4-Acetamido-N-(λ5-triphenyl­phospho­ranyl­idene)benzene­sulfonamide

Biserka Prugovečki; Marina Marinković; Mladen Vinković; Miljenko Dumić

doi:10.1107/S1600536810013620

. 2010 Apr 17;66(Pt 5):o1098–o1099. doi: 10.1107/S1600536810013620

4-Acetamido-N-(λ⁵-triphenylphosphoranylidene)benzenesulfonamide

Biserka Prugovečki ^a,^*, Marina Marinković ^b, Mladen Vinković ^b,^‡, Miljenko Dumić ^c

PMCID: PMC2979042 PMID: 21579151

Abstract

There are two independent molecules per asymmetric unit of the title compound, C₂₆H₂₃N₂O₃PS. Their superposition shows that they differ in the conformation of the CH₃CO– group and the benzene rings from the triphenylphosphorane group. In the crystal structure, independent molecules are interconected by strong N—H⋯O hydrogen bonds, forming infinite chains along the a axis.

Related literature

For related structures, see: Andersen et al. (1999 ▶, 2001 ▶, 2004 ▶); Matano et al. (2002 ▶); Monkowius et al. (2004 ▶); Zhu et al. (1997 ▶). For the synthesis, see: Ashley et al. (1947 ▶); Khmel’nitzkaya & Mikhel’s (1934 ▶). For structural and synthetic studies of azirine antihyperglycaemics, see; Dumić et al. (1993 ▶, 1995 ▶); Filić et al. (1996 ▶); Orešić et al. (2001 ▶); Prugovečki et al. (2005 ▶, 2006 ▶); Vinković et al. (1993 ▶); Žegarac et al. (2010 ▶).

Experimental

Crystal data

C₂₆H₂₃N₂O₃PS
M _r = 474.49
Monoclinic,
a = 15.0419 (10) Å
b = 18.6355 (10) Å
c = 18.5917 (18) Å
β = 113.413 (10)°
V = 4782.4 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.56 × 0.30 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer
32329 measured reflections
8441 independent reflections
6309 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 1.04
8441 reflections
595 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2003 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013620/bg2337sup1.cif

e-66-o1098-sup1.cif^{(30KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013620/bg2337Isup2.hkl

e-66-o1098-Isup2.hkl^{(412.9KB, 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
N2—H2⋯O2′ⁱ	0.86	2.11	2.966 (2)	173
N2′—H2′⋯O2ⁱⁱ	0.86	2.11	2.961 (2)	174

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

Acknowledgments

The authors thank the Ministry of Science and Technology of the Republic of Croatia for partial financial support of this work (grant Nos. 0006543 and 0119632).

supplementary crystallographic information

Comment

As a part of our ongoing research on the synthetic and structural studies of 1-sulfonyl-1a,2,6,6a-tetrahydro-1H,4H-[1,3]dioxepino[5,6-b]azirine antihyperglycaemics (Dumić et al. 1993 ; 1995, Filić et al. 1996, Vinković et al. 1993, Orešić et al. 2001 and Prugovečki et al.2005 ; 2006), we required suitable synthons carrying 4-acetylaminobenzenesulfanyl and 4-acetylaminobenzenesulfonyl pattern. Thus, the 4-acetylaminobenzenesulfonyimino-triphenylphosphorane (Title compound, I) and bis(4-acetylaminophenyl) disulfide compound (II) were chosen for this study. We prepared both of them in the same reaction, i.e. by treatment of 4-acetylaminobenzenesulfonylazide with triphenylphosphine in acetonitrile at room temperature (Scheme 1). 4-Acetylaminobenzenesulfonyimino-triphenylphosphorane (Title compound, I) was obtained as colorless prisms (m.p. 495-497 K). Bis(4-acetylaminophenyl) disulfide (compound II) was obtained as a yellow solid (m.p. 485-488 K), i.e. in one of its three known forms; m.ps. 488 K, 454-455 K and 395 K respectively (Khmel'nitzkaya, et al. 1934). Its structure and solid state behaviour will be published elsewhere (Žegarac et al. 2010).

In the title compound, C₂₆H₂₃N₂O₃PS,(I), there are two independent molecules per asymmetric unit. Their superposition shows that they are different in the conformation of the CH₃CO group and the benzene rings from the triphenylphosphorane group. In the crystal structure independent molecules are interconected by strong N—H···O hydrogen bonds forming infinite one-dimensional chains along the a axis.

Experimental

Triphenylphosphine (28.18 g, 0.107 mol) was added in small portions to a stirred solution of 4-acetylaminobenzenesulfonyl azide (13.0 g, 50.4 mmol) [prepared according Ashley et al. (1947)] in acetonitrile (211 ml) at 273 K. After being stirred for 3 hrs at room temperature, the mixture was concentrated under reduced pressure to dryness. The residue was purified by silicagel column chromatography (dichloromethane-methanol-25 % ammonia, 10:1:0.3 v/v) to afford the title compound (I) as a colorless solid [5.9 g, 22.7 %; m.p. 491-495 K; R_f = 0.32 (dichloromethane-methanol- 25 % ammonia, 10:1:0.3 v/v)]. Single crystals suitable for X-ray diffraction were prepared by recrystallization from ethyl acetate-methanol , 1:1 v/v). M.p. 495-497 K. Spectroscopic analysis: IR (KBr) ν_max/cm^-1: 3305, 3269, 3190, 3116, 3057, 1691, 1594, 1536, 1485, 1437, 1400, 1372, 1315, 1252, 1194, 1170, 1131, 1085, 1031, 1015, 998, 954, 851, 801, 790, 753, 723, 692, 638, 620. ¹H NMR (DMSO-d₆) δ/ppm: 10.12 (s, 1H, NH), 7.52 i 7.40 (d.d., 4H, J=4.3, H-arom.), 7.73-7.68 and 7.59-7.57 (2 m, 15H, H-arom.), 2.06 (s, 3H, CH₃). ¹³C NMR (DMSO-d₆) δ/ppm: 141.10 (s), 140.32 (s), 125.93 (d), 117.96 (d) (C arom.), 133.05 (d), 132.60 (d), 128.90 (d), 126.94 (d, J(C—P)=102.9) (C-arom), 24.04 (q, CH₃).

Evaporation of other selected fractions to dryness afford bis(4-acetylaminophenyl) disulfide (II) as a TLC pure yellow solid [5.7 g, 31.5 % m.p. 485-488 K; R_f = 0.26 (dichloromethane-methanol-25 % ammonia, 10:1:0.3 v/v)]. Spectroscopic analysis: IR (KBr) ν_max/cm^-1: 3291, 3246, 3178, 3105, 3058, 1681, 1658, 1608, 1593, 1538, 1490, 1397, 1367, 1317, 1292, 1263, 1175, 1121, 1014, 967, 838, 825, 816, 758, 703, 604. ¹H NMR (DMSO-d₆) δ/ppm: 10.71 (s, 2H, NH), 7.59 and 7.42 (dd, 8H, H arom, J=8.7), 2.04 (s, 6H, CH₃). ¹³C NMR (DMSO-d₆) δ/ppm: 168.50 (s, CO), 139.50 (s), 130.10 (d), 129.10 (s), 119.50 (d) (C arom), 24.20 (q, CH₃).