A two-dimensional coordination polymer: poly[[bis­[μ2-N-ethyl-N-(pyridin-4-ylmeth­yl)di­thio­carbamato-κ3N:S,S′]cadmium(II)] 3-methyl­pyridine monosolvate]

Arman, H.D.; Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S2056989017003516

research communications

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ISSN: 2056-9890

Volume 73| Part 4| April 2017| Pages 488-492

https://doi.org/10.1107/S2056989017003516

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A two-dimensional coordination polymer: poly[[bis[μ₂-N-ethyl-N-(pyridin-4-ylmethyl)dithiocarbamato-κ³N:S,S′]cadmium(II)] 3-methylpyridine monosolvate]

Hadi D. Arman,^a Pavel Poplaukhin ^b and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, ^bChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio 43202, USA, and ^cCentre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 March 2017; accepted 4 March 2017; online 10 March 2017)

The title compound, {[Cd(C₉H₁₁N₂S₂)₂]·C₆H₇N}_n, features two μ₂-κ³-dithiocarbamate ligands each of which chelates one Cd^II atom, via the S atoms, while simultaneously bridging to another via the pyridyl-N atom. The result is a two-dimensional coordination polymer extending parallel to the ab plane with square channels along the b axis. The Cd^II atom geometry is based on a distorted cis-N₂S₄ octahedron. The 3-methylpyridine molecules reside in the channels aligned along the b axis, being held in place by methylene-C—H⋯N(3-methylpyridine) and (3-methylpyridine)-C—H⋯π(pyridyl) interactions. Pyridyl-C—H⋯S and dithiocarbamate-methyl-C—H⋯π(pyridyl) interactions provide connections between layers along the c axis.

Keywords: crystal structure; coordination polymer; cadmium; dithiocarbamate; hydroxypyridine.

CCDC reference: 1535967

1. Chemical context

Despite the relatively recent observations of one-dimensional coordination polymers for some binary cadmium dithiocarbamates (Tan et al., 2013 , 2016 ; Ferreira et al., 2016 ), i.e. compounds of general formula Cd(S₂CNRR′)₂, for R, R′ = alkyl, aryl, the overwhelming majority of Cd(S₂CNRR′)₂ structures are binuclear and zero-dimensional (i.e. molecular). This arises owing to the presence of equal numbers of chelating ligands and tridentate ligands, with the latter chelating one Cd^II atom while bridging a second. The coordination geometry defined by the resulting S₅ donor set is invariably highly distorted and intermediate between trigonal-bipyramidal and square-pyramidal (Tiekink, 2003 ). The polymeric motifs of Cd(S₂CNRR′)₂ have μ₃-bridging ligands exclusively and six-coordinate, S₆, geometries. Systematic crystallization studies indicate these transform to the binuclear motif with the egress of time (Tan et al., 2013, 2016), suggesting the zero-dimensional motif is the thermodynamic outcome of crystallization. The addition of monodentate pyridyl-N donor molecules during adduct formation more often than not results in the breakdown of the binuclear motif to form a mononuclear species, e.g. as in the structures of Cd{S₂CN[CH₂C(H)Me₂]₂}₂(pyridine) (Rodina et al., 2011 ) and Cd[S₂CN(Me)Ph]₂(pyridine)₂ (Onwudiwe et al., 2013 ). The latter structure shows it is possible for the Cd^II atom to increase its coordination number to six in the presence of N-donors. Hence, bipyridyl donors with suitably disposed nitrogen atoms might be anticipated to produce coordination polymers. This has been realized in several examples, e.g. in the one-dimensional coordination polymers of {Cd(S₂CNEt₂)₂[1,2-bis(pyridin-4-yl)ethylene]}_n (Chai et al., 2003 ) and in its 1,2-bis(pyridin-4-yl)ethane analogue (Avila et al., 2006 ). In these instances, the Cd^II atom exists within a trans-N₂S₄ coordination geometry. However, the reaction outcomes are not always as expected.

Thus, in [{Cd[S₂C(iPr)CH₂CH₂OH]₂}₂[1,2-bis(pyridin-4-yl)ethylene]₃], isolated as its tetra acetonitrile solvate, both bidentate bridging (× 1) and monodentate (× 2) modes of coordination are found for 1,2-bis(pyridin-4-yl)ethylene, resulting in a cis-N₂S₄ coordination geometry (Jotani, Poplaukhin, et al., 2016 ). In another unexpected reaction outcome, only monodentate modes of coordination are found for 3-pyridinealdazine in the structure of {Cd[S₂CN(nPr)CH₂CH₂OH]₂(3-pyridinealdazine)₂} leading to a NS₄ donor set for cadmium (Broker & Tiekink, 2011 ). Very recently, a more surprising structure was reported wherein the binuclear core usually found for Cd(S₂CNRR′)₂, see above, was retained. Thus, the structure of {Cd[S₂CN(iPr)CH₂CH₂OH]₂(3-pyridinealdazine)}₂, isolated as its hydrate (Arman et al., 2016 ), features monodentate binding of the 3-pyridinealdazine ligands to each Cd^II atom, leading to NS₅ coordination geometries.

