Mononuclear and Dinuclear Manganese(II) Complexes from the Use of Methyl(2-pyridyl)ketone Oxime

The reactions of methyl(2-pyridyl)ketone oxime, (py)C(Me)NOH, with manganese(II) sulfate monohydrate have been investigated. The reaction between equimolar quantities of MnSO4 · H2O and (py)C(Me)NOH in H2O lead to the dinuclear complex [Mn2(SO4)2{(py)C(Me)NOH}4] · (py)C(Me)NOH, 1 · (py)C(Me)NOH, while employment of NaOMe as base affords the compound [Mn(HCO2)2{(py)C(Me)NOH}2] (2). The structures of both compounds have been determined by single crystal X-ray diffraction. In both complexes, the organic ligand chelates through its nitrogen atoms. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes.


Introduction
There is currently a renewed interest in the coordination chemistry of oximes [1]. The research efforts are driven by a number of considerations. One of these is that they are considered to be reasonable models for the biologically significant imidazole donor group of the amino acid histidine [2]. Thus, they potentially can be used for the synthesis of various nuclearity metal clusters to model M x sites in biomolecules, including elucidating the structure and mechanism of action of the CaMn 4 core of the water oxidizing complex within the photosynthetic apparatus of green plants and cyanobacteria [3,4]. In addition, metal complexes of oximes can be used in several other applications, that is, the solution of pure chemical problems [5,6], the development of new oxygen activation catalysts based on nickel(II) polyoximate complexes [7] and the application of metal ion/oxime systems as efficient catalysts for the hydrolysis of organonitriles [8]. In the latter, metal ions can behave as extremely strong activators of RCN molecules towards nucleophilic attack by OH − /H 2 O. Other applications of metal complexes of oximes include the design of Ca 2+ -and Ba 2+ -selective receptors based on site-selective transmetallation of polynuclear zinc (II)/polyoxime complexes [9], the study of metal-ion assisted organic transformations [10], and the mechanistic investigation of corrosion inhibition by Acorga P5000 (a modern corrosion inhibitor comprising 5nonylsalicylaldoxime as a mixture of carbon-chain isomers) on iron surfaces [11]. Note also that oximate ligands are employed in the synthesis of homo-and heterometallic [1,12] clusters and coordination polymers [13] with interesting magnetic properties, including single-molecule magnetism [14][15][16], and single-chain magnetism [17] behavior.
Ligands containing one oxime group and one pyridyl group, without other donor sites, are popular in coordination chemistry. Metal-free pyridine oximes exhibit a plethora of biological properties including action on the cardiovascular system, sedative, antidepressant, antispasmodic, cytotoxic, antiviral, and bactericidal activities, while they are good antidotes for poisoning by organophosphorus compounds [18]. Most of these ligands contain a 2-pyridyl group, and thus are named 2-pyridyl oximes, Scheme 2: The common coordination mode of the neutral 2pyridyl oximes and the Harris notation [26] which describes this mode.
(py)C(R)NOH (Scheme 1). The anionic forms of these molecules, (py)C(R)NO − , are versatile ligands for a variety of research objectives, including μ 2 and μ 3 behaviour; the activation of 2-pyridyl oximes by 3d-metal centers towards further reactions is also becoming a fruitful area of research. The majority of the metal complexes of these ligands have been prepared in the last 15 years and much of their chemistry remains to be explored in more detail [1].
With only few exceptions [19,20], the hitherto structurally characterized metal complexes containing neutral 2pyridyl oximes as ligands are mononuclear. The donor atoms of the neutral 2-pyridyl oximes in metal complexes are the nitrogen atom of the oxime group and the nitrogen atom of the pyridyl group. Thus, (py)C(R)NOH behave as N,N -chelating ligands (see Scheme 2) making necessary the employment of additional inorganic or organic anions to complete the coordination sphere of the metal centre or to balance the charge of the complex cation. A variety of monoanions have been used for this reason, for example, PhCO 2 − [21], Cl − [22,23], Br − [24], and NO 3 − [25]. Recently, we have started a research program to explore the use of the sulfate ion, SO 4 2− , in 3d-metal/2-pyridyl oxime chemistry, instead of the abovementioned monoanionic ligands. The possible advantages of using SO 4 2− include (i) the possibility of triggering aggregation of preformed smaller species into new products, and (ii) the possible diversion of known reaction systems developed using inorganic monoanions to new species as a result of the higher charge and higher denticity of the sulfate ligand.
In this paper, we report the synthesis and the X-ray structural characterization of the two new Mn(II) complexes [Mn 2 (SO 4 ) 2 {(py)C(Me)NOH} 4 ]·(py)C(Me)NOH (1·(py)C(Me)NOH) and [Mn(HCO 2 ) 2 {(py)C(Me)NOH} 2 ] (2) which contain the neutral methyl(2-pyridyl)ketone oxime as organic ligand. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes.

Experiments
All manipulations were performed under aerobic conditions using materials and solvents as received. IR spectra were recorded on a Perkin-Elmer PC16 FT-IR spectrometer with samples prepared as KBr pellets. [Mn(HCO 2 ) 2 {(py)C(Me)NOH} 2 ](2). Solid NaOMe (0.090 g, 1.50 mmol) was added to a colourless solution of (py)C(Me)NOH (0.204 g, 1.50 mmol) in CH 2 Cl 2 (20 cm 3 ); the solid soon dissolved. Solid MnSO 4 ·H 2 O (0.250 g, 1.50 mmol) was then added and the resulting solution was stirred for 24 hours at room temperature. A small quantity of undissolved material was removed by filtration and the dark brown filtrate layered with Et 2 O (40 cm 3 ). Slow mixing gave X-ray quality yellow crystals of the product.   Scheme 3: The up to now crystallographically established coordination modes of the sulfato ligand and the Harris notation [26] which describes these modes.
with R int = 0.0084, to give 3727 independent reflections from a total 3964 collected. The structure was solved by direct methods and refined by full-matrix least-squares on F 2 , using 3727 reflections and refining 325 parameters. All nonhydrogen atoms were refined anisotropically. Hydrogen atoms were either located by difference maps and were refined isotropically or were introduced at calculated positions as riding on bonded atoms. For 2, X-ray data were collected at 100 K using a Oxford Diffraction diffractometer with graphite-monochromated Mo-K a radiation (λ = 0.71073Å). Symmetry equivalent data were averaged with R int = 0.0160, to give 9343 independent reflections from a total of 13039 collected. The structure was solved by direct methods and refined by full-matrix leastsquares on F 2 , using 9343 reflections and refining 258 parameters. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were either located by difference maps and were refined isotropically or were introduced at calculated positions as riding on bonded atoms.
Details of the data collection and refinement for 1·(py)C(Me)NOH and 2 are given in Table 1. (1)

Results and Discussion
The nonstoichiometric MnSO 4 ·H 2 O to (py)C(Me)NOH reaction ratio (1 : 1) employed for the preparation of 1·(py)C(Me)NOH (Section 2) did not prove detrimental to the formation of the complex. With the identity of 1·(py)C(Me)NOH established by single-crystal X-ray crystallography, the "correct" stoichiometry (1 : 2.5) was employed and led to the pure compound in high yield.
As a next step, we decided to add base in the reaction mixture targeting the deprotonation of the organic ligand. Thus, treatment of MnSO 4 ·H 2 O with one equivalent of (py)C(Me)NOH and one equivalent of NaOMe in CH 2 Cl 2 gave a dark brown solution from which the mononu- To our surprise, an amount of the methoxide ions did not act as proton acceptors but they got oxidized to formates (HCO 2 − ) during the aerial aggregation process [28]. Thus, the organic ligand in 2 is neutral. As expected, the nature of the base is crucial for the identity of the product; employment of NEt 3 , NMe 4 OH, NEt 4 OH, LiOH·H 2 O etc. leads to dark brown oily materials that have not been characterized. Also, note that: (i) The color of 2 (yellow) is different than the color of the reaction mixture (dark brown, this colour is characteristic of Mn III or Mn II/III species), and (ii) a similar reaction, but with (py)C(ph)NOH instead of (py)C ( [29] whose core consists of two butterfly subunits. These observations indicate that compound 2 is not the only product of the reaction and that, presumably, a higher nuclearity cluster, with the metals at higher oxidation states, is present in solution. Work is in progress to isolate the second product from the reaction mixture.  4 2− oxygen, pyridyl nitrogen and oxime nitrogen atoms, respectively. The cis arrangement of the oxime groups seems unfavourable, probably due to the steric hindrance arising from the methyl group upon oxime coordination. The long Mn · · · Mn distance [5.040(2)Å] is a consequence of the presence of the two syn, anti sulfato bridges.

Description of
The molecular structure of 1·(py)C(Me)NOH is stabilized by intramolecular hydrogen bonds (Table 3). Each coordinated (py)C(Me)NOH oxime group is strongly hydrogen bonded to an uncoordinated O atom of the sulfato ligand (O33 or O33 ). Thus, O33 (and its symmetry equivalent) participates in two hydrogen bonds.  Complex 2 crystallizes in the monoclinic space group P2 1 /n and its structure consists of mononuclear [Mn(HCO 2 ) 2 {(py)C(Me)NOH} 2 ] molecules. Two bidentate chelating (py)C(Me)NOH molecules (1.011 [26], see Scheme 2) and two monodentate HCO 2 − ions create sixcoordination at the Mn II ion. The coordination geometry of the metal ion is distorted octahedral. As 1·(py)C(Me)NOH, complex 2 is the cis-cis-trans isomer considering the positions of the coordinated HCO 2 − oxygen, pyridyl nitrogen and oxime nitrogen atoms, respectively. Intramolecular hydrogen bonds are present in the structure of 2 ( Table 5). The oximic oxygen atom of each (py)C(Me)NOH ligand is very strongly intramolecularly hydrogen bonded to one uncoordinated formate oxygen atom.
Complexes 1·(py)C(Me)NOH and 2 join a small but growing family of structurally characterized metal complexes containing the neutral or anionic forms of methyl(2pyridyl)ketone oxime as ligands. The 1.011 ligation mode is the exclusive one for the metal complexes containing the neutral ligand [22,24,30].
The structurally characterized Mn complexes of (py)C(Me)NOH and/or (py)C(Me)NO − [14,[31][32][33] are collected in Table 6, together with the cores of the polynuclear complexes and the ligands' coordination modes for convenient comparison. Closer inspection of      of the neutral oxime nitrogen [22]. The strong band at 1124 cm −1 in the spectrum of 1·(py)C(Me)NOH should also have a ν(N-O) oxime character resulting from the presence of lattice (py)C(Me)NOH molecules in the structure. Several bonds appear in the 1655-1400 cm −1 region for both complexes; contribution from the ν(C=N) oxime and δ(OH) modes (>1580 cm −1 ) are expected in this region, but overlap with the stretching vibrations of the aromatic rings and the carboxylate groups (for 2) renders assignments and discussion of the coordination shifts difficult. The in-plane deformation band of the 2-pyridyl ring of free (py)C(Me)NOH at 637 cm −1 shifts upwards in 1 (683 cm −1 ) and 2 (683 cm −1 ), confirming the involvement of the ring-N atom in coordination [36]. The appearance of a medium intensity band at 631 cm −1 in the spectrum of 1·(py)C(Me)NOH is indicative of the presence of lattice (py)C(Me)NOH molecules in this complex.
The IR spectrum of the free, that is, ionic, sulfate (the SO 4 2− ion belongs to the T d point group) consists of two bands at ∼1105 and ∼615 cm −1 , assigned to the ν 3 (F 2 ) stretching [ν d (SO)] and ν 4 (F 2 ) bending [δ d (OSO)] modes, respectively [27,37,38]. The ν 1 (A 1 ) stretching [ν s (SO)] and ν 2 (E) bending [δd(OSO)] modes are not IR-active (these are Raman-active). The coordination of SO 4 2− to metal ions decreases the symmetry of the group and the ν 3 and ν 4 modes are split [27,37,38]. In the case, the SO 4 2− -site symmetry is lowered from T d to C 3v (monodentate coordination), both ν 1 and ν 2 appear in the IR spectrum with weak to medium intensity, while ν 3 and ν 4 each splits into two bands in both IR and Raman spectra [37]. When the SO 4 2− -site symmetry is lowered from T d to C 2v (bidentate chelating or bridging coordination), again ν 1 and ν 2 appear in the IR spectrum (ν 2 splits into two Raman modes), while ν 3 and ν 4 each splits into three IR-active and Raman-active vibrations [37]. The crystallographically established symmetry of the sulfato groups in 1·(py)C(Me)NOH is C 2v . The bands at 1215, 1124 and 1080 (overlapping with the N-O oxime stretch) cm −1 are attributed to the ν 3 modes [37,39], while the bands at 592, 631 and 683 cm −1 (the latter two overlapping with the inplane 2-pyridyl deformations) are assigned to the ν 4 modes [37,38]. The band at 1010 cm −1 and the two weak features at 494 and 452 cm −1 can be assigned to the ν 1 and ν 2 modes, respectively. The appearance of two ν 2 bands is consistent with a symmetry at the sulfato groups lower than C 2v [37,39]. Thus, from the vibrational spectroscopy viewpoint, the sulfato ligands of 1·(py)C(Me)NOH appear to have C i symmetry (and not C 2v as deduced from their bidentate character). When the SO 4 2− -site symmetry is lowered from T d to C i , ν 3 and ν 4 each splits into three IR-active vibrations, ν 2 splits into two ones, while ν 1 appears as a single band [37,39]. This spectroscopic feature in 1·(py)C(Me)NOH is attributed to the fact that one uncoordinated oxygen atom of each bidentate bridging sulfate is hydrogen bonded to the oxygen atoms of the neutral oxime groups (see Table 3) resulting in a further lowering of the sulphate symmetry [39].

Bioinorganic Chemistry and Applications
The ν(CO 2 ) bands are difficult to assign in the spectrum of 2 due to the appearance of various stretching vibrations in the 1600-1400 cm −1 region and thus the application of the spectroscopic criterion of Deacon and Phillips [40] is very difficult.

Conclusions
The use of the sulfate ligand in combination with neutral (2), the latter being sulphate-free. In both complexes, the organic ligand chelates through its nitrogen atoms. The sulfate anion bridges the two Mn II atoms in 1. Compounds 1 · (py)C(Me)NOH and 2 join a small family of structurally characterized manganese complexes containing the neutral or anionic forms of methyl(2-pyridyl)ketone oxime as ligands, while they are new examples of structurally characterized compounds in which (py)C(Me)NOH exists exclusively in its neutral form.
Analogues of 1·(py)C(Me)NOH and 2 with phenyl(2pyridyl)ketone oxime, (py)C(ph)NOH, are not known to date, and it is currently not evident whether the stability of these species is dependent on the particular nature of the 2-pyridyl oxime ligand. We are studying this matter. Synthetic efforts are also in progress to "activate" the μ 3 to μ 6 bridging potential of the sulfate ligand in Mn complexes containing 2-pyridyl oximes and/or their anions as a means to get access to clusters and polymers with interesting structural and magnetic properties. Studies on the biological activity of 1·(py)C(Me)NOH and 2 are also planned.