research communications
2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol: and Hirshfeld surface analysis
aDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor Darul Ehsan, Malaysia, bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and cResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The title dithiocarbazate ester, C16H16N2O2S2, comprises two almost planar residues, i.e. the phenyl ring and the remaining 14 non-H atoms (r.m.s. deviation = 0.0410 Å). These are orientated perpendicularly, forming a dihedral angle of 82.72 (5)°. An intramolecular hydroxy-O—H⋯N(imine) hydrogen bond, leading to an S(6) loop, is noted. An analysis of the geometric parameters is consistent with the molecule existing as the thione tautomer, and the conformation about the C=N bond is E. The thione S and imine H atoms lie to the same side of the molecule, facilitating the formation of intermolecular N—H⋯S hydrogen bonds leading to eight-membered {⋯HNCS}2 synthons in the crystal. These aggregates are connected by phenyl-C—H⋯O(hydroxy) interactions into a supramolecular layer in the bc plane; these stack with no directional interactions between them. An analysis of the Hirshfeld surface confirms the nature of the intermolecular interactions.
CCDC reference: 1465209
1. Chemical context
Dithiocarbazate, NH2NHC(=S)S−, and more specifically substituted derivatives, have attracted the attention of researchers for decades (Ali & Livingstone, 1974). While a common motivation for investigating transition metal complexes of these anions relates to potential biological activity (Basha et al., 2012; Vijayan et al., 2015), including our own recent work (Yusof, Ravoof, Jamsari et al., 2015; Yusof, Ravoof, Tiekink et al., 2015), other motivations exist. Thus, recent studies have described the photo-catalytic production of hydrogen mediated by a conjugated nickel(II) bis-dithiocarbazate complex (Wise et al., 2015). The use of a coumarin-based dithiocarbazate as a ratiometric and colormetric chemosensor for cobalt(II) is another recent development (Liu et al., 2015). In rationalizing the electronic structures of metal dithiocarbazates, a knowledge of the uncomplexed or `free ligand' structure is most useful. In keeping with this notion and as a part of an on-going study of the structural chemistry of metal dithiocarbazates and their ligands, the title compound was prepared and characterized both crystallographically and by a Hirshfeld surface analysis.
2. Structural commentary
The title compound, Fig. 1, comprises two almost planar regions, one being the phenyl ring, the other being the remaining 14 non-hydrogen atoms. The maximum deviations from the least-squares plane through the latter plane, with a r.m.s. deviation = 0.0410 Å, are 0.0715 (15) for the O1 atom and −0.0796 (18) for atom C16. To a first approximation, the molecule can be described as having mirror symmetry with the 1,4-atoms of the terminal ring being bisected by the plane. Substantiating this description is the dihedral angle between the planes of 82.72 (5)°, indicating a very close to perpendicular relationship. The observed planarity in the larger fragment may be ascribed, in part, to the presence of an intramolecular hydroxy-O—H⋯N(imine) hydrogen bond (Table 1), which leads to the formation of an S(6) loop. The molecule exists in the thione tautomeric form. Consistent with this assignment, the thione C1=S2 bond length, i.e. 1.670 (2) Å, is considerably shorter than the thiol C1—S1 and, especially, C2—S1 bonds of 1.749 (2) and 1.817 (2) Å, respectively. The conformation about the C=N bond is E, and the amine-N—H atom is flanked on either side by the thione-S and imine-H atoms.
3. Supramolecular features
The most prominent feature of the packing of the title compound is the formation of centrosymmetric, eight-membered {⋯HNCS}2 synthons through the agency of thioamide-N—H⋯S(thione) hydrogen bonds, Table 1. The dimeric aggregates are connected by phenyl-C—H⋯O(hydroxy) interactions to form a supramolecular layer in the bc-plane, Fig. 2a. The layers stack along the a axis with no directional interactions between them, Fig. 2b.
4. Analysis of the Hirshfeld surfaces
Crystal Explorer 3.1 (Wolff et al., 2012) was used to generate Hirshfeld surfaces mapped over dnorm, de, curvedness and electrostatic potential. The latter was calculated using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) which was integrated into Crystal Explorer; the experimental geometry was used as the input. Further, the electrostatic potentials were mapped on the Hirshfeld surface using the STO-3G basis set at the Hartree–Fock level of theory over the range ±0.1 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (Rohl et al., 2008) provides a summary of the intermolecular contacts in the crystal.
