Syntheses, Crystal Structures, and Photocatalytic Properties of a

Article pubs.acs.org/crystal

Syntheses, Crystal Structures, and Photocatalytic Properties of a Series of Mercury Thioantimonates Directed by Transition Metal Complexes Cheng-Yang Yue,*,† Xiao-Wu Lei,*,†,‡ Rui-Qiu Liu,† Hui-Ping Zhang,† Xiu-Rong Zhai,† Wen-Peng Li,† Meng Zhou,† Zhi-Fei Zhao,† Yun-Xiang Ma,† and Ya-Dong Yang† †

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry and Chemical Engineering, Jining University, Qufu, Shandong, 273155, China ‡ State Key Laboratory of Crystal Materials, Institute of Crystal Materials, Shandong University, Jinan, Shandong, 250100, China S Supporting Information *

ABSTRACT: With different transition metal (TM) complexes as structure-directing agents or structure-building units, a series of new mercury thioantimonates with abundant architectures ranging from one-dimensional (1D) ribbons to twodimensional (2D) layers have been solvothermally synthesized and structurally characterized. Compounds [Co(en)3]Hg2Sb2S6 (1) (en = ethylenediamine) and [Ni(1,2-dap)3]2HgSb3S7Cl (2, 1,2-dap = 1,2-diaminopropane) contain a discrete 2D [Hg2Sb2S6]n2n− layer and 1D [HgSb3S7]n3n− chain, respectively. Compounds [Ni(1,2dap)3]HgSb2S5 (3) and [Mn(dien)2]HgSb2S5 (4, dien = diethylenetriamine) feature distinct 2D [HgSb2S5]n2n− layer and 1D [HgSb2S5]n2n− ribbon, respectively, whereas the 1D [HgSb2S5]n2n− chains are attached by [TM(tren)]2+ complexes via TM−S bonds to form 1D {[TM(tren)]HgSb2S5}n ribbons in compounds [TM(tren)]HgSb2S5 (TM = Mn (5), Fe (6), Co (7), tren = tris(2-aminoethyl)amine). Compounds [TM(dien)2]Hg3Sb4S10 (TM = Mn (8), Co(9), Ni(10)) feature 2D [Hg3Sb4S10]n2n− anionic layers separated by [TM(dien)2]2+ cations. The most interesting structural feature of these compounds is the presence of three different types of coordination environments of Hg centers including linear [HgS2] unit, [HgS3] triangle, and [HgS4] tetrahedron. The optical properties and thermal stabilities of the title compounds were studied by UV−vis spectra and thernogravimetric analyses, respectively. The photocatalytic experiments indicated that 3, 4, and 10 were able to degrade rhodamine B (RhB) under visible irradiation.

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INTRODUCTION In the past several decades, metal thioantimonates and selenidoantimonates were investigated intensively because of their fascinating structural diversities and topologies and potential applications in many areas such as fast-ion conductivity, pholocatalyst, nonlinear optical material, etc.1−5 On the one hand, the antimony atom is favored to feature a wide range of coordination numbers from 3 to 6, which would undergo self-condensation to lead to the formation of new secondary building units (SBUs) giving rise to novel chalcogenides with remarkable topologies. On the other hand, the stereochemically active lone pair of Sb3+ ion is likely to induce non-centrosymmetric or even chiral structures, resulting in interesting physical properties, such as secondharmonic generation, enantioselective separation, and catalysis.6−11 In recent years, an effective strategy for the development of new metal thioantimonates and selenidoantimonates is to design and construct new SBUs via incorporation of other heteroatoms into the single metal chalcogenide anionic framework.12−14 Especially, the mild solvothermal reaction in polyamine solutions greatly promotes more and more © 2014 American Chemical Society

transition metals (TM) introduced into the thioantimonates and selenidoantimonates, and such a strategy not only enhances the structural diversity but also integrates the electronic, optical, and magnetic properties of TM ions with the host inorganic framework.15 Generally speaking, the former transition metals, such as Cr2+, Mn2+, Fe2+, Co2+, and Ni2+, are favored to be coordinated by chelating amines, leading to [TM(amine)n]2+ complex cations as structure-directing agents or structurebuilding units via TM−Q (Q = S, Se) bonds, whereas the thiophilic d10 transition metal ions (Cu+, Ag+, Zn2+, Cd2+, Hg2+) are able to form various [TMQx] building units, which further integrate with [SbxQy]n− moieties to form a ternary TM−Sb−Q anionic framework.16−19 For example, it is found that Ag+ ions feature linear AgS2, approximately AgS3 trigonal planar, and AgS4 tetrahedral coordination environments in [C4N2H14][Ag3Sb3S7], [C2N2H9]2[Ag5Sb3S8], and [C6N4H20][Ag5Sb3S8], etc.16,17 Received: January 28, 2014 Revised: March 12, 2014 Published: March 14, 2014 2411

dx.doi.org/10.1021/cg500153u | Cryst. Growth Des. 2014, 14, 2411−2421

Crystal Growth & Design

Article

[Ni(1,2-dap)3]2HgSb3S7Cl (2). The reagents of Ni(CH3COO)2· 4H2O (0.0498 g, 0.2 mmol), HgCl2 (0.0271 g, 0.1 mmol), Sb2S3 (0.0509 g, 0.15 mmol), S (0.0128 g 0.4 mmol), 1,2-dap (4 mL), and H2O (1 mL) were sealed in a stainless steel reactor with a 15 mL Teflon liner, and then heated at 140 °C for 5 days to yield yellow block-shaped crystals of 2. The crystals were selected by hand and washed with distilled water and ethanol. The yield of the crystals of 2 is 0.0305 g, 22% based on Sb. Anal. For C18N12H60Ni2HgSb3S7Cl (2), calcd: C 15.58%, H 4.36%, N 12.11%; found: C 15.43%, H 4.22%, N 12.22%. IR (KBr, cm−1) for 2: 3471 (s), 3260 (s), 2843 (w), 1572 (s), 1420 (m), 1051 (s), 640 (m). [Ni(1,2-dap)3]HgSb2S5 (3). The reagents of Ni(CH3COO)2·4H2O (0.0498 g, 0.2 mmol), HgCl2 (0.0543g, 0.2 mmol), Sb2S3 (0.0679 g, 0.2 mmol), S (0.0192 g 0.6 mmol), 1,2-dap (4 mL), and H2O (1 mL) were sealed in a stainless steel reactor with a 15 mL Teflon liner, and then heated at 160 °C for 5 days to yield yellow block-shaped crystals of 3. The crystals were easily selected by hand and washed with distilled water and ethanol. The yield of the crystals of 3 is 0.062 g, 35% based on Sb. For C9N6H30NiHgSb2S5 (3), calcd: C 12.21%, H 3.41%, N 9.49%; Found: C 12.10%, H 3.35%, N 9.65%. IR (KBr, cm−1) for 3: 3440 (s), 3230 (s), 2950 (w), 1580 (s), 1460 (m), 1020 (s), 654 (m). [Mn(dien)2]HgSb2S5 (4). A mixture of Mn(CH3COO)2·4H2O (0.0490g, 0.2 mmol), HgCl2 (0.0543g, 0.2 mmol), Sb2S3 (0.0679 g, 0.2 mmol), S (0.016 g, 0.5 mmol), dien (4.0 mL), and ethanol (2 mL) was sealed in a stainless steel reactor with a 15 mL Teflon liner and then heated at 140 °C for 5 days. The product consists of light yellow prismatic crystals of 4 as well as a few indefinite dark powders. The crystals were selected by hand and washed with distilled water and ethanol. The yield of the crystals of 4 is 0.0779 g, 45% based on Sb. Anal. For C8N6H26MnHgSb2S5 (4), calcd: C 11.10%, H 3.03%, N 9.71%; found: C 11.28%, H 3.18%, N 9.52%. IR (KBr, cm−1) for 4: 3473(m), 3263 (s), 2852 (m), 1575 (m), 1430 (m), 958 (s), 609 (m). [TM(tren)]HgSb2S5 (5−7, TM = Mn, Fe, Co). The reagents of Co(CH3COO)2·4H2O (0.2 mmol), HgCl2 (0.0543 g, 0.2 mmol), Sb2S3 (0.0679 g, 0.2 mmol), S (0.016 g, 0.5 mmol), tren (4 mL), and H2O (1 mL) were sealed in a stainless steel reactor with a 15 mL Teflon liner and then heated at 130 °C for 5 days and cooled to room temperature. The products contain a large amount of brown and prism-shaped crystals, subsequently determined as [Co(tren)]HgSb2S5, and a small amount of unknown black powder. The compounds 5 and 6 were prepared in an analogous manner to that of 7 with Mn(CH3COO)2·4H2O and FeCl3·6H2O instead of Co(CH3COO)2·4H2O, respectively. The crystals were selected by hand and washed with distilled water and ethanol. The yields of the crystals of 5−7 are 0.012 g (8%) for 5, 0.011 g (7%) for 6, 0.0966 g (60%) for 7 based on Sb, respectively. Anal. For C6N4H18CoHgSb2S5 (7), Calcd: C 8.90%, H 2.24%, N 6.92%; Found: C 8.81%, H 2.14%, N 7.02%. IR (KBr, cm−1): 3506 (m), 3228 (s), 2852 (s), 1564 (s), 1471 (m), 1072 (s), 644 (m). [TM(dien)2]Hg3Sb4S10 (8−10, TM = Mn, Co, Ni). A mixture of TM(CH3COO)2·4H2O (0.2 mmol), HgCl2 (0.1629 g, 0.6 mmol), Sb2S3 (0.1359 g, 0.4 mmol), and S (0.032 g, 1 mmol), dien (4.0 mL), and H2O (1 mL) was sealed in a stainless steel reactor with a 15 mL Teflon liner. The sealed reactor was heated at 160 °C for 5 days to yield orange block-shaped crystals. The crystals were selected by hand and washed with distilled water and ethanol. The yields of the crystals of 8−10 are 0.016 g (9.8%), 0.026 g (8%), and 0.102 g (30%) based on Sb, respectively. Anal. For C8N6H26NiHg3Sb4S10 (10), calcd: C 5.74%, H 1.56%, N 5.02%; Found: C 5.61%, H 1.45%, N 5.21%. IR (KBr, cm−1) for 10: 3489 (m), 3251 (s), 2842 (m), 1502 (s), 1473 (m), 1011 (s), 623 (m). Crystal Structure Determination. Single crystals of the title compounds were selected from the reaction products for X-ray crystal diffraction. Data collections for all compounds were performed on a Bruker SMART CCD-based diffractometer (Mo Kα radiation, graphite monochromator) at 293(2) K. Data integration and cell refinement were done by the INTEGRATE program of the APEX2 software, and Multiscan absorption corrections were applied using the SCALE program for area detector. The structures of the title compounds were

Among these d10 transition metal ions, group 12 metal Hg2+ is a remarkable candidate for incorporating into [SbxQy]n moieties to construct novel heterometallic anionic network due to its diversiform coordination numbers from 2 to 6 as well as typical photoelectric properties of binary HgQ semiconductors.20,21 Hitherto, limited pure inorganic A−Hg−Sb− Q (A = alkali metal) compounds have been reported with A+ serving as structure-directing agents and counterions.22 Subsequently, abundant organic amines were introduced leading to many new Hg−Sb−S/Se phases with fascinating structural diversities and topologies, such as 1D-[(Me)2NH2]2HgSb 8 S 14 , 2D-[enH 2 ] 0.5 HgSbS 3 , and 3D-[(Me) 2 NH 2 ][Hg3Sb3Se8], etc.23 Furthermore, a series of TM complexes oriented Hg−Sb−Se phases were also characterized including 1D-[Ni(1,2-dap)3]HgSb2Se5, 1D-[Mn(dien)2]HgSb2Se5, 1D[TM(tren)]HgSb2Se5 (TM = Mn, Fe, Co), 2D-[Ni(en)3]Hg2Sb2Se6 and 2D-[Ni(en)(teta)]Hg2Sb2Se6, some of which feature photocatalytic properties of degrading organic contaminants. Intrigued by their rich structural types, we performed systematic studies in the Hg−Sb−S system containing TM complexes. So far, only a few TM complexdirected compounds of [Ni(en)3]0.5HgSbS3, [Mn(phen)]2HgSb2S6 and [TM(dien)2]HgSb2S5 (TM = Co, Ni) were characterized with 2D layers and 1D ribbons, respectively.24 By adopting bi-, tri-, or tetra-dentate chelating amines in situ coordinated to TM ions, we explored a series of new TM complexes directed mercury thioantimonates, namely, [Co(en)3]Hg2Sb2S6, [Ni(1,2-dap)3]2HgSb3S7Cl, [Ni(1,2-dap)3]2HgSb2S5, [Mn(dien)2]HgSb2S5, [TM(tren)]HgSb2S5 (TM = Mn, Fe, Co) and [TM(dien)2]Hg3Sb4S10 (TM = Mn, Co, Ni). Under the different structure-directing effects of various TM complexes, the title compounds feature multiple structural characterization based on SbS3 trigonal pyramids, and linear HgS2 unit, HgS3 triangle or HgS4 tetrahedron. Herein, we report their syntheses, crystal structures, optical and photocatalytic properties.

