Planarity of heteroaryl­dithio­carb­azic acid derivatives showing tuberculostatic activity. II. Crystal structures of 3-[amino­(pyrazin-2-yl)­methyl­idene]-2-methyl­carbazic acid esters

Four compounds showing moderate anti­tuberculostatic activity have been studied to test the hypothesis that the planarity of the 2-[amino­(pyrazin-2-yl)methylid­ene]­dithio­car­baz­ate fragment is crucial for activity. N'-Anilino­pyrazine-2-carbox­imid­amide, C₁₁H₁₁N₅, D1, and diethyl 2,2'-[({[am­ino­(pyrazin-2-yl)methyl­idene]­hydrazinyl­idene}­methylidene)­bis­(sulfane­diyl)]­diacetate, C₁₄H₁₉N₅O₄S₂, B1, maintain planarity due to conjugation and attractive intra­molecular hydrogen-bond contacts, while methyl 3-[amino­(pyrazin-2-yl)­methyl­idene]-2-methyldithio­­carbazate, C₈H₁₁N₅S₂, C1, and benzyl 3-[amino­(pyrazin-2-yl)­methyl­idene]-2-methyldithio­­carb­azate, C₁₄H₁₅N₅S₂, C2, are not planar, due to methyl­ation at one of the N atoms of the central N-N bond. The resulting twists of the two mol­ecular halves (parts) of C1 and C2 are indicated by torsion angles of 116.5 (2) and -135.9 (2)°, respectively, compared with values of about 180° in the crystal structures of nonsubstituted compounds. As the methyl­ated derivatives show similar activity against Mycobacterium tuberculosis to that of the nonsubstituted derivatives, maintaining planarity does not seem to be a prerequisite for activity.

S1. Comment

The increasing resistance of Mycobacterium tuberculosis against existing agents and the resulting spread of the pathogen, also in developed countries, makes the search for new tuberculostatics an important issue. 2-, 3- and 4-pyridinecarbonimidoyldithiocarbazonic acid esters and N'-thioamido-substituted pyrazincarboxyamidrazones, of which many compounds have been synthesized by Foks and Orlewska and tested against standard M. tuberculosis strains (Foks & Janowiec, 1979; Foks et al., 1992, 2002, 2004; Orlewska, 1996; Orlewska et al., 1995, 2001), are one of the promising chemical classes showing action against tuberculosis.

Our earlier studies of the crystal structures of the representatives of this class (A in Scheme 1), which all existed in a dipolar form, showed the same molecular features, of which the most significant was the bifurcated intramolecular hydrogen bond between the protonated atom N3 as a donor and two acceptors, the anionic S atom from the thioacid function and the N atom at the ortho position of the pyridine or pyrazine ring (Główka et al., 2005; Olczak et al., 2007; Orlewska et al., 2001). A search of the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) succeeded in finding only two other similar structures (Bermejo et al., 2001; Ketcham et al., 2001) showing the features described above. The attractive intramolecular hydrogen-bond contacts and extensive conjugation, both present in these zwitterionic structures, keep all atoms of the molecules coplanar, except the terminal thioester or thioamide group (A in Scheme 1). In addition, in two crystal structures of S,S'-diesters of pyridinecarbonimidoyldithiocarbazonic acid (B in Scheme 1) showing moderate activity against M. tuberculosis strains, coplanarity was also maintained despite the lack of an active H atom at N3 (Główka et al., 1999).

An analysis of the data available at that time suggested that planarity of the pyridin-2-yl or pyrazin-2-yl-formamide thiosemicarbazone fragment could be a prerequisite for tuberculostatic activity (Olczak et al., 2007). To check the importance and generality of this observation, we have determined and describe in this study four crystal structures of other mono- and diesters of pyridine- or pyrazinecarbonimidoyldithiocarbazonic acid derivatives, B1, C1, C2 and D1, having the same pyridine- or pyrazineamidine fragment but lacking protonation on atom N3 and, as a consequence, lacking crucial intramolecular (bifurcated) hydrogen-bond contacts with N3—H as a donor.

Together with six thioamide and thioester structures found in the CSD (Bermejo et al., 2004, 2005a,b; Castiñeiras et al., 2000; Labisbal et al., 2002; West et al., 1999), these compounds form a sufficient set for statistical analysis and verification of the hypothesis that the planarity of a whole molecule is correlated with activity, especially given that, in two structures presented here (C1 and C2), atom N2 has been substituted by a methyl group. The substitution introduces spatial repulsion between the methyl group at atom N2 and the neighbouring amine group at atom C4, and forces a twist at the N2—N3 bond (Figs. 1 and 2), which also excludes conjugations involving that bond. As a result, we expected a significant difference in their activities.

With the exception of the twist at the N2—N3 bond in structures C1 and C2, both halves of the molecules are planar. The coplanarity of the pyrazinyl ring and the neighbouring imide group in all structures determined in this work, as expected on the basis of known structures (Bermejo et al., 2004, 2005a,b; Castiñeiras et al., 2000; Główka et al., 1999; Labisbal et al., 2002; West et al., 1999), is indicated by the C41—C4═N3—N2 torsion angles of -177.67 (12), -177.88 (13), 176.53 (12) and -178.18 (13)°, respectively, for B1, C1, C2 and D1 (Table 5). The coplanarity is obviously secured by the attractive intramolecular hydrogen-bond contact N5—H···N(pyridine), characterized by H···N42 distances of 2.2–2.7 Å and angles at H of 101–112°, as no significant conjugation between the π systems of the pyrazine ring and imide group (Scheme 1) is observed. This observation is confirmed by the lengths of the formally single bonds C4—C41 and C4—N5, in the ranges 1.473–1.493 and 1.329–1.358 Å, respectively (Table 5). Instead, in C1 and C2, another conjugated system (S═C1—N2) is observed, resulting in the shortening of the C1—N2 bond to about 1.34 Å (Table 5), compared with 1.43–1.48 Å in similar fragments containing a tetrahedral C atom found in the CSD. As expected, the resulting twist around the N2—N3 bond in C1 and C2 breaks the coplanarity of the pyrazinamidrazone and thioacid fragments, which has been observed in all monoesters of heteroarylcarbonamidoyldithiocarbazonic acids studied so far by X-ray diffraction. This is evidenced in this study by the torsion angle C1—N2—N3═C4 being 116.5 (2)° in C1 and -135.9 (2)° in C2, compared with the antiperiplanar conformation observed in B1 and D1 (Figs. 3 and 4) and 24 similar structures found in the CSD. The largest deviation of the C1—N2—N3═C4 torsion angle from 180° is 7.5° found in B1.

Surprisingly, as the tuberculostatic activities of the `non-planar' compounds C1 and C2 against three selected strains of Mycobacterium tuberculosis are similar to those of other tested compounds (Zwolska, 2009), it seems that maintaining planarity of the whole molecule is not important for its biological action. However, the engagement of hydrophilic H atoms in the intramolecular hydrogen-bond contacts commonly observed in these compounds may facilitate the smooth passage of the studied molecules through hydrophobic cell membranes, which may also affect their tuberculostatic activity.

Despite the differences in the chemical structures of the type A, B, C and D compounds, the intermolecular hydrogen-bond contacts observed in their crystal structures reveal a common motif: a C(6) chain (Bernstein et al., 1995) formed through an N5—H5A···N45 hydrogen bond (Tables 1–4). In C2 and B1, the chain runs parallel to the [010] direction, in C1 parallel to [100] and in D1 parallel to [021]. In C2 this is the only hydrogen-bond pattern formed (Fig. 5). The same phenomenon is observed in all structures bearing appropriate functions in analogous positions of the molecules (Olczak et al., 2007; Zhang et al., 2009). In C1, at the first level of graph-set theory an additional motif is formed through an N5—H5B···S2 interaction (Table 2), namely a C(7) chain parallel to the [010] direction (Fig. 6). These two chains form a sheet parallel to the (001) plane in which (at the second level of graph-set theory) an R₄⁴(24) ring can be identified (Fig. 6). In D1, apart from the C(6) chain common to all studied structures, a new C(4) chain parallel to the [001] direction appears through an N5—H5B···N3 hydrogen bond (Fig. 7). These two chains at the second level of graph-set theory cause the appearance of an R₄⁴(18) ring (Fig. 7). The most complex hydrogen-bond pattern is found in B1 because of the existence of four different hydrogen bonds (Fig. 8). At the first level there are four chains: (a) C(6) parallel to [010], (b) C(4) parallel to [001], (c) C(13) parallel to [001] and (d) C(10) parallel to [001]. At the second level, for each pair of hydrogen bonds the following rings can be identified: (ab) R³₃(24), (ac) R₄⁴(32), (ad) R₄⁴(30), (bc) R₄⁴(42), (bd) R₄⁴(36) and (cd) R³₄(32). The smallest rings observed at the third level are as follows: (abc) R⁵₅(32), (abd) R⁵₅(30), (acd) R²₃(7) and (bcd) R³₄(27). At the fourth level, R⁶₆(33) is the smallest ring which is formed in this structure.

Related literature

For related literature, see: Allen (2002); Bermejo et al. (2001, 2004, 2005a, 2005b); Bernstein et al. (1995); Castiñeiras et al. (2000); Foks & Janowiec (1979); Foks et al. (1992, 2002, 2004); Główka et al. (1999, 2005); Ketcham et al. (2001); Labisbal et al. (2002); Olczak et al. (2007); Orlewska (1996); Orlewska et al. (1995, 2001); West et al. (1999); Zhang et al. (2009); Zwolska (2009).

S2. Experimental

The syntheses of the title compounds were as described by Foks & Janowiec (1979) for D1, Foks et al. (1992) for B1, and Orlewska (1996) for C1 and C2.

Single crystals of compounds B1, C1, C2 and D1 suitable for X-ray diffraction were obtained from chloroform–ethanol (Solvent ratio?), chloroform–ethanol (Solvent ratio?), chlorobenzene and chloroform solutions, respectively, by slow evaporation of the solvent at room temperature.

S3. Refinement

H atoms were located in difference Fourier maps and subsequently allowed for as riding atoms, with C—H = 0.95 for aromatic CH and 0.97 Å for secondary CH₂ groups and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007) for B1, C1, D1; APEX2 (Bruker, 2002) for C2. Cell refinement: CrysAlis RED (Oxford Diffraction, 2007) for B1, C1, D1; SAINT-Plus (Bruker, 2003) for C2. Data reduction: CrysAlis RED (Oxford Diffraction, 2007) for B1, C1, D1; SAINT-Plus (Bruker, 2003) for C2. For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of C1, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of C2, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular structure of B1, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The molecular structure of D1, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 5. The intermolecular hydrogen bonds (dashed lines) in the crystal structure of C2, determining the packing of the molecules. Two C(6) chains (related by a centre of symmetry) parallel to [010] run in opposite directions.
	Fig. 6. The intermolecular hydrogen bonds (dashed lines) in the crystal structure of C1, determining the packing of the molecules. Two chains, C(6) parallel to [100] and C(7) parallel to [010], form an R4^4(24) ring at the second level of graph-set theory.
	Fig. 7. The intermolecular hydrogen bonds (dashed lines) in the crystal structure of D1, determining the packing of the molecules. C(6) chains parallel to [021] and C(4) chains parallel to [001] form R4^4(18) rings at the second level of graph-set theory.
	Fig. 8. (a) The intermolecular hydrogen bonds (dashed lines) and (b) the packing of the molecules in the crystal structure of B1. The structure contains four distinct hydrogen bonds, designated a (N5—H5A···N45^i), b (C11—H11A···O12^iii), c (C44—H44···O22^ii) and d (N5—H5B···O22^iv). [Symmetry codes: (i) x, y + 1, z; (ii) x, -y, z - 1/2; (iii) -x + 1/2, y + 1/2, -z + 1/2; (iv) x, -y + 1, z - 1/2.]

(B1) diethyl 2,2'-[({[amino(pyrazin-2- yl)methylidene]hydrazinylidene}methylidene)bis(sulfanediyl)]diacetate

Crystal data

C14H19N5O4S2	F(000) = 1616
Mr = 385.46	Dx = 1.400 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 12369 reflections
a = 29.5249 (14) Å	θ = 2.7–28.5°
b = 8.0969 (9) Å	µ = 0.32 mm^−1
c = 15.4717 (6) Å	T = 291 K
β = 98.635 (4)°	Plate, colourless
V = 3656.7 (5) Å^3	0.4 × 0.3 × 0.1 mm
Z = 8

Data collection

Kuma KM-4 CCD area-detector diffractometer	3722 independent reflections
Radiation source: fine-focus sealed tube	3064 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −36→36
Tmin = 0.729, Tmax = 1.000	k = −8→10
21104 measured reflections	l = −19→19

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)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0593P)^2 + 0.6854P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3722 reflections	Δρmax = 0.36 e Å^−3
227 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (2)

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.13 (release 29–11-2007 CrysAlis171. NET) (compiled Nov 29 2007,17:23:28) 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	0.15561 (5)	0.35264 (17)	0.12965 (9)	0.0341 (3)
C4	0.10830 (5)	0.23775 (18)	−0.07261 (8)	0.0356 (3)
C11	0.20470 (6)	0.20016 (19)	0.27392 (9)	0.0414 (3)
H11A	0.2337	0.2539	0.2700	0.050*
H11B	0.1863	0.2746	0.3034	0.050*
C12	0.21301 (5)	0.04261 (18)	0.32516 (9)	0.0363 (3)
C14	0.24295 (6)	−0.05918 (18)	0.46614 (9)	0.0429 (4)
H14A	0.2609	−0.1406	0.4401	0.051*
H14B	0.2153	−0.1118	0.4794	0.051*
C15	0.26990 (7)	0.0099 (2)	0.54705 (11)	0.0567 (5)
H15A	0.2516	0.0887	0.5726	0.068*
H15B	0.2969	0.0633	0.5328	0.068*
H15C	0.2787	−0.0778	0.5879	0.068*
C21	0.13426 (5)	0.67846 (18)	0.13933 (10)	0.0415 (3)
H21A	0.1418	0.7848	0.1667	0.050*
H21B	0.1424	0.6824	0.0809	0.050*
C22	0.08327 (5)	0.65033 (18)	0.13266 (9)	0.0416 (3)
C24	0.01131 (6)	0.7266 (3)	0.05408 (14)	0.0791 (7)
H24A	−0.0015	0.8015	0.0930	0.095*
H24B	0.0020	0.6151	0.0660	0.095*
C25	−0.00556 (8)	0.7709 (4)	−0.03911 (16)	0.0989 (9)
H25A	−0.0007	0.8866	−0.0478	0.119*
H25B	−0.0377	0.7464	−0.0525	0.119*
H25C	0.0109	0.7081	−0.0769	0.119*
C41	0.09896 (5)	0.08074 (18)	−0.12173 (9)	0.0372 (3)
C43	0.07013 (8)	−0.0511 (3)	−0.24623 (12)	0.0694 (6)
H43	0.0557	−0.0490	−0.3039	0.083*
C44	0.08200 (7)	−0.2004 (2)	−0.20854 (12)	0.0604 (5)
H44	0.0751	−0.2961	−0.2410	0.072*
C46	0.11129 (6)	−0.0708 (2)	−0.08432 (11)	0.0483 (4)
H46	0.1259	−0.0735	−0.0268	0.058*
N2	0.13292 (4)	0.37312 (15)	0.05315 (7)	0.0392 (3)
N3	0.12640 (4)	0.22133 (15)	0.00863 (7)	0.0400 (3)
N5	0.09644 (5)	0.37870 (17)	−0.11533 (8)	0.0498 (3)
H5A	0.1007	0.4717	−0.0885	0.060*
H5B	0.0846	0.3762	−0.1696	0.060*
N42	0.07829 (5)	0.09141 (18)	−0.20412 (9)	0.0581 (4)
N45	0.10316 (6)	−0.21282 (18)	−0.12694 (10)	0.0586 (4)
O12	0.20462 (4)	−0.09417 (14)	0.29774 (7)	0.0523 (3)
O13	0.23145 (4)	0.07862 (12)	0.40646 (7)	0.0462 (3)
O22	0.06498 (4)	0.56275 (15)	0.17990 (7)	0.0532 (3)
O23	0.06124 (4)	0.73868 (17)	0.06809 (8)	0.0621 (4)
S1	0.175323 (13)	0.15511 (4)	0.16549 (2)	0.04032 (13)
S2	0.167798 (13)	0.52195 (5)	0.20082 (2)	0.04149 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0396 (7)	0.0317 (7)	0.0298 (6)	0.0026 (6)	0.0016 (5)	−0.0013 (5)
C4	0.0397 (7)	0.0349 (8)	0.0314 (7)	0.0000 (6)	0.0026 (5)	−0.0001 (6)
C11	0.0528 (9)	0.0339 (8)	0.0340 (7)	0.0006 (7)	−0.0051 (6)	0.0023 (6)
C12	0.0402 (7)	0.0327 (8)	0.0347 (7)	0.0022 (6)	0.0012 (6)	0.0004 (6)
C14	0.0592 (9)	0.0311 (8)	0.0360 (7)	0.0033 (7)	−0.0008 (7)	0.0062 (6)
C15	0.0777 (12)	0.0453 (9)	0.0418 (9)	−0.0028 (9)	−0.0081 (8)	0.0038 (7)
C21	0.0535 (9)	0.0286 (7)	0.0402 (8)	0.0034 (6)	−0.0006 (6)	0.0019 (6)
C22	0.0539 (9)	0.0345 (8)	0.0344 (7)	0.0063 (7)	−0.0001 (6)	−0.0013 (6)
C24	0.0502 (11)	0.1023 (18)	0.0822 (14)	0.0085 (11)	0.0018 (10)	0.0312 (13)
C25	0.0657 (14)	0.133 (2)	0.0912 (17)	0.0060 (15)	−0.0089 (12)	0.0316 (17)
C41	0.0433 (7)	0.0371 (8)	0.0311 (7)	−0.0014 (6)	0.0056 (6)	−0.0033 (6)
C43	0.1009 (15)	0.0554 (12)	0.0450 (10)	−0.0038 (11)	−0.0120 (10)	−0.0166 (9)
C44	0.0806 (13)	0.0453 (10)	0.0560 (10)	−0.0099 (9)	0.0122 (9)	−0.0201 (8)
C46	0.0676 (10)	0.0376 (9)	0.0395 (8)	−0.0002 (7)	0.0068 (7)	−0.0012 (7)
N2	0.0508 (7)	0.0341 (6)	0.0304 (6)	0.0022 (5)	−0.0019 (5)	−0.0029 (5)
N3	0.0539 (7)	0.0332 (6)	0.0305 (6)	0.0031 (6)	−0.0018 (5)	−0.0036 (5)
N5	0.0777 (9)	0.0344 (7)	0.0322 (6)	−0.0001 (7)	−0.0087 (6)	−0.0012 (5)
N42	0.0846 (11)	0.0448 (8)	0.0381 (7)	0.0019 (8)	−0.0128 (7)	−0.0070 (6)
N45	0.0843 (11)	0.0374 (8)	0.0556 (9)	−0.0018 (7)	0.0149 (8)	−0.0065 (7)
O12	0.0722 (8)	0.0335 (6)	0.0457 (6)	−0.0007 (6)	−0.0087 (5)	−0.0013 (5)
O13	0.0720 (7)	0.0288 (5)	0.0340 (5)	0.0029 (5)	−0.0047 (5)	0.0028 (4)
O22	0.0606 (7)	0.0528 (7)	0.0453 (6)	−0.0011 (6)	0.0053 (5)	0.0123 (6)
O23	0.0500 (7)	0.0722 (9)	0.0616 (7)	0.0066 (6)	0.0001 (5)	0.0323 (7)
S1	0.0564 (2)	0.0309 (2)	0.03109 (19)	0.00535 (16)	−0.00190 (15)	−0.00167 (14)
S2	0.0524 (2)	0.0328 (2)	0.0346 (2)	0.00512 (16)	−0.00873 (15)	−0.00556 (15)

Geometric parameters (Å, º)

