Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101007995/iz1013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101007995/iz1013Iat293Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101007995/iz1013Iat10Ksup3.hkl |
Na3Co(NO2)6 (Univar, analytical reagent) was recrystallized by very slow evaporation from aqueous solution.
Room temperature and the very low temperature data sets were collected on a locally assembled Huber 512 goniometer equipped with a Displex 202D cryogenic refrigerator (Hendricksen et al., 1986; Larsen, 1995). A full sphere of data was collected. Lists of calculated and observed structure factors are given in the supplementary material. For the 10 K X-ray data collection correction for the absorption by the beryllium shields was performed by PROFIT (Streltsov & Zavodnik, 1989) program.
For both compounds, data collection: Local diffractometer control software; cell refinement: Local diffractometer control software; data reduction: PROFIT (Streltsov & Zavodnik, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. Environments of the atoms in Na3Co(NO206 at 10 K. Displacement ellipsoids are shown at the 50% probability level. |
Na3Co(NO2)6 | Dx = 2.565 Mg m−3 |
Mr = 403.96 | Melting point: not measured K |
Trigonal, R3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -R 3 | Cell parameters from 12 reflections |
a = 7.806 (1) Å | θ = 22.0–22.0° |
c = 14.867 (2) Å | µ = 1.86 mm−1 |
V = 784.5 (2) Å3 | T = 293 K |
Z = 3 | Prism, dark-red |
F(000) = 594 | 0.38 × 0.26 × 0.25 mm |
Huber 512 goniometer diffractometer | 518 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.025 |
None monochromator | θmax = 30.1°, θmin = 3.3° |
ω–2θ scan | h = −11→11 |
Absorption correction: gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) | k = −10→10 |
Tmin = 0.620, Tmax = 0.673 | l = −21→21 |
3068 measured reflections | 3 standard reflections every 100 reflections |
518 independent reflections | intensity decay: 1% |
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)] = 0.020 | w = 1/[σ2(Fo2) + (0.0315P)2 + 0.9654P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.055 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.40 e Å−3 |
518 reflections | Δρmin = −0.33 e Å−3 |
36 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0096 (13) |
Na3Co(NO2)6 | Z = 3 |
Mr = 403.96 | Mo Kα radiation |
Trigonal, R3 | µ = 1.86 mm−1 |
a = 7.806 (1) Å | T = 293 K |
c = 14.867 (2) Å | 0.38 × 0.26 × 0.25 mm |
V = 784.5 (2) Å3 |
Huber 512 goniometer diffractometer | 518 reflections with I > 2σ(I) |
Absorption correction: gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) | Rint = 0.025 |
Tmin = 0.620, Tmax = 0.673 | 3 standard reflections every 100 reflections |
3068 measured reflections | intensity decay: 1% |
518 independent reflections |
R[F2 > 2σ(F2)] = 0.020 | 36 parameters |
wR(F2) = 0.055 | 0 restraints |
S = 1.10 | Δρmax = 0.40 e Å−3 |
518 reflections | Δρmin = −0.33 e Å−3 |
Experimental. no special details |
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 | ||
Co | 0.0000 | 0.0000 | 0.0000 | 0.01297 (15) | |
Na1 | 0.0000 | 0.0000 | 0.26365 (7) | 0.0293 (2) | |
Na2 | 0.3333 | −0.3333 | 0.1667 | 0.0294 (3) | |
N | 0.1144 (4) | −0.1292 (4) | 0.07212 (8) | 0.0186 (3) | |
O1 | 0.0984 (3) | −0.1450 (3) | 0.15415 (9) | 0.0333 (5) | |
O2 | 0.2034 (4) | −0.2021 (4) | 0.03344 (8) | 0.0308 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.01245 (17) | 0.01245 (17) | 0.0140 (2) | 0.00622 (8) | 0.000 | 0.000 |
Na1 | 0.0336 (4) | 0.0336 (4) | 0.0206 (5) | 0.01682 (18) | 0.000 | 0.000 |
Na2 | 0.0333 (5) | 0.0333 (5) | 0.0217 (7) | 0.0166 (2) | 0.000 | 0.000 |
N | 0.0199 (9) | 0.0175 (9) | 0.0202 (5) | 0.0108 (4) | −0.0004 (6) | 0.0014 (6) |
O1 | 0.0495 (13) | 0.0443 (12) | 0.0205 (5) | 0.0342 (11) | 0.0021 (6) | 0.0057 (6) |
O2 | 0.0368 (13) | 0.0391 (14) | 0.0319 (5) | 0.0307 (5) | 0.0039 (9) | 0.0007 (9) |
Co—N | 1.966 (2) | Na1—O2vii | 2.338 (2) |
N—O1 | 1.226 (2) | Na1—O2viii | 2.338 (2) |
N—O2 | 1.238 (3) | Na1—Na2viii | 3.513 (1) |
Na1—O1 | 2.322 (2) | Na2—O2ix | 2.653 (2) |
Na1—O2i | 2.338 (2) | Na2—O2x | 2.653 (2) |
Na2—O1 | 2.873 (2) | Na2—O2xi | 2.653 (2) |
Na2—O2 | 2.653 (2) | Na2—O2xii | 2.653 (2) |
Co—Nii | 1.966 (2) | Na2—O2xiii | 2.653 (2) |
Co—Niii | 1.966 (2) | Na2—O1x | 2.873 (2) |
Co—Niv | 1.966 (2) | Na2—O1xi | 2.873 (2) |
Co—Nv | 1.966 (2) | Na2—O1ix | 2.873 (2) |
Co—Nvi | 1.966 (2) | Na2—O1xiii | 2.873 (2) |
Na1—O1vi | 2.322 (2) | Na2—O1xii | 2.873 (2) |
Na1—O1iii | 2.322 (2) | O2—Na1xiv | 2.338 (2) |
Nii—Co—Niii | 180.0 | O2xiii—Na2—O1x | 108.73 (7) |
Nii—Co—Niv | 93.09 (5) | O2—Na2—O1 | 44.69 (4) |
Niii—Co—Niv | 86.91 (5) | O2ix—Na2—O1 | 104.17 (8) |
Nii—Co—N | 86.91 (5) | O2x—Na2—O1 | 135.31 (4) |
Niii—Co—N | 93.09 (5) | O2xi—Na2—O1 | 108.73 (7) |
Niv—Co—N | 180.0 | O2xii—Na2—O1 | 75.83 (8) |
Nii—Co—Nv | 93.09 (5) | O2xiii—Na2—O1 | 71.27 (7) |
Niii—Co—Nv | 86.91 (5) | O1x—Na2—O1 | 180.0 |
Niv—Co—Nv | 93.09 (5) | O2—Na2—O1xi | 104.17 (8) |
N—Co—Nv | 86.91 (5) | O2ix—Na2—O1xi | 108.73 (7) |
Nii—Co—Nvi | 86.91 (5) | O2x—Na2—O1xi | 75.83 (8) |
Niii—Co—Nvi | 93.09 (5) | O2xi—Na2—O1xi | 44.69 (4) |
Niv—Co—Nvi | 86.91 (5) | O2xii—Na2—O1xi | 71.27 (7) |
N—Co—Nvi | 93.09 (5) | O2xiii—Na2—O1xi | 135.31 (4) |
Nv—Co—Nvi | 180.0 | O1x—Na2—O1xi | 60.415 (6) |
O1vi—Na1—O1 | 76.26 (6) | O1—Na2—O1xi | 119.585 (6) |
O1vi—Na1—O1iii | 76.26 (6) | O2—Na2—O1ix | 108.73 (7) |
O1—Na1—O1iii | 76.26 (6) | O2ix—Na2—O1ix | 44.69 (4) |
O1vi—Na1—O2i | 174.26 (7) | O2x—Na2—O1ix | 71.27 (7) |
O1—Na1—O2i | 104.00 (7) | O2xi—Na2—O1ix | 104.17 (8) |
O1iii—Na1—O2i | 98.18 (6) | O2xii—Na2—O1ix | 135.31 (4) |
O1vi—Na1—O2vii | 104.00 (7) | O2xiii—Na2—O1ix | 75.83 (8) |
O1—Na1—O2vii | 98.18 (6) | O1x—Na2—O1ix | 60.415 (6) |
O1iii—Na1—O2vii | 174.26 (7) | O1—Na2—O1ix | 119.585 (6) |
O2i—Na1—O2vii | 81.67 (5) | O1xi—Na2—O1ix | 119.585 (6) |
O1vi—Na1—O2viii | 98.18 (6) | O2—Na2—O1xiii | 75.83 (8) |
O1—Na1—O2viii | 174.26 (7) | O2ix—Na2—O1xiii | 71.27 (7) |
O1iii—Na1—O2viii | 104.00 (7) | O2x—Na2—O1xiii | 104.17 (8) |
O2i—Na1—O2viii | 81.67 (5) | O2xi—Na2—O1xiii | 135.31 (4) |
O2vii—Na1—O2viii | 81.67 (5) | O2xii—Na2—O1xiii | 108.73 (7) |
O1vi—Na1—Na2viii | 134.52 (4) | O2xiii—Na2—O1xiii | 44.69 (4) |
O1—Na1—Na2viii | 134.52 (4) | O1x—Na2—O1xiii | 119.585 (6) |
O1iii—Na1—Na2viii | 134.52 (4) | O1—Na2—O1xiii | 60.415 (6) |
O2i—Na1—Na2viii | 49.03 (3) | O1xi—Na2—O1xiii | 180.0 |
O2vii—Na1—Na2viii | 49.03 (3) | O1ix—Na2—O1xiii | 60.416 (6) |
O2viii—Na1—Na2viii | 49.03 (3) | O2—Na2—O1xii | 71.27 (7) |
O2—Na2—O2ix | 70.38 (4) | O2ix—Na2—O1xii | 135.31 (4) |
O2—Na2—O2x | 180.0 | O2x—Na2—O1xii | 108.73 (7) |
O2ix—Na2—O2x | 109.62 (4) | O2xi—Na2—O1xii | 75.83 (8) |
O2—Na2—O2xi | 70.38 (4) | O2xii—Na2—O1xii | 44.69 (4) |
O2ix—Na2—O2xi | 70.38 (4) | O2xiii—Na2—O1xii | 104.17 (8) |
O2x—Na2—O2xi | 109.62 (4) | O1x—Na2—O1xii | 119.585 (6) |
O2—Na2—O2xii | 109.62 (4) | O1—Na2—O1xii | 60.415 (6) |
O2ix—Na2—O2xii | 180.0 | O1xi—Na2—O1xii | 60.416 (6) |
O2x—Na2—O2xii | 70.38 (4) | O1ix—Na2—O1xii | 180.0 |
O2xi—Na2—O2xii | 109.62 (4) | O1xiii—Na2—O1xii | 119.584 (6) |
O2—Na2—O2xiii | 109.62 (4) | O1—N—O2 | 117.9 (2) |
O2ix—Na2—O2xiii | 109.62 (4) | O1—N—Co | 123.0 (1) |
O2x—Na2—O2xiii | 70.38 (4) | O2—N—Co | 119.1 (1) |
O2xi—Na2—O2xiii | 180.0 | N—O1—Na1 | 133.7 (1) |
O2xii—Na2—O2xiii | 70.38 (4) | N—O1—Na2 | 93.3 (1) |
O2—Na2—O1x | 135.31 (4) | Na1—O1—Na2 | 130.95 (6) |
O2ix—Na2—O1x | 75.83 (8) | N—O2—Na1xiv | 166.4 (1) |
O2x—Na2—O1x | 44.69 (4) | N—O2—Na2 | 103.97 (9) |
O2xi—Na2—O1x | 71.27 (7) | Na1xiv—O2—Na2 | 89.25 (4) |
O2xii—Na2—O1x | 104.17 (8) |
