Flat versus twisted rotamers of 2,4-­disubstituted thiazoles: the effect of intermolecular hydrogen bonds

In the title compounds, 2-amino-4-(2-chloro-4,5-di­methoxy­phenyl)-1,3-thia­zole, C₁₁H₁₁ClN₂O₂S, (I), and 4-(2-chloro-4,5-di­methoxy­phenyl)-2-methyl-1,3-thia­zole, C₁₂H₁₂ClNO₂S, (II), the dihedral angles between the thia­zole moiety and the chloro­aryl group are 51.61 (10) and 8.44 (14)°, respectively. This difference is a consequence of intermolecular hydrogen bonds forcing the stabilization of a twisted rotamer in (I). Substitution of the amino function by a methyl group precludes these contacts, giving a flat rotamer in (II).

S1. Comment

During the synthesis of a large series of new polysubstituted 2,4-diarylthiazoles (Sánchez-Viesca & Gómez, 1998, and references therein; Sánchez-Viesca & Berros, 1999), we established, on the basis of ¹H NMR data and IR spectroscopy, that these compounds present different rotamers in solution, A and B, depending on the substitution of the thiazole ring (see Scheme). In the case of 2-amino-4-(2-chloro-4,5-dimethoxyphenyl)-1,3-thiazole, (I), the IR spectrum in the solid state (KBr wafer) indicates the presence of intermolecular associations. In CHCl₃ solution, these interactions disappear, as confirmed by IR spectroscopy and by paramagnetic shifts in the ¹H NMR spectrum. In contrast, 4-(2-chloro-4,5-dimethoxyphenyl)-2-methyl-1,3-thiazole, (II), seems to be stabilized as a unique rotamer both in solution and in the solid state, in agreement with the observed paramagnetic shifts in its ¹H NMR spectrum (Sánchez-Viesca & Berros, 1999; Jeffrey, 1997). In order to assess the influence of the group substituting the 2-position of the thiazole ring, the single-crystal X-ray structures of (I) and (II) have been determined, and the results are presented here. \sch

Compounds (I) and (II) display the same core formula, but the 2-position of the thiazole moiety is substituted by an amino group in (I) and a methyl group in (II). Thus, they have the same F(000)/Z ratio, where F(000) corresponds to a pure electron count. No unusual geometric parameters were observed.

In both molecules, the 4-position of the thiazole is substituted by a chloroaryl group. For (I), the dihedral angle between the mean planes formed by the thiazole ring (S1/C2/N3/C4/C5) and the chloroaryl group (C1'-C6') is 51.61 (10)° (Fig. 1). For compound (II), the equivalent dihedral angle is 8.44 (14)°, yielding a molecule which is virtually planar overall (Fig. 2). For the five similar 2,4-disubstitued thiazoles previously reported, this angle is in the range 6.2–58.8°. However, bite dihedral angles have been observed for 2-amino thiazoles: 6.2° for 2-amino-4-phenylthiazole (Au-Alvarez et al., 1999) and 19.2° for the corresponding hydrobromide monohydrate complex (Form et al., 1974). Substantially larger dihedral angles are observed if the 2-position is substituted by a bulky secondary or tertiary amine (Jain et al., 2000; Maurin et al., 1999; Kutschabsky et al., 1990). For the five examples mentioned above, a phenyl, dimethylphenyl or chlorophenyl group occupies the 4-position of the thiazole, and these probably do not significantly participate in the definition of the dihedral angle.

The present X-ray study unambiguously determines that compounds (I) and (II) are stabilized in the solid state as rotamers A (Scheme). However, it is not possible to invoke steric hindrance in order to explain the very different dihedral angles observed. Rather, this difference is a consequence of the intermolecular hydrogen-bonding schemes in (I) and (II).

In the case of (I), the NH₂ group is able to form hydrogen bonds with the methoxy moieties of a symmetry-related molecule, as well as with the N atom of the thiazole ring of another molecule, this contact being virtually linear (Table 1). These contacts generate infinite chains along the [110] axis (Fig. 3) and seem to force the molecule to adopt a twisted conformation, with the thiazole-chloroaryl dihedral angle far from 0°. This arrangement also explains the absence of intramolecular hydrogen bonds in (I): considering atoms Cl1 and N3 as potential donors, the observed contacts are C5—H5A···Cl1 and C6'-H6'A···N3, with angles of 99.4 and 93.9°, respectively, i.e. with electrostatic interaction energies approaching zero.

