Bis(N-isopropyl-N-methyl­dithio­carbamato-κ2S,S′)(1,10-phenanthroline-κ2N,N′)zinc

Wahab, N.A.A.; Baba, I.; Mohamed Tahir, M.I.; Tiekink, E.R.T.

doi:10.1107/S1600536811012499

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages m553-m554

doi:10.1107/S1600536811012499

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Bis(N-isopropyl-N-methyldithiocarbamato-κ²S,S′)(1,10-phenanthroline-κ²N,N′)zinc

Nor Asiken Abdul Wahab,^a Ibrahim Baba,^a ‡ Mohamed Ibrahim Mohamed Tahir ^b and Edward R. T. Tiekink ^c ^*

^aSchool of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia, ^bDepartment of Chemistry, Universiti Putra Malaysia, 43400 Serdang, Malaysia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 3 April 2011; accepted 4 April 2011; online 7 April 2011)

The Zn^II atom in the title compound, [Zn(C₅H₁₀NS₂)₂(C₁₂H₈N₂)], exists in a distorted cis-octahedral N₂S₄ donor set defined by two chelating dithiocarbamate anions as well as a 1,10-phenanthroline ligand. Each of the ligands coordinates in a symmetric mode. The crystal packing is stabilized by weak C—H⋯S, C—H⋯π(ZnS₂C) and π–π [ring centroid distance between centrosymmetrically related pyridyl rings = 3.5955 (13) Å] interactions.

Related literature

For the use of the parent zinc compound and nitrogen adducts as precursors for ZnS nanoparticles, see: Motevalli et al. (1996 ); Malik et al. (1997 ). For background to supramolecular polymers of zinc-triad dithiocarbamates and related structures, see: Benson et al. (2007 ); Jamaluddin et al. (2011 ). For a description of C—H⋯π(MS₂C) interactions, see: Tiekink & Zukerman-Schpector (2011 ).

Experimental

Crystal data

[Zn(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]
M_r = 542.09
Monoclinic, P 2₁ /n
a = 11.8015 (3) Å
b = 16.6316 (4) Å
c = 13.7505 (3) Å
β = 101.738 (2)°
V = 2642.48 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 150 K
0.25 × 0.20 × 0.12 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.777, T_max = 0.860
33394 measured reflections
6001 independent reflections
4814 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.093
S = 1.04
6001 reflections
286 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn—S1	2.4782 (6)
Zn—S2	2.5408 (7)
Zn—S3	2.5031 (6)
Zn—S4	2.5132 (7)
Zn—N3	2.1939 (18)
Zn—N4	2.1970 (19)

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the Zn,S1,S2,C1 chelate ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7b⋯S2ⁱ	0.98	2.79	3.734 (3)	162
C13—H13⋯S4ⁱⁱ	0.95	2.82	3.634 (2)	145
C21—H21⋯S1ⁱⁱⁱ	0.95	2.84	3.684 (3)	149
C20—H20⋯Cg1^iv	0.95	2.74	3.687 (2)	173
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012499/hb5835sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012499/hb5835Isup2.hkl

checkCIF report

Comment top

The title compound Zn[S₂CN(Me)iPr)₂]₂(1,10-phenanthroline), (I), was investigated as a part of on-going studies of zinc-triad dithiocarbamates and their adducts (Benson et al., 2007; Jamaluddin et al., 2011). The dinuclear parent {Zn[S₂CN(Me)iPr]₂}₂ compound and its nitrogen-based adducts have proven useful as synthetic precursors for ZnS nanoparticles (Motevalli et al., 1996; Malik et al., 1997).

The Zn atom in (I), Fig. 1, is chelated by two symmetrically coordinating dithiocarbamate ligands, Table 1, and also symmetrically by the 1,10-phenanthroline ligand. The symmetric mode of coordination of the dithiocarbamate ligands is reflected in the narrow range of associated C≐ S bond distances, i.e. 1.718 (2) to 1.724 (2) Å, which are in fact experimentally equivalent. The N₂S₄ donor set defines a distorted octahedron with distortions readily explained in terms of the restricted bite distances of the chelating ligands.

