research communications
Bis(μ2-N-methyl-N-phenyldithiocarbamato)-κ3S,S′:S;κ3S:S,S′-bis[(N-methyl-N-phenyldithiocarbamato-κ2S,S′)cadmium]: and Hirshfeld surface analysis
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, bResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia, and cDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India
*Correspondence e-mail: annielee@sunway.edu.my, edwardt@sunway.edu.my
The title compound, [Cd2(C8H8NS2)4], is a centrosymmetric dimer with both chelating and μ2-tridentate dithiocarbamate ligands. The resulting S5 donor set defines a CdII coordination geometry intermediate between square-pyramidal and trigonal–bipyramidal, but tending towards the former. The packing features C—H⋯S and C—H⋯π interactions, which generate a three-dimensional network. The influence of these interactions, along with intra-dimer π–π interactions between chelate rings, has been investigated by an analysis of the Hirshfeld surface.
Keywords: crystal structure; cadmium; dithiocarbamate; Hirshfeld surface analysis.
CCDC reference: 1533246
1. Chemical context
The structural chemistry of the binary zinc-triad (group 12) dithiocarbamates (−S2CNRR′)2 (R/R′ = alkyl/aryl), along with related 1,1-dithiolate ligands, i.e. dithiophosphates [−S2P(OR)2] and dithiocarbonates (xanthates; −S2COR), have long attracted the attention of structural chemists owing to their diversity of structures/supramolecular association patterns in the solid state (Cox & Tiekink, 1997; Tiekink, 2003). The common structural motif adopted by all elements is one that features two chelating ligands and two tridentate ligands (chelating one metal atom and simultaneously bridging to a second), leading, usually, to a centrosymmetric binuclear molecule. Indeed, most zinc dithiocarbamate structures adopt this motif, but when the R/R′ are bulky, a mononuclear species with tetrahedrally coordinated zinc atoms is found; significantly greater structural variety has been noted for the binary zinc dithiophosphates and (Lai et al., 2002; Tan et al., 2015). More diversity in structural motifs is noted in the binary cadmium dithiocarbamates with the recent observation of linear polymeric forms with hexacoordinated cadmium atoms (Tan et al., 2013, 2016; Ferreira et al., 2016). Systematic studies indicated solvent-mediated transformations between polymeric and binuclear structural motifs, with the latter being the thermodynamically more stable (Tan et al., 2013, 2016). The greatest structural diversity among the zinc-triad dithiocarbamates is found for the binary mercury compounds, where mononuclear, binuclear and polymeric structures have been observed, as summarized very recently (Jotani et al., 2016). Complementing the structural motifs already mentioned for zinc and cadmium is a trinuclear species, {Hg[S2CN(tetrahydroquinoline)]2}3 (Rajput et al., 2014), with the central HgII atom being hexacoordinated, as in the polymeric form, and the peripheral HgII atoms being coordinated as in the binuclear form, indicating the possibility that this is an intermediate metastable form in the crystallization of this compound. In light of the above, when crystals of the title compound became available, namely {Cd[S2CN(Me)Ph]2}2, (I), its crystal and molecular structures were studied, along with an evaluation of the supramolecular association in the crystal through an analysis of the Hirshfeld surface.
2. Structural commentary
The centrosymmetric binuclear molecule of (I) (Fig. 1) conforms to the common binuclear motif adopted by binary zinc-triad dithiocarbamates. The S1 dithiocarbamate anion forms a nearly symmetric bridge, as seen in the value of Δ(Cd—S) = 0.09 Å = Cd—Slong − Cd—Sshort. Within the resultant {CdSCS}2 eight-membered ring, which adopts a chair conformation, the bridging S2 atom also forms a longer [S2—Cdi = 2.9331 (8) Å; symmetry code: (i) −x, 1 − y, 1 − z] transannular interaction. The S3 dithiocarbamate ligand is strictly chelating, with Δ(Cd—S) = 0.08 Å. Reflecting the symmetric modes of coordination of the dithiocarbamate ligands, the C—S bond lengths are equal within 5σ (Table 1).
The resultant S5 donor set defines a highly distorted pentacoordinate geometry, with the major distortions due to the disparate Cd—S bond lengths and the acute angles subtended at the CdII atom by the chelating ligands (Table 1). The widest angle at the CdII atom involves the S atoms forming the weaker Cd—S interactions, i.e. S2—Cd—S4 = 161.85 (3)°. A measure of the distortion of a coordination geometry from the ideal square-pyramidal and trigonal–bipyramidal geometries is given by the value of τ (Addison et al., 1984), which computes to 0.0 and 1.0 for the ideal geometries, respectively. In (I), the value of τ is 0.39, i.e. intermediate between the two extremes, but tending towards the former.
3. Supramolecular features
Two specific intermolecular interactions have been identified in the molecular packing of (I), and each involves the participation of phenyl ring C3–C8 (Table 2). Phenyl-C—H⋯π interactions with the C3–C8 ring as the acceptor lead to supramolecular layers parallel to (02), as each binuclear molecule participates in four such interactions. The layers are connected into a three-dimensional architecture by phenyl-C—H⋯S interactions, i.e. with the C3–C8 ring as donor (Fig. 2).
4. Hirshfeld surface analysis
The Hirshfeld surface analysis for (I) was performed as described in a recent report of a related binuclear cadmium dithiocarbamate compound (Jotani et al., 2016). On the Hirshfeld surface mapped over dnorm in the range −0.055 to 1.371 au (Fig. 3), the bright-red spots near the C5, H5 and S1 atoms indicate respective donors and acceptors of intermolecular C—H⋯S interactions; the other pair of faint-red spots near atoms C4 and S1 represent a weaker interaction (Table 3). The donors and acceptors of the specified C—H⋯S and C—H⋯π interactions in Table 2, and short interatomic C⋯H/H⋯C contacts (Table 3) give rise to positive and negative potentials, respectively, and are viewed as the blue and red regions on Hirshfeld surface mapped over electrostatic potential (in the range ±0.048 au) (Fig. 4). The immediate environments about a reference molecule within dnorm and shape-index mapped Hirshfeld surface are illustrated in Figs. 5(a) and 5(b), respectively, and again highlight the influence of C—H⋯S interactions, short C10⋯C15 contacts and C—H⋯π interactions involving phenyl rings (atoms C3–C8) as the acceptor. Thus, the C—H⋯S interactions involving the phenyl-ring C4, C5 and H5 atoms with S1 are shown with black dashed lines in Fig. 5(a); the red dashed lines indicate short interatomic C⋯C contacts (Table 3). The C—H⋯π and their reciprocal contacts, i.e. π⋯H—C, with phenyl-ring atom C14 as donor and phenyl ring C3–C8 as acceptor, are shown with red and white dotted lines, respectively, on the Hirshfeld surface mapped with shape-index property in Fig. 5(b).
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The overall two-dimensional fingerprint plot and those delineated into H⋯H, S⋯H/H⋯S, C⋯H/H⋯C and S⋯S contacts (McKinnon et al., 2007) are illustrated in Figs. 6(a)–(e); their relative contributions to the Hirshfeld surface are summarized quantitatively in Table 4. The relatively low contribution of H⋯H contacts to the Hirshfeld surface results from the involvement of surface H atoms in intermolecular C—H⋯S, C—H⋯π and C⋯H/H⋯C contacts. It is apparent from the fingerprint plot delineated into H⋯H contacts (Fig. 6b) that H⋯H contacts do not exert much influence on the molecular packing, as their interatomic distances are greater than the sum of their van der Waals radii, i.e. de + di > 2.8 Å. A pair of peaks appearing in the fingerprint plot delineated into S⋯H/H⋯S contacts at de + di ∼ 2.8 Å (Fig. 6c) arise from the C5—H5⋯S1 interaction; the weaker C4⋯H4⋯S1 interaction and short interatomic H⋯S/S⋯H contacts involving the S3 atom (Table 3) are viewed as a pair of thin green lines aligned at de + di ∼ 2.9 Å.
