Benzyl (1R*,3S*)-3,6-di­hydro-3-methyl-1λ⁴,2-thia­zine-2-carboxyl­ate 1-oxide

The title compound, C₁₃H₁₅NO₃S, is shown to be the (1R*,3S*) isomer with a cis arrangement of the S=O group and the methyl group on the thia­zine ring.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.107
• Data-to-parameter ratio = 10.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_030  Alert B Refined Extinction parameter within range ....       2.00 Sigma

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.98
         From the CIF: _reflns_number_total               1695
         Count of symmetry unique reflns         1697
         Completeness (_total/calc)             99.88%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

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).

(I)

Crystal data

C13H15NO3S	Dx = 1.319 Mg m^−3
Mr = 265.32	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 6.1961 (14) Å	θ = 9–17°
b = 13.613 (4) Å	µ = 0.24 mm^−1
c = 15.842 (2) Å	T = 298 K
V = 1336.2 (6) Å^3	Block, colourless
Z = 4	0.60 × 0.50 × 0.40 mm
F(000) = 560

Data collection

Enraf-Nonius CAD-4 diffractometer	1245 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.005
Graphite monochromator	θmax = 27.0°, θmin = 2.0°
ω–2θ scans	h = 0→7
Absorption correction: ψ scan (ABSCALC in OSCAIL; McArdle & Daly, 1999; North et al., 1986)	k = 0→17
Tmin = 0.869, Tmax = 0.910	l = 0→20
1734 measured reflections	3 standard reflections every 120 min
1695 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 0.0882P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max = 0.006
S = 1.04	Δρmax = 0.22 e Å^−3
1695 reflections	Δρmin = −0.18 e Å^−3
165 parameters	Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.004 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: (Flack, 1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.22 (14)

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)

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

- 2.5128 (0.0084) x + 9.9056 (0.0148) y - 8.7638 (0.0195) z = 2.6812 (0.0241)

* 0.0009 (0.0022) C8 * 0.0034 (0.0025) C9 * -0.0051 (0.0029) C10 * 0.0023 (0.0030) C11 * 0.0020 (0.0028) C12 * -0.0036 (0.0023) C13 0.0177 (0.0055) C7 - 0.5401 (0.0054) O3 - 0.6974 (0.0075) C6 - 0.4491 (0.0080) O2 - 1.1976 (0.0082) N1

Rms deviation of fitted atoms = 0.0032

- 2.5785 (0.0145) x + 11.0127 (0.0124) y - 6.5767 (0.0274) z = 4.0023 (0.0262)

Angle to previous plane (with approximate e.s.d.) = 9.21 (1/4)

* 0.0027 (0.0010) C1 * -0.0063 (0.0023) C2 * 0.0064 (0.0023) C3 * -0.0027 (0.0010) C4 - 0.6413 (0.0059) S1 0.1723 (0.0057) N1 - 2.0715 (0.0054) O1 - 1.2437 (0.0055) C5 0.7013 (0.0085) C6 1.1218 (0.0088) O2 0.6734 (0.0110) O3 1.2430 (0.0145) C7 1.0086 (0.0173) C8

Rms deviation of fitted atoms = 0.0049

4.2624 (0.0044) x - 6.6330 (0.0183) y + 8.5215 (0.0137) z = 1.3214 (0.0257)

Angle to previous plane (with approximate e.s.d.) = 25.34 (0.23)

* 0.0004 (0.0015) N1 * 0.0020 (0.0024) C6 * 0.0280 (0.0015) O2 * -0.0168 (0.0021) O3 * -0.0598 (0.0030) C7 * 0.0463 (0.0019) C8

Rms deviation of fitted atoms = 0.0337

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	0.08303 (14)	0.76417 (5)	0.73601 (5)	0.0617 (2)
N1	0.0832 (4)	0.87138 (14)	0.79177 (13)	0.0548 (5)
O2	0.2626 (4)	1.01446 (14)	0.81665 (14)	0.0703 (6)
O3	0.3397 (4)	0.92319 (13)	0.70174 (13)	0.0672 (6)
O1	0.1581 (4)	0.68484 (14)	0.79119 (17)	0.0784 (7)
C1	−0.2064 (6)	0.7522 (2)	0.7315 (2)	0.0773 (10)
H1A	−0.2614	0.7964	0.6885	0.100*
H1B	−0.2419	0.6857	0.7144	0.100*
C2	−0.3174 (6)	0.7738 (3)	0.8126 (3)	0.0840 (11)
H2	−0.4525	0.7457	0.8209	0.109*
C3	−0.2422 (6)	0.8283 (2)	0.8725 (3)	0.0776 (10)
H3	−0.3306	0.8371	0.9193	0.101*
C4	−0.0279 (5)	0.8788 (2)	0.87440 (18)	0.0618 (8)
H4	−0.0553	0.9487	0.8848	0.080*
C5	0.1115 (7)	0.8417 (3)	0.9463 (2)	0.0845 (11)
H5A	0.1418	0.7732	0.9380	0.118*
H5B	0.0365	0.8505	0.9988	0.118*
H5C	0.2444	0.8779	0.9475	0.118*
C6	0.2329 (5)	0.94327 (18)	0.77302 (17)	0.0544 (7)
C7	0.4952 (6)	0.9954 (2)	0.6752 (2)	0.0796 (11)
H7A	0.5975	1.0082	0.7202	0.104*
H7B	0.4230	1.0565	0.6612	0.104*
C8	0.6100 (5)	0.9557 (2)	0.59927 (19)	0.0609 (7)
C9	0.5167 (6)	0.8866 (2)	0.54767 (19)	0.0717 (9)
H9	0.3792	0.8633	0.5599	0.093*
C10	0.6256 (8)	0.8516 (3)	0.4778 (2)	0.0929 (13)
H10	0.5617	0.8042	0.4438	0.121*
C11	0.8267 (9)	0.8862 (3)	0.4584 (3)	0.0990 (13)
H11	0.8985	0.8629	0.4109	0.129*
C12	0.9223 (7)	0.9551 (3)	0.5090 (3)	0.0955 (13)
H12	1.0592	0.9786	0.4959	0.124*
C13	0.8148 (6)	0.9899 (2)	0.5798 (2)	0.0785 (10)
H13	0.8804	1.0364	0.6143	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0719 (4)	0.0461 (3)	0.0670 (4)	−0.0085 (4)	0.0011 (4)	−0.0093 (3)
N1	0.0647 (13)	0.0431 (10)	0.0564 (11)	−0.0095 (12)	0.0069 (13)	−0.0045 (9)
O2	0.0954 (16)	0.0457 (10)	0.0697 (13)	−0.0158 (11)	0.0131 (13)	−0.0106 (9)
O3	0.0882 (14)	0.0519 (10)	0.0617 (11)	−0.0213 (11)	0.0171 (11)	−0.0058 (9)
O1	0.0716 (14)	0.0483 (10)	0.1153 (18)	0.0117 (10)	−0.0143 (15)	−0.0034 (12)
C1	0.081 (2)	0.0485 (16)	0.103 (2)	−0.0065 (15)	−0.038 (2)	0.0067 (18)
C2	0.0530 (17)	0.0675 (19)	0.132 (3)	−0.0009 (17)	−0.005 (2)	0.015 (2)
C3	0.064 (2)	0.0659 (18)	0.103 (3)	−0.0031 (17)	0.023 (2)	0.001 (2)
C4	0.068 (2)	0.0519 (14)	0.0657 (17)	−0.0012 (14)	0.0152 (15)	−0.0060 (14)
C5	0.097 (3)	0.097 (2)	0.0599 (17)	−0.007 (2)	−0.001 (2)	−0.0024 (18)
C6	0.0654 (16)	0.0427 (12)	0.0551 (15)	−0.0053 (12)	−0.0006 (15)	0.0018 (12)
C7	0.104 (3)	0.0561 (17)	0.078 (2)	−0.0282 (17)	0.0274 (19)	−0.0034 (16)
C8	0.073 (2)	0.0476 (13)	0.0621 (16)	−0.0037 (15)	0.0055 (16)	0.0111 (13)
C9	0.076 (2)	0.077 (2)	0.0620 (18)	−0.0027 (18)	0.0031 (18)	0.0033 (17)
C10	0.117 (4)	0.093 (3)	0.068 (2)	0.001 (3)	0.013 (2)	−0.010 (2)
C11	0.114 (4)	0.082 (2)	0.101 (3)	0.020 (3)	0.039 (3)	0.014 (2)
C12	0.078 (2)	0.078 (2)	0.130 (3)	0.005 (2)	0.036 (3)	0.028 (3)
C13	0.079 (2)	0.0601 (18)	0.096 (3)	−0.0075 (18)	0.007 (2)	0.0159 (18)

Geometric parameters (Å, º)

