(μ-2,2′-Bipyrimidine-κ4 N 1,N 1′:N 3,N 3′)bis­[triaqua­(sulfato-κO)manganese(II)]

Kwang Ha

doi:10.1107/S160053681103604X

. 2011 Sep 14;67(Pt 10):m1349–m1350. doi: 10.1107/S160053681103604X

(μ-2,2′-Bipyrimidine-κ⁴ N ¹,N ^1′:N ³,N ^3′)bis[triaqua(sulfato-κO)manganese(II)]

Kwang Ha ^a,^*

PMCID: PMC3201432 PMID: 22064892

Abstract

The title complex, [Mn₂(SO₄)₂(C₈H₆N₄)(H₂O)₆], is the second monoclinic polymorph [De Munno et al. (1995 ▶). Inorg. Chem. 34, 408–411; Hong et al. (1996 ▶). Polyhedron, 15, 447–452]. The asymmetric unit contains two crystallographically independent half-molecules of the binuclear Mn^II complex; an inversion centre is located at the centroid of each complex. The two Mn^II atoms in each complex molecules are bridged by a bis-chelating 2,2′-bipyrimidine (bpym) ligand and each Mn^II atom is six-coordinated in a considerably distorted octahedral environment defined by two N atoms of the bridging bpym ligand and four O atoms from one sulfato anionic ligand and three water molecules. In the crystal, the complex molecules are linked by O—H⋯O hydrogen bonds between the water and sulfato ligands, forming a three-dimensional network.

Related literature

For the crystal structure of the title complex in the same space group but with different cell parameters, see: De Munno et al. (1995 ▶); Hong et al. (1996 ▶). For the synthesis and crystal structure of [Mn₂(H₂O)₈(bpym)](SO₄)₂·2H₂O, see: Ha (2011 ▶).

Experimental

Crystal data

[Mn₂(SO₄)₂(C₈H₆N₄)(H₂O)₆]
M _r = 568.26
Monoclinic,
a = 12.4401 (18) Å
b = 13.2640 (19) Å
c = 12.8951 (18) Å
β = 117.199 (3)°
V = 1892.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 200 K
0.33 × 0.23 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.505, T _max = 0.721
13624 measured reflections
4652 independent reflections
3069 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.110
S = 1.08
4652 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.62 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: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681103604X/is2772sup1.cif

e-67-m1349-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103604X/is2772Isup2.hkl

e-67-m1349-Isup2.hkl^{(227.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O4	2.103 (2)
Mn1—O2	2.1295 (19)
Mn1—O1	2.172 (2)
Mn1—O3	2.190 (2)
Mn1—N1	2.303 (2)
Mn1—N2	2.308 (2)
Mn2—O11	2.105 (2)
Mn2—O9	2.1327 (19)
Mn2—O8	2.181 (2)
Mn2—O10	2.184 (2)
Mn2—N3	2.287 (2)
Mn2—N4	2.332 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O6ⁱ	0.84	1.88	2.709 (3)	170
O1—H1B⋯O12ⁱⁱ	0.84	1.90	2.700 (3)	160
O2—H2A⋯O13ⁱⁱⁱ	0.84	1.86	2.655 (3)	158
O2—H2B⋯O14ⁱ	0.84	1.98	2.804 (3)	168
O3—H3A⋯O12ⁱⁱⁱ	0.84	2.60	3.434 (4)	175
O3—H3B⋯O14^iv	0.84	1.93	2.721 (3)	157
O8—H8A⋯O13^v	0.84	1.91	2.745 (3)	177
O8—H8B⋯O5ⁱⁱ	0.84	1.93	2.766 (3)	173
O9—H9A⋯O6	0.84	1.80	2.636 (3)	178
O9—H9B⋯O4ⁱ	0.84	2.06	2.839 (3)	153
O10—H10A⋯O5	0.84	1.98	2.804 (3)	165
O10—H10B⋯O7^vi	0.84	1.87	2.705 (3)	174

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

Acknowledgments

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

supplementary crystallographic information

Comment

The asymmetric unit of the title complex, [Mn₂(SO₄)₂(H₂O)₆(bpym)] (where bpym is 2,2'-bipyrimidine, C₈H₆N₄), contains two crystallographically independent half-molecules of the dinuclear Mn^II complex; an inversion centre is located at the centroid of each complex (Fig. 1). The two complexes are chemically identical, but somewhat different in geometry. The crystal structures of the complex were previously reported in the same space group P2₁/n (De Munno et al., 1995; Hong et al., 1996). The structure presented here is essentially the same as the published, however, the components of a unit cell and the cell parameters are quite different. Each asymmetric unit of the reported structures contains one half-molecule of the dinuclear complex.

In both complexes, two Mn^II ions are bridged by a bis-chelating bpym ligand to form a dinuclear Mn^II complex. Each Mn^II atom is six-coordinated in a considerably distorted octahedral environment defined by two N atoms of the bridging bpym ligand, and four O atoms from one sulfato anionic ligand and three water molecules. However, in the previously reported crystal structure of the analogous dinuclear cationic complex [Mn₂(H₂O)₈(bpym)](SO₄)₂.2H₂O, its single crystals were obtained from a water solution at 50 °C, each Mn^II atom is coordinated by two N atoms from bpym ligand and four O atoms from four water molecules (Ha, 2011).

The main contributions to the distortion of the octahedron are the tight N—Mn—N chelate angles [71.50 (8) and 71.46 (8)°] and the bulky SO₄ groups, which results in non-linear trans axes [<N1—Mn1—O2 = 157.90 (9)° and <N3—Mn2—O9 = 155.79 (9)°], whereas the apical O1—Mn1—O3 and O8—Mn2—O10 bonds are roughly linear with the bond angles of 175.80 (9)° and 176.15 (8)°, respectively. In the two complexes, however, the apical N—Mn—O(SO₄) bond angles are fairly different with <N2—Mn1—O4 = 178.47 (8)° and <N4—Mn2—O11 = 160.35 (8)°, because the coordination modes of the SO₄ anions are somewhat different. Atom O4 in the complex with atom Mn1 occupies the equatorial position, but atom O11 in the other complex is inclined considerably to the equatorial plane. The Mn—N and Mn—O bond lengths are roughly equivalent, respectively (Table 1). The geometry of the SO₄ ligands are nearly tetrahedral with the O—S—O bond angles of 107.83 (13)–111.48 (16)°, and the S—O bond distances are almost equal with 1.437 (2)–1.477 (2) Å. In the crystal structure, the complexes are linked by O—H···O hydrogen bonds between the water and sulfato ligands, forming a three-dimensional network (Fig. 2, Table 2). In addition, the complexes display numerous intermolecular π–π interactions between adjacent pyrimidine rings, the shortest ring centroid-centroid distance being 3.704 (2) Å.

Experimental

MnSO₄.H₂O (0.1688 g, 0.999 mmol) and 2,2'-bipyrimidine (0.1587 g, 1.003 mmol) in H₂O (20 ml) were refluxed for 1 h. After evaporation of the solvent, the residue was washed with ether and dried at 50 °C, to give a light yellow powder (0.3152 g) (Ha, 2011). Crystals suitable for X-ray analysis were obtained by slow evaporation from a mixture of water and dimethyl sulfoxide (DMSO) at 90 °C.