КООРДИНАЦИОННАЯ ХИМИЯ, 2015, том 41, № 10, с. 610-618
УДК 541.49
THREE NEW Co(II)/Ni(II) CORDINATION POLYMERS BASED ON 3,3-BIPHENYL DICARBOXYLIC ACID AND N-DONOR CO-LIGANDS: SYNTHESIS, CRYSTAL STRUCTURES, AND MAGNETIC PROPERTIES
© 2015 H. B. Wang1, Y. P. Wu2, *, G. W. Xu2, J. F. Wang2, and S. S. Guo2
1 College of Mechanical & Power Engineering, China Three Gorges University, Yichang, 443002 P.R. China
2 College of Materials & Chemical Engineering, China Three Gorges University, Yichang, 443002 P.R. China
*E-mail: wyapan2008@163.com Received February 10, 2015
Three new Co(II)/Ni(II) cordination polymers [Co(Bpdc)(Bipy)]n (I) and [Co2(Bpdc)2(Dps)2]n (II) and [Ni(Bpdc](Dps)]n (III) (H2Bpdc = 3,3'-biphenyl dicarboxylic acid, Bipy = 2,2'-bipyridine, and Dps = 4,4'-dipyridyl sulfide) have been synthesized via hydrothermal method and characterized by elemental analysis, FT-IR, PXRD and single-crystal X-ray diffraction (CIF files CCDC nos. 994521 (I), 994522 (II), 1027995 (III)). Compound I is a 3D supremolecular structures extending through 1D double chain by the n---n stack interactions. However, compound II and III are topological isomorphic, which features a 3D four-fold interpenetrated neworks with 4-connected dia topology. Moreover, ther-mogravimetric analysis and magnetic properties of I and II were also discussed.
DOI: 10.7868/S0132344X15100096
INTRODUCTION
Recently, there are a great of interests which are focused on the synthesis, crystal structure and properties study of metal-organic frameworks for their potential application in the field of luminescence, magetism, catalyst and so on [1—9]. In this context, the rational design and synthesis diverse structural topologies with specific functions are always of great challenge for the chemists. In order to solve this problem, the action of organic building blocks with polytropic configurations has been investigated in the process of assembling MOFs. It is well known that the aromatic polycarbox-ylates are widely used in the construction of coordination polymers because of their diverse coordination modes [10—13]. Among these, 4,4'-biphenyl dicarboxylic acid, 3,4'-biphenyl dicarboxylic acid, and 3,3'-biphenyl dicarboxylic acid (H2Bpdc), have extensively employed to construct many coordination polymers with different strutures and properties due to their flexible coordination modes [14—18]. Furthermore, the N-containing ligands, such as pyridine and imidazole derivatives, have supper coordinaition pro-peritity on transition metal ions, and they have different function in the construction of MOFs [19—21].
In our privious work, two Zn (II) and Cd (II) coordination compounds based on H2Bpdc (Scheme 1) have been obtained and characterized [22]. Two possible geometrical configurations of H2Bpdc ligand: cis-configuration (a), trans-configuration (b) are in Scheme 1.
OH
HO
OH
O
O O
O
(a)
(b)
HO
Scheme 1.
In order to do further investigation on the vertial coordination mode of H2Bpdc and the synergic action between the Bpdc ligand and bipyridyl derivates, herein, three new Co(II)/Ni(II) cordination polymers, namely [Co(Bpdc)(Bipy)]„ (I), [Co2(Bpdc)2(Dps)2]„ (II), and [Ni(Bpdc](Dps)]„ (III) (Bipy = 2,2'-bipyridine, Dps = 4,4'-dipyridyl sulfide) have been successfully synthesized and characterized. Moreover, the thermal stability and magnetic properties of compounds I and II has also been investigated.
