Magneto-Structural Relationship of Tetragonally-Compressed Octahedral Iron(II) Complex Surrounded by a pseudo-S₆ Symmetric Hexakis-Dimethylsulfoxide Environment

Abstract

Since the octahedral high-spin iron(II) complex has the ⁵T_2g ground term, the spin-orbit coupling should be considered in magnetic analysis; however, such treatment is rarely seen in recent papers, although the symmetry-sensitive property is of interest to investigate in detail. A method to consider the T-term magnetism was well constructed more than half a century ago. On the other hand, the method has been still improved in recent years. In this study, the octahedral high-spin iron(II) complex [Fe(dmso)₆][BPh₄]₂ (dmso: dimethylsulfoxide) was newly prepared, and the single-crystal X-ray diffraction method revealed the tetragonal compression of the D₄-symmetric coordination geometry around the iron(II) ion and the pseudo-S₆ hexakis-dmso environment. From the magnetic data, the sign of the axial splitting parameter, Δ, was found to be negative, indicating the ⁵E ground state in the D₄ symmetry. The DFT computation showed the electronic configuration of (d_xz)²(d_x²_−y²)¹(d_yz)¹(d_xy)¹(d_z²)¹ due to the tetragonal compression and the pseudo-S₆ environment of dmso π orbitals. The electronic configuration corresponded to the ⁵E ground term, which was in agreement with the negative Δ value. Therefore, the structurally predicted ground state was consistent with the estimation from the magnetic measurements.

1. Introduction

Octahedral high-spin iron(II) complexes have the ⁵T_2g ground terms, and their fundamental magnetic theory was constructed in the 1960s and 1970s [1,2,3]. On the other hand, the theory does not seem to be often used recently, probably because the contribution of the orbital angular momentum is difficult to be treated. However, consideration of the spin-orbit coupling is important for understanding the correct electronic state, which leads to an excellent physical property prediction and material design. In this article, for the purpose of showing how to analyze magnetic data of octahedral high-spin iron(II) complexes, we introduce some of the improved new techniques: (1) How to determine the sign of the ligand field splitting, (2) how to simulate field-effect in the low-temperature region, and (3) how to simulate saturation behavior of magnetization.

Metal complexes possessing the T-term ground states often show unusual magnetic behavior due to the spin-orbit coupling. After Kotani proved the contribution of the spin-orbit coupling for such compounds [4], the effects of the low-symmetry ligand field and the orbital reduction factor were found to play an important role [5,6,7,8], and the temperature dependence of the effective magnetic moment came to be successfully simulated for mononuclear T-ground-term complexes [2,7,8]. Here, we want to emphasize that the spin-orbit splitting caused by the spin–orbit interaction is different from the normal zero-field splitting. The normal zero-field splitting is caused by the spin–spin interaction when the number of unpaired electrons is equal to or larger than two. The spin-orbit splitting is actually a splitting in the zero-field, but is caused by the spin-orbit coupling when the orbital angular momentum remains unquenched. The magnetic behavior caused by the spin-orbit splitting is sometimes approximately analyzed by the theory of zero-field splitting, but it is just an approximation and the data should be analyzed by the theory considering the spin-orbit coupling.

For the octahedral high-spin iron(II) complexes, Griffiths obtained a 15 × 15 secular matrix for the ⁵T_2g term [1], considering the spin-orbit coupling. He obtained an energy diagram of the 15 states from the ⁵T_2g term with respect to the distortion around the iron(II) ion. Figgis also derived the secular matrix for the ⁵T_2g term and successfully simulated the temperature dependence of the effective magnetic moment [2]. Later, Long introduced the orbital reduction factor for the octahedral high-spin iron(II) complexes [3]. Recently, single-ion magnet behavior was observed in high-spin iron(II) complexes [9,10], although they are not octahedral, and the interests to the high-spin iron(II) complexes are increasing. The study on the magneto-structural relationship is expected to give important insight in designing magnetic materials.

When using the theory for the ²T_2g-ground term complexes [1,2,3], the 15 × 15 secular matric were to be solved each time for an octahedral high-spin iron(II) complex. However, recently, the secular matrix was successfully solved to obtain Zeeman energy equations expressed as the functions of three independent parameters, Δ, λ, and κ, where Δ is the axial ligand-field splitting parameter, λ is the spin–orbit coupling parameter, and κ is the orbital reduction factor [11]. With these Zeeman energy equations, magnetic simulation can be performed by simply substituting numerical values for parameters without solving the secular matrix each time. In this study, magnetic analysis was conducted for a newly prepared octahedral high-spin iron(II) complex, [Fe(dmso)₆][BPh₄]₂ (dmso: dimethylsulfoxide), using the equations, for the purpose of gaining further insight into magneto-structural relationship.

2. Results and Discussion

2.1. Crystal Structure of 1

Crystal structure of [Fe(dmso)₆][BPh₄]₂ (1) was determined by the single-crystal X-ray method. Crystallographic data are summarized in

Table 1. Crystallographic data and refinement parameters of 1.

Empirical Formula	C60H76B2FeO6S6
Formula Weight	1163.08
Crystal system	tetragonal
Space group	P42/n
a/Å	17.76361(7)
c/Å	19.46383(12)
V/Å3	6141.73(5)
Z	4
Crystal Dimensions/mm	0.373 × 0.292 × 0.211
T/K	203
λ/Å	0.71073
ρcalcd/g cm−3	1.528
µ/mm−1	0.496
F(000)	2464
2θmax/◦	60.1
No. of Reflections Measured	173,887
No. of independent reflections	8991 (Rint = 0.0201)
Data/restraints/parameters	8991/163/405
R1a (I > 2.00σ(I))	0.0327
wR2b (All reflections)	0.0356
Goodness of Fit Indicator	1.029
Highest peak, deepest hole/e Å−3	0.49, −0.47
CCDC deposition number	1854569

^a R₁ = Σ||Fo| − |Fc||/Σ|Fo|, ^b wR₂ = [Σ(w(Fo² − Fc²)²)/Σw(Fo²)²]^1/2.

, and the structures of the complex cation, [Fe(dmso)₆]²⁺, are shown in Figure 1. The compound consists of the complex cations and the tetraphenyl borate anions in a 1:2 molar ratio. In the complex cation, the six dmso molecules coordinate to the central iron(II) ion through oxygen atoms, forming an octahedral coordination geometry with the O₆ donor set. The cation is centrosymmetric, and tetragonally compressed along the Fe(1)-O(7) direction. The bond distances, Fe(1)-O(5), Fe(1)-O(6), and Fe(1)-O(7), were 2.1408(7), 2.1586(9), and 2.0899(8) Å, respectively. The central FeO₆S₆ unit can be approximated as the S₆ symmetry (Figure 1a). Four inter-ligand CH···O hydrogen bonds were found in a complex cation (Figure 1b), affording a 16-membered chelating ring perpendicular to the tetragonal compression axis. Earlier, the crystal structure of [Fe(dmso)₆][SnCl₆]₂ (2) was reported [12], and phase transition behavior was investigated for [Fe(dmso)₆][ClO₄]₂ [13], but complex 1 has not been reported so far.

Among the six dmso moieties of the [Fe(dmso)₆]²⁺ complex cation in 1, four of them were found to be disordered, suggesting the sulfur-inversion motion as well as the cobalt(II) and zinc(II) derivatives [14,15]. Among the crystals of [Co(dmso)₆][BPh₄]₂, [Zn(dmso)₆][BPh₄]₂, [Mg(dmso)₆][BPh₄]₂ [16], and [Fe(dmso)₆][BPh₄]₂ (1) complexes, the cobalt(II) and zinc(II) complexes form isomorphous crystals, while the iron(II) complex (1) is isomorphous to the magnesium (II) complex. In the magnesium (II) complex cation, a tetragonal compression was observed similar to 1.

