1/2, z − 1/2). (b) Ball-and-stick view of 3D network (purple: Zn; blue: N;
red: O; gray: C). (c) Topological representation of cds network (purple ball: Zn;
sists of large rectangular windows, which are filled via mutual
interpenetration of eight independent equivalent networks,
cyan stick: dimb; green stick: chda).
generating a 8-fold interpenetrated 3D network (Fig. 4d).
According to the interpenetration classification,29 complex 5
belongs to rare Class IIIa interpenetration, that is, the overall
the 4-coordinated node distorted from square-planarity,
causing a distorted cds network.32
interpenetration is generated both by pure translations and by
space group symmetry elements. In detail, the translationally
related four ThSi2 nets are observed showing the only one
translational interpenetrating vector of [001] (the crystallo-
graphic c axis), then, the presence of a non-translational inter-
penetrating symmetry element (inversion center) generates
the overall 8-fold interpenetration. As we know, the 2-, 3-, 4-,
6- and highest 9-fold interpenetrated ThSi2 nets have been
documented in the literature,30 however, 8-fold interpenetrated
ThSi2 nets, especially the Class IIIa interpenetrated ThSi2 net,
has rarely been observed.
Comparison of CPs 1–8 and the factors influencing the
network
In CPs 1–8, flexible dimb has been used as the main ligand,
eight different dicarboxylates were used as the auxiliary
ligands and Zn(II) was the central ion, aiming at exploring the
influence of dicarboxylate on the assembly and structure of
target CPs (Scheme 2). From the structure description above,
we can see that all Zn(II) atoms in 1–8 are located in a tetrahe-
dral four-coordinated environment, and both dimb and
different dicarboxylates are uniformly 2-connected linkers, so
the resulting CPs intuitively should be 4-connected networks
based on a topological viewpoint. However, two exceptions
[Zn(dimb)(chda)·2H2O]n (6)
Complex 6 is a 4-connected non-interpenetrating cds 3D
network. Structural analysis indicates that complex 6 crystal-
lizes in the monoclinic crystal system with space group of
P21/n. The asymmetric unit of 6 consists of one crystallographi-
cally independent Zn(II) atom, two half dimb ligands lying on
an inversion center, one chda dianion and two lattice water
molecules. The coordination environment around the Zn(II)
atom is shown in Fig. 5a. Zn1 is in a slightly ZnN2O2 tetrahe-
dral geometry with τ4 of 0.91. Two crystallographically unique
dimb adopt similar gauche–anti–gauche conformations
with two sets of three torsion angles of 59.3(8), 180, 59.3(8)
and 62.3(8), 180, 62.3(8)°, respectively, whereas chda shows a
e,a-cis conformation.31 The dimb and chda extend the Zn(II)
atom into a 3D network (Fig. 5b).
From the view of topology, by treating the Zn(II) atom as a
single node and connecting the nodes according to the con-
nectivity defined by dimb and chda ligands, a {65·8} 3D
network supported by 4-coordinated nodes is then obtained as
illustrated in Fig. 5c. Although there is only one type of node
in this net, there are two types of linkers identified by three
different node⋯node distances (8.894, 12.356 and 12.431 Å).
The two different linkers and the flexibility of ligands make Scheme 2 Synthesis procedure for 1–8.
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(3 and 5) occurred in this series of CPs. Although Zn(II) atoms 9.8%), 6.1% (calc. 5.2%), 7.2% (calc. 7.8%), 17.0% (calc.
are four-coordinated in 3 and 5, they are 3-connected nodes 16.3%) and 7.1% (calc. 7.9%), respectively.
because of the existence of Zn2(dimb)2 loops and terminal co-
ordinated water molecule; as a result, 3-connected 2D 63-hcb
Photoluminescence properties
and 3D 8-fold interpenetrated 103-ThSi2 networks were
The emission spectra of 1–8 were examined in the solid state
obtained for 3 and 5, respectively. Excluding 3 and 5, what is
interesting is that the basic coordination environment of the
Zn(II) atoms, basically two coordinating imidazoles and two
carboxylates, yields 2D 44-sql and 3D noninterpenetrating cds
networks that are dependent on the conformation and linkage
orientation of dimb and different dicarboxylate ligands. Due
to the different conformations of dimb and dicarboxylate
ligands, the dimensions of windows defined by the length of
them in the 44-sql networks of 1, 2, 4, 7 and 8 are dramatically
different (Table S2, ESI†). Differently, the tetrahedral Zn(II)
atoms are extended by dimb and chda to form a 4-connected
3D cds network of 6, which suggests that the linkage of central
metal ion, the conformation and linkage orientation of
organic ligands have significant effects on the resultant top-
ology of the networks as well as their dimensions.
