cis-Aqua­bis­(2,2′-bipyrimidine-κ2 N 1,N 1′)iodidomanganese(II) iodide dihydrate

Kwang Ha

doi:10.1107/S1600536811037810

. 2011 Sep 30;67(Pt 10):m1414. doi: 10.1107/S1600536811037810

cis-Aquabis(2,2′-bipyrimidine-κ² N ¹,N ^1′)iodidomanganese(II) iodide dihydrate

Kwang Ha ^a,^*

PMCID: PMC3201460 PMID: 22065136

Abstract

The asymmetric unit of the title compound, [MnI(C₈H₆N₄)₂(H₂O)]I·2H₂O, contains a cationic Mn^II complex, an I⁻ anion and two solvent water molecules. In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by four N atoms of the two chelating 2,2′-bipyrimidine (bpym) ligands, one I⁻ anion and one O atom of a water ligand. As a result of the different trans effects of the I and O atoms, the Mn—N bond trans to the I atom is slightly longer than the Mn—N bond trans to the O atom. The dihedral angle between the least-squares planes of the two bpym ligands [maximum deviation = 0.088 (4) Å] is 76.48 (6)°. In the crystal, the complex cation, the anion and the solvent water molecules are linked by intermolecular O—H⋯O, O—H⋯I and O—H⋯N hydrogen bonds.

Related literature

For the crystal structures of mononuclear 2,2′-bipyrimidine Mn^II complexes, see: Hong et al. (1996 ▶); Smith et al. (2001 ▶); Ha (2011 ▶).

Experimental

Crystal data

[MnI(C₈H₆N₄)₂(H₂O)]I·2H₂O
M _r = 679.12
Monoclinic,
a = 14.2105 (12) Å
b = 21.5452 (19) Å
c = 7.7064 (7) Å
β = 102.063 (2)°
V = 2307.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.28 mm⁻¹
T = 200 K
0.25 × 0.23 × 0.11 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.838, T _max = 1.000
17004 measured reflections
5707 independent reflections
3555 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 1.05
5707 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −1.15 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/S1600536811037810/aa2026sup1.cif

e-67-m1414-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037810/aa2026Isup2.hkl

e-67-m1414-Isup2.hkl^{(279.4KB, hkl)}

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

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

Mn1—O1	2.131 (3)
Mn1—N1	2.253 (4)
Mn1—N4	2.266 (4)
Mn1—N5	2.270 (4)
Mn1—N8	2.310 (4)
Mn1—I1	2.8070 (8)

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N1—Mn1—N4	72.96 (13)
N5—Mn1—N8	72.47 (13)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.84	1.93	2.753 (4)	166
O1—H1B⋯O2ⁱ	0.84	1.87	2.693 (4)	166
O2—H2A⋯I2	0.84	2.63	3.419 (3)	157
O2—H2B⋯N6ⁱⁱ	0.84	2.16	2.948 (5)	157
O2—H2B⋯N7ⁱⁱ	0.84	2.29	2.884 (5)	128
O3—H3A⋯I2	0.84	2.82	3.624 (4)	161
O3—H3B⋯I2ⁱⁱⁱ	0.84	2.73	3.517 (4)	157

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

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

Mononuclear Mn^II complexes of 2,2'-bipyrimidine (bpym, C₈H₆N₄) ligand, such as [Mn(bpym)₂(H₂O)₂](ClO₄)₂^.2H₂O (Hong et al., 1996), [Mn(bpym)₂(H₂O)₂](BF₄)₂^.2H₂O (Smith et al., 2001) and [MnBr₂(bpym)₂]^.CH₃CN (Ha, 2011), have been investigated previously.

The asymmetric unit of the title compound, [MnI(bpym)₂(H₂O)]I^.2H₂O, contains a cationic Mn^II complex, an I^- anion and two solvate water molecules (Fig. 1). In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by four N atoms of the two chelating bpym ligands, one I^- anion and one O atom of a water ligand in a cis-N₄IO coordination geometry. The main contribution to the distortion of the ocataheron is the tight N—Mn—N chelating angles (Table 1), which results in non-linear trans axes [<O1—Mn1—N1 = 167.23 (13)°, <I1—Mn1—N8 = 172.44 (9)° and <N4—Mn1—N5 = 158.58 (13)°]. The Mn—N(bpym) bond lengths are slightly different and longer than the Mn—O(H₂O) bond (Table 1). Because of the different trans effects of the I and O atoms, the Mn1—N8 bond trans to the I atom is somewhat longer than the Mn1—N1 bond trans to the O atom. The dihedral angle between the least-squares planes of the two bpym ligands [maximum deviation = 0.088 (4) Å] is 76.48 (6)°. In the crystal structure, the complex, anion and solvate water molecules are linked by intermolecular O—H···O, O—H···I and O—H···N hydrogen bonds (Fig. 2, Table 2). In addition, the complexes display numerous inter- and intramolecular π-π interactions between adjacent pyrimidine rings, the shortest ring centroid-centroid distance being 3.611 (2) Å.

Experimental

To a solution of 2,2'-bipyrimidine (0.1587 g, 1.003 mmol) in acetone (40 ml) was added MnI₂ (0.1540 g, 0.499 mmol) and refluxed for 3 h. The formed precipitate was separated by filtration, washed with acetone and dried at 50 °C, to give a yellow powder (0.0701 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution.