Bis(1,10-phenanthroline-N,N')(thiosulfato-O,S)­nickel(II)-water-methanol (1/0.92/1.4) and bis(2,2'-bi­pyridyl-N,N')(thiosulfato-O,S)nickel(II)-water-methanol (1/2/0.55)

The title compounds, [Ni(S₂O₃)­(C₁₂H₈N₂)₂]·­0.92H₂O·­1.4CH₄O and [Ni(S₂O₃)­(C₁₀H₈N₂)₂]·­2H₂O·­0.55CH₄O, are monomeric, containing nickel(II) in a distorted octahedral coordination environment provided by the four N atoms of two bidentate bipy or phen groups and one S and one O atom from a chelating thio­sulfate anion. The crystals are highly unstable outside their mother liquors and are stabilized in solution by a not fully determined number of water and methanol solvate mol­ecules. The phenanthroline structure includes two independent moieties related by a non-crystallographic inversion center. The thio­sulfate anions display the usual S-O lengthening found when the anion acts in a bidentate mode.

S1. Comment

A search for thiosulfate complexes in the latest version (version 5.18) of the Cambridge Structural Database (Allen & Kennard, 1993) reveals some 32 structures in which the anion behaves as a coordinating ligand, displaying a variety of binding modes. Nickel is the cation in only one of these structures, tetrakis(thiourea-S)(thiosulfato-O,S)-nickel(II) monohydrate (Gasparri et al., 1969), in which the ligand is bidentate, a rather unusual mode of coordination found only in other three complexes with two different metals, viz.: bis(η₅-cyclopentadienyl)(thiosulfato-O,S)molybdenum (Kubas & Ryan, 1984), tetraethylammonium (η₅-cyclopentadienyl)bis(µ₂-thio)(thiosulfato-S,O)bis(oxomolybdenum) (Kim & Coucouvanis, 1993) and cis-bis(ethylenediamine)(thiosulfato)cobalt(II) perchlorate (Murdock et al., 1985). This type of binding to the cation usually results in lengthening of the S—O bond involving the oxygen atom which is coordinated to the metal.

Recently, two crystal structures of nickel thiosulfate complexes have been reported, triaqua(2,2'-bipyridyl-N,N')(thiosulfato-O)-nickel(II) dihydrate and triaqua(1,10-phenanthroline-N,N')(thiosulfato-O)nickel(II) monohydrate) (Freire et al., 1999), in which the anion binds to the cation in a monodentate mode through sulfur. In this case, only slight distortions are observed in the anion geometry. Nickel(II), a borderline acid ion in the Pearson (1973) classification may be expected to bind either to the hard (O) or to the soft (S) end of the thiosulfate group, thus resulting in different modes of coordination, depending on other concurring factors, such as crystal-field stabilization, shapes of accompanying ligands, intermolecular forces such as van der Waals and hydrogen bonding, etc.

The coordination chemistry of nickel(II) is important in some bacterial systems, and complexes in which N, O and/or S atoms are bonded to the metal might provide valuable information about these type of bonds, some of which are present in biological systems (Sigel & Sigel, 1994). In this line of thought we report herein the synthesis, characterization and structure of two novel nickel thiosulfate complexes, namely NiS₂O₃(phen)₂·0.92H₂O·1.40CH₃OH, (I), and NiS₂O₃(bpy)₂·2H₂O·0.55CH₃OH, (II), where bpy = bipyridine and phen = 1,10-phenanthroline. \sch

The compounds are not isostructural, but the two structures have some common features: they are monomeric and all the ligands are bidentate, the organic groups binding through the two N atoms and the thiosulfate through oxygen and sulfur. This leads to very similar nickel environments of a distorted octahedral NiN₄OS type. The steric hindrance imposed by the rigid character of the organic ligands and the chelate (S,O) thiosulfate are largely responsible for the distortions.

Crystals of (I) contain two molecules in the asymmetric unit, occupying general positions in space group P1. There is, however, a striking non-crystallographic center of symmetry at x = 0.252 (4), y = 0.487 (2) and z = 0.255 (2) which relates the two moieties. The degree of this pseudosymmetry can be assessed by a least-squares fit of the atoms of one of the two molecules to the inverted positions of the atoms of the other. When this is done, the r.m.s. deviation of the matching pairs is 0.24 Å, with larger deviations for the thiosulfates and an almost perfect match for the planar phen groups. This fitting worsens dramatically when the solvent molecules are also considered, and this reveals why the structure does not really crystallize in a more symmetric space group (monoclinic with a single molecule per asymmetric unit): the included solvent molecules do not exist in pairs related by the pseudocenter of symmetry. As a result of the pseudosymmetry, both Ni ions have almost identical environments, with the four Ni—N distances (2.072–2.094 Å) being normal for an hexacoordinated nickel cation, and only slightly longer than those observed in S-bonded nickel thiosulfates (2.041–2.070 Å) (Freire et al., 1999). The S,O-chelating thiosulfate completes the coordination sphere, in a way similar to that of the thiourea complex of Gasparri et al. (1969). The mean Ni—S distance, 2.462 (1) Å, compares fairly well with the values reported for Ni—S bonded complexes. A relevant feature in the anion is the considerable lengthening observed in the S—O bonds involving the oxygen atom which coordinates to nickel, as compared to the non-coordinated ones [S—O_coord: 1.495 (3), 1.489 (3) Å versus S—O_non-coord: 1.448 (3), 1.450 (3) Å, for molecules A and B, respectively]. As expected, concomitantly smaller S—S—O angles appear [S—S—O_coord: 102.6 (1), 102.7 (1)° versus S—S—O_non-coord: 110.1 (1), 109.7 (2)°, for molecules A and B, respectively]. Similar effects have already been reported in the literature (Kubas & Ryan, 1984; Murdock et al., 1985; Kim & Coucouvanis, 1993; Gasparri et al., 1969).

The phenanthroline ligands are basically planar (r.m.s. deviations from the best planes: 0.022, 0.026, 0.029 and 0.020 Å for phen groups A, B, C and D). In each octahedron, the groups are very nearly perpendicular to each other and to the closed coordination loop subtended by the chelate thiosulfate (maximum departures from 90°: 4.9 and 6.5° for molecules A and B).

As already mentioned, in complex (II) the four N atoms in the Ni coordination core are provided by two bidentate bipyridine groups, with a range in the Ni—N distances of 2.061–2.097 Å. The same trend as in (I), regarding bonds and angles, is observed in the coordinated thiosulfate as shown by the (mean) values S—O_coord:1.484; S—O_noncoord:1.457 Å, S—S—O_coord:103.2; S—S—O_noncoord:111.1°.

The bipy ligands present a noticeable twisting of the individual pyridinic groups along the C5—C6 bonds [5.1 (3) and 6.2 (3)° in groups A and B respectively], and subtend an angle of 99.7 (1)° to each other. The thiosulfate loop, instead, is almost perfectly perpendicular to both (91.0 and 89.3°).

The quality of the results obtained in both structures precludes a detailed analysis of the hydrogen-bonding schemes. However, the large number of protons known to be available for the interactions, as well as the evidence of many short (<3.00 Å) O···O contacts allows us to speak of a rather complex hydrogen-bonding network interconnecting the monomers, even though the intervening hydrogen atoms could not be found directly. Further evidence of the stabilizing role of these interactions is provided by the fact that the solvent loss taking place at atmospheric conditions practically destroys the crystal lattices in only a few minutes.

