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The X-ray single-crystal structure determinations of the chemically related compounds 2-amino-1,3,4-thia­diazo­lium hydrogen oxalate, C2H4N3S+·C2HO4, (I), 2-amino-1,3,4-thia­diazole–succinic acid (1/2), C2H3N3S·2C4H6O4, (II), 2-amino-1,3,4-thia­diazole–glutaric acid (1/1), C2H3N3S·C5H8O4, (III), and 2-amino-1,3,4-thia­diazole–adipic acid (1/1), C2H3N3S·C6H10O4, (IV), are reported and their hydrogen-bonding patterns are compared. The hydrogen bonds are of the types N—H...O or O—H...N and are of moderate strength. In some cases, weak C—H...O inter­actions are also present. Compound (II) differs from the others not only in the molar ratio of base and acid (1:2), but also in its hydrogen-bonding pattern, which is based on chain motifs. In (I), (III) and (IV), the most prominent feature is the presence of an R22(8) graph-set motif formed by N—H...O and O—H...N hydrogen bonds, which are present in all structures except for (I), where only a pair of N—H...O hydrogen bonds is present, in agreement with the greater acidity of oxalic acid. There are nonbonding S...O inter­actions present in all four structures. The difference electron-density maps show a lack of electron density about the S atom along the S...O vector. In all four structures, the carboxylic acid H atoms are present in a rare configuration with a C—C—O—H torsion angle of ∼0°. In the structures of (II)–(IV), the C—C—O—H torsion angle of the second carboxylic acid group has the more common value of ∼|180|°. The di­carb­oxy­lic acid mol­ecules are situated on crystallographic inversion centres in (II). The Raman and IR spectra of the title compounds are presented and analysed.

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CCDC references: 1018659; 1018660; 1018661; 1018662

Introduction top

The investigation of the title structures has been motivated by the search for novel materials based on organic sulfur-containing heteroaromatic molecules, which might be suitable for nonlinear optics. The present paper follows up our previous investigations on triazolium compounds (Matulková et al., 2007, 2008, 2012, 2013; Matulková, Císařová & Němec, 2011).

Application of the 2-amino-1,3,4-thia­diazole molecule as a constituent part of the structures discussed in the above references was motivated by their calculated hyperpolarizability values (Matulková et al., 2014), which are a factor of ten larger than those for the studied amino­triazoles (Matulková et al., 2012) and amino­thia­zoles (Matulková, Němec et al., 2011; Matulková, Cihelka et al., 2011). The structures described by Matulková et al. (2014), i.e. salts of 2-amino-1,3,4-thia­diazole with hydro­chloric, perchloric, nitric, sulfuric, selenic, phospho­rous and phospho­ric acids, have recently been investigated by vibrational spectroscopy (Matulková & Němec, 2014).

A non-centrosymmetric space group is a necessary prerequisite for the desired physical properties, such as frequency doubling of light (second-harmonic generation) by a crystal (Boulanger & Zyss, 2003). Not all attempts at preparing structures with 2-amino-1,3,4-thia­diazole resulted in non-centrosymmetric crystals. Nevertheless, such structures are inter­esting from the structural point of view and therefore they are reported here. The aim of the present study is a comparison of the title structures, especially a comparison of their hydrogen-bonding patterns.

In addition to structure determinations, FT–IR and FT–Raman spectra were measured. These spectra are included in the supplementary material, along with a table which lists the observed maxima.

AUTHORS: Unfortunately, the original CIF segment for (II) included only one succinic acid molecule in the formula and molecular weight. This will affect various other parameters. Please therefore provide a corrected CIF segment taking the second molecule into account.

Please note that we cannot accept supplementary data as .smi files. These files are also not discussed anywhere. Please supply them in a format which does not require proprietary software, and add a sentence or two to the paper explaining their inclusion.

Experimental top

Synthesis and crystallization top

Crystals of the title compounds were prepared by slow evaporation at room temperature. The preparation for each of the compounds is specified in Table 1.

FT–IR spectra of the polycrystalline samples (diluted by grinding with spectroscopy-grade KBr) were recorded by the DRIFTS (diffuse refle­cta­nce IR Fourier transform spectroscopy) technique on a Nicolet Magna 6700 FTIR spectrometer (4 cm-1 resolution, Happ–Genzel apodization) in the range 400–4000 cm-1. The FT–Raman spectra of the polycrystalline samples were obtained on a Nicolet Magna 6700 FTIR spectrometer equipped with a Nicolet Nexus FT Raman module (4 cm-1 resolution, Happ–Genzel apodization, excitation at 1064 nm by Nd:YVO4 laser, 450 mW power at the sample) in the range 150–3700 cm-1. The spectra and the corresponding table with the listed maxima are included in the supplementary material.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The H-atom refinements differed slightly in the application of restraints and constraints, but in all cases those reflections for which |Io - Ic|/w > 15 have been discarded from the refinement. Reflections with θ < 3°, which could have been affected by shadowing by the beamstop, were also excluded from the refinements.

For (I), the positional parameters of the primary amine H atoms were refined with a distance restraint N—H = 0.88 (1) Å. The positional parameters of the hydroxyl atom H1O4 were refined freely with no restraints. The displacement parameters of the H atoms attached to atoms N2, N3 and C1 were refined with Uiso(H) = 1.2Ueq(parent), while Uiso(H) = 1.5Ueq(O4).

For (II), the positional parameters of the primary amine H atoms were refined with a distance restraint N—H = 0.88 (1) Å. The methyl­ene H atoms bound to C3 and C4 were constrained with C—H = 0.99 Å. The displacement parameters of all the H atoms (the aryl H atom attached to C1, the methyl­ene H atoms and the primary amine H atoms) were refined with Uiso(H) = 1.2Ueq(parent), except for H1O2 and H1O3 where Uiso(H) = 1.5Ueq(O) while their positional parameters were refined freely.

For (III), the positional parameters of the primary amine H atoms were refined with distance restraints N3—H1N3 = N3—H2N3 = 0.88 (1) Å. The displacement parameters of the primary amine H atoms were constrained to Uiso(H) = 1.2Ueq(N). The positional parameters of atoms H1O1 and H1O3 were also restrained, with O1—H1O1 = O3—H1O3 = 0.84 (1) Å. The methyl­ene H atoms bound to C4, C5 and C6 were constrained with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(Cmethyl­ene). For C1, Uiso(H1C1) = 1.2Ueq(C1), while the positional parameters of H1C1 were refined freely. For the hydroxyl H atoms, Uiso(H) = 1.5Ueq(O), while the positional parameters of these H atoms were refined freely.

For (IV), the positional parameters of the primary amine H atoms were refined with distance restraints N3—H1N3 = N3—H2N3 = 0.88 (1) Å. The displacement parameters of the primary amine H atoms were constrained to Uiso(H) = 1.2Ueq(N). The methyl­ene H atoms bound to C4, C5, C6 and C7 were constrained with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(Cmethyl­ene). Atom H1C1 was constrained with Uiso(H1C1) = 1.2Ueq(C1). For the hydroxyl H atoms, Uiso(H) = 1.5Ueq(O), while the positional parameters of these H atoms were refined freely.

Results and discussion top

Compounds (I)–(IV) (Figs. 1–4) were prepared from solutions of 2-amino-1,3,4-thia­diazole and di­carb­oxy­lic acids (oxalic, succinic, glutaric and adipic acids) in the molar ratio 1:1 (Table 1). (It is inter­esting that an aqueous solution of 2-amino-1,3,4-thia­diazole and malonic acid in a 1:1 molar ratio did not yield crystals; instead, the solution turned into a gel-like substance. It is also of inter­est that the solution of 2-amino-1,3,4-thia­diazole and succinic acid in a 1:1 molar ratio yielded crystals with a molar ratio of 1:2.)