The crystal structure is stabilized by weak intermolecular interactions. These include C—H···S and C—H···π(ZnS₂C), Table 2, and π–π interactions. The C—H···π(ZnS₂C) contacts have precedents in the crystal chemistry of metal dithiocarbamates (Tiekink & Zukerman-Schpector, 2011). The π–π interactions occur between centrosymmetrically related pyridyl rings [ring centroid(N3,C11–C15)···ring centroid(N3,C11–C15)ⁱ = 3.5955 (13) Å for i: 1 - x, 1 - y, 1 - z]. A view of the unit-cell contents is shown in Fig. 2 where it can be seen that globally, the crystal packing comprises alternating layers of ZnS₂CN/1,10-phenanthroline residues and alkyl groups.

Related literature top

For the use of the parent zinc compound and nitrogen adducts as precursors for ZnS nanoparticles, see: Motevalli et al. (1996); Malik et al. (1997). For background to supramolecular polymers of zinc-triad dithiocarbamates and related structures, see: Benson et al. (2007); Jamaluddin et al. (2011). For a description of C—H···π(MS₂C) interactions, see: Tiekink & Zukerman-Schpector (2011).

Experimental top

The title compound was prepared using an in situ method by the addition of carbon disulfide (0.02 mol) to an ethanolic solution (20 ml) of isopropropyl(methyl)amine (0.02 mol) and 2,2'-bipyridine (0.01 mol) in ethanol (20 ml). The mixture was stirred for 1 h at 277 K. The resulting solution was added drop-wise to a solution of zinc(II) dichloride (0.01 mol) in ethanol (20 ml). The mixture was stirred for a further 2 h. The yellow precipitate was filtered and washed with cold ethanol, and dried in a desiccator. Crystallization was carried using an ethanol:chloroform (1:2 v/v) solvent system to yield pale yellow prisms of (I); M.pt. 420–421 K. Elemental analysis. Found (calculated) for C₂₂H₃₂CdN₄S₄: C, 46.49 (46.36); H 5.13 (5.45); N 10.74 (10.81) %. UV (CHCl₃) λ_max 306.5 nm (L(π) → L(π*)). IR (KBr): ν(C—H) 2928 s; ν(C≐N) 1564 s; ν(N—C) 1473 s; ν(C≐S) 976 s; ν(Cd—S) 384 s cm^-1.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. A view in projection down the b axis of the unit-cell contents for (I). The intermolecular C—H···S, C—H···π(ZnS₂C) and π–π contacts are shown as orange, blue and purple dashed lines, respectively.

Bis(N-isopropyl-N-methyldithiocarbamato- κ²S,S')(1,10-phenanthroline-κ²N,N')zinc top

Crystal data top

[Zn(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]	F(000) = 1128
M_r = 542.09	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11977 reflections
a = 11.8015 (3) Å	θ = 2–29°
b = 16.6316 (4) Å	µ = 1.26 mm⁻¹
c = 13.7505 (3) Å	T = 150 K
β = 101.738 (2)°	Prism, pale-yellow
V = 2642.48 (11) Å³	0.25 × 0.20 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	6001 independent reflections
Radiation source: fine-focus sealed tube	4814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
Detector resolution: 16.1952 pixels mm^-1	θ_max = 27.5°, θ_min = 2.2°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −21→21
T_min = 0.777, T_max = 0.860	l = −17→17
33394 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0376P)² + 1.5727P] where P = (F_o² + 2F_c²)/3
6001 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.66 e Å⁻³
6 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Zn(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]	V = 2642.48 (11) Å³
M_r = 542.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.8015 (3) Å	µ = 1.26 mm⁻¹
b = 16.6316 (4) Å	T = 150 K
c = 13.7505 (3) Å	0.25 × 0.20 × 0.12 mm
β = 101.738 (2)°