For (II), where the NH₂ group is replaced by a methyl group which is not an efficient donor, the intermolecular hydrogen-bonding scheme is withdrawn, allowing the relaxation of the molecule towards an almost flat rotamer. The only intermolecular contact detected in (II) arises between the two methoxy groups of the chloroaryl moiety (Table 2). Nevertheless, the decrease in the thiazole-chloroaryl dihedral angle is still insufficient for the formation of strong or moderate intramolecular hydrogen bonds: the C5—H5A···Cl1 and C6'-H6'A···N3 contacts display angles of 124.3 and 104.9°, respectively.

In conclusion, we have established that, for the 2,4-disubstituted thiazoles under consideration here, the intermolecular hydrogen bonds determine which rotamer is stabilized in the solid state and a flat rotamer can be obtained by suppressing these intermolecular contacts. In other words, it is possible to tune the level of electronic delocalization between the thiazole and the chloroaryl moieties in the solid state by changing the substituent at the 2-position of the thiazole ring.

S2. Experimental

The new thiazole derivatives (I) and (II) were prepared by known general methods (Sánchez-Viesca & Berros, 1999; Katritzky & Rees, 1984).

S3. Refinement

For both structures, H atoms were placed on idealized positions and refined using a riding model, with free isotropic displacement parameters and fixed distances of N—H = 0.86 Å, aromatic C—H = 0.93 Å and methyl C—H = 0.96 Å (SHELXL97; Sheldrick, 1997).

Computing details

For both compounds, data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I), in a projection normal to the mean plane of the chloroaryl group. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecular structure of (II), in a projection normal to the mean plane of the chloroaryl group. Displacement ellipsoids atoms are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The hydrogen-bond network observed in (I), viewed along the [110] axis of the triclinic cell. For the sake of clarity, H atoms not involved in this network have been omitted.

(I) 2-amino-4-(2-chloro-4,5-dimethoxyphenyl)-1,3-thiazole

Crystal data

C11H11ClN2O2S	Z = 2
Mr = 270.73	F(000) = 280
Triclinic, P1	Dx = 1.467 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2398 (11) Å	Cell parameters from 50 reflections
b = 8.6611 (12) Å	θ = 3.5–11.9°
c = 11.0585 (18) Å	µ = 0.47 mm^−1
α = 107.840 (12)°	T = 293 K
β = 106.719 (13)°	Plate, pale pink
γ = 97.729 (11)°	0.5 × 0.3 × 0.1 mm
V = 613.04 (18) Å^3

