English

• 0.   Introduction

  In recent years, the rational design and construction of coordination polymers have received remarkable attention due to their potential applica-tions, architectures, and topologies^[1-5]. There are many factors, such as the coordination geometry of the metal centers, type and connectivity of organic ligands, stoichiometry, reaction conditions, template effect, presence of auxiliary ligands, and pH values influenc-ing the structures of target coordination polymers during self-assembly^[6-10]. Among these factors, organic ligands play a noteworthy role in constructing coor-dination compounds.

  Multi-carboxylate biphenyl ligands have been certified to be of great significance as constructors due to their strong coordination abilities in various modes, which could satisfy different geometric requi-rements of metal centers^{[8-9, 11-14]}. In order to extend our research in this field, we chose one biphenyl tricar-boxylic acid ligand, 5-(3, 4-dicarboxylphenyl)picolinic acid (H₃dppa), to construct novel coordination comp-ounds. The ligand possesses the following features: (1) it contains a pyridyl and a phenyl ring with structural flexibility and conformation. Rotation of the C-C single bond between pyridyl and phenyl rings could form numbers of coordination geometries of metal ions. (2) It has seven potential coordination sites, one N atom from pyridyl ring and six O atoms of three carboxylate groups, which is benifical to contruct coordination polymerw with interesting structures by its rich coordination modes. (3) It can act as hydrogen-bond acceptor as well as donor, depending upon the degree of deprotonation.

  Taking into account these factors, we herein report the syntheses, crystal structures and magnetic properties of two Cu(Ⅱ) and Mn(Ⅱ) coordination compounds constructed from biphenyl tricarboxylic acid ligands.

  1.   Experimental

  1.1   Reagents and physical measurement

  All chemicals and solvents were of AR grade and used without further purification. Carbon, hydrogen and nitrogen were determined using an Elementar Vario EL elemental analyzer. IR spectra were recorded using KBr pellets and a Bruker EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA) data were collected on a LINSEIS STA PT1600 thermal analyzer with a heating rate of 10 ℃·min^-1. Magnetic susceptibility data were collected in the 2~300 K temperature range with a Quantum Design SQUID Magnetometer MPMS XL-7 with a field of 0.1 T. A correction was made for the diamagnetic contribution prior to data analysis.

  1.2   Synthesis of [Cu₂(Hdppa)₂(4, 4′-bipy)(H₂O)₄]· 4, 4′-bipy·6H₂O (1)

  A mixture of CuCl₂·2H₂O (0.051 g, 0.30 mmol), H₃dppa (0.086 g, 0.30 mmol), 4, 4′-bipy (0.047 g, 0.3 mmol), NaOH (0.024 g, 0.60 mmol), and H₂O (10 mL) was stirred at room temperature for 15 min, and then sealed in a 25 mL Teflon-lined stainless steel vessel, and heated at 160 ℃ for 3 days, followed by cooling to room temperature at a rate of 10 ℃·h^-1. Blue block-shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 55% (based on H₃dppa). Anal. Calcd. for C₄₈H₅₀Cu₂N₆O₂₂(%): C 48.44, H 4.23, N 7.06; Found(%): C 48.59, H 4.27, N 7.02. IR (KBr, cm^-1): 3 667w, 3 317w, 2 979w, 1 726w, 1 603s, 1 557w, 1 493w, 1 423w, 1 382s, 1 347s, 1 307w, 1 254 m, 1 225w, 1 143w, 1 073w, 1 044w, 892w, 852w, 828w, 805m, 700w, 664w, 642w, 583w.

  1.3   Synthesis of {[Mn₃(μ₅-dppa)₂(4, 4′-bipy)(H₂O)₂] ·4H₂O}_n (2)

  The synthesis of 2 was similar as compound 1 using MnCl₂·4H₂O (0.059 g, 0.30 mmol) instead of CuCl₂·2H₂O. Yellow block-shaped crystals of 2 were gained. Yield: 60% (based on H₃dppa). Anal. Calcd. for C₃₈H₃₂Mn₃N₄O₁₈(%): C 45.76, H 3.23, N 5.62; Found(%): C 45.61, H 3.21, N 5.65. IR (KBr, cm^-1): 3 504w, 3 312w, 2 921w, 1 592s, 1 562s, 1 487w, 1 428w, 1 399 m, 1 307w, 1 248w, 1 213w, 1 160w, 1 090w, 1 062w, 1 026w, 1 003w, 921w, 903w, 852m, 811m, 706w, 658w, 630w, 589w. The compounds are insoluble in water and common organic solvents, such as methanol, ethanol, acetone and DMF.

