Diaqua­bis(N,N-diethyl­nicotinamide-κN 1)bis­(4-formyl­benzoato-κO 1)manganese(II)

Mustafa Sertçelik; Barış Tercan; Ertan Şahin; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536809006047

. 2009 Feb 25;65(Pt 3):m324–m325. doi: 10.1107/S1600536809006047

Diaquabis(N,N-diethylnicotinamide-κN ¹)bis(4-formylbenzoato-κO ¹)manganese(II)

Mustafa Sertçelik ^a, Barış Tercan ^b, Ertan Şahin ^c, Hacali Necefoğlu ^a, Tuncer Hökelek ^d,^*

PMCID: PMC2968440 PMID: 21582097

Abstract

The title compound, [Mn(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], contains one Mn^II atom lying on an inversion centre, two 4-formylbenzoate and two diethylnicotinamide ligands and two coordinated water molecules. All ligands are monodentate. The four O atoms around the Mn atom form a slightly distorted equatorial plane, while the distorted octahedral coordination is completed by the two N atoms in the axial positions. An intramolecular O—H⋯O hydrogen bond occurs in the complex. In the crystal structure, O—H⋯O hydrogen bonds link the molecules through an R ₂ ²(16) ring motif, forming a one-dimensional chain along the a axis. The π–π contact between the pyridyl rings [centroid–centroid distance = 3.629 (2) Å] may further stabilize the structure.

Related literature

For general background, see: Antolini et al. (1982 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek et al. (1995 ▶, 1997 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Mn(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M _r = 745.68
Triclinic,
a = 7.3266 (2) Å
b = 8.6618 (2) Å
c = 16.0687 (3) Å
α = 86.381 (8)°
β = 78.272 (7)°
γ = 68.618 (6)°
V = 929.67 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 294 K
0.35 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.904, T _max = 0.935
18356 measured reflections
3799 independent reflections
3317 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.157
S = 1.02
3799 reflections
246 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006047/hy2182sup1.cif

e-65-0m324-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006047/hy2182Isup2.hkl

e-65-0m324-Isup2.hkl^{(106.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O1	2.1596 (18)
Mn1—O5	2.207 (2)
Mn1—N1	2.283 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O4ⁱ	0.92 (3)	1.87 (3)	2.775 (3)	165 (4)
O5—H52⋯O2	0.93 (3)	1.77 (4)	2.669 (3)	162 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are indebted to the Department of Chemistry, Atatürk University, Erzurum, Turkey, for the use of X-ray diffractometer purchased under grant No. 2003/219 of the University Research Fund.

supplementary crystallographic information

Comment

The structural functions and coordination relationships of the arylcarboxylates in transition metal complexes of benzoic acid derivatives change depending on the nature and position of the substituent groups on the benzene ring, the nature of the additional ligand molecules or solvents, and the medium of the synthesis (Nadzhafov et al., 1981; Shnulin et al., 1981). Transition metal complexes with biochemically active ligands frequently show interesting physical and/or chemical properties, and as a result, they may find applications in biological systems (Antolini et al., 1982). The structure determination of the title compound, (I), a manganese complex with two formylbenzoate (FOB) and two diethylnicotinamide (DENA) ligands and two water molecules, was undertaken in order to determine the properties of the ligands and also to compare the results obtained with those reported previously.

Compound (I) is a monomeric complex, with the Mn^II atom lying on a centre of symmetry. It contains two FOB and two DENA ligands and two water molecules (Fig. 1). All ligands are monodentate. The four O atoms [O1, O5, and the symmetry-related atoms, O1ⁱⁱ, O5ⁱⁱ; symmetry code: (ii) 1 - x, 1 - y, 1 - z] around the Mn atom form a slightly distorted equatorial plane, while the slightly distorted octahedral coordination is completed by the two N atoms of the DENA ligands (N1, N1ⁱⁱ) in the axial positions (Table 1 and Fig. 1). The intramolecular O—H···O hydrogen bond (Table 2) results in the formation of a six-membered ring (Mn1, O1, O2, O5, C1, H52), which adopts envelope conformation with C1 atom displaced by -0.235 (3) Å from the plane of the other five atoms.

The near equality of the C1—O1 [1.262 (3) Å] and C1—O2 [1.249 (3) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds, and may be compared with the corresponding distances: 1.256 (6) and 1.245 (6) Å in [Mn(DENA)₂(C₇H₄ClO₂)₂(H₂O)₂], (II), (Hökelek et al., 2008), 1.265 (6) and 1.275 (6) Å in [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O, (III), (Hökelek & Necefoğlu, 2007), 1.260 (4) and 1.252 (4) Å in [Zn(DENA)₂(C₇H₄FO₂)₂(H₂O)₂], (IV), (Hökelek et al., 2007), 1.259 (9) and 1.273 (9) Å in [Cu₂(DENA)₂(C₆H₅COO)₄], (V), (Hökelek et al., 1995), 1.279 (4) and 1.246 (4) Å in [Zn₂(DENA)₂(C₇H₅O₃)₄].2H₂O, (VI), (Hökelek & Necefoğlu, 1996), 1.251 (6) and 1.254 (7) Å in [Co(DENA)₂(C₇H₅O₃)₂(H₂O)₂], (VII), (Hökelek & Necefoğlu, 1997), 1.278 (3) and 1.246 (3) Å in [Cu(DENA)₂(C₇H₄NO₄)₂(H₂O)₂], (VIII), (Hökelek et al., 1997). This may be due to the intramolecular O—H···O hydrogen bond involving the carboxylate O atom (Table 2). In (I), the average Mn—O bond length is 2.183 (2) Å and the Mn atom is displaced out of the least-squares plane of the carboxylate group (O1, C1, O2) by -0.859 (1) Å. They are reported as -0.890 (1) Å in (II) and 2.185 (4) and 1.365 (3) Å in (III). The dihedral angle between the planar carboxylate group and the benzene ring A (C2–C7) is 3.0 (2)°, while that between rings A and B (N1, C9–C13) is 80.0 (1)°.

In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 2) link the molecules through a R²₂(16) ring motif (Bernstein et al., 1995) to form a one-dimensional chain along the a axis (Fig. 2). The π-π contact between the pyridyl rings of DENA ligands, Cg1···Cg1ⁱⁱⁱ [symmetry code: (iii) -x, 2 - y, 1 - z; where Cg1 is the centroid of ring B] may further stabilize the structure, with centroid–centroid distance of 3.629 (2) Å.

Experimental

The title compound was prepared by the reaction of Mn(SO₄).H₂O (1.69 g, 10 mmol) in H₂O (50 ml) and DENA (3.56 g, 20 mmol) in H₂O (15 ml) with sodium 4-formylbenzoate (3.44 g, 20 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.