Bis[(2-pyrid­yl)(2-pyridyl­amino)­methano­lato]manganese(III) nitrate

Shuai Ding; Congjun Xia; Yufei Ji; Zhiliang Liu; Yong Ding

doi:10.1107/S1600536811014371

. 2011 Apr 22;67(Pt 5):m622–m623. doi: 10.1107/S1600536811014371

Bis[(2-pyridyl)(2-pyridylamino)methanolato]manganese(III) nitrate

Shuai Ding ^a, Congjun Xia ^b, Yufei Ji ^a, Zhiliang Liu ^a,^*, Yong Ding ^b

PMCID: PMC3089209 PMID: 21754334

Abstract

The Mn^III atom in the title complex, [Mn(C₁₁H₁₀N₃O)₂]NO₃, is coordinated by the two tridentate (2-pyridyl)(2-pyridylamino)methanolate ligands, forming a six-coordinate environment. The four pyridyl N atoms constitute the equatorial plane on which the manganese(III) ion lies; the coordination plane suffers a slight distortion as indicated by the average plane deviation of 0.058 Å. The methanolate O atoms occupy the axial positions. The coordination geometry is thus octahedral. In the title compound, the cations are linked by nitrate anions via N—H⋯O hydrogen bonds to form one-dimensional chains. Moreover, the one-dimensional structure is stabilized by intermolecular edge-to-face aromatic π–π interactions with a center-of-inversion at a distance of ca 4.634 Å.

Related literature

For related structures, see: Adams et al. (2005 ▶); Liu et al. (2008 ▶); Arulsamy & Hongson (1994 ▶).

Experimental

Crystal data

[Mn(C₁₁H₁₀N₃O)₂]NO₃
M _r = 517.39
Monoclinic,
a = 12.889 (3) Å
b = 10.931 (2) Å
c = 19.309 (6) Å
β = 123.34 (2)°
V = 2272.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 153 K
0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.963, T _max = 0.969
16544 measured reflections
5743 independent reflections
4648 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.166
S = 1.07
5743 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶) and XP (Siemens, 1994 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014371/zk2005sup1.cif

e-67-0m622-sup1.cif^{(25KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014371/zk2005Isup2.hkl

e-67-0m622-Isup2.hkl^{(281.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O2	1.8428 (17)
Mn1—O1	1.8488 (17)
Mn1—N6	2.111 (2)
Mn1—N4	2.139 (2)
Mn1—N3	2.179 (2)
Mn1—N5	2.202 (2)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	2.08	2.931 (4)	171
N2—H2⋯O4ⁱⁱ	0.86	2.07	2.902 (4)	164

Open in a new tab

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

Acknowledgments

Financial support by the NSFC (grant Nos. 20761004 and 21061009) and the Inner Mongolia Autonomous Region Fund for Natural Science (grant No. 2010MS0201) is gratefully acknowledged. This work was supported by the ‘211 project’ postgraduate student programme of Inner Mongolia University.

supplementary crystallographic information

Comment

Selected bond distances and angles are given in Table 1. (2-pyridyl)(2-pyridylamino)-methanolato is a transmutative ligand. There is only four complexes with this ligand reported, such as those of Mn^III (Liu et al. 2008), Co^III (Adams et al. 2005) and Mn^III, Fe^III (Arulsamy & Hongson 1994). We report herein the synthesis and structure of the title compound. The crystal structure of the complex cation shows two tridentate (2-pyridyl)bis(2-pyridylamino)-methanolate ligands coordinated facially to the Mn^III ion to form a distorted octahedral geometry. The Mn^III resides on a pseudo-twofold axis of symmetry and on an equatorial plane formed by the pyridyl N atoms of the two ligands (Fig. 2, Table 2).

Experimental

L¹ was synthesized following literature procedures (Arulsamy & Hongson 1994). 50% Mn(NO₃)₂ (0.356 g, 1 mmol) was added to a solution of L¹ (0.277 g, 1 mmol) in ehanol (20 ml); a brown solution formed over time with continuous stirring at room temperature. This solution was left to evaporate slowly at room temperature. After one week, brown block crystals of the title compound were isolated (yield: 0.1662 g, 60%). Microanalysis found: C 50.91, H 3.89, N 18.90%; calculated for C₂₂H₂₀MnN₇O₅ (Mr = 517.39): C 51.02, H 3.86, N 18.94%.