Cl Supramolecular Coordination Systems

Article pubs.acs.org/crystal

A Family of Fe(II)/Cl Supramolecular Coordination Systems Incorporating 5,5′-Di(pyridin-2-yl)-3,3′-bi(1,2,4-triazole) Peng-Fei Yao,†,‡ Ye Tao,† Hai-Ye Li,† Xiao-Huan Qin,† Dong-Wei Shi,† Fu-Ping Huang,*,† Qing Yu,† Xing-Xing Qin,† and He-Dong Bian*,‡ †

Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), School of Chemistry and Pharmacy, Guangxi Normal University, Guilin, 541004, P. R. China ‡ Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530008, P. R. China S Supporting Information *

ABSTRACT: By using a new N-heterocyclic building block, 5,5′-di(pyridin-2-yl)3,3′-bi(1,2,4-triazole) (2,2′-H2dbpt), five novel coordination complexes, Fe4(2,2′Hdbpt)2Cl6(H2O)6 (1), [Fe(2,2′-H2dbpt)Cl2·H2O]n (2), [Fe(2,2′-H2dbpt)Cl2]n (3), [Fe2(2,2′-H2dbpt)Cl4]n (4), and [Fe(2,2′-H2dbpt)0.5Cl2]n (5), based on a Fe(II)/Cl system with diversiform connectivity from zero- to two-dimensional (2D) were constructed successfully. By regulating the metal−ligand ratio and solvents, 2,2′H2dbpt changed various coordination modes. Consequently, 1 reveals a discrete Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supramolecule. 2 and 3 are pseudo-polymorphic. 2 reveals a helical chain based on the cis-FeCl2N4 unit and the cis-bridging 2,2′-H2dbpt ligand, while 3 reveals a straight-chain based on the trans-FeCl2N4 unit and the transbridging 2,2′-H2dbpt ligand. 4 and 5 are also supramolecular isomers. Different from 2 and 3, both of them have a cis-FeCl2N4 unit. Owing to the different rotation angles of pyridine rings in 2,2′-H2dbpt, 4 and 5 reveal a one-dimensional modified trapezoid chain based on the trans-bridging 2,2′-H2dbpt ligand and a 2D wave-like layer based on the cis-bridging 2,2′-H2dbpt ligand, respectively. Furthermore, compound 4 could also be viewed as a wave banded chain constructed by 3 with μ2-Cl ions replaced by the terminal Cl ions and water molecules from another perspective. 1 reveals weak antiferromagnetic behavior. 2, and 3 both reveal paramagnetic behavior, while 4 and 5 both reveal ferromagnetic behavior. These results indicate that 2,2′-H2dbpt is an excellent multi-connection linker to construct supramolecular coordination complexes with interesting structures and properties.

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complexes with various structures.48 Owing to the presence of the strong chelate effect between the adjacent aromatic rings, it could adopt various conformations, which may lead to unpredictable and interesting structures, by regulating the rotation angles of the four aromatic rings with respect to each other, the effect of deprotonation (2,2′-H2dpbt, 2,2′-Hdpbt−, 2,2′-dpbt2−) and the flexing angles. Besides, considering the wide occurrence of structural and compositional diversity during self-assembly and crystallization, supramolecular isomerism represents an indication of composition control and structure prediction. Actually, supramolecular isomerism is not just a challenge or obstacle, but also a good opportunity for developing novel materials and a better understanding of self-assembly and crystal growth.49 Since the concept “supramolecular isomerism” was discussed by Zaworotko in 2001,50 the design and synthesis of supramolecular isomers have received increasing attention.51−64

INTRODUCTION The design and synthesis of supramolecular coordination complexes have attracted remarkable attention in the realm of supramolecular chemistry and crystal engineering, not only owing to their appealing structural and topological novelty but also because of their tremendous potential applications in gas storage and separation,1−5 electrical conduction,6−9 luminescence materials,10−20 molecular magnets,21−26 and heterogeneous catalysis.27−32 However, how to rationally design and synthesize supramolecular coordination complexes with the desired structure and properties is still a challenge up to now. The assembly of such supramolecular systems may be easily affected by many factors, including the coordination geometry of the central metal ions, solvents,33−35 ligand structure, metal− ligand ratio,36,37 counterions,38−40 pH,41−44 temperature,45,46 and so on. Among the reported studies, much effort has been focused on the rational design and controlled synthesis of coordination polymers using multidentate ligands such as polycarboxylate acids, phosphonic acids, and organic ligands containing heterocyclic triazolyl groups.47 5,5′-Di(pyridin-2-yl)3,3′-bi(1,2,4-triazole)(2,2′-H2dbpt) may be a excellent multidentate ligand to construct supramolecular coordination © XXXX American Chemical Society

Received: May 27, 2015 Revised: July 19, 2015

A

DOI: 10.1021/acs.cgd.5b00724 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Scheme 1. Versatile Coordination Modes of 2,2′-H2dbpt Used in This Work

Table 1. Crystal Data and Structure Refinement for 1−5 1 Empirical formula formula weight (M) crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å 3) Z Dc (Mg m−3) F(000) θ range for data collection (deg) reflections collected/unique goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data)

2

3

5

C14H10Cl2FeN8·H2O 435.05 orthorhombic Pbca 8.9714 (10) 16.053 (6) 23.274 (2) 90.00 90.00 90.00 3351.9 (13) 8 1.716 1744 2.7−29.1

C14H10Cl2FeN8 417.05 triclinic P1̅ 6.7896 (8) 7.6307 (8) 8.3119 (9) 103.798 (8) 110.427 (8) 93.898 (10) 386.46 (7) 1 1.792 210 2.8−26.4

C14H10Cl4Fe2N8 543.80 triclinic P1̅ 6.8424 (4) 9.1998(4) 14.5135 (10) 79.457 (5) 89.008 (6) 88.406 (4) 897.77 (9) 2 2.012 540.0 2.9−29.2

