Bis(quinolinium) tetra­bromido­manganate(II)

Papa, V.; Spannenberg, A.; Beller, M.; Junge, K.

doi:10.1107/S2414314619012318

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191231

https://doi.org/10.1107/S2414314619012318

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Bis(quinolinium) tetrabromidomanganate(II)

Veronica Papa,^a Anke Spannenberg,^a Matthias Beller ^a and Kathrin Junge ^a ^*

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: kathrin.junge@catalysis.de

Edited by J. Simpson, University of Otago, New Zealand (Received 26 August 2019; accepted 4 September 2019; online 10 September 2019)

The title compound, (C₉H₈N)₂[MnBr₄], consists of two quinolinium cations and a [MnBr₄]²⁻ anion. The manganese(II) atom, which lies on a twofold rotation axis, is coordinated by four bromide ligands and exhibits a tetrahedral coordination geometry. The [MnBr₄]²⁻ anion and the quinolinium cations are linked by N—H⋯Br hydrogen bonds. π–π stacking interactions are observed between the quinolinium cations.

Keywords: crystal structure; quinolinium cation; manganese; hydrogen bond.

CCDC reference: 1951407

Structure description

The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit consists of one quinolinium cation and a half [MnBr₄]²⁻ anion with the Mn^II atom lying on a twofold rotation axis. The Mn^II atom exhibits a slightly distorted tetrahedral coordination geometry. The crystal structures of similar compounds with the general formula (QuinH)₂[MX₄] (without co-crystallized H₂O; Quin = quinoline; M = Cu, X = Br (Butcher et al., 2010 ); M = Cu, X = Cl (Lamotte-Brasseur & Vermeire, 1973 ); M = Cd, X = Cl (Paulus & Göttlicher, 1969 ) have been reported. Several crystal structures of compounds with the general formula (QuinH)₂[MX₄]·2H₂O have also been described by Landee et al. (2018 ) (M = Co, Mn, X = Cl; M = Co, Zn, X = Br), Butcher et al. (2010) (M = Cu, X = Br), Ye et al. (2014 ) (M = Co, X = Cl), Lynch & McClenaghan (2002 ) (M = Cu, X = Cl), Slabbert & Rademeyer (2016 ) (M = Hg, X = Cl; M = Cd, X = Br) and Valdés-Martínez et al. (2005 ) (M = Zn, X = Cl).

Figure 1
The molecular entities of the title compound with atom labelling and displacement ellipsoids drawn at the 30% probability level.

In the crystal structure of the title compound, the anion is linked to the cations by N—H⋯Br hydrogen bonds (Table 1, Fig. 2). Additionally, π–π stacking occurs between two quinolinium cations [Cg1⋯Cg1 = 3.799 (1) Å with ring slippage of 1.7 Å and Cg1⋯Cg2 = 3.6368 (10) Å with ring slippage of 1.3 Å, where Cg1 is the centroid of the N1/C1–C4/C9 ring and Cg2 is the centroid of the C4–C9 benzene ring].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.88 (3)	2.69 (3)	3.3815 (14)	137 (2)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
ORTEP representation of the title compound showing the intermolecular hydrogen bonds as dotted lines. Displacement ellipsoids correspond to 30% probability.

Synthesis and crystallization

A mixture containing MnBr₂·4H₂O (1 mmol) and quinoline (2 mmol) in dry toluene (20 mL) was stirred overnight at 60°C. The solvent was removed under vacuum giving a white solid that was then dissolved in dry EtOH (10 mL) and reacted with 1 eq of HBr (48 wt% in H₂O) overnight. The solvent was removed under vacuum giving a white solid (yield: 73%). Colourless crystals suitable for X-ray diffraction analysis were grown from a solution of EtOH layered with Et₂O.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	(C₉H₈N)₂[MnBr₄]
M_r	634.91
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	17.4314 (6), 9.1871 (3), 13.2270 (4)
β (°)	93.7501 (12)
V (Å³)	2113.69 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	8.19
Crystal size (mm)	0.44 × 0.42 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.12, 0.34
No. of measured, independent and observed [I > 2σ(I)] reflections	17446, 2545, 2373
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.041, 1.05
No. of reflections	2545
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.45
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), XP in SHELXTL and SHELXS97 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1951407

