catena-Poly[[[diaqua­bis[4-(diethyl­amino)benzoato-κO]manganese(II)]-μ-aqua] dihydrate]

Tuncer Hökelek; Hakan Dal; Barış Tercan; Özgür Aybirdi; Hacali Necefoğlu

doi:10.1107/S1600536809021060

. 2009 Jun 6;65(Pt 7):m747–m748. doi: 10.1107/S1600536809021060

catena-Poly[[[diaquabis[4-(diethylamino)benzoato-κO]manganese(II)]-μ-aqua] dihydrate]

Tuncer Hökelek ^a, Hakan Dal ^b, Barış Tercan ^c, Özgür Aybirdi ^d, Hacali Necefoğlu ^d,^*

PMCID: PMC2969307 PMID: 21582685

Abstract

In the crystal structure of the title complex, {[Mn(C₁₁H₁₄NO₂)₂(H₂O)₃]·2H₂O}_n, the two independent Mn^II atoms are located on a centre of symmetry and coordinated by two 4-(diethylamino)benzoate (DEAB) anions and two water molecules in the basal plane while another water molecule bridges the Mn atoms in the apical directions, forming polymeric chains. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 11.33 (13) and 10.90 (9)° and the benzene rings are oriented at a dihedral angle of 67.88 (6)°. The uncoordinated water molecules link the carboxylate groups and coordinated water molecules via O—H⋯O hydrogen bonding. Weak C—H⋯π interactions are also found in the crystal structure.

Related literature

For the applications of transition metal complexes with biochemical molecules in biological systems, see: Antolini et al. (1982 ▶). Benzoic acid derivatives such as 4-aminobenzoic acid are used extensively as bifunctional organic ligands in coordination chemistry due to their various coordination modes, see: Chen & Chen (2002 ▶); Amiraslanov et al. (1979 ▶); Hauptmann et al. (2000 ▶). In pellagra disease, niacin deficiency leads to loss of copper from the body with high serum and urinary copper levels (Krishnamachari, 1974 ▶). The nicotinic acid derivative N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ▶). For structure–function–coordination relationships of the arylcarboxylate ion in Mn^II complexes of benzoic acid derivatives, see: Shnulin et al. (1981 ▶); Antsyshkina et al. (1980 ▶); Adiwidjaja et al. (1978 ▶); Catterick et al. (1974 ▶); Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1995 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 1998 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(C₁₁H₁₄NO₂)₂(H₂O)₃]·2H₂O
M _r = 529.48
Monoclinic,
a = 8.1585 (2) Å
b = 11.2907 (2) Å
c = 27.8738 (3) Å
β = 95.644 (2)°
V = 2555.15 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 100 K
0.50 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.870, T _max = 0.920
22676 measured reflections
6299 independent reflections
4556 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.091
S = 1.02
6299 reflections
354 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021060/xu2525sup1.cif

e-65-0m747-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021060/xu2525Isup2.hkl

e-65-0m747-Isup2.hkl^{(302.1KB, hkl)}

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

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

Mn1—O2	2.1071 (14)
Mn1—O5	2.1932 (14)
Mn1—O6	2.2725 (13)
Mn2—O4	2.1120 (13)
Mn2—O6	2.2594 (13)
Mn2—O7	2.1835 (14)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O8	0.97 (2)	1.77 (2)	2.738 (2)	177 (2)
O5—H52⋯O4ⁱⁱⁱ	0.902 (17)	1.846 (17)	2.7457 (19)	175 (3)
O6—H61⋯O3	0.929 (17)	1.778 (19)	2.651 (2)	156 (2)
O6—H62⋯O1ⁱ	0.896 (18)	1.76 (2)	2.608 (2)	156 (3)
O7—H71⋯O9ⁱ	0.97 (2)	1.77 (2)	2.739 (2)	177.0 (2)
O7—H72⋯O2ⁱⁱ	0.893 (18)	1.850 (18)	2.733 (2)	170 (3)
O8—H82⋯O3	0.96 (3)	1.77 (3)	2.694 (2)	160 (3)
O9—H91⋯O1	0.927 (19)	1.80 (2)	2.692 (2)	160 (3)
C6—H6⋯Cg2	0.93	2.91	3.764 (2)	154
C19—H19A⋯Cg2^iv	0.97	2.90	3.830 (2)	162

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C13–C18 ring.

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer.

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). Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002; Amiraslanov et al., 1979; Hauptmann et al., 2000). Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974). The nicotinic acid derivative N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972).

The structure-function-coordination relationships of the arylcarboxylate ion in Mn^II complexes of benzoic acid derivatives may also change 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 pH and temperature of synthesis (Shnulin et al., 1981; Antsyshkina et al., 1980; Adiwidjaja et al., 1978). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974).

The structure determination of the title compound, (I), a polymeric manganese complex with four 4-diethylaminobenzoate (DEAB) ligands and five coordinated and two uncoordinated water molecules, was undertaken in order to determine the properties of the ligands and also to compare the results obtained with those reported previously.

In the polymeric title complex, (I), each Mn atom is located on a centre of symmetry, and surrounded by two DEAB and four water molecules. The DEAB ligands are monodentate and a water molecule bridges the two Mn atoms (Fig. 1). The four O atoms (O2, O2', O5, O5' and O4, O4', O7, O7' atoms) in the equatorial planes around each Mn atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the symmetry related O atoms of the bridging water molecule (O6, O6' and O6'') in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.263 (2) Å], C1—O2 [1.279 (2) Å], C12—O3 [1.263 (2) Å] and C12—O4 [1.278 (2) 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]. 2(H₂O), (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) and 1.254 (2) and 1.251 (2) Å in [Co(NA)₂(C₇H₄NO₄)₂(H₂O)₂], (VIII) (Hökelek & Necefoğlu, 1998).

In (I), the average Mn—O bond length is 2.1880 (14) Å and the Mn atoms are displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C12/O4) by -0.857 (1) Å and 1.004 (1) Å, respectively. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C13—C18) are 11.33 (13)° and 10.90 (9)°, respectively, while those between rings A and B are A/B = 67.88 (6)°. Intramolecular O—H···O hydrogen bonds (Table 2) link the uncoordinated water molecules to the carboxylate groups and coordinated water molecules (Fig. 1).

In the crystal structure, strong intra- and intermolecular O—H···O hydrogen bonds (Table 2) link the molecules into a supramolecular structure, in which they may be effective in the stabilization of the structure. There also exist two weak C—H···π interactions (Table 2).

Experimental

The title compound was prepared by the reaction of MnSO₄.H₂O (0.85 g, 5 mmol) in H₂O (50 ml) and NA (1.22 g, 10 mmol) in H₂O (50 ml) with sodium p-dimethylaminobenzoate (2.16 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving single crystals.