Bis[(acetato-κ²O,O′)bis­(4,4′-dimeth­yl-2,2′-bipyrid­yl-κ²N,N′)zinc(II)] trithion­ate penta­hydrate

The title ionic zinc–acetate complex, [Zn(C₂H₃O₂)(C₁₂H₁₂N₂)₂]₂(S₃O₆)·5H₂O, contains a ZnN₄O₂ nucleus provided by the three bidentate ligands acting in a chelating mode. The trithio­nate unit, in turn, acts as an isolated charge-balancing counter-ion. The structure has a three-dimensional assembly achieved through three different inter­action types, viz. Coulomb, hydrogen bonding and π–π. The trithio­nate group and one of the solvent water mol­ecules are disordered around inversion centers.

S1. Comment

Many synthetic routes are available for the preparation of polythionate anions (O₃S_nO₃²⁻, 2 < = n), even though mechanistic details are frequently obscured due to the numerous simultaneous and competing redox, catenation and/or disproportionation reactions that may occur. We have recently commented (Díaz de Vivar et al., 2004, 2005) on the feasibility of producing novel thiosulfate complexes of group XII metals, complexes that are difficult to obtain by conventional methods, through the decomposition of less common sulfur oxoanions, such as dithionite and/or pyrosulfite. One of the reported ways to obtain trithionate (O₃S₃O₃²⁻) is the reaction between aqueous thiosulfate and sulfur dioxide (Remy, 1956), but structures containing the anion are rare, as a survey in the current structural databases reveals. In the November 2004 update of the Cambridge Structural Database (CSD; Allen, 2002), out of a total of 132 structures containing polythionates of diverse chain lengths (2 < = n < = 6), the most common species by far were dithionates (n = 2), with 112 entries; only one trithionate, viz. cis-amminebromobis(ethylenediamine)cobalt(III) trithionate, hereafter (II) (Chun et al., 2000), was found. Similarly scarce was the outcome of a search of the 2004 release of the ICSD (2001), with only one fully reported structure, dipotassium trithionate, hereafter (III) (Christidis & Rentzeperis, 1985). We report here only the third reported structure containing a trithionate anion, viz. [Zn(dmbpy)₂(acet)⁺]₂(S₃O₆²⁻)·5H₂O (dmbpy is 4,4'-dimethyl-2,2'-bipyridyl and acet is acetate), (I), which was prepared serendipitously.

Fig. 1 shows an ellipsoid diagram of (I). The structure is ionic, and consists of monomeric [Zn(dmbpy)₂(acet)]⁺ cations, balanced by S₃O₆²⁻ anions in a 2:1 ratio, and two and a half independent solvent water molecules.

The six-coordinate Zn cation binds to three chelating ligands and, as a result of the angular restraints in force, the ZnN₄O₂ polyhedron appears highly distorted. However, the mean values of the Zn—N and Zn—O distances [2.110 (14) and 2.22 (3) Å, respectively] depart only slightly from the corresponding means in similar coordination spheres with no geometric restraints [2.14 (8) and 2.19 (15) Å, respectively, for 264 cases found in the CSD].

In spite of its being disordered about an inversion centre, the trithionate ion could be adequately refined. When compared with the only other two reported structures containing this (counter) anion no significant differences could be detected, as the following values given in a (I)/(II)/(III) sequence confirm: <S—O>: 1.43 (3)/1.443 (5)/1.45 (2) Å; <S—S>: 2.10 (4)/2.102 (14)/2.08 (2) Å; S—S—S angle: 107.1 (1)/107.1 (1)/106.4 (1)°. It is noteworthy that the anion shows the same characteristic feature frequently observed in many peroxodisulfates (Harvey, Baggio, Garland, Burton & Baggio, 2001; Harvey, Baggio, Garland & Baggio, 2001). The S—S—S—O groups that are more nearly planar (with a torsion angle of 155–180°) are those that present a terminal S—S—O angle some 10° smaller than the other two S—S—O angles involving the remaining terminal O atoms (Table 1).

A feature in the structure is the three-dimensional assembly achieved through three different interaction types, viz. Coulomb, hydrogen bonding and π–π. Fig. 2 shows a projection on to the (111) plane, where two distinct types of one-dimensional array are apparent, viz. a cationic chain formed by the juxtaposition of π-bonded [Zn(dmbpy)₂(acet)]⁺ monomers, and an anionic one determined by the hydrogen-bonded solvent water molecules and trithionate anions. The former chain in built up around the inversion centers at (0,1/2,1/2) and (1/2,1/2,0), which through the duplication of moieties dmbpy(A) and dmbpy(B), respectively, leads to two symmetry-related pairs of aromatic rings at a graphitic distance to each other (about 3.5 Å; see Table 3). For clarity these chains have been represented in Fig. 2 with consecutive monomers drawn in contrasting line widths. The anionic arrays evolve between these cationic chains as wavy tightly woven strips, where the water molecules cluster around each other and act as connectors between trithionate anions. Details of the hydrogen-bonding scheme are presented in Table 2.

The interaction between the two different types of chains is achieved through the omnipresent Colulomb forces, as well as via a hydrogen bond connecting atom O3W, on the anionic side, with an acetate O atom on the cationic side. The final ensemble, depicted in Fig. 2, is a two-dimensional array some 7 Å in width (the diameter of the rather `globular"'cationic unit). These planes stack along [111], but with a lateral shift of one `interchain spacing' perpendicular to the chain's direction (Fig. 3), thus confronting positively charged columns in one sheet with negative ones in the neighboring sheet, and providing for stabilization of the three-dimensional structure.

S2. Experimental

The compound was obtained by dissolving the aromatic amine in ethanol (96%) and allowing this solution to diffuse slowly into an aqueous solution of [Zn(C₂H₃O₂)₂]·2H₂O and K₂S₂O₅ (molar ratio 1:1:2). After two months, crystals of a size suitable for X-ray analysis had developed.

S3. Refinement

H atoms attached to C atoms were placed at calculated positions (C—H_aromatic = 0.93 Å and C—H_methyl = 0.96 Å) and allowed to ride. Methyl groups were allowed to rotate around the C—C axis. H atoms of water molecules were located from difference Fourier syntheses and refined with restrained O—H distances [0.85 (2) Å]. All H atoms were assigned U_iso(H) values of xU_eq(host), with x = 1.2 for aromatic and water H atoms, and x = 1.5 for methyl H atoms. The trithionate group and one of the solvent water molecules (O1W) are disordered around inversion centers, each with an occupancy of 0.5.

Computing details

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick,1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. An XP diagram (Sheldrick, 1994) of (I), with 50% probability displacement ellipsoids. Only one of the two disordered moieties of the trithionate group is shown, for clarity.
	Fig. 2. A projection of the structure on to the (111) plane. See text and Table 3 for details.
	Fig. 3. A projection of the structure down [101], the chain direction, at 90° from the view in Fig. 2. Note the alternation of cationic (bold lines) and anionic (light lines) chains.

Bis[(acetato-κ²O,O')bis(4,4'-dimethyl-2,2'-bipyridyl-κ²N,N')zinc(II)] trithionate pentahydrate

Crystal data

[Zn(C12H12N2)2(C2H3O2)]2(S3O6)·5H2O	Z = 1
Mr = 1268.04	F(000) = 660
Triclinic, P1	Dx = 1.460 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7456 (11) Å	Cell parameters from 1232 reflections
b = 11.2370 (12) Å	θ = 4.0–23.5°
c = 14.5676 (16) Å	µ = 1.01 mm^−1
α = 73.043 (2)°	T = 295 K
β = 70.943 (2)°	Plate, colorless
γ = 85.260 (2)°	0.25 × 0.12 × 0.08 mm
V = 1442.2 (3) Å^3