The varied and interesting structures notwithstanding, it is obvious that Cd^II will expand its coordination number in the presence of pyridyl-N donors. Hence, in order to encourage the formation of higher-dimensional aggregates, functionalizing the dithiocarbamate ligand with pyridyl substituents offers an opportunity to increase the dimensionality of the structure. Indeed, Cd^II structures with pyridin-4-yl groups included in the dithiocarbamate ligand have appeared in the recent literature, e.g. Cd[S₂CN(ferrocenylmethyl)CH₂Py]₂(1,10-phenanthroline) (Kumar et al., 2016 ). Here, the Cd^II atom is coordinatively saturated within a cis-N₂S₄ donor set so the pyridyl-N atoms of the dithiocarbamate ligand are non-coordinating. However, pyridyl-N bridging has been observed in the binuclear structure, [Cd[S₂CN(1H-indol-3-ylmethyl)CH₂(CH₂py)]₂}₂ (Kumar et al., 2014 ). This structure is in fact very closely related to the common binuclear motif but, instead of a bridging, tridentate dithiocarbamate ligand, via three sulfur donors, the bridges in this structure are provided by the pyridyl-N atoms; the two pendent pyridyl groups are non-coordinating. In a continuation of exploratory work in this field (Arman et al., 2013 ), herein the crystal and molecular structures of the title two-dimensional coordination polymer, (I), {Cd[S₂CN(Et)CH₂py]2.3-methylpyridine}₂, containing a pyridyl-functionalized dithiocarbamate ligand, is described.

2. Structural commentary

The asymmetric unit of (I) comprises a molecule of Cd[S₂CN(Et)CH₂py]₂, Fig. 1, and a molecule of 3-methylpyridine. Referring to Table 1, each dithiocarbamate anion is chelating, forming very similar Cd—S bond lengths. This similarity is reflected in the experimental equivalence of the associated C—S bond lengths. Each dithiocarbamate ligand is in fact tridentate, chelating one Cd^II atom as just described and simultaneously bridging another via the pyridyl-N atom so that the coordination geometry about the Cd^II atom is cis-N₂S₄, distorted octahedral, Table 1. The bridging extends to form two interconnected rows of molecules, with those aligned along the a axis being formed via S3/S4–N4 bridges and those along the b axis being sustained by S1/S2–N2 bridges. The result is a two-dimensional architecture in the ab plane, Fig. 2. Square channels are formed in the b-axis direction and these are occupied by the solvent 3-methylpyridine molecules, Fig. 2a and b. The slats along the a axis are defined by the pyridyl residues and these block access along this direction, Fig. 2c.

Table 1
Selected geometric parameters (Å, °)

Cd—S1	2.6399 (19)	Cd—N4ⁱⁱ	2.346 (5)
Cd—S2	2.6618 (17)	S1—C1	1.714 (6)
Cd—S3	2.6578 (16)	S2—C1	1.715 (6)
Cd—S4	2.6932 (18)	S3—C10	1.715 (6)
Cd—N2ⁱ	2.430 (5)	S4—C10	1.724 (6)

S1—Cd—S2	68.26 (5)	S2—Cd—N4ⁱⁱ	94.15 (14)
S1—Cd—S3	101.88 (6)	S3—Cd—S4	67.58 (5)
S1—Cd—S4	100.71 (5)	S3—Cd—N2ⁱ	158.55 (18)
S1—Cd—N2ⁱ	90.18 (16)	S3—Cd—N4ⁱⁱ	91.47 (13)
S1—Cd—N4ⁱⁱ	159.47 (13)	S4—Cd—N2ⁱ	92.95 (16)
S2—Cd—S3	100.73 (5)	S4—Cd—N4ⁱⁱ	98.77 (14)
S2—Cd—S4	162.67 (5)	N2ⁱ—Cd—N4ⁱⁱ	82.40 (18)
S2—Cd—N2ⁱ	100.20 (17)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z]$ ; (ii) x-1, y, z.

Figure 1
The Cd[S₂CN(Et)CH₂py]₂ component of the asymmetric unit of (I)

, extended to show the immediate coordination geometry about the Cd^II atom, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) −x, − $[{1\over 2}]$ + y, −z; (ii) −1 + x, y, z.]

Figure 2
The two-dimensional architecture in (I)

, showing (a) a view in projection down the a axis, (b) a view slightly off-set from the a axis and (c) a view in projection down the b axis. The 3-methylpyridine molecules are shown in space-filling mode. All H atoms have been removed for reasons of clarity.

