Bis[4-(methyl­amino)benzoato-κO]bis­(nicotinamide-κN)zinc(II)

Barış Tercan; Tuncer Hökelek; Özgür Aybirdi; Hacali Necefoğlu

doi:10.1107/S1600536808042852

. 2008 Dec 20;65(Pt 1):m109–m110. doi: 10.1107/S1600536808042852

Bis[4-(methylamino)benzoato-κO]bis(nicotinamide-κN)zinc(II)

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

PMCID: PMC2968013 PMID: 21581475

Abstract

The title zinc complex, [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂], is composed of two monodentate 4-(methylamino)benzoate and two monodentate nicotinamide ligands. The coordination around the Zn atom is distorted tetrahedral. The dihedral angles between the two benzene rings and the two pyridine rings are 78.30 (6) and 68.86 (5)°. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules into an infinite three-dimensional network.

Related literature

For general backgroud, see: Antolini et al. (1982 ▶); Krishnamachari (1974 ▶); Nadzhafov et al. (1981 ▶). For related structures, see: Necefoğlu et al. (2002 ▶); Hökelek et al. (2007 ▶).

Experimental

Crystal data

[Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂]
M _r = 609.93
Monoclinic,
a = 8.085 (4) Å
b = 16.036 (7) Å
c = 21.333 (4) Å
β = 95.78 (3)°
V = 2751.8 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 294 (2) K
0.55 × 0.20 × 0.10 mm

Data collection

Rigaku AFC-7S diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.624, T _max = 0.911
17939 measured reflections
17079 independent reflections
7521 reflections with I > 2σ(I)
R _int = 0.045
3 standard reflections every 150 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.148
S = 1.00
17079 reflections
380 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994 ▶); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042852/su2084sup1.cif

e-65-0m109-sup1.cif^{(26KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042852/su2084Isup2.hkl

e-65-0m109-Isup2.hkl^{(503.3KB, hkl)}

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

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

Zn1—O1	1.9584 (14)
Zn1—O3	1.9210 (14)
Zn1—N1	2.0722 (15)
Zn1—N3	2.0854 (15)

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O1—Zn1—N1	96.85 (6)
O1—Zn1—N3	105.85 (6)
O3—Zn1—O1	143.41 (6)
O3—Zn1—N1	105.91 (5)
O3—Zn1—N3	95.81 (6)
N1—Zn1—N3	104.58 (5)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O2ⁱ	0.86	2.00	2.839 (3)	166
N4—H4B⋯O6ⁱⁱ	0.86	2.12	2.950 (3)	161
N6—H61⋯O4ⁱⁱ	0.88 (2)	2.10 (2)	2.955 (3)	166 (2)

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

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 structure-function-coordination relationships of the arylcarboxylate ion in Zn^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 (Nadzhafov et al., 1981). Nicotinamide (NA) is one form of niacin, and 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 structure determination of the title compound, a zinc complex with two methylaminobenzoate (MAB) and two nicotinamide (NA) ligands, was undertaken in order to determine the properties of the MAB and NA ligands and also to compare the results obtained with those reported previously.

The molecular structure of the title monomeric complex, containing two monodenate MAB and two monodentate NA ligands, is illustrated in Fig. 1. The coordination around the Zn atom is distorted tetrahedral (Table 1).

The near equalities of the C1—O1 [1.284 (2) Å], C1—O2 [1.248 (2) Å] and C9—O3 [1.278 (2) Å], C9—O4 [1.241 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds, as in the other zinc(II) complexes: bis(4-hydroxybenzoato-κO)bis(nicotinamide-κN)zinc(II) (Necefoğlu et al., 2002) and diaquabis(N,N'-diethylnicotinamide-κN)bis(4-\ fluorobenzoato-κO)- zinc(II) (Hökelek et al., 2007). This may be due to the intramolecular N—H···O hydrogen bonding of the carboxylate O atoms (Table 2).

The Zn atom is displaced out of the least-squares plane of the carboxylate groups (O1/C1/O2) and (O3/C9/O4) by -0.1070 (3) Å and -0.0967 (4) Å, respectively. The dihedral angles between the planar carboxylate groups (O1/C1/O2) and (O3/C9/O4) and the adjacent benzene rings, A (C2—C7) and B (C10—C15), are 7.92 (13)° and 6.60 (13)°, respectively. The dihedral angles between the two benzene rings, A and B, and the two pyridine rings, C (N1/C17—C21) and D (N3/C23—C27), are A/B = 78.30 (6)° and C/D = 68.86 (5)°. The benzene rings are oriented with respect to the pyridine rings at dihedral angles of A/C = 20.95 (5)°, A/D = 77.94 (6)°, B/C = 80.59 (5)° and B/D = 33.66 (6)°.

As can be seen from the crystal packing diagram (Fig. 2), the molecules are linked by intermolecular N—H···O hydrogen bonds to form an infinite three-dimensional network (Table 2).

Experimental

The title compound was prepared by the reaction of ZnNO₄ (1.61 g, 10 mmol) in H₂O (25 ml) and nicotinamide (2.44 g, 20 mmol) in H₂O (100 ml), with sodium 4-N-methylaminobenzoate (3.00 g, 20 mmol) in H₂O (100 ml), at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colorless single crystals.