Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102019212/dn1015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102019212/dn1015Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102019212/dn1015IIsup3.hkl |
CCDC references: 201253; 201254
To a solution of sodium methanolate (0.6 g Na in 100 ml MeOH), 4,5-dimethyloxycarbonyl-2-oxo-1,3-dithiole (3 g) was added; the solution turned yellow. Upon addition of NiCl2 (0.84 g), the solution turned orange and it was then stirred for 90 min. Tetraphenylphosphonium bromide (5.4 g) in water (volume?) was added. The methanol was then evaporated, affording red needles of (I) (yield 4.81 g, 59%). Analyses calculated (found) for C60H52O8S4PNi: C 62.67 (62.63), H 4.56 (4.55)%. A single-crystal was prepared by ether vapour diffusion in an acetonitrile solution. To a solution of (I) (1 g) in methanol (200 ml), I2 (0.11 g) was added and the solution stirred overnight, before being evaporated to dryness. The product was washed with water and ether. The remaining solid was recrystallized from hot acetonitrile, affording dark-red prisms of (II) (yield 0.78 g, 70%). Analyses calculated (found) for C60H52O8S4PINi: C 56.44 (56.46), H 4.10 (4.07), S 10.04 (9.74)%.
H atoms were treated as riding, with C—H distances in the range 0.93–0.96 Å. Is this added text OK?
Data collection: EXPOSE in IPDS (Stoe & Cie, 1995) for (I); CAD-4 EXPRESS (Enraf Nonius, 1994) for (II). Cell refinement: SELECT and CELL, both in IPDS for (I); CAD-4 EXPRESS for (II). Data reduction: INTEGRATE in IPDS for (I); XCAD4 (Harms & Wocadlo, 1995) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(C24H20P)2[Ni(C6H6O4S2)2] | Z = 1 |
Mr = 1149.91 | F(000) = 598 |
Triclinic, P1 | Dx = 1.393 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2994 (14) Å | Cell parameters from 8000 reflections |
b = 11.1508 (16) Å | θ = 1.7–26.1° |
c = 13.8197 (19) Å | µ = 0.62 mm−1 |
α = 68.023 (16)° | T = 200 K |
β = 68.730 (15)° | Prism, red |
γ = 80.092 (17)° | 0.63 × 0.23 × 0.15 mm |
V = 1370.3 (3) Å3 |
Stoe IPDS diffractometer | 3899 reflections with I > 2σ(I) |
Detector resolution: 6.66 pixels mm-1 | Rint = 0.052 |
oscillation, Δϕ = 1.4° scans | θmax = 25.9°, θmin = 2.0° |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1995) | h = −11→12 |
Tmin = 0.777, Tmax = 0.928 | k = −12→13 |
14269 measured reflections | l = 0→16 |
4966 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0386P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.071 | (Δ/σ)max = 0.001 |
S = 0.93 | Δρmax = 0.33 e Å−3 |
4966 reflections | Δρmin = −0.16 e Å−3 |
340 parameters |
(C24H20P)2[Ni(C6H6O4S2)2] | γ = 80.092 (17)° |
Mr = 1149.91 | V = 1370.3 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.2994 (14) Å | Mo Kα radiation |
b = 11.1508 (16) Å | µ = 0.62 mm−1 |
c = 13.8197 (19) Å | T = 200 K |
α = 68.023 (16)° | 0.63 × 0.23 × 0.15 mm |
β = 68.730 (15)° |
Stoe IPDS diffractometer | 4966 independent reflections |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1995) | 3899 reflections with I > 2σ(I) |
Tmin = 0.777, Tmax = 0.928 | Rint = 0.052 |
14269 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.33 e Å−3 |
4966 reflections | Δρmin = −0.16 e Å−3 |
340 parameters |
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 | ||
Ni1 | 0.0 | 0.0 | 0.0 | 0.02188 (10) | |
S1 | −0.09482 (6) | −0.17867 (4) | 0.12403 (4) | 0.02918 (13) | |
S2 | −0.02986 (6) | 0.08252 (4) | 0.12725 (4) | 0.02770 (12) | |
C1 | −0.2417 (3) | −0.24640 (19) | 0.34362 (16) | 0.0325 (5) | |
C2 | −0.1561 (2) | −0.14421 (17) | 0.24564 (15) | 0.0242 (4) | |
C3 | −0.1285 (2) | −0.03120 (17) | 0.24930 (15) | 0.0241 (4) | |
C4 | −0.1688 (2) | 0.00043 (18) | 0.35068 (16) | 0.0291 (5) | |
C5 | −0.4699 (3) | −0.3052 (3) | 0.45821 (19) | 0.0591 (8) | |
H5B | −0.565 | −0.2804 | 0.4614 | 0.089* | |
H5C | −0.455 | −0.2975 | 0.5203 | 0.089* | |
H5D | −0.4509 | −0.3933 | 0.4602 | 0.089* | |
C6 | −0.2965 (4) | −0.0620 (3) | 0.5421 (2) | 0.0802 (12) | |
H6B | −0.3571 | −0.1285 | 0.5987 | 0.12* | |
H6C | −0.344 | 0.0211 | 0.5364 | 0.12* | |
H6D | −0.2143 | −0.0651 | 0.5604 | 0.12* | |
