Bis(N-isopropyl-N-methyl­dithio­carbamato-κ² S,S′)(1,10-phenanthroline-κ² N,N′)zinc

Abstract

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,

• a = 11.8015 (3) Å

• b = 16.6316 (4) Å

• c = 13.7505 (3) Å

• β = 101.738 (2)°

• V = 2642.48 (11) ų

• 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 ▶) 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯Cg1iv	0.95	2.74	3.687 (2)	173

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 1.00 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2 to 1.5U_equiv(C). Disorder was noted in the N-alkyl groups of both dithiocarbamate ligands. However, multiple sites could not be resolved. The C7 atom was refined with the ISOR command in SHELX76 (Sheldrick, 2008) in order to obtain a reasonable displacement ellipsoid. The crystallographic assignment of atom types (in response to a level B alert concerning a Hirshfeld test difference for the N2—C7 bond) was substantiated by the elemental analysis and spectroscopy.

Figures

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.

Crystal data

[Zn(C5H10NS2)2(C12H8N2)]	F(000) = 1128
Mr = 542.09	Dx = 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

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

Refinement

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(Fo2) + (0.0376P)2 + 1.5727P] where P = (Fo2 + 2Fc2)/3
6001 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.66 e Å−3
6 restraints	Δρmin = −0.50 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···Cg1iv	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.