supplementary materials


br2216 scheme

Acta Cryst. (2013). E69, m63-m64    [ doi:10.1107/S1600536812050775 ]

Tris(1,10-phenanthroline-[kappa]2N,N')nickel(II) hexaoxido-[mu]-peroxido-disulfate(VI) N,N-dimethylformamide disolvate monohydrate

M. A. Harvey, S. Suarez, F. Doctorovich and R. Baggio

Abstract top

The asymmetric unit of the title complex, [Ni(C12H8N2)3]S2O8·2C3H7NO·H2O, consists of a complex [Ni(phen)3]2+ cation and one isolated pds anion, with two DMF molecules and one water molecule as solvates (where phen is 1,10-phenanthroline, pds is the hexaoxido-[mu]-peroxoido-disulfate dianion and DMF is dimethylformamide). The [Ni(phen)3]2+ cation is regular, with an almost ideal NiII bond-valence sum of 2.07 v.u. The group, as well as the water solvent molecule, are well behaved in terms of crystallographic order, but the remaining three molecules in the structure display different kinds of disorder, viz. the two DMF molecules mimic a twofold splitting and the pds anion has both S atoms clamped at well-determined positions but with a not-too-well-defined central part. These peculiar behaviours are a consequence of the hydrogen-bonding interactions: the outermost SO3 parts of the pds anion are heavily connected to the complex cations via C-H...O hydrogen bonding, generating an [Ni(phen)3]pds network and providing for the stability of the terminal pds sites. Also, the water solvent molecule is strongly bound to the structure (being a donor of two strong bonds and an acceptor of one) and is accordingly perfectly ordered. The peroxide O atoms in the pds middle region, instead, appear as much less restrained into their sites, which may explain their tendency to disorder. The cation-anion network leaves large embedded holes, amounting to about 28% of the total crystal volume, which are occupied by the DMF molecules. The latter are weakly interacting with the rest of the structure, which renders them much more labile and, accordingly, prone to disorder.

Comment top

The binding behavior of peroxodisulfate (pds) towards a number of transition metal metal cations (Cd(II), Hg(II), Cu(II), Mn(III), Zn(II), Ag(II)) has been well documentated in the literature Youngme et al., 2007; Manson et al., 2009., Blackman et al., 1991; Harrison et al., 1980; Harvey et al., 2011, and references therein) but its rather elusive character as a ligand has also been evidenced in many other structures where the anion wouldn't coordinate, thus acting as a balancing counterion or, in occasions, just as a neutral co-crystallization agent in the form of peroxodisulfuric acid. Among the cations being reluctant towards pds coordination it must be mentioned the case of Cd (Harvey et al., 2005); Co(III) (Singh et al., 2009); Zn(II) (Harvey et al., 2004), Cu(II) (Youngme et al., 2008), Mn(IV) (Baffert et al., 2009), and even the more stringent case of Ni, of which no crystal structure with pds had been reported up to date: in particular, all our previous experiments aimed to produce such a complex had so far been unsuccessful.

Therefore, we present herein the first NiII-pds structure, where the anion did not enter into the NiII coordination sphere but behaves instead as a stabilizing counteranion: [Ni(phen)3]2+.(pds).2DMF.(H2O), where (phen: 1,10-phenanthroline; pds: peroxidisulfate dianion; DMF: dimethylformamide).

The asymmetric unit of the complex consists of a globular [Ni(phen)3]2+ nucleus (Fig 1a), one isolated pds anion, two DMF and one water molecules as solvates.

The [Ni(phen)3]2+ cationic centre is absolutely regular and does not differ from the more than 100 similar groups which appear in the v5.33 version of the CSD (Allen, 2002). The Bond Valence Sum for the NiII cation in the title compound (Brown and Altermatt, 1985) is almost ideal (2.07 v.u.), and the regularity in the NiN6 coordination sphere is shown by the tight range of similar parameters (d(Ni-N): 2.087 (3)-2.100 (3)Å; N-Ni-N cis angles: 79.04 (12)-79.71 (12)° (chelating); 92.79 (12)-96.46 (12)° (non-chelating); N-Ni-N trans angles: 172.06 (12)-170.20 (12)°), but it can perhaps be best assessed by the geometric disposition of the three Bond Valence Vectors associated to the three chelating phen ligands (for details, see Harvey et al., 2006) which define an absolute planar array (sum of internal angles: 360.00°), and a theoretical (almost nil) resultant vector ( 0.017 v.u.). The cationic group as well as the water solvate are well behaved in terms of crystallographic order, but the remaining three groups in the structure display different kinds of disorder, as explained in detail in the refinement section, the two DMF mimicking different kinds of two-fold splitting (Figs. 1c,1d) with occupation factors of 0.546 (12)/0.454 (12) and 0.520 (12)/0.480 (12), respectively. In the case of pds this occurs in a more complicated fashion, having both S's "clamped" at two well determined positions (Fig 1b) and a not-so-well-defined central part (Occupation for O4,O5:0.641 (3)).

These peculiar behaviours may be better understood by inspection of Table 1, which gives the H-bonding interactions, and their representation in Fig 2. It is clearly seen therein that the outermost SO3 parts of the pds anion are strongly connected to the cationic centres via H-bonding (10 donors out of 13 correspond to these groups), generating a sort of stable [Ni(phen)3]-pds network and acting as a clamp for the terminal SO3 groups. The oxygens in the pds middle region, instead, are much less restrained to their sites, and this could explain some tendency to disorder. Similar mobility restrictions apply to the water solvate, donor of two strong bonds (Table 1, entries 1 and 2) and acceptor of one (3rd entry). On the other hand, the above cationic-anionic network leaves large embedded holes (about 28% of the total crystal volume, as calculated by PLATON, Spek, 2009). These holes are occupied by the DMF molecules (in light tracing in Fig 2). Analysis of the acceptors in Table 1 and inspection of Figure 2 reaveals that they hardly interact with the rest of the structure, being thus labile and, accordingly, prone to disorder.

