research communications
Synthesis, a]pyridin-2-ium) tetrachloridomanganate(II)
and Hirshfeld surface analysis of the hybrid salt bis(2-methylimidazo[1,5-aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine, and bSchool of Molecular Sciences, M310, University of Western Australia, Perth, WA 6009, Australia
*Correspondence e-mail: vassilyeva@univ.kiev.ua
The 0-D hybrid salt bis(2-methylimidazo[1,5-a]pyridin-2-ium) tetrachloridomanganate(II), (C8H9N2)2[MnCl4] or [L]2[MnCl4], consists of discrete L+ cations and tetrachloridomanganate(II) anions. The fused heterocyclic rings in the two crystallographically non-equivalent monovalent organic cations are almost coplanar; the bond lengths are as expected. The tetrahedral MnCl42– dianion is slightly distorted with the Mn—Cl bond lengths varying from 2.3577 (7) to 2.3777 (7) Å and the Cl—Mn—Cl angles falling in the range 105.81 (3)–115.23 (3)°. In the crystal, the compound demonstrates a pseudo-layered arrangement of separate organic and inorganic sheets alternating parallel to the bc plane. In the organic layer, pairs of centrosymmetrically related trans-oriented L+ cations are π-stacked. Neighboring MnCl42– dianions in the inorganic sheet show no connectivity, with the minimal Mn⋯Mn distance exceeding 7 Å. The Hirshfeld surface analysis revealed the prevalence of the non-conventional C—H⋯Cl—Mn hydrogen bonding in the crystal packing.
Keywords: crystal structure; organic–inorganic hybrid; pseudo-layered structure; 2-pyridinecarbaldehyde.
CCDC reference: 1959314
1. Chemical context
Hybrid metal halides combining organic cations and inorganic anions are the focus of research attention as novel light-emitting materials because their ). These materials have potential uses in light-emitting diodes (LEDs), solar cells, and photodetectors as well as in laser technology (Li et al., 2021). The Pb element in this family, however, prevents these materials from being used in commercial settings (Gan et al., 2021). Therefore, the development of lead-free hybrid metal halides is of particular interest. Environmentally safe organic–inorganic manganese(II) halides have been shown to exhibit potent luminescence arising from d–d transitions, making them promising for use in X-ray scintillators, sensors, and optical devices (Kumar Das et al., 2022).
properties are conveniently tunable by engineering their organic and inorganic components (Saparov & Mitzi, 2016The title compound [L]2[MnCl4], (I), was synthesized in the course of our study on organic–inorganic hybrid metal halides of transition and main-group metal atoms counterbalanced with imidazo[1,5-a]pyridinium-based cations (Vassilyeva et al., 2020, 2021, 2023). The monovalent 2-methyl-imidazo[1,5-a]pyridinium cation L+ resulted from the oxidative condensation–cyclization between formaldehyde, methylamine hydrochloride and 2-pyridinecarbaldehyde. The reaction of the preformed heterocyclic cation and metal halides yielded hybrid compounds [L]n[PbCl3]n (TURJUO; Vassilyeva et al., 2020), [L]2[ZnCl4] (GOTHAB01; Vassilyeva et al., 2020), [L]2[CdCl4] (GOTJAD01; Vassilyeva et al., 2021), and [L]2[SnCl6] (GIBFAC; Vassilyeva et al., 2023). The photophysical properties of the organic–inorganic 1-D perovskite [L]n[PbCl3]n and 0-D pseudo-layered hybrid [L]2[ZnCl4] were presumed to originate from the synergistic effects of the electronic structure of the cation and the solid-state architectures. Hybrid compound I, isomorphic with the Zn and Cd analogues GOTHAB01 and GOTJAD01, appeared non-emissive. Herein, the synthesis, structure, IR spectroscopic characterization, and the results of the Hirshfeld surface (HS) analysis of I are reported.
