Crystal structure of bis­(1-methyl-1H-imidazole-κN3)(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)iron(II) toluene tris­olvate

Ding, W.; He, M.; Li, J.

doi:10.1107/S2056989025007121

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Volume 81| Part 9| September 2025| Pages 832-835

https://doi.org/10.1107/S2056989025007121

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Crystal structure of bis(1-methyl-1H-imidazole-κN³)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)iron(II) toluene trisolvate

Wei Ding,^a ‡ Mingrui He ^b ‡ and Jianfeng Li ^c ^*

^aBeijing Spacecrafts Co., Ltd., Beijing 100094, People's Republic of China, ^bState Key Laboratory of Biopharmaceutical Preparation and Delivery, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, People's Republic of China, and ^cCollege of Materials Science and Opto-electronic Technology, University of Chinese Academy of Sciences, Huairou, Beijing 101408, People's Republic of China
^*Correspondence e-mail: [email protected]

Edited by J. Reibenspies, Texas A & M University, USA (Received 3 July 2025; accepted 7 August 2025; online 15 August 2025)

The title complex, [Fe(C₄H₆N₂)₂(C₄₄H₂₈N₄)]·3C₇H₈, possesses inversion symmetry with the iron(II) atom located on a center of symmetry. The metal atom is coordinated in a symmetric octahedral geometry by four pyrrole N atoms of the porphyrin ligand in the equatorial plane and two N atoms of 1-methylimidazole ligands in the axial sites; the complex crystallizes with three toluene solvent molecules. The average Fe—N_P (N_P is a porphyrin N atom) bond length is 1.994 (3) Å and the axial Fe—N_Im (N_Im is an imidazole N atom) bond length is 2.0000 (14) Å. The two 1-methylimidazole ligands are mutually parallel. The dihedral angle between the 1-methylimidazole plane and the plane of the closest Fe—N_P vector is 25.54 (10)°. In the crystal, the only significant intermolecular interactions present are C—H⋯π interactions.

Keywords: crystal structure; C—H⋯π interaction; 1-methylimidazole; iron.

CCDC reference: 2478878

1. Chemical context

Cytochrome c oxidases (CcO), a superfamily of proteins, are particularly important in catalyzing O₂ into water (Ferguson-Miller & Babcock, 1996 ; Michel et al., 1998 ; Babcock & Wikstrom, 1992 ). The best-conserved subunit (subunit I) in CcO contains two heme centers (Michel et al., 1998). The first heme, which is low-spin and bis-histidine coordinated, acts as an electron-input device to the second (Pitcher & Watmough, 2004 ). The second heme (heme a₃), which is binuclear with a Cu (Cu_B) as the other metal, is the site of oxygen reduction. Porphyrin models for both catalytic heme centers have been developed and investigated (Walker, 2004 ; Collman et al., 2003 , 2004 ; Nakamura, 2006 ; Ide et al., 2017 ; Ikeue et al., 2011 ; Kim et al., 2004 ). For the bis-histidine coordinated heme, both ferrous and ferric [Fe^II,III(Porph)(L)₂]^0,+ (L: planar N-donor ligand) complexes have been studied to understand the correlation between the crystal structures and the spectroscopic properties. Compared to the extensively studied ferric [Fe^III(Porph)(L)₂]⁺, reports on ferrous [Fe^II(Porph)(L)₂]⁰ complexes are less common. For d⁶ Fe^II porphyrin species, it has been presumed that the axial ligands would align themselves perpendicularly to maximize the π-bonding between the π* orbitals of the ligands and the filled dπ orbitals of Fe^II (Li et al., 2008 ). The first structurally characterized iron(II) bis-imidazole porphyrinate, [Fe(TPP)(1-MeIm)₂], which was personally communicated (Steffen et al., 1978 ), however, showed parallel imidazole orientation with a required symmetry of an inversion center at the iron atom and thus a near planar porphyrin plane (Hu, Roth et al., 2005 ). An iron(II) porphyrin complex with mutually perpendicular ligand orientation was eventually achieved in 2005 by using the hindered axial ligands, i.e. [Fe(TMP)(2-MeHIm)₂] (Hu, Noll, et al., 2005 ). The crystal structure showed a very ruffled porphyrin core, and the Mössbauer spectra showed a large ΔE_Q of ∼1.7 mm s⁻¹ (Hu, Noll, et al., 2005). These geometric and Mössbauer properties are in sharp contrast to those of [Fe(Porph)(1-MeIm)₂] analogues, which showed parallel ligand orientations, near planar porphyrin plane, and ΔE_Q of ∼1.1 mm s⁻¹.

Herein, we report the structural properties of the iron(II) porphyrin complex [Fe^II(TPP)(1-MeIm)₂]·3(C₇H₈) in which the metal center is octahedrally coordinated. Apart from the informally reported [Fe(TPP)(1-MeIm)₂] (Steffen et al., 1978), a similar [(Fe(TPP)(1-MeIm)₂]·2(1-MeIm) where all the 1-MeIm molecules (un)bound to iron were disordered has been reported (Guan et al., 2015 )

2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) contains half of an Fe^II porphyrin complex with the iron(II) atom located on an inversion center, one axial 1-methylimidazole ligand, as well as one full and one-half toluene solvent molecules. The second toluene was refined at ∼44% and was fixed at 50% occupancy in the final refinement. The two 1-methylimidazole ligands of the [Fe^II(TPP)(1-MeIm)₂] are mutually parallel, as required by crystallographic symmetry. Additional quantitative information about the structure is displayed in Fig. 2, which includes the displacement of each porphyrin core atom (in units of 0.01 Å) from the 24-atom mean plane. The orientation of the 1-methylimidazole ligand, including the value of the dihedral angles, is also given. As can be seen in Fig. 2, the porphyrin core of [Fe(II)(TPP)(1-MeIm)₂] is near-planar, and the iron(II) atom sits in the 24-atom plane. The displacement of every porphyrin core atom is ≤ 0.03 Å. The average Fe—N_P bond length of 1.994 (3) Å is similar to 1.993 (6) Å for [Fe^II(TpivPP)(1-EtIm)₂] (Li et al., 2008) and 1.994 (10) Å for [Fe^II(TFPPBr₂)(1-EtIm)₂] (Hu et al., 2016 ), which are typical values for six-coordinate low-spin (porphinato)iron(II) derivatives (Scheidt et al., 1981 ). The axial Fe—N_Im bond length is 2.0000 (14) Å, comparable to 1.9970 (12) Å in [(Fe(TPP)(1-MeIm)₂]·2(1-MeIm) (Guan et al., 2015). The average N_P—Fe—N_P angle is ideal at 90.0 (4)°. The dihedral angle between the 1-methylimidazole plane and the plane of the closest Fe—N_P vector is 25.54 (10)°.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Formal diagram of the porphyrinate core of [Fe^II(TPP)(1-MeIm)₂]. Averaged values of the chemically unique bond distances (in Å) and angles (in degrees) are shown. The numbers in parentheses are the esds calculated on the assumption that the averaged values were all drawn from the same population. The perpendicular displacements (in units of 0.01Å) of the porphyrin core atoms from the 24-atom mean plane are also displayed. Positive values of the displacement are towards the hindered porphyrin side, the solid line and dashed line indicate the plane of imidazole on the unhindered porphyrin side.

3. Supramolecular features

In the title compound, as shown in Fig. 3, the distance between the hydrogen atom H4C (C4) of the methyl group of 1-MeIm and the pyrrole plane of the neighboring porphyrin [the N2, C(A3, C(B3, C(B4, C(A4 ring] is 2.64 (4) Å, smaller than 2.9 Å, which is a limit suggested for the existence of a C—H⋯π interaction interaction (Takahashi et al., 2001 ). Details of this interaction are given in Table 1. The molecular packing is shown in Fig. 4.

Table 1
C—H⋯π interaction geometry (Å, °)

Cg is the centroid of the N2, C(A3, C(B3, C(B4, C(A4 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4C⋯Cgⁱ	0.95 (2)	2.64 (3)	3.408 (2)	137.7 (17)
Symmetry code: (i) .

Figure 3
The C—H⋯π interactions in the title compound. Dashed lines show the distances between hydrogen atoms of 1-methylimidazole and the pyrrole core planes. Solvent (toluene) molecules and other hydrogen atoms have been omitted for clarity.

Figure 4
A view of the molecular packing of the title compound in the crystal structure. Hydrogen atoms have been omitted for clarity.

4. Synthesis and crystallization

4.1. General information

All reactions were carried out using standard Schlenk techniques under argon unless otherwise noted. Toluene and benzene were distilled over sodium, hexanes over potassium–sodium alloy and dichloromethane (CH₂Cl₂) over calcium hydride.

4.2. Synthesis of bis(1-methyl-1H-imidazole-κN³)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)iron(II) toluene trisolvate

The purple powder [Fe(TPP)]₂O (15.9 mg, 0.0234 mmol) was dried in a vacuum for 1h in a Schlenk tube. Benzene (∼5 mL) was transferred into the Schlenk tube by cannula and ethanethiol (∼2 mL) was added via syringe. The mixture was stirred under argon at ambient temperature. After 36 h, the reduction was completed and the solvent was evaporated by pump. Toluene (∼5 mL) was transferred into a Schlenk tube via cannula, and 1-MeIm (∼0.5 mL) was added via syringe. Hexanes were then allowed to diffuse slowly into the reaction solution. Several weeks later, the block-shaped crystalline product was collected.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically (0.95 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Fe(C₄H₆N₂)₂(C₄₄H₂₈N₄)]·3C₇H₈
M_r	1109.17
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.9075 (4), 10.8001 (5), 15.7095 (8)
α, β, γ (°)	78.759 (2), 81.631 (1), 76.356 (1)
V (Å³)	1432.58 (12)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.19 × 0.05

Data collection
Diffractometer	Brucker D8 QUEST System
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.930, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	30552, 5860, 4702
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.095, 1.05
No. of reflections	5860
No. of parameters	403
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.52
Computer programs: APEX2, SAINT, XPREP, XP and XCIF (Bruker, 2013 ), SHELXT2014/6 (Sheldrick, 2015a ), SHELXL2014/6 (Sheldrick, 2015b ) and enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 2478878

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025007121/jy2063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025007121/jy2063Isup3.hkl

checkCIF report

Computing details top

Bis(1-methyl-1H-imidazole-κN³)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)iron(II) toluene trisolvate top

