Poly[[bis­(2,2-bipyridine)­bis­[μ6-5-(carboxyl­atometh­oxy)benzene-1,3-dicarboxyl­ato]trimanganese(II)] monohydrate]

Zhan-Guo Jiang; Jing Chen; Yun-Long Feng

doi:10.1107/S1600536811002819

. 2011 Jan 26;67(Pt 2):m259–m260. doi: 10.1107/S1600536811002819

Poly[[bis(2,2-bipyridine)bis[μ₆-5-(carboxylatomethoxy)benzene-1,3-dicarboxylato]trimanganese(II)] monohydrate]

Zhan-Guo Jiang ^a, Jing Chen ^a, Yun-Long Feng ^a,^*

PMCID: PMC3051434 PMID: 21522911

Abstract

The title compound, {[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O}_n, was synthesized under hydrothermal conditions. Six carboxylate groups of six 5-(carboxylatomethoxy)benzene-1,3-dicarboxylate anions (OABDC³⁻) join three Mn^II ions into a trinuclear centrosymmetric [Mn₃(μ₂-COO)₆] unit with one Mn site situated on a centre of inversion. The latter Mn^II ion exhibits a distorted MnO₆ coordination, whereas the other Mn^II ion has a trigonal–bipyramidal MnN₂O₃ coordination environment resulting from three carboxylate O atoms and the two N atoms of the bipyridine ligand. Adjacent units are linked to each other by OABDC³⁻ ligands into a layer parallel to (010). Within the layer, O—H⋯O hydrogen-bonding interactions involving the uncoordinated and half-occupied water molecule and the free carboxylate O atoms are observed. The layers stack along [010], constructing a three-dimensional structure through π–π interactions between adjacent pyridine rings, with a centroid–centroid distance of 3.473 (5) Å.

Related literature

For the construction of metal-organic frameworks with polycarboxylate ligands, see: Xing et al. (2010 ▶); Cao et al. (2004 ▶, 2007 ▶).

Experimental

Crystal data

[Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]·H₂O
M _r = 969.48
Monoclinic,
a = 8.5683 (1) Å
b = 25.2280 (4) Å
c = 9.7685 (1) Å
β = 114.633 (1)°
V = 1919.41 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 296 K
0.37 × 0.19 × 0.09 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.786, T _max = 0.907
16528 measured reflections
3350 independent reflections
3012 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.123
S = 1.10
3350 reflections
292 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002819/wm2447sup1.cif

e-67-0m259-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002819/wm2447Isup2.hkl

e-67-0m259-Isup2.hkl^{(164.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O7ⁱ	2.100 (2)
Mn1—O3ⁱⁱ	2.148 (2)
Mn1—O1	2.175 (2)
Mn1—N2	2.228 (3)
Mn1—N1	2.251 (3)
Mn2—O4ⁱⁱⁱ	2.108 (2)
Mn2—O6^iv	2.159 (2)
Mn2—O1	2.322 (2)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2ⁱⁱⁱ	0.85 (1)	2.19 (2)	3.015 (5)	164 (6)

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Symmetry code: (iii) Inline graphic .

supplementary crystallographic information

Comment

Aromatic polycarboxylic acids like 1,3,5-benzenetricarboxylate (H₃btc) and 1,2,4,5-benzenetetracarboxylate (H₄btec) are widely used to construct metal-organic frameworks (Xing et al., 2010). Aromatic polycarboxylate ligands with rigid and flexible carboxyl group are less reported. 5-oxyacetato-1,3-benzenebiscarboxylic acid (H₃OABDC) is a ligand with two rigid carboxyl groups and one flexible oxyacetato group. Previous structural studies including this ligand have also been reported (Cao et al., 2004, 2007).

The title compound, [Mn₃(C₁₀H₅O₇)₂(C₁₀H₈N₂)₂]^.H₂O, crystallizes with two Mn^II ions (Mn1 on a general position, Mn2 on a centre of inversion), one OABDC^3- trianion, one chelating 2,2-bipyridine (bipy) ligand and one water molecule (half-occupied) in the asymmetric unit. Mn1 is five-coordinated by two N atoms from the bipy ligand, one O atom from one flexible carboxyl group of the OABDC^3- anion and two O atoms from two rigid carboxyl groups of the OABDC^3- anion to form a distorted trigonal-bipyramidal environment. Mn2 is six-coordinated by two O atoms from two flexible carboxyl groups of the OABDC^3- anion and four oxygen atoms from four rigid carboxyl groups of adjacent OABDC^3- anions to form a distorted octahedral environment (Table 1, Fig. 1).

Six OABDC^3- anions join three Mn^II ions through their carboxyl groups. As a result, trinuclear [Mn₃(µ₂-COO)₆]_n layers are formed in which Mn2 sits on a centre of inversion of each trinuclear unit. These layers are oriented parallel to (010). Uncoordinated water molecules interact with non-bonded O atoms of the carboxylate groups within the layers through relatively weak O—H···O hydrogen-bonding interactions (Table 2, Fig. 2).

The bipy ligands decorate the top and bottom of each layer. Between parallel pyridine rings of adjacent layers exist π–π interactions with a centroid- centroid distance of 3.473 (5) Å that consolidate the packing of the structure along [010] into a three-dimensional framework (Fig. 3).

Experimental

All reagents were purchased commercially and used without further purification. A mixture of 5-oxyacetato-1,3-benzenebiscarboxylic acid (H₃OABDC; 0.1205 g, 0.5 mmol), MnCl₂^.4H₂O (0.0976 g, 0.5 mmol), bipyridine (0.0786 g, 0.5 mmol), was dissolved with NaOH (0.0101 g, 0.25 mmol) in water (15 ml) and loaded in a 25 ml stainless steel reactor with a telflon liner. The autoclave was heated at 433 K for 72 h, and then cooled to room temperature over 3 days with a cooling rate of 5 K per hour. Yellow single crystals of the title compound were obtained by slow evaporation of the filtrate over a few days.