Data collection

Siemens P4 diffractometer	1831 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 27.5°, θmin = 2.1°
θ/2θ scans	h = −1→9
Absorption correction: ψ-scan (XSCANS; Siemens, 1991)	k = −10→10
Tmin = 0.929, Tmax = 0.954	l = −14→14
3417 measured reflections	3 standard reflections every 97 reflections
2756 independent reflections	intensity decay: 4.5%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 0.2732P] where P = (Fo^2 + 2Fc^2)/3
2756 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.29 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	0.09030 (13)	0.06850 (10)	0.37593 (8)	0.0433 (2)
C2	0.0576 (4)	0.0218 (3)	0.2053 (3)	0.0352 (6)
N3	0.1366 (3)	0.1458 (3)	0.1776 (2)	0.0336 (5)
C4	0.2268 (4)	0.2874 (3)	0.2951 (3)	0.0325 (6)
C5	0.2158 (4)	0.2687 (4)	0.4089 (3)	0.0401 (7)
H5A	0.2690	0.3528	0.4943	0.049 (9)*
N6	−0.0370 (4)	−0.1329 (3)	0.1120 (3)	0.0508 (7)
H6A	−0.0479	−0.1543	0.0286	0.069 (12)*
H6B	−0.0862	−0.2098	0.1360	0.077 (12)*
Cl1	0.13559 (13)	0.63211 (10)	0.42450 (9)	0.0564 (3)
C1'	0.3283 (4)	0.4390 (3)	0.2831 (3)	0.0331 (6)
C2'	0.2978 (4)	0.5965 (3)	0.3347 (3)	0.0365 (6)
C3'	0.3931 (4)	0.7341 (3)	0.3166 (3)	0.0394 (7)
H3'A	0.3673	0.8381	0.3505	0.046 (9)*
C4'	0.5253 (4)	0.7159 (3)	0.2484 (3)	0.0376 (7)
C5'	0.5658 (4)	0.5597 (3)	0.1989 (3)	0.0350 (6)
C6'	0.4656 (4)	0.4241 (3)	0.2146 (3)	0.0346 (6)
H6'A	0.4894	0.3198	0.1789	0.034 (7)*
O7'	0.6256 (3)	0.8414 (2)	0.2239 (2)	0.0489 (6)
C8'	0.5666 (6)	0.9950 (4)	0.2510 (5)	0.0711 (12)
H8'A	0.6481	1.0723	0.2297	0.098 (14)*
H8'B	0.5820	1.0411	0.3451	0.14 (2)*
H8'C	0.4298	0.9753	0.1964	0.088 (14)*
O9'	0.7022 (3)	0.5550 (2)	0.1350 (2)	0.0446 (5)
C10'	0.7624 (5)	0.4029 (4)	0.0938 (4)	0.0534 (9)
H10A	0.8576	0.4161	0.0505	0.083 (12)*
H10B	0.6485	0.3145	0.0314	0.061 (10)*
H10C	0.8214	0.3757	0.1718	0.053 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0524 (5)	0.0434 (4)	0.0397 (4)	0.0067 (4)	0.0222 (4)	0.0189 (3)
C2	0.0363 (16)	0.0331 (15)	0.0387 (15)	0.0054 (12)	0.0181 (13)	0.0129 (12)
N3	0.0379 (13)	0.0297 (12)	0.0339 (12)	0.0041 (10)	0.0157 (11)	0.0113 (10)
C4	0.0306 (15)	0.0316 (14)	0.0335 (14)	0.0068 (11)	0.0129 (12)	0.0082 (11)
C5	0.0428 (17)	0.0386 (16)	0.0322 (14)	0.0010 (13)	0.0107 (13)	0.0100 (12)
N6	0.0698 (19)	0.0330 (14)	0.0437 (15)	−0.0076 (13)	0.0258 (14)	0.0091 (11)
Cl1	0.0604 (6)	0.0458 (5)	0.0697 (6)	0.0141 (4)	0.0424 (5)	0.0110 (4)
C1'	0.0346 (15)	0.0289 (14)	0.0291 (13)	0.0034 (12)	0.0075 (12)	0.0067 (11)
C2'	0.0326 (15)	0.0347 (15)	0.0389 (15)	0.0054 (12)	0.0155 (13)	0.0071 (12)
C3'	0.0371 (16)	0.0286 (15)	0.0476 (17)	0.0079 (12)	0.0143 (14)	0.0077 (12)
C4'	0.0333 (16)	0.0288 (14)	0.0462 (16)	0.0023 (12)	0.0103 (13)	0.0134 (12)
C5'	0.0318 (15)	0.0364 (15)	0.0350 (14)	0.0051 (12)	0.0109 (12)	0.0127 (12)
C6'	0.0393 (16)	0.0265 (14)	0.0374 (15)	0.0073 (12)	0.0145 (13)	0.0101 (11)
O7'	0.0447 (13)	0.0332 (11)	0.0757 (15)	0.0087 (10)	0.0257 (12)	0.0250 (11)
C8'	0.062 (3)	0.0383 (19)	0.128 (4)	0.0170 (18)	0.042 (3)	0.041 (2)
O9'	0.0468 (13)	0.0412 (12)	0.0584 (13)	0.0133 (10)	0.0309 (11)	0.0222 (10)
C10'	0.054 (2)	0.053 (2)	0.063 (2)	0.0211 (18)	0.0336 (19)	0.0181 (18)

Geometric parameters (Å, º)

S1—C5	1.722 (3)	C3'—H3'A	0.9300
S1—C2	1.740 (3)	C4'—O7'	1.365 (3)
C2—N3	1.309 (3)	C4'—C5'	1.400 (4)
C2—N6	1.352 (3)	C5'—O9'	1.368 (3)
N3—C4	1.393 (3)	C5'—C6'	1.379 (4)
C4—C5	1.339 (4)	C6'—H6'A	0.9300
C4—C1'	1.478 (4)	O7'—C8'	1.423 (4)
C5—H5A	0.9300	C8'—H8'A	0.9600
N6—H6A	0.8600	C8'—H8'B	0.9600
N6—H6B	0.8600	C8'—H8'C	0.9600
Cl1—C2'	1.744 (3)	O9'—C10'	1.426 (4)
C1'—C2'	1.382 (4)	C10'—H10A	0.9600
C1'—C6'	1.410 (4)	C10'—H10B	0.9600
C2'—C3'	1.394 (4)	C10'—H10C	0.9600
C3'—C4'	1.376 (4)
C5—S1—C2	88.73 (13)	O7'—C4'—C3'	124.8 (3)
N3—C2—N6	123.9 (3)	O7'—C4'—C5'	115.2 (3)
N3—C2—S1	114.6 (2)	C3'—C4'—C5'	120.0 (3)
N6—C2—S1	121.4 (2)	O9'—C5'—C6'	125.2 (3)
C2—N3—C4	110.3 (2)	O9'—C5'—C4'	115.6 (2)
C5—C4—N3	115.3 (2)	C6'—C5'—C4'	119.2 (3)
C5—C4—C1'	126.9 (2)	C5'—C6'—C1'	122.0 (3)
N3—C4—C1'	117.7 (2)	C5'—C6'—H6'A	119.0
C4—C5—S1	111.0 (2)	C1'—C6'—H6'A	119.0
C4—C5—H5A	124.5	C4'—O7'—C8'	117.7 (3)
S1—C5—H5A	124.5	O7'—C8'—H8'A	109.5
C2—N6—H6A	120.0	O7'—C8'—H8'B	109.5
C2—N6—H6B	120.0	H8'A—C8'—H8'B	109.5
H6A—N6—H6B	120.0	O7'—C8'—H8'C	109.5
C2'—C1'—C6'	117.0 (2)	H8'A—C8'—H8'C	109.5
C2'—C1'—C4	124.4 (3)	H8'B—C8'—H8'C	109.5
C6'—C1'—C4	118.6 (2)	C5'—O9'—C10'	117.8 (2)
C1'—C2'—C3'	121.9 (3)	O9'—C10'—H10A	109.5
C1'—C2'—Cl1	121.5 (2)	O9'—C10'—H10B	109.5
C3'—C2'—Cl1	116.6 (2)	H10A—C10'—H10B	109.5
C4'—C3'—C2'	119.9 (3)	O9'—C10'—H10C	109.5
C4'—C3'—H3'A	120.1	H10A—C10'—H10C	109.5
C2'—C3'—H3'A	120.1	H10B—C10'—H10C	109.5
C5—S1—C2—N3	0.7 (2)	C1'—C2'—C3'—C4'	−1.6 (4)
C5—S1—C2—N6	178.7 (3)	Cl1—C2'—C3'—C4'	179.1 (2)
N6—C2—N3—C4	−178.6 (3)	C2'—C3'—C4'—O7'	179.5 (3)
S1—C2—N3—C4	−0.7 (3)	C2'—C3'—C4'—C5'	−0.8 (4)
C2—N3—C4—C5	0.3 (4)	O7'—C4'—C5'—O9'	1.0 (4)
C2—N3—C4—C1'	178.6 (2)	C3'—C4'—C5'—O9'	−178.7 (2)
N3—C4—C5—S1	0.3 (3)	O7'—C4'—C5'—C6'	−177.6 (2)
C1'—C4—C5—S1	−177.9 (2)	C3'—C4'—C5'—C6'	2.7 (4)
C2—S1—C5—C4	−0.5 (2)	O9'—C5'—C6'—C1'	179.3 (3)
C5—C4—C1'—C2'	−52.2 (4)	C4'—C5'—C6'—C1'	−2.2 (4)
N3—C4—C1'—C2'	129.7 (3)	C2'—C1'—C6'—C5'	−0.1 (4)
C5—C4—C1'—C6'	127.9 (3)	C4—C1'—C6'—C5'	179.8 (3)
N3—C4—C1'—C6'	−50.2 (4)	C3'—C4'—O7'—C8'	−10.6 (5)
C6'—C1'—C2'—C3'	2.0 (4)	C5'—C4'—O7'—C8'	169.6 (3)
C4—C1'—C2'—C3'	−177.9 (3)	C6'—C5'—O9'—C10'	−7.1 (4)
C6'—C1'—C2'—Cl1	−178.7 (2)	C4'—C5'—O9'—C10'	174.4 (3)
C4—C1'—C2'—Cl1	1.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···O7′^i	0.86	2.58	3.051 (3)	116
N6—H6B···O9′^i	0.86	2.37	3.204 (3)	162
N6—H6A···N3^ii	0.86	2.21	3.035 (3)	161
C5—H5A···Cl1	0.93	2.95	3.239 (3)	99
C6′—H6′A···N3	0.93	2.78	2.990 (3)	94

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

(II) 4-(2-chloro-4,5-dimethoxyphenyl)-2-methyl-1,3-thiazole

Crystal data

C12H12ClNO2S	F(000) = 560
Mr = 269.74	Dx = 1.448 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 50 reflections
a = 7.3379 (9) Å	θ = 4.7–11.5°
b = 19.242 (2) Å	µ = 0.47 mm^−1
c = 8.7798 (8) Å	T = 298 K
β = 93.738 (9)°	Irregular, colourless
V = 1237.1 (2) Å^3	0.8 × 0.4 × 0.1 mm
Z = 4

Data collection

Siemens P4 diffractometer	1701 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 25°, θmin = 2.1°
ω scans	h = −1→8
Absorption correction: ψ-scan (XSCANS; Siemens, 1991)	k = −22→1
Tmin = 0.808, Tmax = 0.954	l = −10→10
2900 measured reflections	3 standard reflections every 97 reflections
2183 independent reflections	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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.057P)^2 + 0.4857P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2183 reflections	Δρmax = 0.34 e Å^−3
167 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (2)

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	−0.33053 (11)	0.79532 (4)	1.18312 (10)	0.0722 (3)
C2	−0.3850 (3)	0.87335 (15)	1.0948 (3)	0.0526 (6)
N3	−0.2709 (3)	0.89224 (12)	0.9960 (2)	0.0486 (5)
C4	−0.1305 (3)	0.84458 (12)	0.9857 (3)	0.0429 (6)
C5	−0.1432 (4)	0.78866 (15)	1.0785 (3)	0.0618 (7)
H5A	−0.0611	0.7518	1.0842	0.082 (10)*
C6	−0.5483 (4)	0.91500 (19)	1.1344 (4)	0.0678 (8)
H6A	−0.5559	0.9565	1.0735	0.18 (2)*
H6B	−0.5364	0.9273	1.2405	0.133 (16)*
H6C	−0.6570	0.8879	1.1145	0.17 (2)*
Cl1	0.19874 (10)	0.73913 (4)	0.92000 (9)	0.0662 (3)
C1'	0.0151 (3)	0.86356 (11)	0.8830 (2)	0.0393 (5)
C2'	0.1642 (3)	0.82338 (11)	0.8498 (3)	0.0414 (5)
C3'	0.2980 (3)	0.84732 (12)	0.7575 (3)	0.0418 (5)
H3'A	0.3961	0.8187	0.7381	0.041 (6)*
C4'	0.2870 (3)	0.91243 (12)	0.6950 (2)	0.0398 (5)
C5'	0.1369 (3)	0.95490 (11)	0.7256 (3)	0.0400 (5)
C6'	0.0073 (3)	0.93027 (12)	0.8179 (2)	0.0403 (5)
H6'A	−0.0900	0.9590	0.8381	0.040 (6)*
O7'	0.4090 (2)	0.94076 (9)	0.60307 (19)	0.0507 (5)
C8'	0.5680 (3)	0.90079 (14)	0.5767 (3)	0.0528 (7)
H8'A	0.6433	0.9261	0.5105	0.063 (8)*
H8'B	0.5321	0.8574	0.5297	0.064 (8)*
H8'C	0.6355	0.8920	0.6721	0.078 (10)*
O9'	0.1350 (2)	1.01858 (8)	0.6578 (2)	0.0499 (4)
C10'	−0.0189 (3)	1.06159 (13)	0.6765 (3)	0.0527 (6)
H10A	−0.0040	1.1048	0.6239	0.064 (8)*
H10B	−0.0296	1.0705	0.7831	0.057 (8)*
H10C	−0.1272	1.0386	0.6350	0.057 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0709 (5)	0.0672 (5)	0.0828 (6)	−0.0152 (4)	0.0374 (4)	0.0113 (4)
C2	0.0426 (13)	0.0687 (17)	0.0475 (13)	−0.0126 (12)	0.0100 (11)	−0.0067 (12)
N3	0.0384 (11)	0.0617 (13)	0.0466 (11)	−0.0028 (9)	0.0107 (9)	0.0025 (9)
C4	0.0403 (12)	0.0464 (13)	0.0426 (12)	−0.0099 (10)	0.0065 (10)	−0.0028 (10)
C5	0.0612 (17)	0.0527 (16)	0.0746 (18)	−0.0081 (14)	0.0287 (14)	0.0074 (13)
C6	0.0473 (16)	0.093 (2)	0.0657 (18)	−0.0002 (15)	0.0214 (13)	−0.0041 (17)
Cl1	0.0647 (5)	0.0465 (4)	0.0893 (6)	0.0085 (3)	0.0204 (4)	0.0216 (3)
C1'	0.0360 (12)	0.0410 (12)	0.0412 (12)	−0.0055 (9)	0.0055 (9)	−0.0017 (10)
C2'	0.0433 (12)	0.0363 (12)	0.0449 (12)	−0.0010 (10)	0.0047 (10)	0.0029 (10)
C3'	0.0371 (12)	0.0411 (12)	0.0480 (12)	0.0039 (10)	0.0085 (10)	−0.0027 (10)
C4'	0.0369 (12)	0.0408 (12)	0.0427 (12)	0.0000 (10)	0.0103 (9)	−0.0003 (10)
C5'	0.0394 (12)	0.0360 (11)	0.0453 (12)	0.0005 (10)	0.0091 (10)	0.0017 (10)
C6'	0.0361 (12)	0.0410 (12)	0.0447 (12)	0.0035 (10)	0.0092 (9)	−0.0005 (10)
O7'	0.0439 (9)	0.0485 (10)	0.0621 (10)	0.0045 (8)	0.0235 (8)	0.0092 (8)
C8'	0.0388 (13)	0.0577 (16)	0.0643 (16)	0.0048 (11)	0.0212 (12)	0.0052 (13)
O9'	0.0472 (10)	0.0400 (9)	0.0650 (11)	0.0065 (7)	0.0218 (8)	0.0097 (8)
C10'	0.0531 (15)	0.0423 (13)	0.0636 (16)	0.0103 (12)	0.0115 (12)	0.0008 (12)

Geometric parameters (Å, º)