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	6001 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	4814 reflections with I > 2σ(I)
T_min = 0.777, T_max = 0.860	R_int = 0.064
33394 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	6 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.04	Δρ_max = 0.66 e Å⁻³
6001 reflections	Δρ_min = −0.50 e Å⁻³
286 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Zn	0.74542 (2)	0.617296 (16)	0.733396 (19)	0.02087 (9)
S1	0.88167 (5)	0.51904 (4)	0.82966 (4)	0.02410 (14)
S2	0.94125 (6)	0.63431 (4)	0.68609 (4)	0.02614 (15)
S3	0.74451 (5)	0.71890 (4)	0.86753 (4)	0.02513 (15)
S4	0.57158 (5)	0.59097 (4)	0.80817 (4)	0.02474 (14)
N1	1.08885 (19)	0.52534 (15)	0.78012 (17)	0.0349 (5)
N2	0.55956 (18)	0.70121 (13)	0.94727 (15)	0.0289 (5)
N3	0.68974 (16)	0.53855 (11)	0.60453 (13)	0.0188 (4)
N4	0.65988 (16)	0.69879 (11)	0.61528 (14)	0.0206 (4)
C1	0.9824 (2)	0.55502 (15)	0.76623 (17)	0.0239 (5)
C2	1.1701 (3)	0.5547 (2)	0.7204 (3)	0.0553 (9)
H2A	1.1340	0.5512	0.6497	0.083*
H2B	1.2404	0.5218	0.7338	0.083*
H2C	1.1901	0.6108	0.7377	0.083*
C3	1.1290 (3)	0.45930 (18)	0.8512 (2)	0.0450 (8)
H3	1.0679	0.4513	0.8911	0.054*
C4	1.1391 (4)	0.3815 (2)	0.7977 (4)	0.0847 (14)
H4A	1.0650	0.3692	0.7534	0.127*
H4B	1.1594	0.3380	0.8463	0.127*
H4C	1.1995	0.3865	0.7586	0.127*
C5	1.2390 (3)	0.4817 (2)	0.9235 (3)	0.0609 (10)
H5A	1.3038	0.4822	0.8888	0.091*
H5B	1.2543	0.4422	0.9774	0.091*
H5C	1.2302	0.5351	0.9510	0.091*
C6	0.6178 (2)	0.67345 (14)	0.88098 (16)	0.0214 (5)
C7	0.5997 (3)	0.77392 (18)	1.0047 (2)	0.0433 (7)
H7A	0.6762	0.7640	1.0463	0.065*
H7B	0.5450	0.7878	1.0470	0.065*
H7C	0.6046	0.8185	0.9591	0.065*
C8	0.4491 (2)	0.66584 (18)	0.9609 (2)	0.0331 (6)
H8	0.4375	0.6144	0.9225	0.040*
C9	0.3502 (3)	0.7211 (2)	0.9181 (3)	0.0684 (11)
H9A	0.3586	0.7718	0.9551	0.103*
H9B	0.2768	0.6956	0.9234	0.103*
H9C	0.3507	0.7317	0.8481	0.103*
C10	0.4521 (3)	0.6458 (2)	1.0693 (2)	0.0504 (8)
H10A	0.5227	0.6155	1.0964	0.076*
H10B	0.3843	0.6133	1.0743	0.076*
H10C	0.4513	0.6957	1.1071	0.076*
C11	0.7038 (2)	0.45954 (14)	0.60029 (17)	0.0229 (5)
H11	0.7385	0.4319	0.6593	0.027*
C12	0.6698 (2)	0.41511 (14)	0.51280 (17)	0.0231 (5)
H12	0.6806	0.3585	0.5130	0.028*
C13	0.6210 (2)	0.45394 (14)	0.42725 (17)	0.0216 (5)
H13	0.5981	0.4246	0.3672	0.026*
C14	0.60452 (19)	0.53794 (14)	0.42823 (16)	0.0196 (5)
C15	0.64063 (18)	0.57743 (13)	0.51983 (16)	0.0168 (4)
C16	0.62276 (19)	0.66277 (13)	0.52604 (16)	0.0176 (5)
C17	0.56638 (19)	0.70521 (14)	0.44123 (16)	0.0200 (5)
C18	0.5324 (2)	0.66342 (15)	0.34901 (17)	0.0254 (5)
H18	0.4959	0.6921	0.2914	0.031*
C19	0.5516 (2)	0.58322 (15)	0.34272 (16)	0.0245 (5)
H19	0.5295	0.5568	0.2805	0.029*
C20	0.5474 (2)	0.78788 (14)	0.45176 (18)	0.0243 (5)
H20	0.5083	0.8185	0.3968	0.029*
C21	0.5854 (2)	0.82358 (15)	0.54158 (19)	0.0270 (5)
H21	0.5734	0.8795	0.5497	0.032*
C22	0.6422 (2)	0.77763 (14)	0.62167 (18)	0.0258 (5)
H22	0.6694	0.8036	0.6835	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.02263 (16)	0.02294 (16)	0.01688 (14)	0.00262 (11)	0.00360 (10)	−0.00228 (11)
S1	0.0225 (3)	0.0270 (3)	0.0237 (3)	0.0021 (2)	0.0069 (2)	0.0075 (2)
S2	0.0278 (3)	0.0285 (3)	0.0229 (3)	−0.0016 (3)	0.0070 (2)	0.0066 (3)
S3	0.0233 (3)	0.0283 (3)	0.0248 (3)	−0.0056 (2)	0.0073 (2)	−0.0095 (3)
S4	0.0247 (3)	0.0272 (3)	0.0226 (3)	−0.0051 (2)	0.0054 (2)	−0.0087 (2)
N1	0.0247 (12)	0.0447 (14)	0.0387 (12)	0.0059 (10)	0.0144 (10)	0.0145 (11)
N2	0.0262 (12)	0.0332 (12)	0.0304 (11)	−0.0037 (9)	0.0131 (9)	−0.0135 (10)
N3	0.0195 (10)	0.0179 (10)	0.0192 (9)	0.0016 (8)	0.0045 (7)	−0.0008 (8)
N4	0.0206 (10)	0.0198 (10)	0.0213 (9)	0.0018 (8)	0.0039 (8)	−0.0047 (8)
C1	0.0251 (13)	0.0258 (13)	0.0217 (11)	−0.0010 (10)	0.0071 (9)	−0.0021 (10)
C2	0.0346 (18)	0.078 (3)	0.061 (2)	0.0119 (16)	0.0263 (15)	0.0265 (19)
C3	0.0325 (16)	0.0416 (18)	0.065 (2)	0.0149 (13)	0.0184 (14)	0.0241 (16)
C4	0.080 (3)	0.049 (2)	0.119 (4)	0.018 (2)	0.007 (3)	0.003 (2)
C5	0.041 (2)	0.078 (3)	0.061 (2)	0.0160 (18)	0.0045 (16)	0.027 (2)
C6	0.0208 (12)	0.0241 (13)	0.0191 (11)	−0.0006 (9)	0.0034 (9)	−0.0035 (9)
C7	0.0447 (11)	0.0438 (11)	0.0440 (10)	−0.0024 (8)	0.0150 (8)	−0.0098 (8)
C8	0.0276 (15)	0.0411 (16)	0.0346 (14)	−0.0039 (12)	0.0155 (11)	−0.0053 (12)
C9	0.036 (2)	0.089 (3)	0.084 (3)	0.0108 (19)	0.0224 (18)	0.031 (2)
C10	0.061 (2)	0.056 (2)	0.0398 (17)	−0.0082 (17)	0.0231 (15)	−0.0037 (15)
C11	0.0230 (13)	0.0221 (12)	0.0233 (11)	0.0035 (10)	0.0042 (9)	0.0040 (10)
C12	0.0241 (13)	0.0176 (12)	0.0282 (12)	0.0024 (9)	0.0070 (10)	−0.0021 (10)
C13	0.0216 (12)	0.0206 (12)	0.0236 (11)	−0.0012 (9)	0.0071 (9)	−0.0044 (10)
C14	0.0176 (12)	0.0210 (12)	0.0209 (11)	−0.0019 (9)	0.0053 (9)	−0.0024 (9)
C15	0.0141 (11)	0.0177 (11)	0.0191 (10)	0.0002 (9)	0.0048 (8)	0.0000 (9)
C16	0.0161 (11)	0.0167 (11)	0.0205 (11)	−0.0011 (9)	0.0049 (8)	−0.0014 (9)
C17	0.0170 (12)	0.0200 (12)	0.0222 (11)	0.0004 (9)	0.0022 (9)	0.0007 (9)
C18	0.0283 (14)	0.0245 (13)	0.0207 (11)	−0.0016 (10)	−0.0019 (10)	0.0023 (10)
C19	0.0281 (14)	0.0278 (14)	0.0164 (11)	−0.0034 (10)	0.0013 (9)	−0.0021 (10)
C20	0.0224 (13)	0.0212 (13)	0.0285 (12)	0.0014 (10)	0.0029 (10)	0.0043 (10)
C21	0.0286 (14)	0.0175 (12)	0.0364 (14)	0.0033 (10)	0.0104 (11)	−0.0019 (10)
C22	0.0296 (14)	0.0216 (13)	0.0262 (12)	0.0021 (10)	0.0058 (10)	−0.0060 (10)

Geometric parameters (Å, º) top

Zn—S1	2.4782 (6)	C7—H7A	0.9800
Zn—S2	2.5408 (7)	C7—H7B	0.9800
Zn—S3	2.5031 (6)	C7—H7C	0.9800
Zn—S4	2.5132 (7)	C8—C9	1.508 (4)
Zn—N3	2.1939 (18)	C8—C10	1.521 (4)
Zn—N4	2.1970 (19)	C8—H8	1.0000
S1—C1	1.719 (2)	C9—H9A	0.9800
S2—C1	1.724 (2)	C9—H9B	0.9800
S3—C6	1.718 (2)	C9—H9C	0.9800
S4—C6	1.720 (2)	C10—H10A	0.9800
N1—C1	1.326 (3)	C10—H10B	0.9800
N1—C2	1.467 (3)	C10—H10C	0.9800
N1—C3	1.483 (3)	C11—C12	1.399 (3)
N2—C6	1.331 (3)	C11—H11	0.9500
N2—C7	1.469 (3)	C12—C13	1.363 (3)
N2—C8	1.476 (3)	C12—H12	0.9500
N3—C11	1.327 (3)	C13—C14	1.411 (3)
N3—C15	1.355 (3)	C13—H13	0.9500
N4—C22	1.334 (3)	C14—C15	1.407 (3)
N4—C16	1.356 (3)	C14—C19	1.429 (3)
C2—H2A	0.9800	C15—C16	1.440 (3)
C2—H2B	0.9800	C16—C17	1.409 (3)
C2—H2C	0.9800	C17—C20	1.405 (3)
C3—C4	1.506 (5)	C17—C18	1.430 (3)
C3—C5	1.512 (5)	C18—C19	1.359 (4)
C3—H3	1.0000	C18—H18	0.9500
C4—H4A	0.9800	C19—H19	0.9500
C4—H4B	0.9800	C20—C21	1.362 (3)
C4—H4C	0.9800	C20—H20	0.9500
C5—H5A	0.9800	C21—C22	1.395 (3)
C5—H5B	0.9800	C21—H21	0.9500
C5—H5C	0.9800	C22—H22	0.9500

