Synthesis, crystal structure and thermal properties of poly[bis­[μ-3-(amino­meth­yl)pyridine-κ2N:N′]bis(thio­cyanato-κN)manganese(II)]

Krebs, C.; Jess, I.; Näther, C.

doi:10.1107/S2056989021006733

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ISSN: 2056-9890

Volume 77| Part 8| August 2021| Pages 765-769

https://doi.org/10.1107/S2056989021006733

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Synthesis, crystal structure and thermal properties of poly[bis[μ-3-(aminomethyl)pyridine-κ²N:N′]bis(thiocyanato-κN)manganese(II)]

Christoph Krebs,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Str. 2, D-24118 Kiel, Germany
^*Correspondence e-mail: ckrebs@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 June 2021; accepted 28 June 2021; online 2 July 2021)

The reaction of Mn(NCS)₂ with a stoichiometric amount of 3-(aminomethyl)pyridine in ethanol led to the formation of the title compound, [Mn(NCS)₂(C₆H₈N₂)₂]_n, which is isotypic to its Zn, Co and Cd analogues. The manganese cation is located on a centre of inversion and is octahedrally coordinated in an all-trans configuration by two terminal N-bonded thiocyanate anions as well as four 3-(aminomethyl)pyridine co-ligands, of which two coordinate with the pyridine N atom and two with the amino N atom. The 3-(aminomethyl)pyridine co-ligands connect the Mn^II cations into layers extending parallel to (10 $[\overline{1}]$ ). These layers are further connected into a three-dimensional network by relatively strong intermolecular N—H⋯S hydrogen bonding. Comparison of the experimental X-ray powder diffraction pattern with the calculated pattern on the basis of single-crystal data proves the formation of a pure crystalline phase. IR measurements showed the CN stretching vibration of the thiocyanate anions at 2067 cm⁻¹, which is in agreement with the presence of terminally N-bonded anionic ligands. TG–DTA measurements revealed that the title compound decomposes at about 500 K.

Keywords: crystal structure; layered structure; thermal properties; manganese thiocyanate; 3-(aminomethyl)pyridine; isotypism.

CCDC reference: 2092830

1. Chemical context

In contrast to other small-sized ligands such as azide or cyanide anions, thiocyanate anions show many more coordination modes. Therefore, a variety of structures including discrete complexes (Prananto et al., 2017 ; Małecki et al., 2011 ; Wöhlert et al., 2014 ), dimers (Mautner et al., 2015 ; Wei & Luo, 2010 ; Jochim et al., 2018 ), chains (Mautner et al., 2018 ; Rams et al., 2020 ), layers (Suckert et al., 2016 , 2017 ) or in very rare cases three-dimensional networks (Suckert et al., 2017) can be observed. This structural variability is further enhanced by isomerism, because for an octahedral coordination with three pairs of identical ligands, five different isomers exist, including the all-trans, all-cis and three different cis-cis-trans configurations. These features are found in compounds with structures where the metal cations are linked by pairs of anionic ligands into chains. The majority of compounds with μ-1,3-bridging thiocyanate anions shows this behaviour. Depending on the actual metal coordination (all-trans or cis-cis-trans), linear or corrugated chains are observed (Jin et al., 2007 ; Rams et al., 2017 ; Böhme et al., 2020 ; Jochim et al., 2020 ). Moreover, even for compounds with layered thiocyanate structures, different networks are realized, in which the metal cations are linked exclusively by single anionic ligands or by both singly and doubly μ-1,3-bridging thiocyanate anions. For less chalcophilic metal cations like Mn^II, Fe^II, Co^II or Ni^II, the majority of compounds consist of structures with only terminally N-bonding thiocyanate anions, because in this case this coordination is energetically favoured. With only mono-coordinating ligands this usually leads to the formation of discrete metal complexes with an octahedral coordination. If bridging co-ligands are used, chain structures can be realized and networks of higher dimensionality are available if additional μ-1,3-bridging thiocyanate anions are present.

