Synthesis, structure, ADME and biological activity of three 2,6-disubstituted thio­semicarbazone derivatives

Three new 2,6-disubstituted thio­semicarbazone derivatives of pyridine, namely, 2-{amino­[6-(pyrrolidin-1-yl)pyridin-2-yl]methyl­idene}-N,N-di­methyl­hydrazine-1-carbo­thio­amide, C₁₃H₂₀N₆S, 2-{amino­[6-(piperidin-1-yl)pyridin-2-yl]methyl­idene}-N,N-di­methyl­hydrazine-1-carbo­thio­amide, C₁₄H₂₂N₆S, and 2-[amino­(6-phen­oxy­pyridin-2-yl)methyl­idene]-N,N-di­methyl­hydrazine-1-carbo­thio­amide monohydrate, C₁₅H₁₇N₅OS·H₂O, have been synthesized and characterized by NMR spectroscopy and low-temperature single-crystal X-ray diffraction. In addition, their anti­bacterial and anti-yeast activities have been determined. The ability of the tested com­pounds to inhibit bacterial growth was com­parable to vancomycin as a reference drug. Compared to isoniazid (MIC 0.125 and 8 µg ml⁻¹), the com­pounds showed the ability to inhibit the growth of Mycobacterium tuberculosis to a moderate degree for the standard strain and at the same level or higher (MIC 4–8 µg ml⁻¹) for the resistant strain. All three com­pounds adopt the zwitterionic form in the crystal structure regardless of the presence or absence of solvent mol­ecules.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009), ShelXle (Hübschle et al., 2011) and Mercury program (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010) and OLEX2 (Dolomanov et al., 2009).

2-{Amino[6-(pyrrolidin-1-yl)pyridin-2-yl]methylidene}-N,N-dimethylhydrazine-1-carbothioamide (4)

Crystal data

C13H20N6S	F(000) = 624
Mr = 292.41	Dx = 1.332 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 9.1032 (2) Å	Cell parameters from 19769 reflections
b = 10.9034 (1) Å	θ = 5.0–78.4°
c = 15.3748 (2) Å	µ = 1.97 mm^−1
β = 107.202 (2)°	T = 100 K
V = 1457.78 (4) Å^3	Plate, clear light brown
Z = 4	0.66 × 0.53 × 0.07 mm

Data collection

XtaLAB Synergy, Dualflex, Pilatus 300K diffractometer	2926 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2716 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.077
Detector resolution: 5.8140 pixels mm^-1	θmax = 78.5°, θmin = 5.1°
ω scans	h = −10→11
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	k = −13→13
Tmin = 0.463, Tmax = 1.000	l = −18→19
27991 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 0.602P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 0.53 e Å^−3
2926 reflections	Δρmin = −0.37 e Å^−3
196 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0015 (4)
Primary atom site location: dual

Special details

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. Diffraction measurements were performed using an XtaLAB Synergy Dualflex diffractometer, (Rigaku Oxford Diffraction, Poland–Japan–UK), with a Pilatus 300K detector at low temperature [100.0 (2) K] using Cu Kα radiation (1.54184 Å). Diffraction data were processed using CrysAlis PRO software (Rigaku Oxford Diffraction. CrysAlis PRO; Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England). Solving and refinement of the crystal structure was performed with SHELX (Shedrick, 2008, 2015) using full-matrix least-squares minimization on F². All H atoms (except those of NH₂ and –NH– groups which could potentially be engaged in hydrogen bonds) were geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups and 0.99 Å for secondary CH₂ groups, with U_iso(H) = 1.2U_eq(C). In all the studied structures, the methyl H atoms were refined with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). ShelXle software (Hübschle et al., 2011) was used to visualize the molecular structure. Graphical representation of the crystal structures was performed using the Mercury program (Macrae et al., 2020). PublCIF (Westrip, 2010) and OLEX2 programs (Dolomanov et al., 2009) were used for data preparation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.04534 (4)	0.75908 (3)	0.37551 (2)	0.01890 (14)
N1	−0.18255 (14)	0.65105 (12)	0.24490 (9)	0.0230 (3)
N2	0.04897 (14)	0.55753 (11)	0.27110 (8)	0.0201 (3)
N3	0.20290 (14)	0.56162 (12)	0.31890 (8)	0.0181 (3)
N4	0.24591 (17)	0.39043 (12)	0.24336 (9)	0.0219 (3)
N22	0.50248 (14)	0.59473 (11)	0.40280 (8)	0.0181 (3)
N31	0.68835 (14)	0.71376 (12)	0.50042 (9)	0.0215 (3)
C1	−0.03178 (16)	0.64798 (13)	0.29379 (10)	0.0177 (3)
C4	0.29823 (17)	0.48042 (13)	0.30400 (9)	0.0182 (3)
C11	−0.29400 (18)	0.73250 (15)	0.26571 (12)	0.0239 (3)
H11A	−0.323815	0.796436	0.218982	0.036*
H11B	−0.248221	0.770578	0.325331	0.036*
H11C	−0.385110	0.685409	0.266840	0.036*
C12	−0.2454 (2)	0.56785 (16)	0.16875 (13)	0.0331 (4)
H12A	−0.317917	0.612407	0.118890	0.050*
H12B	−0.298871	0.500177	0.188434	0.050*
H12C	−0.161559	0.535029	0.147734	0.050*
C21	0.46085 (17)	0.48744 (13)	0.35892 (9)	0.0177 (3)
C23	0.64784 (16)	0.60524 (14)	0.45664 (10)	0.0186 (3)
C24	0.75565 (17)	0.50775 (15)	0.46824 (10)	0.0211 (3)
H24	0.857993	0.516959	0.506761	0.025*
C25	0.70829 (18)	0.40031 (15)	0.42252 (10)	0.0242 (3)
H25	0.778245	0.333809	0.429467	0.029*
C26	0.55768 (18)	0.38779 (15)	0.36568 (10)	0.0223 (3)
H26	0.523292	0.314057	0.333096	0.027*
C32	0.58185 (17)	0.81708 (14)	0.48718 (11)	0.0230 (3)
H32A	0.483389	0.792270	0.497055	0.028*
H32B	0.560985	0.852035	0.425281	0.028*
C33	0.66818 (19)	0.90798 (16)	0.55941 (12)	0.0312 (4)
H33A	0.640406	0.993467	0.539570	0.037*
H33B	0.645787	0.893661	0.617800	0.037*
C34	0.8362 (2)	0.88260 (16)	0.56860 (13)	0.0327 (4)
H34A	0.903150	0.909418	0.628810	0.039*
H34B	0.868387	0.925225	0.520377	0.039*
C35	0.84309 (18)	0.74405 (14)	0.55830 (11)	0.0225 (3)
H35A	0.921969	0.720686	0.528742	0.027*
H35B	0.865881	0.702534	0.618085	0.027*
H4A	0.311 (3)	0.3524 (19)	0.2181 (15)	0.037 (5)*
H4B	0.155 (3)	0.3930 (18)	0.2153 (14)	0.030 (5)*
H3	0.235 (2)	0.6166 (18)	0.3602 (13)	0.025 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0172 (2)	0.0238 (2)	0.0160 (2)	0.00164 (12)	0.00537 (16)	−0.00062 (12)
N1	0.0141 (6)	0.0244 (7)	0.0291 (7)	0.0009 (5)	0.0046 (5)	−0.0028 (5)
N2	0.0133 (6)	0.0250 (6)	0.0208 (6)	0.0009 (5)	0.0032 (5)	−0.0007 (5)
N3	0.0140 (6)	0.0226 (6)	0.0169 (6)	0.0011 (5)	0.0035 (5)	−0.0019 (5)
N4	0.0169 (7)	0.0275 (7)	0.0200 (6)	0.0024 (5)	0.0036 (6)	−0.0039 (5)
N22	0.0141 (6)	0.0238 (6)	0.0174 (6)	0.0018 (5)	0.0060 (5)	0.0009 (5)
N31	0.0110 (6)	0.0274 (7)	0.0237 (7)	0.0029 (5)	0.0013 (5)	−0.0023 (5)
C1	0.0156 (7)	0.0210 (7)	0.0178 (7)	−0.0009 (5)	0.0069 (6)	0.0034 (5)
C4	0.0186 (8)	0.0234 (7)	0.0142 (7)	0.0014 (6)	0.0071 (6)	0.0023 (5)
C11	0.0148 (8)	0.0317 (8)	0.0266 (8)	0.0040 (6)	0.0085 (6)	0.0038 (6)
C12	0.0195 (8)	0.0312 (9)	0.0421 (10)	0.0014 (6)	−0.0011 (7)	−0.0102 (7)
C21	0.0172 (7)	0.0244 (7)	0.0129 (7)	0.0021 (6)	0.0068 (6)	0.0016 (5)
C23	0.0154 (7)	0.0272 (7)	0.0147 (7)	0.0020 (6)	0.0070 (6)	0.0020 (6)
C24	0.0149 (7)	0.0334 (8)	0.0147 (7)	0.0060 (6)	0.0040 (6)	0.0025 (6)
C25	0.0222 (8)	0.0328 (8)	0.0172 (7)	0.0121 (6)	0.0049 (6)	0.0005 (6)
C26	0.0234 (8)	0.0274 (8)	0.0152 (7)	0.0060 (6)	0.0045 (6)	−0.0027 (6)
C32	0.0146 (8)	0.0264 (8)	0.0254 (8)	0.0024 (6)	0.0020 (6)	−0.0021 (6)
C33	0.0211 (8)	0.0323 (9)	0.0348 (9)	0.0013 (7)	0.0001 (7)	−0.0102 (7)
C34	0.0213 (9)	0.0363 (9)	0.0358 (10)	−0.0020 (7)	0.0014 (7)	−0.0026 (7)
C35	0.0121 (8)	0.0315 (8)	0.0223 (8)	−0.0011 (6)	0.0027 (6)	0.0005 (6)

Geometric parameters (Å, º)

S1—C1	1.7370 (15)	C12—H12B	0.9800
N1—C1	1.356 (2)	C12—H12C	0.9800
N1—C11	1.4534 (19)	C21—C26	1.383 (2)
N1—C12	1.458 (2)	C23—C24	1.422 (2)
N2—N3	1.3771 (17)	C24—H24	0.9500
N2—C1	1.3366 (19)	C24—C25	1.369 (2)
N3—C4	1.3065 (19)	C25—H25	0.9500
N3—H3	0.86 (2)	C25—C26	1.398 (2)
N4—C4	1.340 (2)	C26—H26	0.9500
N4—H4A	0.90 (2)	C32—H32A	0.9900
N4—H4B	0.82 (2)	C32—H32B	0.9900
N22—C21	1.3477 (19)	C32—C33	1.522 (2)
N22—C23	1.3422 (19)	C33—H33A	0.9900
N31—C23	1.357 (2)	C33—H33B	0.9900
N31—C32	1.4608 (19)	C33—C34	1.519 (2)
N31—C35	1.464 (2)	C34—H34A	0.9900
C4—C21	1.473 (2)	C34—H34B	0.9900
C11—H11A	0.9800	C34—C35	1.522 (2)
C11—H11B	0.9800	C35—H35A	0.9900
C11—H11C	0.9800	C35—H35B	0.9900
C12—H12A	0.9800
C1—N1—C11	123.43 (13)	N22—C23—C24	122.11 (14)
C1—N1—C12	121.48 (13)	N31—C23—C24	120.88 (14)
C11—N1—C12	115.05 (13)	C23—C24—H24	120.8
C1—N2—N3	112.84 (12)	C25—C24—C23	118.34 (14)
N2—N3—H3	119.4 (13)	C25—C24—H24	120.8
C4—N3—N2	120.55 (13)	C24—C25—H25	119.8
C4—N3—H3	120.0 (13)	C24—C25—C26	120.43 (14)
C4—N4—H4A	119.8 (14)	C26—C25—H25	119.8
C4—N4—H4B	116.1 (14)	C21—C26—C25	117.11 (14)
H4A—N4—H4B	118.9 (19)	C21—C26—H26	121.4
C23—N22—C21	117.57 (12)	C25—C26—H26	121.4
C23—N31—C32	122.10 (13)	N31—C32—H32A	111.2
C23—N31—C35	124.72 (12)	N31—C32—H32B	111.2
C32—N31—C35	112.97 (12)	N31—C32—C33	102.85 (12)
N1—C1—S1	120.66 (11)	H32A—C32—H32B	109.1
N2—C1—S1	124.58 (11)	C33—C32—H32A	111.2
N2—C1—N1	114.71 (13)	C33—C32—H32B	111.2
N3—C4—N4	120.02 (14)	C32—C33—H33A	111.0
N3—C4—C21	118.11 (13)	C32—C33—H33B	111.0
N4—C4—C21	121.79 (13)	H33A—C33—H33B	109.0
N1—C11—H11A	109.5	C34—C33—C32	103.75 (13)
N1—C11—H11B	109.5	C34—C33—H33A	111.0
N1—C11—H11C	109.5	C34—C33—H33B	111.0
H11A—C11—H11B	109.5	C33—C34—H34A	111.0
H11A—C11—H11C	109.5	C33—C34—H34B	111.0
H11B—C11—H11C	109.5	C33—C34—C35	104.03 (13)
N1—C12—H12A	109.5	H34A—C34—H34B	109.0
N1—C12—H12B	109.5	C35—C34—H34A	111.0
N1—C12—H12C	109.5	C35—C34—H34B	111.0
H12A—C12—H12B	109.5	N31—C35—C34	103.03 (12)
H12A—C12—H12C	109.5	N31—C35—H35A	111.2
H12B—C12—H12C	109.5	N31—C35—H35B	111.2
N22—C21—C4	114.72 (12)	C34—C35—H35A	111.2
N22—C21—C26	124.44 (14)	C34—C35—H35B	111.2
C26—C21—C4	120.81 (13)	H35A—C35—H35B	109.1
N22—C23—N31	117.00 (13)
N2—N3—C4—N4	−1.6 (2)	C12—N1—C1—N2	−5.1 (2)
N2—N3—C4—C21	−178.40 (12)	C21—N22—C23—N31	179.97 (12)
N3—N2—C1—S1	−0.74 (17)	C21—N22—C23—C24	−0.26 (19)
N3—N2—C1—N1	176.74 (11)	C23—N22—C21—C4	177.63 (11)
N3—C4—C21—N22	−16.04 (18)	C23—N22—C21—C26	0.0 (2)
N3—C4—C21—C26	161.68 (13)	C23—N31—C32—C33	171.67 (14)
N4—C4—C21—N22	167.22 (13)	C23—N31—C35—C34	165.39 (14)
N4—C4—C21—C26	−15.1 (2)	C23—C24—C25—C26	0.3 (2)
N22—C21—C26—C25	0.4 (2)	C24—C25—C26—C21	−0.5 (2)
N22—C23—C24—C25	0.1 (2)	C32—N31—C23—N22	−2.6 (2)
N31—C23—C24—C25	179.88 (14)	C32—N31—C23—C24	177.65 (13)
N31—C32—C33—C34	30.65 (17)	C32—N31—C35—C34	−9.43 (17)
C1—N2—N3—C4	−179.19 (12)	C32—C33—C34—C35	−37.12 (18)
C4—C21—C26—C25	−177.10 (13)	C33—C34—C35—N31	28.44 (17)
C11—N1—C1—S1	−9.92 (19)	C35—N31—C23—N22	−176.96 (13)
C11—N1—C1—N2	172.49 (13)	C35—N31—C23—C24	3.3 (2)
C12—N1—C1—S1	172.51 (12)	C35—N31—C32—C33	−13.35 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···S1	0.98	2.56	3.0646 (17)	112
C35—H35A···S1^i	0.99	2.92	3.7915 (16)	147
N4—H4A···S1^ii	0.90 (2)	2.44 (2)	3.3250 (14)	170.1 (19)
N3—H3···S1	0.86 (2)	2.388 (19)	2.8616 (13)	115.2 (15)