  1.4   Structure determinations

  The diffraction data of two single crystals with dimensions of 0.25 mm×0.23 mm×0.21 mm (1) and 0.28 mm×0.23 mm×0.21 mm (2) was collected at 293(2) K on a Bruker SMART APEX Ⅱ CCD diffractometer with Mo Kα radiation (λ=0.071 073 nm). The struc-tures were solved by direct methods and refined by full matrix least-square on F² using the SHELXTL-2014 program^[15]. All non-hydrogen atoms were refined anisotropically. All the hydrogen atoms were positioned geometrically and refined using a riding model. A summary of the crystallography data and structure refinements for 1 and 2 is given in Table 1. The selected bond lengths and angles for compounds 1 and 2 are listed in Table 2. Hydrogen bond para-meters of compounds 1 and 2 are given in Table 3.

  表 1

  

  表 1  Crystal data for compounds 1 and 2

  Table 1.  Crystal data for compounds 1 and 2

  下载: 导出CSV

  Compound	1	2
  Chemical formula	C48H50Cu2N6O22	C38H32Mn3N4O18
  Molecular weight	1 190.02	997.49
  Crystal system	Triclinic	Monoclinic
  Space group	P1	C2/c
  a / nm	0.710 81(6)	2.481 35(10)
  b / nm	0.940 17(5)	0.736 26(3)
  c / nm	1.843 62(10)	2.400 42(9)
  α / (°)	90.217(4)
  β / (°)	96.594(6)	115.444(5)
  γ / (°)	99.334(6)
  V / nm3	1.207 38(14)	3.960 0(3)
  Z	1	4
  F(000)	614	2 028
  Crystal size / mm	0.25×0.23×0.22	0.28×0.23×0.21
  θ range for data collection	3.338~25.049	3.244~25.049
  Limiting indices	-8 ≤ h ≤ 8, -11 ≤ k ≤ 10, -20 ≤ l ≤ 21	-29 ≤ h ≤ 29, -8 ≤ k ≤ 8, -28 ≤ l ≤ 24
  Reflection collected, unique (Rint)	7 727, 4 274 (0.036 5)	7 289, 3 518 (0.038 8)
  Dc / (g·cm-3)	1.637	1.673
  μ / mm-1	0.975	1.028
  Data, restraint, parameter	4 274, 0, 355	3 518, 0, 297
  Goodness-of-fit on F2	1.026	1.053
  Final R indices [I≥2σ(I)] R1, wR2	0.055 8, 0.127 8	0.046 1, 0.100 4
  R indices (all data) R1, wR2	0.075 0, 0.143 1	0.064 8, 0.113 3
  Largest diff. peak and hole / (e·nm-3)	943 and -1 029	518 and -490

  表 2

  

  表 2  Selected bond distances (nm) and bond angles (°) for compounds 1 and 2

  Table 2.  Selected bond distances (nm) and bond angles (°) for compounds 1 and 2

  下载: 导出CSV

  1
  Cu(1)-O(2)	0.196 7(3)	Cu(1)-O(7)	0.222 3(3)	Cu(1)-O(8)	0.197 5(3)
  Cu(1)-N(1)	0.199 4(3)	Cu(1)-N(2)	0.199 9(3)
  O(2)-Cu(1)-O(8)	161.32(13)	O(2)-Cu(1)-N(1)	82.37(13)	O(8)-Cu(1)-N(1)	96.55(13)
  O(2)-Cu(1)-N(2)	87.90(14)	O(8)-Cu(1)-N(2)	91.46(14)	N(1)-Cu(1)-N(2)	169.57(15)
  O(2)-Cu(1)-O(7)	105.19(13)	O(8)-Cu(1)-O(7)	93.49(13)	N(1)-Cu(1)-O(7)	93.56(13)
  N(2)-Cu(1)-O(7)	92.61(13)
  2
  Mn(1)-O(1)	0.218 6(3)	Mn(1)-O(1)A	0.218 6(3)	Mn(1)-O(4)B	0.214 2(2)
  Mn(1)-O(4)C	0.214 2(2)	Mn(1)-O(7)	0.222 7(2)	Mn(1)-O(7)A	0.222 7(2)
  Mn(2)-O(2)	0.221 0(2)	Mn(2)-O(3)	0.215 3(2)	Mn(2)-O(5)D	0.216 5(2)
  Mn(2)-O(6)E	0.214 9(3)	Mn(2)-N(1)D	0.230 2(3)	Mn(2)-N(2)	0.226 6(3)
  O(4)B-Mn(1)-O(4)C	96.63(14)	O(4)B-Mn(1)-O(1)	87.90(10)	O(4)C-Mn(1)-O(1)	170.61(9)
  O(1)-Mn(1)-O(1)A	88.84(15)	O(4)B-Mn(1)-O(7)A	85.31(9)	O(4)C-Mn(1)-O(7)A	94.25(9)
  O(1)-Mn(1)-O(7)A	94.32(9)	O(1)-Mn(1)-O(7)	86.15(9)	O(7)-Mn(1)-O(7)A	179.35(14)
  O(6)E-Mn(2)-O(3)	85.37(10)	O(6)E-Mn(2)-O(5)D	96.99(10)	O(3)-Mn(2)-O(5)D	176.51(10)
  O(6)E-Mn(2)-O(2)	170.00(9)	O(3)-Mn(2)-O(2)	84.78(9)	O(5)D-Mn(2)-O(2)	92.77(10)
  O(6)E-Mn(2)-N(2)	87.30(11)	O(3)-Mn(2)-N(2)	90.95(10)	O(5)D-Mn(2)-N(2)	86.61(10)
  O(2)-Mn(2)-N(2)	91.11(10)	O(6)E-Mn(2)-N(1)D	92.09(10)	O(3)-Mn(2)-N(1)D	108.60(9)
  O(5)D-Mn(2)-N(1)D	73.95(9)	O(2)-Mn(2)-N(1)D	92.71(10)	N(2)-Mn(2)-N(1)D	160.34(10)
  Symmetry codes: A: -x, y, -z+1/2; B: x, y+1, z; C: -x, y+1, -z+1/2; D: -x+1/2, -y+1/2, -z+1; E: x, -y, z-1/2 for 2.

  表 3

  

  表 3  Hydrogen bond parameters of compounds 1 and 2

  Table 3.  Hydrogen bond parameters of compounds 1 and 2

  下载: 导出CSV

  D-H…A	d(D-H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  1
  O(5)-H(1)…N(4)A	0.082	0.183	0.260 3	157.6
  O(7)-H(1W)…O(1)B	0.085	0.187	0.272 3	179.6
  O(7)-H(2W)…O(11)C	0.073	0.199	0.271 5	171.6
  O(8)-H(3W)…O(4)D	0.085	0.184	0.268 8	179.5
  O(8)-H(4W)…O(5)A	0.085	0.175	0.260 3	179.5
  O(9)-H(5W)…O(10)E	0.085	0.188	0.273 3	179.3
  O(9)-H(6W)…O(3)A	0.085	0.184	0.268 5	178.2
  O(10)-H(7W)…O(4)D	0.085	0.194	0.278 8	178.3
  O(11)-H(9W)…O3)A	0.085	0.189	0.274 4	179.0
  O(11)-H(10W)…O(4)D	0.085	0.216	0.300 9	179.2
  2
  O(7)-H(1W)…O(3)A	0.086	0.224	0.294 4	138.8
  O(8)-H(3W)…O(2)B	0.085	0.213	0.293 6	159.0
  Symmetry codes: A: -x+1, -y+1, -z+1; B: x-1, y, z; C: x, y-1, z; D: -x+2, -y+1, -z+1; E: -x+1, -y+1, -z for 1; A: x, y+1, z; B: -x+1/2, y-1/2, -z+1/2 for 2.