S2. Experimental

The synthesis of (I) was performed by direct mixing of the reactants (in the form of aqueous solutions of nickel nitrate and sodium thiosulfate, and a methanolic solution of 1,10-phenanthroline, in a 1:3:2 molar ratio). On standing, well shaped pale grey prisms were obtained, quite stable in solution but which proved absolutely unstable outside their mother liquors, to the extent that they collapsed in a few minutes in a dry atmosphere. This required the mounting of the specimens intended for data collection in sealed capillaries with a drop of stabilizing mother liquors. In this way, the crystals were shown to survive for months without any evidence of decay. The IR spectra contain the characteristic peaks of the coordinated ligands: 1143 cm⁻¹ for thiosulfate and 727, 854 and 1516 cm⁻¹ for phenanthroline.

Crystals of (II) were slightly harder to obtain: direct mixing of solutions as in (I) (with bipyridine replacing phenanthroline, and in the same 1:3:2 molar ratio), resulted in the growth of specimens too small for X-ray analysis. Relatively few, but reasonably good, crystals were then obtained by first allowing the methanolic solution of bipyridine to diffuse into an aqueous solution of the inorganic compounds, followed by several days in which a fraction of the solvent evaporated. Though more stable than crystals of compound (I), they also decayed appreciably when left at atmospheric conditions, and were therefore accordingly encapsulated.

S3. Refinement

The structures were solved by direct methods and difference Fourier synthesis, and refined by least squares on F², using the whole data set. The main molecules posed no problems in the process, but the very elusive solvent molecules (water and methanol) were very difficult to find and refine, a fact which is reflected in the final R factors. Besides, and due to the instability of the compounds outside the mother liquors, no chemical nor TGA analysis were feasible. Thus, single-crystal X-ray diffraction remained the ultimate analytical tool, and the results obtained with this technique for the overall solvate contents were those with which the compounds have been formulated in the present work. These results must, however, be looked at with caution and taken only as a lower bound for the actual values for the compounds in solution. This idea is fully supported by the extreme instability of the solvates and corroborated by the fact that most of the solvent sites appeared disordered or only partially filled. Hydrogen atoms in the organic ligands were included at their expected positions. Those in the solvates, were obviously not found.

Computing details

For both compounds, 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, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).

Figures

	Fig. 1. Molecular diagram for (I). Note the pseudosymmetry center across the two independent moieties. Displacement ellipsoids are drawn at the 50% level.
	Fig. 2. Molecular diagram for (II). Displacement ellipsoids are drawn at the 50% level.

(I) Bis-(2,10-phenanthroline-N,N')-(thiosulfato-O,S)-nickel(II) hydrate, methanol solvate

Crystal data

[Ni(O3S2)(C12H8N2)2]·0.92H2O·1.4CH4O	Z = 4
Mr = 592.66	F(000) = 1225.6
Triclinic, P1	Dx = 1.49 Mg m^−3
a = 12.613 (2) Å	Mo Kα radiation, λ = 0.71070 Å
b = 18.855 (3) Å	Cell parameters from 25 reflections
c = 11.3048 (19) Å	θ = 7.5–15°
α = 90.467 (18)°	µ = 0.94 mm^−1
β = 100.365 (15)°	T = 293 K
γ = 87.202 (13)°	Polyhedra, pale-grey
V = 2641.4 (7) Å^3	0.30 × 0.28 × 0.22 mm

Data collection

Rigaku AFC7S Difractometer diffractometer	7271 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
ω/2θ scans	h = 0→15
Absorption correction: ψ scan MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988)	k = −24→24
Tmin = 0.76, Tmax = 0.80	l = −14→14
12469 measured reflections	3 standard reflections every 150 reflections
11915 independent reflections	intensity decay: <3%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 0.95	Calculated w = 1/[σ^2(Fo^2) + (0.089P)^2 + 2.571P] where P = (Fo^2 + 2Fc^2)/3
11915 reflections	(Δ/σ)max < 0.01
737 parameters	Δρmax = 0.88 e Å^−3
5 restraints	Δρmin = −0.63 e Å^−3

Special details

Experimental. The compound is absolutely unstable outside the mother liquors and required to be encapsulated

