catena-Poly[[[aqua­(di-2-pyridyl­amine-κ2 N 2,N 2′)manganese(II)]-μ-5-ferrocenyl­benzene-1,3-dicarboxyl­ato-κ3 O 1,O 1′:O 3] methanol monosolvate monohydrate]

Wei Liu; Gang Zhang

doi:10.1107/S1600536811022781

. 2011 Jun 25;67(Pt 7):m989–m990. doi: 10.1107/S1600536811022781

catena-Poly[[[aqua(di-2-pyridylamine-κ² N ²,N ^2′)manganese(II)]-μ-5-ferrocenylbenzene-1,3-dicarboxylato-κ³ O ¹,O ^1′:O ³] methanol monosolvate monohydrate]

Wei Liu ^a,^*, Gang Zhang ^a

PMCID: PMC3152059 PMID: 21836962

Abstract

In the title coordination polymer, {[FeMn(C₅H₅)(C₁₃H₇O₄)(C₁₀H₉N₃)(H₂O)]·CH₃OH·H₂O}_n, the Mn^II ion has a distorted octahedral coordination geometry and is ligated by two N atoms from two di-2-pyridylamine molecules, three O atoms from two 5-ferrocenylbenzene-1,3-dicarboxylate anions and one O atom from a coordinated water molecule. The Mn—O distances range from 2.151 (2) to 2.5093 (19) Å, while the Mn—N distances are 2.226 (2) and 2.248 (2) Å. Each 5-ferrocenylbenzene-1,5-dicarboxylate anion links to two Mn^II ions, resulting in a chain along the b axis. A three-dimensional network of N—H⋯O and O—H⋯O hydrogen bonds helps to stabilize the crystal packing.

Related literature

For the chemical, stereochemical, and electrochemical properties of ferrocene and its derivatives, see: Togni & Hayashi (1995 ▶). In coordination chemistry, there is much interest in the introduction of ferrocenyl groups into a ligand framework with the objective of generating materials possessing desired properties, see: Fang et al. (2001 ▶); Hudson (2001 ▶); Li et al. (2003 ▶). We have recently employed a V-shaped ferrocene-containing dicarboxylate ligand, 5-ferrocenylbenzene-1,5-dicarboxylic acid, in the construction of discrete or one-dimensional coordination compounds, see: Li et al. (2008 ▶, 2009 ▶). For a related structure, see: Sengupta et al. (2001 ▶).

Experimental

Crystal data

[FeMn(C₅H₅)(C₁₃H₇O₄)(C₁₀H₉N₃)(H₂O)]·CH₄O·H₂O
M _r = 642.34
Triclinic,
a = 9.4550 (19) Å
b = 10.174 (2) Å
c = 15.153 (3) Å
α = 93.03 (3)°
β = 99.94 (3)°
γ = 94.72 (3)°
V = 1427.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 173 K
0.24 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ▶) T _min = 0.798, T _max = 0.866
8342 measured reflections
5520 independent reflections
4259 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.096
S = 1.03
5520 reflections
430 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrystalClear (Rigaku, 2000 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022781/fj2428sup1.cif

e-67-0m989-sup1.cif^{(35.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022781/fj2428Isup2.hkl

e-67-0m989-Isup2.hkl^{(270.2KB, hkl)}

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
N2—H10⋯O7ⁱ	0.81 (3)	2.01 (3)	2.816 (4)	173 (3)
O7—H7A⋯O3ⁱⁱ	0.75 (4)	2.03 (4)	2.693 (3)	148 (4)
O5—H3⋯O1ⁱⁱⁱ	0.89 (4)	1.84 (4)	2.731 (3)	177 (4)
O6—H6A⋯O4ⁱⁱⁱ	0.85 (1)	1.86 (2)	2.685 (3)	162 (4)
O5—H5⋯O6	0.78 (3)	1.88 (3)	2.655 (4)	171 (3)
O7—H7B⋯O2	0.86 (6)	1.94 (6)	2.753 (4)	156 (5)

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (20771094, 20671083), the Science and Technology Key Task of Henan Province (0524270061) and the China Postdoctoral Science Foundation (20070410877).

supplementary crystallographic information

Comment

Ferrocene and its derivates have been extensively studied due to their special chemical, stereochemical, and electrochemical properties (Togni et al., 1995). In the field of coordination chemistry, chemists are strongly interested in introducing ferrocenyl groups into a ligand framework with the objective of generating materials possessing desired properties (Hudson et al., 2001; Fang et al., 2001; Li et al., 2003). Recently, we have been employed a V-shaped ferrocene-containing dicarboxylate ligand 5-ferrocenylbenzene-1,5-dicarboxylic acid to construct discrete or one-dimentional coordination compounds (Li et al., 2008; Li et al., 2009). As our continuing work for this ligand, we report here the synthesis and crystal structure of the title compound.

In the title coordination polymer, {[MnFe(C₁₈H₁₂O₄)(C₁₀H₉N₃)(H₂O)].CH₃OH.H₂O}_n, the Mn^II ion is six coordinated and located in a distorted octahedral geometry ligated by two nitrogen atoms from two 2,2'-dipyridylamine molecules, three oxygen atoms from two 5-ferrocenylbenzene-1,5-dicarboxylate anions and one oxygen atom from one coordinated water molecule (Fig. 1). The O2, O3, O4 and N3 atoms form an equatorial plane (the deviation of the plane being 0.0666 Å), and O5 and N1 occupy the axial position (O5—Mn1—N1 175.65 (9) °). The Mn—O distances range from 2.151 (2) to 2.5093 (19) Å, while Mn—N distances are 2.226 (2) and 2.248 (2) Å, respectively (Table 1). Each 5-ferrocenylbenzene-1,5-dicarboxylate anion links to two Mn^II ions resulting a chain along the b axis. A three-dimensional network of N—H···O and O—H···O hydrogen bonds (Table 2) help to stabilize the crystal packing.

Experimental

A methanol solution (5 ml) of 2,2'-dipyridylamine (0.0171 g, 0.1 mmol) was added dropwise to an aqueous solution (5 ml) of MnCl₂ (0.0198 g, 0.1 mmol), and then a methanol solution (10 ml) of 5-ferrocenylbenzene-1,5-dicarboxylic acid (0.035 g, 0.1 mmol)(Li et al., 2008) was added slowly to the above mixture solution. Finally, the pH value of the mixture was adjusted to about 7 with NaOH aqueous solution, and the resulting orange solution was allowed to slowly evaporate at ambient temperature. Two weeks later, orange block crystals suitable for X-ray single-crystal diffraction analysis were obtained in 48% yield based on Mn. Analysis calculated for C₂₉H₂₉FeMnN₃O₇: C 54.23, H 4.55, N 6.54; found: C 54.46, H 4.50, N 6.42.