Carolin Anderer , Christian Näther and Wolfgang Bensch

Room temperature synthesis, crystal structure and selected properties of the new compound [Mn2(bipy)4SbS4](ClO4)

De Gruyter | Published online: March 8, 2016

Abstract

The new compound [Mn2(bipy)4SbS4](ClO4) was prepared by a new synthetic route for the preparation of thioantimonates(V) that can be used even at room temperature. Mixing aqueous solutions of [Mn(bipy)3](ClO4)2 and Na3SbS4 · 9H2O leads to immediate crystallization of the pure compound. In the structure an SbS43– anion acts as a tetradentate bridge connecting two Mn2+ cations of [Mn(bipy)3]2+ complexes (bipy = 2,2′-bipyridine). The compound features a hitherto unknown [Mn2(bipy)4SbS4]+ cation. Bipy ligands of adjacent cations are arranged parallel to each other leading to weak off-center parallel π-π interactions stabilizing the crystals. Magnetic measurements indicate weak antiferromagnetic exchange interactions between the Mn2+ centers.

1 Introduction

The thioantimonate chemistry is dominated by Sb(III)Sx (x = 3–5) units which are in most structures further condensed to form larger building units [15] like [Sb3S6]3– or [Sb4S8]4– rings [68], chains or layers with compositions [Sb4S7]2– [917], [Sb3S5] [18], [Sb6S10]2– [1921] or [Sb8S13]2– [17, 20, 2224] or even three-dimensional networks [9, 2528]. Compared to thioantimonates(III) the structural chemistry of [Sb(V)S4]3– is much less developed and in most compounds the cations and the [Sb(V)S4]3– anions are separated [2935]. There are only few exceptions where bond formation between the cation and [SbS4]3– was observed [36, 37]. In these compounds the SbS4 group mostly acts in a monodentate fashion like in [Mn(dach)3][Mn(dach)2(SbS4)2] · 6H2O [38] (dach = 1,2-diaminocyclohexane) or the pseudo-polymorphs [Co(dien)2][Co(tren)SbS4]2 · 4H2O [36] (dien = diethylenetetraamine, tren = tris(2-aminoethyl-)amine) and [Co(dien)2][Co(tren)SbS4]2 · 0.5H2O [39]. However, bi- and tridentately acting [SbS4]3– anions are observed in very few compounds [4043]. There are also few examples for mixed-valent Sb(III,V) thioantimonates like [Mn(dien)2]2[MnSb2S7] [44] or the isostructural compounds [Ni(dien)2]2[Sb4S9] [45] and [Co(dien)2]2[Sb4S9] [46]. Among the examples for an incorporation of transition metal cations into thioantimonates Mn2+ plays a special role. While for ions like Ni2+, Co2+, Fe2+ or Zn2+ synthetic tricks are required to force Sb–S–M2+ (M = Ni, Co, Fe, Zn) bond formation, [10, 4750] Mn2+ is easily integrated into thioantimonate networks [5157].

Recently we reported a new synthesis strategy for the generation of thioantimonates(III) utilizing Na3SbS4·9H2O (Schlippe’s salt) as source. The [SbS4]3– anion undergoes a sequence of chemical reactions with water supplying SbS33– besides other antimony compounds. Applying Ni2+ or Fe2+ complexes, the reactions with Schlippe’s salt afforded crystallization of [Ni(bipy)3][Sb6S10], [Fe(bipy)3][Sb6S10], and [Ni(dibipy)3][Sb6S10] (bipy = 2,2′-bipyridine, dibipy = 4,4′-dimethyl-2,2′-bipyridine) [58]. We now extended the synthetic work to Mn2+ complexes using [Mn(bipy)3](ClO4)2 as starting material. By adding water to a mixture of [Mn(bipy)3](ClO4)2 and Na3SbS4 · 9H2O at room temperature a phase pure polycrystalline powder was obtained. Upon applying solvothermal techniques the slurry yielded single crystals of a compound which could then be identified as [Mn2(bipy)4SbS4](ClO4). The reaction also partially led to a polysulfide, namely [Mn(bipy)2S6] and an unknown compound.

The new compound [Mn2(bipy)4SbS4](ClO4) features a [Mn2(bipy)4SbS4]+ cation and a perchlorate anion. Here we report the preparation, crystal structure and selected properties of this compound.

