Hydrothermal Synthesis of the Oxofluoride FeSbO2F2—An Anti

Article pubs.acs.org/IC

Hydrothermal Synthesis of the Oxofluoride FeSbO2F2An Antiferromagnetic Spin S = 5/2 Compound Sk Imran Ali,*,† Reinhard K. Kremer,‡ and Mats Johnsson*,† †

Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden Max Planck Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart D-70568, Germany

‡

S Supporting Information *

ABSTRACT: The new oxofluoride compound FeSbO2F2 was synthesized by hydrothermal techniques at 230 °C. Its crystal structure was determined from single-crystal Xray diffraction data. The compound crystallizes in the monoclinic space group C2/c with one crystallographic site for Fe3+ and Sb3+, respectively. The crystal structure is made of [FeO2F4] octahedra and seesaw [SbO4] building blocks. These are connected to form [FeO2F2]n layers and [SbO2]n chains that bond together via the oxygen atoms to form the three-dimensional framework structure. Magnetic susceptibility and heat capacity measurements indicate long-range anti-ferromagnetic ordering below a Néel temperature of ∼175 K. Two-dimensional anti-ferromagnetic short-range order in the square planar net of the Fe3+ cations extends to temperatures far above the Néel temperature.

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INTRODUCTION Transition-metal oxides and oxohalides containing p-block elements with a stereochemically active lone pair (such as Se4+, Te4+, Sb3+, etc.) are of particular interest, since they crystallize with unusual structures. Both streochemically active lone pairs and halide ions act to increase the possibility to form noncentrosymmetric crystals with nonlinear optical properties as, for example, second harmonic generation. Further it is common in such systems that the transition-metal ions are grouped in anisotropic arrangements allowing to study magnetic unusual ground states in low-dimensional or frustrated systems.1−9 Most oxohalide compounds containing such p-block elements synthesized until now are oxochlorides or oxobromides. Only relatively few oxofluorides are described in the ML-O-X family (M = transition metal, L = p-element lone-pair cation, X = halide ion). Examples are (Co1−xNix)3Sb4O6F6 (0 ≤ x ≤ 1), FeSeO3F, V2Te2O7F2, In3TeO3F7, YSeO3F, FePbO2F, Co2SeO3F2, Co2TeO3F2, and Bi4Fe5O13F.4,10−16 Difficulties with container corrosion in high-temperature solid-state synthesis is one possible reason why there are relatively few oxofluorides described in literature, so far. In oxochlorides and oxobromides the halide ions and the electronic lone-pairs create nonbonding regions either in form of channels or voids in the crystal structure or by forming layered structures, where lone-pairs and halide ions protrude from the layers so that they connect by weak van der Waals interactions.17−20 Comparing crystal structures of oxochlorides and oxofluorides reflects the differences in electronegativity in between Cl and F. In oxochlorides generally the oxygen atoms connect the different building blocks, and chlorine is very often a terminating ion bonded only to the transition metal.21,22 In oxofluorides both oxygen and fluorine act as bridging ions.23 Therefore, it is more common that oxofluorides are present as © 2017 American Chemical Society

three-dimensional (3D) framework structures and that oxochlorides more often form layered structures with weak van der Waals interactions between the layers. Previously only some few compounds have been described in the Fe 3+−L−O−F system e.g. FeSeO3 F,10 FeTeO3 F,11 FePbO2F,14 Fe5Bi4O13F.16 However, to the best of our knowledge there is no Fe−Sb−O−F phase reported until now. In the present study we utilize a low-temperature hydrothermal synthesis technique to grow single crystals of the new compound FeSbO2F2 that is the first stoichiometric oxofluoride containing both Fe 3+ and Sb 3+ . Magnetic susceptibility and heat capacity measurements are also presented.