  2.   Results and discussion

  2.1   Description of the structure

  2.1.1   [Cu₂(Hdppa)₂(4, 4′-bipy)(H₂O)₄]·4, 4′-bipy·6H₂O (1)

  Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the triclinic space group P1. Its asymmetric unit contains one crystallographically unique Cu(Ⅱ) atom, one Hdppa^2- block, a half of one 4, 4′-bipy moiety, two H₂O ligands, a half of one free 4, 4′-bipy ligand, and three lattice water molecules. As depicted in Fig. 1, Cu1 atom is surrounded by three O and two N atoms in a slightly distorted {CuO₃N₂} square-pyramidal geometry with the τ value of 0.138 (τ=0 for a regular square-pyramidal geometry and τ=1 for a perfect trigonal-bipyramidal geometry)^[16]. The two O (O2 and O8) and two N (N1 and N2) atoms occupy the basal plane, and one O (O7) atom resides at the apical position of the coordination polyhedron. The lengths of the Cu-O bonds range from 0.196 7(3) to 0.222 3(3) nm, whereas the Cu-N distances vary from 0.199 4(3) to 0.199 9(3) nm; these bonding parameters are comparable to those found in other reported Cu(Ⅱ) compounds^{[14, 17]}. In 1, the Hdppa^2- ligand adopts terminal coordination mode (mode Ⅰ, Scheme 1), in which the deprotonated carbo-xylate groups show the monodentate or uncoordinated modes. The dihedral angle between pyridyl and phenyl rings in the Hdppa^2- is 17.51°. Two crystallographi-cally equal Cu(Ⅱ) centers are bridged by the 4, 4′-bipy ligand to form a discrete dinuclear copper(Ⅱ) structure with a Cu…Cu separation of 1.104(3) nm (Fig. 2). These Cu₂ units are assembled to a 3D supramole-cular framework through O-H…O/N hydrogen bond (Fig. 3 and Table 3).

  图 1

  

  图 1  Drawing of the asymmetric unit of compound 1 with 30% probability thermal ellipsoids

  Figure 1.  Drawing of the asymmetric unit of compound 1 with 30% probability thermal ellipsoids

  下载: 全尺寸图片 幻灯片

  图 2

  

  图 2  Dinuclear Cu(Ⅱ) unit of 1

  Figure 2.  Dinuclear Cu(Ⅱ) unit of 1

  下载: 全尺寸图片 幻灯片

  图 3

  

  图 3  Perspective of 3D supramolecular framework parallel to the bc plane in 1

  Figure 3.  Perspective of 3D supramolecular framework parallel to the bc plane in 1

  下载: 全尺寸图片 幻灯片

  Scheme 1

  

  图 Scheme 1  Coordination modes of Hdppa^2- / dppa^3- ligands in compounds 1 and 2

  Scheme 1.  Coordination modes of Hdppa^2- / dppa^3- ligands in compounds 1 and 2

  下载: 全尺寸图片 幻灯片

  2.1.2   {[Mn₃(μ₅-dppa)₂(4, 4′-bipy)(H₂O)₂]·4H₂O}_n (2)

  The asymmetric unit of 2 consists of two crystallographically distinct Mn atoms (Mn1 with half occupancy; Mn2 with full occupancy), one μ₅-appa^3- block, a half of one 4, 4′-bipy ligand, one coordinated and two lattice water molecules. As shown in Fig. 4, six-coordinate Mn1 atom reveals a distorted octahedral {MnO₆} environment, filled by four carboxylate O atoms from four individual μ₅-dppa^3- blocks and two O atoms from two H₂O ligands. The Mn2 center is coordinated by four carboxylate O atoms from three distinct dppa^3- moieties and two N atoms from two different 4, 4′-bipy ligands, thus composing octahedral {MnO₄N₂} geometry. The Mn-O distances range from 0.214 2(2) to 0.222 7(2) nm, whereas the Mn-N distances vary from 0.226 6(3) to 0.230 2(3) nm; these bonding parameters are comparable to those observed in other Mn(Ⅱ) compounds^{[9, 11, 13]}. In 2, the dppa^3- block acts as a μ₅-N, O₆-spacer and its COO^- groups take a bidentate bridging mode (mode Ⅱ, Scheme 1). In dppa^3-, a dihedral angle (between pyridyl and benzene rings) is 46.31°. The carboxylate groups of dppa^3- blocks bridge alternately neighboring Mn atoms to form the infinite right-handed or left-handed helical Mn-O-C-O-Mn chains (Fig. 5) with the Mn…Mn separ-ation of 0.545 7(2) and 0.534 8(2) nm. Two types of these helical chains are interconnected to each other through the Mn(Ⅱ) centers to produce a double-helix chain (Fig. 5). The adjacent double-helix subunits are further linked by the cptc^3- blocks into a 2D sheet (Fig. 6). These 2D sheets are arranged into a 3D framework by further coordination interactions of the dppa^3- and 4, 4′-bipy ligands to Mn atoms (Fig. 7).