Symmetry codes: (i) −x+y+2/3, −x+1/3, z+1/3; (ii) y, −x+y, −z; (iii) −y, x−y, z; (iv) −x, −y, −z; (v) x−y, x, −z; (vi) −x+y, −x, z; (vii) −y−1/3, x−y−2/3, z+1/3; (viii) x−1/3, y+1/3, z+1/3; (ix) −y, x−y−1, z; (x) −x+2/3, −y−2/3, −z+1/3; (xi) −x+y+1, −x, z; (xii) y+2/3, −x+y+1/3, −z+1/3; (xiii) x−y−1/3, x−2/3, −z+1/3; (xiv) x+1/3, y−1/3, z−1/3. |
Na3Co(NO2)6 | Dx = 2.606 Mg m−3 |
Mr = 403.96 | Melting point: not measured K |
Trigonal, R3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -R 3 | Cell parameters from 24 reflections |
a = 7.7724 (4) Å | θ = 29.8–40.1° |
c = 14.763 (2) Å | µ = 1.89 mm−1 |
V = 772.4 (1) Å3 | T = 11 K |
Z = 3 | Prism, dark-red |
F(000) = 594 | 0.38 × 0.26 × 0.25 mm |
Huber 512 goniometer diffractometer | 1819 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.029 |
None monochromator | θmax = 50.1°, θmin = 3.3° |
ω–2θ scan | h = −16→16 |
Absorption correction: gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) | k = −16→16 |
Tmin = 0.591, Tmax = 0.673 | l = −31→31 |
10695 measured reflections | 3 standard reflections every 100 reflections |
1819 independent reflections | intensity decay: 1% |
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)] = 0.021 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.4843P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.061 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.85 e Å−3 |
1819 reflections | Δρmin = −1.39 e Å−3 |
36 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0083 (11) |
Na3Co(NO2)6 | Z = 3 |
Mr = 403.96 | Mo Kα radiation |
Trigonal, R3 | µ = 1.89 mm−1 |
a = 7.7724 (4) Å | T = 11 K |
c = 14.763 (2) Å | 0.38 × 0.26 × 0.25 mm |
V = 772.4 (1) Å3 |
Huber 512 goniometer diffractometer | 1819 reflections with I > 2σ(I) |
Absorption correction: gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) | Rint = 0.029 |
Tmin = 0.591, Tmax = 0.673 | 3 standard reflections every 100 reflections |
10695 measured reflections | intensity decay: 1% |
1819 independent reflections |
R[F2 > 2σ(F2)] = 0.021 | 36 parameters |
wR(F2) = 0.061 | 0 restraints |
S = 1.07 | Δρmax = 0.85 e Å−3 |
1819 reflections | Δρmin = −1.39 e Å−3 |
Experimental. The correction for the absorption by the beryllium shield was performed by PROFIT (Streltsov & Zavodnik, 1989) program. |
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 | ||
Co | 0.0000 | 0.0000 | 0.0000 | 0.00511 (3) | |
Na1 | 0.0000 | 0.0000 | 0.26420 (3) | 0.01020 (6) | |
Na2 | 0.3333 | −0.3333 | 0.1667 | 0.01068 (9) | |
N | 0.11241 (10) | −0.13232 (10) | 0.07273 (3) | 0.00757 (6) | |
O1 | 0.08919 (8) | −0.15443 (8) | 0.15537 (3) | 0.01086 (7) | |
O2 | 0.20588 (12) | −0.20117 (12) | 0.03362 (3) | 0.01024 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.00537 (4) | 0.00537 (4) | 0.00460 (5) | 0.00269 (2) | 0.000 | 0.000 |
Na1 | 0.01132 (9) | 0.01132 (9) | 0.00794 (13) | 0.00566 (5) | 0.000 | 0.000 |
Na2 | 0.01201 (13) | 0.01201 (13) | 0.00802 (19) | 0.00601 (7) | 0.000 | 0.000 |
N | 0.00850 (17) | 0.00829 (16) | 0.00685 (11) | 0.00489 (13) | −0.00007 (12) | 0.00009 (11) |
O1 | 0.01444 (16) | 0.01370 (16) | 0.00683 (12) | 0.00882 (14) | 0.00079 (10) | 0.00151 (11) |
O2 | 0.01193 (19) | 0.01216 (18) | 0.01019 (12) | 0.00868 (11) | 0.00009 (17) | −0.00136 (17) |
Co—N | 1.9679 (4) | Na1—Na2vii | 3.4811 (7) |
Co—Ni | 1.9679 (4) | Na2—O1 | 2.8637 (5) |
Co—Nii | 1.9679 (4) | Na2—O1ix | 2.8637 (5) |
Co—Niii | 1.9679 (4) | Na2—O1x | 2.8637 (5) |
Co—Niv | 1.9679 (4) | Na2—O1xi | 2.8637 (5) |
Co—Nv | 1.9679 (4) | Na2—O1xii | 2.8637 (5) |
N—O1 | 1.2326 (7) | Na2—O1xiii | 2.8637 (5) |
N—O2 | 1.2395 (6) | Na2—O2 | 2.6291 (5) |
Na1—O1 | 2.3098 (6) | Na2—O2ix | 2.6291 (5) |
Na1—O1i | 2.3098 (6) | Na2—O2x | 2.6291 (5) |
Na1—O1ii | 2.3098 (6) | Na2—O2xi | 2.6291 (5) |
Na1—O2vi | 2.3141 (5) | Na2—O2xii | 2.6291 (5) |
Na1—O2vii | 2.3141 (5) | Na2—O2xiii | 2.6291 (5) |
Na1—O2viii | 2.3141 (5) | O2—Na1xiv | 2.3142 (5) |
N—Co—Niii | 180.0 | O2xi—Na2—O1x | 103.28 (2) |
Niv—Co—Ni | 180.0 | O2—Na2—O1x | 110.10 (2) |
Nv—Co—Nii | 180.0 | O2xii—Na2—O1ix | 110.10 (2) |
N—Co—Niv | 86.94 (2) | O2ix—Na2—O1xiii | 110.10 (2) |
N—Co—Nv | 86.94 (2) | O2xiii—Na2—O1xii | 110.10 (2) |
Ni—Co—Niii | 86.94 (2) | O2x—Na2—O1xi | 110.10 (2) |
Ni—Co—Nv | 86.94 (2) | O2xi—Na2—O1 | 110.10 (2) |
Nii—Co—Niii | 86.94 (2) | O2—Na2—O1xii | 134.74 (1) |
Nii—Co—Niv | 86.94 (2) | O2xii—Na2—O1 | 134.74 (1) |
N—Co—Ni | 93.06 (2) | O2ix—Na2—O1x | 134.74 (1) |
N—Co—Nii | 93.06 (2) | O2xiii—Na2—O1xi | 134.74 (1) |
Niii—Co—Niv | 93.06 (2) | O2x—Na2—O1ix | 134.74 (1) |
Niii—Co—Nv | 93.06 (2) | O2xi—Na2—O1xiii | 134.74 (1) |
Niv—Co—Nv | 93.06 (2) | O2—Na2—O1 | 45.26 (1) |
Ni—Co—Nii | 93.06 (2) | O2xii—Na2—O1xii | 45.26 (1) |
O1—Na1—O1i | 76.95 (2) | O2ix—Na2—O1ix | 45.26 (1) |
O1—Na1—O1ii | 76.95 (2) | O2xiii—Na2—O1xiii | 45.26 (1) |
O1ii—Na1—O1i | 76.95 (2) | O2x—Na2—O1x | 45.26 (1) |
O1—Na1—O2vi | 104.74 (2) | O2xi—Na2—O1xi | 45.26 (1) |
O1i—Na1—O2vii | 104.74 (2) | O2—Na2—O1ix | 69.90 (2) |
O1ii—Na1—O2viii | 104.74 (2) | O2xii—Na2—O1x | 69.90 (2) |
O1—Na1—O2vii | 173.21 (2) | O2ix—Na2—O1xi | 69.90 (2) |
O1i—Na1—O2viii | 173.21 (2) | O2xiii—Na2—O1 | 69.90 (2) |
O1ii—Na1—O2vi | 173.21 (2) | O2x—Na2—O1xiii | 69.90 (2) |
O1—Na1—O2viii | 96.93 (2) | O2xi—Na2—O1xii | 69.90 (2) |
