Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021773/ac6021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021773/ac6021Isup2.hkl |
CCDC reference: 202310
2,2'-Bipyridiyl (0.0625 g, 0.400 mmol) was dissolved in 10 ml of methanol. FeCl3·6H2O (0.0915 g, 0.202 mmol) was dissolved in another 10 ml of methanol. The iron solution was slowly added to the bipyridyl solution. The resultant solution was deep red, and was allowed to stand for one week before the volume was reduced by half via rotoevaporation. This solution was then placed in an ethyl acetate bath yielding dark red crystals after five days. Proton NMR on a D2O solution of the crystals gave four broadened peaks at 7.11, 7.26, 7.85 and 8.31 p.p.m..
Data collection: COLLECT (Nonius 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); software used to prepare material for publication: TEXSAN for Windows.
Fig. 1. Displacement ellipsoid plot of the tris-(2,2'-bipyridyl)iron(II) cation, with ellipsoids at the 50% probability level. |
[Fe(C10H8N2)3][FeCl4]2 | F(000) = 1840.0 |
Mr = 919.72 | Dx = 1.668 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 13360 reflections |
a = 18.6108 (4) Å | θ = 2.5–30.0° |
b = 10.7729 (2) Å | µ = 1.79 mm−1 |
c = 18.5661 (6) Å | T = 100 K |
β = 100.381 (2)° | Prism, dark red |
V = 3661.43 (14) Å3 | 0.35 × 0.22 × 0.20 mm |
Z = 4 |
Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 10556 independent reflections |
Radiation source: fine-focus sealed tube | 6113 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.054 |
ω scans with κ offsets | θmax = 30.0°, θmin = 2.5° |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | h = −23→26 |
Tmin = 0.600, Tmax = 0.699 | k = −13→15 |
50254 measured reflections | l = −23→26 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.072 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.0004|Fo|2] |
S = 0.92 | (Δ/σ)max < 0.001 |
6113 reflections | Δρmax = 0.72 e Å−3 |
424 parameters | Δρmin = −0.55 e Å−3 |
[Fe(C10H8N2)3][FeCl4]2 | V = 3661.43 (14) Å3 |
Mr = 919.72 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.6108 (4) Å | µ = 1.79 mm−1 |
b = 10.7729 (2) Å | T = 100 K |
c = 18.5661 (6) Å | 0.35 × 0.22 × 0.20 mm |
β = 100.381 (2)° |
Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 10556 independent reflections |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | 6113 reflections with I > 3σ(I) |
Tmin = 0.600, Tmax = 0.699 | Rint = 0.054 |
50254 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.72 e Å−3 |
6113 reflections | Δρmin = −0.55 e Å−3 |
424 parameters |
Refinement. Refinement of F2. The weighted R-factor wR and goodness of fit are based on F2, conventional R-factors R are based on F. R-factors based on F2 are statistically about twice as large as those based on F. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.75386 (2) | 0.05888 (3) | 0.99014 (2) | 0.01572 (9) | |
Fe2 | 0.61693 (2) | 0.03489 (4) | 0.66489 (2) | 0.02168 (10) | |
Fe3 | 0.88302 (2) | 0.54248 (4) | 0.82609 (2) | 0.02373 (10) | |
Cl1 | 0.55849 (4) | 0.13717 (7) | 0.57039 (4) | 0.0372 (2) | |
Cl2 | 0.66129 (5) | −0.13581 (7) | 0.62506 (4) | 0.0356 (2) | |
Cl3 | 0.54023 (4) | −0.00386 (7) | 0.74024 (4) | 0.0305 (2) | |
Cl4 | 0.70593 (4) | 0.14879 (7) | 0.72311 (4) | 0.0301 (2) | |
Cl5 | 0.90394 (6) | 0.48621 (7) | 0.94071 (4) | 0.0448 (2) | |
Cl6 | 0.89092 (5) | 0.74431 (6) | 0.81280 (4) | 0.0337 (2) | |
Cl7 | 0.96732 (4) | 0.45352 (6) | 0.77338 (4) | 0.0266 (2) | |
Cl8 | 0.77522 (5) | 0.47679 (7) | 0.77280 (5) | 0.0443 (2) | |
N1 | 0.69408 (11) | 0.1980 (2) | 0.94529 (10) | 0.0165 (5) | |
N2 | 0.79939 (11) | 0.1919 (2) | 1.05526 (10) | 0.0162 (5) | |
N3 | 0.67552 (12) | 0.0184 (2) | 1.04435 (11) | 0.0192 (6) | |
N4 | 0.70384 (12) | −0.0695 (2) | 0.92338 (11) | 0.0188 (6) | |
N5 | 0.83083 (12) | 0.0819 (2) | 0.93264 (10) | 0.0175 (5) | |
N6 | 0.81968 (12) | −0.0745 (2) | 1.03467 (11) | 0.0182 (5) | |
C1 | 0.6372 (1) | 0.1907 (2) | 0.88873 (13) | 0.0202 (7) | |
C2 | 0.5957 (2) | 0.2930 (3) | 0.8629 (1) | 0.0250 (7) | |
C3 | 0.6126 (2) | 0.4066 (2) | 0.8955 (2) | 0.0268 (7) | |
C4 | 0.6712 (2) | 0.4162 (2) | 0.9524 (1) | 0.0233 (7) | |
C5 | 0.7106 (1) | 0.3107 (2) | 0.97675 (13) | 0.0177 (6) | |
C6 | 0.7731 (1) | 0.3080 (2) | 1.03804 (13) | 0.0172 (6) | |
C7 | 0.8041 (2) | 0.4122 (2) | 1.0744 (1) | 0.0215 (7) | |
C8 | 0.8643 (2) | 0.3993 (2) | 1.1293 (1) | 0.0238 (7) | |
C9 | 0.8920 (2) | 0.2818 (2) | 1.14680 (13) | 0.0221 (7) | |
C10 | 0.8577 (1) | 0.1810 (2) | 1.10958 (13) | 0.0194 (7) | |
C11 | 0.6630 (2) | 0.0736 (2) | 1.1059 (1) | 0.0231 (7) | |
C12 | 0.6048 (2) | 0.0420 (3) | 1.1388 (2) | 0.0277 (8) | |
C13 | 0.5569 (2) | −0.0489 (3) | 1.1072 (2) | 0.0308 (8) | |
C14 | 0.5684 (2) | −0.1058 (3) | 1.0441 (2) | 0.0273 (8) | |
C15 | 0.6275 (2) | −0.0711 (2) | 1.01319 (13) | 0.0206 (7) | |
C16 | 0.6463 (1) | −0.1245 (2) | 0.94602 (13) | 0.0206 (7) | |
C17 | 0.6087 (2) | −0.2223 (3) | 0.9075 (2) | 0.0313 (8) | |
C18 | 0.6304 (2) | −0.2648 (3) | 0.8448 (2) | 0.0359 (9) | |
C19 | 0.6896 (2) | −0.2113 (2) | 0.8221 (1) | 0.0257 (7) | |
C20 | 0.7248 (2) | −0.1132 (2) | 0.86242 (13) | 0.0214 (7) | |
C21 | 0.8338 (2) | 0.1714 (2) | 0.88278 (13) | 0.0209 (7) | |
C22 | 0.8894 (2) | 0.1781 (3) | 0.8428 (1) | 0.0265 (8) | |
C23 | 0.9449 (2) | 0.0921 (3) | 0.8546 (1) | 0.0263 (8) | |
C24 | 0.9425 (2) | −0.0009 (2) | 0.9062 (1) | 0.0236 (7) | |
C25 | 0.8854 (1) | −0.0038 (2) | 0.94384 (13) | 0.0175 (6) | |
C26 | 0.8768 (1) | −0.0970 (2) | 0.99965 (13) | 0.0180 (6) | |
C27 | 0.9215 (2) | −0.1997 (2) | 1.0167 (1) | 0.0225 (7) | |
C28 | 0.9107 (2) | −0.2784 (2) | 1.0729 (2) | 0.0256 (7) | |
C29 | 0.8549 (2) | −0.2517 (2) | 1.1103 (1) | 0.0253 (7) | |
C30 | 0.8105 (2) | −0.1507 (2) | 1.08964 (13) | 0.0220 (7) | |
H1 | 0.5977 | 0.0822 | 1.1825 | 0.033* | |
H2 | 0.5559 | 0.2851 | 0.8232 | 0.030* | |
H3 | 0.5841 | 0.4777 | 0.8790 | 0.032* | |
H4 | 0.6844 | 0.4944 | 0.9747 | 0.028* | |
H5 | 0.7841 | 0.4921 | 1.0617 | 0.026* | |
H6 | 0.8864 | 0.4700 | 1.1547 | 0.029* | |
H7 | 0.9339 | 0.2707 | 1.1838 | 0.026* | |
H8 | 0.8760 | 0.1003 | 1.1229 | 0.023* | |
H9 | 0.6955 | 0.1367 | 1.1275 | 0.028* | |
H10 | 0.6254 | 0.1126 | 0.8660 | 0.024* | |
H11 | 0.5164 | −0.0719 | 1.1290 | 0.037* | |
H12 | 0.5360 | −0.1686 | 1.0219 | 0.033* | |
H13 | 0.5684 | −0.2595 | 0.9242 | 0.038* | |
H14 | 0.6047 | −0.3307 | 0.8175 | 0.043* | |
H15 | 0.7060 | −0.2408 | 0.7796 | 0.031* | |
H16 | 0.7653 | −0.0754 | 0.8464 | 0.026* | |
H17 | 0.7962 | 0.2322 | 0.8748 | 0.025* | |
H18 | 0.8894 | 0.2418 | 0.8074 | 0.032* | |
H19 | 0.9840 | 0.0961 | 0.8282 | 0.032* | |
H20 | 0.9800 | −0.0618 | 0.9152 | 0.028* | |
H21 | 0.9595 | −0.2161 | 0.9899 | 0.027* | |
H22 | 0.9410 | −0.3490 | 1.0853 | 0.031* | |
H23 | 0.8472 | −0.3026 | 1.1499 | 0.030* | |
H24 | 0.7718 | −0.1342 | 1.1154 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0161 (2) | 0.0149 (2) | 0.0161 (2) | −0.0007 (2) | 0.0026 (1) | 0.00080 (13) |
Fe2 | 0.0190 (2) | 0.0237 (2) | 0.0219 (2) | −0.0002 (2) | 0.0025 (2) | −0.0031 (2) |
Fe3 | 0.0264 (2) | 0.0220 (2) | 0.0231 (2) | −0.0056 (2) | 0.0053 (2) | −0.0041 (2) |
Cl1 | 0.0308 (4) | 0.0520 (5) | 0.0279 (4) | 0.0155 (4) | 0.0028 (3) | 0.0044 (3) |
Cl2 | 0.0449 (5) | 0.0256 (4) | 0.0382 (4) | 0.0047 (4) | 0.0126 (4) | −0.0049 (3) |
Cl3 | 0.0241 (4) | 0.0422 (4) | 0.0258 (3) | −0.0091 (3) | 0.0064 (3) | −0.0065 (3) |
Cl4 | 0.0274 (4) | 0.0343 (4) | 0.0277 (4) | −0.0101 (3) | 0.0028 (3) | −0.0032 (3) |
Cl5 | 0.0758 (7) | 0.0377 (4) | 0.0232 (4) | −0.0105 (4) | 0.0151 (4) | −0.0027 (3) |
Cl6 | 0.0428 (5) | 0.0223 (4) | 0.0350 (4) | −0.0034 (3) | 0.0039 (3) | −0.0040 (3) |
Cl7 | 0.0280 (4) | 0.0259 (4) | 0.0272 (3) | −0.0053 (3) | 0.0088 (3) | −0.0016 (3) |
Cl8 | 0.0273 (4) | 0.0395 (5) | 0.0630 (6) | −0.0069 (4) | −0.0005 (4) | −0.0151 (4) |
N1 | 0.0168 (12) | 0.0163 (10) | 0.0171 (10) | −0.0021 (9) | 0.0048 (9) | 0.0008 (8) |
N2 | 0.0169 (12) | 0.0169 (10) | 0.0157 (10) | 0.0001 (9) | 0.0049 (9) | 0.0011 (8) |
N3 | 0.0185 (12) | 0.0172 (11) | 0.0221 (11) | 0.0015 (9) | 0.0043 (9) | 0.0028 (8) |
N4 | 0.0189 (12) | 0.0163 (10) | 0.0204 (11) | 0.0002 (10) | 0.0015 (9) | 0.0015 (8) |
N5 | 0.0190 (12) | 0.0171 (10) | 0.0162 (10) | −0.0025 (9) | 0.0028 (9) | −0.0030 (8) |
N6 | 0.0206 (12) | 0.0145 (10) | 0.0193 (10) | −0.0016 (9) | 0.0025 (9) | −0.0015 (8) |
C1 | 0.020 (1) | 0.0205 (13) | 0.0201 (12) | −0.0040 (11) | 0.0025 (11) | −0.0001 (10) |
C2 | 0.022 (2) | 0.028 (2) | 0.0234 (13) | 0.0016 (13) | −0.0019 (11) | 0.0039 (11) |
C3 | 0.027 (2) | 0.022 (1) | 0.029 (1) | 0.0041 (13) | −0.0004 (12) | 0.0058 (11) |
C4 | 0.027 (2) | 0.0180 (13) | 0.0242 (13) | 0.0010 (12) | 0.0037 (12) | 0.0019 (10) |
C5 | 0.018 (1) | 0.0172 (12) | 0.0189 (12) | −0.0006 (11) | 0.0051 (11) | 0.0015 (9) |
C6 | 0.017 (1) | 0.0188 (13) | 0.0170 (12) | −0.0010 (11) | 0.0056 (10) | 0.0025 (10) |
C7 | 0.025 (2) | 0.0175 (13) | 0.0225 (13) | −0.0018 (12) | 0.0061 (11) | −0.0002 (10) |
C8 | 0.027 (2) | 0.021 (1) | 0.0233 (13) | −0.0049 (12) | 0.0034 (12) | −0.0034 (10) |
C9 | 0.021 (2) | 0.027 (1) | 0.0177 (12) | −0.0027 (12) | 0.0004 (11) | 0.0006 (10) |
C10 | 0.020 (1) | 0.0216 (13) | 0.0176 (12) | 0.0024 (11) | 0.0044 (11) | 0.0006 (10) |
C11 | 0.026 (2) | 0.0209 (13) | 0.0239 (13) | 0.0009 (12) | 0.0077 (12) | 0.0015 (11) |
C12 | 0.030 (2) | 0.029 (2) | 0.028 (1) | 0.002 (1) | 0.0128 (13) | 0.0017 (12) |
C13 | 0.024 (2) | 0.034 (2) | 0.037 (2) | −0.001 (1) | 0.0123 (13) | 0.0100 (13) |
C14 | 0.024 (2) | 0.028 (2) | 0.031 (2) | −0.0038 (13) | 0.0060 (13) | 0.0036 (12) |
C15 | 0.022 (1) | 0.0179 (13) | 0.0224 (13) | 0.0002 (11) | 0.0046 (11) | 0.0044 (10) |
C16 | 0.021 (2) | 0.0187 (13) | 0.0217 (13) | −0.0033 (11) | 0.0018 (11) | 0.0023 (10) |
C17 | 0.030 (2) | 0.028 (2) | 0.037 (2) | −0.013 (1) | 0.0092 (13) | −0.0007 (13) |
C18 | 0.048 (2) | 0.025 (2) | 0.033 (2) | −0.012 (2) | 0.004 (2) | −0.0071 (12) |
C19 | 0.032 (2) | 0.0207 (13) | 0.0230 (13) | −0.0006 (13) | 0.0008 (12) | −0.0025 (11) |
C20 | 0.022 (2) | 0.0228 (13) | 0.0184 (12) | 0.0010 (12) | 0.0015 (11) | 0.0005 (10) |
C21 | 0.024 (2) | 0.0185 (13) | 0.0203 (13) | −0.0040 (12) | 0.0049 (11) | −0.0003 (10) |
C22 | 0.034 (2) | 0.024 (1) | 0.023 (1) | −0.0100 (13) | 0.0098 (13) | −0.0023 (11) |
C23 | 0.026 (2) | 0.028 (2) | 0.028 (1) | −0.0116 (13) | 0.0142 (12) | −0.0105 (11) |
C24 | 0.021 (2) | 0.023 (1) | 0.028 (1) | −0.0027 (12) | 0.0062 (12) | −0.0077 (11) |
C25 | 0.016 (1) | 0.0186 (13) | 0.0174 (12) | −0.0032 (11) | 0.0013 (11) | −0.0061 (10) |
C26 | 0.017 (1) | 0.0185 (13) | 0.0174 (12) | −0.0015 (11) | −0.0005 (11) | −0.0046 (10) |
C27 | 0.020 (2) | 0.0205 (13) | 0.026 (1) | 0.0024 (12) | 0.0014 (11) | −0.0046 (11) |
C28 | 0.026 (2) | 0.0179 (13) | 0.028 (1) | 0.0041 (12) | −0.0057 (12) | −0.0033 (11) |
C29 | 0.033 (2) | 0.0176 (13) | 0.0234 (13) | −0.0017 (13) | −0.0007 (13) | 0.0004 (10) |
C30 | 0.026 (2) | 0.0211 (13) | 0.0181 (12) | −0.0007 (12) | 0.0015 (11) | 0.0022 (10) |
Fe1—N1 | 1.960 (2) | C8—H6 | 0.95 |
Fe1—N2 | 1.966 (2) | C9—C10 | 1.380 (3) |
Fe1—N3 | 1.964 (2) | C9—H7 | 0.95 |
Fe1—N4 | 1.975 (2) | C10—H8 | 0.95 |
Fe1—N5 | 1.950 (2) | C11—C12 | 1.378 (4) |
Fe1—N6 | 1.971 (2) | C11—H9 | 0.95 |
FE2—CL1 | 2.1880 (8) | C12—C13 | 1.382 (4) |
FE2—CL2 | 2.1978 (8) | C12—H1 | 0.95 |
FE2—CL3 | 2.2109 (8) | C13—C14 | 1.373 (4) |
FE2—CL4 | 2.1847 (7) | C13—H11 | 0.95 |
FE3—CL5 | 2.1793 (8) | C14—C15 | 1.379 (4) |
FE3—CL6 | 2.1962 (8) | C14—H12 | 0.95 |
FE3—CL7 | 2.2116 (8) | C15—C16 | 1.472 (4) |
FE3—CL8 | 2.1884 (9) | C16—C17 | 1.390 (4) |
N1—C1 | 1.353 (3) | C17—C18 | 1.377 (4) |
N1—C5 | 1.358 (3) | C17—H13 | 0.95 |
N2—C6 | 1.360 (3) | C18—C19 | 1.375 (4) |
N2—C10 | 1.347 (3) | C18—H14 | 0.95 |
N3—C11 | 1.345 (3) | C19—C20 | 1.390 (4) |
N3—C15 | 1.370 (3) | C19—H15 | 0.95 |
N4—C16 | 1.355 (3) | C20—H16 | 0.95 |
N4—C20 | 1.347 (3) | C21—C22 | 1.380 (4) |
N5—C21 | 1.345 (3) | C21—H17 | 0.95 |
N5—C25 | 1.361 (3) | C22—C23 | 1.375 (4) |
N6—C26 | 1.363 (4) | C22—H18 | 0.95 |
N6—C30 | 1.344 (3) | C23—C24 | 1.392 (4) |
C1—C2 | 1.381 (4) | C23—H19 | 0.95 |
C1—H10 | 0.95 | C24—C25 | 1.373 (4) |
C2—C3 | 1.376 (4) | C24—H20 | 0.95 |
C2—H2 | 0.95 | C25—C26 | 1.472 (4) |
C3—C4 | 1.380 (4) | C26—C27 | 1.387 (4) |
C3—H3 | 0.95 | C27—C28 | 1.387 (4) |
C4—C5 | 1.384 (3) | C27—H21 | 0.95 |
C4—H4 | 0.95 | C28—C29 | 1.378 (4) |
C5—C6 | 1.473 (3) | C28—H22 | 0.95 |
C6—C7 | 1.382 (3) | C29—C30 | 1.379 (4) |
C7—C8 | 1.379 (4) | C29—H23 | 0.95 |
C7—H5 | 0.95 | C30—H24 | 0.95 |
C8—C9 | 1.383 (4) | ||
Cl1···C4i | 3.345 (3) | Cl6···C24v | 3.295 (3) |
Cl1···C17ii | 3.549 (3) | Cl7···C23vi | 3.457 (3) |
Cl1···C3i | 3.599 (3) | Cl7···C9i | 3.568 (3) |
Cl2···C14iii | 3.472 (3) | Cl8···C11i | 3.454 (3) |
Cl3···C3iv | 3.576 (3) | C14···C14vii | 3.587 (6) |
Cl4···C21 | 3.459 (3) | C23···C27viii | 3.331 (4) |
Cl4···C1 | 3.566 (3) | C23···C28viii | 3.430 (4) |
Cl5···C7 | 3.452 (3) | C24···C27viii | 3.438 (4) |
Cl5···C28v | 3.515 (3) | ||
N1—Fe1—N2 | 81.53 (8) | C9—C8—H6 | 120.5 |
N1—Fe1—N3 | 88.31 (9) | C8—C9—C10 | 118.9 (2) |
N1—Fe1—N4 | 95.82 (8) | C8—C9—H7 | 120.6 |
N1—Fe1—N5 | 94.98 (9) | C10—C9—H7 | 120.6 |
N1—Fe1—N6 | 176.24 (9) | N2—C10—C9 | 123.0 (2) |
N2—Fe1—N3 | 97.13 (9) | N2—C10—H8 | 118.5 |
N2—Fe1—N4 | 177.18 (9) | C9—C10—H8 | 118.5 |
N2—Fe1—N5 | 88.07 (9) | N3—C11—C12 | 122.5 (3) |
N2—Fe1—N6 | 96.14 (8) | N3—C11—H9 | 118.7 |
N3—Fe1—N4 | 81.76 (9) | C12—C11—H9 | 118.7 |
N3—Fe1—N5 | 174.21 (9) | C11—C12—C13 | 119.0 (3) |
N3—Fe1—N6 | 94.92 (9) | C11—C12—H1 | 120.5 |
N4—Fe1—N5 | 93.16 (9) | C13—C12—H1 | 120.5 |
N4—Fe1—N6 | 86.55 (8) | C12—C13—C14 | 119.4 (3) |
N5—Fe1—N6 | 81.95 (9) | C12—C13—H11 | 120.3 |
CL1—FE2—CL2 | 108.31 (3) | C14—C13—H11 | 120.3 |
CL1—FE2—CL3 | 108.55 (3) | C13—C14—C15 | 119.5 (3) |
CL1—FE2—CL4 | 109.69 (3) | C13—C14—H12 | 120.2 |
CL2—FE2—CL3 | 112.29 (3) | C15—C14—H12 | 120.2 |
CL2—FE2—CL4 | 109.82 (3) | N3—C15—C14 | 121.5 (3) |
CL3—FE2—CL4 | 108.14 (3) | N3—C15—C16 | 113.3 (2) |
CL5—FE3—CL6 | 112.41 (3) | C14—C15—C16 | 125.1 (2) |
CL5—FE3—CL7 | 107.18 (4) | N4—C16—C15 | 114.4 (2) |
CL5—FE3—CL8 | 109.84 (4) | N4—C16—C17 | 121.7 (3) |
CL6—FE3—CL7 | 108.19 (3) | C15—C16—C17 | 123.9 (3) |
CL6—FE3—CL8 | 110.11 (4) | C16—C17—C18 | 119.3 (3) |
CL7—FE3—CL8 | 109.00 (3) | C16—C17—H13 | 120.4 |
Fe1—N1—C1 | 126.2 (2) | C18—C17—H13 | 120.4 |
Fe1—N1—C5 | 115.7 (2) | C17—C18—C19 | 119.6 (3) |
C1—N1—C5 | 118.1 (2) | C17—C18—H14 | 120.2 |
Fe1—N2—C6 | 115.4 (2) | C19—C18—H14 | 120.2 |
Fe1—N2—C10 | 126.7 (2) | C18—C19—C20 | 118.6 (3) |
C6—N2—C10 | 117.6 (2) | C18—C19—H15 | 120.7 |
Fe1—N3—C11 | 126.6 (2) | C20—C19—H15 | 120.7 |
Fe1—N3—C15 | 115.3 (2) | N4—C20—C19 | 122.6 (3) |
C11—N3—C15 | 118.0 (2) | N4—C20—H16 | 118.7 |
Fe1—N4—C16 | 114.9 (2) | C19—C20—H16 | 118.7 |
Fe1—N4—C20 | 126.7 (2) | N5—C21—C22 | 122.4 (3) |
C16—N4—C20 | 118.2 (2) | N5—C21—H17 | 118.8 |
Fe1—N5—C21 | 126.4 (2) | C22—C21—H17 | 118.8 |
Fe1—N5—C25 | 115.6 (2) | C21—C22—C23 | 119.5 (3) |
C21—N5—C25 | 118.0 (2) | C21—C22—H18 | 120.2 |
Fe1—N6—C26 | 114.1 (2) | C23—C22—H18 | 120.2 |
Fe1—N6—C30 | 127.5 (2) | C22—C23—C24 | 118.6 (3) |
C26—N6—C30 | 118.1 (2) | C22—C23—H19 | 120.7 |
N1—C1—C2 | 122.3 (2) | C24—C23—H19 | 120.7 |
N1—C1—H10 | 118.9 | C23—C24—C25 | 119.3 (3) |
C2—C1—H10 | 118.9 | C23—C24—H20 | 120.3 |
C1—C2—C3 | 119.2 (2) | C25—C24—H20 | 120.3 |
C1—C2—H2 | 120.4 | N5—C25—C24 | 122.1 (2) |
C3—C2—H2 | 120.4 | N5—C25—C26 | 113.4 (2) |
C2—C3—C4 | 119.4 (2) | C24—C25—C26 | 124.5 (2) |
C2—C3—H3 | 120.3 | N6—C26—C25 | 114.1 (2) |
C4—C3—H3 | 120.3 | N6—C26—C27 | 121.4 (2) |
C3—C4—C5 | 119.2 (2) | C25—C26—C27 | 124.5 (3) |
C3—C4—H4 | 120.4 | C26—C27—C28 | 119.8 (3) |
C5—C4—H4 | 120.4 | C26—C27—H21 | 120.1 |
N1—C5—C4 | 121.9 (2) | C28—C27—H21 | 120.1 |
N1—C5—C6 | 113.6 (2) | C27—C28—C29 | 118.4 (3) |
C4—C5—C6 | 124.5 (2) | C27—C28—H22 | 120.8 |
N2—C6—C5 | 113.6 (2) | C29—C28—H22 | 120.8 |
N2—C6—C7 | 122.1 (2) | C28—C29—C30 | 119.5 (3) |
C5—C6—C7 | 124.3 (2) | C28—C29—H23 | 120.2 |
C6—C7—C8 | 119.4 (2) | C30—C29—H23 | 120.2 |
C6—C7—H5 | 120.3 | N6—C30—C29 | 122.7 (3) |
C8—C7—H5 | 120.3 | N6—C30—H24 | 118.6 |
C7—C8—C9 | 119.0 (2) | C29—C30—H24 | 118.6 |
C7—C8—H6 | 120.5 | ||
Fe1—N1—C1—C2 | 176.6 (2) | N4—C16—C15—C14 | 175.6 (2) |
Fe1—N1—C5—C4 | −177.7 (2) | N4—C16—C17—C18 | 0.2 (4) |
Fe1—N1—C5—C6 | 2.0 (3) | N4—C20—C19—C18 | 0.8 (4) |
Fe1—N2—C6—C5 | 4.8 (3) | N5—Fe1—N1—C1 | 95.8 (2) |
Fe1—N2—C6—C7 | −173.8 (2) | N5—Fe1—N1—C5 | −86.9 (2) |
Fe1—N2—C10—C9 | 171.6 (2) | N5—Fe1—N2—C6 | 92.4 (2) |
Fe1—N3—C11—C12 | 177.5 (2) | N5—Fe1—N2—C10 | −80.6 (2) |
Fe1—N3—C15—C14 | −177.9 (2) | N5—Fe1—N3—C11 | 154.6 (7) |
Fe1—N3—C15—C16 | 2.8 (3) | N5—Fe1—N3—C15 | −28.9 (9) |
Fe1—N4—C16—C15 | 5.0 (3) | N5—Fe1—N4—C16 | 174.4 (2) |
Fe1—N4—C16—C17 | −175.6 (2) | N5—Fe1—N4—C20 | 0.2 (2) |
Fe1—N4—C20—C19 | 174.4 (2) | N5—Fe1—N6—C26 | −8.7 (2) |
Fe1—N5—C21—C22 | −177.8 (2) | N5—Fe1—N6—C30 | 178.1 (2) |
Fe1—N5—C25—C24 | 178.7 (2) | N5—C21—C22—C23 | −1.1 (4) |
Fe1—N5—C25—C26 | −1.6 (2) | N5—C25—C24—C23 | −0.2 (4) |
Fe1—N6—C26—C25 | 10.1 (3) | N5—C25—C26—N6 | −5.6 (3) |
Fe1—N6—C26—C27 | −169.9 (2) | N5—C25—C26—C27 | 174.4 (2) |
Fe1—N6—C30—C29 | 171.1 (2) | N6—Fe1—N1—C1 | 131 (1) |
N1—Fe1—N2—C6 | −2.9 (2) | N6—Fe1—N1—C5 | −52 (1) |
N1—Fe1—N2—C10 | −175.9 (2) | N6—Fe1—N2—C6 | 174.1 (2) |
N1—Fe1—N3—C11 | −80.6 (2) | N6—Fe1—N2—C10 | 1.1 (2) |
N1—Fe1—N3—C15 | 96.0 (2) | N6—Fe1—N3—C11 | 97.5 (2) |
N1—Fe1—N4—C16 | −90.2 (2) | N6—Fe1—N3—C15 | −85.9 (2) |
N1—Fe1—N4—C20 | 95.6 (2) | N6—Fe1—N4—C16 | 92.7 (2) |
N1—Fe1—N5—C21 | 1.8 (2) | N6—Fe1—N4—C20 | −81.5 (2) |
N1—Fe1—N5—C25 | −176.6 (2) | N6—Fe1—N5—C21 | −176.1 (2) |
N1—Fe1—N6—C26 | −44 (1) | N6—Fe1—N5—C25 | 5.6 (2) |
N1—Fe1—N6—C30 | 143 (1) | N6—C26—C25—C24 | 174.1 (2) |
N1—C1—C2—C3 | 0.2 (4) | N6—C26—C27—C28 | −3.2 (4) |
N1—C5—C4—C3 | 1.3 (4) | N6—C30—C29—C28 | −1.0 (4) |
N1—C5—C6—N2 | −4.4 (3) | C1—N1—C5—C4 | −0.1 (4) |
N1—C5—C6—C7 | 174.1 (3) | C1—N1—C5—C6 | 179.6 (2) |
N2—Fe1—N1—C1 | −177.0 (2) | C1—C2—C3—C4 | 1.0 (5) |
N2—Fe1—N1—C5 | 0.4 (2) | C2—C1—N1—C5 | −0.6 (4) |
N2—Fe1—N3—C11 | 0.7 (2) | C2—C3—C4—C5 | −1.7 (4) |
N2—Fe1—N3—C15 | 177.2 (2) | C3—C4—C5—C6 | −178.4 (3) |
N2—Fe1—N4—C16 | −70 (2) | C4—C5—C6—C7 | −6.2 (4) |
N2—Fe1—N4—C20 | 116 (2) | C5—C6—N2—C10 | 178.4 (2) |
N2—Fe1—N5—C21 | −79.6 (2) | C5—C6—C7—C8 | −177.5 (3) |
N2—Fe1—N5—C25 | 102.0 (2) | C6—N2—C10—C9 | −1.3 (4) |
N2—Fe1—N6—C26 | −95.8 (2) | C6—C7—C8—C9 | −0.2 (4) |
N2—Fe1—N6—C30 | 90.9 (2) | C7—C6—N2—C10 | −0.2 (4) |
N2—C6—C5—C4 | 175.3 (3) | C7—C8—C9—C10 | −1.1 (4) |
N2—C6—C7—C8 | 0.9 (4) | C11—N3—C15—C14 | −1.0 (4) |
N2—C10—C9—C8 | 1.9 (4) | C11—N3—C15—C16 | 179.7 (2) |
N3—Fe1—N1—C1 | −79.5 (2) | C11—C12—C13—C14 | 0.1 (4) |
N3—Fe1—N1—C5 | 97.8 (2) | C12—C11—N3—C15 | 1.0 (4) |
N3—Fe1—N2—C6 | −90.1 (2) | C12—C13—C14—C15 | −0.1 (4) |
N3—Fe1—N2—C10 | 96.9 (2) | C13—C14—C15—C16 | 179.8 (3) |
N3—Fe1—N4—C16 | −2.8 (2) | C14—C15—C16—C17 | −3.8 (4) |
N3—Fe1—N4—C20 | −177.0 (2) | C15—C16—N4—C20 | 179.8 (2) |
N3—Fe1—N5—C21 | 126.3 (8) | C15—C16—C17—C18 | 179.5 (3) |
N3—Fe1—N5—C25 | −52.1 (9) | C16—N4—C20—C19 | 0.4 (4) |
N3—Fe1—N6—C26 | 166.4 (2) | C16—C17—C18—C19 | 1.0 (5) |
N3—Fe1—N6—C30 | −6.8 (2) | C17—C16—N4—C20 | −0.9 (4) |
N3—C11—C12—C13 | −0.6 (4) | C17—C18—C19—C20 | −1.5 (4) |
N3—C15—C14—C13 | 0.5 (4) | C21—N5—C25—C24 | 0.2 (3) |
N3—C15—C16—N4 | −5.1 (3) | C21—N5—C25—C26 | 179.8 (2) |
N3—C15—C16—C17 | 175.5 (2) | C21—C22—C23—C24 | 1.0 (4) |
N4—Fe1—N1—C1 | 2.1 (2) | C22—C21—N5—C25 | 0.5 (4) |
N4—Fe1—N1—C5 | 179.4 (2) | C22—C23—C24—C25 | −0.3 (4) |
N4—Fe1—N2—C6 | −23 (2) | C23—C24—C25—C26 | −179.9 (2) |
N4—Fe1—N2—C10 | 164 (2) | C24—C25—C26—C27 | −6.0 (4) |
N4—Fe1—N3—C11 | −176.7 (2) | C25—C26—N6—C30 | −175.9 (2) |
N4—Fe1—N3—C15 | −0.2 (2) | C25—C26—C27—C28 | 176.8 (2) |
N4—Fe1—N5—C21 | 97.9 (2) | C26—N6—C30—C29 | −1.9 (4) |
N4—Fe1—N5—C25 | −80.5 (2) | C26—C27—C28—C29 | 0.2 (4) |
N4—Fe1—N6—C26 | 85.0 (2) | C27—C26—N6—C30 | 4.1 (3) |
N4—Fe1—N6—C30 | −88.2 (2) | C27—C28—C29—C30 | 1.9 (4) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y−1/2, z−1/2; (iv) −x+1, y−1/2, −z+3/2; (v) x, y+1, z; (vi) −x+2, y+1/2, −z+3/2; (vii) −x+1, −y, −z+2; (viii) −x+2, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C10H8N2)3][FeCl4]2 |
Mr | 919.72 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 18.6108 (4), 10.7729 (2), 18.5661 (6) |
β (°) | 100.381 (2) |
V (Å3) | 3661.43 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.79 |
Crystal size (mm) | 0.35 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer |
Absorption correction | Multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.600, 0.699 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 50254, 10556, 6113 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.072, 0.92 |
No. of reflections | 6113 |
No. of parameters | 424 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.55 |
Computer programs: COLLECT (Nonius 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), TEXSAN for Windows.
Fe1—N1 | 1.960 (2) | FE2—CL2 | 2.1978 (8) |
Fe1—N2 | 1.966 (2) | FE2—CL3 | 2.2109 (8) |
Fe1—N3 | 1.964 (2) | FE2—CL4 | 2.1847 (7) |
Fe1—N4 | 1.975 (2) | FE3—CL5 | 2.1793 (8) |
Fe1—N5 | 1.950 (2) | FE3—CL6 | 2.1962 (8) |
Fe1—N6 | 1.971 (2) | FE3—CL7 | 2.2116 (8) |
FE2—CL1 | 2.1880 (8) | FE3—CL8 | 2.1884 (9) |
N1—Fe1—N2 | 81.53 (8) | N2—Fe1—N6 | 96.14 (8) |
N1—Fe1—N3 | 88.31 (9) | N3—Fe1—N4 | 81.76 (9) |
N1—Fe1—N4 | 95.82 (8) | N3—Fe1—N5 | 174.21 (9) |
N1—Fe1—N5 | 94.98 (9) | N3—Fe1—N6 | 94.92 (9) |
N1—Fe1—N6 | 176.24 (9) | N4—Fe1—N5 | 93.16 (9) |
N2—Fe1—N3 | 97.13 (9) | N4—Fe1—N6 | 86.55 (8) |
N2—Fe1—N4 | 177.18 (9) | N5—Fe1—N6 | 81.95 (9) |
N2—Fe1—N5 | 88.07 (9) |
We are currently interested in the relationship between the structure of paramagnetic metal complexes and the paramagnetically shifted nuclear magnetic resonance spectra of these complexes (Ariyananda, L. M. D. & Norman, R. E., unpublished results). During an attempt to synthesize a bis(2,2'-bipyridyl)dichloroiron(III) complex as an example of a d5 cationic species, the title complex, (I), was produced.
The title complex consists of a pseudo-octahedral low-spin iron(II) complex and two tetrachloroferrate(III) anions. Given the eight chlorides charge neutrality requires the presence of one iron(II) and two iron(III) centers. The metrical parameters within the tris(2,2'-bipyridyl)iron(II) cation are typical for iron(II), with an average Fe—N distance of 1.964 (2) Å and an average `bite' angle of 81.75 (5)° (Batten et al., 2000; Decurtins et al., 1993). The metrical parameters within the 2,2'-bipyridyl unit are unremarkable. The identity as iron(II) is confirmed by the Fe—N distances and by the NMR spectrum (see Experimental), since the resonances, while broadened, are not paramagnetically shifted. The metrical parameters within the approximately tetrahedral tetrachloroferrate(III) ions are also typical, with an average Fe—Cl distance of 2.1946 (1) Å; the reported average for 97 structures is 2.18 (1) Å (Cotton et al., 1998, and references therein). Fe—Cl distances for [FeCl4]2− anions are typically longer than 2.3 Å (Alcock et al., 1999).