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EXPERIMENTAL SECTION

Materials and Instruments. All analytical grade chemicals employed in this study were obtained commercially and used without further purification. Elemental analyses (C, H, and N) were performed using a PE2400 II elemental analyzer. The solid-state UV/vis spectra were measured at room temperature using a computer-controlled PE Lambda 900 UV/vis spectrometer equipped with an integrating sphere in the wavelength range of 200−800 nm. Fourier transform infrared (FT-IR) spectra were recorded with a Nicolet Magna-IR 550 spectrometer in dry KBr disks in the 4000−400 cm−1 range. Thermogravimetric analyses (TGA) were carried out with a Mettler TGA/SDTA 851 thermal analyzer under a nitrogen atmosphere with a heating rate of 10 °C min−1 in the temperature region of 30−700 °C. X-ray diffraction (XRD) powder patterns were collected at room temperature on a X’Pert-Pro diffractometer using Cu Kα radiation (λ = 1.5406 Å) in the 2θ range of 5−80°. Syntheses of Compounds 1−10. [Co(en)3]Hg2Sb2S6 (1). A mixture of Co(CH3COO)2·4H2O (0.0498 g, 0.2 mmol), HgCl2 (0.1086g, 0.4 mmol), Sb2S3 (0.0679 g, 0.2 mmol), S (0.0256 g, 0.8 mmol), en (4.0 mL), and H2O (1.0 mL) was sealed in a stainless steel reactor with a 15 mL Teflon liner and heated at 160 °C for 5 days, and then slowly cooled to room temperature. A large amount of yellow block-shaped crystals of 1 were found and subsequently determined to be [Co(en)3]Hg2Sb2S6. The crystals were easily collected by hand and washed with distilled water and ethanol (yield: 0.135 g, 63% based on Sb). Anal. For C6N6H24CoHg2Sb2S6 (1), calcd: C 6.69%, H 2.25%, N 7.81%; Found: C 6.51%, H 2.18%, N 7.98%. IR (KBr, cm−1): 3467 (s), 3253 (s), 1581 (s), 1452 (m), 1012 (s), 637 (m). 2412



Article

Table 1. Crystal Data and Structure Refinements for Compounds 1−4

a

compound

1

2

3

4

chemical formula fw space group a/Å b/Å c/Å β/° V (Å3) Z Dcalcd (g cm−3) temp (K) μ (mm−1) F(000) reflections collected unique reflections reflections (I > 2σ(I)) GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) Δρmax (e/Å3) Δρmin (e/Å3)

C6N6H24CoHg2Sb2S6 1076.36 C2/c (No. 15) 19.907(12) 7.773(5) 14.779(9) 106.600(6) 2192(2) 4 3.262 293(2) 17.712 1947 12260 2512 2312 1.098 0.0278/0.0702 0.0338/0.0839 1.839 −1.422

C18N12H60Ni2HgSb3S7Cl 1387.91 P21/c (No. 14) 14.986(6) 15.072(6) 20.514(8) 104.094(5) 4494(3) 4 2.051 293(2) 6.416 2680 51593 10336 5836 1.008 0.0504/0.1034 0.1176/0.1268 1.653 −1.866

C9N6H30NiHgSb2S5 885.49 P21/c (No. 14) 11.4087(12) 13.2919(14) 18.9376(15) 118.878(4) 2514.7(4) 4 2.339 293(2) 9.371 1664 28824 5778 4620 1.021 0.0348/0.0903 0.0496/0.0973 1.811 −0.692

C8N6H26MnHgSb2S5 865.68 P21/c (No. 14) 10.709(4) 20.740(8) 10.786(4) 114.641(4) 2177.7(14) 4 2.640 293(2) 10.533 1612 25072 4982 4036 1.016 0.0309/0.0718 0.0450/0.0774 1.018 −1.562

R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2.


a

compound

5

6

7

chemical formula fw space group a/Å b/Å c/Å α/° β/° γ/° V (Å3) Z Dcalcd (g cm−3) temp (K) μ (mm−1) F(000) reflections collected unique reflections reflections (I > 2σ(I)) GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) Δρmax (e/Å3) Δρmin (e/Å3)

C6N4H18MnHgSb2S5 805.64 P1̅ (No. 2) 7.427(7) 10.722(10) 12.410(12) 69.156(10) 77.224(11) 85.238(10) 900.7(15) 2 2.971 293(2) 12.719 738 10187 3991 3116 1.001 0.0472/0.1182 0.0648/0.1288 2.084 −2.542

C6N4H18FeHgSb2S5 806.55 P1̅ (No. 2) 7.3752(6) 10.5561(9) 12.3004(10) 69.6770(10) 77.7070(10) 85.8020(10) 877.42(13) 2 3.053 293(2) 13.163 740 10307 3979 3501 1.040 0.0293/0.0730 0.0353/0.0754 1.886 −1.991

C6N4H18CoHgSb2S5 809.63 P1̅ (No. 2) 7.3778(4) 10.5551(6) 12.3071(7) 69.6290(10) 77.7390(10) 85.7230(10) 877.96(9) 2 3.063 293(2) 13.274 742 10241 3987 3723 1.094 0.0243/0.0648 0.0266/0.0658 1.16 −2.10

R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2. Photocatalytic Activity Measurements. The photocatalytic activities of as-prepared samples were evaluated by the degradation of rhodamine B (RhB) under visible light irradiation of a 500 W Xe lamp. The cutoff filter was used to remove all wavelengths less than 400 nm and more than 780 nm ensuring irradiation with visible-light only. In a typical processes, 25 mg of samples as photocatalysts was added into 50 mL of RhB solution (10 mg/L). After being dispersed in an ultrasonic bath for 30 min, the solution was stirred for 2 h in the dark before irradiation to reach adsorption equilibrium between the catalyst and solution and then was exposed to visible light irradiation.

solved by using direct method (SHELXTL) and refined by full-matrix least-squares technique.25 Non-hydrogen atoms were refined with anisotropic displacement parameters, and the hydrogen atoms bonded to C and N atoms were located at geometrically calculated positions. Site occupancy refinements for the title compounds indicated that all sites were fully occupied. Data collection and refinement parameters for all the compounds are summarized in Tables 1−3. Important bond lengths are listed in Tables 4−6. More details on the crystallographic studies are given in Supporting Information. 2413



Article


a

compound

8

9

10

chemical formula fw space group a/Å b/Å c/Å β/° V (Å3) Z Dcalcd (g cm−3) temp (K) μ (mm−1) F(000) reflections collected unique reflections reflections (I > 2σ(I)) GOF on F2 R1, wR2 (I > 2σ(I))a R1, wR2 (all data) Δρmax (e/Å3) Δρmin (e/Å3)

C8N6H26MnHg3Sb4S10 1670.66 P21/c (No. 14) 11.7218(18) 9.9484(15) 14.020(2) 109.557(2) 1540.6(4) 2 3.602 293(2) 19.428 1490 17426 3560 3290 1.025 0.0220/0.0633 0.0253/0.0650 1.560 −1.284

C8N6H26CoHg3Sb4S10 1674.65 P21/c (No. 14) 11.7163(11) 9.9621(9) 14.0344(13) 109.4940(10) 1544.2(2) 2 3.602 293(2) 19.510 1494 17443 3564 3261 1.085 0.0233/0.0535 0.0290/0.0724 1.655 −1.535

C8N6H26NiHg3Sb4S10 1674.43 P21/c (No. 14) 11.659(2) 9.9546(17) 14.011(3) 109.313(2) 1534.5(5) 2 3.624 293(2) 19.706 1496 17466 3549 3267 1.079 0.0209/0.0480 0.0268/0.0709 1.358 −1.443

R1 = ∑||Fo| − |Fc||/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2.