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EXPERIMENTAL SECTION

A mixture of FeF2/Sb2O3 = 2:1 (based on 0.094g FeF2) in 1 mL of deionized water plus one droplet of HF (0.125 mL) was filled into an 18 mL Teflon-lined steel autoclave. The mixture was stirred for half an hour using a magnetic stirrer. The autoclave was heated to 230 °C at a rate of 0.8 °C/min. The plateau temperature was maintained for 4 d, and thereafter the temperature was lowered to 30 °C at a rate of 0.6 °C/min. Similar experiments were also performed without the presence of HF, but they did not yield phase-pure material. The following chemicals were used as starting materials: Sb2O3 (99.97%, Sigma-Aldrich), FeF2 (99.8%, Sigma-Aldrich), and HF (48%, SigmaAldrich). The synthesis product consisted of brick red single crystals and powder of FeSbO2F2 (∼80% by weight) that were washed several times using water and ethanol followed by drying at room temperature. Single-crystal X-ray data were collected using a Bruker D8 Venture diffractometer equipped with a PHOTON 100 detector. Data integration, including the application of a correction for oblique Received: February 3, 2017 Published: March 24, 2017 4662

DOI: 10.1021/acs.inorgchem.7b00301 Inorg. Chem. 2017, 56, 4662−4667

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Inorganic Chemistry incidence, was performed with the software package SAINT.24 Absorption correction was applied by the computer program SADABS.25 The crystal structure was solved using the program Superflip26 and refined utilizing the program JANA2006.27 All atoms are refined with anisotropic thermal displacement parameters. The crystallographic data are summarized in Table 1.

crystallographic parameters are summarized in Table 1. The crystal structure contains one crystallographically independent atom of Fe3+ and Sb3+, respectively. The oxidation state of these ions are supported by bond-valence sum (BVS) calculations;28 see Table 2. Fe2+ was easily oxidized to Fe3+ in aqueous Table 2. Bond Valence Sum Calculations

Table 1. Crystallographic Data for FeSbO2F2 chemical formula formula weight/g mol−1 temperature/K crystal system space group a/Å b/Å c/Å β/deg V/Å3 ρ/g·cm−3 Z crystal size/mm3 radiation type wavelength/Å indices range

No. of reflections measured/unique observed [I > 3σ(I)] Rint (sin θ/λ)max/Å−1 RF/wRF [F > 3σ(F)] all reflections (%) goodness-of-fit (all)

FeSbO2F2 247.59 293 monoclinic C2/c (No. 15) 11.9129(15) 4.9605(5) 5.5000(6) 103.897(7) 315.50(6) 5.2124 4 0.35 × 0.08 × 0.05 Mo Kα 0.71069 −17 ≤ h ≤ 20 −8 ≤ k ≤ 8 −9 ≤ l ≤ 9

a

atoms

BVSa

Fe1 Sb1 O1 F1

2.8 3.0 2.1 0.9

BVS for FeSbO2F2 employing R0(Sb−O) = 1.973 Å.

condition as also observed by Penfold and Taylor.29 Magnetic susceptibility calculations based on Fe3+ also confirm the oxidation of Fe2+ to Fe3+. Each Fe 3+ is coordinated with four fluorine atoms equatorially and with two oxygen atoms axially to form trans[FeO2F4] octahedra. The Fe−F distances are in the range of 1.976(5)−1.981(5) Å, and the Fe−O distance is 1.951(6) Å. The Sb3+ ions are bonded to four oxygen atoms at distances in the range of 1.988(6)−2.209(6) Å to form [SbO4] seesaws. The extended asymmetric unit is shown in Figure 1. The trans-

3970/657 572 0.063 0.80 4.30/7.20 1.65

Figure 1. Asymmetric unit and selected equivalents of FeSbO2F2. There is one crystallographically independent atom of each of the Fe and Sb atoms, respectively. Fe shows slightly distorted octahedral coordination, whereas Sb has trigonal pyramidal coordination. Symmetry codes: (i) 0.5 − x, 0.5 − y, −z; (ii) 0.5 − x, 0.5 + y, 0.5 − z; (iii) x, 1 − y, −0.5 + z; (iv) 0.5 − x, 0.5 − y, −z; (v) x, −y, 0.5 + z; (vi) −x, −y, −z; (vii) −x, y, 0.5 − z.

