Bis(μ2-N-methyl-N-phenyl­dithio­carbamato)-κ3S,S′:S;κ3S:S,S′-bis­[(N-methyl-N-phenyl­dithio­carbamato-κ2S,S′)cadmium]: crystal structure and Hirshfeld surface analysis

Suwardi, S.A.N.; Lee, S.M.; Lo, K.M.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989017002705

research communications

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 429-433

https://doi.org/10.1107/S2056989017002705

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Bis(μ₂-N-methyl-N-phenyldithiocarbamato)-κ³S,S′:S;κ³S:S,S′-bis[(N-methyl-N-phenyldithiocarbamato-κ²S,S′)cadmium]: crystal structure and Hirshfeld surface analysis

Siti Aisyah Nabilah Suwardi,^a See Mun Lee,^b ^* Kong Mun Lo,^b Mukesh M. Jotani ^c and Edward R. T. Tiekink ^b ^*

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 February 2017; accepted 16 February 2017; online 21 February 2017)

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 Cd^II 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 xanthates (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 Hg^II atom being hexacoordinated, as in the polymeric form, and the peripheral Hg^II 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—S_long − Cd—S_short. 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).

Table 1
Selected geometric parameters (Å, °)

Cd—S1	2.5044 (8)	C1—S2	1.739 (3)
Cd—S2	2.9331 (8)	C9—S3	1.730 (3)
Cd—S2ⁱ	2.5942 (8)	C9—S4	1.717 (4)
Cd—S3	2.5397 (9)	C1—N1	1.326 (4)
Cd—S4	2.6196 (8)	C9—N2	1.344 (4)
C1—S1	1.716 (3)

S1—Cd—S2	66.15 (2)	S2—Cd—S4	161.85 (3)
S1—Cd—S3	138.16 (3)	S2—Cd—S2ⁱ	92.58 (2)
S1—Cd—S4	114.48 (3)	S3—Cd—S4	70.93 (3)
S1—Cd—S2ⁱ	104.42 (3)	S3—Cd—S2ⁱ	114.47 (3)
S2—Cd—S3	96.36 (2)	S4—Cd—S2ⁱ	104.38 (3)
Symmetry code: (i) -x, -y+1, -z+1.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. The molecule is located about a centre of inversion and unlabelled atoms are generated by the symmetry operation (−x, 1 − y, 1 − z).

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 Cd^II atom by the chelating ligands (Table 1). The widest angle at the Cd^II 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 ( $[\overline{1}]$ 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).

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the 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) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A view of the unit-cell contents of (I)

in projection down the b axis. The C—H⋯π(chelate ring) and C—H⋯S interactions are shown as purple and orange dashed lines, respectively.

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 d_norm 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 d_norm 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).

Table 3
Short interatomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
S1⋯C4	3.462 (3)	−x, − $[{1\over 2}]$ + y, −z
S1⋯H4	2.94	−x, − $[{1\over 2}]$ + 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

Figure 3
A view of the Hirshfeld surface for (I)

mapped over d_norm in the range −0.055 to 1.371 au.

Figure 4
A view of Hirshfeld surface for (I)

mapped over the electrostatic potential in the range ±0.048 au.

Figure 5
Views of the Hirshfeld surface mapped over (a) d_norm about a reference molecule, highlighting the intermolecular C—H⋯S interactions and short interatomic C⋯C contacts as black and red dashed lines, respectively, and (b) with shape-index property about a reference molecule. The C—H⋯π and π⋯H—C interactions are indicated with red and white dotted lines, respectively.

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. d_e + d_i > 2.8 Å. A pair of peaks appearing in the fingerprint plot delineated into S⋯H/H⋯S contacts at d_e + d_i ∼ 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 d_e + d_i ∼ 2.9 Å.

Table 4
Percentage contributions of the different intermolecular contacts to the Hirshfeld surface in (I)

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

Figure 6
Fingerprint plots for (I)

: (a) overall and those delineated into (b) H⋯H, (c) S⋯H/H⋯S, (d) C⋯H/H⋯C and (e) S⋯S contacts.

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 refinement details are summarized in Table 5. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) values set at 1.2–1.5U_eq(C).

Table 5
Experimental details

Crystal data
Chemical formula	[Cd₂(C₈H₈NS₂)₄]
M_r	953.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.7972 (6), 6.4445 (3), 22.582 (1)
β (°)	98.247 (4)
V (Å³)	1843.11 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.64
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.731, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11881, 4894, 3804
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.086, 1.05
No. of reflections	4894
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.48
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1533246

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017002705/hb7659sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017002705/hb7659Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: 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).

Bis(µ₂-N-methyl-N-phenyldithiocarbamato)-κ³S,S':S;κ³S:S,S'-bis[(N-methyl-N-phenyldithiocarbamato-κ²S,S')cadmium(II)] top

Crystal data top

[Cd₂(C₈H₈NS₂)₄]	F(000) = 952
M_r = 953.92	D_x = 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

Data collection top

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	R_int = 0.037
Detector resolution: 10.4041 pixels mm^-1	θ_max = 30.2°, θ_min = 3.2°
ω scan	h = −12→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −9→8
T_min = 0.731, T_max = 1.000	l = −29→30
11881 measured reflections

Refinement top

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(F_o²) + (0.0331P)² + 0.5876P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4894 reflections	Δρ_max = 0.72 e Å⁻³
210 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Short interatomic contacts (Å) in (I). top

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

Percentage contributions of the different intermolecular contacts to the Hirshfeld surface in (I). top

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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