Data collection

Bruker CCD area detector diffractometer	6282 independent reflections
Radiation source: fine-focus sealed tube	4707 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 28.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→12
Tmin = 0.84, Tmax = 0.92	k = −14→14
10738 measured reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0784P)^2 + 0.0235P] where P = (Fo^2 + 2Fc^2)/3
6282 reflections	(Δ/σ)max = 0.008
412 parameters	Δρmax = 0.62 e Å^−3
10 restraints	Δρmin = −0.34 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.23008 (4)	0.51916 (3)	0.23849 (2)	0.04350 (14)
O13	0.1061 (3)	0.4991 (2)	0.14229 (18)	0.0641 (6)
O23	0.0446 (3)	0.6448 (2)	0.21810 (18)	0.0620 (6)
C13	0.0267 (4)	0.5872 (4)	0.1612 (3)	0.0582 (9)
C23	−0.0929 (5)	0.6258 (5)	0.1153 (3)	0.0864 (13)
H23A	−0.0986	0.5692	0.0784	0.130*
H23B	−0.0733	0.7084	0.0702	0.130*
H23C	−0.1835	0.6244	0.1680	0.130*
N11	0.2678 (3)	0.5547 (2)	0.36138 (18)	0.0406 (5)
N21	0.1033 (3)	0.3789 (2)	0.36288 (18)	0.0435 (6)
C11	0.3574 (3)	0.6436 (3)	0.3555 (2)	0.0495 (8)
H11	0.4010	0.6995	0.2928	0.059*
C21	0.3869 (4)	0.6548 (3)	0.4383 (3)	0.0550 (8)
H21	0.4499	0.7172	0.4310	0.066*
C31	0.3237 (4)	0.5741 (3)	0.5323 (2)	0.0497 (8)
C41	0.2338 (3)	0.4819 (3)	0.5380 (2)	0.0454 (7)
H41	0.1904	0.4247	0.6000	0.055*
C51	0.2076 (3)	0.4738 (3)	0.4523 (2)	0.0382 (6)
C61	0.1108 (3)	0.3770 (3)	0.4535 (2)	0.0395 (6)
C71	0.0362 (3)	0.2887 (3)	0.5396 (2)	0.0469 (7)
H71	0.0422	0.2896	0.6018	0.056*
C81	−0.0484 (3)	0.1976 (3)	0.5351 (3)	0.0521 (8)
C91	−0.0530 (4)	0.2014 (3)	0.4403 (3)	0.0560 (8)
H91	−0.1074	0.1423	0.4333	0.067*
C101	0.0222 (3)	0.2917 (3)	0.3572 (3)	0.0515 (8)
H10A	0.0173	0.2930	0.2942	0.062*
C111	0.3514 (4)	0.5872 (4)	0.6239 (3)	0.0699 (11)
H11B	0.4464	0.6227	0.6048	0.105*
H11C	0.3457	0.5067	0.6718	0.105*
H11D	0.2799	0.6405	0.6541	0.105*
C121	−0.1268 (4)	0.0989 (4)	0.6282 (3)	0.0739 (11)
H12A	−0.2076	0.0676	0.6177	0.111*
H12B	−0.1615	0.1335	0.6845	0.111*
H12C	−0.0618	0.0322	0.6421	0.111*
N12	0.3823 (3)	0.6472 (2)	0.11826 (18)	0.0430 (6)
N22	0.4146 (3)	0.4092 (2)	0.20311 (17)	0.0420 (6)
C12	0.3593 (4)	0.7660 (3)	0.0755 (2)	0.0531 (8)
H12	0.2694	0.7993	0.1016	0.064*
C22	0.4607 (4)	0.8414 (3)	−0.0045 (3)	0.0574 (9)
H22	0.4389	0.9238	−0.0313	0.069*
C32	0.5934 (4)	0.7961 (3)	−0.0451 (2)	0.0563 (9)
C42	0.6191 (3)	0.6715 (3)	−0.0023 (2)	0.0475 (7)
H42	0.7082	0.6367	−0.0282	0.057*
C52	0.5126 (3)	0.6001 (3)	0.0784 (2)	0.0416 (7)
C62	0.5316 (3)	0.4669 (3)	0.1289 (2)	0.0409 (7)
C72	0.6617 (4)	0.4064 (3)	0.1029 (2)	0.0498 (8)
H72	0.7403	0.4472	0.0493	0.060*
C82	0.6747 (4)	0.2840 (3)	0.1572 (3)	0.0574 (9)
C92	0.5534 (4)	0.2274 (3)	0.2342 (3)	0.0576 (9)
H92	0.5579	0.1456	0.2722	0.069*
C102	0.4275 (4)	0.2909 (3)	0.2545 (2)	0.0489 (7)
H10B	0.3467	0.2506	0.3063	0.059*
C112	0.7093 (5)	0.8763 (4)	−0.1309 (3)	0.0798 (12)
H11E	0.6652	0.9384	−0.1731	0.120*
H11F	0.7715	0.8258	−0.1701	0.120*
H11G	0.7653	0.9161	−0.1047	0.120*
C122	0.8173 (5)	0.2178 (5)	0.1338 (4)	0.0927 (15)
H12E	0.8186	0.1500	0.1917	0.139*
H12F	0.8953	0.2749	0.1176	0.139*
H12G	0.8290	0.1862	0.0772	0.139*
S1	−0.6574 (10)	1.0548 (8)	0.5553 (7)	0.0717 (16)	0.50
S2	−0.4254 (2)	1.0526 (2)	0.50873 (18)	0.0716 (6)	0.50
S3	−0.3601 (8)	0.9218 (6)	0.4301 (6)	0.0549 (11)	0.50
O1	−0.6995 (7)	1.1025 (8)	0.4680 (5)	0.109 (3)	0.50
O2	−0.6808 (8)	1.1295 (10)	0.6261 (7)	0.132 (3)	0.50
O3	−0.7027 (7)	0.9312 (6)	0.6047 (5)	0.100 (2)	0.50
O4	−0.4498 (7)	0.9329 (5)	0.3663 (4)	0.0796 (16)	0.50
O5	−0.2118 (6)	0.9681 (6)	0.3697 (4)	0.0812 (16)	0.50
O6	−0.3677 (6)	0.8033 (5)	0.4996 (5)	0.0722 (15)	0.50
O1W	0.1226 (9)	1.0288 (9)	−0.0096 (5)	0.117 (2)	0.50
H1W1	0.081 (4)	1.049 (11)	−0.055 (2)	0.140*	0.50