O1 | −0.1971 (2) | −0.34208 (16) | 0.40061 (14) | 0.0621 (5) | |
O2 | −0.37791 (17) | −0.22188 (15) | 0.35727 (12) | 0.0408 (4) | |
O3 | −0.12698 (17) | 0.08992 (13) | 0.35905 (12) | 0.0368 (4) | |
O4 | −0.2575 (2) | −0.08259 (18) | 0.43793 (13) | 0.0650 (6) | |
P1A | 0.34728 (5) | −0.37810 (4) | 0.17411 (4) | 0.02045 (11) | |
C1A | 0.4223 (2) | −0.25116 (17) | 0.04678 (15) | 0.0222 (4) | |
C2A | 0.5659 (2) | −0.23516 (19) | 0.00322 (17) | 0.0317 (5) | |
H2A | 0.6245 | −0.2914 | 0.0396 | 0.047* | |
C3A | 0.6211 (2) | −0.1351 (2) | −0.09460 (19) | 0.0408 (5) | |
H3A | 0.7168 | −0.1242 | −0.1238 | 0.061* | |
C4A | 0.5339 (2) | −0.0520 (2) | −0.14848 (18) | 0.0374 (5) | |
H4A | 0.5712 | 0.0148 | −0.2142 | 0.056* | |
C5A | 0.3917 (2) | −0.06712 (19) | −0.10557 (17) | 0.0334 (5) | |
H5A | 0.3338 | −0.0103 | −0.1423 | 0.05* | |
C6A | 0.3350 (2) | −0.16620 (18) | −0.00825 (16) | 0.0273 (4) | |
H6A | 0.2392 | −0.1762 | 0.0204 | 0.041* | |
C7A | 0.2542 (2) | −0.31190 (17) | 0.28230 (15) | 0.0229 (4) | |
C8A | 0.2097 (2) | −0.18183 (17) | 0.25765 (16) | 0.0264 (4) | |
H8A | 0.2261 | −0.1281 | 0.1846 | 0.04* | |
C9A | 0.1409 (2) | −0.13329 (19) | 0.34256 (17) | 0.0320 (5) | |
H9A | 0.1129 | −0.0462 | 0.3264 | 0.048* | |
C10A | 0.1137 (2) | −0.2128 (2) | 0.45063 (17) | 0.0356 (5) | |
H10A | 0.0682 | −0.1791 | 0.5071 | 0.053* | |
C11A | 0.1538 (2) | −0.3433 (2) | 0.47605 (17) | 0.0358 (5) | |
H11A | 0.1325 | −0.3974 | 0.5494 | 0.054* | |
C12A | 0.2253 (2) | −0.39271 (19) | 0.39234 (16) | 0.0295 (5) | |
H12A | 0.2543 | −0.4796 | 0.4091 | 0.044* | |
C13A | 0.2341 (2) | −0.46965 (17) | 0.15707 (15) | 0.0226 (4) | |
C14A | 0.2341 (2) | −0.4539 (2) | 0.05239 (16) | 0.0314 (5) | |
H14A | 0.2877 | −0.3915 | −0.0095 | 0.047* | |
C15A | 0.1530 (2) | −0.5328 (2) | 0.04103 (18) | 0.0385 (5) | |
H15A | 0.1516 | −0.5219 | −0.0287 | 0.058* | |
C16A | 0.0757 (2) | −0.6257 (2) | 0.13143 (19) | 0.0370 (5) | |
H16A | 0.0223 | −0.6781 | 0.1231 | 0.055* | |
C17A | 0.0765 (3) | −0.6420 (2) | 0.23512 (19) | 0.0422 (6) | |
H17A | 0.0249 | −0.7065 | 0.2963 | 0.063* | |
C18A | 0.1534 (2) | −0.5630 (2) | 0.24884 (17) | 0.0379 (5) | |
H18A | 0.1511 | −0.5724 | 0.3192 | 0.057* | |
C19A | 0.4831 (2) | −0.48604 (17) | 0.21542 (14) | 0.0221 (4) | |
C20A | 0.5033 (2) | −0.61234 (18) | 0.21257 (15) | 0.0268 (4) | |
H20A | 0.4437 | −0.6435 | 0.1913 | 0.04* | |
C21A | 0.6122 (2) | −0.69012 (18) | 0.24165 (16) | 0.0310 (5) | |
H21A | 0.625 | −0.7744 | 0.2408 | 0.047* | |
C22A | 0.7027 (2) | −0.64412 (19) | 0.27217 (17) | 0.0324 (5) | |
H22A | 0.7757 | −0.6975 | 0.2917 | 0.049* | |
C23A | 0.6846 (2) | −0.5185 (2) | 0.27366 (17) | 0.0327 (5) | |
H23A | 0.7465 | −0.4872 | 0.2927 | 0.049* | |
C24A | 0.5748 (2) | −0.44006 (18) | 0.24682 (16) | 0.0277 (4) | |
H24A | 0.5614 | −0.3566 | 0.2495 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0234 (2) | 0.01795 (17) | 0.02188 (18) | −0.00465 (13) | −0.00635 (15) | −0.00348 (13) |
S1 | 0.0391 (3) | 0.0200 (2) | 0.0245 (2) | −0.0090 (2) | −0.0049 (2) | −0.00522 (19) |
S2 | 0.0356 (3) | 0.0217 (2) | 0.0248 (2) | −0.0107 (2) | −0.0084 (2) | −0.00415 (19) |
C1 | 0.0463 (14) | 0.0255 (10) | 0.0236 (10) | −0.0115 (10) | −0.0085 (10) | −0.0046 (8) |
C2 | 0.0250 (11) | 0.0215 (9) | 0.0227 (9) | −0.0029 (8) | −0.0089 (8) | −0.0020 (7) |
C3 | 0.0243 (11) | 0.0236 (9) | 0.0233 (9) | −0.0030 (8) | −0.0107 (8) | −0.0030 (8) |
C4 | 0.0328 (12) | 0.0261 (10) | 0.0281 (10) | −0.0017 (9) | −0.0121 (9) | −0.0067 (8) |
C5 | 0.0586 (18) | 0.0769 (18) | 0.0318 (13) | −0.0430 (15) | 0.0080 (12) | −0.0122 (13) |
C6 | 0.122 (3) | 0.088 (2) | 0.0299 (14) | −0.055 (2) | 0.0086 (16) | −0.0292 (15) |
O1 | 0.0729 (14) | 0.0374 (9) | 0.0432 (10) | −0.0028 (9) | −0.0108 (10) | 0.0142 (8) |
O2 | 0.0365 (10) | 0.0516 (9) | 0.0297 (8) | −0.0220 (8) | −0.0046 (7) | −0.0062 (7) |
O3 | 0.0528 (10) | 0.0252 (7) | 0.0358 (8) | −0.0057 (7) | −0.0141 (7) | −0.0127 (6) |
O4 | 0.0927 (15) | 0.0741 (12) | 0.0284 (9) | −0.0553 (12) | 0.0102 (9) | −0.0241 (9) |
P1A | 0.0205 (3) | 0.0211 (2) | 0.0185 (2) | −0.00291 (19) | −0.0059 (2) | −0.00487 (18) |
C1A | 0.0235 (11) | 0.0213 (9) | 0.0206 (9) | −0.0032 (8) | −0.0060 (8) | −0.0060 (7) |
