research communications
and Hirshfeld surface analysis of two organic salts based on 1,3,4-thiadiazole derivatives
aInstitute of Bioorganic Chemistry, UzAS, M.Ulugbek Str., 83, 100125, Tashkent, Uzbekistan
*Correspondence e-mail: li_izotova@mail.ru
During attempts to achieve interaction between 2-amino-5-ethyl-1,3,4-thiadiazole with oxalyl chloride and 5-mercapto-3-phenyl-1,3,4-thiadiazol-2-thione with various diacid 4H8N3S+·0.5C2O42−, (I), and 4-(dimethylamino)pyridin-1-ium 4-phenyl-5-sulfanylidene-4,5-dihydro-1,3,4-thiadiazole-2-thiolate, C7H11N2+·C8H5N2S3−, (II). Both solids were investigated by single-crystal X-ray diffraction and by Hirshfeld surface analysis. An infinite one-dimensional chain along [100] is generated through O—H⋯O interactions between the oxalate anion and two 2-amino-5-ethyl-1,3,4-thiadiazol-3-ium cations in compound (I), and a three-dimensional supramolecular framework is generated through C—H⋯O and π–π interactions. In compound (II), an organic salt is formed by a 4-phenyl-5-sulfanylidene-4,5-dihydro-1,3,4-thiadiazole-2-thiolate anion and a 4-(dimethylamino)pyridin-1-ium cation, which are combined by an N—H⋯S hydrogen-bonding interaction, forming a zero-dimensional structural unit. As a result of intermolecular π–π interactions, the structural units are combined into a one-dimensional chain running along the a-axis direction.
we obtained two co-crystals (organic salts), namely, 2-amino-5-ethyl-1,3,4-thiadiazol-3-ium hemioxalate, C1. Chemical context
In the field of medicinal chemistry, the search for new selective drugs with reduced toxicity is ongoing. et al., 2013). The sulfur atom of the thiadiazole moiety gives lipophilic properties to these compounds, which provides better permeability through biological membranes (Song et al., 1999). The thiadiazole nucleus with its N–C–S linkage exhibits a large number of biological activities (Kurtzer et al., 1965). It has been found that derivatives of 1,3,4-thiadiazole have diverse pharmacological activities such as fungicidal, insecticidal, bactericidal, herbicidal, anti-tumor (Shivarama Holla et al., 2002), anti-inflammatory and antiviral (Witkoaski et al.,1972). A number of 1,3,4-thiadiazoles exhibit antibacterial properties similar to those of well-known sulfonamide drugs. 1,3,4-Thiadiazole derivatives have been patented for agricultural use, as herbicides and bactericides. According to these findings and in a continuation of our work on synthesizing various condensed-bridge bioactive molecules bearing multifunctional and pharmaceutically active groups (Priya et al., 2005; Sadashiva et al., 2004), we have investigated the structural properties of two new 1,3,4-thiadiazole derivatives.
with the 1,3,4-thiadiazole structural unit are very attractive for the production of pharmaceuticals as 1,3,4-thiadiazole derivatives exhibit a wide spectrum of biological activities. The 1,3,4-thiadiazole moiety acts as a hydrogen-binding dominant unit on the one hand and as an electron-donor unit on the other (Sharma2. Structural commentary
The molecular structure of compound (I) is illustrated in Fig. 1. The compound consists of two nearly flat 2-amino-5-ethyl-1,3,4-thiadiazol-3-ium cations and an oxalate anion. The ethyl unit of the 2-amino-5-ethyl-1,3,4-thiadiazol-3-ium cation has an extended conformation and is almost in the same plane as the thiadiazole ring, as indicated by the torsion angle S1—C2—C3—C4 = −176.16 (15)°. The oxalate anion is also in the plane of the cation [the angle between the root-mean-square planes of these molecules is 5.71 (2)°]. The molecular structure of compound (II) is illustrated in Fig. 2. In the 4-phenyl-5-sulfanylidene-4,5-dihydro-1,3,4-thiadiazole-2-thiolate moiety, the phenyl ring is inclined by 69.08 (14)° to the plane of the thiadiazole ring. The 4-(dimethylamino)pyridin-1-ium is almost planar, the largest deviation from the root-mean-square plane of the molecule being 0.01 Å.
3. Supramolecular features
In the there is a protonated 2-amino-5-ethyl-1,3,4-thiadiazole molecule (cation) and half of a doubly deprotonated oxalic acid molecule (anion) (it is on a special position: there is a center of inversion in the middle of the molecule), i.e. the molecular ratio is 2:1. The oxygen atoms of the oxalate anion are involved in intermolecular hydrogen bonding (Table 1) with neighboring cationic species, leading to the formation of one-dimensional infinite chains. Such chains are packed parallel to each other in the [100] direction in the (Fig. 3). Each chain consists of alternate eight- and fourteen-membered (including hydrogen atoms) conjugated rings, with the graph-set notations R22(8) and R44(14), respectively, according to the hydrogen-bonding patterns defined by Etter et al. (1993). These chains are interconnected via C—H⋯O (Table 1, Fig. 4) and π–π interactions [Cg1⋯Cg1( + x, − y, + z) = 3.7734 (10) Å, where Cg1 is the centroid of the S1/C1/N2/N3/C2 ring].
of compound (I)In compound (II), the contains a 4-(dimethylamino)pyridin-1-ium cation and a 4-phenyl-5-sulfanylidene-4,5-dihydro-1,3,4-thiadiazole-2-thiolate anion, i.e. the molecular ratio is 1:1. The cation and anion are combined by an N—H⋯S hydrogen-bonding interaction (Table 2) and form 0-D structural units. As a result of intermolecular π–π interactions between the benzene rings of two equivalent anions of the 4-(dimethylamino)pyridin-1-ium unit [Cg1⋯Cg1(1 − x, 1 − y, 1 − z) = 4.311 (2) Å, Cg1 is the centroid of the C3–C8 ring], the structural units combine as a building block of a one-dimensional chain running along the a-axis direction (Fig. 5).
|
4. Database survey
A search of the Cambridge Structural Database (Version 5.41, September 2021; Groom et al., 2016) revealed that there are two structures of organic salts containing the compounds mentioned in this article. The first structure is that of 2-amino-5-ethyl-1,3,4-thiadiazole with 2-4 dichlorophenoxy acetic acid (XAPXIV; Lynch et al., 1999). This structure is considered among proton-transfer complexes and the dominant intermolecular association is an R22(8) graph-set dimer across the N3A/N21A site to the two carboxylate oxygen atoms. The second structure is for bis(4-aminopyridine-N)trimethyltin with 3-phenyl-1,3,4-thiadiazoline-2-thione-5-thiolate (XIGPEI; [Berceanc et al., 2002). In this complex, the 4-N-aminopyridine, being coordinatively bound to the tin atom, participates in a weak hydrogen bond [N—H⋯S = 3.366 (2) Å, 159°] with the 1,3,4-thiadiazole molecule.
5. Hirshfeld surface calculation
In order to visualize the intermolecular interactions in the structures of compounds (I) and (II), a Hirshfeld surface analysis was carried out using CrystalExplorer 17.5 (Turner et al., 2017). The Hirshfeld surface mapped over dnorm (Fig. 6) shows that in (I), the expected bright-red spots near atoms O1 and O2, involved in the hydrogen-bonding interactions. Fingerprint plots (Fig. 8) reveal that O⋯H/H⋯O, H⋯H and H⋯C/C⋯H interactions make the greatest contributions to the surface contacts, while S⋯N/N⋯S, S⋯H/H⋯S, S⋯S contacts are less significant. In (II), the greatest contributions to the surface contacts are from H⋯S/S⋯H, H⋯H and C⋯H/H⋯C interactions, with smaller contributions from N⋯H/H⋯N and C⋯C interactions (Fig. 7, Fig. 9).
6. Synthesis and crystallization
Synthesis of 2-amino-5-ethyl-1,3,4-thiadiazole:
Propionic acid (0.108 mol) was mixed with 16 g of sulfuric acid (94%). The reaction temperature was allowed to reach 333–343 K, and then, under the same conditions, 0.1 mol of thiosemicarbazide were added. The mixture was stirred for 3 h at 333–343 K, water and −1): 3290, 2980, 2780; 1640.
were added, and the mixture was stirred for 40 minutes. At the end of the reaction, the solution was filtered. Then, 44% sodium hydroxide solution was added to get a solution with pH 9.5–10. After cooling the reaction to 303–308 K, the mixture was filtered. The precipitate was washed with water (303 K) and allowed to dry to give the title compound (12 g, 93%), m.p. 460–467 K. IR (cmCompound (I) was obtained using the procedure described by Harris et al. (1984). We tried to achieve interaction between 2-amino-5-ethyl-1,3,4-thiadiazole and oxalyl chloride. For this, 20 mmol oxalyl dichloride were mixed with 40 mmol of 2-amino-5-ethyl-1,3,4-thiadiazole in 15 ml of dry acetone, and stirred under boiling acetone for 10 h. The solvent was then removed by rotary evaporation, and the residue was purified by recristallization from water. Beige block-shaped crystals were obtained after one week of slow evaporation of the solvent. We presume that oxalyl chloride was transformed to oxalic acid upon treatment with water in the last step of the reaction.
Compound (II) was obtained during a typical procedure (Sheikh et al., 2010) for the etherification reaction between 5-mercapto-3-phenyl-1,3,4-thiadiazol-2-thione and glutaric anhydride. The isolated reaction products were amorphous. For purification, the reaction products were treated by filtration in ethyl alcohol. Colorless needle-like single crystals were afforded after 2 days by slow evaporation of the solvent.
7. Refinement
Crystal data, data collection and structure . In (I), atom H1 (at protonated atom N2 of 2-amino-5-ethyl-1,3,4-thiadiazol-3-ium) was located from difference-Fourier maps. All other H atoms were placed in idealized positions (N—H = 0.86, C—H = 0.96–0.97 Å) and refined as riding on their carrier atoms [Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(C-methyl)]. In (II), all hydrogen atoms except those of the methyl groups in 4-(dimethylamino)pyridin-1-ium were located from difference Fourier-maps and freely refined. Methyl H atoms were positioned geometrically and refined as riding [C—H = 0.96 Å; Uiso(H) = 1.5Ueq(C)].
details are summarized in Table 3
|
Supporting information
https://doi.org/10.1107/S2056989022012154/dj2057sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022012154/dj2057Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022012154/dj2057IIsup3.hkl
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2020); cell
CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP (Siemens, 1994), Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).C4H8N3S+·0.5C2O42− | F(000) = 364 |
Mr = 174.20 | Dx = 1.498 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54184 Å |
a = 6.4215 (1) Å | Cell parameters from 2613 reflections |
b = 18.1227 (3) Å | θ = 4.9–70.9° |
c = 7.2155 (2) Å | µ = 3.39 mm−1 |
β = 113.095 (3)° | T = 293 K |
V = 772.41 (3) Å3 | Needle, beige |
Z = 4 | 0.32 × 0.18 × 0.10 mm |
XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer | Rint = 0.019 |
/ω scans | θmax = 71.1°, θmin = 4.9° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | h = −7→7 |
Tmin = 0.131, Tmax = 1.000 | k = −22→11 |
3645 measured reflections | l = −8→8 |
1480 independent reflections | 3 standard reflections every 100 reflections |
1366 reflections with I > 2σ(I) | intensity decay: 2.6% |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.2028P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
1480 reflections | Δρmax = 0.35 e Å−3 |
104 parameters | Δρmin = −0.33 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.38930 (7) | 0.23126 (2) | 0.56878 (7) | 0.03711 (17) | |
O2 | 0.9971 (2) | 0.40285 (7) | 0.5037 (2) | 0.0441 (3) | |
O1 | 0.7585 (2) | 0.48309 (7) | 0.5457 (3) | 0.0525 (4) | |
N2 | 0.7208 (2) | 0.29656 (8) | 0.5395 (2) | 0.0355 (3) | |
N3 | 0.7715 (3) | 0.22308 (8) | 0.5338 (2) | 0.0376 (4) | |