distance of about 6.5 Å. The [Co(en)3]2+ cations as structuredirecting and charge-balancing agents are located at the interlayer spaces and form extensive N−H···S hydrogen bonds with the S atoms of the anionic layer, resulting in a 3D H-bonding network (Figure 1b). 1D-[Ni(1,2-dap)3]2HgSb3S7Cl (2). Compound 2 crystallizes in the monoclinic space group P21/c (No. 14) and belongs to a new structure type, consisting of discrete 1D [HgSb3S7]n3n− anionic chains and charge-compensating complex cations of [Ni(1,2-dap)3]2+ as well as Cl− anions. The asymmetric unit of compound 2 contains two crystallographically independent Ni2+ ions, one Hg2+ center, three Sb3+, one Cl−, and seven S2− ions. As shown in Figure 2a, two independent Ni2+ ions are coordinated by six nitrogen donors from two 1,2-dap ligands with slightly distorted octahedral geometries forming [Ni(1,2dap)3]2+ complex cations, respectively. The Hg2+ ion is surrounded by three S2− ions with a nearly trigonal-planar coordination environment, which is similar to the [HgQ3] triangles of (Me4N)HgAsSe3, [Ph4P]2Hg2As4S9, and [Ph4P]2Hg2As4Se11.21 The Hg−S bond distances fall in the range of 2.345(3)−2.638(3) Å, which are close to those of [Ph4P]2Hg2As4S9.21b As far as we known, the Hg2+ ion prefers tetrahedral coordination with four chalcogen atoms, and the HgQ3 (Q = S, Se, Te) trigonal-planar geometry in inorganic− organic hybrid chalcogenides is still very scarce. All the Sb3+ ions adopt SbS3 trigonal-pyramidal coordination geometries with Sb−S bond lengths of 2.325(3)−2.596(3) Å. Moreover, the Sb(3)3+ ion also features one weak Sb(3)−S(6) secondary bonding interaction at a slightly longer distance of 2.966 Å opposite to the Sb(3)−S(3) bond (2.596(3) Å). So the coordination polyhedron of Sb(3) may be regarded as a distorted Ψ−[SbS4] trigonal bipyramidal geometry with one coordination site occupied by the lone pairs of antimony(III). All the S2− ions feature distinct metal linkers: S(2) and S(6) link one Sb atom acting as terminal atom, S(3) and S(4) bridge two Sb atoms, and others connect with one Hg and one Sb atom, respectively.

About 4 mL suspension was continually taken from the reaction cell and collected by centrifugation at 90 min intervals during the irradiation. The resulting solution was analyzed on a GBC Cintra 2020 UV/vis spectrophotometer.

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RESULTS AND DISCUSSION TM complexes have been widely used in the syntheses of inorganic−organic hybrid chalcogenides because of their excellent template or structure-directing effects. In this paper, we adopt bi- or tridentate chelating amines of en, dien, and 1,2dap, and tetra-dentate chelating amine of tren in situ coordinated to TM ions leading to four different types of TM complexes, which induce six series of new mercury thioantimonates with diversified networks from 1D ribbons and 2D layers based on SbS3 trigonal pyramids and HgS2, HgS3, or HgS4 units (Scheme 1). Here, the structures of compounds 2, 3, and 8−10 will be intensively discussed due to their new structural types, and other isotructural compounds are simply introduced. Structural Descriptions. 2D-[Co(en)3]Hg2Sb2S6 (1). Compound 1 is isostructural with [Ni(en)3]Hg2Sb2Q6 (Q = S, Se) and features a 2D [Hg2Sb2S6]n2n− anionic layer separated by [Co(en)3]2+ complex.23 As shown in Figure 1a, the Hg2+ ion is coordinated by four S2− ions in a distorted tetrahedron coordination environment, and the Sb3+ ion adopts trigonal pyramidal geometry. The Hg−S and Sb−S bond distances of 2.459(2)−2.6675(18) Å and 2.4179(18)−2.4541(17) Å, respectively, are comparable with those reported in mercury thioantimonates.23,24 Two adjacent HgS4 tetrahedra are condensed via edge-sharing to form a [Hg2S6] dimer, and they are bridged by two SbS3 trigonal pyramids via corner sharing into a 1D [Hg2Sb2S8] chain along the b-axis. The neighboring 1D [Hg2Sb2S8] chains are further condensed via sharing S(1) atoms along the c-axis to form the 2D [Hg2Sb2S6]n2n− anionic layer within the bc plane. These 2D [Hg2Sb2S6]n2n− anionic layers feature parallel packing in an AAA sequence along the c-axis with the shortest interlayer S···S 2414



Article

Table 4. Selected Bond Lengths (Å) for Compounds 1−4a

Table 5. Selected Bond Lengths (Å) for Compounds 5−7a

1 Co(1)−N(2) Co(1)−N(2)#1 Co(1)−N(3)#1 Hg(1)−S(1) Hg(1)−S(2)#2 Hg(1)−S(3) Hg(1)−S(3)#3

2.143(5) 2.143(5) 2.174(5) 2.459(2) 2.5202(19) 2.6182(18) 2.6675(18)

5 Co(1)−N(3) Co(1)−N(1)#1 Co(1)−N(1) Sb(1)−S(2) Sb(1)−S(1) Sb(1)−S(3)#2

2.174(5) 2.201(5) 2.201(5) 2.4179(18) 2.4243(19) 2.4541(17)

Ni(1)−N(10) Ni(1)−N(1) Ni(1)−N(4) Ni(2)−N(12) Ni(2)−N(9) Ni(2)−N(11) Sb(1)−S(2) Sb(1)−S(3) Sb(1)−S(1)#1 Sb(3)−S(6) Sb(3)−S(4) Sb(3)−S(3)

2.128(7) 2.136(8) 2.137(8) 2.137(9) 2.140(9) 2.160(9) 2.325(3) 2.440(3) 2.480(3) 2.381(3) 2.479(2) 2.596(3)

Ni(1)−N(3) Ni(1)−N(5) Ni(1)−N(1) Hg(1)−S(2) Hg(1)−S(5) Sb(2)−S(2) Sb(2)−S(5) Sb(2)−S(4)#2

2.119(7) 2.138(7) 2.141(9) 2.7823(18) 2.8737(16) 2.397(2) 2.4081(16) 2.4441(17)

Mn−N(6) Mn−N(2) Mn−N(5) Hg(1)−S(1) Hg(1)−S(4) Sb(2)−S(1) Sb(2)−S(4)#1 Sb(2)−S(5)

2.129(3) 2.142(4) 2.144(3) 2.5809(9) 2.6665(10) 2.4113(9) 2.4272(10) 2.4768(10)

2 Ni(1)−N(5) Ni(1)−N(2) Ni(1)−N(3) Ni(2)−N(8) Ni(2)−N(7) Ni(2)−N(6) Hg(1)−S(1) Hg(1)−S(5) Hg(1)−S(7) Sb(2)−S(7) Sb(2)−S(4) Sb(2)−S(5)

2.116(7) 2.123(7) 2.127(8) 2.103(8) 2.107(9) 2.136(9) 2.345(3) 2.403(3) 2.638(3) 2.399(2) 2.426(2) 2.533(3)

