research communications
a]pyridinium-based hybrid salt (C13H12N3)2[MnCl4]
of imidazo[1,5-aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine, bInstitute for Sorption and Problems of Endoecology, the National Academy of Sciences of Ukraine, 13 General Naumov str., Kyiv 03164, Ukraine, and cSchool of Molecular Sciences, M310, University of Western Australia, Perth, WA 6009, Australia
*Correspondence e-mail: vassilyeva@univ.kiev.ua
A new organic–inorganic hybrid salt [L]2[MnCl4] (I) where L+ is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cation, is built of discrete organic cations and tetrachloridomanganate(II) anions. The L+ cation was formed in situ in the oxidative cyclocondensation of 2-pyridinecarbaldehyde and CH3NH2·HCl in methanol. The structure was refined as a two-component twin using PLATON (Spek, 2020) to de-twin the data. The (−1 0 0 0 − 1 0 0.5 0 1) was applied in the where the twin component fraction refined to 0.155 (1). The compound crystallizes in the P21/c with two crystallographically non-equivalent cations in the which possess similar structural conformations. The fused pyridinium and imidazolium rings of the cations are virtually coplanar [dihedral angles are 0.89 (18) and 0.78 (17)°]; the pendant pyridyl rings are twisted by 36.83 (14) and 36.14 (13)° with respect to the planes of the remaining atoms of the cations. The tetrahedral MnCl42– anion is slightly distorted with the Mn—Cl distances falling in the range 2.3469 (10)–2.3941 (9) Å. The distortion value of 0.044 relative to the ideal tetrahedron was obtained by continuous shape measurement (CShM) analysis. In the crystal, the cations and anions form separate stacks propagating along the a-axis direction. The organic cations display weak π–π stacking. The anions, which are stacked identically one above the other, demonstrate loose packing; the minimum Mn⋯Mn separation in the cation stack is approximately 7.49 Å. The investigation of the fluorescent properties of a powdered sample of (I) showed no emission. X-band EPR data for (I) at 293 and 77 K revealed broad fine structure signals, indicating moderate zero-field splitting.
Keywords: crystal structure; MnII; organic-inorganic hybrid; tetrahalometallate; π–π stacking.
CCDC reference: 1955880
1. Chemical context
Salts comprised of organic cations (A) and halometallate anions are a highly promising class of compounds within the more general domain of organic–inorganic hybrid materials. Hybrid salts A2[MHal4] based on tetrahedral anions of divalent transition metal ions (M = Zn, Mn, Co, Fe, Cd) can exhibit thermochromism (Kelley et al., 2015) and multiferroic properties (Kapustianyk et al., 2015) as well as acting as molecular switchable dielectrics (Ji et al., 2018) and ionic liquids (Miao et al., 2011). Monovalent organic cations, where size, shape and electronic structure can be varied over wide limits, are a valuable tool for introducing useful properties into the hybrid structure. Heterocycles with the imidazo[1,5-a]pyridine skeleton have been identified as highly emissive fluorophores that render them suitable for optoelectronic devices (Hutt et al., 2012; Yagishita et al., 2018). Incorporation of the imidazo[1,5-a]pyridinium moiety in the hybrid structure is expected to extend the applications of the organic material, and also address such issues as mechanical properties, chemical resistance, thermal stability, etc., that limit the applicability of pure organics.
We have previously shown that the introduction of tetrachlorozincate anions significantly changes the optical behaviour of [L][Cl]·1.5H2O, where L+ is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cation, in the solid state, also improving the thermal stability of the resulting hybrid salt (Buvaylo et al., 2015). The L+ cation was formed in situ in the oxidative cyclocondensation of 2-pyridinecarbaldehyde (2-PCA) and CH3NH2·HCl in methanol. Upon excitation at 370 nm, a strong fluorescence was observed for [L][Cl]·1.5H2O at 406 nm, while [L]2[ZnCl4] [CSD (Groom et al., 2016) refcode HUMHII; Buvaylo et al., 2015] showed an intense blue-light fluorescence peak at 455 nm. Recent findings by Wei and coworkers on the unusual behaviour of tetrahedral manganese(II) hybrid compounds, (N-methylpiperidinium)MnCl4 and (N-methylpyrrolidinium)MnCl4 (Wei et al., 2018), prompted us to synthesize the new organic–inorganic hybrid salt [L]2[MnCl4] (I) by the reaction of 2-PCA, CH3NH2·HCl and MnCl2·4H2O in CH3OH.
The investigation of the fluorescent properties of a powdered sample of (I) at room temperature under experimental conditions similar to those for [L]2[ZnCl4] showed no emission. The replacement of ZnII with MnII ions in the hybrid structure, which also changed the from orthorhombic Pbca with Z = 8 to monoclinic P21/c with Z = 4, quenched the fluorescence emission.
