Synthesis, Structure, and Magnetic Properties of Two Mercury Selenite

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Synthesis, Structure, and Magnetic Properties of Two Mercury Selenite Antiferromagnets HgM(SeO3)2(H2O)2 (M = Co, Ni) Zhiying Zhao, Wanwan Zhang, and Zhangzhen He* State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China Inorg. Chem. Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 04/19/19. For personal use only.

S Supporting Information *

ABSTRACT: Two mercury selenite compounds HgM(SeO3)2(H2O)2 (M = Co, Ni) are synthesized using a conventional hydrothermal method. Both compounds crystallize in the monoclinic structure with a C2/c space group, and equivalent Co2+ or Ni2+ ions exhibit a stacked triangular lattice. Magnetic measurements suggest different magnetic properties between these two isostructural compounds, in which HgCo(SeO3)2(H2O)2 undergoes a canted antiferromagnetic order below TN = 7.6 K, while HgNi(SeO3)2(H2O)2 exhibits a collinear antiferromagnetic order below TN = 9.0 K. When applying a magnetic field, two successive magnetic transitions are observed at Bc1 ∼ 1 T and Bc2 ∼ 3.6 T in HgCo(SeO3)2(H2O)2, whereas only one field-induced transition is detected around 3.1 T in HgNi(SeO3)2(H2O)2.

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TeO32− groups are accordingly acted as “chemical scissor” and usually adopted in the design of low-dimensional magnets.14 Besides, d0 transition metal cations with large ionic radius like Cd2+ and Hg2+ can also be employed to construct the lowdimensional spin structure. The combination of both approaches is anticipated to be beneficial to weaken the magnetic correlation and constitute low-dimensional TLAs. In this work, we successfully synthesize two mercury selenite antiferromagnets HgM(SeO3)2(H2O)2 (M = Co, Ni) using a hydrothermal method. Both compounds exhibit a mixed metalchain structure along the (101) direction, forming a stacked triangular lattice in the bc plane. Our results show that HgCo(SeO3)2(H2O)2 undergoes a canted AFM order at TN = 7.6 K, while HgNi(SeO3)2(H2O)2 exhibits a collinear AFM order below TN = 9.0 K. Under the application of a magnetic field, two successive magnetic transitions are observed in HgCo(SeO3)2(H2O)2, whereas only one field-induced magnetic transition is found in HgNi(SeO3)2(H2O)2. The details of the crystal structure and the magnetic properties of both compounds are reported below.

INTRODUCTION Triangular lattice antiferromagnets (TLAs) have attracted great interest due to the fascinating magnetism in the fields of physics and chemistry. Two-dimensional (2D) TLAs are the simplest geometrically frustrated systems. The most engaging phenomenon is the quantum spin liquid ground state, in which quantum fluctuations prevent the establishment of magnetic order and the spins remain disordered even at 0 K.1 κ(ET)2Cu2(CN)3, EtMe3Sb[Pd(dmit)2]2, and κ-H3(Cat-EDTTTF)2 are well-acknowledged 2D quantum spin liquid TLAs.2 Another example of the novel magnetism in 2D TLAs is the 1/ 3 magnetization plateau with an “up−up−down” spin configuration driven by quantum fluctuations.3 This behavior has been found in several compounds, such as Cs2CuBr4,4 Ba3CoSb2O9,5 Ba3CoNb2O9,6 Ba3NiSb2O9,7 Ba3NiNb2O9,8 and Sr3NiNb2O9.9 Besides, stacked TLAs,10 which are composed of one-dimensional (1D) spin chains with antiferromagnetic (AFM) interchain interaction, can also exhibit interesting field-induced magnetic transitions. For example, magnetization plateau was found in Ca3Co2O6 and Sr3Co2O611 with ferromagnetic (FM) intrachain interaction, while a metamagnetic transition was detected in CsCoCl3 and CsCoBr312 with AFM intrachain interaction. On account of the rich physical phenomena, TLAs are therefore ideal candidates to study the exotic quantum magnetism and the field-induced phase transitions. Selenium and tellurium have been shown to be versatile chemical element in terms of crystal chemistry.13 Due to the second-order Jahn−Teller effect, the lone-pair electrons of Se4+ and Te4+ cations push the coordinated oxygen atoms toward one side. The resultant noncentrosymmetrical SeO32− and © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Synthesis. Both compounds were synthesized by a conventional hydrothermal method. The starting materials are listed as follows: (i) 0.4 mmol Hg2Cl2 (AR, 0.1888 g), 0.4 mmol CoO (AR, 0.0300 g), and 1.6 mmol SeO2 (AR, 0.1775 g) for HgCo(SeO3)2(H2O)2; (ii) 0.4 mmol Hg2Cl2 (AR, 0.1888 g), 0.8 mmol NiO (AR, 0.0598 g), and 1.2 mmol SeO2 (AR, 0.1332 g) for HgNi(SeO3)2(H2O)2. The mixtures were respectively dissolved in 6 mL of deionized water and sealed in Received: January 3, 2019