Related literature top

For information on structures with coordinated pds, see: Youngme et al. (2007); Manson et al. (2009); Harrison & Hathaway (1980; Blackman et al. (1991); Harvey et al. (2011) and references therein. For examples of structurers with non-coordinating pds groups, see Baffert et al. (2009); Harvey et al. (2004, 2005); Youngme et al. (2008); Singh et al. (2009). For details of bond-valence analysis and the vector bond-valence model, see: Brown & Altermatt (1985) and Harvey et al. (2006), respectively.

Experimental top

The title compound was prepared by adding DMF to a solid, equimolar mixture of [Ni(CH3COO)2].4H2O, K2S2O8 and phen.H2O in such a way that phen final concentration was 0.500 M. Crystals suitable for X-ray diffraction developed in a few hours.

Refinement top

All C—H atoms were found in a difference map, but treated differently in refinement. Those attached to C were further idealized and finally allowed to ride. CH3 groups were also free to rotate. Water H's were refined with restrained d(O-H). In all cases displacement parameters were taken as Uiso(H) = X × Ueq(host) [d(CH)methyl = 0.96 A°, X = 1.5; d(C—H)arom = 0.93 Å, X = 1.2; O - H = 0.85 (1)Å, X = 1.2].

A rather peculiar characteristic of the structure was its having the two DMF solvates as well as the pds anion disordered, all of them in different ways: in both DMF molecules the disorder mimics a two fold symmetry, with the pseudo two fold axis by force passing throuh the central N; in the case of moieties E (D) this occurs with the pseudo diad being perpendicular (parallel) to one of the to the two C(methyl)—N lines, Fig 1c (1d).

