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.
Supporting information
CCDC reference: 641790
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.
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, Uiso(H) = 1.2Ueq(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.
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).
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(C
10H
8N
2)(H
2O)
4][Zn
2(S
2O
3)
3(C
10H
8N
2)
2]·2H
2O
top
Crystal data top
[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) Å3 | 0.22 × 0.10 × 0.08 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.0321P)2 + 3.2788P] where P = (Fo2 + 2Fc2)/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) |
Crystal data top
[Zn(C10H8N2)(H2O)4][Zn2(S2O3)3(C10H8N2)2]·2H2O | V = 4176.4 (3) Å3 |
Mr = 1109.12 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.6521 (8) Å | µ = 2.08 mm−1 |
b = 15.5103 (7) Å | T = 292 K |
c = 17.8922 (8) Å | 0.22 × 0.10 × 0.08 mm |
β = 115.340 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 11611 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 11255 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.851 | Rint = 0.019 |
29188 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.051 | Δρmax = 0.57 e Å−3 |
S = 0.90 | Δρmin = −0.41 e Å−3 |
11611 reflections | Absolute structure: Flack (1983), 5223 Friedel pairs |
601 parameters | Absolute structure parameter: 0.006 (4) |
33 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Zn1—N1 | 2.0411 (15) | C4—C5 | 1.390 (3) |
Zn1—N2i | 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—N4i | 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—N5ii | 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—Zn2iii | 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—Zn3iv | 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—Zn1iii | 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—N2i | 106.09 (6) | C5—C4—C3 | 122.70 (17) |
N1—Zn1—S2 | 109.97 (5) | C8—C4—C3 | 119.13 (17) |
N2i—Zn1—S2 | 114.43 (5) | C4—C5—C6 | 119.59 (17) |
N1—Zn1—S4 | 112.50 (5) | C4—C5—H5 | 120.2 |
N2i—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—N4i | 101.60 (6) | C5—C6—H6 | 118.9 |
N3—Zn2—N4i | 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 |
N4i—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—N5ii | 89.89 (5) | N1—C10—H10 | 118.8 |
O2W—Zn3—N5ii | 89.21 (5) | C9—C10—H10 | 118.8 |
O3W—Zn3—N5ii | 88.53 (6) | C20—N3—C11 | 118.47 (15) |
N6—Zn3—N5ii | 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—Zn2iii | 121.95 (12) |
N6—Zn3—O1W | 93.44 (6) | C16—N4—Zn2iii | 119.91 (12) |
N5ii—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—Zn3iv | 119.98 (12) |
O8'—S5'—O9' | 110.35 (14) | C30—N5—Zn3iv | 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—Zn1iii | 124.64 (13) | N6—C27—C28 | 123.11 (16) |
C7—N2—Zn1iii | 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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···S4v | 0.80 (2) | 2.71 (2) | 3.4264 (14) | 150 (2) |
O1W—H1WB···O3vi | 0.79 (2) | 1.91 (2) | 2.700 (2) | 175 (3) |
O2W—H2WA···O5Wvii | 0.79 (2) | 1.87 (2) | 2.649 (2) | 171 (3) |
O2W—H2WB···O8viii | 0.77 (2) | 1.94 (2) | 2.699 (3) | 165 (2) |
O3W—H3WA···O4ii | 0.76 (2) | 2.09 (2) | 2.8354 (19) | 168 (3) |
O3W—H3WB···O9viii | 0.79 (2) | 1.89 (2) | 2.678 (4) | 173 (3) |
O4W—H4WA···O2vi | 0.78 (2) | 1.95 (2) | 2.719 (2) | 167 (3) |
O4W—H4WB···O5ii | 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···O5ix | 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···O7x | 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. |
Experimental details
Crystal data |
Chemical formula | [Zn(C10H8N2)(H2O)4][Zn2(S2O3)3(C10H8N2)2]·2H2O |
Mr | 1109.12 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 292 |
a, b, c (Å) | 16.6521 (8), 15.5103 (7), 17.8922 (8) |
β (°) | 115.340 (2) |
V (Å3) | 4176.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.08 |
Crystal size (mm) | 0.22 × 0.10 × 0.08 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.657, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29188, 11611, 11255 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.714 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.051, 0.90 |
No. of reflections | 11611 |
No. of parameters | 601 |
No. of restraints | 33 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.41 |
Absolute structure | Flack (1983), 5223 Friedel pairs |
Absolute structure parameter | 0.006 (4) |
Selected bond lengths (Å) topZn1—N1 | 2.0411 (15) | Zn2—S6 | 2.2719 (5) |
Zn1—N2i | 2.0577 (15) | Zn3—O4W | 2.0924 (13) |
Zn1—S2 | 2.2967 (5) | Zn3—O2W | 2.0927 (13) |
Zn1—S4 | 2.3332 (5) | Zn3—O3W | 2.1090 (15) |
Zn2—O6 | 2.0237 (13) | Zn3—N6 | 2.1446 (15) |
Zn2—N3 | 2.0422 (14) | Zn3—N5ii | 2.1529 (15) |
Zn2—N4i | 2.0457 (15) | Zn3—O1W | 2.1705 (14) |
Symmetry codes: (i) x, −y, z+1/2; (ii) x−1/2, y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···S4iii | 0.797 (17) | 2.71 (2) | 3.4264 (14) | 150 (2) |
O1W—H1WB···O3iv | 0.794 (17) | 1.909 (18) | 2.700 (2) | 175 (3) |
O2W—H2WA···O5Wv | 0.790 (16) | 1.865 (17) | 2.649 (2) | 171 (3) |
O2W—H2WB···O8vi | 0.773 (16) | 1.943 (18) | 2.699 (3) | 165 (2) |
O3W—H3WA···O4ii | 0.759 (17) | 2.088 (18) | 2.8354 (19) | 168 (3) |
O3W—H3WB···O9vi | 0.794 (17) | 1.889 (18) | 2.678 (4) | 173 (3) |
O4W—H4WA···O2iv | 0.782 (17) | 1.952 (18) | 2.719 (2) | 167 (3) |
O4W—H4WB···O5ii | 0.806 (17) | 2.045 (19) | 2.815 (2) | 160 (3) |
O5W—H5WA···O2 | 0.799 (18) | 2.06 (2) | 2.815 (3) | 157 (3) |
O5W—H5WB···O5vii | 0.805 (18) | 1.942 (18) | 2.744 (2) | 174 (3) |
O6W—H6WA···O1 | 0.789 (18) | 2.042 (18) | 2.828 (3) | 175 (3) |
O6W—H6WB···O7viii | 0.789 (18) | 1.950 (19) | 2.722 (3) | 166 (3) |
Symmetry codes: (ii) x−1/2, y+1/2, z; (iii) x−1/2, −y+3/2, z−1/2; (iv) x, y+1, z; (v) x, −y+1, z−1/2; (vi) x−1, −y+1, z−1/2; (vii) x−1/2, y−1/2, z; (viii) x−1, y, z. |
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 ZnII 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.