PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2017 March 1; 73(Pt 3): 429–433.
Published online 2017 February 21. doi:  10.1107/S2056989017002705
PMCID: PMC5347070

Bis(μ2-N-methyl-N-phenyl­dithio­carbamato)-κ3 S,S′:S3 S:S,S′-bis­[(N-methyl-N-phenyl­dithio­carbamato-κ2 S,S′)cadmium]: crystal structure and Hirshfeld surface analysis

Abstract

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

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 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.

An external file that holds a picture, illustration, etc.
Object name is e-73-00429-scheme1.jpg

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  ).

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 ...
Table 1
Selected geometric parameters (Å, °)

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.

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 (An external file that holds a picture, illustration, etc.
Object name is e-73-00429-efi1.jpg02), 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  ).

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.
Table 2
Hydrogen-bond geometry (Å, °)

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).

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

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. 6  b) 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. 6  c) 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.

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

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. 6  d) 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. 6  e), 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.

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  ).

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-d 6 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).

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017002705/hb7659sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017002705/hb7659Isup2.hkl

CCDC reference: 1533246

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful to Sunway University and the Ministry of Higher Education of Malaysia (MOHE) Fundamental Research Grant Scheme for supporting this research.

supplementary crystallographic information

Crystal data

[Cd2(C8H8NS2)4]F(000) = 952
Mr = 953.92Dx = 1.719 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.7972 (6) ÅCell parameters from 4387 reflections
b = 6.4445 (3) Åθ = 3.4–29.8°
c = 22.582 (1) ŵ = 1.64 mm1
β = 98.247 (4)°T = 100 K
V = 1843.11 (15) Å3Block, colourless
Z = 20.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector4894 independent reflections
Radiation source: SuperNova (Mo) X-ray Source3804 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.037
Detector resolution: 10.4041 pixels mm-1θmax = 30.2°, θmin = 3.2°
ω scanh = −12→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)k = −9→8
Tmin = 0.731, Tmax = 1.000l = −29→30
11881 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.086w = 1/[σ2(Fo2) + (0.0331P)2 + 0.5876P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
4894 reflectionsΔρmax = 0.72 e Å3
210 parametersΔρmin = −0.48 e Å3
0 restraints

Special details

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)