Ni(1)−N(2) Ni(1)−N(6) Ni(1)−N(4) Hg(1)−S(3) Hg(1)−S(4) Sb(1)−S(3) Sb(1)−S(1)#1 Sb(1)−S(1)

2.109(7) 2.097(7) 2.109(7) 2.396(2) 2.3983(17) 2.416(2) 2.426(2) 2.550(2)

Mn(1)−N(4) Mn(1)−N(2)

2.172(9) 2.207(9)

Hg(1)−S(4) Hg(1)−S(2) Sb(1)−S(3) Sb(1)−S(5) Sb(1)−S(1)

2.478(3) 2.504(3) 2.425(3) 2.425(4) 2.636(3)

Mn(1)−N(3) Mn(1)−N(1) Mn(1)−S(5) Hg(1)−S(3) Hg(1)−S(1) Sb(2)−S(2)#1 Sb(2)−S(4)#2 Sb(2)−S(1)

2.229(9) 2.394(8) 2.477(4) 2.627(3) 2.771(4) 2.409(3) 2.450(3) 2.485(3)

Fe(1)−N(3) Fe(1)−N(1) Fe(1)−S(5) Hg(1)−S(3) Hg(1)−S(1) Sb(2)−S(2)#2 Sb(2)−S(4) Sb(2)−S(1)

2.090(6) 2.281(5) 2.3678(17) 2.6224(17) 2.7219(16) 2.4026(16) 2.4375(17) 2.4648(16)

Co(1)−N(3) Co(1)−N(1) Co(1)−S(5) Hg(1)−S(3) Hg(1)−S(1) Sb(2)−S(2) Sb(2)−S(4) Sb(2)−S(1)#2

2.088(4) 2.288(4) 2.3689(14) 2.6242(13) 2.7288(12) 2.4028(13) 2.4368(13) 2.4651(12)

6 Fe(1)−N(4) Fe(1)−N(2)

2.054(5) 2.086(5)

Hg(1)−S(4)#1 Hg(1)−S(2) Sb(1)−S(3) Sb(1)−S(5) Sb(1)−S(1)

2.4657(16) 2.4860(17) 2.4154(17) 2.4232(16) 2.6505(15)

Co(1)−N(4) Co(1)−N(2)

2.054(4) 2.081(4)

Hg(1)−S(4)#1 Hg(1)−S(2) Sb(1)−S(3) Sb(1)−S(5) Sb(1)−S(1)

2.4659(12) 2.4896(13) 2.4170(13) 2.4233(12) 2.6467(12)

7

3

a Symmetric codes: for 5: #1 −x, −y, −z + 1; #2 −x + 1, −y, −z + 1; for 6: #1 −x, −y + 1, −z + 1; #2 −x + 1, −y + 1, −z + 1; for 7: #1 x − 1, y, z; #2 −x + 1, −y + 1, −z + 1.

4 Mn−N(3) Mn−N(1) Mn−N(4) Hg(1)−S(3) Hg(1)−S(2) Sb(1)−S(2) Sb(1)−S(3)#1 Sb(1)−S(5)#2

2.115(3) 2.123(4) 2.128(3) 2.5111(9) 2.5469(9) 2.4457(10) 2.4506(9) 2.4869(10)

bonds with S atoms into a 3D H-bonding network structure. The N····S and N····Cl separations are in the range of 3.341(10)−3.886(11) Å and 3.387(9)−3.648(10) Å, respectively. 2D-[Ni(1,2-dap)3]HgSb2S5 (3). Compound 3 crystallizes in the monoclinic space group P21/c (No. 14) and adopts a new structural type. Its structure is composed of 2D [HgSb2S5]n2n− anionic layers and [Ni(1,2-dap)3]2+ complex cations. Here, it should be noted that the structure of compound 3 is completely different from that of [Ni(1,2-dap)3]HgSb2Se5 despite similar chemical compositions, and the latter features a 1D [HgSb2Se5]n2n− ribbon.23c The Ni(1)2+ ion is coordinated by six N atoms of three 1,2dap ligands, forming a distorted octahedral [Ni(1,2-dap)3]2+ complex cation. The 2D [HgSb2S5]n2n− layer contains two crystallographically distinct Sb3+ ions, one Hg2+ ion, and five S2− ions (Figure 3a). All the Sb3+ ions are coordinated by three S2− ions with Sb−S distances in the range of 2.397(2)− 2.550(2) Å, forming typical SbS3 trigonal pyramids. The Hg2+ ion adopts a significantly distorted HgS4 tetrahedron with two shorter Hg−S bonds of 2.396(2)−2.3983(17) Å and two longer Hg−S bonds of 2.7823(18)−2.8737(16) Å, which is similar to those of KHgSbS3.22d Each S2− ion is bonded to two metal cations: S(1) bridge two Sb3+ ions, and others connect with one Sb3+ and one Hg2+ ion, respectively. The HgS4 tetrahedra and Sb(2)S3 trigonal pyramids are alternately interconnected via corner- and edge-sharing to form 1D [HgSbS5] chains along the b-axis, which are further bridged by Sb2S4 dimers composed of two Sb(1)S3 trigonal pyramids via sharing S(3) atoms to form a 2D [HgSb2S5]n2n− anionic

a Symmetric codes: for 1 #1 −x, y, −z + 1/2; #2 −x + 1/2, y− 1/2, −z + 1/2; #3 −x + 1/2, −y + 1/2, −z; for 2 #1 x, −y + 1/2, z − 1/2; for 3: #1 −x + 2, −y − 1, −z, #2 −x + 1, y − 1/2, −z − 1/2; for 4 #1 x, −y + 3/2, z + 1/2, #2 x, −y + 3/2, z − 1/2.

In the 1D [HgSb3S7]n3n− anionic chain, the neighboring Sb(1)S3, Sb(2)S3, and Sb(3)S3 trigonal-pyramids are condensed by sharing the corner S atoms to form [Sb3S7] trimer, which are alternately bridged by [HgS3] triangles via cornerand edge-sharing into the 1D [HgSb3S7]n3n− anionic chain approximately along the c-axis (Figure 2a). The neighboring 1D [HgSb3S7]n3n− chains are antisymmetrically stacked along the baxis, which are further interconnected via the Sb(3)−S(6) secondary bonding interactions to form a 2D [HgSb3S7]n3n− layer. Such connectivity also leads to one type of [Hg4Sb14S18] ring with a rough parallelogram cross-section of 5.49 × 15.70 Å viewed along the a-axis (Figure 2b). These adjacent 2D layers feature parallel packing along the a-axis with the shortest interlayer S···S distance of about 5.021 Å (Figure 2c). The [Ni(1,2-dap)3]2+ complex cations and Cl− anions as chargebalancing agents are located among the space of 2D anionic layers, forming extensive N−H···S and N−H···Cl hydrogen 2415



