Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106018191/gd3016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106018191/gd3016Isup2.hkl |
CCDC reference: 616105
Compound (I) was obtained by reaction of equimolar tetrahydrofuran (THF) solutions of C16H36N[Ni(dmio)2] (Hendrickson et al., 1971) and [Fe(Cp*)2]BF4 (Muller et al., 1997). The two solutions were filtered and slowly added to one another with constant stirring. Rapid precipitation occurred and a polycrystalline precipitate was collected via vacuum filtration. The precipitate was dissolved in THF. Suitable crystals of (I) for X-ray diffraction were obtained by slow evaporation of a saturated THF solution.
Cp* H atoms were treated as riding, with C—H = 0.96 Å and UisoH = 1.5Ueq(C). Solvent H atoms were treated as riding, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). Occupancy refinement for the tetrahydrofuran solvent indicated unit occupancy.
Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell refinement: CAD-4 Software; data reduction: PROCESS in MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SCHAKAL (Keller, 1989) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe(C10H15)2][Ni(C3OS4)2]·C4H8O | F(000) = 1696 |
Mr = 817.70 | Dx = 1.530 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 25 reflections |
a = 16.4733 (17) Å | θ = 7–12° |
b = 11.0224 (10) Å | µ = 1.44 mm−1 |
c = 19.693 (2) Å | T = 295 K |
β = 96.887 (9)° | Plate, dark green |
V = 3550.0 (6) Å3 | 0.50 × 0.30 × 0.04 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 3359 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
ω/2θ scans | h = −20→20 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→0 |
Tmin = 0.613, Tmax = 0.940 | l = −24→0 |
7075 measured reflections | 5 standard reflections every 300 reflections |
6873 independent reflections | intensity decay: none |
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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0535P)2] where P = (Fo2 + 2Fc2)/3 |
6873 reflections | (Δ/σ)max = 0.001 |
401 parameters | Δρmax = 0.43 e Å−3 |
1 restraint | Δρmin = −0.34 e Å−3 |
[Fe(C10H15)2][Ni(C3OS4)2]·C4H8O | V = 3550.0 (6) Å3 |
Mr = 817.70 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 16.4733 (17) Å | µ = 1.44 mm−1 |
b = 11.0224 (10) Å | T = 295 K |
c = 19.693 (2) Å | 0.50 × 0.30 × 0.04 mm |
β = 96.887 (9)° |
Enraf–Nonius CAD-4 diffractometer | 3359 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.613, Tmax = 0.940 | 5 standard reflections every 300 reflections |
7075 measured reflections | intensity decay: none |
6873 independent reflections |
R[F2 > 2σ(F2)] = 0.072 | 1 restraint |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.43 e Å−3 |
6873 reflections | Δρmin = −0.34 e Å−3 |
401 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 | ||
Ni1 | 0.5000 | 0.5000 | 0.0000 | 0.0412 (3) | |
S1 | 0.48927 (9) | 0.48230 (17) | −0.10976 (8) | 0.0504 (5) | |
S2 | 0.62729 (9) | 0.54616 (17) | 0.00796 (9) | 0.0534 (5) | |
C1 | 0.5876 (3) | 0.5094 (6) | −0.1270 (3) | 0.0461 (15) | |
C2 | 0.6467 (4) | 0.5381 (6) | −0.0766 (3) | 0.0467 (17) | |
S3 | 0.61429 (10) | 0.50288 (19) | −0.20981 (9) | 0.0568 (5) | |
S4 | 0.74479 (10) | 0.5617 (2) | −0.09844 (9) | 0.0610 (5) | |
C3 | 0.7195 (4) | 0.5401 (7) | −0.1861 (4) | 0.059 (2) | |
O1 | 0.7686 (3) | 0.5457 (5) | −0.2272 (3) | 0.0798 (17) | |
Ni2 | 0.5000 | 0.0000 | 0.5000 | 0.0537 (3) | |
S5 | 0.42338 (11) | −0.1355 (2) | 0.53812 (11) | 0.0681 (6) | |
S6 | 0.41452 (11) | 0.1448 (2) | 0.51178 (11) | 0.0673 (6) | |
C4 | 0.3420 (4) | −0.0510 (8) | 0.5587 (4) | 0.060 (2) | |
C5 | 0.3385 (4) | 0.0681 (8) | 0.5473 (3) | 0.059 (2) | |
S7 | 0.26335 (13) | −0.1159 (3) | 0.59673 (13) | 0.0930 (8) | |
S8 | 0.25605 (13) | 0.1482 (2) | 0.57418 (12) | 0.0870 (7) | |
C6 | 0.2097 (5) | 0.0216 (10) | 0.6070 (4) | 0.099 (3) | |
O2 | 0.1496 (3) | 0.0248 (7) | 0.6365 (3) | 0.133 (3) | |
Fe | 0.41108 (5) | 0.00228 (9) | 0.19020 (4) | 0.0402 (2) | |
C10 | 0.3666 (4) | 0.1390 (6) | 0.1214 (3) | 0.0433 (15) | |
C11 | 0.3251 (4) | 0.1431 (5) | 0.1819 (3) | 0.0462 (16) | |
C12 | 0.3844 (4) | 0.1640 (6) | 0.2398 (4) | 0.0519 (18) | |
C13 | 0.4611 (4) | 0.1743 (5) | 0.2151 (4) | 0.0476 (17) | |
C14 | 0.4510 (4) | 0.1579 (5) | 0.1439 (3) | 0.0428 (16) | |
C15 | 0.4823 (4) | −0.1450 (6) | 0.1675 (4) | 0.0503 (17) | |
C16 | 0.4874 (4) | −0.1310 (6) | 0.2394 (4) | 0.0534 (18) | |
C17 | 0.4078 (4) | −0.1452 (6) | 0.2584 (4) | 0.062 (2) | |
C18 | 0.3532 (4) | −0.1667 (6) | 0.1986 (4) | 0.0525 (18) | |
C19 | 0.3990 (4) | −0.1675 (5) | 0.1423 (3) | 0.0455 (16) | |
C101 | 0.3289 (4) | 0.1248 (7) | 0.0500 (3) | 0.065 (2) | |
H10A | 0.2745 | 0.0932 | 0.0495 | 0.097* | |
H10B | 0.3610 | 0.0697 | 0.0265 | 0.097* | |
H10C | 0.3267 | 0.2022 | 0.0275 | 0.097* | |
C111 | 0.2329 (4) | 0.1294 (7) | 0.1836 (4) | 0.079 (3) | |
H11A | 0.2088 | 0.0926 | 0.1418 | 0.118* | |
H11B | 0.2090 | 0.2079 | 0.1884 | 0.118* | |
H11C | 0.2231 | 0.0793 | 0.2216 | 0.118* | |
C121 | 0.3661 (5) | 0.1833 (8) | 0.3114 (4) | 0.083 (3) | |
H12A | 0.4120 | 0.1575 | 0.3428 | 0.125* | |
H12B | 0.3188 | 0.1369 | 0.3192 | 0.125* | |
H12C | 0.3559 | 0.2678 | 0.3185 | 0.125* | |
C131 | 0.5414 (4) | 0.2045 (7) | 0.2579 (4) | 0.075 (2) | |
H13A | 0.5367 | 0.1888 | 0.3052 | 0.112* | |
H13B | 0.5541 | 0.2886 | 0.2521 | 0.112* | |
H13C | 0.5842 | 0.1552 | 0.2435 | 0.112* | |
C141 | 0.5168 (4) | 0.1678 (6) | 0.0974 (4) | 0.068 (2) | |
H14A | 0.5050 | 0.1131 | 0.0596 | 0.101* | |
H14B | 0.5686 | 0.1473 | 0.1223 | 0.101* | |
H14C | 0.5186 | 0.2494 | 0.0806 | 0.101* | |
C151 | 0.5530 (4) | −0.1447 (7) | 0.1259 (4) | 0.072 (2) | |
H15A | 0.5344 | −0.1190 | 0.0801 | 0.108* | |
H15B | 0.5753 | −0.2251 | 0.1249 | 0.108* | |
H15C | 0.5943 | −0.0900 | 0.1461 | 0.108* | |
C161 | 0.5637 (4) | −0.1114 (7) | 0.2877 (4) | 0.088 (3) | |