In the related iron(II) complex 2, the [Fe(dmso)₆]²⁺ cation was more symmetrical than that in 1, and the cation in 2 exactly belongs to the S₆ point group. Each dmso moieties in 2 showed the similar disorder at 213 K, suggesting the sulfur-inversion motion in the crystal. The Fe-O distances in 2 [2.121(3) Å] was comparable to the average Fe-O distance in 1 [2.1298(8) Å]. In 2, the octahedral FeO₆ coordination geometry showed the slight trigonal compression along the S₆ axis. Using the conformation notation in [16], the conformer of the main [Fe(dmso)₆]²⁺ structure in 2 was the “α₆” conformation, which was considered to be the most stable one. On the other hand, the conformer of the main [Fe(dmso)₆]²⁺ structure in 1 was “trans-β₂γ₄” conformation, which was not so stable on its own. The reason for this unstable conformation is considered to be due to the crystal-packing effect of the bulky tetraphenylborate anions [15,16,17] as discussed in our previous paper on [Mg(dmso)₆][BPh₄]₂ [16].

In the crystal structure of 1, the complex cation was surrounded by eight tetraphenylborate anions, and the distinct CH···π interactions were observed between the dmso methyl groups and the phenyl rings of the tetraphenylborate anions.

2.2. Magnetic Properties

Magnetic susceptibility (χ_A) was measured in the temperature range of 2–300 K, and the χ_AT versus T plot is shown in Figure 2. The observed χ_AT value at 300 K (3.46 cm³ K mol⁻¹) was larger than the spin-only value for the S = 2 state (3.00 cm³ K mol⁻¹), and this suggests a contribution of the orbital angular momentum. When lowering the temperature, the observed χ_AT value slightly increased until at 120 K (3.47 cm³ K mol⁻¹ at 120 K), and decreased until at 2 K (1.42 cm³ K mol⁻¹ at 2 K). This behavior, possessing a χ_AT maximum, is typical of ⁵T_2g-term magnetism for octahedral high-spin iron(II) complexes [2].

Three typical theoretical curves are depicted in Figure 3, based on the Hamiltonian, H = Δ(L_z² − 2/3) + κλL·S + β(κL_u + g_eS_u)·H_u (u = x, y, z) [11], where Δ is the axial splitting parameter, κ is the orbital reduction factor, and λ is the spin-orbit coupling parameter. In addition, the axiality parameter v, defined as v = Δ/(κλ), was introduced, and a relationship can be seen between the v value and the maximum χ_AT temperature (T_max). That is, the larger the v value, the higher the maximum temperature, T_max. When the T_max value is in the range of 138–150 K, the |v| value is considered to be close to zero; when the T_max value is lower than 138 K, the v value is considered to be positive; when the T_max value is higher than 150 K, the v value is considered to be negative. Therefore, since the T_max value of the observed data is ~120 K, the v value is considered to have a positive sign and the Δ value is considered to be negative, indicating the ⁵E ground state (Figure 4). That is, the ⁵T₂ ground term in the O symmetry splits into ⁵E and ⁵B₂ terms in the D₄ symmetry, and the ⁵E term is lower in energy than the ⁵B₂ term.

In the earlier works [1,2,3], the Hamiltonian had been slightly being modified with respect to handling the orbital reduction factor. Figgis and coworkers introduced the orbital reduction factor in the third term (Zeeman term) of the Hamiltonian [2], and Long and coworker further introduced the orbital reduction factor in the second term (spin-orbit coupling term) of the Hamiltonian [3]. Long and coworker used a parameter v = Δ/λ, but in this study, we used the axiality parameter v = Δ/(κλ) [11], because it has some advantages in expressing coefficients. It is noted that Kahn used a parameter v =Δ/|λ| for an octahedra high-spin cobalt(II) complexes [18]. Since our treatment is slightly different from the others, the simulation results are also slightly different from the earlier works.