O1i—Na1—O2vi | 96.93 (2) | O2—Na2—O1xiii | 76.72 (2) |
O1ii—Na1—O2vii | 96.93 (2) | O2xii—Na2—O1xi | 76.72 (2) |
O2viii—Na1—O2vii | 81.69 (2) | O2ix—Na2—O1 | 76.72 (2) |
O2vi—Na1—O2vii | 81.69 (2) | O2xiii—Na2—O1x | 76.72 (2) |
O2vi—Na1—O2viii | 81.69 (2) | O2x—Na2—O1xii | 76.72 (2) |
O1ii—Na1—Na2vii | 134.08 (2) | O2xi—Na2—O1ix | 76.72 (2) |
O1—Na1—Na2vii | 134.08 (2) | O2—Na2—O2ix | 109.71 (2) |
O1i—Na1—Na2vii | 134.08 (2) | O2—Na2—O2xiii | 109.71 (2) |
O2vi—Na1—Na2vii | 49.04 (1) | O2xii—Na2—O2xi | 109.71 (2) |
O2viii—Na1—Na2vii | 49.04 (1) | O2x—Na2—O2xii | 109.71 (2) |
O2vii—Na1—Na2vii | 49.04 (1) | O2x—Na2—O2xiii | 109.71 (2) |
O1xiii—Na2—O1ix | 119.664 (2) | O2xi—Na2—O2ix | 109.71 (2) |
O1—Na2—O1x | 119.664 (2) | O2—Na2—O2xii | 180.0 |
O1—Na2—O1xi | 119.664 (2) | O2x—Na2—O2ix | 180.0 |
O1xii—Na2—O1ix | 119.664 (2) | O2xi—Na2—O2xiii | 180.0 |
O1xii—Na2—O1xiii | 119.664 (2) | O2—Na2—O2x | 70.29 (2) |
O1xi—Na2—O1x | 119.664 (2) | O2—Na2—O2xi | 70.29 (2) |
O1xii—Na2—O1 | 180.0 | O2xii—Na2—O2ix | 70.29 (2) |
O1x—Na2—O1ix | 180.0 | O2xii—Na2—O2xiii | 70.29 (2) |
O1xi—Na2—O1xiii | 180.0 | O2ix—Na2—O2xiii | 70.29 (2) |
O1—Na2—O1ix | 60.336 (2) | O2x—Na2—O2xi | 70.29 (2) |
O1—Na2—O1xiii | 60.336 (2) | O1—N—O2 | 118.51 (5) |
O1xii—Na2—O1x | 60.336 (2) | O1—N—Co | 122.73 (4) |
O1xii—Na2—O1xi | 60.336 (2) | O2—N—Co | 118.73 (4) |
O1x—Na2—O1xiii | 60.336 (2) | N—O1—Na1 | 132.61 (4) |
O1xi—Na2—O1ix | 60.336 (2) | N—O1—Na2 | 92.24 (3) |
O2—Na2—O1xi | 103.28 (2) | Na1—O1—Na2 | 130.97 (2) |
O2xii—Na2—O1xiii | 103.28 (2) | N—O2—Na1xiv | 166.03 (4) |
O2ix—Na2—O1xii | 103.28 (2) | N—O2—Na2 | 103.73 (3) |
O2xiii—Na2—O1ix | 103.28 (2) | Na1xiv—O2—Na2 | 89.30 (2) |
O2x—Na2—O1 | 103.28 (2) |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −x, −y, −z; (iv) y, −x+y, −z; (v) x−y, x, −z; (vi) −x+y+2/3, −x+1/3, z+1/3; (vii) x−1/3, y+1/3, z+1/3; (viii) −y−1/3, x−y−2/3, z+1/3; (ix) y+2/3, −x+y+1/3, −z+1/3; (x) −y, x−y−1, z; (xi) −x+y+1, −x, z; (xii) −x+2/3, −y−2/3, −z+1/3; (xiii) x−y−1/3, x−2/3, −z+1/3; (xiv) x+1/3, y−1/3, z−1/3. |
Experimental details
(Iat293K) | (Iat10K) | |
Crystal data | ||
Chemical formula | Na3Co(NO2)6 | Na3Co(NO2)6 |
Mr | 403.96 | 403.96 |
Crystal system, space group | Trigonal, R3 | Trigonal, R3 |
Temperature (K) | 293 | 11 |
a, c (Å) | 7.806 (1), 14.867 (2) | 7.7724 (4), 14.763 (2) |
V (Å3) | 784.5 (2) | 772.4 (1) |
Z | 3 | 3 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.86 | 1.89 |
Crystal size (mm) | 0.38 × 0.26 × 0.25 | 0.38 × 0.26 × 0.25 |
Data collection | ||
Diffractometer | Huber 512 goniometer diffractometer | Huber 512 goniometer diffractometer |
