4,6-Dimethoxy-3-methyl-1,3,5-triazine-2(3H)-thione crystallizes in two polymorphic forms, needles and plates. In the needle-shaped crystals (9a) the molecules occupy the crystallographic mirror plane, thus the layers are stacked along the b axis. The molecules of the other polymorph [plate-shape crystals, (9b)] are packed in a herringbone packing mode. Upon heating, (9b) undergoes a phase transition to form (9a). At 378 K the needles undergo O → S topochemically controlled methyl transfer in the solid state to produce 1-methyl-4-methoxy-6-methylthio-1,3,5-triazine-2(1H)-one in 75% yield. The enthalpy of the rearrangement is estimated to be −39.1 kJ mol−1. 1-Methyl-6-methoxy-4-methylthio-1,3,5-triazine-2(1H)-thione crystallizes in space group P21 with two crystallographically independent molecules in the asymmetric unit. Compound (9b) undergoes O → S methyl transfer in the solid state at 373 K. The rearrangement is topochemically assisted and the product, 1-methyl-2,4-bismethylthio-1,3,5-triazine-6(1H)-one, is obtained in quantitative yield. The enthalpy of the rearrangement is estimated to be −58.8 kJ mol−1. The crystal structures of the compounds as well as their DSC thermographs are described and discussed. Energy calculation by ab initio methods shows that the driving force for the reactions is the difference between the molecular energies of the pre-rearranged compounds and their products, 54.2 and 59.3 kJ mol−1 in the two cases, respectively.
Supporting information
CCDC references: 166530; 166531; 166532; 166533
Data collection: Philips PW 1100/20 (Philips, 1973) for (9a), (12); Philips PW 110/20 (Philips, 1973) for (9b); SMART V.4.209 (Siemens, 1995) for (11). Cell refinement: Philips PW 1100/20 (Philips, 1973) for (9a), (12); Philips PW 110/20 (Philips, 1973) for (9b); SAINT V.4.050 (Siemens, 1995) for (11). Data reduction: Philips PW 1100/20 (Philips, 1973) for (9a), (12); Philips PW 110/20 (Philips, 1973) for (9b); SAINT V.4.050 (Siemens, 1995) for (11). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (9a); SHELXS97 (Sheldrick, 1997) for (9b), (11), (12). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997). Software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) for (9a), (9b), (11).
(9a) 4,6-Dimethoxy-3-methyl-1,3,5-triazine-2(3
H)-thione
top
Crystal data top
C6H9N3O2S | F(000) = 392 |
Mr = 187.22 | Dx = 1.396 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 20 reflections |
a = 15.231 (5) Å | θ = 7.2–19.5° |
b = 6.778 (3) Å | µ = 0.33 mm−1 |
c = 8.626 (3) Å | T = 293 K |
V = 890.5 (6) Å3 | Needle, light yellow |
Z = 4 | 0.33 × 0.27 × 0.19 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.055 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.7° |
Graphite monochromator | h = −4→18 |
ω/2θ scans | k = 0→8 |
981 measured reflections | l = −4→10 |
857 independent reflections | 3 standard reflections every 120 min. min |
560 reflections with I > 2σ(I) | intensity decay: 4.2% |
Refinement top
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.2249P] where P = (Fo2 + 2Fc2)/3 |
857 reflections | (Δ/σ)max < 0.001 |
84 parameters | Δρmax = 0.20 e Å−3 |
6 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C6H9N3O2S | V = 890.5 (6) Å3 |
Mr = 187.22 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 15.231 (5) Å | µ = 0.33 mm−1 |
b = 6.778 (3) Å | T = 293 K |
c = 8.626 (3) Å | 0.33 × 0.27 × 0.19 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.055 |
981 measured reflections | 3 standard reflections every 120 min. min |
857 independent reflections | intensity decay: 4.2% |
560 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.061 | 6 restraints |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.20 e Å−3 |
