Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109043728/ln3135sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109043728/ln3135Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109043728/ln3135IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109043728/ln3135IIIsup4.hkl |
CCDC references: 763594; 763595; 763596
Compound (I) was prepared by procedures similar to those previously reported by Arndt et al. (1984). Typically, an aqueous solution (400 ml) of methyl benzoylformate (150 mmol) and thiosemicarbazide (150 mmol) was stirred at 343 K for 1.5 h. After cooling, 30% NaOH aq (ca 40 ml) was slowly added to the solution to adjust the pH to 11 and the mixture was stirred at 353 K for 4 h. By the addition of 6 M HCl to pH = 1, a white powder of (I) was obtained (62% yield). The products of (I) (50 mmol) and dibromoethylene (50 mmol) were added to an EtOH solution (30 ml) of Na (50 mmol), then the mixture was refluxed for 1 h. Na2CO3 (25 mmol) was added to the solution, and the mixture was refluxed for 10 h. After removing the solid by filtering, the solvent was evaporated off to give a white powder of the compounds (II) and (III). The products were purified by column chromatography (silica gel, AcOEt) to give pure products of (II) in 52% yield and (III) in 19% yield. Single crystals of (I), (II) and (III) suitable for X-ray crystallography were obtained by cooling a hot solution of 2-propanol.
IR, MS and NMR were measured by a Shimadzu FTIR-8400S (KBr disc), Shimadzu GCMS QP2010Plus and Varian NMR (Mercury-300 and UNITY-400), respectively. The results of the C═O stretch bands and MS fragments are as follows. For (II): IR 1665 cm-1, MS 231, 128, 60 m/z; 2,3-dihydro-6-methyl-7H-thiazolo[3,2-b]1,2,4-triazin-7-one (methyl derivative): IR 1637 cm-1, MS 169, 128, 60 m/z; 2,3-dihydro-6-ethyl-7H-thiazolo[3,2-b]1,2,4-triazin-7-one (ethyl derivative): IR 1649 cm-1, MS 183, 128, 60 m/z. For (III): IR 1669 cm-1, MS 231, 203, 103 m/z; 6,7-dihydro-3-methyl-4H-thiazolo[2,3-c]1,2,4-triazin-4-one (methyl derivative): IR 1684 cm-1, MS 169, 141, 56 m/z; 6,7-dihydro-3-ethyl-4H-thiazolo[2,3-c] 1,2,4-triazin-4-one (ethyl derivative): IR 1672 cm-1, MS 183, 154, 56 m/z.
All H atoms were placed in geometrically idealized positions and refined as riding, with aromatic C—H = 0.95, aliphatic C—H = 0.99, and N—H distances of 0.88 Å, and with Uiso(H) = 1.2Ueq(parent atom).
For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C9H7N3OS | F(000) = 848 |
Mr = 205.24 | Dx = 1.533 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4230 reflections |
a = 11.1891 (11) Å | θ = 2.6–27.9° |
b = 7.4401 (7) Å | µ = 0.33 mm−1 |
c = 21.359 (2) Å | T = 100 K |
V = 1778.1 (3) Å3 | Prismatic, colorless |
Z = 8 | 0.30 × 0.20 × 0.06 mm |
Bruker APEXII CCD diffractometer | 2023 independent reflections |
Radiation source: fine-focus sealed tube | 1746 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −14→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.908, Tmax = 0.981 | l = −17→27 |
9167 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0411P)2 + 0.9641P] where P = (Fo2 + 2Fc2)/3 |
2023 reflections | (Δ/σ)max = 0.001 |
127 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C9H7N3OS | V = 1778.1 (3) Å3 |
Mr = 205.24 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.1891 (11) Å | µ = 0.33 mm−1 |
b = 7.4401 (7) Å | T = 100 K |
c = 21.359 (2) Å | 0.30 × 0.20 × 0.06 mm |
Bruker APEXII CCD diffractometer | 2023 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1746 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.981 | Rint = 0.021 |
9167 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.35 e Å−3 |
2023 reflections | Δρmin = −0.23 e Å−3 |
127 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
C3 | 0.29011 (12) | 0.51770 (18) | 0.99709 (6) | 0.0139 (3) | |
C5 | 0.11586 (12) | 0.59405 (18) | 0.93372 (6) | 0.0149 (3) | |
C6 | 0.20060 (12) | 0.66472 (18) | 0.88639 (6) | 0.0138 (3) | |
C11 | 0.15989 (11) | 0.73315 (18) | 0.82507 (6) | 0.0134 (3) | |
C12 | 0.23583 (12) | 0.71067 (18) | 0.77352 (6) | 0.0153 (3) | |
H12 | 0.3109 | 0.6529 | 0.7788 | 0.018* | |
C13 | 0.20227 (13) | 0.7722 (2) | 0.71483 (7) | 0.0182 (3) | |
H13 | 0.2539 | 0.7555 | 0.6800 | 0.022* | |
C14 | 0.09264 (13) | 0.8584 (2) | 0.70689 (7) | 0.0197 (3) | |
H14 | 0.0694 | 0.9005 | 0.6667 | 0.024* | |
C15 | 0.01755 (12) | 0.88268 (19) | 0.75794 (7) | 0.0184 (3) | |
H15 | −0.0565 | 0.9431 | 0.7525 | 0.022* | |
C16 | 0.04942 (12) | 0.81956 (18) | 0.81691 (7) | 0.0160 (3) | |
H16 | −0.0032 | 0.8348 | 0.8514 | 0.019* | |
N1 | 0.31571 (10) | 0.66267 (16) | 0.89647 (5) | 0.0161 (3) | |
N2 | 0.35663 (10) | 0.58926 (16) | 0.95071 (6) | 0.0162 (3) | |
H2 | 0.4346 | 0.5884 | 0.9561 | 0.019* | |
N4 | 0.16975 (10) | 0.52311 (16) | 0.98625 (5) | 0.0149 (2) | |
H4 | 0.1227 | 0.4775 | 1.0152 | 0.018* | |
O1 | 0.00699 (8) | 0.59511 (15) | 0.92834 (5) | 0.0207 (2) | |
S1 | 0.34819 (3) | 0.42904 (5) | 1.062000 (17) | 0.01749 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.0133 (6) | 0.0144 (6) | 0.0141 (6) | −0.0003 (5) | −0.0007 (5) | −0.0026 (5) |
C5 | 0.0148 (6) | 0.0163 (6) | 0.0135 (6) | −0.0004 (5) | −0.0001 (5) | −0.0019 (5) |
C6 | 0.0130 (6) | 0.0136 (6) | 0.0148 (6) | −0.0003 (5) | 0.0012 (5) | −0.0022 (5) |
C11 | 0.0127 (6) | 0.0135 (6) | 0.0140 (6) | −0.0019 (5) | −0.0009 (5) | −0.0009 (5) |
C12 | 0.0128 (6) | 0.0159 (6) | 0.0172 (7) | −0.0004 (5) | −0.0001 (5) | −0.0009 (5) |
C13 | 0.0189 (7) | 0.0205 (7) | 0.0153 (7) | −0.0027 (6) | 0.0002 (6) | −0.0007 (5) |
