Propane-1,2-diaminium tris­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)zirconate(IV) trihydrate

Hoda Pasdar; Shahrzad Shakiba; Hossein Aghabozorg; Behrouz Notash

doi:10.1107/S1600536811008488

. 2011 Apr 13;67(Pt 5):m587. doi: 10.1107/S1600536811008488

Propane-1,2-diaminium tris(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)zirconate(IV) trihydrate

Hoda Pasdar ^a,^*, Shahrzad Shakiba ^a, Hossein Aghabozorg ^a, Behrouz Notash ^b

PMCID: PMC3089104 PMID: 21754310

Abstract

In the title compound, (C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O, the Zr^IV cation is chelated by three pyridine-2,6-dicarboxylate anions in a distorted tricapped trigonal–prismatic environment. The crystal structure is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For related structures, see: Aghabozorg et al. (2005 ▶); Daneshvar et al. (2008 ▶); Pasdar et al. (2010a ▶,b ▶, 2011a ▶,b ▶).

Experimental

Crystal data

(C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O
M _r = 716.73
Monoclinic,
a = 10.515 (2) Å
b = 19.195 (4) Å
c = 14.149 (3) Å
β = 103.39 (3)°
V = 2778.1 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 298 K
0.25 × 0.15 × 0.15 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ▶) T _min = 0.915, T _max = 0.926
21838 measured reflections
7481 independent reflections
5264 reflections with I > 2σ(I)
R _int = 0.133

Refinement

R[F ² > 2σ(F ²)] = 0.086
wR(F ²) = 0.206
S = 1.18
7481 reflections
427 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.09 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA (Stoe & Cie, 2005 ▶); data reduction: X-AREA; 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 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008488/xu5157sup1.cif

e-67-0m587-sup1.cif^{(30.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008488/xu5157Isup2.hkl

e-67-0m587-Isup2.hkl^{(366.1KB, 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
O13—H13A⋯O14	0.80 (8)	2.10 (9)	2.745 (11)	138 (13)
O13—H13B⋯O2ⁱ	0.80 (4)	2.10 (8)	2.793 (8)	145 (12)
O14—H14A⋯O5ⁱⁱ	0.91 (8)	2.11 (9)	2.978 (7)	158 (12)
O14—H14B⋯O8	0.85 (4)	1.89 (5)	2.731 (9)	171 (14)
O15—H15A⋯O12	0.98 (9)	1.91 (10)	2.857 (8)	164 (12)
O15—H15B⋯O1ⁱⁱⁱ	0.83 (4)	2.46 (7)	3.227 (9)	155 (13)
N4—H4A⋯O10^iv	0.89	1.92	2.791 (8)	165
N4—H4B⋯O6ⁱⁱ	0.89	2.24	2.851 (7)	125
N4—H4C⋯O15^v	0.89	2.04	2.864 (10)	154
N5—H5A⋯O13	0.89	1.94	2.769 (9)	154
N5—H5B⋯O6^iv	0.89	2.18	2.844 (8)	131
N5—H5C⋯O4	0.89	1.91	2.776 (8)	163

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

Acknowledgments

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

supplementary crystallographic information

Comment

Pyridine-2,6-dicarboxylic acid (pydcH₂) was commonly used by Aghabozorg and his co-workers as an acid in proton transfer systems (Aghabozorg et al. 2008). Our group have been focused on forming ion pairs between 2,6-pydcH₂ and various organic bases (Pasdar et al., 2010a; Pasdar et al. 2011a,b). The structure of two proton transfer compound containing nine-coordinated [Zr^IV(2,6-pydc)₃]^2- moiety were reported with the counter cationic part of 2,6-pyridinediamine(Aghabozorg et al. 2005) and 2,4,6-triamino-1,3,5-triazine (Daneshvar et al. 2008), respectively. Recently, we report the structure of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O (Pasdar et al. 2011a).

Herein, we report the synthesis and crystal structure of (1,2-pdaH₂)[Zr(2,6-pydc)₃].3H₂O. The title compound was prepared by the reaction of ZrCl₄.3H₂O, propane-1,2-diamine and 2,6-pyridinedicarboxylic acid in aqueous solution. Fig.1 present the molecular structure of the title compound. X-ray diffraction study shows that Zirconium(IV) ion is coordinated by three pydc^2- moiety in a distorted tricapped trigonal prismatic geometry and pydc^2- ligands act as tridentate ligand. Coordination environment around Zirconium(IV) ion in the (1,2-pdaH₂)[Zr(2,6-pydc)₃].3H₂O is presented in Fig. 2. The Zr—N and Zr—O bond lengths and angles are in the normal ranges (Aghabozorg et al. 2005; Daneshvar et al. 2008). The crystal packing diagram of the title compound is shown in Fig. 3. In the crystal packing diagram of the title compound, there are several intermolecular N—H···O, O—H···O hydrogen bonds which play an important role in stabilization of crystal structure (Table 1 and Fig. 3).

Experimental

A solution of propane-1,2-diamine (0.074 g, 1 mmol) in water (8 ml) and 2,6-pyridinedicarboxylic acid (0.501 g, 3 mmol) in water (10 ml) were mixed and stirred until clear solution obtained. Then a solution of ZrCl₄.3H₂O (0.116 g, 0.5 mmol) in water (5 ml) was added to the mixture of acid-base and stirrer for 5 h. Crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation after one month at room temperature (m.p: 210 °C).