Planarity of heteroaryl­dithio­carbazic acid derivatives showing tuberculostatic activity. III. Mono- and diesters of 3-(pyrazin-2-ylcarbon­yl)dithio­carbazic acid

Methyl 2-(pyrazin-2-ylcarbon­yl)hydrazinecarbodithio­ate, C₇H₈N₄OS₂, (E1), N′-[bis­(methyl­sulfan­yl)methyl­idene]pyrazine-2-carbohydrazide, C₈H₁₀N₄OS₂, (F1), N′-[bis(methyl­sulfan­yl)methyl­idene]-6-meth­oxy­pyrazine-2-carbohydrazide, C₉H₁₂N₄O₂S₂, (F2), and methyl 1-methyl-2-(pyrazin-2-ylcarbon­yl)hydrazinecarbodithio­ate, C₈H₁₀N₄OS₂, (G1), can be con­sid­ered as derivatives of classical (thio)­amide-type tuber­culo­statics, and all are moderately active against Mycobacterium tuberculosis. This study was undertaken in a search for relationships between activity and specific intra­molecular inter­actions, especially conjugations and hydrogen-bond contacts, and the mol­ecular structures were compared with respective amine analogues, also active against the pathogen. Despite the differences between the amine and carbonyl groups with opposite functions in the hydrogen bond, the two types of structure show a surprisingly similar planar geometry, mostly due to the conjugations aided by the bifurcated intra­molecular hydrogen-bond contact between the N—H group of the central hydrazide group as donor and a pyrazine N atom and an S atom of the dithio function as acceptors. Planarity was suggested to be crucial for the tuberculostatic activity of these compounds. The N-methyl­ated derivative (G1) showed a significant twist at the N—N bond [torsion angle = −121.9 (3)°] due to the methyl substitution, which precludes an intra­molecular N—H...S contact and the planarity of the whole mol­ecule. Nonetheless, the compound shows moderate tuberculostatic activity.

S1. Comment

For many years, tuberculosis was considered a disease of the past, limited mainly to poor countries which could not afford expensive treatment, and this led to decreased interest in searching for more effective drugs. However, a more recent rise in mortality rates and the spread of the disease in developed countries, attributed to the emergence of multi-drug resistant strains, have changed this attitude. The search for new lead compounds was continued by several groups (Foks et al., 2000; Gobis, Foks, Zwolska & Augustynowicz-Kopeć, 2006; Gobis, Foks, Żuralska & Kędzia, 2006), who synthesized several chemical classes of potential antituberculostatic agents, in particular those containing either pyrazin-2-yl-carbonimidoyldithiocarbazic acid esters, heteroaroylcarbonimidoyldithiocarbazate or heteroaroyldithiocarbazate systems. The compounds comprise molecular features present in the classical amide-type tuberculostatics, in particular heteroaroyl, amide and thioacid functions, such as in pyrazinamid, isoniazid and ethionamid (see first scheme), which act through the formation of a covalent adduct with nicotinamide adenine dinucleotide (Wang et al., 2007).

Our earlier crystallographic studies of selected representatives of 3-[amino(pyrazin-2-yl)methylidene]-2-methylthiocarbazic acid esters (see second scheme, formula A) showed that all of them maintained planarity of the whole molecule, except for the terminal aliphatic substituents (Główka et al., 2005; Olczak et al., 2007; Orlewska et al., 2001). The planarity observed in these structures was caused by extensive conjugation aided by a bifurcated intramolecular hydrogen-bond contact between the protonated atom N3 as a donor and two acceptors. One acceptor was a negatively charged S atom and the other an ortho-positioned N atom of a pyrazine or pyridine ring on the other side of the donor (second scheme, formula A). The analysis of these data resulted in a working hypothesis that planarity of the molecules is a prerequisite for their tuberculostatic activity (Orlewska et al., 2001).

Next, we showed that similar planarity was maintained in compounds lacking an H atom at N3, such as the dithioesters (formula B in the second scheme), due to conjugation and, except in thioesters (formula A), an intramolecular N—H···N contact was maintained between the same ortho N atom of the reversed pyridine (or pyrazine) ring as acceptor and the N5 amine group as donor. The overall planarity was lost only in the case of N2 substitution in an appropriate monoester (formula C in the second scheme) (Olczak et al., 2011).

The compounds described here represent both S-monothioesters [(E1) and (G1)] and S,S'-dithioesters [(F1) and (F2)] of heteroaroyldithiocarbazic acids (see third scheme and Figs. 1–4), in which an aryl-C(NH₂)═N– function present in the former study (Olczak et al., 2011) has been replaced by a 2-pyrazine-C(O)—NH– one. Thus, the compounds may be considered derivatives of the well known tuberculostatic pyrazinamid (first scheme). Despite the significant differences between these compounds and their amine analogues A, B and C (second scheme), we supposed that, due to the presence of an H atom at N3 in compounds (E1), (F1) and (F2), an analogous intramolecular hydrogen-bond contact will be formed as in the N—H heteroarylcarbamidoyl hydrazinium cation (compound A in the second scheme). As a result, the molecules should be planar and the compounds may show similar antibacterial activity.

In addition, we included in this study compound (G1) (with a methyl substituent at atom N2), which was unable to maintain planarity of the whole molecule due to spatial repulsion between this methyl group and the carbonyl groups (see second scheme). As the compound showed some tuberculostatic activity, it was important to examine changes in its molecular structure. The question concerning planarity could not be answered by simple inspection of the Cambridge Structural Database (CSD, Version?; Allen, 2002), as among about 20 structures comprising esters of heteroaroyldithiocarbazic acid, N2-substituted derivatives are not present. Structures in which the N atom is incorporated into the pyrazine or pyridine ring at the ortho position, thus playing an important role of acceptor in an N3—H···N(aryl) intramolecular hydrogen-bond contact, are similarly absent.

As we expected, the molecules of compounds (E1), (F1) and (F2) are planar except for the terminal ester group, while the molecule of (G1) shows a twist at N—N bond (Fig. 4) caused by spatial repulsion introduced by the methyl group at N2. Thus, we suppose that the main factor responsible for planarity is conjugation from the aryl ring to the thio group. Conjugation along the C1═N2—N3—C4—C41 chain in (F1) and (F2), or the S═C1—N2—N3—C4—C41 chain in (E1), is confirmed by both the values of the respective torsion angles in these fragments, all being close to 180°, and the shortening of the formally single bonds N3—C4 to 1.338 (2), 1.333 (2) and 1.322 (3) Å in the three independent molecules of (E1), 1.344 (2) Å in (F1), 1.341 (4) Å in (F2) and 1.342 (2) Å in (G1), and C4—C41 to 1.494 (3), 1.493 (2) and 1.498 (3) Å in (E1), 1.502 (2) in (F1), 1.497 (4) Å in (F2) and 1.499 (2) Å in (G1) (Table 5).

Due to the overall planarity of the molecules of (E1), (F1) and (F2), there are two short intramolecular hydrogen-bond contacts, both with the N3—H group as the donor (see second scheme and Tables 1–4). The first contact, N3—H..N(pyrazine), is observed in all compounds studied here having an N3—H group, including (G1). The H···N distances and N—H···N angles are in the ranges 2.21–2.28 Å and 107–110°, respectively (Table 6). Similar contacts are observed in N-substituted picolinamides found in the CSD, i.e. 2.15–2.32 Å and 100–116°. The other intramolecular contact is that of N3—H···S, with H···S distances between 2.42 and 2.55 Å, and N—H···S angles between 108 and 113° (Table 6). The values agree well with those found in similar molecules in the CSD (2.37–2.61 Å and 107–113°). The exception is structure (G1), in which substitution at atom N2 (see second scheme ) makes an intramolecular N3—H···S contact impossible.

