Synthesis, structure and biological activity of four new picolinohydrazonamide derivatives

Four new picolinohydrazonamide derivatives, namely, 6-methyl-N′-(morpholine-4-car­bono­thio­yl)picolinohydrazonamide, C₁₂H₁₇N₅OS, 6-chloro-N′-(mor­pho­line-4-car­bono­thio­yl)picolinohydrazonamide methanol monosolvate, C₁₁H₁₄ClN₅OS·CH₃OH, 6-chloro-N′-(4-phenyl­piperazine-1-carbono­thio­yl)picolino­hy­drazon­amide, C₁₇H₁₉ClN₆S, and 6-chloro­picolinohydrazonamide, C₆H₇ClN₄, have been synthesized and characterized by NMR spectroscopy and single-crystal low-temperature X-ray diffraction. In addition, their anti­bacterial and anti-yeast activities have been determined. The first three com­pounds adopt the zwitterionic form in the crystal structure regardless of the presence or absence of solvent mol­ecules in the structure. They also adopt the same symmetry, i.e. P2₁/c (P2₁/n), unlike the fourth structure which is chiral and has the space group P2₁2₁2₁. For all the studied cases, inter­molecular N—H...O and N—H...N hydrogen bonds play an essential role in the formation of the structures.

Computing details

Data collection: APEX2 (Bruker, 2009) for (3), (4), (5); CrysAlis PRO (Rigaku OD, 2019) for (6). Cell refinement: SAINT-Plus (Bruker, 2009) for (3), (4), (5); CrysAlis PRO (Rigaku OD, 2019) for (6). Data reduction: SAINT-Plus (Bruker, 2009) for (3), (4), (5); CrysAlis PRO (Rigaku OD, 2019) for (6). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (3), (4), (5). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (3), (5); SHELXL2014 (Sheldrick, 2015) for (4), (6). Molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020) for (3), (4), (5). Software used to prepare material for publication: PLATON (Spek, 2020) for (3), (4), (5).

6-Methyl-N'-[(morpholin-4-yl)carbothioylamino]pyridine-2-carboximidamide (3)

Crystal data

C12H17N5OS	F(000) = 592
Mr = 279.36	Dx = 1.387 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 14.0601 (2) Å	Cell parameters from 9888 reflections
b = 10.9903 (2) Å	θ = 3.2–72.3°
c = 8.7228 (2) Å	µ = 2.16 mm^−1
β = 97.16°	T = 100 K
V = 1337.39 (4) Å^3	Needle, colourless
Z = 4	0.99 × 0.46 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer	2645 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scan	θmax = 72.3°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
Tmin = 0.506, Tmax = 0.75	k = −13→13
13619 measured reflections	l = −9→10
2646 independent 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)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0352P)^2 + 0.8311P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.31 e Å^−3
2646 reflections	Δρmin = −0.26 e Å^−3
186 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0251 (8)
Primary atom site location: structure-invariant direct methods

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.70600 (8)	0.50211 (11)	0.55778 (13)	0.0107 (2)
C4	0.76349 (8)	0.19479 (10)	0.56262 (13)	0.0108 (2)
