Poly[1-ethyl-3-methyl­imidazolium [tri-μ-iso­thio­cyanato-manganate(II)]]

Peppel, T.; Köckerling, M.

doi:10.1107/S2414314619016596

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 12| December 2019| x191659

https://doi.org/10.1107/S2414314619016596

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Poly[1-ethyl-3-methylimidazolium [tri-μ-isothiocyanato-manganate(II)]]

Tim Peppel ^a ^* and Martin Köckerling ^b,^c

^aLeibniz-Institut für Katalyse e.V., Heterogene Photokatalyse, Albert-Einstein-Str. 29a, D-18059 Rostock, Germany, ^bUniversität Rostock, Institut für Chemie, Anorganische Festkörperchemie, Albert-Einstein-Str. 3a, D-18059 Rostock, Germany, and ^cDepartment Life, Light and Matter, Universität Rostock, 18051 Rostock, Germany
^*Correspondence e-mail: tim.peppel@catalysis.de

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 23 November 2019; accepted 9 December 2019; online 17 December 2019)

The title compound, {(C₉H₁₁N₂)[Mn(NCS)₃]}_n, has been obtained as a side product of the salt metathesis reaction of 1-ethyl-3-methylimidazolium bromide, (EMIm)Br, and K₂[Mn(NCS)₄]. The structure consists of discrete 1-ethyl-3-methylimidazolium cations and an anionic two-dimensional network of manganese(II)-based complex anions, interconnected by thiocyanate ions. Every Mn²⁺ ion is coordinated by three S atoms of three NCS⁻ ions and three N atoms of further three NCS⁻ ions in a meridional octahedral fashion.

Keywords: manganese; thiocyanate; ionic liquid; crystal structure; network structure.

CCDC reference: 1971102

Structure description

For many years, ionic liquids containing metal ions, especially those with paramagnetic properties have attracted great interest because of their unique properties and possible applications (Santos et al., 2014 ; Clark et al., 2016 ). Our ongoing efforts to investigate such low-melting metal-containing ionic liquids were first focused on compounds containing a cobalt ion (Kozlova et al., 2009 , Geppert-Rybczyńska et al., 2010 ; Peppel et al., 2010 ). Later, Mn containing systems were included (Peppel et al., 2019 ).

The title compound has been obtained as a side product as a result of a slow chemical decomposition of the ionic liquid (EMIm)₂[Mn(NCS)₄].

Fig. 1 shows the molecular structure of the environment of the Mn^II ion, which is coordinated octahedrally by six thiocyanato ligands. Three are N-bonded and the other three S-bonded in a mer fashion. All thiocyanato ligands are bridging two Mn ions. Thereby two-dimensional layers are formed. Fig. 2 shows a cutout of the structure of this anionic layer. Whereas the N atoms have almost linear Mn—N—C angles (average of 172.0°), the S atoms are bonded with a Mn—S—C angle of 98.1° (average).

Figure 1
A view of the molecular structure of the octahedrally coordinated [Mn(NCS)₃(SCN)₃]⁻ units of the polymeric complex anion and the EMIm⁺ cation of the title compound, with the atoms being presented as 50% displacement ellipsoids. Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (iii) x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ − z.

Figure 2
View of the structure of the anionic [Mn(NCS)₃]⁻ layer.

The anionic layers are stacked along the crystallographic a-axis direction and separated by layers of the EMIm⁺ cations (see Fig. 3).

Figure 3
The packing of anionic [Mn(NCS)₃]⁻ and EMIM⁺ layers along a.

A similar type of polymeric structural motive is found in Cd^II complexes containing SCN⁻ ligands (Kuniyasu et al., 1987 ; Chen et al., 2002 ; Gao et al., 2008 ; Dang et al., 2011 ; Cao et al., 2019 ).

Synthesis and crystallization

The title compound, (EMIm)[Mn(NCS)₃], was obtained as light-green single crystals directly from a charge of pure, liquid (EMIm)₂[Mn(NCS)₄] over a time period of several months. (EMIm)₂[Mn(NCS)₄] was prepared via a salt metathesis reaction from 2.05 mmol of (EMIm)Br (Nishida et al., 2003 ) and 1.00 mmol of K₂[Mn(NCS)₄] as a light-green liquid in moderate yield (>70%) (Peppel et al., 2019). Elemental analysis for C₁₆H₂₂MnN₈S₄ % (calc.): C 37.5 (37.7), H 4.1 (4.3), N 20.6 (21.9), S 22.3 (25.1).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One low angle reflection (100) was omitted in the structure refinement because its intensity was affected by the beam stop.

