Syntheses and crystal structures of three coordination polymers based on terphenyl-2,5,2,5-tetracarboxylic acid

Article abstract of DOI:10.1080/00958972.2012.713099

Solvothermal reactions of terphenyl-2,5,2,5-tetracarboxylic acid (H ₄qptc) and M^II (M=Co, Ni, Cu) in the presence of 2,2-bipyridine (2,2-bpy) afford three new coordination polymers, [M(qptc) _0.5(2,2-bpy)(H₂O)]_n (M=Co (1), Ni (2)) and [Cu(H₂qptc)(2,2-bpy)]_n (3). The structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, and TGA. Complexes 1 and 2 are isostructural and display a 2-D layer wherein qptc⁴ is a twisted H-shaped ligand connecting Co^II centers. Furthermore, 3-D structures in 1 and 2 are formed via inter-chain interactions between neighboring 2,2-bpy ligands, with the centroid-centroid distances of 3.619-3.822. In 3, two deprotonated carboxyl groups of H₂qptc² are a Z-shaped ligand linking Cu^II centers to a 1-D zigzag polymeric chain. A 2-D layer structure is built with the help of inter-chain interactions between the 2,2-bpy and H₂qptc².

Full text of DOI:10.1080/00958972.2012.713099

This article was downloaded by: [University of Arizona]
On: 07 August 2012, At: 01:06
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Coordination Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gcoo20
Syntheses and crystal structures of
three coordination polymers based on
terphenyl-2,5,2′,5′-tetracarboxylic
acid
Xiutang Zhang a b , Liming Fan a b , Zhong Sun a , Wei Zhang a ,
Dacheng Li b , Peihai Wei a , Bin Li a & Jianmin Dou b
a Department of Chemistry and Chemical Engineering, Advanced
Material Institute of Research, Qilu Normal University, Jinan
250013, China
b College of Chemistry and Chemical Engineering, Liaocheng
University, Liaocheng 252059, China
Accepted author version posted online: 17 Jul 2012. Version of
record first published: 06 Aug 2012
To cite this article: Xiutang Zhang, Liming Fan, Zhong Sun, Wei Zhang, Dacheng Li, Peihai Wei, Bin
Li & Jianmin Dou (2012): Syntheses and crystal structures of three coordination polymers based on
terphenyl-2,5,2′,5′-tetracarboxylic acid, Journal of Coordination Chemistry, 65:18, 3205-3215
To link to this article: http://dx.doi.org/10.1080/00958972.2012.713099
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-
conditions
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,

demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.