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1A	0.72796 (3)	0.13398 (2)	0.84942 (4)	0.03111 (12)
S1A	0.71271 (8)	0.25973 (5)	0.90695 (8)	0.0409 (2)
S2A	0.75910 (8)	0.21252 (6)	1.06948 (8)	0.0434 (2)
O1A	0.7699 (2)	0.13584 (14)	1.0371 (2)	0.0444 (6)
O2A	0.6760 (3)	0.22396 (18)	1.1415 (3)	0.0686 (9)
O3A	0.8637 (3)	0.2361 (2)	1.1266 (3)	0.0902 (13)
N1A	0.8851 (2)	0.14292 (16)	0.8192 (3)	0.0363 (6)
N2A	0.6975 (2)	0.14962 (15)	0.6650 (3)	0.0347 (6)
C1A	0.9773 (3)	0.1383 (2)	0.8966 (4)	0.0441 (9)
H1A	0.9758	0.1289	0.9769	0.053*
C2A	1.0770 (3)	0.1470 (2)	0.8618 (4)	0.0522 (10)
H2A	1.1403	0.1433	0.9186	0.063*
C3A	1.0812 (3)	0.1607 (2)	0.7459 (4)	0.0538 (11)
H3A	1.1473	0.1666	0.7226	0.065*
C4A	0.9847 (3)	0.1659 (2)	0.6596 (4)	0.0450 (9)
C5A	0.9798 (4)	0.1817 (2)	0.5355 (4)	0.0575 (12)
H5A	1.0436	0.1877	0.5071	0.069*
C6A	0.8854 (4)	0.1880 (2)	0.4587 (4)	0.0557 (11)
H6A	0.8846	0.1998	0.3788	0.067*
C7A	0.7854 (4)	0.1768 (2)	0.4987 (3)	0.0444 (9)
C8A	0.6836 (4)	0.1813 (2)	0.4228 (4)	0.0541 (11)
H8A	0.6780	0.1919	0.3417	0.065*
C9A	0.5939 (4)	0.1700 (2)	0.4691 (4)	0.0525 (10)
H9A	0.5262	0.1728	0.4201	0.063*
C10A	0.6039 (3)	0.1541 (2)	0.5903 (3)	0.0426 (8)
H10A	0.5416	0.1461	0.6205	0.051*
C11A	0.7882 (3)	0.16077 (18)	0.6200 (3)	0.0359 (7)
C12A	0.8883 (3)	0.15598 (18)	0.7019 (3)	0.0357 (7)
N1D	0.5688 (2)	0.11154 (16)	0.8586 (2)	0.0335 (6)
N2D	0.7373 (2)	0.02302 (16)	0.8383 (3)	0.0393 (7)
C1D	0.4878 (3)	0.1564 (2)	0.8719 (3)	0.0423 (8)
H1D	0.5002	0.2046	0.8791	0.051*
C2D	0.3849 (3)	0.1342 (3)	0.8755 (4)	0.0500 (10)
H2D	0.3299	0.1673	0.8853	0.060*
C3D	0.3649 (3)	0.0645 (3)	0.8648 (4)	0.0511 (10)
H3D	0.2962	0.0494	0.8670	0.061*
C4D	0.4482 (3)	0.0150 (2)	0.8504 (3)	0.0440 (9)
C5D	0.4361 (4)	−0.0602 (2)	0.8403 (4)	0.0537 (11)
H5D	0.3695	−0.0785	0.8436	0.064*
C6D	0.5197 (4)	−0.1044 (2)	0.8263 (4)	0.0576 (12)
H6D	0.5091	−0.1528	0.8185	0.069*
C7D	0.6254 (4)	−0.0794 (2)	0.8227 (3)	0.0470 (9)
C8D	0.7150 (4)	−0.1230 (2)	0.8092 (4)	0.0591 (12)
H8D	0.7084	−0.1716	0.7978	0.071*
C9D	0.8123 (4)	−0.0941 (2)	0.8129 (4)	0.0620 (12)
H9D	0.8727	−0.1228	0.8049	0.074*
C10D	0.8206 (4)	−0.0203 (2)	0.8288 (4)	0.0508 (10)
H10D	0.8878	−0.0013	0.8328	0.061*
C11D	0.6392 (3)	−0.00587 (19)	0.8360 (3)	0.0374 (8)
C12D	0.5502 (3)	0.04114 (19)	0.8485 (3)	0.0348 (7)
Ni1B	0.29705 (3)	0.35532 (2)	0.65710 (4)	0.03174 (13)
S1B	0.31710 (8)	0.22862 (5)	0.60692 (8)	0.0386 (2)
S2B	0.27229 (7)	0.27233 (5)	0.44126 (8)	0.0358 (2)
O1B	0.2480 (2)	0.34823 (14)	0.4690 (2)	0.0408 (6)
O2B	0.3605 (2)	0.26521 (15)	0.3748 (2)	0.0495 (7)
O3B	0.1765 (2)	0.23916 (17)	0.3790 (3)	0.0591 (8)
N1B	0.1405 (2)	0.34815 (16)	0.6892 (3)	0.0365 (6)
N2B	0.3290 (2)	0.34171 (16)	0.8424 (3)	0.0354 (6)
C1B	0.0482 (3)	0.3536 (2)	0.6111 (4)	0.0433 (9)
H1B	0.0498	0.3608	0.5302	0.052*
C2B	−0.0515 (3)	0.3487 (2)	0.6476 (4)	0.0538 (11)
H2B	−0.1150	0.3536	0.5913	0.065*
C3B	−0.0558 (3)	0.3368 (2)	0.7646 (4)	0.0540 (11)
H3B	−0.1220	0.3331	0.7889	0.065*
C4B	0.0414 (3)	0.3302 (2)	0.8495 (4)	0.0470 (9)
C5B	0.0462 (4)	0.3154 (3)	0.9748 (4)	0.0592 (12)
H5B	−0.0175	0.3103	1.0038	0.071*
C6B	0.1413 (4)	0.3088 (3)	1.0510 (4)	0.0586 (12)
H6B	0.1422	0.2982	1.1314	0.070*
C7B	0.2409 (4)	0.3177 (2)	1.0104 (4)	0.0473 (9)
C8B	0.3426 (4)	0.3130 (2)	1.0854 (4)	0.0544 (11)
H8B	0.3483	0.3034	1.1670	0.065*
C9B	0.4328 (4)	0.3224 (2)	1.0380 (4)	0.0555 (11)
H9B	0.5006	0.3189	1.0869	0.067*
C10B	0.4229 (3)	0.3371 (2)	0.9166 (3)	0.0440 (9)
H10B	0.4852	0.3441	0.8858	0.053*
C11B	0.2382 (3)	0.33238 (18)	0.8882 (3)	0.0377 (8)
C12B	0.1377 (3)	0.33749 (19)	0.8070 (3)	0.0377 (8)
N1C	0.4554 (2)	0.37770 (15)	0.6461 (3)	0.0332 (6)
N2C	0.2871 (2)	0.46634 (16)	0.6629 (3)	0.0400 (7)
C1C	0.5372 (3)	0.3328 (2)	0.6359 (3)	0.0411 (8)
H1C	0.5256	0.2845	0.6316	0.049*
C2C	0.6402 (3)	0.3551 (2)	0.6312 (4)	0.0502 (10)
H2C	0.6959	0.3220	0.6242	0.060*
C3C	0.6586 (3)	0.4255 (2)	0.6370 (4)	0.0496 (10)
H3C	0.7270	0.4408	0.6341	0.059*
C4C	0.5748 (3)	0.4749 (2)	0.6473 (3)	0.0415 (8)
C5C	0.5848 (4)	0.5502 (2)	0.6521 (4)	0.0527 (11)
H5C	0.6510	0.5687	0.6477	0.063*
C6C	0.5009 (4)	0.5946 (2)	0.6627 (4)	0.0536 (11)
H6C	0.5104	0.6432	0.6664	0.064*
C7C	0.3973 (4)	0.5692 (2)	0.6685 (4)	0.0471 (9)
C8C	0.3065 (4)	0.6130 (2)	0.6784 (5)	0.0643 (13)
H8C	0.3123	0.6619	0.6858	0.077*
C9C	0.2099 (4)	0.5839 (3)	0.6773 (5)	0.0688 (14)
H9C	0.1487	0.6128	0.6814	0.083*
C10C	0.2032 (4)	0.5095 (2)	0.6698 (4)	0.0552 (11)
H10C	0.1368	0.4902	0.6697	0.066*
C11C	0.3836 (3)	0.49564 (19)	0.6618 (3)	0.0371 (8)
C12C	0.4732 (3)	0.44799 (18)	0.6518 (3)	0.0329 (7)
O1W	0.0034 (3)	0.67971 (19)	0.7220 (3)	0.0710 (9)
O2W	0.1217 (6)	0.4819 (4)	0.3949 (8)	0.087 (3)	0.549 (8)
O3W	1.1969 (16)	0.0740 (8)	0.4889 (19)	0.102 (6)	0.290 (9)
O1X	−0.0057 (7)	0.5439 (4)	0.8249 (8)	0.104 (3)	0.580 (7)
C1X	−0.0934 (15)	0.5378 (11)	0.7305 (19)	0.263 (18)	0.580 (7)
O2X	0.1456 (14)	0.4913 (7)	0.9986 (13)	0.146 (6)	0.453 (8)
C2X	0.2482 (15)	0.5191 (15)	1.019 (3)	0.167 (16)	0.453 (8)
O3X	1.2809 (17)	0.0371 (7)	0.5163 (12)	0.179 (7)	0.575 (8)
C3X	1.3851 (18)	0.0537 (15)	0.506 (3)	0.225 (13)	0.575 (8)
C4X	0.348 (3)	0.547 (2)	1.016 (4)	0.21 (2)	0.316 (9)
O4X	0.238 (3)	0.560 (2)	1.015 (4)	0.22 (2)	0.316 (9)
O5X	0.8956 (5)	0.0226 (3)	1.1488 (5)	0.106 (2)	0.882 (7)
C5X	0.9097 (10)	0.0375 (6)	1.2719 (7)	0.149 (4)	0.882 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1A	0.0287 (2)	0.0369 (2)	0.0298 (2)	−0.00615 (18)	0.00940 (16)	0.00266 (17)
S1A	0.0483 (5)	0.0397 (5)	0.0379 (5)	−0.0087 (4)	0.0143 (4)	0.0027 (4)
S2A	0.0490 (5)	0.0540 (6)	0.0288 (4)	−0.0181 (5)	0.0073 (4)	−0.0020 (4)
O1A	0.0477 (15)	0.0508 (16)	0.0344 (13)	−0.0023 (12)	0.0061 (11)	0.0085 (11)
O2A	0.095 (3)	0.072 (2)	0.0484 (18)	−0.0015 (19)	0.0391 (18)	0.0031 (15)
O3A	0.086 (3)	0.112 (3)	0.065 (2)	−0.057 (2)	−0.0224 (19)	0.008 (2)
N1A	0.0287 (15)	0.0421 (16)	0.0409 (16)	−0.0061 (12)	0.0121 (12)	0.0036 (13)
N2A	0.0347 (15)	0.0390 (16)	0.0322 (15)	−0.0012 (12)	0.0108 (12)	0.0014 (12)
C1A	0.0295 (19)	0.053 (2)	0.050 (2)	−0.0067 (16)	0.0074 (16)	0.0049 (18)
C2A	0.038 (2)	0.057 (3)	0.061 (3)	−0.0019 (19)	0.0087 (19)	0.001 (2)
C3A	0.038 (2)	0.056 (3)	0.074 (3)	−0.0104 (18)	0.026 (2)	−0.005 (2)
C4A	0.043 (2)	0.041 (2)	0.059 (2)	−0.0091 (16)	0.0284 (18)	−0.0002 (17)
C5A	0.066 (3)	0.059 (3)	0.061 (3)	−0.016 (2)	0.044 (2)	−0.004 (2)
C6A	0.079 (3)	0.059 (3)	0.038 (2)	−0.014 (2)	0.032 (2)	0.0004 (19)
C7A	0.063 (3)	0.0378 (19)	0.036 (2)	−0.0055 (18)	0.0201 (18)	0.0006 (15)
C8A	0.078 (3)	0.055 (2)	0.0295 (19)	0.001 (2)	0.0097 (19)	0.0035 (17)
C9A	0.054 (2)	0.065 (3)	0.035 (2)	0.008 (2)	0.0014 (18)	0.0014 (19)
C10A	0.041 (2)	0.047 (2)	0.038 (2)	0.0012 (17)	0.0057 (16)	−0.0030 (16)
C11A	0.044 (2)	0.0323 (17)	0.0345 (18)	−0.0030 (15)	0.0142 (15)	0.0001 (14)
C12A	0.0377 (19)	0.0344 (17)	0.0396 (19)	−0.0058 (15)	0.0182 (15)	0.0010 (14)
N1D	0.0291 (14)	0.0421 (16)	0.0316 (15)	−0.0107 (12)	0.0093 (11)	0.0011 (12)
N2D	0.0402 (17)	0.0383 (16)	0.0401 (17)	−0.0019 (13)	0.0091 (13)	0.0038 (13)
C1D	0.0360 (19)	0.051 (2)	0.041 (2)	−0.0015 (17)	0.0092 (15)	0.0048 (17)
C2D	0.034 (2)	0.071 (3)	0.046 (2)	0.0016 (19)	0.0093 (16)	0.004 (2)
C3D	0.035 (2)	0.078 (3)	0.043 (2)	−0.018 (2)	0.0074 (16)	0.009 (2)
C4D	0.045 (2)	0.058 (2)	0.0299 (18)	−0.0211 (19)	0.0044 (15)	0.0050 (16)
C5D	0.059 (3)	0.060 (3)	0.044 (2)	−0.032 (2)	0.0044 (19)	0.0037 (19)
C6D	0.080 (3)	0.047 (2)	0.045 (2)	−0.032 (2)	0.000 (2)	0.0020 (18)
C7D	0.069 (3)	0.038 (2)	0.0339 (19)	−0.0131 (19)	0.0064 (18)	0.0000 (15)