Using the Figgis basis set [2] for the ⁵T_2g term, the secular matrices were constructed [11]. The shapes of the resulting matrices are essentially the same as the Griffiths matrices [1] except for the orbital reduction factor. The exact solution was successfully obtained for the matrices [11], and the zero-field energies and the first- and the second-order Zeeman coefficients were obtained for 15 sub-states of the ⁵T_2g term. The zero-field magnetic susceptibility was obtained as the ordinary Van Vleck equation, and in addition, the field-dependent magnetic susceptibility equation was obtained as expressed in Equations (1)–(3).

$${\chi }_{\mathrm{A},\mathrm{av}}=\frac{{\chi }_z+2{\chi }_x}{3},$$

(1)

$${\chi }_{\mathrm{A},u}=\frac{N{\sum }_n(-E_{n,u}^{(1)}-2E_{n,u}^{(2)}{H}_u)\exp (-E_{n,u}/kT)}{H_u{\sum }_n\exp (-E_{n,u}/kT)}(u=z,x;n=1–15),$$

(2)

$$E_{n,u}=E_{n,u}^{\left(0\right)}+E_{n,u}^{\left(1\right)}{H}_u+E_{n,u}^{\left(2\right)}{H}_u^2\hspace{1em}\hspace{1em}(u=z,x;n=1–15),$$

(3)

The powder average of the magnetization is generally expressed by Equation (4). In this study, the expanded equation [Equation (5) with Equation (6)] [19] by calculating the integrals for the axial symmetry was used. We calculated the powder average of the magnetization using Equation (7) with m = 90.

$$M_{\mathrm{av}}={\left(4\pi \right)}^{-1}{\int }_0^{2\pi }{\int }_0^{\pi }M\left(\theta ,\phi \right)\sin \theta d\theta d\phi ,$$

(4)

$$M_{\mathrm{av}}=\underset{m\to \infty }{\lim }{\sum }_{j=1}^{m}M\left(\frac{\left(j-\frac{45}{m}\right)\pi }{180}\right)\left[\cos \frac{\left(j-1\right)\pi }{180}-\cos \frac{j \pi }{180}\right],$$

(5)

$$M\left(\theta \right)=\frac{N{\sum }_n\left(-E_{n,\theta }^{\left(1\right)}-2E_{n,\theta }^{\left(2\right)}{H}_{\theta }\right)\exp \left(-E_{n,\theta }/kT\right)}{{\sum }_n\exp \left(-E_{n,\theta }/kT\right)},$$

(6)

$$M_{\mathrm{av}}={\sum }_{j=1}^{m}M\left(\frac{\left(j-\frac{45}{m}\right)\pi }{180}\right)\left[\cos \frac{\left(j-1\right)\pi }{180}-\cos \frac{j \pi }{180}\right],$$

(7)

In the analysis, at first, the χ_AT versus T data in the range of 10–300 K were analyzed by the zero-field equation (Figure S1), and the obtained parameter set was obtained as (λ, κ, v) = (−100 cm⁻¹, 0.66, 5.6) with the discrepancy factors of R_χ = 3.9 × 10⁻³ and R_χT = 1.6 × 10⁻³ in the range of 10–300 K, and R_χ = 2.4 × 10⁻¹ and R_χT = 5.1 × 10⁻³ in the range of 2–300 K. The Δ value was calculated to be −370 cm⁻¹. The obtained λ value is consistent with the −ζ/4 value with ζ = 400 cm⁻¹ for iron(II) ion [20], where ζ is the single-electron spin-orbit coupling parameter. The small κ value is thought to be due to the π orbital interaction with the dmso ligands, which will be discussed in the following density functional theory (DFT) computation section. The obtained positive v value is consistent with the initial estimation from the χ_AT versus T curve. The data in the range of 10–300 K were well reproduced with reasonable parameters; however, the decrease in χ_AT below 10 K and the magnetization were not reproduced.

