Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012984/bt6287sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012984/bt6287Isup2.hkl |
CCDC reference: 217388
[Ni(CO)(η5-C5H5)]2 was obtained from a commercial source. Crystals suitable for structural determination were obtained from a concentrated hexane solution at −20°C. Contrary to previous reports, all crystals obtained through sublimation displayed evidence of twinning and were disregarded.
All H atoms were placed in calculated positions (Uiso 1.2 times that of the carbon to which they were attached) using a riding model. The nickel atoms of the minor component of the disorder were identified from difference maps and refined using isotropic thermal parameters.
Data collection: Collect (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); 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 publication routines (Farrugia, 1999).
C12H10Ni2O2 | Z = 4 |
Mr = 303.62 | F(000) = 616 |
Triclinic, P1 | Dx = 1.871 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7498 (1) Å | Cell parameters from 133537 reflections |
b = 10.8752 (1) Å | θ = 1–35.0° |
c = 13.4942 (2) Å | µ = 3.47 mm−1 |
α = 76.776 (1)° | T = 115 K |
β = 81.112 (1)° | Prism, black |
γ = 78.449 (1)° | 0.40 × 0.28 × 0.15 mm |
V = 1077.65 (2) Å3 |
KappaCCD diffractometer | 6276 independent reflections |
Radiation source: Enraf Nonius FR590 | 5839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
CCD rotation images, thick slices scans | θmax = 30°, θmin = 1.6° |
Absorption correction: multi-scan (Blessing, 1995) | h = −10→10 |
Tmin = 0.264, Tmax = 0.594 | k = −15→15 |
84232 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0315P)2 + 0.5418P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
6276 reflections | Δρmax = 0.62 e Å−3 |
307 parameters | Δρmin = −0.64 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0030 (4) |
C12H10Ni2O2 | γ = 78.449 (1)° |
Mr = 303.62 | V = 1077.65 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.7498 (1) Å | Mo Kα radiation |
b = 10.8752 (1) Å | µ = 3.47 mm−1 |
c = 13.4942 (2) Å | T = 115 K |
α = 76.776 (1)° | 0.40 × 0.28 × 0.15 mm |
β = 81.112 (1)° |
KappaCCD diffractometer | 6276 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5839 reflections with I > 2σ(I) |
Tmin = 0.264, Tmax = 0.594 | Rint = 0.071 |
84232 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.62 e Å−3 |
