An unusual methyl­ene aziridine refined in P2₁/c and the nonstandard setting P2₁/n

The unusual methyl­ene aziridine 6-tert-butyl-3-oxa-2-thia-1-aza­bicyclo­[5.1.0]oct-6-ene 2,2-dioxide, C₉H₁₅NO₃S, was found to crystallize with two mol­ecules in the asymmetric unit. The structure was solved in both the approximately orthogonal and the oblique settings of space group No. 14, viz. P2₁/n and P2₁/c, respectively. A comparison of these results clearly displayed an increase in the correlation between coordinates in the ac plane for the oblique cell. The increase in the corresponding covariances makes a significant contribution to the standard uncertainties of derived parameters, e.g. bond lengths. Since there is yet no CIF definition for the full variance-covariance matrix, there are clear advantages to reporting the structure in the nonstandard space-group setting.

S1. Comment

The title compound, 6-tert-butyl-3-oxa-2-thia-1-azabicyclo[5.1.0]oct-6-ene 2,2-dioxide, and related methylene aziridines (Feast et al. 2009) were prepared during our ongoing study of nitrogen-containing 1,3-dipoles (Robertson et al., 2005; White, 2007) in order to probe their potential as 2-aminoallyl cation precursors (Prié et al., 2004).

The structure of the methylene aziridine was initially determined in the monoclinic space group P2₁/_n, (I), with a cell of a = 13.8593 (3) Å, b = 10.5242 (2) Å, c = 14.8044 (4) Å and β = 92.0014 (7)° and two molecules in the asymmetric unit (Fig. 1).

The unusual bond angles at C7/C107 suggested it would be advisable to carry out a comparison with the structures in the Cambridge Structural Database (CSD; Version ?; Allen, 2002) using Mogul (Bruno et al., 2004). For comparison, Mogul uses a figure of merit Z (defined as the difference between observed value and the median divided by the standard deviation of the Mogul distribution). Typically, Z values greater than about 2–3 indicate that a bond length or angle are sufficiently unusual to warrant further investigation. Although (I) gave a Z value greater than 100 for the top eight queries, each of these had only one match in the CSD and the obvious C6—C7—C9/C106—C107—C109 angle had no hits at all. Indeed, more than one-third of the queries generated by CRYSTALS (Betteridge et al., 2003) had fewer than six hits in the CSD, suggesting the structure has little precedence in the literature. Examination of the molecular structure showed why this is the case, with the particularly unusual seven-membered ring (comprising three hetero-atoms and a double bond), fused with a three-membered ring, leading to an extremely strained geometry at atoms S1, C7 and N8 (and the analogous atoms S101,C107 and N108).

The two equivalent molecules have very similar conformations when overlayed (positional, bond and torsion r.m.s. deviations of 0.166, 0.007 Å and 3.542°). Both symmetry equivalents (referred to by the first atom in the residue, S1 and S101) form dimers around an inversion centre. These are held together by C—H···O interactions between chemically equivalent atoms (C9/C109 and O2/O102; Table 1). The dimers form layers parallel to the [101] plane containing exclusively either S1 or S101; in turn, these layers are connected together by further C—H···O interactions (Fig. 2).

Prior to publication, the CIF was verified with the online checking facility checkCIF, which gave the following alert:

PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c···. P21/n

`The reported monoclinic space-group is in a non-standard setting. Transformation to the conventional setting is indicated unless there is a good (scientific) reason not to do so.'

The cell obtained from the initial indexing was then transformed using the matrix A (Eqn. 1) and reprocessed (including integration, scaling and cell final refinement) to give the data in the space group P2₁/c, with a cell of a = 13.8594 (2) Å, b = 10.5243 (2) Å, c = 19.9230 (3) Å and β = 132.0439 (7)°, (II). The atomic coordinates from the original structure were transformed using (A^T)^-1 given in equation (2) and the structure re-refined:

A= (1 0 0, 0 1 0, 1 0 1), (1)

(A^-1)^T= (1 0 1, 0 1 0, 0 0 1). (2)

Comparison of (I) and (II) demonstrated that the bond lengths (and angles) were the same allowing for rounding error. This is as expected, since the structures are the same, merely in a different cell setting. However, it has long been known that refinements in oblique cells have increased correlation between selected parameters, potentially making refinements less stable (Dunitz, 1979). Thus, a large β value, would be expected to give increased correlation between parameters with respect to the a and c axes. In (I), the largest correlations are between the sulfur anisotropic displacement parameters (ADPs) and the scale factor (Table 2). However, although the correlations between the sulfur ADPs and the scale factor in (II) are a similar size, correlations between individual components of the ADPs are increased, for example, the largest correlation is 0.809 between U₃₃(O14) and U₁₃(O14), increased from -0.080. Correlations between the positional parameters are also affected; though the changes are smaller, the effects are visible by comparing the s.u. values calculated with and without covariances. Since only the variances are included in the CIF, this was easily achieved using PLATON (Spek, 2009). Table 3 shows the bond lengths with s.u. values for (I) and (II), and it is clear that the bond lengths are very similar in both cell settings whether determined by PLATON or CRYSTALS. [Unit cell and atomic parameters are held to full machine precision by the refinement software (CRYSTALS). Some of this precision is inevitably lost when these numbers are rounded by the `rule of 19' during the generation of the CIF.] The s.u. values for all the C—C and C—O bonds are also consistent for (I) and (II) calculated from the full variance–covariance matrix, and calculations using only the variances give a good estimate of the s.u. values for (I). However, the corresponding s.u. calculations for (II) are less reliable when the covariances are excluded. This effect is most apparent where the bond is predominantly parallel to the a axis (e.g. S101—N108, C104—C105 and C10—C13) and the s.u. values are nearly doubled.