Absorption correction | Gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) | Gaussian Xtal 3.7 (Hall, du Boulay & Olthof-Hazekamp, 2000) |
Tmin, Tmax | 0.620, 0.673 | 0.591, 0.673 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3068, 518, 518 | 10695, 1819, 1819 |
Rint | 0.025 | 0.029 |
(sin θ/λ)max (Å−1) | 0.705 | 1.080 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.055, 1.10 | 0.021, 0.061, 1.07 |
No. of reflections | 518 | 1819 |
No. of parameters | 36 | 36 |
Δρmax, Δρmin (e Å−3) | 0.40, −0.33 | 0.85, −1.39 |
Computer programs: Local diffractometer control software, PROFIT (Streltsov & Zavodnik, 1989), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Bond (X1-X2) | 293 K | 10.5 K | Symm. trans. X2 |
Co-N | 1.966 (2) | 1.9679 (4) | 0, i, ii, iii, iv, v |
N-O1 | 1.226 (2) | 1.2326 (7) | 0 |
N-O2 | 1.238 (3) | 1.2395 (6) | 0 |
Na1-O1 | 2.322 (2) | 2.3098 (6) | 0, i, ii |
Na1-O2 | 2.338 (2) | 2.3141 (5) | vi, vii, vii |
Na2-O1 | 2.873 (2) | 2.8637 (5) | 0, ix, x, xi, xii, xiii |
Na2-O2 | 2.653 (2) | 2.6291 (5) | 0, ix, x, xi, xii, xiii |
Na1-Na2 | 3.513 (1) | 3.4811 (7) | vi |
Angle (X1-X3-X3) | 293 K | 10.5 K | Symm. trans. X1,X3 |
O1-N-O2 | 117.9 (2) | 118.51 (5) | 0,0 |
O1-N-Co | 123.0 (1) | 122.73 (4) | 0,0 |
O2-N-Co | 119.1 (1) | 118.73 (4) | 0,0 |
N-O1-Na1 | 133.7 (1) | 132.61 (4) | 0,0 |
N-O1-Na2 | 93.3 (1) | 92.24 (3) | 0,0 |
Na1-O1-Na2 | 130.95 (6) | 130.97 (2) | 0,0 |
N-O2-Na2 | 103.97 (9) | 103.73 (3) | 0,0 |
N-Co-N | 180.0 | 180.0 | 0,iii; i,iv; ii,v |
N-Co-N | 86.91 (5) | 86.94 (2) | 0,iv; 0,v; i,iii; i,v; ii,iii; ii,iv |
N-Co-N | 93.09 (5) | 93.06 (2) | 0,ii; 0,xii; i,ii; iii,iv; iii,v; iv,v |
O1-Na1-O1 | 76.26 (6) | 76.95 (2) | 0,ii; 0,xii; i,ii |
O1-Na1-O2 | 104.00 (7) | 104.74 (2) | 0,viii; i,vi; ii,vii |
O1-Na1-O2 | 174.26 (7) | 173.21 (2) | 0,vi; i,vii; ii,viii |
O1-Na1-O2 | 98.18 (6) | 96.93 (2) | 0,vii; i,viii; ii,vi |
O2-Na1-O2 | 81.67 (5) | 81.69 (2) | viii,vi; viii,vii; vi,vii |
O1-Na2-O1 | 119.585 (6) | 119.664 (2) | 0,ix; 0,x; ix,x; xi,xiii; xii,xi; xii,xiii |
O1-Na2-O1 | 180.0 | 180.0 | 0,xi; x,xiii; xii,ix |
O1-Na2-O1 | 60.415 (6) | 60.336 (2) | 0,xii; 0,xiii; ix,xi; ix,xiii; x,xi; xii,x |
O2-Na2-O1 | 104.17 (8) | 103.28 (2) | 0,x; ix,0; x,ix; xi,xiii; xii,xi; xiii,xii |
O2-Na2-O1 | 108.73 (7) | 110.10 (2) | 0,ix; ix,x; x,0; xi,xii; xii,xiii; xiii,xi |
O2-Na2-O1 | 135.31 (4) | 134.74 (1) | 0,xi; ix,xii; x,xiii; xi,0; xii,ix; xiii,x |
O2-Na2-O1 | 44.69 (4) | 45.26 (1) | 0,0; ix,ix; x,x; xi,xi; xii,xii; xiii,xiii |
