Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100005369/br1288sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005369/br1288I293Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005369/br1288I85Ksup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005369/br1288I10Ksup4.hkl |
Cs2K[Mn(CN)6] was prepared by a standard procedure (Brauer, 1963). Single crystals of the complex were obtained by recrystallization 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). The 85 K data were collected on a Syntex P21 diffractometer equipped with a locally developed nitrogen gas stream cooling device.
Data collection: local software for I293K, I10K; P3/P4-PC Software (Siemens, 1991) for I85K. Cell refinement: local software for I293K, I10K; P3/P4-PC Software for I85K. For all compounds, 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 (Sheldrick, 1983); software used to prepare material for publication: SHELXTL.
Fig. 1. Conventional atomic numbering of the [Mn(CN)6]3− octahedron with 50% probability displacement ellipsoids at 85 K. |
Cs2K[Mn(CN)6] | Dx = 2.420 Mg m−3 |
Mr = 515.98 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.207 (2) Å | Cell parameters from 12 reflections |
b = 8.210 (1) Å | θ = 15.2–16.4° |
c = 7.696 (1) Å | µ = 6.28 mm−1 |
β = 90.25 (1)° | T = 293 K |
V = 708.1 (2) Å3 | Prism, dark red–brown |
Z = 2 | 0.36 × 0.23 × 0.23 mm |
F(000) = 464 |
Huber 512 goniometer diffractometer | 1217 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.025 |
None monochromator | θmax = 25.0°, θmin = 3.1° |
ω–2θ scans | h = −13→13 |
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994) | k = −9→9 |
Tmin = 0.197, Tmax = 0.268 | l = −9→9 |
4814 measured reflections | 3 standard reflections every 100 reflections |
1254 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)] = 0.025 | w = 1/[σ2(Fo2) + (0.0311P)2 + 0.9408P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.060 | (Δ/σ)max < 0.001 |
S = 1.12 | Δρmax = 0.48 e Å−3 |
1254 reflections | Δρmin = −1.02 e Å−3 |
77 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0512 (16) |
Cs2K[Mn(CN)6] | V = 708.1 (2) Å3 |
Mr = 515.98 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.207 (2) Å | µ = 6.28 mm−1 |
b = 8.210 (1) Å | T = 293 K |
c = 7.696 (1) Å | 0.36 × 0.23 × 0.23 mm |
β = 90.25 (1)° |
Huber 512 goniometer diffractometer | 1217 reflections with I > 2σ(I) |
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994) | Rint = 0.025 |
Tmin = 0.197, Tmax = 0.268 | 3 standard reflections every 100 reflections |
4814 measured reflections | intensity decay: 1% |
1254 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 77 parameters |
wR(F2) = 0.060 | 0 restraints |
S = 1.12 | Δρmax = 0.48 e Å−3 |
1254 reflections | Δρmin = −1.02 e Å−3 |
Experimental. no special details |
Geometry. All e.s.d.'s (except those in the dihedral angles between pairs of 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 | ||
Cs | 0.25072 (2) | 0.43000 (3) | −0.02177 (4) | 0.05019 (17) | |
K | 0.0000 | 0.5000 | 0.5000 | 0.0330 (2) | |
Mn | 0.0000 | 0.0000 | 0.0000 | 0.02501 (19) | |
C1 | 0.0330 (3) | 0.1298 (4) | −0.2141 (4) | 0.0355 (7) | |
N1 | 0.0540 (3) | 0.2043 (4) | −0.3356 (5) | 0.0594 (9) | |
C2 | 0.0406 (3) | −0.2049 (4) | −0.1269 (4) | 0.0356 (7) | |
N2 | 0.0658 (3) | −0.3212 (4) | −0.2003 (5) | 0.0571 (9) | |
C3 | 0.1698 (3) | 0.0231 (4) | 0.0728 (4) | 0.0364 (7) | |
N3 | 0.2671 (3) | 0.0409 (5) | 0.1165 (5) | 0.0561 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs | 0.0550 (2) | 0.0424 (2) | 0.0532 (2) | −0.00163 (9) | 0.00202 (12) | 0.00519 (9) |
K | 0.0347 (5) | 0.0287 (5) | 0.0356 (5) | −0.0005 (4) | −0.0003 (4) | 0.0009 (4) |
Mn | 0.0263 (3) | 0.0215 (3) | 0.0272 (3) | 0.0011 (2) | 0.0015 (2) | 0.0009 (2) |
C1 | 0.0375 (16) | 0.0304 (16) | 0.0387 (18) | 0.0048 (13) | 0.0037 (13) | 0.0000 (14) |
N1 | 0.081 (2) | 0.0482 (19) | 0.0496 (19) | 0.0127 (17) | 0.0189 (17) | 0.0195 (16) |
C2 | 0.0388 (16) | 0.0341 (17) | 0.0340 (16) | 0.0006 (13) | −0.0028 (13) | 0.0021 (14) |
N2 | 0.077 (2) | 0.0406 (18) | 0.053 (2) | 0.0170 (16) | −0.0083 (17) | −0.0168 (16) |
C3 | 0.0356 (18) | 0.0345 (17) | 0.0392 (18) | 0.0001 (13) | 0.0010 (14) | 0.0045 (14) |
N3 | 0.0326 (17) | 0.067 (2) | 0.069 (2) | −0.0023 (15) | −0.0045 (15) | 0.0081 (19) |
Cs—N1i | 3.330 (4) | Mn—C1 | 1.999 (3) |
Cs—N1 | 3.753 (4) | Mn—C2 | 1.999 (3) |
Cs—N1ii | 3.844 (4) | Mn—C3 | 1.991 (3) |
Cs—N2iii | 3.214 (3) | Mn—C1vii | 1.999 (3) |
