Crystal structure of 2,3,5,6-tetra-kis[(methyl-sulfan-yl)meth-yl]pyrazine.

The title compound, C12H20N2S4, synthesized by the reaction of 2,3,5,6-tetra-kis-(bromo-meth-yl)pyrazine with sodium methane-thiol-ate, crystallizes with a half -mol-ecule in the asymmetric unit. The whole mol-ecule is generated by inversion symmetry; the inversion centre being located in the centre of the pyrazine ring. The mol-ecule has an S-shaped conformation with two (methyl-sulfan-yl)methyl substituent arms directed above the plane of the pyrazine ring and two below. The C(H3)-S-C(H2)-C(aromatic) torsion angles are 70.47 (18) and -67.65 (17)°, respectively. In the crystal, mol-ecules are linked via weak C-H⋯S hydrogen bonds, forming chains along [001] and enclosing R 2 (2)(12) ring motifs. The chains are linked by further weak C-H⋯S hydrogen bonds, forming sheets lying parallel to (101).

Related literature

For syntheses of the starting reagent, 2,3,5,6-tetra­kis­(bromo­meth­yl)pyrazine, see: Ferigo et al. (1994 ▶); Assoumatine (1999 ▶); Assoumatine & Stoeckli-Evans (2014 ▶). For the crystal structures of similar sulfanylmethyl derivatives of pyrazine, such as two triclinic polymorphs of 2,3,5,6 tetra­kis­(naphthalen-2-ylsulfanylmeth­yl)pyrazine both possessing inversion symmetry, see: Pacifico & Stoeckli-Evans (2004 ▶), and for 2,3,5,6-tetra­kis­(phenyl­sulfanylmeth­yl)pyrazine, which also crystallizes in space group P and possesses inversion symmetry, see: Assoumatine et al. (2007 ▶).

Experimental

Crystal data

C12H20N2S4

M = 320.54

Triclinic,

a = 6.6773 (6) Å

b = 6.9433 (4) Å

c = 9.5135 (5) Å

α = 102.635 (6)°

β = 107.539 (5)°

γ = 99.462 (9)°

V = 397.61 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.58 mm−1

T = 293 K

0.40 × 0.40 × 0.23 mm

Data collection

Stoe AED2 four-circle diffractometer

2960 measured reflections

1478 independent reflections

1283 reflections with I > 2σ(I)

R int = 0.018

3 standard reflections every 60 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.088

S = 1.08

1478 reflections

85 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.20 e Å−3

Data collection: STADI4 (Stoe & Cie, 1997 ▶); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL2013, PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814011246/hb0006sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814011246/hb0006Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814011246/hb0006Isup3.cml

Click here for additional data file.

x y+1 z . DOI: 10.1107/S1600536814011246/hb0006fig1.tif

A view of the mol­ecular structure of the title mol­ecule, with atom labelling (unlabelled atoms are generated by inversion symmetry with symmetry code: −x, -y+1, −z + 1). Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S1600536814011246/hb0006fig2.tif

A partial view along the a axis of the crystal packing of the title compound, showing the formation of the C—H⋯S hydrogen-bonded chains along [001], enclosing (12) ring motifs (H atoms not involved in these hydrogen bonds have been omitted for clarity).

CCDC reference: 1004261

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

C12H20N2S4	Z = 1
Mr = 320.54	F(000) = 170
Triclinic, P1	Dx = 1.339 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6773 (6) Å	Cell parameters from 33 reflections
b = 6.9433 (4) Å	θ = 14.2–18.8°
c = 9.5135 (5) Å	µ = 0.58 mm−1
α = 102.635 (6)°	T = 293 K
β = 107.539 (5)°	Plate, yellow
γ = 99.462 (9)°	0.40 × 0.40 × 0.23 mm
V = 397.61 (5) Å3

Stoe AED2 four-circle diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 2.3°
Graphite monochromator	h = −8→7
2θ/ω scans	k = −8→8
2960 measured reflections	l = 0→11
1478 independent reflections	3 standard reflections every 60 min
1283 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.032	H-atom parameters constrained
wR(F2) = 0.088	w = 1/[σ2(Fo2) + (0.0451P)2 + 0.1143P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
1478 reflections	Δρmax = 0.24 e Å−3
85 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.064 (11)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

	x	y	z	Uiso*/Ueq
S1	0.10172 (10)	0.33963 (9)	0.10899 (6)	0.0509 (2)
S2	0.37011 (9)	0.28482 (9)	0.80525 (6)	0.0515 (2)
N1	−0.0169 (2)	0.2930 (2)	0.44718 (16)	0.0326 (4)
C1	−0.0580 (3)	0.4056 (3)	0.34870 (19)	0.0311 (5)
C2	0.0402 (3)	0.3854 (3)	0.59786 (19)	0.0313 (5)
C3	−0.1194 (3)	0.2955 (3)	0.1806 (2)	0.0390 (6)
C4	0.2772 (5)	0.2016 (4)	0.2027 (3)	0.0684 (10)
C5	0.0843 (3)	0.2519 (3)	0.7029 (2)	0.0376 (6)
C6	0.4534 (4)	0.1829 (4)	0.6484 (3)	0.0665 (9)
H3A	−0.23980	0.33950	0.12120	0.0470*
H3B	−0.16800	0.15040	0.16540	0.0470*
H4A	0.33380	0.26610	0.31160	0.1030*
H4B	0.39480	0.20040	0.16450	0.1030*
H4C	0.19730	0.06420	0.18230	0.1030*
H5A	0.02160	0.11060	0.64270	0.0450*
H5B	0.01290	0.28160	0.77720	0.0450*
H6A	0.36700	0.04660	0.59450	0.1000*
H6B	0.60330	0.18130	0.68720	0.1000*
H6C	0.43450	0.26620	0.57940	0.1000*

