Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005522/sk1464sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005522/sk1464Isup2.hkl |
CCDC reference: 166977
For related literature, see: Arca et al. (1997); Barton (1986); Byrom et al. (2000); Chen & Fackler (1978); Harrison & Kikabhai (1987); Hoskins & Tiekink (1985); Huang, Xiong & You (1995); Huang, Xiong, Dong & You (1995); Kovtun et al. (1992); Liu et al. (1987); Naing et al. (1995); Xiong et al. (1997); You et al. (1986, 1994).
The title compound was prepared by mixing a solution of nickel(II) bis(O,O'-di-p-tolyldithiophosphate) (0.1 mmol) in acetone (50 ml) and phen (0.1 mmol) with heating. The solution was cooled to room temperature and was then filtered. Green prismatic single crystals suitable for X-ray analysis were obtained upon slow evaporation of the solvent.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
[Ni(C14H14O2PS2)2(C12H8N2)] | Z = 2 |
Mr = 857.60 | F(000) = 888 |
Triclinic, P1 | Dx = 1.401 Mg m−3 |
a = 11.1819 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.0934 (2) Å | Cell parameters from 8192 reflections |
c = 17.2860 (2) Å | θ = 1.3–28.3° |
α = 107.693 (1)° | µ = 0.80 mm−1 |
β = 96.349 (1)° | T = 293 K |
γ = 109.896 (1)° | Prismatic slab, green |
V = 2033.41 (5) Å3 | 0.40 × 0.24 × 0.16 mm |
Siemens SMART CCD area detector diffractometer | 7040 independent reflections |
Radiation source: fine-focus sealed tube | 5007 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 1.3° |
ω scans | h = −12→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −14→11 |
Tmin = 0.739, Tmax = 0.882 | l = −20→19 |
11570 measured reflections |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0346P)2] where P = (Fo2 + 2Fc2)/3 |
7040 reflections | (Δ/σ)max = 0.001 |
482 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
[Ni(C14H14O2PS2)2(C12H8N2)] | γ = 109.896 (1)° |
Mr = 857.60 | V = 2033.41 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.1819 (2) Å | Mo Kα radiation |
b = 12.0934 (2) Å | µ = 0.80 mm−1 |
c = 17.2860 (2) Å | T = 293 K |
α = 107.693 (1)° | 0.40 × 0.24 × 0.16 mm |
β = 96.349 (1)° |
Siemens SMART CCD area detector diffractometer | 7040 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5007 reflections with I > 2σ(I) |
Tmin = 0.739, Tmax = 0.882 | Rint = 0.055 |
11570 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.40 e Å−3 |
7040 reflections | Δρmin = −0.77 e Å−3 |
482 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.29533 (4) | 0.70430 (4) | 0.16483 (3) | 0.03391 (13) | |
S1 | 0.09570 (8) | 0.75388 (9) | 0.15222 (6) | 0.0478 (2) | |
S2 | 0.40427 (8) | 0.93569 (8) | 0.19900 (6) | 0.0461 (2) | |
S3 | 0.30823 (9) | 0.72581 (8) | 0.31618 (6) | 0.0437 (2) | |
S4 | 0.17047 (9) | 0.47849 (8) | 0.14194 (6) | 0.0444 (2) | |
P1 | 0.22416 (9) | 0.92994 (9) | 0.18729 (6) | 0.0437 (2) | |
P2 | 0.18567 (8) | 0.54798 (8) | 0.26329 (6) | 0.0363 (2) | |
O1 | 0.2063 (3) | 1.0246 (2) | 0.26863 (17) | 0.0556 (7) | |
O2 | 0.1939 (3) | 1.0043 (2) | 0.12992 (17) | 0.0575 (7) | |
O3 | 0.0407 (2) | 0.5264 (2) | 0.27659 (14) | 0.0435 (6) | |
O4 | 0.2121 (2) | 0.4583 (2) | 0.30985 (15) | 0.0443 (6) | |
N1 | 0.2966 (2) | 0.6630 (3) | 0.03899 (17) | 0.0380 (6) | |
N2 | 0.4784 (3) | 0.6947 (3) | 0.16719 (18) | 0.0398 (7) | |
C1 | 0.2034 (4) | 0.6413 (3) | −0.0253 (2) | 0.0515 (9) | |