C22	0.63554 (9)	0.70582 (11)	0.60357 (15)	0.0168 (3)
H22A	0.6633	0.7290	0.5115	0.020*
H22B	0.6689	0.7496	0.6907	0.020*
C23	0.52943 (10)	0.73824 (12)	0.58476 (15)	0.0211 (3)
H23A	0.5223	0.8256	0.5720	0.025*
H23B	0.4977	0.6995	0.4923	0.025*
C25	0.49318 (9)	0.57149 (11)	0.73240 (15)	0.0158 (3)
H25A	0.4608	0.5321	0.6409	0.019*
H25B	0.4620	0.5459	0.8202	0.019*
C26	0.59692 (9)	0.53191 (11)	0.75625 (14)	0.0157 (3)
H26A	0.6281	0.5645	0.8531	0.019*
H26B	0.6005	0.4438	0.7616	0.019*
C41	0.82391 (8)	0.11208 (11)	0.48227 (13)	0.0104 (2)
C42	0.81622 (8)	−0.01364 (11)	0.49654 (13)	0.0127 (2)
H42	0.7771	−0.0478	0.5635	0.015*
C43	0.86884 (9)	−0.08646 (11)	0.40775 (14)	0.0155 (3)
H43	0.8648	−0.1708	0.4127	0.019*
C44	0.92717 (9)	−0.03146 (11)	0.31216 (14)	0.0152 (2)
H44	0.9621	−0.0785	0.2503	0.018*
C45	0.93350 (8)	0.09563 (11)	0.30889 (13)	0.0130 (2)
C451	1.00009 (9)	0.15750 (12)	0.21218 (15)	0.0186 (3)
H45A	0.9659	0.2196	0.1505	0.028*
H45B	1.0249	0.0988	0.1459	0.028*
H45C	1.0522	0.1937	0.2783	0.028*
N2	0.70501 (7)	0.38672 (9)	0.60249 (11)	0.0116 (2)
N3	0.76317 (7)	0.31112 (9)	0.53006 (11)	0.0108 (2)
N4	0.70523 (7)	0.15231 (10)	0.65970 (12)	0.0133 (2)
N21	0.64612 (7)	0.57536 (9)	0.62886 (12)	0.0143 (2)
N46	0.88191 (7)	0.16668 (9)	0.39188 (11)	0.0114 (2)
O24	0.48458 (6)	0.70023 (8)	0.71516 (10)	0.0190 (2)
S1	0.77346 (2)	0.56026 (2)	0.42180 (3)	0.01303 (12)
H4A	0.7184 (12)	0.0856 (17)	0.710 (2)	0.025 (4)*
H4B	0.6746 (12)	0.2051 (15)	0.7020 (18)	0.019 (4)*
H3	0.7968 (12)	0.3385 (15)	0.4673 (19)	0.018 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0086 (5)	0.0128 (5)	0.0105 (5)	−0.0007 (4)	0.0005 (4)	−0.0005 (4)
C4	0.0087 (5)	0.0128 (5)	0.0103 (5)	−0.0002 (4)	−0.0008 (4)	0.0003 (4)
C22	0.0235 (6)	0.0101 (6)	0.0184 (6)	0.0002 (5)	0.0093 (5)	−0.0008 (4)
C23	0.0287 (7)	0.0182 (6)	0.0182 (6)	0.0108 (5)	0.0103 (5)	0.0053 (5)
C25	0.0136 (6)	0.0170 (6)	0.0175 (6)	0.0014 (4)	0.0052 (5)	−0.0015 (5)
C26	0.0149 (6)	0.0163 (6)	0.0173 (6)	0.0042 (5)	0.0083 (5)	0.0043 (5)
C41	0.0084 (5)	0.0129 (6)	0.0095 (5)	0.0003 (4)	−0.0005 (4)	0.0002 (4)
C42	0.0118 (5)	0.0136 (6)	0.0126 (5)	−0.0013 (4)	0.0017 (4)	0.0018 (4)
C43	0.0180 (6)	0.0106 (5)	0.0179 (6)	0.0009 (4)	0.0017 (5)	0.0001 (4)
C44	0.0157 (6)	0.0144 (6)	0.0159 (6)	0.0038 (5)	0.0042 (5)	−0.0013 (5)
C45	0.0108 (5)	0.0149 (6)	0.0133 (6)	0.0024 (4)	0.0019 (4)	0.0014 (4)
C451	0.0181 (6)	0.0165 (6)	0.0237 (7)	0.0039 (5)	0.0119 (5)	0.0040 (5)
N2	0.0108 (5)	0.0116 (5)	0.0131 (5)	0.0019 (4)	0.0045 (4)	0.0001 (4)
N3	0.0101 (5)	0.0118 (5)	0.0115 (5)	0.0010 (4)	0.0051 (4)	0.0010 (4)
N4	0.0141 (5)	0.0115 (5)	0.0155 (5)	0.0023 (4)	0.0068 (4)	0.0022 (4)
N21	0.0152 (5)	0.0114 (5)	0.0179 (5)	0.0029 (4)	0.0089 (4)	0.0029 (4)
N46	0.0099 (5)	0.0119 (5)	0.0123 (5)	0.0007 (4)	0.0018 (4)	0.0010 (4)
O24	0.0223 (5)	0.0186 (5)	0.0180 (4)	0.0094 (4)	0.0095 (4)	0.0026 (3)
S1	0.01600 (17)	0.01045 (16)	0.01414 (17)	−0.00220 (10)	0.00773 (11)	−0.00018 (10)