H16A | 0.5506 | −0.0682 | 0.3272 | 0.131* | |
H16B | 0.6021 | −0.0650 | 0.2653 | 0.131* | |
H16C | 0.5874 | −0.1884 | 0.3014 | 0.131* | |
C171 | 0.3851 (5) | −0.1431 (8) | 0.3297 (4) | 0.092 (3) | |
H17A | 0.4228 | −0.0924 | 0.3578 | 0.138* | |
H17B | 0.3873 | −0.2240 | 0.3478 | 0.138* | |
H17C | 0.3308 | −0.1115 | 0.3291 | 0.138* | |
C181 | 0.2624 (4) | −0.1923 (7) | 0.1957 (5) | 0.089 (3) | |
H18A | 0.2364 | −0.1792 | 0.1500 | 0.134* | |
H18B | 0.2389 | −0.1389 | 0.2266 | 0.134* | |
H18C | 0.2544 | −0.2750 | 0.2088 | 0.134* | |
C191 | 0.3674 (5) | −0.1927 (7) | 0.0695 (4) | 0.081 (3) | |
H19A | 0.3967 | −0.1442 | 0.0400 | 0.121* | |
H19B | 0.3102 | −0.1732 | 0.0617 | 0.121* | |
H19C | 0.3749 | −0.2771 | 0.0598 | 0.121* | |
O3 | 0.1719 (6) | −0.0099 (11) | 0.3308 (5) | 0.203 (5) | |
C20 | 0.0966 (7) | −0.0485 (10) | 0.3104 (6) | 0.118 (4) | |
H20A | 0.0974 | −0.1320 | 0.2948 | 0.142* | |
H20B | 0.0710 | 0.0014 | 0.2732 | 0.142* | |
C21 | 0.0533 (7) | −0.0388 (14) | 0.3692 (8) | 0.164 (6) | |
H21A | 0.0300 | −0.1170 | 0.3784 | 0.197* | |
H21B | 0.0088 | 0.0186 | 0.3597 | 0.197* | |
C22 | 0.1078 (9) | 0.0016 (12) | 0.4298 (6) | 0.149 (5) | |
H22A | 0.0888 | 0.0763 | 0.4486 | 0.179* | |
H22B | 0.1140 | −0.0602 | 0.4652 | 0.179* | |
C23 | 0.1821 (7) | 0.0194 (14) | 0.4000 (6) | 0.181 (7) | |
H23A | 0.1990 | 0.1035 | 0.4055 | 0.218* | |
H23B | 0.2249 | −0.0308 | 0.4236 | 0.218* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0333 (5) | 0.0445 (6) | 0.0474 (7) | 0.0022 (6) | 0.0110 (5) | 0.0054 (6) |
S1 | 0.0358 (8) | 0.0628 (13) | 0.0539 (10) | −0.0039 (8) | 0.0107 (7) | 0.0001 (9) |
S2 | 0.0347 (8) | 0.0741 (13) | 0.0521 (10) | −0.0027 (8) | 0.0083 (7) | 0.0029 (9) |
C1 | 0.042 (3) | 0.046 (4) | 0.052 (4) | 0.001 (3) | 0.010 (3) | 0.002 (4) |
C2 | 0.035 (3) | 0.050 (4) | 0.056 (4) | −0.002 (3) | 0.010 (3) | 0.006 (3) |
S3 | 0.0479 (9) | 0.0712 (12) | 0.0542 (10) | 0.0009 (11) | 0.0174 (8) | 0.0030 (11) |
S4 | 0.0359 (9) | 0.0878 (14) | 0.0610 (12) | −0.0026 (9) | 0.0132 (8) | 0.0087 (11) |
C3 | 0.045 (4) | 0.068 (5) | 0.067 (5) | 0.003 (3) | 0.015 (4) | 0.014 (4) |
O1 | 0.058 (3) | 0.112 (5) | 0.076 (4) | −0.001 (3) | 0.034 (3) | 0.006 (3) |
Ni2 | 0.0449 (6) | 0.0703 (8) | 0.0493 (7) | −0.0033 (7) | 0.0199 (5) | −0.0002 (7) |
S5 | 0.0575 (11) | 0.0731 (15) | 0.0789 (14) | −0.0046 (11) | 0.0292 (10) | 0.0043 (11) |
S6 | 0.0547 (11) | 0.0754 (14) | 0.0758 (13) | 0.0056 (10) | 0.0246 (10) | 0.0020 (12) |
C4 | 0.046 (4) | 0.078 (5) | 0.061 (5) | −0.006 (4) | 0.023 (4) | 0.004 (4) |
C5 | 0.041 (4) | 0.094 (6) | 0.043 (4) | 0.001 (4) | 0.011 (3) | −0.012 (4) |
S7 | 0.0585 (13) | 0.131 (2) | 0.0967 (17) | −0.0107 (14) | 0.0391 (12) | 0.0189 (16) |
S8 | 0.0571 (12) | 0.124 (2) | 0.0842 (16) | 0.0175 (13) | 0.0266 (11) | −0.0075 (15) |
C6 | 0.054 (5) | 0.156 (10) | 0.093 (7) | 0.010 (6) | 0.032 (5) | 0.008 (7) |
O2 | 0.072 (4) | 0.219 (9) | 0.120 (5) | 0.022 (5) | 0.061 (4) | 0.032 (5) |
Fe | 0.0308 (4) | 0.0429 (5) | 0.0479 (5) | −0.0012 (5) | 0.0086 (4) | −0.0004 (5) |
C10 | 0.050 (4) | 0.042 (4) | 0.038 (4) | −0.003 (3) | 0.006 (3) | 0.000 (3) |
C11 | 0.041 (4) | 0.034 (4) | 0.067 (5) | −0.004 (3) | 0.015 (3) | 0.001 (3) |
C12 | 0.050 (4) | 0.051 (4) | 0.057 (5) | 0.010 (3) | 0.017 (4) | −0.004 (4) |
C13 | 0.041 (4) | 0.034 (4) | 0.068 (5) | −0.005 (3) | 0.005 (3) | −0.010 (3) |
C14 | 0.042 (4) | 0.030 (3) | 0.059 (4) | −0.004 (3) | 0.021 (3) | 0.001 (3) |
C15 | 0.038 (4) | 0.033 (4) | 0.081 (5) | 0.001 (3) | 0.013 (3) | −0.008 (4) |
C16 | 0.047 (4) | 0.049 (4) | 0.064 (5) | 0.006 (3) | 0.005 (4) | 0.011 (4) |
C17 | 0.060 (5) | 0.050 (5) | 0.079 (6) | 0.002 (4) | 0.026 (4) | 0.019 (4) |
C18 | 0.036 (4) | 0.040 (4) | 0.082 (5) | −0.003 (3) | 0.010 (4) | 0.004 (4) |
C19 | 0.047 (4) | 0.036 (4) | 0.051 (4) | 0.004 (3) | −0.002 (3) | −0.006 (3) |
C101 | 0.070 (5) | 0.070 (5) | 0.054 (5) | −0.002 (4) | 0.001 (4) | 0.010 (4) |
C111 | 0.040 (4) | 0.067 (6) | 0.132 (7) | 0.010 (4) | 0.021 (4) | 0.015 (5) |
C121 | 0.096 (6) | 0.085 (7) | 0.074 (6) | 0.011 (5) | 0.030 (5) | −0.024 (5) |
C131 | 0.053 (4) | 0.080 (6) | 0.087 (6) | −0.013 (4) | −0.009 (4) | −0.019 (5) |
C141 | 0.072 (5) | 0.053 (5) | 0.086 (6) | −0.003 (4) | 0.039 (4) | 0.004 (4) |
C151 | 0.060 (5) | 0.064 (5) | 0.100 (6) | 0.008 (4) | 0.043 (4) | −0.011 (5) |
C161 | 0.069 (5) | 0.084 (6) | 0.102 (7) | −0.008 (5) | −0.025 (5) | 0.019 (5) |
C171 | 0.105 (7) | 0.104 (7) | 0.074 (6) | −0.011 (6) | 0.038 (5) | 0.021 (5) |
C181 | 0.046 (5) | 0.067 (6) | 0.157 (9) | −0.015 (4) | 0.022 (5) | 0.002 (6) |
C191 | 0.087 (6) | 0.061 (5) | 0.088 (6) | 0.006 (5) | −0.012 (5) | −0.019 (5) |
O3 | 0.132 (7) | 0.371 (17) | 0.104 (7) | −0.027 (9) | 0.006 (6) | −0.043 (8) |
C20 | 0.116 (9) | 0.117 (9) | 0.117 (10) | −0.002 (8) | −0.006 (8) | −0.002 (7) |
C21 | 0.080 (8) | 0.243 (17) | 0.171 (14) | −0.037 (9) | 0.017 (9) | 0.004 (13) |
C22 | 0.188 (13) | 0.151 (11) | 0.118 (10) | −0.039 (11) | 0.055 (10) | −0.012 (9) |
C23 | 0.130 (10) | 0.32 (2) | 0.096 (9) | −0.088 (12) | 0.027 (8) | −0.047 (11) |
Ni1—S2 | 2.1451 (16) | C17—C18 | 1.414 (9) |
Ni1—S2i | 2.1451 (16) | C17—C171 | 1.495 (9) |
Ni1—S1i | 2.1564 (17) | C18—C19 | 1.414 (9) |
Ni1—S1 | 2.1564 (17) | C18—C181 | 1.517 (8) |
S1—C1 | 1.720 (6) | C19—C191 | 1.492 (9) |
S2—C2 | 1.735 (7) | C101—H10A | 0.9600 |
C1—C2 | 1.343 (8) | C101—H10B | 0.9600 |
C1—S3 | 1.741 (6) | C101—H10C | 0.9600 |
C2—S4 | 1.740 (6) | C111—H11A | 0.9600 |
S3—C3 | 1.787 (7) | C111—H11B | 0.9600 |
S4—C3 | 1.743 (7) | C111—H11C | 0.9600 |
C3—O1 | 1.212 (7) | C121—H12A | 0.9600 |
Ni2—S5 | 2.1480 (19) | C121—H12B | 0.9600 |
Ni2—S5ii | 2.1480 (19) | C121—H12C | 0.9600 |
Ni2—S6ii | 2.159 (2) | C131—H13A | 0.9600 |
Ni2—S6 | 2.159 (2) | C131—H13B | 0.9600 |
S5—C4 | 1.720 (7) | C131—H13C | 0.9600 |
S6—C5 | 1.726 (7) | C141—H14A | 0.9600 |
C4—C5 | 1.332 (10) | C141—H14B | 0.9600 |
C4—S7 | 1.728 (7) | C141—H14C | 0.9600 |
C5—S8 | 1.754 (7) | C151—H15A | 0.9600 |
S7—C6 | 1.779 (10) | C151—H15B | 0.9600 |
S8—C6 | 1.751 (10) | C151—H15C | 0.9600 |
C6—O2 | 1.206 (8) | C161—H16A | 0.9600 |
Fe—C15 | 2.083 (6) | C161—H16B | 0.9600 |
Fe—C14 | 2.086 (6) | C161—H16C | 0.9600 |
Fe—C16 | 2.094 (6) | C171—H17A | 0.9600 |
Fe—C11 | 2.094 (6) | C171—H17B | 0.9600 |
Fe—C19 | 2.095 (6) | C171—H17C | 0.9600 |
Fe—C10 | 2.098 (6) | C181—H18A | 0.9600 |
Fe—C13 | 2.102 (6) | C181—H18B | 0.9600 |
Fe—C12 | 2.104 (7) | C181—H18C | 0.9600 |
Fe—C18 | 2.108 (6) | C191—H19A | 0.9600 |
Fe—C17 | 2.113 (7) | C191—H19B | 0.9600 |
C10—C14 | 1.424 (8) | C191—H19C | 0.9600 |
C10—C11 | 1.443 (8) | O3—C20 | 1.328 (10) |
C10—C101 | 1.477 (8) | O3—C23 | 1.390 (12) |
C11—C12 | 1.429 (9) | C20—C21 | 1.435 (14) |
C11—C111 | 1.530 (8) | C20—H20A | 0.9700 |
C12—C13 | 1.413 (8) | C20—H20B | 0.9700 |
C12—C121 | 1.492 (9) | C21—C22 | 1.474 (15) |
C13—C14 | 1.402 (8) | C21—H21A | 0.9700 |
C13—C131 | 1.518 (8) | C21—H21B | 0.9700 |
C14—C141 | 1.504 (8) | C22—C23 | 1.433 (13) |
C15—C16 | 1.416 (9) | C22—H22A | 0.9700 |
C15—C19 | 1.423 (8) | C22—H22B | 0.9700 |
C15—C151 | 1.502 (8) | C23—H23A | 0.9700 |
C16—C17 | 1.414 (9) | C23—H23B | 0.9700 |
C16—C161 | 1.499 (9) | ||
S2—Ni1—S2i | 180.0 | C16—C15—C151 | 126.0 (6) |
S2—Ni1—S1i | 86.75 (6) | C19—C15—C151 | 126.0 (7) |
S2i—Ni1—S1i | 93.25 (6) | C16—C15—Fe | 70.6 (4) |
S2—Ni1—S1 | 93.25 (6) | C19—C15—Fe | 70.5 (4) |
S2i—Ni1—S1 | 86.75 (6) | C151—C15—Fe | 127.5 (5) |
S1i—Ni1—S1 | 180.0 | C17—C16—C15 | 107.9 (6) |
C1—S1—Ni1 | 102.5 (2) | C17—C16—C161 | 125.6 (7) |
C2—S2—Ni1 | 102.1 (2) | C15—C16—C161 | 126.5 (6) |
C2—C1—S1 | 120.8 (5) | C17—C16—Fe | 71.1 (4) |
C2—C1—S3 | 117.4 (5) | C15—C16—Fe | 69.7 (4) |
S1—C1—S3 | 121.8 (4) | C161—C16—Fe | 127.1 (5) |
C1—C2—S2 | 121.4 (5) | C18—C17—C16 | 108.4 (6) |
C1—C2—S4 | 117.7 (5) | C18—C17—C171 | 125.4 (7) |
S2—C2—S4 | 120.9 (4) | C16—C17—C171 | 126.2 (7) |
C1—S3—C3 | 95.3 (3) | C18—C17—Fe | 70.2 (4) |
C2—S4—C3 | 96.1 (3) | C16—C17—Fe | 69.6 (4) |
O1—C3—S4 | 123.7 (6) | C171—C17—Fe | 127.8 (6) |
O1—C3—S3 | 122.8 (6) | C17—C18—C19 | 107.9 (6) |
S4—C3—S3 | 113.5 (4) | C17—C18—C181 | 126.0 (7) |
S5—Ni2—S5ii | 180.00 (8) | C19—C18—C181 | 125.9 (7) |
S5—Ni2—S6ii | 86.67 (7) | C17—C18—Fe | 70.6 (4) |
S5ii—Ni2—S6ii | 93.33 (7) | C19—C18—Fe | 69.8 (4) |
S5—Ni2—S6 | 93.33 (7) | C181—C18—Fe | 127.9 (5) |
S5ii—Ni2—S6 | 86.67 (7) | C18—C19—C15 | 107.9 (6) |
S6ii—Ni2—S6 | 180.00 (11) | C18—C19—C191 | 126.7 (6) |
C4—S5—Ni2 | 102.3 (3) | C15—C19—C191 | 125.4 (7) |
C5—S6—Ni2 | 101.3 (3) | C18—C19—Fe | 70.9 (4) |
C5—C4—S5 | 120.9 (6) | C15—C19—Fe | 69.6 (4) |
C5—C4—S7 | 117.5 (6) | C191—C19—Fe | 127.1 (5) |
S5—C4—S7 | 121.6 (5) | C10—C101—H10A | 109.5 |
C4—C5—S6 | 122.1 (6) | C10—C101—H10B | 109.5 |
C4—C5—S8 | 117.7 (6) | H10A—C101—H10B | 109.5 |