There are some doubts concerning the structural significance of these contacts (Table 6), mostly due to the commonly accepted view that hydrogen bonds with D—H···A angles below 120° do not contribute substantially to the stabilization energy of the structure (Wood et al., 2009). However, the value of 120° refers to intermolecular hydrogen bonds, while in this study we are concerned with intramolecular systems. In the crystallographic literature, arrangements similar to that formed by the N3—H···N contact (i.e. five-membered ring motifs) were discussed by Bilton et al. (2000) and Galek et al. (2010), who found for them a probability of formation of over 70% and an average hydrogen-bond angle of only 109°. Less is known about N—H···S arrangements similar to those present in the structures described in this study. However, it seems from our data (Table 6), and from a couple of examples comprising a five-membered intramolecular N3—H···S motif which were found in the CSD, that N3—H···S contacts are geometrically less stressed than N3—H···N ones. In consequence, we believe that both the N3—H···N and N3—H···S close contacts observed in this study may be considered intramolecular resonance-assisted hydrogen bonds of some structural significance. The bonds aid conjugation along the main molecular chain to maintain planarity of the whole molecule, except for the terminal substituents of the ester group.

The molecular packing in (E1), (F1) and (F2) is determined mainly by their planarity (Fig. 1 and Figs. 5–6) and relatively weak intermolecular hydrogen bonds. In the diesters (F1) and (F2), there is only one weak C—H···O interaction in each structure. In (F1), C44—H···O5(x - 1, y, z) hydrogen bonds join the molecules into infinite C(7) chains parallel to the [100] direction, while in (F2) the molecules form dimers - R²₂(10) rings according to the graph-set definition of Bernstein et al. (1995) - through C46—H···O5(-x + 1, y, 3/2 - z) hydrogen bonds. In ester (E1), which comprises one hydrogen donor group, N2—H, and three independent molecules, the intermolecular interactions are more complicated. Molecules B and C are connected by N2B—H···O5C and N2C—H···O5B hydrogen bonds (Table 1), joining molecules into approximately coplanar dimers which form R²₂(10) rings. Molecules A and B are connected into asymmetric dimers (Fig. 1) by C44B—H···O5A and N2A—H···N45B hydrogen bonds, forming R²₂(8) rings. In the N'-methylated ester (G1), one weak intermolecular C43—H···O5 hydrogen bond is observed (Table 4). The bonds join the molecules into infinite C(6) chains running parallel to the [110] direction. In addition, an intermolecular N3—H3···S1 short contact may be considered a weak hydrogen bond (Fig. 7).

The terms tuberculostatic and antituberculostatic seem to have been used to mean the same thing. Please check and make consistent.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Bilton et al. (2000); Flack (1983); Foks et al. (2000); Główka et al. (2005); Galek et al. (2010); Gobis, Foks, Zwolska & Augustynowicz-Kopeć (2006); Gobis, Foks, Żuralska & Kędzia (2006); Hooft et al. (2008); Olczak et al. (2007, 2011); Orlewska et al. (2001); Sheldrick (2008); Wang et al. (2007); Wood et al. (2009).

S2. Experimental

The syntheses of the title compounds were described by Foks et al. (2000) for (E1) and (F1), by Gobis, Foks, Zwolska & Augustynowicz-Kopeć (2006) for (G1), and by Gobis , Foks, Żuralska & Kędzia (2006) for (F2). Single crystals of compounds (E1), (F1), (F2) and (G1) suitable for X-ray diffraction were obtained from chloroform–ethanol (1:1 v/v), dioxane, ethanol and ethanol solutions, respectively, by slow evaporation of the solvents at room temperature.

S3. Refinement

H atoms were located in difference Fourier maps and subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.95 for aromatic CH groups, 0.97 for secondary CH₂ groups and 0.96 Å for methyl groups, and N—H = 0.86 Å, with U_iso(H) = 1.2U_eq(C,N). For compound (G1), the precision of the Flack x parameter [Flack (1983); x = 0.18 (11)], whether calculated by the `hole-in-one' method or using TWIN/BASF in SHELXL97 (Sheldrick, 2008), indicated that the structure was correctly oriented with respect to the polar axis direction, but was too imprecise to rule out the possibility of partial inversion twinning. However, the value of the Hooft y parameter [Hooft et al. (2008); y = 0.20 (2)], certainly suggests that partial inversion twinning is present.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007) for E1, F1; APEX2 (Bruker, 2002) for F2, G1. Cell refinement: CrysAlis RED (Oxford Diffraction, 2007) for E1, F1; SAINT-Plus (Bruker, 2003) for F2, G1. Data reduction: CrysAlis RED (Oxford Diffraction, 2007) for E1, F1; SAINT-Plus (Bruker, 2003) for F2, G1. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for E1, G1; SHELXTL (Sheldrick, 2008) for F1, F2. For all compounds, molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (E1), showing the atom-numbering scheme. Intermolecular hydrogen bonds determining the packing of the molecules in the crystal structure are indicated as dashed lines. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (F1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The molecular structure of (F2), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The molecular structure of (G1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. The intermolecular hydrogen-bond contact (dashed line) of (F1) determining the packing of the molecules in the crystal structure. [Symmetry code: (i) x - 1, y, z.]
	Fig. 6. The intermolecular hydrogen-bond contacts (dashed lines) of (F2) determining the packing of the molecules in the crystal structure. [Symmetry code: (i) -x + 1, y, -z + 3/2.]
	Fig. 7. The intermolecular hydrogen-bond contacts (dashed lines) of (G1) determining the packing of the molecules in the crystal structure. [Symmetry codes: (i) x - 1, y - 1, z; (ii) x - 1, y, z.]

(E1) Methyl 2-(pyrazin-2-ylcarbonyl)hydrazinecarbodithioate

Crystal data

C7H8N4OS2	Z = 6
Mr = 228.29	F(000) = 708
Triclinic, P1	Dx = 1.497 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2326 (3) Å	Cell parameters from 7143 reflections
b = 12.7207 (4) Å	θ = 3.0–28.6°
c = 17.7516 (5) Å	µ = 0.50 mm^−1
α = 77.877 (3)°	T = 295 K
β = 79.096 (3)°	Prism, colourless
γ = 73.968 (4)°	0.3 × 0.2 × 0.05 mm
V = 1519.67 (9) Å^3

Data collection

Kuma KM4 CCD area-detector diffractometer	6187 independent reflections
Radiation source: fine-focus sealed tube	4162 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −7→9
Tmin = 0.876, Tmax = 1.000	k = −15→15
18215 measured reflections	l = −22→22

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0504P)^2] where P = (Fo^2 + 2Fc^2)/3
6187 reflections	(Δ/σ)max = 0.001
382 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C01A	0.5803 (4)	0.93418 (18)	0.11244 (14)	0.0707 (7)
H01A	0.7066	0.9309	0.0826	0.085*
H02A	0.5631	0.9772	0.1528	0.085*
H03A	0.4825	0.9682	0.0790	0.085*
C1A	0.6331 (3)	0.72665 (16)	0.07501 (11)	0.0421 (5)
C4A	0.6857 (3)	0.44277 (17)	0.06383 (12)	0.0459 (5)
C41A	0.7674 (3)	0.37711 (16)	−0.00071 (11)	0.0426 (5)
C43A	0.9093 (3)	0.3683 (2)	−0.12376 (12)	0.0581 (6)
H43A	0.9617	0.4006	−0.1721	0.070*
C44A	0.9067 (4)	0.2589 (2)	−0.11229 (14)	0.0610 (7)
H44A	0.9580	0.2200	−0.1535	0.073*
C46A	0.7652 (3)	0.26699 (17)	0.01052 (13)	0.0523 (6)
H46A	0.7133	0.2344	0.0589	0.063*
N2A	0.6215 (3)	0.62144 (13)	0.09642 (9)	0.0467 (4)
H2A	0.5740	0.5983	0.1432	0.056*
N3A	0.6862 (3)	0.55006 (13)	0.04312 (9)	0.0493 (5)
H3A	0.7275	0.5748	−0.0042	0.059*
N42A	0.8395 (3)	0.42982 (14)	−0.06819 (9)	0.0495 (5)
N45A	0.8350 (3)	0.20530 (15)	−0.04555 (12)	0.0611 (5)
O5A	0.6208 (3)	0.40357 (13)	0.12862 (8)	0.0775 (6)
S1A	0.55927 (9)	0.79772 (4)	0.15484 (3)	0.05317 (17)
S2A	0.71449 (9)	0.77865 (5)	−0.01443 (3)	0.05572 (18)
C01B	−0.1677 (4)	0.6732 (2)	0.79005 (12)	0.0821 (9)
H01B	−0.2106	0.6073	0.7930	0.099*
H02B	−0.2539	0.7183	0.8256	0.099*
H03B	−0.0386	0.6532	0.8035	0.099*
C1B	−0.0180 (3)	0.65363 (16)	0.63673 (11)	0.0408 (5)
C4B	0.1625 (3)	0.68096 (16)	0.43404 (11)	0.0406 (5)
C41B	0.2845 (3)	0.59841 (15)	0.38473 (10)	0.0369 (5)
C43B	0.4427 (3)	0.42223 (16)	0.37351 (11)	0.0498 (6)
H43B	0.4838	0.3478	0.3949	0.060*
C44B	0.4933 (3)	0.45526 (16)	0.29415 (11)	0.0473 (5)
H44B	0.5661	0.4021	0.2642	0.057*
C46B	0.3346 (3)	0.63171 (16)	0.30648 (11)	0.0426 (5)
H46B	0.2937	0.7062	0.2852	0.051*
N2B	0.0146 (3)	0.70125 (13)	0.56241 (9)	0.0504 (5)
H2B	−0.0319	0.7712	0.5485	0.061*
N3B	0.1230 (3)	0.63722 (13)	0.50854 (9)	0.0514 (5)
H3B	0.1665	0.5672	0.5232	0.062*
N42B	0.3386 (2)	0.49264 (13)	0.41958 (9)	0.0443 (4)
N45B	0.4411 (3)	0.55972 (13)	0.25994 (9)	0.0448 (4)
O5B	0.1056 (2)	0.77963 (11)	0.40820 (8)	0.0586 (4)
S1B	−0.16796 (10)	0.74930 (5)	0.69347 (3)	0.0639 (2)
S2B	0.07308 (9)	0.51988 (4)	0.66708 (3)	0.05409 (17)
C01C	0.0262 (4)	1.0298 (2)	0.14471 (12)	0.0697 (7)
H01C	−0.1046	1.0420	0.1348	0.084*
H02C	0.1141	0.9878	0.1077	0.084*
H03C	0.0568	1.0999	0.1399	0.084*
C1C	−0.1290 (3)	1.04085 (16)	0.29803 (12)	0.0445 (5)
C4C	−0.2617 (3)	1.01784 (16)	0.50341 (12)	0.0449 (5)
C41C	−0.4024 (3)	1.09280 (16)	0.55445 (11)	0.0426 (5)
C43C	−0.6220 (3)	1.25454 (18)	0.56748 (13)	0.0582 (6)
H43C	−0.6933	1.3238	0.5464	0.070*
C44C	−0.6478 (4)	1.22093 (18)	0.64723 (13)	0.0589 (6)
H44C	−0.7357	1.2686	0.6780	0.071*
C46C	−0.4282 (3)	1.05988 (17)	0.63357 (12)	0.0518 (6)
H46C	−0.3569	0.9907	0.6548	0.062*
N2C	−0.1305 (3)	0.99887 (13)	0.37343 (9)	0.0493 (5)
H2C	−0.0540	0.9357	0.3880	0.059*
N3C	−0.2554 (3)	1.05719 (14)	0.42809 (10)	0.0514 (5)
H3C	−0.3307	1.1204	0.4128	0.062*
N42C	−0.4989 (3)	1.19107 (14)	0.52009 (10)	0.0516 (5)
N45C	−0.5526 (3)	1.12401 (15)	0.68122 (10)	0.0578 (5)
O5C	−0.1632 (2)	0.92709 (12)	0.52968 (8)	0.0626 (4)
S1C	0.04954 (10)	0.95473 (5)	0.24070 (3)	0.05990 (19)
S2C	−0.27473 (10)	1.15904 (5)	0.26468 (4)	0.0662 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C01A	0.102 (2)	0.0417 (13)	0.0621 (16)	−0.0158 (13)	0.0037 (14)	−0.0109 (11)
C1A	0.0461 (13)	0.0424 (12)	0.0338 (11)	−0.0074 (10)	0.0002 (9)	−0.0074 (9)
C4A	0.0559 (14)	0.0395 (11)	0.0356 (11)	−0.0020 (10)	−0.0036 (10)	−0.0074 (9)
C41A	0.0433 (13)	0.0425 (12)	0.0368 (11)	0.0003 (10)	−0.0069 (9)	−0.0085 (9)
C43A	0.0673 (17)	0.0609 (15)	0.0361 (12)	−0.0007 (12)	0.0000 (11)	−0.0128 (11)
C44A	0.0638 (17)	0.0660 (16)	0.0520 (15)	0.0005 (13)	−0.0071 (12)	−0.0300 (12)
C46A	0.0572 (15)	0.0452 (13)	0.0475 (13)	−0.0040 (11)	−0.0035 (11)	−0.0074 (10)
N2A	0.0633 (12)	0.0429 (10)	0.0285 (9)	−0.0101 (9)	0.0070 (8)	−0.0101 (7)
N3A	0.0671 (13)	0.0426 (10)	0.0321 (9)	−0.0098 (9)	0.0081 (8)	−0.0116 (7)
N42A	0.0590 (12)	0.0467 (10)	0.0339 (9)	−0.0012 (9)	−0.0003 (8)	−0.0088 (8)
N45A	0.0643 (14)	0.0515 (12)	0.0669 (13)	−0.0024 (10)	−0.0073 (11)	−0.0261 (10)
O5A	0.1318 (16)	0.0500 (10)	0.0370 (9)	−0.0182 (10)	0.0151 (9)	−0.0072 (7)
S1A	0.0754 (4)	0.0422 (3)	0.0372 (3)	−0.0128 (3)	0.0069 (3)	−0.0117 (2)
S2A	0.0714 (4)	0.0557 (3)	0.0344 (3)	−0.0197 (3)	0.0074 (3)	−0.0032 (2)
C01B	0.119 (2)	0.0796 (19)	0.0353 (13)	−0.0172 (17)	0.0142 (14)	−0.0144 (12)
C1B	0.0448 (13)	0.0427 (11)	0.0333 (11)	−0.0116 (9)	0.0021 (9)	−0.0090 (9)
C4B	0.0457 (13)	0.0354 (11)	0.0358 (11)	−0.0056 (9)	0.0010 (9)	−0.0070 (9)
C41B	0.0422 (12)	0.0336 (10)	0.0307 (10)	−0.0054 (9)	−0.0007 (9)	−0.0055 (8)
C43B	0.0677 (16)	0.0314 (10)	0.0386 (12)	0.0014 (10)	−0.0023 (10)	−0.0032 (9)
C44B	0.0598 (15)	0.0380 (11)	0.0354 (11)	−0.0010 (10)	0.0031 (10)	−0.0109 (9)
C46B	0.0538 (14)	0.0332 (10)	0.0328 (10)	−0.0037 (9)	0.0003 (9)	−0.0027 (8)
N2B	0.0700 (13)	0.0340 (9)	0.0334 (9)	0.0001 (8)	0.0086 (8)	−0.0066 (7)
N3B	0.0752 (13)	0.0330 (9)	0.0310 (9)	0.0009 (8)	0.0092 (8)	−0.0064 (7)
N42B	0.0583 (12)	0.0353 (9)	0.0299 (9)	−0.0015 (8)	−0.0017 (8)	−0.0026 (7)
N45B	0.0583 (12)	0.0376 (9)	0.0297 (9)	−0.0036 (8)	0.0018 (8)	−0.0047 (7)
O5B	0.0772 (11)	0.0350 (8)	0.0428 (8)	0.0058 (7)	0.0079 (7)	−0.0019 (6)
S1B	0.0900 (5)	0.0472 (3)	0.0401 (3)	−0.0053 (3)	0.0155 (3)	−0.0136 (2)
S2B	0.0657 (4)	0.0430 (3)	0.0397 (3)	−0.0023 (3)	0.0019 (3)	0.0004 (2)
C01C	0.094 (2)	0.0611 (15)	0.0424 (13)	−0.0142 (14)	0.0060 (13)	−0.0038 (11)
C1C	0.0541 (14)	0.0345 (11)	0.0422 (12)	−0.0086 (10)	−0.0030 (10)	−0.0068 (9)
C4C	0.0574 (15)	0.0349 (11)	0.0415 (12)	−0.0106 (10)	−0.0005 (10)	−0.0111 (9)
C41C	0.0513 (14)	0.0345 (11)	0.0423 (12)	−0.0086 (10)	−0.0031 (10)	−0.0125 (9)
C43C	0.0707 (17)	0.0405 (12)	0.0510 (14)	0.0049 (11)	−0.0036 (12)	−0.0098 (10)
C44C	0.0715 (17)	0.0454 (13)	0.0529 (14)	−0.0036 (12)	0.0043 (12)	−0.0194 (11)
C46C	0.0697 (16)	0.0352 (11)	0.0445 (13)	−0.0054 (11)	−0.0045 (11)	−0.0068 (9)
N2C	0.0611 (12)	0.0357 (9)	0.0401 (10)	0.0068 (8)	−0.0025 (8)	−0.0116 (8)
N3C	0.0623 (13)	0.0383 (9)	0.0436 (11)	0.0065 (9)	−0.0025 (9)	−0.0150 (8)
N42C	0.0644 (13)	0.0390 (10)	0.0433 (10)	−0.0007 (9)	−0.0027 (9)	−0.0095 (8)
N45C	0.0764 (14)	0.0466 (11)	0.0432 (11)	−0.0068 (10)	0.0023 (10)	−0.0122 (9)
O5C	0.0829 (12)	0.0372 (8)	0.0506 (9)	0.0075 (8)	−0.0017 (8)	−0.0069 (7)
S1C	0.0715 (4)	0.0506 (3)	0.0401 (3)	0.0075 (3)	0.0027 (3)	−0.0088 (2)
S2C	0.0782 (5)	0.0431 (3)	0.0582 (4)	0.0113 (3)	−0.0078 (3)	−0.0033 (3)

Geometric parameters (Å, º)

C01A—S1A	1.777 (2)	C41B—C46B	1.374 (2)
C01A—H01A	0.9600	C43B—N42B	1.319 (2)
C01A—H02A	0.9600	C43B—C44B	1.392 (3)
C01A—H03A	0.9600	C43B—H43B	0.9300
C1A—N2A	1.334 (2)	C44B—N45B	1.322 (2)
C1A—S2A	1.6508 (19)	C44B—H44B	0.9300
C1A—S1A	1.7594 (19)	C46B—N45B	1.342 (2)
C4A—O5A	1.215 (2)	C46B—H46B	0.9300
C4A—N3A	1.338 (2)	N2B—N3B	1.372 (2)
C4A—C41A	1.494 (3)	N2B—H2B	0.8600
C41A—N42A	1.333 (2)	N3B—H3B	0.8600
C41A—C46A	1.377 (3)	C01C—S1C	1.783 (2)
C43A—N42A	1.326 (2)	C01C—H01C	0.9600
C43A—C44A	1.369 (3)	C01C—H02C	0.9600
C43A—H43A	0.9300	C01C—H03C	0.9600
C44A—N45A	1.327 (3)	C1C—N2C	1.332 (2)
C44A—H44A	0.9300	C1C—S2C	1.646 (2)
C46A—N45A	1.334 (3)	C1C—S1C	1.759 (2)
C46A—H46A	0.9300	C4C—O5C	1.226 (2)
N2A—N3A	1.377 (2)	C4C—N3C	1.322 (3)
N2A—H2A	0.8600	C4C—C41C	1.498 (3)
N3A—H3A	0.8600	C41C—N42C	1.334 (2)
C01B—S1B	1.783 (2)	C41C—C46C	1.371 (3)
C01B—H01B	0.9600	C43C—N42C	1.326 (3)
C01B—H02B	0.9600	C43C—C44C	1.383 (3)
C01B—H03B	0.9600	C43C—H43C	0.9300
C1B—N2B	1.337 (2)	C44C—N45C	1.317 (3)
C1B—S2B	1.658 (2)	C44C—H44C	0.9300
C1B—S1B	1.7449 (19)	C46C—N45C	1.337 (3)
C4B—O5B	1.225 (2)	C46C—H46C	0.9300
C4B—N3B	1.333 (2)	N2C—N3C	1.382 (2)
C4B—C41B	1.493 (2)	N2C—H2C	0.8600
C41B—N42B	1.341 (2)	N3C—H3C	0.8600
S1A—C01A—H01A	109.5	C44B—C43B—H43B	118.8
S1A—C01A—H02A	109.5	N45B—C44B—C43B	122.12 (17)
H01A—C01A—H02A	109.5	N45B—C44B—H44B	118.9
S1A—C01A—H03A	109.5	C43B—C44B—H44B	118.9
H01A—C01A—H03A	109.5	N45B—C46B—C41B	121.80 (17)
H02A—C01A—H03A	109.5	N45B—C46B—H46B	119.1
N2A—C1A—S2A	123.16 (14)	C41B—C46B—H46B	119.1
N2A—C1A—S1A	110.90 (13)	C1B—N2B—N3B	119.25 (16)
S2A—C1A—S1A	125.90 (12)	C1B—N2B—H2B	120.4
O5A—C4A—N3A	122.82 (18)	N3B—N2B—H2B	120.4
O5A—C4A—C41A	123.54 (19)	C4B—N3B—N2B	121.60 (16)
N3A—C4A—C41A	113.61 (17)	C4B—N3B—H3B	119.2
N42A—C41A—C46A	122.54 (18)	N2B—N3B—H3B	119.2
N42A—C41A—C4A	117.24 (18)	C43B—N42B—C41B	115.44 (16)
C46A—C41A—C4A	120.21 (19)	C44B—N45B—C46B	115.76 (16)
N42A—C43A—C44A	122.2 (2)	C1B—S1B—C01B	103.38 (11)
N42A—C43A—H43A	118.9	S1C—C01C—H01C	109.5
C44A—C43A—H43A	118.9	S1C—C01C—H02C	109.5
N45A—C44A—C43A	123.5 (2)	H01C—C01C—H02C	109.5
N45A—C44A—H44A	118.2	S1C—C01C—H03C	109.5
C43A—C44A—H44A	118.2	H01C—C01C—H03C	109.5
N45A—C46A—C41A	122.4 (2)	H02C—C01C—H03C	109.5
N45A—C46A—H46A	118.8	N2C—C1C—S2C	123.48 (15)
C41A—C46A—H46A	118.8	N2C—C1C—S1C	111.10 (14)
C1A—N2A—N3A	119.58 (16)	S2C—C1C—S1C	125.42 (12)
C1A—N2A—H2A	120.2	O5C—C4C—N3C	123.20 (18)
N3A—N2A—H2A	120.2	O5C—C4C—C41C	122.44 (18)
C4A—N3A—N2A	120.99 (16)	N3C—C4C—C41C	114.35 (18)
C4A—N3A—H3A	119.5	N42C—C41C—C46C	122.21 (18)
N2A—N3A—H3A	119.5	N42C—C41C—C4C	117.66 (18)
C43A—N42A—C41A	115.02 (19)	C46C—C41C—C4C	120.13 (19)
C44A—N45A—C46A	114.4 (2)	N42C—C43C—C44C	122.0 (2)
C1A—S1A—C01A	102.83 (10)	N42C—C43C—H43C	119.0
S1B—C01B—H01B	109.5	C44C—C43C—H43C	119.0
S1B—C01B—H02B	109.5	N45C—C44C—C43C	122.5 (2)
H01B—C01B—H02B	109.5	N45C—C44C—H44C	118.8
S1B—C01B—H03B	109.5	C43C—C44C—H44C	118.8
H01B—C01B—H03B	109.5	N45C—C46C—C41C	122.1 (2)
H02B—C01B—H03B	109.5	N45C—C46C—H46C	119.0
N2B—C1B—S2B	122.37 (14)	C41C—C46C—H46C	119.0
N2B—C1B—S1B	111.18 (14)	C1C—N2C—N3C	119.72 (17)
S2B—C1B—S1B	126.44 (11)	C1C—N2C—H2C	120.1
O5B—C4B—N3B	123.44 (17)	N3C—N2C—H2C	120.1
O5B—C4B—C41B	122.87 (17)	C4C—N3C—N2C	121.41 (17)
N3B—C4B—C41B	113.69 (16)	C4C—N3C—H3C	119.3
N42B—C41B—C46B	122.47 (17)	N2C—N3C—H3C	119.3
N42B—C41B—C4B	117.52 (16)	C43C—N42C—C41C	115.58 (18)
C46B—C41B—C4B	120.00 (17)	C44C—N45C—C46C	115.64 (18)
N42B—C43B—C44B	122.40 (18)	C1C—S1C—C01C	102.27 (11)
N42B—C43B—H43B	118.8
O5A—C4A—C41A—N42A	−177.9 (2)	C41B—C4B—N3B—N2B	179.22 (18)
N3A—C4A—C41A—N42A	3.7 (3)	C1B—N2B—N3B—C4B	−178.79 (19)
O5A—C4A—C41A—C46A	2.5 (3)	C44B—C43B—N42B—C41B	0.1 (3)
N3A—C4A—C41A—C46A	−175.9 (2)	C46B—C41B—N42B—C43B	−0.4 (3)
N42A—C43A—C44A—N45A	0.1 (4)	C4B—C41B—N42B—C43B	178.64 (19)
N42A—C41A—C46A—N45A	−0.1 (3)	C43B—C44B—N45B—C46B	−0.7 (3)
C4A—C41A—C46A—N45A	179.4 (2)	C41B—C46B—N45B—C44B	0.3 (3)
S2A—C1A—N2A—N3A	2.4 (3)	N2B—C1B—S1B—C01B	−173.40 (18)
S1A—C1A—N2A—N3A	−175.47 (14)	S2B—C1B—S1B—C01B	7.8 (2)
O5A—C4A—N3A—N2A	3.6 (3)	O5C—C4C—C41C—N42C	178.3 (2)
C41A—C4A—N3A—N2A	−177.91 (17)	N3C—C4C—C41C—N42C	−2.6 (3)
C1A—N2A—N3A—C4A	176.6 (2)	O5C—C4C—C41C—C46C	−1.5 (3)
C44A—C43A—N42A—C41A	0.1 (3)	N3C—C4C—C41C—C46C	177.6 (2)
C46A—C41A—N42A—C43A	−0.1 (3)	N42C—C43C—C44C—N45C	−0.2 (4)
C4A—C41A—N42A—C43A	−179.65 (18)	N42C—C41C—C46C—N45C	0.4 (4)
C43A—C44A—N45A—C46A	−0.3 (4)	C4C—C41C—C46C—N45C	−179.8 (2)
C41A—C46A—N45A—C44A	0.3 (3)	S2C—C1C—N2C—N3C	−2.0 (3)
N2A—C1A—S1A—C01A	−178.49 (17)	S1C—C1C—N2C—N3C	177.19 (15)
S2A—C1A—S1A—C01A	3.69 (19)	O5C—C4C—N3C—N2C	−2.1 (3)
O5B—C4B—C41B—N42B	179.8 (2)	C41C—C4C—N3C—N2C	178.82 (17)
N3B—C4B—C41B—N42B	0.2 (3)	C1C—N2C—N3C—C4C	179.6 (2)
O5B—C4B—C41B—C46B	−1.2 (3)	C44C—C43C—N42C—C41C	0.2 (4)
N3B—C4B—C41B—C46B	179.26 (19)	C46C—C41C—N42C—C43C	−0.3 (3)
N42B—C43B—C44B—N45B	0.5 (4)	C4C—C41C—N42C—C43C	179.9 (2)
N42B—C41B—C46B—N45B	0.2 (3)	C43C—C44C—N45C—C46C	0.2 (4)
C4B—C41B—C46B—N45B	−178.81 (19)	C41C—C46C—N45C—C44C	−0.3 (3)
S2B—C1B—N2B—N3B	1.7 (3)	N2C—C1C—S1C—C01C	−178.52 (16)
S1B—C1B—N2B—N3B	−177.20 (16)	S2C—C1C—S1C—C01C	0.6 (2)
O5B—C4B—N3B—N2B	−0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2A···N45B	0.86	2.13	2.987 (2)	174
C44B—H44B···O5A	0.93	2.36	3.061 (2)	132
N2B—H2B···O5C	0.86	1.94	2.790 (2)	172
N2C—H2C···O5B	0.86	2.00	2.850 (2)	170