The case of the pds anion was not that clear cut, but interesting anyway: the molecule occupies in the crystal several, slightly offset positons, all of them with the S atoms "clamped" in the S1, S2 reported coordinates (No "ghosts" in their neighbourhood). The central oxygens O4 and O5, instead, presented a clear splitting which needed to be included in the model in order to have a proper refinement. The coresponding outermost minoritarian oxygens, however, could not be clearly disclosed and have to be accordingly disregarded. To compensate for this fact, atoms O1-O3, O6-O8 were given full occupancy. This procedure, fulfilled with some restraints in metrics and in displacement factors, allowed to reduce the R factor by more ~10%, and the s.u.'s for the O4, O5 coordinates in ~30%.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Ellipsoid plot of the different constituents of (I), drawn at a 30% displacement factor level. (a): The Ni(phen)3 nucleus. (b): The S2O82- anion. Note the minoritarian S fractions, around O4 and O5. (c) and (d): the two disordered DMF molecules, with different pseudo two-fold symmetry, and the well behaved water solvate.
[Figure 2] Fig. 2. A packing view of (I) drawn down b and showing the way in which the cationic-anionic H-bonding network builds up. DMF units (in light lining) appear in the structural voids, with almost no connections to the rest. Only H atoms involved in H-bonding have been represented.
Tris(1,10-phenanthroline-κ2N,N')nickel(II) hexaoxido-µ-peroxido-disulfate(VI) N,N-dimethylformamide disolvate monohydrate top
Crystal data top
[Ni(C12H8N2)3](S2O8)·2C3H7NO·H2OZ = 2
Mr = 955.65F(000) = 992
Triclinic, P1Dx = 1.468 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4832 (3) ÅCell parameters from 11752 reflections
b = 12.2221 (4) Åθ = 3.7–28.8°
c = 18.0044 (6) ŵ = 0.62 mm1
α = 79.691 (3)°T = 294 K
β = 76.725 (3)°Block, light brown
γ = 76.190 (3)°0.18 × 0.11 × 0.11 mm
V = 2161.41 (12) Å3
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
10070 independent reflections
Radiation source: fine-focus sealed tube6165 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scans, thick slicesθmax = 28.9°, θmin = 3.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1414
Tmin = 0.945, Tmax = 0.952k = 1516
31646 measured reflectionsl = 2424
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.096P)2]
where P = (Fo2 + 2Fc2)/3
10070 reflections(Δ/σ)max = 0.007
647 parametersΔρmax = 0.65 e Å3
246 restraintsΔρmin = 0.73 e Å3
Crystal data top
[Ni(C12H8N2)3](S2O8)·2C3H7NO·H2Oγ = 76.190 (3)°
Mr = 955.65V = 2161.41 (12) Å3
Triclinic, P1Z = 2
a = 10.4832 (3) ÅMo Kα radiation
b = 12.2221 (4) ŵ = 0.62 mm1
c = 18.0044 (6) ÅT = 294 K
α = 79.691 (3)°0.18 × 0.11 × 0.11 mm
β = 76.725 (3)°
Data collection top
Oxford Diffraction Gemini CCD S Ultra
diffractometer
10070 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
6165 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.952Rint = 0.041
31646 measured reflectionsθmax = 28.9°
Refinement top
R[F2 > 2σ(F2)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.170Δρmax = 0.65 e Å3
S = 1.04Δρmin = 0.73 e Å3
10070 reflectionsAbsolute structure: ?
647 parametersFlack parameter: ?
246 restraintsRogers parameter: ?
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.21814 (5)0.29652 (4)0.27142 (3)0.04038 (18)
N1A0.3061 (3)0.4386 (3)0.25528 (18)0.0449 (8)
N2A0.4160 (3)0.2281 (3)0.22251 (18)0.0441 (8)
C1A0.2489 (5)0.5435 (4)0.2693 (3)0.0564 (11)