Journal of Coordination Chemistry
Vol. 65, No. 18, 20 September 2012, 3205–3215
Syntheses and crystal structures of three coordination polymers
based on terphenyl-2,5,29,59-tetracarboxylic acid
XIUTANG ZHANG*yz, LIMING FANyz, ZHONG SUNy, WEI ZHANGy,
DACHENG LIz, PEIHAI WEIy, BIN LIy and JIANMIN DOUz
yDepartment of Chemistry and Chemical Engineering, Advanced Material Institute of
Research, Qilu Normal University, Jinan 250013, China
zCollege of Chemistry and Chemical Engineering, Liaocheng University,
Liaocheng 252059, China
(Received 29 November 2011; in final form 26 April 2012)
Solvothermal reactions of terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc) and MII (M¼Co,
Ni, Cu) in the presence of 2,20-bipyridine (2,20-bpy) afford three new coordination polymers,
[M(qptc)0.5(2,20-bpy)(H2O)]n (M¼Co (1), Ni (2)) and [Cu(H2qptc)(2,20-bpy)]n (3). The struc-
tures have been determined by single-crystal X-ray diffraction analyses and further character-
ized by elemental analyses, IR, and TGA. Complexes 1 and 2 are isostructural and display a
2-D layer wherein qptc4ꢀ is a twisted H-shaped ligand connecting CoII centers. Furthermore,
3-D structures in 1 and 2 are formed via inter-chain ꢀꢁ ꢁ ꢁꢀ interactions between neighboring
0
˚
2,2 -bpy ligands, with the centroid–centroid distances of 3.619–3.822 A. In 3, two deprotonated
carboxyl groups of H2qptc2ꢀ are a Z-shaped ligand linking CuII centers to a 1-D zigzag
polymeric chain. A 2-D layer structure is built with the help of inter-chain ꢀꢁ ꢁ ꢁꢀ interactions
between the 2,20-bpy and H2qptc2ꢀ
.
Keywords: Terphenyl-2,5,20,50-tetracarboxylic acid; 2,20-Bipyridine; Cobalt(II); Nickel(II);
Copper(II)
1. Introduction
Synthesis of metal–organic frameworks (MOFs) have attracted research for structural
and topological novelty and potential applications in gas storage, microelectronics, ion
exchange, chemical separations, nonlinear optics, and heterogeneous catalysis [1, 2].
Structures of such materials depend on metal ion, template, metal–ligand ratio, pH,
counteranion, and number of coordination sites provided by ligands [3]. In assembly of
MOFs, choice of ligand is very important in construction of MOFs [4, 5]. Metal–
organic structural motifs, including honeycomb, brick wall, bilayer, ladder, herring-
bone, diamondoid, and rectangular grid, have been designed by employing bridging
polycarboxylates, such as 20,50-dimethyl-1,10 : 40,100-terphenyl-3,300,5,500-tetracarboxylic
acid [6a], 20,50-difluoro-1,10 : 40,100terphenyl-3,300,5,500-tetracarboxylic acid [6a], 20,30,50,60-
tetrafluoro-1,10 : 40,100-terphenyl3,300,5,500-tetracarboxylic acid [6a], naphthalene-1,
*Corresponding author. Email: xiutangzhang@yahoo.com.cn
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2012 Taylor & Francis
http://dx.doi.org/10.1080/00958972.2012.713099

3206
X. Zhang et al.
4-diyl-bis(benzene-3,5-dicarboxylic acid) [6a], 5,50-(9,10-anthracenediyl)diisophthalic
acid [6b], and p-terphenyl-3,300,5,5000-tetracarboxylic acid [6c]. Aromatic polycarbox-
ylates serve as excellent candidates for building highly connected, self-penetrating, or
helical coordination frameworks due to bent backbones and versatile bridging [7, 8].
However, MOFs based on terphenyl-2,5,20,50-tetracarboxylic acid have not been
documented to date.
Aromatic dicarboxylates and a flexible dipyridyl linker 1,3-bis(4-pyridyl)propane
(bpp) is a reliable strategy for obtaining new coordination nets [9]. A minor change of
carboxylate building block may be applied to realize structural control of the resulting
coordination polymers (CPs). These considerations inspired us to explore new
coordination frameworks with terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc).
Compared to rigid 1,2,4,5-benzenetetracarboxylic acid, H4qptc is more flexible and
longer and possesses several interesting features: (i) four carboxyl groups that may be
completely or partially deprotonated for structures with higher dimensionalities,
(ii) ability to act as hydrogen-bond acceptor and donor, depending upon the degree of
deprotonation, (iii) two sets of carboxyl groups separated by a phenyl can form
different dihedral angles through rotation of C–C single bonds, and may ligate metal
centers in different orientations. These features may lead to cavities, interpenetration,
helical structures, and other unique topologies. We began to assemble H4qptc and
different transition metal ions into polymeric complexes under solvothermal conditions
and anticipated that the structural features stored in H4qptc will induce new polymeric
structures. In this article, we report syntheses and characterizations of three new CPs,
[M(qptc)0.5(2,20-bpy)(H2O)]n (M¼Co (1), Ni (2)), and [Cu(H2qptc)(2,20-bpy)]n (3),
which exhibit architectures from 1-D zigzag chain to 3-D framework by employing
H4qptc and 2,20-bipy ligands.
2. Experimental
2.1. Materials and methods
5-Bromo-2,5-dimethylbenzene (I), bis(pinacolato)diborane, Pd(dppf)2Cl2, and
Pd(PPh3)4 were purchased from Jinan Camolai Trading Company and used without
purification. C, N, and H analyses were performed on an EA1110 CHNS-0 CE
elemental analyzer. IR (KBr pellet) spectra were recorded on a Nicolet Magna
750FT-IR spectrometer.
2.2. Synthesis of terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc)
2.2.1. Synthesis of 2-bromoterephthalic acid (II). Mixture of I (1000 mmol, 18.5 g),
KOH (110 mmol, 6.0 g), and 600 mL H2O was heated to reflux. KMnO4 (440 mmol,
70.0 g) was added in portions to the refluxing solution. Refluxing was continued until I
was completely oxidized. After cooling to room temperature, the mixture was filtered and
residual manganese dioxide was washed with solution of sodium hydroxide. The
combined filtrates were acidified with concentrated hydrochloric acid. White solid
precipitate was filtered off, washed several times with water, and dried to afford II (82%).

Terphenyl-2,5,20,50-tetracarboxylic acid
3207
EI-MS: m/z [M ꢀ H]– 242.9 (Calcd for C8H5BrO4, 243.9. Anal. Calcd for C8H5BrO4 (%):
C, 39.21; H, 2.06. Found: C, 39.08; H, 2.02.
2.2.2. Synthesis of diethyl 2-bromoyterephthalate (III). Mixture of II (0.1 mol, 24.5 g),
500 mL ethanol, and 10 mL concentrated H2SO4 was refluxed for 12 hours, and then
poured into 500 mL H2O. The solution was extracted with ethyl acetate (200 mL ꢂ 3),
dried with anhydrous magnesium sulfate, and then concentrated on a rotary evaporator
to give a white powder (92%). Anal. Calcd for C12H13BrO4 (%): C, 47.86; H, 4.35.
Found: C, 47.79; H, 4.32.
2.2.3. Synthesis of 4,4,5,5-tetramethyl-2-(diethyl 2,5-dicarboxylatephenyl)-1,3-dioxolane
(IV). The synthetic method was modified from that published for 4,4,5,5-tetramethyl-
2 -(dimethyl 3,5-dicarboxylatephenyl)-1,3-dioxolane [4e]. Mixture of III (100 mmol,
30.0 g), bis(pinacolato)diborane (11.8 mmol, 3.0 g), potassium acetate (0.29 mmol,
28.0 g), Pd (dppf)2Cl2 (7.0 mmol, 5.0 g), and dried 1,4-dioxane (500 mL) reacted at
100ꢃC overnight and afterward was extracted with ethyl acetate (200 mL ꢂ 3). The
organic layer was decolored with activated carbon and dried by anhydrous Na2SO4.
Crude product was obtained from concentration under vacuum and purified by column
chromatography (silica gel, ethyl acetate/petroleum ether, 6 v%). Yield: 78%. Anal.
Calcd for C18H25BO6 (%): C, 62.09; H, 7.24. Found: C, 61.89; H, 7.15.
2.2.4. Synthesis of tetraethyl terphenyl-2,5,20,50-tetracarboxylate (V). Mixture of IV
(100 mmol, 34.82 g), 1,4-dibromobenzene (50 mmol, 11.7 g), and K3PO4 (200 mmol,
42.4 g) were mixed in 1,4-dioxane (500 mL), and the mixture was deaerated using N2 for
10 min. Pd(PPh3)4 (4 mmol, 5.0 g) was added to the stirred reaction mixture and the
mixture was heated to reflux for one week under N2. The crude product of VI was
obtained after 1,4-dioxane was removed under vacuum. Recrystallization from
methanol offered pure tetraethyl terphenyl-2,5,20,50-tetracarboxylate. Anal. Calcd for
C30H30O8 (%): C, 69.49; H, 5.83. Found: C, 69.35; H, 5.71.
2.2.5. Synthesis of terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc, VI). Mixture of V
(50 mmol, 25.9 g) and 10 g NaOH in 500 mL H2O was refluxed for 2 h and then cooled
to room temperature. The solution was neutralized with concentrated HCl. White
powder was obtained in 92% yield. EI-MS: m/z [M ꢀ H]ꢀ, 405.1 (Calcd for C22H14O8,
406.1). Anal. Calcd for C22H14O8 (%): C, 65.03; H, 3.47. Found: C, 64.93; H, 3.39.
2.3. Synthesis of 1–3
2.3.1. Synthesis of 1. The synthesis is performed in 25 mL Teflon-lined stainless steel
vessels. A mixture of H4qptc (0.15 mmol, 0.020 g), cobalt(II) chloride hexahydrate
(0.20 mmol, 0.048 g), 2,20-bpy (0.32 mmol, 0.050 g), NaOH (0.3 mmol, 0.012 g), 6 mL
H2O, and 6 mL EtOH was heated to 120ꢃC for 3 days, followed by slow cooling
(10ꢃC hꢀ1) to room temperature, giving red block crystals. Yield: 36% (based on Co).
Anal. Calcd for C42H30Co2N4O10 (%): C, 58.08; H, 3.48; N, 6.45. Found: C, 56.78;

3208
X. Zhang et al.
H, 3.72; N, 3.81. IR(KBr pellet, cmꢀ1): 3445(vs), 3069(v), 2934(v), 1708(vs), 1589(vs),
1453(vs), 1231(s), 1098(s), 850(m), 779(m), 523 (w).
2.3.2. Synthesis of 2. The synthesis is performed in a 25 mL Teflon-lined stainless steel
vessel. A mixture of H4qptc (0.05 mmol, 0.020 g), nickel(II) sulfate hexahydrate
(0.10 mmol, 0.028 g), 2,20-bpy (0.10 mmol, 0.018 g), NaOH (0.05 mmol, 0.002 g), and
20 mL H2O was heated to 150ꢃC for 4 days, followed by slow cooling (5ꢃC hꢀ1) to room
temperature, giving green block crystals. Yield: 61% (based on Ni). Anal. Calcd for
C42H42Ni2O16N4 (976.2) (%): C, 51.68; H, 4.34; N, 5.74. Found: C, 50.78; H, 4.32; N,
5.51. IR(KBr pellet, cmꢀ1): 3468(vs), 3071(v), 2921(v), 1697(vs), 1569(vs), 1423(vs),
1228(s), 1109(s), 853(m), 767(m), 527 (w).
2.3.3. Synthesis of 3. The synthesis is performed in a 25 mL Teflon-lined stainless steel
vessel. A mixture of H4qptc (0.05 mmol, 0.020 g), copper(II) sulfate pentahydrate
(0.20 mmol, 0.049 g), 2,20-bpy (0.32 mmol, 0.050 g), NaOH (0.3 mmol, 0.012 g), 6 mL
H2O, and 6 mL EtOH was heated to 120ꢃC for 3 days, followed by slow cooling
(10ꢃC hꢀ1) to room temperature, giving blue block crystals. Yield: 36% (based on Cu).
Anal. Calcd for C42H30Cu2N4O10 (840.6) (%): C, 58.08; H, 3.48; N, 6.45. Found: C,
57.78; H, 3.62; N, 6.21. IR(KBr pellet, cmꢀ1): 3436(vs), 3073(v), 2921(v), 1810(vs),
1551(vs), 1417(vs), 1251(s), 1105(s), 852(m), 773(m), 517 (w).
2.4. Structure determination
Intensity data collections were carried out on a Siemens SMART diffractometer
˚
equipped with a CCD detector using Mo-Ka monochromated radiation (ꢁ ¼ 0.71073 A)
at 293(2) K. The absorption correction was based on multiple and symmetry-equivalent
reflections in the data set using SADABS based on the method of Blessing. The
structures were solved by direct methods and refined by full-matrix least-squares using
the SHELX-TL package [10]. Crystallographic data for 1–3 are given in table 1.
3. Results and discussion
3.1. Synthesis
The synthesis of terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc) is shown in scheme 1.
To obtain pure product and high yield, organic solvents should be dried completely
during the syntheses of III and IV. Synthesis of V was performed under N2. The final
H4qptc is white if the obtained crude product was decolorized by refluxing in EtOH
with activated carbon. In this study, 1–3 were prepared from the solvothermal reaction
of transition metal salts and H4qptc in the presence of bpy.
3.2. Coordination modes of the H2qptc2ꢀ and qptc4ꢀ ligands
H2qptc2ꢀ and qptc4ꢀ have different coordination modes for design and synthesis of
functional materials. There are two types of different coordination configurations for
carboxylates of H2qptc2ꢀ and qptc4ꢀ ligands (figure 1).

Terphenyl-2,5,20,50-tetracarboxylic acid
Table 1. Crystallographic data for 1–3.
3209
1
2
3
Formula
C21H15CoN2O8
482.28
296(2)
Triclinic
ꢀ
P1
C21H21N2NiO8
488.11
293(2)
Triclinic
ꢀ
P1
C32H20CuN2O8
624.04
296(2)
Monoclinic
C2/c
Formula weight
Temperature (K)
Crystal system
Space group
ꢃ
˚
Unit cell dimensions (A, )
a
b
c
ꢄ
ꢅ
ꢆ
10.109(1)
10.735(0)
10.928(4)
73.82(5)
64.97(1)
83.59(5)
1032.03(2), 2
1.398
0.865
R1 ¼ 0.0652,
wR2 ¼ 0.2261
R1 ¼ 0.0721,
wR2 ¼ 0.2357
1.000
10.312(1)
11.003(1)
11.297(1)
62.07(2)
78.65(3)
70.72(3)
1067.6(1), 2
1.518
0.960
R1 ¼ 0.0562,
wR2 ¼ 0.1171
R1 ¼ 0.0852,
wR2 ¼ 0.1254
1.001
10.640(6)
16.041(8)
16.498(12)
90.00
104.65(1)
90.00
2724.3(1), 4
1.521
0.860
R1 ¼ 0.0955,
wR2 ¼ 0.1872
R1 ¼ 0.1887,
wR2 ¼ 0.2255
0.992
3
˚
Volume (A ), Z
Calculated density (g cmꢀ3
)
Absorption coefficient (mmꢀ1
)
R [I 4 2ꢇ(I)]a,b
R indices (all data)a,b
Goodness-of-fitc
(Dꢈ)max and (Dꢈ)min (e A
ꢀ3
˚
)
2.140 and ꢀ0.337
0.531 and ꢀ0.698
1.410 and ꢀ0.394
aR1 ¼ Æ||Fobsd| ꢀ |Fcalcd||/Æ|Fobsd|.
bwR2 ¼ {Æ[w(Fo2bsd ꢀ Fc2alcd)2]/Æ[w(Fo2bsd)2]}1/2
.
w ¼ 1/[ꢇ2(Fo2) ¼ xP ¼ (yP)2];
with
c
P ¼ (Fo2 ¼ 2Fc2)/3. Goodness-of-fit on F2 ¼ [Æw(Fo2bsd ꢀ Fc2alcd)2/(n ꢀ p)]1/2, where n ¼ number of reflections, p ¼ parameter
used.
3.3. Structure descriptions
3.3.1. [M(qptc)0.5(2,20-bpy)(H2O)]n (M¼Co (1), Ni (2)). Single-crystal X-ray diffrac-
tion analysis reveals that 1 and 2 are isostructural, crystallizing in the monoclinic
ꢀ
system, P1 space group. Only the structure of 1 will be discussed as representative (bond
distances and angles are given in table 2). The asymmetric unit of 1 consists of one CoII,
one 2,20-bpy, half of a qptc4ꢀ, and one water molecule. Each CoII is a distorted
octahedral geometry, coordinated by chelating 2,20-bpy [Co(1)–N(1) ¼ 2.126(5) and
Co(1)–N(2) ¼ 2.105(4) A], four oxygen atoms from three qptc4ꢀ [Co(1)–O(1) ¼ 2.134(3),
˚
˚
Co(1)–O(3) ¼ 2.065(3),
Co(1)–O(4) ¼ 2.173(3),
and
Co(1)–O(5) ¼ 2.085(4) A],
with distorted octahedral coordination (figure 1a). Axial Co–O distances are a
little shorter than equatorial ones (including Co–O and Co–N) due to the Jahn-Teller
effect.
The carboxyl groups of qptc4ꢀ exhibit ꢂ1ꢀꢃ1 : ꢃ0 and ꢂ2–ꢃ1 : ꢃ1 coordination, acting
as a twisted H-shaped ligand (figure 2a) connecting CoII centers to generate a 2-D layer
(figure 2b). This may be ascribed to dramatic twists between phenyl rings in qptc4ꢀ
.
Two side phenyl rings are approximately vertical (dihedral angle 87.7ꢃ) and
have dihedral angles of 45.5ꢃ and 134.5ꢃ with the central one. Two sides of the
H-shaped building block are perpendicular. Thus, the central metals are
interconnected by such building blocks along different directions to give the final
framework.
Crystal packing of 1 reveals inter-chain ꢀꢁ ꢁ ꢁꢀ interactions exist between neighboring
0
˚
2,2 -bpy ligands, with centroid–centroid distances of 3.619 and 3.822 A, respectively.
Such contacts link 2-D layers into a 3-D structure (figure 2c).

3210
X. Zhang et al.
C H O C
HO C
2
5
2
2
KMnO
EtOH/H SO
2
4
4
CO C H
2 5
CO H
2
2
Br
Br
Br
(I)
(II)
(III)
bis(pinacolato)diborane
Pd (dppf) Cl
2
2
C H O C
2
5 2
C H O C
CO C H
2 5
2
5 2
2
1,4-dibromobenzene
Pd(PPh3)4
CO C H
2 5
2
B
O
O
C H O C
2
5 2
CO C H
2 5
2
(V)
(IV)
NaOH
CO H
CO H
2
2
HO C
HO C
2
2
(VI)
Scheme 1. The scheme for the synthesis of terphenyl-2,5,20,50-tetracarboxylic acid (H4qptc).
(a)
(b)
Figure 1. Coordination modes for H2qptc2ꢀ and qptc4ꢀ: (a) H-shaped for 1 and 2 and (b) Z-shaped for 3.

Terphenyl-2,5,20,50-tetracarboxylic acid
3211

3212
X. Zhang et al.
Figure 2. (a) Coordination environment of CoII in 1 with the thermal ellipsoids at 30% probability
(Symmetry codes: (A): ꢀx, ꢀy þ 1, ꢀz þ 1, (B) ꢀx þ 1, ꢀy þ 1, ꢀzꢀ1, ꢀz þ 1, (C) ꢀx þ 1, ꢀy þ 1, ꢀz),
(b) view of the 2-D layer of 1, and (c) perspective view of the 3-D supramolecular structure of 1 via inter-chain
ꢀ ꢁ ꢁ ꢁ ꢀ interactions.
3.3.2. [Cu(H2qptc)(2,20-bpy)]n (3). Single-crystal X-ray diffraction analysis reveals that
3 crystallizes in the monoclinic system, C2/c space group. The asymmetric unit of 3
consists of half of a CuII, half of a 2,20-bpy and half of a partly deprotonated H2qptc2ꢀ
.
Each CuII locates in a distorted square plane, coordinated by a chelating 2,20-bpy [Cu1–
2ꢀ
˚
˚
N1 ¼ 1.975(6) A] and two oxygen atoms from two H2qptc [Cu1–O1 ¼ 1.941(5) A]
(figure 3a).
Different from 1 and 2, the H4qptc ligand in 3 is only partly deprotonated under the
solvothermal condition. The two deprotonated carboxylates of H2qptc2ꢀ show
ꢂ1–ꢃ1 : ꢃ0 coordination and H2qptc2ꢀ is a Z-shaped ligand (figure 3b) linking CuII
centers to a 1-D zigzag polymeric [Cu(H2qptc)]n chain along the crystallographic [101]
0
˚
direction with adjacent Cuꢁ ꢁ ꢁCu separation of 10.940 A. Terminal 2,2 -bpy ligands
decorate the chain alternately in an outward fashion along the two sides (figure 3b).
Crystal packing of 3 reveals that inter-chain ꢀꢁ ꢁ ꢁꢀ interactions exist between 2,20-bpy
and H2qptc2ꢀ, with centroid–centroid distances of 3.766 A. Such contacts link 1-D
˚
zigzag chains into a 2-D layer structure (figure 3c).
3.4. TGA analysis
TGA measurements have been carried out on a Perkin-Elmer Diamond TG/DTA
instrument with a flow of dry air and a heating rate of 5ꢃC minꢀ1 from room