Thiocyanate coordination polymers are of interest not only because of their variable structural behaviour, but also because this ligand is able to mediate reasonable magnetic exchange. We and other groups have reported many new compounds in which the metal cations are linked by μ-1,3-bridging thiocyanate anions into chains or layers (Werner et al., 2015 ; Bassey et al., 2020 ; Mekuimemba et al., 2018 ; Palion-Gazda et al., 2015 ; Neumann et al., 2019 ; Mousavi et al., 2020 ). In this context, we became interested in 3-(aminomethyl)pyridine, because this ligand is able to link metal cations via the pyridine and the amino N atom. Surprisingly, with Co^II we always obtained only one crystalline phase in which the Co^II cations are coordinated by only terminally N-bonding thiocyanate anions but linked into layers by the 3-(aminomethyl)pyridine co-ligands (Krebs et al., 2021 ). In contrast to the Co^II cation, the Mn^II cation is more chalcophilic and usually behaves like Cd^II, for which compounds with μ-1,3-bridging thiocyanate anions are much easier to obtain. Therefore, we used Mn(NCS)₂ in the present study. However, irrespective of the ratio between Mn(NCS)₂ and 3-(aminomethyl)pyridine, we always obtained only one crystalline phase with composition Mn(NCS)₂(C₆H₈N₂)₂. Single-crystal structure analysis revealed isotypism with the Co^II analogue reported recently (Krebs et al. 2021). Comparison of the experimental X-ray powder diffraction pattern with the calculated pattern based on single-crystal data proved that a pure crystalline phase was obtained (see Fig. S1 in the supporting information); IR investigations revealed that the CN stretching vibration is observed at 2067 cm⁻¹, in agreement with the presence of only terminally N-bound thiocyanate anions (Fig. S2). TG–DTA measurements showed decomposition of the compound at about 500 K, which is accompanied by an endothermic event in the DTA curve (Fig. S3). The first decomposition step might be associated with the removal of the 3-(aminomethyl)pyridine co-ligand. On further heating, an exothermic signal is observed, which indicates the decomposition of the co-ligand.

2. Structural commentary

Mn(NCS)₂(C₆H₈N₂)₂ is isotypic with its recently reported Cd^II, Zn^II and Co^II analogues (Neumann et al., 2017 ; Krebs et al., 2021). The asymmetric unit consists of one Mn^II cation that is located on a centre of inversion as well as one 3-(aminomethyl)pyridine co-ligand and one thiocyanate anion (Fig. 1). The Mn^II cation is octahedrally coordinated by the N atoms of four symmetry-equivalent 3-(aminomethyl)pyridine co-ligands and two symmetry-equivalent thiocyanate anions. Two of these co-ligands coordinate through the pyridine N atom whereas the other two coordinate with the amino N atom. Each pair of identical donor atoms is in a trans-position (Fig. 1). The Mn—N bond length to the negatively charged thiocyanate N atom is significantly shorter than that to the 3-(aminomethyl)pyridine co-ligand; the Mn—N bond length to the pyridine N atom is significantly longer than that to the amino N atom of the 3-(aminomethyl)pyridine ligand (Table 1). As expected, all Mn—N bond lengths are significantly longer and shorter, respectively, compared to the Co^II and Cd^II analogues. The bond angles around Mn^II indicate a considerable distortion (Table 1). This is also indicated by the mean octahedral quadratic elongation of 1.0013 and the octahedral angle variance of 0.8258 (Robinson et al., 1971 ). The Mn^II cations are connected by bridging 3-(aminomethyl)pyridine ligands into chains, which are further linked into layers extending parallel to (10 $[\overline{1}]$ ) by additional co-ligands (Fig. 2).

Table 1
Selected geometric parameters (Å, °)

Mn1—N1	2.1955 (15)	Mn1—N11	2.3154 (14)
Mn1—N12ⁱ	2.2901 (14)

N1—Mn1—N1ⁱⁱ	180.0	N1ⁱⁱ—Mn1—N11	90.82 (5)
N1—Mn1—N12ⁱ	91.17 (6)	N12ⁱ—Mn1—N11	89.52 (5)
N1—Mn1—N12ⁱⁱⁱ	88.83 (6)	N12ⁱⁱⁱ—Mn1—N11	90.48 (5)
N1—Mn1—N11	89.18 (5)	N1—Mn1—N11ⁱⁱ	90.82 (5)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The coordination of the Mn^II cation in the title compound with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (A) −x, −y + 1, −z, (B) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z, (C) − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z.]

Figure 2
Crystal structure of the title compound in a view of a layer along the crystallographic a axis.

3. Supramolecular features

The layers are linked into a three-dimensional network by intermolecular N—H⋯S hydrogen bonds between the amino H atoms and the thiocyanate S atoms (Fig. 3, Table 2). The N—H⋯S angles indicate a relatively strong interaction and the thiocyanate S atom acts as an acceptor for two of these hydrogen bonds. There is also a C—H⋯S interaction but the bonding angle is far from linearity, which points to a weak interaction (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯S1ⁱⁱⁱ	0.95	2.99	3.7264 (19)	136
N12—H12A⋯S1^iv	0.91	2.81	3.7016 (16)	166
N12—H12B⋯S1^v	0.91	2.66	3.5224 (15)	159
Symmetry codes: (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x, y, z+1; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 3
Crystal structure of the title compound in a view along the crystallographic b axis. Intermolecular N—H⋯S hydrogen bonds are shown as dashed lines.

4. Database survey

In the Cambridge Structure Database (CSD, version 5.42, last update November 2020; Groom et al., 2016 ) no Mn–3-(aminomethyl)pyridine compounds are reported but a few compounds based on Zn(NCS)₂ and Cd(NCS)₂ have been deposited. In all of the corresponding structures, the metal cations are octahedrally coordinated. This includes M(NCS)₂[3-(aminomethyl)pyridine]₂ (M = Cd, Zn; Neumann et al., 2017; refcodes: QEKZEO and QEKYUD), which are isotypic to the title compound, as well as M(NCS)₂[3-(aminomethyl)pyridine] (M = Cd, Zn; Neumann, et al. 2017; refcodes: QEKZIS and QEKZAK). In the latter Zn^II compound, dimers are observed in which two Zn^II cations are connected by two 3-(aminomethyl)pyridine ligands. In the Cd^II compound, the metal cations are linked by μ-1,3-bridging thiocyanate anions into chains that are connected into layers by the 3-(aminomethyl)pyridine ligands. This compound is the only one that contains μ-1,3-bridging thiocyanate anions and which shows a cis-cis-trans coordination of the metal cations. There is also one solvate with the composition Cd(NCS)₂[3-(aminomethyl)pyridine]₂-tris[3-(aminomethyl)pyridine] reported in the CSD (refcode: QEKYOX; Neumann et al., 2017). Finally, Co(NCS)₂(3-(aminomethyl)pyridine)₂, which is isotypic to the title compound, is also reported (Krebs et al., 2021).

5. Synthesis and crystallization

Synthesis

Mn(NCS)₂ and 3-(aminomethyl)pyridine were purchased from Alfa Aesar and all chemicals were used without further purification. Single crystals were obtained by reacting 1 mmol of Mn(NCS)₂ (175.1 mg) with 1 mmol of 3-(aminomethyl)pyridine (108.1 mg) in 4 ml of ethanol. After approximately one week, light-brown crystals were obtained, which were suitable for single crystal X-ray analysis. For the synthesis of crystalline powders, the same amounts of reactants were stirred in 2 ml of ethanol for 1 d and the precipitate was filtered off and dried in air.

Elemental analysis calculated for C₁₄H₁₆N₆MnS₂: C 43.41%, H 4.16%, N 21.69%, S 16.55%; found: C 43.32%, H 4.11%, N 21.56, S 16.31%. IR: ν = 2971 (m), 2941 (w), 2928 (w), 2887 (s), 2875 (w), 2067 (s), 2023 (m), 1962(vw), 1861 (vw), 1595 (m), 1583 (w), 1480 (m), 1447 (m), 1426 (m), 1379 (w), 1361 (w), 1332 (w), 1274 (wv), 1244 (w), 1229 (w), 1189 (m), 1148 (w), 1124 (m), 1089 (m), 1048 (vs), 984 (s), 961 (m), 943 (w), 931 (m), 879 (m), 846 (w), 824 (w), 802 (m), 783 (m), 712 (s), 645 (s), 620 (m), 539 (s) cm⁻¹.

Experimental details

The elemental analysis was performed using a EURO EA elemental analyzer fabricated by EURO VECTOR Instruments. The IR spectrum was measured using an ATI Mattson Genesis Series FTIR spectrometer, control software: WINFIRST, from ATI Mattson. The PXRD measurement was performed with Cu Kα₁ radiation (λ = 1.540598 Å) using a Stoe Transmission Powder Diffraction System (STADI P) that is equipped with a MYTHEN 1K detector and a Johansson-type Ge(111) monochromator. Thermogravimetry and differential thermoanalysis (TG–DTA) measurements were performed in a dynamic nitrogen atmosphere in Al₂O₃ crucibles using a STA-PT 1000 thermobalance from Linseis. The instrument was calibrated using standard reference materials.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were located in a difference-Fourier map but were positioned with idealized geometry (N—H = 0.91 Å, C—H = 0.95–0.99 Å) and were refined in a riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for amino H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(NCS)₂(C₆H₈N₂S)₂]
M_r	387.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	8.2157 (3), 12.2356 (5), 8.9601 (3)
β (°)	99.736 (3)
V (Å³)	887.73 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.99
Crystal size (mm)	0.03 × 0.03 × 0.01

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED 32; Stoe, 2002 )
T_min, T_max	0.856, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	12559, 1939, 1755
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.073, 1.14
No. of reflections	1939
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22
Computer programs: X-AREA (Stoe, 2002), SHELXS97 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2092830