xyzUiso*/Ueq
Cd0.12343 (2)0.35538 (4)0.48383 (2)0.02641 (8)
S10.02923 (7)0.37408 (12)0.37881 (4)0.02834 (19)
S20.02121 (6)0.75614 (12)0.45307 (3)0.02341 (17)
S30.28949 (6)0.50187 (12)0.54452 (4)0.02566 (18)
S40.26597 (7)0.06179 (13)0.50220 (4)0.0311 (2)
N1−0.09657 (19)0.6884 (4)0.34672 (11)0.0205 (5)
N20.4316 (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−0.21980.87540.35590.043*
H2B−0.14430.96630.31150.043*
H2C−0.10780.97360.38230.043*
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)
H4−0.03920.69400.24010.033*
C5−0.1334 (3)0.4800 (5)0.19168 (15)0.0314 (8)
H5−0.10550.49990.15530.038*
C6−0.2119 (3)0.3383 (5)0.19425 (16)0.0334 (8)
H6−0.23810.25930.15980.040*
C7−0.2535 (3)0.3093 (5)0.24708 (17)0.0334 (8)
H7−0.30840.21110.24870.040*
C8−0.2150 (2)0.4235 (5)0.29753 (15)0.0271 (7)
H8−0.24320.40450.33380.032*
C90.3372 (2)0.2509 (5)0.54363 (14)0.0257 (7)
C100.4776 (3)0.0001 (5)0.57988 (17)0.0398 (9)
H10A0.55110.00700.57240.060*
H10B0.4372−0.09020.55000.060*
H10C0.4752−0.05600.62000.060*
C110.4909 (2)0.3640 (5)0.61192 (15)0.0278 (7)
C120.4636 (3)0.4133 (5)0.66742 (15)0.0303 (7)
H120.40450.34840.68080.036*
C130.5227 (3)0.5572 (6)0.70328 (16)0.0345 (8)
H130.50380.59200.74120.041*
C140.6088 (3)0.6503 (5)0.68420 (17)0.0378 (9)
H140.64910.74940.70890.045*
C150.6364 (3)0.5989 (6)0.62904 (18)0.0367 (9)
H150.69650.66150.61620.044*
C160.5770 (3)0.4566 (5)0.59235 (16)0.0329 (8)
H160.59530.42320.55420.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd0.02523 (14)0.03538 (16)0.01777 (12)0.00772 (10)0.00019 (9)0.00105 (10)
S10.0369 (5)0.0274 (4)0.0186 (4)0.0104 (4)−0.0034 (3)−0.0032 (3)
S20.0267 (4)0.0251 (4)0.0172 (4)0.0002 (3)−0.0014 (3)−0.0024 (3)
S30.0252 (4)0.0258 (4)0.0251 (4)0.0074 (3)0.0005 (3)0.0023 (3)
S40.0325 (5)0.0277 (4)0.0319 (5)0.0082 (4)0.0001 (3)−0.0026 (4)
N10.0237 (13)0.0209 (13)0.0161 (12)0.0013 (10)−0.0002 (10)0.0015 (10)
N20.0266 (14)0.0273 (14)0.0315 (16)0.0099 (12)0.0017 (12)0.0024 (12)
C10.0239 (16)0.0259 (17)0.0168 (15)−0.0029 (13)0.0051 (12)0.0014 (12)
C20.0355 (19)0.0213 (16)0.0271 (18)0.0041 (14)−0.0019 (14)0.0021 (13)
C30.0238 (15)0.0208 (15)0.0184 (15)0.0022 (13)−0.0039 (11)0.0015 (12)
C40.0293 (17)0.0289 (17)0.0221 (16)−0.0056 (14)0.0000 (13)0.0004 (13)
C50.042 (2)0.0311 (18)0.0196 (16)−0.0015 (16)−0.0005 (14)0.0018 (14)
C60.0358 (19)0.0315 (19)0.0285 (19)−0.0031 (15)−0.0106 (14)−0.0058 (15)
C70.0269 (18)0.0319 (18)0.039 (2)−0.0059 (15)−0.0027 (14)−0.0007 (16)
C80.0249 (16)0.0290 (17)0.0267 (17)0.0022 (14)0.0017 (13)0.0026 (14)
C90.0256 (17)0.0294 (18)0.0230 (16)0.0072 (14)0.0059 (12)0.0042 (14)
C100.041 (2)0.033 (2)0.042 (2)0.0175 (16)−0.0041 (16)0.0032 (17)
C110.0216 (16)0.0307 (18)0.0301 (18)0.0101 (14)0.0002 (13)0.0079 (14)
C120.0242 (17)0.0356 (19)0.0309 (19)0.0053 (15)0.0030 (14)0.0096 (15)
C130.0335 (19)0.039 (2)0.0290 (19)0.0069 (16)−0.0007 (15)0.0040 (16)
C140.033 (2)0.033 (2)0.043 (2)0.0031 (16)−0.0094 (16)0.0071 (17)
C150.0211 (17)0.038 (2)0.051 (2)0.0048 (15)0.0048 (15)0.0161 (17)
C160.0290 (18)0.0348 (19)0.036 (2)0.0103 (16)0.0079 (15)0.0112 (16)

Geometric parameters (Å, º)