From the view of the Hirshfeld surface mapped over dnorm, Fig. 3, the deep-red depressions at atoms H1N and S2 confirm their role as the N—H⋯S hydrogen-bond donor and acceptor, respectively. On the surface mapped over the electrostatic potential, Fig. 4, these atoms appear as the respective blue and red regions. The light-red spots near the phenyl-hydrogen atom, H6, and hydroxyl oxygen, O1, on the dnorm-mapped surface indicate the intermolecular C—H⋯O interaction between them. The immediate environment about the molecule within dnorm-mapped Hirshfeld surface mediated by the above interactions is illustrated in Fig. 5.
The overall two-dimensional fingerprint (FP) plot, Fig. 6a, and those delineated into H⋯H, O⋯H/H⋯O, S⋯H/H⋯S, C⋯H/H⋯C and C⋯C interactions are illustrated in Fig. 6b–f; the relative contributions are summarized in Table 2. The H⋯H contacts appear as the scattered points in nearly the entire plot, Fig. 6b, and make a significant contribution, i.e. 43.4%, to the Hirshfeld surface. The round single peak at de + di ∼ 2.3 Å results from a short interatomic H⋯H contact, Table 3. The FP delineated into O⋯H/H⋯O contacts show a pair of short spikes at de + di ∼ 2.5 Å and the small arcs linked to them are identified with labels 1 and 2 in Fig. 6c. These features correspond to a 10.3% contribution to the Hirshfeld surfaces and reflect the presence of intermolecular C—H⋯O interactions as well as interatomic O⋯H contacts only slightly shorter than their van der Waals separation, i.e. around de + di ∼ 2.7 Å, Table 3. The presence of intermolecular N—H⋯S hydrogen bonds in the crystal is evident from a prominent pair of sharp spikes in the outer region of the FP plot shown in Fig. 6d, i.e. at de + di ∼ 2.45 Å, with a 14.4% contribution to the Hirshfeld surface. The distinct pair of wings corresponding to C⋯H/H⋯C contacts, Fig. 6e, have `forceps-like' tips at de + di ∼ 2.8 Å due to short interatomic C⋯H/H⋯C contacts, Table 3, although C—H⋯π interactions are not evident in the structure within the sum of their van der Waals radii. The 2.5% contribution from C⋯C contacts to the Hirshfeld surface features two overlapping triangles, Fig. 6f, but the minimum (de + di) distance is greater than van der Waals separation, confirming the absence of π–π stacking interactions. This is also evident from the small segments delineated by blue outlines in the Hirshfeld surface mapped over curvedness, Fig. 7.
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The enrichment ratio (ER), based on Hirshfeld surface analysis, gives further description of intermolecular interactions operating in a crystal (Jelsch et al., 2014). The ER values are summarized in Table 4. The ER value close to but slightly less than unity, i.e. 0.97, for H⋯H contacts is in accord with expectation (Jelsch et al., 2014). The sulfur atoms comprise 9.5% of Hirshfeld surface and the overall 14.4% contribution by S⋯H/H⋯S contacts results in an ER value of 1.14, which is in the expected range for N—H⋯S interactions, i.e. 1.0–1.5 (Jelsch et al., 2014). The ER value of 1.28 corresponding to O⋯H/H⋯O contacts show a high propensity to form even though the percentage relative contribution to the overall surface, i.e. 10.3%, is small as is the 6.0% exposure provided by hydroxyl- and methoxy-oxygen atoms. The low ER value of 1.09 corresponding to C⋯C contacts is consistent with a low propensity for π–π stacking interactions in the structure. The presence of short interatomic non-bonded C⋯H/H⋯C contacts result in an ER value close to unity, Table 4, as there is little influence of C—H⋯π interactions on the molecular packing. The other contributions to the surface i.e. N⋯H/H⋯N, S⋯S, S⋯O/O⋯S, C⋯S/S⋯C, etc. are very small and therefore, the ER values are not particularly informative although being > 1 for some interactions.
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5. Database survey
Dithiocarbazate S-esters are well studied with many examples included in the Cambridge Structural Database (Groom & Allen, 2014).
There are three examples, II–IV, of derivatives with a hydroxy group in the 2-position of the ring connected to the imine-C atom (Madanhire et al., 2015; Sethuraman et al., 2002; Begum et al., 2016), with their chemical diagrams shown in Scheme 2. Interestingly, there are four virtually identical molecules comprising the in IV (Begum et al., 2016). A common feature of each of I–IV, is the formation of an intramolecular hydroxy-O—H⋯N(imine) hydrogen bond. By contrast to I, each of the molecules in II–IV is effectively planar. Reflecting the interest in the structural chemistry of this class of compound, there are several structures of S-benzyl with methoxy-substituted terminal rings (Fan et al., 2011a; Fan et al., 2011b; Tan et al., 2015), see Scheme 2 for chemical structures. In each of V–VII, each methoxy group is co-planar with the benzene ring to which it is connected. To a first approximation, the molecules in V and VII adopt approximately the same conformation as in I, i.e. with all but the benzyl rings lying in a plane. The dihedral angles between the two residues are 85.23 (12)° in V and 63.01 (8)° in VII. By contrast, a somewhat twisted conformation is observed for each of the two independent molecules in VI.
6. Synthesis and crystallization
Following procedures adapted from the literature (Ali & Tarafder, 1977), S-benzyldithiocarbazate (SBDTC) (1.98 g, 0.01 mol) was dissolved in hot absolute ethanol (100 cm3) and added to an equimolar amount of 2-hydroxy-3-methoxybenzaldehyde (Merck, 1.52 g) in absolute ethanol (20 cm3). The mixture was heated with continuous stirring for about 30 min and was then allowed to stand overnight. The light-yellow crystals that formed were filtered and washed with absolute ethanol at room temperature. Yield: 70%. M.p.: 446–447 K. Analysis calculated for C16H16N2O2S2: C, 57.81; H, 4.85; N, 8.43. Found: C, 58.21; H, 4.87; N, 8.28%. FT–IR (ATR, cm−1): 3089, ν(N—H); 1598, ν(C=N); 1030, ν(N—N); 720, ν(C=S). 13C NMR (DMSO-d6) δ (p.p.m.): 196.09 (C=S), 148.59 (C=N); 147.45–114.43 (aromatic-C), 56.43 (CH3), 38.10 (CH2). m/z calculated for C16H16N2O2S2 332.44, found 332.
7. Refinement
Crystal data, data collection and structure . The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H-atoms were located in a difference Fourier map but were refined with distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).
details are summarized in Table 5Supporting information
CCDC reference: 1465209
https://doi.org/10.1107/S2056989016004291/hb7572sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016004291/hb7572Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016004291/hb7572Isup3.cml
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C16H16N2O2S2 | F(000) = 1392 |
Mr = 332.43 | Dx = 1.396 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.7896 (10) Å | Cell parameters from 2185 reflections |