Cs—N2i | 3.619 (4) | Mn—C2vii | 1.999 (3) |
Cs—N3iv | 3.256 (4) | Mn—C3vii | 1.991 (3) |
Cs—N3 | 3.372 (4) | Mn—Csvii | 4.5156 (5) |
Cs—C1i | 3.569 (3) | C1—N1 | 1.142 (5) |
Cs—C1 | 3.766 (3) | C1—Csxi | 3.569 (3) |
Cs—C2i | 3.749 (3) | N1—Kxii | 2.803 (3) |
Cs—C3 | 3.538 (3) | N1—Csxi | 3.330 (4) |
Cs—C3iv | 3.645 (3) | N1—Csxiii | 3.844 (4) |
K—N1v | 2.803 (3) | C2—N2 | 1.146 (5) |
K—N1vi | 2.803 (3) | C2—Csxi | 3.749 (3) |
K—N2vii | 2.829 (3) | C2—Csxiv | 3.895 (3) |
K—N2viii | 2.829 (3) | N2—Kxv | 2.829 (3) |
K—N3ix | 2.784 (3) | N2—Csxiv | 3.214 (3) |
K—N3iv | 2.784 (3) | N2—Csxi | 3.619 (4) |
K—Csiv | 4.5046 (5) | C3—N3 | 1.149 (5) |
K—Csix | 4.5046 (5) | C3—Csxvi | 3.645 (3) |
K—Csv | 4.6563 (7) | N3—Kxvi | 2.784 (3) |
K—Csvi | 4.6563 (7) | N3—Csxvi | 3.256 (4) |
K—Csx | 4.9446 (7) | ||
N2iii—Cs—N3iv | 100.93 (9) | Csiv—K—Csv | 107.739 (8) |
N2iii—Cs—N1i | 81.55 (10) | Csix—K—Csv | 72.261 (8) |
N3iv—Cs—N1i | 99.76 (9) | N3ix—K—Csvi | 107.09 (8) |
N2iii—Cs—N3 | 140.44 (9) | N3iv—K—Csvi | 72.91 (8) |
N3iv—Cs—N3 | 88.06 (6) | N1v—K—Csvi | 126.30 (9) |
N1i—Cs—N3 | 135.22 (9) | N1vi—K—Csvi | 53.70 (9) |
N2iii—Cs—C3 | 121.50 (9) | N2vii—K—Csvi | 137.28 (7) |
N3iv—Cs—C3 | 92.88 (9) | N2viii—K—Csvi | 42.72 (7) |
N1i—Cs—C3 | 151.13 (8) | Csiv—K—Csvi | 72.261 (8) |
N3—Cs—C3 | 18.94 (8) | Csix—K—Csvi | 107.739 (8) |
N2iii—Cs—C1i | 84.42 (9) | Csv—K—Csvi | 180.0 |
N3iv—Cs—C1i | 117.47 (8) | N3ix—K—Cs | 141.67 (8) |
N1i—Cs—C1i | 18.64 (8) | N3iv—K—Cs | 38.33 (8) |
N3—Cs—C1i | 125.39 (8) | N1v—K—Cs | 81.74 (7) |
C3—Cs—C1i | 136.59 (8) | N1vi—K—Cs | 98.26 (7) |
N2iii—Cs—N2i | 118.47 (5) | N2vii—K—Cs | 54.86 (8) |
N3iv—Cs—N2i | 139.72 (8) | N2viii—K—Cs | 125.14 (8) |
N1i—Cs—N2i | 79.31 (8) | Csiv—K—Cs | 76.512 (9) |
N3—Cs—N2i | 67.45 (8) | Csix—K—Cs | 103.488 (9) |
C3—Cs—N2i | 74.35 (7) | Csv—K—Cs | 73.473 (13) |
C1i—Cs—N2i | 62.38 (7) | Csvi—K—Cs | 106.527 (13) |
N2iii—Cs—C3iv | 115.24 (8) | N3ix—K—Csx | 38.33 (8) |
N3iv—Cs—C3iv | 18.04 (8) | N3iv—K—Csx | 141.67 (8) |
N1i—Cs—C3iv | 90.71 (8) | N1v—K—Csx | 98.26 (7) |
N3—Cs—C3iv | 83.49 (9) | N1vi—K—Csx | 81.74 (7) |
C3—Cs—C3iv | 93.71 (6) | N2vii—K—Csx | 125.14 (8) |
C1i—Cs—C3iv | 106.24 (8) | N2viii—K—Csx | 54.86 (8) |
N2i—Cs—C3iv | 122.86 (8) | Csiv—K—Csx | 103.488 (9) |
N2iii—Cs—C2i | 106.41 (8) | Csix—K—Csx | 76.512 (8) |
N3iv—Cs—C2i | 144.51 (7) | Csv—K—Csx | 106.527 (13) |
N1i—Cs—C2i | 63.20 (8) | Csvi—K—Csx | 73.473 (13) |
N3—Cs—C2i | 85.11 (8) | Cs—K—Csx | 180.0 |
C3—Cs—C2i | 91.76 (8) | C1—Mn—C2 | 90.1 (1) |
C1i—Cs—C2i | 45.41 (7) | C2—Mn—C3 | 89.9 (1) |
N2i—Cs—C2i | 17.77 (7) | C3—Mn—C1 | 90.1 (1) |
C3iv—Cs—C2i | 126.50 (7) | C3—Mn—C3vii | 180.0 |
N2iii—Cs—N1 | 70.28 (8) | C3vii—Mn—C2 | 90.11 (14) |
N3iv—Cs—N1 | 135.76 (8) | C3—Mn—C2vii | 90.11 (14) |
N1i—Cs—N1 | 120.47 (6) | C3vii—Mn—C2vii | 89.89 (14) |
N3—Cs—N1 | 76.48 (8) | C2—Mn—C2vii | 180.00 (18) |
C3—Cs—N1 | 61.04 (7) | C3—Mn—C1vii | 89.93 (13) |
C1i—Cs—N1 | 105.01 (7) | C3vii—Mn—C1vii | 90.07 (13) |
N2i—Cs—N1 | 70.85 (8) | C2—Mn—C1vii | 89.86 (13) |
C3iv—Cs—N1 | 148.64 (7) | C2vii—Mn—C1vii | 90.14 (13) |
C2i—Cs—N1 | 75.92 (7) | C3vii—Mn—C1 | 89.93 (13) |
N2iii—Cs—C1 | 80.34 (8) | C2vii—Mn—C1 | 89.86 (13) |
N3iv—Cs—C1 | 121.15 (8) | C1vii—Mn—C1 | 180.0 (2) |
N1i—Cs—C1 | 137.61 (8) | C3—Mn—Csvii | 131.17 (10) |
N3—Cs—C1 | 62.51 (8) | C3vii—Mn—Csvii | 48.83 (10) |
C3—Cs—C1 | 45.33 (8) | C2—Mn—Csvii | 60.22 (9) |
C1i—Cs—C1 | 121.15 (4) | C2vii—Mn—Csvii | 119.78 (9) |
N2i—Cs—C1 | 76.33 (7) | C1vii—Mn—Csvii | 55.60 (10) |
C3iv—Cs—C1 | 131.67 (7) | C1—Mn—Csvii | 124.40 (10) |
C2i—Cs—C1 | 85.89 (7) | C3—Mn—Cs | 48.83 (10) |
N1—Cs—C1 | 17.47 (7) | C3vii—Mn—Cs | 131.17 (10) |
N2iii—Cs—N1ii | 155.38 (9) | C2—Mn—Cs | 119.78 (9) |
N3iv—Cs—N1ii | 77.34 (7) | C2vii—Mn—Cs | 60.22 (9) |
N1i—Cs—N1ii | 74.66 (10) | C1vii—Mn—Cs | 124.40 (10) |
N3—Cs—N1ii | 64.15 (8) | C1—Mn—Cs | 55.60 (10) |
C3—Cs—N1ii | 83.08 (8) | Csvii—Mn—Cs | 180.000 (4) |
C1i—Cs—N1ii | 75.09 (8) | N1—C1—Mn | 178.8 (3) |
N2i—Cs—N1ii | 63.45 (7) | N1—C1—Csxi | 68.7 (2) |
C3iv—Cs—N1ii | 59.66 (7) | Mn—C1—Csxi | 110.67 (12) |
C2i—Cs—N1ii | 68.34 (7) | N1—C1—Cs | 80.6 (3) |
N1—Cs—N1ii | 127.90 (4) | Mn—C1—Cs | 98.44 (12) |
C1—Cs—N1ii | 121.94 (7) | Csxi—C1—Cs | 94.83 (7) |
N3ix—K—N3iv | 180.0 | C1—N1—Kxii | 142.0 (3) |
N3ix—K—N1v | 92.82 (11) | C1—N1—Csxi | 92.6 (2) |
N3iv—K—N1v | 87.18 (11) | Kxii—N1—Csxi | 125.30 (11) |
N3ix—K—N1vi | 87.18 (11) | C1—N1—Cs | 81.9 (3) |
N3iv—K—N1vi | 92.82 (11) | Kxii—N1—Cs | 89.30 (10) |
