research communications
1-{(E)-[4-(4-Hydroxyphenyl)butan-2-ylidene]amino}-3-phenylthiourea: Hirshfeld surface analysis and computational study
aDepartment of Physical Science, Faculty of Applied Sciences, Tunku Abdul Rahman University College, 50932 Setapak, Kuala Lumpur, Malaysia, bResearch Centre for Crystalline Materials, School of Medical and Life Sciences, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia, cDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, UPM, Serdang 43400, Malaysia, and dDepartment of Chemistry, St. Francis Xavier University, PO Box 5000, Antigonish, NS B2G 2W5, Canada
*Correspondence e-mail: edwardt@sunway.edu.my
The title thiourea derivative, C17H19N3OS, adopts a U-shaped conformation with the dihedral angle between the terminal aromatic rings being 73.64 (5)°. The major twist in the molecule occurs about the ethane bond with the Ci—Ce—Ce—Cb torsion angle being −78.12 (18)°; i = imine, e = ethane and b = benzene. The configuration about the imine bond is E, the N-bound H atoms lie on opposite sides of the molecule and an intramolecular amine-N—H⋯N(imine) hydrogen bond is evident. In the molecular packing, hydroxyl-O—H⋯S(thione) and amine-N—H⋯O hydrogen bonding feature within a linear, supramolecular chain. The chains are connected into a layer in the ab plane by a combination of methylene-C—H⋯S(thione), methylene-C—H⋯O(hydroxyl), methyl-C—H⋯π(phenyl) and phenyl-C—H⋯π(hydroxybenzene) interactions. The layers stack without directional interactions between them. The analysis of the calculated Hirshfeld surface highlights the presence of weak methyl-C—H⋯O(hydroxyl) and H⋯H interactions in the inter-layer region. Computational chemistry indicates that dispersion energy is the major contributor to the overall stabilization of the molecular packing.
CCDC reference: 2092413
1. Chemical context
Raspberry ketone, also known as 4-(4-hydroxyphenyl)-2-butanone (C10H12O2), is a natural phenolic compound found in raspberries, kiwi fruit, brewed coffee, yew and orchid flowers (Lee, 2016). This ketone is the primary compound responsible for the fruity aroma and has long been used commercially as a fragrance and flavouring agent for cosmetics, perfume, food and beverages. The pharmaceutical attributes exhibited by this ketone include anti-androgenic activity in human breast cancer cells, de-pigmentation, anti-inflammatory activity and cardioprotective action in rats (Dziduch et al., 2020; Yuan et al., 2020). In this work, raspberry ketone was condensed with 4-phenyl-3-thiosemicarbazide to form the title thiourea derivative, C17H19N3OS, hereafter designated as (I). Such compounds are of much interest due to their attractive and widespread pharmacological activities including anti-bacterial, anti-fungal, anti-tubercular, anti-convulsant, anti-tumour, anti-oxidant, anti-malarial and anti-helmintic properties (Dincel & Guzeldemirci, 2020). In a continuation of on-going studies on related derivatives and complexes (Tan, Ho et al. 2020; Tan, Kwong et al. 2020a,b), herein the synthesis, Hirshfeld surface analysis and computational chemistry of (I) are reported.
2. Structural commentary
The molecular structure of (I), Fig. 1, comprises an almost planar central chromophore with the r.m.s. deviation for the C1, N1–N3 and S1 atoms being 0.0039 Å; the maximum deviation from the least-squares plane is 0.0054 (12) Å for the C1 atom. The pendant C2 and C8 atoms lie 0.065 (3) and 0.072 (2) Å out of and to the same side of the central plane. While the N1-bound phenyl ring is approximately co-planar with the central residue, forming a dihedral angle of 7.94 (8)°, the terminal 4-hydroxybenzene ring is not, forming a dihedral angle of 67.00 (4)°; the dihedral angle between the rings is 73.64 (5)°. This conformation arises as there is a twist about the ethane bond, i.e. the C8—C10—C11—C12 torsion angle is −78.12 (18)°. Globally, both aromatic residues lie to the same side of the molecule so that it has a U-shaped conformation.
