Functional self-assembly of hydrogen-bonded 3D coordination networks constructed from 1,2,4,5-benzenetetracarboxylic acid

Article abstract of DOI:10.1134/S1070328407070019

Hydrothermal synthesis, characterization (IR, TG/DTA, element analysis, inductively coupled plasma (ICP)) and single-crystal X-ray structures of H ₄Btec hydrate and its two cobalt complexes, colorless [H ₄Btec ? 2H₂O] _n (I), pink [Co(H ₂O)₆(H₂Btec)] _n (II), and nacarat {[Co(H₂O)₃(H₂Btec)(Phen)] ? H ₂O} _n (III) (H₄Btec = 1,2,4,5- benzenetetracarboxylic acid, Phen = 1,10-phenanthroline) have been solved. The results showed that I forms a 3D O-H...O hydrogen-bonded network generated from H₄Btec and water molecules, II presents a 3D network constructed by mononuclear [Co(H₂O)₆]²⁺ cations and H ₂Btec^2- dianions through extensive hydrogen-bonding interactions, and III gives rise to a pseudo-octahedral coordination geometry. Extensive hydrogen-bonding interactions have significant effects in configuring a 3D network constructed by mononuclear [Co(H₂Btec)(Phen)(H ₂O)₃] neutral molecules and a water molecules.

Full text of DOI:10.1134/S1070328407070019

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2007, Vol. 33, No. 7, pp. 471–481. © Pleiades Publishing, Ltd., 2007.
Functional Self-Assembly of Hydrogen-Bonded
3D Coordination Networks Constructed
from 1,2,4,5-Benzenetetracarboxylic Acid1
Q. B. Bo, S. Y. Zhao, Z. W. Zhang, Y. L. Sheng, Z. X. Sun, G. X. Sun, C. L. Chen, and Y. X. Li
Institute of Chemistry and Chemical Engineering, Jinan University, Jinan, Shandong, 250022 P. R. China
Received June 8, 2006
Abstract—Hydrothermal synthesis, characterization (IR, TG/DTA, element analysis, inductively coupled
plasma (ICP)) and single-crystal X-ray structures of H4Btec hydrate and its two cobalt complexes, colorless
[H4Btec · 2H2O]n (I), pink [Co(H2O)6(H2Btec)]n (II), and nacarat {[Co(H2O)3(H2Btec)(Phen)] · H2O}n (III)
(H4Btec = 1,2,4,5-benzenetetracarboxylic acid, Phen = 1,10-phenanthroline) have been solved. The results showed
that I forms a 3D O–H···O hydrogen-bonded network generated from H4Btec and water molecules, II presents
a 3D network constructed by mononuclear [Co(H2O)6]2+ cations and H2Btec2– dianions through extensive
hydrogen-bonding interactions, and III gives rise to a pseudo-octahedral coordination geometry. Extensive
hydrogen-bonding interactions have significant effects in configuring a 3D network constructed by mononu-
clear [Co(H2Btec)(Phen)(H2O)3] neutral molecules and a water molecules.
DOI: 10.1134/S1070328407070019
1
INTRODUCTION
anionic forms of H4Btec. Therefore, H4Btec was often
chosen as a building unit for the layers being a molecule
with predictable and interesting supramolecular prop-
erties as a consequence of its molecular symmetry and
complementary hydrogen-bonding capabilities.
Considerable effort has recently been given to
understanding a relationship between molecular and
crystal structures, especially from the viewpoint of
crystal engineering [1–3]. Therefore, the crystal engi-
neering of supramolecular architectures or metal-
organic coordination polymers has attracted much
attention in the past decades [4–7]. The ultimate goal of
crystal engineering is to design specific crystal struc-
tures with potential specific physical and chemical
properties based only on the knowledge of the building
blocks. As a result, a particular emphasis is placed on
identifying reliable and robust intermolecular interac-
tions, especially on the use of hydrogen bonds.
It is known that the deprotonated forms of H4Btec
can act not only as hydrogen-bond acceptors but also as
hydrogen-bond donors, depending on the deprotonated
carboxyl groups, to give different supramolecular
adducts. H4Btec is also an excellent bridging ligand,
and a number of one-, two- and three-dimensional infi-
nite metal frameworks have already been generated
[15–22]. However, the above-mentioned frameworks,
are generated directly by coordination bonds. Indeed,
very few organic structures containing H4Btec or its
derivatives are known.
Hydrogen bonds have been recognized to be of fun-
damental importance in determining the supramolecu-
lar structure of organic solids [8–9]. Its usage in crystal
engineering is also found in many references [10–12].