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012318/sj4208sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619012318/sj4208Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(quinolinium) tetrabromidomanganate(II) top

Crystal data top

(C₉H₈N)₂[MnBr₄]	F(000) = 1212
M_r = 634.91	D_x = 1.995 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.4314 (6) Å	Cell parameters from 9902 reflections
b = 9.1871 (3) Å	θ = 2.5–30.5°
c = 13.2270 (4) Å	µ = 8.19 mm⁻¹
β = 93.7501 (12)°	T = 150 K
V = 2113.69 (12) Å³	Prism, colourless
Z = 4	0.44 × 0.42 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	2545 independent reflections
Radiation source: fine-focus sealed tube	2373 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.027
φ and ω scans	θ_max = 28.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −22→22
T_min = 0.12, T_max = 0.34	k = −10→12
17446 measured reflections	l = −17→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0192P)² + 1.7599P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
2545 reflections	Δρ_max = 0.28 e Å⁻³
118 parameters	Δρ_min = −0.45 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
Br1	0.59434 (2)	0.56020 (2)	0.16817 (2)	0.02499 (5)
Br2	0.55967 (2)	0.23982 (2)	0.38636 (2)	0.02340 (5)
C1	0.90430 (11)	0.7807 (2)	0.56459 (13)	0.0302 (4)
H1B	0.9547	0.7726	0.5418	0.036*
C2	0.87027 (11)	0.66136 (19)	0.60845 (13)	0.0308 (4)
H2	0.8972	0.5717	0.6161	0.037*
C3	0.79790 (11)	0.67462 (18)	0.64031 (12)	0.0282 (4)
H3	0.7741	0.5931	0.6694	0.034*
C4	0.75792 (9)	0.80749 (17)	0.63065 (11)	0.0212 (3)
C5	0.68293 (10)	0.8285 (2)	0.66219 (13)	0.0307 (4)
H5	0.6572	0.7507	0.6930	0.037*
C6	0.64737 (11)	0.9590 (2)	0.64878 (15)	0.0365 (4)
H6	0.5969	0.9718	0.6703	0.044*
C7	0.68442 (11)	1.0755 (2)	0.60344 (15)	0.0337 (4)
H7	0.6585	1.1660	0.5944	0.040*
C8	0.75718 (11)	1.06050 (18)	0.57222 (13)	0.0276 (4)
H8	0.7821	1.1398	0.5420	0.033*
C9	0.79424 (9)	0.92592 (16)	0.58566 (11)	0.0195 (3)
Mn1	0.5000	0.39954 (3)	0.2500	0.01891 (7)
N1	0.86666 (8)	0.90510 (16)	0.55456 (10)	0.0248 (3)
H1A	0.8907 (15)	0.975 (3)	0.524 (2)	0.059 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03363 (10)	0.02137 (8)	0.02065 (8)	−0.00760 (6)	0.00703 (6)	−0.00080 (6)
Br2	0.02595 (9)	0.02263 (8)	0.02159 (8)	0.00227 (6)	0.00134 (6)	0.00346 (6)
C1	0.0259 (9)	0.0378 (9)	0.0268 (8)	0.0056 (7)	0.0025 (7)	−0.0062 (7)
C2	0.0416 (10)	0.0227 (8)	0.0268 (8)	0.0084 (7)	−0.0068 (7)	−0.0050 (7)
C3	0.0438 (11)	0.0196 (8)	0.0205 (7)	−0.0060 (7)	−0.0042 (7)	0.0020 (6)
C4	0.0273 (8)	0.0217 (7)	0.0145 (6)	−0.0064 (6)	0.0004 (6)	−0.0019 (6)
C5	0.0288 (9)	0.0384 (10)	0.0257 (8)	−0.0119 (8)	0.0064 (7)	−0.0053 (7)
C6	0.0241 (9)	0.0514 (12)	0.0343 (10)	−0.0012 (8)	0.0034 (8)	−0.0167 (9)
C7	0.0321 (10)	0.0309 (9)	0.0367 (10)	0.0091 (7)	−0.0083 (8)	−0.0116 (8)
C8	0.0323 (9)	0.0203 (8)	0.0294 (8)	−0.0009 (6)	−0.0048 (7)	0.0005 (6)
C9	0.0222 (8)	0.0193 (7)	0.0168 (7)	−0.0028 (6)	−0.0003 (6)	−0.0011 (5)
Mn1	0.02264 (17)	0.01714 (15)	0.01725 (15)	0.000	0.00363 (12)	0.000
N1	0.0253 (7)	0.0276 (7)	0.0219 (7)	−0.0039 (6)	0.0043 (6)	0.0036 (6)

Geometric parameters (Å, º) top

Br1—Mn1	2.5073 (2)	C5—H5	0.9500
Br2—Mn1	2.4986 (2)	C6—C7	1.404 (3)
C1—N1	1.320 (2)	C6—H6	0.9500
C1—C2	1.391 (3)	C7—C8	1.366 (3)
C1—H1B	0.9500	C7—H7	0.9500
C2—C3	1.361 (3)	C8—C9	1.401 (2)
C2—H2	0.9500	C8—H8	0.9500
C3—C4	1.407 (2)	C9—N1	1.366 (2)
C3—H3	0.9500	Mn1—Br2ⁱ	2.4986 (2)
C4—C9	1.410 (2)	Mn1—Br1ⁱ	2.5073 (2)
C4—C5	1.411 (2)	N1—H1A	0.88 (3)
C5—C6	1.356 (3)

N1—C1—C2	120.10 (17)	C8—C7—C6	120.94 (17)
N1—C1—H1B	119.9	C8—C7—H7	119.5
C2—C1—H1B	119.9	C6—C7—H7	119.5
C3—C2—C1	119.18 (16)	C7—C8—C9	118.70 (16)
C3—C2—H2	120.4	C7—C8—H8	120.6
C1—C2—H2	120.4	C9—C8—H8	120.6
C2—C3—C4	120.86 (16)	N1—C9—C8	120.85 (15)
C2—C3—H3	119.6	N1—C9—C4	117.91 (14)
C4—C3—H3	119.6	C8—C9—C4	121.23 (15)
C3—C4—C9	118.32 (15)	Br2—Mn1—Br2ⁱ	108.068 (14)
C3—C4—C5	123.69 (16)	Br2—Mn1—Br1	113.799 (6)
C9—C4—C5	117.98 (15)	Br2ⁱ—Mn1—Br1	106.734 (5)
C6—C5—C4	120.45 (17)	Br2—Mn1—Br1ⁱ	106.733 (5)
C6—C5—H5	119.8	Br2ⁱ—Mn1—Br1ⁱ	113.798 (6)
C4—C5—H5	119.8	Br1—Mn1—Br1ⁱ	107.877 (14)
C5—C6—C7	120.70 (17)	C1—N1—C9	123.62 (15)
C5—C6—H6	119.7	C1—N1—H1A	115.4 (18)
C7—C6—H6	119.7	C9—N1—H1A	121.0 (17)

N1—C1—C2—C3	0.2 (3)	C7—C8—C9—N1	179.22 (16)
C1—C2—C3—C4	−0.9 (2)	C7—C8—C9—C4	−0.2 (2)
C2—C3—C4—C9	1.0 (2)	C3—C4—C9—N1	−0.5 (2)
C2—C3—C4—C5	−179.94 (16)	C5—C4—C9—N1	−179.59 (14)
C3—C4—C5—C6	−178.77 (17)	C3—C4—C9—C8	178.94 (15)
C9—C4—C5—C6	0.3 (2)	C5—C4—C9—C8	−0.2 (2)
C4—C5—C6—C7	−0.1 (3)	C2—C1—N1—C9	0.3 (3)
C5—C6—C7—C8	−0.3 (3)	C8—C9—N1—C1	−179.57 (16)
C6—C7—C8—C9	0.4 (3)	C4—C9—N1—C1	−0.2 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱⁱ	0.88 (3)	2.69 (3)	3.3815 (14)	137 (2)

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

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