H1A | 0.1228 | 0.6401 | −0.0157 | 0.062* | |
C2 | 0.2210 (5) | 0.6201 (4) | −0.1064 (3) | 0.0678 (12) | |
H2A | 0.1533 | 0.6055 | −0.1495 | 0.081* | |
C3 | 0.3370 (5) | 0.6210 (4) | −0.1218 (3) | 0.0707 (12) | |
H3A | 0.3496 | 0.6078 | −0.1757 | 0.085* | |
C4 | 0.4399 (4) | 0.6421 (3) | −0.0558 (2) | 0.0520 (9) | |
C5 | 0.5665 (5) | 0.6441 (4) | −0.0654 (3) | 0.0674 (12) | |
H5A | 0.5847 | 0.6302 | −0.1179 | 0.081* | |
C6 | 0.6587 (4) | 0.6656 (4) | 0.0002 (3) | 0.0690 (12) | |
H6A | 0.7401 | 0.6670 | −0.0078 | 0.083* | |
C7 | 0.6357 (4) | 0.6861 (3) | 0.0816 (3) | 0.0526 (10) | |
C8 | 0.7294 (4) | 0.7098 (4) | 0.1532 (3) | 0.0735 (13) | |
H8A | 0.8137 | 0.7165 | 0.1495 | 0.088* | |
C9 | 0.6952 (4) | 0.7225 (5) | 0.2267 (3) | 0.0766 (14) | |
H9A | 0.7560 | 0.7376 | 0.2740 | 0.092* | |
C10 | 0.5684 (4) | 0.7130 (4) | 0.2324 (3) | 0.0604 (11) | |
H10A | 0.5462 | 0.7196 | 0.2834 | 0.073* | |
C11 | 0.5121 (3) | 0.6824 (3) | 0.0931 (2) | 0.0392 (8) | |
C12 | 0.4133 (3) | 0.6617 (3) | 0.0230 (2) | 0.0375 (8) | |
C13 | 0.2331 (4) | 1.0160 (3) | 0.3482 (3) | 0.0514 (10) | |
C14 | 0.1318 (4) | 0.9501 (4) | 0.3750 (3) | 0.0673 (12) | |
H14A | 0.0473 | 0.9083 | 0.3410 | 0.081* | |
C15 | 0.1588 (5) | 0.9474 (4) | 0.4553 (3) | 0.0771 (14) | |
H15A | 0.0901 | 0.9040 | 0.4745 | 0.093* | |
C16 | 0.2827 (5) | 1.0064 (4) | 0.5068 (3) | 0.0762 (14) | |
C17 | 0.3817 (5) | 1.0745 (4) | 0.4778 (3) | 0.0785 (14) | |
H17A | 0.4661 | 1.1176 | 0.5118 | 0.094* | |
C18 | 0.3572 (4) | 1.0799 (4) | 0.3987 (3) | 0.0682 (12) | |
H18A | 0.4247 | 1.1266 | 0.3802 | 0.082* | |
C19 | 0.3105 (6) | 0.9925 (5) | 0.5903 (3) | 0.119 (2) | |
H19A | 0.3951 | 1.0550 | 0.6230 | 0.179* | |
H19B | 0.3093 | 0.9097 | 0.5813 | 0.179* | |
H19C | 0.2448 | 1.0039 | 0.6195 | 0.179* | |
C20 | 0.1950 (4) | 0.9678 (4) | 0.0447 (3) | 0.0516 (10) | |
C21 | 0.3091 (4) | 1.0147 (4) | 0.0216 (3) | 0.0660 (12) | |
H21A | 0.3870 | 1.0647 | 0.0621 | 0.079* | |
C22 | 0.3083 (5) | 0.9875 (5) | −0.0624 (3) | 0.0795 (14) | |
H22A | 0.3866 | 1.0178 | −0.0778 | 0.095* | |
C23 | 0.1939 (6) | 0.9165 (5) | −0.1233 (3) | 0.0831 (15) | |
C24 | 0.0817 (5) | 0.8697 (5) | −0.0982 (3) | 0.0899 (17) | |
H24A | 0.0040 | 0.8189 | −0.1388 | 0.108* | |
C25 | 0.0787 (4) | 0.8947 (5) | −0.0145 (3) | 0.0754 (14) | |
H25A | 0.0007 | 0.8629 | 0.0009 | 0.091* | |
C26 | 0.1919 (8) | 0.8898 (7) | −0.2152 (3) | 0.143 (3) | |
H26A | 0.1078 | 0.8781 | −0.2446 | 0.214* | |
H26B | 0.2078 | 0.8147 | −0.2382 | 0.214* | |
H26C | 0.2587 | 0.9598 | −0.2209 | 0.214* | |
C27 | 0.0116 (3) | 0.5843 (3) | 0.3511 (2) | 0.0385 (8) | |
C28 | 0.0737 (4) | 0.5969 (4) | 0.4288 (2) | 0.0547 (10) | |
H28A | 0.1425 | 0.5711 | 0.4342 | 0.066* | |
C29 | 0.0324 (4) | 0.6484 (4) | 0.4982 (2) | 0.0538 (10) | |
H29A | 0.0749 | 0.6572 | 0.5504 | 0.065* | |
C30 | −0.0695 (4) | 0.6869 (3) | 0.4926 (2) | 0.0493 (9) | |
C31 | −0.1304 (4) | 0.6740 (4) | 0.4138 (3) | 0.0563 (10) | |
H31A | −0.1993 | 0.6997 | 0.4080 | 0.068* | |
C32 | −0.0888 (3) | 0.6230 (4) | 0.3435 (2) | 0.0488 (9) | |
H32A | −0.1297 | 0.6154 | 0.2911 | 0.059* | |
C33 | −0.1137 (4) | 0.7421 (4) | 0.5693 (3) | 0.0738 (13) | |
H33A | −0.1926 | 0.7527 | 0.5527 | 0.111* | |
H33B | −0.0466 | 0.8227 | 0.6043 | 0.111* | |
H33C | −0.1299 | 0.6861 | 0.5997 | 0.111* | |
C34 | 0.3278 (3) | 0.4367 (3) | 0.3182 (2) | 0.0409 (8) | |
