English

• The design and construction of multifarious complexes has been a hot topic for all researchers owing to their intriguing structural motifs and potential applications in optics, magnetism, recognition, etc^[1-8]. Although the assembly of complexes is affected by varied factors, we haven′t stopped exploring them. In consideration of the superiority of the "mixed-ligand" synthetic strategies^[9-12], which can lead to numerous graceful structures, we choose 1, 4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene (btbb) as the semi-rigid N-donor ligand and different multidentate O-donor carboxylates, m-phenylenediacetic acid (m-H₂phda), 1, 3-adamantanedicarboxylic acid (H₂adtda), 5-tert-buty-lisophthalic acid (H₂tbi), 3-Nitro-1, 2-benzenedicarbo-xylic acid (3-Nitro-o-H₂bdc) as auxiliary ligands in the synthesis of metal-organic coordination polymer mater-ials. Five diverse structural complexes, {[Zn(btbb)_0.5(m-phda)]·0.5H₂O}_n (1), {[Cd₂(btbb)(adtda)₂(H₂O)]·H₂O}_n (2), [Mn₂(btbb)(tbi)₂]_n (3), {[Cd(btbb)_0.5(3-Nitro-o-bdc)(H₂O)]·H₂O}_n (4) and [Cd₂(btbb)(tbi)₂]_n (5) were prep-ared. The structures of 1~5 have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra, elemental analyses.

  1.   Experimental

  1.1   Materials and methods

  All reagents and solvents were commercially available without any further purification, except for ligand btbb, which was synthesized in accordance with the literature^[13]. The data of FT-IR spectra were recorded on a FTIR-7600 spectrophotometer with KBr pellets in a scale of 400~4 000 cm^-1. Elemental analyses of C, H and N were performed introducing a FLASH EA 1112 analyzer.

  1.2   Synthesis of {[Zn(btbb)_0.5(m-phda)]·0.5H₂O}_n (1)

  A mixture of Zn(Ac)₂·2H₂O (0.2 mmol), btbb (0.1 mmol), m-H₂phda (0.1 mmol), NaOH (0.2 mmol) and H₂O (10 mL) was placed in a 25 mL Teflon-lined stainless steel container. The mixture was sealed and heated at 180 ℃ for three days. After the mixture was cooled to ambient temperature at a rate of 5 ℃·h^-1, colorless crystals of 1 were obtained with a yield of 10% (based on Zn). Anal. Calcd. for C₂₄H₂₀ZnN₃O₅S(%): C, 54.60; H, 3.81; N, 7.95. Found(%): C, 54.63; H, 3.79; N, 7.98. IR (KBr, cm^-1): 3 421(s), 2 988(vw), 1 615(s), 1 481(w), 1 448(w), 1 395(m), 1 364(m), 1 314(vw), 1 272(vw), 1 174(w), 1 079(w), 1 001(w), 937(m), 887(w), 828(w), 784(w), 750(w), 622(w).

  1.3   Synthesis of {[Cd₂(btbb)(adtda)₂(H₂O)]·H₂O}_n(2)

  A mixture of Cd(NO₃)₂·4H₂O (0.1 mmol), btbb (0.1 mmol), p-H₂adtda (0.05 mmol), EtOH (5 mL) and H₂O (5 mL) was placed in a 25 mL Teflon-lined stainless steel container. The mixture was sealed and heated at 170 ℃ for three days. After the mixture was cooled to ambient temperature at a rate of 5 ℃·h^-1, colorless crystals of 2 were obtained with a yield of 15% (based on Cd). Anal. Calcd. for C₅₂H₅₂Cd₂N₆O₁₀S₂(%): C, 51.61; H, 4.33; N, 6.94. Found(%): C, 51.59; H, 4.30; N, 6.97. IR (KBr, cm^-1): 3 440(s), 2 908 (m), 2 946(m), 1 616(w), 1 562(s), 1 479(w), 1 448(s), 1 386(s), 1 307(s), 1 241(w), 1 124(w), 1 041(w), 931(m), 889(m), 823(m), 744(s), 713(m), 622(w).

  1.4   Synthesis of [Mn₂(btbb)(tbi)₂]_n (3)

  A mixture of MnCl₂·4H₂O (0.1 mmol), btbb (0.05 mmol), H₂tbi (0.05 mmol), CH₃CN (4 mL) and H₂O (6 mL) was placed in a 25 mL Teflon-lined stainless steel container. The mixture was sealed and heated at 160 ℃ for three days. After the mixture was cooled to ambient temperature at a rate of 5 ℃·h^-1, colorless crystals of 3 were obtained with a yield of 13% (based on Mn). Anal. Calcd. for C₅₂H₄₄Mn₂N₆O₈S₂(%): C, 59.20; H, 4.20; N, 7.96. Found(%): C, 59.23; H, 4.22; N, 7.92. IR (KBr, cm^-1): 3 409(m), 3 091(m), 2 962(s), 2 865(w), 1 604(s), 1 554(s), 1 436(s), 1 371(s), 1 307(s), 1 268(s), 1 108(s), 1 014(m), 923(s), 850(s), 819(s), 725(s).

  1.5   Synthesis of {[Cd(btbb)_0.5(3-Nitro-o-bdc)(H₂O)]·H₂O}n (4)

  A mixture of Cd(NO₃)₂·4H₂O (0.1 mmol), btbb (0.05 mmol), 3-Nitro-o-H₂bdc (0.05 mmol), EtOH (7 mL) and H₂O (3 mL) was placed in a 25 mL Teflon-lined stainless steel container. The mixture was sealed and heated at 120 ℃ for three days. After the mixture was cooled to ambient temperature at a rate of 5 ℃·h^-1, colorless crystals of 4 were obtained with a yield of 16% (based on Cd). Anal. Calcd. for C₂₂H₁₇CdN₄O₈S(%): C, 43.32; H, 2.80; N, 9.18. Found(%): C, 43.27; H, 2.81; N, 9.22. IR (KBr, cm^-1): 3 397(m), 3 139(w), 3 099(w), 3 048(w), 1 581(s), 1 527(s), 1 459(s), 1 394(s), 1 349(s), 1 261(w), 1 162(m), 1 014(m), 935(s), 892(s), 831(s), 752(s), 717(s).

