organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

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

aInstitute of General and Ecological Chemistry, Technical University of Łódź, Poland, and bDepartment of Organic Chemistry, Medical University of Gdańsk, Poland
*Correspondence e-mail: marekglo@p.lodz.pl

(Received 25 March 2011; accepted 6 June 2011; online 17 June 2011)

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.

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, including that of Foks (Foks et al., 2000[Foks, H., Mieczkowska, J. & Sitarz, M. (2000). Phosphorus Sulfur Silicon Relat. Elem. 158, 107-116.]; Gobis, Foks, Zwolska & Augustynowicz-Kopeć, 2006[Gobis, K., Foks, H., Zwolska, Z. & Augustynowicz-Kopeć, E. (2006). Phosphorus Sulfur Silicon Relat. Elem. 181, 965-975.]; Gobis, Foks, Żuralska & Kędzia, 2006[Gobis, K., Foks, H., Żuralska, A. & Kędzia, A. (2006). Heterocycles, 68, 2615-2626.]), who synthesized several chemical classes of potential tuberculostatic 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 Scheme 1[link]), which act through the formation of a covalent adduct with nicotinamide adenine dinucleotide (Wang et al., 2007[Wang, F., Langley, R., Gulten, G., Dover, L. G., Besra, G. S., Jacobs, W. R. Jr & Sacchettini, J. C. (2007). J. Exp. Med. 204, 73-78.]).

[Scheme 1]

Our earlier crystallographic studies of selected representatives of 3-[amino­(pyrazin-2-yl)methyl­idene]thio­car­bazic acid esters (see Scheme 2[link], formula A) showed that all of them maintained planarity of the whole mol­ecule, except for the terminal aliphatic substituents (Główka et al., 2005[Główka, M. L., Martynowski, D., Olczak, A., Orlewska, C., Foks, H., Bojarska, J., Szczesio, M. & Gołka, J. (2005). J. Chem. Crystallogr. 35, 477-480.]; Olczak et al., 2007[Olczak, A., Główka, M. L., Gołka, J., Szczesio, M., Bojarska, J., Kozłowska, K., Foks, H. & Orlewska, C. (2007). J. Mol. Struct. 830, 171-175.]; Orlewska et al., 2001[Orlewska, C., Foks, H., Sowiński, P., Martynowski, D., Olczak, A. & Główka, M. L. (2001). Pol. J. Chem. 75, 1237-1245.]). 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 was an ortho-positioned N atom of a pyrazine or pyridine ring on the other side of the donor (Scheme 2[link], 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[Orlewska, C., Foks, H., Sowiński, P., Martynowski, D., Olczak, A. & Główka, M. L. (2001). Pol. J. Chem. 75, 1237-1245.]).

Next, we showed that similar planarity was maintained in compounds lacking an H atom at N3, such as the dithio­esters (formula B in Scheme 2[link]), 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 Scheme 2[link]) (Olczak et al., 2011[Olczak, A., Szczesio, M., Gołka, J., Orlewska, C., Gobis, K., Foks, H. & Główka, M. L. (2011). Acta Cryst. C67, o37-o42.]).

[Scheme 2]

The compounds described here represent both S-mono­thio­esters [(E1)[link] and (G1)[link]] and S,S′-dithio­esters [(F1)[link] and (F2)[link]] of heteroaroyldithio­carbazic acids (see Scheme 3[link] and Figs. 1[link]–4[link][link][link]), in which an aryl-C(NH2)=N– function present in the former study (Olczak et al., 2011[Olczak, A., Szczesio, M., Gołka, J., Orlewska, C., Gobis, K., Foks, H. & Główka, M. L. (2011). Acta Cryst. C67, o37-o42.]) has been replaced by a 2-pyrazine-C(O)—NH– function. Thus, the compounds may be considered derivatives of the well known tuberculostatic pyrazinamid (Scheme 1[link]). Despite the significant differences between these compounds and their amine analogues A, B and C (Scheme 2[link]), we supposed that, due to the presence of an H atom at N3 in compounds (E1)[link], (F1)[link] and (F2)[link], an analogous intra­molecular hydrogen-bond contact will be formed as in the N—H heteroaryl­carbamidoyl hydrazinium cation (compound A in Scheme 2[link]). As a result, the mol­ecules should be planar and the compounds may show similar anti­bacterial activity.

[Scheme 3]

In addition, we included in this study compound (G1)[link] (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 group (see Scheme 2[link]). 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 5.32; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), 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)[link], (F1)[link] and (F2)[link] are planar except for the terminal ester group, while the mol­ecule of (G1)[link] shows a twist at the N—N bond (Fig. 4[link]) 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)[link] and (F2)[link], or along the S=C1—N2—N3—C4—C41 chain in (E1)[link], 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 and C4—C41 (Table 5[link]).

Due to the overall planarity of the mol­ecules of (E1)[link], (F1)[link] and (F2)[link], there are two short intra­molecular hydrogen-bond contacts, both with the N3—H group as the donor (see Scheme 2[link] and Tables 1[link]–4[link][link][link]). The first contact, N3—H⋯N(pyrazine), is observed in all compounds studied here having an N3—H group, including (G1)[link]. The H⋯N distances and N—H⋯N angles are in the ranges 2.21–2.28 Å and 107–110°, respectively (Table 6[link]). 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[link]). 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)[link], in which substitution at atom N2 twists the molecule (see Scheme 2[link]) and makes an intra­molecular N3—H⋯S contact impossible.

There are some doubts concerning the structural significance of these contacts (Table 6[link]), 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[Wood, P. A., Allen, F. H. & Pidcock, E. (2009). CrystEngComm, 11, 1563-1571.]). 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[Bilton, C., Allen, F. H., Shields, G. P. & Howard, J. A. K. (2000). Acta Cryst. B56, 849-856.]) and Galek et al. (2010[Galek, P. T. A., Fábián, L. & Allen, F. H. (2010). Acta Cryst. B66, 237-252.]), 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[link]), and from a couple of examples comprising a five-membered intra­molecular N—H⋯S motif which were found in the CSD, that N3—H⋯S contacts are geometrically less stressed than N3—H⋯N ones. Consequently, 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)[link], (F1)[link] and (F2)[link] is determined mainly by their planarity (Fig. 1[link] and Figs. 5[link]–6[link]) and relatively weak inter­molecular hydrogen bonds. In the diesters (F1)[link] and (F2)[link], there is only one weak C—H⋯O inter­action in each structure. In (F1)[link], 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)[link] the mol­ecules form dimers – R22(10) rings according to the graph-set definition of Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) – through C46—H⋯O5(−x + 1, y, [{3\over 2}] − z) hydrogen bonds. In ester (E1)[link], which comprises one hydrogen-bond donor group, N2—H, in each of the 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[link]), joining mol­ecules into approximately coplanar dimers in which R22(10) rings are present. Mol­ecules A and B are connected into asymmetric dimers (Fig. 1[link]) by C44B—H⋯O5A and N2A—H⋯N45B hydrogen bonds, forming R22(8) rings. In the N′-methyl­ated ester (G1)[link], one weak inter­molecular C43—H⋯O5(x − 1, y − 1, z) hydrogen bond is observed (Table 4[link]). The bonds join the mol­ecules into infinite C(6) chains running parallel to the [110] direction. In addition, an inter­molecular N3—H3⋯S1(x − 1, y, z) short contact may be considered a weak hydrogen bond (Fig. 7[link]).

[Figure 1]
Figure 1
The mol­ecular structure of (E1)[link], 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.
[Figure 2]
Figure 2
The mol­ecular structure of (F1)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3]
Figure 3
The mol­ecular structure of (F2)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4]
Figure 4
The mol­ecular structure of (G1)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 5]
Figure 5
The inter­molecular hydrogen-bond contact (dotted line) of (F1)[link] determining the packing of the mol­ecules in the crystal structure. [Symmetry code: (i) x − 1, y, z.]
[Figure 6]
Figure 6
The inter­molecular hydrogen-bond contacts (dotted lines) of (F2)[link] determining the packing of the mol­ecules in the crystal structure. [Symmetry code: (i) −x + 1, y, −z + [{3\over 2}].]
[Figure 7]
Figure 7
The inter­molecular hydrogen-bond contacts (dotted lines) of (G1)[link] determining the packing of the mol­ecules in the crystal structure. [Symmetry codes: (i) x − 1, y, z; (ii) x − 1, y − 1, z.]

