Syntheses and Crystal Structures of Two Cobalt (Ⅱ) Compounds Based on 3, 5-Bis (4-pyridyl)-pyridine

Chun-Li ZHANH Hong-Yan WANG He-Gen ZHENG

Citation:  ZHANH Chun-Li, WANG Hong-Yan, ZHENG He-Gen. Syntheses and Crystal Structures of Two Cobalt (Ⅱ) Compounds Based on 3, 5-Bis (4-pyridyl)-pyridine[J]. Chinese Journal of Inorganic Chemistry, 2016, 32(5): 859-863. doi: 10.11862/CJIC.2016.113 shu

基于3, 5-双 (4-吡啶基)-吡啶的两个钴 (Ⅱ) 配合物的合成与晶体结构

    通讯作者: 郑和根, zhenghg@nju.edu.cn
  • 基金项目:

    安徽高校省级自然科学研究重点项目 KJ2015A203

    宿州学院自旋电子与纳米材料安徽省重点实验室开放课题 2014YKF51

    安徽省自然科学基金 1408085MB40

    国家自然科学基金 21371092

摘要: 用3, 5-双 (4-吡啶基)-吡啶 (BPYPY) 分别与反式-1, 4-环己烷二甲酸 (trans-H2chdc) 和4, 4'-联苯醚二甲酸 (H2oba) 组成混合配体, 用温和的溶剂热法与Co (NO3)2·6H2O合成了2个配合物[Co (BPYPY)2(H2O)4]·(trans-chdc)·4H2O (1) 和{[Co (BPYPY)(H2O)4]·(oba)}n(2), 利用X射线单晶衍射、元素分析对它们进行了表征.结果显示, 配合物1为单核结构, 属于单斜晶系, P21/n空间群; 配位聚合物2是一维链通过O-H…O氢键形成的三维超分子结构, 属于正交晶系, Pccn空间群.

English

  • Crystal engineering of coordination polymers has attracted intensive attention due to their variable archite-ctures and potential applications in optical materials[1-3], catalysis[4-5], gas adsorption[6], magnetism[7-8], etc. A large number of coordination polymers (CPs) of N-containing ligands and carboxylic acids have been reported[9-12], not only because they can incorporate virtues of different functional groups and it is easier to get architecture controlled by changing one of the above two kinds of ligands, but also due to allowing free rotation of the imidazole ring to meet the requirement of coordination geometries of metalions[13-14]. To date, however, how to rationally design and synthesize the desired architectures and properties is still a great challenge because the formation of CPs may be easily affected by many factors.

    Considering that mixed-ligand of N-containing ligands and carboxylic acids offers greater tunability of the structural framework, two carboxylate ligands of trans-1, 4-cyclohexanedicarboxylic acid (trans-H2chdc) and 4, 4'-oxydibenzoic acid (H2oba) were introduced to react with 3, 5-bis (4-pyridyl)-pyridine (BPYP) of V-shaped flexible polypyridyl ligand and cobalt nitrate. Then two new compounds [Co (BPYPY)2(H2O)4]·(trans-chdc)·4H2O (1) and {[Co (BPYPY)(H2O)4]·(oba)}n (2) were obtained. Further, we described their syntheses and crystal structures in detail.

    1   Experimental

    1.1   Materials and measurement

    All the chemicals were commercially purchased and used without further purification. Elemental analyses were performed on an Elementar Vario MICRO Elemental Analyzer. Single crystal X-ray diffraction measurements were carried out on a Bruker Smart APEX Ⅱ CCD diffraction.

    1.2   Synthesis of compounds

    [Co (BPYPY)2(H2O)4]·(trans-chdc)·4H2O (1): A mixture of Co (NO3)2·6H2O (29.1 mg, 0.1 mmol), trans-H2chdc (17.2 mg, 0.1 mmol) and BPYPY (23.3 mg, 0.1 mmol) were dissolved in 6 mL of H2O/DMF (2:4, V/V). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) and heated at 90 ℃ for 3 days. After being cooled to room temperature, orange block crystals were obtained. The yield was ca. 63% based on BPYPY ligand. Anal. Calcd. for C38H48CoN6O12(%): C, 54.30; H, 5.72; N, 10.00. Found (%): C, 54.27; H, 5.74; N, 9.88.

    {[Co (BPYPY)(H2O)4]·(oba)}n (2): A mixture of Co (NO3)2·6H2O (29.1 mg, 0.1 mmol), H2oba (25.8 mg, 0.1 mmol) and BPYPY (23.3 mg, 0.1 mmol) were dissolved in 6 mL of H2O/DMF (2:4, V/V). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) and heated at 95 ℃ for 3 days. Orange block crystals were collected. The yield was ca. 60% based on BPYPY ligand. Anal. Calcd. for C29H27CoN3O9(%): C, 56.09; H, 4.35; N, 6.77. Found (%): C, 56.07; H, 4.33; N, 6.79.

