2-Amino­thia­zole and 2-amino­thiazolinone derivatives

The reaction of different substituted [alpha]-cyano­oxiranes with thio­urea resulted in the formation of the 2-amino­thia­zolinone derivative 2-amino-5-(2,5-di­methoxy­phenyl)-1,3-thia­zol-4(5H)-one, C₁₁H₁₂N₂O₃S, (I), and the 2-amino­thia­zole derivative ethyl 2-amino-5-(2,5-di­methoxy­phenyl)-1,3-thia­zole-4-carboxyl­ate, C₁₄H₁₆N₂O₄S, (II). The geometries of the two crystallographically independent mol­ecules in (II) are nearly identical but mirror related. The crystal structures of both compounds contain two types of intermolecular hydrogen bonds.

S1. Comment

Many naturally occurring and synthetic thiazole derivatives exhibit biological activities, such as antibiotic, anti-inflammatory, anthelmintic or fungicide properties (Metzger, 1984; Crews et al., 1988; Shinagawa et al., 1997; Shivarama Holla et al., 2003). The 1,3-thiazole ring can be prepared using several different methods (Metzger, 1984), although the most widely used approach relies on the synthesis described by Hantzsch (1887), which starts from α-halocarbonyl derivatives. This method can be modified by the replacement of α-halocarbonyl derivatives with 2-cyanooxiranes reacting as synthetic equivalents of the ketene dication (Robert et al., 1995, and references therein). We focus our attention here on the synthesis of thiazole and thiazoline derivatives from 2,2-dicyanooxirane and 2-cyano-2-oxiranecarboxylate derivatives. On addition of thiourea, on one hand, geminal dicyano oxirane derivatives were transformed into 2-aminothiazolinones, and on the other hand, ethyl 2-cyano-2-oxiranecarboxylate yielded 2-aminothiazols. In this paper we present the synthesis and structure of 2-amino-5-(2,5-dimethoxyphenyl)-4,5-dihydro-1,3-thiazol-4-one, (I), and ethyl 2-amino-5-(2,5-dimethoxyphenyl)-1,3-thiazole-4-carboxylate, (II). To the best of our knowledge, this is the first report of the crystal structure of the 2-aminothiazole derivative.

The molecular structure of (I) is shown in Fig. 1. The heterocyclic (thiazole) ring is close to perfectly planar, and the angle between the least-square planes of the phenyl and thiazole rings is 86.46 (4)°. Other geometric parameters are listed in Table 1. The two types of hydrogen-bonding interaction are illustrated in Fig. 2. The first involves N—H···N bonds between the amino group and the endocyclic thiazole N atom of two molecules symmetry-related by an inversion centre. These dimers are further connected into chains along the a axis via N—H···O interactions with adjacent dimeric units. For hydrogen-bonding details see Table 2.

X-ray analysis of (II) reveals that the crystals consist of two crystallographically independent molecules (A and B) related by a local pseudo-inversion centre. The atomic labeling schemes for these two molecules include the letter corresponding to the independent molecule (Fig. 3). The two independent mirror-related molecules have similar conformations (Fig. 4), and there are no significant differences in bond lengths and angles for molecules A and B (Table 3). The angles between the planes of dimethoxyphenyl ring and the thiazole ring are 69.32 (12) and 71.44 (12)° in molecules A and B, respectively. As in (I), two types of intermolecular hydrogen bond are present. Amino groups of both molecules are involved in an interaction with the endocyclic N atom and in the formation of an N—H···O bond with a neighbouring molecule. While in compound (I), the carbonyl O atom of the thiazolinone ring acts as a hydrogen-bond acceptor, in compound (II), one of the methoxy groups on both substituted phenyl rings serves as a hydrogen-bond acceptor. For hydrogen bonding details see Table 4.

S2. Experimental

For the preparation of (I), a mixture of 3-(2,5-dimethoxyphenyl)-2,2-oxiranedicarbonitrile (0.230 g, 1 mmol) and thiourea (0.076 g, 1 mmol) was dissolved in acetonitrile (5 ml) and stirred at room temperature for 24 h. The product precipitated from the reaction mixture in 68% yield (m.p. 469–471 K). ¹H NMR (300 MHz, DMSO, p.p.m.): δ 3.68 (s, 3H), 3.70 (s, 3H), 5.34 (s, 1H), 6.73 (d, 1H), 6.87 (dd, 1H), 6.93 (d, 1H), 8.73 (s, 1H), 8.99 (s, 1H). Analysis found: C 52.08, H 4.36, N 10.96%; calculated for C₁₁H₁₂N₂O₃S: C 52.37, H 4.79, N 11.10%. Crystals suitable for X-ray diffraction were obtained by recrystallization from ethanol. For the preparation of (II), a mixture of ethyl 2-cyano-3-(2,5-dimethoxyphenyl)-2-oxiranecarboxylate (0.277 g, 1 mmol) and thiourea (0.076 g, 1 mmol) was dissolved in acetonitrile (5 ml) and refluxed for 6 h. Water (50 ml) was added to the reaction mixture and the solution was extracted with ether (3 x 50 ml). The organic layers were combined and dried over sodium sulfate(VI), and the solid residue was recrystallized from ethanol to give (II) in 49% yield (m.p. 404–405 K). ¹H NMR (300 MHz, DMSO, p.p.m.): δ 1.03 (t, 3H), 3.66 (s, 3H), 3.71 (s, 3H), 4.01 (q, 2H), 6.79 (d, 1H), 6.89 (dd, 1H), 6.99 (d, 1H), 7.20 (s, 2H).