In all four structures except for (I), the carboxyl group is present in two configurations, which can be distinguished by the C—C—O—H torsion angles (Table 3). A C—C—O—H torsion angle of about 0° indicates a configuration of the H atom which is quite rare in di­carb­oxy­lic acids, in contrast with the configuration with a value of about |180|° [Cambridge Structural Database (CSD), Version 5.25 with updates from November 2013 and February 2014; Allen, 2002]. For example, in the searched hydrogen oxalate structures there are only 30 cases from 622 hits with this torsion angle \sim 0°. For hydrogen succinate structures this ratio is 104/2025. An overview of the torsion angles present in the title structures is given in Table 3.

There are non-bonding S···O inter­actions present in all four structures and an overview of these is given in Table 4. The quality of the diffraction data from the title structures reveals details of the electron-density distributions [Fig. 5 for (I); the other structures yielded similar figures]. In all four structures there are lone pairs belonging to atoms N1 and N2, accumulations of electron density between the non-H atoms in the molecules and a decrease in the electron density in the vicinity of S along the S···O vector. In the cases where there are two S···O contacts in the structure, the one with the hydroxyl group involved is shorter (Table 4).

In the following, the hydrogen-bonding pattern of each of the structures will be described.

2-Amino-1,3,4-thia­diazo­lium hydrogen oxalate, (I) top

The product of crystallization with oxalic acid differs from the rest of the structures because one of the acid H atoms is tranferred to N2 (Fig. 1). This transfer of the H atom is in agreement with the higher acidity of oxalic acid compared with other di­carb­oxy­lic acids [pKa(oxalic) = 1.25, pKa(malonic) = 2.85, pKa(succinic) = 4.21, pKa(glutaric) = 4.32 and pKa(adipic) = 4.41; CRC Handbook of Chemistry and Physics, 2010). It should be stressed that a search of the CSD yielded no hits with an H atom attached to N1 instead of N2.

For geometric details of the hydrogen-bonding pattern in (I), see Table 5. Atoms N2 and N3 are hydrogen-bond donors to atoms O2 and O1, respectively, forming an R22(8) graph-set motif (Bernstein et al., 1995) of the second-order level (Fig. 6). (The atoms involved in this pattern are C2—H1N2···O2—C3—O1···H2N3—N3.)

This graph-set motif is complemented by another one, thus forming an overall R22(8)R22(10) motif. The second graph-set motif is centrosymmetric, situated about a crystallographic inversion centre and involving atoms O2–C3–C4–O4–H1O4–O2ii–C3ii–C4ii–O4ii–H1O4ii [symmetry code: (ii) -x, 1 - y, 1 - z]. All these hydrogen bonds are of moderate strength (Gilli & Gilli, 2009).

There are also weak hydrogen bonds present in the structure of (I), forming an R22(6) ring motif about a crystallographic inversion centre and involving atoms H1–C1–N1···H1C1i–C1i–N1i [symmetry code: (i) 1 - x, -y, 1 - z] (Fig. 6).

It is also of inter­est that the primary amine group is inclined with respect to the non-H atoms of the 2-amino-1,3,4-thia­diazo­lium ring by 3.6 (8)°, due to the action of the hydrogen bonds, while its planar configuration including atom C2 is conserved, in agreement with the C2—N3 bond length of 1.3136 (13) Å.

There are two non-bonding S···O inter­actions in the structure (Table 4). Such inter­actions are present in all four title structures, but they are shortest in (I).

2-Amino-1,3,4-thia­diazole bis­(succinic acid), (II) top

This structure contains two independent molecules of succinic acid and one molecule of 2-amino-1,3,4-thia­diazole, so it differs from the other compounds in the ratio of acid and base. Each of the succinic acid molecules is situated on a crystallographic centre of symmetry. However, the acid molecules differ in their configuration of the hydroxyl H atoms, as manifest by the pertinent torsion angles (Table 3).

Due to its different composition, the hydrogen-bonding pattern of (II) (Table 6) also differs from the other compounds in the absence of the R22(8) graph-set motif, which in the other structures links the primary amine group and imine N atoms with the carboxyl or carboxyl­ate groups by a pair of hydrogen bonds.

In (II), there are N—H···O and O—H···N hydrogen bonds present, but not O—H···O hydrogen bonds, i. e. the succinic acid molecules are not linked directly (Fig. 7)

The hydrogen-bonding pattern for the succinic acid molecule consisting of atoms O1(O2–H1O2)–C3–C4 is complicated. The node is the primary amine group with atom N3, which donates each of its H atoms to two different atoms O1. Two chain graph-set motifs involving this O atom can be discerned in the structure: N3—H1N3···O1···H2N3i [C12(4); symmetry code: (i) 1 - x, -1/2 + y, 1/2 - z] and O1viii—C4viii—O2viii—H1O2viii···N2ix—C2ix—N3ix—H2N3ix··· [C22(8); symmetry codes: (viii) x, -1 + y, z; (ix) x, 1/2 - y, 1/2 + z].

The hydrogen-bonding pattern for the molecule of succinic acid consisting of atoms O4(O3–H1O3)–C3–C4 is much simpler. It forms a discrete centrosymmetric motif [D22(10), i.e. involving atoms N1i···H1O3ii–O3ii–C6ii–C5ii–C5xii–C6xii–O3xii–H1O3xii···N1xiii [symmetry codes: (i) 1 - x, -1/2 + y, 1/2 - z; (ii) 1 - x, 1/2 + y, 1/2 - z; (xii) 1 + x, 3/2 - y, 1/2 + z; (xiii) 1 + x, 5/2 - y, 1/2 + z]. Moreover, atom O4xi forms a non-bonding contact to atom S1 [symmetry code: (xi) -x, 1/2 + y, 1/2 - z].

Table 4 lists two non-bonding S···O inter­actions. As in the other structures, the non-bonding S···O inter­action with the O atom pertinent to the hydroxyl group is shorter than that with the oxo-group (Table 4).

2-Amino-1,3,4-thia­diazole glutaric acid, (III) top

The most important structural motif for (III) is R22(8), which links atoms C3–O1–H1O1···N2–C2–N3–H1N3···O2 (Fig. 8, Table 7). Quite inter­esting is the inter­action N3(H1N3/H2N3)···O1 [C12(4)], with a three-centred hydrogen bond. This motif can be extended to C2–N3(H1N3/H2N3)···O1–H1O1···N2 [C23(7)]. Atom S1 is linked by non-bonding inter­actions to atoms O3 and O4. A different mutual inclination of the molecules of (III), which are nearly planar (provided that the methyl­ene H atoms are ignored [Maximum or r.m.s. deviation as evidence of this?]), enables the formation of a three-dimensional structure. Atom H2N3 is donated to atom O4, being involved in O3–H1O3···N1–N2–C2–N3–H2N3···O4–C7 [C22(9)]. There are two non-bonding S···O inter­actions in the structure (Table 4).

2-Amino-1,3,4-thia­diazole adipic acid, (IV) top

Again, there is an R22(8) motif present (Fig. 9, Table 8) between one of the carboxyl groups and the primary amine (N3) and imine (N1) atoms in the C3–O1–H1O1···N2–C2–N3–H1N3···O2 fragment. However, the packing of (IV) is different, which results in a layer-like structure and a graph-set motif O1ii–H1O1ii···N2ii–N1ii···H1O3i–O3i–C8i–C7i–C6i–C5i–C4i–C3i–O2i···H1N3i–N3i–H2N3i···O4ii–C8ii–C7ii–C6ii–C5ii–C4ii–C3ii··· [R44(23); symmetry codes: (i) 1 - x, -1/2 + y, 1/2 - z; (ii) x, -1 + y, z). A motif C3–O2···H1N3–N3–H2N3···O4i–C8i–C7i–C6i–C5i–C4i–C3i–O1i–H1O1i···N2i–N1i···H1O3–O3–C8–C7–C6–C5–C4··· [R44(23)] is attached to the previous one. There is a non-bonding S1iii···O3 inter­action in the structure [symmetry code: (iii) -1 + x, y, 1 + z].

