Diacetato-κO;κ2 O,O′-aqua­(2,4,6-tri-2-pyridyl-1,3,5-triazine-κ3 N 2,N 1,N 6)manganese(II) monohydrate

Kwang Ha

doi:10.1107/S1600536811032016

. 2011 Aug 17;67(Pt 9):m1238–m1239. doi: 10.1107/S1600536811032016

Diacetato-κO;κ² O,O′-aqua(2,4,6-tri-2-pyridyl-1,3,5-triazine-κ³ N ²,N ¹,N ⁶)manganese(II) monohydrate

Kwang Ha ^a,^*

PMCID: PMC3200744 PMID: 22058860

Abstract

The Mn^II ion in the title compound, [Mn(CH₃CO₂)₂(C₁₈H₁₂N₆)(H₂O)]·H₂O, is seven-coordinated in an approximately pentagonal–bipyramidal geometry by three N atoms of the tridentate 2,4,6-tri-2-pyridyl-1,3,5-triazine ligand and four O atoms from two distinct anionic acetato ligands and a water molecule. One acetate anion chelates the Mn atom via two O atoms occupying equatorial positions, and the other anion coordinates the Mn atom as a monodentate ligand via one O atom. The complex and solvent water molecules are linked by inter- and intramolecular O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the crystal structure of 2,4,6-tri-2-pyridyl-1,3,5-triazine (tptz), see: Drew et al. (1998 ▶). For tptz complexes with a five-coordinate Mn(II) atom, see: Ha (2010 ▶), and with a seven-coordinate Mn(II) atom, see: Majumder et al. (2006 ▶); Zhang et al. (2008 ▶); Lo & Ng (2009 ▶).

Experimental

Crystal data

[Mn(C₂H₃O₂)₂(C₁₈H₁₂N₆)(H₂O)]·H₂O
M _r = 521.40
Monoclinic,
a = 10.341 (2) Å
b = 24.977 (5) Å
c = 9.8284 (19) Å
β = 118.073 (4)°
V = 2239.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 200 K
0.32 × 0.24 × 0.17 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.863, T _max = 1.000
16577 measured reflections
5548 independent reflections
3076 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.153
S = 1.00
5548 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.49 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. DOI: 10.1107/S1600536811032016/ng5206sup1.cif

e-67-m1238-sup1.cif^{(26.3KB, cif)}

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

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

Mn1—O3	2.113 (2)
Mn1—O5	2.245 (2)
Mn1—O1	2.284 (2)
Mn1—O2	2.295 (2)
Mn1—N1	2.298 (3)
Mn1—N4	2.387 (3)
Mn1—N6	2.393 (3)

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O3—Mn1—O5	169.93 (10)
O1—Mn1—O2	57.06 (8)
N1—Mn1—N4	68.35 (9)
N1—Mn1—N6	68.43 (9)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯N5ⁱ	0.84	2.16	2.924 (3)	151
O5—H5B⋯O6ⁱⁱ	0.84	1.88	2.704 (3)	168
O6—H6A⋯O2	0.84	1.95	2.791 (3)	175
O6—H6B⋯O4ⁱⁱⁱ	0.84	1.87	2.711 (4)	176
C3—H3⋯O5^iv	0.95	2.46	3.399 (4)	170
C5—H5⋯O3ⁱ	0.95	2.59	3.338 (4)	136
C6—H6⋯O1	0.95	2.33	2.983 (4)	125
C18—H18⋯O2	0.95	2.55	3.198 (4)	125

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

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

The X-ray crystal structures of 2,4,6-tri-2-pyridyl-1,3,5-triazine (tptz) (Drew et al. 1998) and five- or seven-coordinated Mn(II)-tptz complexes, such as [MnCl₂(tptz)] (Ha, 2010), [Mn(C₂H₃O₂)(C₂N₃)(tptz)(H₂O)].(H₂O)₂ (Majumder et al., 2006; Zhang et al., 2008) and [Mn(C₂F₃O₂)(tptz)(H₂O)₂]C₂F₃O₂ (Lo & Ng, 2009), have been investigated previously.

The title compound consists of the neutral Mn(II) complex [Mn(C₂H₃O₂)₂(tptz)(H₂O)] and a solvent water molecule. In the reaction of Mn(CH₃CO₂)₃.2H₂O with tptz, it seems that the Mn^III ion reduced to the Mn^II ion. In the complex, the Mn^II ion is seven-coordinated in an approximately pentagonal-bipyramidal geometry by three N atoms of the tridentate tptz ligand and four O atoms from two distinct anionic acetato ligands and a water molecule (Fig. 1). The coordination modes of the acetate anions are quite different: one anion chelates the Mn atom via two O atoms occupying equatorial positions, and the other anion coordinates the Mn atom as a monodentate ligand via one O atom and occupies the axial sites together with the water ligand. The Mn—O and Mn—N bond lengths are somewhat different, respectively (Table 1). The Mn1—N4/6(pyridyl) bonds are somewhat longer than the Mn1—N1(triazine) bond, and the Mn1—O1/2(equatorial) bonds are slightly longer than the Mn1—O3/5(axial) bonds. The O1—Mn1—O2 chelating angle is considerably smaller than the N1—Mn1—N4/6 chelating angles and the apical O3—Mn1—O5 bond is slightly bent with a bond angle of 169.93 (10)°. The carboxylate groups of the anionic ligands appear to be delocalized on the basis of the C—O bond lengths [C—O: 1.235 (4)–1.269 (4) Å]. In the crystal, the two pyridyl rings coordinated to the Mn atom are located approximately parallel to their carrier triazine ring, making dihedral angles of 1.9 (2)° and 2.8 (2)°. The dihedral angle between the uncoordinated pyridyl ring and triazine ring is 7.8 (2)°. The complex and solvent water molecules are linked by inter- and intramolecular O—H···O, O—H···N and C—H···O hydrogen bonds into a three-dimensional network (Fig. 2 and Table 2). The compounds stack in columns along the [101] direction and display numerous intermolecular π-π interactions between the six-membered rings, with a shortest centroid-centroid distance of 3.493 (2) Å.

Experimental

To a solution of Mn(CH₃CO₂)₃.2H₂O (0.4022 g, 1.50 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. After removal of the formed dark brown precipitate by filtration, the solvent of the filtrate was evaporated, and the residue was washed with acetone and dried under vacuum, to give a yellow powder (0.3207 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃NO₂/MeOH solution.