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006733/wm5613sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006733/wm5613Isup2.hkl

Figure S1. Experimental (top) and calculated X-ray powder pattern (bottom) of the title compound. For the calculation of the powder pattern the lattice parameters obtained from a Pawley fit of a powder pattern measured at room temperature were used. DOI: https://doi.org/10.1107/S2056989021006733/wm5613sup3.png

Figure S2. IR spectra of the title compound. The value of the CN stretching vibration of the thiocyanat anions is given. DOI: https://doi.org/10.1107/S2056989021006733/wm5613sup4.png

Figure S3. DTG (top), TG (middle) and DTA curve (bottom) of the title compound measured with 1K/min in nitrogen atmosphere. DOI: https://doi.org/10.1107/S2056989021006733/wm5613sup5.png

checkCIF report

Computing details top

Data collection: X-AREA (Stoe, 2002); cell refinement: X-AREA (Stoe, 2002); data reduction: X-AREA (Stoe, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[bis[µ-3-(aminomethyl)pyridine-κ²N:N']bis(thiocyanato-κN)manganese(II)] top

Crystal data top

[Mn(NCS)₂(C₆H₈N₂S)₂]	F(000) = 398
M_r = 387.39	D_x = 1.449 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.2157 (3) Å	Cell parameters from 12559 reflections
b = 12.2356 (5) Å	θ = 2.8–27.0°
c = 8.9601 (3) Å	µ = 0.99 mm⁻¹
β = 99.736 (3)°	T = 200 K
V = 887.73 (6) Å³	Block, light-brown
Z = 2	0.03 × 0.03 × 0.01 mm

Data collection top

Stoe IPDS-2 diffractometer	1755 reflections with I > 2σ(I)
ω scans	R_int = 0.040
Absorption correction: numerical (X-Shape and X-Red 32; Stoe, 2002)	θ_max = 27.0°, θ_min = 2.9°
T_min = 0.856, T_max = 0.980	h = −10→10
12559 measured reflections	k = −15→15
1939 independent reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0359P)² + 0.2401P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
1939 reflections	Δρ_max = 0.27 e Å⁻³
106 parameters	Δρ_min = −0.22 e Å⁻³

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
Mn1	0.000000	0.500000	0.000000	0.02622 (11)
N1	0.20857 (19)	0.56497 (13)	−0.09665 (18)	0.0358 (3)
C1	0.3146 (2)	0.62691 (14)	−0.10034 (19)	0.0313 (4)
S1	0.46152 (6)	0.71704 (4)	−0.10505 (6)	0.04157 (14)
N11	0.14907 (18)	0.52888 (12)	0.24007 (16)	0.0306 (3)
C11	0.1329 (2)	0.46441 (15)	0.3576 (2)	0.0333 (4)
H11	0.057240	0.405168	0.340862	0.040*
C12	0.2207 (2)	0.47971 (15)	0.5022 (2)	0.0350 (4)
H12	0.206448	0.431458	0.582080	0.042*
C13	0.3292 (2)	0.56627 (15)	0.5281 (2)	0.0339 (4)
H13	0.391568	0.577949	0.626157	0.041*
C14	0.3466 (2)	0.63626 (14)	0.40992 (19)	0.0295 (3)
C15	0.2556 (2)	0.61299 (14)	0.2685 (2)	0.0316 (3)
H15	0.269345	0.659337	0.186448	0.038*
C16	0.4577 (2)	0.73525 (14)	0.4322 (2)	0.0340 (4)
H16A	0.564073	0.714074	0.494763	0.041*
H16B	0.480824	0.759048	0.332262	0.041*
N12	0.38812 (18)	0.82892 (11)	0.50551 (17)	0.0319 (3)
H12A	0.391635	0.810986	0.604571	0.038*
H12B	0.279589	0.834201	0.463345	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02752 (18)	0.02188 (18)	0.02836 (19)	−0.00181 (13)	0.00218 (13)	0.00086 (13)
N1	0.0343 (8)	0.0370 (8)	0.0371 (8)	−0.0054 (6)	0.0086 (6)	0.0015 (7)
C1	0.0330 (8)	0.0321 (9)	0.0291 (8)	0.0047 (7)	0.0060 (7)	−0.0012 (7)
S1	0.0355 (2)	0.0368 (3)	0.0526 (3)	−0.00815 (19)	0.0079 (2)	−0.0034 (2)
N11	0.0327 (7)	0.0273 (7)	0.0305 (7)	−0.0022 (5)	0.0019 (6)	−0.0013 (5)
C11	0.0362 (9)	0.0276 (8)	0.0361 (9)	−0.0047 (7)	0.0063 (7)	−0.0024 (7)
C12	0.0424 (9)	0.0305 (9)	0.0326 (9)	−0.0020 (7)	0.0074 (7)	0.0022 (7)
C13	0.0396 (9)	0.0322 (9)	0.0291 (8)	0.0000 (7)	0.0039 (7)	−0.0021 (7)
C14	0.0302 (8)	0.0250 (8)	0.0333 (8)	0.0008 (6)	0.0054 (7)	−0.0033 (6)
C15	0.0359 (8)	0.0269 (8)	0.0313 (8)	−0.0010 (7)	0.0038 (7)	0.0012 (6)
C16	0.0348 (9)	0.0281 (9)	0.0389 (9)	−0.0027 (7)	0.0061 (7)	−0.0043 (7)
N12	0.0334 (7)	0.0253 (7)	0.0368 (8)	−0.0023 (6)	0.0048 (6)	−0.0017 (6)

