Templated coordination polymers [Ni(H2O)4(bipy)](BTA)0.5
Coordination polymers are currently of considerable interest and importance because of the scope they offer for the generation by design of new materials with a range of potentially useful properties, such as magnetism, adsorption, ion exchange, and catalysis [
All the reagents were commercially available and used without further purification. Distilled water was used throughout. Elemental (C, H, and N) analyses were performed on a CE-440 (Leeman labs) analyzer. Thermal gravimetric analysis (TGA) was performed on a PerkinElmer TGA 7 instrument in the temperature range of 25–700°C at a heating rate of 10°C/min under air atmosphere. IR spectra were recorded as KBr pellets on a FTIR-8400 spectrometer in the range of 4000–400 cm−1. The single-crystal X-ray structures were determined on a Bruker Smart APEX CCD area detector.
A mixture of Ni(NO3)2
The synthesis method of compound 2 is the same as that for 1 except that the metal salt was replaced by Co(NO3)2
Single-crystal X-ray diffraction was put on a Bruker Smart Apex CCD diffractometer equipped with agraphite-monochromatic
Crystallographic data for complexes
Compound | ||
---|---|---|
Empirical formula | C15H19N2O9Ni | C15H16N2O9Co |
Formula weight | 430.03 | 430.25 |
Crystal dimensions/mm | ||
Crystal system | Monoclinic | Monoclinic |
Space group | C2/c | C2/c |
19.895 (3) | 20.061 (2) | |
11.2693 (19) | 11.3404 (12) | |
15.589 (3) | 15.6579 (17) | |
90.00 | 90.00 | |
94.829 (2) | 95.449 (2) | |
90.00 | 90.00 | |
3482.6 (10) | 3546.0 (7) | |
8 | 8 | |
1.640 | 1.612 | |
Absorption coefficient/mm−1 | 1.168 | 1.021 |
1784 | 2156 | |
296 (2) | 296 (2) | |
Reflections collected | 22849 | 23377 |
Reflections unique | 3340 | 3535 |
0.0537 | 0.0440 | |
Parameters | 289 | 255 |
Goodness-of-fit on | 1.027 | 1.053 |
0.0365 | 0.0440 | |
0.0930 | 0.1272 | |
(Δ | 0.410 | 1.093 |
(Δ | −0.414 | −0.646 |
Selected bond lengths (Å) and bond angles (°) for compounds
Bond | Dist. | Bond | Dist. | Bond | Dist. |
Ni(1)–O(2) | 2.0284 (17) | Ni(1)–N(1) | 2.1502 (19) | Ni(2)–O(4) | 2.1017 (18) |
Ni(1)–O(2)#1 | 2.0284 (17) | Ni(1)–N(1)#1 | 2.1502 (19) | Ni(2)–O(4)#2 | 2.1017 (18) |
Ni(1)–O(1) | 2.0869 (18) | Ni(2)–O(3) | 2.0468 (17) | Ni(2)–N(2) | 2.091 (3) |
Ni(1)–O(1)#1 | 2.0869 (18) | Ni(2)–O(3)#2 | 2.0468 (17) | Ni(2)–N(3)#3 | 2.106 (3) |
Angle | (°) | Angle | (°) | Angle | (°) |
O(2)#1–Ni(1)–O(2) | 180.00 (9) | O(2)–Ni(1)–N(1) | 91.60 (7) | O(3)#2–Ni(2)–N(3)#3 | 91.96 (5) |
O(2)#1–Ni(1)–O(1) | 93.35 (8) | O(2)–Ni(1)–N(1)#1 | 88.40 (7) | O(3)#3–Ni(2)–N(3) | 91.96 (5) |
O(2)–Ni(1)–O(1) | 86.65 (8) | O(1)–Ni(1)–N(1)#1 | 88.32 (7) | O(3)–Ni(2)–N(2) | 88.04 (5) |
O(2)#1–Ni(1)–O(1)#1 | 86.65 (8) | O(1)–Ni(1)–N(1) | 91.68 (7) | O(3)–Ni(2)–N(2)#2 | 88.04 (5) |
O(2)–Ni(1)–O(1)#1 | 93.35 (8) | N(1)–Ni(1)–N(1)#1 | 180.00 (10) | O(4)–Ni(2)–O(4)#2 | 174.17 (9) |
O(2)#1–Ni(1)–N(1) | 88.40 (7) | O(3)–Ni(2)–O(3)#2 | 176.08 (10) | O(4)#2–Ni(2)–N(3)#3 | 91.92 (5) |
O(2)#1–Ni(1)–N(1)#1 | 91.60 (7) | O(3)–Ni(2)–O(4)#2 | 89.09 (7) | O(4)#3–Ni(2)–N(3) | 91.92 (5) |
O(1)#1–Ni(1)–N(1)#1 | 91.68 (7) | O(3)#2–Ni(2)–O(4)#2 | 90.71 (7) | O(4)–Ni(2)–N(2) | 87.08 (5) |
O(1)#1–Ni(1)–N(1) | 88.32 (7) | O(3)#2–Ni(2)–O(4) | 89.09 (7) | O(4)#2–Ni(2)–N(2) | 87.08 (5) |