2. Structural commentary
The organic–inorganic hybrid salt I crystallizes in the triclinic P and is isomorphous with the [L]2[ZnCl4] (GOTHAB; Vassilyeva et al., 2020) and [L]2[CdCl4] (GOTJAD; Vassilyeva et al., 2021) analogues as well as the sister mixed-halide ZnII and CdII tetrahalometalates with the L+ cation involving partial substitution of bromide by chloride and chloride by iodide ions (NOTZAA01, NOVSEZ01 and NOVSOJ01; Vassilyeva et al., 2022). Compound I is composed of discrete L+ cations and tetrahedral MnCl42– anions (Fig. 1). In the there are two crystallographically non-equivalent cations (N22, N23A and N12, N13A) with similar structural configurations, which are very close to those of the isomorphous hybrid salts. In the fused cores, the imidazolium rings show C—N/C bond lengths in the range 1.332 (3)–1.405 (3) Å; the pyridinium rings have normal bond distances; the nitrogen atoms are planar, with a total sum of three angles of 360°. The five- and six-membered rings in the cations are almost coplanar, showing dihedral angles between them of less than 2° [0.61 (N22, N23A) and 1.46° (N12, N13A)].
The geometry of the slightly distorted tetrahedral MnCl42– anion with Mn—Cl distances varying from 2.3577 (7) to 2.3777 (7) Å and the bond angles falling in the range 105.81 (3)–115.23 (3)° (Table 1) is typical for this coordinatively rigid anion.
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3. Supramolecular features
In the crystal of I, there is a pseudo-layered arrangement of the organic and inorganic sheets alternating parallel to the bc plane (Fig. 2). The a-axis length [9.4042 (6) Å] corresponds to the distance between consecutive inorganic planes. Pairs of inversion-related cations in the organic layer are stacked with varying levels of offset, showing the ring-centroid distances of 3.453 (1) (N22, N23A), 3.552 (2) and 4.002 (1) Å (N12, N13A) with the corresponding interplanar distances being 3.263 (1), 3.526 (1) and 2.401 (1) Å, respectively. In the inorganic layer, the tetrachloridomanganate(II) anions are loosely packed with the shortest Mn⋯Mn separations being about 7.098 Å. The closest Cl⋯Cl distance of 4.649 Å is significantly larger than the double value of the Shannon ionic radii of chloride anion [2r(Cl−) = 2 × 1.81 = 3.62 Å], making magnetic interactions between the metal ions barely possible. Additional structure consolidation is provided by numerous C—H⋯Cl—Mn hydrogen bonds between organic and inorganic sublattices (Fig. 2, Table 2) at the H⋯Cl distances below the van der Waals contact limit of 2.85 Å (Mantina et al., 2009).
4. Hirshfeld surface analysis
The Hirshfeld surface mapped over dnorm and fingerprint plots for I were generated using CrystalExplorer (Version 21.5; Spackman et al., 2021). The red spots on the Hirshfeld surface indicate close hydrogen-bond donor and acceptor contacts, while the white and blue areas represent van der Waals and longer contacts, respectively. The bright-red spots are found near chlorine atoms involved in C—H⋯Cl hydrogen-bonding interactions between organic cations and MnCl42– anions (Fig. 3). In the fingerprint plots (Fig. 4), those are associated with sharp spikes of 54.8% of the surface area. The next highest contributions to the surface contacts come from the H⋯H (31%), H⋯C (6%) and C⋯C (2.5%) interactions, whereas other Xi⋯Xd contacts (X = H, N, C, Mn) cover less than 6% (Fig. 4). These numbers show that non-conventional hydrogen bonding predominates in the crystal packing of I, but that C–H⋯π and π–π interactions also make an appreciable contribution.
5. Database survey
Compound I is a new member of the family of salts with imidazo[1,5-a]pyridinium-based cations. More than 50 structures of the compounds including such cations are found in the Cambridge Structural Database (CSD, Version 5.42; Groom et al., 2016) with 24 halometalates (M = Mn, Co, Fe, Ni, Cu, Zn, Cd, Pb and Sn) contributed by our research team. Another large group comprises organic salts with substituted L+ cations and inorganic anions such as perchlorate or hexafluorophosphate. NAKNET (Mishra et al., 2005) and DIWYEP (Kriechbaum et al., 2014) with bulky methylphenyl and dimethylphenyl substituents, respectively, instead of the methyl group in L+ are close analogues. A limited amount of the main-group metal halides with imidazo[1,5-a]pyridinium-based cations are known. The proligand bearing a 6-methylpyridin-2-yl substituent in place of the methyl group in L+ (SOHPUC; Samanta et al., 2014) was reported to stabilize both AuI and AuIII ions, enabling the mixed-valence hybrid salt with [AuCl2]− and [AuCl4]− anions (SUWVIR; Nandy et al., 2016). In the reaction with mercury(II) acetate, a similar ligand that lacked a methyl group, produced an HgII–N-heterocyclic carbene complex of virtually linear geometry [Ccarbene—Hg—Ccarbene = 176.56 (17)°] around the Hg center (IVOWEW; Samanta et al., 2011).
The ubiquitous tetrachloride anion is found in more than 200 structures stored in the CSD. The average Mn—Cl distance of 2.37 Å in I is comparable to those found in the database for other salts containing isolated MnCl42– tetrahedral anions (the range of average Mn—Cl distances for this anion is 2.27–2.42 Å).
6. Synthesis and crystallization
Synthesis of [L]2[MnCl4], (I). Solid CH3NH2·HCl (0.27 g, 4 mmol) was added to the warm formaldehyde solution prepared by dissolving paraform (0.13 g, 4.5 mmol) in boiling deionized water (10 ml) in a 50 ml conical flask. The solution was stirred vigorously for 1 h at room temperature (r.t.), filtered and left open overnight. On the next day, 2-pyridinecarbaldehyde (0.19 ml, 2 mmol) was added to the flask, followed by Mn(OAc)2·4H2O (0.49 g, 2 mmol) dissolved in 5 ml of water, and the solution was magnetically stirred at r.t. for 30 min, then filtered and allowed to evaporate. Very light-brown needles of I suitable for X-ray crystallography formed within two days in the brown solution. The crystals were filtered off, washed with diethyl ether and dried in air. Yield: 67% (based on Mn). FT–IR (ν, cm−1): 3430br, 3122s, 3094s, 3050s, 3014, 2954, 2914, 2826, 1654, 1566, 1544, 1454, 1374, 1352, 1328, 1258, 1222, 1148s, 1130, 1038, 920, 800s, 764, 742, 624s, 498, 468, 434. Elemental analysis calculated for C16H18N4MnCl4 (463.08): C 41.50; H 3.92; N 12.10%. Found: C 41.62; H 3.93; N 12.04%.
The FT–IR spectrum of I in KBr measured in the 4000–400 cm−1 range (Fig. 5) has a distinctive pattern characteristic of the imidazo[1,5-a]pyridinium-based skeleton (Vassilyeva et al., 2020, 2021): the very strong sharp peaks are due to aromatic C—H stretching (3122–3050 cm−1), the medium intensity bands at 1654 and 1544 cm−1 are associated with heterocyclic ring vibrations, an intense absorption at 1148 cm−1 is ascribed to ν(N–CCH3) vibration and there is a prominent set of three peaks in the out-of-plane C—H-bending region (800, 742 and 624 cm−1).
7. Refinement
Crystal data, data collection and structure . All hydrogen atoms were included in calculated positions and refined using a riding model with isotropic displacement parameters based on those of the parent atom (C—H = 0.95 Å, Uiso(H) = 1.2Ueq(C) for CH, C—H = 0.98 Å, Uiso(H) = 1.5Ueq(C) for CH3). Anisotropic displacement parameters were employed for the non-hydrogen atoms.