Geometric parameters (Å, º) top

Mn1—N1	2.1955 (15)	C12—C13	1.378 (3)
Mn1—N1ⁱ	2.1955 (15)	C12—H12	0.9500
Mn1—N12ⁱⁱ	2.2901 (14)	C13—C14	1.388 (2)
Mn1—N12ⁱⁱⁱ	2.2901 (14)	C13—H13	0.9500
Mn1—N11	2.3154 (14)	C14—C15	1.388 (2)
Mn1—N11ⁱ	2.3154 (14)	C14—C16	1.509 (2)
N1—C1	1.159 (2)	C15—H15	0.9500
C1—S1	1.6406 (18)	C16—N12	1.483 (2)
N11—C11	1.340 (2)	C16—H16A	0.9900
N11—C15	1.347 (2)	C16—H16B	0.9900
C11—C12	1.385 (3)	N12—H12A	0.9100
C11—H11	0.9500	N12—H12B	0.9100

N1—Mn1—N1ⁱ	180.0	C13—C12—H12	120.6
N1—Mn1—N12ⁱⁱ	91.17 (6)	C11—C12—H12	120.6
N1ⁱ—Mn1—N12ⁱⁱ	88.83 (6)	C12—C13—C14	119.54 (17)
N1—Mn1—N12ⁱⁱⁱ	88.83 (6)	C12—C13—H13	120.2
N1ⁱ—Mn1—N12ⁱⁱⁱ	91.17 (6)	C14—C13—H13	120.2
N12ⁱⁱ—Mn1—N12ⁱⁱⁱ	180.0	C15—C14—C13	117.45 (16)
N1—Mn1—N11	89.18 (5)	C15—C14—C16	120.37 (16)
N1ⁱ—Mn1—N11	90.82 (5)	C13—C14—C16	122.17 (16)
N12ⁱⁱ—Mn1—N11	89.52 (5)	N11—C15—C14	124.18 (16)
N12ⁱⁱⁱ—Mn1—N11	90.48 (5)	N11—C15—H15	117.9
N1—Mn1—N11ⁱ	90.82 (5)	C14—C15—H15	117.9
N1ⁱ—Mn1—N11ⁱ	89.18 (5)	N12—C16—C14	114.17 (14)
N12ⁱⁱ—Mn1—N11ⁱ	90.48 (5)	N12—C16—H16A	108.7
N12ⁱⁱⁱ—Mn1—N11ⁱ	89.52 (5)	C14—C16—H16A	108.7
N11—Mn1—N11ⁱ	180.0	N12—C16—H16B	108.7
C1—N1—Mn1	152.67 (14)	C14—C16—H16B	108.7
N1—C1—S1	178.57 (16)	H16A—C16—H16B	107.6
C11—N11—C15	116.67 (15)	C16—N12—Mn1^iv	120.72 (11)
C11—N11—Mn1	122.20 (11)	C16—N12—H12A	107.1
C15—N11—Mn1	121.12 (11)	Mn1^iv—N12—H12A	107.1
N11—C11—C12	123.38 (16)	C16—N12—H12B	107.1
N11—C11—H11	118.3	Mn1^iv—N12—H12B	107.1
C12—C11—H11	118.3	H12A—N12—H12B	106.8
C13—C12—C11	118.75 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···S1ⁱⁱⁱ	0.95	2.99	3.7264 (19)	136
N12—H12A···S1^v	0.91	2.81	3.7016 (16)	166
N12—H12B···S1^vi	0.91	2.66	3.5224 (15)	159

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

Funding information

This project was supported by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (grant No. NA720/5-2).

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