N3—Zn—N4	75.76 (7)	N2—C7—H7A	109.5
N3—Zn—S1	95.33 (5)	N2—C7—H7B	109.5
N4—Zn—S1	162.22 (5)	H7A—C7—H7B	109.5
N3—Zn—S3	162.30 (5)	N2—C7—H7C	109.5
N4—Zn—S3	93.33 (5)	H7A—C7—H7C	109.5
S1—Zn—S3	98.69 (2)	H7B—C7—H7C	109.5
N3—Zn—S4	95.23 (5)	N2—C8—C9	110.0 (2)
N4—Zn—S4	96.85 (5)	N2—C8—C10	111.5 (2)
S1—Zn—S4	99.30 (2)	C9—C8—C10	112.2 (3)
S3—Zn—S4	71.94 (2)	N2—C8—H8	107.7
N3—Zn—S2	89.90 (5)	C9—C8—H8	107.7
N4—Zn—S2	92.70 (5)	C10—C8—H8	107.7
S1—Zn—S2	71.65 (2)	C8—C9—H9A	109.5
S3—Zn—S2	104.71 (2)	C8—C9—H9B	109.5
S4—Zn—S2	170.02 (2)	H9A—C9—H9B	109.5
C1—S1—Zn	86.57 (8)	C8—C9—H9C	109.5
C1—S2—Zn	84.50 (8)	H9A—C9—H9C	109.5
C6—S3—Zn	85.22 (8)	H9B—C9—H9C	109.5
C6—S4—Zn	84.85 (8)	C8—C10—H10A	109.5
C1—N1—C2	120.2 (2)	C8—C10—H10B	109.5
C1—N1—C3	122.5 (2)	H10A—C10—H10B	109.5
C2—N1—C3	117.3 (2)	C8—C10—H10C	109.5
C6—N2—C7	119.9 (2)	H10A—C10—H10C	109.5
C6—N2—C8	122.8 (2)	H10B—C10—H10C	109.5
C7—N2—C8	117.2 (2)	N3—C11—C12	123.0 (2)
C11—N3—C15	118.04 (19)	N3—C11—H11	118.5
C11—N3—Zn	127.37 (15)	C12—C11—H11	118.5
C15—N3—Zn	114.51 (14)	C13—C12—C11	119.3 (2)
C22—N4—C16	117.9 (2)	C13—C12—H12	120.4
C22—N4—Zn	127.77 (15)	C11—C12—H12	120.4
C16—N4—Zn	114.32 (15)	C12—C13—C14	119.7 (2)
N1—C1—S1	121.99 (19)	C12—C13—H13	120.1
N1—C1—S2	120.82 (19)	C14—C13—H13	120.1
S1—C1—S2	117.15 (14)	C15—C14—C13	117.0 (2)
N1—C2—H2A	109.5	C15—C14—C19	119.5 (2)
N1—C2—H2B	109.5	C13—C14—C19	123.5 (2)
H2A—C2—H2B	109.5	N3—C15—C14	123.0 (2)
N1—C2—H2C	109.5	N3—C15—C16	117.49 (19)
H2A—C2—H2C	109.5	C14—C15—C16	119.45 (19)
H2B—C2—H2C	109.5	N4—C16—C17	122.6 (2)
N1—C3—C4	111.2 (3)	N4—C16—C15	117.71 (19)
N1—C3—C5	111.6 (3)	C17—C16—C15	119.66 (19)
C4—C3—C5	112.9 (3)	C20—C17—C16	117.6 (2)
N1—C3—H3	106.9	C20—C17—C18	123.0 (2)
C4—C3—H3	106.9	C16—C17—C18	119.4 (2)
C5—C3—H3	106.9	C19—C18—C17	120.9 (2)
C3—C4—H4A	109.5	C19—C18—H18	119.6
C3—C4—H4B	109.5	C17—C18—H18	119.6
H4A—C4—H4B	109.5	C18—C19—C14	121.0 (2)
C3—C4—H4C	109.5	C18—C19—H19	119.5
H4A—C4—H4C	109.5	C14—C19—H19	119.5
H4B—C4—H4C	109.5	C21—C20—C17	119.3 (2)
C3—C5—H5A	109.5	C21—C20—H20	120.3
C3—C5—H5B	109.5	C17—C20—H20	120.3
H5A—C5—H5B	109.5	C20—C21—C22	119.6 (2)
C3—C5—H5C	109.5	C20—C21—H21	120.2
H5A—C5—H5C	109.5	C22—C21—H21	120.2
H5B—C5—H5C	109.5	N4—C22—C21	122.9 (2)
N2—C6—S4	121.87 (19)	N4—C22—H22	118.5
N2—C6—S3	120.21 (18)	C21—C22—H22	118.5
S4—C6—S3	117.92 (14)