C8D	0.089 (4)	0.036 (2)	0.052 (3)	−0.008 (2)	0.012 (2)	−0.0030 (18)
C9D	0.078 (3)	0.044 (2)	0.065 (3)	0.012 (2)	0.020 (3)	−0.001 (2)
C10D	0.048 (2)	0.049 (2)	0.057 (3)	0.0025 (19)	0.0128 (19)	−0.0007 (19)
C11D	0.048 (2)	0.0388 (19)	0.0278 (17)	−0.0151 (16)	0.0082 (14)	0.0017 (14)
C12D	0.0351 (18)	0.0418 (19)	0.0282 (17)	−0.0130 (15)	0.0047 (13)	0.0023 (14)
Ni1B	0.0299 (2)	0.0357 (2)	0.0320 (2)	−0.00446 (18)	0.01126 (17)	0.00113 (18)
S1B	0.0438 (5)	0.0372 (5)	0.0368 (5)	−0.0050 (4)	0.0118 (4)	0.0050 (4)
S2B	0.0345 (4)	0.0438 (5)	0.0304 (4)	−0.0081 (4)	0.0080 (3)	0.0000 (4)
O1B	0.0451 (15)	0.0443 (14)	0.0335 (13)	−0.0010 (12)	0.0083 (11)	0.0061 (11)
O2B	0.0536 (17)	0.0597 (18)	0.0412 (15)	−0.0044 (14)	0.0245 (13)	0.0003 (13)
O3B	0.0474 (17)	0.070 (2)	0.0574 (18)	−0.0196 (15)	−0.0023 (14)	−0.0074 (15)
N1B	0.0311 (15)	0.0422 (17)	0.0402 (16)	−0.0070 (13)	0.0154 (12)	−0.0005 (13)
N2B	0.0350 (15)	0.0386 (16)	0.0344 (15)	−0.0029 (12)	0.0111 (12)	−0.0015 (12)
C1B	0.0342 (19)	0.052 (2)	0.045 (2)	−0.0072 (17)	0.0077 (16)	0.0017 (17)
C2B	0.035 (2)	0.060 (3)	0.068 (3)	−0.0010 (19)	0.0140 (19)	0.002 (2)
C3B	0.037 (2)	0.058 (3)	0.074 (3)	−0.0086 (19)	0.026 (2)	−0.002 (2)
C4B	0.046 (2)	0.046 (2)	0.057 (3)	−0.0069 (18)	0.0277 (19)	0.0003 (18)
C5B	0.063 (3)	0.070 (3)	0.056 (3)	−0.013 (2)	0.039 (2)	−0.003 (2)
C6B	0.071 (3)	0.067 (3)	0.046 (2)	−0.009 (2)	0.032 (2)	0.002 (2)
C7B	0.063 (3)	0.044 (2)	0.039 (2)	−0.0032 (19)	0.0198 (18)	−0.0008 (16)
C8B	0.075 (3)	0.057 (3)	0.031 (2)	−0.006 (2)	0.0107 (19)	−0.0002 (18)
C9B	0.057 (3)	0.065 (3)	0.041 (2)	−0.001 (2)	0.0008 (19)	0.000 (2)
C10B	0.046 (2)	0.049 (2)	0.037 (2)	−0.0022 (18)	0.0088 (16)	−0.0043 (16)
C11B	0.048 (2)	0.0329 (17)	0.0363 (19)	−0.0024 (15)	0.0181 (16)	−0.0024 (14)
C12B	0.0384 (19)	0.0355 (18)	0.043 (2)	−0.0036 (15)	0.0176 (15)	−0.0013 (15)
N1C	0.0296 (14)	0.0360 (15)	0.0361 (15)	−0.0087 (12)	0.0101 (11)	0.0008 (12)
N2C	0.0412 (17)	0.0369 (16)	0.0449 (18)	−0.0015 (13)	0.0160 (14)	0.0001 (13)
C1C	0.0362 (19)	0.044 (2)	0.046 (2)	−0.0007 (16)	0.0152 (16)	0.0031 (16)
C2C	0.038 (2)	0.059 (3)	0.055 (2)	0.0020 (19)	0.0111 (18)	0.001 (2)
C3C	0.034 (2)	0.067 (3)	0.049 (2)	−0.0131 (19)	0.0097 (17)	0.004 (2)
C4C	0.043 (2)	0.049 (2)	0.0351 (19)	−0.0157 (17)	0.0082 (15)	0.0013 (16)
C5C	0.058 (3)	0.055 (3)	0.048 (2)	−0.029 (2)	0.0095 (19)	−0.0006 (19)
C6C	0.078 (3)	0.039 (2)	0.046 (2)	−0.023 (2)	0.010 (2)	−0.0031 (17)
C7C	0.066 (3)	0.0340 (19)	0.043 (2)	−0.0102 (18)	0.0121 (19)	−0.0018 (16)
C8C	0.087 (4)	0.033 (2)	0.075 (3)	0.002 (2)	0.022 (3)	−0.002 (2)
C9C	0.074 (3)	0.047 (3)	0.090 (4)	0.014 (2)	0.031 (3)	−0.003 (2)
C10C	0.046 (2)	0.050 (2)	0.073 (3)	0.0078 (19)	0.023 (2)	0.000 (2)
C11C	0.043 (2)	0.0375 (18)	0.0328 (18)	−0.0066 (16)	0.0118 (15)	−0.0013 (14)
C12C	0.0363 (18)	0.0379 (18)	0.0268 (16)	−0.0097 (14)	0.0096 (13)	0.0007 (13)
O1W	0.0563 (19)	0.075 (2)	0.082 (2)	−0.0002 (17)	0.0139 (17)	−0.0193 (19)
O2W	0.078 (5)	0.061 (5)	0.116 (7)	−0.002 (4)	0.000 (4)	0.018 (4)
O3W	0.118 (14)	0.043 (8)	0.156 (17)	−0.001 (8)	0.055 (12)	−0.005 (8)
O1X	0.104 (6)	0.085 (5)	0.123 (7)	0.002 (5)	0.026 (5)	−0.003 (5)
C1X	0.16 (2)	0.112 (15)	0.53 (6)	−0.051 (15)	0.11 (3)	−0.07 (3)
O2X	0.187 (15)	0.109 (10)	0.146 (12)	−0.016 (10)	0.038 (11)	0.054 (9)
C2X	0.30 (5)	0.093 (18)	0.094 (16)	−0.03 (2)	−0.01 (2)	0.006 (15)
O3X	0.27 (2)	0.110 (10)	0.143 (10)	−0.053 (12)	−0.008 (13)	0.002 (8)
C3X	0.23 (3)	0.20 (3)	0.24 (3)	−0.08 (2)	0.01 (2)	−0.01 (2)
C4X	0.27 (5)	0.16 (4)	0.16 (3)	−0.10 (4)	−0.06 (4)	0.08 (3)
O4X	0.29 (5)	0.17 (3)	0.19 (3)	−0.06 (3)	0.04 (3)	−0.09 (3)
O5X	0.121 (4)	0.083 (3)	0.106 (4)	0.034 (3)	0.014 (3)	0.009 (3)
C5X	0.155 (10)	0.146 (9)	0.144 (10)	0.008 (7)	0.032 (8)	−0.048 (8)