Terphenyl-2,5,20,50-tetracarboxylic acid
3213
Figure 3. (a) Coordination environment of CuII in 3 with the thermal ellipsoids at 30% probability
(Symmetry codes: (A): ꢀx þ 1, y, ꢀz þ 1/2, (B) ꢀx þ 1/2, ꢀy þ 1/2, ꢀz), (b) view of the 1-D zigzag chain of 3,
and (c) perspective view of the 2-D supramolecular layer of 3 via inter-chain ꢀꢁ ꢁ ꢁꢀ interactions.
temperature to 1000ꢃC (Supplementary material). For 1, weight loss takes place from
85ꢃC to 437ꢃC with residual weight of 15.10% (Calcd for CoO: 15.5%). For 2, weight
loss takes place from 65ꢃC to 440ꢃC. The residual weight of the sample is 15.3% (Calcd
for NiO: 15.1%). For 3, weight loss takes place from 291ꢃC. The residual weight of the
sample is 17.8% (Calcd for CuO: 16.9%).

3214
X. Zhang et al.
4. Conclusion
We have developed a strategy for synthesizing CPs by employing terphenyl-2,5,20,50-
tetracarboxylic acid (H4qptc). Three new CPs, [M(qptc)0.5(2,20-bpy)(H2O)]n (M¼Co (1),
Ni (2)), and [Cu(H2qptc)(2,20-bpy)]n (3), based on H4qptc and 2,20-bpy have been
obtained under solvothermal conditions. Structural comparisons among 1–3 indicate
that the backbone of the H4qptc ligand plays an important role in governing the
structures of these metal–organic coordination architectures. Further systematic studies
for the design and synthesis of such crystalline materials with H4qptc and other
N-donor building blocks are underway in our laboratory.
Supplementary material
Further details on the crystal structure investigations can be obtained from the
Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK [Telephone: þ44-(0)1223-762-910, Fax: þ44-(0)1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk; or http://www.ccdc.cam.ac.uk/deposit], on quoting the
depository number CCDC-855668 for 1, 855670 for 2, and 855669 for 3.
Acknowledgments
The financial support by the Natural Science Foundation of China (Grant No.
21 101 097), Natural Science Foundation of Shandong Province (ZR2010BQ023), and
Qilu Normal University is acknowledged.
References
[1] (a) N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O’Keeffe, O.M. Yaghi. Science, 300, 1127
(2003); (b) J. Kido, Y. Okamoto. Chem. Rev., 102, 2357 (2002); (c) S. Qiu, G. Zhu. Coord. Chem. Rev.,
253, 2891 (2009); (d) M. Eddaoudi, D.B. Moler, H.L. Li, B.L. Chen, T.M. Reineke, M. O’Keeffe,
O.M. Yaghi. Acc. Chem. Res., 34, 319 (2001); (e) O.R. Evans, W. Lin. Acc. Chem. Res., 35, 511 (2002).
[2] (a) A.J. Blake, N.R. Champness, P. Hubberstey, W.-S. Li, M.A. Withersby, M. Schroder.
¨
Coord. Chem. Rev., 183, 117 (1999); (b) O.R. Evans, W. Lin. Acc. Chem. Res., 35, 511 (2002);
(c) P.J. Steel. Acc. Chem. Res., 38, 243 (2005); (d) J.W. Cheng, S.T. Zheng, G.Y. Yang. Inorg. Chem., 46,
10261 (2007).
[3] (a) Y.Y. Liu, J.F. Ma, J. Yang, Z.M. Su. Inorg. Chem., 46, 3027 (2007); (b) R.-G. Xiong, X. Xue, H. Zhao,
B.F. Abrahams, X.-Z. You, Z. Xue. Angew. Chem., Int. Ed., 41, 3800 (2002); (c) O.M. Yaghi,
M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi, J. Kim. Nature, 423, 705 (2003); (d) A.Y. Robin,
K.M. Fromm. Coord. Chem. Rev., 250, 2127 (2006).
[4] (a) X. Zhao, B. Xiao, A.J. Fletcher, K.M. Thomas, D. Bradshaw, M.J. Rosseinsky. Science, 306, 1012
(2004); (b) G.P. Yang, Y.Y. Wang, H. Wang, C.J. Wang, G.L. Wen, Q.Z. Shi, S.M. Peng. J. Mol. Struct.,
888, 366 (2008).
[5] (a) L. Beitone, C. Huguenard, A. Gansmuller, M. Henry, F. Taulelle, T. Loiseau, G. Ferey. J. Am.
Chem. Soc., 125, 9102 (2003); (b) D.N. Dybtsev, H. Chun, K. Kim. Angew. Chem., Int. Ed., 43,
5033 (2004).