2. Structural commentary
Monoclinic crystals of [L]2[MnCl4] are built of discrete organic cations and tetrachloridomanganate(II) anions (Fig. 1). In the there are two crystallographically non-equivalent cations, L1 (N12, N13A) and L2 (N22, N23A), with similar structural conformations. The six-membered rings in the flattened imidazo[1,5-a]pyridinium cores have the expected bond lengths; the N/C—C bond distances in the imidazolium entities fall in the range 1.352 (4)–1.400 (4) Å. Both nitrogen atoms in L1 and L2 are planar, showing the sum of the three angles to be 360°. The fused pyridinium and imidazolium rings of the cations are virtually coplanar with dihedral angles of 0.89 (18) (L1) and 0.78 (17)° (L2). The pendant pyridyl rings are twisted by 36.83 (14) and 36.14 (13)° with respect to the planes of the remaining atoms of the cations for L1 and L2, respectively. The geometric parameters of the cations closely resemble those found in the related organic–inorganic hybrids [L]2[MCl4], where M = CoII, ZnII, and [L]2[CdI4] (Buvaylo et al., 2015; Vassilyeva et al., 2019a,b).
The tetrahedral MnCl42– ion is slightly distorted. The Mn—Cl distances fall in the range 2.3469 (10)–2.3941 (9) Å and the Cl—Mn—Cl angles vary from 107.60 (3) to 112.95 (4)° (Table 1). The maximum differences in the lengths and angles are 0.047 Å and 5.35°, respectively. The distortion value of 0.044 relative to the ideal tetrahedron obtained by the continuous shape measurement (CShM) analysis using the SHAPE 2.1 program (Casanova et al., 2005) supports a low degree of deformation.
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3. Supramolecular features
In the crystal, the cations and anions form separate stacks propagating along the a-axis direction (Fig. 2). The alternating L1 and L2 organic cations display offset π–π stacking between the six-membered rings of the fused cores with the ring-centroid distances of 3.556 (2) and 4.0410 (2) Å. The aromatic stacking between the neighbouring pendant pyridyl rings of L1 and L2, which are twisted with respect to each other by 19.41 (17)° is also weak [the ring-centroid separations are 3.724 (2) and 3.956 (2) Å]. The anions, which are stacked identically one above the other, demonstrate loose packing: the shortest distance between the Cl atoms of adjacent anions of 3.79 Å is larger than double the chloride ionic radius (3.62 Å; Shannon, 1976). As a consequence, the minimum Mn⋯Mn separation in the cation stack is approximately 7.49 Å.
Classical hydrogen-bonding interactions are absent in (I). There are five C—H⋯Cl contacts between the cations and adjacent MnCl42– anions shorter than the van der Waals contact limit of 2.95 Å (Table 2). The closest cation–anion distance (C24—H24⋯Cl3—Mn) is 2.64 Å.
4. Database survey
A survey of the Cambridge Structural Database (CSD, Version 5.40, Oct 2019; Groom et al., 2016) reveals that crystal structures containing an L+ cation comprise the structures of two ligands in a salt form, three tetrahalometallates [L]2[MCl4] and [L]2[CdI4], as well as two molecular complexes [MLCl3] (M = CoII and ZnII) published by our group. While the latter are isostructural, the four hybrid tetrahalometallates including (I) possess different unit-cell parameters. The organic–inorganic hybrids exhibit either pseudo-layered structures with alternating layers of organic cations and of tetrahalometallate anions or are built of cations and anions arranged in separate stacks.
The imidazo[1,5-a]pyridinium core can be modified with various substituents on the aromatic rings and N(CH3) atom. Crystal structures of ten organic salts with L+ derivatives as cations but no organic–inorganic hybrids or metal complexes are known. UREYIA (Türkyılmaz et al., 2011) and YIHFEB (Mitra et al., 2007), which bear ethylimidazolium and chlorophenyl substituents, respectively, instead of the methyl group in L+ are the most closely related. The lack of the methyl group turns L+ into a neutral molecule L′ that acts as a κ2(N,N) chelate ligand, forming the molecular MnII complex [Mn{S2P(OEt)2}2(L′)] (Álvarez et al., 2012).
5. IR and EPR spectroscopy measurements
The IR spectrum of (I) is very similar to those of [L]2[CoCl4] and [L]2[ZnCl4] (Vassilyeva et al., 2019a; Buvaylo et al., 2015) and shows a distinctive pattern that can be considered characteristic of L+ (see supporting information). It includes intense absorption in the aromatic =C—H stretching region (3136–3012 cm−1) with several narrow peaks, weak bands below 3000 cm−1 due to alkyl –C—H stretching, sharp bands of medium intensity at 1650, 1586, 1516, 1470 and 1422 cm−1 associated with heterocyclic ring stretching, a very strong band at 780 cm−1 and two less strong absorptions in the out-of-plane C—H bending region 800–600 cm−1 (peaks at 742 and 664 cm−1). The remarkable feature of the spectrum is a gap in absorbance from 1650 to 1586 cm−1.
