Aqua­(thio­sulfato-κ²O,S)[2,4,6-tri-2-pyridyl-1,3,5-triazine-κ³N²,N¹,N⁶]zinc(II) hemihydrate

The title compound, [Zn(S₂O₃)(C₁₈H₁₂N₆)(H₂O)]·0.5H₂O, contains two almost identical independent monomeric moieties composed of an octa­hedral Zn centre coordinated by a tridentate 2,4,6-tri-­2-pyridyl-1,3,5-triazine (tpt) ligand, one aqua ligand and an O,S-chelating thio­sulfate anion. The structure is stabilized by a solvent water mol­ecule. Multiple strong hydrogen bonds with additional weaker π–π inter­actions between tpt groups define a multiple column spatial organization.

S1. Comment

The coordination properties of thiosulfate have been extensively studied by our group with respect to dπ–pπ bonding in sulfur oxoanions. The (S₂O₃)²⁻ group has proved to be quite a versatile ligand, a behaviour related to its content of atoms classified as both soft and hard bases, according to Pearson (1973). This ligand is prone to producing a variety of coordination modes, especially when the metal ion is borderline between Pearson classes `a' and `b'. In an earlier paper (Freire et al., 2000), we presented a brief summary of the reported coordination modes of this anion to transition metals in coordination compounds. When the compound is monomeric, the anion binds either through S (type 1 mode) or S and O (type 3 mode), the former appearing more frequently than the latter [37 and 16 hits, respectively, in the Cambridge Structural Database (CSD, November 2005 version; Allen, 2002)]. We present here the structure of the title compound, [Zn(S₂O₃)(tpt)(H₂O)]₂·H₂O, (I) [tpt is 2,4,6-tris(2-pyridyl)-1,3,5-triazine], a monomeric structure where the coordination mode seems to lie somewhere in between these two cases.

The title compound crystallizes with two independent monomeric moieties, A and B, in the asymmetric unit and one single water molecule of crystallization (Fig. 1). Both units are built up around six-coordinate Zn^II cations (Zn1 and Zn2) bound to a tridentate 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand (tpt), one water molecule and a thiosulfate anion. This last binds strongly via S, with Zn—S1 = 2.286 (3)/2.286 (4) Å (in the following discussion, values separated by a solidus, /, will indicate the corresponding values for moieties A and B, respectively), and in a much weaker way through O, with Zn—O1 = 2.654 (4)/2.662 (4) Å. These latter distances are long enough to lie across the bonding/non-bonding borderline, and the `bonding' assignment remained doubtful until some bond-valence calculations were carried out (Brown & Altermatt, 1985). These produced values of 0.076/0.075, compared with the lower limit of 0.06 proposed by Liebau (2000) for a cation–donor contact to be considered as a weak bonding interaction. This allows us to ascribe, with some confidence, a bidentate character to the anion, although the situation might be better described as a semi-coordination lying somewhere in between the definite (S,O) bi-coordinate character [with an O_coordinated mean bond valence of 0.38 (13) for 16 cases in the CSD] and the (S) mono-coordinated situation, where the nearest-to-metal O atom presents bond valences of less than 0.01 (37 reported cases).

Having accepted the (S,O) coordination of the thiosulfate group, both polyhedra around Zn can be described as two highly distorted octahedra, with atoms S1, N1, N2 and N3 defining the basal plane [maximum deviations from the mean plane are 0.20 (1)/0.22 (1) Å for which atoms?] and cation shifts of 0.34 (1)/0.40 (1) Å towards the apical aqua molecule. The remaining apical site is occupied by the weakly bound atom O1. The apical axes thus defined are slightly `offset', subtending angles at the corresponding metal sites of 172.9 (12)/170.3 (14)°; this deviation from linearity is due to the chelating character displayed by the thiosulfate group. Ascribable to the rigidity of the tpt skeleton, the basal angles around both Zn units show considerable variation around the expected value of 90° [in the ranges 73.42 (15)–104.13 (11)/73.94 (14)–104.64 (11)°]. The `soft' Zn—O interactions, as expected, alter the thiosulfate characteristics, as S-coordinated anions typically do, with an enlargement of the S—S bond and a small contraction of the S—O bonds compared with ionic moieties (Baggio et al., 1996).

The tpt ligand presents its most commonly found binding mode, viz. tridentate to one single cation. In 32 out of 44 entries in the CSD, the tpt group behaves in this fashion, coordinating through the central N2 atom from the triazine ring and through the lateral N1 and N3 atoms from two pyridine rings, leaving the third pyridyl group uncoordinated. In both moieties, the central Zn—N distances [Zn1—N2 = 2.067 (5)/2.069 (4) Å] are distinctly shorter than the lateral ones [range 2.215 (4)—2.287 (4) Å]. This behaviour has already been observed in all the above-mentioned group 12 t pt complexes and also in other [ZnN₃] cores, and it is due to the rather inflexible character of the tpt skeleton, which forces a closer approach of the central N atom [see Harvey et al.(2004) for a detailed discussion]. The tpt core deviates from planarity, mainly through the lateral pyridine rings, subtending angles of 7.7 (1) and 10.5 (1)/5.0 (1) and 4.1 (1)° at the central triazine. In addition, the uncoordinated pyridines are rotated with respect to the central ring (see below). As a result of all this, the ligand presents one of the most distorted geometries reported to date.

