catena-Poly[bis­(4-amino­pyridinium) [[diaqua­manganese(II)]-di-μ-chlorido] dichloride]

Donia Zaouali Zgolli; Habib Boughzala; Ahmed Driss

doi:10.1107/S1600536809026804

. 2009 Jul 15;65(Pt 8):m921. doi: 10.1107/S1600536809026804

catena-Poly[bis(4-aminopyridinium) [[diaquamanganese(II)]-di-μ-chlorido] dichloride]

Donia Zaouali Zgolli ^a, Habib Boughzala ^a,^*, Ahmed Driss ^a

PMCID: PMC2977461 PMID: 21583377

Abstract

Single crystals of the title organic–inorganic hybrid, {(C₅H₇N₂)₂[MnCl₂(H₂O)₂]Cl₂}_n, were synthesized from an ethanol solution containing manganese(II) chloride tetrahydrate and 4-aminopyridine under acidic conditions. The asymmetric unit contains a disordered organic cation (occupancies in the ratio 0.72:0.28), a chloride anion and an MnCl(H₂O) moiety with the Mn^II atom located on an inversion center. The structure is built up of infinite chains of edge-sharing [MnCl₄(H₂O)₂] octahedra developing parallel to the a axis which are separated by the 4-aminopyridinium ions and discrete chloride ions. The organic cations occupy the empty space around each inorganic chain. Structural cohesion is organized through N—H⋯Cl and O—H⋯Cl hydrogen bonds, which build up a three-dimensional network.

Related literature

For general background to organic–inorganic hybride materials, see: Lacroix et al. (1994 ▶); Mitzi (2001 ▶); Calabrese et al. (1991 ▶); Hong et al. (1992 ▶). For related structures, see: Caputo et al. (1976 ▶); Hachuła et al. (2009 ▶); Zeng et al. (2008 ▶).

Experimental

Crystal data

(C₅H₇N₂)₂[MnCl₂(H₂O)₂]Cl₂
M _r = 421.01
Monoclinic,
a = 3.946 (1) Å
b = 17.586 (6) Å
c = 12.845 (4) Å
β = 93.48 (3)°
V = 889.7 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 298 K
0.05 × 0.04 × 0.02 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.916, T _max = 0.999
2516 measured reflections
1892 independent reflections
1473 reflections with I > 2σ(I)
R _int = 0.017
2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.095
S = 1.04
1892 reflections
112 parameters
43 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026804/dn2460sup1.cif

e-65-0m921-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026804/dn2460Isup2.hkl

e-65-0m921-Isup2.hkl^{(91.2KB, 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
O1—HW1⋯Cl1ⁱ	0.87	2.27	3.090 (2)	158
O1—HW2⋯Cl1ⁱⁱ	0.73	2.39	3.082 (2)	159
N1—H1A⋯Cl1	0.86	2.41	3.264 (4)	172
N1—H1B⋯Cl2	0.86	2.57	3.415 (4)	169
N1′—H1′1⋯Cl1ⁱⁱⁱ	0.86	2.47	3.299 (10)	163
N1′—H1′2⋯Cl1ⁱ	0.86	2.58	3.386 (9)	156

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

supplementary crystallographic information

Comment

Studies of organic-inorganic hybrid compounds continue to be a focus area in chemistry and material science because they combine properties of organic and inorganic compounds within one single molecular scale, such as second order nonlinear optical (NLO) response, magnetism, luminescence, and even multifunctional properties (Mitzi et al. (2001); Lacroix et al. (1994)).

This kind of materials, generally expressed as (R—NH₃)₂-MX₄ or (NH₃– R—NH₃) MX₄ (where R: organic group, M: divalent metal and X: halogen) can be regarded as semiconductor/insulator multiple quantum well system consisting of metal halide semiconductor layers sandwiched between organic ammonium insulator layers (Calabrese et al. (1991); Hong et al. (1992). In this paper, we report the synthesis and single-crystal X-ray diffraction studies of the organic-inorganic hybrid compound: [MnCl₂(H₂O)₂].(C₅H₈N₂)₂.Cl₂.

The assymetric unit is built up from a MnCl(H₂O) moiety, a fully disordered 4-ammoniumpyridine and a Cl ion. The Mn atom is located on an inversion center and each managanese atom is octahedrally coordinated to four equatorial chlorine atoms and to two oxygen atoms in axial positions (Fig. 1).

The [MnCl₂(H₂O)₂].(C₅H₈N₂)₂.Cl₂structure is built up of infinite edges sharing octahedra MnCl₄(H₂O)₂ chains running along the [100] direction. Similar arrangement of the inorganic part was reported for [(CH₃)₃NH]MnCl₃. 2H₂O published by Caputo et al. (1976). The organic-inorganic cohesion is ensured by hydrogen bonding that involves two kinds of interactions: N1—H1A···Cl1 and N1—H1B···Cl2 bonds between the organic cation and the chloride and O—HW1···Cl1 and O—HW2···Cl1 between the water molecule and the Cl anion (Fig. 2, Table 1). It is worthy to note that the second kind of hydrogene bonds are stronger than the first one.

The [C₅H₈N₂]⁺cations is disordered over two positions which are rotated with respect to each other by about 141°. Thus, the amine group of one component lies close to the carbon atom C1 of the other component so that both components are more or less coplanar one to another (Fig. 3).

The distances and angles througout the structure are in good agreement with those encountered in several compounds of literature (Zeng et al. (2008); Hachuła et al. (2009)).

Experimental

An aqueous HCl (1M) solution, 4-aminopyridine (C₅H₆N₂) and manganese dichloride tetrahydrate (MnCl₂.4H₂O) in a 2:1:1 molar ratio were mixed and dissolved in sufficient ethanol. Crystal for X-Ray diffraction structural analysis were grown by slow evaporation at room temperature and then set aside for few days to obtain colourless crystals.