Supporting information
CCDC references: 1018659; 1018660; 1018661; 1018662
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.
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.
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.
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.
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).
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).
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).
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].
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.
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).
C2H4N3S+·C2HO4− | F(000) = 392 |
Mr = 191.2 | Dx = 1.813 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4550 reflections |
a = 3.6848 (1) Å | θ = 3.0–30.0° |
b = 10.0617 (2) Å | µ = 0.44 mm−1 |
c = 18.9595 (4) Å | T = 150 K |
β = 94.982 (1)° | Prism, colourless |
V = 700.27 (3) Å3 | 0.56 × 0.35 × 0.22 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2031 independent reflections |
Radiation source: X-ray tube | 1856 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 30.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −5→4 |
Tmin = 0.790, Tmax = 0.911 | k = −14→13 |
6984 measured reflections | l = −25→26 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.023 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.067 | (Δ/σ)max = 0.026 |
S = 2.13 | Δρmax = 0.35 e Å−3 |
2031 reflections | Δρmin = −0.19 e Å−3 |
125 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
2 restraints | Extinction coefficient: 2800 (500) |
5 constraints |
C2H4N3S+·C2HO4− | V = 700.27 (3) Å3 |
Mr = 191.2 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.6848 (1) Å | µ = 0.44 mm−1 |
b = 10.0617 (2) Å | T = 150 K |
c = 18.9595 (4) Å | 0.56 × 0.35 × 0.22 mm |
β = 94.982 (1)° |
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 = 0.911 | Rint = 0.019 |
6984 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 2 restraints |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 2.13 | Δρmax = 0.35 e Å−3 |
2031 reflections | Δρmin = −0.19 e Å−3 |
125 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.79484 (6) | 0.02922 (2) | 0.329515 (12) | 0.01298 (8) | |
C1 | 0.7051 (3) | 0.01362 (10) | 0.41761 (5) | 0.0155 (3) | |
H1C1 | 0.745 (3) | −0.0672 (13) | 0.4420 (7) | 0.0186* | |
N1 | 0.5730 (2) | 0.11718 (8) | 0.44587 (4) | 0.0165 (2) | |
N2 | 0.5392 (2) | 0.21836 (8) | 0.39696 (4) | 0.0145 (2) | |
H1N2 | 0.431 (3) | 0.2958 (13) | 0.4086 (7) | 0.0174* | |
C2 | 0.6399 (2) | 0.19124 (9) | 0.33261 (5) | 0.0127 (2) | |
N3 | 0.6252 (3) | 0.27729 (9) | 0.28034 (5) | 0.0197 (3) | |
H1N3 | 0.677 (3) | 0.2547 (13) | 0.2384 (5) | 0.0237* | |
H2N3 | 0.551 (3) | 0.3591 (9) | 0.2888 (7) | 0.0237* | |
O1 | 0.3875 (2) | 0.52836 (7) | 0.32709 (4) | 0.0186 (2) | |
O2 | 0.2010 (2) | 0.45203 (7) | 0.42940 (4) | 0.0179 (2) | |
C3 | 0.2331 (3) | 0.53837 (9) | 0.38231 (5) | 0.0133 (2) | |
C4 | 0.0620 (3) | 0.67582 (9) | 0.39569 (5) | 0.0139 (2) | |
O3 | 0.0809 (2) | 0.76780 (7) | 0.35515 (4) | 0.0209 (2) | |
O4 | −0.1070 (2) | 0.68824 (7) | 0.45397 (4) | 0.0182 (2) | |
H1O4 | −0.098 (3) | 0.6206 (14) | 0.4768 (7) | 0.0273* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01612 (13) | 0.01060 (13) | 0.01255 (13) | 0.00296 (8) | 0.00317 (9) | −0.00073 (7) |
C1 | 0.0199 (5) | 0.0138 (4) | 0.0131 (4) | 0.0017 (3) | 0.0030 (3) | 0.0014 (3) |
N1 | 0.0221 (4) | 0.0140 (4) | 0.0137 (4) | 0.0021 (3) | 0.0042 (3) | 0.0017 (3) |
N2 | 0.0199 (4) | 0.0108 (4) | 0.0133 (4) | 0.0025 (3) | 0.0049 (3) | 0.0002 (3) |
C2 | 0.0131 (4) | 0.0115 (4) | 0.0138 (4) | 0.0010 (3) | 0.0024 (3) | −0.0010 (3) |
