Synthesis, crystal structure and thermal decomposition pathway of bis­(iso­seleno­cyanato-κN)tetra­kis­(pyridine-κN)manganese(II)

Näther, C.; Mangelsen, S.; Boeckmann, J.

doi:10.1107/S2056989023003535

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 5| May 2023| Pages 482-487

https://doi.org/10.1107/S2056989023003535

Open

access

Synthesis, crystal structure and thermal decomposition pathway of bis(isoselenocyanato-κN)tetrakis(pyridine-κN)manganese(II)

Christian Näther,^a ^* Sebastian Mangelsen ^a and Jan Boeckmann ^a

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: cnaether@ac.uni-kiel.de

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 14 April 2023; accepted 18 April 2023; online 21 April 2023)

The reaction of MnCl₂·2H₂O with KSeCN and pyridine in water leads to the formation of the title complex, [Mn(NCSe)₂(C₅H₅N)₄], which is isotypic to its Fe, Co, Ni, Zn and Cd analogues. In its crystal structure, discrete complexes are observed that are located on centres of inversion. The Mn cations are octahedrally coordinated by four pyridine coligands and two selenocyanate anions that coordinate via the N atom to the metal centres to generate trans-MnN(s)₂N(p)₄ octahedra (s = selenocyanate and p = pyridine). In the extended structure, weak C—H⋯Se contacts are observed. Powder X-ray diffraction (PXRD) investigations prove that a pure sample was obtained and in the IR and Raman spectra, the C—N stretching vibrations are observed at 2058 and 2060 cm⁻¹, respectively, in agreement with the terminal coordination of the selenocyanate anions. Thermogravimetric investigations reveal that the pyridine coligands are removed in two separate steps. In the first mass loss, a compound with the composition Mn(NCSe)₂(C₅H₅N)₂ is formed, whereas in the second mass loss, the remaining pyridine ligands are removed, which is superimposed with the decomposition of Mn(NCSe)₂ formed after ligand removal. In the intermediate compound Mn(NCSe)₂(C₅H₅N)₂, the CN stretching vibration is observed at 2090 cm⁻¹ in the Raman and at 2099 cm⁻¹ in the IR spectra, indicating that the Mn cations are linked by μ-1,3-bridging anionic ligands. PXRD measurements show that a compound has formed that is of poor crystallinity. A comparison of the powder pattern with that calculated for the previously reported Cd(NCSe)₂(C₅H₅N)₂ indicates that these compounds are isotypic, which was proven by a Pawley fit.

Keywords: crystal structure; nickel selenocyanate; discrete complex; thermal properties.

CCDC reference: 2257160

1. Chemical context

Coordination compounds based on transition-metal thio- and selenocyanates can be divided into two major groups. In the first group, the anionic ligands are only terminally coordinated, which leads with monocoordinating ligands to discrete complexes that are of interest, for example, in the field of spin-crossover materials (Gütlich et al., 2000 ; Senthil Kumar & Ruben, 2017 ). In the second group, the anionic ligands act as bridging ligands, which is of structural interest, because a variety of structures with one-, two- or three-dimensional networks can form. Moreover, because these ligands can mediate magnetic exchange, they are also of interest in the field of molecular magnetism (Shurdha et al., 2013 ; Palion-Gazda et al., 2015 ; Prananto et al., 2017 ; Mekuimemba et al., 2018 ). In this context, compounds based on Co^II cations are of special interest because of the strong magnetic anisotropy (Werner et al., 2014 ; Rams et al., 2020a ,b ; Mautner et al., 2018 ).

In the majority of cases, the synthesis of thio- and selenocyanate coordination compounds is performed in solution, that with less chalcophilic metal cations frequently leads to the formation of compounds with terminal anionic ligands. In contrast, the synthesis of compounds with a bridging coordination is more difficult to achieve, even if an excess of the metal salt is used in the synthesis. This behaviour is even more pronounced for selenocyanate compounds. In such cases, an alternative approach was developed, in which precursor complexes with terminal thio- or selenocyanate anions are thermally decomposed, leading to the removal of the coligands in separate steps (Wriedt & Näther, 2010 ; Wöhlert et al., 2012 ). In the course of this irreversible reaction, the desired compounds with bridging anionic ligands are obtained in quantitive yields. This approach is of special interest for the synthesis of selenocyanate coordination polymers because, on one hand, they are frequently difficult to prepare and, on the other hand, only a few such compounds with paramagnetic metal cations are reported in the literature. This method, however, can always be successfully applied for the synthesis of thiocyanates, whereas for selenocyanates sometimes the thermogravimetric (TG) curves are poorly resolved and in some cases poorly crystalline or even amorphous residues are obtained; the reason for this behavior is unknown (Wriedt & Näther, 2010).