Experimental

The syntheses of the title compounds were described by Foks et al. (2000[Foks, H., Mieczkowska, J. & Sitarz, M. (2000). Phosphorus Sulfur Silicon Relat. Elem. 158, 107-116.]) for (E1)[link] and (F1)[link], by Gobis, Foks, Zwolska & Augustynowicz-Kopeć (2006[Gobis, K., Foks, H., Zwolska, Z. & Augustynowicz-Kopeć, E. (2006). Phosphorus Sulfur Silicon Relat. Elem. 181, 965-975.]) for (G1)[link], and by Gobis, Foks, Żuralska & Kędzia (2006[Gobis, K., Foks, H., Żuralska, A. & Kędzia, A. (2006). Heterocycles, 68, 2615-2626.]) for (F2)[link]. Single crystals of compounds (E1)[link], (F1)[link], (F2)[link] and (G1)[link] 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.

Compound (E1)[link]

Crystal data
  • C7H8N4OS2

  • Mr = 228.29

  • Triclinic, [P \overline 1]

  • a = 7.2326 (3) Å

  • b = 12.7207 (4) Å

  • c = 17.7516 (5) Å

  • α = 77.877 (3)°

  • β = 79.096 (3)°

  • γ = 73.968 (4)°

  • V = 1519.67 (9) Å3

  • Z = 6

  • Mo Kα radiation

  • μ = 0.50 mm−1

  • T = 295 K

  • 0.3 × 0.2 × 0.05 mm

Data collection
  • Kuma KM-4 CCD area-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Version 1.171.33.66. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.876, Tmax = 1.000

  • 18215 measured reflections

  • 6187 independent reflections

  • 4162 reflections with I > 2σ(I)

  • Rint = 0.021

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.094

  • S = 1.00

  • 6187 reflections

  • 382 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (E1)[link]

D—H⋯A D—H H⋯A DA 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

Compound (F1)[link]

Crystal data
  • C8H10N4OS2

  • Mr = 242.32

  • Monoclinic, P 21 /c

  • a = 7.8332 (2) Å

  • b = 21.0883 (4) Å

  • c = 7.3920 (2) Å

  • β = 116.121 (4)°

  • V = 1096.36 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.46 mm−1

  • T = 297 K

  • 0.2 × 0.1 × 0.05 mm

Data collection
  • Kuma KM-4 CCD area-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Version 1.171.33.66. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.946, Tmax = 1.000

  • 12975 measured reflections

  • 2236 independent reflections

  • 1960 reflections with I > 2σ(I)

  • Rint = 0.015

Refinement
  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.087

  • S = 1.07

  • 2236 reflections

  • 139 parameters

  • H-atom parameters constrained

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.20 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (F1)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C44—H44⋯O5i 0.93 2.59 3.219 (2) 125
Symmetry code: (i) x-1, y, z.

Compound (F2)[link]

Crystal data
  • C9H12N4O2S2

  • Mr = 272.35

  • Monoclinic, C 2/c

  • a = 23.111 (2) Å

  • b = 7.5812 (7) Å

  • c = 15.6547 (14) Å

  • β = 115.430 (2)°

  • V = 2477.1 (4) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.43 mm−1

  • T = 270 K

  • 0.5 × 0.2 × 0.1 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.516, Tmax = 1.000

  • 27591 measured reflections

  • 3051 independent reflections

  • 2351 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.126

  • S = 1.03

  • 3051 reflections

  • 157 parameters

  • H-atom parameters constrained

  • Δρmax = 0.41 e Å−3

  • Δρmin = −0.41 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (F2)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C46—H46⋯O5i 0.93 2.53 3.385 (3) 153
Symmetry code: (i) [-x+1, y, -z+{\script{3\over 2}}].

Compound (G1)[link]

Crystal data
  • C8H10N4OS2

  • Mr = 242.32

  • Monoclinic, P 21

  • a = 4.0900 (4) Å

  • b = 6.4482 (6) Å

  • c = 20.7828 (19) Å

  • β = 91.151 (2)°

  • V = 548.00 (9) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.47 mm−1

  • T = 290 K

  • 0.35 × 0.2 × 0.1 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.716, Tmax = 1.000

  • 12608 measured reflections

  • 2642 independent reflections

  • 2523 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.123

  • S = 1.10

  • 2642 reflections

  • 138 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.68 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 1175 Friedel pairs

  • Flack parameter: 0.18 (11)

Table 4
Hydrogen-bond geometry (Å, °) for (G1)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯S1i 0.86 2.85 3.473 (3) 131
C43—H43⋯O5ii 0.93 2.37 3.297 (4) 179
Symmetry codes: (i) x-1, y, z; (ii) x-1, y-1, z.

Table 5
Selected bond lengths (Å) and torsion angles (°) for the title compounds

Structure N2—N3 N3—C4 C4—C41 C1—N2—N3—C4
(E1)[link] 1.377 (2) 1.338 (2) 1.494 (3) 176.6 (2)
(E1)[link] 1.372 (2) 1.333 (2) 1.493 (2) −178.79 (19)
(E1)[link] 1.382 (2) 1.322 (3) 1.498 (3) 179.6 (2)
(F1)[link] 1.3785 (17) 1.344 (2) 1.502 (2) 177.07 (15)
(F2)[link] 1.3839 (19) 1.342 (2) 1.499 (2) −177.06 (16)
(G1)[link] 1.395 (3) 1.341 (4) 1.497 (4) −121.9 (3)

Table 6
Intra­molecular hydrogen-bond contact geometry (Å, °) for the title compounds

N3—H3⋯N42 H⋯N N⋯N N—H⋯N
(E1)[link] 2.25 2.641 (2) 108
(E1)[link] 2.25 2.648 (2) 109
(E1)[link] 2.27 2.663 (3) 108
(F1)[link] 2.21 2.625 (2) 110
(F2)[link] 2.25 2.652 (2) 108
(G1)[link] 2.28 2.666 (4) 107
       
N3—H3⋯S H⋯S N⋯S N—H⋯S
(E1)[link] 2.54 2.9228 (18) 108
(E1)[link] 2.50 2.9031 (16) 109
(E1)[link] 2.55 2.9305 (19) 108
(F1)[link] 2.43 2.8775 (14) 113
(F2)[link] 2.42 2.8587 (18) 112

H atoms were located in difference Fourier maps and subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups, 0.97 Å for secondary CH2 groups and 0.96 Å for methyl groups, and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). For (G1)[link], the precision of the Flack x parameter [Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]); x = 0.18 (11)], whether calculated by the `hole-in-one' method or using TWIN/BASF in SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), 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[Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.]); y = 0.20 (2)] certainly suggests that partial inversion twinning is present.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]) for (E1)[link] and (F1)[link]; APEX2 (Bruker, 2002[Bruker (2002). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]) for (F2)[link] and (G1)[link]. Cell refinement: CrysAlis RED (Oxford Diffraction, 2007[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]) for (E1)[link] and (F1)[link]; SAINT-Plus (Bruker, 2003[Bruker (2003). SAINT-Plus (Version 6.45) and SMART (Version 5.629). Bruker AXS Inc., Madison, Wisconsin, USA.]) for (F2)[link] and (G1)[link]. Data reduction: CrysAlis RED for (E1)[link] and (F1)[link]; SAINT-Plus for (F2)[link] and (G1)[link]. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) for (E1)[link] and (G1)[link]; SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) for (F1)[link] and (F2)[link]. For all compounds, molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: PLATON.

Supporting information


Comment top

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 C1N2—N3—C4—C41 chain in (F1) and (F2), or the SC1—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 top

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).