(F1) N'-[bis(methylsulfanyl)methylidene]pyrazine-2-carbohydrazide

Crystal data

C8H10N4OS2	F(000) = 504
Mr = 242.32	Dx = 1.468 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8241 reflections
a = 7.8332 (2) Å	θ = 2.9–28.6°
b = 21.0883 (4) Å	µ = 0.46 mm^−1
c = 7.3920 (2) Å	T = 297 K
β = 116.121 (4)°	Prism, colourless
V = 1096.36 (5) Å^3	0.2 × 0.1 × 0.05 mm
Z = 4

Data collection

Kuma KM4 CCD area-detector diffractometer	2236 independent reflections
Radiation source: fine-focus sealed tube	1960 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ω scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −9→8
Tmin = 0.946, Tmax = 1.000	k = −26→26
12975 measured reflections	l = −9→9

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)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0445P)^2 + 0.2852P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2236 reflections	Δρmax = 0.26 e Å^−3
139 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (11)

Special details

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C1	1.0226 (2)	0.61366 (8)	0.7928 (2)	0.0423 (4)
C01	1.3336 (3)	0.61423 (10)	0.7154 (3)	0.0628 (5)
H01A	1.4011	0.6417	0.8281	0.075*
H01B	1.2553	0.6392	0.5998	0.075*
H01C	1.4230	0.5903	0.6867	0.075*
C02	0.7790 (3)	0.50863 (9)	0.6980 (3)	0.0624 (5)
H02A	0.8867	0.4810	0.7363	0.075*
H02B	0.7338	0.5203	0.5590	0.075*
H02C	0.6798	0.4872	0.7165	0.075*
C4	0.8997 (2)	0.77379 (8)	0.7750 (2)	0.0398 (3)
C41	0.7227 (2)	0.80257 (7)	0.7710 (2)	0.0374 (3)
C43	0.4284 (2)	0.78993 (8)	0.7531 (3)	0.0490 (4)
H43	0.3279	0.7644	0.7431	0.059*
C44	0.4121 (2)	0.85490 (8)	0.7613 (3)	0.0490 (4)
H44	0.3002	0.8716	0.7562	0.059*
C46	0.7053 (2)	0.86748 (8)	0.7796 (3)	0.0458 (4)
H46	0.8049	0.8933	0.7881	0.055*
N2	1.03942 (18)	0.67337 (6)	0.7761 (2)	0.0421 (3)
N3	0.89650 (18)	0.71015 (6)	0.7821 (2)	0.0425 (3)
H3	0.8023	0.6918	0.7906	0.051*
N42	0.58415 (18)	0.76297 (6)	0.7590 (2)	0.0456 (3)
N45	0.5491 (2)	0.89439 (7)	0.7761 (2)	0.0529 (4)
O5	1.02739 (17)	0.80592 (6)	0.7719 (2)	0.0585 (3)
S1	1.18679 (6)	0.56102 (2)	0.77482 (9)	0.05940 (17)
S2	0.84763 (6)	0.57861 (2)	0.85177 (8)	0.05666 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0299 (7)	0.0463 (9)	0.0505 (9)	0.0015 (6)	0.0174 (7)	−0.0056 (7)
C01	0.0438 (9)	0.0729 (13)	0.0832 (14)	0.0051 (9)	0.0384 (10)	−0.0046 (10)
C02	0.0549 (11)	0.0463 (10)	0.0793 (13)	−0.0074 (8)	0.0234 (10)	0.0030 (9)
C4	0.0345 (7)	0.0460 (8)	0.0415 (8)	0.0018 (6)	0.0191 (6)	−0.0010 (6)
C41	0.0337 (7)	0.0420 (8)	0.0382 (7)	0.0018 (6)	0.0174 (6)	−0.0006 (6)
C43	0.0375 (8)	0.0495 (9)	0.0668 (11)	0.0025 (7)	0.0291 (8)	−0.0002 (8)
C44	0.0425 (9)	0.0519 (10)	0.0591 (10)	0.0107 (7)	0.0283 (8)	0.0000 (8)
C46	0.0426 (9)	0.0422 (8)	0.0558 (10)	−0.0018 (7)	0.0246 (8)	−0.0017 (7)
N2	0.0317 (6)	0.0468 (7)	0.0501 (7)	0.0049 (5)	0.0200 (6)	−0.0040 (6)
N3	0.0325 (6)	0.0438 (7)	0.0573 (8)	0.0036 (5)	0.0255 (6)	0.0001 (6)
N42	0.0377 (7)	0.0419 (7)	0.0629 (8)	0.0020 (6)	0.0272 (6)	0.0001 (6)
N45	0.0528 (8)	0.0445 (8)	0.0666 (9)	0.0066 (7)	0.0310 (7)	−0.0040 (7)
O5	0.0461 (7)	0.0540 (7)	0.0896 (9)	−0.0041 (6)	0.0428 (7)	−0.0028 (7)
S1	0.0461 (3)	0.0486 (3)	0.0918 (4)	0.00612 (19)	0.0379 (3)	−0.0082 (2)
S2	0.0465 (3)	0.0522 (3)	0.0816 (4)	−0.00241 (19)	0.0376 (2)	−0.0025 (2)