H1A0.15710.56070.28800.068*
C2A0.3211 (6)0.6290 (4)0.2570 (3)0.0707 (14)
H2A0.27810.70140.26900.085*
C3A0.4549 (6)0.6067 (4)0.2273 (3)0.0678 (14)
H3A0.50370.66360.21910.081*
C4A0.5186 (5)0.4977 (4)0.2092 (2)0.0552 (11)
C5A0.6573 (5)0.4663 (5)0.1758 (3)0.0713 (14)
H5A0.71090.51980.16670.086*
C6A0.7116 (5)0.3623 (5)0.1573 (3)0.0770 (16)
H6A0.80210.34510.13490.092*
C7A0.6338 (4)0.2757 (4)0.1711 (3)0.0603 (12)
C8A0.6837 (5)0.1661 (5)0.1533 (3)0.0751 (15)
H8A0.77350.14470.13070.090*
C9A0.6032 (5)0.0890 (4)0.1684 (3)0.0722 (14)
H9A0.63660.01580.15540.087*
C10A0.4690 (5)0.1224 (4)0.2038 (3)0.0576 (11)
H10A0.41430.06960.21500.069*
C11A0.4973 (4)0.3038 (4)0.2064 (2)0.0457 (9)
C12A0.4382 (4)0.4166 (3)0.2246 (2)0.0441 (9)
N1B0.0317 (3)0.3791 (3)0.32722 (18)0.0429 (7)
N2B0.2391 (3)0.2495 (3)0.38604 (18)0.0448 (8)
C1B0.0697 (4)0.4466 (4)0.2978 (3)0.0546 (11)
H1B0.06170.45830.24460.066*
C2B0.1862 (4)0.5002 (4)0.3420 (3)0.0588 (12)
H2B0.25410.54670.31870.071*
C3B0.2005 (4)0.4843 (4)0.4201 (3)0.0571 (11)
H3B0.27770.52060.45050.068*
C4B0.0975 (4)0.4125 (4)0.4541 (2)0.0496 (10)
C5B0.1039 (5)0.3901 (4)0.5355 (3)0.0626 (12)
H5B0.18070.42180.56850.075*
C6B0.0010 (5)0.3229 (4)0.5651 (2)0.0597 (12)
H6B0.00560.30880.61820.072*
C7B0.1210 (5)0.2737 (4)0.5163 (2)0.0517 (10)
C8B0.2324 (5)0.2047 (4)0.5435 (3)0.0658 (13)
H8B0.23160.18980.59610.079*
C9B0.3413 (5)0.1598 (5)0.4931 (3)0.0715 (14)
H9B0.41540.11350.51080.086*
C10B0.3418 (5)0.1835 (4)0.4142 (3)0.0598 (11)
H10B0.41710.15190.38010.072*
C11B0.1296 (4)0.2931 (3)0.4367 (2)0.0415 (9)
C12B0.0175 (4)0.3637 (3)0.4050 (2)0.0407 (8)
N1C0.1500 (3)0.1494 (3)0.26890 (19)0.0473 (8)
N2C0.1687 (3)0.3320 (3)0.16241 (18)0.0460 (8)
C1C0.1412 (5)0.0598 (4)0.3217 (3)0.0600 (12)
H1C0.16290.06000.36900.072*
C2C0.1005 (5)0.0353 (4)0.3093 (3)0.0705 (14)
H2C0.09490.09670.34790.085*
C3C0.0693 (5)0.0374 (4)0.2410 (4)0.0704 (14)
H3C0.04240.10040.23230.084*
C4C0.0774 (4)0.0547 (4)0.1836 (3)0.0570 (11)
C5C0.0484 (5)0.0587 (5)0.1095 (3)0.0703 (14)
H5C0.02060.00220.09820.084*
C6C0.0606 (5)0.1494 (5)0.0558 (3)0.0718 (15)
H6C0.04290.14900.00750.086*
C7C0.0999 (4)0.2462 (4)0.0706 (2)0.0591 (12)
C8C0.1121 (5)0.3444 (5)0.0179 (3)0.0732 (15)
H8C0.09420.34940.03100.088*
C9C0.1498 (5)0.4320 (5)0.0378 (3)0.0720 (14)
H9C0.15720.49730.00300.086*
C10C0.1774 (5)0.4233 (4)0.1108 (2)0.0576 (11)
H10C0.20300.48400.12390.069*
C11C0.1301 (4)0.2445 (4)0.1436 (2)0.0458 (9)
C12C0.1190 (4)0.1469 (3)0.2003 (2)0.0457 (9)
O1W0.5525 (6)0.4757 (5)0.5714 (3)0.1193 (17)
H1WA0.547 (10)0.410 (3)0.596 (4)0.179*
H1WB0.516 (10)0.522 (5)0.604 (4)0.179*
S10.87231 (13)0.74846 (10)0.19276 (6)0.0597 (3)
S20.51188 (14)0.84299 (10)0.32020 (7)0.0632 (3)
O10.9510 (4)0.7297 (3)0.2484 (2)0.0913 (12)
O20.8815 (4)0.8464 (3)0.13880 (19)0.0892 (12)
O30.8770 (5)0.6481 (3)0.1618 (2)0.0980 (12)
O40.7174 (4)0.7544 (4)0.2327 (3)0.0779 (13)0.617 (3)
O50.6654 (4)0.8441 (5)0.2768 (3)0.0797 (14)0.617 (3)
O60.5143 (6)0.7390 (3)0.3684 (2)0.1142 (16)
O70.5037 (4)0.9379 (3)0.3577 (2)0.0915 (12)
O80.4358 (4)0.8641 (3)0.2626 (2)0.0968 (13)
N1D0.7290 (6)0.1726 (5)0.4231 (3)0.0937 (15)
O1D'0.5753 (9)0.3293 (7)0.3748 (5)0.106 (4)0.544 (12)
C1D0.6338 (8)0.2719 (7)0.4278 (5)0.106 (2)
H1DD0.61000.29980.47500.127*0.544 (12)
H1DA0.62470.29770.47650.159*0.456 (12)
H1DB0.54950.25850.42330.159*0.456 (12)
H1DC0.66080.32880.38690.159*0.456 (12)
O1D"0.8949 (16)0.0480 (15)0.4893 (8)0.167 (7)0.456 (12)
C2D0.7955 (10)0.1257 (8)0.4819 (5)0.128 (3)