6276 reflections | Δρmin = −0.64 e Å−3 |
307 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. |
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 | Occ. (<1) | |
Ni1 | 0.22846 (2) | 0.276719 (17) | 0.470339 (13) | 0.01510 (5) | 0.9893 (6) |
Ni2 | 0.40518 (2) | 0.403569 (17) | 0.345001 (14) | 0.01549 (5) | 0.9893 (6) |
O1 | 0.60220 (15) | 0.19174 (12) | 0.47306 (10) | 0.0311 (3) | |
O2 | 0.07454 (16) | 0.38667 (13) | 0.28323 (9) | 0.0298 (3) | |
C1 | 0.47518 (19) | 0.25718 (14) | 0.44374 (12) | 0.0206 (3) | |
C2 | 0.18366 (19) | 0.36542 (14) | 0.33737 (11) | 0.0195 (3) | |
C11 | −0.0354 (2) | 0.29308 (17) | 0.54332 (12) | 0.0263 (3) | |
H11 | −0.1305 | 0.356 | 0.5172 | 0.032* | |
C12 | 0.0722 (2) | 0.30539 (15) | 0.61484 (12) | 0.0235 (3) | |
H12 | 0.0596 | 0.3759 | 0.6474 | 0.028* | |
C13 | 0.2022 (2) | 0.19308 (15) | 0.62888 (11) | 0.0228 (3) | |
H13 | 0.2961 | 0.177 | 0.6703 | 0.027* | |
C14 | 0.1690 (2) | 0.10783 (16) | 0.57036 (12) | 0.0253 (3) | |
H14 | 0.234 | 0.0244 | 0.5681 | 0.03* | |
C15 | 0.0229 (2) | 0.16948 (18) | 0.51673 (13) | 0.0286 (3) | |
H15 | −0.0278 | 0.1356 | 0.4713 | 0.034* | |
C21 | 0.6220 (2) | 0.50014 (17) | 0.33382 (14) | 0.0298 (4) | |
H21 | 0.7019 | 0.481 | 0.3842 | 0.036* | |
C22 | 0.4677 (2) | 0.59468 (15) | 0.32982 (13) | 0.0255 (3) | |
H22 | 0.4281 | 0.6529 | 0.3747 | 0.031* | |
C23 | 0.3834 (2) | 0.58662 (15) | 0.24689 (12) | 0.0241 (3) | |
H23 | 0.2734 | 0.6362 | 0.2281 | 0.029* | |
C24 | 0.4904 (2) | 0.49164 (16) | 0.19554 (13) | 0.0280 (3) | |
H24 | 0.466 | 0.469 | 0.1358 | 0.034* | |
C25 | 0.6380 (2) | 0.43782 (17) | 0.24927 (15) | 0.0314 (4) | |
H25 | 0.7315 | 0.3721 | 0.2326 | 0.038* | |
Ni3 | 0.27696 (2) | 0.106655 (17) | 0.154043 (14) | 0.01574 (5) | 0.9893 (6) |
Ni4 | 0.08613 (2) | 0.231899 (18) | 0.034791 (14) | 0.01724 (5) | 0.9893 (6) |
O3 | 0.41294 (16) | 0.32257 (12) | 0.02415 (10) | 0.0314 (3) | |
O4 | −0.09044 (16) | 0.13918 (14) | 0.23367 (10) | 0.0365 (3) | |
C3 | 0.3095 (2) | 0.25505 (14) | 0.05641 (11) | 0.0203 (3) | |
C4 | 0.0303 (2) | 0.15367 (15) | 0.17137 (12) | 0.0230 (3) | |
C31 | 0.5362 (2) | −0.00498 (16) | 0.14873 (13) | 0.0267 (3) | |
H31 | 0.6244 | 0.0058 | 0.0916 | 0.032* | |
C32 | 0.5029 (2) | 0.06396 (16) | 0.23048 (15) | 0.0322 (4) | |
H32 | 0.566 | 0.1273 | 0.2377 | 0.039* | |
C33 | 0.3605 (3) | 0.02107 (17) | 0.29782 (13) | 0.0311 (4) | |
H33 | 0.3109 | 0.0493 | 0.3594 | 0.037* | |