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

2-{Amino[6-(piperidin-1-yl)pyridin-2-yl]methylidene}-N,N-dimethylhydrazine-1-carbothioamide (5)

Crystal data

C14H22N6S	F(000) = 1312
Mr = 306.44	Dx = 1.290 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.3148 (2) Å	Cell parameters from 46055 reflections
b = 9.3860 (1) Å	θ = 4.8–78.7°
c = 36.2261 (5) Å	µ = 1.85 mm^−1
β = 94.812 (1)°	T = 100 K
V = 3156.04 (9) Å^3	Plate, clear light brown
Z = 8	0.38 × 0.28 × 0.06 mm

Data collection

XtaLAB Synergy, Dualflex, Pilatus 300K diffractometer	15028 measured reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	15028 independent reflections
Mirror monochromator	13699 reflections with I > 2σ(I)
Detector resolution: 5.8140 pixels mm^-1	θmax = 79.0°, θmin = 4.8°
ω scans	h = −10→11
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2022)	k = −11→11
Tmin = 0.624, Tmax = 0.901	l = −43→45

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.0853P)^2 + 1.9565P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.147	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.33 e Å^−3
15028 reflections	Δρmin = −0.30 e Å^−3
409 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0006 (2)
Primary atom site location: dual

Special details

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. Refined as a 2-component twin.

Diffraction measurements were performed using an XtaLAB Synergy, Dualflex diffractometer, (Rigaku Oxford Diffraction, Poland–Japan–UK), with a Pilatus 300K detector at low temperature [100.0 (2) K] using Cu Kα radiation (1.54184 Å). Diffraction data were processed using CrysAlis PRO software (Rigaku Oxford Diffraction. CrysAlis PRO; Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England). Solving and refinement of the crystal structure was performed with SHELX (Shedrick, 2008, 2015) using full-matrix least-squares minimization on F². All H atoms (except those of NH₂ and –NH– groups which could potentially be engaged in hydrogen bonds) were geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups and 0.99 Å for secondary CH₂ groups, with U_iso(H) = 1.2U_eq(C). In all the studied structures, the methyl H atoms were refined with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). ShelXle software (Hübschle et al., 2011) was used to visualize the molecular structure. Graphical representation of the crystal structures was performed using the Mercury program (Macrae et al., 2020). PublCIF (Westrip, 2010) and OLEX2 programs (Dolomanov et al., 2009) were used for data preparation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1B	0.58601 (6)	0.15564 (6)	0.54552 (2)	0.02414 (16)
N1B	0.8010 (2)	0.1871 (2)	0.50101 (5)	0.0234 (4)
N2B	0.7084 (2)	0.3960 (2)	0.51947 (5)	0.0201 (4)
N3B	0.6122 (2)	0.4567 (2)	0.54158 (5)	0.0190 (4)
H3B	0.566 (3)	0.402 (3)	0.5560 (9)	0.036 (8)*
N4B	0.6525 (2)	0.6779 (2)	0.51724 (6)	0.0242 (4)
H4BA	0.607 (3)	0.756 (4)	0.5081 (9)	0.037 (8)*
H4BB	0.706 (3)	0.632 (3)	0.5017 (9)	0.033 (8)*
N22B	0.4059 (2)	0.54291 (19)	0.58107 (5)	0.0183 (4)
N31B	0.2400 (2)	0.4708 (2)	0.62157 (5)	0.0203 (4)
C1B	0.7030 (2)	0.2533 (2)	0.52092 (6)	0.0201 (4)
C4B	0.5833 (2)	0.5924 (2)	0.53985 (6)	0.0189 (4)
C11B	0.7996 (3)	0.0333 (3)	0.49630 (7)	0.0291 (5)
H11A	0.868148	0.006426	0.478412	0.044*
H11B	0.702627	0.002313	0.487161	0.044*
H11C	0.827160	−0.012537	0.520156	0.044*
C12B	0.9026 (3)	0.2723 (3)	0.48186 (7)	0.0278 (5)
H12A	0.964240	0.209134	0.468526	0.042*
H12B	0.962448	0.328755	0.499963	0.042*
H12C	0.849468	0.336171	0.464211	0.042*
C21B	0.4774 (2)	0.6470 (2)	0.56449 (6)	0.0188 (4)
C23B	0.3074 (2)	0.5798 (2)	0.60401 (6)	0.0190 (4)
C24B	0.2797 (3)	0.7255 (2)	0.61160 (6)	0.0233 (5)
H24B	0.210280	0.750966	0.628209	0.028*
C25B	0.3550 (3)	0.8285 (2)	0.59451 (7)	0.0251 (5)
H25B	0.337765	0.926200	0.599381	0.030*
C26B	0.4570 (2)	0.7908 (2)	0.56996 (6)	0.0222 (5)
H26B	0.509408	0.860724	0.557701	0.027*
C32B	0.2685 (2)	0.3227 (2)	0.61108 (6)	0.0212 (4)
H32A	0.256871	0.259257	0.632458	0.025*
H32B	0.369125	0.314367	0.604469	0.025*
C33B	0.1660 (3)	0.2757 (3)	0.57831 (6)	0.0260 (5)
H33A	0.185043	0.332056	0.556142	0.031*
H33B	0.183001	0.174055	0.572857	0.031*
C34B	0.0097 (3)	0.2963 (3)	0.58672 (7)	0.0267 (5)
H34A	−0.013495	0.228983	0.606395	0.032*
H34B	−0.054654	0.275081	0.564246	0.032*
C35B	−0.0164 (3)	0.4486 (3)	0.59929 (7)	0.0275 (5)
H35A	−0.115587	0.457060	0.606968	0.033*
H35B	−0.006782	0.515031	0.578410	0.033*
C36B	0.0918 (3)	0.4889 (3)	0.63171 (7)	0.0257 (5)
H36A	0.076488	0.589275	0.638790	0.031*
H36B	0.076258	0.428013	0.653331	0.031*
S1A	0.90680 (6)	0.50105 (5)	0.84052 (2)	0.01902 (15)
N1A	1.1219 (2)	0.3200 (2)	0.86330 (5)	0.0231 (4)
N2A	1.03330 (19)	0.28720 (19)	0.80376 (5)	0.0177 (4)
N3A	0.9331 (2)	0.33287 (19)	0.77620 (5)	0.0173 (4)
H3A	0.865 (3)	0.397 (3)	0.7821 (8)	0.027 (7)*
N4A	1.0357 (2)	0.1930 (2)	0.73370 (5)	0.0202 (4)
H4AA	1.038 (3)	0.154 (3)	0.7114 (9)	0.031 (8)*
H4AB	1.095 (3)	0.164 (3)	0.7521 (9)	0.032 (8)*
N22A	0.73244 (19)	0.43459 (18)	0.72953 (5)	0.0167 (4)
N31A	0.5292 (2)	0.57841 (19)	0.72471 (5)	0.0191 (4)
C1A	1.0267 (2)	0.3627 (2)	0.83484 (6)	0.0183 (4)
C4A	0.9362 (2)	0.2861 (2)	0.74221 (6)	0.0165 (4)
C11A	1.1456 (3)	0.4007 (3)	0.89752 (7)	0.0338 (6)
H11D	1.174886	0.335804	0.917969	0.051*
H11E	1.056303	0.449349	0.902647	0.051*
H11F	1.221597	0.471425	0.895027	0.051*
C12A	1.2325 (3)	0.2156 (3)	0.85599 (7)	0.0275 (5)
H12D	1.278703	0.180280	0.879530	0.041*
H12E	1.305011	0.260600	0.841718	0.041*
H12F	1.188004	0.135781	0.841817	0.041*
C21A	0.8204 (2)	0.3394 (2)	0.71496 (6)	0.0164 (4)
C23A	0.6154 (2)	0.4800 (2)	0.70881 (6)	0.0172 (4)
C24A	0.5843 (2)	0.4290 (2)	0.67205 (6)	0.0197 (4)
H24A	0.500097	0.459657	0.657628	0.024*
C25A	0.6774 (2)	0.3350 (2)	0.65769 (6)	0.0201 (4)
H25A	0.658721	0.301837	0.632971	0.024*
C26A	0.8001 (2)	0.2873 (2)	0.67925 (6)	0.0191 (4)
H26A	0.866067	0.222326	0.669751	0.023*
C32A	0.5440 (2)	0.5933 (2)	0.76539 (6)	0.0203 (4)
H32C	0.506182	0.687133	0.772432	0.024*
H32D	0.647106	0.588404	0.774527	0.024*
C33A	0.4613 (3)	0.4750 (2)	0.78312 (6)	0.0231 (5)
H33C	0.466296	0.489759	0.810256	0.028*
H33D	0.506389	0.381963	0.778403	0.028*
C34A	0.3039 (3)	0.4727 (3)	0.76757 (7)	0.0259 (5)
H34C	0.253540	0.555395	0.777498	0.031*
H34D	0.257730	0.385129	0.776147	0.031*
C35A	0.2857 (2)	0.4776 (2)	0.72523 (7)	0.0239 (5)
H35C	0.313467	0.384431	0.715159	0.029*
H35D	0.183218	0.495044	0.716926	0.029*
C36A	0.3784 (2)	0.5948 (2)	0.71028 (6)	0.0209 (4)
H36C	0.371396	0.590496	0.682879	0.025*
H36D	0.342438	0.689049	0.717615	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1B	0.0245 (3)	0.0185 (3)	0.0294 (3)	−0.0004 (2)	0.0025 (2)	0.0053 (2)
N1B	0.0244 (10)	0.0218 (9)	0.0237 (10)	0.0020 (7)	0.0012 (8)	−0.0015 (7)
N2B	0.0194 (9)	0.0206 (9)	0.0202 (9)	0.0001 (7)	0.0015 (7)	0.0003 (7)
N3B	0.0175 (9)	0.0196 (9)	0.0200 (9)	−0.0007 (7)	0.0016 (7)	0.0018 (7)
N4B	0.0246 (11)	0.0208 (10)	0.0273 (10)	−0.0007 (8)	0.0035 (8)	0.0055 (8)
N22B	0.0181 (9)	0.0178 (8)	0.0185 (9)	−0.0002 (7)	−0.0009 (7)	0.0007 (7)
N31B	0.0211 (10)	0.0191 (9)	0.0209 (9)	−0.0003 (7)	0.0031 (7)	−0.0018 (7)
C1B	0.0205 (11)	0.0205 (10)	0.0185 (10)	0.0008 (8)	−0.0038 (8)	0.0013 (8)
C4B	0.0168 (11)	0.0183 (10)	0.0207 (10)	−0.0025 (8)	−0.0030 (8)	0.0016 (8)
C11B	0.0301 (13)	0.0232 (12)	0.0337 (13)	0.0059 (10)	0.0002 (10)	−0.0025 (10)
C12B	0.0269 (13)	0.0309 (12)	0.0260 (12)	0.0038 (10)	0.0053 (9)	0.0015 (10)
C21B	0.0177 (11)	0.0180 (10)	0.0199 (10)	−0.0007 (8)	−0.0036 (8)	0.0008 (8)
C23B	0.0184 (11)	0.0195 (10)	0.0182 (10)	0.0001 (8)	−0.0032 (8)	−0.0004 (8)
C24B	0.0244 (12)	0.0221 (11)	0.0232 (11)	0.0038 (9)	0.0011 (9)	−0.0025 (9)
C25B	0.0299 (13)	0.0163 (10)	0.0281 (12)	0.0033 (9)	−0.0035 (9)	−0.0011 (9)
C26B	0.0221 (11)	0.0173 (10)	0.0265 (11)	−0.0016 (8)	−0.0025 (9)	0.0018 (8)
C32B	0.0224 (11)	0.0178 (10)	0.0234 (11)	−0.0014 (8)	0.0019 (8)	0.0014 (8)
C33B	0.0299 (13)	0.0257 (11)	0.0224 (11)	−0.0039 (9)	0.0027 (9)	−0.0036 (9)
C34B	0.0246 (12)	0.0328 (12)	0.0217 (11)	−0.0058 (10)	−0.0036 (9)	0.0017 (9)
C35B	0.0211 (12)	0.0325 (13)	0.0288 (12)	0.0005 (9)	0.0021 (9)	0.0073 (10)
C36B	0.0245 (12)	0.0276 (12)	0.0258 (12)	0.0000 (9)	0.0068 (9)	−0.0024 (9)
S1A	0.0237 (3)	0.0162 (3)	0.0174 (3)	0.00157 (19)	0.00336 (19)	0.00003 (18)
N1A	0.0265 (10)	0.0230 (9)	0.0187 (9)	0.0043 (8)	−0.0040 (7)	−0.0025 (7)
N2A	0.0159 (9)	0.0194 (9)	0.0175 (9)	0.0012 (7)	−0.0011 (7)	0.0003 (7)
N3A	0.0175 (9)	0.0174 (8)	0.0167 (9)	0.0016 (7)	−0.0007 (7)	−0.0007 (7)
N4A	0.0193 (10)	0.0217 (9)	0.0192 (9)	0.0033 (7)	−0.0006 (7)	−0.0033 (7)
N22A	0.0156 (9)	0.0155 (8)	0.0191 (9)	−0.0013 (6)	0.0012 (7)	0.0000 (7)
N31A	0.0184 (9)	0.0172 (8)	0.0212 (9)	0.0013 (7)	−0.0009 (7)	−0.0004 (7)
C1A	0.0199 (11)	0.0172 (9)	0.0178 (10)	−0.0037 (8)	0.0010 (8)	0.0014 (8)
C4A	0.0171 (10)	0.0145 (9)	0.0178 (10)	−0.0016 (7)	0.0012 (8)	−0.0010 (7)
C11A	0.0456 (16)	0.0332 (13)	0.0205 (12)	0.0057 (11)	−0.0093 (10)	−0.0053 (10)
C12A	0.0264 (13)	0.0295 (12)	0.0258 (12)	0.0070 (10)	−0.0036 (9)	0.0013 (9)
C21A	0.0150 (10)	0.0152 (9)	0.0190 (10)	−0.0024 (7)	0.0022 (8)	0.0010 (7)
C23A	0.0166 (10)	0.0146 (9)	0.0203 (10)	−0.0023 (8)	0.0017 (8)	0.0017 (8)
C24A	0.0170 (11)	0.0203 (10)	0.0211 (10)	−0.0010 (8)	−0.0021 (8)	0.0018 (8)
C25A	0.0207 (11)	0.0222 (10)	0.0170 (10)	−0.0034 (8)	0.0003 (8)	0.0000 (8)
C26A	0.0197 (11)	0.0190 (10)	0.0188 (10)	0.0000 (8)	0.0029 (8)	−0.0001 (8)
C32A	0.0196 (11)	0.0185 (10)	0.0226 (11)	0.0020 (8)	0.0006 (8)	−0.0038 (8)
C33A	0.0287 (12)	0.0194 (10)	0.0215 (11)	0.0030 (9)	0.0041 (9)	−0.0003 (8)
C34A	0.0239 (12)	0.0221 (11)	0.0328 (13)	−0.0003 (9)	0.0085 (9)	0.0000 (9)
C35A	0.0179 (11)	0.0204 (11)	0.0331 (13)	−0.0001 (8)	0.0005 (9)	−0.0032 (9)
C36A	0.0177 (11)	0.0188 (10)	0.0259 (11)	0.0036 (8)	−0.0002 (8)	−0.0002 (8)

Geometric parameters (Å, º)

S1B—C1B	1.727 (2)	S1A—C1A	1.736 (2)
N1B—C1B	1.360 (3)	N1A—C1A	1.362 (3)
N1B—C11B	1.454 (3)	N1A—C11A	1.454 (3)
N1B—C12B	1.458 (3)	N1A—C12A	1.463 (3)
N2B—N3B	1.375 (3)	N2A—N3A	1.377 (2)
N2B—C1B	1.341 (3)	N2A—C1A	1.336 (3)
N3B—H3B	0.87 (3)	N3A—H3A	0.91 (3)
N3B—C4B	1.303 (3)	N3A—C4A	1.310 (3)
N4B—H4BA	0.90 (3)	N4A—H4AA	0.89 (3)
N4B—H4BB	0.89 (3)	N4A—H4AB	0.87 (3)
N4B—C4B	1.349 (3)	N4A—C4A	1.329 (3)
N22B—C21B	1.352 (3)	N22A—C21A	1.349 (3)
N22B—C23B	1.335 (3)	N22A—C23A	1.341 (3)
N31B—C23B	1.383 (3)	N31A—C23A	1.380 (3)
N31B—C32B	1.471 (3)	N31A—C32A	1.475 (3)
N31B—C36B	1.467 (3)	N31A—C36A	1.465 (3)
C4B—C21B	1.476 (3)	C4A—C21A	1.486 (3)
C11B—H11A	0.9800	C11A—H11D	0.9800
C11B—H11B	0.9800	C11A—H11E	0.9800
C11B—H11C	0.9800	C11A—H11F	0.9800
C12B—H12A	0.9800	C12A—H12D	0.9800
C12B—H12B	0.9800	C12A—H12E	0.9800
C12B—H12C	0.9800	C12A—H12F	0.9800
C21B—C26B	1.380 (3)	C21A—C26A	1.381 (3)
C23B—C24B	1.422 (3)	C23A—C24A	1.422 (3)
C24B—H24B	0.9500	C24A—H24A	0.9500
C24B—C25B	1.372 (3)	C24A—C25A	1.370 (3)
C25B—H25B	0.9500	C25A—H25A	0.9500
C25B—C26B	1.400 (3)	C25A—C26A	1.403 (3)
C26B—H26B	0.9500	C26A—H26A	0.9500
C32B—H32A	0.9900	C32A—H32C	0.9900
C32B—H32B	0.9900	C32A—H32D	0.9900
C32B—C33B	1.525 (3)	C32A—C33A	1.524 (3)
C33B—H33A	0.9900	C33A—H33C	0.9900
C33B—H33B	0.9900	C33A—H33D	0.9900
C33B—C34B	1.524 (3)	C33A—C34A	1.526 (3)
C34B—H34A	0.9900	C34A—H34C	0.9900
C34B—H34B	0.9900	C34A—H34D	0.9900
C34B—C35B	1.526 (4)	C34A—C35A	1.530 (3)
C35B—H35A	0.9900	C35A—H35C	0.9900
C35B—H35B	0.9900	C35A—H35D	0.9900
C35B—C36B	1.530 (3)	C35A—C36A	1.526 (3)
C36B—H36A	0.9900	C36A—H36C	0.9900
C36B—H36B	0.9900	C36A—H36D	0.9900
C1B—N1B—C11B	121.1 (2)	C1A—N1A—C11A	122.3 (2)
C1B—N1B—C12B	119.57 (19)	C1A—N1A—C12A	118.93 (19)
C11B—N1B—C12B	119.2 (2)	C11A—N1A—C12A	116.40 (19)
C1B—N2B—N3B	111.25 (18)	C1A—N2A—N3A	111.69 (18)
N2B—N3B—H3B	119 (2)	N2A—N3A—H3A	118.5 (18)
C4B—N3B—N2B	121.32 (19)	C4A—N3A—N2A	120.72 (18)
C4B—N3B—H3B	120 (2)	C4A—N3A—H3A	120.7 (18)
H4BA—N4B—H4BB	116 (3)	H4AA—N4A—H4AB	120 (3)
C4B—N4B—H4BA	118 (2)	C4A—N4A—H4AA	123.5 (19)
C4B—N4B—H4BB	114 (2)	C4A—N4A—H4AB	116 (2)
C23B—N22B—C21B	118.65 (19)	C23A—N22A—C21A	118.94 (18)
C23B—N31B—C32B	118.79 (18)	C23A—N31A—C32A	118.13 (17)
C23B—N31B—C36B	120.13 (19)	C23A—N31A—C36A	119.65 (18)
C36B—N31B—C32B	111.61 (18)	C36A—N31A—C32A	110.66 (17)
N1B—C1B—S1B	120.79 (17)	N1A—C1A—S1A	120.96 (16)
N2B—C1B—S1B	125.27 (18)	N2A—C1A—S1A	124.91 (17)
N2B—C1B—N1B	113.9 (2)	N2A—C1A—N1A	114.1 (2)
N3B—C4B—N4B	120.2 (2)	N3A—C4A—N4A	120.6 (2)
N3B—C4B—C21B	117.16 (19)	N3A—C4A—C21A	116.10 (19)
N4B—C4B—C21B	122.6 (2)	N4A—C4A—C21A	123.28 (19)
N1B—C11B—H11A	109.5	N1A—C11A—H11D	109.5
N1B—C11B—H11B	109.5	N1A—C11A—H11E	109.5
N1B—C11B—H11C	109.5	N1A—C11A—H11F	109.5
H11A—C11B—H11B	109.5	H11D—C11A—H11E	109.5
H11A—C11B—H11C	109.5	H11D—C11A—H11F	109.5
H11B—C11B—H11C	109.5	H11E—C11A—H11F	109.5
N1B—C12B—H12A	109.5	N1A—C12A—H12D	109.5
N1B—C12B—H12B	109.5	N1A—C12A—H12E	109.5
N1B—C12B—H12C	109.5	N1A—C12A—H12F	109.5
H12A—C12B—H12B	109.5	H12D—C12A—H12E	109.5
H12A—C12B—H12C	109.5	H12D—C12A—H12F	109.5
H12B—C12B—H12C	109.5	H12E—C12A—H12F	109.5
N22B—C21B—C4B	113.37 (18)	N22A—C21A—C4A	113.19 (18)
N22B—C21B—C26B	124.4 (2)	N22A—C21A—C26A	124.12 (19)
C26B—C21B—C4B	122.3 (2)	C26A—C21A—C4A	122.51 (19)
N22B—C23B—N31B	117.19 (19)	N22A—C23A—N31A	116.94 (19)
N22B—C23B—C24B	121.0 (2)	N22A—C23A—C24A	120.60 (19)
N31B—C23B—C24B	121.7 (2)	N31A—C23A—C24A	122.45 (19)
C23B—C24B—H24B	120.6	C23A—C24A—H24A	120.4
C25B—C24B—C23B	118.8 (2)	C25A—C24A—C23A	119.2 (2)
C25B—C24B—H24B	120.6	C25A—C24A—H24A	120.4
C24B—C25B—H25B	119.7	C24A—C25A—H25A	119.8
C24B—C25B—C26B	120.6 (2)	C24A—C25A—C26A	120.4 (2)
C26B—C25B—H25B	119.7	C26A—C25A—H25A	119.8
C21B—C26B—C25B	116.6 (2)	C21A—C26A—C25A	116.7 (2)
C21B—C26B—H26B	121.7	C21A—C26A—H26A	121.6
C25B—C26B—H26B	121.7	C25A—C26A—H26A	121.6