Geometric parameters (Å, º)

C1—N2	1.3274 (16)	C26—H26B	0.9700
C1—N21	1.3679 (15)	C41—N46	1.3443 (15)
C1—S1	1.7307 (12)	C41—C42	1.3927 (16)
C4—N3	1.3096 (15)	C42—C43	1.3894 (17)
C4—N4	1.3338 (15)	C42—H42	0.9300
C4—C41	1.4790 (16)	C43—C44	1.3797 (17)
C22—N21	1.4555 (15)	C43—H43	0.9300
C22—C23	1.5227 (18)	C44—C45	1.4002 (17)
C22—H22A	0.9700	C44—H44	0.9300
C22—H22B	0.9700	C45—N46	1.3381 (15)
C23—O24	1.4299 (15)	C45—C451	1.4991 (16)
C23—H23A	0.9700	C451—H45A	0.9600
C23—H23B	0.9700	C451—H45B	0.9600
C25—O24	1.4264 (15)	C451—H45C	0.9600
C25—C26	1.5115 (16)	N2—N3	1.3736 (14)
C25—H25A	0.9700	N3—H3	0.824 (17)
C25—H25B	0.9700	N4—H4A	0.862 (19)
C26—N21	1.4604 (15)	N4—H4B	0.835 (17)
C26—H26A	0.9700
N2—C1—N21	113.55 (10)	C42—C41—C4	120.79 (10)
N2—C1—S1	125.51 (9)	C43—C42—C41	117.97 (11)
N21—C1—S1	120.94 (9)	C43—C42—H42	121.0
N3—C4—N4	119.58 (11)	C41—C42—H42	121.0
N3—C4—C41	118.94 (10)	C44—C43—C42	118.84 (11)
N4—C4—C41	121.34 (10)	C44—C43—H43	120.6
N21—C22—C23	109.10 (10)	C42—C43—H43	120.6
N21—C22—H22A	109.9	C43—C44—C45	119.56 (11)
C23—C22—H22A	109.9	C43—C44—H44	120.2
N21—C22—H22B	109.9	C45—C44—H44	120.2
C23—C22—H22B	109.9	N46—C45—C44	122.07 (11)
H22A—C22—H22B	108.3	N46—C45—C451	117.29 (11)
O24—C23—C22	111.66 (10)	C44—C45—C451	120.64 (11)
O24—C23—H23A	109.3	C45—C451—H45A	109.5
C22—C23—H23A	109.3	C45—C451—H45B	109.5
O24—C23—H23B	109.3	H45A—C451—H45B	109.5
C22—C23—H23B	109.3	C45—C451—H45C	109.5
H23A—C23—H23B	107.9	H45A—C451—H45C	109.5
O24—C25—C26	111.57 (10)	H45B—C451—H45C	109.5
O24—C25—H25A	109.3	C1—N2—N3	114.47 (9)
C26—C25—H25A	109.3	C4—N3—N2	118.48 (10)
O24—C25—H25B	109.3	C4—N3—H3	121.0 (11)
C26—C25—H25B	109.3	N2—N3—H3	120.5 (11)
H25A—C25—H25B	108.0	C4—N4—H4A	120.6 (12)
N21—C26—C25	109.98 (10)	C4—N4—H4B	115.3 (11)
N21—C26—H26A	109.7	H4A—N4—H4B	117.2 (15)
C25—C26—H26A	109.7	C1—N21—C22	124.62 (10)
N21—C26—H26B	109.7	C1—N21—C26	121.95 (10)
C25—C26—H26B	109.7	C22—N21—C26	112.84 (9)
H26A—C26—H26B	108.2	C45—N46—C41	117.79 (10)
N46—C41—C42	123.70 (10)	C25—O24—C23	109.49 (9)
N46—C41—C4	115.45 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O24^i	0.835 (17)	2.437 (17)	3.0523 (14)	131.2 (14)
N4—H4A···S1^ii	0.862 (19)	2.496 (19)	3.3255 (11)	161.7 (15)
N3—H3···S1	0.824 (17)	2.484 (16)	2.9059 (10)	113.0 (13)
N3—H3···N46	0.824 (17)	2.373 (16)	2.6947 (14)	104.1 (13)

