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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106010560/ga3004sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106010560/ga3004Isup2.hkl
Contains datablock I

CCDC reference: 609401

Comment top

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 ZnII 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 Ocoordinated 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 ππ 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—Oaqua bond, shown by the N2—Zn—Oaqua—Haqua 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 ππ contacts between interdigitated aromatic cycles belonging to different column types. (Table 3).

Experimental top

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.

Refinement top

H atoms attached to C were included in their calculated positions, with C—H = 0.93 Å, and treated as riding, with Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.5Ueq(O). Two reflections partially eclipsed by the beam-stop were removed from the data set.

Computing details top

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 top
[Figure 1] 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
[Figure 2] 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 top
Crystal data top
[Zn(S2O3)(C18H12N6)(H2O)]2·H2OF(000) = 2104
Mr = 1033.70Dx = 1.706 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.550 (5) Åθ = 7.5–15°
b = 44.57 (7) ŵ = 1.47 mm1
c = 13.791 (8) ÅT = 295 K
β = 119.88 (3)°Block, colourless
V = 4024 (7) Å30.32 × 0.16 × 0.14 mm
Z = 4
Data collection top
Rigaku AFC-6
diffractometer
4159 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.066
Graphite monochromatorθmax = 26.0°, θmin = 1.9°
ω/2θ scansh = 98
Absorption correction: ψ scan
(North et al., 1968)
k = 054
Tmin = 0.650, Tmax = 0.820l = 016
15672 measured reflections3 standard reflections every 150 reflections
7771 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.003P)2 + 7.8876P]
where P = (Fo2 + 2Fc2)/3
7771 reflections(Δ/σ)max = 0.001
586 parametersΔρmax = 0.43 e Å3
15 restraintsΔρmin = 0.90 e Å3
Crystal data top
[Zn(S2O3)(C18H12N6)(H2O)]2·H2OV = 4024 (7) Å3
Mr = 1033.70Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.550 (5) ŵ = 1.47 mm1
b = 44.57 (7) ÅT = 295 K
c = 13.791 (8) Å0.32 × 0.16 × 0.14 mm
β = 119.88 (3)°
Data collection top
Rigaku AFC-6
diffractometer