C7H5Cl2FeN4 271.90 monoclinic P21/c 14.450 (2) 9.2033 (12) 6.7339 (5) 90.00 92.836 (8) 90.00 894.43 (18) 4 2.019 540.0 3.0−29.0

4108/3414 [R(int) = 0.034] 1.049 R1 = 0.0310, wR2 = 0.0682 R1 = 0.0402, wR2 = 0.0730

3415/1938 [R(int) = 0.142] 1.022 R1 = 0.0648, wR2 = 0.0917 R1 = 0.1313, wR2 = 0.1129

9523/1584 [R(int) = 0.033] 1.087 R1 = 0.0315, wR2 = 0.0934 R1 = 0.0327, wR2 = 0.0960

3673/2792 [R(int) = 0.025] 1.030 R1 = 0.0346, wR2 = 0.0689 R1 = 0.0503, wR2 = 0.0784

1835/1544 [R(int) = 0.044] 1.151 R1 = 0.0535, wR2 = 0.1176 R1 = 0.0644, wR2 = 0.1220

IIIA diffractometer (Cu-Kα, λ = 1.54056 Å). The single crystalline powder samples were prepared by crushing the crystals and were scanned from 3 to 60° with a step of 0.1°/s. Calculated patterns of 1− 5 were generated with PowderCell. Syntheses of Complexes 1− 5. Fe4(2,2′-Hdbpt)2Cl6(H2O)6 (1). A mixture containing 2,2′-H2dbpt (145 mg, 0.5 mmol), FeCl2·4H2O (199 mg, 1 mmol), ethanol (8 mL), and tertiary butanol (8 mL) was sealed in a Teflon-lined stainless steel vessel (25 mL), which was heated at 160 °C for 3 days and then cooled to room temperature at a rate of 10 °C/h. Yellow flake crystals of 1 were obtained and picked out, washed with ethanol, and dried in air. Yield: 27% (based on Fe(II)). Elemental analysis for C28H30Cl6Fe4N16O6 (%) Calcd: C, 29.95; H, 2.69; N, 19.96. Found: C: 29.72; H: 2.75; N: 19.69 IR (KBr, cm−1): 3371(s), 1609(w), 1449(m), 1424(w), 1284(w), 1268(m), 1155(w), 1051(w), 1018(m), 996(s), 988(s), 798(w), 755(w), 722(w), 637(m). [Fe(2,2′- H2dbpt)Cl2·H2O]n (2). A mixture containing 2,2′-H2dbpt (145 mg, 0.5 mmol), FeCl2·4H2O (100 mg, 0.5 mmol), and cyclohexanone (15 mL) was sealed in a Teflon-lined stainless steel vessel (25 mL), which was heated at 160 °C for 3 days and then cooled to room temperature at a rate of 10 °C/h. Yellow flake crystals of 2 were obtained and picked out, washed with ethanol, and dried in air. Yield: 12% (based on Fe(II)). Elemental analysis for C28H22OCl4Fe2N16 (%) Calcd: C, 39.47; H, 2.60; N, 26.30. Found: C: 39.32; H: 2.65; N: 26.26 IR (KBr, cm−1): 3396(s), 1610(w), 1462(m), 1399(w), 1375(w), 1344(m), 1289(w), 1262(w), 1215(m), 1182(s), 1152(s), 1054(w), 1010(w), 796(w), 757(w), 711(m), 639(w), 598(m), 524(m). [Fe(2,2′-H2dbpt)Cl2]n (3). The same synthetic procedure as that for 2 was used except that cyclohexanone was replaced by acetone giving

In this paper, a series of coordination polymers based on 2,2′-H2dbpt, namely, Fe4(2,2′-Hdbpt)2Cl6(H2O)6 (1), [Fe(2,2′-H2dbpt)Cl2·H2O]n (2), [Fe(2,2′-H2dbpt)Cl2]n (3), [Fe2(2,2′-H2dbpt)Cl4]n (4), and [Fe(2,2′-H2dbpt)0.5Cl2]n (5), were constructed successfully. By regulating the metal−ligand ratio and solvents, 2,2′-H2dbpt adopts four different coordination modes (Scheme 1) based on the alteration of the rotation angles, valence state, and the flexing angles. As a result, 1−5 have five different architectures with diversiform connectivity from zero- to two-dimensional. Among them, structures of 2 and 3 are pseudo-polymorphism revealing weak paramagnetic behavior; 4 and 5 are supramolecular isomers revealing ferromagnetic behavior.

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4

C28H30Cl6Fe4N16O6 1122.78 triclinic P1̅ 7.2793 (4) 9.7479 (7) 15.1562 (9) 100.504 (6) 94.495 (5) 105.762 (5) 1008.33 (12) 1 1.849 564 2.9−28.9

EXPERIMENTAL SECTION

Materials and Physical Measurements. With the exception of the ligand of 2,2′-H2dbpt which was prepared according to a literature procedure,65 all reagents and solvents for synthesis and analysis were commercially available and used as received. IR spectra were taken on a PerkinElmer spectrum One FT-IR spectrometer in the 4000−400 cm−1 region with KBr pellets. Elemental analyses for C, H, and N were carried out on a model 2400 II PerkinElmer elemental analyzer. The magnetic susceptibility measurements of the polycrystalline samples were measured over the temperature range of 2−300 K with a Quantum Design MPMS-XL7 SQUID magnetometer using an applied magnetic field of 1000 Oe. A diamagnetic correction to the observed susceptibilities was applied using Pascal’s constants. X-ray powder diffraction (XRPD) intensities were measured on a Rigaku D/maxB



