Poly[[μ-N,N′-bis­(2-hy­droxy­eth­yl)-N,N,N′,N′-tetra­methyl­propane-1,3-diaminium-κ2O:O′]tetra-μ-bromido-dibromidodimanganese(II)]

Rinta, H.; Peuronen, A.; Lahtinen, M.

doi:10.1107/S1600536812044765

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1453-m1454

doi:10.1107/S1600536812044765

Open

access

Poly[[μ-N,N′-bis(2-hydroxyethyl)-N,N,N′,N′-tetramethylpropane-1,3-diaminium-κ²O:O′]tetra-μ-bromido-dibromidodimanganese(II)]

Heikki Rinta,^a Anssi Peuronen ^a and Manu Lahtinen ^a ^*

^aUniversity of Jyväskylä, Department of Chemistry, PO Box 35, FI-40014 JY, Finland
^*Correspondence e-mail: manu.lahtinen@jyu.fi

(Received 16 October 2012; accepted 29 October 2012; online 3 November 2012)

The asymmetric unit of the title three-dimensional coordination polymer, [Mn₂Br₆(C₁₁H₂₈N₂O₂)]_n, consists of one Mn^II cation, half of a dicationic N,N′-bis(2-hydroxyethyl)-N,N,N′,N′-tetramethylpropane-1,3-diaminium ligand (L) (the other half being generated by a twofold rotation axis), and three bromide ions. The Mn^II cation is coordinated by a single L ligand via the hydroxy O atom and by five bromide ions, resulting in a distorted octahedral MnBr₅O coordination geometry. Four of the bromide ions are bridging to two adjacent Mn^II atoms, thereby forming polymeric chains along the a and b axes. The L units act as links between neighbouring Mn—(μ-Br)₂—Mn chains, also forming a polymeric continuum along the c axis, which completes the formation of a three-dimensional network. Classical O—H⋯Br hydrogen bonds are present. The distance between adjacent Mn^II atoms is 4.022 (1) Å.

Related literature

For related structures of M^II transition metal halide one-dimensional coordination polymers, see: Han et al. (2012 ); Englert & Schiffers (2006 ). For two-dimensional networks, see: Hu & Englert (2006 ); Turgunov et al. (2011 ). For properties of metal halides, see: Hitchcock et al. (2003 ); Wang et al. (2011 ). For ligand conformations, see: Kärnä et al. (2010 ).

Experimental

Crystal data

[Mn₂Br₆(C₁₁H₂₈N₂O₂)]
M_r = 809.69
Tetragonal, P 4₃ 2₁ 2
a = 8.0163 (4) Å
c = 35.3103 (18) Å
V = 2269.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 11.69 mm⁻¹
T = 123 K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker–NoniusKappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.440, T_max = 0.746
5076 measured reflections
1966 independent reflections
1856 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.047
S = 1.02
1966 reflections
111 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 690 Friedel pairs
Flack parameter: 0.048 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Br3ⁱ	0.75 (2)	2.49 (2)	3.232 (3)	175 (5)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+{\script{1\over 4}}]$ .

Data collection: COLLECT (Bruker, 2008 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812044765/fj2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044765/fj2604Isup2.hkl

checkCIF report

Comment top

Solid state chemistry of metal halides has been widely studied in order to improve various magnetic and non-linear optical applications. In the crystal structure of the type MX₄L₂, the bridging qualities of the halide anions and the coordination properties of the organic ligands result in various polymeric structures. For example, one-dimensional M-(µ-X)₂—M bridged chains with low-dimensional arrangement have more suitable magnetic properties than classic structures of layered metal halide salts (Han et al. 2012; Wang et al. 2011 and Hitchcock et al. 2003).

The title compound, [Mn^II(µ-Br)₂µ-(C₁₁H₂₈N₂O₂)Br]_n, crystallizes in a tetragonal P4₃2₁2 crystal system showing one Mn^II cation, half of a dicationic [C₁₁H₂₈N₂O₂]²⁺ ligand (L) and three bromide anions in an asymmetric unit (Fig. 1). In this three-dimensional polymer each Mn^II cation is coordinated by four bridging bromo anions in the equatorial plane. A single terminal bromo anion and a ligand are located in the axial positions of the distorted octahedron showing axial Br3—Mn1—O1 angle of 174.03 (8)°. The three-dimensional network structure comprises two alternating crossed Mn-(µ-Br)₂—Mn chains (a- and b-axes) and an undulated L—Mn-(µ-Br)₂—Mn—L chain (c-axis). Distances between parallel Mn-(µ-Br)₂—Mn chains (planes through Mn -centres) are about 17.656 Å and between anti-parallel chains 8.7825 Å. This allows a formation of a structure model having alternating organic cation and a metal halide layers along c-axis (Figures 2 & 3).

In Mn^II cation coordination environment, the terminal Br^- anion fulfills the coordination of the Mn^II cation to octahedral MnBr₅O. The metal–metal distance along the resulting chain of octahedra is 4.022 (1) Å. All the equatorial Mn—Br bridge bond distances are almost identical but still somewhat longer than the axial Mn1—Br3 bond. The bridging bromides and the adjacent Mn -centers form folded square-planar geometry, showing nearly orthogonal contact angle of 94.05 (2)° via Mn4—Br2- Mn4 atoms, and torsion angle of 12.82 (2)° through Mn4—Br2—Mn4—Br1 atoms.

In the structure, the ligands are in S-shaped conformation between the anti-parallel Mn-(µ-Br)₂—Mn chains (Fig. 4). It seems that S-conformation is an ideal conformation for this type of relatively flexible ditopic ligand (Kärnä et al. 2010). The torsion angle C2—N4—N4—C2 is 156.70°. Similar cation conformations are found in ion pair structures [Zn^IIBr₄(C₁₁H₂₈N₂O₂)] and (C₁₁H₂₈N₂O₂) Br₂ H₂O.

Classical Br3···H–O1 hydrogen bonds are present in the Mn^II cation coordination environment between the terminal Br^- anions of Mn^II cation and the hydroxyl group of the neighboring metal center (Fig. 5). Hence, it seems likely that in the parent complex the hydrogen bonding steers the oxygen's coordination to the Mn^II cation. Weak interactions between O1 and halide bridge on the other side of Br1 and Br2 leads to distortions of chains torsion angle. The angle between the Mn1—Br1—Br2 and Mn1—Br1—Br2 planes is 162.6°. For this reason, Mn-(µ-Br)₂—Mn chains zigzag-conformation (Fig. 6).

Related literature top

For related structures of M^II transition metal halide one-dimensional coordination polymers, see: Han et al. (2012); Englert & Schiffers (2006). For two-dimensional networks, see: Hu & Englert (2006); Turgunov et al. (2011). For properties of metal halides, see: Hitchcock et al. (2003); Wang et al. (2011). For ligand conformations, see: Kärnä et al. (2010).

Experimental top

The single crystals of the title compound were obtained in the following two steps: First, dicationic bromide salt, as the precursor, was synthesized in 30 ml of acetone by reacting 2.20 ml (13.15 mmol) of TMPDA, C₇H₁₈N₂, and 2.16 ml (28.93 mmol) of 2-bromo-1-ethanol, C₂H₅BrO, for 48 h at 60 °C in a sealed flask. After removing the solvent, the white precipitation was washed by acetone and dried in vacuo (yield 71.6%; 3.58 g).

¹H-NMR (DMSO, 250 MHz, p.p.m.): 2.08–2.32 (2H, m, CH₂—CH₂-CH₂), 3.16 (12H, s, N—CH₃), 3.31 (2H, s, H₂O), 3.37–3.43 (4H, t, HO—CH₂—CH₂-N), 3.48–3.52 (4H, t, N—CH₂-CH₂—CH₂-N), 3.84 (4H, s, CH₂-OH), 5.29–5.33 (2H, t, OH)

Second, the precursor salt and the dried MnBr₂ 4H₂O (molar ratio ~1:1.5) were dissolved separately in minimum volume of warm methanol before combining the solutions. The title compound was synthesized in an open flask by metathesis reaction of the two aforementioned salts. The combined solution was stirred for about 1 h at 40 °C after which it was slowly cooled to RT and methanol was allowed to evaporate slowly. After several days, purple crystals suitable for X-ray analysis were formed.

Computing details top

Data collection: COLLECT (Bruker, 2008); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: Mercury (Macrae et al. 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008b).

Figures top

	Fig. 1. Asymmetric unit and labeling scheme of the title compound. Ellipsoids are presented at the 50% probability level.
	Fig. 2. The one-dimensional linear chain with (µ-Br)₂ bridges, Mn···Mn contact with a distance of 4.022 (1) Å and hydrogen bonding scheme.
	Fig. 3. Undulated network formed by the L ligands connecting the alternating crossed Mn-(µ-Br)₂—Mn chains, viewed along b-axis.
	Fig. 4. S-shaped conformation of the ligands (only ligand backbone showed) between the anti-parallel Mn-(µ-Br)₂—Mn slightly distorted octahedron chains.
	Fig. 5. The structure is stabilized by weak intermolecular interactions between Br3 and nearby ligands.
	Fig. 6. Zigzag tilting of the adjacent MnBr₅O octahedra.

Poly[[µ-N,N'-bis(2-hydroxyethyl)- N,N,N',N'-tetramethylpropane-1,3-diaminium- κ²O:O']tetra-µ-bromido-dibromidodimanganese(II)] top

Crystal data top

[Mn₂Br₆(C₁₁H₂₈N₂O₂)]	D_x = 2.370 Mg m⁻³
M_r = 809.69	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 1871 reflections
Hall symbol: P 4nw 2abw	θ = 0.4–27.9°
a = 8.0163 (4) Å	µ = 11.69 mm⁻¹
c = 35.3103 (18) Å	T = 123 K
V = 2269.1 (2) Å³	Block, violet
Z = 4	0.25 × 0.25 × 0.20 mm
F(000) = 1536

Data collection top

Bruker–NoniusKappa APEXII diffractometer	1966 independent reflections
Radiation source: fine-focus sealed tube	1856 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 9 pixels mm^-1	θ_max = 25.0°, θ_min = 2.8°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −4→9
T_min = 0.440, T_max = 0.746	l = −22→41
5076 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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
1966 reflections	Δρ_max = 0.36 e Å⁻³
111 parameters	Δρ_min = −0.41 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 690 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.048 (14)

Crystal data top

[Mn₂Br₆(C₁₁H₂₈N₂O₂)]	Z = 4
M_r = 809.69	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 11.69 mm⁻¹
a = 8.0163 (4) Å	T = 123 K
c = 35.3103 (18) Å	0.25 × 0.25 × 0.20 mm
V = 2269.1 (2) Å³

Data collection top

Bruker–NoniusKappa APEXII diffractometer	1966 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1856 reflections with I > 2σ(I)
T_min = 0.440, T_max = 0.746	R_int = 0.032
5076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	Δρ_max = 0.36 e Å⁻³
S = 1.02	Δρ_min = −0.41 e Å⁻³
1966 reflections	Absolute structure: Flack (1983), 690 Friedel pairs
111 parameters	Absolute structure parameter: 0.048 (14)
1 restraint

