Hydrothermal synthesis of five new coordination polymers based on benzophenone-2, 4'-dicarboxylic acid and N-donor spacers

Article abstract of DOI:10.1002/zaac.201200003

Five new coordination polymers, namely, [Ni₂(L)₂(4, 4'-bipy)₃)]·H₂O]_n (1), [Ni ₂(L)₂(O) (bpp)₂]_n (2), [Zn(L)(bib)_0.5]_n (3), [Zn(L)(PyBIm)]_n (4), and [Zn₃(L)₂(OH)(im)]_n (5) [H₂L = benzophenone-2, 4'-dicarboxylic acid, 4, 4'-bipy = 4, 4'-bipyridine, bpp = 1, 3-bis(4-pyridyl)propane, PyBIm = 2-(4-pyridyl)benzimidazole, and im = imidazole] were synthesized under hydrothermal conditions. Structure determination revealed that compound 1 is a 3D network and exhibits a 4-connected metal-organic framework with (4².6³.8) topology, whereas compounds 2, 3, 4, and 5 are two-dimensional layer structures. In compounds 2-4, dinuclear metal clusters are formed through carboxylic groups. In compound 5, trinuclear metal clusters are formed through μ₃-OH and carboxylic groups. The carboxylic groups exhibit three coordination modes in compounds 1-5: monodentately, bidentate-chelating, and bis-monodentately. Furthermore, the luminescent properties for compounds 3, 4, and 5 were investigated. Copyright

Full text of DOI:10.1002/zaac.201200003

ARTICLE
DOI: 10.1002/zaac.201200003
Hydrothermal Synthesis of Five New Coordination Polymers Based on
Benzophenone-2,4Ј-dicarboxylic Acid and N-Donor Spacers
Jiakun Xu,[a,b] Xiaochun Sun,[c] Yuhua Fan,[b] Caifeng Bi,*[b] and Mi Sun*[a]
Keywords: Coordination polymer; Dicarboxylic acid; Nickel; Zinc; Crystal structure
Abstract. Five new coordination polymers, namely, [Ni2(L)2(4,4Ј- compounds 2, 3, 4, and 5 are two-dimensional layer structures. In com-
bipy)3)]·H2O]n (1), [Ni2(L)2(O) (bpp)2]n (2), [Zn(L)(bib)0.5 n
[Zn(L)(PyBIm)]n (4), and [Zn3(L)2(OH)(im)]n (5) [H2L = benzophe- groups. In compound 5, trinuclear metal clusters are formed through
none-2,4Ј-dicarboxylic acid, 4,4Ј-bipy = 4,4Ј-bipyridine, bpp = 1,3- μ3-OH and carboxylic groups. The carboxylic groups exhibit three co-
]
(3),
pounds 2–4, dinuclear metal clusters are formed through carboxylic
bis(4-pyridyl)propane, PyBIm = 2-(4-pyridyl)benzimidazole, and im = ordination modes in compounds 1–5: monodentately, bidentate-chelat-
imidazole] were synthesized under hydrothermal conditions. Structure ing, and bis-monodentately. Furthermore, the luminescent properties
determination revealed that compound 1 is a 3D network and exhibits a
for compounds 3, 4, and 5 were investigated.
4-connected metal-organic framework with (42.63.8) topology, whereas
Introduction
Results and Discussion
Description of Crystal Structures
During the past decades, the design and synthesis of metal-
ligand coordination have attracted great interest due to their
potential application in the fields of gas storage, molecular
magnetism and luminescence.[1–14] Great efforts have been de-
voted to the design of suitable organic ligands to construct new
coordination polymers. Among the reported studies, coordina-
tion polymers with organic ligands that contain carboxylic
groups are of special interest because the carboxylate ligands
are able to adopt various coordination modes (such as mono-
dentately, chelating, bis-monodentately and/or bridging),
which results in a large diversity of the structures.[15–20]
Bisphenyldicarboxylic acids such as 2,2Ј-bisphenyl dicar-
boxylic acid, 2,4Ј-bisphenyldicarboxylic acid, 3,3Ј-bisphenyld-
icarboxylic acid, 3,4Ј-bisphenyldicarboxylic acid, and 4,4Ј-bi-
sphenyldicarboxylic acid, which are able to act as rigid multi-
carboxylate ligands, have been extensively investigated for
their metal-ligand coordination.[21–27] In contrast, semirigid di-
carboxylate ligands with two benzene rings bridged by a non-
metallic atom (C, N, O, S) have been reported less often.[28–31]
Herein we present the syntheses and crystal structures of five
coordination polymers with nickel(II) and zinc(II) ions based
on benzophenone-2,4Ј-carboxylate and N-donor ligands.
{[Ni2(L)2(4,4Ј-bipy)3)]·H2O}n (1)
The fundamental building unit of compound 1 contains one
nickel(II) ion, two L ligands and three 4,4Ј-bipy ligands. The
central NiII ion is coordinated by three oxygen atoms from two
L ligands and three nitrogen atoms form three 4,4Ј-bipy li-
gands in an octahedral arrangement. The Ni–O and Ni–N bond
lengths are in the range of 1.990(4)–2.178(3) Å and 2.076–
2.115(4) Å, respectively. Each L anion adopts two coordination
modes: monodentately and bidentately-chelating, which lead
to form a 24-membered ring (Figure 1b). The 24-membered
bimetal rings are further connected by 4,4Ј-bipy to form a
three-dimensional structure. The separation of Ni–Ni in the
ring is 8.748 Å. Topological analysis reveals compound 1 is a
4-connected net with (42.63.8) topology if the nickel ion is
treated as a 4-connected node (Figure 1c).
[Ni2(L)2(O)(bpp)2]n (2)
Crystallographic analysis reveals that compound [Ni2(L)2-
(O)(bpp)2]n (2) crystallizes in the monoclinic group C2/c. The
coordination environment around the NiII atom of compound
2 is represented in Figure 2a. One bridging oxygen atom and
one bridging carboxylic group from L ligand connect two NiII
ions into a dimeric structure, in which the Ni–Ni distance is
3.542 Å, and the angle of Ni–O–Ni is 116.49(9)°. The central
nickel(II) atom is six-coordinate in a distorted octahedral ar-
rangement. The equatorial positions are occupied by one car-
boxylic oxygen atom [Ni(1)–O(5) = 2.0124(16) Å], one oxy-
gen atom [Ni(1)–O(5) = 2.0825(11) Å] and two nitrogen atoms
from two bpp ligands [Ni(1)–N(1) = 2.0878(18) Å and Ni(1)–
* Dr. M. Sun, Dr. C. Bi
E-Mail: hhsunmi@yeah.net
[a] Yellow Sea Fisheries Research Institute
Chinese Academy of Fishery Sciences
Qingdao, 266071, P. R. China
[b] Key Laboratory of Marine Chemistry Theory and Technology
Ministry of Education
Ocean University of China
Qingdao, 266100, P. R. China
[c] National Oceanographic Center
Qingdao, 266071, P. R. China
Z. Anorg. Allg. Chem. 2012, 638, (᭿), 1–8
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

J. Xu, X. Sun, Y. Fan, C. Bi, M. Sun
ARTICLE
Figure 2. (a) Coordination environment of the NiII ion in 2. Hydrogen
atoms are omitted for clarity. (b) View of the 1D chain formed by the
dinuclear units in 2. (c) 2D layer structure formed through bbp ligands.
atoms from four L ligands [Zn(1)–O(1) = 2.0585(18), Zn(1)–
O(2) = 2.0477(17), Zn(1)–O(4) = 2.0515(18) and Zn(1)–O(5)
= 2.0360(19) Å] and one nitrogen atom [Zn(1)–N(1) =
2.0193(18) Å] from the bbi ligand to give a pentahedral ar-
rangement (Figure 3a). Each L ligand adopts a bis-mono-
dentate coordination mode, which leads to the formation of
1D strand that can be described as double zigzag chains. It is
interesting to note that four μ4-carboxylic groups bridge the
Figure 1. (a) Coordination environment of the NiII ion in 1. Hydrogen
atoms and free water molecules are omitted for clarity. (b) 24-Mem-
bered bimetal rings formed in 1. (c) Schematic description of the 4-
connected 3D polymer with (42.63.8) topology.
