Structures and physicochemical properties of vortioxetine salts

Zhou, X.; Hu, X.; Wu, S.; Ye, J.; Sun, M.; Gu, J.; Zhu, J.; Zhang, Z.

doi:10.1107/S2052520616010556

Structures and physicochemical properties of vortioxetine salts

X. Zhou, X. Hu, S. Wu, J. Ye, M. Sun, J. Gu, J. Zhu and Z. Zhang

In the present work, novel salts of the multimodal antidepressant drug vortioxetine (VT) were crystallized with pharmaceutically acceptable acids, aiming to improve the solubility of VT. The acids for VT were selected based on ΔpK_a being greater than 2 or 3. Salts of hydrobromic acid (HBr), hydrochloric acid (HCl), p-hydroxybenzoic acid (PHBA), saccharin (SAC) and L-aspartic acid (ASP) were reported. All salts were characterized by single-crystal X-ray diffraction, FT–IR, powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC). The acidic proton is transferred to the secondary N atom on the piperazine ring of VT, forming the charge-assisted hydrogen bond N⁺—H

X⁻ (X = Cl, Br, O). Solubility and intrinsic dissolution rate (IDR) experiments were carried out in distilled water (pH = 7.0) to compare the solubilities of the salts with that of VT. The VT–ASP–H₂O (1:1:2) salt showed 414 times higher solubility and 1722 times faster IDR compared with VT. VT–ASP–H₂O (1:1:2) is a high solubility salt that is stable in a slurry experiment at 298 K in 95% ethanol. The experimental data for the VT–ASP–H₂O (1:1:2) salt identify it as a promising drug candidate.

Keywords: vortioxetine; antidepressant; salt; solubility.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616010556/ao5012sup1.cif Contains datablocks 1, 2, 3, 4, 5, 6, 7, 8, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50121sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50122sup3.hkl Contains datablock 2
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50123sup4.hkl Contains datablock 3
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50124sup5.hkl Contains datablock 4
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50125sup6.hkl Contains datablock 5
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50126sup7.hkl Contains datablock 6
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50127sup8.hkl Contains datablock 7
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010556/ao50128sup9.hkl Contains datablock 8

CCDC references: 1432151; 1432152; 1432153; 1432154; 1432185; 1432597; 1432598; 1438705

Computing details top

For all compounds, data collection: PROCESS-AUTO (Rigaku,2006); cell refinement: PROCESS-AUTO (Rigaku,2006); data reduction: CrystalStructure (Rigaku,2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia,1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(1) top

Crystal data top

C₁₈H₂₃N₂S·C₄H₆NO₄·2(H₂O)	F(000) = 500
M_r = 467.57	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7998 reflections
a = 8.3052 (5) Å	θ = 3.1–27.4°
b = 6.1117 (3) Å	µ = 0.18 mm⁻¹
c = 23.7414 (13) Å	T = 296 K
β = 93.652 (2)°	Platelet, colorless
V = 1202.64 (11) Å³	0.41 × 0.34 × 0.08 mm
Z = 2

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4261 independent reflections
Radiation source: rotating anode	2893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 10.00 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan Higashi, T. (1995)	k = −7→6
T_min = 0.926, T_max = 0.986	l = −29→29
10512 measured 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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0418P)² + 0.6887P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4261 reflections	Δρ_max = 0.25 e Å⁻³
292 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: −0.03 (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
C16	0.4634 (4)	1.0549 (6)	0.22110 (15)	0.0460 (9)
H16A	0.3579	0.9922	0.2115	0.055*
H16B	0.4570	1.1414	0.2551	0.055*
C15	0.5864 (4)	0.8744 (6)	0.23104 (14)	0.0448 (8)
H15A	0.5558	0.7822	0.2618	0.054*
H15B	0.5888	0.7845	0.1974	0.054*
C18	0.7955 (4)	1.0990 (6)	0.19725 (14)	0.0438 (8)
H18A	0.7977	1.0084	0.1638	0.053*
H18B	0.9032	1.1568	0.2057	0.053*
C17	0.6783 (4)	1.2853 (6)	0.18640 (15)	0.0452 (9)
H17A	0.6795	1.3795	0.2193	0.054*
H17B	0.7104	1.3717	0.1547	0.054*
C14	0.8599 (4)	0.8030 (6)	0.26493 (14)	0.0394 (8)
C13	0.9738 (4)	0.7096 (7)	0.23220 (15)	0.0521 (10)
H13	0.9826	0.7578	0.1954	0.062*
C12	1.0750 (5)	0.5448 (7)	0.25380 (17)	0.0625 (11)
H12	1.1527	0.4859	0.2317	0.075*
C11	1.0609 (5)	0.4691 (7)	0.30731 (16)	0.0588 (11)
H11	1.1259	0.3546	0.3211	0.071*
C10	0.9500 (5)	0.5626 (7)	0.34100 (16)	0.0578 (11)
H10	0.9407	0.5103	0.3774	0.069*
C9	0.8523 (4)	0.7333 (6)	0.32116 (14)	0.0431 (8)
C1	0.7285 (5)	0.7336 (7)	0.42723 (15)	0.0492 (9)
C6	0.6453 (5)	0.5371 (7)	0.43226 (17)	0.0536 (10)
C5	0.6524 (5)	0.4359 (7)	0.48485 (18)	0.0599 (11)
H5	0.5967	0.3052	0.4887	0.072*
C4	0.7378 (5)	0.5200 (8)	0.53145 (18)	0.0612 (12)
C3	0.8175 (5)	0.7154 (8)	0.52557 (16)	0.0627 (11)
H3	0.8747	0.7770	0.5566	0.075*
C2	0.8135 (5)	0.8214 (7)	0.47378 (16)	0.0557 (10)
H2	0.8685	0.9527	0.4704	0.067*
C8	0.5505 (6)	0.4344 (8)	0.3825 (2)	0.0794 (14)
H8A	0.4798	0.3242	0.3958	0.119*
H8B	0.6236	0.3689	0.3577	0.119*
H8C	0.4879	0.5449	0.3625	0.119*
C7	0.7446 (7)	0.4050 (11)	0.5877 (2)	0.0961 (17)
H7A	0.8380	0.4532	0.6102	0.144*
H7B	0.7509	0.2498	0.5820	0.144*
H7C	0.6492	0.4387	0.6069	0.144*
C19	0.6255 (3)	0.8536 (6)	0.05815 (13)	0.0336 (7)
C20	0.7558 (3)	0.8494 (5)	0.01646 (12)	0.0330 (7)
H20A	0.8336	0.9628	0.0270	0.040*
H20B	0.7069	0.8867	−0.0205	0.040*
C21	0.8462 (3)	0.6351 (5)	0.01138 (13)	0.0295 (7)
H21	0.9175	0.6534	−0.0196	0.035*
C22	0.9541 (3)	0.5725 (5)	0.06368 (12)	0.0314 (7)
N2	0.5127 (3)	1.1970 (5)	0.17386 (11)	0.0415 (7)
H2A	0.5101	1.1187	0.1417	0.050*
H2B	0.4425	1.3086	0.1688	0.050*
N1	0.7472 (3)	0.9665 (4)	0.24479 (11)	0.0375 (7)
N3	0.7366 (3)	0.4491 (4)	−0.00443 (11)	0.0348 (6)
H3A	0.7035	0.3869	0.0267	0.052*
H3B	0.7893	0.3510	−0.0240	0.052*
H3C	0.6517	0.4983	−0.0254	0.052*
O1	0.5579 (3)	1.0380 (4)	0.06489 (10)	0.0443 (6)
O2	0.5906 (3)	0.6819 (4)	0.08196 (11)	0.0548 (7)
O3	0.9330 (2)	0.3917 (4)	0.08561 (9)	0.0428 (5)
O4	1.0631 (2)	0.7108 (4)	0.07782 (9)	0.0416 (6)
O5	0.3420 (3)	0.5782 (4)	0.14528 (10)	0.0468 (6)
H501	0.3763	0.6902	0.1312	0.070*
H502	0.2438	0.5842	0.1383	0.070*
O6	1.1740 (3)	0.1127 (4)	0.13059 (11)	0.0577 (7)
H601	1.1002	0.1953	0.1199	0.087*
H602	1.1404	−0.0111	0.1229	0.087*
S1	0.72259 (14)	0.88432 (18)	0.36320 (4)	0.0606 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C16	0.0387 (18)	0.054 (2)	0.0457 (19)	0.0062 (17)	0.0032 (15)	0.0084 (19)
C15	0.0384 (18)	0.045 (2)	0.0498 (19)	−0.0051 (17)	−0.0056 (15)	0.0065 (19)
C18	0.0397 (19)	0.047 (2)	0.0446 (19)	−0.0038 (17)	0.0040 (15)	0.0074 (17)
C17	0.050 (2)	0.040 (2)	0.0450 (19)	0.0010 (17)	0.0020 (16)	0.0078 (16)
C14	0.0374 (18)	0.0396 (19)	0.0401 (18)	0.0015 (15)	−0.0064 (15)	0.0031 (15)
C13	0.051 (2)	0.060 (3)	0.046 (2)	0.014 (2)	0.0060 (17)	0.007 (2)
C12	0.056 (2)	0.071 (3)	0.061 (3)	0.022 (2)	0.012 (2)	0.006 (2)
C11	0.059 (2)	0.063 (3)	0.055 (2)	0.027 (2)	0.0050 (19)	0.009 (2)
C10	0.065 (2)	0.064 (3)	0.043 (2)	0.017 (2)	−0.0032 (19)	0.012 (2)
C9	0.043 (2)	0.044 (2)	0.0418 (19)	0.0074 (16)	−0.0043 (15)	0.0033 (17)
C1	0.054 (2)	0.049 (2)	0.0444 (19)	0.0069 (18)	0.0074 (17)	−0.0043 (19)
C6	0.055 (2)	0.048 (2)	0.058 (2)	0.0080 (19)	0.0030 (18)	−0.004 (2)
C5	0.057 (2)	0.047 (3)	0.077 (3)	0.004 (2)	0.017 (2)	0.014 (2)
C4	0.058 (2)	0.071 (3)	0.056 (2)	0.016 (2)	0.009 (2)	0.017 (2)
C3	0.068 (3)	0.080 (3)	0.040 (2)	0.001 (3)	0.0001 (19)	0.002 (2)
C2	0.055 (2)	0.054 (3)	0.058 (2)	−0.0058 (19)	0.0060 (19)	−0.004 (2)
C8	0.079 (3)	0.065 (3)	0.092 (3)	0.002 (2)	−0.013 (3)	−0.021 (3)
C7	0.107 (4)	0.105 (4)	0.076 (3)	0.015 (4)	0.011 (3)	0.045 (3)
C19	0.0251 (15)	0.039 (2)	0.0360 (16)	0.0059 (15)	−0.0023 (12)	−0.0029 (16)
C20	0.0297 (16)	0.0335 (19)	0.0360 (16)	0.0034 (14)	0.0050 (13)	0.0032 (15)
C21	0.0219 (15)	0.0319 (17)	0.0345 (16)	−0.0014 (12)	0.0009 (12)	−0.0004 (14)
C22	0.0230 (15)	0.0381 (19)	0.0337 (16)	0.0042 (14)	0.0064 (12)	−0.0032 (15)
N2	0.0450 (17)	0.0435 (17)	0.0359 (15)	0.0106 (14)	0.0014 (12)	0.0015 (14)
N1	0.0342 (14)	0.0362 (15)	0.0415 (15)	0.0006 (12)	−0.0028 (12)	0.0056 (13)
N3	0.0287 (13)	0.0344 (15)	0.0408 (15)	−0.0002 (11)	−0.0011 (11)	−0.0020 (12)
O1	0.0335 (12)	0.0474 (15)	0.0515 (14)	0.0134 (11)	−0.0020 (10)	−0.0133 (12)
O2	0.0551 (16)	0.0457 (16)	0.0667 (17)	0.0017 (13)	0.0278 (13)	0.0059 (14)
O3	0.0396 (13)	0.0369 (13)	0.0511 (13)	−0.0001 (11)	−0.0024 (10)	0.0117 (12)
O4	0.0313 (12)	0.0421 (14)	0.0501 (13)	−0.0074 (11)	−0.0065 (10)	−0.0035 (12)
O5	0.0361 (12)	0.0471 (15)	0.0572 (14)	−0.0007 (11)	0.0026 (11)	0.0137 (12)
O6	0.0513 (15)	0.0496 (16)	0.0698 (17)	0.0013 (12)	−0.0156 (13)	0.0016 (14)
S1	0.0795 (7)	0.0556 (6)	0.0475 (5)	0.0251 (6)	0.0115 (5)	0.0064 (5)

Geometric parameters (Å, º) top

C16—N2	1.496 (4)	C5—H5	0.9300
C16—C15	1.512 (5)	C4—C3	1.377 (6)
C16—H16A	0.9700	C4—C7	1.508 (6)
C16—H16B	0.9700	C3—C2	1.388 (5)
C15—N1	1.467 (4)	C3—H3	0.9300
C15—H15A	0.9700	C2—H2	0.9300
C15—H15B	0.9700	C8—H8A	0.9600
C18—N1	1.466 (4)	C8—H8B	0.9600
C18—C17	1.509 (5)	C8—H8C	0.9600
C18—H18A	0.9700	C7—H7A	0.9600
C18—H18B	0.9700	C7—H7B	0.9600
C17—N2	1.490 (4)	C7—H7C	0.9600
C17—H17A	0.9700	C19—O2	1.235 (4)
C17—H17B	0.9700	C19—O1	1.274 (4)
C14—C13	1.385 (5)	C19—C20	1.512 (4)
C14—C9	1.407 (5)	C20—C21	1.518 (4)
C14—N1	1.431 (4)	C20—H20A	0.9700
C13—C12	1.389 (5)	C20—H20B	0.9700
C13—H13	0.9300	C21—N3	1.489 (4)
C12—C11	1.364 (5)	C21—C22	1.533 (4)
C12—H12	0.9300	C21—H21	0.9800
C11—C10	1.382 (5)	C22—O3	1.239 (4)
C11—H11	0.9300	C22—O4	1.268 (4)
C10—C9	1.386 (5)	N2—H2A	0.9000
C10—H10	0.9300	N2—H2B	0.9000
C9—S1	1.773 (4)	N3—H3A	0.8900
C1—C2	1.381 (5)	N3—H3B	0.8900
C1—C6	1.394 (6)	N3—H3C	0.8900
C1—S1	1.776 (4)	O5—H501	0.8204
C6—C5	1.391 (5)	O5—H502	0.8225
C6—C8	1.513 (6)	O6—H601	0.8223
C5—C4	1.375 (6)	O6—H602	0.8234

N2—C16—C15	109.0 (3)	C4—C3—C2	120.6 (4)
N2—C16—H16A	109.9	C4—C3—H3	119.7
C15—C16—H16A	109.9	C2—C3—H3	119.7
N2—C16—H16B	109.9	C1—C2—C3	120.7 (4)
C15—C16—H16B	109.9	C1—C2—H2	119.7
H16A—C16—H16B	108.3	C3—C2—H2	119.7
N1—C15—C16	110.6 (3)	C6—C8—H8A	109.5
N1—C15—H15A	109.5	C6—C8—H8B	109.5
C16—C15—H15A	109.5	H8A—C8—H8B	109.5
N1—C15—H15B	109.5	C6—C8—H8C	109.5
C16—C15—H15B	109.5	H8A—C8—H8C	109.5
H15A—C15—H15B	108.1	H8B—C8—H8C	109.5
N1—C18—C17	110.1 (3)	C4—C7—H7A	109.5
N1—C18—H18A	109.6	C4—C7—H7B	109.5
C17—C18—H18A	109.6	H7A—C7—H7B	109.5
N1—C18—H18B	109.6	C4—C7—H7C	109.5
C17—C18—H18B	109.6	H7A—C7—H7C	109.5
H18A—C18—H18B	108.2	H7B—C7—H7C	109.5
N2—C17—C18	109.8 (3)	O2—C19—O1	125.1 (3)
N2—C17—H17A	109.7	O2—C19—C20	118.9 (3)
C18—C17—H17A	109.7	O1—C19—C20	115.9 (3)
N2—C17—H17B	109.7	C19—C20—C21	116.4 (3)
C18—C17—H17B	109.7	C19—C20—H20A	108.2
H17A—C17—H17B	108.2	C21—C20—H20A	108.2
C13—C14—C9	118.8 (3)	C19—C20—H20B	108.2
C13—C14—N1	123.8 (3)	C21—C20—H20B	108.2
C9—C14—N1	117.4 (3)	H20A—C20—H20B	107.3
C14—C13—C12	120.7 (3)	N3—C21—C20	112.4 (2)
C14—C13—H13	119.7	N3—C21—C22	109.3 (2)
C12—C13—H13	119.7	C20—C21—C22	114.7 (3)
C11—C12—C13	120.3 (4)	N3—C21—H21	106.7
C11—C12—H12	119.9	C20—C21—H21	106.7
C13—C12—H12	119.9	C22—C21—H21	106.7
C12—C11—C10	119.9 (4)	O3—C22—O4	126.9 (3)
C12—C11—H11	120.1	O3—C22—C21	118.2 (3)
C10—C11—H11	120.1	O4—C22—C21	114.8 (3)
C11—C10—C9	120.8 (4)	C17—N2—C16	110.7 (2)
C11—C10—H10	119.6	C17—N2—H2A	109.5
C9—C10—H10	119.6	C16—N2—H2A	109.5
C10—C9—C14	119.3 (3)	C17—N2—H2B	109.5
C10—C9—S1	124.3 (3)	C16—N2—H2B	109.5
C14—C9—S1	116.2 (3)	H2A—N2—H2B	108.1
C2—C1—C6	119.8 (4)	C14—N1—C18	116.0 (3)
C2—C1—S1	117.9 (3)	C14—N1—C15	111.9 (3)
C6—C1—S1	122.2 (3)	C18—N1—C15	109.3 (2)
C5—C6—C1	117.9 (4)	C21—N3—H3A	109.5
C5—C6—C8	120.4 (4)	C21—N3—H3B	109.5
C1—C6—C8	121.8 (4)	H3A—N3—H3B	109.5
C4—C5—C6	123.1 (4)	C21—N3—H3C	109.5
C4—C5—H5	118.5	H3A—N3—H3C	109.5
C6—C5—H5	118.5	H3B—N3—H3C	109.5
C5—C4—C3	118.0 (4)	H501—O5—H502	104.3
C5—C4—C7	121.8 (5)	H601—O6—H602	105.0
C3—C4—C7	120.2 (4)	C9—S1—C1	103.12 (17)