S3. Refinement

For (I), all H atoms were located in difference Fourier syntheses and were included in the refinement. For (II), H atoms were placed at calculated positions and treated as riding.

Computing details

Data collection: Collect (Nonius, 1998) for (I); Collect Software (Nonius,1998) for (II). Cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (I); DENZO and SCALEPACK (Otwinowski & Minor,1997) for (II). Data reduction: DENZO AND SCALEPACK for (I); DENZO AND SCALEPACK (Otwinowski & Minor, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (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: SHELXL97 and PLATON (Spek, 1998) for (I); SHELXL97 (Sheldrick,1997), PLATON (Spek, 1998) for (II).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The intermolecular hydrogen bonding in (I), showing the formation of a chain of dimeric units that propagates along the a direction.
	Fig. 3. A view of the independent molecules, A and B, of (II), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A superposition of the two independent molecules in (II).

(I) 2-amino-5-(2,5-dimethoxyphenyl)-1,3-thiazol-4(5H)-one

Crystal data

C11H12N2O3S	Z = 2
Mr = 252.29	F(000) = 264
Triclinic, P1	Dx = 1.493 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9572 (5) Å	Cell parameters from all reflections
b = 8.1499 (7) Å	θ = 2.9–27.5°
c = 10.4564 (10) Å	µ = 0.29 mm^−1
α = 99.800 (2)°	T = 293 K
β = 101.050 (2)°	Prism, colourless
γ = 99.540 (2)°	0.40 × 0.35 × 0.30 mm
V = 561.21 (8) Å^3

Data collection

Nonius KappaCCD diffractometer	2349 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.014
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −8→9
3846 measured reflections	k = −10→10
2490 independent reflections	l = −12→13