O(1)#1–Ni(1)–O(1) | 180.00 (10) | O(3)–Ni(2)–O(4) | 90.71 (7) | N(2)#2–Ni(2)–N(3) | 180.000 (1) |
Bond | Dist. | Bond | Dist. | Bond | Dist. |
Co(1)–O(9) | 2.068 (2) | Co(1)–N(2) | 2.125 (3) | Co(2)–O(7)#2 | 2.137 (2) |
Co(1)–O(9)#1 | 2.068 (2) | Co(1)–N(3) | 2.141 (3) | Co(2)–N(1) | 2.210 (2) |
Co(1)–O(8)#1 | 2.154 (2) | Co(2)–O(6) | 2.041 (2) | Co(2)–N(1)#2 | 2.210 (2) |
Co(1)–O(8) | 2.154 (2) | Co(2)–O(7) | 2.137 (2) | Co(2)–O(6)#2 | 2.041 (2) |
Angle | (°) | Angle | (°) | Angle | (°) |
O(9)#1–Co(1)–O(9) | 176.41 (12) | N(2)–Co(1)–O(8) | 87.26 (6) | O(6)#2–Co(2)–O(6) | 180.00 (19) |
O(9)#1–Co(1)–O(8)#1 | 90.11(8) | N(2)–Co(1)–O(8)#1 | 87.26 (6) | O(6)#2–Co(2)–O(7) | 92.65 (10) |
O(9)–Co(1)–O(8) | 90.11 (8) | N(2)–Co(1)–N(3) | 180.000 (1) | O(6)–Co(2)–O(7)#2 | 92.65 (10) |
O(9)–Co(1)–O(8)#1 | 89.72 (8) | N(3)–Co(1)–O(8) | 92.74 (6) | O(6)–Co(2)–O(7) | 87.35 (10) |
O(9)#1–Co(1)–O(8) | 89.72 (8) | N(3)–Co(1)–O(8)#1 | 92.74 (6) | O(6)#2–Co(2)–O(7)#2 | 87.35 (10) |
O(9)–Co(1)–N(2) | 88.21 (6) | N(1)–Co(2)–N(1)#2 | 180.00 (6) | O(7)#2–Co(2)–N(1)#2 | 91.61 (10) |
O(9)#1–Co(1)–N(2) | 88.21 (6) | O(6)#2–Co(2)–N(1)#2 | 92.37 (9) | O(7)–Co(2)–N(1)#2 | 88.39 (10) |
O(9)#1–Co(1)–N(3) | 91.79 (6) | O(6)–Co(2)–N(1) | 92.37 (9) | O(7)#2–Co(2)–N(1) | 88.39 (10) |
O(9)–Co(1)–N(3) | 91.79 (6) | O(6)#2–Co(2)–N(1) | 87. 63 (9) | O(7)–Co(2)–N(1) | 91.61 (10) |
O(8)#1–Co(1)–O(8) | 174.52 (11) | O(6)–Co(2)–N(1)#2 | 87. 63 (9) | O(7)#2–Co(2)–O(7) | 180.00 (18) |
Symmetry transformations used to generate the equivalent atoms: For
The structures of two complexes were determined by single-crystal X-ray diffraction analyses. Complexes
ORTEP drawing of asymmetric unit of complex
In the asymmetric unit of complex
The coordination environment of Ni atom in complex
the cross-structure of one-dimensional chain.
In the coordination environment, as one hydrogen-bond donor and a double hydrogen-bond acceptor, O9 from lattice water with two O atoms of BTA4− and coordinated water, respectively, form intermolecular H-bonding (
Hydrogen bond lengths (Å) and bond angles (°) for compounds
D–H | d(D–H) | d(H···A) | d(D···A) | ∠DHA |
---|---|---|---|---|
O1–H1A | 0.890 | 1.976 | 2.832 | 161.00 |
O4–H4B | 0.818 | 2.081 | 2.858 | 158.74 |
O9–H9A | 0.933 | 1.976 | 2.889 | 165.54 |
O2–H2B | 0.904 | 1.849 | 2.735 | 165.64 |
O6–H6A | 0.851 | 1.907 | 2.639 | 143.44 |
O1–H1A | 0.851 | 1.950 | 2.794 | 173.55 |
O7–H7B | 0.900 | 2.065 | 2.849 | 144.96 |
Symmetry transformations used to generate the equivalent atoms: For
Complex 1 constructed by interchain hydrogen bonds (red dashed lines), in which the water molecules are omitted for clarity.
(a) The 3D structure of 1 constructed by interchain hydrogen bonds (red dashed lines) along the
The structure of complex
IR spectrum (Figures 2s and 3s) shows that: the absorption bonds arising from the skeletal vibration of aromatic rings in the 1450–1650 cm−1 range. A wide band of strong intensity at 3389 cm−1 for
Thermal gravimetric (TG) analysis has been measured for complexes
The PXRD was used to check the purity of compounds
In summary, two novel supramolecular complexes of
This work was supported by the International Scientific and Technological Cooperation Projects of Shanxi Province (no: 2011081022).