This is the case, for example, for compounds with the composition M(NCSe)₂(C₅H₅N)₂, with M = Fe, Co or Ni (C₅H₅N is pyridine). The Fe and Co compounds are isotypic to their thiocyanate analogs and consist of octahedrally coordinated metal cations that are linked by pairs of μ-1,3-bridging anionic ligands into chains (Boeckmann & Näther, 2011 ; Boeckmann et al., 2012 ). None of these compounds can be prepared from solution but the Fe compound is obtained as a pure crystalline material by thermal decomposition of its precursor, whereas the residue obtained for Co is amorphous. However, the Co compound can be prepared in crystalline form by thermal annealing below the decomposition temperature obtained from TG measurements (Boeckmann & Näther, 2011). The Ni compound is also available by thermogravimetry, even if it is of low crystallinity, but comparison of the experimental powder X-ray diffraction (PXRD) pattern obtained after the first mass loss shows that Ni(NCSe)₂(C₅H₅N)₂ is not isotypic to M(NCSe)₂(C₅H₅N)₂, with M = Fe, Co and Cd (Näther & Boeckmann, 2023 ). Its crystal structure is still unknown and in this context it is mentioned that the occurence of different modifications, including polymorphs or isomers, is frequently observed for such thiocyanate coordination compounds (Werner et al., 2015 ). However, in this case, the question arose if the Mn compound is also available as a crystalline material and if it will adopt the structure type of its Fe, Co and Cd analogs or that of Ni(NCSe)₂(C₅H₅N)₂.

To answer this question, much effort was made to synthesize the desired compound Mn(NCSe)₂(C₅H₅N)₂ in solution, but the pyridine-rich title compound Mn(NCSe)₂(C₅H₅N)₄ was always obtained. Single-crystal X-ray diffraction proved that it is isotypic to its Cd, Zn, Fe, Co and Ni analogs (Boeckmann et al., 2011 , 2012; Boeckmann & Näther, 2011; Näther & Boeckmann, 2023) and comparison of the experimental PXRD pattern with that calculated from the single-crystal data proves that a pure phase was obtained (Fig. 1). Therefore, this compound was used as a precursor for TG investigations to check if the pyridine-deficient compound Mn(NCSe)₂(C₅H₅N)₂ can be prepared and if this compound is isotypic to its Cd, Fe and Co analogs (see Section 4, Thermoanalytical investigations).

Figure 1
Experimental (top) and calculated PXRD patterns (bottom) of the title compound.

2. Structural commentary

The single-crystal structure determination proves that the title compound, Mn(NCSe)₂(C₅H₅N)₄, consists of discrete complexes. The asymmetric unit consists of one crystallographically independent Mn²⁺ cation that is located on a centre of inversion, as well as one selenocyanate anion and two pyridine ligands in general positions. The Mn²⁺ cation is octahedrally coordinated by four pyridine coligands and two terminally N-bonded thiocyanate anions that are in trans positions (Fig. 2); the Mn—N bonds to the anions are notably shorter than the bonds to the pyridine molecules (Table 1) and the bond lengths are similar to those in the corresponding Fe and Co compounds. The cis-N—Mn—N angles deviate from the ideal octahedral values by up to 2°, which shows that the octahedra are slightly distorted.

Table 1
Selected geometric parameters (Å, °)

Mn1—N1	2.196 (3)	Mn1—N21	2.317 (3)
Mn1—N11	2.307 (3)

N1—Mn1—N11ⁱ	90.59 (10)	N11—Mn1—N21	92.03 (9)
N1—Mn1—N11	89.41 (10)	N11—Mn1—N21ⁱ	87.97 (9)
N1ⁱ—Mn1—N21	90.02 (10)	N1—C1—Se1	179.1 (3)
N1—Mn1—N21	89.98 (10)	C1—N1—Mn1	151.4 (3)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 2
The crystal structure of the title compound, showing the atom labelling and with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.]

