catena-Poly[[[tetra­aqua­manganese(II)]-μ-4,4′-bipyridine] bis­(3-hydroxy­cinnamate) dihydrate]

Zhi-Wei Tang; Jun-Dan Fu; Long-Ping Jiang; Yi-Hang Wen

doi:10.1107/S1600536809028360

. 2009 Jul 22;65(Pt 8):m979. doi: 10.1107/S1600536809028360

catena-Poly[[[tetraaquamanganese(II)]-μ-4,4′-bipyridine] bis(3-hydroxycinnamate) dihydrate]

Zhi-Wei Tang ^a, Jun-Dan Fu ^a, Long-Ping Jiang ^a, Yi-Hang Wen ^a,^*

PMCID: PMC2977154 PMID: 21583422

Abstract

The title compound, {[Mn(C₁₀H₈N₂)(H₂O)₄](C₉H₇O₃)₂·2H₂O}_n, was obtained by the hydrothermal reaction of manganese chloride with mixed 3-hydroxylcinnamic acid (H₂ L) and 4,4′-bipyridine (4,4′-bipy) ligands. The structure contains [Mn(C₁₀H₈N₂)(H₂O)₄]²⁺ cations with the Mn^II atoms lying on a centres of inversion and bridged into a linear chain along the a axis by 4,4′-bipy ligands, surrounded by HL ⁻ anions and uncoordinated water molecules. Extensive O—H⋯O hydrogen-bonding and weak π–π interactions [centroid–centroid distance = 3.7572 (3) Å] between the constituents lead to the formation of a three-dimensional supramolecular network.

Related literature

For potential applications of compounds with supramolecular architectures, see: Niu et al. (2008 ▶); Xue et al. (2007 ▶); Ye et al. (2005 ▶); Zhang et al. (2009 ▶). For the synthesis of supramolecular coordination compounds containing 4-pyridyl and carboxylate groups, see: Feng et al. (2008 ▶); He et al. (2007 ▶); Li et al. (2008 ▶).

Experimental

Crystal data

[Mn(C₁₀H₈N₂)(H₂O)₄](C₉H₇O₃)₂·2H₂O
M _r = 645.51
Monoclinic,
a = 11.6620 (12) Å
b = 11.2726 (13) Å
c = 11.6238 (13) Å
β = 96.520 (9)°
V = 1518.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.21 × 0.14 × 0.07 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.92, T _max = 0.97
13208 measured reflections
3513 independent reflections
2293 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.118
S = 1.04
3513 reflections
217 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.31 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028360/at2846sup1.cif

e-65-0m979-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028360/at2846Isup2.hkl

e-65-0m979-Isup2.hkl^{(172.3KB, 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
O3W—H3WA⋯O2ⁱ	0.832 (16)	1.912 (18)	2.738 (2)	171 (3)
O1W—H1WA⋯O1ⁱⁱ	0.833 (17)	1.888 (17)	2.719 (2)	174 (3)
O2W—H2WA⋯O3Wⁱⁱⁱ	0.815 (17)	2.024 (17)	2.838 (3)	176 (3)
O3W—H3WB⋯O2^iv	0.842 (16)	1.902 (18)	2.741 (2)	174 (3)
O2W—H2WB⋯O1^v	0.832 (16)	1.878 (16)	2.702 (2)	171 (3)

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

supplementary crystallographic information

Comment

The construction of supramolecular architectures based on metal and organic building blocks is currently of great interest for their aesthetic architectures and potential functions such as adsorption, ion exchange, magnetic and luminescent materials (Niu et al., 2008; Xue et al., 2007; Ye et al., 2005; Zhang et al., 2009). Recently, we are interested in the synthesis of novel supramolecular coordination compounds which contain not only 4-pyridyl but also carboxylate groups in the crystal structure (He et al., 2007; Feng et al., 2008; Li et al., 2008). Here we report the crystal structure of the title compound, [Mn(C₁₀H₈N₂)(H₂O)₄]₂.2(C₉H₇O₃).2H₂O, (I).

The present X-ray single-crystal diffraction study reveals that (I) is a new coordination polymer involving Mn²⁺ and 3-hydroxycinnamate anions, as shown in Fig. 1. The Mn^II is hexacoordinated in an octahedral manner by four water molecules in the equatorial plane and two N atoms in the axial positions from two 4,4'-bipyridine molecules. The bond lengths of Mn—N and Mn—O are 2.2863 (17) Å and in the range 2.1641 (15)—2.1675 (17) Å, respectively. As shown in Fig. 2, the linear cationic chains, 3-Hydroxycinnamate anions and lattice water molecules are linked together through a series of O—H···O bonds with the hydrogen bonds lengths in the range of 2.702 (2)—2.838 (3) Å and bond angles between 171 (3) and 176 (3) °. The extensive hydrogen bonds together with the weak π-π interactions between hca^- anions and 4,4'-bipyridine (the centroid-to-centroid distance is 3.7572 Å) stabilize the crystal structure, forming a three-dimensional network.

Experimental

MnCl₂.4H₂O (0.0973 g, 0.5 mmol), 3-hydroxycinnamic acid (0.1619 g, 1 mmol), NaOH (0.0405 g, 1 mmol), 4,4'-bipy (0.1562 g, 1 mmol) and H₂O-ethanol (4:1, 15 mL) was sealed in a 25 ml stainless-steel reactor with a Telflon liner and was heated at 433 K for 3 d, then the reactor was cooled slowly to room temperature. The solution was filtered, giving yellow single crystals suitable for X-ray analysis in yield 30%.