Bis(N-adamantyl-N′-ethyl­imidazolium) tetra­bromido­manganate(II)

Giltzau, N.O.; Köckerling, M.

doi:10.1107/S2414314620002618

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 3| March 2020| x200261

https://doi.org/10.1107/S2414314620002618

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Bis(N-adamantyl-N′-ethylimidazolium) tetrabromidomanganate(II)

Niels Ole Giltzau ^a and Martin Köckerling ^a,^b ^*

^aUniversität Rostock, Institut für Chemie, Anorganische Festkörperchemie, Albert-Einstein-Str. 3a, D-18059 Rostock, Germany, and ^bDepartment Life, Light and Matter, Universität Rostock, 18051 Rostock, Germany
^*Correspondence e-mail: Martin.Koeckerling@uni-rostock.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 10 January 2020; accepted 25 February 2020; online 3 March 2020)

The title compound, (C₁₅H₂₃N₂)₂[MnBr₄], comprises two N-adamantyl-N′-ethylimidazolium cations and one tetrahedral [MnBr₄]²⁻ anion. Next to Coulombic interactions, weak hydrogen bonds of the type C—H⋯Br consolidate the crystal packing, building up a three-dimensional network.

Keywords: crystal structure; tetrabromidomanganate; imidazolium; adamantyl; N-adamantyl-N′-ethyl-imidazolium; manganese.

CCDC reference: 1986182

Structure description

Compounds comprising the tetrabromidomanganate(II) anion [MnBr₄]^2– are well known and may find applications as green-light-emitting diodes (Xu et al., 2017 ). The title compound is a further member of the so far small group of manganese complexes with imidazolium cations (Del Sesto et al., 2008 ; Peppel et al., 2019 ). To the best of our knowledge, no other structure of a complex salt has been published so far that contains the N-adamantyl-N′-ethyl-imidazolium cation. Nevertheless, several compounds with adamantyl-imidazolium units have been described to be useful in anion-exchange membranes (Wang et al., 2018 ). Compounds containing the adamantyl-substituted imidazolium cation, for which structures have been established, contain two adamantyl (Ad) units, e.g. [(Ad)₂Im]⁺ (Arduengo et al., 1991 ; Grasa et al., 2004 ).

The asymmetric unit of the title compound comprises two N-adamantyl-N′-ethyl-imidazolium cations and one tetrabromidomanganate(II) anion (Fig. 1). The latter has a slightly distorted tetrahedral geometry, with the shortest Mn—Br bond length being 2.4983 (6) Å (Mn1—Br4) and the longest 2.5194 (5) Å (Mn1—Br2). The Mn—Br bond lengths are in good agreement with reference values (Orpen et al., 1989 ). The Br—Mn—Br angles range from 105.88 (2)° for Br4—Mn1—Br2 to 113.61 (2)° for Br1—Mn1—Br2. The molecular entities of the cation, viz. the ethyl group, the imidazole ring and the adamantyl group, have normal distances and angles. In the crystal (Fig. 2), cations and complex anions are linked via an intricate network of weak C—H⋯Br hydrogen bonds into a three-dimensional network (Fig. 3, Table 1). Br1 is the acceptor of four contacts, Br2 of three, Br3 of one and Br4 of four.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br2	0.95	2.84	3.766 (3)	166
C2—H2⋯Br1ⁱ	0.95	2.92	3.864 (3)	170
C3—H3⋯Br4ⁱⁱ	0.95	2.99	3.785 (3)	143
C5—H5C⋯Br4ⁱⁱ	0.98	3.00	3.738 (3)	134
C13—H13A⋯Br2ⁱⁱⁱ	0.99	3.05	3.941 (3)	151
C16—H16⋯Br2	0.95	3.04	3.929 (3)	156
C16—H16⋯Br4	0.95	3.01	3.549 (3)	117
C17—H17⋯Br1^iv	0.95	2.82	3.719 (3)	159
C18—H18⋯Br3^v	0.95	2.82	3.718 (3)	158
C19—H19A⋯Br1^v	0.99	2.81	3.781 (3)	168
C22—H22A⋯Br4	0.99	2.93	3.898 (3)	166
C28—H28A⋯Br1^iv	0.99	3.00	3.939 (3)	160
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The asymmetric unit of (C₁₅H₂₃N₂)₂[MnBr₄] with atom labelling.

Figure 2
A view of the unit-cell contents in projection down the a axis.

Figure 3
Selected hydrogen bonds between the cations and anions in the crystal structure of (C₁₅H₂₃N₂)₂[MnBr₄]. Anisotropic displacement ellipsoids are shown at the 50% probability level. Symmetry operators refer to Table 1

Synthesis and crystallization

N-adamantyl-N′-ethyl-imidazolium bromide (0.19 g, 6 mmol) and MnBr₂·2H₂O (0.07 g, 3 mmol) were mixed in methanol (3 ml). The mixture was heated for 3 d at 453 K in a sand bath. After cooling to room temperature, a clear beige-coloured solution was obtained. The solvent was partly removed and large light-green crystals were grown through slow diffusion of diethyl ether or ethyl acetate into the solution. The yield was nearly quantitative. The compound was also accessible through stirring the starting mixture for several hours at ambient temperature. M.p. 501 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Nine reflections were omitted from the structure refinement because their intensities were affected by the beam stop. Details can be found in the refine_special_details field in the CIF.

Table 2
Experimental details

Crystal data
Chemical formula	(C₁₅H₂₃N₂)₂[MnBr₄]
M_r	837.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	18.020 (1), 18.742 (1), 19.740 (1)
V (Å³)	6666.6 (7)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	5.22
Crystal size (mm)	0.22 × 0.22 × 0.05

Data collection
Diffractometer	Bruker APEX KappaII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
No. of measured, independent and observed [I > 2σ(I)] reflections	182157, 5883, 5029
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 1.21
No. of reflections	5883
No. of parameters	354
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.50
Computer programs: APEX2 and SAINT (Bruker, 2017 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2019 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1986182

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620002618/wm4124sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620002618/wm4124Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2019); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(N-adamantyl-N'-ethylimidazolium) tetrabromidomanganate(II) top

Crystal data top

(C₁₅H₂₃N₂)₂[MnBr₄]	D_x = 1.668 Mg m⁻³
M_r = 837.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9879 reflections
a = 18.020 (1) Å	θ = 2.4–28.3°
b = 18.742 (1) Å	µ = 5.22 mm⁻¹
c = 19.740 (1) Å	T = 123 K
V = 6666.6 (7) Å³	Irregular block, green
Z = 8	0.22 × 0.22 × 0.05 mm
F(000) = 3352