    1.3   Structure determination of Single Crystals

    The regular crystals of compounds 1 and 2 were mounted on a Bruker Smart APEX Ⅱ CCD diffraction (λ=0.071 073 nm). In all cases, empirical absorption corrections by SADABS were applied to the intensity data[15]. The structures were solved by direct methods, and non-hydrogen atoms were refined anisotropically on F2 by the full-matrix least-squares techniques using SHELXL-97 program package[16]. Crystallographic data and structure refinements of compounds 1 and 2 are listed in Table 1. The selected bond lengths and bond angles of compounds are listed in Table 2.

    Table 1.  Crystallographic data for compounds 1 and 2
    Compound 1 2
    Empirical formula C38H48CoN6O12 C29H27CoN3O9
    Formula weight 839.75 620.47
    Crystal system Monoclinic Orthorhombic
    Space group P21/n Pccn
    a / nm 1.479 47(6) 0.800 81(2)
    b/ nm 0.692 80(3) 2.700 75(7)
    c / nm 1.954 89(8) 1.230 98(3)
    β/(°) 99.280 0(10)
    V/ nm3 1.977 49(14) 2.662 35(12)
    Z 2 4
    Dc/(g·cm-3) 1.410 1.548
    Size / mm 0.28×0.26×0.22 0.30×0.28×0.26
    μ/ mm-1 0.504 0.708
    F(000) 882 1284
    θmin, θmax / (°) 2.71, 30.67 2.65, 27.56
    Goodness of fit on F2 1.033 1.058
    Reflections collected 13 752 13 759
    Independent reflections (Rint) 4 892(0.021 1) 3048(0.017 7)
    R1, wR2 [I > 2σ(I)] 0.033 7, 0.086 8 0.030 7, 0.084 9
    R1, wR2 (all data) 0.045 2, 0.093 8 0.035 7, 0.088 5
    ρ) max, (Δρ) min/ (e·nm-3) 413, -298 272, -349
    Table 2.  Selected bond lengths(nm) and bond angles(°) of compounds 1 and 2
    Compound 1
    Co(1)-O(1) 0.207 40(11) Co(1)-N(1) 0.218 06(12) Co(1)-O(2) 0.208 54(11)
    O(1)_Co(1)-O(1)#1 180.00(7) O(1)-Co(1)-O(2) 88.61(5) O(1)#1-Co(1)-O(2) 91.39(5)
    O(1)-Co(1)-O(2)#1 91.39(5) O(2)-Co(1)-O(2)#1 180.00(8) O(2)-Co(1)-N(1)#1 91.04(4)
    O(1)-Co(1)-N(1)#1 87.54(5) O(1)-Co(1)-N(1) 92.46(5) O(1)#1-Co(1)-N(1) 87.54(5)
    N(1)-Co(1)-O(2) 88.96(4) O(2)#1-Co(1)-N(1) 91.04(4) N(1)#1-Co(1)-N(1) 180.00(16)
    Compound 2
    Co(1)-N(1) 0.216 16(11) Co(1)-O(1) 0.209 37(11) Co(1)-O(2) 0.213 65(11)
    O(2)-Co(1)-N(1) 89.77(4) O(1)-Co(1)-O(2)#2 93.38(4) O(2)-Co(1)-O(2)#2 180
    O(1)#2-Co(1)-O(1) 180 O(1)-Co(1)-O(2) 86.62(4) N(1)#2-Co(1)-N(1) 180.00(3)
    O(1)-Co(1)-N(1) 87.11(4) O(2)#2-Co(1)-N(1) 90.23(4) O(1)#2-Co(1)-N(1) 92.89(4)
    Symmetry codes: #1:-x+1, -y+1, -z for 1; #2:-x+1, -y, -z+1 for 2.

    CCDC: 1437803, 1; 1401543, 2.

    2   Result and discussion

    2.1   Crystal structure of compound 1

    Compound 1 crystallizes in the monoclinic crystal system with P21/n space group. The asymmetric unit consists of half of a Co atom, one BPYPY ligand, two coordinated water molecules and half of a free trans-chdc2-, two free water molecules. As shown in Fig. 1, each Co (Ⅱ) atom is six coordinated by two nitrogen atoms from two BPYPY ligands and four oxygen atoms from four coordinated water molecules, to form the nuclear of [Co (BPYPY)2(H2O)4]. The bond distances of Co-N are 0.218 06(12) nm. The Co-O (1) bond length is 0.207 40(11) nm, and Co-O (2) bond length is 0.208 54(11) nm. It is noteworthy that [Co (BPYPY)2(H2O)4] cross-link trans-chdc2- by O-H…O hydrogen bonds generating the 2D network (Fig. 2).

    Figure 1.  Coordination environment of the Co (Ⅱ) cation in compound 1
    Figure 2.  2D network of compound 1

    2.2   Crystal structure of compound 2

    Compound 2 crystallizes in the orthorhombic crystal system with the space group of Pccn, and the asymmetric unit consists of half of a Co atom, half of a BPYPY ligand, two coordinated water molecules, half of a free completely deprotonated oba2- ligand. Each Co (Ⅱ) atom is surrounded by two nitrogen atoms from two BPYPY ligands, and four oxygen atoms from four coordinated water molecules, adopting an octahedral geometry (Fig. 3). The bond distance of Co-N is 0.216 16(11) nm. The Co-O bond lengths are 0.209 37(11) and 0.213 65(11) nm, respectively. The 1D linear chain with a Co…Co distance of 1.408 49 nm and a Co…Co…Co angle of 180.00° is generated by BPYPY ligands and the Co (Ⅱ) cations. Then, the 1D linear chains are held together via O-H…O interaction to generate an infinite 3D network (Fig. 4).

