(Bipyridine-κ2N,N′)chlorido[N-(2-hydroxy­ethyl)-N-isopropyl­dithio­carbamato-κ2S,S′]zinc(II)

Mohamad, F.A.; Baba, I.; Mohamed Tahir, M.I.; Tiekink, E.R.T.

doi:10.1107/S1600536812027626

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m958-m959

https://doi.org/10.1107/S1600536812027626

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(Bipyridine-κ²N,N′)chlorido[N-(2-hydroxyethyl)-N-isopropyldithiocarbamato-κ²S,S′]zinc(II)

Fatin Allia Mohamad,^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 18 June 2012; accepted 18 June 2012; online 23 June 2012)

The Zn^II atom in the title compound, [Zn(C₆H₁₂NOS₂)Cl(C₁₀H₈N₂)], is coordinated by a chelating N-2-hydroxyethyl-N-isopropyldithiocarbamate ligand, a 2,2′-bipyridine ligand and a Cl atom. The resulting ClN₂S₂ donor set defines a distorted square-pyramidal coordination geometry. Helical supramolecular chains sustained by O—H⋯S hydrogen bonds and propagating along the b axis feature in the crystal packing. A three-dimensional architecture is stabilized by C—H⋯O, C—H⋯S and C—H⋯Cl interactions.

Related literature

For crystal engineering studies on zinc complexes with fuctionalized dithiocarbamate ligands, see: Benson et al. (2007 ); Poplaukhin & Tiekink (2010 ). For the distinction between square-pyramidal and trigonal-bipyramidal geometries, see: Addison et al. (1984 ).

Experimental

Crystal data

[Zn(C₆H₁₂NOS₂)Cl(C₁₀H₈N₂)]
M_r = 435.29
Monoclinic, P 2₁ /n
a = 14.5008 (10) Å
b = 8.6216 (4) Å
c = 15.9905 (9) Å
β = 114.423 (7)°
V = 1820.25 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 100 K
0.35 × 0.20 × 0.12 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.882, T_max = 1.000
11927 measured reflections
4061 independent reflections
3603 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.071
S = 1.04
4061 reflections
222 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn—Cl1	2.2503 (5)
Zn—S1	2.4366 (6)
Zn—S2	2.5026 (6)
Zn—N2	2.1097 (18)
Zn—N3	2.1692 (18)
S1—C1	1.736 (2)
S2—C1	1.723 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯S1ⁱ	0.84 (2)	2.42 (2)	3.2528 (18)	167 (2)
C6—H6c⋯O1ⁱ	0.98	2.47	3.438 (3)	169
C13—H13⋯S2ⁱⁱ	0.95	2.81	3.625 (2)	144
C7—H7⋯Cl1ⁱⁱⁱ	0.95	2.79	3.579 (3)	142
C8—H8⋯Cl1^iv	0.95	2.76	3.606 (2)	148
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+1, -y, -z+1; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); 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 for Windows (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: https://doi.org/10.1107/S1600536812027626/bt5940sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027626/bt5940Isup2.hkl

checkCIF report

Comment top

Introducing hydroxylethyl functionality into dithiocarbamate ligands facilitates the formation of higher dimensionality in their crystal structures (Benson et al., 2007; Poplaukhin & Tiekink, 2010). As a continuation of these studies, herein, the title compound, Zn[S₂CN(CH₂CH₂OH)iPr](2,2'-bipyridine)Cl, (I), is described.

The molecular structure of (I), Fig. 1, features a Zn^II atom coordinated by a dithiocarbamate ligand, two N atoms of the 2,2'-bipyridine ligand and a chloride. The dithiocarbamate ligand coordinates essentially in a bidentate mode, an assignment supported by the near equivalence of the C—S bond distances, Table 1. The resulting ClN₂S₂ donor set defines a coordination geometry intermediate between square pyramidal and trigonal bipyramidal geometry. This is quantified by the value of τ = 0.23 which compares to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal geometries, respectively (Addison et al., 1984).

The crystal packing of (I) features helical supramolecular chains along the b axis that are sustained by O—H···S interactions, Fig. 2 and Table 2. Additional stability to the chains are afforded by C—H···O and C—H···S interactions, Table 2. The chains are connected into a three-dimensional architecture by C—H···Cl interactions, Fig. 3 and Table 1.

