Solid-state structure of cyclic dipeptides: an X-ray and computational study of cis- and trans-diketopiperazines of N-methyl-phenyl­alanine with the thia-pipecolic acids and thia-prolines

Budesinsky, M.; Cisarova, I.; Borremans, F.; Martins, J.C.; Pauwels, E.

doi:10.1107/S2052520617014731

Solid-state structure of cyclic dipeptides: an X-ray and computational study of cis- and trans-diketopiperazines of N-methyl-phenylalanine with the thia-pipecolic acids and thia-prolines

M. Budesinsky, I. Cisarova, F. Borremans, J. C. Martins and E. Pauwels

Ten new crystal structures of cis and trans bicyclic diketopiperazines (DKPs) of thia-pipecolic acid (with sulfur in the β, γ or δ position) or thia-proline (with sulfur in the β or γ position) and N-methyl phenylalanine [(NMe)Phe]: cyclo[(β-S)Pip-(NMe)Phe], cyclo[(γ-S)Pip-(NMe)Phe], cyclo[(δ-S)Pip-(NMe)Phe], cyclo[(β-S)Pro-(NMe)Phe] and cyclo[(γ-S)Pro-(NMe)Phe] were determined with X-ray crystallography. Density functional theory calculations of these molecules in the gas phase succeed in reproducing the observed molecular conformations in the crystal remarkably well. This illustrates the weak to moderate impact of intermolecular packing forces in the absence of classical N—H

O hydrogen bonds. The effect of sulfur on the geometry of the DKP ring and details of amide bond non-planarity are discussed. Molecular flexibility of the DKP ring, as estimated from the calculated deformation energies of its endocyclic ring torsion angles, is not in general the decisive factor for the occurrence of multiple symmetry independent molecules in the unit cell (Z′ > 1), though in some cases a correlation is observed.

Keywords: sulfur-containing cyclic dipeptides; X-ray crystal structures; DFT calculations; molecular flexibility.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520617014731/dk5056sup1.cif Contains datablocks 4a, 4b, 6a, 6b, 8a, 8b, 12a, 12b, 14a, 14b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50564asup2.hkl Contains datablock 4a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50564bsup3.hkl Contains datablock 4b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50566asup4.hkl Contains datablock 6a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50566bsup5.hkl Contains datablock 6b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50568asup6.hkl Contains datablock 8a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk50568bsup7.hkl Contains datablock 8b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk505612asup8.hkl Contains datablock 12a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk505612bsup9.hkl Contains datablock 12b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk505614asup10.hkl Contains datablock 14a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617014731/dk505614bsup11.hkl Contains datablock 14b
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520617014731/dk5056sup12.pdf Fig. S1, Tables S1-S2

CCDC references: 1400449; 1400450; 1400451; 1400452; 1400453; 1400454; 1400455; 1400456; 1400457; 1400458

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997) for (4a), (4b), (6a), (6b), (8a), (8b); Bruker APEX2 for (12a), (12b), (14a), (14b). Cell refinement: COLLECT and DENZO for (4a), (4b), (6a), (6b), (8a), (8b); Bruker SAINT for (12a), (12b), (14a), (14b). Data reduction: COLLECT and DENZO for (4a), (4b), (6a), (6b), (8a), (8b); Bruker SAINT for (12a), (12b), (14a), (14b). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (4a), (4b), (6a), (6b), (8a), (8b); SHELXS97 (Sheldrick, 2008) for (12a), (12b), (14a), (14b). For all structures, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014).

(4a) top

Crystal data top

2(C₁₅H₁₈N₂O₂S)·H₂O	D_x = 1.332 Mg m⁻³
M_r = 598.76	Mo Kα radiation, λ = 0.71070 Å
Trigonal, P3₁	Cell parameters from 54195 reflections
Hall symbol: P 31	θ = 1–27.8°
a = 8.4102 (2) Å	µ = 0.22 mm⁻¹
c = 36.562 (1) Å	T = 150 K
V = 2239.61 (10) Å³	Plate, colourless
Z = 3	0.5 × 0.5 × 0.2 mm
F(000) = 954

Data collection top

Nonius KappaCCD area detector diffractometer	5051 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 26.0°, θ_min = 4.0°
Detector resolution: 9.091 pixels mm^-1	h = −10→10
φ and ω scans to fill the Ewald sphere	k = −8→8
15456 measured reflections	l = −44→44
5110 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0502P)² + 1.5374P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
5110 reflections	Δρ_max = 0.37 e Å⁻³
373 parameters	Δρ_min = −0.28 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: 0.01 (12)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
N11	0.3901 (5)	0.5157 (6)	0.13434 (10)	0.0365 (9)
C12	0.5655 (7)	0.6501 (6)	0.13601 (12)	0.0341 (10)
O12	0.6366 (5)	0.7696 (5)	0.11261 (10)	0.0466 (9)
C13	0.6815 (7)	0.6559 (7)	0.16871 (13)	0.0402 (10)
H13	0.7253	0.7750	0.1806	0.048*
N14	0.5804 (6)	0.5150 (6)	0.19644 (10)	0.0386 (9)
C14	0.6782 (9)	0.5387 (9)	0.23141 (13)	0.0539 (14)
H14A	0.5909	0.4897	0.2510	0.081*
H14B	0.7613	0.6669	0.2356	0.081*
H14C	0.7460	0.4748	0.2303	0.081*
C15	0.4104 (7)	0.3733 (7)	0.19289 (12)	0.0393 (11)
O15	0.3273 (6)	0.2514 (6)	0.21654 (10)	0.0548 (10)
C16	0.3100 (7)	0.3562 (7)	0.15723 (12)	0.0392 (11)
H16	0.1858	0.3298	0.1635	0.047*
S17	0.28769 (18)	0.1535 (2)	0.13302 (4)	0.0487 (3)
C18	0.1582 (7)	0.1636 (8)	0.09461 (17)	0.0515 (13)
H18A	0.1434	0.0724	0.0766	0.062*
H18B	0.0370	0.1349	0.1028	0.062*
C19	0.2546 (8)	0.3543 (9)	0.07682 (13)	0.0519 (14)
H19A	0.3749	0.3817	0.0683	0.062*
H19B	0.1843	0.3533	0.0557	0.062*
C110	0.2756 (8)	0.5003 (8)	0.10224 (14)	0.0475 (12)
H11A	0.1554	0.4739	0.1106	0.057*
H11B	0.3317	0.6167	0.0894	0.057*
C111	0.8543 (7)	0.6530 (7)	0.15442 (13)	0.0389 (10)
H11C	0.9284	0.7638	0.1403	0.047*
H11D	0.9269	0.6553	0.1752	0.047*
C112	0.8127 (5)	0.4905 (6)	0.13119 (12)	0.0293 (9)
C113	0.7797 (6)	0.3272 (7)	0.14774 (14)	0.0346 (10)
H113	0.7882	0.3214	0.1730	0.041*
C114	0.7342 (6)	0.1734 (6)	0.12650 (14)	0.0376 (10)
H114	0.7138	0.0651	0.1375	0.045*
C115	0.7190 (7)	0.1818 (8)	0.08865 (15)	0.0465 (12)
H115	0.6851	0.0777	0.0745	0.056*
C116	0.7538 (7)	0.3434 (7)	0.07204 (13)	0.0420 (12)
H116	0.7466	0.3491	0.0467	0.050*
C117	0.8005 (6)	0.4996 (6)	0.09355 (13)	0.0374 (10)
H117	0.8230	0.6086	0.0825	0.045*
N21	0.3464 (5)	0.5511 (5)	0.29836 (10)	0.0334 (8)
C22	0.4839 (6)	0.7289 (6)	0.29613 (11)	0.0318 (9)
O22	0.6062 (4)	0.7998 (5)	0.31883 (10)	0.0426 (8)
C23	0.4884 (6)	0.8361 (6)	0.26299 (12)	0.0331 (9)
H23	0.6059	0.8741	0.2508	0.040*
N24	0.3462 (5)	0.7350 (5)	0.23596 (9)	0.0335 (8)
C24	0.3699 (9)	0.8292 (8)	0.20022 (13)	0.0484 (12)
H24A	0.3113	0.7392	0.1813	0.073*
H24B	0.4984	0.9036	0.1949	0.073*
H24C	0.3152	0.9056	0.2015	0.073*
C25	0.2004 (6)	0.5682 (6)	0.24092 (12)	0.0349 (10)
O25	0.0815 (5)	0.4888 (5)	0.21737 (9)	0.0453 (8)
C26	0.1824 (6)	0.4705 (6)	0.27707 (12)	0.0323 (9)
H26	0.1521	0.3446	0.2713	0.039*
S27	−0.01290 (17)	0.45711 (18)	0.30100 (4)	0.0396 (3)
C28	0.0017 (7)	0.3327 (7)	0.34046 (14)	0.0422 (11)
H28A	−0.0891	0.3194	0.3584	0.051*
H28B	−0.0275	0.2105	0.3328	0.051*
C29	0.1901 (7)	0.4276 (7)	0.35825 (14)	0.0461 (12)
H29A	0.1892	0.3588	0.3796	0.055*
H29B	0.2204	0.5497	0.3661	0.055*
C210	0.3357 (7)	0.4411 (7)	0.33090 (13)	0.0431 (11)
H21A	0.4545	0.4973	0.3428	0.052*
H21B	0.3052	0.3187	0.3232	0.052*
C211	0.4930 (6)	1.0149 (7)	0.27509 (12)	0.0360 (9)
H21C	0.6037	1.0890	0.2892	0.043*
H21D	0.4982	1.0845	0.2535	0.043*
C212	0.3296 (6)	0.9802 (6)	0.29763 (11)	0.0277 (9)
C213	0.3308 (6)	0.9645 (6)	0.33568 (12)	0.0315 (9)
H213	0.4362	0.9817	0.3475	0.038*
C214	0.1767 (7)	0.9236 (6)	0.35570 (12)	0.0354 (10)
H214	0.1792	0.9148	0.3810	0.042*
C215	0.0169 (6)	0.8953 (6)	0.33857 (12)	0.0329 (9)
H215	−0.0883	0.8628	0.3522	0.040*
C216	0.0161 (6)	0.9160 (6)	0.30082 (12)	0.0354 (10)
H216	−0.0875	0.9045	0.2892	0.042*
C217	0.1693 (6)	0.9534 (6)	0.28075 (12)	0.0307 (9)
H217	0.1660	0.9610	0.2554	0.037*
O1W	−0.0873 (5)	1.0814 (5)	0.21503 (12)	0.0500 (9)
H1W	−0.0615	1.1988	0.2196	0.060*
H2W	0.0174	1.1017	0.2099	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.042 (2)	0.046 (2)	0.0288 (17)	0.027 (2)	0.0031 (16)	0.0087 (16)
C12	0.051 (3)	0.031 (2)	0.029 (2)	0.027 (2)	−0.0001 (19)	−0.0031 (18)
O12	0.066 (2)	0.041 (2)	0.0378 (18)	0.0298 (19)	0.0025 (17)	0.0056 (15)
C13	0.056 (3)	0.043 (3)	0.032 (2)	0.033 (2)	−0.006 (2)	−0.008 (2)
N14	0.055 (3)	0.049 (2)	0.0265 (18)	0.037 (2)	0.0031 (17)	0.0053 (17)
C14	0.076 (4)	0.085 (4)	0.027 (2)	0.060 (4)	−0.015 (2)	−0.015 (3)
C15	0.046 (3)	0.056 (3)	0.028 (2)	0.035 (3)	0.0117 (19)	0.011 (2)
O15	0.062 (2)	0.079 (3)	0.0377 (19)	0.045 (2)	0.0034 (17)	0.0206 (19)
C16	0.045 (3)	0.049 (3)	0.038 (2)	0.035 (2)	0.012 (2)	0.021 (2)
S17	0.0398 (7)	0.0447 (7)	0.0619 (8)	0.0213 (6)	−0.0128 (6)	0.0003 (6)
C18	0.032 (2)	0.053 (3)	0.068 (4)	0.021 (2)	−0.006 (2)	−0.003 (3)
C19	0.051 (3)	0.079 (4)	0.031 (2)	0.037 (3)	−0.002 (2)	0.011 (2)
C110	0.046 (3)	0.056 (3)	0.041 (2)	0.026 (2)	−0.007 (2)	0.010 (2)
C111	0.042 (2)	0.031 (2)	0.042 (3)	0.018 (2)	−0.002 (2)	−0.003 (2)
C112	0.025 (2)	0.025 (2)	0.039 (2)	0.0139 (17)	0.0039 (17)	−0.0022 (17)
C113	0.026 (2)	0.042 (3)	0.041 (2)	0.021 (2)	0.0013 (18)	0.002 (2)
C114	0.034 (2)	0.030 (2)	0.047 (3)	0.016 (2)	0.0045 (19)	−0.0024 (19)
C115	0.045 (3)	0.049 (3)	0.051 (3)	0.028 (2)	0.003 (2)	−0.008 (2)
C116	0.045 (3)	0.057 (3)	0.032 (2)	0.032 (2)	−0.001 (2)	−0.009 (2)
C117	0.036 (2)	0.033 (2)	0.045 (3)	0.019 (2)	0.004 (2)	0.0062 (19)
N21	0.034 (2)	0.035 (2)	0.0365 (19)	0.0214 (18)	−0.0015 (16)	0.0008 (15)
C22	0.026 (2)	0.044 (3)	0.029 (2)	0.019 (2)	0.0039 (17)	0.0017 (18)
O22	0.0287 (17)	0.052 (2)	0.049 (2)	0.0214 (16)	−0.0089 (15)	−0.0032 (16)
C23	0.028 (2)	0.044 (3)	0.036 (2)	0.024 (2)	0.0051 (17)	−0.0015 (19)
N24	0.0333 (19)	0.044 (2)	0.0278 (18)	0.0225 (18)	0.0014 (15)	0.0003 (16)
C24	0.074 (4)	0.054 (3)	0.031 (2)	0.043 (3)	0.009 (2)	0.004 (2)
C25	0.040 (3)	0.036 (2)	0.038 (2)	0.026 (2)	−0.0013 (19)	−0.0061 (19)
O25	0.053 (2)	0.049 (2)	0.0373 (18)	0.0278 (17)	−0.0153 (15)	−0.0084 (14)
C26	0.038 (2)	0.030 (2)	0.034 (2)	0.0203 (19)	−0.0046 (19)	−0.0099 (18)
S27	0.0367 (6)	0.0407 (7)	0.0454 (6)	0.0224 (5)	0.0034 (5)	0.0045 (5)
C28	0.044 (3)	0.045 (3)	0.041 (2)	0.026 (2)	0.008 (2)	0.011 (2)
C29	0.063 (3)	0.040 (3)	0.035 (2)	0.025 (3)	−0.009 (2)	0.003 (2)
C210	0.046 (3)	0.045 (3)	0.042 (3)	0.025 (2)	−0.010 (2)	0.001 (2)
C211	0.036 (2)	0.038 (2)	0.038 (2)	0.022 (2)	0.0040 (19)	0.0088 (19)
C212	0.030 (2)	0.030 (2)	0.0268 (19)	0.0176 (18)	−0.0022 (16)	−0.0043 (16)
C213	0.033 (2)	0.037 (2)	0.030 (2)	0.022 (2)	−0.0065 (17)	−0.0038 (18)
C214	0.046 (3)	0.031 (2)	0.027 (2)	0.018 (2)	0.0025 (19)	−0.0060 (18)
C215	0.035 (2)	0.037 (2)	0.032 (2)	0.0213 (19)	0.0063 (18)	−0.0047 (18)
C216	0.033 (2)	0.035 (2)	0.034 (2)	0.0132 (19)	−0.0074 (18)	−0.0122 (17)
C217	0.031 (2)	0.030 (2)	0.034 (2)	0.0182 (18)	−0.0021 (18)	0.0016 (17)
O1W	0.044 (2)	0.0407 (19)	0.056 (2)	0.0145 (16)	0.0004 (17)	0.0040 (17)

Geometric parameters (Å, º) top

N11—C12	1.338 (6)	N21—C26	1.426 (6)
N11—C16	1.431 (6)	N21—C210	1.482 (6)
N11—C110	1.482 (6)	C22—O22	1.220 (6)
C12—O12	1.224 (6)	C22—C23	1.500 (6)
C12—C13	1.528 (7)	C23—N24	1.454 (6)
C13—N14	1.465 (7)	C23—C211	1.549 (6)
C13—C111	1.556 (7)	C23—H23	0.9800
C13—H13	0.9800	N24—C25	1.336 (6)
N14—C15	1.333 (7)	N24—C24	1.489 (6)
N14—C14	1.479 (6)	C24—H24A	0.9600
C14—H14A	0.9600	C24—H24B	0.9600
C14—H14B	0.9600	C24—H24C	0.9600
C14—H14C	0.9600	C25—O25	1.233 (6)
C15—O15	1.253 (6)	C25—C26	1.524 (6)
C15—C16	1.521 (6)	C26—S27	1.814 (5)
C16—S17	1.845 (5)	C26—H26	0.9800
C16—H16	0.9800	S27—C28	1.822 (5)
S17—C18	1.805 (6)	C28—C29	1.518 (7)
C18—C19	1.534 (8)	C28—H28A	0.9700
C18—H18A	0.9700	C28—H28B	0.9700
C18—H18B	0.9700	C29—C210	1.540 (8)
C19—C110	1.478 (8)	C29—H29A	0.9700
C19—H19A	0.9700	C29—H29B	0.9700
C19—H19B	0.9700	C210—H21A	0.9700
C110—H11A	0.9700	C210—H21B	0.9700
C110—H11B	0.9700	C211—C212	1.500 (6)
C111—C112	1.495 (6)	C211—H21C	0.9700
C111—H11C	0.9700	C211—H21D	0.9700
C111—H11D	0.9700	C212—C217	1.394 (6)
C112—C117	1.385 (6)	C212—C213	1.398 (6)
C112—C113	1.395 (6)	C213—C214	1.374 (6)
C113—C114	1.388 (7)	C213—H213	0.9300
C113—H113	0.9300	C214—C215	1.391 (7)
C114—C115	1.395 (7)	C214—H214	0.9300
C114—H114	0.9300	C215—C216	1.392 (6)
C115—C116	1.380 (7)	C215—H215	0.9300
C115—H115	0.9300	C216—C217	1.376 (6)
C116—C117	1.408 (7)	C216—H216	0.9300
C116—H116	0.9300	C217—H217	0.9300
C117—H117	0.9300	O1W—H1W	0.9138
N21—C22	1.360 (6)	O1W—H2W	0.8308

C12—N11—C16	124.6 (4)	C22—N21—C210	119.2 (4)
C12—N11—C110	120.2 (4)	C26—N21—C210	113.5 (4)
C16—N11—C110	113.6 (4)	O22—C22—N21	122.8 (4)
O12—C12—N11	122.8 (4)	O22—C22—C23	119.6 (4)
O12—C12—C13	118.6 (5)	N21—C22—C23	117.5 (4)
N11—C12—C13	118.6 (4)	N24—C23—C22	115.6 (4)
N14—C13—C12	114.4 (4)	N24—C23—C211	112.0 (4)
N14—C13—C111	112.9 (4)	C22—C23—C211	109.5 (3)
C12—C13—C111	108.8 (4)	N24—C23—H23	106.4
N14—C13—H13	106.8	C22—C23—H23	106.4
C12—C13—H13	106.8	C211—C23—H23	106.4
C111—C13—H13	106.8	C25—N24—C23	125.2 (4)
C15—N14—C13	125.8 (4)	C25—N24—C24	119.1 (4)
C15—N14—C14	118.7 (4)	C23—N24—C24	115.7 (4)
C13—N14—C14	115.5 (5)	N24—C24—H24A	109.5
N14—C14—H14A	109.5	N24—C24—H24B	109.5
N14—C14—H14B	109.5	H24A—C24—H24B	109.5
H14A—C14—H14B	109.5	N24—C24—H24C	109.5
N14—C14—H14C	109.5	H24A—C24—H24C	109.5
H14A—C14—H14C	109.5	H24B—C24—H24C	109.5
H14B—C14—H14C	109.5	O25—C25—N24	123.0 (4)
O15—C15—N14	125.0 (4)	O25—C25—C26	118.6 (4)
O15—C15—C16	117.2 (5)	N24—C25—C26	118.4 (4)
N14—C15—C16	117.7 (4)	N21—C26—C25	113.9 (4)
N11—C16—C15	115.7 (4)	N21—C26—S27	113.4 (3)
N11—C16—S17	111.6 (3)	C25—C26—S27	107.1 (3)
C15—C16—S17	107.1 (3)	N21—C26—H26	107.3
N11—C16—H16	107.4	C25—C26—H26	107.3
C15—C16—H16	107.4	S27—C26—H26	107.3
S17—C16—H16	107.4	C26—S27—C28	95.7 (2)
C18—S17—C16	96.6 (2)	C29—C28—S27	112.9 (4)
C19—C18—S17	111.3 (4)	C29—C28—H28A	109.0
C19—C18—H18A	109.4	S27—C28—H28A	109.0
S17—C18—H18A	109.4	C29—C28—H28B	109.0
C19—C18—H18B	109.4	S27—C28—H28B	109.0
S17—C18—H18B	109.4	H28A—C28—H28B	107.8
H18A—C18—H18B	108.0	C28—C29—C210	110.0 (4)
C110—C19—C18	112.5 (4)	C28—C29—H29A	109.7
C110—C19—H19A	109.1	C210—C29—H29A	109.7
C18—C19—H19A	109.1	C28—C29—H29B	109.7
C110—C19—H19B	109.1	C210—C29—H29B	109.7
C18—C19—H19B	109.1	H29A—C29—H29B	108.2
H19A—C19—H19B	107.8	N21—C210—C29	111.4 (4)
C19—C110—N11	111.9 (4)	N21—C210—H21A	109.3
C19—C110—H11A	109.2	C29—C210—H21A	109.3
N11—C110—H11A	109.2	N21—C210—H21B	109.3
C19—C110—H11B	109.2	C29—C210—H21B	109.3
N11—C110—H11B	109.2	H21A—C210—H21B	108.0
H11A—C110—H11B	107.9	C212—C211—C23	113.1 (4)
C112—C111—C13	114.3 (4)	C212—C211—H21C	109.0
C112—C111—H11C	108.7	C23—C211—H21C	109.0
C13—C111—H11C	108.7	C212—C211—H21D	109.0
C112—C111—H11D	108.7	C23—C211—H21D	109.0
C13—C111—H11D	108.7	H21C—C211—H21D	107.8
H11C—C111—H11D	107.6	C217—C212—C213	118.5 (4)
C117—C112—C113	120.1 (4)	C217—C212—C211	120.4 (4)
C117—C112—C111	120.2 (4)	C213—C212—C211	121.0 (4)
C113—C112—C111	119.6 (4)	C214—C213—C212	120.2 (4)
C114—C113—C112	120.0 (4)	C214—C213—H213	119.9
C114—C113—H113	120.0	C212—C213—H213	119.9
C112—C113—H113	120.0	C213—C214—C215	120.8 (4)
C113—C114—C115	119.8 (5)	C213—C214—H214	119.6
C113—C114—H114	120.1	C215—C214—H214	119.6
C115—C114—H114	120.1	C214—C215—C216	119.3 (4)
C116—C115—C114	120.4 (5)	C214—C215—H215	120.3
C116—C115—H115	119.8	C216—C215—H215	120.3
C114—C115—H115	119.8	C217—C216—C215	119.7 (4)
C115—C116—C117	119.7 (4)	C217—C216—H216	120.2
C115—C116—H116	120.1	C215—C216—H216	120.2
C117—C116—H116	120.1	C216—C217—C212	121.3 (4)
C112—C117—C116	119.8 (4)	C216—C217—H217	119.3
C112—C117—H117	120.1	C212—C217—H217	119.3
C116—C117—H117	120.1	H1W—O1W—H2W	99.5
C22—N21—C26	125.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O25ⁱ	0.91	2.11	2.983 (5)	159
O1W—H2W···O15ⁱ	0.83	2.27	3.037 (5)	154

Symmetry code: (i) x, y+1, z.