C2A | 0.0241 (11) | 0.0303 (10) | 0.0333 (11) | −0.0020 (9) | −0.0097 (9) | −0.0022 (9) |
C3A | 0.0253 (12) | 0.0416 (12) | 0.0404 (13) | −0.0091 (10) | −0.0045 (10) | −0.0003 (10) |
C4A | 0.0411 (14) | 0.0298 (11) | 0.0302 (11) | −0.0107 (10) | −0.0084 (10) | 0.0026 (9) |
C5A | 0.0345 (13) | 0.0300 (10) | 0.0322 (11) | −0.0017 (9) | −0.0169 (10) | −0.0008 (9) |
C6A | 0.0232 (11) | 0.0300 (10) | 0.0266 (10) | −0.0012 (8) | −0.0090 (9) | −0.0064 (8) |
C7A | 0.0216 (10) | 0.0256 (9) | 0.0227 (9) | −0.0021 (8) | −0.0082 (8) | −0.0082 (8) |
C8A | 0.0278 (12) | 0.0249 (9) | 0.0247 (10) | −0.0032 (8) | −0.0088 (9) | −0.0054 (8) |
C9A | 0.0321 (13) | 0.0294 (10) | 0.0369 (12) | 0.0042 (9) | −0.0121 (10) | −0.0156 (9) |
C10A | 0.0355 (13) | 0.0456 (12) | 0.0314 (11) | 0.0057 (10) | −0.0098 (10) | −0.0236 (10) |
C11A | 0.0384 (14) | 0.0418 (12) | 0.0216 (10) | 0.0011 (10) | −0.0078 (10) | −0.0078 (9) |
C12A | 0.0322 (12) | 0.0299 (10) | 0.0244 (10) | 0.0039 (9) | −0.0112 (9) | −0.0076 (8) |
C13A | 0.0197 (10) | 0.0238 (9) | 0.0229 (9) | −0.0022 (8) | −0.0058 (8) | −0.0070 (7) |
C14A | 0.0304 (12) | 0.0390 (11) | 0.0249 (10) | −0.0110 (9) | −0.0037 (9) | −0.0120 (9) |
C15A | 0.0387 (14) | 0.0509 (13) | 0.0338 (12) | −0.0092 (11) | −0.0101 (10) | −0.0214 (10) |
C16A | 0.0295 (12) | 0.0390 (12) | 0.0499 (14) | −0.0084 (10) | −0.0090 (11) | −0.0240 (11) |
C17A | 0.0378 (14) | 0.0425 (13) | 0.0410 (13) | −0.0206 (11) | −0.0083 (11) | −0.0047 (10) |
C18A | 0.0367 (14) | 0.0476 (13) | 0.0264 (11) | −0.0178 (11) | −0.0080 (10) | −0.0045 (9) |
C19A | 0.0215 (10) | 0.0236 (9) | 0.0184 (9) | −0.0013 (8) | −0.0050 (8) | −0.0054 (7) |
C20A | 0.0299 (12) | 0.0260 (9) | 0.0227 (10) | −0.0028 (8) | −0.0066 (9) | −0.0074 (8) |
C21A | 0.0331 (12) | 0.0245 (10) | 0.0292 (11) | 0.0043 (9) | −0.0065 (9) | −0.0081 (8) |
C22A | 0.0251 (12) | 0.0350 (11) | 0.0281 (10) | 0.0062 (9) | −0.0077 (9) | −0.0049 (9) |
C23A | 0.0286 (12) | 0.0373 (11) | 0.0335 (11) | −0.0012 (9) | −0.0147 (10) | −0.0090 (9) |
C24A | 0.0292 (12) | 0.0272 (10) | 0.0290 (10) | −0.0006 (8) | −0.0120 (9) | −0.0100 (8) |
Ni1—S2i | 2.1805 (6) | C6A—H6A | 0.9300 |
Ni1—S2 | 2.1805 (6) | C7A—C8A | 1.394 (3) |
Ni1—S1i | 2.1818 (7) | C7A—C12A | 1.397 (3) |
Ni1—S1 | 2.1818 (7) | C8A—C9A | 1.383 (3) |
S1—C2 | 1.7322 (19) | C8A—H8A | 0.9300 |
S2—C3 | 1.7562 (19) | C9A—C10A | 1.373 (3) |
C1—O1 | 1.198 (3) | C9A—H9A | 0.9300 |
C1—O2 | 1.339 (3) | C10A—C11A | 1.388 (3) |
C1—C2 | 1.495 (3) | C10A—H10A | 0.9300 |
C2—C3 | 1.361 (3) | C11A—C12A | 1.379 (3) |
C3—C4 | 1.469 (3) | C11A—H11A | 0.9300 |
C4—O3 | 1.210 (2) | C12A—H12A | 0.9300 |
C4—O4 | 1.343 (3) | C13A—C18A | 1.388 (3) |
C5—O2 | 1.443 (3) | C13A—C14A | 1.390 (3) |
C5—H5B | 0.9600 | C14A—C15A | 1.396 (3) |
C5—H5C | 0.9600 | C14A—H14A | 0.9300 |
C5—H5D | 0.9600 | C15A—C16A | 1.364 (3) |
C6—O4 | 1.443 (3) | C15A—H15A | 0.9300 |
C6—H6B | 0.9600 | C16A—C17A | 1.378 (3) |
C6—H6C | 0.9600 | C16A—H16A | 0.9300 |
C6—H6D | 0.9600 | C17A—C18A | 1.384 (3) |
P1A—C19A | 1.794 (2) | C17A—H17A | 0.9300 |
P1A—C1A | 1.7952 (19) | C18A—H18A | 0.9300 |
P1A—C7A | 1.8007 (18) | C19A—C20A | 1.401 (2) |
P1A—C13A | 1.8014 (19) | C19A—C24A | 1.405 (3) |
C1A—C2A | 1.395 (3) | C20A—C21A | 1.380 (3) |
C1A—C6A | 1.396 (3) | C20A—H20A | 0.9300 |
C2A—C3A | 1.388 (3) | C21A—C22A | 1.386 (3) |
C2A—H2A | 0.9300 | C21A—H21A | 0.9300 |
C3A—C4A | 1.379 (3) | C22A—C23A | 1.388 (3) |
C3A—H3A | 0.9300 | C22A—H22A | 0.9300 |
C4A—C5A | 1.380 (3) | C23A—C24A | 1.380 (3) |
C4A—H4A | 0.9300 | C23A—H23A | 0.9300 |
C5A—C6A | 1.382 (3) | C24A—H24A | 0.9300 |
C5A—H5A | 0.9300 | ||
S2i—Ni1—S2 | 180.000 (18) | C5A—C6A—H6A | 120.2 |
S2i—Ni1—S1i | 91.24 (2) | C1A—C6A—H6A | 120.2 |
S2—Ni1—S1i | 88.76 (2) | C8A—C7A—C12A | 119.79 (17) |
S2i—Ni1—S1 | 88.76 (2) | C8A—C7A—P1A | 120.94 (14) |
S2—Ni1—S1 | 91.24 (2) | C12A—C7A—P1A | 119.27 (14) |
S1i—Ni1—S1 | 180.00 (4) | C9A—C8A—C7A | 119.54 (18) |
C2—S1—Ni1 | 103.60 (6) | C9A—C8A—H8A | 120.2 |
C3—S2—Ni1 | 104.03 (6) | C7A—C8A—H8A | 120.2 |
O1—C1—O2 | 123.0 (2) | C10A—C9A—C8A | 120.47 (18) |
O1—C1—C2 | 125.7 (2) | C10A—C9A—H9A | 119.8 |
O2—C1—C2 | 111.19 (17) | C8A—C9A—H9A | 119.8 |
C3—C2—C1 | 123.56 (17) | C9A—C10A—C11A | 120.40 (18) |
C3—C2—S1 | 121.55 (14) | C9A—C10A—H10A | 119.8 |
C1—C2—S1 | 114.89 (13) | C11A—C10A—H10A | 119.8 |
C2—C3—C4 | 124.38 (17) | C12A—C11A—C10A | 119.86 (19) |
C2—C3—S2 | 118.94 (14) | C12A—C11A—H11A | 120.1 |
C4—C3—S2 | 116.58 (13) | C10A—C11A—H11A | 120.1 |
O3—C4—O4 | 121.26 (18) | C11A—C12A—C7A | 119.89 (18) |
O3—C4—C3 | 125.41 (18) | C11A—C12A—H12A | 120.1 |
O4—C4—C3 | 113.32 (16) | C7A—C12A—H12A | 120.1 |
O2—C5—H5B | 109.5 | C18A—C13A—C14A | 119.82 (17) |
O2—C5—H5C | 109.5 | C18A—C13A—P1A | 119.44 (14) |
H5B—C5—H5C | 109.5 | C14A—C13A—P1A | 120.60 (14) |
O2—C5—H5D | 109.5 | C13A—C14A—C15A | 119.36 (19) |
H5B—C5—H5D | 109.5 | C13A—C14A—H14A | 120.3 |
H5C—C5—H5D | 109.5 | C15A—C14A—H14A | 120.3 |
O4—C6—H6B | 109.5 | C16A—C15A—C14A | 120.50 (19) |
O4—C6—H6C | 109.5 | C16A—C15A—H15A | 119.7 |
H6B—C6—H6C | 109.5 | C14A—C15A—H15A | 119.7 |
O4—C6—H6D | 109.5 | C15A—C16A—C17A | 120.14 (19) |
H6B—C6—H6D | 109.5 | C15A—C16A—H16A | 119.9 |
H6C—C6—H6D | 109.5 | C17A—C16A—H16A | 119.9 |
C1—O2—C5 | 115.13 (19) | C16A—C17A—C18A | 120.5 (2) |
C4—O4—C6 | 116.69 (17) | C16A—C17A—H17A | 119.8 |
C19A—P1A—C1A | 109.68 (9) | C18A—C17A—H17A | 119.8 |
C19A—P1A—C7A | 107.22 (9) | C17A—C18A—C13A | 119.68 (19) |
C1A—P1A—C7A | 110.37 (8) | C17A—C18A—H18A | 120.2 |
C19A—P1A—C13A | 108.29 (9) | C13A—C18A—H18A | 120.2 |
C1A—P1A—C13A | 110.36 (9) | C20A—C19A—C24A | 119.55 (18) |
C7A—P1A—C13A | 110.84 (9) | C20A—C19A—P1A | 121.71 (15) |
C2A—C1A—C6A | 119.71 (17) | C24A—C19A—P1A | 118.68 (14) |
C2A—C1A—P1A | 120.99 (15) | C21A—C20A—C19A | 119.47 (18) |
C6A—C1A—P1A | 119.29 (14) | C21A—C20A—H20A | 120.3 |
C3A—C2A—C1A | 119.9 (2) | C19A—C20A—H20A | 120.3 |
C3A—C2A—H2A | 120.1 | C20A—C21A—C22A | 120.76 (18) |
C1A—C2A—H2A | 120.1 | C20A—C21A—H21A | 119.6 |
C4A—C3A—C2A | 119.9 (2) | C22A—C21A—H21A | 119.6 |
C4A—C3A—H3A | 120.0 | C21A—C22A—C23A | 120.1 (2) |
C2A—C3A—H3A | 120.0 | C21A—C22A—H22A | 119.9 |
C3A—C4A—C5A | 120.44 (19) | C23A—C22A—H22A | 119.9 |
C3A—C4A—H4A | 119.8 | C24A—C23A—C22A | 119.97 (19) |
C5A—C4A—H4A | 119.8 | C24A—C23A—H23A | 120.0 |
C4A—C5A—C6A | 120.4 (2) | C22A—C23A—H23A | 120.0 |
C4A—C5A—H5A | 119.8 | C23A—C24A—C19A | 120.12 (17) |
C6A—C5A—H5A | 119.8 | C23A—C24A—H24A | 119.9 |
C5A—C6A—C1A | 119.66 (19) | C19A—C24A—H24A | 119.9 |
Symmetry code: (i) −x, −y, −z. |
(C24H20P)2[Ni(C6H6O4S2)2]I | Z = 1 |
Mr = 1276.81 | F(000) = 651 |
Triclinic, P1 | Dx = 1.479 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4071 (3) Å | Cell parameters from 25 reflections |
b = 10.2501 (6) Å | θ = 2.2–30° |
c = 15.4642 (7) Å | µ = 1.13 mm−1 |
α = 85.671 (4)° | T = 293 K |
β = 77.541 (4)° | Prism, dark red |
γ = 80.240 (4)° | 0.60 × 0.45 × 0.45 mm |
V = 1433.75 (12) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.017 |
non–profiled ω/2θ scans | θmax = 30.0°, θmin = 2.3° |
Absorption correction: ψ scan (North et al., 1968) | h = −13→13 |
Tmin = 0.529, Tmax = 0.601 | k = −14→0 |
8773 measured reflections | l = −21→21 |
8343 independent reflections | 3 standard reflections every 120 min |
6177 reflections with I > 2σ(I) | intensity decay: 14% |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.055P)2 + 0.1901P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max = 0.001 |
wR(F2) = 0.097 | Δρmax = 0.64 e Å−3 |
S = 1.04 | Δρmin = −0.63 e Å−3 |
8343 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
347 parameters | Extinction coefficient: 0.0107 (9) |
0 restraints |
(C24H20P)2[Ni(C6H6O4S2)2]I | γ = 80.240 (4)° |
Mr = 1276.81 | V = 1433.75 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.4071 (3) Å | Mo Kα radiation |
b = 10.2501 (6) Å | µ = 1.13 mm−1 |
c = 15.4642 (7) Å | T = 293 K |
α = 85.671 (4)° | 0.60 × 0.45 × 0.45 mm |
β = 77.541 (4)° |
Enraf-Nonius CAD-4 diffractometer | 6177 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.017 |
Tmin = 0.529, Tmax = 0.601 | 3 standard reflections every 120 min |
8773 measured reflections | intensity decay: 14% |
8343 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.64 e Å−3 |
8343 reflections | Δρmin = −0.63 e Å−3 |
347 parameters |
Experimental. Number of ψ-scan sets used was 9. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. |
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 | ||
Ni1 | 0.5 | 0.5 | 0.5 | 0.04538 (9) | |
S1 | 0.48213 (7) | 0.33171 (6) | 0.59101 (4) | 0.05556 (14) | |
S2 | 0.31822 (6) | 0.46590 (6) | 0.44680 (4) | 0.05254 (13) | |
C1 | 0.2992 (3) | 0.1470 (2) | 0.62311 (13) | 0.0534 (5) | |
C2 | 0.3332 (2) | 0.2718 (2) | 0.57202 (13) | 0.0476 (4) | |
C3 | 0.2567 (2) | 0.3324 (2) | 0.51033 (13) | 0.0466 (4) | |
C4 | 0.1219 (2) | 0.2856 (2) | 0.49898 (14) | 0.0510 (5) | |
C5 | 0.3067 (4) | −0.0814 (3) | 0.6084 (2) | 0.0818 (8) | |
H5B | 0.3426 | −0.1472 | 0.5646 | 0.123* | |
H5C | 0.2018 | −0.0757 | 0.6274 | 0.123* | |
H5D | 0.3525 | −0.1055 | 0.6583 | 0.123* | |
C6 | −0.0556 (3) | 0.3014 (3) | 0.4107 (2) | 0.0796 (8) | |
H6B | −0.0826 | 0.3498 | 0.3595 | 0.119* | |
H6C | −0.136 | 0.3168 | 0.4608 | 0.119* | |
H6D | −0.0336 | 0.2085 | 0.3997 | 0.119* | |
O1 | 0.2486 (3) | 0.1382 (2) | 0.70080 (11) | 0.0903 (7) | |
O2 | 0.34153 (19) | 0.04528 (16) | 0.57078 (10) | 0.0564 (4) | |
O3 | 0.0632 (2) | 0.2050 (2) | 0.54688 (14) | 0.0765 (5) | |
O4 | 0.07234 (19) | 0.3451 (2) | 0.42897 (11) | 0.0643 (4) | |
I1 | 0 | 0 | 0 | 0.05356 (8) | |
P1A | 0.37232 (5) | 0.28774 (4) | 0.13461 (3) | 0.03201 (9) | |
C1A | 0.53617 (18) | 0.32403 (17) | 0.16268 (11) | 0.0351 (3) | |
C2A | 0.5487 (2) | 0.4519 (2) | 0.18164 (14) | 0.0464 (4) | |
H2A | 0.4687 | 0.5195 | 0.1837 | 0.056* | |
C3A | 0.6802 (3) | 0.4781 (2) | 0.19748 (17) | 0.0587 (5) | |
H3A | 0.6886 | 0.5632 | 0.2105 | 0.07* | |
C4A | 0.7990 (2) | 0.3772 (3) | 0.19391 (15) | 0.0570 (5) | |
H4A | 0.8877 | 0.3951 | 0.2038 | 0.068* | |
C5A | 0.7872 (2) | 0.2509 (3) | 0.17591 (16) | 0.0566 (5) | |
H5A | 0.8678 | 0.1838 | 0.1739 | 0.068* | |
C6A | 0.6562 (2) | 0.2228 (2) | 0.16073 (14) | 0.0477 (4) | |
H6A | 0.6482 | 0.1369 | 0.1493 | 0.057* | |
C7A | 0.30157 (18) | 0.16271 (17) | 0.21234 (11) | 0.0360 (3) | |
C8A | 0.3486 (2) | 0.1390 (2) | 0.29235 (13) | 0.0482 (4) | |
H8A | 0.4174 | 0.1863 | 0.3047 | 0.058* | |
C9A | 0.2928 (3) | 0.0450 (3) | 0.35352 (15) | 0.0608 (6) | |
H9A | 0.3266 | 0.0275 | 0.4061 | 0.073* | |
C10A | 0.1873 (3) | −0.0230 (2) | 0.33710 (16) | 0.0618 (6) | |
H10A | 0.1496 | −0.0855 | 0.3786 | 0.074* | |
C11A | 0.1381 (3) | 0.0020 (2) | 0.25901 (17) | 0.0578 (5) | |
H11A | 0.0661 | −0.0429 | 0.2482 | 0.069* | |
C12A | 0.1953 (2) | 0.0940 (2) | 0.19614 (15) | 0.0491 (4) | |
H12A | 0.1624 | 0.1097 | 0.1432 | 0.059* | |
C13A | 0.41853 (19) | 0.23706 (17) | 0.02183 (11) | 0.0362 (3) | |
C14A | 0.5597 (2) | 0.2402 (2) | −0.02781 (13) | 0.0478 (4) | |
H14A | 0.6314 | 0.2651 | −0.0022 | 0.057* | |
C15A | 0.5936 (3) | 0.2059 (3) | −0.11605 (15) | 0.0578 (5) | |
H15A | 0.6881 | 0.2083 | −0.1494 | 0.069* | |
C16A | 0.4889 (3) | 0.1687 (2) | −0.15422 (14) | 0.0534 (5) | |
H16A | 0.5124 | 0.1467 | −0.2134 | 0.064* | |
C17A | 0.3491 (3) | 0.1638 (2) | −0.10531 (14) | 0.0536 (5) | |
H17A | 0.2788 | 0.1365 | −0.131 | 0.064* | |
C18A | 0.3133 (2) | 0.1994 (2) | −0.01799 (13) | 0.0503 (5) | |
H18A | 0.218 | 0.1983 | 0.0145 | 0.06* | |
C19A | 0.23460 (18) | 0.43363 (17) | 0.14420 (11) | 0.0357 (3) | |
C20A | 0.1953 (2) | 0.5039 (2) | 0.06999 (13) | 0.0461 (4) | |
H20A | 0.2372 | 0.4736 | 0.0135 | 0.055* | |
C21A | 0.0935 (3) | 0.6190 (2) | 0.08087 (17) | 0.0590 (6) | |
H21A | 0.0664 | 0.6661 | 0.0316 | 0.071* | |
C22A | 0.0321 (2) | 0.6638 (2) | 0.16479 (19) | 0.0590 (6) | |
H22A | −0.0357 | 0.7416 | 0.1717 | 0.071* | |
C23A | 0.0702 (2) | 0.5950 (2) | 0.23802 (16) | 0.0558 (5) | |
H23A | 0.0278 | 0.6259 | 0.2943 | 0.067* | |
C24A | 0.1715 (2) | 0.4797 (2) | 0.22850 (13) | 0.0457 (4) | |
H24A | 0.1975 | 0.433 | 0.2782 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0518 (2) | 0.04677 (19) | 0.04355 (19) | −0.01710 (15) | −0.01424 (15) | −0.00576 (14) |
S1 | 0.0666 (3) | 0.0598 (3) | 0.0505 (3) | −0.0248 (3) | −0.0247 (2) | 0.0028 (2) |
S2 | 0.0593 (3) | 0.0560 (3) | 0.0513 (3) | −0.0231 (2) | −0.0218 (2) | 0.0027 (2) |