In conclusion, analysis of this unusual methylene aziridine has demonstrated the effect of excluding the covariances from calculations of the s.u. values and shown how this effect is enhanced for monoclinic structures in a cell setting where β deviates significantly from 90°. Additionally, the increase in the correlation due to the oblique cell setting is apparent, and although there are no obvious consequences in this case, this could give rise to refinement difficulties for more complex structures.

Related literature

For related literature, see: Allen (2002); Betteridge et al. (2003); Bruno et al. (2004); Dunitz (1979); Feast et al. (2009); Prié et al. (2004); Robertson et al. (2005); Spek (2003, 2009); Watkin (1994); White (2007).

S2. Experimental

The title compound was crystallized by evaporation from a saturated solution in diethyl ether. NMR (100 MHz, CDCl₃): δ_C 27.9 [C(CH₃)₃], 28.0 (═ CCH₂), 35.3 (C(CH₃)₃), 40.2 (NCH₂), 75.3 (OCH₂), 114.9 (NC═C), 126.4 (NC═C). In the ¹H NMR at room temperature, very broad peaks are found for the C5 methylene H atoms and a broad peak contains the signals for both the C9 methylene H atoms [δ_H (400 MHz, CDCl₃, 298 K) 2.45 and 2.88 (2 × 1H, 2 × br s, OCH₂CH₂), 3.44 (2H, br s, NCH₂)]. Once the temperature was reduced to 228 K four distinct signals resolved, indicating that conformational change at room temperature is slow on an NMR timescale. Complete data at 228 K: δ_H (500 MHz, CD₂Cl₂) 1.11 [9H, s, (CH₃)₃], 2.39 and 2.90 (1H, d, J = 14.3 Hz and 1H, app. t. J = 14.3 Hz, OCH₂CH₂), 3.45 and 3.53 (2 × 1H, 2 × br s, NCH₂), 4.48–4.57 (2H, m, OCH₂). IR (thin film): ν_max 3075 (m), 2968 (s), 1468 (m), 1359 (s), 1296 (w), 1261 (w), 1183 (s) cm^-1. High resolution mass spectrometry (ESI+): found 240.0670; C₉H₁₅NNaO₃S (MNa⁺) requires 240.0665.

S3. Refinement

The H atoms were all located in a difference map, but were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98 Å) and U_iso(H) values (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints. For both (I) and (II), a Chebychev polynomial weighting scheme was applied (Watkin, 1994; Prince, 1982).

Computing details

For both compounds, data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I); Structure transformed from solution to I for (II). For both compounds, program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. The title compound, (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing, viewed down the b axis, showing the layers. (The residues containing atoms S1 and S101 are shown in green and blue, respectively, in the electronic version of the journal.) C—H···O interactions are shown as dotted lines.

(I) 6-tert-butyl-3-oxa-2-thia-1-azabicyclo[5.1.0]oct-6-ene 2,2-dioxide

Crystal data

C9H15NO3S	F(000) = 928
Mr = 217.29	Dx = 1.338 Mg m^−3
Monoclinic, P21/n	Melting point: 331 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 13.8593 (3) Å	Cell parameters from 4693 reflections
b = 10.5242 (2) Å	θ = 5–27°
c = 14.8044 (4) Å	µ = 0.28 mm^−1
β = 92.0014 (7)°	T = 150 K
V = 2158.02 (9) Å^3	Block, colourless
Z = 8	0.32 × 0.26 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	3768 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 27.5°, θmin = 5.4°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −17→17
Tmin = 0.81, Tmax = 0.96	k = −13→13
19529 measured reflections	l = −19→19
4913 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.123	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 27.2 43.7 25.5 10.4 2.31
S = 0.94	(Δ/σ)max = 0.000257
4913 reflections	Δρmax = 0.43 e Å^−3
253 parameters	Δρmin = −0.44 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
S1	0.39121 (4)	0.61526 (5)	0.63002 (4)	0.0303
O2	0.47797 (11)	0.58690 (16)	0.58492 (11)	0.0367
O3	0.40023 (11)	0.57263 (15)	0.73067 (10)	0.0325
C4	0.44292 (18)	0.4484 (2)	0.75537 (15)	0.0371
C5	0.37343 (17)	0.3388 (2)	0.73970 (14)	0.0342
C6	0.35709 (14)	0.3028 (2)	0.64083 (14)	0.0267
C7	0.32528 (14)	0.3925 (2)	0.58528 (13)	0.0265
N8	0.30018 (12)	0.52508 (17)	0.59397 (12)	0.0292
C9	0.30911 (15)	0.4599 (2)	0.50154 (14)	0.0308
C10	0.37851 (15)	0.1678 (2)	0.60990 (14)	0.0290
C11	0.35496 (18)	0.1517 (2)	0.50870 (15)	0.0377
C12	0.31541 (19)	0.0755 (2)	0.66261 (19)	0.0428
C13	0.48513 (17)	0.1370 (3)	0.62839 (19)	0.0441
O14	0.35905 (13)	0.74312 (15)	0.63205 (13)	0.0436
S101	0.05457 (4)	0.23211 (5)	0.47800 (4)	0.0319
O102	0.05996 (12)	0.11981 (16)	0.53174 (12)	0.0408
O103	0.09829 (11)	0.34692 (15)	0.53243 (10)	0.0339
C104	0.08001 (15)	0.3584 (2)	0.62967 (15)	0.0339
C105	−0.01681 (16)	0.4187 (2)	0.64730 (15)	0.0319
C106	−0.10419 (14)	0.33485 (18)	0.62502 (13)	0.0245
C107	−0.11226 (14)	0.2848 (2)	0.54353 (14)	0.0267
N108	−0.05752 (13)	0.28465 (18)	0.46234 (12)	0.0309
C109	−0.14131 (15)	0.1921 (2)	0.47596 (15)	0.0335
C110	−0.17700 (14)	0.3077 (2)	0.69683 (14)	0.0274
C113	−0.12924 (17)	0.2231 (2)	0.76997 (15)	0.0357
C111	−0.26600 (15)	0.2393 (2)	0.65641 (16)	0.0367
C112	−0.20972 (18)	0.4317 (2)	0.74049 (17)	0.0394
O114	0.09861 (13)	0.2345 (2)	0.39283 (12)	0.0495
H41	0.4605	0.4538	0.8197	0.0451*
H42	0.5007	0.4351	0.7187	0.0452*
H52	0.4032	0.2652	0.7713	0.0405*
H51	0.3102	0.3618	0.7663	0.0406*
H92	0.3651	0.4803	0.4653	0.0363*
H91	0.2483	0.4509	0.4663	0.0376*
H111	0.3663	0.0629	0.4932	0.0578*
H112	0.3957	0.2086	0.4743	0.0581*
H113	0.2869	0.1724	0.4972	0.0580*
H122	0.3327	−0.0091	0.6442	0.0638*
H121	0.3291	0.0859	0.7282	0.0643*
H123	0.2475	0.0902	0.6465	0.0645*