Data collection top

Bruker APEX KappaII CCD diffractometer	5029 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.084
φ and ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −21→21
	k = −22→22
182157 measured reflections	l = −23→23
5883 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: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 1.21	w = 1/[σ²(F_o²) + (0.0237P)² + 8.9922P] where P = (F_o² + 2F_c²)/3
5883 reflections	(Δ/σ)_max = 0.001
354 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Mn1	0.40086 (3)	0.31017 (2)	0.38565 (2)	0.0165 (1)
Br1	0.49923 (2)	0.26519 (2)	0.30615 (2)	0.02108 (8)
Br2	0.45216 (2)	0.37029 (2)	0.48975 (2)	0.02183 (9)
Br3	0.32660 (2)	0.40185 (2)	0.32299 (2)	0.02521 (9)
Br4	0.32464 (2)	0.20800 (2)	0.42767 (2)	0.02693 (9)
N1	0.3626 (2)	0.5761 (1)	0.4061 (1)	0.0195 (6)
C1	0.4241 (2)	0.5403 (2)	0.3913 (2)	0.0175 (7)
H1	0.4393	0.4969	0.4120	0.021*
N2	0.4607 (1)	0.5746 (1)	0.3433 (1)	0.0169 (6)
C2	0.4208 (2)	0.6354 (2)	0.3273 (2)	0.0252 (8)
H2	0.4342	0.6703	0.2946	0.030*
C3	0.3598 (2)	0.6362 (2)	0.3664 (2)	0.0269 (8)
H3	0.3220	0.6715	0.3665	0.032*
C4	0.3072 (2)	0.5525 (2)	0.4560 (2)	0.0257 (8)
H4A	0.3149	0.5013	0.4658	0.031*
H4B	0.2570	0.5580	0.4363	0.031*
C5	0.3115 (2)	0.5940 (2)	0.5210 (2)	0.0256 (8)
H5A	0.3628	0.5942	0.5375	0.038*
H5B	0.2793	0.5718	0.5550	0.038*
H5C	0.2952	0.6432	0.5130	0.038*
C6	0.5299 (2)	0.5498 (2)	0.3095 (2)	0.0169 (7)
C7	0.5569 (2)	0.4811 (2)	0.3433 (2)	0.0187 (7)
H7A	0.5668	0.4900	0.3919	0.022*
H7B	0.5182	0.4438	0.3398	0.022*
C8	0.6278 (2)	0.4557 (2)	0.3085 (2)	0.0201 (7)
H8	0.6456	0.4109	0.3307	0.024*
C9	0.6113 (2)	0.4407 (2)	0.2337 (2)	0.0223 (7)
H9A	0.6569	0.4239	0.2106	0.027*
H9B	0.5731	0.4029	0.2299	0.027*
C10	0.5835 (2)	0.5092 (2)	0.2001 (2)	0.0242 (8)
H10	0.5728	0.4997	0.1512	0.029*
C11	0.6438 (2)	0.5669 (2)	0.2057 (2)	0.0284 (8)
H11A	0.6895	0.5507	0.1824	0.034*
H11B	0.6266	0.6113	0.1836	0.034*
C12	0.6606 (2)	0.5814 (2)	0.2805 (2)	0.0249 (8)
H12	0.6999	0.6189	0.2842	0.030*
C13	0.5895 (2)	0.6073 (2)	0.3154 (2)	0.0206 (7)
H13A	0.5996	0.6174	0.3637	0.025*
H13B	0.5720	0.6519	0.2937	0.025*
C14	0.5133 (2)	0.5353 (2)	0.2349 (2)	0.0224 (7)
H14A	0.4739	0.4988	0.2309	0.027*