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Table 6. Selected Bond Lengths (Å) for Compounds 8−10a 8 Mn(1)−N(3)#1 Mn(1)−N(3) Mn(1)−N(2)#1 Hg(1)−S(1)#2 Hg(2)−S(3) Hg(2)−S(2) Sb(1)−S(4)#3 Sb(1)−S(5) Sb(1)−S(1)

2.194(5) 2.194(5) 2.172(4) 2.3827(12) 2.4787(13) 2.5179(13) 2.4010(13) 2.4834(13) 2.5116(12)

Co(1)−N(3)#1 Co(1)−N(3) Co(1)−N(2)#1 Hg(1)−S(1)#2 Hg(2)−S(3) Hg(2)−S(2) Sb(1)−S(4)#3 Sb(1)−S(5) Sb(1)−S(1)

2.133(6) 2.133(6) 2.160(6) 2.3836(15) 2.4895(16) 2.5235(15) 2.4011(17) 2.4884(16) 2.5091(15)

Mn(1)−N(1)#1 Mn(1)−N(1) Mn(1)−N(2) Hg(1)−S(1) Hg(2)−S(4) Hg(2)−S(1) Sb(2)−S(2) Sb(2)−S(3)#4 Sb(2)−S(5)#5

2.135(5) 2.135(5) 2.172(4) 2.3827(12) 2.5256(14) 2.7270(13) 2.4067(13) 2.4304(13) 2.4565(14)

Co(1)−N(1)#1 Co(1)−N(1) Co(1)−N(2) Hg(1)−S(1) Hg(2)−S(4) Hg(2)−S(1) Sb(2)−S(2) Sb(2)−S(3)#4 Sb(2)−S(5)#5

2.193(6) 2.193(6) 2.160(6) 2.3836(15) 2.5316(17) 2.7389(15) 2.4082(16) 2.4319(16) 2.4537(17)

Ni(1)−N(1)#1 Ni(1)−N(1) Ni(1)−N(2) Hg(1)−S(1) Hg(2)−S(4) Hg(2)−S(1) Sb(2)−S(2) Sb(2)−S(3)#4 Sb(2)−S(5)#5

2.120(6) 2.120(6) 2.145(6) 2.3814(15) 2.5328(18) 2.7378(16) 2.4052(17) 2.4306(17) 2.4530(17)

9

10 Ni(1)−N(3)#1 Ni(1)−N(3) Ni(1)−N(2)#1 Hg(1)−S(1)#2 Hg(2)−S(3) Hg(2)−S(2) Sb(1)−S(4)#3 Sb(1)−S(5) Sb(1)−S(1)

2.095(6) 2.095(6) 2.145(6) 2.3813(15) 2.4856(16) 2.5214(16) 2.3992(17) 2.4868(17) 2.5080(16)

Figure 1. Detailed view of the 2D [Hg2Sb2S6]n2n− anionic layers of 1 (a) and general view of network of compound 1 along the b-axis (b) with TM complexes drawn as light blue colors only for clarity.

1D [HgSb2S5]n2n− anionic ribbons isolated by [Mn(dien)2]2+ complexes. As shown in Figure 4a, both Sb(1)3+ and Sb(2)3+ ions adopt SbS3 trigonal-pyramidal coordination geometries, and the Hg2+ ion is coordinated by four S2− ions to give a slightly distorted tetrahedral geometry. The Sb−S and Hg−S bond lengths are normal and call for no further comments. Two SbS3 trigonal pyramids and one HgS4 tetrahedron are condensed via corner sharing to form a heterometallic [HgSb2S7] unit with a three-membered [HgSb2S3] ring. Such a [HgSb2S7] unit resembles that of [GeSb2S7] in [Co(dien)2]GeSb 2S 7 and [CoSb 2 S 7] in [Co(en) 3 ]CoSb 6 S 14 .26 The neighboring [HgSb2S7] units are alternately condensed via sharing S(1) and S(3) atoms in the contrary direction to form 1D anionic [HgSb2S5]n2n− ribbons along the c-axis (Figure 4a), which simultaneously results in another four-membered [Hg2Sb2S4] rings among the [HgSb2S3] rings. These 1D [HgSb2S5]n2n− ribbons are interconnected by [Mn(dien)2]2+ complexes via N−H···S hydrogen bonds into a 3D H-bonding network (Figure 4b). Herein, it should be noted that the chemical composition of compound 4 is very similar to that of [Mn(dien)2]HgSb2Se5, which both contain the same [Mn(dien)2]2+ complexes and 1D [HgSb2Q5]n2n− (Q = S, Se) anionic ribbons. Differently, compound 4 belongs to the monoclinic system (P21/c), whereas [Mn(dien)2]HgSb2Se5 crystallizes in the orthorhombic system (Pbca).23c In this sense, such compounds are best described as polytypes, the structures of which feature building blocks with identical topology but different stacking manners. 1D-[TM(tren)]HgSb2S5 (TM = Mn (5), Fe (6), Co (7)). Compounds 5−7 crystallize in the triclinic space group P1̅ (No. 2) and are isotypical to [TM(tren)]HgSb2Se5 (TM = Mn, Fe, Co) with S atoms replacing the Se sites.23b In the follow discussion, only the structure of 7 will be discussed as representative. Its structure features a 1D {[Co(tren)]HgSb2S5}n ribbon composed of 1D [HgSb2S5]2− chains and Co(tren)2+ complexes interconnected via Co−S bonds (Figure

a Symmetric codes: for 8: #1 −x, −y − 1, −z; #2 −x + 1,−y + 1,−z; #3 −x + 1,−y, −z; #4 −x + 1, y − 1/2,−z + 1/2; #5 x, −y + 1/2, z + 1/2; for 9: #1 −x − 1,−y − 2,−z; #2 −x, −y,−z; #3 −x,−y − 1,−z; #4 −x, y − 1/2, −z + 1/2; #5 x, −y − 1/2, z + 1/2; for 10: #1 −x + 1,−y + 1,− z; #2−x + 1,−y + 2,−z; #3 −x + 1, y + 1/2,−z + 1/2; #4 x,−y + 3/2, z + 1/2; #5 −x,−y + 3,−z.

Scheme 1. Solvothermal Syntheses of the Title Compounds

layer (Figure 3a). Within the 2D [HgSb2S5]n2n− layer, there is one type of large [Hg6Sb6S12] ring with a rough parallelogram cross-section of 9.85 × 13.29 Å presented in the layer viewed along the a-axis. These [Hg6Sb6S12] rings feature codirectional arrangement along the b-axis whereas present reversed arrangement along the b-axis (Figure 3a). The 2D [HgSb2S5]n2n− anionic layers feature parallel packing along the c-axis, which are bridged by [Ni(1,2-dap)3]2+ complexes via extensive N−H···S hydrogen bonds to form a 3D H-bonding network (Figure 3b). 1D-[Mn(dien)2]HgSb2S5 (4). Compound 4 crystallizes in the monoclinic space group P21/c (No. 14) and is isostructural with [TM(dien)2]HgSb2S5 (TM = Ni, Co).24 Its structure features 2416



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Figure 3. Crystal structure of the 2D [HgSb2S5]n2n− anionic layer in 3 (a), and the crystal packing of 3 viewed down the b-axis with TM complexes drawn as light blue colors only for clarity (b).

