Tri­thio­cyanuric acid: novel cocrystals and analysis of its tautomeric forms

Wzgarda-Raj, K.; Rybarczyk-Pirek, A.J.; Wojtulewski, S.; Palusiak, M.

doi:10.1107/S2053229620016137

Trithiocyanuric acid: novel cocrystals and analysis of its tautomeric forms

K. Wzgarda-Raj, A. J. Rybarczyk-Pirek, S. Wojtulewski and M. Palusiak

Cocrystals of trithiocyanuric acid with 2,2′-bipyridyl [1,3,5-triazinane-2,4,6-trithione–2,2′-bipyridine (2/1), 2C₃H₃N₃S₃·C₁₀H₈N₂, (I)] and 4-methylbenzohydrazide [1,3,5-triazinane-2,4,6-trithione–4-methylbenzohydrazide (1/1), C₈H₁₀N₂O·C₃H₃N₃S₃, (II)] crystallize in the monoclinic crystal system. In the crystals, molecules of both components are linked by hydrogen bonds. The trithiocyanuric acid molecules are connected by N—H

S hydrogen bonds forming R₂²(8) synthons, which are further organized into chain motifs. Computations based on quantum chemistry methods have been performed for a more detailed description of the observed tautomerism of trithiocyanuric acid.

Keywords: trithiocyanuric acid; cocrystal; hydrogen bonding; crystal structure; supramolecular chemistry; quantum chemistry; tautomerism.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620016137/dg3012sup1.cif Contains datablocks structure_I, structure_II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620016137/dg3012structure_Isup2.hkl Contains datablock structure_I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620016137/dg3012structure_IIsup3.hkl Contains datablock structure_II
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229620016137/dg3012structure_Isup4.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229620016137/dg3012structure_IIsup5.cml Supplementary material

CCDC references: 2049682; 2049681

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

1,3,5-Triazinane-2,4,6-trithione–2,2'-bipyridine (2/1) (structure_I) top

Crystal data top

2C₃H₃N₃S₃·C₁₀H₈N₂	F(000) = 1048
M_r = 510.72	D_x = 1.653 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.3039 (4) Å	Cell parameters from 4125 reflections
b = 6.4431 (2) Å	θ = 3.4–76.4°
c = 25.9547 (7) Å	µ = 6.36 mm⁻¹
β = 94.145 (3)°	T = 100 K
V = 2052.18 (11) Å³	Plate, yellow
Z = 4	0.17 × 0.13 × 0.11 mm

Data collection top

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	1896 independent reflections
Radiation source: micro-focus sealed X-ray tube	1717 reflections with I > 2σ(I)
Detector resolution: 10.4052 pixels mm^-1	R_int = 0.054
CrysAlisPro 1.171.39.15e (Rigaku Oxford Diffraction, 2015) scans	θ_max = 68.5°, θ_min = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −14→14
T_min = 0.544, T_max = 1.000	k = −7→7
7707 measured reflections	l = −31→31

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.120	Only H-atom coordinates refined
S = 1.13	w = 1/[σ²(F_o²) + (0.0746P)² + 2.3683P] where P = (F_o² + 2F_c²)/3
1896 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
S6	0.27246 (5)	0.29264 (9)	0.58089 (2)	0.0167 (2)
S2	0.40455 (5)	−0.27434 (10)	0.45165 (2)	0.0155 (2)
S4	0.50048 (5)	−0.35551 (10)	0.65211 (2)	0.0165 (2)
N1	0.34747 (16)	−0.0047 (3)	0.52234 (8)	0.0138 (4)
N5	0.39065 (16)	−0.0348 (3)	0.61046 (8)	0.0137 (4)
N3	0.44939 (17)	−0.2819 (3)	0.55350 (9)	0.0149 (4)
N11	0.37330 (17)	0.8868 (3)	0.20963 (8)	0.0138 (4)
C4	0.4448 (2)	−0.2176 (4)	0.60370 (10)	0.0137 (5)
C13	0.3985 (2)	0.8573 (4)	0.30160 (10)	0.0158 (5)
C14	0.2870 (2)	0.8606 (4)	0.30514 (10)	0.0160 (5)
C12	0.44029 (19)	0.8730 (4)	0.25314 (10)	0.0133 (5)
C6	0.34012 (19)	0.0757 (4)	0.57076 (9)	0.0144 (5)
C2	0.40057 (19)	−0.1838 (4)	0.51161 (10)	0.0132 (5)
C16	0.2656 (2)	0.8822 (4)	0.21372 (10)	0.0153 (5)
C15	0.2185 (2)	0.8710 (4)	0.26015 (10)	0.0163 (5)
H1	0.313 (3)	0.061 (5)	0.4986 (13)	0.020*
H5	0.391 (3)	0.005 (5)	0.6445 (13)	0.020*
H3	0.478 (3)	−0.389 (6)	0.5500 (13)	0.020*
H13	0.453 (3)	0.848 (5)	0.3325 (13)	0.020*
H14	0.259 (3)	0.848 (5)	0.3368 (14)	0.020*
H16	0.220 (3)	0.884 (5)	0.1811 (13)	0.020*
H15	0.146 (3)	0.860 (5)	0.2621 (13)	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S6	0.0166 (4)	0.0142 (3)	0.0191 (3)	0.0052 (2)	0.0001 (2)	−0.0011 (2)
S2	0.0135 (3)	0.0155 (3)	0.0175 (3)	0.0018 (2)	0.0013 (2)	−0.0023 (2)
S4	0.0118 (3)	0.0177 (4)	0.0196 (3)	0.0039 (2)	−0.0004 (2)	0.0021 (2)
N1	0.0099 (10)	0.0141 (10)	0.0171 (10)	0.0016 (9)	−0.0002 (7)	0.0013 (8)
N5	0.0089 (9)	0.0139 (10)	0.0183 (10)	0.0015 (8)	0.0002 (7)	−0.0007 (8)
N3	0.0113 (10)	0.0119 (10)	0.0217 (11)	0.0038 (8)	0.0018 (8)	−0.0007 (8)
N11	0.0105 (10)	0.0108 (10)	0.0197 (10)	−0.0016 (8)	−0.0003 (8)	−0.0014 (7)
C4	0.0072 (11)	0.0135 (12)	0.0205 (12)	−0.0014 (9)	0.0016 (9)	0.0009 (9)
C13	0.0150 (13)	0.0133 (12)	0.0189 (12)	−0.0027 (10)	0.0007 (9)	0.0004 (9)
C14	0.0164 (13)	0.0125 (12)	0.0199 (12)	−0.0020 (10)	0.0059 (10)	−0.0008 (9)
C12	0.0100 (13)	0.0097 (11)	0.0200 (12)	0.0003 (9)	−0.0001 (9)	0.0000 (9)
C6	0.0085 (11)	0.0149 (12)	0.0199 (12)	−0.0034 (9)	0.0014 (9)	0.0005 (9)
C2	0.0051 (10)	0.0132 (12)	0.0218 (12)	−0.0038 (9)	0.0036 (9)	−0.0006 (9)
C16	0.0122 (11)	0.0112 (11)	0.0222 (12)	0.0002 (9)	−0.0005 (9)	−0.0011 (9)
C15	0.0105 (12)	0.0114 (12)	0.0272 (13)	−0.0007 (9)	0.0023 (9)	−0.0006 (9)

Geometric parameters (Å, º) top

S6—C6	1.658 (3)	N11—C16	1.338 (3)
S2—C2	1.666 (3)	N11—C12	1.352 (3)
S4—C4	1.647 (2)	C13—C14	1.382 (4)
N1—C2	1.364 (3)	C13—C12	1.396 (4)
N1—C6	1.368 (3)	C13—H13	1.01 (3)
N1—H1	0.84 (4)	C14—C15	1.391 (4)
N5—C6	1.365 (3)	C14—H14	0.92 (4)
N5—C4	1.371 (3)	C12—C12ⁱ	1.490 (5)
N5—H5	0.92 (3)	C16—C15	1.376 (4)
N3—C2	1.359 (3)	C16—H16	0.98 (3)
N3—C4	1.372 (3)	C15—H15	0.90 (4)
N3—H3	0.78 (4)

C2—N1—C6	124.9 (2)	C13—C14—H14	120 (2)
C2—N1—H1	120 (2)	C15—C14—H14	121 (2)
C6—N1—H1	115 (2)	N11—C12—C13	121.0 (2)
C6—N5—C4	123.4 (2)	N11—C12—C12ⁱ	117.1 (3)
C6—N5—H5	123 (2)	C13—C12—C12ⁱ	121.9 (3)
C4—N5—H5	113 (2)	N5—C6—N1	116.1 (2)
C2—N3—C4	125.0 (2)	N5—C6—S6	121.78 (19)
C2—N3—H3	120 (3)	N1—C6—S6	122.16 (19)
C4—N3—H3	115 (2)	N3—C2—N1	114.9 (2)
C16—N11—C12	118.7 (2)	N3—C2—S2	122.9 (2)
N5—C4—N3	115.7 (2)	N1—C2—S2	122.24 (19)
N5—C4—S4	123.02 (19)	N11—C16—C15	123.6 (2)
N3—C4—S4	121.2 (2)	N11—C16—H16	116 (2)
C14—C13—C12	119.4 (2)	C15—C16—H16	120 (2)
C14—C13—H13	123.8 (19)	C16—C15—C14	118.0 (2)
C12—C13—H13	116.8 (19)	C16—C15—H15	122 (2)
C13—C14—C15	119.3 (2)	C14—C15—H15	119 (2)

C6—N5—C4—N3	2.4 (4)	C4—N5—C6—S6	178.18 (18)
C6—N5—C4—S4	−176.98 (19)	C2—N1—C6—N5	0.1 (4)
C2—N3—C4—N5	−3.3 (4)	C2—N1—C6—S6	−179.03 (18)
C2—N3—C4—S4	176.1 (2)	C4—N3—C2—N1	2.5 (4)
C12—C13—C14—C15	2.5 (4)	C4—N3—C2—S2	−177.37 (19)
C16—N11—C12—C13	−0.9 (4)	C6—N1—C2—N3	−0.8 (4)
C16—N11—C12—C12ⁱ	178.42 (15)	C6—N1—C2—S2	179.05 (19)
C14—C13—C12—N11	−1.4 (4)	C12—N11—C16—C15	2.2 (4)
C14—C13—C12—C12ⁱ	179.26 (17)	N11—C16—C15—C14	−1.1 (4)
C4—N5—C6—N1	−1.0 (4)	C13—C14—C15—C16	−1.4 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

1,3,5-Triazinane-2,4,6-trithione–4-methylbenzohydrazide (1/1) (structure_II) top

Crystal data top

C₈H₁₀N₂O·C₃H₃N₃S₃	F(000) = 1360
M_r = 327.45	D_x = 1.482 Mg m⁻³ D_m = Mg m⁻³ D_m measured by ?
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 24.5777 (4) Å	Cell parameters from 11943 reflections
b = 8.9406 (1) Å	θ = 3.6–76.2°
c = 13.3772 (2) Å	µ = 4.66 mm⁻¹
β = 93.313 (2)°	T = 100 K
V = 2934.58 (7) Å³	Plate, yellow
Z = 8	0.60 × 0.08 × 0.05 mm

Data collection top

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	4831 reflections with I > 2σ(I)
Detector resolution: 10.4052 pixels mm^-1	R_int = 0.037
CrysAlis PRO (Rigaku OD, 2015) scans	θ_max = 68.5°, θ_min = 3.6°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	h = −29→29
T_min = 0.287, T_max = 0.805	k = −10→10
23777 measured reflections	l = −15→16
5403 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Only H-atom coordinates refined
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.055P)² + 4.646P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5403 reflections	Δρ_max = 0.48 e Å⁻³
458 parameters	Δρ_min = −0.34 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
S4A	−0.01114 (2)	−0.17941 (6)	0.37415 (4)	0.01555 (14)
S4	0.10671 (2)	0.69751 (6)	0.22823 (4)	0.01611 (14)
S6A	0.18355 (2)	0.03065 (6)	0.48561 (4)	0.01660 (14)
S6	0.14461 (2)	0.11885 (6)	0.19549 (4)	0.01743 (14)
S2A	0.02217 (2)	0.40454 (6)	0.38376 (4)	0.01698 (14)
S2	0.30926 (2)	0.50070 (7)	0.24101 (5)	0.02362 (16)
O21A	0.17263 (7)	0.42688 (19)	0.43945 (13)	0.0186 (4)
N1A	0.09858 (8)	0.2016 (2)	0.43063 (15)	0.0155 (4)
N5	0.13380 (9)	0.4108 (2)	0.21443 (15)	0.0158 (4)
O21	0.30069 (8)	0.1170 (2)	0.2878 (2)	0.0381 (6)
N1	0.22237 (9)	0.3239 (2)	0.22758 (16)	0.0163 (4)
N3A	0.01524 (9)	0.1097 (2)	0.37066 (15)	0.0152 (4)
N3	0.20498 (8)	0.5769 (2)	0.23699 (15)	0.0157 (4)
N5A	0.08273 (8)	−0.0527 (2)	0.42868 (15)	0.0155 (4)
N21A	0.16695 (8)	0.6515 (2)	0.51323 (16)	0.0175 (4)
N22A	0.11015 (8)	0.6627 (2)	0.49008 (16)	0.0168 (4)
N22	0.23881 (9)	−0.1328 (2)	0.27224 (18)	0.0201 (4)
N21	0.29508 (9)	−0.1319 (2)	0.29810 (18)	0.0224 (5)
C21A	0.19529 (10)	0.5329 (3)	0.48315 (17)	0.0164 (5)
C4A	0.03016 (10)	−0.0345 (3)	0.39137 (16)	0.0144 (5)
C11A	0.25565 (10)	0.5355 (3)	0.50461 (18)	0.0183 (5)
C2A	0.04603 (10)	0.2327 (3)	0.39498 (17)	0.0151 (5)
C4	0.15010 (10)	0.5554 (3)	0.22658 (17)	0.0145 (5)
C2	0.24285 (10)	0.4656 (3)	0.23551 (18)	0.0165 (5)
C21	0.32340 (10)	−0.0039 (3)	0.3004 (2)	0.0200 (5)
C6	0.16802 (10)	0.2906 (3)	0.21349 (17)	0.0159 (5)
C6A	0.11866 (10)	0.0608 (3)	0.44650 (17)	0.0156 (5)
C11	0.38378 (11)	−0.0140 (3)	0.3219 (2)	0.0211 (5)
C12A	0.28552 (11)	0.6646 (3)	0.5265 (2)	0.0232 (5)
C15	0.46809 (12)	−0.1478 (3)	0.3542 (2)	0.0291 (6)
C12	0.41291 (12)	0.1199 (3)	0.3250 (2)	0.0259 (6)
C13A	0.34151 (12)	0.6569 (3)	0.5430 (2)	0.0286 (6)
C16	0.41181 (11)	−0.1481 (3)	0.3370 (2)	0.0261 (6)
C16A	0.28278 (12)	0.3990 (3)	0.5012 (2)	0.0266 (6)
C14A	0.36899 (11)	0.5214 (3)	0.5386 (2)	0.0271 (6)
C14	0.49759 (11)	−0.0150 (3)	0.3571 (2)	0.0282 (6)
C13	0.46887 (12)	0.1184 (3)	0.3427 (2)	0.0302 (6)
C15A	0.33881 (12)	0.3930 (3)	0.5187 (2)	0.0313 (6)
C24	0.55884 (12)	−0.0161 (4)	0.3762 (3)	0.0372 (7)
C24A	0.43021 (13)	0.5149 (4)	0.5558 (3)	0.0373 (7)
H21A	0.1828 (16)	0.735 (5)	0.533 (3)	0.045*
H15	0.4887 (16)	−0.237 (5)	0.361 (3)	0.045*
H13A	0.3625 (16)	0.746 (5)	0.557 (3)	0.045*
H16	0.3941 (16)	−0.242 (5)	0.339 (3)	0.045*
H16A	0.2631 (16)	0.318 (5)	0.483 (3)	0.045*
H13	0.4898 (16)	0.207 (5)	0.343 (3)	0.045*
H15A	0.3575 (16)	0.310 (5)	0.516 (3)	0.045*
H5	0.0992 (12)	0.395 (3)	0.2026 (19)	0.006 (6)*
H21	0.3120 (15)	−0.216 (4)	0.297 (3)	0.034 (9)*
H23A	0.0930 (12)	0.638 (3)	0.545 (2)	0.013 (7)*
H22A	0.1017 (13)	0.601 (4)	0.444 (3)	0.022 (8)*
H22	0.2298 (15)	−0.075 (5)	0.221 (3)	0.041 (10)*
H3A	−0.0157 (13)	0.127 (3)	0.349 (2)	0.012 (7)*
H24A	0.4409 (17)	0.511 (5)	0.622 (3)	0.052 (12)*
H1	0.2441 (14)	0.254 (4)	0.232 (2)	0.028 (9)*
H3	0.2154 (18)	0.659 (5)	0.241 (3)	0.052 (13)*
