4,4′-Dichloro-N,N′-(o-phenyl­ene)dibenzene­sulfonamide

Julia Krainova; Christopher Dares; A B P Lever

doi:10.1107/S1600536808039718

. 2008 Dec 20;65(Pt 1):o178. doi: 10.1107/S1600536808039718

4,4′-Dichloro-N,N′-(o-phenylene)dibenzenesulfonamide

Julia Krainova ^a, Christopher Dares ^a, A B P Lever ^a,^*

PMCID: PMC2968088 PMID: 21581634

Abstract

The title compound, C₁₈H₁₄Cl₂N₂O₄S₂, is a diamine that is a precursor to a quinonoid bidentate redox-active ligand. The dihedral angles between the central phenyl ring and the end rings are 87.5(1) and 60.7(1)°, while the two end rings make a dihedral angle of 82.5(1)°. The crystal structure is stabilized by two weak intermolecular N—H⋯O hydrogen bonds, as well as one intramolecular C—H⋯O and one N—H⋯N hydrogen bond.

Related literature

For the synthesis of related substituted o-phenylenediamines, see: Massacret et al. (1999 ▶). For background to the use of substituted o-benzoquinones as ligands, see: Masui & Lever (1993 ▶); Kalinina et al. (2008 ▶) and references therein.

Experimental

Crystal data

C₁₈H₁₄Cl₂N₂O₄S₂
M _r = 457.33
Triclinic,
a = 7.7225 (4) Å
b = 11.1920 (4) Å
c = 11.9325 (5) Å
α = 109.669 (2)°
β = 91.420 (2)°
γ = 101.782 (2)°
V = 945.79 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 150 (1) K
0.40 × 0.36 × 0.30 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.748, T _max = 0.876
8650 measured reflections
4235 independent reflections
3386 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.122
S = 1.08
4235 reflections
261 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039718/bx2184sup1.cif

e-65-0o178-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039718/bx2184Isup2.hkl

e-65-0o178-Isup2.hkl^{(203.3KB, 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⋯O4ⁱ	0.87 (3)	2.12 (3)	2.936 (3)	157 (2)
N2—H2⋯O2ⁱⁱ	0.85 (3)	2.30 (3)	3.107 (3)	159 (2)
N1—H1⋯N2	0.87 (3)	2.45 (3)	2.811 (3)	106 (2)
C6—H6⋯O1	0.95	2.22	2.900 (3)	128

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

Acknowledgments

The authors thank Dr Alan J. Lough for acquiring the X-ray diffraction data and for helpful discussions. Financial support for this work was provided by the Natural Sciences and Engineering Research Council of Canada (NSERC). CD thanks NSERC for a post-graduate scholarship.

supplementary crystallographic information

Comment

Benzoquinonediimine compounds have been extensively studied as ligands in metal complex systems (Kalinina et al., 2008). As free ligands, they exist in the diamine form, however, they have the ability to bind to a metal in one of three oxidation states: as o-phenylenediamine, its one-electron oxidized o-semiquinonediiminate, or its doubly oxidized and strongly π-accepting o-benzoquinonediimine form. In addition to being redox-active, these ligands also often exhibit non-innocent behaviour. Ruthenium complexes of o-benzoquinonediimines possess highly covalent bonds. The extent of electronic coupling between the metal and diimine ligand can be tuned by using substituented o-benzoquinones (Masui & Lever, 1993, and Kalinina et al., 2008). We present here the synthesis and crystal structure of the title compound (I). In (I) (Fig. 1), highly electron-withdrawing groups (p-chlorophenylsulfonyl, PCPS) are bound to the amine N atoms, and are expected to exhibit a greater covalent metal-benzoquinonediimine ligand bond character than the unsubstituted diimine. The C1—N1—S1—C7 dihedral angle is 81.0 (2) °, while the C2—N2—S2—C13 dihedral angle is only 68.6 (2)°. The p-chlorophenyl rings are essentially perpendicular to the N—S bond, likely due to steric hindrance and intermolecular H bonding between the ortho H atoms, and the sulfonyl O atoms (Fig. 1). The crystal structure is stabilized by two weak intermolecular N—H···O hydrogen bonds (Fig. 2), as well as three intramolecular C—H···O and one N—H···N hydrogen bonds which increases the stability of the crystal, (Table 1). The bonds parameters are similar to those in the other arylsulfonamides.

Experimental

(I) was synthesized for the first time according to methods described by Massacret et al., 1999, using p-chlorophenylsulfonyl chloride (10 mmol) as the arenesulfonyl chloride. o-phenylenediamine (540 mg, 5 mmol) was twice sublimed under reduced pressure prior to use. After purification, (I) was dissolved in a minimal amount of ethanol, and then added to an aqueous solution of CuCl₂ (20 ml, 0.15 M). Colorless block-like crystals suitable for x-ray diffraction studies were obtained after allowing the solution to stand for 2 weeks.