It is noted that the title compound is isotypic to its Fe, Co, Zn and Cd analogues, with selenocyanate ligands, already described in the literature (Boeckmann & Näther, 2011; Boeckmann et al., 2011, 2012). Moreover, the title compound is also isotypic to its thiocyanate analogs with Cu (Gary et al., 2004 ; Li & Zhang, 2004 ), Cd (Qu et al., 2004 ), Ni (Valach et al., 1984 ; Wang et al., 2006 ; Małecki et al., 2010 ), Fe (Søtofte & Rasmussen, 1967 ; Huang & Ogawa, 2006 ), Mn (Yang et al., 2007 ; Małecki et al., 2011 ), Co (Hartl & Brüdgam, 1980 ; Li et al., 2007 ; Deng et al., 2020 ), Mg (Lipkowski & Soldatov, 1993 ), Zn (Wu, 2004 ) and Co (Neumann et al., 2019 ) (see Section 5, Database survey).

3. Supramolecular features

In the crystal structure of the title compound, the complexes are arranged into columns that propagate along the crystallographic c-axis direction (Fig. 3). As in the analogous compounds, there is no indication of aromatic π–π stacking interactions. Within the structure, the Co(NCSe)₂ units form corrugated layers that lie parallel to the the ac plane (Fig. 3). Two C—H⋯Se contacts are observed with C—H⋯Se angles above 150°, which might indicate weak hydrogen-bonding interactions (Table 2). There are additional C—H⋯Se and C—H⋯N contacts, but from the distances and angles, it is concluded that they do not correspond to any significant interaction.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Se1ⁱⁱ	0.95	3.10	3.992 (4)	156
C22—H22⋯Se1ⁱⁱⁱ	0.95	3.11	3.986 (4)	155
C25—H25⋯Se1^iv	0.95	3.04	3.757 (3)	133
C25—H25⋯N1ⁱ	0.95	2.65	3.247 (4)	121
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 3
The crystal structure of the title compound, viewed along the crystallographic c-axis direction. C—H⋯Se interactions are shown as red dashed lines.

4. Thermoanalytical investigations

To investigate the thermal properties of the title compound, measurements using simultaneous differential thermoanalysis and thermogravimetry coupled to mass spectrometry (DTA–TG–MS) were performed. Upon heating, three mass losses are observed that are accompanied by endothermic events in the DTA curve (Fig. 4). The derivative thermogravimetric (DTG) curve shows that these events are reasonably resolved and from the MS trend scan curve it is obvious that in the first endothermic event, pyridine is removed. The experimental mass loss of 27.0% is in good agreement with that calculated for the removal of two pyridine ligands (Δm_calc = −27.2%), whereas that in the second step is higher with a value of 40.5%, indicating that pyridine removal and the decomposition of Mn(NCSe)₂ occur simultaneously. The fact that even in the third step pyridine might be removed indicates that the reaction is more complex, except that the signal at m/z = 79 corresponds to some fragment formed during decomposition.

Figure 4
DTG, TG and DTA curves, and the MS trend scan curve for the title compound measured at 4 °C min⁻¹ in helium. The experimental mass loss is given in % and the peak temperatures are given in °C.

However, to identify the product formed in the first mass loss this residue was isolated in a second TG measurement and investigated by IR and Raman spectroscopy, as well as PXRD. The CN stretching vibration of the selenocyanate anions is observed at 2099 cm⁻¹ in the Raman and at 2090 cm⁻¹ in the IR spectra, clearly proving that μ-1,3-bridging anionic ligands are present (Fig. S2 in the supporting information). The comparison of the experimental pattern with that calculated for Cd(NCSe)₂(C₅H₅N)₂, using single-crystal data retrieved from the literature, indicate that they are isotypic (Fig. S3). The pattern can easily be indexed, leading to a unit cell that is comparable to that of the Cd, Fe and Co compounds. Finally, a Pawley fit of the experimental pattern using the crystallographic data of the cadmium compound (with Mn replacing Cd) as starting model was performed, which supports all these findings. The refined lattice parameters are shown together with the difference plot in Fig. 5. As expected, due to the smaller ionic radii, the unit-cell volume is smaller for the Mn compound compared to its Cd anologue [1117.9 (1) versus 1145.6 (3) Å³] (Boeckmann et al., 2011).

