(TM = Ni, Co): 3D Chiral Framework of Mixed Main ... - ACS Publications

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[TM(en)3][SnSb4S9] (TM = Ni, Co): 3D Chiral Framework of Mixed Main-Group Metals and [Mn(dien)2]2Sb4S9: 1D Chains with MixedValent Sb Centers Cheng-Yang Yue,† Xiao-Wu Lei,*,†,‡ Yun-Xiang Ma,† Ning Sheng,† Ya-Dong Yang,† Guo-Dong Liu,† and Xiu-Rong Zhai† †

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: Two new isostructural quaternary tin(IV) antimony(III) sulfides, [TM(en)3][SnSb4S9] [TM = Ni (1), Co (2); en = ethylenediamine], and one mixed-valent thioantimonate (III and V), [Mn(dien)2]2Sb4S9 (3, dien = diethylenetriamine), have been solvothermally synthesized and structurally characterized. In the structures of 1 and 2, four neighboring SbS3 trigonal pyramids are condensed via corner-sharing to form bow-like Sb4S9 tetramers, which are further interconnected by SnS6 octahedra into the threedimensional (3D) chiral [SnSb4S9]2− framework with two types of onedimensional (1D) chiral channels along the c axis. Compound 3 features a 3D network composed of 1D anionic [Sb4S9]4− chains and [Mn(dien)2]2+ complexes interconnected via various hydrogen bonds. The most interesting structural feature of 3 is the presence of two different oxidation states of antimony centers in the 1D [Sb4S9]4− chain with three different types of coordination environments, respectively. The optical absorption spectra indicate that the band gaps of compounds 1, 2, and 3 are 2.07, 2.04, and 2.29 eV, respectively. The thermal stabilities and magnetic properties of the title compounds are also studied.

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INTRODUCTION Open-framework chalcogenidometalates are investigated intensively in the past several decades because of their fascinating structural diversities and topologies, and potential applications in many areas, such as fast-ion conductivity, absorption, ion exchange, photocatalysis, electrooptics, and chemical sensors.1−5 An effective strategy for the development of new chalcogenidometalates is to design and construct new secondary building units (SBUs) via incorporation of other heteroatoms into the single metal chalcogenidometalates anionic framework.6 Nowadays, most efforts are devoted to studying those combining of groups 13−14 (Ga, In, Ge, Sn) and some transition-metal elements (Zn, Cd, etc).7,8 Most of these compounds are based on the supertetrahedral clusters (Tn, Pn, Cn) as SBUs, which are only constructed from the fundamental building units, namely, metal chalcogenide tetrahedra (e.g., GaS4, InS4, GeS4, CdS4). In recent years, systematic research efforts in this area have led to the extension of combining the group 15 element of Sb with groups 13−14 as well as some transition metals (Hg2+, Ag+, Cu+, etc).9−15 On the one hand, the antimony atom is favored to feature diverse oxidation states with a wide range of coordination numbers from 3 to 6, which would undergo selfcondensation to lead to the formation of new SBUs giving rise to novel open-framework chalcogenidometalates with remark© 2013 American Chemical Society

able topologies. More interesting, a few compounds illustrate that the Sb atom is also able to feature mixed oxidation states, for example, [M(dien)2]Sb4S9 (M = Ni, Co), [Mn(dien)2]MnSb2S7, and [Co(en)3]Sb2Se6, which all contain [SbIIIQ3]3− trigonal pyramids and [SbVQ4]3− tetrahedra (Q = S, Se).16,17 On the other hand, the stereochemically active lone pair of antimony(III) is likely to induce structures with noncentrosymmetric or even chiral structures, resulting in interesting physical properties, such as second-harmonic generation, enantioselective separation, and catalysis. Until now, among these multichalcogenidometalates, those combining transition metal tetrahedra and asymmetric coordination polyhedra of SbIII are relatively well-known;9 however, the reports on those containing mixed main-group metal polyhedra are still scarce. In the Ga/In-Sb-S/Se system, relatively few examples have been synthesized under mild solvothermal conditions but amazedly feature various networks from a 2D layer to a 3D framework, such as [Ni(dien)2]2In2Sb4S11, [(CH3CH2CH2)2NH2]5In5Sb6S19 1.45H2O, [Ni(dien)2]3(In3Sb2S9)2 2H2O, [M(dap)3]InSb3S7 (M = Co, Ni) (dap = 1,2diaminopropane), [Ni(en)3][Ga2Sb2S7], [Ni(en)3][InSbS4], Received: August 8, 2013 Revised: November 15, 2013 Published: November 20, 2013 101