Article

Table 2. Selected Atomic Distances (Å) and Bond Angles (deg) for Complexes 1−5 1 (Symmetry code: (A) −x + 2, −y + 1, −z + 1) Fe1Cl1 2.4864 (7) Fe2Cl1 Fe1Cl2 2.4809 (8) Fe2Cl2 Fe1O1 2.1078 (19) Fe2Cl3 Fe1O2 2.1109 (19) Fe2O3 Fe1N1 2.202 (2) Fe2N7A Fe1N2 2.2380 (18) Fe2N8A Cl2Fe1Cl1 87.45 (2) Cl2Fe2Cl1 O1Fe1Cl1 94.43 (5) Cl3Fe2Cl1 O1Fe1Cl2 175.69 (6) Cl3Fe2Cl2 O1Fe1O2 87.68 (8) O3Fe2Cl1 O1Fe1N1 88.94 (8) O3Fe2Cl2 O1Fe1N2 85.94 (7) O3Fe2Cl3 O2Fe1Cl1 93.14 (5) O3Fe2N8A O2Fe1Cl2 88.34 (6) N7AFe2Cl1 O2Fe1N1 171.85 (7) N7AFe2Cl2 O2Fe1N2 96.09 (7) N7AFe2Cl3 N1Fe1Cl1 94.53 (5) N7AFe2O3 N1Fe1Cl2 94.79 (6) N7AFe2N8A N1Fe1N2 76.26 (7) N8AFe2Cl1 N2Fe1Cl1 170.77 (5) N8AFe2Cl2 N2Fe1Cl2 92.83 (5) N8AFe2Cl3 Fe1Cl1Fe2 92.88 (2) Fe1Cl2Fe2 2 (Symmetry codes: (A) x + 1/2, −y + 3/2, −z + 1) Fe1Cl1 2.4285 (15) Fe1N2 Fe1Cl2 2.4367 (16) Fe1N5A Fe1N1 2.212 (4) Fe1N8A Cl1Fe1Cl2 97.37 (6) N5AFe1Cl1 N1Fe1Cl1 94.81 (11) N5AFe1Cl2 N1Fe1Cl2 93.93 (11) N5AFe1N2 N1Fe1N2 73.69 (14) N5AFe1N8A N1Fe1N5A 158.31 (14) N8AFe1Cl1 N1Fe1N8A 88.14 (15) N8AFe1Cl2 N2Fe1Cl1 167.19 (10) N8AFe1N2 N2Fe1Cl2 89.18 (11) 3 (Symmetry codes: (A) −x + 1, −y + 1, −z + 1; (B) −x, −y + 2, −z + 2) Fe1Cl1 2.5257 (8) Fe2Cl2B Fe1Cl1A 2.5257 (8) Fe2Cl2 Fe1N1 2.204 (2) Fe2N5B Fe1N1A 2.204 (2) Fe2N5 Fe1N3 2.115 (2) Fe2N6B Fe1N3A 2.115 (2) Fe2N6 Cl1AFe1Cl1 180.0 Cl2Fe2Cl2B N1AFe1Cl1 90.97 (6) N5Fe2Cl2B N1Fe1Cl1 89.03 (6) N5B−Fe2Cl2B N1AFe1Cl1A 89.03 (6) N5B−Fe2Cl2 N1Fe1Cl1A 90.97 (6) N5Fe2Cl2 N1Fe1N1A 180.0 N5B−Fe2N5 N3Fe1Cl1A 89.56 (7) N6B−Fe2Cl2 N3AFe1Cl1A 90.44 (7) N6Fe2Cl2 N3AFe1Cl1 89.56 (7) N6Fe2Cl2B N3Fe1Cl1 90.44 (7) N6B−Fe2Cl2B N3Fe1N1A 103.93 (9) N6B−Fe2N5 N3AFe1N1A 76.07 (9) N6Fe2N5 N3AFe1N1 103.93 (9) N6Fe2N5B N3Fe1N1 76.07 (9) N6B−Fe2N5B N3AFe1N3 180.000 (1) N6Fe2N6B 4 (Symmetry codes: (A) −x + 1, −y + 1, − z; (B) x + 1, y, z; (C) x − 1, y, z) Fe1Cl1 2.6427 (9) Fe2Cl1B Fe1Cl2 2.3924 (7) Fe2Cl2B Fe1Cl3 2.5662 (9) Fe2Cl3 Fe1Cl4 2.4404 (8) Fe2Cl4 C

2.5544 (8) 2.5209 (7) 2.3903 (7) 2.207 (2) 2.1451 (19) 2.2345 (19) 85.13 (2) 98.31 (3) 95.99 (2) 167.74 (6) 85.31 (6) 90.30 (5) 95.83 (8) 89.43 (6) 97.46 (5) 165.00 (6) 84.21 (8) 74.62 (7) 92.56 (6) 171.80 (6) 92.14 (5) 93.83 (2) 2.269 (4) 2.234 (4) 2.247 (4) 99.71 (10) 100.04 (11) 89.90 (13) 75.91 (14) 89.98 (11) 172.16 (11) 84.14 (15)

2.5269 (8) 2.5269 (8) 2.206 (2) 2.206 (2) 2.129 (2) 2.129 (2) 180.0 89.21 (7) 90.79 (7) 89.21 (7) 90.79 (7) 180.0 90.23 (7) 89.77 (7) 90.23 (7) 89.77 (7) 103.36 (9) 76.64 (9) 103.36 (9) 76.64 (9) 180.000 (1) 2.3928 2.6390 2.4300 2.6079

(7) (9) (8) (9)



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Table 2. continued Fe1N7A 2.184 (2) Fe1N8A 2.204 (2) Cl2Fe1Cl1 84.25 (3) Cl2Fe1Cl3 98.05 (3) Cl2Fe1Cl4 101.92 (3) Cl3Fe1Cl1 174.35 (3) Cl4Fe1Cl1 99.86 (3) Cl4Fe1Cl3 84.75 (3) N7AFe1Cl1 83.80 (7) N7AFe1Cl2 164.62 (6) N7AFe1Cl3 93.02 (7) N7AFe1Cl4 89.65 (6) N7AFe1N8A 74.95 (8) N8AFe1Cl1 89.44 (6) N8AFe1Cl2 95.29 (6) N8AFe1Cl3 85.22 (6) N8AFe1Cl4 161.12 (6) Fe1Cl2Fe2C 95.44 (3) Fe2Cl3Fe1 96.25 (3) 5 (Symmetry codes: (A) x, −y + 3/2, z + 1/2; (B) x, −y + 3/2, z − 1/2) Fe1Cl1 2.4265 (15) Fe1Cl1A 2.6812 (16) Fe1Cl2A 2.4428 (15) Cl1Fe1Cl1A 102.84 (5) Cl1Fe1Cl2 84.71 (5) Cl1Fe1Cl2A 93.31 (5) Cl2AFe1Cl1A 81.07 (5) Cl2Fe1Cl1A 170.54 (5) Cl2AFe1Cl2 92.94 (5) N1Fe1Cl1 96.82 (11) N1Fe1Cl1A 80.70 (11) N1Fe1Cl2A 160.71 (12)

