Ethyl 2-amino-4-(4-methyl-1,3-thia-zol-5-yl)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3-carboxyl-ate.

There are two independent mol-ecules in the asymmetric unit of the title compound, C19H16N2O5S, in which the thia-zole rings make dihedral angles of 80.89 (11) and 84.81 (11)° with the pyrano[3,2-c]chromene ring systems. An intra-molecular N-H⋯O hydrogen bond involving the amino group occurs in each independent mol-ecule. In the crystal, the amino groups are involved in N-H⋯O and N-H⋯N hydrogen bonds.

Related literature

Similar conformations were observed in the structures of ethyl 2-amino-5-oxo-4-(p-tol­yl)-4H,5H-pyrano[3,2-c]chromene-8-carboxyl­ate (Wang et al., 2004 ▶) and ethyl 2-amino-4-(2,4-di­chloro­phen­yl)-4H-benzo[f]chromene-3-carboxyl­ate (Shi et al., 2003 ▶). For applications of 4H-chromene and its derivatives, see: Jeso & Nicolaou (2009 ▶); Alvey et al. (2008 ▶, 2009 ▶); Bedair et al. (2001 ▶); El-Agrody et al. (2002 ▶, 2011 ▶); Abd-El-Aziz et al. (2004 ▶); Sabry et al. (2011 ▶).

Experimental

Crystal data

C19H16N2O5S

M = 384.41

Monoclinic,

a = 15.6232 (10) Å

b = 15.0696 (9) Å

c = 15.9063 (11) Å

β = 98.873 (2)°

V = 3700.1 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 298 K

0.35 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.931, T max = 0.970

18921 measured reflections

6130 independent reflections

3527 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.145

S = 1.03

6130 reflections

491 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813021703/bx2447sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021703/bx2447Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813021703/bx2447Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H16N2O5S	F(000) = 1600
Mr = 384.41	Dx = 1.380 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.6232 (10) Å	Cell parameters from 3286 reflections
b = 15.0696 (9) Å	θ = 2.4–21.4°
c = 15.9063 (11) Å	µ = 0.21 mm−1
β = 98.873 (2)°	T = 298 K
V = 3700.1 (4) Å3	Rectangular, yellow
Z = 8	0.35 × 0.25 × 0.15 mm

