Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009904/cf6076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009904/cf6076Isup2.hkl |
CCDC reference: 170767
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.032
- wR factor = 0.090
- Data-to-parameter ratio = 8.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5465
Author response: This should involve additional measurements. But the diffraction data were collected in 1991. The results could not be published earlier because of pharmaceutical requirements related to the hypothetical activity of the product. And now I cannot retrieve the compound to recrystallize it and to complete the measurements. I think it should be well if this study could be published because it is a rare example with the nitrogen atom in the 5-position (see the comment section above), and most of the data-validation tests are good. |
Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5465 Proportion of unique data used 1.0000 Ratio reflections to parameters 8.4141
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was synthesized at the Laboratory of Medicinal Chemistry of Liège, according to the method of Kotovskaya et al. (1979). Cystals were obtained by slow evaporation of a methanol solution.
H atoms were constrained (included as riding atoms) except those on N4 and N11, which were refined, with isotropic displacement parameters fixed at 1.2Ueq of the parent atom.
Data collection: DIF4 (Stoe & Cie, 1987); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
C6H6N4O2S | Dx = 1.657 Mg m−3 |
Mr = 198.21 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, Pbca | Cell parameters from 34 reflections |
a = 9.7545 (6) Å | θ = 24.7–40.7° |
b = 12.0427 (9) Å | µ = 3.43 mm−1 |
c = 13.5242 (18) Å | T = 293 K |
V = 1588.7 (3) Å3 | Prism, colourless |
Z = 8 | 0.34 × 0.23 × 0.11 mm |
F(000) = 816 |
Stoe-Siemens AED four-circle diffractometer | 829 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 57.4°, θmin = 6.6° |
ω scans | h = 0→10 |
Absorption correction: ψ-scan (EMPIR; Stoe & Cie, 1987) | k = 0→13 |
Tmin = 0.388, Tmax = 0.704 | l = 0→14 |
1077 measured reflections | 2 standard reflections every 60 min |
1077 independent reflections | intensity decay: 3% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: H atoms were placed at standard calculated positions, except atoms H(N4) and H(N11), which were obtained from difference map. |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.7861P] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
1077 reflections | Δρmax = 0.26 e Å−3 |
128 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0043 (4) |
C6H6N4O2S | V = 1588.7 (3) Å3 |
Mr = 198.21 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 9.7545 (6) Å | µ = 3.43 mm−1 |
b = 12.0427 (9) Å | T = 293 K |
c = 13.5242 (18) Å | 0.34 × 0.23 × 0.11 mm |
Stoe-Siemens AED four-circle diffractometer | 829 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (EMPIR; Stoe & Cie, 1987) | Rint = 0.000 |
Tmin = 0.388, Tmax = 0.704 | θmax = 57.4° |
1077 measured reflections | 2 standard reflections every 60 min |