Related literature top

For crystal engineering studies on zinc complexes with fuctionalized dithiocarbamate ligands, see: Benson et al. (2007); Poplaukhin & Tiekink (2010). For the distinction between square-pyramidal and trigonal-bipyramidal geometries, see: Addison et al. (1984).

Experimental top

This compound was prepared using the in situ method by the addition of carbon disulfide (0.01 mol) to an ethanolic solution of isopropylethanolamine (0.01 mol). The mixture was stirred for one hour at 277 K. Then, it was added drop-wise to a solution of zinc dichloride (0.005 mol) in ethanol (20 ml) followed by 2,2'-bipyridine (0.01 mol) in ethanol (20 ml). The mixture was stirred for another two hours at 277 K. The white precipitate was filtered, washed with cold ethanol and dried in a desiccator. Crystallization was from its ethanol:chloroform (1:2) solution held at room temperature. Yield: 65.5%. M.pt. 424–426 K. Elemental analysis. Found (calculated) for C₁₆H₂₀ClN₃OS₂Zn: C, 45.21 (44.70); H 3.59 (3.50); N 9.69 (9.70); S 15.12 (14.90)%. IR (KBr): ν(O—H) 3391 m; ν(C≐N) 1442 s; ν(C≐S) 944 s; ν(Zn—S) 368 m cm^-1.

Structure description top

For crystal engineering studies on zinc complexes with fuctionalized dithiocarbamate ligands, see: Benson et al. (2007); Poplaukhin & Tiekink (2010). For the distinction between square-pyramidal and trigonal-bipyramidal geometries, see: Addison et al. (1984).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the helical supramolecular chain in (I) mediated by O—H···S hydrogen bonds (orange dashed lines) along the b axis.
	Fig. 3. A view of the crystal packing in projection down the b axis. The O—H···S, C—H···O, C—H···S and C—H···Cl interactions are shown as orange, pink, brown and blue dashed lines, respectively.

(Bipyridine-κ²N,N')chlorido[N-(2-hydroxyethyl)- N-isopropyldithiocarbamato-κ²S,S']zinc(II) top

Crystal data top

[Zn(C₆H₁₂NOS₂)Cl(C₁₀H₈N₂)]	F(000) = 896
M_r = 435.29	D_x = 1.588 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4897 reflections
a = 14.5008 (10) Å	θ = 2.4–28.7°
b = 8.6216 (4) Å	µ = 1.73 mm⁻¹
c = 15.9905 (9) Å	T = 100 K
β = 114.423 (7)°	Block, colourless
V = 1820.25 (18) Å³	0.35 × 0.20 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	4061 independent reflections
Radiation source: fine-focus sealed tube	3603 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.1952 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −17→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→9
T_min = 0.882, T_max = 1.000	l = −20→20
11927 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0245P)² + 1.5375P] where P = (F_o² + 2F_c²)/3
4061 reflections	(Δ/σ)_max = 0.001
222 parameters	Δρ_max = 0.83 e Å⁻³
1 restraint	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Zn(C₆H₁₂NOS₂)Cl(C₁₀H₈N₂)]	V = 1820.25 (18) Å³
M_r = 435.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.5008 (10) Å	µ = 1.73 mm⁻¹
b = 8.6216 (4) Å	T = 100 K
c = 15.9905 (9) Å	0.35 × 0.20 × 0.12 mm
β = 114.423 (7)°

