Catalyst- and solvent-free synthesis of 2-fluoro-N-(3-methyl­sulfanyl-1H-1,2,4-triazol-5-yl)benzamide through a microwave-assisted Fries rearrangement: X-ray structural and theoretical studies

An efficient approach for the regioselective synthesis of (5-amino-3-methyl­sulfanyl-1H-1,2,4-triazol-1-yl)(2-fluoro­phen­yl)methanone, C₁₀H₉FN₄OS, (3), from the N-acyl­ation of 3-amino-5-methyl­sulfanyl-1H-1,2,4-triazole, (1), with 2-fluoro­benzoyl chloride has been developed. Heterocyclic amide (3) was used successfully as a strategic inter­mediate for the preparation of 2-fluoro-N-(3-methyl­sulfanyl-1H-1,2,4-triazol-5-yl)benzamide, C₁₀H₉FN₄OS, (4), through a microwave-assisted Fries rearrangement under catalyst- and solvent-free conditions. Theoretical studies of the prototropy process of (1) and the Fries rearrangement of (3) to provide (4), involving the formation of an intimate ion pair as the key step, were carried out by density functional theory (DFT) calculations. The crystallographic analysis of the inter­molecular inter­actions and the energy frameworks based on the effects of the different mol­ecular con­formations of (3) and (4) are described.

Computing details

For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(5-Amino-3-methylsulfanyl-1H-1,2,4-triazol-1-yl)(2-fluorophenyl)methanon (Compound_3)

Crystal data

C10H9FN4OS	Z = 2
Mr = 252.27	F(000) = 260
Triclinic, P1	Dx = 1.502 Mg m^−3
a = 7.6599 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8079 (8) Å	Cell parameters from 5358 reflections
c = 10.0140 (12) Å	θ = 3.6–27.5°
α = 94.487 (9)°	µ = 0.29 mm^−1
β = 108.668 (11)°	T = 298 K
γ = 97.565 (9)°	Parallelepiped, colorless
V = 557.83 (12) Å^3	0.38 × 0.34 × 0.22 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector'	2450 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2107 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.044
ω scans	θmax = 27.1°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −9→9
Tmin = 0.856, Tmax = 1.000	k = −9→10
12256 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: mixed
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0563P)^2 + 0.4216P] where P = (Fo^2 + 2Fc^2)/3
2450 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.27 e Å^−3
159 restraints	Δρmin = −0.22 e Å^−3