  1.6   Synthesis of [Cd₂(btbb)(tbi)₂]_n (5)

  A mixture of Cd(NO₃)₂·4H₂O (0.05 mmol), btbb (0.05 mmol), H₂tbi (0.05 mmol), EtOH (7 mL) and H₂O (3 mL) was placed in a 25 mL Teflon-lined stainless steel container. The mixture was sealed and heated at 120 ℃ for three days. After the mixture was cooled to ambient temperature at a rate of 5 ℃·h^-1, colorless crystals of 5 were obtained with a yield of 20% (based on Cd). Anal. Calcd. for C₅₂H₄₄Cd₂N₆O₈S₂(%): C, 53.38; H, 3.79; N, 7.18. Found(%): C, 53.35; H, 3.80; N, 7.16. IR (KBr, cm^-1): 3 432(m), 3 112(w), 2 958(w), 1 604(m), 1 550(s), 1 425(s), 1 386(s), 1 311(w), 1 116(vw), 927(s), 854(vw), 767(s), 725(m).

  1.7   Crystal structural determination

  The data of 1~5 were collected on a Rigaku Saturn 724 CCD diffractomer (Mo Kα, λ=0.071 073 nm) at temperature of 293(2) K. Absorption corrections were applied by using multi-scan program. The data were corrected for Lorentz and polarization effects. The structures were solved by direct methods and refined with a full-matrix least-squares technique based on F² with the SHELX-97 crystallographic software package^[14]. The hydrogen atoms were placed at calculated positions and refined as riding atoms with isotropic displacement parameters. Crystallographic crystal data and structure processing parameters for 1~5 are summarized in Table 1. Selected bond lengths and bond angles for 1~5 are listed in Table 2, respectively.

  Table 1

  

  Table 1.  Crystal data and structure refinement details for complexes 1~5

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  Complex	1	2	3	4	5
  Formula	C24H20ZnN3O5S	C52H52Cd2N6O10S2	C52H44Mn2N6O8S2	C22H17CdN4O8S	C52H44Cd2N6O8S2
  Formula weight	527.86	1 207.90	1 054.93	608.85	1 169.85
  Crystal system	Triclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	P1	P21/c	P21/c	P21/c	P21/c
  a / nm	0.862 78(17)	1.987 7(4)	1.024 2(2)	1.332 6(3)	1.033 8(2)
  b / nm	1.075 7(2)	2.118 5(4)	2.218 5(4)	1.094 7(2)	2.222 5(4)
  c / nm	1.322 9(3)	1.164 0(2)	2.027 8(4)	1.575 4(3)	2.015 0(4)
  α / (°)	72.83(3)
  β / (°)	84.65(3)	93.39(3)	96.39(3)	100.31(3)	95.79(3)
  γ / (°)	73.83(3)
  V / nm3	1.126 5(4)	4.892 7(17)	4.578 9(16)	2.261 1(8)	4.605 7(16)
  Z	2	4	4	4	4
  Dc / (g·cm-3)	1.556	1.640	1.530	1.789	1.687
  μ / mm-1	1.225	1.022	0.708	1.117	1.079
  F(000)	542	2 448	2 176	1 216	2 360
  θ range / (°)	1.61~27.90	1.41~25.50	1.37~25.50	1.55~27.89	1.98~25.00
  GOF	1.041	1.036	1.027	1.036	1.037
  R1 [I>2σ(I)]a	0.065 0	0.074 8	0.087 8	0.078 7	0.097 3
  wR2 [I>2σ(I)]b	0.147 9	0.176 7	0.224 1	0.168 3	0.169 0
  a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=[∑w(Fo2-Fc2)2/∑w(Fo2)2]1/2.

  Table 2

  

  Table 2.  Selected bond lengths (nm) and bond angles (°) for 1~5

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  Complex 1
  Zn(1)-O(1)	0.197 8(3)	Zn(1)-O(2)	0.243 2(3)	Zn(1)-O(4)#1	0.213 3(4)
  Zn(1)-O(3)#1	0.233 6(6)	Zn(1)-N(2)	0.214 1(4)	Zn(1)-N(1)	0.205 3(3)
  O(1)-Zn(1)-N(1)	138.48(15)	O(1)-Zn(1)-O(4)#1	114.26(17)	N(1)-Zn(1)-O(4)#1	94.52(14)
  O(1)-Zn(1)-N(2)	100.37(15)	N(1)-Zn(1)-N(2)	77.73(12)	O(4)#1-Zn(1)-N(2)	132.77(16)
  O(1)-Zn(1)-O(3)#1	97.36(18)	N(1)-Zn(1)-O(3)#1	123.88(16)	O(4)#1-Zn(1)-O(3)#1	56.71(16)
  N(2)-Zn(1)-O(3)#1	89.06(15)	O(1)-Zn(1)-O(2)	57.06(12)	N(1)-Zn(1)-O(2)	91.85(12)
  O(4)#1-Zn(1)-O(2)	96.79(16)	N(2)-Zn(1)-O(2)	129.59(14)	O(3)#1-Zn(1)-O(2)	134.10(16)
  Complex 2
  Cd(1)-O(8)#1	0.216 4(7)	Cd(1)-O(2)	0.224 4(5)	Cd(1)-O(3)	0.226 8(5)
  Cd(2)-O(4)	0.226 8(6)	Cd(2)-O(5)	0.253 8(6)	Cd(1)-O(1)	0.258 3(5)
  Cd(2)-O(7)#2	0.219 8(6)	Cd(2)-O(6)	0.221 3(6)	Cd(1)-N(1)	0.227 9(6)
  Cd(2)-N(5)	0.232 4(6)	Cd(2)-N(4)	0.240 2(7)	Cd(1)-N(3)	0.243 7(6)
  O(8)#1-Cd(1)-O(2)	104.9(3)	O(8)#1-Cd(1)-O(3)	111.9(3)	O(2)-Cd(1)-O(3)	95.70(19)
  O(8)#1-Cd(1)-N(1)	87.8(3)	O(2)-Cd(1)-N(1)	105.4(2)	O(3)-Cd(1)-N(1)	146.48(19)
  O(8)#1-Cd(1)-N(3)	89.9(3)	O(2)-Cd(1)-N(3)	164.40(19)	O(3)-Cd(1)-N(3)	82.97(19)
  N(1)-Cd(1)-N(3)	69.7(2)	O(8)#1-Cd(1)-O(1)	155.3(3)	O(2)-Cd(1)-O(1)	53.10(16)
  O(3)-Cd(1)-O(1)	83.91(19)	N(1)-Cd(1)-O(1)	88.20(19)	N(3)-Cd(1)-O(1)	111.37(18)
  O(7)#2-Cd(2)-O(6)	116.9(3)	O(7)#2-Cd(2)-O(4)	86.5(3)	O(6)-Cd(2)-O(4)	91.6(3)
  O(7)#2-Cd(2)-N(5)	107.4(3)	O(6)-Cd(2)-N(5)	131.1(3)	O(4)-Cd(2)-N(5)	111.4(2)
  O(7)#2-Cd(2)-N(4)	90.3(3)	O(6)-Cd(2)-N(4)	89.6(3)	O(4)-Cd(2)-N(4)	176.8(2)
  N(5)-Cd(2)-N(4)	69.9(2)	O(7)#2-Cd(2)-O(5)	139.0(3)	O(6)-Cd(2)-O(5)	78.9(2)
  O(4)-Cd(2)-O(5)	54.01(19)	N(5)-Cd(2)-O(5)	81.19(19)	N(4)-Cd(2)-O(5)	129.2(2)
  Complex 3
  Mn(1)-O(3)	0.213 2(4)	Mn(1)-O(6)#1	0.217 6(4)	Mn(1)-O(2)	0.224 4(4)
  Mn(2)-O(7)#1	0.244 9(4)	Mn(2)-O(4)	0.217 2(4)	Mn(1)-O(1)	0.234 4(4)
  Mn(2)-O(5)#1	0.212 0(4)	Mn(2)-O(8)#1	0.214 1(4)	Mn(1)-N(1)	0.234 3(4)
  Mn(2)-N(5)	0.224 5(5)	Mn(2)-N(4)	0.233 2(6)	Mn(1)-N(2)	0.225 4(5)
  O(3)-Mn(1)-O(6)#1	99.19(15)	O(3)-Mn(1)-O(2)	105.51(16)	O(6)#1-Mn(1)-O(2)	89.71(15)
  O(3)-Mn(1)-N(2)	150.13(17)	O(6)#1-Mn(1)-N(2)	87.97(17)	O(2)-Mn(1)-N(2)	103.47(17)
  O(3)-Mn(1)-N(1)	84.83(16)	O(6)#1-Mn(1)-N(1)	132.10(16)	O(2)-Mn(1)-N(1)	135.48(15)
  N(2)-Mn(1)-N(1)	69.37(17)	O(3)-Mn(1)-O(1)	90.41(15)	O(6)#1-Mn(1)-O(1)	146.30(16)
  O(2)-Mn(1)-O(1)	56.59(14)	N(2)-Mn(1)-O(1)	99.60(16)	N(1)-Mn(1)-O(1)	80.66(15)
  O(5)#1-Mn(2)-O(8)#1	106.90(17)	O(5)#1-Mn(2)-O(4)	102.29(15)	O(8)#1-Mn(2)-O(4)	92.06(15)
  O(5)#1-Mn(2)-N(5)	152.22(17)	O(8)#1-Mn(2)-N(5)	99.64(18)	O(4)-Mn(2)-N(5)	84.52(17)
  O(5)#1-Mn(2)-N(4)	82.89(17)	O(8)#1-Mn(2)-N(4)	142.84(17)	O(4)-Mn(2)-N(4)	121.45(16)
  N(5)-Mn(2)-N(4)	70.87(19)	O(5)#1-Mn(2)-O(7)#1	89.07(14)	O(8)#1-Mn(2)-O(7)#1	56.73(14)
  O(4)-Mn(2)-O(7)#1	148.78(14)	N(5)-Mn(2)-O(7)#1	98.92(16)	N(4)-Mn(2)-O(7)#1	88.50(16)
  Complex 4
  Cd(1)-O(1)	0.256 8(7)	Cd(1)-O(3)#1	0.245 6(5)	Cd(1)-O(2)	0.234 8(5)
  Cd(1)-O(7)	0.237 1(6)	Cd(1)-O(4)#1	0.238 9(6)	Cd(1)-N(1)	0.234 5(6)
  Cd(1)-N(2)	0.229 8(5)
  N(2)-Cd(1)-N(1)	72.2(2)	N(2)-Cd(1)-O(2)	128.60(18)	N(1)-Cd(1)-O(2)	98.0(2)
  N(2)-Cd(1)-O(7)	99.84(19)	N(1)-Cd(1)-O(7)	170.8(2)	O(2)-Cd(1)-O(7)	83.30(19)
  N(2)-Cd(1)-O(4)#1	94.42(18)	N(1)-Cd(1)-O(4)#1	107.4(2)	O(2)-Cd(1)-O(4)#1	135.36(18)
  O(7)-Cd(1)-O(4)#1	77.3(2)	N(2)-Cd(1)-O(3)#1	141.95(18)	N(1)-Cd(1)-O(3)#1	95.8(2)
  O(2)-Cd(1)-O(3)#1	88.12(17)	O(7)-Cd(1)-O(3)#1	93.4(2)	O(4)#1-Cd(1)-O(3)#1	53.91(18)
  N(2)-Cd(1)-O(1)	76.71(19)	N(1)-Cd(1)-O(1)	87.8(3)	O(2)-Cd(1)-O(1)	52.19(18)
  O(7)-Cd(1)-O(1)	85.7(3)	O(4)#1-Cd(1)-O(1)	159.3(2)	O(3)#1-Cd(1)-O(1)	140.19(19)
  Complex 5
  Cd(1)-O(3)	0.228 7(7)	Cd(1)-O(5)	0.228 7(7)	Cd(1)-O(1)#1	0.230 5(7)
  Cd(2)-O(6)	0.229 5(7)	Cd(2)-O(8)#2	0.253 9(7)	Cd(1)-O(2)#1	0.248 4(7)
  Cd(2)-O(7)#2	0.224 7(7)	Cd(2)-O(4)	0.226 3(8)	Cd(1)-N(1)	0.233 7(10)
  Cd(2)-N(4)	0.231 1(11)	Cd(2)-N(6)	0.243 5(13)	Cd(1)-N(3)	0.240 9(9)
  O(3)-Cd(1)-O(5)	101.4(3)	O(3)-Cd(1)-O(1)#1	87.5(3)	O(5)-Cd(1)-O(1)#1	106.2(3)
  O(3)-Cd(1)-N(1)	89.0(3)	O(5)-Cd(1)-N(1)	148.6(3)	O(1)#1-Cd(1)-N(1)	103.8(3)
  O(3)-Cd(1)-N(3)	137.1(3)	O(5)-Cd(1)-N(3)	85.1(3)	O(1)#1-Cd(1)-N(3)	131.8(3)
  N(1)-Cd(1)-N(3)	67.8(3)	O(3)-Cd(1)-O(2)#1	141.5(3)	O(5)-Cd(1)-O(2)#1	89.6(3)
  O(1)#1-Cd(1)-O(2)#1	54.0(3)	N(1)-Cd(1)-O(2)#1	100.6(3)	N(3)-Cd(1)-O(2)#1	80.1(3)
  O(7)#2-Cd(2)-O(4)	107.6(3)	O(7)#2-Cd(2)-O(6)	90.8(3)	O(4)-Cd(2)-O(6)	101.5(3)
  O(7)#2-Cd(2)-N(4)	101.6(4)	O(4)-Cd(2)-N(4)	149.6(4)	O(6)-Cd(2)-N(4)	86.0(3)
  O(7)#2-Cd(2)-N(6)	141.5(3)	O(4)-Cd(2)-N(6)	83.3(4)	O(6)-Cd(2)-N(6)	123.9(3)
  N(4)-Cd(2)-N(6)	68.5(4)	O(7)#2-Cd(2)-O(8)#2	54.5(3)	O(4)-Cd(2)-O(8)#2	90.6(3)
  O(6)-Cd(2)-O(8)#2	145.3(3)	N(4)-Cd(2)-O(8)#2	99.8(3)	N(6)-Cd(2)-O(8)#2	89.5(3)
  Symmetry codes: #1: -x, -y, -z+1 for 1; #1: -x+1, -y+1, -z+1; #2: -x, -y+1, -z+1 for 2; #1: x+1, y, z for 3; #1: -x, -y+1, -z for 4; #1: x+1, y, z; #2: x-1, y, z for 5.

  CCDC: 1883643, 1; 1883644, 2; 1883645, 3; 1883646, 4; 1883647, 5.

  2.   Results and discussion

  2.1   Crystal structure of {[Zn(btbb)_0.5(m-phda)]·0.5H₂O}_n (1)

  For complex 1, it consists of one crystallogra-phically independent Zn(Ⅱ) ion, half a btbb ligand, one m-phda^2- ligand, and half a lattice water molecule. As illustrated in Fig. 1a, Zn1(Ⅱ) ion is six-coordinated by four O atoms of carboxylate groups (O1, O2, O3#1, O4#1) provided by two different m-phda^2- ligands, and two nitrogen atoms (N1, N2) deriving from one btbb ligand to give a octahedral coordination geometry. The distances of Zn1-N1/N2 is 0.205 1(3)/0.213 4(3) nm, while the Zn1-O bond lengths range from 0.197 8(3) to 0.242 9(3) nm. Ligand btbb exhibit asymmetrical trans-conformation. N_donor…N-C_sp³…C_sp³ torsion angles of btbb is 143.613° and 143.614°, respectively. Ligand m-phda^2- adopts asymmetric cis-conformation, and the angles of two -CH_2^- are 112.478° and 116.908°. In 1, two carboxylic groups of the "V" shape ligand m-phda^2- take a chelating bidentate coordination modes. The m-phda2- anions connect two adjacent Zn(Ⅱ) ions using its two carboxylate groups resulting in a 22-membered rings along a-axis (Fig. 1b). The 22-membered rings are linked by btbb leading to a 1D chain along the a-axis (Fig. 1c). The Zn…Zn distances across btbb ligands are 1.322 17 nm.

  Figure 1

  

  Figure 1.  (a) Coordination environments of Zn(Ⅱ) in complex 1; (b) View of 22-membered rings constructed by two m-phda^2- ligands and two Zn(Ⅱ) ions along the a-axis; (c) 1D chain structure containing 22-membered rings along the a-axis

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x, -y, 1-z

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  2.2   Crystal structure of {[Cd₂(btbb)(adtda)₂(H₂O)]·H₂O}_n (2)

  Single crystal X-ray diffraction analysis reveals that 2 crystallizes in monoclinic space group P2₁/c. The asymmetric unit of 2 consists of two Cd(Ⅱ) ions, one btbb ligand, two adtda^2- anions, one coordinated water molecule and one lattice water molecule. As shown in Fig. 2a, the Cd1(Ⅱ) ion adopts a distorted octahedral geometry via coordinating with four oxygen atoms (O1, O2, O8#1) from two adtda^2- anions, one oxygen atom (O3) from one coordinated water molecule and two nitrogen atoms (N1 and N3) from one btbb ligand. The Cd1-O bond distances vary from 0.216 4(7) to 0.258 3(5) nm, while the Cd1-N1/N3 bond length is 0.227 9(6)/0.243 7(6) nm, separately. While the octahedral coordination geometry of the central Cd2(Ⅱ) ion is completed by two N atoms (N4 and N5) of one btbb ligand, and four O atoms (O4, O5, O6, O7#2) of three adtda^2- anions. The Cd2-O bond distances vary from 0.219 8(6) to 0.253 8(6) nm, while the Cd2-N4/N5 bond length is 0.240 2(7)/0.232 4(6) nm. The btbb ligand adopts asymmetric trans-conformation with two different N_donor…N-C_sp³…C_sp³ torsion angles of 71.150° and 93.156°. The ligand adtda^2- takes two different coordination modes. The first type (adtda^2--Ⅰ) is that one carboxylate group of adtda^2- ligand is in a bridging bidentate mode, and the other adopts a monodentate mode, whereas the two carboxylate groups of the second type (adtda^2--Ⅱ) both adopt chelating bidentate modes. The adtda^2--Ⅰ and adtda^2--Ⅱ anions link Cd(Ⅱ) ions to produce a one-dimensional (1D) chain structure having a dinuclear units [Cd₂(OCO)₂] with a Cd…Cd separation of 0.424 84 nm (Fig. 2b). Interestingly, 1D Cd(Ⅱ)/adtda^2- chain is further embellished by btbb giving rise to a more complex and beautiful 1D chain structure, and the Cd…Cd separation across btbb bridge is 1.013 00 nm (Fig. 2c).