N1v—K—N1vi | 180.0 | Csxi—N1—Cs | 99.25 (10) |
N3ix—K—N2vii | 87.63 (11) | C1—N1—Csxiii | 88.1 (3) |
N3iv—K—N2vii | 92.37 (11) | Kxii—N1—Csxiii | 83.77 (9) |
N1v—K—N2vii | 91.51 (11) | Csxi—N1—Csxiii | 105.34 (10) |
N1vi—K—N2vii | 88.49 (11) | Cs—N1—Csxiii | 153.84 (10) |
N3ix—K—N2viii | 92.37 (11) | N2—C2—Mn | 178.9 (3) |
N3iv—K—N2viii | 87.63 (11) | N2—C2—Csxi | 74.7 (3) |
N1v—K—N2viii | 88.49 (11) | Mn—C2—Csxi | 104.37 (12) |
N1vi—K—N2viii | 91.51 (11) | N2—C2—Csxiv | 46.4 (2) |
N2vii—K—N2viii | 180.0 | Mn—C2—Csxiv | 133.23 (13) |
N3ix—K—Csiv | 131.67 (8) | Csxi—C2—Csxiv | 89.93 (7) |
N3iv—K—Csiv | 48.33 (8) | C2—N2—Kxv | 140.4 (3) |
N1v—K—Csiv | 58.02 (9) | C2—N2—Csxiv | 118.6 (3) |
N1vi—K—Csiv | 121.98 (9) | Kxv—N2—Csxiv | 100.61 (9) |
N2vii—K—Csiv | 126.60 (8) | C2—N2—Csxi | 87.5 (3) |
N2viii—K—Csiv | 53.40 (8) | Kxv—N2—Csxi | 87.73 (9) |
N3ix—K—Csix | 48.33 (8) | Csxiv—N2—Csxi | 104.34 (10) |
N3iv—K—Csix | 131.67 (8) | N3—C3—Mn | 178.0 (3) |
N1v—K—Csix | 121.98 (9) | N3—C3—Cs | 72.3 (2) |
N1vi—K—Csix | 58.02 (9) | Mn—C3—Cs | 106.11 (12) |
N2vii—K—Csix | 53.40 (8) | N3—C3—Csxvi | 61.4 (2) |
N2viii—K—Csix | 126.60 (8) | Mn—C3—Csxvi | 118.44 (13) |
Csiv—K—Csix | 180.0 | Cs—C3—Csxvi | 109.34 (9) |
N3ix—K—Csv | 72.91 (8) | C3—N3—Kxvi | 141.3 (3) |
N3iv—K—Csv | 107.09 (8) | C3—N3—Csxvi | 100.5 (3) |
N1v—K—Csv | 53.70 (9) | Kxvi—N3—Csxvi | 109.64 (11) |
N1vi—K—Csv | 126.30 (9) | C3—N3—Cs | 88.8 (3) |
N2vii—K—Csv | 42.72 (7) | Kxvi—N3—Cs | 93.58 (10) |
N2viii—K—Csv | 137.28 (7) | Csxvi—N3—Cs | 124.33 (12) |
Symmetry codes: (i) −x+1/2, y+1/2, −z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y+1, −z; (vi) x, y, z+1; (vii) −x, −y, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2. |
Cs2K[Mn(CN)6] | Dx = 2.472 Mg m−3 |
Mr = 515.98 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.084 (2) Å | Cell parameters from 14 reflections |
b = 8.213 (1) Å | θ = 16.3–20.3° |
c = 7.617 (1) Å | µ = 6.41 mm−1 |
β = 90.77 (1)° | T = 85 K |
V = 693.3 (2) Å3 | Prism, dark red–brown |
Z = 2 | 0.41 × 0.27 × 0.23 mm |
F(000) = 464 |
Syntex P21 diffractometer | 6386 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 50.2°, θmin = 3.1° |
ω–2θ scans | h = −21→23 |
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994) | k = −17→17 |
Tmin = 0.192, Tmax = 0.323 | l = −16→16 |
39456 measured reflections | 6 standard reflections every 100 reflections |
7328 independent reflections | intensity decay: 2% |
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)] = 0.031 | w = 1/[σ2(Fo2) + (0.0369P)2 + 0.4475P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.079 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 2.95 e Å−3 |
7328 reflections | Δρmin = −1.63 e Å−3 |
77 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0044 (4) |
Cs2K[Mn(CN)6] | V = 693.3 (2) Å3 |
Mr = 515.98 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.084 (2) Å | µ = 6.41 mm−1 |
b = 8.213 (1) Å | T = 85 K |
c = 7.617 (1) Å | 0.41 × 0.27 × 0.23 mm |
β = 90.77 (1)° |
Syntex P21 diffractometer | 6386 reflections with I > 2σ(I) |
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994) | Rint = 0.032 |
Tmin = 0.192, Tmax = 0.323 | 6 standard reflections every 100 reflections |
39456 measured reflections | intensity decay: 2% |
7328 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 77 parameters |
wR(F2) = 0.079 | 0 restraints |
S = 1.09 | Δρmax = 2.95 e Å−3 |
7328 reflections | Δρmin = −1.63 e Å−3 |
Experimental. no special details |
Geometry. All e.s.d.'s (except those in the dihedral angles between pairs of 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 | ||
Cs | 0.251911 (8) | 0.423963 (10) | −0.025547 (12) | 0.01871 (2) | |
K | 0.0000 | 0.5000 | 0.5000 | 0.01310 (4) | |
Mn | 0.0000 | 0.0000 | 0.0000 | 0.00965 (3) | |
C1 | 0.03440 (11) | 0.12972 (14) | −0.21405 (16) | 0.01479 (15) | |
N1 | 0.05668 (14) | 0.20427 (16) | −0.33885 (19) | 0.0241 (2) | |
C2 | 0.04302 (12) | −0.20430 (14) | −0.12643 (16) | 0.01511 (15) | |
N2 | 0.06954 (15) | −0.32167 (15) | −0.20088 (19) | 0.0237 (2) | |
C3 | 0.17029 (11) | 0.02527 (15) | 0.07806 (17) | 0.01544 (16) | |
N3 | 0.26909 (12) | 0.04408 (19) | 0.1257 (2) | 0.0234 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs | 0.02143 (4) | 0.01474 (3) | 0.01999 (4) | −0.00067 (2) | 0.00096 (3) | 0.00118 (2) |
K | 0.01399 (11) | 0.01182 (10) | 0.01348 (10) | −0.00029 (8) | −0.00024 (8) | 0.00033 (8) |
Mn | 0.00971 (7) | 0.00861 (6) | 0.01065 (7) | 0.00034 (5) | 0.00041 (5) | 0.00042 (5) |