dx.doi.org/10.1021/cg401208p | Cryst. Growth Des. 2014, 14, 101−109

Crystal Growth & Design

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Table 1. Crystal Data and Structure Refinements for [Ni(en)3][SnSb4S9] (1), [Co(en)3][SnSb4S9] (2), and [Mn(dien)2]2Sb4S9 (3) compound chemical formula fw space group a/Ǻ b/Ǻ c/Ǻ β/deg V(Ǻ 3) Z Dcalcd (g cm−3) temp (K) μ (mm−1) GOF on F2 flack parameter R1, wR2 (I > 2σ(I))a R1, wR2 (all data) a

1

2

3

C6N6H24NiSnSb4S9 1133.25 P3221 (No. 154) 14.4328(8) 14.4328(8) 11.3654(13) 90 2050.3(3) 3 2.753 293(2) 6.167 1.029 0.00(2) 0.0206/0.0409 0.0240/0.0419

C6N6H24CoSnSb4S9 1133.47 P3221 (No. 154) 14.4431(10) 14.4431(10) 11.3790(17) 90 2055.7(4) 3 2.747 293(2) 6.069 1.032 0.01(2) 0.0212/0.0353 0.0265/0.0366

C16N12H52Mn2Sb4S9 1298.12 P21/c (No. 14) 11.6991(7) 11.1853(7) 32.2459(19) 95.5660(10) 4199.7(4) 4 2.053 293(2) 3.596 1.067 0.0408/0.0725 0.0696/0.0795

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

and so on.10 As for the Ge-Sb-S system, the limited examples, including [Me 2 NH 2 ] 6 [(Ge 2 Sb 2 S 7 )(Ge 4 S 10 )], [M(en) 3 ][GeSb2S6] (M = Ni, Co), [(Me)2NH2]2[GeSb2S6], and [(Me)2NH2]2[DabcoH]2[Ge2Sb3S10] (Dabco = triethylenediamine), have been reported.11 More interestingly, [(Me)2NH2]2[GeSb2S6] features a 3D chiral framework and has a high ion-exchange capacity and high selectivity for Cs+ ions.11b Among these mixed main-group metal sulfides, the reports on the Sn-Sb-S system are relatively scarce comparing with those Ga/In/Ge-Sb-S phases. So far, several inorganic Sn-Sb-S compounds have been synthesized and characterized, including Sn4Sb6S13, Sn2Sb2S5, Sn3Sb2S6, etc.;18 however, only one inorganic−organic hybrid compound of [La(en)4SbSnS5]2· 0.5H2O was reported with an isolated hexanuclear molecule composed of SbS3 trigonal pyramids and SnS4 tetrahedra.19 Our exploratory studies in the Sn-Sb-S system led to two new isostructural quaternary tin(IV) antimony(III) sulfides, [TM(en)3][SnSb4S9] [TM = Ni (1), Co (2)], featuring 3D chiral frameworks based on SbS3 trigonal pyramids and SnS6 octahedra. Furthermore, we also obtained one new mixedvalent thioantimonate, [Mn(dien)2]2Sb4S9 (3), which contains 1D anionic [Sb4S9]4− chains composed of SbIIIS3 trigonal pyramids, SbIIIS4 trigonal bipyramids, and SbVS4 tetrahedra. Herein, we report their syntheses, crystal structures, and physical properties.