  Figure 2

  

  Figure 2.  (a) Perspective view of the coordination environment of Cd(Ⅱ) ion in 2; (b) 1D chain constructed by Cd(Ⅱ) ions and adtda^2- anions having a 8-membered rings; (c) 1D chain embellished by btbb

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x+1, -y+1, -z+1; #2: -x, -y+1, -z+1

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  2.3   Crystal structure of [Mn₂(btbb)(tbi)₂]_n(3)

  The asymmetric unit of complex 3 contains two Mn(Ⅱ) ions, one btbb ligand and two tbi^2- ligands in the monoclinic space group P2₁/c. As shown in Fig. 3a, the Mn1 center is six-coordinated by four oxygen atoms (O1, O2, O3 and O6) belonging to three separated tbi^2- ligands as well as two nitrogen atoms (N1 and N2) from one btbb ligand to generate a distorted octahedral coordination geometry. The Mn1-O bond distances lie in a range of 0.213 2(4)~0.234 4(4) nm, and Mn1-N1/N2 bond distances are 0.234 3(4)/0.225 4(5) nm, respectively. The Mn2 center also adopts a distorted octahedral coordination environment, which is provided by two nitrogen atoms (N4, N5) from one separate btbb and four oxygen atoms (O4, O5, O7, O8) from three tbi^2-. The Mn2-O bond distances lie in a range of 0.212 0(4)~0.244 9(4) nm, and Mn2-N4/N5 bond distances are 0.233 2(6)/0.224 5(5) nm. As shown in Fig. 3b, both carboxylate groups of rigid tbi^2- anions adopt the mono-bidentate-bridging coordination fashion and chelating bidentate mode, separately, linking Mn(Ⅱ) ions to a 1D chain, which contains a dual-core unit [Mn₂(OCO)₂] with the Mn…Mn distance of 0.413 54 nm. The ligand btbb adopts asymmetric trans-conformation with two different N_donor…N-C_sp³…C_sp³ torsion angles of 44.822° and 78.136°, and it connects two adjacent 1D Mn(Ⅱ)/tbi^2- chain by sharing the Mn(Ⅱ) ions resulting in a 1D double chain (Fig. 3c).

  Figure 3

  

  Figure 3.  (a) Coordination environments of Mn(Ⅱ) in complex 3; (b) View of 1D Mn(Ⅱ)/tbi^2- chain; (c) 1D double chain structure of 3

  Hydrogen atoms are omitted for clarity

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  2.4   Crystal structure of {[Cd(btbb)_0.5(3-Nitro-o-bdc)(H₂O)]·H₂O}_n (4)

  Structural analysis indicates that complex 4 is a 1D chain structure and crystallizes in the monoclinic P2₁/c space group. The asymmetric unit of 4 is composed of one crystallographically independent Cd(Ⅱ) ion, half a btbb ligand, and one 3-Nitro-o-bdc^2- ligand, a coordination water molecule and a free water molecule. As shown in Fig. 4a, the Cd(Ⅱ) ion adopts a seven-coordinated environment, which is provided by two nitrogen atoms (N1, N2) from one btbb ligand, four oxygen atoms (O1, O2, O3#1, O4#1) from two 3-Nitro-o-bdc^2- anions and one oxygen atom (O7) from a coordination water molecule. The Cd-O distances are in a range of 0.234 8(5)~0.256 8(7) nm, while the Cd-N1/N2 bond length are 0.234 5(6)/2.298(5) nm, separately. The ligand btbb shows the symmetric trans-conformation with the N_donor…N-C_sp³…C_sp³ torsion angle of 162.223°. The carboxylic groups of each 3-Nitro-o-bdc^2- anion both adopt chelating bidentate coordination modes. By this way, two 3-Nitro-o-bdc^2- anions bridge two adjacent Cd(Ⅱ) ions to form a 14-membered ring along c-axis (Fig. 4b). Interestingly, the neighboring 14-membered rings are connected by the trans-conformational btbb ligands generating the 1D chain of 4 (Fig. 4c), with a Cd…Cd distance of 1.334 02 nm.

  Figure 4

  

  Figure 4.  Coordination environments of Cd(Ⅱ) in complex 4; (b) View of 14-membered rings constructed by two 3-Nitro-o-bdc^2- anions and two Cd(Ⅱ) ions along the c-axis; (c) 1D chain structure containing 14-membered rings along the c-axis

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x, 1-y, -z

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  2.5   Crystal structure of [Cd₂(btbb)(tbi)₂]_n (5)