C14 | 0.0216 (7) | 0.0203 (7) | 0.0173 (7) | −0.0043 (6) | −0.0064 (6) | 0.0027 (6) |
C15 | 0.0142 (6) | 0.0167 (7) | 0.0244 (8) | −0.0007 (5) | −0.0048 (6) | 0.0014 (6) |
C16 | 0.0123 (6) | 0.0165 (7) | 0.0191 (7) | −0.0010 (5) | 0.0007 (5) | −0.0016 (5) |
N1 | 0.0142 (5) | 0.0197 (6) | 0.0143 (6) | 0.0000 (5) | −0.0011 (5) | 0.0009 (5) |
N2 | 0.0098 (5) | 0.0231 (6) | 0.0157 (6) | −0.0005 (4) | −0.0010 (4) | 0.0033 (5) |
N4 | 0.0121 (6) | 0.0203 (6) | 0.0123 (6) | −0.0019 (4) | 0.0011 (4) | 0.0004 (5) |
O1 | 0.0119 (5) | 0.0329 (6) | 0.0173 (5) | −0.0017 (4) | 0.0001 (4) | 0.0039 (4) |
S1 | 0.01445 (19) | 0.0238 (2) | 0.01423 (18) | −0.00027 (13) | −0.00180 (12) | 0.00336 (13) |
C3—N2 | 1.3487 (18) | C12—H12 | 0.9500 |
C3—N4 | 1.3670 (17) | C13—C14 | 1.395 (2) |
C3—S1 | 1.6673 (14) | C13—H13 | 0.9500 |
C5—O1 | 1.2236 (17) | C14—C15 | 1.388 (2) |
C5—N4 | 1.3789 (17) | C14—H14 | 0.9500 |
C5—C6 | 1.4823 (19) | C15—C16 | 1.391 (2) |
C6—N1 | 1.3059 (17) | C15—H15 | 0.9500 |
C6—C11 | 1.4773 (19) | C16—H16 | 0.9500 |
C11—C12 | 1.4008 (19) | N1—N2 | 1.3603 (16) |
C11—C16 | 1.4040 (18) | N2—H2 | 0.8800 |
C12—C13 | 1.386 (2) | N4—H4 | 0.8800 |
N2—C3—N4 | 114.06 (12) | C14—C13—H13 | 120.0 |
N2—C3—S1 | 123.49 (10) | C15—C14—C13 | 119.77 (13) |
N4—C3—S1 | 122.45 (11) | C15—C14—H14 | 120.1 |
O1—C5—N4 | 120.95 (13) | C13—C14—H14 | 120.1 |
O1—C5—C6 | 124.78 (13) | C14—C15—C16 | 120.81 (13) |
N4—C5—C6 | 114.27 (12) | C14—C15—H15 | 119.6 |
N1—C6—C11 | 117.02 (12) | C16—C15—H15 | 119.6 |
N1—C6—C5 | 120.95 (12) | C15—C16—C11 | 119.52 (13) |
C11—C6—C5 | 121.98 (12) | C15—C16—H16 | 120.2 |
C12—C11—C16 | 119.42 (13) | C11—C16—H16 | 120.2 |
C12—C11—C6 | 117.95 (12) | C6—N1—N2 | 118.49 (12) |
C16—C11—C6 | 122.63 (12) | C3—N2—N1 | 126.75 (12) |
C13—C12—C11 | 120.47 (13) | C3—N2—H2 | 116.6 |
C13—C12—H12 | 119.8 | N1—N2—H2 | 116.6 |
C11—C12—H12 | 119.8 | C3—N4—C5 | 125.44 (12) |
C12—C13—C14 | 120.00 (13) | C3—N4—H4 | 117.3 |
C12—C13—H13 | 120.0 | C5—N4—H4 | 117.3 |
O1—C5—C6—N1 | 178.24 (14) | C14—C15—C16—C11 | 1.2 (2) |
N4—C5—C6—N1 | −2.13 (19) | C12—C11—C16—C15 | −0.5 (2) |
O1—C5—C6—C11 | −4.4 (2) | C6—C11—C16—C15 | 179.17 (13) |
N4—C5—C6—C11 | 175.26 (12) | C11—C6—N1—N2 | −175.61 (11) |
N1—C6—C11—C12 | 29.78 (18) | C5—C6—N1—N2 | 1.9 (2) |
C5—C6—C11—C12 | −147.71 (13) | N4—C3—N2—N1 | −0.1 (2) |
N1—C6—C11—C16 | −149.90 (13) | S1—C3—N2—N1 | 179.55 (11) |
C5—C6—C11—C16 | 32.6 (2) | C6—N1—N2—C3 | −0.7 (2) |
C16—C11—C12—C13 | −0.3 (2) | N2—C3—N4—C5 | −0.2 (2) |
C6—C11—C12—C13 | 179.98 (12) | S1—C3—N4—C5 | −179.92 (11) |
C11—C12—C13—C14 | 0.5 (2) | O1—C5—N4—C3 | −179.09 (13) |
C12—C13—C14—C15 | 0.1 (2) | C6—C5—N4—C3 | 1.27 (19) |
C13—C14—C15—C16 | −1.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1i | 0.88 | 1.96 | 2.8307 (15) | 169 |
N2—H2···S1ii | 0.88 | 2.46 | 3.3166 (13) | 163 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
C11H9N3OS | F(000) = 480 |
Mr = 231.27 | Dx = 1.486 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4742 reflections |
a = 8.1257 (4) Å | θ = 2.6–27.8° |
b = 11.3239 (5) Å | µ = 0.29 mm−1 |
c = 11.3860 (5) Å | T = 100 K |
β = 99.363 (1)° | Prismatic, colorless |
V = 1033.72 (8) Å3 | 0.45 × 0.40 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2992 independent reflections |
Radiation source: fine-focus sealed tube | 2939 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
ϕ and ω scans | h = −9→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −14→6 |
Tmin = 0.880, Tmax = 0.944 | l = −14→14 |
5756 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.2617P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2992 reflections | Δρmax = 0.29 e Å−3 |
290 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), 577 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (7) |
C11H9N3OS | V = 1033.72 (8) Å3 |
Mr = 231.27 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.1257 (4) Å | µ = 0.29 mm−1 |
b = 11.3239 (5) Å | T = 100 K |
c = 11.3860 (5) Å | 0.45 × 0.40 × 0.20 mm |
β = 99.363 (1)° |
Bruker APEXII CCD diffractometer | 2992 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2939 reflections with I > 2σ(I) |
Tmin = 0.880, Tmax = 0.944 | Rint = 0.014 |
5756 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
2992 reflections | Absolute structure: Flack & Bernardinelli (2000), 577 Friedel pairs |
290 parameters | Absolute structure parameter: 0.02 (7) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4266 (2) | 1.06970 (19) | 0.56607 (16) | 0.0209 (4) | |
H1A | 0.3673 | 1.1334 | 0.6016 | 0.025* | |
H1B | 0.5394 | 1.0609 | 0.6135 | 0.025* | |
C2 | 0.4386 (2) | 1.09884 (18) | 0.43657 (16) | 0.0208 (4) | |
H2A | 0.3438 | 1.1489 | 0.4007 | 0.025* | |
H2B | 0.5440 | 1.1409 | 0.4313 | 0.025* | |
C3 | 0.3606 (2) | 0.89446 (17) | 0.42480 (14) | 0.0158 (3) | |
C5 | 0.3652 (2) | 0.77605 (17) | 0.26161 (15) | 0.0171 (3) | |
C6 | 0.4402 (2) | 0.87934 (17) | 0.20820 (15) | 0.0148 (3) | |
C11 | 0.4838 (2) | 0.87549 (17) | 0.08656 (15) | 0.0155 (3) | |
C12 | 0.6080 (2) | 0.95126 (17) | 0.05781 (15) | 0.0180 (4) | |
H12 | 0.6651 | 1.0025 | 0.1169 | 0.022* | |
C13 | 0.6482 (2) | 0.95202 (18) | −0.05589 (16) | 0.0208 (4) | |
H13 | 0.7337 | 1.0028 | −0.0741 | 0.025* | |
C14 | 0.5635 (2) | 0.8786 (2) | −0.14334 (16) | 0.0223 (4) | |
H14 | 0.5907 | 0.8795 | −0.2214 | 0.027* | |
C15 | 0.4392 (2) | 0.8039 (2) | −0.11654 (17) | 0.0226 (4) | |
H15 | 0.3806 | 0.7545 | −0.1766 | 0.027* | |
C16 | 0.4003 (2) | 0.80114 (18) | −0.00196 (16) | 0.0186 (4) | |
H16 | 0.3168 | 0.7487 | 0.0163 | 0.022* | |
C21 | 0.7847 (2) | 0.59748 (18) | −0.02063 (15) | 0.0177 (4) | |
H21A | 0.6807 | 0.6274 | −0.0689 | 0.021* | |
H21B | 0.8044 | 0.5160 | −0.0465 | 0.021* | |
C22 | 0.7706 (2) | 0.59932 (17) | 0.11135 (16) | 0.0190 (4) | |
H22A | 0.6525 | 0.5930 | 0.1223 | 0.023* | |
H22B | 0.8339 | 0.5330 | 0.1537 | 0.023* | |
C23 | 0.9434 (2) | 0.76919 (17) | 0.09170 (14) | 0.0143 (3) | |
C25 | 0.9978 (2) | 0.91738 (17) | 0.23010 (14) | 0.0154 (3) | |
C26 | 0.9012 (2) | 0.84520 (16) | 0.30510 (15) | 0.0143 (3) | |
C31 | 0.89419 (19) | 0.87809 (17) | 0.43064 (15) | 0.0156 (3) | |
C32 | 0.9134 (2) | 0.78876 (18) | 0.51682 (16) | 0.0188 (4) | |
H32 | 0.9285 | 0.7093 | 0.4941 | 0.023* | |
C33 | 0.9105 (2) | 0.8159 (2) | 0.63569 (17) | 0.0235 (4) | |
H33 | 0.9248 | 0.7553 | 0.6942 | 0.028* | |
C34 | 0.8867 (2) | 0.9319 (2) | 0.66839 (16) | 0.0260 (4) | |
H34 | 0.8848 | 0.9506 | 0.7495 | 0.031* | |
C35 | 0.8657 (2) | 1.0208 (2) | 0.58350 (18) | 0.0244 (4) | |
H35 | 0.8481 | 1.0998 | 0.6066 | 0.029* | |
C36 | 0.8704 (2) | 0.99464 (18) | 0.46448 (17) | 0.0194 (4) | |
H36 | 0.8575 | 1.0558 | 0.4066 | 0.023* | |
N1 | 0.47033 (17) | 0.97927 (14) | 0.26439 (12) | 0.0155 (3) | |
N2 | 0.43395 (18) | 0.98461 (14) | 0.37602 (13) | 0.0160 (3) | |
N4 | 0.32664 (19) | 0.79177 (15) | 0.37511 (13) | 0.0189 (3) | |
N21 | 0.82573 (17) | 0.74777 (14) | 0.26775 (12) | 0.0153 (3) | |
N22 | 0.84133 (16) | 0.71298 (14) | 0.15618 (12) | 0.0145 (3) | |
N24 | 1.02182 (17) | 0.86729 (15) | 0.12326 (13) | 0.0160 (3) | |
O1 | 0.33957 (18) | 0.68178 (14) | 0.21024 (11) | 0.0251 (3) | |
O2 | 1.05539 (16) | 1.01443 (12) | 0.26137 (11) | 0.0203 (3) | |
S1 | 0.31134 (5) | 0.93121 (5) | 0.56369 (4) | 0.02183 (11) | |
S2 | 0.96032 (5) | 0.69245 (5) | −0.03887 (4) | 0.01873 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0194 (8) | 0.0230 (10) | 0.0205 (9) | −0.0020 (8) | 0.0034 (6) | −0.0073 (8) |
C2 | 0.0248 (9) | 0.0155 (9) | 0.0226 (9) | 0.0009 (7) | 0.0051 (7) | −0.0051 (7) |
C3 | 0.0142 (7) | 0.0194 (9) | 0.0134 (7) | 0.0011 (7) | 0.0007 (6) | 0.0009 (7) |
C5 | 0.0194 (8) | 0.0156 (9) | 0.0152 (8) | 0.0007 (7) | −0.0007 (6) | 0.0021 (7) |
C6 | 0.0132 (7) | 0.0161 (9) | 0.0144 (8) | 0.0029 (7) | 0.0003 (6) | 0.0011 (7) |
C11 | 0.0148 (7) | 0.0159 (9) | 0.0156 (8) | 0.0044 (7) | 0.0017 (6) | 0.0015 (7) |
C12 | 0.0169 (8) | 0.0168 (9) | 0.0196 (8) | 0.0028 (7) | 0.0014 (6) | 0.0017 (7) |
C13 | 0.0172 (8) | 0.0218 (10) | 0.0242 (8) | 0.0040 (7) | 0.0058 (6) | 0.0070 (8) |
C14 | 0.0238 (9) | 0.0281 (10) | 0.0160 (8) | 0.0071 (8) | 0.0064 (6) | 0.0035 (8) |
C15 | 0.0221 (9) | 0.0266 (10) | 0.0186 (8) | 0.0028 (8) | 0.0018 (7) | −0.0026 (8) |
C16 | 0.0175 (8) | 0.0198 (9) | 0.0185 (8) | 0.0010 (7) | 0.0026 (6) | −0.0013 (7) |
C21 | 0.0163 (8) | 0.0178 (9) | 0.0187 (8) | −0.0025 (7) | 0.0017 (6) | −0.0057 (7) |
C22 | 0.0216 (8) | 0.0148 (9) | 0.0201 (8) | −0.0046 (7) | 0.0024 (6) | −0.0033 (7) |
C23 | 0.0132 (7) | 0.0169 (9) | 0.0128 (7) | 0.0029 (7) | 0.0018 (6) | −0.0002 (7) |
C25 | 0.0135 (7) | 0.0160 (8) | 0.0165 (7) | 0.0002 (7) | 0.0013 (5) | 0.0024 (7) |
C26 | 0.0137 (7) | 0.0139 (8) | 0.0150 (8) | 0.0019 (6) | 0.0018 (6) | 0.0008 (7) |
C31 | 0.0116 (7) | 0.0192 (9) | 0.0163 (8) | −0.0021 (7) | 0.0035 (6) | −0.0021 (7) |
C32 | 0.0189 (8) | 0.0197 (9) | 0.0182 (8) | −0.0025 (7) | 0.0040 (6) | −0.0004 (7) |
C33 | 0.0229 (9) | 0.0317 (11) | 0.0163 (9) | −0.0082 (8) | 0.0048 (7) | 0.0009 (8) |
C34 | 0.0206 (8) | 0.0399 (12) | 0.0194 (8) | −0.0112 (9) | 0.0093 (6) | −0.0106 (9) |
C35 | 0.0195 (8) | 0.0257 (10) | 0.0304 (10) | −0.0041 (8) | 0.0109 (7) | −0.0129 (9) |
C36 | 0.0152 (8) | 0.0192 (9) | 0.0245 (9) | −0.0013 (7) | 0.0052 (7) | −0.0026 (8) |
N1 | 0.0150 (6) | 0.0173 (7) | 0.0144 (7) | 0.0012 (6) | 0.0030 (5) | 0.0006 (6) |
N2 | 0.0175 (7) | 0.0152 (8) | 0.0152 (7) | −0.0003 (6) | 0.0026 (5) | −0.0018 (6) |
N4 | 0.0224 (7) | 0.0188 (8) | 0.0151 (7) | −0.0025 (6) | 0.0021 (5) | 0.0008 (6) |
N21 | 0.0158 (6) | 0.0165 (8) | 0.0137 (7) | 0.0003 (6) | 0.0026 (5) | −0.0003 (6) |
N22 | 0.0164 (6) | 0.0140 (8) | 0.0133 (6) | −0.0032 (6) | 0.0034 (5) | −0.0019 (6) |
N24 | 0.0166 (7) | 0.0156 (8) | 0.0164 (7) | −0.0024 (6) | 0.0041 (5) | −0.0007 (6) |
O1 | 0.0422 (7) | 0.0144 (7) | 0.0179 (6) | −0.0021 (6) | 0.0022 (5) | 0.0010 (6) |
O2 | 0.0263 (6) | 0.0147 (6) | 0.0203 (6) | −0.0058 (5) | 0.0051 (5) | −0.0015 (5) |
S1 | 0.0218 (2) | 0.0292 (3) | 0.01515 (19) | −0.0051 (2) | 0.00506 (15) | −0.00395 (19) |
S2 | 0.01945 (19) | 0.0210 (2) | 0.01678 (19) | −0.00308 (18) | 0.00601 (14) | −0.00520 (18) |
C1—C2 | 1.530 (2) | C21—S2 | 1.8257 (18) |
C1—S1 | 1.825 (2) | C21—H21A | 0.9900 |
C1—H1A | 0.9900 | C21—H21B | 0.9900 |
C1—H1B | 0.9900 | C22—N22 | 1.467 (2) |
C2—N2 | 1.463 (2) | C22—H22A | 0.9900 |
C2—H2A | 0.9900 | C22—H22B | 0.9900 |
C2—H2B | 0.9900 | C23—N24 | 1.302 (2) |
C3—N4 | 1.303 (2) | C23—N22 | 1.353 (2) |
C3—N2 | 1.347 (2) | C23—S2 | 1.7467 (17) |
C3—S1 | 1.7436 (17) | C25—O2 | 1.224 (2) |
C5—O1 | 1.219 (2) | C25—N24 | 1.385 (2) |
C5—N4 | 1.390 (2) | C25—C26 | 1.494 (2) |
C5—C6 | 1.493 (3) | C26—N21 | 1.300 (2) |
C6—N1 | 1.303 (2) | C26—C31 | 1.487 (2) |
C6—C11 | 1.485 (2) | C31—C36 | 1.397 (3) |
C11—C16 | 1.401 (3) | C31—C32 | 1.400 (3) |
C11—C12 | 1.403 (2) | C32—C33 | 1.392 (3) |
C12—C13 | 1.386 (2) | C32—H32 | 0.9500 |
C12—H12 | 0.9500 | C33—C34 | 1.388 (3) |
C13—C14 | 1.390 (3) | C33—H33 | 0.9500 |
C13—H13 | 0.9500 | C34—C35 | 1.386 (3) |
C14—C15 | 1.389 (3) | C34—H34 | 0.9500 |
C14—H14 | 0.9500 | C35—C36 | 1.394 (3) |
C15—C16 | 1.392 (3) | C35—H35 | 0.9500 |
C15—H15 | 0.9500 | C36—H36 | 0.9500 |
C16—H16 | 0.9500 | N1—N2 | 1.352 (2) |
C21—C22 | 1.526 (2) | N21—N22 | 1.3556 (19) |
C2—C1—S1 | 106.51 (12) | N22—C22—C21 | 105.46 (14) |
C2—C1—H1A | 110.4 | N22—C22—H22A | 110.6 |
S1—C1—H1A | 110.4 | C21—C22—H22A | 110.6 |
C2—C1—H1B | 110.4 | N22—C22—H22B | 110.6 |
S1—C1—H1B | 110.4 | C21—C22—H22B | 110.6 |
H1A—C1—H1B | 108.6 | H22A—C22—H22B | 108.8 |
N2—C2—C1 | 105.22 (16) | N24—C23—N22 | 124.58 (15) |
N2—C2—H2A | 110.7 | N24—C23—S2 | 123.82 (13) |
C1—C2—H2A | 110.7 | N22—C23—S2 | 111.59 (13) |
N2—C2—H2B | 110.7 | O2—C25—N24 | 121.42 (15) |
C1—C2—H2B | 110.7 | O2—C25—C26 | 122.45 (15) |
H2A—C2—H2B | 108.8 | N24—C25—C26 | 116.13 (16) |
N4—C3—N2 | 125.04 (16) | N21—C26—C31 | 115.93 (15) |
N4—C3—S1 | 122.91 (14) | N21—C26—C25 | 122.77 (15) |
N2—C3—S1 | 112.05 (14) | C31—C26—C25 | 121.21 (15) |
O1—C5—N4 | 120.76 (17) | C36—C31—C32 | 119.60 (16) |
O1—C5—C6 | 122.68 (16) | C36—C31—C26 | 122.03 (16) |
N4—C5—C6 | 116.55 (16) | C32—C31—C26 | 118.37 (17) |
N1—C6—C11 | 115.39 (16) | C33—C32—C31 | 120.27 (19) |
N1—C6—C5 | 122.47 (15) | C33—C32—H32 | 119.9 |
C11—C6—C5 | 122.13 (16) | C31—C32—H32 | 119.9 |
C16—C11—C12 | 118.83 (15) | C34—C33—C32 | 119.69 (19) |
C16—C11—C6 | 121.82 (16) | C34—C33—H33 | 120.2 |
C12—C11—C6 | 119.31 (15) | C32—C33—H33 | 120.2 |
C13—C12—C11 | 120.63 (17) | C35—C34—C33 | 120.45 (17) |
C13—C12—H12 | 119.7 | C35—C34—H34 | 119.8 |
C11—C12—H12 | 119.7 | C33—C34—H34 | 119.8 |
C12—C13—C14 | 120.07 (17) | C34—C35—C36 | 120.2 (2) |
C12—C13—H13 | 120.0 | C34—C35—H35 | 119.9 |
C14—C13—H13 | 120.0 | C36—C35—H35 | 119.9 |
C15—C14—C13 | 119.97 (16) | C35—C36—C31 | 119.73 (19) |
C15—C14—H14 | 120.0 | C35—C36—H36 | 120.1 |
C13—C14—H14 | 120.0 | C31—C36—H36 | 120.1 |
C14—C15—C16 | 120.26 (18) | C6—N1—N2 | 116.60 (15) |
C14—C15—H15 | 119.9 | C3—N2—N1 | 122.19 (15) |
C16—C15—H15 | 119.9 | C3—N2—C2 | 117.07 (14) |
C15—C16—C11 | 120.23 (17) | N1—N2—C2 | 119.30 (15) |
C15—C16—H16 | 119.9 | C3—N4—C5 | 117.01 (16) |
C11—C16—H16 | 119.9 | C26—N21—N22 | 116.24 (14) |
C22—C21—S2 | 106.82 (12) | C23—N22—N21 | 122.07 (14) |
C22—C21—H21A | 110.4 | C23—N22—C22 | 117.66 (14) |
S2—C21—H21A | 110.4 | N21—N22—C22 | 119.33 (13) |
C22—C21—H21B | 110.4 | C23—N24—C25 | 117.35 (14) |
S2—C21—H21B | 110.4 | C3—S1—C1 | 91.47 (8) |
H21A—C21—H21B | 108.6 | C23—S2—C21 | 91.43 (8) |
S1—C1—C2—N2 | −28.20 (17) | C11—C6—N1—N2 | −179.08 (13) |
O1—C5—C6—N1 | −178.65 (16) | C5—C6—N1—N2 | 1.5 (2) |
N4—C5—C6—N1 | 0.7 (2) | N4—C3—N2—N1 | 4.5 (3) |
O1—C5—C6—C11 | 2.0 (3) | S1—C3—N2—N1 | −174.42 (12) |
N4—C5—C6—C11 | −178.61 (15) | N4—C3—N2—C2 | 170.77 (16) |
N1—C6—C11—C16 | −152.22 (17) | S1—C3—N2—C2 | −8.2 (2) |
C5—C6—C11—C16 | 27.2 (2) | C6—N1—N2—C3 | −4.1 (2) |
N1—C6—C11—C12 | 25.5 (2) | C6—N1—N2—C2 | −170.01 (16) |
C5—C6—C11—C12 | −155.16 (16) | C1—C2—N2—C3 | 24.4 (2) |
C16—C11—C12—C13 | −0.4 (3) | C1—C2—N2—N1 | −168.96 (14) |
C6—C11—C12—C13 | −178.19 (16) | N2—C3—N4—C5 | −1.9 (3) |
C11—C12—C13—C14 | 1.0 (3) | S1—C3—N4—C5 | 176.91 (13) |
C12—C13—C14—C15 | −0.4 (3) | O1—C5—N4—C3 | 178.81 (17) |
C13—C14—C15—C16 | −0.8 (3) | C6—C5—N4—C3 | −0.6 (2) |
C14—C15—C16—C11 | 1.3 (3) | C31—C26—N21—N22 | −175.59 (14) |
C12—C11—C16—C15 | −0.7 (3) | C25—C26—N21—N22 | 1.1 (2) |
C6—C11—C16—C15 | 176.98 (17) | N24—C23—N22—N21 | −7.5 (3) |
S2—C21—C22—N22 | 26.76 (16) | S2—C23—N22—N21 | 171.45 (12) |
O2—C25—C26—N21 | 172.98 (16) | N24—C23—N22—C22 | −176.32 (16) |
N24—C25—C26—N21 | −8.2 (2) | S2—C23—N22—C22 | 2.63 (19) |
O2—C25—C26—C31 | −10.5 (3) | C26—N21—N22—C23 | 6.7 (2) |
N24—C25—C26—C31 | 168.27 (14) | C26—N21—N22—C22 | 175.30 (15) |
N21—C26—C31—C36 | −139.66 (17) | C21—C22—N22—C23 | −19.9 (2) |
C25—C26—C31—C36 | 43.6 (2) | C21—C22—N22—N21 | 170.99 (14) |
N21—C26—C31—C32 | 40.8 (2) | N22—C23—N24—C25 | −0.4 (2) |
C25—C26—C31—C32 | −135.91 (17) | S2—C23—N24—C25 | −179.20 (13) |
C36—C31—C32—C33 | −0.6 (3) | O2—C25—N24—C23 | −173.69 (16) |
C26—C31—C32—C33 | 178.92 (16) | C26—C25—N24—C23 | 7.5 (2) |
C31—C32—C33—C34 | 0.7 (3) | N4—C3—S1—C1 | 172.19 (15) |
C32—C33—C34—C35 | 0.0 (3) | N2—C3—S1—C1 | −8.81 (14) |
C33—C34—C35—C36 | −0.8 (3) | C2—C1—S1—C3 | 21.75 (13) |
C34—C35—C36—C31 | 0.8 (3) | N24—C23—S2—C21 | −168.58 (15) |
C32—C31—C36—C35 | −0.1 (3) | N22—C23—S2—C21 | 12.46 (14) |
C26—C31—C36—C35 | −179.65 (15) | C22—C21—S2—C23 | −22.94 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1i | 0.99 | 2.50 | 3.183 (2) | 126 |
C13—H13···O1ii | 0.95 | 2.56 | 3.150 (2) | 120 |
C21—H21B···N24iii | 0.99 | 2.45 | 3.351 (2) | 151 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y+1/2, −z; (iii) −x+2, y−1/2, −z. |
C11H9N3OS | F(000) = 960 |
Mr = 231.27 | Dx = 1.520 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4011 reflections |
a = 21.627 (3) Å | θ = 2.7–27.7° |
b = 8.1222 (10) Å | µ = 0.30 mm−1 |
c = 11.8888 (15) Å | T = 100 K |
β = 104.638 (2)° | Block, colorless |
V = 2020.6 (4) Å3 | 0.30 × 0.30 × 0.10 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | 4517 independent reflections |
Radiation source: fine-focus sealed tube | 3632 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ and ω scans | h = −27→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −10→10 |
Tmin = 0.916, Tmax = 0.971 | l = −13→15 |
10860 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0469P)2 + 1.0379P] where P = (Fo2 + 2Fc2)/3 |
4517 reflections | (Δ/σ)max = 0.001 |
289 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C11H9N3OS | V = 2020.6 (4) Å3 |
Mr = 231.27 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 21.627 (3) Å | µ = 0.30 mm−1 |
b = 8.1222 (10) Å | T = 100 K |
c = 11.8888 (15) Å | 0.30 × 0.30 × 0.10 mm |
β = 104.638 (2)° |
Bruker APEXII CCD diffractometer | 4517 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3632 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.971 | Rint = 0.023 |
10860 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.56 e Å−3 |
4517 reflections | Δρmin = −0.50 e Å−3 |
289 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.32791 (10) | 0.4391 (3) | 0.75224 (19) | 0.0355 (5) | |
H1A | 0.3005 | 0.5351 | 0.7220 | 0.043* | |
H1B | 0.3195 | 0.4055 | 0.8271 | 0.043* | |
C2 | 0.39778 (8) | 0.4846 (2) | 0.77028 (15) | 0.0222 (4) | |
H2A | 0.4022 | 0.6052 | 0.7630 | 0.027* | |
H2B | 0.4223 | 0.4509 | 0.8489 | 0.027* | |
C3 | 0.38304 (8) | 0.2888 (2) | 0.61371 (15) | 0.0191 (4) | |
C5 | 0.48389 (8) | 0.4270 (2) | 0.67158 (14) | 0.0188 (4) | |
C6 | 0.49918 (8) | 0.3229 (2) | 0.58033 (14) | 0.0174 (3) | |
C11 | 0.56367 (8) | 0.3248 (2) | 0.55718 (14) | 0.0181 (3) | |
C12 | 0.57745 (9) | 0.2090 (2) | 0.47880 (15) | 0.0213 (4) | |
H12 | 0.5454 | 0.1339 | 0.4404 | 0.026* | |
C13 | 0.63739 (9) | 0.2040 (2) | 0.45735 (16) | 0.0250 (4) | |
H13 | 0.6462 | 0.1250 | 0.4045 | 0.030* | |
C14 | 0.68486 (9) | 0.3135 (2) | 0.51242 (16) | 0.0255 (4) | |
H14 | 0.7260 | 0.3092 | 0.4977 | 0.031* | |
C15 | 0.67157 (9) | 0.4288 (2) | 0.58891 (16) | 0.0245 (4) | |
H15 | 0.7037 | 0.5045 | 0.6262 | 0.029* | |
C16 | 0.61167 (8) | 0.4350 (2) | 0.61172 (15) | 0.0204 (4) | |
H16 | 0.6033 | 0.5145 | 0.6646 | 0.024* | |
C21 | 0.16178 (10) | 0.4367 (4) | 0.4046 (2) | 0.0523 (7) | |
H21A | 0.1686 | 0.4002 | 0.4863 | 0.063* | |
H21B | 0.1899 | 0.5324 | 0.4032 | 0.063* | |
C22 | 0.09343 (9) | 0.4853 (2) | 0.35684 (15) | 0.0254 (4) | |
H22A | 0.0678 | 0.4531 | 0.4116 | 0.031* | |
H22B | 0.0901 | 0.6060 | 0.3456 | 0.031* | |
C23 | 0.10903 (8) | 0.2906 (2) | 0.21353 (15) | 0.0202 (4) | |
C25 | 0.00847 (8) | 0.4299 (2) | 0.17702 (15) | 0.0194 (4) | |
C26 | −0.00682 (8) | 0.3257 (2) | 0.07212 (14) | 0.0183 (3) | |
C31 | −0.07151 (8) | 0.3247 (2) | −0.00950 (15) | 0.0190 (4) | |
C32 | −0.08497 (9) | 0.2097 (2) | −0.10055 (16) | 0.0249 (4) | |
H32 | −0.0524 | 0.1370 | −0.1105 | 0.030* | |
C33 | −0.14525 (10) | 0.2010 (2) | −0.17605 (17) | 0.0294 (4) | |
H33 | −0.1537 | 0.1223 | −0.2372 | 0.035* | |
C34 | −0.19334 (9) | 0.3062 (2) | −0.16294 (18) | 0.0308 (5) | |
H34 | −0.2346 | 0.3000 | −0.2148 | 0.037* | |
C35 | −0.18082 (9) | 0.4205 (3) | −0.07368 (18) | 0.0300 (4) | |
H35 | −0.2138 | 0.4928 | −0.0646 | 0.036* | |
C36 | −0.12059 (9) | 0.4308 (2) | 0.00275 (17) | 0.0246 (4) | |
H36 | −0.1126 | 0.5099 | 0.0635 | 0.030* | |
N1 | 0.45743 (7) | 0.22165 (18) | 0.51665 (13) | 0.0201 (3) | |
N2 | 0.39686 (7) | 0.20253 (18) | 0.53141 (13) | 0.0218 (3) | |
N4 | 0.42228 (7) | 0.39948 (17) | 0.68153 (12) | 0.0183 (3) | |
N21 | 0.03514 (7) | 0.22516 (18) | 0.04688 (13) | 0.0211 (3) | |
N22 | 0.09563 (7) | 0.20606 (18) | 0.11785 (13) | 0.0227 (3) | |
N24 | 0.06947 (7) | 0.40080 (18) | 0.24500 (12) | 0.0189 (3) | |
O1 | 0.51799 (6) | 0.52754 (16) | 0.73436 (11) | 0.0248 (3) | |
O2 | −0.02550 (6) | 0.53237 (16) | 0.20753 (11) | 0.0270 (3) | |
S1 | 0.30970 (2) | 0.26990 (6) | 0.64887 (4) | 0.02690 (13) | |
S2 | 0.18175 (2) | 0.27044 (6) | 0.31750 (4) | 0.02798 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0289 (11) | 0.0447 (13) | 0.0340 (11) | −0.0023 (9) | 0.0099 (9) | −0.0124 (10) |
C2 | 0.0268 (9) | 0.0228 (9) | 0.0176 (8) | 0.0013 (7) | 0.0063 (7) | −0.0006 (7) |
C3 | 0.0190 (8) | 0.0154 (8) | 0.0208 (8) | −0.0002 (7) | 0.0013 (7) | 0.0046 (7) |
C5 | 0.0224 (9) | 0.0170 (8) | 0.0152 (8) | 0.0005 (7) | 0.0017 (7) | 0.0026 (6) |
C6 | 0.0225 (9) | 0.0128 (8) | 0.0151 (8) | 0.0011 (6) | 0.0017 (7) | 0.0024 (6) |
C11 | 0.0210 (8) | 0.0151 (8) | 0.0168 (8) | 0.0015 (6) | 0.0019 (6) | 0.0042 (6) |
C12 | 0.0261 (9) | 0.0177 (8) | 0.0192 (8) | −0.0008 (7) | 0.0038 (7) | 0.0007 (7) |
C13 | 0.0312 (10) | 0.0200 (9) | 0.0251 (9) | 0.0041 (8) | 0.0097 (8) | −0.0010 (7) |
C14 | 0.0253 (10) | 0.0248 (10) | 0.0277 (10) | 0.0020 (8) | 0.0091 (8) | 0.0038 (8) |
C15 | 0.0234 (9) | 0.0226 (9) | 0.0257 (9) | −0.0028 (7) | 0.0026 (7) | 0.0008 (7) |
C16 | 0.0229 (9) | 0.0168 (8) | 0.0206 (9) | 0.0002 (7) | 0.0040 (7) | 0.0012 (7) |
C21 | 0.0252 (11) | 0.093 (2) | 0.0374 (13) | 0.0016 (12) | 0.0051 (9) | −0.0277 (13) |
C22 | 0.0312 (10) | 0.0270 (10) | 0.0187 (9) | −0.0048 (8) | 0.0073 (7) | −0.0024 (7) |
C23 | 0.0189 (8) | 0.0179 (8) | 0.0248 (9) | −0.0027 (7) | 0.0077 (7) | 0.0050 (7) |
C25 | 0.0215 (9) | 0.0192 (8) | 0.0201 (9) | −0.0013 (7) | 0.0103 (7) | 0.0017 (7) |
C26 | 0.0216 (9) | 0.0159 (8) | 0.0192 (8) | −0.0012 (7) | 0.0084 (7) | 0.0017 (6) |
C31 | 0.0227 (9) | 0.0162 (8) | 0.0191 (8) | −0.0018 (7) | 0.0068 (7) | 0.0047 (7) |
C32 | 0.0291 (10) | 0.0206 (9) | 0.0248 (9) | −0.0014 (8) | 0.0064 (8) | 0.0013 (7) |
C33 | 0.0349 (11) | 0.0261 (10) | 0.0241 (10) | −0.0067 (8) | 0.0015 (8) | 0.0022 (8) |
C34 | 0.0245 (10) | 0.0303 (11) | 0.0326 (11) | −0.0057 (8) | −0.0018 (8) | 0.0125 (8) |
C35 | 0.0245 (10) | 0.0274 (10) | 0.0374 (11) | 0.0027 (8) | 0.0062 (8) | 0.0103 (9) |
C36 | 0.0266 (10) | 0.0194 (9) | 0.0286 (10) | 0.0005 (7) | 0.0084 (8) | 0.0034 (7) |
N1 | 0.0211 (8) | 0.0169 (7) | 0.0213 (7) | −0.0007 (6) | 0.0037 (6) | −0.0004 (6) |
N2 | 0.0228 (8) | 0.0167 (7) | 0.0256 (8) | −0.0018 (6) | 0.0055 (6) | −0.0028 (6) |
N4 | 0.0221 (7) | 0.0169 (7) | 0.0151 (7) | 0.0001 (6) | 0.0031 (6) | 0.0001 (6) |
N21 | 0.0220 (8) | 0.0183 (7) | 0.0238 (8) | −0.0001 (6) | 0.0073 (6) | −0.0009 (6) |
N22 | 0.0213 (8) | 0.0184 (7) | 0.0289 (8) | 0.0013 (6) | 0.0072 (6) | −0.0008 (6) |
N24 | 0.0208 (7) | 0.0194 (7) | 0.0183 (7) | −0.0020 (6) | 0.0080 (6) | 0.0000 (6) |
O1 | 0.0267 (7) | 0.0265 (7) | 0.0204 (6) | −0.0052 (5) | 0.0042 (5) | −0.0075 (5) |
O2 | 0.0285 (7) | 0.0283 (7) | 0.0263 (7) | 0.0059 (6) | 0.0105 (6) | −0.0058 (6) |
S1 | 0.0234 (2) | 0.0255 (2) | 0.0329 (3) | −0.00412 (19) | 0.00939 (19) | −0.0022 (2) |
S2 | 0.0221 (2) | 0.0261 (3) | 0.0327 (3) | −0.00063 (19) | 0.00128 (19) | 0.0042 (2) |
C1—C2 | 1.518 (3) | C21—S2 | 1.819 (2) |
C1—S1 | 1.819 (2) | C21—H21A | 0.9900 |
C1—H1A | 0.9900 | C21—H21B | 0.9900 |
C1—H1B | 0.9900 | C22—N24 | 1.469 (2) |
C2—N4 | 1.468 (2) | C22—H22A | 0.9900 |
C2—H2A | 0.9900 | C22—H22B | 0.9900 |
C2—H2B | 0.9900 | C23—N22 | 1.297 (2) |
C3—N2 | 1.298 (2) | C23—N24 | 1.354 (2) |
C3—N4 | 1.354 (2) | C23—S2 | 1.7452 (18) |
C3—S1 | 1.7462 (18) | C25—O2 | 1.224 (2) |
C5—O1 | 1.221 (2) | C25—N24 | 1.382 (2) |
C5—N4 | 1.385 (2) | C25—C26 | 1.474 (2) |
C5—C6 | 1.477 (2) | C26—N21 | 1.311 (2) |
C6—N1 | 1.311 (2) | C26—C31 | 1.488 (2) |
C6—C11 | 1.488 (2) | C31—C36 | 1.403 (2) |
C11—C16 | 1.400 (2) | C31—C32 | 1.403 (3) |
C11—C12 | 1.408 (2) | C32—C33 | 1.385 (3) |
C12—C13 | 1.383 (3) | C32—H32 | 0.9500 |
C12—H12 | 0.9500 | C33—C34 | 1.385 (3) |
C13—C14 | 1.391 (3) | C33—H33 | 0.9500 |
C13—H13 | 0.9500 | C34—C35 | 1.384 (3) |
C14—C15 | 1.385 (3) | C34—H34 | 0.9500 |
C14—H14 | 0.9500 | C35—C36 | 1.390 (3) |
C15—C16 | 1.390 (3) | C35—H35 | 0.9500 |
C15—H15 | 0.9500 | C36—H36 | 0.9500 |
C16—H16 | 0.9500 | N1—N2 | 1.374 (2) |
C21—C22 | 1.496 (3) | N21—N22 | 1.375 (2) |
C2—C1—S1 | 108.52 (13) | N24—C22—C21 | 108.00 (16) |
C2—C1—H1A | 110.0 | N24—C22—H22A | 110.1 |
S1—C1—H1A | 110.0 | C21—C22—H22A | 110.1 |
C2—C1—H1B | 110.0 | N24—C22—H22B | 110.1 |
S1—C1—H1B | 110.0 | C21—C22—H22B | 110.1 |
H1A—C1—H1B | 108.4 | H22A—C22—H22B | 108.4 |
N4—C2—C1 | 108.11 (15) | N22—C23—N24 | 125.13 (16) |
N4—C2—H2A | 110.1 | N22—C23—S2 | 122.19 (14) |
C1—C2—H2A | 110.1 | N24—C23—S2 | 112.68 (13) |
N4—C2—H2B | 110.1 | O2—C25—N24 | 119.91 (16) |
C1—C2—H2B | 110.1 | O2—C25—C26 | 128.18 (16) |
H2A—C2—H2B | 108.4 | N24—C25—C26 | 111.91 (14) |
N2—C3—N4 | 125.33 (16) | N21—C26—C25 | 122.10 (16) |
N2—C3—S1 | 121.94 (13) | N21—C26—C31 | 116.03 (15) |
N4—C3—S1 | 112.73 (13) | C25—C26—C31 | 121.85 (15) |
O1—C5—N4 | 120.07 (16) | C36—C31—C32 | 118.28 (16) |
O1—C5—C6 | 128.26 (16) | C36—C31—C26 | 122.72 (16) |
N4—C5—C6 | 111.66 (14) | C32—C31—C26 | 118.97 (16) |
N1—C6—C5 | 122.25 (16) | C33—C32—C31 | 120.78 (18) |
N1—C6—C11 | 116.14 (15) | C33—C32—H32 | 119.6 |
C5—C6—C11 | 121.60 (15) | C31—C32—H32 | 119.6 |
C16—C11—C12 | 118.52 (16) | C32—C33—C34 | 120.39 (19) |
C16—C11—C6 | 122.74 (16) | C32—C33—H33 | 119.8 |
C12—C11—C6 | 118.72 (15) | C34—C33—H33 | 119.8 |
C13—C12—C11 | 120.45 (17) | C35—C34—C33 | 119.56 (18) |
C13—C12—H12 | 119.8 | C35—C34—H34 | 120.2 |
C11—C12—H12 | 119.8 | C33—C34—H34 | 120.2 |
C12—C13—C14 | 120.59 (17) | C34—C35—C36 | 120.72 (19) |
C12—C13—H13 | 119.7 | C34—C35—H35 | 119.6 |
C14—C13—H13 | 119.7 | C36—C35—H35 | 119.6 |
C15—C14—C13 | 119.37 (18) | C35—C36—C31 | 120.28 (18) |
C15—C14—H14 | 120.3 | C35—C36—H36 | 119.9 |
C13—C14—H14 | 120.3 | C31—C36—H36 | 119.9 |
C14—C15—C16 | 120.73 (17) | C6—N1—N2 | 122.47 (15) |
C14—C15—H15 | 119.6 | C3—N2—N1 | 116.35 (14) |
C16—C15—H15 | 119.6 | C3—N4—C5 | 121.87 (15) |
C15—C16—C11 | 120.34 (17) | C3—N4—C2 | 117.08 (15) |
C15—C16—H16 | 119.8 | C5—N4—C2 | 121.00 (14) |
C11—C16—H16 | 119.8 | C26—N21—N22 | 122.44 (15) |
C22—C21—S2 | 109.48 (15) | C23—N22—N21 | 116.45 (15) |
C22—C21—H21A | 109.8 | C23—N24—C25 | 121.85 (15) |
S2—C21—H21A | 109.8 | C23—N24—C22 | 117.10 (15) |
C22—C21—H21B | 109.8 | C25—N24—C22 | 121.03 (14) |
S2—C21—H21B | 109.8 | C3—S1—C1 | 92.33 (9) |
H21A—C21—H21B | 108.2 | C23—S2—C21 | 91.86 (9) |
S1—C1—C2—N4 | 11.09 (19) | C11—C6—N1—N2 | 177.55 (14) |
O1—C5—C6—N1 | −178.37 (17) | N4—C3—N2—N1 | 3.0 (3) |
N4—C5—C6—N1 | 1.6 (2) | S1—C3—N2—N1 | −176.36 (12) |
O1—C5—C6—C11 | 2.9 (3) | C6—N1—N2—C3 | −1.0 (2) |
N4—C5—C6—C11 | −177.11 (14) | N2—C3—N4—C5 | −2.6 (3) |
N1—C6—C11—C16 | 175.00 (16) | S1—C3—N4—C5 | 176.81 (12) |
C5—C6—C11—C16 | −6.2 (2) | N2—C3—N4—C2 | −179.91 (16) |
N1—C6—C11—C12 | −6.2 (2) | S1—C3—N4—C2 | −0.53 (19) |
C5—C6—C11—C12 | 172.59 (15) | O1—C5—N4—C3 | −179.86 (15) |
C16—C11—C12—C13 | 0.6 (2) | C6—C5—N4—C3 | 0.2 (2) |
C6—C11—C12—C13 | −178.27 (15) | O1—C5—N4—C2 | −2.6 (2) |
C11—C12—C13—C14 | −0.3 (3) | C6—C5—N4—C2 | 177.41 (14) |
C12—C13—C14—C15 | −0.3 (3) | C1—C2—N4—C3 | −7.2 (2) |
C13—C14—C15—C16 | 0.6 (3) | C1—C2—N4—C5 | 175.47 (16) |
C14—C15—C16—C11 | −0.2 (3) | C25—C26—N21—N22 | 2.0 (3) |
C12—C11—C16—C15 | −0.3 (2) | C31—C26—N21—N22 | −176.22 (14) |
C6—C11—C16—C15 | 178.48 (16) | N24—C23—N22—N21 | −3.5 (3) |
S2—C21—C22—N24 | −9.3 (2) | S2—C23—N22—N21 | 175.74 (12) |
O2—C25—C26—N21 | 176.96 (17) | C26—N21—N22—C23 | 1.4 (2) |
N24—C25—C26—N21 | −3.2 (2) | N22—C23—N24—C25 | 2.1 (3) |
O2—C25—C26—C31 | −5.0 (3) | S2—C23—N24—C25 | −177.25 (12) |
N24—C25—C26—C31 | 174.86 (14) | N22—C23—N24—C22 | −179.70 (17) |
N21—C26—C31—C36 | −176.93 (16) | S2—C23—N24—C22 | 0.97 (19) |
C25—C26—C31—C36 | 4.9 (3) | O2—C25—N24—C23 | −178.85 (16) |
N21—C26—C31—C32 | 5.2 (2) | C26—C25—N24—C23 | 1.3 (2) |
C25—C26—C31—C32 | −173.03 (16) | O2—C25—N24—C22 | 3.0 (2) |
C36—C31—C32—C33 | −0.2 (3) | C26—C25—N24—C22 | −176.83 (15) |
C26—C31—C32—C33 | 177.78 (16) | C21—C22—N24—C23 | 5.7 (2) |
C31—C32—C33—C34 | 0.1 (3) | C21—C22—N24—C25 | −176.11 (18) |
C32—C33—C34—C35 | 0.0 (3) | N2—C3—S1—C1 | −174.21 (16) |
C33—C34—C35—C36 | 0.0 (3) | N4—C3—S1—C1 | 6.39 (14) |
C34—C35—C36—C31 | −0.1 (3) | C2—C1—S1—C3 | −10.07 (15) |
C32—C31—C36—C35 | 0.2 (3) | N22—C23—S2—C21 | 174.95 (18) |
C26—C31—C36—C35 | −177.71 (16) | N24—C23—S2—C21 | −5.69 (15) |
C5—C6—N1—N2 | −1.2 (2) | C22—C21—S2—C23 | 8.69 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···N1i | 0.99 | 2.40 | 3.338 (2) | 158 |
C22—H22A···N21i | 0.99 | 2.40 | 3.325 (2) | 155 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C9H7N3OS | C11H9N3OS | C11H9N3OS |
Mr | 205.24 | 231.27 | 231.27 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21 | Monoclinic, P21/c |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 11.1891 (11), 7.4401 (7), 21.359 (2) | 8.1257 (4), 11.3239 (5), 11.3860 (5) | 21.627 (3), 8.1222 (10), 11.8888 (15) |
α, β, γ (°) | 90, 90, 90 | 90, 99.363 (1), 90 | 90, 104.638 (2), 90 |
V (Å3) | 1778.1 (3) | 1033.72 (8) | 2020.6 (4) |
Z | 8 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.29 | 0.30 |
Crystal size (mm) | 0.30 × 0.20 × 0.06 | 0.45 × 0.40 × 0.20 | 0.30 × 0.30 × 0.10 |
Data collection | |||
Diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.908, 0.981 | 0.880, 0.944 | 0.916, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9167, 2023, 1746 | 5756, 2992, 2939 | 10860, 4517, 3632 |
Rint | 0.021 | 0.014 | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.082, 1.07 | 0.024, 0.061, 1.04 | 0.040, 0.101, 1.03 |
No. of reflections | 2023 | 2992 | 4517 |
No. of parameters | 127 | 290 | 289 |
No. of restraints | 0 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.23 | 0.29, −0.20 | 0.56, −0.50 |
Absolute structure | ? | Flack & Bernardinelli (2000), 577 Friedel pairs | ? |
Absolute structure parameter | ? | 0.02 (7) | ? |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1i | 0.88 | 1.96 | 2.8307 (15) | 169 |
N2—H2···S1ii | 0.88 | 2.46 | 3.3166 (13) | 163 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1i | 0.99 | 2.50 | 3.183 (2) | 126 |
C13—H13···O1ii | 0.95 | 2.56 | 3.150 (2) | 120 |
C21—H21B···N24iii | 0.99 | 2.45 | 3.351 (2) | 151 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y+1/2, −z; (iii) −x+2, y−1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···N1i | 0.99 | 2.40 | 3.338 (2) | 158 |
C22—H22A···N21i | 0.99 | 2.40 | 3.325 (2) | 155 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
(I) | (II-a) | (II-b) | (III-a) | (III-b) | |
N1-N2 | 1.3603 (16) | 1.352 (2) | 1.3556 (19) | 1.374 (2) | 1.375 (2) |
N2-C3 | 1.3487 (18) | 1.347 (2) | 1.353 (2) | 1.298 (2) | 1.297 (2) |
C3-N4 | 1.3670 (17) | 1.303 (3) | 1.302 (2) | 1.354 (2) | 1.354 (2) |
N4-C5 | 1.3789 (17) | 1.390 (2) | 1.385 (2) | 1.385 (2) | 1.382 (2) |
C6-C5 | 1.4823 (19) | 1.493 (3) | 1.494 (2) | 1.477 (2) | 1.474 (2) |
C6-N1 | 1.3059 (17) | 1.303 (2) | 1.300 (2) | 1.311 (2) | 1.311 (2) |
C3-S1 | 1.6673 (14) | 1.7436 (17) | 1.7476 (17) | 1.7462 (18) | 1.7452 (18) |
C5-O1 | 1.2236 (17) | 1.219 (2) | 1.224 (2) | 1.221 (2) | 1.224 (2) |
The title compound, 6-phenyl-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-5-one, (I), was prepared as an intermediate in the synthesis of thioheterocyclic derivatives (Arndt et al., 1984; Nyitrai et al., 1967), which are used in the creation of biologically active reagents (Odds & Abbott, 1984; Boschelli et al., 1993). Because the base part of thioxotriazinone, i.e. 5-hydroxy-3-mercapto-1,2,4-triazine, in (I) is widely considered to be an active substituent of biomolecules (Fotouhi et al., 2008), information about its structure and intermolecular interactions is crucial for chemists and pharmacologists. While many synthetic studies have been reported, few crystal structure analyses of derivatives of thioxotriazinone are known. Only four reports of the methyl derivatives (Ferrari et al., 1995; Voutsas et al., 1978) and its coordination complexes (Ghassemzadeh et al., 2004, 2005) were found during a search of the Cambridge Structural Database (CSD, Version 5.30, November 2008; Allen, 2002). Thus, we hope that this paper, concerning the results of structural studies of the title compound, (I), and the reaction products, 6-phenyl-2,3-dihydro-7H-1,3-thiazolo[3,2-b][1,2,4]triazin-7-one, (II), and 3-phenyl-6,7-dihydro-4H-1,3-thiazolo[2,3-c][1,2,4]triazin-4-one, (III), will provide a good basis for understanding the intermolecular interactions and for designing further reactions.
Generally, two isomeric substances of thiazolotriazinone, 7H-thiazolo[3,2-b]-1,2,4-triazine-7-one and 4H-thiazolo[2,3-c]-1,2,4-triazine-4-one derivatives [analogues of (II) and (III), respectively], are obtained by the reaction of the respective dihalogenoalkanes and thioxotriazinones [analogues of (I)], which can be substituted by various alkyl, cycloalkyl, aryl, heteroaryl and benzyl groups. However, the isomers were mainly identified from the results of the synthetic approach and several spectroscopic studies. Only one crystallographic study has been carried out on the benzyl-substituted 7H-thiazolo[3,2-b]-1,2,4-triazin-7-one (Miyamoto et al., 1991). Thus, we considered that full characterization of the two isomers is essential to understand the difference in the molecular structures and the spectroscopic results. Therefore, the crystal structures of the starting compound, (I), and both of the phenyl-substituted isomers, (II) and (III), are now discussed, along with the results of the condensation reaction.