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room temperature on an X′Pert-Pro diffractometer using Cu Kα radiation (λ = 1.5406 Å) in the 2θ range of 5−85° with a step size of 0.04° and a 10 s/step counting time. Magnetic susceptibility measurements were performed on a Quantum Design PPMS-9T magnetometer at a field of 1000 Oe in the temperature range of 5−300 K. Synthesis of [Ni(en)3][SnSb4S9] (1). The reagents of Ni(CH3COO)2·4H2O (0.0497 g, 0.2 mmol), Sn (0.0237 g, 0.2 mmol), Sb (0.0974 g, 0.8 mmol), S (0.0577 g, 1.8 mmol), ethylenediamine (4 mL), and H2O (1 mL) were sealed in a stainless steel reactor with a 25 mL Teflon liner, and then heated at 130 °C for 7 days and quickly cooled to room temperature by turning off the furnace. The product consisted of red block-shaped crystals of 1 and a lot of an unknown black powder. The crystals were collected by hand and washed with ethanol, dried, and stored under vacuum (yield: 0.045 g, 20% based on Sb). The compounds are stable under ambient conditions and insoluble in common solvents. Microprobe elemental analyses on clean surfaces of several single crystals of 1 gave a Ni/Sn/Sb/S molar ratio of 0.91(8):1.21(2):3.89(3):9.18(5), which was in good agreement with the result determined by single-crystal X-ray diffraction study. Elemental analysis for C6N6H24NiSnSb4S9, found: C 6.41%, H 2.21%, N 7.52%; calcd: C 6.36%, H 2.14%, N 7.41%. IR (cm−1): 3280 (s), 3240 (s), 2930 (w), 2870 (w), 1620 (m), 1580 (m), 1460 (w), 1320 (w), 1020 (s), 654 (m), 519 (m). Synthesis of [Co(en)3][SnSb4S9] (2). The compound 2 was prepared in a manner analogous to that of 1 except that Co(CH3COO)2·4H2O was used instead of Ni(CH3COO)2·4H2O. Red crystals of 2 were filtered, washed with ethanol, and air-dried (yield: 0.020 g, 9% on the basis of Sb). Microprobe elemental analyses on clean surfaces of several single crystals of compound 2 gave a Co/ Sn/Sb/S molar ratio of 0.92(3):0.98(1):4.17(8):9.18(5), which was in good agreement with that determined by single-crystal X-ray diffraction study. Elemental analysis for For C6N6H24CoSnSb4S9, found: C 6.29%, H 2.20%, N 7.58%; calcd: C 6.36%, H 2.13%, N 7.41%. IR (cm−1): 3271 (s), 3230 (s), 2915 (w), 2862 (w), 1611 (m), 1561 (m), 1478 (w), 1329 (w), 1010 (s), 667 (w), 523 (w). Synthesis of [Mn(dien)2]2[Sb4S9] (3). A mixture of Mn(CH3COO)2·4H2O (0.0980 g, 0.4 mmol), Sb (0.0974 g, 0.8 mmol), S (0.064 g, 2 mmol), dien (4 mL), and H2O (1 mL) was sealed into a stainless steel reactor with a 25 mL Teflon liner, and then heated at 140 °C for 7 days and cooled to room temperature. Yellow blockshaped crystals of 3 were collected by hand, and washed with ethanol and air-dried in the yield of 8% (0.021 g) based on Sb. Microprobe elemental analyses on clean surfaces of several single crystals of 3 gave a Mn/Sb/S molar ratio of 1.89(3):3.90(1):9.27(8), which was in good agreement with that determined by single-crystal X-ray diffraction

EXPERIMENTAL SECTION

Materials and Instruments. All analytical grade chemicals were obtained commercially and used without further purification. Elemental analyses (C, H, and N) were performed using a PE2400 II elemental analyzer. Semiquantitative elemental analyses for Co, Ni, Mn, Sn, Sb, and S were performed on a JSM-6700F scanning electron microscope (SEM) equipped with an energy-dispersive spectroscope (EDS) detector. The UV/vis spectra were recorded 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. 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 performed using a Mettler TGA/SDTA 851 thermal analyzer under a N2 atmosphere with a heating rate of 10 °C min−1 in the temperature region of 30− 800 °C. X-ray diffraction (XRD) powder patterns were collected at 102



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turned off the furnace at 130 °C, which forced the reaction system to quickly cool to room temperature, leading to relatively higher yields of compounds 1 and 2. Hence, the degree of crystallization of compounds 1 and 2 is sensitive to the reaction temperature and cooling rate, and such phenomenon may be due to their lower thermodynamic stabilities. Differently, the reaction temperature and cooling rate play unimportant roles in the synthesis of compound 3, but the dosage of S powder had some effect on the yield of 3. A little superfluous S powder is able to feature relatively strong oxidation abilities and slightly increase the yield of 3. Crystal Structures of 1 and 2. Compounds 1 and 2 are isostructural; hence, only 1 is discussed here in detail. Structure refinement reveals that compound 1 features a 3D chiral [SnSb4S9]2− framework composed of SnS6 octahedra and bowlike Sb4S9 units built from the corner-sharing of four SbS3 trigonal pyramids (Figure 1). The asymmetric unit of 1

