Bis[2,6-bis­(4,5-dihydro-1H-imidazol-2-yl)pyridine]manganese(II) bis­(per­chlorate) acetonitrile solvate

Shao-Ming Shang; Chun-Xia Ren; Xin Wang; Lu-De Lu; Xu-Jie Yang

doi:10.1107/S1600536809029195

. 2009 Aug 8;65(Pt 9):m1023–m1024. doi: 10.1107/S1600536809029195

Bis[2,6-bis(4,5-dihydro-1H-imidazol-2-yl)pyridine]manganese(II) bis(perchlorate) acetonitrile solvate

Shao-Ming Shang ^a, Chun-Xia Ren ^b, Xin Wang ^a,^*, Lu-De Lu ^a, Xu-Jie Yang ^a

PMCID: PMC2970088 PMID: 21577391

Abstract

In the cation of the title compound, [Mn(C₁₁H₁₃N₅)₂](ClO₄)₂·CH₃CN, the metal atom is located on a twofold rotation axis and is six-coordinated by six N atoms from two different 2,6-bis(4,5-dihydro-1H-imidazol-2-yl)pyridine (bip) ligands in a distorted octahedral geometry. The O atoms of the perchlorate anions are disordered with occupancies in the ratio 0.593 (10):0.407 (10). In the crystal, molecules are stabilized by two N—H⋯O hydrogen bonds, forming zigzag chains along the a axis, which are further interconnected by N—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.50 (1) Å] into a three-dimensional network.

Related literature

For the network topologies and potential applications of supramolecular architectures, see: Yaghi et al. (1998 ▶); Hagrman et al. (1999 ▶). The protonation and deprotonation of an imidazole ligand is believed to play an important role in the mechanism of the coordination chemistry, see: Bordo et al. (2001 ▶). Our studies of such complexes involving an imidazole ligand indicate that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism, see: Ren et al. (2007 ▶, 2009 ▶); Ren, Ye, He et al. (2004 ▶); Ren, Ye, Zhu et al. (2004 ▶). For metal–imidazole bond lengths, see: Stupka et al. (2004 ▶); Hammes et al. (2005 ▶); Haga et al. (1996 ▶); Böca et al. (2005 ▶). For metal–imidazole bond lengths, see: Ren et al. (2009 ▶). For the synthesis of 2,6-bis(4,5-dihydro-1H-imidazol-2-yl)pyridine, see: Baker et al. (1991 ▶).

Experimental

Crystal data

[Mn(C₁₁H₁₃N₅)₂](ClO₄)₂·C₂H₃N
M _r = 725.42
Monoclinic,
a = 20.521 (5) Å
b = 12.732 (5) Å
c = 14.602 (6) Å
β = 123.893 (10)°
V = 3167.0 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 273 K
0.28 × 0.21 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.837, T _max = 0.912
7799 measured reflections
2821 independent reflections
1277 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.121
S = 0.79
2821 reflections
246 parameters
94 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029195/tk2501sup1.cif

e-65-m1023-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029195/tk2501Isup2.hkl

e-65-m1023-Isup2.hkl^{(138.6KB, hkl)}

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

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

Mn1—N4	2.247 (3)
Mn1—N2	2.283 (3)
Mn1—N1	2.287 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O2ⁱⁱ	0.86	2.50	3.237 (12)	144
N5—H5A⋯O3ⁱⁱ	0.86	2.25	2.942 (12)	137
N5—H5A⋯O2′ⁱⁱ	0.86	2.11	2.965 (8)	176
N3—H3A⋯O4ⁱⁱⁱ	0.86	2.52	3.26 (2)	144
N3—H3A⋯O3′ⁱⁱⁱ	0.86	2.16	3.015 (8)	178

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

Acknowledgments

This work was generously supported by the National Natural Science Foundation of China (grant No. 20701016).

supplementary crystallographic information

Comment

The construction supramolecular architectures is currently of great interest owing to their intriguing network topologies and potential functions such as adsorption, ion exchange, shape-selective catalysis, non-linear and magnetic materials (Yaghi et al., 1998; Hagrman et al., 1999). The protonation and deprotonation of an imidazole ligand is believed to play an important role in the mechanism of the coordination chemistry (Bordo, et al., 2001). We described previously a number of such metal complexes, including imidazole ligand, and have concluded that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism (Ren, Ye, He et al., 2004; Ren, Ye, Zhu et al., 2004; Ren et al., 2007, 2009). We report here the preparation and crystal structure of a mononuclear coordination complex, [Mn(bip)₂](ClO₄)₂.CH₃CN (I) (bip is 2,6-bis(4,5-dihydro-1H-imidazol-2-yl)pyridine).

The crystal structure of (I) crystallizes in the monoclinic space group C2/c. As shown in Fig. 1, the title compound consists of a [Mn(bip)₂]²⁺ cation, two perchlorate counter ions and one Acetonitride molecular. The manganese(II) atom in the cation is in a distorted tetrahedral geometry, being coordinated with six nitrogen atoms from two neutral tridentate ligands bip. The Mn(1)—N bond lengths of The equatorial 2.292 (4), 2.284 (4), 2.251 (4) Å, which are slightly shorter than the metal-imidazole (Stupka, et al., 2004; Hammes et al., 2005; Haga et al., 1996; Böca et al., 2005) and longer than the metal-imidazole (Ren, et al., 2009). The N—Mn(1)—N bond angle is in the range of 70.17 (15)–147.1 (2) /%. Two bip ligands of adjacent molecules are parallel to each other with a distance of 3.50 Å, showing the presence of π-π interaction. The molecules further interconnected into three-dimensional network through hydrogen bond between the oxygen atom of perchlorate counter-ion and the uncoordination nitrogen atoms of bip ligands.

Experimental

All the reagents and solvents employed were commercially available and used as received without further purification. The ligand 2,6-bis(4,5-dihydro-1H-imidazol-2-yl)pyridine (bip) was synthesized by literature methods (Baker et al., 1991).

A solution of MnCl₂4H₂O (0.2 mmol, 40 mg) and NaClO₄ (0.4 mmol, 50 mg) in acetonitrile (10 ml), was added dropwise to a stirred solution of bip (0.4 mmol, 86 mg) in methanol(10 ml) at 60 K. Yellow single crystals suitable for X-ray diffraction were obtained by slow diffusion of diethyl ether into the clear filtrate for two days in 60% yield. Elemental analysis, Found: C, 39.68; H, 3.93; N, 21.15%. Calc. for C₂₄H₂₉C_l2MnN₁₁O₈: C, 39.70; H, 4.00; N, 21.23%. Main IR bands (KBr, cm_-1): 3370m, 3204 s, 2938m, 2887m, 1595m, 1567 s, 1531 s, 1453 s, 1283 s, 1209w, 1144 s,1116 s, 1089 s, 1028w, 1010m, 953w, 830w, 752w, 663w, 636m, 628m.