N(2) = 2.1062(18) Å], the axial positions are occupied by two dinuclear central ZnII atoms in syn-syn coordination, which
carboxylic oxygen atoms [Ni(1)–O(1) = 2.0811(15) Å and lead to a paddle wheel secondary building units (SBUs). The
Ni(1)–O(4) = 2.0637(15) Å]. Each ligand L adopts mono- Zn–Zn separation in the SBUs is 3.094 Å (Figure 3b). The 1D
dentate and bis-monodentate coordination modes, which lead zigzag chains are further connected by bib ligands to form a
to one-dimensional zigzag chains (Figure 2b). The 1D chains 2D layer structure (Figure 3c).
are bridged together by ligands to generate a 2D (4,4) layer
framework (Figure 2c)
[Zn(L)(PyBIm)]n (4)
Complex 4 crystallizes in the monoclinic space group P21/c.
[Zn(L)(bib)0.5]n (3)
The zinc(II) ion holds the ZnO4N pentahedral arrangement.
Single-crystal X-ray reveals that complex 3 crystallizes in The five atoms coordinated to the ZnII ion come from one
¯
the triclinic space group P1. In the asymmetry unit, exists an nitrogen atom of PyBIm ligand [Zn(1)–N(1) = 2.0143(17) Å]
independent ZnII ion, which is coordinated by four oxygen and four carboxylic oxygen atoms from three L ligands (Fig-
2
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–8

Coordination Polymers with Benzophenone-2,4Ј-dicarboxylic Acid
Figure 3. (a) Coordination environment of the ZnII ion in 3. Hydrogen
atoms are omitted for clarity. (b) 1D chain structure of 3. (c) 2D (4,4)
layer structure of 3.
Figure 4. (a) Coordination environment of the ZnII ion in 4. Hydrogen
atoms are omitted for clarity. (b) The 2D layer structure of 4.
ure 4a). The ligand L acts as in a μ3-mode (μ2-η1:η1 and
μ1-η1:η1) with one carboxylic group bridging two ZnII atoms
through a bis-monodentate mode and the other carboxylic
group bridging the ZnII atom in a bidentate chelating mode.
The ligands L link the inorganic ZnII nodes to form a 2D layer
structure. The PyBIm ligand displays a monodentate coordina-
tion mode hanging on the both sides to the 2D layer (Fig-
ure 4b).
1.9486(13)–2.0829(12) Å, all of them are within the normal
range as reported in other literature.[30,31] The trinuclear clus-
ters Zn3 (μ3-OH) can be considered as the secondary building
units (SBUs) for construction of the metal-organic architecture
of compound 5. From a topological viewpoint, the neighboring
SBUs can be viewed 6-connected node with the Schläfli sym-
bol of (36.46.53} shown in Figure 5b.
Photoluminescent Properties
[Zn3(L)2(μ3-OH)(im)]n (5)
The solid-state fluorescent properties of H2L and compounds
X-ray diffraction structure analysis reveals compound 5 3–5 at room temperature are shown in Figure 6. The ligand
¯
crystallizes in the triclinic space group P1 with three crystallo- H2L exhibits a broad weak fluorescent emission centered at
graphically independent zinc ions. The three zinc(II) atoms 394 nm with an excitation maximum at 280 nm. Compounds 3,
Zn1, Zn2, and Zn3 form a trinuclear unit through μ3-OH 4, and 5 display a fluorescent emission at around 445 nm (λex
[Zn(1)–O(1) = 2.0201(13), Zn(2)–O(1) = 2.0610(13), and = 400 nm), 499 nm (λex = 427 nm), and 485 nm (λex = 412 nm),
Zn(3)–O(1) = 1.9824(13) Å]. The atoms Zn1 and Zn3 are both respectively. The free ligands bib and PyBIm display fluores-
coordinated by three oxygen atoms and one nitrogen atom cent emission bands at ca. 465 nm (λex = 280 nm) and 492 nm
[Zn(1)–N(2) = 1.9523(15) Å and Zn(3)–N(1) = 1.9537(15) Å] (λex = 370 nm), respectively.[34–36] The much more enhanced
forming a distorted ZnO3N tetrahedral arrangement. The cen- fluorescent intensities of compound 3, 4, and 5 could be attrib-
tral Zn2 atom adopts a distorted pentahedral ZnO4N coordina- uted to the increased rigidity of the ligand after coordination to
tion. The Zn–Ocarboxylate distances are in the range of the zinc(II) ions compared to that of the free ligands, which
Z. Anorg. Allg. Chem. 2012, 1–8
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

J. Xu, X. Sun, Y. Fan, C. Bi, M. Sun
ARTICLE
Experimental Section
Materials and Physical Measurements: All reagents and solvents
employed were commercially available and were used as received
without further purification. Elemental analysis was carried out with a
Carlo Erba 1106 full-automatic trace organic elemental analyzer. FT-IR
spectra were recorded with a Bruker Equinox 55 FT-IR spectrometer as
a dry KBr pellet in the 400–4000 cm–1 range. Solid-state fluorescence
spectra were recorded with a F-4600 equipped with a xenon lamp and
a quartz carrier at room temperature.