2 Results and discussion

[Mn2(bipy)4SbS4](ClO4) crystallizes in the monoclinic space group C2/c with two unique S atoms and one Mn atom as well as two bipy ligands on general positions. The perchlorate anion is disordered over two positions around a two-fold axis. The Mn2+ ion is in a distorted octahedral environment of four N atoms of the two bipyridine ligands and two S atoms of a [SbS4]3– unit (Fig. 1). The Mn–N and Mn–S bond lengths (2.222(4)–2.305(4) Å for Mn–N and 2.5804(13) and 2.6429(13) Å for Mn–S) and angles (Table 1) are in the range known from other thioantimonates [10, 38, 41, 56, 5963]. The [SbS4]3– unit acts as a tetradentate bridging ligand and exhibits a distorted tetrahedral geometry. The Sb–S bond lengths in the [SbS4]3– unit are in the normal range (2.3246(11)–2.3342(11) Å) known from other thioantimonates(V) [36, 38, 39, 41, 64]. The S–Sb–S angles (100.53–116.95°) indicate a moderate distortion of the tetrahedral geometry.

Table 1

Selected bond lengths (Å) and angles (deg) of [Mn2(bipy)4SbS4](ClO4).

Sb(1)–S(1) 2.3246(11) N(2)–Mn(1)–S(2) 98.03(11)
Sb(1)–S(2) 2.3342(11) N(2)–Mn(1)–S(1) 173.14(11)
Mn(1)–N(1) 2.222(4) N(11)–Mn(1)–N(2) 90.61(14)
Mn(1)–N(12) 2.223(4) N(11)–Mn(1)–S(1) 85.44(10)
Mn(1)–N(11) 2.291(4) N(11)–Mn(1)–S(2) 168.94(11)
Mn(1)–N(2) 2.305(4) N(12)–Mn(1)–N(2) 90.05(14)
Mn(1)–S(2) 2.5804(13) N(12)–Mn(1)–N(11) 72.72(14)
Mn(1)–S(1) 2.6429(13) N(12)–Mn(1)–S(1) 94.11(11)
S(1)–Sb(1)–S(1A) 112.63(6) N(12)–Mn(1)–S(2) 100.24(11)
S(1)–Sb(1)–S(2) 100.53(4) S(1)–Sb(1)–S(2A) 116.95(4)
S(1A)–Sb(1)–S(2) 116.95(4) S(1A)–Sb(1)–S(2A) 100.53(4)
N(1)–Mn(1)–N(2) 72.30(15) S(2)–Sb(1)–S(2A) 110.04(7)
N(1)–Mn(1)–N(12) 157.61(15) S(2)–Mn(1)–S(1) 86.60(4)
N(1)–Mn(1)–N(11) 93.30(14) Sb(1)–S(1)–Mn(1) 84.46(4)
N(1)–Mn(1)–S(2) 95.89(11) Sb(1)–S(2)–Mn(1) 85.70(4)
N(1)–Mn(1)–S(1) 102.29(11)
Fig. 1: Structure of the [Mn2(bipy)4SbS4]+ cation of the title compound. H atoms are omitted for clarity.

Fig. 1:

Structure of the [Mn2(bipy)4SbS4]+ cation of the title compound. H atoms are omitted for clarity.

The cations form rods running along [001]. Along [010] the cations and anions alternate in the fashion ···cation-cation-anion-cation-cation···. Between the cations and the anions C–H···O (O···H distances: 2.33–2.63 Å; C–H···O angles: 131.7–155.7°) and C–H···S interactions (H···S distances 2.86–2.89 Å. C–H···S angles 148.0–168.3°) are observed (Table 2).

Table 2

Hydrogen bonds (Å, deg) of [Mn2(bipy)4SbS4](ClO4).a

D–H···A d(D–H) d(H···A) d(D···A) <(DHA)
C(7)–H(7)···S(2)#1 0.95 2.86 3.701(5) 148.0
C(9)–H(9)···O(2)#2 0.95 2.54 3.43(2) 155.7
C(9)–H(9)···O(4′)#2 0.95 2.33 3.15(3) 143.5
C(17)–H(17)···S(2)#3 0.95 2.89 3.822(5) 168.3
C(19)–H(19)···O(4′)#1 0.95 2.63 3.34(3) 131.7

aSymmetry transformations used to generate equivalent atoms: #1 – x + 1/2, –y + 1/2, –z + 1; #2 x + 1/2, y – 1/2, z; #3 x + 1/2, –y + 1/2, z + 1/2.

Off-center parallel interactions of bipyridine ligands of adjacent complexes with distances ranging from 3.19 to 3.54 Å (Fig. 2) lead to a two-dimensional layer-like arrangement in the (010) plane (Fig. 3). The intermolecular distances between stacked bipyridine ligands indicate attractive interactions as was already demonstrated for arenes of different sizes in reference [65]. Recently, the interaction energy for the stacking of phen molecules was calculated for [Mn2(phen)4(Sn2S6)] [66] exhibiting similar separations of the aromatic rings. The values obtained are around 10 kcal/mol and one can assume that these intermolecular interactions contribute to the arrangements of the complexes and the stability of the crystals [65].

Fig. 2: Different arrangements of the bipy molecules in the structure of [Mn2(bipy)4SbS4](ClO4). The dashed red lines show the shortest distances (values in Å).

Fig. 2:

Different arrangements of the bipy molecules in the structure of [Mn2(bipy)4SbS4](ClO4). The dashed red lines show the shortest distances (values in Å).

Fig. 3: Arrangement of the [Mn2(bipy)4SbS4]+ cations in the crystallographic ac plane. H atoms are omitted for clarity and π-π interactions are indicated by dashed lines.

Fig. 3:

Arrangement of the [Mn2(bipy)4SbS4]+ cations in the crystallographic ac plane. H atoms are omitted for clarity and π-π interactions are indicated by dashed lines.

The new compound contains a hitherto unknown [Mn2(bipy)4SbS4]+ cation. There is only one example reported in thioantimonate(III) chemistry, where a cationic species containing a thioantimonate anion is observed [67]. In the crystal structure of {[Eu(dien)2]2(μ4-Sb2S5)}Cl2 the [Sb2S5]4– anion connects two [Eu(dien)2]3+ complexes to form the [Eu(dien)2]2(μ4-Sb2S5)]2+ cation which is charge balanced by two chloride anions [67].

Another interesting feature is the fact that the [SbS4]3– anion acts as a tetradentate ligand. The majority of the thioantimonate(V) compounds consist of separated cations and tetrahedral [SbS4]3– anions, or of monodentately acting [SbS4]3–. Only a few thioantimonates(V) contain [SbS4]3– acting as a bidentate or tridentate ligand. Examples for the bidentate mode are [Mn(dien)2][Mn(dien)SbS4]2 [41] and [Ln(en)3(H2O)SbS4 ] (Ln = Sm [37], Pr [68]). The μ3-bridinging mode is more often observed, especially in rare earth cation containing compounds in which [SbS4]3– anions serve as ligands to form one-dimensional chains [43, 64, 69]. The first example for the μ4-mode of the anion has now been detected in [Mn2(bipy)4SbS4](ClO4).

The title compound was prepared under similar conditions as used for the synthesis of [Ni(bipy)3][Sb6S10], [Fe(bipy)3][Sb6S10] and [Ni(DiBipy)3][Sb6S10] [58] reported recently. Using the corresponding Mn2+ complex in the synthesis leads to the formation of the title compound instead of anionic thioantimonate(III) layers. One reason may be that [Mn2(bipy)4SbS4](ClO4) crystallized very fast and first crystallites are already observed within a few seconds after mixing the educts in water at room temperature. Hence one can assume that the concentration of the slowly generated [SbS3]3– anion is too low to allow formation of the anionic network by condensation of thioantimonate(III) species. This assumption is supported by time dependent synthesis studies where small needles of [Ni(bipy)3]Sb6S10 were formed only after 3.5 h. For the title compound, the formation mechanism might be a ligand exchange reaction in which one bipy ligand of a [Mn(bipy)3]2+ complex is replaced by a [SbS4]3– unit according to the following equation.