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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F^2) = 0.078	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 0.1774P] where P = (Fo^2 + 2Fc^2)/3
2490 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.22 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	0.55666 (4)	0.59805 (4)	0.66437 (3)	0.03000 (11)
O4	0.07240 (13)	0.62722 (12)	0.78502 (9)	0.0365 (2)
O12	0.41528 (15)	0.95265 (11)	0.77662 (9)	0.0393 (2)
O14	0.05392 (16)	0.82197 (14)	0.24062 (10)	0.0481 (3)
N2	0.71460 (17)	0.55027 (16)	0.90370 (11)	0.0368 (2)
N3	0.38166 (15)	0.57493 (13)	0.86499 (9)	0.0296 (2)
C2	0.55238 (17)	0.57240 (14)	0.82656 (11)	0.0263 (2)
C4	0.23831 (16)	0.60987 (13)	0.77023 (11)	0.0262 (2)
C5	0.29562 (16)	0.61638 (14)	0.63517 (11)	0.0249 (2)
C6	0.25934 (16)	0.76502 (14)	0.57272 (11)	0.0253 (2)
C7	0.16979 (17)	0.73475 (15)	0.43822 (12)	0.0285 (2)
C8	0.14498 (18)	0.86868 (17)	0.37384 (13)	0.0343 (3)
C9	0.2108 (2)	1.03383 (17)	0.44517 (15)	0.0394 (3)
C10	0.3012 (2)	1.06602 (16)	0.57982 (15)	0.0376 (3)
C11	0.32656 (17)	0.93353 (15)	0.64472 (12)	0.0303 (2)
C13	0.4826 (3)	1.1233 (2)	0.85348 (19)	0.0529 (4)
C15	0.0463 (3)	0.9545 (3)	0.1677 (2)	0.0575 (4)
H7	0.126 (2)	0.6212 (19)	0.3880 (15)	0.035 (4)*
H5	0.219 (2)	0.5100 (18)	0.5741 (14)	0.030 (3)*
H13A	0.367 (3)	1.180 (3)	0.854 (2)	0.069 (6)*
H2A	0.705 (3)	0.524 (2)	0.9833 (19)	0.054 (5)*
H13B	0.585 (3)	1.185 (3)	0.815 (2)	0.067 (6)*
H13C	0.545 (3)	1.112 (3)	0.943 (2)	0.073 (6)*
H15A	−0.016 (3)	0.894 (3)	0.075 (2)	0.079 (7)*
H15B	0.180 (3)	1.022 (2)	0.1770 (19)	0.060 (5)*
H15C	−0.039 (3)	1.032 (3)	0.197 (2)	0.075 (6)*
H2B	0.824 (3)	0.554 (2)	0.8758 (17)	0.047 (4)*
H10	0.348 (3)	1.181 (2)	0.6283 (17)	0.050 (4)*
H9	0.189 (3)	1.124 (2)	0.4044 (18)	0.055 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.03223 (17)	0.04005 (18)	0.02628 (16)	0.01544 (12)	0.01433 (11)	0.01368 (12)
O4	0.0290 (4)	0.0438 (5)	0.0412 (5)	0.0088 (4)	0.0157 (4)	0.0111 (4)
O12	0.0463 (5)	0.0287 (4)	0.0359 (5)	0.0031 (4)	0.0042 (4)	−0.0016 (4)
O14	0.0514 (6)	0.0577 (6)	0.0395 (5)	0.0122 (5)	0.0050 (4)	0.0268 (5)
N2	0.0310 (5)	0.0559 (7)	0.0302 (5)	0.0133 (5)	0.0110 (4)	0.0182 (5)
N3	0.0309 (5)	0.0362 (5)	0.0250 (5)	0.0068 (4)	0.0111 (4)	0.0102 (4)
C2	0.0304 (5)	0.0259 (5)	0.0243 (5)	0.0051 (4)	0.0094 (4)	0.0068 (4)
C4	0.0281 (5)	0.0231 (5)	0.0278 (5)	0.0026 (4)	0.0107 (4)	0.0047 (4)
C5	0.0270 (5)	0.0239 (5)	0.0245 (5)	0.0051 (4)	0.0077 (4)	0.0047 (4)
C6	0.0234 (5)	0.0250 (5)	0.0299 (5)	0.0057 (4)	0.0094 (4)	0.0082 (4)
C7	0.0250 (5)	0.0311 (6)	0.0321 (6)	0.0065 (4)	0.0088 (4)	0.0100 (5)
C8	0.0274 (6)	0.0443 (7)	0.0382 (6)	0.0110 (5)	0.0111 (5)	0.0198 (5)
C9	0.0356 (6)	0.0367 (7)	0.0569 (8)	0.0126 (5)	0.0178 (6)	0.0261 (6)
C10	0.0350 (6)	0.0246 (6)	0.0564 (8)	0.0061 (5)	0.0161 (6)	0.0107 (5)
C11	0.0268 (5)	0.0273 (5)	0.0373 (6)	0.0051 (4)	0.0102 (5)	0.0057 (5)
C13	0.0547 (9)	0.0348 (7)	0.0569 (10)	0.0022 (7)	0.0079 (8)	−0.0118 (7)
C15	0.0536 (10)	0.0758 (12)	0.0562 (10)	0.0195 (9)	0.0121 (8)	0.0443 (9)

Geometric parameters (Å, º)

S1—C2	1.7488 (11)	C8—O14	1.3741 (16)
S1—C5	1.8185 (11)	C8—C9	1.379 (2)
C2—N2	1.3134 (16)	C9—C10	1.388 (2)
C2—N3	1.3270 (15)	C9—H9	0.928 (18)
N3—C4	1.3671 (15)	C10—C11	1.3871 (17)
C4—O4	1.2211 (14)	C10—H10	0.956 (18)
C4—C5	1.5462 (15)	C11—O12	1.3697 (16)
C5—C6	1.5051 (15)	O12—C13	1.4350 (16)
C5—H5	0.986 (14)	C13—H13A	0.99 (2)
N2—H2A	0.905 (19)	C13—H13B	0.99 (2)
N2—H2B	0.860 (18)	C13—H13C	0.98 (2)
C6—C7	1.3863 (16)	O14—C15	1.4264 (18)
C6—C11	1.4042 (16)	C15—H15A	0.99 (2)
C7—C8	1.3937 (17)	C15—H15B	0.98 (2)
C7—H7	0.952 (15)	C15—H15C	0.99 (2)
C2—S1—C5	90.41 (5)	C9—C8—C7	119.40 (12)
N2—C2—N3	123.15 (11)	C8—C9—C10	120.16 (12)
N2—C2—S1	119.43 (9)	C8—C9—H9	120.1 (11)
N3—C2—S1	117.41 (9)	C10—C9—H9	119.7 (11)
C2—N3—C4	112.25 (9)	C11—C10—C9	120.84 (12)
O4—C4—N3	124.39 (10)	C11—C10—H10	119.4 (10)
O4—C4—C5	120.63 (10)	C9—C10—H10	119.7 (10)
N3—C4—C5	114.90 (9)	O12—C11—C10	125.04 (11)
C6—C5—C4	117.84 (9)	O12—C11—C6	115.68 (10)
C6—C5—S1	112.49 (7)	C10—C11—C6	119.28 (12)
C4—C5—S1	104.59 (7)	C11—O12—C13	117.02 (12)
C6—C5—H5	109.3 (8)	O12—C13—H13A	109.6 (12)
C4—C5—H5	105.4 (8)	O12—C13—H13B	108.8 (12)
S1—C5—H5	106.4 (8)	H13A—C13—H13B	111.4 (17)
C2—N2—H2A	118.1 (12)	O12—C13—H13C	105.2 (13)
C2—N2—H2B	120.0 (11)	H13A—C13—H13C	112.2 (17)
H2A—N2—H2B	121.8 (16)	H13B—C13—H13C	109.3 (17)
C7—C6—C11	119.27 (11)	C8—O14—C15	117.14 (13)
C7—C6—C5	118.89 (10)	O14—C15—H15A	104.3 (13)
C11—C6—C5	121.68 (10)	O14—C15—H15B	111.0 (11)
C6—C7—C8	121.05 (11)	H15A—C15—H15B	112.5 (17)
C6—C7—H7	120.1 (9)	O14—C15—H15C	112.4 (13)
C8—C7—H7	118.9 (9)	H15A—C15—H15C	108.3 (18)
O14—C8—C9	125.16 (12)	H15B—C15—H15C	108.4 (17)
O14—C8—C7	115.44 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3^i	0.905 (19)	2.04 (2)	2.9281 (15)	165.3 (17)
N2—H2B···O4^ii	0.860 (18)	2.176 (19)	3.0102 (15)	163.1 (16)

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

(II) ethyl 2-amino-5-(2,5-dimethoxyphenyl)-1,3-thiazole-4-carboxylate

Crystal data

C14H16N2O4S	F(000) = 648
Mr = 308.35	Dx = 1.358 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from all reflections
a = 8.1740 (5) Å	θ = 2.8–27.5°
b = 22.8266 (12) Å	µ = 0.23 mm^−1
c = 9.0300 (5) Å	T = 293 K
β = 116.444 (1)°	Prismatic, colourless
V = 1508.57 (15) Å^3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Nonius Kappa CCD diffractometer	5468 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −10→10
6339 measured reflections	k = −29→23
6339 independent reflections	l = −11→11

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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0772P)^2 + 0.6156P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6339 reflections	Δρmax = 0.83 e Å^−3
385 parameters	Δρmin = −0.23 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (8)