N2—C16—C15—N1	58.7 (4)	S1—C1—C2—C3	177.6 (3)
N1—C18—C17—N2	−58.9 (4)	C4—C3—C2—C1	0.4 (6)
C9—C14—C13—C12	2.2 (6)	O2—C19—C20—C21	−5.9 (4)
N1—C14—C13—C12	−177.2 (3)	O1—C19—C20—C21	175.4 (3)
C14—C13—C12—C11	1.5 (6)	C19—C20—C21—N3	57.7 (3)
C13—C12—C11—C10	−2.6 (7)	C19—C20—C21—C22	−67.9 (3)
C12—C11—C10—C9	−0.1 (7)	N3—C21—C22—O3	−2.6 (4)
C11—C10—C9—C14	3.8 (6)	C20—C21—C22—O3	124.6 (3)
C11—C10—C9—S1	−172.7 (3)	N3—C21—C22—O4	173.5 (2)
C13—C14—C9—C10	−4.8 (5)	C20—C21—C22—O4	−59.2 (3)
N1—C14—C9—C10	174.7 (3)	C18—C17—N2—C16	56.9 (4)
C13—C14—C9—S1	171.9 (3)	C15—C16—N2—C17	−56.5 (4)
N1—C14—C9—S1	−8.6 (4)	C13—C14—N1—C18	−24.8 (5)
C2—C1—C6—C5	−0.3 (6)	C9—C14—N1—C18	155.8 (3)
S1—C1—C6—C5	−177.5 (3)	C13—C14—N1—C15	101.5 (4)
C2—C1—C6—C8	180.0 (4)	C9—C14—N1—C15	−77.9 (4)
S1—C1—C6—C8	2.8 (5)	C17—C18—N1—C14	−171.4 (3)
C1—C6—C5—C4	−0.4 (6)	C17—C18—N1—C15	61.0 (4)
C8—C6—C5—C4	179.3 (4)	C16—C15—N1—C14	168.8 (3)
C6—C5—C4—C3	1.1 (6)	C16—C15—N1—C18	−61.3 (4)
C6—C5—C4—C7	−179.3 (4)	C10—C9—S1—C1	−9.4 (4)
C5—C4—C3—C2	−1.1 (6)	C14—C9—S1—C1	174.1 (3)
C7—C4—C3—C2	179.3 (4)	C2—C1—S1—C9	106.8 (3)
C6—C1—C2—C3	0.3 (6)	C6—C1—S1—C9	−76.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.90	1.95	2.811 (4)	159
O5—H501···O2	0.82	2.19	2.706 (3)	121
O6—H601···O3	0.82	1.97	2.790 (3)	173
N3—H3A···O2	0.89	2.45	2.832 (4)	106
N2—H2B···O5ⁱ	0.90	1.91	2.789 (4)	163
N3—H3B···O4ⁱⁱ	0.89	2.02	2.880 (3)	163
N3—H3C···O1ⁱⁱⁱ	0.89	1.94	2.809 (3)	166
O5—H502···O4^iv	0.82	2.15	2.848 (3)	142
O6—H602···O4^v	0.82	2.09	2.882 (4)	162

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

(2) top

Crystal data top

C₁₈H₂₃N₂S·C₇H₅O₃·H₂O	F(000) = 968
M_r = 454.57	D_x = 1.196 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11817 reflections
a = 16.9513 (9) Å	θ = 3.1–27.5°
b = 6.9458 (5) Å	µ = 0.16 mm⁻¹
c = 21.5346 (11) Å	T = 296 K
β = 95.409 (1)°	Platelet, colorless
V = 2524.2 (3) Å³	0.53 × 0.47 × 0.16 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	5708 independent reflections
Radiation source: rotating anode	2836 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −21→21
Absorption correction: multi-scan Higashi, T. (1995)	k = −9→8
T_min = 0.920, T_max = 0.975	l = −23→27
23055 measured 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)] = 0.068	H-atom parameters constrained
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.070P)² + 1.3245P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
5708 reflections	Δρ_max = 0.30 e Å⁻³
292 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.019 (2)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.9819 (2)	0.3543 (7)	0.63561 (16)	0.0815 (11)
C2	1.0569 (2)	0.4319 (7)	0.63985 (17)	0.0970 (14)
H2	1.0660	0.5457	0.6190	0.116*
C3	1.1188 (2)	0.3419 (9)	0.67488 (19)	0.1155 (18)
H3	1.1690	0.3972	0.6777	0.139*
C4	1.1076 (3)	0.1731 (10)	0.70551 (18)	0.118 (2)
C5	1.0334 (4)	0.0953 (8)	0.69998 (19)	0.1153 (17)
H5	1.0255	−0.0205	0.7201	0.138*
C6	0.9686 (3)	0.1808 (7)	0.66556 (19)	0.0950 (13)
C7	1.1768 (3)	0.0789 (10)	0.7441 (2)	0.179 (3)
H7A	1.2255	0.1149	0.7278	0.268*
H7B	1.1709	−0.0585	0.7423	0.268*
H7C	1.1777	0.1208	0.7867	0.268*
C8	0.8882 (3)	0.0848 (8)	0.6609 (3)	0.1389 (19)
H8A	0.8475	0.1814	0.6590	0.208*
H8B	0.8841	0.0051	0.6969	0.208*
H8C	0.8818	0.0070	0.6239	0.208*
C9	0.87838 (19)	0.3589 (5)	0.52761 (16)	0.0732 (10)
C10	0.9202 (3)	0.2033 (7)	0.5071 (2)	0.1177 (18)
H10	0.9660	0.1627	0.5307	0.141*
C11	0.8958 (3)	0.1079 (7)	0.4529 (2)	0.1148 (17)
H11	0.9244	0.0026	0.4405	0.138*
C12	0.8305 (2)	0.1668 (6)	0.41753 (18)	0.0871 (12)
H12	0.8142	0.1027	0.3806	0.104*
C13	0.78824 (19)	0.3207 (5)	0.43597 (16)	0.0685 (9)
H13	0.7434	0.3607	0.4111	0.082*
C14	0.81071 (16)	0.4179 (4)	0.49056 (14)	0.0572 (8)
C15	0.70611 (17)	0.5142 (4)	0.55130 (14)	0.0590 (8)
H15A	0.7297	0.4312	0.5842	0.071*
H15B	0.6663	0.4404	0.5262	0.071*
C16	0.66769 (18)	0.6836 (5)	0.57954 (14)	0.0626 (8)
H16A	0.6261	0.6396	0.6041	0.075*
H16B	0.7066	0.7529	0.6069	0.075*
C17	0.6958 (2)	0.8767 (5)	0.48995 (16)	0.0731 (10)
H17A	0.7361	0.9493	0.5149	0.088*
H17B	0.6725	0.9598	0.4570	0.088*
C18	0.7327 (2)	0.7034 (5)	0.46206 (14)	0.0671 (9)
H18A	0.6928	0.6333	0.4360	0.081*
H18B	0.7735	0.7446	0.4363	0.081*
C19	0.47299 (17)	0.7501 (4)	0.41954 (12)	0.0502 (7)
C20	0.44314 (17)	0.7460 (4)	0.35223 (12)	0.0511 (7)
C21	0.48988 (19)	0.6729 (5)	0.30822 (13)	0.0608 (8)
H21	0.5400	0.6252	0.3212	0.073*
C22	0.4635 (2)	0.6697 (5)	0.24564 (14)	0.0672 (9)
H22	0.4956	0.6205	0.2168	0.081*
C23	0.38943 (19)	0.7396 (5)	0.22611 (13)	0.0667 (9)
C24	0.34174 (19)	0.8130 (6)	0.26920 (14)	0.0740 (10)
H24	0.2915	0.8597	0.2561	0.089*
C25	0.36907 (18)	0.8169 (5)	0.33168 (14)	0.0632 (9)
H25	0.3371	0.8679	0.3604	0.076*
N1	0.76746 (13)	0.5781 (3)	0.51217 (11)	0.0541 (6)
N2	0.63402 (14)	0.8122 (4)	0.52939 (11)	0.0588 (7)
H2A	0.6121	0.9154	0.5463	0.071*
H2B	0.5957	0.7496	0.5056	0.071*
O2	0.43593 (12)	0.8472 (3)	0.45674 (8)	0.0604 (6)
O1	0.53378 (13)	0.6534 (3)	0.43715 (9)	0.0679 (6)
O3	0.35915 (15)	0.7412 (5)	0.16519 (10)	0.1004 (9)
H3A	0.3916	0.6950	0.1435	0.151*
O4	0.46355 (14)	0.7404 (3)	0.58120 (9)	0.0747 (7)
H41	0.4617	0.7754	0.5429	0.112*
H42	0.4782	0.6037	0.5747	0.112*
S1	0.90446 (6)	0.49192 (16)	0.59616 (5)	0.0857 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.073 (2)	0.107 (3)	0.064 (2)	0.027 (2)	0.0067 (17)	0.003 (2)
C2	0.073 (2)	0.149 (4)	0.068 (2)	0.022 (3)	0.0008 (19)	0.016 (2)
C3	0.076 (3)	0.203 (6)	0.067 (2)	0.032 (3)	0.001 (2)	−0.002 (3)
C4	0.109 (4)	0.192 (6)	0.053 (2)	0.078 (4)	0.006 (2)	0.008 (3)
C5	0.142 (4)	0.130 (4)	0.076 (3)	0.062 (4)	0.021 (3)	0.020 (3)
C6	0.098 (3)	0.109 (4)	0.079 (3)	0.030 (3)	0.016 (2)	0.006 (2)
C7	0.175 (5)	0.281 (8)	0.076 (3)	0.141 (6)	−0.013 (3)	0.015 (4)
C8	0.144 (5)	0.114 (4)	0.163 (5)	0.004 (4)	0.033 (4)	0.014 (4)
C9	0.0638 (19)	0.082 (3)	0.074 (2)	0.0283 (18)	0.0043 (16)	−0.0014 (18)
C10	0.107 (3)	0.146 (4)	0.095 (3)	0.084 (3)	−0.016 (2)	−0.024 (3)
C11	0.119 (3)	0.121 (4)	0.101 (3)	0.071 (3)	−0.003 (3)	−0.030 (3)
C12	0.100 (3)	0.074 (3)	0.086 (3)	0.022 (2)	0.006 (2)	−0.020 (2)
C13	0.0652 (19)	0.065 (2)	0.075 (2)	0.0065 (17)	0.0046 (16)	−0.0065 (18)
C14	0.0497 (16)	0.0512 (19)	0.072 (2)	0.0098 (14)	0.0139 (14)	0.0037 (15)
C15	0.0569 (17)	0.055 (2)	0.0664 (18)	0.0069 (15)	0.0129 (14)	0.0142 (15)
C16	0.0559 (17)	0.073 (2)	0.0595 (18)	0.0133 (16)	0.0070 (14)	0.0071 (16)
C17	0.082 (2)	0.057 (2)	0.082 (2)	0.0180 (18)	0.0181 (18)	0.0170 (17)
C18	0.076 (2)	0.058 (2)	0.071 (2)	0.0181 (17)	0.0230 (16)	0.0184 (16)
C19	0.0613 (17)	0.0432 (17)	0.0458 (15)	0.0029 (14)	0.0038 (13)	0.0041 (13)
C20	0.0611 (17)	0.0464 (17)	0.0456 (14)	0.0044 (14)	0.0039 (13)	0.0035 (13)
C21	0.0680 (18)	0.065 (2)	0.0482 (16)	0.0133 (16)	0.0011 (14)	−0.0003 (14)
C22	0.079 (2)	0.073 (2)	0.0493 (17)	0.0064 (18)	0.0087 (15)	−0.0025 (15)
C23	0.071 (2)	0.085 (3)	0.0433 (16)	−0.0094 (18)	−0.0005 (15)	0.0047 (16)
C24	0.0566 (18)	0.108 (3)	0.0557 (18)	−0.0008 (18)	−0.0053 (15)	0.0134 (18)
C25	0.0584 (18)	0.077 (2)	0.0549 (17)	0.0054 (16)	0.0058 (14)	0.0068 (16)
N1	0.0477 (12)	0.0497 (15)	0.0660 (14)	0.0072 (11)	0.0117 (11)	0.0082 (12)
N2	0.0583 (14)	0.0603 (17)	0.0576 (14)	0.0176 (12)	0.0037 (11)	−0.0016 (12)
O2	0.0774 (13)	0.0553 (13)	0.0489 (11)	0.0137 (11)	0.0085 (10)	−0.0007 (9)
O1	0.0774 (14)	0.0687 (15)	0.0552 (12)	0.0272 (12)	−0.0062 (10)	−0.0036 (10)
O3	0.0902 (17)	0.163 (3)	0.0451 (12)	−0.0075 (17)	−0.0109 (12)	0.0059 (15)
O4	0.1038 (17)	0.0709 (16)	0.0495 (11)	0.0150 (13)	0.0078 (11)	0.0026 (11)
S1	0.0751 (6)	0.1004 (8)	0.0794 (6)	0.0299 (5)	−0.0048 (5)	−0.0099 (5)

Geometric parameters (Å, º) top

C1—C2	1.376 (5)	C15—H15A	0.9700
C1—C6	1.395 (6)	C15—H15B	0.9700
C1—S1	1.774 (4)	C16—N2	1.474 (4)
C2—C3	1.383 (5)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.368 (7)	C17—N2	1.479 (4)
C3—H3	0.9300	C17—C18	1.507 (4)
C4—C5	1.363 (7)	C17—H17A	0.9700
C4—C7	1.521 (6)	C17—H17B	0.9700
C5—C6	1.398 (6)	C18—N1	1.466 (4)
C5—H5	0.9300	C18—H18A	0.9700
C6—C8	1.512 (7)	C18—H18B	0.9700
C7—H7A	0.9600	C19—O1	1.258 (3)
C7—H7B	0.9600	C19—O2	1.259 (3)
C7—H7C	0.9600	C19—C20	1.490 (4)
C8—H8A	0.9600	C20—C25	1.382 (4)
C8—H8B	0.9600	C20—C21	1.387 (4)
C8—H8C	0.9600	C21—C22	1.380 (4)
C9—C10	1.387 (5)	C21—H21	0.9300
C9—C14	1.396 (4)	C22—C23	1.374 (4)
C9—S1	1.762 (4)	C22—H22	0.9300
C10—C11	1.373 (6)	C23—O3	1.363 (3)
C10—H10	0.9300	C23—C24	1.384 (5)
C11—C12	1.346 (5)	C24—C25	1.381 (4)
C11—H11	0.9300	C24—H24	0.9300
C12—C13	1.366 (5)	C25—H25	0.9300
C12—H12	0.9300	N2—H2A	0.9000
C13—C14	1.378 (4)	N2—H2B	0.9000
C13—H13	0.9300	O3—H3A	0.8200
C14—N1	1.434 (4)	O4—H41	0.8579
C15—N1	1.468 (4)	O4—H42	0.9947
C15—C16	1.502 (4)