    Figure 3.  Coordination environment of the Co (Ⅱ) cation in compound 2
    Figure 4.  3D infinite network of compound 2

    3   Conclusions

    In summary, by using the V-shaped ligand, 3, 5-bis (4-pyridyl)-pyridine (BPYPY), and two kinds of dicarboxylates, trans-1, 4'-cyclohexanedicarboxylic acid (trans-chdc) and 4, 4'-oxydibenzoic acid (H2oba), we have synthesized two new compounds in mild hydrothermal method. Compound 1 has a 2D network generated by hydrogen bond cross-linked [Co (BPYPY)2(H2O)4] and trans-chdc2-. Compound 2 is a 1D chain and further extended via O-H…O interaction to generate infinite 3D supramolecular structure.

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  • Figure 1  Coordination environment of the Co (Ⅱ) cation in compound 1

    Thermal ellipsoids were drawn at the 30% level, and the hydrogen atoms were omitted for clarity; Symmetry codes: #1:-x+1, -y+1, -z

    Figure 2  2D network of compound 1

    Figure 3  Coordination environment of the Co (Ⅱ) cation in compound 2

    All hydrogen atoms were omitted for clarity; Symmetry codes: #2:-x+1, -y, -z+1

    Figure 4  3D infinite network of compound 2

    The O-H…O hydrogen bonds are shown as dashed lines

    Table 1.  Crystallographic data for compounds 1 and 2

    Compound 1 2
    Empirical formula C38H48CoN6O12 C29H27CoN3O9
    Formula weight 839.75 620.47
    Crystal system Monoclinic Orthorhombic
    Space group P21/n Pccn
    a / nm 1.479 47(6) 0.800 81(2)
    b/ nm 0.692 80(3) 2.700 75(7)
    c / nm 1.954 89(8) 1.230 98(3)
    β/(°) 99.280 0(10)
    V/ nm3 1.977 49(14) 2.662 35(12)
    Z 2 4
    Dc/(g·cm-3) 1.410 1.548
    Size / mm 0.28×0.26×0.22 0.30×0.28×0.26
    μ/ mm-1 0.504 0.708
    F(000) 882 1284
    θmin, θmax / (°) 2.71, 30.67 2.65, 27.56
    Goodness of fit on F2 1.033 1.058
    Reflections collected 13 752 13 759
    Independent reflections (Rint) 4 892(0.021 1) 3048(0.017 7)
    R1, wR2 [I > 2σ(I)] 0.033 7, 0.086 8 0.030 7, 0.084 9
    R1, wR2 (all data) 0.045 2, 0.093 8 0.035 7, 0.088 5
    ρ) max, (Δρ) min/ (e·nm-3) 413, -298 272, -349
    下载: 导出CSV

    Table 2.  Selected bond lengths(nm) and bond angles(°) of compounds 1 and 2

    Compound 1
    Co(1)-O(1) 0.207 40(11) Co(1)-N(1) 0.218 06(12) Co(1)-O(2) 0.208 54(11)
    O(1)_Co(1)-O(1)#1 180.00(7) O(1)-Co(1)-O(2) 88.61(5) O(1)#1-Co(1)-O(2) 91.39(5)
    O(1)-Co(1)-O(2)#1 91.39(5) O(2)-Co(1)-O(2)#1 180.00(8) O(2)-Co(1)-N(1)#1 91.04(4)
    O(1)-Co(1)-N(1)#1 87.54(5) O(1)-Co(1)-N(1) 92.46(5) O(1)#1-Co(1)-N(1) 87.54(5)
    N(1)-Co(1)-O(2) 88.96(4) O(2)#1-Co(1)-N(1) 91.04(4) N(1)#1-Co(1)-N(1) 180.00(16)
    Compound 2
    Co(1)-N(1) 0.216 16(11) Co(1)-O(1) 0.209 37(11) Co(1)-O(2) 0.213 65(11)
    O(2)-Co(1)-N(1) 89.77(4) O(1)-Co(1)-O(2)#2 93.38(4) O(2)-Co(1)-O(2)#2 180
    O(1)#2-Co(1)-O(1) 180 O(1)-Co(1)-O(2) 86.62(4) N(1)#2-Co(1)-N(1) 180.00(3)
    O(1)-Co(1)-N(1) 87.11(4) O(2)#2-Co(1)-N(1) 90.23(4) O(1)#2-Co(1)-N(1) 92.89(4)
    Symmetry codes: #1:-x+1, -y+1, -z for 1; #2:-x+1, -y, -z+1 for 2.
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  • 发布日期:  2016-05-10
  • 收稿日期:  2015-11-23
  • 修回日期:  2016-01-30
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