Here we report the preparation and crystal structures
of three novel 3D organic–inorganic hybrid networks
self-assembled by hydrogen-bonding interactions in
which 2D coordination sheets formed by the self-
assembly of organic molecules or hydrated metal–ion
building blocks are generated first and further extended
into 3D networks by hydrogen-bonding interactions. At
the same time, their thermal stabilities and FT-IR
modes are also discussed.
Assemblies based on the carboxylic group (−COOH)
are very well-known because of its ability to form robust
hydrogen bonds on its own and also with several other
compounds forming either O–H···N or O–H···N/C–H···O
hydrogen bonds, as well as dative bonds through the car-
boxylate group [13, 14].
H4Btec with four carboxylic acid groups symmetri-
cally arranged around a benzene ring has been exten-
sively studied. The interest in the inorganic–organic
solids has been focused upon hydrogen-bonded net-
works that are sustained by partially deprotonated
EXPERIMENTAL
Materials and apparatus. All starting materials
were reagent grade, purchased commercially, and used
without further purification.
1
The article was submitted by the authors in English.
471

472
BO et al.
Elemental analyses (C, H, and N) were carried out on
Synthesis of {[Co(H2O)3(H2Btec)(Phen)] · H2O}n
a Perkin Elmer 2400 Series II CHNS/O elemental ana- (III). Compound was prepared hydrothermally from
lyzer. Inductively coupled plasma (ICP) analysis (Co) a mixture of CoCl2 · 6H2O, 1,2,4,5-benzentetracarbox-
was performed on a Perkin Elmer Optima 3300DV spec- ylic dianhydride, Phen, and H2O in a molar ratio of
trometer. FT-IR spectra were measured on a Perkin 1 : 2 : 1: 1340 by heating in a teflon-lined stainless steel
Elmer FT-IR spectrometer in the 4000–200 cm−1 region autoclave at 200°C for 3 days under static conditions,
with the pressed CsI pellets. The thermal stability of the and the filling volume is 75%. After cooling the reac-
compounds was examined by TG/DTA experiments, tion mixture to room temperature, the saffron prism-
which were carried out under a flow of dry air and at a like crystals appeared on the bottom of the reaction
heating rate of 10 K min–1 with a Perkin Elmer Diamond container together with colorless solutions. The crys-
TG/DTA instrument.
tals obtained were separated and washed with distilled
water and ethanol many times. Finally, the products
were dried in air at room temperature. The yield was
80%.
Synthesis of [H4Btec · 2H2O]n (I). Compound was
prepared hydrothermally from a mixture of CoCl2 ·
6H2O, 1,2,4,5-benzentetracarboxylic dianhydride, and
H2O in a molar ratio of 1 : 1 : 1200 by heating in a
teflon-lined stainless steel autoclave at 140°C for
3 days under static conditions, and the filling volume is
75%. After cooling the reaction mixture to room tem-
perature, only the colorless grain-like crystals appeared
together with pink solutions. The crystals obtained
were separated and multiply washed with distilled
water and ethanol. Finally, the products were dried in
air at room temperature. The yield was 40%.
For C22H20CoN2O12
anal. calcd, %: C, 46.91; H, 3.58; N, 4.97; Co, 10.46.
Found, %:
C, 46.81; H, 3.65; N, 4.90; Co, 10.35.
IR spectrum (ν, cm–1): 425 m, 461 w, 481 w, 599 m,
644 w, 674 s, 730 vs, 755 s, 775 w, 848 vs, 869 m, 959 w,
1104 w, 1149 m, 1223 w, 1294 m, 1349 vs, 1426 s,
1516 w, 1582 w, 1692 s, 1819 w, 1994 w, 2367 w, 3459 s.
Crystal structure determination and refinement.
Suitable single crystals with dimensions of 0.53 ×
0.47 × 0.45 mm for I, 0.50 × 0.48 × 0.41 mm for II and
0.25 × 0.18 × 0.12 mm for III were carefully selected
under an optical microscope and glued to a thin glass
fiber with epoxy resin. X-ray intensity data were mea-
sured at 298(2) K on a Bruker SMART APEX CCD-
based diffractometer (MoKα radiation, λ = 0.71073 Å).
The raw frame data for the compound were integrated
into SHELX-format reflection files and corrected for
Lorentz and polarization effects using SAINT [23].
Corrections for incident and diffracted beam absorption
effects were applied using SADABS [23]. Compounds
I, II, and III crystallized in the space group P1, P2/m,
and P21/n, respectively, as determined by systematic
absences in the intensity data, intensity statistics, and
the successful solution and refinement of the structures.
All structures were solved by a combination of direct
methods and difference Fourier syntheses and refined
against F2 by the full-matrix least-squares technique.
Crystal data, collection parameters, and refinement sta-
tistics for compounds I–III are listed in Table 1.
Selected bond distances and bond angles are given in
Table 2. The atomic coordinates and thermal parame-
ters are listed in Table 3. Hydrogen bond geometry in
structures I–III is showed in Table 4.
For C10H10O10
anal. calcd, %:
Found, %:
C, 41.39;
C, 41.30;
H, 3.47.
H, 3.54.
IR spectrum (ν, cm–1): 272 w, 278 w, 349 m, 401 w,
461 m, 510 w, 557 m, 651 m, 754 s, 816 s, 932 w,
959 m, 1077 w, 1118 s, 1250 vs, 1279 sh, 1306 vs,
1415 sh, 1445 m, 1511 s, 1612 m, 1674 vs, 1709 ssh,
1901 w, 2017 m, 2510 m, 2603 w, 2652 w, 2822 w,
2960 w, 3059 w, 3141 s, 3398 m, 3529 ssh.
Synthesis of [Co(H2O)6(H2Btec)]n (II). The com-
pound was prepared hydrothermally from a mixture of
CoCl2 · 6H2O, 1,2,4,5-benzentetracarboxylic dianhy-
dride, ammonium molybdate (NH4)Mo7O24 · 6H2O, and
H2O in a molar ratio of 1 : 2 : 1 : 900 by heating in a
teflon-lined stainless steel autoclave at 160°C for 3 days
under static conditions, and the filling volume is 75%.
After cooling the reaction mixture to room temperature,
only the pink grain-like crystals appeared on the walls
of the reaction container together with pink solutions
and an amorphous substance. The crystals obtained
were separated and washed with distilled water and eth-
anol many times. Finally, the products were dried in air
at room temperature. The yield was 20%.
For C10H16CoO14
RESULTS AND DISCUSSIONS
anal. calcd, %:
Found, %:
C, 28.65;
C, 28.73;
H, 3.85.
H, 3.76.
Co, 14.06.
Co, 14.01.
Synthesis and characterization. Hydrothermal
synthesis was employed to obtain single crystals suit-
able for detailed structure studies, and all the single
IR spectrum (ν, cm–1): 245 w, 341 w, 425 m, 705 s, crystals obtained are very stable in air. Compounds I
745 s, 889 w, 1101m, 1157 vs, 1284 s, 1349 vs, 1586 s, and II were obtained in low yield despite little varia-
1666 s, 3457 vs.
tions in the synthesis conditions. Experiments with var-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

FUNCTIONAL SELF-ASSEMBLY OF 3D NETWORKS
473
Table 1. Summary of crystallographic data and structure re-
finement for I–III
ious reactant ratios and temperature were carried out
but no satisfactory high-yield synthesis has yet been
developed for the two compounds. A noteworthy find-
ing is that no crystals were found for II except for the
pink solutions if ammonium molybadate (NH4)Mo7O24 ·
6H2O used as the mineralization reagent was not added.
At the same time, the replacing (NH4)Mo7O24 · 6H2O
with NH4Cl, NaCl and other neutral salts does not form
suitable single crystals.
Compound
I
II
III
Formula weight
290.18
419.16
563.33
Crystal system Triclinic
Monoclinic Monoclinic
Space group
a, Å
P1
P2/m
P21/n
7.081(4)
22.533(12)
14.772(8)
90
The composition analyzing for I–III is in good
agreement with the calculated values based on the
empirical formulas C10H10O10, C10H16O14Co, and
C22H20N2O12Co given by single-crystal structure analy-
ses. Compounds II and III showed a similar thermal
behaviour and have higher thermal stability than I. For
I, a weight loss from 70 to 110°C (12.40%) corresponds
well to the loss of the uncoordinated water (calcd
12.41%). Decomposition of I begins at 210°C and is
complete at about 300°C (Fig. 1a). Three steps are
observed in the TG/DTA curves of II (Fig. 1b): the first
one occurs at 100°C and a weight loss of 25.71% corre-
sponding to the water release (calcd 25.77%) takes
place together with an obviously endothermic peak.