C2—C1—C6	119.7 (4)	H15A—C15—H15B	108.1
C2—C1—S1	117.3 (3)	N2—C16—C15	109.3 (2)
C6—C1—S1	122.8 (3)	N2—C16—H16A	109.8
C1—C2—C3	120.6 (5)	C15—C16—H16A	109.8
C1—C2—H2	119.7	N2—C16—H16B	109.8
C3—C2—H2	119.7	C15—C16—H16B	109.8
C4—C3—C2	121.1 (5)	H16A—C16—H16B	108.3
C4—C3—H3	119.4	N2—C17—C18	109.3 (3)
C2—C3—H3	119.4	N2—C17—H17A	109.8
C5—C4—C3	117.9 (4)	C18—C17—H17A	109.8
C5—C4—C7	122.4 (6)	N2—C17—H17B	109.8
C3—C4—C7	119.8 (6)	C18—C17—H17B	109.8
C4—C5—C6	123.4 (5)	H17A—C17—H17B	108.3
C4—C5—H5	118.3	N1—C18—C17	109.5 (3)
C6—C5—H5	118.3	N1—C18—H18A	109.8
C1—C6—C5	117.3 (5)	C17—C18—H18A	109.8
C1—C6—C8	122.3 (4)	N1—C18—H18B	109.8
C5—C6—C8	120.4 (5)	C17—C18—H18B	109.8
C4—C7—H7A	109.5	H18A—C18—H18B	108.2
C4—C7—H7B	109.5	O1—C19—O2	122.5 (2)
H7A—C7—H7B	109.5	O1—C19—C20	118.4 (3)
C4—C7—H7C	109.5	O2—C19—C20	119.0 (3)
H7A—C7—H7C	109.5	C25—C20—C21	118.1 (3)
H7B—C7—H7C	109.5	C25—C20—C19	121.3 (3)
C6—C8—H8A	109.5	C21—C20—C19	120.5 (3)
C6—C8—H8B	109.5	C22—C21—C20	121.3 (3)
H8A—C8—H8B	109.5	C22—C21—H21	119.4
C6—C8—H8C	109.5	C20—C21—H21	119.4
H8A—C8—H8C	109.5	C23—C22—C21	119.8 (3)
H8B—C8—H8C	109.5	C23—C22—H22	120.1
C10—C9—C14	117.7 (3)	C21—C22—H22	120.1
C10—C9—S1	125.4 (3)	O3—C23—C22	123.2 (3)
C14—C9—S1	116.9 (2)	O3—C23—C24	116.8 (3)
C11—C10—C9	121.6 (3)	C22—C23—C24	119.9 (3)
C11—C10—H10	119.2	C25—C24—C23	119.8 (3)
C9—C10—H10	119.2	C25—C24—H24	120.1
C12—C11—C10	120.1 (4)	C23—C24—H24	120.1
C12—C11—H11	120.0	C24—C25—C20	121.1 (3)
C10—C11—H11	120.0	C24—C25—H25	119.5
C11—C12—C13	119.9 (4)	C20—C25—H25	119.5
C11—C12—H12	120.0	C14—N1—C18	113.8 (2)
C13—C12—H12	120.0	C14—N1—C15	111.3 (2)
C12—C13—C14	121.4 (3)	C18—N1—C15	110.2 (2)
C12—C13—H13	119.3	C16—N2—C17	111.0 (2)
C14—C13—H13	119.3	C16—N2—H2A	109.4
C13—C14—C9	119.4 (3)	C17—N2—H2A	109.4
C13—C14—N1	123.3 (3)	C16—N2—H2B	109.4
C9—C14—N1	117.4 (3)	C17—N2—H2B	109.4
N1—C15—C16	110.7 (2)	H2A—N2—H2B	108.0
N1—C15—H15A	109.5	C23—O3—H3A	109.5
C16—C15—H15A	109.5	H41—O4—H42	97.0
N1—C15—H15B	109.5	C9—S1—C1	103.56 (17)
C16—C15—H15B	109.5

C6—C1—C2—C3	−1.7 (6)	O2—C19—C20—C25	−11.6 (4)
S1—C1—C2—C3	173.9 (3)	O1—C19—C20—C21	−13.7 (4)
C1—C2—C3—C4	0.8 (7)	O2—C19—C20—C21	167.4 (3)
C2—C3—C4—C5	0.5 (7)	C25—C20—C21—C22	−0.3 (5)
C2—C3—C4—C7	−179.4 (4)	C19—C20—C21—C22	−179.4 (3)
C3—C4—C5—C6	−1.0 (7)	C20—C21—C22—C23	−0.1 (5)
C7—C4—C5—C6	179.0 (4)	C21—C22—C23—O3	−179.9 (3)
C2—C1—C6—C5	1.2 (6)	C21—C22—C23—C24	0.1 (5)
S1—C1—C6—C5	−174.1 (3)	O3—C23—C24—C25	−179.6 (3)
C2—C1—C6—C8	−177.9 (4)	C22—C23—C24—C25	0.4 (5)
S1—C1—C6—C8	6.8 (6)	C23—C24—C25—C20	−0.9 (5)
C4—C5—C6—C1	0.1 (7)	C21—C20—C25—C24	0.8 (5)
C4—C5—C6—C8	179.3 (5)	C19—C20—C25—C24	179.9 (3)
C14—C9—C10—C11	−1.0 (7)	C13—C14—N1—C18	−36.1 (4)
S1—C9—C10—C11	−179.8 (4)	C9—C14—N1—C18	144.4 (3)
C9—C10—C11—C12	1.1 (9)	C13—C14—N1—C15	89.2 (3)
C10—C11—C12—C13	−0.5 (8)	C9—C14—N1—C15	−90.3 (3)
C11—C12—C13—C14	−0.3 (6)	C17—C18—N1—C14	−174.4 (3)
C12—C13—C14—C9	0.5 (5)	C17—C18—N1—C15	59.7 (3)
C12—C13—C14—N1	−179.0 (3)	C16—C15—N1—C14	173.5 (2)
C10—C9—C14—C13	0.1 (5)	C16—C15—N1—C18	−59.3 (3)
S1—C9—C14—C13	179.1 (3)	C15—C16—N2—C17	−57.7 (3)
C10—C9—C14—N1	179.7 (4)	C18—C17—N2—C16	58.8 (3)
S1—C9—C14—N1	−1.4 (4)	C10—C9—S1—C1	−9.9 (5)
N1—C15—C16—N2	57.5 (3)	C14—C9—S1—C1	171.3 (3)
N2—C17—C18—N1	−59.2 (3)	C2—C1—S1—C9	111.1 (3)
O1—C19—C20—C25	167.2 (3)	C6—C1—S1—C9	−73.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.90	1.85	2.723 (3)	162
O4—H41···O2	0.86	1.93	2.778 (3)	169
N2—H2A···O2ⁱ	0.90	1.84	2.676 (3)	154
O3—H3A···O4ⁱⁱ	0.82	1.95	2.650 (3)	143
O4—H42···O1ⁱⁱⁱ	0.99	1.81	2.765 (3)	159

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

(3) top

Crystal data top

C₁₈H₂₃N₂S·C₇H₅O₃	F(000) = 928
M_r = 436.55	D_x = 1.260 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13019 reflections
a = 8.6363 (3) Å	θ = 3.1–27.4°
b = 20.6504 (8) Å	µ = 0.17 mm⁻¹
c = 12.9243 (6) Å	T = 296 K
β = 93.435 (1)°	Chunk, colorless
V = 2300.82 (16) Å³	0.48 × 0.29 × 0.16 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	5230 independent reflections
Radiation source: rotating anode	3088 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −11→10
Absorption correction: multi-scan Higashi, T. (1995)	k = −26→26
T_min = 0.913, T_max = 0.973	l = −16→16
22208 measured 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.137	w = 1/[σ²(F_o²) + (0.0548P)² + 0.821P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
5230 reflections	Δρ_max = 0.27 e Å⁻³
284 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0176 (14)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.1287 (2)	0.50743 (10)	0.38634 (16)	0.0414 (5)
C2	0.0397 (2)	0.54874 (10)	0.32343 (18)	0.0466 (5)
H2	0.0314	0.5922	0.3414	0.056*
C3	−0.0373 (3)	0.52594 (11)	0.23396 (19)	0.0516 (6)
H3	−0.0962	0.5544	0.1921	0.062*
C4	−0.0283 (3)	0.46123 (11)	0.20538 (18)	0.0507 (6)
C5	0.0570 (3)	0.42025 (11)	0.27146 (18)	0.0487 (6)
H5	0.0621	0.3766	0.2543	0.058*
C6	0.1351 (2)	0.44133 (10)	0.36217 (17)	0.0437 (5)
C7	−0.1097 (3)	0.43717 (15)	0.1064 (2)	0.0786 (9)
H7A	−0.0371	0.4144	0.0662	0.118*
H7B	−0.1517	0.4733	0.0672	0.118*
H7C	−0.1922	0.4084	0.1226	0.118*
C8	0.2218 (3)	0.39424 (11)	0.4329 (2)	0.0643 (7)
H8A	0.1995	0.3508	0.4100	0.096*
H8B	0.1901	0.3996	0.5023	0.096*
H8C	0.3312	0.4022	0.4316	0.096*
C9	0.2609 (3)	0.61786 (11)	0.48385 (17)	0.0469 (5)
C10	0.2192 (3)	0.65766 (13)	0.5644 (2)	0.0662 (7)
H10	0.1776	0.6396	0.6225	0.079*
C11	0.2392 (4)	0.72403 (14)	0.5586 (3)	0.0804 (9)
H11	0.2121	0.7504	0.6131	0.097*
C12	0.2990 (4)	0.75097 (13)	0.4727 (3)	0.0805 (9)
H12	0.3112	0.7956	0.4684	0.097*
C13	0.3413 (3)	0.71173 (11)	0.3925 (2)	0.0637 (7)
H13	0.3813	0.7305	0.3344	0.076*
C14	0.3253 (2)	0.64496 (10)	0.39680 (17)	0.0440 (5)
C15	0.3403 (3)	0.62509 (11)	0.21028 (17)	0.0508 (6)
H15A	0.4191	0.6561	0.1930	0.061*
H15B	0.2400	0.6462	0.2024	0.061*
C16	0.3438 (3)	0.56731 (12)	0.13877 (18)	0.0543 (6)
H16A	0.2611	0.5376	0.1538	0.065*
H16B	0.3268	0.5815	0.0675	0.065*
C17	0.5328 (3)	0.51576 (11)	0.26245 (17)	0.0484 (5)
H17A	0.6369	0.4981	0.2698	0.058*
H17B	0.4612	0.4827	0.2833	0.058*
C18	0.5219 (2)	0.57402 (11)	0.33155 (17)	0.0464 (5)
H18A	0.5396	0.5611	0.4035	0.056*
H18B	0.6009	0.6053	0.3157	0.056*
C19	0.3626 (3)	0.37479 (10)	0.03152 (18)	0.0444 (5)
C20	0.3017 (2)	0.32396 (9)	0.10119 (16)	0.0402 (5)
C21	0.3725 (3)	0.31279 (10)	0.19855 (17)	0.0447 (5)
H21	0.4579	0.3377	0.2206	0.054*
C22	0.3197 (3)	0.26553 (10)	0.26412 (17)	0.0470 (5)
H22	0.3706	0.2583	0.3285	0.056*
C23	0.1905 (3)	0.22923 (10)	0.23279 (17)	0.0459 (5)
C24	0.1164 (3)	0.24045 (11)	0.13676 (18)	0.0533 (6)
H24	0.0285	0.2167	0.1159	0.064*
C25	0.1723 (3)	0.28684 (10)	0.07159 (17)	0.0485 (5)
H25	0.1223	0.2934	0.0067	0.058*
N1	0.3690 (2)	0.60334 (8)	0.31585 (13)	0.0419 (4)
N2	0.4953 (2)	0.53367 (9)	0.15226 (13)	0.0467 (5)
H2A	0.5703	0.5597	0.1303	0.056*
H2B	0.4929	0.4976	0.1130	0.056*
O1	0.4650 (2)	0.41301 (8)	0.06850 (13)	0.0597 (5)
O2	0.31152 (19)	0.37677 (7)	−0.06250 (12)	0.0540 (4)
O3	0.1286 (2)	0.18274 (8)	0.29356 (14)	0.0637 (5)
H3A	0.1922	0.1728	0.3406	0.096*
S1	0.23686 (7)	0.53347 (3)	0.50000 (4)	0.0525 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0432 (11)	0.0413 (11)	0.0400 (12)	−0.0029 (9)	0.0054 (9)	−0.0013 (9)
C2	0.0468 (12)	0.0391 (11)	0.0538 (14)	−0.0015 (9)	0.0018 (10)	0.0004 (10)
C3	0.0434 (12)	0.0527 (13)	0.0577 (15)	0.0003 (10)	−0.0061 (11)	0.0052 (11)
C4	0.0426 (12)	0.0588 (14)	0.0499 (14)	−0.0044 (11)	−0.0037 (10)	−0.0065 (11)
C5	0.0502 (13)	0.0439 (12)	0.0521 (15)	−0.0021 (10)	0.0028 (11)	−0.0087 (10)
C6	0.0478 (12)	0.0408 (11)	0.0430 (13)	0.0017 (10)	0.0058 (10)	−0.0003 (9)
C7	0.0764 (19)	0.086 (2)	0.070 (2)	−0.0008 (16)	−0.0225 (15)	−0.0167 (16)
C8	0.094 (2)	0.0454 (12)	0.0526 (16)	0.0110 (13)	−0.0056 (14)	−0.0018 (11)
C9	0.0495 (13)	0.0477 (12)	0.0434 (13)	−0.0074 (10)	0.0023 (10)	−0.0087 (10)
C10	0.0744 (18)	0.0700 (16)	0.0556 (16)	−0.0159 (14)	0.0158 (13)	−0.0249 (13)
C11	0.089 (2)	0.0652 (17)	0.089 (2)	−0.0172 (16)	0.0225 (18)	−0.0388 (17)
C12	0.092 (2)	0.0444 (14)	0.106 (3)	−0.0156 (14)	0.0140 (19)	−0.0253 (15)
C13	0.0694 (17)	0.0461 (13)	0.0766 (19)	−0.0144 (12)	0.0125 (14)	−0.0055 (13)
C14	0.0442 (12)	0.0411 (11)	0.0468 (13)	−0.0042 (9)	0.0025 (10)	−0.0074 (9)
C15	0.0537 (13)	0.0542 (13)	0.0439 (14)	0.0037 (11)	−0.0018 (10)	0.0117 (11)
C16	0.0498 (13)	0.0752 (16)	0.0372 (13)	−0.0050 (12)	−0.0043 (10)	0.0043 (11)
C17	0.0579 (14)	0.0497 (12)	0.0377 (13)	0.0051 (11)	0.0036 (10)	0.0052 (10)
C18	0.0463 (12)	0.0555 (13)	0.0367 (12)	0.0024 (10)	−0.0042 (9)	−0.0023 (10)
C19	0.0519 (13)	0.0392 (11)	0.0427 (13)	−0.0008 (10)	0.0088 (10)	−0.0070 (9)
C20	0.0463 (12)	0.0350 (10)	0.0399 (12)	−0.0008 (9)	0.0076 (9)	−0.0029 (9)
C21	0.0456 (12)	0.0445 (11)	0.0437 (13)	0.0011 (10)	0.0008 (10)	−0.0062 (10)
C22	0.0547 (13)	0.0461 (12)	0.0398 (13)	0.0052 (11)	−0.0015 (10)	0.0002 (10)
C23	0.0579 (13)	0.0369 (11)	0.0434 (13)	0.0019 (10)	0.0055 (10)	0.0045 (9)
C24	0.0609 (15)	0.0510 (13)	0.0473 (14)	−0.0132 (11)	−0.0043 (11)	0.0060 (11)
C25	0.0571 (14)	0.0490 (12)	0.0387 (13)	−0.0046 (11)	−0.0040 (10)	0.0037 (10)
N1	0.0439 (10)	0.0452 (9)	0.0363 (10)	0.0020 (8)	0.0003 (8)	0.0003 (8)
N2	0.0543 (11)	0.0506 (10)	0.0355 (10)	−0.0093 (9)	0.0056 (8)	−0.0046 (8)
O1	0.0734 (11)	0.0547 (9)	0.0511 (10)	−0.0214 (8)	0.0062 (8)	−0.0085 (8)
O2	0.0675 (10)	0.0546 (9)	0.0399 (10)	−0.0131 (8)	0.0026 (8)	0.0035 (7)
O3	0.0808 (12)	0.0545 (9)	0.0549 (11)	−0.0114 (9)	−0.0031 (9)	0.0194 (8)
S1	0.0722 (4)	0.0475 (3)	0.0373 (3)	−0.0079 (3)	−0.0016 (3)	0.0008 (2)