Geometric parameters (Å, º)

C1—N2	1.278 (2)	C4—C41	1.502 (2)
C1—S1	1.7478 (15)	C41—N42	1.3411 (19)
C1—S2	1.7723 (16)	C41—C46	1.380 (2)
C01—S1	1.794 (2)	C43—N42	1.329 (2)
C01—H01A	0.9600	C43—C44	1.380 (2)
C01—H01B	0.9600	C43—H43	0.9300
C01—H01C	0.9600	C44—N45	1.324 (2)
C02—S2	1.795 (2)	C44—H44	0.9300
C02—H02A	0.9600	C46—N45	1.339 (2)
C02—H02B	0.9600	C46—H46	0.9300
C02—H02C	0.9600	N2—N3	1.3785 (17)
C4—O5	1.2165 (19)	N3—H3	0.8600
C4—N3	1.344 (2)
N2—C1—S1	120.54 (12)	N42—C41—C4	117.57 (14)
N2—C1—S2	123.95 (12)	C46—C41—C4	120.60 (14)
S1—C1—S2	115.37 (9)	N42—C43—C44	121.67 (16)
S1—C01—H01A	109.5	N42—C43—H43	119.2
S1—C01—H01B	109.5	C44—C43—H43	119.2
H01A—C01—H01B	109.5	N45—C44—C43	122.71 (15)
S1—C01—H01C	109.5	N45—C44—H44	118.6
H01A—C01—H01C	109.5	C43—C44—H44	118.6
H01B—C01—H01C	109.5	N45—C46—C41	121.85 (15)
S2—C02—H02A	109.5	N45—C46—H46	119.1
S2—C02—H02B	109.5	C41—C46—H46	119.1
H02A—C02—H02B	109.5	C1—N2—N3	115.58 (13)
S2—C02—H02C	109.5	C4—N3—N2	122.10 (13)
H02A—C02—H02C	109.5	C4—N3—H3	119.0
H02B—C02—H02C	109.5	N2—N3—H3	119.0
O5—C4—N3	125.92 (14)	C43—N42—C41	116.10 (14)
O5—C4—C41	122.27 (14)	C44—N45—C46	115.82 (14)
N3—C4—C41	111.81 (13)	C1—S1—C01	101.17 (9)
N42—C41—C46	121.83 (14)	C1—S2—C02	103.63 (9)
O5—C4—C41—N42	174.91 (15)	C1—N2—N3—C4	177.07 (15)
N3—C4—C41—N42	−5.0 (2)	C44—C43—N42—C41	−0.8 (3)
O5—C4—C41—C46	−5.2 (2)	C46—C41—N42—C43	0.9 (2)
N3—C4—C41—C46	174.88 (15)	C4—C41—N42—C43	−179.16 (14)
N42—C43—C44—N45	−0.2 (3)	C43—C44—N45—C46	1.0 (3)
N42—C41—C46—N45	−0.1 (3)	C41—C46—N45—C44	−0.8 (3)
C4—C41—C46—N45	179.96 (14)	N2—C1—S1—C01	−4.05 (17)
S1—C1—N2—N3	176.70 (11)	S2—C1—S1—C01	−179.90 (10)
S2—C1—N2—N3	−7.8 (2)	N2—C1—S2—C02	141.69 (15)
O5—C4—N3—N2	−3.4 (3)	S1—C1—S2—C02	−42.62 (12)
C41—C4—N3—N2	176.49 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C44—H44···O5^i	0.93	2.59	3.219 (2)	125

Symmetry code: (i) x−1, y, z.

(F2) N'-[bis(methylsulfanyl)methylidene]-6-methoxypyrazine-2-carbohydrazide

Crystal data

C9H12N4O2S2	F(000) = 1136
Mr = 272.35	Dx = 1.461 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8658 reflections
a = 23.111 (2) Å	θ = 2.7–27.0°
b = 7.5812 (7) Å	µ = 0.43 mm^−1
c = 15.6547 (14) Å	T = 270 K
β = 115.430 (2)°	Prisme, colourless
V = 2477.1 (4) Å^3	0.5 × 0.2 × 0.1 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3051 independent reflections
Radiation source: fine-focus sealed tube	2351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −30→30
Tmin = 0.516, Tmax = 1	k = −10→9
27591 measured reflections	l = −20→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.072P)^2 + 1.1533P] where P = (Fo^2 + 2Fc^2)/3
3051 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.41 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
C1	0.32187 (8)	0.0500 (2)	0.93843 (13)	0.0441 (4)
C01	0.30859 (12)	0.0459 (3)	1.10871 (16)	0.0677 (6)
H01A	0.2641	0.0784	1.0808	0.081*
H01B	0.3278	0.0790	1.1743	0.081*
H01C	0.3124	−0.0793	1.1034	0.081*
C02	0.23931 (11)	−0.1431 (3)	0.78714 (16)	0.0634 (5)
H02A	0.2379	−0.0503	0.7446	0.076*
H02B	0.2007	−0.2115	0.7593	0.076*
H02C	0.2755	−0.2177	0.7991	0.076*
C4	0.44767 (9)	0.1438 (2)	0.87865 (12)	0.0460 (4)
C11	0.56273 (13)	0.3733 (3)	1.20507 (16)	0.0721 (6)
H11A	0.5205	0.4214	1.1714	0.086*
H11B	0.5820	0.4214	1.2679	0.086*
H11C	0.5600	0.2473	1.2085	0.086*
C41	0.51134 (8)	0.2302 (2)	0.93364 (12)	0.0431 (4)
C43	0.58091 (9)	0.3626 (2)	1.06730 (14)	0.0513 (4)
C44	0.62150 (10)	0.3955 (3)	1.02402 (17)	0.0635 (6)
H44	0.6592	0.4578	1.0573	0.076*
C46	0.55275 (9)	0.2544 (3)	0.89284 (14)	0.0552 (5)
H46	0.5422	0.2096	0.8327	0.066*
N2	0.35298 (7)	0.05000 (19)	0.88799 (10)	0.0447 (3)
N3	0.41252 (7)	0.13022 (19)	0.92788 (10)	0.0434 (3)
H3	0.4271	0.1716	0.9844	0.052*
N42	0.52559 (7)	0.28252 (19)	1.02262 (10)	0.0438 (3)
N45	0.60835 (9)	0.3418 (3)	0.93820 (15)	0.0655 (5)
O5	0.43033 (8)	0.0961 (2)	0.79736 (10)	0.0717 (5)
O6	0.60084 (8)	0.4175 (2)	1.15676 (11)	0.0686 (4)
S1	0.34869 (3)	0.15723 (7)	1.04845 (4)	0.06153 (19)
S2	0.24630 (2)	−0.05000 (7)	0.89574 (4)	0.06069 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0410 (9)	0.0385 (8)	0.0517 (9)	−0.0059 (6)	0.0191 (7)	0.0012 (7)
C01	0.0616 (12)	0.0903 (16)	0.0595 (12)	−0.0078 (12)	0.0340 (10)	0.0074 (11)
C02	0.0565 (12)	0.0572 (12)	0.0619 (12)	−0.0108 (9)	0.0115 (9)	−0.0041 (9)
C4	0.0451 (9)	0.0483 (9)	0.0460 (9)	−0.0047 (7)	0.0208 (7)	0.0025 (7)
C11	0.0822 (17)	0.0718 (14)	0.0557 (12)	0.0029 (12)	0.0234 (12)	−0.0056 (10)
C41	0.0397 (8)	0.0414 (8)	0.0493 (9)	0.0000 (7)	0.0200 (7)	0.0060 (7)
C43	0.0416 (9)	0.0437 (9)	0.0598 (11)	−0.0002 (7)	0.0137 (8)	0.0026 (8)
C44	0.0413 (10)	0.0619 (12)	0.0793 (15)	−0.0096 (9)	0.0182 (10)	0.0054 (10)
C46	0.0467 (10)	0.0636 (12)	0.0600 (11)	−0.0008 (9)	0.0273 (9)	0.0060 (9)
N2	0.0389 (7)	0.0456 (8)	0.0472 (7)	−0.0075 (6)	0.0162 (6)	0.0003 (6)
N3	0.0394 (7)	0.0484 (8)	0.0425 (7)	−0.0087 (6)	0.0177 (6)	−0.0004 (6)
N42	0.0384 (7)	0.0407 (7)	0.0504 (8)	0.0002 (6)	0.0174 (6)	0.0033 (6)
N45	0.0445 (9)	0.0780 (12)	0.0789 (13)	−0.0065 (8)	0.0312 (9)	0.0111 (9)
O5	0.0675 (10)	0.1027 (12)	0.0505 (8)	−0.0296 (9)	0.0305 (7)	−0.0154 (8)
O6	0.0584 (9)	0.0720 (9)	0.0619 (9)	−0.0125 (7)	0.0131 (7)	−0.0119 (7)
S1	0.0646 (3)	0.0686 (3)	0.0621 (3)	−0.0243 (3)	0.0374 (3)	−0.0169 (2)
S2	0.0445 (3)	0.0661 (3)	0.0731 (3)	−0.0184 (2)	0.0267 (2)	−0.0089 (2)

Geometric parameters (Å, º)

C1—N2	1.276 (2)	C11—H11A	0.9600
C1—S2	1.7519 (17)	C11—H11B	0.9600
C1—S1	1.7592 (18)	C11—H11C	0.9600
C01—S1	1.792 (2)	C41—N42	1.346 (2)
C01—H01A	0.9600	C41—C46	1.372 (3)
C01—H01B	0.9600	C43—N42	1.313 (2)
C01—H01C	0.9600	C43—O6	1.339 (3)
C02—S2	1.783 (2)	C43—C44	1.395 (3)
C02—H02A	0.9600	C44—N45	1.308 (3)
C02—H02B	0.9600	C44—H44	0.9300
C02—H02C	0.9600	C46—N45	1.345 (3)
C4—O5	1.214 (2)	C46—H46	0.9300
C4—N3	1.342 (2)	N2—N3	1.3839 (19)
C4—C41	1.499 (2)	N3—H3	0.8600
C11—O6	1.425 (3)
N2—C1—S2	119.89 (13)	H11B—C11—H11C	109.5
N2—C1—S1	123.41 (13)	N42—C41—C46	122.19 (17)
S2—C1—S1	116.61 (10)	N42—C41—C4	117.81 (15)
S1—C01—H01A	109.5	C46—C41—C4	120.00 (17)
S1—C01—H01B	109.5	N42—C43—O6	121.31 (18)
H01A—C01—H01B	109.5	N42—C43—C44	121.85 (19)
S1—C01—H01C	109.5	O6—C43—C44	116.84 (18)
H01A—C01—H01C	109.5	N45—C44—C43	122.32 (19)
H01B—C01—H01C	109.5	N45—C44—H44	118.8
S2—C02—H02A	109.5	C43—C44—H44	118.8
S2—C02—H02B	109.5	N45—C46—C41	121.27 (19)
H02A—C02—H02B	109.5	N45—C46—H46	119.4
S2—C02—H02C	109.5	C41—C46—H46	119.4
H02A—C02—H02C	109.5	C1—N2—N3	115.85 (14)
H02B—C02—H02C	109.5	C4—N3—N2	120.27 (14)
O5—C4—N3	124.78 (17)	C4—N3—H3	119.9
O5—C4—C41	122.21 (16)	N2—N3—H3	119.9
N3—C4—C41	112.99 (15)	C43—N42—C41	115.91 (16)
O6—C11—H11A	109.5	C44—N45—C46	116.32 (18)
O6—C11—H11B	109.5	C43—O6—C11	117.95 (16)
H11A—C11—H11B	109.5	C1—S1—C01	104.67 (10)
O6—C11—H11C	109.5	C1—S2—C02	101.68 (10)
H11A—C11—H11C	109.5
O5—C4—C41—N42	178.34 (18)	O6—C43—N42—C41	−178.65 (16)
N3—C4—C41—N42	0.0 (2)	C44—C43—N42—C41	1.7 (3)
O5—C4—C41—C46	−1.3 (3)	C46—C41—N42—C43	1.8 (3)
N3—C4—C41—C46	−179.71 (16)	C4—C41—N42—C43	−177.90 (15)
N42—C43—C44—N45	−3.1 (3)	C43—C44—N45—C46	0.9 (3)
O6—C43—C44—N45	177.2 (2)	C41—C46—N45—C44	2.6 (3)
N42—C41—C46—N45	−4.1 (3)	N42—C43—O6—C11	5.2 (3)
C4—C41—C46—N45	175.60 (17)	C44—C43—O6—C11	−175.1 (2)
S2—C1—N2—N3	−179.29 (11)	N2—C1—S1—C01	−156.84 (16)
S1—C1—N2—N3	4.4 (2)	S2—C1—S1—C01	26.73 (14)
O5—C4—N3—N2	3.1 (3)	N2—C1—S2—C02	4.43 (17)
C41—C4—N3—N2	−178.58 (14)	S1—C1—S2—C02	−179.00 (11)
C1—N2—N3—C4	−177.06 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C46—H46···O5^i	0.93	2.53	3.385 (3)	153

Symmetry code: (i) −x+1, y, −z+3/2.