4159 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.066
Tmin = 0.650, Tmax = 0.8203 standard reflections every 150 reflections
15672 measured reflections intensity decay: none
7771 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04915 restraints
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.43 e Å3
7771 reflectionsΔρmin = 0.90 e Å3
586 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.62864 (10)0.454676 (12)0.13133 (5)0.03851 (16)
S1A0.7748 (2)0.50121 (3)0.16398 (11)0.0410 (3)
S2A1.0638 (2)0.48221 (3)0.23751 (11)0.0423 (3)
O1A1.0320 (6)0.45137 (7)0.2573 (3)0.0535 (10)
O2A1.1340 (6)0.48455 (9)0.1572 (3)0.0708 (12)
O3A1.1880 (6)0.49917 (9)0.3377 (3)0.0808 (14)
N1A0.6445 (6)0.43814 (9)0.0211 (3)0.0389 (11)
N2A0.6421 (6)0.40838 (8)0.1411 (3)0.0340 (9)
N3A0.6254 (6)0.44385 (9)0.2872 (3)0.0355 (10)
N4A0.6376 (6)0.36134 (9)0.0615 (3)0.0361 (10)
N5A0.6655 (6)0.36440 (8)0.2420 (3)0.0336 (10)
N6A0.7202 (6)0.30441 (9)0.2654 (3)0.0412 (11)
C1A0.6695 (8)0.45457 (12)0.0950 (4)0.0489 (14)
H1A0.68070.47530.08560.059*
C2A0.6795 (8)0.44233 (12)0.1840 (4)0.0485 (14)
H2A0.69660.45460.23320.058*
C3A0.6639 (8)0.41189 (12)0.1992 (4)0.0431 (14)
H3A0.66810.40320.25930.052*
C4A0.6418 (7)0.39425 (12)0.1232 (4)0.0367 (13)
H4A0.63160.37350.13120.044*
C5A0.6349 (7)0.40832 (11)0.0335 (4)0.0338 (12)
C6A0.6379 (6)0.39114 (11)0.0605 (4)0.0278 (11)
C7A0.6596 (8)0.34938 (11)0.1572 (4)0.0359 (12)
C8A0.6498 (7)0.39412 (11)0.2283 (4)0.0347 (12)
C9A0.6396 (7)0.41429 (10)0.3126 (4)0.0340 (12)
C10A0.6332 (8)0.40315 (11)0.4047 (4)0.0394 (12)
H10A0.64390.38270.42020.047*
C11A0.6101 (8)0.42368 (11)0.4723 (4)0.0423 (14)
H11A0.60300.41720.53430.051*
C12A0.5977 (8)0.45368 (11)0.4484 (4)0.0434 (13)
H12A0.58450.46770.49430.052*
C13A0.6052 (8)0.46259 (10)0.3550 (4)0.0420 (13)
H13A0.59540.48300.33880.050*
C14A0.6808 (7)0.31603 (10)0.1658 (4)0.0336 (12)
C15A0.6621 (8)0.29847 (11)0.0801 (4)0.0409 (13)
H15A0.63970.30730.01380.049*
C16A0.6763 (9)0.26788 (11)0.0908 (5)0.0545 (16)
H16A0.65870.25570.03190.065*
C17A0.7174 (8)0.25594 (11)0.1916 (5)0.0485 (14)
H17A0.73220.23530.20340.058*
C18A0.7366 (8)0.27509 (11)0.2764 (5)0.0490 (15)
H18A0.76230.26670.34390.059*
Zn21.15633 (9)0.335595 (13)0.57263 (5)0.03780 (15)
S1B1.3216 (2)0.32962 (3)0.47287 (11)0.0491 (4)
S2B1.5981 (2)0.33522 (3)0.61643 (11)0.0394 (3)
O1B1.5579 (5)0.33113 (9)0.7088 (3)0.0568 (11)
O2B1.6729 (6)0.36509 (8)0.6152 (3)0.0573 (11)
O3B1.7323 (5)0.31212 (7)0.6144 (3)0.0488 (9)
N1B1.1554 (6)0.38596 (9)0.5871 (3)0.0346 (10)
N2B1.1616 (6)0.34437 (9)0.7214 (3)0.0349 (10)
N3B1.1836 (6)0.29068 (8)0.6537 (3)0.0324 (10)
N4B1.1384 (6)0.37900 (9)0.8432 (3)0.0342 (10)
N5B1.1660 (6)0.32653 (8)0.8840 (3)0.0346 (10)
N6B1.1486 (7)0.33813 (8)1.0729 (3)0.0424 (11)
C1B1.1598 (8)0.40642 (12)0.5174 (4)0.0465 (14)
H1B1.17320.39960.45760.056*
C2B1.1458 (9)0.43673 (12)0.5286 (4)0.0512 (15)
H2B1.15370.45010.47910.061*
C3B1.1196 (8)0.44691 (11)0.6153 (4)0.0444 (14)
H3B1.10200.46730.62290.053*
C4B1.1199 (7)0.42627 (10)0.6906 (4)0.0332 (12)
H4B1.11010.43260.75200.040*
C5B1.1350 (7)0.39638 (10)0.6726 (4)0.0333 (12)
C6B1.1428 (7)0.37249 (11)0.7498 (4)0.0313 (11)
C7B1.1478 (7)0.35537 (11)0.9057 (4)0.0340 (12)
C8B1.1711 (7)0.32247 (11)0.7885 (4)0.0357 (12)
C9B1.1915 (7)0.29172 (10)0.7545 (4)0.0322 (12)
C10B1.2232 (8)0.26702 (10)0.8189 (4)0.0393 (13)
H10B1.23150.26860.88830.047*
C11B1.2430 (9)0.23948 (12)0.7792 (5)0.0550 (16)
H11B1.26310.22220.82110.066*
C12B1.2326 (9)0.23808 (12)0.6774 (5)0.0532 (15)
H12B1.24480.21980.64880.064*
C13B1.2036 (9)0.26429 (11)0.6180 (5)0.0493 (15)
H13B1.19800.26320.54920.059*
C14B1.1474 (7)0.36229 (11)1.0133 (4)0.0332 (12)
C15B1.1457 (7)0.39142 (11)1.0449 (4)0.0361 (12)
H15B1.14180.40720.99990.043*
C16B1.1499 (8)0.39692 (11)1.1456 (4)0.0449 (14)
H16B1.15070.41641.16980.054*
C17B1.1529 (8)0.37306 (12)1.2069 (4)0.0450 (14)
H17B1.15600.37591.27450.054*
C18B1.1512 (9)0.34415 (13)1.1677 (4)0.0537 (16)
H18B1.15200.32811.21090.064*
O1W0.3129 (5)0.46038 (7)0.0484 (3)0.0440 (9)
H1WA0.268 (7)0.4671 (9)0.090 (3)0.066*
H1WB0.299 (7)0.4719 (8)0.004 (2)0.066*
O2W0.8543 (5)0.33133 (8)0.4705 (3)0.0472 (9)
H2WA0.807 (7)0.3260 (9)0.513 (3)0.071*
H2WB0.815 (7)0.3207 (9)0.412 (2)0.071*
O3W0.8105 (8)0.29118 (10)0.8991 (3)0.0849 (15)
H3WA0.729 (7)0.3005 (9)0.839 (3)0.127*
H3WB0.927 (3)0.2992 (8)0.940 (4)0.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0510 (4)0.0296 (3)0.0379 (3)0.0004 (3)0.0244 (3)0.0000 (3)
S1A0.0468 (9)0.0343 (7)0.0413 (8)0.0020 (7)0.0214 (7)0.0002 (6)
S2A0.0455 (9)0.0403 (8)0.0407 (8)0.0004 (7)0.0211 (7)0.0051 (6)
O1A0.076 (3)0.030 (2)0.062 (2)0.010 (2)0.040 (2)0.0103 (18)
O2A0.072 (3)0.083 (3)0.089 (3)0.009 (3)0.064 (3)0.005 (3)
O3A0.060 (3)0.072 (3)0.066 (3)0.017 (2)0.002 (2)0.035 (2)
N1A0.050 (3)0.028 (2)0.035 (2)0.002 (2)0.018 (2)0.0035 (19)
N2A0.033 (2)0.037 (2)0.034 (2)0.002 (2)0.018 (2)0.002 (2)
