Poly[tetra­aqua­(μ6-9,10-dioxo-9,10-dihydro­anthracene-1,4,5,8-tetra­carboxyl­ato)dimanganese(II)]

Rui Xu; Jian-Lan Liu

doi:10.1107/S1600536812027158

. 2012 Jun 20;68(Pt 7):m957. doi: 10.1107/S1600536812027158

Poly[tetraaqua(μ₆-9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylato)dimanganese(II)]

Rui Xu ^a, Jian-Lan Liu ^a,^*

PMCID: PMC3393211 PMID: 22807779

Abstract

The title complex, [Mn₂(C₁₈H₄O₁₀)(H₂O)₄]_n, was synthesized from manganese(II) chloride tetrahydrate and 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylic acid (H₄AQTC) in water. The anthraquinone unit is located about a crystallographic center of inversion. Each asymmetric unit therefore contains one Mn^II atom, two water ligands and one half AQTC⁴⁻ anion. The Mn^II atom is coordinated in a distorted octahedral geometry by four O atoms from three AQTC⁴⁻ ligands and two water O atoms. Two of the carboxylate groups coordinate one Mn^II atom in a chelating mode, whereas the others each coordinate two Mn^II atoms. Each AQTC⁴⁻ tetra-anion therefore coordinates six different Mn^II ions and, as a result, a three-dimensional coordination polymer is formed. O—H⋯O hydrogen bonds, some of them bifurcated, between water ligands and neighboring water or anthraquinone ligands are observed in the crystal structure.

Related literature

For general background to metal-organic frameworks, see: Li et al. (1999 ▶, 2012 ▶); Cheng et al. (2010 ▶); Hong et al. (2009 ▶); Miller & Gatteschi (2011 ▶); Liu et al. (2010 ▶).

Experimental

Crystal data

[Mn₂(C₁₈H₄O₁₀)(H₂O)₄]
M _r = 562.16
Monoclinic,
a = 11.2255 (16) Å
b = 8.4153 (13) Å
c = 9.7252 (14) Å
β = 92.355 (2)°
V = 917.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 273 K
0.46 × 0.32 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.553, T _max = 0.702
4340 measured reflections
1609 independent reflections
1499 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.076
S = 1.08
1609 reflections
170 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.41 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027158/im2383sup1.cif

e-68-0m957-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027158/im2383Isup2.hkl

e-68-0m957-Isup2.hkl^{(79.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H3⋯O2ⁱ	0.78 (3)	2.03 (3)	2.775 (2)	160 (3)
O8—H4⋯O3ⁱⁱ	0.89 (4)	1.86 (4)	2.742 (2)	174 (3)
O8—H4⋯O6ⁱⁱ	0.89 (4)	2.60 (3)	3.159 (2)	121 (3)
O9—H5⋯O8ⁱⁱⁱ	0.81 (1)	2.03 (1)	2.832 (3)	168 (4)
O9—H6⋯O6ⁱⁱ	0.81 (1)	2.38 (2)	3.135 (3)	157 (5)
O9—H6⋯O7ⁱⁱⁱ	0.81 (1)	2.50 (4)	3.031 (3)	124 (4)

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Porous solid materials, such as MOFs (metal-organic frameworks) have been widely studied for their potential applications in gas absorption, separation, catalysis and magnetic materials. Explorations of advanced porous materials for these applications are an intense subject of scientific research (Li et al.,1999; Li et al., 2012; Cheng et al., 2010; Hong et al., 2009; Miller & Gatteschi, 2011; Liu et al., 2010.) Herein we report the crystal structure of the title compound.

The molecular structure of (I) is illustrated in Fig. 1., a summary of the observed hydrogen bonds and the corresponding angles are given in Table 1.

Each asymmetric unit therefore contains one manganese(II) atom, two water ligands and one half AQTC^4- ligand. The coordination sphere around manganese is distorted octahedral due to the coordination of four O atoms from three AQTC^4- ligands and two O atoms from two water molecules. Two of the carboxylate groups coordinate one manganese in a chelating mode whereas the others each coordinate two manganese center. Each AQTC^4-therefore coordinates six different manganese ions and as a result a three-dimensional coordination polymer is formed.

Experimental

A mixture of 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylic acid (H₄AQTC; 0.025 mmol, 9.8 mg) was added to distilled water (4 ml) and ultra-sounded for 10 min. The pH value of the mixture was then adjusted to 7.0 with sodium hydroxide (0.5 mol L^-1), prior to the addition of manganese(II) chloride tetrahydrate (0.05 mmol, 9.9 mg). The reactants were placed in a Teflon-lined stainless steel vessel, heated for 3 days, and then cooled to ambient temperature over 12 h. The solution was exposed to air for three days leading to the precipitation of brown crystals (yield 10%).