The electronic structure of (I) was probed through X-band EPR spectroscopy at room temperature (r.t.) and 77 K. The EPR spectra of the neat powder sample are temperature-dependent (Fig. 3). At both temperatures, they are dominated by a strong line at 3500 G (geff ∼2) flanked by broad fine structure signals at approximately 900, 2200, 5000 and 6000 G (77 K; geff ∼7.97, 3.20, 1.42 and 1.16, respectively). The outer lines indicate zero-field splitting (ZFS) of the spin states for the high-spin d5 metal ion. As expected for neat-powder EPR spectra, the 55Mn hyperfine structure due to the coupling of the unpaired electron spins with the I = 55Mn nucleus is not resolved. The intermolecular dipole–dipole interactions and the D-strain (D is the axial ZFS parameter) broaden the lines, thus preventing observation of the hyperfine structure in the spectra of neat powders (Duboc et al., 2010). Computer simulation of the 77 K spectrum performed with the program SPIN (S > ; Ozarowski, 2019) yielded axial and rhombic ZFS parameters D of 0.062 cm−1 and E close to D/3, respectively. The highest field lines at ∼6000 and 5000 G result from a mixture of the Z and Y transitions | > → |> and | > → | >, respectively.
For high-spin MnII complexes, a very small anisotropy of the Zeeman interaction leads to g values close to 2, and the shape of the spectra depends on the ZFS terms only (Pilbrow, 1990). ZFS is highly sensitive to the coordination environment of the metal ion and if all bonds in the MnCl4 tetrahedron are equal, one may expect only a strong and broadened single resonance line at g = 2 recorded in the EPR spectra. Indeed, one isotropic line with an unchanged linewidth of about 100 mT and a g-value of 2.0039 was observed in the X-band EPR spectrum of the organic–inorganic hybrid [(CH3)4N]2MnCl4 from 400 down to 20 K (Köksal et al., 1999). The EPR spectra of another hybrid, [(C2H5)4N]2MnCl4, also consist of a broadened line with the isotropic g-value of 2.001 (3) in the temperature range 170–300 K (Ostrowski & Ciżman, 2008). The appearance of fine structure in the spectrum of (I) needs further study that requires the high-field/high-frequency EPR spectroscopy experiments to be undertaken at lower temperatures (Gagnon et al., 2019).
6. Synthesis and crystallization
2-PCA (0.38 ml, 4 mmol) was stirred with CH3NH2·HCl (0.27 g, 4 mmol) in 20 ml of methanol in a 50 ml conical flask at room temperature for half an hour. The resultant yellow solution was left in open air overnight and used as the ligand without further purification. Dry MnCl2·4H2O (0.40 g, 2 mmol) was added to the solution of the ligand (which had turned olive) and the mixture was magnetically stirred under mild heating for 20 min to ensure dissolution of the metal salt. The resulting solution was filtered and left to cool at r.t. Colourless needles of (I) suitable for X-ray analysis were deposited next day. They were filtered off, washed with diethyl ether and finally dried in air. More product was obtained upon slow evaporation in air of the mother liquor. Total yield: 88%. Analysis calculated for (I), C26H24Cl4N6Mn (617.25): C, 50.59; H 3.92; N 13.62%. Found: C 50.69; H 3.75; N 13.39%. IR (ν, cm−1, KBr): 3402 (br), 3168, 3136, 3110, 3090, 3054, 3012, 2952, 2922, 1650, 1586, 1568, 1528 (sh), 1516, 1470, 1422, 1366, 1332, 1252, 1190, 1156, 1104, 1040, 992, 942, 780 (vs), 742 (s), 664, 610, 556, 500, 434.
7. Refinement
Crystal data, data collection and structure . The structure was refined as a two-component twin using PLATON (Spek, 2020) to de-twin the data. The (−1 0 0 0 − 1 0 0.5 0 1) was applied in the where the twin component fraction refined to 0.155 (1). Anisotropic displacement parameters were employed for the non-hydrogen atoms. All hydrogen atoms were added at calculated positions and refined by use of a riding model with isotropic displacement parameters based on those of the parent atom (C—H = 0.95 Å, Uiso(H) = 1.2UeqC for CH, C—H = 0.98 Å, Uiso(H) = 1.5UeqC for CH3).