H132	0.4952	0.0491	0.6123	0.0671*
H131	0.5016	0.1505	0.6932	0.0669*
H133	0.5234	0.1910	0.5911	0.0673*
H1041	0.1315	0.4128	0.6537	0.0414*
H1042	0.0837	0.2726	0.6566	0.0409*
H1052	−0.0175	0.4379	0.7133	0.0398*
H1051	−0.0216	0.4980	0.6111	0.0398*
H1092	−0.1273	0.1027	0.4861	0.0425*
H1091	−0.1971	0.2047	0.4353	0.0421*
H1131	−0.1735	0.2076	0.8185	0.0526*
H1132	−0.0720	0.2647	0.7961	0.0533*
H1133	−0.1102	0.1411	0.7449	0.0526*
H1112	−0.3119	0.2243	0.7041	0.0555*
H1111	−0.2969	0.2911	0.6078	0.0562*
H1113	−0.2481	0.1560	0.6315	0.0557*
H1122	−0.2579	0.4118	0.7853	0.0602*
H1121	−0.1544	0.4766	0.7703	0.0604*
H1123	−0.2397	0.4865	0.6946	0.0600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0305 (3)	0.0260 (3)	0.0341 (3)	−0.0011 (2)	−0.0012 (2)	−0.0003 (2)
O2	0.0288 (7)	0.0444 (9)	0.0370 (8)	−0.0075 (7)	0.0039 (6)	−0.0043 (7)
O3	0.0367 (8)	0.0315 (8)	0.0294 (7)	0.0022 (6)	0.0006 (6)	−0.0052 (6)
C4	0.0453 (13)	0.0374 (12)	0.0278 (10)	0.0030 (10)	−0.0094 (9)	0.0001 (9)
C5	0.0425 (12)	0.0343 (11)	0.0258 (10)	0.0025 (9)	0.0008 (9)	0.0036 (8)
C6	0.0241 (9)	0.0284 (10)	0.0278 (9)	−0.0015 (7)	0.0007 (7)	0.0022 (8)
C7	0.0225 (9)	0.0285 (10)	0.0284 (10)	−0.0018 (7)	0.0010 (7)	0.0001 (8)
N8	0.0266 (8)	0.0287 (9)	0.0320 (9)	−0.0002 (7)	−0.0015 (7)	0.0018 (7)
C9	0.0308 (10)	0.0301 (10)	0.0310 (10)	−0.0025 (8)	−0.0045 (8)	0.0036 (8)
C10	0.0262 (9)	0.0264 (10)	0.0344 (11)	0.0012 (8)	0.0013 (8)	0.0028 (8)
C11	0.0420 (12)	0.0351 (12)	0.0360 (12)	0.0011 (10)	0.0002 (9)	−0.0069 (9)
C12	0.0451 (13)	0.0302 (11)	0.0537 (15)	0.0003 (10)	0.0086 (11)	0.0065 (10)
C13	0.0307 (11)	0.0468 (14)	0.0545 (15)	0.0074 (10)	0.0008 (10)	0.0029 (12)
O14	0.0467 (10)	0.0231 (8)	0.0602 (11)	0.0025 (7)	−0.0077 (8)	−0.0017 (7)
S101	0.0276 (2)	0.0362 (3)	0.0321 (3)	0.0008 (2)	0.00173 (19)	−0.0057 (2)
O102	0.0390 (9)	0.0307 (8)	0.0523 (10)	0.0043 (7)	−0.0044 (7)	−0.0036 (7)
O103	0.0308 (8)	0.0368 (8)	0.0343 (8)	−0.0081 (6)	0.0046 (6)	−0.0033 (7)
C104	0.0300 (10)	0.0401 (12)	0.0316 (11)	−0.0086 (9)	0.0006 (8)	−0.0069 (9)
C105	0.0345 (11)	0.0289 (10)	0.0324 (10)	−0.0073 (9)	0.0031 (8)	−0.0044 (8)
C106	0.0256 (9)	0.0221 (9)	0.0257 (9)	0.0021 (7)	−0.0012 (7)	0.0012 (7)
C107	0.0244 (9)	0.0275 (10)	0.0282 (9)	0.0003 (8)	−0.0001 (7)	0.0014 (8)
N108	0.0290 (9)	0.0380 (10)	0.0255 (8)	−0.0012 (7)	−0.0002 (7)	0.0005 (7)
C109	0.0286 (10)	0.0412 (12)	0.0305 (10)	−0.0037 (9)	−0.0020 (8)	−0.0089 (9)
C110	0.0255 (9)	0.0290 (10)	0.0277 (9)	0.0032 (8)	0.0005 (7)	0.0038 (8)
C113	0.0354 (11)	0.0377 (12)	0.0338 (11)	0.0018 (9)	−0.0013 (9)	0.0085 (9)
C111	0.0274 (10)	0.0457 (13)	0.0368 (11)	−0.0068 (9)	−0.0010 (8)	0.0060 (10)
C112	0.0415 (12)	0.0369 (12)	0.0403 (12)	0.0082 (10)	0.0082 (10)	−0.0013 (10)
O114	0.0394 (9)	0.0711 (13)	0.0386 (9)	0.0018 (9)	0.0110 (7)	−0.0121 (9)

Geometric parameters (Å, º)

S1—O2	1.4271 (16)	S101—O103	1.5628 (16)
S1—O3	1.5569 (16)	S101—N108	1.6577 (18)
S1—N8	1.6524 (18)	S101—O114	1.4200 (18)
S1—O14	1.4182 (16)	S101—O102	1.4252 (18)
O3—C4	1.476 (3)	O103—C104	1.475 (3)
C4—C5	1.515 (3)	C104—C105	1.515 (3)
C4—H41	0.976	C104—H1041	0.972
C4—H42	0.993	C104—H1042	0.988
C5—C6	1.521 (3)	C105—C106	1.525 (3)
C5—H52	0.988	C105—H1052	0.997
C5—H51	1.003	C105—H1051	0.994
C6—C7	1.317 (3)	C106—C107	1.317 (3)
C6—C10	1.525 (3)	C106—C110	1.518 (3)
C7—N8	1.445 (3)	C107—N108	1.444 (3)
C7—C9	1.439 (3)	C107—C109	1.445 (3)
N8—C9	1.540 (3)	N108—C109	1.535 (3)
C9—H92	0.982	C109—H1092	0.972
C9—H91	0.981	C109—H1091	0.972
C10—C11	1.532 (3)	C110—C113	1.534 (3)
C10—C12	1.538 (3)	C110—C111	1.532 (3)
C10—C13	1.528 (3)	C110—C112	1.533 (3)
C11—H111	0.977	C113—H1131	0.975
C11—H112	0.978	C113—H1132	0.975
C11—H113	0.977	C113—H1133	0.979
C12—H122	0.964	C111—H1112	0.979
C12—H121	0.989	C111—H1111	0.989
C12—H123	0.976	C111—H1113	0.986
C13—H132	0.967	C112—H1122	0.980
C13—H131	0.989	C112—H1121	0.992
C13—H133	0.964	C112—H1123	0.973
O2—S1—O3	110.29 (9)	O103—S101—N108	99.14 (9)
O2—S1—N8	112.02 (9)	O103—S101—O114	105.86 (10)
O3—S1—N8	100.28 (9)	N108—S101—O114	107.45 (10)
O2—S1—O14	118.62 (11)	O103—S101—O102	109.97 (10)
O3—S1—O14	105.55 (10)	N108—S101—O102	112.65 (10)
N8—S1—O14	108.34 (10)	O114—S101—O102	119.63 (12)
S1—O3—C4	120.70 (13)	S101—O103—C104	119.32 (13)
O3—C4—C5	112.90 (18)	O103—C104—C105	112.69 (18)
O3—C4—H41	105.9	O103—C104—H1041	104.8
C5—C4—H41	109.2	C105—C104—H1041	109.5
O3—C4—H42	108.3	O103—C104—H1042	108.1
C5—C4—H42	109.3	C105—C104—H1042	110.3
H41—C4—H42	111.3	H1041—C104—H1042	111.3
C4—C5—C6	114.16 (18)	C104—C105—C106	114.97 (17)
C4—C5—H52	105.8	C104—C105—H1052	107.0
C6—C5—H52	107.8	C106—C105—H1052	107.1
C4—C5—H51	108.4	C104—C105—H1051	107.5
C6—C5—H51	109.5	C106—C105—H1051	109.4
H52—C5—H51	111.1	H1052—C105—H1051	110.8
C5—C6—C7	117.23 (19)	C105—C106—C107	118.07 (18)
C5—C6—C10	119.80 (18)	C105—C106—C110	119.98 (17)
C7—C6—C10	122.97 (19)	C107—C106—C110	121.91 (18)
C6—C7—N8	135.43 (19)	C106—C107—N108	137.12 (19)
C6—C7—C9	158.3 (2)	C106—C107—C109	156.4 (2)
N8—C7—C9	64.54 (14)	N108—C107—C109	64.18 (14)
C7—N8—S1	113.58 (13)	C107—N108—S101	113.66 (13)
C7—N8—C9	57.54 (13)	C107—N108—C109	57.95 (13)
S1—N8—C9	117.31 (13)	S101—N108—C109	118.67 (15)
N8—C9—C7	57.92 (13)	N108—C109—C107	57.86 (13)
N8—C9—H92	118.5	N108—C109—H1092	119.1
C7—C9—H92	118.5	C107—C109—H1092	119.9
N8—C9—H91	114.9	N108—C109—H1091	114.9
C7—C9—H91	121.1	C107—C109—H1091	122.2
H92—C9—H91	114.3	H1092—C109—H1091	112.3
C6—C10—C11	111.09 (17)	C106—C110—C113	108.82 (17)
C6—C10—C12	108.42 (18)	C106—C110—C111	111.15 (17)
C11—C10—C12	108.72 (19)	C113—C110—C111	108.95 (18)
C6—C10—C13	109.94 (18)	C106—C110—C112	110.38 (17)
C11—C10—C13	108.87 (19)	C113—C110—C112	108.88 (18)
C12—C10—C13	109.79 (19)	C111—C110—C112	108.61 (18)
C10—C11—H111	107.8	C110—C113—H1131	110.5
C10—C11—H112	109.5	C110—C113—H1132	110.2
H111—C11—H112	111.3	H1131—C113—H1132	107.9
C10—C11—H113	108.5	C110—C113—H1133	111.0
H111—C11—H113	109.5	H1131—C113—H1133	108.5
H112—C11—H113	110.2	H1132—C113—H1133	108.7
C10—C12—H122	106.8	C110—C111—H1112	109.2
C10—C12—H121	109.6	C110—C111—H1111	110.3
H122—C12—H121	109.8	H1112—C111—H1111	109.7
C10—C12—H123	109.7	C110—C111—H1113	110.7
H122—C12—H123	108.9	H1112—C111—H1113	107.7
H121—C12—H123	111.9	H1111—C111—H1113	109.1
C10—C13—H132	107.8	C110—C112—H1122	108.7
C10—C13—H131	109.4	C110—C112—H1121	111.0
H132—C13—H131	110.2	H1122—C112—H1121	109.6
C10—C13—H133	108.7	C110—C112—H1123	109.6
H132—C13—H133	109.7	H1122—C112—H1123	108.4
H131—C13—H133	111.0	H1121—C112—H1123	109.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H92···O2^i	0.98	2.43	3.294 (3)	147
C9—H91···O103	0.98	2.57	3.202 (3)	122
C109—H1092···O102^ii	0.97	2.54	3.474 (3)	162
C109—H1091···O14^iii	0.97	2.49	3.434 (3)	165

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

(II)

