LIU BoLI Xiu-MeiZHOU ShiWANG Qing-WeiLI Chuan-Bi

(1Department of Chemistry,Jilin Normal University,Key Laboratory of Preparation and Applications of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,Siping,Jilin 136000,China)

(2Department of Chemistry,Tonghua Teachers College,Tonghua,Jilin 134002,China)

Synthesis and Crystal Structure of Two Complexes of Cobalt, Nickel Assembled by Isonicotinamide

LIU Bo＊,1LI Xiu-Mei2ZHOU Shi1WANG Qing-Wei1LI Chuan-Bi1

(1Department of Chemistry,Jilin Normal University,Key Laboratory of Preparation and Applications of Environmental Friendly Materials(Jilin Normal University),Ministry of Education,Siping,Jilin136000,China)

(2Department of Chemistry,Tonghua Teachers College,Tonghua,Jilin 134002,China)

Two transitional metal complex[Co(inta)2(H2O)4][Co(H2O)6](tdc)2·2H2O(1)and[Ni(inta)2(H2O)4](tdc)·2H2O (2)(inta=isonicotinamide,H2tdc=2,5-thiophenedicarboxylic acid)have been synthesized by employing the solution a preparation method at room temperature.They were structurally characterized by elemental analysis,IR spectrum, UV spectrum,TG and single-crystal X-ray diffraction.They are further extended into a three-dimensional supramolecular network structure through hydrogen bonds and π-π interactions.CCDC:862125,1;862126,2.

crystal structure;cobalt complex;nickel complex

0 Introduction

The rational design and synthesis of metaldirected supramolecular frameworks have received much attention in coordination chemistry because of their interesting molecular topologies and tremendous potential applications in host-guest chemistry,catalysis, molecular selection,nonlinear optics,ion exchange and microelectronics[1-6].In this field,the metals often have different valences,making a number of building blocks to fulfill special needs.Many important properties of coordination polymers depend largely on their structures and topology.Therefore,the selection of special inorganic and organic building blocks is the key to the construction of a desired framework[7].In this respect,the 2,5-thiophenedicarboxylic acid(H2tdc) ligand is proved to be a good candidate due to its various bridging abilities and strong coordinationtendency with transition metals to form 2D and 3D moderately robust networks[8-9].On the other hand,the introduction of bi-or multi-dentate ligands containing N-or O-donors to the metal-oxalate system may lead to new structural evolution since the binding of these ligands to metal centers may adjust the dimensionality of metal-organic coordination polymers[10-11].Among the organic N-donors,isonicotinamide(inta)is an excellent rigid ligand for the construction of novel metal-organic coordination frameworks because of its three donor sites[12-13].In this paper,we report two new compounds, [Co(inta)2(H2O)4][Co(H2O)6](tdc)2·2H2O(1)and[Ni(inta)2(H2O)4](tdc)·2H2O(2),which exhibit 3D supramolecular framework through hydrogen bonds and π-π stacking interactions and are reported scarcely.

1 Experimental

1.1 General procedures

All materials were commercially purchased and used without further purification.Infrared spectra(KBr pellets)were taken on a Perkin-Elmer 2400LSⅡspectrometer and elemental analyses for C,H and N were performed on a Perkin-Elmer 240C analyzer.The TG studies were performed on a Perkin-Elmer TGA7 analyzer.

1.2 Synthesis

[Co(inta)2(H2O)4][Co(H2O)6](tdc)2·2H2O (1).An aqueous solution of CoCl2·6H2O(0.2 mmol,10 mL)was slowly dropped into an acetonitrile solution of isonicotinamide (0.2 mmol,10 mL)under stirring.After stirring for 30 min,an aqueous solution of sodium tdc (0.2 mmol,10 mL)was added into the above solution, the precipitate was filtered and the filtrate was stood for 10 d,obtaining pink block crystals suitable for X-ray structural analysis.The elemental analyses found(%): C,31.1;H,4.2;N,5.9.Calcd.for C24H40Co2N4O22S2(%): C,31.4;H,4.4;N,6.1.

[Ni(inta)2(H2O)4](tdc)·2H2O(2).An aqueous solution of Ni(OAc)2·2H2O(0.2 mmol,10 mL)was slowly dropped into an acetonitrile solution of isonicotinamide (0.2 mmol,10 mL)under stirring.After stirring for 30 min,an aqueous solution of sodium tdc(0.2 mmol,10 mL)was added into the above solution,the precipitate was filtered and the filtrate was stood for 10 d, obtaining blue block crystalssuitable forX-ray structural analysis.The elemental analyses found(%): C,39.2;H,4.5;N,10.0.Calcd.for C18H26N4NiO12(%):C, 39.4;H,4.8;N,10.2.