N1 | 0.4525 (3) | 0.37853 (8) | 0.5616 (3) | 0.0443 (4) | |
H3A | 0.532006 | 0.415948 | 0.555662 | 0.053* | |
H3B | 0.324769 | 0.385097 | 0.571813 | 0.053* | |
C5 | 0.9282 (3) | 0.46721 (9) | 0.5139 (3) | 0.0325 (4) | |
C1 | 0.5255 (3) | 0.31189 (9) | 0.5552 (3) | 0.0327 (4) | |
C2 | 0.6144 (3) | 0.18227 (10) | 0.5465 (3) | 0.0349 (4) | |
C3 | 0.6113 (4) | 0.09996 (10) | 0.5415 (3) | 0.0456 (5) | |
H1B | 0.482610 | 0.083694 | 0.423726 | 0.055* | |
H1C | 0.590798 | 0.081757 | 0.659693 | 0.055* | |
C4 | 0.8242 (4) | 0.06663 (12) | 0.5359 (4) | 0.0592 (6) | |
H2B | 0.812072 | 0.013808 | 0.532857 | 0.089* | |
H2C | 0.843836 | 0.083416 | 0.417603 | 0.089* | |
H2D | 0.952085 | 0.081478 | 0.653703 | 0.089* | |
H1 | 0.816 (4) | 0.3332 (16) | 0.530 (4) | 0.065 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0324 (3) | 0.0330 (3) | 0.0516 (3) | −0.00368 (16) | 0.0226 (2) | 0.00117 (17) |
O2 | 0.0398 (7) | 0.0253 (6) | 0.0797 (9) | −0.0001 (5) | 0.0368 (7) | −0.0005 (6) |
O1 | 0.0431 (8) | 0.0321 (7) | 0.1006 (11) | 0.0011 (6) | 0.0480 (8) | 0.0010 (7) |
N2 | 0.0316 (7) | 0.0275 (7) | 0.0542 (9) | 0.0018 (6) | 0.0243 (7) | 0.0047 (6) |
N3 | 0.0364 (8) | 0.0304 (7) | 0.0516 (9) | 0.0046 (6) | 0.0231 (7) | 0.0037 (6) |
N1 | 0.0372 (8) | 0.0303 (8) | 0.0750 (11) | 0.0040 (6) | 0.0324 (8) | 0.0048 (7) |
C5 | 0.0298 (8) | 0.0271 (8) | 0.0447 (9) | −0.0014 (7) | 0.0191 (7) | −0.0001 (7) |
C1 | 0.0274 (8) | 0.0329 (9) | 0.0405 (9) | 0.0007 (6) | 0.0163 (7) | 0.0037 (7) |
C2 | 0.0376 (9) | 0.0312 (9) | 0.0390 (9) | 0.0009 (7) | 0.0185 (7) | 0.0029 (7) |
C3 | 0.0579 (12) | 0.0298 (9) | 0.0549 (11) | 0.0000 (8) | 0.0282 (9) | 0.0009 (8) |
C4 | 0.0751 (15) | 0.0377 (11) | 0.0743 (14) | 0.0152 (11) | 0.0394 (12) | 0.0029 (10) |
S1—C1 | 1.7255 (17) | N1—H3B | 0.8600 |
S1—C2 | 1.7565 (18) | C5—C5i | 1.564 (3) |
O2—C5 | 1.260 (2) | C2—C3 | 1.492 (3) |
O1—C5 | 1.232 (2) | C3—C4 | 1.510 (3) |
N2—C1 | 1.332 (2) | C3—H1B | 0.9700 |
N2—N3 | 1.375 (2) | C3—H1C | 0.9700 |
N2—H1 | 0.92 (3) | C4—H2B | 0.9600 |
N3—C2 | 1.283 (2) | C4—H2C | 0.9600 |
N1—C1 | 1.303 (2) | C4—H2D | 0.9600 |
N1—H3A | 0.8600 | ||
C1—S1—C2 | 88.23 (8) | N3—C2—S1 | 114.42 (13) |
C1—N2—N3 | 116.50 (14) | C3—C2—S1 | 120.25 (14) |
C1—N2—H1 | 122.0 (17) | C2—C3—C4 | 113.38 (17) |
N3—N2—H1 | 121.5 (17) | C2—C3—H1B | 108.9 |
C2—N3—N2 | 110.74 (15) | C4—C3—H1B | 108.9 |
C1—N1—H3A | 120.0 | C2—C3—H1C | 108.9 |
C1—N1—H3B | 120.0 | C4—C3—H1C | 108.9 |
H3A—N1—H3B | 120.0 | H1B—C3—H1C | 107.7 |
O1—C5—O2 | 125.68 (16) | C3—C4—H2B | 109.5 |
O1—C5—C5i | 117.07 (18) | C3—C4—H2C | 109.5 |
O2—C5—C5i | 117.25 (18) | H2B—C4—H2C | 109.5 |
N1—C1—N2 | 124.08 (16) | C3—C4—H2D | 109.5 |
N1—C1—S1 | 125.82 (13) | H2B—C4—H2D | 109.5 |
N2—C1—S1 | 110.09 (13) | H2C—C4—H2D | 109.5 |
N3—C2—C3 | 125.32 (17) | ||
C1—N2—N3—C2 | −0.4 (2) | N2—N3—C2—S1 | −0.44 (19) |
N3—N2—C1—N1 | −179.71 (16) | C1—S1—C2—N3 | 0.89 (14) |
N3—N2—C1—S1 | 1.1 (2) | C1—S1—C2—C3 | −178.47 (15) |
C2—S1—C1—N1 | 179.76 (17) | N3—C2—C3—C4 | 4.6 (3) |
C2—S1—C1—N2 | −1.07 (13) | S1—C2—C3—C4 | −176.16 (15) |
N2—N3—C2—C3 | 178.87 (16) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3A···O1 | 0.86 | 1.92 | 2.765 (2) | 167 |
N1—H3B···O2ii | 0.86 | 1.99 | 2.821 (2) | 162 |
N2—H1···O2 | 0.92 (3) | 1.78 (3) | 2.6989 (19) | 178 (2) |
C3—H1C···O1iii | 0.97 | 2.65 | 3.479 (2) | 143 |
Symmetry codes: (ii) x−1, y, z; (iii) −x+3/2, y−1/2, −z+3/2. |
C7H11N2+·C8H5N2S3− | F(000) = 728 |
Mr = 348.50 | Dx = 1.336 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54184 Å |
a = 9.6422 (2) Å | Cell parameters from 6977 reflections |
b = 17.1758 (3) Å | θ = 2.5–70.7° |
c = 10.6080 (2) Å | µ = 3.92 mm−1 |
β = 99.546 (2)° | T = 293 K |
V = 1732.49 (6) Å3 | Needle, colourless |
Z = 4 | 0.20 × 0.17 × 0.12 mm |
XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer | 2681 reflections with I > 2σ(I) |
Detector resolution: 10.0000 pixels mm-1 | Rint = 0.047 |
/ω scans | θmax = 71.4°, θmin = 5.0° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | h = −11→11 |
Tmin = 0.123, Tmax = 1.000 | k = −18→21 |
16519 measured reflections | l = −13→12 |
3341 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.070P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3341 reflections | Δρmax = 0.43 e Å−3 |
234 parameters | Δρmin = −0.48 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.98676 (7) | 0.65986 (4) | 0.81645 (7) | 0.0706 (2) | |
S2 | 1.24460 (7) | 0.58869 (4) | 0.73915 (8) | 0.0745 (2) | |
S3 | 0.68531 (7) | 0.63843 (5) | 0.85224 (7) | 0.0758 (2) | |
N2 | 0.9940 (2) | 0.52129 (11) | 0.75216 (19) | 0.0578 (5) | |
N1 | 0.8566 (2) | 0.52989 (13) | 0.7759 (2) | 0.0655 (5) | |
N4 | 0.3738 (3) | 0.62373 (15) | 0.1821 (2) | 0.0773 (6) | |
N3 | 0.5545 (3) | 0.61788 (18) | 0.5594 (3) | 0.0861 (7) | |
C3 | 1.0350 (3) | 0.44426 (13) | 0.7193 (2) | 0.0592 (6) | |
C11 | 0.4299 (3) | 0.62077 (14) | 0.3046 (2) | 0.0597 (6) | |
C2 | 1.0800 (3) | 0.58276 (14) | 0.7660 (2) | 0.0581 (6) | |
C1 | 0.8367 (3) | 0.60132 (16) | 0.8129 (2) | 0.0601 (6) | |
C12 | 0.3763 (3) | 0.66388 (16) | 0.3991 (3) | 0.0679 (7) | |
C4 | 1.1299 (3) | 0.40347 (16) | 0.8063 (3) | 0.0704 (7) | |
C8 | 0.9777 (3) | 0.41273 (15) | 0.6033 (3) | 0.0706 (7) | |
C10 | 0.5502 (4) | 0.57518 (18) | 0.3494 (3) | 0.0783 (8) | |
C13 | 0.4416 (4) | 0.66102 (18) | 0.5222 (3) | 0.0781 (8) | |
C5 | 1.1668 (4) | 0.32861 (18) | 0.7750 (4) | 0.0859 (9) | |
C7 | 1.0156 (4) | 0.33772 (18) | 0.5741 (4) | 0.0852 (9) | |
C6 | 1.1092 (4) | 0.29664 (18) | 0.6601 (4) | 0.0890 (10) | |
C9 | 0.6068 (4) | 0.5752 (2) | 0.4736 (4) | 0.0905 (10) | |
C14 | 0.2475 (4) | 0.6678 (3) | 0.1364 (4) | 0.1091 (13) | |
H14A | 0.224003 | 0.662573 | 0.045294 | 0.164* | |
H14B | 0.171551 | 0.648329 | 0.175580 | 0.164* | |
H14C | 0.263244 | 0.721689 | 0.158169 | 0.164* | |
C15 | 0.4305 (5) | 0.5763 (2) | 0.0877 (4) | 0.1113 (12)* | |
H15A | 0.377399 | 0.585714 | 0.004314 | 0.167* | |
H15B | 0.527201 | 0.589807 | 0.088255 | 0.167* | |
H15C | 0.424084 | 0.522178 | 0.108847 | 0.167* | |
H8 | 0.910 (3) | 0.4407 (17) | 0.543 (3) | 0.076 (8)* | |
H12 | 0.302 (3) | 0.6942 (18) | 0.379 (3) | 0.073 (8)* | |
H4 | 1.168 (3) | 0.4241 (18) | 0.883 (3) | 0.083 (10)* | |
H5 | 1.235 (4) | 0.300 (2) | 0.840 (3) | 0.104 (11)* | |
H6 | 1.130 (4) | 0.247 (2) | 0.638 (4) | 0.107 (11)* | |
H7 | 0.976 (4) | 0.316 (2) | 0.490 (4) | 0.094 (10)* | |
H13 | 0.411 (4) | 0.689 (2) | 0.582 (3) | 0.094 (11)* | |
H11 | 0.594 (4) | 0.544 (2) | 0.297 (4) | 0.103 (11)* | |
H9 | 0.689 (4) | 0.549 (2) | 0.509 (4) | 0.112 (12)* | |
H3 | 0.596 (5) | 0.619 (3) | 0.654 (5) | 0.141 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0638 (4) | 0.0629 (4) | 0.0867 (5) | 0.0005 (3) | 0.0171 (3) | −0.0164 (3) |
S2 | 0.0614 (4) | 0.0636 (4) | 0.1027 (6) | −0.0064 (3) | 0.0262 (4) | −0.0117 (3) |
S3 | 0.0628 (4) | 0.0961 (5) | 0.0710 (4) | 0.0094 (3) | 0.0188 (3) | −0.0041 (3) |
N2 | 0.0532 (10) | 0.0552 (10) | 0.0656 (12) | −0.0011 (8) | 0.0111 (9) | −0.0017 (9) |
N1 | 0.0545 (11) | 0.0690 (13) | 0.0740 (13) | −0.0029 (9) | 0.0140 (10) | −0.0001 (10) |
N4 | 0.0913 (17) | 0.0815 (16) | 0.0605 (13) | −0.0169 (13) | 0.0170 (12) | −0.0015 (11) |
N3 | 0.0877 (18) | 0.0956 (19) | 0.0729 (17) | −0.0155 (15) | 0.0071 (14) | 0.0087 (14) |
C3 | 0.0622 (13) | 0.0476 (12) | 0.0691 (15) | −0.0027 (10) | 0.0144 (11) | 0.0033 (10) |
C11 | 0.0661 (14) | 0.0540 (12) | 0.0633 (14) | −0.0110 (10) | 0.0235 (11) | 0.0004 (10) |
C2 | 0.0612 (13) | 0.0561 (13) | 0.0570 (13) | −0.0007 (10) | 0.0093 (10) | −0.0025 (10) |
C1 | 0.0578 (13) | 0.0724 (15) | 0.0501 (12) | 0.0025 (11) | 0.0086 (10) | 0.0009 (11) |
C12 | 0.0692 (16) | 0.0629 (15) | 0.0768 (18) | 0.0049 (12) | 0.0272 (14) | 0.0039 (12) |
C4 | 0.0733 (17) | 0.0611 (15) | 0.0756 (18) | −0.0016 (12) | 0.0087 (14) | 0.0102 (13) |
C8 | 0.0805 (18) | 0.0574 (14) | 0.0718 (17) | −0.0006 (12) | 0.0066 (14) | −0.0005 (12) |
C10 | 0.0807 (19) | 0.0698 (17) | 0.091 (2) | 0.0110 (14) | 0.0347 (17) | −0.0001 (15) |
C13 | 0.100 (2) | 0.0739 (18) | 0.0672 (18) | −0.0099 (16) | 0.0321 (17) | −0.0075 (14) |
C5 | 0.086 (2) | 0.0613 (17) | 0.110 (3) | 0.0093 (14) | 0.0164 (19) | 0.0230 (17) |
C7 | 0.112 (3) | 0.0602 (16) | 0.086 (2) | −0.0047 (16) | 0.0224 (19) | −0.0119 (15) |
C6 | 0.100 (2) | 0.0514 (15) | 0.121 (3) | 0.0044 (15) | 0.035 (2) | 0.0034 (17) |
C9 | 0.076 (2) | 0.098 (2) | 0.098 (3) | 0.0119 (17) | 0.0139 (18) | 0.0213 (19) |
C14 | 0.096 (3) | 0.135 (3) | 0.088 (2) | −0.019 (2) | −0.009 (2) | 0.029 (2) |
S1—C2 | 1.735 (2) | C4—C5 | 1.389 (4) |
S1—C1 | 1.757 (3) | C4—H4 | 0.91 (3) |