Geometric parameters (Å, º) top

C1—C2	1.380 (3)	C15—C16	1.510 (3)
C1—C6	1.402 (3)	C15—H15A	0.9700
C1—S1	1.776 (2)	C15—H15B	0.9700
C2—C3	1.381 (3)	C16—N2	1.483 (3)
C2—H2	0.9300	C16—H16A	0.9700
C3—C4	1.390 (3)	C16—H16B	0.9700
C3—H3	0.9300	C17—N2	1.488 (3)
C4—C5	1.383 (3)	C17—C18	1.505 (3)
C4—C7	1.507 (3)	C17—H17A	0.9700
C5—C6	1.387 (3)	C17—H17B	0.9700
C5—H5	0.9300	C18—N1	1.456 (3)
C6—C8	1.504 (3)	C18—H18A	0.9700
C7—H7A	0.9600	C18—H18B	0.9700
C7—H7B	0.9600	C19—O1	1.258 (3)
C7—H7C	0.9600	C19—O2	1.268 (3)
C8—H8A	0.9600	C19—C20	1.499 (3)
C8—H8B	0.9600	C20—C21	1.385 (3)
C8—H8C	0.9600	C20—C25	1.390 (3)
C9—C10	1.391 (3)	C21—C22	1.388 (3)
C9—C14	1.401 (3)	C21—H21	0.9300
C9—S1	1.769 (2)	C22—C23	1.384 (3)
C10—C11	1.384 (4)	C22—H22	0.9300
C10—H10	0.9300	C23—O3	1.369 (2)
C11—C12	1.371 (4)	C23—C24	1.382 (3)
C11—H11	0.9300	C24—C25	1.382 (3)
C12—C13	1.381 (4)	C24—H24	0.9300
C12—H12	0.9300	C25—H25	0.9300
C13—C14	1.387 (3)	N2—H2A	0.9000
C13—H13	0.9300	N2—H2B	0.9000
C14—N1	1.422 (3)	O3—H3A	0.8200
C15—N1	1.444 (3)

C2—C1—C6	119.9 (2)	C16—C15—H15B	109.9
C2—C1—S1	123.15 (16)	H15A—C15—H15B	108.3
C6—C1—S1	116.96 (16)	N2—C16—C15	110.34 (18)
C1—C2—C3	120.4 (2)	N2—C16—H16A	109.6
C1—C2—H2	119.8	C15—C16—H16A	109.6
C3—C2—H2	119.8	N2—C16—H16B	109.6
C2—C3—C4	121.2 (2)	C15—C16—H16B	109.6
C2—C3—H3	119.4	H16A—C16—H16B	108.1
C4—C3—H3	119.4	N2—C17—C18	110.59 (17)
C5—C4—C3	117.4 (2)	N2—C17—H17A	109.5
C5—C4—C7	121.8 (2)	C18—C17—H17A	109.5
C3—C4—C7	120.8 (2)	N2—C17—H17B	109.5
C4—C5—C6	122.9 (2)	C18—C17—H17B	109.5
C4—C5—H5	118.5	H17A—C17—H17B	108.1
C6—C5—H5	118.5	N1—C18—C17	109.78 (17)
C5—C6—C1	118.0 (2)	N1—C18—H18A	109.7
C5—C6—C8	120.7 (2)	C17—C18—H18A	109.7
C1—C6—C8	121.3 (2)	N1—C18—H18B	109.7
C4—C7—H7A	109.5	C17—C18—H18B	109.7
C4—C7—H7B	109.5	H18A—C18—H18B	108.2
H7A—C7—H7B	109.5	O1—C19—O2	122.7 (2)
C4—C7—H7C	109.5	O1—C19—C20	118.4 (2)
H7A—C7—H7C	109.5	O2—C19—C20	118.94 (19)
H7B—C7—H7C	109.5	C21—C20—C25	117.52 (19)
C6—C8—H8A	109.5	C21—C20—C19	120.73 (19)
C6—C8—H8B	109.5	C25—C20—C19	121.7 (2)
H8A—C8—H8B	109.5	C20—C21—C22	121.9 (2)
C6—C8—H8C	109.5	C20—C21—H21	119.0
H8A—C8—H8C	109.5	C22—C21—H21	119.0
H8B—C8—H8C	109.5	C23—C22—C21	119.4 (2)
C10—C9—C14	119.9 (2)	C23—C22—H22	120.3
C10—C9—S1	117.15 (19)	C21—C22—H22	120.3
C14—C9—S1	122.90 (16)	O3—C23—C24	117.2 (2)
C11—C10—C9	120.4 (3)	O3—C23—C22	123.2 (2)
C11—C10—H10	119.8	C24—C23—C22	119.6 (2)
C9—C10—H10	119.8	C23—C24—C25	120.3 (2)
C12—C11—C10	120.0 (3)	C23—C24—H24	119.9
C12—C11—H11	120.0	C25—C24—H24	119.9
C10—C11—H11	120.0	C24—C25—C20	121.3 (2)
C11—C12—C13	119.9 (2)	C24—C25—H25	119.4
C11—C12—H12	120.0	C20—C25—H25	119.4
C13—C12—H12	120.0	C14—N1—C15	117.99 (17)
C12—C13—C14	121.5 (3)	C14—N1—C18	115.29 (17)
C12—C13—H13	119.3	C15—N1—C18	111.33 (18)
C14—C13—H13	119.3	C16—N2—C17	111.64 (17)
C13—C14—C9	118.3 (2)	C16—N2—H2A	109.3
C13—C14—N1	122.7 (2)	C17—N2—H2A	109.3
C9—C14—N1	119.01 (18)	C16—N2—H2B	109.3
N1—C15—C16	108.91 (18)	C17—N2—H2B	109.3
N1—C15—H15A	109.9	H2A—N2—H2B	108.0
C16—C15—H15A	109.9	C23—O3—H3A	109.5
N1—C15—H15B	109.9	C9—S1—C1	105.09 (10)

C6—C1—C2—C3	−3.2 (3)	O2—C19—C20—C21	168.8 (2)
S1—C1—C2—C3	177.61 (17)	O1—C19—C20—C25	169.6 (2)
C1—C2—C3—C4	0.5 (4)	O2—C19—C20—C25	−11.9 (3)
C2—C3—C4—C5	1.8 (4)	C25—C20—C21—C22	1.4 (3)
C2—C3—C4—C7	−178.6 (2)	C19—C20—C21—C22	−179.22 (19)
C3—C4—C5—C6	−1.5 (4)	C20—C21—C22—C23	−1.4 (3)
C7—C4—C5—C6	178.9 (2)	C21—C22—C23—O3	−178.4 (2)
C4—C5—C6—C1	−1.1 (3)	C21—C22—C23—C24	0.1 (3)
C4—C5—C6—C8	178.0 (2)	O3—C23—C24—C25	179.8 (2)
C2—C1—C6—C5	3.4 (3)	C22—C23—C24—C25	1.1 (3)
S1—C1—C6—C5	−177.32 (16)	C23—C24—C25—C20	−1.1 (4)
C2—C1—C6—C8	−175.7 (2)	C21—C20—C25—C24	−0.1 (3)
S1—C1—C6—C8	3.6 (3)	C19—C20—C25—C24	−179.5 (2)
C14—C9—C10—C11	0.8 (4)	C13—C14—N1—C15	−37.7 (3)
S1—C9—C10—C11	178.0 (2)	C9—C14—N1—C15	141.2 (2)
C9—C10—C11—C12	0.7 (5)	C13—C14—N1—C18	97.3 (3)
C10—C11—C12—C13	−0.9 (5)	C9—C14—N1—C18	−83.8 (2)
C11—C12—C13—C14	−0.3 (5)	C16—C15—N1—C14	−161.23 (18)
C12—C13—C14—C9	1.6 (4)	C16—C15—N1—C18	62.1 (2)
C12—C13—C14—N1	−179.5 (2)	C17—C18—N1—C14	160.91 (18)
C10—C9—C14—C13	−1.9 (3)	C17—C18—N1—C15	−61.2 (2)
S1—C9—C14—C13	−178.96 (18)	C15—C16—N2—C17	54.5 (2)
C10—C9—C14—N1	179.2 (2)	C18—C17—N2—C16	−53.2 (2)
S1—C9—C14—N1	2.1 (3)	C10—C9—S1—C1	128.30 (19)
N1—C15—C16—N2	−58.0 (2)	C14—C9—S1—C1	−54.5 (2)
N2—C17—C18—N1	55.5 (2)	C2—C1—S1—C9	−20.8 (2)
O1—C19—C20—C21	−9.8 (3)	C6—C1—S1—C9	159.94 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.90	1.85	2.723 (2)	163
N2—H2A···O2ⁱ	0.90	1.91	2.789 (2)	166
O3—H3A···O2ⁱⁱ	0.82	1.88	2.667 (2)	161

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

(4) top

Crystal data top

C₁₈H₂₃N₂S·C₇H₄NO₃S	F(000) = 1016
M_r = 481.62	D_x = 1.269 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13112 reflections
a = 6.8375 (3) Å	θ = 3.1–27.4°
b = 15.8835 (7) Å	µ = 0.24 mm⁻¹
c = 23.2329 (9) Å	T = 296 K
β = 92.451 (1)°	Chunk, colorless
V = 2520.86 (18) Å³	0.46 × 0.39 × 0.20 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4910 independent reflections
Radiation source: rotating anode	3001 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 10.00 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan Higashi, T. (1995)	k = −18→19
T_min = 0.897, T_max = 0.953	l = −28→28
20672 measured 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0569P)² + 1.9621P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4910 reflections	Δρ_max = 0.44 e Å⁻³
301 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0212 (14)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.5606 (5)	0.54205 (18)	0.18239 (13)	0.0556 (8)
C2	0.6134 (6)	0.5579 (2)	0.12678 (14)	0.0790 (10)
H2	0.7377	0.5434	0.1154	0.095*
C3	0.4810 (8)	0.5956 (3)	0.08795 (16)	0.0962 (14)
H3	0.5195	0.6064	0.0508	0.115*
C4	0.2963 (7)	0.6173 (2)	0.10225 (16)	0.0765 (11)
C5	0.2478 (6)	0.6022 (2)	0.15760 (15)	0.0767 (10)
H5	0.1233	0.6173	0.1686	0.092*
C6	0.3756 (5)	0.5652 (2)	0.19859 (13)	0.0688 (9)
C7	0.1522 (7)	0.6567 (3)	0.0587 (2)	0.1228 (19)
H7A	0.1047	0.6144	0.0321	0.184*
H7B	0.2163	0.7004	0.0381	0.184*
H7C	0.0443	0.6802	0.0784	0.184*
C8	0.3081 (7)	0.5500 (4)	0.25865 (17)	0.135 (2)
H8A	0.3346	0.4927	0.2696	0.203*
H8B	0.1700	0.5605	0.2596	0.203*
H8C	0.3767	0.5872	0.2851	0.203*
C9	0.6665 (4)	0.39309 (18)	0.23725 (12)	0.0547 (7)
C10	0.5292 (5)	0.3557 (2)	0.19991 (14)	0.0716 (10)
H10	0.4580	0.3889	0.1735	0.086*
C11	0.4967 (6)	0.2704 (2)	0.20131 (17)	0.0867 (12)
H11	0.4021	0.2462	0.1765	0.104*
C12	0.6038 (7)	0.2210 (2)	0.23919 (19)	0.0972 (14)
H12	0.5870	0.1629	0.2389	0.117*
C13	0.7368 (6)	0.2576 (2)	0.27785 (16)	0.0812 (11)
H13	0.8068	0.2236	0.3040	0.097*
C14	0.7683 (4)	0.34304 (18)	0.27861 (12)	0.0545 (7)
C15	1.0584 (5)	0.3318 (2)	0.34359 (15)	0.0682 (9)
H15A	1.1246	0.3034	0.3130	0.082*
H15B	1.0048	0.2894	0.3684	0.082*
C16	1.2025 (5)	0.3861 (2)	0.37788 (15)	0.0731 (10)
H16A	1.3054	0.3511	0.3951	0.088*
H16B	1.2622	0.4262	0.3525	0.088*
C17	0.9340 (4)	0.4817 (2)	0.39972 (13)	0.0612 (8)
H17A	0.9815	0.5263	0.3754	0.073*
H17B	0.8653	0.5074	0.4309	0.073*
C18	0.7969 (4)	0.4257 (2)	0.36515 (12)	0.0540 (7)
H18A	0.7433	0.3833	0.3901	0.065*
H18B	0.6892	0.4588	0.3488	0.065*
C19	0.5579 (4)	0.28238 (19)	0.57044 (12)	0.0506 (7)
C20	0.4306 (6)	0.2354 (3)	0.60181 (16)	0.0822 (11)
H20	0.3177	0.2589	0.6160	0.099*
C21	0.4782 (7)	0.1518 (3)	0.61129 (19)	0.0981 (14)
H21	0.3961	0.1185	0.6327	0.118*
C22	0.6421 (7)	0.1171 (2)	0.59009 (17)	0.0875 (12)
H22	0.6690	0.0604	0.5968	0.105*
C23	0.7684 (6)	0.1641 (2)	0.55897 (14)	0.0691 (9)
H23	0.8811	0.1403	0.5449	0.083*
C24	0.7236 (4)	0.24800 (18)	0.54898 (11)	0.0497 (7)
C25	0.8340 (5)	0.3132 (2)	0.51677 (13)	0.0578 (8)
N1	0.8998 (3)	0.38451 (15)	0.31881 (10)	0.0531 (6)
N2	1.1015 (4)	0.43166 (18)	0.42360 (11)	0.0641 (7)
H2A	1.1871	0.4662	0.4423	0.077*
H2B	1.0581	0.3943	0.4492	0.077*
N3	0.7516 (4)	0.38955 (17)	0.51677 (11)	0.0623 (7)
O1	0.9866 (4)	0.29579 (19)	0.49223 (11)	0.0882 (8)
O2	0.5630 (4)	0.44340 (15)	0.59810 (10)	0.0837 (8)
O3	0.3857 (3)	0.40264 (15)	0.51036 (11)	0.0791 (7)
S1	0.73721 (13)	0.49966 (5)	0.23268 (4)	0.0642 (3)
S2	0.55065 (12)	0.38844 (5)	0.54906 (3)	0.0567 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.068 (2)	0.0444 (16)	0.0539 (17)	−0.0083 (14)	−0.0055 (15)	0.0048 (13)
C2	0.095 (3)	0.084 (3)	0.059 (2)	−0.004 (2)	0.008 (2)	0.0121 (18)
C3	0.130 (4)	0.107 (3)	0.051 (2)	−0.010 (3)	−0.003 (2)	0.032 (2)
C4	0.104 (3)	0.057 (2)	0.066 (2)	−0.015 (2)	−0.025 (2)	0.0200 (16)
C5	0.078 (2)	0.080 (2)	0.070 (2)	0.0049 (19)	−0.0183 (19)	0.0119 (18)
C6	0.077 (2)	0.079 (2)	0.0495 (17)	−0.0015 (18)	−0.0074 (17)	0.0119 (16)
C7	0.146 (4)	0.112 (4)	0.104 (3)	−0.018 (3)	−0.057 (3)	0.050 (3)
C8	0.096 (3)	0.243 (7)	0.068 (3)	0.043 (4)	0.013 (3)	0.043 (3)
C9	0.0621 (18)	0.0488 (17)	0.0521 (16)	−0.0038 (14)	−0.0079 (14)	0.0067 (13)
C10	0.087 (2)	0.056 (2)	0.070 (2)	−0.0131 (17)	−0.0281 (19)	0.0088 (16)
C11	0.112 (3)	0.056 (2)	0.089 (3)	−0.024 (2)	−0.031 (2)	0.0008 (19)
C12	0.137 (4)	0.047 (2)	0.105 (3)	−0.017 (2)	−0.031 (3)	0.012 (2)
C13	0.109 (3)	0.050 (2)	0.082 (2)	−0.0008 (19)	−0.024 (2)	0.0121 (17)
C14	0.0622 (18)	0.0478 (17)	0.0530 (16)	0.0004 (14)	−0.0032 (15)	0.0038 (13)
C15	0.065 (2)	0.072 (2)	0.068 (2)	0.0177 (17)	−0.0030 (17)	0.0102 (17)
C16	0.0518 (18)	0.098 (3)	0.069 (2)	0.0042 (18)	−0.0050 (17)	0.0223 (19)
C17	0.0643 (19)	0.066 (2)	0.0526 (17)	−0.0003 (15)	−0.0084 (15)	0.0092 (14)
C18	0.0482 (16)	0.0644 (19)	0.0488 (16)	0.0037 (14)	−0.0034 (14)	0.0017 (14)
C19	0.0520 (17)	0.0575 (18)	0.0420 (14)	−0.0044 (14)	−0.0013 (13)	0.0085 (12)
C20	0.074 (2)	0.092 (3)	0.082 (2)	−0.006 (2)	0.021 (2)	0.016 (2)
C21	0.117 (4)	0.081 (3)	0.097 (3)	−0.028 (3)	0.013 (3)	0.039 (2)
C22	0.126 (4)	0.054 (2)	0.081 (3)	−0.005 (2)	−0.015 (3)	0.0229 (19)
C23	0.089 (2)	0.060 (2)	0.0575 (19)	0.0133 (18)	−0.0089 (18)	0.0055 (16)
C24	0.0573 (18)	0.0537 (17)	0.0375 (13)	−0.0015 (14)	−0.0050 (13)	0.0066 (12)
C25	0.0517 (18)	0.075 (2)	0.0465 (16)	−0.0023 (16)	0.0018 (15)	0.0117 (15)
N1	0.0527 (14)	0.0556 (15)	0.0505 (13)	0.0051 (11)	−0.0055 (12)	0.0050 (11)
N2	0.0568 (15)	0.0824 (19)	0.0521 (14)	−0.0111 (13)	−0.0076 (13)	0.0166 (13)
N3	0.0614 (16)	0.0596 (17)	0.0655 (16)	−0.0070 (13)	−0.0024 (13)	0.0162 (13)
O1	0.0683 (15)	0.113 (2)	0.0848 (17)	0.0108 (14)	0.0240 (14)	0.0220 (15)
O2	0.1069 (19)	0.0666 (16)	0.0760 (15)	0.0170 (13)	−0.0153 (14)	−0.0216 (12)
O3	0.0666 (14)	0.0782 (16)	0.0891 (16)	0.0073 (12)	−0.0357 (13)	0.0139 (13)
S1	0.0708 (5)	0.0482 (5)	0.0719 (5)	−0.0099 (4)	−0.0184 (4)	0.0103 (4)
S2	0.0619 (5)	0.0509 (4)	0.0560 (4)	0.0024 (3)	−0.0129 (4)	0.0044 (3)

Geometric parameters (Å, º) top

C1—C2	1.380 (4)	C15—H15A	0.9700
C1—C6	1.384 (5)	C15—H15B	0.9700
C1—S1	1.777 (3)	C16—N2	1.481 (4)
C2—C3	1.386 (5)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.364 (6)	C17—N2	1.482 (4)
C3—H3	0.9300	C17—C18	1.501 (4)
C4—C5	1.363 (5)	C17—H17A	0.9700
C4—C7	1.516 (5)	C17—H17B	0.9700
C5—C6	1.395 (4)	C18—N1	1.465 (4)
C5—H5	0.9300	C18—H18A	0.9700
C6—C8	1.508 (5)	C18—H18B	0.9700
C7—H7A	0.9600	C19—C24	1.371 (4)
C7—H7B	0.9600	C19—C20	1.378 (4)
C7—H7C	0.9600	C19—S2	1.756 (3)
C8—H8A	0.9600	C20—C21	1.383 (6)
C8—H8B	0.9600	C20—H20	0.9300
C8—H8C	0.9600	C21—C22	1.361 (6)
C9—C10	1.384 (4)	C21—H21	0.9300
C9—C14	1.408 (4)	C22—C23	1.371 (5)
C9—S1	1.765 (3)	C22—H22	0.9300
C10—C11	1.375 (5)	C23—C24	1.385 (4)
C10—H10	0.9300	C23—H23	0.9300
C11—C12	1.367 (5)	C24—C25	1.500 (4)
C11—H11	0.9300	C25—O1	1.242 (4)
C12—C13	1.378 (5)	C25—N3	1.337 (4)
C12—H12	0.9300	N2—H2A	0.9000
C13—C14	1.375 (4)	N2—H2B	0.9000
C13—H13	0.9300	N3—S2	1.593 (3)
C14—N1	1.429 (4)	O2—S2	1.435 (2)
C15—N1	1.468 (4)	O3—S2	1.430 (2)
C15—C16	1.510 (5)

C2—C1—C6	119.0 (3)	N2—C16—H16A	109.6
C2—C1—S1	119.2 (3)	C15—C16—H16A	109.6
C6—C1—S1	121.7 (2)	N2—C16—H16B	109.6
C1—C2—C3	119.9 (4)	C15—C16—H16B	109.6
C1—C2—H2	120.1	H16A—C16—H16B	108.2
C3—C2—H2	120.1	N2—C17—C18	109.7 (3)
C4—C3—C2	122.5 (4)	N2—C17—H17A	109.7
C4—C3—H3	118.8	C18—C17—H17A	109.7
C2—C3—H3	118.8	N2—C17—H17B	109.7
C3—C4—C5	116.8 (3)	C18—C17—H17B	109.7
C3—C4—C7	121.6 (4)	H17A—C17—H17B	108.2
C5—C4—C7	121.6 (4)	N1—C18—C17	110.5 (2)
C4—C5—C6	123.2 (4)	N1—C18—H18A	109.6
C4—C5—H5	118.4	C17—C18—H18A	109.6
C6—C5—H5	118.4	N1—C18—H18B	109.6
C1—C6—C5	118.6 (3)	C17—C18—H18B	109.6
C1—C6—C8	121.9 (3)	H18A—C18—H18B	108.1
C5—C6—C8	119.4 (4)	C24—C19—C20	121.8 (3)
C4—C7—H7A	109.5	C24—C19—S2	107.0 (2)
C4—C7—H7B	109.5	C20—C19—S2	131.1 (3)
H7A—C7—H7B	109.5	C19—C20—C21	117.0 (4)
C4—C7—H7C	109.5	C19—C20—H20	121.5
H7A—C7—H7C	109.5	C21—C20—H20	121.5
H7B—C7—H7C	109.5	C22—C21—C20	121.6 (4)
C6—C8—H8A	109.5	C22—C21—H21	119.2
C6—C8—H8B	109.5	C20—C21—H21	119.2
H8A—C8—H8B	109.5	C21—C22—C23	121.2 (4)
C6—C8—H8C	109.5	C21—C22—H22	119.4
H8A—C8—H8C	109.5	C23—C22—H22	119.4
H8B—C8—H8C	109.5	C22—C23—C24	118.2 (4)
C10—C9—C14	119.2 (3)	C22—C23—H23	120.9
C10—C9—S1	123.6 (2)	C24—C23—H23	120.9
C14—C9—S1	117.0 (2)	C19—C24—C23	120.2 (3)
C11—C10—C9	120.9 (3)	C19—C24—C25	110.4 (3)
C11—C10—H10	119.5	C23—C24—C25	129.5 (3)
C9—C10—H10	119.5	O1—C25—N3	124.4 (3)
C12—C11—C10	119.8 (3)	O1—C25—C24	121.7 (3)
C12—C11—H11	120.1	N3—C25—C24	113.9 (3)
C10—C11—H11	120.1	C14—N1—C18	112.2 (2)
C11—C12—C13	119.9 (3)	C14—N1—C15	115.3 (2)
C11—C12—H12	120.1	C18—N1—C15	109.7 (2)
C13—C12—H12	120.1	C16—N2—C17	111.7 (2)
C14—C13—C12	121.5 (3)	C16—N2—H2A	109.3
C14—C13—H13	119.2	C17—N2—H2A	109.3
C12—C13—H13	119.2	C16—N2—H2B	109.3
C13—C14—C9	118.4 (3)	C17—N2—H2B	109.3
C13—C14—N1	123.9 (3)	H2A—N2—H2B	107.9
C9—C14—N1	117.7 (3)	C25—N3—S2	111.2 (2)
N1—C15—C16	109.6 (3)	C9—S1—C1	102.86 (13)
N1—C15—H15A	109.7	O3—S2—O2	114.91 (15)
C16—C15—H15A	109.7	O3—S2—N3	112.03 (15)
N1—C15—H15B	109.7	O2—S2—N3	110.15 (16)
C16—C15—H15B	109.7	O3—S2—C19	109.94 (14)
H15A—C15—H15B	108.2	O2—S2—C19	111.04 (14)
N2—C16—C15	110.1 (3)	N3—S2—C19	97.43 (14)

C6—C1—C2—C3	−0.8 (5)	C20—C19—C24—C25	180.0 (3)
S1—C1—C2—C3	−176.2 (3)	S2—C19—C24—C25	0.7 (3)
C1—C2—C3—C4	−0.7 (6)	C22—C23—C24—C19	0.7 (4)
C2—C3—C4—C5	1.6 (6)	C22—C23—C24—C25	180.0 (3)
C2—C3—C4—C7	−178.6 (4)	C19—C24—C25—O1	−178.0 (3)
C3—C4—C5—C6	−1.0 (6)	C23—C24—C25—O1	2.6 (5)
C7—C4—C5—C6	179.2 (4)	C19—C24—C25—N3	1.2 (3)
C2—C1—C6—C5	1.3 (5)	C23—C24—C25—N3	−178.1 (3)
S1—C1—C6—C5	176.6 (3)	C13—C14—N1—C18	−102.0 (4)
C2—C1—C6—C8	−179.8 (4)	C9—C14—N1—C18	78.4 (3)
S1—C1—C6—C8	−4.5 (5)	C13—C14—N1—C15	24.4 (4)
C4—C5—C6—C1	−0.4 (6)	C9—C14—N1—C15	−155.1 (3)
C4—C5—C6—C8	−179.3 (4)	C17—C18—N1—C14	−169.2 (2)
C14—C9—C10—C11	−2.5 (6)	C17—C18—N1—C15	61.3 (3)
S1—C9—C10—C11	172.3 (3)	C16—C15—N1—C14	171.5 (3)
C9—C10—C11—C12	−1.4 (7)	C16—C15—N1—C18	−60.8 (3)
C10—C11—C12—C13	3.3 (7)	C15—C16—N2—C17	−55.5 (3)
C11—C12—C13—C14	−1.4 (7)	C18—C17—N2—C16	55.2 (3)
C12—C13—C14—C9	−2.4 (6)	O1—C25—N3—S2	176.5 (3)
C12—C13—C14—N1	178.0 (4)	C24—C25—N3—S2	−2.7 (3)
C10—C9—C14—C13	4.3 (5)	C10—C9—S1—C1	11.1 (3)
S1—C9—C14—C13	−170.8 (3)	C14—C9—S1—C1	−174.0 (2)
C10—C9—C14—N1	−176.1 (3)	C2—C1—S1—C9	−104.0 (3)
S1—C9—C14—N1	8.8 (4)	C6—C1—S1—C9	80.7 (3)
N1—C15—C16—N2	57.7 (3)	C25—N3—S2—O3	−112.3 (2)
N2—C17—C18—N1	−57.8 (3)	C25—N3—S2—O2	118.4 (2)
C24—C19—C20—C21	0.6 (5)	C25—N3—S2—C19	2.7 (2)
S2—C19—C20—C21	179.7 (3)	C24—C19—S2—O3	114.7 (2)
C19—C20—C21—C22	−0.7 (6)	C20—C19—S2—O3	−64.4 (3)
C20—C21—C22—C23	0.8 (7)	C24—C19—S2—O2	−117.0 (2)
C21—C22—C23—C24	−0.8 (5)	C20—C19—S2—O2	63.9 (3)
C20—C19—C24—C23	−0.6 (4)	C24—C19—S2—N3	−2.0 (2)
S2—C19—C24—C23	−179.9 (2)	C20—C19—S2—N3	178.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.90	1.93	2.815 (4)	167
N2—H2A···O3ⁱ	0.90	2.28	2.778 (3)	115

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

(5) top

Crystal data top

C₁₈H₂₃N₂S·Cl	F(000) = 712
M_r = 334.89	D_x = 1.213 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10193 reflections
a = 16.9383 (8) Å	θ = 3.1–27.4°
b = 6.5283 (3) Å	µ = 0.32 mm⁻¹
c = 17.8173 (9) Å	T = 296 K
β = 111.406 (2)°	Needle, colorless
V = 1834.30 (15) Å³	0.53 × 0.20 × 0.16 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4198 independent reflections
Radiation source: rotating anode	2440 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −21→21
Absorption correction: multi-scan Higashi, T. (1995)	k = −8→8
T_min = 0.848, T_max = 0.951	l = −23→21
17262 measured 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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0414P)² + 1.5518P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4198 reflections	Δρ_max = 0.41 e Å⁻³
202 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0123 (13)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.57012 (19)	0.0827 (5)	0.4118 (2)	0.0606 (8)
C2	0.5116 (2)	0.1712 (6)	0.3433 (2)	0.0776 (10)
H2	0.5234	0.2970	0.3252	0.093*
C3	0.4362 (2)	0.0730 (8)	0.3021 (2)	0.0946 (13)
H3	0.3973	0.1342	0.2564	0.113*
C4	0.4172 (3)	−0.1125 (8)	0.3269 (3)	0.0920 (13)
C5	0.4761 (2)	−0.1993 (6)	0.3940 (3)	0.0810 (11)
H5	0.4640	−0.3262	0.4110	0.097*
C6	0.5529 (2)	−0.1065 (5)	0.4378 (2)	0.0638 (8)
C8	0.6149 (3)	−0.2103 (6)	0.5111 (3)	0.0982 (13)
H8A	0.5866	−0.3179	0.5281	0.147*
H8B	0.6370	−0.1121	0.5538	0.147*
H8C	0.6606	−0.2671	0.4981	0.147*
C7	0.3329 (3)	−0.2182 (10)	0.2831 (3)	0.161 (3)
H7A	0.3383	−0.3621	0.2951	0.241*
H7B	0.3168	−0.1987	0.2260	0.241*
H7C	0.2902	−0.1607	0.3004	0.241*
C9	0.74195 (17)	0.1127 (4)	0.43822 (17)	0.0513 (7)
C10	0.72882 (19)	−0.0522 (5)	0.38589 (18)	0.0600 (8)
H10	0.6761	−0.1158	0.3663	0.072*
C11	0.7935 (2)	−0.1231 (5)	0.36255 (17)	0.0587 (8)
H11	0.7842	−0.2339	0.3276	0.070*
C12	0.8710 (2)	−0.0301 (5)	0.39095 (18)	0.0602 (8)
H12	0.9139	−0.0754	0.3742	0.072*
C13	0.88576 (18)	0.1316 (4)	0.44464 (17)	0.0555 (7)
H13	0.9390	0.1928	0.4643	0.067*
C14	0.82210 (17)	0.2034 (4)	0.46938 (15)	0.0452 (6)
C15	0.89790 (19)	0.5181 (4)	0.52786 (18)	0.0541 (7)
H15A	0.8879	0.5649	0.4735	0.065*
H15B	0.9539	0.4571	0.5494	0.065*
C16	0.89318 (19)	0.6968 (4)	0.57967 (18)	0.0579 (7)
H16A	0.9357	0.7979	0.5811	0.070*
H16B	0.8378	0.7608	0.5570	0.070*
C17	0.8468 (2)	0.4604 (4)	0.66285 (19)	0.0578 (7)
H17A	0.7898	0.5161	0.6444	0.069*
H17B	0.8604	0.4089	0.7172	0.069*
C18	0.85121 (19)	0.2890 (4)	0.60819 (16)	0.0512 (7)
H18A	0.9070	0.2266	0.6292	0.061*
H18B	0.8097	0.1849	0.6065	0.061*
Cl1	0.90598 (5)	0.97548 (10)	0.77657 (4)	0.0560 (2)
N1	0.83447 (13)	0.3666 (3)	0.52639 (12)	0.0452 (5)
N2	0.90794 (14)	0.6239 (3)	0.66270 (14)	0.0539 (6)
H2A	0.9028	0.7299	0.6929	0.065*
H2B	0.9611	0.5751	0.6850	0.065*
S1	0.66188 (5)	0.22723 (15)	0.46592 (7)	0.0816 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0512 (17)	0.0638 (19)	0.069 (2)	0.0003 (15)	0.0244 (16)	−0.0162 (16)
C2	0.066 (2)	0.090 (2)	0.080 (2)	0.003 (2)	0.030 (2)	0.004 (2)
C3	0.058 (2)	0.151 (4)	0.068 (2)	0.005 (3)	0.0151 (19)	−0.010 (3)
C4	0.065 (2)	0.132 (4)	0.086 (3)	−0.028 (3)	0.035 (2)	−0.050 (3)
C5	0.086 (3)	0.076 (2)	0.100 (3)	−0.023 (2)	0.056 (3)	−0.029 (2)
C6	0.0653 (19)	0.0641 (19)	0.066 (2)	0.0023 (16)	0.0291 (17)	−0.0148 (16)
C8	0.124 (3)	0.084 (3)	0.094 (3)	0.026 (3)	0.047 (3)	0.004 (2)
C7	0.081 (3)	0.244 (7)	0.156 (5)	−0.071 (4)	0.043 (3)	−0.108 (5)
C9	0.0503 (15)	0.0513 (15)	0.0516 (16)	0.0027 (13)	0.0176 (13)	−0.0077 (13)
C10	0.0561 (17)	0.0610 (17)	0.0592 (18)	−0.0014 (14)	0.0164 (15)	−0.0138 (15)
C11	0.070 (2)	0.0585 (17)	0.0477 (17)	0.0087 (16)	0.0219 (15)	−0.0063 (14)
C12	0.0662 (19)	0.0663 (18)	0.0569 (18)	0.0070 (16)	0.0330 (16)	−0.0010 (15)
C13	0.0534 (16)	0.0589 (17)	0.0589 (18)	−0.0013 (14)	0.0262 (15)	0.0025 (15)
C14	0.0502 (15)	0.0439 (14)	0.0401 (14)	0.0013 (12)	0.0149 (12)	0.0041 (11)
C15	0.0628 (17)	0.0478 (15)	0.0540 (17)	−0.0067 (13)	0.0241 (15)	0.0078 (13)
C16	0.0598 (18)	0.0435 (15)	0.067 (2)	−0.0051 (13)	0.0184 (15)	0.0053 (14)
C17	0.0656 (18)	0.0536 (16)	0.0582 (18)	−0.0076 (14)	0.0272 (15)	−0.0059 (14)
C18	0.0660 (18)	0.0436 (14)	0.0464 (16)	−0.0083 (13)	0.0234 (14)	−0.0012 (12)
Cl1	0.0581 (4)	0.0510 (4)	0.0603 (5)	−0.0035 (3)	0.0232 (3)	−0.0017 (3)
N1	0.0493 (12)	0.0414 (11)	0.0451 (13)	−0.0045 (10)	0.0173 (10)	0.0005 (10)
N2	0.0517 (13)	0.0446 (12)	0.0605 (15)	−0.0012 (11)	0.0147 (12)	−0.0086 (11)
S1	0.0530 (5)	0.0816 (6)	0.1120 (8)	−0.0080 (4)	0.0323 (5)	−0.0489 (6)