C35 | 0.4315 (4) | 0.5172 (4) | 0.3859 (3) | 0.0568 (10) | |
H35A | 0.4294 | 0.5905 | 0.4225 | 0.068* | |
C36 | 0.5393 (4) | 0.4866 (4) | 0.3982 (3) | 0.0672 (12) | |
H36A | 0.6100 | 0.5413 | 0.4433 | 0.081* | |
C37 | 0.5450 (4) | 0.3785 (4) | 0.3460 (3) | 0.0577 (11) | |
C38 | 0.4387 (4) | 0.2994 (4) | 0.2785 (3) | 0.0543 (10) | |
H38A | 0.4404 | 0.2257 | 0.2421 | 0.065* | |
C39 | 0.3303 (3) | 0.3279 (3) | 0.2643 (2) | 0.0471 (9) | |
H39A | 0.2600 | 0.2739 | 0.2188 | 0.057* | |
C40 | 0.6608 (4) | 0.3426 (5) | 0.3621 (4) | 0.0944 (18) | |
H40A | 0.6310 | 0.2523 | 0.3430 | 0.142* | |
H40B | 0.7008 | 0.3784 | 0.4209 | 0.142* | |
H40C | 0.7238 | 0.3746 | 0.3325 | 0.142* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0324 (2) | 0.0376 (3) | 0.0397 (3) | 0.01933 (19) | 0.01263 (18) | 0.01698 (19) |
S1 | 0.0346 (5) | 0.0443 (5) | 0.0718 (7) | 0.0204 (4) | 0.0161 (4) | 0.0242 (5) |
S2 | 0.0386 (5) | 0.0414 (5) | 0.0648 (6) | 0.0171 (4) | 0.0176 (4) | 0.0248 (5) |
S3 | 0.0496 (5) | 0.0371 (5) | 0.0426 (5) | 0.0147 (4) | 0.0135 (4) | 0.0140 (4) |
S4 | 0.0525 (5) | 0.0378 (5) | 0.0434 (5) | 0.0191 (4) | 0.0183 (4) | 0.0117 (4) |
P1 | 0.0454 (5) | 0.0409 (5) | 0.0590 (6) | 0.0258 (4) | 0.0187 (5) | 0.0253 (5) |
P2 | 0.0377 (5) | 0.0374 (5) | 0.0424 (5) | 0.0197 (4) | 0.0157 (4) | 0.0184 (4) |
O1 | 0.0697 (17) | 0.0487 (15) | 0.0660 (18) | 0.0367 (14) | 0.0284 (14) | 0.0248 (13) |
O2 | 0.0743 (18) | 0.0486 (16) | 0.0717 (19) | 0.0401 (14) | 0.0201 (15) | 0.0322 (14) |
O3 | 0.0370 (12) | 0.0549 (15) | 0.0449 (14) | 0.0239 (12) | 0.0164 (11) | 0.0179 (12) |
O4 | 0.0429 (13) | 0.0497 (15) | 0.0630 (16) | 0.0275 (12) | 0.0253 (12) | 0.0357 (12) |
N1 | 0.0359 (15) | 0.0397 (16) | 0.0411 (17) | 0.0158 (13) | 0.0112 (13) | 0.0166 (13) |
N2 | 0.0360 (15) | 0.0471 (17) | 0.0473 (18) | 0.0263 (14) | 0.0116 (13) | 0.0199 (14) |
C1 | 0.048 (2) | 0.056 (2) | 0.045 (2) | 0.0198 (19) | 0.0061 (18) | 0.0151 (18) |
C2 | 0.077 (3) | 0.076 (3) | 0.041 (2) | 0.030 (3) | 0.001 (2) | 0.013 (2) |
C3 | 0.095 (3) | 0.072 (3) | 0.043 (3) | 0.028 (3) | 0.028 (2) | 0.019 (2) |
C4 | 0.063 (2) | 0.042 (2) | 0.053 (2) | 0.021 (2) | 0.024 (2) | 0.0158 (18) |
C5 | 0.084 (3) | 0.061 (3) | 0.067 (3) | 0.032 (3) | 0.051 (3) | 0.022 (2) |
C6 | 0.060 (3) | 0.068 (3) | 0.093 (4) | 0.037 (2) | 0.048 (3) | 0.026 (3) |
C7 | 0.047 (2) | 0.047 (2) | 0.075 (3) | 0.0269 (19) | 0.028 (2) | 0.023 (2) |
C8 | 0.045 (2) | 0.081 (3) | 0.108 (4) | 0.041 (2) | 0.020 (3) | 0.034 (3) |
C9 | 0.058 (3) | 0.106 (4) | 0.084 (4) | 0.054 (3) | 0.006 (3) | 0.036 (3) |
C10 | 0.055 (2) | 0.081 (3) | 0.064 (3) | 0.046 (2) | 0.011 (2) | 0.031 (2) |
C11 | 0.0390 (18) | 0.0341 (18) | 0.055 (2) | 0.0214 (16) | 0.0193 (17) | 0.0190 (16) |
C12 | 0.0421 (19) | 0.0295 (17) | 0.044 (2) | 0.0159 (15) | 0.0198 (16) | 0.0128 (15) |
C13 | 0.063 (3) | 0.033 (2) | 0.062 (3) | 0.0210 (19) | 0.027 (2) | 0.0140 (18) |
C14 | 0.067 (3) | 0.052 (3) | 0.080 (3) | 0.016 (2) | 0.029 (2) | 0.024 (2) |
C15 | 0.089 (3) | 0.058 (3) | 0.080 (4) | 0.013 (3) | 0.044 (3) | 0.028 (3) |
C16 | 0.110 (4) | 0.046 (3) | 0.057 (3) | 0.014 (3) | 0.030 (3) | 0.013 (2) |
C17 | 0.085 (3) | 0.063 (3) | 0.064 (3) | 0.008 (3) | 0.016 (3) | 0.017 (2) |
C18 | 0.070 (3) | 0.057 (3) | 0.068 (3) | 0.013 (2) | 0.027 (2) | 0.021 (2) |
C19 | 0.167 (6) | 0.093 (4) | 0.058 (3) | 0.008 (4) | 0.021 (4) | 0.024 (3) |