details are summarized in Table 3Supporting information
CCDC reference: 1955880
https://doi.org/10.1107/S2056989020001425/lh5945sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001425/lh5945Isup2.hkl
IR spectrum. DOI: https://doi.org/10.1107/S2056989020001425/lh5945sup3.pdf
Data collection: CrysAlis PRO (Rigaku OD, 2016); cell
CrysAlis PRO (Rigaku OD, 2016); data reduction: CrysAlis PRO (Rigaku OD, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).(C13H12N3)2[MnCl4] | F(000) = 1260 |
Mr = 617.25 | Dx = 1.536 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10548 reflections |
a = 7.4892 (1) Å | θ = 3.6–34.6° |
b = 15.9488 (4) Å | µ = 0.92 mm−1 |
c = 22.4266 (5) Å | T = 100 K |
β = 94.896 (2)° | Needle, colourless |
V = 2668.94 (10) Å3 | 0.36 × 0.1 × 0.08 mm |
Z = 4 |
Oxford Diffraction Gemini diffractometer | 7856 independent reflections |
Graphite monochromator | 6781 reflections with I > 2σ(I) |
Detector resolution: 10.4738 pixels mm-1 | Rint = 0.069 |
ω scans | θmax = 30.1°, θmin = 3.6° |
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2016) | h = −10→10 |
Tmin = 0.753, Tmax = 0.942 | k = −22→22 |
7856 measured reflections | l = −4→31 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.186 | w = 1/[σ2(Fo2) + (0.106P)2 + 2.4383P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max < 0.001 |
7856 reflections | Δρmax = 0.58 e Å−3 |
337 parameters | Δρmin = −0.69 e Å−3 |
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. Refined as a 2-component twin using PLATON to de-twin the data. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.18155 (7) | 0.24718 (3) | 0.12270 (2) | 0.01416 (13) | |
Cl1 | −0.09406 (11) | 0.17752 (5) | 0.10546 (4) | 0.01936 (17) | |
Cl2 | 0.41361 (11) | 0.14691 (5) | 0.12578 (3) | 0.01805 (17) | |
Cl3 | 0.18969 (12) | 0.31455 (5) | 0.21748 (3) | 0.01903 (17) | |
Cl4 | 0.22558 (12) | 0.35257 (5) | 0.04936 (4) | 0.02042 (18) | |
C11 | 0.7917 (5) | 0.1463 (2) | 0.25204 (15) | 0.0163 (6) | |
H11 | 0.743093 | 0.121304 | 0.215771 | 0.02* | |
N12 | 0.7856 (4) | 0.22928 (17) | 0.26666 (12) | 0.0149 (5) | |
C12 | 0.6912 (5) | 0.2909 (2) | 0.22796 (16) | 0.0207 (7) | |
H12A | 0.619181 | 0.327043 | 0.251868 | 0.031* | |
H12B | 0.612553 | 0.262038 | 0.197364 | 0.031* | |
H12C | 0.778253 | 0.32509 | 0.208559 | 0.031* | |
C13 | 0.8700 (4) | 0.2431 (2) | 0.32148 (14) | 0.0143 (6) | |
N13A | 0.9302 (4) | 0.16698 (17) | 0.34265 (12) | 0.0139 (5) | |
C14 | 1.0262 (5) | 0.1464 (2) | 0.39668 (15) | 0.0171 (6) | |
H14 | 1.05983 | 0.188652 | 0.425342 | 0.02* | |
C15 | 1.0708 (5) | 0.0651 (2) | 0.40762 (15) | 0.0197 (6) | |
H15 | 1.137344 | 0.050607 | 0.444133 | 0.024* | |
C16 | 1.0194 (5) | 0.0007 (2) | 0.36519 (16) | 0.0211 (7) | |
H16 | 1.04999 | −0.056041 | 0.374005 | 0.025* | |
C17 | 0.9270 (5) | 0.0205 (2) | 0.31227 (16) | 0.0191 (6) | |
H17 | 0.893137 | −0.022108 | 0.283952 | 0.023* | |
C17A | 0.8815 (4) | 0.1056 (2) | 0.29965 (14) | 0.0150 (6) | |
C21 | 0.6189 (4) | 0.0675 (2) | 0.43736 (16) | 0.0182 (6) | |
H21 | 0.676985 | 0.022658 | 0.459085 | 0.022* | |
N22 | 0.6065 (4) | 0.14828 (18) | 0.45664 (12) | 0.0161 (5) | |
