Introducing Stereochemically Active Lone-Pairs into Transition Metal

Article pubs.acs.org/crystal

A Synthetic Route toward Layered Materials: Introducing Stereochemically Active Lone-Pairs into Transition Metal Oxohalides Iwan Zimmermann and Mats Johnsson* Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden S Supporting Information *

ABSTRACT: The synthesis and crystal structure of eight new layered compounds in the (Mn2+, Fe2+)-(Sb3+, Te4+)-O-(Cl, Br) system are presented. Mn5Te4O12Cl2 (1), MnSb4O6Cl2 (2), Mn2Sb3O6Cl (3), Mn9Sb8O16Cl10 (4), Fe3Sb2O4Br4 (5), Fe7Sb10O18X8 [X = Cl (6), Br (7)], and Mn7Sb10O18Br8 (8). All of the compounds are made up of charge neutral layers held together through van der Waals interactions, except for compound 2, which has positively charged layers with halide ions between them that act as counterions. The transition metal atoms are confined in sheets within the layers and are thus well separated from each other along the stacking direction. The synthesis concept is based on utilizing both halide ions and p-elements having a stereochemically active lone pair that both act to open up crystal structures. This combination has proven to be a successful synthetic approach for finding new layered inorganic materials containing transition metals.

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form, for example, Fe6Ca2(SeO3)9Cl47 and [Te32Ni30X3O90]5+[Ni4X13]5−,8 or compounds with cluster entities as in Cu20Sb35O44Cl37.9 To search for oxohalides and oxides comprising a p-block element having a stereochemically active lone pair has shown to be successful also for finding new materials with interesting physical properties, such as ferroelectric materials like (NH4)2Te2WO810 or magnetically frustrated compounds like Cu2Te2O5X2,11 FeTe2O5X (X = Cl, Br),12 or Ba2Sn2ZnGa3Cr7O22,13 of which FeTe2O5X has shown also to be intrinsically multiferroic.14 There are also improved chances for finding noncentrosymmetric crystal structures, which may exhibit a large second harmonic generation (SHG) effect, such as Au2(SeO3)2(SeO4),15 Hg2BrI3,16 K(VO)2O2(IO3)3,17 or Na2TeW2O9.18,19 In this work, we present eight new oxohalide compounds having six different crystal structures in the (Mn2+, Fe2+)-(Sb3+, Te4+)-O-(Cl, Br) system. All the compounds except for one are made up of charge neutral layers held together by weak van der Waals interactions, and the remaining one has positively charged layers with halide ions between them.

INTRODUCTION There is no synthesis strategy that always gives layered compounds containing transition metals when searching for new compounds. However, the concept presented in this article where the one sided coordination of p-element lone pair cations is utilized in combination with simple chemical rules such as Lewis acidity and the hard−soft/acid−base (HSAB) concept to choose between coordination to oxygen or Cl/Br has proven to very often result in layered compounds with charge neutral layers that are connected with only weak van der Waals interactions. Halide ions can act as terminating species like the lone-pairs in the M-L-O-X system (L = lone pair pelement, M = late transition metal, X = Cl, Br). While the hard lone pair cations are almost exclusively coordinated by oxygen, the transition metal ions coordinate to both oxygen and Cl−/ Br− that divide up the crystal structures into an oxide part and a halide part so that both the lone pairs and the halide ions act as terminating species in the crystal structures, which is the reason for forming layers, for example. The transition metal ions embedded within the layers thus arrange in two-dimensional nets well separated from each other along the direction that the layers are stacked. Examples of p-block elements with ns2np0 electronic configuration are Se4+, Te4+, and Sb3+. Those ions have stereochemically active lone-pairs that cause the one-sided coordination1,2 and act as a terminal ligand that opens up the crystal structure by introducing nonbonding volumes. Some examples of layered oxide and oxohalide compounds where the lone pairs protrude from the layers are FeSb 2 O 4 , 3 Cd6V2Se5O21,4 Bi3Te4O10Cl5,5 and Cr3Te5O13Cl3.6 Instead of layered compounds, crystal structures with pore volumes may © XXXX American Chemical Society

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EXPERIMENTAL SECTION

All chemicals used for the synthesis were purchased from commercial suppliers and used without further purification. Compounds 1−8 were synthesized by chemical reactions of powder mixtures in sealed and evacuated silica tubes yielding plate like single crystals of the compounds mixed with unreacted starting materials and unidentified powders. The Fe-containing compounds were orange, and the MnReceived: July 10, 2014 Revised: August 26, 2014