C34 | 0.3030 (2) | −0.07296 (15) | 0.25739 (12) | 0.0257 (3) | |
H34 | 0.2057 | −0.1156 | 0.2861 | 0.031* | |
C35 | 0.4162 (2) | −0.09125 (14) | 0.16744 (12) | 0.0235 (3) | |
H35 | 0.412 | −0.1511 | 0.1268 | 0.028* | |
C41 | 0.0077 (2) | 0.38819 (16) | −0.08238 (12) | 0.0261 (3) | |
H41 | 0.0409 | 0.4699 | −0.0918 | 0.031* | |
C42 | −0.1419 (2) | 0.34940 (19) | −0.02176 (13) | 0.0316 (4) | |
H42 | −0.2292 | 0.3996 | 0.017 | 0.038* | |
C43 | −0.1397 (2) | 0.2193 (2) | −0.02877 (15) | 0.0379 (4) | |
H43 | −0.2236 | 0.167 | 0.0067 | 0.045* | |
C44 | 0.0096 (3) | 0.18205 (18) | −0.09793 (15) | 0.0362 (4) | |
H44 | 0.0402 | 0.1025 | −0.1196 | 0.043* | |
C45 | 0.1028 (2) | 0.28468 (18) | −0.12799 (12) | 0.0282 (3) | |
H45 | 0.2114 | 0.2853 | −0.1716 | 0.034* | |
Ni1A | 0.365 (2) | 0.0565 (16) | 0.6844 (13) | 0.015 (4)* | 0.0107 (6) |
Ni2A | 0.183 (2) | 0.174 (2) | 0.5624 (15) | 0.019 (4)* | 0.0107 (6) |
Ni3A | 0.865 (2) | 0.6841 (17) | 0.0648 (13) | 0.016 (4)* | 0.0107 (6) |
Ni4A | 0.687 (2) | 0.5609 (16) | 0.1891 (12) | 0.014 (4)* | 0.0107 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01393 (9) | 0.01538 (9) | 0.01476 (9) | −0.00276 (6) | −0.00137 (6) | −0.00058 (6) |
Ni2 | 0.01394 (9) | 0.01544 (9) | 0.01568 (9) | −0.00304 (6) | −0.00117 (6) | −0.00022 (6) |
O1 | 0.0190 (5) | 0.0299 (6) | 0.0369 (7) | 0.0010 (4) | −0.0059 (5) | 0.0058 (5) |
O2 | 0.0258 (6) | 0.0370 (7) | 0.0259 (6) | −0.0102 (5) | −0.0106 (5) | 0.0043 (5) |
C1 | 0.0180 (6) | 0.0195 (6) | 0.0223 (7) | −0.0032 (5) | −0.0015 (5) | −0.0010 (5) |
C2 | 0.0186 (6) | 0.0206 (6) | 0.0187 (6) | −0.0052 (5) | −0.0021 (5) | −0.0008 (5) |
C11 | 0.0156 (6) | 0.0338 (8) | 0.0233 (7) | −0.0028 (6) | 0.0015 (5) | 0.0029 (6) |
C12 | 0.0247 (7) | 0.0230 (7) | 0.0194 (7) | −0.0018 (6) | 0.0032 (5) | −0.0033 (5) |
C13 | 0.0245 (7) | 0.0250 (7) | 0.0155 (6) | −0.0022 (6) | −0.0020 (5) | 0.0006 (5) |
C14 | 0.0308 (8) | 0.0178 (7) | 0.0232 (7) | −0.0068 (6) | 0.0050 (6) | 0.0009 (6) |
C15 | 0.0265 (8) | 0.0363 (9) | 0.0262 (8) | −0.0191 (7) | 0.0020 (6) | −0.0042 (7) |
C21 | 0.0231 (7) | 0.0316 (8) | 0.0332 (8) | −0.0137 (6) | −0.0083 (6) | 0.0075 (7) |
C22 | 0.0304 (8) | 0.0206 (7) | 0.0265 (7) | −0.0106 (6) | 0.0002 (6) | −0.0036 (6) |
C23 | 0.0235 (7) | 0.0194 (7) | 0.0260 (7) | −0.0058 (5) | −0.0039 (6) | 0.0046 (6) |
C24 | 0.0355 (8) | 0.0274 (8) | 0.0201 (7) | −0.0122 (7) | 0.0032 (6) | −0.0013 (6) |
