Crystal structures of the water and acetone monosolvates of bis[4′-(pyridin-4-yl)-2,2′:6′,2′′-terpyridine]manganese(II) bis(hexafluoridophosphate)

The structure of the water and acetone solvates of bis[4′-(pyridin-4-yl)-2,2′:6′,2′′-terpyridine]manganese(II) bis(hexafluoridophosphate) were obtained. The compounds crystallize in the monoclinic P21/c and orthorhombic C2221 space groups, respectively.


Chemical context
The synthesis of new metal-organic frameworks (MOFs) can be achieved by several ways with different degrees of reaction control. One way of having a tighter control on the reactions is the use of metalloligands. A metalloligand is a kind of ligand in which the bonding capabilities of the ligand are combined with the directionallity of a metal centre (Halper et al., 2006;Kitagawa et al., 2006;Noro et al., 2005).

Figure 2
The crystal packing of (1) along the [100] direction. The components for the disordered organic ligand and hexafluoridophosphate with the lowest occupation factors are not represented. Supramolecular interactions are not represented for clarity.

Structural commentary
Except for the type of the co-crystallizing solvent, compound (2) (Fig. 3) is very similar to (1). However, the molecule of (2) exhibits a twofold rotation axis which is coincident to the axis of the coordination complex, which passes through atoms N13, C109, C8, N2, Mn1, N4, C19, C20 and N6. Thus, the asymmetric unit comprises one half of the A view of the molecular species present in the crystal of (2). Displacement ellipsoids are drawn at the 50% probability level and the atomic labelling is provided for all non-H atoms of the components with highest occupancies. Non-H atoms represented by spheres were isotropically refined and H atoms are depicted by spheres with arbitrary radius. The componenents with least occupancies are not numbered for the sake of clarity and represented as transparent.   Symmetry codes: (ii) x À 1 2 , Ày þ 3 2 , Àz þ 1; (iii) x À 1 2 , y þ 1 2 , z; (iv) Àx þ 1, Ày þ 2, z þ 1 2 .

Figure 4
The crystal packing of (2)  dicationic coordination compound, one disordered charge balancing hexafluoridophosphate anion and half of an acetone molecule. In the cation, only one of the noncoordinating pyridine moieties is affected by disorder. Nevertheless, the geometrical environment around the metal cation is still a distorted octahedron (with a symmetry axis in one of the diagonals), with Mn-N distances in the 2.180 (13)-2.247 (11) Å range, and the cis and trans octahedral angles in the intervals 72.3 (3)-107.7 (5) and 144.7 (5)-180.0 , respectively. The angle between the medium planes of the terpyridine moieties is 89.5 (3) , and the angles between the medium planes of non-coordinating pyridines and the terpyridine to which they are attached are 35.3 (non-disordered), 62.3 (12) and 65.8 (13) (disordered) (see Table 4 for details).
All the cations exhibit a distorted octahedral geometry, with the Pyterpy ligands in a meridional coordination. Some of the crystal structures sharing the same anion are isotypical. This is the case of the nitrate-containing crystals of Fe 2+ , Co 2+  have similar cell parameters, despite of not sharing the same anion (OFUKIK and UGEKEX). None of compounds described in this work is isotypical with a previously reported structure.

Synthesis and crystallization
All the reactants were purchased from commercial suppliers and used as received.

Title compounds
A solution of Pyterpy (132.7 mg, 0.42 mmol) in MeOH (50 mL) was added dropwise to a solution of [Mn(CH 3 COO) 2 ]Á4H 2 O (52.4 mg, 0.21 mmol) in 5 mL of water. The mixture refluxed at 338 K overnight to obtain a complete reaction. After this period, the solution was concentrated until a light-brown solid was obtained. The solid was filtrated and washed with water and ethanol to remove the impurities. The solid was dried at 333 K. Analysis calculated for [C 40 H 28 F 12 MnN 8 ][PF 6 ] 2 ÁH 2 O: C 47.97, H 3.22, N 11.19%; found: C 47.37, H 3.19, N 11.09%.
Suitable crystals for X-ray diffraction were obtained by diffusion of water into a solution of the title compound in acetone. Two types of crystals were harvested corresponding to two different solvates.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 9.
H atoms bound to carbon were placed at their idealized positions and were included in the final structural model in riding-motion approximation, with C-H = 0.95 Å (aromatic C-H) or C-H = 0.98 Å (aliphatic C-H). The isotropic displacement parameters for these atoms were fixed at 1.2 times U eq of the respective parent carbon atom. Some parts of the two crystal structures are subjected to spatial disorder.
coincidence of the central P atoms, and occupancies 2/3:1/3, 2/3:1/3. The P atoms were refined anisotropically, and the F atoms isotropically with a common U iso . The water molecule of crystallization was distributed over four distinct locations, which were isotropically refined with a common U iso , and total occupancy equal to 1. The H atoms of the solvent were not located, but were added in the formula unit.