  图 4

  

  图 4  Drawing of the asymmetric unit of compound 2 with 30% probability thermal ellipsoids

  Figure 4.  Drawing of the asymmetric unit of compound 2 with 30% probability thermal ellipsoids

  下载: 全尺寸图片 幻灯片

  图 5

  

  图 5  Double-helix chain unit in compound 2

  Figure 5.  Double-helix chain unit in compound 2

  下载: 全尺寸图片 幻灯片

  图 6

  

  图 6  Two dimensional sheet along the c axis in compound 2

  Figure 6.  Two dimensional sheet along the c axis in compound 2

  下载: 全尺寸图片 幻灯片

  图 7

  

  图 7  Three dimensional framework along the b axis in compound 2

  Figure 7.  Three dimensional framework along the b axis in compound 2

  下载: 全尺寸图片 幻灯片

  2.2   TGA analysis

  To determine the thermal stability of compounds 1 and 2, their thermal behaviors were investigated under nitrogen atmosphere by thermogravimetric analysis (TGA). As shown in Fig. 8, compound 1 loses its six lattice water molecules in the range of 41~162 ℃ (Obsd. 8.8%, Calcd. 9.1%), followed by the decom-position at 218 ℃. The TGA curve of 2 reveals that four lattice and two coordinated water molecules are released between 78 and 230 ℃ (Obsd. 10.5%, Calcd. 10.8%), and the dehydrated solid begins to decompose at 334 ℃.

  图 8

  

  图 8  TGA curves of compounds 1 and 2

  Figure 8.  TGA curves of compounds 1 and 2

  下载: 全尺寸图片 幻灯片

  2.3   Magnetic properties

  Variable-temperature magnetic susceptibility studies were carried out on powder sample of 2 in the 2~300 K temperature range. The χ_MT value at 300 K is 14.48 cm³·mol^-1·K, which is larger than the value of 13.12 cm³·mol^-1·K expected for three magnetically isolated high-spin Mn(Ⅱ) centers (S_Mn=5/2, g=2.0). Upon cooling, the χ_MT value drops down very slowly from 14.48 cm³·mol^-1·K at 300 K to 13.97 cm³·mol^-1·K at 100 K and then decreases steeply to 3.04 cm³·mol^-1·K at 2 K (Fig. 9). The χ_M^-1 vs T plot for 2 in the 2~300 K range obeys the Curie-Weiss law with a Weiss constant θ of -6.88 K and a Curie constant C of 14.78 cm³·mol^-1·K. The negative value of θ and the decr-ease of the χ_MT should be attributed to the overall antiferromagnetic coupling between the Mn(Ⅱ) centers within double-helix chain unit. We attempted to fit the data for 2 by applying the following expression^[18] for a 1D Mn(Ⅱ) chain:

  $ \begin{array}{l} H{\rm{ = - }}J{S_i}{S_j}\\ {\chi _{{\rm{chain}}}}{\rm{ = [}}N{g^{\rm{2}}}{\beta ^{\rm{2}}}{\rm{(}}kT{\rm{)](}}A + B{x^{\rm{2}}}{\rm{)(1 + }}Cx + D{x^{\rm{3}}}{{\rm{)}}^{{\rm{ - 1}}}} \end{array} $

  图 9

  

  图 9  Temperature dependence of χ_M^T (○) and 1/χ_M(□) vs T for compound 2

  Figure 9.  Temperature dependence of χ_M^T (○) and 1/χ_M(□) vs T for compound 2

  下载: 全尺寸图片 幻灯片

  with A=2.916 7, B=208.04, C=15.543, D=2 707.2, and x=|J|/(kT).

  The susceptibility for 2 was simulated using this rough model, and resulting in J=-3.01 cm^-1, g=2.07, and R=4.98×10^-5. The negative J parameter indicates a weak antiferromagnetic exchange coupling between the adjacent Mn(Ⅱ) centers in 2, which is in agree-ment with a negative θ value.

