Nitrato(5,10,15,20-tetra­phenyl­porphinato)manganese(III)–benzene–n-hexa­ne (2/1/1)

Cao, H.; Wang, J.; Li, J.

doi:10.1107/S2414314622003868

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 4| April 2022| x220386

https://doi.org/10.1107/S2414314622003868

Open

access

Nitrato(5,10,15,20-tetraphenylporphinato)manganese(III)–benzene–n-hexane (2/1/1)

Hongli Cao,^a Junwen Wang ^a ^* and Jianfeng Li ^b ^*

^aKey Laboratory of Magnetic Molecules, Magnetic Information Materials, Ministry of Education, School of Chemical and Material Science, Shanxi Normal University, Taiyu Road, Taiyuan 030032, People's Republic of China, and ^bCollege of Materials Science and Opto-electronic Technology, CAS Center for Excellence in Topological Quantum Computation & Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Yanqi Lake, Huairou District, Beijing 101408, People's Republic of China
^*Correspondence e-mail: wangjunwen2013@126.com, jfli@ucas.ac.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 March 2022; accepted 7 April 2022; online 22 April 2022)

The crystal structure of solvated [Mn(TPP)(NO₃)] (TPP = 5,10,15,20-tetraphenylporphyrinato, C₄₄H₂₈N₄), [Mn(C₄₄H₂₈N₄O₃)(NO₃)]·0.5C₆H₁₄·0.5C₆H₆, has been determined in the space group Pccn. The Mn^III atom has a distorted square-pyramidal environment, being coordinated by four pyrrole N atoms of the porphyrin ligand in the basal plane and an O atom of the nitrato ligand in the apical site. The Mn^III atom is displaced out of the porphyrin plane by 0.22 (4) Å with the average Mn—Np distance being 2.011 (6) Å (where Np is a porphyrin N atom). The Mn—O bond length is 2.1246 (18) Å. Two kinds of intermolecular C—H⋯O hydrogen bonds exist in the crystal structure, with the apical nitrato ligands interacting with solvent molecules and adjacent molecules, respectively.

Keywords: crystal structure; manganese(III) porphyrin; nitrate.

CCDC reference: 2165166

Structure description

Interactions between metalloporphyrins and nitrate ligands occur in many areas of bioinorganic chemistry. Nitrates play a key role in fixing atmospheric nitrogen into a more bioavailable form, as detailed in the nitrogen cycle (Averill, 1996 ). A series of nitrate-coordinating Fe^III derivatives have been reported, whereby the denticity of the nitrate ligands shows differences for complexes of the general type [Fe(Por)(NO₃)] (where Por is porphyrin). Among them, [Fe(OEP)(NO₃)] (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato, space group P $[\overline{1}]$ ; Ellison et al., 1996 ), [Fe(OEP)(NO₃)] (space group P2₁/c, Wyllie et al., 2007 ) and [Fe(4-Me-TTP)(NO₃)] (TTP = 5,10,15,20-tetrakis(4-methylphenyl)porphyrinato; Bhuyan & Sarkar, 2013 ) have a nitrate group monodentately binding to the central metal cation, while [Fe(TPP)(NO₃)] (Wyllie et al., 2007), [Fe(4-OMe-TPP)(NO₃) (4-OMe-TPP = 5,10,15,20-tetrakis(4-methoxyphenyl)-porphyrinato; Bhuyan & Sarkar, 2013) and [Fe(TpivPP)(NO₃)] (TpivPP = α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato; Munro & Scheidt, 1998 ) have a nitrate group bidentately binding to the central cation. Herein, we report the structural properties of a related manganese(III) compound, viz. [Mn(TPP)(NO₃)], crystallizing as a hemisolvate of benzene and n-hexane. In accordance with the benzene disolvate of [Mn(TPP)(NO₃)] (Suslick & Watson, 1991 ), the nitrato ligand binds monodentately. The key crystal structural parameters of all the above-mentioned metalloporphyrin nitrate complexes are given in Table 1. It is seen that the average Mn—Np bond length and the Mn—O1 bond length of the title complex are 2.011 (6) and 2.1246 (18) Å, respectively, both of which are slightly longer than the values of 2.007 (9) and 2.101 (3) Å found in the structure of the triclinic benzene disolvate [Mn(TPP)(NO₃)]·2C₆H₆ (Suslick & Watson, 1991).

Table 1
Selected structural parameters (Å) for related metalloporphyrin nitrato complexes

Δ₄ is the displacement of the metal atom from the mean plane of the four pyrrole nitrogen atoms and Δ₂₄ is the displacement of the metal atom from the 24-atom mean plane.

Complex	Δ₄	Δ₂₄	M—O	N—O1	M—N_p	Ref.
[Mn(TPP)(NO₃)] (Pccn) benzene and n-hexane hemisolvate	0.23	0.22	2.1246 (18)	1.260 (3) 1.236 (3) 1.230 (3)	2.011 (6)	This work
[Mn(TPP)(NO₃)] (P $[\overline{1}]$ ) benzene disolvate	0.21	0.20	2.101 (3)	1.298 (4) 1.226 (5) 1.226 (5)	2.007 (9)	(Suslick & Watson, 1991)
[Fe(OEP)(NO₃)] (P2₁/c)	0.40	0.45	1.966 (2)	1.301 (3) 1.199 (3) 1.212 (3)	2.047 (6)	(Wyllie et al., 2007)
[Fe(OEP)(NO₃)] (P $[\overline{1}]$ )	0.46	0.50	2.016 (3)	1.206 (5) 1.198 (4) 1.208 (6)	2.056 (1)	(Ellison et al., 1996)
[Fe(4—Me-TTP)(NO₃)]	0.47	0.53	1.971 (3)	1.262 (5) 1.252 (5) 1.221 (4)	2.063 (13)	(Bhuyan & Sarkar, 2013)
[Fe(TPP)(NO₃)]	0.54	0.63	2.121 (6) 2.19 (10)	1.27 (10) 1.285 (21) 1.217 (3)	2.085 (10)	(Wyllie et al., 2007)
[Fe(TpivPP)(NO₃)]	0.42	0.49	2.123 (3) 2.226 (3)	1.271 (4) 1.252 (4) 1.214 (3)	2.070 (16)	(Munro & Scheidt, 1998)
[Fe(4-OMe-TPP)(NO₃)]	0.55	0.62	2.169 (5) 2.169 (5)	1.216 (5) 1.276 (8) 1.216 (5)	2.05 (3)	(Bhuyan & Sarkar, 2013)

In the crystal structure of the title five-coordinate manganese(III) nitrate complex (Fig. 1), the asymmetric unit contains one porphyrin molecule, half of a benzene solvate molecule, and half of an n-hexane solvate molecule. The Mn1^III atom has a distorted square-pyramidal environment, defined by the four pyrrole N atoms of the porphyrin ligand in the basal plane and an O atom of the nitrato ligand in the apical site. Additional quantitative information about the structure is given in Fig. 2, which includes the displacement of each porphyrin core atom (in units of 0.01 Å) from the 24-atom mean plane. Averaged values of the chemically unique bond lengths (in Å) and angles (in °) are also shown. The mean absolute core-atom displacements of C_a, C_b, C_m and C_av are 0.11 (2), 0.28 (3), 0.04 (2) and 0.16 (10) Å, respectively, and the monodentate nitrato ligand forms a dihedral angle of 43.69 (13)° with the plane defined by the Mn1, N3 and O1 atoms.

Figure 1
The molecular structure of the title compound, drawn with displacement ellipsoids at the 50% probability level. Only one of the two orientations of the disordered benzene solvate molecules is shown. [Symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z.]

Figure 2
A formal diagram of the porphyrin core of the title compound. Averaged values of the chemically unique bond lengths (Å) and angles (°) are shown. The perpendicular displacements (in units of 0.01 Å) of the porphyrin core atoms from the 24-atom mean plane are also displayed. The positive numbers indicate a displacement towards the nitrate ligand, the dashed line indicates the plane of the nitrate ligand on the unhindered porphyrin side.

The porphyrin core shows a characteristic saddle-shaped distortion and the Mn1^III atom is displaced by 0.22 (4) Å from the 24-atom porphyrin plane in the direction of the nitrato ligand. This value is smaller than the displacement of the iron atom (0.63 Å) in [Fe(TPP)(NO)₃] reported by Wyllie et al. (2007). This difference is explained by the high-spin configuration of 3d⁵ Fe^III where the occupied d_(x2–y2) orbital `pushes' the metal out of the porphyrin plane, and the empty d_(x2–y2) orbital of 3d⁴ Mn^III allows a more in-plane conformation (Suslick & Watson, 1991).

In the title compound, C—H⋯O hydrogen-bonding interactions are found between the disordered benzene solvent molecule (C4S) and the apical nitrato ligand (O3), as illustrated in Fig. 3 and detailed in Table 2. Similar hydrogen bonds are also found between the apical ligand and phenyl rings of adjacent porphyrin molecules (Fig. 4, Table 2). All these structural parameters are consistent with literature data where C—H⋯O bonds range from 3.00–4.00 Å (Desiraju, 1996 ), with angles of 120–180° (Steiner & Desiraju, 1998 ). The molecular packing of the title compound is shown in Fig. 5.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4S—H4S⋯O3	0.95	2.38	3.177 (8)	141
C10—H10⋯O2ⁱ	0.95	2.50	3.182 (3)	129
C17—H17⋯O2ⁱⁱ	0.95	2.53	3.350 (4)	145
C22—H22⋯O2ⁱⁱⁱ	0.95	2.49	3.085 (3)	120
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+1, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+1, -z+{\script{1\over 2}}]$ .

Figure 3
The C—H⋯O interactions between the apical nitrato ligand and the benzene solvent molecule.

Figure 4
C—H⋯O hydrogen-bonding interactions between adjacent porphyrin molecules (dashed lines).

Figure 5
A view of the molecular packing of the title compound in the crystal structure, as seen in a projection along [100]. H atoms have been omitted for clarity.

Synthesis and crystallization

General information. All experimental manipulations were performed under a purified nitrogen atmosphere using Schlenk techniques. Except for the solvent used in column chromatography, all solvents used in the experimental process were treated under dry conditions and exclusion of oxygen. Benzene and n-hexane were distilled under argon protection, and then refluxed over sodium/benzophenone and potassium–sodium alloy, respectively. All solvents used in the anhydrous and anaerobic operation (Schlenk system) were treated with the pump–freeze–thaw method three times before use.

The title compound was obtained serendipitously in an unsuccessful attempt to isolate the five-coordinate manganese(II) nitrosyl species [Mn(TPP)(NO)]. [Mn(TPP)OH] was prepared according to a reported method (He et al., 2016 ). The purple [Mn(TPP)OH] powder (10 mg, 0.0015 mmol) was reduced by ethyl mercaptan for 48 h with benzene as solvent, then the solution was evaporated to dryness. NO gas was then bubbled slowly in a solution of the residue in degassed benzene for 5 minutes under an argon atmosphere. There was a dramatic color change from greenish yellow to red. The red solution was finally layered with hexanes. Black, block-shaped crystals were obtained several weeks later.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The benzene molecule is disordered around a twofold rotation axis. Thus, the occupancy of all atoms was constrained to 1/2, and the C4S—C9S distance constrained to 1.45 Å. One outlier reflection, 332, was omitted from the refinement.

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(C₄₄H₂₈N₄O₃)(NO₃)]·0.5C₆H₁₄·0.5C₆H₆
M_r	811.79
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	100
a, b, c (Å)	20.1021 (10), 21.5505 (9), 17.9807 (9)
V (Å³)	7789.4 (6)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.33 × 0.29 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.763, 0.865
No. of measured, independent and observed [I > 2σ(I)] reflections	58775, 8270, 6163
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 1.07
No. of reflections	8270
No. of parameters	560
No. of restraints	37
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.48
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2165166

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622003868/wm4162sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622003868/wm4162Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Nitrato(5,10,15,20-tetraphenylporphinato)manganese(III)–benzene–n-hexane (2/1/1) top

Crystal data top

[Mn(C₄₄H₂₈N₄O₃)(NO₃)]·0.5C₆H₁₄·0.5C₆H₆	D_x = 1.384 Mg m⁻³
M_r = 811.79	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 9845 reflections
a = 20.1021 (10) Å	θ = 2.5–26.7°
b = 21.5505 (9) Å	µ = 0.39 mm⁻¹
c = 17.9807 (9) Å	T = 100 K
V = 7789.4 (6) Å³	Block, black
Z = 8	0.33 × 0.29 × 0.12 mm
F(000) = 3376

Data collection top

Bruker APEXII CCD diffractometer	6163 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.058
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.7°, θ_min = 2.3°
T_min = 0.763, T_max = 0.865	h = −25→23
58775 measured reflections	k = −27→24
8270 independent reflections	l = −22→21