S2—C2 | 1.661 (3) | C8—C7 | 1.388 (4) |
S3—C1 | 1.707 (3) | C8—H8 | 0.96 (3) |
N2—C2 | 1.336 (3) | C10—C9 | 1.340 (5) |
N2—N1 | 1.397 (3) | C10—H11 | 0.93 (4) |
N2—C3 | 1.440 (3) | C13—H13 | 0.89 (3) |
N1—C1 | 1.312 (3) | C5—C6 | 1.368 (5) |
N4—C11 | 1.323 (4) | C5—H5 | 1.00 (4) |
N4—C14 | 1.447 (5) | C7—C6 | 1.368 (5) |
N4—C15 | 1.465 (5) | C7—H7 | 0.98 (4) |
N3—C13 | 1.322 (5) | C6—H6 | 0.92 (4) |
N3—C9 | 1.331 (5) | C9—H9 | 0.94 (4) |
N3—H3 | 1.02 (5) | C14—H14A | 0.9600 |
C3—C8 | 1.374 (4) | C14—H14B | 0.9600 |
C3—C4 | 1.378 (4) | C14—H14C | 0.9600 |
C11—C12 | 1.411 (4) | C15—H15A | 0.9600 |
C11—C10 | 1.415 (4) | C15—H15B | 0.9600 |
C12—C13 | 1.353 (5) | C15—H15C | 0.9600 |
C12—H12 | 0.88 (3) | ||
C2—S1—C1 | 91.37 (12) | C7—C8—H8 | 119.5 (17) |
C2—N2—N1 | 119.1 (2) | C9—C10—C11 | 120.5 (3) |
C2—N2—C3 | 124.2 (2) | C9—C10—H11 | 116 (2) |
N1—N2—C3 | 116.58 (19) | C11—C10—H11 | 124 (2) |
C1—N1—N2 | 110.1 (2) | N3—C13—C12 | 122.4 (3) |
C11—N4—C14 | 122.2 (3) | N3—C13—H13 | 117 (2) |
C11—N4—C15 | 120.8 (3) | C12—C13—H13 | 121 (2) |
C14—N4—C15 | 116.8 (3) | C6—C5—C4 | 120.2 (3) |
C13—N3—C9 | 119.5 (3) | C6—C5—H5 | 123 (2) |
C13—N3—H3 | 117 (3) | C4—C5—H5 | 117 (2) |
C9—N3—H3 | 124 (3) | C6—C7—C8 | 120.0 (3) |
C8—C3—C4 | 121.6 (2) | C6—C7—H7 | 121 (2) |
C8—C3—N2 | 119.6 (2) | C8—C7—H7 | 119 (2) |
C4—C3—N2 | 118.9 (2) | C7—C6—C5 | 120.8 (3) |
N4—C11—C12 | 122.6 (3) | C7—C6—H6 | 117 (2) |
N4—C11—C10 | 122.0 (3) | C5—C6—H6 | 122 (2) |
C12—C11—C10 | 115.4 (3) | N3—C9—C10 | 122.2 (3) |
N2—C2—S2 | 128.55 (19) | N3—C9—H9 | 113 (2) |
N2—C2—S1 | 107.04 (18) | C10—C9—H9 | 125 (2) |
S2—C2—S1 | 124.40 (15) | N4—C14—H14A | 109.5 |
N1—C1—S3 | 126.6 (2) | N4—C14—H14B | 109.5 |
N1—C1—S1 | 112.37 (18) | H14A—C14—H14B | 109.5 |
S3—C1—S1 | 121.04 (16) | N4—C14—H14C | 109.5 |
C13—C12—C11 | 120.0 (3) | H14A—C14—H14C | 109.5 |
C13—C12—H12 | 119 (2) | H14B—C14—H14C | 109.5 |
C11—C12—H12 | 121 (2) | N4—C15—H15A | 109.5 |
C3—C4—C5 | 118.6 (3) | N4—C15—H15B | 109.5 |
C3—C4—H4 | 122 (2) | H15A—C15—H15B | 109.5 |
C5—C4—H4 | 120 (2) | N4—C15—H15C | 109.5 |
C3—C8—C7 | 118.9 (3) | H15A—C15—H15C | 109.5 |
C3—C8—H8 | 121.6 (17) | H15B—C15—H15C | 109.5 |
C2—N2—N1—C1 | −1.6 (3) | C2—S1—C1—N1 | −0.3 (2) |
C3—N2—N1—C1 | 175.7 (2) | C2—S1—C1—S3 | −179.33 (16) |
C2—N2—C3—C8 | −113.1 (3) | N4—C11—C12—C13 | −177.2 (3) |
N1—N2—C3—C8 | 69.7 (3) | C10—C11—C12—C13 | 1.4 (4) |
C2—N2—C3—C4 | 67.7 (3) | C8—C3—C4—C5 | −0.4 (4) |
N1—N2—C3—C4 | −109.4 (3) | N2—C3—C4—C5 | 178.7 (3) |
C14—N4—C11—C12 | −4.0 (4) | C4—C3—C8—C7 | 0.6 (4) |
C15—N4—C11—C12 | −178.3 (3) | N2—C3—C8—C7 | −178.5 (3) |
C14—N4—C11—C10 | 177.5 (3) | N4—C11—C10—C9 | 178.1 (3) |
C15—N4—C11—C10 | 3.2 (4) | C12—C11—C10—C9 | −0.5 (4) |
N1—N2—C2—S2 | −177.69 (18) | C9—N3—C13—C12 | −0.2 (5) |
C3—N2—C2—S2 | 5.2 (4) | C11—C12—C13—N3 | −1.1 (5) |