For the decrease in χ_AT, in this case, there are two possible reasons, the field-saturation effect and the intermolecular antiferromagnetic interactions. If the magnetic field effect of 3000 Oe was considered, using the field-dependent susceptibility equation [Equations (1)–(3)], the obtained parameter set was the same, but the discrepancy factors became slightly better (R_χ = 3.8 × 10⁻³ and R_χT = 1.5 × 10⁻³ in the range of 10–300 K; R_χ = 2.4 × 10⁻¹ and R_χT = 4.3 × 10⁻³ in the range of 2–300 K). By the field effect of 3000 Oe, the calculated χ_AT value became 6% smaller at 2 K, and 1.5% smaller at 4 K Therefore, the small contribution of field-saturation effect was confirmed, indicating that the field-saturation effect was not dominant in the χ_AT decrease.

In the next approach, the intermolecular interaction was also considered in addition to the field effect, introducing the Weiss constant, θ, for the intermolecular interaction. The full χ_AT versus T data (2–300 K) and the field-dependent data of the magnetization were simultaneously analyzed, and both data were successfully fitted as shown in Figure 2. The best-fitting parameter set was obtained as (λ, κ, v, θ) = (−100 cm⁻¹, 0.66, 5.5, −1.5 K) at H = 3000 Oe, with discrepancy factors of R_χ = 2.6 ×10⁻³ and R_χT = 4.3 ×10⁻⁴ (in the full temperature range). The Δ value was calculated to be −363 cm⁻¹, and the obtained θ value corresponded to zJ = ~−0.5 cm⁻¹. The zJ value is consistent with the intermolecular antiferromagnetic interaction through CH···π interactions observed in the crystal structure. Both the full χ_AT versus T data and the field dependent data of the magnetization were successfully analyzed with reasonable parameters, and the intermolecular interaction was found to be the dominant factor for the decrease in χ_AT below 10 K.

Using the Figgis basis set [2], the lowest three states from the ⁵T_2g term are described by the wave functions expressed in Equations (8)–(10), where $|M_L,M_S\rangle$ ($M_L$ = 0, ±1, ±2 and $M_S$ = 0, ±1, ±2) are wave functions and c_k (k = 0 − 35) are coefficients. It is noted that the coefficients c_k depend only on two parameters κ and v. When the Δ value is negative, the ground state corresponds to the wave functions ${\Psi }_2$ and ${\Psi }_3$, and the coefficients c₄ and c₇ will be dominant. Therefore, the ground state can be approximated as the $M_S$ = ±2 states. This enables us to calculate the g values of the ground state from the first-order Zeeman coefficients as g_z = 2.21 and g_x = 0.00, although these values are not ascertained by the electron spin resonance (ESR), because the compound is unfortunately ESR-silent. Further investigation has not been conducted on the single molecule magnet properties.

$${\Psi }_1=c_1|1,1\rangle +c_2\frac{\sqrt{2}}{2}\left\{|2,0\rangle -|-2,0\rangle \right\}+c_3|-1,-1\rangle ,$$

(8)

$${\Psi }_2=c_4|1,2\rangle +c_5\frac{\sqrt{2}}{2}\left\{|2,1\rangle -|-2,1\rangle \right\}+c_6|-1,0\rangle ,$$

(9)

$${\Psi }_3=c_7|-1,-2\rangle +c_8\frac{\sqrt{2}}{2}\left\{|2,-1\rangle -|-2,-1\rangle \right\}+c_9|1,0\rangle ,$$

(10)

2.3. Density Functional Theory (DFT) Computation

The restricted open-shell Hartree-Fock (ROHF) DFT calculation was conducted for the [Fe(dmso)₆]²⁺ complex cation, using the crystal structure. The ROHF calculation is suitable for considering d-orbitals with unpaired electrons. The energy levels of five molecular orbitals related to the d-orbitals are shown in Figure 5 together with the depiction of the molecular orbitals. The tetragonal compression axis was taken as the principal axis along the z direction. The x and y axes were taken along the two bisecting directions of the adjacent equatorial donor atoms, because the dmso π orbitals were considered to be oriented parallel to the bisecting directions. Therefore, the resulting d_σ orbitals are d_z² and d_xy, and the d_π orbitals are d_x²_−y², d_xz, and d_yz. From the calculation, the d_xz orbital was found to be the lowest among the five d-orbitals and to be filled with two electrons, whereas other four orbitals were found to be singly occupied. The energy level of the lowest d_xz orbital may look unusually low compared with the d-d separation in the octahedral coordination geometry, but this is normal because only this orbital is doubly occupied. The order of the d_σ orbitals were d_xy < d_z², and this is consistent with the tetragonal compression along the z axis. From the point of view of the crystal field theory, the splitting of the d_π orbitals is not so much because the tetragonal compression is very small in this case and the effect of the π orbitals is generally less than 10% of the σ orbital. The order of the calculated d_π orbitals were d_xz < d_x²_−y² < d_yz, and this seems to be consistent with the orientation of the dmso π orbitals arranged in the pseudo-S₆ symmetry. That is, the larger the overlap between the d-orbital and the dmso π orbitals, the higher in energy. Therefore, the electronic configuration becomes (d_xz)²(d_x²_−y²)¹(d_yz)¹(d_xy)¹(d_z²)¹, and this electronic configuration is consistent with the combination of the tetragonal compression and the orientation of the pseudo-S₆ symmetric dmso π orbital environment. The small orbital reduction factor (κ = 0.66), estimated from the magnetic data, was shown to be consistent with the significant interaction with the dmso π orbitals. Since the (d_xz, d_yz) orbitals in the tetragonally compressed D₄ coordination geometry were filled with three electrons, the ground state became ⁵E in the D₄ approximation. This is consistent with the negative Δ value found from the magnetic analysis.

2.4. Magneto-Structural Relationship

Now we discuss the magneto-structural relationship especially between the structure and the Δ value. In the crystal structure, the tetragonal compression was observed; however, the order of the d_π orbitals was found to be determined by the orientation of the dmso π orbitals, which was significantly influenced by the orientation of the dmso moieties. In this complex cation, the central iron(II) ion was surrounded by the pseudo-S₆ symmetric hexakis-dmso environment, and the combination of the tetragonal compression and the pseudo-S₆ environment was found to generate the d-orbital splitting in Figure 5, generating the electronic configuration of (d_xz)²(d_x²_−y²)¹(d_yz)¹(d_xy)¹(d_z²)¹. In the ideal D₄ symmetric coordination geometry due to the tetragonal-compression, the (d_xz, d_yz) orbitals are degenerate. However, in the (d_xz, d_yz) orbitals, the d_xz orbital becomes lower in energy due to the less overlap with the dmso π orbitals, and the (d_xz, d_yz) orbitals became filled with three electrons. This electronic configuration corresponded to the ⁵E ground state in the D₄ symmetric coordination geometry. The ⁵E ground state directly indicated the negative Δ value, which was consistent with the magnetic measurements. Judging from the negative sign of the Δ value, the magnetic anisotropy is considered to be uniaxial, and the tetragonal compression axis (z axis) is considered to be the easy axis.

In the case of the related cobalt(II) complex, [Co(dmso)₆][BPh₄]₂ [14], tetragonal elongation (along the z axis) was observed, and judging from the large orbital reduction factor, close to the free-ion value, the effect of the dmso π orbitals was thought to be smaller than that in the present iron(II) complex. The pseudo-degenerate (d_xz, d_yz) orbitals in the cobalt(II) complex were considered to be higher than the d_xy orbital, affording the ⁴E ground state. This leads to the negative Δ value and the easy-axis anisotropy along the z axis.

