catena-Poly[[manganese(II)-tris­(μ-bet­aine-κ2O:O′)] tetra­bromido­manganate(IV)

Kocadag, M.; Fleck, M.; Bohatý, L.

doi:10.1107/S1600536808028912

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1273-m1274

doi:10.1107/S1600536808028912

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catena-Poly[[manganese(II)-tris(μ-betaine-κ²O:O′)] tetrabromidomanganate(IV)

Maria Kocadag,^a ^* Michel Fleck ^a and Ladislav Bohatý ^b

^aUniversität Wien – Geozentrum, Institut für Mineralogie und Kristallographie, Althanstrasse 14, A-1090 Wien, Austria, and ^bUniversität zu Köln, Institut für Kristallographie, Zülpicher Strasse 49b, D-50674 Köln, Germany
^*Correspondence e-mail: maria.kocadag@hotmail.com

(Received 11 August 2008; accepted 9 September 2008; online 17 September 2008)

The title compound, [Mn(C₅H₁₁NO₂)₃]·MnBr₄, contains polymeric cationic chains of distorted MnO₆ octahedra and bridging betaine molecules, running parallel to the a axis. There are two distinct Mn²⁺ cations in the chain, both with site symmetry $[\overline{1}]$ . Distorted [MnBr₄]²⁻ tetrahedra occupy the spaces between the chains.

Related literature

For related literature, see: Chen & Mak (1994 ); Haussühl (1988 , 1989 ); Haussühl & Schreuer (2001 ); Haussühl & Wang (1989 ); Mak (1990 ); Viertorinne et al. (1999 ); Wang et al. (1986 ); Wiehl et al. (2006a ,b )); Chen & Mak (1991 ); Schreuer & Haussühl (1993 ).

Experimental

Crystal data

[Mn(C₅H₁₁NO₂)₃]·MnBr₄
M_r = 780.96
Triclinic, $[P \overline 1]$
a = 9.140 (2) Å
b = 12.700 (2) Å
c = 12.871 (3) Å
α = 66.557 (6)°
β = 86.063 (7)°
γ = 89.249 (7)°
V = 1367.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 6.80 mm⁻¹
T = 293 (2) K
0.50 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (Otwinowski & Minor, 1997 ) T_min = 0.073, T_max = 0.130
17423 measured reflections
7836 independent reflections
5085 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.115
S = 1.05
7836 reflections
326 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.77 e Å⁻³
Δρ_min = −1.88 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O2C	2.173 (3)
Mn1—O1B	2.176 (3)
Mn1—O1Aⁱ	2.219 (3)
Mn2—O1C	2.131 (3)
Mn2—O2B	2.163 (3)
Mn2—O2A	2.192 (3)
Mn3—Br2	2.4724 (11)
Mn3—Br4	2.4932 (11)
Mn3—Br1	2.5019 (12)
Mn3—Br3	2.5179 (11)
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2004 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028912/hb2779sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028912/hb2779Isup2.hkl

checkCIF report

Comment top

The physical properties of compounds of metal salts with the zwitterionic ligand betaine have been investigated intensively in the past (Haussühl & Schreuer, 2001; Haussühl & Wang, 1989; Haussühl, 1989; Haussühl, 1988; Wang et al., 1986; Chen & Mak, 1994, and references therein).

In particular, the low-dimensional magnetic properties of the isomorphic trigonal group of betaine manganese metal chlorides [(C₅H₁₁NO₂)₃Mn].MCl₄ (M = Mn, Co, Zn, space group P3) has been analysed in detail (Wiehl et al., 2006b). In these crystals, the betaine ligands operate as µ-(O,O') bridges between Mn²⁺ cations thus forming chains of the octahedrally coordinated mangnetic cations (S = 5/2). A model of an antiferromagnetic Heisenberg spin fits well the magnetic proerties of these crystals (Wiehl et al., 2006b).

Here, we present the crystal structure of the title compound, (I) (Fig. 1). The crystal structure of (I) contains three crystallographically non-equivalent mangenese atoms. Two of them, Mn1 and Mn2, located on centres of inversion, are sixfold coordinated by oxygen atoms of the carboxylate groups of betaine molecules, which act as bridging ligands to form an one-dimensional tris(carboxylato-O,O')-bridged Mn²⁺ complex (Table 1). The cationic chains are oriented along the a axis and possess approximately the rod symmetry P3 (Fig. 2). In the interstices between these chains, anionic distorted tetrahedral groups [Mn(3)Br₄]^2- are located.

Apart from the triclinic symmetry, the structural features of (I) are analogous to those of the trigonal chlorides [(C₅H₁₁NO₂)₃Mn].MCl₄ [M = Mn (Chen & Mak, 1991; Schreuer & Haussühl, 1993), Co (Wiehl et al., 2006a) and Zn (Wiehl et al., 2006b)]. The type of structural units [(C₅H₁₁NO₂)₃Mn]_∞ and [MnBr₄], and the structural packing of these chains and tetrahedra are analogous to the atomic arrangement in the structure of the chloride compounds. Both, the translation period in the direction of the chain axis [a in (I), c ≈ 9.08 Å in the chloride compounds] as well as the interchain distances [b and c in (I), a = b ≈ 12.8 Å in the chloride compounds] correspond well. The interatomic distances and angles within the betaine molecules agree well with the values given in the literature (Viertorinne et al., 1999; Mak, 1990), the carboxylate C—O distances indicate the delocalization of the electrons to a mesomeric state [C—O-distances range from 1.245 (5) to 1.255 (5) Å].

Related literature top

For related literature, see: Chen & Mak (1994); Haussühl (1988, 1989); Haussühl & Schreuer (2001); Haussühl & Wang (1989); Mak (1990); Viertorinne et al. (1999); Wang et al. (1986); Wiehl et al. (2006a,b)); Chen & Mak (1991); Schreuer & Haussühl (1993).

Experimental top

The title compound crystallizes from 3:2 stoichiometry aqueous solutions of betaine and MnBr₂ in the temperature range 290 to 300 K in thick tabular prismatic crystals of sulfur-yellow colour. Crystals of optical quality with dimensions up to 25 × 7 × 3 mm were grown from a solution of 167 g betaine and 272 g MnBr₂.4H₂O by very slow evaporation at 295 K during a period of 11 months.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), shown with displacement ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity.
	Fig. 2. Packing diagram for (I) (left) in comparison with the structure of ([(betaine)₃Mn](MCl₄)] (Wiehl et al., 2006a, right), viewed along and perpendicular to the chains (top and bottom). Hydrogen atoms are omitted for clarity.

catena-Poly[[manganese(II)-tris(µ-betaine-κ²O:O')] tetrabromidomanganese(IV)] top

Crystal data top

[Mn(C₅H₁₁NO₂)₃]·MnBr₄	Z = 2
M_r = 780.96	F(000) = 764
Triclinic, P1	D_x = 1.897 Mg m⁻³
Hall symbol: -P 1	Melting point: not determined K
a = 9.140 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.700 (2) Å	Cell parameters from 1294 reflections
c = 12.871 (3) Å	θ = 2.8–26.4°
α = 66.557 (6)°	µ = 6.80 mm⁻¹
β = 86.063 (7)°	T = 293 K
γ = 89.249 (7)°	Prism, yellow
V = 1367.3 (4) Å³	0.50 × 0.30 × 0.30 mm

Data collection top

Bruker SMART CCD diffractometer	7836 independent reflections
Radiation source: fine-focus sealed tube	5085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 0.1 pixels mm^-1	θ_max = 30°, θ_min = 1.8°
ϕ–scan and ω–scans	h = −13→13
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	k = −18→18
T_min = 0.073, T_max = 0.130	l = −15→18
17423 measured reflections

Refinement top

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0151P)² + 6.4946P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
7836 reflections	Δρ_max = 1.77 e Å⁻³
326 parameters	Δρ_min = −1.88 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0015 (3)

Crystal data top

[Mn(C₅H₁₁NO₂)₃]·MnBr₄	γ = 89.249 (7)°
M_r = 780.96	V = 1367.3 (4) Å³
Triclinic, P1	Z = 2
a = 9.140 (2) Å	Mo Kα radiation
b = 12.700 (2) Å	µ = 6.80 mm⁻¹
c = 12.871 (3) Å	T = 293 K
α = 66.557 (6)°	0.50 × 0.30 × 0.30 mm
β = 86.063 (7)°

Data collection top

Bruker SMART CCD diffractometer	7836 independent reflections
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	5085 reflections with I > 2σ(I)
T_min = 0.073, T_max = 0.130	R_int = 0.030
17423 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.77 e Å⁻³
7836 reflections	Δρ_min = −1.88 e Å⁻³
326 parameters

Special details top

Experimental. Single-crystal X-ray intensity data were collected at 293 K on a Nonius APEXII diffractometer with CCD-area detector, using 673 frames with phi- and omega-increments of 1 degree and a counting time of 60 s per frame. The crystal-to-detector-distance was 30 mm. The whole ewald sphere was measured. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by Direct methods (SHELXS97, Sheldrick, 2008) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F² (SHELXL97, Sheldrick, 2008). All hydrogen atoms were treated as riding. Using anisotropic treatment of the non-H atoms and unrestrained isotropic treatment of the H atoms, the refinement converged at an R-value of 0.053.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	1.0000	0.0000	1.0000	0.0226 (2)
Mn2	0.5000	0.0000	1.0000	0.0234 (2)
Mn3	0.77120 (8)	0.62332 (7)	0.69412 (7)	0.0388 (2)
Br1	0.72670 (6)	0.62971 (5)	0.88548 (5)	0.04926 (17)
Br2	0.73289 (7)	0.43013 (5)	0.69615 (7)	0.05729 (19)
Br3	1.03439 (7)	0.68376 (6)	0.62887 (6)	0.05688 (19)
Br4	0.60829 (11)	0.76456 (8)	0.56062 (8)	0.0922 (3)
O1A	0.1462 (3)	0.1052 (3)	0.8505 (3)	0.0338 (8)
O2A	0.3773 (3)	0.0449 (3)	0.8480 (3)	0.0301 (7)
C1A	0.2801 (4)	0.1200 (4)	0.8221 (4)	0.0256 (9)
C2A	0.3415 (5)	0.2387 (4)	0.7460 (6)	0.0372 (12)
H2A1	0.426 (6)	0.258 (5)	0.781 (5)	0.046 (16)*