N31B—C32B—H32A	109.4	N31A—C32A—H32C	109.6
N31B—C32B—H32B	109.4	N31A—C32A—H32D	109.6
N31B—C32B—C33B	111.07 (19)	N31A—C32A—C33A	110.10 (18)
H32A—C32B—H32B	108.0	H32C—C32A—H32D	108.2
C33B—C32B—H32A	109.4	C33A—C32A—H32C	109.6
C33B—C32B—H32B	109.4	C33A—C32A—H32D	109.6
C32B—C33B—H33A	109.5	C32A—C33A—H33C	109.4
C32B—C33B—H33B	109.5	C32A—C33A—H33D	109.4
H33A—C33B—H33B	108.1	C32A—C33A—C34A	111.02 (19)
C34B—C33B—C32B	110.73 (19)	H33C—C33A—H33D	108.0
C34B—C33B—H33A	109.5	C34A—C33A—H33C	109.4
C34B—C33B—H33B	109.5	C34A—C33A—H33D	109.4
C33B—C34B—H34A	109.5	C33A—C34A—H34C	109.0
C33B—C34B—H34B	109.5	C33A—C34A—H34D	109.0
C33B—C34B—C35B	110.9 (2)	C33A—C34A—C35A	113.10 (19)
H34A—C34B—H34B	108.0	H34C—C34A—H34D	107.8
C35B—C34B—H34A	109.5	C35A—C34A—H34C	109.0
C35B—C34B—H34B	109.5	C35A—C34A—H34D	109.0
C34B—C35B—H35A	109.6	C34A—C35A—H35C	109.4
C34B—C35B—H35B	109.6	C34A—C35A—H35D	109.4
C34B—C35B—C36B	110.4 (2)	H35C—C35A—H35D	108.0
H35A—C35B—H35B	108.1	C36A—C35A—C34A	111.02 (19)
C36B—C35B—H35A	109.6	C36A—C35A—H35C	109.4
C36B—C35B—H35B	109.6	C36A—C35A—H35D	109.4
N31B—C36B—C35B	110.62 (19)	N31A—C36A—C35A	110.60 (18)
N31B—C36B—H36A	109.5	N31A—C36A—H36C	109.5
N31B—C36B—H36B	109.5	N31A—C36A—H36D	109.5
C35B—C36B—H36A	109.5	C35A—C36A—H36C	109.5
C35B—C36B—H36B	109.5	C35A—C36A—H36D	109.5
H36A—C36B—H36B	108.1	H36C—C36A—H36D	108.1
N2B—N3B—C4B—N4B	−2.9 (3)	N2A—N3A—C4A—N4A	0.3 (3)
N2B—N3B—C4B—C21B	179.44 (18)	N2A—N3A—C4A—C21A	178.33 (18)
N3B—N2B—C1B—S1B	2.6 (3)	N3A—N2A—C1A—S1A	0.4 (3)
N3B—N2B—C1B—N1B	−176.89 (17)	N3A—N2A—C1A—N1A	178.79 (18)
N3B—C4B—C21B—N22B	−10.9 (3)	N3A—C4A—C21A—N22A	2.9 (3)
N3B—C4B—C21B—C26B	168.3 (2)	N3A—C4A—C21A—C26A	−172.49 (19)
N4B—C4B—C21B—N22B	171.5 (2)	N4A—C4A—C21A—N22A	−179.20 (19)
N4B—C4B—C21B—C26B	−9.3 (3)	N4A—C4A—C21A—C26A	5.4 (3)
N22B—C21B—C26B—C25B	0.1 (3)	N22A—C21A—C26A—C25A	−1.8 (3)
N22B—C23B—C24B—C25B	0.8 (3)	N22A—C23A—C24A—C25A	−1.5 (3)
N31B—C23B—C24B—C25B	177.0 (2)	N31A—C23A—C24A—C25A	177.8 (2)
N31B—C32B—C33B—C34B	−55.5 (3)	N31A—C32A—C33A—C34A	−55.2 (2)
C1B—N2B—N3B—C4B	−169.0 (2)	C1A—N2A—N3A—C4A	170.24 (19)
C4B—C21B—C26B—C25B	−178.95 (19)	C4A—C21A—C26A—C25A	172.99 (19)
C11B—N1B—C1B—S1B	7.2 (3)	C11A—N1A—C1A—S1A	−10.4 (3)
C11B—N1B—C1B—N2B	−173.3 (2)	C11A—N1A—C1A—N2A	171.1 (2)
C12B—N1B—C1B—S1B	−177.29 (17)	C12A—N1A—C1A—S1A	−172.44 (17)
C12B—N1B—C1B—N2B	2.3 (3)	C12A—N1A—C1A—N2A	9.1 (3)
C21B—N22B—C23B—N31B	−177.67 (18)	C21A—N22A—C23A—N31A	−179.39 (18)
C21B—N22B—C23B—C24B	−1.3 (3)	C21A—N22A—C23A—C24A	−0.1 (3)
C23B—N22B—C21B—C4B	179.99 (18)	C23A—N22A—C21A—C4A	−173.47 (18)
C23B—N22B—C21B—C26B	0.8 (3)	C23A—N22A—C21A—C26A	1.8 (3)
C23B—N31B—C32B—C33B	−87.3 (2)	C23A—N31A—C32A—C33A	−80.2 (2)
C23B—N31B—C36B—C35B	86.3 (2)	C23A—N31A—C36A—C35A	79.9 (2)
C23B—C24B—C25B—C26B	0.2 (3)	C23A—C24A—C25A—C26A	1.4 (3)
C24B—C25B—C26B—C21B	−0.6 (3)	C24A—C25A—C26A—C21A	0.2 (3)
C32B—N31B—C23B—N22B	−6.5 (3)	C32A—N31A—C23A—N22A	−18.4 (3)
C32B—N31B—C23B—C24B	177.1 (2)	C32A—N31A—C23A—C24A	162.33 (19)
C32B—N31B—C36B—C35B	−59.6 (2)	C32A—N31A—C36A—C35A	−62.7 (2)
C32B—C33B—C34B—C35B	53.1 (3)	C32A—C33A—C34A—C35A	48.6 (3)
C33B—C34B—C35B—C36B	−53.6 (3)	C33A—C34A—C35A—C36A	−48.0 (3)
C34B—C35B—C36B—N31B	56.6 (3)	C34A—C35A—C36A—N31A	54.3 (2)
C36B—N31B—C23B—N22B	−150.1 (2)	C36A—N31A—C23A—N22A	−158.24 (19)
C36B—N31B—C23B—C24B	33.5 (3)	C36A—N31A—C23A—C24A	22.5 (3)
C36B—N31B—C32B—C33B	59.2 (2)	C36A—N31A—C32A—C33A	63.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3B—H3B···S1B	0.87 (3)	2.35 (3)	2.841 (2)	116 (2)
N4B—H4BA···S1B^i	0.90 (3)	2.66 (3)	3.421 (2)	143 (3)
C24B—H24B···S1A^ii	0.95	2.86	3.636 (2)	139
C26B—H26B···S1B^iii	0.95	2.90	3.759 (2)	151
N3A—H3A···S1A	0.91 (3)	2.34 (3)	2.8420 (19)	115 (2)
N4A—H4AA···S1A^iv	0.89 (3)	2.45 (3)	3.317 (2)	164 (3)
C24A—H24A···N31B	0.95	2.66	3.578 (3)	164
C26A—H26A···S1A^iv	0.95	3.01	3.938 (2)	166
C36A—H36C···N31B	0.99	2.69	3.557 (3)	146

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

2-[Amino(6-phenoxypyridin-2-yl)methylidene]-N,N-dimethylhydrazine-1-carbothioamide monohydrate (6)

Crystal data

C15H17N5OS·H2O	F(000) = 704
Mr = 333.41	Dx = 1.382 Mg m^−3
Monoclinic, Ia	Cu Kα radiation, λ = 1.54184 Å
a = 7.96887 (14) Å	Cell parameters from 4154 reflections
b = 10.94707 (18) Å	θ = 4.7–78.2°
c = 18.4759 (3) Å	µ = 1.95 mm^−1
β = 96.2420 (16)°	T = 100 K
V = 1602.20 (5) Å^3	Block, clear light yellow
Z = 4	0.89 × 0.15 × 0.11 mm

Data collection

XtaLAB Synergy, Dualflex, Pilatus 300K diffractometer	2248 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2238 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 5.8140 pixels mm^-1	θmax = 78.4°, θmin = 4.7°
ω scans	h = −8→10
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −13→8
Tmin = 0.300, Tmax = 1.000	l = −23→20
4550 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 0.5698P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.022	(Δ/σ)max < 0.001
wR(F^2) = 0.058	Δρmax = 0.21 e Å^−3
S = 1.05	Δρmin = −0.13 e Å^−3
2248 reflections	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
231 parameters	Extinction coefficient: 0.0037 (2)
2 restraints	Absolute structure: Flack x determined using 690 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: −0.012 (11)

Special details

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. Diffraction measurements were performed using an XtaLAB Synergy, Dualflex diffractometer, (Rigaku Oxford Diffraction, Poland–Japan–UK), with a Pilatus 300K detector at low temperature [100.0 (2) K] using Cu Kα radiation (1.54184 Å). Diffraction data were processed using CrysAlis PRO software (Rigaku Oxford Diffraction. CrysAlis PRO; Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England). Solving and refinement of the crystal structure was performed with SHELX (Shedrick, 2008, 2015) using full-matrix least-squares minimization on F². All H atoms (except those of NH₂ and –NH– groups which could potentially be engaged in hydrogen bonds) were geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups and 0.99 Å for secondary CH₂ groups, with U_iso(H) = 1.2U_eq(C). In all the studied structures, the methyl H atoms were refined with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). ShelXle software (Hübschle et al., 2011) was used to visualize the molecular structure. Graphical representation of the crystal structures was performed using the Mercury program (Macrae et al., 2020). publCIF (Westrip, 2010) and OLEX2 programs (Dolomanov et al., 2009) were used for data preparation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.44296 (5)	0.13644 (4)	0.44382 (3)	0.01699 (14)
O23	0.8357 (2)	0.39728 (14)	0.66962 (9)	0.0224 (3)
N1	0.2453 (2)	0.20072 (15)	0.32176 (10)	0.0177 (4)
N2	0.3704 (2)	0.35990 (15)	0.38403 (10)	0.0159 (4)
N3	0.4771 (2)	0.39687 (15)	0.44359 (10)	0.0148 (4)
H3	0.531 (3)	0.345 (2)	0.4784 (16)	0.016 (6)*
N4	0.4151 (2)	0.59408 (17)	0.41104 (11)	0.0180 (4)
H4A	0.420 (3)	0.677 (3)	0.4210 (15)	0.027 (8)*
H4B	0.346 (4)	0.559 (3)	0.3758 (18)	0.030 (7)*
N22	0.6693 (2)	0.45894 (16)	0.56467 (10)	0.0153 (4)
C1	0.3494 (3)	0.23926 (18)	0.38007 (11)	0.0149 (4)
C4	0.4962 (2)	0.51462 (18)	0.45634 (11)	0.0143 (4)
C11	0.1929 (3)	0.0734 (2)	0.31350 (13)	0.0201 (5)
H11A	0.116577	0.064046	0.268538	0.030*
H11B	0.134314	0.049086	0.355197	0.030*
H11C	0.292441	0.021632	0.311217	0.030*
C12	0.1644 (3)	0.29158 (19)	0.27192 (12)	0.0189 (4)
H12A	0.250730	0.344401	0.254409	0.028*
H12B	0.086906	0.341144	0.297373	0.028*
H12C	0.101267	0.250291	0.230468	0.028*
C21	0.6110 (2)	0.55207 (18)	0.52060 (12)	0.0148 (4)
C23	0.7730 (2)	0.4871 (2)	0.62228 (11)	0.0171 (4)
C24	0.8290 (3)	0.6053 (2)	0.64053 (12)	0.0193 (4)
H24	0.904417	0.620766	0.682994	0.023*
C25	0.7705 (3)	0.6984 (2)	0.59448 (12)	0.0196 (4)
H25	0.807024	0.779934	0.604288	0.024*
C26	0.6573 (3)	0.67264 (19)	0.53328 (12)	0.0174 (4)
H26	0.613516	0.735827	0.501393	0.021*
C31	0.7604 (3)	0.28104 (19)	0.66677 (12)	0.0188 (4)
C32	0.7688 (3)	0.2050 (2)	0.60747 (13)	0.0217 (5)
H32	0.822391	0.231009	0.566641	0.026*
C33	0.6966 (3)	0.0894 (2)	0.60922 (14)	0.0270 (5)
H33	0.700738	0.035707	0.569064	0.032*
C34	0.6188 (3)	0.0519 (2)	0.66882 (15)	0.0294 (5)
H34	0.566989	−0.026228	0.668777	0.035*
C35	0.6163 (3)	0.1280 (2)	0.72848 (15)	0.0288 (6)
H35	0.565393	0.101255	0.769863	0.035*
C36	0.6885 (3)	0.2438 (2)	0.72785 (14)	0.0245 (5)
H36	0.688317	0.296291	0.768766	0.029*
O1W	0.3474 (2)	0.84344 (15)	0.42837 (10)	0.0258 (4)
H1WA	0.239 (6)	0.849 (3)	0.429 (2)	0.053 (10)*
H1WB	0.383 (5)	0.918 (4)	0.4279 (18)	0.043 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0205 (2)	0.0129 (2)	0.0163 (2)	0.00138 (18)	−0.00362 (17)	0.0000 (2)
O23	0.0235 (8)	0.0200 (8)	0.0214 (8)	−0.0016 (6)	−0.0078 (6)	0.0004 (6)
N1	0.0225 (10)	0.0121 (8)	0.0167 (9)	−0.0016 (7)	−0.0054 (7)	0.0003 (7)
N2	0.0172 (9)	0.0149 (9)	0.0150 (9)	−0.0005 (6)	−0.0019 (7)	−0.0007 (7)
N3	0.0158 (9)	0.0130 (8)	0.0149 (8)	−0.0001 (6)	−0.0017 (7)	0.0004 (7)
N4	0.0206 (9)	0.0135 (9)	0.0189 (9)	−0.0001 (7)	−0.0022 (7)	−0.0004 (8)
N22	0.0141 (8)	0.0160 (8)	0.0158 (9)	−0.0008 (6)	0.0010 (7)	−0.0001 (7)
C1	0.0163 (9)	0.0140 (9)	0.0142 (10)	0.0007 (7)	0.0018 (8)	0.0000 (7)
C4	0.0130 (9)	0.0144 (9)	0.0160 (10)	0.0001 (7)	0.0044 (7)	−0.0012 (8)
C11	0.0245 (11)	0.0150 (10)	0.0195 (11)	−0.0046 (8)	−0.0029 (9)	−0.0017 (8)
C12	0.0215 (10)	0.0174 (10)	0.0169 (11)	0.0017 (8)	−0.0022 (9)	0.0017 (8)
C21	0.0138 (9)	0.0158 (10)	0.0156 (10)	−0.0010 (8)	0.0050 (7)	−0.0016 (8)
C23	0.0147 (9)	0.0203 (10)	0.0166 (10)	−0.0001 (8)	0.0024 (8)	−0.0013 (8)
C24	0.0165 (10)	0.0246 (11)	0.0167 (11)	−0.0053 (8)	0.0017 (8)	−0.0043 (9)
C25	0.0220 (11)	0.0175 (10)	0.0200 (11)	−0.0066 (8)	0.0047 (9)	−0.0046 (8)
C26	0.0183 (10)	0.0168 (10)	0.0177 (10)	−0.0021 (8)	0.0042 (8)	−0.0002 (8)
C31	0.0145 (10)	0.0189 (10)	0.0215 (11)	0.0015 (7)	−0.0047 (8)	0.0030 (8)
C32	0.0222 (11)	0.0222 (11)	0.0198 (12)	0.0034 (8)	−0.0014 (9)	0.0032 (8)
C33	0.0325 (13)	0.0191 (11)	0.0261 (13)	0.0030 (9)	−0.0111 (10)	0.0007 (10)
C34	0.0262 (12)	0.0227 (11)	0.0361 (14)	−0.0012 (9)	−0.0105 (10)	0.0123 (10)
C35	0.0217 (12)	0.0344 (13)	0.0300 (13)	0.0044 (9)	0.0017 (10)	0.0160 (11)
C36	0.0235 (11)	0.0284 (11)	0.0207 (11)	0.0080 (9)	−0.0010 (9)	0.0041 (9)
O1W	0.0262 (10)	0.0151 (8)	0.0360 (10)	0.0018 (7)	0.0035 (8)	0.0029 (7)