study. Anal. for C16N12H52Mn2Sb4S9, found: C 14.71%, H 4.15%, N: 12.81%; calcd: C 14.80%, H 4.04%, N 12.95%. IR (cm−1): 3250 (s), 2870 (m), 1580 (w), 1420 (m), 1180 (w), 1060 (w), 995 (m), 883 (w) and 627 (w). Crystal Structure Determination. Single-crystal X-ray diffraction data of the title compounds were recorded on a Bruker SMART CCDbased diffractometer (Mo Kα radiation, graphite monochromator) at 293(2) K. Absorption corrections were applied using the multiscan technique. All the data sets were corrected for the Lorentz factor, polarization, air absorption because of variations in the path length through the detector faceplate. All the structures were solved using direct methods and refined by full-matrix least-squares with atomic coordinates and anisotropic displacement parameters for all non-hydrogen atoms using the SHELX program.20 The space groups of the compounds 1 and 2 were determined to be P3221 (No. 154), and 3 belongs to P21/c (No. 14) based on the systematic absences, E-value statistics, and satisfactory refinements. The hydrogen atoms attached to C and N atoms were positioned with idealized geometry and refined with fixed isotropic displacement parameters. Site occupancy refinements for these compounds indicated that all sites were fully occupied. For compounds 1 and 2, the final R = 0.0206 and 0.0212, wR = 0.0409 and 0.0353 for 3149 and 3151 observed reflections (I > 2σ(I)) with 124 parameters, respectively. For compound 3, the final R = 0.0408, wR = 0.0725 for 9665 observed reflections (I > 2σ(I)) with 389 parameters. Relevant crystal and collection data parameters and refinement results can be found in Table 1. Selected bond lengths (Å) and angles (deg) for the title compounds are listed in the Supporting Information. Electronic Structure Calculations. Single-crystal structural data of the compound 1 was used for the theoretical calculation. The density of state (DOS) was performed with the total energy code, CASTEP.21 The total energy is calculated with the density functional theory (DFT) using the Perdew−Burke−Ernzerhof generalized gradient approximation (GGA).21c The interactions among the ionic cores and the electrons were described by the norm-conserving pseudopotential. The following orbital electrons are treated as valence electrons: H-1s2, N-2s22p2, C-2s22p2, S-3s23p4, Ni-3s23p63d84s2, Sn5s25p2, and Sb-5s25p3. The number of plane waves included in the basis was determined by a cutoff energy of 780 eV, and the numerical integration of the Brillouin zone was performed using a 2 × 2 × 2 Monkhorst−Pack k-point. The other calculating parameters and convergent criteria were the default values of the CASTEP code.

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Figure 1. Coordination environment of the Ni2+ ion, and the structure of the SnSb4S13 unit and the 3D [SnSb4S9]2− framework of compound 1 along the c axis.

RESULTS AND DISCUSSION Our exploratory studies of the Sn-Sb-S system in en solvent led to two new isostructural quaternary tin(IV) antimony(III) sulfides, [TM(en)3][SnSb4S9] [TM = Ni (1), Co (2)], which feature 3D chiral frameworks based on SnS6 octahedra and SbS3 trigonal pyramids. Studies in diethylenetriamine solvent led to a new mixed-valent thioantimonate of [Mn(dien)2]2Sb4S9 (3) composed of SbS3 trigonal pyramids, Ψ-SbS4 trigonal bipyramids, and SbS4 tetrahedra. The solvothermal reaction of Ni(CH3COO)2·4H2O (or Co(CH3COO)2·4H2O), Sn, Sb, and S produced very fine red crystals of 1 and 2 as well as a lot of unknown black powder. During the syntheses, the [TM(en)3]2+ (TM = Ni, Co) complexes as counterions were in situ formed, which has been found in many thio-, seleno-, or or tellurometalates.22,23 It was found that the reaction temperature had a significant influence on the crystal growth of 1 and 2. When the reaction temperature is higher than 130 °C, the same shaped red crystals of 1 and 2 were obtained, but with very lower yields. Furthermore, if the reaction system was slowly cooled to room temperature in 2 days, the product mainly consisted of simple thiostannates and thioantimonates, such as [TM(en)3]Sn2S6, [TM(en)3]Sb2S5, and so on. In the work here, we directly

