(μ-3,4-Diacetyl­hexa-2,4-diene-2,5-diol­ato-κ4 O 2,O 3:O 4,O 5)bis­[aqua(1,10-phen­an­thro­line-κ2 N,N′)copper(II)] bis­(tetra­fluorid­oborate) monohydrate

Jorge A Tovilla; Simón Hernández-Ortega; Jesús Valdés-Martínez

doi:10.1107/S1600536809006898

. 2009 Mar 6;65(Pt 4):m366–m367. doi: 10.1107/S1600536809006898

(μ-3,4-Diacetylhexa-2,4-diene-2,5-diolato-κ⁴ O ²,O ³:O ⁴,O ⁵)bis[aqua(1,10-phenanthroline-κ² N,N′)copper(II)] bis(tetrafluoridoborate) monohydrate

Jorge A Tovilla ^a, Simón Hernández-Ortega ^a, Jesús Valdés-Martínez ^a,^*

PMCID: PMC2969010 PMID: 21582322

Abstract

In the title compound, [Cu₂(C₁₀H₁₂O₄)(C₁₂H₈N₂)₂(H₂O)₂](BF₄)₂·H₂O, the two Cu atoms are each chelated by the acetylacetonate unit of the 3,4-diacetylhexa-2,4-diene-2,5-diolate (tae) ligand. The Cu atoms are square-pyramidally pentacoordinated, with one bidentate 1,10-phenanthroline (phen) and the tae ligand basal and one water molecule apical. The pyridyl rings of the phen ligands participate in π–π [centroid–centroid distance = 3.894 (3) Å] and C—H ⋯ π interactions, generating layers which are interconnected through O—H⋯O and O—H⋯F hydrogen bonds between the water molecules and the tetrafluoridoborate anions. The F atoms of both tetrafluoridoborate anions are each disordered over two positions of equal occupancy.

Related literature

For related Cu(II)–tae²⁻–diimine complexes, see: Shen et al. (1999a ▶,b ▶); Lim et al. (1994 ▶); Fukuda et al. (1994 ▶); Zhang et al. (1999 ▶). For other similar metal complexes, see: Zhang et al. (1998 ▶, 1999 ▶); Mei et al. (2006a ▶,b ▶).

Experimental

Crystal data

[Cu₂(C₁₀H₁₂O₄)(C₁₂H₈N₂)₂(H₂O)₂](BF₄)₂·H₂O
M _r = 911.35
Triclinic,
a = 11.5555 (9) Å
b = 12.0954 (9) Å
c = 15.4446 (12) Å
α = 67.654 (1)°
β = 78.890 (1)°
γ = 72.784 (1)°
V = 1899.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.21 mm⁻¹
T = 298 K
0.16 × 0.08 × 0.04 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.858, T _max = 0.949
15806 measured reflections
6928 independent reflections
3558 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.114
S = 0.84
6928 reflections
606 parameters
326 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶), publCIF (Westrip, 2009 ▶) and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006898/ng2549sup1.cif

e-65-0m366-sup1.cif^{(35KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006898/ng2549Isup2.hkl

e-65-0m366-Isup2.hkl^{(339KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O2	1.886 (3)
Cu1—O1	1.892 (3)
Cu1—N2	2.008 (4)
Cu1—N1	2.013 (4)
Cu1—O5	2.320 (4)
Cu2—O3	1.884 (3)
Cu2—O4	1.895 (3)
Cu2—N4	1.990 (4)
Cu2—N3	2.004 (4)
Cu2—O6	2.363 (5)

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O1—Cu1—N2	166.92 (15)
O2—Cu1—N1	171.40 (16)
O4—Cu2—N4	168.61 (17)
O3—Cu2—N3	172.57 (17)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯F1Aⁱ	0.845 (11)	1.91 (2)	2.737 (11)	166 (8)
O7—H7A⋯F6A	0.850 (11)	1.90 (3)	2.728 (9)	164 (8)
O7—H7A⋯F7	0.850 (11)	1.99 (4)	2.782 (8)	155 (8)
O6—H6E⋯F4ⁱⁱ	0.852 (11)	2.054 (18)	2.898 (9)	171 (7)
O6—H6D⋯F2Aⁱⁱⁱ	0.852 (11)	2.080 (16)	2.930 (10)	175 (7)
O6—H6D⋯F2ⁱⁱⁱ	0.852 (11)	1.90 (3)	2.694 (10)	155 (7)
O5—H5E⋯F3A	0.846 (11)	1.96 (2)	2.776 (8)	163 (6)
O5—H5D⋯O7^iv	0.842 (11)	2.000 (15)	2.837 (7)	173 (6)
O7—H7A⋯F7	0.850 (11)	1.99 (4)	2.782 (8)	155 (8)
O7—H7A⋯F6A	0.850 (11)	1.90 (3)	2.728 (9)	164 (8)
C29—H29⋯Cgⁱⁱ	0.93	2.75	3.522 (7)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg is the centroid of the N1,C12,C11,C13,C21,C20 ring.

Acknowledgments

JAT thanks CONACYT for a postdoctoral position. We thank CSCI, Spain, for a licence to use the Cambridge Structural Database.

supplementary crystallographic information

Comment

The asymmetric structure of 1 consists of one dinuclear [(phen)(H₂O)Cu(tae)Cu(H₂O)(phen)]²⁺ complex cation, two disordered BF₄^- anions and a water molecule, where phen represents the 1,10-phenanthroline, and tae the 3,4-diacetylhexa-2,4-diene-2,5-diolate, see Figure 1. In the cation one Cu atom coordinates to each acac^- moiety of the tae^2-. The Cu atoms are pentacoordinated with one bidentate phen and one water molecule in addition to the tae^2- ligand. The geometry around both Cu atoms is square pyramidal as indicated by the values of the τ parameter, 0.07 for both Cu1 and Cu2. The two acac moieties of the tae ligand deviate from the ideal geometry as indicated by the torsion angles C4—C3—C8—C7 and C2—C3—C8—C9, 99.9 (6) and 101.1 (6)°, respectively (ideal values 90°). The deviation of the ideal geometry is also reflected in the angle the central rings of the phen ligands C(14)—C(15)—C(22)—C(19)—C(20)—C(21) and C(26)—C(27)—C(34)—C(31)—C(32)—C(33) which has a value of 73.6 (3)°, ideal value 90°. The water molecule coordinated to Cu1 forms a hydrogen bond with the free water molecule, O(5) ···O(7) 2.835 (6) Å. In addition the three water molecules present interactions with the disordered BF₄^- anions. Two of the py rings of each phen ligands coordinated to the Cu1 present π-π interactions between them: N(1)—C(12)—C(11)—C(13)—C(21)—C(20) and N(2)—C(18)—C(17)—C(16)—C(22)—C(19)[2 - x,-y,2 - z], have centroid···centroid distance, Cg···Cg, of 3.894 (3) Å. H-bonded dimers are formed through C—H ··· π interactions between one py ring of the phen coordinated to Cu2 and a phen coordinated to Cu1, C(29)—H(29)···N(1)—C(12)—C(11)—C(13)—C(21)—C(20) [2 - x,1 - y,1 - z] with a C···Cg = 3.522 (7) Å, Figure 2.

Experimental

Copper(II) tetrafluoroborate hydrate (H₂O-31.2%) (0.188 g, 0.69 mmol) was added to a freshly made mixture of 1,10-phenanthroline (0.124 g, 0.69 mmol) and tetraacetylethane (0.068 g, 0.34 mmol) in methanol (15 ml) to give a dark green-blue suspension. The reaction mixture was stirred for 3 hrs at 45°C in a water bath, firstly and then at room temperature overnight. The blue-green solid was recovered by filtration and it was air-dried. 12 mg of the product were suspended in acetone (1 ml) and water (ca 1 ml) was added in order to achieve complete dissolution. Crystals suitable for X-ray analysis were obtained after 2 weeks of slow evaporation.