Crystal data top

[Fe(C₄H₆N₂)₂(C₄₄H₂₈N₄)]·3C₇H₈	Z = 1
M_r = 1109.17	F(000) = 584
Triclinic, P1	D_x = 1.286 Mg m⁻³
a = 8.9075 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8001 (5) Å	Cell parameters from 9832 reflections
c = 15.7095 (8) Å	θ = 2.2–26.4°
α = 78.759 (2)°	µ = 0.32 mm⁻¹
β = 81.631 (1)°	T = 100 K
γ = 76.356 (1)°	Block, purple
V = 1432.58 (12) Å³	0.30 × 0.19 × 0.05 mm

Data collection top

Brucker D8 QUEST System diffractometer	4702 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.063
φ and ω scans	θ_max = 26.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.930, T_max = 0.984	k = −13→13
30552 measured reflections	l = −19→19
5860 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0323P)² + 1.1455P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
5860 reflections	Δρ_max = 0.35 e Å⁻³
403 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.500000	0.000000	0.000000	0.00883 (10)
N1	0.47642 (16)	−0.09968 (14)	0.12018 (10)	0.0105 (3)
N2	0.37571 (16)	0.16048 (14)	0.04180 (9)	0.0098 (3)
N3	0.69083 (16)	0.04655 (14)	0.02624 (10)	0.0113 (3)
N4	0.86999 (17)	0.15783 (14)	0.02447 (10)	0.0132 (3)
C(A1	0.5336 (2)	−0.22972 (17)	0.14810 (12)	0.0119 (4)
C(A2	0.3964 (2)	−0.05378 (17)	0.19379 (12)	0.0121 (4)
C(A3	0.31083 (19)	0.17303 (17)	0.12577 (12)	0.0110 (4)
C(A4	0.34227 (19)	0.28360 (16)	−0.00590 (11)	0.0099 (4)
C(B1	0.4892 (2)	−0.26427 (18)	0.24014 (12)	0.0153 (4)
H(BD	0.514690	−0.347544	0.274557	0.018*
C(B2	0.4046 (2)	−0.15590 (17)	0.26806 (12)	0.0154 (4)
H(BC	0.358960	−0.148416	0.325887	0.019*
C(B3	0.2340 (2)	0.30540 (17)	0.13036 (12)	0.0131 (4)
H(BB	0.179863	0.338354	0.180716	0.016*
C(B4	0.2537 (2)	0.37342 (17)	0.04928 (12)	0.0129 (4)
H(BA	0.216325	0.463512	0.031846	0.015*
C(M1	0.3196 (2)	0.07365 (17)	0.19732 (12)	0.0124 (4)
C(M2	0.38241 (19)	0.31732 (16)	−0.09500 (12)	0.0106 (4)
C1	0.7894 (2)	−0.01666 (17)	0.08864 (12)	0.0138 (4)
H1A	0.781054	−0.095491	0.126425	0.017*
C2	0.7435 (2)	0.15140 (17)	−0.01067 (12)	0.0130 (4)
H2A	0.697834	0.214163	−0.056207	0.016*
C3	0.9003 (2)	0.05152 (18)	0.08763 (12)	0.0155 (4)
H3A	0.982582	0.029450	0.123762	0.019*
C4	0.9546 (2)	0.2618 (2)	0.00219 (15)	0.0186 (4)
H4A	0.933 (3)	0.306 (2)	−0.0580 (16)	0.028 (6)*
H4B	0.921 (3)	0.322 (2)	0.0432 (15)	0.028 (6)*
H4C	1.062 (3)	0.223 (2)	0.0037 (15)	0.030 (6)*
C5	0.2435 (2)	0.10492 (17)	0.28448 (12)	0.0150 (4)
C6	0.3167 (3)	0.1595 (2)	0.33512 (14)	0.0291 (5)
H6A	0.416121	0.177704	0.314372	0.035*
C7	0.2459 (3)	0.1879 (2)	0.41611 (15)	0.0368 (6)
H7A	0.297289	0.225417	0.450103	0.044*
C8	0.1021 (3)	0.1619 (2)	0.44731 (14)	0.0284 (5)
H8A	0.053948	0.181660	0.502528	0.034*
C9	0.0285 (2)	0.1071 (2)	0.39775 (14)	0.0257 (5)
H9A	−0.070619	0.088624	0.418934	0.031*
