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The Fe atom of the title compound, [Fe(bipy)2(CN)2](NO3) (bipy is 2,2'-bi­pyridine, C10H8N2), 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)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005918/bt6032sup1.cif
Contains datablocks bipy, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005918/bt6032Isup2.hkl
Contains datablock I

CCDC reference: 165627

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.031
  • wR factor = 0.038
  • Data-to-parameter ratio = 14.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_030 Alert C Refined Extinction parameter within range .... 3.00 Sigma General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.80 From the CIF: _reflns_number_total 5807 Count of symmetry unique reflns 3288 Completeness (_total/calc) 176.61% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2519 Fraction of Friedel pairs measured 0.766 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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.

Experimental top

The title compound was prepared as described by Schilt (1960).

Refinement top

H atoms were kept in calculated positions (C—H = 0.95 Å) with Uiso = 1.2Ueq for the atom to which they are attached.

Computing details top

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.

Figures top
[Figure 1] 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.
bis(2,2'-bipyridine-N,N')-dicyano-iron(III) nitrate top
Crystal data top
[Fe(C10H8N2)2(CN)2](NO3)F(000) = 988.0
Mr = 482.28Dx = 1.567 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 8263 reflections
a = 10.7902 (6) Åθ = 2.1–29.8°
b = 11.7031 (6) ŵ = 0.78 mm1
c = 16.1857 (9) ÅT = 120 K
V = 2043.9 (1) Å3Block, red
Z = 40.40 × 0.34 × 0.34 mm
Data collection top
Siemens SMART CCD
diffractometer
5807 independent reflections
Radiation source: x-ray tube4302 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.058
ω rotation scans with narrow framesθmax = 29.8°, θmin = 2.1°
Absorption correction: integration
(XPREP; Siemens, 1995)
h = 1415
Tmin = 0.718, Tmax = 0.836k = 1514
19837 measured reflectionsl = 1921
Refinement top
Refinement on FH-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) = 0.038Δρmax = 0.80 (8) e Å3
S = 1.20Δρmin = 0.64 (8) e Å3
4302 reflectionsExtinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974)
300 parametersExtinction coefficient: 24 (8)
0 restraintsAbsolute structure: 1815 Friedel pairs (84%)
0 constraintsRogers parameter: 1.02 (3)
Crystal data top
[Fe(C10H8N2)2(CN)2](NO3)V = 2043.9 (1) Å3
Mr = 482.28Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.7902 (6) ŵ = 0.78 mm1
b = 11.7031 (6) ÅT = 120 K
c = 16.1857 (9) Å0.40 × 0.34 × 0.34 mm
Data collection top
Siemens SMART CCD
diffractometer
5807 independent reflections
Absorption correction: integration
(XPREP; Siemens, 1995)
4302 reflections with I > 3σ(I)
Tmin = 0.718, Tmax = 0.836Rint = 0.058
19837 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.038Δρmax = 0.80 (8) e Å3
S = 1.20Δρmin = 0.64 (8) e Å3
4302 reflectionsAbsolute structure: 1815 Friedel pairs (84%)
300 parametersRogers parameter: 1.02 (3)
0 restraints
Special details top