H1W2	0.072 (7)	0.984 (10)	0.048 (3)	0.140*	0.50
O2W	0.4026 (6)	1.1220 (6)	−0.1859 (4)	0.1627 (19)
H2W1	0.420 (8)	1.117 (8)	−0.247 (2)	0.195*
H2W2	0.324 (5)	1.084 (7)	−0.143 (4)	0.195*
O3W	−0.0581 (6)	0.8944 (4)	0.1887 (3)	0.1218 (14)
H3W1	−0.017 (6)	0.824 (3)	0.193 (4)	0.146*
H3W2	−0.122 (5)	0.901 (5)	0.244 (2)	0.146*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0450 (2)	0.0490 (2)	0.0343 (2)	−0.00609 (15)	−0.00921 (15)	−0.01040 (16)
O13	0.0641 (16)	0.0697 (17)	0.0547 (14)	−0.0046 (13)	−0.0167 (12)	−0.0125 (13)
O23	0.0566 (15)	0.0740 (17)	0.0552 (14)	0.0015 (12)	−0.0200 (12)	−0.0154 (13)
C13	0.051 (2)	0.068 (2)	0.0476 (19)	−0.0120 (18)	−0.0146 (16)	−0.0015 (18)
C23	0.073 (3)	0.105 (4)	0.090 (3)	−0.006 (2)	−0.047 (2)	−0.015 (3)
N11	0.0405 (13)	0.0407 (13)	0.0392 (13)	−0.0051 (10)	−0.0083 (10)	−0.0126 (11)
N21	0.0419 (14)	0.0476 (15)	0.0396 (13)	−0.0075 (11)	−0.0080 (11)	−0.0138 (11)
C11	0.0553 (19)	0.0426 (17)	0.0491 (18)	−0.0081 (14)	−0.0109 (15)	−0.0144 (14)
C21	0.060 (2)	0.0494 (19)	0.064 (2)	−0.0089 (16)	−0.0209 (17)	−0.0237 (17)
C31	0.0547 (19)	0.0518 (19)	0.0497 (18)	0.0027 (15)	−0.0190 (15)	−0.0227 (16)
C41	0.0513 (18)	0.0488 (18)	0.0367 (15)	0.0007 (14)	−0.0138 (13)	−0.0129 (13)
C51	0.0379 (15)	0.0367 (15)	0.0382 (14)	−0.0008 (12)	−0.0072 (12)	−0.0130 (12)
C61	0.0372 (15)	0.0406 (16)	0.0394 (15)	0.0009 (12)	−0.0095 (12)	−0.0125 (13)
C71	0.0483 (18)	0.0448 (17)	0.0440 (16)	0.0009 (14)	−0.0140 (14)	−0.0080 (14)
C81	0.0476 (18)	0.0416 (17)	0.058 (2)	−0.0021 (14)	−0.0092 (15)	−0.0081 (15)
C91	0.0488 (19)	0.0514 (19)	0.068 (2)	−0.0123 (15)	−0.0149 (17)	−0.0182 (17)
C101	0.0447 (17)	0.062 (2)	0.0520 (18)	−0.0106 (15)	−0.0112 (14)	−0.0242 (16)
C111	0.084 (3)	0.081 (3)	0.060 (2)	−0.006 (2)	−0.033 (2)	−0.029 (2)
C121	0.076 (3)	0.054 (2)	0.072 (3)	−0.0218 (19)	−0.013 (2)	0.0058 (19)
N12	0.0486 (15)	0.0409 (14)	0.0359 (12)	−0.0046 (11)	−0.0094 (11)	−0.0085 (11)
N22	0.0482 (14)	0.0421 (14)	0.0347 (12)	−0.0029 (11)	−0.0122 (11)	−0.0095 (11)
C12	0.061 (2)	0.0464 (19)	0.0486 (18)	−0.0023 (15)	−0.0142 (16)	−0.0106 (15)
C22	0.076 (2)	0.0404 (18)	0.053 (2)	−0.0072 (17)	−0.0212 (18)	−0.0065 (15)
C32	0.070 (2)	0.055 (2)	0.0441 (17)	−0.0211 (17)	−0.0176 (16)	−0.0092 (16)
C42	0.0482 (18)	0.0550 (19)	0.0385 (15)	−0.0104 (14)	−0.0098 (13)	−0.0135 (14)
C52	0.0474 (17)	0.0474 (17)	0.0331 (14)	−0.0087 (13)	−0.0139 (13)	−0.0119 (13)
C62	0.0495 (17)	0.0445 (17)	0.0324 (14)	−0.0026 (13)	−0.0148 (13)	−0.0133 (13)
C72	0.0491 (18)	0.056 (2)	0.0450 (17)	−0.0001 (15)	−0.0119 (14)	−0.0186 (15)
C82	0.063 (2)	0.060 (2)	0.054 (2)	0.0106 (17)	−0.0216 (17)	−0.0233 (17)
C92	0.078 (2)	0.0460 (19)	0.0501 (19)	0.0077 (17)	−0.0259 (18)	−0.0115 (16)
C102	0.060 (2)	0.0456 (18)	0.0399 (16)	−0.0024 (15)	−0.0156 (14)	−0.0092 (14)
C112	0.087 (3)	0.069 (3)	0.064 (2)	−0.031 (2)	−0.005 (2)	−0.002 (2)
C122	0.077 (3)	0.088 (3)	0.097 (3)	0.035 (3)	−0.022 (3)	−0.016 (3)
S1	0.055 (2)	0.074 (4)	0.080 (3)	−0.008 (2)	−0.0275 (17)	−0.004 (2)
S2	0.0518 (10)	0.0794 (14)	0.0959 (15)	−0.0100 (9)	−0.0186 (10)	−0.0452 (12)
S3	0.048 (2)	0.0442 (19)	0.064 (2)	−0.0024 (14)	−0.0156 (16)	−0.0055 (14)
O1	0.077 (4)	0.148 (6)	0.068 (4)	0.029 (4)	−0.025 (3)	0.013 (4)
O2	0.070 (5)	0.191 (9)	0.165 (8)	0.007 (5)	−0.011 (5)	−0.127 (8)
O3	0.084 (4)	0.088 (5)	0.117 (5)	−0.033 (4)	−0.053 (4)	0.018 (4)
O4	0.115 (5)	0.063 (3)	0.078 (4)	−0.012 (3)	−0.053 (4)	−0.016 (3)
O5	0.067 (4)	0.081 (4)	0.081 (4)	−0.016 (3)	−0.002 (3)	−0.020 (3)
O6	0.072 (3)	0.050 (3)	0.085 (4)	−0.006 (3)	−0.030 (3)	0.002 (3)
O1W	0.140 (7)	0.133 (7)	0.080 (5)	0.001 (5)	−0.043 (5)	−0.025 (5)
O2W	0.174 (5)	0.174 (5)	0.140 (4)	−0.042 (4)	−0.064 (4)	−0.016 (4)
O3W	0.180 (4)	0.100 (3)	0.084 (2)	0.038 (3)	−0.046 (3)	−0.028 (2)

Geometric parameters (Å, º)

Zn1—N11	2.091 (2)	N12—C52	1.348 (4)
Zn1—N22	2.104 (2)	N22—C102	1.341 (4)
Zn1—N21	2.119 (2)	N22—C62	1.341 (4)
Zn1—N12	2.127 (2)	C12—C22	1.365 (5)
Zn1—O13	2.193 (2)	C12—H12	0.93
Zn1—O23	2.243 (2)	C22—C32	1.360 (5)
O13—C13	1.244 (4)	C22—H22	0.93
O23—C13	1.250 (4)	C32—C42	1.395 (5)
C13—C23	1.500 (5)	C32—C112	1.496 (5)
C23—H23A	0.96	C42—C52	1.376 (4)
C23—H23B	0.96	C42—H42	0.93
C23—H23C	0.96	C52—C62	1.488 (4)
N11—C11	1.346 (4)	C62—C72	1.382 (4)
N11—C51	1.343 (4)	C72—C82	1.392 (5)
N21—C61	1.339 (4)	C72—H72	0.93
N21—C101	1.345 (4)	C82—C92	1.379 (5)
C11—C21	1.370 (4)	C82—C122	1.507 (5)
C11—H11	0.93	C92—C102	1.358 (5)
C21—C31	1.376 (5)	C92—H92	0.93
C21—H21	0.93	C102—H10B	0.93
C31—C41	1.379 (4)	C112—H11E	0.96
C31—C111	1.494 (4)	C112—H11F	0.96
C41—C51	1.383 (4)	C112—H11G	0.96
C41—H41	0.93	C122—H12E	0.96
C51—C61	1.491 (4)	C122—H12F	0.96
C61—C71	1.372 (4)	C122—H12G	0.96
C71—C81	1.395 (4)	S1—O3	1.397 (10)
C71—H71	0.93	S1—O1	1.407 (11)
C81—C91	1.384 (5)	S1—O2	1.463 (9)
C81—C121	1.497 (5)	S1—S2	2.138 (9)
C91—C101	1.364 (5)	S2—S3	2.056 (7)
C91—H91	0.93	S3—O6	1.409 (9)
C101—H10A	0.93	S3—O4	1.445 (9)
C111—H11B	0.96	S3—O5	1.470 (10)
C111—H11C	0.96	O1W—H1W1	0.85 (4)
C111—H11D	0.96	O1W—H1W2	0.85 (4)
C121—H12A	0.96	O2W—H2W1	0.86 (5)
C121—H12B	0.96	O2W—H2W2	0.86 (4)
C121—H12C	0.96	O3W—H3W1	0.85 (4)
N12—C12	1.332 (4)	O3W—H3W2	0.86 (4)
N11—Zn1—N22	95.87 (9)	C31—C111—H11D	109.5
N11—Zn1—N21	77.56 (9)	H11B—C111—H11D	109.5
N22—Zn1—N21	95.93 (9)	H11C—C111—H11D	109.5
N11—Zn1—N12	99.29 (9)	C81—C121—H12A	109.5
N22—Zn1—N12	77.21 (9)	C81—C121—H12B	109.5
N21—Zn1—N12	172.22 (10)	H12A—C121—H12B	109.5
N11—Zn1—O13	157.81 (10)	C81—C121—H12C	109.5
N22—Zn1—O13	104.59 (10)	H12A—C121—H12C	109.5
N21—Zn1—O13	91.67 (9)	H12B—C121—H12C	109.5
N12—Zn1—O13	93.61 (9)	C12—N12—C52	117.3 (3)
N11—Zn1—O23	102.80 (9)	C12—N12—Zn1	126.9 (2)
N22—Zn1—O23	159.58 (9)	C52—N12—Zn1	115.71 (19)
N21—Zn1—O23	96.10 (9)	C102—N22—C62	118.3 (3)
N12—Zn1—O23	91.53 (9)	C102—N22—Zn1	125.1 (2)
O13—Zn1—O23	58.62 (10)	C62—N22—Zn1	116.32 (19)
N11—Zn1—C13	131.19 (12)	N12—C12—C22	123.6 (3)
N22—Zn1—C13	132.94 (11)	N12—C12—H12	118.2
N21—Zn1—C13	94.38 (10)	C22—C12—H12	118.2
N12—Zn1—C13	93.01 (10)	C32—C22—C12	120.0 (3)
O13—Zn1—C13	29.24 (10)	C32—C22—H22	120.0
O23—Zn1—C13	29.38 (10)	C12—C22—H22	120.0
C13—O13—Zn1	91.3 (2)	C22—C32—C42	117.4 (3)
C13—O23—Zn1	88.9 (2)	C22—C32—C112	121.8 (3)
O13—C13—O23	121.2 (3)	C42—C32—C112	120.8 (3)
O13—C13—C23	119.9 (4)	C52—C42—C32	119.9 (3)
O23—C13—C23	119.0 (4)	C52—C42—H42	120.0