Cd—S12.5044 (8)C4—H40.9500
Cd—S22.9331 (8)C5—C61.365 (5)
Cd—S2i2.5942 (8)C5—H50.9500
Cd—S32.5397 (9)C6—C71.387 (5)
Cd—S42.6196 (8)C6—H60.9500
C1—S11.716 (3)C7—C81.386 (5)
C1—S21.739 (3)C7—H70.9500
S2—Cdi2.5942 (8)C8—H80.9500
C9—S31.730 (3)C10—H10A0.9800
C9—S41.717 (4)C10—H10B0.9800
C1—N11.326 (4)C10—H10C0.9800
N1—C31.453 (4)C11—C161.380 (5)
N1—C21.468 (4)C11—C121.386 (5)
C9—N21.344 (4)C12—C131.383 (5)
N2—C111.438 (4)C12—H120.9500
N2—C101.467 (4)C13—C141.377 (5)
C2—H2A0.9800C13—H130.9500
C2—H2B0.9800C14—C151.383 (5)
C2—H2C0.9800C14—H140.9500
C3—C81.378 (4)C15—C161.387 (5)
C3—C41.379 (4)C15—H150.9500
C4—C51.389 (4)C16—H160.9500
S1—Cd—S266.15 (2)C6—C5—H5119.8
S1—Cd—S3138.16 (3)C4—C5—H5119.8
S1—Cd—S4114.48 (3)C5—C6—C7120.1 (3)
S1—Cd—S2i104.42 (3)C5—C6—H6119.9
S2—Cd—S396.36 (2)C7—C6—H6119.9
S2—Cd—S4161.85 (3)C8—C7—C6120.0 (3)
S2—Cd—S2i92.58 (2)C8—C7—H7120.0
S3—Cd—S470.93 (3)C6—C7—H7120.0
S3—Cd—S2i114.47 (3)C3—C8—C7119.1 (3)
S4—Cd—S2i104.38 (3)C3—C8—H8120.5
C1—S1—Cd93.49 (11)C7—C8—H8120.5
C1—S2—Cdi97.54 (10)N2—C9—S4121.1 (2)
C1—S2—Cd79.34 (11)N2—C9—S3118.3 (3)
Cdi—S2—Cd87.43 (2)S4—C9—S3120.62 (19)
C9—S3—Cd85.16 (11)N2—C10—H10A109.5
C9—S4—Cd82.93 (11)N2—C10—H10B109.5
C1—N1—C3120.7 (3)H10A—C10—H10B109.5
C1—N1—C2124.1 (3)N2—C10—H10C109.5
C3—N1—C2115.2 (2)H10A—C10—H10C109.5
C9—N2—C11121.8 (3)H10B—C10—H10C109.5
C9—N2—C10122.8 (3)C16—C11—C12120.5 (3)
C11—N2—C10115.3 (3)C16—C11—N2119.9 (3)
N1—C1—S1118.6 (2)C12—C11—N2119.6 (3)
N1—C1—S2121.5 (2)C13—C12—C11119.7 (3)
S1—C1—S2119.82 (18)C13—C12—H12120.1
N1—C2—H2A109.5C11—C12—H12120.1
N1—C2—H2B109.5C14—C13—C12120.3 (3)
H2A—C2—H2B109.5C14—C13—H13119.9
N1—C2—H2C109.5C12—C13—H13119.9
H2A—C2—H2C109.5C13—C14—C15119.8 (4)
H2B—C2—H2C109.5C13—C14—H14120.1
C8—C3—C4121.2 (3)C15—C14—H14120.1
C8—C3—N1119.2 (3)C14—C15—C16120.5 (3)
C4—C3—N1119.6 (3)C14—C15—H15119.8
C3—C4—C5119.0 (3)C16—C15—H15119.8
C3—C4—H4120.5C11—C16—C15119.3 (3)
C5—C4—H4120.5C11—C16—H16120.4
C6—C5—C4120.5 (3)C15—C16—H16120.4
C3—N1—C1—S13.9 (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—S32.5 (4)
Cd—S1—C1—N1−170.8 (2)C10—N2—C9—S3177.6 (2)
Cd—S1—C1—S211.52 (17)Cd—S4—C9—N2174.9 (3)
Cdi—S2—C1—N186.5 (2)Cd—S4—C9—S3−5.81 (16)
Cd—S2—C1—N1172.4 (2)Cd—S3—C9—N2−174.7 (3)
Cdi—S2—C1—S1−95.91 (17)Cd—S3—C9—S45.96 (17)
Cd—S2—C1—S1−9.98 (15)C9—N2—C11—C16−103.8 (4)
C1—N1—C3—C883.8 (4)C10—N2—C11—C1680.7 (4)
C2—N1—C3—C8−94.1 (3)C9—N2—C11—C1278.8 (4)
C1—N1—C3—C4−98.0 (3)C10—N2—C11—C12−96.7 (4)
C2—N1—C3—C484.1 (3)C16—C11—C12—C130.4 (5)
C8—C3—C4—C5−0.3 (5)N2—C11—C12—C13177.8 (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—C70.4 (5)C13—C14—C15—C161.0 (5)
C5—C6—C7—C8−0.4 (5)C12—C11—C16—C150.4 (5)
C4—C3—C8—C70.4 (5)N2—C11—C16—C15−177.0 (3)
N1—C3—C8—C7178.5 (3)C14—C15—C16—C11−1.1 (5)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