C1 | 0.0169 (4) | 0.0126 (3) | 0.0149 (4) | 0.0010 (3) | 0.0018 (3) | 0.0023 (3) |
N1 | 0.0321 (6) | 0.0196 (4) | 0.0209 (5) | 0.0046 (4) | 0.0067 (4) | 0.0083 (4) |
C2 | 0.0181 (4) | 0.0122 (3) | 0.0150 (4) | 0.0016 (3) | 0.0004 (3) | −0.0012 (3) |
N2 | 0.0329 (6) | 0.0166 (4) | 0.0215 (5) | 0.0066 (4) | −0.0024 (4) | −0.0062 (3) |
C3 | 0.0128 (4) | 0.0152 (4) | 0.0182 (4) | −0.0006 (3) | 0.0001 (3) | 0.0022 (3) |
N3 | 0.0131 (4) | 0.0278 (5) | 0.0292 (6) | −0.0013 (4) | −0.0018 (4) | 0.0047 (5) |
Mn—C1 | 1.989 (1) | K—N1vii | 2.7893 (13) |
Mn—C2 | 1.996 (1) | K—N2i | 2.8077 (13) |
Mn—C3 | 1.982 (1) | K—N2viii | 2.8077 (13) |
Mn—C1i | 1.9888 (11) | K—N3ix | 2.7684 (15) |
Mn—C2i | 1.9956 (11) | K—N3v | 2.7684 (15) |
Mn—C3i | 1.9822 (13) | K—Csv | 4.4395 (5) |
C1—N1 | 1.160 (2) | K—Csix | 4.4395 (5) |
C2—N2 | 1.158 (2) | K—Csvi | 4.5799 (6) |
C3—N3 | 1.159 (2) | K—Csvii | 4.5799 (6) |
Mn—Csi | 4.4691 (5) | K—Csx | 4.9509 (7) |
Cs—N1ii | 3.3056 (15) | C1—Csxi | 3.5392 (13) |
Cs—N1 | 3.6735 (17) | N1—Kxii | 2.7893 (13) |
Cs—N1iii | 3.7965 (18) | N1—Csxi | 3.3056 (15) |
Cs—N2iv | 3.1877 (14) | N1—Csxiii | 3.7965 (18) |
Cs—N2ii | 3.5269 (17) | C2—Csxi | 3.6695 (13) |
Cs—N3v | 3.2129 (16) | C2—Csxiv | 3.9019 (12) |
Cs—N3 | 3.3304 (16) | N2—Kxv | 2.8077 (13) |
Cs—C1ii | 3.5392 (13) | N2—Csxiv | 3.1877 (14) |
Cs—C1 | 3.6907 (13) | N2—Csxi | 3.5269 (17) |
Cs—C2ii | 3.6695 (13) | C3—Csxvi | 3.6020 (13) |
Cs—C3 | 3.4903 (13) | N3—Kxvi | 2.7684 (15) |
Cs—C3v | 3.6020 (13) | N3—Csxvi | 3.2129 (16) |
K—N1vi | 2.7893 (13) | ||
N2iv—Cs—N3v | 98.18 (4) | Csv—K—Csvi | 72.642 (8) |
N2iv—Cs—N1ii | 79.55 (4) | Csix—K—Csvi | 107.358 (8) |
N3v—Cs—N1ii | 97.89 (4) | N3ix—K—Csvii | 74.58 (4) |
N2iv—Cs—N3 | 142.36 (4) | N3v—K—Csvii | 105.42 (4) |
N3v—Cs—N3 | 87.95 (2) | N1vi—K—Csvii | 126.68 (4) |
N1ii—Cs—N3 | 136.60 (4) | N1vii—K—Csvii | 53.32 (3) |
N2iv—Cs—C3 | 123.01 (4) | N2i—K—Csvii | 43.36 (3) |
N3v—Cs—C3 | 92.95 (4) | N2viii—K—Csvii | 136.64 (3) |
N1ii—Cs—C3 | 153.31 (3) | Csv—K—Csvii | 107.358 (8) |
N3—Cs—C3 | 19.39 (3) | Csix—K—Csvii | 72.642 (8) |
N2iv—Cs—N2ii | 119.01 (2) | Csvi—K—Csvii | 180.0 |
N3v—Cs—N2ii | 141.63 (3) | N3ix—K—Csx | 37.14 (3) |
N1ii—Cs—N2ii | 81.15 (3) | N3v—K—Csx | 142.86 (3) |
N3—Cs—N2ii | 68.81 (3) | N1vi—K—Csx | 83.12 (3) |
C3—Cs—N2ii | 75.30 (3) | N1vii—K—Csx | 96.88 (3) |
N2iv—Cs—C1ii | 82.97 (4) | N2i—K—Csx | 124.77 (4) |
N3v—Cs—C1ii | 116.25 (3) | N2viii—K—Csx | 55.23 (4) |
N1ii—Cs—C1ii | 19.12 (3) | Csv—K—Csx | 102.788 (8) |
N3—Cs—C1ii | 127.27 (3) | Csix—K—Csx | 77.212 (8) |
C3—Cs—C1ii | 138.77 (3) | Csvi—K—Csx | 73.958 (12) |
N2ii—Cs—C1ii | 63.70 (3) | Csvii—K—Csx | 106.042 (12) |
N2iv—Cs—C3v | 112.80 (3) | N3ix—K—Cs | 142.86 (3) |
N3v—Cs—C3v | 18.47 (3) | N3v—K—Cs | 37.14 (3) |
N1ii—Cs—C3v | 89.33 (3) | N1vi—K—Cs | 96.88 (3) |
N3—Cs—C3v | 82.95 (4) | N1vii—K—Cs | 83.12 (3) |
C3—Cs—C3v | 93.57 (2) | N2i—K—Cs | 55.23 (4) |
N2ii—Cs—C3v | 124.20 (3) | N2viii—K—Cs | 124.77 (4) |
C1ii—Cs—C3v | 105.46 (3) | Csv—K—Cs | 77.212 (8) |
N2iv—Cs—C2ii | 106.32 (3) | Csix—K—Cs | 102.788 (8) |
N3v—Cs—C2ii | 145.73 (3) | Csvi—K—Cs | 106.042 (12) |
N1ii—Cs—C2ii | 64.39 (3) | Csvii—K—Cs | 73.958 (12) |
N3—Cs—C2ii | 87.01 (3) | Csx—K—Cs | 180.0 |
C3—Cs—C2ii | 93.38 (3) | C1—Mn—C2 | 90.29 (5) |
N2ii—Cs—C2ii | 18.39 (3) | C2—Mn—C3 | 90.00 (5) |
C1ii—Cs—C2ii | 46.09 (3) | C3—Mn—C1 | 89.86 (5) |
C3v—Cs—C2ii | 127.39 (3) | C3—Mn—C3i | 180.00 (8) |
N2iv—Cs—N1 | 71.64 (3) | C3i—Mn—C1 | 90.14 (5) |
N3v—Cs—N1 | 135.82 (3) | C3—Mn—C1i | 90.14 (5) |
N1ii—Cs—N1 | 120.93 (2) | C3i—Mn—C1i | 89.86 (5) |
N3—Cs—N1 | 78.17 (3) | C1—Mn—C1i | 180.00 (9) |
C3—Cs—N1 | 62.22 (3) | C3—Mn—C2i | 90.00 (5) |
N2ii—Cs—N1 | 70.46 (3) | C3i—Mn—C2i | 90.00 (5) |
C1ii—Cs—N1 | 105.26 (3) | C1—Mn—C2i | 89.71 (5) |
C3v—Cs—N1 | 149.27 (3) | C1i—Mn—C2i | 90.29 (5) |
C2ii—Cs—N1 | 75.81 (3) | C3i—Mn—C2 | 90.00 (5) |
N2iv—Cs—C1 | 81.89 (3) | C1i—Mn—C2 | 89.71 (5) |
N3v—Cs—C1 | 120.97 (3) | C2i—Mn—C2 | 180.00 (9) |
N1ii—Cs—C1 | 138.86 (3) | C3—Mn—Cs | 48.59 (4) |
N3—Cs—C1 | 63.59 (3) | C3i—Mn—Cs | 131.41 (4) |
C3—Cs—C1 | 45.87 (3) | C1—Mn—Cs | 54.56 (4) |
N2ii—Cs—C1 | 76.37 (3) | C1i—Mn—Cs | 125.44 (4) |
C1ii—Cs—C1 | 122.222 (18) | C2i—Mn—Cs | 61.28 (4) |
C3v—Cs—C1 | 131.78 (3) | C2—Mn—Cs | 118.72 (4) |
C2ii—Cs—C1 | 86.49 (3) | C3—Mn—Csi | 131.41 (4) |
N1—Cs—C1 | 18.13 (3) | C3i—Mn—Csi | 48.59 (4) |
N2iv—Cs—N1iii | 153.48 (4) | C1—Mn—Csi | 125.44 (4) |
N3v—Cs—N1iii | 78.79 (3) | C1i—Mn—Csi | 54.56 (4) |