Refinement. Sfls: F calc weight full matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe0.49538 (3)0.22630 (3)0.62687 (2)0.0168 (1)
O10.5776 (2)0.1398 (2)0.4201 (1)0.044 (1)
O20.4937 (2)0.2940 (1)0.3758 (1)0.048 (1)
O30.4399 (2)0.1339 (2)0.3224 (1)0.044 (1)
N10.4888 (2)0.2189 (2)0.7479 (1)0.020 (1)
N20.6404 (2)0.1270 (2)0.6454 (1)0.019 (1)
N30.3930 (2)0.0895 (2)0.6065 (1)0.018 (1)
N40.5049 (2)0.2250 (2)0.5062 (1)0.018 (1)
N50.2773 (2)0.3905 (2)0.6018 (1)0.024 (1)
N60.6502 (2)0.4433 (2)0.6509 (1)0.027 (1)
N70.5029 (2)0.1892 (2)0.3723 (1)0.028 (1)
C10.4020 (2)0.2661 (2)0.7959 (2)0.027 (1)
C20.4070 (3)0.2606 (2)0.8808 (2)0.029 (1)
C30.5053 (3)0.2051 (2)0.9179 (1)0.027 (1)
C40.5949 (2)0.1555 (2)0.8687 (2)0.023 (1)
C50.5848 (2)0.1635 (2)0.7837 (2)0.020 (1)
C60.6728 (2)0.1131 (2)0.7254 (1)0.018 (1)
C70.7779 (2)0.0543 (2)0.7481 (2)0.023 (1)
C80.8487 (2)0.0046 (2)0.6867 (2)0.024 (1)
C90.8142 (2)0.0150 (2)0.6060 (2)0.025 (1)
C100.7092 (2)0.0782 (2)0.5865 (2)0.024 (1)
C110.3366 (2)0.0256 (2)0.6645 (2)0.023 (1)
C120.2670 (2)0.0687 (2)0.6441 (2)0.025 (1)
C130.2556 (2)0.0994 (2)0.5621 (2)0.024 (1)
C140.3151 (2)0.0353 (2)0.5021 (2)0.022 (1)
C150.3824 (2)0.0594 (2)0.5258 (1)0.020 (1)
C160.4445 (2)0.1375 (2)0.4687 (1)0.018 (1)
C170.4414 (2)0.1270 (2)0.3837 (2)0.021 (1)
C180.4979 (3)0.2090 (2)0.3360 (1)0.023 (1)
C190.5576 (2)0.2980 (2)0.3745 (2)0.022 (1)
C200.5602 (2)0.3038 (2)0.4587 (2)0.021 (1)
C210.3578 (2)0.3289 (2)0.6129 (1)0.019 (1)
C220.5937 (2)0.3617 (2)0.6417 (1)0.020 (1)
H10.33450.30470.77060.032*
H20.34370.29460.91340.034*
H30.51120.20120.97640.033*
H40.66280.11630.89290.027*
H70.80110.04800.80450.027*
H80.92160.03680.70070.029*
H90.86140.02060.56360.030*
H100.68590.08690.53030.028*
H110.34510.04610.72100.028*
H120.22710.11220.68600.030*
H130.20740.16410.54700.029*
H140.30960.05630.44550.026*
H170.40070.06400.35850.026*
H180.49570.20420.27740.028*
H190.59710.35550.34250.027*
H200.60250.36550.48440.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0187 (1)0.0171 (1)0.0148 (1)0.0010 (2)0.0002 (2)0.0000 (1)
O10.051 (1)0.048 (1)0.034 (1)0.019 (1)0.000 (1)0.000 (1)
O20.090 (2)0.022 (1)0.031 (1)0.003 (1)0.010 (2)0.001 (1)
O30.065 (1)0.038 (1)0.028 (1)0.025 (1)0.005 (1)0.003 (1)
N10.025 (1)0.018 (1)0.017 (1)0.001 (1)0.001 (1)0.002 (1)
N20.021 (1)0.018 (1)0.017 (1)0.000 (1)0.001 (1)0.002 (1)
N30.019 (1)0.017 (1)0.018 (1)0.002 (1)0.002 (1)0.002 (1)
N40.018 (1)0.017 (1)0.018 (1)0.003 (1)0.002 (1)0.001 (1)
N50.026 (1)0.027 (1)0.020 (1)0.003 (1)0.001 (1)0.003 (1)
N60.032 (1)0.029 (1)0.021 (1)0.005 (1)0.002 (1)0.004 (1)
N70.035 (1)0.026 (1)0.022 (1)0.001 (1)0.012 (1)0.000 (1)
C10.031 (1)0.026 (1)0.023 (1)0.006 (1)0.003 (1)0.001 (1)
C20.040 (1)0.026 (1)0.020 (1)0.004 (1)0.007 (1)0.003 (1)
C30.040 (1)0.026 (1)0.016 (1)0.005 (1)0.002 (1)0.001 (1)
C40.028 (1)0.019 (1)0.021 (1)0.002 (1)0.001 (1)0.001 (1)
C50.023 (1)0.015 (1)0.021 (1)0.004 (1)0.000 (1)0.001 (1)
C60.020 (1)0.016 (1)0.019 (1)0.005 (1)0.000 (1)0.000 (1)
C70.023 (1)0.022 (1)0.023 (1)0.003 (1)0.003 (1)0.003 (1)
C80.019 (1)0.022 (1)0.032 (1)0.003 (1)0.000 (1)0.004 (1)
C90.025 (1)0.025 (1)0.025 (1)0.003 (1)0.003 (1)0.002 (1)