Figure 5
Pawley fit of Mn(NCSe)₂(pyridine)₂ obtained by TG measurements of the title compound Mn(NCSe)₂(pyridine)₄.

5. Database survey

A search in the Cambridge Structural Database (Version 5.43, last update November 2022; Groom et al., 2016 ) using ConQuest (Bruno et al., 2002 ) reveals that some selenocyanate compounds with pyridine coligands have been reported in the literature. These comprise discrete complexes with an octahedral coordination with the composition M(NCSe)₂(C₅H₅N)₄, with M = Fe (CSD refcode CAQVEX; Boeckmann et al., 2012), Co (ITISOU; Boeckmann & Näther, 2011), Zn (OWOHUE; Boeckmann et al., 2011) and Cd (OWOJAM; Boeckmann et al., 2011). The isotypic Ni compound M(NCSe)₂(pyridine)₄ was reported recently (Näther & Boeckmann, 2023). For the Co compound, mixed crystals with the composition Co(NCS)_x(NCSe)_2–x(C₅H₅N)₄ have also been reported (TIXDOW and TIXDOW01; Neumann et al., 2019).

As mentioned in the Chemical context section (Section 1) with pyridine, there also exist isotypic pyridine-deficient compounds with the composition M(NCSe)₂(C₅H₅N)₂, with M = Fe (CAQVIB; Boeckmann et al., 2012), Co (ITISUA; Boeckmann & Näther, 2011), Zn (OWOJEQ; Boeckmann et al., 2011) and Cd (OWOHOY; Boeckmann et al., 2011). In the first compounds, M(NCSe)₂ chains are observed, whereas the Zn compound consists of discrete complexes.

One mixed-metal compound with the composition HgSr(NCSe)₄(C₅H₅N)₆ (CICLOP; Brodersen et al., 1984 ), a dinuclear complex with the composition [Fe(NCS)₂]₂(C₅H₅N)₂[(3,5-bis(pyridin-2-yl)pyrazolyl]₂ (FIZYEU; Sy et al., 2014 ) and a complex with the composition Fe(NCSe)₂(C₅H₅N)₂(2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) pyridine solvate (TISWOI; Tao et al., 2007 ) are also reported in the literature.

6. Synthesis and crystallization

MnCl₂·2H₂O, KNCSe and pyridine were purchased from Alfa Aesar and used without any further purification.

6.1. Synthesis

0.25 mmol (49.7 mg) MnCl₂·2H₂O and 0.5 mmol (72.0 mg) KNCSe were reacted with a mixture of 1.5 ml of pyridine and 1.5 ml of water. The mixture was stirred for 2 d at room temperature and the precipitate was filtered off, washed with very small amounts of water and dried in air. Single crystals were obtained under the same conditions but without stirring.

It is noted that even if a large excess of MnCl₂·2H₂O and KNCSe was used in the synthesis, there are no hints for the formation of a pyridine-deficient compound with the composition Mn(NCSe)₂(pyridine)₂.

6.2. Experimental details

Single-crystal X-ray data were measured using an Image Plate Diffraction System (IPDS-2) from Stoe & Cie. Differential thermal analysis and thermogravimetric (DTA–TG–MS) measurements were performed in a dynamic helium atmosphere in Al₂O₃ crucibles using a Netzsch thermobalance with a skimmer coupling and a Balzer Quadrupol MS. The PXRD measurements were performed with a Stoe Transmission Powder Diffraction System (STADI P) with Cu Kα₁ radiation equipped with a linear position-sensitive MYTHEN 1K detector from Stoe & Cie. The IR data were measured using a Bruker Alpha-P ATR–IR spectrometer and the Raman spectra were measured with a Bruker Vertex 70 spectrometer.

7. Refinement

H atoms were positioned with idealized geometry (C—H = 0.95 Å) and refined with U_iso(H) = 1.2U_eq(C) using a riding model. Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(NCSe)₂(C₅H₅N)₂]
M_r	581.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	170
a, b, c (Å)	12.5335 (9), 13.4331 (8), 15.1300 (12)
β (°)	108.608 (8)
V (Å³)	2414.2 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.58
Crystal size (mm)	0.25 × 0.2 × 0.17

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical
T_min, T_max	0.332, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	8352, 2636, 2124
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.088, 1.03
No. of reflections	2636
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.59
Computer programs: X-AREA (Stoe & Cie, 2008 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 ) and publCIF (Westrip, 2010 ).

