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

Tuncer Hökelek; Nagihan Çaylak; Hacali Necefoğlu

doi:10.1107/S1600536808005540

. 2008 Feb 29;64(Pt 3):m505–m506. doi: 10.1107/S1600536808005540

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

Tuncer Hökelek ^a,^*, Nagihan Çaylak ^b, Hacali Necefoğlu ^c

PMCID: PMC2960864 PMID: 21201885

Abstract

The title compound, [Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], is a monomeric complex with the Mn^II atom lying on an inversion center. It contains two 4-chlorobenzoate and two diethylnicotinamide ligands and two water molecules, all of which are monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octahedral geometry is completed by two N atoms in the axial positions. In the crystal structure, O—H⋯O hydrogen bonds link the molecules into an infinite chain.

Related literature

For general background, see: Adiwidjaja et al. (1978 ▶); Amiraslanov et al. (1979 ▶); Antolini et al. (1982 ▶); Antsyshkina et al. (1980 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek et al. (1995 ▶, 1997 ▶); Hökelek et al. (2007 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M _r = 758.54
Triclinic,
a = 7.3552 (1) Å
b = 8.6465 (2) Å
c = 15.9847 (3) Å
α = 84.500 (16)°
β = 78.616 (17)°
γ = 68.154 (17)°
V = 924.73 (12) Å³
Z = 1
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 294 (2) K
0.30 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.902, T _max = 0.950
4010 measured reflections
3752 independent reflections
2604 reflections with I > 2σ(I)
R _int = 0.062
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.080
wR(F ²) = 0.254
S = 1.04
3752 reflections
225 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.26 e Å⁻³
Δρ_min = −1.31 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); 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/S1600536808005540/hy2120sup1.cif

e-64-0m505-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005540/hy2120Isup2.hkl

e-64-0m505-Isup2.hkl^{(103.7KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Mn—O1	2.141 (3)
Mn—O4	2.205 (4)
Mn—N1	2.281 (4)

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O1ⁱ—Mn—O4	90.38 (14)
O1—Mn—O4	89.62 (14)
O1—Mn—N1ⁱ	92.23 (14)
O4—Mn—N1ⁱ	92.72 (14)
O1—Mn—N1	87.77 (14)
O4—Mn—N1	87.28 (14)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2ⁱ	0.99 (4)	1.71 (5)	2.670 (6)	162 (7)
O4—H42⋯O3ⁱⁱ	0.93 (5)	1.85 (5)	2.766 (6)	168 (7)

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

Acknowledgments

The authors acknowledge the purchase of a CAD-4 diffractometer under grant DPT/TBAG1 of the Scientific and Technical Research Council of Turkey.

supplementary crystallographic information

Comment

Transition metal complexes with biochemical molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982). The structural functions and coordination relationships of the arylcarboxylate ions in manganese(II) complexes of benzoic acid derivatives may be changed, depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the medium of the synthesis (Adiwidjaja et al., 1978; Amiraslanov et al., 1979; Antsyshkina et al., 1980; Nadzhafov et al., 1981; Shnulin et al., 1981).

N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant. The structures of several complexes obtained by reacting divalent transition metal ions with DENA have been determined in our laboratory, including those of Cu₂(DENA)₂(C₆H₅COO)₄, (II), (Hökelek et al., 1995), [Zn₂(DENA)₂(C₇H₅O₃)₄].2H₂O, (III), (Hökelek & Necefoğlu, 1996), [Co(DENA)₂(C₇H₅O₃)₂(H₂O)₂], (IV), (Hökelek & Necefoğlu, 1997), [Cu(DENA)₂(C₇H₄NO₄)₂(H₂O)₂], (V), (Hökelek et al., 1997) and [Zn(DENA)₂(C₇H₄FO₂)₂(H₂O)₂], (VI), (Hökelek et al., 2007). The structure determination of the title compound, (I), a manganese(II) complex with two chlorobenzoate (CB), two DENA ligands and two water molecules, was undertaken in order to determine the properties of the CB and DENA ligands and also to compare the results obtained with those reported previously.

Compound (I) is a monomeric complex, with the Mn atom lying on a center of symmetry. It contains two CB, two DENA ligands and two water molecules (Fig. 1). All ligands are monodentate. The four O atoms (O1, O4, and their symmetry-related atoms) in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination geometry is completed by the two N atoms of the DENA ligands in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.256 (6) Å] and C1—O2 [1.245 (6) 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: 1.259 (9) and 1.273 (9) Å in (II), 1.279 (4) and 1.246 (4) Å in (III), 1.251 (6) and 1.254 (7) Å in (IV), 1.278 (3) and 1.246 (3) Å in (V) and 1.265 (6) and 1.275 (6) Å in [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O, (VII), (Hökelek & Necefoğlu, 2007). 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 2.173 (3) Å. The Mn atom is displaced out of the least-squares plane of the carboxylate group (O1/C1/O2) by 0.890 (1) Å; this is reported as 2.185 (4) and 1.365 (3) Å, respectively, in (VII). The dihedral angle between the planar carboxylate group and the benzene ring A (C2 to C7) is 3.0 (4)°, while that between rings A and B (N1/C8 to C12) is 81.0 (4)°.

As can be seen from the packing diagram (Fig. 2), the Mn atoms are located at the corners of the unit cell and the molecules of (I) are linked into infinite chains along the a-axis by intermolecular O—H···O hydrogen bonds (Table 2).

Experimental

The title compound was prepared by the reaction of Mn(NO₃)₂ (1.79 g, 10 mmol) in H₂O (25 ml) and DENA (3.56 g, 20 mmol) in H₂O (25 ml) with sodium p-chlorobenzoate (3.57 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colorless single crystals.