3. Supramolecular features

A summary of specific intermolecular interactions contributing to the molecular packing of (I) is given in Table 2. The main interactions between the host framework and the guest 3-methylpyridine molecules are of the type methylene-C—H⋯N(3-methylpyridine) and (3-methylpyridine)-C—H⋯π(pyridyl). The connections between layers stacking along the c axis are of the type pyridyl-C—H⋯S and dithiocarbamate-methyl-C—H⋯π(pyridyl). Two illustrations of the molecular packing are given in Fig. 3.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N2/C5–C9 and N4/C14–C17 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯N5ⁱⁱⁱ	0.99	2.62	3.264 (15)	123
C24—H24C⋯Cg1^iv	0.98	2.72	3.662 (12)	163
C15—H15⋯S3ⁱⁱⁱ	0.95	2.81	3.738 (7)	167
C3—H3C⋯Cg2^v	0.98	2.73	3.633 (8)	154
Symmetry codes: (iii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Figure 3
Two representations of the molecular packing in (I)

, showing (a) a view of the unit-cell contents in projection down the b axis and (b) a simplified view where all H atoms not participating in the specified intermolecular contacts are removed, adjacent layers are coloured in green and brown, and 3-methylpyridine molecules are coloured orange. The C—H⋯S, C—H⋯N and C—H⋯π interactions are shown as orange, blue and purple dashed lines, respectively.

4. Database survey

The dithiocarbamate anion, ⁻[S₂CN(Et)CH₂py], found in (I) has been reported in a series of diorganotin bis(dithiocarbamate)s (Barba et al., 2012 ) but there was no evidence for intermolecular Sn—N(py) interactions, the structures rather conforming to the expected motifs (Tiekink, 2008 ). There are also examples of structures of the general formula M[S₂CN(R)CH₂py]₂, a notable example being one with R = CH₂py, namely, {Hg[S₂CN(CH₂Py)₂]₂]}_n (Yadav et al., 2014 ), i.e. with two pyridyl groups per dithiocarbamate ligand, which adopts a relatively rare one-dimensional coordination polymer with a twisted topology (Jotani, Tan et al., 2016 ). In the other structures, R is a non-coordinating residue. For example, in the centrosymmetric Zn^II compound with R = CH₂(ferrocenyl) (Kumar et al., 2016), a two-dimensional architecture is found. Reverting back to Hg^II structures, when R = CH₂(furyl) (Kumar et al., 2016), a flat, two-dimensional architecture is found as the Hg^II atom lies on a centre on inversion. In the case of {Hg[S₂CN(Me)CH₂Py]₂}_n (Singh et al., 2014 ), molecules self-assemble into a one-dimensional coordination polymer as one pyridyl-N atom coordinates a neighbouring Hg^II atom while the other is non-coordinating. Finally, when R = CH₂(1-methyl-1H-pyrrol-2-yl) (Yadav et al., 2014), no Hg—N interactions are found. The Hg^II atom has a distorted tetrahedral geometry defined by an S₄ donor set. Such a variety in structures warrants continuing interest in this area.

5. Synthesis and crystallization

The Cd[S₂CN(Et₂)CH₂py]₂ precursor (268 mg, 0.50 mmol) was dissolved in an excess of 3-methylpyridine (ca 10 ml). The solution was filtered, transferred to a 50 ml test tube and layered with hexanes (ca 60 ml). Colourless crystals of (I) formed on the test tube walls within a week. IR (cm⁻¹): 2973(w), 2923(w), 1608(s), 1473(s), 1408(s), 1283(m), 1249(m), 1219(s), 1167(s), 1107(m), 1071(m), 991(s), 946(s). NMR ¹H: δ (ppm) 8.56 (dd, Ar, 2.98, 5.49 Hz), 8.43 (t, Ar, 1.00 Hz), 8.38 (dd, Ar, 0.89, 3.88 Hz), 7.61 (dq, Ar, 1.49, 7.82 Hz), 7.30 (d, Ar, 6.02 Hz), 5.19 (s, –CH₂–Ar), 3.88 (q, –CH₂CH₃, 6.49 Hz), 2.30 (s, pyridyl-CH₃), 1.22 (t, –CH₂CH₃, 4.80 Hz). M.p. 531 – 533 K (uncorrected). TGA: two steps, the first corresponding to loss of 3-methylpyridine (onset 410 K, mid-point 420 K, endset 431 K; theoretical mass loss 14.8%, observed mass loss 13.3%), the second step corresponds to the decomposition to CdS (onset 603 K, mid-point 604 K, endset 613 K; theoretical mass loss 62.3%, observed mass loss 57.4%). Total theoretical mass loss 77.1%, observed mass loss 74.9%.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). Owing to interference from the beam-stop, the (100) reflection was removed from the final cycles of refinement.

Table 3
Experimental details

Crystal data
Chemical formula	[Cd(C₉H₁₁N₂S₂)₂]·C₆H₇N
M_r	628.16
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	98
a, b, c (Å)	9.5842 (15), 11.0788 (16), 12.989 (2)
β (°)	100.014 (4)
V (Å³)	1358.2 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.13
Crystal size (mm)	0.23 × 0.20 × 0.10

Data collection
Diffractometer	AFC12/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.802, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10508, 5618, 5586
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.091, 1.08
No. of reflections	5618
No. of parameters	310
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −1.20
Absolute structure	Flack x determined using 2244 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.035 (15)
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1535967

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017003516/hb7664sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003516/hb7664Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); 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).

Poly[[bis[µ₂-N-ethyl-N-(pyridin-4-ylmethyl)dithiocarbamato-κ³N:S,S']cadmium(II)] 3-methylpyridine monosolvate] top

Crystal data top

[Cd(C₉H₁₁N₂S₂)₂]·C₆H₇N	F(000) = 640
M_r = 628.16	D_x = 1.536 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71069 Å
a = 9.5842 (15) Å	Cell parameters from 6543 reflections
b = 11.0788 (16) Å	θ = 2.4–40.7°
c = 12.989 (2) Å	µ = 1.13 mm⁻¹
β = 100.014 (4)°	T = 98 K
V = 1358.2 (4) Å³	Block, colourless
Z = 2	0.23 × 0.20 × 0.10 mm

Data collection top

AFC12K/SATURN724 diffractometer	5618 independent reflections
Radiation source: fine-focus sealed tube	5586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.802, T_max = 1.000	k = −14→13
10508 measured reflections	l = −15→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0304P)² + 3.8335P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.95 e Å⁻³
5618 reflections	Δρ_min = −1.20 e Å⁻³
310 parameters	Absolute structure: Flack x determined using 2244 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.035 (15)

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.

Refinement. Being affected by the beamstop, the (100) reflection was omitted from the final cycles of refinement.

