Crystal structure of 4-methyl-sulfanyl-2-(2H-tetra-zol-2-yl)pyrimidine.

The title compound, C6H6N6S, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. The conformation of the two mol-ecules differs slightly. While the tetra-zole ring is inclined to the pyrim-idene ring by 5.48 (7) and 4.24 (7)° in mol-ecules A and B, respectively, the N-C-S-C torsion angles of the thio-methyl groups differ by ca 180°. In the crystal, the A and B mol-ecules are linked via a C-H⋯N hydrogen bond. They stack along the b-axis direction forming columns within which there are weak π-π inter-actions present [shortest inter-centroid distance = 3.6933 (13) Å].

Related literature

For applications of tetra­zolyl-substituted aromatic systems in metal–ligand research, see: Kim et al. (2008 ▸); Stoessel et al. (2010 ▸); in drug development, see: Pasternak et al. (2012 ▸); Biswas et al. (2015 ▸); in polymer synthesis, see: Yu et al. (2008 ▸); Sengupta et al. (2010 ▸). For the synthesis of 4-methyl­sulfanyl-2-(1H-tetra­zol-1-yl)pyrimidine and the title compound, see: Thomann et al. (2014 ▸).

Experimental

Crystal data

C6H6N6S

M = 194.23

Triclinic,

a = 6.3001 (17) Å

b = 7.393 (2) Å

c = 18.159 (5) Å

α = 91.407 (7)°

β = 95.864 (7)°

γ = 102.695 (8)°

V = 819.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.35 mm−1

T = 143 K

0.22 × 0.22 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▸) T min = 0.716, T max = 0.746

15501 measured reflections

4581 independent reflections

3596 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.086

S = 1.01

4581 reflections

283 parameters

All H-atom parameters refined

Δρmax = 0.35 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2010 ▸); cell refinement: SAINT (Bruker, 2010 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL2014 and PLATON.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015023634/su5253sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023634/su5253Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023634/su5253Isup3.cml

Click here for additional data file.

A B . DOI: 10.1107/S2056989015023634/su5253fig1.tif

The mol­ecular structure of the two independent mol­ecules (A and B) of the title compound (2), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

A B a . DOI: 10.1107/S2056989015023634/su5253fig2.tif

The crystal packing of the two independent mol­ecules (A black; B red) of the title compound (2), viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1).

Click here for additional data file.

. DOI: 10.1107/S2056989015023634/su5253fig3.tif

Compounds (1) and (2).

CCDC reference: 1441424

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H6N6S	Z = 4
Mr = 194.23	F(000) = 400
Triclinic, P1	Dx = 1.574 Mg m−3
a = 6.3001 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.393 (2) Å	Cell parameters from 728 reflections
c = 18.159 (5) Å	θ = 3.6–24.3°
α = 91.407 (7)°	µ = 0.35 mm−1
β = 95.864 (7)°	T = 143 K
γ = 102.695 (8)°	Cuboid, colourless
V = 819.9 (4) Å3	0.22 × 0.22 × 0.01 mm

Bruker APEXII CCD diffractometer	3596 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.028
Absorption correction: multi-scan (SADABS; Bruker, 2010)	θmax = 29.6°, θmin = 2.3°
Tmin = 0.716, Tmax = 0.746	h = −8→8
15501 measured reflections	k = −10→10
4581 independent reflections	l = −24→25

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034	All H-atom parameters refined
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0376P)2 + 0.2718P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
4581 reflections	Δρmax = 0.35 e Å−3
283 parameters	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.84117 (6)	0.83334 (5)	0.58281 (2)	0.01975 (9)
N1	1.04303 (18)	0.69484 (15)	0.84617 (6)	0.0152 (2)
N2	1.00906 (19)	0.60999 (17)	0.90974 (6)	0.0208 (3)
N3	1.24517 (19)	0.79683 (17)	0.84553 (7)	0.0209 (3)
N4	1.3498 (2)	0.77865 (18)	0.91059 (7)	0.0233 (3)
N5	0.93885 (18)	0.76012 (15)	0.72442 (6)	0.0159 (2)
N6	0.56784 (19)	0.65519 (16)	0.66803 (7)	0.0200 (3)
C1	0.8749 (2)	0.67900 (17)	0.78527 (7)	0.0148 (3)
C2	0.6647 (2)	0.58341 (19)	0.79335 (8)	0.0184 (3)
C3	0.5146 (2)	0.5770 (2)	0.73096 (8)	0.0203 (3)
C4	0.7801 (2)	0.74205 (18)	0.66783 (8)	0.0162 (3)
C5	1.2034 (2)	0.6651 (2)	0.94818 (8)	0.0209 (3)
C6	1.1309 (2)	0.9298 (2)	0.60068 (9)	0.0230 (3)
H1	0.629 (3)	0.532 (2)	0.8352 (10)	0.028 (5)*
H2	0.366 (3)	0.512 (2)	0.7313 (9)	0.023 (4)*
H3	1.235 (3)	0.634 (2)	0.9944 (11)	0.030 (5)*
H4	1.204 (3)	0.833 (2)	0.6178 (10)	0.032 (5)*
H5	1.160 (3)	1.037 (2)	0.6366 (10)	0.030 (5)*
H6	1.172 (3)	0.969 (3)	0.5531 (11)	0.040 (5)*
S2	0.91337 (6)	0.35407 (5)	0.59998 (2)	0.02003 (10)
N7	1.07557 (18)	0.19569 (15)	0.85809 (6)	0.0156 (2)
N8	1.0376 (2)	0.11547 (17)	0.92240 (7)	0.0219 (3)
N9	1.28032 (19)	0.29223 (17)	0.85739 (7)	0.0218 (3)
N10	1.3817 (2)	0.27602 (18)	0.92304 (7)	0.0241 (3)
N11	0.97742 (18)	0.26119 (15)	0.73636 (6)	0.0159 (2)
N12	0.60819 (19)	0.16413 (16)	0.67866 (7)	0.0192 (2)
C7	0.9101 (2)	0.18161 (17)	0.79690 (7)	0.0146 (3)
C8	0.6975 (2)	0.08981 (19)	0.80433 (8)	0.0181 (3)
C9	0.5511 (2)	0.0862 (2)	0.74162 (8)	0.0204 (3)
C10	0.8194 (2)	0.24779 (18)	0.67912 (8)	0.0162 (3)
C11	1.2311 (2)	0.1686 (2)	0.96118 (8)	0.0218 (3)
C12	0.6629 (3)	0.3216 (2)	0.53901 (9)	0.0256 (3)
H7	0.658 (3)	0.041 (2)	0.8462 (10)	0.028 (5)*
H8	0.400 (3)	0.022 (2)	0.7410 (10)	0.027 (4)*
H9	1.264 (3)	0.138 (3)	1.0104 (11)	0.035 (5)*
H10	0.564 (3)	0.385 (2)	0.5600 (10)	0.035 (5)*
H11	0.702 (3)	0.373 (3)	0.4949 (11)	0.037 (5)*
H12	0.600 (3)	0.192 (3)	0.5294 (10)	0.038 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.02103 (18)	0.02210 (18)	0.01490 (18)	0.00253 (13)	−0.00004 (13)	0.00614 (13)
N1	0.0152 (5)	0.0167 (5)	0.0130 (5)	0.0007 (4)	0.0036 (4)	0.0040 (4)
N2	0.0216 (6)	0.0250 (6)	0.0152 (6)	0.0020 (5)	0.0040 (5)	0.0078 (5)
N3	0.0155 (6)	0.0260 (6)	0.0190 (6)	−0.0011 (5)	0.0024 (5)	0.0049 (5)
N4	0.0203 (6)	0.0295 (7)	0.0186 (6)	0.0031 (5)	0.0005 (5)	0.0046 (5)
N5	0.0166 (5)	0.0159 (5)	0.0149 (6)	0.0028 (4)	0.0030 (4)	0.0019 (4)
N6	0.0182 (6)	0.0193 (6)	0.0212 (6)	0.0019 (4)	0.0009 (5)	0.0034 (5)
C1	0.0155 (6)	0.0138 (6)	0.0150 (6)	0.0030 (5)	0.0025 (5)	0.0011 (5)
C2	0.0186 (7)	0.0180 (7)	0.0181 (7)	0.0012 (5)	0.0057 (5)	0.0042 (5)
C3	0.0168 (7)	0.0200 (7)	0.0232 (8)	0.0008 (5)	0.0039 (6)	0.0026 (5)
C4	0.0181 (6)	0.0149 (6)	0.0157 (7)	0.0034 (5)	0.0026 (5)	0.0020 (5)
C5	0.0221 (7)	0.0251 (7)	0.0153 (7)	0.0044 (6)	0.0022 (6)	0.0045 (5)
C6	0.0203 (7)	0.0305 (8)	0.0190 (7)	0.0053 (6)	0.0042 (6)	0.0093 (6)
S2	0.02219 (18)	0.02074 (18)	0.01648 (18)	0.00230 (13)	0.00321 (14)	0.00600 (13)
N7	0.0134 (5)	0.0181 (5)	0.0149 (6)	0.0015 (4)	0.0037 (4)	0.0045 (4)
N8	0.0203 (6)	0.0281 (7)	0.0170 (6)	0.0028 (5)	0.0044 (5)	0.0090 (5)
N9	0.0152 (6)	0.0265 (6)	0.0213 (6)	−0.0005 (5)	0.0014 (5)	0.0057 (5)
N10	0.0182 (6)	0.0316 (7)	0.0203 (7)	0.0015 (5)	−0.0004 (5)	0.0048 (5)
N11	0.0159 (5)	0.0160 (5)	0.0155 (6)	0.0021 (4)	0.0029 (4)	0.0033 (4)
N12	0.0170 (6)	0.0214 (6)	0.0184 (6)	0.0020 (5)	0.0026 (5)	0.0016 (5)
C7	0.0139 (6)	0.0142 (6)	0.0160 (6)	0.0039 (5)	0.0019 (5)	0.0008 (5)
C8	0.0171 (7)	0.0200 (7)	0.0170 (7)	0.0018 (5)	0.0056 (5)	0.0036 (5)
C9	0.0164 (7)	0.0233 (7)	0.0206 (7)	0.0019 (5)	0.0034 (6)	0.0014 (5)
C10	0.0189 (7)	0.0139 (6)	0.0160 (7)	0.0039 (5)	0.0023 (5)	0.0008 (5)
C11	0.0188 (7)	0.0294 (8)	0.0168 (7)	0.0039 (6)	0.0023 (6)	0.0060 (6)
C12	0.0305 (8)	0.0281 (8)	0.0181 (8)	0.0075 (7)	−0.0006 (6)	0.0034 (6)