857 reflections | Δρmin = −0.36 e Å−3 |
84 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.56102 (10) | 0.2500 | 0.63092 (18) | 0.0695 (6) | |
O1 | 0.2548 (2) | 0.2500 | 0.4603 (4) | 0.0762 (13) | |
O2 | 0.4658 (3) | 0.2500 | 0.0876 (4) | 0.0762 (13) | |
N1 | 0.3977 (3) | 0.2500 | 0.5394 (4) | 0.0484 (11) | |
N2 | 0.3543 (3) | 0.2500 | 0.2733 (4) | 0.0581 (12) | |
N3 | 0.5038 (3) | 0.2500 | 0.3413 (5) | 0.0514 (11) | |
C1 | 0.4835 (3) | 0.2500 | 0.5007 (6) | 0.0452 (12) | |
C2 | 0.3408 (3) | 0.2500 | 0.4282 (6) | 0.0533 (14) | |
C3 | 0.4376 (4) | 0.2500 | 0.2391 (6) | 0.0583 (14) | |
C4 | 0.2304 (5) | 0.2500 | 0.6214 (8) | 0.092 (2) | |
C5 | 0.3937 (7) | 0.2500 | −0.0280 (7) | 0.110 (3) | |
C6 | 0.5966 (4) | 0.2500 | 0.2931 (8) | 0.082 (2) | |
H4A | 0.253 (3) | 0.134 (8) | 0.672 (6) | 0.138* | |
H4B | 0.1681 (14) | 0.2500 | 0.626 (9) | 0.138* | |
H5A | 0.427 (3) | 0.2500 | −0.124 (3) | 0.165* | |
H5B | 0.363 (3) | 0.372 (5) | −0.011 (4) | 0.165* | |
H6A | 0.6168 | 0.1165 | 0.2830 | 0.124* | 0.50 |
H6B | 0.6312 | 0.3172 | 0.3696 | 0.124* | 0.50 |
H6C | 0.6022 | 0.3163 | 0.1952 | 0.124* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0659 (10) | 0.0652 (10) | 0.0774 (11) | 0.000 | −0.0211 (9) | 0.000 |
O1 | 0.044 (2) | 0.121 (4) | 0.064 (2) | 0.000 | −0.001 (2) | 0.000 |
O2 | 0.120 (4) | 0.071 (3) | 0.0378 (19) | 0.000 | 0.012 (2) | 0.000 |
N1 | 0.051 (3) | 0.054 (3) | 0.040 (2) | 0.000 | −0.001 (2) | 0.000 |
N2 | 0.069 (3) | 0.068 (3) | 0.038 (2) | 0.000 | −0.004 (2) | 0.000 |
N3 | 0.055 (3) | 0.047 (3) | 0.052 (3) | 0.000 | 0.016 (2) | 0.000 |
C1 | 0.043 (3) | 0.038 (3) | 0.054 (3) | 0.000 | 0.002 (2) | 0.000 |
C2 | 0.061 (4) | 0.057 (3) | 0.042 (3) | 0.000 | 0.008 (3) | 0.000 |
C3 | 0.088 (4) | 0.049 (3) | 0.037 (3) | 0.000 | 0.009 (3) | 0.000 |
C4 | 0.058 (4) | 0.141 (7) | 0.075 (4) | 0.000 | 0.025 (4) | 0.000 |
C5 | 0.178 (9) | 0.117 (7) | 0.035 (3) | 0.000 | −0.008 (4) | 0.000 |
C6 | 0.069 (4) | 0.081 (4) | 0.097 (5) | 0.000 | 0.039 (4) | 0.000 |
Geometric parameters (Å, º) top
S1—C1 | 1.630 (5) | N3—C1 | 1.409 (6) |
O1—C2 | 1.338 (6) | N3—C6 | 1.474 (7) |
O1—C4 | 1.439 (8) | C4—H4A | 0.96 (5) |
O2—C3 | 1.376 (6) | C4—H4B | 0.95 (2) |
O2—C5 | 1.484 (9) | C5—H5A | 0.973 (19) |
N1—C2 | 1.293 (6) | C5—H5B | 0.963 (18) |
N1—C1 | 1.349 (6) | C6—H6A | 0.9600 |
N2—C3 | 1.303 (7) | C6—H6B | 0.9600 |
N2—C2 | 1.352 (6) | C6—H6C | 0.9600 |
N3—C3 | 1.339 (7) | | |
| | | |
C2—O1—C4 | 116.9 (5) | N2—C3—O2 | 121.3 (5) |
C3—O2—C5 | 114.0 (5) | N3—C3—O2 | 113.0 (5) |
C2—N1—C1 | 117.7 (4) | O1—C4—H4A | 110 (3) |
C3—N2—C2 | 111.9 (4) | O1—C4—H4B | 108 (5) |
C3—N3—C1 | 118.5 (4) | H4A—C4—H4B | 110 (4) |
C3—N3—C6 | 122.4 (5) | O2—C5—H5A | 100 (3) |
C1—N3—C6 | 119.1 (5) | O2—C5—H5B | 105 (3) |
N1—C1—N3 | 117.0 (4) | H5A—C5—H5B | 113 (3) |
N1—C1—S1 | 122.1 (4) | N3—C6—H6A | 109.5 |
N3—C1—S1 | 120.9 (4) | N3—C6—H6B | 109.5 |
N1—C2—O1 | 120.2 (4) | H6A—C6—H6B | 109.5 |
N1—C2—N2 | 129.2 (5) | N3—C6—H6C | 109.5 |
O1—C2—N2 | 110.7 (5) | H6A—C6—H6C | 109.5 |
N2—C3—N3 | 125.7 (4) | H6B—C6—H6C | 109.5 |
| | | |
C2—N1—C1—N3 | 0.0 | C3—N2—C2—N1 | 0.0 |
C2—N1—C1—S1 | 180.0 | C3—N2—C2—O1 | 180.0 |
C3—N3—C1—N1 | 0.0 | C2—N2—C3—N3 | 0.0 |
C6—N3—C1—N1 | 180.0 | C2—N2—C3—O2 | 180.0 |
C3—N3—C1—S1 | 180.0 | C1—N3—C3—N2 | 0.0 |
C6—N3—C1—S1 | 0.0 | C6—N3—C3—N2 | 180.0 |
C1—N1—C2—O1 | 180.0 | C1—N3—C3—O2 | 180.0 |
C1—N1—C2—N2 | 0.0 | C6—N3—C3—O2 | 0.0 |
C4—O1—C2—N1 | 0.0 | C5—O2—C3—N2 | 0.0 |
C4—O1—C2—N2 | 180.0 | C5—O2—C3—N3 | 180.0 |
(9b) 4,6-Dimethoxy-3-methyl-1,3,5-triazine-2(3
H)-thion
top
Crystal data top
C6H9N3O2S | F(000) = 392 |
