Bis(tetra­phenyl­phospho­nium) bis­[N-(trifluoro­methyl­sulfon­yl)dithio­carbimato(2−)-κ2S,S′]zincate(II)

Pinto, P.S.; Rubinger, M.M.M.; Guilardi, S.; Paixão, D.A.; Oliveira, M.R.L.

doi:10.1107/S160053681105207X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages m33-m34

doi:10.1107/S160053681105207X

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Bis(tetraphenylphosphonium) bis[N-(trifluoromethylsulfonyl)dithiocarbimato(2−)-κ²S,S′]zincate(II)

Paula S. Pinto,^a Mayura M. M. Rubinger,^a Silvana Guilardi,^b ^* Drielly A. Paixão ^b and Marcelo R. L. Oliveira ^a

^aDepartamento de Química – UFV, Viçosa MG, Brazil, and ^bInstituto de Química – UFU, Uberlândia, MG, Brazil
^*Correspondence e-mail: silvana@ufu.br

(Received 23 November 2011; accepted 2 December 2011; online 10 December 2011)

The title salt, (C₂₄H₂₀P)₂[Zn(C₂F₃NO₂S₃)₂], consists of a complex dianion and two tetraphenylphosphonium cations. The Zn^II ion displays a distorted tetrahedral coordination environment with four S atoms from two S,S′-chelated N-(trifluoromethylsulfonyl)dithiocarbimate anions. In the crystal, besides the ionic interaction of the oppositely charged ions, intermolecular C—H⋯O interactions between cations and anions are observed. One of the cations interacts with an inversion-related equivalent by π–π stacking between phenyl rings, with a centroid–centroid distance of 3.932 (4) Å.

Related literature

For the antifungal and vulcanization activities and crystal structures of dithiocarbimato complexes, see: Amim et al. (2011 ); Alves et al. (2009 ); Mariano et al. (2007 ); Oliveira et al. (2007 ); Perpétuo et al. (2003 ). For further synthetic details, see: Franca et al. (2006 ). For other literature related to fungicides, see: Hogarth (2005 ).

Experimental

Crystal data

(C₂₄H₂₀P)₂[Zn(C₂F₃NO₂S₃)₂]
M_r = 1190.53
Monoclinic, P 2₁ /c
a = 8.8461 (1) Å
b = 29.1869 (5) Å
c = 20.6963 (3) Å
β = 93.578 (1)°
V = 5333.17 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 295 K
0.42 × 0.18 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.758, T_max = 0.950
57739 measured reflections
11977 independent reflections
8307 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.169
S = 1.05
11977 reflections
646 parameters
H-atom parameters constrained
Δρ_max = 1.18 e Å⁻³
Δρ_min = −1.66 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn—S1	2.3346 (10)
Zn—S2	2.3340 (10)
Zn—S4	2.3376 (9)
Zn—S5	2.3566 (10)

S2—Zn—S1	77.84 (3)
S4—Zn—S5	77.63 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1	0.93	2.68	3.424 (4)	138
C31—H31⋯O4	0.93	2.62	3.470 (4)	153
C33—H33⋯O2ⁱ	0.93	2.47	3.283 (4)	145
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681105207X/pk2371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105207X/pk2371Isup2.hkl

checkCIF report

Comment top

We became interested in the syntheses and characterization of dithiocarbimato-metal complexes due to their similarities with dithiocarbamato complexes, which are important fungicides (Hogarth, 2005). While the dithiocarbamato- metal(II) are neutral substances, the analogous dithiocarbimato-complexes are necessarily anionic species. Thus, the choice of metallic ion, active counter ions or the use of different R groups on the dithiocarbimate structures could improve and/or modulate the antifungal activity.

The title complex is a new member of the class of Zn complexes with general formula [Zn(RSO₂N═CS₂)₂]^2- (Amim et al., 2011; Alves et al., 2009; Mariano et al., 2007; Perpétuo et al., 2003). The literature describes only one complex of this class having an alkyl group (methyl) attached to the SO₂ moiety (Oliveira et al., 2007). The asymmetric unit of the title compound is shown in Fig. 1, and consists of one [Zn(CF₃SO₂N═CS₂)₂]^2- anion and two Ph₄P⁺ cations. The Zn^II ion is coordinated by two S,S'-chelated N-trifluoromethylsulfonyldithiocarbimate ligands, resulting in a slightly distorted ZnS₄ tetrahedral geometry. Due to the formation of the two ZnS₂C four membered rings, the two S—Zn—S angles containing both sulfur atoms of the same ligand are significantly smaller than those containing the sulfur atoms from two ligands (Table 1). The dihedral angle between the two ZnS₂C four membered rings [87.40 (4)°] is greater than that found in the salt (Ph₄P)₂[Zn(CH₃SO₂N═CS₂)₂] of 79.1 (1)° (Oliveira et al., 2007). The C—S [average value of 1.731 Å] and C═N bond distances [1.315 (4) and 1.314 (4) Å] have double bond character. This behavior indicates that the electron density is delocalized over the entire NCS₂ moiety. The S1–C1–N1 and S5–C3–N2 angles are significantly greater than S2–C1–N1 and S4–C3–N2 due to the repulsive interactions between the two SO₂CF₃ groups and the S1 and S5 atoms, respectively, which are cis in relation to the C1–N1 and C3–N2 bonds. Similar behavior is observed for other zinc complexes with dithiocarbimato ligands (Amim et al., 2011; Alves et al., 2009; Oliveira et al., 2007; Perpétuo et al., 2003). The torsion angles of C1–N1–S3–C2 and C3–N2–S6–C4 describing the conformation of the dithiocarbimato ligands are -175.9 (3)° and 180.0 (3)°, respectively. These angles are -67.1 (2)° and 159.6 (2)° in the compound (Ph₄P)₂[Zn(CH₃SO₂N═CS₂)₂] (Oliveira et al., 2007), probably due to the larger size of the CF₃ group and the intermolecular interaction present in the title compound.

In both tetraphenylphosphonium cations, the P–C bond lengths range from 1.785 (3) to 1.803 (3) Å, the C–P–C angles range from 106.6 (2) to 112.1 (1)°, and the P atoms display slightly distorted tetrahedral geometry. The arrangement of molecules is mainly determined by the electrostatic interactions between oppositely charged units. Moreover, there are intermolecular C—H···O interactions between cations and anions (Table 2) and π-π stacking between phenyl rings on inversion related (1-x, -y, 2-z) cations.

Related literature top

For the antifungal and vulcanization activities and crystal structures of dithiocarbimato complexes, see: Amim et al. (2011); Alves et al. (2009); Mariano et al. (2007); Oliveira et al. (2007); Perpétuo et al. (2003). For further synthetic details, see: Franca et al. (2006). For other literature related to fungicides, see: Hogarth (2005).

Experimental top

The potassium trifluoromethylsulfonyldithiocarbimate dihydrate was prepared in dimethylformamide from trifluoromethanesulfonamide as described in the literature (Franca et al., 2006). The title compound was prepared in 1:1 (10 ml) methanol:water by the reaction of zinc acetate dihydrate (1.0 mmol) with trifluoromethylsulfonyldithiocarbimate dihydrate (2.0 mmol) and tetraphenylphosphanium chloride (2.0 mmol). The reaction mixture was stirred for 1 h at room temperature. The white solid obtained was filtered, washed with distilled water and dried under reduced pressure. The title compound is insoluble in water but soluble in chloroform, methanol and dichloromethane. Suitable crystals were obtained after slow evaporation of the solution in dichloromethene:ethanol 2:1 mixture. M.p. 161.5–163.3 °C. IR (selected bands, cm^-1): 1395, 1378 v(C═N); 1315, 1183 (vCF₃), 1298 v_as(SO₂); 1110 v_sym(SO₂); 951 v_as(CS₂) and 323 v(ZnS). ¹³C NMR (dithiocarbimate anion signals) (δ): 119.3 (q, CF₃, J = 317,2 Hz), 226.3 (s, C═N). All spectra (IR, ¹H NMR and ¹³C NMR) showed the expected signals for the tetraphenylphosphonium cation.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Representation of the title compound, with displacement ellipsoids drawn at the 30% probability level.

Bis(tetraphenylphosphonium) bis[N-(trifluoromethylsulfonyl)dithiocarbimato(2-)- κ²S,S']zincate(II) top

Crystal data top

(C₂₄H₂₀P)₂[Zn(C₂F₃NO₂S₃)₂]	F(000) = 2432
M_r = 1190.53	D_x = 1.483 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.8461 (1) Å	Cell parameters from 80040 reflections
b = 29.1869 (5) Å	θ = 2.9–27.5°
c = 20.6963 (3) Å	µ = 0.82 mm⁻¹
β = 93.578 (1)°	T = 295 K
V = 5333.17 (13) Å³	Prism, colourless
Z = 4	0.42 × 0.18 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	11977 independent reflections
Radiation source: Enraf Nonius FR590	8307 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
CCD rotation images, thick slices scans	h = −11→7
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −37→37
T_min = 0.758, T_max = 0.950	l = −26→26
57739 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0872P)² + 2.420P] where P = (F_o² + 2F_c²)/3
11977 reflections	(Δ/σ)_max = 0.003
646 parameters	Δρ_max = 1.18 e Å⁻³
0 restraints	Δρ_min = −1.66 e Å⁻³

Crystal data top

(C₂₄H₂₀P)₂[Zn(C₂F₃NO₂S₃)₂]	V = 5333.17 (13) Å³
M_r = 1190.53	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8461 (1) Å	µ = 0.82 mm⁻¹
b = 29.1869 (5) Å	T = 295 K
c = 20.6963 (3) Å	0.42 × 0.18 × 0.12 mm
β = 93.578 (1)°