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DOI: 10.1021/acs.inorgchem.9b00008 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry autoclaves equipped with 28 mL Teflon liners. The autoclaves were then kept at 235 °C for 2 days and slowly cooled to room temperature at a rate of ∼1.4 °C/h for 6 days. During the preparations, nitric acid was added to adjust the pH value of the reaction (∼0.04 mL for Co and ∼0.13 mL for Ni). Small single crystals were obtained by this growth process and the purity was checked using the powder X-ray diffraction (XRD), which was collected on a Rigaku MiniFlex 600 diffractometer equipped with graphite monochromated Cu radiation with λ = 1.54 Å (see Figure S1). Determination of the Single Crystal Structure. Single crystal XRD measurement for HgCo(SeO3)2(H2O)2 was performed on a Rigaku Mercury CCD diffractometer equipped with a graphitemonochromated Mo Kα radiation with λ = 0.71 Å at room temperature. The structure was solved by direct method and refined by Olex2.15 All nonhydron atoms were refined with anisotropic thermal parameters. The hydrogen atoms were located at calculated positions and refined with isotropic thermal parameters. The final refined structural parameters were checked by PLATON.16 Crystallographic data and structure refinement of HgCo(SeO3)2(H2O)2 single crystal are listed in Table 1. The final refined atomic positions and structural parameters are listed in Tables S1−S3.

asymmetrical unit: one Hg, one Co, and one Se. Their coordination environments are given in Figure S2. Equivalent Co2+ ions are surrounded by six oxygen atoms, and two of them are further connected to two hydrogen atoms forming H2O molecules. The resultant CoO6 octahedra are distorted and the Co−O bond lengths fall in the range of 2.075−2.103 Å (Table S3). Hg atoms are coordinated with six oxygen atoms with Hg−O distance ranging from 2.263 to 2.626 Å. Se atoms are in a trigonal pyramid geometry, and the Se−O bond lengths are around 1.70 Å. The result of bond valence sum18 indicates that the oxidation states of Hg, Co, and Se atoms are +2, +2, and +4, respectively. As shown in Figure 1, the isolated CoO6 octahedra are linked by corner-shared SeO32− groups to constitute a 2D

Table 1. Crystal Data and Structure Refinements for HgM(SeO3)2(H2O)2 (M = Co, Ni) at Room Temperature compound formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc (g cm−3) GOF on F2 R1, wR2 [I > 2σ(I)]a R1, wR2 (all data)

HgCo(SeO3)2(H2O)2 549.47 monoclinic C2/c 12.4353(7) 7.7000(3) 9.3421(4) 90 123.365(3) 90 747.09(6) 4 4.885 1.076 0.0561, 0.1430 0.0583, 0.1486

HgNi(SeO3)2(H2O)2 549.23 monoclinic C2/c 12.3732(2) 7.6539(2) 9.3475(2) 90 123.205(1) 90 4

Figure 1. Crystal structure of HgCo(SeO3)2(H2O)2. (a) 2D layer projected in the bc plane. (b) 3D framework viewed along the b direction.

