3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carb­oxy­pyridine-2-carboxyl­ato)(pyridine-2,6-dicarboxyl­ato)cuprate(II) trihydrate

S Yousuf; A S Johnson; S A Kazmi; O E Offiong; Hoong-Kun Fun

doi:10.1107/S1600536811011147

. 2011 Mar 31;67(Pt 4):m509–m510. doi: 10.1107/S1600536811011147

3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cuprate(II) trihydrate

S Yousuf ^a, A S Johnson ^b, S A Kazmi ^a, O E Offiong ^b, Hoong-Kun Fun ^c,^*,^‡

PMCID: PMC3099907 PMID: 21754014

Abstract

In the complex anion of the title compound, (C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O, the Cu^II atom is coordinated by tridentate 6-carboxypyridine-2-carboxylate and pyridine-2,6-dicarboxylate ligands and is surrounded by four O atoms in the equatorial plane and two N atoms in axial positions in a distorted octahedral geometry. In the crystal, the components are linked into a three dimensional network by O—H⋯O, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds and a π–π interaction with a centroid–centroid distance of 3.6080 (8) Å.

Related literature

For general background to and applications of supramolecular arrangements, see: Lehn (1995 ▶); Aghajani et al. (2009 ▶); Tshuva & Lippard (2004 ▶); Kuzelka et al. (2003 ▶). For crystal structures of related complexes, see: Aghabozorg et al. (2007 ▶); Ramos Silva et al. (2008 ▶); Wang et al. (2004 ▶); MacDonald et al. (2004 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

(C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O
M _r = 548.92
Orthorhombic,
a = 11.3091 (2) Å
b = 14.9442 (3) Å
c = 24.6045 (5) Å
V = 4158.29 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 100 K
0.54 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.583, T _max = 0.921
55434 measured reflections
9184 independent reflections
6619 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.098
S = 1.05
9184 reflections
368 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011147/is2693sup1.cif

e-67-0m509-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011147/is2693Isup2.hkl

e-67-0m509-Isup2.hkl^{(440.2KB, 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
O8—H1O8⋯O1ⁱ	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3⋯O2Wⁱⁱ	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5⋯O3Wⁱⁱⁱ	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5⋯N4^iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6⋯O2Wⁱⁱ	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6⋯O3^v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7⋯O3Wⁱⁱⁱ	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7⋯O7^vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1⋯O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1⋯O5^v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2⋯O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2⋯O1ⁱ	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3⋯O6^vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3⋯O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A⋯O6^viii	0.93	2.35	3.2042 (18)	153
C12—H12A⋯O7ⁱ	0.93	2.47	3.3960 (17)	176

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

Acknowledgments

AJ thanks The Academy of Sciences for the Developing World (TWAS) for the award of a Research and Advanced Training Fellowship and the H·E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, for providing research facilities. SY thanks the School of Physics, Universiti Sains Malaysia, for providing X-ray diffraction research facilities. HKF thanks the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Non-covalent supramolecular arrangements due to the non-covalent interactions between two or more molecular sub-units are responsible for influencing different structural properties and the addition of metal in the coordination is considered to be an effective tool to study and control the connectivity and linkages (Lehn et al., 1995). The study of the construction of metal organic frameworks indicates that under suitable conditions, the transfer of the acidic protons to appropriate bases will result in increased intermolecular interactions and as a result enhanced stabilization of the resulting system (Aghajani et al., 2009). The study of metal carboxylates has always been fascinating for the researchers because they play important roles not only in synthetic chemistry, considering the vast array of coordination modes of the carboxylate group, but also in biological activities (Tshuva et al., 2004; Kuzelka et al., 2003) and physiological effects (Aghabozorg et al., 2007). In our ongoing research to study the packing features of molecules containing metal chelate and triazole rings, the title Cu complex (I) was prepared from 3,5-diamino-1,2,4-triazole and dipicolinic acid.

The title complex, (C₂H₆N₅)⁺[Cu(C₇H₄NO₄)(C₇H₃NO₄)]^-.3H₂O, contains two tridentate dipicolinate ligands (one neutral and one protonated) coordinated with Cu(II) to reveal a distorted octahedral geometry, one independent protonated triazole and three water molecules (Fig. 1). The coordination environment around the Cu(II) ion is such that the two dipiconilate ligands are assembled perpendicular to each other with two axially oriented N atoms [Cu1—N1 = 1.9057 (12) Å, Cu1—N2 = 1.9723 (2) Å] and four O atoms on the basal positions [Cu1—O1 = 2.0889 (10) Å, Cu1—O2 = 2.0453 (10) Å, Cu1—O3 = 2.2727 (10) Å, Cu1—O4 = 2.3939 (10) Å]. Coordination of Cu^II ion with N1, O1, O2 and N2, O3, O4 of the two chelating dipicolinate ligands is responsible for the formation of four five-membered rings, A, (Cu1/O1/C1/C2/N1, with a maximum deviation of 0.049 (1) Å for atom O1), B (Cu1/N1/C6/C7/O2, with a maximum deviation of -0.042 (1) Å for atom O2), C (Cu1/O3/C8/C9/N2, with a maximum deviation of -0.043 (1) Å for atom C8) and D (Cu1/N2/C13/C14/O4, with a maximum deviation of -0.040 (1) Å for atom N2). The dihedral angles between them are 4.34 (6)° (A/B), 82.15 (6)° (A/C), 84.95 (6)° (A/D), 79.10 (6)° (B/C), 81.79 (6)° (B/D) and 3.58 (5)° (C/D). The independent triazole ring (N3/C15/N4/N5/C16) is essentially planar. All bond lengths are in agreement with another related structure (Ramos Silva et al., 2008). O—H···O, N—H···O, N—H···N and C—H···O hydrogen bonds play important roles in stabilizing the crystal structure by forming a two-dimensional-network, which is further extended to three-dimensional-network due to the intermolecular linkages made by water solvates (Table 2 and Fig. 2). The three-dimensional network is further strengthened by significant π–π interactions between (N1/C1–C5) pyridine (centroid Cg5) and triazole (N3/C15/N4/N5/C16) (centroid Cg7) rings [Cg5···Cg7^vii distance = 3.6080 (8) Å; (vii) -1/2 + x, 1/2 - y, -z].

Experimental

Pyridine-2,6-dicarboxylic acid (dipicolinic acid, H2dipic) and 3,5-diamino-1,2,4-triazole (datrz) were purchased from Merck and Molekula, respectively. Copper (II) sulfate pentahydrate (CuSO₄.5H₂O) and HPLC grade methanol were Uni- Chem and M TEDIA products, respectively. Deionized water was also used in the procedures when needed.

Synthesis of (Hdatrz)⁺[Cu(Hdipic)(dipic)]^-.3H₂O 1 mmol (0.099 g) of 3,5-diamino-1,2,4-triazole(datrz) and 1 mmol of dipicolinic acid (0.167 g) were dissolved in a mixture of methanol/water solution (1:10, 11 ml). The resulting solution was heated to 600 °C with stirring. An aqueous solution (1 ml) containing 0.5 mmol (0.125 g) of CuSO₄.5H₂O was added to the stirred solution. The greenish suspension was allowed to stir further for 1 hr, and then filtered while hot. The filtrate was kept at room temperature. Well shaped blue crystals of the title compound were formed by slow evaporation of the solution after 5 days. Percentage yield based on copper is 51.67%.