Di-μ4-succinato-tetra­kis[aqua­phenanthrolinecopper(II)] tetra­nitrate tetra­hydrate

Panana Kitiphaisalnont; Sutatip Siripaisarnpipat; Narongsak Chaichit

doi:10.1107/S1600536809039580

. 2009 Oct 3;65(Pt 11):m1284. doi: 10.1107/S1600536809039580

Di-μ₄-succinato-tetrakis[aquaphenanthrolinecopper(II)] tetranitrate tetrahydrate

Panana Kitiphaisalnont ^a, Sutatip Siripaisarnpipat ^a,^*, Narongsak Chaichit ^b

PMCID: PMC2971199 PMID: 21578054

Abstract

In the title compound, [Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O, the complete tetracation is generated by crystallographic inversion symmetry. Both unique Cu²⁺ ions are coordinated by an N,N′-bidentate phenanthroline molecule, two O-monodentate bis-bridging succinate dianions and a water molecule, resulting in distorted CuN₂O₃ square-based pyramidal geometries for the metal ions, with the water molecule occupying the apical site. In the crystal, the components are linked by O—H⋯O hydrogen bonds and aromatic π–π stacking interactions [minimum centroid–centroid separation = 3.537 (2) Å].

Related literature

For related structures, see: McCann et al. (1998 ▶); Padmanabhan et al. (2005 ▶); Ghosh et al. (2007 ▶).

Experimental

Crystal data

[Cu₄(C₄H₄O₄)₂(C₁₂H₈N₂)₄(H₂O)₄](NO₃)₄·4H₂O
M _r = 1599.29
Monoclinic,
a = 8.9180 (1) Å
b = 34.1090 (2) Å
c = 10.3620 (2) Å
β = 96.031 (1)°
V = 3134.51 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.10 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: none
23089 measured reflections
8980 independent reflections
7772 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.191
S = 1.05
8980 reflections
463 parameters
101 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.88 e Å⁻³
Δρ_min = −1.59 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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/S1600536809039580/hb5112sup1.cif

e-65-m1284-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039580/hb5112Isup2.hkl

e-65-m1284-Isup2.hkl^{(439.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—O2	1.948 (3)
Cu1—O5	1.966 (3)
Cu1—N2	2.011 (3)
Cu1—N1	2.015 (3)
Cu1—O4	2.240 (3)
Cu2—O1	1.946 (3)
Cu2—O6	1.952 (3)
Cu2—N4	2.007 (3)
Cu2—N3	2.025 (3)
Cu2—O3	2.160 (3)

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H4⋯O14	0.73 (7)	1.99 (7)	2.707 (7)	169 (7)
O3—H16⋯O13	0.70 (6)	2.07 (6)	2.772 (6)	177 (9)
O4—H23⋯O12	0.82 (6)	2.27 (6)	3.015 (7)	153 (5)
O4—H24⋯O10ⁱ	0.82 (5)	2.03 (6)	2.816 (6)	161 (8)
O13—H13C⋯O5ⁱⁱ	0.77 (7)	2.24 (7)	3.000 (5)	167 (7)
O13—H13D⋯O10ⁱⁱⁱ	0.71 (7)	2.23 (7)	2.899 (7)	159 (8)
O14—H14B⋯O9^iv	0.83 (7)	2.15 (6)	2.846 (13)	142 (6)
O14—H14C⋯O7^v	0.82 (9)	2.10 (9)	2.874 (14)	158 (10)

Open in a new tab

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

Acknowledgments

The authors thank the Royal Golden Jubilee PhD Program (RGJ) for financial support.

supplementary crystallographic information

Comment

The moleculular structure of the title compound, (I), consists of a tetranuclear [Cu₄(phen)₄(suc)₂(H₂O)₄].⁴⁺ species and uncoordinated water molecules and nitrate anions. Each Cu(II) ion (Table 1) exhibits a distorted square pyramidal coordination geometry through one apical water oxygen atom, two phen N atoms and two carboxylate O atoms from two succinate dianions which act as bis bridging ligands toward the Cu1 and Cu2 atoms (Fig. 1). The Cu1···Cu2 distance is 3.0318 (4) Å. The succinate ions also bridge two Cu(II) ions (Cu1' and Cu2'). The Cu1 and Cu2' distance separated by the bridging succinate anion is 6.396 Å. The face-to-face π-π interactions between the phenanthroline ring enhance the stability of the structure.

The apical water molecules form hydrogen bonds with nitrate O atoms (O···O distances of 2.810–2.920 Å) and uncoordinated water O atoms (O···O distances of 2.709–2.768Å): Table 2.

Experimental

The solvothermal systhesis was carried out in telflon-lined stainless steel autoclave. A mixture of Cu(NO₃)₂.2H₂O, phenantholine and succinic acid (mole ratio 1:1:1) in (H₂O)/MeOH (2:1) was heated at 423 K for 72 h. Green slabs of (I) in a green solution were obtained.