Powder X-ray diffraction was used to check the phase purity of the samples used for magnetic susceptibility and heat capacity measurements. These data were collected by employing a Panalytical X’Pert PRO X-ray powder diffractometer in Bragg−Brentano geometry with Cu Kα radiation (λ = 1.540 60 Å). A fast scanning mode from 4° to 70° in 2θ with a step size of 0.0131° was employed for the data collection. All observed reflections could be indexed on the basis of the crystal structure refined from the single-crystal data. The full powder diffraction pattern was fitted using the program Jana2006. The refined data agree well with the data obtained from the single-crystal structure refinement. Chemical compositions were obtained by EDS using a Hitachi M3000 Tabletop scanning electron microscope (see Supporting Information). Field cooled (fc) magnetic susceptibilities of a polycrystalline sample of FeSbO2F2 (∼10.2 mg) were measured with an MPMS SQUID magnetometer (Quantum Design, 6325 Lusk Boulevard, San Diego) in the temperature range of 1.9−750 K. Heat capacities were determined on a powder sample (∼3 mg) intimately mixed with Apiezon N vacuum grease using a PPMS system (Quantum Design, 6325 Lusk Boulevard, San Diego) in the temperature range of 2.9−200 K. The heat capacity of the sample holder and the vacuum grease were determined in a preceding measurement cycle and subsequently subtracted from the total heat capacities.

[FeO2F4] octahedra are linked by corner-sharing to form [FeO2F2]n layers parallel to (011); see Figure 2a. The [SbO4] units connect to each other by edge-sharing to form [SbO2]n chains along [001]; see Figure 2b. The [FeO2F2]n and [SbO2]n units connect to each other via oxygen bridges to build the framework structure; see Figure 2c. The Sb−O distances are comparable to what has been observed for seesaw [SbO3F] units in Sb3O4F and longer than in the trigonal pyramidal [SbO3] units in Sb3O4F and in cubic Sb2O3.23,30 When comparing with other Fe3+−L−O−F systems, clearly there is a large variation in the coordination around Fe3+. The compounds FeSeO3F and FeTeO3F have cis[FeO4F2] octahedra and [LO3] (L = Se or Te) trigonal pyramid units.10,11 The cis-[FeO4F2] octahedra are edge-sharing via two O as well as via two F atoms to form [FeO3F]n chains. The [FeO3F]n chains connect to [LO3] by corner-sharing through Fe−O−L bonds. The cubic perovskite FePbO2F has [Fe(O,F)6] octahedra, where O and F mix on the same position.14 In the compound Bi4Fe5O13F the Fe atoms are coordinated by only O and Bi bonds only to F.16

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RESULTS AND DISCUSSIONS Crystal Structure. The new compound FeSbO2F2 crystallizes in the monoclinic space group C2/c with the unit cell parameters a = 11.9129(15) Å, b = 4.9605(5) Å, c = 5.5000(6) Å, β = 103.897(7)° and four formula units in the unit cell. The 4663

DOI: 10.1021/acs.inorgchem.7b00301 Inorg. Chem. 2017, 56, 4662−4667

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Inorganic Chemistry

Comparing the present compound FeSbO2F2 with compounds in the Fe2+−Sb3+−O−X (X = Cl, Br, I) systems, for example, Fe 3 Sb 5 O 9 I 3 , Fe 7 Sb 10 O 18 Cl 8 , Fe 7 Sb 10 O 18 Br 8 , Fe3Sb2O4Br4,31 it becomes clear that fluorine behaves more like oxygen to build a network, while the other halides act as terminating ions resulting in that such oxohalide compounds have layered structures with only weak connections between the layers. Magnetic Properties. The magnetic properties of FeSbO2F2 were investigated by magnetic susceptibility and heat capacity experiments. The polycrystalline sample used for the magnetic susceptibility and heat capacity experiments was characterized by X-ray powder diffraction; see Figure 3. The unit cell was found to be a = 11.9121(4) Å, b = 4.9581(1) Å, c = 5.5003(3) Å, and β = 103.945(3)°, which are close to the values for the unit cell obtained from single-crystal X-ray data; see Table 1. The Rietveld profile refinement of the powder diffraction pattern resulted in a reliability factor Rp = 11.21 and a goodness-of-fit (GOF) = 1.54. Figure 4 (mainframe) shows the magnetic susceptibilities χmol(T) = Mmol(T,H)/H, measured in a magnetic field of 1 T and the heat capacities (inset) versus temperature. The magnetic susceptibility exhibits a cusp indicating onset of bulk long-range anti-ferromagnetic ordering at a Néel temperature TN = 175(3) K. Below the cusp the susceptibility drops and increases again toward low temperatures, which we ascribe to a minute magnetic impurity phase that amounts to ∼1% assuming spin S = 5/2 entities. A shoulder at ∼35 K could be tentatively ascribed to some magnetic ordering processes in this impurity phase. Above the Néel temperature, the magnetic susceptibility decreases monotonously approaching a Curie−Weiss law toward very high temperatures, T ≫ TN, given by

Figure 2. (a) Corner-sharing trans-[FeO2F4] octahedra form [FeO2F2]n layers parallel to (011). (b) Edge-sharing seesaw [SbO4] units make [SbO2]n chains along [001]. (c) Overview of the crystal structure of FeSbO2F2. [FeO2F4] = green, Sb atoms gray, O atoms red.

χ (T ) =

C + χdia T − ΘCW

(1)

Figure 3. Comparison of the observed (green) and calculated (red) X-ray powder diffraction pattern of FeSbO2F2. The calculated pattern is based on the single-crystal X-ray determination of the crystal structure. 4664

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Inorganic Chemistry NAg 2μB 2

∞

χsq (t )Jintra

Θcw = −

Θcw = −235(5) K

indicating predominant anti-ferromagnetic spin-exchange interaction and a Curie constant C 3kB

= 4.37cm 3K/mol

(2)

where NA represents Avogadro’s constant, kB indicates the Boltzmann constant, and μB is the Bohr magneton. For the spin we used value of S = 5/2 appropriate for Fe3+ ions with the electronic configuration 3d5, and for the g-factor, g, a value of 2 appropriate for a spin-only moment in a half-filled electronic shell was used. The temperature-independent diamagnetic susceptibility of the closed electronic shells, χdia, was estimated from the increments listed in Selwood’s table32 to χdia = −73 × 10−6 cm3/mol per formula unit FeSbO2F2. The high-temperature susceptibility data unequivocally prove the Fe cations to be in the oxidation state +3. The increasing deviations of the experimental data from the Curie−Weiss law toward lower temperatures indicate growing anti-ferromagnetic short-range order due to a buildup of low-dimensional correlations in the square-planar Fe3+ layers in the b−c planes (see Figure 2a). The zero-field magnetic susceptibility in the paramagnetic regime of a square net arrangement of spin S = 5/ 2 entities, χ sq(t), in powers of the reduced temperature t t=

kBT Jintra S(S + 1)

t

(5)

Jintra znnS(S + 1) 3

= −235(5) K

(6)

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CONCLUSIONS Single crystals of the new quaternary oxofluoride FeSbO2F2 were successfully synthesized by hydrothermal synthesis at 230 °C. The new compound crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 11.9129 (15) Å, b = 4.9605 (5) Å, c = 5.5000 (6) Å, β = 103.897 (7)°, and Z = 4. There is one crystallographically independent Fe3+ and Sb3+ ion, respectively, that forms the building blocks; [SbO4] seesaws and trans-[FeO2F4] octahedra. The [SbO4] seesaw units are connected to each other by edge-sharing to form [SbO2]n chains along [001]. The trans-[FeO2F4] octahedra are connected via corner-sharing F atoms to form [FeO2F2]n layers parallel to (011). The [FeO2F2]n layers bond via O atoms to the [SbO2]n chains to make up the layered 3D framework structure of FeSbO2F2. Long-range anti-ferromagnetic ordering below ∼175 K is evidenced by magnetic susceptibility and heat capacity data. The magnetic susceptibility at high temperatures is consistent with a spin-only moment of S = 5/2 indicating an oxidation state of +3 for the Fe cations. Deviations from a pure Curie− Weiss type susceptibility and a significant reduction of the magnetic ordering entropy derived from the heat capacity data

(3)

where Jintra is the intralayer spin exchange for a systems coupled by the Heisenberg Hamiltonian H = Jintra ∑ Si⃗ Sj⃗ (4)

⟨ij⟩

n=1

cn n−1

where znn = 4 is the number of nearest neighbor spin moments in the square layer, one obtains for the intralayer exchange a value of 20.1(5) K, close to the value found to reproduce best the magnetic susceptibility data above the Néel temperature. The heat capacity data exhibit a small anomaly at 174(3) K close to the Néel temperature as identified from the magnetic susceptibility data; see inset in Figure 4. The magnetic entropy removed by the long-range anti-ferromagnetic ordering amounts to 0.7(1) J/(mol K), which is ∼5% of the entropy R × ln(2 × S + 1) ≈ 14.9 J/(mol K) expected for a spin S = 5/2 magnetic system. In view of the pronounced one-dimensional character of the crystal structure this discrepancy suggests that the majority of the magnetic entropy has already been removed by anti-ferromagnetic short-range ordering. Short-range ordering could also explain the extended critical regime seen in the magnetic susceptibility leading to the discrepancy between the extended Curie−Weiss law and the experimental data when approaching the Néel temperature.

with a Curie−Weiss temperature ΘCW of

NAg 2μB2 S(S + 1)

∑

The coefficients up to n = 6 are tabulated in the work by Lines.33 Using these coefficients we calculated the susceptibility of a Heisenberg spin S = 5/2 square net assuming Jintra = 20 K. The results are represented by the red dashed (χsq) and dotted (1/ χsq) lines in Figure 4. The square net susceptibility reduces over a large temperature range the deviations to the Curie−Weiss law. Long-range anti-ferromagnetic order at ∼175 K due to interlayer exchange and critical fluctuations above the Néel temperature can explain the decrease of the experimental data below the susceptibility of the square net. The antiferromagnetic intralayer spin exchange of ∼20 K matches favorably with the results for Curie−Weiss temperature ΘCW obtained from the high-temperature Curie−Weiss fit, where a value of −235 K was found. Using the relation35

Figure 4. Molar and inverse molar magnetic susceptibility of FeSbO2F2. The (black) dashed line represents the inverse magnetic susceptibility of a spin S = 5/2 system with a g-factor g = 2, a Curie− Weiss temperature of Θcw = −235 K, and a temperature-independent diamagnetic contribution of −73 × 10−6 cm3/mol. The (red) dashed and dotted lines are the direct and inverse magnetic susceptibilities of a square planar net of spin S = 5/2 entities coupled with an antiferromagnetic Heisenberg spin exchange of 20 K. (inset) Heat capacity Cp/T of FeSbO2F2. The anomaly at 175 K marked by the red vertical arrow corresponds to the cusp in the magnetic susceptibility due to long-range anti-ferromagnetic order seen in the magnetic susceptibility.

C=

= 3t +

33

has been calculated by Lines following Rushbrooke and Wood34 and casted into a power series of the reciprocal reduced temperature according to 4665

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are attributed to magnetic short-range ordering consistent with the pronounced square-planar character of the crystal structure.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b00301. EDS data on the heavy elements Fe and Sb (PDF) X-ray crystallographic information (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. (M.J.) *E-mail: [email protected]. (I.A.) ORCID

Mats Johnsson: 0000-0003-4319-1540 Notes

The authors declare no competing financial interest. Also, Supporting Information has been sent to Fachinformationzentrum Karlsruhe, Abt. PROKA, 76344 EggensteinLeopoldshafen, Germany (fax +49-7247-808-666; E-mail: crysdata@fiz-karlsruhe.de), and it can be obtained on quoting the deposit number CSD-432196 for the compound FeSbO2F2.

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ACKNOWLEDGMENTS The work has in part been performed with financial support from Stiftelsen Olle Engkvist Byggmästare and the Swedish Research Council. We thank E. Brücher and G. Siegle for expert experimental assistance with the magnetic and heat capacity measurements.

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