Experimental top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. The molecular structure of (F1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. The molecular structure of (F2), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. The molecular structure of (G1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 5] 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.]
[Figure 6] 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.]
[Figure 7] 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 top
Crystal data top
C7H8N4OS2Z = 6
Mr = 228.29F(000) = 708
Triclinic, P1Dx = 1.497 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2326 (3) ÅCell parameters from 7143 reflections
b = 12.7207 (4) Åθ = 3.0–28.6°
c = 17.7516 (5) ŵ = 0.50 mm1
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) Å3
Data collection top
Kuma KM4 CCD area-detector
diffractometer
6187 independent reflections
Radiation source: fine-focus sealed tube4162 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
h = 79
Tmin = 0.876, Tmax = 1.000k = 1515
18215 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0504P)2]
where P = (Fo2 + 2Fc2)/3
6187 reflections(Δ/σ)max = 0.001
382 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C7H8N4OS2γ = 73.968 (4)°
Mr = 228.29V = 1519.67 (9) Å3
Triclinic, P1Z = 6
a = 7.2326 (3) ÅMo Kα radiation
b = 12.7207 (4) ŵ = 0.50 mm1
c = 17.7516 (5) ÅT = 295 K
α = 77.877 (3)°0.3 × 0.2 × 0.05 mm
β = 79.096 (3)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
6187 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
4162 reflections with I > 2σ(I)
Tmin = 0.876, Tmax = 1.000Rint = 0.021
18215 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.00Δρmax = 0.23 e Å3
6187 reflectionsΔρmin = 0.20 e Å3
382 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C01A0.5803 (4)0.93418 (18)0.11244 (14)0.0707 (7)
H01A0.70660.93090.08260.085*
H02A0.56310.97720.15280.085*
H03A0.48250.96820.07900.085*
C1A0.6331 (3)0.72665 (16)0.07501 (11)0.0421 (5)
C4A0.6857 (3)0.44277 (17)0.06383 (12)0.0459 (5)
C41A0.7674 (3)0.37711 (16)0.00071 (11)0.0426 (5)
C43A0.9093 (3)0.3683 (2)0.12376 (12)0.0581 (6)
H43A0.96170.40060.17210.070*
C44A0.9067 (4)0.2589 (2)0.11229 (14)0.0610 (7)
H44A0.95800.22000.15350.073*
C46A0.7652 (3)0.26699 (17)0.01052 (13)0.0523 (6)
H46A0.71330.23440.05890.063*
N2A0.6215 (3)0.62144 (13)0.09642 (9)0.0467 (4)
H2A0.57400.59830.14320.056*
N3A0.6862 (3)0.55006 (13)0.04312 (9)0.0493 (5)
H3A0.72750.57480.00420.059*
N42A0.8395 (3)0.42982 (14)0.06819 (9)0.0495 (5)
N45A0.8350 (3)0.20530 (15)0.04555 (12)0.0611 (5)
O5A0.6208 (3)0.40357 (13)0.12862 (8)0.0775 (6)
S1A0.55927 (9)0.79772 (4)0.15484 (3)0.05317 (17)
S2A0.71449 (9)0.77865 (5)0.01443 (3)0.05572 (18)
C01B0.1677 (4)0.6732 (2)0.79005 (12)0.0821 (9)
H01B0.21060.60730.79300.099*
H02B0.25390.71830.82560.099*
H03B0.03860.65320.80350.099*
C1B0.0180 (3)0.65363 (16)0.63673 (11)0.0408 (5)
C4B0.1625 (3)0.68096 (16)0.43404 (11)0.0406 (5)
C41B0.2845 (3)0.59841 (15)0.38473 (10)0.0369 (5)
C43B0.4427 (3)0.42223 (16)0.37351 (11)0.0498 (6)
H43B0.48380.34780.39490.060*
C44B0.4933 (3)0.45526 (16)0.29415 (11)0.0473 (5)
H44B0.56610.40210.26420.057*
C46B0.3346 (3)0.63171 (16)0.30648 (11)0.0426 (5)
H46B0.29370.70620.28520.051*
N2B0.0146 (3)0.70125 (13)0.56241 (9)0.0504 (5)
H2B0.03190.77120.54850.061*
N3B0.1230 (3)0.63722 (13)0.50854 (9)0.0514 (5)
H3B0.16650.56720.52320.062*
N42B0.3386 (2)0.49264 (13)0.41958 (9)0.0443 (4)
N45B0.4411 (3)0.55972 (13)0.25994 (9)0.0448 (4)
O5B0.1056 (2)0.77963 (11)0.40820 (8)0.0586 (4)
S1B0.16796 (10)0.74930 (5)0.69347 (3)0.0639 (2)
S2B0.07308 (9)0.51988 (4)0.66708 (3)0.05409 (17)
C01C0.0262 (4)1.0298 (2)0.14471 (12)0.0697 (7)
H01C0.10461.04200.13480.084*
H02C0.11410.98780.10770.084*
H03C0.05681.09990.13990.084*
C1C0.1290 (3)1.04085 (16)0.29803 (12)0.0445 (5)
C4C0.2617 (3)1.01784 (16)0.50341 (12)0.0449 (5)
C41C0.4024 (3)1.09280 (16)0.55445 (11)0.0426 (5)
C43C0.6220 (3)1.25454 (18)0.56748 (13)0.0582 (6)
H43C0.69331.32380.54640.070*
C44C0.6478 (4)1.22093 (18)0.64723 (13)0.0589 (6)
H44C0.73571.26860.67800.071*
C46C0.4282 (3)1.05988 (17)0.63357 (12)0.0518 (6)
H46C0.35690.99070.65480.062*
N2C0.1305 (3)0.99887 (13)0.37343 (9)0.0493 (5)
H2C0.05400.93570.38800.059*
N3C0.2554 (3)1.05719 (14)0.42809 (10)0.0514 (5)
H3C0.33071.12040.41280.062*
N42C0.4989 (3)1.19107 (14)0.52009 (10)0.0516 (5)
N45C0.5526 (3)1.12401 (15)0.68122 (10)0.0578 (5)
O5C0.1632 (2)0.92709 (12)0.52968 (8)0.0626 (4)
S1C0.04954 (10)0.95473 (5)0.24070 (3)0.05990 (19)
S2C0.27473 (10)1.15904 (5)0.26468 (4)0.0662 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C01A0.102 (2)0.0417 (13)0.0621 (16)0.0158 (13)0.0037 (14)0.0109 (11)
C1A0.0461 (13)0.0424 (12)0.0338 (11)0.0074 (10)0.0002 (9)0.0074 (9)
C4A0.0559 (14)0.0395 (11)0.0356 (11)0.0020 (10)0.0036 (10)0.0074 (9)
C41A0.0433 (13)0.0425 (12)0.0368 (11)0.0003 (10)0.0069 (9)0.0085 (9)
C43A0.0673 (17)0.0609 (15)0.0361 (12)0.0007 (12)0.0000 (11)0.0128 (11)
C44A0.0638 (17)0.0660 (16)0.0520 (15)0.0005 (13)0.0071 (12)0.0300 (12)
C46A0.0572 (15)0.0452 (13)0.0475 (13)0.0040 (11)0.0035 (11)0.0074 (10)
N2A0.0633 (12)0.0429 (10)0.0285 (9)0.0101 (9)0.0070 (8)0.0101 (7)
N3A0.0671 (13)0.0426 (10)0.0321 (9)0.0098 (9)0.0081 (8)0.0116 (7)
N42A0.0590 (12)0.0467 (10)0.0339 (9)0.0012 (9)0.0003 (8)0.0088 (8)
N45A0.0643 (14)0.0515 (12)0.0669 (13)0.0024 (10)0.0073 (11)0.0261 (10)
O5A0.1318 (16)0.0500 (10)0.0370 (9)0.0182 (10)0.0151 (9)0.0072 (7)
S1A0.0754 (4)0.0422 (3)0.0372 (3)0.0128 (3)0.0069 (3)0.0117 (2)
S2A0.0714 (4)0.0557 (3)0.0344 (3)0.0197 (3)0.0074 (3)0.0032 (2)
C01B0.119 (2)0.0796 (19)0.0353 (13)0.0172 (17)0.0142 (14)0.0144 (12)
C1B0.0448 (13)0.0427 (11)0.0333 (11)0.0116 (9)0.0021 (9)0.0090 (9)
C4B0.0457 (13)0.0354 (11)0.0358 (11)0.0056 (9)0.0010 (9)0.0070 (9)
C41B0.0422 (12)0.0336 (10)0.0307 (10)0.0054 (9)0.0007 (9)0.0055 (8)
C43B0.0677 (16)0.0314 (10)0.0386 (12)0.0014 (10)0.0023 (10)0.0032 (9)
C44B0.0598 (15)0.0380 (11)0.0354 (11)0.0010 (10)0.0031 (10)0.0109 (9)
C46B0.0538 (14)0.0332 (10)0.0328 (10)0.0037 (9)0.0003 (9)0.0027 (8)
N2B0.0700 (13)0.0340 (9)0.0334 (9)0.0001 (8)0.0086 (8)0.0066 (7)
N3B0.0752 (13)0.0330 (9)0.0310 (9)0.0009 (8)0.0092 (8)0.0064 (7)