Geometric parameters (Å, º) top

C1—C6	1.386 (5)	C11—C12	1.364 (4)
C1—C2	1.387 (5)	C11—H11	0.9300
C1—S1	1.772 (3)	C12—C13	1.385 (4)
C2—C3	1.378 (5)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.387 (4)
C3—C4	1.367 (6)	C13—H13	0.9300
C3—H3	0.9300	C14—N1	1.434 (3)
C4—C5	1.369 (6)	C15—N1	1.453 (3)
C4—C7	1.521 (5)	C15—C16	1.508 (4)
C5—C6	1.390 (5)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C8	1.505 (5)	C16—N2	1.486 (4)
C8—H8A	0.9600	C16—H16A	0.9700
C8—H8B	0.9600	C16—H16B	0.9700
C8—H8C	0.9600	C17—N2	1.488 (3)
C7—H7A	0.9600	C17—C18	1.503 (4)
C7—H7B	0.9600	C17—H17A	0.9700
C7—H7C	0.9600	C17—H17B	0.9700
C9—C10	1.388 (4)	C18—N1	1.470 (3)
C9—C14	1.397 (4)	C18—H18A	0.9700
C9—S1	1.769 (3)	C18—H18B	0.9700
C10—C11	1.386 (4)	N2—H2A	0.9000
C10—H10	0.9300	N2—H2B	0.9000

C6—C1—C2	119.7 (3)	C13—C12—H12	119.9
C6—C1—S1	122.8 (3)	C12—C13—C14	120.8 (3)
C2—C1—S1	117.4 (3)	C12—C13—H13	119.6
C3—C2—C1	120.0 (4)	C14—C13—H13	119.6
C3—C2—H2	120.0	C13—C14—C9	119.1 (2)
C1—C2—H2	120.0	C13—C14—N1	123.1 (2)
C4—C3—C2	121.4 (4)	C9—C14—N1	117.8 (2)
C4—C3—H3	119.3	N1—C15—C16	109.5 (2)
C2—C3—H3	119.3	N1—C15—H15A	109.8
C3—C4—C5	117.8 (4)	C16—C15—H15A	109.8
C3—C4—C7	121.6 (5)	N1—C15—H15B	109.8
C5—C4—C7	120.6 (5)	C16—C15—H15B	109.8
C4—C5—C6	123.0 (4)	H15A—C15—H15B	108.2
C4—C5—H5	118.5	N2—C16—C15	109.5 (2)
C6—C5—H5	118.5	N2—C16—H16A	109.8
C1—C6—C5	117.9 (3)	C15—C16—H16A	109.8
C1—C6—C8	121.7 (3)	N2—C16—H16B	109.8
C5—C6—C8	120.3 (4)	C15—C16—H16B	109.8
C6—C8—H8A	109.5	H16A—C16—H16B	108.2
C6—C8—H8B	109.5	N2—C17—C18	109.5 (2)
H7A—C8—H8B	109.5	N2—C17—H17A	109.8
C6—C8—H8C	109.5	C18—C17—H17A	109.8
H7A—C8—H8C	109.5	N2—C17—H17B	109.8
H7B—C8—H8C	109.5	C18—C17—H17B	109.8
C4—C7—H7A	109.5	H17A—C17—H17B	108.2
C4—C7—H7B	109.5	N1—C18—C17	110.4 (2)
H8A—C7—H7B	109.5	N1—C18—H18A	109.6
C4—C7—H7C	109.5	C17—C18—H18A	109.6
H8A—C7—H7C	109.5	N1—C18—H18B	109.6
H8B—C7—H7C	109.5	C17—C18—H18B	109.6
C10—C9—C14	119.3 (2)	H18A—C18—H18B	108.1
C10—C9—S1	124.3 (2)	C14—N1—C15	115.7 (2)
C14—C9—S1	116.3 (2)	C14—N1—C18	111.84 (19)
C11—C10—C9	120.7 (3)	C15—N1—C18	110.1 (2)
C11—C10—H10	119.7	C16—N2—C17	111.5 (2)
C9—C10—H10	119.7	C16—N2—H2A	109.3
C12—C11—C10	119.9 (3)	C17—N2—H2A	109.3
C12—C11—H11	120.0	C16—N2—H2B	109.3
C10—C11—H11	120.0	C17—N2—H2B	109.3
C11—C12—C13	120.2 (3)	H2A—N2—H2B	108.0
C11—C12—H12	119.9	C9—S1—C1	103.46 (13)

C6—C1—C2—C3	1.1 (5)	C10—C9—C14—C13	2.6 (4)
S1—C1—C2—C3	−175.2 (3)	S1—C9—C14—C13	−174.7 (2)
C1—C2—C3—C4	−0.3 (6)	C10—C9—C14—N1	−176.9 (2)
C2—C3—C4—C5	−0.6 (6)	S1—C9—C14—N1	5.8 (3)
C2—C3—C4—C7	178.1 (4)	N1—C15—C16—N2	59.1 (3)
C3—C4—C5—C6	0.8 (5)	N2—C17—C18—N1	−56.9 (3)
C7—C4—C5—C6	−177.9 (3)	C13—C14—N1—C15	29.4 (3)
C2—C1—C6—C5	−0.9 (4)	C9—C14—N1—C15	−151.1 (2)
S1—C1—C6—C5	175.2 (2)	C13—C14—N1—C18	−97.7 (3)
C2—C1—C6—C8	179.1 (3)	C9—C14—N1—C18	81.8 (3)
S1—C1—C6—C8	−4.8 (4)	C16—C15—N1—C14	170.4 (2)
C4—C5—C6—C1	0.0 (5)	C16—C15—N1—C18	−61.6 (3)
C4—C5—C6—C8	180.0 (3)	C17—C18—N1—C14	−168.8 (2)
C14—C9—C10—C11	−2.0 (4)	C17—C18—N1—C15	61.0 (3)
S1—C9—C10—C11	175.1 (2)	C15—C16—N2—C17	−56.5 (3)
C9—C10—C11—C12	−0.2 (5)	C18—C17—N2—C16	55.3 (3)
C10—C11—C12—C13	1.6 (5)	C10—C9—S1—C1	−0.2 (3)
C11—C12—C13—C14	−1.0 (4)	C14—C9—S1—C1	176.9 (2)
C12—C13—C14—C9	−1.2 (4)	C6—C1—S1—C9	80.6 (3)
C12—C13—C14—N1	178.3 (2)	C2—C1—S1—C9	−103.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.90	2.18	3.072 (2)	173
N2—H2B···Cl1ⁱ	0.90	2.20	3.091 (2)	171

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

(6) top

Crystal data top

C₃₆H₄₅N₄S₂·Cl	F(000) = 676
M_r = 633.33	D_x = 1.223 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9413 reflections
a = 20.9755 (12) Å	θ = 3.2–27.5°
b = 7.7160 (4) Å	µ = 0.26 mm⁻¹
c = 10.6432 (7) Å	T = 296 K
β = 93.067 (2)°	Platelet, colorless
V = 1720.10 (17) Å³	0.50 × 0.38 × 0.10 mm
Z = 2

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	3028 independent reflections
Radiation source: rotating anode	1917 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.0°, θ_min = 3.3°
ω scans	h = −24→24
Absorption correction: multi-scan Higashi, T. (1995)	k = −9→8
T_min = 0.860, T_max = 0.974	l = −12→12
13112 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.097	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.296	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1424P)² + 4.1586P] where P = (F_o² + 2F_c²)/3
3028 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3373 (3)	0.4608 (7)	0.2359 (7)	0.0688 (16)
C2	0.3646 (3)	0.4408 (10)	0.1257 (8)	0.090 (2)
H2	0.3395	0.4426	0.0509	0.108*
C3	0.4308 (4)	0.4171 (10)	0.1229 (9)	0.093 (2)
H3	0.4484	0.4060	0.0450	0.112*
C4	0.4698 (3)	0.4095 (8)	0.2261 (9)	0.089 (2)
C5	0.4410 (4)	0.4292 (10)	0.3398 (8)	0.097 (2)
H5	0.4663	0.4250	0.4141	0.116*
C6	0.3739 (4)	0.4558 (8)	0.3467 (7)	0.086 (2)
C7	0.5410 (3)	0.3894 (12)	0.2199 (12)	0.131 (4)
H7A	0.5504	0.3314	0.1432	0.197*
H7B	0.5573	0.3223	0.2905	0.197*
H7C	0.5608	0.5017	0.2220	0.197*
C8	0.3466 (6)	0.4830 (15)	0.4709 (9)	0.148 (4)
H8A	0.3555	0.5991	0.4991	0.222*
H8B	0.3653	0.4021	0.5306	0.222*
H8C	0.3012	0.4655	0.4633	0.222*
C9	0.2415 (2)	0.6928 (7)	0.2894 (6)	0.0601 (14)
C10	0.2817 (3)	0.8262 (7)	0.2524 (7)	0.0733 (18)
H10	0.3159	0.8016	0.2034	0.088*
C11	0.2703 (3)	0.9928 (7)	0.2887 (6)	0.0703 (17)
H11	0.2988	1.0802	0.2697	0.084*
C12	0.2180 (3)	1.0312 (7)	0.3520 (7)	0.0745 (18)
H12	0.2090	1.1460	0.3710	0.089*
C13	0.1777 (3)	0.9010 (7)	0.3887 (6)	0.0671 (16)
H13	0.1423	0.9285	0.4340	0.081*
C14	0.1895 (2)	0.7315 (6)	0.3588 (5)	0.0471 (11)
C15	0.0944 (3)	0.5618 (7)	0.3111 (5)	0.0563 (13)
H15A	0.1068	0.5619	0.2247	0.068*
H15B	0.0638	0.6547	0.3206	0.068*
C16	0.0640 (3)	0.3904 (7)	0.3407 (5)	0.0665 (16)
H16A	0.0256	0.3743	0.2869	0.080*
H16B	0.0932	0.2969	0.3241	0.080*
C17	0.1038 (3)	0.4226 (7)	0.5594 (5)	0.0636 (15)
H17A	0.1356	0.3326	0.5518	0.076*
H17B	0.0912	0.4243	0.6458	0.076*
C18	0.1317 (3)	0.5956 (7)	0.5267 (5)	0.0579 (14)
H18A	0.1005	0.6866	0.5372	0.069*
H18B	0.1689	0.6200	0.5820	0.069*
Cl1	0.0000	0.0000	0.5000	0.0784 (8)
N1	0.14994 (18)	0.5905 (5)	0.3953 (4)	0.0473 (10)
N2	0.04764 (19)	0.3850 (5)	0.4740 (4)	0.0518 (11)
H2A	0.0323	0.2794	0.4918	0.062*
H2B	0.0168	0.4632	0.4868	0.062*	0.50
S1	0.25296 (8)	0.4753 (2)	0.2394 (2)	0.0927 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.070 (4)	0.043 (3)	0.096 (5)	0.000 (3)	0.021 (4)	−0.001 (3)
C2	0.079 (4)	0.091 (5)	0.100 (5)	−0.009 (4)	0.023 (4)	−0.007 (4)
C3	0.070 (4)	0.098 (5)	0.113 (6)	−0.004 (4)	0.033 (4)	−0.018 (5)
C4	0.069 (4)	0.055 (4)	0.145 (7)	0.010 (3)	0.022 (5)	−0.007 (4)
C5	0.103 (6)	0.075 (4)	0.111 (6)	0.013 (4)	−0.006 (5)	0.005 (4)
C6	0.125 (6)	0.054 (3)	0.082 (5)	0.013 (4)	0.037 (5)	0.002 (3)
C7	0.064 (4)	0.099 (6)	0.232 (12)	0.013 (4)	0.019 (6)	−0.006 (7)
C8	0.206 (12)	0.153 (10)	0.087 (6)	0.048 (8)	0.028 (7)	0.023 (6)
C9	0.044 (3)	0.044 (3)	0.094 (4)	−0.006 (2)	0.015 (3)	0.008 (3)
C10	0.052 (3)	0.049 (3)	0.122 (5)	−0.009 (3)	0.028 (3)	0.011 (3)
C11	0.057 (3)	0.044 (3)	0.111 (5)	−0.012 (2)	0.015 (3)	0.013 (3)
C12	0.078 (4)	0.035 (3)	0.113 (5)	−0.003 (3)	0.027 (4)	0.002 (3)
C13	0.063 (3)	0.045 (3)	0.096 (4)	−0.004 (3)	0.023 (3)	0.002 (3)
C14	0.040 (2)	0.043 (2)	0.058 (3)	−0.007 (2)	0.001 (2)	0.008 (2)
C15	0.061 (3)	0.064 (3)	0.044 (3)	−0.023 (3)	0.002 (2)	0.000 (2)
C16	0.069 (3)	0.059 (3)	0.074 (4)	−0.025 (3)	0.017 (3)	−0.021 (3)
C17	0.062 (3)	0.063 (3)	0.066 (3)	−0.005 (3)	0.003 (3)	0.025 (3)
C18	0.054 (3)	0.068 (3)	0.050 (3)	−0.018 (3)	−0.009 (2)	0.012 (3)
Cl1	0.0846 (15)	0.0365 (9)	0.1119 (18)	−0.0070 (9)	−0.0157 (13)	0.0063 (10)
N1	0.043 (2)	0.043 (2)	0.057 (2)	−0.0105 (17)	0.0058 (18)	0.0067 (18)
N2	0.051 (2)	0.035 (2)	0.072 (3)	−0.0098 (17)	0.017 (2)	0.0039 (19)
S1	0.0693 (11)	0.0543 (10)	0.158 (2)	−0.0122 (7)	0.0375 (11)	−0.0158 (10)

