Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
X-ray diffraction studies reveal that pyrazine-2-thiol undergoes condensation to 2,2′-di­thio­bis­pyrazine [systematic name: 2-(pyrazin-2-yldisulfanyl)pyrazine], C8H6N4S2 (I), under aerial conditions. In the mol­ecule of I, the pyrazine rings are arranged in an almost perpendicular manner, with an absolute value of the C—S—S—C torsion angle of −91.45 (6)°. A search in the Cambridge Structural Database confirmed that such a conformation is typical for di­sulfide com­pounds. Three different rotamers of di­sulfide I were studied using quantum theoretical studies. The rotamer of lowest energy was observed in the crystalline state in the structure stabilized by hydrogen-bond, chalcogen-bond and stacking inter­actions. Further quantum chemical com­putations confirm that 2,2′-di­thio­bis­pyrazine can react according to the SN2 mechanism.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229623007416/dg3042sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229623007416/dg3042Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229623007416/dg3042Isup3.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229623007416/dg3042sup4.pdf
Selected geometrical parameters for disulfide compounds

CCDC reference: 2290145

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-(Pyrazin-2-yldisulfanyl)pyrazine top
Crystal data top
C8H6N4S2Z = 2
Mr = 222.29F(000) = 228
Triclinic, P1Dx = 1.550 Mg m3
a = 5.6832 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.4639 (2) ÅCell parameters from 6130 reflections
c = 11.7473 (3) Åθ = 2.8–29.2°
α = 91.524 (2)°µ = 0.52 mm1
β = 95.245 (2)°T = 293 K
γ = 106.024 (2)°Cut plate, yellow
V = 476.24 (2) Å30.24 × 0.08 × 0.03 mm
Data collection top
Rigaku XtaLAB Synergy Dualflex
diffractometer with a HyPix detector
2551 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source1990 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.032
Detector resolution: 10.0000 pixels mm-1θmax = 31.1°, θmin = 2.8°
ω scansh = 77
Absorption correction: gaussian
(CrysAlis PRO; Rigaku OD, 2020)
k = 1010
Tmin = 0.646, Tmax = 1.000l = 1616
13219 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.087 w = 1/[σ2(Fo2) + (0.0388P)2 + 0.0599P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2551 reflectionsΔρmax = 0.24 e Å3
127 parametersΔρmin = 0.26 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S12A0.88777 (8)0.82515 (5)0.24527 (3)0.05535 (14)
S120.51768 (8)0.75339 (6)0.21054 (3)0.05632 (14)
N11A1.1678 (2)0.85466 (18)0.43568 (11)0.0534 (3)
N110.5985 (2)0.42008 (18)0.16399 (12)0.0542 (3)
N14A0.8155 (3)0.6392 (2)0.56361 (12)0.0586 (3)
N140.1119 (2)0.2607 (2)0.07399 (12)0.0613 (4)
C120.4351 (3)0.5157 (2)0.15903 (11)0.0416 (3)
C12A0.9380 (3)0.77714 (18)0.39184 (12)0.0435 (3)
C13A0.7614 (3)0.6697 (2)0.45469 (13)0.0512 (4)
H13A0.6021920.6180270.4200520.061*
C150.2761 (3)0.1648 (2)0.07863 (13)0.0531 (4)
H150.2274970.0406960.0512160.064*
C130.1918 (3)0.4365 (2)0.11467 (13)0.0558 (4)
H130.0821790.5088590.1135400.067*
C16A1.2209 (3)0.8212 (2)0.54463 (15)0.0591 (4)
H16A1.3806390.8712810.5790860.071*
C160.5152 (3)0.2425 (2)0.12250 (15)0.0574 (4)
H160.6239870.1694610.1235870.069*
C15A1.0470 (3)0.7152 (2)0.60712 (14)0.0589 (4)
H15A1.0925510.6958130.6828460.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S12A0.0613 (3)0.0465 (2)0.0493 (2)0.00156 (17)0.01245 (17)0.00042 (15)
S120.0651 (3)0.0501 (2)0.0575 (2)0.02468 (19)0.00036 (18)0.00203 (17)