2  [Mn ( bipy ) 3 ] 2 + + 4 ClO 4 + 3 Na + +  SbS 4 3  [Mn 2 ( bipy ) 4 SbS 4 ](ClO 4 ) + 3 Na + + 3 ClO 4 + 2 bipy

The stability constants of [TM(bipy)3]2+ complexes provide an explanation for this pathway. With log β3 = 20.1 and 17.5 for Ni2+ and Fe2+ complexes, the stability constants are about three times larger than for the Mn2+ complex (β3 = 6) [70]. Hence, it can be assumed that [Mn(bipy)3]2+ is labile so that it dissociates and the tetrathioantimonate ion coordinates to Mn2+ cations within seconds. The robust Ni2+/Fe2+ complexes are stable in the presence of the Sb(III)S3 species generated in time which then condense around the complexes forming the [Sb6S10]2– networks. Even though the title compound immediately crystallized as a pure material when the two solutions were mixed, solvothermal conditions were required for the growth of crystals suitable for the structure analysis (Fig. 4). During the solvothermal reaction the title compound was only found as a by-product besides the polysulfide complex [Mn(bipy)2S6] [71] and an unknown compound (Fig. 5) containing Sb, S and Mn according to EDX analysis (Mn 17.9, Sb 22.9, S 59.2 at%). The appearance of the polysulfide anion and the sulfur rich unknown compound suggests that redox reactions take place during the synthesis at 140 °C and that the unknown compound might contain Sb(III).

Fig. 4: Experimental X-ray powder pattern of [Mn2(bipy)4SbS4](ClO4) obtained by room temperature synthesis, together with the simulated pattern.

Fig. 4:

Experimental X-ray powder pattern of [Mn2(bipy)4SbS4](ClO4) obtained by room temperature synthesis, together with the simulated pattern.

Fig. 5: Simulated X-ray powder patterns of [Mn2(bipy)4SbS4](ClO4) and [Mn(bipy)2S6] and experimental X-ray powder pattern of the product of the solvothermal synthesis.

Fig. 5:

Simulated X-ray powder patterns of [Mn2(bipy)4SbS4](ClO4) and [Mn(bipy)2S6] and experimental X-ray powder pattern of the product of the solvothermal synthesis.

2.1 UV/Vis spectroscopy

By applying the Kubelka–Munk method, the band gap was estimated to 2.4 eV. In the spectrum further maxima are observed at 4.9 and 4.2 eV, which are also observed for [Mn(bipy)3]2+ complexes and that can be assigned to charge-transfer transitions (Fig. 6) [72].

Fig. 6: UV/Vis diffuse reflectance spectrum of [Mn2(bipy)4SbS4](ClO4). The red line indicates the estimation of the band gap.

Fig. 6:

UV/Vis diffuse reflectance spectrum of [Mn2(bipy)4SbS4](ClO4). The red line indicates the estimation of the band gap.

2.2 Magnetic properties

The inverse magnetic susceptibility of the title compound is shown in Fig. 7. The evolution of χT with decreasing temperature indicates very weak ferromagnetic interactions and below 40 K the curve exhibits a pronounced drop. Evaluation of the data with the Curie–Weiss law yields an effective magnetic moment of 5.54 μB per Mn2+ ion which is lower than the spin only value of 5.92 μB. The Weiss constant of –2.3 K may indicate weak antiferromagnetic exchange interactions between the two Mn2+ centers mediated by the thioantimonate ion.

Fig. 7: Temperature dependence of the product χT of [Mn2(bipy)4SbS4](ClO4). The insert shows the inverse magnetic susceptibility.

Fig. 7:

Temperature dependence of the product χT of [Mn2(bipy)4SbS4](ClO4). The insert shows the inverse magnetic susceptibility.

3 Conclusion

A simple room temperature synthetic route afforded the new thioantimonate(V) compound [Mn2(bipy)4SbS4](ClO4) featuring the novel [Mn2(bipy)4SbS4]+ cation. The SbS43– anion acts as a tetradentate bridging ligand, a connection mode observed here for the first time. Under solvothermal conditions the compound is at least partially decomposed and [Mn(bipy)2S6] is formed. In further investigations the synthetic potential of the new room temperature approach for the generation of new thioantimonate compounds will be explored.