The Pawely fit for the diffraction pattern of Mn(NCSe)₂(C₅H₅N)₂ obtained by thermal decomposition was carried out using TOPAS Academic (Version 6.0; Coelho 2018 ). Initial lattice parameters were taken from Cd(NCSe)₂(C₅H₅N)₂: R_wp = 2.98%, R_exp = 2.08% and GOF = 1.44.

Supporting information

CCDC reference: 2257160

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989023003535/hb8063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023003535/hb8063Isup2.hkl

Additional spectra. DOI: https://doi.org/10.1107/S2056989023003535/hb8063sup3.pdf

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(isoselenocyanato-κN)tetrakis(pyridine-κN)manganese(II) top

Crystal data top

[Mn(NCSe)₂(C₅H₅N)₂]	F(000) = 1148
M_r = 581.30	D_x = 1.599 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.5335 (9) Å	Cell parameters from 8352 reflections
b = 13.4331 (8) Å	θ = 2.4–27.0°
c = 15.1300 (12) Å	µ = 3.58 mm⁻¹
β = 108.608 (8)°	T = 170 K
V = 2414.2 (3) Å³	Block, colorless
Z = 4	0.25 × 0.2 × 0.17 mm

Data collection top

Stoe IPDS-2 diffractometer	2124 reflections with I > 2σ(I)
ω scans	R_int = 0.056
Absorption correction: numerical	θ_max = 27.0°, θ_min = 2.4°
T_min = 0.332, T_max = 0.678	h = −16→16
8352 measured reflections	k = −17→16
2636 independent reflections	l = −18→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0376P)² + 6.3344P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2636 reflections	Δρ_max = 0.56 e Å⁻³
142 parameters	Δρ_min = −0.59 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	0.750000	0.750000	0.500000	0.01953 (15)
N11	0.6262 (2)	0.6231 (2)	0.43418 (18)	0.0238 (6)
C11	0.6575 (3)	0.5279 (3)	0.4461 (2)	0.0318 (8)
H11	0.734043	0.513251	0.479058	0.038*
C12	0.5845 (3)	0.4496 (3)	0.4129 (3)	0.0406 (9)
H12	0.610081	0.382797	0.423720	0.049*
C13	0.4740 (3)	0.4701 (3)	0.3639 (3)	0.0454 (10)
H13	0.421823	0.417644	0.340179	0.054*
C14	0.4403 (3)	0.5677 (3)	0.3500 (3)	0.0480 (11)
H14	0.364597	0.583892	0.315879	0.058*
C15	0.5183 (3)	0.6422 (3)	0.3864 (3)	0.0347 (8)
H15	0.494330	0.709602	0.376995	0.042*
N21	0.7901 (2)	0.6823 (2)	0.64791 (18)	0.0222 (5)
C21	0.7567 (3)	0.7256 (3)	0.7149 (2)	0.0284 (7)
H21	0.717815	0.787259	0.701489	0.034*
C22	0.7765 (3)	0.6842 (3)	0.8025 (2)	0.0356 (8)
H22	0.752223	0.717571	0.848060	0.043*
C23	0.8319 (3)	0.5938 (3)	0.8230 (2)	0.0322 (8)
H23	0.846555	0.564051	0.882662	0.039*
C24	0.8654 (3)	0.5481 (3)	0.7544 (2)	0.0303 (7)
H24	0.902487	0.485410	0.765582	0.036*
C25	0.8441 (3)	0.5951 (3)	0.6690 (2)	0.0268 (7)
H25	0.869203	0.563732	0.622887	0.032*
Se1	0.41161 (3)	0.84748 (3)	0.58422 (3)	0.03339 (12)
C1	0.5323 (3)	0.8406 (2)	0.5460 (2)	0.0220 (6)
N1	0.6105 (2)	0.8349 (2)	0.5213 (2)	0.0291 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0146 (3)	0.0198 (3)	0.0244 (3)	0.0001 (2)	0.0065 (2)	−0.0004 (3)
N11	0.0202 (12)	0.0227 (14)	0.0273 (14)	−0.0022 (10)	0.0058 (10)	−0.0023 (11)
C11	0.0340 (18)	0.0243 (18)	0.0366 (19)	−0.0002 (14)	0.0106 (15)	−0.0059 (14)
C12	0.054 (2)	0.0227 (18)	0.048 (2)	−0.0072 (18)	0.0202 (18)	−0.0072 (17)
C13	0.042 (2)	0.042 (2)	0.054 (2)	−0.0259 (19)	0.0172 (18)	−0.0170 (19)
C14	0.0282 (18)	0.047 (3)	0.059 (3)	−0.0131 (18)	−0.0003 (18)	−0.008 (2)
C15	0.0248 (16)	0.0302 (19)	0.043 (2)	−0.0020 (15)	0.0023 (15)	0.0006 (16)
N21	0.0169 (12)	0.0243 (14)	0.0243 (13)	−0.0015 (10)	0.0050 (10)	−0.0021 (10)
C21	0.0251 (15)	0.0305 (18)	0.0289 (17)	0.0007 (13)	0.0077 (13)	−0.0075 (13)
C22	0.0363 (19)	0.047 (2)	0.0261 (17)	−0.0025 (17)	0.0132 (14)	−0.0077 (15)
C23	0.0258 (16)	0.045 (2)	0.0255 (17)	−0.0024 (15)	0.0076 (13)	0.0036 (15)
C24	0.0242 (15)	0.0310 (18)	0.0338 (17)	0.0053 (14)	0.0066 (13)	0.0075 (15)
C25	0.0263 (16)	0.0279 (18)	0.0257 (16)	0.0040 (13)	0.0077 (13)	0.0007 (12)
Se1	0.0337 (2)	0.0309 (2)	0.0452 (2)	0.00150 (15)	0.02617 (16)	−0.00001 (16)
C1	0.0236 (14)	0.0158 (14)	0.0221 (15)	0.0007 (12)	0.0010 (12)	0.0007 (12)
N1	0.0211 (13)	0.0334 (16)	0.0351 (15)	0.0070 (12)	0.0120 (11)	0.0015 (12)