C25 | 0.0206 (7) | 0.0248 (8) | 0.0410 (9) | −0.0043 (6) | 0.0110 (7) | −0.0002 (7) |
Ni3 | 0.01522 (9) | 0.01507 (9) | 0.01543 (9) | −0.00127 (6) | −0.00317 (6) | −0.00030 (6) |
Ni4 | 0.01623 (9) | 0.01686 (9) | 0.01767 (9) | −0.00220 (7) | −0.00520 (7) | 0.00006 (7) |
O3 | 0.0285 (6) | 0.0321 (6) | 0.0325 (6) | −0.0144 (5) | −0.0092 (5) | 0.0075 (5) |
O4 | 0.0211 (6) | 0.0423 (7) | 0.0340 (7) | −0.0008 (5) | 0.0045 (5) | 0.0077 (6) |
C3 | 0.0197 (6) | 0.0207 (7) | 0.0195 (6) | −0.0037 (5) | −0.0054 (5) | 0.0002 (5) |
C4 | 0.0195 (6) | 0.0216 (7) | 0.0243 (7) | −0.0007 (5) | −0.0037 (5) | 0.0011 (5) |
C31 | 0.0176 (6) | 0.0238 (7) | 0.0319 (8) | 0.0007 (5) | −0.0011 (6) | 0.0031 (6) |
C32 | 0.0315 (8) | 0.0234 (8) | 0.0444 (10) | −0.0011 (6) | −0.0241 (8) | −0.0026 (7) |
C33 | 0.0433 (10) | 0.0270 (8) | 0.0185 (7) | 0.0100 (7) | −0.0117 (7) | −0.0040 (6) |
C34 | 0.0256 (7) | 0.0205 (7) | 0.0238 (7) | −0.0005 (6) | −0.0002 (6) | 0.0054 (6) |
C35 | 0.0275 (7) | 0.0167 (6) | 0.0240 (7) | 0.0011 (5) | −0.0054 (6) | −0.0025 (5) |
C41 | 0.0340 (8) | 0.0224 (7) | 0.0211 (7) | −0.0021 (6) | −0.0122 (6) | 0.0008 (6) |
C42 | 0.0236 (7) | 0.0421 (10) | 0.0232 (7) | 0.0079 (7) | −0.0084 (6) | −0.0028 (7) |
C43 | 0.0302 (9) | 0.0455 (11) | 0.0382 (10) | −0.0182 (8) | −0.0198 (8) | 0.0115 (8) |
C44 | 0.0477 (11) | 0.0265 (8) | 0.0407 (10) | 0.0003 (7) | −0.0273 (8) | −0.0107 (7) |
C45 | 0.0277 (8) | 0.0385 (9) | 0.0176 (7) | −0.0006 (7) | −0.0072 (6) | −0.0053 (6) |
Ni1—C1 | 1.8681 (15) | Ni3—C4 | 1.8696 (15) |
Ni1—C2 | 1.8807 (15) | Ni3—C32 | 2.0879 (16) |
Ni1—C15 | 2.0956 (15) | Ni3—C33 | 2.0905 (16) |
Ni1—C14 | 2.1023 (16) | Ni3—C34 | 2.1176 (15) |
Ni1—C13 | 2.1202 (15) | Ni3—C31 | 2.1295 (15) |
Ni1—C11 | 2.1205 (15) | Ni3—C35 | 2.1867 (15) |
Ni1—C12 | 2.1825 (15) | Ni3—Ni4 | 2.3575 (3) |
Ni1—Ni2 | 2.3691 (3) | Ni4—C4 | 1.8685 (16) |
Ni2—C2 | 1.8679 (15) | Ni4—C3 | 1.8733 (15) |
Ni2—C1 | 1.8738 (15) | Ni4—C42 | 2.0989 (16) |
Ni2—C24 | 2.0925 (16) | Ni4—C41 | 2.1006 (15) |
Ni2—C25 | 2.0957 (16) | Ni4—C43 | 2.1049 (17) |
Ni2—C23 | 2.1149 (15) | Ni4—C45 | 2.1299 (16) |
Ni2—C21 | 2.1224 (16) | Ni4—C44 | 2.1806 (17) |
Ni2—C22 | 2.1848 (15) | O3—C3 | 1.1632 (19) |
O1—C1 | 1.1589 (19) | O4—C4 | 1.1672 (19) |
O2—C2 | 1.1566 (18) | C31—C35 | 1.406 (2) |
C11—C12 | 1.413 (2) | C31—C32 | 1.435 (3) |
C11—C15 | 1.438 (3) | C31—H31 | 0.95 |
C11—H11 | 0.95 | C32—C33 | 1.401 (3) |
C12—C13 | 1.416 (2) | C32—H32 | 0.95 |