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dx.doi.org/10.1021/cg5010374 | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Table 1. Crystallographic information for Compounds 1−8 compound empirical formula formula wt (g/mol) temp (K) wavelength (Å) space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) vol (Å3) Z color density (calcd) (g cm−3) absorp coeff (mm−1) F(000) θ range for data collection (deg) GOF on F Flack parameter final R indices [I > 2σ(I)] R indices (all data) compound empirical formula formula wt (g/mol) temp (K) wavelength (Å) space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) vol (Å3) Z color density (calcd) (g cm−3) absorp coeff (mm−1) F(000) θ range for data collection (deg) GOF on F Flack parameter final R indices [I > 2σ(I)] R indices (all data)

1 Mn5Te4O12Cl2 1048.00 293 0.71073 P21/c (No. 14) 8.6904(2) 5.48080(13) 16.144(5) 90 107.570(3) 90 733.1(2) 2 colorless 4.748 12.409 926 4.12−32.14 0.909 R1 = 0.0334 wR2 = 0.0588 R1 = 0.0534 wR2 = 0.0625 5 Fe3Sb2O4Br2 794.69 293 0.71073 Cmca (No. 64) 6.30990(10) 12.3959(3) 14.5287(3) 90 90 90 1136.39(4) 4 orange 4.645 22.471 1408 3.29−32.05 0.865

2 MnSb4O6Cl2 708.84 293 0.71073 P212121 (No. 19) 5.4698(2) 5.5479(2) 31.0882(9) 90 90 90 943.40(6) 4 colorless 4.991 13.166 1244 3.73−33.75 0.872 0.00(4) R1 = 0.0306 wR2 = 0.0429 R1 = 0.0413 wR2 = 0.0443 6 Fe7Sb10O18Cl8 2180.05 293 0.71073 P1̅ (No. 2) 9.6600(4) 9.9264(3) 9.8549(3) 72.656(2) 65.874(3) 63.865(3) 766.18(5) 1 orange 4.725 12.613 972 4.21−33.63 1.010

3 Mn2Sb3O6Cl 1213.16 293 0.71073 P2/c (No.13) 7.2406(6) 9.8413(7) 11.7694(10) 90 104.596(9) 90 811.59(12) 2 colorless 4.964 13.196 1072 3.57−32.27 0.666 R1 = 0.0521 wR2 = 0.0601 R1 = 0.1447 wR2 = 0.0738 7 Fe7Sb10O18Br8 2535.73 293 0.71073 P1̅ (No. 2) 9.9229(3) 10.0059(3) 10.1097(3) 72.723(2) 64.669(3) 64.836(3) 813.00(4) 1 orange 5.179 21.060 1116 3.42−32.26 0.899

4 Mn9Sb8O16Cl10 2078.96 293 0.71073 P21 (No. 4) 8.2744(9) 17.2532(12) 11.0608(10) 90 102.849(10) 90 1539.5(2) 2 colorless 4.485 11.360 1862 3.46−29.43 0.897 0.49(7) R1 = 0.0631 wR2 = 0.0925 R1 = 0.1229 wR2 = 0.1039 8 Mn7Sb10O18Br8 2529.36 293 0.71073 P1̅ (No. 2) 9.9492(3) 10.1015(3) 10.1338(4) 74.149(3) 66.166(4) 65.097(3) 838.46(5) 1 colorless 5.009 20.028 1109 3.34−29.07 1.102

