3-Methyl­sulfanyl-5-phenyl-1,2,4-triazine

In the mol­ecule of the title compound, C₁₀H₉N₃S, the dihedral angle between the triazine and phenyl rings is 11.77 (7)°. In the crystal, mol­ecules are linked by π–π stacking inter­actions [centroid–centroid distances = 3.7359 (3) and 3.7944 (4) Å], forming layers parallel to the bc plane.

Related literature

For the biological activity of sulfonamides, see: Abd el-Samii (1992); Kidwai et al. (1998); Holla et al. (2001); Abdel-Rahman et al. (1999); Hay et al. (2004); Sztanke et al. (2005). For the structure of a similar compound, see: Wen et al. (2006).

Experimental

Crystal data

• C₁₀H₉N₃S

• M_r = 203.26

• Monoclinic, P 2₁ /c

• a = 7.7513 (3) Å

• b = 12.9191 (5) Å

• c = 9.8262 (3) Å

• β = 94.584 (2)°

• V = 980.85 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.29 mm⁻¹

• T = 296 K

• 0.41 × 0.35 × 0.29 mm

Data collection

• Bruker X8 APEX diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.693, T_max = 0.747

• 15588 measured reflections

• 2859 independent reflections

• 2544 reflections with I > 2σ(I)

• R_int = 0.023

Refinement

• R[F² > 2σ(F²)] = 0.037

• wR(F²) = 0.110

• S = 1.10

• 2859 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Supporting information

S1. Comment

1,2,4-Triazine derivatives have been widely studied in terms of their synthetic methodologies and reactivity since some of these compounds were reported to have promising biological activities, including antimicrobial, inflammatory, analgesic, antiviral and anthelminitic activities (Abd el-Samii, 1992; Kidwai et al., 1998; Holla et al., 2001; Abdel-Rahman et al., 1999; Hay et al., 2004; Sztanke et al., 2005). We synthesized the title compound and describe its structure here.

The molecular structure of 3-methylsulfanyl-5-phenyl-1,2,4-triazine is shown in Fig. 1. The triazine ring (N1–N3/C2–C4) forms a dihedral angle of 11.77 (7)° with the phenyl ring. Bond lengths and angles are compatible with those found in a related compound (Wen et al., 2006). The cohesion of the crystal structure is ensured by π···π stacking interaction between triazine and phenyl rings [intercentroid distance = 3.7944 (4) Å] and between centrosymmetrically related triazine rings [intercentroid distance = 3.7359 (3) Å], forming molecular layers parallel to the bc plane.

Related literature

For the biological activity of sulfonamides, see: Abd el-Samii (1992); Kidwai et al. (1998); Holla et al. (2001); Abdel-Rahman et al. (1999); Hay et al. (2004); Sztanke et al. (2005). For the structure of a similar compound, see: Wen et al. (2006).

S2. Experimental

To a solution of thiosemicarbazide (50 g, 0.55 mol) in absolute ethanol (500 ml) was added iodomethane (34.1 ml, 0.55 mol). The reaction mixture was stirred at reflux for 3 h then cooled overnight in the refrigerator. The crystals formed were filtered on a Buchner funnel, washed with ethanol and dried in vacuo to give the S-methylthiosemicarbazide iodohydrate beige powder (123 g). An aqueous solution (200 ml) of S-methylthiosemicarbazide iodohydrate (20 g, 85.8 mmol) was added to an aqueous solution (120 ml) of phenyl glyoxal (15.65 g, 103 mmol) and sodium bicarbonate (10 g, 94.4 mmol) at 5°C. The temperature was maintained at 5°C for 6 h then the reaction medium was extracted with dichloromethane. The organic phases are combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material was purified by column on silica (hexane/EtOAc 9:1 v/v) as eluent. The title compound (13.95 g) was obtained as yellow crystals (79% yield) on slow evaporation of the solvent.

S3. Refinement

H atoms were located in a difference Fourier map and treated as riding, with C–H = 0.93–0.96 Å and U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms. One outlier (-1 7 1) was omitted in the last cycles of refinement.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.

3-Methylsulfanyl-5-phenyl-1,2,4-triazine

Crystal data

C10H9N3S	F(000) = 424
Mr = 203.26	Dx = 1.376 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2859 reflections
a = 7.7513 (3) Å	θ = 2.6–30.0°
b = 12.9191 (5) Å	µ = 0.29 mm^−1
c = 9.8262 (3) Å	T = 296 K
β = 94.584 (2)°	Block, yellow
V = 980.85 (6) Å^3	0.41 × 0.35 × 0.29 mm
Z = 4

Data collection

Bruker X8 APEX diffractometer	2859 independent reflections
Radiation source: fine-focus sealed tube	2544 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.693, Tmax = 0.747	k = −18→16
15588 measured reflections	l = −11→13

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0567P)^2 + 0.210P] where P = (Fo^2 + 2Fc^2)/3
2859 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.32 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
S	0.23977 (4)	0.83039 (3)	0.60310 (3)	0.04391 (12)
N1	0.55958 (14)	0.87884 (9)	0.70043 (10)	0.0411 (2)
N2	0.49883 (12)	0.86358 (7)	0.45807 (9)	0.0321 (2)
N3	0.72612 (15)	0.90131 (11)	0.68242 (11)	0.0492 (3)
C1	0.2219 (2)	0.83401 (12)	0.78375 (15)	0.0478 (3)
H1A	0.1053	0.8176	0.8025	0.072*
H1B	0.2509	0.9020	0.8177	0.072*
H1C	0.2997	0.7844	0.8278	0.072*
C2	0.45673 (14)	0.86159 (8)	0.58822 (11)	0.0315 (2)
C3	0.77637 (16)	0.90344 (12)	0.55773 (13)	0.0434 (3)
H3	0.8915	0.9188	0.5461	0.052*
C4	0.66358 (14)	0.88349 (8)	0.44103 (11)	0.0308 (2)
C5	0.72027 (15)	0.88557 (8)	0.30105 (11)	0.0324 (2)
C6	0.89529 (17)	0.88858 (11)	0.27791 (14)	0.0439 (3)
H6	0.9785	0.8887	0.3515	0.053*
C7	0.9461 (2)	0.89133 (13)	0.14577 (16)	0.0537 (4)
H7	1.0631	0.8939	0.1311	0.064*
C8	0.8234 (2)	0.89027 (12)	0.03593 (15)	0.0539 (4)
H8	0.8576	0.8917	−0.0526	0.065*
C9	0.6501 (2)	0.88713 (12)	0.05779 (13)	0.0499 (3)
H9	0.5677	0.8863	−0.0164	0.060*
C10	0.59717 (17)	0.88521 (10)	0.18942 (12)	0.0403 (3)
H10	0.4799	0.8837	0.2032	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.03440 (17)	0.0619 (2)	0.03562 (17)	−0.00433 (12)	0.00418 (12)	0.00196 (13)
N1	0.0413 (5)	0.0550 (6)	0.0266 (4)	−0.0031 (4)	0.0003 (4)	0.0005 (4)
N2	0.0327 (4)	0.0367 (5)	0.0264 (4)	−0.0001 (3)	0.0000 (3)	0.0010 (3)
N3	0.0410 (6)	0.0750 (8)	0.0305 (5)	−0.0083 (5)	−0.0042 (4)	−0.0019 (5)
C1	0.0498 (7)	0.0555 (8)	0.0397 (7)	−0.0018 (6)	0.0137 (5)	0.0043 (5)
C2	0.0339 (5)	0.0325 (5)	0.0280 (5)	0.0015 (4)	0.0020 (4)	0.0023 (4)
C3	0.0328 (5)	0.0640 (8)	0.0324 (6)	−0.0063 (5)	−0.0023 (4)	−0.0007 (5)
C4	0.0330 (5)	0.0318 (5)	0.0271 (5)	0.0006 (4)	−0.0003 (4)	0.0008 (4)
C5	0.0374 (5)	0.0321 (5)	0.0280 (5)	0.0004 (4)	0.0033 (4)	−0.0002 (4)
C6	0.0389 (6)	0.0537 (7)	0.0396 (6)	0.0064 (5)	0.0060 (5)	0.0013 (5)
C7	0.0509 (8)	0.0642 (9)	0.0485 (8)	0.0080 (7)	0.0197 (6)	0.0016 (7)
C8	0.0753 (10)	0.0539 (8)	0.0350 (6)	0.0041 (7)	0.0192 (6)	−0.0014 (6)
C9	0.0675 (9)	0.0546 (8)	0.0271 (5)	−0.0046 (6)	−0.0002 (5)	−0.0023 (5)
C10	0.0443 (6)	0.0467 (6)	0.0294 (5)	−0.0060 (5)	−0.0006 (4)	−0.0012 (5)

Geometric parameters (Å, º)

S—C2	1.7469 (11)	C4—C5	1.4773 (15)
S—C1	1.7921 (14)	C5—C6	1.3939 (17)
N1—C2	1.3268 (15)	C5—C10	1.3951 (16)
N1—N3	1.3486 (16)	C6—C7	1.3872 (18)
N2—C4	1.3263 (14)	C6—H6	0.9300
N2—C2	1.3451 (14)	C7—C8	1.381 (2)
N3—C3	1.3153 (17)	C7—H7	0.9300
C1—H1A	0.9600	C8—C9	1.378 (2)
C1—H1B	0.9600	C8—H8	0.9300
C1—H1C	0.9600	C9—C10	1.3880 (17)
C3—C4	1.4091 (15)	C9—H9	0.9300
C3—H3	0.9300	C10—H10	0.9300
C2—S—C1	103.19 (6)	C6—C5—C10	119.03 (11)
C2—N1—N3	116.42 (10)	C6—C5—C4	121.21 (10)
C4—N2—C2	115.65 (9)	C10—C5—C4	119.76 (11)
C3—N3—N1	118.99 (10)	C7—C6—C5	120.43 (13)
S—C1—H1A	109.5	C7—C6—H6	119.8
S—C1—H1B	109.5	C5—C6—H6	119.8
H1A—C1—H1B	109.5	C8—C7—C6	120.11 (14)
S—C1—H1C	109.5	C8—C7—H7	119.9
H1A—C1—H1C	109.5	C6—C7—H7	119.9
H1B—C1—H1C	109.5	C9—C8—C7	119.87 (12)
N1—C2—N2	127.71 (10)	C9—C8—H8	120.1
N1—C2—S	119.19 (9)	C7—C8—H8	120.1
N2—C2—S	113.10 (8)	C8—C9—C10	120.68 (13)
N3—C3—C4	122.93 (11)	C8—C9—H9	119.7
N3—C3—H3	118.5	C10—C9—H9	119.7
C4—C3—H3	118.5	C9—C10—C5	119.88 (13)
N2—C4—C3	118.28 (10)	C9—C10—H10	120.1
N2—C4—C5	118.82 (10)	C5—C10—H10	120.1
C3—C4—C5	122.89 (10)