details are summarized in Table 3
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Supporting information
CCDC reference: 1959314
https://doi.org/10.1107/S2056989023002761/jq2027sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023002761/jq2027Isup2.hkl
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: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).(C8H9N2)2[MnCl4] | Z = 2 |
Mr = 463.08 | F(000) = 470 |
Triclinic, P1 | Dx = 1.548 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4042 (6) Å | Cell parameters from 3962 reflections |
b = 10.7074 (6) Å | θ = 2.1–31.2° |
c = 10.7401 (6) Å | µ = 1.21 mm−1 |
α = 99.211 (5)° | T = 100 K |
β = 110.852 (6)° | Needle, light brown |
γ = 91.515 (5)° | 0.43 × 0.16 × 0.1 mm |
V = 993.52 (11) Å3 |
Oxford Diffraction Xcalibur diffractometer | 6374 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5151 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 16.0009 pixels mm-1 | θmax = 32.1°, θmin = 2.1° |
ω scans | h = −13→13 |
Absorption correction: analytical (CrysAlis Pro; Rigaku OD, 2016) | k = −15→13 |
Tmin = 0.706, Tmax = 0.908 | l = −11→15 |
11038 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.8647P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
6374 reflections | Δρmax = 1.32 e Å−3 |
228 parameters | Δρmin = −0.65 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. One reflection which was considered to be obscured by the beam stop was omitted from the refinement. |
x | y | z | Uiso*/Ueq | ||
C11 | 0.7645 (3) | 0.5468 (2) | 0.2669 (2) | 0.0213 (4) | |
H11 | 0.838597 | 0.50728 | 0.330658 | 0.026* | |
N12 | 0.7899 (2) | 0.61515 (18) | 0.18183 (18) | 0.0182 (3) | |
C12 | 0.9382 (3) | 0.6391 (2) | 0.1700 (3) | 0.0256 (5) | |
H12A | 0.989164 | 0.719825 | 0.228348 | 0.038* | |
H12B | 0.922869 | 0.643492 | 0.075695 | 0.038* | |
H12C | 1.001665 | 0.570072 | 0.198003 | 0.038* | |
C13 | 0.6572 (2) | 0.6572 (2) | 0.1041 (2) | 0.0204 (4) | |
H13 | 0.645655 | 0.70732 | 0.036315 | 0.024* | |
N13A | 0.5446 (2) | 0.6135 (2) | 0.1425 (2) | 0.0266 (4) | |
C14 | 0.3856 (3) | 0.6248 (2) | 0.1000 (3) | 0.0253 (5) | |
H14 | 0.336093 | 0.668856 | 0.02843 | 0.03* | |
C15 | 0.3062 (3) | 0.5714 (3) | 0.1637 (3) | 0.0315 (6) | |
H15 | 0.199452 | 0.578985 | 0.136942 | 0.038* | |
C16 | 0.3786 (3) | 0.5039 (3) | 0.2702 (3) | 0.0352 (6) | |
H16 | 0.319686 | 0.468677 | 0.314078 | 0.042* | |
C17 | 0.5293 (3) | 0.4893 (2) | 0.3098 (3) | 0.0303 (5) | |
H17 | 0.576756 | 0.442786 | 0.37962 | 0.036* | |
C17A | 0.6142 (2) | 0.54440 (19) | 0.2455 (2) | 0.0153 (4) | |
C21 | 0.2932 (3) | 0.8976 (2) | 0.3195 (2) | 0.0250 (5) | |
H21 | 0.196989 | 0.897717 | 0.329702 | 0.03* | |
N22 | 0.3271 (3) | 0.9359 (2) | 0.2170 (2) | 0.0267 (4) | |
C22 | 0.2201 (4) | 0.9879 (3) | 0.1047 (3) | 0.0370 (6) | |
H22A | 0.275187 | 1.01841 | 0.051736 | 0.056* | |
H22B | 0.173674 | 1.058598 | 0.14116 | 0.056* | |
H22C | 0.139884 | 0.921389 | 0.046435 | 0.056* | |
C23 | 0.4729 (3) | 0.9225 (2) | 0.2345 (2) | 0.0260 (5) | |
H23 | 0.523166 | 0.942318 | 0.176507 | 0.031* | |
N23A | 0.5364 (2) | 0.87586 (19) | 0.3492 (2) | 0.0232 (4) | |
C24 | 0.6858 (3) | 0.8453 (2) | 0.4119 (3) | 0.0289 (5) | |
H24 | 0.761335 | 0.85674 | 0.374017 | 0.035* | |
C25 | 0.7194 (3) | 0.7991 (3) | 0.5275 (3) | 0.0337 (6) | |
H25 | 0.819593 | 0.775808 | 0.570203 | 0.04* | |
C26 | 0.6093 (3) | 0.7844 (2) | 0.5870 (3) | 0.0334 (6) | |
H26 | 0.63787 | 0.75435 | 0.670355 | 0.04* | |
C27 | 0.4650 (3) | 0.8124 (2) | 0.5276 (3) | 0.0281 (5) | |
H27 | 0.391259 | 0.800913 | 0.567407 | 0.034* | |
C27A | 0.4246 (3) | 0.8592 (2) | 0.4045 (2) | 0.0202 (4) | |
Mn1 | 0.84578 (4) | 0.19104 (3) | 0.25082 (3) | 0.02042 (9) | |
Cl1 | 0.57864 (6) | 0.18756 (6) | 0.13323 (6) | 0.02657 (13) | |
Cl2 | 0.98756 (7) | 0.30020 (6) | 0.15037 (6) | 0.02681 (13) | |
Cl3 | 0.90155 (8) | −0.02287 (6) | 0.24168 (7) | 0.03208 (14) | |
Cl4 | 0.89538 (7) | 0.30780 (6) | 0.47087 (6) | 0.03045 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.0187 (10) | 0.0201 (10) | 0.0247 (10) | 0.0026 (8) | 0.0079 (8) | 0.0028 (8) |
N12 | 0.0148 (8) | 0.0185 (8) | 0.0206 (8) | 0.0023 (6) | 0.0062 (7) | 0.0017 (7) |
C12 | 0.0172 (10) | 0.0271 (12) | 0.0339 (12) | 0.0024 (8) | 0.0117 (9) | 0.0042 (10) |
C13 | 0.0160 (9) | 0.0213 (10) | 0.0218 (10) | 0.0043 (8) | 0.0049 (8) | 0.0026 (8) |
N13A | 0.0225 (10) | 0.0232 (10) | 0.0312 (10) | 0.0030 (8) | 0.0089 (8) | −0.0013 (8) |
C14 | 0.0178 (10) | 0.0263 (11) | 0.0294 (12) | 0.0050 (8) | 0.0081 (9) | −0.0011 (9) |
C15 | 0.0176 (11) | 0.0306 (13) | 0.0439 (15) | −0.0008 (9) | 0.0141 (10) | −0.0066 (11) |
C16 | 0.0377 (15) | 0.0282 (13) | 0.0479 (16) | −0.0028 (11) | 0.0280 (13) | 0.0018 (12) |
C17 | 0.0370 (14) | 0.0231 (12) | 0.0355 (13) | 0.0020 (10) | 0.0187 (11) | 0.0067 (10) |
C17A | 0.0139 (9) | 0.0119 (8) | 0.0185 (9) | 0.0009 (7) | 0.0051 (7) | 0.0005 (7) |
C21 | 0.0221 (11) | 0.0229 (11) | 0.0291 (12) | 0.0023 (9) | 0.0108 (9) | −0.0015 (9) |
N22 | 0.0305 (11) | 0.0218 (10) | 0.0236 (10) | 0.0055 (8) | 0.0063 (8) | 0.0005 (8) |
C22 | 0.0420 (16) | 0.0320 (14) | 0.0273 (13) | 0.0125 (12) | 0.0011 (11) | 0.0036 (11) |
C23 | 0.0343 (13) | 0.0219 (11) | 0.0236 (11) | 0.0024 (9) | 0.0138 (10) | 0.0018 (9) |
N23A | 0.0243 (10) | 0.0186 (9) | 0.0274 (10) | −0.0005 (7) | 0.0124 (8) | 0.0001 (7) |
C24 | 0.0201 (11) | 0.0262 (12) | 0.0385 (13) | −0.0014 (9) | 0.0143 (10) | −0.0069 (10) |
C25 | 0.0244 (12) | 0.0270 (13) | 0.0378 (14) | 0.0041 (10) | 0.0012 (10) | −0.0043 (11) |
C26 | 0.0438 (16) | 0.0223 (12) | 0.0267 (12) | 0.0001 (11) | 0.0036 (11) | 0.0054 (10) |
C27 | 0.0356 (13) | 0.0225 (11) | 0.0275 (12) | −0.0050 (10) | 0.0151 (10) | 0.0010 (9) |
C27A | 0.0196 (10) | 0.0180 (10) | 0.0242 (10) | −0.0008 (8) | 0.0114 (8) | −0.0003 (8) |
Mn1 | 0.01803 (16) | 0.02251 (18) | 0.01970 (17) | 0.00204 (12) | 0.00538 (13) | 0.00445 (13) |
Cl1 | 0.0187 (2) | 0.0328 (3) | 0.0268 (3) | 0.0030 (2) | 0.0047 (2) | 0.0100 (2) |
Cl2 | 0.0266 (3) | 0.0264 (3) | 0.0307 (3) | 0.0014 (2) | 0.0136 (2) | 0.0072 (2) |
Cl3 | 0.0350 (3) | 0.0268 (3) | 0.0395 (3) | 0.0103 (2) | 0.0161 (3) | 0.0133 (3) |
Cl4 | 0.0269 (3) | 0.0380 (3) | 0.0222 (3) | −0.0009 (2) | 0.0062 (2) | 0.0003 (2) |
C11—N12 | 1.337 (3) | C21—H21 | 0.95 |
C11—C17A | 1.347 (3) | N22—C23 | 1.332 (3) |
C11—H11 | 0.95 | N22—C22 | 1.468 (3) |
N12—C13 | 1.366 (3) | C22—H22A | 0.98 |
N12—C12 | 1.464 (3) | C22—H22B | 0.98 |
C12—H12A | 0.98 | C22—H22C | 0.98 |
C12—H12B | 0.98 | C23—N23A | 1.346 (3) |
C12—H12C | 0.98 | C23—H23 | 0.95 |
C13—N13A | 1.363 (3) | N23A—C24 | 1.399 (3) |
C13—H13 | 0.95 | N23A—C27A | 1.400 (3) |
N13A—C17A | 1.405 (3) | C24—C25 | 1.346 (4) |
N13A—C14 | 1.414 (3) | C24—H24 | 0.95 |
C14—C15 | 1.350 (4) | C25—C26 | 1.414 (4) |
C14—H14 | 0.95 | C25—H25 | 0.95 |
C15—C16 | 1.425 (4) | C26—C27 | 1.343 (4) |
C15—H15 | 0.95 | C26—H26 | 0.95 |
C16—C17 | 1.349 (4) | C27—C27A | 1.416 (3) |
C16—H16 | 0.95 | C27—H27 | 0.95 |
C17—C17A | 1.400 (3) | Mn1—Cl3 | 2.3577 (7) |
C17—H17 | 0.95 | Mn1—Cl4 | 2.3674 (7) |
C21—N22 | 1.366 (3) | Mn1—Cl1 | 2.3725 (7) |
C21—C27A | 1.369 (3) | Mn1—Cl2 | 2.3777 (7) |
N12—C11—C17A | 107.34 (19) | C23—N22—C21 | 110.4 (2) |
N12—C11—H11 | 126.3 | C23—N22—C22 | 124.2 (2) |
C17A—C11—H11 | 126.3 | C21—N22—C22 | 125.3 (2) |
C11—N12—C13 | 110.61 (19) | N22—C22—H22A | 109.5 |
C11—N12—C12 | 125.11 (19) | N22—C22—H22B | 109.5 |
C13—N12—C12 | 124.3 (2) | H22A—C22—H22B | 109.5 |
N12—C12—H12A | 109.5 | N22—C22—H22C | 109.5 |
N12—C12—H12B | 109.5 | H22A—C22—H22C | 109.5 |
H12A—C12—H12B | 109.5 | H22B—C22—H22C | 109.5 |
N12—C12—H12C | 109.5 | N22—C23—N23A | 107.7 (2) |
H12A—C12—H12C | 109.5 | N22—C23—H23 | 126.2 |
H12B—C12—H12C | 109.5 | N23A—C23—H23 | 126.2 |
N13A—C13—N12 | 106.9 (2) | C23—N23A—C24 | 130.2 (2) |
N13A—C13—H13 | 126.5 | C23—N23A—C27A | 108.6 (2) |
N12—C13—H13 | 126.5 | C24—N23A—C27A | 121.2 (2) |
C13—N13A—C17A | 106.65 (18) | C25—C24—N23A | 118.0 (2) |
C13—N13A—C14 | 133.6 (2) | C25—C24—H24 | 121 |
C17A—N13A—C14 | 119.8 (2) | N23A—C24—H24 | 121 |
C15—C14—N13A | 118.2 (2) | C24—C25—C26 | 121.7 (2) |
C15—C14—H14 | 120.9 | C24—C25—H25 | 119.1 |
N13A—C14—H14 | 120.9 | C26—C25—H25 | 119.1 |
C14—C15—C16 | 121.5 (2) | C27—C26—C25 | 121.0 (2) |
C14—C15—H15 | 119.2 | C27—C26—H26 | 119.5 |