N3—Zn—S1—C1	85.85 (10)	C2—N1—C3—C5	56.7 (4)
N4—Zn—S1—C1	27.03 (19)	C7—N2—C6—S4	−177.3 (2)
S3—Zn—S1—C1	−104.98 (8)	C8—N2—C6—S4	−2.4 (3)
S4—Zn—S1—C1	−177.95 (8)	C7—N2—C6—S3	3.8 (3)
S2—Zn—S1—C1	−2.27 (8)	C8—N2—C6—S3	178.72 (19)
N3—Zn—S2—C1	−93.38 (9)	Zn—S4—C6—N2	178.5 (2)
N4—Zn—S2—C1	−169.12 (9)	Zn—S4—C6—S3	−2.66 (13)
S1—Zn—S2—C1	2.27 (8)	Zn—S3—C6—N2	−178.4 (2)
S3—Zn—S2—C1	96.72 (8)	Zn—S3—C6—S4	2.67 (13)
S4—Zn—S2—C1	27.68 (16)	C6—N2—C8—C9	−106.7 (3)
N3—Zn—S3—C6	43.33 (19)	C7—N2—C8—C9	68.4 (3)
N4—Zn—S3—C6	94.43 (9)	C6—N2—C8—C10	128.3 (3)
S1—Zn—S3—C6	−98.71 (8)	C7—N2—C8—C10	−56.7 (3)
S4—Zn—S3—C6	−1.70 (8)	C15—N3—C11—C12	−0.3 (3)
S2—Zn—S3—C6	−171.90 (8)	Zn—N3—C11—C12	−176.88 (17)
N3—Zn—S4—C6	−165.83 (9)	N3—C11—C12—C13	0.7 (4)
N4—Zn—S4—C6	−89.58 (9)	C11—C12—C13—C14	−0.6 (3)
S1—Zn—S4—C6	97.88 (8)	C12—C13—C14—C15	0.1 (3)
S3—Zn—S4—C6	1.70 (8)	C12—C13—C14—C19	−178.4 (2)
S2—Zn—S4—C6	73.51 (16)	C11—N3—C15—C14	−0.2 (3)
N4—Zn—N3—C11	−179.2 (2)	Zn—N3—C15—C14	176.82 (17)
S1—Zn—N3—C11	16.4 (2)	C11—N3—C15—C16	178.2 (2)
S3—Zn—N3—C11	−125.9 (2)	Zn—N3—C15—C16	−4.8 (2)
S4—Zn—N3—C11	−83.45 (19)	C13—C14—C15—N3	0.3 (3)
S2—Zn—N3—C11	87.97 (19)	C19—C14—C15—N3	178.9 (2)
N4—Zn—N3—C15	4.09 (15)	C13—C14—C15—C16	−178.1 (2)
S1—Zn—N3—C15	−160.28 (15)	C19—C14—C15—C16	0.5 (3)
S3—Zn—N3—C15	57.4 (3)	C22—N4—C16—C17	−0.3 (3)
S4—Zn—N3—C15	99.85 (15)	Zn—N4—C16—C17	−179.72 (17)
S2—Zn—N3—C15	−88.72 (15)	C22—N4—C16—C15	−179.2 (2)
N3—Zn—N4—C22	177.8 (2)	Zn—N4—C16—C15	1.5 (3)
S1—Zn—N4—C22	−120.7 (2)	N3—C15—C16—N4	2.2 (3)
S3—Zn—N4—C22	11.9 (2)	C14—C15—C16—N4	−179.3 (2)
S4—Zn—N4—C22	84.1 (2)	N3—C15—C16—C17	−176.6 (2)
S2—Zn—N4—C22	−93.0 (2)	C14—C15—C16—C17	1.9 (3)
N3—Zn—N4—C16	−2.91 (15)	N4—C16—C17—C20	−0.9 (3)
S1—Zn—N4—C16	58.6 (3)	C15—C16—C17—C20	177.9 (2)
S3—Zn—N4—C16	−168.78 (15)	N4—C16—C17—C18	178.4 (2)
S4—Zn—N4—C16	−96.59 (15)	C15—C16—C17—C18	−2.8 (3)
S2—Zn—N4—C16	86.31 (15)	C20—C17—C18—C19	−179.3 (2)
C2—N1—C1—S1	176.6 (2)	C16—C17—C18—C19	1.4 (4)
C3—N1—C1—S1	−0.1 (4)	C17—C18—C19—C14	1.0 (4)
C2—N1—C1—S2	−5.7 (4)	C15—C14—C19—C18	−2.0 (4)
C3—N1—C1—S2	177.6 (2)	C13—C14—C19—C18	176.5 (2)
Zn—S1—C1—N1	−178.6 (2)	C16—C17—C20—C21	1.2 (3)
Zn—S1—C1—S2	3.58 (13)	C18—C17—C20—C21	−178.1 (2)
Zn—S2—C1—N1	178.6 (2)	C17—C20—C21—C22	−0.2 (4)
Zn—S2—C1—S1	−3.50 (12)	C16—N4—C22—C21	1.4 (4)
C1—N1—C3—C4	106.4 (3)	Zn—N4—C22—C21	−179.31 (18)
C2—N1—C3—C4	−70.4 (4)	C20—C21—C22—N4	−1.1 (4)
C1—N1—C3—C5	−126.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the Zn,S1,S2,C1 chelate ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7b···S2ⁱ	0.98	2.79	3.734 (3)	162
C13—H13···S4ⁱⁱ	0.95	2.82	3.634 (2)	145
C21—H21···S1ⁱⁱⁱ	0.95	2.84	3.684 (3)	149
C20—H20···Cg1^iv	0.95	2.74	3.687 (2)	173