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

	x	y	z	U_iso*/U_eq
Cd	0.07792 (4)	0.11775 (5)	0.28476 (3)	0.01706 (11)
S1	0.23327 (18)	0.29766 (16)	0.23386 (13)	0.0188 (3)
S2	−0.01802 (17)	0.33065 (15)	0.33697 (13)	0.0208 (3)
S3	0.22627 (17)	0.04779 (16)	0.46716 (12)	0.0215 (3)
S4	0.24814 (18)	−0.07121 (16)	0.26516 (13)	0.0198 (3)
N1	0.1324 (5)	0.5121 (5)	0.2772 (4)	0.0171 (10)
N2	0.0426 (5)	0.6032 (7)	−0.1044 (4)	0.0216 (12)
N3	0.4308 (5)	−0.1054 (5)	0.4433 (4)	0.0182 (10)
N4	0.8778 (5)	0.0113 (5)	0.3160 (4)	0.0163 (10)
C1	0.1167 (6)	0.3905 (6)	0.2819 (4)	0.0160 (11)
C2	0.0472 (7)	0.5963 (6)	0.3283 (5)	0.0242 (15)
H2A	−0.0413	0.5561	0.3394	0.029*
H2B	0.0213	0.6674	0.2829	0.029*
C3	0.1312 (8)	0.6364 (8)	0.4323 (5)	0.0316 (18)
H3A	0.0725	0.6894	0.4675	0.047*
H3B	0.2159	0.6802	0.4206	0.047*
H3C	0.1595	0.5655	0.4761	0.047*
C4	0.2370 (7)	0.5677 (7)	0.2207 (5)	0.0238 (14)
H4A	0.3221	0.5157	0.2271	0.029*
H4B	0.2664	0.6472	0.2520	0.029*
C5	0.1735 (7)	0.5838 (6)	0.1065 (5)	0.0243 (15)
C6	0.1958 (8)	0.4960 (7)	0.0331 (6)	0.0314 (16)
H6	0.2563	0.4289	0.0528	0.038*
C7	0.1261 (8)	0.5106 (7)	−0.0692 (6)	0.0313 (16)
H7	0.1392	0.4496	−0.1181	0.038*
C8	0.0322 (9)	0.6904 (7)	−0.0345 (6)	0.0357 (18)
H8	−0.0213	0.7607	−0.0571	0.043*
C9	0.0971 (10)	0.6820 (8)	0.0704 (6)	0.0378 (19)
H9	0.0872	0.7463	0.1169	0.045*
C10	0.3130 (6)	−0.0482 (6)	0.3960 (5)	0.0158 (11)
C11	0.4862 (6)	−0.0914 (7)	0.5560 (5)	0.0239 (14)
H11A	0.4691	−0.0078	0.5778	0.029*
H11B	0.5898	−0.1056	0.5694	0.029*
C12	0.4151 (8)	−0.1797 (9)	0.6200 (6)	0.0344 (19)
H12A	0.4554	−0.1706	0.6942	0.052*
H12B	0.4308	−0.2624	0.5977	0.052*
H12C	0.3131	−0.1632	0.6092	0.052*
C13	0.5156 (6)	−0.1836 (6)	0.3869 (5)	0.0216 (13)
H13A	0.4562	−0.2126	0.3216	0.026*
H13B	0.5485	−0.2548	0.4305	0.026*
C14	0.6427 (7)	−0.1156 (6)	0.3609 (5)	0.0216 (13)
C15	0.7786 (6)	−0.1612 (6)	0.3879 (5)	0.0225 (13)
H15	0.7938	−0.2369	0.4224	0.027*
C16	0.8927 (7)	−0.0960 (6)	0.3645 (5)	0.0243 (14)
H16	0.9852	−0.1288	0.3836	0.029*
C17	0.7450 (7)	0.0563 (6)	0.2896 (5)	0.0214 (13)
H17	0.7326	0.1319	0.2547	0.026*
C18	0.6265 (7)	−0.0034 (6)	0.3115 (5)	0.0218 (13)
H18	0.5351	0.0318	0.2930	0.026*
N5	0.4417 (12)	0.1672 (11)	0.8221 (11)	0.084 (4)
C19	0.3520 (10)	0.0783 (11)	0.8364 (9)	0.059 (3)
H19	0.3143	0.0284	0.7787	0.071*
C20	0.3115 (11)	0.0565 (10)	0.9343 (8)	0.052 (2)
C21	0.3647 (10)	0.1275 (16)	1.0165 (8)	0.060 (3)
H21	0.3389	0.1126	1.0827	0.072*
C22	0.4575 (14)	0.2230 (14)	1.0056 (12)	0.081 (4)
H22	0.4972	0.2730	1.0627	0.097*
C23	0.4878 (15)	0.2396 (15)	0.9037 (12)	0.081 (4)
H23	0.5448	0.3068	0.8923	0.097*
C24	0.2137 (11)	−0.0448 (12)	0.9431 (9)	0.063 (3)
H24A	0.2640	−0.1078	0.9879	0.094*
H24B	0.1789	−0.0782	0.8735	0.094*
H24C	0.1335	−0.0156	0.9736	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.01767 (18)	0.01518 (19)	0.01811 (19)	0.0001 (2)	0.00250 (13)	0.00003 (19)
S1	0.0144 (7)	0.0213 (9)	0.0207 (7)	−0.0016 (6)	0.0030 (6)	−0.0033 (6)
S2	0.0208 (7)	0.0181 (8)	0.0255 (8)	−0.0002 (6)	0.0095 (6)	−0.0005 (6)
S3	0.0231 (8)	0.0224 (9)	0.0183 (7)	0.0048 (6)	0.0016 (6)	−0.0022 (6)
S4	0.0218 (8)	0.0182 (9)	0.0187 (7)	0.0025 (6)	0.0021 (6)	−0.0031 (6)
N1	0.017 (2)	0.018 (3)	0.016 (2)	−0.002 (2)	0.0005 (19)	0.0004 (19)
N2	0.027 (2)	0.019 (3)	0.019 (2)	0.000 (2)	0.0026 (18)	0.000 (2)
N3	0.010 (2)	0.022 (3)	0.022 (3)	−0.003 (2)	0.0009 (18)	0.000 (2)
N4	0.014 (2)	0.015 (3)	0.021 (2)	0.0000 (19)	0.0028 (18)	0.0007 (19)
C1	0.011 (3)	0.020 (3)	0.013 (3)	−0.001 (2)	−0.0073 (19)	0.000 (2)
C2	0.027 (3)	0.015 (4)	0.030 (3)	0.003 (2)	0.002 (2)	0.002 (2)
C3	0.046 (4)	0.028 (5)	0.020 (3)	0.004 (3)	0.005 (3)	−0.001 (3)
C4	0.024 (3)	0.023 (3)	0.024 (3)	−0.009 (3)	0.001 (2)	0.002 (2)
C5	0.029 (3)	0.022 (4)	0.020 (3)	−0.007 (2)	0.000 (3)	0.002 (2)
C6	0.035 (4)	0.032 (4)	0.027 (4)	0.008 (3)	0.005 (3)	0.008 (3)
C7	0.038 (4)	0.034 (4)	0.023 (3)	0.008 (3)	0.008 (3)	0.003 (3)
C8	0.051 (5)	0.021 (4)	0.031 (4)	0.009 (3)	−0.004 (3)	0.000 (3)
C9	0.055 (5)	0.028 (5)	0.027 (4)	−0.006 (4)	−0.004 (3)	−0.007 (3)
C10	0.008 (2)	0.017 (3)	0.020 (3)	−0.004 (2)	−0.003 (2)	0.002 (2)
C11	0.011 (3)	0.032 (4)	0.027 (3)	−0.003 (3)	−0.002 (2)	0.005 (3)
C12	0.026 (4)	0.050 (6)	0.024 (3)	−0.012 (4)	−0.004 (3)	0.016 (3)
C13	0.014 (3)	0.020 (3)	0.031 (3)	0.000 (2)	0.004 (2)	0.004 (3)
C14	0.024 (3)	0.016 (3)	0.026 (3)	0.001 (3)	0.007 (3)	−0.001 (2)
C15	0.016 (3)	0.018 (3)	0.035 (4)	0.000 (2)	0.007 (2)	0.006 (3)
C16	0.024 (3)	0.021 (3)	0.028 (3)	0.006 (3)	0.004 (3)	0.003 (3)
C17	0.020 (3)	0.018 (3)	0.026 (3)	0.002 (2)	0.003 (2)	0.004 (3)
C18	0.017 (3)	0.020 (3)	0.028 (3)	0.000 (2)	0.002 (2)	0.004 (3)
N5	0.068 (7)	0.083 (9)	0.114 (10)	0.023 (6)	0.054 (7)	0.041 (7)
C19	0.038 (5)	0.082 (10)	0.061 (6)	0.014 (5)	0.018 (4)	0.014 (5)
C20	0.051 (6)	0.052 (6)	0.059 (6)	0.010 (5)	0.023 (5)	0.001 (5)
C21	0.055 (5)	0.076 (8)	0.053 (5)	−0.006 (7)	0.021 (4)	−0.009 (7)
C22	0.066 (8)	0.078 (10)	0.109 (11)	0.009 (7)	0.042 (8)	0.008 (8)
C23	0.071 (9)	0.081 (10)	0.100 (11)	0.005 (7)	0.042 (8)	0.025 (8)
C24	0.047 (6)	0.074 (8)	0.067 (7)	−0.003 (5)	0.010 (5)	−0.001 (6)