Mr = 187.22 | Dx = 1.436 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
a = 7.657 (3) Å | Cell parameters from 25 reflections |
b = 14.361 (7) Å | θ = 2.9–12.7° |
c = 8.433 (4) Å | µ = 0.34 mm−1 |
β = 110.99 (3)° | T = 293 K |
V = 865.8 (7) Å3 | Plates, light yellow |
Z = 4 | 0.45 × 0.38 × 0.24 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.091 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.8° |
Graphite monochromator | h = −9→9 |
ω/2θ scans | k = 0→16 |
1730 measured reflections | l = −10→9 |
1520 independent reflections | 3 standard reflections every 120 min min |
902 reflections with I > 2σ(I) | intensity decay: 4.0% |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0325P)2 + 2.0096P] where P = (Fo2 + 2Fc2)/3 |
1520 reflections | (Δ/σ)max < 0.001 |
112 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C6H9N3O2S | V = 865.8 (7) Å3 |
Mr = 187.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.657 (3) Å | µ = 0.34 mm−1 |
b = 14.361 (7) Å | T = 293 K |
c = 8.433 (4) Å | 0.45 × 0.38 × 0.24 mm |
β = 110.99 (3)° | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.091 |
1730 measured reflections | 3 standard reflections every 120 min min |
1520 independent reflections | intensity decay: 4.0% |
902 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.37 e Å−3 |
1520 reflections | Δρmin = −0.36 e Å−3 |
112 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.65350 (18) | 0.12203 (8) | 0.20454 (15) | 0.0449 (4) | |
O1 | 0.9234 (5) | −0.17846 (19) | 0.1274 (4) | 0.0416 (8) | |
O2 | 0.7225 (4) | 0.0157 (2) | −0.3240 (3) | 0.0417 (8) | |
N1 | 0.7932 (5) | −0.0396 (2) | 0.1616 (4) | 0.0323 (8) | |
N2 | 0.8312 (5) | −0.0847 (2) | −0.0980 (4) | 0.0343 (8) | |
N3 | 0.6989 (5) | 0.0607 (2) | −0.0761 (4) | 0.0334 (8) | |
C1 | 0.7182 (6) | 0.0433 (3) | 0.0925 (5) | 0.0304 (9) | |
C2 | 0.8461 (6) | −0.0965 (3) | 0.0652 (5) | 0.0334 (10) | |
C3 | 0.7529 (6) | −0.0061 (3) | −0.1635 (5) | 0.0332 (10) | |
C4 | 0.9514 (7) | −0.1985 (3) | 0.3029 (5) | 0.0464 (12) | |
C5 | 0.7756 (8) | −0.0555 (4) | −0.4234 (6) | 0.0521 (13) | |
C6 | 0.6206 (7) | 0.1495 (3) | −0.1590 (6) | 0.0444 (12) | |
H4A | 1.0239 | −0.1496 | 0.3739 | 0.070* | |
H4B | 1.0166 | −0.2566 | 0.3350 | 0.070* | |
H4C | 0.8323 | −0.2026 | 0.3162 | 0.070* | |
H5A | 0.9058 | −0.0703 | −0.3689 | 0.078* | |
H5B | 0.7539 | −0.0322 | −0.5355 | 0.078* | |
H5C | 0.7020 | −0.1105 | −0.4307 | 0.078* | |
H6A | 0.6170 | 0.1491 | −0.2740 | 0.067* | |
H6B | 0.6977 | 0.2000 | −0.0983 | 0.067* | |
H6C | 0.4962 | 0.1571 | −0.1587 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0576 (8) | 0.0325 (6) | 0.0474 (7) | 0.0010 (6) | 0.0220 (6) | −0.0064 (5) |
C1 | 0.029 (2) | 0.030 (2) | 0.030 (2) | −0.0070 (17) | 0.0084 (18) | −0.0033 (17) |
C2 | 0.035 (2) | 0.033 (2) | 0.031 (2) | 0.0013 (18) | 0.0095 (19) | 0.0051 (17) |
C3 | 0.036 (2) | 0.031 (2) | 0.029 (2) | −0.0038 (19) | 0.0066 (18) | 0.0037 (17) |
C4 | 0.066 (3) | 0.038 (2) | 0.035 (3) | 0.012 (2) | 0.018 (2) | 0.012 (2) |
C5 | 0.068 (4) | 0.062 (3) | 0.025 (2) | 0.004 (3) | 0.015 (2) | −0.001 (2) |
C6 | 0.055 (3) | 0.029 (2) | 0.045 (3) | 0.004 (2) | 0.013 (2) | 0.0090 (19) |
N1 | 0.039 (2) | 0.0274 (18) | 0.0293 (18) | 0.0008 (15) | 0.0103 (16) | 0.0015 (14) |
N2 | 0.043 (2) | 0.0300 (17) | 0.0287 (18) | −0.0010 (16) | 0.0109 (16) | −0.0010 (15) |
N3 | 0.037 (2) | 0.0246 (17) | 0.036 (2) | −0.0015 (15) | 0.0104 (16) | 0.0039 (14) |
O1 | 0.061 (2) | 0.0325 (16) | 0.0316 (16) | 0.0079 (14) | 0.0164 (15) | 0.0058 (13) |
O2 | 0.0493 (19) | 0.0486 (18) | 0.0267 (16) | 0.0000 (15) | 0.0130 (14) | 0.0038 (13) |
Geometric parameters (Å, º) top
S—C1 | 1.659 (4) | C6—N3 | 1.474 (5) |
C1—N1 | 1.360 (5) | C4—H4A | 0.9600 |
C1—N3 | 1.398 (5) | C4—H4B | 0.9600 |
C2—N1 | 1.315 (5) | C4—H4C | 0.9600 |
C2—O1 | 1.338 (5) | C5—H5A | 0.9600 |
C2—N2 | 1.350 (5) | C5—H5B | 0.9600 |
C3—N2 | 1.305 (5) | C5—H5C | 0.9600 |
C3—O2 | 1.326 (5) | C6—H6A | 0.9600 |
C3—N3 | 1.362 (5) | C6—H6B | 0.9600 |
C4—O1 | 1.446 (5) | C6—H6C | 0.9600 |
C5—O2 | 1.469 (5) | | |
| | | |
N1—C1—N3 | 117.8 (4) | O1—C4—H4B | 109.5 |
N1—C1—S | 121.3 (3) | H4A—C4—H4B | 109.5 |
N3—C1—S | 120.9 (3) | O1—C4—H4C | 109.5 |
N1—C2—O1 | 119.7 (3) | H4A—C4—H4C | 109.5 |
N1—C2—N2 | 128.4 (4) | H4B—C4—H4C | 109.5 |
O1—C2—N2 | 112.0 (4) | O2—C5—H5A | 109.5 |
N2—C3—O2 | 121.6 (4) | O2—C5—H5B | 109.5 |
N2—C3—N3 | 124.3 (4) | H5A—C5—H5B | 109.5 |
O2—C3—N3 | 114.1 (3) | O2—C5—H5C | 109.5 |
C2—N1—C1 | 117.1 (3) | H5A—C5—H5C | 109.5 |
C3—N2—C2 | 113.5 (4) | H5B—C5—H5C | 109.5 |
C3—N3—C1 | 118.9 (3) | N3—C6—H6A | 109.5 |
C3—N3—C6 | 120.3 (3) | N3—C6—H6B | 109.5 |
C1—N3—C6 | 120.9 (3) | H6A—C6—H6B | 109.5 |
C2—O1—C4 | 117.3 (3) | N3—C6—H6C | 109.5 |
C3—O2—C5 | 115.7 (3) | H6A—C6—H6C | 109.5 |
O1—C4—H4A | 109.5 | H6B—C6—H6C | 109.5 |
| | | |
O1—C2—N1—C1 | 179.0 (4) | N2—C3—N3—C6 | 176.7 (4) |
N2—C2—N1—C1 | −2.0 (6) | O2—C3—N3—C6 | −2.0 (6) |
N3—C1—N1—C2 | 1.6 (5) | N1—C1—N3—C3 | 1.0 (5) |
S—C1—N1—C2 | −177.8 (3) | S—C1—N3—C3 | −179.6 (3) |
O2—C3—N2—C2 | −178.1 (4) | N1—C1—N3—C6 | −179.4 (4) |
N3—C3—N2—C2 | 3.2 (6) | S—C1—N3—C6 | 0.0 (5) |
N1—C2—N2—C3 | −0.3 (6) | N1—C2—O1—C4 | −2.4 (6) |
O1—C2—N2—C3 | 178.8 (4) | N2—C2—O1—C4 | 178.5 (4) |
N2—C3—N3—C1 | −3.6 (6) | N2—C3—O2—C5 | 2.3 (6) |
O2—C3—N3—C1 | 177.6 (3) | N3—C3—O2—C5 | −178.8 (4) |
(11) 1-Methyl-6-methoxy-4-methlthio-1,3,5-triazine-2(1
H)-thione
top
Crystal data top
C6H9N3OS2 | F(000) = 424 |
Mr = 203.28 | Dx = 1.454 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7771 (8) Å | Cell parameters from 2592 reflections |
b = 7.9991 (7) Å | θ = 3.9–24.4° |
c = 14.9762 (16) Å | µ = 0.53 mm−1 |
β = 94.629 (1)° | T = 300 K |
V = 928.63 (16) Å3 | Plate, light yellow |
Z = 4 | 0.40 × 0.30 × 0.25 mm |
Data collection top
Siemens SMART diffractometer | 2629 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 28.3°, θmin = 3.6° |
ω scans | h = −10→10 |
10006 measured reflections | k = −5→6 |
3203 independent reflections | l = −19→13 |
Refinement top
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)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0803P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3203 reflections | Δρmax = 0.64 e Å−3 |
217 parameters | Δρmin = −0.23 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.12 (9) |
Crystal data top
C6H9N3OS2 | V = 928.63 (16) Å3 |
Mr = 203.28 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.7771 (8) Å | µ = 0.53 mm−1 |
b = 7.9991 (7) Å | T = 300 K |
c = 14.9762 (16) Å | 0.40 × 0.30 × 0.25 mm |
β = 94.629 (1)° | |
Data collection top
Siemens SMART diffractometer | 2629 reflections with I > 2σ(I) |
10006 measured reflections | Rint = 0.025 |
3203 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.120 | Δρmax = 0.64 e Å−3 |
S = 1.05 | Δρmin = −0.23 e Å−3 |
3203 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
217 parameters | Absolute structure parameter: −0.12 (9) |
1 restraint | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1A | 1.07894 (10) | 0.20171 (15) | 0.77050 (6) | 0.0617 (3) | |
S2A | 0.56969 (12) | 0.52285 (17) | 0.91255 (5) | 0.0729 (4) | |
O1A | 0.5677 (3) | 0.3946 (4) | 0.59231 (13) | 0.0652 (9) | |
N1A | 0.5821 (3) | 0.4572 (4) | 0.73866 (16) | 0.0507 (9) | |
N2A | 0.8181 (3) | 0.3675 (5) | 0.83596 (16) | 0.0544 (9) | |
N3A | 0.8066 (3) | 0.3066 (4) | 0.67956 (16) | 0.0541 (9) | |
C1A | 0.6589 (4) | 0.3820 (6) | 0.67047 (19) | 0.0511 (10) | |