Crystal data

C9H15NO3S	F(000) = 928
Mr = 217.29	Dx = 1.337 Mg m^−3
Monoclinic, P21/c	Melting point: 331 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.8594 (2) Å	Cell parameters from 4694 reflections
b = 10.5243 (2) Å	θ = 5–27°
c = 19.9230 (3) Å	µ = 0.28 mm^−1
β = 132.0439 (7)°	T = 150 K
V = 2158.07 (7) Å^3	Block, colourless
Z = 8	0.32 × 0.26 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	3769 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 5.4°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −17→17
Tmin = 0.81, Tmax = 0.96	k = −13→13
9037 measured reflections	l = −25→25
4913 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.120	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 18.1 26.7 12.7 3.26
S = 0.94	(Δ/σ)max = 0.001
4913 reflections	Δρmax = 0.44 e Å^−3
253 parameters	Δρmin = −0.45 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
S1	0.76119 (5)	0.38474 (5)	0.36998 (4)	0.0300
O2	0.89308 (15)	0.41318 (17)	0.41507 (11)	0.0364
O3	0.66953 (15)	0.42735 (15)	0.26930 (10)	0.0323
C4	0.6878 (3)	0.5516 (2)	0.24470 (16)	0.0367
C5	0.6338 (2)	0.6612 (2)	0.26038 (15)	0.0339
C6	0.7163 (2)	0.6973 (2)	0.35921 (14)	0.0264
C7	0.7400 (2)	0.6076 (2)	0.41473 (14)	0.0263
N8	0.70607 (18)	0.47484 (18)	0.40600 (12)	0.0290
C9	0.8076 (2)	0.5400 (2)	0.49846 (15)	0.0304
C10	0.7686 (2)	0.8320 (2)	0.39004 (15)	0.0287
C11	0.8463 (2)	0.8483 (2)	0.49132 (16)	0.0375
C12	0.6527 (3)	0.9245 (2)	0.33738 (19)	0.0422
C13	0.8567 (3)	0.8629 (3)	0.37153 (19)	0.0437
O14	0.7270 (2)	0.25681 (15)	0.36795 (13)	0.0432
S101	0.57657 (5)	0.76790 (6)	0.52200 (4)	0.0317
O102	0.52818 (18)	0.88029 (16)	0.46823 (13)	0.0406
O103	0.56585 (15)	0.65307 (16)	0.46757 (11)	0.0336
C104	0.4504 (2)	0.6417 (2)	0.37043 (15)	0.0337
C105	0.3360 (2)	0.5815 (2)	0.35276 (15)	0.0315
C106	0.2709 (2)	0.66518 (19)	0.37506 (13)	0.0242
C107	0.3442 (2)	0.7152 (2)	0.45643 (14)	0.0267
N108	0.48021 (18)	0.71538 (19)	0.53769 (12)	0.0306
C109	0.3827 (2)	0.8079 (2)	0.52405 (15)	0.0333
C110	0.1261 (2)	0.6922 (2)	0.30314 (14)	0.0272
C113	0.1009 (2)	0.7770 (2)	0.23011 (16)	0.0355
C111	0.0776 (2)	0.7607 (2)	0.34358 (16)	0.0366
C112	0.0498 (2)	0.5682 (2)	0.25950 (17)	0.0392
O114	0.70583 (17)	0.7655 (2)	0.60715 (12)	0.0490
H41	0.6410	0.5462	0.1804	0.0451*
H42	0.7822	0.5649	0.2814	0.0452*
H52	0.6319	0.7348	0.2288	0.0405*
H51	0.5439	0.6382	0.2338	0.0406*
H92	0.8998	0.5196	0.5347	0.0363*
H91	0.7820	0.5490	0.5337	0.0376*
H111	0.8731	0.9371	0.5069	0.0578*
H112	0.9214	0.7914	0.5257	0.0581*
H113	0.7897	0.8276	0.5028	0.0580*
H122	0.6884	1.0092	0.3558	0.0638*
H121	0.6007	0.9142	0.2717	0.0643*
H123	0.6009	0.9099	0.3535	0.0645*
H132	0.8828	0.9509	0.3876	0.0671*
H131	0.8083	0.8494	0.3067	0.0669*
H133	0.9323	0.8090	0.4088	0.0673*
H1041	0.4779	0.5873	0.3464	0.0414*
H1042	0.4272	0.7275	0.3435	0.0409*
H1052	0.2694	0.5622	0.2868	0.0398*
H1051	0.3675	0.5021	0.3890	0.0398*
H1092	0.3866	0.8973	0.5139	0.0425*
H1091	0.3677	0.7953	0.5647	0.0421*
H1131	0.0080	0.7924	0.1816	0.0526*
H1132	0.1320	0.7354	0.2039	0.0533*
H1133	0.1450	0.8590	0.2552	0.0526*
H1112	−0.0160	0.7757	0.2959	0.0555*
H1111	0.0953	0.7089	0.3922	0.0562*
H1113	0.1204	0.8440	0.3685	0.0557*
H1122	−0.0432	0.5882	0.2147	0.0602*
H1121	0.0753	0.5233	0.2297	0.0604*
H1123	0.0657	0.5134	0.3054	0.0600*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0344 (3)	0.0258 (3)	0.0339 (3)	0.0005 (2)	0.0245 (2)	−0.0004 (2)
O2	0.0295 (8)	0.0442 (10)	0.0366 (8)	0.0026 (7)	0.0226 (7)	−0.0043 (7)
O3	0.0338 (8)	0.0312 (8)	0.0287 (8)	−0.0050 (6)	0.0196 (7)	−0.0047 (6)
C4	0.0477 (13)	0.0368 (12)	0.0275 (11)	−0.0023 (10)	0.0259 (11)	−0.0002 (9)
C5	0.0352 (11)	0.0339 (12)	0.0255 (10)	0.0003 (9)	0.0174 (9)	0.0031 (9)
C6	0.0259 (10)	0.0280 (10)	0.0271 (10)	0.0025 (8)	0.0185 (9)	0.0022 (8)
C7	0.0255 (9)	0.0282 (10)	0.0282 (10)	0.0013 (8)	0.0191 (9)	0.0001 (8)
N8	0.0317 (9)	0.0281 (9)	0.0323 (9)	0.0014 (7)	0.0235 (8)	0.0015 (7)
C9	0.0365 (11)	0.0299 (11)	0.0301 (10)	0.0051 (9)	0.0244 (10)	0.0043 (9)
C10	0.0294 (10)	0.0260 (10)	0.0345 (11)	0.0013 (8)	0.0229 (9)	0.0029 (8)
C11	0.0402 (12)	0.0351 (12)	0.0351 (12)	−0.0055 (10)	0.0243 (11)	−0.0069 (10)
C12	0.0413 (13)	0.0300 (12)	0.0523 (15)	0.0042 (10)	0.0301 (12)	0.0063 (11)
C13	0.0421 (14)	0.0467 (15)	0.0539 (15)	−0.0037 (11)	0.0369 (13)	0.0027 (12)
O14	0.0624 (12)	0.0229 (8)	0.0595 (12)	−0.0032 (8)	0.0470 (11)	−0.0015 (7)
S101	0.0287 (3)	0.0360 (3)	0.0318 (3)	−0.0046 (2)	0.0209 (2)	−0.0057 (2)
O102	0.0512 (10)	0.0306 (9)	0.0519 (10)	−0.0060 (7)	0.0395 (9)	−0.0037 (8)
O103	0.0288 (8)	0.0365 (9)	0.0336 (8)	0.0039 (7)	0.0201 (7)	−0.0035 (7)
C104	0.0307 (11)	0.0400 (12)	0.0316 (11)	0.0011 (9)	0.0214 (10)	−0.0073 (9)
C105	0.0312 (11)	0.0285 (11)	0.0322 (11)	0.0022 (9)	0.020 (1)	−0.0043 (9)
C106	0.0280 (10)	0.0218 (9)	0.0255 (9)	−0.0009 (8)	0.0190 (8)	0.0008 (7)
C107	0.0270 (10)	0.0277 (10)	0.0279 (10)	0.0007 (8)	0.0194 (9)	0.0014 (8)
N108	0.0279 (9)	0.0381 (10)	0.0254 (8)	0.0011 (8)	0.0177 (8)	0.0005 (8)
C109	0.0326 (11)	0.0410 (13)	0.0298 (11)	−0.0034 (9)	0.0224 (10)	−0.0089 (9)
C110	0.0267 (10)	0.0287 (10)	0.0275 (10)	0.0006 (8)	0.0187 (9)	0.0042 (8)
C113	0.0371 (12)	0.0375 (12)	0.0331 (11)	0.0044 (10)	0.0240 (10)	0.0084 (10)
C111	0.0341 (12)	0.0457 (14)	0.0366 (12)	0.0093 (10)	0.0264 (11)	0.0061 (10)
C112	0.0340 (12)	0.0365 (13)	0.0407 (13)	−0.0070 (10)	0.0223 (11)	−0.0011 (10)
O114	0.0285 (9)	0.0710 (14)	0.0377 (9)	−0.0099 (8)	0.0181 (8)	−0.0121 (9)

Geometric parameters (Å, º)

S1—O2	1.4278 (17)	S101—O103	1.5628 (16)
S1—O3	1.5573 (16)	S101—N108	1.6571 (19)
S1—N8	1.6527 (18)	S101—O114	1.4204 (18)
S1—O14	1.4189 (17)	S101—O102	1.4262 (19)
O3—C4	1.476 (3)	O103—C104	1.474 (3)
C4—C5	1.517 (3)	C104—C105	1.514 (3)
C4—H41	0.976	C104—H1041	0.972
C4—H42	0.993	C104—H1042	0.988
C5—C6	1.521 (3)	C105—C106	1.525 (3)
C5—H52	0.988	C105—H1052	0.998
C5—H51	1.003	C105—H1051	0.994
C6—C7	1.318 (3)	C106—C107	1.316 (3)
C6—C10	1.522 (3)	C106—C110	1.519 (3)
C7—N8	1.447 (3)	C107—N108	1.445 (3)
C7—C9	1.440 (3)	C107—C109	1.445 (3)
N8—C9	1.540 (3)	N108—C109	1.535 (3)
C9—H92	0.982	C109—H1092	0.972
C9—H91	0.981	C109—H1091	0.972
C10—C11	1.533 (3)	C110—C113	1.535 (3)
C10—C12	1.540 (3)	C110—C111	1.532 (3)
C10—C13	1.529 (3)	C110—C112	1.532 (3)
C11—H111	0.977	C113—H1131	0.975
C11—H112	0.978	C113—H1132	0.975
C11—H113	0.977	C113—H1133	0.979
C12—H122	0.964	C111—H1112	0.979
C12—H121	0.989	C111—H1111	0.989
C12—H123	0.976	C111—H1113	0.986
C13—H132	0.967	C112—H1122	0.980
C13—H131	0.989	C112—H1121	0.992
C13—H133	0.964	C112—H1123	0.973
O2—S1—O3	110.26 (10)	O103—S101—N108	99.14 (10)
O2—S1—N8	112.07 (10)	O103—S101—O114	105.83 (11)
O3—S1—N8	100.28 (9)	N108—S101—O114	107.45 (11)
O2—S1—O14	118.64 (11)	O103—S101—O102	109.99 (10)
O3—S1—O14	105.53 (11)	N108—S101—O102	112.66 (10)
N8—S1—O14	108.31 (10)	O114—S101—O102	119.62 (12)
S1—O3—C4	120.62 (14)	S101—O103—C104	119.29 (14)
O3—C4—C5	112.78 (19)	O103—C104—C105	112.71 (18)
O3—C4—H41	105.9	O103—C104—H1041	104.8
C5—C4—H41	109.3	C105—C104—H1041	109.5
O3—C4—H42	108.3	O103—C104—H1042	108.2
C5—C4—H42	109.3	C105—C104—H1042	110.3
H41—C4—H42	111.3	H1041—C104—H1042	111.3
C4—C5—C6	114.16 (19)	C104—C105—C106	115.00 (18)
C4—C5—H52	105.7	C104—C105—H1052	107.0
C6—C5—H52	107.8	C106—C105—H1052	107.1
C4—C5—H51	108.5	C104—C105—H1051	107.5
C6—C5—H51	109.6	C106—C105—H1051	109.4
H52—C5—H51	111.1	H1052—C105—H1051	110.8
C5—C6—C7	117.2 (2)	C105—C106—C107	118.06 (19)
C5—C6—C10	119.81 (18)	C105—C106—C110	119.92 (18)
C7—C6—C10	123.01 (19)	C107—C106—C110	121.99 (19)
C6—C7—N8	135.4 (2)	C106—C107—N108	137.1 (2)
C6—C7—C9	158.4 (2)	C106—C107—C109	156.5 (2)
N8—C7—C9	64.49 (15)	N108—C107—C109	64.17 (15)
C7—N8—S1	113.52 (14)	C107—N108—S101	113.62 (14)
C7—N8—C9	57.53 (13)	C107—N108—C109	57.94 (13)
S1—N8—C9	117.21 (14)	S101—N108—C109	118.68 (15)
N8—C9—C7	57.98 (13)	N108—C109—C107	57.89 (13)
N8—C9—H92	118.6	N108—C109—H1092	119.1
C7—C9—H92	118.5	C107—C109—H1092	119.8
N8—C9—H91	114.9	N108—C109—H1091	114.9
C7—C9—H91	121.0	C107—C109—H1091	122.2
H92—C9—H91	114.3	H1092—C109—H1091	112.3
C6—C10—C11	111.09 (18)	C106—C110—C113	108.76 (17)
C6—C10—C12	108.48 (18)	C106—C110—C111	111.08 (18)
C11—C10—C12	108.6 (2)	C113—C110—C111	108.86 (18)
C6—C10—C13	110.01 (19)	C106—C110—C112	110.47 (18)
C11—C10—C13	108.9 (2)	C113—C110—C112	108.97 (19)
C12—C10—C13	109.8 (2)	C111—C110—C112	108.66 (19)
C10—C11—H111	107.8	C110—C113—H1131	110.4
C10—C11—H112	109.5	C110—C113—H1132	110.1
H111—C11—H112	111.3	H1131—C113—H1132	107.9
C10—C11—H113	108.5	C110—C113—H1133	111.2
H111—C11—H113	109.5	H1131—C113—H1133	108.5
H112—C11—H113	110.2	H1132—C113—H1133	108.7
C10—C12—H122	106.9	C110—C111—H1112	109.2
C10—C12—H121	109.6	C110—C111—H1111	110.3
H122—C12—H121	109.8	H1112—C111—H1111	109.7
C10—C12—H123	109.7	C110—C111—H1113	110.8
H122—C12—H123	108.9	H1112—C111—H1113	107.7
H121—C12—H123	111.9	H1111—C111—H1113	109.1
C10—C13—H132	107.8	C110—C112—H1122	108.8
C10—C13—H131	109.4	C110—C112—H1121	111.0
H132—C13—H131	110.2	H1122—C112—H1121	109.6
C10—C13—H133	108.7	C110—C112—H1123	109.6
H132—C13—H133	109.7	H1122—C112—H1123	108.4
H131—C13—H133	111.0	H1121—C112—H1123	109.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H92···O2^i	0.98	2.43	3.294 (4)	147
C9—H91···O103	0.98	2.57	3.203 (4)	122
C109—H1092···O102^ii	0.97	2.54	3.473 (4)	162
C109—H1091···O14^iii	0.97	2.49	3.433 (4)	165

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