Summary top

It is of inter­est that the four title structures show such a diversity in both their hydrogen-bonding patterns and their packings, despite the close similarity of the constituent molecules. It is also of inter­est that the crystals of the 2-amino-1,3,4-thia­diazole–malonic acid analogue could not be prepared.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Boulanger & Zyss (2003); Gilli & Gilli (2009); Matulková & Němec (2014); Matulková et al. (2007, 2008, 2012, 2013); Matulková, Císařová & Němec (2011); Matulková, Cihelka, Němec, Pojarová & Dušek (2011); Matulková, Cihelka, Pojarová, Fejfarová, Dušek, Císařová, Vaněk, Kroupa, Němec, Tesařová & Němec (2014); Matulková, Němec, Cihelka, Pojarová & Dušek (2011).

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SIR97 (Altomare et al., 1999). Program(s) used to refine structure: JANA2006 (Petříček et al., 2014) for (I), (III), (IV); JANA2006 (Petříček et al., 2006) for (II). For all compounds, molecular graphics: DIAMOND (Brandenburg & Putz, 2005), PLATON (Spek, 2009) and JANA2006 (Petříček et al., 2014); software used to prepare material for publication: JANA2006 (Petříček et al., 2014).

Figures top
[Figure 1] Fig. 1. The two ions of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate N—H···O hydrogen bonds.
[Figure 2] Fig. 2. The three component molecules of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are generated by symmetry. [It would help the reader if at least the first of these were shown for each succinic acid molecule, with symmetry codes indicated and given in the caption]
[Figure 3] Fig. 3. The two molecules of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate N—H···O hydrogen bonds.
[Figure 4] Fig. 4. The two molecules of (IV), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate N—H···O hydrogen bonds.
[Figure 5] Fig. 5. A section of the difference electron-density map for (I). Positive and negative electron densities are indicated by continuous and dashed lines, respectively. The increment is 0.05 e Å-3. C atoms are indicated by grey spheres, H by light grey, N by green, O by red and S by yellow.
[Figure 6] Fig. 6. Detail of the hydrogen-bonding (purple dashed lines) and S···O (orange dashed lines) patterns in (I) . [Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) x, 1 - y, 1 - z; (iii) 1 + x, -1 + y, z.]
[Figure 7] Fig. 7. Detail of the hydrogen-bonding (purple dashed lines) and S···O (orange dashed lines) patterns in (II). [Symmetry codes: (i) x, -y+3/2, z+1/2; (ii) x, y-1, z; (iii) -x+1, y-1/2, -z+1/2; (iv) -x, y+1/2, -z+1/2; (v) -x+1, y+1/2, -z+1/2; (vi) x, y+1, z; (vii) -x+1, -y+1, -z+1; (viii) -x+1, y+3/2, -z+1/2 (ix) x+1, -y+3/2, z+1/2; (x) x, -y+1/2, z+1/2; (xi) -x+1, y-3/2, -z+1/2; (xii) x, -y+3/2, z-1/2.]
[Figure 8] Fig. 8. Detail of the hydrogen-bonding (purple dashed lines) and S···O (orange dashed lines) patterns in (III). [Symmetry codes: (i) -x+1/2, y+1/2, z; (ii) x-1/2, -y+3/2, -z+1; (iii) x+1/2, -y+1/2, -z+1; (iv) -x+1/2, y-1/2, z; (v) -x+1, -y+1, -z+1; (vi) x-1/2, -y+1/2, -z+1; (vii) -x, y-1/2, -z+3/2; (viii) -x+1/2, -y+1, z+1/2.]
[Figure 9] Fig. 9. Detail of the hydrogen-bonding (purple dashed lines) and S···O (orange dashed lines) patterns in (IV). [Symmetry codes: (i) -x+1, y-1/2, -z+1/2; (ii) x, y-1, z; (iii) x-1, y, z+1; (iv) Please complete.] [Please also provide a revised plot with no labels overlapping atoms or bonds. Symmetry codes should ideally be superscript, with no parentheses.]
(I) 2-amino-1,3,4-thiadiazolium hydrogen oxalate top
Crystal data top
C2H4N3S+·C2HO4F(000) = 392
Mr = 191.2Dx = 1.813 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4550 reflections
a = 3.6848 (1) Åθ = 3.0–30.0°
b = 10.0617 (2) ŵ = 0.44 mm1
c = 18.9595 (4) ÅT = 150 K
β = 94.982 (1)°Prism, colourless
V = 700.27 (3) Å30.56 × 0.35 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2031 independent reflections
Radiation source: X-ray tube1856 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.019
φ and ω scansθmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 54
Tmin = 0.790, Tmax = 0.911k = 1413
6984 measured reflectionsl = 2526
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.023Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.067(Δ/σ)max = 0.026
S = 2.13Δρmax = 0.35 e Å3
2031 reflectionsΔρmin = 0.19 e Å3
125 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
2 restraintsExtinction coefficient: 2800 (500)
5 constraints
Crystal data top
C2H4N3S+·C2HO4V = 700.27 (3) Å3
Mr = 191.2Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.6848 (1) ŵ = 0.44 mm1
b = 10.0617 (2) ÅT = 150 K
c = 18.9595 (4) Å0.56 × 0.35 × 0.22 mm
β = 94.982 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2031 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1856 reflections with I > 3σ(I)
Tmin = 0.790, Tmax = 0.911Rint = 0.019
6984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0232 restraints
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 2.13Δρmax = 0.35 e Å3
2031 reflectionsΔρmin = 0.19 e Å3
125 parameters
Special details top

Refinement. The diffractions for which |Io - Ic|/w > 15 have been discarded from the refinement. The diffractions with θ < 3° which could have been affected by shadowing by the beam-stop were excluded from the refinement as well.

The condition for exclusion of the diffractions for which |Io - Ic|/w > 15.

The following diffractions have been from the refinement: h k l Io σ(Io) observed/unobserved 1 2 0 25.56 0.51 o 0 3 1 53.44 0.63 o -2 0 2 65.31 1.27 o 0 0 2 -6.33 0.25 u 0 2 2 -0.13 0.13 u 0 5 5 33.66 0.63 o 0 5 9 51.13 1.14 o

Indicators of the refinement with these diffractions included into the refinement: _refine_ls_R_factor_gt 0.0238 _refine_ls_wR_factor_gt 0.0724 _refine_ls_R_factor_all 0.0267 _refine_ls_wR_factor_ref 0.0763 _refine_ls_goodness_of_fit_ref 2.41 _refine_ls_goodness_of_fit_gt 2.40

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.79484 (6)0.02922 (2)0.329515 (12)0.01298 (8)
C10.7051 (3)0.01362 (10)0.41761 (5)0.0155 (3)
H1C10.745 (3)0.0672 (13)0.4420 (7)0.0186*
N10.5730 (2)0.11718 (8)0.44587 (4)0.0165 (2)
N20.5392 (2)0.21836 (8)0.39696 (4)0.0145 (2)
H1N20.431 (3)0.2958 (13)0.4086 (7)0.0174*
C20.6399 (2)0.19124 (9)0.33261 (5)0.0127 (2)
N30.6252 (3)0.27729 (9)0.28034 (5)0.0197 (3)
H1N30.677 (3)0.2547 (13)0.2384 (5)0.0237*
H2N30.551 (3)0.3591 (9)0.2888 (7)0.0237*
O10.3875 (2)0.52836 (7)0.32709 (4)0.0186 (2)
O20.2010 (2)0.45203 (7)0.42940 (4)0.0179 (2)
C30.2331 (3)0.53837 (9)0.38231 (5)0.0133 (2)
C40.0620 (3)0.67582 (9)0.39569 (5)0.0139 (2)
O30.0809 (2)0.76780 (7)0.35515 (4)0.0209 (2)
O40.1070 (2)0.68824 (7)0.45397 (4)0.0182 (2)
H1O40.098 (3)0.6206 (14)0.4768 (7)0.0273*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01612 (13)0.01060 (13)0.01255 (13)0.00296 (8)0.00317 (9)0.00073 (7)
C10.0199 (5)0.0138 (4)0.0131 (4)0.0017 (3)0.0030 (3)0.0014 (3)
N10.0221 (4)0.0140 (4)0.0137 (4)0.0021 (3)0.0042 (3)0.0017 (3)
N20.0199 (4)0.0108 (4)0.0133 (4)0.0025 (3)0.0049 (3)0.0002 (3)
C20.0131 (4)0.0115 (4)0.0138 (4)0.0010 (3)0.0024 (3)0.0010 (3)
N30.0315 (5)0.0138 (4)0.0148 (4)0.0073 (3)0.0079 (3)0.0021 (3)
O10.0267 (4)0.0157 (4)0.0147 (3)0.0042 (3)0.0087 (3)0.0002 (2)
O20.0269 (4)0.0125 (3)0.0155 (3)0.0054 (3)0.0080 (3)0.0025 (2)
C30.0155 (4)0.0111 (4)0.0134 (4)0.0013 (3)0.0022 (3)0.0011 (3)
C40.0173 (4)0.0122 (4)0.0126 (4)0.0018 (3)0.0034 (3)0.0008 (3)
O30.0322 (4)0.0130 (3)0.0188 (3)0.0058 (3)0.0103 (3)0.0042 (3)
O40.0286 (4)0.0122 (3)0.0152 (3)0.0056 (3)0.0098 (3)0.0027 (3)
Geometric parameters (Å, º) top
S1—C11.7377 (10)H1N3—H2N31.519 (16)
S1—C21.7300 (9)O1—C31.2382 (12)
C1—H1C10.941 (13)O2—C31.2586 (12)
C1—N11.2865 (13)C3—C41.5500 (13)
N1—N21.3755 (11)C4—O31.2089 (12)
N2—H1N20.911 (13)C4—O41.3207 (12)
N2—C21.3339 (12)O4—H1O40.805 (14)
C2—N31.3135 (12)S1—O1i2.9868 (8)
N3—H1N30.864 (10)S1—O3ii2.8595 (7)
N3—H2N30.886 (10)
S1—C1—H1C1121.1 (8)C2—N3—H2N3118.0 (8)
S1—C1—N1115.95 (7)H1N3—N3—H2N3120.4 (12)
H1C1—C1—N1122.9 (8)O1—C3—O2128.47 (9)
C1—N1—N2109.51 (8)O1—C3—C4115.73 (8)
N1—N2—H1N2119.0 (8)O2—C3—C4115.79 (8)
N1—N2—C2116.69 (8)C3—C4—O3122.16 (9)
H1N2—N2—C2124.0 (8)C3—C4—O4116.71 (8)
S1—C2—N2110.03 (7)O3—C4—O4121.13 (9)
S1—C2—N3125.99 (8)O3—C4—H1O4146.0 (5)
N2—C2—N3123.97 (9)C4—O4—H1O4111.6 (10)
C2—N3—H1N3121.6 (9)
C3—C4—O4—H1O40.9 (10)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H1O4···O20.809 (14)2.245 (14)2.6914 (10)115.2 (12)
O4—H1O4···O2iii0.809 (14)1.990 (14)2.6709 (10)141.4 (14)
N2—H1N2···O20.923 (13)1.833 (13)2.7553 (11)177.7 (11)
N3—H1N3···O1i0.867 (10)2.594 (13)3.2260 (11)130.6 (11)
N3—H1N3···O3i0.867 (10)2.055 (11)2.8745 (12)157.4 (12)
N3—H2N3···O10.888 (10)1.966 (10)2.8407 (11)168.4 (12)
C1—H1C1···O4ii0.946 (13)2.520 (13)3.4044 (12)155.6 (11)
C1—H1C1···N1iv0.946 (13)2.563 (13)3.1531 (13)120.7 (10)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y1, z; (iii) x, y+1, z+1; (iv) x+1, y, z+1.
(II) 2-Amino-1,3,4-thiadiazole–succinic acid (1/2) top
Crystal data top
C2H3N3S·2C4H6O4F(000) = 456
Mr = 337.35Dx = 2.481 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3671 reflections
a = 11.9022 (3) Åθ = 3.2–27.4°
b = 5.3284 (2) ŵ = 0.43 mm1
c = 14.3267 (4) ÅT = 150 K
β = 96.375 (1)°Prism, colourless
V = 902.98 (5) Å30.42 × 0.20 × 0.16 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2059 independent reflections
Radiation source: fine-focus sealed tube1802 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.017
φ and ω scansθmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 1515
Tmin = 0.867, Tmax = 0.945k = 66
7307 measured reflectionsl = 1818
Refinement top
Refinement on F221 constraints
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 2.23(Δ/σ)max = 0.015
2059 reflectionsΔρmax = 0.33 e Å3
142 parametersΔρmin = 0.24 e Å3
2 restraints
Crystal data top
C2H3N3S·2C4H6O4V = 902.98 (5) Å3
Mr = 337.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.9022 (3) ŵ = 0.43 mm1
b = 5.3284 (2) ÅT = 150 K
c = 14.3267 (4) Å0.42 × 0.20 × 0.16 mm
β = 96.375 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2059 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1802 reflections with I > 3σ(I)
Tmin = 0.867, Tmax = 0.945Rint = 0.017
7307 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0302 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 2.23Δρmax = 0.33 e Å3
2059 reflectionsΔρmin = 0.24 e Å3
142 parameters
Special details top

Refinement. The diffractions for which |Io - Ic|/w > 15 have been discarded from the refinement. The diffractions with θ < 3° which could have been affected by shadowing by the beam-stop were excluded from the refinement as well.

The condition for exclusion of the diffractions for which |Io - Ic|/w > 15.

The following diffraction has been removed from the refinement: h k l Io σ(Io) observed/unobserved -3 2 3 73.50 1.24 o

Indicators of the refinement with this diffraction included into the refinement:

_refine_ls_R_factor_gt 0.0303 _refine_ls_wR_factor_gt 0.0795 _refine_ls_R_factor_all 0.0353 _refine_ls_wR_factor_ref 0.0822 _refine_ls_goodness_of_fit_ref 2.26 _refine_ls_goodness_of_fit_gt 2.35

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.21112 (3)0.42956 (7)0.31351 (3)0.02313 (13)
C10.16065 (12)0.6838 (3)0.24681 (11)0.0235 (5)
H1C10.0986 (12)0.783 (3)0.2648 (11)0.0282*
N10.21467 (9)0.7284 (2)0.17521 (8)0.0207 (4)
N20.30255 (9)0.5626 (2)0.16689 (8)0.0179 (4)
C20.31147 (11)0.3944 (3)0.23516 (9)0.0172 (4)
N30.39064 (11)0.2166 (2)0.24449 (9)0.0250 (4)
H1N30.3916 (13)0.095 (2)0.2880 (9)0.03*
H2N30.4434 (11)0.218 (3)0.2049 (9)0.03*
C30.45445 (10)0.5775 (2)0.51965 (9)0.0154 (4)
H1C30.3898450.4678650.5300560.0185*
H2C30.4838160.6432390.5822630.0185*
C40.41353 (10)0.7917 (3)0.45670 (9)0.0141 (4)
O10.43435 (7)0.80915 (19)0.37551 (6)0.0188 (3)
O20.35066 (8)0.96516 (19)0.49118 (7)0.0187 (3)
H1O20.3419 (13)0.947 (3)0.5536 (12)0.028*
C50.04858 (10)0.4182 (3)0.01168 (10)0.0188 (4)
H1C50.1157050.5242760.0176120.0226*
H2C50.0289610.3394860.0739560.0226*
C60.07850 (11)0.2177 (3)0.06046 (10)0.0173 (4)
O30.16923 (9)0.0877 (2)0.04430 (8)0.0272 (4)
H1O30.1828 (14)0.030 (3)0.0871 (13)0.0408*
O40.02640 (9)0.1755 (2)0.12657 (8)0.0314 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0244 (2)0.0282 (2)0.0179 (2)0.00497 (16)0.00756 (14)0.00321 (15)
C10.0228 (7)0.0245 (9)0.0240 (8)0.0012 (6)0.0061 (6)0.0008 (6)
N10.0206 (6)0.0187 (7)0.0232 (7)0.0033 (5)0.0047 (5)0.0023 (5)
N20.0207 (6)0.0161 (7)0.0174 (6)0.0012 (5)0.0046 (5)0.0036 (5)
C20.0179 (6)0.0185 (8)0.0152 (7)0.0040 (6)0.0013 (5)0.0009 (6)
N30.0280 (7)0.0231 (7)0.0253 (7)0.0045 (6)0.0089 (5)0.0099 (6)
C30.0187 (6)0.0145 (7)0.0134 (7)0.0013 (5)0.0036 (5)0.0019 (5)
C40.0121 (6)0.0126 (7)0.0173 (7)0.0033 (5)0.0009 (5)0.0006 (5)
O10.0227 (5)0.0198 (6)0.0145 (5)0.0028 (4)0.0045 (4)0.0034 (4)
O20.0231 (5)0.0167 (5)0.0169 (5)0.0051 (4)0.0051 (4)0.0004 (4)
C50.0182 (6)0.0186 (8)0.0198 (7)0.0026 (6)0.0033 (5)0.0009 (6)
C60.0157 (6)0.0166 (8)0.0195 (7)0.0012 (6)0.0018 (5)0.0013 (6)
O30.0275 (5)0.0270 (7)0.0288 (6)0.0131 (5)0.0108 (5)0.0105 (5)
O40.0315 (6)0.0334 (7)0.0321 (7)0.0118 (5)0.0157 (5)0.0126 (5)
Geometric parameters (Å, º) top
S1—C11.7266 (16)H1C3—H2C31.5805
S1—C21.7376 (14)C4—O11.2194 (16)
C1—H1C10.966 (16)C4—O21.3192 (17)
C1—N11.292 (2)O2—H1O20.917 (17)
N1—N21.3843 (16)C5—C5ii1.5152 (19)
N2—C21.3220 (18)C5—H1C50.99
C2—N31.3326 (19)C5—H2C50.99
N3—H1N30.900 (13)C5—C61.5013 (19)
N3—H2N30.892 (14)H1C5—H2C51.5818
H1N3—H2N31.55 (2)C6—O31.3248 (17)
C3—C3i1.5198 (18)C6—O41.2094 (18)
C3—H1C30.99O3—H1O30.880 (18)
C3—H2C30.99S1—O3iii3.3995 (12)
C3—C41.5021 (18)S1—O4iv3.3145 (12)
S1—C1—H1C1120.7 (10)H1C3—C3—C4109.47
S1—C1—N1114.25 (11)H2C3—C3—C4109.47
H1C1—C1—N1125.0 (10)C3—C4—O1122.95 (12)
C1—N1—N2113.47 (12)C3—C4—O2117.85 (12)
N1—N2—C2111.61 (12)O1—C4—O2119.19 (12)
N1—N2—H1O2v112.5 (5)C4—O2—H1O2114.9 (10)
C2—N2—H1O2v131.5 (5)N2vi—H1o2—O2170.0 (15)
S1—C2—N2113.60 (10)C5ii—C5—H1C5109.47
S1—C2—N3122.74 (11)C5ii—C5—H2C5109.47
N2—C2—N3123.65 (13)C5ii—C5—C6112.69 (12)
C2—N3—H1N3122.5 (10)H1C5—C5—H2C5106.04
C2—N3—H2N3118.0 (10)H1C5—C5—C6109.47
H1N3—N3—H2N3119.6 (14)H2C5—C5—C6109.47
C3i—C3—H1C3109.47C5—C6—O3112.79 (12)
C3i—C3—H2C3109.47C5—C6—O4124.64 (12)
C3i—C3—C4112.80 (11)O3—C6—O4122.57 (13)
H1C3—C3—H2C3105.92C6—O3—H1O3109.9 (12)
C5—C6—O3—H1O3178.5 (12)C3—C4—O2—H1o24.9 (11)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z; (iii) x, y+1/2, z+1/2; (iv) x, y+1/2, z+1/2; (v) x, y+3/2, z1/2; (vi) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O2···N2vi0.909 (17)1.747 (17)2.6470 (16)170.1 (15)
O3—H1O3···N1vii0.873 (18)1.820 (18)2.6926 (16)178.4 (17)
N3—H1N3···O1vii0.900 (13)2.001 (13)2.8794 (16)164.9 (14)
N3—H2N3···O1viii0.893 (14)2.012 (14)2.8869 (17)166.1 (15)
C1—H1C1···O4iv0.965 (16)2.340 (16)3.0243 (19)127.3 (12)
Symmetry codes: (iv) x, y+1/2, z+1/2; (vi) x, y+3/2, z+1/2; (vii) x, y1, z; (viii) x+1, y1/2, z+1/2.
(III) 2-Amino-1,3,4-thiadiazole–glutaric acid (1/1) top
Crystal data top
C2H3N3S·C5H8O4F(000) = 976
Mr = 233.2Dx = 1.550 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3659 reflections
a = 7.1620 (2) Åθ = 2.9–27.4°
b = 10.0096 (2) ŵ = 0.32 mm1
c = 27.8847 (7) ÅT = 150 K
V = 1999.02 (9) Å3Prism, colourless
Z = 80.42 × 0.16 × 0.14 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2295 independent reflections
Radiation source: fine-focus sealed tube1881 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 98
Tmin = 0.876, Tmax = 0.957k = 1212
9941 measured reflectionsl = 1836
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.028Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.067(Δ/σ)max = 0.042
S = 1.66Δρmax = 0.23 e Å3
2295 reflectionsΔρmin = 0.22 e Å3
152 parametersExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
4 restraintsExtinction coefficient: 2400 (500)
29 constraints
Crystal data top
C2H3N3S·C5H8O4V = 1999.02 (9) Å3
Mr = 233.2Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.1620 (2) ŵ = 0.32 mm1
b = 10.0096 (2) ÅT = 150 K
c = 27.8847 (7) Å0.42 × 0.16 × 0.14 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2295 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1881 reflections with I > 3σ(I)
Tmin = 0.876, Tmax = 0.957Rint = 0.025
9941 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0284 restraints
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.66Δρmax = 0.23 e Å3
2295 reflectionsΔρmin = 0.22 e Å3
152 parameters
Special details top

Refinement. The diffractions for which |Io - Ic|/w > 15 have been discarded from the refinement. The diffractions with θ < 3° which could have been affected by shadowing by the beam-stop were excluded from the refinement as well.

The condition for exclusion of the diffractions for which |Io - Ic|/w > 15.