C22 | 0.6955 (5) | 0.1792 (2) | 0.51343 (15) | 0.0216 (7) | |
H22A | 0.734725 | 0.237161 | 0.508343 | 0.032* | |
H22B | 0.79976 | 0.143911 | 0.525234 | 0.032* | |
H22C | 0.61138 | 0.17701 | 0.544551 | 0.032* | |
C23 | 0.5132 (4) | 0.1952 (2) | 0.41441 (14) | 0.0153 (6) | |
N23A | 0.4677 (4) | 0.14328 (17) | 0.36724 (12) | 0.0148 (5) | |
C24 | 0.3675 (4) | 0.1610 (2) | 0.31331 (14) | 0.0170 (6) | |
H24 | 0.320143 | 0.215412 | 0.305083 | 0.02* | |
C25 | 0.3403 (5) | 0.0979 (2) | 0.27312 (16) | 0.0205 (7) | |
H25 | 0.274347 | 0.108817 | 0.23585 | 0.025* | |
C26 | 0.4079 (5) | 0.0154 (2) | 0.28524 (16) | 0.0210 (7) | |
H26 | 0.38685 | −0.0273 | 0.255977 | 0.025* | |
C27 | 0.5020 (5) | −0.0026 (2) | 0.33805 (16) | 0.0199 (6) | |
H27 | 0.546507 | −0.05758 | 0.34619 | 0.024* | |
C27A | 0.5324 (4) | 0.0626 (2) | 0.38099 (15) | 0.0155 (6) | |
C131 | 0.8898 (4) | 0.3228 (2) | 0.35385 (14) | 0.0147 (6) | |
C136 | 0.9174 (5) | 0.3981 (2) | 0.32441 (14) | 0.0164 (6) | |
H136 | 0.930694 | 0.398767 | 0.28266 | 0.02* | |
C135 | 0.9251 (5) | 0.4717 (2) | 0.35712 (16) | 0.0201 (7) | |
H135 | 0.941632 | 0.524 | 0.338116 | 0.024* | |
C134 | 0.9082 (5) | 0.4677 (2) | 0.41862 (16) | 0.0200 (7) | |
H134 | 0.911474 | 0.51718 | 0.442251 | 0.024* | |
C133 | 0.8864 (5) | 0.3896 (2) | 0.44431 (14) | 0.0187 (6) | |
H133 | 0.87798 | 0.386788 | 0.486295 | 0.022* | |
N132 | 0.8764 (4) | 0.31762 (18) | 0.41298 (13) | 0.0180 (5) | |
C231 | 0.4668 (4) | 0.2846 (2) | 0.41729 (14) | 0.0143 (6) | |
C236 | 0.4232 (5) | 0.3215 (2) | 0.47027 (15) | 0.0185 (6) | |
H236 | 0.421074 | 0.289572 | 0.505961 | 0.022* | |
C235 | 0.3827 (5) | 0.4069 (2) | 0.46946 (16) | 0.0219 (7) | |
H235 | 0.35516 | 0.434543 | 0.505041 | 0.026* | |
C234 | 0.3830 (5) | 0.4504 (2) | 0.41675 (17) | 0.0234 (7) | |
H234 | 0.355126 | 0.508481 | 0.415031 | 0.028* | |
C233 | 0.4251 (5) | 0.4074 (2) | 0.36591 (17) | 0.0219 (7) | |
H233 | 0.423424 | 0.437845 | 0.329457 | 0.026* | |
N232 | 0.4674 (4) | 0.32664 (18) | 0.36493 (13) | 0.0173 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0153 (2) | 0.0128 (2) | 0.0146 (2) | 0.00108 (18) | 0.00254 (17) | 0.00018 (17) |
Cl1 | 0.0168 (4) | 0.0201 (4) | 0.0213 (4) | −0.0013 (3) | 0.0021 (3) | 0.0024 (3) |
Cl2 | 0.0175 (3) | 0.0190 (4) | 0.0177 (3) | 0.0041 (3) | 0.0019 (3) | −0.0019 (3) |
Cl3 | 0.0244 (4) | 0.0162 (3) | 0.0166 (3) | 0.0054 (3) | 0.0023 (3) | −0.0013 (3) |
Cl4 | 0.0271 (4) | 0.0148 (3) | 0.0200 (4) | 0.0001 (3) | 0.0054 (3) | 0.0025 (3) |
C11 | 0.0196 (15) | 0.0131 (13) | 0.0165 (14) | −0.0046 (12) | 0.0028 (12) | −0.0042 (11) |
N12 | 0.0161 (13) | 0.0110 (11) | 0.0176 (12) | −0.0003 (10) | 0.0018 (10) | −0.0003 (9) |
C12 | 0.0257 (17) | 0.0140 (14) | 0.0216 (15) | 0.0030 (13) | −0.0032 (13) | 0.0016 (12) |
C13 | 0.0131 (13) | 0.0138 (14) | 0.0163 (14) | −0.0017 (11) | 0.0044 (11) | −0.0008 (11) |
N13A | 0.0145 (12) | 0.0124 (11) | 0.0152 (12) | −0.0005 (10) | 0.0041 (10) | −0.0004 (9) |
C14 | 0.0158 (14) | 0.0172 (15) | 0.0181 (14) | 0.0005 (12) | 0.0004 (11) | 0.0000 (12) |
C15 | 0.0204 (16) | 0.0178 (15) | 0.0212 (15) | 0.0031 (13) | 0.0043 (12) | 0.0043 (12) |