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
S1A	1.13783 (11)	−0.00152 (3)	−0.04470 (10)	0.04194 (19)
C2A	1.0425 (4)	0.05598 (14)	−0.1861 (4)	0.0397 (7)
N2A	1.1069 (5)	0.06959 (15)	−0.2937 (4)	0.0593 (9)
H2A	1.0611	0.0986	−0.3604	0.071*
H2B	1.1944	0.0494	−0.2964	0.071*
N3A	0.9104 (3)	0.08360 (11)	−0.1714 (3)	0.0376 (5)
C4A	0.8840 (4)	0.06114 (13)	−0.0416 (3)	0.0335 (6)
C5A	0.9910 (4)	0.01458 (13)	0.0420 (3)	0.0323 (6)
C6A	1.0072 (4)	−0.01893 (12)	0.1880 (3)	0.0332 (6)
C7A	1.1627 (4)	−0.01171 (14)	0.3369 (4)	0.0375 (7)
H7A	1.2538	0.0139	0.3424	0.045*
C8A	1.1843 (5)	−0.04215 (16)	0.4777 (4)	0.0423 (8)
C9A	1.0498 (5)	−0.08051 (17)	0.4681 (4)	0.0482 (8)
H9A	1.0640	−0.1011	0.5619	0.058*
C10A	0.8941 (5)	−0.08886 (17)	0.3214 (4)	0.0450 (8)
H10A	0.8051	−0.1153	0.3163	0.054*
C11A	0.8712 (4)	−0.05736 (14)	0.1807 (4)	0.0362 (6)
O12A	0.7222 (3)	−0.06278 (11)	0.0288 (3)	0.0500 (6)
C13A	0.5775 (5)	−0.0996 (2)	0.0164 (5)	0.0676 (12)
H13A	0.6194	−0.1394	0.0365	0.101*
H13B	0.4780	−0.0964	−0.0925	0.101*
H13C	0.5370	−0.0880	0.0968	0.101*
O14A	1.3304 (4)	−0.03468 (14)	0.6318 (3)	0.0621 (7)
C15A	1.4820 (5)	−0.0023 (2)	0.6411 (5)	0.0573 (10)
H15A	1.5210	−0.0177	0.5631	0.086*
H15B	1.5802	−0.0052	0.7508	0.086*
H15C	1.4478	0.0381	0.6156	0.086*
C17A	0.7405 (4)	0.08922 (14)	−0.0075 (4)	0.0368 (6)
O18A	0.6388 (4)	0.12646 (13)	−0.0924 (4)	0.0631 (7)
O19A	0.7417 (3)	0.06896 (11)	0.1308 (3)	0.0477 (6)
C20A	0.6021 (4)	0.09115 (16)	0.1732 (4)	0.0456 (8)
H20A	0.4817	0.0854	0.0821	0.055*
H20B	0.6199	0.1327	0.1983	0.055*
C21A	0.6204 (6)	0.0573 (2)	0.3220 (5)	0.0619 (10)
H21A	0.5906	0.0169	0.2924	0.093*
H21B	0.5386	0.0731	0.3618	0.093*
H21C	0.7438	0.0601	0.4071	0.093*
S1B	0.70083 (11)	0.26178 (3)	0.38645 (10)	0.0451 (2)
C2B	0.7944 (4)	0.20365 (15)	0.5258 (4)	0.0420 (7)
N2B	0.7292 (5)	0.18978 (16)	0.6345 (4)	0.0608 (9)
H2C	0.7724	0.1600	0.6987	0.073*
H2D	0.6444	0.2107	0.6398	0.073*
N3B	0.9218 (3)	0.17508 (11)	0.5079 (3)	0.0377 (5)
C4B	0.9503 (4)	0.19837 (13)	0.3795 (3)	0.0332 (6)
C5B	0.8457 (4)	0.24461 (13)	0.2981 (4)	0.0345 (6)
C6B	0.8284 (4)	0.27817 (12)	0.1507 (3)	0.0333 (6)
C7B	0.6754 (4)	0.26925 (14)	0.0022 (4)	0.0370 (7)
H7B	0.5846	0.2436	−0.0031	0.044*
C8B	0.6571 (4)	0.29882 (14)	−0.1404 (4)	0.0381 (7)
C9B	0.7933 (5)	0.33668 (15)	−0.1306 (4)	0.0452 (7)
H9B	0.7821	0.3563	−0.2249	0.054*
C10B	0.9455 (5)	0.34567 (15)	0.0174 (4)	0.0445 (7)
H10B	1.0364	0.3712	0.0220	0.053*
C11B	0.9646 (4)	0.31690 (15)	0.1606 (4)	0.0374 (7)
O12B	1.1103 (3)	0.32378 (11)	0.3123 (3)	0.0516 (6)
C13B	1.2519 (6)	0.3615 (3)	0.3255 (5)	0.0717 (13)
H13D	1.3011	0.3485	0.2525	0.108*
H13E	1.3464	0.3613	0.4373	0.108*
H13F	1.2048	0.4006	0.2959	0.108*
O14B	0.5110 (3)	0.29203 (12)	−0.2930 (3)	0.0545 (6)
C15B	0.3604 (5)	0.2577 (2)	−0.3027 (5)	0.0569 (9)
H15D	0.3967	0.2174	−0.2808	0.085*
H15E	0.2607	0.2612	−0.4115	0.085*
H15F	0.3224	0.2716	−0.2225	0.085*
C17B	1.0913 (4)	0.16904 (14)	0.3448 (4)	0.0363 (6)
O18B	1.1909 (4)	0.13113 (12)	0.4278 (3)	0.0607 (7)
O19B	1.0945 (3)	0.19020 (11)	0.2086 (3)	0.0478 (6)
C20B	1.2327 (4)	0.16804 (16)	0.1654 (4)	0.0450 (7)
H20C	1.2128	0.1267	0.1382	0.054*
H20D	1.3530	0.1729	0.2573	0.054*
C21B	1.2185 (6)	0.20242 (19)	0.0186 (5)	0.0578 (10)
H21D	1.0950	0.2010	−0.0669	0.087*
H21E	1.2989	0.1859	−0.0218	0.087*
H21F	1.2525	0.2424	0.0506	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0478 (4)	0.0416 (4)	0.0462 (4)	0.0106 (3)	0.0298 (3)	0.0115 (3)
C2A	0.0478 (16)	0.0393 (17)	0.0368 (15)	0.0033 (13)	0.0233 (13)	0.0075 (12)
N2A	0.078 (2)	0.062 (2)	0.0621 (19)	0.0233 (17)	0.0528 (18)	0.0252 (16)
N3A	0.0442 (13)	0.0390 (14)	0.0361 (12)	0.0037 (11)	0.0238 (11)	0.0067 (10)
C4A	0.0351 (14)	0.0357 (16)	0.0323 (14)	−0.0016 (11)	0.0173 (12)	0.0031 (11)
C5A	0.0337 (13)	0.0339 (16)	0.0310 (13)	0.0008 (11)	0.0159 (11)	0.0025 (11)
C6A	0.0387 (14)	0.0300 (15)	0.0362 (14)	0.0045 (11)	0.0215 (12)	0.0042 (11)
C7A	0.0387 (14)	0.0397 (18)	0.0357 (14)	0.0000 (13)	0.0181 (12)	0.0068 (12)
C8A	0.0440 (17)	0.048 (2)	0.0317 (15)	0.0021 (14)	0.0142 (13)	0.0037 (13)
C9A	0.0559 (19)	0.055 (2)	0.0384 (16)	−0.0025 (16)	0.0250 (15)	0.0117 (14)
C10A	0.0520 (18)	0.0430 (19)	0.0453 (17)	−0.0083 (15)	0.0264 (15)	0.0082 (15)
C11A	0.0396 (14)	0.0344 (16)	0.0373 (15)	−0.0023 (12)	0.0197 (12)	0.0027 (12)
O12A	0.0461 (12)	0.0540 (15)	0.0448 (12)	−0.0159 (11)	0.0157 (10)	0.0051 (11)
C13A	0.050 (2)	0.083 (3)	0.059 (2)	−0.025 (2)	0.0142 (18)	0.015 (2)
O14A	0.0570 (15)	0.085 (2)	0.0337 (12)	−0.0096 (14)	0.0106 (11)	0.0116 (12)
C15A	0.0442 (18)	0.074 (3)	0.0437 (18)	−0.004 (2)	0.0106 (15)	0.0036 (19)
C17A	0.0391 (15)	0.0364 (16)	0.0392 (15)	0.0014 (13)	0.0215 (13)	0.0041 (12)
O18A	0.0668 (16)	0.0699 (18)	0.0622 (16)	0.0328 (14)	0.0373 (13)	0.0276 (14)
O19A	0.0474 (12)	0.0585 (15)	0.0505 (13)	0.0174 (11)	0.0338 (11)	0.0161 (11)
C20A	0.0440 (16)	0.048 (2)	0.057 (2)	0.0036 (14)	0.0336 (15)	0.0015 (15)
C21A	0.073 (2)	0.069 (3)	0.068 (2)	0.001 (2)	0.053 (2)	0.0051 (19)
S1B	0.0524 (4)	0.0455 (5)	0.0489 (4)	0.0143 (3)	0.0328 (4)	0.0140 (3)
C2B	0.0504 (17)	0.0447 (18)	0.0386 (16)	0.0078 (14)	0.0266 (14)	0.0058 (13)
N2B	0.081 (2)	0.064 (2)	0.0633 (19)	0.0268 (17)	0.0559 (18)	0.0272 (16)
N3B	0.0439 (13)	0.0398 (14)	0.0339 (12)	0.0065 (11)	0.0214 (11)	0.0109 (10)
C4B	0.0354 (13)	0.0336 (15)	0.0318 (14)	0.0007 (11)	0.0161 (11)	0.0045 (11)
C5B	0.0356 (14)	0.0355 (16)	0.0358 (15)	0.0008 (11)	0.0189 (12)	0.0040 (11)
C6B	0.0379 (14)	0.0328 (16)	0.0319 (14)	0.0027 (11)	0.0181 (12)	0.0079 (11)
C7B	0.0380 (15)	0.0348 (17)	0.0397 (16)	0.0001 (13)	0.0185 (13)	0.0041 (13)
C8B	0.0440 (15)	0.0386 (17)	0.0328 (14)	0.0054 (13)	0.0180 (12)	0.0064 (12)
C9B	0.0547 (18)	0.0429 (18)	0.0425 (17)	0.0046 (14)	0.0258 (15)	0.0141 (13)
C10B	0.0496 (17)	0.0381 (18)	0.0490 (18)	−0.0041 (14)	0.0249 (15)	0.0101 (14)
C11B	0.0392 (15)	0.0369 (17)	0.0367 (15)	0.0009 (13)	0.0175 (13)	0.0030 (12)
O12B	0.0454 (12)	0.0596 (16)	0.0410 (12)	−0.0128 (11)	0.0111 (10)	0.0087 (11)
C13B	0.055 (2)	0.086 (3)	0.059 (2)	−0.028 (2)	0.012 (2)	0.006 (2)
O14B	0.0513 (13)	0.0683 (17)	0.0353 (12)	−0.0068 (12)	0.0116 (10)	0.0108 (11)
C15B	0.0515 (19)	0.064 (2)	0.0428 (18)	−0.0089 (18)	0.0093 (15)	0.0013 (17)
C17B	0.0357 (14)	0.0396 (17)	0.0337 (14)	0.0020 (13)	0.0154 (12)	0.0039 (12)
O18B	0.0707 (16)	0.0624 (17)	0.0612 (16)	0.0299 (14)	0.0403 (14)	0.0250 (14)
O19B	0.0511 (13)	0.0554 (15)	0.0517 (13)	0.0164 (11)	0.0363 (11)	0.0173 (11)
C20B	0.0447 (16)	0.048 (2)	0.0540 (19)	0.0034 (14)	0.0327 (15)	0.0012 (15)
C21B	0.067 (2)	0.062 (2)	0.065 (2)	0.0026 (18)	0.048 (2)	0.0077 (18)

Geometric parameters (Å, º)

S1A—C5A	1.739 (3)	S1B—C5B	1.742 (3)
S1A—C2A	1.753 (3)	S1B—C2B	1.753 (3)
C2A—N3A	1.307 (4)	C2B—N3B	1.298 (4)
C2A—N2A	1.332 (4)	C2B—N2B	1.347 (4)
N2A—H2A	0.8600	N2B—H2C	0.8600
N2A—H2B	0.8600	N2B—H2D	0.8600
N3A—C4A	1.381 (4)	N3B—C4B	1.386 (4)
C4A—C5A	1.370 (4)	C4B—C5B	1.351 (4)
C4A—C17A	1.484 (4)	C4B—C17B	1.482 (4)
C5A—C6A	1.478 (4)	C5B—C6B	1.487 (4)
C6A—C7A	1.388 (4)	C6B—C7B	1.382 (4)
C6A—C11A	1.394 (4)	C6B—C11B	1.393 (4)
C7A—C8A	1.390 (4)	C7B—C8B	1.401 (4)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—C9A	1.377 (5)	C8B—O14B	1.373 (4)
C8A—O14A	1.382 (4)	C8B—C9B	1.381 (5)
C9A—C10A	1.382 (5)	C9B—C10B	1.376 (5)
C9A—H9A	0.9300	C9B—H9B	0.9300
C10A—C11A	1.398 (4)	C10B—C11B	1.395 (4)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—O12A	1.376 (4)	C11B—O12B	1.366 (4)
O12A—C13A	1.414 (4)	O12B—C13B	1.405 (5)
C13A—H13A	0.9600	C13B—H13D	0.9600
C13A—H13B	0.9600	C13B—H13E	0.9600
C13A—H13C	0.9600	C13B—H13F	0.9600
O14A—C15A	1.413 (5)	O14B—C15B	1.428 (5)
C15A—H15A	0.9600	C15B—H15D	0.9600
C15A—H15B	0.9600	C15B—H15E	0.9600
C15A—H15C	0.9600	C15B—H15F	0.9600
C17A—O18A	1.198 (4)	C17B—O18B	1.196 (4)
C17A—O19A	1.328 (4)	C17B—O19B	1.332 (4)
O19A—C20A	1.447 (4)	O19B—C20B	1.441 (4)
C20A—C21A	1.498 (5)	C20B—C21B	1.499 (5)
C20A—H20A	0.9700	C20B—H20C	0.9700
C20A—H20B	0.9700	C20B—H20D	0.9700
C21A—H21A	0.9600	C21B—H21D	0.9600
C21A—H21B	0.9600	C21B—H21E	0.9600
C21A—H21C	0.9600	C21B—H21F	0.9600
C5A—S1A—C2A	89.86 (14)	C5B—S1B—C2B	89.43 (14)
N3A—C2A—N2A	125.1 (3)	N3B—C2B—N2B	124.9 (3)
N3A—C2A—S1A	114.0 (2)	N3B—C2B—S1B	114.1 (2)
N2A—C2A—S1A	120.9 (3)	N2B—C2B—S1B	120.9 (3)
C2A—N2A—H2A	120.0	C2B—N2B—H2C	120.0
C2A—N2A—H2B	120.0	C2B—N2B—H2D	120.0
H2A—N2A—H2B	120.0	H2C—N2B—H2D	120.0
C2A—N3A—C4A	110.8 (3)	C2B—N3B—C4B	110.8 (3)
C5A—C4A—N3A	116.9 (3)	C5B—C4B—N3B	117.0 (3)
C5A—C4A—C17A	126.2 (3)	C5B—C4B—C17B	126.9 (3)
N3A—C4A—C17A	116.9 (3)	N3B—C4B—C17B	116.1 (3)
C4A—C5A—C6A	132.4 (3)	C4B—C5B—C6B	132.4 (3)
C4A—C5A—S1A	108.3 (2)	C4B—C5B—S1B	108.7 (2)
C6A—C5A—S1A	119.1 (2)	C6B—C5B—S1B	118.8 (2)
C7A—C6A—C11A	119.2 (3)	C7B—C6B—C11B	120.5 (3)
C7A—C6A—C5A	118.8 (3)	C7B—C6B—C5B	118.5 (3)
C11A—C6A—C5A	122.0 (3)	C11B—C6B—C5B	121.0 (3)