The other two overlapped weight loss sidesteps are
observed from 200 to 400°C, which are ascribed to
complex II decomposing and further forming metal
oxides like Co2O3. While for III one sidestep and three
overlapped sidesteps in TG curves were found
(Fig. 1c). The first one (12.29%) is attributed to the
release of water (calcd 12.31%) together with a weak
endothermic peak. The other three ones are followed by
two weak endothermic peaks and one strong exother-
mic peak, whose weight losses corresponded to the
release of H2Btec, and Phen groups and the formation
of Co2O3, respectively. Stretching frequencies of the
infrared spectra at 3141, 2652, 2510, 1709 and
1674 cm–1 for I confirmed the presence of the non-ion-
ized COOH [24]. The infrared spectra of II and III are
quite similar with a broad band centred at 3457 and
3459 cm–1, which is due to the O–H stretching vibration
of water molecules involved in extensive hydrogen
bonding interactions [25]. The stretching frequencies at
1666, 1586, and 1349 cm–1 for II attributed to
νas(COO) and νs(COO) vibrations of the carboxylate
groups. At the same time, the main FT-IR spectra of
compound III exhibit the νas(COO) and νs(COO) vibra-
tions of the carboxylate groups at 1692 and 1426 cm–1.
It is known that the difference in νas(COO) and
νs(COO) (∆ν), is currently employed to determine the
corresponding mode of the carboxylate group. ∆ν is ca.
266 cm–1 for complex III, and the value suggests the
occurrence of monodentate coordination of the carbox-
ylate groups [26]. This is also in agreement with the
crystal structure proved by the single crystal results
below.
5.4804(19) 6.513(5)
b, Å
6.475(2)
9.138(3)
72.114(4)
88.896(5)
73.436(5)
294.97(17)
1
9.940(8)
6.549(5)
90
c, Å
α, deg
β, deg
γ, deg
Volume, Å3
Z
115.388(8)
90
97.807(9)
90
383.0(5)
1
2335(2)
4
ρ
calcd/g cm–3
1.634
1.817
1.198
1884
1.602
µ, mm–1
0.151
0.806
Reflections
collected
1518
11390
Independent
reflections
1014
688
3955
(Rint = 0.0220) (Rint = 0.0471) (Rint = 0.0912)
Final R indices R1 = 0.0563, R1 = 0.0657, R1 = 0.0878,
(I > 2σ(I))
wR2 = 0.1338 wR2 = 0.1820 wR2 = 0.1915
R indices
(all data)
R1 = 0.0618, R1 = 0.0687, R1 = 0.154,
wR2 = 0.1433 wR2 = 0.1838 wR2 = 0.2258
endocyclic angles in the benzene ring of H4Btec are
119.63(16)° and 119.64(16)° for the substituted C atoms
and 120.72(17)° for the unsubstituted C atoms. The exo-
cyclic angles C(2)C(4)C(3), C(4)C(3)C(1) and their
corresponding complementary angles C(5)C(4)C(2)
and C(5)#1C(3)C(1) are 120.23(15)°, 121.81(16)°,
120.06(16)°, and 118.35(16)° (symmetry code: #1 – x +
3, –y+ 3, –z + 3), respectively (Fig. 2a). It is obvious that
all of the exocyclic, endocyclic, and their complemen-
tary angles are close to 120° in the parent acid H4Btec.
The structure analysis also reveals that the mole-
cules are arranged in such a manner that adjacent acid
molecules constitute chains through O(1)–H(1)···O(3)
hydrogen bonds (distances of H(1)···O(3) and
O(3)···O(1) and angles ofO(1)–H···O(3) are 1.88 and
2.683 Å and 164.23°, respectively) as shown in Fig. 3a.
Water molecules hold these chains together by forming
Crystal structure of I. The structure of the H4Btec O(4)−H(4)···O(5) and O(5)–H(6)···O(2) hydrogen bonds
hydrate was solved. It forms a 3D O–H···O hydrogen- or O(4)–H(4)···O(5) and O(5)–H(7)···O(2) hydrogen
bonded network with water molecules. The arrange- bonds leading to the formation of a closed network with
ment of the molecules in complex I showed that the two kinds of adjacent cavities, and the water molecules
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

474
BO et al.
tutes bilayers, which stack further, to generate, a 3D
Weight, %
100
Heat flow endo down, mW
(‡)
O−H···O hydrogen-bonded network.
0
Crystal structure of II. Crystalline compound II
has an ionic structure built of [Co(H2O)6]2+ dications
and dianions of doubly deprotonated H2Btec2–, which
are linked to each other only through hydrogen bonds
and ionic interactions. The local environment around
the [Co(H2O)6]2+ ion is depicted in Fig. 2b. The endocy-
clic angles in the benzene ring of the H2Btec2– is
117.7(2)° for the substituted C atoms and 124.6(5)° for
the unsubstituted C atoms. The exocyclic angle
C(3)C(2)C(1) is 113.7(4)°, while a complementary
angle C(2)#2C(2)C(1) is 128.6(2)° (symmetry code:
#2 x, –y, z) is obviously wider. This is different from
compound I, in which all the exocyclic angles are close
to 120°.