C16 | 0.0199 (16) | 0.0172 (15) | 0.0277 (17) | 0.0015 (13) | 0.0104 (13) | 0.0039 (13) |
C17 | 0.0195 (16) | 0.0125 (14) | 0.0260 (16) | −0.0007 (12) | 0.0068 (13) | −0.0016 (12) |
C17A | 0.0147 (14) | 0.0135 (14) | 0.0172 (14) | −0.0015 (11) | 0.0035 (11) | −0.0030 (11) |
C21 | 0.0143 (14) | 0.0134 (14) | 0.0266 (16) | 0.0024 (12) | 0.0006 (12) | 0.0037 (12) |
N22 | 0.0155 (12) | 0.0166 (12) | 0.0164 (12) | 0.0005 (11) | 0.0022 (10) | 0.0013 (10) |
C22 | 0.0224 (17) | 0.0240 (17) | 0.0174 (15) | −0.0004 (14) | −0.0037 (13) | 0.0019 (13) |
C23 | 0.0151 (14) | 0.0169 (14) | 0.0144 (13) | −0.0005 (12) | 0.0044 (11) | −0.0005 (11) |
N23A | 0.0132 (12) | 0.0130 (12) | 0.0182 (12) | −0.0010 (10) | 0.0011 (10) | −0.0003 (10) |
C24 | 0.0158 (14) | 0.0199 (15) | 0.0155 (14) | −0.0026 (12) | 0.0030 (11) | −0.0002 (12) |
C25 | 0.0198 (16) | 0.0217 (16) | 0.0201 (15) | −0.0083 (14) | 0.0026 (12) | −0.0015 (13) |
C26 | 0.0217 (16) | 0.0188 (15) | 0.0235 (16) | −0.0056 (13) | 0.0072 (13) | −0.0062 (13) |
C27 | 0.0191 (16) | 0.0128 (14) | 0.0286 (17) | −0.0009 (12) | 0.0057 (13) | −0.0008 (12) |
C27A | 0.0125 (13) | 0.0133 (13) | 0.0205 (15) | −0.0002 (11) | 0.0007 (11) | −0.0003 (11) |
C131 | 0.0129 (13) | 0.0123 (13) | 0.0187 (14) | −0.0019 (11) | 0.0002 (11) | −0.0015 (11) |
C136 | 0.0181 (15) | 0.0146 (14) | 0.0168 (14) | −0.0008 (12) | 0.0029 (12) | −0.0005 (11) |
C135 | 0.0208 (16) | 0.0130 (14) | 0.0265 (17) | 0.0005 (13) | 0.0018 (13) | 0.0004 (12) |
C134 | 0.0217 (16) | 0.0117 (14) | 0.0264 (17) | 0.0010 (12) | 0.0020 (13) | −0.0057 (12) |
C133 | 0.0205 (16) | 0.0227 (16) | 0.0132 (13) | −0.0019 (13) | 0.0025 (12) | −0.0026 (12) |
N132 | 0.0182 (13) | 0.0152 (13) | 0.0212 (13) | −0.0017 (11) | 0.0052 (11) | −0.0015 (10) |
C231 | 0.0140 (14) | 0.0127 (13) | 0.0163 (14) | −0.0013 (11) | 0.0016 (11) | −0.0002 (11) |
C236 | 0.0203 (16) | 0.0177 (15) | 0.0186 (15) | −0.0012 (13) | 0.0074 (12) | 0.0013 (12) |
C235 | 0.0255 (17) | 0.0157 (15) | 0.0258 (17) | −0.0015 (14) | 0.0096 (14) | −0.0053 (13) |
C234 | 0.0253 (17) | 0.0121 (14) | 0.0338 (19) | −0.0001 (13) | 0.0085 (15) | −0.0013 (13) |
C233 | 0.0226 (16) | 0.0165 (15) | 0.0266 (17) | 0.0020 (13) | 0.0024 (13) | 0.0036 (13) |
N232 | 0.0164 (13) | 0.0148 (12) | 0.0207 (13) | −0.0007 (11) | 0.0015 (10) | 0.0010 (10) |
Mn1—Cl1 | 2.3469 (10) | C23—N23A | 1.364 (4) |
Mn1—Cl2 | 2.3585 (9) | C23—C231 | 1.471 (5) |
Mn1—Cl3 | 2.3779 (9) | N23A—C24 | 1.396 (4) |
Mn1—Cl4 | 2.3941 (9) | N23A—C27A | 1.400 (4) |
C11—N12 | 1.366 (4) | C24—C25 | 1.355 (5) |
C11—C17A | 1.375 (5) | C24—H24 | 0.95 |
C11—H11 | 0.95 | C25—C26 | 1.427 (5) |
N12—C13 | 1.352 (4) | C25—H25 | 0.95 |
N12—C12 | 1.454 (4) | C26—C27 | 1.356 (5) |
C12—H12A | 0.98 | C26—H26 | 0.95 |
C12—H12B | 0.98 | C27—C27A | 1.423 (5) |
C12—H12C | 0.98 | C27—H27 | 0.95 |
C13—N13A | 1.367 (4) | C131—N132 | 1.341 (4) |
C13—C131 | 1.465 (4) | C131—C136 | 1.394 (4) |
N13A—C14 | 1.394 (4) | C136—C135 | 1.383 (5) |
N13A—C17A | 1.400 (4) | C136—H136 | 0.95 |
C14—C15 | 1.357 (5) | C135—C134 | 1.397 (5) |
C14—H14 | 0.95 | C135—H135 | 0.95 |