4 Experimental section

4.1 Synthesis

[Mn(bipy)3](ClO4)2 was synthesized according to the procedure reported for [Ni(bipy)3]Cl2 · 5.5H2O [73]. To a solution of 361.9 mg (1 mmol) Mn(ClO4)2 · 6H2O in ethanol a solution of 468.8 mg (3 mmol) bipy in ethanol was added under stirring. Polycrystalline samples were obtained at room temperature by mixing aqueous solutions of [Mn(bipy)3](ClO)4 and of Na3SbS4·9H2O in a 1:1 mmolar ratio. The compound was immediately formed with 50 % yield based on antimony. – Elemental analysis (%): calcd. C 44.32, H 2.98, N 10.34, S 11.83; found: C 43.53, H 2.99, N 9.97, S 10.70. EDX analysis proves the presence of Mn, Sb, S and Cl. – IR (ATR): νmax = 1591 (m), 1468 (w), 1437 (s), 1311 (w), 1088 (s), 1011 (s), 764 (s), 739 (m), 642 (w), 621 (s), 403 (s).

Single crystals of [Mn2(bipy)4SbS4](ClO4) were obtained by adding 2 mL H2O to a mixture of 180.6 mg (0.25 mmol) [Mn(bipy)3](ClO)4 and 120.3 mg (0.25 mmol) Na3SbS4·9H2O in a Duran glass tube. The mixture was heated to 140 °C for 8 d. Yellow block shaped crystals with a yield of only 7 % based on antimony could be obtained next to red crystals of the polysulfide [Mn(bipy)2S6] and a hitherto unknown by-product.

4.2 Structure refinement

A STOE Imaging Plate Diffraction System (IPDS 2) with MoKα radiation was used to collect the single crystal X-ray intensity data. The structure was solved with Direct Methods using Shelxs-97 [74, 75] and the structure refinement was performed against F2 with Shelxl-97 [76, 77]. All non-hydrogen atoms were refined anisotropically. The C–H H atoms were positioned with idealized geometry and refined isotropically with Uiso(H) = 1.2 × Ueq(C) using a rigid model. The asymmetric unit contains half a perchlorate anion which is disordered in two positions and additionally disordered around a 2-fold axis. This anion was refined using a split model and geometrical restraints in order that two nearly perfect tetrahedrally coordinated anions are obtained. It is noted that the structure was also refined in space group Cc, where the 2-fold axis is absent. In this case an identical disorder was observed and the absolute structure cannot be determined. From reciprocal space plots there are also no hints for super structure reflections. Table 3 contains the crystal data and other numbers pertinent to data collection and structure refinement.

Table 3

Selected crystallographic data of [Mn2(bipy)4SbS4](ClO4).

Empirical formula C40H32ClMn2N8O4S4Sb
Molecular mass 1084.06
Crystal system Monoclinic
Space group C2/c
a, Å 16.5298(6)
b, Å 19.0463(5)
c, Å 14.4126(5)
β, deg 102.315(3)
V, Å3 4433.1(3)
Z 4
Temperature, K 200
2θ range, deg 1.65–27.99
Index range hkl –21 ≤ h ≤ 21
–25 ≤ k ≤ 24
–18 ≤ l ≤ 17
Dcalcd., g cm–3 1.62
μ(MoKα), mm–1 1.5
Reflections collected 25468
Independent reflections 5307
Rint 0.0453
Reflections with I > 2 σ(I) 4789
Number of parameters 293
R1 (I > 2 σ(I) 0.0519
R1 (all data) 0.0593
wR2 (all data) 0.1296
GOF 1.175
Δρfin (max/min), e Å–3 1.71/–0.91

CCDC 1439774 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

4.3 X-ray powder diffractometry

A STOE Stadi-P powder diffractometer with CuKα1 radiation a Mythen detector and a Ge monochromator was used to measure the X-ray powder patterns.

4.4 Magnetic measurements

Magnetic susceptibility measurements were performed in a PPMS (Quantum Design) with a 1 T external field. The raw data were corrected for the core diamagnetism.

4.5 UV/Vis spectroscopy

Powdered samples were measured at room temperature with a UV/Vis-NIR two channel spectrometer Cary 5 from Varian Techtron Pty. BaSO4 was used as a reference. The Kubelka–Munk relation was applied to determine the band gap.

