research communications
(N,N-Diisopropyldithiocarbamato)triphenyltin(IV): Hirshfeld surface analysis and computational study
aEnvironmental Health and Industrial Safety Programme, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia, bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The crystal and molecular structures of the title triorganotin dithiocarbamate, [Sn(C6H5)3(C7H14NS2)], are described. The molecular geometry about the metal atom is highly distorted being based on a C3S tetrahedron as the dithiocarbamate ligand is asymmetrically chelating to the tin centre. The close approach of the second thione-S atom [Sn⋯S = 2.9264 (4) Å] is largely responsible for the distortion. The molecular packing is almost devoid of directional interactions with only weak phenyl-C—H⋯C(phenyl) interactions, leading to centrosymmetric dimeric aggregates, being noted. An analysis of the calculated Hirshfeld surface points to the significance of H⋯H contacts, which contribute 66.6% of all contacts to the surface, with C⋯H/H⋯C [26.8%] and S⋯H/H⋯H [6.6%] contacts making up the balance.
Keywords: crystal structure; organotin; dithiocarbamate; Hirshfeld surface analysis; computational chemistry.
CCDC reference: 1952056
1. Chemical context
Organotin(IV) compounds have long been investigated as potential anti-cancer agents (Gielen & Tiekink, 2005) and studies in this area continue. Further, organotin compounds have received much attention owing to their potential therapeutic potential as anti-fungal, anti-bacterial, anti-malarial and schizonticidal agents (Khan et al., 2014). Metal dithiocarbamates have also encouraged much interest in the context of chemotherapeutic agents (Hogarth, 2012) and these include organotin(IV) dithiocarbamate compounds (Tiekink, 2008; Adeyemi & Onwudiwe, 2018). In view of the wide-range of applications/potential of organotin(IV) dithiocarbamate compounds and in continuation of on-going studies in this area (Khan et al., 2015; Mohamad et al. 2016, 2017, 2018), the title compound, Ph3Sn[S2CN(i-Pr)2], (I), was synthesized and characterized spectroscopically. Herein, the crystal and molecular structures of (I) are described along with a detailed analysis of the molecular packing via the calculated Hirshfeld surfaces and computational chemistry study.
2. Structural commentary
The tin atom in (I), Fig. 1, is coordinated by an asymmetrically bound dithiocarbamate ligand and three ipso-carbon atoms of the phenyl groups (Table 1). The disparity in the Sn—S separations, i.e. Δ(Sn—S) = [(Sn—Sl) − (Sn—Ss)] = 0.45 Å (l = long, s = short), is rather great suggesting that the Sn⋯S2 interaction is weak. This is supported in the pattern of C—S bond lengths with that involving the more tightly bound S1 atom being nearly 0.06 Å longer than the equivalent bond with the weakly bound S2 atom. Despite this, a clear influence of the S2 atom is noted on the Sn—C bond lengths with the Sn—C31 bond length being significantly longer than the other Sn—C bonds, Table 1. The S2—Sn—C31 bond angle is 158.41 (4)° and is suggestive of a trans-influence exerted by the S2 atom; there is no other trans angle about the tin atom. If the coordination geometry is considered as tetrahedral, the range of tetrahedral angles is 93.24 (4)°, for S1—Sn—C31, to 119.87 (6)°, for C11—Sn—C21. The range of angles assuming a five-coordinate, C3S2, geometry is 65.260 (11)°, for the S1—Sn—S2 chelate angle to the aforementioned 158.41 (4)°. A descriptor for assigning coordination geometries to five-coordinate species is τ (Addison et al., 1984). In the case of (I), this computes to 0.64, which indicates a geometry somewhat closer to an ideal trigonal bipyramid (τ = 1.0) than to an ideal square pyramid (τ = 0.0). Also included in Table 1 are the C—N bond lengths, which show C1—N1 to be significantly shorter than the C2—N1 and C5—N1 bond lengths, an observation consistent with a significant contribution of the 2−S2C=N+(i-Pr)2 to the overall electronic structure of the dithiocarbamate ligand.
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3. Supramolecular features
The geometric parameters characterizing the identified intermolecular interaction operating in the crystal of (I) are collated in Table 2. A phenyl-C—H⋯C(phenyl) contact less than the sum of the sum of the Waals radii (Spek, 2009) is noted to occur between centrosymmetrically related molecules, Fig. 2(a). This is an example of a localized C—H⋯π contact whereby the hydrogen atom directed towards a single carbon atom of the ring as opposed to a delocalized interaction where the hydrogen atom (or halide atom or lone-pair of electrons) is directed towards the centroid of the ring (Schollmeyer et al., 2008; Tiekink, 2017).