1077 independent reflections | intensity decay: 3% |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.26 e Å−3 |
1077 reflections | Δρmin = −0.23 e Å−3 |
128 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 | ||
S1 | 0.25128 (6) | 0.15663 (5) | 0.15784 (4) | 0.0349 (3) | |
N2 | 0.2634 (2) | 0.23379 (17) | 0.06191 (16) | 0.0375 (6) | |
C3 | 0.3872 (2) | 0.2671 (2) | 0.03169 (17) | 0.0342 (6) | |
N4 | 0.5058 (2) | 0.21512 (17) | 0.05706 (17) | 0.0365 (6) | |
H4 | 0.579 (3) | 0.233 (2) | 0.0290 (19) | 0.044* | |
C5 | 0.5073 (2) | 0.1097 (2) | 0.10053 (17) | 0.0327 (6) | |
N6 | 0.6239 (2) | 0.05258 (17) | 0.09079 (14) | 0.0362 (5) | |
C7 | 0.6238 (3) | −0.0509 (2) | 0.12950 (19) | 0.0390 (6) | |
H7 | 0.7044 | −0.0919 | 0.1255 | 0.047* | |
C8 | 0.5124 (3) | −0.0996 (2) | 0.17444 (19) | 0.0417 (7) | |
H8 | 0.5177 | −0.1717 | 0.1988 | 0.050* | |
C9 | 0.3936 (3) | −0.0398 (2) | 0.18253 (19) | 0.0399 (6) | |
H9 | 0.3158 | −0.0710 | 0.2110 | 0.048* | |
C10 | 0.3920 (3) | 0.06849 (19) | 0.14730 (17) | 0.0323 (6) | |
N11 | 0.3949 (3) | 0.35321 (18) | −0.02874 (18) | 0.0446 (6) | |
H111 | 0.316 (3) | 0.381 (2) | −0.044 (2) | 0.054* | |
H112 | 0.474 (3) | 0.369 (2) | −0.063 (2) | 0.054* | |
O1 | 0.12740 (19) | 0.09326 (15) | 0.14953 (14) | 0.0489 (5) | |
O2 | 0.26608 (18) | 0.21993 (15) | 0.24652 (13) | 0.0471 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0324 (4) | 0.0353 (4) | 0.0369 (4) | 0.0001 (3) | 0.0012 (3) | 0.0056 (3) |
N2 | 0.0336 (11) | 0.0383 (12) | 0.0406 (12) | 0.0034 (10) | 0.0021 (10) | 0.0110 (10) |
C3 | 0.0324 (13) | 0.0344 (13) | 0.0357 (13) | 0.0016 (12) | −0.0001 (11) | 0.0011 (12) |
N4 | 0.0325 (12) | 0.0343 (12) | 0.0426 (13) | −0.0029 (9) | 0.0013 (10) | 0.0065 (11) |
C5 | 0.0356 (14) | 0.0319 (14) | 0.0306 (13) | −0.0020 (11) | −0.0055 (11) | −0.0037 (11) |
N6 | 0.0351 (12) | 0.0366 (12) | 0.0368 (13) | 0.0026 (10) | −0.0053 (9) | −0.0015 (9) |
C7 | 0.0438 (15) | 0.0353 (14) | 0.0379 (14) | 0.0095 (13) | −0.0095 (12) | −0.0052 (11) |
C8 | 0.0500 (17) | 0.0325 (14) | 0.0425 (15) | 0.0005 (12) | −0.0039 (13) | 0.0014 (12) |
C9 | 0.0431 (15) | 0.0353 (13) | 0.0411 (15) | −0.0029 (13) | −0.0004 (12) | 0.0067 (12) |
C10 | 0.0338 (14) | 0.0322 (13) | 0.0311 (13) | −0.0012 (11) | −0.0036 (10) | −0.0020 (10) |
N11 | 0.0356 (13) | 0.0431 (14) | 0.0552 (15) | 0.0048 (11) | 0.0055 (11) | 0.0190 (11) |
O1 | 0.0344 (10) | 0.0504 (11) | 0.0620 (13) | −0.0066 (9) | −0.0048 (8) | 0.0180 (9) |
O2 | 0.0537 (11) | 0.0494 (10) | 0.0382 (10) | 0.0061 (9) | 0.0043 (9) | −0.0031 (10) |
S1—O2 | 1.4285 (19) | C5—C10 | 1.382 (3) |
S1—O1 | 1.4336 (19) | N6—C7 | 1.351 (3) |
S1—N2 | 1.600 (2) | C7—C8 | 1.377 (4) |
S1—C10 | 1.741 (2) | C7—H7 | 0.930 |
N2—C3 | 1.336 (3) | C8—C9 | 1.369 (4) |
C3—N11 | 1.323 (3) | C8—H8 | 0.930 |
C3—N4 | 1.359 (3) | C9—C10 | 1.389 (4) |
N4—C5 | 1.399 (3) | C9—H9 | 0.930 |
N4—H4 | 0.84 (3) | N11—H111 | 0.86 (3) |
C5—N6 | 1.335 (3) | N11—H112 | 0.92 (3) |
O2—S1—O1 | 115.79 (12) | C5—N6—C7 | 115.9 (2) |
O2—S1—N2 | 111.31 (12) | N6—C7—C8 | 124.4 (2) |
O1—S1—N2 | 107.94 (11) | N6—C7—H7 | 117.8 |
O2—S1—C10 | 108.32 (11) | C8—C7—H7 | 117.8 |
O1—S1—C10 | 109.49 (12) | C9—C8—C7 | 118.6 (2) |
N2—S1—C10 | 103.25 (11) | C9—C8—H8 | 120.7 |
C3—N2—S1 | 119.27 (16) | C7—C8—H8 | 120.7 |
N11—C3—N2 | 118.4 (2) | C8—C9—C10 | 118.5 (2) |
N11—C3—N4 | 117.9 (2) | C8—C9—H9 | 120.8 |
N2—C3—N4 | 123.6 (2) | C10—C9—H9 | 120.8 |
C3—N4—C5 | 122.2 (2) | C5—C10—C9 | 119.0 (2) |
C3—N4—H4 | 119.4 (19) | C5—C10—S1 | 117.40 (18) |
C5—N4—H4 | 115 (2) | C9—C10—S1 | 123.6 (2) |
N6—C5—C10 | 123.6 (2) | C3—N11—H111 | 114 (2) |
N6—C5—N4 | 115.8 (2) | C3—N11—H112 | 121.3 (19) |
C10—C5—N4 | 120.6 (2) | H111—N11—H112 | 123 (3) |
O2—S1—N2—C3 | 77.8 (2) | C7—C8—C9—C10 | −1.7 (4) |
O1—S1—N2—C3 | −154.1 (2) | N6—C5—C10—C9 | −3.1 (4) |
C10—S1—N2—C3 | −38.2 (2) | N4—C5—C10—C9 | 174.8 (2) |
S1—N2—C3—N11 | −161.57 (19) | N6—C5—C10—S1 | 177.35 (18) |
S1—N2—C3—N4 | 20.6 (3) | N4—C5—C10—S1 | −4.8 (3) |
N11—C3—N4—C5 | −164.7 (2) | C8—C9—C10—C5 | 3.6 (4) |
N2—C3—N4—C5 | 13.2 (4) | C8—C9—C10—S1 | −176.82 (19) |
C3—N4—C5—N6 | 157.7 (2) | O2—S1—C10—C5 | −87.7 (2) |
C3—N4—C5—C10 | −20.3 (4) | O1—S1—C10—C5 | 145.21 (19) |
C10—C5—N6—C7 | 0.3 (3) | N2—S1—C10—C5 | 30.4 (2) |
N4—C5—N6—C7 | −177.6 (2) | O2—S1—C10—C9 | 92.8 (2) |
C5—N6—C7—C8 | 1.8 (4) | O1—S1—C10—C9 | −34.4 (2) |
N6—C7—C8—C9 | −1.1 (4) | N2—S1—C10—C9 | −149.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N2i | 0.84 (3) | 2.22 (3) | 3.047 (3) | 172 (3) |
N11—H112···O1i | 0.92 (3) | 1.96 (3) | 2.868 (3) | 173 (3) |
N11—H111···N6ii | 0.86 (3) | 2.13 (3) | 2.997 (3) | 177 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C6H6N4O2S |
Mr | 198.21 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 9.7545 (6), 12.0427 (9), 13.5242 (18) |
V (Å3) | 1588.7 (3) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 3.43 |
Crystal size (mm) | 0.34 × 0.23 × 0.11 |
Data collection | |
Diffractometer | Stoe-Siemens AED four-circle diffractometer |
Absorption correction | ψ-scan (EMPIR; Stoe & Cie, 1987) |
Tmin, Tmax | 0.388, 0.704 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1077, 1077, 829 |
Rint | 0.000 |
θmax (°) | 57.4 |
(sin θ/λ)max (Å−1) | 0.546 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.090, 0.96 |
No. of reflections | 1077 |
No. of parameters | 128 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.23 |
Computer programs: DIF4 (Stoe & Cie, 1987), DIF4, REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N2i | 0.84 (3) | 2.22 (3) | 3.047 (3) | 172 (3) |
N11—H112···O1i | 0.92 (3) | 1.96 (3) | 2.868 (3) | 173 (3) |
N11—H111···N6ii | 0.86 (3) | 2.13 (3) | 2.997 (3) | 177 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z. |
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Although most of the published X-ray data on pyridothiadiazine dioxides are related to compounds with the pyridinic nitrogen in the 7-position of the pyridothiadiazine ring, this example, (I), of a compound with the N atom in the 5-position will complete our information on the influence of this position on the tautomeric behavior of pyridothiadiazine dioxides. It confirms the predominance of the 4H-tautomeric form. These results may help to establish in such molecules which are the important chemical and geometrical parameters required (pharmacophore) for their biological activity.