80
60
40
20
–10
–20
–30
–40
0
0
100
200
300
400
500
Figure 2b also shows that the Co2+ ion is surrounded
by six water ligands, exhibiting a slightly distorted
octahedral stereochemistry. The Co2+ ion occupies a
special position on a twofold axis, one pair of the O
atoms being on the twofold axis and the other four O
atoms being related to each other in pairs by this axis.
The Co–O distances are in the range 2.045(4)—
2.115(5) Å, and OCoO angles are between 89.4(3)° and
90.6 (3)° in a parallelogram plane.
At the same time, it is evident that two neighboring
H2Btec2– anions are connected by water molecules
through weakly intermolecular hydrogen bond
O(1)°(5), O(1)°(4), O(2)°(3) and strongly intramolecular
hydrogen bond O(2)°(2)#1 (symmetry code: #1 – x + 3,
–y + 3, –z + 3) with the bonding distances 2.809, 2.788,
2.823, and 2.386 Å, respectively. The diagram shows
that the ions are held together by a very extensive
hydrogen-bonding system. All the hydrogen atoms of
the aqua ligands are involved in intermolecular hydro-
gen bonds with the carboxylate oxygen atoms or
between themselves and play an important stabilizing
role in the crystal packing energy. As a result, the sand-
wich-like structure exhibiting supramolecular isomers
was formed (Fig. 3c).
150
100
50
(b)
100
80
60
0
40
–50
20
0
200
400
(c)
600
800
1000
100
80
60
40
20
150
100
50
0
Crystal structure of III. Single-crystal X-ray anal-
ysis reveals that complex III exhibits a 3D framework
built from mononuclear units. The central cobalt ion is
depicted as shown in Fig. 2c. The endocyclic angles in
the benzene ring of H2Btec2– are 126.9(5)° and 125.6(6)°
for the unsubstituted C atoms and 115.6(6)°, 117.1(6)°,
and 117.5(5)° for the substituted C atoms. The exocy-
clic angles C(5)C(6)C(2), C(8)C(9)(4), C(6)C(5)C(1),
and C(9)C(8)C(3) and their corresponding complemen-
–50
0
0
200
400
600
800
1000
Temperature, °C
Fig. 1. TG–DTA curves for compounds (a) I, (b) II, and (c) III.
tary
angles
C(7)C(6)C(2),
C(10)C(9)C(4),
C(10)C(5)C(1), and C(7)C(8)C(3) are 117.5(5)°,
129.1(6)°, 129.3(5)°, 129.4(6)°, 114.3(6)°, 113.8(6)°,
115.1(6)°, and 113.4(6)°, respectively.
can be regarded as filling small cavities. In the arrange-
ment above, the layers are stacked in such a way that
the cavities similarly align to yield two kinds of adja-
cent channels as shown in Fig. 3b, and water molecules
lie in small channels. Therefore, the stacking of the
sheets is quite interesting as each of the two adjacent
Figure 2c also shows that each cobalt atom has a six-
coordinate distorted octahedral environment, which is
defined by two nitrogen donors from Phen molecule,
three aqua O atoms, and the carboxylate O atom from
layers connected by O−H···O hydrogen bonds consti- one H2Btec2– ligand (thereinto, two carboxylate groups
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

FUNCTIONAL SELF-ASSEMBLY OF 3D NETWORKS
475
(‡)
O(4)
C(5)
C(2)
C(4)
O(3)
O(5)
C(3)
(b)
C(1)
O(2)
O(1)
O(2)
C(1)
O(1)
C(2)
O(5)
Co(1)
O(3)
C(3)
O(4)
(c)
O(12)
O(3)'
O(9)
O(2)'
O(11)
O(4)
C(20)
C(16)
C(19)
C(18)
O(2)
C(5)
N(2)
O(3)
C(2)
Co(1)
O(1)
C(6)
C(7)
C(1)
C(17)
C(22)
O(5)
N(1)
C(14)
O(10)
C(10)
C(15)
C(8)
C(9)
O(7)
C(3)
C(11)
C(12)
C(21)
C(4)
O(8)
C(13)
O(6)
Fig. 2. Structure of compounds (a) I, (b) II, and (c) III.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

476
BO et al.