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0686P)² + 10.1161P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.097
8270 reflections	Δρ_max = 0.80 e Å⁻³
560 parameters	Δρ_min = −0.48 e Å⁻³
37 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.42182 (2)	0.50321 (2)	0.38016 (2)	0.01235 (11)
O1	0.42711 (8)	0.52498 (8)	0.26507 (10)	0.0206 (4)
O2	0.41592 (10)	0.58633 (9)	0.17166 (11)	0.0311 (5)
O3	0.42351 (12)	0.62345 (10)	0.28275 (12)	0.0416 (6)
N1	0.49166 (9)	0.43691 (8)	0.36975 (11)	0.0144 (4)
N2	0.35071 (9)	0.43777 (8)	0.36889 (11)	0.0148 (4)
N3	0.35138 (9)	0.56361 (9)	0.41173 (11)	0.0151 (4)
N4	0.49211 (9)	0.56102 (8)	0.41874 (11)	0.0147 (4)
N5	0.42152 (11)	0.57920 (11)	0.23960 (13)	0.0259 (5)
C1	0.42051 (11)	0.28091 (11)	0.31319 (15)	0.0183 (5)
C2	0.44918 (13)	0.23571 (11)	0.35761 (16)	0.0259 (6)
H2	0.467963	0.247013	0.404159	0.031*
C3	0.45086 (14)	0.17416 (12)	0.33504 (18)	0.0304 (6)
H3	0.470578	0.143610	0.366108	0.036*
C4	0.42397 (14)	0.15745 (12)	0.26773 (19)	0.0341 (7)
H4	0.425615	0.115394	0.251982	0.041*
C5	0.39436 (16)	0.20192 (13)	0.22261 (18)	0.0369 (7)
H5	0.375509	0.190271	0.176218	0.044*
C6	0.39240 (14)	0.26347 (12)	0.24550 (16)	0.0298 (6)
H6	0.371794	0.293805	0.214858	0.036*
C7	0.17559 (12)	0.50079 (10)	0.38931 (13)	0.0158 (5)
C8	0.14138 (12)	0.47327 (11)	0.44853 (15)	0.0198 (5)
H8	0.165523	0.456573	0.489306	0.024*
C9	0.07229 (12)	0.47019 (12)	0.44807 (16)	0.0243 (6)
H9	0.049340	0.451340	0.488358	0.029*
C10	0.03678 (13)	0.49480 (12)	0.38843 (15)	0.0244 (6)
H10	−0.010419	0.492704	0.387856	0.029*
C11	0.07056 (13)	0.52232 (13)	0.33002 (16)	0.0256 (6)
H11	0.046353	0.539209	0.289402	0.031*
C12	0.13958 (12)	0.52542 (11)	0.33034 (15)	0.0217 (5)
H12	0.162274	0.544480	0.290016	0.026*
C13	0.42453 (11)	0.72160 (11)	0.45726 (15)	0.0189 (5)
C14	0.45003 (16)	0.75859 (13)	0.4016 (2)	0.0404 (8)
H14	0.466560	0.740272	0.357213	0.048*
C15	0.45157 (18)	0.82290 (14)	0.4103 (2)	0.0527 (10)
H15	0.468977	0.848052	0.371515	0.063*
C16	0.42877 (14)	0.84987 (13)	0.4729 (2)	0.0398 (8)
H16	0.429418	0.893761	0.477800	0.048*
C17	0.40443 (17)	0.81338 (14)	0.5299 (2)	0.0430 (9)
H17	0.389609	0.832124	0.574726	0.052*
C18	0.40157 (16)	0.74907 (13)	0.52169 (17)	0.0338 (7)
H18	0.383801	0.724157	0.560487	0.041*
C19	0.66708 (12)	0.50305 (10)	0.38165 (13)	0.0154 (5)
C20	0.70957 (12)	0.45885 (11)	0.41236 (14)	0.0198 (5)
H20	0.691967	0.426573	0.442483	0.024*
C21	0.77752 (13)	0.46181 (13)	0.39912 (15)	0.0256 (6)
H21	0.806087	0.431261	0.419872	0.031*
C22	0.80410 (13)	0.50902 (13)	0.35582 (16)	0.0271 (6)
H22	0.850647	0.510865	0.346956	0.032*
C23	0.76238 (13)	0.55324 (13)	0.32574 (15)	0.0277 (6)
H23	0.780381	0.585843	0.296427	0.033*
C24	0.69414 (13)	0.55040 (12)	0.33805 (15)	0.0226 (5)
H24	0.665777	0.580821	0.316693	0.027*
C(A1	0.55989 (11)	0.44641 (10)	0.36743 (13)	0.0146 (5)
C(A2	0.48166 (12)	0.37726 (10)	0.34335 (13)	0.0157 (5)
C(A3	0.35993 (12)	0.37606 (10)	0.35121 (14)	0.0169 (5)
C(A4	0.28251 (12)	0.44579 (10)	0.37543 (13)	0.0159 (5)
C(A5	0.28327 (12)	0.55656 (11)	0.40428 (14)	0.0174 (5)
C(A6	0.36142 (12)	0.62527 (10)	0.43015 (14)	0.0173 (5)
C(A7	0.48260 (12)	0.62090 (10)	0.44399 (13)	0.0162 (5)
C(A8	0.56024 (11)	0.55124 (10)	0.42006 (13)	0.0150 (5)
C(B1	0.59185 (12)	0.39247 (11)	0.33697 (14)	0.0194 (5)
H(B1	0.638168	0.387514	0.328321	0.023*
C(B2	0.54403 (12)	0.35015 (11)	0.32289 (14)	0.0191 (5)
H(B2	0.550561	0.309748	0.303040	0.023*
C(B3	0.29657 (12)	0.34533 (11)	0.34796 (15)	0.0216 (5)
H(B3	0.289310	0.302652	0.337501	0.026*
C(B4	0.24941 (12)	0.38788 (11)	0.36239 (15)	0.0213 (5)
H(B4	0.202762	0.380878	0.363712	0.026*
C(B5	0.25083 (13)	0.61474 (11)	0.41847 (15)	0.0230 (6)
H(B5	0.204257	0.622200	0.417728	0.028*
C(B6	0.29864 (12)	0.65671 (11)	0.43303 (16)	0.0230 (6)
H(B6	0.291982	0.699496	0.443361	0.028*
C(B7	0.54509 (12)	0.64704 (11)	0.46568 (14)	0.0182 (5)
H(B7	0.551968	0.687212	0.486043	0.022*
C(B8	0.59258 (12)	0.60410 (11)	0.45188 (14)	0.0176 (5)
H(B8	0.638833	0.608255	0.461525	0.021*
C(M1	0.42063 (12)	0.34755 (10)	0.33679 (13)	0.0162 (5)
C(M2	0.25010 (12)	0.50150 (10)	0.38919 (13)	0.0153 (5)
C(M3	0.42232 (11)	0.65274 (10)	0.44520 (14)	0.0168 (5)
C(M4	0.59319 (12)	0.49958 (10)	0.39124 (13)	0.0145 (5)
C1S	0.28678 (18)	0.23978 (17)	0.4985 (2)	0.0488 (9)
H1SA	0.315264	0.276355	0.508279	0.059*
H1SB	0.298393	0.223535	0.448647	0.059*
C2S	0.30152 (18)	0.18932 (17)	0.5575 (2)	0.0509 (9)
H2SA	0.289087	0.204976	0.607336	0.061*
H2SB	0.274282	0.152072	0.546955	0.061*
C3S	0.37423 (19)	0.17186 (17)	0.5572 (2)	0.0571 (10)
H3SA	0.387512	0.159787	0.506761	0.086*
H3SB	0.381507	0.136996	0.591202	0.086*
H3SC	0.400895	0.207461	0.573341	0.086*
C4S	0.3238 (4)	0.7350 (3)	0.2525 (4)	0.0454 (15)	0.5
H4S	0.363543	0.718301	0.272952	0.054*	0.5
C5S	0.2861 (11)	0.7015 (10)	0.2020 (13)	0.069 (6)	0.5
H5S	0.299310	0.660302	0.190509	0.083*	0.5
C6S	0.2325 (5)	0.7245 (4)	0.1690 (6)	0.077 (3)	0.5
H6S	0.210217	0.701910	0.131113	0.093*	0.5
C7S	0.2079 (11)	0.7868 (11)	0.1930 (17)	0.075 (6)	0.5