C10	0.0989 (2)	0.0788 (2)	0.31692 (13)	0.0209 (4)
H10A	0.047190	0.040844	0.283323	0.025*
C11	0.3376 (2)	0.45610 (17)	−0.13678 (11)	0.0115 (4)
C12	0.2191 (2)	0.49692 (17)	−0.19150 (12)	0.0146 (4)
H12A	0.163160	0.436903	−0.201010	0.018*
C13	0.1824 (2)	0.62492 (18)	−0.23217 (12)	0.0169 (4)
H13A	0.102160	0.651872	−0.269763	0.020*
C14	0.2623 (2)	0.71339 (18)	−0.21817 (12)	0.0173 (4)
H14A	0.236944	0.800821	−0.246156	0.021*
C15	0.3795 (2)	0.67427 (18)	−0.16324 (13)	0.0174 (4)
H15A	0.434025	0.734932	−0.153191	0.021*
C16	0.4168 (2)	0.54630 (17)	−0.12304 (12)	0.0153 (4)
H16A	0.497417	0.519748	−0.085648	0.018*
C1SB	0.7609 (3)	0.8872 (2)	0.32950 (17)	0.0425 (6)
H23A	0.673860	0.873752	0.373637	0.064*
H23B	0.812557	0.949129	0.345084	0.064*
H23C	0.721977	0.921204	0.272446	0.064*
C2SB	0.8751 (3)	0.7605 (2)	0.32540 (15)	0.0342 (6)
C3SB	0.8474 (4)	0.6483 (2)	0.38067 (16)	0.0424 (7)
H18A	0.754871	0.652034	0.419631	0.051*
C4SB	0.9527 (4)	0.5323 (3)	0.37932 (17)	0.0490 (8)
H19A	0.933230	0.456915	0.417786	0.059*
C5SB	1.0869 (3)	0.5256 (3)	0.32193 (19)	0.0465 (7)
H20A	1.159488	0.445668	0.321101	0.056*
C6SB	1.1151 (3)	0.6351 (3)	0.26591 (19)	0.0457 (7)
H21A	1.206433	0.630454	0.225956	0.055*
C7SB	1.0101 (3)	0.7512 (2)	0.26824 (18)	0.0404 (6)
H22A	1.030608	0.826308	0.229888	0.048*
C1SA	0.6379 (7)	0.2791 (6)	0.4655 (4)	0.0481 (15)	0.5
H1S1	0.716863	0.239817	0.505858	0.072*	0.5
H1S2	0.565505	0.221984	0.469878	0.072*	0.5
H1S3	0.688444	0.292076	0.405691	0.072*	0.5
C2SA	0.5491 (4)	0.4093 (2)	0.4890 (2)	0.0299 (11)	0.5
C3SA	0.4311 (5)	0.4818 (3)	0.4397 (2)	0.0337 (16)	0.5
H3SA	0.408661	0.451358	0.391152	0.040*	0.5
C4SA	0.3458 (4)	0.5989 (3)	0.4614 (3)	0.0414 (14)	0.5
H4SA	0.265082	0.648485	0.427675	0.050*	0.5
C5SA	0.3785 (4)	0.6435 (3)	0.5324 (3)	0.0426 (15)	0.5
H5SA	0.320248	0.723487	0.547244	0.051*	0.5
C6SA	0.4966 (5)	0.5709 (4)	0.5817 (2)	0.0405 (14)	0.5
H6SA	0.518992	0.601363	0.630291	0.049*	0.5
C7SA	0.5819 (4)	0.4538 (3)	0.5601 (2)	0.0309 (15)	0.5
H7SA	0.662573	0.404235	0.593768	0.037*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.00937 (18)	0.00819 (18)	0.0094 (2)	−0.00260 (14)	−0.00160 (14)	−0.00121 (14)
N1	0.0104 (7)	0.0096 (7)	0.0118 (8)	−0.0021 (6)	−0.0020 (6)	−0.0020 (6)
N2	0.0096 (7)	0.0105 (7)	0.0102 (8)	−0.0041 (6)	−0.0020 (6)	−0.0007 (6)
N3	0.0106 (7)	0.0105 (7)	0.0128 (8)	−0.0012 (6)	−0.0004 (6)	−0.0034 (6)
N4	0.0105 (7)	0.0119 (8)	0.0189 (8)	−0.0032 (6)	−0.0015 (6)	−0.0056 (6)
C(A1	0.0104 (8)	0.0113 (9)	0.0143 (9)	−0.0036 (7)	−0.0043 (7)	0.0007 (7)
C(A2	0.0128 (9)	0.0119 (9)	0.0124 (9)	−0.0049 (7)	−0.0018 (7)	−0.0010 (7)
C(A3	0.0100 (8)	0.0115 (9)	0.0131 (9)	−0.0044 (7)	−0.0010 (7)	−0.0035 (7)
C(A4	0.0088 (8)	0.0094 (8)	0.0125 (9)	−0.0029 (7)	−0.0035 (7)	−0.0013 (7)