Bruker APEXII CCD area-detector diffractometer	3527 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→18
Tmin = 0.931, Tmax = 0.970	k = −16→14
18921 measured reflections	l = −18→18
6130 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0714P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.003
6130 reflections	Δρmax = 0.20 e Å−3
491 parameters	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.3585 (2)	0.4642 (2)	0.70875 (18)	0.0433 (8)
H1	0.3209	0.4686	0.7485	0.052*
C2	0.3845 (2)	0.5395 (2)	0.67213 (19)	0.0500 (9)
H2	0.3639	0.5946	0.6862	0.060*
C3	0.4417 (2)	0.5334 (2)	0.61380 (19)	0.0510 (9)
H3	0.4599	0.5847	0.5894	0.061*
C4	0.4715 (2)	0.4524 (2)	0.59173 (18)	0.0483 (9)
H4	0.5098	0.4484	0.5526	0.058*
C5	0.44379 (18)	0.3771 (2)	0.62839 (17)	0.0360 (7)
C6	0.38746 (18)	0.38107 (19)	0.68747 (16)	0.0332 (7)
C7	0.45393 (19)	0.2176 (2)	0.63881 (17)	0.0380 (7)
C8	0.39486 (18)	0.22000 (19)	0.69980 (16)	0.0334 (7)
C9	0.36581 (18)	0.2982 (2)	0.72308 (16)	0.0343 (7)
C10	0.37038 (19)	0.13370 (18)	0.73763 (17)	0.0357 (7)
H10	0.4235	0.0987	0.7523	0.043*
C11	0.33538 (19)	0.15276 (19)	0.81953 (17)	0.0357 (7)
C12	0.30737 (19)	0.2347 (2)	0.83743 (17)	0.0374 (7)
C13	0.30880 (19)	0.08051 (18)	0.67326 (17)	0.0359 (7)
C14	0.3214 (2)	−0.0002 (2)	0.63837 (19)	0.0453 (8)
C15	0.1869 (3)	0.0224 (2)	0.5769 (2)	0.0572 (10)
H15	0.1343	0.0116	0.5422	0.069*
C16	0.3354 (2)	0.0848 (2)	0.88338 (19)	0.0449 (8)
C17	0.3666 (4)	−0.0665 (3)	0.9178 (2)	0.1105 (19)
H17A	0.4128	−0.0588	0.9656	0.133*
H17B	0.3120	−0.0676	0.9397	0.133*
C18	0.3781 (3)	−0.1472 (3)	0.8767 (3)	0.1049 (16)
H18A	0.3376	−0.1507	0.8248	0.157*
H18B	0.3684	−0.1957	0.9132	0.157*
H18C	0.4361	−0.1503	0.8639	0.157*
C19	0.4028 (3)	−0.0539 (2)	0.6518 (2)	0.0752 (12)
H19A	0.4459	−0.0238	0.6912	0.113*
H19B	0.4235	−0.0613	0.5985	0.113*
H19C	0.3912	−0.1110	0.6743	0.113*
C1A	0.3840 (2)	0.7211 (2)	0.20315 (18)	0.0483 (9)
H1A	0.3506	0.7324	0.2456	0.058*
C2A	0.4120 (2)	0.7901 (2)	0.1583 (2)	0.0562 (9)
H2A	0.3975	0.8481	0.1703	0.067*
C3A	0.4616 (2)	0.7739 (3)	0.0952 (2)	0.0599 (10)
H3A	0.4804	0.8212	0.0653	0.072*
C4A	0.4834 (2)	0.6890 (3)	0.07611 (19)	0.0579 (10)
H4A	0.5165	0.6783	0.0333	0.069*
C5A	0.4555 (2)	0.6196 (2)	0.12157 (18)	0.0450 (8)
C6A	0.40567 (19)	0.6337 (2)	0.18521 (17)	0.0395 (8)
C7A	0.4552 (2)	0.4608 (2)	0.14276 (19)	0.0480 (9)
C8A	0.40041 (19)	0.4741 (2)	0.20780 (17)	0.0392 (8)
C9A	0.37984 (19)	0.5566 (2)	0.22772 (17)	0.0392 (8)
C10A	0.3687 (2)	0.39270 (19)	0.24977 (18)	0.0415 (8)
H10A	0.4182	0.3532	0.2665	0.050*
C11A	0.33376 (19)	0.4208 (2)	0.32967 (17)	0.0382 (8)
C12A	0.3164 (2)	0.5074 (2)	0.34506 (18)	0.0413 (8)
C13A	0.30238 (19)	0.34343 (19)	0.18653 (18)	0.0394 (8)
C14A	0.1765 (2)	0.2990 (2)	0.08913 (18)	0.0489 (9)
H14A	0.1233	0.2933	0.0542	0.059*
C15A	0.3095 (2)	0.2642 (2)	0.14837 (19)	0.0449 (8)
C16A	0.3177 (2)	0.3561 (2)	0.3915 (2)	0.0472 (8)
C17A	0.3257 (3)	0.2039 (2)	0.4303 (2)	0.0780 (13)
H17C	0.2641	0.1987	0.4319	0.094*
H17D	0.3546	0.2182	0.4871	0.094*
C18A	0.3591 (4)	0.1201 (3)	0.4024 (3)	0.132 (2)
H18D	0.3315	0.1071	0.3455	0.198*
H18E	0.3471	0.0733	0.4399	0.198*
H18F	0.4205	0.1248	0.4034	0.198*
C19A	0.3861 (2)	0.2038 (2)	0.1600 (2)	0.0764 (12)
H20X	0.4044	0.1934	0.1059	0.115*
H19X	0.3706	0.1484	0.1834	0.115*
H21X	0.4325	0.2307	0.1981	0.115*
N1	0.27345 (17)	0.26186 (17)	0.90444 (15)	0.0552 (8)
H1B	0.2668	0.2250	0.9442	0.066*
H1C	0.2581	0.3164	0.9082	0.066*
N2	0.2506 (2)	−0.03345 (19)	0.58422 (16)	0.0541 (7)
N1A	0.28373 (18)	0.54145 (17)	0.40989 (15)	0.0577 (8)
H1A1	0.2706	0.5073	0.4493	0.069*
H1A2	0.2756	0.5978	0.4126	0.069*
N2A	0.23690 (18)	0.23858 (17)	0.09262 (15)	0.0473 (7)
O1	0.47619 (13)	0.29715 (14)	0.60465 (11)	0.0430 (5)
O2	0.48555 (14)	0.15115 (14)	0.61402 (13)	0.0505 (6)
O3	0.31266 (13)	0.30626 (12)	0.78376 (12)	0.0434 (5)
O4	0.31017 (17)	0.09227 (14)	0.95117 (14)	0.0642 (7)
O5	0.36704 (17)	0.00778 (15)	0.85867 (13)	0.0666 (7)
O1A	0.47929 (14)	0.53504 (16)	0.10116 (12)	0.0537 (6)
O2A	0.48122 (15)	0.39022 (17)	0.12158 (15)	0.0656 (7)
O3A	0.33117 (14)	0.57478 (12)	0.29067 (12)	0.0453 (6)
O4A	0.28704 (17)	0.36983 (14)	0.45668 (14)	0.0619 (7)
O5A	0.34104 (15)	0.27344 (14)	0.37173 (13)	0.0590 (6)
S1	0.20650 (6)	0.11782 (6)	0.63551 (5)	0.0507 (3)
S1A	0.20197 (5)	0.38856 (5)	0.15289 (5)	0.0484 (3)

	U11	U22	U33	U12	U13	U23
C1	0.049 (2)	0.042 (2)	0.0415 (18)	−0.0003 (16)	0.0142 (15)	0.0060 (16)
C2	0.060 (2)	0.037 (2)	0.053 (2)	−0.0018 (17)	0.0116 (18)	0.0078 (16)
C3	0.064 (2)	0.044 (2)	0.0453 (19)	−0.0088 (18)	0.0071 (17)	0.0127 (16)
C4	0.057 (2)	0.054 (2)	0.0367 (18)	−0.0094 (19)	0.0154 (16)	0.0099 (16)
C5	0.0385 (18)	0.038 (2)	0.0321 (16)	−0.0052 (15)	0.0058 (14)	0.0017 (14)
C6	0.0364 (17)	0.0336 (19)	0.0297 (15)	−0.0022 (15)	0.0054 (13)	0.0035 (13)
C7	0.0371 (18)	0.042 (2)	0.0356 (17)	−0.0046 (16)	0.0073 (14)	−0.0029 (15)
C8	0.0348 (18)	0.0332 (19)	0.0331 (16)	−0.0007 (14)	0.0086 (14)	−0.0013 (13)
C9	0.0341 (18)	0.042 (2)	0.0287 (15)	−0.0054 (15)	0.0091 (13)	0.0040 (14)
C10	0.0395 (18)	0.0319 (18)	0.0375 (16)	−0.0021 (14)	0.0117 (14)	0.0029 (13)
C11	0.0462 (19)	0.0272 (19)	0.0343 (16)	−0.0032 (15)	0.0087 (14)	0.0055 (13)
C12	0.0440 (19)	0.036 (2)	0.0338 (16)	−0.0011 (15)	0.0126 (14)	0.0060 (14)
C13	0.0435 (19)	0.0272 (18)	0.0389 (17)	−0.0025 (14)	0.0122 (14)	0.0020 (13)
C14	0.054 (2)	0.040 (2)	0.0455 (19)	−0.0012 (17)	0.0175 (17)	−0.0026 (15)
C15	0.064 (3)	0.059 (3)	0.047 (2)	−0.018 (2)	0.0033 (18)	−0.0006 (17)
C16	0.062 (2)	0.033 (2)	0.0415 (19)	−0.0010 (17)	0.0118 (17)	−0.0003 (16)
C17	0.229 (6)	0.041 (3)	0.066 (3)	0.024 (3)	0.037 (3)	0.024 (2)
C18	0.152 (5)	0.048 (3)	0.103 (3)	0.003 (3)	−0.018 (3)	0.014 (2)
C19	0.078 (3)	0.054 (3)	0.097 (3)	0.011 (2)	0.024 (2)	−0.020 (2)
C1A	0.055 (2)	0.048 (2)	0.0406 (18)	−0.0030 (18)	0.0042 (16)	0.0028 (16)
C2A	0.060 (2)	0.052 (2)	0.053 (2)	−0.0077 (19)	−0.0011 (19)	0.0086 (18)
C3A	0.066 (3)	0.064 (3)	0.045 (2)	−0.020 (2)	−0.0038 (19)	0.0170 (19)
C4A	0.059 (2)	0.080 (3)	0.0356 (18)	−0.016 (2)	0.0104 (16)	0.0028 (19)
C5A	0.044 (2)	0.055 (2)	0.0348 (17)	−0.0073 (18)	0.0022 (15)	−0.0017 (16)
C6A	0.0421 (19)	0.047 (2)	0.0291 (16)	−0.0042 (16)	0.0041 (14)	0.0013 (14)
C7A	0.045 (2)	0.057 (3)	0.0427 (19)	−0.0045 (19)	0.0114 (16)	−0.0123 (18)
C8A	0.0362 (19)	0.044 (2)	0.0379 (17)	−0.0043 (15)	0.0094 (14)	−0.0087 (15)
C9A	0.0403 (19)	0.045 (2)	0.0329 (17)	−0.0008 (16)	0.0064 (14)	−0.0064 (15)
C10A	0.0434 (19)	0.038 (2)	0.0440 (18)	0.0058 (16)	0.0110 (15)	−0.0054 (15)
C11A	0.045 (2)	0.031 (2)	0.0392 (17)	−0.0036 (15)	0.0090 (15)	−0.0037 (14)
C12A	0.048 (2)	0.041 (2)	0.0375 (18)	−0.0030 (16)	0.0149 (15)	0.0013 (15)
C13A	0.042 (2)	0.0343 (19)	0.0441 (18)	0.0028 (15)	0.0128 (15)	−0.0048 (15)
C14A	0.052 (2)	0.053 (2)	0.0424 (19)	−0.0091 (19)	0.0088 (16)	−0.0053 (16)
C15A	0.047 (2)	0.039 (2)	0.0494 (19)	0.0021 (17)	0.0112 (17)	−0.0092 (16)
C16A	0.056 (2)	0.037 (2)	0.048 (2)	−0.0064 (17)	0.0073 (17)	−0.0043 (16)
C17A	0.114 (4)	0.051 (3)	0.060 (2)	−0.009 (2)	−0.014 (2)	0.015 (2)
C18A	0.224 (7)	0.041 (3)	0.134 (4)	0.026 (3)	0.038 (4)	0.008 (3)
C19A	0.070 (3)	0.059 (3)	0.097 (3)	0.019 (2)	0.002 (2)	−0.029 (2)
N1	0.088 (2)	0.0408 (17)	0.0458 (16)	0.0083 (15)	0.0388 (16)	0.0078 (13)
N2	0.066 (2)	0.0483 (19)	0.0489 (17)	−0.0119 (17)	0.0105 (15)	−0.0081 (14)
N1A	0.090 (2)	0.0409 (17)	0.0509 (17)	0.0079 (15)	0.0370 (16)	0.0016 (13)
N2A	0.0552 (19)	0.0448 (18)	0.0449 (16)	−0.0033 (15)	0.0168 (14)	−0.0096 (13)
O1	0.0501 (14)	0.0427 (14)	0.0400 (12)	−0.0067 (11)	0.0194 (10)	0.0034 (10)
O2	0.0545 (15)	0.0446 (15)	0.0574 (14)	0.0001 (12)	0.0247 (12)	−0.0051 (11)
O3	0.0574 (14)	0.0333 (12)	0.0454 (12)	0.0046 (10)	0.0272 (11)	0.0093 (10)
O4	0.110 (2)	0.0454 (14)	0.0434 (13)	−0.0031 (14)	0.0307 (14)	0.0088 (11)
O5	0.114 (2)	0.0379 (15)	0.0519 (14)	0.0119 (14)	0.0255 (14)	0.0121 (11)
O1A	0.0576 (15)	0.0633 (17)	0.0442 (13)	−0.0056 (13)	0.0208 (11)	−0.0059 (12)
O2A	0.0713 (18)	0.0610 (17)	0.0717 (16)	0.0015 (14)	0.0345 (14)	−0.0232 (13)
O3A	0.0601 (15)	0.0358 (13)	0.0453 (12)	0.0057 (11)	0.0251 (11)	0.0003 (10)
O4A	0.0930 (19)	0.0478 (15)	0.0487 (14)	−0.0059 (13)	0.0231 (13)	0.0018 (11)
O5A	0.0852 (19)	0.0352 (15)	0.0562 (14)	0.0033 (13)	0.0094 (13)	0.0022 (11)
S1	0.0503 (6)	0.0434 (6)	0.0562 (5)	−0.0018 (4)	0.0015 (4)	0.0026 (4)
S1A	0.0482 (5)	0.0384 (5)	0.0594 (5)	0.0043 (4)	0.0107 (4)	−0.0031 (4)