Geometric parameters (Å, º) top

Cd—S1	2.6399 (19)	C7—H7	0.9500
Cd—S2	2.6618 (17)	C8—C9	1.398 (11)
Cd—S3	2.6578 (16)	C8—H8	0.9500
Cd—S4	2.6932 (18)	C9—H9	0.9500
Cd—N2ⁱ	2.430 (5)	C11—C12	1.520 (9)
Cd—N4ⁱⁱ	2.346 (5)	C11—H11A	0.9900
S1—C1	1.714 (6)	C11—H11B	0.9900
S2—C1	1.715 (6)	C12—H12A	0.9800
S3—C10	1.715 (6)	C12—H12B	0.9800
S4—C10	1.724 (6)	C12—H12C	0.9800
N1—C1	1.357 (8)	C13—C14	1.519 (9)
N1—C4	1.477 (8)	C13—H13A	0.9900
N1—C2	1.471 (8)	C13—H13B	0.9900
N2—C8	1.342 (10)	C14—C15	1.385 (9)
N2—C7	1.332 (10)	C14—C18	1.396 (9)
N2—Cdⁱⁱⁱ	2.430 (5)	C15—C16	1.388 (9)
N3—C10	1.347 (8)	C15—H15	0.9500
N3—C13	1.467 (8)	C16—H16	0.9500
N3—C11	1.477 (8)	C17—C18	1.386 (9)
N4—C16	1.341 (9)	C17—H17	0.9500
N4—C17	1.354 (8)	C18—H18	0.9500
N4—Cd^iv	2.346 (5)	N5—C23	1.341 (19)
C2—C3	1.514 (9)	N5—C19	1.341 (15)
C2—H2A	0.9900	C19—C20	1.413 (13)
C2—H2B	0.9900	C19—H19	0.9500
C3—H3A	0.9800	C20—C21	1.353 (16)
C3—H3B	0.9800	C20—C24	1.479 (15)
C3—H3C	0.9800	C21—C22	1.40 (2)
C4—C5	1.513 (9)	C21—H21	0.9500
C4—H4A	0.9900	C22—C23	1.415 (18)
C4—H4B	0.9900	C22—H22	0.9500
C5—C9	1.349 (11)	C23—H23	0.9500
C5—C6	1.403 (10)	C24—H24A	0.9800
C6—C7	1.389 (10)	C24—H24B	0.9800
C6—H6	0.9500	C24—H24C	0.9800