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

6-Chloro-N'-[(morpholin-4-yl)carbothioylamino]pyridine-2-carboximidamide methanol monosolvate (4)

Crystal data

C11H14ClN5OS·CH4O	F(000) = 696
Mr = 331.82	Dx = 1.429 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 6.8829 (2) Å	Cell parameters from 9914 reflections
b = 11.8924 (3) Å	θ = 14.7–72.4°
c = 19.0594 (5) Å	µ = 3.57 mm^−1
β = 98.737 (1)°	T = 100 K
V = 1541.99 (7) Å^3	Needle, yellow
Z = 4	0.90 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer	3036 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scan	θmax = 72.4°, θmin = 4.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.45, Tmax = 0.75	k = −14→14
20940 measured reflections	l = −23→23
3044 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0357P)^2 + 0.7351P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3044 reflections	Δρmax = 0.31 e Å^−3
207 parameters	Δρmin = −0.26 e Å^−3
0 restraints

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.24876 (16)	0.46997 (9)	0.26360 (6)	0.0121 (2)
C4	0.22193 (16)	0.44387 (10)	0.44313 (6)	0.0115 (2)
C22	0.30585 (18)	0.43117 (10)	0.14032 (6)	0.0160 (2)
H22A	0.4291	0.3906	0.1435	0.019*
H22B	0.3337	0.5109	0.1382	0.019*
C23	0.16976 (19)	0.39584 (10)	0.07396 (6)	0.0175 (3)
H23A	0.0512	0.4411	0.0689	0.021*
H23B	0.2337	0.4089	0.0327	0.021*
C25	0.02334 (19)	0.25810 (10)	0.13772 (6)	0.0174 (2)
H25A	−0.0109	0.1791	0.1389	0.021*
H25B	−0.0973	0.3014	0.1335	0.021*
C26	0.15393 (19)	0.28920 (10)	0.20618 (6)	0.0163 (2)
H26A	0.0835	0.2782	0.2460	0.020*
H26B	0.2695	0.2414	0.2130	0.020*
C41	0.26000 (16)	0.52292 (10)	0.50414 (6)	0.0122 (2)
C42	0.26582 (17)	0.48853 (10)	0.57407 (6)	0.0155 (2)
H42	0.2482	0.4134	0.5852	0.019*
C43	0.29883 (18)	0.57000 (11)	0.62711 (6)	0.0179 (2)
H43	0.3013	0.5499	0.6744	0.021*
C44	0.32789 (17)	0.68068 (11)	0.60927 (6)	0.0174 (2)
H44	0.3494	0.7368	0.6435	0.021*
C45	0.32330 (17)	0.70397 (10)	0.53745 (6)	0.0152 (2)
Cl45	0.36447 (5)	0.84157 (2)	0.51155 (2)	0.02304 (10)
C1M	0.2063 (2)	0.07917 (12)	0.34298 (8)	0.0244 (3)
H1M1	0.3128	0.1280	0.3361	0.037*
H1M2	0.1583	0.0413	0.2993	0.037*
H1M3	0.2518	0.0246	0.3788	0.037*
N2	0.21282 (14)	0.41701 (8)	0.32159 (5)	0.0129 (2)
N3	0.24055 (14)	0.48499 (8)	0.38071 (5)	0.0122 (2)
N4	0.17197 (15)	0.33769 (8)	0.45102 (5)	0.0133 (2)
N21	0.21286 (15)	0.40710 (8)	0.20268 (5)	0.0144 (2)
N46	0.29054 (14)	0.63014 (9)	0.48571 (5)	0.0141 (2)
O24	0.11880 (14)	0.27914 (7)	0.07720 (4)	0.01854 (19)
O1M	0.05224 (14)	0.14354 (8)	0.36480 (5)	0.0205 (2)
S1	0.32735 (4)	0.60830 (2)	0.26091 (2)	0.01463 (9)
H4A	0.153 (2)	0.3113 (14)	0.4923 (9)	0.022 (4)*
H4B	0.146 (2)	0.2949 (15)	0.4143 (10)	0.025 (4)*
H3	0.281 (2)	0.5534 (15)	0.3771 (8)	0.022 (4)*
H2M	−0.038 (3)	0.1421 (17)	0.3352 (11)	0.037 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0135 (5)	0.0114 (5)	0.0111 (5)	−0.0002 (4)	0.0006 (4)	−0.0001 (4)
C4	0.0112 (5)	0.0127 (5)	0.0104 (5)	0.0019 (4)	0.0006 (4)	0.0001 (4)
C22	0.0230 (6)	0.0145 (6)	0.0115 (5)	−0.0036 (5)	0.0059 (4)	−0.0003 (4)
C23	0.0290 (6)	0.0134 (6)	0.0110 (5)	−0.0027 (5)	0.0059 (5)	−0.0008 (4)
C25	0.0255 (6)	0.0159 (6)	0.0118 (5)	−0.0059 (5)	0.0054 (5)	−0.0028 (4)
C26	0.0262 (6)	0.0110 (5)	0.0119 (5)	−0.0041 (5)	0.0036 (5)	−0.0003 (4)
C41	0.0113 (5)	0.0134 (5)	0.0116 (5)	0.0013 (4)	0.0009 (4)	−0.0020 (4)
C42	0.0167 (5)	0.0167 (6)	0.0125 (5)	0.0012 (4)	0.0008 (4)	0.0003 (4)
C43	0.0191 (6)	0.0239 (6)	0.0100 (5)	0.0029 (5)	0.0006 (4)	−0.0020 (5)
C44	0.0160 (5)	0.0207 (6)	0.0144 (6)	0.0024 (5)	−0.0008 (4)	−0.0080 (5)
C45	0.0143 (5)	0.0134 (5)	0.0172 (6)	0.0010 (4)	0.0003 (4)	−0.0025 (4)
Cl45	0.03262 (18)	0.01269 (15)	0.02289 (17)	−0.00350 (11)	0.00123 (12)	−0.00447 (11)
C1M	0.0222 (6)	0.0229 (7)	0.0283 (7)	0.0000 (5)	0.0045 (5)	0.0005 (5)
N2	0.0190 (5)	0.0108 (4)	0.0084 (4)	−0.0012 (4)	0.0012 (4)	−0.0016 (4)
N3	0.0176 (5)	0.0097 (5)	0.0093 (4)	−0.0011 (4)	0.0015 (4)	−0.0014 (4)
N4	0.0205 (5)	0.0112 (5)	0.0078 (5)	−0.0005 (4)	0.0013 (4)	−0.0003 (4)
N21	0.0234 (5)	0.0113 (5)	0.0089 (5)	−0.0050 (4)	0.0037 (4)	−0.0004 (4)
N46	0.0151 (5)	0.0138 (5)	0.0130 (5)	0.0009 (4)	0.0011 (4)	−0.0019 (4)
O24	0.0317 (5)	0.0141 (4)	0.0112 (4)	−0.0053 (3)	0.0076 (3)	−0.0039 (3)
O1M	0.0224 (5)	0.0186 (4)	0.0197 (5)	−0.0013 (4)	0.0006 (4)	−0.0043 (4)
S1	0.02275 (16)	0.00997 (15)	0.01107 (14)	−0.00387 (10)	0.00229 (11)	0.00043 (9)

