Bis(dimethyl­ammonium) tetra­bromidomanganate(II)

The title compound, (C₂H₁₀N)₂[MnBr₄], consists of discrete dimethyl­ammonium cations and tetrabromidomanganate(II) anions which are held together in the crystal structure by N—H...Br hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](r-Mn) = 0.001 Å
• R factor = 0.050
• wR factor = 0.113
• Data-to-parameter ratio = 26.7

checkCIF/PLATON results

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PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
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S1. Comment

Recently we have found that the manganese complex [Mn(CO)₅Br] can easily transformed into Mn(II) and [Mn(CO)₅]₂ in the presence of strong nucleophiles such as NaSSitBu₃ or Na₂PSitBu₃ (Kückmann, 2007; Lerner et al., 2005). In attempting to synthesize the 1,4-phenylene-brigded Mn(I) scorpionate (I) from the corresponding lithium scorpionate and [Mn(CO)₅Br] in the presence of [NMe₂H₂][Br], we obtained [NMe₂H₂]₂[MnBr₄] as a side-product. X-ray quality crystals of [NMe₂H₂]₂[MnBr₄] were grown by diffusion of hexane into a solution of [NMe₂H₂]₂[MnBr₄] in tetrahydrofuran at ambient temperature.

The title compound, 2(C₂H₁₀N)⁺.MnBr₄^2-, consists of discrete dimethylammonium cations und tetrabromo-manganese anions which are held together in the crystal by N—H···Br hydrogen bonds. The title compound is isostructural with 2(C₂H₁₀N)^+.HgBr₄^2- (Pabst et al., 1990) 2(C₂H₁₀N)^+.CdBr₄^2- (Daoud, 1976; Waskowska, 1994), 2(C₂H₁₀N)^+.HgCl₄^2- (Salah et al., 1982) and 2(C₂H₁₀N)^+.CoCl₄^2- (Williams et al., 1992).

Related literature

For related literature, see: Daoud (1976); Kückmann (2007); Lerner et al. (2005); Pabst et al. (1990); Waskowska (1994); Williams et al. (1992); Salah et al. (1982).

S2. Experimental

By the reaction of the 1,4-phenylene-brigded Li scorpionate (I) (0.59 g, 1.10 mmol) with [Mn(CO)₅Br] (0.64 g, 2.31 mmol) and [NMe₂H₂][Br] (ca 0.2 mmol) in 30 ml THF [NMe₂H₂]₂[MnBr₄] was obtained as a side-product. X-ray quality crystals of [NMe₂H₂]₂[MnBr₄] were grown by diffusion of hexane into a solution of [NMe₂H₂]₂[MnBr₄] in tetrahydrofuran at ambient temperature.

S3. Refinement

H atoms were refined with fixed individual displacement parameters [U_iso(H) = 1.2 U_eq(C, N)] using a riding model with N—H = 0.92Å or C—H = 0.98 Å.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Perspective view of the title compound, with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii.

Bis(dimethylammonium) tetrabromidoomanganese(II)

Crystal data

(C2H8N)2[MnBr4]	F(000) = 876
Mr = 466.77	Dx = 2.137 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10816 reflections
a = 8.1854 (7) Å	θ = 3.5–25.4°
b = 11.7492 (9) Å	µ = 11.89 mm^−1
c = 15.1444 (11) Å	T = 173 K
β = 95.087 (6)°	Block, yellow
V = 1450.7 (2) Å^3	0.22 × 0.21 × 0.18 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer	2693 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
ω scans	θmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −9→9
Tmin = 0.090, Tmax = 0.114	k = −14→14
12230 measured reflections	l = −18→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0617P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2693 reflections	Δρmax = 1.57 e Å^−3
101 parameters	Δρmin = −0.85 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0058 (5)

Special details

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.28760 (13)	0.70597 (8)	0.54751 (8)	0.0256 (3)
Br1	0.53567 (9)	0.78194 (6)	0.63851 (6)	0.0345 (2)
Br2	0.28514 (9)	0.49320 (6)	0.55910 (6)	0.0334 (2)
Br3	0.03107 (10)	0.79225 (7)	0.59464 (6)	0.0391 (2)
Br4	0.32489 (10)	0.76510 (6)	0.38986 (5)	0.0325 (2)
N1	0.6983 (9)	0.5194 (5)	0.6703 (5)	0.0348 (15)
H1A	0.6640	0.4705	0.6250	0.042*
H1B	0.6635	0.5913	0.6536	0.042*
C1	0.6192 (11)	0.4864 (7)	0.7498 (6)	0.0393 (19)
H1C	0.4998	0.4886	0.7369	0.059*
H1D	0.6518	0.5395	0.7981	0.059*
H1E	0.6533	0.4091	0.7675	0.059*
C2	0.8784 (10)	0.5188 (8)	0.6814 (7)	0.046 (2)
H2C	0.9215	0.5413	0.6257	0.068*
H2D	0.9173	0.4421	0.6978	0.068*
H2E	0.9168	0.5725	0.7283	0.068*
N2	0.2655 (9)	0.1858 (5)	0.5713 (5)	0.0383 (16)
H2A	0.3660	0.2205	0.5698	0.046*
H2B	0.1967	0.2153	0.5257	0.046*
C3	0.2002 (14)	0.2138 (8)	0.6547 (8)	0.055 (3)
H3A	0.1902	0.2966	0.6599	0.082*
H3B	0.2744	0.1849	0.7040	0.082*
H3C	0.0919	0.1787	0.6566	0.082*
C4	0.2855 (13)	0.0612 (8)	0.5559 (9)	0.061 (3)
H4A	0.3293	0.0493	0.4984	0.092*
H4B	0.1787	0.0235	0.5560	0.092*
H4C	0.3615	0.0292	0.6030	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0270 (6)	0.0230 (5)	0.0264 (6)	0.0006 (4)	−0.0006 (4)	0.0000 (4)
Br1	0.0352 (4)	0.0282 (4)	0.0379 (5)	−0.0011 (3)	−0.0093 (3)	−0.0036 (3)
Br2	0.0396 (4)	0.0233 (3)	0.0368 (4)	−0.0012 (3)	0.0013 (3)	0.0034 (3)
Br3	0.0315 (4)	0.0391 (4)	0.0475 (5)	0.0064 (3)	0.0072 (3)	−0.0062 (4)
Br4	0.0392 (4)	0.0292 (4)	0.0283 (4)	−0.0015 (3)	−0.0014 (3)	0.0054 (3)
N1	0.051 (4)	0.026 (3)	0.028 (4)	0.006 (3)	0.001 (3)	0.005 (3)
C1	0.047 (5)	0.037 (4)	0.034 (5)	−0.004 (3)	−0.001 (4)	−0.004 (3)
C2	0.035 (4)	0.052 (5)	0.050 (6)	−0.006 (4)	0.008 (4)	0.004 (4)
N2	0.038 (4)	0.030 (3)	0.045 (5)	−0.006 (3)	−0.001 (3)	0.006 (3)
C3	0.062 (6)	0.049 (5)	0.056 (7)	−0.004 (4)	0.017 (5)	0.010 (5)
C4	0.062 (6)	0.033 (4)	0.089 (9)	−0.004 (4)	0.010 (6)	0.011 (5)

Geometric parameters (Å, º)

Mn1—Br3	2.4924 (13)	C2—H2D	0.9800
Mn1—Br2	2.5062 (12)	C2—H2E	0.9800
Mn1—Br1	2.5145 (13)	N2—C3	1.453 (13)
Mn1—Br4	2.5309 (14)	N2—C4	1.493 (11)
N1—C2	1.469 (11)	N2—H2A	0.9200
N1—C1	1.469 (11)	N2—H2B	0.9200
N1—H1A	0.9200	C3—H3A	0.9800
N1—H1B	0.9200	C3—H3B	0.9800
C1—H1C	0.9800	C3—H3C	0.9800
C1—H1D	0.9800	C4—H4A	0.9800
C1—H1E	0.9800	C4—H4B	0.9800
C2—H2C	0.9800	C4—H4C	0.9800
Br3—Mn1—Br2	111.93 (5)	N1—C2—H2E	109.5
Br3—Mn1—Br1	111.01 (5)	H2C—C2—H2E	109.5
Br2—Mn1—Br1	109.08 (5)	H2D—C2—H2E	109.5
Br3—Mn1—Br4	109.49 (5)	C3—N2—C4	114.3 (8)
Br2—Mn1—Br4	110.02 (5)	C3—N2—H2A	108.7
Br1—Mn1—Br4	105.10 (5)	C4—N2—H2A	108.7
C2—N1—C1	114.5 (7)	C3—N2—H2B	108.7
C2—N1—H1A	108.6	C4—N2—H2B	108.7
C1—N1—H1A	108.6	H2A—N2—H2B	107.6
C2—N1—H1B	108.6	N2—C3—H3A	109.5
C1—N1—H1B	108.6	N2—C3—H3B	109.5
H1A—N1—H1B	107.6	H3A—C3—H3B	109.5
N1—C1—H1C	109.5	N2—C3—H3C	109.5
N1—C1—H1D	109.5	H3A—C3—H3C	109.5
H1C—C1—H1D	109.5	H3B—C3—H3C	109.5
N1—C1—H1E	109.5	N2—C4—H4A	109.5
H1C—C1—H1E	109.5	N2—C4—H4B	109.5
H1D—C1—H1E	109.5	H4A—C4—H4B	109.5
N1—C2—H2C	109.5	N2—C4—H4C	109.5
N1—C2—H2D	109.5	H4A—C4—H4C	109.5
H2C—C2—H2D	109.5	H4B—C4—H4C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1	0.92	2.47	3.377 (6)	167
N1—H1A···Br2^i	0.92	2.89	3.492 (7)	125
N1—H1A···Br4^i	0.92	2.78	3.466 (6)	132
N2—H2A···Br4^i	0.92	2.56	3.401 (7)	153
N2—H2B···Br3^ii	0.92	2.49	3.346 (7)	155

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