N1ii—Cs—N1iii | 74.85 (4) | C2i—Mn—Csi | 118.72 (4) |
N3—Cs—N1iii | 64.16 (3) | C2—Mn—Csi | 61.28 (4) |
C3—Cs—N1iii | 83.52 (3) | Cs—Mn—Csi | 180.000 (3) |
N2ii—Cs—N1iii | 63.84 (3) | N1—C1—Mn | 178.7 (1) |
C1ii—Cs—N1iii | 75.14 (3) | N1—C1—Csxi | 68.98 (9) |
C3v—Cs—N1iii | 60.60 (3) | Mn—C1—Csxi | 109.92 (4) |
C2ii—Cs—N1iii | 68.55 (3) | N1—C1—Cs | 80.10 (10) |
N1—Cs—N1iii | 128.35 (2) | Mn—C1—Cs | 99.40 (5) |
C1—Cs—N1iii | 122.51 (3) | Csxi—C1—Cs | 95.28 (3) |
N3ix—K—N3v | 180.0 | C1—N1—Kxii | 140.45 (11) |
N3ix—K—N1vi | 86.43 (5) | C1—N1—Csxi | 91.89 (9) |
N3v—K—N1vi | 93.57 (5) | Kxii—N1—Csxi | 127.64 (5) |
N3ix—K—N1vii | 93.57 (5) | C1—N1—Cs | 81.78 (10) |
N3v—K—N1vii | 86.43 (5) | Kxii—N1—Cs | 89.16 (4) |
N1vi—K—N1vii | 180.0 | Csxi—N1—Cs | 99.79 (4) |
N3ix—K—N2i | 88.13 (5) | C1—N1—Csxiii | 87.85 (11) |
N3v—K—N2i | 91.87 (5) | Kxii—N1—Csxiii | 83.26 (4) |
N1vi—K—N2i | 87.74 (4) | Csxi—N1—Csxiii | 105.15 (4) |
N1vii—K—N2i | 92.26 (4) | Cs—N1—Csxiii | 153.25 (4) |
N3ix—K—N2viii | 91.87 (5) | N2—C2—Mn | 178.9 (1) |
N3v—K—N2viii | 88.13 (5) | N2—C2—Csxi | 73.83 (10) |
N1vi—K—N2viii | 92.26 (4) | Mn—C2—Csxi | 105.16 (4) |
N1vii—K—N2viii | 87.74 (4) | N2—C2—Csxiv | 44.88 (9) |
N2i—K—N2viii | 180.0 | Mn—C2—Csxiv | 135.06 (5) |
N3ix—K—Csv | 131.48 (3) | Csxi—C2—Csxiv | 89.73 (3) |
N3v—K—Csv | 48.52 (3) | C2—N2—Kxv | 139.70 (12) |
N1vi—K—Csv | 121.87 (4) | C2—N2—Csxiv | 120.26 (11) |
N1vii—K—Csv | 58.13 (4) | Kxv—N2—Csxiv | 99.42 (4) |
N2i—K—Csv | 127.43 (3) | C2—N2—Csxi | 87.78 (10) |
N2viii—K—Csv | 52.57 (3) | Kxv—N2—Csxi | 88.23 (4) |
N3ix—K—Csix | 48.52 (3) | Csxiv—N2—Csxi | 105.35 (5) |
N3v—K—Csix | 131.48 (3) | N3—C3—Mn | 178.2 (1) |
N1vi—K—Csix | 58.13 (4) | N3—C3—Cs | 72.49 (9) |
N1vii—K—Csix | 121.87 (4) | Mn—C3—Cs | 106.21 (4) |
N2i—K—Csix | 52.57 (3) | N3—C3—Csxvi | 61.42 (10) |
N2viii—K—Csix | 127.43 (3) | Mn—C3—Csxvi | 118.33 (5) |
Csv—K—Csix | 180.000 (2) | Cs—C3—Csxvi | 111.79 (3) |
N3ix—K—Csvi | 105.42 (4) | C3—N3—Kxvi | 138.43 (13) |
N3v—K—Csvi | 74.58 (4) | C3—N3—Csxvi | 100.11 (10) |
N1vi—K—Csvi | 53.32 (4) | Kxvi—N3—Csxvi | 111.52 (5) |
N1vii—K—Csvi | 126.68 (3) | C3—N3—Cs | 88.12 (10) |
N2i—K—Csvi | 136.64 (3) | Kxvi—N3—Cs | 92.96 (4) |
N2viii—K—Csvi | 43.36 (3) | Csxvi—N3—Cs | 127.66 (5) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x, y+1, z; (v) −x+1/2, y+1/2, −z+1/2; (vi) x, y, z+1; (vii) −x, −y+1, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2. |
Cs2K[Mn(CN)6] | Dx = 2.471 Mg m−3 |
Mr = 515.98 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.074 (7) Å | Cell parameters from 16 reflections |
b = 8.227 (2) Å | θ = 37.4–42.7° |
c = 7.6135 (5) Å | µ = 6.41 mm−1 |
β = 90.95 (4)° | T = 10 K |
V = 693.5 (5) Å3 | Prism, dark red-brown |
Z = 2 | 0.36 × 0.23 × 0.23 mm |
F(000) = 464 |
Huber 512 goniometer diffractometer | 7143 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.039 |
None monochromator | θmax = 50.2°, θmin = 3.1° |
ω–2θ scans | h = −23→23 |
Absorption correction: gaussian (PROFIT; Streltsov & Zavodnik, 1989) | k = −17→17 |
Tmin = 0.192, Tmax = 0.291 | l = −16→16 |
28154 measured reflections | 3 standard reflections every 100 reflections |
7317 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)] = 0.031 | w = 1/[σ2(Fo2) + (0.0341P)2 + 0.778P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.077 | (Δ/σ)max = 0.001 |
S = 1.22 | Δρmax = 2.18 e Å−3 |
7317 reflections | Δρmin = −3.75 e Å−3 |
77 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0535 (12) |
Cs2K[Mn(CN)6] | V = 693.5 (5) Å3 |
Mr = 515.98 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.074 (7) Å | µ = 6.41 mm−1 |
b = 8.227 (2) Å | T = 10 K |
c = 7.6135 (5) Å | 0.36 × 0.23 × 0.23 mm |
β = 90.95 (4)° |
Huber 512 goniometer diffractometer | 7143 reflections with I > 2σ(I) |
Absorption correction: gaussian (PROFIT; Streltsov & Zavodnik, 1989) | Rint = 0.039 |
Tmin = 0.192, Tmax = 0.291 | 3 standard reflections every 100 reflections |
28154 measured reflections | intensity decay: 1% |
7317 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 77 parameters |
wR(F2) = 0.077 | 0 restraints |
S = 1.22 | Δρmax = 2.18 e Å−3 |
7317 reflections | Δρmin = −3.75 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 those in the dihedral angles between pairs of 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 | ||
Cs | 0.252711 (6) | 0.421945 (8) | −0.026975 (9) | 0.00883 (2) | |
K | 0.0000 | 0.5000 | 0.5000 | 0.00896 (5) | |
Mn | 0.0000 | 0.0000 | 0.0000 | 0.00650 (3) | |
C1 | 0.03499 (12) | 0.12958 (15) | −0.21408 (16) | 0.01033 (14) | |
N1 | 0.05787 (13) | 0.20445 (16) | −0.33885 (17) | 0.01469 (17) | |
C2 | 0.04456 (12) | −0.20376 (15) | −0.12616 (16) | 0.01046 (14) | |
N2 | 0.07206 (13) | −0.32080 (15) | −0.20091 (17) | 0.01414 (16) | |
C3 | 0.17055 (11) | 0.02607 (15) | 0.08083 (17) | 0.01070 (15) | |
N3 | 0.26977 (11) | 0.04553 (17) | 0.12979 (18) | 0.01415 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs | 0.00929 (4) | 0.00759 (3) | 0.00964 (3) | −0.00016 (1) | 0.00060 (2) | 0.00016 (1) |
K | 0.00900 (11) | 0.00869 (10) | 0.00918 (10) | −0.00023 (8) | 0.00009 (8) | 0.00019 (8) |
Mn | 0.00633 (7) | 0.00632 (7) | 0.00685 (7) | 0.00007 (5) | 0.00042 (5) | 0.00014 (5) |
C1 | 0.0114 (4) | 0.0097 (3) | 0.0100 (3) | 0.0002 (3) | 0.0013 (3) | 0.0012 (3) |
N1 | 0.0183 (5) | 0.0128 (4) | 0.0131 (4) | 0.0014 (3) | 0.0033 (3) | 0.0043 (3) |
C2 | 0.0119 (4) | 0.0092 (3) | 0.0103 (3) | 0.0005 (3) | 0.0008 (3) | −0.0007 (3) |
N2 | 0.0182 (5) | 0.0110 (3) | 0.0133 (4) | 0.0028 (3) | −0.0003 (3) | −0.0027 (3) |
C3 | 0.0089 (3) | 0.0110 (4) | 0.0122 (4) | −0.0004 (3) | −0.0007 (3) | 0.0012 (3) |
N3 | 0.0096 (4) | 0.0167 (4) | 0.0162 (4) | −0.0012 (3) | −0.0011 (3) | 0.0012 (3) |
Cs—N1i | 3.3040 (17) | Mn—C1 | 1.991 (1) |
Cs—N1 | 3.650 (2) | Mn—C2 | 1.998 (1) |
Cs—N1ii | 3.794 (3) | Mn—C3 | 1.988 (2) |
Cs—N2iii | 3.1855 (17) | Mn—C1vii | 1.9910 (12) |
Cs—N2i | 3.4898 (18) | Mn—C2vii | 1.9980 (12) |
Cs—N3iv | 3.2039 (14) | Mn—C3vii | 1.9883 (17) |
Cs—N3 | 3.3230 (16) | Mn—Csvii | 4.4658 (13) |
Cs—C1i | 3.5335 (18) | C1—N1 | 1.164 (2) |
Cs—C1 | 3.6762 (18) | C1—Csxi | 3.5335 (18) |
Cs—C2i | 3.6442 (19) | N1—Kxii | 2.7932 (13) |
Cs—C3 | 3.4833 (15) | N1—Csxi | 3.3040 (17) |
Cs—C3iv | 3.5914 (14) | N1—Csxiii | 3.794 (3) |
K—N1v | 2.7932 (13) | C2—N2 | 1.162 (2) |
K—N1vi | 2.7932 (13) | C2—Csxi | 3.6442 (19) |
K—N2vii | 2.8170 (14) | C2—Csxiv | 3.9126 (17) |
K—N2viii | 2.8170 (14) | N2—Kxv | 2.8170 (14) |
K—N3ix | 2.775 (2) | N2—Csxiv | 3.1855 (17) |
K—N3iv | 2.775 (2) | N2—Csxi | 3.4898 (18) |
K—Csix | 4.4241 (13) | C3—N3 | 1.165 (2) |
K—Csiv | 4.4241 (13) | C3—Csxvi | 3.5914 (14) |
K—Csv | 4.5694 (19) | N3—Kxvi | 2.775 (2) |
K—Csvi | 4.5694 (19) | N3—Csxvi | 3.2039 (14) |
K—Csx | 4.9713 (19) | ||
N2iii—Cs—N3iv | 97.09 (4) | Csix—K—Csv | 72.73 (3) |
N2iii—Cs—N1i | 78.56 (5) | Csiv—K—Csv | 107.27 (3) |
N3iv—Cs—N1i | 97.37 (4) | N3ix—K—Csvi | 104.75 (5) |
N2iii—Cs—N3 | 143.13 (4) | N3iv—K—Csvi | 75.25 (5) |
N3iv—Cs—N3 | 87.80 (2) | N1v—K—Csvi | 126.98 (3) |
N1i—Cs—N3 | 137.22 (4) | N1vi—K—Csvi | 53.02 (3) |
N2iii—Cs—C3 | 123.68 (4) | N2vii—K—Csvi | 136.48 (3) |
N3iv—Cs—C3 | 92.85 (4) | N2viii—K—Csvi | 43.52 (3) |
N1i—Cs—C3 | 154.19 (3) | Csix—K—Csvi | 107.27 (3) |
N3—Cs—C3 | 19.53 (3) | Csiv—K—Csvi | 72.73 (3) |
N2iii—Cs—N2i | 119.01 (2) | Csv—K—Csvi | 180.000 (2) |
N3iv—Cs—N2i | 142.61 (4) | N3ix—K—Cs | 143.40 (4) |
N1i—Cs—N2i | 81.77 (4) | N3iv—K—Cs | 36.60 (4) |
N3—Cs—N2i | 69.58 (3) | N1v—K—Cs | 83.46 (3) |
C3—Cs—N2i | 75.81 (4) | N1vi—K—Cs | 96.54 (3) |
N2iii—Cs—C1i | 82.30 (5) | N2vii—K—Cs | 55.65 (4) |
N3iv—Cs—C1i | 115.85 (4) | N2viii—K—Cs | 124.35 (4) |
N1i—Cs—C1i | 19.22 (3) | Csix—K—Cs | 102.56 (3) |
N3—Cs—C1i | 128.06 (3) | Csiv—K—Cs | 77.44 (3) |
C3—Cs—C1i | 139.66 (3) | Csv—K—Cs | 74.20 (3) |
N2i—Cs—C1i | 64.14 (4) | Csvi—K—Cs | 105.80 (3) |
N2iii—Cs—C3iv | 111.83 (4) | N3ix—K—Csx | 36.60 (4) |
N3iv—Cs—C3iv | 18.65 (3) | N3iv—K—Csx | 143.40 (4) |
N1i—Cs—C3iv | 89.04 (4) | N1v—K—Csx | 96.54 (3) |
N3—Cs—C3iv | 82.61 (3) | N1vi—K—Csx | 83.46 (3) |
C3—Cs—C3iv | 93.37 (2) | N2vii—K—Csx | 124.35 (4) |
N2i—Cs—C3iv | 124.94 (4) | N2viii—K—Csx | 55.65 (4) |
C1i—Cs—C3iv | 105.26 (4) | Csix—K—Csx | 77.44 (3) |
N2iii—Cs—C2i | 106.11 (4) | Csiv—K—Csx | 102.56 (3) |
N3iv—Cs—C2i | 146.35 (4) | Csv—K—Csx | 105.80 (3) |
N1i—Cs—C2i | 64.76 (4) | Csvi—K—Csx | 74.20 (3) |
N3—Cs—C2i | 87.93 (3) | Cs—K—Csx | 180.000 (2) |
C3—Cs—C2i | 94.12 (3) | C1—Mn—C2 | 90.15 (5) |
N2i—Cs—C2i | 18.58 (3) | C2—Mn—C3 | 89.91 (6) |
C1i—Cs—C2i | 46.31 (3) | C3—Mn—C1 | 89.94 (6) |
C3iv—Cs—C2i | 127.89 (4) | C3—Mn—C3vii | 180.00 (8) |
N2iii—Cs—N1 | 72.24 (4) | C3vii—Mn—C1 | 90.06 (6) |
N3iv—Cs—N1 | 135.66 (4) | C3—Mn—C1vii | 90.06 (6) |
N1i—Cs—N1 | 121.01 (3) | C3vii—Mn—C1vii | 89.94 (6) |
N3—Cs—N1 | 78.83 (3) | C1—Mn—C1vii | 180.00 (6) |
C3—Cs—N1 | 62.68 (3) | C3vii—Mn—C2 | 90.09 (6) |
N2i—Cs—N1 | 70.24 (5) | C1vii—Mn—C2 | 89.85 (5) |