(4b) top

Crystal data top

C₁₅H₁₈N₂O₂S	F(000) = 616
M_r = 290.37	D_x = 1.329 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10583 reflections
a = 6.2287 (1) Å	θ = 1–27.5°
b = 8.9737 (3) Å	µ = 0.23 mm⁻¹
c = 25.9694 (7) Å	T = 150 K
V = 1451.55 (7) Å³	Bar, colourless
Z = 4	0.4 × 0.25 × 0.25 mm

Data collection top

Nonius KappaCCD area detector diffractometer	2975 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
Detector resolution: 9.091 pixels mm^-1	h = −8→8
φ and ω scans to fill the Ewald sphere	k = −11→11
11349 measured reflections	l = −33→33
3296 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0234P)² + 0.431P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.073	(Δ/σ)_max = 0.002
S = 1.04	Δρ_max = 0.18 e Å⁻³
3296 reflections	Δρ_min = −0.23 e Å⁻³
183 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.036 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (6)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.4052 (2)	0.92175 (15)	0.68106 (5)	0.0206 (3)
C2	0.6083 (2)	0.91855 (18)	0.66408 (6)	0.0209 (3)
C3	0.6519 (3)	0.85243 (18)	0.61181 (6)	0.0231 (3)
H3	0.7807	0.7903	0.6147	0.028*
N4	0.4801 (2)	0.75947 (16)	0.59111 (5)	0.0226 (3)
C4	0.5337 (3)	0.6728 (2)	0.54519 (6)	0.0311 (4)
H4A	0.4379	0.5894	0.5424	0.047*
H4B	0.6788	0.6375	0.5478	0.047*
H4C	0.5196	0.7346	0.5152	0.047*
C5	0.2757 (2)	0.76196 (18)	0.60745 (6)	0.0217 (3)
C6	0.2306 (2)	0.83673 (19)	0.65878 (6)	0.0202 (3)
H6	0.1072	0.9033	0.6544	0.024*
S7	0.15137 (7)	0.68411 (5)	0.702119 (16)	0.02814 (12)
C8	0.1114 (3)	0.7946 (2)	0.76006 (6)	0.0290 (4)
H8A	−0.0153	0.8562	0.7557	0.035*
H8B	0.0856	0.7282	0.7889	0.035*
O2	0.75784 (18)	0.97884 (13)	0.68699 (4)	0.0280 (3)
O5	0.12814 (18)	0.69978 (14)	0.58448 (4)	0.0292 (3)
C9	0.3017 (3)	0.8936 (2)	0.77244 (6)	0.0268 (4)
H9A	0.4264	0.8318	0.7791	0.032*
H9B	0.2712	0.9500	0.8035	0.032*
C10	0.3527 (3)	1.00125 (18)	0.72882 (6)	0.0242 (3)
H10A	0.2299	1.0655	0.7229	0.029*
H10B	0.4731	1.0636	0.7387	0.029*
C11	0.7055 (3)	0.9840 (2)	0.57508 (6)	0.0291 (4)
H11A	0.8363	1.0320	0.5867	0.035*
H11B	0.7311	0.9452	0.5408	0.035*
C12	0.5283 (3)	1.0979 (2)	0.57273 (6)	0.0271 (4)
C13	0.3553 (3)	1.0807 (2)	0.53912 (7)	0.0322 (4)
H13	0.3518	0.9993	0.5169	0.039*
C14	0.1895 (3)	1.1825 (2)	0.53832 (7)	0.0402 (5)
H14	0.0759	1.1696	0.5155	0.048*
C15	0.1910 (3)	1.3029 (2)	0.57103 (8)	0.0438 (5)
H15	0.0786	1.3710	0.5705	0.053*
C16	0.3615 (4)	1.3220 (2)	0.60485 (7)	0.0445 (5)
H16	0.3632	1.4029	0.6273	0.053*
C17	0.5288 (3)	1.2207 (2)	0.60510 (7)	0.0350 (4)
H17	0.6437	1.2352	0.6274	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0207 (6)	0.0218 (7)	0.0195 (6)	−0.0001 (6)	0.0012 (5)	−0.0019 (6)
C2	0.0176 (7)	0.0217 (8)	0.0234 (8)	0.0032 (6)	−0.0029 (6)	0.0012 (7)
C3	0.0161 (7)	0.0278 (9)	0.0253 (8)	0.0008 (7)	0.0011 (7)	−0.0032 (6)
N4	0.0202 (6)	0.0252 (7)	0.0223 (7)	0.0002 (6)	0.0005 (5)	−0.0040 (6)
C4	0.0292 (9)	0.0361 (10)	0.0281 (8)	0.0005 (8)	0.0032 (7)	−0.0104 (8)
C5	0.0214 (7)	0.0215 (8)	0.0223 (8)	0.0010 (6)	−0.0015 (6)	0.0010 (7)
C6	0.0158 (7)	0.0228 (8)	0.0219 (7)	0.0009 (6)	−0.0005 (6)	0.0015 (7)
S7	0.0314 (2)	0.0253 (2)	0.0278 (2)	−0.00572 (19)	0.00419 (18)	0.00170 (18)
C8	0.0310 (9)	0.0327 (10)	0.0233 (8)	0.0001 (8)	0.0044 (7)	0.0046 (7)
O2	0.0206 (6)	0.0328 (7)	0.0306 (6)	−0.0003 (5)	−0.0043 (5)	−0.0053 (5)
O5	0.0226 (6)	0.0347 (7)	0.0302 (6)	−0.0026 (6)	−0.0042 (5)	−0.0067 (5)
C9	0.0299 (9)	0.0295 (9)	0.0211 (8)	0.0051 (7)	0.0000 (7)	−0.0013 (7)
C10	0.0259 (8)	0.0234 (8)	0.0232 (7)	−0.0001 (7)	0.0032 (7)	−0.0049 (7)
C11	0.0248 (8)	0.0381 (10)	0.0245 (8)	−0.0082 (8)	0.0068 (7)	−0.0027 (8)
C12	0.0322 (9)	0.0287 (10)	0.0205 (8)	−0.0078 (8)	0.0035 (7)	0.0057 (7)
C13	0.0381 (10)	0.0299 (9)	0.0286 (9)	−0.0114 (9)	−0.0043 (8)	0.0076 (7)
C14	0.0400 (10)	0.0381 (11)	0.0425 (10)	−0.0099 (10)	−0.0112 (8)	0.0165 (10)
C15	0.0470 (11)	0.0366 (11)	0.0478 (11)	0.0072 (10)	−0.0025 (9)	0.0144 (10)
C16	0.0671 (13)	0.0327 (10)	0.0339 (9)	0.0075 (12)	−0.0062 (10)	0.0000 (9)
C17	0.0460 (11)	0.0327 (11)	0.0263 (9)	−0.0024 (9)	−0.0077 (8)	0.0021 (8)

Geometric parameters (Å, º) top

N1—C2	1.340 (2)	C8—H8B	0.9700
N1—C6	1.449 (2)	C9—C10	1.522 (2)
N1—C10	1.468 (2)	C9—H9A	0.9700
C2—O2	1.2305 (19)	C9—H9B	0.9700
C2—C3	1.506 (2)	C10—H10A	0.9700
C3—N4	1.459 (2)	C10—H10B	0.9700
C3—C11	1.554 (2)	C11—C12	1.505 (3)
C3—H3	0.9800	C11—H11A	0.9700
N4—C5	1.342 (2)	C11—H11B	0.9700
N4—C4	1.462 (2)	C12—C17	1.386 (3)
C4—H4A	0.9600	C12—C13	1.395 (2)
C4—H4B	0.9600	C13—C14	1.379 (3)
C4—H4C	0.9600	C13—H13	0.9300
C5—O5	1.2297 (19)	C14—C15	1.374 (3)
C5—C6	1.519 (2)	C14—H14	0.9300
C6—S7	1.8400 (16)	C15—C16	1.389 (3)
C6—H6	0.9800	C15—H15	0.9300
S7—C8	1.8189 (17)	C16—C17	1.383 (3)
C8—C9	1.516 (2)	C16—H16	0.9300
C8—H8A	0.9700	C17—H17	0.9300

C2—N1—C6	124.48 (13)	C8—C9—C10	112.15 (14)
C2—N1—C10	119.92 (13)	C8—C9—H9A	109.2
C6—N1—C10	115.21 (12)	C10—C9—H9A	109.2
O2—C2—N1	123.10 (15)	C8—C9—H9B	109.2
O2—C2—C3	118.20 (14)	C10—C9—H9B	109.2
N1—C2—C3	118.36 (13)	H9A—C9—H9B	107.9
N4—C3—C2	115.15 (13)	N1—C10—C9	111.54 (13)
N4—C3—C11	111.44 (13)	N1—C10—H10A	109.3
C2—C3—C11	107.02 (13)	C9—C10—H10A	109.3
N4—C3—H3	107.6	N1—C10—H10B	109.3
C2—C3—H3	107.6	C9—C10—H10B	109.3
C11—C3—H3	107.6	H10A—C10—H10B	108.0
C5—N4—C3	124.71 (13)	C12—C11—C3	112.54 (13)
C5—N4—C4	118.89 (14)	C12—C11—H11A	109.1
C3—N4—C4	115.93 (13)	C3—C11—H11A	109.1
N4—C4—H4A	109.5	C12—C11—H11B	109.1
N4—C4—H4B	109.5	C3—C11—H11B	109.1
H4A—C4—H4B	109.5	H11A—C11—H11B	107.8
N4—C4—H4C	109.5	C17—C12—C13	117.97 (17)
H4A—C4—H4C	109.5	C17—C12—C11	120.90 (16)
H4B—C4—H4C	109.5	C13—C12—C11	121.10 (16)
O5—C5—N4	123.24 (15)	C14—C13—C12	120.98 (18)
O5—C5—C6	119.20 (13)	C14—C13—H13	119.5
N4—C5—C6	117.42 (13)	C12—C13—H13	119.5
N1—C6—C5	116.37 (12)	C15—C14—C13	120.40 (18)
N1—C6—S7	110.43 (10)	C15—C14—H14	119.8
C5—C6—S7	104.93 (11)	C13—C14—H14	119.8
N1—C6—H6	108.3	C14—C15—C16	119.6 (2)
C5—C6—H6	108.3	C14—C15—H15	120.2
S7—C6—H6	108.3	C16—C15—H15	120.2
C8—S7—C6	97.88 (8)	C17—C16—C15	119.84 (19)
C9—C8—S7	112.82 (12)	C17—C16—H16	120.1
C9—C8—H8A	109.0	C15—C16—H16	120.1
S7—C8—H8A	109.0	C16—C17—C12	121.22 (18)
C9—C8—H8B	109.0	C16—C17—H17	119.4
S7—C8—H8B	109.0	C12—C17—H17	119.4
H8A—C8—H8B	107.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.98	2.44	3.3435 (19)	153
C6—H6···O2ⁱⁱ	0.98	2.43	3.2916 (19)	146
C8—H8A···O2ⁱⁱ	0.97	2.53	3.344 (2)	142
C8—H8B···O2ⁱⁱⁱ	0.97	2.52	3.253 (2)	132

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2.

(6a) top

Crystal data top

C₁₅H₁₈N₂O₂S	F(000) = 616
M_r = 290.37	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2yb	Cell parameters from 28687 reflections
a = 7.3126 (1) Å	θ = 1–27.5°
b = 27.1077 (5) Å	µ = 0.23 mm⁻¹
c = 7.3745 (1) Å	T = 150 K
β = 106.0640 (11)°	Plate, colourless
V = 1404.75 (4) Å³	0.42 × 0.42 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD area detector diffractometer	5572 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 27.4°, θ_min = 2.9°
Detector resolution: 9.091 pixels mm^-1	h = −9→9
φ and ω scans to fill the Ewald sphere	k = −35→34
22183 measured reflections	l = −9→9
6211 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0376P)² + 0.3225P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
6211 reflections	Δρ_max = 0.16 e Å⁻³
363 parameters	Δρ_min = −0.22 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: −0.03 (6)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6695 (2)	0.82534 (6)	0.2140 (2)	0.0204 (3)
C2	0.8202 (2)	0.85551 (7)	0.2369 (2)	0.0210 (4)
O2	0.91482 (19)	0.85832 (5)	0.12241 (18)	0.0309 (3)
C3	0.8767 (2)	0.88835 (6)	0.4094 (2)	0.0199 (4)
H3	0.8886	0.9219	0.3641	0.024*
N4	0.7370 (2)	0.89062 (5)	0.5170 (2)	0.0208 (3)
C4	0.7637 (3)	0.92884 (7)	0.6628 (3)	0.0290 (4)
H4A	0.6420	0.9392	0.6746	0.044*
H4B	0.8284	0.9566	0.6281	0.044*
H4C	0.8384	0.9158	0.7812	0.044*
C5	0.6088 (2)	0.85508 (7)	0.5159 (2)	0.0213 (4)
O5	0.51521 (18)	0.85330 (6)	0.63010 (19)	0.0315 (3)
C6	0.5693 (2)	0.81742 (7)	0.3573 (2)	0.0208 (4)
H6	0.4332	0.8198	0.2924	0.025*
C7	0.6024 (3)	0.76511 (7)	0.4384 (3)	0.0249 (4)
H7A	0.5375	0.7613	0.5358	0.030*
H7B	0.7374	0.7602	0.4960	0.030*
S8	0.51661 (8)	0.71900 (2)	0.25788 (7)	0.03646 (13)
C9	0.6426 (3)	0.74036 (8)	0.0920 (3)	0.0343 (5)
H9A	0.7780	0.7351	0.1458	0.041*
H9B	0.6021	0.7211	−0.0230	0.041*
C10	0.6069 (3)	0.79455 (7)	0.0445 (3)	0.0274 (4)
H10A	0.6750	0.8042	−0.0457	0.033*
H10B	0.4722	0.7998	−0.0136	0.033*
C11	1.0765 (2)	0.87324 (7)	0.5329 (3)	0.0241 (4)
H11A	1.1665	0.8762	0.4584	0.029*
H11B	1.1155	0.8960	0.6380	0.029*
C12	1.0851 (2)	0.82146 (7)	0.6089 (3)	0.0219 (4)
C13	1.1236 (2)	0.78173 (7)	0.5059 (3)	0.0268 (4)
H13	1.1437	0.7872	0.3884	0.032*
C14	1.1325 (3)	0.73414 (8)	0.5757 (3)	0.0370 (5)
H14	1.1585	0.7079	0.5054	0.044*
C15	1.1026 (3)	0.72561 (8)	0.7511 (4)	0.0426 (6)
H15	1.1096	0.6937	0.7988	0.051*
C16	1.0626 (3)	0.76446 (9)	0.8540 (3)	0.0393 (5)
H16	1.0416	0.7588	0.9710	0.047*
C17	1.0536 (3)	0.81206 (8)	0.7832 (3)	0.0285 (4)
H17	1.0260	0.8381	0.8534	0.034*
N21	1.0345 (2)	0.52543 (5)	1.0909 (2)	0.0205 (3)
C22	1.0110 (2)	0.49609 (7)	0.9391 (2)	0.0211 (3)
O22	1.12701 (18)	0.49369 (5)	0.84587 (19)	0.0306 (3)
C23	0.8353 (2)	0.46406 (7)	0.8797 (2)	0.0203 (4)
H23	0.8792	0.4305	0.8652	0.024*
N24	0.7251 (2)	0.46122 (6)	1.0170 (2)	0.0211 (3)
C24	0.5776 (3)	0.42313 (7)	0.9868 (3)	0.0287 (4)
H24A	0.5687	0.4111	1.1065	0.043*
H24B	0.6100	0.3964	0.9161	0.043*
H24C	0.4576	0.4369	0.9179	0.043*
C25	0.7300 (2)	0.49543 (7)	1.1490 (2)	0.0210 (4)
O25	0.61701 (19)	0.49628 (5)	1.24486 (18)	0.0313 (3)
C26	0.8884 (3)	0.53334 (7)	1.1898 (2)	0.0211 (4)
H26	0.9529	0.5310	1.3250	0.025*
C27	0.8058 (3)	0.58555 (7)	1.1555 (3)	0.0266 (4)
H27A	0.7082	0.5895	1.2206	0.032*
H27B	0.7467	0.5901	1.0216	0.032*
S28	0.98609 (8)	0.632028 (19)	1.23693 (8)	0.03969 (15)
C29	1.1537 (3)	0.61042 (8)	1.1143 (3)	0.0380 (5)
H29A	1.0993	0.6150	0.9797	0.046*
H29B	1.2688	0.6301	1.1529	0.046*
C210	1.2044 (3)	0.55644 (7)	1.1538 (3)	0.0298 (4)
H21A	1.2970	0.5467	1.0885	0.036*
H21B	1.2612	0.5518	1.2880	0.036*
C211	0.7127 (3)	0.48051 (7)	0.6822 (2)	0.0256 (4)
H21C	0.7873	0.4769	0.5928	0.031*
H21D	0.6037	0.4587	0.6425	0.031*
C212	0.6428 (3)	0.53313 (7)	0.6757 (2)	0.0228 (4)
C213	0.7540 (3)	0.57185 (7)	0.6387 (3)	0.0270 (4)
H213	0.8712	0.5649	0.6178	0.032*
C214	0.6922 (3)	0.62023 (8)	0.6327 (3)	0.0334 (5)
H214	0.7675	0.6456	0.6080	0.040*
C215	0.5181 (3)	0.63075 (9)	0.6635 (3)	0.0381 (5)
H215	0.4759	0.6632	0.6594	0.046*
C216	0.4071 (3)	0.59288 (9)	0.7004 (3)	0.0373 (5)
H216	0.2899	0.5999	0.7207	0.045*
C217	0.4696 (3)	0.54443 (8)	0.7073 (3)	0.0287 (4)
H217	0.3943	0.5193	0.7334	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0234 (7)	0.0190 (7)	0.0191 (7)	−0.0015 (6)	0.0063 (6)	−0.0008 (6)
C2	0.0228 (8)	0.0184 (9)	0.0217 (8)	0.0007 (7)	0.0062 (7)	0.0019 (7)
O2	0.0368 (7)	0.0333 (8)	0.0284 (7)	−0.0069 (6)	0.0191 (6)	−0.0027 (6)
C3	0.0193 (8)	0.0179 (9)	0.0241 (9)	−0.0027 (7)	0.0084 (7)	−0.0012 (7)
N4	0.0199 (7)	0.0198 (8)	0.0241 (8)	0.0008 (6)	0.0083 (6)	−0.0033 (6)
C4	0.0310 (10)	0.0252 (10)	0.0313 (10)	0.0022 (8)	0.0094 (8)	−0.0084 (8)
C5	0.0165 (7)	0.0239 (9)	0.0231 (8)	0.0020 (7)	0.0047 (7)	0.0014 (7)
O5	0.0248 (6)	0.0415 (8)	0.0327 (7)	−0.0019 (6)	0.0154 (6)	−0.0017 (6)
C6	0.0170 (8)	0.0205 (9)	0.0235 (9)	−0.0004 (7)	0.0036 (7)	0.0021 (7)
C7	0.0243 (9)	0.0241 (10)	0.0251 (9)	−0.0023 (7)	0.0046 (7)	0.0035 (8)
S8	0.0470 (3)	0.0228 (3)	0.0361 (3)	−0.0120 (2)	0.0056 (2)	0.0013 (2)
C9	0.0483 (12)	0.0237 (10)	0.0310 (11)	−0.0027 (9)	0.0113 (10)	−0.0046 (8)
C10	0.0335 (10)	0.0256 (10)	0.0207 (9)	−0.0033 (8)	0.0036 (8)	−0.0026 (8)
C11	0.0189 (8)	0.0232 (9)	0.0300 (9)	−0.0029 (7)	0.0065 (8)	−0.0010 (7)
C12	0.0134 (7)	0.0242 (9)	0.0266 (9)	−0.0009 (7)	0.0028 (7)	−0.0008 (7)
C13	0.0174 (8)	0.0305 (11)	0.0315 (10)	0.0002 (7)	0.0052 (8)	−0.0046 (8)
C14	0.0252 (9)	0.0259 (11)	0.0543 (14)	0.0037 (8)	0.0018 (9)	−0.0065 (9)
C15	0.0311 (11)	0.0302 (12)	0.0584 (15)	−0.0021 (9)	−0.0009 (10)	0.0160 (11)
C16	0.0319 (11)	0.0508 (14)	0.0336 (11)	0.0017 (10)	0.0066 (9)	0.0171 (10)
C17	0.0214 (9)	0.0360 (12)	0.0268 (10)	0.0021 (8)	0.0046 (8)	−0.0010 (8)
N21	0.0188 (7)	0.0191 (7)	0.0236 (7)	−0.0020 (6)	0.0060 (6)	−0.0021 (6)
C22	0.0215 (8)	0.0182 (9)	0.0241 (8)	0.0004 (7)	0.0071 (7)	0.0016 (7)
O22	0.0267 (7)	0.0326 (8)	0.0381 (7)	−0.0030 (6)	0.0184 (6)	−0.0050 (6)
C23	0.0218 (8)	0.0187 (9)	0.0213 (8)	−0.0002 (7)	0.0079 (7)	−0.0029 (7)
N24	0.0229 (7)	0.0200 (8)	0.0211 (7)	−0.0042 (6)	0.0074 (6)	−0.0007 (6)
C24	0.0268 (9)	0.0270 (10)	0.0329 (10)	−0.0082 (8)	0.0090 (8)	0.0004 (8)
C25	0.0235 (8)	0.0222 (9)	0.0173 (8)	0.0021 (7)	0.0055 (7)	0.0030 (7)
O25	0.0331 (7)	0.0396 (8)	0.0260 (7)	−0.0021 (6)	0.0162 (6)	−0.0015 (6)
C26	0.0245 (9)	0.0211 (9)	0.0169 (8)	0.0017 (7)	0.0044 (7)	−0.0013 (7)
C27	0.0288 (10)	0.0225 (10)	0.0268 (9)	0.0040 (7)	0.0048 (8)	−0.0021 (8)
S28	0.0426 (3)	0.0207 (3)	0.0504 (3)	−0.0008 (2)	0.0039 (3)	−0.0115 (2)
C29	0.0370 (12)	0.0255 (11)	0.0501 (13)	−0.0110 (9)	0.0093 (10)	−0.0016 (10)
C210	0.0224 (9)	0.0285 (11)	0.0364 (11)	−0.0058 (8)	0.0045 (8)	−0.0025 (8)
C211	0.0312 (10)	0.0280 (10)	0.0175 (8)	−0.0028 (8)	0.0064 (8)	−0.0042 (7)
C212	0.0262 (9)	0.0265 (10)	0.0143 (8)	−0.0008 (7)	0.0035 (7)	−0.0005 (7)
C213	0.0293 (10)	0.0319 (11)	0.0216 (9)	0.0024 (8)	0.0101 (8)	0.0032 (8)
C214	0.0416 (12)	0.0298 (12)	0.0285 (10)	0.0007 (9)	0.0091 (9)	0.0064 (8)
C215	0.0462 (12)	0.0328 (12)	0.0323 (11)	0.0135 (10)	0.0057 (10)	0.0049 (9)
C216	0.0282 (11)	0.0507 (14)	0.0326 (11)	0.0141 (10)	0.0078 (9)	0.0051 (10)
C217	0.0241 (9)	0.0384 (12)	0.0224 (9)	−0.0006 (8)	0.0045 (8)	0.0034 (8)