N42B0.0583 (12)0.0353 (9)0.0299 (9)0.0015 (8)0.0017 (8)0.0026 (7)
N45B0.0583 (12)0.0376 (9)0.0297 (9)0.0036 (8)0.0018 (8)0.0047 (7)
O5B0.0772 (11)0.0350 (8)0.0428 (8)0.0058 (7)0.0079 (7)0.0019 (6)
S1B0.0900 (5)0.0472 (3)0.0401 (3)0.0053 (3)0.0155 (3)0.0136 (2)
S2B0.0657 (4)0.0430 (3)0.0397 (3)0.0023 (3)0.0019 (3)0.0004 (2)
C01C0.094 (2)0.0611 (15)0.0424 (13)0.0142 (14)0.0060 (13)0.0038 (11)
C1C0.0541 (14)0.0345 (11)0.0422 (12)0.0086 (10)0.0030 (10)0.0068 (9)
C4C0.0574 (15)0.0349 (11)0.0415 (12)0.0106 (10)0.0005 (10)0.0111 (9)
C41C0.0513 (14)0.0345 (11)0.0423 (12)0.0086 (10)0.0031 (10)0.0125 (9)
C43C0.0707 (17)0.0405 (12)0.0510 (14)0.0049 (11)0.0036 (12)0.0098 (10)
C44C0.0715 (17)0.0454 (13)0.0529 (14)0.0036 (12)0.0043 (12)0.0194 (11)
C46C0.0697 (16)0.0352 (11)0.0445 (13)0.0054 (11)0.0045 (11)0.0068 (9)
N2C0.0611 (12)0.0357 (9)0.0401 (10)0.0068 (8)0.0025 (8)0.0116 (8)
N3C0.0623 (13)0.0383 (9)0.0436 (11)0.0065 (9)0.0025 (9)0.0150 (8)
N42C0.0644 (13)0.0390 (10)0.0433 (10)0.0007 (9)0.0027 (9)0.0095 (8)
N45C0.0764 (14)0.0466 (11)0.0432 (11)0.0068 (10)0.0023 (10)0.0122 (9)
O5C0.0829 (12)0.0372 (8)0.0506 (9)0.0075 (8)0.0017 (8)0.0069 (7)
S1C0.0715 (4)0.0506 (3)0.0401 (3)0.0075 (3)0.0027 (3)0.0088 (2)
S2C0.0782 (5)0.0431 (3)0.0582 (4)0.0113 (3)0.0078 (3)0.0033 (3)
Geometric parameters (Å, º) top
C01A—S1A1.777 (2)C41B—C46B1.374 (2)
C01A—H01A0.9600C43B—N42B1.319 (2)
C01A—H02A0.9600C43B—C44B1.392 (3)
C01A—H03A0.9600C43B—H43B0.9300
C1A—N2A1.334 (2)C44B—N45B1.322 (2)
C1A—S2A1.6508 (19)C44B—H44B0.9300
C1A—S1A1.7594 (19)C46B—N45B1.342 (2)
C4A—O5A1.215 (2)C46B—H46B0.9300
C4A—N3A1.338 (2)N2B—N3B1.372 (2)
C4A—C41A1.494 (3)N2B—H2B0.8600
C41A—N42A1.333 (2)N3B—H3B0.8600
C41A—C46A1.377 (3)C01C—S1C1.783 (2)
C43A—N42A1.326 (2)C01C—H01C0.9600
C43A—C44A1.369 (3)C01C—H02C0.9600
C43A—H43A0.9300C01C—H03C0.9600
C44A—N45A1.327 (3)C1C—N2C1.332 (2)
C44A—H44A0.9300C1C—S2C1.646 (2)
C46A—N45A1.334 (3)C1C—S1C1.759 (2)
C46A—H46A0.9300C4C—O5C1.226 (2)
N2A—N3A1.377 (2)C4C—N3C1.322 (3)
N2A—H2A0.8600C4C—C41C1.498 (3)
N3A—H3A0.8600C41C—N42C1.334 (2)
C01B—S1B1.783 (2)C41C—C46C1.371 (3)
C01B—H01B0.9600C43C—N42C1.326 (3)
C01B—H02B0.9600C43C—C44C1.383 (3)
C01B—H03B0.9600C43C—H43C0.9300
C1B—N2B1.337 (2)C44C—N45C1.317 (3)
C1B—S2B1.658 (2)C44C—H44C0.9300
C1B—S1B1.7449 (19)C46C—N45C1.337 (3)
C4B—O5B1.225 (2)C46C—H46C0.9300
C4B—N3B1.333 (2)N2C—N3C1.382 (2)
C4B—C41B1.493 (2)N2C—H2C0.8600
C41B—N42B1.341 (2)N3C—H3C0.8600
S1A—C01A—H01A109.5C44B—C43B—H43B118.8
S1A—C01A—H02A109.5N45B—C44B—C43B122.12 (17)
H01A—C01A—H02A109.5N45B—C44B—H44B118.9
S1A—C01A—H03A109.5C43B—C44B—H44B118.9
H01A—C01A—H03A109.5N45B—C46B—C41B121.80 (17)
H02A—C01A—H03A109.5N45B—C46B—H46B119.1
N2A—C1A—S2A123.16 (14)C41B—C46B—H46B119.1
N2A—C1A—S1A110.90 (13)C1B—N2B—N3B119.25 (16)
S2A—C1A—S1A125.90 (12)C1B—N2B—H2B120.4
O5A—C4A—N3A122.82 (18)N3B—N2B—H2B120.4
O5A—C4A—C41A123.54 (19)C4B—N3B—N2B121.60 (16)
N3A—C4A—C41A113.61 (17)C4B—N3B—H3B119.2
N42A—C41A—C46A122.54 (18)N2B—N3B—H3B119.2
N42A—C41A—C4A117.24 (18)C43B—N42B—C41B115.44 (16)
C46A—C41A—C4A120.21 (19)C44B—N45B—C46B115.76 (16)
N42A—C43A—C44A122.2 (2)C1B—S1B—C01B103.38 (11)
N42A—C43A—H43A118.9S1C—C01C—H01C109.5
C44A—C43A—H43A118.9S1C—C01C—H02C109.5
N45A—C44A—C43A123.5 (2)H01C—C01C—H02C109.5
N45A—C44A—H44A118.2S1C—C01C—H03C109.5
C43A—C44A—H44A118.2H01C—C01C—H03C109.5
N45A—C46A—C41A122.4 (2)H02C—C01C—H03C109.5
N45A—C46A—H46A118.8N2C—C1C—S2C123.48 (15)
C41A—C46A—H46A118.8N2C—C1C—S1C111.10 (14)
C1A—N2A—N3A119.58 (16)S2C—C1C—S1C125.42 (12)
C1A—N2A—H2A120.2O5C—C4C—N3C123.20 (18)
N3A—N2A—H2A120.2O5C—C4C—C41C122.44 (18)
C4A—N3A—N2A120.99 (16)N3C—C4C—C41C114.35 (18)
C4A—N3A—H3A119.5N42C—C41C—C46C122.21 (18)
N2A—N3A—H3A119.5N42C—C41C—C4C117.66 (18)
C43A—N42A—C41A115.02 (19)C46C—C41C—C4C120.13 (19)
C44A—N45A—C46A114.4 (2)N42C—C43C—C44C122.0 (2)
C1A—S1A—C01A102.83 (10)N42C—C43C—H43C119.0
S1B—C01B—H01B109.5C44C—C43C—H43C119.0
S1B—C01B—H02B109.5N45C—C44C—C43C122.5 (2)
H01B—C01B—H02B109.5N45C—C44C—H44C118.8
S1B—C01B—H03B109.5C43C—C44C—H44C118.8
H01B—C01B—H03B109.5N45C—C46C—C41C122.1 (2)
H02B—C01B—H03B109.5N45C—C46C—H46C119.0
N2B—C1B—S2B122.37 (14)C41C—C46C—H46C119.0
N2B—C1B—S1B111.18 (14)C1C—N2C—N3C119.72 (17)
S2B—C1B—S1B126.44 (11)C1C—N2C—H2C120.1
O5B—C4B—N3B123.44 (17)N3C—N2C—H2C120.1
O5B—C4B—C41B122.87 (17)C4C—N3C—N2C121.41 (17)
N3B—C4B—C41B113.69 (16)C4C—N3C—H3C119.3
N42B—C41B—C46B122.47 (17)N2C—N3C—H3C119.3
N42B—C41B—C4B117.52 (16)C43C—N42C—C41C115.58 (18)
C46B—C41B—C4B120.00 (17)C44C—N45C—C46C115.64 (18)
N42B—C43B—C44B122.40 (18)C1C—S1C—C01C102.27 (11)
N42B—C43B—H43B118.8
O5A—C4A—C41A—N42A177.9 (2)C41B—C4B—N3B—N2B179.22 (18)
N3A—C4A—C41A—N42A3.7 (3)C1B—N2B—N3B—C4B178.79 (19)
O5A—C4A—C41A—C46A2.5 (3)C44B—C43B—N42B—C41B0.1 (3)
N3A—C4A—C41A—C46A175.9 (2)C46B—C41B—N42B—C43B0.4 (3)
N42A—C43A—C44A—N45A0.1 (4)C4B—C41B—N42B—C43B178.64 (19)
N42A—C41A—C46A—N45A0.1 (3)C43B—C44B—N45B—C46B0.7 (3)
C4A—C41A—C46A—N45A179.4 (2)C41B—C46B—N45B—C44B0.3 (3)
S2A—C1A—N2A—N3A2.4 (3)N2B—C1B—S1B—C01B173.40 (18)
S1A—C1A—N2A—N3A175.47 (14)S2B—C1B—S1B—C01B7.8 (2)
O5A—C4A—N3A—N2A3.6 (3)O5C—C4C—C41C—N42C178.3 (2)
C41A—C4A—N3A—N2A177.91 (17)N3C—C4C—C41C—N42C2.6 (3)
C1A—N2A—N3A—C4A176.6 (2)O5C—C4C—C41C—C46C1.5 (3)
C44A—C43A—N42A—C41A0.1 (3)N3C—C4C—C41C—C46C177.6 (2)
C46A—C41A—N42A—C43A0.1 (3)N42C—C43C—C44C—N45C0.2 (4)
C4A—C41A—N42A—C43A179.65 (18)N42C—C41C—C46C—N45C0.4 (4)
C43A—C44A—N45A—C46A0.3 (4)C4C—C41C—C46C—N45C179.8 (2)
C41A—C46A—N45A—C44A0.3 (3)S2C—C1C—N2C—N3C2.0 (3)
N2A—C1A—S1A—C01A178.49 (17)S1C—C1C—N2C—N3C177.19 (15)
S2A—C1A—S1A—C01A3.69 (19)O5C—C4C—N3C—N2C2.1 (3)
O5B—C4B—C41B—N42B179.8 (2)C41C—C4C—N3C—N2C178.82 (17)
N3B—C4B—C41B—N42B0.2 (3)C1C—N2C—N3C—C4C179.6 (2)
O5B—C4B—C41B—C46B1.2 (3)C44C—C43C—N42C—C41C0.2 (4)
N3B—C4B—C41B—C46B179.26 (19)C46C—C41C—N42C—C43C0.3 (3)
N42B—C43B—C44B—N45B0.5 (4)C4C—C41C—N42C—C43C179.9 (2)
N42B—C41B—C46B—N45B0.2 (3)C43C—C44C—N45C—C46C0.2 (4)
C4B—C41B—C46B—N45B178.81 (19)C41C—C46C—N45C—C44C0.3 (3)
S2B—C1B—N2B—N3B1.7 (3)N2C—C1C—S1C—C01C178.52 (16)
S1B—C1B—N2B—N3B177.20 (16)S2C—C1C—S1C—C01C0.6 (2)
O5B—C4B—N3B—N2B0.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H2A···N45B0.862.132.987 (2)174
C44B—H44B···O5A0.932.363.061 (2)132
N2B—H2B···O5C0.861.942.790 (2)172
N2C—H2C···O5B0.862.002.850 (2)170
(F1) N'-[bis(methylsulfanyl)methylidene]pyrazine-2-carbohydrazide top
Crystal data top
C8H10N4OS2F(000) = 504
Mr = 242.32Dx = 1.468 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8241 reflections
a = 7.8332 (2) Åθ = 2.9–28.6°
b = 21.0883 (4) ŵ = 0.46 mm1
c = 7.3920 (2) ÅT = 297 K
β = 116.121 (4)°Prism, colourless
V = 1096.36 (5) Å30.2 × 0.1 × 0.05 mm
Z = 4
Data collection top
Kuma KM4 CCD area-detector
diffractometer
2236 independent reflections
Radiation source: fine-focus sealed tube1960 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
h = 98
Tmin = 0.946, Tmax = 1.000k = 2626
12975 measured reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.087 w = 1/[σ2(Fo2) + (0.0445P)2 + 0.2852P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2236 reflectionsΔρmax = 0.26 e Å3
139 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (11)
Crystal data top
C8H10N4OS2V = 1096.36 (5) Å3
Mr = 242.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.8332 (2) ŵ = 0.46 mm1
b = 21.0883 (4) ÅT = 297 K
c = 7.3920 (2) Å0.2 × 0.1 × 0.05 mm
β = 116.121 (4)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
2236 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
1960 reflections with I > 2σ(I)
Tmin = 0.946, Tmax = 1.000Rint = 0.015
12975 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.07Δρmax = 0.26 e Å3
2236 reflectionsΔρmin = 0.20 e Å3
139 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C11.0226 (2)0.61366 (8)0.7928 (2)0.0423 (4)
C011.3336 (3)0.61423 (10)0.7154 (3)0.0628 (5)
H01A1.40110.64170.82810.075*
H01B1.25530.63920.59980.075*
H01C1.42300.59030.68670.075*
C020.7790 (3)0.50863 (9)0.6980 (3)0.0624 (5)
H02A0.88670.48100.73630.075*
H02B0.73380.52030.55900.075*
H02C0.67980.48720.71650.075*
C40.8997 (2)0.77379 (8)0.7750 (2)0.0398 (3)
C410.7227 (2)0.80257 (7)0.7710 (2)0.0374 (3)
C430.4284 (2)0.78993 (8)0.7531 (3)0.0490 (4)
H430.32790.76440.74310.059*
C440.4121 (2)0.85490 (8)0.7613 (3)0.0490 (4)
H440.30020.87160.75620.059*
C460.7053 (2)0.86748 (8)0.7796 (3)0.0458 (4)
H460.80490.89330.78810.055*
N21.03942 (18)0.67337 (6)0.7761 (2)0.0421 (3)
N30.89650 (18)0.71015 (6)0.7821 (2)0.0425 (3)
H30.80230.69180.79060.051*
N420.58415 (18)0.76297 (6)0.7590 (2)0.0456 (3)
N450.5491 (2)0.89439 (7)0.7761 (2)0.0529 (4)
O51.02739 (17)0.80592 (6)0.7719 (2)0.0585 (3)
S11.18679 (6)0.56102 (2)0.77482 (9)0.05940 (17)
S20.84763 (6)0.57861 (2)0.85177 (8)0.05666 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0299 (7)0.0463 (9)0.0505 (9)0.0015 (6)0.0174 (7)0.0056 (7)
C010.0438 (9)0.0729 (13)0.0832 (14)0.0051 (9)0.0384 (10)0.0046 (10)
C020.0549 (11)0.0463 (10)0.0793 (13)0.0074 (8)0.0234 (10)0.0030 (9)
C40.0345 (7)0.0460 (8)0.0415 (8)0.0018 (6)0.0191 (6)0.0010 (6)
C410.0337 (7)0.0420 (8)0.0382 (7)0.0018 (6)0.0174 (6)0.0006 (6)
C430.0375 (8)0.0495 (9)0.0668 (11)0.0025 (7)0.0291 (8)0.0002 (8)
C440.0425 (9)0.0519 (10)0.0591 (10)0.0107 (7)0.0283 (8)0.0000 (8)
C460.0426 (9)0.0422 (8)0.0558 (10)0.0018 (7)0.0246 (8)0.0017 (7)
N20.0317 (6)0.0468 (7)0.0501 (7)0.0049 (5)0.0200 (6)0.0040 (6)
N30.0325 (6)0.0438 (7)0.0573 (8)0.0036 (5)0.0255 (6)0.0001 (6)
N420.0377 (7)0.0419 (7)0.0629 (8)0.0020 (6)0.0272 (6)0.0001 (6)
N450.0528 (8)0.0445 (8)0.0666 (9)0.0066 (7)0.0310 (7)0.0040 (7)
O50.0461 (7)0.0540 (7)0.0896 (9)0.0041 (6)0.0428 (7)0.0028 (7)
S10.0461 (3)0.0486 (3)0.0918 (4)0.00612 (19)0.0379 (3)0.0082 (2)
S20.0465 (3)0.0522 (3)0.0816 (4)0.00241 (19)0.0376 (2)0.0025 (2)
Geometric parameters (Å, º) top
C1—N21.278 (2)C4—C411.502 (2)
C1—S11.7478 (15)C41—N421.3411 (19)
C1—S21.7723 (16)C41—C461.380 (2)
C01—S11.794 (2)C43—N421.329 (2)
C01—H01A0.9600C43—C441.380 (2)
C01—H01B0.9600C43—H430.9300
C01—H01C0.9600C44—N451.324 (2)
C02—S21.795 (2)C44—H440.9300
C02—H02A0.9600C46—N451.339 (2)
C02—H02B0.9600C46—H460.9300
C02—H02C0.9600N2—N31.3785 (17)
C4—O51.2165 (19)N3—H30.8600
C4—N31.344 (2)
N2—C1—S1120.54 (12)N42—C41—C4117.57 (14)
N2—C1—S2123.95 (12)C46—C41—C4120.60 (14)
S1—C1—S2115.37 (9)N42—C43—C44121.67 (16)
S1—C01—H01A109.5N42—C43—H43119.2
S1—C01—H01B109.5C44—C43—H43119.2
H01A—C01—H01B109.5N45—C44—C43122.71 (15)
S1—C01—H01C109.5N45—C44—H44118.6
H01A—C01—H01C109.5C43—C44—H44118.6
H01B—C01—H01C109.5N45—C46—C41121.85 (15)
S2—C02—H02A109.5N45—C46—H46119.1
S2—C02—H02B109.5C41—C46—H46119.1
H02A—C02—H02B109.5C1—N2—N3115.58 (13)
S2—C02—H02C109.5C4—N3—N2122.10 (13)
H02A—C02—H02C109.5C4—N3—H3119.0
H02B—C02—H02C109.5N2—N3—H3119.0
O5—C4—N3125.92 (14)C43—N42—C41116.10 (14)
O5—C4—C41122.27 (14)C44—N45—C46115.82 (14)
N3—C4—C41111.81 (13)C1—S1—C01101.17 (9)
N42—C41—C46121.83 (14)C1—S2—C02103.63 (9)
O5—C4—C41—N42174.91 (15)C1—N2—N3—C4177.07 (15)
N3—C4—C41—N425.0 (2)C44—C43—N42—C410.8 (3)
O5—C4—C41—C465.2 (2)C46—C41—N42—C430.9 (2)
N3—C4—C41—C46174.88 (15)C4—C41—N42—C43179.16 (14)
N42—C43—C44—N450.2 (3)C43—C44—N45—C461.0 (3)
N42—C41—C46—N450.1 (3)C41—C46—N45—C440.8 (3)
C4—C41—C46—N45179.96 (14)N2—C1—S1—C014.05 (17)
S1—C1—N2—N3176.70 (11)S2—C1—S1—C01179.90 (10)
S2—C1—N2—N37.8 (2)N2—C1—S2—C02141.69 (15)
O5—C4—N3—N23.4 (3)S1—C1—S2—C0242.62 (12)
C41—C4—N3—N2176.49 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C44—H44···O5i0.932.593.219 (2)125
Symmetry code: (i) x1, y, z.
(F2) N'-[bis(methylsulfanyl)methylidene]-6-methoxypyrazine-2-carbohydrazide top
Crystal data top
C9H12N4O2S2F(000) = 1136
Mr = 272.35Dx = 1.461 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8658 reflections
a = 23.111 (2) Åθ = 2.7–27.0°
b = 7.5812 (7) ŵ = 0.43 mm1
c = 15.6547 (14) ÅT = 270 K
β = 115.430 (2)°Prisme, colourless
V = 2477.1 (4) Å30.5 × 0.2 × 0.1 mm
Z = 8
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3051 independent reflections
Radiation source: fine-focus sealed tube2351 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 3030
Tmin = 0.516, Tmax = 1k = 109
27591 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.072P)2 + 1.1533P]
where P = (Fo2 + 2Fc2)/3
3051 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C9H12N4O2S2V = 2477.1 (4) Å3
Mr = 272.35Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.111 (2) ŵ = 0.43 mm1
b = 7.5812 (7) ÅT = 270 K
c = 15.6547 (14) Å0.5 × 0.2 × 0.1 mm