R 1 = ∑||F o| − |F c ||/∑F o|, wR 2 = {∑w[(F o) 2 − (F c )2 ]2 / ∑w[(Fo)2]2}1/2.

a

It should be mentioned that the quality of HgNi(SeO3)2(H2O)2 single crystals is not good enough to give reliable crystal data. Since both compounds are isostructural as confirmed by the powder XRD, in this work the lattice parameters of HgNi(SeO3)2(H2O)2 are determined by refining the powder XRD pattern (see Figure S1b) using FullProf Suite software17 and are also given in Table 1. Magnetic Measurements. Magnetic properties were investigated on a SQUID (Quantum Design). A collection of powder sample (about 25.56 mg for HgCo(SeO3)2(H2O)2 and 26.62 mg for HgNi(SeO3)2(H2O)2) were prepared by crashing small crystals. Magnetic susceptibility was measured between 2 and 300 K in 0.1 and 5 T. Magnetization was carried out at 2 and 50 K with magnetic field applied up to 5 T. Thermal Analysis. Thermogravimetric (TG) analysis was carried out with a NETZCH STA 449F3 instrument under a N2 atmosphere. The samples were placed in Al2O3 crucibles and heated up to 800 °C with a heating rate of 10 °C/min.

network in the bc plane, which are further separated by Hg2+ cations along the a axis with a b/2 displacement alternately. Removing the nonmagnetic Hg2+ cations and SeO32− groups, the topology of the spin−lattice can be considered in two ways. As shown in Figure 2a, the arrangement of Co2+ ions can feature a rhombus lattice in the bc plane with the nearest neighboring Co−Co bond length of 6.05 Å, and the intralayer exchange coupling is via the SeO32− groups. In addition, there is probably a magnetic exchange along the short diagonal direction of the rhombus through Co−OH···O−Se−O−Co pathway. The resultant exchange couplings are along the b axis with Co−Co distance of ∼7.70 Å. It has been reported that hydrogen bonds can play an important role in propagating magnetic exchange in many magnets.19 Considering such exchange pathway, the spin−lattice of Co2+ ions can therefore be viewed as an isosceles triangular lattice instead. Since the exchange coupling via hydrogen bond (J2) should be weaker than those bridged by direct SeO32− groups (J1), the frustration effect is therefore expected to be weak. Alternatively, it is found that the nearest Co−Co distance between adjacent bc planes is 5.34 Å, which is shorter than those which are in-plane.

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RESULTS AND DISCUSSION Crystal Structure. Both compounds crystallize in the same monoclinic structure with a C2/c space group. Here the crystal structure of HgCo(SeO3)2(H2O)2 is described in detail as an example. There are crystallographic sites as follows in an B

DOI: 10.1021/acs.inorgchem.9b00008 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. Topological structure of HgCo(SeO3)2(H2O)2. (a) 2D spin arrangement of Co2+ ions in the bc plane and (b) 1D spin arrangement of Co2+ ions in the ac plane. J1 and J2 in panel (a) are the intraplane exchange couplings through Co−O−Se−O−Co and Co−OH···O−Se−O−Co pathways, respectively. J in panel (b) is the intrachain interaction. (c) Stacked triangular lattice.

= χ0 + C/(T − θCW), giving the temperature-independent term χ0 = −1.3(3) × 10−4 emu/mol, the Curie−Weiss temperature θCW = −23.6(4) K and the effective moment μeff = 5.00 μB/f.u. Here χ0 is contributed from the Van Vleck paramagnetism and core electron diamagnetism. The negative θCW suggests a dominant AFM interaction among Co2+ spins. The yielded μeff is much larger than the spin-only value of 3.87 μB/Co2+ ion (S = 3/2), demonstrating that at high temperatures Co2+ ions in HgCo(SeO3)2(H2O)2 are in the high-spin state and have a significant orbital moment. This behavior is usually found in cobalt oxides, such as CoV2O6,10 Co3V2O8,20 BaCo2V2O8,21 BiCo2BP2O10,22 Co2(TeO3)(SO4)·H2O,23 and so on. Figure 4 shows the magnetization as a function of the magnetic field. Two prominent features are observed at T = 2

Therefore, the spin−lattice of Co2+ ions can also be looked as 1D chain as displayed in Figure 2b, and the intrachain exchange coupling (J) is propagated through the Co−O−Hg− O−Co pathway. These 1D spin chains are further arranged on a triangular lattice with the presence of J1 and J2, as shown in Figure 2c. Magnetic Properties of HgCo(SeO3)2(H2O)2. Figure 3a shows the magnetic susceptibility χ(T) measured in B = 0.1 T.

Figure 4. Field dependence of magnetization measured at 2 and 50 K. Bc1 and Bc2 are the critical fields. Inset shows the magnetic susceptibility measured in B = 5 T. Figure 3. (a) Temperature dependencies of the magnetic susceptibility of HgCo(SeO3)2(H2O)2 measured in B = 0.1 T. (b) Reciprocal of the field-cooling magnetic susceptibility by subtracting the temperature-independent term χ0. The solid line is a fit to the Curie−Weiss law.

K. First, two successive magnetic transitions are observed at Bc1 ∼ 1 T and Bc2 ∼ 3.6 T, and a possible magnetization plateau is existent in between. In many cobalt oxides, the Co2+ ion in a cubic crystal field can be considered to have an effective spin of 1/2 under the effect of spin−orbit coupling and trigonal distortion at low temperatures.24 In HgCo(SeO3)2(H2O)2, the magnetic moment between Bc1 and Bc2 is around 0.5 μB, which is about 1/3 of the saturated moment for 1/2 spin. Similar phenomenon with comparable magnetic moment is also found in the well-studied TLA Ba3CoSb2O9.5 On account of the random crystal orientation in the powder sample, the magnetization plateau is usually not as obvious as in singe

χ(T) is increased with lowering temperature, and a sharp peak is observed at TN = 7.6 K which is associated with the AFM order of Co2+ spins. Zero-field-cooling (ZFC) and field-cooling (FC) curves start to bifurcate below TN, indicating that Co2+ ions are aligned in a canted AFM manner. As seen in Figure 3b, above 100 K χ(T) follows well the Curie−Weiss behavior χ C

DOI: 10.1021/acs.inorgchem.9b00008 Inorg. Chem. XXXX, XXX, XXX−XXX

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order, and TN is decreased to 8.4 K in 5 T. Furthermore, χ(T) is enhanced significantly below TN and seems to upturn at lower temperatures. Above 100 K χ(T) is well-described by the Curie−Weiss law χ = χ0 + C/(T − θCW) with χ0 = −1.24(5) × 10−4 emu/mol, as the solid line shown in Figure 5b. The yielded Curie−Weiss temperature is θCW = −19.6(1) K, suggesting a dominant AFM interaction among Ni2+ spins. The effective moment is calculated to be μeff = 3.22 μB/f.u., which is larger than the spin-only value of 2.83 μB/Ni2+ ion (S = 1). The large effective moment is often found in nickel oxides, such as Ni2V2O7,25 Ni3V2O8,20 BiNi2BP2O10,22 and so on. The magnetization as a function of the magnetic field is plotted in Figure 6. At 2 K, the magnetization is linearly

crystals. High-field magnetization performed on sizable single crystals is therefore called for to confirm the plateau behavior. The second feature of the magnetization is the clear hysteresis below Bc2, which is especially evident around Bc1. The irreversible magnetization is consistent with the bifurcation in χ(T) and confirms the canted AFM ground state. It is noted that the magnetization seems to be reversible above Bc2, which is, however, principally due to the limitation of the laboratory magnetic field in this work. It is possible that the hysteresis behavior could exist in a wider field window if the field is applied higher. This expectation is supported by the magnetic susceptibility measured in 5 T. As shown in the inset to Figure 4, a weak splitting between FC and ZFC branches is visible at low temperatures. The sharp peak observed in 0.1 T is evolved into a broad peak centered around 6 K, which means that the Co2+ spins enter into a different ordered state above Bc2. Magnetic Properties of HgNi(SeO3)2(H2O)2. Figure 5a shows the temperature dependencies of the magnetic

Figure 6. Field dependencies of magnetization measured at 2 and 50 K. The solid lines are guides for the eyes.

increased with increasing field. A slope change is observed at Bc ∼ 3.1 T, which indicates a field-induced magnetic transition. Above Bc, the magnetization is linearly increased again. The magnetic moment is only about 0.3 μB in 5 T, which is much smaller than the saturated moment of a Ni2+ ion. If there is also a magnetization plateau, then the critical fields might be higher as compared with HgCo(SeO3)2(H2O)2 due to the larger spin and stronger nearest-neighboring interaction of Ni2+ ions. For example, the critical field entering into the plateau in Ba3CoSb2O9 is about 10 T,5 while it is enhanced to 35 T when replacing Co2+ by Ni2+ ions in Ba3NiSb2O9.7 High-field magnetization performed on sizeable single crystals is therefore required to search for the possible plateau behavior. Topological Structure. In frustrated antiferromagnets, the frustration factor f = θCW/TN is usually defined as a measure of the frustration level, and materials with f > 10 are called strongly geometrically frustrated systems. In this work, f is calculated to be 3.11 for HgCo(SeO3)2(H2O)2 and 2.18 for HgNi(SeO3)2(H2O)2. The small f implies that both compounds are weakly frustrated. As mentioned before, the topology of magnetic ions can be considered as either 2D triangular lattice or 1D spin chain arranged on a triangular lattice. The weak frustration in the 2D triangular lattice is understandable due to a nonequilateral triangle with J1 > J2, in which J2 is quite weak. As seen in Figure S3, both compounds can also be fitted well by the Fisher’s expression for a linear spin chain model,26 giving J = −1.68(3) and −5.57(1) K for Co and Ni compounds, respectively. This suggests that both compounds can be considered as a stacked triangular lattice

Figure 5. (a) Temperature dependencies of the magnetic susceptibility of HgNi(SeO3)2(H2O)2 measured in B = 0.1 and 5 T. The derivative of the magnetic susceptibility in 0.1 T is also plotted. (b) Reciprocal of the magnetic susceptibility in 0.1 T by subtracting the temperature-independent term χ0. The solid line is a fit to the Curie−Weiss law.

susceptibility measured in 0.1 T. Different from the Co compound, there is no splitting between ZFC and FC curves down to 2 K. Upon cooling, a broad peak is present around 10 K, which is a sign for the establishment of the short-range AFM correlation. With further lowering of temperature, a long-range AFM order is realized below TN = 9.0 K and χ(T) starts to decrease rapidly. The onset temperature of the AFM transition is defined as the peak position from the derivative curve. The application of a magnetic field can suppress the magnetic D

DOI: 10.1021/acs.inorgchem.9b00008 Inorg. Chem. XXXX, XXX, XXX−XXX

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with AFM intrachain interaction (Figure 2c). Such situation is similar to those of CsCoCl3 and CsCoBr3,12 and the competition between the intrachain and interchain interactions can also lead to exotic field-induced magnetic transitions. It should be stated that estimation of the spin exchange pathways from geometrical considerations alone is difficult. To clarify the nature of the topology, further experiments such as neutron scattering and nuclear magnetic resonance need to be carried out. Thermal Analysis. The thermal stability is examined by heating the samples up to 800 °C. As shown in Figure 7, both

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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.9b00008. Powder XRD patterns; crystallography data; fitting of Fisher’s model (PDF) Accession Codes

CCDC 1887860 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Zhiying Zhao: 0000-0002-7878-8972 Zhangzhen He: 0000-0002-8496-1532 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. U1832166, 51702320, 21573235, and U1632159), the Opening Project of Wuhan National High Magnetic Field Center (Grant No. 2015KF08), and the Chinese Academy of Sciences under Grant No. KJZDEW-M05.

Figure 7. Thermogravimetric curves for HgM(SeO3)2(H2O)2 (M = Co, Ni).

compounds exhibit a similar thermal behavior of the weight loss when the temperature is increased. HgCo(SeO3)2(H2O)2 is found to be stable below 280 °C, and then a rapid loss of the weight is followed. The observed weight loss from 280 to 315 °C is about 6.7%, which is close to the calculated value 6.6% of two water molecules in HgCo(SeO3)2(H2O)2. Upon warming, weight is significantly lost above 500 °C and finally stabilized at 640 °C, indicating a further decomposition of this compound. HgNi(SeO3)2(H2O)2 exhibits a similar thermal behavior with the starting temperature of releasing water molecules occurring at 340 °C.

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REFERENCES

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CONCLUSIONS

In this work, two mercury selenite antiferromagnets HgM(SeO3)2(H2O)2 (M = Co, Ni) have been synthesized using a conventional hydrothermal method. Both compounds are isostructural and crystallize in the monoclinic structure with a C2/c space group. One of the most remarkable structural features is that two compounds may be considered as a stacked triangular lattice antiferromagnets with AFM intrachain interaction. Magnetic measurements suggest that HgCo(SeO3)2(H2O)2 undergoes a canted AFM order below TN = 7.6 K, while HgNi(SeO3)2(H2O)2 exhibits a collinear AFM order below TN = 9.0 K. When applying the magnetic field, two successive magnetic transitions are observed in HgCo(SeO3)2(H2O)2, whereas only one field-induced magnetic transition is found in HgNi(SeO3)2(H2O)2. E

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Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.9b00008 Inorg. Chem. XXXX, XXX, XXX−XXX