S1—C5	1.708 (3)	C3'—C4'	1.368 (3)
S1—C2	1.725 (3)	C3'—H3'A	0.9300
C2—N3	1.296 (3)	C4'—O7'	1.358 (3)
C2—C6	1.501 (4)	C4'—C5'	1.411 (3)
N3—C4	1.387 (3)	C5'—O9'	1.362 (3)
C4—C5	1.356 (4)	C5'—C6'	1.373 (3)
C4—C1'	1.488 (3)	C6'—H6'A	0.9300
C5—H5A	0.9300	O7'—C8'	1.429 (3)
C6—H6A	0.9600	C8'—H8'A	0.9600
C6—H6B	0.9600	C8'—H8'B	0.9600
C6—H6C	0.9600	C8'—H8'C	0.9600
Cl1—C2'	1.747 (2)	O9'—C10'	1.418 (3)
C1'—C2'	1.386 (3)	C10'—H10A	0.9600
C1'—C6'	1.405 (3)	C10'—H10B	0.9600
C2'—C3'	1.392 (3)	C10'—H10C	0.9600
C5—S1—C2	89.69 (13)	C2'—C3'—H3'A	119.6
N3—C2—C6	124.4 (3)	O7'—C4'—C3'	125.6 (2)
N3—C2—S1	113.8 (2)	O7'—C4'—C5'	115.70 (19)
C6—C2—S1	121.7 (2)	C3'—C4'—C5'	118.7 (2)
C2—N3—C4	111.9 (2)	O9'—C5'—C6'	125.5 (2)
C5—C4—N3	113.9 (2)	O9'—C5'—C4'	115.07 (19)
C5—C4—C1'	129.7 (2)	C6'—C5'—C4'	119.4 (2)
N3—C4—C1'	116.3 (2)	C5'—C6'—C1'	123.0 (2)
C4—C5—S1	110.6 (2)	C5'—C6'—H6'A	118.5
C4—C5—H5A	124.7	C1'—C6'—H6'A	118.5
S1—C5—H5A	124.7	C4'—O7'—C8'	117.20 (18)
C2—C6—H6A	109.5	O7'—C8'—H8'A	109.5
C2—C6—H6B	109.5	O7'—C8'—H8'B	109.5
H6A—C6—H6B	109.5	H8'A—C8'—H8'B	109.5
C2—C6—H6C	109.5	O7'—C8'—H8'C	109.5
H6A—C6—H6C	109.5	H8'A—C8'—H8'C	109.5
H6B—C6—H6C	109.5	H8'B—C8'—H8'C	109.5
C2'—C1'—C6'	115.9 (2)	C5'—O9'—C10'	117.40 (18)
C2'—C1'—C4	126.7 (2)	O9'—C10'—H10A	109.5
C6'—C1'—C4	117.3 (2)	O9'—C10'—H10B	109.5
C1'—C2'—C3'	122.3 (2)	H10A—C10'—H10B	109.5
C1'—C2'—Cl1	122.82 (17)	O9'—C10'—H10C	109.5
C3'—C2'—Cl1	114.89 (17)	H10A—C10'—H10C	109.5
C4'—C3'—C2'	120.7 (2)	H10B—C10'—H10C	109.5
C4'—C3'—H3'A	119.6
C5—S1—C2—N3	−0.2 (2)	C1'—C2'—C3'—C4'	−0.1 (4)
C5—S1—C2—C6	−178.8 (2)	Cl1—C2'—C3'—C4'	179.88 (18)
C6—C2—N3—C4	178.3 (2)	C2'—C3'—C4'—O7'	−179.6 (2)
S1—C2—N3—C4	−0.3 (3)	C2'—C3'—C4'—C5'	−0.2 (3)
C2—N3—C4—C5	0.8 (3)	O7'—C4'—C5'—O9'	0.2 (3)
C2—N3—C4—C1'	−176.1 (2)	C3'—C4'—C5'—O9'	−179.3 (2)
N3—C4—C5—S1	−0.9 (3)	O7'—C4'—C5'—C6'	−179.9 (2)
C1'—C4—C5—S1	175.4 (2)	C3'—C4'—C5'—C6'	0.6 (3)
C2—S1—C5—C4	0.6 (2)	O9'—C5'—C6'—C1'	179.0 (2)
C5—C4—C1'—C2'	6.5 (4)	C4'—C5'—C6'—C1'	−0.8 (3)
N3—C4—C1'—C2'	−177.3 (2)	C2'—C1'—C6'—C5'	0.6 (3)
C5—C4—C1'—C6'	−170.1 (3)	C4—C1'—C6'—C5'	177.6 (2)
N3—C4—C1'—C6'	6.1 (3)	C3'—C4'—O7'—C8'	−4.0 (3)
C6'—C1'—C2'—C3'	−0.2 (3)	C5'—C4'—O7'—C8'	176.5 (2)
C4—C1'—C2'—C3'	−176.8 (2)	C6'—C5'—O9'—C10'	−3.9 (3)
C6'—C1'—C2'—Cl1	179.91 (17)	C4'—C5'—O9'—C10'	175.9 (2)
C4—C1'—C2'—Cl1	3.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8′—H8′A···O9′^i	0.96	2.51	3.461 (3)	174
C5—H5A···Cl1	0.93	2.48	3.097 (3)	124
C6′—H6′A···N3	0.93	2.36	2.751 (3)	105

Symmetry code: (i) −x+1, −y+2, −z+1.