b = 4.6965 (2) Å | θ = 2–29° |
c = 32.5217 (13) Å | µ = 0.35 mm−1 |
β = 95.004 (4)° | T = 100 K |
V = 3163.3 (2) Å3 | Plate, light-yellow |
Z = 8 | 0.25 × 0.15 × 0.07 mm |
Agilent Xcalibur Eos Gemini diffractometer | 3270 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2595 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 16.1952 pixels mm-1 | θmax = 26.5°, θmin = 2.4° |
ω scans | h = −25→26 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −5→5 |
Tmin = 0.87, Tmax = 0.98 | l = −27→40 |
6979 measured reflections |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0382P)2 + 1.7624P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max = 0.002 |
S = 1.06 | Δρmax = 0.33 e Å−3 |
3270 reflections | Δρmin = −0.24 e Å−3 |
206 parameters |
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 | 0.22247 (2) | 0.46299 (12) | 0.61684 (2) | 0.02185 (15) | |
S2 | 0.17478 (3) | 0.80851 (12) | 0.54164 (2) | 0.02258 (15) | |
O1 | 0.35672 (7) | −0.0373 (3) | 0.63252 (4) | 0.0239 (3) | |
H1O | 0.3342 (10) | 0.086 (4) | 0.6194 (7) | 0.036* | |
O2 | 0.43677 (8) | −0.4115 (3) | 0.66547 (5) | 0.0305 (4) | |
N1 | 0.27458 (8) | 0.4630 (4) | 0.54712 (5) | 0.0203 (4) | |
H1N | 0.2819 (10) | 0.519 (5) | 0.5223 (4) | 0.024* | |
N2 | 0.31479 (8) | 0.2682 (4) | 0.56753 (5) | 0.0194 (4) | |
C1 | 0.22604 (9) | 0.5777 (4) | 0.56594 (6) | 0.0179 (4) | |
C2 | 0.15287 (10) | 0.6579 (5) | 0.63209 (6) | 0.0237 (5) | |
H2A | 0.1579 | 0.8639 | 0.6268 | 0.028* | |
H2B | 0.1130 | 0.5907 | 0.6161 | 0.028* | |
C3 | 0.14873 (10) | 0.6059 (5) | 0.67741 (6) | 0.0223 (5) | |
C4 | 0.18779 (13) | 0.7499 (6) | 0.70649 (8) | 0.0395 (6) | |
H4 | 0.2181 | 0.8838 | 0.6979 | 0.047* | |
C5 | 0.18365 (13) | 0.7029 (6) | 0.74845 (8) | 0.0432 (7) | |
H5 | 0.2108 | 0.8059 | 0.7682 | 0.052* | |
C6 | 0.14056 (12) | 0.5086 (5) | 0.76139 (7) | 0.0356 (6) | |
H6 | 0.1381 | 0.4735 | 0.7900 | 0.043* | |
C7 | 0.10141 (14) | 0.3670 (7) | 0.73262 (8) | 0.0502 (8) | |
H7 | 0.0708 | 0.2346 | 0.7413 | 0.060* | |
C8 | 0.10538 (13) | 0.4127 (6) | 0.69076 (8) | 0.0404 (7) | |
H8 | 0.0779 | 0.3096 | 0.6712 | 0.048* | |
C9 | 0.35930 (10) | 0.1553 (4) | 0.54759 (6) | 0.0192 (4) | |
H9 | 0.3635 | 0.2118 | 0.5199 | 0.023* | |
C10 | 0.40308 (9) | −0.0564 (4) | 0.56664 (6) | 0.0188 (4) | |
C11 | 0.40002 (9) | −0.1423 (4) | 0.60766 (6) | 0.0191 (4) | |
C12 | 0.44376 (10) | −0.3469 (5) | 0.62508 (7) | 0.0236 (5) | |
C13 | 0.48986 (10) | −0.4610 (5) | 0.60167 (7) | 0.0282 (5) | |
H13 | 0.5196 | −0.5984 | 0.6134 | 0.034* | |
C14 | 0.49292 (11) | −0.3747 (5) | 0.56070 (7) | 0.0286 (5) | |
H14 | 0.5246 | −0.4541 | 0.5448 | 0.034* | |
C15 | 0.45042 (10) | −0.1762 (5) | 0.54345 (7) | 0.0239 (5) | |
H15 | 0.4529 | −0.1189 | 0.5156 | 0.029* | |
C16 | 0.47583 (12) | −0.6366 (5) | 0.68359 (8) | 0.0346 (6) | |
H16A | 0.4679 | −0.8109 | 0.6674 | 0.052* | |
H16B | 0.4649 | −0.6693 | 0.7119 | 0.052* | |
H16C | 0.5215 | −0.5840 | 0.6839 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0221 (3) | 0.0271 (3) | 0.0169 (3) | 0.0071 (2) | 0.0051 (2) | 0.0040 (2) |
S2 | 0.0225 (3) | 0.0273 (3) | 0.0180 (3) | 0.0075 (2) | 0.0024 (2) | 0.0047 (2) |
O1 | 0.0258 (8) | 0.0281 (9) | 0.0183 (7) | 0.0072 (7) | 0.0044 (6) | 0.0034 (7) |
O2 | 0.0399 (9) | 0.0269 (9) | 0.0238 (8) | 0.0075 (7) | −0.0035 (7) | 0.0064 (7) |
N1 | 0.0206 (9) | 0.0253 (10) | 0.0154 (8) | 0.0044 (8) | 0.0040 (7) | 0.0058 (8) |
N2 | 0.0180 (8) | 0.0208 (9) | 0.0194 (9) | 0.0039 (7) | 0.0024 (7) | 0.0026 (8) |
C1 | 0.0181 (10) | 0.0179 (10) | 0.0176 (10) | −0.0018 (8) | 0.0016 (8) | 0.0000 (9) |
C2 | 0.0239 (11) | 0.0257 (12) | 0.0222 (11) | 0.0080 (9) | 0.0061 (9) | 0.0038 (10) |
C3 | 0.0234 (11) | 0.0231 (12) | 0.0212 (11) | 0.0093 (9) | 0.0059 (9) | 0.0005 (9) |
C4 | 0.0430 (15) | 0.0457 (16) | 0.0293 (13) | −0.0093 (13) | 0.0010 (12) | 0.0040 (12) |
C5 | 0.0523 (17) | 0.0504 (17) | 0.0258 (13) | −0.0002 (14) | −0.0034 (12) | −0.0029 (13) |
C6 | 0.0411 (14) | 0.0470 (16) | 0.0200 (11) | 0.0152 (12) | 0.0103 (11) | 0.0032 (12) |
C7 | 0.0549 (18) | 0.066 (2) | 0.0310 (14) | −0.0188 (16) | 0.0104 (13) | 0.0078 (14) |
C8 | 0.0493 (16) | 0.0480 (16) | 0.0244 (12) | −0.0172 (13) | 0.0063 (12) | −0.0001 (12) |
C9 | 0.0225 (10) | 0.0203 (11) | 0.0150 (10) | −0.0017 (9) | 0.0028 (9) | 0.0010 (9) |
C10 | 0.0184 (10) | 0.0170 (10) | 0.0210 (10) | −0.0013 (9) | 0.0015 (8) | −0.0030 (9) |
C11 | 0.0185 (10) | 0.0189 (11) | 0.0197 (10) | −0.0013 (8) | 0.0004 (9) | −0.0039 (9) |
C12 | 0.0264 (11) | 0.0194 (11) | 0.0239 (11) | −0.0004 (9) | −0.0046 (9) | −0.0011 (9) |
C13 | 0.0239 (11) | 0.0238 (12) | 0.0355 (13) | 0.0068 (10) | −0.0067 (10) | −0.0046 (11) |
C14 | 0.0228 (11) | 0.0301 (13) | 0.0331 (13) | 0.0063 (10) | 0.0035 (10) | −0.0077 (11) |
C15 | 0.0223 (11) | 0.0269 (12) | 0.0228 (11) | 0.0012 (9) | 0.0041 (9) | −0.0030 (10) |
C16 | 0.0411 (14) | 0.0237 (13) | 0.0363 (14) | −0.0008 (11) | −0.0129 (12) | 0.0070 (11) |
S1—C1 | 1.749 (2) | C6—C7 | 1.359 (4) |
S1—C2 | 1.817 (2) | C6—H6 | 0.9500 |
S2—C1 | 1.670 (2) | C7—C8 | 1.388 (3) |
O1—C11 | 1.354 (2) | C7—H7 | 0.9500 |
O1—H1O | 0.836 (10) | C8—H8 | 0.9500 |
O2—C12 | 1.368 (3) | C9—C10 | 1.450 (3) |
O2—C16 | 1.429 (3) | C9—H9 | 0.9500 |
N1—C1 | 1.338 (2) | C10—C11 | 1.401 (3) |
N1—N2 | 1.371 (2) | C10—C15 | 1.408 (3) |
N1—H1N | 0.874 (9) | C11—C12 | 1.408 (3) |
N2—C9 | 1.290 (2) | C12—C13 | 1.383 (3) |
C2—C3 | 1.504 (3) | C13—C14 | 1.400 (3) |
C2—H2A | 0.9900 | C13—H13 | 0.9500 |
C2—H2B | 0.9900 | C14—C15 | 1.370 (3) |
C3—C4 | 1.370 (3) | C14—H14 | 0.9500 |
C3—C8 | 1.376 (3) | C15—H15 | 0.9500 |
C4—C5 | 1.392 (3) | C16—H16A | 0.9800 |
C4—H4 | 0.9500 | C16—H16B | 0.9800 |
C5—C6 | 1.370 (4) | C16—H16C | 0.9800 |
C5—H5 | 0.9500 | ||
C1—S1—C2 | 101.75 (10) | C3—C8—C7 | 120.5 (2) |
C11—O1—H1O | 108.6 (16) | C3—C8—H8 | 119.7 |
C12—O2—C16 | 117.13 (17) | C7—C8—H8 | 119.7 |
C1—N1—N2 | 119.96 (16) | N2—C9—C10 | 121.21 (18) |
C1—N1—H1N | 120.0 (15) | N2—C9—H9 | 119.4 |
N2—N1—H1N | 120.0 (15) | C10—C9—H9 | 119.4 |
C9—N2—N1 | 117.70 (17) | C11—C10—C15 | 119.1 (2) |
N1—C1—S2 | 121.37 (15) | C11—C10—C9 | 121.72 (18) |
N1—C1—S1 | 113.89 (15) | C15—C10—C9 | 119.15 (18) |
S2—C1—S1 | 124.74 (11) | O1—C11—C10 | 123.47 (19) |
C3—C2—S1 | 107.49 (14) | O1—C11—C12 | 116.60 (18) |
C3—C2—H2A | 110.2 | C10—C11—C12 | 119.92 (18) |
S1—C2—H2A | 110.2 | O2—C12—C13 | 125.4 (2) |
C3—C2—H2B | 110.2 | O2—C12—C11 | 114.77 (18) |
S1—C2—H2B | 110.2 | C13—C12—C11 | 119.8 (2) |
H2A—C2—H2B | 108.5 | C12—C13—C14 | 120.2 (2) |
C4—C3—C8 | 118.2 (2) | C12—C13—H13 | 119.9 |
C4—C3—C2 | 121.0 (2) | C14—C13—H13 | 119.9 |
C8—C3—C2 | 120.8 (2) | C15—C14—C13 | 120.4 (2) |
C3—C4—C5 | 121.0 (2) | C15—C14—H14 | 119.8 |
C3—C4—H4 | 119.5 | C13—C14—H14 | 119.8 |
C5—C4—H4 | 119.5 | C14—C15—C10 | 120.6 (2) |
C6—C5—C4 | 120.3 (3) | C14—C15—H15 | 119.7 |
C6—C5—H5 | 119.8 | C10—C15—H15 | 119.7 |
C4—C5—H5 | 119.8 | O2—C16—H16A | 109.5 |
C7—C6—C5 | 118.8 (2) | O2—C16—H16B | 109.5 |
C7—C6—H6 | 120.6 | H16A—C16—H16B | 109.5 |
C5—C6—H6 | 120.6 | O2—C16—H16C | 109.5 |
C6—C7—C8 | 121.1 (3) | H16A—C16—H16C | 109.5 |
C6—C7—H7 | 119.4 | H16B—C16—H16C | 109.5 |
C8—C7—H7 | 119.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N2 | 0.84 (2) | 1.90 (2) | 2.639 (2) | 146 (2) |
N1—H1N···S2i | 0.88 (2) | 2.47 (2) | 3.3351 (18) | 168 (2) |
C6—H6···O1ii | 0.95 | 2.51 | 3.453 (3) | 170 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2. |
Contact | % |
H···H | 43.4 |
O···H/H···O | 10.3 |
S···H/H···S | 14.4 |
C···H/H···C | 21.3 |
N···H/H···N | 0.8 |
C···C | 2.5 |
S···S | 0.4 |
C···N/N···C | 2.9 |
S···O/O···S | 1.4 |
S···N/N···S | 1.4 |
C···S/S···C | 0.9 |
Interaction | distance | symmetry operation |
H8···H16C | 2.25 | -1/2 + x, 1/2 + y, z |
C6···H16B | 2.86 | 1/2 - x, 3/2 + y, 3/2 - z |
O1···H16A | 2.70 | x, 1 + y, z |
C11···H16A | 2.78 | x, 1 + y, z |
C12···H16A | 2.89 | x, 1 + y, z |
Interaction | ER |
H···H | 0.97 |
O···H/H···O | 1.28 |
S···H/H···S | 1.14 |
C···C | 1.09 |
C···H/H···C | 1.05 |
S···O/O···S | 1.24 |
S···S | 0.45 |
C···S/S···C | 0.31 |
Footnotes
‡Additional correspondence author, e-mail: thahira@upm.edu.my.
Acknowledgements
We thank the Department of Chemistry, the Molecular Genetics Laboratory and the Department of Obstetrics and Gynaecology, Universiti Putra Malaysia, for access to facilities. This research was funded by Universiti Putra Malaysia (UPM) and the Malaysian Government under the Research University Grant Scheme (RUGS No. 9419400), the Malaysian Fundamental Research Grant Scheme (FRGS No. 01/02-13-1344FR) and the ScienceFund under the Ministry of Science, Technology and Innovation (MOSTI) (06-01-04-SF1810). ENMY also wishes to acknowledge the MyPhD Malaysian Government Scholarship (MyBrain15).
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