CN103242376A - 5-iodobenzene-1,3-cobalt dioxoroacetate coordination compound and preparation method thereof - Google Patents
5-iodobenzene-1,3-cobalt dioxoroacetate coordination compound and preparation method thereof Download PDFInfo
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- CN103242376A CN103242376A CN2013101868498A CN201310186849A CN103242376A CN 103242376 A CN103242376 A CN 103242376A CN 2013101868498 A CN2013101868498 A CN 2013101868498A CN 201310186849 A CN201310186849 A CN 201310186849A CN 103242376 A CN103242376 A CN 103242376A
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Abstract
The invention discloses a cobalt coordination compound and a preparation method thereof and in particular relates to a 5-iodobenzene-1,3-cobalt dioxoroacetate coordination compound and a preparation method thereof, belonging to the field of coordination chemistry. The coordination compound has the structural formula of [Co(L)(bpe)0.5(H2O)2]n, wherein L is 5-iodobenzene-1,3-dioxoroacetate anionic ligand; and bpe is 1,2-bi(4-pyridyl) ethylene. The preparation method comprises the following steps: dissolving 5-iodobenzene-1,3-dioxoroacetate, inorganic base, bpe and inorganic cobalt salt in water under hydrothermal conditions, sealing in a reaction kettle, keeping the constant temperature at the temperature of 130 DEG C for three days, and cooling to room temperature under natural conditions to obtain the coordination compound. The coordination compound is readily available in synthesis raw materials, low in cost, simple in synthesis, convenient in operation and high in yield and repeatability and is stable in a natural state, and diversified coordination modes and conformations are adopted in the process of self-assembling the coordination compound.
Description
Technical field
The present invention relates to a kind of 5-iodo benzene-1,3-dioxy cobaltous acetate title complex and preparation method belong to the coordination chemistry field.
Background technology
At present, explore the new multi-functional part flexible or functionalization that has and caused great concern in the coordination chemistry research field.Compare with rigid ligand, flexible part has more coordination mode and conformation, has bigger geometry degree of freedom to go to satisfy the process of title complex self-assembly, and it is more charming to be expected to obtain structure, the title complex of more excellent performance.Especially it should be noted that flexible polydentate ligand when forming title complex because its easy distortion can improve the helicity of polymeric chain.The flexible di-carboxylic acid that contains the iodine atom such as 5-iodo benzene-1,3-two fluoroacetic acid, its iodine atom and two carboxyl methoxy group be positioned at phenyl ring between the position, because the nonlinear flexibility around the ether oxygen atom, the distortion of aromatic ring and carboxyl, this part are expected to take diversified coordination mode and conformation in the self-assembly of title complex.In addition, the iodine atom pairs title complex that it has synthetic has inducing action, constructs out novel three-dimensional supramolecular structure.The specific functional group of this selection goes to induce the method that produces complicated super molecular compound to enrich appropriate design and the concept of constructing function supramolecule material.Do not see 5-iodo benzene-1 at present, 3-dioxy cobaltous acetate title complex and preparation method's relevant report.
Summary of the invention
The object of the present invention is to provide a kind of 5-iodo benzene-1 with flexible part, 3-dioxy cobaltous acetate title complex and preparation method thereof.
For realizing the object of the invention, cobalt complex provided by the invention is divalence cobalt and 5-iodo benzene-1, the title complex that 3-two fluoroacetic acid and bpe form.The structural formula of described title complex is: [Co (L) (bpe)
0.5(H
2O)
2]
n , belonging to oblique system, spacer is
P2
1/
c,
a=9.806 (2),
b=6.5492 (13),
c=28.187 (8),
b=100.12 (3) °,
V=1782.0 (7)
3Wherein L is 5-iodo benzene-1,3-two fluoroacetic acid anion ligands, and skeleton symbol is as follows:
Wherein bpe is 1,2-two (4-pyridyl) ethene, and skeleton symbol is as follows:
The preparation method of described title complex: with cobalt salt and 5-iodo benzene-1,3-two fluoroacetic acid, bpe and mineral alkali are soluble in water, encloses in the reactor, and under the hydrothermal method condition, 130
oC constant temperature three days, natural condition drop to room temperature, obtain target compound, are the purple bulk crystals.
Described title complex is the three-dimensional structure of a uniqueness, and the layer that is formed by the simple helix of different chiralitys and triple helical is formed by connecting by bpe, and its topological symbol is (610
2) (6
210
4).
Described cobalt salt is Xiao Suangu or Cobaltous diacetate.
Described mineral alkali is potassium hydroxide or sodium hydroxide.
Title complex of the present invention is with the 5-iodo benzene-1 that contains the iodine atom of flexibility, 3-two fluoroacetic acid are part, iodine atom wherein and two carboxyl methoxy group be positioned at phenyl ring between the position, because its easy distortion can improve the helicity of polymeric chain, stable under state of nature when forming title complex.This part is conducive to take diversified coordination mode and conformation in the self-assembly of title complex.Synthesis material is easy to get, and cost is low, and is synthetic simple, easy to operate, productive rate height and favorable reproducibility.
Description of drawings
The 5-iodo benzene-1 of Fig. 1 embodiment 1 preparation, the coordination environment figure of cobalt in the 3-dioxy cobaltous acetate title complex;
The 5-iodo benzene-1 of Fig. 2 embodiment 1 preparation, the three-dimensional framework synoptic diagram of 3-dioxy cobaltous acetate title complex;
The 5-iodo benzene-1 of Fig. 3 embodiment 1 preparation, the topology diagram of 3-dioxy cobaltous acetate title complex;
The 5-iodo benzene-1 of Fig. 4 embodiment 1 preparation, 3-dioxy cobaltous acetate title complex infrared spectrum;
The 5-iodo benzene-1 of Fig. 5 embodiment 1 preparation, 3-dioxy cobaltous acetate title complex thermogravimetric curve figure.
Embodiment
The preparation of embodiment one title complex
With 5-iodo benzene-1,3-two fluoroacetic acid (0.0176 g, 0.05 mmol), potassium hydroxide (5.6 mg, 0.1 mmol), bpe (18.2 mg, 0.1 mmol) and Co (NO
3)
26H
2O (0.0146 g, 0.05 mmol) in water-soluble (7 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, kept this temperature 3 days, naturally be down to room temperature then, can obtain the purple bulk crystals, this crystal separation is come out, successively through washing, drying treatment, obtain target product, productive rate about 73%.Main infrared absorption peak is: 3477 (w), 3066 (w), 2923 (w), 1607 (vs), 1416 (s), 1265 (m), 1152 (m), 1065 (w), 1051 (w), 1016 (w), 832 (m), 722 (w), 551 (m).
The preparation of embodiment two title complexs
With 5-iodo benzene-1,3-two fluoroacetic acid (0.0176 g, 0.05 mmol), potassium hydroxide (5.6 mg, 0.1 mmol), bpe (18.2 mg, 0.1 mmol) and Co (CH
3CO
2)
24H
2O (0.0124 g, 0.05 mmol) in water-soluble (7 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, kept this temperature 3 days, naturally be down to room temperature then, can obtain the purple bulk crystals, this crystal separation is come out, successively through washing, drying treatment, obtain target product, productive rate about 56%.
The preparation of embodiment three title complexs
With 5-iodo benzene-1,3-two fluoroacetic acid (0.0176 g, 0.05 mmol), sodium hydroxide (4.0 mg, 0.1 mmol), bpe (18.2 mg, 0.1 mmol) and Co (NO
3)
26H
2O (0.0146 g, 0.05 mmol) in water-soluble (7 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, kept this temperature 3 days, naturally be down to room temperature then, can obtain the purple bulk crystals, this crystal separation is come out, successively through washing, drying treatment, obtain target product, productive rate about 45%.
The preparation of embodiment four title complexs
With 5-iodo benzene-1,3-two fluoroacetic acid (0.0176 g, 0.05 mmol), sodium hydroxide (4.0 mg, 0.1 mmol), bpe (18.2 mg, 0.1 mmol) and Co (CH
3CO
2)
24H
2O (0.0124 g, 0.05 mmol) in water-soluble (7 mL), enclose in the reactor of 25mL, be heated to 130 ℃ with 10 ℃ speed per hour, kept this temperature 3 days, naturally be down to room temperature then, can obtain the purple bulk crystals, this crystal separation is come out, successively through washing, drying treatment, obtain target product, productive rate about 50%.
Complex crystal of the present invention belongs to oblique system, and spacer is
P2
1/
c,
a=9.806 (2),
b=6.5492 (13),
c=28.187 (8),
b=100.12 (3) °,
V=1782.0 (7)
3Title complex basic structure is the three-dimensional structure of a uniqueness, and the layer that is formed by the simple helix of different chiralitys and triple helical is formed by connecting by bpe, and its topological symbol is (610
2) (6
210
4).
Get the 5-iodo benzene-1 that embodiment one makes, 3-dioxy cobaltous acetate title complex further characterizes, and its process is as follows:
(1) crystal structure determination of title complex
The X ray single crystal diffraction data of title complex are measured at Bruker SMART APEX CCD diffractometer with sizeable single crystal samples.Data are all used through the MoK of graphite monochromatization alpha-ray (λ=0.71073) and are at room temperature collected by the ω scan mode for diffraction source, and through Lp factor correction and semiempirical absorption correction.Structure elucidation is to obtain structure just by the SHELXS-97 program with direct method earlier, uses the complete matrix method of least squares refine of SHELXL-97 program then.All non-hydrogen atoms all adopt the refine of anisotropic thermal parameter method.The hydrogen atom coordinate of coordinated water and part is obtained by theoretical hydrogenation, and the hydrogen atom on the solvent then obtains by the difference Fourier method, and all hydrogen atoms all adopt the refine of isotropy thermal parameter method.Detailed axonometry data see Table 1; Important bond distance and bond angle data see Table 2.Crystalline structure is seen Fig. 1 and Fig. 2, and the topological network of title complex is seen Fig. 3.
The main crystallographic data of table 1 title complex
| |
1 |
| Empirical formula | C 16H 16CoINO 8 |
| Formula weight | 536.13 |
| Cryst. size, mm 3 | 0.22′ 0.20′ 0.19 |
| Temperature, K | 296(2) |
| Radiation; wavelength, | Mo Kα; 0.71073 |
| Crystal system | Monoclinic |
| Space group | P 2 1/ c |
| a, | 9.806(2) |
| b, | 6.5492(13) |
| c, | 28.187(8) |
| α, deg | 90.00 |
| β, deg | 100.12(3) |
| γ, deg | 90.00 |
| V , 3 | 1782.0(7) |
| Z | 4 |
| D calcd, g cm 3 | 1.998 |
| μ(Mo Kα), mm -1 | 2.741 |
| F(000), e | 1052 |
| θ range data collection, deg | 2.35–25.00 |
| Re ns. collected / independent / R int | 17115 / 3134 / 0.0433 |
| Param. refined | 244 |
| R 1 a / wR 2 b [I>2σ (I )] | 0.0393/0.0858 |
| R 1 a / wR 2 b (all data) | 0.0445/0.0898 |
| GoF c on F 2 | 1.031 |
| Δ ρ fin (max / min), e –3 | 0.623, -0.601 |
R
1
=Σ||F
o
| |F
c
||/Σ|F
o
|.
b
wR
2
=[Σ[w(F
o
2
F
c
2
)
2
]/Σw(F
o
2
)
2
]
1/2
Bond distance's () that table 2 is important and bond angle (°)
| Co(1)-O(1)#1 | 2.082(3) | Co(1)-O(1W) | 2.102(3) | Co(1)-O(2W) | 2.110(3) |
| Co(1)-O(4) | 2.121(3) | Co(1)-O(2)#2 | 2.139(3) | Co(1)-N(1) | 2.148(3) |
| O(1)#1-Co(1)-O(1W) | 177.39(13) | O(1)#1-Co(1)-O(2W) | 90.25(12) | O(1W)-Co(1)-O(2W) | 91.82(12) |
| O(1)#1-Co(1)-O(4) | 95.14(13) | O(1W)-Co(1)-O(4) | 86.49(13) | O(2W)-Co(1)-O(4) | 89.25(12) |
| O(1)#1-Co(1)-O(2)#2 | 87.42(12) | O(1W)-Co(1)-O(2)#2 | 91.01(12) | O(2W)-Co(1)-O(2)#2 | 89.11(12) |
| O(4)-Co(1)-O(2)#2 | 176.97(12) | O(1)#1-Co(1)-N(1) | 85.46(13) | O(1W)-Co(1)-N(1) | 92.49(13) |
| O(2W)-Co(1)-N(1) | 175.64(13) | O(4)-Co(1)-N(1) | 90.38(13) | O(2)#2-Co(1)-N(1) | 91.44(12) |
Symmetry code: #1
x+ 1,
y + 1,
z; #2-
x,
y+ 3/2 ,-
z+ 3/2.
(2) Infrared Characterization of title complex
The infrared spectrum of title complex of the present invention is seen Fig. 4.(instrument model: Bruker VECTOR 22 type infrared spectrometers).
(3) thermostability of title complex characterizes
The thermogravimetric analysis of title complex of the present invention characterizes and shows that it has lost the coordinated water molecule gradually between 95 to 192 ° of C, actual weightlessness is 6.68%, theoretical weightlessness is 6.71%, but skeleton still can be stablized up to about 324 ℃, has certain thermostability, for its further Application and Development as material provides the thermostability assurance, see Fig. 5.(instrument model: SDT 2960 type thermal analyzers).
Above embodiment only is used for explanation content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replaces or technical scheme that the equivalent deformation mode forms all drops in protection scope of the present invention.
Claims (5)
1.5-iodo benzene-1,3-dioxy cobaltous acetate title complex, it is characterized in that: the structural formula of described title complex is: [Co (L) is (bpe)
0.5(H
2O)
2]
n , belonging to oblique system, spacer is
P2
1/
c,
a=9.806 (2),
b=6.5492 (13),
c=28.187 (8),
b=100.12 (3) °,
V=1782.0 (7)
3, wherein L is 5-iodo benzene-1,3-two fluoroacetic acid anion ligands, and skeleton symbol is as follows:
Wherein bpe is 1,2-two (4-pyridyl) ethene, and skeleton symbol is as follows:
。
2. 5-iodo benzene-1 as claimed in claim 1,3-dioxy cobaltous acetate title complex, it is characterized in that: title complex is three-dimensional structure, and the layer that is formed by simple helix and the triple helical of different chiralitys is formed by connecting by bpe, and its topological symbol is (610
2) (6
210
4).
3. prepare the described 5-iodo of claim 1 benzene-1, the method for 3-dioxy cobaltous acetate title complex is characterized in that: with cobalt salt and 5-iodo benzene-1,3-two fluoroacetic acid, 1,2-two (4-pyridyl) ethene and mineral alkali are soluble in water, and enclose in the reactor, under the hydrothermal method condition, 130
oC constant temperature three days, natural condition drop to room temperature then, obtain the target compound crystal.
4. 5-iodo benzene-1 according to claim 3,3-dioxy cobaltous acetate title complex preparation method, it is characterized in that: described cobalt salt is Xiao Suangu or Cobaltous diacetate.
5. 5-iodo benzene-1 according to claim 3,3-dioxy cobaltous acetate title complex preparation method, it is characterized in that: described mineral alkali is potassium hydroxide or sodium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951708A (en) * | 2014-04-18 | 2014-07-30 | 海南大学 | Multidentate carboxylic acid coordination polymer and preparation method thereof |
| CN105601506A (en) * | 2016-01-05 | 2016-05-25 | 天津师范大学 | 2,5-dibromo-1,4-biphenoxyl cobaltous diacetate complex single crystals and application |
-
2013
- 2013-05-20 CN CN2013101868498A patent/CN103242376A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| YAN ZHAO等,: "Two metal–organic coordination polymers assembled from a flexible iodo-dicarboxylate ligand and N-donor ancillary ligands", 《INORGANICA CHIMICA ACTA》 * |
| 樊亚娟,: "碘代多羧酸配合物的合成、结构与性能研究", 《郑州大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951708A (en) * | 2014-04-18 | 2014-07-30 | 海南大学 | Multidentate carboxylic acid coordination polymer and preparation method thereof |
| CN105601506A (en) * | 2016-01-05 | 2016-05-25 | 天津师范大学 | 2,5-dibromo-1,4-biphenoxyl cobaltous diacetate complex single crystals and application |
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Application publication date: 20130814 |