Data collection top

Nonius KappaCCD diffractometer	11977 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	8307 reflections with I > 2σ(I)
T_min = 0.758, T_max = 0.950	R_int = 0.082
57739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.05	Δρ_max = 1.18 e Å⁻³
11977 reflections	Δρ_min = −1.66 e Å⁻³
646 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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	0.76875 (4)	0.258126 (13)	1.300410 (19)	0.05905 (14)
S1	0.76765 (13)	0.32502 (3)	1.36222 (5)	0.0744 (3)
S2	0.89252 (11)	0.30995 (3)	1.23596 (4)	0.0636 (2)
S3	0.88481 (12)	0.42771 (3)	1.34592 (5)	0.0706 (2)
S4	0.57897 (9)	0.20559 (3)	1.26862 (5)	0.0615 (2)
S5	0.87243 (10)	0.18826 (3)	1.33924 (5)	0.0658 (2)
S6	0.77346 (10)	0.08409 (3)	1.33543 (4)	0.0600 (2)
P1	0.58019 (9)	0.36494 (3)	1.07700 (4)	0.0529 (2)
P2	0.41864 (8)	0.12861 (3)	1.04277 (4)	0.04373 (18)
F1	0.8570 (4)	0.48605 (10)	1.25094 (14)	0.1171 (10)
F2	1.0842 (3)	0.47099 (9)	1.28085 (14)	0.1085 (9)
F3	0.9532 (4)	0.51320 (8)	1.33994 (13)	0.1030 (9)
F4	0.6206 (4)	0.03089 (10)	1.25260 (17)	0.1194 (10)
F5	0.7129 (4)	−0.00242 (9)	1.33781 (18)	0.1227 (11)
F6	0.5171 (3)	0.03994 (10)	1.34194 (19)	0.1285 (11)
N1	0.9004 (3)	0.39051 (10)	1.29069 (13)	0.0605 (7)
N2	0.6657 (3)	0.12278 (9)	1.30365 (13)	0.0559 (6)
O1	0.7346 (3)	0.43889 (9)	1.36095 (12)	0.0706 (2)
O2	0.9950 (3)	0.42280 (8)	1.39932 (12)	0.0706 (2)
O3	0.7885 (4)	0.08521 (10)	1.40437 (13)	0.0839 (8)
O4	0.9063 (3)	0.07468 (9)	1.30165 (13)	0.0758 (7)
C1	0.8577 (3)	0.34775 (11)	1.29750 (15)	0.0537 (7)
C2	0.9492 (5)	0.47687 (14)	1.3012 (2)	0.0765 (11)
C3	0.7047 (3)	0.16624 (11)	1.30466 (14)	0.0503 (7)
C4	0.6486 (5)	0.03583 (14)	1.3155 (3)	0.0853 (12)
C5	0.4940 (4)	0.36160 (13)	1.15287 (17)	0.0638 (9)
C6	0.3858 (6)	0.32851 (19)	1.1625 (2)	0.0986 (15)
H6	0.3616	0.3069	1.1305	0.118*
C7	0.3137 (7)	0.3277 (3)	1.2198 (3)	0.128 (2)
H7	0.2419	0.3052	1.2268	0.153*
C8	0.3489 (7)	0.3605 (3)	1.2668 (3)	0.125 (2)
H8	0.2972	0.3608	1.3046	0.151*
C9	0.4583 (6)	0.3920 (2)	1.2581 (2)	0.1071 (17)
H9	0.4846	0.413	1.2908	0.129*
C10	0.5303 (4)	0.39325 (15)	1.20132 (18)	0.0744 (10)
H10	0.6037	0.4154	1.1953	0.089*
C11	0.6968 (4)	0.31543 (11)	1.06493 (16)	0.0558 (8)
C12	0.6925 (4)	0.27720 (12)	1.10471 (17)	0.0664 (9)
H12	0.6242	0.2759	1.1371	0.08*
C13	0.7902 (6)	0.24120 (13)	1.0960 (2)	0.0816 (13)
H13	0.7874	0.2157	1.1228	0.098*
C14	0.8906 (6)	0.24230 (15)	1.0487 (3)	0.0889 (14)
H14	0.9562	0.2178	1.0436	0.107*
C15	0.8946 (5)	0.27990 (17)	1.0084 (2)	0.0878 (12)
H15	0.9617	0.2805	0.9755	0.105*
C16	0.7991 (4)	0.31657 (14)	1.01673 (18)	0.0693 (9)
H16	0.8034	0.3421	0.99	0.083*
C17	0.7020 (4)	0.41366 (11)	1.07582 (15)	0.0537 (7)
C18	0.8430 (4)	0.41156 (14)	1.11035 (18)	0.0672 (9)
H18	0.8731	0.3851	1.1326	0.081*
C19	0.9370 (5)	0.44945 (15)	1.1109 (2)	0.0793 (11)
H19	1.0305	0.4485	1.1341	0.095*
C20	0.8941 (6)	0.48820 (16)	1.0781 (2)	0.0939 (14)
H20	0.9586	0.5134	1.0787	0.113*
C21	0.7568 (6)	0.49019 (16)	1.0441 (3)	0.1064 (17)
H21	0.7281	0.5167	1.0216	0.128*
C22	0.6601 (5)	0.45280 (13)	1.0432 (2)	0.0794 (11)
H22	0.5664	0.4543	1.0203	0.095*
C23	0.4320 (3)	0.37039 (11)	1.01393 (16)	0.0536 (7)
C24	0.2849 (4)	0.38278 (15)	1.0277 (2)	0.0750 (10)
H24	0.2615	0.3879	1.0703	0.09*
C25	0.1748 (4)	0.38742 (15)	0.9783 (2)	0.0790 (11)
H25	0.0768	0.3953	0.9879	0.095*
C26	0.2071 (4)	0.38068 (13)	0.9152 (2)	0.0698 (10)
H26	0.1316	0.3839	0.8822	0.084*
C27	0.3520 (4)	0.36912 (14)	0.90089 (19)	0.0698 (9)
H27	0.3748	0.3649	0.858	0.084*
C28	0.4642 (4)	0.36372 (12)	0.95011 (16)	0.0616 (8)
H28	0.5617	0.3556	0.9401	0.074*
C29	0.6183 (3)	0.12592 (9)	1.06577 (13)	0.0418 (6)