H2A2	0.375 (7)	0.234 (5)	0.682 (6)	0.06 (2)*
N3A	0.2438 (4)	0.3404 (3)	0.7206 (4)	0.0366 (10)
C4A	0.1914 (11)	0.3524 (6)	0.8271 (7)	0.082 (3)
H4A1	0.1203	0.4122	0.8106	0.10 (3)*
H4A2	0.2728	0.3715	0.8600	0.13 (4)*
H4A3	0.1472	0.2813	0.8797	0.11 (3)*
C5A	0.3320 (7)	0.4447 (5)	0.6441 (8)	0.068 (2)
H5A1	0.3296	0.4528	0.5668	0.17 (5)*
H5A2	0.4316	0.4364	0.6650	0.11 (3)*
H5A3	0.2912	0.5116	0.6515	0.09 (3)*
C6A	0.1167 (7)	0.3324 (6)	0.6576 (7)	0.067 (2)
H6A1	0.0802	0.4078	0.6166	0.08 (2)*
H6A2	0.0406	0.2857	0.7104	0.10 (3)*
H6A3	0.1474	0.2984	0.6053	0.14 (4)*
O1B	0.8835 (3)	−0.0491 (3)	0.8839 (3)	0.0326 (7)
O2B	0.6524 (3)	−0.1059 (3)	0.9500 (3)	0.0333 (7)
C1B	0.7526 (4)	−0.0671 (3)	0.8728 (4)	0.0265 (9)
C2B	0.7027 (6)	−0.0439 (5)	0.7562 (5)	0.0423 (13)
H2B1	0.718 (5)	−0.112 (5)	0.743 (5)	0.036 (14)*
H2B2	0.601 (8)	−0.024 (6)	0.750 (7)	0.08 (2)*
N3B	0.7830 (4)	0.0477 (3)	0.6558 (4)	0.0329 (9)
C4B	0.9394 (6)	0.0214 (7)	0.6382 (6)	0.0612 (19)
H4B1	0.9462	−0.0541	0.6382	0.11 (3)*
H4B2	0.9934	0.0246	0.6983	0.10 (3)*
H4B3	0.9798	0.0767	0.5667	0.08 (2)*
C5B	0.7081 (8)	0.0607 (7)	0.5518 (6)	0.069 (2)
H5B1	0.7560	0.1207	0.4868	0.07 (2)*
H5B2	0.6073	0.0799	0.5602	0.10 (3)*
H5B3	0.7131	−0.0101	0.5415	0.12 (4)*
C6B	0.7741 (9)	0.1589 (5)	0.6699 (6)	0.0625 (19)
H6B1	0.8302	0.2167	0.6083	0.07 (2)*
H6B2	0.8128	0.1496	0.7405	0.08 (2)*
H6B3	0.6736	0.1817	0.6701	0.14 (4)*
O1C	0.6456 (3)	0.1430 (3)	0.9163 (3)	0.0290 (7)
O2C	0.8693 (3)	0.1519 (3)	0.9718 (3)	0.0323 (7)
C1C	0.7365 (4)	0.1769 (3)	0.9644 (4)	0.0248 (9)
C2C	0.6737 (5)	0.2597 (4)	1.0147 (5)	0.0322 (11)
H2C1	0.668 (6)	0.336 (5)	0.954 (5)	0.041 (15)*
H2C2	0.579 (5)	0.235 (4)	1.044 (4)	0.030 (13)*
N3C	0.7558 (4)	0.2747 (3)	1.1054 (4)	0.0313 (9)
C4C	0.6680 (6)	0.3497 (5)	1.1501 (6)	0.0476 (14)
H4C1	0.5749	0.3134	1.1829	0.06 (2)*
H4C2	0.6528	0.4223	1.0891	0.06 (2)*
H4C3	0.7200	0.3615	1.2070	0.061 (19)*
C5C	0.7746 (7)	0.1616 (5)	1.2014 (5)	0.0526 (15)
H5C1	0.8323	0.1127	1.1745	0.062 (19)*
H5C2	0.6802	0.1265	1.2316	0.08 (2)*
H5C3	0.8236	0.1731	1.2598	0.07 (2)*
C6C	0.9027 (6)	0.3312 (5)	1.0602 (6)	0.0526 (16)
H6C1	0.9568	0.3300	1.1219	0.09 (3)*
H6C2	0.8897	0.4093	1.0086	0.08 (2)*
H6C3	0.9557	0.2907	1.0209	0.063 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0179 (4)	0.0249 (4)	0.0249 (5)	0.0018 (3)	−0.0021 (3)	−0.0098 (4)