Geometric parameters (Å, º) top

N1—C2	1.345 (2)	N21—C22	1.345 (2)
N1—C6	1.459 (2)	N21—C210	1.465 (2)
N1—C10	1.467 (2)	N21—C26	1.467 (2)
C2—O2	1.233 (2)	C22—O22	1.233 (2)
C2—C3	1.514 (2)	C22—C23	1.512 (2)
C3—N4	1.459 (2)	C23—N24	1.461 (2)
C3—C11	1.547 (3)	C23—C211	1.549 (2)
C3—H3	0.9800	C23—H23	0.9800
N4—C5	1.343 (2)	N24—C25	1.338 (2)
N4—C4	1.467 (2)	N24—C24	1.465 (2)
C4—H4A	0.9600	C24—H24A	0.9600
C4—H4B	0.9600	C24—H24B	0.9600
C4—H4C	0.9600	C24—H24C	0.9600
C5—O5	1.224 (2)	C25—O25	1.227 (2)
C5—C6	1.519 (3)	C25—C26	1.515 (3)
C6—C7	1.532 (3)	C26—C27	1.532 (3)
C6—H6	0.9800	C26—H26	0.9800
C7—S8	1.8072 (19)	C27—S28	1.802 (2)
C7—H7A	0.9700	C27—H27A	0.9700
C7—H7B	0.9700	C27—H27B	0.9700
S8—C9	1.817 (2)	S28—C29	1.810 (2)
C9—C10	1.516 (3)	C29—C210	1.518 (3)
C9—H9A	0.9700	C29—H29A	0.9700
C9—H9B	0.9700	C29—H29B	0.9700
C10—H10A	0.9700	C210—H21A	0.9700
C10—H10B	0.9700	C210—H21B	0.9700
C11—C12	1.506 (3)	C211—C212	1.512 (3)
C11—H11A	0.9700	C211—H21C	0.9700
C11—H11B	0.9700	C211—H21D	0.9700
C12—C17	1.391 (3)	C212—C217	1.384 (3)
C12—C13	1.391 (3)	C212—C213	1.400 (3)
C13—C14	1.384 (3)	C213—C214	1.384 (3)
C13—H13	0.9300	C213—H213	0.9300
C14—C15	1.389 (4)	C214—C215	1.384 (3)
C14—H14	0.9300	C214—H214	0.9300
C15—C16	1.376 (4)	C215—C216	1.381 (3)
C15—H15	0.9300	C215—H215	0.9300
C16—C17	1.387 (3)	C216—C217	1.387 (3)
C16—H16	0.9300	C216—H216	0.9300
C17—H17	0.9300	C217—H217	0.9300

C2—N1—C6	123.85 (14)	C22—N21—C210	120.33 (15)
C2—N1—C10	120.27 (15)	C22—N21—C26	123.87 (14)
C6—N1—C10	115.66 (14)	C210—N21—C26	115.43 (14)
O2—C2—N1	123.18 (16)	O22—C22—N21	123.10 (16)
O2—C2—C3	117.70 (15)	O22—C22—C23	117.95 (15)
N1—C2—C3	119.12 (14)	N21—C22—C23	118.94 (14)
N4—C3—C2	114.38 (14)	N24—C23—C22	114.64 (14)
N4—C3—C11	112.35 (14)	N24—C23—C211	112.34 (14)
C2—C3—C11	109.43 (14)	C22—C23—C211	109.38 (15)
N4—C3—H3	106.7	N24—C23—H23	106.7
C2—C3—H3	106.7	C22—C23—H23	106.7
C11—C3—H3	106.7	C211—C23—H23	106.7
C5—N4—C3	124.02 (14)	C25—N24—C23	124.01 (14)
C5—N4—C4	117.57 (15)	C25—N24—C24	118.03 (15)
C3—N4—C4	117.21 (14)	C23—N24—C24	117.11 (14)
N4—C4—H4A	109.5	N24—C24—H24A	109.5
N4—C4—H4B	109.5	N24—C24—H24B	109.5
H4A—C4—H4B	109.5	H24A—C24—H24B	109.5
N4—C4—H4C	109.5	N24—C24—H24C	109.5
H4A—C4—H4C	109.5	H24A—C24—H24C	109.5
H4B—C4—H4C	109.5	H24B—C24—H24C	109.5
O5—C5—N4	123.10 (17)	O25—C25—N24	123.05 (16)
O5—C5—C6	118.68 (15)	O25—C25—C26	118.20 (15)
N4—C5—C6	118.10 (14)	N24—C25—C26	118.67 (14)
N1—C6—C5	115.62 (14)	N21—C26—C25	115.12 (14)
N1—C6—C7	111.25 (14)	N21—C26—C27	111.14 (15)
C5—C6—C7	110.23 (14)	C25—C26—C27	110.45 (14)
N1—C6—H6	106.4	N21—C26—H26	106.5
C5—C6—H6	106.4	C25—C26—H26	106.5
C7—C6—H6	106.4	C27—C26—H26	106.5
C6—C7—S8	111.56 (12)	C26—C27—S28	111.88 (13)
C6—C7—H7A	109.3	C26—C27—H27A	109.2
S8—C7—H7A	109.3	S28—C27—H27A	109.2
C6—C7—H7B	109.3	C26—C27—H27B	109.2
S8—C7—H7B	109.3	S28—C27—H27B	109.2
H7A—C7—H7B	108.0	H27A—C27—H27B	107.9
C7—S8—C9	97.94 (9)	C27—S28—C29	98.12 (9)
C10—C9—S8	112.20 (15)	C210—C29—S28	112.30 (16)
C10—C9—H9A	109.2	C210—C29—H29A	109.1
S8—C9—H9A	109.2	S28—C29—H29A	109.1
C10—C9—H9B	109.2	C210—C29—H29B	109.1
S8—C9—H9B	109.2	S28—C29—H29B	109.1
H9A—C9—H9B	107.9	H29A—C29—H29B	107.9
N1—C10—C9	111.16 (16)	N21—C210—C29	110.59 (16)
N1—C10—H10A	109.4	N21—C210—H21A	109.5
C9—C10—H10A	109.4	C29—C210—H21A	109.5
N1—C10—H10B	109.4	N21—C210—H21B	109.5
C9—C10—H10B	109.4	C29—C210—H21B	109.5
H10A—C10—H10B	108.0	H21A—C210—H21B	108.1
C12—C11—C3	113.65 (14)	C212—C211—C23	113.86 (14)
C12—C11—H11A	108.8	C212—C211—H21C	108.8
C3—C11—H11A	108.8	C23—C211—H21C	108.8
C12—C11—H11B	108.8	C212—C211—H21D	108.8
C3—C11—H11B	108.8	C23—C211—H21D	108.8
H11A—C11—H11B	107.7	H21C—C211—H21D	107.7
C17—C12—C13	118.23 (18)	C217—C212—C213	118.36 (18)
C17—C12—C11	120.96 (17)	C217—C212—C211	121.38 (18)
C13—C12—C11	120.80 (17)	C213—C212—C211	120.25 (17)
C14—C13—C12	120.97 (19)	C214—C213—C212	120.95 (18)
C14—C13—H13	119.5	C214—C213—H213	119.5
C12—C13—H13	119.5	C212—C213—H213	119.5
C13—C14—C15	119.9 (2)	C215—C214—C213	119.8 (2)
C13—C14—H14	120.1	C215—C214—H214	120.1
C15—C14—H14	120.1	C213—C214—H214	120.1
C16—C15—C14	119.9 (2)	C216—C215—C214	119.8 (2)
C16—C15—H15	120.1	C216—C215—H215	120.1
C14—C15—H15	120.1	C214—C215—H215	120.1
C15—C16—C17	120.0 (2)	C215—C216—C217	120.37 (19)
C15—C16—H16	120.0	C215—C216—H216	119.8
C17—C16—H16	120.0	C217—C216—H216	119.8
C16—C17—C12	121.0 (2)	C212—C217—C216	120.7 (2)
C16—C17—H17	119.5	C212—C217—H217	119.6
C12—C17—H17	119.5	C216—C217—H217	119.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O22ⁱ	0.98	2.47	3.416 (2)	162
C11—H11A···O5ⁱⁱ	0.97	2.59	3.135 (2)	116
C17—H17···O2ⁱⁱⁱ	0.93	2.41	3.204 (2)	144
C211—H21C···O25^iv	0.97	2.58	3.135 (2)	117
C23—H23···O2^v	0.98	2.46	3.402 (2)	162
C217—H217···O22^vi	0.93	2.43	3.260 (2)	149

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

(6b) top

Crystal data top

C₁₅H₁₈N₂O₂S	F(000) = 616
M_r = 290.37	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2yb	Cell parameters from 16855 reflections
a = 9.8928 (2) Å	θ = 1–27.5°
b = 9.0312 (2) Å	µ = 0.23 mm⁻¹
c = 16.4470 (5) Å	T = 150 K
β = 97.8246 (15)°	Bar, colourless
V = 1455.76 (6) Å³	0.5 × 0.15 × 0.1 mm
Z = 4

Data collection top

Nonius KappaCCD area detector diffractometer	5781 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
Detector resolution: 9.091 pixels mm^-1	h = −12→12
φ and ω scans to fill the Ewald sphere	k = −11→11
23095 measured reflections	l = −21→21
6621 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0316P)² + 0.3753P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
6621 reflections	Δρ_max = 0.22 e Å⁻³
363 parameters	Δρ_min = −0.22 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: −0.06 (5)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.26974 (15)	0.09585 (17)	0.37766 (9)	0.0226 (3)
C2	0.36775 (19)	0.04534 (19)	0.33489 (11)	0.0231 (4)
O2	0.34415 (14)	−0.03944 (14)	0.27615 (8)	0.0323 (3)
C3	0.51233 (19)	0.0982 (2)	0.35878 (12)	0.0248 (4)
H3	0.5720	0.0112	0.3610	0.030*
N4	0.53693 (14)	0.17062 (17)	0.43830 (9)	0.0237 (3)
C4	0.67909 (19)	0.1838 (3)	0.47573 (13)	0.0359 (5)
H4A	0.7204	0.2671	0.4525	0.054*
H4B	0.7276	0.0951	0.4655	0.054*
H4C	0.6827	0.1979	0.5338	0.054*
C5	0.44075 (19)	0.24650 (19)	0.47023 (11)	0.0236 (4)
O5	0.46557 (13)	0.33206 (15)	0.52862 (8)	0.0319 (3)
C6	0.29172 (18)	0.21877 (19)	0.43574 (11)	0.0222 (4)
H6	0.2552	0.3090	0.4079	0.027*
C7	0.21595 (18)	0.1919 (2)	0.50931 (12)	0.0302 (4)
H7A	0.2340	0.2737	0.5474	0.036*
H7B	0.2513	0.1026	0.5373	0.036*
S8	0.03443 (5)	0.17300 (7)	0.48181 (3)	0.03746 (13)
C9	0.0414 (2)	0.0221 (2)	0.41060 (13)	0.0341 (5)
H9A	0.0791	−0.0646	0.4402	0.041*
H9B	−0.0504	−0.0018	0.3853	0.041*
C10	0.12734 (19)	0.0608 (2)	0.34480 (12)	0.0303 (4)
H10A	0.1264	−0.0218	0.3070	0.036*
H10B	0.0872	0.1453	0.3141	0.036*
C11	0.54995 (19)	0.2002 (2)	0.28941 (12)	0.0281 (4)
H11A	0.6460	0.2251	0.3008	0.034*
H11B	0.5360	0.1462	0.2380	0.034*
C12	0.46810 (18)	0.3411 (2)	0.27977 (11)	0.0258 (4)
C13	0.5105 (2)	0.4683 (2)	0.32414 (12)	0.0290 (4)
H13	0.5908	0.4660	0.3609	0.035*
C14	0.4355 (2)	0.5978 (2)	0.31452 (13)	0.0319 (4)
H14	0.4660	0.6818	0.3442	0.038*
C15	0.3155 (2)	0.6026 (2)	0.26090 (13)	0.0328 (5)
H15	0.2649	0.6896	0.2544	0.039*
C16	0.2707 (2)	0.4774 (2)	0.21691 (14)	0.0354 (5)
H16	0.1891	0.4797	0.1814	0.042*
C17	0.34728 (19)	0.3483 (2)	0.22556 (12)	0.0298 (4)
H17	0.3175	0.2654	0.1947	0.036*
N21	0.79215 (15)	0.66563 (17)	0.22461 (9)	0.0244 (3)
C22	0.73000 (18)	0.7944 (2)	0.23921 (11)	0.0229 (4)
O22	0.76346 (13)	0.87162 (14)	0.29992 (8)	0.0300 (3)
C23	0.61717 (17)	0.8489 (2)	0.17468 (10)	0.0225 (4)
H23	0.5458	0.8911	0.2035	0.027*
N24	0.55451 (16)	0.73322 (16)	0.12097 (9)	0.0253 (3)
C24	0.4176 (2)	0.7611 (2)	0.07789 (14)	0.0361 (5)
H24A	0.4244	0.8041	0.0252	0.054*
H24B	0.3703	0.8280	0.1095	0.054*
H24C	0.3683	0.6694	0.0706	0.054*
C25	0.6247 (2)	0.6169 (2)	0.09895 (12)	0.0305 (4)
O25	0.57947 (18)	0.53368 (18)	0.04268 (10)	0.0502 (4)
C26	0.76157 (19)	0.5811 (2)	0.14838 (11)	0.0250 (4)
H26	0.8334	0.6001	0.1142	0.030*
C27	0.7582 (2)	0.4150 (2)	0.16631 (13)	0.0292 (4)
H27A	0.7385	0.3623	0.1147	0.035*
H27B	0.6841	0.3954	0.1979	0.035*
S28	0.91319 (6)	0.34311 (6)	0.22139 (3)	0.03858 (14)
C29	0.9283 (2)	0.4728 (2)	0.30545 (13)	0.0379 (5)
H29A	0.8550	0.4558	0.3380	0.046*
H29B	1.0141	0.4563	0.3404	0.046*
C210	0.9224 (2)	0.6310 (2)	0.27577 (13)	0.0318 (5)
H21A	0.9345	0.6969	0.3228	0.038*
H21B	0.9968	0.6484	0.2442	0.038*
C211	0.67422 (19)	0.9770 (2)	0.12559 (12)	0.0257 (4)
H21C	0.6033	1.0106	0.0830	0.031*
H21D	0.6992	1.0596	0.1623	0.031*
C212	0.7969 (2)	0.9300 (2)	0.08679 (12)	0.0271 (4)
C213	0.7833 (2)	0.8635 (2)	0.00970 (12)	0.0344 (5)
H213	0.6976	0.8564	−0.0213	0.041*
C214	0.8968 (3)	0.8079 (3)	−0.02118 (14)	0.0482 (6)
H214	0.8865	0.7609	−0.0720	0.058*
C215	1.0254 (3)	0.8222 (3)	0.02349 (15)	0.0580 (7)
H215	1.1014	0.7853	0.0026	0.070*
C216	1.0402 (2)	0.8911 (3)	0.09866 (15)	0.0495 (7)
H216	1.1265	0.9015	0.1285	0.059*
C217	0.9277 (2)	0.9447 (2)	0.12983 (13)	0.0359 (5)
H217	0.9390	0.9916	0.1806	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0204 (7)	0.0213 (7)	0.0257 (8)	0.0002 (6)	0.0012 (6)	−0.0042 (6)
C2	0.0299 (10)	0.0158 (8)	0.0240 (9)	0.0038 (7)	0.0053 (8)	0.0024 (7)
O2	0.0402 (8)	0.0252 (7)	0.0327 (7)	−0.0007 (6)	0.0095 (6)	−0.0085 (6)
C3	0.0262 (9)	0.0177 (8)	0.0318 (10)	0.0035 (8)	0.0083 (8)	0.0018 (8)
N4	0.0182 (7)	0.0239 (7)	0.0286 (8)	0.0015 (7)	0.0018 (6)	0.0003 (7)
C4	0.0207 (9)	0.0415 (11)	0.0450 (12)	0.0004 (9)	0.0020 (9)	0.0040 (11)
C5	0.0258 (9)	0.0193 (9)	0.0254 (9)	−0.0004 (7)	0.0030 (8)	0.0015 (8)
O5	0.0317 (7)	0.0316 (7)	0.0311 (7)	−0.0041 (6)	−0.0002 (6)	−0.0095 (6)
C6	0.0227 (9)	0.0195 (9)	0.0240 (9)	0.0024 (7)	0.0017 (7)	−0.0013 (7)
C7	0.0244 (9)	0.0397 (11)	0.0261 (9)	−0.0019 (9)	0.0022 (8)	−0.0048 (9)
S8	0.0222 (2)	0.0525 (3)	0.0387 (3)	0.0000 (2)	0.0078 (2)	−0.0081 (3)
C9	0.0221 (10)	0.0367 (11)	0.0426 (12)	−0.0052 (9)	0.0013 (9)	−0.0015 (10)
C10	0.0245 (10)	0.0338 (11)	0.0307 (11)	0.0006 (8)	−0.0037 (8)	−0.0057 (9)
C11	0.0289 (10)	0.0236 (9)	0.0343 (11)	0.0002 (8)	0.0128 (8)	0.0012 (8)
C12	0.0299 (10)	0.0225 (8)	0.0274 (9)	−0.0021 (8)	0.0125 (8)	0.0029 (8)
C13	0.0288 (10)	0.0257 (10)	0.0317 (10)	−0.0031 (8)	0.0016 (8)	0.0000 (8)
C14	0.0385 (12)	0.0217 (9)	0.0369 (11)	−0.0029 (9)	0.0096 (9)	−0.0035 (9)
C15	0.0366 (11)	0.0221 (9)	0.0408 (12)	0.0054 (9)	0.0089 (9)	0.0027 (9)
C16	0.0317 (11)	0.0312 (11)	0.0413 (12)	0.0014 (9)	−0.0024 (9)	0.0012 (9)
C17	0.0365 (11)	0.0218 (9)	0.0305 (10)	−0.0045 (9)	0.0026 (8)	−0.0038 (9)
N21	0.0256 (8)	0.0240 (8)	0.0227 (8)	0.0044 (7)	−0.0002 (6)	0.0000 (7)
C22	0.0228 (9)	0.0235 (9)	0.0232 (10)	−0.0017 (7)	0.0057 (8)	0.0006 (7)
O22	0.0350 (7)	0.0298 (7)	0.0249 (7)	0.0010 (6)	0.0030 (6)	−0.0064 (6)
C23	0.0231 (9)	0.0220 (8)	0.0226 (9)	0.0023 (8)	0.0035 (7)	−0.0037 (8)
N24	0.0229 (8)	0.0252 (8)	0.0264 (8)	0.0000 (6)	−0.0013 (6)	−0.0012 (7)
C24	0.0279 (11)	0.0348 (11)	0.0421 (12)	−0.0006 (9)	−0.0085 (9)	0.0054 (10)
C25	0.0362 (11)	0.0246 (10)	0.0287 (10)	0.0011 (9)	−0.0026 (9)	−0.0016 (8)
O25	0.0594 (11)	0.0387 (9)	0.0449 (9)	0.0107 (8)	−0.0198 (8)	−0.0166 (8)
C26	0.0297 (10)	0.0223 (9)	0.0231 (9)	0.0024 (8)	0.0041 (8)	−0.0028 (7)
C27	0.0301 (11)	0.0236 (9)	0.0342 (11)	0.0033 (8)	0.0060 (9)	−0.0016 (8)
S28	0.0402 (3)	0.0279 (3)	0.0460 (3)	0.0122 (2)	−0.0001 (2)	0.0018 (2)
C29	0.0387 (12)	0.0391 (12)	0.0336 (11)	0.0105 (10)	−0.0036 (9)	0.0036 (10)
C210	0.0294 (10)	0.0343 (11)	0.0294 (10)	0.0036 (8)	−0.0047 (8)	−0.0006 (9)
C211	0.0264 (10)	0.0218 (9)	0.0288 (10)	0.0024 (8)	0.0034 (8)	0.0016 (8)
C212	0.0279 (10)	0.0257 (10)	0.0280 (10)	0.0018 (8)	0.0049 (8)	0.0063 (8)
C213	0.0359 (11)	0.0400 (12)	0.0277 (10)	0.0054 (10)	0.0060 (9)	0.0076 (9)
C214	0.0573 (15)	0.0616 (16)	0.0282 (11)	0.0189 (12)	0.0152 (11)	0.0072 (11)
C215	0.0452 (14)	0.087 (2)	0.0476 (15)	0.0241 (14)	0.0260 (12)	0.0161 (14)
C216	0.0277 (12)	0.0770 (18)	0.0451 (14)	0.0060 (11)	0.0094 (10)	0.0129 (13)
C217	0.0317 (11)	0.0435 (12)	0.0333 (11)	−0.0028 (9)	0.0066 (9)	0.0048 (10)

Geometric parameters (Å, º) top

N1—C2	1.352 (2)	N21—C22	1.352 (2)
N1—C6	1.461 (2)	N21—C26	1.464 (2)
N1—C10	1.473 (2)	N21—C210	1.473 (2)
C2—O2	1.230 (2)	C22—O22	1.226 (2)
C2—C3	1.508 (3)	C22—C23	1.514 (2)
C3—N4	1.453 (2)	C23—N24	1.452 (2)
C3—C11	1.551 (3)	C23—C211	1.560 (3)
C3—H3	0.9800	C23—H23	0.9800
N4—C5	1.337 (2)	N24—C25	1.336 (2)
N4—C4	1.461 (2)	N24—C24	1.462 (2)
C4—H4A	0.9600	C24—H24A	0.9600
C4—H4B	0.9600	C24—H24B	0.9600
C4—H4C	0.9600	C24—H24C	0.9600
C5—O5	1.231 (2)	C25—O25	1.228 (2)
C5—C6	1.527 (2)	C25—C26	1.517 (3)
C6—C7	1.527 (3)	C26—C27	1.530 (3)
C6—H6	0.9800	C26—H26	0.9800
C7—S8	1.7992 (18)	C27—S28	1.793 (2)
C7—H7A	0.9700	C27—H27A	0.9700
C7—H7B	0.9700	C27—H27B	0.9700
S8—C9	1.804 (2)	S28—C29	1.803 (2)
C9—C10	1.506 (3)	C29—C210	1.508 (3)
C9—H9A	0.9700	C29—H29A	0.9700
C9—H9B	0.9700	C29—H29B	0.9700
C10—H10A	0.9700	C210—H21A	0.9700
C10—H10B	0.9700	C210—H21B	0.9700
C11—C12	1.505 (3)	C211—C212	1.507 (3)
C11—H11A	0.9700	C211—H21C	0.9700
C11—H11B	0.9700	C211—H21D	0.9700
C12—C17	1.392 (3)	C212—C213	1.393 (3)
C12—C13	1.395 (3)	C212—C217	1.394 (3)
C13—C14	1.382 (3)	C213—C214	1.388 (3)
C13—H13	0.9300	C213—H213	0.9300
C14—C15	1.380 (3)	C214—C215	1.385 (4)
C14—H14	0.9300	C214—H214	0.9300
C15—C16	1.382 (3)	C215—C216	1.374 (4)
C15—H15	0.9300	C215—H215	0.9300
C16—C17	1.387 (3)	C216—C217	1.376 (3)
C16—H16	0.9300	C216—H216	0.9300
C17—H17	0.9300	C217—H217	0.9300

C2—N1—C6	122.88 (15)	C22—N21—C26	123.69 (15)
C2—N1—C10	117.02 (15)	C22—N21—C210	117.69 (15)
C6—N1—C10	116.93 (14)	C26—N21—C210	116.17 (15)
O2—C2—N1	123.08 (17)	O22—C22—N21	123.71 (16)
O2—C2—C3	118.27 (16)	O22—C22—C23	118.54 (16)
N1—C2—C3	118.64 (15)	N21—C22—C23	117.69 (15)
N4—C3—C2	114.44 (15)	N24—C23—C22	113.92 (15)
N4—C3—C11	111.56 (15)	N24—C23—C211	111.94 (14)
C2—C3—C11	108.08 (15)	C22—C23—C211	108.65 (15)
N4—C3—H3	107.5	N24—C23—H23	107.3
C2—C3—H3	107.5	C22—C23—H23	107.3
C11—C3—H3	107.5	C211—C23—H23	107.3
C5—N4—C3	122.92 (14)	C25—N24—C23	122.44 (15)
C5—N4—C4	119.24 (16)	C25—N24—C24	119.01 (16)
C3—N4—C4	116.72 (15)	C23—N24—C24	117.49 (15)
N4—C4—H4A	109.5	N24—C24—H24A	109.5
N4—C4—H4B	109.5	N24—C24—H24B	109.5
H4A—C4—H4B	109.5	H24A—C24—H24B	109.5
N4—C4—H4C	109.5	N24—C24—H24C	109.5
H4A—C4—H4C	109.5	H24A—C24—H24C	109.5
H4B—C4—H4C	109.5	H24B—C24—H24C	109.5
O5—C5—N4	123.45 (17)	O25—C25—N24	122.42 (18)
O5—C5—C6	118.22 (16)	O25—C25—C26	118.71 (17)
N4—C5—C6	118.23 (15)	N24—C25—C26	118.77 (16)
N1—C6—C5	114.69 (14)	N21—C26—C25	114.41 (15)
N1—C6—C7	110.59 (15)	N21—C26—C27	110.71 (15)
C5—C6—C7	106.56 (14)	C25—C26—C27	105.71 (15)
N1—C6—H6	108.3	N21—C26—H26	108.6
C5—C6—H6	108.3	C25—C26—H26	108.6
C7—C6—H6	108.3	C27—C26—H26	108.6
C6—C7—S8	113.37 (13)	C26—C27—S28	114.37 (14)
C6—C7—H7A	108.9	C26—C27—H27A	108.7
S8—C7—H7A	108.9	S28—C27—H27A	108.7
C6—C7—H7B	108.9	C26—C27—H27B	108.7
S8—C7—H7B	108.9	S28—C27—H27B	108.7
H7A—C7—H7B	107.7	H27A—C27—H27B	107.6
C7—S8—C9	96.30 (9)	C27—S28—C29	97.35 (9)
C10—C9—S8	111.52 (14)	C210—C29—S28	111.83 (15)
C10—C9—H9A	109.3	C210—C29—H29A	109.3
S8—C9—H9A	109.3	S28—C29—H29A	109.3
C10—C9—H9B	109.3	C210—C29—H29B	109.3
S8—C9—H9B	109.3	S28—C29—H29B	109.3
H9A—C9—H9B	108.0	H29A—C29—H29B	107.9
N1—C10—C9	113.06 (16)	N21—C210—C29	112.23 (17)
N1—C10—H10A	109.0	N21—C210—H21A	109.2
C9—C10—H10A	109.0	C29—C210—H21A	109.2
N1—C10—H10B	109.0	N21—C210—H21B	109.2
C9—C10—H10B	109.0	C29—C210—H21B	109.2
H10A—C10—H10B	107.8	H21A—C210—H21B	107.9
C12—C11—C3	113.59 (15)	C212—C211—C23	112.29 (15)
C12—C11—H11A	108.8	C212—C211—H21C	109.1
C3—C11—H11A	108.8	C23—C211—H21C	109.1
C12—C11—H11B	108.8	C212—C211—H21D	109.1
C3—C11—H11B	108.8	C23—C211—H21D	109.1
H11A—C11—H11B	107.7	H21C—C211—H21D	107.9
C17—C12—C13	117.87 (18)	C213—C212—C217	118.12 (19)
C17—C12—C11	120.65 (18)	C213—C212—C211	121.54 (17)
C13—C12—C11	121.48 (17)	C217—C212—C211	120.24 (18)
C14—C13—C12	121.23 (18)	C214—C213—C212	120.4 (2)
C14—C13—H13	119.4	C214—C213—H213	119.8
C12—C13—H13	119.4	C212—C213—H213	119.8
C15—C14—C13	120.08 (19)	C215—C214—C213	120.2 (2)
C15—C14—H14	120.0	C215—C214—H214	119.9
C13—C14—H14	120.0	C213—C214—H214	119.9
C14—C15—C16	119.70 (19)	C216—C215—C214	119.8 (2)
C14—C15—H15	120.2	C216—C215—H215	120.1
C16—C15—H15	120.2	C214—C215—H215	120.1
C15—C16—C17	120.14 (18)	C215—C216—C217	120.1 (2)
C15—C16—H16	119.9	C215—C216—H216	120.0
C17—C16—H16	119.9	C217—C216—H216	120.0
C16—C17—C12	120.96 (18)	C216—C217—C212	121.3 (2)
C16—C17—H17	119.5	C216—C217—H217	119.3
C12—C17—H17	119.5	C212—C217—H217	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O22ⁱ	0.98	2.59	3.457 (2)	148
C3—H3···O5ⁱⁱ	0.98	2.50	3.024 (2)	114
C9—H9B···O22ⁱⁱⁱ	0.97	2.44	3.370 (2)	160
C10—H10B···S28^iv	0.97	2.79	3.733 (2)	166
C15—H15···O2^v	0.93	2.58	3.252 (2)	130
C211—H21C···O25^vi	0.97	2.56	3.511 (2)	166
C23—H23···O2^v	0.98	2.54	3.511 (2)	171
C24—H24A···O25^vi	0.96	2.35	3.164 (3)	142
C14—H14···O5^vii	0.93	2.51	3.377 (2)	156

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

(8a) top

Crystal data top

C₁₅H₁₈N₂O₂S	Z = 2
M_r = 290.37	F(000) = 308
Triclinic, P1	D_x = 1.387 Mg m⁻³
a = 7.4536 (1) Å	Mo Kα radiation, λ = 0.7107 Å
b = 7.4603 (2) Å	Cell parameters from 11838 reflections
c = 13.6011 (3) Å	θ = 1–27.5°
α = 79.6877 (12)°	µ = 0.24 mm⁻¹
β = 89.2981 (14)°	T = 150 K
γ = 69.3688 (12)°	Plate, colourless
V = 695.31 (3) Å³	0.45 × 0.32 × 0.2 mm

Data collection top

Nonius KappaCCD area detector diffractometer	R_int = 0.031
Radiation source: fine-focus sealed tube	θ_max = 27.4°, θ_min = 3.0°
φ and ω scans to fill the Ewald sphere	h = −9→9
17028 measured reflections	k = −9→9
6242 independent reflections	l = −17→17
6027 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.029	w = 1/[σ²(F_o²) + (0.0468P)² + 0.0971P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.22 e Å⁻³
6242 reflections	Δρ_min = −0.20 e Å⁻³
363 parameters	Absolute structure: Flack x determined using 2865 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
3 restraints	Absolute structure parameter: 0.022 (19)
Secondary atom site location: difference Fourier map

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.1876 (3)	0.2874 (3)	0.04004 (13)	0.0175 (4)
C2	0.2259 (3)	0.1522 (3)	−0.01870 (15)	0.0182 (4)
O2	0.1243 (2)	0.0558 (3)	−0.02513 (13)	0.0280 (4)
C3	0.3987 (3)	0.1223 (3)	−0.08201 (16)	0.0171 (4)
H3	0.3518	0.1368	−0.1510	0.020*
N4	0.4902 (3)	0.2669 (3)	−0.08300 (14)	0.0178 (4)
C4	0.6324 (3)	0.2706 (4)	−0.15787 (18)	0.0243 (5)
H4A	0.6340	0.4004	−0.1758	0.037*
H4B	0.5992	0.2307	−0.2163	0.037*
H4C	0.7571	0.1830	−0.1306	0.037*
C5	0.4782 (3)	0.3689 (3)	−0.00977 (17)	0.0190 (4)
O5	0.5825 (3)	0.4630 (2)	−0.00267 (14)	0.0290 (4)
C6	0.3232 (3)	0.3770 (3)	0.06461 (16)	0.0182 (4)
H6	0.2482	0.5154	0.0621	0.022*
C7	0.4106 (3)	0.2946 (3)	0.17251 (17)	0.0217 (4)
H7A	0.4860	0.1571	0.1785	0.026*
H7B	0.4961	0.3604	0.1866	0.026*
C8	0.2572 (4)	0.3202 (4)	0.24932 (19)	0.0263 (5)
H8A	0.1859	0.4582	0.2455	0.032*
H8B	0.3190	0.2681	0.3159	0.032*
S9	0.09101 (7)	0.19901 (8)	0.23000 (4)	0.02701 (15)
C10	0.0216 (3)	0.3201 (4)	0.10145 (17)	0.0228 (5)
H10A	−0.0686	0.2716	0.0747	0.027*
H10B	−0.0421	0.4589	0.0990	0.027*
C11	0.5430 (3)	−0.0889 (3)	−0.05250 (17)	0.0205 (4)
H11A	0.4770	−0.1781	−0.0581	0.025*
H11B	0.6435	−0.1095	−0.0997	0.025*
C12	0.6340 (3)	−0.1376 (3)	0.05179 (17)	0.0195 (4)
C13	0.5541 (3)	−0.2198 (3)	0.13250 (18)	0.0222 (5)
H13	0.4424	−0.2442	0.1220	0.027*
C14	0.6392 (4)	−0.2661 (4)	0.22882 (19)	0.0276 (5)
H14	0.5850	−0.3223	0.2819	0.033*
C15	0.8044 (4)	−0.2287 (3)	0.24563 (19)	0.0284 (5)
H15	0.8612	−0.2589	0.3099	0.034*
C16	0.8843 (4)	−0.1455 (4)	0.1655 (2)	0.0282 (5)
H16	0.9949	−0.1195	0.1764	0.034*
C17	0.8008 (3)	−0.1011 (3)	0.06986 (19)	0.0240 (5)
H17	0.8564	−0.0462	0.0169	0.029*
N21	−0.1328 (3)	0.1550 (3)	−0.35899 (13)	0.0182 (4)
C22	0.0295 (3)	0.0907 (3)	−0.30047 (16)	0.0184 (4)
O22	0.1282 (3)	0.1905 (2)	−0.29408 (13)	0.0279 (4)
C23	0.0905 (3)	−0.1113 (3)	−0.23659 (16)	0.0172 (4)
H23	0.1088	−0.0962	−0.1677	0.021*
N24	−0.0528 (3)	−0.2046 (3)	−0.23505 (14)	0.0179 (4)
C24	−0.0188 (3)	−0.3823 (3)	−0.16022 (18)	0.0241 (5)
H24A	−0.1396	−0.3939	−0.1418	0.036*
H24B	0.0488	−0.3760	−0.1021	0.036*
H24C	0.0565	−0.4935	−0.1877	0.036*
C25	−0.1903 (3)	−0.1596 (3)	−0.30785 (17)	0.0196 (4)
O25	−0.2873 (2)	−0.2605 (3)	−0.31402 (14)	0.0292 (4)
C26	−0.2338 (3)	0.0303 (3)	−0.38275 (16)	0.0186 (4)
H26	−0.3711	0.1038	−0.3803	0.022*
C27	−0.2020 (3)	−0.0090 (3)	−0.49018 (16)	0.0211 (4)
H27A	−0.0671	−0.0819	−0.4959	0.025*
H27B	−0.2744	−0.0884	−0.5035	0.025*
C28	−0.2637 (4)	0.1794 (4)	−0.56857 (18)	0.0259 (5)
H28A	−0.4002	0.2487	−0.5654	0.031*
H28B	−0.2416	0.1469	−0.6347	0.031*
S29	−0.13449 (8)	0.33726 (8)	−0.55012 (4)	0.02691 (14)
C210	−0.1954 (3)	0.3488 (3)	−0.42137 (17)	0.0235 (5)
H21A	−0.1350	0.4277	−0.3953	0.028*
H21B	−0.3333	0.4107	−0.4189	0.028*
C211	0.2882 (3)	−0.2410 (3)	−0.26655 (17)	0.0218 (4)
H21C	0.3807	−0.1789	−0.2597	0.026*
H21D	0.3304	−0.3651	−0.2204	0.026*
C212	0.2875 (3)	−0.2782 (3)	−0.37139 (17)	0.0192 (4)
C213	0.2435 (3)	−0.4345 (3)	−0.39265 (19)	0.0251 (5)
H213	0.2166	−0.5193	−0.3408	0.030*
C214	0.2394 (4)	−0.4652 (4)	−0.4906 (2)	0.0315 (6)
H214	0.2085	−0.5692	−0.5038	0.038*
C215	0.2811 (4)	−0.3415 (4)	−0.56785 (19)	0.0312 (6)
H215	0.2794	−0.3627	−0.6331	0.037*
C216	0.3258 (4)	−0.1852 (4)	−0.54826 (19)	0.0276 (5)
H216	0.3539	−0.1015	−0.6003	0.033*
C217	0.3283 (3)	−0.1546 (3)	−0.45085 (18)	0.0221 (5)
H217	0.3577	−0.0493	−0.4382	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0174 (9)	0.0208 (9)	0.0150 (9)	−0.0072 (7)	0.0008 (7)	−0.0048 (7)
C2	0.0182 (10)	0.0206 (10)	0.0157 (10)	−0.0067 (8)	0.0000 (8)	−0.0033 (8)
O2	0.0271 (9)	0.0370 (9)	0.0298 (9)	−0.0196 (8)	0.0068 (7)	−0.0150 (8)
C3	0.0198 (11)	0.0187 (10)	0.0158 (10)	−0.0093 (8)	0.0014 (8)	−0.0057 (8)
N4	0.0179 (9)	0.0179 (8)	0.0179 (9)	−0.0076 (7)	0.0036 (7)	−0.0015 (7)
C4	0.0226 (11)	0.0240 (11)	0.0234 (12)	−0.0067 (9)	0.0073 (9)	−0.0007 (9)
C5	0.0177 (10)	0.0145 (9)	0.0225 (11)	−0.0037 (8)	−0.0010 (8)	−0.0018 (8)
O5	0.0310 (9)	0.0252 (9)	0.0382 (10)	−0.0175 (7)	0.0042 (7)	−0.0089 (7)
C6	0.0194 (10)	0.0153 (9)	0.0197 (10)	−0.0052 (8)	−0.0011 (8)	−0.0052 (8)
C7	0.0241 (11)	0.0199 (10)	0.0208 (11)	−0.0068 (9)	−0.0040 (9)	−0.0053 (8)
C8	0.0322 (13)	0.0273 (12)	0.0193 (11)	−0.0086 (10)	−0.0014 (9)	−0.0081 (9)
S9	0.0292 (3)	0.0359 (3)	0.0174 (3)	−0.0132 (3)	0.0048 (2)	−0.0058 (2)
C10	0.0182 (10)	0.0284 (12)	0.0210 (11)	−0.0057 (9)	0.0030 (8)	−0.0079 (9)
C11	0.0252 (11)	0.0169 (10)	0.0208 (11)	−0.0076 (9)	0.0042 (9)	−0.0067 (8)
C12	0.0202 (11)	0.0121 (9)	0.0246 (11)	−0.0031 (8)	0.0032 (9)	−0.0050 (8)
C13	0.0214 (11)	0.0189 (11)	0.0268 (12)	−0.0074 (9)	0.0031 (9)	−0.0051 (9)
C14	0.0316 (14)	0.0224 (12)	0.0236 (12)	−0.0052 (10)	0.0049 (10)	−0.0005 (9)
C15	0.0328 (13)	0.0216 (11)	0.0238 (12)	−0.0022 (10)	−0.0075 (10)	−0.0014 (9)
C16	0.0230 (11)	0.0225 (11)	0.0381 (14)	−0.0078 (9)	−0.0051 (10)	−0.0035 (10)
C17	0.0216 (11)	0.0183 (11)	0.0305 (13)	−0.0075 (9)	0.0020 (9)	0.0001 (9)
N21	0.0202 (9)	0.0165 (8)	0.0165 (9)	−0.0055 (7)	−0.0004 (7)	−0.0016 (7)
C22	0.0215 (10)	0.0181 (10)	0.0159 (10)	−0.0072 (8)	0.0018 (8)	−0.0041 (8)
O22	0.0336 (9)	0.0248 (8)	0.0297 (9)	−0.0173 (7)	−0.0056 (7)	−0.0013 (7)
C23	0.0176 (10)	0.0195 (10)	0.0142 (10)	−0.0071 (8)	−0.0017 (7)	−0.0014 (8)
N24	0.0186 (9)	0.0168 (8)	0.0176 (9)	−0.0070 (7)	0.0010 (7)	0.0005 (7)
C24	0.0253 (11)	0.0195 (10)	0.0232 (11)	−0.0059 (9)	0.0028 (9)	0.0026 (9)
C25	0.0150 (10)	0.0216 (10)	0.0218 (11)	−0.0054 (8)	0.0037 (8)	−0.0060 (9)
O25	0.0230 (8)	0.0317 (9)	0.0371 (10)	−0.0162 (7)	0.0000 (7)	−0.0036 (8)
C26	0.0135 (10)	0.0225 (11)	0.0190 (10)	−0.0052 (8)	−0.0004 (8)	−0.0039 (8)
C27	0.0184 (10)	0.0263 (11)	0.0192 (11)	−0.0074 (9)	0.0000 (8)	−0.0069 (9)
C28	0.0243 (12)	0.0345 (13)	0.0162 (11)	−0.0078 (10)	−0.0013 (9)	−0.0034 (9)
S29	0.0321 (3)	0.0273 (3)	0.0182 (3)	−0.0099 (2)	−0.0001 (2)	0.0021 (2)
C210	0.0276 (12)	0.0177 (10)	0.0213 (11)	−0.0045 (9)	0.0008 (9)	−0.0012 (9)
C211	0.0167 (10)	0.0238 (11)	0.0219 (11)	−0.0053 (9)	−0.0025 (8)	−0.0003 (9)
C212	0.0119 (10)	0.0214 (10)	0.0215 (11)	−0.0027 (8)	0.0006 (8)	−0.0038 (9)
C213	0.0197 (11)	0.0207 (11)	0.0344 (13)	−0.0058 (9)	0.0066 (9)	−0.0070 (10)
C214	0.0231 (12)	0.0312 (13)	0.0453 (15)	−0.0097 (10)	0.0061 (11)	−0.0206 (12)
C215	0.0240 (12)	0.0431 (15)	0.0291 (13)	−0.0098 (11)	0.0039 (10)	−0.0182 (11)
C216	0.0237 (13)	0.0344 (14)	0.0240 (12)	−0.0095 (10)	0.0038 (10)	−0.0051 (11)
C217	0.0183 (11)	0.0230 (11)	0.0258 (11)	−0.0080 (9)	0.0008 (8)	−0.0049 (9)

Geometric parameters (Å, º) top

N1—C2	1.348 (3)	N21—C22	1.343 (3)
N1—C10	1.457 (3)	N21—C210	1.457 (3)
N1—C6	1.464 (3)	N21—C26	1.464 (3)
C2—O2	1.228 (3)	C22—O22	1.231 (3)
C2—C3	1.513 (3)	C22—C23	1.514 (3)
C3—N4	1.463 (3)	C23—N24	1.464 (3)
C3—C11	1.546 (3)	C23—C211	1.548 (3)
C3—H3	0.9800	C23—H23	0.9800
N4—C5	1.342 (3)	N24—C25	1.344 (3)
N4—C4	1.464 (3)	N24—C24	1.464 (3)
C4—H4A	0.9600	C24—H24A	0.9600
C4—H4B	0.9600	C24—H24B	0.9600
C4—H4C	0.9600	C24—H24C	0.9600
C5—O5	1.232 (3)	C25—O25	1.227 (3)
C5—C6	1.519 (3)	C25—C26	1.522 (3)
C6—C7	1.541 (3)	C26—C27	1.540 (3)
C6—H6	0.9800	C26—H26	0.9800
C7—C8	1.524 (3)	C27—C28	1.531 (3)
C7—H7A	0.9700	C27—H27A	0.9700
C7—H7B	0.9700	C27—H27B	0.9700
C8—S9	1.817 (3)	C28—S29	1.814 (3)
C8—H8A	0.9700	C28—H28A	0.9700
C8—H8B	0.9700	C28—H28B	0.9700
S9—C10	1.808 (2)	S29—C210	1.813 (2)
C10—H10A	0.9700	C210—H21A	0.9700
C10—H10B	0.9700	C210—H21B	0.9700
C11—C12	1.507 (3)	C211—C212	1.501 (3)
C11—H11A	0.9700	C211—H21C	0.9700
C11—H11B	0.9700	C211—H21D	0.9700
C12—C13	1.392 (3)	C212—C213	1.393 (3)
C12—C17	1.397 (3)	C212—C217	1.395 (3)
C13—C14	1.394 (4)	C213—C214	1.394 (4)
C13—H13	0.9300	C213—H213	0.9300
C14—C15	1.385 (4)	C214—C215	1.378 (4)
C14—H14	0.9300	C214—H214	0.9300
C15—C16	1.389 (4)	C215—C216	1.388 (4)
C15—H15	0.9300	C215—H215	0.9300
C16—C17	1.382 (4)	C216—C217	1.386 (4)
C16—H16	0.9300	C216—H216	0.9300
C17—H17	0.9300	C217—H217	0.9300

C2—N1—C10	119.68 (18)	C22—N21—C210	119.92 (18)
C2—N1—C6	124.19 (18)	C22—N21—C26	124.30 (17)
C10—N1—C6	114.75 (18)	C210—N21—C26	114.44 (18)
O2—C2—N1	123.0 (2)	O22—C22—N21	123.10 (19)
O2—C2—C3	118.52 (19)	O22—C22—C23	118.28 (19)
N1—C2—C3	118.44 (18)	N21—C22—C23	118.58 (18)
N4—C3—C2	114.36 (17)	N24—C23—C22	114.30 (17)
N4—C3—C11	112.27 (17)	N24—C23—C211	112.13 (18)
C2—C3—C11	110.31 (17)	C22—C23—C211	110.22 (18)
N4—C3—H3	106.4	N24—C23—H23	106.6
C2—C3—H3	106.4	C22—C23—H23	106.6
C11—C3—H3	106.4	C211—C23—H23	106.6
C5—N4—C3	123.86 (18)	C25—N24—C24	117.99 (18)
C5—N4—C4	118.07 (19)	C25—N24—C23	124.06 (18)
C3—N4—C4	116.92 (18)	C24—N24—C23	116.76 (17)
N4—C4—H4A	109.5	N24—C24—H24A	109.5
N4—C4—H4B	109.5	N24—C24—H24B	109.5
H4A—C4—H4B	109.5	H24A—C24—H24B	109.5
N4—C4—H4C	109.5	N24—C24—H24C	109.5
H4A—C4—H4C	109.5	H24A—C24—H24C	109.5
H4B—C4—H4C	109.5	H24B—C24—H24C	109.5
O5—C5—N4	122.8 (2)	O25—C25—N24	122.9 (2)
O5—C5—C6	118.5 (2)	O25—C25—C26	118.7 (2)
N4—C5—C6	118.68 (19)	N24—C25—C26	118.34 (19)
N1—C6—C5	114.10 (18)	N21—C26—C25	114.26 (18)
N1—C6—C7	111.66 (18)	N21—C26—C27	111.84 (17)
C5—C6—C7	111.32 (18)	C25—C26—C27	110.85 (18)
N1—C6—H6	106.4	N21—C26—H26	106.4
C5—C6—H6	106.4	C25—C26—H26	106.4
C7—C6—H6	106.4	C27—C26—H26	106.4
C8—C7—C6	112.16 (19)	C28—C27—C26	112.33 (19)
C8—C7—H7A	109.2	C28—C27—H27A	109.1
C6—C7—H7A	109.2	C26—C27—H27A	109.1
C8—C7—H7B	109.2	C28—C27—H27B	109.1
C6—C7—H7B	109.2	C26—C27—H27B	109.1
H7A—C7—H7B	107.9	H27A—C27—H27B	107.9
C7—C8—S9	112.48 (16)	C27—C28—S29	112.34 (16)
C7—C8—H8A	109.1	C27—C28—H28A	109.1
S9—C8—H8A	109.1	S29—C28—H28A	109.1
C7—C8—H8B	109.1	C27—C28—H28B	109.1
S9—C8—H8B	109.1	S29—C28—H28B	109.1
H8A—C8—H8B	107.8	H28A—C28—H28B	107.9
C10—S9—C8	95.64 (11)	C210—S29—C28	95.87 (11)
N1—C10—S9	111.34 (15)	N21—C210—S29	111.30 (15)
N1—C10—H10A	109.4	N21—C210—H21A	109.4
S9—C10—H10A	109.4	S29—C210—H21A	109.4
N1—C10—H10B	109.4	N21—C210—H21B	109.4
S9—C10—H10B	109.4	S29—C210—H21B	109.4
H10A—C10—H10B	108.0	H21A—C210—H21B	108.0
C12—C11—C3	114.16 (17)	C212—C211—C23	113.88 (17)
C12—C11—H11A	108.7	C212—C211—H21C	108.8
C3—C11—H11A	108.7	C23—C211—H21C	108.8
C12—C11—H11B	108.7	C212—C211—H21D	108.8
C3—C11—H11B	108.7	C23—C211—H21D	108.8
H11A—C11—H11B	107.6	H21C—C211—H21D	107.7
C13—C12—C17	118.3 (2)	C213—C212—C217	118.0 (2)
C13—C12—C11	120.9 (2)	C213—C212—C211	121.4 (2)
C17—C12—C11	120.8 (2)	C217—C212—C211	120.6 (2)
C12—C13—C14	120.8 (2)	C212—C213—C214	120.9 (2)
C12—C13—H13	119.6	C212—C213—H213	119.6
C14—C13—H13	119.6	C214—C213—H213	119.6
C15—C14—C13	120.2 (2)	C215—C214—C213	120.0 (2)
C15—C14—H14	119.9	C215—C214—H214	120.0
C13—C14—H14	119.9	C213—C214—H214	120.0
C14—C15—C16	119.3 (2)	C214—C215—C216	120.0 (2)
C14—C15—H15	120.3	C214—C215—H215	120.0
C16—C15—H15	120.3	C216—C215—H215	120.0
C17—C16—C15	120.5 (2)	C217—C216—C215	119.7 (2)
C17—C16—H16	119.7	C217—C216—H216	120.1
C15—C16—H16	119.7	C215—C216—H216	120.1
C16—C17—C12	120.8 (2)	C216—C217—C212	121.3 (2)
C16—C17—H17	119.6	C216—C217—H217	119.3
C12—C17—H17	119.6	C212—C217—H217	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O22	0.98	2.46	3.397 (3)	160
C11—H11A···O5ⁱ	0.97	2.48	3.197 (3)	130
C17—H17···O2ⁱⁱ	0.93	2.40	3.197 (3)	143
C211—H21C···O25ⁱⁱ	0.97	2.47	3.179 (3)	130
C23—H23···O2	0.98	2.44	3.378 (3)	161
C213—H213···O22ⁱ	0.93	2.45	3.269 (3)	146

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

(8b) top

Crystal data top

C₁₅H₁₈N₂O₂S	F(000) = 616
M_r = 290.37	D_x = 1.341 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14664 reflections
a = 9.8689 (2) Å	θ = 1–27.5°
b = 10.6838 (2) Å	µ = 0.23 mm⁻¹
c = 13.6421 (2) Å	T = 150 K
V = 1438.39 (4) Å³	Prism, colourles
Z = 4	0.4 × 0.25 × 0.25 mm

Data collection top

Nonius KappaCCD area detector diffractometer	3045 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 2.8°
Detector resolution: 9.091 pixels mm^-1	h = 0→12
φ and ω scans to fill the Ewald sphere	k = 0→13
25952 measured reflections	l = −17→17
3291 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0369P)² + 0.3211P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.20 e Å⁻³
3291 reflections	Δρ_min = −0.18 e Å⁻³
183 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.044 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (7)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.28236 (13)	0.78426 (11)	0.10568 (8)	0.0256 (3)
C2	0.21533 (15)	0.88543 (13)	0.13948 (11)	0.0260 (3)
C3	0.13535 (14)	0.87245 (12)	0.23322 (10)	0.0247 (3)
H3	0.0510	0.9198	0.2252	0.030*
N4	0.09891 (11)	0.74383 (11)	0.25736 (9)	0.0230 (3)
C4	−0.00986 (16)	0.72775 (15)	0.32923 (11)	0.0325 (3)
H4A	−0.0588	0.6522	0.3151	0.049*
H4B	−0.0705	0.7979	0.3259	0.049*
H4C	0.0284	0.7226	0.3938	0.049*
C5	0.16656 (13)	0.64327 (13)	0.22624 (10)	0.0215 (3)
C6	0.27321 (14)	0.65846 (13)	0.14681 (10)	0.0225 (3)
H6	0.3614	0.6379	0.1756	0.027*
C7	0.24381 (16)	0.56212 (14)	0.06594 (11)	0.0295 (3)
H7A	0.2403	0.4794	0.0951	0.035*
H7B	0.1554	0.5796	0.0381	0.035*
C8	0.3480 (2)	0.56163 (17)	−0.01575 (12)	0.0403 (4)
H8A	0.3257	0.4964	−0.0625	0.048*
H8B	0.4366	0.5431	0.0114	0.048*
S9	0.35366 (5)	0.71083 (4)	−0.07809 (3)	0.04405 (14)
C10	0.38512 (16)	0.80154 (17)	0.03036 (11)	0.0352 (4)
H10A	0.4728	0.7784	0.0570	0.042*
H10B	0.3889	0.8894	0.0127	0.042*
C11	0.21673 (16)	0.93424 (15)	0.31800 (12)	0.0300 (3)
H11A	0.2338	1.0213	0.3021	0.036*
H11B	0.1631	0.9318	0.3776	0.036*
C12	0.34986 (16)	0.86860 (13)	0.33545 (10)	0.0267 (3)
C13	0.46417 (15)	0.90170 (15)	0.28157 (12)	0.0319 (3)
H13	0.4605	0.9702	0.2396	0.038*
C14	0.58348 (16)	0.83375 (16)	0.28969 (14)	0.0377 (4)
H14	0.6592	0.8571	0.2535	0.045*
C15	0.58988 (17)	0.73134 (16)	0.35165 (13)	0.0383 (4)
H15	0.6693	0.6850	0.3565	0.046*
C16	0.47739 (18)	0.69845 (16)	0.40622 (12)	0.0377 (4)
H16	0.4814	0.6300	0.4483	0.045*
C17	0.35842 (17)	0.76714 (15)	0.39854 (11)	0.0322 (3)
H17	0.2836	0.7448	0.4361	0.039*
O2	0.22419 (12)	0.98925 (10)	0.10066 (9)	0.0373 (3)
O5	0.14323 (11)	0.53662 (9)	0.25671 (8)	0.0301 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0293 (6)	0.0238 (6)	0.0236 (6)	−0.0026 (5)	0.0033 (5)	0.0010 (5)
C2	0.0270 (7)	0.0232 (7)	0.0278 (7)	−0.0025 (6)	−0.0062 (6)	0.0008 (6)
C3	0.0235 (6)	0.0196 (6)	0.0311 (7)	0.0022 (6)	−0.0011 (6)	−0.0018 (5)
N4	0.0210 (5)	0.0230 (6)	0.0250 (6)	−0.0004 (4)	0.0015 (5)	−0.0008 (5)
C4	0.0292 (7)	0.0359 (8)	0.0325 (8)	−0.0002 (7)	0.0092 (6)	−0.0026 (7)
C5	0.0203 (6)	0.0231 (7)	0.0211 (6)	−0.0009 (5)	−0.0020 (5)	0.0012 (5)
C6	0.0221 (6)	0.0241 (7)	0.0214 (6)	0.0012 (5)	−0.0001 (5)	0.0000 (5)
C7	0.0369 (8)	0.0261 (7)	0.0256 (7)	0.0009 (6)	0.0010 (6)	−0.0027 (6)
C8	0.0528 (10)	0.0406 (9)	0.0275 (7)	0.0073 (9)	0.0095 (8)	−0.0070 (7)
S9	0.0579 (3)	0.0510 (3)	0.02326 (19)	−0.0009 (2)	0.01065 (19)	0.00207 (18)
C10	0.0364 (8)	0.0381 (9)	0.0312 (8)	−0.0074 (7)	0.0091 (6)	0.0032 (7)
C11	0.0313 (8)	0.0267 (7)	0.0319 (8)	0.0021 (6)	−0.0021 (6)	−0.0070 (6)
C12	0.0301 (7)	0.0249 (7)	0.0251 (7)	−0.0012 (6)	−0.0053 (6)	−0.0075 (5)
C13	0.0317 (8)	0.0293 (8)	0.0348 (8)	−0.0066 (6)	−0.0059 (7)	−0.0003 (6)
C14	0.0272 (7)	0.0418 (10)	0.0441 (9)	−0.0059 (7)	−0.0016 (7)	−0.0068 (8)
C15	0.0314 (8)	0.0355 (9)	0.0478 (10)	0.0062 (7)	−0.0110 (7)	−0.0115 (7)
C16	0.0454 (9)	0.0318 (8)	0.0360 (9)	0.0030 (7)	−0.0128 (7)	0.0017 (7)
C17	0.0354 (8)	0.0360 (8)	0.0251 (7)	−0.0035 (7)	−0.0024 (6)	−0.0009 (6)
O2	0.0445 (6)	0.0241 (5)	0.0432 (7)	−0.0029 (5)	−0.0011 (5)	0.0079 (5)
O5	0.0345 (5)	0.0227 (5)	0.0332 (5)	−0.0008 (4)	0.0069 (5)	0.0038 (4)

Geometric parameters (Å, º) top

N1—C2	1.3486 (19)	C8—S9	1.8076 (18)
N1—C10	1.4554 (18)	C8—H8A	0.9700
N1—C6	1.4593 (18)	C8—H8B	0.9700
C2—O2	1.2322 (18)	S9—C10	1.7956 (18)
C2—C3	1.509 (2)	C10—H10A	0.9700
C3—N4	1.4581 (18)	C10—H10B	0.9700
C3—C11	1.555 (2)	C11—C12	1.508 (2)
C3—H3	0.9800	C11—H11A	0.9700
N4—C5	1.3342 (18)	C11—H11B	0.9700
N4—C4	1.4638 (18)	C12—C17	1.387 (2)
C4—H4A	0.9600	C12—C13	1.392 (2)
C4—H4B	0.9600	C13—C14	1.388 (2)
C4—H4C	0.9600	C13—H13	0.9300
C5—O5	1.2346 (17)	C14—C15	1.384 (3)
C5—C6	1.5193 (19)	C14—H14	0.9300
C6—C7	1.5365 (19)	C15—C16	1.382 (3)
C6—H6	0.9800	C15—H15	0.9300
C7—C8	1.516 (2)	C16—C17	1.388 (2)
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	C17—H17	0.9300

C2—N1—C10	118.79 (13)	C7—C8—H8A	109.4
C2—N1—C6	125.19 (12)	S9—C8—H8A	109.4
C10—N1—C6	115.56 (12)	C7—C8—H8B	109.4
O2—C2—N1	122.66 (14)	S9—C8—H8B	109.4
O2—C2—C3	118.95 (13)	H8A—C8—H8B	108.0
N1—C2—C3	118.21 (12)	C10—S9—C8	95.38 (8)
N4—C3—C2	114.02 (11)	N1—C10—S9	113.12 (11)
N4—C3—C11	111.06 (12)	N1—C10—H10A	109.0
C2—C3—C11	108.72 (12)	S9—C10—H10A	109.0
N4—C3—H3	107.6	N1—C10—H10B	109.0
C2—C3—H3	107.6	S9—C10—H10B	109.0
C11—C3—H3	107.6	H10A—C10—H10B	107.8
C5—N4—C3	124.30 (11)	C12—C11—C3	111.71 (12)
C5—N4—C4	119.05 (12)	C12—C11—H11A	109.3
C3—N4—C4	116.28 (11)	C3—C11—H11A	109.3
N4—C4—H4A	109.5	C12—C11—H11B	109.3
N4—C4—H4B	109.5	C3—C11—H11B	109.3
H4A—C4—H4B	109.5	H11A—C11—H11B	107.9
N4—C4—H4C	109.5	C17—C12—C13	118.48 (14)
H4A—C4—H4C	109.5	C17—C12—C11	120.97 (14)
H4B—C4—H4C	109.5	C13—C12—C11	120.29 (13)
O5—C5—N4	122.86 (12)	C14—C13—C12	120.83 (15)
O5—C5—C6	117.90 (12)	C14—C13—H13	119.6
N4—C5—C6	119.19 (12)	C12—C13—H13	119.6
N1—C6—C5	114.55 (11)	C15—C14—C13	120.07 (16)
N1—C6—C7	110.64 (11)	C15—C14—H14	120.0
C5—C6—C7	108.04 (11)	C13—C14—H14	120.0
N1—C6—H6	107.8	C16—C15—C14	119.56 (15)
C5—C6—H6	107.8	C16—C15—H15	120.2
C7—C6—H6	107.8	C14—C15—H15	120.2
C8—C7—C6	113.71 (13)	C15—C16—C17	120.28 (15)
C8—C7—H7A	108.8	C15—C16—H16	119.9
C6—C7—H7A	108.8	C17—C16—H16	119.9
C8—C7—H7B	108.8	C12—C17—C16	120.76 (15)
C6—C7—H7B	108.8	C12—C17—H17	119.6
H7A—C7—H7B	107.7	C16—C17—H17	119.6
C7—C8—S9	111.33 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5ⁱ	0.98	2.30	3.2641 (17)	167
C8—H8A···O5ⁱⁱ	0.97	2.51	3.2779 (19)	136
C15—H15···O2ⁱⁱⁱ	0.93	2.41	3.237 (2)	148

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

(12a) top

Crystal data top

C₁₄H₁₆N₂O₂S	D_x = 1.407 Mg m⁻³
M_r = 276.35	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 6416 reflections
Hall symbol: P 4nw 2abw	θ = 3.2–27.5°
a = 7.7430 (2) Å	µ = 0.25 mm⁻¹
c = 43.5343 (14) Å	T = 150 K
V = 2610.06 (13) Å³	Bar, colourless
Z = 8	0.46 × 0.18 × 0.18 mm
F(000) = 1168

Data collection top

Bruker APEX-II CCD diffractometer	2992 independent reflections
Radiation source: fine-focus sealed tube	2800 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	h = −7→10
T_min = 0.894, T_max = 0.957	k = −8→10
15598 measured reflections	l = −52→56

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0398P)² + 0.4448P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
2992 reflections	Δρ_max = 0.21 e Å⁻³
173 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (7)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.38721 (17)	0.01940 (16)	0.73082 (3)	0.0197 (3)
C2	0.4236 (2)	−0.14453 (19)	0.72231 (3)	0.0182 (3)
C3	0.28391 (19)	−0.24774 (18)	0.70624 (3)	0.0174 (3)
H3	0.2694	−0.3576	0.7180	0.021*
N4	0.11398 (16)	−0.16492 (16)	0.70493 (3)	0.0180 (3)
C5	0.0860 (2)	0.0049 (2)	0.70881 (3)	0.0204 (3)
C6	0.2319 (2)	0.11047 (18)	0.72197 (3)	0.0197 (3)
H6	0.1869	0.1711	0.7406	0.024*
S7	0.30515 (6)	0.27642 (5)	0.694748 (9)	0.02662 (11)
C8	0.5216 (2)	0.2738 (3)	0.71089 (4)	0.0377 (5)
H8A	0.6063	0.2395	0.6950	0.045*
H8B	0.5528	0.3902	0.7185	0.045*
C9	0.5242 (2)	0.1450 (2)	0.73721 (4)	0.0280 (4)
H9A	0.6378	0.0866	0.7383	0.034*
H9B	0.5024	0.2042	0.7570	0.034*
C10	−0.0291 (2)	−0.2728 (2)	0.69390 (4)	0.0254 (3)
H10A	−0.1367	−0.2364	0.7038	0.038*
H10B	−0.0059	−0.3940	0.6989	0.038*
H10C	−0.0403	−0.2600	0.6716	0.038*
C11	0.3505 (2)	−0.29767 (19)	0.67383 (3)	0.0197 (3)
H11A	0.4602	−0.3622	0.6761	0.024*
H11B	0.2657	−0.3764	0.6642	0.024*
C12	0.3810 (2)	−0.14716 (19)	0.65245 (3)	0.0193 (3)
C13	0.2488 (2)	−0.08414 (19)	0.63401 (3)	0.0221 (3)
H13	0.1365	−0.1328	0.6356	0.027*
C14	0.2785 (3)	0.0489 (2)	0.61329 (4)	0.0303 (4)
H14	0.1869	0.0902	0.6008	0.036*
C15	0.4409 (3)	0.1214 (2)	0.61085 (4)	0.0346 (4)
H15	0.4613	0.2121	0.5966	0.042*
C16	0.5740 (3)	0.0614 (2)	0.62924 (4)	0.0330 (4)
H16	0.6857	0.1112	0.6276	0.040*
C17	0.5444 (2)	−0.0718 (2)	0.65010 (4)	0.0248 (3)
H17	0.6359	−0.1117	0.6628	0.030*
O2	0.56338 (14)	−0.21299 (15)	0.72714 (3)	0.0270 (3)
O5	−0.05266 (15)	0.07533 (16)	0.70351 (3)	0.0334 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0219 (7)	0.0169 (6)	0.0202 (6)	−0.0028 (5)	−0.0043 (5)	−0.0001 (5)
C2	0.0226 (8)	0.0182 (7)	0.0138 (6)	−0.0008 (6)	0.0007 (6)	0.0038 (6)
C3	0.0201 (7)	0.0143 (7)	0.0178 (6)	−0.0005 (5)	0.0002 (6)	0.0015 (5)
N4	0.0159 (6)	0.0198 (6)	0.0183 (6)	−0.0018 (5)	0.0002 (5)	−0.0011 (5)
C5	0.0210 (8)	0.0209 (8)	0.0193 (7)	0.0013 (6)	0.0016 (6)	0.0028 (6)
C6	0.0248 (8)	0.0142 (7)	0.0201 (7)	0.0009 (6)	−0.0008 (6)	−0.0005 (6)
S7	0.0361 (2)	0.01715 (18)	0.02665 (19)	−0.00488 (15)	−0.00655 (17)	0.00451 (15)
C8	0.0351 (10)	0.0368 (11)	0.0412 (10)	−0.0176 (8)	−0.0097 (8)	0.0117 (9)
C9	0.0296 (9)	0.0260 (9)	0.0284 (8)	−0.0107 (7)	−0.0083 (7)	−0.0002 (7)
C10	0.0214 (8)	0.0286 (8)	0.0262 (7)	−0.0088 (6)	0.0001 (6)	−0.0020 (7)
C11	0.0252 (7)	0.0146 (7)	0.0192 (7)	0.0006 (6)	0.0013 (6)	−0.0019 (5)
C12	0.0255 (8)	0.0146 (7)	0.0177 (7)	0.0002 (6)	0.0047 (6)	−0.0043 (6)
C13	0.0290 (9)	0.0186 (7)	0.0188 (7)	−0.0004 (6)	0.0006 (6)	−0.0038 (6)
C14	0.0498 (11)	0.0219 (8)	0.0192 (7)	0.0069 (8)	−0.0002 (8)	−0.0005 (6)
C15	0.0596 (13)	0.0173 (8)	0.0269 (8)	−0.0008 (8)	0.0183 (9)	0.0006 (7)
C16	0.0376 (10)	0.0218 (8)	0.0396 (10)	−0.0082 (7)	0.0199 (8)	−0.0075 (7)
C17	0.0236 (8)	0.0210 (8)	0.0297 (8)	0.0011 (6)	0.0064 (7)	−0.0048 (6)
O2	0.0228 (6)	0.0277 (6)	0.0306 (6)	0.0039 (5)	−0.0069 (5)	0.0024 (5)
O5	0.0213 (6)	0.0290 (7)	0.0499 (8)	0.0056 (5)	−0.0027 (6)	0.0018 (6)

Geometric parameters (Å, º) top

N1—C2	1.352 (2)	C9—H9B	0.9900
N1—C6	1.4464 (19)	C10—H10A	0.9800
N1—C9	1.4658 (19)	C10—H10B	0.9800
C2—O2	1.2236 (19)	C10—H10C	0.9800
C2—C3	1.516 (2)	C11—C12	1.510 (2)
C3—N4	1.4648 (18)	C11—H11A	0.9900
C3—C11	1.5515 (19)	C11—H11B	0.9900
C3—H3	1.0000	C12—C13	1.390 (2)
N4—C5	1.343 (2)	C12—C17	1.397 (2)
N4—C10	1.4684 (19)	C13—C14	1.389 (2)
C5—O5	1.2262 (19)	C13—H13	0.9500
C5—C6	1.507 (2)	C14—C15	1.381 (3)
C6—S7	1.8378 (15)	C14—H14	0.9500
C6—H6	1.0000	C15—C16	1.385 (3)
S7—C8	1.8178 (19)	C15—H15	0.9500
C8—C9	1.519 (2)	C16—C17	1.393 (2)
C8—H8A	0.9900	C16—H16	0.9500
C8—H8B	0.9900	C17—H17	0.9500
C9—H9A	0.9900

C2—N1—C6	123.92 (13)	N1—C9—H9B	110.4
C2—N1—C9	121.61 (14)	C8—C9—H9B	110.4
C6—N1—C9	109.21 (12)	H9A—C9—H9B	108.6
O2—C2—N1	122.95 (14)	N4—C10—H10A	109.5
O2—C2—C3	118.82 (14)	N4—C10—H10B	109.5
N1—C2—C3	118.22 (13)	H10A—C10—H10B	109.5
N4—C3—C2	115.34 (12)	N4—C10—H10C	109.5
N4—C3—C11	111.86 (12)	H10A—C10—H10C	109.5
C2—C3—C11	108.29 (12)	H10B—C10—H10C	109.5
N4—C3—H3	107.0	C12—C11—C3	114.85 (12)
C2—C3—H3	107.0	C12—C11—H11A	108.6
C11—C3—H3	107.0	C3—C11—H11A	108.6
C5—N4—C3	124.65 (12)	C12—C11—H11B	108.6
C5—N4—C10	118.44 (13)	C3—C11—H11B	108.6
C3—N4—C10	116.21 (12)	H11A—C11—H11B	107.5
O5—C5—N4	123.57 (15)	C13—C12—C17	118.58 (15)
O5—C5—C6	119.11 (14)	C13—C12—C11	120.79 (14)
N4—C5—C6	117.25 (13)	C17—C12—C11	120.60 (14)
N1—C6—C5	117.38 (12)	C14—C13—C12	120.93 (16)
N1—C6—S7	104.82 (10)	C14—C13—H13	119.5
C5—C6—S7	111.43 (10)	C12—C13—H13	119.5
N1—C6—H6	107.6	C15—C14—C13	120.14 (17)
C5—C6—H6	107.6	C15—C14—H14	119.9
S7—C6—H6	107.6	C13—C14—H14	119.9
C8—S7—C6	91.57 (8)	C14—C15—C16	119.76 (16)
C9—C8—S7	108.13 (12)	C14—C15—H15	120.1
C9—C8—H8A	110.1	C16—C15—H15	120.1
S7—C8—H8A	110.1	C15—C16—C17	120.21 (17)
C9—C8—H8B	110.1	C15—C16—H16	119.9
S7—C8—H8B	110.1	C17—C16—H16	119.9
H8A—C8—H8B	108.4	C16—C17—C12	120.37 (16)
N1—C9—C8	106.42 (13)	C16—C17—H17	119.8
N1—C9—H9A	110.4	C12—C17—H17	119.8
C8—C9—H9A	110.4

C6—N1—C2—O2	171.76 (14)	N4—C5—C6—N1	−3.0 (2)
C9—N1—C2—O2	20.2 (2)	O5—C5—C6—S7	−65.32 (17)
C6—N1—C2—C3	−8.6 (2)	N4—C5—C6—S7	117.83 (13)
C9—N1—C2—C3	−160.19 (13)	N1—C6—S7—C8	−24.08 (12)
O2—C2—C3—N4	172.33 (13)	C5—C6—S7—C8	−152.02 (12)
N1—C2—C3—N4	−7.31 (18)	C6—S7—C8—C9	−1.01 (15)
O2—C2—C3—C11	−61.48 (16)	C2—N1—C9—C8	108.88 (17)
N1—C2—C3—C11	118.88 (14)	C6—N1—C9—C8	−46.39 (18)
C2—C3—N4—C5	19.1 (2)	S7—C8—C9—N1	25.71 (19)
C11—C3—N4—C5	−105.20 (16)	N4—C3—C11—C12	63.34 (16)
C2—C3—N4—C10	−170.70 (12)	C2—C3—C11—C12	−64.85 (16)
C11—C3—N4—C10	64.96 (16)	C3—C11—C12—C13	−88.38 (17)
C3—N4—C5—O5	169.62 (15)	C3—C11—C12—C17	93.65 (17)
C10—N4—C5—O5	−0.3 (2)	C17—C12—C13—C14	1.0 (2)
C3—N4—C5—C6	−13.7 (2)	C11—C12—C13—C14	−176.96 (13)
C10—N4—C5—C6	176.37 (13)	C12—C13—C14—C15	−0.3 (2)
C2—N1—C6—C5	14.4 (2)	C13—C14—C15—C16	−0.3 (2)
C9—N1—C6—C5	168.93 (13)	C14—C15—C16—C17	0.1 (2)
C2—N1—C6—S7	−109.88 (14)	C15—C16—C17—C12	0.6 (2)
C9—N1—C6—S7	44.70 (13)	C13—C12—C17—C16	−1.2 (2)
O5—C5—C6—N1	173.84 (14)	C11—C12—C17—C16	176.81 (14)

(12b) top

Crystal data top

C₁₄H₁₆N₂O₂S	F(000) = 584
M_r = 276.35	D_x = 1.357 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4807 reflections
a = 10.0987 (4) Å	θ = 2.6–27.4°
b = 11.0883 (4) Å	µ = 0.24 mm⁻¹
c = 12.0825 (5) Å	T = 150 K
V = 1352.97 (9) Å³	Prism, colourless
Z = 4	0.54 × 0.41 × 0.26 mm

Data collection top

Bruker APEX-II CCD diffractometer	3096 independent reflections
Radiation source: fine-focus sealed tube	2931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	h = −13→12
T_min = 0.863, T_max = 0.941	k = −14→10
8542 measured reflections	l = −15→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0351P)² + 0.2268P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3096 reflections	Δρ_max = 0.18 e Å⁻³
173 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (6)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.22369 (12)	0.77660 (10)	0.41260 (9)	0.0210 (2)
C2	0.28328 (13)	0.87153 (12)	0.36511 (11)	0.0197 (3)
C3	0.35435 (12)	0.84942 (11)	0.25659 (11)	0.0180 (2)
H3	0.4353	0.9013	0.2574	0.022*
N4	0.40000 (11)	0.72480 (10)	0.24390 (9)	0.0184 (2)
C5	0.34087 (13)	0.62907 (12)	0.29054 (11)	0.0188 (3)
C6	0.22785 (13)	0.65444 (11)	0.36909 (10)	0.0181 (3)
H6	0.1423	0.6368	0.3307	0.022*
S7	0.23985 (4)	0.56073 (3)	0.49162 (3)	0.03100 (10)
C8	0.12233 (18)	0.66080 (15)	0.55673 (13)	0.0343 (4)
H8A	0.0312	0.6424	0.5316	0.041*
H8B	0.1260	0.6523	0.6382	0.041*
C9	0.16183 (18)	0.78775 (14)	0.52223 (13)	0.0347 (4)
H9A	0.0830	0.8406	0.5184	0.042*
H9B	0.2252	0.8225	0.5760	0.042*
C10	0.50501 (15)	0.70247 (15)	0.16278 (13)	0.0295 (3)
H10A	0.4654	0.6776	0.0923	0.044*
H10B	0.5634	0.6384	0.1900	0.044*
H10C	0.5565	0.7764	0.1517	0.044*
C11	0.26820 (14)	0.89321 (12)	0.15834 (11)	0.0221 (3)
H11A	0.2531	0.9811	0.1657	0.026*
H11B	0.3170	0.8794	0.0884	0.026*
C12	0.13645 (14)	0.83005 (11)	0.15212 (11)	0.0198 (3)
C13	0.02472 (15)	0.88075 (14)	0.20006 (13)	0.0289 (3)
H13	0.0306	0.9581	0.2335	0.035*
C14	−0.09570 (16)	0.82002 (17)	0.19984 (16)	0.0376 (4)
H14	−0.1716	0.8562	0.2323	0.045*
C15	−0.10488 (15)	0.70704 (15)	0.15234 (14)	0.0329 (4)
H15	−0.1867	0.6648	0.1530	0.040*
C16	0.00535 (15)	0.65563 (13)	0.10387 (13)	0.0278 (3)
H16	−0.0008	0.5779	0.0712	0.033*
C17	0.12537 (14)	0.71713 (12)	0.10266 (11)	0.0226 (3)
H17	0.2003	0.6818	0.0679	0.027*
O2	0.28006 (11)	0.97279 (9)	0.40579 (9)	0.0306 (2)
O5	0.37353 (11)	0.52417 (9)	0.27289 (9)	0.0301 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0259 (6)	0.0164 (5)	0.0208 (5)	0.0033 (5)	0.0063 (5)	0.0013 (4)
C2	0.0182 (6)	0.0176 (6)	0.0234 (6)	0.0024 (5)	−0.0022 (5)	0.0008 (5)
C3	0.0157 (6)	0.0158 (6)	0.0225 (6)	−0.0022 (5)	0.0001 (5)	0.0035 (5)
N4	0.0153 (5)	0.0191 (5)	0.0209 (5)	0.0013 (4)	0.0027 (4)	0.0024 (4)
C5	0.0177 (6)	0.0182 (6)	0.0206 (6)	0.0002 (5)	−0.0006 (5)	0.0004 (5)
C6	0.0179 (6)	0.0158 (6)	0.0207 (6)	−0.0003 (5)	0.0016 (5)	0.0028 (4)
S7	0.0407 (2)	0.02351 (17)	0.02876 (18)	0.00466 (15)	0.00626 (17)	0.01102 (13)
C8	0.0350 (9)	0.0396 (9)	0.0284 (7)	0.0016 (7)	0.0120 (7)	0.0067 (7)
C9	0.0461 (9)	0.0297 (8)	0.0282 (8)	0.0073 (7)	0.0175 (7)	0.0015 (6)
C10	0.0237 (8)	0.0325 (8)	0.0323 (8)	0.0010 (6)	0.0118 (6)	0.0017 (7)
C11	0.0222 (7)	0.0206 (6)	0.0234 (6)	−0.0015 (5)	−0.0015 (6)	0.0078 (5)
C12	0.0212 (6)	0.0183 (6)	0.0198 (6)	0.0014 (5)	−0.0042 (5)	0.0052 (5)
C13	0.0248 (7)	0.0219 (7)	0.0398 (8)	0.0041 (6)	−0.0025 (6)	−0.0045 (6)
C14	0.0214 (7)	0.0387 (9)	0.0529 (10)	0.0044 (7)	0.0044 (7)	−0.0047 (8)
C15	0.0222 (8)	0.0319 (8)	0.0447 (9)	−0.0048 (6)	−0.0064 (7)	0.0062 (7)
C16	0.0315 (8)	0.0222 (7)	0.0297 (7)	−0.0008 (6)	−0.0102 (6)	−0.0009 (6)
C17	0.0240 (7)	0.0231 (7)	0.0206 (6)	0.0034 (6)	−0.0025 (6)	−0.0002 (5)
O2	0.0380 (6)	0.0174 (5)	0.0363 (5)	0.0019 (4)	0.0033 (5)	−0.0043 (4)
O5	0.0313 (6)	0.0168 (5)	0.0423 (6)	0.0033 (4)	0.0092 (5)	−0.0022 (4)