1.3 Structure determination

Single crystal diffraction data of 1 and 2 were respectively collected on a Bruker SMART APEX-CCD diffractometer equipped with a graphite-monochromatic Mo Kα(λ=0.071073 nm)radiation at room temperature. The structure was solved by direct methods with SHELXS-97 program[14]and refined by full-matrix leastsquares techniques on F2with SHELXL-97[15].All nonhydrogen atoms were refined anisotropically and the hydrogen atoms of organic ligands were generated geometrically.The selected bond parameters are given in Table 1.

Crystal data for 1:C24H40Co2N4O22S,triclinic, space group P1,Mr=918.58,a=0.67382(5)nm,b=0.699 53(6)nm,c=2.014 64(16)nm,α=81.316 0(10)°, β=81.502 0(10)°,γ=75.904 0(10)°,V=0.904 34(13) nm3,Z=1,F(000)=474,μ(Mo Kα)=1.126 mm-1,Dc= 1.687 g·cm-3,4991 reflections measured,3543 unique (Rint=0.012 8),3 284 observed reflections with I＞2σ(I), R=0.0298,wR=0.0756,S=1.046.

Table 1 Selected bond lengths(nm)and bond angles(°)complound for 1 and 2

Continued Table 1

Crystal data for 2:C18H26N4NiO12S,triclinic,space group P1,Mr=581.2,a=0.9068(5)nm,b=0.9165(5)nm, c=1.553 3(5)nm,α=80.695(5)°,β=88.325(5)°,γ= 73.535(5)°,V=1.221 5(10)nm3,Z=2,F(000)=604, μ(Mo Kα)=0.949 mm-1,Dc=1.580 g·cm-3,6765 reflections measured,4 766 unique (Rint=0.011 6),4 173 observed reflections with I＞2σ(I),R=0.0298,wR= 0.0710,S=1.026.

CCDC:862125,1;862126,2.

2 Results and discussion

2.1 IR spectrum

The FTIR spectra of compound 1 (in KBr)show the bands as follows:3 442,1 680,1 558,1 403,1 350, 1128,785,760,620,542 and 468 cm-1.IR spectrum of the compound shows the typical anti-symmetric(1558 cm-1)and symmetric (1 350 cm-1)stretching bands of carboxylate groups.The absence of the characteristic band around 1700 cm-1in compound 1 attributed to the protonated carboxylic group indicates that the presence deprotonation of tdc ligand.In addition,the strong and broad band centered at 3 442 cm-1for 1 is attributable to the H-O-H stretching vibration of water molecule on the basis of the known structure.

The FTIR spectra of compound 2 (in KBr)show the bands as follows:3 358,1 679,1 600,1 555,1 418, 1400,1351,1312,1222,1151,1103,1064,881,786, 762,662,623,550 and 473 cm-1.IR spectrum of the compound shows the typical anti-symmetric(1555 cm-1) and symmetric (1 351 cm-1)stretching bands of carboxylate groups.The absence of the characteristic band around 1700 cm-1in compound 1 attributed to the protonated carboxylic group indicates that the present deprotonation of tdc ligand.In addition,the strong and broad band centered at 3 358 cm-1for 1 is attributable to the H-O-H stretching vibration of water molecule on the basis of the known structure.

2.2 Description of the structure

Fig.1 Molecular structure of the title compound 1

Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in P1 space group.The molecular structure of 1 is shown in Fig.1.There are two different coordination centers,Co(1)and Co(2),in the crystal with different coordination modes.The Co(1) ion is six-coordinated by two nitrogen atoms from different inta ligands(Co(1)-N(1)0.2169 4(16)nm, Co(1)-N(1A)0.216 94(16)nm)and four coordinated water molecules(Co(1)-O(1W)0.211 33(16)nm,Co(1)-O(1WA)0.211 33(16)nm,Co(1)-O(2W)0.209 01(15) nm,Co(1)-O(2WA)0.20901(15)nm),showing a slightly distorted octahedral geometry.The Co(2)ion is sixcoordinated by six coordinated water molecules(Co(2)-O(3W)0.208 27(14)nm,Co(2)-O(3WA)0.208 27(14) nm,Co(2)-O(4W)0.205 75(15)nm,Co(2)-O(4WA) 0.20575(15)nm,Co(2)-O(5W)0.21450(13)nm,Co(2)-O(5WA)0.214 50(13)nm),showing a slightly distorted octahedral geometry too.

Hydrogen bonding interactions are usually important in the synthesis of supramolecular architecture.There are persistent N-H…O and O-H…O hydrogen bonding interactions (Table 2)in thecomplex,which play an important role in stabilizing the network structure.Moreover,there are π-π interactions in compound 1 (Table 3)between inta ligands and free tdc anion.Therefore,through hydrogen bonds and π-π interactions,the network structures are further extended into a three-dimensionalsupramolecular framework(Fig.2).

Table 2 Hydrogen bonds for compound 1 and 2

Table 3 Parameters between the planes in compound 1

Fig.2 Hydrogen binding interactions in 1

Single-crystal X-ray diffraction analysis reveals that complex 2 crystallizes in P1 space group.The coordination environment of Ni（Ⅱ） in complex 2 is shown in Fig.3.There are two same coordination centers,Ni(1)and Ni(2),in the crystal with same coordination modes.The Ni(1)ion is six-coordinated by four coordinated water molecules(Ni(1)-O(1W)0.20498(17) nm,Ni(1)-O(1WA)0.204 98(17)nm,Ni(1)-O(2W) 0.205 33(15)nm,Ni(1)-O(2WA)0.205 33(15)nm)and two nitrogen atoms from different inta ligands(Ni(1)-N(1)0.211 91(19)nm,Ni(1)-N(1A)0.211 91(19)nm), showing a slightly distorted octahedral geometry.

Fig.3 Molecular structure of the title compound 2

There are persistent N-H…O and O-H…O hydrogen bonding interactions(Table 2)in the complex 2,which play an important role in stabilizing the network structure.Moreover,there are many significant π-π interactions in the packing diagram between the neighboring aromatic cycles contained in inta ligands and free tdc anion.The centroid-to-centroid distances between adjacent aromatic rings is 0.394 3 nm for N3C7C8C9C11C12 and S1C15C16C17C18 aromatic rings.The perpendicular distance is 0.365 0 nm for N3C7C8C9C11C12 and S1C15C16C17C18 aromatic rings.Therefore,through hydrogen bonds and π-π interactions,the network structures are further extended into a three-dimensionalsupramolecular framework(Fig.4).

Fig.4 Hydrogen binding interactions in 2

2.3 Thermal analysis

TG curve of 1 show that the first weight loss of 58.6%from 17 to 117℃corresponds to the removal of water and tdc molecules(calcd.60.5%).Upon further heating,an obvious weight loss(28.50%)occurs in the temperature range of 117～450℃,corresponding to the release of inta ligands(calcd.26.6%).After 450℃no weight loss is observed,which means the complete decomposition of 1.The residual weight should be CoO.

TG curve of 2 shows that the first weight loss of 33.1%from 15 to 151℃corresponds to the removal of free water and tdc molecules (calcd.35.5%).Upon further heating,an obvious weight loss(88.5%)occurs in the temperature range of 151～549℃,corresponding to the release of coordinated water molecules and inta ligands(calcd.89.9%).After 554℃no weight loss is observed,which means the complete decomposition of 2.The residual weight should be NiO.

2.4 UV spectrum

The UV spectra for the title compound 1 and inta ligand have been investigated in the solid state.Both the title compound and inta have one absorption band at about 271 nm,which should be assigned to the n→π*[16]transition of inta.However,after inta coordinating to the Co2+ion,the absorption intensity slightly increases.It is clearly that the absorption band in inta remains in the same position with that in the title compound,showing that they are not affected basically by the metal coordination.

The UV spectra for the title compound 2 and inta ligand have been investigated in the solid state.For compound 2,there is no absorption band.

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兩個由異煙酰胺構筑的鈷、鎳配合物的合成及晶體結構

劉 博＊,1李秀梅2周 實1王慶偉1李傳碧1

(1吉林師范大學化學學院，吉林師范大學環(huán)境友好材料制備與應用省部共建教育部重點實驗室，四平 136000)
(2通化師范學院化學系，通化 134002)

采用溶液培養(yǎng)法，在室溫下合成了2個新的過渡金屬配合物[Co(inta)2(H2O)4][Co(H2O)6](tdc)2·2H2O(1)和[Ni(inta)2(H2O)4](tdc) ·2H2O(2)(inta=異煙酰胺，H2tdc=2,5-噻吩二甲酸)。并對其進行了元素分析、紅外光譜、紫外光譜、熱重和X-射線單晶衍射測定。這兩個配合物通過氫鍵和π-π相互作用形成了三維超分子網(wǎng)狀結構。

晶體結構；鈷配合物；鎳配合物

O614.81+2；O614.81+3

A

1001-4861(2012)05-1019-06

2011-09-18。收修改稿日期：2011-12-24。

吉林省教育廳科學技術研究(吉教科合字(2012)第479號)資助項目。＊

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