  3.   Conclusions

  In summary, two new coordination compounds, namely [Cu₂(Hdppa)₂(4, 4′-bipy)(H₂O)₄]·4, 4′-bipy·6H₂O (1) and {[Mn₃(μ₅-dppa)₂(4, 4′-bipy)(H₂O)₂]·4H₂O}_n (2), have been synthesized under hydrothermal conditions. The compounds feature the 0D dinuclear and 3D framework structures, respectively. Magnetic studies show an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers in 2.

• 1. [1]

     Hu Z G, Zhao D. CrystEngComm, 2017, 19:4066-4081 doi: 10.1039/C6CE02660E

  2. [2]

     Lv R, Li H, Su J, et al. Inorg. Chem., 2017, 56:12348-12356 doi: 10.1021/acs.inorgchem.7b01822

  3. [3]

     Li P Z, Wang X J, Liu J, et al. CrystEngComm, 2017, 19:4157-4161 doi: 10.1039/C7CE00100B

  4. [4]

     Cui Y, Yue Y, Qian G, et al. Chem. Rev., 2012, 112:1126-1162

  5. [5]

     Kuppler R J, Timmons D J, Fang Q R, et al. Coord. Chem. Rev., 2009, 253:3042-3066 doi: 10.1016/j.ccr.2009.05.019

  6. [6]

     Gu J Z, Cui Y H, Liang X X, et al. Cryst. Growth Des., 2016, 16:4658-4670 doi: 10.1021/acs.cgd.6b00735

  7. [7]

     Ji P F, Manna K, Lin Z, et al. J. Am. Chem. Soc., 2016, 138:12234-12242 doi: 10.1021/jacs.6b06759

  8. [8]

     Gu J Z, Gao Z Q, Tang Y. Cryst. Growth Des., 2012, 12:3312-3323 doi: 10.1021/cg300442b

  9. [9]

     Gu J Z, Wu J, Lv D Y, et al. Dalton Trans., 2013, 42:4822-4830 doi: 10.1039/c2dt32674d

  10. [10]

      Du M, Li C P, Liu C S, et al. Coord. Chem. Rev., 2013, 257:1282-1305 doi: 10.1016/j.ccr.2012.10.002

  11. [11]

      Gu J Z, Liang X X, Cui Y H, et al. CrystEngComm, 2017, 19:117-128 doi: 10.1039/C6CE02115H

  12. [12]

      鲁雅, 吕天喜, 胡未极, 等.无机化学学报, 2017, 33(10):1869-1875 doi: 10.11862/CJIC.2017.215LU Ya, LÜTian-Xi, HU Wei-Ji, et al. Chinese J. Inorg. Chem., 2017, 33(10):1869-1875 doi: 10.11862/CJIC.2017.215

  13. [13]

      赵素琴, 顾金忠.无机化学学报, 2016, 32(9):1611-1618ZHAO Su-Qin, GU Jin-Zhong. Chinese J. Inorg. Chem., 2016, 32(9):1611-1618

  14. [14]

      陈金伟, 温炳松, 曹芳利, 等.无机化学学报, 2017, 33(12):2322-2328 doi: 10.11862/CJIC.2017.229CHEN Jin-Wei, WEN Bing-Song, CAO Fang-Li, et al. Chinese J. Inorg. Chem., 2017, 33(12):2322-2328 doi: 10.11862/CJIC.2017.229

  15. [15]

      Spek A L. Acta Crystallogr. Sect. C:Struct. Chem., 2015, C71:9-18

  16. [16]

      Addison A W, Rao T N, Reedijk J, et al. J. Chem. Soc. Dalton Trans., 1984:1349-1356 doi: 10.1107/S1600536805006173/pdf

  17. [17]

      Gu J Z, Liang X X, Cai Y, et al. Dalton Trans., 2017, 46:10908-10925 doi: 10.1039/C7DT01742A

  18. [18]

      Hiller W, Strhel J, Datz A, et al. J. Am. Chem. Soc., 1984, 106:329-335 doi: 10.1021/ja00314a013

• 

  Figure 1  Drawing of the asymmetric unit of compound 1 with 30% probability thermal ellipsoids

  H atoms are omitted for clarity except the H atoms of the COOH groups; Symmetry codes: A:-x+1, -y, -z