Geometric parameters (Å, º)

C1—N2	1.3276 (15)	C41—N46	1.3475 (16)
C1—N21	1.3715 (15)	C41—C42	1.3888 (16)
C1—S1	1.7349 (12)	C42—C43	1.3937 (17)
C4—N3	1.3106 (15)	C42—H42	0.9300
C4—N4	1.3233 (15)	C43—C44	1.3815 (19)
C4—C41	1.4873 (15)	C43—H43	0.9300
C22—N21	1.4613 (14)	C44—C45	1.3922 (17)
C22—C23	1.5144 (16)	C44—H44	0.9300
C22—H22A	0.9700	C45—N46	1.3141 (16)
C22—H22B	0.9700	C45—Cl45	1.7448 (12)
C23—O24	1.4351 (14)	C1M—O1M	1.4202 (16)
C23—H23A	0.9700	C1M—H1M1	0.9600
C23—H23B	0.9700	C1M—H1M2	0.9600
C25—O24	1.4335 (14)	C1M—H1M3	0.9600
C25—C26	1.5137 (16)	N2—N3	1.3762 (13)
C25—H25A	0.9700	N3—H3	0.865 (18)
C25—H25B	0.9700	N4—H4A	0.875 (17)
C26—N21	1.4640 (14)	N4—H4B	0.863 (18)
C26—H26A	0.9700	O1M—H2M	0.77 (2)
C26—H26B	0.9700
N2—C1—N21	114.45 (10)	C42—C41—C4	122.69 (11)
N2—C1—S1	124.94 (9)	C41—C42—C43	117.98 (11)
N21—C1—S1	120.58 (8)	C41—C42—H42	121.0
N3—C4—N4	121.48 (11)	C43—C42—H42	121.0
N3—C4—C41	116.36 (10)	C44—C43—C42	119.84 (11)
N4—C4—C41	122.16 (10)	C44—C43—H43	120.1
N21—C22—C23	109.46 (10)	C42—C43—H43	120.1
N21—C22—H22A	109.8	C43—C44—C45	116.68 (11)
C23—C22—H22A	109.8	C43—C44—H44	121.7
N21—C22—H22B	109.8	C45—C44—H44	121.7
C23—C22—H22B	109.8	N46—C45—C44	125.49 (11)
H22A—C22—H22B	108.2	N46—C45—Cl45	115.53 (9)
O24—C23—C22	110.89 (10)	C44—C45—Cl45	118.97 (9)
O24—C23—H23A	109.5	O1M—C1M—H1M1	109.5
C22—C23—H23A	109.5	O1M—C1M—H1M2	109.5
O24—C23—H23B	109.5	H1M1—C1M—H1M2	109.5
C22—C23—H23B	109.5	O1M—C1M—H1M3	109.5
H23A—C23—H23B	108.0	H1M1—C1M—H1M3	109.5
O24—C25—C26	111.48 (10)	H1M2—C1M—H1M3	109.5
O24—C25—H25A	109.3	C1—N2—N3	112.50 (9)
C26—C25—H25A	109.3	C4—N3—N2	120.23 (10)
O24—C25—H25B	109.3	C4—N3—H3	120.0 (11)
C26—C25—H25B	109.3	N2—N3—H3	119.5 (11)
H25A—C25—H25B	108.0	C4—N4—H4A	121.4 (11)
N21—C26—C25	109.09 (9)	C4—N4—H4B	119.8 (11)
N21—C26—H26A	109.9	H4A—N4—H4B	118.5 (16)
C25—C26—H26A	109.9	C1—N21—C22	122.48 (10)
N21—C26—H26B	109.9	C1—N21—C26	119.94 (9)
C25—C26—H26B	109.9	C22—N21—C26	112.53 (9)
H26A—C26—H26B	108.3	C45—N46—C41	116.90 (10)
N46—C41—C42	123.09 (11)	C25—O24—C23	110.38 (9)
N46—C41—C4	114.22 (10)	C1M—O1M—H2M	109.2 (15)
N21—C22—C23—O24	−56.73 (13)	C1—N2—N3—C4	−176.18 (10)
O24—C25—C26—N21	56.31 (13)	N2—C1—N21—C22	−157.18 (11)
N3—C4—C41—N46	6.08 (14)	S1—C1—N21—C22	24.66 (15)
N4—C4—C41—N46	−173.93 (10)	N2—C1—N21—C26	−4.20 (16)
N3—C4—C41—C42	−173.16 (10)	S1—C1—N21—C26	177.65 (9)
N4—C4—C41—C42	6.82 (17)	C23—C22—N21—C1	−149.93 (11)
N46—C41—C42—C43	2.06 (17)	C23—C22—N21—C26	55.29 (13)
C4—C41—C42—C43	−178.76 (10)	C25—C26—N21—C1	149.67 (11)
C41—C42—C43—C44	−1.12 (17)	C25—C26—N21—C22	−54.84 (13)
C42—C43—C44—C45	−0.39 (17)	C44—C45—N46—C41	−0.38 (17)
C43—C44—C45—N46	1.21 (18)	Cl45—C45—N46—C41	179.42 (8)
C43—C44—C45—Cl45	−178.57 (9)	C42—C41—N46—C45	−1.32 (16)
N21—C1—N2—N3	−176.70 (9)	C4—C41—N46—C45	179.44 (10)
S1—C1—N2—N3	1.36 (14)	C26—C25—O24—C23	−59.41 (13)
N4—C4—N3—N2	−1.60 (16)	C22—C23—O24—C25	59.33 (13)
C41—C4—N3—N2	178.39 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1M—H2M···S1^i	0.77 (2)	2.52 (2)	3.2925 (10)	172.1 (19)
N4—H4B···O1M	0.863 (18)	2.087 (18)	2.8808 (14)	152.6 (16)
N4—H4A···O24^ii	0.875 (17)	1.987 (18)	2.8487 (13)	168.3 (16)
N3—H3···S1	0.865 (18)	2.376 (16)	2.8521 (10)	115.0 (13)
N3—H3···N46	0.870 (18)	2.260 (17)	2.6267 (12)	105.3 (13)