(a)
0
z
x
y
(b)
Fig. 3. (a) 3D O–H···O hydrogen bonded network of I, (b) packing diagram of compound I, (c) 3D O–H···O hydrogen bonded net-
work of II, and (d) 3D O–H···O hydrogen bonded network of III.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

FUNCTIONAL SELF-ASSEMBLY OF 3D NETWORKS
477
(c)
y
0
x
z
(d)
z
x
0
y
Fig. 3. Continued.
at the meta position are deprotoned; only one charge-compensating anions). At the same time, the
(C(1)O(2)O(1)) binds to the cobalt ions in a monoden- octahedrally coordinated cobalt complex consists of
date manner, and the other (C(4)O(8)O(7)) used as the two peak sites occupied by atoms O(9) and O(10) with
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

478
BO et al.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

FUNCTIONAL SELF-ASSEMBLY OF 3D NETWORKS
479
Table 3. Coordinates (×104) and equivalent isotropic termal parameters (×103) of atoms in crystal structures I–III
Atom
x
y
z
Ueq, Å2
Atom
x
y
z
Ueq, Å2
I
O(5)
O(6)
O(7)
O(8)
O(9)
7126(11) 5186(3)
825(4)
612(3)
101(2)
70(2)
64(2)
63(2)
55(1)
92(2)
61(2)
129(3)
46(2)
51(2)
60(2)
45(2)
34(2)
34(2)
38(2)
36(2)
34(2)
39(2)
69(3)
72(3)
62(2)
44(2)
41(2)
41(2)
46(2)
60(2)
61(2)
60(2)
50(2)
50(2)
O(1)
O(2)
O(3)
O(4)
O(5)
C(1)
C(2)
C(3)
C(4)
C(5)
17389(3) 15940(3) 11156(1)
13268(3) 17841(3) 10871(1)
13488(3) 12955(3) 11907(1)
11149(3) 11945(3) 13875(2)
9212(2) 10181(2) 12192(2)
15149(3) 16566(3) 11679(2)
12799(3) 12940(3) 13181(2)
15145(3) 15660(3) 13403(2)
13881(3) 14049(3) 14115(2)
13744(3) 13410(3) 15705(2)
II
41(1)
44(1)
40(1)
40(1)
35(1)
27(1)
26(1)
25(1)
25(1)
26(1)
7767(8)
7809(8)
7149(8)
4496(7)
6107(3)
7032(2)
7353(2)
6834(2)
6747(2)
5977(2)
1461(3)
2766(3)
6288(3)
6910(5)
7231(3)
8801(5)
5080(5)
3965(5)
1136(5)
2272(5)
4084(4)
3595(4)
2652(4)
2151(4)
2632(4)
3560(4)
5130(6)
4813(5)
5454(5)
6363(5)
6601(5)
7536(5)
8192(5)
9088(5)
9266(5)
8587(5)
7066(6)
7927(5)
O(10) 10227(8)
O(11)
O(12)
C(1)
7142(8)
5931(12) 5600(4)
7522(11) 5865(3)
7568(12) 4600(3)
7459(13) 5673(4)
7480(10) 6949(3)
C(2)
C(3)
C(4)
Co(1)
O(1)
O(2)
O(3)
O(4)
O(5)
C(1)
C(2)
C(3)
5000
5000
0
20(1)
40(1)
37(1)
36(1)
43(1)
48(1)
25(1)
20(1)
20(1)
C(5)
7519(9)
7539(9)
7521(9)
7504(9)
7469(9)
7458(9)
5767(3)
5226(3)
5261(3)
5778(3)
6315(3)
6279(3)
1233(5)
–1142(5)
5000
2883(3)
1200(3)
7128(4)
5000
3056(6)
1997(6)
0
C(6)
C(7)
C(8)
8236(7)
2520(9)
2418(10)
2923(7)
3933(6)
5000
C(9)
3755(10) 5000
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
884(7)
2909(7)
5000
1672(4)
7553(13) 7813(3)
7604(14) 8402(4)
7663(12) 8854(3)
7592(10) 8719(3)
7494(10) 8115(3)
7426(10) 7962(3)
7394(10) 8405(3)
7307(12) 8215(4)
7120(13) 7634(3)
7189(12) 7230(3)
7543(10) 9159(3)
7484(10) 9020(3)
710(4)
1363(5)
III
Co(1)
N(1)
N(2)
O(1)
O(2)
O(3)
O(2')
O(3')
O(4)
7380(2)
7518(9)
7314(8)
7553(8)
6813(1)
7670(2)
7383(2)
6377(2)
6597(1)
6003(4)
7730(4)
5358(3)
5652(10)
4829(11)
44(1)
49(2)
44(2)
58(2)
65(5)
68(6)
63(7)
68(7)
57(1)
7730(50) 5426(6)
7920(50) 4505(7)
6670(90) 5466(15) 5540(20)
6880(90) 4519(14) 4770(20)
7517(8)
4187(2)
3443(4)
angles of 177.0(2)° for O(10)Co(1)O(9), and the dis- 77.5(2)°, and 93.07(19)° for O(1)Co(1)O(11),
O(11)Co(1)N(2), N(2)Co(1)N(1), and N(1)Co(1)O(1),
respectively.
