Propane-1,2-diaminium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cuprate(II) tetra­hydrate

Hossein Aghabozorg; Ali Akbar Agah; Behrouz Notash; Masoud Mirzaei

doi:10.1107/S1600536811024378

. 2011 Jun 30;67(Pt 7):m992–m993. doi: 10.1107/S1600536811024378

Propane-1,2-diaminium bis(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)cuprate(II) tetrahydrate

Hossein Aghabozorg ^a,^*, Ali Akbar Agah ^a, Behrouz Notash ^b, Masoud Mirzaei ^c

PMCID: PMC3152145 PMID: 21836964

Abstract

In the title compound, (C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O, the Cu^II atom is six-coordinated in a distorted octahedral geometry by two tridentate pyridine-2,6-dicarboxylate (pydc) ligands. In the crystal, intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds, as well as π–π stacking interactions between the pyridine rings of the pydc ligands [centroid–centroid distance = 3.4714 (14) Å] are present. C=O⋯π interactions between the carbonyl groups and pyridine rings [O⋯centroid distances = 3.150 (2) and 3.2233 (19) Å] are also observed.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008d ▶). For related structures, see: Aghabozorg et al. (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O
M _r = 541.97
Orthorhombic,
a = 20.919 (4) Å
b = 8.2015 (16) Å
c = 12.739 (3) Å
V = 2185.6 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 120 K
0.50 × 0.40 × 0.35 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ▶) T _min = 0.602, T _max = 0.684
9693 measured reflections
5040 independent reflections
4803 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.075
S = 1.09
5040 reflections
350 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ▶), 1969 Friedel pairs
Flack parameter: −0.001 (10)

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; 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 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811024378/hy2413sup1.cif

e-67-0m992-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024378/hy2413Isup2.hkl

e-67-0m992-Isup2.hkl^{(246.9KB, 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
C10—H10⋯O11ⁱ	0.93	2.59	3.476 (3)	160
C11—H11⋯O7ⁱⁱ	0.93	2.56	3.301 (3)	137
C15—H15A⋯O8ⁱⁱⁱ	0.97	2.30	3.245 (3)	165
C16—H16⋯O5^iv	0.98	2.53	3.321 (3)	138
N3—H3A⋯O6^iv	0.89 (4)	1.93 (4)	2.812 (3)	170 (3)
N3—H3B⋯O11	0.95 (4)	1.88 (4)	2.773 (3)	155 (3)
N3—H3C⋯O2	0.90 (4)	1.91 (4)	2.794 (2)	167 (4)
N4—H4A⋯O10^iv	0.86 (3)	1.94 (3)	2.786 (3)	165 (3)
N4—H4B⋯O12	0.83 (4)	2.00 (4)	2.811 (3)	165 (3)
N4—H4C⋯O4^v	0.84 (2)	2.01 (2)	2.829 (3)	167 (3)
O9—H9A⋯O1	0.84 (2)	1.93 (2)	2.739 (3)	163 (3)
O9—H9B⋯O4^vi	0.82 (2)	2.04 (2)	2.826 (3)	160 (3)
O10—H10A⋯O9	0.78 (4)	1.97 (4)	2.731 (3)	164 (4)
O10—H10B⋯O8^v	0.85 (4)	1.88 (4)	2.724 (3)	170 (3)
O11—H11A⋯O3^v	0.82 (2)	2.41 (3)	3.080 (2)	140 (3)
O11—H11A⋯O7^v	0.82 (2)	2.30 (3)	2.957 (2)	138 (3)
O11—H11B⋯O10	0.82 (4)	1.98 (4)	2.781 (3)	169 (3)
O12—H12A⋯O2^vii	0.79 (2)	1.99 (2)	2.770 (3)	170 (3)
O12—H12B⋯O6^iv	0.81 (2)	2.09 (3)	2.786 (2)	144 (3)

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

Acknowledgments

We are grateful to Tarbiat Moallem University for financial support.

supplementary crystallographic information

Comment

Our group has previously reported some proton-transfer systems (Aghabozorg et al., 2008d), using pyridine-2,6-dicarboxylic acid (pydcH₂), propane-1,2-diamine (p-1,2-da) and propane-1,3-diamine (p-1,3-da), which formed the proton-transfer compounds (p-1,2-daH₂)(pydcH)₂.2H₂O (Aghabozorg et al., 2008c), (p-1,2-daH₂)[Ni(pydc)₂].4H₂O (Aghabozorg et al., 2008b), (p-1,3-daH₂)[Cd(pydc)₂].3.5H₂O, (p-1,3-daH₂)[Cu(pydc)₂].4H₂O and (p-1,3-daH2)[Co(pydc)₂].4H₂O (Aghabozorg et al., 2008a).

We describe here the crystal structure of the title compound (Fig. 1). In the complex anion, the Cu^II ion is six-coordinated by two (pydc)^2- ligands in a distorted octahedral geometry. In the crystal, there are N—H···O, O—H···O and weak C—H···O intermolecular hydrogen bonds (Table 1, Fig. 2). There are also π–π stacking interactions between the pyridine rings of the pydc ligands [centroid–centroid distance = 3.4714 (14) Å], as shown in Fig. 3. In addition, there are C═O···π interactions (Fig. 4) between the carbonyl groups and pyridine rings [O···centroid distances = 3.150 (2) and 3.2233 (19) Å].

Experimental

By mixing Cu(OAc)₂.H₂O (1 mmol), pyridine-2,6-dicarboxylic acid (2 mmol) and propane-1,2-diamine (1 mmol) in 20 ml water, a blue solution was obtained. Blue crystals of the title compound were obtained by allowing the mixture to stand at room temperature for a week.