C1—N2	1.2803 (17)	C21—H21B	0.9700
C1—S2	1.7613 (14)	C22—O22	1.2031 (19)
C1—S1	1.7628 (14)	C22—O23	1.3183 (18)
C4—N3	1.2966 (17)	C24—O23	1.461 (2)
C4—N5	1.3389 (19)	C24—C25	1.497 (3)
C4—C41	1.486 (2)	C24—H24A	0.9700
C11—C12	1.5026 (19)	C24—H24B	0.9700
C11—S1	1.8062 (14)	C25—H25A	0.9600
C11—H11A	0.9700	C25—H25B	0.9600
C11—H11B	0.9700	C25—H25C	0.9600
C12—O12	1.1985 (18)	C41—N42	1.3309 (18)
C12—O13	1.3258 (17)	C41—C46	1.382 (2)
C14—O13	1.4555 (17)	C43—N42	1.330 (2)
C14—C15	1.488 (2)	C43—C44	1.365 (3)
C14—H14A	0.9700	C43—H43	0.9300
C14—H14B	0.9700	C44—N45	1.326 (2)
C15—H15A	0.9600	C44—H44	0.9300
C15—H15B	0.9600	C46—N45	1.330 (2)
C15—H15C	0.9600	C46—H46	0.9300
C21—C22	1.511 (2)	N2—N3	1.4079 (17)
C21—S2	1.7912 (14)	N5—H5A	0.8600
C21—H21A	0.9700	N5—H5B	0.8600
N2—C1—S2	120.44 (11)	O23—C24—C25	108.02 (17)
N2—C1—S1	120.70 (11)	O23—C24—H24A	110.1
S2—C1—S1	118.86 (8)	C25—C24—H24A	110.1
N3—C4—N5	127.24 (14)	O23—C24—H24B	110.1
N3—C4—C41	115.22 (13)	C25—C24—H24B	110.1
N5—C4—C41	117.53 (12)	H24A—C24—H24B	108.4
C12—C11—S1	109.65 (10)	C24—C25—H25A	109.5
C12—C11—H11A	109.7	C24—C25—H25B	109.5
S1—C11—H11A	109.7	H25A—C25—H25B	109.5
C12—C11—H11B	109.7	C24—C25—H25C	109.5
S1—C11—H11B	109.7	H25A—C25—H25C	109.5
H11A—C11—H11B	108.2	H25B—C25—H25C	109.5
O12—C12—O13	124.94 (13)	N42—C41—C46	120.87 (14)
O12—C12—C11	126.08 (13)	N42—C41—C4	117.24 (13)
O13—C12—C11	108.98 (12)	C46—C41—C4	121.90 (13)
O13—C14—C15	106.86 (12)	N42—C43—C44	122.92 (17)
O13—C14—H14A	110.4	N42—C43—H43	118.5
C15—C14—H14A	110.4	C44—C43—H43	118.5
O13—C14—H14B	110.4	N45—C44—C43	121.89 (17)
C15—C14—H14B	110.4	N45—C44—H44	119.1
H14A—C14—H14B	108.6	C43—C44—H44	119.1
C14—C15—H15A	109.5	N45—C46—C41	122.93 (15)
C14—C15—H15B	109.5	N45—C46—H46	118.5
H15A—C15—H15B	109.5	C41—C46—H46	118.5
C14—C15—H15C	109.5	C1—N2—N3	110.69 (12)
H15A—C15—H15C	109.5	C4—N3—N2	113.01 (12)
H15B—C15—H15C	109.5	C4—N5—H5A	120.0
C22—C21—S2	113.29 (10)	C4—N5—H5B	120.0
C22—C21—H21A	108.9	H5A—N5—H5B	120.0
S2—C21—H21A	108.9	C43—N42—C41	115.87 (16)
C22—C21—H21B	108.9	C44—N45—C46	115.52 (16)
S2—C21—H21B	108.9	C12—O13—C14	117.17 (11)
H21A—C21—H21B	107.7	C22—O23—C24	116.63 (14)
O22—C22—O23	124.39 (15)	C1—S1—C11	101.46 (7)
O22—C22—C21	125.53 (14)	C1—S2—C21	100.01 (7)
O23—C22—C21	110.07 (13)
S1—C11—C12—O12	4.8 (2)	C46—C41—N42—C43	0.8 (3)
S1—C11—C12—O13	−175.35 (10)	C4—C41—N42—C43	−179.58 (16)
S2—C21—C22—O22	19.1 (2)	C43—C44—N45—C46	1.0 (3)
S2—C21—C22—O23	−162.16 (11)	C41—C46—N45—C44	−0.3 (3)
N3—C4—C41—N42	176.74 (14)	O12—C12—O13—C14	1.1 (2)
N5—C4—C41—N42	−1.8 (2)	C11—C12—O13—C14	−178.77 (13)
N3—C4—C41—C46	−3.6 (2)	C15—C14—O13—C12	170.58 (14)
N5—C4—C41—C46	177.84 (15)	O22—C22—O23—C24	−0.3 (3)
N42—C43—C44—N45	−0.8 (3)	C21—C22—O23—C24	−179.12 (17)
N42—C41—C46—N45	−0.6 (3)	C25—C24—O23—C22	−156.0 (2)
C4—C41—C46—N45	179.78 (16)	N2—C1—S1—C11	179.31 (12)
S2—C1—N2—N3	−178.75 (10)	S2—C1—S1—C11	−0.51 (11)
S1—C1—N2—N3	1.44 (18)	C12—C11—S1—C1	164.53 (11)
N5—C4—N3—N2	0.7 (2)	N2—C1—S2—C21	7.65 (14)
C41—C4—N3—N2	−177.67 (12)	S1—C1—S2—C21	−172.53 (9)
C1—N2—N3—C4	−172.45 (13)	C22—C21—S2—C1	68.14 (12)
C44—C43—N42—C41	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N45^i	0.86	2.63	3.320 (2)	139
C44—H44···O22^ii	0.93	2.48	3.403 (2)	174
C11—H11A···O12^iii	0.97	2.55	3.473 (2)	159
N5—H5B···O22^iv	0.86	2.37	3.2002 (17)	164

Symmetry codes: (i) x, y+1, z; (ii) x, −y, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y+1, z−1/2.

(C1) methyl 3-[amino(pyrazin-2-yl)methylidene]-2-methylcarbazate

Crystal data

C8H11N5S2	Z = 2
Mr = 241.34	F(000) = 252
Triclinic, P1	Dx = 1.409 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7213 (1) Å	Cell parameters from 6100 reflections
b = 8.1004 (1) Å	θ = 2.7–31.1°
c = 9.3331 (1) Å	µ = 0.44 mm^−1
α = 87.9959 (11)°	T = 290 K
β = 79.0802 (12)°	Cube, colourless
γ = 82.8402 (10)°	0.3 × 0.3 × 0.3 mm
V = 568.67 (1) Å^3

Data collection

Kuma KM-4 CCD area-detector diffractometer	2319 independent reflections
Radiation source: fine-focus sealed tube	2161 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.009
ω scans	θmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.940, Tmax = 1.000	k = −10→10
7633 measured reflections	l = −11→8

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.2235P] where P = (Fo^2 + 2Fc^2)/3
2319 reflections	(Δ/σ)max < 0.001
138 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.13 (release 29–11-2007 CrysAlis171. NET) (compiled Nov 29 2007,17:23:28) 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	0.24407 (19)	0.98717 (18)	0.27399 (17)	0.0307 (3)
C2	0.2193 (2)	0.8475 (2)	0.51399 (19)	0.0418 (4)
H2A	0.1401	0.7764	0.5696	0.050*
H2B	0.2051	0.9528	0.5615	0.050*
H2C	0.3397	0.7966	0.5069	0.050*
C4	0.06103 (19)	0.64381 (19)	0.31377 (17)	0.0307 (3)
C11	0.2721 (3)	1.1454 (3)	0.0021 (2)	0.0554 (5)
H11A	0.2466	1.1456	−0.0946	0.067*
H11B	0.3977	1.1189	−0.0022	0.067*
H11C	0.2338	1.2534	0.0442	0.067*
C41	−0.09111 (19)	0.56783 (18)	0.27686 (17)	0.0298 (3)
C43	−0.1821 (2)	0.3755 (2)	0.1478 (2)	0.0472 (4)
H43	−0.1578	0.2846	0.0861	0.057*
C44	−0.3550 (2)	0.4433 (2)	0.1917 (2)	0.0434 (4)
H44	−0.4440	0.3984	0.1568	0.052*
C46	−0.2661 (2)	0.6339 (2)	0.3249 (2)	0.0369 (4)
H46	−0.2908	0.7238	0.3879	0.044*
N2	0.17814 (17)	0.87278 (16)	0.36805 (15)	0.0323 (3)
N3	0.02973 (17)	0.80159 (16)	0.33818 (17)	0.0356 (3)
N5	0.21119 (19)	0.54388 (19)	0.3137 (2)	0.0517 (4)
H5A	0.3032	0.5833	0.3316	0.062*
H5B	0.2164	0.4398	0.2958	0.062*
N42	−0.04782 (18)	0.43563 (18)	0.19073 (18)	0.0411 (3)
N45	−0.39984 (18)	0.57125 (19)	0.28263 (18)	0.0427 (4)
S1	0.15698 (7)	0.99294 (6)	0.11240 (5)	0.04526 (15)
S2	0.39250 (6)	1.10689 (6)	0.30620 (5)	0.04579 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0290 (7)	0.0263 (7)	0.0386 (8)	−0.0043 (6)	−0.0089 (6)	−0.0060 (6)
C2	0.0488 (10)	0.0407 (9)	0.0400 (9)	−0.0110 (7)	−0.0150 (7)	0.0018 (7)
C4	0.0248 (7)	0.0309 (7)	0.0382 (8)	−0.0075 (6)	−0.0073 (6)	−0.0013 (6)
C11	0.0680 (13)	0.0504 (11)	0.0428 (10)	−0.0002 (10)	−0.0033 (9)	0.0081 (9)
C41	0.0274 (7)	0.0264 (7)	0.0378 (8)	−0.0091 (5)	−0.0085 (6)	0.0014 (6)
C43	0.0445 (10)	0.0412 (10)	0.0600 (12)	−0.0116 (8)	−0.0131 (8)	−0.0169 (8)
C44	0.0378 (9)	0.0422 (9)	0.0575 (11)	−0.0185 (7)	−0.0182 (8)	−0.0009 (8)
C46	0.0284 (7)	0.0352 (8)	0.0487 (9)	−0.0091 (6)	−0.0070 (7)	−0.0061 (7)
N2	0.0309 (6)	0.0294 (6)	0.0415 (7)	−0.0107 (5)	−0.0140 (5)	−0.0011 (5)
N3	0.0269 (6)	0.0294 (7)	0.0548 (9)	−0.0094 (5)	−0.0143 (6)	−0.0017 (6)
N5	0.0294 (7)	0.0345 (8)	0.0967 (14)	−0.0027 (6)	−0.0235 (8)	−0.0163 (8)
N42	0.0331 (7)	0.0362 (7)	0.0559 (9)	−0.0072 (6)	−0.0087 (6)	−0.0126 (7)
N45	0.0274 (7)	0.0423 (8)	0.0616 (10)	−0.0112 (6)	−0.0108 (6)	−0.0040 (7)
S1	0.0605 (3)	0.0396 (3)	0.0426 (3)	−0.0100 (2)	−0.0247 (2)	−0.00047 (18)
S2	0.0454 (3)	0.0432 (3)	0.0559 (3)	−0.0244 (2)	−0.0150 (2)	−0.0019 (2)

Geometric parameters (Å, º)

C1—N2	1.334 (2)	C11—H11C	0.9600
C1—S2	1.6650 (15)	C41—N42	1.332 (2)
C1—S1	1.7607 (16)	C41—C46	1.386 (2)
C2—N2	1.458 (2)	C43—N42	1.330 (2)
C2—H2A	0.9600	C43—C44	1.370 (3)
C2—H2B	0.9600	C43—H43	0.9300
C2—H2C	0.9600	C44—N45	1.333 (2)
C4—N3	1.291 (2)	C44—H44	0.9300
C4—N5	1.329 (2)	C46—N45	1.334 (2)
C4—C41	1.4919 (19)	C46—H46	0.9300
C11—S1	1.792 (2)	N2—N3	1.4214 (16)
C11—H11A	0.9600	N5—H5A	0.8600
C11—H11B	0.9600	N5—H5B	0.8600
N2—C1—S2	123.63 (12)	C46—C41—C4	122.18 (14)
N2—C1—S1	111.64 (11)	N42—C43—C44	122.16 (16)
S2—C1—S1	124.72 (10)	N42—C43—H43	118.9
N2—C2—H2A	109.5	C44—C43—H43	118.9
N2—C2—H2B	109.5	N45—C44—C43	122.14 (15)
H2A—C2—H2B	109.5	N45—C44—H44	118.9
N2—C2—H2C	109.5	C43—C44—H44	118.9
H2A—C2—H2C	109.5	N45—C46—C41	121.34 (15)
H2B—C2—H2C	109.5	N45—C46—H46	119.3
N3—C4—N5	128.27 (14)	C41—C46—H46	119.3
N3—C4—C41	114.71 (13)	C1—N2—N3	117.29 (13)
N5—C4—C41	116.99 (14)	C1—N2—C2	123.42 (13)
S1—C11—H11A	109.5	N3—N2—C2	117.50 (13)
S1—C11—H11B	109.5	C4—N3—N2	113.87 (12)
H11A—C11—H11B	109.5	C4—N5—H5A	120.0
S1—C11—H11C	109.5	C4—N5—H5B	120.0
H11A—C11—H11C	109.5	H5A—N5—H5B	120.0
H11B—C11—H11C	109.5	C43—N42—C41	115.98 (14)
N42—C41—C46	122.08 (14)	C44—N45—C46	116.21 (14)
N42—C41—C4	115.71 (13)	C1—S1—C11	103.26 (9)
N3—C4—C41—N42	150.81 (16)	N5—C4—N3—N2	0.1 (3)
N5—C4—C41—N42	−27.4 (2)	C41—C4—N3—N2	−177.88 (13)
N3—C4—C41—C46	−27.0 (2)	C1—N2—N3—C4	116.53 (16)
N5—C4—C41—C46	154.72 (17)	C2—N2—N3—C4	−78.18 (18)
N42—C43—C44—N45	−1.5 (3)	C44—C43—N42—C41	−1.2 (3)
N42—C41—C46—N45	−2.4 (3)	C46—C41—N42—C43	3.1 (3)
C4—C41—C46—N45	175.32 (16)	C4—C41—N42—C43	−174.76 (16)
S2—C1—N2—N3	168.75 (11)	C43—C44—N45—C46	2.3 (3)
S1—C1—N2—N3	−12.05 (17)	C41—C46—N45—C44	−0.4 (3)
S2—C1—N2—C2	4.4 (2)	N2—C1—S1—C11	−177.15 (12)
S1—C1—N2—C2	−176.39 (12)	S2—C1—S1—C11	2.05 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N45^i	0.86	2.24	2.9975 (19)	147
N5—H5B···S2^ii	0.86	2.87	3.6387 (16)	149

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

(C2) benzyl 3-[amino(pyrazin-2-yl)methylidene]-2-methylcarbazate

Crystal data

C14H15N5S2	Z = 2
Mr = 317.43	F(000) = 332
Triclinic, P1	Dx = 1.363 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 7.2329 (1) Å	Cell parameters from 7068 reflections
b = 7.9041 (1) Å	θ = 5.8–70.1°
c = 14.0969 (2) Å	µ = 3.12 mm^−1
α = 105.717 (1)°	T = 290 K
β = 91.368 (1)°	Plate, colourless
γ = 93.863 (1)°	0.3 × 0.2 × 0.05 mm
V = 773.27 (2) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2647 independent reflections
Radiation source: fine-focus sealed tube	2549 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scans	θmax = 66.5°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.735, Tmax = 1.000	k = −9→8
8491 measured reflections	l = −16→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.059P)^2 + 0.1869P] where P = (Fo^2 + 2Fc^2)/3
2647 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.27 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	−0.0621 (2)	1.1792 (2)	0.76968 (12)	0.0445 (4)
C2	−0.3422 (3)	1.2506 (3)	0.69269 (15)	0.0585 (4)
H2A	−0.4360	1.1869	0.6445	0.070*
H2B	−0.2963	1.3548	0.6756	0.070*
H2C	−0.3946	1.2834	0.7565	0.070*
C4	−0.22584 (19)	0.92725 (19)	0.54636 (11)	0.0392 (3)
C11	0.2344 (3)	1.0885 (3)	0.87292 (15)	0.0616 (5)
H11A	0.3166	1.1833	0.8624	0.074*
H11B	0.1675	1.1339	0.9322	0.074*
C12	0.3433 (2)	0.9375 (2)	0.88251 (12)	0.0497 (4)
C13	0.2750 (3)	0.8186 (3)	0.93081 (14)	0.0635 (5)
H13	0.1592	0.8314	0.9581	0.076*
C14	0.3746 (3)	0.6812 (3)	0.93953 (16)	0.0720 (6)
H14	0.3258	0.6022	0.9725	0.086*
C15	0.5455 (3)	0.6599 (3)	0.89999 (15)	0.0697 (6)
H15	0.6136	0.5677	0.9066	0.084*
C16	0.6147 (3)	0.7747 (3)	0.85095 (17)	0.0717 (6)
H16	0.7302	0.7604	0.8235	0.086*
C17	0.5147 (3)	0.9125 (3)	0.84164 (15)	0.0622 (5)
H17	0.5632	0.9895	0.8074	0.075*
C41	−0.2385 (2)	0.7360 (2)	0.49210 (11)	0.0398 (3)
C43	−0.2553 (3)	0.5263 (3)	0.34587 (14)	0.0617 (5)
H43	−0.2602	0.4934	0.2773	0.074*
C44	−0.2599 (3)	0.3979 (2)	0.39448 (14)	0.0626 (5)
H44	−0.2704	0.2804	0.3577	0.075*
C46	−0.2398 (3)	0.6056 (2)	0.54085 (13)	0.0515 (4)
H46	−0.2336	0.6381	0.6094	0.062*
N2	−0.19016 (19)	1.13931 (17)	0.69507 (10)	0.0458 (3)
N3	−0.21313 (19)	0.95915 (17)	0.64099 (10)	0.0450 (3)
N5	−0.2275 (2)	1.03913 (18)	0.49009 (10)	0.0510 (3)
H5A	−0.2192	1.1510	0.5171	0.061*
H5B	−0.2368	0.9992	0.4269	0.061*
N42	−0.2439 (2)	0.69693 (19)	0.39410 (10)	0.0517 (3)
N45	−0.2499 (3)	0.43501 (19)	0.49252 (12)	0.0615 (4)
S1	0.07348 (6)	1.00020 (5)	0.76729 (3)	0.04975 (15)
S2	−0.03356 (7)	1.37263 (6)	0.85344 (4)	0.06241 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0492 (8)	0.0376 (8)	0.0443 (8)	0.0037 (6)	0.0061 (6)	0.0067 (6)
C2	0.0654 (11)	0.0486 (10)	0.0620 (11)	0.0186 (8)	0.0018 (8)	0.0127 (8)
C4	0.0379 (7)	0.0357 (8)	0.0442 (8)	0.0018 (6)	−0.0034 (6)	0.0118 (6)
C11	0.0632 (11)	0.0543 (11)	0.0581 (10)	0.0069 (8)	−0.0135 (8)	0.0005 (8)
C12	0.0514 (9)	0.0500 (9)	0.0422 (8)	0.0018 (7)	−0.0069 (7)	0.0047 (7)
C13	0.0553 (10)	0.0777 (14)	0.0567 (11)	−0.0001 (9)	0.0034 (8)	0.0184 (10)
C14	0.0898 (15)	0.0674 (13)	0.0621 (12)	−0.0046 (11)	−0.0102 (11)	0.0267 (10)
C15	0.0880 (15)	0.0584 (12)	0.0570 (11)	0.0182 (10)	−0.0168 (10)	0.0046 (9)
C16	0.0599 (11)	0.0825 (15)	0.0685 (12)	0.0180 (10)	0.0070 (9)	0.0101 (11)
C17	0.0618 (11)	0.0651 (12)	0.0621 (11)	0.0024 (9)	0.0078 (9)	0.0214 (9)
C41	0.0398 (7)	0.0367 (8)	0.0421 (8)	0.0024 (6)	−0.0037 (6)	0.0100 (6)
C43	0.0877 (14)	0.0488 (10)	0.0428 (9)	0.0063 (9)	−0.0030 (9)	0.0029 (8)
C44	0.0894 (14)	0.0363 (9)	0.0570 (11)	0.0069 (8)	−0.0005 (9)	0.0040 (8)
C46	0.0715 (11)	0.0382 (8)	0.0446 (8)	0.0028 (7)	−0.0015 (7)	0.0114 (7)
N2	0.0544 (7)	0.0341 (7)	0.0462 (7)	0.0071 (5)	0.0001 (6)	0.0057 (6)
N3	0.0558 (8)	0.0330 (7)	0.0442 (7)	0.0033 (5)	−0.0031 (6)	0.0077 (5)
N5	0.0713 (9)	0.0351 (7)	0.0472 (7)	0.0030 (6)	−0.0027 (6)	0.0130 (6)
N42	0.0686 (9)	0.0431 (8)	0.0427 (7)	0.0038 (6)	−0.0043 (6)	0.0112 (6)
N45	0.0919 (12)	0.0363 (8)	0.0562 (9)	0.0061 (7)	0.0003 (8)	0.0122 (7)
S1	0.0578 (3)	0.0409 (2)	0.0457 (2)	0.00983 (18)	−0.00520 (17)	0.00269 (17)
S2	0.0686 (3)	0.0421 (3)	0.0632 (3)	0.0075 (2)	−0.0018 (2)	−0.0087 (2)

Geometric parameters (Å, º)

C1—N2	1.341 (2)	C14—H14	0.9300
C1—S2	1.6562 (16)	C15—C16	1.359 (3)
C1—S1	1.7680 (16)	C15—H15	0.9300
C2—N2	1.459 (2)	C16—C17	1.380 (3)
C2—H2A	0.9600	C16—H16	0.9300
C2—H2B	0.9600	C17—H17	0.9300
C2—H2C	0.9600	C41—N42	1.330 (2)
C4—N3	1.289 (2)	C41—C46	1.385 (2)
C4—N5	1.339 (2)	C43—N42	1.332 (2)
C4—C41	1.493 (2)	C43—C44	1.369 (3)
C11—C12	1.507 (3)	C43—H43	0.9300
C11—S1	1.8176 (18)	C44—N45	1.332 (3)
C11—H11A	0.9700	C44—H44	0.9300
C11—H11B	0.9700	C46—N45	1.332 (2)
C12—C13	1.376 (3)	C46—H46	0.9300
C12—C17	1.383 (3)	N2—N3	1.4180 (18)
C13—C14	1.374 (3)	N5—H5A	0.8600
C13—H13	0.9300	N5—H5B	0.8600
C14—C15	1.370 (3)
N2—C1—S2	124.15 (12)	C14—C15—H15	120.3
N2—C1—S1	111.71 (11)	C15—C16—C17	120.5 (2)
S2—C1—S1	124.14 (10)	C15—C16—H16	119.8
N2—C2—H2A	109.5	C17—C16—H16	119.8
N2—C2—H2B	109.5	C16—C17—C12	120.90 (19)
H2A—C2—H2B	109.5	C16—C17—H17	119.5
N2—C2—H2C	109.5	C12—C17—H17	119.5
H2A—C2—H2C	109.5	N42—C41—C46	121.46 (15)
H2B—C2—H2C	109.5	N42—C41—C4	116.55 (13)
N3—C4—N5	129.82 (15)	C46—C41—C4	121.98 (14)
N3—C4—C41	114.44 (13)	N42—C43—C44	121.82 (17)
N5—C4—C41	115.74 (13)	N42—C43—H43	119.1
C12—C11—S1	106.23 (12)	C44—C43—H43	119.1
C12—C11—H11A	110.5	N45—C44—C43	122.44 (17)
S1—C11—H11A	110.5	N45—C44—H44	118.8
C12—C11—H11B	110.5	C43—C44—H44	118.8
S1—C11—H11B	110.5	N45—C46—C41	122.03 (16)
H11A—C11—H11B	108.7	N45—C46—H46	119.0
C13—C12—C17	117.67 (18)	C41—C46—H46	119.0
C13—C12—C11	121.34 (17)	C1—N2—N3	115.55 (12)
C17—C12—C11	120.98 (17)	C1—N2—C2	121.70 (14)
C14—C13—C12	121.23 (19)	N3—N2—C2	118.64 (14)
C14—C13—H13	119.4	C4—N3—N2	116.18 (13)
C12—C13—H13	119.4	C4—N5—H5A	120.0
C15—C14—C13	120.4 (2)	C4—N5—H5B	120.0
C15—C14—H14	119.8	H5A—N5—H5B	120.0
C13—C14—H14	119.8	C41—N42—C43	116.43 (15)
C16—C15—C14	119.4 (2)	C44—N45—C46	115.78 (16)
C16—C15—H15	120.3	C1—S1—C11	102.79 (8)
S1—C11—C12—C13	−83.42 (19)	S2—C1—N2—N3	−170.04 (11)
S1—C11—C12—C17	95.62 (19)	S1—C1—N2—N3	10.27 (17)
C17—C12—C13—C14	1.0 (3)	S2—C1—N2—C2	−13.2 (2)
C11—C12—C13—C14	−179.94 (18)	S1—C1—N2—C2	167.12 (13)
C12—C13—C14—C15	0.0 (3)	N5—C4—N3—N2	−2.7 (2)
C13—C14—C15—C16	−0.8 (3)	C41—C4—N3—N2	176.52 (12)
C14—C15—C16—C17	0.5 (3)	C1—N2—N3—C4	−135.84 (15)
C15—C16—C17—C12	0.5 (3)	C2—N2—N3—C4	66.56 (19)
C13—C12—C17—C16	−1.3 (3)	C46—C41—N42—C43	1.6 (2)
C11—C12—C17—C16	179.64 (18)	C4—C41—N42—C43	−179.97 (15)
N3—C4—C41—N42	−177.25 (14)	C44—C43—N42—C41	−0.4 (3)
N5—C4—C41—N42	2.1 (2)	C43—C44—N45—C46	1.6 (3)
N3—C4—C41—C46	1.2 (2)	C41—C46—N45—C44	−0.5 (3)
N5—C4—C41—C46	−179.45 (15)	N2—C1—S1—C11	179.30 (13)
N42—C43—C44—N45	−1.3 (3)	S2—C1—S1—C11	−0.39 (14)
N42—C41—C46—N45	−1.2 (3)	C12—C11—S1—C1	174.38 (13)
C4—C41—C46—N45	−179.56 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N45^i	0.86	2.39	3.135 (2)	146

Symmetry code: (i) x, y+1, z.

(D1) N'-Anilinopyrazine-2-carboximidamide

Crystal data

C11H11N5	F(000) = 448
Mr = 213.25	Dx = 1.300 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2c -2ac	Cell parameters from 5484 reflections
a = 20.7274 (6) Å	θ = 2.9–31.6°
b = 5.7456 (1) Å	µ = 0.09 mm^−1
c = 9.1455 (3) Å	T = 290 K
V = 1089.15 (5) Å^3	Plate, colourless
Z = 4	0.4 × 0.3 × 0.05 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	1415 independent reflections
Radiation source: fine-focus sealed tube	1055 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 28.3°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −27→27
Tmin = 0.728, Tmax = 1.000	k = −7→7
15567 measured reflections	l = −9→12

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0458P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max < 0.001
1415 reflections	Δρmax = 0.11 e Å^−3
154 parameters	Δρmin = −0.12 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 (10)

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.13 (release 29–11-2007 CrysAlis171. NET) (compiled Nov 29 2007,17:23:28) 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
C4	0.25837 (8)	0.8077 (2)	−0.02592 (15)	0.0399 (3)
C11	0.39995 (8)	1.0962 (3)	0.0866 (2)	0.0472 (4)
C12	0.42684 (7)	0.9455 (3)	0.1875 (2)	0.0538 (4)
H12	0.4076	0.8023	0.2061	0.065*
C13	0.48259 (9)	1.0090 (4)	0.2608 (3)	0.0708 (6)
H13	0.5005	0.9066	0.3283	0.085*
C14	0.51185 (9)	1.2179 (4)	0.2364 (3)	0.0781 (7)
H14	0.5497	1.2569	0.2851	0.094*
C15	0.48431 (10)	1.3700 (4)	0.1385 (3)	0.0801 (7)
H15	0.5036	1.5139	0.1223	0.096*
C16	0.42865 (9)	1.3130 (3)	0.0639 (2)	0.0638 (6)
H16	0.4104	1.4184	−0.0012	0.077*
C41	0.21834 (7)	0.6080 (3)	0.01839 (18)	0.0398 (3)
C43	0.12908 (8)	0.3876 (3)	−0.0203 (2)	0.0576 (5)
H43	0.0927	0.3505	−0.0753	0.069*
C44	0.14321 (9)	0.2574 (3)	0.1009 (2)	0.0587 (5)
H44	0.1154	0.1376	0.1274	0.070*
C46	0.23302 (8)	0.4698 (3)	0.13907 (17)	0.0477 (4)
H46	0.2706	0.5002	0.1914	0.057*
H2	0.3263 (9)	1.145 (3)	−0.034 (2)	0.057*
H5A	0.2623 (8)	1.040 (3)	−0.180 (2)	0.057*
H5B	0.1981 (8)	0.881 (3)	−0.177 (2)	0.057*
N2	0.34609 (7)	1.0361 (2)	0.00504 (18)	0.0527 (4)
N3	0.31069 (6)	0.8440 (2)	0.04645 (14)	0.0445 (3)
N5	0.23487 (8)	0.9418 (3)	−0.13588 (16)	0.0561 (4)
N42	0.16588 (6)	0.5658 (2)	−0.06184 (15)	0.0487 (4)
N45	0.19526 (7)	0.2965 (2)	0.18176 (17)	0.0556 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.0518 (9)	0.0400 (7)	0.0278 (8)	0.0039 (7)	0.0021 (7)	0.0063 (6)
C11	0.0468 (9)	0.0453 (8)	0.0494 (10)	−0.0023 (7)	0.0121 (8)	−0.0012 (7)
C12	0.0519 (9)	0.0506 (9)	0.0588 (11)	−0.0012 (7)	0.0010 (9)	0.0018 (9)
C13	0.0557 (11)	0.0753 (13)	0.0813 (15)	0.0069 (10)	−0.0102 (11)	−0.0106 (12)
C14	0.0477 (10)	0.0786 (14)	0.1080 (19)	−0.0029 (10)	0.0010 (12)	−0.0339 (14)
C15	0.0603 (12)	0.0597 (11)	0.120 (2)	−0.0180 (10)	0.0247 (14)	−0.0216 (14)
C16	0.0653 (11)	0.0488 (10)	0.0773 (15)	−0.0085 (9)	0.0181 (10)	0.0025 (9)
C41	0.0464 (8)	0.0438 (8)	0.0292 (7)	0.0028 (6)	0.0016 (7)	0.0042 (7)
C43	0.0489 (10)	0.0686 (11)	0.0551 (12)	−0.0061 (8)	−0.0053 (9)	0.0072 (10)
C44	0.0548 (10)	0.0586 (10)	0.0626 (12)	−0.0106 (9)	0.0064 (9)	0.0112 (9)
C46	0.0570 (10)	0.0488 (8)	0.0373 (9)	−0.0038 (7)	−0.0073 (8)	0.0106 (8)
N2	0.0609 (9)	0.0472 (8)	0.0499 (9)	−0.0078 (7)	−0.0024 (8)	0.0170 (7)
N3	0.0524 (7)	0.0449 (7)	0.0361 (7)	−0.0048 (6)	0.0015 (6)	0.0103 (6)
N5	0.0702 (10)	0.0576 (8)	0.0404 (8)	−0.0095 (8)	−0.0114 (7)	0.0191 (7)
N42	0.0479 (7)	0.0579 (8)	0.0403 (8)	−0.0013 (6)	−0.0047 (7)	0.0105 (7)
N45	0.0651 (9)	0.0529 (8)	0.0488 (9)	−0.0062 (7)	0.0006 (8)	0.0169 (7)

Geometric parameters (Å, º)

C4—N3	1.288 (2)	C16—H16	0.9300
C4—N5	1.3573 (19)	C41—N42	1.334 (2)
C4—C41	1.473 (2)	C41—C46	1.393 (2)
C11—C12	1.383 (3)	C43—N42	1.332 (2)
C11—N2	1.386 (2)	C43—C44	1.369 (3)
C11—C16	1.396 (2)	C43—H43	0.9300
C12—C13	1.385 (3)	C44—N45	1.327 (2)
C12—H12	0.9300	C44—H44	0.9300
C13—C14	1.363 (3)	C46—N45	1.3253 (19)
C13—H13	0.9300	C46—H46	0.9300
C14—C15	1.376 (3)	N2—N3	1.3784 (18)
C14—H14	0.9300	N2—H2	0.827 (18)
C15—C16	1.380 (3)	N5—H5A	0.894 (18)
C15—H15	0.9300	N5—H5B	0.921 (18)
N3—C4—N5	126.24 (14)	N42—C41—C46	120.70 (13)
N3—C4—C41	117.35 (12)	N42—C41—C4	116.70 (13)
N5—C4—C41	116.35 (14)	C46—C41—C4	122.60 (14)
C12—C11—N2	121.86 (14)	N42—C43—C44	121.89 (16)
C12—C11—C16	119.09 (17)	N42—C43—H43	119.1
N2—C11—C16	119.03 (17)	C44—C43—H43	119.1
C11—C12—C13	119.61 (17)	N45—C44—C43	122.19 (16)
C11—C12—H12	120.2	N45—C44—H44	118.9
C13—C12—H12	120.2	C43—C44—H44	118.9
C14—C13—C12	121.6 (2)	N45—C46—C41	122.17 (14)
C14—C13—H13	119.2	N45—C46—H46	118.9
C12—C13—H13	119.2	C41—C46—H46	118.9
C13—C14—C15	118.77 (19)	N3—N2—C11	118.70 (15)
C13—C14—H14	120.6	N3—N2—H2	117.2 (13)
C15—C14—H14	120.6	C11—N2—H2	116.4 (13)
C14—C15—C16	121.21 (18)	C4—N3—N2	115.90 (13)
C14—C15—H15	119.4	C4—N5—H5A	117.4 (11)
C16—C15—H15	119.4	C4—N5—H5B	112.6 (12)
C15—C16—C11	119.6 (2)	H5A—N5—H5B	125.7 (18)
C15—C16—H16	120.2	C43—N42—C41	116.70 (14)
C11—C16—H16	120.2	C46—N45—C44	116.30 (15)
N2—C11—C12—C13	176.69 (16)	N42—C41—C46—N45	−1.9 (3)
C16—C11—C12—C13	−1.9 (3)	C4—C41—C46—N45	177.09 (14)
C11—C12—C13—C14	0.2 (3)	C12—C11—N2—N3	13.7 (2)
C12—C13—C14—C15	1.2 (3)	C16—C11—N2—N3	−167.66 (15)
C13—C14—C15—C16	−1.0 (3)	N5—C4—N3—N2	−1.2 (2)
C14—C15—C16—C11	−0.7 (3)	C41—C4—N3—N2	−178.19 (13)
C12—C11—C16—C15	2.1 (3)	C11—N2—N3—C4	174.57 (14)
N2—C11—C16—C15	−176.50 (18)	C44—C43—N42—C41	1.7 (2)
N3—C4—C41—N42	−176.93 (14)	C46—C41—N42—C43	0.1 (2)
N5—C4—C41—N42	5.8 (2)	C4—C41—N42—C43	−178.91 (15)
N3—C4—C41—C46	4.1 (2)	C41—C46—N45—C44	1.6 (3)
N5—C4—C41—C46	−173.24 (15)	C43—C44—N45—C46	0.2 (3)
N42—C43—C44—N45	−2.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···N3^i	0.921 (18)	2.54 (2)	3.106 (2)	119.9 (15)
N5—H5A···N45^ii	0.894 (18)	2.135 (19)	3.005 (2)	164.1 (15)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y+1, z−1/2.