contains two crystallographically independent Sb3+, one unique Sn4+, five S2−, and one [Ni(en)3]2+ cation, respectively. Both Sb3+ ions adopt SbS3 trigonal-pyramidal coordination geometries with Sb−S bond lengths ranging from 2.3984(12) to 2.4815(12) Å and S−Sb−S angles in the range of 85.18(5)− 104.50(4)°. The Sn4+ ion is coordinated by six S atoms to give a slightly distorted octahedral geometry with Sn−S bond distances in the range of 2.5028(12)−2.6652(12) Å, which are evidently longer than those of SnS4 tetrahedra reported in many thiostannates(IV).24 However, these lengths are comparable with those of SnS6 octahedra in Sn5S12(N2C4H11)(N4C10H24) and K2SnAs2S6.12b,25 The cis and trans S−Sn−S bond angles vary from 82.53(4) to 99.03(3)° and 166.13(6) to 176.30(4)°, respectively, which indicate a slight deviation from the ideal octahedral geometry. As far as we know, Sn prefers tetrahedral coordination with chalcogen atoms, and the SnQ6 (Q = S, Se, Te) octahedral geometry in inorganic−organic hybrid thiostannates is still scarce. Each S2− is bonded to two metal cations: S(1), S(2) and S(3) connect with one Sn and 103



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one Sb atom, and S(4) and S(5) bridge two Sb atoms, respectively. Two neighboring Sb(2)S3 trigonal pyramids are condensed by sharing the corner S atoms to form an Sb2S5 dimer, which are attached by two Sb(1)S3 trigonal pyramids on both sides via corner sharing into a bow-like Sb4S9 tetramer as a new SBU (Figure 1). The Sb4S9 tetramers are further waved using SnS6 octahedra to form a right-handed helical chain running along the 31 axis parallel to the c axis (Figure 2a). Two such parallel right-handed helical chains are intertwined together to form a 1D chiral channel along the c axis (Figure 2b). Such chiral channels with a rough hexagonal cross section of 8.54 × 8.54 Å2 are presented in this framework along the c axis. One full turn of the Sn-S-Sb4-S-Sn right-handed helix contains three SnS6 octahedra and three Sb4S9 tetramers with a pitch of 22.73 Å. Each right-handed helix further connects to six neighboring ones by sharing S atoms to generate a 3D anionic [SnSb4S9]2− framework. Such connectivity also leads to another type of 1D chiral channel based on the single left-handed helical chain along the c axis (Figure 2c). This helix is built from the alternating arrays of Sb2S5 dimers and SnS6 octahedra interconnected by corner-sharing running along the 31 axis parallel to the c axis. One full turn of the Sn-S-Sb2-S-Sn lefthanded helix contains three Sb2S5 dimers and three SnS6 octahedra with a pitch of 11.37 Å. Such a chiral channel has a nearly hexagonal cross section of 6.14 × 6.14 Å2 presented in this framework along the c axis. Another interesting structural feature of 1 is that it also features two types of opposite chiral channels based on two different kinds of helical chains running along the a or b axis (Figure 3). The single right-handed chain is composed of alternating Sb2S5 dimers and SnS6 octahedra, and the intertwined double left-handed chains are formed by alternating Sb4S9 tetramers, SnS6 octahedra, and Sb2S5 dimers via cornersharing, respectively. The full turn of these right- and lefthanded helices include 12 (4 SnS6 and 8 SbS3) and 16 (4 SnS6 and 12 SbS3) polyhedra with pitches of 28.89 and 14.43 Å, respectively. The [Ni(en)3]2+ complexes as structure-directing molecules and charge-balancing agents are located at the space among the SnS6 octahedra and form extensive N−H···S hydrogen bonds with S atoms of the anionic network (Figure S2 in the Supporting Information). The N−H···S hydrogen bond distances and angles fall in the range of 3.512(4)−3.669(4) Å and 134.6−159.1°, respectively. A PLATON analysis, performed only on the framework of the structure, suggested a solvent-accessible volume of approximately 44.8%.26 It should be noted that all the bond lengths and angles of compound 2 are close to those of compound 1 due to the very similar ionic radii of Co2+ and Ni2+. It is reported that the trigonal-pyramidal SbS3 or trigonalbipyramidal ψ-SbS4 anions are often self-condensed to form various oligomeric chains or rings as SBUs, which are able to further polymerize, leading to 2D or 3D framework chalcogenidometalates. However, in the mixed 13/15 or 14/ 15 group metal thiometalates, the SbS3 or ψ-SbS4 units tend to feature discrete anions, dimer, or trimer, and then connect with other metal ions to form new heterometallic SBUs.10,11 The bow-like [Sb4S9] tetramer as a new SBU constructing 3D framework in compound 1 has not been reported in the mixed group metal thiometalates. Crystal Structures of 3. Compound 3 belongs to the monoclinic space group P21/c (No. 14) and consists of 1D