R1 = 0.0237 wR2 = 0.0480 R1 = 0.0337 wR2 = 0.0494

R1 = 0.0340 wR2 = 0.0808 R1 = 0.0399 wR2 = 0.0833

R1 = 0.0239 wR2 = 0.0511 R1 = 0.0307 wR2 = 0.0545

R1 = 0.0349 wR2 = 0.0703 R1 = 0.0455 wR2 = 0.0751

for 70 h. Attempts were also made to synthesize phase pure material of compounds 1−6 using stoichiometric molar ratios of the starting materials. The following molar ratios were used: Mn5Te4O12Cl2 (1), MnCl2/MnO/TeO2 = 1:4:4; MnSb4O6Cl2 (2), MnCl2/Sb2O3 = 1:2; Mn2Sb3O6Cl (3), MnCl2/MnO/Sb2O3 = 1:3:3; Mn9Sb8O16Cl10 (4), MnCl2/MnO/Sb2O3 =5:4:4; Fe3Sb2O4Br4 (5), FeBr2/FeO/Sb2O3 = 2:1:1; Fe7Sb10O18Cl8 (6), FeCl2/FeO/Sb2O3 = 4:3:5. Single crystal X-ray diffraction experiments were carried out on an Oxford Diffraction Xcalibur3 diffractometer equipped with a graphite monochromator. The data collection was carried out at 293 K using Mo Kα radiation, λ = 0.71073 Å. Data reduction was done with the software CrysAlis RED, which was also employed for the analytical

containing compounds were transparent. The single crystals used for crystal structure determination were prepared from the following nonstoichiometric mixtures of starting materials: Mn5Te4O12Cl2 (1), a 1:1:1 mixture of MnCl2/MnO/TeO2 was heated to 550 °C for 70 h; MnSb4O6Cl2 (2), a 1:1:4 mixture of MnCl2/MnO/Sb2O3 was heated to 650 °C for 70 h; Mn2Sb3O6Cl (3), a 1:1:2 mixture of MnCl2/MnO/ Sb2O3 was heated to 600 °C for 95 h; Mn9Sb8O16Cl10 (4), a 1:1:1 mixture of MnCl2/MnO/Sb2O3 was heated to 650 °C for 70 h; Fe3Sb2O4Br4 (5), a 4:1:2 mixture of FeBr2/FeO/Sb2O3 was heated to 650 °C for 70 h; Fe7Sb10O18X8, X = Cl (6), Br (7), an 8:6:10 mixture of FeX2/FeO/Sb2O3 was heated to 600 °C for 70 h; Mn7Sb10O18Br8 (8), an 8:6:10 mixture of MnBr2/MnO/Sb2O3 was heated to 600 °C B



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Figure 1. Overview of the crystal structures 1−6 showing that all compounds are layered. All compounds except for 2 have no net charge and are held together by weak van der Waals interactions. Compound 2 has positively charged layers with Cl-ions between them. absorption correction.20 The structure solution was carried out with SHELXS and the refinement with SHELXL21 in the WINGX22 environment. All atoms were refined anisotropically, except for compounds 3 and 4 where the oxygen atoms were refined isotropically. The crystals of 4 turned out to be twinned by reticular merohedry with the twin law being a −2 rotoinversion around the [001] axis. The twinning is the origin of the Flack parameter, which is close to 0.5 as both twin fractions, and therefore both enantiomers are equally present; hklf5 refinement in SHELXL has been performed to resolve the twinning. The unit cell of compound 6 has been transformed to the same cell setting as for 7 and 8 to facilitate comparison of the three isostructural compounds. Atomic coordinates and isotropic temperature parameters for all atoms as well as tables

with selected bond distances are given in the Supporting Information. Structure data are reported in Table 1. Structure drawings are made with the program DIAMOND.23 Powder X-ray data were collected on a Panalytical X’Pert PRO powder X-ray diffractometer in Bragg−Brentano geometry with Cu Kα radiation.

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RESULTS AND DISCUSSION The crystal structures for the new compounds are first described below, followed by a discussion on their common features. Mn5Te4O12Cl2 (1). Compound 1 crystallizes in the monoclinic space group P21/c. The crystal structure is made C



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Figure 2. Asymmetric units and selected symmetry equivalents for compounds 1−6.

an asymmetrical one-sided coordination due to the stereochemically active lone pair. Te1 and Te2 both have a trigonal pyramidal [TeO3] coordination with Te−O bond lengths between 1.845(4) and 1.900(4) Å. Te1 has a fourth oxygen ligand at ca. 2.54 Å outside the primary bonding sphere, which is very common for Te4+.24 The tellurium oxide building blocks do not polymerize as commonly observed among other tellurites.25 The manganese oxide octahedra build [Mn3O14] entities through edge sharing, which are further connected by corner sharing to build manganese oxide sheets in the (011) plane. The [MnO4Cl] and [TeO3] polyhedra are connected to those sheets so the halide ions and the tellurium lone pairs are pointing out from the layers, see Figure 1 and 3. The shortest Te···Cl interaction between two layers is ∼3.2 Å, and the shortest Cl··Cl interaction is ∼3.6 Å. MnSb4O6Cl2 (2). Compound 2 crystallizes in the noncentrosymmetric orthorhombic space group P212121. The crystal structure is built from two identical layers differently oriented stacked along [001]. The layers are built from polymerizing antimony oxide building blocks in which the

