Tris(2,2′-bipyridyl-N,N′)­nickel(II) thio­sulfate heptahydrate

The structure of the title compound, [Ni(C₁₀H₈­N₂)₃](S₂O₃)·7H₂O, consists of monomeric Ni(bipy)₃²⁺ cations embedded in an anionic network made up of S₂O₃²⁻ ions and hydration water mol­ecules. The structure presents the unusual feature of two neighbouring thio­sulfates approaching linearly head-to-head with an unusually short S...S contact distance of 3.25 Å.

S1. Comment

The nickel thiosulfate complexes reported so far number five: in three of them the anion behaves as an S,O chelato (Fava Gasparri et al., 1969; Freire et al., 2000), while in the remaining two (Freire et al., 1999) it acts as monodentate, binding through oxygen. In all cases, the coordination scheme gives rise to monomeric species. The present structure, (I), also monomeric, displays a different scheme where the thiosulfate anion does not coordinate directly neither to the distorted octahedral Ni(bipy)₃²⁺ cations nor to any ligand molecule. The anionic group is instead involved in a number of hydrogen bonds leading to an anionic network (Figure 1).

The anion displays a rather regular geometry, with a slight spread on homologous parameters range in S—O distances: 1.439 (5)–1.453 (5) Å; range in S—S—O angles: 108.1 (3)–109.2 (3)°. These values, as well as the S—S bond length of 1.969 (3) Å, are in good agreement with those previously reported in other ionic moieties (Teng et al., 1984; Baggio et al., 1997).

The Ni²⁺ cation, situated in a general, unconstrained position, is attached to three independent bipyridine groups in a `propeller like' binding mode which provides a somewhat distorted octahedral coordination. This Ni(bipy)₃ group is rather common in the literature: 17 entries in the CSD, 9 of them with R factors below 10%. A systematic analysis of this latter selected group revealed a rather rigid structural pattern for the Ni coordination polyhedron, with bond distances and bite angles ranging in a very narrow band: Ni—N:2.066–2.138 Å, N—Ni—N:78.14–79.80°. The values in the present structure [2.086 (3)–2.101 (3) Å, 78.36 (12)–78.63 (14)°] fit perfectly well in this pattern.

Interatomic bonds and angles in the bipyridine ligands are unexceptional, the six individual heterocyclic groups being basically planar, the maximum departure from the weighted least squares planes as calculated with PARST (Nardelli, 1983) being for atom C9B, 0.019 (5) Å. However, none of the three independent bipyridine moieties is planar as a whole, as they display a variety of twist angles around the C5—C6 bond which range from 4.2 (1) for bipy A to 11.3 (1)° for bipy B.

The structure is completed by seven hydration water molecules (TGA measurements in bulk give a slightly lower figure of 6.5), three of which appear scattered in seven different positions (O5W to O11W). This characteristics prevented the finding of all the H_water atoms, so as to allow a precise discussion of the hydrogen-bonding interactions. However, inspection of a schematic unit cell diagram (Figure 2) allows a simple description of the packing: the hydration water molecules form a narrow cloud normal to the c axis at heights c ~0 and c ~0.5. Besides, the thiosulfate groups couple into pairs through a head to head (O₃S—S)···(S—SO₃)[2 - x,y,1.5 - z] interaction where the sulfur atoms lay 3.250 (3) Å apart, a much shorter distance than the sum of the most commonly accepted Van der Waal's radii (~3.60 Å, Taylor & Kennard, 1982; ~3.70 Å, Pauling, 1960). A search in the Cambridge Structural Database showed that out of some 14330 entries with reported S···S intermolecular contacts in the range 3.75 Å down to 2.51 Å, only 295 (ca 2%) showed values below the 3.25 Å reported herein. These thiosulfate linear pairs, with their centers at c ~0.25 and c ~0.75 lie normal to the water planes, and bridge them into an anionic network through a dense hydrogen-bonding interaction scheme involving two thiosulfate O atoms as well as all the hydration water molecules (Table 2). The resulting `niches' are occupied by the Ni(bipy)₃²⁺ cations. The interaction of the latter with the anionic network takes place mainly by weak C—H···O interactions.