Geometric parameters (Å, º)

Ni1A—N2A	2.071 (3)	Ni1B—N2C	2.092 (3)
Ni1A—N1A	2.086 (3)	Ni1B—O1B	2.110 (3)
Ni1A—N1D	2.092 (3)	Ni1B—S1B	2.4624 (11)
Ni1A—O1A	2.093 (3)	S1B—S2B	2.0260 (13)
Ni1A—N2D	2.094 (3)	S2B—O2B	1.450 (3)
Ni1A—S1A	2.4613 (11)	S2B—O3B	1.452 (3)
S1A—S2A	2.0249 (14)	S2B—O1B	1.492 (3)
S2A—O3A	1.449 (3)	N1B—C1B	1.329 (5)
S2A—O2A	1.445 (3)	N1B—C12B	1.355 (5)
S2A—O1A	1.494 (3)	N2B—C10B	1.322 (5)
N1A—C1A	1.323 (5)	N2B—C11B	1.358 (4)
N1A—C12A	1.359 (4)	C1B—C2B	1.399 (5)
N2A—C10A	1.321 (5)	C2B—C3B	1.354 (6)
N2A—C11A	1.359 (4)	C3B—C4B	1.416 (6)
C1A—C2A	1.401 (5)	C4B—C12B	1.397 (5)
C2A—C3A	1.349 (6)	C4B—C5B	1.436 (6)
C3A—C4A	1.416 (6)	C5B—C6B	1.346 (7)
C4A—C12A	1.405 (5)	C6B—C7B	1.431 (6)
C4A—C5A	1.427 (6)	C7B—C8B	1.403 (6)
C5A—C6A	1.342 (7)	C7B—C11B	1.405 (5)
C6A—C7A	1.440 (6)	C8B—C9B	1.362 (6)
C7A—C11A	1.400 (5)	C9B—C10B	1.385 (6)
C7A—C8A	1.410 (6)	C11B—C12B	1.425 (5)
C8A—C9A	1.356 (6)	N1C—C1C	1.322 (5)
C9A—C10A	1.387 (5)	N1C—C12C	1.354 (4)
C11A—C12A	1.425 (5)	N2C—C10C	1.317 (5)
N1D—C1D	1.324 (5)	N2C—C11C	1.362 (5)
N1D—C12D	1.359 (4)	C1C—C2C	1.394 (5)
N2D—C10D	1.319 (5)	C2C—C3C	1.358 (6)
N2D—C11D	1.372 (5)	C3C—C4C	1.395 (6)
C1D—C2D	1.391 (5)	C4C—C12C	1.411 (5)
C2D—C3D	1.352 (6)	C4C—C5C	1.431 (6)
C3D—C4D	1.402 (6)	C5C—C6C	1.339 (6)
C4D—C12D	1.404 (5)	C6C—C7C	1.427 (6)
C4D—C5D	1.435 (6)	C7C—C8C	1.400 (6)
C5D—C6D	1.344 (7)	C7C—C11C	1.405 (5)
C6D—C7D	1.442 (6)	C8C—C9C	1.359 (7)
C7D—C8D	1.395 (6)	C9C—C10C	1.410 (6)
C7D—C11D	1.410 (5)	C11C—C12C	1.429 (5)
C8D—C9D	1.359 (7)	O1X—C1X	1.401 (5)
C9D—C10D	1.409 (6)	O2X—C2X	1.401 (5)
C11D—C12D	1.422 (5)	O3X—C3X	1.390 (5)
Ni1B—N2B	2.076 (3)	C4X—O4X	1.401 (5)
Ni1B—N1B	2.082 (3)	O5X—C5X	1.400 (5)
Ni1B—N1C	2.087 (3)
N2A—Ni1A—N1A	80.02 (12)	N2B—Ni1B—N1B	80.10 (12)
N2A—Ni1A—N1D	94.56 (11)	N2B—Ni1B—N1C	94.39 (11)
N1A—Ni1A—N1D	170.52 (12)	N1B—Ni1B—N1C	169.79 (11)
N2A—Ni1A—O1A	169.94 (11)	N2B—Ni1B—N2C	95.30 (12)
N1A—Ni1A—O1A	95.12 (11)	N1B—Ni1B—N2C	92.47 (12)
N1D—Ni1A—O1A	91.40 (11)	N1C—Ni1B—N2C	79.41 (12)
N2A—Ni1A—N2D	94.76 (12)	N2B—Ni1B—O1B	167.59 (11)
N1A—Ni1A—N2D	93.05 (12)	N1B—Ni1B—O1B	93.02 (11)
N1D—Ni1A—N2D	79.57 (12)	N1C—Ni1B—O1B	93.87 (11)
O1A—Ni1A—N2D	94.29 (11)	N2C—Ni1B—O1B	95.31 (11)
N2A—Ni1A—S1A	96.96 (9)	N2B—Ni1B—S1B	96.04 (9)
N1A—Ni1A—S1A	92.39 (9)	N1B—Ni1B—S1B	94.09 (9)
N1D—Ni1A—S1A	96.01 (9)	N1C—Ni1B—S1B	95.03 (8)
O1A—Ni1A—S1A	74.32 (8)	N2C—Ni1B—S1B	167.73 (9)
N2D—Ni1A—S1A	167.77 (9)	O1B—Ni1B—S1B	74.01 (8)
S2A—S1A—Ni1A	78.56 (5)	S2B—S1B—Ni1B	78.69 (4)
O3A—S2A—O2A	113.8 (2)	O2B—S2B—O3B	111.90 (18)
O3A—S2A—O1A	109.2 (2)	O2B—S2B—O1B	111.27 (16)
O2A—S2A—O1A	110.50 (18)	O3B—S2B—O1B	111.14 (17)
O3A—S2A—S1A	110.15 (16)	O2B—S2B—S1B	110.24 (13)
O2A—S2A—S1A	110.09 (15)	O3B—S2B—S1B	109.25 (14)
O1A—S2A—S1A	102.59 (11)	O1B—S2B—S1B	102.64 (11)
S2A—O1A—Ni1A	104.52 (14)	S2B—O1B—Ni1B	104.11 (13)
C1A—N1A—C12A	118.3 (3)	C1B—N1B—C12B	119.0 (3)
C1A—N1A—Ni1A	129.3 (3)	C1B—N1B—Ni1B	128.6 (2)
C12A—N1A—Ni1A	112.3 (2)	C12B—N1B—Ni1B	112.5 (2)
C10A—N2A—C11A	118.0 (3)	C10B—N2B—C11B	118.2 (3)
C10A—N2A—Ni1A	129.0 (2)	C10B—N2B—Ni1B	129.2 (3)
C11A—N2A—Ni1A	112.9 (2)	C11B—N2B—Ni1B	112.5 (2)
N1A—C1A—C2A	122.3 (4)	N1B—C1B—C2B	121.7 (4)
C3A—C2A—C1A	119.9 (4)	C3B—C2B—C1B	120.2 (4)
C2A—C3A—C4A	119.8 (4)	C2B—C3B—C4B	119.3 (4)
C12A—C4A—C5A	119.1 (4)	C12B—C4B—C3B	117.3 (4)
C12A—C4A—C3A	116.6 (4)	C12B—C4B—C5B	118.9 (4)
C5A—C4A—C3A	124.3 (4)	C3B—C4B—C5B	123.9 (4)
C6A—C5A—C4A	121.5 (4)	C6B—C5B—C4B	121.1 (4)
C5A—C6A—C7A	120.7 (4)	C5B—C6B—C7B	121.2 (4)
C11A—C7A—C8A	117.4 (4)	C8B—C7B—C11B	117.2 (4)
C11A—C7A—C6A	118.8 (4)	C8B—C7B—C6B	124.1 (4)
C8A—C7A—C6A	123.8 (4)	C11B—C7B—C6B	118.7 (4)
C9A—C8A—C7A	119.4 (4)	C9B—C8B—C7B	119.6 (4)
C8A—C9A—C10A	119.4 (4)	C8B—C9B—C10B	119.5 (4)
N2A—C10A—C9A	123.3 (4)	N2B—C10B—C9B	123.0 (4)
N2A—C11A—C7A	122.4 (3)	N2B—C11B—C7B	122.5 (4)
N2A—C11A—C12A	117.2 (3)	N2B—C11B—C12B	117.5 (3)
C7A—C11A—C12A	120.3 (3)	C7B—C11B—C12B	120.1 (3)
N1A—C12A—C4A	123.0 (3)	N1B—C12B—C4B	122.6 (4)
N1A—C12A—C11A	117.4 (3)	N1B—C12B—C11B	117.4 (3)
C4A—C12A—C11A	119.5 (3)	C4B—C12B—C11B	120.0 (3)
C1D—N1D—C12D	118.5 (3)	C1C—N1C—C12C	118.2 (3)
C1D—N1D—Ni1A	128.4 (3)	C1C—N1C—Ni1B	128.6 (2)
C12D—N1D—Ni1A	113.1 (2)	C12C—N1C—Ni1B	113.2 (2)
C10D—N2D—C11D	118.1 (3)	C10C—N2C—C11C	117.9 (3)
C10D—N2D—Ni1A	129.5 (3)	C10C—N2C—Ni1B	129.2 (3)
C11D—N2D—Ni1A	112.4 (2)	C11C—N2C—Ni1B	112.9 (2)
N1D—C1D—C2D	122.5 (4)	N1C—C1C—C2C	122.7 (4)
C3D—C2D—C1D	119.8 (4)	C3C—C2C—C1C	119.4 (4)
C2D—C3D—C4D	119.7 (4)	C2C—C3C—C4C	120.1 (4)
C3D—C4D—C12D	117.4 (4)	C3C—C4C—C12C	116.9 (3)
C3D—C4D—C5D	124.1 (4)	C3C—C4C—C5C	124.6 (4)
C12D—C4D—C5D	118.5 (4)	C12C—C4C—C5C	118.4 (4)
C6D—C5D—C4D	120.8 (4)	C6C—C5C—C4C	121.4 (4)
C5D—C6D—C7D	122.3 (4)	C5C—C6C—C7C	121.7 (4)
C8D—C7D—C11D	117.8 (4)	C8C—C7C—C11C	117.1 (4)
C8D—C7D—C6D	124.6 (4)	C8C—C7C—C6C	124.2 (4)
C11D—C7D—C6D	117.5 (4)	C11C—C7C—C6C	118.7 (4)
C9D—C8D—C7D	119.7 (4)	C9C—C8C—C7C	119.8 (4)
C8D—C9D—C10D	119.4 (4)	C8C—C9C—C10C	119.4 (4)
N2D—C10D—C9D	122.8 (4)	N2C—C10C—C9C	122.7 (4)
N2D—C11D—C7D	122.1 (4)	N2C—C11C—C7C	123.1 (4)
N2D—C11D—C12D	117.6 (3)	N2C—C11C—C12C	117.0 (3)
C7D—C11D—C12D	120.2 (3)	C7C—C11C—C12C	119.9 (3)
N1D—C12D—C4D	122.2 (3)	N1C—C12C—C4C	122.7 (3)
N1D—C12D—C11D	117.2 (3)	N1C—C12C—C11C	117.4 (3)
C4D—C12D—C11D	120.7 (3)	C4C—C12C—C11C	119.9 (3)

(II) Bis-(2,2'-bipyridyl-N,N')-(thiosulfato-O,S)-nickel(II), hydrate, methanol solvate

Crystal data

[Ni(O3S2)(C10H8N2)2]·2H2O·0.55CH4O	F(000) = 2223
Mr = 536.84	Dx = 1.56 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.754 (4) Å	Cell parameters from 25 reflections
b = 20.895 (4) Å	θ = 7.5–15°
c = 14.402 (3) Å	µ = 1.07 mm^−1
β = 132.919 (12)°	T = 293 K
V = 4573.7 (17) Å^3	Polyhedra, pale-grey
Z = 8	0.33 × 0.30 × 0.28 mm

Data collection

Rigaku AFC7S Difractometer diffractometer	2159 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.075
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ω/2θ scans	h = −24→18
Absorption correction: ψ scan MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988)	k = 0→24
Tmin = 0.71, Tmax = 0.74	l = 0→17
4123 measured reflections	3 standard reflections every 150 reflections
3914 independent reflections	intensity decay: <3%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.183	H-atom parameters constrained
S = 0.97	Calculated w = 1/[σ^2(Fo^2) + (0.085P)^2 + 8.029P] where P = (Fo^2 + 2Fc^2)/3
3914 reflections	(Δ/σ)max < 0.01
325 parameters	Δρmax = 0.67 e Å^−3
28 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. The compound is absolutely unstable outside the mother liquors and required to be encapsulated

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.21820 (6)	0.09475 (4)	0.83918 (8)	0.0405 (3)
S1	0.24397 (13)	0.08333 (9)	0.69632 (18)	0.0553 (5)
S2	0.35144 (12)	0.13402 (9)	0.84032 (18)	0.0494 (5)
O1	0.3395 (3)	0.1416 (2)	0.9303 (4)	0.0484 (12)
O2	0.4315 (3)	0.0982 (3)	0.8990 (5)	0.0698 (16)
O3	0.3515 (4)	0.1963 (2)	0.7949 (6)	0.0744 (18)
N1A	0.2167 (3)	0.1216 (2)	0.9766 (5)	0.0422 (14)
N2A	0.1478 (4)	0.1809 (3)	0.7651 (6)	0.0519 (16)
C1A	0.2522 (5)	0.0895 (3)	1.0826 (6)	0.0496 (18)
H1A	0.2821	0.0517	1.0992	0.060*
C2A	0.2469 (6)	0.1092 (4)	1.1685 (8)	0.065 (2)
H2A	0.2708	0.0844	1.2392	0.078*
C3A	0.2059 (6)	0.1660 (4)	1.1477 (9)	0.075 (3)
H3A	0.2027	0.1810	1.2053	0.090*
C4A	0.1695 (5)	0.2003 (4)	1.0404 (8)	0.068 (2)
H4A	0.1402	0.2385	1.0233	0.081*
C5A	0.1771 (4)	0.1773 (3)	0.9570 (7)	0.0476 (18)
C6A	0.1412 (4)	0.2120 (3)	0.8406 (7)	0.055 (2)
C7A	0.1042 (5)	0.2727 (3)	0.8096 (9)	0.069 (3)
H7A	0.1026	0.2942	0.8645	0.082*
C8A	0.0702 (6)	0.3005 (5)	0.6989 (10)	0.087 (3)
H8A	0.0448	0.3410	0.6773	0.104*
C9A	0.0737 (6)	0.2683 (4)	0.6196 (9)	0.080 (3)
H9A	0.0495	0.2860	0.5423	0.096*
C10A	0.1141 (5)	0.2090 (4)	0.6569 (7)	0.066 (2)
H10A	0.1179	0.1878	0.6041	0.080*
N1B	0.1101 (3)	0.0344 (2)	0.7418 (5)	0.0434 (14)
N2B	0.2788 (3)	0.0085 (2)	0.9252 (5)	0.0428 (14)
C1B	0.0259 (4)	0.0508 (4)	0.6467 (7)	0.060 (2)
H1B	0.0122	0.0939	0.6261	0.072*
C2B	−0.0417 (5)	0.0066 (4)	0.5776 (8)	0.071 (3)
H2B	−0.0996	0.0197	0.5121	0.085*
C3B	−0.0213 (5)	−0.0567 (4)	0.6077 (8)	0.074 (3)
H3B	−0.0655	−0.0874	0.5629	0.089*
C4B	0.0652 (5)	−0.0747 (4)	0.7050 (7)	0.060 (2)
H4B	0.0801	−0.1177	0.7252	0.072*
C5B	0.1298 (4)	−0.0278 (3)	0.7722 (6)	0.0447 (17)
C6B	0.2235 (4)	−0.0415 (3)	0.8796 (6)	0.0432 (17)
C7B	0.2548 (5)	−0.1022 (3)	0.9307 (7)	0.061 (2)
H7B	0.2161	−0.1363	0.9000	0.073*
C8B	0.3435 (6)	−0.1111 (4)	1.0270 (8)	0.076 (3)
H8B	0.3656	−0.1515	1.0629	0.091*
C9B	0.3999 (5)	−0.0606 (4)	1.0705 (7)	0.061 (2)
H9B	0.4605	−0.0665	1.1334	0.074*
C10B	0.3651 (4)	−0.0008 (4)	1.0193 (7)	0.056 (2)
H10B	0.4029	0.0341	1.0514	0.067*
O1W	0.5654 (4)	0.0382 (3)	1.1495 (6)	0.096 (2)
O2WA	0.170 (7)	0.216 (6)	0.504 (9)	0.09 (3)	0.26 (13)
O2WB	0.218 (6)	0.238 (2)	0.538 (4)	0.15 (2)	0.74 (13)
O1X	0.4176 (11)	0.2678 (6)	0.7110 (17)	0.118 (6)	0.548 (8)
C1X	0.4949 (13)	0.2661 (9)	0.8428 (18)	0.093 (7)	0.548 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0376 (5)	0.0341 (5)	0.0401 (5)	0.0018 (4)	0.0227 (4)	−0.0004 (4)
S1	0.0578 (12)	0.0549 (12)	0.0441 (11)	−0.0054 (9)	0.0312 (10)	−0.0091 (9)
S2	0.0496 (11)	0.0449 (11)	0.0525 (11)	−0.0030 (9)	0.0343 (10)	−0.0032 (9)
O1	0.049 (3)	0.045 (3)	0.046 (3)	−0.010 (2)	0.030 (3)	−0.008 (2)
O2	0.049 (3)	0.082 (4)	0.069 (4)	0.006 (3)	0.037 (3)	−0.011 (3)
O3	0.109 (5)	0.045 (3)	0.087 (4)	−0.017 (3)	0.074 (4)	−0.001 (3)
N1A	0.036 (3)	0.037 (3)	0.045 (4)	−0.002 (2)	0.024 (3)	−0.005 (3)
N2A	0.046 (3)	0.037 (3)	0.057 (4)	0.004 (3)	0.029 (3)	0.008 (3)
C1A	0.049 (4)	0.048 (4)	0.046 (4)	−0.005 (4)	0.029 (4)	−0.007 (4)
C2A	0.078 (6)	0.063 (5)	0.059 (5)	−0.008 (5)	0.048 (5)	−0.012 (4)
C3A	0.075 (6)	0.083 (7)	0.075 (7)	−0.012 (5)	0.054 (6)	−0.021 (5)
C4A	0.063 (5)	0.055 (5)	0.094 (7)	−0.007 (4)	0.058 (5)	−0.023 (5)
C5A	0.044 (4)	0.035 (4)	0.066 (5)	−0.007 (3)	0.038 (4)	−0.011 (4)
C6A	0.033 (4)	0.052 (5)	0.068 (5)	−0.003 (3)	0.030 (4)	−0.005 (4)
C7A	0.065 (5)	0.034 (4)	0.115 (8)	0.014 (4)	0.064 (6)	0.007 (5)
C8A	0.065 (6)	0.054 (6)	0.133 (10)	0.022 (5)	0.064 (7)	0.029 (6)
C9A	0.058 (5)	0.070 (6)	0.082 (7)	0.017 (5)	0.036 (5)	0.037 (6)
C10A	0.053 (5)	0.059 (5)	0.056 (5)	0.000 (4)	0.025 (4)	0.008 (4)
N1B	0.036 (3)	0.044 (3)	0.046 (3)	0.000 (3)	0.026 (3)	−0.005 (3)
N2B	0.045 (3)	0.041 (3)	0.045 (3)	0.003 (3)	0.031 (3)	0.002 (3)
C1B	0.045 (5)	0.064 (5)	0.061 (5)	0.003 (4)	0.032 (4)	−0.002 (4)
C2B	0.042 (5)	0.093 (7)	0.052 (5)	−0.008 (5)	0.022 (4)	−0.012 (5)
C3B	0.060 (6)	0.093 (7)	0.063 (6)	−0.038 (5)	0.039 (5)	−0.033 (5)
C4B	0.065 (5)	0.054 (5)	0.061 (5)	−0.019 (4)	0.043 (5)	−0.020 (4)
C5B	0.055 (5)	0.046 (4)	0.049 (4)	−0.003 (3)	0.042 (4)	−0.005 (3)
C6B	0.053 (4)	0.040 (4)	0.043 (4)	0.001 (3)	0.036 (4)	0.000 (3)
C7B	0.071 (6)	0.047 (5)	0.056 (5)	0.001 (4)	0.040 (5)	0.007 (4)
C8B	0.103 (8)	0.045 (5)	0.083 (7)	0.028 (5)	0.064 (7)	0.031 (5)
C9B	0.059 (5)	0.072 (6)	0.052 (5)	0.031 (5)	0.037 (4)	0.030 (4)
C10B	0.041 (4)	0.063 (5)	0.060 (5)	0.010 (4)	0.033 (4)	0.017 (4)
O1W	0.080 (5)	0.087 (5)	0.095 (5)	−0.009 (4)	0.050 (4)	−0.029 (4)
O2WA	0.12 (5)	0.09 (4)	0.13 (4)	0.05 (3)	0.11 (4)	0.08 (3)
O2WB	0.25 (5)	0.093 (14)	0.166 (16)	0.07 (2)	0.17 (2)	0.063 (14)
O1X	0.169 (15)	0.066 (8)	0.195 (18)	−0.026 (9)	0.154 (15)	−0.010 (10)
C1X	0.123 (18)	0.077 (13)	0.112 (17)	−0.017 (12)	0.093 (16)	0.016 (12)