The following diffraction has been from the refinement: h k l Io σ(Io) observed/unobserved 0 0 2 289.46 5.13 o

Indicators of the refinement with this diffraction included into the refinement:

_refine_ls_R_factor_gt 0.0277 _refine_ls_wR_factor_gt 0.0673 _refine_ls_R_factor_all 0.0363 _refine_ls_wR_factor_ref 0.0701 _refine_ls_goodness_of_fit_ref 1.73 _refine_ls_goodness_of_fit_gt 1.85

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.01814 (5)0.62369 (3)0.706072 (12)0.02054 (10)
C10.0041 (2)0.45455 (13)0.71681 (5)0.0219 (4)
H1c10.021 (2)0.4166 (16)0.7463 (6)0.0263*
N10.05342 (16)0.38491 (11)0.68001 (4)0.0203 (3)
N20.07899 (16)0.46137 (10)0.63913 (4)0.0179 (3)
C20.04678 (17)0.58919 (12)0.64731 (5)0.0167 (4)
N30.06418 (18)0.68320 (11)0.61380 (4)0.0228 (4)
H1n30.1059 (19)0.6610 (14)0.5853 (4)0.0273*
H2n30.0391 (19)0.7658 (9)0.6201 (6)0.0273*
O10.19448 (14)0.35803 (9)0.55517 (4)0.0243 (3)
H1o10.156 (2)0.3957 (14)0.5805 (4)0.0365*
O20.19376 (13)0.56229 (9)0.52272 (4)0.0236 (3)
C30.22331 (17)0.44300 (13)0.51953 (5)0.0164 (4)
C40.29937 (18)0.37397 (12)0.47607 (5)0.0197 (4)
H1c40.4160130.3265330.484620.0236*
H2c40.2149570.2999910.4668390.0236*
C50.33436 (17)0.46313 (12)0.43282 (5)0.0166 (4)
H1c50.2144940.5012560.421630.02*
H2c50.4200730.536440.4419480.02*
C60.42163 (18)0.38131 (12)0.39283 (5)0.0177 (4)
H1c60.5358890.3368890.4048730.0212*
H2c60.3397440.3045410.3851650.0212*
C70.46625 (17)0.45629 (12)0.34767 (5)0.0166 (4)
O30.54004 (13)0.38516 (9)0.31209 (4)0.0201 (3)
H1o30.543 (2)0.3021 (9)0.3172 (6)0.0302*
O40.44135 (14)0.57526 (9)0.34197 (4)0.0232 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.03127 (19)0.01649 (17)0.01386 (18)0.00020 (13)0.00432 (14)0.00241 (14)
C10.0335 (8)0.0182 (7)0.0140 (7)0.0009 (5)0.0013 (6)0.0011 (6)
N10.0299 (6)0.0182 (5)0.0127 (6)0.0001 (5)0.0003 (5)0.0008 (5)
N20.0265 (6)0.0151 (5)0.0120 (6)0.0003 (4)0.0009 (5)0.0010 (5)
C20.0185 (6)0.0185 (6)0.0131 (7)0.0005 (5)0.0006 (5)0.0022 (5)
N30.0364 (7)0.0154 (5)0.0166 (6)0.0007 (5)0.0070 (5)0.0001 (5)
O10.0424 (6)0.0166 (5)0.0141 (5)0.0059 (4)0.0082 (4)0.0021 (4)
O20.0380 (6)0.0145 (5)0.0182 (5)0.0018 (4)0.0050 (5)0.0004 (4)
C30.0181 (6)0.0179 (6)0.0131 (7)0.0001 (5)0.0018 (5)0.0012 (5)
C40.0285 (7)0.0155 (6)0.0151 (7)0.0028 (5)0.0027 (6)0.0001 (6)
C50.0212 (6)0.0162 (6)0.0125 (7)0.0010 (5)0.0001 (5)0.0003 (5)
C60.0235 (6)0.0162 (6)0.0134 (7)0.0021 (5)0.0010 (5)0.0014 (5)
C70.0190 (6)0.0172 (6)0.0135 (7)0.0024 (5)0.0034 (6)0.0014 (5)
O30.0319 (5)0.0149 (4)0.0135 (5)0.0002 (4)0.0028 (4)0.0004 (4)
O40.0368 (6)0.0140 (5)0.0188 (5)0.0009 (4)0.0008 (5)0.0012 (4)
Geometric parameters (Å, º) top
S1—C11.7266 (14)C4—H1c40.99
S1—C21.7379 (14)C4—H2c40.99
C1—H1c10.923 (17)C4—C51.5210 (18)
C1—N11.2898 (18)C5—H1c50.99
N1—N21.3853 (16)C5—H2c50.99
N2—C21.3199 (16)C5—C61.5183 (18)
C2—N31.3318 (17)C6—H1c60.99
N3—H1n30.879 (11)C6—H2c60.99
N3—H2n30.865 (10)C6—C71.5002 (18)
H1n3—H2n31.509 (18)C7—O31.3306 (16)
O1—H1o10.845 (12)C7—O41.2146 (15)
O1—C31.3243 (16)O3—H1o30.844 (9)
O2—C31.2160 (15)S1—O3i2.9619 (10)
C3—C41.4976 (18)S1—O4ii3.3105 (9)
S1—C1—H1c1122.6 (10)H1c4—C4—C5109.47
S1—C1—N1114.66 (11)H2c4—C4—C5109.47
H1c1—C1—N1122.7 (10)C4—C5—H1c5109.47
C1—N1—N2113.09 (11)C4—C5—H2c5109.47
N1—N2—C2111.73 (11)C4—C5—C6109.49 (10)
S1—C2—N2113.72 (10)H1c5—C5—H2c5109.45
S1—C2—N3123.10 (10)H1c5—C5—C6109.47
N2—C2—N3123.18 (12)H2c5—C5—C6109.47
C2—N3—H1n3119.2 (9)C5—C6—H1c6109.47
C2—N3—H2n3120.9 (10)C5—C6—H2c6109.47
H1n3—N3—H2n3119.9 (14)C5—C6—C7115.74 (10)
H1o1—O1—C3112.9 (9)H1c6—C6—H2c6102.37
O1—C3—O2123.28 (12)H1c6—C6—C7109.47
O1—C3—C4111.58 (11)H2c6—C6—C7109.47
O2—C3—C4125.14 (12)C6—C7—O3116.28 (10)
C3—C4—H1c4109.47C6—C7—O4124.69 (12)
C3—C4—H2c4109.47O3—C7—O4119.03 (12)
C3—C4—C5115.52 (10)C7—O3—H1o3114.4 (10)
H1c4—C4—H2c4102.66
C4—C3—O1—H1O1177.3 (11)C6—C7—O3—H1O36.8 (11)
Symmetry codes: (i) x+1/2, y+1, z+1/2; (ii) x1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O1iii0.88 (1)2.58 (1)2.9535 (15)107 (1)
N3—H2N3···O1iii0.87 (1)2.79 (1)2.9535 (15)92 (1)
N3—H1N3···O20.88 (1)2.10 (1)2.9627 (16)167 (1)
N3—H2N3···O4ii0.87 (1)2.03 (1)2.8531 (15)158 (1)
O1—H1O1···N20.85 (1)1.85 (1)2.6898 (15)174 (1)
O3—H1O3···N1iv0.84 (1)1.88 (1)2.7139 (14)173 (2)
O3—H1O3···N2iv0.84 (1)2.92 (1)3.7362 (14)165 (1)
C6—H1C6···O1iv0.992.523.4148 (16)151
Symmetry codes: (ii) x1/2, y+3/2, z+1; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+1/2, z+1.
(IV) 2-amino-1,3,4-thiadiazole–adipic acid (1/1) top
Crystal data top
C2H3N3S·C6H10O4F(000) = 520
Mr = 247.3Dx = 1.504 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4518 reflections
a = 11.1790 (2) Åθ = 2.7–30.0°
b = 10.2187 (2) ŵ = 0.30 mm1
c = 9.6532 (2) ÅT = 150 K
β = 98.116 (1)°Prism, colourless
V = 1091.69 (4) Å30.36 × 0.31 × 0.23 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3182 independent reflections
Radiation source: fine-focus sealed tube2616 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.020
φ and ω scansθmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
h = 1215
Tmin = 0.900, Tmax = 0.933k = 1414
10441 measured reflectionsl = 1310
Refinement top
Refinement on F237 constraints
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 1.88(Δ/σ)max = 0.022
3182 reflectionsΔρmax = 0.30 e Å3
160 parametersΔρmin = 0.21 e Å3
2 restraints
Crystal data top
C2H3N3S·C6H10O4V = 1091.69 (4) Å3
Mr = 247.3Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.1790 (2) ŵ = 0.30 mm1
b = 10.2187 (2) ÅT = 150 K
c = 9.6532 (2) Å0.36 × 0.31 × 0.23 mm
β = 98.116 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3182 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
2616 reflections with I > 3σ(I)
Tmin = 0.900, Tmax = 0.933Rint = 0.020
10441 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0292 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.88Δρmax = 0.30 e Å3
3182 reflectionsΔρmin = 0.21 e Å3
160 parameters
Special details top

Refinement. The diffractions for which |Io - Ic|/w > 15 have been discarded from the refinement. The diffractions with θ < 3° which could have been affected by shadowing by the beam-stop were excluded from the refinement as well.

