(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxyl­ato)bis­(1,10-phenanthroline)nickel(II) 3.5-hydrate

Sergey Malinkin; Anatoliy A Kapshuk; Elzbieta Gumienna-Kontecka; Elena V Prisyazhnaya; Turganbay S Iskenderov

doi:10.1107/S1600536813017194

. 2013 Jun 26;69(Pt 7):m417–m418. doi: 10.1107/S1600536813017194

(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxylato)bis(1,10-phenanthroline)nickel(II) 3.5-hydrate

Sergey Malinkin ^a, Anatoliy A Kapshuk ^a, Elzbieta Gumienna-Kontecka ^b, Elena V Prisyazhnaya ^c, Turganbay S Iskenderov ^a,^*

PMCID: PMC3772441 PMID: 24046584

Abstract

The title compound, [Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O, crystallizes as a neutral mononuclear complex with 3.5 solvent water molecules. One of the water molecules lies on an inversion centre, so that its H atoms are disordered over two sites. The coordination environment of Ni^II has a slightly distorted octahedral geometry, which is formed by one O and five N atoms belonging to the N,O-chelating pyrazol-1-ide-5-carboxylate and two N,N′-chelating phenanthroline molecules. In the crystal, O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds involving the solvent water molecules and pyrazole-5-carboxylate ligands form layers parallel to the ab plane. These layers are linked further via weak π–π interactions between two adjacent phenanthroline molecules, with centroid-to-centroid distances in the range 3.886 (2)–4.018 (1) Å, together with C—H⋯π contacts, forming a three-dimensional network.

Related literature

The work presented here continues studies of complexes based on pyrazolate ligands with transition metals, see: Klingele et al. (2009 ▶); Malinkin et al. (2009 ▶, 2012a ▶,b ▶,c ▶); Ng et al. (2011 ▶); Penkova et al. (2008 ▶, 2009 ▶); Meyer & Pritzkow (2000 ▶); Bauer-Siebenlist et al. (2005 ▶); Świątek-Kozłowska et al. (2000 ▶). For related structures, see: Zhong et al. (2009 ▶); Zheng et al. (2009 ▶); Bouchene et al. (2013 ▶); Fang & Wang (2010 ▶); Fritsky et al. (2004 ▶, 2006 ▶); Kanderal et al. (2005 ▶); Moroz et al. (2010 ▶). For the starting material, see: Sachse et al. (2008 ▶).

Experimental

Crystal data

[Ni(C₇H₆N₂O₃)(C₁₂H₈N₂)₂]·3.5H₂O
M _r = 648.29
Triclinic,
a = 9.865 (3) Å
b = 11.659 (4) Å
c = 13.561 (5) Å
α = 91.91 (3)°
β = 98.85 (3)°
γ = 105.20 (4)°
V = 1482.8 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 170 K
0.23 × 0.18 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.857, T _max = 0.929
12624 measured reflections
6830 independent reflections
3040 reflections with I > 2σ(I)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.153
S = 0.85
6830 reflections
405 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: WinGX (Farrugia, 2012 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813017194/sj5334sup1.cif

e-69-0m417-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017194/sj5334Isup2.hkl

e-69-0m417-Isup2.hkl^{(334.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

N1—Ni1	2.041 (4)
N3—Ni1	2.085 (4)
N4—Ni1	2.080 (4)
N5—Ni1	2.078 (3)
N6—Ni1	2.093 (4)
O2—Ni1	2.066 (3)

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

Cg is the centroid of the N1/N2/C2/C3/C4 pyrazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.95	2.31	3.088 (6)	139
O4—H4B⋯N2ⁱ	0.94	2.01	2.906 (6)	157
O5—H5A⋯O4ⁱⁱ	0.86	2.02	2.875 (6)	172
O5—H5B⋯O1	0.90	2.00	2.787 (5)	145
O6—H6D⋯O5	0.87	2.05	2.895 (6)	163
O6—H6E⋯O2	0.88	1.98	2.827 (5)	163
O7—H7D⋯O3	0.89	2.16	2.964 (4)	150
O7—H7E⋯O4	0.89	2.02	2.821 (5)	149
C12—H12⋯Cg1ⁱⁱⁱ	0.93	2.77	3.646 (6)	158

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

Acknowledgments

The authors are grateful for financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Swedish Institute (Visby Program).

supplementary crystallographic information

Comment

The bridging nature of pyrazolate provides the possibility to bring metal ions into close proximity, which results in arrays with interesting magnetic and catalytic properties (Klingele et al., 2009; Malinkin et al., 2012b; Ng et al., 2011). Therefore, research focused on pyrazolate complexes with higher nuclearity is of special interest in the field of supramolecular and bioinorganic chemistry (Penkova et al., 2008, 2009; Meyer & Pritzkow, 2000; Bauer-Siebenlist et al., 2005). Mononuclear pyrazolate-based complexes bearing non-coordinated donor groups can potentially be used as building blocks for the synthesis of discrete clusters as well as extended frameworks that offer a wide range of possible applications. On the other hand, phenanthroline is often used in the synthesis of discrete polynuclear complexes in order to prevent formation of coordination polymers by blocking a certain number of vacant sites in the coordination sphere of a metal ion (Fritsky et al., 2004, 2006). Herein we report the synthesis and crystal structure of the title compound, (I), as a continuation of our earlier work devoted to complexes based on non-symmetrical pyrazole ligands (Penkova et al., 2008; Malinkin et al., 2012a,b), in particular, 3-acetyl-4-methyl-1H-pyrazole-5 carboxylic acid (Malinkin et al., 2009, 2012c).

As shown in Figure 1, the Ni^II ion is coordinated by one pyrazolate ligand viaN,O-chelating groups and two N,N-chelating phenanthroline molecules forming a slightly distorted octahedral coordination environment. The Ni—N_pz, Ni—N_phen and Ni—O distances are consistent with the reported data for related complexes (Fang & Wang, 2010; Zheng et al., 2009; Zhong et al., 2009; Bouchene et al., 2013).

The coordinated pyrazolate ligand exhibits C—C, C—N, N—N bond lengths which are normal for bridging pyrazolate rings (Penkova et al., 2008; Malinkin et al., 2012a,b; Świątek-Kozłowska et al., 2000). The C—O bond lengths in the deprotonated carboxylic groups differs significantly (1.239 (2) and 1.292 (2) Å) which is typical for monodentate coordinated carboxylates (Malinkin et al., 2012a,b). Also the C—N and C—C bond lengths in the phenanthroline ligand are similar to those separations observed in other 2-substituted pyridine derivatives (Kanderal et al., 2005; Moroz et al., 2010).

In the crystal packing the complex molecules are associated via intermolecular hydrogen bonds (Table 1) that involve O—H and N—H interactions between the donor atoms of pyrazolate ligand and solvate water molecules forming layers which are parallel to the xy plane (Fig. 2). In addition layers are stabilized by a weak π–π interactions between phenanthroline moieties with intercentroid distances of 4.018 (1) Å. Further complex species are united into three-dimensional motif through a π–π interactions found between two adjacent phenanthroline molecules belonging to the different layers (intercentroid distances 3.886 (2) and 3.950 (2) Å) and a C—H(phenanthroline)···π(pyrazole) contacts (the shortest H—centroid separation is around 2.77 Å).

Experimental

The compound was prepared by addition of 4 ml of a methanolic solution containing 0.0360 g (0.2 mmol) of phenanthroline and 0.0366 g (0.1 mmol) Ni(ClO₄)₂.6H₂O to a mixture containing 0.0167 g (0.1 mmol) L (Sachse et al., 2008) and 0.2 ml of aqueous NaOH solution (0.1 M) in 5 ml methanol.

Light-green crystals appeared after several days. Yield: 0.0227 g (35%). Elemental analysis calc. (%) for C₃₁H₂₉N_6NiO_6.5: C 57.38; H 4.47; N 12.96; found: C 57.22; H 4.30; N 13.05.