C1 | 0.0621 (13) | 0.0688 (13) | 0.0346 (9) | −0.0257 (11) | −0.0099 (8) | −0.0002 (9) |
C2 | 0.0570 (11) | 0.0543 (11) | 0.0349 (9) | −0.0194 (9) | −0.0071 (8) | −0.0067 (8) |
C3 | 0.0499 (10) | 0.0551 (11) | 0.0384 (9) | −0.0190 (9) | −0.0069 (8) | −0.0073 (8) |
C4 | 0.0470 (10) | 0.0635 (12) | 0.0445 (10) | −0.0190 (9) | −0.0032 (8) | −0.0110 (9) |
C5 | 0.102 (2) | 0.0637 (16) | 0.088 (2) | −0.0340 (15) | −0.0281 (17) | 0.0170 (14) |
C6 | 0.0555 (14) | 0.115 (2) | 0.0801 (18) | −0.0287 (15) | −0.0209 (13) | −0.0252 (17) |
O1 | 0.1359 (19) | 0.1017 (15) | 0.0358 (8) | −0.0512 (14) | 0.0009 (10) | 0.0005 (9) |
O2 | 0.0717 (10) | 0.0541 (8) | 0.0455 (8) | −0.0211 (7) | −0.0100 (7) | 0.0035 (6) |
O3 | 0.0606 (10) | 0.0960 (14) | 0.0800 (12) | −0.0397 (10) | −0.0165 (9) | 0.0185 (11) |
O4 | 0.0585 (9) | 0.0941 (13) | 0.0509 (9) | −0.0331 (9) | −0.0187 (7) | −0.0012 (8) |
I1 | 0.05420 (12) | 0.04939 (11) | 0.06204 (13) | −0.01813 (8) | −0.01473 (9) | −0.00305 (8) |
P1A | 0.03066 (19) | 0.0343 (2) | 0.03214 (19) | −0.00639 (15) | −0.00830 (15) | −0.00019 (15) |
C1A | 0.0324 (7) | 0.0400 (8) | 0.0348 (8) | −0.0078 (6) | −0.0098 (6) | −0.0009 (6) |
C2A | 0.0444 (10) | 0.0436 (9) | 0.0545 (11) | −0.0091 (8) | −0.0152 (8) | −0.0047 (8) |
C3A | 0.0598 (13) | 0.0601 (13) | 0.0673 (14) | −0.0260 (10) | −0.0245 (11) | −0.0031 (10) |
C4A | 0.0427 (10) | 0.0825 (16) | 0.0541 (12) | −0.0227 (10) | −0.0189 (9) | 0.0002 (11) |
C5A | 0.0361 (9) | 0.0730 (14) | 0.0617 (13) | −0.0012 (9) | −0.0184 (9) | −0.0011 (11) |
C6A | 0.0400 (9) | 0.0476 (10) | 0.0571 (11) | −0.0027 (8) | −0.0164 (8) | −0.0043 (8) |
C7A | 0.0348 (8) | 0.0347 (8) | 0.0372 (8) | −0.0048 (6) | −0.0054 (6) | −0.0008 (6) |
C8A | 0.0558 (11) | 0.0542 (11) | 0.0370 (9) | −0.0159 (9) | −0.0108 (8) | 0.0025 (8) |
C9A | 0.0739 (15) | 0.0659 (14) | 0.0392 (10) | −0.0129 (12) | −0.0067 (10) | 0.0100 (10) |
C10A | 0.0697 (15) | 0.0525 (12) | 0.0538 (12) | −0.0161 (11) | 0.0083 (11) | 0.0106 (10) |
C11A | 0.0555 (12) | 0.0506 (11) | 0.0679 (14) | −0.0229 (10) | −0.0043 (10) | 0.0019 (10) |
C12A | 0.0477 (10) | 0.0504 (11) | 0.0533 (11) | −0.0169 (8) | −0.0144 (9) | 0.0043 (9) |
C13A | 0.0380 (8) | 0.0383 (8) | 0.0336 (8) | −0.0087 (7) | −0.0074 (6) | −0.0027 (6) |
C14A | 0.0405 (9) | 0.0616 (12) | 0.0427 (10) | −0.0146 (8) | −0.0036 (8) | −0.0098 (8) |
C15A | 0.0508 (11) | 0.0747 (15) | 0.0440 (11) | −0.0135 (11) | 0.0049 (9) | −0.0132 (10) |
C16A | 0.0666 (13) | 0.0542 (11) | 0.0372 (9) | −0.0064 (10) | −0.0050 (9) | −0.0108 (8) |
C17A | 0.0599 (12) | 0.0630 (13) | 0.0435 (10) | −0.0150 (10) | −0.0164 (9) | −0.0095 (9) |
C18A | 0.0429 (10) | 0.0710 (13) | 0.0409 (10) | −0.0180 (9) | −0.0084 (8) | −0.0077 (9) |
C19A | 0.0311 (7) | 0.0371 (8) | 0.0388 (8) | −0.0048 (6) | −0.0082 (6) | 0.0001 (6) |
C20A | 0.0458 (10) | 0.0481 (10) | 0.0433 (10) | −0.0045 (8) | −0.0121 (8) | 0.0072 (8) |
C21A | 0.0566 (12) | 0.0512 (11) | 0.0695 (14) | −0.0009 (10) | −0.0248 (11) | 0.0125 (10) |
C22A | 0.0437 (11) | 0.0453 (11) | 0.0850 (17) | 0.0042 (9) | −0.0149 (11) | −0.0048 (11) |
C23A | 0.0477 (11) | 0.0542 (12) | 0.0611 (13) | −0.0012 (9) | −0.0030 (9) | −0.0137 (10) |
C24A | 0.0444 (10) | 0.0496 (10) | 0.0418 (9) | −0.0022 (8) | −0.0091 (8) | −0.0041 (8) |
Ni1—S2 | 2.1392 (5) | C6A—H6A | 0.9300 |
Ni1—S2i | 2.1392 (5) | C7A—C12A | 1.390 (3) |
Ni1—S1i | 2.1481 (6) | C7A—C8A | 1.393 (3) |
Ni1—S1 | 2.1481 (6) | C8A—C9A | 1.385 (3) |
S1—C2 | 1.710 (2) | C8A—H8A | 0.9300 |
S2—C3 | 1.730 (2) | C9A—C10A | 1.380 (4) |
C1—O1 | 1.196 (3) | C9A—H9A | 0.9300 |
C1—O2 | 1.322 (3) | C10A—C11A | 1.376 (4) |
C1—C2 | 1.497 (3) | C10A—H10A | 0.9300 |
C2—C3 | 1.367 (3) | C11A—C12A | 1.390 (3) |
C3—C4 | 1.477 (3) | C11A—H11A | 0.9300 |
C4—O3 | 1.192 (3) | C12A—H12A | 0.9300 |
C4—O4 | 1.336 (3) | C13A—C14A | 1.388 (3) |
C5—O2 | 1.442 (3) | C13A—C18A | 1.391 (3) |
C5—H5B | 0.9600 | C14A—C15A | 1.391 (3) |
C5—H5C | 0.9600 | C14A—H14A | 0.9300 |
C5—H5D | 0.9600 | C15A—C16A | 1.370 (3) |
C6—O4 | 1.442 (3) | C15A—H15A | 0.9300 |
C6—H6B | 0.9600 | C16A—C17A | 1.375 (3) |
C6—H6C | 0.9600 | C16A—H16A | 0.9300 |
C6—H6D | 0.9600 | C17A—C18A | 1.381 (3) |
P1A—C1A | 1.7916 (16) | C17A—H17A | 0.9300 |
P1A—C19A | 1.7974 (17) | C18A—H18A | 0.9300 |
P1A—C13A | 1.7982 (17) | C19A—C24A | 1.392 (3) |
P1A—C7A | 1.8004 (17) | C19A—C20A | 1.393 (2) |
C1A—C2A | 1.394 (3) | C20A—C21A | 1.384 (3) |
C1A—C6A | 1.395 (3) | C20A—H20A | 0.9300 |
C2A—C3A | 1.384 (3) | C21A—C22A | 1.380 (4) |
C2A—H2A | 0.9300 | C21A—H21A | 0.9300 |
C3A—C4A | 1.383 (3) | C22A—C23A | 1.370 (3) |
C3A—H3A | 0.9300 | C22A—H22A | 0.9300 |
C4A—C5A | 1.371 (4) | C23A—C24A | 1.382 (3) |
C4A—H4A | 0.9300 | C23A—H23A | 0.9300 |
C5A—C6A | 1.382 (3) | C24A—H24A | 0.9300 |
C5A—H5A | 0.9300 | ||
S2—Ni1—S2i | 180.00 (2) | C5A—C6A—H6A | 120.2 |
S2—Ni1—S1i | 87.79 (2) | C1A—C6A—H6A | 120.2 |
S2i—Ni1—S1i | 92.21 (2) | C12A—C7A—C8A | 119.21 (17) |
S2—Ni1—S1 | 92.21 (2) | C12A—C7A—P1A | 121.30 (14) |
S2i—Ni1—S1 | 87.79 (2) | C8A—C7A—P1A | 119.40 (14) |
S1i—Ni1—S1 | 180.0 | C9A—C8A—C7A | 120.0 (2) |
C2—S1—Ni1 | 103.65 (8) | C9A—C8A—H8A | 120.0 |
C3—S2—Ni1 | 103.92 (7) | C7A—C8A—H8A | 120.0 |
O1—C1—O2 | 124.4 (2) | C10A—C9A—C8A | 120.6 (2) |
O1—C1—C2 | 125.5 (2) | C10A—C9A—H9A | 119.7 |
O2—C1—C2 | 110.01 (17) | C8A—C9A—H9A | 119.7 |
C3—C2—C1 | 123.32 (18) | C11A—C10A—C9A | 119.7 (2) |
C3—C2—S1 | 120.87 (16) | C11A—C10A—H10A | 120.2 |
C1—C2—S1 | 115.73 (16) | C9A—C10A—H10A | 120.2 |
C2—C3—C4 | 120.38 (19) | C10A—C11A—C12A | 120.4 (2) |
C2—C3—S2 | 119.18 (16) | C10A—C11A—H11A | 119.8 |
C4—C3—S2 | 120.43 (16) | C12A—C11A—H11A | 119.8 |
O3—C4—O4 | 123.7 (2) | C7A—C12A—C11A | 120.1 (2) |
O3—C4—C3 | 124.2 (2) | C7A—C12A—H12A | 120.0 |
O4—C4—C3 | 112.05 (18) | C11A—C12A—H12A | 120.0 |
O2—C5—H5B | 109.5 | C14A—C13A—C18A | 119.08 (17) |
O2—C5—H5C | 109.5 | C14A—C13A—P1A | 119.77 (14) |
H5B—C5—H5C | 109.5 | C18A—C13A—P1A | 121.11 (14) |
O2—C5—H5D | 109.5 | C13A—C14A—C15A | 119.67 (19) |
H5B—C5—H5D | 109.5 | C13A—C14A—H14A | 120.2 |
H5C—C5—H5D | 109.5 | C15A—C14A—H14A | 120.2 |
O4—C6—H6B | 109.5 | C16A—C15A—C14A | 120.5 (2) |
O4—C6—H6C | 109.5 | C16A—C15A—H15A | 119.7 |
H6B—C6—H6C | 109.5 | C14A—C15A—H15A | 119.7 |
O4—C6—H6D | 109.5 | C15A—C16A—C17A | 120.24 (19) |
H6B—C6—H6D | 109.5 | C15A—C16A—H16A | 119.9 |
H6C—C6—H6D | 109.5 | C17A—C16A—H16A | 119.9 |
C1—O2—C5 | 116.9 (2) | C16A—C17A—C18A | 119.8 (2) |
C4—O4—C6 | 115.8 (2) | C16A—C17A—H17A | 120.1 |
C1A—P1A—C19A | 109.71 (8) | C18A—C17A—H17A | 120.1 |
C1A—P1A—C13A | 107.97 (8) | C17A—C18A—C13A | 120.63 (19) |
C19A—P1A—C13A | 109.44 (8) | C17A—C18A—H18A | 119.7 |
C1A—P1A—C7A | 108.59 (8) | C13A—C18A—H18A | 119.7 |
C19A—P1A—C7A | 107.99 (8) | C24A—C19A—C20A | 119.88 (17) |
C13A—P1A—C7A | 113.12 (8) | C24A—C19A—P1A | 118.20 (13) |
C2A—C1A—C6A | 119.59 (17) | C20A—C19A—P1A | 121.86 (14) |
C2A—C1A—P1A | 121.53 (13) | C21A—C20A—C19A | 119.5 (2) |
C6A—C1A—P1A | 118.79 (14) | C21A—C20A—H20A | 120.2 |
C3A—C2A—C1A | 120.01 (19) | C19A—C20A—H20A | 120.2 |
C3A—C2A—H2A | 120.0 | C22A—C21A—C20A | 120.0 (2) |
C1A—C2A—H2A | 120.0 | C22A—C21A—H21A | 120.0 |
C4A—C3A—C2A | 119.7 (2) | C20A—C21A—H21A | 120.0 |
C4A—C3A—H3A | 120.1 | C23A—C22A—C21A | 120.7 (2) |
C2A—C3A—H3A | 120.1 | C23A—C22A—H22A | 119.7 |
C5A—C4A—C3A | 120.61 (19) | C21A—C22A—H22A | 119.7 |
C5A—C4A—H4A | 119.7 | C22A—C23A—C24A | 120.1 (2) |
C3A—C4A—H4A | 119.7 | C22A—C23A—H23A | 119.9 |
C4A—C5A—C6A | 120.4 (2) | C24A—C23A—H23A | 119.9 |
C4A—C5A—H5A | 119.8 | C23A—C24A—C19A | 119.73 (19) |
C6A—C5A—H5A | 119.8 | C23A—C24A—H24A | 120.1 |
C5A—C6A—C1A | 119.7 (2) | C19A—C24A—H24A | 120.1 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C24H20P)2[Ni(C6H6O4S2)2] | (C24H20P)2[Ni(C6H6O4S2)2]I |
Mr | 1149.91 | 1276.81 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 200 | 293 |
a, b, c (Å) | 10.2994 (14), 11.1508 (16), 13.8197 (19) | 9.4071 (3), 10.2501 (6), 15.4642 (7) |
α, β, γ (°) | 68.023 (16), 68.730 (15), 80.092 (17) | 85.671 (4), 77.541 (4), 80.240 (4) |
V (Å3) | 1370.3 (3) | 1433.75 (12) |
Z | 1 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.62 | 1.13 |
Crystal size (mm) | 0.63 × 0.23 × 0.15 | 0.60 × 0.45 × 0.45 |
Data collection | ||
