Diaqua­iodido(2,3,5,6-tetra-2-pyridyl­pyrazine-κ3 N 2,N 1,N 6)manganese(II) iodide monohydrate

Kwang Ha

doi:10.1107/S1600536811035434

. 2011 Sep 14;67(Pt 10):m1333. doi: 10.1107/S1600536811035434

Diaquaiodido(2,3,5,6-tetra-2-pyridylpyrazine-κ³ N ²,N ¹,N ⁶)manganese(II) iodide monohydrate

Kwang Ha ^a,^*

PMCID: PMC3201512 PMID: 22058685

Abstract

The asymmetric unit of the title compound, [MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O, consists of a cationic Mn^II complex, an I⁻ anion and a solvent water molecule. In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz) ligand, one I⁻ anion and two O atoms of two water ligands. The dihedral angles between the pyridyl rings [maximum deviation = 0.034 (6) Å] and their carrier pyrazine ring [maximum deviation = 0.020 (6) Å] are 26.5 (2) and 27.0 (2)° for the coordinated pyridyl rings, and 51.3 (3) and 43.2 (2)° for the uncoordinated pyridyl rings. Intermolecular O—H⋯O, O—H⋯N and O—H⋯I hydrogen bonds stabilize the crystal structure.

Related literature

For the crystal structures of mono- and dinuclear Mn^II complexes with tppz, see: Callejo et al. (2009 ▶); Ha (2011 ▶).

Experimental

Crystal data

[MnI(C₂₄H₁₆N₆)(H₂O)₂]I·H₂O
M _r = 751.22
Monoclinic,
a = 7.977 (3) Å
b = 13.880 (5) Å
c = 12.134 (4) Å
β = 97.944 (7)°
V = 1330.5 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.85 mm⁻¹
T = 200 K
0.28 × 0.20 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.828, T _max = 1.000
9685 measured reflections
5463 independent reflections
4463 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.115
S = 1.23
5463 reflections
325 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −1.41 e Å⁻³
Absolute structure: Flack (1983 ▶); 2033 Friedel pairs
Flack parameter: −0.01 (4)

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/S1600536811035434/zq2121sup1.cif

e-67-m1333-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035434/zq2121Isup2.hkl

e-67-m1333-Isup2.hkl^{(267.5KB, hkl)}

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

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

Mn1—O1	2.163 (6)
Mn1—O2	2.182 (6)
Mn1—N6	2.245 (7)
Mn1—N1	2.253 (7)
Mn1—N3	2.259 (7)
Mn1—I1	2.7772 (16)

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N6—Mn1—N1	71.7 (3)
N1—Mn1—N3	71.4 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱ	0.84	1.92	2.726 (10)	160
O1—H1B⋯N2ⁱⁱ	0.84	2.10	2.890 (10)	156
O2—H2A⋯N4ⁱⁱⁱ	0.84	2.04	2.876 (10)	174
O2—H2B⋯N5ⁱⁱⁱ	0.84	2.03	2.834 (10)	160
O3—H3A⋯I1^iv	0.84	2.88	3.615 (9)	148
O3—H3B⋯I2	0.84	2.83	3.646 (8)	163

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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

Mono- and dinuclear Mn^II complexes of 2,3,5,6-tetra-2-pyridylpyrazine (tppz; C₂₄H₁₆N₆) ligand, such as [Mn(C₂N₃)(NO₃)(tppz)(H₂O)] (Callejo et al., 2009) and [Mn₂Cl₄(tppz)₂] (Ha, 2011), have been investigated previously.

The asymmetric unit of the title compound, [MnI(tppz)(H₂O)₂]I.H₂O, consists of a cationic Mn^II complex, an I^- anion and a solvent water molecule (Fig. 1). In the complex, the Mn^II ion is six-coordinated in a considerably distorted octahedral environment defined by three N atoms of the tridentate tppz ligand, one I^- anion and two O atoms of two water ligands. The main contribution to the distortion is the tight N—Mn—N chelating angles (Table 1), which results in non-linear trans arrangement of the N3—Mn1—N6 bond [N3—Mn1—N6 = 143.1 (3)°]. The apical O1—Mn1—O2 and I1—Mn1—N1 bond angles are 167.0 (2)° and 173.04 (19)°, respectively. The three Mn—N(pyrazine or pyridyl) bond lengths are roughly equivalent and slightly longer than the Mn—O(H₂O) bonds (Table 1). In the crystal structure, the pyrazine and pyridyl rings are nearly planar [maximum deviation = 0.020 (6) Å for pyrazine and 0.034 (6) Å for pyridyl]. The dihedral angles between the pyridyl rings and their carrier pyrazine ring are 26.5 (2)° and 27.0 (2)° for the coordinated pyridyl rings, and 51.3 (3)° and 43.2 (2)° for the uncoordinated pyridyl rings, respectively. The complex, anion and solvent water molecule are linked by intermolecular O—H···O, O—H···N and O—H···I hydrogen bonds (Fig. 2, Table 2). In addition, the complex displays numerous inter- and intramolecular π-π interactions between adjacent six-membered rings, the shortest ring centroid-centroid distance being 4.032 (5) Å.

Experimental

To a suspension of 2,3,5,6-tetra-2-pyridylpyrazine (0.1945 g, 0.501 mmol) in acetone (20 ml) was added MnI₂ (0.1575 g, 0.510 mmol) in acetone (30 ml) and refluxed for 5 h. The formed precipitate was separated by filtration, washed with acetone and dried at 50 °C, to give an orange powder (0.0779 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a 2-butanone solution.