Geometric parameters (Å, º) top

Mn1—N1ⁱ	2.196 (3)	C14—H14	0.9500
Mn1—N1	2.196 (3)	C15—H15	0.9500
Mn1—N11ⁱ	2.307 (3)	N21—C25	1.340 (4)
Mn1—N11	2.307 (3)	N21—C21	1.346 (4)
Mn1—N21	2.317 (3)	C21—C22	1.384 (5)
Mn1—N21ⁱ	2.317 (3)	C21—H21	0.9500
N11—C11	1.332 (4)	C22—C23	1.384 (5)
N11—C15	1.339 (4)	C22—H22	0.9500
C11—C12	1.379 (5)	C23—C24	1.383 (5)
C11—H11	0.9500	C23—H23	0.9500
C12—C13	1.374 (6)	C24—C25	1.385 (5)
C12—H12	0.9500	C24—H24	0.9500
C13—C14	1.373 (6)	C25—H25	0.9500
C13—H13	0.9500	Se1—C1	1.786 (3)
C14—C15	1.384 (5)	C1—N1	1.157 (4)

N1ⁱ—Mn1—N1	180.00 (15)	C13—C14—C15	119.1 (4)
N1ⁱ—Mn1—N11ⁱ	89.41 (10)	C13—C14—H14	120.4
N1—Mn1—N11ⁱ	90.59 (10)	C15—C14—H14	120.4
N1ⁱ—Mn1—N11	90.59 (10)	N11—C15—C14	122.6 (4)
N1—Mn1—N11	89.41 (10)	N11—C15—H15	118.7
N11ⁱ—Mn1—N11	180.0	C14—C15—H15	118.7
N1ⁱ—Mn1—N21	90.02 (10)	C25—N21—C21	117.0 (3)
N1—Mn1—N21	89.98 (10)	C25—N21—Mn1	120.7 (2)
N11ⁱ—Mn1—N21	87.97 (9)	C21—N21—Mn1	122.3 (2)
N11—Mn1—N21	92.03 (9)	N21—C21—C22	122.9 (3)
N1ⁱ—Mn1—N21ⁱ	89.98 (10)	N21—C21—H21	118.5
N1—Mn1—N21ⁱ	90.02 (10)	C22—C21—H21	118.5
N11ⁱ—Mn1—N21ⁱ	92.03 (9)	C21—C22—C23	119.4 (3)
N11—Mn1—N21ⁱ	87.97 (9)	C21—C22—H22	120.3
N21—Mn1—N21ⁱ	180.0	C23—C22—H22	120.3
C11—N11—C15	117.4 (3)	C24—C23—C22	118.2 (3)
C11—N11—Mn1	121.5 (2)	C24—C23—H23	120.9
C15—N11—Mn1	121.0 (2)	C22—C23—H23	120.9
N11—C11—C12	123.3 (3)	C23—C24—C25	118.9 (3)
N11—C11—H11	118.3	C23—C24—H24	120.5
C12—C11—H11	118.3	C25—C24—H24	120.5
C13—C12—C11	118.8 (4)	N21—C25—C24	123.6 (3)
C13—C12—H12	120.6	N21—C25—H25	118.2
C11—C12—H12	120.6	C24—C25—H25	118.2
C14—C13—C12	118.7 (3)	N1—C1—Se1	179.1 (3)
C14—C13—H13	120.6	C1—N1—Mn1	151.4 (3)
C12—C13—H13	120.6

Symmetry code: (i) −x+3/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Se1ⁱⁱ	0.95	3.10	3.992 (4)	156
C22—H22···Se1ⁱⁱⁱ	0.95	3.11	3.986 (4)	155
C25—H25···Se1^iv	0.95	3.04	3.757 (3)	133
C25—H25···N1ⁱ	0.95	2.65	3.247 (4)	121

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

Acknowledgements

This work was supported by the state of Schleswig-Holstein.

