Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100006880/da1130sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006880/da1130Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006880/da1130IIsup3.hkl |
CCDC references: 150308; 150309
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.
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.
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).
[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) Å3 | 0.30 × 0.28 × 0.22 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 0.95 | Calculated w = 1/[σ2(Fo2) + (0.089P)2 + 2.571P] where P = (Fo2 + 2Fc2)/3 |
11915 reflections | (Δ/σ)max < 0.01 |
737 parameters | Δρmax = 0.88 e Å−3 |
5 restraints | Δρmin = −0.63 e Å−3 |
[Ni(O3S2)(C12H8N2)2]·0.92H2O·1.4CH4O | γ = 87.202 (13)° |
Mr = 592.66 | V = 2641.4 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 12.613 (2) Å | Mo Kα radiation |
b = 18.855 (3) Å | µ = 0.94 mm−1 |
c = 11.3048 (19) Å | T = 293 K |
α = 90.467 (18)° | 0.30 × 0.28 × 0.22 mm |
β = 100.365 (15)° |
Rigaku AFC7S Difractometer diffractometer | 7271 reflections with I > 2σ(I) |
Absorption correction: ψ scan MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | Rint = 0.018 |
Tmin = 0.76, Tmax = 0.80 | 3 standard reflections every 150 reflections |
12469 measured reflections | intensity decay: <3% |
11915 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 5 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.88 e Å−3 |
11915 reflections | Δρmin = −0.63 e Å−3 |
737 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
[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) Å3 | Polyhedra, pale-grey |
Z = 8 | 0.33 × 0.30 × 0.28 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 0.97 | Calculated w = 1/[σ2(Fo2) + (0.085P)2 + 8.029P] where P = (Fo2 + 2Fc2)/3 |
3914 reflections | (Δ/σ)max < 0.01 |
325 parameters | Δρmax = 0.67 e Å−3 |
28 restraints | Δρmin = −0.40 e Å−3 |
[Ni(O3S2)(C10H8N2)2]·2H2O·0.55CH4O | V = 4573.7 (17) Å3 |
Mr = 536.84 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.754 (4) Å | µ = 1.07 mm−1 |
b = 20.895 (4) Å | T = 293 K |
c = 14.402 (3) Å | 0.33 × 0.30 × 0.28 mm |
β = 132.919 (12)° |
Rigaku AFC7S Difractometer diffractometer | 2159 reflections with I > 2σ(I) |
Absorption correction: ψ scan MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | Rint = 0.075 |
Tmin = 0.71, Tmax = 0.74 | 3 standard reflections every 150 reflections |
4123 measured reflections | intensity decay: <3% |
3914 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 28 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.67 e Å−3 |
3914 reflections | Δρmin = −0.40 e Å−3 |
325 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ni(O3S2)(C12H8N2)2]·0.92H2O·1.4CH4O | [Ni(O3S2)(C10H8N2)2]·2H2O·0.55CH4O |
Mr | 592.66 | 536.84 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.613 (2), 18.855 (3), 11.3048 (19) | 20.754 (4), 20.895 (4), 14.402 (3) |
α, β, γ (°) | 90.467 (18), 100.365 (15), 87.202 (13) | 90, 132.919 (12), 90 |
V (Å3) | 2641.4 (7) | 4573.7 (17) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.94 | 1.07 |
Crystal size (mm) | 0.30 × 0.28 × 0.22 | 0.33 × 0.30 × 0.28 |
Data collection | ||
Diffractometer | Rigaku AFC7S Difractometer diffractometer | Rigaku AFC7S Difractometer diffractometer |
Absorption correction | ψ scan MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1988) | ψ scan MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) |
Tmin, Tmax | 0.76, 0.80 | 0.71, 0.74 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12469, 11915, 7271 | 4123, 3914, 2159 |
Rint | 0.018 | 0.075 |
(sin θ/λ)max (Å−1) | 0.650 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.164, 0.95 | 0.064, 0.183, 0.97 |
No. of reflections | 11915 | 3914 |
No. of parameters | 737 | 325 |
No. of restraints | 5 | 28 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.63 | 0.67, −0.40 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1994), PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).
Ni1A—N2A | 2.071 (3) | Ni1B—N2B | 2.076 (3) |
Ni1A—N1A | 2.086 (3) | Ni1B—N1B | 2.082 (3) |
Ni1A—N1D | 2.092 (3) | Ni1B—N1C | 2.087 (3) |
Ni1A—O1A | 2.093 (3) | Ni1B—N2C | 2.092 (3) |
Ni1A—N2D | 2.094 (3) | Ni1B—O1B | 2.110 (3) |
Ni1A—S1A | 2.4613 (11) | Ni1B—S1B | 2.4624 (11) |
S1A—S2A | 2.0249 (14) | S1B—S2B | 2.0260 (13) |
S2A—O3A | 1.449 (3) | S2B—O2B | 1.450 (3) |
S2A—O2A | 1.445 (3) | S2B—O3B | 1.452 (3) |
S2A—O1A | 1.494 (3) | S2B—O1B | 1.492 (3) |
Ni1—N2B | 2.060 (5) | Ni1—S1 | 2.465 (2) |
Ni1—N1B | 2.076 (5) | S1—S2 | 2.024 (3) |
Ni1—N1A | 2.078 (6) | S2—O3 | 1.456 (5) |
Ni1—N2A | 2.095 (6) | S2—O2 | 1.457 (5) |
Ni1—O1 | 2.125 (5) | S2—O1 | 1.485 (5) |
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—Ocoord: 1.495 (3), 1.489 (3) Å versus S—Onon-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—Ocoord: 102.6 (1), 102.7 (1)° versus S—S—Onon-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—Ocoord:1.484; S—Ononcoord:1.457 Å, S—S—Ocoord:103.2; S—S—Ononcoord: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.