The two identical independent moieties are quite similar. In addition to geometric similarities (Table 1), both molecules have an approximate (non-crystallographic) pseudo-mirror plane defined by atoms S1A/O1W/Zn1/N2A/C7A/C17A (in molecule A). The differences between them can be linked to the deviations from a real m symmetry and to the relevant torsion angles. Note that the atomic coordinates reported for A and B reference molecules were chosen so as to facilitate the packing discussion and have opposite `handedness', so that inversion-related torsion angles are quoted in Table 1.

Our analysis shows the main deviations to fall into three categories, as follows. Firstly, there is a slight rotation of the S₃ group around the Zn—S bond, constrained by the Zn—O1 interaction and leading to small and very similar Zn—S1—S2—O1 torsion angles [ΔΦ = 1.9 (2)°]. Secondly, there are different orientations of the terminal pyridyl groups with respect to the mean tpt plane. Their relative rotation around C4—C14 in opposite directions (ΔΦ ~10°; see N5—C7—C14—N6 angles in Table 1) can be related to π–π interaction with only one of them (Cg5; entry 2 in Table 3).

Finally, there is a different orientation of the aqua H atoms bound to atoms O1W and O2W, as the result of an H₂O rotation around the Zn—O_aqua bond, shown by the N2—Zn—O_aqua—H_aqua torsion angles in both moieties (Table 1 and Fig 1). The two relative orientations of the aqua molecule are almost at right angles to one another. This major difference introduces a most significant effect in the molecular packing, namely completely diverse substructures involving the independent A and B moieties, which aggregate into dissimilar `pure A' and `pure B' columns, propagating along the very short a axis. Both array types are held together by hydrogen bonds involving the aqua H atoms. In the case of type A molecules, the bonds form double chains or strips (hereinafter symbolized as `A=A' and shown as heavy lines in Fig. 2) built up around symmetry centres (Table 2, entries 1 and 2). For type B molecules, they form a simple linear array (`B', lighter lines in Fig. 2), with an additional bridging interaction provided by the solvent water molecule O3W (Table 2, entries 3–5).

These arrays interact with each other in turn through a strong hydrogen bond having O2W as donor and N6A as acceptor (entry 6 in Table 2), linking A=A and B columns into a strongly connected complex structure of the B=A=A=B type which behaves as the building block of the packing. These units interact with each other through much weaker C—H···O interactions (entries 7–9 in Table 2) and a few π–π contacts between interdigitated aromatic cycles belonging to different column types. (Table 3).

S2. Experimental

2,4,6-Tris(2-pyridyl)-1,3,5-triazine and zinc acetate were dissolved together in 96% ethanol and were left to diffuse over an aqueous sodium thiosulfate solution, in a 1:1:1 molar ratio. After three months, colourless crystals of (I) suitable for X-ray analysis were obtained.

S3. Refinement

H atoms attached to C were included in their calculated positions, with C—H = 0.93 Å, and treated as riding, with U_iso(H) = 1.2U_eq(C). H atoms attached to water molecules were found in the difference Fourier synthesis and refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.30 (2) Å and with U_iso(H) = 1.5U_eq(O). Two reflections partially eclipsed by the beam-stop were removed from the data set.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2000); software used to prepare material for publication: SHELXTL-NT (Bruker, 2000) and PLATON (Spek, 2003).

Figures

	Fig. 1. Views of the independent monomeric units of (I). Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity
	Fig. 2. A packing view of (I), down the b axis, showing the different hydrogen-bonded columnar units propagating upwards along a. Heavy lines denote double columns of type A=A and lighter lines denote columns of type B, laterally attached to the former to define a B=A=A=B structure (see text).

Bis[aqua(thiosulfato-κ²O,S)[2,4,6-tris(2-pyridyl)-1,3,5-triazine- κ³N,N',N'']zinc(II)] monohydrate

Crystal data

[Zn(S2O3)(C18H12N6)(H2O)]2·H2O	F(000) = 2104
Mr = 1033.70	Dx = 1.706 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.550 (5) Å	θ = 7.5–15°
b = 44.57 (7) Å	µ = 1.47 mm^−1
c = 13.791 (8) Å	T = 295 K
β = 119.88 (3)°	Block, colourless
V = 4024 (7) Å^3	0.32 × 0.16 × 0.14 mm
Z = 4

Data collection

Rigaku AFC-6 diffractometer	4159 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 26.0°, θmin = 1.9°
ω/2θ scans	h = −9→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→54
Tmin = 0.650, Tmax = 0.820	l = 0→16
15672 measured reflections	3 standard reflections every 150 reflections
7771 independent reflections	intensity decay: none