H24	0.5685 (16)	−0.001 (4)	0.448 (3)	0.044 (11)*
H5A	0.0939 (13)	−0.145 (4)	0.452 (2)	0.025 (8)*
H12	0.3923 (13)	0.205 (4)	0.313 (2)	0.021 (7)*
H23	0.2221 (14)	−0.096 (4)	0.325 (3)	0.031 (9)*
H1A	0.1208 (14)	0.273 (4)	0.445 (2)	0.022 (8)*
H12A	0.2672 (14)	0.755 (4)	0.527 (2)	0.031 (9)*
H26A	0.4445 (18)	0.436 (5)	0.521 (3)	0.056 (13)*
H26	0.5732 (16)	−0.104 (5)	0.349 (3)	0.046 (11)*
H25	0.5769 (19)	0.063 (6)	0.343 (3)	0.063 (13)*
H25A	0.4452 (19)	0.597 (6)	0.527 (4)	0.063 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S4A	0.0172 (3)	0.0090 (3)	0.0203 (3)	−0.0013 (2)	−0.0003 (2)	0.0001 (2)
S4	0.0162 (3)	0.0086 (3)	0.0235 (3)	0.0014 (2)	0.0006 (2)	0.0000 (2)
S6A	0.0155 (3)	0.0122 (3)	0.0218 (3)	0.0003 (2)	−0.0010 (2)	−0.0010 (2)
S6	0.0202 (3)	0.0081 (3)	0.0238 (3)	−0.0003 (2)	0.0000 (2)	−0.0016 (2)
S2A	0.0198 (3)	0.0084 (3)	0.0227 (3)	0.0012 (2)	0.0002 (2)	0.0006 (2)
S2	0.0143 (3)	0.0125 (3)	0.0442 (4)	−0.0002 (2)	0.0022 (3)	−0.0004 (2)
O21A	0.0215 (8)	0.0108 (8)	0.0236 (9)	−0.0023 (7)	0.0011 (7)	−0.0007 (7)
N1A	0.0177 (10)	0.0098 (9)	0.0189 (10)	−0.0015 (8)	0.0000 (8)	−0.0013 (8)
N5	0.0152 (10)	0.0102 (10)	0.0219 (10)	−0.0009 (8)	0.0009 (8)	−0.0002 (8)
O21	0.0227 (10)	0.0114 (9)	0.0788 (17)	0.0014 (8)	−0.0090 (10)	0.0052 (10)
N1	0.0162 (10)	0.0087 (9)	0.0239 (11)	0.0025 (8)	0.0014 (8)	0.0001 (8)
N3A	0.0167 (10)	0.0095 (10)	0.0190 (10)	0.0001 (8)	−0.0018 (8)	−0.0007 (8)
N3	0.0169 (10)	0.0081 (9)	0.0220 (10)	−0.0008 (8)	0.0006 (8)	0.0001 (8)
N5A	0.0164 (10)	0.0077 (9)	0.0222 (10)	0.0006 (8)	−0.0007 (8)	−0.0010 (8)
N21A	0.0158 (10)	0.0108 (10)	0.0258 (11)	−0.0007 (8)	−0.0008 (8)	−0.0013 (8)
N22A	0.0175 (10)	0.0139 (10)	0.0187 (10)	0.0000 (8)	−0.0003 (8)	−0.0003 (9)
N22	0.0180 (10)	0.0134 (10)	0.0286 (12)	0.0010 (8)	0.0000 (9)	−0.0009 (9)
N21	0.0150 (10)	0.0109 (10)	0.0407 (13)	0.0015 (8)	−0.0025 (9)	−0.0018 (9)
C21A	0.0241 (12)	0.0092 (11)	0.0158 (11)	−0.0014 (9)	0.0014 (9)	0.0030 (9)
C4A	0.0191 (11)	0.0127 (11)	0.0115 (10)	0.0017 (9)	0.0020 (9)	−0.0007 (8)
C11A	0.0220 (12)	0.0155 (12)	0.0175 (12)	0.0003 (10)	0.0015 (9)	0.0008 (9)
C2A	0.0203 (12)	0.0114 (11)	0.0141 (11)	0.0007 (9)	0.0037 (9)	0.0010 (9)
C4	0.0196 (11)	0.0108 (11)	0.0130 (11)	−0.0008 (9)	0.0012 (8)	0.0001 (8)
C2	0.0175 (12)	0.0112 (11)	0.0207 (12)	−0.0004 (9)	0.0012 (9)	−0.0009 (9)
C21	0.0209 (13)	0.0117 (12)	0.0274 (13)	0.0001 (10)	0.0006 (10)	0.0016 (9)
C6	0.0211 (12)	0.0127 (11)	0.0139 (11)	0.0010 (9)	0.0013 (9)	−0.0008 (8)
C6A	0.0199 (12)	0.0113 (11)	0.0158 (11)	−0.0002 (9)	0.0014 (9)	−0.0017 (9)
C11	0.0193 (12)	0.0150 (12)	0.0290 (13)	−0.0007 (10)	0.0002 (10)	0.0001 (10)
C12A	0.0229 (13)	0.0143 (12)	0.0323 (14)	−0.0010 (10)	0.0013 (10)	−0.0018 (10)
C15	0.0228 (14)	0.0228 (14)	0.0415 (17)	0.0046 (11)	−0.0003 (12)	0.0007 (12)
C12	0.0252 (14)	0.0153 (13)	0.0370 (15)	−0.0021 (11)	−0.0005 (11)	0.0005 (11)
C13A	0.0228 (14)	0.0239 (14)	0.0391 (16)	−0.0063 (11)	0.0000 (11)	−0.0022 (12)
C16	0.0214 (13)	0.0157 (13)	0.0410 (16)	0.0006 (10)	0.0006 (11)	0.0009 (11)
C16A	0.0255 (14)	0.0150 (13)	0.0390 (16)	0.0001 (11)	−0.0005 (11)	−0.0011 (11)
C14A	0.0195 (13)	0.0328 (15)	0.0288 (14)	0.0010 (11)	−0.0002 (11)	0.0026 (12)
C14	0.0194 (13)	0.0317 (15)	0.0334 (15)	−0.0014 (11)	0.0006 (11)	−0.0038 (12)
C13	0.0251 (14)	0.0231 (14)	0.0423 (17)	−0.0087 (12)	0.0014 (12)	−0.0023 (12)
C15A	0.0251 (14)	0.0237 (15)	0.0453 (18)	0.0075 (12)	0.0022 (12)	0.0005 (12)
C24	0.0198 (14)	0.0437 (19)	0.048 (2)	−0.0019 (13)	0.0011 (13)	−0.0056 (16)
C24A	0.0205 (14)	0.0426 (19)	0.048 (2)	0.0009 (13)	−0.0009 (13)	0.0050 (16)