Data collection top

Oxford Diffraction Xcaliber Eos Gemini diffractometer	4061 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3603 reflections with I > 2σ(I)
T_min = 0.882, T_max = 1.000	R_int = 0.034
11927 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.83 e Å⁻³
4061 reflections	Δρ_min = −0.37 e Å⁻³
222 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	0.330691 (19)	0.17193 (3)	0.503343 (15)	0.01377 (8)
Cl1	0.35450 (4)	0.06878 (6)	0.38450 (3)	0.01704 (12)
S1	0.17619 (4)	0.07781 (6)	0.51151 (3)	0.01631 (12)
S2	0.38248 (4)	−0.02253 (6)	0.63081 (3)	0.01617 (12)
O1	0.29263 (14)	−0.1242 (2)	0.85472 (11)	0.0279 (4)
H1o	0.294 (2)	−0.194 (2)	0.8922 (15)	0.030*
N1	0.21773 (14)	−0.1346 (2)	0.64509 (12)	0.0164 (4)
N2	0.44495 (14)	0.3303 (2)	0.58105 (11)	0.0142 (4)
N3	0.26566 (14)	0.3969 (2)	0.45052 (11)	0.0148 (4)
C1	0.25446 (16)	−0.0378 (2)	0.60191 (13)	0.0146 (4)
C2	0.28503 (17)	−0.2471 (3)	0.71296 (14)	0.0183 (5)
H2A	0.3303	−0.2945	0.6878	0.022*
H2B	0.2429	−0.3310	0.7211	0.022*
C3	0.34975 (19)	−0.1781 (3)	0.80665 (15)	0.0239 (5)
H3A	0.3983	−0.2578	0.8444	0.029*
H3B	0.3894	−0.0906	0.7984	0.029*
C4	0.10593 (17)	−0.1546 (3)	0.61485 (15)	0.0179 (5)
H4	0.0724	−0.0613	0.5774	0.021*
C5	0.07640 (18)	−0.1600 (3)	0.69567 (15)	0.0225 (5)
H5A	0.0974	−0.2595	0.7276	0.034*
H5B	0.0028	−0.1489	0.6733	0.034*
H5C	0.1099	−0.0752	0.7382	0.034*
C6	0.06906 (18)	−0.2952 (3)	0.55214 (15)	0.0238 (5)
H6A	0.0830	−0.2801	0.4977	0.036*
H6B	−0.0040	−0.3080	0.5332	0.036*
H6C	0.1045	−0.3882	0.5852	0.036*
C7	0.53526 (17)	0.2870 (3)	0.64499 (14)	0.0181 (5)
H7	0.5487	0.1796	0.6569	0.022*
C8	0.61006 (17)	0.3927 (3)	0.69449 (15)	0.0198 (5)
H8	0.6734	0.3585	0.7396	0.024*
C9	0.59019 (17)	0.5490 (3)	0.67659 (14)	0.0198 (5)
H9	0.6401	0.6241	0.7092	0.024*
C10	0.49646 (17)	0.5954 (3)	0.61041 (14)	0.0172 (5)
H10	0.4815	0.7024	0.5974	0.021*
C11	0.42524 (16)	0.4830 (2)	0.56367 (13)	0.0138 (4)
C12	0.32424 (16)	0.5203 (3)	0.48989 (13)	0.0141 (4)
C13	0.29299 (18)	0.6707 (3)	0.46101 (14)	0.0188 (5)
H13	0.3355	0.7563	0.4897	0.023*
C14	0.19875 (19)	0.6939 (3)	0.38968 (14)	0.0215 (5)
H14	0.1757	0.7960	0.3692	0.026*
C15	0.13850 (18)	0.5670 (3)	0.34845 (15)	0.0224 (5)
H15	0.0740	0.5801	0.2989	0.027*
C16	0.17453 (17)	0.4209 (3)	0.38117 (14)	0.0199 (5)
H16	0.1331	0.3336	0.3535	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.01493 (14)	0.01139 (14)	0.01590 (12)	−0.00257 (10)	0.00730 (10)	−0.00175 (9)
Cl1	0.0189 (3)	0.0167 (3)	0.0165 (2)	0.0009 (2)	0.0083 (2)	−0.00189 (19)
S1	0.0165 (3)	0.0150 (3)	0.0181 (2)	0.0020 (2)	0.0078 (2)	0.0045 (2)
S2	0.0143 (3)	0.0157 (3)	0.0171 (2)	−0.0017 (2)	0.0050 (2)	0.0012 (2)
O1	0.0363 (11)	0.0248 (10)	0.0236 (8)	−0.0009 (8)	0.0135 (8)	0.0025 (7)
N1	0.0153 (9)	0.0171 (10)	0.0164 (8)	0.0000 (8)	0.0063 (7)	0.0021 (7)
N2	0.0166 (9)	0.0127 (9)	0.0157 (8)	−0.0020 (7)	0.0091 (7)	−0.0006 (7)
N3	0.0163 (9)	0.0140 (9)	0.0156 (8)	−0.0029 (8)	0.0081 (7)	−0.0023 (7)
C1	0.0166 (11)	0.0131 (11)	0.0144 (9)	0.0006 (9)	0.0067 (8)	−0.0018 (8)
C2	0.0184 (11)	0.0154 (12)	0.0199 (10)	0.0021 (10)	0.0066 (9)	0.0059 (9)
C3	0.0245 (13)	0.0265 (13)	0.0193 (11)	−0.0029 (11)	0.0077 (9)	0.0032 (9)
C4	0.0144 (11)	0.0188 (12)	0.0209 (10)	−0.0009 (9)	0.0077 (9)	0.0033 (9)
C5	0.0186 (12)	0.0288 (14)	0.0226 (11)	−0.0058 (10)	0.0110 (9)	−0.0003 (10)
C6	0.0164 (12)	0.0291 (14)	0.0239 (11)	−0.0027 (11)	0.0064 (9)	−0.0041 (10)
C7	0.0169 (11)	0.0187 (12)	0.0209 (10)	0.0005 (10)	0.0099 (9)	0.0026 (9)
C8	0.0155 (11)	0.0261 (13)	0.0178 (10)	−0.0018 (10)	0.0070 (8)	0.0007 (9)
C9	0.0186 (12)	0.0250 (13)	0.0184 (10)	−0.0082 (10)	0.0103 (9)	−0.0058 (9)
C10	0.0197 (12)	0.0154 (11)	0.0191 (10)	−0.0030 (9)	0.0107 (9)	−0.0033 (8)
C11	0.0178 (11)	0.0126 (11)	0.0150 (9)	−0.0035 (9)	0.0105 (8)	−0.0020 (8)
C12	0.0187 (11)	0.0142 (11)	0.0125 (9)	−0.0011 (9)	0.0096 (8)	−0.0022 (8)
C13	0.0274 (13)	0.0127 (11)	0.0162 (10)	−0.0017 (10)	0.0089 (9)	−0.0008 (8)
C14	0.0298 (14)	0.0176 (12)	0.0171 (10)	0.0048 (10)	0.0096 (9)	0.0030 (9)
C15	0.0207 (12)	0.0267 (13)	0.0177 (10)	0.0032 (10)	0.0059 (9)	0.0003 (9)
C16	0.0179 (12)	0.0233 (13)	0.0176 (10)	−0.0029 (10)	0.0065 (9)	−0.0020 (9)

Geometric parameters (Å, º) top

Zn—Cl1	2.2503 (5)	C5—H5A	0.9800
Zn—S1	2.4366 (6)	C5—H5B	0.9800
Zn—S2	2.5026 (6)	C5—H5C	0.9800
Zn—N2	2.1097 (18)	C6—H6A	0.9800
Zn—N3	2.1692 (18)	C6—H6B	0.9800
S1—C1	1.736 (2)	C6—H6C	0.9800
S2—C1	1.723 (2)	C7—C8	1.386 (3)
O1—C3	1.421 (3)	C7—H7	0.9500
O1—H1o	0.844 (10)	C8—C9	1.383 (3)
N1—C1	1.327 (3)	C8—H8	0.9500
N1—C2	1.482 (3)	C9—C10	1.392 (3)
N1—C4	1.498 (3)	C9—H9	0.9500
N2—C7	1.339 (3)	C10—C11	1.388 (3)
N2—C11	1.351 (3)	C10—H10	0.9500
N3—C16	1.344 (3)	C11—C12	1.487 (3)
N3—C12	1.344 (3)	C12—C13	1.388 (3)
C2—C3	1.522 (3)	C13—C14	1.386 (3)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2B	0.9900	C14—C15	1.386 (3)
C3—H3A	0.9900	C14—H14	0.9500
C3—H3B	0.9900	C15—C16	1.381 (3)
C4—C5	1.521 (3)	C15—H15	0.9500
C4—C6	1.523 (3)	C16—H16	0.9500
C4—H4	1.0000