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.003P)^2 + 7.8876P] where P = (Fo^2 + 2Fc^2)/3
7771 reflections	(Δ/σ)max = 0.001
586 parameters	Δρmax = 0.43 e Å^−3
15 restraints	Δρmin = −0.90 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
Zn1	0.62864 (10)	0.454676 (12)	0.13133 (5)	0.03851 (16)
S1A	0.7748 (2)	0.50121 (3)	0.16398 (11)	0.0410 (3)
S2A	1.0638 (2)	0.48221 (3)	0.23751 (11)	0.0423 (3)
O1A	1.0320 (6)	0.45137 (7)	0.2573 (3)	0.0535 (10)
O2A	1.1340 (6)	0.48455 (9)	0.1572 (3)	0.0708 (12)
O3A	1.1880 (6)	0.49917 (9)	0.3377 (3)	0.0808 (14)
N1A	0.6445 (6)	0.43814 (9)	−0.0211 (3)	0.0389 (11)
N2A	0.6421 (6)	0.40838 (8)	0.1411 (3)	0.0340 (9)
N3A	0.6254 (6)	0.44385 (9)	0.2872 (3)	0.0355 (10)
N4A	0.6376 (6)	0.36134 (9)	0.0615 (3)	0.0361 (10)
N5A	0.6655 (6)	0.36440 (8)	0.2420 (3)	0.0336 (10)
N6A	0.7202 (6)	0.30441 (9)	0.2654 (3)	0.0412 (11)
C1A	0.6695 (8)	0.45457 (12)	−0.0950 (4)	0.0489 (14)
H1A	0.6807	0.4753	−0.0856	0.059*
C2A	0.6795 (8)	0.44233 (12)	−0.1840 (4)	0.0485 (14)
H2A	0.6966	0.4546	−0.2332	0.058*
C3A	0.6639 (8)	0.41189 (12)	−0.1992 (4)	0.0431 (14)
H3A	0.6681	0.4032	−0.2593	0.052*
C4A	0.6418 (7)	0.39425 (12)	−0.1232 (4)	0.0367 (13)
H4A	0.6316	0.3735	−0.1312	0.044*
C5A	0.6349 (7)	0.40832 (11)	−0.0335 (4)	0.0338 (12)
C6A	0.6379 (6)	0.39114 (11)	0.0605 (4)	0.0278 (11)
C7A	0.6596 (8)	0.34938 (11)	0.1572 (4)	0.0359 (12)
C8A	0.6498 (7)	0.39412 (11)	0.2283 (4)	0.0347 (12)
C9A	0.6396 (7)	0.41429 (10)	0.3126 (4)	0.0340 (12)
C10A	0.6332 (8)	0.40315 (11)	0.4047 (4)	0.0394 (12)
H10A	0.6439	0.3827	0.4202	0.047*
C11A	0.6101 (8)	0.42368 (11)	0.4723 (4)	0.0423 (14)
H11A	0.6030	0.4172	0.5343	0.051*
C12A	0.5977 (8)	0.45368 (11)	0.4484 (4)	0.0434 (13)
H12A	0.5845	0.4677	0.4943	0.052*
C13A	0.6052 (8)	0.46259 (10)	0.3550 (4)	0.0420 (13)
H13A	0.5954	0.4830	0.3388	0.050*
C14A	0.6808 (7)	0.31603 (10)	0.1658 (4)	0.0336 (12)
C15A	0.6621 (8)	0.29847 (11)	0.0801 (4)	0.0409 (13)
H15A	0.6397	0.3073	0.0138	0.049*
C16A	0.6763 (9)	0.26788 (11)	0.0908 (5)	0.0545 (16)
H16A	0.6587	0.2557	0.0319	0.065*
C17A	0.7174 (8)	0.25594 (11)	0.1916 (5)	0.0485 (14)
H17A	0.7322	0.2353	0.2034	0.058*
C18A	0.7366 (8)	0.27509 (11)	0.2764 (5)	0.0490 (15)
H18A	0.7623	0.2667	0.3439	0.059*
Zn2	1.15633 (9)	0.335595 (13)	0.57263 (5)	0.03780 (15)
S1B	1.3216 (2)	0.32962 (3)	0.47287 (11)	0.0491 (4)
S2B	1.5981 (2)	0.33522 (3)	0.61643 (11)	0.0394 (3)
O1B	1.5579 (5)	0.33113 (9)	0.7088 (3)	0.0568 (11)
O2B	1.6729 (6)	0.36509 (8)	0.6152 (3)	0.0573 (11)
O3B	1.7323 (5)	0.31212 (7)	0.6144 (3)	0.0488 (9)
N1B	1.1554 (6)	0.38596 (9)	0.5871 (3)	0.0346 (10)
N2B	1.1616 (6)	0.34437 (9)	0.7214 (3)	0.0349 (10)
N3B	1.1836 (6)	0.29068 (8)	0.6537 (3)	0.0324 (10)
N4B	1.1384 (6)	0.37900 (9)	0.8432 (3)	0.0342 (10)
N5B	1.1660 (6)	0.32653 (8)	0.8840 (3)	0.0346 (10)
N6B	1.1486 (7)	0.33813 (8)	1.0729 (3)	0.0424 (11)
C1B	1.1598 (8)	0.40642 (12)	0.5174 (4)	0.0465 (14)
H1B	1.1732	0.3996	0.4576	0.056*
C2B	1.1458 (9)	0.43673 (12)	0.5286 (4)	0.0512 (15)
H2B	1.1537	0.4501	0.4791	0.061*
C3B	1.1196 (8)	0.44691 (11)	0.6153 (4)	0.0444 (14)
H3B	1.1020	0.4673	0.6229	0.053*
C4B	1.1199 (7)	0.42627 (10)	0.6906 (4)	0.0332 (12)
H4B	1.1101	0.4326	0.7520	0.040*
C5B	1.1350 (7)	0.39638 (10)	0.6726 (4)	0.0333 (12)
C6B	1.1428 (7)	0.37249 (11)	0.7498 (4)	0.0313 (11)
C7B	1.1478 (7)	0.35537 (11)	0.9057 (4)	0.0340 (12)
C8B	1.1711 (7)	0.32247 (11)	0.7885 (4)	0.0357 (12)
C9B	1.1915 (7)	0.29172 (10)	0.7545 (4)	0.0322 (12)
C10B	1.2232 (8)	0.26702 (10)	0.8189 (4)	0.0393 (13)
H10B	1.2315	0.2686	0.8883	0.047*
C11B	1.2430 (9)	0.23948 (12)	0.7792 (5)	0.0550 (16)
H11B	1.2631	0.2222	0.8211	0.066*
C12B	1.2326 (9)	0.23808 (12)	0.6774 (5)	0.0532 (15)
H12B	1.2448	0.2198	0.6488	0.064*
C13B	1.2036 (9)	0.26429 (11)	0.6180 (5)	0.0493 (15)
H13B	1.1980	0.2632	0.5492	0.059*
C14B	1.1474 (7)	0.36229 (11)	1.0133 (4)	0.0332 (12)
C15B	1.1457 (7)	0.39142 (11)	1.0449 (4)	0.0361 (12)
H15B	1.1418	0.4072	0.9999	0.043*
C16B	1.1499 (8)	0.39692 (11)	1.1456 (4)	0.0449 (14)
H16B	1.1507	0.4164	1.1698	0.054*
C17B	1.1529 (8)	0.37306 (12)	1.2069 (4)	0.0450 (14)
H17B	1.1560	0.3759	1.2745	0.054*
C18B	1.1512 (9)	0.34415 (13)	1.1677 (4)	0.0537 (16)
H18B	1.1520	0.3281	1.2109	0.064*
O1W	0.3129 (5)	0.46038 (7)	0.0484 (3)	0.0440 (9)
H1WA	0.268 (7)	0.4671 (9)	0.090 (3)	0.066*
H1WB	0.299 (7)	0.4719 (8)	−0.004 (2)	0.066*
O2W	0.8543 (5)	0.33133 (8)	0.4705 (3)	0.0472 (9)
H2WA	0.807 (7)	0.3260 (9)	0.513 (3)	0.071*
H2WB	0.815 (7)	0.3207 (9)	0.412 (2)	0.071*
O3W	0.8105 (8)	0.29118 (10)	0.8991 (3)	0.0849 (15)
H3WA	0.729 (7)	0.3005 (9)	0.839 (3)	0.127*
H3WB	0.927 (3)	0.2992 (8)	0.940 (4)	0.127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0510 (4)	0.0296 (3)	0.0379 (3)	−0.0004 (3)	0.0244 (3)	0.0000 (3)
S1A	0.0468 (9)	0.0343 (7)	0.0413 (8)	0.0020 (7)	0.0214 (7)	0.0002 (6)
S2A	0.0455 (9)	0.0403 (8)	0.0407 (8)	0.0004 (7)	0.0211 (7)	−0.0051 (6)
O1A	0.076 (3)	0.030 (2)	0.062 (2)	0.010 (2)	0.040 (2)	0.0103 (18)
O2A	0.072 (3)	0.083 (3)	0.089 (3)	0.009 (3)	0.064 (3)	0.005 (3)
O3A	0.060 (3)	0.072 (3)	0.066 (3)	0.017 (2)	−0.002 (2)	−0.035 (2)
N1A	0.050 (3)	0.028 (2)	0.035 (2)	−0.002 (2)	0.018 (2)	−0.0035 (19)
N2A	0.033 (2)	0.037 (2)	0.034 (2)	−0.002 (2)	0.018 (2)	−0.002 (2)
N3A	0.033 (2)	0.039 (3)	0.038 (2)	0.010 (2)	0.020 (2)	0.003 (2)
N4A	0.040 (3)	0.041 (3)	0.025 (2)	0.003 (2)	0.014 (2)	−0.001 (2)
N5A	0.048 (3)	0.019 (2)	0.037 (2)	0.0032 (19)	0.024 (2)	−0.0019 (18)
N6A	0.055 (3)	0.036 (3)	0.039 (2)	0.004 (2)	0.028 (2)	0.000 (2)
C1A	0.070 (4)	0.040 (3)	0.042 (3)	−0.006 (3)	0.033 (3)	0.002 (3)
C2A	0.062 (4)	0.043 (3)	0.044 (3)	−0.009 (3)	0.030 (3)	−0.003 (3)
C3A	0.047 (4)	0.061 (4)	0.028 (3)	0.010 (3)	0.023 (3)	−0.002 (3)
C4A	0.018 (3)	0.054 (3)	0.032 (3)	−0.008 (2)	0.007 (2)	−0.011 (2)
C5A	0.029 (3)	0.043 (3)	0.024 (3)	−0.004 (2)	0.010 (2)	0.001 (2)
C6A	0.012 (2)	0.042 (3)	0.019 (2)	−0.001 (2)	0.001 (2)	0.004 (2)
C7A	0.039 (3)	0.039 (3)	0.032 (3)	0.007 (2)	0.020 (3)	0.005 (2)
