1,4-Ditosyl-1,4-diazepane

Shuang-Hua Yang; Zhi-Wei Zhai

doi:10.1107/S1600536812020958

. 2012 May 12;68(Pt 6):o1716. doi: 10.1107/S1600536812020958

1,4-Ditosyl-1,4-diazepane

Shuang-Hua Yang ^a, Zhi-Wei Zhai ^a,^*

PMCID: PMC3379307 PMID: 22719505

Abstract

In the title compound, C₁₉H₂₄N₂O₄S₂, the dihedral angle formed by the benzene rings is 82.88 (7)°, and the molecular conformation is enforced by weak intramolecular C—H⋯O contacts. Two C atoms of the 1,4-diazepane ring are disordered over two sets of sites with a refined occupancy ratio of 0.534 (13):0.466 (13). In the crystal, molecules are linked by weak intermolecular C—H⋯O interactions into chains parallel to the a axis.

Related literature

For related structures, see: Romba et al. (2002 ▶). For the biological activity of heterocyclic compounds, see: Xu et al. (2006 ▶); Yu et al. (2009 ▶). graphic file with name e-68-o1716-scheme1.jpg

Experimental

Crystal data

C₁₉H₂₄N₂O₄S₂
M _r = 408.52
Orthorhombic,
a = 6.3407 (13) Å
b = 10.367 (2) Å
c = 30.516 (6) Å
V = 2005.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.20 × 0.20 × 0.10 mm

Data collection

Rigaku Mercury CCD/AFC diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.944, T _max = 0.971
11747 measured reflections
3531 independent reflections
3430 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.083
S = 1.07
3531 reflections
265 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ▶), 1442 Friedel pairs
Flack parameter: −0.03 (7)

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020958/rz2746sup1.cif

e-68-o1716-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020958/rz2746Isup2.hkl

e-68-o1716-Isup2.hkl^{(173.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812020958/rz2746Isup3.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
C10—H10B⋯O3	0.97	2.40	2.886 (3)	110
C12—H12A⋯O1	0.97	2.39	2.878 (3)	111
C10—H10B⋯O4ⁱ	0.97	2.52	3.142 (3)	122
C12—H12A⋯O2ⁱ	0.97	2.50	3.035 (3)	115

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Many heterocyclic compounds have been widely used as potent and broad-spectrum fungicides (Xu et al., 2006; Yu et al., 2009). In order to search for new heterocylic compounds with higher biological activities, we synthesized the title compound and describe its structure herein.

In title compound (Fig. 1), all bond lengths are normal and in a good agreement with those reported for related compounds (Romba et al., 2002). Two atoms (C8 and C9) of the 1,4-diazepane ring are disordered over two orientations with refined occupancy ratio of 0.466 (13)/0.534 (13). The dihedral angle formed by the phenyl rings is 82.88 (7)°. The molecular conformation is stabilized by intramolecular C—H···O hydrogen bonds (Table 1). In the crystal packing, molecules are linked by intermolecular C—H···O hydrogen bonds to form chains parallel to the a axis.

Experimental

NaH (1.9 g, 0.08 mol) was dissolved in 30 ml DMF and cooled with an ice bath, then N,N'-di(p-toluenesulfonyl)ethane-1,2-diamine (7.4 g, 0.02 mol) in 10 ml DMF was added dropwise to the solution. After stirring 30 min, 1,3-dibromopropane in 5 ml DMF was added dropwise and the resulting suspension stirred overnight at room temperature. The residue was quenched by saturated NH₄Cl and extracted with ethyl acetate (3 × 200 ml). The combined organic layer was washed with saturated NaCl and dried over sodium sulfate. The solvent was removed and the residue was recrystallized from EtOH/DMF (5:1 v/v) to give the title compound (6.7 g, 82%). Single crystals suitable for X-ray measurements were obtained by recrystallization from acetonitrile at room temperature.