C6A—C7A—C8A	121.0 (3)	C6B—C7B—C8B	120.0 (3)
C6A—C7A—H7A	119.5	C6B—C7B—H7B	120.0
C8A—C7A—H7A	119.5	C8B—C7B—H7B	120.0
C9A—C8A—O14A	116.7 (3)	O14B—C8B—C9B	116.8 (3)
C9A—C8A—C7A	119.2 (3)	O14B—C8B—C7B	123.9 (3)
O14A—C8A—C7A	124.1 (3)	C9B—C8B—C7B	119.3 (3)
C8A—C9A—C10A	121.1 (3)	C10B—C9B—C8B	120.6 (3)
C8A—C9A—H9A	119.5	C10B—C9B—H9B	119.7
C10A—C9A—H9A	119.5	C8B—C9B—H9B	119.7
C9A—C10A—C11A	119.6 (3)	C9B—C10B—C11B	120.6 (3)
C9A—C10A—H10A	120.2	C9B—C10B—H10B	119.7
C11A—C10A—H10A	120.2	C11B—C10B—H10B	119.7
O12A—C11A—C6A	115.9 (3)	O12B—C11B—C6B	116.9 (3)
O12A—C11A—C10A	124.1 (3)	O12B—C11B—C10B	124.3 (3)
C6A—C11A—C10A	119.9 (3)	C6B—C11B—C10B	118.9 (3)
C11A—O12A—C13A	118.0 (3)	C11B—O12B—C13B	118.2 (3)
O12A—C13A—H13A	109.5	O12B—C13B—H13D	109.5
O12A—C13A—H13B	109.5	O12B—C13B—H13E	109.5
H13A—C13A—H13B	109.5	H13D—C13B—H13E	109.5
O12A—C13A—H13C	109.5	O12B—C13B—H13F	109.5
H13A—C13A—H13C	109.5	H13D—C13B—H13F	109.5
H13B—C13A—H13C	109.5	H13E—C13B—H13F	109.5
C8A—O14A—C15A	117.8 (3)	C8B—O14B—C15B	117.7 (3)
O14A—C15A—H15A	109.5	O14B—C15B—H15D	109.5
O14A—C15A—H15B	109.5	O14B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
O14A—C15A—H15C	109.5	O14B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
O18A—C17A—O19A	124.2 (3)	O18B—C17B—O19B	123.6 (3)
O18A—C17A—C4A	124.1 (3)	O18B—C17B—C4B	124.8 (3)
O19A—C17A—C4A	111.7 (3)	O19B—C17B—C4B	111.6 (2)
C17A—O19A—C20A	116.8 (3)	C17B—O19B—C20B	117.5 (3)
O19A—C20A—C21A	106.3 (3)	O19B—C20B—C21B	107.1 (3)
O19A—C20A—H20A	110.5	O19B—C20B—H20C	110.3
C21A—C20A—H20A	110.5	C21B—C20B—H20C	110.3
O19A—C20A—H20B	110.5	O19B—C20B—H20D	110.3
C21A—C20A—H20B	110.5	C21B—C20B—H20D	110.3
H20A—C20A—H20B	108.7	H20C—C20B—H20D	108.5
C20A—C21A—H21A	109.5	C20B—C21B—H21D	109.5
C20A—C21A—H21B	109.5	C20B—C21B—H21E	109.5
H21A—C21A—H21B	109.5	H21D—C21B—H21E	109.5
C20A—C21A—H21C	109.5	C20B—C21B—H21F	109.5
H21A—C21A—H21C	109.5	H21D—C21B—H21F	109.5
H21B—C21A—H21C	109.5	H21E—C21B—H21F	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2A···N3B^i	0.86	2.13	2.980 (4)	168
N2A—H2B···O14A^i	0.86	2.45	3.248 (4)	156
N2B—H2C···N3A^ii	0.86	2.12	2.971 (4)	168
N2B—H2D···O14B^ii	0.86	2.37	3.178 (4)	158

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