Synthesis of [Ni2(L)2(4,4Ј-bipy)3)]·H2O]n (1): Compound 1 was pre-
pared by hydrothermal reaction. A mixture of NiCl2·6H2O (0.119 g.
0.5 mmol), H2L (0.135 g, 0.5 mmol), 4,4Ј-bipy(0.156 g, 0.5 mmol),
NaOH (0.04 g, 1 mmol) and distilled water (15 mL) was heated to
160 °C for 96 h in a 25 mL stainless steel reactor with a Teflon liner,
followed by slow cooling to room temperature. Yield 56% for 1 (based
on Ni). Elemental analysis for C60H42Ni2N6O11: calcd. C 63.19; H
3.71; N 10.29%; found: C,63.12; H,3.70; N, 10.22%. IR (KBr): ν˜ =
3414 b, 3066 m, 1633 s, 1564 s, 1442 s, 1400 s, 1233 w, 1160 m, 862
m, 740 m, 664 w, 582 m cm–1.
[Ni2(L)2(O)(bpp)2]n (2): The preparation of 2 was similar to that of 1
except that bpp (0.099g. 0.5 mmol) was used in place of 4,4Ј-bipy.
Green crystals of 2 were collected in 42% (based on Ni). Elemental
analysis for C56H44Ni2N4O11: calcd. C 63.07; H 4.16; N 5.25%; found:
C 63.12; H 4.18; N 5.22%. IR (KBr): ν˜ = 1624 s, 1466 s, 1411 s,
1365 w, 1037 m, 996 m, 872 m, 764 m, 661 w, 581 m, 516 m cm–1.
Figure 5. (a) Coordination environment of the ZnII ion in 5. Hydrogen
atoms are omitted for clarity. (b) Schematic description of the 6-con-
nected framework with (36.46.53} topology.
[Zn(L)(bib)0.5]n (3): A mixture of H2L (0.135 g, 0.5 mmol), Zn(OAc)2·
2H2O (0.108 g, 0.5 mmol), bib (0.109 g, 0.5 mmol), NaOH (0.04 g,
1 mmol), and distilled water (15 mL) was heated to 160 °C for 96 h
in a 25 mL stainless steel reactor with a Teflon liner, followed by slow
cooling to room temperature. Colorless crystals of compound 3 were
obtained in 53% yield (based on Zn). Elemental analysis for
C21H17ZnN2O5: calcd. C 56.96; H 3.87; N 6.33%; found: C 56.93; H
3.84; N 6.32%. IR (KBr): ν˜ = 1617 s, 1455 s, 1388m, 1227 m,1164
m, 1015 m, 948 w, 894 m, 814 m, 627 m, 557 m, 462 m cm–1.
effectively reduced the loss of energy.[37–39] The shifts of emis-
sion bands occurring in complexes 3, 4, and 5 are probably due
to the cooperative effects of intraligand emission and the li-
gand-to-metal charge transfer (LMCT).[30–42]
[Zn(L)(PyBIm)]n (4): The preparation of compound 4 was similar to
that of compound 3 except that PyBIm (0.098 g. 0.5 mmol) was used
in place of bib. Colorless crystals of 4 were collected in 42% (based
on Zn). Elemental analysis for C27H17ZnN3O5: calcd. C 61.32; H 3.24;
N 7.95%; found: C 61.30; H 3.24; N 7.94%. IR (KBr): ν˜ = 1609 s,
1533 s, 1394 s, 1310 w, 1241 m, 1103 m,1016 m, 943 m, 834 m, 716
m, 694 w, 553 m cm–1.