EXPERIMENTAL
Materials and instrumentation. The organic ligands employed were received from Alfa Aesar and other inorganic salt and solvents were received as reagent grade and used without any further purification. Elemental analyses were performed with a PerkinElmer 2400 Series II analyzer. The IR spectra were measured as KBr pellets with a FT-IR Nexus spectrophotometer from 4000 to 400 cm-1. Powder X-ray diffractions (PXRD) patterns were recorded on a Rigaku Ultima IV diffrac-
tometer with CuK"a radiation (k = 1.5406 A). The simulated powder patterns were calculated using Mercury 1.4. The purity and homogeneity of the bulk products were determined by comparison of the simulated and experimental X-ray powder diffraction patterns. Thermogravimetric analysis (TGA) was taken with a NETZSCH STA 449C microanalyzer in under an air atmosphere at a heating rate of 10°C min-1. Variable-temperature magnetic measurements were carried out on a Quantum Design SQUID MPMS XL-7 instrument in the magnetic field of 1 kOe, and the diamagne-tic corrections were evaluated using Pascal's constants.
Synthesis of compound I. A mixture of Co(NO3)2 • • 6H2O (29.7 mg, 0.10 mmol), 3,3'-H2Bpdc (24.2 mg, 0.10 mmol), 2,2'-Bipy (15.6 mg, 0.10 mmol), and NaOH (8.0 mg, 0.20 mmol) in a solution of H2O (7 mL) were sealed into a 23 mL Teflon-lined stainless steel container under autogenous pressure, heated at 140°C for 3 days and cooled to room temperature for 24 h. Purple prismatic single crystals suitable for X-ray analyses were obtained. The yield was 67% (based on Co(II)).
For C24H16N2O4Co
anal. calcd., %: C, 63.31; H, 3.54; N, 6.15. Found., %: C, 63.22; H, 3.49; N, 6.23.
IR (KBr pellet; v, cm-1): 2968 w, 1606 w, 1560 m, 1542 s, 1473 w, 1441 m, 1419 s, 1385 m, 1361 s, 1269 w, 1157 w, 1081w, 1022 w, 904 w, 863 w, 757 s.
Synthesis of compound II was carried out in a similar method used for I except that Bipy was rehlaced by Dps (18.8 mg, 0.10 mmol). The yield was 43% (based on Co(II)).
For C48H32N4O8S2Co2
anal. calcd., %: Found., %:
C, 59.14; C, 59.35;
H, 3.31; H, 3.53;
N, 5.75. N, 5.83.
IR (KBr pellet; v, cm-1): 3217 w, 1589 m, 1534 m, 1481 w,1413 s, 1372 m, 1266 w 1183 w, 1057 w, 1022 w, 862 w, 830 w, 812 w, 793 m, 760 s, 732 m.
Synthesis of compound III was carried out in a similar method to that of II. The yield was 38% (based on Ni(II)).
Fig. 1. The coordination enviroment center of Co(II) in I. Symmetry codes: #1 x — 1, y, z + 1; #2 —x + 1, -y + 1, —z.
phite monochromated MoAa radiation (k = 0.71073 A). The collected data were reduced using the program CRYSTALCLEAR and an empirical absorption correction was applied [23]. The structure was solved by direct methods and refined based on F2 by the full matrix least-squares methods using SHELXTL [24, 25]. The hydrogen atoms were assigned with common iso-tropic displacement factors and included in the nal re-nement by use of geometrical restrains. Generally, the positions of C/N-bound H atoms were generated by a riding model on idealized geometries. The crystallo-graphic data for I—III are listed in Table 1 and selected bond lengths and angles are given in Table 2.
The supplementary crystallographic data for I—III been deposited the Cambridge Crystallographic Data Centre (CCDC nos. 994521 (I), 994522 (II), 1027995 (III); deposit@ccdc.cam.ac.uk or http://www.ccdc. cam.ac.uk).
For C24H16N2O4SNi
anal. calcd., %: C, 59.17; H, 3.31; N, 5.75. Found., %: C, 59.25; H, 3.27; N, 5.93.
IR (KBr pellet; v, cm-1): 3445 m, 2922 w, 2981 w, 1622 s, 1584 s, 1540 m, 1480 w, 1409 s, 1384 s, 1315 w, 1213 w, 828 w, 756 m.
