Acta Cryst. (2007). E63, m1433 [ doi:10.1107/S160053680701882X ]
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.
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.
H atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C, N)] using a riding model with N—H = 0.92Å or C—H = 0.98 Å.
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.
![[Figure 1]](./at2275fig1thm.gif)
| 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. |
| (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) Å3 | 0.22 × 0.21 × 0.18 mm |
| Z = 4 |
| Stoe IPDSII two-circle diffractometer | 2693 independent reflections |
| Radiation source: fine-focus sealed tube | 2105 reflections with I > 2σ(I) |
| graphite | 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 on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0617P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0058 (5) |
| (C2H8N)2[MnBr4] | V = 1450.7 (2) Å3 |
| Mr = 466.77 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.1854 (7) Å | µ = 11.89 mm−1 |
| b = 11.7492 (9) Å | T = 173 K |
| c = 15.1444 (11) Å | 0.22 × 0.21 × 0.18 mm |
| β = 95.087 (6)° |
| Stoe IPDSII two-circle diffractometer | 2693 independent reflections |
| Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2105 reflections with I > 2σ(I) |
| Tmin = 0.090, Tmax = 0.114 | Rint = 0.079 |
| 12230 measured reflections | θmax = 25.6° |
| R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.113 | Δρmax = 1.57 e Å−3 |
| S = 1.06 | Δρmin = −0.85 e Å−3 |
| 2693 reflections | Absolute structure: ? |
| 101 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| 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* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| 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) |
| 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 |
| 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···Br2i | 0.92 | 2.89 | 3.492 (7) | 125 |
| N1—H1A···Br4i | 0.92 | 2.78 | 3.466 (6) | 132 |
| N2—H2A···Br4i | 0.92 | 2.56 | 3.401 (7) | 153 |
| N2—H2B···Br3ii | 0.92 | 2.49 | 3.346 (7) | 155 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
| 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···Br2i | 0.92 | 2.89 | 3.492 (7) | 125 |
| N1—H1A···Br4i | 0.92 | 2.78 | 3.466 (6) | 132 |
| N2—H2A···Br4i | 0.92 | 2.56 | 3.401 (7) | 153 |
| N2—H2B···Br3ii | 0.92 | 2.49 | 3.346 (7) | 155 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
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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)+·MnBr42−, 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)+.HgBr42− (Pabst et al., 1990) 2(C2H10N)+.CdBr42− (Daoud, 1976; Waskowska, 1994), 2(C2H10N)+.HgCl42− (Salah et al., 1982) and 2(C2H10N)+.CoCl42− (Williams et al., 1992).