4.6 IR spectroscopy

An ATI Mattson Genesis spectrometer was used to record the MIR spectrum (450–3000 cm–1).

4.7 EDX analysis

Energy dispersive X-ray analyses (EDX) were carried out done with a Philips Environmental Scanning Electron Microscope ESEM XL30 with an EDAX detector.

Acknowledgments

Financial support by the State of Schleswig-Holstein is gratefully acknowledged.

References

[1] B. Seidlhofer, N. Pienack, W. Bensch, Z. Naturforsch.2010, 65b, 937. Search in Google Scholar

[2] S. Dehnen, M. Melullis, Coord. Chem. Rev.2007, 251, 1259. Search in Google Scholar

[3] W. S. Sheldrick, M. Wachhold, Angew. Chem. Int. Ed. Engl.1997, 36, 206. Search in Google Scholar

[4] W. S. Sheldrick, M. Wachhold, Coord. Chem. Rev.1988, 176, 211. Search in Google Scholar

[5] J. Zhou, J. Dai, G.-Q. Bian, C.-Y. Li, Coord. Chem. Rev.2009, 253, 1221. Search in Google Scholar

[6] R. Kiebach, F. Studt, C. Näther, W. Bensch, Eur. J. Inorg. Chem.2004, 2553. Search in Google Scholar

[7] W. Bensch, C. Näther, R. Stähler, Chem. Commun.2001, 477. Search in Google Scholar

[8] L. Engelke, W. Bensch, Acta Crystallogr.2003, E59, m378. Search in Google Scholar

[9] R. Stähler, C. Näther, W. Bensch, J. Solid State Chem.2003, 174, 264. Search in Google Scholar

[10] H. Lühmann, Z. Rejai, K. Möller, P. Leisner, M.-E. Ordolff, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2008, 634, 1687. Search in Google Scholar

[11] B. Seidlhofer, V. Spetzler, E. Quiroga-Gonzalez, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2011, 637, 1295. Search in Google Scholar

[12] V. Spetzler, C. Näther, W. Bensch, Z. Naturforsch.2006, 61b, 715. Search in Google Scholar

[13] W. Bensch, M. Schur, Eur. J. Solid State Inorg. Chem.1997, 34, 457. Search in Google Scholar

[14] R. Kiebach, A. Griebe, C. Näther, W. Bensch, Solid State Sci.2006, 8, 541. Search in Google Scholar

[15] A. Puls, M. Schaefer, C. Näther, W. Bensch, A. V. Powell, S. Boissière, A. M. Chippindale, J. Solid State Chem.2005, 178, 1171. Search in Google Scholar

[16] J. Zhou, G.-Q. Bian, Y. Zhang, J. Dai, N. Cheng, Z. Anorg. Allg. Chem.2007, 633, 2701. Search in Google Scholar

[17] M. Zhang, T. L. Sheng, X. H. Huang, R. B. Fu, X. Wang, S. M. Hu, S. C. Xiang, X. T. Wu, Eur. J. Inorg. Chem.2007, 1606. Search in Google Scholar

[18] L. Engelke, C. Näther, W. Bensch, Eur. J. Inorg. Chem.2002, 2936. Search in Google Scholar

[19] R. J. E. Lees, A. V. Powell, D. J. Watkin, A. M. Chippindale, Acta Crystallogr.2007, C63, m27. Search in Google Scholar

[20] R. J. E. Lees, A. V. Powell, A. M. Chippindale, J. Phys. Chem. Solids2007, 68, 1215. Search in Google Scholar

[21] R. Stähler, C. Näther, W. Bensch, Eur. J. Inorg. Chem.2001, 1835. Search in Google Scholar

[22] A. Puls, C. Näther, R. Kiebach, W. Bensch, Solid State Sci.2006, 8, 1085. Search in Google Scholar

[23] X. Wang, T.-L. Sheng, J.-S. Chen, S.-M. Hu, R.-B. Fu, X.-T. Wu, J. Mol. Struct.2009, 936, 142. Search in Google Scholar

[24] Y. Ko, K. Tan, J. B. Parise, A. Darovsky, Chem. Mater.1996, 8, 493. Search in Google Scholar