Diffractometer | Stoe IPDS diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Numerical (FACEIT in IPDS; Stoe & Cie, 1995) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.777, 0.928 | 0.529, 0.601 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14269, 4966, 3899 | 8773, 8343, 6177 |
Rint | 0.052 | 0.017 |
(sin θ/λ)max (Å−1) | 0.615 | 0.703 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.071, 0.93 | 0.032, 0.097, 1.04 |
No. of reflections | 4966 | 8343 |
No. of parameters | 340 | 347 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.16 | 0.64, −0.63 |
Computer programs: EXPOSE in IPDS (Stoe & Cie, 1995), CAD-4 EXPRESS (Enraf Nonius, 1994), SELECT and CELL, both in IPDS, CAD-4 EXPRESS, INTEGRATE in IPDS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
parameter | (I) | (II) |
Ni1-S1 | 2.1818 (7) | 2.1481 (6) |
Ni1-S2 | 2.1805 (6) | 2.1392 (5) |
S1-C2 | 1.7322 (19) | 1.710 (2) |
S2-C3 | 1.7562 (19) | 1.730 (2) |
C2-C3 | 1.361 (3) | 1.367 (3) |
C1-O1 | 1.198 (3) | 1.196 (3) |
C4-O3 | 1.210 (2) | 1.192 (3) |
S1-Ni1-S2 | 91.24 (2) | 92.21 (2) |
In the course of our study of the flexibility of functional groups with respect to redox-active conjugated cores (Baudron et al., 2002), we became interested in studying nickel dithiolene complexes, [Ni(S2C2R2)2]x (R is?, x is?; Robertson & Cronin, 2002). These compounds are very attractive for the construction of magnetic or conducting materials (Cassoux, 1999). Our attention was raised by the [Ni{S2C2(CO2Me)2}2]- anion, which has been shown to display several conformations in the solid state as a result of rotation of the ester groups (Brown et al., 1983). In an attempt to prepare this compound, we were able to isolate the reduced (2-) complex, (PPh4)2[Ni{S2C2(CO2Me)2}2], (I). This compound, air-stable in its crystalline state, is oxidized in hot acetonitrile. When it is oxidized with iodine in acetonitrile, a new crystalline form is identified which incorporates the I- anion, namely (PPh4)2[Ni{S2C2(CO2Me)2}2]I, (II). \sch
In both compounds, the Ni atoms lie on an inversion centre, requiring an exactly planar arrangement of the NiS4 core. The Ni—S bond lengths are longer in (I) than in (II) or the reported crystal structure of (AsPh4)[Ni{S2C2(CO2Me)2}2] [2.129 (6) Å; Brown et al., 1983]. This is normally observed for nickel dithiolene complexes of different oxidation states (Lim et al., 2001). These values compare favourably with the Ni—S bond lengths in [Ni(mnt)2]n- [mnt is?; 2.174 (2) Å when n = 2 and 2.147 (3) Å when n = 1; Mahadevan et al., 1984; Kobayashi & Suzuki, 1977].
Another feature is the relative orientation of the ester groups, which are almost orthogonal in both compounds. The salient difference lies in the position of the ester group that is in the NiS4 plane. While it is in a cis position with respect to the C═C of the dithiolene ring in (I), it is in a trans position in (II). This shows the solid-state expression of the free rotation of these functional groups that exists in solution. This feature is observed for other related compounds (Beswick et al., 2002) and it is of interest to note that it has an influence on the S—C bond lengths. Indeed, in both compounds, one S—C bond is shorter that the other, revealing the existence of a mesomeric form involving the ester group in the NiS4 plane along the S1—C2═C3—C4═O3 conjugated path. As a consequence, this S—C bond has a somewhat double-bond nature. This phenomenon has been highlighted in amide-functionalized tetrathiafulvalene (Heuzé et al., 1999; Batsanov et al., 1995). A closer look at other coordination compounds involving this kind of ligand, such as (PPh4)2[Fe2{S2C2(CO2Me)2}4]·2DMF (DMF is dimethylformamide; Kanatzidis & Coucouvanis, 1984), (Et4N)[NbO{S2C2(CO2Me)2}2(S2)(bpy)]·DMF (bpy is 2,2'-bypyridine; Kim et al., 2001), (Pr4N)2[W2(µ-S)2{S2C2(CO2Et)2}4] (Umakoshi et al., 2000) and (Et4N)[W(S2CNMe2){S2C2(CO2Me)2}2] (Lim et al., 2000), reveals the same phenomenon.
In compound (II), the paramagnetic centres are well separated and no short S···S contact is observed. As a consequence, the temperature evolution of the magnetic susceptibility obeys the Curie law, with µeff = 1.79 µB, close to the S = 1/2 value of 1.73 µB.