The condition for exclusion of the diffractions for which |Io - Ic|/w > 15. The following diffraction has been removed from the refinement: h k l Io σ(Io) observed/unobserved -3 3 2 297.44 3.31 o

Indicators of the refinement with this diffraction included into the refinement:

_refine_ls_R_factor_gt 0.0292 _refine_ls_wR_factor_gt 0.0738 _refine_ls_R_factor_all 0.0380 _refine_ls_wR_factor_ref 0.0763 _refine_ls_goodness_of_fit_ref 1.90 _refine_ls_goodness_of_fit_gt 2.04

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.92798 (2)0.58212 (3)0.16637 (3)0.01828 (8)
C10.93970 (10)0.74918 (11)0.18192 (12)0.0189 (3)
H1c10.9901 (11)0.7888 (13)0.2422 (14)0.0227*
N10.87422 (8)0.81559 (9)0.10641 (10)0.0189 (3)
N20.80693 (8)0.73784 (9)0.02887 (10)0.0176 (3)
C20.82499 (9)0.61224 (11)0.05088 (12)0.0167 (3)
N30.77004 (9)0.51588 (10)0.00746 (12)0.0267 (3)
H1n30.7232 (10)0.5383 (13)0.0692 (11)0.032*
H2n30.7877 (12)0.4339 (9)0.0117 (14)0.032*
O10.64820 (7)0.82007 (8)0.14962 (9)0.0221 (3)
H1o10.6971 (13)0.7895 (13)0.0965 (15)0.0331*
O20.61559 (8)0.60863 (8)0.19340 (10)0.0314 (3)
C30.59450 (9)0.72358 (11)0.20916 (12)0.0186 (3)
C40.50333 (9)0.77157 (11)0.29840 (11)0.0179 (3)
H1c40.4492270.8362980.2451090.0215*
H2c40.5454060.8197730.3800260.0215*
C50.42806 (9)0.66197 (11)0.34890 (12)0.0191 (3)
H1c50.4816040.6008670.408310.0229*
H2c50.3885880.6115490.2674670.0229*
C60.33238 (9)0.71488 (11)0.43140 (12)0.0170 (3)
H1c60.3712520.7709030.5085750.0204*
H2c60.2768960.7732580.3708270.0204*
C70.25987 (9)0.60774 (11)0.49075 (11)0.0185 (3)
H1c70.2178820.5542750.4131970.0223*
H2c70.3157030.5463570.5467690.0223*
C80.16922 (9)0.65874 (10)0.57891 (12)0.0170 (3)
O30.10549 (8)0.57162 (8)0.63762 (10)0.0265 (3)
H1o30.1194 (12)0.4948 (14)0.6180 (14)0.0397*
O40.15287 (7)0.77487 (8)0.59926 (9)0.0228 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02002 (13)0.01443 (15)0.02273 (15)0.00142 (10)0.01118 (10)0.00105 (11)
C10.0200 (5)0.0158 (6)0.0222 (6)0.0013 (4)0.0078 (4)0.0008 (5)
N10.0211 (4)0.0146 (5)0.0224 (5)0.0013 (4)0.0082 (4)0.0001 (4)
N20.0211 (4)0.0127 (5)0.0211 (5)0.0005 (3)0.0098 (4)0.0003 (4)
C20.0175 (5)0.0158 (5)0.0181 (5)0.0019 (4)0.0073 (4)0.0001 (4)
N30.0347 (5)0.0128 (5)0.0385 (6)0.0016 (4)0.0257 (5)0.0004 (5)
O10.0251 (4)0.0187 (4)0.0257 (5)0.0002 (3)0.0147 (3)0.0011 (4)
O20.0383 (5)0.0161 (4)0.0464 (6)0.0008 (4)0.0291 (4)0.0026 (4)
C30.0176 (5)0.0196 (6)0.0196 (5)0.0009 (4)0.0066 (4)0.0007 (5)
C40.0185 (5)0.0171 (6)0.0198 (5)0.0003 (4)0.0086 (4)0.0016 (5)
C50.0197 (5)0.0166 (6)0.0234 (6)0.0009 (4)0.0115 (4)0.0011 (5)
C60.0183 (5)0.0152 (5)0.0192 (5)0.0003 (4)0.0083 (4)0.0001 (4)
C70.0205 (5)0.0160 (6)0.0211 (6)0.0001 (4)0.0096 (4)0.0022 (5)
C80.0183 (5)0.0153 (5)0.0184 (5)0.0003 (4)0.0067 (4)0.0000 (5)
O30.0350 (4)0.0117 (4)0.0384 (5)0.0003 (3)0.0250 (4)0.0012 (4)
O40.0283 (4)0.0125 (4)0.0308 (5)0.0003 (3)0.0156 (3)0.0005 (4)
Geometric parameters (Å, º) top
S1—C11.7203 (12)C5—H1c50.99
S1—C21.7394 (12)C5—H2c50.99
C1—H1c10.955 (14)C5—C61.5203 (16)
C1—N11.2956 (15)H1c5—H2c51.5945
N1—N21.3843 (14)C6—H1c60.99
N2—C21.3211 (14)C6—H2c60.99
C2—N31.3273 (16)C6—C71.5215 (16)
N3—H1n30.878 (12)H1c6—H2c61.5765
N3—H2n30.886 (10)C7—H1c70.99
H1n3—H2n31.558 (17)C7—H2c70.99
O1—H1o10.859 (15)C7—C81.5055 (16)
O1—C31.3268 (14)H1c7—H2c71.5706
O2—C31.2119 (14)C8—O31.3173 (14)
C3—C41.5064 (16)C8—O41.2208 (13)
C4—H1c40.99O3—H1o30.827 (14)
C4—H2c40.99S1—O3i2.9308 (10)
C4—C51.5217 (16)S1—O4ii3.3556 (8)
H1c4—H2c41.5765
S1—C1—H1c1122.2 (8)C4—C5—H2c5109.47
S1—C1—N1114.49 (9)C4—C5—C6111.58 (9)
H1c1—C1—N1123.3 (8)H1c5—C5—H2c5107.28
C1—N1—N2113.39 (9)H1c5—C5—C6109.47
N1—N2—C2111.32 (9)H2c5—C5—C6109.47
S1—C2—N2113.89 (8)C5—C6—H1c6109.47
S1—C2—N3121.91 (9)C5—C6—H2c6109.47
N2—C2—N3124.20 (11)C5—C6—C7113.14 (9)
C2—N3—H1n3116.8 (9)H1c6—C6—H2c6105.54
C2—N3—H2n3118.9 (9)H1c6—C6—C7109.47
H1n3—N3—H2n3124.1 (12)H2c6—C6—C7109.47
H1o1—O1—C3110.7 (9)C6—C7—H1c7109.47
O1—C3—O2123.91 (11)C6—C7—H2c7109.47
O1—C3—C4112.95 (10)C6—C7—C8113.62 (9)
O2—C3—C4123.14 (11)H1c7—C7—H2c7104.98
C3—C4—H1c4109.47H1c7—C7—C8109.47
C3—C4—H2c4109.47H2c7—C7—C8109.47
C3—C4—C5113.14 (9)C7—C8—O3117.22 (9)
H1c4—C4—H2c4105.54C7—C8—O4123.75 (10)
H1c4—C4—C5109.47O3—C8—O4119.04 (10)
H2c4—C4—C5109.47C8—O3—H1o3114.3 (10)
C4—C5—H1c5109.47
C4—C3—O1—H1o1177.3 (9)C7—C8—O3—H1o32.2 (10)
Symmetry codes: (i) x+1, y, z1; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O20.88 (1)1.95 (1)2.8242 (15)173 (1)
N3—H2N3···O4ii0.89 (1)1.99 (1)2.8496 (13)163 (1)
O1—H1O1···N20.86 (2)1.92 (2)2.7725 (13)175 (1)
O3—H1O3···N1ii0.83 (1)1.84 (1)2.6470 (12)166 (1)
Symmetry code: (ii) x+1, y1/2, z+1/2.
Quantities of acid base (g) used for the preparation of the title structures. The base and the acid were dissolved in the given volume of water before mixing these solutions. The methanol was added in the case of solutions of succinic and adipic acids. Also given are the average sizes of the obtained crystals. top
CompoundAcid (g)/H2O (ml)/CH3OH (ml)Base (g)/H2O (ml)
(I)0.1255 g/12 ml/0 ml0.1005 g/2 ml
(II)0.1173 g/6 ml/6 ml0.1010 g/2 ml
(III)0.1303 g/11 ml/0 ml0.1012 g/2 ml
(IV)0.1453 g/5 ml/6 ml0.1002 g/2 ml
Average sizes (mm) of the obtained crystals were: 1.0 × 1.0 × 6.0 for (I); 0.8 × 0.9 × 1.0 for (II); 0.8 × 0.9 × 1.0 for (III); and 0.5 × 0.5 × 3.0 for (IV).