C8A	0.035 (3)	0.042 (3)	0.028 (3)	−0.007 (2)	0.015 (2)	0.001 (2)
C9A	0.043 (3)	0.034 (3)	0.020 (2)	−0.002 (2)	0.011 (2)	−0.015 (2)
C10A	0.054 (3)	0.031 (3)	0.033 (3)	−0.008 (3)	0.021 (3)	−0.002 (2)
C11A	0.056 (4)	0.051 (4)	0.028 (3)	0.005 (3)	0.026 (3)	−0.006 (3)
C12A	0.054 (4)	0.034 (3)	0.038 (3)	−0.001 (3)	0.020 (3)	−0.011 (3)
C13A	0.067 (4)	0.023 (3)	0.039 (3)	−0.003 (3)	0.029 (3)	−0.007 (2)
C14A	0.040 (3)	0.026 (3)	0.034 (3)	−0.001 (2)	0.017 (3)	0.002 (2)
C15A	0.058 (4)	0.039 (3)	0.033 (3)	−0.008 (3)	0.028 (3)	−0.008 (3)
C16A	0.071 (4)	0.030 (3)	0.071 (4)	−0.014 (3)	0.041 (4)	−0.014 (3)
C17A	0.044 (4)	0.028 (3)	0.062 (4)	0.007 (3)	0.018 (3)	0.000 (3)
C18A	0.060 (4)	0.031 (3)	0.051 (4)	−0.003 (3)	0.024 (3)	0.000 (3)
Zn2	0.0451 (4)	0.0405 (3)	0.0328 (3)	−0.0001 (3)	0.0233 (3)	−0.0032 (3)
S1B	0.0506 (9)	0.0667 (10)	0.0346 (7)	0.0042 (8)	0.0246 (7)	−0.0078 (7)
S2B	0.0421 (8)	0.0422 (8)	0.0421 (8)	0.0022 (7)	0.0273 (7)	0.0027 (7)
O1B	0.046 (2)	0.095 (3)	0.039 (2)	−0.023 (2)	0.0285 (19)	−0.007 (2)
O2B	0.078 (3)	0.041 (2)	0.063 (3)	−0.013 (2)	0.043 (2)	−0.0079 (19)
O3B	0.050 (2)	0.038 (2)	0.069 (3)	0.0069 (18)	0.037 (2)	0.0074 (19)
N1B	0.034 (2)	0.042 (2)	0.030 (2)	−0.001 (2)	0.018 (2)	−0.003 (2)
N2B	0.044 (3)	0.035 (2)	0.028 (2)	−0.001 (2)	0.020 (2)	0.0043 (19)
N3B	0.035 (3)	0.035 (2)	0.034 (2)	0.0037 (19)	0.022 (2)	0.0001 (19)
N4B	0.036 (3)	0.038 (2)	0.030 (2)	−0.007 (2)	0.017 (2)	−0.0034 (19)
N5B	0.037 (3)	0.025 (2)	0.040 (3)	0.0018 (18)	0.017 (2)	−0.0001 (18)
N6B	0.069 (3)	0.029 (2)	0.033 (2)	−0.006 (2)	0.028 (2)	−0.002 (2)
C1B	0.058 (4)	0.059 (4)	0.031 (3)	−0.011 (3)	0.029 (3)	−0.007 (3)
C2B	0.074 (4)	0.047 (4)	0.048 (3)	−0.002 (3)	0.042 (3)	0.016 (3)
C3B	0.063 (4)	0.034 (3)	0.044 (3)	−0.002 (3)	0.033 (3)	0.009 (3)
C4B	0.036 (3)	0.042 (3)	0.021 (2)	−0.001 (2)	0.014 (2)	−0.007 (2)
C5B	0.035 (3)	0.031 (3)	0.035 (3)	0.001 (2)	0.019 (3)	−0.004 (2)
C6B	0.027 (3)	0.040 (3)	0.031 (3)	−0.003 (2)	0.018 (2)	0.005 (2)
C7B	0.029 (3)	0.044 (3)	0.027 (3)	0.002 (2)	0.012 (2)	0.010 (2)
C8B	0.026 (3)	0.040 (3)	0.033 (3)	−0.011 (2)	0.009 (2)	0.000 (2)
C9B	0.032 (3)	0.020 (3)	0.046 (3)	0.002 (2)	0.020 (3)	0.002 (2)
C10B	0.053 (4)	0.038 (3)	0.027 (3)	−0.003 (3)	0.020 (3)	0.005 (2)
C11B	0.066 (4)	0.035 (3)	0.054 (4)	−0.004 (3)	0.023 (3)	−0.005 (3)
C12B	0.060 (4)	0.044 (3)	0.061 (4)	−0.001 (3)	0.034 (3)	−0.011 (3)
C13B	0.070 (4)	0.029 (3)	0.055 (4)	0.008 (3)	0.035 (3)	−0.005 (3)
C14B	0.019 (3)	0.045 (3)	0.032 (3)	−0.008 (2)	0.010 (2)	−0.006 (2)
C15B	0.041 (3)	0.032 (3)	0.035 (3)	0.001 (2)	0.019 (3)	−0.004 (2)
C16B	0.053 (4)	0.037 (3)	0.042 (3)	−0.013 (3)	0.021 (3)	−0.012 (3)
C17B	0.065 (4)	0.048 (3)	0.034 (3)	0.006 (3)	0.033 (3)	−0.004 (3)
C18B	0.068 (4)	0.066 (4)	0.034 (3)	−0.005 (3)	0.031 (3)	0.005 (3)
O1W	0.043 (2)	0.052 (2)	0.041 (2)	0.0013 (18)	0.0232 (19)	0.0096 (18)
O2W	0.047 (2)	0.062 (3)	0.032 (2)	−0.005 (2)	0.0200 (19)	−0.0045 (19)
O3W	0.109 (4)	0.084 (3)	0.063 (3)	−0.037 (3)	0.044 (3)	−0.018 (3)

Geometric parameters (Å, º)

Zn1—N2A	2.067 (5)	Zn2—N1B	2.254 (5)
Zn1—O1W	2.083 (4)	Zn2—S1B	2.286 (4)
Zn1—N3A	2.215 (4)	Zn2—O1B	2.662 (4)
Zn1—S1A	2.286 (3)	S1B—S2B	2.055 (2)
Zn1—N1A	2.287 (4)	S2B—O2B	1.449 (4)
Zn1—O1A	2.654 (4)	S2B—O3B	1.455 (4)
S1A—S2A	2.074 (2)	S2B—O1B	1.461 (3)
S2A—O3A	1.438 (4)	N1B—C1B	1.337 (6)
S2A—O1A	1.445 (4)	N1B—C5B	1.345 (5)
S2A—O2A	1.451 (4)	N2B—C8B	1.323 (6)
N1A—C5A	1.337 (6)	N2B—C6B	1.342 (6)
N1A—C1A	1.342 (6)	N3B—C13B	1.313 (6)
N2A—C8A	1.335 (6)	N3B—C9B	1.363 (6)
N2A—C6A	1.339 (6)	N4B—C6B	1.336 (5)
N3A—C13A	1.318 (6)	N4B—C7B	1.341 (6)
N3A—C9A	1.353 (6)	N5B—C7B	1.342 (6)
N4A—C6A	1.329 (6)	N5B—C8B	1.350 (6)
N4A—C7A	1.355 (6)	N6B—C18B	1.326 (6)
N5A—C7A	1.329 (6)	N6B—C14B	1.352 (6)
N5A—C8A	1.335 (6)	C1B—C2B	1.370 (7)
N6A—C18A	1.314 (6)	C1B—H1B	0.9300
N6A—C14A	1.355 (5)	C2B—C3B	1.382 (7)
C1A—C2A	1.380 (7)	C2B—H2B	0.9300
C1A—H1A	0.9300	C3B—C4B	1.387 (6)
C2A—C3A	1.369 (7)	C3B—H3B	0.9300
C2A—H2A	0.9300	C4B—C5B	1.370 (6)
C3A—C4A	1.385 (6)	C4B—H4B	0.9300
C3A—H3A	0.9300	C5B—C6B	1.486 (6)
C4A—C5A	1.411 (6)	C7B—C14B	1.517 (6)
C4A—H4A	0.9300	C8B—C9B	1.481 (6)
C5A—C6A	1.495 (6)	C9B—C10B	1.358 (6)
C7A—C14A	1.493 (6)	C10B—C11B	1.382 (7)
C8A—C9A	1.502 (6)	C10B—H10B	0.9300
C9A—C10A	1.388 (6)	C11B—C12B	1.368 (7)
C10A—C11A	1.378 (6)	C11B—H11B	0.9300
C10A—H10A	0.9300	C12B—C13B	1.380 (7)
C11A—C12A	1.369 (7)	C12B—H12B	0.9300
C11A—H11A	0.9300	C13B—H13B	0.9300
C12A—C13A	1.376 (6)	C14B—C15B	1.372 (6)
C12A—H12A	0.9300	C15B—C16B	1.395 (6)
C13A—H13A	0.9300	C15B—H15B	0.9300
C14A—C15A	1.365 (6)	C16B—C17B	1.351 (7)
C15A—C16A	1.370 (7)	C16B—H16B	0.9300
C15A—H15A	0.9300	C17B—C18B	1.395 (7)
C16A—C17A	1.373 (7)	C17B—H17B	0.9300
C16A—H16A	0.9300	C18B—H18B	0.9300
C17A—C18A	1.395 (7)	O1W—H1WA	0.85 (5)
C17A—H17A	0.9300	O1W—H1WB	0.85 (3)
C18A—H18A	0.9300	O2W—H2WA	0.86 (5)
Zn2—O2W	2.005 (4)	O2W—H2WB	0.85 (3)
Zn2—N2B	2.069 (4)	O3W—H3WA	0.85 (5)
Zn2—N3B	2.251 (5)	O3W—H3WB	0.85 (4)
N2A—Zn1—O1W	99.39 (15)	N2B—Zn2—N3B	73.99 (15)
N2A—Zn1—N3A	75.13 (15)	O2W—Zn2—N1B	95.97 (15)
O1W—Zn1—N3A	89.82 (14)	N2B—Zn2—N1B	73.94 (14)
N2A—Zn1—S1A	152.83 (13)	N3B—Zn2—N1B	147.68 (15)
O1W—Zn1—S1A	107.78 (11)	O2W—Zn2—S1B	109.70 (11)
N3A—Zn1—S1A	104.13 (11)	N2B—Zn2—S1B	150.63 (12)
N2A—Zn1—N1A	73.42 (15)	N3B—Zn2—S1B	104.64 (11)
O1W—Zn1—N1A	95.98 (14)	N1B—Zn2—S1B	101.29 (11)