H7S	0.167838	0.803904	0.173935	0.090*	0.5
C8S	0.2462 (4)	0.8181 (4)	0.2438 (5)	0.0518 (19)	0.5
H8S	0.233013	0.858391	0.259270	0.062*	0.5
C9S	0.3018 (3)	0.7930 (3)	0.2721 (4)	0.0414 (15)	0.5
H9S	0.326862	0.816292	0.307085	0.050*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01075 (19)	0.00928 (18)	0.0170 (2)	0.00011 (12)	−0.00051 (13)	−0.00002 (13)
O1	0.0168 (9)	0.0267 (9)	0.0183 (9)	0.0015 (7)	−0.0016 (7)	0.0008 (7)
O2	0.0329 (11)	0.0353 (11)	0.0252 (11)	−0.0007 (8)	−0.0020 (8)	0.0095 (9)
O3	0.0610 (15)	0.0309 (11)	0.0328 (12)	−0.0039 (10)	0.0025 (10)	−0.0002 (9)
N1	0.0149 (10)	0.0101 (9)	0.0181 (10)	−0.0004 (7)	−0.0014 (8)	−0.0002 (8)
N2	0.0134 (10)	0.0104 (9)	0.0206 (11)	−0.0001 (7)	0.0007 (8)	0.0002 (8)
N3	0.0117 (9)	0.0115 (9)	0.0220 (11)	−0.0004 (7)	0.0000 (8)	0.0009 (8)
N4	0.0149 (10)	0.0100 (9)	0.0191 (11)	0.0013 (7)	0.0001 (8)	0.0005 (8)
N5	0.0201 (11)	0.0309 (12)	0.0268 (13)	−0.0047 (9)	0.0010 (9)	−0.0002 (10)
C1	0.0126 (11)	0.0137 (11)	0.0286 (14)	−0.0017 (9)	0.0024 (10)	−0.0036 (10)
C2	0.0255 (14)	0.0180 (12)	0.0342 (15)	0.0028 (10)	−0.0041 (12)	−0.0024 (11)
C3	0.0262 (14)	0.0138 (12)	0.0511 (19)	0.0033 (10)	−0.0036 (13)	−0.0017 (12)
C4	0.0252 (14)	0.0164 (13)	0.061 (2)	0.0002 (11)	−0.0031 (14)	−0.0159 (13)
C5	0.0428 (18)	0.0290 (15)	0.0390 (18)	−0.0024 (13)	−0.0086 (14)	−0.0149 (13)
C6	0.0345 (15)	0.0233 (14)	0.0317 (16)	0.0017 (11)	−0.0060 (13)	−0.0038 (11)
C7	0.0138 (11)	0.0128 (11)	0.0209 (12)	−0.0001 (8)	0.0010 (9)	−0.0044 (9)
C8	0.0176 (12)	0.0173 (12)	0.0247 (13)	−0.0006 (9)	−0.0012 (10)	0.0000 (10)
C9	0.0196 (13)	0.0219 (13)	0.0313 (15)	−0.0043 (10)	0.0077 (11)	−0.0043 (11)
C10	0.0120 (12)	0.0269 (14)	0.0343 (16)	−0.0011 (10)	0.0009 (10)	−0.0107 (11)
C11	0.0172 (13)	0.0303 (14)	0.0293 (15)	0.0033 (10)	−0.0036 (11)	−0.0083 (12)
C12	0.0183 (13)	0.0225 (12)	0.0243 (14)	0.0032 (10)	0.0001 (10)	0.0005 (10)
C13	0.0128 (11)	0.0130 (11)	0.0309 (14)	0.0013 (9)	−0.0068 (10)	−0.0024 (10)
C14	0.0412 (18)	0.0175 (14)	0.062 (2)	0.0008 (12)	0.0178 (16)	0.0018 (14)
C15	0.044 (2)	0.0170 (14)	0.097 (3)	−0.0012 (13)	0.024 (2)	0.0097 (17)
C16	0.0225 (14)	0.0127 (12)	0.084 (3)	0.0005 (11)	−0.0136 (15)	−0.0049 (15)
C17	0.052 (2)	0.0296 (16)	0.048 (2)	0.0194 (14)	−0.0259 (16)	−0.0189 (15)
C18	0.0496 (18)	0.0196 (13)	0.0321 (16)	0.0122 (12)	−0.0080 (14)	−0.0017 (12)
C19	0.0130 (11)	0.0159 (11)	0.0173 (12)	−0.0024 (9)	0.0003 (9)	−0.0027 (9)
C20	0.0194 (13)	0.0184 (12)	0.0216 (13)	0.0013 (9)	−0.0010 (10)	−0.0002 (10)
C21	0.0183 (13)	0.0278 (14)	0.0308 (15)	0.0066 (10)	−0.0019 (11)	−0.0055 (11)
C22	0.0155 (13)	0.0340 (15)	0.0317 (15)	−0.0039 (10)	0.0045 (11)	−0.0089 (12)
C23	0.0241 (14)	0.0313 (14)	0.0276 (14)	−0.0080 (11)	0.0063 (11)	0.0013 (12)
C24	0.0212 (13)	0.0217 (13)	0.0249 (14)	−0.0017 (10)	−0.0010 (10)	0.0026 (10)
C(A1	0.0141 (11)	0.0130 (11)	0.0167 (12)	0.0011 (8)	0.0011 (9)	0.0022 (9)
C(A2	0.0184 (12)	0.0117 (10)	0.0171 (12)	0.0026 (9)	−0.0004 (9)	0.0006 (9)
C(A3	0.0170 (12)	0.0122 (11)	0.0214 (13)	−0.0010 (9)	−0.0021 (10)	0.0002 (9)
C(A4	0.0148 (11)	0.0143 (11)	0.0185 (12)	−0.0012 (9)	−0.0007 (9)	0.0010 (9)
C(A5	0.0150 (12)	0.0139 (11)	0.0232 (13)	0.0020 (9)	0.0011 (10)	0.0011 (9)
C(A6	0.0165 (12)	0.0126 (11)	0.0227 (13)	0.0011 (9)	0.0008 (10)	0.0011 (9)
C(A7	0.0167 (12)	0.0127 (11)	0.0191 (12)	0.0001 (9)	−0.0012 (9)	−0.0002 (9)
C(A8	0.0132 (11)	0.0139 (11)	0.0180 (12)	−0.0005 (8)	−0.0014 (9)	0.0016 (9)
C(B1	0.0176 (12)	0.0161 (11)	0.0245 (14)	0.0023 (9)	0.0023 (10)	−0.0003 (10)
C(B2	0.0182 (12)	0.0133 (11)	0.0258 (13)	0.0031 (9)	0.0009 (10)	−0.0029 (10)
C(B3	0.0175 (12)	0.0138 (11)	0.0336 (15)	−0.0041 (9)	−0.0002 (11)	−0.0024 (10)
C(B4	0.0149 (12)	0.0170 (11)	0.0320 (15)	−0.0030 (9)	0.0005 (10)	−0.0003 (10)
C(B5	0.0147 (12)	0.0158 (11)	0.0386 (16)	0.0022 (9)	−0.0011 (11)	−0.0022 (11)
C(B6	0.0162 (12)	0.0141 (11)	0.0386 (16)	0.0024 (9)	−0.0017 (11)	−0.0025 (11)
C(B7	0.0192 (12)	0.0131 (11)	0.0224 (13)	−0.0021 (9)	−0.0011 (10)	−0.0018 (9)
C(B8	0.0156 (12)	0.0170 (11)	0.0202 (13)	−0.0011 (9)	−0.0021 (9)	−0.0007 (9)
C(M1	0.0179 (12)	0.0112 (10)	0.0196 (13)	0.0007 (9)	−0.0016 (9)	0.0001 (9)
C(M2	0.0135 (11)	0.0149 (11)	0.0175 (12)	0.0002 (9)	−0.0002 (9)	0.0025 (9)
C(M3	0.0173 (12)	0.0114 (10)	0.0215 (13)	0.0006 (9)	−0.0012 (10)	−0.0003 (9)
C(M4	0.0119 (11)	0.0145 (11)	0.0170 (12)	0.0007 (8)	−0.0007 (8)	0.0019 (9)
C1S	0.059 (2)	0.0438 (19)	0.043 (2)	0.0006 (17)	−0.0063 (17)	−0.0030 (16)
C2S	0.049 (2)	0.046 (2)	0.057 (2)	−0.0065 (16)	0.0016 (18)	−0.0077 (17)
C3S	0.060 (2)	0.045 (2)	0.067 (3)	−0.0008 (18)	−0.001 (2)	−0.0046 (18)
C4S	0.050 (4)	0.048 (4)	0.038 (4)	0.001 (3)	0.003 (3)	0.004 (3)
C5S	0.074 (10)	0.046 (7)	0.087 (12)	0.001 (6)	−0.014 (9)	−0.015 (8)
C6S	0.068 (6)	0.060 (5)	0.104 (8)	−0.016 (4)	−0.024 (5)	−0.012 (5)
C7S	0.046 (7)	0.077 (9)	0.103 (11)	0.010 (6)	−0.043 (7)	−0.015 (8)
C8S	0.044 (4)	0.053 (4)	0.059 (5)	−0.001 (3)	−0.006 (4)	−0.011 (4)
C9S	0.042 (3)	0.044 (3)	0.038 (4)	0.004 (3)	0.006 (3)	−0.001 (3)