C12—H12 | 0.95 | C33—C34 | 1.433 (3) |
C13—C14 | 1.429 (2) | C33—H33 | 0.95 |
C13—H13 | 0.95 | C34—C35 | 1.412 (2) |
C14—C15 | 1.408 (2) | C34—H34 | 0.95 |
C14—H14 | 0.95 | C35—H35 | 0.95 |
C15—H15 | 0.95 | C41—C42 | 1.391 (2) |
C21—C22 | 1.411 (2) | C41—C45 | 1.426 (2) |
C21—C25 | 1.433 (3) | C41—H41 | 0.95 |
C21—H21 | 0.95 | C42—C43 | 1.436 (3) |
C22—C23 | 1.407 (2) | C42—H42 | 0.95 |
C22—H22 | 0.95 | C43—C44 | 1.423 (3) |
C23—C24 | 1.429 (2) | C43—H43 | 0.95 |
C23—H23 | 0.95 | C44—C45 | 1.399 (3) |
C24—C25 | 1.404 (3) | C44—H44 | 0.95 |
C24—H24 | 0.95 | C45—H45 | 0.95 |
C25—H25 | 0.95 | Ni1A—Ni2A | 2.32 (2) |
Ni3—C3 | 1.8685 (15) | Ni3A—Ni4A | 2.34 (2) |
C1—Ni1—C2 | 95.61 (6) | C3—Ni3—C4 | 93.72 (7) |
C1—Ni1—C15 | 141.48 (7) | C3—Ni3—C32 | 103.64 (7) |
C2—Ni1—C15 | 103.16 (7) | C4—Ni3—C32 | 143.36 (8) |
C1—Ni1—C14 | 107.02 (7) | C3—Ni3—C33 | 135.63 (7) |
C2—Ni1—C14 | 136.92 (7) | C4—Ni3—C33 | 108.03 (7) |
C15—Ni1—C14 | 39.19 (7) | C32—Ni3—C33 | 39.19 (8) |
C1—Ni1—C13 | 100.01 (6) | C3—Ni3—C34 | 167.00 (6) |
C2—Ni1—C13 | 164.09 (6) | C4—Ni3—C34 | 99.25 (6) |
C15—Ni1—C13 | 65.90 (7) | C32—Ni3—C34 | 66.03 (7) |
C14—Ni1—C13 | 39.57 (7) | C33—Ni3—C34 | 39.82 (7) |
C1—Ni1—C11 | 163.84 (7) | C3—Ni3—C31 | 102.22 (6) |
C2—Ni1—C11 | 99.15 (6) | C4—Ni3—C31 | 162.05 (7) |
C15—Ni1—C11 | 39.87 (7) | C32—Ni3—C31 | 39.76 (7) |
C14—Ni1—C11 | 65.83 (6) | C33—Ni3—C31 | 65.70 (7) |
C13—Ni1—C11 | 64.98 (6) | C34—Ni3—C31 | 64.83 (6) |
C1—Ni1—C12 | 125.85 (6) | C3—Ni3—C35 | 131.30 (6) |
C2—Ni1—C12 | 127.51 (6) | C4—Ni3—C35 | 124.15 (7) |
C15—Ni1—C12 | 65.49 (7) | C32—Ni3—C35 | 65.21 (6) |
C14—Ni1—C12 | 65.27 (6) | C33—Ni3—C35 | 65.16 (6) |
C13—Ni1—C12 | 38.38 (6) | C34—Ni3—C35 | 38.26 (6) |
C11—Ni1—C12 | 38.31 (6) | C31—Ni3—C35 | 38.00 (6) |
C1—Ni1—Ni2 | 50.82 (5) | C3—Ni3—Ni4 | 51.04 (5) |
C2—Ni1—Ni2 | 50.56 (4) | C4—Ni3—Ni4 | 50.88 (5) |
C15—Ni1—Ni2 | 152.70 (5) | C32—Ni3—Ni4 | 154.58 (5) |
C14—Ni1—Ni2 | 155.60 (5) | C33—Ni3—Ni4 | 157.47 (5) |
C13—Ni1—Ni2 | 141.38 (5) | C34—Ni3—Ni4 | 139.31 (5) |
C11—Ni1—Ni2 | 138.33 (5) | C31—Ni3—Ni4 | 136.82 (5) |
C12—Ni1—Ni2 | 133.39 (4) | C35—Ni3—Ni4 | 130.50 (4) |
C2—Ni2—C1 | 95.85 (6) | C4—Ni4—C3 | 93.59 (7) |
C2—Ni2—C24 | 105.03 (7) | C4—Ni4—C42 | 109.41 (7) |
C1—Ni2—C24 | 139.17 (7) | C3—Ni4—C42 | 136.44 (7) |
C2—Ni2—C25 | 139.33 (7) | C4—Ni4—C41 | 144.21 (7) |
C1—Ni2—C25 | 105.10 (7) | C3—Ni4—C41 | 104.05 (7) |
C24—Ni2—C25 | 39.17 (7) | C42—Ni4—C41 | 38.70 (7) |