C2A | 0.6628 (4) | 0.4452 (5) | 0.8254 (2) | 0.0522 (11) | |
C3A | 0.8805 (4) | 0.3044 (5) | 0.7640 (2) | 0.0469 (9) | |
C4A | 0.6371 (5) | 0.3030 (8) | 0.5186 (2) | 0.0875 (17) | |
C5A | 0.4123 (4) | 0.5381 (6) | 0.7206 (2) | 0.0682 (13) | |
C6A | 1.1547 (5) | 0.2236 (7) | 0.8857 (2) | 0.0765 (13) | |
H4AA | 0.7479 | 0.3479 | 0.5075 | 0.131* | |
H4AB | 0.5599 | 0.3141 | 0.4656 | 0.131* | |
H4AC | 0.6491 | 0.1870 | 0.5342 | 0.131* | |
H5AA | 0.4047 | 0.5867 | 0.6618 | 0.102* | |
H5AB | 0.3988 | 0.6240 | 0.7643 | 0.102* | |
H5AC | 0.3228 | 0.4562 | 0.7240 | 0.102* | |
H6AA | 1.0816 | 0.3001 | 0.9144 | 0.115* | |
H6AB | 1.2706 | 0.2659 | 0.8899 | 0.115* | |
H6AC | 1.1528 | 0.1167 | 0.9147 | 0.115* | |
S1B | 0.02702 (12) | 0.19521 (18) | 0.41605 (6) | 0.0737 (4) | |
S2B | 0.54698 (11) | 0.51916 (16) | 0.28721 (6) | 0.0691 (4) | |
O1B | 0.0399 (3) | 0.3255 (4) | 0.09984 (13) | 0.0643 (9) | |
N1B | 0.2701 (3) | 0.4066 (4) | 0.18966 (15) | 0.0497 (8) | |
N2B | 0.2820 (3) | 0.3578 (4) | 0.34536 (16) | 0.0526 (9) | |
N3B | 0.0444 (3) | 0.2588 (4) | 0.24900 (16) | 0.0538 (10) | |
C1B | 0.1145 (4) | 0.3264 (5) | 0.1825 (2) | 0.0519 (10) | |
C2B | 0.3568 (3) | 0.4227 (6) | 0.2736 (2) | 0.0504 (10) | |
C3B | 0.1331 (4) | 0.2806 (5) | 0.32915 (19) | 0.0490 (10) | |
C4B | −0.1303 (5) | 0.2442 (8) | 0.0893 (3) | 0.0926 (17) | |
C5B | 0.3435 (4) | 0.4727 (6) | 0.1089 (2) | 0.0629 (12) | |
C6B | 0.1622 (6) | 0.2506 (9) | 0.5140 (2) | 0.0941 (18) | |
H4BA | −0.1155 | 0.1252 | 0.0859 | 0.139* | |
H4BB | −0.1925 | 0.2833 | 0.0353 | 0.139* | |
H4BC | −0.1940 | 0.2709 | 0.1397 | 0.139* | |
H5BA | 0.4430 | 0.4081 | 0.0968 | 0.094* | |
H5BB | 0.3764 | 0.5873 | 0.1186 | 0.094* | |
H5BC | 0.2588 | 0.4656 | 0.0587 | 0.094* | |
H6BA | 0.2641 | 0.1824 | 0.5177 | 0.141* | |
H6BB | 0.1007 | 0.2330 | 0.5663 | 0.141* | |
H6BC | 0.1943 | 0.3661 | 0.5106 | 0.141* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1A | 0.0464 (3) | 0.0776 (10) | 0.0609 (4) | 0.0053 (5) | 0.0024 (3) | 0.0046 (5) |
S2A | 0.0706 (5) | 0.0934 (12) | 0.0558 (4) | 0.0065 (6) | 0.0122 (4) | −0.0109 (5) |
O1A | 0.0566 (12) | 0.090 (3) | 0.0485 (11) | 0.0080 (13) | −0.0007 (10) | −0.0004 (13) |
N1A | 0.0455 (11) | 0.057 (3) | 0.0501 (13) | −0.0041 (13) | 0.0031 (10) | 0.0030 (13) |
N2A | 0.0493 (12) | 0.068 (3) | 0.0457 (12) | −0.0047 (13) | 0.0033 (10) | 0.0060 (13) |
N3A | 0.0473 (12) | 0.065 (3) | 0.0497 (13) | −0.0001 (15) | 0.0054 (10) | 0.0031 (14) |
C1A | 0.0472 (14) | 0.062 (4) | 0.0443 (14) | −0.0045 (16) | 0.0045 (12) | 0.0001 (15) |
C2A | 0.0540 (15) | 0.054 (4) | 0.0495 (15) | −0.0052 (16) | 0.0087 (12) | 0.0037 (16) |
C3A | 0.0462 (14) | 0.041 (3) | 0.0537 (15) | −0.0059 (15) | 0.0052 (12) | 0.0022 (15) |
C4A | 0.075 (2) | 0.141 (6) | 0.0458 (16) | 0.017 (3) | −0.0017 (15) | −0.009 (2) |
C5A | 0.0492 (16) | 0.087 (4) | 0.0678 (19) | 0.010 (2) | 0.0046 (15) | 0.004 (2) |
C6A | 0.0622 (18) | 0.093 (4) | 0.071 (2) | 0.009 (2) | −0.0128 (16) | 0.009 (2) |
S1B | 0.0642 (5) | 0.1000 (11) | 0.0587 (4) | −0.0073 (6) | 0.0165 (4) | 0.0094 (6) |
S2B | 0.0525 (4) | 0.0867 (12) | 0.0674 (5) | −0.0141 (5) | 0.0002 (4) | 0.0006 (6) |
O1B | 0.0631 (13) | 0.079 (3) | 0.0488 (11) | −0.0116 (13) | −0.0059 (10) | −0.0030 (12) |
N1B | 0.0474 (12) | 0.056 (3) | 0.0455 (12) | 0.0012 (14) | 0.0047 (10) | −0.0012 (13) |
N2B | 0.0464 (12) | 0.065 (3) | 0.0466 (12) | −0.0008 (13) | 0.0044 (10) | 0.0027 (13) |
N3B | 0.0532 (13) | 0.058 (3) | 0.0508 (13) | −0.0024 (13) | 0.0059 (11) | 0.0003 (14) |
C1B | 0.0485 (14) | 0.052 (4) | 0.0542 (16) | 0.0052 (16) | −0.0014 (12) | −0.0050 (17) |
C2B | 0.0432 (13) | 0.057 (3) | 0.0513 (15) | 0.0026 (16) | 0.0035 (12) | −0.0027 (17) |