  下载: 全尺寸图片 幻灯片
  

  Figure 2  Dinuclear Cu(Ⅱ) unit of 1

  H atoms are omitted for clarity except the H atoms of the COOH groups; Symmetry codes: A:-x+1, -y, -z

  下载: 全尺寸图片 幻灯片
  

  Figure 3  Perspective of 3D supramolecular framework parallel to the bc plane in 1

  下载: 全尺寸图片 幻灯片
  

  Scheme 1  Coordination modes of Hdppa^2- / dppa^3- ligands in compounds 1 and 2

  下载: 全尺寸图片 幻灯片
  

  Figure 4  Drawing of the asymmetric unit of compound 2 with 30% probability thermal ellipsoids

  H atoms were omitted for clarity; Symmetry codes: A:-x, y, -z+1/2; B: x, y+1, z; C:-x, y+1, -z+1/2; D: -x+1/2, -y+1/2, -z+1; E: x, -y, z-1/2; F: -x, -y+1, -z

  下载: 全尺寸图片 幻灯片
  

  Figure 5  Double-helix chain unit in compound 2

  下载: 全尺寸图片 幻灯片
  

  Figure 6  Two dimensional sheet along the c axis in compound 2

  下载: 全尺寸图片 幻灯片
  

  Figure 7  Three dimensional framework along the b axis in compound 2

  下载: 全尺寸图片 幻灯片
  

  Figure 8  TGA curves of compounds 1 and 2

  下载: 全尺寸图片 幻灯片
  

  Figure 9  Temperature dependence of χ_M^T (○) and 1/χ_M(□) vs T for compound 2

  Solid curve represents the best fit to the equations in the text and the line shows the Curie-Weiss fitting

  下载: 全尺寸图片 幻灯片

  Table 1.  Crystal data for compounds 1 and 2

  Compound	1	2
  Chemical formula	C48H50Cu2N6O22	C38H32Mn3N4O18
  Molecular weight	1 190.02	997.49
  Crystal system	Triclinic	Monoclinic
  Space group	P1	C2/c
  a / nm	0.710 81(6)	2.481 35(10)
  b / nm	0.940 17(5)	0.736 26(3)
  c / nm	1.843 62(10)	2.400 42(9)
  α / (°)	90.217(4)
  β / (°)	96.594(6)	115.444(5)
  γ / (°)	99.334(6)
  V / nm3	1.207 38(14)	3.960 0(3)
  Z	1	4
  F(000)	614	2 028
  Crystal size / mm	0.25×0.23×0.22	0.28×0.23×0.21
  θ range for data collection	3.338~25.049	3.244~25.049
  Limiting indices	-8 ≤ h ≤ 8, -11 ≤ k ≤ 10, -20 ≤ l ≤ 21	-29 ≤ h ≤ 29, -8 ≤ k ≤ 8, -28 ≤ l ≤ 24
  Reflection collected, unique (Rint)	7 727, 4 274 (0.036 5)	7 289, 3 518 (0.038 8)
  Dc / (g·cm-3)	1.637	1.673
  μ / mm-1	0.975	1.028
  Data, restraint, parameter	4 274, 0, 355	3 518, 0, 297
  Goodness-of-fit on F2	1.026	1.053
  Final R indices [I≥2σ(I)] R1, wR2	0.055 8, 0.127 8	0.046 1, 0.100 4
  R indices (all data) R1, wR2	0.075 0, 0.143 1	0.064 8, 0.113 3
  Largest diff. peak and hole / (e·nm-3)	943 and -1 029	518 and -490