Fe2N1 Fe2N2 Cl1B−Fe2Cl2B Cl1B−Fe2Cl3 Cl1B−Fe2Cl4 Cl3Fe2Cl2B Cl3Fe2Cl4 Cl4Fe2Cl2B N1Fe2Cl1B N1Fe2Cl2B N1Fe2Cl3 N1Fe2Cl4 N1Fe2N2 N2Fe2Cl1B N2Fe2Cl2B N2Fe2Cl3 N2Fe2Cl4 Fe1Cl4Fe2

2.193 (2) 2.239 (2) 84.33 (3) 97.08 (3) 99.39 (3) 95.15 (3) 84.06 (3) 176.26 (3) 165.56 (7) 84.61 (7) 93.13 (6) 91.78 (7) 76.54 (8) 95.12 (6) 94.54 (6) 165.10 (6) 85.54 (6) 94.92 (3)

Fe1Cl2 Fe1N1 Fe1N4 N1Fe1Cl2 N4Fe1Cl1A N4Fe1Cl1 N4Fe1Cl2 N4Fe1Cl2A N4Fe1N1 Fe1Cl1Fe1B Fe1B−Cl2Fe1

2.5222 (16) 2.321 (4) 2.160 (4) 104.28 (11) 87.09 (12) 167.02 (12) 86.34 (12) 96.53 (12) 76.32 (15) 93.61 (5) 97.30 (5)

was performed with SAINT.66 The crystal structures were solved by the direct method using the program SHELXS-9767 and refined by the full-matrix least-squares method on F2 for all non-hydrogen atoms using SHELXL-9768 with anisotropic thermal parameters. All hydrogen atoms were located in calculated positions and refined isotropically, except the hydrogen atoms of water molecules were fixed in a difference Fourier map and refined isotropically. The details of the crystal data were summarized in Table 1, and selected bond lengths and angles for compounds 1−5 are listed in Table 2. The crystallographic data of 1−5 in CIF format has been deposited in the Cambridge Crystallographic Data Center (CCDC reference number: 1058602−1058606). XRPD Results. To confirm whether the crystal structures are truly representative of the bulk materials, X-ray powder diffraction (XRPD) experiments also were carried out for 1−5. The XRPD experimental and computer-simulated patterns of the corresponding complexes are shown in Figure S1. Although the experimental patterns have a few unindexed diffraction lines and some are slightly broadened in comparison with those simulated from the single crystal models, it can still be considered favorably that the bulk synthesized materials and the as-grown crystals are homogeneous for 1−5.

orange block X-ray-quality crystals of 3 in a 39% yield (based on Fe(II)). Anal. Calcd for (C14H10Cl2FeN8): C, 40.32; H, 2.42; N, 26.87. Found: C, 40.26; H, 2.35; N, 26.79. IR (KBr, cm−1): 3423(s), 2879(w), 2736(m), 2660(w), 1605(w), 1539(m), 1476(w), 1447(w), 1300(m), 1262(s), 1141(s), 1180(w), 1116(w), 1084(w), 1056(w), 1018(m), 999(w), 963(m), 819(w), 798(w), 749(w), 708(w), 680(m), 639(m), 502(m). [Fe2(2,2′-H2dbpt)Cl4]n (4). A mixture containing 2,2′-H2dbpt (145 mg, 0.5 mmol), FeCl2·4H2O (199 mg, 1 mmol), and cyclohexanone (15 mL) was sealed in a Teflon-lined stainless steel vessel (25 mL), which was heated at 160 °C for 3 days and then cooled to room temperature at a rate of 10 °C/h. Yellow block crystals of 4 were obtained and picked out, washed with ethanol, and dried in air. Yield: 13% (based on Fe(II)). Anal. Calcd for (C14H10Cl4Fe2N8): C, 30.92; H, 1.85; N, 20.61. Found: C, 30.98; H, 1.78; N, 20.58. IR (KBr, cm−1): 3423(s), 2879(w), 2736(m), 2660(w), 1605(w), 1539(m), 1476(w), 1447(w), 1300(m), 1262(s), 1141(s), 1180(w), 1116(w), 1084(w), 1056(w), 1018(m), 999(w), 963(m), 819(w), 798(w), 749(w), 708(w), 680(m), 639(m), 502(m). [Fe(2,2′-H2dbpt)0.5Cl2]n (5). The same synthetic procedure as that for 4 was used except that the cyclohexanone was replaced by ethanol giving yellow flake X-ray-quality crystals of 5 in a 29% yield (based on Fe(II)). Anal. Calcd for (C7H5Cl2FeN4): C, 30.92; H, 1.85; N, 20.61. Found: C, 30.86; H, 1.76; N, 20.69. IR (KBr, cm−1): 3368(s), 3121(w), 2989(m), 2923(w), 2874(w), 2819(m), 1605(w), 1501(w), 1457(m), 1445(s), 1284(s), 1268(w), 1182(w), 1155(w), 1100(w), 1050(m), 1015(w), 976(m), 793(w), 757(w), 724(w), 637(w), 551(m). X-ray Crystallographic Determination. All reflection data were collected on an Agilent Supernova diffractometer (Mo, λ = 0.71073 Å) at room temperature. A semiempirical absorption correction by using the SADABS program was applied, and the raw data frame integration

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RESULTS AND DISCUSSION Description of the Crystal Structures. Fe 4 (2,2′Hdbpt)2Cl6(H2O)6 (1). Single-crystal X-ray structural analysis shows that compound 1 crystallizes in space group P1̅ (Table 1) and consists of a Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supermolecule. Selected bond lengths and angles are presented in Table 2. There are two independent Fe ions in the Fe4(HL)2Cl6(H2O)6 unit (Figure 1). Fe1 adopts a N2O2Cl2 D



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Figure 1. (a) The coordination environment of the FeII atoms and the structure of the Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supramolecule in 1; (b) the 2D layer connected by Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supramolecules through H-bonds; (c) the 3D architecture constructed by the 2D layer.

Scheme 2. (a) The Fe2 Subunit in 1; (b) the cis-FeCl2N4 Unit in 2; (c) the trans-FeCl2N4 Unit in 3; (d) the Beaded Chain Based on the cis-FeCl4N2 Unit in 4 and 5

Figure 2. (Top left) The coordination environment of the FeII atoms in 2; (right) view of helical chain; (bottom left) the 3D architecture constructed by the helical chains.

distorted octahedral geometry, surrounded by a 2,2′-Hdbpt anion [Fe1−N1 = 2.202(2) Å, Fe1−N2 = 2.238 (2) Å], two μ2Cl atoms [Fe1−Cl1 = 2.486 (1) Å, Fe1−Cl2 = 2.481(1) Å], and two water molecule [Fe1−O1 = 2.108(2) Å, Fe1−O2 = 2.111(2) Å]. Fe2 adopts a N2OCl3 distorted octahedral geometry, surrounded by a 2,2′-Hdbpt anion [Fe2−N7A = 2.145(2) Å, Fe2−N8A = 2.235(2) Å, symmetry codes: A −x + 2, −y + 1, −z + 1], one terminal Cl atom, two μ2-Cl atoms

[Fe2−Cl distances from 2.390 (1) Å to 2.554(1) Å], and one water molecule [Fe2−O3 = 2.207(2) Å]. The neighboring Fe1 and Fe2 units were connected by two μ2-Cl atoms [Fe1−Cl1− Fe2 = 92.88(5)°, Fe1−Cl2−Fe2 = 85.13(4)°] to form a Fe2 subunit (Scheme 2 a). Two Fe2 subunits were clamped by two 2,2′-H2dbpt ligands with the fashions of mode 1 (Scheme 1) to form a centrosymmetric Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supermolecule. The Fe−Fe distance connected by the 2,2′-H2dbpt E



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Figure 3. (a) View of straight-chain and the coordination environment of FeII atoms in 3; (b) the 2D layer connected by the straight-chain through hydrogen bonds; (c) the 3D architecture constructed by the 2D layer.

Figure 4. (a) The coordination environment of the FeII atoms in 4; (b) view of modified trapezoid chain; (c) the schematic description for the 2D architecture with the (42.6) symbol; (d) the 3D architecture constructed by the modified trapezoid chains.

2.269(4) Å], and two chlorine atoms [Fe−Cl distances from 2.429(2) Å to 2.437(2) Å] form a cis-FeCl2N4 octahedral coordination configuration (Scheme 2b, three nitrogen atoms and one chlorine atom in the equatorial plane and the other one nitrogen atom and one chlorine atom locate in the axial position). The neighboring Fe units were connected by 2,2′H2dbpt with the fashion of mode 2 (Scheme 1) to form a helical chain running along the a axis [Fe−Fe distance is 7.063(1) Å]. The adjacent helical chains arranged parallel to each other through a hydrogen bond and π−π stake interactions along the b and c axis, respectively.

ligand is 6.520(1) Å. The neighbor Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supermolecules connected to each other through a hydrogen bond to form a 2D layer extended in the ab plane (Figure 1b). The neighbor 2D layers were connected by a hydrogen bond arranged parallel to each other along the c axis through π−π stake interactions (Figure 1c). [Fe(2,2′-H2dbpt)Cl2·H2O]n (2). Compound 2 crystallizes in space group Pbca, and the asymmetric unit (Figure 2) contains one independent Fe(II) ion, one 2,2′-H2dbpt ligand, two Cl− ions, and one lattice water. Each crystallographically independent Fe(II) ion is coordinated by four nitrogen atoms from two 2,2′-H2dbpt ligands [Fe−N distances from 2.212(4) Å to F



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Figure 5. (a) Coordination environment of the FeII atoms in 5; (b) view of the wave-like layer; (c) the schematic description for the 2D architecture with 63 symbol; (d) the 3D architecture constructed by the wave-like layers.

2.239(2) Å] and four μ2-Cl atoms [Fe−Cl distances from 2.392(1) Å to 2.643(1) Å]. Fe1 and Fe2 are connected by two μ2-Cl− ions to form a beaded chain (Scheme 2d) running along the a axis [the Fe−Fe distance connected by μ2-Cl is 3.721(2) Å, Fe1−Cl1−Fe2C = 95.34(3)°, Fe1−Cl2−Fe2C = 95.44(3)°, Fe1−Cl3−Fe2 = 96.25(3)°, Fe1−Cl4−Fe2 = 94.92(3)°, C: x − 1, y, z]. The neighbor parallel beaded chains were clamped by a string of 2,2′-H2dbpt ligands which arranged upper and lower alternately with the fashion of mode 2 (Scheme 1) to form a 1D wave banded structure. The Fe−Fe distance connected by the 2,2′-H2dbpt ligand is 7.164(4) Å. The adjacent trapezoid chains arrange parallel to each other through hydrogen bonds and other weak interactions along the b and c axis, respectively. A topological analysis reveals that both μ2-Cl− and 2,2′-H2dbpt serve as linkers. According to Wells’ topology definition,69−72 a simple topology with the short Schläfli symbol of (42.6) is formed (Figure 4c). [Fe(2,2′-H2dbpt)0.5Cl2]n (5). Compound 5 crystallizes in space groups of P21/c. The asymmetric unit contains one independent Fe(II) ion, half a 2,2′-H2dbpt ligand, and two μ2Cl− ions (Figure 5). Each crystallographically independent Fe(II) ion is coordinated by two nitrogen atoms from a 2,2′H2dbpt [Fe−N distances from 2.160(4) Å to 2.321(4) Å] and four μ2-Cl atoms [Fe−Cl distances from 2.427(2) Å to 2.681(2) Å] to form a cis-FeCl4N2 octahedral coordination

[Fe(2,2′-H2dbpt)Cl2]n (3). Compound 3 crystallizes in space groups of P1̅, and the asymmetric unit contains one independent Fe(II) ion, one 2,2′-H2dbpt ligand, and two Cl− ions (Figure 3). Each crystallographically independent Fe(II) ion lies on symmetrical centers, which are equatorially coordinated by four nitrogen atoms from two 2,2′-H2dbpt ligands [Fe−N distances from 2.204(2) Å to 2.129(2) Å] and two chlorine atoms [Fe−Cl distances from 2.526(1) Å to 2.527(1) Å] to form a trans-FeCl2N4 octahedral coordination configuration (Scheme 2c, the equatorial plane was occupied by four nitrogen atoms from two 2,2′-H2dbpt ligands, and the axial position was occupied by two chlorine atoms). The neighboring Fe units were connected by 2,2′-H2dbpt with the fashion of mode 3 (Scheme 1) to form a linear chain [Fe−Fe distance is 9.863(1) Å]. The neighboring stright-chains were connected to each other through a hydrogen bond to form a 2D layer. The adjacent layers arranged parallel to each other through π−π stack interactions. [Fe2(2,2′-H2dbpt)Cl4]n (4). Compound 4, which is a modified trapezoid chain, crystallizes in space group P1̅, and the asymmetric unit contains two independent Fe(II) ions, one 2,2′-H2dbpt ligand, and four μ2-Cl− ions (Figure 4). Both Fe1 and Fe2 adopt cis-FeCl4N2 octahedral coordination configuration, which are coordinated by two nitrogen atoms from a 2,2′-H2dbpt ligand [Fe−N distances from 2.184(2) Å to G



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Figure 6. Plots of χMT vs T and 1/χM vs T (inset) for 1−5 (a), and the plots of χM vs T for 1−5 (b−f). Solid lines (in χM and 1/χM) represent the best theoretical fit (see text for the model and parameters).

bridging 2,2′-H2dbpt ligand. Compounds 4 and 5 are supramolecular isomers. Different from 2 and 3, both of them have a cis-FeCl2N4 unit. Owing to the different rotation angles of pyridine rings in 2,2′- H2dbpt, 4 and 5 reveal a 1D modified trapezoid chain based on the trans-bridging 2,2′H2dbpt ligand and a 2D wave-like layer based on the cisbridging 2,2′-H2dbpt ligand, respectively. Furthermore, compound 4 could also be viewed as a wave banded chain constructed by 1 with μ2-Cl ions replaced by the terminal Cl ions and water molecules from another perspective (the deprotonation of the 2,2′-H2dbpt ligand in 1 is to ensure the charge balance). In short, structural correlation and diversification of 1−5 are revealed interestingly, based on the same raw material and the different assembly conditions, respectively. Clearly, the phenomenon of structural diversification in 1−5 may arise from the three sources as follows. First of all, the 2,2′H2dbpt ligand plays a dominating effect on constructing the polymer structures. Owing to the different rotation angles of the four aromatic rings with respect to each other, a deprotonation effect (2,2′-H2dpbt, 2,2′-Hdpbt−, 2,2′-dpbt2−),

configuration. The neighboring Fe units were connected by two μ2-Cl atoms to form a beaded chain (Scheme 2d) running along the c axis [the Fe−Fe distance connected by μ2-Cl is 3.727(3) Å, Fe1−Cl1−Fe1B = 93.61(5)°, Fe1−Cl2−Fe1B = 97.30(5)°, B: x, −y + 3/2, z − 1/2]. The neighboring chains were connected by 2,2′-H2dbpt with the fashion of mode 4 (Scheme 1), giving rise to a 2D wave-like layer structure extended in the bc plane. The Fe−Fe distance connected by the 2,2′-H2dbpt ligand is 7.670(7) Å. The adjacent 2D layers arranged parallel to each other alongthe a axis. A topological analysis reveals that both μ2-Cl− and 2,2′-H2dbpt serve as linkers. In this way, a simple topology with the short Schläfli symbol of 63 is formed (Figure 5c). Five novel coordination complexes from one to three dimensions based on the 2,2′-H2dbpt ligand are presented. Compound 1 reveals a discrete Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supramolecule. Compounds 2 and 3 are pseudo-polymorphism.73,74 2 reveals a helical chain based on the cis-FeCl2N4 unit and the cis-bridging 2,2′-H2dbpt ligand, while 3 reveals a straight chain based on the trans-FeCl2N4 unit and the transH



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and the flexing angles, it could adopt various conformations, which may lead to unpredictable and interesting structures. Second, the different solvent environment may be possible to regulate the coordination modes of the 2,2′-H2dbpt ligand. In this paper, the 2,2′-H2dbpt ligand adopts four different conformations, relying on the different solvent environment (Scheme 1). Third, the assembly condition of the metal−ligand ratio which may possibly regulate the coordination configuration (Scheme 2) of the FeII centers is also not ignorable. When we regulate the ratio of (FeCl2·4H2O): (2,2′-H2dbpt) to 1:1, compounds 2 and 3 based on the FeCl2N4 unit are formed, whereas when we regulate ratio of (FeCl2·4H2O): (2,2′H2dbpt) to 2:1, compound 1 based on FeN2O2Cl2 and FeN2OCl3 units, compounds 4 and 5 based on FeCl2N4 unit are formed. Magnetic Properties. Solid-state, variable-temperature magnetic susceptibility measurements were performed on a powder sample of complexes 1−5 in the 2−300 K range in a 1 kOe magnetic field (Figure 6). For 1, the data above 3 K follow the Curie−Weiss law with C = 13.97 cm3 K mol−1 and θ = −4.78 K. The significantly negative Weiss constant indicate antiferromagnetic interactions between the FeII centers. The χMT value (per FeII center) at 300 K is about 3.42 cm3·K·mol−1, much larger than the spinonly value 3.00 cm3·K·mol−1 for a magnetically FeII ions with (S = 2, g = 2.0), as expected for the presence of a orbital contribution in octahedral FeII. As the temperature is lowered, the χMT value decreases smoothly to 3.04 cm3 K mol−1 at 35 K, after which it drops rapidly to reach a minimum value of 0.68 cm3 K mol−1 at 2 K, possibly due to antiferromagnetic interactions between FeII ions connected by two μ2-Cl atoms. The distance of the adjacent FeII ions connected by the 2,2′H2dbpt ligand is 6.520 (1) Å, indicating the weak interactions between them could be ignored at high temperature (above 3 K). To analyze the magnetic data of 1, we tried to use an approximate approach similar to the [FeII2 ]2 dimeric molecules eq 1.75 Using this rough model, a good fit of the susceptibility above 3 K was obtained, shown as the solid line in Figure 6b, with parameters g = 2.11 and J = −0.4866 cm−1. χM =

