Cocrystals of trithiocyanuric acid with 2,2′-bipyridyl [1,3,5-triazinane-2,4,6-trithione–2,2′-bipyridine (2/1), 2C
3H
3N
3S
3·C
10H
8N
2, (
I)] and 4-methylbenzohydrazide [1,3,5-triazinane-2,4,6-trithione–4-methylbenzohydrazide (1/1), C
8H
10N
2O·C
3H
3N
3S
3, (
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.
Supporting information
CCDC references: 2049682; 2049681
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 |
Mr = 510.72 | Dx = 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 | Rint = 0.054 |
CrysAlisPro 1.171.39.15e (Rigaku Oxford Diffraction, 2015) scans | θmax = 68.5°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | h = −14→14 |
Tmin = 0.544, Tmax = 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(Fo2) + (0.0746P)2 + 2.3683P] where P = (Fo2 + 2Fc2)/3 |
1896 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −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 | Uiso*/Ueq | |
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 |
Mr = 327.45 | Dx = 1.482 Mg m−3 Dm = Mg m−3 Dm 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 | Rint = 0.037 |
CrysAlis PRO (Rigaku OD, 2015) scans | θmax = 68.5°, θmin = 3.6° |
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015) | h = −29→29 |
Tmin = 0.287, Tmax = 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(Fo2) + (0.055P)2 + 4.646P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
5403 reflections | Δρmax = 0.48 e Å−3 |
458 parameters | Δρmin = −0.34 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 | Uiso*/Ueq | |
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, °) topπ–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 (Etot 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) topTautomer | Etot | 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 |