A new heterocylic ring system in (4SR,6SR)-6-(2-phenyl­ethyl)-4-phenyl-1,4,3-oxa­thia­zin-2(6H)-one

The title compound, C₁₇H₁₇NO₂S, is formed by reaction of 2-azido­carbonyl­oxy-4-phenyl-1-thio­phenyl­butane with iron(II) chloride as catalyst. This is the first example of the 1,4,3-oxa­thia­zin-2(6H)-one ring system.

Key indicators

• Single-crystal X-ray study
• T = 213 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.038
• wR factor = 0.105
• Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

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S1. Comment

During our studies on iron(II)-catalyzed nitrogen transfer, we developed an intramolecular variant generating cyclic systems (Bach et al., 2000a,b; Bach & Körber, 1998, 1999, 2000). By treating a thio-substituted alkoxycarbonylazide with catalytic amounts of iron(II) chloride in dichloromethane, the title compound, (I), was precipitated as a mixture of diastereoisomers (55:45). After recrystallization it could be obtained in diastereoisomerically pure form.

The interesting 1,4,3-oxathiazin-2(6H)-one ring system constitutes a new class of heterocycles. The ring atoms N3, C2 with O2, O1 and C6 are approximately planar [maximum deviation from the best plane 0.047 (1) Å], S4 is 0.559 (1) Å and C5 is 1.030 (2) Å above this plane. The phenyl rest at S4 shows a remarkable rotation towards the N5 atom [torsion angle N3—S4—C7—C12 - 24.4 (2)°]. The corresponding 1,4,3-oxathiazin-2(6H)-one 4-oxides have been prepared earlier and an X-ray structure analysis was reported (Hwang et al., 1987). Heterocyclic sulfoximines show a wide variety of physiological activities (Kennewell & Taylor 1980).

S2. Experimental

The title compound was prepared by reaction of 2-azidocarbonyloxy-4-phenyl-1-thiophenylbutane with iron(II) chloride in dichloromethane according to the scheme in the Comment. The product was purified by chromatography and then dissolved in dichloromethane/tert-butyl methyl ether. Upon standing at room temperature, crystals suitable for X-ray analysis were obtained.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. DIAMOND (Brandenburg, 1999) drawing of a molecule of (I) with the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

(4SR,6SR)-6-(2-Phenylethyl)-4-phenyl-1,4,3-oxathiazin-2(6H)-one

Crystal data

C17H17NO2S	Dx = 1.359 Mg m^−3
Mr = 299.38	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 25 reflections
a = 9.0561 (4) Å	θ = 18.2–19.9°
b = 11.5330 (5) Å	µ = 1.99 mm^−1
c = 28.0118 (13) Å	T = 213 K
V = 2925.7 (2) Å^3	Square plate, colourless
Z = 8	0.25 × 0.22 × 0.06 mm
F(000) = 1264

Data collection

Enraf-Nonius CAD-4 diffractometer	2222 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 70.3°, θmin = 3.2°
ω scans	h = 0→11
Absorption correction: numerical via indexed faces (SHELXTL; Sheldrick, 1996)	k = 0→14
Tmin = 0.636, Tmax = 0.886	l = −34→34
5578 measured reflections	2 standard reflections every 120 min
2779 independent reflections	intensity decay: 1.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.7475P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2779 reflections	Δρmax = 0.26 e Å^−3
191 parameters	Δρmin = −0.49 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00049 (9)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.41569 (15)	0.74573 (11)	0.57084 (5)	0.0282 (3)
C2	0.3501 (2)	0.65490 (16)	0.54712 (7)	0.0287 (4)
O2	0.39286 (16)	0.55847 (11)	0.55811 (5)	0.0360 (4)
N3	0.23811 (19)	0.67350 (14)	0.51586 (6)	0.0330 (4)
S4	0.21478 (5)	0.79553 (4)	0.488402 (17)	0.02732 (15)
C5	0.3537 (2)	0.89111 (15)	0.51218 (6)	0.0260 (4)
H5B	0.4493	0.8771	0.4969	0.031*
H5A	0.3259	0.9724	0.5073	0.031*
C6	0.3606 (2)	0.86256 (15)	0.56495 (7)	0.0252 (4)
H6	0.2611	0.8693	0.5793	0.030*
C7	0.2856 (2)	0.77366 (17)	0.42934 (7)	0.0289 (4)
C8	0.2289 (2)	0.84315 (18)	0.39375 (7)	0.0331 (5)
H8	0.1562	0.8988	0.4007	0.040*
C9	0.2810 (3)	0.8295 (2)	0.34747 (8)	0.0432 (6)
H9	0.2442	0.8763	0.3227	0.052*
C10	0.3875 (3)	0.7465 (2)	0.33799 (9)	0.0498 (6)
H10	0.4236	0.7377	0.3067	0.060*
C11	0.4415 (3)	0.6763 (2)	0.37408 (9)	0.0484 (6)
H11	0.5128	0.6195	0.3671	0.058*
C12	0.3911 (2)	0.68919 (19)	0.42039 (8)	0.0379 (5)
H12	0.4273	0.6420	0.4451	0.045*
C13	0.4683 (2)	0.94188 (17)	0.59093 (7)	0.0295 (4)
H13A	0.4404	1.0226	0.5848	0.035*
H13B	0.5674	0.9299	0.5778	0.035*
C14	0.4737 (2)	0.92227 (18)	0.64498 (7)	0.0330 (4)
H14B	0.4952	0.8402	0.6509	0.040*
H14A	0.5559	0.9675	0.6581	0.040*
C15	0.3349 (2)	0.95408 (17)	0.67191 (7)	0.0318 (4)
C16	0.2552 (3)	1.05343 (18)	0.66148 (8)	0.0382 (5)
H16	0.2872	1.1024	0.6367	0.046*
C17	0.1284 (3)	1.0819 (2)	0.68708 (9)	0.0460 (6)
H17	0.0742	1.1484	0.6788	0.055*
C18	0.0817 (3)	1.0134 (2)	0.72454 (9)	0.0486 (6)
H18	−0.0025	1.0337	0.7423	0.058*
C19	0.1602 (3)	0.9152 (2)	0.73545 (8)	0.0487 (6)
H19	0.1296	0.8677	0.7609	0.058*
C20	0.2845 (3)	0.8853 (2)	0.70924 (8)	0.0407 (5)
H20	0.3359	0.8170	0.7169	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0283 (7)	0.0260 (6)	0.0303 (7)	−0.0006 (5)	−0.0050 (6)	0.0000 (6)
C2	0.0261 (9)	0.0319 (10)	0.0281 (10)	−0.0038 (8)	0.0038 (8)	0.0003 (8)
O2	0.0386 (8)	0.0278 (7)	0.0417 (9)	0.0003 (6)	−0.0017 (7)	0.0045 (6)
N3	0.0298 (9)	0.0312 (8)	0.0381 (10)	−0.0094 (7)	−0.0068 (8)	0.0054 (7)
S4	0.0214 (2)	0.0337 (3)	0.0269 (3)	−0.00003 (18)	−0.00068 (17)	−0.00076 (19)
C5	0.0264 (9)	0.0254 (9)	0.0261 (10)	−0.0012 (7)	0.0005 (8)	−0.0009 (7)
C6	0.0244 (9)	0.0258 (9)	0.0255 (9)	0.0021 (8)	0.0018 (7)	−0.0009 (8)
C7	0.0235 (10)	0.0356 (10)	0.0277 (10)	−0.0049 (8)	0.0002 (8)	−0.0045 (8)
C8	0.0279 (10)	0.0383 (11)	0.0332 (11)	−0.0039 (9)	−0.0001 (9)	−0.0002 (9)
C9	0.0406 (13)	0.0565 (14)	0.0325 (12)	−0.0103 (11)	−0.0020 (9)	0.0026 (11)
C10	0.0428 (13)	0.0747 (16)	0.0319 (12)	−0.0082 (12)	0.0077 (10)	−0.0150 (13)
C11	0.0378 (13)	0.0629 (15)	0.0444 (14)	0.0062 (11)	0.0022 (10)	−0.0188 (12)
C12	0.0315 (11)	0.0446 (12)	0.0376 (12)	0.0043 (9)	−0.0030 (9)	−0.0093 (10)
C13	0.0289 (9)	0.0320 (9)	0.0276 (10)	−0.0043 (8)	0.0004 (8)	−0.0014 (8)
C14	0.0337 (10)	0.0364 (10)	0.0288 (10)	−0.0042 (9)	−0.0062 (8)	−0.0002 (9)
C15	0.0373 (11)	0.0351 (10)	0.0230 (9)	−0.0068 (9)	−0.0050 (8)	−0.0039 (8)
C16	0.0474 (12)	0.0347 (11)	0.0323 (11)	−0.0005 (9)	−0.0016 (10)	0.0005 (9)
C17	0.0488 (14)	0.0434 (12)	0.0458 (14)	0.0046 (11)	0.0003 (11)	−0.0051 (11)
C18	0.0494 (14)	0.0563 (14)	0.0399 (13)	−0.0014 (12)	0.0089 (11)	−0.0096 (12)
C19	0.0555 (15)	0.0573 (14)	0.0333 (12)	−0.0081 (12)	0.0082 (12)	0.0031 (11)
C20	0.0482 (14)	0.0424 (12)	0.0316 (11)	−0.0013 (10)	−0.0020 (10)	0.0034 (10)

Geometric parameters (Å, º)

O1—C2	1.375 (2)	C9—C10	1.385 (3)
O1—C6	1.446 (2)	C10—C11	1.384 (4)
C2—O2	1.217 (2)	C11—C12	1.383 (3)
C2—N3	1.357 (3)	C13—C14	1.532 (3)
N3—S4	1.6176 (17)	C14—C15	1.511 (3)
S4—C7	1.792 (2)	C15—C16	1.385 (3)
S4—C5	1.8002 (19)	C15—C20	1.389 (3)
C5—C6	1.516 (2)	C16—C17	1.393 (3)
C6—C13	1.522 (3)	C17—C18	1.380 (3)
C7—C8	1.378 (3)	C18—C19	1.372 (4)
C7—C12	1.387 (3)	C19—C20	1.387 (3)
C8—C9	1.388 (3)
C2—O1—C6	120.37 (15)	C7—C8—C9	118.9 (2)
O2—C2—N3	123.06 (18)	C10—C9—C8	119.6 (2)
O2—C2—O1	115.86 (18)	C11—C10—C9	120.7 (2)
N3—C2—O1	120.94 (17)	C10—C11—C12	120.4 (2)
C2—N3—S4	122.82 (14)	C11—C12—C7	118.2 (2)
N3—S4—C7	105.65 (9)	C6—C13—C14	113.86 (16)
N3—S4—C5	105.40 (9)	C15—C14—C13	115.52 (17)
C7—S4—C5	100.24 (9)	C16—C15—C20	117.4 (2)
C6—C5—S4	104.89 (12)	C16—C15—C14	121.94 (19)
O1—C6—C5	109.15 (14)	C20—C15—C14	120.67 (19)
O1—C6—C13	106.54 (15)	C15—C16—C17	121.1 (2)
C5—C6—C13	111.25 (15)	C18—C17—C16	120.6 (2)
C8—C7—C12	122.3 (2)	C19—C18—C17	118.9 (2)
C8—C7—S4	116.91 (15)	C18—C19—C20	120.5 (2)
C12—C7—S4	120.81 (16)	C19—C20—C15	121.5 (2)
C6—O1—C2—O2	−172.27 (17)	C8—C9—C10—C11	0.7 (4)
C6—O1—C2—N3	3.6 (3)	C9—C10—C11—C12	−0.9 (4)
O2—C2—N3—S4	−159.80 (16)	C10—C11—C12—C7	0.2 (3)
O1—C2—N3—S4	24.6 (3)	C8—C7—C12—C11	0.9 (3)
C2—N3—S4—C7	101.39 (18)	S4—C7—C12—C11	179.94 (17)
C2—N3—S4—C5	−4.2 (2)	O1—C6—C13—C14	−64.6 (2)
N3—S4—C5—C6	−38.78 (14)	C5—C6—C13—C14	176.58 (16)
C7—S4—C5—C6	−148.29 (13)	C6—C13—C14—C15	−67.0 (2)
C2—O1—C6—C5	−53.1 (2)	C13—C14—C15—C16	−41.3 (3)
C2—O1—C6—C13	−173.30 (16)	C13—C14—C15—C20	140.4 (2)
S4—C5—C6—O1	65.97 (16)	C20—C15—C16—C17	−0.9 (3)
S4—C5—C6—C13	−176.75 (13)	C14—C15—C16—C17	−179.2 (2)
N3—S4—C7—C8	154.71 (15)	C15—C16—C17—C18	2.0 (4)
C5—S4—C7—C8	−95.97 (16)	C16—C17—C18—C19	−1.5 (4)
N3—S4—C7—C12	−24.42 (18)	C17—C18—C19—C20	0.0 (4)
C5—S4—C7—C12	84.90 (17)	C18—C19—C20—C15	1.1 (4)
C12—C7—C8—C9	−1.1 (3)	C16—C15—C20—C19	−0.6 (3)
S4—C7—C8—C9	179.77 (16)	C14—C15—C20—C19	177.7 (2)
C7—C8—C9—C10	0.3 (3)