at 298 and 77 K, shown in Fig. S7 (ESI†). The free ligand dimb
displays photoluminescence with emission maxima at 398 nm,
assigned to π*→π or π*→n transition.33 To the best of our
knowledge, the emission of dicarboxylate belongs to π*→n
transitions which is very weak compared to that of the π*→π
transition of dimb, so the polycarboxylates almost have no
contribution to the fluorescent emission of as-synthesized
CPs.34 At 298 K, the emission spectra exhibit maximum emis-
sion peaks at 450 nm for 1, 438 nm for 2, 458 nm for 3,
448 nm for 4, 446 nm for 5, 456 nm for 6, 439 nm for 7, and
437 nm for 8, respectively, under excitation at 365 nm. Accord-
ing to the literature, the Zn(II) ion is difficult to oxidize or
reduce because of the d10 configuration. As a result, the emis-
sions of these CPs are neither metal-to-ligand charge transfer
(MLCT) nor ligand-to-metal charge transfer (LMCT) in
nature.35 Thus, they may be assigned to a mixture character-
istic of intraligand and ligand-to-ligand charge transition
(LLCT), as reported for other Zn(II) CPs constructed from
mixed N-donor and O-donor ligands.36 The difference of the
emission behaviors for 1–8 probably derive from the differ-
ences in the rigidity of solid-state crystal packing. In explora-
tion of luminescence thermochromic complexes,37 the
photoluminescent properties of as-synthesized CPs were also
investigated at 77 K. Upon cooling by liquid nitrogen, the
emission spectra exhibit maximum emission peaks at 447 nm
for 1, 448 nm for 2, 454 nm for 3, 449 nm for 4, 441 nm for 5,
458 nm for 6, 439 nm for 7, and 460 nm for 8, respectively,
under excitation at 365 nm. The emission intensities of 1, 2, 5,
7 and 8 were enhanced, whereas the others were diminished at
77 K. Photoluminescence intensity differences among the
same samples at different temperature are reliable, because
the same powder sample was used for all measurements. The
slightly different emission behaviours of 1–8 at different temp-
eratures may arise from the temperature-induced variation of
solid-state crystal packing.38
PXRD results and thermal analysis
To confirm whether the crystal structures are truly representa-
tive of the bulk materials, PXRD experiments were carried
out for 1–8. The PXRD experimental and computer-simulated
patterns of the corresponding complexes are shown in Fig. S6,
ESI.† They show that the synthesized bulk materials and the
measured single crystals are the same.
The TG analysis was performed in N2 atmosphere with a
heating rate of 10 °C min−1 on polycrystalline samples of CPs
1–8, and the TG curves are shown in Fig. 6. The TGA curves for
1–8 suggested that their host networks were stable up to 277,
310, 267, 259, 271, 282, 200 and 310 °C, respectively, then they
start to gradually lose their ligands as a result of thermal
decomposition. The removal of solvent molecules was
observed for 1–8 with weight losses of 28.5% (calc. 28.2%),
11.2% (calc. 10.8%), 20.8% (calc. 21.4%) and 8.9% (calc.
Conclusions
In conclusion, eight new Zn(II) CPs constructed from a biden-
tate imidazole-based ligand and different dicarboxylates have
been successfully obtained by ultrasonic treatment or sol-
vothermal method. Based on four-coordinated metal centers
and two-connected linkers, a series of networks ranging form
3-connected 2D 63-hcb (3) and 3D 8-fold interpenetrating
ThSi2 networks (5) to 2D 44-sql (1, 2, 4, 7 and 8) and non-inter-
penetrating cds networks (6), were constructed. Interestingly,
an infinite T4(2)6(2) water tape and a D2h cyclic water tetramer
are also unmasked in complexes 2 and 3, respectively.
The structural analysis indicates that the linkage of metal
centers, and conformation of organic ligands have important
Fig. 6 TGA curves for CPs 1–8.
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Paper
influences on the resulting network topology. Furthermore,
the solid-state photoluminescence properties of the CPs at 298
and 77 K were investigated.
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Acknowledgements
This work was supported by the NSFC (Grant No. 21201110),
Independent Innovation Foundation of Shandong University
(2011GN030), the Special Fund for Postdoctoral Innovation
Program of Shandong Province (201101007) and the China
Postdoctoral Science Foundation Funded Project (2013T60663).
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