Geometric parameters (Å, º) top

Mn1—O1	2.1246 (18)	C21—H21	0.9500
Mn1—N1	2.0119 (19)	C21—C22	1.388 (4)
Mn1—N2	2.0184 (19)	C22—H22	0.9500
Mn1—N3	2.0052 (19)	C22—C23	1.380 (4)
Mn1—N4	2.0074 (19)	C23—H23	0.9500
O1—N5	1.260 (3)	C23—C24	1.391 (4)
O2—N5	1.236 (3)	C24—H24	0.9500
O3—N5	1.230 (3)	C(A1—C(B1	1.437 (3)
N1—C(A1	1.387 (3)	C(A1—C(M4	1.394 (3)
N1—C(A2	1.385 (3)	C(A2—C(B2	1.431 (3)
N2—C(A3	1.380 (3)	C(A2—C(M1	1.389 (3)
N2—C(A4	1.387 (3)	C(A3—C(B3	1.437 (3)
N3—C(A5	1.384 (3)	C(A3—C(M1	1.391 (3)
N3—C(A6	1.384 (3)	C(A4—C(B4	1.434 (3)
N4—C(A7	1.381 (3)	C(A4—C(M2	1.388 (3)
N4—C(A8	1.386 (3)	C(A5—C(B5	1.436 (3)
C1—C2	1.385 (4)	C(A5—C(M2	1.388 (3)
C1—C6	1.394 (4)	C(A6—C(B6	1.433 (3)
C1—C(M1	1.497 (3)	C(A6—C(M3	1.386 (3)
C2—H2	0.9500	C(A7—C(B7	1.431 (3)
C2—C3	1.388 (3)	C(A7—C(M3	1.393 (3)
C3—H3	0.9500	C(A8—C(B8	1.431 (3)
C3—C4	1.374 (4)	C(A8—C(M4	1.395 (3)
C4—H4	0.9500	C(B1—H(B1	0.9500
C4—C5	1.390 (4)	C(B1—C(B2	1.349 (3)
C5—H5	0.9500	C(B2—H(B2	0.9500
C5—C6	1.389 (4)	C(B3—H(B3	0.9500
C6—H6	0.9500	C(B3—C(B4	1.344 (3)
C7—C8	1.399 (3)	C(B4—H(B4	0.9500
C7—C12	1.389 (3)	C(B5—H(B5	0.9500
C7—C(M2	1.498 (3)	C(B5—C(B6	1.346 (3)
C8—H8	0.9500	C(B6—H(B6	0.9500
C8—C9	1.391 (3)	C(B7—H(B7	0.9500
C9—H9	0.9500	C(B7—C(B8	1.353 (3)
C9—C10	1.393 (4)	C(B8—H(B8	0.9500
C10—H10	0.9500	C1S—C1Sⁱ	1.543 (7)
C10—C11	1.384 (4)	C1S—H1SA	0.9900
C11—H11	0.9500	C1S—H1SB	0.9900
C11—C12	1.389 (4)	C1S—C2S	1.548 (5)
C12—H12	0.9500	C2S—H2SA	0.9900
C13—C14	1.379 (4)	C2S—H2SB	0.9900
C13—C18	1.380 (4)	C2S—C3S	1.509 (5)
C13—C(M3	1.500 (3)	C3S—H3SA	0.9800
C14—H14	0.9500	C3S—H3SB	0.9800
C14—C15	1.395 (4)	C3S—H3SC	0.9800
C15—H15	0.9500	C4S—H4S	0.9500
C15—C16	1.347 (5)	C4S—C5S	1.38 (2)
C16—H16	0.9500	C4S—C9S	1.372 (9)
C16—C17	1.381 (5)	C5S—H5S	0.9500
C17—H17	0.9500	C5S—C6S	1.33 (2)
C17—C18	1.395 (4)	C6S—H6S	0.9500
C18—H18	0.9500	C6S—C7S	1.49 (3)
C19—C20	1.393 (3)	C7S—H7S	0.9500
C19—C24	1.397 (3)	C7S—C8S	1.37 (2)
C19—C(M4	1.497 (3)	C8S—H8S	0.9500
C20—H20	0.9500	C8S—C9S	1.342 (10)
C20—C21	1.388 (4)	C9S—H9S	0.9500