3. Materials and Methods

3.1. Materials and Methods

All the chemicals were commercial products and were used as supplied. Elemental analyses (C, H, and N) were obtained on Elemental Analyzers, Yanaco (Tokyo, Japan) CHN Corder MT-5 and MT-6, at the Elemental Analysis Service Centre of Kyushu University (Fukuoka, Japan). IR spectra were recorded on a JASCO (Tokyo, Japan) FT/IR-4100 FT-IR spectrometer. Differential scanning calorimetry (DSC) measurements were conducted on PerkinElmer DSC 8500 in the temperature range of 303–203 K at scan rate of 30, 10, 5, and 1 K/min. Magnetic susceptibility measurements were made on Quantum Design (San Diego, CA, USA) MPMS XL5min SQUID susceptometer with scan rates of 10.0 K /min for 40–300 K and 0.5 K/min 2–40 K at 0.3 T. The isothermal magnetization was measured on Quantum Design MPMS XL5min SQUID susceptometer at 2 K in an applied field of 0–5 T. The magnetic correction for the sample holder was performed by measurement for the empty capsule. The susceptibilities were corrected for the diamagnetism of the constituent atoms using Pascal’s constant.

3.2. Synthetic Procedures

[Fe(dmso)₆][BPh₄]₂ (1). Deoxygenated solvents were beforehand prepared by bubbling with nitrogen, and all operations were carried out under nitrogen. Iron(II) sulfate—water (1/7) (0.84 g, 3.0 mmol) was dissolved in hot water (1 mL), and to this was added dmso (3 mL) and 2-propanol solution (6 mL) of sodium tetraphenylborate (2.1 g, 6.1 mmol). The solution was refluxed for 20 min, and after the addition of 2-propanol (4 mL), the suspension was refluxed for 10 min to obtain white microcrystals. Recrystallized from hot dmso/2-propanol. Yield: 0.84 g (24%) (Found: C, 61.60; H, 6.45; Fe, 5.0%. Calc. for C₆₀H₇₆B₂FeO₆S₆ (1): C, 61.95; H, 6.60; Fe, 4.80%). Selected IR data [$\tilde{\mathrm{\nu }}$/cm⁻¹] using a KBr disk: 3055-2910, 1578, 1476, 1425, 1314, 1151, 1011, 998, 949, 740, 705, 611.

3.3. Crystallography

Colorless single-crystals suitable for X-ray analysis were obtained by slow diffusion of 2-propanol to a dmso solution of 1 under nitrogen. Single-crystal diffraction data were measured on a Rigaku (Tokyo, Japan) XtaLAB PRO MM007 diffractometer. The structure was solved by direct methods and expanded using Fourier techniques. The non-hydrogen atoms were refined anisotropically except for the disordered dmso ligand, and hydrogen atoms were refined using the riding model. The final cycle of full-matrix least squares refinement on F₂ was let to satisfactory converge with R₁ = 0.0327 [I > 2σ(I)]. Final R(F), wR(F₂), and goodness of fit agreement factors, as well as details on data collection and analysis are in Table 1.

3.4. Computations

Magnetic analyses and magnetic simulation were conducted using MagSaki(FeII, β0.2.3) program of MagSaki series. The DFT computations were performed using GAMESS program [21,22] on Fujitsu PRIMERGY CX2550/CX2560 M4 (ITO super computer system) at Kyushu University. Structural optimizations were conducted with LC-BOP/def2-tzvp [23,24,25].

4. Conclusions

The octahedral high-spin iron(II) complex [Fe(dmso)₆][BPh₄]₂ (1) was newly prepared, and the single-crystal X-ray diffraction method revealed the tetragonal compression of the D₄-symmetric coordination geometry around the iron(II) ion and the pseudo-S₆ hexakis-dmso environment. From the magnetic data, the sign of the axial splitting parameter, Δ, was found to be negative, indicating the ⁵E ground state in the D₄ symmetry. That is, the ⁵T₂ ground term in the O symmetry splits into ⁵E and ⁵B₂ terms in the D₄ symmetry, and the ⁵E term is lower in energy than the ⁵B₂ term. The DFT computation showed the electronic configuration of (d_xz)²(d_x²_−y²)¹(d_yz)¹(d_xy)¹(d_z²)¹ due to the tetragonal compression and the pseudo-S₆ environment of dmso π orbitals. The electronic configuration corresponded to the ⁵E ground term, which was in agreement with the negative Δ value. Therefore, the structurally predicted ground state was consistent with the estimation from the magnetic measurements.