Tetra­aqua­(2,2′-bipyridine-κ2 N,N′)manganese(II) di-μ-aqua-bis­[aqua­(2,2′-bipyridine-κ2 N,N′)(5-sulfonatoisophthalato-κO)manganate(II)] tetra­hydrate

Bing-Yu Zhang; Jing-Jing Nie; Duan-Jun Xu

doi:10.1107/S1600536808020540

. 2008 Jul 9;64(Pt 8):m1003–m1004. doi: 10.1107/S1600536808020540

Tetraaqua(2,2′-bipyridine-κ² N,N′)manganese(II) di-μ-aqua-bis[aqua(2,2′-bipyridine-κ² N,N′)(5-sulfonatoisophthalato-κO)manganate(II)] tetrahydrate

Bing-Yu Zhang ^a, Jing-Jing Nie ^a, Duan-Jun Xu ^a,^*

PMCID: PMC2961927 PMID: 21202998

Abstract

The crystal structure of the title salt, [Mn(C₁₀H₈N₂)(H₂O)₄][Mn₂(C₈H₃O₇S)₂(C₁₀H₈N₂)₂(H₂O)₄]·4H₂O, consists of mononuclear manganese(II) cations, dinuclear manganate(II) dianions and uncoordinated water molecules. The dianion is located about an inversion center; the Mn^II atom is coordinated by a 2,2′-bipyridine ligand, a sulfonatoisophthalate group, a water molecule along with two bridging water molecules in an octahedral geometry. The cation lies on a twofold rotation axis; the Mn^II atom is coordinated by four water molecules and a chelating 2,2′-bipyridine ligand in a distorted octahedral geometry. A partially overlapped arrangement between the bipyridine ligands and the aromatic ring of the sulfoisophthalate group of adjacent anions is observed; the distance (3.357 Å) indicates π–π stacking. Hydrogen bonds, with the water molecules serving as hydrogen-bond donors, lead to a three-dimensional network architecture.

Related literature

For general background, see: Deisenhofer & Michel (1989 ▶); Pan et al. (2006 ▶); Su & Xu (2004 ▶). For a related structure, see: Zhang et al. (2008 ▶). For the thickness of the aromatic ring, see: Cotton & Wilkinson (1972 ▶).

Experimental

Crystal data

[Mn(C₁₀H₈N₂)(H₂O)₄][Mn₂(C₈H₃O₇S)₂(C₁₀H₈N₂)₂(H₂O)₄]·4H₂O
M _r = 1335.89
Monoclinic,
a = 19.656 (4) Å
b = 9.1286 (17) Å
c = 32.035 (6) Å
β = 96.584 (7)°
V = 5710.1 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 295 (2) K
0.40 × 0.36 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.742, T _max = 0.850
32384 measured reflections
6179 independent reflections
4071 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.123
S = 1.09
6179 reflections
375 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020540/ng2471sup1.cif

e-64-m1003-sup1.cif^{(24KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020540/ng2471Isup2.hkl

e-64-m1003-Isup2.hkl^{(296.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—N1	2.253 (3)
Mn1—N2	2.212 (3)
Mn1—O1	2.116 (2)
Mn1—O1W	2.278 (2)
Mn1—O1Wⁱ	2.305 (2)
Mn1—O2W	2.161 (2)
Mn2—N3	2.282 (3)
Mn2—O3W	2.145 (2)
Mn2—O4W	2.1707 (19)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O5W	0.85	1.87	2.701 (3)	164
O1W—H1B⋯O2	0.93	1.62	2.548 (3)	173
O2W—H2A⋯O3ⁱⁱ	0.85	1.87	2.716 (3)	170
O2W—H2B⋯O6ⁱⁱⁱ	0.89	1.91	2.789 (3)	167
O3W—H3A⋯O5^iv	0.90	1.85	2.746 (3)	176
O3W—H3B⋯O4ⁱⁱ	0.95	1.68	2.621 (3)	170
O4W—H4A⋯O3^v	0.95	1.82	2.727 (3)	157
O4W—H4B⋯O7^iv	0.89	1.90	2.780 (3)	168
O5W—H5A⋯O7ⁱⁱⁱ	0.95	1.83	2.770 (4)	170
O5W—H5B⋯O6Wⁱ	0.95	2.04	2.749 (5)	131
O6W—H6A⋯O6^vi	0.91	2.26	3.128 (5)	160
O6W—H6B⋯O3	0.92	2.27	3.109 (5)	151

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

Acknowledgments

This work was supported by the ZIJIN project of Zhejiang University, China.

supplementary crystallographic information

Comment

As π-π stacking between aromatic rings plays an important role in electron transfer process in some biological system (Deisenhofer & Michel, 1989), π-π stacking has attracted our much attention in past years (Su & Xu, 2004; Pan et al., 2006). In order to investigate the influence of substituents of the aromatic compounds on stacking between parallel aromatic rings, the title Mn^II compound incorporating sulfoisophthalate ligand has recently been prepared and its crystal structure is reported here.

The crystal structure of the title compound consists of dimeric Mn^II complex anions, monomeric Mn^II complex cations and lattice water molecules (Fig. 1).

The complex anion is located across on an inversion center, two independent parts are bridged by two water molecules with approximately identical Mn—O(bridge) bond distances (Table 1) and a normal Mn—O—Mnⁱ bond angle of 103.85 (8)° [symmetry code: (i) 1 - x, -y, 1 - z]. Each Mn^II ion is coordinated by one 2,2'-bipyridine (bipy) ligand, one sulfoisophtalate anion, two bridge water molecules and one terminal water molecule in a distorted octahedral geometry. The Mn—O(bridge) bond distances are significantly longer than Mn—O(terminal) bond distances. In the Mn₂O₂ core the Mn···Mn and O···O distances are 3.6071 (11) and 2.826 (4) Å, respectively. The benzene ring of sulfoisophthalate and bipy ring system coordinated to the same Mn^II ion are nearly co-planar, the dihedral angle being 2.62 (14)°.

The complex cation has twofold rotation symmetry, with the Mn2 and the mid-point of the C23—C23^II bond located on the twofold rotation axis [symmetry code: (ii) 1 - x, y, 3/2 - z]. The Mn2 ion is coordinated by four water molecules and chelated by one bipy in a distorted octahedral geometry.

Partially overlapped arrangement between nearly parallel [dihedral angle 3.49 (19)°] bipy and benzene ring of sulfoisophthalate of the adjacent complex anion is observed in the crystal structure (Fig. 2). The perpendicular distance of the centroid of the N2-pyridine ring on the C6ⁱⁱⁱ-benzene ring is 3.357 Å, and the perpendicular distance of the centroid of the C6ⁱⁱⁱ-benzene ring on the N2-pyridine ring is 3.425 Å, they are significantly shorter than the van der Waals thickness of the aromatic ring (Cotton & Wilkinson, 1972) and indicate the existence of π-π stacking involving sulfoisophthalate anion, similar to that found in a related Co^II complex with sulfoisophthalate ligand (Zhang et al., 2008).

The extensive O—H···O and C—H···O hydrogen bonding network presents in the crystal structure (Table 2), which helps to stabilize the crystal structure.

Experimental

The monosodium 5-sulfoisophthalate (0.27 g, 1 mmol), sodium carbonate (0.11 g, 1 mmol), 2,2'-bipyridine (0.16 g, 1 mmol), manganese chloride tetrahydrate (0.20 g, 1 mmol), water (8 ml) and ethanol (2 ml) were sealed in a 20-ml Teflon-lined, stainless-steel autoclave. The autoclave was heated to 398 K for 36 h and then cooled to room temperature over 24 h. The solution was filtered and the single crystals of the title compound were obtained from the filtrate after 10 d.