4Ng 2β 2 kT e 2J / kT + 5e 6J / kT + 14e12J / kT + 30e 20J / kT × 1 + 3e 2J / kT + 5e 6J / kT + 7e12J / kT + 9e 20J / kT

K was obtained, shown as the solid line in Figure 6c, with parameters g = 2.29 and zj′ = −0.1873 cm−1. χ=

Ng 2β 2 S(S + 1) 3kT

χM =

χ 1 − (2zj′/Ng 2β 2)χM

(2)

For 3, the data above 3 K follow the Curie−Weiss law with C = 3.45 cm3 K mol−1 and θ = −1.25 K. The χMT value (per FeII center) at 300 K is about 3.43 cm3·K·mol−1, which is larger than the spin-only value 3.00 cm3·K·mol−1 for a magnetically FeII ion with (S = 2, g = 2.0), as expected for the presence of a orbital contribution in octahedral FeII. As the temperature is lowered, the χMT value decreases smoothly to 3.32 cm3 K mol−1 at 30 K. After which it drops rapidly to reach a minimum value of 1.80 cm3 K mol−1 at 2 K, which is perhaps attributable to magnetic anisotropy, but could also be due to long-range antiferromagnetic interactions between FeII ions and/or magnetic saturation (the Zeeman effect) at the very lowest temperatures.76 The distance of the adjacent FeII ions connected by the 2,2′-H2dbpt ligand is 9.863(1) Å, indicating the weak interactions between them could be ignored at high temperature (above 3 K). Like compound 2, we tried to use an approximate approach similar to the mononuclear FeII complexes (eq 2, S = 2)77,78 to analyze the magnetic data of 2. A good fit of the susceptibility above 3 K was obtained, shown as the solid line in Figure 6d, with parameters g = 2.17 and zj′ = −0.3330 cm−1. For 4, the data above 3 K follow the Curie−Weiss law with C = 6.26 cm3 K mol−1 and θ = 3.45 K. The significantly positive Weiss constant indicates that ferromagnetic interactions between the FeII centers. The χMT value (per FeII center) at 300 K is about 3.16 cm3·K·mol−1, which is larger than the spinonly value 3.00 cm3·K·mol−1 for a magnetically FeII ion with (S = 2, g = 2.0), as expected for the presence of a orbital contribution in octahedral FeII. As the temperature is lowered, the χMT value increases smoothly to 3.47 cm3 K mol−1 at 30 K, after which it increases rapidly to reach a maximum value of 4.80 cm3 K mol−1 at 8 K, possibly due to the weak ferromagnetic interactions between FeII ions. Finally, it drops rapidly to reach a minimum value of 0.94 cm3 K mol−1 at 2 K, possibly due to a magnetic phase transition.79 The distance of the adjacent FeII ions connected by the 2,2′-H2dbpt ligand is 7.164(4) Å, indicating the weak interactions between them could be ignored at high temperature (above 3 K). To analyze the magnetic data of 4, we tried to use an approximate approach similar to the 1D [FeII∞]2 complexes (eq 3, S = 2).80 Using this rough model, a good fit of the susceptibility above 10 K was obtained, shown as the solid line in Figure 6e, with parameters g = 2.00 and J = 0.3822 cm−1.

(1)

For 2, the data above 3 K follow the Curie−Weiss law with C = 3.61 cm3 K mol−1 and θ = −1.08 K. The χMT value (per FeII center) at 300 K is about 3.60 cm3·K·mol−1, which is larger than the spin-only value 3.00 cm3·K·mol−1 for a magnetically FeII ion with (S = 2, g = 2.0), as expected for the presence of a orbital contribution in octahedral FeII, and is relatively constant down to approximately 30 K. Below this temperature, it collapses to reach a minimum value of 1.14 cm3 K mol−1 at 2 K, which is perhaps attributable to magnetic anisotropy, but could also be due to long-range antiferromagnetic interactions between FeII ions and/or magnetic saturation (the Zeeman effect) at the very lowest temperatures.76 The distance of the adjacent FeII ions connected by the 2,2′-H2dbpt ligand is 7.063(1) Å, indicating the weak interactions between them could be ignored at high temperature (above 3 K). To analyze the magnetic data of 2, we tried to use an approximate approach similar to the mononuclear FeII complexes (eq 2, S = 2).25 Using this rough model, a good fit of the susceptibility above 3

2Ng 2β 2S(S + 1) 1 + u 3kT 1 − u′ ⎤ ⎡ JS(S + 1) ⎤ ⎡ kT u = coth⎢ ⎥ ⎥−⎢ ⎦ ⎣ JS(S + 1) ⎦ ⎣ kT

χM =

(3)