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	Occ. (<1)
S1	1.02515 (8)	0.25941 (8)	1.09852 (5)	0.05278 (19)
H1	1.373 (3)	0.476 (3)	0.7053 (6)	0.063*
H2	1.4957 (16)	0.518 (3)	0.8587 (18)	0.063*
C10A	0.8191 (3)	0.2346 (10)	0.5115 (8)	0.0367 (4)	0.633 (3)
C11A	0.7667 (7)	0.1073 (11)	0.3944 (7)	0.0377 (5)	0.633 (3)
C12A	0.5846 (5)	0.0481 (9)	0.3128 (7)	0.0465 (12)	0.633 (3)
H12A	0.554375	−0.037357	0.235294	0.056*	0.633 (3)
C13A	0.4464 (5)	0.1184 (5)	0.3483 (4)	0.0399 (5)	0.633 (3)
H13A	0.321606	0.079988	0.294066	0.048*	0.633 (3)
C14A	0.4925 (5)	0.2463 (5)	0.4645 (4)	0.0391 (4)	0.633 (3)
H14A	0.399095	0.295157	0.486343	0.047*	0.633 (3)
C15A	0.6781 (2)	0.3005 (7)	0.5474 (5)	0.0380 (4)	0.633 (3)
H15A	0.708397	0.381670	0.627779	0.046*	0.633 (3)
F1A	0.9121 (3)	0.0504 (3)	0.3615 (2)	0.0532 (6)	0.633 (3)
C10B	0.8175 (4)	0.2377 (16)	0.5144 (14)	0.0371 (4)	0.367 (3)
C11B	0.7981 (9)	0.1168 (17)	0.3994 (10)	0.0371 (16)	0.367 (3)
H11B	0.903845	0.091889	0.380400	0.045*	0.367 (3)
C12B	0.6220 (13)	0.0324 (17)	0.3122 (13)	0.0390 (5)	0.367 (3)
H12B	0.612361	−0.055916	0.241001	0.047*	0.367 (3)
C13B	0.4644 (11)	0.0767 (9)	0.3292 (7)	0.0394 (5)	0.367 (3)
H13B	0.347918	0.018856	0.269960	0.047*	0.367 (3)
C14B	0.4765 (9)	0.2065 (9)	0.4335 (7)	0.0389 (4)	0.367 (3)
H14B	0.368949	0.241264	0.442838	0.047*	0.367 (3)
C15B	0.6519 (3)	0.2856 (12)	0.5254 (8)	0.0380 (4)	0.367 (3)
F1B	0.6863 (5)	0.4163 (5)	0.6360 (4)	0.0557 (11)	0.367 (3)
N3	0.9653 (2)	0.2605 (2)	0.81764 (16)	0.0400 (4)
N4	1.0763 (2)	0.3271 (2)	0.74015 (16)	0.0392 (4)
C5	1.2529 (3)	0.3998 (3)	0.8343 (2)	0.0426 (4)
N6	1.2581 (2)	0.3836 (2)	0.96490 (18)	0.0466 (4)
N7	1.3908 (3)	0.4744 (3)	0.7944 (2)	0.0603 (5)
C2	1.0807 (3)	0.3004 (3)	0.9475 (2)	0.0412 (4)
C8	1.01785 (18)	0.3102 (2)	0.59287 (17)	0.0372 (4)
O9	1.12866 (18)	0.3549 (2)	0.53342 (15)	0.0490 (4)
C18	0.7830 (3)	0.1643 (3)	1.0186 (2)	0.0593 (6)
H18A	0.724733	0.160853	1.090360	0.089*
H18B	0.773136	0.047986	0.974666	0.089*
H18C	0.721750	0.233088	0.948057	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0504 (3)	0.0689 (4)	0.0336 (3)	0.0007 (3)	0.0098 (2)	0.0081 (2)
C10A	0.0323 (6)	0.0437 (8)	0.0337 (8)	0.0040 (6)	0.0108 (6)	0.0064 (6)
C11A	0.0327 (8)	0.0447 (10)	0.0346 (9)	0.0044 (8)	0.0107 (7)	0.0053 (7)
C12A	0.033 (2)	0.062 (3)	0.0362 (16)	0.004 (2)	0.002 (2)	0.0024 (16)
C13A	0.0332 (7)	0.0470 (10)	0.0367 (9)	0.0049 (7)	0.0090 (7)	0.0031 (7)
C14A	0.0328 (6)	0.0465 (9)	0.0360 (9)	0.0044 (7)	0.0100 (6)	0.0037 (7)
C15A	0.0325 (6)	0.0454 (9)	0.0348 (9)	0.0039 (6)	0.0104 (6)	0.0048 (7)
F1A	0.0518 (12)	0.0632 (13)	0.0447 (11)	0.0182 (9)	0.0155 (9)	−0.0049 (9)
C10B	0.0324 (7)	0.0441 (9)	0.0340 (8)	0.0040 (7)	0.0107 (6)	0.0060 (7)
C11B	0.021 (3)	0.054 (4)	0.034 (3)	−0.001 (3)	0.008 (3)	0.009 (2)
C12B	0.0329 (8)	0.0462 (10)	0.0358 (10)	0.0049 (8)	0.0098 (8)	0.0038 (8)
C13B	0.0331 (7)	0.0466 (10)	0.0362 (9)	0.0049 (7)	0.0095 (7)	0.0030 (8)
C14B	0.0327 (6)	0.0462 (10)	0.0358 (9)	0.0044 (7)	0.0100 (6)	0.0035 (7)
C15B	0.0326 (6)	0.0453 (9)	0.0348 (9)	0.0041 (7)	0.0104 (6)	0.0047 (7)
F1B	0.056 (2)	0.062 (2)	0.054 (2)	0.0153 (16)	0.0248 (16)	−0.0005 (16)
N3	0.0366 (8)	0.0471 (9)	0.0338 (8)	−0.0019 (6)	0.0119 (6)	0.0042 (6)
N4	0.0319 (8)	0.0479 (9)	0.0339 (8)	−0.0032 (6)	0.0103 (6)	0.0012 (6)
C5	0.0322 (9)	0.0475 (11)	0.0418 (10)	−0.0003 (8)	0.0077 (8)	0.0003 (8)
N6	0.0355 (8)	0.0572 (10)	0.0396 (9)	−0.0008 (7)	0.0065 (7)	0.0021 (7)
N7	0.0349 (9)	0.0893 (15)	0.0445 (10)	−0.0158 (9)	0.0088 (8)	0.0000 (10)
C2	0.0362 (9)	0.0458 (10)	0.0377 (10)	0.0021 (8)	0.0090 (8)	0.0047 (8)
C8	0.0342 (9)	0.0409 (9)	0.0375 (9)	0.0054 (7)	0.0137 (7)	0.0050 (7)
O9	0.0373 (7)	0.0676 (10)	0.0435 (8)	0.0012 (6)	0.0184 (6)	0.0064 (7)
C18	0.0531 (13)	0.0743 (16)	0.0490 (12)	−0.0062 (11)	0.0220 (10)	0.0059 (11)

Geometric parameters (Å, º)

S1—C2	1.739 (2)	C12B—H12B	0.9300
S1—C18	1.796 (2)	C13B—C14B	1.369 (7)
C10A—C15A	1.388 (5)	C13B—H13B	0.9300
C10A—C11A	1.391 (5)	C14B—C15B	1.391 (6)
C10A—C8	1.491 (2)	C14B—H14B	0.9300
C11A—C12A	1.367 (6)	C15B—F1B	1.380 (8)
C11A—F1A	1.374 (6)	N3—C2	1.303 (2)
C12A—C13A	1.382 (5)	N3—N4	1.402 (2)
C12A—H12A	0.9300	N4—C8	1.387 (2)
C13A—C14A	1.392 (4)	N4—C5	1.393 (2)
C13A—H13A	0.9300	C5—N6	1.312 (3)
C14A—C15A	1.386 (4)	C5—N7	1.326 (3)
C14A—H14A	0.9300	N6—C2	1.377 (2)
C15A—H15A	0.9300	N7—H1	0.8600 (11)
C10B—C11B	1.386 (9)	N7—H2	0.8600 (11)
C10B—C15B	1.403 (7)	C8—O9	1.214 (2)
C10B—C8	1.491 (2)	C18—H18A	0.9600
C11B—C12B	1.392 (10)	C18—H18B	0.9600
C11B—H11B	0.9300	C18—H18C	0.9600
C12B—C13B	1.356 (9)
C2—S1—C18	100.21 (10)	C13B—C14B—C15B	119.0 (6)
C15A—C10A—C11A	117.7 (3)	C13B—C14B—H14B	120.5
C15A—C10A—C8	119.2 (3)	C15B—C14B—H14B	120.5
C11A—C10A—C8	123.0 (4)	F1B—C15B—C14B	125.7 (4)
C12A—C11A—F1A	121.8 (4)	F1B—C15B—C10B	112.1 (4)
C12A—C11A—C10A	123.0 (5)	C14B—C15B—C10B	122.2 (6)
F1A—C11A—C10A	115.2 (3)	C2—N3—N4	101.36 (14)
C11A—C12A—C13A	118.4 (5)	C8—N4—C5	127.12 (15)
C11A—C12A—H12A	120.8	C8—N4—N3	123.84 (14)
C13A—C12A—H12A	120.8	C5—N4—N3	108.91 (15)
C12A—C13A—C14A	120.5 (4)	N6—C5—N7	126.71 (18)
C12A—C13A—H13A	119.7	N6—C5—N4	109.42 (16)
C14A—C13A—H13A	119.7	N7—C5—N4	123.86 (18)
C15A—C14A—C13A	119.8 (3)	C5—N6—C2	103.34 (16)
C15A—C14A—H14A	120.1	C5—N7—H1	119.0 (17)
C13A—C14A—H14A	120.1	C5—N7—H2	118.8 (17)
C14A—C15A—C10A	120.5 (3)	H1—N7—H2	122 (2)
C14A—C15A—H15A	119.7	N3—C2—N6	116.95 (17)
C10A—C15A—H15A	119.7	N3—C2—S1	124.73 (15)
C11B—C10B—C15B	116.3 (5)	N6—C2—S1	118.31 (14)
C11B—C10B—C8	111.4 (5)	O9—C8—N4	119.78 (14)
C15B—C10B—C8	131.7 (6)	O9—C8—C10B	122.9 (6)
C10B—C11B—C12B	120.7 (7)	N4—C8—C10B	117.4 (6)
C10B—C11B—H11B	119.6	O9—C8—C10A	121.7 (4)
C12B—C11B—H11B	119.6	N4—C8—C10A	118.5 (4)
C13B—C12B—C11B	121.1 (10)	S1—C18—H18A	109.5
C13B—C12B—H12B	119.4	S1—C18—H18B	109.5
C11B—C12B—H12B	119.4	H18A—C18—H18B	109.5
C12B—C13B—C14B	120.1 (7)	S1—C18—H18C	109.5
C12B—C13B—H13B	120.0	H18A—C18—H18C	109.5
C14B—C13B—H13B	120.0	H18B—C18—H18C	109.5
C15A—C10A—C11A—C12A	1.4 (15)	N3—N4—C5—N6	−0.4 (2)
C8—C10A—C11A—C12A	−174.5 (8)	C8—N4—C5—N7	4.2 (3)
C15A—C10A—C11A—F1A	178.3 (8)	N3—N4—C5—N7	−179.8 (2)
C8—C10A—C11A—F1A	2.4 (14)	N7—C5—N6—C2	179.1 (2)
F1A—C11A—C12A—C13A	−176.6 (7)	N4—C5—N6—C2	−0.3 (2)
C10A—C11A—C12A—C13A	0.1 (14)	N4—N3—C2—N6	−1.2 (2)
C11A—C12A—C13A—C14A	0.0 (9)	N4—N3—C2—S1	177.63 (14)
C12A—C13A—C14A—C15A	−1.6 (7)	C5—N6—C2—N3	1.0 (2)
C13A—C14A—C15A—C10A	3.2 (8)	C5—N6—C2—S1	−177.93 (15)
C11A—C10A—C15A—C14A	−3.1 (12)	C18—S1—C2—N3	−1.9 (2)
C8—C10A—C15A—C14A	173.0 (6)	C18—S1—C2—N6	176.86 (17)
C15B—C10B—C11B—C12B	−8 (2)	C5—N4—C8—O9	3.3 (3)
C8—C10B—C11B—C12B	179.6 (13)	N3—N4—C8—O9	−172.11 (17)
C10B—C11B—C12B—C13B	6 (2)	C5—N4—C8—C10B	−176.2 (6)
C11B—C12B—C13B—C14B	0.0 (17)	N3—N4—C8—C10B	8.4 (6)
C12B—C13B—C14B—C15B	−3.1 (12)	C5—N4—C8—C10A	−177.5 (4)
C13B—C14B—C15B—F1B	−179.4 (8)	N3—N4—C8—C10A	7.1 (4)
C13B—C14B—C15B—C10B	0.4 (15)	C11B—C10B—C8—O9	44.0 (16)
C11B—C10B—C15B—F1B	−175.0 (13)	C15B—C10B—C8—O9	−126.6 (15)
C8—C10B—C15B—F1B	−5 (2)	C11B—C10B—C8—N4	−136.5 (11)
C11B—C10B—C15B—C14B	5 (2)	C15B—C10B—C8—N4	52.9 (19)
C8—C10B—C15B—C14B	175.4 (12)	C15A—C10A—C8—O9	−130.7 (7)
C2—N3—N4—C8	177.04 (17)	C11A—C10A—C8—O9	45.2 (11)
C2—N3—N4—C5	0.9 (2)	C15A—C10A—C8—N4	50.1 (9)
C8—N4—C5—N6	−176.37 (18)	C11A—C10A—C8—N4	−134.0 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H1···O9	0.86 (1)	2.14 (2)	2.738 (2)	126 (2)
C15A—H15A···N3	0.93	2.60	2.960 (5)	104
N7—H2···N6^i	0.86 (2)	2.13 (2)	2.987 (3)	174 (2)
C14A—H14A···O9^ii	0.93	2.36	3.275 (4)	167

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

2-Fluoro-N-(3-methylsulfanyl-1H-1,2,4-triazol-5-yl)benzamide (Compound_4)

Crystal data

C10H9FN4OS	F(000) = 520
Mr = 252.27	Dx = 1.556 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.0509 (11) Å	Cell parameters from 3138 reflections
b = 26.640 (5) Å	θ = 4.0–24.7°
c = 8.0251 (16) Å	µ = 0.30 mm^−1
β = 94.12 (2)°	T = 298 K
V = 1077.0 (4) Å^3	Parallelepiped, colorless
Z = 4	0.23 × 0.08 × 0.05 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	5060 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3267 reflections with I > 2σ(I)
Detector resolution: 5.3072 pixels mm^-1	Rint = 0.080
ω scans	θmax = 26.8°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −6→6
Tmin = 0.734, Tmax = 1.000	k = −33→33
5060 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.071	Hydrogen site location: mixed
wR(F^2) = 0.237	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.1329P)^2] where P = (Fo^2 + 2Fc^2)/3
5060 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

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 3-component twin

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

	x	y	z	Uiso*/Ueq
S1	0.1477 (4)	0.27586 (4)	0.0007 (2)	0.0449 (5)
F1	0.1660 (7)	0.53895 (10)	0.1032 (4)	0.0505 (9)
H1	0.223 (15)	0.461 (2)	0.206 (8)	0.06 (2)*
O1	0.8265 (8)	0.46221 (12)	0.2805 (5)	0.0404 (10)
N1	0.5883 (9)	0.32664 (13)	0.1083 (6)	0.0357 (11)
C1	0.4195 (13)	0.23505 (19)	−0.0417 (9)	0.0544 (18)
H1A	0.351155	0.204771	−0.093496	0.082*
H1B	0.519322	0.226953	0.061054	0.082*
H1C	0.532742	0.251692	−0.115383	0.082*
C2	0.3270 (11)	0.32716 (16)	0.0838 (6)	0.0303 (11)
N2	0.6408 (10)	0.37462 (14)	0.1623 (6)	0.0344 (11)
C3	0.4156 (10)	0.40049 (16)	0.1636 (6)	0.0301 (12)
N3	0.2102 (9)	0.37196 (14)	0.1168 (6)	0.0358 (11)
C4	0.6041 (11)	0.48003 (17)	0.2559 (6)	0.0307 (12)
H4	0.81 (2)	0.386 (3)	0.187 (12)	0.11 (3)*
N4	0.3965 (9)	0.45071 (14)	0.1992 (6)	0.0342 (10)
C6	0.3445 (12)	0.56183 (17)	0.2127 (7)	0.0361 (13)
C5	0.5514 (10)	0.53388 (16)	0.2864 (6)	0.0305 (12)
C7	0.3142 (13)	0.61226 (18)	0.2366 (7)	0.0448 (15)
H7	0.173297	0.629657	0.182589	0.054*
C9	0.7035 (14)	0.60997 (19)	0.4223 (8)	0.0497 (16)
H9	0.824367	0.626244	0.496651	0.060*
C8	0.4989 (14)	0.63664 (19)	0.3431 (8)	0.0520 (17)
H8	0.484520	0.670992	0.361139	0.062*
C10	0.7318 (12)	0.55995 (18)	0.3933 (7)	0.0388 (13)
H10	0.874783	0.542851	0.446041	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0279 (8)	0.0374 (7)	0.0688 (11)	−0.0045 (6)	−0.0013 (7)	−0.0100 (6)
F1	0.044 (2)	0.0498 (17)	0.055 (2)	0.0030 (15)	−0.0163 (17)	0.0033 (15)
O1	0.025 (2)	0.0422 (19)	0.053 (2)	0.0033 (16)	−0.0032 (18)	−0.0046 (16)
N1	0.027 (3)	0.033 (2)	0.047 (3)	−0.0011 (18)	0.004 (2)	−0.0006 (18)
C1	0.040 (4)	0.043 (3)	0.082 (5)	0.001 (3)	0.009 (4)	−0.019 (3)
C2	0.019 (3)	0.035 (2)	0.037 (3)	0.000 (2)	0.001 (2)	0.001 (2)
N2	0.020 (3)	0.034 (2)	0.049 (3)	0.0007 (19)	0.002 (2)	−0.0024 (18)
C3	0.024 (3)	0.033 (2)	0.034 (3)	0.004 (2)	−0.001 (2)	0.000 (2)
N3	0.024 (3)	0.033 (2)	0.051 (3)	−0.0016 (18)	0.005 (2)	−0.0025 (19)
C4	0.026 (3)	0.035 (2)	0.031 (3)	−0.003 (2)	0.005 (2)	−0.002 (2)
N4	0.018 (3)	0.036 (2)	0.050 (3)	0.0030 (19)	0.005 (2)	−0.0010 (18)
C6	0.037 (4)	0.037 (3)	0.036 (3)	−0.003 (2)	0.010 (3)	0.003 (2)
C5	0.028 (3)	0.035 (2)	0.028 (3)	−0.002 (2)	0.006 (2)	0.002 (2)
C7	0.044 (4)	0.044 (3)	0.048 (4)	0.007 (3)	0.015 (3)	0.010 (2)
C9	0.056 (5)	0.045 (3)	0.049 (4)	−0.012 (3)	0.007 (3)	−0.006 (3)
C8	0.065 (5)	0.036 (3)	0.058 (4)	−0.002 (3)	0.021 (3)	−0.002 (3)
C10	0.033 (4)	0.045 (3)	0.038 (3)	−0.004 (2)	0.004 (3)	−0.007 (2)

Geometric parameters (Å, º)