C3B | 0.0503 (15) | 0.050 (3) | 0.0480 (14) | 0.0081 (15) | 0.0108 (12) | 0.0003 (15) |
C4B | 0.078 (2) | 0.117 (5) | 0.078 (2) | −0.026 (3) | −0.025 (2) | 0.007 (3) |
C5B | 0.0651 (18) | 0.075 (4) | 0.0499 (16) | −0.0078 (19) | 0.0113 (14) | 0.0021 (17) |
C6B | 0.097 (3) | 0.137 (6) | 0.0485 (18) | 0.001 (3) | 0.0064 (18) | 0.009 (2) |
Geometric parameters (Å, º) top
S1A—C3A | 1.744 (3) | S1B—C3B | 1.736 (3) |
S1A—C6A | 1.786 (3) | S1B—C6B | 1.790 (4) |
S2A—C2A | 1.663 (3) | S2B—C2B | 1.666 (3) |
O1A—C1A | 1.323 (3) | O1B—C1B | 1.324 (3) |
O1A—C4A | 1.465 (5) | O1B—C4B | 1.472 (5) |
N1A—C1A | 1.364 (4) | N1B—C1B | 1.366 (4) |
N1A—C2A | 1.399 (4) | N1B—C2B | 1.383 (4) |
N1A—C5A | 1.476 (4) | N1B—C5B | 1.477 (4) |
N2A—C3A | 1.317 (4) | N2B—C3B | 1.318 (4) |
N2A—C2A | 1.356 (4) | N2B—C2B | 1.366 (4) |
N3A—C1A | 1.295 (4) | N3B—C1B | 1.292 (4) |
N3A—C3A | 1.347 (4) | N3B—C3B | 1.347 (4) |
C4A—H4AA | 0.9600 | C4B—H4BA | 0.9600 |
C4A—H4AB | 0.9600 | C4B—H4BB | 0.9600 |
C4A—H4AC | 0.9600 | C4B—H4BC | 0.9600 |
C5A—H5AA | 0.9600 | C5B—H5BA | 0.9600 |
C5A—H5AB | 0.9600 | C5B—H5BB | 0.9600 |
C5A—H5AC | 0.9600 | C5B—H5BC | 0.9600 |
C6A—H6AA | 0.9600 | C6B—H6BA | 0.9600 |
C6A—H6AB | 0.9600 | C6B—H6BB | 0.9600 |
C6A—H6AC | 0.9600 | C6B—H6BC | 0.9600 |
| | | |
C3A—S1A—C6A | 103.24 (18) | C3B—S1B—C6B | 103.5 (2) |
C1A—O1A—C4A | 115.2 (3) | C1B—O1B—C4B | 115.2 (3) |
C1A—N1A—C2A | 118.3 (3) | C1B—N1B—C2B | 118.6 (3) |
C1A—N1A—C5A | 119.7 (3) | C1B—N1B—C5B | 120.2 (3) |
C2A—N1A—C5A | 121.9 (3) | C2B—N1B—C5B | 121.2 (3) |
C3A—N2A—C2A | 117.6 (3) | C3B—N2B—C2B | 117.2 (3) |
C1A—N3A—C3A | 114.4 (3) | C1B—N3B—C3B | 114.5 (3) |
N3A—C1A—O1A | 122.4 (3) | N3B—C1B—O1B | 122.6 (3) |
N3A—C1A—N1A | 124.4 (3) | N3B—C1B—N1B | 124.2 (3) |
O1A—C1A—N1A | 113.1 (3) | O1B—C1B—N1B | 113.2 (3) |
N2A—C2A—N1A | 117.9 (3) | N2B—C2B—N1B | 118.2 (3) |
N2A—C2A—S2A | 121.3 (2) | N2B—C2B—S2B | 120.7 (2) |
N1A—C2A—S2A | 120.8 (2) | N1B—C2B—S2B | 121.2 (2) |
N2A—C3A—N3A | 127.3 (3) | N2B—C3B—N3B | 127.2 (3) |
N2A—C3A—S1A | 121.2 (2) | N2B—C3B—S1B | 120.7 (2) |
N3A—C3A—S1A | 111.5 (2) | N3B—C3B—S1B | 112.1 (2) |
O1A—C4A—H4AA | 109.4 | O1B—C4B—H4BA | 109.5 |
O1A—C4A—H4AB | 109.5 | O1B—C4B—H4BB | 109.5 |
H4AA—C4A—H4AB | 109.5 | H4BA—C4B—H4BB | 109.5 |
O1A—C4A—H4AC | 109.5 | O1B—C4B—H4BC | 109.4 |
H4AA—C4A—H4AC | 109.5 | H4BA—C4B—H4BC | 109.5 |
H4AB—C4A—H4AC | 109.5 | H4BB—C4B—H4BC | 109.5 |
N1A—C5A—H5AA | 109.5 | N1B—C5B—H5BA | 109.4 |
N1A—C5A—H5AB | 109.5 | N1B—C5B—H5BB | 109.5 |
H5AA—C5A—H5AB | 109.5 | H5BA—C5B—H5BB | 109.5 |
N1A—C5A—H5AC | 109.4 | N1B—C5B—H5BC | 109.5 |
H5AA—C5A—H5AC | 109.5 | H5BA—C5B—H5BC | 109.5 |
H5AB—C5A—H5AC | 109.5 | H5BB—C5B—H5BC | 109.5 |
S1A—C6A—H6AA | 109.5 | S1B—C6B—H6BA | 109.5 |
S1A—C6A—H6AB | 109.5 | S1B—C6B—H6BB | 109.5 |
H6AA—C6A—H6AB | 109.5 | H6BA—C6B—H6BB | 109.5 |
S1A—C6A—H6AC | 109.5 | S1B—C6B—H6BC | 109.4 |
H6AA—C6A—H6AC | 109.5 | H6BA—C6B—H6BC | 109.5 |
H6AB—C6A—H6AC | 109.5 | H6BB—C6B—H6BC | 109.5 |
| | | |
C3A—N3A—C1A—O1A | −179.4 (3) | C3B—N3B—C1B—O1B | −176.0 (3) |
C3A—N3A—C1A—N1A | 1.3 (6) | C3B—N3B—C1B—N1B | 3.4 (5) |
C4A—O1A—C1A—N3A | 5.9 (6) | C4B—O1B—C1B—N3B | 0.9 (5) |
C4A—O1A—C1A—N1A | −174.7 (4) | C4B—O1B—C1B—N1B | −178.5 (4) |
C2A—N1A—C1A—N3A | −3.6 (6) | C2B—N1B—C1B—N3B | −2.5 (6) |
C5A—N1A—C1A—N3A | −179.4 (4) | C5B—N1B—C1B—N3B | 177.0 (3) |
C2A—N1A—C1A—O1A | 177.1 (3) | C2B—N1B—C1B—O1B | 177.0 (3) |
C5A—N1A—C1A—O1A | 1.2 (5) | C5B—N1B—C1B—O1B | −3.6 (5) |
C3A—N2A—C2A—N1A | −1.8 (6) | C3B—N2B—C2B—N1B | 1.5 (5) |
C3A—N2A—C2A—S2A | 177.8 (3) | C3B—N2B—C2B—S2B | −178.8 (3) |
C1A—N1A—C2A—N2A | 3.7 (5) | C1B—N1B—C2B—N2B | −0.2 (5) |
C5A—N1A—C2A—N2A | 179.5 (4) | C5B—N1B—C2B—N2B | −179.6 (3) |
C1A—N1A—C2A—S2A | −175.9 (3) | C1B—N1B—C2B—S2B | −180.0 (3) |
C5A—N1A—C2A—S2A | −0.1 (5) | C5B—N1B—C2B—S2B | 0.6 (5) |
C2A—N2A—C3A—N3A | −0.6 (6) | C2B—N2B—C3B—N3B | −0.4 (6) |
C2A—N2A—C3A—S1A | −179.9 (3) | C2B—N2B—C3B—S1B | −179.5 (3) |
C1A—N3A—C3A—N2A | 0.9 (6) | C1B—N3B—C3B—N2B | −2.0 (5) |
C1A—N3A—C3A—S1A | −179.7 (3) | C1B—N3B—C3B—S1B | 177.2 (3) |
C6A—S1A—C3A—N2A | −3.3 (4) | C6B—S1B—C3B—N2B | 2.5 (4) |
C6A—S1A—C3A—N3A | 177.3 (3) | C6B—S1B—C3B—N3B | −176.7 (3) |
(12) 1-methyl-2,4-bismethylthio-1,3,5-triazine-6(1
H)-one
top
Crystal data top
C6H9N3OS2 | Dx = 1.463 Mg m−3 |
Mr = 203.28 | Melting point: 150 K |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 25 reflections |
a = 15.712 (7) Å | θ = 2.6–18.5° |
b = 6.730 (3) Å | µ = 0.53 mm−1 |
c = 8.731 (4) Å | T = 293 K |
V = 923.2 (6) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.22 × 0.17 mm |
F(000) = 424 | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.032 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.6° |
Graphite monochromator | h = −4→18 |
ω/2θ scans | k = 0→8 |
934 measured reflections | l = −3→10 |
891 independent reflections | 3 standard reflections every 120 min. min |
639 reflections with I > 2σ(I) | intensity decay: 3.0% |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0495P)2] where P = (Fo2 + 2Fc2)/3 |
891 reflections | (Δ/σ)max < 0.001 |
76 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C6H9N3OS2 | V = 923.2 (6) Å3 |
Mr = 203.28 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 15.712 (7) Å | µ = 0.53 mm−1 |
b = 6.730 (3) Å | T = 293 K |
c = 8.731 (4) Å | 0.30 × 0.22 × 0.17 mm |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.032 |
934 measured reflections | 3 standard reflections every 120 min. min |
891 independent reflections | intensity decay: 3.0% |
639 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.28 e Å−3 |
891 reflections | Δρmin = −0.24 e Å−3 |
76 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.24212 (6) | 1.2500 | 0.02198 (15) | 0.0581 (4) | |
S2 | 0.49776 (7) | 1.2500 | 0.40352 (14) | 0.0570 (4) | |
O1 | 0.54068 (17) | 1.2500 | −0.1553 (4) | 0.0646 (10) | |
N1 | 0.51564 (19) | 1.2500 | 0.1017 (4) | 0.0397 (8) | |
N2 | 0.3752 (2) | 1.2500 | 0.1942 (4) | 0.0426 (9) | |
N3 | 0.40189 (19) | 1.2500 | −0.0767 (4) | 0.0428 (9) | |
C1 | 0.4884 (3) | 1.2500 | −0.0516 (5) | 0.0428 (10) | |
C2 | 0.4580 (3) | 1.2500 | 0.2169 (5) | 0.0415 (11) | |
C3 | 0.3523 (3) | 1.2500 | 0.0437 (5) | 0.0399 (10) | |
C4 | 0.4016 (3) | 1.2500 | 0.5127 (5) | 0.0637 (14) | |
C5 | 0.6080 (2) | 1.2500 | 0.1339 (6) | 0.0560 (13) | |
C6 | 0.2289 (3) | 1.2500 | −0.1816 (6) | 0.0687 (15) | |
H4A | 0.3751 | 1.1218 | 0.5059 | 0.096* | 0.50 |
H4B | 0.3636 | 1.3492 | 0.4730 | 0.096* | 0.50 |
H4C | 0.4144 | 1.2791 | 0.6179 | 0.096* | 0.50 |
H5A | 0.6252 | 1.1199 | 0.1666 | 0.084* | 0.50 |
H5B | 0.6202 | 1.3445 | 0.2132 | 0.084* | 0.50 |
H5C | 0.6385 | 1.2856 | 0.0427 | 0.084* | 0.50 |
H6A | 0.1717 | 1.2121 | −0.2064 | 0.103* | 0.50 |
H6B | 0.2680 | 1.1572 | −0.2267 | 0.103* | 0.50 |
H6C | 0.2400 | 1.3807 | −0.2208 | 0.103* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0319 (6) | 0.0957 (10) | 0.0468 (7) | 0.000 | 0.0004 (5) | 0.000 |
S2 | 0.0582 (8) | 0.0771 (9) | 0.0357 (7) | 0.000 | −0.0124 (5) | 0.000 |
O1 | 0.0417 (16) | 0.108 (3) | 0.0435 (19) | 0.000 | 0.0106 (16) | 0.000 |
N1 | 0.0338 (16) | 0.049 (2) | 0.0361 (19) | 0.000 | −0.0019 (16) | 0.000 |
N2 | 0.0408 (18) | 0.058 (2) | 0.029 (2) | 0.000 | 0.0001 (15) | 0.000 |
N3 | 0.0340 (17) | 0.064 (2) | 0.0302 (19) | 0.000 | −0.0011 (15) | 0.000 |
C1 | 0.040 (2) | 0.049 (2) | 0.039 (2) | 0.000 | 0.001 (2) | 0.000 |
C2 | 0.046 (2) | 0.042 (2) | 0.037 (2) | 0.000 | −0.008 (2) | 0.000 |
C3 | 0.038 (2) | 0.047 (2) | 0.035 (2) | 0.000 | −0.0009 (19) | 0.000 |
C4 | 0.075 (4) | 0.086 (4) | 0.030 (3) | 0.000 | 0.001 (2) | 0.000 |
C5 | 0.034 (2) | 0.072 (3) | 0.062 (3) | 0.000 | −0.004 (2) | 0.000 |
C6 | 0.046 (2) | 0.106 (4) | 0.054 (3) | 0.000 | −0.017 (3) | 0.000 |
Geometric parameters (Å, º) top
S1—C3 | 1.742 (4) | N3—C1 | 1.377 (5) |
S1—C6 | 1.789 (5) | C4—H4A | 0.9600 |
S2—C2 | 1.745 (4) | C4—H4B | 0.9600 |
S2—C4 | 1.787 (5) | C4—H4C | 0.9600 |
O1—C1 | 1.222 (5) | C5—H5A | 0.9600 |
N1—C2 | 1.353 (5) | C5—H5B | 0.9600 |
N1—C1 | 1.406 (5) | C5—H5C | 0.9600 |
N1—C5 | 1.478 (5) | C6—H6A | 0.9600 |
N2—C2 | 1.315 (5) | C6—H6B | 0.9600 |
N2—C3 | 1.362 (5) | C6—H6C | 0.9600 |
N3—C3 | 1.308 (5) | | |
| | | |
C3—S1—C6 | 102.9 (2) | S2—C4—H4B | 109.5 |
C2—S2—C4 | 101.3 (2) | H4A—C4—H4B | 109.5 |
C2—N1—C1 | 120.2 (3) | S2—C4—H4C | 109.5 |
C2—N1—C5 | 121.1 (3) | H4A—C4—H4C | 109.5 |
C1—N1—C5 | 118.7 (3) | H4B—C4—H4C | 109.5 |
C2—N2—C3 | 114.0 (4) | N1—C5—H5A | 109.5 |
C3—N3—C1 | 117.4 (4) | N1—C5—H5B | 109.5 |
O1—C1—N3 | 123.1 (4) | H5A—C5—H5B | 109.5 |
O1—C1—N1 | 120.1 (4) | N1—C5—H5C | 109.5 |
N3—C1—N1 | 116.9 (4) | H5A—C5—H5C | 109.5 |
N2—C2—N1 | 123.4 (4) | H5B—C5—H5C | 109.5 |
N2—C2—S2 | 119.7 (3) | S1—C6—H6A | 109.5 |
N1—C2—S2 | 117.0 (3) | S1—C6—H6B | 109.5 |
N3—C3—N2 | 128.1 (4) | H6A—C6—H6B | 109.5 |
N3—C3—S1 | 120.3 (3) | S1—C6—H6C | 109.5 |
N2—C3—S1 | 111.6 (3) | H6A—C6—H6C | 109.5 |
S2—C4—H4A | 109.5 | H6B—C6—H6C | 109.5 |
| | | |
C3—N3—C1—O1 | 180.0 | C1—N1—C2—S2 | 180.0 |
C3—N3—C1—N1 | 0.000 (1) | C5—N1—C2—S2 | 0.0 |
C2—N1—C1—O1 | 180.000 (1) | C4—S2—C2—N2 | 0.0 |
C5—N1—C1—O1 | 0.0 | C4—S2—C2—N1 | 180.000 (1) |
C2—N1—C1—N3 | 0.0 | C1—N3—C3—N2 | 0.000 (2) |
C5—N1—C1—N3 | 180.0 | C1—N3—C3—S1 | 180.0 |
C3—N2—C2—N1 | 0.0 | C2—N2—C3—N3 | 0.000 (2) |
C3—N2—C2—S2 | 180.0 | C2—N2—C3—S1 | 180.0 |
C1—N1—C2—N2 | 0.0 | C6—S1—C3—N3 | 0.0 |
C5—N1—C2—N2 | 180.0 | C6—S1—C3—N2 | 180.000 (1) |
Experimental details
| (9a) | (9b) | (11) | (12) |
Crystal data |
Chemical formula | C6H9N3O2S | C6H9N3O2S | C6H9N3OS2 | C6H9N3OS2 |
Mr | 187.22 | 187.22 | 203.28 | 203.28 |
Crystal system, space group | Orthorhombic, Pnma | Monoclinic, P21/c | Monoclinic, P21 | Orthorhombic, Pnma |
Temperature (K) | 293 | 293 | 300 | 293 |
a, b, c (Å) | 15.231 (5), 6.778 (3), 8.626 (3) | 7.657 (3), 14.361 (7), 8.433 (4) | 7.7771 (8), 7.9991 (7), 14.9762 (16) | 15.712 (7), 6.730 (3), 8.731 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 110.99 (3), 90 | 90, 94.629 (1), 90 | 90, 90, 90 |
V (Å3) | 890.5 (6) | 865.8 (7) | 928.63 (16) | 923.2 (6) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.34 | 0.53 | 0.53 |
Crystal size (mm) | 0.33 × 0.27 × 0.19 | 0.45 × 0.38 × 0.24 | 0.40 × 0.30 × 0.25 | 0.30 × 0.22 × 0.17 |
|
Data collection |
Diffractometer | Philips PW 1100 diffractometer | Philips PW 1100 diffractometer | Siemens SMART diffractometer | Philips PW 1100 diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 981, 857, 560 | 1730, 1520, 902 | 10006, 3203, 2629 | 934, 891, 639 |
Rint | 0.055 | 0.091 | 0.025 | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.667 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.154, 1.10 | 0.053, 0.159, 1.08 | 0.050, 0.120, 1.05 | 0.049, 0.117, 1.08 |
No. of reflections | 857 | 1520 | 3203 | 891 |
No. of parameters | 84 | 112 | 217 | 76 |
No. of restraints | 6 | 0 | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.36 | 0.37, −0.36 | 0.64, −0.23 | 0.28, −0.24 |
Absolute structure | ? | ? | Flack H D (1983), Acta Cryst. A39, 876-881 | ? |
Absolute structure parameter | ? | ? | −0.12 (9) | ? |
See the attached manuscript