C1—C2	1.365 (4)	C1A—H1A	0.9300
C1—C6	1.392 (4)	C2A—C3A	1.380 (4)
C1—H1	0.9300	C2A—H2A	0.9300
C2—C3	1.387 (4)	C3A—C4A	1.370 (5)
C2—H2	0.9300	C3A—H3A	0.9300
C3—C4	1.372 (4)	C4A—C5A	1.380 (4)
C3—H3	0.9300	C4A—H4A	0.9300
C4—C5	1.375 (4)	C5A—O1A	1.380 (4)
C4—H4	0.9300	C5A—C6A	1.385 (4)
C5—O1	1.382 (3)	C6A—C9A	1.433 (4)
C5—C6	1.384 (4)	C7A—O2A	1.205 (4)
C6—C9	1.433 (4)	C7A—O1A	1.381 (4)
C7—O2	1.209 (3)	C7A—C8A	1.455 (4)
C7—O1	1.383 (3)	C8A—C9A	1.335 (4)
C7—C8	1.439 (4)	C8A—C10A	1.516 (4)
C8—C9	1.336 (4)	C9A—O3A	1.375 (3)
C8—C10	1.507 (4)	C10A—C11A	1.518 (4)
C9—O3	1.372 (3)	C10A—C13A	1.521 (4)
C10—C11	1.516 (4)	C10A—H10A	0.9800
C10—C13	1.521 (4)	C11A—C12A	1.363 (4)
C10—H10	0.9800	C11A—C16A	1.434 (4)
C11—C12	1.355 (4)	C12A—N1A	1.323 (3)
C11—C16	1.442 (4)	C12A—O3A	1.376 (3)
C12—N1	1.326 (3)	C13A—C15A	1.352 (4)
C12—O3	1.385 (3)	C13A—S1A	1.718 (3)
C13—C14	1.364 (4)	C14A—N2A	1.305 (4)
C13—S1	1.713 (3)	C14A—S1A	1.699 (3)
C14—N2	1.387 (4)	C14A—H14A	0.9300
C14—C19	1.494 (5)	C15A—N2A	1.382 (4)
C15—N2	1.294 (4)	C15A—C19A	1.492 (4)
C15—S1	1.715 (3)	C16A—O4A	1.225 (3)
C15—H15	0.9300	C16A—O5A	1.349 (4)
C16—O4	1.209 (3)	C17A—O5A	1.446 (4)
C16—O5	1.344 (4)	C17A—C18A	1.461 (5)
C17—C18	1.406 (5)	C17A—H17C	0.9700
C17—O5	1.463 (4)	C17A—H17D	0.9700
C17—H17A	0.9700	C18A—H18D	0.9600
C17—H17B	0.9700	C18A—H18E	0.9600
C18—H18A	0.9600	C18A—H18F	0.9600
C18—H18B	0.9600	C19A—H20X	0.9600
C18—H18C	0.9600	C19A—H19X	0.9600
C19—H19A	0.9600	C19A—H21X	0.9600
C19—H19B	0.9600	N1—H1B	0.8600
C19—H19C	0.9600	N1—H1C	0.8600
C1A—C2A	1.371 (4)	N1A—H1A1	0.8600
C1A—C6A	1.401 (4)	N1A—H1A2	0.8600
C2—C1—C6	121.0 (3)	C2A—C3A—H3A	119.5
C2—C1—H1	119.5	C3A—C4A—C5A	118.8 (3)
C6—C1—H1	119.5	C3A—C4A—H4A	120.6
C1—C2—C3	119.7 (3)	C5A—C4A—H4A	120.6
C1—C2—H2	120.2	O1A—C5A—C4A	117.2 (3)
C3—C2—H2	120.2	O1A—C5A—C6A	121.1 (3)
C4—C3—C2	120.6 (3)	C4A—C5A—C6A	121.7 (3)
C4—C3—H3	119.7	C5A—C6A—C1A	118.3 (3)
C2—C3—H3	119.7	C5A—C6A—C9A	116.8 (3)
C3—C4—C5	118.9 (3)	C1A—C6A—C9A	124.9 (3)
C3—C4—H4	120.5	O2A—C7A—O1A	116.9 (3)
C5—C4—H4	120.5	O2A—C7A—C8A	125.5 (3)
C4—C5—O1	116.8 (3)	O1A—C7A—C8A	117.6 (3)
C4—C5—C6	121.8 (3)	C9A—C8A—C7A	119.1 (3)
O1—C5—C6	121.4 (3)	C9A—C8A—C10A	122.8 (3)