Mn2	0.0181 (4)	0.0239 (4)	0.0285 (6)	0.0012 (3)	−0.0028 (3)	−0.0106 (4)
Mn3	0.0387 (4)	0.0352 (4)	0.0424 (5)	0.0046 (3)	−0.0074 (3)	−0.0146 (4)
Br1	0.0429 (3)	0.0614 (4)	0.0466 (4)	0.0068 (2)	−0.0049 (2)	−0.0247 (3)
Br2	0.0566 (4)	0.0403 (3)	0.0771 (5)	−0.0048 (2)	−0.0039 (3)	−0.0255 (3)
Br3	0.0526 (3)	0.0688 (4)	0.0461 (4)	−0.0236 (3)	0.0062 (3)	−0.0204 (3)
Br4	0.1235 (7)	0.0924 (6)	0.0730 (6)	0.0703 (5)	−0.0529 (5)	−0.0408 (5)
O1A	0.0239 (15)	0.0365 (17)	0.033 (2)	−0.0015 (12)	0.0014 (13)	−0.0057 (15)
O2A	0.0284 (15)	0.0291 (15)	0.032 (2)	0.0063 (12)	−0.0075 (13)	−0.0110 (14)
C1A	0.0254 (19)	0.030 (2)	0.021 (2)	0.0010 (16)	−0.0029 (16)	−0.0093 (18)
C2A	0.024 (2)	0.031 (2)	0.049 (4)	0.0024 (17)	−0.001 (2)	−0.007 (2)
N3A	0.032 (2)	0.0296 (19)	0.043 (3)	0.0016 (15)	−0.0035 (18)	−0.0094 (19)
C4A	0.142 (8)	0.047 (4)	0.059 (5)	0.013 (4)	0.014 (5)	−0.027 (4)
C5A	0.052 (4)	0.031 (3)	0.093 (7)	−0.007 (2)	0.001 (3)	0.005 (3)
C6A	0.043 (3)	0.052 (4)	0.087 (6)	0.010 (3)	−0.031 (3)	−0.004 (4)
O1B	0.0256 (15)	0.0440 (18)	0.033 (2)	0.0013 (13)	−0.0051 (13)	−0.0200 (16)
O2B	0.0291 (16)	0.0305 (16)	0.042 (2)	0.0028 (12)	0.0042 (14)	−0.0171 (15)
C1B	0.025 (2)	0.0241 (19)	0.033 (3)	0.0046 (15)	−0.0050 (17)	−0.0139 (19)
C2B	0.040 (3)	0.046 (3)	0.036 (3)	−0.013 (2)	−0.009 (2)	−0.010 (2)
N3B	0.033 (2)	0.036 (2)	0.029 (2)	0.0030 (16)	−0.0049 (16)	−0.0125 (18)
C4B	0.049 (3)	0.089 (5)	0.037 (4)	0.026 (3)	0.005 (3)	−0.018 (4)
C5B	0.074 (5)	0.077 (5)	0.037 (4)	−0.018 (4)	−0.024 (3)	−0.001 (3)
C6B	0.095 (5)	0.038 (3)	0.050 (5)	0.003 (3)	0.016 (4)	−0.016 (3)
O1C	0.0289 (15)	0.0280 (15)	0.029 (2)	−0.0044 (12)	−0.0020 (13)	−0.0105 (13)
O2C	0.0261 (15)	0.0288 (15)	0.045 (2)	0.0060 (12)	−0.0052 (14)	−0.0168 (15)
C1C	0.0258 (19)	0.0199 (18)	0.026 (3)	−0.0009 (14)	−0.0003 (16)	−0.0070 (17)
C2C	0.021 (2)	0.039 (3)	0.042 (3)	0.0059 (18)	−0.0085 (19)	−0.022 (2)
N3C	0.0264 (18)	0.0337 (19)	0.039 (3)	0.0031 (15)	−0.0048 (16)	−0.0196 (18)
C4C	0.042 (3)	0.059 (4)	0.058 (4)	0.011 (3)	−0.005 (3)	−0.040 (3)
C5C	0.073 (4)	0.044 (3)	0.044 (4)	0.008 (3)	−0.017 (3)	−0.019 (3)
C6C	0.031 (3)	0.060 (4)	0.082 (5)	−0.011 (2)	0.003 (3)	−0.044 (4)