C1i—Cs—N1 | 105.40 (4) | C3—Mn—C2vii | 90.09 (6) |
C3iv—Cs—N1 | 149.33 (3) | C3vii—Mn—C2vii | 89.91 (6) |
C2i—Cs—N1 | 75.77 (4) | C1—Mn—C2vii | 89.85 (5) |
N2iii—Cs—C1 | 82.55 (5) | C1vii—Mn—C2vii | 90.15 (5) |
N3iv—Cs—C1 | 120.84 (4) | C2—Mn—C2vii | 180.00 (7) |
N1i—Cs—C1 | 139.12 (3) | C3—Mn—Cs | 48.52 (4) |
N3—Cs—C1 | 64.05 (4) | C3vii—Mn—Cs | 131.48 (4) |
C3—Cs—C1 | 46.16 (3) | C1—Mn—Cs | 54.24 (4) |
N2i—Cs—C1 | 76.30 (5) | C1vii—Mn—Cs | 125.76 (4) |
C1i—Cs—C1 | 122.57 (2) | C2—Mn—Cs | 118.04 (5) |
C3iv—Cs—C1 | 131.76 (3) | C2vii—Mn—Cs | 61.96 (5) |
C2i—Cs—C1 | 86.64 (4) | C3—Mn—Csvii | 131.48 (4) |
N1—Cs—C1 | 18.27 (3) | C3vii—Mn—Csvii | 48.52 (4) |
N2iii—Cs—N1ii | 152.67 (3) | C1—Mn—Csvii | 125.76 (4) |
N3iv—Cs—N1ii | 79.24 (4) | C1vii—Mn—Csvii | 54.24 (4) |
N1i—Cs—N1ii | 75.13 (5) | C2—Mn—Csvii | 61.96 (5) |
N3—Cs—N1ii | 64.15 (3) | C2vii—Mn—Csvii | 118.04 (5) |
C3—Cs—N1ii | 83.64 (4) | Cs—Mn—Csvii | 180.000 (1) |
N2i—Cs—N1ii | 64.32 (4) | N1—C1—Mn | 178.6 (1) |
C1i—Cs—N1ii | 75.31 (5) | N1—C1—Csxi | 69.18 (9) |
C3iv—Cs—N1ii | 60.85 (4) | Mn—C1—Csxi | 109.77 (5) |
C2i—Cs—N1ii | 68.91 (4) | N1—C1—Cs | 79.61 (10) |
N1—Cs—N1ii | 128.64 (3) | Mn—C1—Cs | 99.69 (5) |
C1—Cs—N1ii | 122.78 (4) | Csxi—C1—Cs | 95.41 (5) |
N3ix—K—N3iv | 180.0 | C1—N1—Kxii | 140.17 (11) |
N3ix—K—N1v | 93.93 (5) | C1—N1—Csxi | 91.60 (10) |
N3iv—K—N1v | 86.07 (5) | Kxii—N1—Csxi | 128.22 (4) |
N3ix—K—N1vi | 86.07 (5) | C1—N1—Cs | 82.12 (10) |
N3iv—K—N1vi | 93.93 (5) | Kxii—N1—Cs | 89.30 (4) |
N1v—K—N1vi | 180.0 | Csxi—N1—Cs | 100.05 (5) |
N3ix—K—N2vii | 88.14 (5) | C1—N1—Csxiii | 87.62 (10) |
N3iv—K—N2vii | 91.86 (5) | Kxii—N1—Csxiii | 82.90 (4) |
N1v—K—N2vii | 92.33 (4) | Csxi—N1—Csxiii | 104.87 (5) |
N1vi—K—N2vii | 87.67 (4) | Cs—N1—Csxiii | 153.27 (4) |
N3ix—K—N2viii | 91.86 (5) | N2—C2—Mn | 178.8 (1) |
N3iv—K—N2viii | 88.14 (5) | N2—C2—Csxi | 73.18 (9) |
N1v—K—N2viii | 87.67 (4) | Mn—C2—Csxi | 105.69 (5) |
N1vi—K—N2viii | 92.33 (4) | N2—C2—Csxiv | 44.26 (9) |
N2vii—K—N2viii | 180.0 | Mn—C2—Csxiv | 135.80 (5) |
N3ix—K—Csix | 48.62 (3) | Csxi—C2—Csxiv | 89.72 (4) |
N3iv—K—Csix | 131.38 (3) | C2—N2—Kxv | 139.18 (11) |
N1v—K—Csix | 121.69 (4) | C2—N2—Csxiv | 121.00 (10) |
N1vi—K—Csix | 58.31 (4) | Kxv—N2—Csxiv | 98.97 (4) |
N2vii—K—Csix | 52.05 (3) | C2—N2—Csxi | 88.24 (10) |
N2viii—K—Csix | 127.95 (3) | Kxv—N2—Csxi | 88.42 (4) |
N3ix—K—Csiv | 131.38 (3) | Csxiv—N2—Csxi | 105.99 (5) |
N3iv—K—Csiv | 48.62 (3) | N3—C3—Mn | 178.2 (1) |
N1v—K—Csiv | 58.31 (4) | N3—C3—Cs | 72.44 (9) |
N1vi—K—Csiv | 121.69 (4) | Mn—C3—Cs | 106.17 (5) |
N2vii—K—Csiv | 127.95 (3) | N3—C3—Csxvi | 61.52 (9) |
N2viii—K—Csiv | 52.05 (3) | Mn—C3—Csxvi | 118.40 (6) |
Csix—K—Csiv | 180.0 | Cs—C3—Csxvi | 112.78 (4) |
N3ix—K—Csv | 75.25 (5) | C3—N3—Kxvi | 137.26 (12) |
N3iv—K—Csv | 104.75 (5) | C3—N3—Csxvi | 99.83 (10) |
N1v—K—Csv | 53.02 (3) | Kxvi—N3—Csxvi | 112.30 (5) |
N1vi—K—Csv | 126.98 (3) | C3—N3—Cs | 88.02 (10) |
N2vii—K—Csv | 43.52 (3) | Kxvi—N3—Cs | 92.58 (4) |
N2viii—K—Csv | 136.48 (3) | Csxvi—N3—Cs | 129.04 (5) |
Symmetry codes: (i) −x+1/2, y+1/2, −z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y+1, −z; (vi) x, y, z+1; (vii) −x, −y, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2. |
Experimental details
(I293K) | (I85K) | (I10K) | |
Crystal data | |||
Chemical formula | Cs2K[Mn(CN)6] | Cs2K[Mn(CN)6] | Cs2K[Mn(CN)6] |
Mr | 515.98 | 515.98 | 515.98 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 85 | 10 |
a, b, c (Å) | 11.207 (2), 8.210 (1), 7.696 (1) | 11.084 (2), 8.213 (1), 7.617 (1) | 11.074 (7), 8.227 (2), 7.6135 (5) |
β (°) | 90.25 (1) | 90.77 (1) | 90.95 (4) |
V (Å3) | 708.1 (2) | 693.3 (2) | 693.5 (5) |
Z | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 6.28 | 6.41 | 6.41 |
Crystal size (mm) | 0.36 × 0.23 × 0.23 | 0.41 × 0.27 × 0.23 | 0.36 × 0.23 × 0.23 |
Data collection | |||
Diffractometer | Huber 512 goniometer diffractometer | Syntex P21 diffractometer | Huber 512 goniometer diffractometer |
Absorption correction | Gaussian (Xtal3.4; Hall et al., 1994) | Gaussian (Xtal3.4; Hall et al., 1994) | Gaussian (PROFIT; Streltsov & Zavodnik, 1989) |
Tmin, Tmax | 0.197, 0.268 | 0.192, 0.323 | 0.192, 0.291 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4814, 1254, 1217 | 39456, 7328, 6386 | 28154, 7317, 7143 |
Rint | 0.025 | 0.032 | 0.039 |
(sin θ/λ)max (Å−1) | 0.596 | 1.081 | 1.080 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.060, 1.12 | 0.031, 0.079, 1.09 | 0.031, 0.077, 1.22 |