N3A0.033 (2)0.039 (3)0.038 (2)0.010 (2)0.020 (2)0.003 (2)
N4A0.040 (3)0.041 (3)0.025 (2)0.003 (2)0.014 (2)0.001 (2)
N5A0.048 (3)0.019 (2)0.037 (2)0.0032 (19)0.024 (2)0.0019 (18)
N6A0.055 (3)0.036 (3)0.039 (2)0.004 (2)0.028 (2)0.000 (2)
C1A0.070 (4)0.040 (3)0.042 (3)0.006 (3)0.033 (3)0.002 (3)
C2A0.062 (4)0.043 (3)0.044 (3)0.009 (3)0.030 (3)0.003 (3)
C3A0.047 (4)0.061 (4)0.028 (3)0.010 (3)0.023 (3)0.002 (3)
C4A0.018 (3)0.054 (3)0.032 (3)0.008 (2)0.007 (2)0.011 (2)
C5A0.029 (3)0.043 (3)0.024 (3)0.004 (2)0.010 (2)0.001 (2)
C6A0.012 (2)0.042 (3)0.019 (2)0.001 (2)0.001 (2)0.004 (2)
C7A0.039 (3)0.039 (3)0.032 (3)0.007 (2)0.020 (3)0.005 (2)
C8A0.035 (3)0.042 (3)0.028 (3)0.007 (2)0.015 (2)0.001 (2)
C9A0.043 (3)0.034 (3)0.020 (2)0.002 (2)0.011 (2)0.015 (2)
C10A0.054 (3)0.031 (3)0.033 (3)0.008 (3)0.021 (3)0.002 (2)
C11A0.056 (4)0.051 (4)0.028 (3)0.005 (3)0.026 (3)0.006 (3)
C12A0.054 (4)0.034 (3)0.038 (3)0.001 (3)0.020 (3)0.011 (3)
C13A0.067 (4)0.023 (3)0.039 (3)0.003 (3)0.029 (3)0.007 (2)
C14A0.040 (3)0.026 (3)0.034 (3)0.001 (2)0.017 (3)0.002 (2)
C15A0.058 (4)0.039 (3)0.033 (3)0.008 (3)0.028 (3)0.008 (3)
C16A0.071 (4)0.030 (3)0.071 (4)0.014 (3)0.041 (4)0.014 (3)
C17A0.044 (4)0.028 (3)0.062 (4)0.007 (3)0.018 (3)0.000 (3)
C18A0.060 (4)0.031 (3)0.051 (4)0.003 (3)0.024 (3)0.000 (3)
Zn20.0451 (4)0.0405 (3)0.0328 (3)0.0001 (3)0.0233 (3)0.0032 (3)
S1B0.0506 (9)0.0667 (10)0.0346 (7)0.0042 (8)0.0246 (7)0.0078 (7)
S2B0.0421 (8)0.0422 (8)0.0421 (8)0.0022 (7)0.0273 (7)0.0027 (7)
O1B0.046 (2)0.095 (3)0.039 (2)0.023 (2)0.0285 (19)0.007 (2)
O2B0.078 (3)0.041 (2)0.063 (3)0.013 (2)0.043 (2)0.0079 (19)
O3B0.050 (2)0.038 (2)0.069 (3)0.0069 (18)0.037 (2)0.0074 (19)
N1B0.034 (2)0.042 (2)0.030 (2)0.001 (2)0.018 (2)0.003 (2)
N2B0.044 (3)0.035 (2)0.028 (2)0.001 (2)0.020 (2)0.0043 (19)
N3B0.035 (3)0.035 (2)0.034 (2)0.0037 (19)0.022 (2)0.0001 (19)
N4B0.036 (3)0.038 (2)0.030 (2)0.007 (2)0.017 (2)0.0034 (19)
N5B0.037 (3)0.025 (2)0.040 (3)0.0018 (18)0.017 (2)0.0001 (18)
N6B0.069 (3)0.029 (2)0.033 (2)0.006 (2)0.028 (2)0.002 (2)
C1B0.058 (4)0.059 (4)0.031 (3)0.011 (3)0.029 (3)0.007 (3)
C2B0.074 (4)0.047 (4)0.048 (3)0.002 (3)0.042 (3)0.016 (3)
C3B0.063 (4)0.034 (3)0.044 (3)0.002 (3)0.033 (3)0.009 (3)
C4B0.036 (3)0.042 (3)0.021 (2)0.001 (2)0.014 (2)0.007 (2)
C5B0.035 (3)0.031 (3)0.035 (3)0.001 (2)0.019 (3)0.004 (2)
C6B0.027 (3)0.040 (3)0.031 (3)0.003 (2)0.018 (2)0.005 (2)
C7B0.029 (3)0.044 (3)0.027 (3)0.002 (2)0.012 (2)0.010 (2)
C8B0.026 (3)0.040 (3)0.033 (3)0.011 (2)0.009 (2)0.000 (2)
C9B0.032 (3)0.020 (3)0.046 (3)0.002 (2)0.020 (3)0.002 (2)
C10B0.053 (4)0.038 (3)0.027 (3)0.003 (3)0.020 (3)0.005 (2)
C11B0.066 (4)0.035 (3)0.054 (4)0.004 (3)0.023 (3)0.005 (3)
C12B0.060 (4)0.044 (3)0.061 (4)0.001 (3)0.034 (3)0.011 (3)
C13B0.070 (4)0.029 (3)0.055 (4)0.008 (3)0.035 (3)0.005 (3)
C14B0.019 (3)0.045 (3)0.032 (3)0.008 (2)0.010 (2)0.006 (2)
C15B0.041 (3)0.032 (3)0.035 (3)0.001 (2)0.019 (3)0.004 (2)
C16B0.053 (4)0.037 (3)0.042 (3)0.013 (3)0.021 (3)0.012 (3)
C17B0.065 (4)0.048 (3)0.034 (3)0.006 (3)0.033 (3)0.004 (3)
C18B0.068 (4)0.066 (4)0.034 (3)0.005 (3)0.031 (3)0.005 (3)
O1W0.043 (2)0.052 (2)0.041 (2)0.0013 (18)0.0232 (19)0.0096 (18)
O2W0.047 (2)0.062 (3)0.032 (2)0.005 (2)0.0200 (19)0.0045 (19)
O3W0.109 (4)0.084 (3)0.063 (3)0.037 (3)0.044 (3)0.018 (3)
Geometric parameters (Å, º) top
Zn1—N2A2.067 (5)Zn2—N1B2.254 (5)
Zn1—O1W2.083 (4)Zn2—S1B2.286 (4)
Zn1—N3A2.215 (4)Zn2—O1B2.662 (4)
Zn1—S1A2.286 (3)S1B—S2B2.055 (2)
Zn1—N1A2.287 (4)S2B—O2B1.449 (4)
Zn1—O1A2.654 (4)S2B—O3B1.455 (4)
S1A—S2A2.074 (2)S2B—O1B1.461 (3)
S2A—O3A1.438 (4)N1B—C1B1.337 (6)
S2A—O1A1.445 (4)N1B—C5B1.345 (5)
S2A—O2A1.451 (4)N2B—C8B1.323 (6)
N1A—C5A1.337 (6)N2B—C6B1.342 (6)
N1A—C1A1.342 (6)N3B—C13B1.313 (6)
N2A—C8A1.335 (6)N3B—C9B1.363 (6)
N2A—C6A1.339 (6)N4B—C6B1.336 (5)
N3A—C13A1.318 (6)N4B—C7B1.341 (6)
N3A—C9A1.353 (6)N5B—C7B1.342 (6)
N4A—C6A1.329 (6)N5B—C8B1.350 (6)
N4A—C7A1.355 (6)N6B—C18B1.326 (6)
N5A—C7A1.329 (6)N6B—C14B1.352 (6)
N5A—C8A1.335 (6)C1B—C2B1.370 (7)
N6A—C18A1.314 (6)C1B—H1B0.9300
N6A—C14A1.355 (5)C2B—C3B1.382 (7)
C1A—C2A1.380 (7)C2B—H2B0.9300
C1A—H1A0.9300C3B—C4B1.387 (6)
C2A—C3A1.369 (7)C3B—H3B0.9300
C2A—H2A0.9300C4B—C5B1.370 (6)
C3A—C4A1.385 (6)C4B—H4B0.9300
C3A—H3A0.9300C5B—C6B1.486 (6)
C4A—C5A1.411 (6)C7B—C14B1.517 (6)
C4A—H4A0.9300C8B—C9B1.481 (6)
C5A—C6A1.495 (6)C9B—C10B1.358 (6)
C7A—C14A1.493 (6)C10B—C11B1.382 (7)
C8A—C9A1.502 (6)C10B—H10B0.9300
C9A—C10A1.388 (6)C11B—C12B1.368 (7)
C10A—C11A1.378 (6)C11B—H11B0.9300
C10A—H10A0.9300C12B—C13B1.380 (7)
C11A—C12A1.369 (7)C12B—H12B0.9300
C11A—H11A0.9300C13B—H13B0.9300
C12A—C13A1.376 (6)C14B—C15B1.372 (6)
C12A—H12A0.9300C15B—C16B1.395 (6)
C13A—H13A0.9300C15B—H15B0.9300
C14A—C15A1.365 (6)C16B—C17B1.351 (7)
C15A—C16A1.370 (7)C16B—H16B0.9300
C15A—H15A0.9300C17B—C18B1.395 (7)
C16A—C17A1.373 (7)C17B—H17B0.9300
C16A—H16A0.9300C18B—H18B0.9300
C17A—C18A1.395 (7)O1W—H1WA0.85 (5)
C17A—H17A0.9300O1W—H1WB0.85 (3)
C18A—H18A0.9300O2W—H2WA0.86 (5)
Zn2—O2W2.005 (4)O2W—H2WB0.85 (3)
Zn2—N2B2.069 (4)O3W—H3WA0.85 (5)
Zn2—N3B2.251 (5)O3W—H3WB0.85 (4)
N2A—Zn1—O1W99.39 (15)N2B—Zn2—N3B73.99 (15)
N2A—Zn1—N3A75.13 (15)O2W—Zn2—N1B95.97 (15)
O1W—Zn1—N3A89.82 (14)N2B—Zn2—N1B73.94 (14)
N2A—Zn1—S1A152.83 (13)N3B—Zn2—N1B147.68 (15)
O1W—Zn1—S1A107.78 (11)O2W—Zn2—S1B109.70 (11)
N3A—Zn1—S1A104.13 (11)N2B—Zn2—S1B150.63 (12)
N2A—Zn1—N1A73.42 (15)N3B—Zn2—S1B104.64 (11)
O1W—Zn1—N1A95.98 (14)N1B—Zn2—S1B101.29 (11)
N3A—Zn1—N1A148.53 (15)O2W—Zn2—O1B170.28 (14)
S1A—Zn1—N1A103.43 (11)N2B—Zn2—O1B82.06 (14)
N2A—Zn1—O1A84.19 (13)N3B—Zn2—O1B78.06 (13)
O1W—Zn1—O1A172.93 (12)N1B—Zn2—O1B93.70 (13)
N3A—Zn1—O1A85.20 (13)S1B—Zn2—O1B69.19 (9)
S1A—Zn1—O1A68.76 (9)S2B—S1B—Zn290.19 (8)
N1A—Zn1—O1A90.87 (14)O2B—S2B—O3B111.8 (2)
S2A—S1A—Zn190.73 (10)O2B—S2B—O1B112.1 (2)
O3A—S2A—O1A114.1 (3)O3B—S2B—O1B112.2 (2)
O3A—S2A—O2A112.6 (3)O2B—S2B—S1B108.35 (18)
O1A—S2A—O2A111.8 (2)O3B—S2B—S1B106.17 (17)
O3A—S2A—S1A106.17 (19)O1B—S2B—S1B105.80 (16)
O1A—S2A—S1A104.33 (18)O2B—S2B—Zn2112.50 (17)
O2A—S2A—S1A107.04 (19)O3B—S2B—Zn2134.17 (16)
O3A—S2A—Zn1133.7 (2)O1B—S2B—Zn259.75 (15)
O1A—S2A—Zn158.46 (16)S1B—S2B—Zn247.97 (6)
O2A—S2A—Zn1111.81 (19)S2B—O1B—Zn291.94 (17)
S1A—S2A—Zn147.38 (9)C1B—N1B—C5B116.7 (4)
S2A—O1A—Zn193.89 (18)C1B—N1B—Zn2127.8 (3)
C5A—N1A—C1A117.7 (4)C5B—N1B—Zn2115.4 (3)
C5A—N1A—Zn1114.4 (3)C8B—N2B—C6B117.5 (4)
C1A—N1A—Zn1127.8 (3)C8B—N2B—Zn2121.5 (3)
C8A—N2A—C6A116.5 (4)C6B—N2B—Zn2120.9 (3)
C8A—N2A—Zn1120.8 (3)C13B—N3B—C9B117.3 (4)
C6A—N2A—Zn1122.6 (3)C13B—N3B—Zn2127.6 (3)
C13A—N3A—C9A117.1 (4)C9B—N3B—Zn2115.0 (3)
C13A—N3A—Zn1127.7 (3)C6B—N4B—C7B115.5 (4)
C9A—N3A—Zn1115.2 (3)C7B—N5B—C8B113.7 (4)
C6A—N4A—C7A113.8 (4)C18B—N6B—C14B115.5 (4)
C7A—N5A—C8A114.4 (4)N1B—C1B—C2B124.1 (5)
C18A—N6A—C14A117.2 (4)N1B—C1B—H1B117.9
N1A—C1A—C2A123.4 (5)C2B—C1B—H1B117.9
N1A—C1A—H1A118.3C1B—C2B—C3B118.2 (5)
C2A—C1A—H1A118.3C1B—C2B—H2B120.9
C3A—C2A—C1A119.3 (5)C3B—C2B—H2B120.9
C3A—C2A—H2A120.3C2B—C3B—C4B118.9 (5)
C1A—C2A—H2A120.3C2B—C3B—H3B120.6
C2A—C3A—C4A118.7 (5)C4B—C3B—H3B120.6
C2A—C3A—H3A120.6C5B—C4B—C3B118.6 (4)
C4A—C3A—H3A120.6C5B—C4B—H4B120.7
C3A—C4A—C5A118.8 (5)C3B—C4B—H4B120.7
C3A—C4A—H4A120.6N1B—C5B—C4B123.4 (4)
C5A—C4A—H4A120.6N1B—C5B—C6B113.5 (4)
N1A—C5A—C4A122.0 (5)C4B—C5B—C6B122.9 (4)
N1A—C5A—C6A115.0 (4)N4B—C6B—N2B122.8 (4)
C4A—C5A—C6A122.8 (5)N4B—C6B—C5B121.6 (4)
N4A—C6A—N2A124.4 (4)N2B—C6B—C5B115.6 (4)
N4A—C6A—C5A121.5 (4)N4B—C7B—N5B126.0 (4)
N2A—C6A—C5A114.2 (4)N4B—C7B—C14B116.4 (4)
N5A—C7A—N4A126.4 (4)N5B—C7B—C14B117.6 (4)
N5A—C7A—C14A118.4 (4)N2B—C8B—N5B124.5 (4)
N4A—C7A—C14A115.2 (4)N2B—C8B—C9B116.1 (4)
N5A—C8A—N2A124.1 (4)N5B—C8B—C9B119.4 (4)
N5A—C8A—C9A121.3 (4)C10B—C9B—N3B122.9 (4)
N2A—C8A—C9A114.6 (4)C10B—C9B—C8B123.8 (4)
N3A—C9A—C10A123.4 (4)N3B—C9B—C8B113.3 (4)
N3A—C9A—C8A114.2 (4)C9B—C10B—C11B118.6 (5)
C10A—C9A—C8A122.2 (4)C9B—C10B—H10B120.7
C11A—C10A—C9A117.1 (5)C11B—C10B—H10B120.7
C11A—C10A—H10A121.5C12B—C11B—C10B119.0 (5)
C9A—C10A—H10A121.5C12B—C11B—H11B120.5
C12A—C11A—C10A120.2 (5)C10B—C11B—H11B120.5
C12A—C11A—H11A119.9C11B—C12B—C13B118.8 (5)
C10A—C11A—H11A119.9C11B—C12B—H12B120.6
C11A—C12A—C13A118.5 (5)C13B—C12B—H12B120.6
C11A—C12A—H12A120.7N3B—C13B—C12B123.4 (5)
C13A—C12A—H12A120.7N3B—C13B—H13B118.3
N3A—C13A—C12A123.7 (5)C12B—C13B—H13B118.3
N3A—C13A—H13A118.2N6B—C14B—C15B124.0 (4)
C12A—C13A—H13A118.2N6B—C14B—C7B115.5 (4)
N6A—C14A—C15A122.3 (4)C15B—C14B—C7B120.5 (4)
N6A—C14A—C7A114.9 (4)C14B—C15B—C16B118.9 (5)
C15A—C14A—C7A122.8 (4)C14B—C15B—H15B120.6
C14A—C15A—C16A120.6 (5)C16B—C15B—H15B120.6
C14A—C15A—H15A119.7C17B—C16B—C15B118.0 (5)
C16A—C15A—H15A119.7C17B—C16B—H16B121.0
C15A—C16A—C17A117.4 (5)C15B—C16B—H16B121.0
C15A—C16A—H16A121.3C16B—C17B—C18B119.4 (5)
C17A—C16A—H16A121.3C16B—C17B—H17B120.3
C16A—C17A—C18A119.2 (5)C18B—C17B—H17B120.3
C16A—C17A—H17A120.4N6B—C18B—C17B124.2 (5)
C18A—C17A—H17A120.4N6B—C18B—H18B117.9
N6A—C18A—C17A123.2 (5)C17B—C18B—H18B117.9
N6A—C18A—H18A118.4H1WA—O1W—H1WB116 (4)
C17A—C18A—H18A118.4H2WA—O2W—H2WB115 (4)
O2W—Zn2—N2B99.65 (15)H3WA—O3W—H3WB116 (4)
O2W—Zn2—N3B93.16 (15)
Zn1—S1A—S2A—O1A14.37 (17)N5Bi—C7Bi—C14Bi—N6Bi5.3 (6)
Zn2i—S1Bi—S2Bi—O1Bi16.27 (19)N2A—Zn1—O1W—H1WA107 (3)
N5A—C7A—C14A—N6A4.8 (7)N2Bi—Zn2i—O2Wi—H2WAi25 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2Aii0.85 (5)1.85 (5)2.694 (7)170 (4)
O1W—H1WB···S1Aiii0.85 (3)2.32 (3)3.165 (6)172 (5)
O2W—H2WA···O3Bii0.86 (5)1.86 (5)2.710 (7)174 (5)
O2W—H2WB···N6A0.85 (3)1.92 (3)2.759 (7)168 (4)
O3W—H3WA···O1Bii0.85 (4)2.11 (4)2.951 (7)169 (4)
O3W—H3WB···N6B0.85 (4)2.47 (4)3.247 (8)152 (3)
C3A—H3A···O2Biv0.932.443.329 (8)160
C17A—H17A···O3Bv0.932.453.235 (8)143
C16B—H16B···O1Avi0.932.403.228 (8)148
Symmetry codes: (ii) x1, y, z; (iii) x+1, y+1, z; (iv) x1, y, z1; (v) x1, y+1/2, z1/2; (vi) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Zn(S2O3)(C18H12N6)(H2O)]2·H2O
Mr1033.70
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)7.550 (5), 44.57 (7), 13.791 (8)
β (°) 119.88 (3)
V3)4024 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.47
Crystal size (mm)0.32 × 0.16 × 0.14
Data collection
DiffractometerRigaku AFC-6
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.650, 0.820
No. of measured, independent and
observed [I > 2σ(I)] reflections
15672, 7771, 4159
Rint0.066
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.083, 1.11
No. of reflections7771
No. of parameters586
No. of restraints15
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.90

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Bruker, 2000) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Zn1—N2A2.067 (5)Zn2—O2W2.005 (4)
Zn1—O1W2.083 (4)Zn2—N2B2.069 (4)
Zn1—N3A2.215 (4)Zn2—N3B2.251 (5)
Zn1—S1A2.286 (3)Zn2—N1B2.254 (5)
Zn1—N1A2.287 (4)Zn2—S1B2.286 (4)
Zn1—O1A2.654 (4)Zn2—O1B2.662 (4)
S1A—S2A2.074 (2)S1B—S2B2.055 (2)
S2A—O3A1.438 (4)S2B—O2B1.449 (4)
S2A—O1A1.445 (4)S2B—O3B1.455 (4)
S2A—O2A1.451 (4)S2B—O1B1.461 (3)
Zn1—S1A—S2A—O1A14.37 (17)N5Bi—C7Bi—C14Bi—N6Bi5.3 (6)
Zn2i—S1Bi—S2Bi—O1Bi16.27 (19)N2A—Zn1—O1W—H1WA107 (3)
N5A—C7A—C14A—N6A4.8 (7)N2Bi—Zn2i—O2Wi—H2WAi25 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2Aii0.85 (5)1.85 (5)2.694 (7)170 (4)
O1W—H1WB···S1Aiii0.85 (3)2.32 (3)3.165 (6)172 (5)
O2W—H2WA···O3Bii0.86 (5)1.86 (5)2.710 (7)174 (5)
O2W—H2WB···N6A0.85 (3)1.92 (3)2.759 (7)168 (4)
O3W—H3WA···O1Bii0.85 (4)2.11 (4)2.951 (7)169 (4)
O3W—H3WB···N6B0.85 (4)2.47 (4)3.247 (8)152 (3)
C3A—H3A···O2Biv0.932.443.329 (8)160
C17A—H17A···O3Bv0.932.453.235 (8)143
C16B—H16B···O1Avi0.932.403.228 (8)148
Symmetry codes: (ii) x1, y, z; (iii) x+1, y+1, z; (iv) x1, y, z1; (v) x1, y+1/2, z1/2; (vi) x, y, z+1.
ππ contacts in (I) (Å, °) top
Cg···Cgccdsaipd
Cg1···Cg4iv3.966 (7)27.1 (9)3.53 (3)
Cg2···Cg5iv3.560 (7)20.8 (15)3.33 (3)
Cg3···Cg43.663 (7)21.1 (7)3.42 (2)
Symmetry codes are as in Table 2. ccd is the centre-to-centre distance, sa is the (mean) slippage angle and ipd is the (mean) interplanar distance. Cg1 is the centroid of the ring N1A/C1A–C5A, Cg2 that of ring N2A/C6A/N4A/C7A/N5A/C8A, Cg3 that of ring N3A/C9A–C13A, Cg4 that of ring N1B/C2B–C5B and Cg5 that of ring N6B/C14B–C18B.
 

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