A second monoclinic polymorph of bis­(2,2′-bipyridine-κ2 N,N′)diiodido­manganese(II)

Kwang Ha

doi:10.1107/S1600536811036051

. 2011 Sep 14;67(Pt 10):m1351. doi: 10.1107/S1600536811036051

A second monoclinic polymorph of bis(2,2′-bipyridine-κ² N,N′)diiodidomanganese(II)

Kwang Ha ^a,^*

PMCID: PMC3201270 PMID: 22065514

Abstract

The Mn^II ion in the title complex, [MnI₂(C₁₀H₈N₂)₂], is six-coordinated in a distorted cis-N₄I₂Mn octahedral environment by four N atoms of the two chelating 2,2′-bipyridine ligands and two iodide anions. As a result of the different trans effects of the N and I atoms, the Mn—N bonds trans to the I atom are slightly longer than the Mn—N bonds trans to the N atom. The dihedral angle between the approximately planar ligands [maximum deviation = 0.064 (7) Å] is 75.0 (1)°. Numerous inter- and intramolecular π–π interactions between the pyridyl rings are present, the shortest centroid–centroid distance being 3.905 (5) Å. The structure reported herein represents a new monoclinic polymorph of the previously reported monoclinic (P2₁/c) form [Ha (2011 ▶). Z. Kristallogr. New Cryst. Struct. 226, 187–188].

Related literature

For the P2₁/c polymorph, see: Ha (2011 ▶).

Experimental

Crystal data

[MnI₂(C₁₀H₈N₂)₂]
M _r = 621.11
Monoclinic,
a = 16.491 (4) Å
b = 15.403 (4) Å
c = 17.719 (4) Å
β = 110.187 (5)°
V = 4224.6 (18) Å³
Z = 8
Mo Kα radiation
μ = 3.56 mm⁻¹
T = 200 K
0.16 × 0.13 × 0.06 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.804, T _max = 1.000
15547 measured reflections
5222 independent reflections
2330 reflections with I > 2σ(I)
R _int = 0.089

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.101
S = 0.89
5222 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 1.21 e Å⁻³
Δρ_min = −0.83 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) I. DOI: 10.1107/S1600536811036051/ng5226sup1.cif

e-67-m1351-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036051/ng5226Isup2.hkl

e-67-m1351-Isup2.hkl^{(255.8KB, hkl)}

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

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 crystal structure of the title complex, [MnI₂(bipy)₂] (bipy = 2,2'-bipyridine, C₁₀H₈N₂), was previously reported in the monoclinic space group P2₁/c (Ha, 2011). The structure presented herein is essentially the same as the published structure and represents a new monoclinic polymorph with the space group C2/c.

The Mn^II ion in the complex is six-coordinated in a considerably distorted octahedral environment by four N atoms of the two chelating bipy ligands and two iodide anions in a cis-N₄I₂ coordination geometry (Fig. 1). The tight N—Mn—N chelating angles and the I—I repelling (Table 1) contribute the distortion of the ocataheron, which results in non-linear trans axes [<I1—Mn1—N1 = 169.67 (14)°, <I2—Mn1—N3 = 166.94 (15)° and <N2—Mn1—N4 = 153.33 (19)°]. The Mn—I bond lengths are nearly equal, but the Mn—N bond distances occur in two distinct sets, because of the different trans effects of the N and I atoms (Table 1). The Mn—N bonds trans to the I atom are slightly longer than the Mn—N bonds trans to the N atom. The dihedral angle between the nearly planar bipy ligands [maximum deviation = 0.064 (7) Å] is 75.0 (1)°. The dihedral angles between the pyridyl rings containing N1 and N2 as well as N3 and N4 are 4.5 (5)° and 4.1 (5)°, respectively. In the crystal structure, the complex displays numerous inter- and intramolecular π-π interactions between the pyridyl rings, the shortest ring centroid-centroid distance being 3.905 (5) Å (Fig. 2).

Experimental

To a solution of MnI₂ (0.3078 g, 0.997 mmol) in EtOH (30 ml) was added 2,2'-bipyridine (0.3131 g, 2.005 mmol) and stirred for 3 h at room temperature. The precipitate was separated by filtration, washed with acetone and dried at 50 °C, to give a yellow powder (0.0854 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution.