Aqua­(dicyanamido-κN 1)(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)(nitrato-κ2 O,O′)cobalt(II)–2,9-dimethyl-1,10-phenanthroline–water (2/1/2)

Feng-Hua Cui; Pei-Zheng Zhao

doi:10.1107/S1600536811035148

. 2011 Sep 14;67(Pt 10):m1341–m1342. doi: 10.1107/S1600536811035148

Aqua(dicyanamido-κN ¹)(2,9-dimethyl-1,10-phenanthroline-κ² N,N′)(nitrato-κ² O,O′)cobalt(II)–2,9-dimethyl-1,10-phenanthroline–water (2/1/2)

Feng-Hua Cui ^a,^b, Pei-Zheng Zhao ^a,^*

PMCID: PMC3201307 PMID: 22065101

Abstract

In the title compound, 2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O, the Co^II ion is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, a bidentate nitrate anion, a water molecule and a monodentate dicyanamide group in a distorted octahedral geometry. One uncoordinated dmphen molecule is situated on a crystallographic twofold axis and the asymmetric unit is completed by one water molecule. In the crystal, molecules form a one-dimensional framework in the [001] direction through O—H⋯N and O—H⋯O hydrogen bonds. The crystal packing is further stabilized by π–π stacking interactions between the dmphen rings of neighboring molecules, with a centroid–centroid separation of 3.5641 (8) Å and a partially overlapped arrangement of parallel dmphen rings with a distance of 3.407 (2) Å.

Related literature

For background to metal–phenanthroline complexes, see: Naing et al. (1995 ▶); Wang et al. (1996 ▶); Wall et al. (1999 ▶). For related Co(II)–phenanthroline structures, see: Ding et al. (2006 ▶); Xuan & Zhao (2007 ▶); Zhao et al. (2008 ▶).

Experimental

Crystal data

2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O
M _r = 1070.82
Monoclinic,
a = 17.993 (6) Å
b = 11.770 (4) Å
c = 23.428 (7) Å
β = 106.981 (4)°
V = 4745 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 291 K
0.34 × 0.18 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.781, T _max = 0.917
17592 measured reflections
4400 independent reflections
2862 reflections with I > 2σ(I)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.196
S = 1.04
4400 reflections
328 parameters
36 restraints
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035148/bh2369sup1.cif

e-67-m1341-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035148/bh2369Isup2.hkl

e-67-m1341-Isup2.hkl^{(215.7KB, 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
O4—H1W⋯O5ⁱ	0.85	2.57	3.111 (9)	123
O4—H2W⋯N7	0.85	1.97	2.810 (6)	167
O5—H4W⋯N5ⁱⁱ	0.85	2.25	2.830 (15)	126

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

Financial support from the National Natural Science Foundation of Henan Educational Committee (2011 A150018) is gratefully acknowledged.

supplementary crystallographic information

Comment

Metal-phenanthroline complexes and their derivatives have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Some Co(II)-phenanthroline complexes have been synthesized and structures were determined (Ding et al., 2006; Xuan & Zhao, 2007; Zhao et al., 2008). Recently, we obtained the title cobalt(II) complex, by reacting 2,9-dimethyl-1,10-phenanthroline, NaN(CN)₂ and Co(NO₃)₂ in an ethanol/water mixture. The structure of the title compound, 2[Co(C₁₄H₁₂N₂)N(CN)₂NO₃H₂O]^.C₁₄H₁₂N₂^.2H₂O is described below.

Each Co^II ion is six-coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, two O atoms from a nitrate anion, one O atom from a water molecule and one N from a dicyanamide anion. The water and N3/C15/N4/C16/N5 ligands occupy the axial positions, with a N3—Co1—O4 bond angle of 171.71 (16)°. The Co^II ion locates in the center, and CoO₃N₃ unit forms a distorted octahedral geometry. The uncoordinated dmphen molecule is placed on a crystallographic twofold axis (Fig. 1).

In the crystal structure, molecules are linked into a one-dimensional framework by O—H···N and O—H···O hydrogen bonds (Fig. 2). A partially overlapped arrangement of neighboring parallel Co1A-dmphen and Co1B-dmphen [symmetry code: (A) -x + 1, y, -z + 1/2; (B) -x + 1, -y + 1, -z + 1] rings with distance of 3.4065 (20) Å is observed. The shorter face-to-face separation clearly indicates the existence of π-π stacking between the dmphen rings. Uncoordinated N7A-dmphen and N7B-dmphen rings are also parallel with distance of 10.4286 (19) Å. In addition, the distance between the ring centroids Cg (C4A···C7A/C11A/C12A) and Cg (C17A···C20A/C22A/N7A) is 3.5641 (8) Å (Fig. 3). This value is close to the van der Waals thickness of the π-π stacking between nearly parallel dmphen (N7A-dmphen with Co1A-dmphen and Co1B-dmphen with N7B-dmphen) rings [dihedral angle: 3.4 (1)°].

Experimental

NaN(CN)₂ (0.0892 g, 1 mmol) was dissolved in distilled water (10 ml) and Co(NO₃)₂.6H₂O (0.1456 g, 0.5 mmol) was added. This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C₁₄H₁₂N₂.0.5H₂O, 0.1088 g, 0.5 mmol) in ethanol (10 ml). The mixture was stirred at 323 K and then refluxed for 5 h, cooled to room temperature and filtered. Pink single crystals appeared over a period of 8 days by slow evaporation at room temperature.