Aqua­(2-hydrazino-1,10-phenanthroline)nitratocopper(II) nitrate

Hong Liang Li; Qi Sheng Liu

doi:10.1107/S1600536808015523

. 2008 May 30;64(Pt 6):m847. doi: 10.1107/S1600536808015523

Aqua(2-hydrazino-1,10-phenanthroline)nitratocopper(II) nitrate

Hong Liang Li ^a,^*, Qi Sheng Liu ^b

PMCID: PMC2961415 PMID: 21202525

Abstract

In the title mononuclear complex, [Cu(NO₃)(C₁₂H₁₀N₄)(H₂O)]NO₃, the Cu^II ion assumes a distorted square-pyramidal geometry. There is a π–π stacking interaction between the five-membered ring containing the Cu atom and a pyridine ring of a neighboring complex [centroid–centroid distance = 3.567 (2) Å and a perpendicular distance of 3.394 Å]. The crystal structure also contains intermolecular N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, linking cations and anions. In addition, there is a short intermolecular contact [2.784 (6) Å] between an O atom of the coordinated nitrate group and its symmetry-related atom.

Related literature

For related structures, see: Liu et al. (2008 ▶); Lewis et al. (1980 ▶).

Experimental

Crystal data

[Cu(NO₃)(C₁₂H₁₀N₄)(H₂O)]NO₃
M _r = 415.82
Monoclinic,
a = 8.7175 (8) Å
b = 10.7746 (10) Å
c = 16.4725 (16) Å
β = 97.175 (2)°
V = 1535.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 298 (2) K
0.50 × 0.20 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.525, T _max = 0.843
8857 measured reflections
3329 independent reflections
2735 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.112
S = 1.03
3329 reflections
235 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 local programs.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015523/wn2264sup1.cif

e-64-0m847-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015523/wn2264Isup2.hkl

e-64-0m847-Isup2.hkl^{(163.3KB, 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
N1—H1⋯O6ⁱ	0.86	2.18	2.936 (4)	146
N1—H1⋯O7ⁱ	0.86	2.54	3.181 (4)	132
N2—H2A⋯O3ⁱⁱ	0.90	2.22	3.111 (4)	169
N2—H2B⋯O7ⁱⁱⁱ	0.90	2.17	3.055 (4)	168
O1—H9⋯O5ⁱⁱⁱ	0.84	1.98	2.818 (3)	175
O1—H9⋯O7ⁱⁱⁱ	0.84	2.58	3.185 (3)	130
O1—H13⋯O6^iv	0.85	1.99	2.821 (3)	167
C2—H2⋯O6ⁱ	0.93	2.56	3.253 (4)	132
C3—H3⋯O1^v	0.93	2.48	3.280 (4)	144
C11—H11⋯O4^vi	0.93	2.43	3.118 (5)	131

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

supplementary crystallographic information

Comment

Derivatives of 1,10-phenanthroline play an important role in modern coordination chemistry (Liu et al., 2008), and although complexes with 2,9-dihydrazino-1,10-phenanthroline as ligand have been published (Lewis et al., 1980), to the best of our knowledge, no crystal structure of the title complex has been published.

Fig. 1 shows the structure, revealing that the Cu atom is in a distorted square-pyramidal environment, with atom O1 in the apical position. There is a single π-π stacking interaction involving symmetry-related 1,10-phenanthroline ligands, the relevant distances being Cg1···Cg2^v = 3.567 (2) Å and Cg1···Cg2^v_perp = 3.394 Å and α = 3.76° [symmetry code: (v) -x, 1 - y, -z; Cg1 and Cg2 are the centroids of the Cu1/N5/N6/C8/C9 ring and N6/C7/C8/C10-C12 ring, respectively; Cg1···Cg2¹_perp is the perpendicular distance from ring Cg1 to ring Cg2ⁱ; α is the dihedral angle between ring plane Cg1 and ring plane Cg2ⁱ]. There exists a short contact [2.784 (6) Å] between atom O3 and its symmetry-related atom O3ⁱⁱ [symmetry code: (ii) 1-x,-y,-z], as shown in Fig. 2 (double dashed lines). In addition, the crystal structure contains classical N—H..O and O—H···O hydrogen bonds, also non-classical C—H···O hydrogen bonds, as shown in Table 1 and Fig. 2. The π-π stacking interaction, the short contact between atom O3 and its symmetry-related atom O3ⁱⁱ and the hydrogen bonds stabilize the crystal structure.

Experimental

10 ml methanol solution of 2-hydrazino-1,10-phenanthroline (0.0105 g, 0.0576 mmol) was added to 5 ml aqueous solution of Cu(NO₃)₂.3H₂O (0.0390 g, 0.161 mmol) and the mixture was stirred for a few minutes. Deep-green single crystals were obtained after the filtrate had been allowed to stand at room temperature for two weeks.