Terphenyl-2,5,20,50-tetracarboxylic acid
3215
[6] (a) X. Lin, I. Telepeni, A.J. Blake, A. Dailly, C.M. Brown, J.M. Simmons, M. Zoppi, G.S. Walker,
K.M. Thomas, T.J. Mays, P. Hubberstey, N.R. Champness, M. Schroder. J. Am. Chem. Soc., 131, 2159
¨
(2009); (b) S.-Q. Ma, J.-P. Simmons, D.-F. Sun, D.-Q. Yuan, H.-C. Zhou. Inorg. Chem., 48, 5263 (2009);
(c) X. Lin, J.-H. Jia, X.-B. Zhao, K.M. Thomas, A.J. Blake, G.S. Walker, N.R. Champness,
P. Hubberstey, M. Schroder. Angew. Chem., Int. Ed. Engl., 45, 7358 (2006).
¨
[7] (a) G.X. Liu, K. Zhu, H. Chen, R.Y. Huang, X.M. Ren. Z. Anorg. Allg. Chem., 635, 156 (2009);
(b) X.L. Wang, C. Qin, E.B. Wang, L. Xu. Eur. J. Inorg. Chem., 3418 (2005); (c) L.X. Sun, Y. Qi,
Y.M. Wang, Y.X. Che, J.M. Zheng. CrystEngComm, 12, 1540 (2010); (d) Y.Q. Lan, X.L. Wang, S.L. Li,
Z.M. Su, K.Z. Shao, E.B. Wang. Chem. Commun., 4863 (2007); (e) D.S. Li, Y.P. Wu, P. Zhang, M. Du,
J. Zhao, C.P. Li, Y.U. Wang. Cryst. Growth Des., 10, 2037 (2010).
[8] (a) D. Tian, Y. Pang, S.-Q. Guo, X.-F. Zhu, H. Zhang. J. Coord. Chem., 64, 1006 (2011); (b) L.-J. Gao,
P.-X. Cao, J.-J. Wang, Y.-P. Wu, F. Fu, M.-L. Zhang, Y.-X. Ren, X.-Y. Hou. J. Coord. Chem., 64,
1299 (2011); (c) A.-H. Yang, H.-L. Gao, S.-R. Fang, J.-Z. Cui. J. Coord. Chem., 64, 2302 (2011);
(d) H. Lin, H.-L. Hu, X.-L. Wang, B. Mu, J. Li. J. Coord. Chem., 63, 1295 (2010).
[9] (a) D. Tian, Y. Pang, Y.H. Zhou, L. Guan, H. Zhang. CrystEngComm, 13, 957 (2011); (b) D. Tian,
Y. Pang, S.Q. Guo, X.F. Zhu, H. Zhang. J. Coord. Chem., 64, 1006 (2011).
[10] G.M. Sheldrick. SHELXS-97 and SHELXL-97, Programs for the Solution and Refinement of Crystal
Structures, University of Gottingen, Germany (1997).