The C1—S1 bond length is 1.6910 (15) Å, the C1—N1 bond [1.340 (2) Å] is marginally shorter than the C1—N2 [1.356 (2) Å] bond, the formally C8—N3 double bond is 1.284 (2) Å and N2—N3 is 1.3857 (18) Å. These values, coupled with the observed planarity in this region of the molecule, is suggestive of some delocalization of π-electron density over this residue. The configuration about the C8=N3 imine bond is E. The N-bound H atoms lie to opposite sides of the molecule, a conformation that allows for the formation of an intramolecular amine-N—H⋯N(imine) hydrogen bond, Table 1.
3. Supramolecular features
In the crystal, hydrogen bonding leads to the formation of a linear, supramolecular chain parallel to [73]. These chains arise because the hydroxyl-O—H atom forms a hydrogen bond to the thione-S1 atom and the hydroxyl-O1 atom simultaneously accepts a N—H⋯O hydrogen bond from the amine-N2—H atom, Fig. 2(a). They are connected into a supramolecular layer parallel to the c axis via methylene-C—H⋯S(thione) and methylene-C—H⋯O(hydroxyl) interactions as well as methyl-C—H⋯π(phenyl) and phenyl-C—H⋯π(hydroxybenzene) contacts, Table 1 and Fig. 2(b). The layers thus formed are two molecules thick and stack along the c-axis direction without directional interactions between them, Fig. 2(c). Finally, as indicated in Fig. 2(b) and (c), the supramolecular connectivity brings two sulfur atoms into close proximity, with an S1⋯S1i separation of 3.3534 (6) Å, cf. the sum of the van der Waals radii of 3.60 Å (Spek, 2020); (i): 2 − x, −y, 1 − z.
4. Analysis of the Hirshfeld surfaces
The Hirshfeld surface analysis comprising the calculation of the dnorm surface (McKinnon et al., 2004), electrostatic potential (Spackman et al., 2008), using the wave function at the HF/STO-3G level of theory, and two-dimensional fingerprint plots (Spackman & McKinnon, 2002) were generated to further elucidate the interactions in the crystal of (I), in particular within the inter-layer region. This study was carried out using Crystal Explorer 17 (Turner et al., 2017) following literature procedures (Tan et al., 2019).
The bright-red spots on the Hirshfeld surface mapped over dnorm in Fig. 3(a), i.e. near the amine-H2N and thione-S1 atoms, correspond to the amine-N2—H2N⋯O1(hydroxyl), hydroxyl-O1—H1O⋯S1(thione) hydrogen bonds and the thione-S1⋯S1(thione) short contact; these and other short contacts calculated using Crystal Explorer 17 are collated in Table 2. These hydrogen bonds are also reflected in the Hirshfeld surface mapped over the electrostatic potential shown in Fig. 3(b), where the positive electrostatic potential (blue) and negative electrostatic potential (red) regions are observed around the amine-H2N and thione-S1 atoms, respectively. The faint red spots appearing near the thione-S1, hydroxyl-O1 and methylene-H11A and H11B atoms (Fig. 4) correspond to methylene-C—H⋯S(thione) and methylene-C—H⋯O1(hydroxyl) interactions, with separations ∼0.2 Å shorter than the sum of their respective van der Waals radii, Table 2. The methyl-C9—H9A⋯π(C2–C7; Cg1) and phenyl-C6—H6⋯π(C12–C17; Cg2) interactions are shown as faint red spots on the dnorm surface in Fig. 5(a) and as two distinctive orange `potholes' on the shape-index-mapped over Hirshfeld surface in Fig. 5(b). It is noted that the phenyl-C4—H4⋯π(C12–C17, Cg2) interaction, Table 1, was not manifested on the dnorm-mapped Hirshfeld surface. However, this interaction clearly shows up as an orange `pothole' on the shape-index-mapped Hirshfeld surface in Fig. 6.