C16—C15—H15 | 119.2 | C25—C26—H26 | 119.5 |
C17—C16—C15 | 121.1 (2) | C26—C27—C27A | 118.9 (2) |
C17—C16—H16 | 119.5 | C26—C27—H27 | 120.5 |
C15—C16—H16 | 119.5 | C27A—C27—H27 | 120.5 |
C16—C17—C17A | 118.4 (2) | C21—C27A—N23A | 106.4 (2) |
C16—C17—H17 | 120.8 | C21—C27A—C27 | 134.5 (2) |
C17A—C17—H17 | 120.8 | N23A—C27A—C27 | 119.0 (2) |
C11—C17A—C17 | 130.5 (2) | Cl3—Mn1—Cl4 | 115.23 (3) |
C11—C17A—N13A | 108.49 (19) | Cl3—Mn1—Cl1 | 106.36 (3) |
C17—C17A—N13A | 121.0 (2) | Cl4—Mn1—Cl1 | 105.81 (3) |
N22—C21—C27A | 106.9 (2) | Cl3—Mn1—Cl2 | 110.21 (3) |
N22—C21—H21 | 126.5 | Cl4—Mn1—Cl2 | 107.51 (3) |
C27A—C21—H21 | 126.5 | Cl1—Mn1—Cl2 | 111.72 (2) |
C17A—C11—N12—C13 | −0.3 (3) | C27A—C21—N22—C23 | 0.2 (3) |
C17A—C11—N12—C12 | −178.7 (2) | C27A—C21—N22—C22 | −178.2 (2) |
C11—N12—C13—N13A | 0.1 (2) | C21—N22—C23—N23A | −0.3 (3) |
C12—N12—C13—N13A | 178.5 (2) | C22—N22—C23—N23A | 178.2 (2) |
N12—C13—N13A—C17A | 0.1 (2) | N22—C23—N23A—C24 | −179.9 (2) |
N12—C13—N13A—C14 | −179.8 (2) | N22—C23—N23A—C27A | 0.3 (3) |
C13—N13A—C14—C15 | −178.1 (2) | C23—N23A—C24—C25 | −179.8 (2) |
C17A—N13A—C14—C15 | 2.0 (3) | C27A—N23A—C24—C25 | 0.0 (3) |
N13A—C14—C15—C16 | −0.7 (4) | N23A—C24—C25—C26 | −1.6 (4) |
C14—C15—C16—C17 | −1.1 (4) | C24—C25—C26—C27 | 2.2 (4) |
C15—C16—C17—C17A | 1.3 (4) | C25—C26—C27—C27A | −1.1 (4) |
N12—C11—C17A—C17 | −178.0 (2) | N22—C21—C27A—N23A | 0.0 (2) |
N12—C11—C17A—N13A | 0.4 (2) | N22—C21—C27A—C27 | 178.7 (3) |
C16—C17—C17A—C11 | 178.4 (2) | C23—N23A—C27A—C21 | −0.1 (3) |
C16—C17—C17A—N13A | 0.1 (4) | C24—N23A—C27A—C21 | 180.0 (2) |
C13—N13A—C17A—C11 | −0.3 (2) | C23—N23A—C27A—C27 | −179.1 (2) |
C14—N13A—C17A—C11 | 179.6 (2) | C24—N23A—C27A—C27 | 1.0 (3) |
C13—N13A—C17A—C17 | 178.3 (2) | C26—C27—C27A—C21 | −179.1 (3) |
C14—N13A—C17A—C17 | −1.8 (3) | C26—C27—C27A—N23A | −0.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···Cl4 | 0.95 | 2.76 | 3.592 (2) | 146 |
C13—H13···Cl1i | 0.95 | 2.66 | 3.422 (2) | 138 |
C14—H14···Cl1i | 0.95 | 2.79 | 3.549 (3) | 137 |
C21—H21···Cl3ii | 0.95 | 2.80 | 3.632 (2) | 147 |
C22—H22C···Cl2i | 0.98 | 2.82 | 3.742 (3) | 156 |
C23—H23···Cl1iii | 0.95 | 2.81 | 3.440 (3) | 125 |
C24—H24···Cl3iii | 0.95 | 2.69 | 3.573 (3) | 154 |
C27—H27···Cl4iv | 0.95 | 2.77 | 3.600 (3) | 146 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y+1, z; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1. |
Funding information
Funding for this research was provided by: Ministry of Education and Science of Ukraine (project 22BP037-13; grant for the perspective development of the scientific direction `Mathematical sciences and natural sciences' at the Taras Shevchenko National University of Kyiv).
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