4. Hirshfeld surface analysis
The Hirshfeld surface calculations for (I) were performed employing Crystal Explorer 17 (Turner et al., 2017) and recently published protocols (Tan et al., 2019). In the absence of classical hydrogen bonds, the influence of the localized C—H⋯π interaction, Table 2, as well as interatomic H⋯H and C⋯H/H⋯C contacts, Table 3, upon the molecular packing are evident as the diminutive-red spots near the participating carbon and hydrogen atoms on the Hirshfeld surfaces mapped over dnorm in Fig. 3. It is also noted that with the exception of the methyl-H7A atom, all of the specified interatomic contacts only involve the carbon and hydrogen atoms of the coordinated phenyl rings, Table 3. On the Hirshfeld surface mapped over electrostatic potential in Fig. 4, the light-blue and faint-red regions, corresponding to positive and negative electrostatic potential, respectively, occur about the di-iso-propyl and triphenyltin groups, respectively.
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As reported recently (Pinto et al., 2019), in addition to analysing the nature and strength of intermolecular interactions among molecules, the analyses of Hirshfeld surfaces can also provide useful insight into metal–ligand/donor atom interactions in coordination compounds. Thus, the distance from the surface to the nearest external (de) and internal (di) nuclei, the shape-index (S) and the curvedness (C) can also be plotted. Accordingly, Fig. 5 illustrates the Hirshfeld surfaces for the tin atom coordinated by dithiocarbamate ligand as well as by the three phenyl groups. The close proximity of the dithiocarbamate-S1 and phenyl-C11, C21 and C31 atoms to the tin centre are characterized as bright-red regions perpendicular to bond directions on the Hirshfeld surfaces mapped over de, Fig. 5(a), and dnorm, Fig. 5(b), whereas the comparatively weak Sn—S2 interaction appears as the faint-red region. The longer Sn—C31 bond compared to other two Sn—C bonds, Table 1, is also characterized from these Hirshfeld surfaces through the curvature of the red region. The Sn—S1 and Sn—C bonds result in the large red regions on the shape-index mapping in Fig. 5(c) compared to a small red region for the Sn—S2 bond. On the Hirshfeld surfaces mapped over curvedness in Fig. 5(d), the strength of the tin–ligand bonds are characterized as the yellow areas separated by green regions. The coordination bonds for tin are also rationalized in the fingerprint plot taking into account only the Hirshfeld surface about the metal atom, Fig. 6. The distribution of green points having upper short spike at de + di ∼2.4 Å and the lower, long red spike at de + di ∼2.1 Å are the result of the Sn—S and Sn—C bonds, respectively. This asymmetric distribution of points about the diagonal lacking in colouration is due to the distorted coordination geometry about the tin atom.
It is clear from the the calculation of the overall two-dimensional fingerprint plot for (I), Fig. 7(a), that the plot is asymmetric about the (de, di) diagonal in the longer distance regions and have contributions only from the interatomic contacts involving carbon, hydrogen and sulfur atoms, Table 4. The two-dimensional fingerprint plots delineated into H⋯H, C⋯H/H⋯C, C⋯C and S⋯H/H⋯S contacts are shown in Fig. 7(b)–(d), respectively. In the fingerprint plot delineated into H⋯H contacts in Fig. 7(b), the presence of the short interatomic H⋯H interaction involving the methyl-H7A and phenyl-H12 atoms is evident as the pair of short overlapping peaks at de + di ∼2.1 Å with the other short interatomic H⋯H contact (Table 3) merged within the plot. The intermolecular C—H⋯C interactions describing the localized C—H⋯π contacts are evidenced by a pronounced pair of characteristic wings around (de, di) ∼(1.2 Å, 1.8Å) and ∼(1.8 Å, 1.2 Å) in the fingerprint plot delineated into C⋯H/H⋯C contacts shown in Fig. 7(c). The other short interatomic C⋯H contacts summarized in Table 3 appear as the pair of forceps-like tips at de + di ∼2.7 Å. The fingerprint plot delineated into S⋯H/H⋯S contacts in Fig. 7(d) indicate that sulfur atoms are nearly at van der Waals separation from the symmetry-related hydrogen atoms.
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5. Computational chemistry
The pairwise interaction energies between the molecules within the crystal were calculated using Crystal Explorer 17 (Turner et al., 2017) and summing up the four energy components: electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep). The energies were obtained using the wave function calculated at the HF/STO-3G level of theory. The strength and the nature of intermolecular interactions in terms of their energies are summarized in Table 5. An analysis of these reveals that the dispersion energy component makes the greatest contribution to the energies in the absence of classical hydrogen (electrostatic) bonds. Among the short interatomic contacts listed in Table 5, the intermolecular phenyl-C—H36⋯C12 contact combined with the methyl-H7A⋯H12(phenyl) interaction, occurring between the same pair of symmetry-related molecules, gives rise to the maximum total energy of interaction, compared to the other interactions, which have almost the same energy values.
The graphical representation of the magnitudes of intermolecular energies in Fig. 8, i.e. energy frameworks, relies on a red, green and blue colour code scheme, reflecting the Eele, Edisp and Etot components, respectively. For the direct comparison of magnitudes of interaction energies, their magnitudes were adjusted to same scale factor of 30 with a cut-off value of 3 kJ mol−1 within 2 × 2 × 2 unit cells. It is clear from Fig. 8 that the green cylinders joining the centroids of molecular pairs highlighting the dispersion components make a significant contribution to the supramolecular architecture in the crystal.
6. Database survey
As indicated in a recent report (Mohamad et al., 2018), there are nearly 50 crystal structures available for molecules of the general formula Ph3Sn(S2CNRR′) and, with a number of these having multiple molecules in the there are almost 60 independent molecules. These conform to the same structural motif. An analysis of the key geometric parameters defining the mode of coordination of the dithiocarbamate ligands showed that there were no systematic variations that could be correlated with the nature of the dithiocarbamate ligand, i.e. R/R′ substituents. This observation is borne out by DFT calculations on different organotin systems that proved the influence of molecular packing on (non-systematic) geometric parameters, including metal–sulfur/halide bonds (Buntine et al., 1998a,b, 1999). In terms of Ph3Sn(S2CNRR′), the mean Sn—Ss bond length is 2.47 Å (standard deviation = 0.013 Å) and the average Sn—Sl bond length is 3.04 Å (0.070 Å). The Sn—Ss and Sn—Sl bond lengths in (I) both fall within 2σ of their respective means.
The 3Sn(S2CNRR′) is quite remarkable. Structural diversity is well-established for the organotin dithiocarbamates (Tiekink, 2008; Muthalib et al., 2014) such as for molecules of the general formula R′′2Sn(S2CNRR′)2, for which four distinct structural motifs are known (Zaldi et al., 2017). Also, the behaviour of triphenyltin dithiocarbamates contrasts the analogous chemistry of triphenyltin carboxylates (Tiekink, 1991). These are often monomeric (e.g. Basu Baul et al., 2001), as for (I), but, polymeric examples are known (e.g. Willem et al., 1997; Smyth & Tiekink, 2000). The polymeric structures occur when the carboxylate ligands are bidentate bridging, leading to trans-C3O2 trigonal–bipyramidal coordination geometries for the tin atoms. This fundamental difference in structural chemistry arises as a result of the significant contribution of the 2−S2C=N+RR′ to the electronic structure of the dithiocarbamate anion, as discussed above. The formal negative charge on each sulfur atom makes this ligand a very efficient chelator which effectively reduces the of the tin centre. Far from being a curiosity, such behaviour, i.e. dithiocarbamate ligands reducing the of metal centres, when compared to related xanthate (−S2COR) and dithiophopshate [(−S2P(OR)2] ligands, leads to stark differences in coordination propensities in zinc-triad element 1,1-dithiolate compounds, as has been reviewed recently (Tiekink, 2018a,b).
in the molecular structures of Ph7. Synthesis and crystallization
All chemicals and solvents were used as purchased without purification. The melting point was determined using an automated melting point apparatus (MPA 120 EZ-Melt). Carbon, hydrogen, nitrogen and sulfur analyses were performed on a Leco CHNS-932 Elemental Analyzer.
Di-iso-propylamine (Aldrich; 1.41 ml, 10 mmol) dissolved in ethanol (30 ml) was stirred under ice-bath conditions at 277 K for 20 mins. A 25% ammonia solution (1–2 ml) was added to provide basic conditions. Then, a cold ethanolic solution of carbon disulfide (0.60 ml, 10 mmol) was added dropwise into the solution followed by stirring for 2 h. After that, triphenyltin(IV) chloride (Merck; 3.85 g, 10 mmol) dissolved in ethanol (20–30 ml) was added dropwise into the solution followed by further stirring for 2 h. The precipitate that formed was filtered and washed a few times with cold ethanol to remove impurities. Finally, the colourless precipitate was dried in a desiccator. Recrystallization was carried out by dissolving the compound in a chloroform and ethanol mixture (1:1 v/v). This solution was allowed to slowly evaporate at room temperature yielding colourless slabs of (I). Yield: 47%, m. p.: 437.8–440.2 K. Elemental analysis: Calculated (%): C 57.07, H 5.51, N 2.66, S 12.19. Found (%): C 57.39, H 5.31, N 2.48, S 11.26.
8. Refinement
Crystal data, data collection and structure . Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C).
details are summarized in Table 6
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Supporting information
CCDC reference: 1952056
https://doi.org/10.1107/S2056989019012490/hb7851sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012490/hb7851Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2018); cell
CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Sn(C6H5)3(C7H14NS2)] | Z = 2 |
Mr = 526.30 | F(000) = 536 |
Triclinic, P1 | Dx = 1.469 Mg m−3 |
a = 9.7572 (1) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 11.7030 (2) Å | Cell parameters from 24601 reflections |
c = 11.7602 (2) Å | θ = 3.9–76.3° |
α = 74.419 (1)° | µ = 10.25 mm−1 |
β = 80.114 (1)° | T = 100 K |
γ = 67.285 (2)° | Prism, colourless |
V = 1189.71 (4) Å3 | 0.12 × 0.11 × 0.08 mm |
Rigaku XtaLAB Synergy Dualflex AtlasS2 diffractometer | 4231 reflections with I > 2σ(I) |
Detector resolution: 5.2558 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 67.1°, θmin = 3.9° |
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018) | h = −11→11 |
Tmin = 0.840, Tmax = 1.000 | k = −13→13 |
28219 measured reflections | l = −13→14 |
4248 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)] = 0.015 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.040 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.026P)2 + 0.5977P] where P = (Fo2 + 2Fc2)/3 |
4248 reflections | (Δ/σ)max = 0.001 |
266 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.44 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 | ||
Sn | 0.39008 (2) | 0.31848 (2) | 0.21713 (2) | 0.01326 (4) | |
S1 | 0.19166 (4) | 0.50402 (3) | 0.11108 (3) | 0.01639 (8) | |
S2 | 0.17439 (4) | 0.47895 (4) | 0.36811 (3) | 0.01880 (8) | |
N1 | −0.00996 (14) | 0.67737 (12) | 0.22420 (12) | 0.0176 (3) | |
C1 | 0.10482 (15) | 0.56682 (14) | 0.23615 (14) | 0.0157 (3) | |
C2 | −0.08409 (18) | 0.72965 (17) | 0.33124 (16) | 0.0259 (4) | |
H2 | −0.0355 | 0.6655 | 0.4017 | 0.031* | |
C3 | −0.24831 (19) | 0.74782 (18) | 0.34878 (17) | 0.0301 (4) | |
H3A | −0.3009 | 0.8147 | 0.2840 | 0.045* | |
H3B | −0.2902 | 0.7723 | 0.4243 | 0.045* | |
H3C | −0.2600 | 0.6682 | 0.3493 | 0.045* | |
C4 | −0.0574 (2) | 0.8507 (2) | 0.3257 (2) | 0.0454 (5) | |
H4A | 0.0498 | 0.8342 | 0.3141 | 0.068* | |
H4B | −0.0976 | 0.8788 | 0.3998 | 0.068* | |
H4C | −0.1073 | 0.9170 | 0.2594 | 0.068* | |
C5 | −0.07259 (17) | 0.75964 (14) | 0.11003 (14) | 0.0196 (3) | |
H5 | −0.1546 | 0.8354 | 0.1323 | 0.023* | |
C6 | −0.1481 (2) | 0.69886 (17) | 0.05404 (17) | 0.0273 (4) | |
H6A | −0.2025 | 0.7616 | −0.0122 | 0.041* | |
H6B | −0.2180 | 0.6691 | 0.1132 | 0.041* | |
H6C | −0.0727 | 0.6267 | 0.0250 | 0.041* | |
C7 | 0.03571 (19) | 0.81240 (16) | 0.02586 (16) | 0.0278 (4) | |
H7A | 0.1147 | 0.7437 | −0.0056 | 0.042* | |
H7B | 0.0798 | 0.8497 | 0.0683 | 0.042* | |
H7C | −0.0173 | 0.8779 | −0.0396 | 0.042* | |
C11 | 0.55885 (16) | 0.34926 (13) | 0.28704 (13) | 0.0147 (3) | |
C12 | 0.68313 (16) | 0.35637 (15) | 0.21077 (14) | 0.0191 (3) | |
H12 | 0.6918 | 0.3435 | 0.1331 | 0.023* | |
C13 | 0.79426 (17) | 0.38199 (16) | 0.24707 (15) | 0.0228 (3) | |
H13 | 0.8761 | 0.3902 | 0.1931 | 0.027* | |
C14 | 0.78624 (17) | 0.39561 (15) | 0.36188 (16) | 0.0220 (3) | |
H14 | 0.8633 | 0.4115 | 0.3872 | 0.026* | |
C15 | 0.66454 (17) | 0.38591 (14) | 0.43962 (15) | 0.0195 (3) | |
H15 | 0.6594 | 0.3934 | 0.5188 | 0.023* | |
C16 | 0.55062 (16) | 0.36527 (14) | 0.40185 (14) | 0.0167 (3) | |
H16 | 0.4661 | 0.3620 | 0.4546 | 0.020* | |
C21 | 0.31244 (16) | 0.16861 (14) | 0.31013 (13) | 0.0161 (3) | |
C22 | 0.40747 (18) | 0.05244 (15) | 0.37020 (15) | 0.0215 (3) | |
H22 | 0.5088 | 0.0403 | 0.3739 | 0.026* | |
C23 | 0.3558 (2) | −0.04562 (16) | 0.42466 (16) | 0.0256 (4) | |
H23 | 0.4216 | −0.1239 | 0.4661 | 0.031* | |
C24 | 0.20910 (19) | −0.03021 (16) | 0.41896 (15) | 0.0227 (3) | |
H24 | 0.1740 | −0.0975 | 0.4565 | 0.027* | |
C25 | 0.11378 (18) | 0.08408 (17) | 0.35814 (16) | 0.0255 (4) | |
H25 | 0.0132 | 0.0950 | 0.3529 | 0.031* | |
C26 | 0.16529 (18) | 0.18255 (16) | 0.30497 (15) | 0.0234 (3) | |
H26 | 0.0989 | 0.2610 | 0.2643 | 0.028* | |
C31 | 0.50078 (15) | 0.25703 (14) | 0.05537 (14) | 0.0162 (3) | |
C32 | 0.55917 (18) | 0.12811 (15) | 0.05353 (16) | 0.0229 (3) | |
H32 | 0.5551 | 0.0668 | 0.1246 | 0.027* | |
C33 | 0.62313 (19) | 0.08811 (16) | −0.05083 (17) | 0.0282 (4) | |
H33 | 0.6622 | 0.0000 | −0.0505 | 0.034* | |
C34 | 0.63013 (19) | 0.17592 (18) | −0.15492 (16) | 0.0272 (4) | |
H34 | 0.6732 | 0.1483 | −0.2262 | 0.033* | |
C35 | 0.57407 (19) | 0.30455 (17) | −0.15524 (15) | 0.0249 (3) | |
H35 | 0.5790 | 0.3653 | −0.2265 | 0.030* | |
C36 | 0.51064 (17) | 0.34382 (15) | −0.05060 (14) | 0.0197 (3) | |
H36 | 0.4731 | 0.4319 | −0.0512 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.01301 (6) | 0.01352 (6) | 0.01339 (6) | −0.00463 (4) | −0.00068 (4) | −0.00360 (4) |
S1 | 0.01698 (17) | 0.01653 (17) | 0.01422 (18) | −0.00254 (13) | −0.00113 (13) | −0.00638 (13) |
S2 | 0.01615 (17) | 0.02318 (18) | 0.01490 (18) | −0.00338 (14) | −0.00031 (13) | −0.00680 (14) |
N1 | 0.0147 (6) | 0.0194 (6) | 0.0190 (7) | −0.0035 (5) | −0.0015 (5) | −0.0083 (5) |
C1 | 0.0122 (6) | 0.0189 (7) | 0.0187 (8) | −0.0070 (6) | 0.0006 (5) | −0.0076 (6) |
C2 | 0.0201 (8) | 0.0305 (9) | 0.0226 (9) | 0.0009 (7) | 0.0008 (6) | −0.0153 (7) |
C3 | 0.0253 (9) | 0.0306 (9) | 0.0286 (10) | −0.0063 (7) | 0.0080 (7) | −0.0087 (7) |
C4 | 0.0423 (11) | 0.0616 (14) | 0.0523 (14) | −0.0251 (10) | 0.0112 (10) | −0.0445 (12) |
C5 | 0.0184 (7) | 0.0170 (7) | 0.0221 (8) | −0.0032 (6) | −0.0043 (6) | −0.0053 (6) |
C6 | 0.0278 (9) | 0.0265 (9) | 0.0297 (10) | −0.0086 (7) | −0.0116 (7) | −0.0057 (7) |
C7 | 0.0280 (9) | 0.0232 (8) | 0.0295 (10) | −0.0081 (7) | 0.0028 (7) | −0.0061 (7) |
C11 | 0.0136 (6) | 0.0116 (6) | 0.0173 (8) | −0.0025 (5) | −0.0032 (5) | −0.0026 (5) |
C12 | 0.0153 (7) | 0.0211 (7) | 0.0178 (8) | −0.0027 (6) | −0.0015 (6) | −0.0048 (6) |
C13 | 0.0134 (7) | 0.0265 (8) | 0.0256 (9) | −0.0058 (6) | 0.0005 (6) | −0.0045 (7) |
C14 | 0.0154 (7) | 0.0208 (8) | 0.0312 (9) | −0.0049 (6) | −0.0071 (6) | −0.0068 (7) |
C15 | 0.0217 (7) | 0.0157 (7) | 0.0200 (8) | −0.0025 (6) | −0.0053 (6) | −0.0065 (6) |
C16 | 0.0159 (7) | 0.0142 (7) | 0.0178 (8) | −0.0031 (5) | −0.0009 (6) | −0.0038 (6) |
C21 | 0.0192 (7) | 0.0169 (7) | 0.0139 (7) | −0.0078 (6) | 0.0014 (6) | −0.0058 (6) |
C22 | 0.0210 (8) | 0.0211 (8) | 0.0230 (8) | −0.0084 (6) | −0.0041 (6) | −0.0029 (6) |
C23 | 0.0315 (9) | 0.0184 (8) | 0.0249 (9) | −0.0081 (7) | −0.0041 (7) | −0.0019 (7) |
C24 | 0.0314 (9) | 0.0233 (8) | 0.0192 (8) | −0.0168 (7) | 0.0075 (6) | −0.0094 (6) |
C25 | 0.0204 (8) | 0.0312 (9) | 0.0291 (9) | −0.0140 (7) | 0.0047 (7) | −0.0104 (7) |
C26 | 0.0182 (8) | 0.0229 (8) | 0.0264 (9) | −0.0060 (6) | −0.0006 (6) | −0.0036 (7) |
C31 | 0.0131 (7) | 0.0189 (7) | 0.0179 (8) | −0.0054 (6) | −0.0003 (5) | −0.0071 (6) |
C32 | 0.0225 (8) | 0.0194 (8) | 0.0260 (9) | −0.0062 (6) | 0.0008 (6) | −0.0074 (7) |
C33 | 0.0265 (8) | 0.0225 (8) | 0.0389 (10) | −0.0074 (7) | 0.0034 (7) | −0.0180 (8) |
C34 | 0.0241 (8) | 0.0378 (10) | 0.0267 (9) | −0.0127 (7) | 0.0062 (7) | −0.0212 (8) |
C35 | 0.0270 (8) | 0.0312 (9) | 0.0189 (8) | −0.0134 (7) | 0.0027 (6) | −0.0079 (7) |
C36 | 0.0201 (7) | 0.0201 (8) | 0.0201 (8) | −0.0071 (6) | 0.0001 (6) | −0.0078 (6) |
Sn—S1 | 2.4792 (4) | C12—H12 | 0.9500 |
Sn—S2 | 2.9264 (4) | C13—C14 | 1.387 (3) |
Sn—C11 | 2.1446 (14) | C13—H13 | 0.9500 |
Sn—C21 | 2.1349 (15) | C14—C15 | 1.391 (2) |
Sn—C31 | 2.1754 (15) | C14—H14 | 0.9500 |
C1—S1 | 1.7587 (15) | C15—C16 | 1.388 (2) |
C1—S2 | 1.7006 (16) | C15—H15 | 0.9500 |
C1—N1 | 1.336 (2) | C16—H16 | 0.9500 |
C5—N1 | 1.495 (2) | C21—C26 | 1.391 (2) |
C2—N1 | 1.497 (2) | C21—C22 | 1.394 (2) |
C2—C3 | 1.517 (2) | C22—C23 | 1.387 (2) |
C2—C4 | 1.519 (3) | C22—H22 | 0.9500 |
C2—H2 | 1.0000 | C23—C24 | 1.383 (2) |
C3—H3A | 0.9800 | C23—H23 | 0.9500 |
C3—H3B | 0.9800 | C24—C25 | 1.385 (3) |
C3—H3C | 0.9800 | C24—H24 | 0.9500 |
C4—H4A | 0.9800 | C25—C26 | 1.387 (2) |
C4—H4B | 0.9800 | C25—H25 | 0.9500 |
C4—H4C | 0.9800 | C26—H26 | 0.9500 |
C5—C7 | 1.515 (2) | C31—C32 | 1.397 (2) |
C5—C6 | 1.519 (2) | C31—C36 | 1.396 (2) |
C5—H5 | 1.0000 | C32—C33 | 1.391 (3) |
C6—H6A | 0.9800 | C32—H32 | 0.9500 |
C6—H6B | 0.9800 | C33—C34 | 1.382 (3) |
C6—H6C | 0.9800 | C33—H33 | 0.9500 |
C7—H7A | 0.9800 | C34—C35 | 1.388 (3) |
C7—H7B | 0.9800 | C34—H34 | 0.9500 |
C7—H7C | 0.9800 | C35—C36 | 1.390 (2) |
C11—C12 | 1.395 (2) | C35—H35 | 0.9500 |
C11—C16 | 1.397 (2) | C36—H36 | 0.9500 |
C12—C13 | 1.388 (2) | ||
C21—Sn—C11 | 119.87 (6) | C12—C11—C16 | 118.47 (14) |
C21—Sn—C31 | 102.73 (6) | C12—C11—Sn | 117.04 (11) |
C11—Sn—C31 | 103.38 (5) | C16—C11—Sn | 124.47 (11) |
C21—Sn—S1 | 112.27 (4) | C13—C12—C11 | 120.79 (15) |
C11—Sn—S1 | 119.12 (4) | C13—C12—H12 | 119.6 |
C31—Sn—S1 | 93.24 (4) | C11—C12—H12 | 119.6 |
C21—Sn—S2 | 88.10 (4) | C14—C13—C12 | 120.24 (15) |
C11—Sn—S2 | 86.68 (4) | C14—C13—H13 | 119.9 |
C31—Sn—S2 | 158.41 (4) | C12—C13—H13 | 119.9 |
S1—Sn—S2 | 65.260 (11) | C13—C14—C15 | 119.49 (15) |
C1—S1—Sn | 95.87 (5) | C13—C14—H14 | 120.3 |
C1—S2—Sn | 82.36 (5) | C15—C14—H14 | 120.3 |
C1—N1—C5 | 125.74 (13) | C14—C15—C16 | 120.21 (15) |
C1—N1—C2 | 119.61 (13) | C14—C15—H15 | 119.9 |
C5—N1—C2 | 114.62 (12) | C16—C15—H15 | 119.9 |
N1—C1—S2 | 123.73 (12) | C15—C16—C11 | 120.71 (14) |
N1—C1—S1 | 119.94 (12) | C15—C16—H16 | 119.6 |
S2—C1—S1 | 116.33 (8) | C11—C16—H16 | 119.6 |
N1—C2—C3 | 111.83 (14) | C26—C21—C22 | 118.14 (14) |
N1—C2—C4 | 110.44 (15) | C26—C21—Sn | 119.77 (11) |
C3—C2—C4 | 112.51 (15) | C22—C21—Sn | 121.95 (11) |
N1—C2—H2 | 107.3 | C23—C22—C21 | 120.74 (15) |
C3—C2—H2 | 107.3 | C23—C22—H22 | 119.6 |
C4—C2—H2 | 107.3 | C21—C22—H22 | 119.6 |
C2—C3—H3A | 109.5 | C24—C23—C22 | 120.43 (15) |
C2—C3—H3B | 109.5 | C24—C23—H23 | 119.8 |
H3A—C3—H3B | 109.5 | C22—C23—H23 | 119.8 |
C2—C3—H3C | 109.5 | C23—C24—C25 | 119.52 (15) |
H3A—C3—H3C | 109.5 | C23—C24—H24 | 120.2 |
H3B—C3—H3C | 109.5 | C25—C24—H24 | 120.2 |
C2—C4—H4A | 109.5 | C24—C25—C26 | 119.94 (15) |
C2—C4—H4B | 109.5 | C24—C25—H25 | 120.0 |
H4A—C4—H4B | 109.5 | C26—C25—H25 | 120.0 |
C2—C4—H4C | 109.5 | C21—C26—C25 | 121.22 (15) |
H4A—C4—H4C | 109.5 | C21—C26—H26 | 119.4 |
H4B—C4—H4C | 109.5 | C25—C26—H26 | 119.4 |
N1—C5—C7 | 113.59 (13) | C32—C31—C36 | 117.70 (14) |
N1—C5—C6 | 112.50 (13) | C32—C31—Sn | 120.43 (12) |
C7—C5—C6 | 114.30 (15) | C36—C31—Sn | 121.81 (11) |
N1—C5—H5 | 105.1 | C33—C32—C31 | 120.96 (16) |
C7—C5—H5 | 105.1 | C33—C32—H32 | 119.5 |
C6—C5—H5 | 105.1 | C31—C32—H32 | 119.5 |
C5—C6—H6A | 109.5 | C34—C33—C32 | 120.27 (16) |
C5—C6—H6B | 109.5 | C34—C33—H33 | 119.9 |
H6A—C6—H6B | 109.5 | C32—C33—H33 | 119.9 |
C5—C6—H6C | 109.5 | C33—C34—C35 | 119.89 (16) |
H6A—C6—H6C | 109.5 | C33—C34—H34 | 120.1 |
H6B—C6—H6C | 109.5 | C35—C34—H34 | 120.1 |
C5—C7—H7A | 109.5 | C36—C35—C34 | 119.53 (16) |
C5—C7—H7B | 109.5 | C36—C35—H35 | 120.2 |
H7A—C7—H7B | 109.5 | C34—C35—H35 | 120.2 |
C5—C7—H7C | 109.5 | C35—C36—C31 | 121.64 (15) |
H7A—C7—H7C | 109.5 | C35—C36—H36 | 119.2 |
H7B—C7—H7C | 109.5 | C31—C36—H36 | 119.2 |
C5—N1—C1—S2 | 178.33 (11) | C13—C14—C15—C16 | −1.3 (2) |
C2—N1—C1—S2 | 0.0 (2) | C14—C15—C16—C11 | 2.4 (2) |
C5—N1—C1—S1 | −2.2 (2) | C12—C11—C16—C15 | −0.9 (2) |