β = 115.430 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3051 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2351 reflections with I > 2σ(I)
Tmin = 0.516, Tmax = 1Rint = 0.043
27591 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.03Δρmax = 0.41 e Å3
3051 reflectionsΔρmin = 0.41 e Å3
157 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.32187 (8)0.0500 (2)0.93843 (13)0.0441 (4)
C010.30859 (12)0.0459 (3)1.10871 (16)0.0677 (6)
H01A0.26410.07841.08080.081*
H01B0.32780.07901.17430.081*
H01C0.31240.07931.10340.081*
C020.23931 (11)0.1431 (3)0.78714 (16)0.0634 (5)
H02A0.23790.05030.74460.076*
H02B0.20070.21150.75930.076*
H02C0.27550.21770.79910.076*
C40.44767 (9)0.1438 (2)0.87865 (12)0.0460 (4)
C110.56273 (13)0.3733 (3)1.20507 (16)0.0721 (6)
H11A0.52050.42141.17140.086*
H11B0.58200.42141.26790.086*
H11C0.56000.24731.20850.086*
C410.51134 (8)0.2302 (2)0.93364 (12)0.0431 (4)
C430.58091 (9)0.3626 (2)1.06730 (14)0.0513 (4)
C440.62150 (10)0.3955 (3)1.02402 (17)0.0635 (6)
H440.65920.45781.05730.076*
C460.55275 (9)0.2544 (3)0.89284 (14)0.0552 (5)
H460.54220.20960.83270.066*
N20.35298 (7)0.05000 (19)0.88799 (10)0.0447 (3)
N30.41252 (7)0.13022 (19)0.92788 (10)0.0434 (3)
H30.42710.17160.98440.052*
N420.52559 (7)0.28252 (19)1.02262 (10)0.0438 (3)
N450.60835 (9)0.3418 (3)0.93820 (15)0.0655 (5)
O50.43033 (8)0.0961 (2)0.79736 (10)0.0717 (5)
O60.60084 (8)0.4175 (2)1.15676 (11)0.0686 (4)
S10.34869 (3)0.15723 (7)1.04845 (4)0.06153 (19)
S20.24630 (2)0.05000 (7)0.89574 (4)0.06069 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0410 (9)0.0385 (8)0.0517 (9)0.0059 (6)0.0191 (7)0.0012 (7)
C010.0616 (12)0.0903 (16)0.0595 (12)0.0078 (12)0.0340 (10)0.0074 (11)
C020.0565 (12)0.0572 (12)0.0619 (12)0.0108 (9)0.0115 (9)0.0041 (9)
C40.0451 (9)0.0483 (9)0.0460 (9)0.0047 (7)0.0208 (7)0.0025 (7)
C110.0822 (17)0.0718 (14)0.0557 (12)0.0029 (12)0.0234 (12)0.0056 (10)
C410.0397 (8)0.0414 (8)0.0493 (9)0.0000 (7)0.0200 (7)0.0060 (7)
C430.0416 (9)0.0437 (9)0.0598 (11)0.0002 (7)0.0137 (8)0.0026 (8)
C440.0413 (10)0.0619 (12)0.0793 (15)0.0096 (9)0.0182 (10)0.0054 (10)
C460.0467 (10)0.0636 (12)0.0600 (11)0.0008 (9)0.0273 (9)0.0060 (9)
N20.0389 (7)0.0456 (8)0.0472 (7)0.0075 (6)0.0162 (6)0.0003 (6)
N30.0394 (7)0.0484 (8)0.0425 (7)0.0087 (6)0.0177 (6)0.0004 (6)
N420.0384 (7)0.0407 (7)0.0504 (8)0.0002 (6)0.0174 (6)0.0033 (6)
N450.0445 (9)0.0780 (12)0.0789 (13)0.0065 (8)0.0312 (9)0.0111 (9)
O50.0675 (10)0.1027 (12)0.0505 (8)0.0296 (9)0.0305 (7)0.0154 (8)
O60.0584 (9)0.0720 (9)0.0619 (9)0.0125 (7)0.0131 (7)0.0119 (7)
S10.0646 (3)0.0686 (3)0.0621 (3)0.0243 (3)0.0374 (3)0.0169 (2)
S20.0445 (3)0.0661 (3)0.0731 (3)0.0184 (2)0.0267 (2)0.0089 (2)
Geometric parameters (Å, º) top
C1—N21.276 (2)C11—H11A0.9600
C1—S21.7519 (17)C11—H11B0.9600
C1—S11.7592 (18)C11—H11C0.9600
C01—S11.792 (2)C41—N421.346 (2)
C01—H01A0.9600C41—C461.372 (3)
C01—H01B0.9600C43—N421.313 (2)
C01—H01C0.9600C43—O61.339 (3)
C02—S21.783 (2)C43—C441.395 (3)
C02—H02A0.9600C44—N451.308 (3)
C02—H02B0.9600C44—H440.9300
C02—H02C0.9600C46—N451.345 (3)
C4—O51.214 (2)C46—H460.9300
C4—N31.342 (2)N2—N31.3839 (19)
C4—C411.499 (2)N3—H30.8600
C11—O61.425 (3)
N2—C1—S2119.89 (13)H11B—C11—H11C109.5
N2—C1—S1123.41 (13)N42—C41—C46122.19 (17)
S2—C1—S1116.61 (10)N42—C41—C4117.81 (15)
S1—C01—H01A109.5C46—C41—C4120.00 (17)
S1—C01—H01B109.5N42—C43—O6121.31 (18)
H01A—C01—H01B109.5N42—C43—C44121.85 (19)
S1—C01—H01C109.5O6—C43—C44116.84 (18)
H01A—C01—H01C109.5N45—C44—C43122.32 (19)
H01B—C01—H01C109.5N45—C44—H44118.8
S2—C02—H02A109.5C43—C44—H44118.8
S2—C02—H02B109.5N45—C46—C41121.27 (19)
H02A—C02—H02B109.5N45—C46—H46119.4
S2—C02—H02C109.5C41—C46—H46119.4
H02A—C02—H02C109.5C1—N2—N3115.85 (14)
H02B—C02—H02C109.5C4—N3—N2120.27 (14)
O5—C4—N3124.78 (17)C4—N3—H3119.9
O5—C4—C41122.21 (16)N2—N3—H3119.9
N3—C4—C41112.99 (15)C43—N42—C41115.91 (16)
O6—C11—H11A109.5C44—N45—C46116.32 (18)
O6—C11—H11B109.5C43—O6—C11117.95 (16)
H11A—C11—H11B109.5C1—S1—C01104.67 (10)
O6—C11—H11C109.5C1—S2—C02101.68 (10)
H11A—C11—H11C109.5
O5—C4—C41—N42178.34 (18)O6—C43—N42—C41178.65 (16)
N3—C4—C41—N420.0 (2)C44—C43—N42—C411.7 (3)
O5—C4—C41—C461.3 (3)C46—C41—N42—C431.8 (3)
N3—C4—C41—C46179.71 (16)C4—C41—N42—C43177.90 (15)
N42—C43—C44—N453.1 (3)C43—C44—N45—C460.9 (3)
O6—C43—C44—N45177.2 (2)C41—C46—N45—C442.6 (3)
N42—C41—C46—N454.1 (3)N42—C43—O6—C115.2 (3)
C4—C41—C46—N45175.60 (17)C44—C43—O6—C11175.1 (2)
S2—C1—N2—N3179.29 (11)N2—C1—S1—C01156.84 (16)
S1—C1—N2—N34.4 (2)S2—C1—S1—C0126.73 (14)
O5—C4—N3—N23.1 (3)N2—C1—S2—C024.43 (17)
C41—C4—N3—N2178.58 (14)S1—C1—S2—C02179.00 (11)
C1—N2—N3—C4177.06 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C46—H46···O5i0.932.533.385 (3)153
Symmetry code: (i) x+1, y, z+3/2.
(G1) methyl 1-methyl-2-(pyrazin-2-ylcarbonyl)hydrazinecarbodithioate top
Crystal data top
C8H10N4OS2F(000) = 252
Mr = 242.32Dx = 1.469 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 8014 reflections
a = 4.0900 (4) Åθ = 2.9–30.4°
b = 6.4482 (6) ŵ = 0.47 mm1
c = 20.7828 (19) ÅT = 290 K
β = 91.151 (2)°Prism, colourless
V = 548.00 (9) Å30.35 × 0.2 × 0.1 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2642 independent reflections
Radiation source: fine-focus sealed tube2523 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 55
Tmin = 0.716, Tmax = 1k = 88
12608 measured reflectionsl = 2627
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0713P)2 + 0.2203P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2642 reflectionsΔρmax = 0.68 e Å3
138 parametersΔρmin = 0.21 e Å3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.18 (11)
Crystal data top
C8H10N4OS2V = 548.00 (9) Å3
Mr = 242.32Z = 2
Monoclinic, P21Mo Kα radiation
a = 4.0900 (4) ŵ = 0.47 mm1
b = 6.4482 (6) ÅT = 290 K
c = 20.7828 (19) Å0.35 × 0.2 × 0.1 mm
β = 91.151 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2642 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2523 reflections with I > 2σ(I)
Tmin = 0.716, Tmax = 1Rint = 0.023
12608 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.68 e Å3
S = 1.10Δρmin = 0.21 e Å3
2642 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
138 parametersAbsolute structure parameter: 0.18 (11)
1 restraint
Special details top

