Bis(7-amino-2,4-dimethyl-1,8-naphthyridine)dinitratocadmium(II)

Shou-Wen Jin; Qi-Jun Zhao; Xian-Gang Qian; Ru-Xiang Chen; Yan-Fen Shi

doi:10.1107/S160053680706271X

. 2007 Dec 6;64(Pt 1):m54–m55. doi: 10.1107/S160053680706271X

Bis(7-amino-2,4-dimethyl-1,8-naphthyridine)dinitratocadmium(II)

Shou-Wen Jin ^a,^*, Qi-Jun Zhao ^a, Xian-Gang Qian ^a, Ru-Xiang Chen ^a, Yan-Fen Shi ^a

PMCID: PMC2914938 PMID: 21200626

Abstract

In the title compound, [Cd(NO₃)₂(C₁₀H₁₁N₃)₂], two naphthyridine ring systems are coordinated to the Cd ion through the two N atoms in a bidentate chelating mode, whereas the remaining coordination sites are occupied by two O atoms from two different nitrate groups to complete the octahedral geometry. Intermoleular N—H⋯O hydrogen bonds link the molecules to form a one-dimensionnal sheet parallel to the ac plane. Weak slipped π–π stacking involving the naphthyridine ring systems stabilizes the structure.

Related literature

For related literature, see: Bayer (1979 ▶); Che et al. (2001 ▶); Gavrilova & Bosnich (2004 ▶); Jin et al. (2007 ▶); Kukrek et al. (2006 ▶); Mintert & Sheldrick (1995a ▶,b ▶); Oskui & Sheldrick (1999 ▶); Oskui, Mintert & Sheldrick (1999 ▶).

Experimental

Crystal data

[Cd(NO₃)₂(C₁₀H₁₁N₃)₂]
M _r = 582.86
Triclinic,
a = 9.308 (2) Å
b = 9.584 (2) Å
c = 15.067 (4) Å
α = 95.497 (3)°
β = 95.224 (3)°
γ = 116.865 (3)°
V = 1179.8 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 298 (2) K
0.45 × 0.37 × 0.31 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.667, T _max = 0.751
6136 measured reflections
4101 independent reflections
3346 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.081
S = 1.09
4101 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706271X/dn2283sup1.cif

e-64-00m54-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706271X/dn2283Isup2.hkl

e-64-00m54-Isup2.hkl^{(201KB, 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
N3—H3A⋯O2	0.86	2.23	3.033 (4)	155
N3—H3B⋯O5ⁱ	0.86	2.38	3.161 (4)	151
N6—H6A⋯O5	0.86	2.11	2.902 (4)	153
N6—H6B⋯O3ⁱⁱ	0.86	2.18	2.979 (4)	154

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

Table 2. Main π–π interactions (Å, °).

α is the dihedral angle between the planes. DCC is the length of the CC vector (centroid to centroid). τ is the angle(s) subtended by the plane(s) normal to CC (offset angle). Cg1 is the centroid of ring N1/C1/C5–C8; Cg2 is the centroid of ring N2/C1/C5–C2.

Centroid 1	Centroid 2	α	DCC	τ
Cg1	Cg2ⁱⁱⁱ	1.32	3.862 (2)	26
Cg2	Cg2ⁱⁱⁱ	0.0	3.823 (2)	25

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Symmetry code: (iii) Inline graphic .

Acknowledgments

The authors thank the Zhejiang Forestry University Science Foundation for financial support.

supplementary crystallographic information

Comment

Molecular structures and chemical properties of transition metal complexes of 1,8-naphthyridine (napy) and its derivatives have received much attention(Kukrek et al., 2006; Che et al., 2001), because the ligands can link to metals with several coordination modes such as monodentate, chelating bidentate, and dinuclear bridging binding fashion (Gavrilova & Bosnich, 2004). 5,7-dimethyl-1,8-naphthyridin-2-amine (L) is a potentially tridentate ligand and is capable of linking two to four metal atoms together to form metal aggregates (Oskui et al., 1999; Mintert & Sheldrick, 1995a; Oskui & Sheldrick, 1999; Mintert & Sheldrick, 1995b). The coordination chemistry of 5,7-dimethyl-1,8-naphthyridine-2-amine has not been well studied before although a series of transiton metal complex (M₍_L₎2_Cl2) were once described in a US patent (Bayer, 1979). As an extension of our study on naphthyridine coordination chemistry(Jin et al., 2007), herein the title complex [Cd(L)₂(NO₃)_2] is reported.

In the title compound, two naphthyridine are coordinated to the Cd ion through two nitrogen atoms in bidentate chelating mode whereas the remaining coordination sites are occupied by two oxygen atoms from two different nitrates (Fig. 1). The two nitrate ligands display a dissymetric chelating mode with Cd—O distances of 2.357 (4) and 2.718 (4). The remaining distances are within the usual range. The two naphthyridine rings were almost perpendicular to each other making dihedral angle of 80.22 (7)°. The two chelating Cd—O—N—O group make dihedral angle of 81.21 (12)°.

Intermoleular N—H···O hydrogen bonds link the molecules to form a one dimensionnal sheet parallel to the a axis (Table 1, Fig. 2). Weak slippest π-π stackings involving the naphthyridine rings stabilize the structure (Table 2).

Experimental

All reagents and solvents were used as obtained without further purification. The CHN elemental analyses were performed on a Perkin-Elmer model 2400 elemental analyzer. A solution of cadmium nitrate tetrahydrate (31.4 mg, 0.1 mmol) in methanol (3 ml) was added to L (52.2 mg, 0.3 mmol) in methanol (10 ml) to give a colorless solution. The methanol solution was filtered. The solution was left standing at room temperature for several days, colorless block crystals were isolated. Yield: 41 mg, 70.3%. Anal. Calcd. for C₂₀H₂₂Cd_N8_O6: C, 41.18; H, 3.77; N, 19.22. Found: C, 41.14; H, 3.72; N, 19.18.