Geometric parameters (Å, º) top

N1—C2	1.3414 (17)	C9—H9B	0.9900
N1—C6	1.4536 (16)	C10—H10A	0.9800
N1—C9	1.4697 (18)	C10—H10B	0.9800
C2—O2	1.2260 (16)	C10—H10C	0.9800
C2—C3	1.5149 (18)	C11—C12	1.5054 (19)
C3—N4	1.4647 (17)	C11—H11A	0.9900
C3—C11	1.5498 (18)	C11—H11B	0.9900
C3—H3	1.0000	C12—C13	1.387 (2)
N4—C5	1.3420 (17)	C12—C17	1.3919 (19)
N4—C10	1.4651 (18)	C13—C14	1.390 (2)
C5—O5	1.2278 (16)	C13—H13	0.9500
C5—C6	1.5108 (18)	C14—C15	1.381 (2)
C6—S7	1.8128 (12)	C14—H14	0.9500
C6—H6	1.0000	C15—C16	1.381 (2)
S7—C8	1.8051 (17)	C15—H15	0.9500
C8—C9	1.521 (2)	C16—C17	1.391 (2)
C8—H8A	0.9900	C16—H16	0.9500
C8—H8B	0.9900	C17—H17	0.9500
C9—H9A	0.9900

C2—N1—C6	124.31 (11)	N1—C9—H9B	110.5
C2—N1—C9	120.67 (11)	C8—C9—H9B	110.5
C6—N1—C9	114.62 (11)	H9A—C9—H9B	108.7
O2—C2—N1	122.36 (12)	N4—C10—H10A	109.5
O2—C2—C3	120.52 (12)	N4—C10—H10B	109.5
N1—C2—C3	117.11 (11)	H10A—C10—H10B	109.5
N4—C3—C2	113.11 (10)	N4—C10—H10C	109.5
N4—C3—C11	113.08 (11)	H10A—C10—H10C	109.5
C2—C3—C11	110.26 (11)	H10B—C10—H10C	109.5
N4—C3—H3	106.6	C12—C11—C3	112.87 (10)
C2—C3—H3	106.6	C12—C11—H11A	109.0
C11—C3—H3	106.6	C3—C11—H11A	109.0
C5—N4—C3	124.21 (11)	C12—C11—H11B	109.0
C5—N4—C10	117.99 (11)	C3—C11—H11B	109.0
C3—N4—C10	117.21 (11)	H11A—C11—H11B	107.8
O5—C5—N4	123.84 (13)	C13—C12—C17	118.58 (13)
O5—C5—C6	119.24 (12)	C13—C12—C11	120.63 (12)
N4—C5—C6	116.92 (11)	C17—C12—C11	120.72 (13)
N1—C6—C5	114.99 (11)	C12—C13—C14	120.96 (14)
N1—C6—S7	103.93 (8)	C12—C13—H13	119.5
C5—C6—S7	110.85 (9)	C14—C13—H13	119.5
N1—C6—H6	109.0	C15—C14—C13	119.93 (15)
C5—C6—H6	109.0	C15—C14—H14	120.0
S7—C6—H6	109.0	C13—C14—H14	120.0
C8—S7—C6	87.69 (6)	C16—C15—C14	119.77 (14)
C9—C8—S7	106.08 (11)	C16—C15—H15	120.1
C9—C8—H8A	110.5	C14—C15—H15	120.1
S7—C8—H8A	110.5	C15—C16—C17	120.30 (14)
C9—C8—H8B	110.5	C15—C16—H16	119.9
S7—C8—H8B	110.5	C17—C16—H16	119.9
H8A—C8—H8B	108.7	C16—C17—C12	120.44 (13)
N1—C9—C8	106.29 (12)	C16—C17—H17	119.8
N1—C9—H9A	110.5	C12—C17—H17	119.8
C8—C9—H9A	110.5

(14a) top

Crystal data top

C₁₄H₁₆N₂O₂S	D_x = 1.378 Mg m⁻³
M_r = 276.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3930 reflections
a = 7.7112 (7) Å	θ = 2.8–27.4°
b = 11.6576 (12) Å	µ = 0.24 mm⁻¹
c = 14.8171 (14) Å	T = 150 K
V = 1332.0 (2) Å³	Prism, colourless
Z = 4	0.47 × 0.32 × 0.22 mm
F(000) = 584

Data collection top

Bruker APEX-II CCD diffractometer	2789 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
φ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	h = −10→6
T_min = 0.895, T_max = 0.948	k = −15→14
8310 measured reflections	l = −19→17
3051 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0393P)² + 0.0987P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.082	(Δ/σ)_max = 0.005
S = 1.04	Δρ_max = 0.28 e Å⁻³
3051 reflections	Δρ_min = −0.22 e Å⁻³
173 parameters	Absolute structure: Flack x determined using 1085 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: −0.03 (5)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.7342 (2)	0.91146 (15)	0.95285 (12)	0.0172 (4)
C2	0.6237 (3)	0.87146 (18)	0.89056 (15)	0.0171 (5)
C3	0.4971 (3)	0.95500 (18)	0.84832 (15)	0.0173 (4)
H3	0.3783	0.9220	0.8562	0.021*
N4	0.4954 (2)	1.06933 (16)	0.88879 (12)	0.0179 (4)
C5	0.6271 (3)	1.11390 (19)	0.93647 (15)	0.0206 (5)
C6	0.7600 (3)	1.03238 (18)	0.97499 (15)	0.0181 (4)
H6	0.7551	1.0395	1.0422	0.022*
C7	0.9456 (3)	1.05934 (19)	0.94594 (16)	0.0211 (5)
H7A	0.9877	1.1307	0.9748	0.025*
H7B	0.9536	1.0676	0.8796	0.025*
S8	1.06830 (7)	0.93579 (5)	0.98469 (5)	0.02899 (17)
C9	0.8777 (3)	0.84158 (19)	0.98550 (16)	0.0211 (5)
H9A	0.8963	0.7747	0.9455	0.025*
H9B	0.8540	0.8135	1.0473	0.025*
C10	0.3559 (3)	1.1466 (2)	0.86001 (18)	0.0249 (5)
H10A	0.3948	1.1917	0.8080	0.037*
H10B	0.3259	1.1984	0.9097	0.037*
H10C	0.2538	1.1014	0.8431	0.037*
C11	0.5332 (2)	0.96046 (19)	0.74573 (15)	0.0182 (5)
H11A	0.5154	0.8833	0.7194	0.022*
H11B	0.4486	1.0131	0.7173	0.022*
C12	0.7149 (3)	1.00079 (19)	0.72346 (14)	0.0169 (5)
C13	0.8497 (3)	0.9231 (2)	0.71145 (14)	0.0212 (5)
H13	0.8286	0.8435	0.7197	0.025*
C14	1.0150 (3)	0.9601 (2)	0.68745 (18)	0.0260 (5)
H14	1.1055	0.9059	0.6787	0.031*
C15	1.0474 (3)	1.0762 (2)	0.67630 (15)	0.0256 (5)
H15	1.1595	1.1017	0.6590	0.031*
C16	0.9155 (3)	1.1546 (2)	0.69046 (16)	0.0256 (5)
H16	0.9383	1.2343	0.6846	0.031*
C17	0.7492 (3)	1.1174 (2)	0.71336 (15)	0.0217 (5)
H17	0.6591	1.1719	0.7221	0.026*
O2	0.6208 (2)	0.77031 (12)	0.86597 (11)	0.0235 (4)
O5	0.6384 (2)	1.21630 (14)	0.95518 (13)	0.0335 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0156 (8)	0.0167 (9)	0.0194 (9)	0.0033 (7)	0.0011 (7)	−0.0001 (7)
C2	0.0132 (10)	0.0188 (11)	0.0194 (12)	−0.0035 (8)	0.0058 (8)	0.0033 (9)
C3	0.0122 (9)	0.0162 (10)	0.0234 (11)	−0.0028 (8)	0.0002 (9)	0.0001 (9)
N4	0.0139 (8)	0.0156 (9)	0.0242 (10)	0.0036 (7)	0.0008 (7)	−0.0004 (8)
C5	0.0165 (10)	0.0232 (12)	0.0221 (12)	0.0040 (9)	0.0029 (9)	−0.0054 (9)
C6	0.0186 (10)	0.0194 (11)	0.0164 (10)	0.0022 (8)	−0.0002 (8)	−0.0052 (9)
C7	0.0165 (9)	0.0194 (11)	0.0273 (12)	0.0029 (9)	−0.0036 (9)	0.0002 (9)
S8	0.0153 (2)	0.0309 (3)	0.0408 (4)	0.0034 (2)	−0.0051 (2)	0.0057 (3)
C9	0.0195 (10)	0.0223 (11)	0.0213 (11)	0.0054 (9)	0.0012 (9)	0.0023 (10)
C10	0.0159 (10)	0.0229 (12)	0.0358 (14)	0.0077 (9)	0.0002 (10)	−0.0007 (11)
C11	0.0134 (10)	0.0206 (11)	0.0205 (11)	−0.0017 (8)	−0.0036 (8)	−0.0015 (9)
C12	0.0170 (10)	0.0216 (11)	0.0120 (10)	−0.0005 (9)	−0.0019 (9)	0.0004 (9)
C13	0.0183 (10)	0.0236 (12)	0.0218 (12)	0.0001 (10)	−0.0015 (9)	0.0001 (10)
C14	0.0166 (11)	0.0320 (14)	0.0292 (13)	0.0016 (10)	−0.0001 (10)	0.0030 (10)
C15	0.0168 (10)	0.0361 (13)	0.0238 (12)	−0.0065 (11)	−0.0004 (9)	0.0070 (11)
C16	0.0278 (13)	0.0243 (12)	0.0245 (12)	−0.0071 (10)	0.0025 (10)	0.0060 (10)
C17	0.0226 (11)	0.0230 (12)	0.0196 (12)	0.0011 (9)	0.0004 (9)	0.0031 (9)
O2	0.0223 (8)	0.0147 (8)	0.0335 (9)	−0.0035 (6)	0.0011 (7)	0.0001 (7)
O5	0.0285 (9)	0.0200 (9)	0.0521 (12)	0.0071 (7)	−0.0072 (9)	−0.0141 (8)

Geometric parameters (Å, º) top

N1—C2	1.340 (3)	C9—H9B	0.9900
N1—C9	1.457 (3)	C10—H10A	0.9800
N1—C6	1.461 (3)	C10—H10B	0.9800
C2—O2	1.234 (3)	C10—H10C	0.9800
C2—C3	1.514 (3)	C11—C12	1.514 (3)
C3—N4	1.462 (3)	C11—H11A	0.9900
C3—C11	1.547 (3)	C11—H11B	0.9900
C3—H3	1.0000	C12—C13	1.390 (3)
N4—C5	1.342 (3)	C12—C17	1.394 (3)
N4—C10	1.467 (3)	C13—C14	1.392 (3)
C5—O5	1.229 (3)	C13—H13	0.9500
C5—C6	1.509 (3)	C14—C15	1.385 (3)
C6—C7	1.527 (3)	C14—H14	0.9500
C6—H6	1.0000	C15—C16	1.384 (3)
C7—S8	1.817 (2)	C15—H15	0.9500
C7—H7A	0.9900	C16—C17	1.395 (3)
C7—H7B	0.9900	C16—H16	0.9500
S8—C9	1.835 (2)	C17—H17	0.9500
C9—H9A	0.9900

C2—N1—C9	121.15 (18)	N1—C9—H9B	110.6
C2—N1—C6	125.23 (17)	S8—C9—H9B	110.6
C9—N1—C6	111.21 (17)	H9A—C9—H9B	108.7
O2—C2—N1	123.2 (2)	N4—C10—H10A	109.5
O2—C2—C3	118.7 (2)	N4—C10—H10B	109.5
N1—C2—C3	118.10 (18)	H10A—C10—H10B	109.5
N4—C3—C2	115.00 (18)	N4—C10—H10C	109.5
N4—C3—C11	111.56 (17)	H10A—C10—H10C	109.5
C2—C3—C11	108.45 (18)	H10B—C10—H10C	109.5
N4—C3—H3	107.2	C12—C11—C3	113.18 (18)
C2—C3—H3	107.2	C12—C11—H11A	108.9
C11—C3—H3	107.2	C3—C11—H11A	108.9
C5—N4—C3	124.22 (18)	C12—C11—H11B	108.9
C5—N4—C10	118.06 (18)	C3—C11—H11B	108.9
C3—N4—C10	116.58 (18)	H11A—C11—H11B	107.8
O5—C5—N4	123.3 (2)	C13—C12—C17	118.7 (2)
O5—C5—C6	118.6 (2)	C13—C12—C11	121.2 (2)
N4—C5—C6	117.97 (19)	C17—C12—C11	120.2 (2)
N1—C6—C5	115.49 (18)	C12—C13—C14	121.0 (2)
N1—C6—C7	105.23 (17)	C12—C13—H13	119.5
C5—C6—C7	113.57 (18)	C14—C13—H13	119.5
N1—C6—H6	107.4	C15—C14—C13	119.9 (2)
C5—C6—H6	107.4	C15—C14—H14	120.1
C7—C6—H6	107.4	C13—C14—H14	120.1
C6—C7—S8	103.65 (15)	C16—C15—C14	119.7 (2)
C6—C7—H7A	111.0	C16—C15—H15	120.2
S8—C7—H7A	111.0	C14—C15—H15	120.2
C6—C7—H7B	111.0	C15—C16—C17	120.5 (2)
S8—C7—H7B	111.0	C15—C16—H16	119.8
H7A—C7—H7B	109.0	C17—C16—H16	119.8
C7—S8—C9	93.40 (10)	C12—C17—C16	120.2 (2)
N1—C9—S8	105.75 (14)	C12—C17—H17	119.9
N1—C9—H9A	110.6	C16—C17—H17	119.9
S8—C9—H9A	110.6

(14b) top

Crystal data top

C₁₄H₁₆N₂O₂S	F(000) = 1752
M_r = 276.35	D_x = 1.361 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9979 reflections
a = 13.4996 (5) Å	θ = 2.3–26.9°
b = 14.5841 (5) Å	µ = 0.24 mm⁻¹
c = 20.5461 (8) Å	T = 150 K
V = 4045.1 (3) Å³	Prism, colourless
Z = 12	0.56 × 0.39 × 0.37 mm

Data collection top

Bruker APEX-II CCD diffractometer	8811 independent reflections
Radiation source: fine-focus sealed tube	7668 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 27.0°, θ_min = 1.7°
Absorption correction: multi-scan SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	h = −13→17
T_min = 0.839, T_max = 0.917	k = −18→16
23583 measured reflections	l = −26→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0533P)² + 0.9427P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.003
8811 reflections	Δρ_max = 0.39 e Å⁻³
517 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (5)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N11	0.60480 (14)	0.32716 (12)	−0.07200 (9)	0.0262 (4)
C21	0.58491 (17)	0.30207 (14)	−0.13301 (10)	0.0251 (4)
C31	0.48098 (17)	0.26865 (15)	−0.14798 (10)	0.0258 (4)
H31	0.4602	0.2985	−0.1896	0.031*
N41	0.40698 (13)	0.29299 (12)	−0.09876 (9)	0.0264 (4)
C51	0.42813 (17)	0.31012 (14)	−0.03634 (10)	0.0269 (4)
C61	0.53587 (15)	0.32280 (14)	−0.01736 (10)	0.0244 (4)
H61	0.5560	0.2716	0.0122	0.029*
C71	0.54925 (16)	0.41394 (14)	0.01833 (11)	0.0280 (4)
H71A	0.5262	0.4090	0.0639	0.034*
H71B	0.5116	0.4633	−0.0036	0.034*
S81	0.68112 (5)	0.43720 (4)	0.01543 (3)	0.03865 (15)
C91	0.70182 (17)	0.36268 (17)	−0.05501 (12)	0.0333 (5)
H91A	0.7303	0.3979	−0.0917	0.040*
H91B	0.7476	0.3121	−0.0438	0.040*
C101	0.30269 (17)	0.28412 (17)	−0.11739 (12)	0.0352 (5)
H10A	0.2793	0.2222	−0.1069	0.053*
H10B	0.2958	0.2949	−0.1642	0.053*
H10C	0.2631	0.3292	−0.0935	0.053*
C111	0.48490 (18)	0.16381 (15)	−0.16082 (11)	0.0299 (5)
H11A	0.4194	0.1429	−0.1765	0.036*
H11B	0.5341	0.1511	−0.1954	0.036*
C121	0.51231 (17)	0.11065 (14)	−0.10070 (11)	0.0280 (5)
C131	0.61036 (19)	0.10116 (17)	−0.08142 (12)	0.0366 (5)
H131	0.6616	0.1252	−0.1081	0.044*
C141	0.63450 (19)	0.05691 (19)	−0.02363 (13)	0.0419 (6)
H141	0.7019	0.0516	−0.0109	0.050*
C151	0.5611 (2)	0.02076 (17)	0.01526 (13)	0.0419 (6)
H151	0.5777	−0.0100	0.0545	0.050*
C161	0.4630 (2)	0.02974 (18)	−0.00344 (12)	0.0402 (6)
H161	0.4120	0.0053	0.0233	0.048*
C171	0.43891 (18)	0.07419 (15)	−0.06084 (11)	0.0319 (5)
H171	0.3714	0.0799	−0.0732	0.038*
O21	0.64754 (12)	0.30304 (11)	−0.17623 (7)	0.0326 (4)
O51	0.36396 (12)	0.31954 (12)	0.00598 (8)	0.0363 (4)
N12	0.35662 (15)	−0.17699 (13)	−0.08737 (9)	0.0293 (4)
C22	0.40428 (19)	−0.19563 (15)	−0.03202 (10)	0.0316 (5)
C32	0.5139 (2)	−0.21435 (18)	−0.03580 (11)	0.0379 (6)
H32	0.5458	−0.1801	0.0008	0.045*
N42	0.56056 (15)	−0.18232 (14)	−0.09646 (10)	0.0363 (5)
C52	0.51233 (19)	−0.16795 (17)	−0.15212 (11)	0.0341 (5)
C62	0.40045 (18)	−0.17579 (15)	−0.15235 (10)	0.0290 (5)
H62	0.3813	−0.2333	−0.1757	0.035*
C72	0.35293 (18)	−0.09420 (16)	−0.18677 (11)	0.0346 (5)
H72A	0.3578	−0.1010	−0.2346	0.041*
H72B	0.3857	−0.0362	−0.1738	0.041*
S82	0.22375 (5)	−0.09506 (4)	−0.16072 (3)	0.03748 (14)
C92	0.25013 (18)	−0.16048 (17)	−0.08686 (12)	0.0349 (5)
H92A	0.2308	−0.1251	−0.0477	0.042*
H92B	0.2134	−0.2192	−0.0870	0.042*
C102	0.6689 (2)	−0.1749 (2)	−0.09628 (15)	0.0508 (7)
H10D	0.6979	−0.2321	−0.1125	0.076*
H10E	0.6921	−0.1635	−0.0518	0.076*
H10F	0.6892	−0.1240	−0.1244	0.076*
C112	0.5330 (2)	−0.31743 (18)	−0.02376 (13)	0.0416 (6)
H11C	0.6052	−0.3288	−0.0245	0.050*
H11D	0.5084	−0.3338	0.0201	0.050*
C122	0.48358 (18)	−0.37890 (16)	−0.07339 (11)	0.0333 (5)
C132	0.38367 (18)	−0.40155 (16)	−0.06889 (11)	0.0326 (5)
H132	0.3453	−0.3785	−0.0338	0.039*
C142	0.3395 (2)	−0.45759 (16)	−0.11535 (12)	0.0369 (5)
H142	0.2714	−0.4731	−0.1115	0.044*
C152	0.3944 (2)	−0.49074 (17)	−0.16709 (12)	0.0422 (6)
H152	0.3642	−0.5286	−0.1991	0.051*
C162	0.4932 (2)	−0.46846 (18)	−0.17187 (13)	0.0468 (7)
H162	0.5313	−0.4912	−0.2072	0.056*
C172	0.5377 (2)	−0.41291 (18)	−0.12535 (13)	0.0424 (6)
H172	0.6060	−0.3981	−0.1292	0.051*
O22	0.36184 (14)	−0.20075 (13)	0.02087 (8)	0.0428 (4)
O52	0.55408 (14)	−0.14734 (15)	−0.20364 (9)	0.0491 (5)
N13	0.53199 (13)	0.37714 (12)	0.29698 (8)	0.0255 (4)
C23	0.44281 (17)	0.34175 (14)	0.31160 (10)	0.0268 (4)
C33	0.38564 (17)	0.29795 (14)	0.25687 (10)	0.0268 (4)
H33	0.3548	0.2412	0.2751	0.032*
N43	0.44733 (13)	0.26897 (12)	0.20248 (9)	0.0256 (4)
C53	0.53506 (16)	0.30643 (14)	0.18708 (10)	0.0248 (4)
C63	0.57306 (15)	0.38195 (14)	0.23116 (10)	0.0245 (4)
H63	0.5557	0.4427	0.2116	0.029*
C73	0.68418 (17)	0.37675 (15)	0.23994 (12)	0.0319 (5)
H73A	0.7191	0.3987	0.2005	0.038*
H73B	0.7055	0.3132	0.2494	0.038*
S83	0.70814 (5)	0.45137 (5)	0.30873 (3)	0.04241 (16)
C93	0.59071 (18)	0.42212 (16)	0.34718 (11)	0.0335 (5)
H93A	0.6015	0.3804	0.3845	0.040*
H93B	0.5568	0.4781	0.3630	0.040*
C103	0.40747 (19)	0.19818 (17)	0.15918 (12)	0.0371 (5)
H10G	0.3971	0.2242	0.1157	0.056*
H10H	0.3442	0.1759	0.1765	0.056*
H10I	0.4545	0.1471	0.1564	0.056*
C113	0.29966 (16)	0.36076 (15)	0.23529 (11)	0.0293 (5)
H11E	0.2606	0.3291	0.2012	0.035*
H11F	0.2554	0.3719	0.2729	0.035*
C123	0.33569 (15)	0.45208 (14)	0.20894 (11)	0.0261 (4)
C133	0.35170 (18)	0.52535 (16)	0.25129 (12)	0.0333 (5)
H133	0.3377	0.5185	0.2963	0.040*
C143	0.3879 (2)	0.60818 (16)	0.22804 (13)	0.0413 (6)
H143	0.3984	0.6576	0.2573	0.050*
C153	0.4086 (2)	0.61926 (17)	0.16313 (14)	0.0418 (6)
H153	0.4333	0.6761	0.1474	0.050*
C163	0.39291 (18)	0.54662 (17)	0.12048 (12)	0.0364 (5)
H163	0.4072	0.5537	0.0755	0.044*
C173	0.35638 (16)	0.46356 (15)	0.14363 (11)	0.0294 (5)
H173	0.3456	0.4143	0.1142	0.035*
O23	0.40791 (14)	0.34572 (12)	0.36696 (8)	0.0392 (4)
O53	0.58457 (12)	0.28290 (11)	0.14017 (7)	0.0326 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0215 (9)	0.0263 (9)	0.0307 (9)	−0.0007 (7)	0.0025 (7)	0.0001 (7)
C21	0.0289 (12)	0.0178 (9)	0.0287 (10)	0.0038 (8)	0.0051 (9)	0.0038 (8)
C31	0.0294 (12)	0.0239 (10)	0.0241 (10)	0.0023 (9)	0.0004 (8)	0.0021 (8)
N41	0.0228 (9)	0.0243 (9)	0.0320 (9)	0.0000 (7)	0.0007 (7)	0.0003 (7)
C51	0.0272 (12)	0.0214 (10)	0.0320 (11)	0.0007 (8)	0.0024 (9)	0.0010 (8)
C61	0.0238 (11)	0.0237 (10)	0.0259 (10)	0.0016 (8)	0.0020 (8)	0.0016 (8)
C71	0.0265 (11)	0.0249 (10)	0.0325 (11)	0.0032 (8)	−0.0003 (9)	−0.0015 (8)
S81	0.0301 (3)	0.0359 (3)	0.0499 (4)	−0.0037 (3)	−0.0030 (3)	−0.0115 (3)
C91	0.0240 (12)	0.0365 (12)	0.0395 (13)	−0.0029 (9)	0.0020 (9)	−0.0074 (10)
C101	0.0256 (12)	0.0377 (13)	0.0424 (13)	0.0010 (10)	−0.0053 (10)	−0.0020 (10)
C111	0.0375 (13)	0.0235 (11)	0.0288 (10)	−0.0023 (9)	0.0022 (9)	−0.0027 (8)
C121	0.0329 (12)	0.0207 (10)	0.0306 (11)	0.0005 (9)	0.0051 (9)	−0.0038 (8)
C131	0.0341 (13)	0.0300 (12)	0.0456 (13)	0.0042 (10)	0.0119 (11)	0.0090 (10)
C141	0.0295 (12)	0.0424 (14)	0.0538 (15)	0.0061 (11)	0.0006 (11)	0.0132 (12)
C151	0.0467 (15)	0.0364 (13)	0.0426 (13)	0.0027 (11)	0.0002 (12)	0.0129 (11)
C161	0.0415 (15)	0.0381 (13)	0.0408 (13)	−0.0027 (11)	0.0076 (11)	0.0091 (10)
C171	0.0291 (12)	0.0294 (12)	0.0373 (12)	−0.0044 (9)	0.0024 (9)	0.0015 (9)
O21	0.0319 (9)	0.0330 (8)	0.0328 (8)	0.0044 (7)	0.0084 (7)	0.0043 (6)
O51	0.0280 (9)	0.0445 (10)	0.0364 (9)	−0.0017 (7)	0.0080 (7)	−0.0071 (7)
N12	0.0326 (10)	0.0283 (9)	0.0270 (9)	−0.0047 (8)	0.0047 (8)	−0.0016 (7)
C22	0.0453 (14)	0.0248 (11)	0.0247 (11)	−0.0095 (10)	0.0014 (9)	−0.0022 (8)
C32	0.0433 (15)	0.0434 (14)	0.0270 (11)	−0.0121 (12)	−0.0058 (10)	0.0012 (10)
N42	0.0315 (11)	0.0405 (12)	0.0369 (11)	−0.0109 (9)	0.0014 (9)	0.0023 (8)
C52	0.0371 (13)	0.0390 (13)	0.0261 (11)	−0.0085 (11)	0.0033 (10)	−0.0040 (9)
C62	0.0329 (12)	0.0290 (11)	0.0252 (10)	−0.0067 (9)	0.0019 (9)	−0.0038 (8)
C72	0.0434 (14)	0.0280 (11)	0.0323 (11)	−0.0069 (10)	0.0003 (10)	−0.0008 (9)
S82	0.0400 (3)	0.0305 (3)	0.0419 (3)	0.0015 (3)	−0.0029 (3)	−0.0031 (2)
C92	0.0365 (13)	0.0319 (12)	0.0364 (13)	−0.0007 (10)	0.0051 (10)	−0.0019 (9)
C102	0.0315 (14)	0.0625 (19)	0.0584 (17)	−0.0129 (13)	−0.0045 (13)	0.0036 (14)
C112	0.0373 (14)	0.0443 (14)	0.0431 (14)	−0.0034 (11)	−0.0127 (11)	0.0103 (11)
C122	0.0350 (13)	0.0278 (12)	0.0369 (12)	0.0042 (10)	−0.0066 (10)	0.0097 (9)
C132	0.0340 (13)	0.0298 (11)	0.0341 (11)	0.0020 (10)	−0.0009 (9)	0.0046 (9)
C142	0.0380 (14)	0.0309 (12)	0.0419 (13)	0.0021 (11)	−0.0047 (10)	0.0028 (10)
C152	0.0574 (17)	0.0274 (12)	0.0419 (13)	0.0052 (12)	−0.0009 (12)	0.0010 (10)
C162	0.0579 (18)	0.0351 (14)	0.0475 (15)	0.0149 (12)	0.0140 (13)	0.0003 (11)
C172	0.0338 (14)	0.0396 (14)	0.0538 (15)	0.0083 (11)	0.0090 (11)	0.0070 (12)
O22	0.0560 (12)	0.0462 (10)	0.0262 (8)	−0.0116 (9)	0.0059 (8)	−0.0037 (7)
O52	0.0411 (10)	0.0729 (13)	0.0333 (9)	−0.0158 (10)	0.0074 (8)	−0.0012 (9)
N13	0.0259 (9)	0.0244 (9)	0.0262 (9)	−0.0027 (7)	−0.0032 (7)	0.0007 (7)
C23	0.0313 (11)	0.0234 (10)	0.0258 (10)	0.0006 (9)	0.0013 (9)	0.0025 (8)
C33	0.0279 (11)	0.0194 (10)	0.0331 (11)	−0.0055 (8)	0.0020 (9)	0.0011 (8)
N43	0.0257 (9)	0.0195 (8)	0.0315 (9)	−0.0016 (7)	−0.0013 (8)	−0.0041 (7)
C53	0.0269 (11)	0.0215 (10)	0.0261 (10)	0.0031 (8)	−0.0047 (8)	0.0044 (8)
C63	0.0229 (10)	0.0212 (10)	0.0294 (10)	−0.0002 (8)	−0.0005 (8)	0.0018 (8)
C73	0.0258 (11)	0.0274 (11)	0.0424 (13)	−0.0008 (9)	−0.0014 (10)	−0.0059 (9)
S83	0.0290 (3)	0.0448 (4)	0.0534 (4)	−0.0071 (3)	−0.0060 (3)	−0.0126 (3)
C93	0.0377 (13)	0.0319 (12)	0.0308 (11)	−0.0049 (10)	−0.0053 (10)	−0.0021 (9)
C103	0.0356 (13)	0.0297 (12)	0.0459 (13)	−0.0033 (10)	−0.0026 (11)	−0.0130 (10)
C113	0.0232 (11)	0.0263 (10)	0.0386 (12)	−0.0039 (9)	0.0015 (9)	−0.0034 (9)
C123	0.0180 (10)	0.0216 (10)	0.0387 (11)	0.0021 (8)	−0.0018 (8)	−0.0040 (8)
C133	0.0327 (13)	0.0296 (12)	0.0377 (12)	0.0005 (10)	−0.0004 (10)	−0.0069 (9)
C143	0.0408 (14)	0.0244 (12)	0.0586 (16)	−0.0016 (10)	−0.0051 (12)	−0.0125 (11)
C153	0.0367 (14)	0.0259 (12)	0.0628 (16)	0.0003 (10)	0.0040 (12)	0.0050 (11)
C163	0.0339 (13)	0.0339 (12)	0.0415 (13)	0.0079 (11)	0.0025 (10)	0.0063 (10)
C173	0.0235 (11)	0.0300 (11)	0.0346 (12)	0.0063 (9)	−0.0023 (9)	−0.0050 (9)
O23	0.0445 (11)	0.0421 (10)	0.0309 (8)	−0.0064 (8)	0.0079 (8)	0.0000 (7)
O53	0.0312 (9)	0.0349 (9)	0.0316 (8)	0.0012 (7)	0.0028 (7)	−0.0029 (6)

Geometric parameters (Å, º) top

N11—C21	1.333 (3)	C92—H92B	0.9900
N11—C91	1.451 (3)	C102—H10D	0.9800
N11—C61	1.460 (3)	C102—H10E	0.9800
C21—O21	1.226 (3)	C102—H10F	0.9800
C21—C31	1.517 (3)	C112—C122	1.513 (3)
C31—N41	1.465 (3)	C112—H11C	0.9900
C31—C111	1.553 (3)	C112—H11D	0.9900
C31—H31	1.0000	C122—C172	1.385 (3)
N41—C51	1.337 (3)	C122—C132	1.392 (3)
N41—C101	1.465 (3)	C132—C142	1.391 (3)
C51—O51	1.235 (3)	C132—H132	0.9500
C51—C61	1.517 (3)	C142—C152	1.383 (4)
C61—C71	1.529 (3)	C142—H142	0.9500
C61—H61	1.0000	C152—C162	1.376 (4)
C71—S81	1.813 (2)	C152—H152	0.9500
C71—H71A	0.9900	C162—C172	1.390 (4)
C71—H71B	0.9900	C162—H162	0.9500
S81—C91	1.831 (2)	C172—H172	0.9500
C91—H91A	0.9900	N13—C23	1.344 (3)
C91—H91B	0.9900	N13—C93	1.457 (3)
C101—H10A	0.9800	N13—C63	1.463 (3)
C101—H10B	0.9800	C23—O23	1.232 (3)
C101—H10C	0.9800	C23—C33	1.506 (3)
C111—C121	1.505 (3)	C33—N43	1.456 (3)
C111—H11A	0.9900	C33—C113	1.544 (3)
C111—H11B	0.9900	C33—H33	1.0000
C121—C131	1.389 (3)	N43—C53	1.342 (3)
C121—C171	1.391 (3)	N43—C103	1.465 (3)
C131—C141	1.390 (3)	C53—O53	1.222 (3)
C131—H131	0.9500	C53—C63	1.516 (3)
C141—C151	1.377 (4)	C63—C73	1.513 (3)
C141—H141	0.9500	C63—H63	1.0000
C151—C161	1.386 (4)	C73—S83	1.813 (2)
C151—H151	0.9500	C73—H73A	0.9900
C161—C171	1.384 (3)	C73—H73B	0.9900
C161—H161	0.9500	S83—C93	1.822 (3)
C171—H171	0.9500	C93—H93A	0.9900
N12—C22	1.335 (3)	C93—H93B	0.9900
N12—C92	1.458 (3)	C103—H10G	0.9800
N12—C62	1.460 (3)	C103—H10H	0.9800
C22—O22	1.231 (3)	C103—H10I	0.9800
C22—C32	1.507 (4)	C113—C123	1.518 (3)
C32—N42	1.472 (3)	C113—H11E	0.9900
C32—C112	1.545 (4)	C113—H11F	0.9900
C32—H32	1.0000	C123—C173	1.381 (3)
N42—C52	1.333 (3)	C123—C133	1.395 (3)
N42—C102	1.467 (3)	C133—C143	1.388 (3)
C52—O52	1.236 (3)	C133—H133	0.9500
C52—C62	1.515 (3)	C143—C153	1.372 (4)
C62—C72	1.526 (3)	C143—H143	0.9500
C62—H62	1.0000	C153—C163	1.391 (4)
C72—S82	1.824 (3)	C153—H153	0.9500
C72—H72A	0.9900	C163—C173	1.392 (3)
C72—H72B	0.9900	C163—H163	0.9500
S82—C92	1.828 (2)	C173—H173	0.9500
C92—H92A	0.9900

C21—N11—C91	120.39 (18)	N12—C92—H92B	110.6
C21—N11—C61	125.65 (18)	S82—C92—H92B	110.6
C91—N11—C61	113.96 (17)	H92A—C92—H92B	108.7
O21—C21—N11	122.6 (2)	N42—C102—H10D	109.5
O21—C21—C31	119.65 (19)	N42—C102—H10E	109.5
N11—C21—C31	117.72 (18)	H10D—C102—H10E	109.5
N41—C31—C21	114.38 (17)	N42—C102—H10F	109.5
N41—C31—C111	112.29 (18)	H10D—C102—H10F	109.5
C21—C31—C111	108.63 (18)	H10E—C102—H10F	109.5
N41—C31—H31	107.1	C122—C112—C32	113.29 (19)
C21—C31—H31	107.1	C122—C112—H11C	108.9
C111—C31—H31	107.1	C32—C112—H11C	108.9
C51—N41—C101	118.18 (18)	C122—C112—H11D	108.9
C51—N41—C31	124.17 (18)	C32—C112—H11D	108.9
C101—N41—C31	116.97 (18)	H11C—C112—H11D	107.7
O51—C51—N41	123.1 (2)	C172—C122—C132	118.5 (2)
O51—C51—C61	118.54 (19)	C172—C122—C112	120.0 (2)
N41—C51—C61	118.29 (18)	C132—C122—C112	121.5 (2)
N11—C61—C51	114.75 (17)	C142—C132—C122	120.6 (2)
N11—C61—C71	104.82 (17)	C142—C132—H132	119.7
C51—C61—C71	110.03 (17)	C122—C132—H132	119.7
N11—C61—H61	109.0	C152—C142—C132	120.2 (3)
C51—C61—H61	109.0	C152—C142—H142	119.9
C71—C61—H61	109.0	C132—C142—H142	119.9
C61—C71—S81	105.24 (14)	C162—C152—C142	119.5 (3)
C61—C71—H71A	110.7	C162—C152—H152	120.3
S81—C71—H71A	110.7	C142—C152—H152	120.3
C61—C71—H71B	110.7	C152—C162—C172	120.5 (2)
S81—C71—H71B	110.7	C152—C162—H162	119.8
H71A—C71—H71B	108.8	C172—C162—H162	119.8
C71—S81—C91	93.71 (10)	C122—C172—C162	120.7 (3)
N11—C91—S81	105.32 (15)	C122—C172—H172	119.6
N11—C91—H91A	110.7	C162—C172—H172	119.6
S81—C91—H91A	110.7	C23—N13—C93	120.15 (18)
N11—C91—H91B	110.7	C23—N13—C63	124.36 (17)
S81—C91—H91B	110.7	C93—N13—C63	115.24 (17)
H91A—C91—H91B	108.8	O23—C23—N13	122.0 (2)
N41—C101—H10A	109.5	O23—C23—C33	120.9 (2)
N41—C101—H10B	109.5	N13—C23—C33	117.07 (18)
H10A—C101—H10B	109.5	N43—C33—C23	113.77 (18)
N41—C101—H10C	109.5	N43—C33—C113	112.44 (17)
H10A—C101—H10C	109.5	C23—C33—C113	110.38 (18)
H10B—C101—H10C	109.5	N43—C33—H33	106.6
C121—C111—C31	112.10 (18)	C23—C33—H33	106.6
C121—C111—H11A	109.2	C113—C33—H33	106.6
C31—C111—H11A	109.2	C53—N43—C33	124.57 (18)
C121—C111—H11B	109.2	C53—N43—C103	117.88 (19)
C31—C111—H11B	109.2	C33—N43—C103	117.41 (18)
H11A—C111—H11B	107.9	O53—C53—N43	123.7 (2)
C131—C121—C171	118.2 (2)	O53—C53—C63	119.36 (19)
C131—C121—C111	121.3 (2)	N43—C53—C63	116.98 (18)
C171—C121—C111	120.3 (2)	N13—C63—C73	105.26 (17)
C121—C131—C141	120.9 (2)	N13—C63—C53	112.90 (17)
C121—C131—H131	119.6	C73—C63—C53	111.75 (17)
C141—C131—H131	119.6	N13—C63—H63	108.9
C151—C141—C131	120.3 (2)	C73—C63—H63	108.9
C151—C141—H141	119.8	C53—C63—H63	108.9
C131—C141—H141	119.8	C63—C73—S83	103.87 (15)
C141—C151—C161	119.4 (2)	C63—C73—H73A	111.0
C141—C151—H151	120.3	S83—C73—H73A	111.0
C161—C151—H151	120.3	C63—C73—H73B	111.0
C171—C161—C151	120.3 (2)	S83—C73—H73B	111.0
C171—C161—H161	119.8	H73A—C73—H73B	109.0
C151—C161—H161	119.8	C73—S83—C93	92.42 (10)
C161—C171—C121	120.9 (2)	N13—C93—S83	105.79 (15)
C161—C171—H171	119.6	N13—C93—H93A	110.6
C121—C171—H171	119.6	S83—C93—H93A	110.6
C22—N12—C92	120.20 (19)	N13—C93—H93B	110.6
C22—N12—C62	125.9 (2)	S83—C93—H93B	110.6
C92—N12—C62	113.85 (19)	H93A—C93—H93B	108.7
O22—C22—N12	122.7 (2)	N43—C103—H10G	109.5
O22—C22—C32	119.4 (2)	N43—C103—H10H	109.5
N12—C22—C32	117.8 (2)	H10G—C103—H10H	109.5
N42—C32—C22	114.0 (2)	N43—C103—H10I	109.5
N42—C32—C112	111.9 (2)	H10G—C103—H10I	109.5
C22—C32—C112	109.3 (2)	H10H—C103—H10I	109.5
N42—C32—H32	107.1	C123—C113—C33	112.47 (17)
C22—C32—H32	107.1	C123—C113—H11E	109.1
C112—C32—H32	107.1	C33—C113—H11E	109.1
C52—N42—C102	118.5 (2)	C123—C113—H11F	109.1
C52—N42—C32	124.6 (2)	C33—C113—H11F	109.1
C102—N42—C32	116.6 (2)	H11E—C113—H11F	107.8
O52—C52—N42	123.4 (2)	C173—C123—C133	118.8 (2)
O52—C52—C62	118.1 (2)	C173—C123—C113	121.19 (19)
N42—C52—C62	118.5 (2)	C133—C123—C113	120.0 (2)
N12—C62—C52	113.72 (19)	C143—C133—C123	120.4 (2)
N12—C62—C72	105.23 (18)	C143—C133—H133	119.8
C52—C62—C72	111.21 (19)	C123—C133—H133	119.8
N12—C62—H62	108.8	C153—C143—C133	120.6 (2)
C52—C62—H62	108.8	C153—C143—H143	119.7
C72—C62—H62	108.8	C133—C143—H143	119.7
C62—C72—S82	105.10 (15)	C143—C153—C163	119.5 (2)
C62—C72—H72A	110.7	C143—C153—H153	120.3
S82—C72—H72A	110.7	C163—C153—H153	120.3
C62—C72—H72B	110.7	C153—C163—C173	120.1 (2)
S82—C72—H72B	110.7	C153—C163—H163	120.0
H72A—C72—H72B	108.8	C173—C163—H163	120.0
C72—S82—C92	93.49 (11)	C123—C173—C163	120.6 (2)
N12—C92—S82	105.81 (16)	C123—C173—H173	119.7
N12—C92—H92A	110.6	C163—C173—H173	119.7
S82—C92—H92A	110.6

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Format		BIBTeX
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Solid-state structure of cyclic dipeptides: an X-ray and computational study of cis- and trans-diketopiperazines of N-methyl-phenyl­alanine with the thia-pipecolic acids and thia-prolines

Supporting information

Solid-state structure of cyclic dipeptides: an X-ray and computational study of cis- and trans-diketopiperazines of N-methyl-phenylalanine with the thia-pipecolic acids and thia-prolines