A similar disposition has been found in two compounds very nearly isostructural to the one herein reported: the homologous tris(2,2'-bipyridyl)zinc(II) thiosulfate heptahydrate (Baggio et al., 1997) and tris(2,2'-bipyridyl) nickel(II) sulfate hydrate (Wada et al., 1976). The former structure presents a similar `inter thiosulfate' interaction, though a bit softer (S···S 3.36 Å). The latter, instead, presents a slight modification: the coupling between opposed anions (too far apart for any direct interaction) is bridged by a water molecule, 2.63 Å apart from each one of the two innermost O atoms.

S2. Experimental

The compound appeared as a by-product in the synthesis of bis-(2,2'-bipyridyl-N,N')(thiosulfato-O,S)nickel(II), hydrate, methanol solvate (Freire et al., 2000). During the synthesis reported therein (slow diffusion of an aqueous solution of nickel nitrate and sodium thiosulfate into a methanolic solution of 1,10-phenanthroline in a 1:3:2 molar ratio) a few, quite imperfect reddish crystals of some secondary phase appeared. This suggested that some other composition besides the dominant NiS₂O₃(bpy)₂.nH₂O.mCH₃OH could also be stable, and so attempts were made to obtain them starting from different reactant concentrations. The best results were obtained with a 1:3:2.5 ratio, where deep red, very stable, prismatic crystals were obtained, by the same diffusion method.

S3. Refinement

The structure appeared unusually difficult to solve by direct methods: in the (lately proved) correct space group, C2/c, the procedure yielded no acceptable solutions whatsoever; in C2, instead, it gave a set of two, almost complete but wrongly positioned molecules, both in absolute as well as in their relative position. In spite of this, the model would misleadingly refine down to a surprisingly low R = 10%. The structure was finally solved through a Patterson synthesis, (from where only the Ni ion was picked up), and completed by difference Fourier cycling. Refinement on F² was performed using the whole data set. The water content as determined from TGA measurements gave an hydration number of ca 6.5, in fair agreement with the refinement results. Only four water molecules (O1W to O4W) appeared well defined and refined to full occupancy. The remaining three were found to be scattered into seven different disordered sites O5W to O11W. Due to their poor definition they were refined isotropically. H atoms bonded to carbon were added at their expected positions and allowed to ride. Those from the well behaved water molecules were found in the difference Fourier and refined without restraints; the ones from O5W to O11W, instead, could not be located and were accordingly ignored.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 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 Cambridge Structure Database (Allen & Kennard, 1993).

Figures

	Fig. 1. View of the ions making up the structure showing the numbering scheme used, as well as displacement ellipsoids drawn at a 50% level.
	Fig. 2. Simplified packing diagram showing the anionic network with the embedded cations occupying the voids. Hydrogen atoms are not represented.

Tris(2,2'-bipyridyl)nickel(II) thiosulfate heptahydrate

Crystal data

[Ni(C10H8N2)(S2O3)·7H2O	F(000) = 3200
Mr = 765.49	Dx = 1.465 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.934 (5) Å	Cell parameters from 25 reflections
b = 13.481 (3) Å	θ = 7.5–15°
c = 24.904 (5) Å	µ = 0.74 mm^−1
β = 115.65 (3)°	T = 293 K
V = 6941 (2) Å^3	Polyhedra, red
Z = 8	0.30 × 0.28 × 0.22 mm

Data collection

Rigaku AFC7S Difractometer diffractometer	4723 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
ω/2θ scans	h = −29→1
Absorption correction: ψ scan (Molecular Structure Corporation, 1988)	k = −17→1
Tmin = 0.80, Tmax = 0.83	l = −29→32
9294 measured reflections	3 standard reflections every 150 reflections
7963 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)] = 0.059	Hydrogen site location: geom+difmap
wR(F^2) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Calculated w = 1/[σ^2(Fo^2) + (0.118P)^2 + 6.806P] where P = (Fo^2 + 2Fc^2)/3
7963 reflections	(Δ/σ)max < 0.01
483 parameters	Δρmax = 0.68 e Å^−3
13 restraints	Δρmin = −0.89 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.84096 (2)	0.06871 (3)	0.75897 (2)	0.03578 (16)
S1	1.02850 (9)	0.56856 (11)	0.82217 (10)	0.0931 (5)
S2	1.06849 (8)	0.56730 (11)	0.90985 (10)	0.0880 (5)
O1	1.0200 (3)	0.5363 (4)	0.9288 (3)	0.1211 (18)
O2	1.0921 (3)	0.6653 (3)	0.9311 (3)	0.1197 (18)
O3	1.1224 (3)	0.4982 (5)	0.9314 (3)	0.144 (2)
N1A	0.82984 (17)	0.2010 (2)	0.71178 (15)	0.0455 (8)
N2A	0.92424 (15)	0.1468 (2)	0.81472 (14)	0.0423 (7)
C1A	0.7804 (2)	0.2242 (3)	0.6594 (2)	0.0606 (12)
H1AA	0.7454	0.1811	0.6432	0.073*
C2A	0.7798 (3)	0.3101 (4)	0.6288 (2)	0.0743 (15)
H2AA	0.7451	0.3242	0.5926	0.089*
C3A	0.8311 (3)	0.3741 (4)	0.6527 (3)	0.0797 (17)
H3AA	0.8320	0.4315	0.6324	0.096*
C4A	0.8812 (3)	0.3522 (3)	0.7070 (2)	0.0637 (13)
H4AA	0.9160	0.3956	0.7242	0.076*
C5A	0.8797 (2)	0.2650 (3)	0.73589 (19)	0.0473 (9)
C6A	0.93121 (19)	0.2363 (3)	0.79425 (19)	0.0461 (9)
C7A	0.9841 (2)	0.2968 (4)	0.8271 (3)	0.0670 (13)
H7AA	0.9885	0.3582	0.8123	0.080*
C8A	1.0294 (3)	0.2648 (4)	0.8814 (3)	0.0736 (15)
H8AA	1.0651	0.3041	0.9037	0.088*
C9A	1.0219 (2)	0.1750 (4)	0.9025 (2)	0.0696 (13)
H9AA	1.0520	0.1528	0.9396	0.084*
C10A	0.9691 (2)	0.1173 (4)	0.86842 (19)	0.0539 (10)
H10A	0.9643	0.0559	0.8830	0.065*
N1B	0.88708 (15)	−0.0068 (2)	0.71445 (14)	0.0420 (7)
N2B	0.86788 (16)	−0.0639 (2)	0.80753 (15)	0.0436 (7)
C1B	0.8913 (2)	0.0248 (3)	0.66515 (19)	0.0545 (10)
H1BA	0.8819	0.0907	0.6537	0.065*
C2B	0.9093 (2)	−0.0379 (4)	0.6307 (2)	0.0619 (12)
H2BA	0.9115	−0.0146	0.5965	0.074*
C3B	0.9238 (2)	−0.1344 (4)	0.6480 (2)	0.0674 (14)
H3BA	0.9353	−0.1780	0.6252	0.081*
C4B	0.9213 (2)	−0.1671 (3)	0.6997 (2)	0.0585 (11)
H4BA	0.9320	−0.2322	0.7125	0.070*
C5B	0.90276 (18)	−0.1015 (3)	0.73191 (18)	0.0420 (8)
C6B	0.89682 (18)	−0.1307 (3)	0.78671 (18)	0.0445 (9)
C7B	0.9209 (2)	−0.2194 (3)	0.8159 (2)	0.0636 (12)
H7BA	0.9406	−0.2648	0.8009	0.076*
C8B	0.9150 (3)	−0.2391 (4)	0.8679 (3)	0.0769 (16)
H8BA	0.9309	−0.2982	0.8883	0.092*
C9B	0.8860 (3)	−0.1719 (4)	0.8893 (2)	0.0707 (14)
H9BA	0.8823	−0.1840	0.9244	0.085*
C10B	0.8621 (2)	−0.0850 (3)	0.8576 (2)	0.0573 (11)
H10B	0.8413	−0.0397	0.8716	0.069*
N1C	0.74990 (15)	0.0123 (2)	0.70104 (14)	0.0440 (7)
N2C	0.78391 (16)	0.1175 (2)	0.80006 (14)	0.0429 (7)
C1C	0.7349 (2)	−0.0370 (3)	0.6500 (2)	0.0563 (11)
H1CA	0.7679	−0.0524	0.6393	0.068*
C2C	0.6726 (3)	−0.0659 (4)	0.6125 (2)	0.0661 (13)
H2CA	0.6638	−0.0980	0.5767	0.079*
C3C	0.6244 (2)	−0.0464 (4)	0.6291 (2)	0.0672 (13)
H3CA	0.5822	−0.0668	0.6053	0.081*
C4C	0.6389 (2)	0.0043 (4)	0.6818 (2)	0.0604 (12)
H4CA	0.6063	0.0189	0.6933	0.072*
C5C	0.70147 (18)	0.0329 (3)	0.71702 (18)	0.0444 (9)
C6C	0.72206 (19)	0.0888 (3)	0.77401 (19)	0.0448 (9)
C7C	0.6799 (2)	0.1093 (4)	0.7992 (2)	0.0572 (11)
H7CA	0.6369	0.0895	0.7803	0.069*
C8C	0.7026 (3)	0.1587 (4)	0.8518 (2)	0.0662 (13)
H8CA	0.6751	0.1719	0.8695	0.079*
C9C	0.7660 (3)	0.1895 (4)	0.8790 (2)	0.0633 (12)
H9CA	0.7817	0.2244	0.9147	0.076*
C10C	0.8058 (2)	0.1674 (3)	0.8519 (2)	0.0537 (10)
H10C	0.8489	0.1874	0.8700	0.064*
O1W	1.0433 (3)	0.3803 (4)	1.0062 (3)	0.1069 (15)
H1WA	1.041 (3)	0.427 (3)	0.980 (2)	0.08 (2)*
H1WB	1.027 (4)	0.403 (5)	1.031 (3)	0.17 (4)*
O2W	1.0642 (3)	0.7539 (4)	1.0182 (2)	0.0980 (13)
H2WA	1.072 (3)	0.734 (4)	0.989 (2)	0.09 (2)*
H2WB	1.041 (4)	0.711 (5)	1.028 (4)	0.18 (5)*
O3W	0.9492 (3)	−0.0456 (4)	0.5050 (3)	0.1124 (17)
H3WA	0.9080 (18)	−0.024 (4)	0.487 (3)	0.10 (2)*
H3WB	0.950 (3)	−0.111 (2)	0.500 (3)	0.10 (2)*
O4W	1.1739 (4)	0.3441 (7)	1.0168 (3)	0.142 (2)
H4WA	1.140 (3)	0.347 (6)	1.025 (4)	0.13 (4)*
H4WB	1.193 (5)	0.404 (4)	1.020 (6)	0.23 (8)*
O5W	1.3106 (3)	0.3343 (5)	1.0349 (3)	0.100 (3)*	0.731 (12)
O6W	1.3188 (4)	0.4959 (7)	0.9728 (3)	0.109 (4)*	0.74 (2)
O7W	1.2249 (8)	0.6763 (15)	1.0008 (6)	0.122 (7)*	0.43 (2)
O8W	1.2473 (6)	0.6174 (12)	1.0102 (5)	0.106 (5)*	0.50 (2)
O9W	1.2476 (11)	0.4974 (18)	1.0108 (10)	0.116 (6)*	0.236 (9)
O10W	1.3397 (13)	0.432 (2)	0.9833 (11)	0.095 (12)*	0.20 (2)
O11W	1.3010 (15)	0.444 (2)	1.0035 (14)	0.100 (14)*	0.170 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0394 (3)	0.0308 (2)	0.0407 (3)	0.00044 (19)	0.02065 (19)	0.00019 (19)
S1	0.0907 (11)	0.0590 (8)	0.1560 (17)	0.0020 (7)	0.0783 (12)	0.0050 (9)
S2	0.0905 (11)	0.0539 (8)	0.1466 (15)	0.0044 (7)	0.0767 (11)	0.0080 (8)
O1	0.127 (4)	0.092 (3)	0.180 (5)	−0.018 (3)	0.099 (4)	0.008 (3)
O2	0.143 (4)	0.065 (3)	0.180 (5)	−0.024 (3)	0.097 (4)	−0.001 (3)
O3	0.153 (5)	0.126 (5)	0.170 (5)	0.062 (4)	0.085 (5)	0.022 (4)
N1A	0.058 (2)	0.0323 (16)	0.0535 (19)	0.0054 (14)	0.0306 (17)	0.0070 (14)
N2A	0.0409 (17)	0.0377 (17)	0.0530 (18)	−0.0052 (13)	0.0248 (15)	−0.0029 (14)
C1A	0.071 (3)	0.051 (3)	0.056 (3)	0.013 (2)	0.024 (2)	0.013 (2)
C2A	0.107 (4)	0.057 (3)	0.062 (3)	0.026 (3)	0.040 (3)	0.020 (2)
C3A	0.141 (6)	0.041 (3)	0.082 (4)	0.013 (3)	0.072 (4)	0.017 (3)
C4A	0.090 (4)	0.039 (2)	0.081 (3)	−0.002 (2)	0.055 (3)	0.004 (2)
C5A	0.062 (2)	0.0318 (18)	0.062 (2)	0.0012 (17)	0.040 (2)	−0.0002 (17)
C6A	0.049 (2)	0.038 (2)	0.062 (2)	−0.0025 (16)	0.034 (2)	−0.0058 (18)
C7A	0.065 (3)	0.047 (3)	0.099 (4)	−0.015 (2)	0.045 (3)	−0.013 (3)
C8A	0.057 (3)	0.065 (3)	0.095 (4)	−0.018 (2)	0.029 (3)	−0.027 (3)
C9A	0.054 (3)	0.075 (3)	0.071 (3)	−0.005 (2)	0.019 (2)	−0.016 (3)
C10A	0.049 (2)	0.058 (3)	0.050 (2)	−0.003 (2)	0.0174 (19)	−0.004 (2)
N1B	0.0462 (17)	0.0370 (16)	0.0501 (18)	0.0023 (13)	0.0277 (15)	−0.0019 (14)
N2B	0.0504 (18)	0.0326 (15)	0.0489 (17)	−0.0009 (14)	0.0226 (15)	0.0073 (14)
C1B	0.069 (3)	0.053 (2)	0.057 (2)	−0.002 (2)	0.043 (2)	0.000 (2)
C2B	0.063 (3)	0.078 (3)	0.056 (3)	−0.007 (2)	0.037 (2)	−0.013 (2)
C3B	0.059 (3)	0.077 (3)	0.073 (3)	−0.001 (2)	0.036 (2)	−0.031 (3)
C4B	0.053 (2)	0.047 (2)	0.076 (3)	0.005 (2)	0.028 (2)	−0.014 (2)
C5B	0.0409 (19)	0.0344 (18)	0.052 (2)	0.0010 (15)	0.0216 (17)	−0.0015 (16)
C6B	0.0408 (19)	0.0322 (18)	0.057 (2)	0.0000 (15)	0.0177 (17)	0.0024 (17)
C7B	0.066 (3)	0.039 (2)	0.077 (3)	0.008 (2)	0.023 (3)	0.012 (2)
C8B	0.082 (4)	0.050 (3)	0.079 (3)	0.000 (3)	0.017 (3)	0.027 (3)
C9B	0.092 (4)	0.060 (3)	0.059 (3)	−0.005 (3)	0.032 (3)	0.022 (2)
C10B	0.072 (3)	0.051 (3)	0.054 (2)	−0.005 (2)	0.032 (2)	0.008 (2)
N1C	0.0417 (17)	0.0375 (17)	0.0495 (18)	−0.0003 (13)	0.0166 (15)	−0.0037 (14)
N2C	0.0475 (18)	0.0390 (17)	0.0518 (18)	0.0002 (14)	0.0303 (15)	−0.0027 (14)
C1C	0.057 (3)	0.053 (2)	0.055 (2)	0.000 (2)	0.021 (2)	−0.012 (2)
C2C	0.064 (3)	0.055 (3)	0.063 (3)	−0.005 (2)	0.013 (2)	−0.014 (2)
C3C	0.051 (3)	0.057 (3)	0.074 (3)	−0.010 (2)	0.009 (2)	−0.005 (2)
C4C	0.046 (2)	0.056 (3)	0.075 (3)	−0.003 (2)	0.024 (2)	0.005 (2)
C5C	0.0404 (19)	0.0355 (18)	0.057 (2)	−0.0005 (16)	0.0204 (18)	0.0050 (17)
C6C	0.045 (2)	0.0366 (19)	0.060 (2)	0.0051 (16)	0.0290 (19)	0.0066 (17)
C7C	0.055 (3)	0.057 (3)	0.073 (3)	0.006 (2)	0.040 (2)	0.005 (2)
C8C	0.078 (3)	0.063 (3)	0.084 (3)	0.016 (3)	0.060 (3)	0.011 (3)
C9C	0.087 (4)	0.056 (3)	0.065 (3)	0.006 (2)	0.050 (3)	−0.007 (2)
C10C	0.063 (3)	0.051 (2)	0.058 (2)	−0.004 (2)	0.036 (2)	−0.011 (2)
O1W	0.150 (5)	0.078 (3)	0.108 (4)	−0.001 (3)	0.071 (4)	−0.003 (3)
O2W	0.104 (4)	0.086 (3)	0.100 (4)	0.004 (3)	0.040 (3)	−0.002 (3)
O3W	0.118 (4)	0.088 (4)	0.158 (5)	0.000 (3)	0.085 (4)	−0.014 (3)
O4W	0.110 (5)	0.149 (7)	0.140 (5)	0.027 (4)	0.030 (4)	0.004 (4)

Geometric parameters (Å, º)

Ni1—N2C	2.086 (3)	N2B—C10B	1.341 (5)
Ni1—N1A	2.090 (3)	N2B—C6B	1.348 (5)
Ni1—N2A	2.095 (3)	C1B—C2B	1.388 (6)
Ni1—N2B	2.096 (3)	C2B—C3B	1.366 (7)
Ni1—N1B	2.097 (3)	C3B—C4B	1.386 (7)
Ni1—N1C	2.101 (3)	C4B—C5B	1.379 (6)
S1—S2	1.969 (3)	C5B—C6B	1.482 (6)
S2—O2	1.439 (5)	C6B—C7B	1.384 (5)
S2—O1	1.445 (5)	C7B—C8B	1.386 (7)
S2—O3	1.453 (5)	C8B—C9B	1.361 (8)
N1A—C1A	1.344 (5)	C9B—C10B	1.386 (6)
N1A—C5A	1.348 (5)	N1C—C1C	1.341 (5)
N2A—C6A	1.347 (5)	N1C—C5C	1.361 (5)
N2A—C10A	1.346 (5)	N2C—C6C	1.337 (5)
C1A—C2A	1.382 (6)	N2C—C10C	1.346 (5)
C2A—C3A	1.369 (8)	C1C—C2C	1.382 (7)
C3A—C4A	1.375 (8)	C2C—C3C	1.363 (8)
C4A—C5A	1.387 (6)	C3C—C4C	1.386 (7)
C5A—C6A	1.474 (6)	C4C—C5C	1.374 (6)
C6A—C7A	1.394 (6)	C5C—C6C	1.492 (6)
C7A—C8A	1.371 (8)	C6C—C7C	1.389 (6)
C8A—C9A	1.360 (8)	C7C—C8C	1.357 (7)
C9A—C10A	1.379 (6)	C8C—C9C	1.376 (7)
N1B—C1B	1.342 (5)	C9C—C10C	1.383 (6)
N1B—C5B	1.348 (5)
N2C—Ni1—N1A	93.26 (13)	C1B—N1B—C5B	118.7 (3)
N2C—Ni1—N2A	95.85 (13)	C1B—N1B—Ni1	125.7 (3)
N1A—Ni1—N2A	78.36 (13)	C5B—N1B—Ni1	114.5 (2)
N2C—Ni1—N2B	94.39 (13)	C10B—N2B—C6B	118.7 (3)
N1A—Ni1—N2B	170.45 (13)	C10B—N2B—Ni1	126.5 (3)
N2A—Ni1—N2B	95.16 (13)	C6B—N2B—Ni1	114.7 (3)
N2C—Ni1—N1B	168.33 (13)	N1B—C1B—C2B	122.1 (4)
N1A—Ni1—N1B	94.78 (12)	C3B—C2B—C1B	118.9 (4)
N2A—Ni1—N1B	94.04 (12)	C2B—C3B—C4B	119.5 (4)
N2B—Ni1—N1B	78.54 (13)	C5B—C4B—C3B	119.0 (4)
N2C—Ni1—N1C	78.63 (13)	N1B—C5B—C4B	121.8 (4)
N1A—Ni1—N1C	94.56 (13)	N1B—C5B—C6B	115.5 (3)
N2A—Ni1—N1C	170.85 (12)	C4B—C5B—C6B	122.7 (4)
N2B—Ni1—N1C	92.55 (13)	N2B—C6B—C7B	121.7 (4)
N1B—Ni1—N1C	92.31 (13)	N2B—C6B—C5B	115.7 (3)
O2—S2—O1	111.5 (3)	C7B—C6B—C5B	122.5 (4)
O2—S2—O3	109.2 (4)	C6B—C7B—C8B	118.6 (5)
O1—S2—O3	110.2 (4)	C9B—C8B—C7B	120.0 (4)
O2—S2—S1	108.7 (3)	C8B—C9B—C10B	118.7 (5)
O1—S2—S1	108.1 (3)	N2B—C10B—C9B	122.3 (5)
O3—S2—S1	109.2 (3)	C1C—N1C—C5C	118.1 (4)
C1A—N1A—C5A	118.7 (4)	C1C—N1C—Ni1	127.0 (3)
C1A—N1A—Ni1	126.2 (3)	C5C—N1C—Ni1	114.8 (3)
C5A—N1A—Ni1	115.0 (3)	C6C—N2C—C10C	119.2 (3)
C6A—N2A—C10A	118.4 (4)	C6C—N2C—Ni1	115.5 (3)
C6A—N2A—Ni1	115.0 (3)	C10C—N2C—Ni1	125.1 (3)
C10A—N2A—Ni1	126.5 (3)	N1C—C1C—C2C	123.2 (4)
N1A—C1A—C2A	122.2 (5)	C3C—C2C—C1C	118.5 (5)
C3A—C2A—C1A	119.2 (5)	C2C—C3C—C4C	119.2 (4)
C2A—C3A—C4A	119.1 (5)	C5C—C4C—C3C	120.0 (5)
C3A—C4A—C5A	119.6 (5)	N1C—C5C—C4C	121.0 (4)
N1A—C5A—C4A	121.3 (4)	N1C—C5C—C6C	114.8 (3)
N1A—C5A—C6A	115.7 (3)	C4C—C5C—C6C	124.2 (4)
C4A—C5A—C6A	123.0 (4)	N2C—C6C—C7C	121.6 (4)
N2A—C6A—C7A	121.1 (4)	N2C—C6C—C5C	116.1 (3)
N2A—C6A—C5A	115.6 (3)	C7C—C6C—C5C	122.3 (4)
C7A—C6A—C5A	123.2 (4)	C8C—C7C—C6C	118.9 (4)
C8A—C7A—C6A	119.4 (5)	C7C—C8C—C9C	120.3 (4)
C9A—C8A—C7A	119.5 (5)	C8C—C9C—C10C	118.4 (4)
C8A—C9A—C10A	119.2 (5)	N2C—C10C—C9C	121.6 (4)
N2A—C10A—C9A	122.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.89 (5)	1.87 (5)	2.744 (8)	166 (4)
O1W—H1WB···O1^i	0.91 (9)	1.94 (9)	2.834 (11)	169 (7)
O2W—H2WA···O2	0.88 (7)	1.91 (7)	2.783 (10)	168 (5)
O2W—H2WB···O1W^i	0.89 (9)	2.13 (8)	2.905 (9)	145 (7)
O3W—H3WA···O6W^ii	0.90 (4)	1.95 (5)	2.821 (11)	161 (4)
O3W—H3WA···O10W^ii	0.90 (4)	1.97 (6)	2.79 (3)	150 (4)
O3W—H3WB···O2W^iii	0.90 (4)	1.86 (4)	2.753 (8)	170 (3)
O4W—H4WA···O1W	0.89 (9)	2.10 (7)	2.931 (12)	154 (7)
O4W—H4WB···O9W	0.90 (7)	1.87 (9)	2.72 (3)	156 (6)
O5W···O6W	?	?	2.72 (1)	?
O5W···O9W	?	?	2.55 (2)	?
O5W···O10W	?	?	2.13 (3)	?
O6W···O8W	?	?	2.74 (1)	?
O6W···O9W	?	?	2.21 (3)	?
O7W···O9W	?	?	2.45 (3)	?
O8W···O11W	?	?	2.67 (3)	?
O9W···O10W	?	?	2.64 (4)	?
O5W···O4W^iv	?	?	2.82 (1)	?
O7W···O8W^v	?	?	2.89 (2)	?

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+2, y−1, −z+3/2; (iv) −x+5/2, −y+1/2, −z+2; (v) −x+5/2, −y+3/2, −z+2.