Topochemically controlled solid-state methyl ­rearrangement in thiocyanurates

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.

S1. Comment

See the attached manuscript

Computing details

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).

Figures

(9a) 4,6-Dimethoxy-3-methyl-1,3,5-triazine-2(3H)-thione

Crystal data

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) Å^3	Needle, light yellow
Z = 4	0.33 × 0.27 × 0.19 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0635P)^2 + 0.2249P] where P = (Fo^2 + 2Fc^2)/3
857 reflections	(Δ/σ)max < 0.001
84 parameters	Δρmax = 0.20 e Å^−3
6 restraints	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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(3H)-thion

Crystal data

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) Å^3	Plates, light yellow
Z = 4	0.45 × 0.38 × 0.24 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 2.0096P] where P = (Fo^2 + 2Fc^2)/3
1520 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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(1H)-thione

Crystal data

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) Å^3	Plate, light yellow
Z = 4	0.40 × 0.30 × 0.25 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0803P)^2] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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(1H)-one

Crystal data

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) Å^3	Prism, colourless
Z = 4	0.30 × 0.22 × 0.17 mm
F(000) = 424

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0495P)^2] where P = (Fo^2 + 2Fc^2)/3
891 reflections	(Δ/σ)max < 0.001
76 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)