C5—C6—C1	117.9 (3)	C7A—C8A—C10A	118.1 (3)
C5—C6—C9	116.4 (3)	C8A—C9A—O3A	122.6 (3)
C1—C6—C9	125.7 (3)	C8A—C9A—C6A	123.2 (3)
O2—C7—O1	116.7 (3)	O3A—C9A—C6A	114.2 (3)
O2—C7—C8	125.3 (3)	C8A—C10A—C11A	109.1 (2)
O1—C7—C8	118.0 (3)	C8A—C10A—C13A	109.8 (2)
C9—C8—C7	119.3 (3)	C11A—C10A—C13A	113.2 (2)
C9—C8—C10	122.2 (2)	C8A—C10A—H10A	108.2
C7—C8—C10	118.4 (3)	C11A—C10A—H10A	108.2
C8—C9—O3	122.8 (2)	C13A—C10A—H10A	108.2
C8—C9—C6	123.2 (2)	C12A—C11A—C16A	117.8 (3)
O3—C9—C6	114.0 (2)	C12A—C11A—C10A	121.6 (3)
C8—C10—C11	109.1 (2)	C16A—C11A—C10A	120.5 (3)
C8—C10—C13	111.1 (2)	N1A—C12A—C11A	128.5 (3)
C11—C10—C13	113.8 (2)	N1A—C12A—O3A	109.0 (3)
C8—C10—H10	107.5	C11A—C12A—O3A	122.4 (2)
C11—C10—H10	107.5	C15A—C13A—C10A	129.3 (3)
C13—C10—H10	107.5	C15A—C13A—S1A	110.1 (2)
C12—C11—C16	117.6 (3)	C10A—C13A—S1A	120.6 (2)
C12—C11—C10	121.6 (2)	N2A—C14A—S1A	115.3 (3)
C16—C11—C10	120.7 (3)	N2A—C14A—H14A	122.3
N1—C12—C11	129.2 (3)	S1A—C14A—H14A	122.3
N1—C12—O3	108.9 (3)	C13A—C15A—N2A	114.7 (3)
C11—C12—O3	121.9 (2)	C13A—C15A—C19A	127.1 (3)
C14—C13—C10	128.9 (3)	N2A—C15A—C19A	118.2 (3)
C14—C13—S1	109.6 (2)	O4A—C16A—O5A	120.5 (3)
C10—C13—S1	121.5 (2)	O4A—C16A—C11A	126.8 (3)
C13—C14—N2	115.1 (3)	O5A—C16A—C11A	112.7 (3)
C13—C14—C19	126.7 (3)	O5A—C17A—C18A	109.2 (3)
N2—C14—C19	118.2 (3)	O5A—C17A—H17C	109.8
N2—C15—S1	115.2 (3)	C18A—C17A—H17C	109.8
N2—C15—H15	122.4	O5A—C17A—H17D	109.8
S1—C15—H15	122.4	C18A—C17A—H17D	109.8
O4—C16—O5	121.7 (3)	H17C—C17A—H17D	108.3
O4—C16—C11	126.7 (3)	C17A—C18A—H18D	109.5
O5—C16—C11	111.5 (3)	C17A—C18A—H18E	109.5
C18—C17—O5	110.4 (3)	H18D—C18A—H18E	109.5
C18—C17—H17A	109.6	C17A—C18A—H18F	109.5
O5—C17—H17A	109.6	H18D—C18A—H18F	109.5
C18—C17—H17B	109.6	H18E—C18A—H18F	109.5
O5—C17—H17B	109.6	C15A—C19A—H20X	109.5
H17A—C17—H17B	108.1	C15A—C19A—H19X	109.5
C17—C18—H18A	109.5	H20X—C19A—H19X	109.5
C17—C18—H18B	109.5	C15A—C19A—H21X	109.5
H18A—C18—H18B	109.5	H20X—C19A—H21X	109.5
C17—C18—H18C	109.5	H19X—C19A—H21X	109.5
H18A—C18—H18C	109.5	C12—N1—H1B	120.0
H18B—C18—H18C	109.5	C12—N1—H1C	120.0
C14—C19—H19A	109.5	H1B—N1—H1C	120.0
C14—C19—H19B	109.5	C15—N2—C14	110.4 (3)
H19A—C19—H19B	109.5	C12A—N1A—H1A1	120.0
C14—C19—H19C	109.5	C12A—N1A—H1A2	120.0
H19A—C19—H19C	109.5	H1A1—N1A—H1A2	120.0
H19B—C19—H19C	109.5	C14A—N2A—C15A	110.4 (3)
C2A—C1A—C6A	120.0 (3)	C5—O1—C7	121.6 (2)
C2A—C1A—H1A	120.0	C9—O3—C12	117.7 (2)
C6A—C1A—H1A	120.0	C16—O5—C17	115.7 (3)
C1A—C2A—C3A	120.2 (3)	C5A—O1A—C7A	122.1 (2)
C1A—C2A—H2A	119.9	C9A—O3A—C12A	118.4 (2)
C3A—C2A—H2A	119.9	C16A—O5A—C17A	116.2 (3)
C4A—C3A—C2A	121.0 (3)	C13—S1—C15	89.65 (17)
C4A—C3A—H3A	119.5	C14A—S1A—C13A	89.39 (16)
C6—C1—C2—C3	−1.0 (5)	C7A—C8A—C9A—C6A	3.1 (5)
C1—C2—C3—C4	0.8 (5)	C10A—C8A—C9A—C6A	−176.5 (3)
C2—C3—C4—C5	0.0 (5)	C5A—C6A—C9A—C8A	−1.0 (5)
C3—C4—C5—O1	−179.5 (3)	C1A—C6A—C9A—C8A	178.7 (3)
C3—C4—C5—C6	−0.7 (5)	C5A—C6A—C9A—O3A	179.5 (3)
C4—C5—C6—C1	0.5 (4)	C1A—C6A—C9A—O3A	−0.8 (4)
O1—C5—C6—C1	179.3 (2)	C9A—C8A—C10A—C11A	−15.1 (4)
C4—C5—C6—C9	−178.0 (3)	C7A—C8A—C10A—C11A	165.2 (3)
O1—C5—C6—C9	0.8 (4)	C9A—C8A—C10A—C13A	109.5 (3)
C2—C1—C6—C5	0.3 (5)	C7A—C8A—C10A—C13A	−70.2 (3)
C2—C1—C6—C9	178.7 (3)	C8A—C10A—C11A—C12A	14.3 (4)
O2—C7—C8—C9	178.7 (3)	C13A—C10A—C11A—C12A	−108.3 (3)
O1—C7—C8—C9	−2.0 (4)	C8A—C10A—C11A—C16A	−165.9 (3)
O2—C7—C8—C10	0.9 (5)	C13A—C10A—C11A—C16A	71.4 (4)
O1—C7—C8—C10	−179.8 (2)	C16A—C11A—C12A—N1A	−1.9 (5)
C7—C8—C9—O3	−176.8 (2)	C10A—C11A—C12A—N1A	177.8 (3)
C10—C8—C9—O3	0.9 (4)	C16A—C11A—C12A—O3A	178.7 (3)
C7—C8—C9—C6	2.9 (4)	C10A—C11A—C12A—O3A	−1.6 (5)
C10—C8—C9—C6	−179.4 (3)	C8A—C10A—C13A—C15A	109.8 (3)
C5—C6—C9—C8	−2.3 (4)	C11A—C10A—C13A—C15A	−128.0 (3)
C1—C6—C9—C8	179.4 (3)	C8A—C10A—C13A—S1A	−69.4 (3)
C5—C6—C9—O3	177.5 (2)	C11A—C10A—C13A—S1A	52.8 (3)
C1—C6—C9—O3	−0.9 (4)	C10A—C13A—C15A—N2A	−179.1 (3)
C9—C8—C10—C11	−17.5 (4)	S1A—C13A—C15A—N2A	0.2 (3)
C7—C8—C10—C11	160.3 (3)	C10A—C13A—C15A—C19A	0.6 (5)
C9—C8—C10—C13	108.7 (3)	S1A—C13A—C15A—C19A	179.9 (3)
C7—C8—C10—C13	−73.5 (3)	C12A—C11A—C16A—O4A	2.4 (5)
C8—C10—C11—C12	18.3 (4)	C10A—C11A—C16A—O4A	−177.4 (3)
C13—C10—C11—C12	−106.3 (3)	C12A—C11A—C16A—O5A	−177.0 (3)
C8—C10—C11—C16	−158.2 (3)	C10A—C11A—C16A—O5A	3.3 (4)
C13—C10—C11—C16	77.2 (3)	S1—C15—N2—C14	−1.1 (3)
C16—C11—C12—N1	−5.1 (5)	C13—C14—N2—C15	1.7 (4)
C10—C11—C12—N1	178.3 (3)	C19—C14—N2—C15	−177.3 (3)
C16—C11—C12—O3	173.7 (3)	S1A—C14A—N2A—C15A	−0.9 (3)
C10—C11—C12—O3	−2.9 (4)	C13A—C15A—N2A—C14A	0.4 (4)
C8—C10—C13—C14	116.2 (3)	C19A—C15A—N2A—C14A	−179.2 (3)
C11—C10—C13—C14	−120.3 (3)	C4—C5—O1—C7	178.8 (3)
C8—C10—C13—S1	−65.5 (3)	C6—C5—O1—C7	−0.1 (4)
C11—C10—C13—S1	58.1 (3)	O2—C7—O1—C5	180.0 (3)
C10—C13—C14—N2	176.9 (3)	C8—C7—O1—C5	0.6 (4)
S1—C13—C14—N2	−1.6 (3)	C8—C9—O3—C12	16.9 (4)
C10—C13—C14—C19	−4.1 (5)	C6—C9—O3—C12	−162.8 (2)
S1—C13—C14—C19	177.4 (3)	N1—C12—O3—C9	163.3 (2)
C12—C11—C16—O4	2.6 (5)	C11—C12—O3—C9	−15.8 (4)
C10—C11—C16—O4	179.2 (3)	O4—C16—O5—C17	1.7 (5)
C12—C11—C16—O5	−178.1 (3)	C11—C16—O5—C17	−177.7 (3)
C10—C11—C16—O5	−1.5 (4)	C18—C17—O5—C16	163.9 (4)
C6A—C1A—C2A—C3A	0.0 (5)	C4A—C5A—O1A—C7A	179.7 (3)
C1A—C2A—C3A—C4A	0.2 (5)	C6A—C5A—O1A—C7A	−0.2 (4)
C2A—C3A—C4A—C5A	−0.5 (5)	O2A—C7A—O1A—C5A	−178.2 (3)
C3A—C4A—C5A—O1A	−179.5 (3)	C8A—C7A—O1A—C5A	2.3 (4)
C3A—C4A—C5A—C6A	0.5 (5)	C8A—C9A—O3A—C12A	12.0 (4)
O1A—C5A—C6A—C1A	179.7 (3)	C6A—C9A—O3A—C12A	−168.6 (2)
C4A—C5A—C6A—C1A	−0.2 (5)	N1A—C12A—O3A—C9A	167.9 (3)
O1A—C5A—C6A—C9A	−0.5 (4)	C11A—C12A—O3A—C9A	−12.6 (4)
C4A—C5A—C6A—C9A	179.6 (3)	O4A—C16A—O5A—C17A	1.5 (5)
C2A—C1A—C6A—C5A	−0.1 (5)	C11A—C16A—O5A—C17A	−179.1 (3)
C2A—C1A—C6A—C9A	−179.8 (3)	C18A—C17A—O5A—C16A	−176.8 (4)
O2A—C7A—C8A—C9A	176.8 (3)	C14—C13—S1—C15	0.8 (2)
O1A—C7A—C8A—C9A	−3.7 (4)	C10—C13—S1—C15	−177.8 (2)
O2A—C7A—C8A—C10A	−3.5 (5)	N2—C15—S1—C13	0.2 (3)
O1A—C7A—C8A—C10A	176.0 (2)	N2A—C14A—S1A—C13A	0.9 (2)
C7A—C8A—C9A—O3A	−177.4 (3)	C15A—C13A—S1A—C14A	−0.6 (2)
C10A—C8A—C9A—O3A	2.9 (5)	C10A—C13A—S1A—C14A	178.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4	0.86	2.11	2.698 (3)	125
N1—H1B···N2Ai	0.86	2.49	3.152 (3)	135
N1—H1C···N2ii	0.86	2.27	3.116 (4)	167
N1A—H1A2···N2Aiii	0.86	2.13	2.988 (4)	174
N1A—H1A1···O4A	0.86	2.09	2.690 (3)	126
N1A—H1A1···O4ii	0.86	2.52	2.936 (3)	111

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O4	0.86	2.11	2.698 (3)	125
N1—H1B⋯N2A i	0.86	2.49	3.152 (3)	135
N1—H1C⋯N2ii	0.86	2.27	3.116 (4)	167
N1A—H1A2⋯N2A iii	0.86	2.13	2.988 (4)	174
N1A—H1A1⋯O4A	0.86	2.09	2.690 (3)	126
N1A—H1A1⋯O4ii	0.86	2.52	2.936 (3)	111

Symmetry codes: (i) ; (ii) ; (iii) .