N1—Mn1—O1	91.79 (7)	C23—C24—H24	119.8
N1—Mn1—N2	89.34 (8)	N1—C(A1—C(B1	109.5 (2)
N2—Mn1—O1	95.27 (7)	N1—C(A1—C(M4	125.9 (2)
N3—Mn1—O1	99.66 (7)	C(M4—C(A1—C(B1	124.6 (2)
N3—Mn1—N1	168.53 (8)	N1—C(A2—C(B2	109.9 (2)
N3—Mn1—N2	88.96 (8)	N1—C(A2—C(M1	125.8 (2)
N3—Mn1—N4	89.79 (8)	C(M1—C(A2—C(B2	124.3 (2)
N4—Mn1—O1	99.46 (7)	N2—C(A3—C(B3	109.5 (2)
N4—Mn1—N1	88.95 (8)	N2—C(A3—C(M1	125.9 (2)
N4—Mn1—N2	165.21 (8)	C(M1—C(A3—C(B3	124.5 (2)
N5—O1—Mn1	123.66 (15)	N2—C(A4—C(B4	109.7 (2)
C(A1—N1—Mn1	126.01 (15)	N2—C(A4—C(M2	125.9 (2)
C(A2—N1—Mn1	126.15 (15)	C(M2—C(A4—C(B4	124.3 (2)
C(A2—N1—C(A1	105.67 (18)	N3—C(A5—C(B5	109.7 (2)
C(A3—N2—Mn1	126.98 (16)	N3—C(A5—C(M2	126.0 (2)
C(A3—N2—C(A4	105.81 (19)	C(M2—C(A5—C(B5	124.3 (2)
C(A4—N2—Mn1	127.19 (15)	N3—C(A6—C(B6	109.5 (2)
C(A5—N3—Mn1	126.86 (16)	N3—C(A6—C(M3	125.8 (2)
C(A6—N3—Mn1	126.00 (15)	C(M3—C(A6—C(B6	124.6 (2)
C(A6—N3—C(A5	105.82 (18)	N4—C(A7—C(B7	109.6 (2)
C(A7—N4—Mn1	126.58 (15)	N4—C(A7—C(M3	125.9 (2)
C(A7—N4—C(A8	105.85 (18)	C(M3—C(A7—C(B7	124.4 (2)
C(A8—N4—Mn1	127.38 (15)	N4—C(A8—C(B8	109.6 (2)
O2—N5—O1	118.8 (2)	N4—C(A8—C(M4	125.7 (2)
O3—N5—O1	119.1 (2)	C(M4—C(A8—C(B8	124.6 (2)
O3—N5—O2	122.0 (2)	C(A1—C(B1—H(B1	126.3
C2—C1—C6	118.9 (2)	C(B2—C(B1—C(A1	107.5 (2)
C2—C1—C(M1	120.7 (2)	C(B2—C(B1—H(B1	126.3
C6—C1—C(M1	120.5 (2)	C(A2—C(B2—H(B2	126.3
C1—C2—H2	119.5	C(B1—C(B2—C(A2	107.4 (2)
C1—C2—C3	120.9 (3)	C(B1—C(B2—H(B2	126.3
C3—C2—H2	119.5	C(A3—C(B3—H(B3	126.2
C2—C3—H3	120.0	C(B4—C(B3—C(A3	107.6 (2)
C4—C3—C2	119.9 (3)	C(B4—C(B3—H(B3	126.2
C4—C3—H3	120.0	C(A4—C(B4—H(B4	126.3
C3—C4—H4	119.9	C(B3—C(B4—C(A4	107.3 (2)
C3—C4—C5	120.1 (2)	C(B3—C(B4—H(B4	126.3
C5—C4—H4	119.9	C(A5—C(B5—H(B5	126.4
C4—C5—H5	120.1	C(B6—C(B5—C(A5	107.3 (2)
C6—C5—C4	119.9 (3)	C(B6—C(B5—H(B5	126.4
C6—C5—H5	120.1	C(A6—C(B6—H(B6	126.1
C1—C6—H6	119.8	C(B5—C(B6—C(A6	107.7 (2)
C5—C6—C1	120.3 (3)	C(B5—C(B6—H(B6	126.2
C5—C6—H6	119.8	C(A7—C(B7—H(B7	126.3
C8—C7—C(M2	119.8 (2)	C(B8—C(B7—C(A7	107.5 (2)
C12—C7—C8	119.1 (2)	C(B8—C(B7—H(B7	126.3
C12—C7—C(M2	121.1 (2)	C(A8—C(B8—H(B8	126.3
C7—C8—H8	119.8	C(B7—C(B8—C(A8	107.3 (2)
C9—C8—C7	120.4 (2)	C(B7—C(B8—H(B8	126.3
C9—C8—H8	119.8	C(A2—C(M1—C1	117.9 (2)
C8—C9—H9	120.1	C(A2—C(M1—C(A3	123.7 (2)
C8—C9—C10	119.9 (2)	C(A3—C(M1—C1	118.4 (2)
C10—C9—H9	120.1	C(A4—C(M2—C7	117.4 (2)
C9—C10—H10	120.1	C(A5—C(M2—C7	119.3 (2)
C11—C10—C9	119.7 (2)	C(A5—C(M2—C(A4	123.3 (2)
C11—C10—H10	120.1	C(A6—C(M3—C13	118.5 (2)
C10—C11—H11	119.8	C(A6—C(M3—C(A7	123.7 (2)
C10—C11—C12	120.5 (3)	C(A7—C(M3—C13	117.6 (2)
C12—C11—H11	119.8	C(A1—C(M4—C19	118.8 (2)
C7—C12—H12	119.8	C(A1—C(M4—C(A8	122.8 (2)
C11—C12—C7	120.3 (2)	C(A8—C(M4—C19	118.3 (2)
C11—C12—H12	119.8	C1Sⁱ—C1S—H1SA	109.1
C14—C13—C18	119.1 (2)	C1Sⁱ—C1S—H1SB	109.1
C14—C13—C(M3	118.5 (2)	C1Sⁱ—C1S—C2S	112.6 (3)
C18—C13—C(M3	122.4 (2)	H1SA—C1S—H1SB	107.8
C13—C14—H14	120.0	C2S—C1S—H1SA	109.1
C13—C14—C15	120.1 (3)	C2S—C1S—H1SB	109.1
C15—C14—H14	120.0	C1S—C2S—H2SA	109.4
C14—C15—H15	119.5	C1S—C2S—H2SB	109.4
C16—C15—C14	121.0 (3)	H2SA—C2S—H2SB	108.0
C16—C15—H15	119.5	C3S—C2S—C1S	111.0 (3)
C15—C16—H16	120.2	C3S—C2S—H2SA	109.4
C15—C16—C17	119.6 (3)	C3S—C2S—H2SB	109.4
C17—C16—H16	120.2	C2S—C3S—H3SA	109.5
C16—C17—H17	119.9	C2S—C3S—H3SB	109.5
C16—C17—C18	120.1 (3)	C2S—C3S—H3SC	109.5
C18—C17—H17	119.9	H3SA—C3S—H3SB	109.5
C13—C18—C17	120.1 (3)	H3SA—C3S—H3SC	109.5
C13—C18—H18	120.0	H3SB—C3S—H3SC	109.5
C17—C18—H18	120.0	C5S—C4S—H4S	121.1
C20—C19—C24	118.9 (2)	C5S—C4S—C9S	117.8 (11)
C20—C19—C(M4	121.9 (2)	C9S—C4S—H4S	121.1
C24—C19—C(M4	119.2 (2)	C4S—C5S—H5S	118.5
C19—C20—H20	119.9	C6S—C5S—C4S	122.9 (16)
C21—C20—C19	120.3 (2)	C6S—C5S—H5S	118.6
C21—C20—H20	119.9	C5S—C6S—H6S	120.8
C20—C21—H21	119.7	C5S—C6S—C7S	118.4 (12)
C22—C21—C20	120.6 (2)	C7S—C6S—H6S	120.8
C22—C21—H21	119.7	C6S—C7S—H7S	121.6
C21—C22—H22	120.3	C8S—C7S—C6S	116.7 (14)
C23—C22—C21	119.5 (2)	C8S—C7S—H7S	121.7
C23—C22—H22	120.3	C7S—C8S—H8S	119.3
C22—C23—H23	119.8	C9S—C8S—C7S	121.5 (11)
C22—C23—C24	120.4 (2)	C9S—C8S—H8S	119.3
C24—C23—H23	119.8	C4S—C9S—H9S	118.7
C19—C24—H24	119.8	C8S—C9S—C4S	122.6 (7)
C23—C24—C19	120.4 (2)	C8S—C9S—H9S	118.7