H14B	0.4956	0.5796	0.2128	0.027*
C15	0.6877 (2)	0.5128 (2)	0.3142 (2)	0.0254 (8)
H15A	0.7337	0.4961	0.2918	0.030*
H15B	0.6989	0.5220	0.3625	0.030*
N3	0.3189 (1)	0.2326 (1)	0.6412 (1)	0.0188 (6)
C16	0.2941 (2)	0.2756 (2)	0.5933 (2)	0.0170 (7)
H16	0.3227	0.2938	0.5567	0.020*
N4	0.2229 (1)	0.2893 (1)	0.6046 (1)	0.0176 (6)
C17	0.2018 (2)	0.2531 (2)	0.6622 (2)	0.0241 (7)
H17	0.1538	0.2532	0.6821	0.029*
C18	0.2615 (2)	0.2178 (2)	0.6850 (2)	0.0244 (8)
H18	0.2638	0.1883	0.7240	0.029*
C19	0.3932 (2)	0.2006 (2)	0.6441 (2)	0.0238 (7)
H19A	0.4137	0.2065	0.6903	0.029*
H19B	0.4264	0.2259	0.6121	0.029*
C20	0.3911 (2)	0.1228 (2)	0.6265 (2)	0.0339 (9)
H20A	0.3746	0.1171	0.5795	0.051*
H20B	0.3565	0.0981	0.6568	0.051*
H20C	0.4409	0.1023	0.6317	0.051*
C21	0.1721 (2)	0.3319 (2)	0.5610 (2)	0.0151 (6)
C22	0.2154 (2)	0.3683 (2)	0.5044 (2)	0.0184 (7)
H22A	0.2416	0.3320	0.4769	0.022*
H22B	0.2528	0.4010	0.5240	0.022*
C23	0.1614 (2)	0.4104 (2)	0.4596 (2)	0.0200 (7)
H23	0.1895	0.4342	0.4223	0.024*
C24	0.1223 (2)	0.4669 (2)	0.5024 (2)	0.0234 (7)
H24A	0.1594	0.5001	0.5218	0.028*
H24B	0.0878	0.4948	0.4737	0.028*
C25	0.0792 (2)	0.4307 (2)	0.5594 (2)	0.0223 (7)
H25	0.0535	0.4678	0.5873	0.027*
C26	0.0218 (2)	0.3798 (2)	0.5297 (2)	0.0263 (8)
H26A	−0.0139	0.4068	0.5015	0.032*
H26B	−0.0061	0.3563	0.5667	0.032*
C27	0.0606 (2)	0.3233 (2)	0.4863 (2)	0.0250 (7)
H27	0.0228	0.2903	0.4666	0.030*
C28	0.1149 (2)	0.2810 (2)	0.5303 (2)	0.0198 (7)
H28A	0.0876	0.2562	0.5669	0.024*
H28B	0.1404	0.2445	0.5024	0.024*
C29	0.1040 (2)	0.3593 (2)	0.4292 (2)	0.0245 (8)
H29A	0.0695	0.3861	0.3995	0.029*
H29B	0.1293	0.3227	0.4014	0.029*
C30	0.1326 (2)	0.3882 (2)	0.6044 (2)	0.0198 (7)
H30A	0.1047	0.3646	0.6414	0.024*
H30B	0.1696	0.4207	0.6250	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0176 (3)	0.0162 (2)	0.0156 (2)	−0.0006 (2)	0.0003 (2)	−0.0033 (2)
Br1	0.0200 (2)	0.0267 (2)	0.0165 (2)	0.0050 (1)	0.0003 (1)	−0.0028 (1)
Br2	0.0295 (2)	0.0212 (2)	0.0148 (2)	−0.0047 (1)	−0.0028 (1)	−0.0020 (1)
Br3	0.0272 (2)	0.0236 (2)	0.0249 (2)	0.0070 (1)	−0.0093 (1)	−0.0060 (1)
Br4	0.0278 (2)	0.0201 (2)	0.0330 (2)	−0.0077 (1)	0.0104 (2)	−0.0088 (1)
