Two thia­zolino­[2,3-a]­iso­quinolinone S-oxides

The structures of two racemic thia­zolino­[2,3-a]­isoquinolinone S-oxides, i.e. 8,9-di­methoxy-2,3,5,6-tetra­hydro-10bH-thia­zolo­[2,3-a]­isoquinolin-3-one 1-oxide [C₁₃H₁₅NO₄S, (IIa)] and 8,9-di­methoxy-10b-methyl-2,3,5,6-tetra­hydro-10bH-thia­zolo­[2,3-a]­isoquinolin-3-one 1-oxide [C₁₄H₁₇NO₄S, (IIb)], are described. The thia­zolinone ring in (IIa) exists in an envelope conformation, while in (IIb), it assumes a half-chair conformation. In (IIa) and (IIb), the six-membered heterocyclic ring adopts an envelope conformation. The O atom at sulfur is oriented in a pseudo-axial position, whereas the H atom in (IIa) and the methyl group in (IIb), linked to the stereogenic C centre, occupy a bisectional position with respect to the partially saturated pyridine ring and a pseudo-axial position with respect to the thia­zolinone ring. In both structures, the S=O group and the substituent at the stereogenic C centre are trans with respect to one another. Intermolecular C—H...O hydrogen bonds are observed in the crystal lattice of (IIa) and (IIb).

S1. Comment

Our studies of the sulfur-mediated synthesis of isoquinoline alkaloids (Brózda, 1994; Chrzanowska et al., 1998) have stimulated our interest in partially reduced thiazolo[2,3-a]isoquinoline-type heterocycles. We anticipated that the corresponding S-oxides with stereogenic sulfur may be attractive for the preparation of chiral non-racemic alkaloids. It turned out, however, that no systematic investigation has been carried out in this area. Thus, we have undertaken studies to learn more about this type of compound (Rozwadowska & Sulima, 2001). The relative configuration between the substituents at the C-10b and S-1 stereogenic centres was one of the most important problems to be solved. In order to solve the problem, the X-ray crystal structure analyses of two racemic thiazolino[2,3-a]isoquinolinone S-oxides, namely 8,9-dimethoxy-2,3,5,6-tetrahydro-10bH-thiazolo[2,3-a]isoquinolin-3-one 1-oxide, (IIa), and 8,9-dimethoxy-10b-methyl-2,3,5,6-tetrahydro-10bH-thiazolo[2,3-a]isoquinolin- 3-one 1-oxide, (IIb), have been carried out.

The molecular structures of compounds (IIa) and (IIb) and the atom-labeling schemes are illustrated in Figs. 1 and 2, respectively. In both structures, the O atom at S1 is in a pseudo-axial position [the angles to the Cremer & Pople thiazolinone plane normals are 3.21 (11) and 3.56 (8)° for (IIa) and (IIb), respectively]. The H atom in (IIa) and the methyl group in (IIb) at C10b occupy a bisectional position with respect to the partialy saturated pyridine ring [at 30.05 (7) and 37.66 (9)°, respectively] and a pseudo-axial position with respect to the five-membered thiazolinone ring [at 9.38 (8) and 7.24 (10)°, respectively]. The S1═O1 bond is trans with respect to C10b—H10b in (IIa) and C10b—C13 in (IIb) [the torsion angle H10b—C10b—S1—O1 is 170° in (IIa) and C13—C10b—S1—O1 is 170.36 (11)° in (IIb)].

Both methoxy groups on the fused aromatic ring in (IIa) are coplanar with the ring, whereas those in (IIb) are rotated by 12.65 (18) (C8—OCH₃) and 12.00 (7)° (C9—OCH₃) out of the plane of the ring.

The five-membered thiazolinone ring has an envelope conformation in (IIa) [Cremer & Pople (1975) puckering parameters: Q = 0.415 (2) Å and Φ = 358.2 (3)°], with the S atom 0.730 (3) Å out of the plane defined by the remaining four atoms. For (IIb), the thiazolinone ring is found to be in a half-chair conformation twisted on S1—C10b [Cremer & Pople (1975) puckering parameters: Q = 0.421 (1) Å and Φ = 350.6 (2)°]. In both compounds, the partially hydrogenated pyridine moiety shows an envelope conformation [Cremer & Pople (1975) puckering parameters: for (IIa), Q = 0.437 (3) Å, Θ = 51.3 (3)° and Φ = 56.4 (4)°; for (IIb), Q = 0.451 (2) Å, Θ = 52.6 (3)° and Φ = 60.0 (3)°].

The dihedral angles between the best-fit planes of the central ring of the tricyclic skeleton and the outer six- and five-membered rings are 8.24 (14) and 36.82 (9)° in (IIa), and 10.01 (7) and 41.05 (7)° in (IIb). The angles between the outer rings are 37.12 (10) and 41.37 (7)° in (IIa) and (IIb), respectively.

The bond lengths and angles in the partially reduced dimethoxyisoquinoline core of both compounds are similar to those observed in other structures (Pavkovic et al., 1981; Chrzanowska et al., 1987; Lee et al., 1997; Warrener et al., 1998; Maurin et al., 1996; CSD, version 5.20, Allen et al., 1993). In the five-membered thiazolinone rings, the C3—N4 bond distances [1.342 (3) and 1.349 (2) Å in (IIa) and (IIb), respectively] are typical of a tertiary amide distance [1.346 (5) Å; Allen et al., 1987]. The S1—O1 distances are similar [1.4836 (18) Å in (IIa) and 1.4817 (13) Å in (IIb)] and somewhat shorter than the C—S(═ O)—C double bond [1.497 (1) Å; Allen et al., 1987].

Apart from normal van der Waals interactions, the molecular packing in the solid state in both compounds is stabilized by possible C—H···O non-classical intermolecular hydrogen bonds (Tables 1 and 2).

Examination of the structures of (IIa) and (IIb) with PLATON (Spek, 1998) showed that there were no solvent-accessible voids in the crystal lattices.

Related literature

For related literature, see: Allen & Kennard (1993); Allen et al. (1987); Brózda (1994); Chrzanowska et al. (1987, 1998); Cremer & Pople (1975); Lee et al. (1997); Maurin et al. (1996); Pavkovic et al. (1981); Rozwadowska & Sulima (2001); Warrener et al. (1998).

S2. Experimental

Compounds (IIa) and (IIb) were prepared from the corresponding thiazolino[2,3-a]isoquinolinones, (Ia) and (Ib), by oxidation with hydrogen peroxide in methanol/water (1:1) solution (see Scheme). Sulfoxides (IIa) and (IIb) were isolated as single diastereomers in yields of 42 and 44%, respectively.

S3. Refinement

In both compounds, all H atoms were located in difference Fourier maps and refined with a riding model (C—H = 0.93–0.97 Å), and with U_iso constrained to be 1.2 (1.5 for methyl groups) times U_eq of the parent atom. The methyl-H atoms were refined as rigid groups, which were allowed to rotate.

Computing details

For both compounds, data collection: KM-4 Software (Kuma, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS7 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (IIa) showing the atomic labeling scheme. Non-H atoms are drawn as 30% probability displacement ellipsoids and H atoms are shown as spheres of an arbitrary size.
	Fig. 2. The molecular structure of (IIb) showing the atomic labeling scheme. Non-H atoms are drawn as 30% probability displacement ellipsoids and H atoms are shown as spheres of an arbitrary size.

(IIa) 8,9-Dimethoxy-6,10b-dihydro-1-oxo-5H-thiazolo[2,3-a]isoquinolin-3-one

Crystal data

C13H15NO4S	F(000) = 592
Mr = 281.32	Dx = 1.388 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 19.967 (2) Å	Cell parameters from 49 reflections
b = 7.5484 (9) Å	θ = 14.3–27.8°
c = 9.1666 (13) Å	µ = 2.24 mm^−1
β = 102.967 (11)°	T = 293 K
V = 1346.3 (3) Å^3	Plate, colourless
Z = 4	0.50 × 0.33 × 0.22 mm

Data collection

Kuma KM-4 diffractometer	2119 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 70.2°, θmin = 2.3°
ω/2θ scans	h = −24→23
Absorption correction: psi-scan (North et al., 1968)	k = −9→0
Tmin = 0.455, Tmax = 0.611	l = 0→11
2735 measured reflections	2 standard reflections every 100 reflections
2556 independent reflections	intensity decay: 3.5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.112P)^2 + 0.441P] where P = (Fo^2 + 2Fc^2)/3
2556 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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
S1	0.13739 (3)	0.30932 (7)	0.08402 (6)	0.0381 (2)
C2	0.04978 (12)	0.2658 (3)	−0.0144 (3)	0.0394 (5)
H2A	0.0199	0.2591	0.0556	0.047*
H2B	0.0333	0.3595	−0.0859	0.047*
C3	0.05037 (11)	0.0913 (3)	−0.0942 (2)	0.0372 (5)
N4	0.10504 (10)	−0.0061 (2)	−0.0283 (2)	0.0382 (4)
C5	0.12147 (14)	−0.1796 (3)	−0.0795 (3)	0.0486 (6)
H5A	0.0893	−0.2090	−0.1725	0.058*
H5B	0.1174	−0.2685	−0.0056	0.058*
C6	0.19420 (14)	−0.1792 (3)	−0.1039 (3)	0.0483 (6)
H6A	0.2074	−0.2995	−0.1221	0.058*
H6B	0.1956	−0.1091	−0.1918	0.058*
C6A	0.24505 (12)	−0.1045 (3)	0.0293 (2)	0.0389 (5)
C7	0.31396 (13)	−0.1563 (3)	0.0586 (3)	0.0464 (6)
H7A	0.3281	−0.2366	−0.0053	0.056*
C8	0.36166 (12)	−0.0910 (3)	0.1801 (3)	0.0449 (6)
C9	0.33926 (12)	0.0297 (3)	0.2768 (2)	0.0400 (5)
C10	0.27133 (12)	0.0793 (3)	0.2498 (2)	0.0371 (5)
H10	0.2569	0.1576	0.3149	0.044*
C10A	0.22341 (11)	0.0135 (3)	0.1255 (2)	0.0336 (5)
C10B	0.14946 (11)	0.0668 (3)	0.1052 (2)	0.0337 (5)
H10B	0.1329	0.0278	0.1928	0.040*
O1	0.17430 (10)	0.3703 (3)	−0.0304 (2)	0.0565 (5)
O2	0.00588 (9)	0.0465 (2)	−0.20395 (19)	0.0504 (5)
O3	0.42959 (10)	−0.1315 (3)	0.2172 (2)	0.0677 (6)
C11	0.4545 (2)	−0.2540 (9)	0.1233 (6)	0.129 (2)
H11A	0.4304	−0.3644	0.1213	0.193*
H11B	0.5028	−0.2732	0.1617	0.193*
H11C	0.4470	−0.2069	0.0236	0.193*
O4	0.38964 (9)	0.0877 (3)	0.3936 (2)	0.0575 (5)
C12	0.3690 (2)	0.2088 (7)	0.4925 (5)	0.1003 (17)
H12A	0.3535	0.3165	0.4399	0.150*
H12B	0.4073	0.2341	0.5741	0.150*
H12C	0.3323	0.1582	0.5308	0.150*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0407 (4)	0.0315 (3)	0.0431 (4)	0.0005 (2)	0.0117 (2)	−0.0041 (2)
C2	0.0381 (12)	0.0405 (12)	0.0402 (11)	0.0060 (9)	0.0100 (9)	−0.0004 (9)
C3	0.0380 (11)	0.0369 (11)	0.0368 (11)	−0.0005 (9)	0.0087 (9)	0.0021 (9)
N4	0.0409 (10)	0.0321 (9)	0.0392 (9)	−0.0004 (8)	0.0040 (8)	−0.0046 (8)
C5	0.0504 (14)	0.0324 (12)	0.0573 (15)	0.0015 (10)	0.0000 (11)	−0.0104 (10)
C6	0.0509 (14)	0.0438 (14)	0.0463 (13)	0.0065 (11)	0.0027 (11)	−0.0154 (10)
C6A	0.0449 (12)	0.0338 (11)	0.0374 (11)	0.0017 (9)	0.0083 (9)	−0.0033 (9)
C7	0.0470 (13)	0.0444 (13)	0.0488 (13)	0.0061 (10)	0.0133 (10)	−0.0104 (11)
C8	0.0387 (12)	0.0465 (13)	0.0496 (13)	0.0039 (10)	0.0103 (10)	−0.0038 (11)
C9	0.0384 (12)	0.0421 (12)	0.0384 (11)	−0.0025 (9)	0.0065 (9)	−0.0028 (9)
C10	0.0400 (12)	0.0371 (11)	0.0358 (11)	−0.0031 (9)	0.0122 (9)	−0.0047 (9)
C10A	0.0379 (11)	0.0311 (10)	0.0329 (10)	−0.0008 (8)	0.0100 (8)	0.0020 (8)
C10B	0.0385 (11)	0.0322 (11)	0.0310 (10)	−0.0017 (8)	0.0088 (8)	0.0000 (8)
O1	0.0575 (11)	0.0463 (10)	0.0726 (12)	−0.0016 (8)	0.0289 (9)	0.0140 (9)
O2	0.0477 (10)	0.0510 (11)	0.0460 (9)	−0.0002 (8)	−0.0031 (8)	−0.0046 (8)
O3	0.0409 (10)	0.0851 (15)	0.0736 (13)	0.0146 (10)	0.0055 (9)	−0.0263 (12)
C11	0.064 (2)	0.184 (5)	0.128 (4)	0.057 (3)	0.000 (2)	−0.075 (4)
O4	0.0392 (9)	0.0722 (13)	0.0569 (11)	0.0009 (8)	0.0020 (8)	−0.0225 (10)
C12	0.067 (2)	0.129 (4)	0.091 (3)	0.019 (2)	−0.0104 (19)	−0.070 (3)

Geometric parameters (Å, º)

S1—O1	1.4836 (18)	C7—C8	1.384 (3)
S1—C2	1.809 (2)	C7—H7A	0.9300
S1—C10B	1.851 (2)	C8—O3	1.357 (3)
C2—C3	1.508 (3)	C8—C9	1.412 (3)
C2—H2A	0.9700	C9—O4	1.366 (3)
C2—H2B	0.9700	C9—C10	1.375 (3)
C3—O2	1.231 (3)	C10—C10A	1.405 (3)
C3—N4	1.342 (3)	C10—H10	0.9300
N4—C10B	1.449 (3)	C10A—C10B	1.501 (3)
N4—C5	1.454 (3)	C10B—H10B	0.9800
C5—C6	1.518 (4)	O3—C11	1.427 (4)
C5—H5A	0.9700	C11—H11A	0.9600
C5—H5B	0.9700	C11—H11B	0.9600
C6—C6A	1.511 (3)	C11—H11C	0.9600
C6—H6A	0.9700	O4—C12	1.413 (4)
C6—H6B	0.9700	C12—H12A	0.9600
C6A—C10A	1.389 (3)	C12—H12B	0.9600
C6A—C7	1.397 (3)	C12—H12C	0.9600
O1—S1—C2	106.37 (11)	O3—C8—C7	126.2 (2)
O1—S1—C10B	107.90 (10)	O3—C8—C9	115.3 (2)
C2—S1—C10B	87.79 (11)	C7—C8—C9	118.5 (2)
C3—C2—S1	106.77 (15)	O4—C9—C10	125.2 (2)
C3—C2—H2A	110.4	O4—C9—C8	114.7 (2)
S1—C2—H2A	110.4	C10—C9—C8	120.1 (2)
C3—C2—H2B	110.4	C9—C10—C10A	120.9 (2)
S1—C2—H2B	110.4	C9—C10—H10	119.5
H2A—C2—H2B	108.6	C10A—C10—H10	119.5
O2—C3—N4	125.6 (2)	C6A—C10A—C10	119.3 (2)
O2—C3—C2	123.6 (2)	C6A—C10A—C10B	122.1 (2)
N4—C3—C2	110.75 (19)	C10—C10A—C10B	118.54 (19)
C3—N4—C10B	117.02 (18)	N4—C10B—C10A	113.67 (17)
C3—N4—C5	124.59 (19)	N4—C10B—S1	104.24 (14)
C10B—N4—C5	118.37 (18)	C10A—C10B—S1	112.28 (15)
N4—C5—C6	109.8 (2)	N4—C10B—H10B	108.8
N4—C5—H5A	109.7	C10A—C10B—H10B	108.8
C6—C5—H5A	109.7	S1—C10B—H10B	108.8
N4—C5—H5B	109.7	C8—O3—C11	117.3 (2)
C6—C5—H5B	109.7	O3—C11—H11A	109.5
H5A—C5—H5B	108.2	O3—C11—H11B	109.5
C6A—C6—C5	111.9 (2)	H11A—C11—H11B	109.5
C6A—C6—H6A	109.2	O3—C11—H11C	109.5
C5—C6—H6A	109.2	H11A—C11—H11C	109.5
C6A—C6—H6B	109.2	H11B—C11—H11C	109.5
C5—C6—H6B	109.2	C9—O4—C12	116.2 (2)
H6A—C6—H6B	107.9	O4—C12—H12A	109.5
C10A—C6A—C7	119.4 (2)	O4—C12—H12B	109.5
C10A—C6A—C6	120.2 (2)	H12A—C12—H12B	109.5
C7—C6A—C6	120.3 (2)	O4—C12—H12C	109.5
C8—C7—C6A	121.7 (2)	H12A—C12—H12C	109.5
C8—C7—H7A	119.2	H12B—C12—H12C	109.5
C6A—C7—H7A	119.2
O1—S1—C2—C3	76.65 (17)	C7—C6A—C10A—C10	0.3 (3)
C10B—S1—C2—C3	−31.37 (16)	C6—C6A—C10A—C10	179.1 (2)
S1—C2—C3—O2	−157.67 (19)	C7—C6A—C10A—C10B	−176.6 (2)
S1—C2—C3—N4	22.9 (2)	C6—C6A—C10A—C10B	2.1 (3)
O2—C3—N4—C10B	−176.6 (2)	C9—C10—C10A—C6A	0.5 (3)
C2—C3—N4—C10B	2.8 (3)	C9—C10—C10A—C10B	177.6 (2)
O2—C3—N4—C5	1.9 (4)	C3—N4—C10B—C10A	−148.8 (2)
C2—C3—N4—C5	−178.7 (2)	C5—N4—C10B—C10A	32.6 (3)
C3—N4—C5—C6	125.4 (2)	C3—N4—C10B—S1	−26.3 (2)
C10B—N4—C5—C6	−56.1 (3)	C5—N4—C10B—S1	155.14 (18)
N4—C5—C6—C6A	49.7 (3)	C6A—C10A—C10B—N4	−4.2 (3)
C5—C6—C6A—C10A	−25.3 (3)	C10—C10A—C10B—N4	178.81 (18)
C5—C6—C6A—C7	153.4 (2)	C6A—C10A—C10B—S1	−122.2 (2)
C10A—C6A—C7—C8	−0.9 (4)	C10—C10A—C10B—S1	60.8 (2)
C6—C6A—C7—C8	−179.6 (2)	O1—S1—C10B—N4	−74.42 (16)
C6A—C7—C8—O3	−179.3 (3)	C2—S1—C10B—N4	32.08 (14)
C6A—C7—C8—C9	0.5 (4)	O1—S1—C10B—C10A	49.07 (17)
O3—C8—C9—O4	0.0 (3)	C2—S1—C10B—C10A	155.56 (16)
C7—C8—C9—O4	−179.9 (2)	C7—C8—O3—C11	−0.6 (6)
O3—C8—C9—C10	−179.8 (2)	C9—C8—O3—C11	179.6 (4)
C7—C8—C9—C10	0.4 (4)	C10—C9—O4—C12	−0.3 (5)
O4—C9—C10—C10A	179.4 (2)	C8—C9—O4—C12	179.9 (3)
C8—C9—C10—C10A	−0.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O2^i	0.97	2.37	3.332 (3)	169
C10—H10···O1^ii	0.93	2.41	3.116 (3)	132
C11—H11B···O4^iii	0.96	2.54	3.370 (4)	144

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

(IIb) 8,9-Dimethoxy-10b-methyl-1-oxo-6,10b-dihydro-5H- thiazolo[2,3-a]isoquinolin-3-one

Crystal data

C14H17NO4S	Dx = 1.411 Mg m^−3
Mr = 295.35	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 47 reflections
a = 15.9407 (15) Å	θ = 15.0–29.9°
b = 9.1737 (10) Å	µ = 2.20 mm^−1
c = 19.015 (2) Å	T = 293 K
V = 2780.7 (5) Å^3	Prism, colourless
Z = 8	0.33 × 0.31 × 0.20 mm
F(000) = 1248

Data collection

Kuma KM-4 diffractometer	2252 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 70.1°, θmin = 4.7°
ω/2θ scans	h = 0→19
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
Tmin = 0.509, Tmax = 0.645	l = −23→0
2643 measured reflections	2 standard reflections every 100 reflections
2643 independent reflections	intensity decay: 7.1%

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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 0.9585P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2643 reflections	Δρmax = 0.20 e Å^−3
185 parameters	Δρmin = −0.23 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: 0.00190 (15)

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
S1	0.25137 (3)	0.12856 (4)	0.44033 (2)	0.04041 (15)
C2	0.27792 (12)	0.0366 (2)	0.52145 (9)	0.0490 (4)
H2A	0.2967	0.1066	0.5563	0.059*
H2B	0.2293	−0.0141	0.5399	0.059*
C3	0.34702 (11)	−0.07046 (18)	0.50522 (8)	0.0425 (4)
N4	0.38423 (9)	−0.03797 (15)	0.44348 (7)	0.0405 (3)
C5	0.44589 (12)	−0.1309 (2)	0.40989 (10)	0.0498 (4)
H5A	0.4518	−0.2211	0.4361	0.060*
H5B	0.4999	−0.0824	0.4088	0.060*
C6	0.41712 (12)	−0.16321 (19)	0.33598 (10)	0.0484 (4)
H6A	0.3684	−0.2264	0.3375	0.058*
H6B	0.4613	−0.2139	0.3108	0.058*
C6A	0.39521 (10)	−0.02449 (17)	0.29758 (9)	0.0392 (4)
C7	0.40452 (11)	−0.01801 (18)	0.22430 (9)	0.0424 (4)
H7	0.4229	−0.1002	0.2002	0.051*
C8	0.38709 (11)	0.10700 (17)	0.18743 (8)	0.0389 (4)
C9	0.35971 (10)	0.23192 (17)	0.22336 (8)	0.0383 (4)
C10	0.35043 (10)	0.22667 (17)	0.29556 (8)	0.0387 (4)
H10	0.3320	0.3089	0.3197	0.046*
C10A	0.36851 (10)	0.09837 (17)	0.33281 (8)	0.0366 (4)
C10B	0.36221 (10)	0.10128 (16)	0.41171 (8)	0.0355 (3)
O1	0.19727 (8)	0.02683 (15)	0.40025 (7)	0.0543 (3)
O2	0.36523 (9)	−0.17314 (15)	0.54328 (7)	0.0576 (4)
O3	0.39587 (8)	0.12164 (12)	0.11634 (6)	0.0466 (3)
C11	0.44023 (15)	0.0080 (2)	0.08183 (10)	0.0596 (5)
H11A	0.4950	−0.0018	0.1024	0.089*
H11B	0.4457	0.0309	0.0328	0.089*
H11C	0.4100	−0.0819	0.0870	0.089*
O4	0.34611 (9)	0.35200 (13)	0.18269 (6)	0.0505 (3)
C12	0.33515 (15)	0.48769 (19)	0.21733 (10)	0.0584 (5)
H12A	0.2855	0.4841	0.2458	0.088*
H12B	0.3297	0.5638	0.1830	0.088*
H12C	0.3829	0.5070	0.2466	0.088*
C13	0.41274 (12)	0.2247 (2)	0.44441 (9)	0.0481 (4)
H13A	0.4057	0.2232	0.4945	0.072*
H13B	0.3934	0.3163	0.4262	0.072*
H13C	0.4710	0.2124	0.4331	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0427 (2)	0.0409 (3)	0.0376 (2)	0.00452 (17)	0.00164 (16)	0.00195 (16)
C2	0.0569 (10)	0.0526 (11)	0.0375 (8)	0.0017 (8)	0.0029 (8)	0.0041 (8)
C3	0.0529 (9)	0.0384 (8)	0.0362 (8)	−0.0039 (7)	−0.0076 (7)	0.0024 (7)
N4	0.0484 (8)	0.0352 (7)	0.0379 (7)	0.0050 (6)	−0.0008 (6)	0.0047 (6)
C5	0.0541 (10)	0.0458 (10)	0.0495 (10)	0.0157 (8)	−0.0005 (8)	0.0081 (8)
C6	0.0615 (11)	0.0364 (9)	0.0474 (10)	0.0130 (8)	0.0063 (8)	0.0048 (7)
C6A	0.0426 (8)	0.0335 (8)	0.0415 (8)	0.0037 (7)	0.0024 (7)	0.0050 (7)
C7	0.0520 (9)	0.0347 (8)	0.0405 (8)	0.0054 (7)	0.0078 (7)	−0.0037 (7)
C8	0.0445 (8)	0.0385 (8)	0.0336 (8)	0.0012 (7)	0.0039 (6)	0.0012 (6)
C9	0.0447 (8)	0.0335 (8)	0.0366 (8)	0.0041 (7)	0.0018 (6)	0.0026 (6)
C10	0.0465 (9)	0.0330 (8)	0.0367 (8)	0.0057 (7)	0.0036 (7)	0.0000 (6)
C10A	0.0380 (8)	0.0364 (8)	0.0355 (8)	0.0021 (6)	0.0007 (6)	0.0031 (6)
C10B	0.0392 (8)	0.0315 (8)	0.0359 (8)	0.0018 (6)	−0.0016 (6)	0.0023 (6)
O1	0.0487 (7)	0.0589 (8)	0.0554 (7)	−0.0098 (6)	−0.0085 (6)	0.0051 (6)
O2	0.0729 (9)	0.0512 (7)	0.0488 (7)	0.0016 (7)	−0.0076 (6)	0.0174 (6)
O3	0.0655 (8)	0.0411 (6)	0.0332 (6)	0.0104 (6)	0.0087 (5)	0.0005 (5)
C11	0.0849 (14)	0.0506 (11)	0.0434 (10)	0.0167 (10)	0.0151 (9)	−0.0049 (9)
O4	0.0808 (9)	0.0349 (6)	0.0360 (6)	0.0125 (6)	0.0041 (6)	0.0061 (5)
C12	0.0902 (15)	0.0355 (9)	0.0495 (10)	0.0145 (10)	0.0054 (10)	0.0024 (8)
C13	0.0559 (10)	0.0418 (10)	0.0465 (9)	−0.0076 (8)	−0.0104 (8)	0.0025 (7)