Figure 2. View of the profiles of single, double right-handed helical chains (a, b) and left-handed helical chain (c) running along the c axis. The double helical chains are represented as green and purple only for clarity, respectively. 104



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Figure 4. View of the structures of 1D [Sb4S9]4− chains composed of SbIIIS3 trigonal pyramids, SbIIIS4 trigonal bipyramids, and SbVS4 tetrahedra in compound 3. The different polyhedra are drawn as different colors.

pair of the antimony(III). Both the Sb(2) and the Sb(3) atoms adopt SbS3 trigonal-pyramidal coordination geometries with Sb−S bond lengths ranging from 2.3264(17) to 2.4982(16) Å and S−Sb−S angles in the range of 94.39(5)−101.46(6)°, which are comparable with those of compounds 1 and 2. The Sb(4) atom is also coordinated by four S2− ions (S(1), S(7), S(8), and S(9) atoms) similar to that of the Sb(1) atom but with a slightly distorted tetrahedral coordination environment. The Sb(4)−S bond lengths fall in the range of 2.3048(15)− 2.3611(15) Å, which are slightly shorter than some of Sb(1), Sb(2), and Sb(3) atoms. The S−Sb(4)−S angles are in the range of 107.13(6)−112.57(6)°, which indicate a slight deviation from the ideal tetrahedral geometry. These values are in the normal range found in the literature.28 All the above Ψ-SbS4 trigonal bipyramids, SbS3 trigonal pyramids, and SbS4 tetrahedra have been reported in many thioantimonates.21 Hence, we easily conclude that the Sb(1), Sb(2), and Sb(3) centers should be of the +3 oxidation state, and the Sb(4) is of the +5 oxidation state, respectively. Therefore, the chargebalanced formula of 3 can be described as {[Mn(dien)2]2}4+{(Sb1)3+(Sb2)3+(Sb3)3+(Sb4)5+(S2−)9}. Using Brown’s bondvalence model, the calculated valence sums surrounding Sb(1), Sb(2), Sb(3), and Sb(4) atoms are 2.88, 3.18, 3.10, and 5.17, respectively, which are in good agreement with the assigned valences.29 The Ψ-Sb(1)S4 trigonal bipyramids and Sb(2)S3 and Sb(3)S3 trigonal pyramids are condensed via edge-sharing to form an Sb3S7 trimer with three-membered [Sb3S3] rings. Such a ringed Sb3S7 trimer is similar to that of [Ni(dien)2]9[Sb22S42]·0.5H2O and [Ni(dien)2]3[Sb12S21]·H2O, etc.30 Each Sb3S7 trimer is attached by one Sb(4)S4 tetrahedron via sharing S(1) atom into the Sb4S10 unit, which are further interconnected in a contrary direction via sharing the S(4) atom to form 1D [Sb4S9]4− anionic chains along the b axis. These 1D [Sb4S9]4− chains feature parallel packing along the a and c axes (Figure 5). In 3, all the S atoms of the 1D [Sb4S9]4− anionic chains are involved in hydrogen bonding with the dien ligands of [Mn(dien) 2 ]2+ cations with N···S separations between

Figure 3. View of the 3D framework of 1 along the a axis (a), and the cross section of left-/right-handed helices (b).

anionic [Sb4S9]4− chains and two charge-compensating complex cations of [Mn(dien)2]2+. The asymmetric unit of compound 3 contains four crystallographically independent Sb3+ centers, nine S2−, two Mn2+ ions, and four dien molecules as ligands. Both the Mn(1)2+ and Mn(2)2+ ions are coordinated by six nitrogen donors from four dien ligands with slightly distorted octahedral geometries, respectively. The cis and trans N−Mn−N bond angles vary from 75.4(2) to 122.71(19)° and 147.4(2) to 161.7(2)°, respectively, and the Mn−N bond distances are in the range of 2.235(5)−2.350(6) Å, which are in the normal ranges found in other Mn2+ complexes with amino ligands.27 The 1D anionic [Sb4S9]4− chain is composed of SbS3 trigonal pyramids, SbS4 trigonal bipyramids, and SbS4 tetrahedra interconnected by corner-sharing and propagates along the crystallographic b axis. As shown in Figure 4, the Sb(1) atom is surrounded by four S2− ions with a Ψ-SbS4 trigonal-bipyramidal coordination geometry with two short (2.4601(14) and 2.5190(16) Å) and two long (2.7099(17) and 2.8277(17) Å) Sb−S distances, in which two long Sb−S bonds are nearly trans to each other; the fifth coordination site is occupied by the lone 105



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and selenidoantimonates always feature low-dimensional anionic structures containing monodentate and bidentate [SbVQ4] anions. Optical Properties and Thermal Stabilities. The optical diffuse reflection spectra of compounds 1, 2, and 3 were measured at room temperature. As shown in Figure 6, the

Figure 5. Stacking manner of the 1D {[Sb4S9]4−}∞ chains in compound 3. The [Mn(dien)2]2+ complexes are deleted only for clarity.