N1	0.020 (2)	0.017 (1)	0.022 (1)	−0.003 (1)	0.004 (1)	−0.002 (1)
C1	0.022 (2)	0.013 (2)	0.018 (2)	0.000 (1)	0.000 (1)	−0.001 (1)
N2	0.021 (1)	0.014 (1)	0.016 (1)	0.000 (1)	0.002 (1)	0.000 (1)
C2	0.030 (2)	0.019 (2)	0.026 (2)	0.005 (1)	0.005 (2)	0.006 (1)
C3	0.029 (2)	0.021 (2)	0.031 (2)	0.008 (2)	0.005 (2)	0.003 (2)
C4	0.025 (2)	0.021 (2)	0.032 (2)	−0.003 (1)	0.010 (2)	0.001 (1)
C5	0.022 (2)	0.032 (2)	0.022 (2)	−0.001 (2)	0.002 (1)	0.007 (2)
C6	0.021 (2)	0.015 (2)	0.015 (2)	0.001 (1)	0.002 (1)	0.000 (1)
C7	0.025 (2)	0.016 (2)	0.015 (2)	0.001 (1)	0.000 (1)	0.002 (1)
C8	0.022 (2)	0.019 (2)	0.020 (2)	0.003 (1)	0.001 (1)	0.000 (1)
C9	0.026 (2)	0.021 (2)	0.020 (2)	0.002 (1)	0.004 (1)	−0.006 (1)
C10	0.033 (2)	0.026 (2)	0.013 (2)	0.005 (2)	0.001 (1)	−0.001 (1)
C11	0.035 (2)	0.027 (2)	0.024 (2)	0.004 (2)	0.012 (2)	0.006 (2)
C12	0.024 (2)	0.022 (2)	0.028 (2)	−0.005 (1)	0.008 (2)	−0.001 (1)
C13	0.026 (2)	0.015 (2)	0.021 (2)	−0.006 (1)	0.002 (1)	−0.001 (1)
C14	0.029 (2)	0.023 (2)	0.015 (2)	0.004 (1)	−0.003 (1)	−0.001 (1)
C15	0.021 (2)	0.032 (2)	0.023 (2)	0.001 (2)	0.001 (1)	−0.001 (1)
N3	0.018 (1)	0.020 (1)	0.019 (1)	0.004 (1)	−0.002 (1)	0.001 (1)
C16	0.017 (2)	0.018 (2)	0.016 (2)	−0.001 (1)	−0.001 (1)	−0.002 (1)
N4	0.016 (1)	0.020 (1)	0.017 (1)	0.001 (1)	0.001 (1)	0.001 (1)
C17	0.020 (2)	0.030 (2)	0.023 (2)	0.002 (2)	0.003 (1)	0.012 (1)
C18	0.027 (2)	0.027 (2)	0.019 (2)	0.002 (2)	0.002 (2)	0.007 (1)
C19	0.020 (2)	0.027 (2)	0.025 (2)	0.006 (1)	−0.007 (1)	−0.003 (1)
C20	0.032 (2)	0.028 (2)	0.043 (2)	0.010 (2)	0.003 (2)	−0.004 (2)
C21	0.013 (2)	0.017 (2)	0.015 (2)	0.003 (1)	−0.001 (1)	0.002 (1)
C22	0.017 (2)	0.020 (2)	0.018 (2)	0.003 (1)	0.005 (1)	0.002 (1)
C23	0.025 (2)	0.018 (2)	0.017 (2)	0.002 (1)	0.004 (1)	0.006 (1)
C24	0.027 (2)	0.016 (2)	0.027 (2)	0.004 (1)	0.003 (2)	0.004 (1)
C25	0.023 (2)	0.020 (2)	0.024 (2)	0.008 (1)	0.007 (1)	0.002 (1)
C26	0.020 (2)	0.031 (2)	0.029 (2)	0.006 (2)	−0.001 (2)	0.011 (2)
C27	0.024 (2)	0.025 (2)	0.027 (2)	−0.004 (2)	−0.009 (2)	0.004 (1)
C28	0.023 (2)	0.016 (2)	0.021 (2)	−0.001 (1)	−0.001 (1)	0.003 (1)
C29	0.034 (2)	0.023 (2)	0.018 (2)	0.004 (2)	−0.004 (2)	0.002 (1)
C30	0.022 (2)	0.020 (2)	0.017 (2)	0.002 (1)	0.005 (1)	0.000 (1)