N1—N2—C2—S1 | 1.3 (3) | C3—C4—C5—C6 | −0.2 (5) |
C3—N2—C2—S1 | −175.83 (19) | C3—C8—C7—C6 | −0.3 (5) |
C1—S1—C2—N2 | −0.50 (18) | C8—C7—C6—C5 | −0.2 (5) |
C1—S1—C2—S2 | 178.52 (17) | C4—C5—C6—C7 | 0.5 (5) |
N2—N1—C1—S3 | 179.97 (17) | C13—N3—C9—C10 | 1.2 (5) |
N2—N1—C1—S1 | 1.0 (3) | C11—C10—C9—N3 | −0.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S3 | 1.02 (5) | 2.16 (5) | 3.173 (3) | 173 (4) |
Funding information
Funding for this research was provided by: Ministry of Innovation of the Republic of Uzbekistan.
References
Berceanc, V., Crainic, C., Haiduc, I., Mahon, M. F., Molloy, K. C., Venter, M. M. & Wilson, P. J. (2002). J. Chem. Soc. Dalton Trans. pp. 1036–1045. Web of Science CSD CrossRef Google Scholar
Etter, M. C. (1993). Acc. Chem. Res. 32, 120–126. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Harris, J. M., Struck, E. C., Case, M. G., Paley, M. S., Yalpani, M., Van Alstine, J. M. & Brooks, D. E. (1984). J. Polym. Sci. Polym. Chem. Ed. 22, 341–352. CrossRef CAS Web of Science Google Scholar
Kurtzer, F., Katritzky, A. R. & Boulton, A. J. (1965). Advances in Heterocyclic Chemistry, pp. 165–209. New York: Academic Press. Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Priya, B. S., Basappa, B., Nanjunda Swamy, S. & Rangappa, K. S. (2005). Bioorg. Med. Chem. 13, 2623–2628. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku OD (2020). CrysAlis PRO. Rigaku Corporation, Wroclaw, Poland. Google Scholar
Sadashiva, M. P., Mallesha, H., Hitesh, N. A. & Rangappa, K. S. (2004). Bioorg. Med. Chem. 12, 6389–6395. Web of Science CrossRef PubMed CAS Google Scholar
Sharma, B., Verma, A., Prajapati, S. & Sharma, U. K. (2013). Int. J. Med. Chem. https://doi.org/10.1155/2013/348948. Google Scholar
Sheikh, M. C., Takagi, S., Yoshimura, T. & Morita, H. (2010). Tetrahedron, 66, 7272–7278. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shivarama Holla, B., Narayana Poojary, K., Sooryanarayana Rao, B. & Shivananda, M. K. (2002). Eur. J. Med. Chem. 37, 511–517. CrossRef PubMed CAS Google Scholar
Siemens (1994). XP. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Smith, G., Cooper, C. J., Chauhan, V., Lynch, D. E., Parsons, S. & Healy, P. (1999). Aust. J. Chem. 52, 695–703. CSD CrossRef Google Scholar
Song, Y., Connor, D. T., Sercel, A. D., Sorenson, R. J., Doubleday, R., Unangst, P. C., Roth, B. D., Beylin, V. G., Gilbertsen, R. B., Chan, K., Schrier, D. J., Guglietta, A., Bornemeier, D. A. & Dyer, R. D. (1999). J. Med. Chem. 42, 1161–1169. Web of Science CrossRef PubMed CAS Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17.5. University of Western Australia. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Witkoaski, J. T., Robins, R. K., Sidwell, R. W. & Simon, L. N. (1972). J. Med. Chem. 15, 150–154. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.