	U11	U22	U33	U12	U13	U23
S1	0.0731 (4)	0.0608 (4)	0.0394 (3)	0.0318 (3)	0.0335 (3)	0.0242 (3)
S2	0.0568 (4)	0.0584 (4)	0.0352 (3)	0.0256 (3)	0.0050 (2)	0.0128 (2)
N1	0.0386 (8)	0.0332 (8)	0.0285 (7)	0.0114 (6)	0.0133 (6)	0.0097 (6)
C1	0.0355 (9)	0.0350 (9)	0.0252 (8)	0.0112 (7)	0.0123 (7)	0.0092 (7)
C2	0.0340 (9)	0.0371 (9)	0.0272 (8)	0.0112 (7)	0.0134 (7)	0.0123 (7)
C3	0.0492 (11)	0.0408 (10)	0.0265 (9)	0.0141 (8)	0.0124 (8)	0.0076 (8)
C4	0.0750 (17)	0.0855 (19)	0.0741 (17)	0.0467 (15)	0.0399 (14)	0.0415 (15)
C5	0.0493 (11)	0.0384 (10)	0.0307 (9)	0.0154 (8)	0.0164 (8)	0.0145 (8)
C6	0.0570 (15)	0.0784 (18)	0.0633 (16)	0.0307 (13)	0.0207 (12)	0.0090 (13)

S1—C3	1.813 (2)	C3—H3B	0.9700
S1—C4	1.789 (3)	C4—H4A	0.9600
S2—C5	1.812 (2)	C4—H4B	0.9600
S2—C6	1.790 (3)	C4—H4C	0.9600
N1—C1	1.342 (2)	C5—H5A	0.9700
N1—C2	1.342 (2)	C5—H5B	0.9700
C1—C3	1.509 (2)	C6—H6A	0.9600
C1—C2i	1.401 (3)	C6—H6B	0.9600
C2—C5	1.504 (3)	C6—H6C	0.9600
C3—H3A	0.9700
C3—S1—C4	101.45 (13)	S1—C4—H4B	109.00
C5—S2—C6	100.09 (11)	S1—C4—H4C	109.00
C1—N1—C2	118.31 (16)	H4A—C4—H4B	109.00
N1—C1—C3	116.40 (17)	H4A—C4—H4C	109.00
N1—C1—C2i	120.78 (15)	H4B—C4—H4C	109.00
C2i—C1—C3	122.82 (17)	S2—C5—H5A	109.00
N1—C2—C5	116.03 (17)	S2—C5—H5B	109.00
N1—C2—C1i	120.91 (17)	C2—C5—H5A	109.00
C1i—C2—C5	123.05 (15)	C2—C5—H5B	109.00
S1—C3—C1	113.18 (14)	H5A—C5—H5B	108.00
S2—C5—C2	113.56 (15)	S2—C6—H6A	109.00
S1—C3—H3A	109.00	S2—C6—H6B	109.00
S1—C3—H3B	109.00	S2—C6—H6C	109.00
C1—C3—H3A	109.00	H6A—C6—H6B	110.00
C1—C3—H3B	109.00	H6A—C6—H6C	109.00
H3A—C3—H3B	108.00	H6B—C6—H6C	109.00
S1—C4—H4A	109.00
C4—S1—C3—C1	70.47 (18)	C2i—C1—C3—S1	77.1 (2)
C6—S2—C5—C2	−67.65 (17)	N1—C1—C2i—N1i	−0.5 (3)
C2—N1—C1—C3	179.41 (18)	N1—C1—C2i—C5i	−180.00 (19)
C2—N1—C1—C2i	0.4 (3)	C3—C1—C2i—N1i	−179.35 (18)
C1—N1—C2—C5	179.98 (18)	C3—C1—C2i—C5i	1.1 (3)
C1—N1—C2—C1i	−0.4 (3)	N1—C2—C5—S2	103.98 (18)
N1—C1—C3—S1	−101.84 (19)	C1i—C2—C5—S2	−75.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···S2i	0.97	2.89	3.589 (2)	130
C5—H5B···S1ii	0.97	2.95	3.7395 (19)	139
C5—H5B···S1i	0.97	2.93	3.614 (2)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯S2i	0.97	2.89	3.589 (2)	130
C5—H5B⋯S1ii	0.97	2.95	3.7395 (19)	139
C5—H5B⋯S1i	0.97	2.93	3.614 (2)	128

Symmetry codes: (i) ; (ii) .