Geometric parameters (Å, º) top

Mn1—Br4	2.4983 (6)	C15—H15A	0.9900
Mn1—Br3	2.5046 (6)	C15—H15B	0.9900
Mn1—Br1	2.5130 (6)	N3—C16	1.321 (4)
Mn1—Br2	2.5194 (5)	N3—C18	1.375 (4)
N1—C1	1.327 (4)	N3—C19	1.468 (4)
N1—C3	1.373 (4)	C16—N4	1.327 (4)
N1—C4	1.470 (4)	C16—H16	0.9500
C1—N2	1.322 (4)	N4—C17	1.379 (4)
C1—H1	0.9500	N4—C21	1.488 (4)
N2—C2	1.384 (4)	C17—C18	1.340 (5)
N2—C6	1.488 (4)	C17—H17	0.9500
C2—C3	1.343 (5)	C18—H18	0.9500
C2—H2	0.9500	C19—C20	1.501 (5)
C3—H3	0.9500	C19—H19A	0.9900
C4—C5	1.503 (5)	C19—H19B	0.9900
C4—H4A	0.9900	C20—H20A	0.9800
C4—H4B	0.9900	C20—H20B	0.9800
C5—H5A	0.9800	C20—H20C	0.9800
C5—H5B	0.9800	C21—C22	1.524 (4)
C5—H5C	0.9800	C21—C28	1.529 (4)
C6—C13	1.526 (4)	C21—C30	1.534 (4)
C6—C14	1.527 (4)	C22—C23	1.533 (4)
C6—C7	1.531 (4)	C22—H22A	0.9900
C7—C8	1.527 (4)	C22—H22B	0.9900
C7—H7A	0.9900	C23—C24	1.527 (4)
C7—H7B	0.9900	C23—C29	1.531 (5)
C8—C15	1.522 (5)	C23—H23	1.0000
C8—C9	1.532 (4)	C24—C25	1.526 (4)
C8—H8	1.0000	C24—H24A	0.9900
C9—C10	1.530 (4)	C24—H24B	0.9900
C9—H9A	0.9900	C25—C26	1.525 (5)
C9—H9B	0.9900	C25—C30	1.533 (4)
C10—C14	1.520 (5)	C25—H25	1.0000
C10—C11	1.537 (5)	C26—C27	1.530 (5)
C10—H10	1.0000	C26—H26A	0.9900
C11—C12	1.531 (5)	C26—H26B	0.9900
C11—H11A	0.9900	C27—C29	1.529 (5)
C11—H11B	0.9900	C27—C28	1.532 (4)
C12—C15	1.527 (5)	C27—H27	1.0000
C12—C13	1.534 (5)	C28—H28A	0.9900
C12—H12	1.0000	C28—H28B	0.9900
C13—H13A	0.9900	C29—H29A	0.9900
C13—H13B	0.9900	C29—H29B	0.9900
C14—H14A	0.9900	C30—H30A	0.9900
C14—H14B	0.9900	C30—H30B	0.9900