Geometric parameters (Å, º) top

Mn1—O2Cⁱ	2.173 (3)	O2B—C1B	1.252 (5)
Mn1—O2C	2.173 (3)	C1B—C2B	1.512 (7)
Mn1—O1B	2.176 (3)	C2B—N3B	1.503 (7)
Mn1—O1Bⁱ	2.176 (3)	C2B—H2B1	0.95 (5)
Mn1—O1Aⁱⁱ	2.219 (3)	C2B—H2B2	0.96 (7)
Mn1—O1Aⁱⁱⁱ	2.219 (3)	N3B—C4B	1.487 (6)
Mn2—O1Cⁱⁱ	2.131 (3)	N3B—C6B	1.493 (7)
Mn2—O1C	2.131 (3)	N3B—C5B	1.495 (7)
Mn2—O2B	2.163 (3)	C4B—H4B1	0.9600
Mn2—O2Bⁱⁱ	2.163 (3)	C4B—H4B2	0.9600
Mn2—O2Aⁱⁱ	2.192 (3)	C4B—H4B3	0.9600
Mn2—O2A	2.192 (3)	C5B—H5B1	0.9600
Mn3—Br2	2.4724 (11)	C5B—H5B2	0.9600
Mn3—Br4	2.4932 (11)	C5B—H5B3	0.9600
Mn3—Br1	2.5019 (12)	C6B—H6B1	0.9600
Mn3—Br3	2.5179 (11)	C6B—H6B2	0.9600
O1A—C1A	1.247 (5)	C6B—H6B3	0.9600
O2A—C1A	1.255 (5)	O1C—C1C	1.245 (5)
C1A—C2A	1.522 (6)	O2C—C1C	1.251 (5)
C2A—N3A	1.499 (6)	C1C—C2C	1.527 (6)
C2A—H2A1	1.00 (6)	C2C—N3C	1.505 (6)
C2A—H2A2	0.89 (7)	C2C—H2C1	0.97 (6)
N3A—C4A	1.485 (8)	C2C—H2C2	0.92 (5)
N3A—C6A	1.488 (7)	N3C—C5C	1.493 (7)
N3A—C5A	1.502 (7)	N3C—C4C	1.495 (6)
C4A—H4A1	0.9600	N3C—C6C	1.497 (6)
C4A—H4A2	0.9600	C4C—H4C1	0.9600
C4A—H4A3	0.9600	C4C—H4C2	0.9600
C5A—H5A1	0.9600	C4C—H4C3	0.9600
C5A—H5A2	0.9600	C5C—H5C1	0.9600
C5A—H5A3	0.9600	C5C—H5C2	0.9600
C6A—H6A1	0.9600	C5C—H5C3	0.9600
C6A—H6A2	0.9600	C6C—H6C1	0.9600
C6A—H6A3	0.9600	C6C—H6C2	0.9600
O1B—C1B	1.249 (5)	C6C—H6C3	0.9600

O2Cⁱ—Mn1—O2C	180.0	C1B—O1B—Mn1	135.7 (3)
O2Cⁱ—Mn1—O1B	86.19 (12)	C1B—O2B—Mn2	124.0 (3)
O2C—Mn1—O1B	93.81 (12)	O1B—C1B—O2B	127.1 (5)
O2Cⁱ—Mn1—O1Bⁱ	93.81 (12)	O1B—C1B—C2B	119.7 (4)
O2C—Mn1—O1Bⁱ	86.19 (12)	O2B—C1B—C2B	113.1 (4)
O1B—Mn1—O1Bⁱ	180.0	N3B—C2B—C1B	117.9 (4)
O2Cⁱ—Mn1—O1Aⁱⁱ	88.25 (12)	N3B—C2B—H2B1	104 (3)
O2C—Mn1—O1Aⁱⁱ	91.75 (12)	C1B—C2B—H2B1	107 (3)
O1B—Mn1—O1Aⁱⁱ	93.30 (13)	N3B—C2B—H2B2	105 (5)
O1Bⁱ—Mn1—O1Aⁱⁱ	86.70 (13)	C1B—C2B—H2B2	113 (5)
O2Cⁱ—Mn1—O1Aⁱⁱⁱ	91.75 (12)	H2B1—C2B—H2B2	109 (5)
O2C—Mn1—O1Aⁱⁱⁱ	88.25 (12)	C4B—N3B—C6B	109.3 (5)
O1B—Mn1—O1Aⁱⁱⁱ	86.70 (13)	C4B—N3B—C5B	107.8 (5)
O1Bⁱ—Mn1—O1Aⁱⁱⁱ	93.30 (13)	C6B—N3B—C5B	108.5 (5)
O1Aⁱⁱ—Mn1—O1Aⁱⁱⁱ	180.0	C4B—N3B—C2B	113.8 (4)
O1Cⁱⁱ—Mn2—O1C	180.0	C6B—N3B—C2B	109.1 (4)
O1Cⁱⁱ—Mn2—O2B	90.79 (12)	C5B—N3B—C2B	108.2 (4)
O1C—Mn2—O2B	89.21 (12)	N3B—C4B—H4B1	109.5
O1Cⁱⁱ—Mn2—O2Bⁱⁱ	89.21 (12)	N3B—C4B—H4B2	109.5
O1C—Mn2—O2Bⁱⁱ	90.79 (12)	H4B1—C4B—H4B2	109.5
O2B—Mn2—O2Bⁱⁱ	180.0	N3B—C4B—H4B3	109.5
O1Cⁱⁱ—Mn2—O2Aⁱⁱ	91.45 (12)	H4B1—C4B—H4B3	109.5
O1C—Mn2—O2Aⁱⁱ	88.55 (12)	H4B2—C4B—H4B3	109.5
O2B—Mn2—O2Aⁱⁱ	86.67 (12)	N3B—C5B—H5B1	109.5
O2Bⁱⁱ—Mn2—O2Aⁱⁱ	93.33 (12)	N3B—C5B—H5B2	109.5
O1Cⁱⁱ—Mn2—O2A	88.55 (12)	H5B1—C5B—H5B2	109.5
O1C—Mn2—O2A	91.45 (12)	N3B—C5B—H5B3	109.5
O2B—Mn2—O2A	93.33 (12)	H5B1—C5B—H5B3	109.5
O2Bⁱⁱ—Mn2—O2A	86.67 (12)	H5B2—C5B—H5B3	109.5
O2Aⁱⁱ—Mn2—O2A	180.0	N3B—C6B—H6B1	109.5
Br2—Mn3—Br4	110.42 (4)	N3B—C6B—H6B2	109.5
Br2—Mn3—Br1	113.26 (4)	H6B1—C6B—H6B2	109.5
Br4—Mn3—Br1	108.64 (4)	N3B—C6B—H6B3	109.5
Br2—Mn3—Br3	108.51 (4)	H6B1—C6B—H6B3	109.5
Br4—Mn3—Br3	108.99 (5)	H6B2—C6B—H6B3	109.5
Br1—Mn3—Br3	106.89 (4)	C1C—O1C—Mn2	124.6 (3)
C1A—O1A—Mn1^iv	138.8 (3)	C1C—O2C—Mn1	136.7 (3)
C1A—O2A—Mn2	123.0 (3)	O1C—C1C—O2C	126.7 (4)
O1A—C1A—O2A	127.0 (4)	O1C—C1C—C2C	113.7 (4)
O1A—C1A—C2A	120.5 (4)	O2C—C1C—C2C	119.5 (4)
O2A—C1A—C2A	112.5 (4)	N3C—C2C—C1C	117.5 (4)
N3A—C2A—C1A	119.0 (4)	N3C—C2C—H2C1	106 (3)
N3A—C2A—H2A1	104 (3)	C1C—C2C—H2C1	109 (3)
C1A—C2A—H2A1	110 (3)	N3C—C2C—H2C2	108 (3)
N3A—C2A—H2A2	110 (4)	C1C—C2C—H2C2	108 (3)
C1A—C2A—H2A2	106 (4)	H2C1—C2C—H2C2	108 (4)
H2A1—C2A—H2A2	108 (5)	C5C—N3C—C4C	108.2 (5)
C4A—N3A—C6A	110.1 (6)	C5C—N3C—C6C	109.6 (4)
C4A—N3A—C2A	110.4 (5)	C4C—N3C—C6C	108.0 (4)
C6A—N3A—C2A	111.7 (5)	C5C—N3C—C2C	110.5 (4)
C4A—N3A—C5A	110.2 (6)	C4C—N3C—C2C	108.4 (4)
C6A—N3A—C5A	106.9 (5)	C6C—N3C—C2C	112.0 (4)
C2A—N3A—C5A	107.4 (4)	N3C—C4C—H4C1	109.5
N3A—C4A—H4A1	109.5	N3C—C4C—H4C2	109.5
N3A—C4A—H4A2	109.5	H4C1—C4C—H4C2	109.5
H4A1—C4A—H4A2	109.5	N3C—C4C—H4C3	109.5
N3A—C4A—H4A3	109.5	H4C1—C4C—H4C3	109.5
H4A1—C4A—H4A3	109.5	H4C2—C4C—H4C3	109.5
H4A2—C4A—H4A3	109.5	N3C—C5C—H5C1	109.5
N3A—C5A—H5A1	109.5	N3C—C5C—H5C2	109.5
N3A—C5A—H5A2	109.5	H5C1—C5C—H5C2	109.5
H5A1—C5A—H5A2	109.5	N3C—C5C—H5C3	109.5
N3A—C5A—H5A3	109.5	H5C1—C5C—H5C3	109.5
H5A1—C5A—H5A3	109.5	H5C2—C5C—H5C3	109.5
H5A2—C5A—H5A3	109.5	N3C—C6C—H6C1	109.5
N3A—C6A—H6A1	109.5	N3C—C6C—H6C2	109.5
N3A—C6A—H6A2	109.5	H6C1—C6C—H6C2	109.5
H6A1—C6A—H6A2	109.5	N3C—C6C—H6C3	109.5
N3A—C6A—H6A3	109.5	H6C1—C6C—H6C3	109.5
H6A1—C6A—H6A3	109.5	H6C2—C6C—H6C3	109.5
H6A2—C6A—H6A3	109.5