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
C2	0.8227 (5)	0.8960 (5)	0.15487 (11)	0.0158 (9)
H2A	0.8379	0.8507	0.1290	0.019*
H2B	0.7031	0.9236	0.1580	0.019*
C3	0.8705 (5)	0.7633 (5)	0.18350 (10)	0.0143 (9)
H3A	0.8340	0.6538	0.1735	0.017*
H3B	0.9937	0.7605	0.1853	0.017*
C5	0.6146 (5)	0.7687 (6)	0.22206 (11)	0.0197 (10)
H5A	0.5825	0.6644	0.2095	0.030*
H5B	0.5680	0.8634	0.2081	0.030*
H5C	0.5713	0.7693	0.2480	0.030*
C6	0.8652 (5)	0.6412 (5)	0.24628 (11)	0.0172 (10)
H6A	0.8250	0.6531	0.2724	0.026*
H6B	0.9874	0.6423	0.2461	0.026*
H6C	0.8250	0.5356	0.2357	0.026*
C7	0.8412 (5)	0.9495 (5)	0.24099 (11)	0.0116 (9)
H7A	0.7764	0.9603	0.2647	0.014*
H7B	0.8049	1.0396	0.2237	0.014*
C8	1.0268 (5)	0.9732 (5)	0.2500	0.0140 (13)
H8A	1.0594	0.9039	0.2720	0.017*	0.50
H8B	1.0961	0.9406	0.2280	0.017*	0.50
N4	0.8013 (4)	0.7825 (4)	0.22294 (9)	0.0130 (8)
O1	0.9205 (3)	1.0470 (4)	0.15874 (8)	0.0140 (6)
Br1	0.61915 (5)	1.32320 (5)	0.175357 (11)	0.01348 (10)
Br2	1.13256 (5)	1.39037 (5)	0.167113 (10)	0.01205 (10)
Br3	0.81111 (5)	1.55274 (5)	0.090982 (11)	0.01279 (11)
Mn1	0.87136 (8)	1.27065 (7)	0.124710 (17)	0.01152 (14)
H1	1.010 (3)	1.021 (5)	0.1575 (13)	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.024 (2)	0.0120 (19)	0.011 (2)	−0.004 (2)	−0.003 (2)	−0.0030 (18)
C3	0.021 (2)	0.014 (2)	0.009 (2)	0.001 (2)	0.0015 (19)	0.0001 (17)
C5	0.013 (2)	0.025 (2)	0.021 (2)	−0.001 (2)	0.001 (2)	−0.006 (2)
C6	0.023 (2)	0.013 (2)	0.015 (2)	−0.0018 (19)	−0.0049 (19)	0.0016 (18)
C7	0.015 (2)	0.0074 (18)	0.012 (2)	−0.0020 (19)	−0.0027 (18)	−0.0025 (17)
C8	0.0114 (19)	0.0114 (19)	0.019 (3)	0.002 (3)	0.0015 (19)	0.0015 (19)
N4	0.0139 (16)	0.0157 (17)	0.0094 (17)	0.0011 (16)	−0.0017 (14)	0.0004 (15)
O1	0.0105 (14)	0.0137 (14)	0.0178 (15)	0.0010 (13)	0.0016 (14)	0.0026 (14)
Br1	0.01241 (19)	0.0168 (2)	0.01122 (19)	−0.00105 (19)	0.00124 (18)	−0.00200 (18)
Br2	0.01210 (19)	0.01371 (19)	0.01035 (19)	0.00068 (18)	0.00073 (16)	0.00004 (17)
Br3	0.01400 (19)	0.01200 (19)	0.0124 (2)	−0.00096 (19)	−0.00056 (18)	0.00178 (17)
Mn1	0.0117 (3)	0.0115 (3)	0.0113 (3)	−0.0001 (3)	0.0003 (3)	0.0014 (3)

Geometric parameters (Å, º) top

C2—O1	1.449 (5)	C7—C8	1.533 (5)
C2—C3	1.517 (5)	C7—H7A	0.9900
C2—H2A	0.9900	C7—H7B	0.9900
C2—H2B	0.9900	C8—C7ⁱ	1.533 (5)
C3—N4	1.507 (4)	C8—H8A	0.9900
C3—H3A	0.9900	C8—H8B	0.9900
C3—H3B	0.9900	O1—Mn1	2.194 (3)
C5—N4	1.501 (5)	O1—H1	0.748 (19)
C5—H5A	0.9800	Br1—Mn1	2.7319 (7)
C5—H5B	0.9800	Br1—Mn1ⁱⁱ	2.7635 (7)
C5—H5C	0.9800	Br2—Mn1ⁱⁱⁱ	2.7407 (7)
C6—N4	1.491 (5)	Br2—Mn1	2.7472 (8)
C6—H6A	0.9800	Br3—Mn1	2.6010 (7)
C6—H6B	0.9800	Mn1—Br2ⁱⁱ	2.7407 (7)
C6—H6C	0.9800	Mn1—Br1ⁱⁱⁱ	2.7635 (7)
C7—N4	1.517 (5)

O1—C2—C3	112.7 (3)	C7ⁱ—C8—H8A	110.4
O1—C2—H2A	109.0	C7—C8—H8A	110.4
C3—C2—H2A	109.0	C7ⁱ—C8—H8B	110.4
O1—C2—H2B	109.0	C7—C8—H8B	110.4
C3—C2—H2B	109.0	H8A—C8—H8B	108.6
H2A—C2—H2B	107.8	C6—N4—C5	107.3 (3)
N4—C3—C2	116.8 (3)	C6—N4—C3	107.9 (3)
N4—C3—H3A	108.1	C5—N4—C3	109.9 (3)
C2—C3—H3A	108.1	C6—N4—C7	111.4 (3)
N4—C3—H3B	108.1	C5—N4—C7	106.5 (3)
C2—C3—H3B	108.1	C3—N4—C7	113.6 (3)
H3A—C3—H3B	107.3	C2—O1—Mn1	122.3 (2)
N4—C5—H5A	109.5	C2—O1—H1	106 (4)
N4—C5—H5B	109.5	Mn1—O1—H1	112 (4)
H5A—C5—H5B	109.5	Mn1—Br1—Mn1ⁱⁱ	94.082 (12)
N4—C5—H5C	109.5	Mn1ⁱⁱⁱ—Br2—Mn1	94.254 (12)
H5A—C5—H5C	109.5	O1—Mn1—Br3	174.03 (8)
H5B—C5—H5C	109.5	O1—Mn1—Br1	84.28 (8)
N4—C6—H6A	109.5	Br3—Mn1—Br1	91.62 (2)
N4—C6—H6B	109.5	O1—Mn1—Br2ⁱⁱ	92.05 (8)
H6A—C6—H6B	109.5	Br3—Mn1—Br2ⁱⁱ	91.89 (2)
N4—C6—H6C	109.5	Br1—Mn1—Br2ⁱⁱ	84.75 (2)
H6A—C6—H6C	109.5	O1—Mn1—Br2	81.38 (8)
H6B—C6—H6C	109.5	Br3—Mn1—Br2	95.01 (2)
N4—C7—C8	113.7 (3)	Br1—Mn1—Br2	98.83 (2)
N4—C7—H7A	108.8	Br2ⁱⁱ—Mn1—Br2	172.12 (3)
C8—C7—H7A	108.8	O1—Mn1—Br1ⁱⁱⁱ	89.94 (8)
N4—C7—H7B	108.8	Br3—Mn1—Br1ⁱⁱⁱ	94.43 (2)
C8—C7—H7B	108.8	Br1—Mn1—Br1ⁱⁱⁱ	173.07 (2)
H7A—C7—H7B	107.7	Br2ⁱⁱ—Mn1—Br1ⁱⁱⁱ	91.67 (2)
C7ⁱ—C8—C7	106.5 (4)	Br2—Mn1—Br1ⁱⁱⁱ	84.03 (2)

O1—C2—C3—N4	79.7 (4)	C2—O1—Mn1—Br2	179.1 (3)
N4—C7—C8—C7ⁱ	167.0 (4)	C2—O1—Mn1—Br1ⁱⁱⁱ	−96.9 (3)
C2—C3—N4—C6	−179.3 (3)	Mn1ⁱⁱ—Br1—Mn1—O1	−105.44 (8)
C2—C3—N4—C5	64.0 (5)	Mn1ⁱⁱ—Br1—Mn1—Br3	78.92 (2)
C2—C3—N4—C7	−55.2 (5)	Mn1ⁱⁱ—Br1—Mn1—Br2ⁱⁱ	−12.838 (12)
C8—C7—N4—C6	54.1 (4)	Mn1ⁱⁱ—Br1—Mn1—Br2	174.24 (3)
C8—C7—N4—C5	170.8 (3)	Mn1ⁱⁱⁱ—Br2—Mn1—O1	78.06 (8)
C8—C7—N4—C3	−68.1 (4)	Mn1ⁱⁱⁱ—Br2—Mn1—Br3	−106.73 (2)
C3—C2—O1—Mn1	−175.3 (2)	Mn1ⁱⁱⁱ—Br2—Mn1—Br1	160.85 (3)
C2—O1—Mn1—Br1	79.3 (3)	Mn1ⁱⁱⁱ—Br2—Mn1—Br1ⁱⁱⁱ	−12.785 (11)
C2—O1—Mn1—Br2ⁱⁱ	−5.2 (3)

Symmetry codes: (i) −y+2, −x+2, −z+1/2; (ii) x−1/2, −y+5/2, −z+1/4; (iii) x+1/2, −y+5/2, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br3ⁱⁱⁱ	0.75 (2)	2.49 (2)	3.232 (3)	175 (5)

Symmetry code: (iii) x+1/2, −y+5/2, −z+1/4.

Experimental details

Crystal data
Chemical formula	[Mn₂Br₆(C₁₁H₂₈N₂O₂)]
M_r	809.69
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	123
a, c (Å)	8.0163 (4), 35.3103 (18)
V (Å³)	2269.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.69
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Bruker–NoniusKappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.440, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	5076, 1966, 1856
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.047, 1.02
No. of reflections	1966
No. of parameters	111
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.41
Absolute structure	Flack (1983), 690 Friedel pairs
Absolute structure parameter	0.048 (14)

Computer programs: COLLECT (Bruker, 2008), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), Mercury (Macrae et al. 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br3ⁱ	0.748 (19)	2.49 (2)	3.232 (3)	175 (5)

Symmetry code: (i) x+1/2, −y+5/2, −z+1/4.

Acknowledgements

The financial support of University of Jyväskylä is gratefully acknowledged.

References

Bruker (2008). COLLECT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Englert, U. & Schiffers, S. (2006). Acta Cryst. E62, m295–m296. Web of Science CSD CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Han, S., Liu, X.-Y., Cai, Z.-F. Z.-P., Yin, W.-T., Xie, X.-D., Zhou, J.-R., Yang, L.-M. & Ni, C.-L. (2012). Inorg. Chem. Commun. 24, 91–94. Web of Science CSD CrossRef CAS Google Scholar
Hitchcock, P. B., Lee, T. H. & Leigh, G. J. (2003). Dalton Trans. pp. 2276–2279. Web of Science CSD CrossRef Google Scholar
Hu, C. & Englert, U. (2006). Angew. Chem. Int. Ed. Engl. 45, 3457–3459. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kärnä, M., Lahtinen, M., Hakkarainen, P.-L. & Valkonen, J. (2010). Aust. J. Chem. 63, 1122–1137. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turgunov, K. K., Wang, Y., Englert, U. & Shakhidoyatov, K. M. (2011). Acta Cryst. E67, m953–m954. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, Y.-Q., Sun, Q., Yue, Q., Cheng, A.-L., Song, Y. & Gao, E.-Q. (2011). Dalton Trans. 40, 10966–10974. Web of Science CSD CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.