N11A0.0421 (7)0.0502 (7)0.0609 (8)0.0008 (5)0.0103 (5)0.0097 (6)
N110.0383 (7)0.0471 (7)0.0743 (8)0.0114 (5)0.0045 (6)0.0062 (6)
N14A0.0550 (8)0.0572 (8)0.0553 (7)0.0016 (6)0.0059 (6)0.0074 (6)
N140.0394 (7)0.0701 (9)0.0683 (8)0.0094 (6)0.0052 (6)0.0069 (7)
C120.0414 (7)0.0488 (7)0.0364 (6)0.0151 (6)0.0041 (5)0.0044 (5)
C12A0.0441 (8)0.0329 (6)0.0497 (7)0.0039 (5)0.0089 (6)0.0047 (5)
C13A0.0425 (8)0.0489 (8)0.0540 (8)0.0005 (6)0.0042 (6)0.0040 (6)
C150.0444 (8)0.0508 (8)0.0573 (8)0.0033 (7)0.0037 (6)0.0045 (7)
C130.0415 (8)0.0699 (11)0.0592 (9)0.0237 (8)0.0027 (6)0.0004 (8)
C16A0.0432 (8)0.0613 (10)0.0672 (10)0.0089 (7)0.0017 (7)0.0119 (8)
C160.0424 (8)0.0472 (8)0.0815 (11)0.0141 (7)0.0015 (7)0.0068 (7)
C15A0.0591 (10)0.0608 (10)0.0537 (9)0.0144 (8)0.0015 (7)0.0011 (7)
Geometric parameters (Å, º) top
S12A—S122.0216 (6)C12—C131.391 (2)
S12A—C12A1.7816 (14)C12A—C13A1.385 (2)
S12—C121.7792 (15)C13A—H13A0.9300
N11A—C12A1.3227 (19)C15—H150.9300
N11A—C16A1.334 (2)C15—C161.367 (2)
N11—C121.3166 (19)C13—H130.9300
N11—C161.340 (2)C16A—H16A0.9300
N14A—C13A1.329 (2)C16A—C15A1.369 (3)
N14A—C15A1.328 (2)C16—H160.9300
N14—C151.321 (2)C15A—H15A0.9300
N14—C131.324 (2)
C12A—S12A—S12104.70 (5)N14—C15—H15119.0
C12—S12—S12A104.87 (5)N14—C15—C16122.02 (15)
C12A—N11A—C16A115.79 (13)C16—C15—H15119.0
C12—N11—C16115.54 (13)N14—C13—C12121.76 (15)
C15A—N14A—C13A116.19 (14)N14—C13—H13119.1
C15—N14—C13116.23 (13)C12—C13—H13119.1
N11—C12—S12120.89 (11)N11A—C16A—H16A119.1
N11—C12—C13122.03 (14)N11A—C16A—C15A121.84 (15)
C13—C12—S12117.08 (11)C15A—C16A—H16A119.1
N11A—C12A—S12A112.32 (10)N11—C16—C15122.42 (15)
N11A—C12A—C13A122.57 (13)N11—C16—H16118.8
C13A—C12A—S12A125.10 (11)C15—C16—H16118.8
N14A—C13A—C12A121.17 (14)N14A—C15A—C16A122.42 (15)
N14A—C13A—H13A119.4N14A—C15A—H15A118.8
C12A—C13A—H13A119.4C16A—C15A—H15A118.8
S12A—S12—C12—N118.43 (12)C12—N11—C16—C150.5 (2)
S12A—S12—C12—C13172.07 (10)C12A—N11A—C16A—C15A0.8 (2)
S12A—C12A—C13A—N14A179.24 (12)C13A—N14A—C15A—C16A0.8 (3)
S12—S12A—C12A—N11A165.73 (10)C15—N14—C13—C120.4 (2)
S12—S12A—C12A—C13A15.01 (14)C13—N14—C15—C160.2 (2)
S12—C12—C13—N14179.87 (13)C16A—N11A—C12A—S12A178.51 (11)
N11A—C12A—C13A—N14A0.0 (2)C16A—N11A—C12A—C13A0.8 (2)
N11A—C16A—C15A—N14A0.1 (3)C16—N11—C12—S12179.90 (12)
N11—C12—C13—N140.6 (2)C16—N11—C12—C130.6 (2)
N14—C15—C16—N110.3 (3)C15A—N14A—C13A—C12A0.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13A—H13A···S120.932.743.2220 (16)113
C13A—H13A···N14Ai0.932.643.433 (2)144
Symmetry code: (i) x+1, y+1, z+1.
Comparison of conformers structural parameters: selected torsion and dihedral angles between pyrazine planes (°); (I) is the present experimental X-ray data and A, B and C are conformers obtained in the optimization process at the RI-MP2/def2-TZVPP level top
(I)Conformer AConformer BConformer C
C12A—S12A—S12—C12-91.5 (1)-81.20-79.12-76.02
N11A—C12A—S12A—S12-165.73 (10)-171.60-176.657.13
N11—C12—S12—S12A8.43 (12)22.24-174.949.26
C13A—C12A—S12A—S1215.01 (14)10.014.89-174.32
C13—C12—S12—S12A-172.07 (10)-171.606.76-172.23
<(PLN1/PLN2)84.0 (3)69.5574.7169.54
Selected geometrical parameters (Å, °) of the intermolecular interactions in I top
D—H/S···AD—H/SH/S···AD···AD—H/S···A
C13—H13···N11i0.932.763.443 (2)130.3
C16—H16···N14i0.932.793.456 (2)129.8
C16A—H16A···N11Ai0.932.833.628 (1)144.6
S12A—S12···S12Ai2.0216 (6)3.819 (2)152.0 (1)
C12A···C15A3.701 (1)
Symmetry code: (i) x+1, y, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds