exo-3,6-Di­hydro-3-methyl-2-(toluene-4-sulfonyl)-1λ⁴,2-thia­zine 1-oxide

The title compound, C₁₂H₁₅NO₃S₂, is shown to be the exo isomer with a cis arrangement of the S=O group and the methyl group in the thia­zine ring.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.057
• wR factor = 0.162
• Data-to-parameter ratio = 10.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.94
         From the CIF: _reflns_number_total               1669
         Count of symmetry unique reflns         1668
         Completeness (_total/calc)            100.06%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         1
         Fraction of Friedel pairs measured     0.001
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure

---

S1. Comment

Hetero-[4 + 2]-cycloadditions of N-sulfinyl compounds (R—N═S═O) and dienes provide 1,2-thiazine 1-oxides, which can be further transformed into synthetically useful derivatives, e.g. homoallylic amines or vicinal aminoalcohols (Weinreb, 1988). The title compound, (I), was obtained by a [2 + 4]-cycloaddition of trans-1,3-pentadiene and N-sulfinyl-4-toluenesulfonamide at room temperature in CH₂Cl₂ (Kresze & Wagner, 1972). The reaction product contained two isomers in the ratio 4:1 with different orientations of the S═O bond relative to the methyl group. The exo isomer has the S═O bond cis to the methyl group, while the endo isomer has a trans orientation. Here, the structure of the major compound is reported. The major compound was found to be the exo isomer.

The title compound crystallizes in the orthorhombic non-centrosymmetric space group P2₁2₁2₁ and is therefore a conglomerate under the applied conditions of crystallization. A molecule with the atomic numbering scheme is shown in Fig. 1. The thiazine part of the molecule is found to be in a half-chair conformation, and one also sees that the S═O and the C4—C5 bonds are on the same side of the thiazine ring, giving the exo isomer. Least-squares planes through the phenyl part (atoms C6—C11) and the thiazine part (atoms C1—C4) show an angle of 71.2 (2)° between the two planes. Atoms S1 and N1 are displaced by 0.525 (9) and 0.261 (8) Å, respectively, on opposite sides with respect to the plane through atoms C1–C4. The total puckering amplitude parameter (Cremer & Pople, 1975) Q_T = 0.499 (3) Å and one notices the presence of a local twofold axis running along the midpoints of the S1—N1 and C2—C3 bonds. Atoms C12 and S2 nearly lie in the phenyl group plane, being displaced by 0.016 (9) and 0.099 (6) Å on the same side with respect to that plane. A selection of bond lengths shows that these are all within the normal range of such bonds (Allen et al., 1987). The S2═O2 and S2═O3 are both 1.428 (3) Å, while the S1═O1 distance is 1.473 (4) Å. The molecules are packed in the crystal through a series of intra- and intermolecular short contacts (Taylor & Kennard, 1982) (see Table 1).

S2. Experimental

The 1,4-thiazine 1-oxide was dissolved in CH₂Cl₂ and heptane was added until saturation. Crystals were grown by vapour diffusion of the solvent in the refrigerator.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CELDIM in CAD-4-PC Software; data reduction: XCAD4 (McArdle & Higgins, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: OSCAIL (McArdle, 1993).

Figures

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 20% probability level.

(I)

Crystal data

C12H15NO3S2	Dx = 1.427 Mg m^−3
Mr = 285.37	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 8.277 (2) Å	θ = 8–14°
b = 9.723 (2) Å	µ = 0.40 mm^−1
c = 16.500 (2) Å	T = 298 K
V = 1327.9 (5) Å^3	Block, colourless
Z = 4	0.5 × 0.3 × 0.2 mm
F(000) = 600

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.020
Radiation source: fine-focus sealed tube	θmax = 26.9°, θmin = 2.4°
Graphite monochromator	h = 0→10
ω–2θ scans	k = −3→12
1710 measured reflections	l = −6→21
1669 independent reflections	3 standard reflections every 120 min
1386 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.162	w = 1/[σ^2(Fo^2) + (0.1332P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1669 reflections	Δρmax = 0.91 e Å^−3
165 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (19)