No. of reflections | 1254 | 7328 | 7317 |
No. of parameters | 77 | 77 | 77 |
Δρmax, Δρmin (e Å−3) | 0.48, −1.02 | 2.95, −1.63 | 2.18, −3.75 |
Computer programs: local software, P3/P4-PC Software (Siemens, 1991), P3/P4-PC Software, PROFIT (Streltsov & Zavodnik, 1989), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1983), SHELXTL.
293 K | 85 K | 10 K | |
Mn-C1 | 1.999 (3) | 1.989 (1) | 1.991 (1) |
Mn-C2 | 1.999 (3) | 1.996 (1) | 1.998 (1) |
Mn-C3 | 1.991 (3) | 1.982 (1) | 1.988 (2) |
C1-N1 | 1.142 (5) | 1.160 (2) | 1.164 (2) |
C2-N2 | 1.146 (5) | 1.158 (2) | 1.162 (2) |
C3-N3 | 1.149 (5) | 1.159 (2) | 1.165 (2) |
C1-Mn-C2 | 90.1 (1) | 90.29 (5) | 90.15 (5) |
C2-Mn-C3 | 89.9 (1) | 90.00 (5) | 89.91 (6) |
C3-Mn-C1 | 90.1 (1) | 89.86 (5) | 89.94 (6) |
N1-C1-Mn | 178.8 (3) | 178.7 (1) | 178.6 (1) |
N2-C2-Mn | 178.9 (3) | 178.9 (1) | 178.8 (1) |
N3-C3-Mn | 178.0 (3) | 178.2 (1) | 178.2 (1) |
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The trivalent first transition series metals from Cr to Co and some second and third series elements form complexes of formulation Cs2MI[MIII(CN)6] (MI = Li–Cs), with the elpasolite structure. They crystallize well and are of interest in inorganic chemistry as classical coordination complexes involving the most covalently bonding of ligands, the cyanide ion, and for which the physical properties are well defined. There are previous structural studies of these elpasolites by X-ray and neutron diffraction both at room and at lower temperatures, for example, Cs2K[Cr(CN)6] (Figgis et al., 1983; Brown et al., 1987), Cs2K[Mn(CN)6] (Ziegler et al., 1989; Blake et al., 1994) and Cs2K[Fe(CN)6] (Fletcher & Gibb, 1977; Herren et al., 1979; Figgis et al., 1990).
In particular, for MI = K, magnetic susceptibility and polarized neutron diffraction experiments have been performed on their single crystals (Figgis et al., 1985; Brown et al., 1987; Figgis & Reynolds, 1987; Reynolds et al., 1992; Blake et al., 1994). Also, for MI = Li, the complexities of thermal motion have received attention; see, for example, Chadwick et al. (1988) and Ryan & Swanson (1974).
We have determined by X-ray diffraction the crystal structure of Cs2K[Mn(CN)6] at 293, 85 and 10 K. Salts of this type are made up of Cs+ and K+ cations and [M(CN)6]3− anions, and this anion is illustrated in Fig. 1. The structural features have been described before and the present case presents no unusual results. Selected bond lengths and angles for the [Mn(CN)6]3− ion at the three temperatures are given in the Table 1. The results for the 293 K study are very similar to those of Ziegler et al. (1989) at ambient temperature, but with s.u.'s lower by a factor approaching 2.
The [Mn(CN)6]3− ion is very close to regular octahedral stereochemistry at each of the temperatures, with the bond from Mn to C3 just significantly shorter than those to C1 and C2. All the C—Mn—C angles for adjacent ligands differ from 90° by ca 0.15°, and the C—Mn—N angles are all ca 1.5° off the linear configuration. The Mn—C bond lengths are essentially independent of temperaure although the C—N bonds apparently lengthen significantly, presumably due to reduced libration, as we lower the temperature from 293 to 10 K. The mean Mn—C bond length at 85 K [1.989 (4) Å] lies between those in the [Cr(CN)6]3− ion [2.066 (4) Å; Figgis & Reynolds, 1987] and in the [Fe(CN)6]3− ion (1.932 Å; Figgis et al., 1990), while the average C—N separation of 1.159 (1) Å matches that for the Cr salt [1.160 (1) Å] and is slightly lower than for the Fe salt [1.166 (2) Å]. The Mn (d4) and Fe (d5) cases are low spin and have orbitally degenerate ground states and so are formally Jahn–Teller unstable. On the other hand, the Cr (d3) case has an orbital singlet ground state and is Jahn–Teller stable. However, the bond lengths within the respective [M(CN)6]3− ions do not show the differences which might be expected on that account. The Cs atomic displacement parameters (adp's) are quite isotropic at all temperatures. This contrasts with the results for the Cs adp's of Cs2K[Cr(CN)6] at 120 K and, to a lesser extent, of Cs2K[Fe(CN)6] at 85 K, where apparent anomalies in the thermal motion placed limitations on the interpretation of the X-ray data in terms of valence orbital parameters in a charge–density analysis. Such anomalies appear to even greater degree in the analagous Co salt (Figgis & Sobolev, 2000) and preclude its use in a charge–density study.