  Single crystal X-ray diffraction analysis shows that 5 crystallizes in the space group P2₁/c. As shown in Fig. 5a, Cd1(Ⅱ) ion adopts a distorted octahedral coordination environment, defined by four oxygen atoms (O1#1, O2#1, O3, O5) deriving from three different tbi^2- anions and two nitrogen atoms (N1, N3) originating from one btbb ligand. The distances of Cd1-N1/N3 are 0.233 7(10)/0.240 9(9) nm, while the Cd1-O bond lengths range from 0.228 7(7) to 0.248 4(7) nm. It can be clearly seen that the Cd2(Ⅱ) ion also sits in a distorted octahedral coordination geometry defined by four oxygen atoms (O4, O6, O7#2, O8#2) from three different tbi^2- anions and two nitrogen atoms (N4, N6) from one btbb ligand. The distances of Cd2-N4/N6 are 0.231 1(11)/0.243 5(13) nm, while the Cd2-O bond lengths range from 0.224 7(7) to 0.253 9(7) nm. Interestingly, there are one kind of independent tbi^2-, in which one carboxylate group adopts a bisdentate chelated coordination mode and the other adopts a bridging bidentate mode. The tbi^2- anions connect two Cd(Ⅱ) ions resulting in a Cd₂(OCO)₂, and Cd…Cd distance is 0.403 32 nm. The dual-core Cd₂(OCO)₂ units are further linked and extended by tbi^2- anions leading to the production of a 1D Cd(Ⅱ)/tbi^2- chain (Fig. 5b). While the btbb ligand adopts asymmetric trans-conformation with two different N_donor…N-C_sp³…C_sp³ torsion angles of 78.334° and 43.989°, and the bridged Cd…Cd distances along μ-btbb are 1.099 83 nm. Finally, the Cd1(Ⅱ) ion and Cd2(Ⅱ) ion are connected by btbb to afford a 1D double chain taking on stair-step (Fig. 5c).

  Figure 5

  

  Figure 5.  Perspective view of the coordination environment of Cd(Ⅱ) ion in 5; (b) 1D chain constructed by Cd (Ⅱ) ions and tbi^2- anions; (c) 1D double chain of 5

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1: x+1, y, z; #2: x-1, y, z

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  3.   Conclusions

  In short, the synergistic effect of the btbb and various carboxylates to react with Zn(Ⅱ)/Cd(Ⅱ)/Mn(Ⅱ)ions gains five different complexes. Complexes 1~5 exhibit captivating structural motifs.

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     Lu Z Z, Zhang R, Li Y Z, et al. J. Am. Chem. Soc., 2011, 133:4172-4174 doi: 10.1021/ja109437d

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     Blake K M, Johnston L L, Nettleman J H, et al. CrystEngComm, 2010, 12:1927-1934 doi: 10.1039/b925239h

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     喻敏, 宣芳, 刘光祥.无机化学学报, 2019, 35(1):133-140 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20190116&flag=1YU Min, XUAN Fang, LIU Guang-Xiang. Chinese J. Inorg. Chem., 2019, 35(1):133-140 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20190116&flag=1

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     梁丽丽, 刘从森, 宗智慧, 等.无机化学学报, 2018, 34(7):1365-1372 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20180719&flag=1LIANG Li-Li, LIU Cong-Sen, ZONG Zhi-Hui, et al. Chinese J. Inorg. Chem., 2018, 34(7):1365-1372 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20180719&flag=1

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     黎彧, 邹训重, 顾金忠, 等.无机化学学报, 2018, 34(6):1159-1165 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20180620&flag=1LI Yu, ZOU Xun-Zhong, GU Jin-Zhong, et al. Chinese J. Inorg. Chem., 2018, 34(6):1159-1165 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20180620&flag=1

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     Hu J S, Shang Y J, Yao X Q, et al. Cryst. Growth Des., 2010, 10:4135-4142 doi: 10.1021/cg1008208

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      Huang S L, Lin Y J, Andy Hor T S, et al. J. Am. Chem. Soc., 2013, 135:8125-8128 doi: 10.1021/ja402630g

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      Sheldrick G M. Acta Crystallogr. Sect. A:Found. Crystallogr., 2008, 64:112-122 doi: 10.1107/S0108767307043930

• 

  Figure 1  (a) Coordination environments of Zn(Ⅱ) in complex 1; (b) View of 22-membered rings constructed by two m-phda^2- ligands and two Zn(Ⅱ) ions along the a-axis; (c) 1D chain structure containing 22-membered rings along the a-axis

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x, -y, 1-z

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  Figure 2  (a) Perspective view of the coordination environment of Cd(Ⅱ) ion in 2; (b) 1D chain constructed by Cd(Ⅱ) ions and adtda^2- anions having a 8-membered rings; (c) 1D chain embellished by btbb

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x+1, -y+1, -z+1; #2: -x, -y+1, -z+1

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  Figure 3  (a) Coordination environments of Mn(Ⅱ) in complex 3; (b) View of 1D Mn(Ⅱ)/tbi^2- chain; (c) 1D double chain structure of 3

  Hydrogen atoms are omitted for clarity

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  Figure 4  Coordination environments of Cd(Ⅱ) in complex 4; (b) View of 14-membered rings constructed by two 3-Nitro-o-bdc^2- anions and two Cd(Ⅱ) ions along the c-axis; (c) 1D chain structure containing 14-membered rings along the c-axis

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1:-x, 1-y, -z

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  Figure 5  Perspective view of the coordination environment of Cd(Ⅱ) ion in 5; (b) 1D chain constructed by Cd (Ⅱ) ions and tbi^2- anions; (c) 1D double chain of 5

  Hydrogen atoms are omitted for clarity; Symmetry codes: #1: x+1, y, z; #2: x-1, y, z

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  Table 1.  Crystal data and structure refinement details for complexes 1~5

  Complex	1	2	3	4	5
  Formula	C24H20ZnN3O5S	C52H52Cd2N6O10S2	C52H44Mn2N6O8S2	C22H17CdN4O8S	C52H44Cd2N6O8S2
  Formula weight	527.86	1 207.90	1 054.93	608.85	1 169.85
  Crystal system	Triclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	P1	P21/c	P21/c	P21/c	P21/c
  a / nm	0.862 78(17)	1.987 7(4)	1.024 2(2)	1.332 6(3)	1.033 8(2)
  b / nm	1.075 7(2)	2.118 5(4)	2.218 5(4)	1.094 7(2)	2.222 5(4)
  c / nm	1.322 9(3)	1.164 0(2)	2.027 8(4)	1.575 4(3)	2.015 0(4)
  α / (°)	72.83(3)
  β / (°)	84.65(3)	93.39(3)	96.39(3)	100.31(3)	95.79(3)
  γ / (°)	73.83(3)
  V / nm3	1.126 5(4)	4.892 7(17)	4.578 9(16)	2.261 1(8)	4.605 7(16)
  Z	2	4	4	4	4
  Dc / (g·cm-3)	1.556	1.640	1.530	1.789	1.687
  μ / mm-1	1.225	1.022	0.708	1.117	1.079
  F(000)	542	2 448	2 176	1 216	2 360
  θ range / (°)	1.61~27.90	1.41~25.50	1.37~25.50	1.55~27.89	1.98~25.00
  GOF	1.041	1.036	1.027	1.036	1.037
  R1 [I>2σ(I)]a	0.065 0	0.074 8	0.087 8	0.078 7	0.097 3
  wR2 [I>2σ(I)]b	0.147 9	0.176 7	0.224 1	0.168 3	0.169 0
  a R1=∑||Fo|-|Fc||/∑|Fo|; b wR2=[∑w(Fo2-Fc2)2/∑w(Fo2)2]1/2.

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  Table 2.  Selected bond lengths (nm) and bond angles (°) for 1~5

  Complex 1
  Zn(1)-O(1)	0.197 8(3)	Zn(1)-O(2)	0.243 2(3)	Zn(1)-O(4)#1	0.213 3(4)
  Zn(1)-O(3)#1	0.233 6(6)	Zn(1)-N(2)	0.214 1(4)	Zn(1)-N(1)	0.205 3(3)
  O(1)-Zn(1)-N(1)	138.48(15)	O(1)-Zn(1)-O(4)#1	114.26(17)	N(1)-Zn(1)-O(4)#1	94.52(14)
  O(1)-Zn(1)-N(2)	100.37(15)	N(1)-Zn(1)-N(2)	77.73(12)	O(4)#1-Zn(1)-N(2)	132.77(16)
  O(1)-Zn(1)-O(3)#1	97.36(18)	N(1)-Zn(1)-O(3)#1	123.88(16)	O(4)#1-Zn(1)-O(3)#1	56.71(16)
  N(2)-Zn(1)-O(3)#1	89.06(15)	O(1)-Zn(1)-O(2)	57.06(12)	N(1)-Zn(1)-O(2)	91.85(12)
  O(4)#1-Zn(1)-O(2)	96.79(16)	N(2)-Zn(1)-O(2)	129.59(14)	O(3)#1-Zn(1)-O(2)	134.10(16)
  Complex 2
  Cd(1)-O(8)#1	0.216 4(7)	Cd(1)-O(2)	0.224 4(5)	Cd(1)-O(3)	0.226 8(5)
  Cd(2)-O(4)	0.226 8(6)	Cd(2)-O(5)	0.253 8(6)	Cd(1)-O(1)	0.258 3(5)
  Cd(2)-O(7)#2	0.219 8(6)	Cd(2)-O(6)	0.221 3(6)	Cd(1)-N(1)	0.227 9(6)
  Cd(2)-N(5)	0.232 4(6)	Cd(2)-N(4)	0.240 2(7)	Cd(1)-N(3)	0.243 7(6)
  O(8)#1-Cd(1)-O(2)	104.9(3)	O(8)#1-Cd(1)-O(3)	111.9(3)	O(2)-Cd(1)-O(3)	95.70(19)
  O(8)#1-Cd(1)-N(1)	87.8(3)	O(2)-Cd(1)-N(1)	105.4(2)	O(3)-Cd(1)-N(1)	146.48(19)
  O(8)#1-Cd(1)-N(3)	89.9(3)	O(2)-Cd(1)-N(3)	164.40(19)	O(3)-Cd(1)-N(3)	82.97(19)
  N(1)-Cd(1)-N(3)	69.7(2)	O(8)#1-Cd(1)-O(1)	155.3(3)	O(2)-Cd(1)-O(1)	53.10(16)
  O(3)-Cd(1)-O(1)	83.91(19)	N(1)-Cd(1)-O(1)	88.20(19)	N(3)-Cd(1)-O(1)	111.37(18)
  O(7)#2-Cd(2)-O(6)	116.9(3)	O(7)#2-Cd(2)-O(4)	86.5(3)	O(6)-Cd(2)-O(4)	91.6(3)
  O(7)#2-Cd(2)-N(5)	107.4(3)	O(6)-Cd(2)-N(5)	131.1(3)	O(4)-Cd(2)-N(5)	111.4(2)
  O(7)#2-Cd(2)-N(4)	90.3(3)	O(6)-Cd(2)-N(4)	89.6(3)	O(4)-Cd(2)-N(4)	176.8(2)
  N(5)-Cd(2)-N(4)	69.9(2)	O(7)#2-Cd(2)-O(5)	139.0(3)	O(6)-Cd(2)-O(5)	78.9(2)
  O(4)-Cd(2)-O(5)	54.01(19)	N(5)-Cd(2)-O(5)	81.19(19)	N(4)-Cd(2)-O(5)	129.2(2)
  Complex 3
  Mn(1)-O(3)	0.213 2(4)	Mn(1)-O(6)#1	0.217 6(4)	Mn(1)-O(2)	0.224 4(4)
  Mn(2)-O(7)#1	0.244 9(4)	Mn(2)-O(4)	0.217 2(4)	Mn(1)-O(1)	0.234 4(4)
  Mn(2)-O(5)#1	0.212 0(4)	Mn(2)-O(8)#1	0.214 1(4)	Mn(1)-N(1)	0.234 3(4)
  Mn(2)-N(5)	0.224 5(5)	Mn(2)-N(4)	0.233 2(6)	Mn(1)-N(2)	0.225 4(5)
  O(3)-Mn(1)-O(6)#1	99.19(15)	O(3)-Mn(1)-O(2)	105.51(16)	O(6)#1-Mn(1)-O(2)	89.71(15)
  O(3)-Mn(1)-N(2)	150.13(17)	O(6)#1-Mn(1)-N(2)	87.97(17)	O(2)-Mn(1)-N(2)	103.47(17)
  O(3)-Mn(1)-N(1)	84.83(16)	O(6)#1-Mn(1)-N(1)	132.10(16)	O(2)-Mn(1)-N(1)	135.48(15)
  N(2)-Mn(1)-N(1)	69.37(17)	O(3)-Mn(1)-O(1)	90.41(15)	O(6)#1-Mn(1)-O(1)	146.30(16)
  O(2)-Mn(1)-O(1)	56.59(14)	N(2)-Mn(1)-O(1)	99.60(16)	N(1)-Mn(1)-O(1)	80.66(15)
  O(5)#1-Mn(2)-O(8)#1	106.90(17)	O(5)#1-Mn(2)-O(4)	102.29(15)	O(8)#1-Mn(2)-O(4)	92.06(15)
  O(5)#1-Mn(2)-N(5)	152.22(17)	O(8)#1-Mn(2)-N(5)	99.64(18)	O(4)-Mn(2)-N(5)	84.52(17)
  O(5)#1-Mn(2)-N(4)	82.89(17)	O(8)#1-Mn(2)-N(4)	142.84(17)	O(4)-Mn(2)-N(4)	121.45(16)
  N(5)-Mn(2)-N(4)	70.87(19)	O(5)#1-Mn(2)-O(7)#1	89.07(14)	O(8)#1-Mn(2)-O(7)#1	56.73(14)
  O(4)-Mn(2)-O(7)#1	148.78(14)	N(5)-Mn(2)-O(7)#1	98.92(16)	N(4)-Mn(2)-O(7)#1	88.50(16)
  Complex 4
  Cd(1)-O(1)	0.256 8(7)	Cd(1)-O(3)#1	0.245 6(5)	Cd(1)-O(2)	0.234 8(5)
  Cd(1)-O(7)	0.237 1(6)	Cd(1)-O(4)#1	0.238 9(6)	Cd(1)-N(1)	0.234 5(6)
  Cd(1)-N(2)	0.229 8(5)
  N(2)-Cd(1)-N(1)	72.2(2)	N(2)-Cd(1)-O(2)	128.60(18)	N(1)-Cd(1)-O(2)	98.0(2)
  N(2)-Cd(1)-O(7)	99.84(19)	N(1)-Cd(1)-O(7)	170.8(2)	O(2)-Cd(1)-O(7)	83.30(19)
  N(2)-Cd(1)-O(4)#1	94.42(18)	N(1)-Cd(1)-O(4)#1	107.4(2)	O(2)-Cd(1)-O(4)#1	135.36(18)
  O(7)-Cd(1)-O(4)#1	77.3(2)	N(2)-Cd(1)-O(3)#1	141.95(18)	N(1)-Cd(1)-O(3)#1	95.8(2)
  O(2)-Cd(1)-O(3)#1	88.12(17)	O(7)-Cd(1)-O(3)#1	93.4(2)	O(4)#1-Cd(1)-O(3)#1	53.91(18)
  N(2)-Cd(1)-O(1)	76.71(19)	N(1)-Cd(1)-O(1)	87.8(3)	O(2)-Cd(1)-O(1)	52.19(18)
  O(7)-Cd(1)-O(1)	85.7(3)	O(4)#1-Cd(1)-O(1)	159.3(2)	O(3)#1-Cd(1)-O(1)	140.19(19)
  Complex 5
  Cd(1)-O(3)	0.228 7(7)	Cd(1)-O(5)	0.228 7(7)	Cd(1)-O(1)#1	0.230 5(7)
  Cd(2)-O(6)	0.229 5(7)	Cd(2)-O(8)#2	0.253 9(7)	Cd(1)-O(2)#1	0.248 4(7)
  Cd(2)-O(7)#2	0.224 7(7)	Cd(2)-O(4)	0.226 3(8)	Cd(1)-N(1)	0.233 7(10)
  Cd(2)-N(4)	0.231 1(11)	Cd(2)-N(6)	0.243 5(13)	Cd(1)-N(3)	0.240 9(9)
  O(3)-Cd(1)-O(5)	101.4(3)	O(3)-Cd(1)-O(1)#1	87.5(3)	O(5)-Cd(1)-O(1)#1	106.2(3)
  O(3)-Cd(1)-N(1)	89.0(3)	O(5)-Cd(1)-N(1)	148.6(3)	O(1)#1-Cd(1)-N(1)	103.8(3)
  O(3)-Cd(1)-N(3)	137.1(3)	O(5)-Cd(1)-N(3)	85.1(3)	O(1)#1-Cd(1)-N(3)	131.8(3)
  N(1)-Cd(1)-N(3)	67.8(3)	O(3)-Cd(1)-O(2)#1	141.5(3)	O(5)-Cd(1)-O(2)#1	89.6(3)
  O(1)#1-Cd(1)-O(2)#1	54.0(3)	N(1)-Cd(1)-O(2)#1	100.6(3)	N(3)-Cd(1)-O(2)#1	80.1(3)
  O(7)#2-Cd(2)-O(4)	107.6(3)	O(7)#2-Cd(2)-O(6)	90.8(3)	O(4)-Cd(2)-O(6)	101.5(3)
  O(7)#2-Cd(2)-N(4)	101.6(4)	O(4)-Cd(2)-N(4)	149.6(4)	O(6)-Cd(2)-N(4)	86.0(3)
  O(7)#2-Cd(2)-N(6)	141.5(3)	O(4)-Cd(2)-N(6)	83.3(4)	O(6)-Cd(2)-N(6)	123.9(3)
  N(4)-Cd(2)-N(6)	68.5(4)	O(7)#2-Cd(2)-O(8)#2	54.5(3)	O(4)-Cd(2)-O(8)#2	90.6(3)
  O(6)-Cd(2)-O(8)#2	145.3(3)	N(4)-Cd(2)-O(8)#2	99.8(3)	N(6)-Cd(2)-O(8)#2	89.5(3)
  Symmetry codes: #1: -x, -y, -z+1 for 1; #1: -x+1, -y+1, -z+1; #2: -x, -y+1, -z+1 for 2; #1: x+1, y, z for 3; #1: -x, -y+1, -z for 4; #1: x+1, y, z; #2: x-1, y, z for 5.

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