N2—Zn—N3	76.10 (7)	C4—C5—H5A	109.5
N2—Zn—Cl1	113.32 (5)	C4—C5—H5B	109.5
N3—Zn—Cl1	102.61 (5)	H5A—C5—H5B	109.5
N2—Zn—S1	134.39 (5)	C4—C5—H5C	109.5
N3—Zn—S1	93.28 (5)	H5A—C5—H5C	109.5
Cl1—Zn—S1	112.28 (2)	H5B—C5—H5C	109.5
N2—Zn—S2	93.20 (5)	C4—C6—H6A	109.5
N3—Zn—S2	148.41 (5)	C4—C6—H6B	109.5
Cl1—Zn—S2	108.90 (2)	H6A—C6—H6B	109.5
S1—Zn—S2	72.914 (19)	C4—C6—H6C	109.5
C1—S1—Zn	86.37 (8)	H6A—C6—H6C	109.5
C1—S2—Zn	84.58 (7)	H6B—C6—H6C	109.5
C3—O1—H1o	107 (2)	N2—C7—C8	122.7 (2)
C1—N1—C2	120.56 (19)	N2—C7—H7	118.6
C1—N1—C4	121.19 (18)	C8—C7—H7	118.6
C2—N1—C4	117.28 (17)	C9—C8—C7	118.4 (2)
C7—N2—C11	119.03 (19)	C9—C8—H8	120.8
C7—N2—Zn	123.48 (15)	C7—C8—H8	120.8
C11—N2—Zn	117.49 (14)	C8—C9—C10	119.5 (2)
C16—N3—C12	118.67 (19)	C8—C9—H9	120.3
C16—N3—Zn	125.42 (15)	C10—C9—H9	120.3
C12—N3—Zn	115.87 (14)	C11—C10—C9	118.9 (2)
N1—C1—S2	121.89 (16)	C11—C10—H10	120.5
N1—C1—S1	121.97 (17)	C9—C10—H10	120.5
S2—C1—S1	116.13 (12)	N2—C11—C10	121.5 (2)
N1—C2—C3	114.61 (19)	N2—C11—C12	115.40 (18)
N1—C2—H2A	108.6	C10—C11—C12	123.1 (2)
C3—C2—H2A	108.6	N3—C12—C13	121.8 (2)
N1—C2—H2B	108.6	N3—C12—C11	115.14 (19)
C3—C2—H2B	108.6	C13—C12—C11	123.0 (2)
H2A—C2—H2B	107.6	C14—C13—C12	119.0 (2)
O1—C3—C2	113.6 (2)	C14—C13—H13	120.5
O1—C3—H3A	108.8	C12—C13—H13	120.5
C2—C3—H3A	108.8	C13—C14—C15	119.4 (2)
O1—C3—H3B	108.8	C13—C14—H14	120.3
C2—C3—H3B	108.8	C15—C14—H14	120.3
H3A—C3—H3B	107.7	C16—C15—C14	118.4 (2)
N1—C4—C5	112.13 (17)	C16—C15—H15	120.8
N1—C4—C6	110.02 (18)	C14—C15—H15	120.8
C5—C4—C6	112.90 (19)	N3—C16—C15	122.8 (2)
N1—C4—H4	107.2	N3—C16—H16	118.6
C5—C4—H4	107.2	C15—C16—H16	118.6
C6—C4—H4	107.2

N2—Zn—S1—C1	−77.16 (10)	C4—N1—C2—C3	−113.0 (2)
N3—Zn—S1—C1	−150.87 (8)	N1—C2—C3—O1	66.0 (3)
Cl1—Zn—S1—C1	104.07 (7)	C1—N1—C4—C5	−137.2 (2)
S2—Zn—S1—C1	0.17 (7)	C2—N1—C4—C5	54.0 (3)
N2—Zn—S2—C1	135.54 (9)	C1—N1—C4—C6	96.3 (2)
N3—Zn—S2—C1	67.16 (12)	C2—N1—C4—C6	−72.5 (2)
Cl1—Zn—S2—C1	−108.48 (7)	C11—N2—C7—C8	0.0 (3)
S1—Zn—S2—C1	−0.17 (7)	Zn—N2—C7—C8	179.02 (16)
N3—Zn—N2—C7	−178.42 (18)	N2—C7—C8—C9	−0.2 (3)
Cl1—Zn—N2—C7	−80.48 (17)	C7—C8—C9—C10	0.3 (3)
S1—Zn—N2—C7	100.76 (17)	C8—C9—C10—C11	−0.2 (3)
S2—Zn—N2—C7	31.69 (16)	C7—N2—C11—C10	0.1 (3)
N3—Zn—N2—C11	0.66 (14)	Zn—N2—C11—C10	−179.00 (15)
Cl1—Zn—N2—C11	98.60 (15)	C7—N2—C11—C12	178.38 (18)
S1—Zn—N2—C11	−80.16 (16)	Zn—N2—C11—C12	−0.7 (2)
S2—Zn—N2—C11	−149.23 (14)	C9—C10—C11—N2	0.0 (3)
N2—Zn—N3—C16	177.47 (18)	C9—C10—C11—C12	−178.10 (19)
Cl1—Zn—N3—C16	66.22 (17)	C16—N3—C12—C13	0.2 (3)
S1—Zn—N3—C16	−47.48 (17)	Zn—N3—C12—C13	178.27 (16)
S2—Zn—N3—C16	−109.55 (17)	C16—N3—C12—C11	−177.85 (18)
N2—Zn—N3—C12	−0.47 (14)	Zn—N3—C12—C11	0.2 (2)
Cl1—Zn—N3—C12	−111.72 (14)	N2—C11—C12—N3	0.3 (3)
S1—Zn—N3—C12	134.57 (14)	C10—C11—C12—N3	178.54 (19)
S2—Zn—N3—C12	72.51 (18)	N2—C11—C12—C13	−177.68 (19)
C2—N1—C1—S2	−7.2 (3)	C10—C11—C12—C13	0.5 (3)
C4—N1—C1—S2	−175.69 (15)	N3—C12—C13—C14	0.1 (3)
C2—N1—C1—S1	171.42 (15)	C11—C12—C13—C14	177.9 (2)
C4—N1—C1—S1	2.9 (3)	C12—C13—C14—C15	−0.6 (3)
Zn—S2—C1—N1	178.96 (18)	C13—C14—C15—C16	0.8 (3)
Zn—S2—C1—S1	0.26 (11)	C12—N3—C16—C15	0.1 (3)
Zn—S1—C1—N1	−178.97 (18)	Zn—N3—C16—C15	−177.77 (17)
Zn—S1—C1—S2	−0.26 (11)	C14—C15—C16—N3	−0.6 (3)
C1—N1—C2—C3	78.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···S1ⁱ	0.84 (2)	2.42 (2)	3.2528 (18)	167 (2)
C6—H6c···O1ⁱ	0.98	2.47	3.438 (3)	169
C13—H13···S2ⁱⁱ	0.95	2.81	3.625 (2)	144
C7—H7···Cl1ⁱⁱⁱ	0.95	2.79	3.579 (3)	142
C8—H8···Cl1^iv	0.95	2.76	3.606 (2)	148

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

Experimental details

Crystal data
Chemical formula	[Zn(C₆H₁₂NOS₂)Cl(C₁₀H₈N₂)]
M_r	435.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	14.5008 (10), 8.6216 (4), 15.9905 (9)
β (°)	114.423 (7)
V (Å³)	1820.25 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.35 × 0.20 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcaliber Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.882, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11927, 4061, 3603
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.071, 1.04
No. of reflections	4061
No. of parameters	222
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.37

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn—Cl1	2.2503 (5)	Zn—N3	2.1692 (18)
Zn—S1	2.4366 (6)	S1—C1	1.736 (2)
Zn—S2	2.5026 (6)	S2—C1	1.723 (2)
Zn—N2	2.1097 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···S1ⁱ	0.84 (2)	2.424 (19)	3.2528 (18)	167 (2)
C6—H6c···O1ⁱ	0.98	2.47	3.438 (3)	169
C13—H13···S2ⁱⁱ	0.95	2.81	3.625 (2)	144
C7—H7···Cl1ⁱⁱⁱ	0.95	2.79	3.579 (3)	142
C8—H8···Cl1^iv	0.95	2.76	3.606 (2)	148

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+1, −y, −z+1; (iv) x+1/2, −y+1/2, 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) and Universiti Putra Malaysia for supporting this study. Structural studies are supported by the Ministry of Higher Education through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/3).

References

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