C2—Ni2—C23 | 99.29 (6) | C4—Ni4—C43 | 100.68 (7) |
C1—Ni2—C23 | 164.11 (7) | C3—Ni4—C43 | 165.45 (7) |
C24—Ni2—C23 | 39.69 (7) | C42—Ni4—C43 | 39.94 (8) |
C25—Ni2—C23 | 65.79 (6) | C41—Ni4—C43 | 65.51 (7) |
C2—Ni2—C21 | 163.55 (7) | C4—Ni4—C45 | 163.26 (7) |
C1—Ni2—C21 | 99.77 (7) | C3—Ni4—C45 | 100.65 (7) |
C24—Ni2—C21 | 65.75 (7) | C42—Ni4—C45 | 65.50 (7) |
C25—Ni2—C21 | 39.71 (8) | C41—Ni4—C45 | 39.39 (7) |
C23—Ni2—C21 | 64.75 (6) | C43—Ni4—C45 | 64.81 (7) |
C2—Ni2—C22 | 126.19 (6) | C4—Ni4—C44 | 125.46 (8) |
C1—Ni2—C22 | 126.88 (7) | C3—Ni4—C44 | 128.61 (8) |
C24—Ni2—C22 | 65.23 (6) | C42—Ni4—C44 | 65.57 (7) |
C25—Ni2—C22 | 65.29 (7) | C41—Ni4—C44 | 64.83 (7) |
C23—Ni2—C22 | 38.16 (6) | C43—Ni4—C44 | 38.74 (8) |
C21—Ni2—C22 | 38.22 (7) | C45—Ni4—C44 | 37.85 (7) |
C2—Ni2—Ni1 | 51.04 (4) | C4—Ni4—Ni3 | 50.92 (5) |
C1—Ni2—Ni1 | 50.61 (5) | C3—Ni4—Ni3 | 50.86 (5) |
C24—Ni2—Ni1 | 154.52 (5) | C42—Ni4—Ni3 | 159.27 (5) |
C25—Ni2—Ni1 | 154.30 (5) | C41—Ni4—Ni3 | 154.88 (5) |
C23—Ni2—Ni1 | 139.85 (4) | C43—Ni4—Ni3 | 139.25 (5) |
C21—Ni2—Ni1 | 139.65 (5) | C45—Ni4—Ni3 | 135.24 (5) |
C22—Ni2—Ni1 | 133.18 (4) | C44—Ni4—Ni3 | 128.75 (5) |
O1—C1—Ni1 | 140.83 (13) | O3—C3—Ni3 | 141.24 (13) |
O1—C1—Ni2 | 140.60 (13) | O3—C3—Ni4 | 140.61 (12) |
Ni1—C1—Ni2 | 78.56 (6) | Ni3—C3—Ni4 | 78.11 (6) |
O2—C2—Ni2 | 141.60 (12) | O4—C4—Ni4 | 141.57 (13) |
O2—C2—Ni1 | 139.97 (12) | O4—C4—Ni3 | 140.22 (13) |
Ni2—C2—Ni1 | 78.39 (6) | Ni4—C4—Ni3 | 78.20 (6) |
C12—C11—C15 | 108.60 (14) | C35—C31—C32 | 108.43 (15) |
C12—C11—Ni1 | 73.22 (9) | C35—C31—Ni3 | 73.20 (9) |
C15—C11—Ni1 | 69.13 (9) | C32—C31—Ni3 | 68.56 (9) |
C12—C11—H11 | 125.7 | C35—C31—H31 | 125.8 |
C15—C11—H11 | 125.7 | C32—C31—H31 | 125.8 |
Ni1—C11—H11 | 123.5 | Ni3—C31—H31 | 124 |
C11—C12—C13 | 107.27 (14) | C33—C32—C31 | 107.66 (15) |
C11—C12—Ni1 | 68.47 (9) | C33—C32—Ni3 | 70.51 (10) |
C13—C12—Ni1 | 68.43 (8) | C31—C32—Ni3 | 71.68 (9) |
C11—C12—H12 | 126.4 | C33—C32—H32 | 126.2 |
C13—C12—H12 | 126.4 | C31—C32—H32 | 126.2 |
Ni1—C12—H12 | 128.3 | Ni3—C32—H32 | 123.3 |
C12—C13—C14 | 108.70 (14) | C32—C33—C34 | 107.87 (15) |
C12—C13—Ni1 | 73.19 (9) | C32—C33—Ni3 | 70.30 (9) |
C14—C13—Ni1 | 69.54 (9) | C34—C33—Ni3 | 71.11 (9) |
C12—C13—H13 | 125.6 | C32—C33—H33 | 126.1 |
C14—C13—H13 | 125.6 | C34—C33—H33 | 126.1 |
Ni1—C13—H13 | 123.2 | Ni3—C33—H33 | 124.1 |
C15—C14—C13 | 107.84 (15) | C35—C34—C33 | 108.18 (15) |
C15—C14—Ni1 | 70.15 (9) | C35—C34—Ni3 | 73.52 (9) |
C13—C14—Ni1 | 70.89 (9) | C33—C34—Ni3 | 69.07 (9) |
C15—C14—H14 | 126.1 | C35—C34—H34 | 125.9 |
C13—C14—H14 | 126.1 | C33—C34—H34 | 125.9 |
Ni1—C14—H14 | 124.5 | Ni3—C34—H34 | 123.1 |
C14—C15—C11 | 107.49 (15) | C31—C35—C34 | 107.76 (15) |
C14—C15—Ni1 | 70.66 (9) | C31—C35—Ni3 | 68.80 (9) |
C11—C15—Ni1 | 70.99 (9) | C34—C35—Ni3 | 68.22 (8) |
C14—C15—H15 | 126.3 | C31—C35—H35 | 126.1 |
C11—C15—H15 | 126.3 | C34—C35—H35 | 126.1 |
Ni1—C15—H15 | 123.7 | Ni3—C35—H35 | 128.4 |
C22—C21—C25 | 108.63 (15) | C42—C41—C45 | 108.57 (16) |
C22—C21—Ni2 | 73.28 (9) | C42—C41—Ni4 | 70.58 (9) |
C25—C21—Ni2 | 69.14 (9) | C45—C41—Ni4 | 71.41 (9) |
C22—C21—H21 | 125.7 | C42—C41—H41 | 125.7 |
C25—C21—H21 | 125.7 | C45—C41—H41 | 125.7 |
Ni2—C21—H21 | 123.5 | Ni4—C41—H41 | 123.9 |
C23—C22—C21 | 107.22 (15) | C41—C42—C43 | 107.17 (16) |
C23—C22—Ni2 | 68.23 (9) | C41—C42—Ni4 | 70.72 (9) |
C21—C22—Ni2 | 68.49 (9) | C43—C42—Ni4 | 70.26 (10) |
C23—C22—H22 | 126.4 | C41—C42—H42 | 126.4 |
C21—C22—H22 | 126.4 | C43—C42—H42 | 126.4 |
Ni2—C22—H22 | 128.4 | Ni4—C42—H42 | 124.2 |
C22—C23—C24 | 108.87 (14) | C44—C43—C42 | 108.37 (16) |
C22—C23—Ni2 | 73.61 (9) | C44—C43—Ni4 | 73.50 (10) |
C24—C23—Ni2 | 69.31 (9) | C42—C43—Ni4 | 69.80 (10) |
C22—C23—H23 | 125.6 | C44—C43—H43 | 125.8 |
C24—C23—H23 | 125.6 | C42—C43—H43 | 125.8 |
Ni2—C23—H23 | 123.1 | Ni4—C43—H43 | 122.5 |
C25—C24—C23 | 107.67 (15) | C45—C44—C43 | 107.07 (16) |
C25—C24—Ni2 | 70.53 (9) | C45—C44—Ni4 | 69.11 (9) |
C23—C24—Ni2 | 71.00 (9) | C43—C44—Ni4 | 67.76 (10) |
C25—C24—H24 | 126.2 | C45—C44—H44 | 126.5 |
C23—C24—H24 | 126.2 | C43—C44—H44 | 126.5 |
Ni2—C24—H24 | 123.9 | Ni4—C44—H44 | 128.2 |
C24—C25—C21 | 107.52 (15) | C44—C45—C41 | 108.71 (16) |
C24—C25—Ni2 | 70.29 (9) | C44—C45—Ni4 | 73.04 (10) |
C21—C25—Ni2 | 71.15 (9) | C41—C45—Ni4 | 69.19 (9) |
C24—C25—H25 | 126.2 | C44—C45—H45 | 125.6 |
C21—C25—H25 | 126.2 | C41—C45—H45 | 125.6 |
Ni2—C25—H25 | 123.9 | Ni4—C45—H45 | 123.7 |
Experimental details
Crystal data | |
Chemical formula | C12H10Ni2O2 |
Mr | 303.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 115 |
a, b, c (Å) | 7.7498 (1), 10.8752 (1), 13.4942 (2) |
α, β, γ (°) | 76.776 (1), 81.112 (1), 78.449 (1) |
V (Å3) | 1077.65 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.47 |