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

6-Chloro-N'-[(4-phenylpiperazin-1-yl)carbothioylamino]pyridine-2-carboximidamide (5)

Crystal data

C17H19ClN6S[+solvent]	F(000) = 784
Mr = 374.89	Dx = 1.263 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.2996 (3) Å	Cell parameters from 9962 reflections
b = 9.3870 (3) Å	θ = 4.0–72.4°
c = 18.9935 (5) Å	µ = 2.80 mm^−1
β = 101.800 (1)°	T = 100 K
V = 1972.05 (10) Å^3	Needle, pink
Z = 4	0.6 × 0.19 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer	3747 reflections with I > 2σ(I)
ω scan	Rint = 0.020
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θmax = 72.1°, θmin = 4.2°
Tmin = 0.506, Tmax = 0.75	h = −13→12
14116 measured reflections	k = −10→11
3863 independent reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 1.2462P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3863 reflections	Δρmax = 0.37 e Å^−3
238 parameters	Δρmin = −0.38 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
S1	0.31558 (3)	0.84505 (4)	0.43511 (2)	0.02667 (10)
Cl45	−0.11603 (4)	0.96031 (5)	0.27563 (2)	0.04443 (13)
N2	0.37275 (10)	0.64612 (12)	0.34313 (6)	0.0230 (2)
N3	0.25414 (10)	0.67339 (13)	0.31115 (6)	0.0224 (2)
H3	0.2128 (18)	0.728 (2)	0.3331 (10)	0.036 (5)*
N15	0.26421 (12)	0.52799 (14)	0.21558 (7)	0.0269 (3)
H15A	0.3367 (18)	0.502 (2)	0.2366 (10)	0.034 (5)*
H15B	0.2324 (16)	0.4894 (19)	0.1765 (11)	0.029 (4)*
N21	0.52161 (11)	0.69802 (13)	0.44053 (6)	0.0254 (3)
N24	0.75666 (10)	0.63611 (13)	0.52456 (6)	0.0253 (3)
N46	0.04064 (11)	0.77499 (14)	0.25160 (6)	0.0257 (3)
C1	0.40663 (12)	0.72325 (14)	0.40290 (7)	0.0224 (3)
C4	0.20399 (12)	0.61721 (15)	0.24938 (7)	0.0223 (3)
C22	0.58224 (16)	0.79622 (18)	0.49551 (9)	0.0409 (4)
H22A	0.521262	0.847816	0.516475	0.049*
H22B	0.628351	0.867219	0.473471	0.049*
C23	0.66733 (15)	0.71664 (19)	0.55428 (8)	0.0364 (4)
H23A	0.709338	0.785257	0.590509	0.044*
H23B	0.620399	0.650512	0.578600	0.044*
C25	0.69544 (13)	0.53666 (17)	0.46937 (8)	0.0294 (3)
H25A	0.651763	0.464202	0.492113	0.035*
H25B	0.756585	0.486759	0.447808	0.035*
C26	0.60667 (13)	0.61240 (18)	0.41057 (8)	0.0300 (3)
H26A	0.651565	0.674551	0.383021	0.036*
H26B	0.561695	0.541092	0.377016	0.036*
C31	0.85784 (12)	0.58389 (16)	0.57476 (7)	0.0248 (3)
C32	0.90762 (14)	0.66290 (18)	0.63635 (9)	0.0342 (4)
H32	0.868567	0.747518	0.646944	0.041*
C33	1.01326 (15)	0.6189 (2)	0.68198 (9)	0.0392 (4)
H33	1.045915	0.674361	0.723202	0.047*
C34	1.07158 (13)	0.49624 (19)	0.66860 (9)	0.0360 (4)
H34	1.144848	0.467935	0.699555	0.043*
C35	1.02162 (14)	0.4151 (2)	0.60935 (9)	0.0357 (4)
H35	1.060225	0.329283	0.600026	0.043*
C36	0.91570 (14)	0.45726 (18)	0.56318 (8)	0.0311 (3)
H36	0.882148	0.399056	0.523150	0.037*
C41	0.07759 (12)	0.66077 (16)	0.21925 (7)	0.0246 (3)
C42	0.00317 (14)	0.5884 (2)	0.16353 (8)	0.0351 (4)
H42	0.031997	0.508328	0.141438	0.042*
C43	−0.11527 (15)	0.6366 (2)	0.14096 (9)	0.0436 (4)
H43	−0.168106	0.590414	0.102388	0.052*
C44	−0.15541 (14)	0.7512 (2)	0.17459 (8)	0.0381 (4)
H44	−0.236026	0.785154	0.160768	0.046*
C45	−0.07246 (14)	0.81520 (18)	0.22989 (8)	0.0301 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02827 (19)	0.03003 (19)	0.01785 (17)	0.00664 (13)	−0.00435 (13)	−0.00146 (12)
Cl45	0.0306 (2)	0.0551 (3)	0.0417 (2)	0.01582 (17)	−0.00630 (16)	−0.01175 (18)
N2	0.0193 (6)	0.0273 (6)	0.0187 (5)	0.0009 (4)	−0.0045 (4)	0.0002 (4)
N3	0.0184 (6)	0.0281 (6)	0.0179 (5)	0.0013 (5)	−0.0026 (4)	0.0004 (5)
N15	0.0209 (6)	0.0364 (7)	0.0199 (6)	0.0023 (5)	−0.0044 (5)	−0.0052 (5)
N21	0.0236 (6)	0.0266 (6)	0.0210 (6)	0.0022 (5)	−0.0069 (5)	−0.0034 (5)
N24	0.0198 (6)	0.0327 (6)	0.0198 (6)	−0.0006 (5)	−0.0046 (4)	−0.0004 (5)
N46	0.0206 (6)	0.0334 (6)	0.0210 (6)	0.0010 (5)	−0.0007 (4)	0.0032 (5)
C1	0.0231 (7)	0.0234 (7)	0.0174 (6)	−0.0001 (5)	−0.0034 (5)	0.0036 (5)
C4	0.0204 (6)	0.0277 (7)	0.0168 (6)	−0.0022 (5)	−0.0005 (5)	0.0026 (5)
C22	0.0394 (9)	0.0300 (8)	0.0400 (9)	0.0068 (7)	−0.0228 (7)	−0.0106 (7)
C23	0.0320 (8)	0.0428 (9)	0.0263 (7)	0.0123 (7)	−0.0128 (6)	−0.0109 (7)
C25	0.0208 (7)	0.0357 (8)	0.0273 (7)	0.0033 (6)	−0.0053 (6)	−0.0069 (6)
C26	0.0212 (7)	0.0444 (9)	0.0210 (7)	0.0017 (6)	−0.0038 (5)	−0.0055 (6)
C31	0.0183 (6)	0.0329 (7)	0.0211 (6)	−0.0036 (5)	−0.0007 (5)	0.0055 (6)
C32	0.0279 (8)	0.0383 (9)	0.0304 (8)	0.0001 (6)	−0.0077 (6)	−0.0017 (7)
C33	0.0306 (8)	0.0462 (10)	0.0328 (8)	−0.0074 (7)	−0.0124 (7)	0.0014 (7)
C34	0.0193 (7)	0.0478 (9)	0.0357 (8)	−0.0032 (6)	−0.0066 (6)	0.0134 (7)
C35	0.0264 (8)	0.0447 (9)	0.0337 (8)	0.0069 (7)	0.0008 (6)	0.0086 (7)
C36	0.0262 (7)	0.0396 (8)	0.0248 (7)	0.0018 (6)	−0.0011 (6)	0.0022 (6)
C41	0.0198 (7)	0.0359 (8)	0.0166 (6)	0.0000 (6)	−0.0002 (5)	0.0027 (5)
C42	0.0240 (7)	0.0561 (10)	0.0214 (7)	0.0053 (7)	−0.0041 (6)	−0.0093 (7)
C43	0.0268 (8)	0.0736 (13)	0.0242 (8)	0.0071 (8)	−0.0089 (6)	−0.0137 (8)
C44	0.0219 (7)	0.0629 (11)	0.0254 (7)	0.0089 (7)	−0.0049 (6)	−0.0021 (7)
C45	0.0242 (7)	0.0411 (8)	0.0230 (7)	0.0060 (6)	0.0004 (6)	0.0011 (6)