N3A—Zn1—N1A	148.53 (15)	O2W—Zn2—O1B	170.28 (14)
S1A—Zn1—N1A	103.43 (11)	N2B—Zn2—O1B	82.06 (14)
N2A—Zn1—O1A	84.19 (13)	N3B—Zn2—O1B	78.06 (13)
O1W—Zn1—O1A	172.93 (12)	N1B—Zn2—O1B	93.70 (13)
N3A—Zn1—O1A	85.20 (13)	S1B—Zn2—O1B	69.19 (9)
S1A—Zn1—O1A	68.76 (9)	S2B—S1B—Zn2	90.19 (8)
N1A—Zn1—O1A	90.87 (14)	O2B—S2B—O3B	111.8 (2)
S2A—S1A—Zn1	90.73 (10)	O2B—S2B—O1B	112.1 (2)
O3A—S2A—O1A	114.1 (3)	O3B—S2B—O1B	112.2 (2)
O3A—S2A—O2A	112.6 (3)	O2B—S2B—S1B	108.35 (18)
O1A—S2A—O2A	111.8 (2)	O3B—S2B—S1B	106.17 (17)
O3A—S2A—S1A	106.17 (19)	O1B—S2B—S1B	105.80 (16)
O1A—S2A—S1A	104.33 (18)	O2B—S2B—Zn2	112.50 (17)
O2A—S2A—S1A	107.04 (19)	O3B—S2B—Zn2	134.17 (16)
O3A—S2A—Zn1	133.7 (2)	O1B—S2B—Zn2	59.75 (15)
O1A—S2A—Zn1	58.46 (16)	S1B—S2B—Zn2	47.97 (6)
O2A—S2A—Zn1	111.81 (19)	S2B—O1B—Zn2	91.94 (17)
S1A—S2A—Zn1	47.38 (9)	C1B—N1B—C5B	116.7 (4)
S2A—O1A—Zn1	93.89 (18)	C1B—N1B—Zn2	127.8 (3)
C5A—N1A—C1A	117.7 (4)	C5B—N1B—Zn2	115.4 (3)
C5A—N1A—Zn1	114.4 (3)	C8B—N2B—C6B	117.5 (4)
C1A—N1A—Zn1	127.8 (3)	C8B—N2B—Zn2	121.5 (3)
C8A—N2A—C6A	116.5 (4)	C6B—N2B—Zn2	120.9 (3)
C8A—N2A—Zn1	120.8 (3)	C13B—N3B—C9B	117.3 (4)
C6A—N2A—Zn1	122.6 (3)	C13B—N3B—Zn2	127.6 (3)
C13A—N3A—C9A	117.1 (4)	C9B—N3B—Zn2	115.0 (3)
C13A—N3A—Zn1	127.7 (3)	C6B—N4B—C7B	115.5 (4)
C9A—N3A—Zn1	115.2 (3)	C7B—N5B—C8B	113.7 (4)
C6A—N4A—C7A	113.8 (4)	C18B—N6B—C14B	115.5 (4)
C7A—N5A—C8A	114.4 (4)	N1B—C1B—C2B	124.1 (5)
C18A—N6A—C14A	117.2 (4)	N1B—C1B—H1B	117.9
N1A—C1A—C2A	123.4 (5)	C2B—C1B—H1B	117.9
N1A—C1A—H1A	118.3	C1B—C2B—C3B	118.2 (5)
C2A—C1A—H1A	118.3	C1B—C2B—H2B	120.9
C3A—C2A—C1A	119.3 (5)	C3B—C2B—H2B	120.9
C3A—C2A—H2A	120.3	C2B—C3B—C4B	118.9 (5)
C1A—C2A—H2A	120.3	C2B—C3B—H3B	120.6
C2A—C3A—C4A	118.7 (5)	C4B—C3B—H3B	120.6
C2A—C3A—H3A	120.6	C5B—C4B—C3B	118.6 (4)
C4A—C3A—H3A	120.6	C5B—C4B—H4B	120.7
C3A—C4A—C5A	118.8 (5)	C3B—C4B—H4B	120.7
C3A—C4A—H4A	120.6	N1B—C5B—C4B	123.4 (4)
C5A—C4A—H4A	120.6	N1B—C5B—C6B	113.5 (4)
N1A—C5A—C4A	122.0 (5)	C4B—C5B—C6B	122.9 (4)
N1A—C5A—C6A	115.0 (4)	N4B—C6B—N2B	122.8 (4)
C4A—C5A—C6A	122.8 (5)	N4B—C6B—C5B	121.6 (4)
N4A—C6A—N2A	124.4 (4)	N2B—C6B—C5B	115.6 (4)
N4A—C6A—C5A	121.5 (4)	N4B—C7B—N5B	126.0 (4)
N2A—C6A—C5A	114.2 (4)	N4B—C7B—C14B	116.4 (4)
N5A—C7A—N4A	126.4 (4)	N5B—C7B—C14B	117.6 (4)
N5A—C7A—C14A	118.4 (4)	N2B—C8B—N5B	124.5 (4)
N4A—C7A—C14A	115.2 (4)	N2B—C8B—C9B	116.1 (4)
N5A—C8A—N2A	124.1 (4)	N5B—C8B—C9B	119.4 (4)
N5A—C8A—C9A	121.3 (4)	C10B—C9B—N3B	122.9 (4)
N2A—C8A—C9A	114.6 (4)	C10B—C9B—C8B	123.8 (4)
N3A—C9A—C10A	123.4 (4)	N3B—C9B—C8B	113.3 (4)
N3A—C9A—C8A	114.2 (4)	C9B—C10B—C11B	118.6 (5)
C10A—C9A—C8A	122.2 (4)	C9B—C10B—H10B	120.7
C11A—C10A—C9A	117.1 (5)	C11B—C10B—H10B	120.7
C11A—C10A—H10A	121.5	C12B—C11B—C10B	119.0 (5)
C9A—C10A—H10A	121.5	C12B—C11B—H11B	120.5
C12A—C11A—C10A	120.2 (5)	C10B—C11B—H11B	120.5
C12A—C11A—H11A	119.9	C11B—C12B—C13B	118.8 (5)
C10A—C11A—H11A	119.9	C11B—C12B—H12B	120.6
C11A—C12A—C13A	118.5 (5)	C13B—C12B—H12B	120.6
C11A—C12A—H12A	120.7	N3B—C13B—C12B	123.4 (5)
C13A—C12A—H12A	120.7	N3B—C13B—H13B	118.3
N3A—C13A—C12A	123.7 (5)	C12B—C13B—H13B	118.3
N3A—C13A—H13A	118.2	N6B—C14B—C15B	124.0 (4)
C12A—C13A—H13A	118.2	N6B—C14B—C7B	115.5 (4)
N6A—C14A—C15A	122.3 (4)	C15B—C14B—C7B	120.5 (4)
N6A—C14A—C7A	114.9 (4)	C14B—C15B—C16B	118.9 (5)
C15A—C14A—C7A	122.8 (4)	C14B—C15B—H15B	120.6
C14A—C15A—C16A	120.6 (5)	C16B—C15B—H15B	120.6
C14A—C15A—H15A	119.7	C17B—C16B—C15B	118.0 (5)
C16A—C15A—H15A	119.7	C17B—C16B—H16B	121.0
C15A—C16A—C17A	117.4 (5)	C15B—C16B—H16B	121.0
C15A—C16A—H16A	121.3	C16B—C17B—C18B	119.4 (5)
C17A—C16A—H16A	121.3	C16B—C17B—H17B	120.3
C16A—C17A—C18A	119.2 (5)	C18B—C17B—H17B	120.3
C16A—C17A—H17A	120.4	N6B—C18B—C17B	124.2 (5)
C18A—C17A—H17A	120.4	N6B—C18B—H18B	117.9
N6A—C18A—C17A	123.2 (5)	C17B—C18B—H18B	117.9
N6A—C18A—H18A	118.4	H1WA—O1W—H1WB	116 (4)
C17A—C18A—H18A	118.4	H2WA—O2W—H2WB	115 (4)
O2W—Zn2—N2B	99.65 (15)	H3WA—O3W—H3WB	116 (4)
O2W—Zn2—N3B	93.16 (15)
Zn1—S1A—S2A—O1A	−14.37 (17)	N5B^i—C7B^i—C14B^i—N6B^i	5.3 (6)
Zn2^i—S1B^i—S2B^i—O1B^i	−16.27 (19)	N2A—Zn1—O1W—H1WA	107 (3)
N5A—C7A—C14A—N6A	−4.8 (7)	N2B^i—Zn2^i—O2W^i—H2WA^i	25 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2A^ii	0.85 (5)	1.85 (5)	2.694 (7)	170 (4)
O1W—H1WB···S1A^iii	0.85 (3)	2.32 (3)	3.165 (6)	172 (5)
O2W—H2WA···O3B^ii	0.86 (5)	1.86 (5)	2.710 (7)	174 (5)
O2W—H2WB···N6A	0.85 (3)	1.92 (3)	2.759 (7)	168 (4)
O3W—H3WA···O1B^ii	0.85 (4)	2.11 (4)	2.951 (7)	169 (4)
O3W—H3WB···N6B	0.85 (4)	2.47 (4)	3.247 (8)	152 (3)
C3A—H3A···O2B^iv	0.93	2.44	3.329 (8)	160
C17A—H17A···O3B^v	0.93	2.45	3.235 (8)	143
C16B—H16B···O1A^vi	0.93	2.40	3.228 (8)	148

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