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The overall two-dimensional fingerprint plot computed for (I) is shown in Fig. 7(a) and those delineated into H⋯H, H⋯C/C⋯H, H⋯S/S⋯H and H⋯O/O⋯H contacts are illustrated in Fig. 7(b)–(e), respectively. The percentage contributions to the Hirshfeld surface of (I) from the different interatomic contacts are summarized in Table 3. The H⋯H contacts are the most prominent of all contacts and contribute 49.6% to the entire surface. The H⋯H contact manifested as a duckbill peak tipped at de = di ∼2.1 Å, Fig. 7(b), corresponds to the intra-layer H1O⋯H2N contact listed in Table 2. The H⋯C/C⋯H contacts contribute 22.6% to the Hirshfeld surface, Fig. 7(c), reflecting the significant C—H⋯π interactions evinced in the packing analysis, Table 1. Consistent with the O—H⋯S and N—H⋯O hydrogen bonds occurring in the crystal, H⋯S/S⋯H and H⋯O/O⋯H contacts contribute 10.5 and 6.4%, respectively, to the overall Hirshfeld surface. These two contacts appear as two sharp spikes in the fingerprint plots at de = di ≃ 2.2 Å in Fig. 7(d) and (e), respectively. The contributions from the other six interatomic contacts summarized in Table 3 have a reduced influence on the calculated Hirshfeld surface of (I), as each contributes less than 3.0%.
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5. Computational chemistry
The energy frameworks were calculated for (I) by summing the four energy components – the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energy components (Turner et al., 2017). The individual energy components as well as the total energy for the identified intermolecular interactions are summarized in Table 4. As the intra-layer region is mainly consolidated by C—H⋯π and C—H⋯S/O interactions, the Edis component makes the major contribution to the interaction energies. The most significant stabilization energies are found in the intra-layer region, as outlined in Supramolecular Features. The S1⋯S1 short contact is dominated by the Eele (−8.9 kJ mol−1) and Erep (12.2 kJ mol−1) terms and having a total energy of 11.7 kJ mol−1 is non-attractive.
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The stabilization energies in the inter-layer region are dominated by the Edis component. The greatest stabilization energy in the inter-layer region arises from methyl-C9—H9B⋯O1(hydroxyl) [2.87 Å; −x + 1, −y + 2, −z] and methylene-H10⋯H16(hydroxybenzene) interactions [2.59 Å; −x + 1, −y + 2, −z], which sum to −30.7 kJ mol−1. Generally, the long-range H⋯H contacts are the major interactions stabilizing the molecules within the inter-layer region.
Views of the energy framework diagrams down the a axis direction are shown in Fig. 8 and serve to emphasize the contribution of dispersion forces to the overall molecular packing. The total Eele of all pairwise interactions sum to −145.4 kJ mol−1, while the Edis totals −342.1 kJ mol−1.
6. Database survey
In the crystallographic literature, there are two precedents for molecules related to (I) in which the imine bond is connected to an aromatic residue via an ethane link. Each of these is a N-methyl species, i.e. MeN(H)C(=S)N(H)N=C(Me)CH2CH2Ar, one with Ar = phenyl (Tan, Kwong et al., 2020a) and the other with Ar = 4-methoxybenzene (Tan et al., 2012). In the former, the molecule has a distinctive U-shaped conformation with a twist about the CH2—CH2 bond [the Ci—Cm—Cm—Cp (i = imine, m = methylene, p = phenyl) torsion angle = −62.76 (16)°], a conformation stabilized, at least in part, by an intramolecular amine-N—H⋯π(phenyl) interaction. By contrast, in the species with Ar = 4-methoxybenzene, the molecule is close to planar as indicated by the Ci—Cm—Cm—Cp torsion angles of 177.51 (12) and −175.80 (12)°, respectively, for the two independent molecules comprising the Thus, to a first approximation, the conformation observed in (I) matches that seen in the species with Ar = phenyl, even though no intramolecular N—H⋯π(hydroxybenzene) interaction was noted in (I).
7. Synthesis and crystallization
4-Phenyl-3-thiosemicarbazide (10 mmol) dissolved in hot absolute ethanol (50 ml) was combined with 4-(4-hydroxyphenyl)-2-butanone (10 mmol), dissolved in hot absolute ethanol (50 ml) with a few drops of concentrated hydrochloric acid added as catalyst. The mixture was heated (348 K) and stirred for about 30 min. The mixture was allowed to cool to room temperature while stirring. The white precipitate was filtered, washed with cold ethanol and dried in vacuo. Single crystals were grown at room temperature in mixed solvents of dimethyformamide and acetonitrile (1:2 v/v) by slow evaporation. 1H NMR (500 MHz, CDCl3, referenced to TMS): δ 9.14 (s, 1H), 8.59 (s, 1H), 7.59 (d, 2H), 7.37 (t, 2H), 7.22 (t, 1H), 7.03 (d, 2H), 6.76 (d, 2H), 5.46 (s, 1H), 2.83 (t, 2H), 2.61 (t, 2H), 1.90 (s, 3H). 13C NMR (500 MHz, CDCl3, referenced to solvent, 77.16 ppm): δ 176.22, 154.16, 152.02, 137.93, 132.72, 129.39, 128.84, 126.16, 124.39, 115.57, 40.38, 31.58, 16.19.
8. 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 1.2–1.5Ueq(C). The O-bound and N-bound H atoms were located in a difference-Fourier map but were refined with O—H = 0.84±0.01 and N—H = 0.88±0.01 Å distance restraints, respectively, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).
details are summarized in Table 5
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Supporting information
CCDC reference: 2092413
https://doi.org/10.1107/S2056989021006666/hb7978sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021006666/hb7978Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989021006666/hb7978Isup3.cml
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C17H19N3OS | Z = 2 |
Mr = 313.41 | F(000) = 332 |
Triclinic, P1 | Dx = 1.343 Mg m−3 |
a = 8.0605 (6) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 9.5635 (6) Å | Cell parameters from 7107 reflections |
c = 11.4397 (6) Å | θ = 4–72° |
α = 70.578 (5)° | µ = 1.89 mm−1 |
β = 82.671 (5)° | T = 100 K |
γ = 68.723 (6)° | Plate, colourless |
V = 774.95 (9) Å3 | 0.35 × 0.21 × 0.04 mm |
Oxford Diffraction Gemini diffractometer | 2712 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 71.9°, θmin = 4.1° |
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2012) | h = −9→9 |
Tmin = 0.52, Tmax = 0.93 | k = −11→11 |
15291 measured reflections | l = −13→13 |
2982 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0658P)2 + 0.2814P] where P = (Fo2 + 2Fc2)/3 |
2982 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.36 e Å−3 |
3 restraints | Δρmin = −0.21 e Å−3 |
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 | 0.93080 (5) | 0.19624 (4) | 0.46989 (4) | 0.02796 (15) | |
O1 | 0.12066 (15) | 1.17646 (14) | 0.21473 (11) | 0.0292 (3) | |
H1O | 0.082 (3) | 1.159 (3) | 0.2882 (11) | 0.044* | |
N1 | 0.77812 (17) | 0.49550 (15) | 0.48469 (12) | 0.0233 (3) | |
H1N | 0.774 (2) | 0.5919 (13) | 0.4427 (16) | 0.028* | |
N2 | 0.95702 (17) | 0.46117 (15) | 0.31940 (12) | 0.0237 (3) | |
H2N | 1.024 (2) | 0.3997 (19) | 0.2772 (15) | 0.028* | |
N3 | 0.92493 (17) | 0.62221 (15) | 0.27822 (12) | 0.0235 (3) | |
C1 | 0.8821 (2) | 0.39389 (18) | 0.42601 (14) | 0.0223 (3) | |
C2 | 0.6701 (2) | 0.47628 (18) | 0.59294 (14) | 0.0219 (3) | |
C3 | 0.6397 (2) | 0.33626 (18) | 0.66028 (15) | 0.0247 (3) | |
H3 | 0.695700 | 0.243795 | 0.636170 | 0.030* | |
C4 | 0.5271 (2) | 0.33353 (19) | 0.76263 (15) | 0.0254 (3) | |
H4 | 0.506601 | 0.238203 | 0.808407 | 0.030* | |
C5 | 0.4437 (2) | 0.4669 (2) | 0.79964 (15) | 0.0268 (4) | |
H5 | 0.366970 | 0.463257 | 0.870039 | 0.032* | |
C6 | 0.4742 (2) | 0.6063 (2) | 0.73207 (16) | 0.0300 (4) | |
H6 | 0.417842 | 0.698703 | 0.756202 | 0.036* | |
C7 | 0.5864 (2) | 0.61034 (19) | 0.62989 (15) | 0.0271 (4) | |
H7 | 0.606583 | 0.705860 | 0.584298 | 0.033* | |
C8 | 0.9943 (2) | 0.67483 (18) | 0.17277 (15) | 0.0241 (3) | |
C9 | 1.1028 (2) | 0.5771 (2) | 0.09267 (16) | 0.0323 (4) | |
H9A | 1.224584 | 0.522396 | 0.124235 | 0.048* | |
H9B | 1.104985 | 0.645704 | 0.007433 | 0.048* | |
H9C | 1.049551 | 0.499250 | 0.094012 | 0.048* | |
C10 | 0.9738 (2) | 0.84652 (19) | 0.12493 (15) | 0.0265 (4) | |
H10A | 0.909132 | 0.893089 | 0.045447 | 0.032* | |
H10B | 1.094242 | 0.854018 | 0.106361 | 0.032* | |
C11 | 0.8784 (2) | 0.94844 (19) | 0.20771 (15) | 0.0269 (4) | |
H11A | 0.922435 | 0.889481 | 0.293362 | 0.032* | |
H11B | 0.911704 | 1.044499 | 0.179824 | 0.032* | |
C12 | 0.6776 (2) | 0.99862 (17) | 0.21054 (15) | 0.0234 (3) | |
C13 | 0.5843 (2) | 0.97100 (18) | 0.32206 (15) | 0.0254 (3) | |
H13 | 0.648932 | 0.912561 | 0.396999 | 0.030* | |
C14 | 0.3991 (2) | 1.02660 (18) | 0.32684 (15) | 0.0260 (3) | |
H14 | 0.338550 | 1.005371 | 0.404055 | 0.031* | |
C15 | 0.3032 (2) | 1.11362 (18) | 0.21756 (15) | 0.0247 (3) | |
C16 | 0.3935 (2) | 1.14113 (18) | 0.10509 (15) | 0.0257 (3) | |
H16 | 0.328803 | 1.198894 | 0.030121 | 0.031* | |
C17 | 0.5781 (2) | 1.08424 (18) | 0.10229 (15) | 0.0253 (3) | |
H17 | 0.638311 | 1.103991 | 0.024812 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0328 (2) | 0.0182 (2) | 0.0289 (2) | −0.00720 (17) | 0.00688 (16) | −0.00644 (16) |
O1 | 0.0263 (6) | 0.0318 (6) | 0.0311 (6) | −0.0113 (5) | 0.0057 (5) | −0.0126 (5) |
N1 | 0.0245 (7) | 0.0172 (6) | 0.0265 (7) | −0.0084 (5) | 0.0031 (5) | −0.0044 (5) |
N2 | 0.0239 (7) | 0.0194 (6) | 0.0260 (7) | −0.0073 (5) | 0.0050 (5) | −0.0067 (5) |
N3 | 0.0212 (6) | 0.0201 (6) | 0.0280 (7) | −0.0085 (5) | 0.0002 (5) | −0.0044 (5) |
C1 | 0.0192 (7) | 0.0218 (8) | 0.0252 (8) | −0.0069 (6) | −0.0010 (6) | −0.0064 (6) |
C2 | 0.0190 (7) | 0.0232 (8) | 0.0231 (7) | −0.0072 (6) | −0.0002 (6) | −0.0067 (6) |
C3 | 0.0243 (8) | 0.0222 (8) | 0.0287 (8) | −0.0088 (6) | 0.0013 (6) | −0.0086 (6) |
C4 | 0.0253 (8) | 0.0247 (8) | 0.0260 (8) | −0.0116 (7) | 0.0008 (6) | −0.0046 (6) |
C5 | 0.0256 (8) | 0.0302 (8) | 0.0245 (8) | −0.0105 (7) | 0.0045 (6) | −0.0090 (7) |
C6 | 0.0338 (9) | 0.0255 (8) | 0.0311 (9) | −0.0089 (7) | 0.0041 (7) | −0.0124 (7) |
C7 | 0.0326 (9) | 0.0213 (8) | 0.0273 (8) | −0.0106 (7) | 0.0028 (7) | −0.0069 (6) |
C8 | 0.0177 (7) | 0.0250 (8) | 0.0266 (8) | −0.0068 (6) | −0.0010 (6) | −0.0045 (6) |
C9 | 0.0331 (9) | 0.0321 (9) | 0.0275 (9) | −0.0096 (7) | 0.0034 (7) | −0.0073 (7) |
C10 | 0.0222 (8) | 0.0257 (8) | 0.0284 (8) | −0.0110 (6) | 0.0025 (6) | −0.0021 (7) |
C11 | 0.0291 (9) | 0.0238 (8) | 0.0291 (8) | −0.0140 (7) | −0.0023 (7) | −0.0037 (6) |
C12 | 0.0287 (8) | 0.0174 (7) | 0.0270 (8) | −0.0116 (6) | 0.0008 (6) | −0.0069 (6) |
C13 | 0.0342 (9) | 0.0193 (7) | 0.0238 (8) | −0.0115 (6) | −0.0017 (6) | −0.0051 (6) |
C14 | 0.0352 (9) | 0.0218 (8) | 0.0250 (8) | −0.0143 (7) | 0.0076 (7) | −0.0100 (6) |
C15 | 0.0270 (8) | 0.0205 (7) | 0.0307 (8) | −0.0114 (6) | 0.0045 (6) | −0.0113 (6) |
C16 | 0.0294 (8) | 0.0239 (8) | 0.0243 (8) | −0.0096 (7) | −0.0002 (6) | −0.0076 (6) |
C17 | 0.0295 (8) | 0.0240 (8) | 0.0240 (8) | −0.0120 (6) | 0.0038 (6) | −0.0078 (6) |
S1—C1 | 1.6910 (15) | C8—C9 | 1.500 (2) |
O1—C15 | 1.373 (2) | C8—C10 | 1.501 (2) |
O1—H1O | 0.842 (10) | C9—H9A | 0.9800 |
N1—C1 | 1.340 (2) | C9—H9B | 0.9800 |
N1—C2 | 1.419 (2) | C9—H9C | 0.9800 |
N1—H1N | 0.877 (9) | C10—C11 | 1.524 (2) |
N2—C1 | 1.356 (2) | C10—H10A | 0.9900 |
N2—N3 | 1.3857 (18) | C10—H10B | 0.9900 |
N2—H2N | 0.874 (9) | C11—C12 | 1.512 (2) |
N3—C8 | 1.284 (2) | C11—H11A | 0.9900 |
C2—C7 | 1.392 (2) | C11—H11B | 0.9900 |
C2—C3 | 1.397 (2) | C12—C13 | 1.392 (2) |
C3—C4 | 1.386 (2) | C12—C17 | 1.396 (2) |
C3—H3 | 0.9500 | C13—C14 | 1.392 (2) |
C4—C5 | 1.387 (2) | C13—H13 | 0.9500 |
C4—H4 | 0.9500 | C14—C15 | 1.393 (2) |
C5—C6 | 1.392 (2) | C14—H14 | 0.9500 |
C5—H5 | 0.9500 | C15—C16 | 1.389 (2) |
C6—C7 | 1.382 (2) | C16—C17 | 1.387 (2) |
C6—H6 | 0.9500 | C16—H16 | 0.9500 |
C7—H7 | 0.9500 | C17—H17 | 0.9500 |
C15—O1—H1O | 108.4 (15) | H9A—C9—H9B | 109.5 |
C1—N1—C2 | 132.42 (13) | C8—C9—H9C | 109.5 |
C1—N1—H1N | 110.3 (13) | H9A—C9—H9C | 109.5 |
C2—N1—H1N | 117.2 (13) | H9B—C9—H9C | 109.5 |
C1—N2—N3 | 120.90 (13) | C8—C10—C11 | 117.78 (14) |
C1—N2—H2N | 117.6 (13) | C8—C10—H10A | 107.9 |
N3—N2—H2N | 121.4 (13) | C11—C10—H10A | 107.9 |
C8—N3—N2 | 115.76 (14) | C8—C10—H10B | 107.9 |
N1—C1—N2 | 114.40 (13) | C11—C10—H10B | 107.9 |
N1—C1—S1 | 128.00 (12) | H10A—C10—H10B | 107.2 |
N2—C1—S1 | 117.60 (12) | C12—C11—C10 | 115.73 (13) |
C7—C2—C3 | 119.28 (15) | C12—C11—H11A | 108.3 |
C7—C2—N1 | 115.94 (13) | C10—C11—H11A | 108.3 |
C3—C2—N1 | 124.75 (15) | C12—C11—H11B | 108.3 |
C4—C3—C2 | 119.36 (15) | C10—C11—H11B | 108.3 |
C4—C3—H3 | 120.3 | H11A—C11—H11B | 107.4 |
C2—C3—H3 | 120.3 | C13—C12—C17 | 117.43 (15) |
C3—C4—C5 | 121.43 (14) | C13—C12—C11 | 121.19 (14) |
C3—C4—H4 | 119.3 | C17—C12—C11 | 121.22 (14) |
C5—C4—H4 | 119.3 | C14—C13—C12 | 121.84 (15) |
C4—C5—C6 | 119.00 (15) | C14—C13—H13 | 119.1 |
C4—C5—H5 | 120.5 | C12—C13—H13 | 119.1 |
C6—C5—H5 | 120.5 | C13—C14—C15 | 119.51 (15) |
C7—C6—C5 | 120.06 (16) | C13—C14—H14 | 120.2 |
C7—C6—H6 | 120.0 | C15—C14—H14 | 120.2 |
C5—C6—H6 | 120.0 | O1—C15—C16 | 117.28 (14) |
C6—C7—C2 | 120.87 (15) | O1—C15—C14 | 123.09 (15) |
C6—C7—H7 | 119.6 | C16—C15—C14 | 119.62 (15) |
C2—C7—H7 | 119.6 | C17—C16—C15 | 119.96 (15) |
N3—C8—C9 | 125.38 (14) | C17—C16—H16 | 120.0 |
N3—C8—C10 | 118.97 (15) | C15—C16—H16 | 120.0 |
C9—C8—C10 | 115.60 (14) | C16—C17—C12 | 121.62 (15) |
C8—C9—H9A | 109.5 | C16—C17—H17 | 119.2 |
C8—C9—H9B | 109.5 | C12—C17—H17 | 119.2 |
C1—N2—N3—C8 | −176.20 (13) | N2—N3—C8—C10 | −176.77 (12) |
C2—N1—C1—N2 | 176.34 (14) | N3—C8—C10—C11 | 2.8 (2) |
C2—N1—C1—S1 | −4.5 (2) | C9—C8—C10—C11 | −174.92 (13) |
N3—N2—C1—N1 | 0.0 (2) | C8—C10—C11—C12 | −78.12 (18) |
N3—N2—C1—S1 | −179.27 (11) | C10—C11—C12—C13 | 126.58 (16) |
C1—N1—C2—C7 | 176.90 (15) | C10—C11—C12—C17 | −58.04 (19) |
C1—N1—C2—C3 | −5.1 (3) | C17—C12—C13—C14 | −0.3 (2) |
C7—C2—C3—C4 | −0.1 (2) | C11—C12—C13—C14 | 175.22 (14) |
N1—C2—C3—C4 | −178.09 (14) | C12—C13—C14—C15 | −0.6 (2) |
C2—C3—C4—C5 | 0.1 (2) | C13—C14—C15—O1 | −178.06 (14) |
C3—C4—C5—C6 | 0.1 (2) | C13—C14—C15—C16 | 1.3 (2) |
C4—C5—C6—C7 | −0.1 (2) | O1—C15—C16—C17 | 178.31 (13) |
C5—C6—C7—C2 | 0.0 (3) | C14—C15—C16—C17 | −1.0 (2) |
C3—C2—C7—C6 | 0.1 (2) | C15—C16—C17—C12 | 0.1 (2) |
N1—C2—C7—C6 | 178.22 (14) | C13—C12—C17—C16 | 0.5 (2) |
N2—N3—C8—C9 | 0.7 (2) | C11—C12—C17—C16 | −175.00 (14) |
Cg1 and Cg2 are the centroids of the (C2–C7) and (C12–C17) rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N3 | 0.88 (2) | 2.10 (2) | 2.6214 (19) | 117 (1) |
O1—H1O···S1i | 0.84 (1) | 2.34 (2) | 3.1489 (13) | 162 (2) |
N2—H2N···O1ii | 0.87 (2) | 2.31 (2) | 3.1219 (19) | 155 (2) |
C11—H11A···S1iii | 0.99 | 2.84 | 3.7936 (17) | 163 |
C11—H11B···O1iv | 0.99 | 2.58 | 3.438 (2) | 145 |
C9—H9A···Cg1iii | 0.98 | 2.90 | 3.6862 (19) | 138 |
C4—H4···Cg2v | 0.95 | 2.90 | 3.6939 (19) | 142 |
C6—H6···Cg2vi | 0.98 | 2.84 | 3.601 (2) | 138 |
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z; (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+2, −z+1. |
Contact | Distance | Symmetry operation |
O1—H1O···S1b | 2.20 | x - 1, y + 1, z |
N2—H2N···O1b | 2.19 | x + 1, y - 1, z |
S1···S1 | 3.35 | -x + 2, -y + 1, -z + 1 |
C11—H11A···S1 | 2.75 | -x + 2, -y + 1, -z + 1 |
C11—H11B···O1 | 2.50 | x + 1, y, z |
C9—H9A···Cg(C2–C7) | 2.90 | -x + 2, -y + 1, -z + 1 |
C6—H6···Cg(C12–C17) | 2.84 | -x + 1, -y + 2, -z + 1 |
C4—H4···Cg(C12–C17) | 2.90 | -x + 1, -y + 1, -z + 1 |
H1O···H2N | 2.05 | x - 1, y +1 , z |
Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) with the X—H bond lengths adjusted to their neutron values. (b) This contact corresponds to a conventional hydrogen bond. |
Contact | Percentage contribution |
H···H | 49.6 |
H···C/C···H | 22.6 |
H···S/S···H | 10.5 |
H···O/O···H | 6.4 |
C···C | 2.9 |
N···C/C···N | 2.9 |
H···N/N···H | 2.8 |
N···N | 1.0 |
S···S | 0.8 |
S···C/C···S | 0.5 |
Contact | R (Å) | Eele | Epol | Edis | Erep | Etot |
Intra-layer region | ||||||
C11—H11A···S1iii + | ||||||
C9—H9A···Cg(C2-C7)v | 5.43 | -38.9 | -11.6 | -84.9 | 76.0 | -76.7 |
C4—H4···Cg(C12-C17)vi | 5.30 | -26.8 | -7.3 | -95.7 | 66.8 | -75.8 |
O1—H1O···S1i + | ||||||
N2—H2N···O1ii | 10.02 | -64.6 | -14.9 | -21.3 | 84.4 | -45.7 |
C6—H6···Cg(C12-C17)vii | 7.12 | -5.8 | -2.1 | -44.2 | 30.4 | -27.4 |
C11—H11B···O1iv | 8.06 | -2.2 | -1.0 | -9.9 | 6.5 | -7.7 |
C6···H1Oviii | 11.11 | -0.3 | -0.4 | -3.5 | 0.0 | -3.6 |
S1···S1ix | 11.56 | 8.9 | -1.8 | -4.4 | 12.2 | 11.7 |
Inter-layer region | ||||||
C9—H9B···O1x + | ||||||
H10A···H16x | 8.90 | -11.2 | -2.7 | -28.8 | 13.3 | -30.7 |
H10A···H10Bxi + | ||||||
H10B···H17xi | 10.63 | 0.8 | -1.8 | -24.9 | 17.1 | -11.6 |
H4···H17xii + | ||||||
H5···H16xii | 12.23 | -4.0 | -0.5 | -11.1 | 6.6 | -10.2 |
H9C···H9Cxiii | 10.35 | -2.8 | -1.4 | -9.5 | 7.3 | -7.8 |
H5···H9Bxiv | 13.13 | 1.5 | -0.3 | -3.9 | 1.2 | -1.4 |
Symmetry codes: (i) x - 1, y + 1, z; (ii) x + 1, y - 1, z; (iii) -x + 2, -y + 1, -z + 1; (iv) x + 1, y, z; (v) -x + 2, -y + 1, -z + 1; (vi) -x + 1, -y + 1, -z + 1; (vii) -x + 1, -y + 2, -z + 1; (viii) -x, -y + 2, -z + 1; (ix) -x + 2, -y, -z + 1; (x) -x + 1, -y + 2, -z; (xi) -x + 2, -y + 2, -z; (xii) x, y - 1, z + 1; (xiii) -x + 2, -y, -z + 1; (xiv) x - 1, y, z + 1. |
Footnotes
‡Additional correspondence author, email: kacrouse@gmail.com.
Acknowledgements
The intensity data were collected by M. I. M. Tahir, Universiti Putra Malaysia.
Funding information
Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (grant No. GRTIN-IRG-01–2021).
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