Tetra­aqua­bis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN 2}manganese(II) dihydrate

Tuoping Hu

doi:10.1107/S1600536808012464

. 2008 May 3;64(Pt 6):m772. doi: 10.1107/S1600536808012464

Tetraaquabis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN ²}manganese(II) dihydrate

Tuoping Hu ^a,^*

PMCID: PMC2961402 PMID: 21202464

Abstract

The title compound, [Mn(C₄H₃N₈)₂(H₂O)₄]·2H₂O, represents the first structurally characterized transition metal complex of the 1,2-bis(tetrazol-5-yl)ethene ligand. The complex molecule occupies a special position on an inversion centre and the Mn atom has a tetragonally distorted octahedral coordination. The bis(tetrazolyl)ethene ligand is planar within 0.0366 (7) Å. All ‘active’ H atoms participate in hydrogen bonds, which link molecules of the complex and the uncoordinated water molecules into an infinite three-dimensional framework.

Related literature

For related literature, see: Huang et al. (2005 ▶); Demko & Sharpless (2001 ▶).

Experimental

Crystal data

[Mn(C₄H₃N₈)₂(H₂O)₄]·2H₂O
M _r = 489.32
Triclinic,
a = 6.2296 (2) Å
b = 7.0093 (2) Å
c = 12.1212 (3) Å
α = 84.405 (1)°
β = 89.457 (1)°
γ = 67.016 (1)°
V = 484.70 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 273 (2) K
0.36 × 0.28 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.717, T _max = 0.887
9107 measured reflections
3246 independent reflections
3149 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.068
S = 1.04
3246 reflections
179 parameters
All H-atom parameters refined
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536808012464/ya2068sup1.cif

e-64-0m772-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012464/ya2068Isup2.hkl

e-64-0m772-Isup2.hkl^{(159.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Mn1—O1	2.1923 (7)
Mn1—O2	2.1835 (8)
Mn1—N2	2.2538 (7)

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O2—Mn1—O1	84.57 (3)
O2—Mn1—N2	91.07 (3)
O1—Mn1—N2	90.24 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N1ⁱ	0.833 (18)	2.021 (18)	2.8419 (10)	168.8 (17)
O1—H1A⋯O3ⁱⁱ	0.823 (18)	1.940 (18)	2.7599 (11)	174.0 (16)
O2—H2B⋯O3ⁱⁱⁱ	0.790 (18)	1.996 (19)	2.7797 (11)	171.4 (18)
O2—H2A⋯N6^iv	0.81 (2)	2.04 (2)	2.8472 (10)	173.7 (18)
O3—H3A⋯N5^v	0.82 (2)	2.09 (2)	2.8922 (11)	164.2 (19)
O3—H3B⋯O1	0.80 (2)	2.30 (2)	3.0693 (12)	160 (2)
N8—H8⋯N4^vi	0.926 (18)	1.792 (18)	2.7171 (10)	176.6 (16)

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

Acknowledgments

The author is grateful for funding from the Natural Science Foundation of Shanxi Province (2007011033), the Program of Technological Industrialization in Universities of Shanxi Province (20070308) and the Start-up Fund of the Northern University of China.

supplementary crystallographic information

Comment

The 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene ligand (H₂BTAE) was previously reported in its twice deprotonated form in the cystal structure of its sodium salt pentahydrate (Huang et al., 2005). The present paper provides the fist example of its structurally characterized complex with a transition metal; the ligand in this complex is monodeprotonated.

The molecule of Mn(H-BTAE)₂(H₂O)₄ occupies a special position in the inversion centre (Fig. 1); the Mn1 atom has a tetragonally distorted octahedral coordination (Table 1). The H-BTAE ligand has essentailly planar conformation, the maximum deviation of the N6 atom from its mean plane being 0.0366 (7) Å. The geometry of the ligand is similar to the one observed in Huang et al. (2005).

All "active" hydrogen atoms in the structure participate in the H-bonding (Table 2); the extensive H-bond system links molecules of the complex and non-coordinated water molecules into three-dimensional infinite network (Fig. 2).

Experimental

MnCl₂.4H₂O (0.5 mmol, 99 mg) and 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene (1 mmol, 192 mg) (Demko & Sharpless, 2001) were added to 30 ml of water:MeOH (1:1) mixture. After stirring for 30 min at room temperature, the pH value was adjusted to 7 by 1M NaOH, and clear solution was allowed to evaporate in the air. Nice prism-shaped crystals of the title compound were obtained after 3 days. The crystals were filtered, washed by EtOH and dried in the air.