C(B1	0.0180 (9)	0.0130 (9)	0.0142 (10)	−0.0043 (7)	−0.0033 (7)	0.0015 (7)
C(B2	0.0188 (10)	0.0149 (9)	0.0112 (9)	−0.0032 (8)	0.0002 (7)	−0.0006 (7)
C(B3	0.0130 (9)	0.0123 (9)	0.0148 (10)	−0.0026 (7)	−0.0011 (7)	−0.0046 (7)
C(B4	0.0122 (9)	0.0091 (8)	0.0182 (10)	−0.0026 (7)	−0.0034 (7)	−0.0029 (7)
C(M1	0.0129 (9)	0.0141 (9)	0.0116 (9)	−0.0044 (7)	−0.0015 (7)	−0.0034 (7)
C(M2	0.0088 (8)	0.0096 (8)	0.0147 (9)	−0.0033 (7)	−0.0050 (7)	−0.0004 (7)
C1	0.0151 (9)	0.0131 (9)	0.0129 (9)	−0.0014 (7)	−0.0040 (7)	−0.0012 (7)
C2	0.0118 (9)	0.0110 (9)	0.0167 (10)	−0.0026 (7)	−0.0026 (7)	−0.0022 (7)
C3	0.0138 (9)	0.0169 (9)	0.0161 (10)	0.0004 (7)	−0.0060 (7)	−0.0050 (8)
C4	0.0137 (10)	0.0177 (10)	0.0268 (12)	−0.0071 (8)	−0.0016 (8)	−0.0058 (9)
C5	0.0222 (10)	0.0092 (9)	0.0106 (9)	0.0001 (7)	−0.0012 (7)	0.0004 (7)
C6	0.0392 (13)	0.0352 (13)	0.0193 (11)	−0.0213 (11)	0.0050 (10)	−0.0095 (10)
C7	0.0580 (16)	0.0420 (14)	0.0202 (12)	−0.0271 (12)	0.0030 (11)	−0.0138 (11)
C8	0.0450 (14)	0.0231 (11)	0.0136 (11)	−0.0051 (10)	0.0062 (9)	−0.0045 (9)
C9	0.0230 (11)	0.0274 (11)	0.0195 (11)	0.0019 (9)	0.0033 (8)	0.0003 (9)
C10	0.0195 (10)	0.0260 (11)	0.0160 (10)	−0.0025 (8)	−0.0016 (8)	−0.0040 (8)
C11	0.0126 (9)	0.0107 (9)	0.0104 (9)	−0.0016 (7)	0.0001 (7)	−0.0019 (7)
C12	0.0140 (9)	0.0133 (9)	0.0174 (10)	−0.0031 (7)	−0.0031 (7)	−0.0035 (7)
C13	0.0187 (10)	0.0147 (9)	0.0152 (10)	−0.0001 (8)	−0.0045 (8)	0.0002 (8)
C14	0.0235 (10)	0.0097 (9)	0.0153 (10)	−0.0016 (8)	0.0019 (8)	0.0004 (7)
C15	0.0221 (10)	0.0124 (9)	0.0193 (10)	−0.0084 (8)	0.0004 (8)	−0.0029 (8)
C16	0.0156 (9)	0.0149 (9)	0.0164 (10)	−0.0049 (7)	−0.0029 (7)	−0.0022 (8)
C1SB	0.0585 (17)	0.0388 (15)	0.0346 (15)	−0.0166 (13)	−0.0153 (12)	−0.0015 (11)
C2SB	0.0528 (15)	0.0299 (12)	0.0282 (13)	−0.0181 (11)	−0.0211 (11)	−0.0011 (10)
C3SB	0.0758 (19)	0.0377 (14)	0.0229 (13)	−0.0234 (14)	−0.0135 (12)	−0.0067 (11)
C4SB	0.096 (2)	0.0317 (14)	0.0292 (14)	−0.0231 (15)	−0.0279 (15)	−0.0003 (11)
C5SB	0.0588 (18)	0.0398 (15)	0.0492 (17)	−0.0079 (13)	−0.0344 (15)	−0.0096 (13)
C6SB	0.0399 (15)	0.0502 (17)	0.0541 (18)	−0.0137 (13)	−0.0221 (13)	−0.0081 (14)
C7SB	0.0460 (15)	0.0368 (14)	0.0443 (16)	−0.0222 (12)	−0.0188 (12)	0.0056 (12)
C1SA	0.048 (3)	0.049 (4)	0.041 (3)	0.000 (3)	0.009 (3)	−0.016 (3)
C2SA	0.028 (3)	0.038 (3)	0.023 (3)	−0.015 (2)	0.001 (2)	0.003 (2)
C3SA	0.041 (4)	0.041 (5)	0.021 (3)	−0.023 (4)	−0.006 (2)	0.011 (3)
C4SA	0.040 (3)	0.046 (4)	0.033 (3)	−0.012 (3)	−0.002 (3)	0.008 (3)
C5SA	0.043 (4)	0.031 (3)	0.043 (4)	−0.003 (3)	0.011 (3)	−0.001 (3)
C6SA	0.040 (3)	0.049 (4)	0.033 (3)	−0.014 (3)	0.003 (3)	−0.009 (3)
C7SA	0.029 (3)	0.042 (5)	0.021 (3)	−0.015 (3)	0.002 (2)	0.003 (3)