X-ray structure determination. Single crystal X-ray diffraction analysis of compounds I—III were carried out on a Rigaku XtaLAB mini diffractometer with gra-
RESULTS AND DISCUSSION
Single crystal structure analysis shows that the asymmetric unit of compound I consists of one Co2+ ion, one Bpdc and one Bipy ligand. Each Co2+ ion is six-coordinated by two nitrogen donors (N(1) and N(2)) from one bipy ligand and four carboxylate oxygen donors (O(1), O(2), O(3)#1 and O(3)#2, symmetry codes: #1 x — 1, y, z + 1; #2 —x + 1, —y + 1, —z) from three 3,3'-Bpdc ligands, thus generating an octhedral geometrical configuration (Fig. 1). The coordination
(a) (b)
(c)
(d)
z X
Fig. 2. View of the 1D double chain along the zaxis (a); the 2D layer constructed by 1D double chain via the n—n interaction (b); the adjacent layers via the weak interaction (c); the packing 3D supramolecular structures of I (d).
Co-O/N bonds, varying from 2.344(3) to 2.608(3) A, are within the reported results [26].
Four coordination modes of Bpdc in I—III:
i^-n^nW (A); i^-n1:^1 (B); ^2-n1:n1:n1 (C); ^2-n1:n1:n1:^1 (D) are given in Scheme 2:
Scheme 2.
In I, the adjacent Co2+ ions are linked by two Bpdc result in the 1D double chain structures along the z ax-ligands with the |3-n1:n1:n2 (type A; Scheme 2), wich is (Fig. 2a). These chains extended into the 2D layer in
Table 1. Crystallographic data and structure refinement information for compounds I—III
Parameter Value
I II III
Formula weight 455.32 974.76 487.16
Temperature (K) 296(2) 296(2) 296(2)
Crystal system Triclinic Monoclinic Orthorhombic
Space group P1 P2x/c Pbca
Unit cell dimensions
a, A 10.173(6) 17.409(7) 17.7833(3)
b, A 10.396(6) 11.827(5) 11.9359(2)
c, A 11.940(7) 20.220(8) 19.3104(3)
a, deg 72.60(3) 90 90
P, deg 66.70(3) 92.757(6) 90
Y, deg 61.04(3) 90 90
Volume, A3; Z 1005.6(10); 2 4158(3); 4 4098.82; 8
Pcalcd mg/m3 1.504 1.557 1.579
^(MoZa), mm-1 0.888 0.961 1.085
/(000) 466 1992 2000
9 Range, deg 2.45-27.53 3.02-27.46 2.11-27.56
Limiting indices -13 < h < 13 -13 < k < 13 -15 < l < 15 -22 < h < 22 -15 < k < 15 -26 < l < 26 -20 < h < 23 -15 < k < 13 -19 < l < 25
Crystal size, mm 0.23 x 0.21 x 0.16 0.16 x 0.14 x 0.10 0.18 x 0.16 x 0.15
Reections collected 10724 43410 19106
Independent reflection (Rint) 4607 (0.0730) 9496 (0.0894) 4736 (0.0274)
Data/restraints/parameters 4607/0/280 9496/0/577 4736/0/289
Goodness-of-fit on F2 1.011 1.098 1.021
R1*, wR2** (I> 2ct(I)) 0.0595, 0.1642 0.0538, 0.1114 0.0328, 0.0838
R1*, wR2** (all data) 0.0719, 0.1727 0.0750, 0.1219 0.0492, 0.0927
^max^mi^ e A-3 1.212/—0.880 0.549/-0.497 0.341/-0.428
* Rl = S([F0i - I Fc|)/S|F0|; ** wR2 = {S[w(|F0|2 - |Fc|2)2]/S[w(|F0|2)2]}
1/2
the xy plane via the n—n stack interaction ofpyridyl ring (centroid-to-centroid distance is 3.729 A) (Fig. 2b). Furthermore, the 2D layers are linked into 3D su-pramolecular structure by the little weaker n—n interaction of aromatic rings of Bpd
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