C20 | 0.062 (3) | 0.044 (2) | 0.061 (3) | 0.029 (2) | 0.010 (2) | 0.029 (2) |
C21 | 0.064 (3) | 0.061 (3) | 0.067 (3) | 0.013 (2) | 0.009 (2) | 0.031 (2) |
C22 | 0.082 (3) | 0.085 (3) | 0.076 (4) | 0.025 (3) | 0.024 (3) | 0.042 (3) |
C23 | 0.104 (4) | 0.084 (4) | 0.067 (3) | 0.039 (3) | 0.013 (3) | 0.037 (3) |
C24 | 0.077 (4) | 0.097 (4) | 0.078 (4) | 0.023 (3) | −0.016 (3) | 0.032 (3) |
C25 | 0.058 (3) | 0.082 (3) | 0.088 (4) | 0.023 (3) | 0.004 (3) | 0.043 (3) |
C26 | 0.194 (7) | 0.178 (7) | 0.062 (4) | 0.085 (6) | 0.024 (4) | 0.039 (4) |
C27 | 0.0362 (18) | 0.041 (2) | 0.045 (2) | 0.0169 (16) | 0.0168 (16) | 0.0203 (16) |
C28 | 0.058 (2) | 0.075 (3) | 0.052 (2) | 0.044 (2) | 0.0183 (19) | 0.028 (2) |
C29 | 0.060 (2) | 0.069 (3) | 0.048 (2) | 0.034 (2) | 0.0208 (19) | 0.029 (2) |
C30 | 0.056 (2) | 0.045 (2) | 0.056 (2) | 0.0221 (19) | 0.0276 (19) | 0.0229 (18) |
C31 | 0.054 (2) | 0.066 (3) | 0.074 (3) | 0.041 (2) | 0.029 (2) | 0.035 (2) |
C32 | 0.048 (2) | 0.061 (2) | 0.053 (2) | 0.033 (2) | 0.0180 (18) | 0.0272 (19) |
C33 | 0.089 (3) | 0.076 (3) | 0.073 (3) | 0.043 (3) | 0.047 (3) | 0.028 (2) |
C34 | 0.0409 (19) | 0.046 (2) | 0.053 (2) | 0.0219 (17) | 0.0181 (17) | 0.0323 (18) |
C35 | 0.057 (2) | 0.053 (2) | 0.057 (3) | 0.023 (2) | 0.011 (2) | 0.014 (2) |
C36 | 0.053 (2) | 0.073 (3) | 0.067 (3) | 0.021 (2) | −0.002 (2) | 0.024 (2) |
C37 | 0.044 (2) | 0.060 (3) | 0.087 (3) | 0.025 (2) | 0.016 (2) | 0.045 (2) |
C38 | 0.054 (2) | 0.042 (2) | 0.082 (3) | 0.028 (2) | 0.026 (2) | 0.030 (2) |
C39 | 0.047 (2) | 0.040 (2) | 0.058 (2) | 0.0197 (18) | 0.0106 (18) | 0.0211 (18) |
C40 | 0.051 (3) | 0.098 (4) | 0.160 (6) | 0.041 (3) | 0.017 (3) | 0.072 (4) |
Ni—N1 | 2.082 (3) | C16—C19 | 1.514 (6) |
Ni—N2 | 2.086 (3) | C17—C18 | 1.390 (6) |
Ni—S2 | 2.486 (1) | C17—H17A | 0.9300 |
Ni—S4 | 2.488 (1) | C18—H18A | 0.9300 |
Ni—S1 | 2.505 (1) | C19—H19A | 0.9600 |
Ni—S3 | 2.532 (1) | C19—H19B | 0.9600 |
S1—P1 | 1.976 (1) | C19—H19C | 0.9600 |
S2—P1 | 1.977 (1) | C20—C21 | 1.367 (6) |
S3—P2 | 1.965 (1) | C20—C25 | 1.375 (5) |
S4—P2 | 1.972 (1) | C21—C22 | 1.386 (6) |
P1—O1 | 1.602 (3) | C21—H21A | 0.9300 |
P1—O2 | 1.607 (2) | C22—C23 | 1.373 (6) |
P2—O3 | 1.607 (2) | C22—H22A | 0.9300 |
P2—O4 | 1.615 (2) | C23—C24 | 1.367 (7) |
O1—C13 | 1.417 (4) | C23—C26 | 1.518 (7) |
O2—C20 | 1.406 (4) | C24—C25 | 1.392 (7) |
O3—C27 | 1.398 (4) | C24—H24A | 0.9300 |
O4—C34 | 1.405 (4) | C25—H25A | 0.9300 |
N1—C1 | 1.330 (4) | C26—H26A | 0.9600 |
N1—C12 | 1.367 (4) | C26—H26B | 0.9600 |
N2—C10 | 1.334 (4) | C26—H26C | 0.9600 |
N2—C11 | 1.354 (4) | C27—C32 | 1.364 (5) |
C1—C2 | 1.395 (5) | C27—C28 | 1.380 (5) |
C1—H1A | 0.9300 | C28—C29 | 1.380 (5) |
C2—C3 | 1.350 (6) | C28—H28A | 0.9300 |
C2—H2A | 0.9300 | C29—C30 | 1.374 (5) |
C3—C4 | 1.423 (6) | C29—H29A | 0.9300 |
C3—H3A | 0.9300 | C30—C31 | 1.392 (5) |
C4—C12 | 1.394 (5) | C30—C33 | 1.511 (5) |
C4—C5 | 1.436 (6) | C31—C32 | 1.392 (5) |
C5—C6 | 1.340 (6) | C31—H31A | 0.9300 |
C5—H5A | 0.9300 | C32—H32A | 0.9300 |
C6—C7 | 1.421 (6) | C33—H33A | 0.9600 |
C6—H6A | 0.9300 | C33—H33B | 0.9600 |
C7—C11 | 1.405 (5) | C33—H33C | 0.9600 |
C7—C8 | 1.417 (6) | C34—C39 | 1.374 (5) |
C8—C9 | 1.348 (6) | C34—C35 | 1.378 (5) |
C8—H8A | 0.9300 | C35—C36 | 1.389 (6) |
C9—C10 | 1.399 (6) | C35—H35A | 0.9300 |
C9—H9A | 0.9300 | C36—C37 | 1.371 (6) |
C10—H10A | 0.9300 | C36—H36A | 0.9300 |
C11—C12 | 1.443 (5) | C37—C38 | 1.389 (5) |
C13—C14 | 1.364 (5) | C37—C40 | 1.523 (5) |
C13—C18 | 1.370 (5) | C38—C39 | 1.385 (5) |
C14—C15 | 1.399 (6) | C38—H38A | 0.9300 |
C14—H14A | 0.9300 | C39—H39A | 0.9300 |
C15—C16 | 1.375 (6) | C40—H40A | 0.9600 |
C15—H15A | 0.9300 | C40—H40B | 0.9600 |
C16—C17 | 1.382 (6) | C40—H40C | 0.9600 |
N1—Ni—N2 | 79.8 (1) | C15—C16—C19 | 121.3 (4) |
N1—Ni—S2 | 92.65 (8) | C17—C16—C19 | 121.3 (5) |
N2—Ni—S2 | 88.45 (8) | C16—C17—C18 | 121.1 (5) |
N1—Ni—S4 | 92.44 (8) | C16—C17—H17A | 119.4 |
N2—Ni—S4 | 96.59 (8) | C18—C17—H17A | 119.4 |
S2—Ni—S4 | 173.40 (3) | C13—C18—C17 | 119.6 (4) |
N1—Ni—S1 | 94.54 (8) | C13—C18—H18A | 120.2 |
N2—Ni—S1 | 167.94 (8) | C17—C18—H18A | 120.2 |
S2—Ni—S1 | 81.13 (3) | C16—C19—H19A | 109.5 |
S4—Ni—S1 | 94.27 (3) | C16—C19—H19B | 109.5 |
N1—Ni—S3 | 170.38 (8) | H19A—C19—H19B | 109.5 |
N2—Ni—S3 | 93.34 (8) | C16—C19—H19C | 109.5 |
S2—Ni—S3 | 93.92 (3) | H19A—C19—H19C | 109.5 |
S4—Ni—S3 | 81.57 (3) | H19B—C19—H19C | 109.5 |
S1—Ni—S3 | 93.42 (3) | C21—C20—C25 | 120.7 (4) |
P1—S1—Ni | 83.94 (4) | C21—C20—O2 | 119.7 (4) |
P1—S2—Ni | 84.42 (4) | C25—C20—O2 | 119.3 (4) |
P2—S3—Ni | 81.58 (4) | C20—C21—C22 | 119.9 (4) |
P2—S4—Ni | 82.60 (4) | C20—C21—H21A | 120.1 |
O1—P1—O2 | 92.49 (14) | C22—C21—H21A | 120.1 |
O1—P1—S1 | 113.40 (11) | C23—C22—C21 | 121.1 (5) |
O2—P1—S1 | 113.96 (11) | C23—C22—H22A | 119.4 |
O1—P1—S2 | 112.80 (11) | C21—C22—H22A | 119.4 |
O2—P1—S2 | 112.86 (11) | C24—C23—C22 | 117.6 (5) |
S1—P1—S2 | 110.37 (6) | C24—C23—C26 | 121.0 (5) |
O3—P2—O4 | 96.81 (12) | C22—C23—C26 | 121.4 (5) |
O3—P2—S3 | 112.61 (10) | C23—C24—C25 | 122.9 (5) |
O4—P2—S3 | 113.76 (10) | C23—C24—H24A | 118.6 |
O3—P2—S4 | 107.37 (10) | C25—C24—H24A | 118.6 |
O4—P2—S4 | 112.28 (10) | C20—C25—C24 | 117.8 (4) |
S3—P2—S4 | 112.81 (5) | C20—C25—H25A | 121.1 |
C13—O1—P1 | 121.3 (2) | C24—C25—H25A | 121.1 |
C20—O2—P1 | 122.7 (2) | C23—C26—H26A | 109.5 |
C27—O3—P2 | 125.1 (2) | C23—C26—H26B | 109.5 |
C34—O4—P2 | 124.30 (19) | H26A—C26—H26B | 109.5 |
C1—N1—C12 | 117.4 (3) | C23—C26—H26C | 109.5 |
C1—N1—Ni | 129.6 (2) | H26A—C26—H26C | 109.5 |
C12—N1—Ni | 113.0 (2) | H26B—C26—H26C | 109.5 |
C10—N2—C11 | 117.8 (3) | C32—C27—C28 | 120.1 (3) |
C10—N2—Ni | 128.8 (3) | C32—C27—O3 | 116.2 (3) |
C11—N2—Ni | 112.9 (2) | C28—C27—O3 | 123.5 (3) |
N1—C1—C2 | 123.0 (4) | C29—C28—C27 | 119.2 (4) |
N1—C1—H1A | 118.5 | C29—C28—H28A | 120.4 |
C2—C1—H1A | 118.5 | C27—C28—H28A | 120.4 |
C3—C2—C1 | 119.6 (4) | C30—C29—C28 | 122.1 (3) |
C3—C2—H2A | 120.2 | C30—C29—H29A | 119.0 |
C1—C2—H2A | 120.2 | C28—C29—H29A | 119.0 |
C2—C3—C4 | 120.0 (4) | C29—C30—C31 | 117.8 (4) |
C2—C3—H3A | 120.0 | C29—C30—C33 | 121.2 (4) |
C4—C3—H3A | 120.0 | C31—C30—C33 | 120.9 (4) |
C12—C4—C3 | 116.4 (4) | C30—C31—C32 | 120.5 (4) |
C12—C4—C5 | 119.0 (4) | C30—C31—H31A | 119.8 |
C3—C4—C5 | 124.6 (4) | C32—C31—H31A | 119.8 |
C6—C5—C4 | 121.0 (4) | C27—C32—C31 | 120.2 (3) |
C6—C5—H5A | 119.5 | C27—C32—H32A | 119.9 |
C4—C5—H5A | 119.5 | C31—C32—H32A | 119.9 |
C5—C6—C7 | 121.8 (4) | C30—C33—H33A | 109.5 |
C5—C6—H6A | 119.1 | C30—C33—H33B | 109.5 |
C7—C6—H6A | 119.1 | H33A—C33—H33B | 109.5 |
C11—C7—C8 | 116.8 (4) | C30—C33—H33C | 109.5 |
C11—C7—C6 | 118.9 (4) | H33A—C33—H33C | 109.5 |
C8—C7—C6 | 124.3 (4) | H33B—C33—H33C | 109.5 |
C9—C8—C7 | 119.4 (4) | C39—C34—C35 | 120.8 (3) |
C9—C8—H8A | 120.3 | C39—C34—O4 | 119.3 (3) |
C7—C8—H8A | 120.3 | C35—C34—O4 | 119.5 (3) |
C8—C9—C10 | 120.3 (4) | C34—C35—C36 | 118.7 (4) |
C8—C9—H9A | 119.9 | C34—C35—H35A | 120.7 |
C10—C9—H9A | 119.9 | C36—C35—H35A | 120.7 |
N2—C10—C9 | 122.3 (4) | C37—C36—C35 | 122.2 (4) |
N2—C10—H10A | 118.8 | C37—C36—H36A | 118.9 |
C9—C10—H10A | 118.8 | C35—C36—H36A | 118.9 |
N2—C11—C7 | 123.4 (3) | C36—C37—C38 | 117.6 (3) |
N2—C11—C12 | 117.1 (3) | C36—C37—C40 | 121.9 (4) |
C7—C11—C12 | 119.5 (3) | C38—C37—C40 | 120.5 (4) |
N1—C12—C4 | 123.6 (3) | C39—C38—C37 | 121.5 (4) |
N1—C12—C11 | 116.6 (3) | C39—C38—H38A | 119.2 |
C4—C12—C11 | 119.8 (3) | C37—C38—H38A | 119.2 |
C14—C13—C18 | 121.2 (4) | C34—C39—C38 | 119.2 (3) |
C14—C13—O1 | 118.7 (4) | C34—C39—H39A | 120.4 |
C18—C13—O1 | 120.0 (3) | C38—C39—H39A | 120.4 |
C13—C14—C15 | 118.0 (4) | C37—C40—H40A | 109.5 |
C13—C14—H14A | 121.0 | C37—C40—H40B | 109.5 |
C15—C14—H14A | 121.0 | H40A—C40—H40B | 109.5 |
C16—C15—C14 | 122.7 (4) | C37—C40—H40C | 109.5 |
C16—C15—H15A | 118.7 | H40A—C40—H40C | 109.5 |
C14—C15—H15A | 118.7 | H40B—C40—H40C | 109.5 |
C15—C16—C17 | 117.3 (4) | ||
N1—Ni—S1—P1 | −94.46 (8) | C7—C8—C9—C10 | −0.3 (7) |
N2—Ni—S1—P1 | −33.1 (4) | C11—N2—C10—C9 | 1.5 (6) |
S2—Ni—S1—P1 | −2.49 (4) | Ni—N2—C10—C9 | −170.0 (3) |
S4—Ni—S1—P1 | 172.74 (4) | C8—C9—C10—N2 | −1.8 (7) |
S3—Ni—S1—P1 | 90.95 (4) | C10—N2—C11—C7 | 0.9 (5) |
N1—Ni—S2—P1 | 96.67 (8) | Ni—N2—C11—C7 | 173.7 (3) |
N2—Ni—S2—P1 | 176.38 (8) | C10—N2—C11—C12 | 179.5 (3) |
S1—Ni—S2—P1 | 2.48 (4) | Ni—N2—C11—C12 | −7.7 (4) |
S3—Ni—S2—P1 | −90.37 (4) | C8—C7—C11—N2 | −2.9 (5) |
N2—Ni—S3—P2 | −103.97 (8) | C6—C7—C11—N2 | 176.7 (3) |
S2—Ni—S3—P2 | 167.35 (4) | C8—C7—C11—C12 | 178.6 (3) |
S4—Ni—S3—P2 | −7.80 (4) | C6—C7—C11—C12 | −1.8 (5) |
S1—Ni—S3—P2 | 86.02 (4) | C1—N1—C12—C4 | 1.7 (5) |
N1—Ni—S4—P2 | −179.82 (8) | Ni—N1—C12—C4 | −176.9 (2) |
N2—Ni—S4—P2 | 100.17 (8) | C1—N1—C12—C11 | −178.6 (3) |
S1—Ni—S4—P2 | −85.08 (4) | Ni—N1—C12—C11 | 2.8 (3) |
S3—Ni—S4—P2 | 7.75 (4) | C3—C4—C12—N1 | −0.9 (5) |
Ni—S1—P1—O1 | −124.37 (11) | C5—C4—C12—N1 | 179.3 (3) |
Ni—S1—P1—O2 | 131.50 (12) | C3—C4—C12—C11 | 179.3 (3) |
Ni—S1—P1—S2 | 3.30 (6) | C5—C4—C12—C11 | −0.5 (5) |
Ni—S2—P1—O1 | 124.67 (11) | N2—C11—C12—N1 | 3.3 (4) |
Ni—S2—P1—O2 | −132.12 (12) | C7—C11—C12—N1 | −178.0 (3) |
Ni—S2—P1—S1 | −3.32 (6) | N2—C11—C12—C4 | −176.9 (3) |
Ni—S3—P2—O3 | −111.14 (10) | C7—C11—C12—C4 | 1.7 (5) |
Ni—S3—P2—O4 | 139.98 (10) | P1—O1—C13—C14 | −96.1 (4) |
Ni—S3—P2—S4 | 10.59 (5) | P1—O1—C13—C18 | 88.1 (4) |
Ni—S4—P2—O3 | 113.89 (10) | C18—C13—C14—C15 | −1.3 (6) |
Ni—S4—P2—O4 | −140.89 (9) | O1—C13—C14—C15 | −177.1 (4) |
Ni—S4—P2—S3 | −10.75 (5) | C13—C14—C15—C16 | −1.1 (7) |
O2—P1—O1—C13 | −174.2 (3) | C14—C15—C16—C17 | 2.6 (7) |
S1—P1—O1—C13 | 68.3 (3) | C14—C15—C16—C19 | −174.8 (5) |
S2—P1—O1—C13 | −58.0 (3) | C15—C16—C17—C18 | −1.8 (7) |
O1—P1—O2—C20 | 179.4 (3) | C19—C16—C17—C18 | 175.5 (5) |
S1—P1—O2—C20 | −63.6 (3) | C14—C13—C18—C17 | 2.1 (7) |
S2—P1—O2—C20 | 63.3 (3) | O1—C13—C18—C17 | 177.7 (4) |
O4—P2—O3—C27 | 77.9 (3) | C16—C17—C18—C13 | −0.4 (7) |
S3—P2—O3—C27 | −41.4 (3) | P1—O2—C20—C21 | −88.8 (4) |
S4—P2—O3—C27 | −166.2 (2) | P1—O2—C20—C25 | 97.2 (4) |
O3—P2—O4—C34 | 179.3 (3) | C25—C20—C21—C22 | −0.6 (6) |
S3—P2—O4—C34 | −62.3 (3) | O2—C20—C21—C22 | −174.5 (3) |
S4—P2—O4—C34 | 67.3 (3) | C20—C21—C22—C23 | 1.7 (7) |
N2—Ni—N1—C1 | 176.4 (3) | C21—C22—C23—C24 | −2.4 (7) |
S2—Ni—N1—C1 | −95.7 (3) | C21—C22—C23—C26 | 178.1 (5) |
S4—Ni—N1—C1 | 80.1 (3) | C22—C23—C24—C25 | 2.3 (8) |
S1—Ni—N1—C1 | −14.4 (3) | C26—C23—C24—C25 | −178.2 (5) |
N2—Ni—N1—C12 | −5.2 (2) | C21—C20—C25—C24 | 0.4 (6) |
S2—Ni—N1—C12 | 82.7 (2) | O2—C20—C25—C24 | 174.3 (4) |
S4—Ni—N1—C12 | −101.5 (2) | C23—C24—C25—C20 | −1.3 (7) |
S1—Ni—N1—C12 | 164.0 (2) | P2—O3—C27—C32 | 140.0 (3) |
N1—Ni—N2—C10 | 178.8 (3) | P2—O3—C27—C28 | −43.6 (4) |
S2—Ni—N2—C10 | 85.9 (3) | C32—C27—C28—C29 | 0.4 (5) |
S4—Ni—N2—C10 | −89.9 (3) | O3—C27—C28—C29 | −175.9 (3) |
S1—Ni—N2—C10 | 116.0 (4) | C27—C28—C29—C30 | 0.4 (6) |
S3—Ni—N2—C10 | −8.0 (3) | C28—C29—C30—C31 | −0.8 (6) |
N1—Ni—N2—C11 | 7.0 (2) | C28—C29—C30—C33 | 179.6 (4) |
S2—Ni—N2—C11 | −86.0 (2) | C29—C30—C31—C32 | 0.3 (5) |
S4—Ni—N2—C11 | 98.3 (2) | C33—C30—C31—C32 | 180.0 (4) |
S1—Ni—N2—C11 | −55.8 (5) | C28—C27—C32—C31 | −0.8 (5) |
S3—Ni—N2—C11 | −179.8 (2) | O3—C27—C32—C31 | 175.7 (3) |
C12—N1—C1—C2 | −1.3 (5) | C30—C31—C32—C27 | 0.5 (6) |
Ni—N1—C1—C2 | 177.1 (3) | P2—O4—C34—C39 | −99.4 (3) |
N1—C1—C2—C3 | 0.2 (6) | P2—O4—C34—C35 | 88.1 (4) |
C1—C2—C3—C4 | 0.6 (7) | C39—C34—C35—C36 | 0.5 (6) |
C2—C3—C4—C12 | −0.3 (6) | O4—C34—C35—C36 | 172.9 (3) |
C2—C3—C4—C5 | 179.5 (4) | C34—C35—C36—C37 | −0.9 (6) |
C12—C4—C5—C6 | −0.7 (6) | C35—C36—C37—C38 | 0.8 (6) |
C3—C4—C5—C6 | 179.5 (4) | C35—C36—C37—C40 | −177.2 (4) |
C4—C5—C6—C7 | 0.6 (7) | C36—C37—C38—C39 | −0.3 (6) |
C5—C6—C7—C11 | 0.7 (6) | C40—C37—C38—C39 | 177.8 (4) |
C5—C6—C7—C8 | −179.7 (4) | C35—C34—C39—C38 | 0.0 (5) |
C11—C7—C8—C9 | 2.5 (6) | O4—C34—C39—C38 | −172.5 (3) |
C6—C7—C8—C9 | −177.1 (4) | C37—C38—C39—C34 | −0.1 (5) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C14H14O2PS2)2(C12H8N2)] |
Mr | 857.60 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.1819 (2), 12.0934 (2), 17.2860 (2) |
α, β, γ (°) | 107.693 (1), 96.349 (1), 109.896 (1) |
V (Å3) | 2033.41 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.40 × 0.24 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.739, 0.882 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11570, 7040, 5007 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.120, 0.93 |
No. of reflections | 7040 |
No. of parameters | 482 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.77 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
Ni—N1 | 2.082 (3) | S2—P1 | 1.977 (1) |
Ni—N2 | 2.086 (3) | S3—P2 | 1.965 (1) |
Ni—S2 | 2.486 (1) | S4—P2 | 1.972 (1) |
Ni—S4 | 2.488 (1) | O1—C13 | 1.417 (4) |
Ni—S1 | 2.505 (1) | O2—C20 | 1.406 (4) |
Ni—S3 | 2.532 (1) | O3—C27 | 1.398 (4) |
S1—P1 | 1.976 (1) | O4—C34 | 1.405 (4) |
N1—Ni—N2 | 79.8 (1) | S1—P1—S2 | 110.37 (6) |
S2—Ni—S1 | 81.13 (3) | S3—P2—S4 | 112.81 (5) |
S4—Ni—S3 | 81.57 (3) |