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₁₀NS₂)₂(C₁₂H₈N₂)]
M_r	542.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	11.8015 (3), 16.6316 (4), 13.7505 (3)
β (°)	101.738 (2)
V (Å³)	2642.48 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.25 × 0.20 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.777, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	33394, 6001, 4814
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.093, 1.04
No. of reflections	6001
No. of parameters	286
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.50

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn—S1	2.4782 (6)	Zn—S4	2.5132 (7)
Zn—S2	2.5408 (7)	Zn—N3	2.1939 (18)
Zn—S3	2.5031 (6)	Zn—N4	2.1970 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the Zn,S1,S2,C1 chelate ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7b···S2ⁱ	0.98	2.79	3.734 (3)	162
C13—H13···S4ⁱⁱ	0.95	2.82	3.634 (2)	145
C21—H21···S1ⁱⁱⁱ	0.95	2.84	3.684 (3)	149
C20—H20···Cg1^iv	0.95	2.74	3.687 (2)	173

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, z−1/2.

Footnotes

‡Additional correspondence author, e-mail: aibi@ukm.my.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia (UKM-GUP-NBT-08–27-111), the Ministry of Higher Education (UKM-ST-06-FRGS0092–2010), Universiti Putra Malaysia and the University of Malaya for supporting this study.

References

Benson, R. E., Ellis, C. A., Lewis, C. E. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 930–940. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Jamaluddin, N. A., Baba, I., Mohamed Tahir, M. I. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m384–m385. Web of Science CSD CrossRef IUCr Journals Google Scholar
Malik, M. A., Motevalli, M., O'Brien, P. & Walsh, J. R. (1997). Inorg. Chem. 36, 1263–1264. CSD CrossRef PubMed CAS Web of Science Google Scholar
Motevalli, M., O'Brien, P., Walsh, J. R. & Watson, I. M. (1996). Polyhedron, 15, 2801–2808. CrossRef CAS Google Scholar
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Volume 67| Part 5| May 2011| Pages m553-m554

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