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

Experimental details

Crystal data
Chemical formula	[Mn(C₅H₁₁NO₂)₃]·MnBr₄
M_r	780.96
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.140 (2), 12.700 (2), 12.871 (3)
α, β, γ (°)	66.557 (6), 86.063 (7), 89.249 (7)
V (Å³)	1367.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.80
Crystal size (mm)	0.50 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (Otwinowski & Minor, 1997)
T_min, T_max	0.073, 0.130
No. of measured, independent and observed [I > 2σ(I)] reflections	17423, 7836, 5085
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.115, 1.05
No. of reflections	7836
No. of parameters	326
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.77, −1.88

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Bergerhoff et al., 1996).

Selected bond lengths (Å) top

Mn1—O2C	2.173 (3)	Mn2—O2A	2.192 (3)
Mn1—O1B	2.176 (3)	Mn3—Br2	2.4724 (11)
Mn1—O1Aⁱ	2.219 (3)	Mn3—Br4	2.4932 (11)
Mn2—O1C	2.131 (3)	Mn3—Br1	2.5019 (12)
Mn2—O2B	2.163 (3)	Mn3—Br3	2.5179 (11)

Symmetry code: (i) x+1, y, z.

Acknowledgements

The author thanks the International Centre for Diffraction Data for financial assistance of this work (grant No. 90-03 ET).

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