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The distribution of points showing the superimposition of a forceps-like shape on characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C contacts (Fig. 6d) indicate the significance of these contacts through the presence of C—H⋯π interactions and short interatomic C⋯H/H⋯C contacts in the crystal. A pair of green lines within the forceps also indicates the influence of these contacts. Finally, an arrow-shaped distribution of green points in the centre in the plot corresponding to S⋯S contacts (Fig. 6e), together with the contribution from Cd⋯S/S⋯Cd contacts to the Hirshfeld surface (Table 4), show the presence of intramolecular π–π stacking interactions between the Cd/S1/C1/S2 chelate rings of inversion-related molecules [Cg⋯Cg = 3.6117 (11) Å; symmetry code: −x, 1 − y, 1 − z]. The small contributions from Cd⋯H/H⋯Cd and N⋯H/H⋯N contacts (Table 4) do not impact significantly on the molecular packing.
5. Database survey
The dithiocarbamate ligand featured in (I) has been reported in several other crystal structures (Groom et al., 2016). Indeed, the binary zinc (Baba et al., 2002) and mercury (Onwudiwe & Ajibade, 2011a,b) structures have been reported already, so, in this sense, the structure of (I) completes the series. The zinc compound adopts the common binuclear motif (Baba et al., 2002). More interesting is the fact that for the mercury structure, both mononuclear (Onwudiwe & Ajibade, 2011a) and binuclear (Onwudiwe & Ajibade, 2011b) forms have been reported (Tan et al., 2015). As to the other main group element structures, the binary dithiocarbamate compounds of antimony(III) (Baba et al., 2003) and bismuth(III) (Yin et al., 2004), including an acetonitrile solvate (Lai & Tiekink, 2007), have been described. These, too, present the same structural features as reported for the overwhelming majority of related antimony(III) (Liu & Tiekink, 2005) and bismuth(III) dithiocarbamate compounds (Lai & Tiekink, 2007).
6. Synthesis and crystallization
All chemicals and solvents were used as purchased without purification, and all reactions were carried out under ambient conditions. The melting point was determined using an Electrothermal digital melting-point apparatus and was uncorrected. The IR spectrum was obtained on a PerkinElmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer from 4000 to 400 cm−1. 1H and 13C NMR spectra were recorded at room temperature in DMSO-d6 solution on a Jeol ECA 400 MHz FT–NMR spectrometer.
Sodium methylphenyldithiocarbamate (1.0 mmol, 0.205 g) in methanol (25 ml) was added to cadmium chloride (1.0 mmol, 0.183 g) in methanol (10 ml). The resulting mixture was stirred and refluxed for 2 h. The filtrate was evaporated until an off-white precipitate was obtained, which was recrystallized in methanol. Slow evaporation of the filtrate yielded colourless crystals of the title compound (yield: 0.194 g, 61%; m.p. 473 K). IR (cm−1): 1491 (m) [ν(C—N)], 1160 (m), 964 (s) [ν(C—S)] cm−1. 1H NMR: δ 7.26–7.42 (m, 5H, aromatic H), 2.05 (s, 3H, CH3). 13C NMR: δ 46.6 (Me) 125.6, 128.4, 129.6, 147.9 (aromatic C), 207.8 (CS2).
7. Refinement
Crystal data, data collection and structure . Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) values set at 1.2–1.5Ueq(C).
details are summarized in Table 5
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Supporting information
CCDC reference: 1533246
https://doi.org/10.1107/S2056989017002705/hb7659sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002705/hb7659Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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).[Cd2(C8H8NS2)4] | F(000) = 952 |
Mr = 953.92 | Dx = 1.719 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7972 (6) Å | Cell parameters from 4387 reflections |
b = 6.4445 (3) Å | θ = 3.4–29.8° |
c = 22.582 (1) Å | µ = 1.64 mm−1 |
β = 98.247 (4)° | T = 100 K |
V = 1843.11 (15) Å3 | Block, colourless |
Z = 2 | 0.20 × 0.15 × 0.10 mm |
Agilent SuperNova Dual Source diffractometer with an Atlas detector | 4894 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 3804 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.037 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 30.2°, θmin = 3.2° |
ω scan | h = −12→17 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −9→8 |
Tmin = 0.731, Tmax = 1.000 | l = −29→30 |
11881 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.086 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.5876P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4894 reflections | Δρmax = 0.72 e Å−3 |
210 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 | ||
Cd | 0.12343 (2) | 0.35538 (4) | 0.48383 (2) | 0.02641 (8) | |
S1 | 0.02923 (7) | 0.37408 (12) | 0.37881 (4) | 0.02834 (19) | |
S2 | 0.02121 (6) | 0.75614 (12) | 0.45307 (3) | 0.02341 (17) | |
S3 | 0.28949 (6) | 0.50187 (12) | 0.54452 (4) | 0.02566 (18) | |
S4 | 0.26597 (7) | 0.06179 (13) | 0.50220 (4) | 0.0311 (2) | |
N1 | −0.09657 (19) | 0.6884 (4) | 0.34672 (11) | 0.0205 (5) | |
N2 | 0.4316 (2) | 0.2090 (4) | 0.57566 (12) | 0.0287 (6) | |
C1 | −0.0239 (2) | 0.6135 (5) | 0.38915 (13) | 0.0220 (6) | |
C2 | −0.1463 (3) | 0.8929 (5) | 0.34931 (15) | 0.0286 (7) | |
H2A | −0.2198 | 0.8754 | 0.3559 | 0.043* | |
H2B | −0.1443 | 0.9663 | 0.3115 | 0.043* | |
H2C | −0.1078 | 0.9736 | 0.3823 | 0.043* | |
C3 | −0.1353 (2) | 0.5650 (5) | 0.29431 (13) | 0.0217 (6) | |
C4 | −0.0939 (3) | 0.5954 (5) | 0.24187 (14) | 0.0271 (7) | |
H4 | −0.0392 | 0.6940 | 0.2401 | 0.033* | |
C5 | −0.1334 (3) | 0.4800 (5) | 0.19168 (15) | 0.0314 (8) | |
H5 | −0.1055 | 0.4999 | 0.1553 | 0.038* | |
C6 | −0.2119 (3) | 0.3383 (5) | 0.19425 (16) | 0.0334 (8) | |
H6 | −0.2381 | 0.2593 | 0.1598 | 0.040* | |
C7 | −0.2535 (3) | 0.3093 (5) | 0.24708 (17) | 0.0334 (8) | |
H7 | −0.3084 | 0.2111 | 0.2487 | 0.040* | |
C8 | −0.2150 (2) | 0.4235 (5) | 0.29753 (15) | 0.0271 (7) | |
H8 | −0.2432 | 0.4045 | 0.3338 | 0.032* | |
C9 | 0.3372 (2) | 0.2509 (5) | 0.54363 (14) | 0.0257 (7) | |
C10 | 0.4776 (3) | 0.0001 (5) | 0.57988 (17) | 0.0398 (9) | |
H10A | 0.5511 | 0.0070 | 0.5724 | 0.060* | |
H10B | 0.4372 | −0.0902 | 0.5500 | 0.060* | |
H10C | 0.4752 | −0.0560 | 0.6200 | 0.060* | |
C11 | 0.4909 (2) | 0.3640 (5) | 0.61192 (15) | 0.0278 (7) | |
C12 | 0.4636 (3) | 0.4133 (5) | 0.66742 (15) | 0.0303 (7) | |
H12 | 0.4045 | 0.3484 | 0.6808 | 0.036* | |
C13 | 0.5227 (3) | 0.5572 (6) | 0.70328 (16) | 0.0345 (8) | |
H13 | 0.5038 | 0.5920 | 0.7412 | 0.041* | |
C14 | 0.6088 (3) | 0.6503 (5) | 0.68420 (17) | 0.0378 (9) | |
H14 | 0.6491 | 0.7494 | 0.7089 | 0.045* | |
C15 | 0.6364 (3) | 0.5989 (6) | 0.62904 (18) | 0.0367 (9) | |
H15 | 0.6965 | 0.6615 | 0.6162 | 0.044* | |
C16 | 0.5770 (3) | 0.4566 (5) | 0.59235 (16) | 0.0329 (8) | |
H16 | 0.5953 | 0.4232 | 0.5542 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.02523 (14) | 0.03538 (16) | 0.01777 (12) | 0.00772 (10) | 0.00019 (9) | 0.00105 (10) |
S1 | 0.0369 (5) | 0.0274 (4) | 0.0186 (4) | 0.0104 (4) | −0.0034 (3) | −0.0032 (3) |
S2 | 0.0267 (4) | 0.0251 (4) | 0.0172 (4) | 0.0002 (3) | −0.0014 (3) | −0.0024 (3) |
S3 | 0.0252 (4) | 0.0258 (4) | 0.0251 (4) | 0.0074 (3) | 0.0005 (3) | 0.0023 (3) |
S4 | 0.0325 (5) | 0.0277 (4) | 0.0319 (5) | 0.0082 (4) | 0.0001 (3) | −0.0026 (4) |
N1 | 0.0237 (13) | 0.0209 (13) | 0.0161 (12) | 0.0013 (10) | −0.0002 (10) | 0.0015 (10) |
N2 | 0.0266 (14) | 0.0273 (14) | 0.0315 (16) | 0.0099 (12) | 0.0017 (12) | 0.0024 (12) |
C1 | 0.0239 (16) | 0.0259 (17) | 0.0168 (15) | −0.0029 (13) | 0.0051 (12) | 0.0014 (12) |
C2 | 0.0355 (19) | 0.0213 (16) | 0.0271 (18) | 0.0041 (14) | −0.0019 (14) | 0.0021 (13) |
C3 | 0.0238 (15) | 0.0208 (15) | 0.0184 (15) | 0.0022 (13) | −0.0039 (11) | 0.0015 (12) |
C4 | 0.0293 (17) | 0.0289 (17) | 0.0221 (16) | −0.0056 (14) | 0.0000 (13) | 0.0004 (13) |
C5 | 0.042 (2) | 0.0311 (18) | 0.0196 (16) | −0.0015 (16) | −0.0005 (14) | 0.0018 (14) |
C6 | 0.0358 (19) | 0.0315 (19) | 0.0285 (19) | −0.0031 (15) | −0.0106 (14) | −0.0058 (15) |
C7 | 0.0269 (18) | 0.0319 (18) | 0.039 (2) | −0.0059 (15) | −0.0027 (14) | −0.0007 (16) |
C8 | 0.0249 (16) | 0.0290 (17) | 0.0267 (17) | 0.0022 (14) | 0.0017 (13) | 0.0026 (14) |
C9 | 0.0256 (17) | 0.0294 (18) | 0.0230 (16) | 0.0072 (14) | 0.0059 (12) | 0.0042 (14) |
C10 | 0.041 (2) | 0.033 (2) | 0.042 (2) | 0.0175 (16) | −0.0041 (16) | 0.0032 (17) |
C11 | 0.0216 (16) | 0.0307 (18) | 0.0301 (18) | 0.0101 (14) | 0.0002 (13) | 0.0079 (14) |
C12 | 0.0242 (17) | 0.0356 (19) | 0.0309 (19) | 0.0053 (15) | 0.0030 (14) | 0.0096 (15) |