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC2H4N3S+·C2HO4C2H3N3S·2C4H6O4C2H3N3S·C5H8O4C2H3N3S·C6H10O4
Mr191.2337.35233.2247.3
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, PbcaMonoclinic, P21/c
Temperature (K)150150150150
a, b, c (Å)3.6848 (1), 10.0617 (2), 18.9595 (4)11.9022 (3), 5.3284 (2), 14.3267 (4)7.1620 (2), 10.0096 (2), 27.8847 (7)11.1790 (2), 10.2187 (2), 9.6532 (2)
α, β, γ (°)90, 94.982 (1), 9090, 96.375 (1), 9090, 90, 9090, 98.116 (1), 90
V3)700.27 (3)902.98 (5)1999.02 (9)1091.69 (4)
Z4484
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.440.430.320.30
Crystal size (mm)0.56 × 0.35 × 0.220.42 × 0.20 × 0.160.42 × 0.16 × 0.140.36 × 0.31 × 0.23
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2013)
Multi-scan
(SADABS; Bruker, 2013)
Multi-scan
(SADABS; Bruker, 2013)
Multi-scan
(SADABS; Bruker, 2013)
Tmin, Tmax0.790, 0.9110.867, 0.9450.876, 0.9570.900, 0.933
No. of measured, independent and
observed [I > 3σ(I)] reflections
6984, 2031, 1856 7307, 2059, 1802 9941, 2295, 1881 10441, 3182, 2616
Rint0.0190.0170.0250.020
(sin θ/λ)max1)0.7040.6500.6500.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.067, 2.13 0.030, 0.081, 2.23 0.028, 0.067, 1.66 0.029, 0.075, 1.88
No. of reflections2031205922953182
No. of parameters125142152160
No. of restraints2242
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.190.33, 0.240.23, 0.220.30, 0.21

Computer programs: APEX2 (Bruker, 2013), SAINT (Bruker, 2013), SIR97 (Altomare et al., 1999), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005), PLATON (Spek, 2009) and JANA2006 (Petříček et al., 2014).

Torsion angles relevant for the carboxyl groups in the title structures top
CompoundTorsion angleValue (°)
(I)C3—C4—O4—H1O40.9 (10)
(II)C5—C6—O3—H1O3-178.5 (12)
(II)C3—C4—O2—H1O24.9 (11)
(III)C4—C3—O1—H1O1177.3 (11)
(III)C6—C7—O3—H1O36.8 (11)
(IV)C4—C3—O1—H1O1-177.3 (9)
(IV)C7—C8—O3—H1O3-2.3 (10)
Non-bonding S···O distances in the title structures top
CompoundAtomsDistance (Å)Symmetry code
(I)S1—O12.9868 (8)-x + 2, y - 1/2, -z + 1/2
(I)S1—O32.8595 (7)x + 2, y - 1, z
(II)S1—O3(H)3.3995 (12)x, -y + 1/2, -z + 1/2
(II)S1—O43.3145 (12)-x, y + 1/2, z + 1/2
(III)S1—O3(H)2.9619 (10)-x + 1/2, -y + 1, z + 1/2
(III)S1—O43.3105 (9)x - 1/2, -y + 3/2, -z + 1
(IV)S1—O3(H)2.9308 (10)x + 2, y, z - 1
(IV)S1—O43.3556 (8)-x + 2, y - 1/2, -z + 1/2
The suffix (H) means that the pertinent O atom is a part of the hydroxyl group.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O4—H1O4···O2i0.809 (14)1.990 (14)2.6709 (10)141.4 (14)
N2—H1N2···O20.923 (13)1.833 (13)2.7553 (11)177.7 (11)
N3—H1N3···O3ii0.867 (10)2.055 (11)2.8745 (12)157.4 (12)
N3—H2N3···O10.888 (10)1.966 (10)2.8407 (11)168.4 (12)
C1—H1C1···O4iii0.946 (13)2.520 (13)3.4044 (12)155.6 (11)
C1—H1C1···N1iv0.946 (13)2.563 (13)3.1531 (13)120.7 (10)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y1/2, z+1/2; (iii) x+1, y1, z; (iv) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H1O2···N2i0.909 (17)1.747 (17)2.6470 (16)170.1 (15)
O3—H1O3···N1ii0.873 (18)1.820 (18)2.6926 (16)178.4 (17)
N3—H1N3···O1ii0.900 (13)2.001 (13)2.8794 (16)164.9 (14)
N3—H2N3···O1iii0.893 (14)2.012 (14)2.8869 (17)166.1 (15)
C1—H1C1···O4iv0.965 (16)2.340 (16)3.0243 (19)127.3 (12)
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y1, z; (iii) x+1, y1/2, z+1/2; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O1i0.879 (11)2.577 (14)2.9535 (15)106.8 (10)
N3—H2N3···O1i0.865 (10)2.788 (14)2.9535 (15)92.4 (11)
N3—H1N3···O20.879 (11)2.101 (12)2.9627 (16)166.6 (13)
N3—H2N3···O4ii0.865 (10)2.034 (12)2.8531 (15)157.8 (14)
O1—H1O1···N20.845 (12)1.848 (12)2.6898 (15)173.9 (13)
O3—H1O3···N1iii0.844 (9)1.875 (9)2.7139 (14)172.7 (15)
O3—H1O3···N2iii0.844 (9)2.916 (11)3.7362 (14)164.5 (13)
C6—H1C6···O1iii0.992.523.4148 (16)150.59
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x1/2, y+3/2, z+1; (iii) x+1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O20.878 (12)1.951 (12)2.8242 (15)172.8 (12)
N3—H2N3···O4ii0.886 (10)1.989 (11)2.8496 (13)163.4 (12)
O1—H1O1···N20.859 (15)1.916 (15)2.7725 (13)174.6 (13)
O3—H1O3···N1ii0.827 (14)1.837 (14)2.6470 (12)165.9 (14)
Symmetry code: (ii) x+1, y1/2, z+1/2.
 

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