References

Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106. Web of Science CSD CrossRef CAS Google Scholar
Boeckmann, J., Reinert, T. & Näther, C. (2011). Z. Anorg. Allg. Chem. 637, 940–946. Web of Science CSD CrossRef CAS Google Scholar
Boeckmann, J., Wriedt, M. & Näther, C. (2012). Chem. Eur. J. 18, 5284–5289. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brodersen, K., Cygan, M. & Hummel, H. U. (1984). Z. Naturforsch. B, 39, 2582–2585. CrossRef Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Coelho, A. A. (2018). J. Appl. Cryst. 51, 210–218. Web of Science CrossRef CAS IUCr Journals Google Scholar
Deng, Y. F., Singh, M. K., Gan, D., Xiao, T., Wang, Y., Liu, S., Wang, Z., Ouyang, Z., Zhang, Y. Z. & Dunbar, K. R. (2020). Inorg. Chem. 59, 7622–7630. CSD CrossRef CAS PubMed Google Scholar
Gary, J. B., Kautz, J. A., Klausmeyer, K. K. & Wong, C.-W. (2004). Acta Cryst. E60, m328–m329. Web of Science CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gütlich, P., Garcia, Y. & Goodwin, H. A. (2000). Chem. Soc. Rev. 29, 419–427. Web of Science CrossRef CAS Google Scholar
Hartl, H. & Brüdgam, I. (1980). Acta Cryst. B36, 162–165. CSD CrossRef IUCr Journals Google Scholar
Huang, W. & Ogawa, T. (2006). J. Mol. Struct. 785, 21–26. CSD CrossRef CAS Google Scholar
Li, Y., Zhang, Z. X., Li, Q. S., Song, W. D., Li, K. C., Xu, J. Q., Miao, Y. L. & Pan, L. Y. (2007). J. Coord. Chem. 60, 795–803. CSD CrossRef CAS Google Scholar
Li, Z.-X. & Zhang, X.-L. (2004). Acta Cryst. E60, m1597–m1598. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lipkowski, J. & Soldatov, D. (1993). J. Coord. Chem. 28, 265–269. CSD CrossRef CAS Google Scholar
Małecki, J. G., Machura, B., Świtlicka, A., Groń, T. & Bałanda, M. (2011). Polyhedron, 30, 746–753. Google Scholar
Małecki, J. G., Świtlicka, A., Groń, T. & Bałanda, M. (2010). Polyhedron, 29, 3198–3206. Google Scholar
Mautner, F. A., Traber, M., Fischer, R. C., Torvisco, A., Reichmann, K., Speed, S., Vicente, R. & Massoud, S. S. (2018). Polyhedron, 154, 436–442. Web of Science CSD CrossRef CAS Google Scholar
Mekuimemba, C. D., Conan, F., Mota, A. J., Palacios, M. A., Colacio, E. & Triki, S. (2018). Inorg. Chem. 57, 2184–2192. Web of Science CSD CrossRef CAS PubMed Google Scholar
Näther, C. & Boeckmann, J. (2023). Acta Cryst. E79, 90–94. CSD CrossRef IUCr Journals Google Scholar
Neumann, T., Rams, M., Tomkowicz, Z., Jess, I. & Näther, C. (2019). Chem. Commun. 55, 2652–2655. Web of Science CSD CrossRef CAS Google Scholar
Palion-Gazda, J., Machura, B., Lloret, F. & Julve, M. (2015). Cryst. Growth Des. 15, 2380–2388. CAS Google Scholar