Cg1 is the ring centroid of the C3–C8 ring.

D—H···AD—HH···AD···AD—H···A
C14—H14···Cg1ii0.952.993.883 (4)156
C5—H5···S1iii0.952.753.372 (4)124

Symmetry codes: (ii) x+1, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2.

References

  • Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.
  • Agilent (2013). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA.
  • Baba, I., Lee, L. H., Farina, Y., Othman, A. H., Ibrahim, A. R., Usman, A., Fun, H.-K. & Ng, S. W. (2002). Acta Cryst. E58, m744–m745.
  • Baba, I., Skelton, B. W. & White, A. H. (2003). Aust. J. Chem. 56, 27–29.
  • Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Cox, M. J. & Tiekink, E. R. T. (1997). Rev. Inorg. Chem. 17, 1–23.
  • Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
  • Ferreira, I. P., de Lima, G. M., Paniago, E. B., Pinheiro, C. B., Wardell, J. L. & Wardell, S. M. S. V. (2016). Inorg. Chim. Acta, 441, 137–145.
  • Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [PMC free article] [PubMed]
  • Jotani, M. M., Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1085–1092.
  • Lai, C. S., Lim, Y. X., Yap, T. C. & Tiekink, E. R. T. (2002). CrystEngComm, 4, 596–600.
  • Lai, C. S. & Tiekink, E. R. T. (2007). Z. Kristallogr. 222, 532–538.
  • Liu, Y. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 20–27.
  • McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. [PubMed]
  • Onwudiwe, D. C. & Ajibade, P. A. (2011a). J. Coord. Chem. 64, 2963–2973.
  • Onwudiwe, D. C. & Ajibade, P. A. (2011b). Int. J. Mol. Sci. 12, 1964–1978.
  • Rajput, G., Yadav, M. K., Thakur, T. S., Drew, M. G. B. & Singh, N. (2014). Polyhedron, 69, 225–233.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. [PMC free article] [PubMed]
  • Tan, Y. S., Halim, S. N. A. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 113–126.
  • Tan, Y. S., Ooi, K. K., Ang, K. P., Akim, A. M., Cheah, Y.-K., Halim, S. N. A., Seng, H.-L. & Tiekink, E. R. T. (2015). J. Inorg. Biochem. 150, 48–62. [PubMed]
  • Tan, Y. S., Sudlow, A. L., Molloy, K. C., Morishima, Y., Fujisawa, K., Jackson, W. J., Henderson, W., Halim, S. N., Bt, A., Ng, S. W. & Tiekink, E. R. T. (2013). Cryst. Growth Des. 13, 3046–3056.
  • Tiekink, E. R. T. (2003). CrystEngComm, 5, 101–113.
  • Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
  • Yin, H.-D., Wang, C.-H. & Wang, Y. (2004). Appl. Organomet. Chem. 18, 199–200.

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography