A polymeric zinc thio­sulfate complex containing anionic and cationic chains based on tetra­hedral and octa­hedral zinc sites

catena-Poly[[[tetra­aqua­zinc(II)]-μ-4,4′-bipyridine-κ²N:N′] [[μ-thio­sulfato-κ²O:S-bis­[(thio­sulfato-κS)zinc(II)]]-di-μ-4,4′-pyridine-κ⁴N:N′] dihydrate], {[Zn(C₁₀H₈N₂)(H₂O)₄][Zn₂(S₂O₃)₃(C₁₀H₈N₂)₂]·2H₂O}_n, is a polymeric zinc complex built up from thio­sulfate-containing anionic chains, where the Zn atom is tetra­hedrally coordinated, and aqua-containing cationic chains incorporating octa­hedrally coordinated Zn. In each type of chain, the 4,4′-bipyridine units act as spacers, and the chains run along three non-inter­secting almost orthogonal directions in space. The profusion of hydrogen-bond donors (all the H atoms of the water mol­ecules) and acceptors (the thio­sulfate O and S atoms) generates a very complex hydrogen-bonding scheme.

S1. Comment

Sulfur oxoanions (such as sulfate, sulfite and thiosulfate) are usually good ligands towards transition metal cations, and when used as the unique connecting agent their multidentate capacity makes them prone to generating tight and compact three-dimensional structures (e.g. Bear & Mumme, 1970; Bugli & Carré, 1980; Magnusson & Johansson,1981). In order to `open' the framework, it is possible to include bulkier (usually organic) ligands in the synthesis, whose connectivity properties might modify the final structural outcome. Thus, `chelating' N-heterocyclic bases, such as 2,2'-bipyridine and 1,10-phenanthroline, tend to act as `terminal' points in the connectivity chains, with a splitting action leading to monomers/dimers, chains or sheets, often tightly interdigitated and held together through aromatic π–π interactions (Díaz de Vivar et al., 2004, 2005, 2006).

On the other hand, when these chelating ligands are replaced by their `bridging' counterparts, such as 4,4'-bipyridine, more open frameworks are often obtained, which are becoming the object of active research owing to the interesting catalytic properties that some of these compounds display (Wu et al., 2002, and references therein). Here we report an interesting structure, ([Zn(C₁₀H₈N₂)(H₂O)₄][Zn(C₁₀H₈N₂)]₂(S₂O₃)₃]·2(H₂O), (I), which contains an open framework where 4,4'-bipyridine acts as a spacer. To our knowledge, this is the first Zn^II complex containing thiosulfate and 4,4'-bipyridine (4,4'-bipy).

In this structure two different one-dimensional arrays coexist, viz. a cationic chain consisting of one heterocyclic base unit and four water molecules bound to hexacoordinated Zn atom (Zn3), and a second array, describable as an anionic double chain providing for charge balance and built up around the two remaining four-coordinated Zn centres (Zn1 and Zn2), bound to two heterocyclic base units and to three thiosulfate anions (Fig. 1).

The environment around the Zn3 cation is a nearly perfect octahedron, with the equatorial plane formed by four evenly distributed water molecules [O1W–O4W; the angular span around Zn3 is 86.32 (5)–95.53 (6)°; the mean deviation from the least-squares equatorial plane is 0.01 (1) Å]. Two N atoms [N5ⁱⁱ and N6; symmetry code: (ii) x - 1/2, y + 1/2, z] from two symmetry-related 4,4'-bipy units occupy the axial positions [N5ⁱⁱ—Zn3—N6 = 176.36 (6)°; the largest deviation from the mean-plane normal is 3.5 (1)° for the Zn3—N5ⁱⁱ vector] and serve as the connector for the cationic one-dimensional structure which builds up along [110] and, due to the c-glide, also along [110], c/2 apart from the former.

On the other hand, the coordination polyhedra around Zn1 and Zn2 are similar to each other in with regard to coordination number (n = 4), but diverse both in their components and in their distortions with respect to an expected ideal tetrahedral geometry. Atom Zn1 coordinates to two donor N atoms [N1 and N2ⁱ; (i) x, -y, z + 1/2] from two symmetry-related 4,4'-bipy groups, and two S atoms (S2 and S4) from two different thiosulfate anions, determining a linear polymer where the organic ligand acts as a spacer between two symmetry-related metal ions. Zn2 is also four-coordinated and bound to two symmetry-related, independent 4,4'-bipy groups via two N atoms (N3 and N4ⁱ) and to two thiosulfate anions, this time through one O (O6) and one S (S6) atoms. When connected through the 4,4'-bipy molecule, these groups also define linear chains, parallel to the Zn1 couterpart. Each one of the Zn1 and Zn2 centers are in turn connected by one of the thiosulfate anions (acting in a bridging mode), thus forming a two-dimensional net through the Zn1—S4—S3—O6—Zn2 bridge.

The result is that the anionic part of the structure can be seen as ribbons resembling a twisted ladder (Fig 1), with the `uprights' defined by pairs of parallel 4,4'-bipy units and the `steps' by extended Zn₂(S₂O₃)₃ groups. At each `step' the expected straight direction of the ladder `breaks' in a 120° zigzag fashion (see insert in Fig. 1). The strips evolve parallel to each other along the c axis.

The thiosulfate anions display two different coordination modes, i.e. monodentate (µ-S) and bidentate (µ₂– S,O), both of them quite frequent in the coordination behaviour of the anion. Both monodentate units present some kind of disorder (see Experimental).

As already stated, the three independent 4,4'-bipy units in the structure act as spacers, and all of the individual bipy groups lie out of the common mean plane [the dihedral angles are 39.3 (1), 30.8 (1) and 32.1 (1)° for the 4,4'-bipy units in the Zn1, Zn2 and Zn3 chains, respectively].

Fig. 2 shows how the three individual one-dimensional structures pack, the straight cationic chains running parallel to the [110] and [110] diagonals (each family c/2 away from one another; Fig. 2a), and the zigzag anionic ribbons running along [001] (Fig. 2b). The three types of chains evolve in space in much the way as the three independent sets of screw axes do in space group P2₁2₁2₁, confirming a set of three non-intersecting one-dimensional structures. There is, however, a strong interaction between different chains, due to the very complex hydrogen-bonding scheme (Table 2), having the water molecules of the cationic chain as the donors and the thiosulfate units of the anionic chains as the acceptors.

Related literature

For related literature, see: Bear & Mumme (1970); Bugli & Carré (1980); Díaz de Vivar, Baggio & Baggio (2004); Díaz de Vivar, Baggio, Garland & Baggio (2006); Díaz de Vivar, Baggio, Muñoz & Baggio (2005); Flack (1983); Magnusson & Johansson (1981); Wu et al. (2002).

S2. Experimental

4,4'-Bipyridine was dissolved in methanol and left to diffuse slowly at room temperature over an aqueous solution of Na₂S₂O₃ and Zn acetate in a 1:1:1 molar ratio. Colorless crystalline aggregates of (I) appeared after ten days, from which crystals suitable for X-ray analysis could be separated.

S3. Refinement

The H atoms attached to C atoms were placed at calculated positions with C—H distances of 0.93 Å and allowed to ride. Those bound to O were located in difference maps and then refined with the sole restraint of a common, refinable O—H distance which converged to O—O = 0.78 (2) Å. For all H atoms, U_iso(H) = 1.2U_eq(carrier). Both monocoordinated thiosulfates (S1/S2/O1–O3 and S5/S6/O7–O9) presented some kind of disorder in the non-coordinated atoms and were refined with split models. The occupation factors for the major/minor components in each one refined to 0.727 (2)/0.273 (2) and 0.746 (8)/0.254 (8), respectively. The correct orientation of the structure with respect to the polar axis direction was determined by means of the Flack (1983) parameter.

Computing details

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2001 ); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2001); software used to prepare material for publication: SHELXTL-NT and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I). The independent (symmetry-related) part is drawn in full (empty) 60% displacement ellipsoids. [Symmetry codes as in Table 1.] Insert: A lateral view of the anionic chain showing its zigzag character. See text for details.
	Fig. 2. Partial (and superimposable) projections of the structure along [110]. (a) The straight cationic chains, running along [110] (top to bottom in the figure) and [110] (coming out of the figure); the anionic chains have been omitted for clarity. (b) The zigzag anionic chains, running parallel to [001]. The cationic chains have been omitted for clarity.

catena-Poly[[[tetraaquazinc(II)]-µ-4,4'-bipyridine-κ²N:N'] [[µ-thiosulfato-bis[(thiosulfato-κS)zinc(II)]]-δi-µ-4,4'-bipyridine- κ⁴N:N'] dihydrate], {[Zn(C₁₀H₈N₂)(H₂O)₄][Zn₂(S₂O₃)₃(C₁₀H₈N₂)₂]·2H₂O

Crystal data

[Zn(C10H8N2)(H2O)4][Zn2(S2O3)3(C10H8N2)2]·2H2O	F(000) = 2256
Mr = 1109.12	Dx = 1.764 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 8976 reflections
a = 16.6521 (8) Å	θ = 2.2–26.8°
b = 15.5103 (7) Å	µ = 2.08 mm^−1
c = 17.8922 (8) Å	T = 292 K
β = 115.340 (2)°	Needles, colourless
V = 4176.4 (3) Å^3	0.22 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	11611 independent reflections
Radiation source: fine-focus sealed tube	11255 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 30.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −23→23
Tmin = 0.657, Tmax = 0.851	k = −21→21
29188 measured reflections	l = −24→25

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.0321P)^2 + 3.2788P] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.001
11611 reflections	Δρmax = 0.57 e Å^−3
601 parameters	Δρmin = −0.41 e Å^−3
33 restraints	Absolute structure: Flack (1983), 5223 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (4)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.506296 (16)	0.214055 (12)	0.764435 (14)	0.01624 (4)
Zn2	0.815865 (16)	0.214606 (12)	0.756011 (14)	0.01682 (4)
Zn3	0.187644 (16)	0.943038 (12)	0.494361 (15)	0.01606 (4)
S1	0.28056 (3)	0.20858 (3)	0.63651 (3)	0.02315 (9)
S2	0.37876 (3)	0.29449 (3)	0.70333 (3)	0.02001 (8)
O1	0.19702 (13)	0.25547 (14)	0.62438 (14)	0.0347 (5)	0.727 (2)
O2	0.29080 (13)	0.13075 (11)	0.68136 (11)	0.0240 (4)	0.727 (2)
O3	0.28276 (18)	0.19666 (14)	0.55588 (12)	0.0360 (7)	0.727 (2)
O1'	0.2193 (2)	0.2078 (3)	0.6703 (3)	0.0347 (5)	0.273 (2)
O2'	0.3345 (3)	0.11557 (13)	0.6663 (3)	0.0240 (4)	0.273 (2)
O3'	0.2565 (4)	0.2141 (3)	0.55357 (16)	0.0360 (7)	0.273 (2)
S3	0.64585 (3)	0.32708 (3)	0.71417 (3)	0.01710 (7)
S4	0.62986 (3)	0.30474 (3)	0.81847 (3)	0.02232 (9)
O4	0.56063 (9)	0.34455 (9)	0.64475 (9)	0.0239 (3)
O5	0.70769 (9)	0.39970 (8)	0.73298 (9)	0.0241 (3)
O6	0.68629 (9)	0.24840 (8)	0.69697 (8)	0.0203 (2)
S6	0.89218 (3)	0.34017 (3)	0.79887 (3)	0.02089 (8)
S5	1.01481 (7)	0.28980 (14)	0.82700 (10)	0.0213 (2)	0.746 (8)
O7	1.0497 (2)	0.3359 (3)	0.7772 (2)	0.0586 (11)	0.746 (8)
O8	0.9964 (2)	0.1984 (2)	0.8026 (2)	0.0418 (9)	0.746 (8)
O9	1.0722 (2)	0.2968 (2)	0.91566 (15)	0.0237 (6)	0.746 (8)
S5'	1.00633 (19)	0.2716 (3)	0.8283 (3)	0.0213 (2)	0.254 (8)
O7'	1.0486 (6)	0.2916 (8)	0.7747 (6)	0.0586 (11)	0.254 (8)
O8'	0.9861 (6)	0.1789 (3)	0.8276 (7)	0.0418 (9)	0.254 (8)
O9'	1.0582 (8)	0.3015 (6)	0.9132 (4)	0.0237 (6)	0.254 (8)
O1W	0.25487 (10)	1.04994 (8)	0.46700 (9)	0.0228 (3)
H1WA	0.2312 (16)	1.0701 (15)	0.4218 (11)	0.027*
H1WB	0.2647 (17)	1.0912 (14)	0.4959 (13)	0.027*
O2W	0.11426 (9)	0.93124 (8)	0.36631 (8)	0.0184 (2)
H2WA	0.1382 (15)	0.9329 (15)	0.3366 (14)	0.022*
H2WB	0.0782 (14)	0.8959 (14)	0.3546 (15)	0.022*
O3W	0.11534 (11)	0.84142 (9)	0.51492 (9)	0.0281 (3)
H3WA	0.0937 (18)	0.8423 (17)	0.5446 (15)	0.034*
H3WB	0.0985 (19)	0.8008 (14)	0.4853 (15)	0.034*
O4W	0.26703 (9)	0.96777 (9)	0.61957 (8)	0.0217 (3)
H4WA	0.2812 (17)	1.0144 (11)	0.6368 (15)	0.026*
H4WB	0.2610 (17)	0.9406 (14)	0.6552 (14)	0.026*
O5W	0.21065 (14)	0.06823 (11)	0.78084 (12)	0.0408 (4)
H5WA	0.226 (2)	0.0982 (16)	0.7528 (18)	0.049*
H5WB	0.209 (2)	0.0201 (12)	0.7633 (19)	0.049*
O6W	0.20182 (11)	0.35697 (11)	0.75755 (10)	0.0342 (3)
H6WA	0.2026 (19)	0.3265 (18)	0.7226 (15)	0.041*
H6WB	0.1615 (17)	0.3432 (18)	0.7671 (19)	0.041*
N1	0.51344 (11)	0.12740 (10)	0.68164 (9)	0.0198 (3)
N2	0.51540 (11)	−0.14315 (10)	0.36497 (9)	0.0197 (3)
C1	0.54338 (15)	0.04666 (13)	0.69979 (12)	0.0281 (4)
H1	0.5620	0.0273	0.7538	0.034*
C2	0.54790 (15)	−0.00944 (13)	0.64156 (12)	0.0302 (4)
H2	0.5704	−0.0648	0.6567	0.036*
C3	0.51852 (13)	0.01799 (12)	0.56033 (11)	0.0208 (3)
C4	0.51798 (13)	−0.04008 (12)	0.49416 (11)	0.0202 (3)
C5	0.58620 (13)	−0.09795 (14)	0.50645 (11)	0.0251 (4)
H5	0.6338	−0.1031	0.5583	0.030*
C6	0.58287 (13)	−0.14819 (13)	0.44075 (11)	0.0229 (4)
H6	0.6290	−0.1866	0.4496	0.027*
C7	0.44739 (14)	−0.09023 (14)	0.35419 (12)	0.0282 (4)
H7	0.3992	−0.0886	0.3025	0.034*
C8	0.44545 (14)	−0.03790 (13)	0.41635 (12)	0.0264 (4)
H8	0.3971	−0.0022	0.4065	0.032*
C9	0.48578 (14)	0.10159 (12)	0.54081 (11)	0.0238 (4)
H9	0.4653	0.1219	0.4869	0.029*
C10	0.48416 (15)	0.15412 (12)	0.60273 (12)	0.0247 (4)
H10	0.4620	0.2099	0.5893	0.030*
N3	0.81107 (10)	0.13083 (9)	0.66614 (9)	0.0173 (3)
N4	0.81513 (11)	−0.13647 (9)	0.34783 (9)	0.0197 (3)
C11	0.87227 (12)	0.06798 (11)	0.68251 (11)	0.0189 (3)
H11	0.9160	0.0620	0.7363	0.023*
C12	0.87256 (12)	0.01191 (11)	0.62214 (10)	0.0181 (3)
H12	0.9154	−0.0311	0.6356	0.022*
C13	0.80766 (12)	0.02078 (11)	0.54101 (11)	0.0169 (3)
C14	0.80893 (12)	−0.03473 (11)	0.47386 (10)	0.0173 (3)
C15	0.84242 (14)	−0.11850 (12)	0.48972 (11)	0.0236 (4)
H15	0.8632	−0.1416	0.5427	0.028*
C16	0.84429 (15)	−0.16675 (12)	0.42538 (12)	0.0252 (4)
H16	0.8667	−0.2226	0.4363	0.030*
C17	0.78189 (14)	−0.05641 (12)	0.33254 (11)	0.0231 (4)
H17	0.7611	−0.0351	0.2789	0.028*
C18	0.77718 (14)	−0.00409 (12)	0.39310 (11)	0.0233 (4)
H18	0.7531	0.0510	0.3800	0.028*
C19	0.74361 (12)	0.08519 (12)	0.52497 (11)	0.0199 (3)
H19	0.6986	0.0922	0.4719	0.024*
C20	0.74755 (12)	0.13852 (12)	0.58861 (11)	0.0202 (3)
H20	0.7046	0.1812	0.5772	0.024*
N5	0.58913 (10)	0.53134 (10)	0.49699 (9)	0.0183 (3)
N6	0.28520 (10)	0.85075 (9)	0.49811 (9)	0.0179 (3)
C21	0.53659 (12)	0.57403 (12)	0.42838 (11)	0.0204 (3)
H21	0.5400	0.5607	0.3792	0.024*
C22	0.47732 (12)	0.63721 (11)	0.42735 (11)	0.0203 (3)
H22	0.4416	0.6650	0.3782	0.024*
C23	0.47169 (11)	0.65888 (11)	0.50055 (11)	0.0164 (3)
C24	0.40875 (11)	0.72623 (10)	0.50079 (10)	0.0163 (3)
C25	0.32883 (12)	0.73809 (11)	0.43085 (10)	0.0185 (3)
H25	0.3156	0.7052	0.3836	0.022*
C26	0.26955 (12)	0.79947 (11)	0.43279 (11)	0.0190 (3)
H26	0.2158	0.8056	0.3863	0.023*
C27	0.36312 (13)	0.83934 (12)	0.56534 (11)	0.0223 (3)
H27	0.3758	0.8745	0.6111	0.027*
C28	0.42491 (12)	0.77790 (12)	0.56929 (11)	0.0208 (3)
H28	0.4769	0.7711	0.6174	0.025*
C29	0.52583 (12)	0.61430 (12)	0.57197 (11)	0.0186 (3)
H29	0.5245	0.6271	0.6222	0.022*
C30	0.58168 (12)	0.55069 (11)	0.56711 (11)	0.0190 (3)
H30	0.6158	0.5197	0.6147	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02311 (10)	0.01515 (9)	0.01188 (8)	−0.00213 (7)	0.00885 (7)	−0.00093 (7)
Zn2	0.02526 (10)	0.01402 (8)	0.01251 (8)	0.00142 (7)	0.00935 (7)	0.00042 (7)
Zn3	0.01805 (8)	0.01595 (8)	0.01451 (8)	0.00518 (7)	0.00727 (7)	0.00002 (7)
S1	0.0254 (2)	0.0270 (2)	0.01743 (19)	−0.00822 (17)	0.00956 (16)	−0.00593 (16)
S2	0.0235 (2)	0.01519 (17)	0.02064 (19)	−0.00259 (15)	0.00876 (16)	−0.00050 (15)
O1	0.0245 (9)	0.0313 (10)	0.0398 (11)	0.0014 (8)	0.0056 (8)	−0.0091 (8)
O2	0.0287 (10)	0.0167 (7)	0.0232 (8)	−0.0039 (7)	0.0078 (7)	0.0024 (6)
O3	0.0672 (17)	0.0219 (10)	0.0195 (7)	−0.0096 (11)	0.0192 (9)	−0.0070 (7)
O1'	0.0245 (9)	0.0313 (10)	0.0398 (11)	0.0014 (8)	0.0056 (8)	−0.0091 (8)
O2'	0.0287 (10)	0.0167 (7)	0.0232 (8)	−0.0039 (7)	0.0078 (7)	0.0024 (6)
O3'	0.0672 (17)	0.0219 (10)	0.0195 (7)	−0.0096 (11)	0.0192 (9)	−0.0070 (7)
S3	0.01949 (18)	0.01656 (17)	0.01780 (18)	0.00122 (14)	0.01040 (15)	0.00127 (14)
S4	0.0273 (2)	0.0270 (2)	0.01579 (19)	−0.00875 (17)	0.01217 (17)	−0.00633 (16)
O4	0.0224 (6)	0.0299 (7)	0.0219 (6)	0.0040 (5)	0.0119 (5)	0.0049 (5)
O5	0.0236 (6)	0.0184 (6)	0.0340 (7)	0.0002 (5)	0.0160 (6)	0.0030 (5)
O6	0.0244 (6)	0.0191 (6)	0.0192 (6)	0.0026 (5)	0.0111 (5)	−0.0014 (5)
S6	0.02029 (19)	0.01776 (18)	0.02089 (19)	0.00043 (15)	0.00524 (15)	0.00147 (15)
S5	0.0179 (3)	0.0283 (6)	0.0175 (2)	−0.0005 (3)	0.0073 (2)	0.0016 (4)
O7	0.0411 (12)	0.093 (3)	0.0547 (14)	0.0212 (18)	0.0334 (11)	0.047 (2)
O8	0.0354 (12)	0.0327 (13)	0.0324 (17)	0.0155 (10)	−0.0091 (11)	−0.0138 (12)
O9	0.0162 (13)	0.0254 (7)	0.0191 (6)	0.0015 (8)	−0.0023 (6)	−0.0003 (5)
S5'	0.0179 (3)	0.0283 (6)	0.0175 (2)	−0.0005 (3)	0.0073 (2)	0.0016 (4)
O7'	0.0411 (12)	0.093 (3)	0.0547 (14)	0.0212 (18)	0.0334 (11)	0.047 (2)
O8'	0.0354 (12)	0.0327 (13)	0.0324 (17)	0.0155 (10)	−0.0091 (11)	−0.0138 (12)
O9'	0.0162 (13)	0.0254 (7)	0.0191 (6)	0.0015 (8)	−0.0023 (6)	−0.0003 (5)
O1W	0.0275 (7)	0.0187 (6)	0.0195 (6)	−0.0017 (5)	0.0075 (5)	−0.0010 (5)
O2W	0.0198 (6)	0.0188 (6)	0.0177 (6)	0.0013 (5)	0.0092 (5)	−0.0016 (4)
O3W	0.0436 (9)	0.0242 (7)	0.0249 (7)	−0.0065 (6)	0.0227 (6)	−0.0048 (5)
O4W	0.0275 (7)	0.0206 (6)	0.0166 (6)	0.0071 (5)	0.0092 (5)	0.0010 (5)
O5W	0.0641 (12)	0.0336 (8)	0.0453 (10)	−0.0111 (8)	0.0429 (10)	−0.0116 (7)
O6W	0.0289 (8)	0.0382 (9)	0.0313 (8)	0.0063 (7)	0.0089 (6)	−0.0060 (7)
N1	0.0271 (8)	0.0178 (7)	0.0134 (6)	−0.0007 (6)	0.0078 (6)	−0.0028 (5)
N2	0.0261 (8)	0.0169 (7)	0.0165 (7)	0.0015 (6)	0.0095 (6)	−0.0002 (5)
C1	0.0431 (11)	0.0235 (9)	0.0129 (8)	0.0101 (8)	0.0073 (8)	0.0004 (7)
C2	0.0445 (12)	0.0245 (9)	0.0157 (8)	0.0141 (8)	0.0072 (8)	0.0009 (7)
C3	0.0256 (9)	0.0201 (8)	0.0150 (8)	0.0027 (7)	0.0072 (7)	−0.0029 (6)
C4	0.0288 (9)	0.0167 (8)	0.0146 (7)	−0.0004 (7)	0.0088 (7)	−0.0025 (6)
C5	0.0248 (9)	0.0318 (10)	0.0130 (7)	0.0050 (7)	0.0026 (7)	−0.0047 (7)
C6	0.0235 (9)	0.0259 (9)	0.0174 (8)	0.0040 (7)	0.0069 (7)	−0.0048 (6)
C7	0.0303 (10)	0.0322 (10)	0.0152 (8)	0.0108 (8)	0.0030 (7)	−0.0044 (7)
C8	0.0287 (9)	0.0282 (9)	0.0180 (8)	0.0089 (8)	0.0058 (7)	−0.0044 (7)
C9	0.0367 (10)	0.0215 (8)	0.0152 (7)	0.0019 (7)	0.0130 (7)	0.0012 (6)
C10	0.0414 (11)	0.0164 (8)	0.0171 (8)	0.0009 (7)	0.0132 (8)	0.0005 (6)
N3	0.0239 (7)	0.0164 (6)	0.0128 (6)	0.0008 (5)	0.0089 (6)	−0.0010 (5)
N4	0.0280 (8)	0.0151 (6)	0.0166 (7)	0.0001 (6)	0.0100 (6)	−0.0005 (5)
C11	0.0235 (8)	0.0174 (7)	0.0134 (7)	0.0023 (6)	0.0056 (6)	−0.0001 (6)
C12	0.0230 (8)	0.0160 (7)	0.0149 (7)	0.0019 (6)	0.0077 (6)	−0.0001 (6)
C13	0.0230 (8)	0.0132 (7)	0.0149 (7)	0.0011 (6)	0.0086 (6)	−0.0005 (6)
C14	0.0213 (8)	0.0163 (7)	0.0152 (7)	−0.0006 (6)	0.0086 (6)	−0.0020 (6)
C15	0.0371 (10)	0.0182 (8)	0.0148 (8)	0.0048 (7)	0.0105 (7)	0.0010 (6)
C16	0.0417 (11)	0.0164 (8)	0.0176 (8)	0.0051 (7)	0.0129 (8)	0.0001 (6)
C17	0.0352 (10)	0.0210 (8)	0.0123 (7)	0.0044 (7)	0.0095 (7)	0.0018 (6)
C18	0.0352 (10)	0.0172 (8)	0.0172 (8)	0.0074 (7)	0.0111 (7)	0.0022 (6)
C19	0.0230 (8)	0.0205 (8)	0.0140 (7)	0.0035 (6)	0.0059 (6)	−0.0001 (6)
C20	0.0234 (8)	0.0190 (8)	0.0182 (8)	0.0054 (6)	0.0088 (7)	0.0014 (6)
N5	0.0198 (7)	0.0185 (7)	0.0181 (7)	0.0031 (5)	0.0097 (6)	0.0014 (5)
N6	0.0213 (7)	0.0169 (6)	0.0166 (6)	0.0038 (5)	0.0092 (6)	0.0004 (5)
C21	0.0250 (8)	0.0232 (8)	0.0170 (7)	0.0066 (7)	0.0130 (7)	0.0030 (6)
C22	0.0252 (8)	0.0208 (8)	0.0175 (8)	0.0086 (7)	0.0116 (7)	0.0058 (6)
C23	0.0163 (7)	0.0161 (7)	0.0176 (7)	0.0031 (6)	0.0081 (6)	0.0002 (6)
C24	0.0173 (7)	0.0168 (7)	0.0169 (8)	0.0040 (6)	0.0092 (6)	0.0017 (6)
C25	0.0212 (8)	0.0174 (7)	0.0162 (7)	0.0041 (6)	0.0074 (6)	−0.0008 (6)
C26	0.0192 (8)	0.0187 (7)	0.0173 (7)	0.0047 (6)	0.0061 (6)	0.0005 (6)
C27	0.0235 (9)	0.0249 (9)	0.0175 (8)	0.0057 (7)	0.0078 (7)	−0.0047 (6)
C28	0.0182 (8)	0.0245 (8)	0.0174 (8)	0.0060 (6)	0.0055 (6)	−0.0016 (6)
C29	0.0189 (7)	0.0226 (8)	0.0156 (7)	0.0043 (6)	0.0085 (6)	0.0008 (6)
C30	0.0202 (8)	0.0208 (8)	0.0171 (7)	0.0062 (6)	0.0092 (6)	0.0032 (6)

Geometric parameters (Å, º)

Zn1—N1	2.0411 (15)	C4—C5	1.390 (3)
Zn1—N2^i	2.0577 (15)	C4—C8	1.400 (3)
Zn1—S2	2.2967 (5)	C5—C6	1.391 (3)
Zn1—S4	2.3332 (5)	C5—H5	0.9300
Zn2—O6	2.0237 (13)	C6—H6	0.9300
Zn2—N3	2.0422 (14)	C7—C8	1.388 (3)
Zn2—N4^i	2.0457 (15)	C7—H7	0.9300
Zn2—S6	2.2719 (5)	C8—H8	0.9300
Zn3—O4W	2.0924 (13)	C9—C10	1.385 (3)
Zn3—O2W	2.0927 (13)	C9—H9	0.9300
Zn3—O3W	2.1090 (15)	C10—H10	0.9300
Zn3—N6	2.1446 (15)	N3—C20	1.342 (2)
Zn3—N5^ii	2.1529 (15)	N3—C11	1.349 (2)
Zn3—O1W	2.1705 (14)	N4—C17	1.339 (2)
S1—O3'	1.364 (3)	N4—C16	1.343 (2)
S1—O1'	1.392 (4)	N4—Zn2^iii	2.0457 (15)
S1—O2	1.4189 (17)	C11—C12	1.388 (2)
S1—O3	1.4703 (19)	C11—H11	0.9300
S1—O1	1.501 (2)	C12—C13	1.397 (2)
S1—O2'	1.662 (3)	C12—H12	0.9300
S1—S2	2.0507 (6)	C13—C19	1.398 (2)
S3—O4	1.4565 (14)	C13—C14	1.486 (2)
S3—O5	1.4649 (14)	C14—C18	1.393 (2)
S3—O6	1.4882 (13)	C14—C15	1.394 (2)
S3—S4	2.0246 (6)	C15—C16	1.384 (2)
S6—S5	2.0380 (7)	C15—H15	0.9300
S6—S5'	2.0405 (10)	C16—H16	0.9300
S5—O7	1.444 (2)	C17—C18	1.383 (3)
S5—O9	1.4643 (15)	C17—H17	0.9300
S5—O8	1.476 (2)	C18—H18	0.9300
S5'—O7'	1.445 (2)	C19—C20	1.386 (2)
S5'—O8'	1.476 (2)	C19—H19	0.9300
S5'—O9'	1.4647 (17)	C20—H20	0.9300
O1W—H1WA	0.797 (17)	N5—C21	1.339 (2)
O1W—H1WB	0.794 (17)	N5—C30	1.346 (2)
O2W—H2WA	0.790 (16)	N5—Zn3^iv	2.1529 (15)
O2W—H2WB	0.773 (16)	N6—C26	1.344 (2)
O3W—H3WA	0.759 (17)	N6—C27	1.351 (2)
O3W—H3WB	0.794 (17)	C21—C22	1.385 (2)
O4W—H4WA	0.782 (17)	C21—H21	0.9300
O4W—H4WB	0.806 (17)	C22—C23	1.394 (2)
O5W—H5WA	0.799 (18)	C22—H22	0.9300
O5W—H5WB	0.805 (18)	C23—C29	1.392 (2)
O6W—H6WA	0.789 (18)	C23—C24	1.481 (2)
O6W—H6WB	0.789 (18)	C24—C28	1.391 (2)
N1—C1	1.335 (2)	C24—C25	1.395 (2)
N1—C10	1.347 (2)	C25—C26	1.382 (2)
N2—C6	1.343 (2)	C25—H25	0.9300
N2—C7	1.344 (2)	C26—H26	0.9300
N2—Zn1^iii	2.0577 (15)	C27—C28	1.382 (2)
C1—C2	1.384 (3)	C27—H27	0.9300
C1—H1	0.9300	C28—H28	0.9300
C2—C3	1.387 (3)	C29—C30	1.384 (2)
C2—H2	0.9300	C29—H29	0.9300
C3—C9	1.392 (3)	C30—H30	0.9300
C3—C4	1.484 (2)
N1—Zn1—N2^i	106.09 (6)	C5—C4—C3	122.70 (17)
N1—Zn1—S2	109.97 (5)	C8—C4—C3	119.13 (17)
N2^i—Zn1—S2	114.43 (5)	C4—C5—C6	119.59 (17)
N1—Zn1—S4	112.50 (5)	C4—C5—H5	120.2
N2^i—Zn1—S4	103.77 (5)	C6—C5—H5	120.2
S2—Zn1—S4	109.976 (18)	N2—C6—C5	122.28 (17)
O6—Zn2—N3	94.60 (6)	N2—C6—H6	118.9
O6—Zn2—N4^i	101.60 (6)	C5—C6—H6	118.9
N3—Zn2—N4^i	104.10 (6)	N2—C7—C8	123.31 (18)
O6—Zn2—S6	105.76 (4)	N2—C7—H7	118.3
N3—Zn2—S6	129.71 (5)	C8—C7—H7	118.3
N4^i—Zn2—S6	115.56 (5)	C7—C8—C4	118.47 (18)
O4W—Zn3—O2W	173.45 (6)	C7—C8—H8	120.8
O4W—Zn3—O3W	95.53 (6)	C4—C8—H8	120.8
O2W—Zn3—O3W	90.93 (6)	C10—C9—C3	119.14 (17)
O4W—Zn3—N6	88.04 (5)	C10—C9—H9	120.4
O2W—Zn3—N6	93.18 (5)	C3—C9—H9	120.4
O3W—Zn3—N6	88.69 (6)	N1—C10—C9	122.36 (17)
O4W—Zn3—N5^ii	89.89 (5)	N1—C10—H10	118.8
O2W—Zn3—N5^ii	89.21 (5)	C9—C10—H10	118.8
O3W—Zn3—N5^ii	88.53 (6)	C20—N3—C11	118.47 (15)
N6—Zn3—N5^ii	176.36 (6)	C20—N3—Zn2	120.34 (12)
O4W—Zn3—O1W	87.19 (6)	C11—N3—Zn2	121.17 (12)
O2W—Zn3—O1W	86.32 (5)	C17—N4—C16	118.05 (16)
O3W—Zn3—O1W	176.60 (6)	C17—N4—Zn2^iii	121.95 (12)
N6—Zn3—O1W	93.44 (6)	C16—N4—Zn2^iii	119.91 (12)
N5^ii—Zn3—O1W	89.45 (6)	N3—C11—C12	122.53 (16)
O3'—S1—O1'	123.1 (2)	N3—C11—H11	118.7
O2—S1—O3	113.62 (12)	C12—C11—H11	118.7
O2—S1—O1	111.94 (13)	C11—C12—C13	119.21 (16)
O3—S1—O1	109.26 (15)	C11—C12—H12	120.4
O3'—S1—O2'	105.6 (2)	C13—C12—H12	120.4
O1'—S1—O2'	104.4 (2)	C12—C13—C19	117.81 (16)
O3'—S1—S2	112.51 (16)	C12—C13—C14	120.72 (15)
O1'—S1—S2	107.60 (15)	C19—C13—C14	121.44 (15)
O2—S1—S2	110.50 (8)	C18—C14—C15	118.06 (16)
O3—S1—S2	107.77 (9)	C18—C14—C13	120.72 (16)
O1—S1—S2	103.17 (8)	C15—C14—C13	121.22 (15)
O2'—S1—S2	100.98 (11)	C16—C15—C14	118.93 (17)
S1—S2—Zn1	105.59 (2)	C16—C15—H15	120.5
O4—S3—O5	112.67 (8)	C14—C15—H15	120.5
O4—S3—O6	109.76 (8)	N4—C16—C15	122.89 (17)
O5—S3—O6	110.01 (8)	N4—C16—H16	118.6
O4—S3—S4	110.70 (6)	C15—C16—H16	118.6
O5—S3—S4	106.06 (6)	N4—C17—C18	122.77 (17)
O6—S3—S4	107.45 (6)	N4—C17—H17	118.6
S3—S4—Zn1	99.31 (2)	C18—C17—H17	118.6
S3—O6—Zn2	125.46 (8)	C17—C18—C14	119.29 (17)
S5—S6—Zn2	96.39 (7)	C17—C18—H18	120.4
S5'—S6—Zn2	88.01 (15)	C14—C18—H18	120.4
O7—S5—O9	112.51 (15)	C20—C19—C13	119.60 (16)
O7—S5—O8	112.3 (2)	C20—C19—H19	120.2
O9—S5—O8	110.41 (12)	C13—C19—H19	120.2
O7—S5—S6	106.48 (13)	N3—C20—C19	122.37 (16)
O9—S5—S6	111.08 (17)	N3—C20—H20	118.8
O8—S5—S6	103.62 (14)	C19—C20—H20	118.8
O7'—S5'—O8'	112.2 (2)	C21—N5—C30	117.36 (15)
O7'—S5'—O9'	112.44 (18)	C21—N5—Zn3^iv	119.98 (12)
O8'—S5'—O9'	110.35 (14)	C30—N5—Zn3^iv	122.49 (12)
O7'—S5'—S6	112.4 (5)	C26—N6—C27	116.84 (15)
O8'—S5'—S6	108.7 (4)	C26—N6—Zn3	120.36 (12)
O9'—S5'—S6	100.0 (6)	C27—N6—Zn3	122.77 (12)
Zn3—O1W—H1WA	116.8 (19)	N5—C21—C22	122.98 (16)
Zn3—O1W—H1WB	116.9 (19)	N5—C21—H21	118.5
H1WA—O1W—H1WB	103 (2)	C22—C21—H21	118.5
Zn3—O2W—H2WA	120.5 (18)	C21—C22—C23	119.48 (16)
Zn3—O2W—H2WB	112.4 (18)	C21—C22—H22	120.3
H2WA—O2W—H2WB	113 (2)	C23—C22—H22	120.3
Zn3—O3W—H3WA	126 (2)	C29—C23—C22	117.74 (15)
Zn3—O3W—H3WB	122.9 (19)	C29—C23—C24	121.92 (15)
H3WA—O3W—H3WB	110 (2)	C22—C23—C24	120.33 (15)
Zn3—O4W—H4WA	122.5 (18)	C28—C24—C25	117.71 (15)
Zn3—O4W—H4WB	121.1 (18)	C28—C24—C23	122.60 (15)
H4WA—O4W—H4WB	107 (2)	C25—C24—C23	119.68 (15)
H5WA—O5W—H5WB	105 (2)	C26—C25—C24	119.06 (16)
H6WA—O6W—H6WB	108 (2)	C26—C25—H25	120.5
C1—N1—C10	118.27 (16)	C24—C25—H25	120.5
C1—N1—Zn1	124.93 (13)	N6—C26—C25	123.69 (16)
C10—N1—Zn1	116.79 (13)	N6—C26—H26	118.2
C6—N2—C7	118.03 (16)	C25—C26—H26	118.2
C6—N2—Zn1^iii	124.64 (13)	N6—C27—C28	123.11 (16)
C7—N2—Zn1^iii	117.30 (12)	N6—C27—H27	118.4
N1—C1—C2	122.77 (18)	C28—C27—H27	118.4
N1—C1—H1	118.6	C27—C28—C24	119.56 (16)
C2—C1—H1	118.6	C27—C28—H28	120.2
C1—C2—C3	119.18 (18)	C24—C28—H28	120.2
C1—C2—H2	120.4	C30—C29—C23	119.02 (16)
C3—C2—H2	120.4	C30—C29—H29	120.5
C2—C3—C9	118.25 (17)	C23—C29—H29	120.5
C2—C3—C4	121.90 (17)	N5—C30—C29	123.36 (16)
C9—C3—C4	119.80 (16)	N5—C30—H30	118.3
C5—C4—C8	118.16 (16)	C29—C30—H30	118.3

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···S4^v	0.80 (2)	2.71 (2)	3.4264 (14)	150 (2)
O1W—H1WB···O3^vi	0.79 (2)	1.91 (2)	2.700 (2)	175 (3)
O2W—H2WA···O5W^vii	0.79 (2)	1.87 (2)	2.649 (2)	171 (3)
O2W—H2WB···O8^viii	0.77 (2)	1.94 (2)	2.699 (3)	165 (2)
O3W—H3WA···O4^ii	0.76 (2)	2.09 (2)	2.8354 (19)	168 (3)
O3W—H3WB···O9^viii	0.79 (2)	1.89 (2)	2.678 (4)	173 (3)
O4W—H4WA···O2^vi	0.78 (2)	1.95 (2)	2.719 (2)	167 (3)
O4W—H4WB···O5^ii	0.81 (2)	2.05 (2)	2.815 (2)	160 (3)
O5W—H5WA···O2	0.80 (2)	2.06 (2)	2.815 (3)	157 (3)
O5W—H5WB···O5^ix	0.81 (2)	1.94 (2)	2.744 (2)	174 (3)
O6W—H6WA···O1	0.79 (2)	2.04 (2)	2.828 (3)	175 (3)
O6W—H6WB···O7^x	0.79 (2)	1.95 (2)	2.722 (3)	166 (3)

Symmetry codes: (ii) x−1/2, y+1/2, z; (v) x−1/2, −y+3/2, z−1/2; (vi) x, y+1, z; (vii) x, −y+1, z−1/2; (viii) x−1, −y+1, z−1/2; (ix) x−1/2, y−1/2, z; (x) x−1, y, z.