Poly[[hexa­kis­(μ-benzene-1,4-dicarboxyl­ato)octa­kis­(N,N-dimethyl­acetamide)­hexa­manganese(II)] monohydrate]

Ying Zhang; Chao-Xia Chu; Yi-Zhi Li

doi:10.1107/S1600536811020010

. 2011 Jun 4;67(Pt 7):m843–m844. doi: 10.1107/S1600536811020010

Poly[[hexakis(μ-benzene-1,4-dicarboxylato)octakis(N,N-dimethylacetamide)hexamanganese(II)] monohydrate]

Ying Zhang ^a,^*, Chao-Xia Chu ^a, Yi-Zhi Li ^b

PMCID: PMC3151841 PMID: 21836847

Abstract

In the title compound, {[Mn₆(C₈H₄O₄)₆(C₄H₉NO)₈]·H₂O}_n, two of the Mn atoms are six-coordinated by six O atoms from three benzene-1,4-dicarboxylate (bdc) ligands and two trans DMA (dimethylacetamide) molecules, whereas two other Mn atoms, located on inversion centers, are both in octahedral coordinations by six bdc O atoms. The discrete trinuclear manganese secondary building units (SBU) of Mn₃(O₂CR)₆ ({–Mn—Mn—Mn-}) are linked through bdc ligands, forming a chain, while the discrete trinuclear SBU of {–Mn—Mn—Mn-} are bridged, forming another chain]. The two types of chains are linked through bdc ligands, resulting in the formation of a layer with 3⁶ topology. Weak O—H⋯O and O—H⋯N hydrogen-bonding interactions involving the disordered water molecule (half-occupation) extend the two-dimensional layers into a three-dimensional supramolecular framework.

Related literature

For related structures, see: Hawxwell et al. (2006 ▶); He et al. (2006 ▶); Williams et al. (2005 ▶). For general background to porous materials, see: Li et al. (2009 ▶).

Experimental

Crystal data

[Mn₆(C₈H₄O₄)₆(C₄H₉NO)₈]·H₂O
M _r = 2029.30
Triclinic,
a = 9.924 (9) Å
b = 14.533 (13) Å
c = 16.990 (16) Å
α = 69.947 (13)°
β = 86.549 (14)°
γ = 83.807 (14)°
V = 2288 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 291 K
0.18 × 0.16 × 0.14 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.776, T _max = 0.815
18098 measured reflections
8890 independent reflections
6477 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.121
S = 1.04
8890 reflections
591 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020010/bx2348sup1.cif

e-67-0m843-sup1.cif^{(40.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020010/bx2348Isup2.hkl

e-67-0m843-Isup2.hkl^{(434.8KB, 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
O17—H17B⋯O16ⁱ	0.85	2.61	3.236 (7)	131
O17—H17B⋯N4ⁱ	0.85	2.62	3.463 (8)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

The work was supported by the Project of the Priority Academic Program Development of Jiangsu Higher Education Institutions.

supplementary crystallographic information

Comment

Metal-organic frameworks (MOFs) are currently under massive investigation due to their fascinating properties and high potential as a new class of porous materials (Li et al., 2009). Our particular interest is to construct three-dimensional (three-dimensional) frameworks with more open porosity using benzene-1,4-dicarboxylicacid (H₂bdc) and pillar bidentate ligands as mixed ligands, and to probe the influence of pillar ligands on the topological networks. Recently, we have employed the pillar bidentate ligand 4,4'-azopyridine. Unexpectedly, a new MOF without the pillared ligand, {[Mn₆(bdc)₆(DMA)₈].H₂O}_n, has been obtained.

The title compound contains two types of crystallographically equivalent six-coordinated Mn centers, and bdc ligands adopt two coordination modes. Mn1 and Mn4 atoms are both six-coordinated to six oxygen atoms from three bdc ligands and two trans-DMA molecules,whereas Mn2 and Mn3 located on an inversion center are both in octahedral coordination with six oxygen atoms of bdc species. The average bond distances of Mn1—O, Mn2—O, Mn3—O, and Mn4—O are 2.213, 2.167, 2.146, and 2.207 Å, respectively. The discrete trinuclear manganese secondary building unit (SBU) of Mn₃(O₂CR)₆ ({–Mn4—Mn3—Mn4-}) are linked through bdc ligands to form a one-dimensional chain, while the discrete trinuclear SBU of {–Mn1—Mn2—Mn1-} are bridged to form another one-dimensional chain.Two types of one-dimensional chains are linked through bdc ligands, resulting in the formation of a two-dimensional layer with 3⁶ topology. The 3⁶ net also displays an interdigitated structure, with the interplanar distance between adjacent nets being 7.043 Å. The structure of the 3⁶ layer has been also observed in other MOFs (Hawxwell et al., 2006; He et al., 2006; Williams et al., 2005).The weak hydrogen-bonding interactions extend the two-dimensional layers into a three-dimensional supramolecular framework.

Experimental

A mixture of MnCl₂.4H₂O (0.0198 g, 0.1 mmol), benzene-1,4-dicarboxylic acid (0.0166 g, 0.1 mmol), 4,4'-azopyridine (0.0184 g, 0.1 mmol) combined with 6 ml DMA was stirred for 20 min at room temperature. Then the solution was heated solvothermally in a 25 ml Teflon-lined stainless-steel vessel at 160 ^oC for 72 h under autogenous pressure. Slow cooling of the resulting solution to room temperature at the rate of 10 ^oC.h^-1 afforded colorless block-shaped crystals suitable for single-crystal X-ray structure analysis. Yield based on based on MnCl₂.4H₂O: 41%.