Geometric parameters (Å, º) top

Fe1—N1	1.9915 (15)	C8—H8A	0.9500
Fe1—N1ⁱ	1.9916 (15)	C9—C10	1.389 (3)
Fe1—N2ⁱ	1.9969 (14)	C9—H9A	0.9500
Fe1—N2	1.9969 (14)	C10—H10A	0.9500
Fe1—N3ⁱ	2.0000 (14)	C11—C12	1.394 (2)
Fe1—N3	2.0000 (14)	C11—C16	1.394 (2)
N1—C(A2	1.381 (2)	C12—C13	1.389 (3)
N1—C(A1	1.383 (2)	C12—H12A	0.9500
N2—C(A3	1.380 (2)	C13—C14	1.384 (3)
N2—C(A4	1.381 (2)	C13—H13A	0.9500
N3—C2	1.325 (2)	C14—C15	1.387 (3)
N3—C1	1.380 (2)	C14—H14A	0.9500
N4—C2	1.346 (2)	C15—C16	1.387 (3)
N4—C3	1.365 (2)	C15—H15A	0.9500
N4—C4	1.456 (2)	C16—H16A	0.9500
C(A1—C(M2ⁱ	1.394 (2)	C1SB—C2SB	1.507 (4)
C(A1—C(B1	1.442 (3)	C1SB—H23A	0.9800
C(A2—C(M1	1.393 (2)	C1SB—H23B	0.9800
C(A2—C(B2	1.438 (3)	C1SB—H23C	0.9800
C(A3—C(M1	1.392 (3)	C2SB—C7SB	1.388 (4)
C(A3—C(B3	1.443 (2)	C2SB—C3SB	1.397 (3)
C(A4—C(M2	1.392 (2)	C3SB—C4SB	1.379 (4)
C(A4—C(B4	1.443 (2)	C3SB—H18A	0.9500
C(B1—C(B2	1.348 (3)	C4SB—C5SB	1.385 (4)
C(B1—H(BD	0.9500	C4SB—H19A	0.9500
C(B2—H(BC	0.9500	C5SB—C6SB	1.380 (4)
C(B3—C(B4	1.351 (3)	C5SB—H20A	0.9500
C(B3—H(BB	0.9500	C6SB—C7SB	1.380 (4)
C(B4—H(BA	0.9500	C6SB—H21A	0.9500
C(M1—C5	1.500 (2)	C7SB—H22A	0.9500
C(M2—C11	1.499 (2)	C1SA—C2SA	1.526 (6)
C1—C3	1.361 (3)	C1SA—H1S1	0.9800
C1—H1A	0.9500	C1SA—H1S2	0.9800
C2—H2A	0.9500	C1SA—H1S3	0.9800
C3—H3A	0.9500	C2SA—C3SA	1.3900
C4—H4A	1.00 (2)	C2SA—C7SA	1.3900
C4—H4B	0.97 (2)	C3SA—C4SA	1.3900
C4—H4C	0.95 (2)	C3SA—H3SA	0.9500
C5—C6	1.386 (3)	C4SA—C5SA	1.3900
C5—C10	1.386 (3)	C4SA—H4SA	0.9500
C6—C7	1.392 (3)	C5SA—C6SA	1.3900
C6—H6A	0.9500	C5SA—H5SA	0.9500
C7—C8	1.376 (3)	C6SA—C7SA	1.3900
C7—H7A	0.9500	C6SA—H6SA	0.9500
C8—C9	1.377 (3)	C7SA—H7SA	0.9500

N1—Fe1—N2	90.33 (6)	C7—C8—H8A	120.3
N1ⁱ—Fe1—N2	89.67 (6)	C9—C8—H8A	120.3
N2ⁱ—Fe1—N2	180.0	C8—C9—C10	120.2 (2)
N1—Fe1—N3	90.34 (6)	C8—C9—H9A	119.9
N1ⁱ—Fe1—N3	89.66 (6)	C10—C9—H9A	119.9
N2ⁱ—Fe1—N3	91.77 (6)	C5—C10—C9	121.03 (19)
N2—Fe1—N3	88.23 (6)	C5—C10—H10A	119.5
N3ⁱ—Fe1—N3	180.0	C9—C10—H10A	119.5
C(A2—N1—C(A1	104.88 (14)	C12—C11—C16	118.79 (16)
C(A2—N1—Fe1	127.23 (12)	C12—C11—C(M2	120.94 (15)
C(A1—N1—Fe1	127.89 (12)	C16—C11—C(M2	120.25 (16)
C(A3—N2—C(A4	105.18 (14)	C13—C12—C11	120.32 (17)
C(A3—N2—Fe1	127.17 (12)	C13—C12—H12A	119.8
C(A4—N2—Fe1	127.59 (12)	C11—C12—H12A	119.8
C2—N3—C1	105.36 (15)	C14—C13—C12	120.30 (17)
C2—N3—Fe1	126.00 (12)	C14—C13—H13A	119.9
C1—N3—Fe1	128.53 (12)	C12—C13—H13A	119.9
C2—N4—C3	107.28 (15)	C13—C14—C15	119.95 (17)
C2—N4—C4	126.43 (16)	C13—C14—H14A	120.0
C3—N4—C4	126.24 (16)	C15—C14—H14A	120.0
N1—C(A1—C(M2ⁱ	125.38 (16)	C16—C15—C14	119.77 (17)
N1—C(A1—C(B1	110.47 (15)	C16—C15—H15A	120.1
C(M2ⁱ—C(A1—C(B1	124.11 (16)	C14—C15—H15A	120.1
N1—C(A2—C(M1	125.52 (16)	C15—C16—C11	120.86 (17)
N1—C(A2—C(B2	110.63 (15)	C15—C16—H16A	119.6
C(M1—C(A2—C(B2	123.85 (17)	C11—C16—H16A	119.6
N2—C(A3—C(M1	125.50 (16)	C2SB—C1SB—H23A	109.5
N2—C(A3—C(B3	110.59 (15)	C2SB—C1SB—H23B	109.5
C(M1—C(A3—C(B3	123.90 (16)	H23A—C1SB—H23B	109.5
N2—C(A4—C(M2	125.60 (16)	C2SB—C1SB—H23C	109.5
N2—C(A4—C(B4	110.28 (15)	H23A—C1SB—H23C	109.5
C(M2—C(A4—C(B4	124.08 (16)	H23B—C1SB—H23C	109.5
C(B2—C(B1—C(A1	106.95 (16)	C7SB—C2SB—C3SB	118.1 (2)
C(B2—C(B1—H(BD	126.5	C7SB—C2SB—C1SB	121.9 (2)
C(A1—C(B1—H(BD	126.5	C3SB—C2SB—C1SB	120.1 (2)
C(B1—C(B2—C(A2	107.07 (16)	C4SB—C3SB—C2SB	120.8 (3)
C(B1—C(B2—H(BC	126.5	C4SB—C3SB—H18A	119.6
C(A2—C(B2—H(BC	126.5	C2SB—C3SB—H18A	119.6
C(B4—C(B3—C(A3	106.78 (16)	C3SB—C4SB—C5SB	120.0 (3)
C(B4—C(B3—H(BB	126.6	C3SB—C4SB—H19A	120.0
C(A3—C(B3—H(BB	126.6	C5SB—C4SB—H19A	120.0
C(B3—C(B4—C(A4	107.16 (16)	C6SB—C5SB—C4SB	120.0 (3)
C(B3—C(B4—H(BA	126.4	C6SB—C5SB—H20A	120.0
C(A4—C(B4—H(BA	126.4	C4SB—C5SB—H20A	120.0
C(A3—C(M1—C(A2	124.24 (17)	C7SB—C6SB—C5SB	119.7 (3)
C(A3—C(M1—C5	118.42 (16)	C7SB—C6SB—H21A	120.2
C(A2—C(M1—C5	117.33 (16)	C5SB—C6SB—H21A	120.2
C(A4—C(M2—C11	118.82 (15)	C6SB—C7SB—C2SB	121.4 (2)
C(A1ⁱ—C(M2—C11	117.40 (16)	C6SB—C7SB—H22A	119.3
C3—C1—N3	109.40 (16)	C2SB—C7SB—H22A	119.3
C3—C1—H1A	125.3	C2SA—C1SA—H1S1	109.5
N3—C1—H1A	125.3	C2SA—C1SA—H1S2	109.5
N3—C2—N4	111.47 (16)	H1S1—C1SA—H1S2	109.5
N3—C2—H2A	124.3	C2SA—C1SA—H1S3	109.5
N4—C2—H2A	124.3	H1S1—C1SA—H1S3	109.5
C1—C3—N4	106.49 (16)	H1S2—C1SA—H1S3	109.5
C1—C3—H3A	126.8	C3SA—C2SA—C7SA	120.0
N4—C3—H3A	126.8	C3SA—C2SA—C1SA	119.0 (4)
N4—C4—H4A	107.0 (13)	C7SA—C2SA—C1SA	121.0 (4)
N4—C4—H4B	110.5 (13)	C4SA—C3SA—C2SA	120.0
H4A—C4—H4B	110.6 (18)	C4SA—C3SA—H3SA	120.0
N4—C4—H4C	107.0 (14)	C2SA—C3SA—H3SA	120.0
H4A—C4—H4C	110.6 (19)	C3SA—C4SA—C5SA	120.0
H4B—C4—H4C	111.1 (19)	C3SA—C4SA—H4SA	120.0
C6—C5—C10	118.25 (18)	C5SA—C4SA—H4SA	120.0
C6—C5—C(M1	120.81 (17)	C6SA—C5SA—C4SA	120.0
C10—C5—C(M1	120.94 (17)	C6SA—C5SA—H5SA	120.0
C5—C6—C7	120.6 (2)	C4SA—C5SA—H5SA	120.0
C5—C6—H6A	119.7	C5SA—C6SA—C7SA	120.0
C7—C6—H6A	119.7	C5SA—C6SA—H6SA	120.0
C8—C7—C6	120.5 (2)	C7SA—C6SA—H6SA	120.0
C8—C7—H7A	119.7	C6SA—C7SA—C2SA	120.0
C6—C7—H7A	119.7	C6SA—C7SA—H7SA	120.0
C7—C8—C9	119.4 (2)	C2SA—C7SA—H7SA	120.0