C2—N1—C1—S1 | 179.49 (11) | Sn—C11—C16—C15 | −179.42 (11) |
Sn—S2—C1—N1 | −176.75 (13) | C26—C21—C22—C23 | −0.9 (2) |
Sn—S2—C1—S1 | 3.78 (7) | Sn—C21—C22—C23 | −176.59 (13) |
Sn—S1—C1—N1 | 176.06 (11) | C21—C22—C23—C24 | 0.8 (3) |
Sn—S1—C1—S2 | −4.44 (8) | C22—C23—C24—C25 | 0.1 (3) |
C1—N1—C2—C3 | −120.82 (16) | C23—C24—C25—C26 | −0.9 (3) |
C5—N1—C2—C3 | 60.70 (19) | C22—C21—C26—C25 | 0.1 (2) |
C1—N1—C2—C4 | 113.06 (18) | Sn—C21—C26—C25 | 175.91 (13) |
C5—N1—C2—C4 | −65.42 (18) | C24—C25—C26—C21 | 0.8 (3) |
C1—N1—C5—C7 | −64.0 (2) | C36—C31—C32—C33 | −0.8 (2) |
C2—N1—C5—C7 | 114.38 (15) | Sn—C31—C32—C33 | 176.56 (12) |
C1—N1—C5—C6 | 67.84 (19) | C31—C32—C33—C34 | 0.1 (3) |
C2—N1—C5—C6 | −113.79 (15) | C32—C33—C34—C35 | 0.5 (3) |
C16—C11—C12—C13 | −1.6 (2) | C33—C34—C35—C36 | −0.3 (3) |
Sn—C11—C12—C13 | 176.97 (12) | C34—C35—C36—C31 | −0.4 (2) |
C11—C12—C13—C14 | 2.7 (2) | C32—C31—C36—C35 | 1.0 (2) |
C12—C13—C14—C15 | −1.3 (2) | Sn—C31—C36—C35 | −176.35 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C34—H34···C24i | 0.95 | 2.82 | 3.757 (3) | 171 |
Symmetry code: (i) −x+1, −y, −z. |
The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values. |
Contact | Distance | Symmetry operation |
H7A···H12 | 2.09 | 1 - x, 1 - y, -z |
H13···H26 | 2.26 | 1 + x, y, z |
C12···H36 | 2.65 | 1 - x, 1 - y, -z |
C13···H26 | 2.68 | 1 + x, y, z |
C16···H23 | 2.65 | 1 - x, -y, 1 - z |
C24···H34 | 2.68 | 1 - x, -y -z |
Contact | Percentage contribution |
H···H | 66.5 |
C···H/H···C | 26.8 |
S···H/H···S | 6.6 |
C···S/S···C | 0.1 |
Contact | R (Å) | Eele | Epol | Edis | Erep | Etot |
H7A···H12i + | 6.30 | |||||
H36···C12i | 6.30 | -17.5 | -7.0 | -112.7 | 68.0 | -68.8 |
H13···H26ii + | 9.76 | |||||
C13···H26ii | 9.76 | -8.7 | -2.0 | -31.6 | 18.0 | -24.0 |
C16···H23iii | 9.46 | -12.9 | -2.0 | -41.9 | 29.5 | -28.2 |
C24···H34iv | 10.62 | -11.0 | -2.8 | -33.8 | 21.6 | -26.0 |
Notes: Symmetry operations: (i) 1 - x, 1 - y, -z; (ii) 1 + x, y, z; (iii) 1 - x, -y, 1 - z; (iv) 1 - x, -y, -z. |
Footnotes
‡Additional correspondence author, e-mail: awang_normah@yahoo.com.
Acknowledgements
We gratefully acknowledge the Faculty of Health Sciences and the Faculty of Science and Technology of the Universiti Kebangsaan Malaysia for providing essential laboratory facilities and for technical support from the laboratory assistants. The Universiti Malaysia Terengganu is thanked for the elemental analysis. The authors also thank the Research Centre of Crystalline Materials X-ray crystallography laboratory for the
data.Funding information
This work was supported by the Fundamental Research Grant Scheme (FRGS/1/2018/STG01/UKM/02/20) awarded by the Ministry of Education (MOE). Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (grant No. STR-RCTR-RCCM-001-2019).
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