N3 | 0.0315 (5) | 0.0138 (4) | 0.0148 (4) | 0.0073 (3) | 0.0079 (3) | 0.0021 (3) |
O1 | 0.0267 (4) | 0.0157 (4) | 0.0147 (3) | 0.0042 (3) | 0.0087 (3) | 0.0002 (2) |
O2 | 0.0269 (4) | 0.0125 (3) | 0.0155 (3) | 0.0054 (3) | 0.0080 (3) | 0.0025 (2) |
C3 | 0.0155 (4) | 0.0111 (4) | 0.0134 (4) | 0.0013 (3) | 0.0022 (3) | −0.0011 (3) |
C4 | 0.0173 (4) | 0.0122 (4) | 0.0126 (4) | 0.0018 (3) | 0.0034 (3) | −0.0008 (3) |
O3 | 0.0322 (4) | 0.0130 (3) | 0.0188 (3) | 0.0058 (3) | 0.0103 (3) | 0.0042 (3) |
O4 | 0.0286 (4) | 0.0122 (3) | 0.0152 (3) | 0.0056 (3) | 0.0098 (3) | 0.0027 (3) |
S1—C1 | 1.7377 (10) | H1N3—H2N3 | 1.519 (16) |
S1—C2 | 1.7300 (9) | O1—C3 | 1.2382 (12) |
C1—H1C1 | 0.941 (13) | O2—C3 | 1.2586 (12) |
C1—N1 | 1.2865 (13) | C3—C4 | 1.5500 (13) |
N1—N2 | 1.3755 (11) | C4—O3 | 1.2089 (12) |
N2—H1N2 | 0.911 (13) | C4—O4 | 1.3207 (12) |
N2—C2 | 1.3339 (12) | O4—H1O4 | 0.805 (14) |
C2—N3 | 1.3135 (12) | S1—O1i | 2.9868 (8) |
N3—H1N3 | 0.864 (10) | S1—O3ii | 2.8595 (7) |
N3—H2N3 | 0.886 (10) | ||
S1—C1—H1C1 | 121.1 (8) | C2—N3—H2N3 | 118.0 (8) |
S1—C1—N1 | 115.95 (7) | H1N3—N3—H2N3 | 120.4 (12) |
H1C1—C1—N1 | 122.9 (8) | O1—C3—O2 | 128.47 (9) |
C1—N1—N2 | 109.51 (8) | O1—C3—C4 | 115.73 (8) |
N1—N2—H1N2 | 119.0 (8) | O2—C3—C4 | 115.79 (8) |
N1—N2—C2 | 116.69 (8) | C3—C4—O3 | 122.16 (9) |
H1N2—N2—C2 | 124.0 (8) | C3—C4—O4 | 116.71 (8) |
S1—C2—N2 | 110.03 (7) | O3—C4—O4 | 121.13 (9) |
S1—C2—N3 | 125.99 (8) | O3—C4—H1O4 | 146.0 (5) |
N2—C2—N3 | 123.97 (9) | C4—O4—H1O4 | 111.6 (10) |
C2—N3—H1N3 | 121.6 (9) | ||
C3—C4—O4—H1O4 | 0.9 (10) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1O4···O2 | 0.809 (14) | 2.245 (14) | 2.6914 (10) | 115.2 (12) |
O4—H1O4···O2iii | 0.809 (14) | 1.990 (14) | 2.6709 (10) | 141.4 (14) |
N2—H1N2···O2 | 0.923 (13) | 1.833 (13) | 2.7553 (11) | 177.7 (11) |
N3—H1N3···O1i | 0.867 (10) | 2.594 (13) | 3.2260 (11) | 130.6 (11) |
N3—H1N3···O3i | 0.867 (10) | 2.055 (11) | 2.8745 (12) | 157.4 (12) |
N3—H2N3···O1 | 0.888 (10) | 1.966 (10) | 2.8407 (11) | 168.4 (12) |
C1—H1C1···O4ii | 0.946 (13) | 2.520 (13) | 3.4044 (12) | 155.6 (11) |
C1—H1C1···N1iv | 0.946 (13) | 2.563 (13) | 3.1531 (13) | 120.7 (10) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y−1, z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z+1. |
C2H3N3S·2C4H6O4 | F(000) = 456 |
Mr = 337.35 | Dx = 2.481 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3671 reflections |
a = 11.9022 (3) Å | θ = 3.2–27.4° |
b = 5.3284 (2) Å | µ = 0.43 mm−1 |
c = 14.3267 (4) Å | T = 150 K |
β = 96.375 (1)° | Prism, colourless |
V = 902.98 (5) Å3 | 0.42 × 0.20 × 0.16 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2059 independent reflections |
Radiation source: fine-focus sealed tube | 1802 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −15→15 |
Tmin = 0.867, Tmax = 0.945 | k = −6→6 |
7307 measured reflections | l = −18→18 |
Refinement on F2 | 21 constraints |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
S = 2.23 | (Δ/σ)max = 0.015 |
2059 reflections | Δρmax = 0.33 e Å−3 |
142 parameters | Δρmin = −0.24 e Å−3 |
2 restraints |
C2H3N3S·2C4H6O4 | V = 902.98 (5) Å3 |
Mr = 337.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.9022 (3) Å | µ = 0.43 mm−1 |
b = 5.3284 (2) Å | T = 150 K |
c = 14.3267 (4) Å | 0.42 × 0.20 × 0.16 mm |
β = 96.375 (1)° |
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 = 0.945 | Rint = 0.017 |
7307 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 2 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 2.23 | Δρmax = 0.33 e Å−3 |
2059 reflections | Δρmin = −0.24 e Å−3 |
142 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.21112 (3) | 0.42956 (7) | 0.31351 (3) | 0.02313 (13) | |
C1 | 0.16065 (12) | 0.6838 (3) | 0.24681 (11) | 0.0235 (5) | |
H1C1 | 0.0986 (12) | 0.783 (3) | 0.2648 (11) | 0.0282* | |
N1 | 0.21467 (9) | 0.7284 (2) | 0.17521 (8) | 0.0207 (4) | |
N2 | 0.30255 (9) | 0.5626 (2) | 0.16689 (8) | 0.0179 (4) | |
C2 | 0.31147 (11) | 0.3944 (3) | 0.23516 (9) | 0.0172 (4) | |
N3 | 0.39064 (11) | 0.2166 (2) | 0.24449 (9) | 0.0250 (4) | |
H1N3 | 0.3916 (13) | 0.095 (2) | 0.2880 (9) | 0.03* | |
H2N3 | 0.4434 (11) | 0.218 (3) | 0.2049 (9) | 0.03* | |
C3 | 0.45445 (10) | 0.5775 (2) | 0.51965 (9) | 0.0154 (4) | |
H1C3 | 0.389845 | 0.467865 | 0.530056 | 0.0185* | |
H2C3 | 0.483816 | 0.643239 | 0.582263 | 0.0185* | |
C4 | 0.41353 (10) | 0.7917 (3) | 0.45670 (9) | 0.0141 (4) | |
O1 | 0.43435 (7) | 0.80915 (19) | 0.37551 (6) | 0.0188 (3) | |
O2 | 0.35066 (8) | 0.96516 (19) | 0.49118 (7) | 0.0187 (3) | |
H1O2 | 0.3419 (13) | 0.947 (3) | 0.5536 (12) | 0.028* | |
C5 | 0.04858 (10) | 0.4182 (3) | −0.01168 (10) | 0.0188 (4) | |
H1C5 | 0.115705 | 0.524276 | −0.017612 | 0.0226* | |
H2C5 | 0.028961 | 0.339486 | −0.073956 | 0.0226* | |
C6 | 0.07850 (11) | 0.2177 (3) | 0.06046 (10) | 0.0173 (4) | |
O3 | 0.16923 (9) | 0.0877 (2) | 0.04430 (8) | 0.0272 (4) | |
H1O3 | 0.1828 (14) | −0.030 (3) | 0.0871 (13) | 0.0408* | |
O4 | 0.02640 (9) | 0.1755 (2) | 0.12657 (8) | 0.0314 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0244 (2) | 0.0282 (2) | 0.0179 (2) | −0.00497 (16) | 0.00756 (14) | 0.00321 (15) |
C1 | 0.0228 (7) | 0.0245 (9) | 0.0240 (8) | −0.0012 (6) | 0.0061 (6) | −0.0008 (6) |
N1 | 0.0206 (6) | 0.0187 (7) | 0.0232 (7) | 0.0033 (5) | 0.0047 (5) | 0.0023 (5) |
N2 | 0.0207 (6) | 0.0161 (7) | 0.0174 (6) | 0.0012 (5) | 0.0046 (5) | 0.0036 (5) |
C2 | 0.0179 (6) | 0.0185 (8) | 0.0152 (7) | −0.0040 (6) | 0.0013 (5) | 0.0009 (6) |
N3 | 0.0280 (7) | 0.0231 (7) | 0.0253 (7) | 0.0045 (6) | 0.0089 (5) | 0.0099 (6) |
C3 | 0.0187 (6) | 0.0145 (7) | 0.0134 (7) | 0.0013 (5) | 0.0036 (5) | 0.0019 (5) |
C4 | 0.0121 (6) | 0.0126 (7) | 0.0173 (7) | −0.0033 (5) | 0.0009 (5) | −0.0006 (5) |
O1 | 0.0227 (5) | 0.0198 (6) | 0.0145 (5) | 0.0028 (4) | 0.0045 (4) | 0.0034 (4) |
O2 | 0.0231 (5) | 0.0167 (5) | 0.0169 (5) | 0.0051 (4) | 0.0051 (4) | 0.0004 (4) |
C5 | 0.0182 (6) | 0.0186 (8) | 0.0198 (7) | 0.0026 (6) | 0.0033 (5) | 0.0009 (6) |
C6 | 0.0157 (6) | 0.0166 (8) | 0.0195 (7) | −0.0012 (6) | 0.0018 (5) | −0.0013 (6) |
O3 | 0.0275 (5) | 0.0270 (7) | 0.0288 (6) | 0.0131 (5) | 0.0108 (5) | 0.0105 (5) |
O4 | 0.0315 (6) | 0.0334 (7) | 0.0321 (7) | 0.0118 (5) | 0.0157 (5) | 0.0126 (5) |
S1—C1 | 1.7266 (16) | H1C3—H2C3 | 1.5805 |
S1—C2 | 1.7376 (14) | C4—O1 | 1.2194 (16) |
C1—H1C1 | 0.966 (16) | C4—O2 | 1.3192 (17) |
C1—N1 | 1.292 (2) | O2—H1O2 | 0.917 (17) |
N1—N2 | 1.3843 (16) | C5—C5ii | 1.5152 (19) |
N2—C2 | 1.3220 (18) | C5—H1C5 | 0.99 |
C2—N3 | 1.3326 (19) | C5—H2C5 | 0.99 |
N3—H1N3 | 0.900 (13) | C5—C6 | 1.5013 (19) |
N3—H2N3 | 0.892 (14) | H1C5—H2C5 | 1.5818 |
H1N3—H2N3 | 1.55 (2) | C6—O3 | 1.3248 (17) |
C3—C3i | 1.5198 (18) | C6—O4 | 1.2094 (18) |
C3—H1C3 | 0.99 | O3—H1O3 | 0.880 (18) |
C3—H2C3 | 0.99 | S1—O3iii | 3.3995 (12) |
C3—C4 | 1.5021 (18) | S1—O4iv | 3.3145 (12) |
S1—C1—H1C1 | 120.7 (10) | H1C3—C3—C4 | 109.47 |
S1—C1—N1 | 114.25 (11) | H2C3—C3—C4 | 109.47 |
H1C1—C1—N1 | 125.0 (10) | C3—C4—O1 | 122.95 (12) |
C1—N1—N2 | 113.47 (12) | C3—C4—O2 | 117.85 (12) |
N1—N2—C2 | 111.61 (12) | O1—C4—O2 | 119.19 (12) |
N1—N2—H1O2v | 112.5 (5) | C4—O2—H1O2 | 114.9 (10) |
C2—N2—H1O2v | 131.5 (5) | N2vi—H1o2—O2 | 170.0 (15) |
S1—C2—N2 | 113.60 (10) | C5ii—C5—H1C5 | 109.47 |
S1—C2—N3 | 122.74 (11) | C5ii—C5—H2C5 | 109.47 |
N2—C2—N3 | 123.65 (13) | C5ii—C5—C6 | 112.69 (12) |
C2—N3—H1N3 | 122.5 (10) | H1C5—C5—H2C5 | 106.04 |
C2—N3—H2N3 | 118.0 (10) | H1C5—C5—C6 | 109.47 |
H1N3—N3—H2N3 | 119.6 (14) | H2C5—C5—C6 | 109.47 |
C3i—C3—H1C3 | 109.47 | C5—C6—O3 | 112.79 (12) |
C3i—C3—H2C3 | 109.47 | C5—C6—O4 | 124.64 (12) |
C3i—C3—C4 | 112.80 (11) | O3—C6—O4 | 122.57 (13) |
H1C3—C3—H2C3 | 105.92 | C6—O3—H1O3 | 109.9 (12) |
C5—C6—O3—H1O3 | −178.5 (12) | C3—C4—O2—H1o2 | 4.9 (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, z−1/2; (vi) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N2vi | 0.909 (17) | 1.747 (17) | 2.6470 (16) | 170.1 (15) |
O3—H1O3···N1vii | 0.873 (18) | 1.820 (18) | 2.6926 (16) | 178.4 (17) |
N3—H1N3···O1vii | 0.900 (13) | 2.001 (13) | 2.8794 (16) | 164.9 (14) |
N3—H2N3···O1viii | 0.893 (14) | 2.012 (14) | 2.8869 (17) | 166.1 (15) |
C1—H1C1···O4iv | 0.965 (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, y−1, z; (viii) −x+1, y−1/2, −z+1/2. |
C2H3N3S·C5H8O4 | F(000) = 976 |
Mr = 233.2 | Dx = 1.550 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3659 reflections |
a = 7.1620 (2) Å | θ = 2.9–27.4° |
b = 10.0096 (2) Å | µ = 0.32 mm−1 |
c = 27.8847 (7) Å | T = 150 K |
V = 1999.02 (9) Å3 | Prism, colourless |
Z = 8 | 0.42 × 0.16 × 0.14 mm |
Bruker APEXII CCD area-detector diffractometer | 2295 independent reflections |
Radiation source: fine-focus sealed tube | 1881 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.025 |
φ and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −9→8 |
Tmin = 0.876, Tmax = 0.957 | k = −12→12 |
9941 measured reflections | l = −18→36 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 0.067 | (Δ/σ)max = 0.042 |
S = 1.66 | Δρmax = 0.23 e Å−3 |
2295 reflections | Δρmin = −0.22 e Å−3 |
152 parameters | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
4 restraints | Extinction coefficient: 2400 (500) |
29 constraints |
C2H3N3S·C5H8O4 | V = 1999.02 (9) Å3 |
Mr = 233.2 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.1620 (2) Å | µ = 0.32 mm−1 |
b = 10.0096 (2) Å | T = 150 K |
c = 27.8847 (7) Å | 0.42 × 0.16 × 0.14 mm |
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 = 0.957 | Rint = 0.025 |
9941 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 4 restraints |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.66 | Δρmax = 0.23 e Å−3 |
2295 reflections | Δρmin = −0.22 e Å−3 |
152 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | −0.01814 (5) | 0.62369 (3) | 0.706072 (12) | 0.02054 (10) | |
C1 | 0.0041 (2) | 0.45455 (13) | 0.71681 (5) | 0.0219 (4) | |
H1c1 | −0.021 (2) | 0.4166 (16) | 0.7463 (6) | 0.0263* | |
N1 | 0.05342 (16) | 0.38491 (11) | 0.68001 (4) | 0.0203 (3) | |
N2 | 0.07899 (16) | 0.46137 (10) | 0.63913 (4) | 0.0179 (3) | |
C2 | 0.04678 (17) | 0.58919 (12) | 0.64731 (5) | 0.0167 (4) | |
N3 | 0.06418 (18) | 0.68320 (11) | 0.61380 (4) | 0.0228 (4) | |
H1n3 | 0.1059 (19) | 0.6610 (14) | 0.5853 (4) | 0.0273* | |
H2n3 | 0.0391 (19) | 0.7658 (9) | 0.6201 (6) | 0.0273* | |
O1 | 0.19448 (14) | 0.35803 (9) | 0.55517 (4) | 0.0243 (3) | |
H1o1 | 0.156 (2) | 0.3957 (14) | 0.5805 (4) | 0.0365* | |
O2 | 0.19376 (13) | 0.56229 (9) | 0.52272 (4) | 0.0236 (3) | |
C3 | 0.22331 (17) | 0.44300 (13) | 0.51953 (5) | 0.0164 (4) | |
C4 | 0.29937 (18) | 0.37397 (12) | 0.47607 (5) | 0.0197 (4) | |
H1c4 | 0.416013 | 0.326533 | 0.48462 | 0.0236* | |
H2c4 | 0.214957 | 0.299991 | 0.466839 | 0.0236* | |
C5 | 0.33436 (17) | 0.46313 (12) | 0.43282 (5) | 0.0166 (4) | |
H1c5 | 0.214494 | 0.501256 | 0.42163 | 0.02* | |
H2c5 | 0.420073 | 0.53644 | 0.441948 | 0.02* | |
C6 | 0.42163 (18) | 0.38131 (12) | 0.39283 (5) | 0.0177 (4) | |
H1c6 | 0.535889 | 0.336889 | 0.404873 | 0.0212* | |
H2c6 | 0.339744 | 0.304541 | 0.385165 | 0.0212* | |
C7 | 0.46625 (17) | 0.45629 (12) | 0.34767 (5) | 0.0166 (4) | |
O3 | 0.54004 (13) | 0.38516 (9) | 0.31209 (4) | 0.0201 (3) | |
H1o3 | 0.543 (2) | 0.3021 (9) | 0.3172 (6) | 0.0302* | |
O4 | 0.44135 (14) | 0.57526 (9) | 0.34197 (4) | 0.0232 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03127 (19) | 0.01649 (17) | 0.01386 (18) | 0.00020 (13) | 0.00432 (14) | −0.00241 (14) |
C1 | 0.0335 (8) | 0.0182 (7) | 0.0140 (7) | −0.0009 (5) | 0.0013 (6) | 0.0011 (6) |
N1 | 0.0299 (6) | 0.0182 (5) | 0.0127 (6) | −0.0001 (5) | 0.0003 (5) | 0.0008 (5) |
N2 | 0.0265 (6) | 0.0151 (5) | 0.0120 (6) | −0.0003 (4) | 0.0009 (5) | 0.0010 (5) |
C2 | 0.0185 (6) | 0.0185 (6) | 0.0131 (7) | −0.0005 (5) | 0.0006 (5) | −0.0022 (5) |
N3 | 0.0364 (7) | 0.0154 (5) | 0.0166 (6) | 0.0007 (5) | 0.0070 (5) | 0.0001 (5) |
O1 | 0.0424 (6) | 0.0166 (5) | 0.0141 (5) | 0.0059 (4) | 0.0082 (4) | 0.0021 (4) |
O2 | 0.0380 (6) | 0.0145 (5) | 0.0182 (5) | 0.0018 (4) | 0.0050 (5) | −0.0004 (4) |
C3 | 0.0181 (6) | 0.0179 (6) | 0.0131 (7) | −0.0001 (5) | −0.0018 (5) | 0.0012 (5) |
C4 | 0.0285 (7) | 0.0155 (6) | 0.0151 (7) | 0.0028 (5) | 0.0027 (6) | 0.0001 (6) |
C5 | 0.0212 (6) | 0.0162 (6) | 0.0125 (7) | 0.0010 (5) | −0.0001 (5) | −0.0003 (5) |
C6 | 0.0235 (6) | 0.0162 (6) | 0.0134 (7) | 0.0021 (5) | 0.0010 (5) | 0.0014 (5) |
C7 | 0.0190 (6) | 0.0172 (6) | 0.0135 (7) | −0.0024 (5) | −0.0034 (6) | −0.0014 (5) |
O3 | 0.0319 (5) | 0.0149 (4) | 0.0135 (5) | −0.0002 (4) | 0.0028 (4) | 0.0004 (4) |
O4 | 0.0368 (6) | 0.0140 (5) | 0.0188 (5) | −0.0009 (4) | −0.0008 (5) | 0.0012 (4) |
S1—C1 | 1.7266 (14) | C4—H1c4 | 0.99 |
S1—C2 | 1.7379 (14) | C4—H2c4 | 0.99 |
C1—H1c1 | 0.923 (17) | C4—C5 | 1.5210 (18) |
C1—N1 | 1.2898 (18) | C5—H1c5 | 0.99 |
N1—N2 | 1.3853 (16) | C5—H2c5 | 0.99 |
N2—C2 | 1.3199 (16) | C5—C6 | 1.5183 (18) |
C2—N3 | 1.3318 (17) | C6—H1c6 | 0.99 |
N3—H1n3 | 0.879 (11) | C6—H2c6 | 0.99 |
N3—H2n3 | 0.865 (10) | C6—C7 | 1.5002 (18) |
H1n3—H2n3 | 1.509 (18) | C7—O3 | 1.3306 (16) |
O1—H1o1 | 0.845 (12) | C7—O4 | 1.2146 (15) |
O1—C3 | 1.3243 (16) | O3—H1o3 | 0.844 (9) |
O2—C3 | 1.2160 (15) | S1—O3i | 2.9619 (10) |
C3—C4 | 1.4976 (18) | S1—O4ii | 3.3105 (9) |
S1—C1—H1c1 | 122.6 (10) | H1c4—C4—C5 | 109.47 |
S1—C1—N1 | 114.66 (11) | H2c4—C4—C5 | 109.47 |
H1c1—C1—N1 | 122.7 (10) | C4—C5—H1c5 | 109.47 |
C1—N1—N2 | 113.09 (11) | C4—C5—H2c5 | 109.47 |
N1—N2—C2 | 111.73 (11) | C4—C5—C6 | 109.49 (10) |
S1—C2—N2 | 113.72 (10) | H1c5—C5—H2c5 | 109.45 |
S1—C2—N3 | 123.10 (10) | H1c5—C5—C6 | 109.47 |
N2—C2—N3 | 123.18 (12) | H2c5—C5—C6 | 109.47 |
C2—N3—H1n3 | 119.2 (9) | C5—C6—H1c6 | 109.47 |
C2—N3—H2n3 | 120.9 (10) | C5—C6—H2c6 | 109.47 |
H1n3—N3—H2n3 | 119.9 (14) | C5—C6—C7 | 115.74 (10) |
H1o1—O1—C3 | 112.9 (9) | H1c6—C6—H2c6 | 102.37 |
O1—C3—O2 | 123.28 (12) | H1c6—C6—C7 | 109.47 |
O1—C3—C4 | 111.58 (11) | H2c6—C6—C7 | 109.47 |
O2—C3—C4 | 125.14 (12) | C6—C7—O3 | 116.28 (10) |
C3—C4—H1c4 | 109.47 | C6—C7—O4 | 124.69 (12) |
C3—C4—H2c4 | 109.47 | O3—C7—O4 | 119.03 (12) |
C3—C4—C5 | 115.52 (10) | C7—O3—H1o3 | 114.4 (10) |
H1c4—C4—H2c4 | 102.66 | ||
C4—C3—O1—H1O1 | 177.3 (11) | C6—C7—O3—H1O3 | 6.8 (11) |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O1iii | 0.88 (1) | 2.58 (1) | 2.9535 (15) | 107 (1) |
N3—H2N3···O1iii | 0.87 (1) | 2.79 (1) | 2.9535 (15) | 92 (1) |
N3—H1N3···O2 | 0.88 (1) | 2.10 (1) | 2.9627 (16) | 167 (1) |
N3—H2N3···O4ii | 0.87 (1) | 2.03 (1) | 2.8531 (15) | 158 (1) |
O1—H1O1···N2 | 0.85 (1) | 1.85 (1) | 2.6898 (15) | 174 (1) |
O3—H1O3···N1iv | 0.84 (1) | 1.88 (1) | 2.7139 (14) | 173 (2) |
O3—H1O3···N2iv | 0.84 (1) | 2.92 (1) | 3.7362 (14) | 165 (1) |
C6—H1C6···O1iv | 0.99 | 2.52 | 3.4148 (16) | 151 |
Symmetry codes: (ii) x−1/2, −y+3/2, −z+1; (iii) −x+1/2, y+1/2, z; (iv) x+1/2, −y+1/2, −z+1. |
C2H3N3S·C6H10O4 | F(000) = 520 |
Mr = 247.3 | Dx = 1.504 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4518 reflections |
a = 11.1790 (2) Å | θ = 2.7–30.0° |
b = 10.2187 (2) Å | µ = 0.30 mm−1 |
c = 9.6532 (2) Å | T = 150 K |
β = 98.116 (1)° | Prism, colourless |
V = 1091.69 (4) Å3 | 0.36 × 0.31 × 0.23 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 3182 independent reflections |
Radiation source: fine-focus sealed tube | 2616 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.020 |
φ and ω scans | θmax = 30.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −12→15 |
Tmin = 0.900, Tmax = 0.933 | k = −14→14 |
10441 measured reflections | l = −13→10 |
Refinement on F2 | 37 constraints |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
S = 1.88 | (Δ/σ)max = 0.022 |
3182 reflections | Δρmax = 0.30 e Å−3 |
160 parameters | Δρmin = −0.21 e Å−3 |
2 restraints |
C2H3N3S·C6H10O4 | V = 1091.69 (4) Å3 |
Mr = 247.3 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1790 (2) Å | µ = 0.30 mm−1 |
b = 10.2187 (2) Å | T = 150 K |
c = 9.6532 (2) Å | 0.36 × 0.31 × 0.23 mm |
β = 98.116 (1)° |
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 = 0.933 | Rint = 0.020 |
10441 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 2 restraints |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.88 | Δρmax = 0.30 e Å−3 |
3182 reflections | Δρmin = −0.21 e Å−3 |
160 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.92798 (2) | 0.58212 (3) | −0.16637 (3) | 0.01828 (8) | |
C1 | 0.93970 (10) | 0.74918 (11) | −0.18192 (12) | 0.0189 (3) | |
H1c1 | 0.9901 (11) | 0.7888 (13) | −0.2422 (14) | 0.0227* | |
N1 | 0.87422 (8) | 0.81559 (9) | −0.10641 (10) | 0.0189 (3) | |
N2 | 0.80693 (8) | 0.73784 (9) | −0.02887 (10) | 0.0176 (3) | |
C2 | 0.82499 (9) | 0.61224 (11) | −0.05088 (12) | 0.0167 (3) | |
N3 | 0.77004 (9) | 0.51588 (10) | 0.00746 (12) | 0.0267 (3) | |
H1n3 | 0.7232 (10) | 0.5383 (13) | 0.0692 (11) | 0.032* | |
H2n3 | 0.7877 (12) | 0.4339 (9) | −0.0117 (14) | 0.032* | |
O1 | 0.64820 (7) | 0.82007 (8) | 0.14962 (9) | 0.0221 (3) | |
H1o1 | 0.6971 (13) | 0.7895 (13) | 0.0965 (15) | 0.0331* | |
O2 | 0.61559 (8) | 0.60863 (8) | 0.19340 (10) | 0.0314 (3) | |
C3 | 0.59450 (9) | 0.72358 (11) | 0.20916 (12) | 0.0186 (3) | |
C4 | 0.50333 (9) | 0.77157 (11) | 0.29840 (11) | 0.0179 (3) | |
H1c4 | 0.449227 | 0.836298 | 0.245109 | 0.0215* | |
H2c4 | 0.545406 | 0.819773 | 0.380026 | 0.0215* | |
C5 | 0.42806 (9) | 0.66197 (11) | 0.34890 (12) | 0.0191 (3) | |
H1c5 | 0.481604 | 0.600867 | 0.40831 | 0.0229* | |
H2c5 | 0.388588 | 0.611549 | 0.267467 | 0.0229* | |
C6 | 0.33238 (9) | 0.71488 (11) | 0.43140 (12) | 0.0170 (3) | |
H1c6 | 0.371252 | 0.770903 | 0.508575 | 0.0204* | |
H2c6 | 0.276896 | 0.773258 | 0.370827 | 0.0204* | |
C7 | 0.25987 (9) | 0.60774 (11) | 0.49075 (11) | 0.0185 (3) | |
H1c7 | 0.217882 | 0.554275 | 0.413197 | 0.0223* | |
H2c7 | 0.315703 | 0.546357 | 0.546769 | 0.0223* | |
C8 | 0.16922 (9) | 0.65874 (10) | 0.57891 (12) | 0.0170 (3) | |
O3 | 0.10549 (8) | 0.57162 (8) | 0.63762 (10) | 0.0265 (3) | |
H1o3 | 0.1194 (12) | 0.4948 (14) | 0.6180 (14) | 0.0397* | |
O4 | 0.15287 (7) | 0.77487 (8) | 0.59926 (9) | 0.0228 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02002 (13) | 0.01443 (15) | 0.02273 (15) | 0.00142 (10) | 0.01118 (10) | −0.00105 (11) |
C1 | 0.0200 (5) | 0.0158 (6) | 0.0222 (6) | −0.0013 (4) | 0.0078 (4) | 0.0008 (5) |
N1 | 0.0211 (4) | 0.0146 (5) | 0.0224 (5) | −0.0013 (4) | 0.0082 (4) | 0.0001 (4) |
N2 | 0.0211 (4) | 0.0127 (5) | 0.0211 (5) | −0.0005 (3) | 0.0098 (4) | −0.0003 (4) |
C2 | 0.0175 (5) | 0.0158 (5) | 0.0181 (5) | 0.0019 (4) | 0.0073 (4) | −0.0001 (4) |
N3 | 0.0347 (5) | 0.0128 (5) | 0.0385 (6) | 0.0016 (4) | 0.0257 (5) | 0.0004 (5) |
O1 | 0.0251 (4) | 0.0187 (4) | 0.0257 (5) | −0.0002 (3) | 0.0147 (3) | 0.0011 (4) |
O2 | 0.0383 (5) | 0.0161 (4) | 0.0464 (6) | −0.0008 (4) | 0.0291 (4) | −0.0026 (4) |
C3 | 0.0176 (5) | 0.0196 (6) | 0.0196 (5) | −0.0009 (4) | 0.0066 (4) | −0.0007 (5) |
C4 | 0.0185 (5) | 0.0171 (6) | 0.0198 (5) | 0.0003 (4) | 0.0086 (4) | −0.0016 (5) |
C5 | 0.0197 (5) | 0.0166 (6) | 0.0234 (6) | 0.0009 (4) | 0.0115 (4) | −0.0011 (5) |
C6 | 0.0183 (5) | 0.0152 (5) | 0.0192 (5) | 0.0003 (4) | 0.0083 (4) | −0.0001 (4) |
C7 | 0.0205 (5) | 0.0160 (6) | 0.0211 (6) | 0.0001 (4) | 0.0096 (4) | −0.0022 (5) |
C8 | 0.0183 (5) | 0.0153 (5) | 0.0184 (5) | −0.0003 (4) | 0.0067 (4) | 0.0000 (5) |
O3 | 0.0350 (4) | 0.0117 (4) | 0.0384 (5) | 0.0003 (3) | 0.0250 (4) | 0.0012 (4) |
O4 | 0.0283 (4) | 0.0125 (4) | 0.0308 (5) | 0.0003 (3) | 0.0156 (3) | −0.0005 (4) |
S1—C1 | 1.7203 (12) | C5—H1c5 | 0.99 |
S1—C2 | 1.7394 (12) | C5—H2c5 | 0.99 |
C1—H1c1 | 0.955 (14) | C5—C6 | 1.5203 (16) |
C1—N1 | 1.2956 (15) | H1c5—H2c5 | 1.5945 |
N1—N2 | 1.3843 (14) | C6—H1c6 | 0.99 |
N2—C2 | 1.3211 (14) | C6—H2c6 | 0.99 |
C2—N3 | 1.3273 (16) | C6—C7 | 1.5215 (16) |
N3—H1n3 | 0.878 (12) | H1c6—H2c6 | 1.5765 |
N3—H2n3 | 0.886 (10) | C7—H1c7 | 0.99 |
H1n3—H2n3 | 1.558 (17) | C7—H2c7 | 0.99 |
O1—H1o1 | 0.859 (15) | C7—C8 | 1.5055 (16) |
O1—C3 | 1.3268 (14) | H1c7—H2c7 | 1.5706 |
O2—C3 | 1.2119 (14) | C8—O3 | 1.3173 (14) |
C3—C4 | 1.5064 (16) | C8—O4 | 1.2208 (13) |
C4—H1c4 | 0.99 | O3—H1o3 | 0.827 (14) |
C4—H2c4 | 0.99 | S1—O3i | 2.9308 (10) |
C4—C5 | 1.5217 (16) | S1—O4ii | 3.3556 (8) |
H1c4—H2c4 | 1.5765 | ||
S1—C1—H1c1 | 122.2 (8) | C4—C5—H2c5 | 109.47 |
S1—C1—N1 | 114.49 (9) | C4—C5—C6 | 111.58 (9) |
H1c1—C1—N1 | 123.3 (8) | H1c5—C5—H2c5 | 107.28 |
C1—N1—N2 | 113.39 (9) | H1c5—C5—C6 | 109.47 |
N1—N2—C2 | 111.32 (9) | H2c5—C5—C6 | 109.47 |
S1—C2—N2 | 113.89 (8) | C5—C6—H1c6 | 109.47 |
S1—C2—N3 | 121.91 (9) | C5—C6—H2c6 | 109.47 |
N2—C2—N3 | 124.20 (11) | C5—C6—C7 | 113.14 (9) |
C2—N3—H1n3 | 116.8 (9) | H1c6—C6—H2c6 | 105.54 |
C2—N3—H2n3 | 118.9 (9) | H1c6—C6—C7 | 109.47 |
H1n3—N3—H2n3 | 124.1 (12) | H2c6—C6—C7 | 109.47 |
H1o1—O1—C3 | 110.7 (9) | C6—C7—H1c7 | 109.47 |
O1—C3—O2 | 123.91 (11) | C6—C7—H2c7 | 109.47 |
O1—C3—C4 | 112.95 (10) | C6—C7—C8 | 113.62 (9) |
O2—C3—C4 | 123.14 (11) | H1c7—C7—H2c7 | 104.98 |
C3—C4—H1c4 | 109.47 | H1c7—C7—C8 | 109.47 |
C3—C4—H2c4 | 109.47 | H2c7—C7—C8 | 109.47 |
C3—C4—C5 | 113.14 (9) | C7—C8—O3 | 117.22 (9) |
H1c4—C4—H2c4 | 105.54 | C7—C8—O4 | 123.75 (10) |
H1c4—C4—C5 | 109.47 | O3—C8—O4 | 119.04 (10) |
H2c4—C4—C5 | 109.47 | C8—O3—H1o3 | 114.3 (10) |
C4—C5—H1c5 | 109.47 | ||
C4—C3—O1—H1o1 | −177.3 (9) | C7—C8—O3—H1o3 | −2.2 (10) |
Symmetry codes: (i) x+1, y, z−1; (ii) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O2 | 0.88 (1) | 1.95 (1) | 2.8242 (15) | 173 (1) |
N3—H2N3···O4ii | 0.89 (1) | 1.99 (1) | 2.8496 (13) | 163 (1) |
O1—H1O1···N2 | 0.86 (2) | 1.92 (2) | 2.7725 (13) | 175 (1) |
O3—H1O3···N1ii | 0.83 (1) | 1.84 (1) | 2.6470 (12) | 166 (1) |
Symmetry code: (ii) −x+1, y−1/2, −z+1/2. |
Compound | Acid (g)/H2O (ml)/CH3OH (ml) | Base (g)/H2O (ml) |
(I) | 0.1255 g/12 ml/0 ml | 0.1005 g/2 ml |
(II) | 0.1173 g/6 ml/6 ml | 0.1010 g/2 ml |
(III) | 0.1303 g/11 ml/0 ml | 0.1012 g/2 ml |
(IV) | 0.1453 g/5 ml/6 ml | 0.1002 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 formula | C2H4N3S+·C2HO4− | C2H3N3S·2C4H6O4 | C2H3N3S·C5H8O4 | C2H3N3S·C6H10O4 |
Mr | 191.2 | 337.35 | 233.2 | 247.3 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 150 | 150 | 150 | 150 |
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), 90 | 90, 96.375 (1), 90 | 90, 90, 90 | 90, 98.116 (1), 90 |
V (Å3) | 700.27 (3) | 902.98 (5) | 1999.02 (9) | 1091.69 (4) |
Z | 4 | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.43 | 0.32 | 0.30 |
Crystal size (mm) | 0.56 × 0.35 × 0.22 | 0.42 × 0.20 × 0.16 | 0.42 × 0.16 × 0.14 | 0.36 × 0.31 × 0.23 |
Data collection | ||||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2013) | Multi-scan (SADABS; Bruker, 2013) | Multi-scan (SADABS; Bruker, 2013) | Multi-scan (SADABS; Bruker, 2013) |
Tmin, Tmax | 0.790, 0.911 | 0.867, 0.945 | 0.876, 0.957 | 0.900, 0.933 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 6984, 2031, 1856 | 7307, 2059, 1802 | 9941, 2295, 1881 | 10441, 3182, 2616 |
Rint | 0.019 | 0.017 | 0.025 | 0.020 |
(sin θ/λ)max (Å−1) | 0.704 | 0.650 | 0.650 | 0.704 |
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 reflections | 2031 | 2059 | 2295 | 3182 |
No. of parameters | 125 | 142 | 152 | 160 |
No. of restraints | 2 | 2 | 4 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.19 | 0.33, −0.24 | 0.23, −0.22 | 0.30, −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).
Compound | Torsion angle | Value (°) |
(I) | C3—C4—O4—H1O4 | 0.9 (10) |
(II) | C5—C6—O3—H1O3 | -178.5 (12) |
(II) | C3—C4—O2—H1O2 | 4.9 (11) |
(III) | C4—C3—O1—H1O1 | 177.3 (11) |
(III) | C6—C7—O3—H1O3 | 6.8 (11) |
(IV) | C4—C3—O1—H1O1 | -177.3 (9) |
(IV) | C7—C8—O3—H1O3 | -2.3 (10) |
Compound | Atoms | Distance (Å) | Symmetry code |
(I) | S1—O1 | 2.9868 (8) | -x + 2, y - 1/2, -z + 1/2 |
(I) | S1—O3 | 2.8595 (7) | x + 2, y - 1, z |
(II) | S1—O3(H) | 3.3995 (12) | x, -y + 1/2, -z + 1/2 |
(II) | S1—O4 | 3.3145 (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—O4 | 3.3105 (9) | x - 1/2, -y + 3/2, -z + 1 |
(IV) | S1—O3(H) | 2.9308 (10) | x + 2, y, z - 1 |
(IV) | S1—O4 | 3.3556 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1O4···O2i | 0.809 (14) | 1.990 (14) | 2.6709 (10) | 141.4 (14) |
N2—H1N2···O2 | 0.923 (13) | 1.833 (13) | 2.7553 (11) | 177.7 (11) |
N3—H1N3···O3ii | 0.867 (10) | 2.055 (11) | 2.8745 (12) | 157.4 (12) |
N3—H2N3···O1 | 0.888 (10) | 1.966 (10) | 2.8407 (11) | 168.4 (12) |
C1—H1C1···O4iii | 0.946 (13) | 2.520 (13) | 3.4044 (12) | 155.6 (11) |
C1—H1C1···N1iv | 0.946 (13) | 2.563 (13) | 3.1531 (13) | 120.7 (10) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y−1, z; (iv) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N2i | 0.909 (17) | 1.747 (17) | 2.6470 (16) | 170.1 (15) |
O3—H1O3···N1ii | 0.873 (18) | 1.820 (18) | 2.6926 (16) | 178.4 (17) |
N3—H1N3···O1ii | 0.900 (13) | 2.001 (13) | 2.8794 (16) | 164.9 (14) |
N3—H2N3···O1iii | 0.893 (14) | 2.012 (14) | 2.8869 (17) | 166.1 (15) |
C1—H1C1···O4iv | 0.965 (16) | 2.340 (16) | 3.0243 (19) | 127.3 (12) |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O1i | 0.879 (11) | 2.577 (14) | 2.9535 (15) | 106.8 (10) |
N3—H2N3···O1i | 0.865 (10) | 2.788 (14) | 2.9535 (15) | 92.4 (11) |
N3—H1N3···O2 | 0.879 (11) | 2.101 (12) | 2.9627 (16) | 166.6 (13) |
N3—H2N3···O4ii | 0.865 (10) | 2.034 (12) | 2.8531 (15) | 157.8 (14) |
O1—H1O1···N2 | 0.845 (12) | 1.848 (12) | 2.6898 (15) | 173.9 (13) |
O3—H1O3···N1iii | 0.844 (9) | 1.875 (9) | 2.7139 (14) | 172.7 (15) |
O3—H1O3···N2iii | 0.844 (9) | 2.916 (11) | 3.7362 (14) | 164.5 (13) |
C6—H1C6···O1iii | 0.99 | 2.52 | 3.4148 (16) | 150.59 |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···O2 | 0.878 (12) | 1.951 (12) | 2.8242 (15) | 172.8 (12) |
N3—H2N3···O4ii | 0.886 (10) | 1.989 (11) | 2.8496 (13) | 163.4 (12) |
O1—H1O1···N2 | 0.859 (15) | 1.916 (15) | 2.7725 (13) | 174.6 (13) |
O3—H1O3···N1ii | 0.827 (14) | 1.837 (14) | 2.6470 (12) | 165.9 (14) |
Symmetry code: (ii) −x+1, y−1/2, −z+1/2. |