Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005918/bt6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005918/bt6032Isup2.hkl |
CCDC reference: 165627
H atoms were kept in calculated positions (C—H = 0.95 Å) with Uiso = 1.2Ueq for the atom to which they are attached.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.
Fig. 1. View of [Fe(bipy)2(CN)2](NO3) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability level and H atoms are drawn as small circles of arbitrary radius. |
[Fe(C10H8N2)2(CN)2](NO3) | F(000) = 988.0 |
Mr = 482.28 | Dx = 1.567 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8263 reflections |
a = 10.7902 (6) Å | θ = 2.1–29.8° |
b = 11.7031 (6) Å | µ = 0.78 mm−1 |
c = 16.1857 (9) Å | T = 120 K |
V = 2043.9 (1) Å3 | Block, red |
Z = 4 | 0.40 × 0.34 × 0.34 mm |
Siemens SMART CCD diffractometer | 5807 independent reflections |
Radiation source: x-ray tube | 4302 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.058 |
ω rotation scans with narrow frames | θmax = 29.8°, θmin = 2.1° |
Absorption correction: integration (XPREP; Siemens, 1995) | h = −14→15 |
Tmin = 0.718, Tmax = 0.836 | k = −15→14 |
19837 measured reflections | l = −19→21 |
Refinement on F | H-atom parameters constrained |
Least-squares matrix: full | w = 1/{[σcs(F2) + 1.03F2]1/2-|F|}2 |
R[F2 > 2σ(F2)] = 0.031 | (Δ/σ)max = 0.001 |
wR(F2) = 0.038 | Δρmax = 0.80 (8) e Å−3 |
S = 1.20 | Δρmin = −0.64 (8) e Å−3 |
4302 reflections | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
300 parameters | Extinction coefficient: 24 (8) |
0 restraints | Absolute structure: 1815 Friedel pairs (84%) |
0 constraints | Rogers parameter: 1.02 (3) |
[Fe(C10H8N2)2(CN)2](NO3) | V = 2043.9 (1) Å3 |
Mr = 482.28 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.7902 (6) Å | µ = 0.78 mm−1 |
b = 11.7031 (6) Å | T = 120 K |
c = 16.1857 (9) Å | 0.40 × 0.34 × 0.34 mm |
Siemens SMART CCD diffractometer | 5807 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1995) | 4302 reflections with I > 3σ(I) |
Tmin = 0.718, Tmax = 0.836 | Rint = 0.058 |
19837 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.038 | Δρmax = 0.80 (8) e Å−3 |
S = 1.20 | Δρmin = −0.64 (8) e Å−3 |
4302 reflections | Absolute structure: 1815 Friedel pairs (84%) |
300 parameters | Rogers parameter: 1.02 (3) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Fe | 0.49538 (3) | 0.22630 (3) | 0.62687 (2) | 0.0168 (1) | |
O1 | 0.5776 (2) | −0.1398 (2) | 0.4201 (1) | 0.044 (1) | |
O2 | 0.4937 (2) | −0.2940 (1) | 0.3758 (1) | 0.048 (1) | |
O3 | 0.4399 (2) | −0.1339 (2) | 0.3224 (1) | 0.044 (1) | |
N1 | 0.4888 (2) | 0.2189 (2) | 0.7479 (1) | 0.020 (1) | |
N2 | 0.6404 (2) | 0.1270 (2) | 0.6454 (1) | 0.019 (1) | |
N3 | 0.3930 (2) | 0.0895 (2) | 0.6065 (1) | 0.018 (1) | |
N4 | 0.5049 (2) | 0.2250 (2) | 0.5062 (1) | 0.018 (1) | |
N5 | 0.2773 (2) | 0.3905 (2) | 0.6018 (1) | 0.024 (1) | |
N6 | 0.6502 (2) | 0.4433 (2) | 0.6509 (1) | 0.027 (1) | |
N7 | 0.5029 (2) | −0.1892 (2) | 0.3723 (1) | 0.028 (1) | |
C1 | 0.4020 (2) | 0.2661 (2) | 0.7959 (2) | 0.027 (1) | |
C2 | 0.4070 (3) | 0.2606 (2) | 0.8808 (2) | 0.029 (1) | |
C3 | 0.5053 (3) | 0.2051 (2) | 0.9179 (1) | 0.027 (1) | |
C4 | 0.5949 (2) | 0.1555 (2) | 0.8687 (2) | 0.023 (1) | |
C5 | 0.5848 (2) | 0.1635 (2) | 0.7837 (2) | 0.020 (1) | |
C6 | 0.6728 (2) | 0.1131 (2) | 0.7254 (1) | 0.018 (1) | |
C7 | 0.7779 (2) | 0.0543 (2) | 0.7481 (2) | 0.023 (1) | |
C8 | 0.8487 (2) | 0.0046 (2) | 0.6867 (2) | 0.024 (1) | |
C9 | 0.8142 (2) | 0.0150 (2) | 0.6060 (2) | 0.025 (1) | |
C10 | 0.7092 (2) | 0.0782 (2) | 0.5865 (2) | 0.024 (1) | |
C11 | 0.3366 (2) | 0.0256 (2) | 0.6645 (2) | 0.023 (1) | |
C12 | 0.2670 (2) | −0.0687 (2) | 0.6441 (2) | 0.025 (1) | |
C13 | 0.2556 (2) | −0.0994 (2) | 0.5621 (2) | 0.024 (1) | |
C14 | 0.3151 (2) | −0.0353 (2) | 0.5021 (2) | 0.022 (1) | |
C15 | 0.3824 (2) | 0.0594 (2) | 0.5258 (1) | 0.020 (1) | |
C16 | 0.4445 (2) | 0.1375 (2) | 0.4687 (1) | 0.018 (1) | |
C17 | 0.4414 (2) | 0.1270 (2) | 0.3837 (2) | 0.021 (1) | |
C18 | 0.4979 (3) | 0.2090 (2) | 0.3360 (1) | 0.023 (1) | |
C19 | 0.5576 (2) | 0.2980 (2) | 0.3745 (2) | 0.022 (1) | |
C20 | 0.5602 (2) | 0.3038 (2) | 0.4587 (2) | 0.021 (1) | |
C21 | 0.3578 (2) | 0.3289 (2) | 0.6129 (1) | 0.019 (1) | |
C22 | 0.5937 (2) | 0.3617 (2) | 0.6417 (1) | 0.020 (1) | |
H1 | 0.3345 | 0.3047 | 0.7706 | 0.032* | |
H2 | 0.3437 | 0.2946 | 0.9134 | 0.034* | |
H3 | 0.5112 | 0.2012 | 0.9764 | 0.033* | |
H4 | 0.6628 | 0.1163 | 0.8929 | 0.027* | |
H7 | 0.8011 | 0.0480 | 0.8045 | 0.027* | |
H8 | 0.9216 | −0.0368 | 0.7007 | 0.029* | |
H9 | 0.8614 | −0.0206 | 0.5636 | 0.030* | |
H10 | 0.6859 | 0.0869 | 0.5303 | 0.028* | |
H11 | 0.3451 | 0.0461 | 0.7210 | 0.028* | |
H12 | 0.2271 | −0.1122 | 0.6860 | 0.030* | |
H13 | 0.2074 | −0.1641 | 0.5470 | 0.029* | |
H14 | 0.3096 | −0.0563 | 0.4455 | 0.026* | |
H17 | 0.4007 | 0.0640 | 0.3585 | 0.026* | |
H18 | 0.4957 | 0.2042 | 0.2774 | 0.028* | |
H19 | 0.5971 | 0.3555 | 0.3425 | 0.027* | |
H20 | 0.6025 | 0.3655 | 0.4844 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0187 (1) | 0.0171 (1) | 0.0148 (1) | 0.0010 (2) | 0.0002 (2) | 0.0000 (1) |
O1 | 0.051 (1) | 0.048 (1) | 0.034 (1) | −0.019 (1) | 0.000 (1) | 0.000 (1) |
O2 | 0.090 (2) | 0.022 (1) | 0.031 (1) | −0.003 (1) | −0.010 (2) | −0.001 (1) |
O3 | 0.065 (1) | 0.038 (1) | 0.028 (1) | 0.025 (1) | −0.005 (1) | −0.003 (1) |
N1 | 0.025 (1) | 0.018 (1) | 0.017 (1) | −0.001 (1) | −0.001 (1) | −0.002 (1) |
N2 | 0.021 (1) | 0.018 (1) | 0.017 (1) | 0.000 (1) | −0.001 (1) | 0.002 (1) |
N3 | 0.019 (1) | 0.017 (1) | 0.018 (1) | 0.002 (1) | −0.002 (1) | 0.002 (1) |
N4 | 0.018 (1) | 0.017 (1) | 0.018 (1) | 0.003 (1) | −0.002 (1) | 0.001 (1) |
N5 | 0.026 (1) | 0.027 (1) | 0.020 (1) | 0.003 (1) | −0.001 (1) | −0.003 (1) |
N6 | 0.032 (1) | 0.029 (1) | 0.021 (1) | −0.005 (1) | 0.002 (1) | −0.004 (1) |
N7 | 0.035 (1) | 0.026 (1) | 0.022 (1) | 0.001 (1) | 0.012 (1) | 0.000 (1) |
C1 | 0.031 (1) | 0.026 (1) | 0.023 (1) | 0.006 (1) | 0.003 (1) | −0.001 (1) |
C2 | 0.040 (1) | 0.026 (1) | 0.020 (1) | 0.004 (1) | 0.007 (1) | −0.003 (1) |
C3 | 0.040 (1) | 0.026 (1) | 0.016 (1) | −0.005 (1) | 0.002 (1) | −0.001 (1) |
C4 | 0.028 (1) | 0.019 (1) | 0.021 (1) | −0.002 (1) | −0.001 (1) | 0.001 (1) |
C5 | 0.023 (1) | 0.015 (1) | 0.021 (1) | −0.004 (1) | 0.000 (1) | 0.001 (1) |
C6 | 0.020 (1) | 0.016 (1) | 0.019 (1) | −0.005 (1) | 0.000 (1) | 0.000 (1) |
C7 | 0.023 (1) | 0.022 (1) | 0.023 (1) | −0.003 (1) | −0.003 (1) | 0.003 (1) |
C8 | 0.019 (1) | 0.022 (1) | 0.032 (1) | 0.003 (1) | 0.000 (1) | 0.004 (1) |
C9 | 0.025 (1) | 0.025 (1) | 0.025 (1) | 0.003 (1) | 0.003 (1) | −0.002 (1) |
C10 | 0.026 (1) | 0.025 (1) | 0.021 (1) | 0.000 (1) | 0.001 (1) | 0.001 (1) |
C11 | 0.023 (1) | 0.024 (1) | 0.022 (1) | 0.003 (1) | −0.001 (1) | 0.003 (1) |
C12 | 0.027 (1) | 0.021 (1) | 0.028 (2) | −0.002 (1) | 0.002 (1) | 0.005 (1) |
C13 | 0.024 (1) | 0.020 (1) | 0.029 (1) | −0.004 (1) | −0.005 (1) | 0.001 (1) |
C14 | 0.024 (1) | 0.021 (1) | 0.021 (1) | 0.002 (1) | −0.004 (1) | −0.001 (1) |
C15 | 0.018 (1) | 0.019 (1) | 0.021 (1) | 0.004 (1) | −0.001 (1) | 0.001 (1) |
C16 | 0.017 (1) | 0.017 (1) | 0.019 (1) | 0.002 (1) | −0.002 (1) | −0.001 (1) |
C17 | 0.026 (1) | 0.020 (1) | 0.019 (1) | 0.001 (1) | −0.002 (1) | −0.002 (1) |
C18 | 0.027 (1) | 0.027 (1) | 0.016 (1) | 0.003 (1) | 0.004 (1) | −0.001 (1) |
C19 | 0.022 (1) | 0.024 (1) | 0.021 (1) | 0.002 (1) | 0.003 (1) | 0.006 (1) |
C20 | 0.021 (1) | 0.019 (1) | 0.022 (1) | 0.000 (1) | 0.000 (1) | 0.000 (1) |
C21 | 0.024 (1) | 0.018 (1) | 0.013 (1) | −0.004 (1) | 0.001 (1) | −0.003 (1) |
C22 | 0.020 (1) | 0.023 (1) | 0.017 (1) | 0.004 (1) | −0.001 (1) | −0.001 (1) |
Fe—C21 | 1.923 (2) | C9—C10 | 1.389 (4) |
Fe—C22 | 1.922 (3) | C11—C12 | 1.375 (3) |
Fe—N1 | 1.962 (2) | C12—C13 | 1.380 (4) |
Fe—N2 | 1.972 (2) | C13—C14 | 1.385 (4) |
Fe—N3 | 1.973 (2) | C14—C15 | 1.379 (3) |
Fe—N4 | 1.955 (2) | C15—C16 | 1.462 (3) |
O1—N7 | 1.258 (3) | C16—C17 | 1.382 (3) |
O2—N7 | 1.232 (3) | C17—C18 | 1.374 (3) |
O3—N7 | 1.238 (3) | C18—C19 | 1.374 (3) |
N1—C1 | 1.337 (3) | C19—C20 | 1.365 (4) |
N1—C5 | 1.352 (3) | C1—H1 | 0.95 |
N2—C10 | 1.336 (3) | C2—H2 | 0.95 |
N2—C6 | 1.352 (3) | C3—H3 | 0.95 |
N3—C11 | 1.345 (3) | C4—H4 | 0.95 |
N3—C15 | 1.359 (3) | C7—H7 | 0.95 |
N4—C20 | 1.342 (3) | C8—H8 | 0.95 |
N4—C16 | 1.358 (3) | C9—H9 | 0.95 |
N5—C21 | 1.143 (3) | C10—H10 | 0.95 |
N6—C22 | 1.143 (3) | C11—H11 | 0.95 |
C1—C2 | 1.375 (4) | C12—H12 | 0.95 |
C2—C3 | 1.382 (4) | C13—H13 | 0.95 |
C3—C4 | 1.381 (4) | C14—H14 | 0.95 |
C4—C5 | 1.383 (3) | C17—H17 | 0.95 |
C5—C6 | 1.463 (3) | C18—H18 | 0.95 |
C6—C7 | 1.376 (3) | C19—H19 | 0.95 |
C7—C8 | 1.382 (4) | C20—H20 | 0.95 |
C8—C9 | 1.364 (4) | ||
C21—Fe—C22 | 85.8 (1) | N3—C11—C12 | 121.7 (2) |
N4—Fe—C22 | 95.89 (9) | C11—C12—C13 | 119.3 (2) |
N1—Fe—C22 | 86.07 (9) | C12—C13—C14 | 119.4 (2) |
N2—Fe—C22 | 91.66 (9) | C13—C14—C15 | 119.0 (2) |
N3—Fe—C22 | 177.47 (9) | N3—C15—C14 | 121.3 (2) |
N4—Fe—C21 | 85.86 (9) | N3—C15—C16 | 114.0 (2) |
N1—Fe—C21 | 96.74 (9) | C14—C15—C16 | 124.6 (2) |
N2—Fe—C21 | 176.95 (9) | N4—C16—C17 | 121.6 (2) |
N3—Fe—C21 | 93.15 (9) | N4—C16—C15 | 114.1 (2) |
N1—Fe—N4 | 176.87 (8) | C15—C16—C17 | 124.3 (2) |
N2—Fe—N4 | 96.05 (8) | C16—C17—C18 | 119.1 (2) |
N3—Fe—N4 | 81.74 (8) | C17—C18—C19 | 118.9 (2) |
N1—Fe—N2 | 81.43 (8) | C18—C19—C20 | 120.0 (2) |
N1—Fe—N3 | 96.34 (8) | N4—C20—C19 | 122.0 (2) |
N2—Fe—N3 | 89.49 (8) | N1—C1—H1 | 118.9 |
Fe—N1—C1 | 126.0 (2) | C2—C1—H1 | 118.9 |
Fe—N1—C5 | 114.9 (2) | C1—C2—H2 | 120.4 |
Fe—N2—C10 | 125.8 (2) | C3—C2—H2 | 120.4 |
Fe—N2—C6 | 114.9 (2) | C4—C3—H3 | 120.6 |
Fe—N3—C11 | 126.0 (2) | C2—C3—H3 | 120.5 |
Fe—N3—C15 | 114.7 (2) | C3—C4—H4 | 120.3 |
Fe—N4—C20 | 126.2 (2) | C5—C4—H4 | 120.3 |
Fe—N4—C16 | 115.4 (2) | C6—C7—H7 | 120.8 |
Fe—C21—N5 | 177.6 (2) | C8—C7—H7 | 120.8 |
Fe—C22—N6 | 178.7 (2) | C9—C8—H8 | 120.0 |
C1—N1—C5 | 119.1 (2) | C7—C8—H8 | 120.0 |
C6—N2—C10 | 119.2 (2) | C8—C9—H9 | 120.4 |
C11—N3—C15 | 119.2 (2) | C10—C9—H9 | 120.4 |
C16—N4—C20 | 118.3 (2) | N2—C10—H10 | 119.3 |
O2—N7—O3 | 120.4 (3) | C9—C10—H10 | 119.4 |
O1—N7—O2 | 118.7 (2) | N3—C11—H11 | 119.2 |
O1—N7—O3 | 120.8 (2) | C12—C11—H11 | 119.1 |
N1—C1—C2 | 122.3 (2) | C11—C12—H12 | 120.4 |
C1—C2—C3 | 119.1 (2) | C13—C12—H12 | 120.3 |
C2—C3—C4 | 118.9 (2) | C12—C13—H13 | 120.3 |
C3—C4—C5 | 119.4 (2) | C14—C13—H13 | 120.3 |
N1—C5—C4 | 121.3 (2) | C15—C14—H14 | 120.5 |
N1—C5—C6 | 114.5 (2) | C13—C14—H14 | 120.5 |
C4—C5—C6 | 124.3 (2) | C18—C17—H17 | 120.4 |
N2—C6—C7 | 121.9 (2) | C16—C17—H17 | 120.5 |
N2—C6—C5 | 113.7 (2) | C19—C18—H18 | 120.6 |
C5—C6—C7 | 124.4 (2) | C17—C18—H18 | 120.5 |
C6—C7—C8 | 118.4 (2) | C20—C19—H19 | 120.0 |
C7—C8—C9 | 120.0 (2) | C18—C19—H19 | 120.0 |
C8—C9—C10 | 119.2 (2) | N4—C20—H20 | 119.0 |
N2—C10—C9 | 121.3 (2) | C19—C20—H20 | 119.0 |
N1—C5—C6—N2 | −2.4 (3) | N3—C15—C16—N4 | 1.6 (3) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C10H8N2)2(CN)2](NO3) |
Mr | 482.28 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 10.7902 (6), 11.7031 (6), 16.1857 (9) |
V (Å3) | 2043.9 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.40 × 0.34 × 0.34 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Integration (XPREP; Siemens, 1995) |
Tmin, Tmax | 0.718, 0.836 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 19837, 5807, 4302 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.038, 1.20 |
No. of reflections | 4302 |
No. of parameters | 300 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80 (8), −0.64 (8) |
Absolute structure | 1815 Friedel pairs (84%) |
Rogers parameter | 1.02 (3) |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995), modified ORFLS (Busing et al., 1962) and KRYSTAL, ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.
Fe—C21 | 1.923 (2) | Fe—N2 | 1.972 (2) |
Fe—C22 | 1.922 (3) | Fe—N3 | 1.973 (2) |
Fe—N1 | 1.962 (2) | Fe—N4 | 1.955 (2) |
C21—Fe—C22 | 85.8 (1) | N3—Fe—C21 | 93.15 (9) |
N4—Fe—C22 | 95.89 (9) | N1—Fe—N4 | 176.87 (8) |
N1—Fe—C22 | 86.07 (9) | N2—Fe—N4 | 96.05 (8) |
N2—Fe—C22 | 91.66 (9) | N3—Fe—N4 | 81.74 (8) |
N3—Fe—C22 | 177.47 (9) | N1—Fe—N2 | 81.43 (8) |
N4—Fe—C21 | 85.86 (9) | N1—Fe—N3 | 96.34 (8) |
N1—Fe—C21 | 96.74 (9) | N2—Fe—N3 | 89.49 (8) |
N2—Fe—C21 | 176.95 (9) |
During an investigation of reactions between iron diimine complexes and the hexacyanoferrate anion, we prepared the title compound, [Fe(bipy)2(CN)2](NO3) (bipy is 2,2'-bipyridine), (I), and determined its crystal structure.
The Fe atom is octahedrally coordinated to the N atoms of the bipyridines and to the C atoms of the cyanide groups, which are cis to each other. The Fe—C distances are 1.922 (3) and 1.923 (2) Å, and the Fe—N bonds trans to CN are 1.972 (2) and 1.973 (2) Å and are longer than those cis to the CN groups, viz. 1.955 (2) and 1.962 (2) Å. The bipyridine groups are close to being planar, with N—C—C—N torsion angles of -2.4 (3) and 1.6 (3)°, and bite angles of 81.43 (8) and 81.74 (8)°. The bond distances are very similar to those found for the corresponding perchlorate complex (Lu et al., 1988), i.e. Fe—C 1.928 (7) and 1.931 (7) Å, Fe—N(trans to CN) 1.993 (5) and 1.988 (5) Å, and Fe—N(cis to CN) 1.955 (4) and 1.972 (4) Å. The two compounds have the same space group and very similar cell dimensions.