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 (Å2) top
xyzUiso*/Ueq
C11.0937 (7)0.8741 (5)0.85674 (13)0.0386 (6)
C011.4285 (9)0.5824 (6)0.93116 (16)0.0562 (9)
H01A1.26950.60550.96380.067*
H01B1.60460.67970.93660.067*
H01C1.51230.44380.93490.067*
C40.9719 (7)0.8113 (5)0.69513 (14)0.0388 (6)
C100.7799 (9)1.1372 (6)0.79370 (16)0.0524 (7)
H10A0.94191.23460.78010.063*
H10B0.69031.18260.83370.063*
H10C0.60841.12820.76160.063*
C410.8459 (7)0.6519 (4)0.64844 (12)0.0362 (5)
C430.5792 (9)0.3512 (5)0.62875 (18)0.0534 (8)
H430.45880.23800.64270.064*
C440.6554 (10)0.3659 (6)0.56436 (18)0.0576 (8)
H440.59010.25990.53660.069*
C460.9132 (9)0.6699 (5)0.58369 (14)0.0488 (7)
H461.02750.78540.56960.059*
N20.9302 (7)0.9338 (4)0.80247 (11)0.0419 (5)
N30.8641 (6)0.7856 (4)0.75509 (11)0.0402 (5)
H30.75320.67670.76440.048*
N420.6733 (7)0.4945 (4)0.67133 (12)0.0451 (6)
N450.8187 (9)0.5261 (6)0.54075 (13)0.0591 (7)
O51.1584 (6)0.9485 (4)0.67904 (12)0.0572 (6)
S11.23971 (17)0.61678 (12)0.85307 (3)0.04268 (18)
S21.1449 (2)1.03003 (14)0.91904 (4)0.0560 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0403 (13)0.0456 (14)0.0299 (12)0.0142 (11)0.0015 (9)0.0026 (11)
C010.0605 (18)0.064 (2)0.0433 (15)0.0092 (16)0.0072 (13)0.0087 (15)
C40.0428 (14)0.0384 (14)0.0351 (13)0.0074 (11)0.0021 (10)0.0015 (11)
C100.0706 (19)0.0403 (16)0.0461 (16)0.0038 (15)0.0042 (13)0.0019 (13)
C410.0427 (12)0.0339 (14)0.0320 (12)0.0024 (10)0.0019 (9)0.0011 (9)
C430.067 (2)0.0418 (16)0.0508 (17)0.0136 (14)0.0067 (14)0.0026 (14)
C440.077 (2)0.0509 (18)0.0440 (17)0.0065 (16)0.0115 (15)0.0130 (15)
C460.0645 (17)0.0498 (18)0.0320 (13)0.0082 (13)0.0021 (12)0.0011 (11)
N20.0574 (14)0.0380 (12)0.0302 (11)0.0095 (10)0.0044 (9)0.0016 (10)
N30.0541 (14)0.0356 (12)0.0308 (11)0.0154 (10)0.0023 (9)0.0030 (9)
N420.0606 (15)0.0401 (13)0.0343 (11)0.0129 (11)0.0026 (10)0.0026 (10)
N450.0846 (19)0.0588 (16)0.0338 (12)0.0037 (16)0.0001 (12)0.0049 (13)
O50.0711 (15)0.0531 (13)0.0476 (12)0.0294 (12)0.0079 (11)0.0005 (10)
S10.0502 (3)0.0432 (3)0.0346 (3)0.0061 (3)0.0022 (2)0.0018 (3)
S20.0715 (5)0.0599 (5)0.0363 (3)0.0106 (4)0.0040 (3)0.0148 (3)
Geometric parameters (Å, º) top
C1—N21.355 (4)C10—H10C0.9600
C1—S21.649 (3)C41—N421.330 (4)
C1—S11.765 (3)C41—C461.384 (4)
C01—S11.797 (3)C43—N421.331 (4)
C01—H01A0.9600C43—C441.383 (5)
C01—H01B0.9600C43—H430.9300
C01—H01C0.9600C44—N451.329 (5)
C4—O51.219 (4)C44—H440.9300
C4—N31.341 (4)C46—N451.338 (4)
C4—C411.497 (4)C46—H460.9300
C10—N21.458 (4)N2—N31.395 (3)
C10—H10A0.9600N3—H30.8600
C10—H10B0.9600
N2—C1—S2122.2 (2)C46—C41—C4120.0 (3)
N2—C1—S1113.1 (2)N42—C43—C44121.9 (3)
S2—C1—S1124.69 (18)N42—C43—H43119.1
S1—C01—H01A109.5C44—C43—H43119.1
S1—C01—H01B109.5N45—C44—C43122.3 (3)
H01A—C01—H01B109.5N45—C44—H44118.8
S1—C01—H01C109.5C43—C44—H44118.8
H01A—C01—H01C109.5N45—C46—C41122.0 (3)
H01B—C01—H01C109.5N45—C46—H46119.0
O5—C4—N3124.3 (3)C41—C46—H46119.0
O5—C4—C41121.9 (3)C1—N2—N3118.6 (3)
N3—C4—C41113.7 (2)C1—N2—C10124.0 (3)
N2—C10—H10A109.5N3—N2—C10116.9 (2)
N2—C10—H10B109.5C4—N3—N2120.6 (2)
H10A—C10—H10B109.5C4—N3—H3119.7
N2—C10—H10C109.5N2—N3—H3119.7
H10A—C10—H10C109.5C41—N42—C43116.1 (3)
H10B—C10—H10C109.5C44—N45—C46115.6 (3)
N42—C41—C46121.9 (3)C1—S1—C01102.50 (16)
N42—C41—C4118.0 (2)
O5—C4—C41—N42172.6 (3)O5—C4—N3—N28.0 (5)
N3—C4—C41—N426.5 (4)C41—C4—N3—N2172.9 (3)
O5—C4—C41—C466.7 (5)C1—N2—N3—C4121.9 (3)
N3—C4—C41—C46174.2 (3)C10—N2—N3—C466.0 (4)
N42—C43—C44—N451.9 (6)C46—C41—N42—C432.4 (5)
N42—C41—C46—N452.5 (5)C4—C41—N42—C43176.9 (3)
C4—C41—C46—N45176.8 (3)C44—C43—N42—C410.3 (5)
S2—C1—N2—N3172.5 (2)C43—C44—N45—C461.9 (6)
S1—C1—N2—N37.3 (3)C41—C46—N45—C440.2 (6)
S2—C1—N2—C101.0 (4)N2—C1—S1—C01178.2 (2)
S1—C1—N2—C10178.8 (2)S2—C1—S1—C011.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···S1i0.862.853.473 (3)131
C43—H43···O5ii0.932.373.297 (4)179
Symmetry codes: (i) x1, y, z; (ii) x1, y1, z.