Br4—Mn1—Br3	113.33 (2)	C8—C15—H15B	109.8
Br4—Mn1—Br1	109.76 (2)	C12—C15—H15B	109.8
Br3—Mn1—Br1	107.37 (2)	H15A—C15—H15B	108.2
Br4—Mn1—Br2	105.88 (2)	C16—N3—C18	108.6 (3)
Br3—Mn1—Br2	106.98 (2)	C16—N3—C19	125.8 (3)
Br1—Mn1—Br2	113.61 (2)	C18—N3—C19	125.4 (3)
C1—N1—C3	108.6 (3)	N3—C16—N4	108.9 (3)
C1—N1—C4	124.2 (3)	N3—C16—H16	125.5
C3—N1—C4	127.2 (3)	N4—C16—H16	125.5
N2—C1—N1	109.2 (3)	C16—N4—C17	108.1 (3)
N2—C1—H1	125.4	C16—N4—C21	127.0 (3)
N1—C1—H1	125.4	C17—N4—C21	124.8 (3)
C1—N2—C2	107.8 (3)	C18—C17—N4	107.4 (3)
C1—N2—C6	126.0 (3)	C18—C17—H17	126.3
C2—N2—C6	126.1 (3)	N4—C17—H17	126.3
C3—C2—N2	107.6 (3)	C17—C18—N3	107.0 (3)
C3—C2—H2	126.2	C17—C18—H18	126.5
N2—C2—H2	126.2	N3—C18—H18	126.5
C2—C3—N1	106.8 (3)	N3—C19—C20	111.4 (3)
C2—C3—H3	126.6	N3—C19—H19A	109.4
N1—C3—H3	126.6	C20—C19—H19A	109.4
N1—C4—C5	112.4 (3)	N3—C19—H19B	109.4
N1—C4—H4A	109.1	C20—C19—H19B	109.4
C5—C4—H4A	109.1	H19A—C19—H19B	108.0
N1—C4—H4B	109.1	C19—C20—H20A	109.5
C5—C4—H4B	109.1	C19—C20—H20B	109.5
H4A—C4—H4B	107.9	H20A—C20—H20B	109.5
C4—C5—H5A	109.5	C19—C20—H20C	109.5
C4—C5—H5B	109.5	H20A—C20—H20C	109.5
H5A—C5—H5B	109.5	H20B—C20—H20C	109.5
C4—C5—H5C	109.5	N4—C21—C22	110.4 (2)
H5A—C5—H5C	109.5	N4—C21—C28	108.0 (2)
H5B—C5—H5C	109.5	C22—C21—C28	109.5 (2)
N2—C6—C13	109.5 (2)	N4—C21—C30	109.3 (2)
N2—C6—C14	109.0 (3)	C22—C21—C30	109.8 (2)
C13—C6—C14	109.7 (3)	C28—C21—C30	109.8 (3)
N2—C6—C7	109.5 (2)	C21—C22—C23	109.1 (3)
C13—C6—C7	109.7 (3)	C21—C22—H22A	109.9
C14—C6—C7	109.5 (2)	C23—C22—H22A	109.9
C8—C7—C6	109.3 (2)	C21—C22—H22B	109.9
C8—C7—H7A	109.8	C23—C22—H22B	109.9
C6—C7—H7A	109.8	H22A—C22—H22B	108.3
C8—C7—H7B	109.8	C24—C23—C29	109.8 (3)
C6—C7—H7B	109.8	C24—C23—C22	109.3 (3)
H7A—C7—H7B	108.3	C29—C23—C22	109.5 (3)
C15—C8—C7	109.9 (3)	C24—C23—H23	109.4
C15—C8—C9	109.8 (3)	C29—C23—H23	109.4
C7—C8—C9	109.2 (3)	C22—C23—H23	109.4
C15—C8—H8	109.3	C25—C24—C23	109.5 (3)
C7—C8—H8	109.3	C25—C24—H24A	109.8
C9—C8—H8	109.3	C23—C24—H24A	109.8
C10—C9—C8	109.1 (3)	C25—C24—H24B	109.8
C10—C9—H9A	109.9	C23—C24—H24B	109.8
C8—C9—H9A	109.9	H24A—C24—H24B	108.2
C10—C9—H9B	109.9	C26—C25—C24	109.8 (3)
C8—C9—H9B	109.9	C26—C25—C30	108.9 (3)
H9A—C9—H9B	108.3	C24—C25—C30	109.8 (3)
C14—C10—C9	110.3 (3)	C26—C25—H25	109.4
C14—C10—C11	109.2 (3)	C24—C25—H25	109.4
C9—C10—C11	109.1 (3)	C30—C25—H25	109.4
C14—C10—H10	109.4	C25—C26—C27	109.8 (3)
C9—C10—H10	109.4	C25—C26—H26A	109.7
C11—C10—H10	109.4	C27—C26—H26A	109.7
C12—C11—C10	109.6 (3)	C25—C26—H26B	109.7
C12—C11—H11A	109.8	C27—C26—H26B	109.7
C10—C11—H11A	109.8	H26A—C26—H26B	108.2
C12—C11—H11B	109.8	C29—C27—C26	109.9 (3)
C10—C11—H11B	109.8	C29—C27—C28	108.7 (3)
H11A—C11—H11B	108.2	C26—C27—C28	109.5 (3)
C15—C12—C11	109.5 (3)	C29—C27—H27	109.6
C15—C12—C13	109.7 (3)	C26—C27—H27	109.6
C11—C12—C13	108.9 (3)	C28—C27—H27	109.6
C15—C12—H12	109.6	C21—C28—C27	109.4 (2)
C11—C12—H12	109.6	C21—C28—H28A	109.8
C13—C12—H12	109.6	C27—C28—H28A	109.8
C6—C13—C12	109.3 (3)	C21—C28—H28B	109.8
C6—C13—H13A	109.8	C27—C28—H28B	109.8
C12—C13—H13A	109.8	H28A—C28—H28B	108.2
C6—C13—H13B	109.8	C27—C29—C23	109.4 (3)
C12—C13—H13B	109.8	C27—C29—H29A	109.8
H13A—C13—H13B	108.3	C23—C29—H29A	109.8
C10—C14—C6	109.3 (3)	C27—C29—H29B	109.8
C10—C14—H14A	109.8	C23—C29—H29B	109.8
C6—C14—H14A	109.8	H29A—C29—H29B	108.2
C10—C14—H14B	109.8	C25—C30—C21	108.9 (2)
C6—C14—H14B	109.8	C25—C30—H30A	109.9
H14A—C14—H14B	108.3	C21—C30—H30A	109.9
C8—C15—C12	109.5 (3)	C25—C30—H30B	109.9
C8—C15—H15A	109.8	C21—C30—H30B	109.9
C12—C15—H15A	109.8	H30A—C30—H30B	108.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br2	0.95	2.84	3.766 (3)	166
C2—H2···Br1ⁱ	0.95	2.92	3.864 (3)	170
C3—H3···Br4ⁱⁱ	0.95	2.99	3.785 (3)	143
C5—H5C···Br4ⁱⁱ	0.98	3.00	3.738 (3)	134
C13—H13A···Br2ⁱⁱⁱ	0.99	3.05	3.941 (3)	151
C16—H16···Br2	0.95	3.04	3.929 (3)	156
C16—H16···Br4	0.95	3.01	3.549 (3)	117
C17—H17···Br1^iv	0.95	2.82	3.719 (3)	159
C18—H18···Br3^v	0.95	2.82	3.718 (3)	158
C19—H19A···Br1^v	0.99	2.81	3.781 (3)	168
C22—H22A···Br4	0.99	2.93	3.898 (3)	166
C28—H28A···Br1^iv	0.99	3.00	3.939 (3)	160

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

Acknowledgements

We gratefully acknowledge the maintenance of the XRD equipment through Dr Alexander Villinger (University of Rostock).

Funding information

Funding for this research was provided by: DFG-SPP 1708, Material Synthesis Near Room Temperature.

References

Arduengo, A. J. III, Harlow, R. L. & Kline, M. (1991). J. Am. Chem. Soc. 113, 361–363. CSD CrossRef CAS Web of Science Google Scholar
Brandenburg, K. & Putz, H. (2019). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2017). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Del Sesto, R. E., McCleskey, T. M., Burrell, A. K., Baker, G. A., Thompson, J. D., Scott, B. L., Wilkes, J. S. & Williams, P. (2008). Chem. Commun. pp. 447–449. Web of Science CSD CrossRef Google Scholar
Grasa, G. A., Singh, R., Scott, N. M., Stevens, E. D. & Nolan, S. P. (2004). Chem. Commun. pp. 2890–2891. Web of Science CSD CrossRef Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1–S83. CrossRef Web of Science Google Scholar
Peppel, T., Geppert-Rybczyńska, M., Neise, C., Kragl, U. & Köckerling, M. (2019). Materials, 12, 3764–3779. Web of Science CrossRef 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
Wang, J., Wang, X., Zu, D., Hua, Y., Li, Y., Yang, S., Wei, H. & Ding, Y. (2018). J. Membr. Sci. 545, 116–125. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, L.-J., Sun, C.-Z., Xiao, H., Wu, Y. & Chen, Z.-N. (2017). Adv. Mater. 29, 1605739. Web of Science CSD CrossRef Google Scholar