In the crystal structure of (I), the phenyl and heterocyclic rings in the molecule are not coplanar and the dihedral angle between the planes of the two rings defined by atoms N1—N2—C3—N4—C5—C6 and C11—C12—C13—C14—C15—C16 is 31.38 (4)° (Fig. 1). The bond lengths in the heterocyclic rings are given in Table 1. The N1—N2, N2—C3, C3—N4 and N4—C5 distances correspond with those predicted for the conjugated bond lengths between the single and double bonds, and the bond distances C6—C5 and C6—N1 are those for localized single and double bonds, respectively. The heterocyclic ring is planar and the r.m.s. deviation of the six ring atoms from the mean ring plane is 0.006 Å. In the crystal packing (Fig. 2), there are pairs of N—H···O hydrogen bonds that link the amino N4 atom in the reference molecule at (x, y, z), via atom H4, across a centre of inversion to the carbonyl O1 atom of the molecule at (-x, -y + 1, -z + 2) and vice versa, while pairs of N—H···S hydrogen bonds link the amino N2 atom, via atom H2, across a centre of inversion on the other side of the reference molecule to the thiocarbonyl S1 atom of the molecule at (-x + 1, -y + 1, -z + 2) and back again (Table 2). Accordingly, these interactions link the molecules of (I) into one-dimensional ribbons which propagate parallel to the [100] direction. The ribbons are crosslinked by two different intermolecular C—H···π(arene) interactions between the phenyl moieties of adjacent molecules: C12···Cg1iii = 3.4527 (15), H12···Cg1iii = 2.76 Å, C12—H12···Cg1iii = 130°, C15···Cg1iv = 3.5085 (16), H15···Cg1iv = 2.77 Å, C15—H15···Cg1iv = 135°, where Cg1 is the centroid of the phenyl ring [symmetry codes: (iii) -x + 1/2, y - 1/2, z, (iv) -x, y + 1/2, -z + 1.5].
The same hydrogen-bonded ribbons are also found in the methyl-substituted derivative (Ferrari et al., 1995). The overlay (Macrae et al., 2006) of the atoms of the thioheterocyclic rings of (I) and the methyl derivative shows the same structural characteristics (the r.m.s. deviation of the atoms is 0.03 Å), which indicates that the conformations of the thioheterocyclic rings are almost independent of the substitution of phenyl and methyl groups.
The reaction of (I) and 1,2-dibromoethane gave the thioheterocyclic compounds (II) and (III) in 52 and 19% yields, respectively. Both compounds were isolated by column chromatography and crystallized from 2-propanol. The greater yield of (II) compared with that of (III) is consistent with the previous report (Arndt et al., 1984), meaning that the acidity of the proton at N2—H2 is higher than that at N4–H4 in the starting compound, (I), because of the expanding π-conjugation of N2. According to this aspect, the N2—C3 bond length in (I) [1.3487 (18) Å] is slightly but significantly shorter than that of C3—N4 [1.3670 (17) Å].
The crystal structures of (II) and (III) each have two crystallographically independent molecules in the asymmetric unit. Here, only one of the symmetry-independent molecules of each structure, (IIa) and (IIIa), is shown in Fig. 3. Selected bond lengths in the heterocyclic rings are summarized in Table 1. The molecular structure of (IIa) in Fig. 3(a) shows that the lateral ethylene chain combines atoms N2 and S1 in a pseudo-eclipsed conformation; the torsion angle of S1—C1—C2—N2 is -28.20 (17)° and that of S2—C21—C22—N22 in (IIb) is 26.76 (16)°. The C3—N4 and C6—N1 bonds in the heterocyclic ring are double bonds and C5—C6 is a single bond. The planes of the phenyl and six-membered heterocyclic rings in the molecule are not coplanar and the dihedral angle between the planes of the two rings defined by atoms N1—N2—C3—N4—C5—C6 and C11—C12—C13—C14—C15—C16 in (IIa) is 26.17 (8)°, while the corresponding dihedral angle in molecule (IIb) is 44.25 (5)°. The molecular structure of (IIIa) in Fig. 3(b) shows that the lateral ethylene chain combines atoms N4 and S1 in an eclipsed conformation; the torsion angle of S1—C1—C2—N4 is 11.09 (19)° and that of S2—C21—C22—N24 in (IIIb) is -9.3 (2)°. The N2—C3 and C6—N1 bonds in the heterocyclic ring are double bonds and C5—C6 is a single bond. The phenyl and six-membered heterocyclic rings in the molecule are almost coplanar, as the dihedral angle between the planes of these rings in (IIIa) is 7.38 (10)° and that in (IIIb) is 7.81 (11)°. The molecules of (III) are overall much more planar than those of (II), being influenced by the crystal packing as discussed below. The five-membered rings, including the S atom and sp3 C atoms, in (III) are flatter than those in (II): the r.m.s. deviations of the ring atoms from their mean planes are are 0.1272 (IIa), 0.1256 (IIb), 0.0532 (IIIa), 0.0450 (IIIb) Å. The changes in the conformations of the heterocyclic six-membered ring in (I) upon the condensation reaction to give (II) and (III) have been analysed by superimposing the molecules and finding the best fit to the six ring atoms plus atoms O1 and S1. Because the average r.m.s. deviations of these atoms in the overlay between (I)/(IIa) [or (IIIa)] is smaller than that of (I)/(IIb) [or (IIIb)], the conformational difference after the reaction was estimated by using (IIa) and (IIIa) in Fig. 4. While the average r.m.s. deviations for (I)/(II) and (I)/(III) show high similarity, 0.07 Å, the differences in the positions of atoms N4, C3 and S1 in (II) and atoms N2, C3 and S1 in (III) are larger than those for the other atoms.
Characterization of the derivatives, (II) and (III), was also performed using IR, MS and NMR spectroscopies. In the IR spectra, the distinctive C═O band is observed at 1665 cm-1 for (II) and 1669 cm-1 for (III), the former being slightly shifted towards a lower wavenumber when compared with the latter. The difference in the C═O, N4—C5 and C5—C6 bond lengths for compounds (II) and (III) indicate that the double bond of (II) is more localized than that of (III). Because the π-conjugation is less expanded in (II) than in (III), the lower energy of the C═O stretching for (II) is consistent. Here, IR shifts between the phenyl-substituted derivatives were smaller than for the methyl- and ethyl-substituted derivatives (see Experimental), probably because the π-systems compensate the localization of the C═O double bonds. In the detailed analysis of the mass spectra fragments, the peak at m/z=128 was observed without the 'phenyl—C6—N1 unit (m/z=103)' for (II) and the peak at m/z=203 was observed without the 'ethylene unit (m/z=28)' for (III). These facts are also well related to the crystal structures. Because the C6—N1 bond length of (II) is shorter than that of (III) and the localized π-conjugation cannot expand to the N2 atoms, the fragment of m/z=103 was observed for (II). These differences were also observed for the methyl- and ethyl-substituted derivatives. Additionally, the heteronuclear multiple bond correlation (HMBC) of the two-dimensional NMR spectrum of (III) showed a correlation peak between C5 and H2, while no correlation was observed between C5 and the ethylene protons for (II).
The crystal packings of (II) and (III) are quite different, as shown in Figs. 5(a) and 5(b), respectively. In the crystal of (II), the planes of the condensed heterocyclic rings in (IIa) and (IIb) involve a significant offset of the centroids of the rings to give columnar arrangements of alternating (IIa) and (IIb) molecules along the a axis. The five-membered rings and the phenyl rings have face-to-face contact, but this does not appear to involve π···π stacking. The columns are linked by weak hydrogen bonds through C1—H1B···O1i, C13—H13···O1ii and C21—H21B···N24iii interactions (symmetry codes are as in Table 3). In the crystal packing of (III), however, the molecules associate pairwise between (IIIa)/(IIIa) or (IIIb)/(IIIb). These pairs of molecules clearly show intermolecular π···π stacking between the electron-rich phenyl ring and the electron-poor six-membered ring of centrosymmetrically related molecules. The shortest intermolecular atom-to-atom distances are 3.320 (2) (C3···C15ii), 3.332 (2) (C5···C11ii), 3.342 (2) (C25···C31iii) and 3.362 (2) Å (C26···C26iii), while the centroid···centroid distances between the rings containing atoms C3 and C15ii and between the rings containing atoms C25 and C31iii are 3.7000 (11) and 3.6689 (12) Å, respectively, with corresponding angles between the ring planes of 5.78 (8) and 7.33 (9)° [symmetry codes: (ii) -x + 1, -y + 1, -z +1; (iii) -x, -y + 1, -z]. The pairs are further linked by weak hydrogen bonds through C2—H2B···N1i and C22—H22A···N21i [symmetry code: (i) x, -y + 1/2, z + 1/2] (Table 4).
In conclusion, this study clearly characterizes two isomers of the phenyl-substituted thioheterocyclic triazine by means of crystal structure analyses and spectroscopic studies, and highlights the π-conjugation within the triazine ring of (II) and (III).