Crystal size (mm) | 0.40 × 0.28 × 0.15 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.264, 0.594 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 84232, 6276, 5839 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.10 |
No. of reflections | 6276 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.64 |
Computer programs: Collect (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
The structure of [Ni(CO)(η5-C5H5)]2 had been determined previously on two separate occassions, both at room temperature (Byers & Dahl, 1980; Madach et al., 1980). The advances made in crystallographic techniques since this time allowed for a redetermination of the structure at lower temperature with a significant increase in the quality of the structural solution.
As previously reported, there are two independent molecules within the asymmetric unit (Figure 1). The Ni—Ni distances [2.3691 (3) and 2.3575 (3) Å for Ni(1)—Ni(2) and Ni(3)—Ni(4) respectively] are greater than those previously reported [2.3627 (9) and 2.3510 (9) Å Byers & Dahl, 1980; 2.361 (2) and 2.348 (2) Å Madach et al., 1980] though the remaining bond parameters of the molecules display no significant differences. Both molecules possess non-planar Ni2(CO)2 units, analogous to that found for Co2(CO)8 (Sumner et al., 1964; Leung & Coppens, 1983), with the η5-C5H5 rings tilted in the opposite direction. The angle between the η5-C5H5 and NiC2 planes ranges from 80.3–82.6° across the two molecules.
A minor component of disorder was noted from difference maps and the positions of the nickel atoms in this component identified. Refinement indicated the extent of the disorder to be approximately 1% with the Ni—Ni distances in the minor component [2.32 (2) and 2.34 (2) Å for Ni(1a)—Ni(2a) and Ni(3a)—Ni(4a) respectively] similar to those in the main structure. The positions of the nickel atoms in the minor component of the disorder appear related to those of the major component by a translation of 6.3–6.4 Å along the c axis of the unit cell (Figure 2). The possibility that this electron density was a result of twinning rather than disorder was examined using the ROTAX program (Cooper et al., 2002) to test for the presence of a 2-fold axis though none was identified. Similarly, the set comprising the weakest 655 reflections provided a K-factor of 1.87, lower than generally observed for a genuine twinned structure. There was also no evidence from the diffraction pattern observed for a twinned crystal.