Geometric parameters (Å, º) top

C1—C2	1.341 (9)	C11—C12	1.351 (8)
C1—C6	1.373 (10)	C11—H11	0.9300
C1—S1	1.776 (6)	C12—C13	1.383 (8)
C2—C3	1.402 (10)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.372 (7)
C3—C4	1.336 (11)	C13—H13	0.9300
C3—H3	0.9300	C14—N1	1.433 (6)
C4—C5	1.389 (11)	C15—N1	1.449 (6)
C4—C7	1.507 (10)	C15—C16	1.509 (7)
C5—C6	1.428 (11)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C8	1.483 (11)	C16—N2	1.478 (7)
C7—H7A	0.9600	C16—H16A	0.9700
C7—H7B	0.9600	C16—H16B	0.9700
C7—H7C	0.9600	C17—N2	1.477 (7)
C8—H8A	0.9600	C17—C18	1.506 (7)
C8—H8B	0.9600	C17—H17A	0.9700
C8—H8C	0.9600	C17—H17B	0.9700
C9—C14	1.383 (7)	C18—N1	1.470 (6)
C9—C10	1.400 (7)	C18—H18A	0.9700
C9—S1	1.781 (6)	C18—H18B	0.9700
C10—C11	1.367 (8)	N2—H2A	0.9000
C10—H10	0.9300	N2—H2B	0.9000

C2—C1—C6	120.2 (7)	C13—C12—H12	119.8
C2—C1—S1	119.9 (6)	C14—C13—C12	120.4 (5)
C6—C1—S1	119.7 (5)	C14—C13—H13	119.8
C1—C2—C3	120.2 (8)	C12—C13—H13	119.8
C1—C2—H2	119.9	C13—C14—C9	119.1 (4)
C3—C2—H2	119.9	C13—C14—N1	123.1 (4)
C4—C3—C2	123.5 (7)	C9—C14—N1	117.8 (4)
C4—C3—H3	118.3	N1—C15—C16	109.9 (4)
C2—C3—H3	118.3	N1—C15—H15A	109.7
C3—C4—C5	115.8 (7)	C16—C15—H15A	109.7
C3—C4—C7	122.2 (9)	N1—C15—H15B	109.7
C5—C4—C7	121.9 (9)	C16—C15—H15B	109.7
C4—C5—C6	122.5 (8)	H15A—C15—H15B	108.2
C4—C5—H5	118.8	N2—C16—C15	110.3 (4)
C6—C5—H5	118.8	N2—C16—H16A	109.6
C1—C6—C5	117.8 (6)	C15—C16—H16A	109.6
C1—C6—C8	122.5 (8)	N2—C16—H16B	109.6
C5—C6—C8	119.7 (9)	C15—C16—H16B	109.6
C4—C7—H7A	109.5	H16A—C16—H16B	108.1
C4—C7—H7B	109.5	N2—C17—C18	109.8 (4)
H7A—C7—H7B	109.5	N2—C17—H17A	109.7
C4—C7—H7C	109.5	C18—C17—H17A	109.7
H7A—C7—H7C	109.5	N2—C17—H17B	109.7
H7B—C7—H7C	109.5	C18—C17—H17B	109.7
C6—C8—H8A	109.5	H17A—C17—H17B	108.2
C6—C8—H8B	109.5	N1—C18—C17	108.7 (4)
H8A—C8—H8B	109.5	N1—C18—H18A	109.9
C6—C8—H8C	109.5	C17—C18—H18A	109.9
H8A—C8—H8C	109.5	N1—C18—H18B	109.9
H8B—C8—H8C	109.5	C17—C18—H18B	109.9
C14—C9—C10	119.7 (5)	H18A—C18—H18B	108.3
C14—C9—S1	119.1 (4)	C14—N1—C15	114.0 (4)
C10—C9—S1	121.1 (4)	C14—N1—C18	114.9 (4)
C11—C10—C9	119.7 (5)	C15—N1—C18	110.5 (4)
C11—C10—H10	120.1	C16—N2—C17	111.6 (4)
C9—C10—H10	120.1	C16—N2—H2A	109.3
C12—C11—C10	120.4 (5)	C17—N2—H2A	109.3
C12—C11—H11	119.8	C16—N2—H2B	109.3
C10—C11—H11	119.8	C17—N2—H2B	109.3
C11—C12—C13	120.4 (5)	H2A—N2—H2B	108.0
C11—C12—H12	119.8	C1—S1—C9	102.5 (3)

C6—C1—C2—C3	−0.9 (10)	C10—C9—C14—C13	0.9 (9)
S1—C1—C2—C3	−175.5 (6)	S1—C9—C14—C13	−174.8 (5)
C1—C2—C3—C4	1.3 (12)	C10—C9—C14—N1	−179.6 (5)
C2—C3—C4—C5	−0.9 (11)	S1—C9—C14—N1	4.7 (7)
C2—C3—C4—C7	−178.1 (7)	N1—C15—C16—N2	56.5 (6)
C3—C4—C5—C6	0.1 (11)	N2—C17—C18—N1	−58.9 (6)
C7—C4—C5—C6	177.3 (7)	C13—C14—N1—C15	83.8 (6)
C2—C1—C6—C5	0.1 (9)	C9—C14—N1—C15	−95.6 (6)
S1—C1—C6—C5	174.8 (5)	C13—C14—N1—C18	−45.2 (7)
C2—C1—C6—C8	177.9 (8)	C9—C14—N1—C18	135.3 (5)
S1—C1—C6—C8	−7.5 (9)	C16—C15—N1—C14	167.9 (4)
C4—C5—C6—C1	0.3 (11)	C16—C15—N1—C18	−60.9 (6)
C4—C5—C6—C8	−177.5 (8)	C17—C18—N1—C14	−167.2 (4)
C14—C9—C10—C11	2.1 (10)	C17—C18—N1—C15	62.1 (5)
S1—C9—C10—C11	177.7 (5)	C15—C16—N2—C17	−54.8 (6)
C9—C10—C11—C12	−4.9 (11)	C18—C17—N2—C16	56.4 (6)
C10—C11—C12—C13	4.6 (11)	C2—C1—S1—C9	−113.1 (6)
C11—C12—C13—C14	−1.5 (11)	C6—C1—S1—C9	72.2 (5)
C12—C13—C14—C9	−1.2 (9)	C14—C9—S1—C1	−149.6 (5)
C12—C13—C14—N1	179.3 (6)	C10—C9—S1—C1	34.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.90	2.26	3.151 (4)	169

(7) top

Crystal data top

C₁₈H₂₃N₂S·Br	F(000) = 784
M_r = 379.35	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9477 reflections
a = 13.0982 (8) Å	θ = 3.0–27.8°
b = 18.2551 (9) Å	µ = 2.35 mm⁻¹
c = 7.8088 (4) Å	T = 296 K
β = 100.698 (2)°	Platelet, colorless
V = 1834.70 (17) Å³	0.50 × 0.48 × 0.16 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	4179 independent reflections
Radiation source: rotating anode	2317 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −17→16
Absorption correction: multi-scan Higashi, T. (1995)	k = −23→23
T_min = 0.306, T_max = 0.695	l = −10→9
17291 measured 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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0579P)² + 1.5412P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4179 reflections	Δρ_max = 0.53 e Å⁻³
200 parameters	Δρ_min = −0.80 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0122 (12)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.1502 (3)	0.5710 (2)	0.1072 (5)	0.0510 (10)
C2	0.1862 (4)	0.5949 (3)	−0.0389 (6)	0.0599 (12)
H2	0.2541	0.5846	−0.0505	0.072*
C3	0.1227 (5)	0.6339 (3)	−0.1668 (6)	0.0727 (15)
H3	0.1487	0.6500	−0.2633	0.087*
C4	0.0220 (5)	0.6496 (3)	−0.1550 (7)	0.0726 (15)
C5	−0.0134 (4)	0.6242 (3)	−0.0103 (7)	0.0668 (13)
H5	−0.0820	0.6338	−0.0014	0.080*
C6	0.0478 (4)	0.5854 (2)	0.1220 (6)	0.0562 (11)
C7	−0.0483 (6)	0.6927 (4)	−0.2942 (9)	0.125 (3)
H7A	−0.0112	0.7054	−0.3851	0.188*
H7B	−0.0706	0.7366	−0.2442	0.188*
H7C	−0.1079	0.6636	−0.3418	0.188*
C8	0.0038 (4)	0.5598 (3)	0.2785 (7)	0.0857 (17)
H8A	0.0564	0.5338	0.3573	0.129*
H8B	−0.0543	0.5280	0.2403	0.129*
H8C	−0.0185	0.6015	0.3369	0.129*
C9	0.2796 (3)	0.5848 (2)	0.4300 (5)	0.0472 (10)
C10	0.2591 (4)	0.6596 (2)	0.4136 (6)	0.0534 (11)
H10	0.2135	0.6771	0.3165	0.064*
C11	0.3056 (4)	0.7080 (2)	0.5399 (6)	0.0570 (11)
H11	0.2902	0.7577	0.5285	0.068*
C12	0.3744 (4)	0.6833 (2)	0.6819 (6)	0.0595 (12)
H12	0.4080	0.7163	0.7640	0.071*
C13	0.3936 (3)	0.6089 (2)	0.7027 (5)	0.0502 (10)
H13	0.4396	0.5923	0.8003	0.060*
C14	0.3453 (3)	0.5590 (2)	0.5807 (5)	0.0448 (9)
C15	0.2728 (3)	0.4420 (2)	0.6412 (6)	0.0513 (10)
H15A	0.2087	0.4606	0.5724	0.062*
H15B	0.2703	0.4491	0.7634	0.062*
C16	0.2840 (4)	0.3618 (2)	0.6043 (6)	0.0551 (11)
H16A	0.2260	0.3349	0.6344	0.066*
H16B	0.2835	0.3547	0.4810	0.066*
C17	0.4729 (4)	0.3762 (2)	0.6742 (6)	0.0598 (12)
H17A	0.4814	0.3694	0.5544	0.072*
H17B	0.5354	0.3589	0.7500	0.072*
C18	0.4572 (3)	0.4568 (2)	0.7082 (6)	0.0514 (10)
H18A	0.4525	0.4641	0.8295	0.062*
H18B	0.5159	0.4848	0.6841	0.062*
N1	0.3621 (3)	0.48179 (17)	0.5965 (4)	0.0453 (8)
N2	0.3821 (3)	0.33361 (16)	0.7066 (5)	0.0516 (9)
H2A	0.3899	0.2864	0.6786	0.062*
H2B	0.3792	0.3357	0.8208	0.062*
S1	0.23556 (10)	0.51918 (6)	0.26458 (15)	0.0617 (4)
Br1	0.33920 (4)	0.16416 (2)	0.60005 (6)	0.0657 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (3)	0.049 (2)	0.052 (2)	−0.0055 (19)	0.008 (2)	−0.0034 (19)
C2	0.053 (3)	0.073 (3)	0.055 (3)	−0.008 (2)	0.013 (2)	−0.006 (2)
C3	0.080 (4)	0.085 (4)	0.051 (3)	−0.023 (3)	0.007 (3)	0.003 (3)
C4	0.076 (4)	0.064 (3)	0.069 (3)	−0.008 (3)	−0.010 (3)	0.003 (3)
C5	0.048 (3)	0.066 (3)	0.082 (3)	0.000 (2)	0.003 (3)	−0.006 (3)
C6	0.054 (3)	0.054 (2)	0.062 (3)	−0.011 (2)	0.015 (2)	−0.006 (2)
C7	0.135 (7)	0.122 (5)	0.096 (5)	0.014 (5)	−0.036 (5)	0.030 (4)
C8	0.077 (4)	0.103 (4)	0.087 (4)	−0.011 (3)	0.041 (3)	0.009 (3)
C9	0.052 (3)	0.042 (2)	0.050 (2)	−0.0002 (18)	0.0139 (19)	0.0009 (18)
C10	0.060 (3)	0.044 (2)	0.058 (3)	0.003 (2)	0.016 (2)	0.003 (2)
C11	0.070 (3)	0.037 (2)	0.068 (3)	0.000 (2)	0.023 (2)	−0.004 (2)
C12	0.066 (3)	0.050 (2)	0.065 (3)	−0.009 (2)	0.016 (2)	−0.009 (2)
C13	0.055 (3)	0.047 (2)	0.049 (2)	−0.0063 (19)	0.011 (2)	−0.0054 (19)
C14	0.044 (3)	0.040 (2)	0.053 (2)	−0.0010 (17)	0.0167 (19)	0.0017 (18)
C15	0.046 (3)	0.044 (2)	0.067 (3)	0.0007 (18)	0.016 (2)	0.007 (2)
C16	0.053 (3)	0.047 (2)	0.065 (3)	−0.006 (2)	0.010 (2)	0.006 (2)
C17	0.051 (3)	0.052 (2)	0.079 (3)	0.006 (2)	0.020 (2)	0.007 (2)
C18	0.045 (3)	0.046 (2)	0.064 (3)	−0.0002 (19)	0.012 (2)	0.005 (2)
N1	0.041 (2)	0.0401 (17)	0.0548 (19)	−0.0016 (14)	0.0079 (16)	0.0040 (15)
N2	0.058 (2)	0.0383 (17)	0.060 (2)	0.0012 (16)	0.0146 (18)	0.0007 (15)
S1	0.0743 (9)	0.0451 (6)	0.0621 (7)	0.0059 (5)	0.0031 (6)	−0.0061 (5)
Br1	0.0868 (5)	0.0515 (3)	0.0608 (3)	−0.0061 (2)	0.0191 (3)	−0.0025 (2)

Geometric parameters (Å, º) top

C1—C2	1.384 (6)	C11—C12	1.368 (7)
C1—C6	1.392 (6)	C11—H11	0.9300
C1—S1	1.773 (4)	C12—C13	1.386 (6)
C2—C3	1.374 (7)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.384 (6)
C3—C4	1.369 (8)	C13—H13	0.9300
C3—H3	0.9300	C14—N1	1.428 (5)
C4—C5	1.379 (7)	C15—N1	1.474 (5)
C4—C7	1.510 (8)	C15—C16	1.506 (5)
C5—C6	1.381 (7)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C8	1.518 (6)	C16—N2	1.473 (6)
C7—H7A	0.9600	C16—H16A	0.9700
C7—H7B	0.9600	C16—H16B	0.9700
C7—H7C	0.9600	C17—N2	1.482 (5)
C8—H8A	0.9600	C17—C18	1.515 (6)
C8—H8B	0.9600	C17—H17A	0.9700
C8—H8C	0.9600	C17—H17B	0.9700
C9—C10	1.394 (5)	C18—N1	1.455 (5)
C9—C14	1.404 (6)	C18—H18A	0.9700
C9—S1	1.777 (4)	C18—H18B	0.9700
C10—C11	1.379 (6)	N2—H2A	0.9000
C10—H10	0.9300	N2—H2B	0.9000

C2—C1—C6	119.3 (4)	C13—C12—H12	120.1
C2—C1—S1	118.2 (4)	C14—C13—C12	121.0 (4)
C6—C1—S1	122.5 (3)	C14—C13—H13	119.5
C3—C2—C1	120.7 (5)	C12—C13—H13	119.5
C3—C2—H2	119.7	C13—C14—C9	119.1 (4)
C1—C2—H2	119.7	C13—C14—N1	123.1 (4)
C4—C3—C2	121.3 (5)	C9—C14—N1	117.7 (3)
C4—C3—H3	119.4	N1—C15—C16	108.9 (3)
C2—C3—H3	119.4	N1—C15—H15A	109.9
C3—C4—C5	117.4 (5)	C16—C15—H15A	109.9
C3—C4—C7	121.8 (6)	N1—C15—H15B	109.9
C5—C4—C7	120.8 (6)	C16—C15—H15B	109.9
C4—C5—C6	123.2 (5)	H15A—C15—H15B	108.3
C4—C5—H5	118.4	N2—C16—C15	110.0 (4)
C6—C5—H5	118.4	N2—C16—H16A	109.7
C5—C6—C1	118.0 (4)	C15—C16—H16A	109.7
C5—C6—C8	120.4 (5)	N2—C16—H16B	109.7
C1—C6—C8	121.6 (4)	C15—C16—H16B	109.7
C4—C7—H7A	109.5	H16A—C16—H16B	108.2
C4—C7—H7B	109.5	N2—C17—C18	109.9 (3)
H7A—C7—H7B	109.5	N2—C17—H17A	109.7
C4—C7—H7C	109.5	C18—C17—H17A	109.7
H7A—C7—H7C	109.5	N2—C17—H17B	109.7
H7B—C7—H7C	109.5	C18—C17—H17B	109.7
C6—C8—H8A	109.5	H17A—C17—H17B	108.2
C6—C8—H8B	109.5	N1—C18—C17	109.1 (3)
H8A—C8—H8B	109.5	N1—C18—H18A	109.9
C6—C8—H8C	109.5	C17—C18—H18A	109.9
H8A—C8—H8C	109.5	N1—C18—H18B	109.9
H8B—C8—H8C	109.5	C17—C18—H18B	109.9
C10—C9—C14	118.9 (4)	H18A—C18—H18B	108.3
C10—C9—S1	124.2 (3)	C14—N1—C18	117.5 (3)
C14—C9—S1	116.7 (3)	C14—N1—C15	113.0 (3)
C11—C10—C9	120.7 (4)	C18—N1—C15	109.5 (3)
C11—C10—H10	119.7	C16—N2—C17	111.8 (3)
C9—C10—H10	119.7	C16—N2—H2A	109.3
C12—C11—C10	120.4 (4)	C17—N2—H2A	109.3
C12—C11—H11	119.8	C16—N2—H2B	109.3
C10—C11—H11	119.8	C17—N2—H2B	109.3
C11—C12—C13	119.7 (4)	H2A—N2—H2B	107.9
C11—C12—H12	120.1	C1—S1—C9	102.85 (19)