Figure 2. Detailed view of the 1D [HgSb3S7]n3n− anionic chain along the c-axis (a), the 2D [HgSb3S7]n3n− layer (b), and the packing structure of compound 2 along the b-axis with TM complexes drawn as light blue colors only for clarity (c).

5). The asymmetric unit of 7 contains two crystallographically independent Sb3+, one unique Hg2+, four S2‑, one Co2+ cation, and a molecule of tren ligand, respectively. All the Sb3+ ions adopt trigonal-pyramidal coordination geometries, and the Hg(1)2+ ion is surrounded by four S2− ions to form a distorted tetrahedron with normal Sb−S and Hg−S bond distances, respectively. Two HgS4 tetrahedra and two Sb(2)S3 trigonalpyramids are interconnected via sharing S atom to form two types of [Hg2Sb2S4] four-membered rings, which are similar to those of compound 1 and [enH2]Hg2Sb2S6. The neighboring [Hg2Sb2S4] rings are further condensed via edge-sharing to form a 1D [HgSbS4] chain along the a-axis. Such 1D [HgSbS4] chains and [Co(tren)]2+ complexes are bridged by Sb(1)S3 trigonal-pyramids via sharing the terminal S atoms of [HgS4] tetrahedra and Co−S bonds to form a 1D infinite {[Co(tren)]HgSb2S5}n ribbon along the a-axis (Figure 5a). Similar to that of [TM(tren)]HgSb 2 Se 5 , the 1D {[Co(tren)]HgSb 2 S 5 } n ribbons can be interconnected by the Sb(1)−S(5) secondary bonding interactions (3.047 Å) along the b-axis and various

Figure 4. General view of the 1D [HgSb2S5]n2n− anionic ribbon of 4 along the c-axis (a) and packing structure of compound 4 viewed down the c-axis with TM complexes drawn as light blue colors (b).

inter-ribbon N−H···S hydrogen bonds into a 2D layer extended within the ab plane (Figure 5b). It is very interesting to compare the structures of [HgSb2S5]2− units in compounds 3, 4, and 5−7 as well as [Ni(1,2-dap)]HgSb2Se5. In compound 3, the [HgSb2S5]2− unit features a 2D layer composed of 1D [HgSbS5] chains and [Sb2S4] dimers, and the [HgSb2S5]2− unit belongs to 1D ribbons composed of [Sb2S5] dimers and [HgS4] tetrahedra in compound 4, whereas the 1D [HgSb2S5]2− unit belongs to another type of 1D ribbon composed of 1D [HgSbS4] chains and [SbS3] trigonal pyramids, and it further integrates with unsaturated [Co(tren)]2+ complex to form a 1D {[TM(tren)]2417



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The Sb(1)S3 and Sb(2)S3 trigonal pyramids are interconnected by corner-sharing to form a [Sb2S5] dimer. The alternative connections of [Sb2S5] dimers and individual Hg(2)S4 tetrahedra by corner-sharing give rise to 1D [HgSb 2 S 7 ] chains along the b-axis. Then, a pair of centrosymmetry-related [HgSb2S7] chains and Hg(1)S2 units are condensed to form 1D [Hg3Sb4S12] ribbons along the baxis. (Figure 6a). Within 1D [Hg3Sb4S12] ribbons, there are two

Figure 5. A close-up view of 1D {[TM(tren)]HgSb2S5}n ribbon along the a-axis in compound 7 (a) and general view of the packing manner of the 1D {[TM(tren)]HgSb2S5}n ribbon in 7 viewed along the a-axis (b).

HgSb2S5}n ribbon in compound 7. More interestingly, under the direction of the same [Ni(1,2-dap)]2+ cations, the 2D [HgSb2S5]n2n− layer of compound 3 is completely different from that of [Ni(1,2-dap)]HgSb2Se5, which contains a 1D [HgSb2S5]n2n− ribbon similar to that of [TM(dien)2]HgSb2S5.23 2D-[TM(dien)2]Hg3Sb4S10 (TM = Mn (8), Co (9), Ni (10)). Compounds 8−10 crystallize in their own structural type with monoclinic space group P21/c (No. 14). In the follow discussion, only the structure of 10 will be discussed as representative. Its structure features 2D [Hg3Sb4S10]n2n− anionic layers separated by [Co(dien)2]2+ complexes. The asymmetric unit of compound 10 contains one crystallographically independent Ni2+, two Hg2+, two Sb3+, five S2− ions, and two dien molecules as ligand. The Ni2+ ion is coordinated by six N atoms of two chelating dien amines with a distorted octahedral environment. In the 2D [Hg3Sb4S10]n2n− anionic layers, both Sb(1)3+ and Sb(2)3+ ions adopt SbS3 trigonalpyramidal coordination geometries with Sb−S bond lengths ranging from 2.3992(17) to 2.5080(16) Å. The Hg(1)2+ ion is coordinated by two S2− ions in a linear configuration with a Hg−S bond distance of 2.3813(15) Å and S−Hg−S angle of 180°. Such coordination environment of Hg2+ ion is the same as that of [Me2NH2]2HgSb8S14. The Hg(2)2+ ion is coordinated by four S2− ions to give a distorted tetrahedral geometry with Hg−S bond distances of 2.4856(16)−2.7378(16) Å, which are similar to those of compounds 1 and 2. It should be noted that most of the Hg−As/Sb−Q (Q = S, Se, Te) phases only contain one type of HgQn unit, and there are a few chalcogenides composed of different types of HgQn units. Compound 10 is a new chalcogenidometalate simultaneously including HgS2 and HgS4 units, which is similar to that of [Ph4P]2Hg2As4Se11 containing HgSe3 trigonal-planar and HgSe4 tetrahedron.21a All the S2− ions feature distinct metal linkers: S(1) connects one Sb and two Hg atoms, and other S2− ions bridge one Sb and one Hg atom, respectively.

Figure 6. A close-up view of the 2D [Hg3Sb4S10]n2n− anionic layers in compound 10 (a) and the crystal structure of compound 10 along the b-axis with TM complexes drawn as light blue colors (b).

types of similar four-membered rings with different linking order: one is of [Hg−Hg−Sb-Sb] order and another is of [Hg− Sb−Hg-Sb] order, and the latter is similar to that of compounds 1 and 7. The neighboring 1D [Hg3Sb4S12] ribbons are further condensed via sharing terminal S(2) atoms to form wave-type 2D [Hg3Sb4S10]n2n− anionic layers within the bc plane. Such connectivity also simultaneously leads to another five-membered [Hg2Sb3S5] ring among the 1D [Hg3Sb4S12] ribbons. Hence, the 2D [Hg3Sb4S10]n2n− layer can also be considered as the condensation of two different types of [Hg2Sb2S4] rings and one type of [Hg2Sb3S5] rings via edgesharing. These 2D [Hg3Sb4S10]n2n− anionic layers feature parallel packing along the a-axis, which are further connected by [Ni(dien)2]2+ cations via N−H····S hydrogen bonds resulting in a 3D network (Figure 6b). Optical Properties. The solid-state optical diffuse reflection spectra of the compounds 1−4, 7, and 10 were measured at room temperature. The optical absorption spectra indicate that these compounds are semiconductors. As shown in Figure 7, the optical band gaps obtained by extrapolation of the linear portion of the absorption edge is estimated as 2.52 eV, 2.47 eV, 2.42 eV, 2.48 eV, 2.03 eV, and 2.29 eV for compounds 1−4, 7, and 10, respectively. It should be noted 2418