[Zn3(L)2(μ3-OH)(im)]n (5): The preparation of compound 5 was sim-
ilar to that of compound 3 except that im (0.068 g. 0.5 mmol) was
used in place of bib. Colorless crystals of 5 were collected in 40%
(based on Zn). Elemental analysis for C33H19N2O11Zn3: calcd. C
48.59; H 2.35; N 3.43%; found: C 48.56; H 2.34; N 3.45%. IR (KBr):
ν˜ = 1631 s, 1470 s, 1402 s, 1344 m, 1257 m, 1075 m, 925 m, 874 w,
738 m cm–1.
Figure 6. Solid-state emission spectra of H2L and compounds 3–5 at
room temperature.
X-ray Crystallography: Diffraction intensity data of the single crystal
of the five compounds were collected with a Bruker SMART APEX
II CCD diffractometer equipped with a graphite monochromated Mo-
Kα radiation (λ = 0.71073 Å) by using a ω-scan mode. Empirical ab-
sorption correction was applied using the SADABS programs.[43] All
the structures were solved by direct methods and refined by full-matrix
least-squares methods on F2 using the program SHEXL 97.[44] All
non-hydrogen atoms were refined anisotropically. The hydrogen atoms
were located by geometrically calculations, and their positions and
Conclusions
Five metal-organic polymers were synthesized and charac-
terized based on benzophenone-2,4Ј-carboxylate and N-donor
ligands, which formed different frameworks. Furthermore, the
solid state luminescent spectra demonstrated that complexes
3–5 could serve as good candidates for optical materials.
4
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–8

Coordination Polymers with Benzophenone-2,4Ј-dicarboxylic Acid
Table 1. Crystallographic data and structure refinement summary for complexes 1–5.
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
C60H42N6Ni2O11
1140.42
monoclinic
C56H44Ni2N4O11
1066.37
monoclinic
C21H17ZnN2O5
442.74
C27H17ZnN3O5
528.81
monoclinic
C33H19Zn3N2O11
815.61
triclinic
triclinic
¯
¯
Space group
C2/c
C2/c
P1
P21/c
P1
Unit cell dimensions
a = 15.303(3) Å
b = 33.873 Å
c = 10.825(2) Å
a = 21.887(10) Å
b = 9.997(5) Å
c = 23.855(11) Å
a = 9.6099(7) Å
b = 9.8590(7) Å
c = 11.2613(8) Å
α = 90.9650(10)°
β = 106.9690 (10)° β = 115.839(13)°
γ = 108.6200 (10)°
a = 11.505(7) Å
b = 9.076(6) Å
c = 24.058(14) Å
a = 10.949(6) Å
b = 12.293(7) Å
c = 12.519(7) Å
α = 76.987(7)°
β = 73.293(6)°
γ = 80.099(7)°
1562.02(15)
2
β = 104.483°
β = 101.547(5)°
Volume /Å3
Z
5433(2)
4
5114(3)
4
959.92(12)
2
2261.0(17)
4
Calculated density /
1.394
1.385
1.532
1.554
1.734
mg·m–3
Independent reflections 2760
4699
3558
4324
6121
[I Ͼ 2σ(I)]
F(000)
2352
2208
454
1080
818
θ range for data collec- 1.20–27.45
1.74–27.48
1.90–27.49
1.88–27.48
2.19–27.53
tion
Limiting indices
–19 Յ h Յ 19
–28 Յ k Յ 43
–13 Յ l Յ 13
–18 Յ h Յ 28
–12 Յ k Յ 12
–30 Յ l Յ 30
1.021
R1 = 0.0346
wR2 = 0.0890
R1 = 0.0459
wR2 = 0.0953
0.568 and-0.254
–10 Յ h Յ 12
–12 Յ k Յ 10
–12 Յ l Յ 14
1.026
R1 = 0.0359
wR2 = 0.0834
R1 = 0.0455
wR2 = 0.0876
0.462 and –0.219
–14 Յ h Յ 13
–11 Յ k Յ 11
–27 Յ l Յ 31
1.003
R1 = 0.0299
wR2 = 0.0748
R1 = 0.0381
wR2 = 0.0785
0.352and –0.318
–14 Յ h Յ 14
–15 Յ k Յ 12
–13 Յ l Յ 16
1.017
R1 = 0.0234
wR2 = 0.0624
R1 = 0.0276
wR2 = 0.0644
0.308 and-0.421
Goodness-of-fit on F2 1.069
b)
R1a),wR2 [I Ͼ 2σ(I)] R1 = 0.0595
wR2 = 0.1070
R1 = 0.1133
wR2 = 0.1165
b)
R1a),wR2 (all data)
Largest diff. peak and 0.484 and –0.421
hole /e·Å–3
2
a) R = Σ(||Fo|–|Fc||)/Σ|Fo|. b) wR = [Σw(|Fo|2–|Fc|2)2/Σw(Fo )]1/2
.