tance 2.012(6) Å of Co(1)–O(10) is shorter than
2.032(5) Å of Co(1)–O(9) owing to of the Jahn–Teller
effect. The quadrilateral plane was formed by the O(1),
O(11), N(1), and N(2) atoms. The Co(1)–O(1),
Co(1)−O(11), Co(1)–N(1), and Co(1)–N(2) distances
are 2.096(4), 2.121(5), 2.128(6), and 2.114(5) Å,
respectively. The angles of the type OCo(1)O,
At the same time, a difference between the C–O
bond distances is observed. The C(3)–O(6) distance
(1.284(9) Å) is longer than C(3)–O(5) (1.200(10) Å) in
the protonated carboxylic group. Similarly, the
C(4)−O(8) distance (1.208(8) Å) is shorter than
NCo(1)N, and OCo(1)N are 89.25(19)°, 100.3(2)°, C(4)−O(7) (1.266(9) Å) in the deprotonated carboxylic
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

480
BO et al.
Table 4. Hydrogen bond geometry in structures I–III
ized by elemental analysis, FT-IR, TG/DTA, and sin-
gle-crystal XRD.
H bond
Distance, Å
D···A
Single-crystal XRD results showed that I forms a
3D O–H···O hydrogen-bonded network generated from
H4Btec and water molecules. Compound II presents a
3D network constructed by mononuclear [Co(H2O)6]2+
and H2Btec2– through extensive hydrogen-bonding
interactions. Compound III features a 3D hydrogen-
bonded network linking octahedral hexaaquacobalt(II)
dications and (H2Btec)2– dianions, and intramolecular
hydrogen bonds between adjacent carboxyl groups in
(H2Btec)2– were also found.
Crystallographic information on C10H10O10,
C10H16O14Co, and C22H20O12N2Co has been deposited
in the Cambridge Crystallographic Data Center as sup-
plementary publication number CCDC 608247,
295866, and 608248, respectively. Copies of the data
can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax:
+44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk
or web-site: http://www.ccdc.cam.ac.uk).
Coordinates of atom A
D–H···A
I
2.683
2.574
2.792
2.876
3.109
II
O(1)–H(1)···O(3)
O(4)–H(4)···O(5)
O(5)–H(6)···O(2)
O(5)–H(7)···O(2)
O(5)–H(7)···O(3)
–x + 3, –y + 3, –z + 2
x, y, z
x, y –1, z
–x + 2, –y + 3, –z + 2
x – 1, y, z
O(2)–H(2)···O(2)
O(3)–H(4)···O(2)
O(4)–H(5)···O(1)
O(5)–H(6)···O(1)
2.386
2.823
2.788
2.809
III
x, –y, –z
x + 1, –y + 1, z
x + 1, –y + 1, z
x, –y + 1, z
O(3)–H(3)···O(2)
2.418
2.435
2.431
2.763
3.282
2.847
3.282
2.665
2.725
2.728
3.334
x, –y, –z
ACKNOWLEDGMENTS
O(3')–H(3')···O(2')
O(6)–H(6)···O(7)
x, –y, –z
x, –y, –z
This work was supported by the Doctoral Founda-
tion of Jinan University.
O(9)–H(23)···O(4)
O(9)–H(23)···O(10)
O(9)–H(24)···O(7)
O(10)–H(25)···O(9)
O(100–H(26)···O(8)
O(11)–H(27)···O(2)
O(11)–H(27)···O(2')
O(11)–H(28)···O(4)
–x + 1, –y + 1, –z + 1
x – 1, y, z
REFERENCES
x – 1/2, –y + 3/2, z + 1/2
x + 1, y, z
1. Jones, W., Organic molecular solids: Properties and
Applications, New York: CRC Press, 1997, p. 149.
2. Bond, A.D. and Jones, W., Supramolecular Organiza-
tion and Materials Design, eds. W. Jones and
C.N.R. Rao, Cambridge: Cambridge Univ. Press, 2002,
p. 391.
x + 1/2, –y + 3/2, z + 1/2
x, –y, –z
x, –y, –z
3. Desiraju, G.R., Crystal engineering: The Design of Or-
ganic Solids, Amsterdam: Elsevier, 1989.