[25] A. V. Powell, R. J. E. Lees, A. M. Chippindale, Inorg. Chem.2006, 45, 4261. Search in Google Scholar

[26] P. Vaqueiro, A. M. Chippindale, A. V. Powell, Inorg. Chem.2004, 43, 7963. Search in Google Scholar

[27] K.-Z. Du, M.-L. Feng, L.-H. Li, B. Hu, Z.-J. Ma, P. Wang, J.-R. Li, Y.-L. Wang, G.-D. Zou, X.-Y. Huang, Inorg. Chem.2012, 51, 3926. Search in Google Scholar

[28] Y. Liu, J. Lu, F. Wang, Y. Shen, C. Tang, Y. Zhang, D. Jia, J. Coord. Chem.2015, 68, 2334. Search in Google Scholar

[29] D.-X. Jia, Y. Zhang, J. Dai, Q.-Y. Zhu, X.-M. Gu, J. Solid State Chem.2004, 177, 2477. Search in Google Scholar

[30] M. Schur, W. Bensch, Acta Crystallogr.2000, C56, 1107. Search in Google Scholar

[31] M. Schur, H. Rijnberk, C. Näther, W. Bensch, Polyhedron.1998, 18, 101. Search in Google Scholar

[32] R. Stähler, C. Näther, W. Bensch, Acta Crystallogr.2001, C57, 26. Search in Google Scholar

[33] M.-F. Wang, C.-Y. Yue, Z.-D. Yuan, X.-W. Lei, Acta Crystallogr.2013, C69, 855. Search in Google Scholar

[34] M. Poisot, C. Näther, W. Bensch, Acta Crystallogr.2007, E63, m1751. Search in Google Scholar

[35] C.-Y. Yue, X.-W. Lei, H.-P. Zang, X.-R. Zhai, L.-J. Feng, Z.-F. Zhao, J.-Q. Zhao, X.-Y. Liu, CrystEngComm.2014, 16, 3424. Search in Google Scholar

[36] L. Engelke, C. Näther, P. Leisner, W. Bensch, Z. Anorg. Allg. Chem.2008, 634, 2959. Search in Google Scholar

[37] D.-X. Jia, Q.-Y. Zhu, J. Dai, W. Lu, W.-J. Guo, Inorg. Chem.2005, 44, 819. Search in Google Scholar

[38] M. Schaefer, L. Engelke, W. Bensch, Z. Anorg. Allg. Chem.2003, 629, 1912. Search in Google Scholar

[39] J. Lichte, H. Lühmann, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2009, 635, 2021. Search in Google Scholar

[40] R. Stähler, W. Bensch, Acta Crystallogr.2002, C58, m537. Search in Google Scholar

[41] N. Herzberg, C. Näther, W. Bensch, Z. Naturforsch.2013, 68b, 605. Search in Google Scholar

[42] J. Lichte, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2010, 636, 108. Search in Google Scholar

[43] Y.-L. Pan, J.-F. Chen, J. Wang, Y. Zhang, D.-X. Jia, Inorg. Chem. Commun.2010, 13, 1569. Search in Google Scholar

[44] N. Herzberg, C. Näther, W. Bensch, Z. Kristallogr.2012, 227, 552. Search in Google Scholar

[45] R. Stähler, B.-D. Mosel, H. Eckert, W. Bensch, Angew. Chem. Int. Ed.2002, 41, 4487. Search in Google Scholar

[46] X. Liu, J. Zhou, Inorg. Chem. Commun.2011, 14, 1286. Search in Google Scholar

[47] R. Stähler, W. Bensch, Eur. J. Inorg. Chem.2001, 3073. Search in Google Scholar

[48] R. Stähler, W. Bensch, Dalton Trans.2001, 2518. Search in Google Scholar

[49] M. Schaefer, C. Näther, W. Bensch, Monatsh. Chem.2004, 135, 461. Search in Google Scholar

[50] M. Schaefer, R. Stähler, W.-R. Kiebach, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2004, 630, 1816. Search in Google Scholar

[51] W. Bensch, M. Schur, Eur. J. Solid State Inorg. Chem.1996, 33, 1149. Search in Google Scholar

[52] L. Engelke, R. Stähler, M. Schur, C. Näther, W. Bensch, R. Pöttgen, M. H. Möller, Z. Naturforsch.2004, 59b, 869. Search in Google Scholar