H2DB0.76390.17180.52300.192*0.544 (12)
H2DC0.88980.12190.46360.192*0.544 (12)
H2DD0.77960.05050.50040.192*0.544 (12)
H2DA0.75810.15940.52650.154*0.456 (12)
C3D0.7575 (9)0.1204 (9)0.3550 (5)0.156 (4)
H3D10.78900.17200.31150.235*
H3D20.67770.10160.34790.235*
H3D30.82530.05250.35940.235*
N1E0.4039 (7)0.7569 (6)0.0434 (4)0.1133 (18)
C1E'0.506 (2)0.689 (2)0.0074 (13)0.166 (9)0.524 (12)
H1EA0.58680.71400.00620.250*0.524 (12)
H1EB0.49510.69060.04430.250*0.524 (12)
H1EC0.51120.61320.03390.250*0.524 (12)
C2E'0.399 (3)0.8651 (17)0.0685 (14)0.173 (8)0.524 (12)
H2EA0.48860.87760.06100.259*0.524 (12)
H2EB0.35850.86330.12210.259*0.524 (12)
H2EC0.34750.92550.03910.259*0.524 (12)
C3E'0.265 (2)0.7430 (19)0.0550 (11)0.128 (5)0.524 (12)
H3EA0.19690.79610.07960.154*0.524 (12)
O1E'0.238 (2)0.6704 (15)0.0354 (9)0.171 (6)0.524 (12)
C1E"0.296 (3)0.826 (3)0.0685 (15)0.179 (10)0.476 (12)
H1ED0.22070.79180.07220.268*0.476 (12)
H1EE0.28790.89510.03370.268*0.476 (12)
H1EF0.29890.84120.11840.268*0.476 (12)
C2E"0.539 (2)0.797 (2)0.0370 (14)0.164 (8)0.476 (12)
H2ED0.51880.87390.04850.246*0.476 (12)
H2EE0.59040.79390.01430.246*0.476 (12)
H2EF0.58920.74840.07290.246*0.476 (12)
C3E"0.436 (3)0.6469 (19)0.0256 (13)0.122 (5)0.476 (12)
H3EB0.52460.61160.01050.146*0.476 (12)
O1E"0.356 (3)0.602 (2)0.0292 (11)0.181 (7)0.476 (12)
O4'0.7492 (13)0.8086 (11)0.2641 (7)0.100 (4)*0.383 (3)
O5'0.650 (2)0.759 (2)0.3001 (13)0.078 (8)*0.180 (10)
O5"0.6248 (15)0.8221 (12)0.2377 (9)0.050 (5)*0.202 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0430 (3)0.0411 (3)0.0384 (3)0.0093 (2)0.0099 (2)0.0055 (2)
N1A0.052 (2)0.0410 (18)0.0427 (18)0.0085 (15)0.0085 (15)0.0111 (14)
N2A0.0477 (19)0.0378 (18)0.0443 (18)0.0061 (15)0.0075 (15)0.0042 (14)
C1A0.065 (3)0.050 (3)0.056 (3)0.010 (2)0.007 (2)0.019 (2)
C2A0.099 (4)0.045 (3)0.074 (3)0.021 (3)0.010 (3)0.023 (2)
C3A0.092 (4)0.061 (3)0.064 (3)0.042 (3)0.013 (3)0.012 (2)
C4A0.066 (3)0.062 (3)0.048 (2)0.029 (2)0.016 (2)0.006 (2)
C5A0.063 (3)0.092 (4)0.071 (3)0.044 (3)0.011 (3)0.006 (3)
C6A0.046 (3)0.101 (5)0.083 (4)0.027 (3)0.005 (3)0.005 (3)
C7A0.045 (2)0.069 (3)0.059 (3)0.007 (2)0.005 (2)0.002 (2)
C8A0.051 (3)0.077 (4)0.077 (3)0.010 (3)0.002 (2)0.006 (3)
C9A0.068 (3)0.053 (3)0.077 (3)0.014 (3)0.003 (3)0.009 (2)
C10A0.064 (3)0.050 (3)0.054 (3)0.007 (2)0.009 (2)0.003 (2)
C11A0.044 (2)0.053 (2)0.040 (2)0.0096 (19)0.0093 (17)0.0028 (18)
C12A0.045 (2)0.051 (2)0.039 (2)0.0152 (19)0.0107 (17)0.0042 (17)
N1B0.0424 (18)0.0446 (18)0.0401 (17)0.0111 (15)0.0093 (14)0.0034 (14)
N2B0.0461 (19)0.0437 (18)0.0460 (18)0.0046 (15)0.0145 (15)0.0087 (15)
C1B0.045 (2)0.066 (3)0.047 (2)0.005 (2)0.0110 (19)0.001 (2)
C2B0.040 (2)0.058 (3)0.070 (3)0.003 (2)0.010 (2)0.002 (2)
C3B0.040 (2)0.063 (3)0.062 (3)0.007 (2)0.002 (2)0.013 (2)
C4B0.047 (2)0.053 (2)0.048 (2)0.018 (2)0.0004 (18)0.0088 (19)
C5B0.061 (3)0.080 (3)0.049 (3)0.024 (3)0.003 (2)0.018 (2)
C6B0.073 (3)0.071 (3)0.038 (2)0.023 (3)0.004 (2)0.012 (2)
C7B0.061 (3)0.057 (3)0.040 (2)0.018 (2)0.013 (2)0.0051 (19)
C8B0.079 (3)0.080 (3)0.044 (2)0.013 (3)0.026 (2)0.007 (2)
C9B0.070 (3)0.085 (4)0.061 (3)0.001 (3)0.034 (3)0.006 (3)
C10B0.053 (3)0.067 (3)0.059 (3)0.001 (2)0.022 (2)0.010 (2)
C11B0.048 (2)0.043 (2)0.039 (2)0.0168 (18)0.0115 (17)0.0066 (16)
C12B0.042 (2)0.042 (2)0.041 (2)0.0174 (17)0.0052 (16)0.0070 (16)
N1C0.0462 (19)0.053 (2)0.0458 (19)0.0155 (16)0.0105 (15)0.0049 (16)
N2C0.0463 (19)0.051 (2)0.0401 (17)0.0078 (16)0.0085 (15)0.0060 (15)
C1C0.070 (3)0.052 (3)0.062 (3)0.022 (2)0.018 (2)0.001 (2)
C2C0.074 (3)0.052 (3)0.089 (4)0.023 (3)0.020 (3)0.001 (3)
C3C0.059 (3)0.060 (3)0.104 (4)0.019 (2)0.018 (3)0.029 (3)
C4C0.041 (2)0.061 (3)0.074 (3)0.010 (2)0.010 (2)0.026 (2)
C5C0.059 (3)0.082 (4)0.083 (4)0.014 (3)0.015 (3)0.044 (3)
C6C0.059 (3)0.102 (4)0.064 (3)0.003 (3)0.021 (2)0.043 (3)
C7C0.044 (2)0.087 (3)0.047 (2)0.000 (2)0.0112 (19)0.026 (2)
C8C0.067 (3)0.106 (4)0.042 (3)0.001 (3)0.019 (2)0.013 (3)
C9C0.078 (3)0.083 (4)0.045 (3)0.006 (3)0.017 (2)0.010 (3)
C10C0.062 (3)0.061 (3)0.045 (2)0.010 (2)0.012 (2)0.002 (2)
C11C0.0330 (19)0.061 (3)0.042 (2)0.0020 (18)0.0055 (16)0.0170 (19)
C12C0.035 (2)0.052 (2)0.052 (2)0.0083 (18)0.0062 (17)0.0164 (19)
O1W0.096 (3)0.109 (4)0.127 (4)0.023 (3)0.002 (3)0.029 (3)
S10.0785 (8)0.0605 (7)0.0471 (6)0.0279 (6)0.0163 (6)0.0020 (5)
S20.0782 (8)0.0452 (6)0.0671 (7)0.0088 (6)0.0203 (6)0.0065 (5)
O10.113 (3)0.085 (3)0.096 (3)0.028 (2)0.059 (2)0.002 (2)
O20.127 (3)0.075 (2)0.067 (2)0.039 (2)0.019 (2)0.0123 (17)
O30.166 (4)0.079 (2)0.066 (2)0.047 (2)0.032 (2)0.0130 (17)
O40.085 (2)0.082 (3)0.084 (3)0.034 (3)0.021 (2)0.028 (2)
O50.080 (2)0.066 (3)0.104 (4)0.016 (2)0.025 (2)0.027 (2)
O60.182 (5)0.066 (2)0.090 (3)0.041 (3)0.021 (3)0.0140 (19)
O70.132 (3)0.063 (2)0.088 (3)0.008 (2)0.037 (2)0.0262 (18)
O80.108 (3)0.062 (2)0.141 (3)0.004 (2)0.074 (3)0.021 (2)
N1D0.094 (4)0.109 (4)0.084 (3)0.041 (3)0.013 (3)0.008 (3)
O1D'0.115 (7)0.096 (6)0.120 (7)0.034 (5)0.049 (6)0.006 (5)
C1D0.110 (5)0.100 (5)0.120 (6)0.044 (4)0.030 (4)0.006 (4)
O1D"0.152 (12)0.213 (16)0.108 (9)0.004 (9)0.034 (8)0.019 (9)
C2D0.146 (7)0.135 (7)0.107 (5)0.041 (5)0.042 (5)0.013 (5)
C3D0.122 (7)0.223 (10)0.121 (6)0.005 (7)0.018 (5)0.076 (7)
N1E0.117 (5)0.102 (4)0.100 (4)0.005 (4)0.003 (4)0.006 (3)
C1E'0.156 (13)0.162 (17)0.126 (14)0.037 (13)0.000 (13)0.003 (12)
C2E'0.183 (18)0.131 (12)0.206 (18)0.065 (12)0.003 (16)0.035 (11)
C3E'0.139 (9)0.107 (11)0.135 (12)0.038 (9)0.006 (10)0.015 (10)
O1E'0.226 (16)0.144 (12)0.152 (11)0.085 (12)0.001 (12)0.029 (9)
C1E"0.132 (12)0.175 (18)0.173 (17)0.027 (14)0.015 (15)0.017 (17)
C2E"0.146 (12)0.138 (15)0.204 (19)0.051 (12)0.010 (15)0.011 (14)
C3E"0.146 (14)0.121 (10)0.103 (11)0.045 (9)0.025 (11)0.001 (10)
O1E"0.220 (19)0.204 (15)0.152 (12)0.120 (14)0.040 (14)0.000 (12)
Geometric parameters (Å, º) top
Ni1—N2B2.088 (3)C4C—C12C1.402 (6)
Ni1—N2C2.089 (3)C4C—C5C1.425 (7)
Ni1—N1B2.090 (3)C5C—C6C1.344 (7)
Ni1—N2A2.091 (3)C5C—H5C0.9300
Ni1—N1C2.098 (3)C6C—C7C1.428 (7)
Ni1—N1A2.100 (3)C6C—H6C0.9300
N1A—C1A1.321 (5)C7C—C8C1.403 (7)
N1A—C12A1.349 (5)C7C—C11C1.416 (5)
N2A—C10A1.347 (5)C8C—C9C1.356 (7)
N2A—C11A1.355 (5)C8C—H8C0.9300
C1A—C2A1.391 (6)C9C—C10C1.390 (6)
C1A—H1A0.9300C9C—H9C0.9300
C2A—C3A1.361 (7)C10C—H10C0.9300
C2A—H2A0.9300C11C—C12C1.433 (6)
C3A—C4A1.399 (7)O1W—H1WA0.854 (13)
C3A—H3A0.9300O1W—H1WB0.850 (13)
C4A—C12A1.400 (6)S1—O11.395 (3)
C4A—C5A1.428 (7)S1—O21.408 (3)
C5A—C6A1.330 (8)S1—O31.422 (3)
C5A—H5A0.9300S1—O41.608 (3)
C6A—C7A1.439 (7)S2—O81.401 (3)
C6A—H6A0.9300S2—O61.403 (3)
C7A—C8A1.384 (7)S2—O71.420 (3)
C7A—C11A1.412 (6)S2—O51.622 (3)
C8A—C9A1.362 (7)O4—O51.399 (4)
C8A—H8A0.9300N1D—C2D1.366 (9)
C9A—C10A1.400 (7)N1D—C1D1.377 (9)
C9A—H9A0.9300N1D—C3D1.422 (9)
C10A—H10A0.9300O1D'—C1D1.267 (10)
C11A—C12A1.433 (6)C1D—H1DD0.9300
N1B—C1B1.332 (5)C1D—H1DA0.9600
N1B—C12B1.357 (5)C1D—H1DB0.9600
N2B—C10B1.326 (5)C1D—H1DC0.9600
N2B—C11B1.354 (5)O1D"—C2D1.246 (15)
C1B—C2B1.383 (6)C2D—H2DB0.9600
C1B—H1B0.9300C2D—H2DC0.9600
C2B—C3B1.362 (6)C2D—H2DD0.9600
C2B—H2B0.9300C2D—H2DA0.9300
C3B—C4B1.403 (6)C3D—H3D10.9600
C3B—H3B0.9300C3D—H3D20.9600
C4B—C12B1.395 (5)C3D—H3D30.9600
C4B—C5B1.431 (6)N1E—C1E"1.28 (2)
C5B—C6B1.360 (7)N1E—C1E'1.30 (2)
C5B—H5B0.9300N1E—C3E"1.38 (2)
C6B—C7B1.427 (6)N1E—C2E'1.46 (2)
C6B—H6B0.9300N1E—C3E'1.47 (2)
C7B—C11B1.395 (5)N1E—C2E"1.58 (2)
C7B—C8B1.400 (6)C1E'—H1EA0.9600
C8B—C9B1.354 (7)C1E'—H1EB0.9600
C8B—H8B0.9300C1E'—H1EC0.9600
C9B—C10B1.397 (6)C2E'—H2EA0.9600
C9B—H9B0.9300C2E'—H2EB0.9600
C10B—H10B0.9300C2E'—H2EC0.9600
C11B—C12B1.449 (5)C3E'—O1E'1.13 (2)
N1C—C1C1.322 (5)C3E'—H3EA0.9300
N1C—C12C1.354 (5)C1E"—H1ED0.9600
N2C—C10C1.326 (5)C1E"—H1EE0.9600
N2C—C11C1.349 (5)C1E"—H1EF0.9600
C1C—C2C1.398 (6)C2E"—H2ED0.9600
C1C—H1C0.9300C2E"—H2EE0.9600
C2C—C3C1.350 (7)C2E"—H2EF0.9600
C2C—H2C0.9300C3E"—O1E"1.09 (2)
C3C—C4C1.390 (7)C3E"—H3EB0.9300
C3C—H3C0.9300
N2B—Ni1—N2C170.47 (12)C3C—C4C—C5C123.6 (4)
N2B—Ni1—N1B79.71 (12)C12C—C4C—C5C119.3 (5)
N2C—Ni1—N1B94.79 (12)C6C—C5C—C4C120.8 (5)
N2B—Ni1—N2A96.45 (13)C6C—C5C—H5C119.6
N2C—Ni1—N2A89.93 (13)C4C—C5C—H5C119.6
N1B—Ni1—N2A172.08 (12)C5C—C6C—C7C122.0 (4)
N2B—Ni1—N1C92.80 (13)C5C—C6C—H6C119.0
N2C—Ni1—N1C79.70 (13)C7C—C6C—H6C119.0
N1B—Ni1—N1C93.56 (13)C8C—C7C—C11C116.6 (4)
N2A—Ni1—N1C93.54 (13)C8C—C7C—C6C125.0 (4)
N2B—Ni1—N1A94.40 (12)C11C—C7C—C6C118.5 (5)
N2C—Ni1—N1A93.77 (13)C9C—C8C—C7C120.3 (4)
N1B—Ni1—N1A94.29 (13)C9C—C8C—H8C119.9
N2A—Ni1—N1A79.02 (13)C7C—C8C—H8C119.9
N1C—Ni1—N1A170.17 (13)C8C—C9C—C10C119.4 (5)
C1A—N1A—C12A117.9 (4)C8C—C9C—H9C120.3
C1A—N1A—Ni1128.8 (3)C10C—C9C—H9C120.3
C12A—N1A—Ni1113.3 (3)N2C—C10C—C9C122.6 (5)
C10A—N2A—C11A117.9 (4)N2C—C10C—H10C118.7
C10A—N2A—Ni1128.7 (3)C9C—C10C—H10C118.7
C11A—N2A—Ni1113.4 (3)N2C—C11C—C7C122.5 (4)
N1A—C1A—C2A122.4 (5)N2C—C11C—C12C118.2 (3)
N1A—C1A—H1A118.8C7C—C11C—C12C119.4 (4)
C2A—C1A—H1A118.8N1C—C12C—C4C123.0 (4)
C3A—C2A—C1A119.8 (5)N1C—C12C—C11C116.9 (3)
C3A—C2A—H2A120.1C4C—C12C—C11C120.1 (4)
C1A—C2A—H2A120.1H1WA—O1W—H1WB105 (3)
C2A—C3A—C4A119.6 (4)O1—S1—O2115.5 (2)
C2A—C3A—H3A120.2O1—S1—O3112.9 (3)
C4A—C3A—H3A120.2O2—S1—O3115.6 (2)
C12A—C4A—C3A116.5 (4)O1—S1—O4110.5 (3)
C12A—C4A—C5A119.4 (4)O2—S1—O4108.3 (3)
C3A—C4A—C5A124.1 (4)O3—S1—O491.0 (2)
C6A—C5A—C4A121.5 (4)O8—S2—O6117.0 (3)
C6A—C5A—H5A119.2O8—S2—O7115.2 (2)
C4A—C5A—H5A119.2O6—S2—O7115.1 (3)
C5A—C6A—C7A121.6 (5)O8—S2—O5106.7 (3)
C5A—C6A—H6A119.2O6—S2—O5106.5 (3)
C7A—C6A—H6A119.2O7—S2—O592.5 (2)
C8A—C7A—C11A117.4 (4)O5—O4—S1112.6 (3)
C8A—C7A—C6A124.6 (5)O4—O5—S2111.3 (3)
C11A—C7A—C6A117.9 (5)C2D—N1D—C1D121.1 (7)
C9A—C8A—C7A121.0 (5)C2D—N1D—C3D120.7 (8)
C9A—C8A—H8A119.5C1D—N1D—C3D118.2 (7)
C7A—C8A—H8A119.5O1D'—C1D—N1D127.0 (9)
C8A—C9A—C10A118.5 (5)O1D'—C1D—H1DD116.5
C8A—C9A—H9A120.7N1D—C1D—H1DD116.5
C10A—C9A—H9A120.7O1D'—C1D—H1DA123.2
N2A—C10A—C9A122.7 (4)N1D—C1D—H1DA109.5
N2A—C10A—H10A118.6N1D—C1D—H1DB109.5
C9A—C10A—H10A118.6H1DD—C1D—H1DB100.5
N2A—C11A—C7A122.5 (4)H1DA—C1D—H1DB109.5
N2A—C11A—C12A117.1 (4)N1D—C1D—H1DC109.5
C7A—C11A—C12A120.4 (4)H1DD—C1D—H1DC110.9
N1A—C12A—C4A123.7 (4)H1DA—C1D—H1DC109.5
N1A—C12A—C11A117.2 (3)H1DB—C1D—H1DC109.5
C4A—C12A—C11A119.1 (4)O1D"—C2D—N1D134.5 (12)
C1B—N1B—C12B116.9 (4)O1D"—C2D—H2DB115.3
C1B—N1B—Ni1129.8 (3)N1D—C2D—H2DB109.5
C12B—N1B—Ni1113.2 (2)N1D—C2D—H2DC109.5
C10B—N2B—C11B117.8 (4)H2DB—C2D—H2DC109.5
C10B—N2B—Ni1129.0 (3)N1D—C2D—H2DD109.5
C11B—N2B—Ni1113.2 (2)H2DB—C2D—H2DD109.5
N1B—C1B—C2B123.7 (4)H2DC—C2D—H2DD109.5
N1B—C1B—H1B118.2O1D"—C2D—H2DA112.8
C2B—C1B—H1B118.2N1D—C2D—H2DA112.8
C3B—C2B—C1B119.3 (4)H2DC—C2D—H2DA115.8
C3B—C2B—H2B120.3H2DD—C2D—H2DA99.3
C1B—C2B—H2B120.3N1D—C3D—H3D1109.5
C2B—C3B—C4B119.3 (4)N1D—C3D—H3D2109.5
C2B—C3B—H3B120.3H3D1—C3D—H3D2109.5
C4B—C3B—H3B120.3N1D—C3D—H3D3109.5
C12B—C4B—C3B117.4 (4)H3D1—C3D—H3D3109.5
C12B—C4B—C5B119.2 (4)H3D2—C3D—H3D3109.5
C3B—C4B—C5B123.3 (4)C1E"—N1E—C1E'170.5 (19)
C6B—C5B—C4B120.7 (4)C1E"—N1E—C3E"135 (2)
C6B—C5B—H5B119.6C1E'—N1E—C2E'128.9 (19)
C4B—C5B—H5B119.6C3E"—N1E—C2E'166.9 (17)
C5B—C6B—C7B121.3 (4)C1E'—N1E—C3E'123.3 (18)
C5B—C6B—H6B119.4C3E"—N1E—C3E'83.9 (15)
C7B—C6B—H6B119.4C2E'—N1E—C3E'107.2 (14)
C11B—C7B—C8B117.0 (4)C1E"—N1E—C2E"116.1 (19)
C11B—C7B—C6B119.3 (4)C1E'—N1E—C2E"68.7 (15)
C8B—C7B—C6B123.7 (4)C3E"—N1E—C2E"108.3 (15)
C9B—C8B—C7B119.8 (4)C3E'—N1E—C2E"167.8 (14)
C9B—C8B—H8B120.1N1E—C1E'—H1EA109.5
C7B—C8B—H8B120.1N1E—C1E'—H1EB109.5
C8B—C9B—C10B119.6 (5)H1EA—C1E'—H1EB109.5
C8B—C9B—H9B120.2N1E—C1E'—H1EC109.5
C10B—C9B—H9B120.2H1EA—C1E'—H1EC109.5
N2B—C10B—C9B122.4 (5)H1EB—C1E'—H1EC109.5
N2B—C10B—H10B118.8N1E—C2E'—H2EA109.5
C9B—C10B—H10B118.8N1E—C2E'—H2EB109.5
N2B—C11B—C7B123.4 (4)H2EA—C2E'—H2EB109.5
N2B—C11B—C12B117.0 (3)N1E—C2E'—H2EC109.5
C7B—C11B—C12B119.6 (4)H2EA—C2E'—H2EC109.5
N1B—C12B—C4B123.3 (4)H2EB—C2E'—H2EC109.5
N1B—C12B—C11B116.9 (3)O1E'—C3E'—N1E123 (2)
C4B—C12B—C11B119.9 (3)O1E'—C3E'—H3EA118.7
C1C—N1C—C12C117.7 (4)N1E—C3E'—H3EA118.7
C1C—N1C—Ni1129.6 (3)N1E—C1E"—H1ED109.5
C12C—N1C—Ni1112.6 (3)N1E—C1E"—H1EE109.5
C10C—N2C—C11C118.7 (3)H1ED—C1E"—H1EE109.5
C10C—N2C—Ni1128.9 (3)N1E—C1E"—H1EF109.5
C11C—N2C—Ni1112.4 (3)H1ED—C1E"—H1EF109.5
N1C—C1C—C2C122.6 (4)H1EE—C1E"—H1EF109.5
N1C—C1C—H1C118.7N1E—C2E"—H2ED109.5
C2C—C1C—H1C118.7N1E—C2E"—H2EE109.5
C3C—C2C—C1C119.6 (5)H2ED—C2E"—H2EE109.5
C3C—C2C—H2C120.2N1E—C2E"—H2EF109.5
C1C—C2C—H2C120.2H2ED—C2E"—H2EF109.5
C2C—C3C—C4C120.0 (4)H2EE—C2E"—H2EF109.5
C2C—C3C—H3C120.0O1E"—C3E"—N1E120 (3)
C4C—C3C—H3C120.0O1E"—C3E"—H3EB120.0
C3C—C4C—C12C117.1 (4)N1E—C3E"—H3EB120.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O6i0.85 (5)2.02 (6)2.839 (7)160 (10)
O1W—H1WB···O1Di0.85 (7)1.90 (7)2.668 (10)149 (7)
C3B—H3B···O1Wii0.932.543.305 (8)139
C1B—H1B···O3ii0.932.553.192 (6)126
C3A—H3A···O80.932.593.271 (6)130
C3C—H3C···O1iii0.932.433.337 (6)164
C5A—H5A···O30.932.583.505 (7)170
C5C—H5C···O2iii0.932.533.365 (7)150
C6B—H6B···O1i0.932.533.434 (5)163
C6C—H6C···O2iv0.932.563.409 (6)151
C8C—H8C···O3iv0.932.303.197 (6)162
C10A—H10A···O8v0.932.483.220 (6)137
C10C—H10C···O1E0.932.593.228 (19)126
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x1, y1, z; (iv) x+1, y+1, z; (v) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O6i0.85 (5)2.02 (6)2.839 (7)160 (10)
O1W—H1WB···O1D'i0.85 (7)1.90 (7)2.668 (10)149 (7)
C3B—H3B···O1Wii0.932.543.305 (8)139
C1B—H1B···O3ii0.932.553.192 (6)126
C3A—H3A···O80.932.593.271 (6)130
C3C—H3C···O1iii0.932.433.337 (6)164
C5A—H5A···O30.932.583.505 (7)170
C5C—H5C···O2iii0.932.533.365 (7)150
C6B—H6B···O1i0.932.533.434 (5)163
C6C—H6C···O2iv0.932.563.409 (6)151
C8C—H8C···O3iv0.932.303.197 (6)162
C10A—H10A···O8v0.932.483.220 (6)137
C10C—H10C···O1E'0.932.593.228 (19)126
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y, z; (iii) x1, y1, z; (iv) x+1, y+1, z; (v) x, y1, z.
Acknowledgements top

The authors acknowledge the ANPCyT (project No. PME 2006–01113) for the purchase of the Oxford Gemini CCD diffractometer and the Spanish Research Council (CSIC) for provision of a free-of-charge license to the Cambridge Structural Database (Allen, 2002).

references
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