Tetra­aqua­bis­[5-(pyridin-4-yl)tetra­zolido N 5-oxide-κN 2]manganese(II)

Xiang Jing; Ya Luo

doi:10.1107/S1600536812032618

. 2012 Jul 28;68(Pt 8):m1130. doi: 10.1107/S1600536812032618

Tetraaquabis[5-(pyridin-4-yl)tetrazolido N ⁵-oxide-κN ²]manganese(II)

Xiang Jing ^a,^*, Ya Luo ^a

PMCID: PMC3414170 PMID: 22904777

Abstract

The title compound, [Mn(C₆H₄N₅O)₂(H₂O)₄], is isotypic with its Zn, Ni and Cd analogues reported recently. In the crystal, the Mn^II cations are coordinated by four O atoms from four aqua ligands and two N atoms from two 5-(pyridin-4-yl)tetrazolide N⁵-oxide ligands in a distorted octahedral coordination environment. The asymmetric unit consists of one Mn^II cation located on a crystallographic twofold axis, and two crystallographically independent water molecules and one N-donor ligand in general positions. The discrete complex molecules are arranged in alternating rows parallel to [100] and are linked by O—H⋯N and O—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For related structures, see: Yang et al. (2009 ▶); Yu et al. (2004a ▶,b ▶). For the coordination properties of tetrazolate ligands, see: Aromí et al. (2011 ▶).

Experimental

Crystal data

[Mn(C₆H₄N₅O)₂(H₂O)₄]
M _r = 451.29
Monoclinic,
a = 21.828 (2) Å
b = 7.0620 (9) Å
c = 11.3229 (13) Å
β = 96.515 (10)°
V = 1734.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 293 K
0.32 × 0.25 × 0.20 mm

Data collection

Bruker APEX area-dectector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.782, T _max = 0.849
5196 measured reflections
1530 independent reflections
1149 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.080
S = 1.05
1530 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032618/nc2281sup1.cif

e-68-m1130-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032618/nc2281Isup2.hkl

e-68-m1130-Isup2.hkl^{(75.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032618/nc2281Isup3.cdx

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
O2—H9⋯O3ⁱ	0.87 (3)	1.80 (3)	2.658 (3)	170 (3)
O1—H11⋯O3ⁱⁱ	0.80 (3)	1.98 (3)	2.770 (3)	173 (3)
O2—H10⋯O3ⁱⁱⁱ	0.87 (3)	1.88 (3)	2.751 (3)	172 (3)
O1—H12⋯N3^iv	0.81 (3)	2.05 (3)	2.861 (3)	171 (3)

Open in a new tab

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

Acknowledgments

The authors thank the Research Office of Yangtze University for supporting this work.

supplementary crystallographic information

Comment

Ligands based on tetrazolates have attracted wide attention because of their versatile coordination modes and therefore, a large number of metal complexes containing these types of ligands are reported in literature (Aromí et al., 2011). Several of them have been prepared via in situ synthesis of nitriles and azides. In view of this we have reacted 4-cyanopyridine 1-oxide with manganese chloride and sodium azide, which results in the formation of crystals of the title compound that is isotypic to its Zn, Ni and Cd analogs (Yu et al., 2004a,b; Yang et al., 2009).

The coordination geometry of the Mn atom is a slightly distorted octahedron formed by the coordination of four water molecules and two tetrazolate ligands (Fig. 1). The oxygen atoms from the four water molecules form a square planar arrangement around the Mn center and the tetrazolate ligands coordinate via the N atom to the Mn cations. The discrete complex molecules are arranged in alternating rows parallel to [100] and are linked by O—H···N and O—H···O hydrogen bonds into a three-dimensional network. (Fig. 2 and Table 1)

Experimental

The mixture of 4-cyanopyridine 1-oxide (0.42 mmol, 50.3 mg), MnCl₂.6H₂O (0.50 mmol, 116.5 mg) and NaN₃ (0.70 mmol, 45.6 mg) in 15 ml EtOH and H₂O (v/v = 2:1) were heated in a 25 ml bomb at 393 K for 3 d, then cooled to room temperature at a rate of 6 K h^-1. Colorless block-shaped crystals suitable for X-ray analysis were obtained in a yield of 40% based on the ligand 4-cyanopyridine 1-oxide. The product was washed with EtOH and H₂O, and then air-dried at ambient temperature. Elemental analysis for C₁₂H₁₆N₁₀O₆Mn found: C 31.75, H 3.52, N 30.97; calculated: C 31.94, H 3.57, N 31.04. Selected IR (KBr, cm^-1): 3118 (w), 3058(w), 1532 (m), 1462 (m), 1439 (m), 1215 (s), 1193 (s), 856 (s).