C100.026 (1)0.025 (1)0.021 (1)0.000 (1)0.001 (1)0.001 (1)
C110.023 (1)0.024 (1)0.022 (1)0.003 (1)0.001 (1)0.003 (1)
C120.027 (1)0.021 (1)0.028 (2)0.002 (1)0.002 (1)0.005 (1)
C130.024 (1)0.020 (1)0.029 (1)0.004 (1)0.005 (1)0.001 (1)
C140.024 (1)0.021 (1)0.021 (1)0.002 (1)0.004 (1)0.001 (1)
C150.018 (1)0.019 (1)0.021 (1)0.004 (1)0.001 (1)0.001 (1)
C160.017 (1)0.017 (1)0.019 (1)0.002 (1)0.002 (1)0.001 (1)
C170.026 (1)0.020 (1)0.019 (1)0.001 (1)0.002 (1)0.002 (1)
C180.027 (1)0.027 (1)0.016 (1)0.003 (1)0.004 (1)0.001 (1)
C190.022 (1)0.024 (1)0.021 (1)0.002 (1)0.003 (1)0.006 (1)
C200.021 (1)0.019 (1)0.022 (1)0.000 (1)0.000 (1)0.000 (1)
C210.024 (1)0.018 (1)0.013 (1)0.004 (1)0.001 (1)0.003 (1)
C220.020 (1)0.023 (1)0.017 (1)0.004 (1)0.001 (1)0.001 (1)
Geometric parameters (Å, º) top
Fe—C211.923 (2)C9—C101.389 (4)
Fe—C221.922 (3)C11—C121.375 (3)
Fe—N11.962 (2)C12—C131.380 (4)
Fe—N21.972 (2)C13—C141.385 (4)
Fe—N31.973 (2)C14—C151.379 (3)
Fe—N41.955 (2)C15—C161.462 (3)
O1—N71.258 (3)C16—C171.382 (3)
O2—N71.232 (3)C17—C181.374 (3)
O3—N71.238 (3)C18—C191.374 (3)
N1—C11.337 (3)C19—C201.365 (4)
N1—C51.352 (3)C1—H10.95
N2—C101.336 (3)C2—H20.95
N2—C61.352 (3)C3—H30.95
N3—C111.345 (3)C4—H40.95
N3—C151.359 (3)C7—H70.95
N4—C201.342 (3)C8—H80.95
N4—C161.358 (3)C9—H90.95
N5—C211.143 (3)C10—H100.95
N6—C221.143 (3)C11—H110.95
C1—C21.375 (4)C12—H120.95
C2—C31.382 (4)C13—H130.95
C3—C41.381 (4)C14—H140.95
C4—C51.383 (3)C17—H170.95
C5—C61.463 (3)C18—H180.95
C6—C71.376 (3)C19—H190.95
C7—C81.382 (4)C20—H200.95
C8—C91.364 (4)
C21—Fe—C2285.8 (1)N3—C11—C12121.7 (2)
N4—Fe—C2295.89 (9)C11—C12—C13119.3 (2)
N1—Fe—C2286.07 (9)C12—C13—C14119.4 (2)
N2—Fe—C2291.66 (9)C13—C14—C15119.0 (2)
N3—Fe—C22177.47 (9)N3—C15—C14121.3 (2)
N4—Fe—C2185.86 (9)N3—C15—C16114.0 (2)
N1—Fe—C2196.74 (9)C14—C15—C16124.6 (2)
N2—Fe—C21176.95 (9)N4—C16—C17121.6 (2)
N3—Fe—C2193.15 (9)N4—C16—C15114.1 (2)
N1—Fe—N4176.87 (8)C15—C16—C17124.3 (2)
N2—Fe—N496.05 (8)C16—C17—C18119.1 (2)
N3—Fe—N481.74 (8)C17—C18—C19118.9 (2)
N1—Fe—N281.43 (8)C18—C19—C20120.0 (2)
N1—Fe—N396.34 (8)N4—C20—C19122.0 (2)
N2—Fe—N389.49 (8)N1—C1—H1118.9
Fe—N1—C1126.0 (2)C2—C1—H1118.9
Fe—N1—C5114.9 (2)C1—C2—H2120.4
Fe—N2—C10125.8 (2)C3—C2—H2120.4
Fe—N2—C6114.9 (2)C4—C3—H3120.6
Fe—N3—C11126.0 (2)C2—C3—H3120.5
Fe—N3—C15114.7 (2)C3—C4—H4120.3
Fe—N4—C20126.2 (2)C5—C4—H4120.3
Fe—N4—C16115.4 (2)C6—C7—H7120.8
Fe—C21—N5177.6 (2)C8—C7—H7120.8
Fe—C22—N6178.7 (2)C9—C8—H8120.0
C1—N1—C5119.1 (2)C7—C8—H8120.0
C6—N2—C10119.2 (2)C8—C9—H9120.4
C11—N3—C15119.2 (2)C10—C9—H9120.4
C16—N4—C20118.3 (2)N2—C10—H10119.3
O2—N7—O3120.4 (3)C9—C10—H10119.4
O1—N7—O2118.7 (2)N3—C11—H11119.2
O1—N7—O3120.8 (2)C12—C11—H11119.1
N1—C1—C2122.3 (2)C11—C12—H12120.4
C1—C2—C3119.1 (2)C13—C12—H12120.3
C2—C3—C4118.9 (2)C12—C13—H13120.3
C3—C4—C5119.4 (2)C14—C13—H13120.3
N1—C5—C4121.3 (2)C15—C14—H14120.5
N1—C5—C6114.5 (2)C13—C14—H14120.5
C4—C5—C6124.3 (2)C18—C17—H17120.4
N2—C6—C7121.9 (2)C16—C17—H17120.5
N2—C6—C5113.7 (2)C19—C18—H18120.6
C5—C6—C7124.4 (2)C17—C18—H18120.5
C6—C7—C8118.4 (2)C20—C19—H19120.0
C7—C8—C9120.0 (2)C18—C19—H19120.0
C8—C9—C10119.2 (2)N4—C20—H20119.0
N2—C10—C9121.3 (2)C19—C20—H20119.0
N1—C5—C6—N22.4 (3)N3—C15—C16—N41.6 (3)

Experimental details

Crystal data
Chemical formula[Fe(C10H8N2)2(CN)2](NO3)
Mr482.28
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)10.7902 (6), 11.7031 (6), 16.1857 (9)
V3)2043.9 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.78
Crystal size (mm)0.40 × 0.34 × 0.34
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionIntegration
(XPREP; Siemens, 1995)
Tmin, Tmax0.718, 0.836
No. of measured, independent and
observed [I > 3σ(I)] reflections
19837, 5807, 4302
Rint0.058
(sin θ/λ)max1)0.699
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.038, 1.20
No. of reflections4302
No. of parameters300
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.80 (8), 0.64 (8)
Absolute structure1815 Friedel pairs (84%)
Rogers parameter1.02 (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.

Selected geometric parameters (Å, º) top
Fe—C211.923 (2)Fe—N21.972 (2)
Fe—C221.922 (3)Fe—N31.973 (2)
Fe—N11.962 (2)Fe—N41.955 (2)
C21—Fe—C2285.8 (1)N3—Fe—C2193.15 (9)
N4—Fe—C2295.89 (9)N1—Fe—N4176.87 (8)
N1—Fe—C2286.07 (9)N2—Fe—N496.05 (8)
N2—Fe—C2291.66 (9)N3—Fe—N481.74 (8)
N3—Fe—C22177.47 (9)N1—Fe—N281.43 (8)
N4—Fe—C2185.86 (9)N1—Fe—N396.34 (8)
N1—Fe—C2196.74 (9)N2—Fe—N389.49 (8)
N2—Fe—C21176.95 (9)
 

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