C30	0.6682 (3)	0.12508 (10)	1.13043 (14)	0.0475 (6)
H30	0.5996	0.129	1.1623	0.057*
C31	0.8211 (3)	0.11840 (11)	1.14776 (15)	0.0525 (7)
H31	0.8553	0.1173	1.1911	0.063*
C32	0.9212 (3)	0.11350 (11)	1.09979 (16)	0.0527 (7)
H32	1.0234	0.1087	1.1112	0.063*
C33	0.8732 (3)	0.11551 (11)	1.03584 (16)	0.0528 (7)
H33	0.9427	0.1127	1.0042	0.063*
C34	0.7213 (3)	0.12172 (11)	1.01815 (15)	0.0507 (7)
H34	0.6883	0.1231	0.9746	0.061*
C35	0.3211 (3)	0.13903 (11)	1.11472 (15)	0.0510 (7)
C36	0.2516 (4)	0.18093 (13)	1.12335 (18)	0.0625 (8)
H36	0.2526	0.2033	1.0914	0.075*
C37	0.1799 (4)	0.18924 (16)	1.1806 (2)	0.0781 (12)
H37	0.1345	0.2175	1.1871	0.094*
C38	0.1766 (4)	0.15591 (19)	1.22685 (19)	0.0811 (13)
H38	0.126	0.1614	1.2642	0.097*
C39	0.2459 (4)	0.11501 (17)	1.21909 (17)	0.0741 (11)
H39	0.2439	0.0929	1.2514	0.089*
C40	0.3192 (3)	0.10597 (13)	1.16364 (15)	0.0588 (8)
H40	0.3673	0.078	1.1588	0.071*
C41	0.3778 (3)	0.17355 (10)	0.98562 (14)	0.0489 (7)
C42	0.4799 (4)	0.20877 (11)	0.97580 (18)	0.0634 (9)
H42	0.5729	0.2095	0.9994	0.076*
C43	0.4427 (5)	0.24267 (13)	0.9309 (2)	0.0813 (12)
H43	0.5116	0.2659	0.9238	0.098*
C44	0.3046 (5)	0.24214 (14)	0.8969 (2)	0.0821 (12)
H44	0.2797	0.2652	0.8672	0.099*
C45	0.2028 (5)	0.20768 (15)	0.90656 (19)	0.0764 (11)
H45	0.1087	0.2079	0.8838	0.092*
C46	0.2388 (4)	0.17285 (13)	0.94965 (17)	0.0637 (9)
H46	0.171	0.149	0.9548	0.076*
C47	0.3599 (3)	0.07588 (10)	1.00384 (14)	0.0472 (6)
C48	0.2587 (4)	0.04559 (11)	1.02871 (16)	0.0559 (7)
H48	0.2166	0.0519	1.0678	0.067*
C49	0.2205 (4)	0.00612 (12)	0.99541 (19)	0.0668 (9)
H49	0.1515	−0.0141	1.012	0.08*
C50	0.2826 (4)	−0.00369 (12)	0.93823 (19)	0.0652 (9)
H50	0.257	−0.0307	0.9164	0.078*
C51	0.3832 (4)	0.02640 (14)	0.91288 (19)	0.0718 (10)
H51	0.4256	0.0197	0.874	0.086*
C52	0.4205 (4)	0.06620 (13)	0.94506 (17)	0.0670 (9)
H52	0.4868	0.0868	0.9275	0.08*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0568 (2)	0.0545 (2)	0.0660 (3)	−0.00555 (17)	0.00531 (18)	−0.00531 (17)
S1	0.0976 (7)	0.0628 (5)	0.0662 (6)	−0.0187 (5)	0.0324 (5)	−0.0122 (4)
S2	0.0715 (6)	0.0615 (5)	0.0595 (5)	−0.0087 (4)	0.0170 (4)	−0.0105 (4)
S3	0.0793 (5)	0.0670 (5)	0.0670 (5)	−0.0189 (4)	0.0169 (4)	−0.0131 (4)
S4	0.0452 (4)	0.0540 (5)	0.0840 (6)	0.0023 (3)	−0.0067 (4)	−0.0026 (4)
S5	0.0505 (5)	0.0657 (5)	0.0792 (6)	−0.0007 (4)	−0.0113 (4)	0.0004 (4)
S6	0.0575 (5)	0.0567 (5)	0.0661 (5)	0.0069 (4)	0.0063 (4)	0.0033 (4)
P1	0.0490 (4)	0.0558 (5)	0.0538 (5)	−0.0078 (4)	0.0028 (3)	−0.0004 (4)
P2	0.0310 (3)	0.0516 (4)	0.0485 (4)	−0.0019 (3)	0.0015 (3)	−0.0016 (3)
F1	0.167 (3)	0.0894 (18)	0.0918 (18)	0.0078 (18)	−0.0169 (19)	0.0137 (14)
F2	0.114 (2)	0.0865 (17)	0.131 (2)	−0.0304 (16)	0.0558 (18)	−0.0042 (16)
F3	0.149 (3)	0.0613 (13)	0.0995 (18)	−0.0193 (15)	0.0172 (17)	−0.0187 (12)
F4	0.129 (2)	0.0855 (18)	0.139 (3)	−0.0078 (17)	−0.028 (2)	−0.0277 (17)
F5	0.119 (2)	0.0566 (14)	0.191 (3)	0.0091 (14)	0.003 (2)	0.0182 (17)
F6	0.0822 (18)	0.0841 (18)	0.223 (4)	−0.0127 (15)	0.042 (2)	0.006 (2)
N1	0.0680 (17)	0.0590 (16)	0.0557 (15)	−0.0102 (13)	0.0132 (13)	−0.0067 (12)
N2	0.0491 (14)	0.0513 (15)	0.0670 (17)	0.0027 (11)	0.0029 (12)	−0.0022 (12)
O1	0.0793 (5)	0.0670 (5)	0.0670 (5)	−0.0189 (4)	0.0169 (4)	−0.0131 (4)
O2	0.0793 (5)	0.0670 (5)	0.0670 (5)	−0.0189 (4)	0.0169 (4)	−0.0131 (4)
O3	0.102 (2)	0.0844 (18)	0.0650 (16)	0.0128 (16)	0.0061 (14)	0.0117 (13)
O4	0.0603 (14)	0.0793 (17)	0.0889 (18)	0.0176 (13)	0.0128 (13)	0.0008 (14)
C1	0.0469 (16)	0.0598 (19)	0.0545 (18)	−0.0038 (14)	0.0030 (14)	−0.0058 (14)
C2	0.097 (3)	0.062 (2)	0.072 (2)	−0.013 (2)	0.008 (2)	−0.0079 (19)