S1—C4	1.7453 (15)	S2—C10	1.7487 (15)
S1—C6	1.8004 (16)	S2—C12	1.7992 (16)
N1—N3	1.3311 (16)	N7—N9	1.3314 (16)
N1—N2	1.3412 (16)	N7—N8	1.3421 (16)
N1—C1	1.4347 (17)	N7—C7	1.4291 (17)
N2—C5	1.3207 (19)	N8—C11	1.3182 (19)
N3—N4	1.3176 (17)	N9—N10	1.3148 (17)
N4—C5	1.356 (2)	N10—C11	1.3566 (19)
N5—C1	1.3267 (17)	N11—C7	1.3237 (17)
N5—C4	1.3412 (17)	N11—C10	1.3496 (17)
N6—C3	1.3336 (19)	N12—C10	1.3377 (18)
N6—C4	1.3506 (18)	N12—C9	1.3393 (19)
C1—C2	1.3815 (19)	C7—C8	1.3837 (19)
C2—C3	1.393 (2)	C8—C9	1.386 (2)
C2—H1	0.885 (19)	C8—H7	0.886 (19)
C3—H2	0.951 (17)	C9—H8	0.965 (18)
C5—H3	0.891 (19)	C11—H9	0.940 (19)
C6—H4	0.974 (17)	C12—H10	0.955 (19)
C6—H5	0.988 (17)	C12—H11	0.93 (2)
C6—H6	0.96 (2)	C12—H12	0.957 (19)
C4—S1—C6	101.92 (7)	C10—S2—C12	101.37 (8)
N3—N1—N2	113.78 (11)	N9—N7—N8	113.63 (11)
N3—N1—C1	123.45 (11)	N9—N7—C7	123.40 (11)
N2—N1—C1	122.75 (11)	N8—N7—C7	122.96 (11)
C5—N2—N1	101.28 (11)	C11—N8—N7	101.34 (12)
N4—N3—N1	105.82 (12)	N10—N9—N7	105.89 (12)
N3—N4—C5	106.17 (12)	N9—N10—C11	106.19 (12)
C1—N5—C4	114.47 (12)	C7—N11—C10	114.67 (12)
C3—N6—C4	115.71 (12)	C10—N12—C9	115.82 (12)
N5—C1—C2	125.31 (12)	N11—C7—C8	125.20 (12)
N5—C1—N1	115.33 (12)	N11—C7—N7	115.25 (12)
C2—C1—N1	119.36 (12)	C8—C7—N7	119.55 (12)
C1—C2—C3	114.59 (13)	C7—C8—C9	114.40 (13)
C1—C2—H1	122.4 (11)	C7—C8—H7	122.5 (11)
C3—C2—H1	123.0 (12)	C9—C8—H7	123.1 (12)
N6—C3—C2	123.19 (13)	N12—C9—C8	123.46 (14)
N6—C3—H2	116.5 (10)	N12—C9—H8	116.1 (11)
C2—C3—H2	120.3 (10)	C8—C9—H8	120.5 (11)
N5—C4—N6	126.72 (13)	N12—C10—N11	126.44 (13)
N5—C4—S1	119.87 (10)	N12—C10—S2	119.96 (10)
N6—C4—S1	113.41 (10)	N11—C10—S2	113.60 (10)
N2—C5—N4	112.96 (13)	N8—C11—N10	112.94 (13)
N2—C5—H3	124.0 (12)	N8—C11—H9	124.6 (12)
N4—C5—H3	123.0 (12)	N10—C11—H9	122.5 (12)
S1—C6—H4	108.9 (11)	S2—C12—H10	109.7 (11)
S1—C6—H5	110.3 (10)	S2—C12—H11	105.7 (12)
H4—C6—H5	112.5 (14)	H10—C12—H11	110.6 (16)
S1—C6—H6	103.5 (11)	S2—C12—H12	110.3 (11)
H4—C6—H6	110.8 (15)	H10—C12—H12	111.9 (16)
H5—C6—H6	110.4 (15)	H11—C12—H12	108.4 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H1···N9i	0.89 (2)	2.58 (2)	3.203 (2)	129 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H1⋯N9i	0.89 (2)	2.58 (2)	3.203 (2)	129 (2)

Symmetry code: (i) .