O13—C13—Zn1	59.42 (19)	C32—C42—H42	120.0
O23—C13—Zn1	61.74 (19)	N12—C52—C42	121.8 (3)
C23—C13—Zn1	179.3 (3)	N12—C52—C62	114.9 (2)
C13—C23—H23A	109.5	C42—C52—C62	123.3 (3)
C13—C23—H23B	109.5	N22—C62—C72	121.6 (3)
H23A—C23—H23B	109.5	N22—C62—C52	115.7 (3)
C13—C23—H23C	109.5	C72—C62—C52	122.6 (3)
H23A—C23—H23C	109.5	C62—C72—C82	119.7 (3)
H23B—C23—H23C	109.5	C62—C72—H72	120.2
C11—N11—C51	117.9 (3)	C82—C72—H72	120.2
C11—N11—Zn1	125.6 (2)	C92—C82—C72	117.5 (3)
C51—N11—Zn1	116.20 (19)	C92—C82—C122	121.7 (3)
C61—N21—C101	118.8 (3)	C72—C82—C122	120.8 (3)
C61—N21—Zn1	115.47 (19)	C102—C92—C82	120.1 (3)
C101—N21—Zn1	125.6 (2)	C102—C92—H92	120.0
N11—C11—C21	122.4 (3)	C82—C92—H92	120.0
N11—C11—H11	118.8	N22—C102—C92	122.7 (3)
C21—C11—H11	118.8	N22—C102—H10B	118.6
C11—C21—C31	120.3 (3)	C92—C102—H10B	118.6
C11—C21—H21	119.8	C32—C112—H11E	109.5
C31—C21—H21	119.8	C32—C112—H11F	109.5
C21—C31—C41	117.2 (3)	H11E—C112—H11F	109.5
C21—C31—C111	121.0 (3)	C32—C112—H11G	109.5
C41—C31—C111	121.8 (3)	H11E—C112—H11G	109.5
C31—C41—C51	120.6 (3)	H11F—C112—H11G	109.5
C31—C41—H41	119.7	C82—C122—H12E	109.5
C51—C41—H41	119.7	C82—C122—H12F	109.5
N11—C51—C41	121.6 (3)	H12E—C122—H12F	109.5
N11—C51—C61	115.2 (2)	C82—C122—H12G	109.5
C41—C51—C61	123.2 (3)	H12E—C122—H12G	109.5
N21—C61—C71	121.0 (3)	H12F—C122—H12G	109.5
N21—C61—C51	115.3 (2)	O3—S1—O1	112.0 (6)
C71—C61—C51	123.7 (3)	O3—S1—O2	112.2 (9)
C61—C71—C81	120.9 (3)	O1—S1—O2	119.1 (9)
C61—C71—H71	119.5	O3—S1—S2	105.8 (6)
C81—C71—H71	119.5	O1—S1—S2	107.9 (6)
C91—C81—C71	116.7 (3)	O2—S1—S2	98.1 (4)
C91—C81—C121	121.9 (3)	S3—S2—S1	107.1 (2)
C71—C81—C121	121.3 (3)	O6—S3—O4	113.6 (5)
C101—C91—C81	120.0 (3)	O6—S3—O5	114.5 (6)
C101—C91—H91	120.0	O4—S3—O5	111.0 (6)
C81—C91—H91	120.0	O6—S3—S2	108.9 (5)
N21—C101—C91	122.5 (3)	O4—S3—S2	108.2 (5)
N21—C101—H10A	118.7	O5—S3—S2	99.5 (4)
C91—C101—H10A	118.7	H1W1—O1W—H1W2	116 (6)
C31—C111—H11B	109.5	H2W1—O2W—H2W2	114 (7)
C31—C111—H11C	109.5	H3W1—O3W—H3W2	115 (7)
H11B—C111—H11C	109.5
S1—S2—S3—O6	−82.9 (6)	O3—S1—S2—S3	52.3 (8)
S1—S2—S3—O5	157.0 (3)	O2—S1—S2—S3	168.2 (5)
S1—S2—S3—O4	41.0 (7)	O1—S1—S2—S3	−67.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3W^i	0.85 (4)	1.94 (5)	2.759 (8)	160 (6)
O1W—H1W2···O3W	0.85 (4)	2.03 (5)	2.881 (9)	174 (9)
O2W—H2W1···O4^i	0.86 (5)	1.91 (4)	2.759 (8)	167 (8)
O2W—H2W2···O1W	0.86 (4)	2.24 (4)	3.077 (10)	163 (7)
O3W—H3W1···O23	0.85 (5)	2.02 (4)	2.858 (5)	169 (5)
O3W—H3W2···O5	0.86 (4)	2.09 (5)	2.894 (7)	157 (6)

Symmetry code: (i) −x, −y+2, −z.