Geometric parameters (Å, º) top

S4A—C4A	1.654 (2)	N22—H23	0.90 (4)
S4—C4	1.660 (2)	N21—C21	1.339 (3)
S6A—C6A	1.671 (2)	N21—H21	0.86 (4)
S6—C6	1.653 (2)	C21A—C11A	1.495 (3)
S2A—C2A	1.648 (2)	C11A—C12A	1.390 (4)
S2—C2	1.659 (2)	C11A—C16A	1.393 (4)
O21A—C21A	1.230 (3)	C21—C11	1.498 (3)
N1A—C6A	1.364 (3)	C11—C16	1.392 (4)
N1A—C2A	1.379 (3)	C11—C12	1.394 (4)
N1A—H1A	0.86 (4)	C12A—C13A	1.383 (4)
N5—C4	1.361 (3)	C12A—H12A	0.93 (4)
N5—C6	1.365 (3)	C15—C16	1.389 (4)
N5—H5	0.87 (3)	C15—C14	1.391 (4)
O21—C21	1.223 (3)	C15—H15	0.95 (4)
N1—C2	1.365 (3)	C12—C13	1.382 (4)
N1—C6	1.371 (3)	C12—H12	0.92 (3)
N1—H1	0.82 (4)	C13A—C14A	1.390 (4)
N3A—C2A	1.363 (3)	C13A—H13A	0.96 (4)
N3A—C4A	1.364 (3)	C16—H16	0.94 (4)
N3A—H3A	0.81 (3)	C16A—C15A	1.385 (4)
N3—C4	1.362 (3)	C16A—H16A	0.90 (4)
N3—C2	1.364 (3)	C14A—C15A	1.384 (4)
N3—H3	0.78 (5)	C14A—C24A	1.510 (4)
N5A—C6A	1.357 (3)	C14—C13	1.394 (4)
N5A—C4A	1.368 (3)	C14—C24	1.512 (4)
N5A—H5A	0.92 (4)	C13—H13	0.94 (4)
N21A—C21A	1.343 (3)	C15A—H15A	0.88 (4)
N21A—N22A	1.416 (3)	C24—H24	0.99 (4)
N21A—H21A	0.88 (4)	C24—H26	0.94 (4)
N22A—H23A	0.89 (3)	C24—H25	0.95 (5)
N22A—H22A	0.84 (4)	C24A—H24A	0.91 (5)
N22—N21	1.406 (3)	C24A—H26A	0.92 (5)
N22—H22	0.88 (4)	C24A—H25A	0.91 (5)

C6A—N1A—C2A	124.3 (2)	N5—C6—N1	115.1 (2)
C6A—N1A—H1A	116 (2)	N5—C6—S6	121.55 (19)
C2A—N1A—H1A	120 (2)	N1—C6—S6	123.36 (19)
C4—N5—C6	124.9 (2)	N5A—C6A—N1A	115.9 (2)
C4—N5—H5	116.9 (18)	N5A—C6A—S6A	122.26 (18)
C6—N5—H5	118.1 (18)	N1A—C6A—S6A	121.83 (18)
C2—N1—C6	124.3 (2)	C16—C11—C12	119.1 (2)
C2—N1—H1	118 (2)	C16—C11—C21	123.8 (2)
C6—N1—H1	118 (2)	C12—C11—C21	117.1 (2)
C2A—N3A—C4A	125.1 (2)	C13A—C12A—C11A	120.1 (3)
C2A—N3A—H3A	115 (2)	C13A—C12A—H12A	122 (2)
C4A—N3A—H3A	119 (2)	C11A—C12A—H12A	118 (2)
C4—N3—C2	124.6 (2)	C16—C15—C14	121.2 (3)
C4—N3—H3	117 (3)	C16—C15—H15	122 (2)
C2—N3—H3	118 (3)	C14—C15—H15	116 (2)
C6A—N5A—C4A	124.5 (2)	C13—C12—C11	120.1 (3)
C6A—N5A—H5A	116 (2)	C13—C12—H12	125 (2)
C4A—N5A—H5A	119 (2)	C11—C12—H12	115 (2)
C21A—N21A—N22A	120.8 (2)	C12A—C13A—C14A	121.2 (3)
C21A—N21A—H21A	122 (3)	C12A—C13A—H13A	121 (2)
N22A—N21A—H21A	115 (3)	C14A—C13A—H13A	118 (2)
N21A—N22A—H23A	108.0 (18)	C15—C16—C11	120.2 (3)
N21A—N22A—H22A	108 (2)	C15—C16—H16	117 (2)
H23A—N22A—H22A	109 (3)	C11—C16—H16	123 (2)
N21—N22—H22	113 (3)	C15A—C16A—C11A	120.1 (3)
N21—N22—H23	107 (2)	C15A—C16A—H16A	122 (3)
H22—N22—H23	107 (3)	C11A—C16A—H16A	118 (3)
C21—N21—N22	120.9 (2)	C15A—C14A—C13A	118.3 (3)
C21—N21—H21	120 (2)	C15A—C14A—C24A	121.0 (3)
N22—N21—H21	117 (2)	C13A—C14A—C24A	120.6 (3)
O21A—C21A—N21A	121.5 (2)	C15—C14—C13	117.9 (3)
O21A—C21A—C11A	121.3 (2)	C15—C14—C24	120.7 (3)
N21A—C21A—C11A	117.2 (2)	C13—C14—C24	121.4 (3)
N3A—C4A—N5A	115.1 (2)	C12—C13—C14	121.5 (3)
N3A—C4A—S4A	123.81 (18)	C12—C13—H13	122 (2)
N5A—C4A—S4A	121.11 (18)	C14—C13—H13	116 (2)
C12A—C11A—C16A	119.1 (2)	C14A—C15A—C16A	121.1 (3)
C12A—C11A—C21A	124.0 (2)	C14A—C15A—H15A	116 (3)
C16A—C11A—C21A	116.9 (2)	C16A—C15A—H15A	123 (3)
N3A—C2A—N1A	114.6 (2)	C14—C24—H24	110 (2)
N3A—C2A—S2A	122.71 (19)	C14—C24—H26	109 (2)
N1A—C2A—S2A	122.73 (18)	H24—C24—H26	114 (3)
N5—C4—N3	115.4 (2)	C14—C24—H25	114 (3)
N5—C4—S4	122.97 (19)	H24—C24—H25	105 (4)
N3—C4—S4	121.59 (18)	H26—C24—H25	104 (4)
N3—C2—N1	115.4 (2)	C14A—C24A—H24A	112 (3)
N3—C2—S2	122.13 (18)	C14A—C24A—H26A	111 (3)
N1—C2—S2	122.43 (19)	H24A—C24A—H26A	112 (4)
O21—C21—N21	121.3 (2)	C14A—C24A—H25A	109 (3)
O21—C21—C11	121.2 (2)	H24A—C24A—H25A	109 (4)
N21—C21—C11	117.4 (2)	H26A—C24A—H25A	103 (4)

N22A—N21A—C21A—O21A	−4.0 (4)	C4A—N5A—C6A—N1A	3.9 (3)
N22A—N21A—C21A—C11A	175.8 (2)	C4A—N5A—C6A—S6A	−176.18 (18)
C2A—N3A—C4A—N5A	−8.0 (3)	C2A—N1A—C6A—N5A	−2.5 (3)
C2A—N3A—C4A—S4A	171.75 (18)	C2A—N1A—C6A—S6A	177.54 (18)
C6A—N5A—C4A—N3A	1.0 (3)	O21—C21—C11—C16	179.9 (3)
C6A—N5A—C4A—S4A	−178.77 (18)	N21—C21—C11—C16	1.5 (4)
O21A—C21A—C11A—C12A	160.7 (2)	O21—C21—C11—C12	−1.2 (4)
N21A—C21A—C11A—C12A	−19.0 (4)	N21—C21—C11—C12	−179.5 (3)
O21A—C21A—C11A—C16A	−18.7 (4)	C16A—C11A—C12A—C13A	1.0 (4)
N21A—C21A—C11A—C16A	161.6 (2)	C21A—C11A—C12A—C13A	−178.4 (3)
C4A—N3A—C2A—N1A	9.1 (3)	C16—C11—C12—C13	0.1 (4)
C4A—N3A—C2A—S2A	−170.30 (19)	C21—C11—C12—C13	−178.9 (3)
C6A—N1A—C2A—N3A	−3.5 (3)	C11A—C12A—C13A—C14A	−0.3 (4)
C6A—N1A—C2A—S2A	175.91 (18)	C14—C15—C16—C11	0.3 (5)
C6—N5—C4—N3	0.9 (3)	C12—C11—C16—C15	−0.5 (4)
C6—N5—C4—S4	−179.40 (18)	C21—C11—C16—C15	178.4 (3)
C2—N3—C4—N5	0.3 (3)	C12A—C11A—C16A—C15A	−0.5 (4)
C2—N3—C4—S4	−179.43 (19)	C21A—C11A—C16A—C15A	179.0 (3)
C4—N3—C2—N1	−3.2 (3)	C12A—C13A—C14A—C15A	−1.0 (5)
C4—N3—C2—S2	175.81 (18)	C12A—C13A—C14A—C24A	179.5 (3)
C6—N1—C2—N3	5.3 (3)	C16—C15—C14—C13	0.3 (5)
C6—N1—C2—S2	−173.67 (19)	C16—C15—C14—C24	179.8 (3)
N22—N21—C21—O21	5.7 (4)	C11—C12—C13—C14	0.6 (5)
N22—N21—C21—C11	−175.9 (2)	C15—C14—C13—C12	−0.8 (5)
C4—N5—C6—N1	1.0 (3)	C24—C14—C13—C12	179.8 (3)
C4—N5—C6—S6	−178.48 (18)	C13A—C14A—C15A—C16A	1.5 (5)
C2—N1—C6—N5	−4.3 (3)	C24A—C14A—C15A—C16A	−178.9 (3)
C2—N1—C6—S6	175.16 (19)	C11A—C16A—C15A—C14A	−0.8 (5)

