Di­aqua­bis­(ethyl­enedi­amine-κ2 N,N′)copper(II) bis­(sulfamerazinate)

Amani Direm; Wahiba Falek; Guillaume Pilet; Nourredine Benali-Cherif

doi:10.1107/S160053681401068X

. 2014 May 17;70(Pt 6):m222–m223. doi: 10.1107/S160053681401068X

Diaquabis(ethylenediamine-κ² N,N′)copper(II) bis(sulfamerazinate)

Amani Direm ^a,^*, Wahiba Falek ^a, Guillaume Pilet ^b, Nourredine Benali-Cherif ^a

PMCID: PMC4051046 PMID: 24940207

Abstract

The asymmetric unit of the title compound, [Cu(C₂H₈N₂)₂(H₂O)₂](C₁₁H₁₁N₄O₂S)₂, contains one sulfamerazinate anion in a general position and one half-cation that is located on a center of inversion. The Cu^II cation shows a strong Jahn–Teller distortion. It is coordinated by four N atoms of two ethylenediamine ligands in the basal plane and two O atoms at much longer distances in the axial positions in a bipyramidal coordination. In the crystal, the building blocks are connected by N—H⋯N, O—H⋯N, N—H⋯O and O—H⋯O hydrogen bonding into a two-dimensional network parallel to (001).

Related literature

For the antibacterial activity of sulfonamides, see: Anand (1980 ▶); Kratz et al. (2000 ▶); Grave et al. (2010 ▶). For uses of sulfamerazine, see: Murphy et al. (1943 ▶); Clark et al. (1943 ▶); Earle (1944 ▶); Forbes et al. (1946 ▶). The crystal structure of sulfamerazine was reported by Acharya et al. (1982 ▶). For a related compound in which sulfathiazole acts as a deprotonated counter-ion, see: Anacona et al. (2002 ▶). graphic file with name e-70-0m222-scheme1.jpg

Experimental

Crystal data

[Cu(C₂H₈N₂)₂(H₂O)₂](C₁₁H₁₁N₄O₂S)₂
M _r = 746.41
Triclinic,
a = 7.5429 (4) Å
b = 8.1800 (5) Å
c = 14.8434 (8) Å
α = 75.299 (5)°
β = 82.800 (5)°
γ = 78.873 (5)°
V = 866.40 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.41 × 0.36 × 0.17 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T _min = 0.723, T _max = 0.869
4738 measured reflections
4020 independent reflections
3361 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.05
4020 reflections
215 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: GEMINI (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401068X/nc2325sup1.cif

e-70-0m222-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401068X/nc2325Isup2.hkl

e-70-0m222-Isup2.hkl^{(220.5KB, hkl)}

CCDC reference: 1002145

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
N1—H1NA⋯O2ⁱ	0.97	2.09	3.022 (3)	162
O1W—H1W⋯O1	0.85	2.07	2.816 (2)	145
N1—H1NB⋯O1	0.97	2.41	3.219 (2)	140
O1W—H2W⋯N11ⁱⁱ	0.95	1.92	2.858 (2)	171
N2—H2NA⋯O2ⁱⁱ	0.97	2.33	3.189 (3)	147
N2—H2NA⋯N11ⁱⁱ	0.97	2.47	3.319 (3)	145
N2—H2NB⋯O2ⁱⁱⁱ	0.97	2.42	3.277 (3)	147
N14—H14A⋯N12^iv	0.93	2.09	3.003 (3)	166
N14—H14B⋯O1^v	0.95	2.21	2.993 (3)	140
N14—H14B⋯N13^v	0.95	2.44	3.215 (3)	139

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

Acknowledgments

The authors acknowledge the Université "Abbes Laghrour", Khenchela, Algeria for financial support.

supplementary crystallographic information

1. Comment

It is well known that many sulfonamide derivatives possess antibacterial activity (Anand, 1980; Kratz et al., 2000; Grave et al., 2010) including sulfamerazine which is widely used to treat susceptible microbial infections (Murphy et al., 1943; Clark et al., 1943). Faster absorption, low overall excretion rate by the kidneys, and an equal therapeutic and toxic effect of sulfamerazine compared to other sulfonamide drugs, such as sulfadiazine and sulfathiazole, have been claimed for its wider usage (Earle, 1944; Forbes et al., 1946).

The first crystal structure of sulfamerazine have been reported by (Acharya et al., 1982). The presence of several potential donor sites, namely the amino, pyrimidine and sulfonamide N atoms and the sulfonyl O atoms, make this ligand a versatile complexing agent.

As part of our efforts to investigate metal(II) complexes based on sulfonamides, we report herein the crystal structure of the new copper(II) complex: Diaquabis(ethylenediamine-κ2 N,N')copper(II) bis(sulfamerazinate).

The asymmetric unit of the title compound contains one sulfamerazinate counter-ion and a half [Cu(en)₂(H₂O)₂]²⁺ cation (en = ethylenediamine) (Fig. 1). The metal ion is located in a ML6 environment and coordinated by four N atoms of two ethylenediamine ligands and two O atoms of two water molecules. The four N atoms of the ligands in the equatorial plane form a square-planar arrangement, while the 6-fold coordination is completed by the two water O atoms in the axial positions. The apical Cu—O bridging separation is 2.513 (2) Å while the equatorial Cu—N bridging bond lengths are 2.0168 (19) Å and 2.0016 (18) Å, which is typical for a Jahn-Teller distortion. A sulfamerazine anion that is deprotonated at the N11 N atom is present in the structure (Fig. 1). To the best of our knowledge, a search in the Cambridge Structural Database reveal, that this is the first crystal structure where a sulfamerazinate anion act as a counter ion. A similar situation is observed in [Cu(en)₂(OH₂)₂](Stz)₂·2H₂O (Anacona et al., 2002) where a sulfathiazole acts as a deprotonated counter ion too.

In the crystal strcuture of the title compound every complex cation is linked via O—H···N, N—H···O and O—H···O hydrogen bonding to the counter cations, while the cations are interconnected via the N—H···N interaction, which lead to the formation of a two dimensional network (Fig. 2).

2. Experimental

The single crystals of [Cu(C₂H₈N₂)₂(H₂O)₂](C₁₁H₁₂N₄SO₂)₂ were formed in a methanolic solution (50 ml) of Cu(CH₃CO₂)₂ (0.362 g, 2 mmol) and sulfamerazine (1.057 g, 4 mmol) by adding ethylenediamine (0.5 ml, 7.3 mmol). The precipitate obtained immediately was filtred out and the resulting filtrate was left to slowly evaporate at room temperature which lead to the formation of blue single crystals suitable for X-Ray diffraction.