C6—C1—C2—C3	1.4 (7)	C10—C9—C14—C13	−4.5 (6)
S1—C1—C2—C3	178.6 (4)	S1—C9—C14—C13	171.0 (3)
C1—C2—C3—C4	−0.7 (8)	C10—C9—C14—N1	177.9 (3)
C2—C3—C4—C5	−0.4 (8)	S1—C9—C14—N1	−6.5 (5)
C2—C3—C4—C7	179.6 (5)	N1—C15—C16—N2	58.7 (5)
C3—C4—C5—C6	0.9 (8)	N2—C17—C18—N1	−58.1 (5)
C7—C4—C5—C6	−179.1 (5)	C13—C14—N1—C18	−21.6 (5)
C4—C5—C6—C1	−0.3 (7)	C9—C14—N1—C18	155.8 (4)
C4—C5—C6—C8	179.4 (5)	C13—C14—N1—C15	107.3 (4)
C2—C1—C6—C5	−0.9 (6)	C9—C14—N1—C15	−75.3 (4)
S1—C1—C6—C5	−178.0 (3)	C17—C18—N1—C14	−166.6 (3)
C2—C1—C6—C8	179.4 (4)	C17—C18—N1—C15	62.8 (4)
S1—C1—C6—C8	2.3 (6)	C16—C15—N1—C14	163.7 (3)
C14—C9—C10—C11	2.5 (6)	C16—C15—N1—C18	−63.2 (4)
S1—C9—C10—C11	−172.7 (3)	C15—C16—N2—C17	−55.5 (5)
C9—C10—C11—C12	1.2 (7)	C18—C17—N2—C16	54.9 (5)
C10—C11—C12—C13	−3.0 (7)	C2—C1—S1—C9	101.2 (4)
C11—C12—C13—C14	0.9 (6)	C6—C1—S1—C9	−81.7 (4)
C12—C13—C14—C9	2.9 (6)	C10—C9—S1—C1	−8.3 (4)
C12—C13—C14—N1	−179.8 (4)	C14—C9—S1—C1	176.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Br1	0.90	2.38	3.225 (3)	157
N2—H2B···Br1ⁱ	0.90	2.34	3.224 (4)	169

Symmetry code: (i) x, −y+1/2, z+1/2.

(8) top

Crystal data top

C₃₆H₄₅N₄S₂·Br	F(000) = 712
M_r = 677.79	D_x = 1.284 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8791 reflections
a = 21.1781 (12) Å	θ = 3.2–27.4°
b = 7.8799 (4) Å	µ = 1.32 mm⁻¹
c = 10.5126 (8) Å	T = 296 K
β = 87.993 (2)°	Chunk, colorless
V = 1753.28 (19) Å³	0.50 × 0.36 × 0.30 mm
Z = 2

Data collection top

Rigaku RAXIS-RAPID/ZJUG diffractometer	3126 independent reflections
Radiation source: rotating anode	1927 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.1°, θ_min = 3.2°
ω scans	h = −25→25
Absorption correction: multi-scan Higashi, T. (1995)	k = −9→8
T_min = 0.508, T_max = 0.683	l = −12→12
13386 measured 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)] = 0.092	H-atom parameters constrained
wR(F²) = 0.287	w = 1/[σ²(F_o²) + (0.1501P)² + 4.4364P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3126 reflections	Δρ_max = 2.02 e Å⁻³
199 parameters	Δρ_min = −0.99 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (4)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.3387 (4)	0.4586 (10)	0.2423 (10)	0.083 (2)
C2	0.3653 (5)	0.4366 (15)	0.1301 (11)	0.110 (3)
H2	0.3418	0.4381	0.0571	0.132*
C3	0.4304 (5)	0.4107 (15)	0.1234 (13)	0.119 (4)
H3	0.4493	0.3961	0.0430	0.143*
C4	0.4698 (5)	0.4049 (11)	0.2279 (12)	0.103 (3)
C5	0.4416 (5)	0.4239 (14)	0.3416 (12)	0.115 (3)
H5	0.4649	0.4195	0.4149	0.139*
C6	0.3739 (5)	0.4515 (12)	0.3503 (10)	0.102 (3)
C7	0.5398 (4)	0.3808 (16)	0.2170 (15)	0.152 (5)
H7A	0.5602	0.4895	0.2125	0.228*
H7B	0.5505	0.3171	0.1414	0.228*
H7C	0.5537	0.3202	0.2901	0.228*
C8	0.3465 (9)	0.483 (2)	0.4786 (13)	0.179 (7)
H8A	0.3478	0.6022	0.4966	0.268*
H8B	0.3704	0.4225	0.5400	0.268*
H8C	0.3035	0.4443	0.4829	0.268*
C9	0.2445 (3)	0.6879 (9)	0.2971 (8)	0.078 (2)
C10	0.2838 (3)	0.8175 (10)	0.2569 (10)	0.097 (3)
H10	0.3189	0.7913	0.2049	0.116*
C11	0.2736 (4)	0.9829 (8)	0.2899 (10)	0.086 (2)
H11	0.3024	1.0664	0.2649	0.103*
C12	0.2217 (4)	1.0228 (9)	0.3585 (9)	0.084 (2)
H12	0.2131	1.1354	0.3795	0.101*
C13	0.1810 (3)	0.8971 (9)	0.3977 (7)	0.0728 (19)
H13	0.1447	0.9255	0.4451	0.087*
C14	0.1926 (3)	0.7298 (7)	0.3688 (6)	0.0547 (14)
C15	0.1001 (3)	0.5579 (10)	0.3197 (6)	0.0665 (17)
H15A	0.0685	0.6468	0.3273	0.080*
H15B	0.1166	0.5562	0.2325	0.080*
C16	0.0706 (3)	0.3908 (9)	0.3518 (7)	0.074 (2)
H16A	0.0348	0.3712	0.2987	0.089*
H16B	0.1010	0.3003	0.3365	0.089*
C17	0.1026 (3)	0.4369 (9)	0.5743 (7)	0.0699 (18)
H17A	0.0856	0.4416	0.6612	0.084*
H17B	0.1350	0.3500	0.5697	0.084*
C18	0.1306 (3)	0.6051 (8)	0.5378 (6)	0.0613 (16)
H18A	0.0991	0.6939	0.5476	0.074*
H18B	0.1655	0.6318	0.5918	0.074*
N1	0.1525 (2)	0.5935 (6)	0.4078 (5)	0.0563 (13)
N2	0.0500 (2)	0.3922 (6)	0.4846 (5)	0.0640 (15)
H2A	0.0344	0.2893	0.5056	0.077*	0.50
H2B	0.0238	0.4623	0.4952	0.077*
S1	0.25476 (12)	0.4743 (3)	0.2491 (4)	0.1172 (11)
Br1	0.0000	0.0000	0.5000	0.0856 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.084 (5)	0.061 (4)	0.103 (7)	0.001 (4)	0.019 (5)	0.000 (4)
C2	0.088 (6)	0.123 (8)	0.117 (8)	−0.010 (6)	0.019 (6)	−0.010 (6)
C3	0.092 (7)	0.114 (8)	0.148 (10)	−0.002 (6)	0.044 (7)	−0.018 (7)
C4	0.085 (6)	0.073 (5)	0.147 (9)	0.005 (5)	0.030 (6)	−0.009 (6)
C5	0.111 (8)	0.100 (7)	0.136 (9)	0.007 (6)	−0.008 (7)	−0.002 (6)
C6	0.129 (8)	0.070 (5)	0.104 (7)	0.012 (5)	0.047 (7)	0.003 (5)
C7	0.076 (6)	0.118 (9)	0.260 (15)	0.018 (6)	0.033 (8)	0.001 (9)
C8	0.221 (18)	0.193 (17)	0.118 (10)	0.051 (12)	0.053 (11)	0.033 (9)
C9	0.055 (4)	0.051 (4)	0.126 (6)	−0.007 (3)	0.020 (4)	0.010 (4)
C10	0.060 (4)	0.061 (4)	0.166 (8)	−0.006 (3)	0.041 (5)	0.010 (5)
C11	0.063 (4)	0.050 (4)	0.144 (8)	−0.014 (3)	0.013 (4)	0.012 (4)
C12	0.076 (5)	0.045 (4)	0.129 (7)	−0.005 (3)	0.016 (5)	0.007 (4)
C13	0.066 (4)	0.055 (4)	0.096 (5)	−0.008 (3)	0.021 (4)	0.006 (3)
C14	0.048 (3)	0.051 (3)	0.065 (4)	−0.008 (3)	−0.001 (3)	0.010 (3)
C15	0.065 (4)	0.071 (4)	0.062 (4)	−0.020 (3)	0.013 (3)	−0.004 (3)
C16	0.071 (4)	0.065 (4)	0.085 (5)	−0.017 (3)	0.014 (4)	−0.023 (4)
C17	0.070 (4)	0.065 (4)	0.074 (5)	−0.005 (3)	0.005 (3)	0.016 (3)
C18	0.063 (4)	0.059 (4)	0.062 (4)	−0.010 (3)	−0.003 (3)	0.008 (3)
N1	0.054 (3)	0.052 (3)	0.063 (3)	−0.014 (2)	0.005 (2)	0.007 (2)
N2	0.060 (3)	0.043 (3)	0.088 (4)	−0.006 (2)	0.019 (3)	0.004 (2)
S1	0.0763 (14)	0.0667 (13)	0.205 (3)	−0.0106 (10)	0.0429 (17)	−0.0171 (14)
Br1	0.0832 (8)	0.0414 (6)	0.1327 (12)	−0.0050 (4)	−0.0122 (6)	0.0069 (5)

Geometric parameters (Å, º) top

C1—C2	1.300 (12)	C11—C12	1.331 (11)
C1—C6	1.382 (14)	C11—H11	0.9300
C1—S1	1.780 (9)	C12—C13	1.366 (9)
C2—C3	1.392 (13)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.373 (9)
C3—C4	1.403 (15)	C13—H13	0.9300
C3—H3	0.9300	C14—N1	1.422 (7)
C4—C5	1.326 (13)	C15—C16	1.491 (10)
C4—C7	1.496 (12)	C15—N1	1.496 (8)
C5—C6	1.451 (14)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C8	1.469 (15)	C16—N2	1.448 (8)
C7—H7A	0.9600	C16—H16A	0.9700
C7—H7B	0.9600	C16—H16B	0.9700
C7—H7C	0.9600	C17—C18	1.498 (9)
C8—H8A	0.9600	C17—N2	1.526 (9)
C8—H8B	0.9600	C17—H17A	0.9700
C8—H8C	0.9600	C17—H17B	0.9700
C9—C14	1.352 (9)	C18—N1	1.430 (8)
C9—C10	1.375 (9)	C18—H18A	0.9700
C9—S1	1.768 (7)	C18—H18B	0.9700
C10—C11	1.364 (10)	N2—H2A	0.9000
C10—H10	0.9300	N2—H2B	0.7888

C2—C1—C6	120.7 (9)	C13—C12—H12	120.3
C2—C1—S1	116.5 (8)	C12—C13—C14	121.6 (7)
C6—C1—S1	122.4 (7)	C12—C13—H13	119.2
C1—C2—C3	117.5 (11)	C14—C13—H13	119.2
C1—C2—H2	121.2	C9—C14—C13	119.6 (6)
C3—C2—H2	121.2	C9—C14—N1	116.3 (6)
C2—C3—C4	125.5 (10)	C13—C14—N1	124.1 (5)
C2—C3—H3	117.3	C16—C15—N1	109.9 (6)
C4—C3—H3	117.3	C16—C15—H15A	109.7
C5—C4—C3	116.1 (10)	N1—C15—H15A	109.7
C5—C4—C7	119.8 (13)	C16—C15—H15B	109.7
C3—C4—C7	124.0 (11)	N1—C15—H15B	109.7
C4—C5—C6	119.1 (11)	H15A—C15—H15B	108.2
C4—C5—H5	120.4	N2—C16—C15	108.8 (5)
C6—C5—H5	120.4	N2—C16—H16A	109.9
C1—C6—C5	121.0 (9)	C15—C16—H16A	109.9
C1—C6—C8	122.7 (12)	N2—C16—H16B	109.9
C5—C6—C8	116.1 (13)	C15—C16—H16B	109.9
C4—C7—H7A	109.5	H16A—C16—H16B	108.3
C4—C7—H7B	109.5	C18—C17—N2	109.7 (5)
H7A—C7—H7B	109.5	C18—C17—H17A	109.7
C4—C7—H7C	109.5	N2—C17—H17A	109.7
H7A—C7—H7C	109.5	C18—C17—H17B	109.7
H7B—C7—H7C	109.5	N2—C17—H17B	109.7
C6—C8—H8A	109.5	H17A—C17—H17B	108.2
C6—C8—H8B	109.5	N1—C18—C17	107.5 (5)
H8A—C8—H8B	109.5	N1—C18—H18A	110.2
C6—C8—H8C	109.5	C17—C18—H18A	110.2
H8A—C8—H8C	109.5	N1—C18—H18B	110.2
H8B—C8—H8C	109.5	C17—C18—H18B	110.2
C14—C9—C10	117.5 (7)	H18A—C18—H18B	108.5
C14—C9—S1	118.7 (5)	C14—N1—C18	113.4 (5)
C10—C9—S1	123.5 (6)	C14—N1—C15	114.3 (5)
C11—C10—C9	122.8 (7)	C18—N1—C15	112.5 (5)
C11—C10—H10	118.6	C16—N2—C17	113.3 (5)
C9—C10—H10	118.6	C16—N2—H2A	109.0
C12—C11—C10	119.0 (7)	C17—N2—H2A	109.0
C12—C11—H11	120.5	C16—N2—H2B	109.2
C10—C11—H11	120.5	C17—N2—H2B	106.0
C11—C12—C13	119.4 (7)	H2A—N2—H2B	110.3
C11—C12—H12	120.3	C9—S1—C1	100.9 (4)

C6—C1—C2—C3	−1.7 (15)	C10—C9—C14—N1	179.3 (7)
S1—C1—C2—C3	−175.1 (8)	S1—C9—C14—N1	4.6 (9)
C1—C2—C3—C4	0.6 (18)	C12—C13—C14—C9	−1.7 (12)
C2—C3—C4—C5	0.8 (17)	C12—C13—C14—N1	179.4 (7)
C2—C3—C4—C7	−178.5 (11)	N1—C15—C16—N2	55.6 (8)
C3—C4—C5—C6	−1.0 (15)	N2—C17—C18—N1	−57.0 (7)
C7—C4—C5—C6	178.4 (10)	C9—C14—N1—C18	137.0 (7)
C2—C1—C6—C5	1.6 (14)	C13—C14—N1—C18	−44.1 (9)
S1—C1—C6—C5	174.6 (8)	C9—C14—N1—C15	−92.3 (7)
C2—C1—C6—C8	177.3 (11)	C13—C14—N1—C15	86.6 (8)
S1—C1—C6—C8	−9.8 (14)	C17—C18—N1—C14	−166.7 (5)
C4—C5—C6—C1	−0.1 (15)	C17—C18—N1—C15	61.6 (7)
C4—C5—C6—C8	−176.0 (11)	C16—C15—N1—C14	166.8 (5)
C14—C9—C10—C11	2.3 (14)	C16—C15—N1—C18	−62.0 (7)
S1—C9—C10—C11	176.7 (8)	C15—C16—N2—C17	−54.8 (8)
C9—C10—C11—C12	−3.6 (16)	C18—C17—N2—C16	56.4 (7)
C10—C11—C12—C13	2.1 (15)	C14—C9—S1—C1	−149.2 (7)
C11—C12—C13—C14	0.4 (14)	C10—C9—S1—C1	36.5 (9)
C10—C9—C14—C13	0.3 (12)	C2—C1—S1—C9	−113.2 (8)
S1—C9—C14—C13	−174.4 (6)	C6—C1—S1—C9	73.6 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···Br1	0.90	2.39	3.269 (5)	164

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Format		BIBTeX
		EndNote
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		Refer
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		CIF
		SGML
		Text
		Plain Text