Parameters of selected hydrogen bonds for I and II (Å, °) top

	Hydrogen bond	D—H	H···A	D···A	D—H···A	Symmetry code
I	N3—H3···S2	0.76 (4)	2.64 (4)	3.388 (3)	172 (3)	-x+1, -y-1, -z+1
	N1—H1···S6	0.84 (4)	2.43 (4)	3.264 (2)	169 (4)	-x+1/2, -y+1/2, -z+1
	N5—H5···N11	0.93 (4)	1.85 (4)	2.768 (3)	171 (3)	x, -y+1, z+1/2
II	N1—H1···O21	0.82 (4)	1.97 (3)	2.757 (3)	161 (3)	x, y-1, z
	N1A—H1A···O21A	0.86 (4)	1.88 (3)	2.713 (3)	165 (3)	x, y, z
	N3—H3···N22	0.78 (5)	1.98 (4)	2.758 (3)	173 (4)	x, y, z
	N3A—H3A···S4	0.81 (3)	2.49 (3)	3.300 (2)	175 (3)	-x, y-1/2, -z+1/2
	N5—H5···S4A	0.87 (3)	2.43 (3)	3.276 (2)	164 (2)	-x, y+1/2, -z+1/2
	N5A—H5A···N22A	0.92 (3)	1.83 (3)	2.746 (3)	110 (2)	x, y+1, z
	N21—H21···S2	0.86 (4)	2.65 (4)	3.395 (3)	147 (3)	x, y, z
	N21A—H21A···S6A	0.88 (4)	2.72 (4)	3.437 (2)	140 (3)	x, y+1, z
	N22—H22..S6	0.88 (4)	2.72 (4)	3.347 (2)	129 (3)	x, y+1, z
	N22A—H22A···S2A	0.84 (4)	2.72 (3)	3.416 (2)	141 (3)	x, y, z
	N22—H23···S6A	0.90 (4)	2.65 (4)	3.546 (2)	173 (3)	x, y+1, z
	N22A—H23A···S4	0.90 (3)	2.86 (3)	3.428 (2)	123 (2)	x, -y+3/2, z+1/2

Parameters of selected π–π stacking interactions for crystal structure (II) (Å, °) top

π–π stacking interaction	Cg···Cg	(PLN1, PLN2)	d (PLN1, PLN2)	Slippage
Cg(TAH)···Cg(TAH)	5.925 (2)	7.7 (1)	2.567 (1),3.167 (1)	5.007
Cg(TAH)···Cg(TAH)	5.056 (2)	0	3.783 (1),3.783 (1)	3.355
Cg(TAH)···Cg(TAH-A)	5.144(2	3.8 (1)	3.673 (1),3.695 (1)	3.578
Cg(TAH-A)···Cg(TAH)	5.787 (2)	11.5 (1)	2.672 (1),3.476 (1)	4.627
Cg(TAH-A)···Cg(TAH)	5.144 (2)	3.8 (1)	3.695 (1),3.673 (1)	3.601
Cg(TAH-A)···Cg(TTCA)	4.943 (2)	5.1 (1)	3.588 (1), 3.280 (1)	3.698
Cg(TAH-A)···Cg(TTCA)	5.932 (2)	13.1 (1)	2.661 (1), 3.753 (1)	4.593
Cg(TTCA)···Cg(TAH-A)	4.943 (2)	5.1 (1)	3.280 (1), 3.588 (1)	3.401
Cg(TTCA)···Cg(TTCA-A)	5.076 (2)	17.5 (1)	3.293 (1), 3.005 (1)	4.091
Cg(TTCA)···Cg(TTCA-A)	5.033 (2)	16.0 (1)	2.908 (1), 3.899 (1)	3.184
Cg(TTCA-A)···Cg(TTCA)	5.076 (2)	17.49 (11)	3.005 (1), 3.293 (1)	3.863
Cg(TTCA-A)···Cg(TTCA-A)	5.033 (2)	15.99 (1)	3.898 (1), 2.908 (1)	4.108
Cg(TTCA-A)···Cg(TTCA-A)	4.392 (2)	0	3.371 (1), 3.371 (1)	2.814

Notes: Cg is the centre of ring gravity for the trithiocyanuric acid molecule; TAH is 4-methylbenzohydrazide; TTCA is trithiocyanuric acid; slippage is the distance between Cg and d (PLN1, PLN2); A denotes the second molecule of the asymmetric unit.

Total molecular energies estimated for all possible trithiocyanuric acid tautomers (E_tot in Hartrees) and the relative energies estimated as a difference between a given tautomer and the one of lowest energy (ΔE in kcal mol^-1) top

Tautomer	E_tot	ΔE
NHNHNH (form A in Scheme 2)	-1473.0743	0.00
SHNHNH (form B in Scheme 2)	-1473.0472	17.00
SHSHNH (form C in Scheme 2)	-1473.0336	25.54
SHSHSH (form D in Scheme 2)	-1473.0408	21.02

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Tri­thio­cyanuric acid: novel cocrystals and analysis of its tautomeric forms

Supporting information

Trithiocyanuric acid: novel cocrystals and analysis of its tautomeric forms