Dibromido(2,4,6-tri-2-pyridyl-1,3,5-triazine-κ3 N 2,N 1,N 6)manganese(II)

Kwang Ha

doi:10.1107/S1600536811045211

. 2011 Nov 5;67(Pt 12):m1655. doi: 10.1107/S1600536811045211

Dibromido(2,4,6-tri-2-pyridyl-1,3,5-triazine-κ³ N ²,N ¹,N ⁶)manganese(II)

Kwang Ha ^a,^*

PMCID: PMC3238591 PMID: 22199482

Abstract

The Mn^II ion in the title complex, [MnBr₂(C₁₈H₁₂N₆)], is five-coordinated in a distorted square-pyramidal geometry by three N atoms of the tridentate 2,4,6-tri-2-pyridyl-1,3,5-triazine (tptz) ligand and two bromide anions. In the crystal, the pyridyl rings coordinated to the Mn atom are inclined slightly to their carrier triazine ring [dihedral angles = 8.0 (3) and 7.5 (3)°], whereas the uncoordinated pyridyl ring is located approximately parallel to the triazine ring [dihedral angle = 3.7 (3)°]. The complexes are stacked in columns along the a axis and linked by intermolecular C—H⋯Br hydrogen bonds, forming chains. In the column, intermolecular π–π interactions between the six-membered rings are present, the shortest centroid–centroid distance being 3.750 (4) Å.

Related literature

For the crystal structure of the related compound [MnBr₂(tptz)(H₂O)]·H₂O, see: Ha (2011 ▶).

Experimental

Crystal data

[MnBr₂(C₁₈H₁₂N₆)]
M _r = 527.10
Triclinic,
a = 8.7095 (19) Å
b = 10.498 (2) Å
c = 11.213 (3) Å
α = 110.094 (4)°
β = 98.471 (4)°
γ = 91.820 (5)°
V = 948.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 4.92 mm⁻¹
T = 200 K
0.27 × 0.17 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.695, T _max = 1.000
6897 measured reflections
4548 independent reflections
3124 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.114
S = 1.14
4548 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811045211/zq2132sup1.cif

e-67-m1655-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045211/zq2132Isup2.hkl

e-67-m1655-Isup2.hkl^{(222.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Mn1—N1	2.181 (4)
Mn1—N4	2.314 (5)
Mn1—N6	2.331 (4)
Mn1—Br2	2.4884 (11)
Mn1—Br1	2.4957 (11)

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N1—Mn1—N4	70.43 (15)
N1—Mn1—N6	71.07 (16)
Br2—Mn1—Br1	111.10 (4)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Br1ⁱ	0.95	2.91	3.782 (6)	153
C15—H15⋯Br1ⁱⁱ	0.95	2.91	3.744 (6)	148

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

supplementary crystallographic information

Comment

In the title complex, [MnBr₂(tptz)] (tptz = 2,4,6-tri-2-pyridyl-1,3,5-triazine, C₁₈H₁₂N₆), the Mn^II ion is five-coordinated in a distorted square-pyramidal geometry by three N atoms of the tridentate tptz ligand and two bromide anions (Fig. 1). By contrast, in the previously reported analogous complex [MnBr₂(tptz)(H₂O)].H₂O, obtained from a CH₃CN solution, the Mn^II ion is six-coordinated in a distorted octahedral environment by three N atoms, two Br atoms and one O atom from the water ligand (Ha, 2011).

While the Mn—Br bond lengths are almost equal, the Mn—N bond lengths are somewhat different (Table 1). The Mn1—N4/6(pyridyl) bonds are slightly longer than the Mn1—N1(triazine) bond. In the crystal, the pyridyl rings coordinated to the Mn atom are inclined slightly to their carrier triazine ring [dihedral angles = 8.0 (3)° and 7.5 (3)°], whereas the uncoordinated pyridyl ring is located approximately parallel to the triazine ring [dihedral angle = 3.7 (3)°]. The complexes are stacked in columns along the a axis and linked by intermolecular C—H···Br hydrogen bonds, forming one-dimensional chains (Fig. 2 and Table 2). In the column, intermolecular π-π interactions between the six-membered rings are present, the shortest centroid-centroid distance being 3.750 (4) Å.

Experimental

To a solution of MnBr₂.4H₂O (0.2868 g, 1.00 mmol) in MeOH (30 ml) was added 2,4,6-tri-2-pyridyl-1,3,5-triazine (0.1561 g, 0.50 mmol) and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with MeOH and dried under vacuum, to give an orange powder (0.1065 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a dimethyl sulfoxide (DMSO) solution at 90 °C.