–x + 1, –y + 1, –z + 1
x, –y, –z
O(12)–H(29)···O(11) 2.715
4. Lightfoot, P. and Snedden, A., Dalton Trans., 1999,
p. 3549.
5. Dong, Y.B., Smith, M.D., Layland, R.C. , zur Loye, H.-C.,
Dalton Trans., 2000, p. 775.
O(12)–H(30)···O(6)
O(12)–H(30)···O(5)
3.035
3.137
x, y, z + 1
x, y, z + 1
6. Biradha, K., Domasevitch, K.V., Moulton, B., et al.,
Chem. Commun., 1999, p. 1327.
7. Gudbjartson, H., Biradha, K., Poirier, K.M., Zaworot-
ko, M.J., J. Am. Chem. Soc., 1999, vol. 121, no. 11.
p. 2599.
8. Jeffrey, G.A., An Introduction to Hydrogen Bonding,
New York: Oxford Univ. Press Inc., 1997.
9. Desiraju, G.R. and Steiner, T., The Weak Hydrogen
Bond in Structural Chemistry and Biology, Oxford: Ox-
ford Univ. Press, 1999.
10. Row, T.N.G., Coord. Chem. Rev., 1999, vol. 183,
no. 1, p. 81.
11. Aakeroy, C.B., Acta Crystallogr., 1997, vol. 53B,
p. 569.
group. This is due to the presence of the intermolecular
hydrogen bond O(6)°(12) and intramolecular hydrogen
bond O(6)°(7). On the other hand, the disordered atoms
(O(3)', H(3)' and O(2)') were also found, and the angles
C(2)O(3)'H(3)', O(1)C(1)O(2)', and O(4)C(2)O(3)' are
109.5°, 117.2(17)°, and 118.2(15)°, respectively. To sum
up, several kinds of hydrogen bonds generated from the
H2Btec2– anions, coordinated water and uncoordinated
water molecules in the title compound are present (see
Table 4). These interactions link the mononulear units
into a 3d network structure as shown in Fig. 3d.
So three novel inorganic–organic complexes formu-
lated as [H4Btec · 2H2O]n (I), [Co(H2O)6(H2Btec)]n (II),
and {[Co(H2O)3(H2Btec)(Phen)] · H2O}n (III) were
prepared under hydrothermal conditions and character-
12. Allen, F.H., Howard, J.A.K., Hoy, V.J., et al., J. Am.
Chem. Soc., 1996, vol. 118, p. 4081.
13. Pedireddi, V.R., Jones, W., Chorlton, A.P., and Docher-
ty, R., Chem. Commun., 1996, p. 997.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007

FUNCTIONAL SELF-ASSEMBLY OF 3D NETWORKS
481
14. Pedireddi, V.R., Ranganathan, A., and Chatterjee, S., 20. Shi, X., Zhu, G., Wang, X., et al., Crystal Growth & De-
Tetrahedron Lett., 1998, vol. 39, p. 9831.
sign., 2005, vol. 5, no. 1, p. 207.
21. Wu C.D., Lu C.Z., and Yang, W.B., Eur. J. Inorg.
Chem., 2002, p. 797.
22. Wan, Y., Zhang, L., Jin, L., et al., Inorg. Chem., 2003,
vol. 42, no. 16, p. 4985.
23. Bruker Analytical X-ray Systems, Inc., Madison (WI,
USA), 1998.
24. Chapman D., J. Chem. Soc., 1955, p. 1766.
25. Cecconi, F., Ghilardi, C.A., et al., Inorg. Chem. Com-
mum., 2002, vol. 5, p. 1041.
26. Nakamoto, K., Infrared and Raman Spectra of Inorganic
and Coordination Compounds. Wiley-Interscience Pub-
lication. John wiley & Sons, Inc. 1986.
15. Li, Y.G., Hao, N.H., Wang, E.B., et al., Eur. J. Inorg.
Chem., 2003, p. 2567.
16. Ghosh, S.K. and Bharadwaj, P.K., Inorg. Chem., 2004,
vol. 43, no. 17, p. 5180.
17. Cao, R., Shi, Q., Sun, D.F., et al., Inorg. Chem., 2002,
vol. 41, no. 23, p. 6161.
18. Delgado, L.C., Fabelo, O., Poerez, C.R., and
Delgado, S., Crystal Growth & Design., 2006, vol. 6,
no. 1, p. 87.
19. Perez, C.R., Luis, P.L., Molina, M.H., et al., Eur. J. In-
org. Chem., 2004, p. 3873.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 7 2007