(3-{[N-(5-Chloro-2-hy­droxy­phen­yl)oxamo­yl]amino}­prop­yl)dimethyl­aza­nium perchlorate

Xi-Teng Yue; Xiao-Wen Li; Zhi-Yong Wu

doi:10.1107/S1600536811050653

. 2011 Dec 3;68(Pt 1):o8. doi: 10.1107/S1600536811050653

(3-{[N-(5-Chloro-2-hydroxyphenyl)oxamoyl]amino}propyl)dimethylazanium perchlorate

Xi-Teng Yue ^a, Xiao-Wen Li ^b, Zhi-Yong Wu ^b,^*

PMCID: PMC3254288 PMID: 22259579

Abstract

In the title compound, C₁₃H₁₉ClN₃O₃ ⁺·ClO₄ ⁻, the 3-(dimethylammonio)propyl group of the cation is disordered over two sets of sites with occupancies 0.772 (6) and 0.228 (6). The cations are joined by pairs of N—H⋯O hydrogen bonds into centrosymmetric dimers and these dimers are assembled into chains along the a-axis direction, also through N—H⋯O hydrogen bonds. The perchlorate anions are linked to the hydroxy groups of the cations by O—H⋯O hydrogen bonds. The positively charged ammonium groups and the anions give rise to folded layers parallel to the ab plane.

Related literature

For DNA binding of oxamide complexes, see: Li et al. (2010 ▶). For the synthesis, see: Tao et al. (2003 ▶).

Experimental

Crystal data

C₁₃H₁₉ClN₃O₃ ⁺·ClO₄ ⁻
M _r = 400.21
Monoclinic,
a = 6.7423 (5) Å
b = 12.8169 (10) Å
c = 21.6454 (17) Å
β = 98.275 (1)°
V = 1851.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 296 K
0.52 × 0.28 × 0.13 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.823, T _max = 0.951
10727 measured reflections
4204 independent reflections
2526 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.179
S = 1.03
4204 reflections
297 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811050653/yk2031sup1.cif

e-68-000o8-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050653/yk2031Isup2.hkl

e-68-000o8-Isup2.hkl^{(201.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811050653/yk2031Isup3.cml

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
O1—H1⋯O5	0.89 (4)	1.80 (4)	2.693 (3)	174 (3)
N2—H2A⋯O2ⁱ	0.88 (3)	2.12 (3)	2.905 (3)	149 (2)
N3A—H3A⋯O3ⁱⁱ	0.91	2.04	2.814 (6)	142
N3B—H3B⋯O3ⁱⁱ	0.91	2.13	2.905 (18)	143

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

Acknowledgments

This project was supported by the Natural Science Foundation of China (No. 21071133) and the Natural Science Foundation of Qingdao City (No. 09–1-3–73-jch)

supplementary crystallographic information

Comment

Aimed for the DNA-binding study of a series of asymmetric N,N-disubstituted oxamide complexes (Li et al., 2010), we attempted to prepare a binuclear copper(II) complex with N-(5-chloro-2-hydroxyphenyl)-N'-(3-(dimethylammonio)propyl) oxamide (H₃chdpoxd). Unexpectedly, the perchlorate salt of the ligand, (H₄chdpoxd)ClO₄, I, was obtained.

The title compound consists of a H₄chdpoxd⁺ cations and a ClO4^- anions (Fig. 1). In the cation, the oxamide group adopts transoid conformation. The benzene ring is nearly parallel to the oxamide plane, with a dihedral angle of 5.39 (15)°. As for the alkyl substituent, the torsion angles of C8—N2—C9A—C10A and C8—N2—C9B—C10B are 86.1 (6)° and 117.6 (19)°, respectively.

In the crystal, the positively charged ammonium N atoms (N3A and N3B) together with the perchlorate anions form a folded layer structure with a quadrilateral pattern (Fig. 2). Such a charge-balanced layer is paralled to a0b plane. Cations related by an inversion center are linked by the hydrogen bonds involving oxamide groups (N2—H2A···O2, Table 3) to form a dimer. These dimers form chains parallel to a direction through the hydrogen bonds involving the ammonium groups (Fig. 3). The perchlorate ions append to the chains through the hydrogen bonds with phenolic hydroxy groups.

Experimental

The ligand, H₃chdpoxd, was prepared according to the method proposed by Tao et al., (2003). To a solution of H₃chdpoxd (0.0299 g, 0.1 mmol) in methanol (10 ml) were added sequentially piperidine (0.2 mmol) and a solution of Cu(ClO₄)₂.6H₂O (0.0742 g, 0.2 mmol) in methanol (10 ml). The mixture was intensively stirred until the solution became clear, and then 2,9-dimethyl-1,10-phenanthroline (dmphen, 0.0432 g, 0.4 mmol) in methanol (10 ml) was added. Stirring of the reaction mixture was continued at 333 K for 2 h. Although our original goal was to prepare a dinuclear copper(II) complex with chdpoxd^3- as a bridge ligand and 2,9-dimethyl-1,10-phenanthroline as a terminal ligand, the colourless crystals of the title compound, (H₄chdpoxd)ClO₄, unexpectedly precipitated on the seventh day, after the solution had been left to stand at room temperature.

Anal. Calcd for C₁₃H₁₉Cl₂N₃O₇ (%): C, 39.01; H, 4.79; N, 10.50. Found: C, 38.49, H, 4.72, N, 11.06.