A new polymorph of aqua­bis­(1,10-phenanthroline-κ2 N,N′)copper(II) dinitrate

Mehdi Boutebdja; Asma Lehleh; Adel Beghidja; Zouaoui Setifi; Hocine Merazig

doi:10.1107/S1600536814008198

. 2014 Apr 18;70(Pt 5):m185–m186. doi: 10.1107/S1600536814008198

A new polymorph of aquabis(1,10-phenanthroline-κ² N,N′)copper(II) dinitrate

Mehdi Boutebdja ^a, Asma Lehleh ^a, Adel Beghidja ^a,^*, Zouaoui Setifi ^a, Hocine Merazig ^a

PMCID: PMC4011280 PMID: 24860316

Abstract

The title molecule, [Cu(C₁₂H₈N₂)₂(H₂O)](NO₃)₂, is a new polymorph of a compound which up to now has been reported to crystallize space groups in C2/c and Cc. The crystal studied was twinned by non-merohedry (final BASF factor of 0.40043) with the structure being solved and refined in P-1. The Cu^II atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and an O atom from a water molecule in an approximate trigonal–bipyramidal geometry. Discrete entities of one cation and two nitrate anions are formed by water–nitrate O—H⋯O hydrogen bonds. The components are further assembled into a three-dimensional network by C—H⋯O hydrogen bonds.

Related literature

For structural analyses of the other polymorphs, see: Nakai & Deguchi (1975 ▶); Catalan et al. (1995 ▶); Szpakolski et al. (2010 ▶); Zhou (2011 ▶).

Experimental

Crystal data

[Cu(C₁₂H₈N₂)₂(H₂O)](NO₃)₂
M _r = 565.99
Triclinic,
a = 7.0836 (3) Å
b = 11.7898 (3) Å
c = 14.2951 (4) Å
α = 78.079 (2)°
β = 79.862 (3)°
γ = 73.782 (3)°
V = 1112.68 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 150 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
17314 measured reflections
11903 independent reflections
10562 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.172
S = 1.17
11903 reflections
344 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); 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: ATOMS (Dowty, 1995 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814008198/im2451sup1.cif

e-70-0m185-sup1.cif^{(35.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008198/im2451Isup2.hkl

e-70-0m185-Isup2.hkl^{(651.6KB, hkl)}

CCDC reference: 996861

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2ⁱ	0.79	1.92	2.709 (5)	176
O1W—H2W⋯O6	0.87	1.89	2.718 (5)	159
C2—H2⋯O1ⁱⁱ	0.93	2.57	3.313 (5)	137
C5—H5⋯O5ⁱⁱⁱ	0.93	2.40	3.271 (5)	156
C6—H6⋯O6^iv	0.93	2.56	3.417 (6)	154
C8—H8⋯O3^v	0.93	2.50	3.194 (5)	131
C17—H17⋯O2^vi	0.93	2.49	3.363 (5)	157
C18—H18⋯O1^vii	0.93	2.50	3.406 (5)	166
C20—H20⋯O3^vii	0.93	2.49	3.357 (5)	155

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

Acknowledgments

The authors thank the MESRS (Algeria) for financial support. AL also thanks the DG–RSDT and ANDRU (Direction Générale de la Recherche Scientifique et du Dévelopement Technologique et l’Agence Nationale pour le Développement de la Recherche Universitaire, Algeria) for support through the PNR project.

supplementary crystallographic information

1. Comment

The reported structure of complex (I) is a polymorph of previously reported material. It crystallizes as a non-merohedral twin in the triclinic system with the space group P1, contrary to what has been observed in other structural analyses which three times report the crystal symmetry to correspond to the space group C2/c (Nakai & Deguchi (1975); Szpakolski et al. (2010); Zhou (2011)), while the fourth crystal structure was reported in the space group Cc (Catalan et al., 1995).

Compound (I) has a discrete structure containing monomeric [Cu(H₂O)(1,10'-phen)]²⁺ cations and two counter-balanced nitrate anions which are connected to the cation via O–H···O hydrogen bonds. The Cu(II) ion is coordinated by two 1,10'-phenantroline molecules each acting as a bidentate ligand (through the four nitrogen atoms (N1,N2, N4,N3)) and one water molecule O1w (Fig. 1). The geometry around the metal is of distorted trigonal bipyramidal geometry and all distances are in a normal range. The dihedral angle between the two 1,10'-phenantroline molecules is 34.92 (3)°, while the dihedral angle varies in its analogous between 37.89 (3)° and 53.46 (3)°. In the crystal, molecules are linked by extensive hydrogen bonds involving the nitrate anions and phenantroline and water molecules, producing a three-dimensional network (Fig 2).

2. Experimental

A methanolic solution containing Cu(NO₃)₂ × 3 H₂O (0.1208 g, 0.5 mmol) was added with stirring to a methanolic solution containing 1,10'-phenantroline (0.9 g, 0.5 mmol). After a few minutes a blue green precipitate appears and was filtrated. The blue green filtrate was kept for several weeks at room temperature. Green crystals suitable for X-ray analysis were obtained (yield: 0.20 g, 70% on the basis of Cu(NO₃)₂.3H₂O).