Bis(9-amino­acridinium) bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)nickelate(II) trihydrate

Zohreh Derikvand; Marilyn M Olmstead

doi:10.1107/S1600536810016776

. 2010 May 15;66(Pt 6):m642–m643. doi: 10.1107/S1600536810016776

Bis(9-aminoacridinium) bis(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)nickelate(II) trihydrate

Zohreh Derikvand ^a,^*, Marilyn M Olmstead ^b

PMCID: PMC2979467 PMID: 21579293

Abstract

The title compound, (C₁₃H₁₁N₂)₂[Ni(C₇H₃NO₄)₂]·3H₂O, consists of a mononuclear anionic complex, two 9-aminoacridinium cations and three uncoordinated water molecules. Two pyridine-2,6-dicarboxylate (pydc) ligands are bound to the Ni^II ion, giving an NiN₂O₄ bonded set. The coordination geometry around the Ni^II atom is distorted octahedral. There are two types of robust O—H⋯O hydrogen-bond synthons, namely R ₆ ⁶(24) and R ₂ ⁴(8), which link the complex anions and water molecules to each other. N—H⋯O hydrogen bonds connect the stacks of anions and cations in the structure. Other intermolecular interactions, including weak C—H⋯O hydrogen bonds, π–π [shortest centroid–centroid distance = 3.336 (7) Å] and C—O⋯π [O⋯centroid distance = 3.562 (10) Å] interactions, connect the various components.

Related literature

For related structures containing [Ni(pydc)₂]²⁻ species, see: Aghabozorg et al. (2008 ▶, 2009 ▶); Attar Gharamaleki et al. (2009 ▶); Cui et al. (2009 ▶); Hadadzadeh et al. (2010 ▶); Safaei-Ghomi et al. (2009 ▶).

Experimental

Crystal data

(C₁₃H₁₁N₂)₂[Ni(C₇H₃NO₄)₂]·3H₂O
M _r = 833.44
Triclinic,
a = 10.7939 (10) Å
b = 13.3335 (12) Å
c = 13.9370 (13) Å
α = 102.288 (2)°
β = 103.609 (2)°
γ = 105.482 (2)°
V = 1795.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 90 K
0.36 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.809, T _max = 0.887
29993 measured reflections
11816 independent reflections
10951 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.076
S = 1.04
11816 reflections
659 parameters
All H-atom parameters refined
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.34 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: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810016776/hy2305sup1.cif

e-66-0m642-sup1.cif^{(33.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016776/hy2305Isup2.hkl

e-66-0m642-Isup2.hkl^{(577.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2Wⁱ	0.873 (18)	2.053 (18)	2.8793 (12)	157.6 (16)
N3—H3B⋯O7ⁱⁱ	0.878 (17)	2.109 (17)	2.9337 (11)	156.1 (15)
N4—H4A⋯O6	0.884 (17)	1.838 (17)	2.7214 (11)	178.1 (16)
N5—H5A⋯O3ⁱⁱⁱ	0.894 (17)	1.925 (17)	2.7945 (11)	163.9 (16)
N5—H5B⋯O5	0.889 (17)	2.046 (17)	2.9096 (11)	163.6 (15)
N6—H6A⋯O3W	0.836 (18)	1.863 (18)	2.6903 (11)	170.3 (18)
O1W—H1A⋯O7	0.83 (2)	1.99 (2)	2.8138 (11)	171 (2)
O1W—H1B⋯O7^iv	0.861 (19)	1.955 (19)	2.8161 (11)	178.7 (17)
O2W—H2A⋯O8^v	0.813 (19)	2.067 (19)	2.8717 (11)	170.1 (17)
O2W—H2B⋯O2	0.79 (2)	2.02 (2)	2.8033 (11)	177 (2)
O3W—H3C⋯O3^vi	0.79 (2)	1.97 (2)	2.7595 (11)	169.8 (19)
O3W—H3D⋯O1W^vii	0.856 (19)	1.879 (19)	2.7328 (11)	175.4 (17)
C30—H30⋯O3ⁱⁱⁱ	0.931 (16)	2.437 (16)	3.3386 (12)	163 (14)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

9-Aminoacridine is a highly fluorescent dye clinically used as a topical antiseptic and experimentally as a mutagen, an intracellular pH indicator and as a MALDI matrix. Acridine and related derivatives bind to DNA and RNA due to their abilities to intercalate. Many complexes containing pyridine-2,6-dicarboxylate (pydc), Ni^II ions and various bases have been reported (Aghabozorg et al., 2008, 2009; Attar Gharamaleki et al., 2009; Cui et al., 2009; Hadadzadeh et al., 2010; Safaei-Ghomi et al., 2009).

The asymmetric unit of the title compound consists of one [Ni(pydc)₂]^2- anion, two 9-aminoacridinuum cations and three uncoordinated water molecules (Fig. 1). In the synthesis, two carboxylic acid protons are transferred to the endocyclic N atoms of 9-aminoacridines. Two pydc ligands are bound to the metal ion to give a NiN₂O₄ bonded set, using all the coordination sites of the pydc ligand. The resulting coordination polyhedron can be described as distorted octahedral. In the anionic complex, the Ni—N bond distances [1.9648 (8) and 1.9760 (8) Å] are shorter than the Ni—O bond distances [2.1003 (7), 2.1120 (7), 2.1360 (7) and 2.1776 (7) Å]. It is worth pointing out that there are two types of robust hydrogen bond synthons, namely R⁶₆(24) and R²₄(8), which link the complex anions and water molecules to each other, as shown in Fig. 2. The dihedral angle between two coordinated pydc ligands is 85.14 (3)°, which shows that two ligands are almost perpendicular to each other. A feature of the title compound is the presence of π–π and C—O···π interactions. The shortest π–π distance is 3.336 (7) Å and C—O···π distances is 3.562 (10) Å (Fig. 3). Another feature in this crystal structure is intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds with D···A distances ranging from 2.6903 (11) to 3.3386 (12)Å (Table 1).

The packing consists of distinctive stacks of cations and anions that propagate along the a direction. These stacks are connected to each other by N—H···O hydrogen bonds, as shown in Fig. 4. This crystal structure is comparable to (H₃O)⁺(creatH)⁺[Ni(pydc)₂].3H₂O (creat = creatinine) (Attar Gharamaleki et al., 2009).

Experimental

An aqueous solution of Ni(NO₃)₂.6H₂O (145 mg, 0.5 mmol) in distilled water (5 ml) was added to methanolic solution of pyridine-2,6-dicarboxylic acid (167 mg, 1 mmol) in water (20 ml) and 9-aminoacridine (194 mg, 1 mmol) in methanol (5 ml) under stirring at 80°C in a 1:2:2 molar ratio. The green colored precipitated product was obtained. The precipitation was dissolved in solution of H₂O/DMSO in a volume ratio of 1:2 (5/10 ml). Green block crystals, suitable for X-ray characterization, were obtained after 4 d at room temperature.