Geometric parameters (Å, º)

Ni1—N2B	2.060 (5)	C6A—C7A	1.388 (8)
Ni1—N1B	2.076 (5)	C7A—C8A	1.359 (9)
Ni1—N1A	2.078 (6)	C8A—C9A	1.370 (10)
Ni1—N2A	2.095 (6)	C9A—C10A	1.383 (9)
Ni1—O1	2.125 (5)	N1B—C1B	1.337 (7)
Ni1—S1	2.465 (2)	N1B—C5B	1.344 (7)
S1—S2	2.024 (3)	N2B—C10B	1.332 (7)
S2—O3	1.456 (5)	N2B—C6B	1.347 (7)
S2—O2	1.457 (5)	C1B—C2B	1.381 (8)
S2—O1	1.485 (5)	C2B—C3B	1.367 (9)
N1A—C1A	1.338 (7)	C3B—C4B	1.380 (9)
N1A—C5A	1.341 (7)	C4B—C5B	1.388 (8)
N2A—C10A	1.333 (8)	C5B—C6B	1.470 (8)
N2A—C6A	1.352 (8)	C6B—C7B	1.386 (8)
C1A—C2A	1.376 (9)	C7B—C8B	1.368 (9)
C2A—C3A	1.371 (9)	C8B—C9B	1.370 (9)
C3A—C4A	1.373 (9)	C9B—C10B	1.379 (8)
C4A—C5A	1.397 (8)	O2WA—O2WB	0.88 (5)
C5A—C6A	1.481 (9)	O1X—C1X	1.425 (10)
N2B—Ni1—N1B	79.1 (2)	C3A—C4A—C5A	119.4 (8)
N2B—Ni1—N1A	93.6 (2)	N1A—C5A—C4A	122.0 (7)
N1B—Ni1—N1A	95.6 (2)	N1A—C5A—C6A	115.3 (6)
N2B—Ni1—N2A	170.6 (2)	C4A—C5A—C6A	122.7 (6)
N1B—Ni1—N2A	96.9 (2)	N2A—C6A—C7A	121.2 (7)
N1A—Ni1—N2A	78.2 (2)	N2A—C6A—C5A	115.3 (6)
N2B—Ni1—O1	92.9 (2)	C7A—C6A—C5A	123.5 (7)
N1B—Ni1—O1	168.0 (2)	C8A—C7A—C6A	120.0 (8)
N1A—Ni1—O1	93.8 (2)	C7A—C8A—C9A	119.2 (9)
N2A—Ni1—O1	92.3 (2)	C8A—C9A—C10A	118.6 (9)
N2B—Ni1—S1	91.50 (17)	N2A—C10A—C9A	123.1 (9)
N1B—Ni1—S1	97.27 (17)	C1B—N1B—C5B	118.5 (6)
N1A—Ni1—S1	166.88 (16)	C1B—N1B—Ni1	126.4 (5)
N2A—Ni1—S1	97.49 (19)	C5B—N1B—Ni1	114.8 (4)
O1—Ni1—S1	73.81 (15)	C10B—N2B—C6B	119.5 (6)
S2—S1—Ni1	78.94 (9)	C10B—N2B—Ni1	125.9 (5)
O3—S2—O2	111.7 (4)	C6B—N2B—Ni1	114.6 (4)
O3—S2—O1	110.4 (3)	N1B—C1B—C2B	122.9 (7)
O2—S2—O1	110.6 (3)	C3B—C2B—C1B	118.4 (7)
O3—S2—S1	110.2 (3)	C2B—C3B—C4B	119.6 (7)
O2—S2—S1	110.6 (2)	C3B—C4B—C5B	119.1 (7)
O1—S2—S1	103.2 (2)	N1B—C5B—C4B	121.4 (6)
S2—O1—Ni1	104.1 (2)	N1B—C5B—C6B	115.0 (5)
C1A—N1A—C5A	117.2 (6)	C4B—C5B—C6B	123.7 (6)
C1A—N1A—Ni1	126.7 (5)	N2B—C6B—C7B	121.0 (6)
C5A—N1A—Ni1	116.0 (5)	N2B—C6B—C5B	116.1 (5)
C10A—N2A—C6A	117.8 (7)	C7B—C6B—C5B	122.8 (6)
C10A—N2A—Ni1	127.1 (6)	C8B—C7B—C6B	118.9 (7)
C6A—N2A—Ni1	114.9 (5)	C7B—C8B—C9B	120.0 (7)
N1A—C1A—C2A	123.8 (7)	C8B—C9B—C10B	118.7 (7)
C3A—C2A—C1A	118.7 (8)	N2B—C10B—C9B	121.8 (7)
C2A—C3A—C4A	118.8 (8)