S1—O1	1.465 (2)	C5—H5A	0.9600
S1—N1	1.706 (2)	C5—H5B	0.9600
S1—C1	1.802 (4)	C5—H5C	0.9600
N1—C6	1.381 (3)	C7—C8	1.499 (4)
N1—C4	1.482 (4)	C7—H7A	0.9700
O2—C6	1.204 (3)	C7—H7B	0.9700
O3—C6	1.337 (3)	C8—C9	1.373 (4)
O3—C7	1.439 (3)	C8—C13	1.386 (5)
C1—C2	1.487 (6)	C9—C10	1.381 (5)
C1—H1A	0.9700	C9—H9	0.9300
C1—H1B	0.9700	C10—C11	1.367 (6)
C2—C3	1.292 (5)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.369 (6)
C3—C4	1.495 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.388 (5)
C4—C5	1.516 (5)	C12—H12	0.9300
C4—H4	0.9800	C13—H13	0.9300
O1—S1—N1	108.75 (13)	H5A—C5—H5C	109.5
O1—S1—C1	105.84 (15)	H5B—C5—H5C	109.5
N1—S1—C1	95.65 (14)	O2—C6—O3	125.0 (3)
C6—N1—C4	117.0 (2)	O2—C6—N1	123.3 (3)
C6—N1—S1	119.69 (19)	O3—C6—N1	111.7 (2)
C4—N1—S1	121.02 (18)	O3—C7—C8	107.8 (2)
C6—O3—C7	116.0 (2)	O3—C7—H7A	110.1
C2—C1—S1	114.1 (2)	C8—C7—H7A	110.1
C2—C1—H1A	108.7	O3—C7—H7B	110.1
S1—C1—H1A	108.7	C8—C7—H7B	110.1
C2—C1—H1B	108.7	H7A—C7—H7B	108.5
S1—C1—H1B	108.7	C9—C8—C13	118.9 (3)
H1A—C1—H1B	107.6	C9—C8—C7	121.7 (3)
C3—C2—C1	125.6 (3)	C13—C8—C7	119.5 (3)
C3—C2—H2	117.2	C8—C9—C10	120.5 (4)
C1—C2—H2	117.2	C8—C9—H9	119.7
C2—C3—C4	126.8 (3)	C10—C9—H9	119.7
C2—C3—H3	116.6	C11—C10—C9	120.4 (4)
C4—C3—H3	116.6	C11—C10—H10	119.8
N1—C4—C3	111.3 (3)	C9—C10—H10	119.8
N1—C4—C5	112.1 (3)	C12—C11—C10	119.9 (4)
C3—C4—C5	111.6 (3)	C12—C11—H11	120.0
N1—C4—H4	107.2	C10—C11—H11	120.0
C3—C4—H4	107.2	C11—C12—C13	120.0 (4)
C5—C4—H4	107.2	C11—C12—H12	120.0
C4—C5—H5A	109.5	C13—C12—H12	120.0
C4—C5—H5B	109.5	C8—C13—C12	120.3 (4)
H5A—C5—H5B	109.5	C8—C13—H13	119.8
C4—C5—H5C	109.5	C12—C13—H13	119.8
O1—S1—N1—C6	109.8 (2)	C4—N1—C6—O2	−6.5 (4)
C1—S1—N1—C6	−141.4 (2)	S1—N1—C6—O2	−169.4 (2)
O1—S1—N1—C4	−52.4 (3)	C4—N1—C6—O3	173.0 (2)
C1—S1—N1—C4	56.4 (3)	S1—N1—C6—O3	10.1 (3)
O1—S1—C1—C2	67.6 (3)	C6—O3—C7—C8	175.1 (3)
N1—S1—C1—C2	−43.7 (3)	O3—C7—C8—C9	24.8 (4)
S1—C1—C2—C3	24.2 (5)	O3—C7—C8—C13	−155.9 (3)
C1—C2—C3—C4	−1.7 (6)	C13—C8—C9—C10	0.3 (5)
C6—N1—C4—C3	155.1 (3)	C7—C8—C9—C10	179.7 (3)
S1—N1—C4—C3	−42.2 (3)	C8—C9—C10—C11	−0.9 (6)
C6—N1—C4—C5	−79.2 (3)	C9—C10—C11—C12	0.8 (6)
S1—N1—C4—C5	83.5 (3)	C10—C11—C12—C13	−0.1 (6)
C2—C3—C4—N1	8.4 (5)	C9—C8—C13—C12	0.4 (4)
C2—C3—C4—C5	−117.6 (4)	C7—C8—C13—C12	−179.0 (3)
C7—O3—C6—O2	−2.5 (4)	C11—C12—C13—C8	−0.5 (5)
C7—O3—C6—N1	178.1 (3)

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	3.345 (4)	169
C9—H9···O3	0.93	2.40	2.722 (4)	100
C5—H5A···O1	0.96	2.62	3.269 (4)	125
C2—H2···O1^ii	0.93	2.59	3.485 (5)	161
C4—H4···O2	0.98	2.42	2.736 (4)	98
C7—H7A···O2	0.97	2.58	2.677 (4)	85
C13—H13···O1^iii	0.93	2.53	3.354 (4)	148

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