  下载: 导出CSV

  Table 2.  Selected bond distances (nm) and bond angles (°) for compounds 1 and 2

  1
  Cu(1)-O(2)	0.196 7(3)	Cu(1)-O(7)	0.222 3(3)	Cu(1)-O(8)	0.197 5(3)
  Cu(1)-N(1)	0.199 4(3)	Cu(1)-N(2)	0.199 9(3)
  O(2)-Cu(1)-O(8)	161.32(13)	O(2)-Cu(1)-N(1)	82.37(13)	O(8)-Cu(1)-N(1)	96.55(13)
  O(2)-Cu(1)-N(2)	87.90(14)	O(8)-Cu(1)-N(2)	91.46(14)	N(1)-Cu(1)-N(2)	169.57(15)
  O(2)-Cu(1)-O(7)	105.19(13)	O(8)-Cu(1)-O(7)	93.49(13)	N(1)-Cu(1)-O(7)	93.56(13)
  N(2)-Cu(1)-O(7)	92.61(13)
  2
  Mn(1)-O(1)	0.218 6(3)	Mn(1)-O(1)A	0.218 6(3)	Mn(1)-O(4)B	0.214 2(2)
  Mn(1)-O(4)C	0.214 2(2)	Mn(1)-O(7)	0.222 7(2)	Mn(1)-O(7)A	0.222 7(2)
  Mn(2)-O(2)	0.221 0(2)	Mn(2)-O(3)	0.215 3(2)	Mn(2)-O(5)D	0.216 5(2)
  Mn(2)-O(6)E	0.214 9(3)	Mn(2)-N(1)D	0.230 2(3)	Mn(2)-N(2)	0.226 6(3)
  O(4)B-Mn(1)-O(4)C	96.63(14)	O(4)B-Mn(1)-O(1)	87.90(10)	O(4)C-Mn(1)-O(1)	170.61(9)
  O(1)-Mn(1)-O(1)A	88.84(15)	O(4)B-Mn(1)-O(7)A	85.31(9)	O(4)C-Mn(1)-O(7)A	94.25(9)
  O(1)-Mn(1)-O(7)A	94.32(9)	O(1)-Mn(1)-O(7)	86.15(9)	O(7)-Mn(1)-O(7)A	179.35(14)
  O(6)E-Mn(2)-O(3)	85.37(10)	O(6)E-Mn(2)-O(5)D	96.99(10)	O(3)-Mn(2)-O(5)D	176.51(10)
  O(6)E-Mn(2)-O(2)	170.00(9)	O(3)-Mn(2)-O(2)	84.78(9)	O(5)D-Mn(2)-O(2)	92.77(10)
  O(6)E-Mn(2)-N(2)	87.30(11)	O(3)-Mn(2)-N(2)	90.95(10)	O(5)D-Mn(2)-N(2)	86.61(10)
  O(2)-Mn(2)-N(2)	91.11(10)	O(6)E-Mn(2)-N(1)D	92.09(10)	O(3)-Mn(2)-N(1)D	108.60(9)
  O(5)D-Mn(2)-N(1)D	73.95(9)	O(2)-Mn(2)-N(1)D	92.71(10)	N(2)-Mn(2)-N(1)D	160.34(10)
  Symmetry codes: A: -x, y, -z+1/2; B: x, y+1, z; C: -x, y+1, -z+1/2; D: -x+1/2, -y+1/2, -z+1; E: x, -y, z-1/2 for 2.

  下载: 导出CSV

  Table 3.  Hydrogen bond parameters of compounds 1 and 2

  D-H…A	d(D-H) / nm	d(H…A) / nm	d(D…A) / nm	∠DHA / (°)
  1
  O(5)-H(1)…N(4)A	0.082	0.183	0.260 3	157.6
  O(7)-H(1W)…O(1)B	0.085	0.187	0.272 3	179.6
  O(7)-H(2W)…O(11)C	0.073	0.199	0.271 5	171.6
  O(8)-H(3W)…O(4)D	0.085	0.184	0.268 8	179.5
  O(8)-H(4W)…O(5)A	0.085	0.175	0.260 3	179.5
  O(9)-H(5W)…O(10)E	0.085	0.188	0.273 3	179.3
  O(9)-H(6W)…O(3)A	0.085	0.184	0.268 5	178.2
  O(10)-H(7W)…O(4)D	0.085	0.194	0.278 8	178.3
  O(11)-H(9W)…O3)A	0.085	0.189	0.274 4	179.0
  O(11)-H(10W)…O(4)D	0.085	0.216	0.300 9	179.2
  2
  O(7)-H(1W)…O(3)A	0.086	0.224	0.294 4	138.8
  O(8)-H(3W)…O(2)B	0.085	0.213	0.293 6	159.0
  Symmetry codes: A: -x+1, -y+1, -z+1; B: x-1, y, z; C: x, y-1, z; D: -x+2, -y+1, -z+1; E: -x+1, -y+1, -z for 1; A: x, y+1, z; B: -x+1/2, y-1/2, -z+1/2 for 2.

  下载: 导出CSV
•