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thermal parameters were fixed during the structure refinement. The
crystallographic data and experimental details of structural analyses
for coordination polymers are summarized in Table 1. Selected bond
and angle parameters are listed in Table 2. The carbon atoms (C26,
C27, C29, and C30) in the 4,4Ј-bipy ligand in compound 1 are disor-
dered.
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Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-822057, -822058, -822059, -822060, and -822061
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
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the International Scientific and Technological Cooperation Projects of
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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5

J. Xu, X. Sun, Y. Fan, C. Bi, M. Sun
ARTICLE
Table 2. Selected bond lengths /Å and angles /° for complexes 1–5.
1
Ni(1)–O(2)
1.990(4)
Ni(1)–O(4)ii
2.112(3)
Ni(1)–N(1)
2.076(3)
2.098(3)
Ni(1)–N(3)
2.115(4)
2.178(3)
Ni(1)–N(2)i
Ni(1)–O(5)ii
O(2)–Ni(1)–N(1)
O(2)–Ni(1)–N(2)i
N(1)–Ni(1)–N(2)i
O(2)–Ni(1)–O(4)ii
N(1)–Ni(1)–O(4)ii
N(2)i–Ni(1)–O(4)ii
104.61(15)
91.34(14)
92.43(12)
96.23(13)
159.16(15)
87.03(12)
O(2)–Ni(1)–N(3)
N(1)–Ni(1)–N(3)
N(2)i–Ni(1)–N(3)
O(4)ii–Ni(1)–N(3)
O(2)–Ni(1)–O(5)ii
N(1)–Ni(1)–O(5)ii
88.16(15)
94.24(13)
173.22(13)
86.31(12)
157.84(12)
97.55(14)
2
Ni(1)–O(5)
2.0120(15)
2.0636(14)
2.0808(14)
2.0822(10)
89.30(7)
88.17(7)
174.86(6)
91.77(6)
94.65(5)
89.90(5)
87.16(6)
176.97(5)
Ni(1)–N(1)
Ni(1)–N(2)iii
O(4)–Ni(1)i
2.0876(17)
2.1059(16)
2.0636(14)
Ni(1)–O(4)i
Ni(1)–O(1)ii
Ni(1)–O(6)
O(5)–Ni(1)–O(4)i
O(5)–Ni(1)–O(1)ii
O(4)i–Ni(1)–O(1)ii
O(5)–Ni(1)–O(6)
O(4)i–Ni(1)–O(6)
O(1)ii–Ni(1)–O(6)
O(1)ii–Ni(1)–N(2)iii
O(6)–Ni(1)–N(2)iii
O(5)–Ni(1)–N(1)
O(4)i–Ni(1)–N(1)
O(1)ii–Ni(1)–N(1)
O(6)–Ni(1)–N(1)
O(5)–Ni(1)–N(2)iii
O(4)i–Ni(1)–N(2)iii
N(1)–Ni(1)–N(2)iii
177.55(6)
92.23(6)
90.14(6)
90.01(6)
87.40(7)
88.25(6)
90.74(7)
3
Zn(1)–N(1)
2.0193(18)
2.0360(19)
2.0477(17)
104.97(8)
101.32(8)
89.80(9)
Zn(1)–O(4)iii
Zn(1)–O(1)
2.0515(18)
2.0585(18)
Zn(1)–O(5)i
ZN(1)–O(2)ii
N(1)–Zn(1)–O(5)i
N(1)–Zn(1)–O(2)ii
O(5)i–Zn(1)–O(2)ii
N(1)–Zn(1)–O(4)iii
O(5)i–Zn(1)–O(4)iii
O(2)ii–Zn(1)–O(4)iii
N(1)–Zn(1)–O(1)