Geometric parameters (Å, º)

S1—C1	1.7312 (15)	C25—C26	1.517 (2)
Cl45—C45	1.7400 (16)	C25—H25A	0.9900
N2—C1	1.3348 (18)	C25—H25B	0.9900
N2—N3	1.3776 (16)	C26—H26A	0.9900
N3—C4	1.3053 (18)	C26—H26B	0.9900
N3—H3	0.86 (2)	C31—C36	1.396 (2)
N15—C4	1.3248 (19)	C31—C32	1.402 (2)
N15—H15A	0.87 (2)	C32—C33	1.387 (2)
N15—H15B	0.84 (2)	C32—H32	0.9500
N21—C1	1.3694 (17)	C33—C34	1.376 (3)
N21—C22	1.4549 (18)	C33—H33	0.9500
N21—C26	1.4550 (19)	C34—C35	1.380 (2)
N24—C31	1.4179 (17)	C34—H34	0.9500
N24—C23	1.464 (2)	C35—C36	1.389 (2)
N24—C25	1.4671 (18)	C35—H35	0.9500
N46—C45	1.3153 (19)	C36—H36	0.9500
N46—C41	1.344 (2)	C41—C42	1.388 (2)
C4—C41	1.4835 (19)	C42—C43	1.395 (2)
C22—C23	1.513 (2)	C42—H42	0.9500
C22—H22A	0.9900	C43—C44	1.374 (3)
C22—H22B	0.9900	C43—H43	0.9500
C23—H23A	0.9900	C44—C45	1.393 (2)
C23—H23B	0.9900	C44—H44	0.9500
C1—N2—N3	110.99 (11)	N21—C26—H26A	109.4
C4—N3—N2	121.71 (12)	C25—C26—H26A	109.4
C4—N3—H3	120.0 (13)	N21—C26—H26B	109.4
N2—N3—H3	118.3 (13)	C25—C26—H26B	109.4
C4—N15—H15A	119.0 (12)	H26A—C26—H26B	108.0
C4—N15—H15B	122.2 (12)	C36—C31—C32	117.45 (13)
H15A—N15—H15B	118.5 (17)	C36—C31—N24	121.86 (13)
C1—N21—C22	121.48 (12)	C32—C31—N24	120.59 (14)
C1—N21—C26	121.57 (11)	C33—C32—C31	120.72 (16)
C22—N21—C26	112.27 (12)	C33—C32—H32	119.6
C31—N24—C23	116.36 (11)	C31—C32—H32	119.6
C31—N24—C25	117.26 (12)	C34—C33—C32	121.17 (16)
C23—N24—C25	110.04 (11)	C34—C33—H33	119.4
C45—N46—C41	117.28 (13)	C32—C33—H33	119.4
N2—C1—N21	115.25 (12)	C33—C34—C35	118.73 (14)
N2—C1—S1	124.81 (10)	C33—C34—H34	120.6
N21—C1—S1	119.92 (10)	C35—C34—H34	120.6
N3—C4—N15	121.30 (13)	C34—C35—C36	120.91 (16)
N3—C4—C41	116.24 (13)	C34—C35—H35	119.5
N15—C4—C41	122.46 (12)	C36—C35—H35	119.5
N21—C22—C23	110.58 (13)	C35—C36—C31	120.94 (15)
N21—C22—H22A	109.5	C35—C36—H36	119.5
C23—C22—H22A	109.5	C31—C36—H36	119.5
N21—C22—H22B	109.5	N46—C41—C42	122.89 (13)
C23—C22—H22B	109.5	N46—C41—C4	114.09 (12)
H22A—C22—H22B	108.1	C42—C41—C4	123.01 (14)
N24—C23—C22	110.78 (14)	C41—C42—C43	117.97 (15)
N24—C23—H23A	109.5	C41—C42—H42	121.0
C22—C23—H23A	109.5	C43—C42—H42	121.0
N24—C23—H23B	109.5	C44—C43—C42	119.90 (15)
C22—C23—H23B	109.5	C44—C43—H43	120.1
H23A—C23—H23B	108.1	C42—C43—H43	120.1
N24—C25—C26	111.84 (12)	C43—C44—C45	116.93 (14)
N24—C25—H25A	109.2	C43—C44—H44	121.5
C26—C25—H25A	109.2	C45—C44—H44	121.5
N24—C25—H25B	109.2	N46—C45—C44	125.00 (15)
C26—C25—H25B	109.2	N46—C45—Cl45	115.09 (12)
H25A—C25—H25B	107.9	C44—C45—Cl45	119.91 (12)
N21—C26—C25	111.18 (12)
C1—N2—N3—C4	175.29 (13)	C36—C31—C32—C33	2.7 (2)
N3—N2—C1—N21	176.84 (11)	N24—C31—C32—C33	−173.84 (15)
N3—N2—C1—S1	−1.58 (17)	C31—C32—C33—C34	−0.6 (3)
C22—N21—C1—N2	164.24 (14)	C32—C33—C34—C35	−1.4 (3)
C26—N21—C1—N2	10.4 (2)	C33—C34—C35—C36	1.2 (3)
C22—N21—C1—S1	−17.3 (2)	C34—C35—C36—C31	1.0 (2)
C26—N21—C1—S1	−171.12 (11)	C32—C31—C36—C35	−2.9 (2)
N2—N3—C4—N15	1.9 (2)	N24—C31—C36—C35	173.57 (14)
N2—N3—C4—C41	−177.15 (12)	C45—N46—C41—C42	2.0 (2)
C1—N21—C22—C23	148.23 (15)	C45—N46—C41—C4	−176.77 (13)
C26—N21—C22—C23	−55.7 (2)	N3—C4—C41—N46	13.75 (18)
C31—N24—C23—C22	165.91 (13)	N15—C4—C41—N46	−165.32 (13)
C25—N24—C23—C22	−57.64 (18)	N3—C4—C41—C42	−165.02 (14)
N21—C22—C23—N24	57.7 (2)	N15—C4—C41—C42	15.9 (2)
C31—N24—C25—C26	−168.17 (12)	N46—C41—C42—C43	−0.5 (3)
C23—N24—C25—C26	55.81 (17)	C4—C41—C42—C43	178.18 (15)
C1—N21—C26—C25	−150.32 (13)	C41—C42—C43—C44	−1.1 (3)
C22—N21—C26—C25	53.63 (18)	C42—C43—C44—C45	1.1 (3)
N24—C25—C26—N21	−53.68 (17)	C41—N46—C45—C44	−2.1 (2)
C23—N24—C31—C36	148.46 (15)	C41—N46—C45—Cl45	178.16 (11)
C25—N24—C31—C36	15.2 (2)	C43—C44—C45—N46	0.6 (3)
C23—N24—C31—C32	−35.2 (2)	C43—C44—C45—Cl45	−179.67 (14)
C25—N24—C31—C32	−168.47 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N46	0.86 (2)	2.268 (19)	2.6255 (16)	105.1 (15)
N15—H15A···N2	0.87 (2)	2.400 (19)	2.7181 (17)	102.1 (14)
N15—H15A···N46^i	0.87 (2)	2.53 (2)	3.2139 (18)	136.6 (16)

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

N'-Amino-6-chloropyridine-2-carboximidamide (6)

Crystal data

C6H7ClN4	Dx = 1.616 Mg m^−3
Mr = 170.61	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 16896 reflections
a = 3.77379 (4) Å	θ = 4.0–78.5°
b = 5.63483 (4) Å	µ = 4.26 mm^−1
c = 32.9783 (2) Å	T = 100 K
V = 701.27 (1) Å^3	Plate, colourless
Z = 4.0	0.83 × 0.11 × 0.03 mm
F(000) = 352

Data collection

XtaLAB Synergy Dualflex Pilatus 300K diffractometer	1471 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1460 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.051
Detector resolution: 5.8140 pixels mm^-1	θmax = 78.7°, θmin = 4.0°
ω scans	h = −4→4
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2019)	k = −6→7
Tmin = 0.22, Tmax = 1.00	l = −40→41
19459 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)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 0.1754P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.056	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.20 e Å^−3
1471 reflections	Δρmin = −0.22 e Å^−3
112 parameters	Absolute structure: Flack x determined using 533 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.014 (5)
Primary atom site location: structure-invariant direct methods

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.