S6—C5—S8 | 120.1 (5) | C10—C101—H10C | 109.5 |
C4—S7—C6 | 96.1 (4) | H10A—C101—H10C | 109.5 |
C6—S8—C5 | 95.7 (4) | H10B—C101—H10C | 109.5 |
O2—C6—S8 | 125.0 (9) | C11—C111—H11A | 109.5 |
O2—C6—S7 | 121.9 (9) | C11—C111—H11B | 109.5 |
S8—C6—S7 | 113.1 (4) | H11A—C111—H11B | 109.5 |
C15—Fe—C14 | 109.4 (2) | C11—C111—H11C | 109.5 |
C15—Fe—C16 | 39.6 (2) | H11A—C111—H11C | 109.5 |
C14—Fe—C16 | 125.2 (3) | H11B—C111—H11C | 109.5 |
C15—Fe—C11 | 162.6 (3) | C12—C121—H12A | 109.5 |
C14—Fe—C11 | 66.6 (2) | C12—C121—H12B | 109.5 |
C16—Fe—C11 | 156.8 (3) | H12A—C121—H12B | 109.5 |
C15—Fe—C19 | 39.8 (2) | C12—C121—H12C | 109.5 |
C14—Fe—C19 | 123.8 (3) | H12A—C121—H12C | 109.5 |
C16—Fe—C19 | 66.5 (3) | H12B—C121—H12C | 109.5 |
C11—Fe—C19 | 126.9 (2) | C13—C131—H13A | 109.5 |
C15—Fe—C10 | 125.7 (3) | C13—C131—H13B | 109.5 |
C14—Fe—C10 | 39.8 (2) | H13A—C131—H13B | 109.5 |
C16—Fe—C10 | 161.1 (3) | C13—C131—H13C | 109.5 |
C11—Fe—C10 | 40.3 (2) | H13A—C131—H13C | 109.5 |
C19—Fe—C10 | 110.1 (3) | H13B—C131—H13C | 109.5 |
C15—Fe—C13 | 122.6 (2) | C14—C141—H14A | 109.5 |
C14—Fe—C13 | 39.1 (2) | C14—C141—H14B | 109.5 |
C16—Fe—C13 | 109.2 (3) | H14A—C141—H14B | 109.5 |
C11—Fe—C13 | 65.9 (2) | C14—C141—H14C | 109.5 |
C19—Fe—C13 | 157.6 (3) | H14A—C141—H14C | 109.5 |
C10—Fe—C13 | 66.4 (2) | H14B—C141—H14C | 109.5 |
C15—Fe—C12 | 156.1 (3) | C15—C151—H15A | 109.5 |
C14—Fe—C12 | 66.5 (2) | C15—C151—H15B | 109.5 |
C16—Fe—C12 | 121.8 (3) | H15A—C151—H15B | 109.5 |
C11—Fe—C12 | 39.8 (2) | C15—C151—H15C | 109.5 |
C19—Fe—C12 | 162.2 (3) | H15A—C151—H15C | 109.5 |
C10—Fe—C12 | 67.4 (2) | H15B—C151—H15C | 109.5 |
C13—Fe—C12 | 39.3 (2) | C16—C161—H16A | 109.5 |
C15—Fe—C18 | 66.4 (2) | C16—C161—H16B | 109.5 |
C14—Fe—C18 | 158.5 (3) | H16A—C161—H16B | 109.5 |
C16—Fe—C18 | 66.1 (3) | C16—C161—H16C | 109.5 |
C11—Fe—C18 | 110.7 (2) | H16A—C161—H16C | 109.5 |
C19—Fe—C18 | 39.3 (2) | H16B—C161—H16C | 109.5 |
C10—Fe—C18 | 124.0 (3) | C17—C171—H17A | 109.5 |
C13—Fe—C18 | 161.3 (3) | C17—C171—H17B | 109.5 |
C12—Fe—C18 | 126.2 (3) | H17A—C171—H17B | 109.5 |
C15—Fe—C17 | 66.1 (3) | C17—C171—H17C | 109.5 |
C14—Fe—C17 | 160.7 (3) | H17A—C171—H17C | 109.5 |
C16—Fe—C17 | 39.3 (2) | H17B—C171—H17C | 109.5 |
C11—Fe—C17 | 123.4 (3) | C18—C181—H18A | 109.5 |
C19—Fe—C17 | 65.9 (3) | C18—C181—H18B | 109.5 |
C10—Fe—C17 | 158.3 (3) | H18A—C181—H18B | 109.5 |
C13—Fe—C17 | 125.8 (3) | C18—C181—H18C | 109.5 |
C12—Fe—C17 | 109.5 (3) | H18A—C181—H18C | 109.5 |
C18—Fe—C17 | 39.1 (3) | H18B—C181—H18C | 109.5 |
C14—C10—C11 | 106.3 (5) | C19—C191—H19A | 109.5 |
C14—C10—C101 | 126.5 (6) | C19—C191—H19B | 109.5 |
C11—C10—C101 | 127.1 (6) | H19A—C191—H19B | 109.5 |
C14—C10—Fe | 69.6 (3) | C19—C191—H19C | 109.5 |
C11—C10—Fe | 69.7 (3) | H19A—C191—H19C | 109.5 |
C101—C10—Fe | 127.8 (5) | H19B—C191—H19C | 109.5 |
C12—C11—C10 | 108.5 (5) | C20—O3—C23 | 111.7 (10) |
C12—C11—C111 | 125.7 (6) | O3—C20—C21 | 105.5 (10) |
C10—C11—C111 | 125.8 (6) | O3—C20—H20A | 110.6 |
C12—C11—Fe | 70.5 (4) | C21—C20—H20A | 110.6 |
C10—C11—Fe | 70.0 (3) | O3—C20—H20B | 110.6 |
C111—C11—Fe | 126.1 (5) | C21—C20—H20B | 110.6 |
C13—C12—C11 | 107.0 (6) | H20A—C20—H20B | 108.8 |
C13—C12—C121 | 127.2 (7) | C20—C21—C22 | 111.3 (10) |
C11—C12—C121 | 125.6 (6) | C20—C21—H21A | 109.4 |
C13—C12—Fe | 70.3 (4) | C22—C21—H21A | 109.4 |
C11—C12—Fe | 69.7 (4) | C20—C21—H21B | 109.4 |
C121—C12—Fe | 129.5 (5) | C22—C21—H21B | 109.4 |
C14—C13—C12 | 109.3 (6) | H21A—C21—H21B | 108.0 |
C14—C13—C131 | 125.0 (6) | C23—C22—C21 | 100.1 (10) |
C12—C13—C131 | 125.6 (6) | C23—C22—H22A | 111.8 |
C14—C13—Fe | 69.8 (3) | C21—C22—H22A | 111.8 |
C12—C13—Fe | 70.5 (4) | C23—C22—H22B | 111.8 |
C131—C13—Fe | 128.2 (5) | C21—C22—H22B | 111.8 |
C13—C14—C10 | 108.9 (5) | H22A—C22—H22B | 109.5 |
C13—C14—C141 | 126.3 (6) | O3—C23—C22 | 111.2 (10) |
C10—C14—C141 | 124.7 (6) | O3—C23—H23A | 109.4 |
C13—C14—Fe | 71.1 (4) | C22—C23—H23A | 109.4 |
C10—C14—Fe | 70.6 (3) | O3—C23—H23B | 109.4 |
C141—C14—Fe | 127.9 (4) | C22—C23—H23B | 109.4 |
C16—C15—C19 | 107.9 (6) | H23A—C23—H23B | 108.0 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C10H15)2][Ni(C3OS4)2]·C4H8O |
Mr | 817.70 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 295 |
a, b, c (Å) | 16.4733 (17), 11.0224 (10), 19.693 (2) |
β (°) | 96.887 (9) |
V (Å3) | 3550.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.44 |
Crystal size (mm) | 0.50 × 0.30 × 0.04 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.613, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7075, 6873, 3359 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.149, 1.02 |
No. of reflections | 6873 |
No. of parameters | 401 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.34 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1994), CAD-4 Software, PROCESS in MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SCHAKAL (Keller, 1989) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Following the report of bulk molecular magnets (Miller et al., 1986; Pei et al., 1986), significant research effort has been devoted to this type of material. We have focused our attention on charge-transfer salts based on decamethylmetallocenium donors and monoanionic planar metal dithiolate acceptors, with S = 1/2. These materials seem adequate to obtain new molecular magnets. The ligand dmio2−, the 2-oxo-1,3-dithiole-4,5-dithiolate dianion, C3S4O2−, contains several peripheral S atoms which could contribute to the existence of extended magnetic interactions, and here we report the structure of the title salt, (I).