For 5, the data above 3 K follow the Curie−Weiss law with C = 3.52 cm3 K mol−1 and θ = 3.78 K. The significantly positive Weiss constant indicates ferromagnetic interactions between the FeII centers. The χMT value (per FeII center) at 300 K is about 3.57 cm3·K·mol−1, which is larger than the spin-only value 3.00 cm3·K·mol−1 for a magnetically FeII ion with (S = 2, g = 2.0), as expected for the presence of a orbital contribution in octahedral FeII. As the temperature is lowered, the χMT value increases smoothly to 4.03 cm3 K mol−1 at 30 K, after which it I



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162 °C corresponds to the release of the lattice water molecules (calculated, 4.14%). The residual framework decomposed beyond 361 °C in a series of complicated weight losses until 898 °C. Compounds 3−5 have no coordinated or interstitial solvent molecules, and hence, no mass loss was observed between 81 and 404 °C, 80 and 346 °C, and 83 and 378 °C, respectively. For 3, the framework decomposed beyond 404 °C in a series of complicated weight losses until 832 °C. For 4, the framework decomposed beyond 346 °C in a series of complicated weight losses until 662 °C. For 5, the framework decomposed beyond 378 °C in a series of complicated weight losses until 862 °C.

increases rapidly to reach a maximum value of 10.89 cm3 K mol−1 at 5 K, possibly due to the weak ferromagnetic interactions between FeII ions. Finally, it drops rapidly to reach a minimum value of 5.89 cm3 K mol−1 at 2 K, possibly due to a magnetic phase transition.26 The distance of the adjacent FeII ions connected by the 2,2′-H2dbpt ligand is 7.670(7) Å, indicating the weak interactions between them could be ignored in high temperature (above 3 K). To analyze the magnetic data of 5, we also tried to use an approximate approach similar to the 1D FeII complexes (eq 4, S = 2).80 Using this rough model, a good fit of the susceptibility above 10 K was obtained, shown as the solid line in Figure 6f, with parameters g = 2.04 and J = 0.6350 cm−1. Ng 2β 2S(S + 1) 1 + u χM = 3kT 1 − u′ ⎤ ⎡ JS(S + 1) ⎤ ⎡ kT u = coth⎢ ⎥ ⎥−⎢ ⎦ ⎣ JS(S + 1) ⎦ ⎣ kT

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CONCLUSIONS In summary, five novel coordination complexes based on the Fe(II)/Cl system with diversiform connectivity from zero- to two-dimensional were constructed successfully relying on the various coordination modes of 2,2′-H2dbpt. 1 reveals a discrete Fe4(2,2′-Hdbpt)2Cl6(H2O)6 supramolecule. 2 and 3 which are pseudopolymorphism, reveal a helical chain based on a cisFeCl2N4 unit and a stright-chain based on a trans-FeCl2N4 unit, respectively. 4 and 5 are also supramolecular isomers, based on the different rotation angles of pyridine rings in 2,2′-H2dbpt. 4 reveals a 1D modified trapezoid chain based on the transbridging 2,2′-H2dbpt. 5 reveals a 2D wave-like layer based on the cis-bridging 2,2′-H2dbpt. 1 reveals weak antiferromagnetic behavior. 2 and 3 both reveal paramagnetic behavior, while 4 and 5 both reveal ferromagnetic behavior. These results indicate that 2,2′-H2dbpt could revealed diverse coordination modes by altering the important reaction environments, such as the metal−ligand ratio, solvents, coordination geometry of central metal, ancillary ligands, pH, and so on. By applying this synthetic method, we have already prepared a large number of new supramolecular coordination complexes with new structural features and potentially interesting physical properties that will be reported in future papers.

(4)

In 1−5, the long distance (range from 6.520 (1) to 9.863(1) Å) of the adjacent FeII ions connected by the 2,2′-H2dbpt ligand conduce the very weak interactions between them. As a result, 2 and 3 both reveal paramagnetic behavior. And in 1, 4, and 5, the interactions between adjacent FeII ions bridged by μ2-Cl play a leading part in the magnetic behavior. Interestingly, 1 with a [FeII2 ]2 dimeric molecule reveals weak antiferromagnetic behavior, and 4 and 5 based on the [FeII2Cl2]n beaded chain both reveal ferromagnetic behavior. At low temperature (below 10 K), 4 reveals weak ferromagnetic behavior, which may be attributed to the synergistic effect between the ferromagnetic interactions in the [FeII2Cl2]n beaded chain and the weak antiferromagnetic interactions in the adjacent [FeII2Cl2]n beaded chains connected by 2,2′-H2dbpt ligands, while the strong ferromagnetic behavior of 5 at low temperature (below 10 K) may be attributed to the synergistic effect between the ferromagnetic interactions in the [FeII2Cl2]n beaded chain and the weak ferromagnetic interactions in the adjacent [FeII2Cl2]n beaded chains connected by 2,2′-H2dbpt ligands. Thermal Analyses. The thermogravimetric (TG) analysis was performed in N2 atmosphere on polycrystalline samples of complexes 1−5, and the TG curves are shown in Figure 7. For 1, the first weight loss of 9.62% between 80 and 405 °C corresponds to the release of the six coordinated water molecules (calculated, 9.18%). And then the residual framework decomposed in a series of complicated weight losses until 675 °C. For 2, the first weight loss of 4.60% between 81 and

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b00724. Comparation of the structures for 4 and 5; powder X-ray diffraction patterns of 1−5; in-phase and out-of-phase ac magnetic susceptibilities of 5 (PDF) Crystallographic files (CIF1, CIF2, CIF3, CIF4, CIF5, CIF6)

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AUTHOR INFORMATION

Corresponding Authors

*(F.-P.H.) E-mail: [email protected]. *(H.-D.B.) E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the National Nature Science Foundation of China (Nos. 21101035, 21361003, and 21461003), Guangxi Natural Science Foundation of China (2012GXNSFBA053017, 2012GXNSFAA053035, and 2014GXNSFBA118056) and the Foundation of Key Laboratory for Chemistry and Molecular Engineering of Medicinal

Figure 7. TG curves for complexes 1−5. J



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Resources, Ministry of Education of China (CMEMR2011-20, CMEMR2013-A05).

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