S1—C2	1.746 (5)	C4—N4	1.360 (7)
S1—C1	1.803 (6)	C4—C5	1.483 (7)
F1—C6	1.357 (6)	N4—H1	0.93 (7)
O1—C4	1.222 (6)	C6—C7	1.367 (7)
N1—C2	1.320 (7)	C6—C5	1.381 (7)
N1—N2	1.370 (6)	C5—C10	1.391 (7)
C1—H1A	0.9600	C7—C8	1.381 (9)
C1—H1B	0.9600	C7—H7	0.9300
C1—H1C	0.9600	C9—C10	1.362 (7)
C2—N3	1.366 (6)	C9—C8	1.372 (9)
N2—C3	1.331 (7)	C9—H9	0.9300
N2—H4	0.90 (10)	C8—H8	0.9300
C3—N3	1.319 (7)	C10—H10	0.9300
C3—N4	1.373 (6)
C2—S1—C1	99.4 (3)	C4—N4—C3	124.4 (5)
C2—N1—N2	101.9 (4)	C4—N4—H1	121 (4)
S1—C1—H1A	109.5	C3—N4—H1	113 (4)
S1—C1—H1B	109.5	F1—C6—C7	117.2 (5)
H1A—C1—H1B	109.5	F1—C6—C5	118.8 (4)
S1—C1—H1C	109.5	C7—C6—C5	124.0 (5)
H1A—C1—H1C	109.5	C6—C5—C10	115.9 (4)
H1B—C1—H1C	109.5	C6—C5—C4	126.2 (5)
N1—C2—N3	114.9 (4)	C10—C5—C4	117.9 (5)
N1—C2—S1	122.3 (3)	C6—C7—C8	118.1 (6)
N3—C2—S1	122.6 (4)	C6—C7—H7	120.9
C3—N2—N1	109.8 (4)	C8—C7—H7	120.9
C3—N2—H4	128 (5)	C10—C9—C8	120.8 (6)
N1—N2—H4	122 (5)	C10—C9—H9	119.6
N3—C3—N2	110.8 (4)	C8—C9—H9	119.6
N3—C3—N4	123.7 (5)	C9—C8—C7	119.7 (5)
N2—C3—N4	125.4 (5)	C9—C8—H8	120.1
C3—N3—C2	102.5 (4)	C7—C8—H8	120.1
O1—C4—N4	120.6 (4)	C9—C10—C5	121.4 (5)
O1—C4—C5	121.5 (5)	C9—C10—H10	119.3
N4—C4—C5	117.9 (5)	C5—C10—H10	119.3
N2—N1—C2—N3	0.6 (6)	F1—C6—C5—C10	178.1 (5)
N2—N1—C2—S1	176.0 (4)	C7—C6—C5—C10	1.4 (8)
C1—S1—C2—N1	−3.9 (5)	F1—C6—C5—C4	1.2 (8)
C1—S1—C2—N3	171.2 (4)	C7—C6—C5—C4	−175.5 (5)
C2—N1—N2—C3	−1.3 (5)	O1—C4—C5—C6	155.9 (5)
N1—N2—C3—N3	1.6 (6)	N4—C4—C5—C6	−24.1 (7)
N1—N2—C3—N4	−175.0 (4)	O1—C4—C5—C10	−21.0 (7)
N2—C3—N3—C2	−1.2 (5)	N4—C4—C5—C10	159.0 (5)
N4—C3—N3—C2	175.5 (5)	F1—C6—C7—C8	−177.9 (5)
N1—C2—N3—C3	0.3 (6)	C5—C6—C7—C8	−1.2 (8)
S1—C2—N3—C3	−175.0 (4)	C10—C9—C8—C7	2.0 (9)
O1—C4—N4—C3	−0.8 (8)	C6—C7—C8—C9	−0.6 (9)
C5—C4—N4—C3	179.2 (4)	C8—C9—C10—C5	−1.7 (9)
N3—C3—N4—C4	176.4 (5)	C6—C5—C10—C9	0.0 (8)
N2—C3—N4—C4	−7.4 (8)	C4—C5—C10—C9	177.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1···F1	0.92 (7)	2.25 (6)	2.710 (5)	111 (5)
N2—H4···O1	0.92 (10)	2.16 (8)	2.664 (5)	114 (7)
N4—H1···O1^i	0.92 (7)	2.13 (8)	3.013 (6)	159 (5)
N2—H4···N3^ii	0.92 (10)	2.17 (10)	2.926 (7)	140 (8)
C10—H10···O1^iii	0.93	2.58	3.367 (7)	143
C1—H1A···N1^iv	0.96	2.78	3.566 (8)	140

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