C13 | 0.0335 (19) | 0.039 (2) | 0.0290 (19) | 0.0069 (16) | −0.0007 (15) | 0.0040 (16) |
C14 | 0.033 (2) | 0.033 (2) | 0.043 (2) | 0.0031 (16) | −0.0094 (16) | 0.0071 (17) |
C15 | 0.0211 (17) | 0.038 (2) | 0.051 (2) | 0.0048 (15) | 0.0048 (15) | 0.0161 (17) |
C16 | 0.0290 (18) | 0.0348 (19) | 0.036 (2) | 0.0103 (16) | 0.0079 (15) | 0.0112 (16) |
Cd—S1 | 2.5044 (8) | C4—H4 | 0.9500 |
Cd—S2 | 2.9331 (8) | C5—C6 | 1.365 (5) |
Cd—S2i | 2.5942 (8) | C5—H5 | 0.9500 |
Cd—S3 | 2.5397 (9) | C6—C7 | 1.387 (5) |
Cd—S4 | 2.6196 (8) | C6—H6 | 0.9500 |
C1—S1 | 1.716 (3) | C7—C8 | 1.386 (5) |
C1—S2 | 1.739 (3) | C7—H7 | 0.9500 |
S2—Cdi | 2.5942 (8) | C8—H8 | 0.9500 |
C9—S3 | 1.730 (3) | C10—H10A | 0.9800 |
C9—S4 | 1.717 (4) | C10—H10B | 0.9800 |
C1—N1 | 1.326 (4) | C10—H10C | 0.9800 |
N1—C3 | 1.453 (4) | C11—C16 | 1.380 (5) |
N1—C2 | 1.468 (4) | C11—C12 | 1.386 (5) |
C9—N2 | 1.344 (4) | C12—C13 | 1.383 (5) |
N2—C11 | 1.438 (4) | C12—H12 | 0.9500 |
N2—C10 | 1.467 (4) | C13—C14 | 1.377 (5) |
C2—H2A | 0.9800 | C13—H13 | 0.9500 |
C2—H2B | 0.9800 | C14—C15 | 1.383 (5) |
C2—H2C | 0.9800 | C14—H14 | 0.9500 |
C3—C8 | 1.378 (4) | C15—C16 | 1.387 (5) |
C3—C4 | 1.379 (4) | C15—H15 | 0.9500 |
C4—C5 | 1.389 (4) | C16—H16 | 0.9500 |
S1—Cd—S2 | 66.15 (2) | C6—C5—H5 | 119.8 |
S1—Cd—S3 | 138.16 (3) | C4—C5—H5 | 119.8 |
S1—Cd—S4 | 114.48 (3) | C5—C6—C7 | 120.1 (3) |
S1—Cd—S2i | 104.42 (3) | C5—C6—H6 | 119.9 |
S2—Cd—S3 | 96.36 (2) | C7—C6—H6 | 119.9 |
S2—Cd—S4 | 161.85 (3) | C8—C7—C6 | 120.0 (3) |
S2—Cd—S2i | 92.58 (2) | C8—C7—H7 | 120.0 |
S3—Cd—S4 | 70.93 (3) | C6—C7—H7 | 120.0 |
S3—Cd—S2i | 114.47 (3) | C3—C8—C7 | 119.1 (3) |
S4—Cd—S2i | 104.38 (3) | C3—C8—H8 | 120.5 |
C1—S1—Cd | 93.49 (11) | C7—C8—H8 | 120.5 |
C1—S2—Cdi | 97.54 (10) | N2—C9—S4 | 121.1 (2) |
C1—S2—Cd | 79.34 (11) | N2—C9—S3 | 118.3 (3) |
Cdi—S2—Cd | 87.43 (2) | S4—C9—S3 | 120.62 (19) |
C9—S3—Cd | 85.16 (11) | N2—C10—H10A | 109.5 |
C9—S4—Cd | 82.93 (11) | N2—C10—H10B | 109.5 |
C1—N1—C3 | 120.7 (3) | H10A—C10—H10B | 109.5 |
C1—N1—C2 | 124.1 (3) | N2—C10—H10C | 109.5 |
C3—N1—C2 | 115.2 (2) | H10A—C10—H10C | 109.5 |
C9—N2—C11 | 121.8 (3) | H10B—C10—H10C | 109.5 |
C9—N2—C10 | 122.8 (3) | C16—C11—C12 | 120.5 (3) |
C11—N2—C10 | 115.3 (3) | C16—C11—N2 | 119.9 (3) |
N1—C1—S1 | 118.6 (2) | C12—C11—N2 | 119.6 (3) |
N1—C1—S2 | 121.5 (2) | C13—C12—C11 | 119.7 (3) |
S1—C1—S2 | 119.82 (18) | C13—C12—H12 | 120.1 |
N1—C2—H2A | 109.5 | C11—C12—H12 | 120.1 |
N1—C2—H2B | 109.5 | C14—C13—C12 | 120.3 (3) |
H2A—C2—H2B | 109.5 | C14—C13—H13 | 119.9 |
N1—C2—H2C | 109.5 | C12—C13—H13 | 119.9 |
H2A—C2—H2C | 109.5 | C13—C14—C15 | 119.8 (4) |
H2B—C2—H2C | 109.5 | C13—C14—H14 | 120.1 |
C8—C3—C4 | 121.2 (3) | C15—C14—H14 | 120.1 |
C8—C3—N1 | 119.2 (3) | C14—C15—C16 | 120.5 (3) |
C4—C3—N1 | 119.6 (3) | C14—C15—H15 | 119.8 |
C3—C4—C5 | 119.0 (3) | C16—C15—H15 | 119.8 |
C3—C4—H4 | 120.5 | C11—C16—C15 | 119.3 (3) |
C5—C4—H4 | 120.5 | C11—C16—H16 | 120.4 |
C6—C5—C4 | 120.5 (3) | C15—C16—H16 | 120.4 |
C3—N1—C1—S1 | 3.9 (4) | C6—C7—C8—C3 | −0.1 (5) |
C2—N1—C1—S1 | −178.4 (2) | C11—N2—C9—S4 | −178.2 (2) |
C3—N1—C1—S2 | −178.5 (2) | C10—N2—C9—S4 | −3.1 (4) |
C2—N1—C1—S2 | −0.7 (4) | C11—N2—C9—S3 | 2.5 (4) |
Cd—S1—C1—N1 | −170.8 (2) | C10—N2—C9—S3 | 177.6 (2) |
Cd—S1—C1—S2 | 11.52 (17) | Cd—S4—C9—N2 | 174.9 (3) |
Cdi—S2—C1—N1 | 86.5 (2) | Cd—S4—C9—S3 | −5.81 (16) |
Cd—S2—C1—N1 | 172.4 (2) | Cd—S3—C9—N2 | −174.7 (3) |
Cdi—S2—C1—S1 | −95.91 (17) | Cd—S3—C9—S4 | 5.96 (17) |
Cd—S2—C1—S1 | −9.98 (15) | C9—N2—C11—C16 | −103.8 (4) |
C1—N1—C3—C8 | 83.8 (4) | C10—N2—C11—C16 | 80.7 (4) |
C2—N1—C3—C8 | −94.1 (3) | C9—N2—C11—C12 | 78.8 (4) |
C1—N1—C3—C4 | −98.0 (3) | C10—N2—C11—C12 | −96.7 (4) |
C2—N1—C3—C4 | 84.1 (3) | C16—C11—C12—C13 | 0.4 (5) |
C8—C3—C4—C5 | −0.3 (5) | N2—C11—C12—C13 | 177.8 (3) |
N1—C3—C4—C5 | −178.4 (3) | C11—C12—C13—C14 | −0.5 (5) |
C3—C4—C5—C6 | −0.1 (5) | C12—C13—C14—C15 | −0.2 (5) |
C4—C5—C6—C7 | 0.4 (5) | C13—C14—C15—C16 | 1.0 (5) |
C5—C6—C7—C8 | −0.4 (5) | C12—C11—C16—C15 | 0.4 (5) |
C4—C3—C8—C7 | 0.4 (5) | N2—C11—C16—C15 | −177.0 (3) |
N1—C3—C8—C7 | 178.5 (3) | C14—C15—C16—C11 | −1.1 (5) |
Symmetry code: (i) −x, −y+1, −z+1. |
Cg1 is the ring centroid of the C3–C8 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Cg1ii | 0.95 | 2.99 | 3.883 (4) | 156 |
C5—H5···S1iii | 0.95 | 2.75 | 3.372 (4) | 124 |
Symmetry codes: (ii) x+1, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2. |
Contact | Distance | Symmetry operation |
S1···C4 | 3.462 (3) | -x, -1/2+y, -z |
S1···H4 | 2.94 | -x, -1/2+y, -z |
S3···H16 | 2.88 | 1-x, 1-y, 1-z |
C10···C15 | 3.376 (5) | x, -1+y, z |
C7···H2B | 2.89 | x, -1+y, z |
C13···H7 | 2.84 | 1-x, -y, z |
C14···H7 | 2.87 | 1-x, -y, z |
C14···H10C | 2.81 | x, 1+y, z |
C15···H6 | 2.84 | 1-x, -y, z |
Contact | % Contribution in (I) |
H···H | 40.0 |
S···H/H···S | 26.7 |
C···H/H···C | 24.8 |
S···S | 5.8 |
Cd···H/H···Cd | 1.2 |
N···H/H···N | 0.8 |
Cd···S/S···Cd | 0.7 |
Acknowledgements
The authors are grateful to Sunway University and the Ministry of Higher Education of Malaysia (MOHE) Fundamental Research Grant Scheme for supporting this research.
Funding information
Funding for this research was provided by: Ministry of Higher Education of Malaysia (MOHE) (award No. FP033-2014B).
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