The structure of (I) consists of [Fe(Cp*)2]+ cations, two centrosymmetric [Ni(dmio)2]− anions and a tetrahydrofuran (THF) solvent molecule (Fig. 1). The [Fe(Cp*)2]+ cations shows approximate C5 local symmetry and the two Cp* rings (Cp* = C10H15) exhibit an almost eclipsed conformation, unlike that observed in most [Fe(Cp*)2]+-based charge-transfer salts, which generally contain staggered conformations. The bond distances and angles in the cations and anions are in the expected ranges (Reference for standard values?). As expected, the centrosymmetric [Ni(dmio)2]− anions adopt a square-planar coordination geometry, with approximate D2h local symmetry. The anions are essentially planar (the atomic deviations from the average molecular plane are less than 0.0186 Å for the [Ni1(dmio)2]− unit and less than 0.0577 Å for the [Ni2(dmio)2]− unit). The average Ni—S distance (Table 1) is in good agreement with values found in other square-planar NiIII dithiolate complexes (Mahadevan et al., 1985). The dihedral angle between the average planes of the two [Ni(dmio)2]− units is 87.79 Å.
The crystal structure of (I) consists of two-dimensional layers composed of parallel mixed chains, where side-by-side pairs of donors alternate with the isolated acceptor, ···D+D+A−D+D+A−··· (Figs. 2 and 3). Within the chains, there is a net charge (+) per repeated unit (D+D+A−), and the layers are separated by sheets of anions and THF molecules which are responsible for charge neutralization.
The supramolecular arrangement observed in (I) is similar to that reported for [Fe(Cp*)2][Ni(dmio)2]·CH3CN (Fettouhi et al., 1995). The Cp* fragment of the cation sits above the dmio2− ligand of the anion. The shorter DA intrachain separation (S···C) exceeds the sum of the van der Waals radii by ca 4% (Reference for van der Waals radii?). The chains in the layers are quite isolated, and S···O short contacts (3.167 Å), involving anions from the chains and the anionic sheets, are observed (Fig. 3).
A different type of structure was observed for decamethylferrocenium charge-transfer salts based on similar acceptors, but without solvent molecules in the crystal structure, such as [Fe(Cp*)2][M(dmit)2], with M = Ni (Broderik et al., 1989) or Pt (Rabaça et al., 1999), and [Fe(Cp*)2][M(dmio)2], with M = Pd or Pt (Rabaça et al., 1999). For these compounds, the crystal structure consists of an arrangement of parallel stacks, where side-by-side pairs of donors alternate with face-to-face pairs of acceptors.
At high temperatures, the magnetic susceptibility of (I) follows the Curie–Weiss law, χ = C/(T - θ), with a θ value of 10.5 K. The dominant ferromagnetic (FM) interactions can be assigned to the FM intrachain DA magnetic coupling (Rabaça et al., 2003), in view of the McConnell I mechanism (McConnell, 1963), due to a spin-polarization effect in the donor, where the C atoms in the C5 rings of the donor ligand present a negative spin density (Rabaça et al., 2001).
In compound (I), the interchain contacts involving the peripheral S atoms seem to be quite weak and the anticipated increase of dimensionality in the magnetic interactions is not observed.