Propane-1,2-diammonium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O,N,O′)nickelate(II) tetra­hydrate

Hossein Aghabozorg; Mohammad Heidari; Sara Bagheri; Jafar Attar Gharamaleki; Mohammad Ghadermazi

doi:10.1107/S1600536808016309

. 2008 Jun 7;64(Pt 7):m874–m875. doi: 10.1107/S1600536808016309

Propane-1,2-diammonium bis(pyridine-2,6-dicarboxylato-κ³ O,N,O′)nickelate(II) tetrahydrate

Hossein Aghabozorg ^a,^*, Mohammad Heidari ^a, Sara Bagheri ^b, Jafar Attar Gharamaleki ^a, Mohammad Ghadermazi ^c

PMCID: PMC2961796 PMID: 21202746

Abstract

The reaction of nickel(II) nitrate hexahydrate, propane-1,2-diamine and pyridine-2,6-dicarboxylic acid in a 1:2:2 molar ratio in aqueous solution resulted in the formation of the title compound, (C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O or (p-1,2-daH₂)[Ni(pydc)₂]·4H₂O (where p-1,2-da is propane-1,2-diamine and pydcH₂ is pyridine-2,6-dicarboxylic acid). The geometry of the resulting NiN₂O₄ coordination can be described as distorted octahedral. Considerable C=O⋯π stacking interactions are observed between the carboxylate C=O groups and the pyridine rings of the (pydc)²⁻ fragments, with O⋯π distances of 3.1563 (12) and 3.2523 (12) Å and C=O⋯π angles of 95.14 (8) and 94.64 (8)°. In the crystal structure, a wide range of non-covalent interactions, consisting of hydrogen bonding [O—H⋯O, N—H⋯O and C—H⋯O, with D⋯A distances ranging from 2.712 (2) to 3.484 (2) Å], ion pairing, π–π [centroid-to-centroid distance = 3.4825 (8) Å] and C=O⋯π stacking, connect the various components to form a supramolecular structure.

Related literature

For related literature, see: Aghabozorg et al. (2007 ▶); Aghabozorg, Ghadermazi & Attar Gharamaleki (2006 ▶); Aghabozorg, Ghadermazi & Ramezanipour (2006 ▶); Aghabozorg, Heidari et al. (2008 ▶); Aghabozorg, Manteghi & Sheshmani (2008 ▶).

Experimental

Crystal data

(C₃H₁₂N₂)[Ni(C₇H₃NO₄)₂]·4H₂O
M _r = 537.13
Orthorhombic,
a = 20.7598 (6) Å
b = 8.2582 (2) Å
c = 12.7242 (4) Å
V = 2181.42 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 100 (2) K
0.26 × 0.22 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.781, T _max = 0.898
36654 measured reflections
6379 independent reflections
6016 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.059
S = 1.01
6379 reflections
310 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ▶), 2846 Friedel pairs
Flack parameter: 0.004 (7)

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 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016309/su2054sup1.cif

e-64-0m874-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016309/su2054Isup2.hkl

e-64-0m874-Isup2.hkl^{(312.2KB, 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
O1W—H1WA⋯O4W	0.82	1.97	2.788 (2)	173
O1W—H1WB⋯O2	0.82	2.47	3.109 (2)	135
O1W—H1WB⋯O6	0.82	2.21	2.912 (2)	144
O2W—H2WA⋯O3	0.82	2.21	2.759 (2)	125
N3—H3B⋯O4ⁱ	0.91	1.90	2.795 (2)	168
N3—H3C⋯O1W	0.91	1.91	2.763 (2)	155
N3—H3D⋯O8ⁱⁱ	0.91	1.88	2.783 (2)	176
O2W—H2WB⋯O1ⁱⁱⁱ	0.82	2.07	2.849 (2)	160
N4—H4B⋯O3Wⁱⁱ	0.91	1.92	2.812 (2)	165
N4—H4C⋯O1	0.91	1.92	2.813 (2)	168
N4—H4D⋯O4W^iv	0.91	1.91	2.777 (2)	160
O3W—H3WA⋯O8	0.82	2.03	2.771 (2)	149
O3W—H3WB⋯O4^v	0.82	1.99	2.787 (2)	166
O4W—H4WA⋯O2Wⁱ	0.82	1.99	2.749 (2)	153
O4W—H4WB⋯O5	0.82	1.90	2.712 (2)	171
C10—H10A⋯O6^vi	0.95	2.54	3.289 (2)	136
C11—H11A⋯O1W^vi	0.95	2.58	3.484 (2)	160
C15—H15B⋯O5^vii	0.99	2.30	3.268 (2)	164
C16—H16A⋯O7ⁱⁱ	1.00	2.49	3.291 (2)	137