up of layers having no net charge stacking along [100]. The layers consist of interconnected manganese oxide and manganese oxochloride polyhedra to which the tellurium oxide building blocks are attached. The halide ions as well as the tellurium lone pairs protrude from the layers allowing weak van der Waals interactions to occur between the layers, see Figure 1. The coordination around the cations is shown in Figure 2. Mn1 is five coordinated and forms a distorted [MnO4Cl] tetragonal pyramid with Mn−O bond distances between 2.072(4) and 2.216(4) Å and a Mn−Cl bond distance of 2.459(2) Å. An octahedron would be completed if O3 was also included, but at just over 2.7 Å, this Mn−O distance is too long to be considered as bonded. Mn2 can be regarded as an extremely distorted [MnO6] octahedron with a wide range in Mn−O bond distances (2.176(4)−2.414(4) Å). The distortion is mainly caused by O5, which at 2.69 Å is just outside the primary bonding sphere of Mn2. Mn3 adopts a more regular [MnO6] octahedral coordination with Mn−O bond distances in the range of 2.156(4)−2.220(4) Å. The tellurium atoms have D



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Figure 3. Overview of individual layers in the different compounds 1−6 and the arrangement of Fe and Mn atoms, respectively.

range from 2.693(3) to 2.903(7) Å. There are three different antimony atoms in the asymmetric cell, which are all one sided coordinated due to the stereochemically active lone pair. Sb1 and Sb2 have a distorted seesaw coordination with three short (1.939(8)−2.053(8) Å) and one long (2.393(8) Å) Sb−O bonds for Sb1 and two short (1.911(7), 2.031(8) Å) and two long (2.170(8), 2.231(8) Å) Sb−O bonds for Sb2. Sb3 adopts a more regular [SbO3] trigonal pyramid with Sb−O bond distances between 1.940(8) and 1.967(8) Å. The asymmetric unit is shown in Figure 2. The [MnO4Cl2] and [MnO5Cl] polyhedra are mainly connected by edge sharing to form manganese oxochloride sheets. The antimony oxide building blocks are attached to these sheets by edge and corner sharing and form ladders along [100]. The ladders are built from repeating [Sb6O12]−6 units. The lone pairs of the antimony atoms are protruding from the layers and interact with neighboring layers through weak van der Waals interactions, see Figures 1 and 3. The shortest Sb···O and Sb···Sb interactions between layers are ∼3.3 and ∼4.1 Å respectively. Mn9Sb8O16Cl10 (4). Compound 4 crystallizes in the noncentrosymmetric monoclinic space group P21. The crystal structure is built from layers connected by weak van der Waals interactions with [100] being the stacking direction. The manganese atoms bind to oxygen and chlorine and arrange in extended 2D nets within the (011) plane to which the antimony oxide building blocks are connected, see Figure 1. Antimony adopts an asymmetric one sided coordination due to the stereochemically active lone pair. Among the eight crystallographically unique Sb atoms Sb4, Sb7, and Sb8 have a trigonal pyramidal coordination with Sb−O bond lengths

manganese oxochloride octahedra are embedded. The positively charged MnSb4O6Cl+ layers are separated by chlorine ions, which are only weakly bond to the antimony atoms, see Figure 1. The manganese atoms form distorted [MnO5Cl] octahedra with Mn−O distances between 2.108(4) and 2.316(4) Å and a Mn−Cl distance of 2.491(2) Å. There are four unique antimony atoms in the asymmetric unit, which all adopt a trigonal pyramidal [SbO3] coordination with Sb−O bond distances in the narrow range of 1.965(4)−2.038(4) Å. An overview of the different coordination polyhedra is shown in Figure 2. The antimony oxide building blocks polymerize to build layers parallel to the (110) plane, see Figure 3. Along [100] small tubular cavities are formed by the antimony oxide net in which the [MnO5Cl] octahedra are located. Each cavity can be seen as a tube built from Sb12 rings. Similar tubular arrangements are described, for example, in the mineral onoratoite where the tubes are built from Sb8 rings,26 or in Sb3O4Cl where oxide rings involving six Sb atoms are found.27 The [SbO4] ladder arrangement commonly observed in antimony oxide compounds is not present due to the [SbO3] coordination. The individual layers are separated through chlorine atoms, which act as counterions, and the shortest Sb··· Cl distance is ∼3.1 Å. Mn2Sb3O6Cl (3). Compound 3 crystallizes in the monoclinic space group P2/c. The crystal structure is built from layers stacking along [010], see Figure 1. Mn1 has a distorted octahedral [MnO4Cl2] coordination, and Mn2 adopts a distorted [MnO5Cl] trigonal prism. Mn−O bond lengths are between 2.042(8) and 2.372(8) Å, and Mn−Cl bond lengths E