O(5)i–Zn(1)–O(1)
O(2)ii–Zn(1)–O(1)
O(4)iii–Zn(1)–O(1)
87.87(8)
102.92(8)
85.00(9)
155.74(8)
87.02(8)
99.79(8)
155.11(7)
4
Zn(1)–O(1)
1.9294(14)
1.9551(13)
116.69(6)
94.30(6)
Zn(1)–O(4)ii
Zn(1)–N(1)
O(1)–Zn(1)–N(1)
O(5)i–Zn(1)–N(1)
O(4)ii–Zn(1)–N(1)
2.0009(16)
2.0131(17)
118.34(7)
110.08(6)
101.15(7)
Zn(1)–O(5)i
O(1)–Zn(1)–O(5)i
O(1)–Zn(1)–O(4)ii
O(5)i–Zn(1)–O(4)ii
114.17(6)
5
Zn(1)–O(2)
1.9486(13)
1.9523(15)
2.0201(14)
2.0201(13)
2.0829(12)
1.9537(15)
1.9561(14)
107.22(6)
103.91(6)
103.10(6)
109.40(5)
135.44(6)
91.92(6)
Zn(2)–O(6)ii
Zn(2)–O(1)1iii
Zn(2)–O(1)
Zn(2)–O(3)
Zn(3)–O(8)
Zn(3)–O(1)
1.9742(13)
2.0163(12)
2.0610(13)
2.0656(13)
1.9560(14)
1.9824(13)
Zn(1)–N(2)i
Zn(1)–O(5)ii
Zn(1)–O(1)
Zn(2)–O(7)
Zn(3)–N(1)
Zn(3)–O(1)0iv
O(2)–Zn(1)–N(2)i
O(2)–Zn(1)–O(5)ii
N(2)i–Zn(1)–O(5)ii
O(2)–Zn(1)–O(1)
N(2)i–Zn(1)–O(1)
O(5)ii–Zn(1)–O(1)
O(6)ii–Zn(2)–O(7)
O(1)1iii–Zn(2)–O(7)
O(1)–Zn(2)–O(7)
O(3)–Zn(2)–O(7)
O(1)0iv–Zn(3)–O(1)
O(6)ii–Zn(2)–O(1)1iii
O(6)ii–Zn(2)–O(1)
O(1)1iii–Zn(2)–O(1)
O(6)ii–Zn(2)–O(3)
O(1)1iii–Zn(2)–O(3)
O(1)–Zn(2)–O(3)
N(1)–Zn(3)–O(1)0iv
N(1)–Zn(3)–O(8)
O(1)0iv–Zn(3)–O(8)
N(1)–Zn(3)–O(1)
O(8)–Zn(3)–O(1)
112.87(6)
98.00(5)
149.12(6)
103.97(6)
80.47(5)
93.17(5)
103.42(6)
78.74(5)
93.95(5)
150.40(5)
117.97(6)
102.25(6)
111.59(6)
104.35(7)
114.96(6)
105.35(5)
Symmetry code for compounds: (1): (i) x+1/2, –y+1/2, z+1/2; (ii) –x+1, y, –z+3/2. (2) (i) –x+1, y, –z+1/2; (ii) x, y+1, z; (iii) –x+1/2, –y+1/2, –
z. (3) (i) x, y+1, z; (ii) –x, –y+2, –z+2; (iii) –x, –y+1, –z+2. (4) (i) x+1, –y+3/2, z+1/2; (ii) –x, y–1/2, –z+3/2. (5) (ii) –x+1, –y, –z; (iii) –x+1, –
y, –z+1; (iv) x–1, y, z.
6
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Z. Anorg. Allg. Chem. 2012, 1–8

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Received: January 8, 2012
Published Online: ᭿
Z. Anorg. Allg. Chem. 2012, 1–8
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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7

J. Xu, X. Sun, Y. Fan, C. Bi, M. Sun
ARTICLE
J. Xu, X. Sun, Y. Fan, C. Bi,* M. Sun* ............................ 1–8
Hydrothermal Synthesis of Five New Coordination Polymers
Based on Benzophenone-2,4Ј-dicarboxylic Acid and N-Donor
Spacers
8
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Z. Anorg. Allg. Chem. 2012, 1–8