(G1) methyl 1-methyl-2-(pyrazin-2-ylcarbonyl)hydrazinecarbodithioate

Crystal data

C8H10N4OS2	F(000) = 252
Mr = 242.32	Dx = 1.469 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8014 reflections
a = 4.0900 (4) Å	θ = 2.9–30.4°
b = 6.4482 (6) Å	µ = 0.47 mm^−1
c = 20.7828 (19) Å	T = 290 K
β = 91.151 (2)°	Prism, colourless
V = 548.00 (9) Å^3	0.35 × 0.2 × 0.1 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2642 independent reflections
Radiation source: fine-focus sealed tube	2523 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −5→5
Tmin = 0.716, Tmax = 1	k = −8→8
12608 measured reflections	l = −26→27

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0713P)^2 + 0.2203P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2642 reflections	Δρmax = 0.68 e Å^−3
138 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.18 (11)

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
C1	1.0937 (7)	0.8741 (5)	0.85674 (13)	0.0386 (6)
C01	1.4285 (9)	0.5824 (6)	0.93116 (16)	0.0562 (9)
H01A	1.2695	0.6055	0.9638	0.067*
H01B	1.6046	0.6797	0.9366	0.067*
H01C	1.5123	0.4438	0.9349	0.067*
C4	0.9719 (7)	0.8113 (5)	0.69513 (14)	0.0388 (6)
C10	0.7799 (9)	1.1372 (6)	0.79370 (16)	0.0524 (7)
H10A	0.9419	1.2346	0.7801	0.063*
H10B	0.6903	1.1826	0.8337	0.063*
H10C	0.6084	1.1282	0.7616	0.063*
C41	0.8459 (7)	0.6519 (4)	0.64844 (12)	0.0362 (5)
C43	0.5792 (9)	0.3512 (5)	0.62875 (18)	0.0534 (8)
H43	0.4588	0.2380	0.6427	0.064*
C44	0.6554 (10)	0.3659 (6)	0.56436 (18)	0.0576 (8)
H44	0.5901	0.2599	0.5366	0.069*
C46	0.9132 (9)	0.6699 (5)	0.58369 (14)	0.0488 (7)
H46	1.0275	0.7854	0.5696	0.059*
N2	0.9302 (7)	0.9338 (4)	0.80247 (11)	0.0419 (5)
N3	0.8641 (6)	0.7856 (4)	0.75509 (11)	0.0402 (5)
H3	0.7532	0.6767	0.7644	0.048*
N42	0.6733 (7)	0.4945 (4)	0.67133 (12)	0.0451 (6)
N45	0.8187 (9)	0.5261 (6)	0.54075 (13)	0.0591 (7)
O5	1.1584 (6)	0.9485 (4)	0.67904 (12)	0.0572 (6)
S1	1.23971 (17)	0.61678 (12)	0.85307 (3)	0.04268 (18)
S2	1.1449 (2)	1.03003 (14)	0.91904 (4)	0.0560 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0403 (13)	0.0456 (14)	0.0299 (12)	−0.0142 (11)	0.0015 (9)	−0.0026 (11)
C01	0.0605 (18)	0.064 (2)	0.0433 (15)	−0.0092 (16)	−0.0072 (13)	0.0087 (15)
C4	0.0428 (14)	0.0384 (14)	0.0351 (13)	−0.0074 (11)	−0.0021 (10)	0.0015 (11)
C10	0.0706 (19)	0.0403 (16)	0.0461 (16)	−0.0038 (15)	−0.0042 (13)	−0.0019 (13)
C41	0.0427 (12)	0.0339 (14)	0.0320 (12)	−0.0024 (10)	−0.0019 (9)	0.0011 (9)
C43	0.067 (2)	0.0418 (16)	0.0508 (17)	−0.0136 (14)	−0.0067 (14)	−0.0026 (14)
C44	0.077 (2)	0.0509 (18)	0.0440 (17)	−0.0065 (16)	−0.0115 (15)	−0.0130 (15)
C46	0.0645 (17)	0.0498 (18)	0.0320 (13)	−0.0082 (13)	0.0021 (12)	0.0011 (11)
N2	0.0574 (14)	0.0380 (12)	0.0302 (11)	−0.0095 (10)	−0.0044 (9)	−0.0016 (10)
N3	0.0541 (14)	0.0356 (12)	0.0308 (11)	−0.0154 (10)	−0.0023 (9)	−0.0030 (9)
N42	0.0606 (15)	0.0401 (13)	0.0343 (11)	−0.0129 (11)	−0.0026 (10)	0.0026 (10)
N45	0.0846 (19)	0.0588 (16)	0.0338 (12)	−0.0037 (16)	−0.0001 (12)	−0.0049 (13)
O5	0.0711 (15)	0.0531 (13)	0.0476 (12)	−0.0294 (12)	0.0079 (11)	−0.0005 (10)
S1	0.0502 (3)	0.0432 (3)	0.0346 (3)	−0.0061 (3)	−0.0022 (2)	0.0018 (3)
S2	0.0715 (5)	0.0599 (5)	0.0363 (3)	−0.0106 (4)	−0.0040 (3)	−0.0148 (3)

Geometric parameters (Å, º)

C1—N2	1.355 (4)	C10—H10C	0.9600
C1—S2	1.649 (3)	C41—N42	1.330 (4)
C1—S1	1.765 (3)	C41—C46	1.384 (4)
C01—S1	1.797 (3)	C43—N42	1.331 (4)
C01—H01A	0.9600	C43—C44	1.383 (5)
C01—H01B	0.9600	C43—H43	0.9300
C01—H01C	0.9600	C44—N45	1.329 (5)
C4—O5	1.219 (4)	C44—H44	0.9300
C4—N3	1.341 (4)	C46—N45	1.338 (4)
C4—C41	1.497 (4)	C46—H46	0.9300
C10—N2	1.458 (4)	N2—N3	1.395 (3)
C10—H10A	0.9600	N3—H3	0.8600
C10—H10B	0.9600
N2—C1—S2	122.2 (2)	C46—C41—C4	120.0 (3)
N2—C1—S1	113.1 (2)	N42—C43—C44	121.9 (3)
S2—C1—S1	124.69 (18)	N42—C43—H43	119.1
S1—C01—H01A	109.5	C44—C43—H43	119.1
S1—C01—H01B	109.5	N45—C44—C43	122.3 (3)
H01A—C01—H01B	109.5	N45—C44—H44	118.8
S1—C01—H01C	109.5	C43—C44—H44	118.8
H01A—C01—H01C	109.5	N45—C46—C41	122.0 (3)
H01B—C01—H01C	109.5	N45—C46—H46	119.0
O5—C4—N3	124.3 (3)	C41—C46—H46	119.0
O5—C4—C41	121.9 (3)	C1—N2—N3	118.6 (3)
N3—C4—C41	113.7 (2)	C1—N2—C10	124.0 (3)
N2—C10—H10A	109.5	N3—N2—C10	116.9 (2)
N2—C10—H10B	109.5	C4—N3—N2	120.6 (2)
H10A—C10—H10B	109.5	C4—N3—H3	119.7
N2—C10—H10C	109.5	N2—N3—H3	119.7
H10A—C10—H10C	109.5	C41—N42—C43	116.1 (3)
H10B—C10—H10C	109.5	C44—N45—C46	115.6 (3)
N42—C41—C46	121.9 (3)	C1—S1—C01	102.50 (16)
N42—C41—C4	118.0 (2)
O5—C4—C41—N42	172.6 (3)	O5—C4—N3—N2	8.0 (5)
N3—C4—C41—N42	−6.5 (4)	C41—C4—N3—N2	−172.9 (3)
O5—C4—C41—C46	−6.7 (5)	C1—N2—N3—C4	−121.9 (3)
N3—C4—C41—C46	174.2 (3)	C10—N2—N3—C4	66.0 (4)
N42—C43—C44—N45	−1.9 (6)	C46—C41—N42—C43	2.4 (5)
N42—C41—C46—N45	−2.5 (5)	C4—C41—N42—C43	−176.9 (3)
C4—C41—C46—N45	176.8 (3)	C44—C43—N42—C41	−0.3 (5)
S2—C1—N2—N3	−172.5 (2)	C43—C44—N45—C46	1.9 (6)
S1—C1—N2—N3	7.3 (3)	C41—C46—N45—C44	0.2 (6)
S2—C1—N2—C10	−1.0 (4)	N2—C1—S1—C01	−178.2 (2)
S1—C1—N2—C10	178.8 (2)	S2—C1—S1—C01	1.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1^i	0.86	2.85	3.473 (3)	131
C43—H43···O5^ii	0.93	2.37	3.297 (4)	179

Symmetry codes: (i) x−1, y, z; (ii) x−1, y−1, z.