3.436(5) and 3.729(6) Å and N−H···S angles between 122.3 and 174.4°, respectively, indicating the weak N−H···S hydrogen bonding interactions (Figure S3 in the Supporting Information). These values are close to those reported in inorganic−organic hybrid thioantimonates. The [(dien)2Mn]2+ and [Sb4S9]4− anionic chains are interlinked via hydrogen bonds into a 3D H-bonding network structure. It is very interesting to compare the structures of compound 3 with the other two isostructural compounds of [Co(dien)2]2[Sb4S9] and [Ni(dien)2]2[Sb4S9],16 which all feature 1D [Sb4S9]4− anionic chains containing SbIII and SbV centers. Despite their similar structural compositions, the Sb centers feature slightly different coordination geometries. In compound 3, the Sb(1) atom obviously adopts a Ψ-SbS4 trigonal bipyramid coordination geometry with two short (2.4601(14) and 2.5190(16) Å) and two long (2.7099(17) and 2.8277(17) Å) Sb−S distances, whereas the Sb centers at the same position in [Co(dien)2]2[Sb4S9] and [Ni(dien)2]2[Sb4S9] are both coordinated by three Sb atoms with near Sb−S distances of 2.453−2.637 Å as well as a S atom with a weak Sb−S secondary bonding interconnection at longer distances of 2.982 and 2.963 Å, respectively (Figure S4, Supporting Information). The latter are significantly larger than the sum of the ionic radii of Sb and S.31 Strictly speaking, the coordination environments of these Sb atoms should be considered as trigonal-pyramidal geometries. Hence, the 1D [Sb4S9]4− chain of compound 3 is composed of three different types of polyhedra: Ψ-SbS4 trigonal bipyramids, SbS3 trigonal pyramids, and SbS4 tetrahedra, whereas the 1D [Sb4S9]4− chains of [Co(dien)2]2[Sb4S9] and [Ni(dien)2]2[Sb4S9] can be considered as only consisting of SbS3 trigonal pyramids and SbS4 tetrahedra. Speaking from this perspective, compound 3 represents a new thioantimonate combining three different types of Sb chalcogenide polyhedra with mixed valency, and such a structural character is very similar to those of [TM(dien)2]Sb4Se9 (TM = Mn, Fe).17 The result also implies that the different [TM(amine)x]2+ (TM = transition metal) complexes have different structure-directing effects on the formation of inorganic−organic hybrid thiometalates. Furthermore, some other thioantimonates and selenidoantimonates containing mixed-valent Sb centers have also been reported. For example, [Co(dien)2]2Sb2Se6 contains a discrete [Sb2Se6]4− anion formed by an [SbIIISe3] trigonal pyramid and an [SbVSe4] tetrahedron sharing a common corner, and the main structural motif of the [MnSb2S7]4− anion in [Mn(dien) 2 ]MnSb 2 S 7 is constructed by a [MnS 4 ] 6− tetrahedron, a [SbIIIS3]3−, and a [SbVS4]3− anion interconnected via sharing edges.17 These mixed-valent thioantimonates

Figure 6. Solid-state optical absorption spectra of compounds 1, 2, and 3.

optical band gaps obtained by extrapolation of the linear portion of the absorption edges are estimated as 2.07, 2.04, and 2.29 eV, for 1, 2, and 3, respectively. These band gaps were close to those of other thioantimonates, such as [Ni(phen)3]2Sb18S29 (2.16 eV) and Mn2Sb2S5(N2H4)3 (2.09 eV), and tin antimony sulfide of [La(en)4SbSnS5]2 0.5H2O (2.36 eV).10f,19 The thermal stabilities of 1, 2, and 3 were examined by thermogravimetric analysis (TGA) in a N2 atmosphere from 30 to 800 °C (Figure 7). The TGA curve revealed that 1 and 2 lost

Figure 7. Thermogravimetric curves for compounds 1, 2, and 3.

one en ligand below 306 °C with mass loss of 5.1% and 5.8%, respectively, which are close to the theoretical value of 5.3%. In the range of 306−335 °C, the other two en ligands are further removed in one step with a total observed weight loss of 16.2% and 16.3%, respectively, in accordance with the theoretical value of 15.9%. Compound 3 lost all organic amine molecules from 240 to 336 °C. The observed weight loss of 32.0% is close to the theoretical value of 31.8%. After losing the organic amine molecules, all the compounds 1, 2, and 3 continued to slowly lose weight and still did not achieve the balance to 800 °C. Theoretical Studies. To gain further insight into the electronic structure of the compounds, 1 was selected as the representative to calculate their band structures and density of 106



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states (DOS). It is found that 1 has a band gap of about 1.45 eV, which is smaller than the experimental optical band gap. Such a discrepancy is due to the discontinuity of the exchangecorrelation potential that underestimates the band gap in semiconductors and insulators. In the DOS curve, the conduction bands just above the Fermi level in the range of 0−2 eV are mainly contributed by Sn-5p, Sb-5p, and S-3p orbitals, and the valence bands just below the Fermi level are also derived from the Sn-5p, Sb-5p, and S-3p orbitals (Figure 8). Therefore, the band gap of compound 1 is primarily the

Figure 9. Temperature dependence of the χm and 1/χm curves for 1 (a) and 2 (b).

thioantimonate (III and V), [Mn(dien)2]2[Sb4S9], directed by transitional metal complexes have been solvothermally synthesized and structurally, thermally, optically, and magnetically characterized. It is very interesting to combine SnS6 octahedra and SbS3 asymmetric coordination geometries in a single-crystal structure to form a new chiral 3D framework, which is very scarce for inorganic−organic hybrid openframework chalcogenidometalates. It is also available to combine three different types of SbS3, Ψ-SbS4, and SbS4 polyhedra into a single compound, which will afford a diversiform linking node, leading to more interesting structures. The successful syntheses of the title compounds provide possibilities of constructing other novel open-framework chalcogenidometalates based on SbS3 trigonal pyramids, ΨSbS4 trigonal bipyramids, and nontetrahedral coordination geometries (SnS6, GeS6, etc), not only group 13 metal supertetrahedral clusters. Research on this subject is in progress.

Figure 8. Total density of states and partial density of states for 1. The Fermi level is set at 0 eV (dotted line).

result of the charge-transfer transition in the anionic framework, while C, N, and H contribute little. This is similar to the previously reported antimony sulfides, such as [Cr(tren)]Sb4S7 and [Ni(dien)2]Sb6S10.32 Magnetic Properties. The magnetic susceptibilities of 1 and 2 were investigated as examples in the temperature range of 5−300 K, and the temperature dependence of the molar susceptibility χm and 1/χm is shown in Figure 9. Both compounds 1 and 2 show the Curie−Weiss behavior in the temperature range of 10−300 K. The Curie−Weiss fits to the 10−300 K susceptibility data yield C = 1.07 and 3.25 emu·K mol−1 and θ = −3.2 and −13 K for compounds 1 and 2, respectively. The small negative Weiss content indicates the weak antiferromagnetic interactions. The calculated effective magnetic moment of compound 1 at room temperature is 2.85 μB per Ni2+ atom, which is comparable with the spin-only value of 2.83 μB for one Ni2+ ion. The calculated effective magnetic moment of compound 2 at room temperature is 5.02 μB per Co2+ atom, which is higher than the spin-only value for hs-Co2+ (3.87 μB) due to an orbital contribution arising from the 4T1g ground state of Co2+. Such value is comparable with those of octahedrally coordinated Co2+ compounds (4.7−5.1 μB).22

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format (CCDC numbers 954114 for 1, 954115 for 2, and 954116 for 3), and tables of hydrogen bonds, structures, and XRD. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected].

CONCLUSION In the work reported here, two novel quaternary tin antimony sulfides, [TM(en)3][SnSb4S9], and one new mixed-valent

Notes

The authors declare no competing financial interest. 107



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ACKNOWLEDGMENTS We thank the 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 BS2012CL008), the China Postdoctoral Science Foundation funded project (No. 2012M521321), the Post Doctoral Innovation Project of Shandong Province (201303097), the High Educational Science & Research Foundation of Shandong Province (Nos. J11LB52 and J13D58), and the Scientific Research and Technological Development Program of Jining City (No. 20125014). We thank Prof. Jiang-Gao Mao at FJIRSM for help with the electronic structure calculation.

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