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

	x	y	z	Uiso*/Ueq
C4	0.4858 (4)	0.5683 (3)	0.56871 (5)	0.0101 (3)
C41	0.3457 (4)	0.4871 (3)	0.60868 (5)	0.0105 (3)
C43	0.3056 (4)	0.5605 (3)	0.67637 (5)	0.0126 (3)
C44	0.1294 (5)	0.3501 (3)	0.68446 (5)	0.0145 (3)
H44	0.0606	0.3092	0.7106	0.017*
C45	0.0607 (5)	0.2030 (3)	0.65155 (5)	0.0143 (3)
H45	−0.0579	0.0600	0.6553	0.017*
C46	0.1700 (4)	0.2708 (3)	0.61310 (5)	0.0125 (3)
H46	0.1271	0.1742	0.5908	0.015*
Cl43	0.40807 (11)	0.75195 (7)	0.71649 (2)	0.01704 (13)
N2	0.5959 (4)	0.5093 (3)	0.50120 (4)	0.0121 (3)
H2A	0.789 (6)	0.591 (4)	0.5045 (6)	0.015*
H2B	0.651 (6)	0.382 (4)	0.4876 (6)	0.015*
N3	0.4582 (4)	0.4232 (2)	0.53853 (4)	0.0110 (3)
N4	0.6340 (4)	0.7887 (2)	0.56824 (4)	0.0137 (3)
H4A	0.764 (6)	0.841 (4)	0.5478 (6)	0.016*
H4B	0.658 (6)	0.847 (4)	0.5915 (7)	0.016*
N42	0.4116 (4)	0.6328 (2)	0.64006 (4)	0.0118 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.0086 (7)	0.0102 (7)	0.0115 (7)	0.0015 (6)	−0.0007 (6)	0.0007 (6)
C41	0.0086 (8)	0.0118 (7)	0.0112 (7)	0.0029 (6)	−0.0011 (6)	0.0007 (6)
C43	0.0120 (8)	0.0158 (8)	0.0100 (7)	0.0035 (7)	−0.0018 (6)	−0.0012 (6)
C44	0.0135 (8)	0.0187 (8)	0.0112 (7)	0.0045 (7)	0.0016 (7)	0.0040 (6)
C45	0.0118 (8)	0.0127 (7)	0.0184 (7)	0.0006 (6)	0.0011 (6)	0.0035 (6)
C46	0.0118 (8)	0.0120 (7)	0.0138 (7)	0.0015 (7)	−0.0011 (6)	−0.0001 (6)
Cl43	0.0205 (2)	0.0207 (2)	0.00985 (19)	0.0006 (2)	−0.00066 (13)	−0.00299 (15)
N2	0.0157 (7)	0.0121 (7)	0.0085 (6)	0.0003 (6)	0.0013 (6)	−0.0008 (5)
N3	0.0127 (7)	0.0113 (6)	0.0092 (6)	0.0004 (6)	0.0002 (5)	0.0009 (5)
N4	0.0190 (7)	0.0129 (7)	0.0092 (6)	−0.0038 (6)	0.0017 (6)	−0.0013 (5)
N42	0.0109 (7)	0.0128 (6)	0.0116 (6)	0.0017 (6)	0.0003 (5)	−0.0003 (5)

Geometric parameters (Å, º)

C4—N3	1.292 (2)	C44—H44	0.9300
C4—N4	1.362 (2)	C45—C46	1.387 (2)
C4—C41	1.492 (2)	C45—H45	0.9300
C41—N42	1.344 (2)	C46—H46	0.9300
C41—C46	1.395 (2)	N2—N3	1.4216 (17)
C43—N42	1.327 (2)	N2—H2A	0.87 (2)
C43—C44	1.385 (3)	N2—H2B	0.87 (2)
C43—Cl43	1.7506 (16)	N4—H4A	0.88 (2)
C44—C45	1.390 (2)	N4—H4B	0.84 (2)
N3—C4—N4	126.95 (15)	C46—C45—H45	120.2
N3—C4—C41	117.23 (14)	C44—C45—H45	120.2
N4—C4—C41	115.81 (14)	C45—C46—C41	118.51 (16)
N42—C41—C46	122.76 (15)	C45—C46—H46	120.7
N42—C41—C4	115.28 (14)	C41—C46—H46	120.7
C46—C41—C4	121.92 (14)	N3—N2—H2A	112.3 (13)
N42—C43—C44	125.55 (15)	N3—N2—H2B	104.6 (14)
N42—C43—Cl43	115.23 (13)	H2A—N2—H2B	108 (2)
C44—C43—Cl43	119.21 (12)	C4—N3—N2	114.95 (13)
C43—C44—C45	116.72 (15)	C4—N4—H4A	122.5 (14)
C43—C44—H44	121.6	C4—N4—H4B	113.0 (15)
C45—C44—H44	121.6	H4A—N4—H4B	121 (2)
C46—C45—C44	119.62 (16)	C43—N42—C41	116.83 (14)
N3—C4—C41—N42	173.55 (15)	N42—C41—C46—C45	−0.4 (3)
N4—C4—C41—N42	−5.7 (2)	C4—C41—C46—C45	177.31 (15)
N3—C4—C41—C46	−4.3 (2)	N4—C4—N3—N2	−0.8 (2)
N4—C4—C41—C46	176.46 (15)	C41—C4—N3—N2	−179.96 (14)
N42—C43—C44—C45	0.3 (3)	C44—C43—N42—C41	−1.0 (3)
Cl43—C43—C44—C45	−178.87 (13)	Cl43—C43—N42—C41	178.26 (12)
C43—C44—C45—C46	0.3 (2)	C46—C41—N42—C43	1.0 (2)
C44—C45—C46—C41	−0.3 (2)	C4—C41—N42—C43	−176.86 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N42	0.84 (2)	2.21 (2)	2.662 (2)	113.8 (19)
N4—H4A···N2^i	0.88 (2)	2.21 (2)	3.095 (2)	176.4 (19)
N2—H2B···N3^ii	0.87 (2)	2.25 (2)	3.0862 (19)	162 (2)
N2—H2A···N2^i	0.87 (2)	2.54 (2)	3.306 (2)	147.5 (19)

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