C(A2—N1—C(A1—C(M2ⁱ	177.45 (16)	N3—C1—C3—N4	0.2 (2)
Fe1—N1—C(A1—C(M2ⁱ	−1.5 (2)	C2—N4—C3—C1	0.0 (2)
C(A2—N1—C(A1—C(B1	−0.38 (18)	C4—N4—C3—C1	177.35 (17)
Fe1—N1—C(A1—C(B1	−179.34 (12)	C(A3—C(M1—C5—C6	−80.8 (2)
C(A1—N1—C(A2—C(M1	179.45 (17)	C(A2—C(M1—C5—C6	98.5 (2)
Fe1—N1—C(A2—C(M1	−1.6 (3)	C(A3—C(M1—C5—C10	99.9 (2)
C(A1—N1—C(A2—C(B2	0.27 (19)	C(A2—C(M1—C5—C10	−80.8 (2)
Fe1—N1—C(A2—C(B2	179.25 (11)	C10—C5—C6—C7	−0.4 (3)
C(A4—N2—C(A3—C(M1	−178.01 (16)	C(M1—C5—C6—C7	−179.7 (2)
Fe1—N2—C(A3—C(M1	−0.7 (2)	C5—C6—C7—C8	0.1 (4)
C(A4—N2—C(A3—C(B3	0.82 (18)	C6—C7—C8—C9	0.2 (4)
Fe1—N2—C(A3—C(B3	178.13 (11)	C7—C8—C9—C10	−0.2 (3)
C(A3—N2—C(A4—C(M2	−178.57 (16)	C6—C5—C10—C9	0.4 (3)
Fe1—N2—C(A4—C(M2	4.1 (2)	C(M1—C5—C10—C9	179.71 (18)
C(A3—N2—C(A4—C(B4	−0.68 (18)	C8—C9—C10—C5	−0.1 (3)
Fe1—N2—C(A4—C(B4	−177.98 (11)	C(A4—C(M2—C11—C12	−107.6 (2)
N1—C(A1—C(B1—C(B2	0.3 (2)	C(A1ⁱ—C(M2—C11—C12	74.1 (2)
C(M2ⁱ—C(A1—C(B1—C(B2	−177.51 (17)	C(A4—C(M2—C11—C16	73.9 (2)
C(A1—C(B1—C(B2—C(A2	−0.2 (2)	C(A1ⁱ—C(M2—C11—C16	−104.3 (2)
N1—C(A2—C(B2—C(B1	−0.1 (2)	C16—C11—C12—C13	0.7 (3)
C(M1—C(A2—C(B2—C(B1	−179.26 (17)	C(M2—C11—C12—C13	−177.76 (17)
N2—C(A3—C(B3—C(B4	−0.7 (2)	C11—C12—C13—C14	−0.5 (3)
C(M1—C(A3—C(B3—C(B4	178.19 (16)	C12—C13—C14—C15	−0.1 (3)
C(A3—C(B3—C(B4—C(A4	0.21 (19)	C13—C14—C15—C16	0.5 (3)
N2—C(A4—C(B4—C(B3	0.29 (19)	C14—C15—C16—C11	−0.3 (3)
C(M2—C(A4—C(B4—C(B3	178.22 (16)	C12—C11—C16—C15	−0.3 (3)
N2—C(A3—C(M1—C(A2	0.1 (3)	C(M2—C11—C16—C15	178.17 (17)
C(B3—C(A3—C(M1—C(A2	−178.55 (16)	C7SB—C2SB—C3SB—C4SB	1.1 (3)
N2—C(A3—C(M1—C5	179.32 (16)	C1SB—C2SB—C3SB—C4SB	−178.3 (2)
C(B3—C(A3—C(M1—C5	0.6 (3)	C2SB—C3SB—C4SB—C5SB	−0.9 (4)
N1—C(A2—C(M1—C(A3	1.1 (3)	C3SB—C4SB—C5SB—C6SB	−0.1 (4)
C(B2—C(A2—C(M1—C(A3	−179.87 (17)	C4SB—C5SB—C6SB—C7SB	0.8 (4)
N1—C(A2—C(M1—C5	−178.14 (16)	C5SB—C6SB—C7SB—C2SB	−0.5 (4)
C(B2—C(A2—C(M1—C5	0.9 (3)	C3SB—C2SB—C7SB—C6SB	−0.4 (4)
N2—C(A4—C(M2—C(A1ⁱ	−1.6 (3)	C1SB—C2SB—C7SB—C6SB	179.0 (2)
C(B4—C(A4—C(M2—C(A1ⁱ	−179.22 (16)	C7SA—C2SA—C3SA—C4SA	0.0
N2—C(A4—C(M2—C11	−179.75 (15)	C1SA—C2SA—C3SA—C4SA	178.2 (4)
C(B4—C(A4—C(M2—C11	2.6 (2)	C2SA—C3SA—C4SA—C5SA	0.0
C2—N3—C1—C3	−0.3 (2)	C3SA—C4SA—C5SA—C6SA	0.0
Fe1—N3—C1—C3	−176.66 (12)	C4SA—C5SA—C6SA—C7SA	0.0
C1—N3—C2—N4	0.3 (2)	C5SA—C6SA—C7SA—C2SA	0.0
Fe1—N3—C2—N4	176.76 (11)	C3SA—C2SA—C7SA—C6SA	0.0
C3—N4—C2—N3	−0.2 (2)	C1SA—C2SA—C7SA—C6SA	−178.2 (4)
C4—N4—C2—N3	−177.55 (16)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N2, C(A3, C(B3, C(B4, C(A4 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···Cgⁱⁱ	0.95 (2)	2.64 (3)	3.408 (2)	137.7 (17)

Symmetry code: (ii) x+1, y, z.

Footnotes

‡These authors contributed equally to this work.

Acknowledgements

We thank the staff members of the WM5 (https://cstr.cn/31125.02.SHMFF·WM5) at the Steady High Magnetic Field Facility, CAS (https://cstr.cn/31125.02.SHMFF), for providing technical support and assistance in data collection and analysis. We also thank the BL13SSW beamline at the Shanghai Synchrotron Radiation Facility (https://cstr.cn/31124.02.SSRF. BL13SSW) for the XAFS experiments and the Shanghai Synchrotron Radiation Facility of BL14B1 (31124.02.SSRF·BL14B1) for the GIWAXS measurements.

Funding information

The authors acknowledge the support of this project by National Key R&D Program of the People's Republic of China (grant No. 2022YFA1405100); National Natural Science Foundation of the People's Republic of China (21771176, 21977093, 22477120).

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