Geometric parameters (Å, º)

S1—C1	1.738 (2)	C12—H12C	0.9800
O23—C23	1.373 (3)	C21—C26	1.384 (3)
O23—C31	1.405 (3)	C23—C24	1.399 (3)
N1—C1	1.354 (3)	C24—H24	0.9500
N1—C11	1.458 (3)	C24—C25	1.376 (3)
N1—C12	1.457 (3)	C25—H25	0.9500
N2—N3	1.376 (2)	C25—C26	1.397 (3)
N2—C1	1.332 (3)	C26—H26	0.9500
N3—H3	0.93 (3)	C31—C32	1.383 (3)
N3—C4	1.316 (3)	C31—C36	1.382 (3)
N4—H4A	0.93 (3)	C32—H32	0.9500
N4—H4B	0.90 (3)	C32—C33	1.392 (3)
N4—C4	1.325 (3)	C33—H33	0.9500
N22—C21	1.355 (3)	C33—C34	1.383 (4)
N22—C23	1.311 (3)	C34—H34	0.9500
C4—C21	1.476 (3)	C34—C35	1.383 (4)
C11—H11A	0.9800	C35—H35	0.9500
C11—H11B	0.9800	C35—C36	1.392 (4)
C11—H11C	0.9800	C36—H36	0.9500
C12—H12A	0.9800	O1W—H1WA	0.87 (4)
C12—H12B	0.9800	O1W—H1WB	0.86 (4)
C23—O23—C31	120.02 (16)	C26—C21—C4	122.12 (19)
C1—N1—C11	121.67 (17)	O23—C23—C24	115.13 (18)
C1—N1—C12	118.74 (17)	N22—C23—O23	120.16 (18)
C12—N1—C11	118.96 (17)	N22—C23—C24	124.7 (2)
C1—N2—N3	113.48 (17)	C23—C24—H24	121.4
N2—N3—H3	125.1 (16)	C25—C24—C23	117.3 (2)
C4—N3—N2	118.72 (18)	C25—C24—H24	121.4
C4—N3—H3	116.0 (16)	C24—C25—H25	120.1
H4A—N4—H4B	125 (3)	C24—C25—C26	119.79 (19)
C4—N4—H4A	120.9 (17)	C26—C25—H25	120.1
C4—N4—H4B	113 (2)	C21—C26—C25	117.8 (2)
C23—N22—C21	117.13 (17)	C21—C26—H26	121.1
N1—C1—S1	121.21 (15)	C25—C26—H26	121.1
N2—C1—S1	124.25 (16)	C32—C31—O23	121.2 (2)
N2—C1—N1	114.53 (18)	C36—C31—O23	116.7 (2)
N3—C4—N4	119.4 (2)	C36—C31—C32	122.0 (2)
N3—C4—C21	117.75 (18)	C31—C32—H32	120.9
N4—C4—C21	122.86 (18)	C31—C32—C33	118.2 (2)
N1—C11—H11A	109.5	C33—C32—H32	120.9
N1—C11—H11B	109.5	C32—C33—H33	119.7
N1—C11—H11C	109.5	C34—C33—C32	120.7 (2)
H11A—C11—H11B	109.5	C34—C33—H33	119.7
H11A—C11—H11C	109.5	C33—C34—H34	119.9
H11B—C11—H11C	109.5	C33—C34—C35	120.1 (2)
N1—C12—H12A	109.5	C35—C34—H34	119.9
N1—C12—H12B	109.5	C34—C35—H35	120.0
N1—C12—H12C	109.5	C34—C35—C36	120.0 (2)
H12A—C12—H12B	109.5	C36—C35—H35	120.0
H12A—C12—H12C	109.5	C31—C36—C35	119.0 (2)
H12B—C12—H12C	109.5	C31—C36—H36	120.5
N22—C21—C4	114.62 (17)	C35—C36—H36	120.5
N22—C21—C26	123.24 (19)	H1WA—O1W—H1WB	106 (3)
O23—C23—C24—C25	179.61 (19)	C12—N1—C1—N2	−2.0 (3)
O23—C31—C32—C33	177.85 (19)	C21—N22—C23—O23	179.39 (17)
O23—C31—C36—C35	−178.31 (19)	C21—N22—C23—C24	−1.1 (3)
N2—N3—C4—N4	−1.2 (3)	C23—O23—C31—C32	67.2 (3)
N2—N3—C4—C21	179.89 (17)	C23—O23—C31—C36	−117.1 (2)
N3—N2—C1—S1	1.0 (3)	C23—N22—C21—C4	179.45 (18)
N3—N2—C1—N1	−179.79 (16)	C23—N22—C21—C26	0.9 (3)
N3—C4—C21—N22	−7.5 (3)	C23—C24—C25—C26	1.2 (3)
N3—C4—C21—C26	171.11 (19)	C24—C25—C26—C21	−1.4 (3)
N4—C4—C21—N22	173.65 (19)	C31—O23—C23—N22	−15.0 (3)
N4—C4—C21—C26	−7.7 (3)	C31—O23—C23—C24	165.4 (2)
N22—C21—C26—C25	0.4 (3)	C31—C32—C33—C34	−0.1 (3)
N22—C23—C24—C25	0.0 (3)	C32—C31—C36—C35	−2.6 (3)
C1—N2—N3—C4	−174.43 (19)	C32—C33—C34—C35	−1.9 (4)
C4—C21—C26—C25	−178.14 (18)	C33—C34—C35—C36	1.6 (3)
C11—N1—C1—S1	6.5 (3)	C34—C35—C36—C31	0.6 (3)
C11—N1—C1—N2	−172.75 (19)	C36—C31—C32—C33	2.3 (3)
C12—N1—C1—S1	177.23 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1W	0.93 (3)	1.92 (3)	2.808 (2)	160 (2)
O1W—H1WA···S1^i	0.87 (4)	2.41 (4)	3.2734 (19)	173 (4)
O1W—H1WB···S1^ii	0.86 (4)	2.45 (4)	3.3018 (18)	168 (3)

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