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be attributed to the removal of all 1,2-dap molecules and one Hg atom per formula. Compound 3 loses three 1,2-dap molecules, one Hg, and one S atom per formula in the range of 300−370 °C with the observed weight loss of 51.3%, which is close to the theoretical value of 51.4%. Compound 4 features two-step weight loss of two dien molecules, one Hg and one S atom per formula in the range of 230−310 °C and 310−410 °C, respectively. The observed weight loss of 50.2% is close to the theoretical values of 50.7%, respectively. From 260 to 320 °C, compound 7 has a one-step weight loss of 43.0% (theoretical value of 42.8%), corresponding to the loss of one tren molecule and one Hg atom per formula. Compound 10 loses the organic amine molecules, three Hg atoms, and two S atoms per formula in the range of 270−400 °C with the observed weight loss of 51.9%, which is close to the theoretical value of 52.1%. After the major weight loss, compounds 1−4, 7, and 10 continue to slowly lose weight and do not achieve the balance until 700 °C. Photocatalytic Properties. The photocatalytic activities of the compounds 3, 4, and 10 were evaluated by the degradation of RhB under visible light irradiation at room temperature as the test pollutant. Temporal changes in the concentration of RhB were monitored by examining the variations of the intensities in the maximal absorption in UV−vis spectra at 554 nm. Figure 9 illustrates the time-dependent absorption spectra of RhB degraded by 3, 4, and 10. The degradation efficiencies are defined as C/C0, where C and C0 represent the remnant and initial concentration of RhB, respectively. Samples 3 and 4 feature similar photocatalytic effects, and the degradation ratio of RhB reached 92% exposed to visible light for 180 min, and achieved nearly 100% after 360 min, resulting in complete decolorization. Such phenomena are also demonstrated by the change in the color of the dispersion from an initial red to a nearly colorless (the inset of Figure 9a,b). Compared to compounds 3 and 4, compound 10 shows a slightly slower photocatalytic effect at the initial reaction, but it also completely degrades RhB after 360 min (Figure 9c,d). The photocatalytic efficiencies of these compounds are comparable to those of other mercury thioantimonates, such as [Mn(tren)]HgSb2Se5,23b but evidently lag behind other photocatalyst, such as copper coordination polymer materials.27 The XRD characterizations show that there are no changes before and after the photocatalytic process, demonstrating the stability of compounds 3, 4, and 10 as the catalyst (Figure S1, Supporting Information).

Figure 7. Solid-state optical absorption spectra of compounds 1−4, 7, and 10.

that the band gap of compound 7 is evidently more narrow than those of compounds 1−4 and 10, which is in accordance with the distinction between their colors (brown for compound 7 and approximately yellow for others). According to the calculated results of similar mercury selenidoantimonates, such a difference is mainly originated from the different coordination environments of the TM2+ ions.23c The band gaps of the title compounds are comparable to those of other Hg−Sb−S compounds, such as [enH2]0.5HgSbS3 (2.49 eV), [Ni(en)3]Hg2Sb2S6 (2.68 eV), and [tetaH2]0.5HgSbS3 (2.40 eV).23a Obviously, the title compounds exhibit a red shift of the absorption edge compared to those of the reported isostructural Hg−Sb−Se compounds, such as [Co(tren)]HgSb2Se5 (1.90 eV), [Mn(dien)2]HgSb2Se5 (2.08 eV), and [Ni(en)3]Hg2Sb2Se6 (2.03 eV).23b,c Thermal Stabilities. The thermal stabilities of 1−4, 7, and 10 were examined by thermogravimetric analysis (TGA) in N2 atmosphere from 30 to 700 °C (Figure 8). Compound 1 removes organic amine molecules and Hg species from 190 to 380 °C with the observed weight loss of 53.6%, which is close to the theoretical value of 54.0%. Compound 2 begins to lose weight at about 220 °C, and it has a final weight loss of 46.8% (calcd 46.5%) when the temperature reaches 342 °C. This can

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CONCLUSIONS In conclusion, a series of new inorganic−organic hybrid mercury thioantimonates have been solvothermally synthesized and structurally, optically, and thermally characterized. Under the different structure-directing effects of various TM complexes, these compounds feature diversified structural topologies based on SbS3 trigonal pyramids, and linear HgS2 unit, HgS3 trigonal planar, or HgS4 tetrahedron. First, compound 2 features a novel 1D [HgSb3S7]n3n− chain containing a scarce [HgS3] trigonal planar coordination environment. Second, the [HgSb2S5] unit wondrously belongs to a new 2D anionic layer in compound 3 but not similar to the 1D [HgSb2S5]n2n− ribbons of [Ni(1,2-dap)3]2HgSb2Se5. Third, it is also interesting to combine two different types of HgS2 and HgS4 units into one structure of compound 10, which is relatively scarce for inorganic−organic hybrid Hg−As/Sb−Q phases. The photocatalytic experiments show our materials

Figure 8. Thermogravimetric curves for compounds 1−4, 7, and 10. 2419



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Figure 9. Absorption spectra of a solution of RhB (10 mg/L, 50 mL) in the presence of compounds 3, 4, and 10 (15 mg) under exposure to visible light (a−c); the photodegradation of RhB by compounds 3, 4, and 10 monitored as the normalized change in concentration as a function of irradiation time (d).

BS2012CL008); China Postdoctoral Science Foundation Funded project (No. 2012M521321); High Educational Science & Research Foundation of Shandong Province (Nos. J11LB52 and J13D58), Postdoctoral Innovation Project of Shandong Province (201303097), and Scientific Research and Technological Development Program of Jining City (No. 20125014).

have the ability to degrade the organic contaminant, demonstrating the photochemical properties of the inorganic−organic hybrid mercury thioantimonates. Research on this subject is in progress.

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ASSOCIATED CONTENT

S Supporting Information *

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Crystallographic data in CIF format (CCDC nos. 956503 for 1, 975192 for 2, 981011 for 3, 956502 for 4, 956499 for 5, 956500 for 6, 956498 for 7, 977931 for 8, 975193 for 9, and 977930 for 10), tables of hydrogen bonds and XRD powder patterns. This material is available free of charge via the Internet at http:// pubs.acs.org.

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REFERENCES

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AUTHOR INFORMATION

Corresponding Authors

*(C.-Y.Y.) E-mail: [email protected]. *(X.-W.L.) E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge financial support from the National Nature Science Foundation of China (Nos. 21101075 and 21201081); the Research Foundation for Excellent Young and Middle-aged Scientists of Shandong Province (Nos. BS2011CL009 and 2420



Article

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