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1.896(3) to 2.206(3) Å and from 2.4748(14) to 2.801(3) Å, respectively. The iron oxochloride building blocks are mainly connected through edge sharing and build the iron oxochloride net in which pores the antimony oxide are located, see Figure 3. The antimony oxide entities form linear arrangements of Sb10O18 units, which consist of Sb6O12 rings linked by Sb4O6 chains of polymerizing antimony oxide building blocks. The shortest Sb···Cl interaction is ∼3.6 Å between two layers. Attempts To Synthesize Phase Pure Powder. Attempts were made to synthesize phase pure powder of compounds (1− 6). The result of those experiments obtained at different synthesis temperatures in the range 500−650 °C for 90 h are summarized in Table 2. The optimum synthesis temperature for most of the compounds is close to 550 °C and for two of the compounds, 3 and 4, it was possible to get phase pure powder according to the results from powder X-ray diffraction experiments. For the other compounds, the powder was almost pure but contained most often some unidentified diffraction peaks from an impurity phase. Common Features among the Crystal Structures. Despite the fact that there is a large variation among the crystal structures, there are also many similarities. Sb3+ and Te4+ always coordinate to only oxygen, while Mn2+ and Fe2+ bond to either only O2− or both O2− and Cl−/Br− ions. The halide ions most often form only one or two bonds, and due to the low coordination number, they often protrude from the layers together with the stereochemically active lone pairs.

ranging from 1.945(11) to 2.005(9) Å, while Sb1, Sb2, Sb3, Sb5, and Sb6 adopt a distorted seesaw coordination with two short (1.943(9)−2.093(10) Å) and two long (2.105(10)− 2.268(10) Å) Sb−O bonds. There are nine unique Mn atoms in the asymmetric unit, which build different rather distorted polyhedra. A wide range of Mn−O and Mn−Cl bond lengths is observed, and bond lengths shorter than 2.6 and 3.0 Å for Mn− O and Mn−Cl, respectively, were regarded as bonded. This arbitrary limit is in agreement with the practical rule by Brown28 that each bond should contribute at least 4% to the total bond valence of the cation to be considered as bonded. The different coordination polyhedra for Mn2+ are (i) very distorted capped trigonal prisms [MnO5Cl2] for Mn1 and Mn2, (ii) [MnO3Cl2] tetragonal pyramids for Mn3, (iii) [MnO3Cl3] octahedra for Mn4 and Mn8, (iv) [MnO2Cl4] octahedra for Mn5 and Mn7, (v) [MnO2Cl3] tetragonal pyramids for Mn6, and (vi) capped trigonal prisms [MnO4Cl3] for Mn9. The Mn− O bond lengths vary from 2.060(10) to 2.556(11) Å, and Mn− Cl are in the range 2.478(7)−2.931(19) Å. Coordination behavior of the different metal cations can be seen in Figure 2. The antimony oxide building blocks polymerize into chains of repeating [Sb8O16]−8 units. The manganese oxohalide polyhedra arrange in a complex 2D net within the (011) plane by edge and corner sharing. Considering the arrangement of manganese atoms only, one can observe a distorted triangular lattice, see Figure 3. The antimony oxide chains are connected to the manganese oxochloride sheets so that the lone pairs protrude from the layers and only weakly interact by van der Waals forces with chlorine atoms from the next layer. The shortest Sb−Cl interactions between the layers are ∼3.4 Å. Fe 3 Sb 2 O 4 Br 4 (5). Compound 5 crystallizes in the orthorhombic space group Cmca. The crystal structure is built from layers stacking along [010]. The layers consist of iron oxo bromide sheets to which the antimony oxide building blocks are connected. The layers are charge neutral and connected by weak van der Waals interactions, see Figure 1. There are two crystallographically unique iron atoms in the asymmetric unit. Fe1 adopts distorted [FeO2Cl4] octahedra, and Fe2 forms very distorted [FeO2Cl2] tetrahedra. At ∼3.1 Å, the two Fe2−Br3 bonds that would complete the octahedera for Fe2 lie just outside the primary bonding sphere. Fe−O and Fe−Cl bond distances are in the range of 1.929(3)−1.9601(19) Å and 2.6504(7)−2.8060(5) Å, respectively. The antimony atoms adopt a typical one-sided trigonal pyramidal [SbO3] coordination with Sb−O bond lengths of 1.942(3) and 2.0169(18) Å, see Figure 2. The [FeO2Cl2] tetrahedra are connected to each other via edge sharing to form chains along [100]. The chains are linked through corner sharing [FeO2Cl4] octahedra to build sheets in the (101) plane. The [SbO3] polyhedra are connected via corner sharing to the iron oxobromide net, see Figures 1 and 3. Shortest Sb···Br interactions between the layers are ∼3.4 Å. Fe7Sb10O18Cl8 (6), Fe7Sb10O18Br8 (7), and Mn7Sb10O18Br8 (8). The compounds 6−8 are isostructural, and the structure description here is based on 6. The crystal structure is built up from charge neutral layers stacking along [110]. Antimony lone pairs and halide ions protrude from the layers allowing only weak van der Waals interactions between the layers, as shown in Figure 1. There are four different iron atoms in the asymmetric unit, see Figure 2, all having distorted octahedral coordination. The different coordination polyhedra are [FeO4Cl2] for Fe2 and Fe3, [FeO3Cl3] for Fe1, and [FeO2Cl4] for Fe4. The Fe−O and Fe−Cl distances range from

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CONCLUSION To include halide ions and p-element cations with a stereochemically active lone pair into late transition metal oxohalides has proven to be a powerful synthetic approach for finding new compounds having layered crystal structures where the transition metal coordination polyhedra then form 2D nets that are well separated from each other. All the eight compounds presented were synthesized in sealed evacuated silica tubes at temperatures between 500 and 650 °C by solid reactions starting with MO, MX2, and LxOy (M = Fe2+ or Mn2+; L = Te4+ or Sb3+; X = Cl or Br). The layer coherence results in single crystals having thin plate like morphology in the macroscopic scale, due to slow crystal growth along the stacking direction. Eight layered compounds in the oxohalide system M-L-O-X have been synthesized. The p-element cations Te4+ and Sb3+ both have a stereochemically active lone pair due to the ns2np0 electronic configuration and show one-sided asymmetric coordination. Bonding in this kind of oxohalides is dictated by simple chemical rules such as Lewis acidity and hardness− softness properties of the ingoing ions. Both manganese and iron coordinate to both oxygen and halide atoms, while the more chemically hard lone-pair elements only bond to oxygen; this divides the crystal structures into an oxide part and a halide part so that both the lone pairs and the halide ions act as terminating species in the crystal structures, and this is the course for forming the layered crystal structures. The layers can be considered as molecular entities that either (i) they have a zero charge like in the compounds 1 and 3−8 where the lonepairs and the halide ions protrude from the layers and the crystal structure is held together by only weak van der Waals interactions or (ii) they consist of layers from which the lonepairs protrude and which have a positive net charge and the halide ions more act as counterions and are found between the oxide layers like in compound 2. The transition metals Fe2+ and F


target phase + unidentified peaks target phase + few very weak unidentified impurity peaks

Mn2+ arrange in different ways within the sheets, and due to the absence of ligand field stabilization energy for Mn2+ d5 ions, distorted coordination polyhedra with variable bond lengths can be observed.

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Atomic coordinates and bond lengths (Å), powder diffraction patterns, and crystallographic information in cif format. This material is available free of charge via the Internet at http:// pubs.acs.org. Further details on the crystal structure investigation of 1−8 can be obtained from the Fachinformationszentrum Karlsruhe, Abt. PROKA, 76344 Eggenstein-Leopoldshafen, Germany (fax +49−7247−808−666; E-mail: crysdata@fizkarlsruhe.de) on quoting the depository numbers CSD-427876 for 1, CSD-427879 for 2, CSD-427875 for 3, CSD-427878 for 4, CSD-427872 for 5, CSD-427874 for 6, CSD-427873 for 7. and CSD-427877 for 8.