Prananto, Y. P., Urbatsch, A., Moubaraki, B., Murray, K. S., Turner, D. R., Deacon, G. B. & Batten, S. R. (2017). Aust. J. Chem. 70, 516–528. Web of Science CSD CrossRef CAS Google Scholar
Qu, Y., Liu, Z.-D., Zhu, H.-L. & Tan, M.-Y. (2004). Acta Cryst. E60, m1013–m1014. CSD CrossRef IUCr Journals Google Scholar
Rams, M., Böhme, M., Kataev, V., Krupskaya, Y., Büchner, B., Plass, W., Neumann, T., Tomkowicz, Z. & Näther, C. (2020a). Phys. Chem. Chem. Phys. 19, 24534–24544. CrossRef Google Scholar
Rams, M., Jochim, A., Böhme, M., Lohmiller, T., Ceglarska, M., Rams, M. M., Schnegg, A., Plass, W. & Näther, C. (2020b). Chem. Eur. J. 26, 2837–2851. CSD CrossRef CAS PubMed Google Scholar
Senthil Kumar, K. & Ruben, M. (2017). Coord. Chem. Rev. 346, 176–205. Web of Science CrossRef 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
Shurdha, E., Moore, C. E., Rheingold, A. L., Lapidus, S. H., Stephens, P. W., Arif, A. M. & Miller, J. S. (2013). Inorg. Chem. 52, 10583–10594. Web of Science CSD CrossRef CAS PubMed Google Scholar
Søtofte, I. & Rasmussen, S. E. (1967). Acta Chem. Scand. 21, 2028–2040. Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Sy, M., Varret, F., Boukheddaden, K., Bouchez, G., Marrot, S., Kawata, S. & Kaizaki, S. (2014). Angew. Chem. Int. Ed. 53, 7539–7542. Web of Science CSD CrossRef CAS Google Scholar
Tao, J. Q., Gu, Z. G., Wang, T. W., Yang, Q. F., Zuo, J. L. & You, X. Z. (2007). Inorg. Chim. Acta, 360, 4125–4132. Web of Science CSD CrossRef CAS Google Scholar
Valach, F., Sivý, P. & Koreň, B. (1984). Acta Cryst. C40, 957–959. CSD CrossRef CAS IUCr Journals Google Scholar
Wang, C. F., Zhu, Z. Y., Zhou, X. G., Weng, L. H., Shen, Q. S. & Yan, Y. G. (2006). Inorg. Chem. Commun. 9, 1326–1330. CSD CrossRef CAS Google Scholar
Werner, J., Rams, M., Tomkowicz, Z. & Näther, C. (2014). Dalton Trans. 43, 17333–17342. Web of Science CSD CrossRef CAS PubMed Google Scholar
Werner, J., Runčevski, T., Dinnebier, R., Ebbinghaus, S. G., Suckert, S. & Näther, C. (2015). Eur. J. Inorg. Chem. 2015, 3236–3245. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S., Ruschewitz, U. & Näther, C. (2012). Cryst. Growth Des. 12, 2715–2718. Google Scholar
Wriedt, M. & Näther, C. (2010). Chem. Commun. 46, 4707–4709. Web of Science CSD CrossRef CAS Google Scholar
Wu, C.-B. (2004). Acta Cryst. E60, m1490–m1491. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yang, H., Chen, Y., Li, D. & Wang, D. (2007). Acta Cryst. E63, m3186. CSD CrossRef IUCr Journals 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.