Geometric parameters (Å, º)

S1—O1	1.4817 (13)	C8—O3	1.3656 (19)
S1—C2	1.8083 (18)	C8—C9	1.404 (2)
S1—C10B	1.8656 (16)	C9—O4	1.3632 (19)
C2—C3	1.508 (3)	C9—C10	1.382 (2)
C2—H2A	0.9700	C10—C10A	1.404 (2)
C2—H2B	0.9700	C10—H10	0.9300
C3—O2	1.223 (2)	C10A—C10B	1.504 (2)
C3—N4	1.349 (2)	C10B—C13	1.522 (2)
N4—C5	1.450 (2)	O3—C11	1.420 (2)
N4—C10B	1.4560 (19)	C11—H11A	0.9600
C5—C6	1.508 (3)	C11—H11B	0.9600
C5—H5A	0.9700	C11—H11C	0.9600
C5—H5B	0.9700	O4—C12	1.419 (2)
C6—C6A	1.508 (2)	C12—H12A	0.9600
C6—H6A	0.9700	C12—H12B	0.9600
C6—H6B	0.9700	C12—H12C	0.9600
C6A—C10A	1.379 (2)	C13—H13A	0.9600
C6A—C7	1.403 (2)	C13—H13B	0.9600
C7—C8	1.373 (2)	C13—H13C	0.9600
C7—H7	0.9300
O1—S1—C2	106.33 (8)	O4—C9—C10	125.08 (14)
O1—S1—C10B	108.47 (7)	O4—C9—C8	115.66 (14)
C2—S1—C10B	87.97 (8)	C10—C9—C8	119.23 (14)
C3—C2—S1	107.47 (12)	C9—C10—C10A	120.58 (15)
C3—C2—H2A	110.2	C9—C10—H10	119.7
S1—C2—H2A	110.2	C10A—C10—H10	119.7
C3—C2—H2B	110.2	C6A—C10A—C10	120.24 (15)
S1—C2—H2B	110.2	C6A—C10A—C10B	121.33 (14)
H2A—C2—H2B	108.5	C10—C10A—C10B	118.35 (14)
O2—C3—N4	125.52 (17)	N4—C10B—C10A	112.47 (13)
O2—C3—C2	123.65 (16)	N4—C10B—C13	110.83 (13)
N4—C3—C2	110.83 (14)	C10A—C10B—C13	112.66 (14)
C3—N4—C5	123.49 (14)	N4—C10B—S1	103.00 (10)
C3—N4—C10B	116.68 (14)	C10A—C10B—S1	110.89 (11)
C5—N4—C10B	119.78 (13)	C13—C10B—S1	106.40 (11)
N4—C5—C6	108.67 (14)	C8—O3—C11	115.86 (13)
N4—C5—H5A	110.0	O3—C11—H11A	109.5
C6—C5—H5A	110.0	O3—C11—H11B	109.5
N4—C5—H5B	110.0	H11A—C11—H11B	109.5
C6—C5—H5B	110.0	O3—C11—H11C	109.5
H5A—C5—H5B	108.3	H11A—C11—H11C	109.5
C5—C6—C6A	110.85 (15)	H11B—C11—H11C	109.5
C5—C6—H6A	109.5	C9—O4—C12	117.72 (13)
C6A—C6—H6A	109.5	O4—C12—H12A	109.5
C5—C6—H6B	109.5	O4—C12—H12B	109.5
C6A—C6—H6B	109.5	H12A—C12—H12B	109.5
H6A—C6—H6B	108.1	O4—C12—H12C	109.5
C10A—C6A—C7	118.74 (15)	H12A—C12—H12C	109.5
C10A—C6A—C6	121.75 (15)	H12B—C12—H12C	109.5
C7—C6A—C6	119.49 (15)	C10B—C13—H13A	109.5
C8—C7—C6A	121.44 (15)	C10B—C13—H13B	109.5
C8—C7—H7	119.3	H13A—C13—H13B	109.5
C6A—C7—H7	119.3	C10B—C13—H13C	109.5
O3—C8—C7	124.55 (14)	H13A—C13—H13C	109.5
O3—C8—C9	115.68 (14)	H13B—C13—H13C	109.5
C7—C8—C9	119.76 (15)
O1—S1—C2—C3	79.00 (14)	C6—C6A—C10A—C10B	1.7 (2)
C10B—S1—C2—C3	−29.66 (13)	C9—C10—C10A—C6A	−0.5 (2)
S1—C2—C3—O2	−161.58 (15)	C9—C10—C10A—C10B	176.45 (15)
S1—C2—C3—N4	17.68 (18)	C3—N4—C10B—C10A	−151.01 (14)
O2—C3—N4—C5	6.9 (3)	C5—N4—C10B—C10A	31.3 (2)
C2—C3—N4—C5	−172.37 (16)	C3—N4—C10B—C13	81.88 (18)
O2—C3—N4—C10B	−170.73 (16)	C5—N4—C10B—C13	−95.81 (18)
C2—C3—N4—C10B	10.0 (2)	C3—N4—C10B—S1	−31.57 (16)
C3—N4—C5—C6	125.39 (17)	C5—N4—C10B—S1	150.75 (14)
C10B—N4—C5—C6	−57.1 (2)	C6A—C10A—C10B—N4	−2.0 (2)
N4—C5—C6—C6A	51.3 (2)	C10—C10A—C10B—N4	−178.86 (14)
C5—C6—C6A—C10A	−27.2 (2)	C6A—C10A—C10B—C13	124.18 (17)
C5—C6—C6A—C7	150.84 (17)	C10—C10A—C10B—C13	−52.7 (2)
C10A—C6A—C7—C8	−0.5 (3)	C6A—C10A—C10B—S1	−116.69 (15)
C6—C6A—C7—C8	−178.55 (16)	C10—C10A—C10B—S1	66.41 (17)
C6A—C7—C8—O3	179.03 (16)	O1—S1—C10B—N4	−73.00 (11)
C6A—C7—C8—C9	0.3 (3)	C2—S1—C10B—N4	33.54 (11)
O3—C8—C9—O4	−0.5 (2)	O1—S1—C10B—C10A	47.53 (13)
C7—C8—C9—O4	178.29 (16)	C2—S1—C10B—C10A	154.07 (12)
O3—C8—C9—C10	−179.07 (15)	O1—S1—C10B—C13	170.36 (11)
C7—C8—C9—C10	−0.2 (3)	C2—S1—C10B—C13	−83.10 (12)
O4—C9—C10—C10A	−178.06 (16)	C7—C8—O3—C11	−11.9 (3)
C8—C9—C10—C10A	0.3 (2)	C9—C8—O3—C11	166.88 (16)
C7—C6A—C10A—C10	0.5 (2)	C10—C9—O4—C12	11.0 (3)
C6—C6A—C10A—C10	178.57 (16)	C8—C9—O4—C12	−167.44 (17)
C7—C6A—C10A—C10B	−176.30 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O4^i	0.97	2.56	3.410 (2)	147
C10—H10···O1^ii	0.93	2.56	3.482 (2)	170
C11—H11C···O2^iii	0.96	2.50	3.377 (3)	152
C13—H13B···O1^ii	0.96	2.46	3.386 (2)	161

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