Experimental details

(E1)(F1)(F2)(G1)
Crystal data
Chemical formulaC7H8N4OS2C8H10N4OS2C9H12N4O2S2C8H10N4OS2
Mr228.29242.32272.35242.32
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, C2/cMonoclinic, P21
Temperature (K)295297270290
a, b, c (Å)7.2326 (3), 12.7207 (4), 17.7516 (5)7.8332 (2), 21.0883 (4), 7.3920 (2)23.111 (2), 7.5812 (7), 15.6547 (14)4.0900 (4), 6.4482 (6), 20.7828 (19)
α, β, γ (°)77.877 (3), 79.096 (3), 73.968 (4)90, 116.121 (4), 9090, 115.430 (2), 9090, 91.151 (2), 90
V3)1519.67 (9)1096.36 (5)2477.1 (4)548.00 (9)
Z6482
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.500.460.430.47
Crystal size (mm)0.3 × 0.2 × 0.050.2 × 0.1 × 0.050.5 × 0.2 × 0.10.35 × 0.2 × 0.1
Data collection
DiffractometerKuma KM4 CCD area-detector
diffractometer
Kuma KM4 CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.876, 1.0000.946, 1.0000.516, 10.716, 1
No. of measured, independent and
observed [I > 2σ(I)] reflections
18215, 6187, 4162 12975, 2236, 1960 27591, 3051, 2351 12608, 2642, 2523
Rint0.0210.0150.0430.023
(sin θ/λ)max1)0.6250.6250.6670.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.094, 1.00 0.031, 0.087, 1.07 0.043, 0.126, 1.03 0.046, 0.123, 1.10
No. of reflections6187223630512642
No. of parameters382139157138
No. of restraints0001
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.200.26, 0.200.41, 0.410.68, 0.21
Absolute structure???Flack (1983), with how many Friedel pairs?
Absolute structure parameter???0.18 (11)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), APEX2 (Bruker, 2002), CrysAlis RED (Oxford Diffraction, 2007), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (E1) top
D—H···AD—HH···AD···AD—H···A
N2A—H2A···N45B0.862.132.987 (2)174
C44B—H44B···O5A0.932.363.061 (2)132
N2B—H2B···O5C0.861.942.790 (2)172
N2C—H2C···O5B0.862.002.850 (2)170
Hydrogen-bond geometry (Å, º) for (F1) top
D—H···AD—HH···AD···AD—H···A
C44—H44···O5i0.932.593.219 (2)125
Symmetry code: (i) x1, y, z.
Hydrogen-bond geometry (Å, º) for (F2) top
D—H···AD—HH···AD···AD—H···A
C46—H46···O5i0.932.533.385 (3)153
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) for (G1) top
D—H···AD—HH···AD···AD—H···A
N3—H3···S1i0.862.853.473 (3)131
C43—H43···O5ii0.932.373.297 (4)179
Symmetry codes: (i) x1, y, z; (ii) x1, y1, z.
Selected bond lengths (Å) and torsion angles (°) top
StructureN2—N3N3—C4C4—C41C1—N2—N3—C4
(E1)1.377 (2)1.338 (2)1.494 (3)176.6 (2)
(E1)1.372 (2)1.333 (2)1.493 (2)-178.79 (19)
(E1)1.382 (2)1.322 (3)1.498 (3)179.6 (2)
(F1)1.3785 (17)1.344 (2)1.502 (2)177.07 (15)
(F2)1.3839 (19)1.342 (2)1.499 (2)-177.06 (16)
(G1)1.395 (3)1.341 (4)1.497 (4)-121.9 (3)
Intramolecular hydrogen-bond contact geometry (Å, °) top
N3—H3···N42H···NN···NN—H···N
(E1)2.252.641 (2)108
(E1)2.252.648 (2)109
(E1)2.272.663 (3)108
(F1)2.212.625 (2)110
(F2)2.252.652 (2)108
(G1)2.282.666 (4)107
N3—H3···S2H···SN···SN—H···S
(E1)2.542.9228 (18)108
(E1)2.502.9031 (16)109
(E1)2.552.9305 (19)108
(F1)2.432.8775 (14)113
(F2)2.422.8587 (18)112
(G1)
 

Footnotes

For Part II, see Olczak et al. (2011[Olczak, A., Szczesio, M., Gołka, J., Orlewska, C., Gobis, K., Foks, H. & Główka, M. L. (2011). Acta Cryst. C67, o37-o42.]).

Acknowledgements

This study was supported by the Ministry of Science and Higher Education under project No. N204 111735.

References

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