C15—C16 | 1.430 (5) | C134—C133 | 1.388 (5) |
C15—H15 | 0.95 | C134—H134 | 0.95 |
C16—C17 | 1.359 (5) | C133—N132 | 1.344 (4) |
C16—H16 | 0.95 | C133—H133 | 0.95 |
C17—C17A | 1.422 (4) | C231—N232 | 1.353 (4) |
C17—H17 | 0.95 | C231—C236 | 1.390 (4) |
C21—N22 | 1.364 (4) | C236—C235 | 1.394 (5) |
C21—C27A | 1.373 (5) | C236—H236 | 0.95 |
C21—H21 | 0.95 | C235—C234 | 1.371 (5) |
N22—C23 | 1.353 (4) | C235—H235 | 0.95 |
N22—C22 | 1.471 (4) | C234—C233 | 1.389 (5) |
C22—H22A | 0.98 | C234—H234 | 0.95 |
C22—H22B | 0.98 | C233—N232 | 1.327 (4) |
C22—H22C | 0.98 | C233—H233 | 0.95 |
Cl1—Mn1—Cl2 | 108.62 (3) | N22—C23—C231 | 128.0 (3) |
Cl1—Mn1—Cl3 | 108.44 (3) | N23A—C23—C231 | 125.3 (3) |
Cl2—Mn1—Cl3 | 108.51 (3) | C23—N23A—C24 | 129.0 (3) |
Cl1—Mn1—Cl4 | 112.95 (4) | C23—N23A—C27A | 109.2 (3) |
Cl2—Mn1—Cl4 | 110.60 (3) | C24—N23A—C27A | 121.8 (3) |
Cl3—Mn1—Cl4 | 107.60 (3) | C25—C24—N23A | 117.7 (3) |
N12—C11—C17A | 107.2 (3) | C25—C24—H24 | 121.1 |
N12—C11—H11 | 126.4 | N23A—C24—H24 | 121.1 |
C17A—C11—H11 | 126.4 | C24—C25—C26 | 121.8 (3) |
C13—N12—C11 | 110.7 (3) | C24—C25—H25 | 119.1 |
C13—N12—C12 | 126.7 (3) | C26—C25—H25 | 119.1 |
C11—N12—C12 | 122.4 (3) | C27—C26—C25 | 120.8 (3) |
N12—C12—H12A | 109.5 | C27—C26—H26 | 119.6 |
N12—C12—H12B | 109.5 | C25—C26—H26 | 119.6 |
H12A—C12—H12B | 109.5 | C26—C27—C27A | 118.5 (3) |
N12—C12—H12C | 109.5 | C26—C27—H27 | 120.8 |
H12A—C12—H12C | 109.5 | C27A—C27—H27 | 120.8 |
H12B—C12—H12C | 109.5 | C21—C27A—N23A | 106.1 (3) |
N12—C13—N13A | 106.6 (3) | C21—C27A—C27 | 134.5 (3) |
N12—C13—C131 | 127.8 (3) | N23A—C27A—C27 | 119.4 (3) |
N13A—C13—C131 | 125.6 (3) | N132—C131—C136 | 123.3 (3) |
C13—N13A—C14 | 129.9 (3) | N132—C131—C13 | 115.1 (3) |
C13—N13A—C17A | 108.9 (3) | C136—C131—C13 | 121.7 (3) |
C14—N13A—C17A | 121.2 (3) | C135—C136—C131 | 118.7 (3) |
C15—C14—N13A | 118.9 (3) | C135—C136—H136 | 120.6 |
C15—C14—H14 | 120.6 | C131—C136—H136 | 120.6 |
N13A—C14—H14 | 120.6 | C136—C135—C134 | 118.8 (3) |
C14—C15—C16 | 121.2 (3) | C136—C135—H135 | 120.6 |
C14—C15—H15 | 119.4 | C134—C135—H135 | 120.6 |
C16—C15—H15 | 119.4 | C133—C134—C135 | 118.3 (3) |
C17—C16—C15 | 120.1 (3) | C133—C134—H134 | 120.8 |
C17—C16—H16 | 119.9 | C135—C134—H134 | 120.8 |
C15—C16—H16 | 119.9 | N132—C133—C134 | 123.5 (3) |
C16—C17—C17A | 119.4 (3) | N132—C133—H133 | 118.2 |
C16—C17—H17 | 120.3 | C134—C133—H133 | 118.2 |
C17A—C17—H17 | 120.3 | C131—N132—C133 | 117.3 (3) |
C11—C17A—N13A | 106.6 (3) | N232—C231—C236 | 123.4 (3) |
C11—C17A—C17 | 134.3 (3) | N232—C231—C23 | 115.1 (3) |
N13A—C17A—C17 | 119.1 (3) | C236—C231—C23 | 121.5 (3) |
N22—C21—C27A | 107.8 (3) | C231—C236—C235 | 118.0 (3) |
N22—C21—H21 | 126.1 | C231—C236—H236 | 121 |
C27A—C21—H21 | 126.1 | C235—C236—H236 | 121 |
C23—N22—C21 | 110.2 (3) | C234—C235—C236 | 119.3 (3) |
C23—N22—C22 | 126.1 (3) | C234—C235—H235 | 120.4 |
C21—N22—C22 | 123.5 (3) | C236—C235—H235 | 120.4 |
N22—C22—H22A | 109.5 | C235—C234—C233 | 118.4 (3) |
N22—C22—H22B | 109.5 | C235—C234—H234 | 120.8 |
H22A—C22—H22B | 109.5 | C233—C234—H234 | 120.8 |
N22—C22—H22C | 109.5 | N232—C233—C234 | 124.3 (3) |
H22A—C22—H22C | 109.5 | N232—C233—H233 | 117.8 |
H22B—C22—H22C | 109.5 | C234—C233—H233 | 117.8 |
N22—C23—N23A | 106.7 (3) | C233—N232—C231 | 116.6 (3) |
C17A—C11—N12—C13 | 0.7 (4) | N23A—C24—C25—C26 | 1.1 (5) |
C17A—C11—N12—C12 | −176.4 (3) | C24—C25—C26—C27 | 0.3 (5) |
C11—N12—C13—N13A | −0.5 (4) | C25—C26—C27—C27A | −0.3 (5) |
C12—N12—C13—N13A | 176.5 (3) | N22—C21—C27A—N23A | 0.0 (4) |
C11—N12—C13—C131 | −178.6 (3) | N22—C21—C27A—C27 | 178.9 (4) |
C12—N12—C13—C131 | −1.6 (5) | C23—N23A—C27A—C21 | −0.4 (4) |
N12—C13—N13A—C14 | 179.6 (3) | C24—N23A—C27A—C21 | −178.2 (3) |
C131—C13—N13A—C14 | −2.3 (5) | C23—N23A—C27A—C27 | −179.6 (3) |
N12—C13—N13A—C17A | 0.1 (4) | C24—N23A—C27A—C27 | 2.6 (5) |
C131—C13—N13A—C17A | 178.2 (3) | C26—C27—C27A—C21 | −180.0 (4) |
C13—N13A—C14—C15 | 179.8 (3) | C26—C27—C27A—N23A | −1.1 (5) |
C17A—N13A—C14—C15 | −0.8 (5) | N12—C13—C131—N132 | 141.6 (3) |
N13A—C14—C15—C16 | −0.7 (5) | N13A—C13—C131—N132 | −36.1 (5) |
C14—C15—C16—C17 | 1.2 (5) | N12—C13—C131—C136 | −37.3 (5) |
C15—C16—C17—C17A | −0.2 (5) | N13A—C13—C131—C136 | 144.9 (3) |
N12—C11—C17A—N13A | −0.7 (4) | N132—C131—C136—C135 | −2.4 (5) |
N12—C11—C17A—C17 | 178.3 (4) | C13—C131—C136—C135 | 176.5 (3) |
C13—N13A—C17A—C11 | 0.4 (4) | C131—C136—C135—C134 | 1.1 (5) |
C14—N13A—C17A—C11 | −179.2 (3) | C136—C135—C134—C133 | 0.7 (5) |
C13—N13A—C17A—C17 | −178.8 (3) | C135—C134—C133—N132 | −1.6 (5) |
C14—N13A—C17A—C17 | 1.7 (5) | C136—C131—N132—C133 | 1.6 (5) |
C16—C17—C17A—C11 | 180.0 (4) | C13—C131—N132—C133 | −177.3 (3) |
C16—C17—C17A—N13A | −1.2 (5) | C134—C133—N132—C131 | 0.4 (5) |
C27A—C21—N22—C23 | 0.5 (4) | N22—C23—C231—N232 | 144.4 (3) |
C27A—C21—N22—C22 | −175.1 (3) | N23A—C23—C231—N232 | −35.8 (5) |
C21—N22—C23—N23A | −0.7 (4) | N22—C23—C231—C236 | −36.6 (5) |
C22—N22—C23—N23A | 174.7 (3) | N23A—C23—C231—C236 | 143.2 (3) |
C21—N22—C23—C231 | 179.0 (3) | N232—C231—C236—C235 | −1.8 (5) |
C22—N22—C23—C231 | −5.5 (5) | C23—C231—C236—C235 | 179.3 (3) |
N22—C23—N23A—C24 | 178.3 (3) | C231—C236—C235—C234 | 1.6 (5) |
C231—C23—N23A—C24 | −1.5 (5) | C236—C235—C234—C233 | −0.4 (6) |
N22—C23—N23A—C27A | 0.7 (4) | C235—C234—C233—N232 | −0.8 (6) |
C231—C23—N23A—C27A | −179.1 (3) | C234—C233—N232—C231 | 0.7 (5) |
C23—N23A—C24—C25 | −179.9 (3) | C236—C231—N232—C233 | 0.6 (5) |
C27A—N23A—C24—C25 | −2.6 (5) | C23—C231—N232—C233 | 179.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···Cl2 | 0.98 | 2.79 | 3.746 (4) | 167 |
C14—H14···N132 | 0.95 | 2.48 | 2.986 (4) | 114 |
C17—H17···Cl3i | 0.95 | 2.68 | 3.450 (3) | 139 |
C21—H21···Cl4i | 0.95 | 2.82 | 3.625 (3) | 143 |
C22—H22A···Cl1ii | 0.98 | 2.79 | 3.378 (4) | 120 |
C24—H24···Cl3 | 0.95 | 2.64 | 3.450 (4) | 143 |
C24—H24···N232 | 0.95 | 2.43 | 2.955 (4) | 115 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, −y+1/2, z+1/2. |
Acknowledgements
We are thankful to Andrew Ozarowski (NHMFL) for helpful discussion and simulation of the EPR spectrum.
Funding information
Funding for this research was provided by: Ministry of Education and Science of Ukraine (project No. 19BF037-05).
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