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AUTHOR INFORMATION

Corresponding Author

target phase + large amounts of Sb2O3 target phase + Sb2O3

*E-mail: [email protected]. Tel: +46-8-162169. Fax: +46-8-152187. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The Swedish research council is acknowledged for financial support.

mixture melted or reacted with the silica tube; phase may be present in minor amounts crystallizing on top of the melt

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REFERENCES

(1) Pearson, R. G. J. Am. Chem. Soc. 1969, 91, 4947−4955. (2) Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C.; Seshadri, R. Phys. Rev. B 2003, 67, No. 125111. (3) Chater, R.; Gavarri, J. R.; Hewat, A. J. Solid State Chem. 1985, 60, 78−86. (4) Jiang, H.-L.; Kong, F.; Fan, Y.; Mao, J.-G. Inorg. Chem. 2008, 47, 7430−7437. (5) Kim, M. K.; Jo, V.; Lee, D. W.; Ok, K. M. Dalton Trans. 2010, 39, 6037−6042. (6) Zimmermann, I.; Kremer, R. K.; Reuvekamp, P.; Johnsson, M. Dalton Trans. 2013, 42, 8815−8819. (7) Hu, S.; Johnsson, M. Dalton Trans. 2013, 42, 7859−7862. (8) Johnsson, M.; Lidin, S.; Törnroos, K. W.; Bürgi, H.-B.; Millet, P. Angew. Chem., Int. Ed. 2004, 43, 4292−4295. (9) Mayerová, Z.; Johnsson, M.; Lidin, S. Angew. Chem., Int. Ed. 2006, 45, 5602−5606. (10) Kim, J.-H.; Baek, J.; Halasyamani, P. S. Chem. Mater. 2007, 19, 5637−5641. (11) Johnsson, M.; Törnroos, K. W.; Mila; Millet, P. Chem. Mater. 2000, 12, 2853−2857. (12) Becker, R.; Johnsson, M.; Kremer, R. K.; Klauss, H.-H.; Lemmens, P. J. Am. Chem. Soc. 2006, 128, 15469−15475. (13) Hagemann, I. S.; Huang, Q.; Gao, X. P. A.; Ramirez, A. P.; Cava, R. J. Phys. Rev. Lett. 2001, 86, 894−897. (14) Pregelj, M.; Zorko, A.; Zaharko, O.; Jeglič, P.; Kutnjak, Z.; Jagličić, Z.; Jazbec, S.; Luetkens, H.; Hillier, A. D.; Berger, H.; Arčon, D. Phys. Rev. B 2013, 88, No. 224421. (15) Wickleder, M. S.; Buchner, O.; Wickleder, C.; el Sheik, S.; Brunklaus, G.; Eckert, H. Inorg. Chem. 2004, 43, 5860−5864. (16) Zhang, G.; Qin, J.; Liu, T.; Li, Y.; Wu, Y.; Chen, C. Appl. Phys. Lett. 2009, 95, No. 261104. (17) Sun, C.-F.; Hu, C.-L.; Xu, X.; Yang, B.-P.; Mao, J.-G. J. Am. Chem. Soc. 2011, 133, 5561−5572.

650

peaks at higher angles do not match the target phase indicating a structural change; Mn2Te3O8 + other unidentified impurities present. 600

ASSOCIATED CONTENT

S Supporting Information *

minor amount of target phase + unidentified phase partially melted; not enough material for PXD

target phase + weak unidentified impurity peaks target phase + FeCl2 and Sb2O3 + unidentified peaks no impurity peaks observed target phase + Sb2O3 target phase + Mn2Te3O8 550

Mn2Sb3O6Cl (3) MnSb4O6Cl2 (2)

target phase + Sb2O3 target phase + few very weak unidentified impurity peaks

Mn5Te4O12Cl2 (1)

target phase + small amounts of Sb2O3 no impurity peaks observed

Fe7Sb10O18Cl8 (6) Fe3Sb2O4Br4 (5) Mn9Sb8O16Cl10 (4)

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500

temp (°C)

Table 2. Experiments Carried out at Different Reaction Temperatures Starting with Stoichiometric Molar Ratios of the Starting Materials Attempting To Synthesize Phase Pure Powder for Some of the Compounds


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Article

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