S1—Cd—S2	68.26 (5)	C9—C8—H8	118.7
S1—Cd—S3	101.88 (6)	C5—C9—C8	121.0 (8)
S1—Cd—S4	100.71 (5)	C5—C9—H9	119.5
S1—Cd—N2ⁱ	90.18 (16)	C8—C9—H9	119.5
S1—Cd—N4ⁱⁱ	159.47 (13)	N3—C10—S3	119.5 (5)
S2—Cd—S3	100.73 (5)	N3—C10—S4	120.6 (5)
S2—Cd—S4	162.67 (5)	S3—C10—S4	119.8 (3)
S2—Cd—N2ⁱ	100.20 (17)	N3—C11—C12	110.8 (6)
S2—Cd—N4ⁱⁱ	94.15 (14)	N3—C11—H11A	109.5
S3—Cd—S4	67.58 (5)	C12—C11—H11A	109.5
S3—Cd—N2ⁱ	158.55 (18)	N3—C11—H11B	109.5
S3—Cd—N4ⁱⁱ	91.47 (13)	C12—C11—H11B	109.5
S4—Cd—N2ⁱ	92.95 (16)	H11A—C11—H11B	108.1
S4—Cd—N4ⁱⁱ	98.77 (14)	C11—C12—H12A	109.5
N2ⁱ—Cd—N4ⁱⁱ	82.40 (18)	C11—C12—H12B	109.5
C1—S1—Cd	86.0 (2)	H12A—C12—H12B	109.5
C1—S2—Cd	85.3 (2)	C11—C12—H12C	109.5
C10—S3—Cd	86.3 (2)	H12A—C12—H12C	109.5
C10—S4—Cd	85.0 (2)	H12B—C12—H12C	109.5
C1—N1—C4	121.8 (5)	N3—C13—C14	110.7 (6)
C1—N1—C2	122.3 (5)	N3—C13—H13A	109.5
C4—N1—C2	115.9 (5)	C14—C13—H13A	109.5
C8—N2—C7	115.6 (6)	N3—C13—H13B	109.5
C8—N2—Cdⁱⁱⁱ	121.7 (5)	C14—C13—H13B	109.5
C7—N2—Cdⁱⁱⁱ	122.6 (5)	H13A—C13—H13B	108.1
C10—N3—C13	123.0 (5)	C15—C14—C18	117.8 (6)
C10—N3—C11	122.1 (5)	C15—C14—C13	121.2 (6)
C13—N3—C11	115.0 (5)	C18—C14—C13	121.0 (6)
C16—N4—C17	117.6 (5)	C14—C15—C16	119.8 (6)
C16—N4—Cd^iv	120.2 (4)	C14—C15—H15	120.1
C17—N4—Cd^iv	122.1 (4)	C16—C15—H15	120.1
N1—C1—S1	119.7 (5)	N4—C16—C15	122.7 (6)
N1—C1—S2	120.0 (5)	N4—C16—H16	118.6
S1—C1—S2	120.3 (4)	C15—C16—H16	118.6
N1—C2—C3	109.8 (5)	N4—C17—C18	122.7 (6)
N1—C2—H2A	109.7	N4—C17—H17	118.6
C3—C2—H2A	109.7	C18—C17—H17	118.6
N1—C2—H2B	109.7	C17—C18—C14	119.3 (6)
C3—C2—H2B	109.7	C17—C18—H18	120.3
H2A—C2—H2B	108.2	C14—C18—H18	120.3
C2—C3—H3A	109.5	C23—N5—C19	117.4 (11)
C2—C3—H3B	109.5	N5—C19—C20	122.2 (12)
H3A—C3—H3B	109.5	N5—C19—H19	118.9
C2—C3—H3C	109.5	C20—C19—H19	118.9
H3A—C3—H3C	109.5	C21—C20—C19	119.0 (11)
H3B—C3—H3C	109.5	C21—C20—C24	122.5 (10)
N1—C4—C5	110.1 (5)	C19—C20—C24	118.5 (10)
N1—C4—H4A	109.6	C20—C21—C22	121.2 (11)
C5—C4—H4A	109.6	C20—C21—H21	119.4
N1—C4—H4B	109.6	C22—C21—H21	119.4
C5—C4—H4B	109.6	C23—C22—C21	115.3 (14)
H4A—C4—H4B	108.2	C23—C22—H22	122.3
C9—C5—C6	117.4 (7)	C21—C22—H22	122.3
C9—C5—C4	122.5 (7)	N5—C23—C22	124.6 (14)
C6—C5—C4	120.1 (6)	N5—C23—H23	117.7
C7—C6—C5	117.7 (7)	C22—C23—H23	117.7
C7—C6—H6	121.2	C20—C24—H24A	109.5
C5—C6—H6	121.2	C20—C24—H24B	109.5
N2—C7—C6	125.3 (7)	H24A—C24—H24B	109.5
N2—C7—H7	117.3	C20—C24—H24C	109.5
C6—C7—H7	117.3	H24A—C24—H24C	109.5
N2—C8—C9	122.6 (7)	H24B—C24—H24C	109.5
N2—C8—H8	118.7

C4—N1—C1—S1	7.3 (7)	Cd—S3—C10—N3	168.9 (5)
C2—N1—C1—S1	−172.3 (4)	Cd—S3—C10—S4	−11.5 (3)
C4—N1—C1—S2	−173.4 (4)	Cd—S4—C10—N3	−169.0 (5)
C2—N1—C1—S2	7.0 (8)	Cd—S4—C10—S3	11.3 (3)
Cd—S1—C1—N1	−177.9 (5)	C10—N3—C11—C12	85.9 (8)
Cd—S1—C1—S2	2.8 (3)	C13—N3—C11—C12	−95.6 (7)
Cd—S2—C1—N1	177.9 (5)	C10—N3—C13—C14	98.4 (7)
Cd—S2—C1—S1	−2.8 (3)	C11—N3—C13—C14	−80.2 (7)
C1—N1—C2—C3	98.4 (7)	N3—C13—C14—C15	127.2 (7)
C4—N1—C2—C3	−81.3 (7)	N3—C13—C14—C18	−50.9 (8)
C1—N1—C4—C5	86.5 (7)	C18—C14—C15—C16	−0.7 (10)
C2—N1—C4—C5	−93.9 (6)	C13—C14—C15—C16	−179.0 (6)
N1—C4—C5—C9	86.4 (8)	C17—N4—C16—C15	0.0 (10)
N1—C4—C5—C6	−95.1 (8)	Cd^iv—N4—C16—C15	178.0 (5)
C9—C5—C6—C7	−6.3 (11)	C14—C15—C16—N4	0.1 (11)
C4—C5—C6—C7	175.2 (7)	C16—N4—C17—C18	0.6 (10)
C8—N2—C7—C6	3.1 (12)	Cd^iv—N4—C17—C18	−177.3 (5)
Cdⁱⁱⁱ—N2—C7—C6	−178.8 (6)	N4—C17—C18—C14	−1.3 (10)
C5—C6—C7—N2	2.0 (12)	C15—C14—C18—C17	1.3 (10)
C7—N2—C8—C9	−4.0 (12)	C13—C14—C18—C17	179.5 (6)
Cdⁱⁱⁱ—N2—C8—C9	177.9 (6)	C23—N5—C19—C20	−3.1 (17)
C6—C5—C9—C8	5.6 (12)	N5—C19—C20—C21	0.1 (16)
C4—C5—C9—C8	−175.9 (7)	N5—C19—C20—C24	−179.1 (10)
N2—C8—C9—C5	−0.4 (14)	C19—C20—C21—C22	0.8 (19)
C13—N3—C10—S3	−176.5 (5)	C24—C20—C21—C22	180.0 (12)
C11—N3—C10—S3	2.0 (8)	C20—C21—C22—C23	1 (2)
C13—N3—C10—S4	3.9 (8)	C19—N5—C23—C22	5 (2)
C11—N3—C10—S4	−177.7 (5)	C21—C22—C23—N5	−4 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N2/C5–C9 and N4/C14–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···N5^v	0.99	2.62	3.264 (15)	123
C24—H24C···Cg1^vi	0.98	2.72	3.662 (12)	163
C15—H15···S3^v	0.95	2.81	3.738 (7)	167
C3—H3C···Cg2^vii	0.98	2.73	3.633 (8)	154

Symmetry codes: (v) −x+1, y−1/2, −z+1; (vi) −x, y−1/2, −z+1; (vii) −x+1, y+1/2, −z+1.

Acknowledgements

We thank Sunway University for support of biological and crystal engineering studies of metal dithiocarbamates.

References

Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2013). Acta Cryst. E69, m479–m480. CSD CrossRef IUCr Journals Google Scholar
Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1234–1238. Web of Science CSD CrossRef IUCr Journals Google Scholar
Avila, V., Benson, R. E., Broker, G. A., Daniels, L. M. & Tiekink, E. R. T. (2006). Acta Cryst. E62, m1425–m1427. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barba, V. B., Arenaza, B., Guerrero, J. & Reyes, R. (2012). Heteroat. Chem. 23, 422–428. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Broker, G. A. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m320–m321. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Chai, J., Lai, C.-S., Yan, J. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 249–250. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Jotani, M. M., Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1085–1092. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jotani, M. M., Tan, Y. S. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 403–413. CAS Google Scholar
Kumar, V., Manar, K. K., Gupta, A. N., Singh, V., Drew, M. G. B. & Singh, N. (2016). J. Organomet. Chem. 820, 62–69. Web of Science CSD CrossRef CAS Google Scholar
Kumar, V., Singh, V., Gupta, A. N., Manar, K. K., Drew, M. G. B. & Singh, N. (2014). CrystEngComm, 16, 6765–6774. Web of Science CSD CrossRef CAS Google Scholar
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Onwudiwe, D. C., Strydom, C. A. & Hosten, E. C. (2013). Inorg. Chim. Acta, 401, 1–10. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rodina, T. A. V., Ivanov, A., Gerasimenko, A. V., Ivanov, M. A., Zaeva, A. S., Philippova, T. S. & Antzutkin, O. N. (2011). Inorg. Chim. Acta, 368, 263–270. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Singh, V., Kumar, V., Gupta, A. N., Drew, M. G. B. & Singh, N. (2014). New J. Chem. 38, 3737–3748. Web of Science CSD CrossRef CAS Google Scholar
Tan, Y. S., Halim, S. N. A. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 113–126. CAS Google Scholar
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. Google Scholar
Tiekink, E. R. T. (2003). CrystEngComm, 5, 101–113. Web of Science CrossRef CAS Google Scholar
Tiekink, E. R. T. (2008). Appl. Organomet. Chem. 22, 533–550. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yadav, M. K., Rajput, G., Gupta, A. N., Kumar, V., Drew, M. G. B. & Singh, N. (2014). Inorg. Chim. Acta, 421, 210–217. Web of Science CSD CrossRef CAS Google Scholar

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