Bis(guanidinium) tris­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)zirconate(II) tetra­hydrate

Masoumeh Tabatabaee; Mahnaz Adineh; Zohreh Derikvand; Jafar Attar Gharamaleki

doi:10.1107/S1600536812011439

. 2012 Mar 24;68(Pt 4):m462–m463. doi: 10.1107/S1600536812011439

Bis(guanidinium) tris(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)zirconate(II) tetrahydrate

Masoumeh Tabatabaee ^a,^*, Mahnaz Adineh ^a, Zohreh Derikvand ^b, Jafar Attar Gharamaleki ^c

PMCID: PMC3343856 PMID: 22589830

Abstract

In the title complex, (CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O, the Zr^IV ion lies on a twofold rotation axes and is coordinated by six O and three N atoms of three tridentate pyridine-2,6-dicarboxylate ligands, forming a slightly distorted tricapped trigonal–prismatic geometry. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the components into a three-dimensional network.

Related literature

For related structures, see: Aghabozorg et al. (2005 ▶); Tabatabaee (2010 ▶); Tabatabaee et al. (2009 ▶, 2011a ▶,b ▶,c ▶, 2012 ▶); Derikvand et al. (2010 ▶); Attar Gharamaleki et al. (2009 ▶).

Experimental

Crystal data

(CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O
M _r = 778.77
Orthorhombic,
a = 17.2444 (9) Å
b = 10.8583 (5) Å
c = 16.5268 (8) Å
V = 3094.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 120 K
0.17 × 0.15 × 0.07 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.884, T _max = 0.970
32229 measured reflections
4116 independent reflections
2884 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.146
S = 1.07
4116 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL, DIAMOND (Brandenburg, 1999 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812011439/lh5430sup1.cif

e-68-0m462-sup1.cif^{(23KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011439/lh5430Isup2.hkl

e-68-0m462-Isup2.hkl^{(201.8KB, 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—H3NA⋯O1	0.77	2.23	3.003 (4)	175
N3—H3NB⋯O2Wⁱ	0.86	2.15	2.930 (4)	150
N4—H4NA⋯O2Wⁱ	0.83	2.04	2.818 (4)	156
N4—H4NB⋯O1Wⁱⁱ	0.78	2.06	2.834 (4)	175
N5—H5NA⋯O2	0.88	1.95	2.828 (4)	171
N5—H5NB⋯O3ⁱⁱⁱ	0.79	2.45	3.143 (4)	148
N5—H5NB⋯O4ⁱⁱⁱ	0.79	2.52	3.171 (4)	141
O1W—H1WA⋯O3^iv	0.84	2.33	3.041 (3)	143
O1W—H1WA⋯O5^iv	0.84	2.38	3.076 (3)	140
O1W—H1WB⋯O6	0.89	1.87	2.761 (3)	175
O2W—H2WA⋯O5^iv	0.86	2.07	2.909 (3)	165
O2W—H2WA⋯O6^iv	0.86	2.57	3.085 (3)	119
O2W—H2WB⋯O4^v	0.94	1.84	2.745 (3)	160

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

Acknowledgments

The authors wish to express their deepest appreciation to the late Professor Dr. H Aghabozorg who has inspired, advised and assisted during this study.

supplementary crystallographic information

Comment

In recent years, our research group has been interested in the synthesis of proton transfer compounds and study of their behavior with metal ions. We have focused on the proton delivery of polycarboxylic acids. Pyridine-2,6-dicarboxylic acid (pydcH₂) is a very important carboxylate derivative and has attracted much interest in coordination chemistry. This is the acid we have utilized widely in our studies (Tabatabaee et al., 2010, 2011a, 2011b, 2011c, 2012; Derikvand et al., 2010; Attar Gharamaleki et al., 2009). In this paper we report the crystal structure of the title complex (I). The Zr^IV ion lies on a twofold rotation axis. The asymmetric unit and the symmetry complete cation is shown in Fig. 1. The Zr^IV atom is coordinated by three tridentate pydc ligands forming a slightly distorted tricapped trigonal prismatic environment (Fig. 2). The Zr—N distances and Zr—O distances are consistent with those found in (pydaH)₂[Zr(pydc)₃].5H₂O (Aghabozorg et al., 2005). In the crystal, O—H···O and N—H···O hydrogen bonds (Table 1) link the components into a three-dimensional network (Fig. 3).

Experimental

An aqueous solution of ZrOCl₂.8H₂O, (161 mg, 0.5 mmol) in water (5 ml) was added to a stirring solution of (20 ml) pyridine-2,6-dicarboxylic acid (176 mg, 1 mmol) and guanidine hydrochloride (95 mg, 1 mmol). The reaction mixture was stirred at 298K for 1 h. Colorless crystals of the title compound were obtained after 4 days by slow evaporation of the solvent at room temperature.