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.4526 (0.0163) x + 5.3390 (0.0161) y - 11.9495 (0.0225) z = 0.9846 (0.0259)

* -0.0051 (0.0031) C6 * 0.0008 (0.0032) C7 * 0.0037 (0.0037) C8 * -0.0037 (0.0037) C9 * -0.0005 (0.0033) C10 * 0.0050 (0.0033) C11 - 0.0161 (0.0091) C12 - 0.0987 (0.0063) S2

Rms deviation of fitted atoms = 0.0036

- 1.4833 (0.0207) x + 5.7272 (0.0287) y + 13.0017 (0.0330) z = 7.6614 (0.0293)

Angle to previous plane (with approximate e.s.d.) = 71.22 (0.17)

* 0.0030 (0.0015) C1 * -0.0071 (0.0035) C2 * 0.0070 (0.0034) C3 * -0.0029 (0.0014) C4 - 0.5248 (0.0091) S1 0.2608 (0.0083) N1 - 1.9755 (0.0088) O1 - 1.2537 (0.0080) C5 1.1633 (0.0120) S2

Rms deviation of fitted atoms = 0.0054

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
S1	0.74634 (13)	0.66531 (11)	0.34097 (7)	0.0440 (3)
S2	0.43335 (12)	0.76310 (10)	0.39203 (7)	0.0402 (3)
O2	0.2908 (4)	0.7647 (4)	0.3433 (2)	0.0624 (11)
O3	0.4625 (5)	0.6472 (3)	0.4432 (2)	0.0576 (10)
N1	0.5910 (4)	0.7800 (3)	0.3331 (2)	0.0362 (7)
O1	0.7622 (5)	0.5939 (4)	0.2627 (2)	0.0640 (10)
C1	0.9025 (5)	0.7917 (6)	0.3437 (3)	0.0550 (13)
H1A	0.9109	0.8265	0.3986	0.072*
H1B	1.0041	0.7472	0.3307	0.072*
C2	0.8808 (7)	0.9100 (6)	0.2883 (3)	0.0563 (13)
H2	0.9730	0.9601	0.2754	0.073*
C3	0.7485 (8)	0.9504 (5)	0.2566 (3)	0.0534 (12)
H3	0.7531	1.0284	0.2241	0.069*
C4	0.5847 (6)	0.8831 (5)	0.2667 (2)	0.0449 (10)
H4	0.5095	0.9553	0.2839	0.058*
C5	0.5206 (8)	0.8254 (7)	0.1887 (3)	0.0687 (16)
H5A	0.5838	0.7469	0.1731	0.096*
H5B	0.5268	0.8942	0.1471	0.096*
H5C	0.4100	0.7980	0.1959	0.096*
C6	0.4325 (5)	0.9148 (4)	0.4517 (2)	0.0350 (8)
C7	0.5624 (6)	0.9424 (5)	0.5011 (2)	0.0501 (11)
H7	0.6520	0.8847	0.5010	0.065*
C8	0.5584 (7)	1.0562 (6)	0.5506 (3)	0.0592 (14)
H8	0.6461	1.0754	0.5839	0.077*
C9	0.4249 (7)	1.1427 (5)	0.5513 (3)	0.0499 (11)
C10	0.3004 (6)	1.1126 (5)	0.5015 (3)	0.0541 (12)
H10	0.2107	1.1702	0.5015	0.070*
C11	0.3002 (6)	0.9994 (5)	0.4505 (3)	0.0472 (11)
H11	0.2131	0.9815	0.4165	0.061*
C12	0.4215 (9)	1.2674 (7)	0.6070 (4)	0.0819 (19)
H12A	0.3657	1.2443	0.6561	0.115*
H12B	0.3666	1.3418	0.5805	0.115*
H12C	0.5301	1.2947	0.6195	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0320 (5)	0.0395 (5)	0.0605 (7)	0.0075 (5)	0.0027 (5)	0.0082 (5)
S2	0.0263 (5)	0.0362 (5)	0.0579 (6)	−0.0050 (4)	0.0082 (4)	−0.0070 (4)
O2	0.0237 (14)	0.072 (2)	0.092 (3)	−0.0072 (16)	−0.0037 (15)	−0.034 (2)
O3	0.065 (2)	0.0373 (16)	0.070 (2)	−0.0059 (17)	0.0250 (19)	0.0081 (15)
N1	0.0285 (16)	0.0340 (17)	0.0462 (17)	0.0025 (15)	0.0051 (14)	0.0036 (16)
O1	0.049 (2)	0.0509 (18)	0.092 (3)	0.0104 (19)	0.011 (2)	−0.0201 (18)
C1	0.027 (2)	0.074 (3)	0.064 (3)	−0.010 (2)	−0.003 (2)	−0.001 (3)
C2	0.057 (3)	0.051 (3)	0.062 (3)	−0.022 (3)	0.009 (3)	−0.004 (2)
C3	0.066 (3)	0.036 (2)	0.057 (3)	−0.002 (3)	0.014 (3)	0.0043 (19)
C4	0.046 (2)	0.044 (2)	0.045 (2)	0.013 (2)	0.002 (2)	0.0128 (19)
C5	0.063 (4)	0.083 (4)	0.061 (3)	0.004 (3)	−0.016 (3)	0.006 (3)
C6	0.0251 (17)	0.0352 (17)	0.045 (2)	−0.0008 (17)	0.0009 (17)	−0.0038 (16)
C7	0.034 (2)	0.056 (3)	0.059 (3)	0.008 (2)	−0.006 (2)	−0.007 (2)
C8	0.051 (3)	0.070 (3)	0.056 (3)	−0.004 (3)	−0.009 (2)	−0.015 (2)
C9	0.055 (3)	0.048 (2)	0.046 (2)	−0.007 (2)	0.006 (2)	−0.010 (2)
C10	0.049 (3)	0.048 (2)	0.065 (3)	0.011 (2)	−0.001 (2)	−0.009 (2)
C11	0.035 (2)	0.044 (2)	0.063 (3)	0.005 (2)	−0.0063 (19)	−0.009 (2)
C12	0.078 (4)	0.078 (4)	0.090 (4)	−0.011 (4)	0.009 (4)	−0.044 (4)

Geometric parameters (Å, º)

S1—O1	1.473 (4)	C5—H5A	0.9600
S1—N1	1.707 (3)	C5—H5B	0.9600
S1—C1	1.784 (5)	C5—H5C	0.9600
S2—O2	1.428 (3)	C6—C11	1.370 (6)
S2—O3	1.428 (3)	C6—C7	1.376 (6)
S2—N1	1.635 (3)	C7—C8	1.376 (7)
S2—C6	1.773 (4)	C7—H7	0.9300
N1—C4	1.486 (5)	C8—C9	1.389 (8)
C1—C2	1.479 (7)	C8—H8	0.9300
C1—H1A	0.9700	C9—C10	1.350 (7)
C1—H1B	0.9700	C9—C12	1.521 (6)
C2—C3	1.276 (8)	C10—C11	1.386 (7)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.515 (8)	C11—H11	0.9300
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.502 (7)	C12—H12B	0.9600
C4—H4	0.9800	C12—H12C	0.9600
O1—S1—N1	108.0 (2)	C4—C5—H5A	109.5
O1—S1—C1	106.4 (3)	C4—C5—H5B	109.5
N1—S1—C1	95.6 (2)	H5A—C5—H5B	109.5
O2—S2—O3	118.7 (2)	C4—C5—H5C	109.5
O2—S2—N1	108.89 (18)	H5A—C5—H5C	109.5
O3—S2—N1	107.2 (2)	H5B—C5—H5C	109.5
O2—S2—C6	107.5 (2)	C11—C6—C7	121.1 (4)
O3—S2—C6	109.18 (19)	C11—C6—S2	119.7 (3)
N1—S2—C6	104.44 (19)	C7—C6—S2	119.2 (3)
C4—N1—S2	118.6 (3)	C8—C7—C6	119.3 (4)
C4—N1—S1	121.5 (3)	C8—C7—H7	120.3
S2—N1—S1	119.4 (2)	C6—C7—H7	120.3
C2—C1—S1	115.6 (3)	C7—C8—C9	120.8 (5)
C2—C1—H1A	108.4	C7—C8—H8	119.6
S1—C1—H1A	108.4	C9—C8—H8	119.6
C2—C1—H1B	108.4	C10—C9—C8	118.1 (4)
S1—C1—H1B	108.4	C10—C9—C12	121.7 (5)
H1A—C1—H1B	107.4	C8—C9—C12	120.2 (5)
C3—C2—C1	126.7 (5)	C9—C10—C11	122.9 (5)
C3—C2—H2	116.7	C9—C10—H10	118.6
C1—C2—H2	116.7	C11—C10—H10	118.6
C2—C3—C4	126.2 (4)	C6—C11—C10	117.9 (4)
C2—C3—H3	116.9	C6—C11—H11	121.1
C4—C3—H3	116.9	C10—C11—H11	121.1
N1—C4—C5	113.1 (4)	C9—C12—H12A	109.5
N1—C4—C3	110.0 (4)	C9—C12—H12B	109.5
C5—C4—C3	112.5 (4)	H12A—C12—H12B	109.5
N1—C4—H4	107.0	C9—C12—H12C	109.5
C5—C4—H4	107.0	H12A—C12—H12C	109.5
C3—C4—H4	107.0	H12B—C12—H12C	109.5
O2—S2—N1—C4	43.1 (3)	C2—C3—C4—N1	12.1 (7)
O3—S2—N1—C4	172.8 (3)	C2—C3—C4—C5	−115.0 (6)
C6—S2—N1—C4	−71.4 (3)	O2—S2—C6—C11	6.4 (4)
O2—S2—N1—S1	−128.5 (3)	O3—S2—C6—C11	−123.7 (4)
O3—S2—N1—S1	1.1 (3)	N1—S2—C6—C11	121.9 (4)
C6—S2—N1—S1	116.9 (2)	O2—S2—C6—C7	−176.3 (3)
O1—S1—N1—C4	−53.1 (4)	O3—S2—C6—C7	53.7 (4)
C1—S1—N1—C4	56.2 (4)	N1—S2—C6—C7	−60.7 (4)
O1—S1—N1—S2	118.3 (3)	C11—C6—C7—C8	0.6 (7)
C1—S1—N1—S2	−132.4 (3)	S2—C6—C7—C8	−176.7 (4)
O1—S1—C1—C2	70.7 (4)	C6—C7—C8—C9	0.2 (8)
N1—S1—C1—C2	−39.9 (4)	C7—C8—C9—C10	−0.6 (8)
S1—C1—C2—C3	20.4 (8)	C7—C8—C9—C12	179.3 (5)
C1—C2—C3—C4	−1.9 (9)	C8—C9—C10—C11	0.2 (8)
S2—N1—C4—C5	−90.2 (4)	C12—C9—C10—C11	−179.7 (5)
S1—N1—C4—C5	81.3 (5)	C7—C6—C11—C10	−1.0 (7)
S2—N1—C4—C3	143.1 (3)	S2—C6—C11—C10	176.3 (3)
S1—N1—C4—C3	−45.4 (5)	C9—C10—C11—C6	0.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O2^i	0.97	2.39	3.225 (6)	144
C11—H11···O2	0.93	2.51	2.888 (6)	104
C3—H3···O2^ii	0.93	2.58	3.487 (6)	165
C1—H1A···O3^iii	0.97	2.66	3.601 (6)	164
C5—H5A···O1	0.96	2.56	3.249 (8)	128
C2—H2···O1^iv	0.93	2.63	3.555 (6)	178

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+2, y+1/2, −z+1/2.