[53] M. Schur, C. Näther, W. Bensch, Z. Naturforsch.2001, 56b, 79. Search in Google Scholar

[54] M. Schur, W. Bensch, Z. Naturforsch.2002, 57b, 1. Search in Google Scholar

[55] M. Schaefer, C. Näther, N. Lehnert, W. Bensch, Inorg. Chem.2004, 43, 2914. Search in Google Scholar

[56] C. Anderer, C. Näther, W. Bensch, Inorg. Chem. Commun.2014, 46, 335. Search in Google Scholar

[57] X. Wang, T.-L. Sheng, S.-M. Hu, R.-B. Fu, X.-T. Wu, Inorg. Chem. Commun.2009, 12, 399. Search in Google Scholar

[58] C. Anderer, N. Delwa de Alarcón, C. Näther, W. Bensch, Chem. Eur. J.2014, 20, 16953. Search in Google Scholar

[59] M. Schaefer, C. Näther, W. Bensch, Solid State Sci.2003, 5, 1135. Search in Google Scholar

[60] M. Schaefer, D. Kurowski, A. Pfitzner, C. Näther, Z. Rejai, K. Möller, N. Ziegler, W. Bensch, Inorg. Chem.2006, 45, 3726. Search in Google Scholar

[61] A. Puls, C. Näther, W. Bensch, Z. Anorg. Allg. Chem.2006, 632, 1239. Search in Google Scholar

[62] Z. Rejai, H. Lühmann, C. Näther, R. K. Kremer, W. Bensch, Inorg. Chem.2010, 49, 1651. Search in Google Scholar

[63] B. Seidlhofer, V. Spetzler, C. Näther, W. Bensch, J. Solid State Chem.2012, 187, 269. Search in Google Scholar

[64] D. Jia, Q. Zhao, Y. Zhang, J. Dai, J. Zuo, Inorg. Chem.2005, 44, 8861. Search in Google Scholar

[65] S. Grimme, Angew. Chem. Int. Ed.2008, 47, 3430. Search in Google Scholar

[66] J. Hilbert, C. Näther, W. Bensch, Inorg. Chem.2014, 53, 5619. Search in Google Scholar

[67] J. Zhou, X.-H. Yin, F. Zhang, CrystEngComm.2011, 13, 4806. Search in Google Scholar

[68] D.-X. Jia, J. Deng, Q.-X. Zhao, Y. Zhang, J. Mol. Struct.2007, 833, 114. Search in Google Scholar

[69] W. Tang, R. Chen, J. Zhao, W. Jiang, Y. Zhang, D. Jia, CrystEngComm.2012, 14, 5021. Search in Google Scholar

[70] H. Irving, D. H. Mellor, J. Chem. Soc.1962, 5222. Search in Google Scholar

[71] Y. Li, Z.-X. Zhang, F.-Y. Fang, W.-D. Song, K.-C. Li, Y.-L. Miao, C.-S. Gu, L.-Y. Pan, J. Mol. Struct.2007, 837, 269. Search in Google Scholar

[72] C. Baffert, S. Dumas, J. Chauvin, J.-C. Leprêtre, M.-N. Collomb, A. Deronzier, Phys. Chem. Chem. Phys.2005, 7, 202. Search in Google Scholar

[73] C. Ruiz-Pérez, P. A. Lorenzo Luis, F. Lloret, M. Julve, Inorg. Chim. Acta2002, 336, 131. Search in Google Scholar

[74] G. M. Sheldrick, shelxs-97, Program for the Solution of Crystal Structures, University of Göttingen, Göttingen (Germany) 1997. Search in Google Scholar

[75] G. M. Sheldrick, Acta Crystallogr.1990, A46, 467. Search in Google Scholar

[76] G. M. Sheldrick, Shelxl-97, Program for the Refinement of Crystal Structures, University of Göttingen, Göttingen (Germany) 1997. Search in Google Scholar

[77] G. M. Sheldrick, Acta Crystallogr.2008, A64, 112. Search in Google Scholar

Received: 2015-12-7
Accepted: 2015-12-19
Published Online: 2016-3-8
Published in Print: 2016-5-1

©2016 by De Gruyter