C3	0.0435 (15)	0.0583 (18)	0.0501 (16)	0.0029 (13)	0.0112 (13)	−0.0027 (13)
C4	0.076 (3)	0.060 (2)	0.121 (4)	0.006 (2)	0.009 (3)	0.003 (2)
C5	0.0565 (19)	0.073 (2)	0.062 (2)	−0.0092 (17)	0.0054 (16)	0.0066 (17)
C6	0.090 (3)	0.122 (4)	0.087 (3)	−0.046 (3)	0.023 (2)	−0.005 (3)
C7	0.105 (4)	0.172 (6)	0.110 (4)	−0.057 (4)	0.043 (3)	0.012 (4)
C8	0.110 (4)	0.183 (6)	0.088 (4)	−0.026 (4)	0.045 (3)	0.007 (4)
C9	0.111 (4)	0.142 (5)	0.071 (3)	−0.010 (4)	0.028 (3)	−0.014 (3)
C10	0.067 (2)	0.096 (3)	0.061 (2)	−0.006 (2)	0.0141 (18)	−0.010 (2)
C11	0.0572 (18)	0.0539 (17)	0.0546 (18)	−0.0058 (14)	−0.0099 (15)	−0.0023 (14)
C12	0.077 (2)	0.057 (2)	0.062 (2)	−0.0165 (18)	−0.0148 (18)	0.0035 (16)
C13	0.096 (3)	0.052 (2)	0.092 (3)	−0.008 (2)	−0.035 (3)	0.0041 (19)
C14	0.089 (3)	0.067 (3)	0.106 (3)	0.018 (2)	−0.030 (3)	−0.014 (2)
C15	0.083 (3)	0.093 (3)	0.086 (3)	0.030 (2)	0.000 (2)	0.002 (2)
C16	0.072 (2)	0.074 (2)	0.062 (2)	0.0119 (19)	0.0010 (18)	0.0075 (17)
C17	0.0503 (17)	0.0574 (18)	0.0541 (17)	−0.0048 (14)	0.0080 (14)	−0.0067 (14)
C18	0.0544 (19)	0.076 (2)	0.071 (2)	−0.0137 (17)	0.0012 (16)	0.0005 (18)
C19	0.063 (2)	0.090 (3)	0.085 (3)	−0.026 (2)	0.004 (2)	−0.012 (2)
C20	0.101 (3)	0.076 (3)	0.105 (3)	−0.038 (3)	0.012 (3)	−0.008 (3)
C21	0.109 (4)	0.063 (2)	0.143 (5)	−0.025 (3)	−0.024 (3)	0.016 (3)
C22	0.079 (3)	0.061 (2)	0.096 (3)	−0.0155 (19)	−0.011 (2)	0.005 (2)
C23	0.0469 (16)	0.0531 (17)	0.0607 (19)	−0.0063 (13)	0.0032 (14)	−0.0014 (14)
C24	0.0534 (19)	0.095 (3)	0.077 (2)	0.0010 (19)	0.0082 (18)	−0.008 (2)
C25	0.0465 (19)	0.094 (3)	0.096 (3)	−0.0001 (19)	0.0016 (19)	−0.004 (2)
C26	0.056 (2)	0.065 (2)	0.085 (3)	−0.0047 (16)	−0.0183 (18)	−0.0004 (19)
C27	0.063 (2)	0.079 (2)	0.065 (2)	0.0018 (18)	−0.0080 (17)	−0.0002 (18)
C28	0.0518 (18)	0.071 (2)	0.062 (2)	0.0013 (16)	0.0013 (15)	0.0037 (16)
C29	0.0331 (12)	0.0454 (14)	0.0469 (15)	−0.0032 (11)	0.0020 (11)	−0.0006 (12)
C30	0.0348 (13)	0.0587 (17)	0.0494 (16)	−0.0034 (12)	0.0041 (12)	−0.0051 (13)
C31	0.0399 (14)	0.0650 (19)	0.0520 (17)	−0.0042 (13)	−0.0019 (13)	0.0009 (14)
C32	0.0306 (13)	0.0585 (18)	0.069 (2)	−0.0038 (12)	0.0005 (13)	−0.0011 (15)
C33	0.0365 (14)	0.0634 (19)	0.0599 (19)	−0.0062 (13)	0.0134 (13)	−0.0071 (14)
C34	0.0394 (14)	0.0643 (18)	0.0487 (16)	−0.0062 (13)	0.0043 (12)	−0.0005 (14)
C35	0.0295 (12)	0.071 (2)	0.0521 (17)	−0.0027 (13)	0.0025 (12)	−0.0085 (15)
C36	0.0449 (16)	0.072 (2)	0.071 (2)	−0.0025 (15)	0.0037 (15)	−0.0159 (17)
C37	0.0470 (19)	0.104 (3)	0.083 (3)	0.0028 (19)	0.0070 (18)	−0.037 (2)
C38	0.0469 (19)	0.140 (4)	0.058 (2)	−0.009 (2)	0.0088 (16)	−0.025 (3)
C39	0.0489 (18)	0.122 (3)	0.0514 (19)	−0.011 (2)	0.0017 (15)	−0.002 (2)
C40	0.0377 (15)	0.085 (2)	0.0541 (18)	−0.0022 (15)	0.0026 (13)	0.0011 (16)
C41	0.0399 (14)	0.0518 (16)	0.0545 (17)	0.0022 (12)	−0.0009 (12)	−0.0022 (13)
C42	0.0588 (19)	0.0536 (18)	0.076 (2)	−0.0053 (15)	−0.0123 (17)	0.0027 (16)
C43	0.086 (3)	0.056 (2)	0.100 (3)	−0.0090 (19)	−0.011 (2)	0.019 (2)
C44	0.091 (3)	0.070 (2)	0.083 (3)	0.012 (2)	−0.014 (2)	0.014 (2)
C45	0.064 (2)	0.086 (3)	0.077 (3)	0.012 (2)	−0.0208 (19)	0.006 (2)
C46	0.0435 (16)	0.071 (2)	0.075 (2)	−0.0003 (15)	−0.0071 (16)	0.0052 (18)
C47	0.0342 (13)	0.0515 (16)	0.0554 (17)	−0.0028 (12)	−0.0011 (12)	−0.0014 (13)
C48	0.0513 (17)	0.0577 (18)	0.0594 (18)	−0.0017 (14)	0.0090 (14)	0.0051 (15)
C49	0.067 (2)	0.0517 (18)	0.082 (2)	−0.0154 (16)	0.0069 (19)	0.0053 (17)
C50	0.068 (2)	0.0477 (17)	0.079 (2)	−0.0017 (15)	−0.0035 (19)	−0.0047 (16)
C51	0.067 (2)	0.076 (2)	0.073 (2)	−0.0100 (19)	0.0159 (18)	−0.0179 (19)
C52	0.0578 (19)	0.076 (2)	0.068 (2)	−0.0235 (17)	0.0161 (16)	−0.0166 (18)

Geometric parameters (Å, º) top

Zn—S1	2.3346 (10)	C20—C21	1.366 (7)
Zn—S2	2.3340 (10)	C20—H20	0.93
Zn—S4	2.3376 (9)	C21—C22	1.386 (6)
Zn—S5	2.3566 (10)	C21—H21	0.93
S1—C1	1.733 (3)	C22—H22	0.93
S2—C1	1.727 (3)	C23—C28	1.382 (5)
S3—O1	1.421 (3)	C23—C24	1.397 (5)
S3—O2	1.435 (3)	C24—C25	1.375 (5)
S3—N1	1.589 (3)	C24—H24	0.93
S3—C2	1.818 (4)	C25—C26	1.369 (6)
S4—C3	1.735 (3)	C25—H25	0.93
S5—C3	1.730 (3)	C26—C27	1.375 (5)
S6—O3	1.425 (3)	C26—H26	0.93
S6—O4	1.431 (3)	C27—C28	1.386 (5)
S6—N2	1.593 (3)	C27—H27	0.93
S6—C4	1.821 (5)	C28—H28	0.93
P1—C17	1.785 (3)	C29—C30	1.383 (4)
P1—C5	1.790 (4)	C29—C34	1.389 (4)
P1—C23	1.798 (3)	C30—C31	1.391 (4)
P1—C11	1.802 (3)	C30—H30	0.93
P2—C41	1.788 (3)	C31—C32	1.379 (4)
P2—C35	1.793 (3)	C31—H31	0.93
P2—C47	1.799 (3)	C32—C33	1.366 (4)
P2—C29	1.802 (3)	C32—H32	0.93
F1—C2	1.309 (5)	C33—C34	1.383 (4)
F2—C2	1.303 (5)	C33—H33	0.93
F3—C2	1.328 (4)	C34—H34	0.93
F4—C4	1.319 (6)	C35—C36	1.385 (5)
F5—C4	1.323 (5)	C35—C40	1.400 (5)
F6—C4	1.321 (5)	C36—C37	1.399 (5)
N1—C1	1.314 (4)	C36—H36	0.93
N2—C3	1.314 (4)	C37—C38	1.367 (7)
C5—C6	1.383 (5)	C37—H37	0.93
C5—C10	1.386 (5)	C38—C39	1.356 (6)
C6—C7	1.381 (7)	C38—H38	0.93
C6—H6	0.93	C39—C40	1.379 (5)
C7—C8	1.387 (8)	C39—H39	0.93
C7—H7	0.93	C40—H40	0.93
C8—C9	1.356 (8)	C41—C42	1.391 (4)
C8—H8	0.93	C41—C46	1.397 (4)
C9—C10	1.372 (6)	C42—C43	1.382 (5)
C9—H9	0.93	C42—H42	0.93
C10—H10	0.93	C43—C44	1.372 (6)
C11—C12	1.389 (5)	C43—H43	0.93
C11—C16	1.389 (5)	C44—C45	1.373 (6)
C12—C13	1.380 (6)	C44—H44	0.93
C12—H12	0.93	C45—C46	1.377 (5)
C13—C14	1.362 (7)	C45—H45	0.93
C13—H13	0.93	C46—H46	0.93
C14—C15	1.381 (7)	C47—C48	1.381 (4)
C14—H14	0.93	C47—C52	1.389 (4)
C15—C16	1.381 (6)	C48—C49	1.374 (5)
C15—H15	0.93	C48—H48	0.93
C16—H16	0.93	C49—C50	1.366 (5)
C17—C22	1.366 (5)	C49—H49	0.93
C17—C18	1.400 (5)	C50—C51	1.377 (5)
C18—C19	1.383 (5)	C50—H50	0.93
C18—H18	0.93	C51—C52	1.369 (5)
C19—C20	1.362 (7)	C51—H51	0.93
C19—H19	0.93	C52—H52	0.93

S2—Zn—S1	77.84 (3)	C19—C20—C21	120.2 (4)
S2—Zn—S4	128.21 (4)	C19—C20—H20	119.9
S1—Zn—S4	132.48 (4)	C21—C20—H20	119.9
S2—Zn—S5	124.69 (4)	C20—C21—C22	120.1 (4)
S1—Zn—S5	123.49 (4)	C20—C21—H21	119.9
S4—Zn—S5	77.63 (3)	C22—C21—H21	119.9
C1—S1—Zn	83.04 (11)	C17—C22—C21	120.2 (4)
C1—S2—Zn	83.17 (11)	C17—C22—H22	119.9
O1—S3—O2	117.00 (15)	C21—C22—H22	119.9
O1—S3—N1	116.02 (16)	C28—C23—C24	118.8 (3)
O2—S3—N1	113.61 (16)	C28—C23—P1	119.8 (2)
O1—S3—C2	104.9 (2)	C24—C23—P1	121.4 (3)
O2—S3—C2	104.58 (19)	C25—C24—C23	120.0 (4)
N1—S3—C2	97.43 (17)	C25—C24—H24	120
C3—S4—Zn	83.31 (11)	C23—C24—H24	120
C3—S5—Zn	82.82 (11)	C26—C25—C24	121.0 (4)
O3—S6—O4	117.73 (18)	C26—C25—H25	119.5
O3—S6—N2	114.39 (16)	C24—C25—H25	119.5
O4—S6—N2	115.02 (15)	C25—C26—C27	119.6 (3)
O3—S6—C4	105.2 (2)	C25—C26—H26	120.2
O4—S6—C4	104.2 (2)	C27—C26—H26	120.2
N2—S6—C4	96.67 (18)	C26—C27—C28	120.3 (4)
C17—P1—C5	110.23 (16)	C26—C27—H27	119.9
C17—P1—C23	109.44 (15)	C28—C27—H27	119.9
C5—P1—C23	108.09 (16)	C23—C28—C27	120.3 (3)
C17—P1—C11	106.60 (15)	C23—C28—H28	119.8
C5—P1—C11	110.89 (17)	C27—C28—H28	119.8
C23—P1—C11	111.59 (15)	C30—C29—C34	120.1 (3)
C41—P2—C35	109.70 (15)	C30—C29—P2	120.3 (2)
C41—P2—C47	106.90 (14)	C34—C29—P2	119.5 (2)
C35—P2—C47	112.13 (14)	C29—C30—C31	119.9 (3)
C41—P2—C29	111.16 (13)	C29—C30—H30	120.1
C35—P2—C29	107.61 (13)	C31—C30—H30	120.1
C47—P2—C29	109.39 (13)	C32—C31—C30	119.2 (3)
C1—N1—S3	122.3 (2)	C32—C31—H31	120.4
C3—N2—S6	121.9 (2)	C30—C31—H31	120.4
N1—C1—S2	117.5 (2)	C33—C32—C31	121.2 (3)
N1—C1—S1	126.6 (3)	C33—C32—H32	119.4
S2—C1—S1	115.92 (19)	C31—C32—H32	119.4
F2—C2—F1	108.0 (4)	C32—C33—C34	120.1 (3)
F2—C2—F3	108.0 (4)	C32—C33—H33	120
F1—C2—F3	108.0 (4)	C34—C33—H33	120
F2—C2—S3	112.5 (3)	C33—C34—C29	119.6 (3)
F1—C2—S3	111.5 (3)	C33—C34—H34	120.2
F3—C2—S3	108.7 (3)	C29—C34—H34	120.2
N2—C3—S5	125.6 (2)	C36—C35—C40	119.3 (3)
N2—C3—S4	118.1 (2)	C36—C35—P2	119.8 (3)
S5—C3—S4	116.24 (18)	C40—C35—P2	120.8 (2)
F4—C4—F6	107.6 (4)	C35—C36—C37	119.4 (4)
F4—C4—F5	107.6 (4)	C35—C36—H36	120.3
F6—C4—F5	107.6 (4)	C37—C36—H36	120.3
F4—C4—S6	112.5 (3)	C38—C37—C36	120.1 (4)
F6—C4—S6	111.9 (3)	C38—C37—H37	120
F5—C4—S6	109.4 (3)	C36—C37—H37	120
C6—C5—C10	119.5 (4)	C39—C38—C37	120.9 (4)
C6—C5—P1	120.1 (3)	C39—C38—H38	119.5
C10—C5—P1	120.4 (3)	C37—C38—H38	119.5
C7—C6—C5	119.8 (5)	C38—C39—C40	120.5 (4)
C7—C6—H6	120.1	C38—C39—H39	119.8
C5—C6—H6	120.1	C40—C39—H39	119.8
C6—C7—C8	119.7 (5)	C39—C40—C35	119.8 (4)
C6—C7—H7	120.2	C39—C40—H40	120.1
C8—C7—H7	120.2	C35—C40—H40	120.1
C9—C8—C7	120.5 (5)	C42—C41—C46	119.4 (3)
C9—C8—H8	119.8	C42—C41—P2	122.2 (2)
C7—C8—H8	119.8	C46—C41—P2	118.5 (2)
C8—C9—C10	120.3 (5)	C43—C42—C41	119.8 (3)
C8—C9—H9	119.9	C43—C42—H42	120.1
C10—C9—H9	119.9	C41—C42—H42	120.1
C9—C10—C5	120.3 (4)	C44—C43—C42	120.2 (4)
C9—C10—H10	119.9	C44—C43—H43	119.9
C5—C10—H10	119.9	C42—C43—H43	119.9
C12—C11—C16	119.2 (3)	C43—C44—C45	120.3 (4)
C12—C11—P1	121.7 (3)	C43—C44—H44	119.8
C16—C11—P1	119.0 (3)	C45—C44—H44	119.8
C13—C12—C11	119.6 (4)	C44—C45—C46	120.5 (4)
C13—C12—H12	120.2	C44—C45—H45	119.8
C11—C12—H12	120.2	C46—C45—H45	119.8
C14—C13—C12	121.2 (4)	C45—C46—C41	119.7 (3)
C14—C13—H13	119.4	C45—C46—H46	120.2
C12—C13—H13	119.4	C41—C46—H46	120.2
C13—C14—C15	119.7 (4)	C48—C47—C52	119.4 (3)
C13—C14—H14	120.2	C48—C47—P2	123.8 (2)
C15—C14—H14	120.2	C52—C47—P2	116.7 (2)
C14—C15—C16	120.1 (4)	C49—C48—C47	119.7 (3)
C14—C15—H15	119.9	C49—C48—H48	120.2
C16—C15—H15	119.9	C47—C48—H48	120.2
C15—C16—C11	120.2 (4)	C50—C49—C48	120.7 (3)
C15—C16—H16	119.9	C50—C49—H49	119.7
C11—C16—H16	119.9	C48—C49—H49	119.7
C22—C17—C18	119.6 (3)	C49—C50—C51	120.1 (3)
C22—C17—P1	121.8 (3)	C49—C50—H50	120
C18—C17—P1	118.5 (3)	C51—C50—H50	120
C19—C18—C17	119.1 (4)	C52—C51—C50	119.8 (3)
C19—C18—H18	120.5	C52—C51—H51	120.1
C17—C18—H18	120.5	C50—C51—H51	120.1
C20—C19—C18	120.7 (4)	C51—C52—C47	120.3 (3)
C20—C19—H19	119.6	C51—C52—H52	119.9
C18—C19—H19	119.6	C47—C52—H52	119.9

S2—Zn—S1—C1	1.16 (11)	C23—P1—C17—C18	−165.3 (3)
S4—Zn—S1—C1	−130.18 (11)	C11—P1—C17—C18	−44.5 (3)
S5—Zn—S1—C1	124.91 (11)	C22—C17—C18—C19	0.3 (6)
S1—Zn—S2—C1	−1.17 (11)	P1—C17—C18—C19	−178.6 (3)
S4—Zn—S2—C1	134.03 (11)	C17—C18—C19—C20	−0.5 (6)
S5—Zn—S2—C1	−123.66 (11)	C18—C19—C20—C21	0.3 (7)
S2—Zn—S4—C3	123.96 (10)	C19—C20—C21—C22	0.2 (8)
S1—Zn—S4—C3	−125.12 (10)	C18—C17—C22—C21	0.2 (6)
S5—Zn—S4—C3	−0.72 (10)	P1—C17—C22—C21	179.1 (4)
S2—Zn—S5—C3	−127.47 (10)	C20—C21—C22—C17	−0.4 (8)
S1—Zn—S5—C3	133.86 (10)	C17—P1—C23—C28	73.9 (3)
S4—Zn—S5—C3	0.72 (10)	C5—P1—C23—C28	−166.0 (3)
O1—S3—N1—C1	−65.2 (3)	C11—P1—C23—C28	−43.8 (3)
O2—S3—N1—C1	74.6 (3)	C17—P1—C23—C24	−103.9 (3)
C2—S3—N1—C1	−175.9 (3)	C5—P1—C23—C24	16.1 (3)
O3—S6—N2—C3	70.0 (3)	C11—P1—C23—C24	138.3 (3)
O4—S6—N2—C3	−70.8 (3)	C28—C23—C24—C25	1.0 (6)
C4—S6—N2—C3	−180.0 (3)	P1—C23—C24—C25	178.9 (3)
S3—N1—C1—S2	−175.78 (19)	C23—C24—C25—C26	−0.9 (7)
S3—N1—C1—S1	4.8 (5)	C24—C25—C26—C27	−0.1 (6)
Zn—S2—C1—N1	−177.8 (3)	C25—C26—C27—C28	0.9 (6)
Zn—S2—C1—S1	1.71 (16)	C24—C23—C28—C27	−0.2 (5)
Zn—S1—C1—N1	177.7 (3)	P1—C23—C28—C27	−178.1 (3)
Zn—S1—C1—S2	−1.71 (16)	C26—C27—C28—C23	−0.7 (6)
O1—S3—C2—F2	−176.8 (3)	C41—P2—C29—C30	129.3 (2)
O2—S3—C2—F2	59.5 (3)	C35—P2—C29—C30	9.2 (3)
N1—S3—C2—F2	−57.3 (3)	C47—P2—C29—C30	−112.9 (2)
O1—S3—C2—F1	−55.3 (3)	C41—P2—C29—C34	−54.8 (3)
O2—S3—C2—F1	−179.0 (3)	C35—P2—C29—C34	−175.0 (2)
N1—S3—C2—F1	64.2 (3)	C47—P2—C29—C34	63.0 (3)
O1—S3—C2—F3	63.6 (4)	C34—C29—C30—C31	−2.3 (4)
O2—S3—C2—F3	−60.1 (4)	P2—C29—C30—C31	173.6 (2)
N1—S3—C2—F3	−176.9 (3)	C29—C30—C31—C32	1.1 (5)
S6—N2—C3—S5	−0.1 (4)	C30—C31—C32—C33	0.6 (5)
S6—N2—C3—S4	179.99 (16)	C31—C32—C33—C34	−1.2 (5)
Zn—S5—C3—N2	179.0 (3)	C32—C33—C34—C29	0.0 (5)
Zn—S5—C3—S4	−1.06 (15)	C30—C29—C34—C33	1.7 (5)
Zn—S4—C3—N2	−179.0 (2)	P2—C29—C34—C33	−174.2 (2)
Zn—S4—C3—S5	1.07 (15)	C41—P2—C35—C36	−10.6 (3)
O3—S6—C4—F4	178.5 (3)	C47—P2—C35—C36	−129.2 (2)
O4—S6—C4—F4	−57.0 (3)	C29—P2—C35—C36	110.5 (3)
N2—S6—C4—F4	61.0 (3)	C41—P2—C35—C40	172.0 (2)
O3—S6—C4—F6	57.3 (4)	C47—P2—C35—C40	53.3 (3)
O4—S6—C4—F6	−178.3 (3)	C29—P2—C35—C40	−67.0 (3)
N2—S6—C4—F6	−60.3 (4)	C40—C35—C36—C37	−0.5 (5)
O3—S6—C4—F5	−62.0 (4)	P2—C35—C36—C37	−178.0 (3)
O4—S6—C4—F5	62.5 (4)	C35—C36—C37—C38	−1.1 (5)
N2—S6—C4—F5	−179.5 (3)	C36—C37—C38—C39	1.9 (6)
C17—P1—C5—C6	174.8 (4)	C37—C38—C39—C40	−1.1 (6)
C23—P1—C5—C6	55.3 (4)	C38—C39—C40—C35	−0.6 (5)
C11—P1—C5—C6	−67.4 (4)	C36—C35—C40—C39	1.3 (5)
C17—P1—C5—C10	−2.4 (4)	P2—C35—C40—C39	178.8 (2)
C23—P1—C5—C10	−122.0 (3)	C35—P2—C41—C42	102.1 (3)
C11—P1—C5—C10	115.4 (3)	C47—P2—C41—C42	−136.1 (3)
C10—C5—C6—C7	0.8 (8)	C29—P2—C41—C42	−16.8 (3)
P1—C5—C6—C7	−176.5 (5)	C35—P2—C41—C46	−78.2 (3)
C5—C6—C7—C8	0.9 (10)	C47—P2—C41—C46	43.6 (3)
C6—C7—C8—C9	−2.9 (11)	C29—P2—C41—C46	162.9 (3)
C7—C8—C9—C10	3.1 (10)	C46—C41—C42—C43	0.2 (5)
C8—C9—C10—C5	−1.3 (8)	P2—C41—C42—C43	179.9 (3)
C6—C5—C10—C9	−0.7 (7)	C41—C42—C43—C44	1.1 (6)
P1—C5—C10—C9	176.6 (4)	C42—C43—C44—C45	−0.7 (7)
C17—P1—C11—C12	131.2 (3)	C43—C44—C45—C46	−1.1 (7)
C5—P1—C11—C12	11.2 (3)	C44—C45—C46—C41	2.5 (6)
C23—P1—C11—C12	−109.4 (3)	C42—C41—C46—C45	−2.0 (5)
C17—P1—C11—C16	−45.4 (3)	P2—C41—C46—C45	178.3 (3)
C5—P1—C11—C16	−165.4 (3)	C41—P2—C47—C48	−124.1 (3)
C23—P1—C11—C16	74.1 (3)	C35—P2—C47—C48	−3.9 (3)
C16—C11—C12—C13	0.3 (5)	C29—P2—C47—C48	115.4 (3)
P1—C11—C12—C13	−176.2 (3)	C41—P2—C47—C52	55.2 (3)
C11—C12—C13—C14	−0.3 (6)	C35—P2—C47—C52	175.4 (3)
C12—C13—C14—C15	−0.4 (6)	C29—P2—C47—C52	−65.3 (3)
C13—C14—C15—C16	1.2 (7)	C52—C47—C48—C49	0.7 (5)
C14—C15—C16—C11	−1.2 (7)	P2—C47—C48—C49	179.9 (3)
C12—C11—C16—C15	0.4 (5)	C47—C48—C49—C50	0.6 (5)
P1—C11—C16—C15	177.1 (3)	C48—C49—C50—C51	−0.9 (6)
C5—P1—C17—C22	−103.0 (3)	C49—C50—C51—C52	−0.1 (6)
C23—P1—C17—C22	15.8 (4)	C50—C51—C52—C47	1.4 (6)
C11—P1—C17—C22	136.6 (3)	C48—C47—C52—C51	−1.7 (5)
C5—P1—C17—C18	75.9 (3)	P2—C47—C52—C51	179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1	0.93	2.68	3.424 (4)	138
C31—H31···O4	0.93	2.62	3.470 (4)	153
C33—H33···O2ⁱ	0.93	2.47	3.283 (4)	145

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	(C₂₄H₂₀P)₂[Zn(C₂F₃NO₂S₃)₂]
M_r	1190.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.8461 (1), 29.1869 (5), 20.6963 (3)
β (°)	93.578 (1)
V (Å³)	5333.17 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.42 × 0.18 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.758, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	57739, 11977, 8307
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.169, 1.05
No. of reflections	11977
No. of parameters	646
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.18, −1.66

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn—S1	2.3346 (10)	Zn—S4	2.3376 (9)
Zn—S2	2.3340 (10)	Zn—S5	2.3566 (10)

S2—Zn—S1	77.84 (3)	S4—Zn—S5	77.63 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1	0.93	2.68	3.424 (4)	137.8
C31—H31···O4	0.93	2.62	3.470 (4)	152.7
C33—H33···O2ⁱ	0.93	2.47	3.283 (4)	145.4

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank Professor Dr Javier Ellena of the IFSC, USP, Brazil, for the X-ray data collection. This work was supported financially by FAPEMIG and CAPES.

References

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