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

supplementary crystallographic information

Comment

Recently, we have defined a plan to prepare water soluble proton transfer compounds as novel self-assembled systems that can function as suitable ligands in the synthesis of metal complexes. In this regard, we have reported cases in which proton transfers from pyridine-2,6-dicarboxylic acid (pydcH₂), and benzene-1,2,4,5-tetracarboxylic acid (btcH₄), to propane-1,3-diamine (pda), propane-1,2-diamine (p-1,2-da) and 1,10-phenanthroline, (phen). This work has resulted in the formation of some novel proton transfer compounds such as (pdaH₂)(pydc).(pydcH₂).2.5H₂O (Aghabozorg, Ghadermazi & Ramezanipour, 2006), (pdaH₂)₂(btc).2H₂O (Aghabozorg et al., 2007), (p-1,2-daH₂)(pydcH)₂.2H₂O (Aghabozorg, Heidari et al., 2008) and (phenH)₄(btcH₃)₂(btcH₂) (Aghabozorg, Ghadermazi & Attar Gharamaleki, 2006). For more details and related literature see our recent review article (Aghabozorg, Manteghi & Sheshmani, 2008).

The molecular structure and crystal packing diagram of the title compound are presented in Figs. 1 and 2, respectively. The Ni^II atom is six-coordinated by two pyridine-2,6-dicarboxylate, or (pydc)^2-, groups, i.e. each (pydc)^2- ligand is coordinated through one pyridine N atom and two carboxylate O atoms. As it can be seen, atoms N1 and N2 of the two (pydc)^2- fragments occupy the axial positions, while atoms O2, O3, O6 and O7 form the equatorial plane [with Ni—O distances ranging from 2.1178 (11) to 2.1477 (10) Å]. The N1—Ni1—N2 angle [176.17 (5)°] deviates from linearity. Therefore, the geometry of the resulting NiN₂O₄ coordination can be described as distorted octahedral. The O2—Ni1—O6 and O3—Ni1—O7 bond angles are equal to 87.26 (4)° and 90.55 (4)°, respectively. On the other hand, the torsion angles O3—Ni1—O7—C14 and O7—Ni1—O3—C7 are 92.68 (10)° and 95.05 (10)°, respectively, indicating that the two (pydc)^2- units are almost perpendicular to one another. The O2—Ni1—O3 [155.41 (4)°] and O6—Ni1—O7 [155.96 (4)°] bond angles indicate that the four carboxylate groups of the two dianions are oriented in a flattened tetrahedral arrangement around the Ni1 atom.

It is interesting to note that the crystal packing shows a layered structure. The space between the layers of [Ni(pydc)₂]^2- units is occupied by (p-1,2-daH₂)²⁺ cations and uncoordinated water molecules, which bridge the [Ni(pydc)₂]^2- units via hydrogen bonds (Fig 3 and Table 1). A noticeable feature of the title compound is the presence of C═O···π stacking interactions, between C═O groups of the carboxylate with aromatic rings of pyridine-2,6-dicarboxylate, with O···π distances of 3.1563 (12) Å for C13–O5···Cg1 (1/2 - x, 1/2 + y, -1/2 + z) and 3.2523 (12) Å for C6–O1···Cg2 (1/2 - x, -1/2 + y, 1/2 + z) [Cg1 and Cg2 are the centroids of the rings N1/C1–C5 and N2/C8–C12, respectively]. There is also considerable π–π stacking interactions between the two aromatic rings of the (pydc)^2- units, with a centorid–centroid distance of 3.4825 (8) Å (1/2 - x, -1/2 + y, -1/2 + z) [see Fig. 4]. In the crystal structure, a wide range of non-covalent interactions consisting of hydrogen bonding (of the type O—H···O, N—H···O and C—H···O with D···A ranging from 2.712 (2) Å to 3.484 (2) Å), ion pairing, π···π and C═ O···π stacking connect the various components to form a supramolecular structure.

Experimental

An aqueous solution of Ni(NO₃)₂.6H₂O (290 mg, 1 mmol), propane-1,2-diamine (80 mg, 2 mmol) and pyridine-2,6-dicarboxylic acid (360 mg, 2 mmol) was added to each other in a 1:2:2 molar ratio, and the reaction mixture was heated at about 40°C for 5 h. Green crystals of the title compound were obtained from the solution after four weeks at room temperature.