Table 1
Experimental details

Crystal data
Chemical formula	(C₉H₁₁N₂)[Mn(NCS)₃]
M_r	340.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.9355 (5), 17.025 (1), 9.7743 (6)
β (°)	116.107 (1)
V (Å³)	1484.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.29
Crystal size (mm)	0.45 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEX X8 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
No. of measured, independent and observed [I > 2σ(I)] reflections	20690, 5123, 4084
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.745

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.065, 1.00
No. of reflections	5123
No. of parameters	207
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1971102

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016596/rz4036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016596/rz4036Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[1-ethyl-3-methylimidazolium [tri-µ-isothiocyanato-manganate(II)]] top

Crystal data top

(C₆H₁₁N₂)[Mn(NCS)₃]	F(000) = 692
M_r = 340.35	D_x = 1.523 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9355 (5) Å	Cell parameters from 5662 reflections
b = 17.025 (1) Å	θ = 2.6–31.8°
c = 9.7743 (6) Å	µ = 1.29 mm⁻¹
β = 116.107 (1)°	T = 173 K
V = 1484.7 (2) Å³	Irregular block, light green
Z = 4	0.45 × 0.25 × 0.20 mm

Data collection top

Bruker APEX X8 CCD diffractometer	4084 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.038
φ and ω scans	θ_max = 32.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
	k = −25→25
20690 measured reflections	l = −14→14
5123 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: difference Fourier map
wR(F²) = 0.065	All H-atom parameters refined
S = 1.00	w = 1/[σ²(F_o²) + (0.0256P)² + 0.2744P] where P = (F_o² + 2F_c²)/3
5123 reflections	(Δ/σ)_max = 0.001
207 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.27 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.

Refinement. All H atoms were located in a difference Fourier map and refined freely.

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

	x	y	z	U_iso*/U_eq
Mn	0.46124 (2)	0.33563 (2)	0.56139 (2)	0.02086 (5)
S1	0.67894 (4)	0.54391 (2)	0.37158 (4)	0.02376 (7)
C1	0.6170 (1)	0.46966 (7)	0.4348 (1)	0.0205 (2)
N1	0.5757 (1)	0.41700 (7)	0.4816 (1)	0.0263 (2)
S2	0.69073 (4)	0.15417 (2)	0.34079 (4)	0.02725 (8)
C2	0.6135 (1)	0.20229 (7)	0.4342 (1)	0.0229 (2)
N2	0.5587 (1)	0.23630 (7)	0.4990 (1)	0.0297 (2)
S3	0.21484 (4)	0.15971 (2)	0.78181 (4)	0.02471 (7)
C3	0.2818 (1)	0.21887 (7)	0.6940 (1)	0.0206 (2)
N3	0.3295 (1)	0.26164 (7)	0.6338 (1)	0.0262 (2)
N4	0.2096 (1)	0.43795 (7)	0.9264 (1)	0.0247 (2)
C4	0.1592 (2)	0.37295 (8)	0.8450 (1)	0.0243 (3)
H4A	0.209 (2)	0.3268 (9)	0.862 (2)	0.029 (4)*
N5	0.0219 (1)	0.38560 (7)	0.7376 (1)	0.0254 (2)
C5	−0.0165 (2)	0.46184 (9)	0.7513 (2)	0.0394 (4)
H5A	−0.108 (2)	0.485 (1)	0.685 (2)	0.058 (6)*
C6	0.1005 (2)	0.4941 (1)	0.8692 (2)	0.0369 (3)
H6A	0.113 (2)	0.542 (1)	0.911 (2)	0.048 (5)*
C7	0.3582 (2)	0.4484 (1)	1.0528 (2)	0.0340 (3)
H7A	0.419 (2)	0.414 (1)	1.052 (2)	0.061 (7)*
H7B	0.351 (2)	0.449 (1)	1.144 (3)	0.069 (7)*
H7C	0.392 (2)	0.496 (1)	1.039 (2)	0.048 (5)*
C8	−0.0702 (2)	0.32934 (9)	0.6187 (2)	0.0290 (3)
H8A	−0.170 (2)	0.3302 (9)	0.610 (2)	0.027 (4)*
H8B	−0.031 (2)	0.2779 (9)	0.653 (2)	0.026 (4)*
C9	−0.0690 (2)	0.3471 (1)	0.4682 (2)	0.0363 (3)
H9A	−0.135 (2)	0.311 (1)	0.395 (2)	0.045 (5)*
H9B	0.035 (2)	0.343 (1)	0.476 (2)	0.047 (5)*
H9C	−0.101 (2)	0.398 (1)	0.441 (2)	0.048 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0247 (1)	0.01898 (9)	0.02218 (9)	−0.00214 (7)	0.01328 (8)	0.00021 (7)
S1	0.0270 (2)	0.0216 (2)	0.0291 (2)	−0.0018 (1)	0.0182 (1)	0.0014 (1)
C1	0.0178 (5)	0.0237 (6)	0.0211 (5)	0.0019 (5)	0.0095 (5)	−0.0006 (4)
N1	0.0267 (6)	0.0243 (5)	0.0336 (6)	0.0027 (4)	0.0186 (5)	0.0037 (5)
S2	0.0265 (2)	0.0290 (2)	0.0260 (2)	0.0055 (1)	0.0112 (1)	−0.0003 (1)
C2	0.0239 (6)	0.0192 (6)	0.0214 (5)	−0.0007 (5)	0.0061 (5)	0.0017 (4)
N2	0.0347 (6)	0.0271 (6)	0.0258 (5)	0.0037 (5)	0.0119 (5)	−0.0010 (5)
S3	0.0267 (2)	0.0252 (2)	0.0250 (2)	−0.0042 (1)	0.0138 (1)	0.0024 (1)
C3	0.0214 (6)	0.0203 (6)	0.0191 (5)	0.0005 (5)	0.0079 (5)	−0.0018 (4)
N3	0.0288 (6)	0.0263 (6)	0.0231 (5)	−0.0038 (5)	0.0110 (4)	0.0013 (4)
N4	0.0256 (5)	0.0252 (5)	0.0225 (5)	−0.0018 (4)	0.0099 (4)	0.0006 (4)
C4	0.0243 (6)	0.0235 (6)	0.0251 (6)	0.0019 (5)	0.0109 (5)	0.0020 (5)
N5	0.0229 (5)	0.0239 (5)	0.0273 (5)	0.0005 (4)	0.0091 (4)	−0.0022 (4)
C5	0.0337 (8)	0.0302 (8)	0.0414 (8)	0.0109 (6)	0.0047 (7)	−0.0072 (6)
C6	0.0388 (8)	0.0269 (7)	0.0366 (8)	0.0051 (6)	0.0089 (7)	−0.0070 (6)
C7	0.0294 (8)	0.0363 (8)	0.0298 (7)	−0.0072 (7)	0.0073 (6)	−0.0003 (6)
C8	0.0230 (7)	0.0269 (7)	0.0330 (7)	−0.0023 (5)	0.0086 (6)	−0.0057 (6)
C9	0.0337 (8)	0.0393 (9)	0.0347 (8)	−0.0055 (7)	0.0140 (7)	−0.0098 (7)

Geometric parameters (Å, º) top

Mn—N1	2.145 (1)	N4—C7	1.460 (2)
Mn—N3	2.149 (1)	C4—N5	1.322 (2)
Mn—N2	2.165 (1)	C4—H4A	0.90 (2)
Mn—S2ⁱ	2.6845 (4)	N5—C5	1.376 (2)
Mn—S1ⁱⁱ	2.7163 (4)	N5—C8	1.473 (2)
Mn—S3ⁱⁱⁱ	2.7530 (4)	C5—C6	1.343 (2)
S1—C1	1.641 (1)	C5—H5A	0.94 (2)
S1—Mnⁱⁱ	2.7163 (4)	C6—H6A	0.89 (2)
C1—N1	1.161 (2)	C7—H7A	0.84 (2)
S2—C2	1.646 (1)	C7—H7B	0.92 (2)
S2—Mnⁱⁱⁱ	2.6846 (4)	C7—H7C	0.91 (2)
C2—N2	1.156 (2)	C8—C9	1.506 (2)
S3—C3	1.643 (1)	C8—H8A	0.96 (2)
S3—Mnⁱ	2.7530 (4)	C8—H8B	0.96 (2)
C3—N3	1.160 (2)	C9—H9A	0.96 (2)
N4—C4	1.326 (2)	C9—H9B	1.00 (2)
N4—C6	1.367 (2)	C9—H9C	0.93 (2)

N1—Mn—N3	174.68 (4)	N4—C4—H4A	126 (1)
N1—Mn—N2	91.59 (4)	C4—N5—C5	108.0 (1)
N3—Mn—N2	92.73 (5)	C4—N5—C8	125.9 (1)
N1—Mn—S2ⁱ	88.82 (3)	C5—N5—C8	126.0 (1)
N3—Mn—S2ⁱ	94.04 (3)	C6—C5—N5	107.3 (1)
N2—Mn—S2ⁱ	92.99 (3)	C6—C5—H5A	129 (1)
N1—Mn—S1ⁱⁱ	90.58 (3)	N5—C5—H5A	124 (1)
N3—Mn—S1ⁱⁱ	84.94 (3)	C5—C6—N4	107.2 (1)
N2—Mn—S1ⁱⁱ	176.25 (3)	C5—C6—H6A	131 (1)
S2ⁱ—Mn—S1ⁱⁱ	90.11 (1)	N4—C6—H6A	122 (1)
N1—Mn—S3ⁱⁱⁱ	90.14 (3)	N4—C7—H7A	112 (1)
N3—Mn—S3ⁱⁱⁱ	86.53 (3)	N4—C7—H7B	110 (1)
N2—Mn—S3ⁱⁱⁱ	93.18 (3)	H7A—C7—H7B	112 (2)
S2ⁱ—Mn—S3ⁱⁱⁱ	173.77 (1)	N4—C7—H7C	106 (1)
S1ⁱⁱ—Mn—S3ⁱⁱⁱ	83.76 (1)	H7A—C7—H7C	108 (2)
C1—S1—Mnⁱⁱ	100.02 (4)	H7B—C7—H7C	109 (2)
N1—C1—S1	178.8 (1)	N5—C8—C9	111.8 (1)
C1—N1—Mn	168.1 (1)	N5—C8—H8A	108.5 (9)
C2—S2—Mnⁱⁱⁱ	97.91 (5)	C9—C8—H8A	111.5 (9)
N2—C2—S2	179.6 (1)	N5—C8—H8B	107.5 (9)
C2—N2—Mn	157.2 (1)	C9—C8—H8B	110.7 (9)
C3—S3—Mnⁱ	96.51 (4)	H8A—C8—H8B	107 (1)
N3—C3—S3	178.8 (1)	C8—C9—H9A	108 (1)
C3—N3—Mn	168.2 (1)	C8—C9—H9B	111 (1)
C4—N4—C6	108.4 (1)	H9A—C9—H9B	111 (2)
C4—N4—C7	125.7 (1)	C8—C9—H9C	109 (1)
C6—N4—C7	125.8 (1)	H9A—C9—H9C	111 (2)
N5—C4—N4	109.0 (1)	H9B—C9—H9C	107 (2)
N5—C4—H4A	125 (1)

C6—N4—C4—N5	0.1 (2)	N5—C5—C6—N4	0.3 (2)
C7—N4—C4—N5	−178.2 (1)	C4—N4—C6—C5	−0.2 (2)
N4—C4—N5—C5	0.1 (2)	C7—N4—C6—C5	178.0 (1)
N4—C4—N5—C8	176.8 (1)	C4—N5—C8—C9	−100.8 (2)
C4—N5—C5—C6	−0.2 (2)	C5—N5—C8—C9	75.3 (2)
C8—N5—C5—C6	−176.9 (1)

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

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft, SPP 1191 (grant No. KO 1616/4-1 und 4-2).

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