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In recent years, the adducts of nickel(II) dithiophosphate with neutral nitrogen ligands have received increasing attention owing to their extensive applications as both antioxidants and antiwear additives in the rubber industry and lubrication engineering (Harrison & Kikabhai, 1987; Kovtun et al., 1992). Additionally, the adducts and their formation reactions have also been found useful in a wide variety of ways, such as biological application and acting as both ultraviolet absorber and antioxidants. In addition to their syntheses and various physico-chemical investigations, the crystal structures of many nickel(II) complexes and their adducts with nitrogen bases have been reported (Huang et al., 1995; You et al., 1994). Metal complexes of the type [M(LL)3] ion, where LL is either 1,10-phenanthroline (phen) or a modified phen ligand, are particularly attractive species for developing new diagnostic and therapeutic agents that can recognize and cleave DNA (Barton, 1986; Naing et al., 1995). Thus the crystal structure of [Ni{(pMePh-dtp)2}(phen)], (I), was determined. \sch
A perspective view of the title complex with the atomic numbering scheme is shown in Fig. 1. In the title complex, the NiII atom lies in the centre of the octahedral geometry of the NiN2S4 chromophore. Crystals of this compound are composed of the discrete molecules.
The Ni—S distances of the title complex (Table 1) are in good agreement with similar distances found in six-coordinate complex [Ni{(C4H9O)2PS2}2(bipy)] [2.466 (2), 2.524 (2), 2.463 (2) and 2.522 (2) Å; You et al., 1986]. However the distances are much longer than those in the four-coordinate compounds such as Ni[S2COPh-4-tBu]2 [2.219 (4), 2.213 (6) Å; Chen & Fackler, 1978], [Ni{(iso-C3H7O)2PS2}2] [2.227 (1), 2.216 (1) Å; Hoskins & Tiekink, 1985] and [Ni{(OC2H5)(4-CH3OPh)PS2}2] [2.1297 (8) and 2.2225 (8) Å; Arca et al., 1997]. This probably reflects the change from octahedral coordination in the title compound to square planar or tetrahedral complexes.
The Ni—N distances of the title compound (Table 1) are in good agreement with similar distances found in the compound [Ni{(C4H9O)2PS2}2(bipy)] [2.089 (4), 2.088 (4) Å] and [Ni{(C2H5O)CS2}2(phen)]·(H2O)3 [2.074 (4) and 2.076 (4) Å; Xiong et al., 1997].
The distances between the atom P1 and two sulfur atoms (Table 1) are nearly equal. However the distances between the atom P2 and the other two sulfur atoms are different. It is noteworthy that all the P—S bonds lengths are intermediate between the single bond (2.09 Å) and the double bond (1.87 Å) values, which results from substantial delocalization of electrons throughout the two NiS2P four-membered rings. This is similar to that found for analogous dtp complexes, [Ni{(C2H5O)2PS2}2(C5H6N2)2] [Huang et al., 1995], [Ni{(C4H9O)2PS2}2(py)2] (Liu et al., 1987), [Ni{(C4H9O)2PS2}2(bipy)] and [M2{(i-C3H7O)2PS2}4], M=Zn or Cd (Byrom et al., 2000).
The C—O distances are much shorter than those found in [Ni{(C2H5O)2PS2}2(C5H6N2)2] [1.446 (5) and 1.430 (5) Å]. This is probably a result of the electronic effect of the benzene rings.
The S—Ni—S bond angles (Table 1) are similar to those found in [Ni{(C4H9O)2PS2}2(bipy)] [81.40 (7), 81.63 (7)°]. The N1—Ni—N2 bond angle (Table 1) is also similar to that found in [Ni{(C4H9O)2PS2}2(bipy)] [79.5 (2)°].
The (phen) ligand and Ni atom are also coplanar; the mean deviation from the best plane is 0.065 (1) Å. The two planes through Ni, P and S2 form the dihedral angle of 89.18 (4) Å. The dihedral angles between the plane of phen ligand and these two NiS2P planes are 89.21 (7) and 74.92 (7) Å. This indicates that the structure of NiN2S4 is obviously a distorted octahedra.