O2-Na2-O1 | 71.27 (7) | 69.90 (2) | 0,xii; ix,xiii; x,xi; xi,ix; xii,x; xiii,0 |
O2-Na2-O1 | 75.83 (8) | 76.72 (2) | 0,xiii; ix,xi; x,xii; xi,x; xii,0; xiii,ix |
O2-Na2-O2 | 109.62 (4) | 109.71 (2) | 0,xii; 0,xiii; ix,xi; ix,xiii; x,xi; xii,x |
O2-Na2-O2 | 180.0 | 180.0 | 0,xi; x,xiii; xii,ix |
O2-Na2-O2 | 70.38 (4) | 70.29 (2) | 0,ix; 0,x; i,xi; ix,x; xi,xiii; xii,xiii |
Na3Co(NO2)6 is a classical transition metal coordination complex and the high site symmetry of the almost octahedral Co(NO2)63- ion present in the trigonal space group makes it an attractive candidate for charge-density studies. Unit-cell parameters of the compound were reported by Okaya et al. (1957) and the structure was determined at ambient temperature by powder methods (Gromilov et al., 1992). Here, we report, from X-ray diffraction, a more much accurate room-temperature structure and at 10 K an accurate extensive data set that should be suitable for such charge density analysis.
The crystal structure was solved on an X-ray data set collected at room temperature in the space group R-3 m, and refined on F2 to R = 0.0330 using anisotropic temperature factors. In that space group the NO2 group is situated on a crystal mirror plane. Close inspection of the thermal parameters of atoms which lie on the mirror plane (e.g. atom O1 has U11 = U22 = 0.076 and U33 = 0.021 Å-2) led us to the conclusion that the crystal is a merohedral twin, in which the reciprocal lattices coincide exactly. If the twinning population ratio is 50:50 the -3 m Laue symmetry is retained for given Bragg peak positions. Accordingly, we refined the structure in both the 293 and the 10 K cases in the space group R3, using the twin option of SHELXL97. and We obtained distinctly better results, R = 0.0197, than without the twinning option. At 10 K the R-factors without and with the twinning option were 0.0784 and 0.0213, respectively.
The environments of the sodium cations and the anion are shown in Fig. 1. In the Co(NO2)63- anion, the CoN6 unit is almost octahedral. The angle between nitrogen atoms related by the threefold rotation axis and subtended at the cobalt atom is 86.9°, contrasting with the ideal octahedral value of 90°. The Na+ ions are situated on two crystallographically non-equivalent threefold axes. Atom Na1 is surrounded by six oxygen atoms which form a distorted octahedron with Na—O distances typical for this type of polyhedron. The coordination sphere of Na2 is more complicated, with twelve oxygen atoms surrounding the sodium in a distorted dodecahedron. The table lists important bond lengths and angles.