Mn1—O1—N5—O2	−169.95 (16)	C18—C13—C(M3—C(A7	−110.9 (3)
Mn1—O1—N5—O3	11.9 (3)	C19—C20—C21—C22	0.6 (4)
Mn1—N1—C(A1—C(B1	−162.14 (16)	C20—C19—C24—C23	−0.1 (4)
Mn1—N1—C(A1—C(M4	18.3 (3)	C20—C19—C(M4—C(A1	−57.4 (3)
Mn1—N1—C(A2—C(B2	162.58 (16)	C20—C19—C(M4—C(A8	125.9 (2)
Mn1—N1—C(A2—C(M1	−17.0 (3)	C20—C21—C22—C23	−0.1 (4)
Mn1—N2—C(A3—C(B3	−179.46 (17)	C21—C22—C23—C24	−0.6 (4)
Mn1—N2—C(A3—C(M1	−0.9 (4)	C22—C23—C24—C19	0.6 (4)
Mn1—N2—C(A4—C(B4	179.21 (16)	C24—C19—C20—C21	−0.5 (4)
Mn1—N2—C(A4—C(M2	1.9 (4)	C24—C19—C(M4—C(A1	119.8 (2)
Mn1—N3—C(A5—C(B5	−167.60 (17)	C24—C19—C(M4—C(A8	−56.8 (3)
Mn1—N3—C(A5—C(M2	15.5 (4)	C(A1—N1—C(A2—C(B2	−1.3 (3)
Mn1—N3—C(A6—C(B6	166.81 (17)	C(A1—N1—C(A2—C(M1	179.1 (2)
Mn1—N3—C(A6—C(M3	−14.5 (4)	C(A1—C(B1—C(B2—C(A2	0.8 (3)
Mn1—N4—C(A7—C(B7	−179.11 (16)	C(A2—N1—C(A1—C(B1	1.8 (3)
Mn1—N4—C(A7—C(M3	−2.0 (4)	C(A2—N1—C(A1—C(M4	−177.7 (2)
Mn1—N4—C(A8—C(B8	179.77 (16)	C(A3—N2—C(A4—C(B4	0.7 (3)
Mn1—N4—C(A8—C(M4	3.1 (3)	C(A3—N2—C(A4—C(M2	−176.7 (2)
N1—C(A1—C(B1—C(B2	−1.6 (3)	C(A3—C(B3—C(B4—C(A4	−0.4 (3)
N1—C(A1—C(M4—C19	−177.4 (2)	C(A4—N2—C(A3—C(B3	−0.9 (3)
N1—C(A1—C(M4—C(A8	−1.0 (4)	C(A4—N2—C(A3—C(M1	177.6 (2)
N1—C(A2—C(B2—C(B1	0.4 (3)	C(A5—N3—C(A6—C(B6	−0.8 (3)
N1—C(A2—C(M1—C1	−174.8 (2)	C(A5—N3—C(A6—C(M3	177.9 (2)
N1—C(A2—C(M1—C(A3	4.9 (4)	C(A5—C(B5—C(B6—C(A6	−1.5 (3)
N2—C(A3—C(B3—C(B4	0.9 (3)	C(A6—N3—C(A5—C(B5	−0.1 (3)
N2—C(A3—C(M1—C1	−175.7 (2)	C(A6—N3—C(A5—C(M2	−177.1 (2)
N2—C(A3—C(M1—C(A2	4.6 (4)	C(A7—N4—C(A8—C(B8	4.5 (3)
N2—C(A4—C(B4—C(B3	−0.2 (3)	C(A7—N4—C(A8—C(M4	−172.3 (2)
N2—C(A4—C(M2—C7	176.1 (2)	C(A7—C(B7—C(B8—C(A8	1.1 (3)
N2—C(A4—C(M2—C(A5	−5.4 (4)	C(A8—N4—C(A7—C(B7	−3.7 (3)
N3—C(A5—C(B5—C(B6	1.1 (3)	C(A8—N4—C(A7—C(M3	173.4 (2)
N3—C(A5—C(M2—C7	174.8 (2)	C(B1—C(A1—C(M4—C19	3.1 (3)
N3—C(A5—C(M2—C(A4	−3.7 (4)	C(B1—C(A1—C(M4—C(A8	179.5 (2)
N3—C(A6—C(B6—C(B5	1.5 (3)	C(B2—C(A2—C(M1—C1	5.7 (4)
N3—C(A6—C(M3—C13	174.4 (2)	C(B2—C(A2—C(M1—C(A3	−174.6 (2)
N3—C(A6—C(M3—C(A7	−0.3 (4)	C(B3—C(A3—C(M1—C1	2.6 (4)
N4—C(A7—C(B7—C(B8	1.6 (3)	C(B3—C(A3—C(M1—C(A2	−177.1 (2)
N4—C(A7—C(M3—C13	−165.7 (2)	C(B4—C(A4—C(M2—C7	−0.9 (4)
N4—C(A7—C(M3—C(A6	9.0 (4)	C(B4—C(A4—C(M2—C(A5	177.6 (2)
N4—C(A8—C(B8—C(B7	−3.5 (3)	C(B5—C(A5—C(M2—C7	−1.7 (4)
N4—C(A8—C(M4—C19	166.2 (2)	C(B5—C(A5—C(M2—C(A4	179.8 (2)
N4—C(A8—C(M4—C(A1	−10.3 (4)	C(B6—C(A6—C(M3—C13	−7.1 (4)
C1—C2—C3—C4	0.2 (4)	C(B6—C(A6—C(M3—C(A7	178.2 (2)
C2—C1—C6—C5	−1.2 (4)	C(B7—C(A7—C(M3—C13	11.0 (4)
C2—C1—C(M1—C(A2	64.2 (3)	C(B7—C(A7—C(M3—C(A6	−174.2 (2)
C2—C1—C(M1—C(A3	−115.5 (3)	C(B8—C(A8—C(M4—C19	−10.0 (4)
C2—C3—C4—C5	−0.8 (5)	C(B8—C(A8—C(M4—C(A1	173.5 (2)
C3—C4—C5—C6	0.4 (5)	C(M1—C1—C2—C3	−178.2 (2)
C4—C5—C6—C1	0.6 (5)	C(M1—C1—C6—C5	177.8 (3)
C6—C1—C2—C3	0.8 (4)	C(M1—C(A2—C(B2—C(B1	180.0 (2)
C6—C1—C(M1—C(A2	−114.8 (3)	C(M1—C(A3—C(B3—C(B4	−177.7 (2)
C6—C1—C(M1—C(A3	65.5 (3)	C(M2—C7—C8—C9	−177.6 (2)
C7—C8—C9—C10	−0.2 (4)	C(M2—C7—C12—C11	177.6 (2)
C8—C7—C12—C11	−0.5 (4)	C(M2—C(A4—C(B4—C(B3	177.2 (2)
C8—C7—C(M2—C(A4	72.7 (3)	C(M2—C(A5—C(B5—C(B6	178.1 (2)
C8—C7—C(M2—C(A5	−105.9 (3)	C(M3—C13—C14—C15	178.7 (3)
C8—C9—C10—C11	−0.1 (4)	C(M3—C13—C18—C17	−179.6 (3)
C9—C10—C11—C12	0.2 (4)	C(M3—C(A6—C(B6—C(B5	−177.3 (3)
C10—C11—C12—C7	0.1 (4)	C(M3—C(A7—C(B7—C(B8	−175.6 (2)
C12—C7—C8—C9	0.5 (3)	C(M4—C19—C20—C21	176.7 (2)
C12—C7—C(M2—C(A4	−105.3 (3)	C(M4—C19—C24—C23	−177.4 (2)
C12—C7—C(M2—C(A5	76.1 (3)	C(M4—C(A1—C(B1—C(B2	177.9 (2)
C13—C14—C15—C16	0.4 (6)	C(M4—C(A8—C(B8—C(B7	173.2 (2)
C14—C13—C18—C17	−0.1 (4)	C1Sⁱ—C1S—C2S—C3S	−178.4 (3)
C14—C13—C(M3—C(A6	−105.4 (3)	C4S—C5S—C6S—C7S	−6 (3)
C14—C13—C(M3—C(A7	69.6 (3)	C5S—C4S—C9S—C8S	−0.6 (15)
C14—C15—C16—C17	1.0 (5)	C5S—C6S—C7S—C8S	5 (3)
C15—C16—C17—C18	−2.0 (5)	C6S—C7S—C8S—C9S	−2 (3)
C16—C17—C18—C13	1.5 (5)	C7S—C8S—C9S—C4S	−0.2 (19)
C18—C13—C14—C15	−0.8 (5)	C9S—C4S—C5S—C6S	4 (3)
C18—C13—C(M3—C(A6	74.1 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4S—H4S···O3	0.95	2.38	3.177 (8)	141
C10—H10···O2ⁱⁱ	0.95	2.50	3.182 (3)	129
C17—H17···O2ⁱⁱⁱ	0.95	2.53	3.350 (4)	145
C22—H22···O2^iv	0.95	2.49	3.085 (3)	120

Symmetry codes: (ii) x−1/2, −y+1, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) x+1/2, −y+1, −z+1/2.

Selected structural parameters (Å) for related metalloporphyrin nitrato complexes top

Δ₄ is the displacement of the metal atom from the mean plane of the four pyrrole nitrogen atoms and Δ₂₄ is the displacement of the metal atom from the 24-atom mean plane.

Complex	Δ₄	Δ₂₄	M—O	N—O1	M—N_p	Ref.
[Mn(TPP)(NO₃)] (Pccn) benzene and n-hexane hemisolvate	0.23	0.22	2.1246 (18)	1.260 (3) 1.236 (3) 1.230 (3)	2.011 (6)	This work
[Mn(TPP)(NO₃)] (P1) benzene disolvate	0.21	0.20	2.101 (3)	1.298 (4) 1.226 (5) 1.226 (5)	2.007 (9)	(Suslick & Watson, 1991)
[Fe(OEP)(NO₃)] (P2₁/c)	0.40	0.45	1.966 (2)	1.301 (3) 1.199 (3) 1.212 (3)	2.047 (6)	(Wyllie et al., 2007)
[Fe(OEP)(NO₃)] (P1)	0.46	0.50	2.016 (3)	1.206 (5) 1.198 (4) 1.208 (6)	2.056 (1)	(Ellison et al., 1996)
[Fe(4-Me-TTP)(NO₃)]	0.47	0.53	1.971 (3)	1.262 (5) 1.252 (5) 1.221 (4)	2.063 (13)	(Bhuyan & Sarkar, 2013)
[Fe(TPP)(NO₃)]	0.54	0.63	2.121 (6) 2.19 (10)	1.27 (10) 1.285 (21) 1.217 (3)	2.085 (10)	(Wyllie et al., 2007)
[Fe(TpivPP)(NO₃)]	0.42	0.49	2.123 (3) 2.226 (3)	1.271 (4) 1.252 (4) 1.214 (3)	2.070 (16)	(Munro & Scheidt, 1998)
[Fe(4-OMe-TPP)(NO₃)]	0.55	0.62	2.169 (5) 2.169 (5)	1.216 (5) 1.276 (8) 1.216 (5)	2.05 (3)	(Bhuyan & Sarkar, 2013)

Funding information

The authors thank the National Natural Science Foundation of China (grant No. 21977093 to JL) for support. This work was supported in part by the Strategic Priority Research Program of the Chinese Academy of Sciences, grant No. XDB28000000.

References

Averill, B. A. (1996). Chem. Rev. 96, 2951–2964. CrossRef PubMed CAS Web of Science Google Scholar
Bhuyan, J. & Sarkar, S. (2013). J. Chem. Sci. 125, 707–714. CSD CrossRef CAS Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. (1996). Acc. Chem. Res. 29, 441–449. CrossRef CAS PubMed Web of Science Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ellison, M. K., Shang, M., Kim, J. & Scheidt, W. R. (1996). Acta Cryst. C52, 3040–3043. CSD CrossRef CAS IUCr Journals Google Scholar
He, M., Li, X., Liu, Y. & Li, J. (2016). Inorg. Chem. 55, 5871–5879. Web of Science CSD CrossRef CAS PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Munro, O. Q. & Scheidt, W. R. (1998). Inorg. Chem. 37, 2308–2316. CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Steiner, T. & Desiraju, G. R. (1998). Chem. Commun. pp. 891–892. Web of Science CrossRef Google Scholar
Suslick, K. S. & Watson, R. A. (1991). Inorg. Chem. 30, 912–919. CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wyllie, G. R., Munro, O. Q., Schulz, C. E. & Scheidt, W. R. (2007). Polyhedron, 26, 4664–4672. CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 4| April 2022| x220386

https://doi.org/10.1107/S2414314622003868

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Nitrato(5,10,15,20-tetra­phenyl­porphinato)manganese(III)–benzene–n-hexa­ne (2/1/1)

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

metal-organic compounds

Nitrato(5,10,15,20-tetraphenylporphinato)manganese(III)–benzene–n-hexane (2/1/1)