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An accurate experimental charge density study at 100 K of Mn2(CO)10 [bis(pentacarbonylmanganese)(Mn—Mn)] has been undertaken. A comparison with previously reported structural determinations reveals no evidence for significant Mn—Mn bond lengthening between 100 and 296 K. The nature of the metal–metal and metal–ligand atom interactions has been studied by topological analysis using the Atoms in Molecules (AIM) approach of Bader [(1990), Atoms in Molecules: a Quantum Theory.Oxford: Clarendon Press]. An analysis of the density ρ(r), the Laplacian of the density ∇2ρ(rb) and the total energy densities H(rb) at the bond critical points is used to classify all the chemical bonds as covalent in nature. The results are compared qualitatively and quantitatively with previous charge density studies on this molecule and DFT calculations at the 6-311+G* B3LYP level. The topological properties of the theoretical and experimental densities are in close agreement.
Supporting information
CCDC references: 210871; 210872
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (2). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (2); Koritsanszky et al., (1995) for (3). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (2); Koritsanszky et al., (1995) for (3). Software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) for (2); Koritsanszky et al., (1995) for (3).
Crystal data top
C10MnO10 | V = 1343.01 (4) Å3 |
Mr = 389.98 | Z = 4 |
Monoclinic, I2/a | F(000) = 760 |
Hall symbol: -I 2ya | Dx = 1.929 Mg m−3 |
a = 14.1257 (2) Å | Mo Kα radiation, λ = ? Å |
b = 6.8799 (1) Å | Approximately spherical, orange-yellow |
c = 14.3121 (3) Å | 0.45 × 0.45 × 0.4 mm |
β = 105.078 (1)° | |
Data collection top
7052 independent reflections | k = ?→? |
6664 reflections with I > 2σ(I) | l = ?→? |
h = ?→? | |
Refinement top
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) + (0.0288P)2 + 0.3769P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max = 0.001 |
S = 1.11 | Δρmax = 0.62 e Å−3 |
7052 reflections | Δρmin = −0.81 e Å−3 |
101 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0107 (5) |
Crystal data top
C10MnO10 | β = 105.078 (1)° |
Mr = 389.98 | V = 1343.01 (4) Å3 |
Monoclinic, I2/a | Z = 4 |
a = 14.1257 (2) Å | Mo Kα radiation |
b = 6.8799 (1) Å | 0.45 × 0.45 × 0.4 mm |
c = 14.3121 (3) Å | |
Data collection top
7052 independent reflections | 6664 reflections with I > 2σ(I) |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | 101 parameters |
wR(F2) = 0.062 | 0 restraints |
S = 1.11 | Δρmax = 0.62 e Å−3 |
7052 reflections | Δρmin = −0.81 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.345608 (4) | 0.236587 (9) | 0.069064 (4) | 0.01293 (2) | |
O1 | 0.53285 (4) | 0.25081 (9) | 0.22218 (5) | 0.03935 (15) | |
O2 | 0.23744 (4) | 0.04643 (7) | 0.19924 (3) | 0.02622 (8) | |
O3 | 0.39561 (3) | −0.14901 (6) | −0.00299 (4) | 0.02605 (8) | |
O4 | 0.42231 (3) | 0.40678 (7) | −0.08994 (3) | 0.02391 (7) | |
O5 | 0.28892 (3) | 0.63559 (5) | 0.12092 (3) | 0.02114 (6) | |
C1 | 0.46124 (4) | 0.24531 (8) | 0.16240 (4) | 0.02395 (9) | |
C2 | 0.27780 (4) | 0.11905 (6) | 0.14908 (3) | 0.01763 (6) | |
C3 | 0.37340 (3) | −0.00467 (7) | 0.02464 (4) | 0.01809 (6) | |
C4 | 0.39292 (3) | 0.34525 (7) | −0.02889 (3) | 0.01701 (6) | |
C5 | 0.30926 (3) | 0.48348 (6) | 0.10165 (3) | 0.01570 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01140 (2) | 0.01308 (3) | 0.01356 (3) | −0.000410 (10) | 0.00190 (2) | 0.002570 (10) |
O1 | 0.0231 (2) | 0.0474 (3) | 0.0360 (3) | −0.00510 (18) | −0.01315 (19) | 0.0132 (2) |
O2 | 0.0391 (2) | 0.02224 (15) | 0.02236 (15) | −0.00596 (15) | 0.01708 (15) | 0.00087 (12) |
O3 | 0.02665 (17) | 0.01799 (14) | 0.0365 (2) | 0.00515 (12) | 0.01349 (16) | 0.00106 (13) |
O4 | 0.02275 (15) | 0.02674 (17) | 0.02476 (15) | −0.00248 (12) | 0.01069 (12) | 0.00668 (13) |
O5 | 0.02828 (16) | 0.01498 (11) | 0.01890 (12) | −0.00142 (11) | 0.00388 (11) | −0.00150 (9) |
C1 | 0.01757 (17) | 0.0260 (2) | 0.0236 (2) | −0.00174 (13) | −0.00305 (15) | 0.00763 (15) |
C2 | 0.02279 (16) | 0.01520 (13) | 0.01604 (13) | −0.00175 (11) | 0.00710 (12) | 0.00074 (10) |
C3 | 0.01655 (13) | 0.01598 (14) | 0.02303 (16) | 0.00201 (11) | 0.00746 (12) | 0.00349 (12) |
C4 | 0.01462 (12) | 0.01737 (14) | 0.01939 (14) | −0.00070 (10) | 0.00506 (11) | 0.00352 (11) |
C5 | 0.01743 (13) | 0.01485 (12) | 0.01350 (12) | −0.00222 (10) | 0.00167 (10) | 0.00106 (9) |
Geometric parameters (Å, º) top
Mn1—C1 | 1.8223 (5) | O1—C1 | 1.1430 (7) |
Mn1—C3 | 1.8556 (5) | O2—C2 | 1.1416 (6) |
Mn1—C2 | 1.8583 (4) | O3—C3 | 1.1426 (6) |
Mn1—C4 | 1.8597 (4) | O4—C4 | 1.1417 (6) |
Mn1—C5 | 1.8684 (4) | O5—C5 | 1.1380 (6) |
Mn1—Mn1i | 2.9027 (1) | | |
| | | |
C1—Mn1—C3 | 92.95 (3) | C1—Mn1—Mn1i | 175.60 (2) |
C1—Mn1—C2 | 94.01 (2) | C3—Mn1—Mn1i | 90.512 (15) |
C3—Mn1—C2 | 90.62 (2) | C2—Mn1—Mn1i | 83.235 (15) |
C1—Mn1—C4 | 96.32 (2) | C4—Mn1—Mn1i | 86.548 (14) |
C3—Mn1—C4 | 87.23 (2) | C5—Mn1—Mn1i | 84.410 (12) |
C2—Mn1—C4 | 169.54 (2) | O1—C1—Mn1 | 178.77 (7) |
C1—Mn1—C5 | 92.24 (2) | O2—C2—Mn1 | 178.98 (5) |
C3—Mn1—C5 | 174.324 (19) | O3—C3—Mn1 | 176.05 (4) |
C2—Mn1—C5 | 91.296 (19) | O4—C4—Mn1 | 178.06 (5) |
C4—Mn1—C5 | 89.924 (19) | O5—C5—Mn1 | 178.44 (4) |
Symmetry code: (i) −x+1/2, y, −z. |
Crystal data top
C10Mn2O10 | V = 1343.01 (4) Å3 |
Mr = 389.98 | Z = 4 |
Monoclinic, I2/a | Dx = 1.929 Mg m−3 |
a = 14.1257 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.8799 (1) Å | Approximately spherical, orange-yellow |
c = 14.3121 (3) Å | 0.45 × 0.45 × 0.40 mm |
β = 105.078 (1)° | |
Data collection top
7052 independent reflections | h = ?→? |
6532 reflections with I > 3u(I) | k = ?→? |
θmax = 50.1°, θmin = 3.3° | l = ?→? |
Refinement top
Refinement on F | (Δ/σ)max = 0.004 |
R[F2 > 2σ(F2)] = 0.014 | Δρmax = 0.27 e Å−3 |
wR(F2) = 0.016 | Δρmin = −0.20 e Å−3 |
6532 reflections | Extinction correction: Becker-Coppens type 1 isotropic |
296 parameters | Extinction coefficient: 0.231 (7) |
Weighting scheme based on measured s.u.'s | |
Crystal data top
C10Mn2O10 | β = 105.078 (1)° |
Mr = 389.98 | V = 1343.01 (4) Å3 |
Monoclinic, I2/a | Z = 4 |
a = 14.1257 (2) Å | Mo Kα radiation |
b = 6.8799 (1) Å | 0.45 × 0.45 × 0.40 mm |
c = 14.3121 (3) Å | |
Data collection top
7052 independent reflections | 6532 reflections with I > 3u(I) |
Refinement top
R[F2 > 2σ(F2)] = 0.014 | 296 parameters |
wR(F2) = 0.016 | Δρmax = 0.27 e Å−3 |
6532 reflections | Δρmin = −0.20 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn(1) | 0.345618 (7) | 0.236664 (18) | 0.069074 (7) | 0.013 | |
O(1) | 0.53310 (5) | 0.25158 (10) | 0.22244 (5) | 0.039 | |
O(2) | 0.23745 (3) | 0.04633 (6) | 0.19933 (3) | 0.028 | |
O(3) | 0.39564 (3) | −0.14917 (6) | −0.00310 (3) | 0.028 | |
O(4) | 0.42233 (3) | 0.40697 (6) | −0.08996 (3) | 0.025 | |
O(5) | 0.28882 (3) | 0.63587 (5) | 0.12099 (2) | 0.022 | |
C(1) | 0.46121 (3) | 0.24537 (4) | 0.16248 (3) | 0.024 | |
C(2) | 0.27779 (2) | 0.11903 (4) | 0.14913 (2) | 0.018 | |
C(3) | 0.37337 (2) | −0.00477 (4) | 0.02461 (2) | 0.019 | |
C(4) | 0.39290 (2) | 0.34522 (4) | −0.02886 (2) | 0.018 | |
C(5) | 0.30933 (2) | 0.48337 (4) | 0.10154 (2) | 0.016 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn(1) | 0.01125 (4) | 0.01326 (3) | 0.01359 (3) | −0.00044 (1) | 0.00178 (2) | 0.00258 (1) |
O(1) | 0.0231 (2) | 0.0475 (3) | 0.0371 (2) | −0.0049 (2) | −0.0143 (2) | 0.0140 (2) |
O(2) | 0.0391 (2) | 0.0228 (1) | 0.0224 (1) | −0.0064 (1) | 0.0177 (1) | 0.0012 (1) |
O(3) | 0.0272 (2) | 0.0175 (1) | 0.0372 (2) | 0.0056 (1) | 0.0138 (1) | 0.0006 (1) |
O(4) | 0.0230 (1) | 0.0272 (1) | 0.0247 (1) | −0.0027 (1) | 0.0113 (1) | 0.0069 (1) |
O(5) | 0.0289 (1) | 0.0144 (1) | 0.0191 (1) | −0.0010 (1) | 0.0040 (1) | −0.0017 (1) |
C(1) | 0.0171 (1) | 0.0265 (1) | 0.0235 (1) | −0.0016 (1) | −0.0036 (1) | 0.0075 (1) |
C(2) | 0.0231 (1) | 0.0155 (1) | 0.0158 (1) | −0.0021 (1) | 0.0076 (1) | 0.0011 (1) |
C(3) | 0.0169 (1) | 0.0156 (1) | 0.0234 (1) | 0.0023 (1) | 0.0076 (1) | 0.0031 (1) |
C(4) | 0.0150 (1) | 0.0177 (1) | 0.0191 (1) | −0.0010 (1) | 0.0055 (1) | 0.0037 (1) |
C(5) | 0.0181 (1) | 0.0142 (1) | 0.0139 (1) | −0.0018 (1) | 0.0019 (1) | 0.0007 (1) |
Geometric parameters (Å, º) top
Mn(1)—Mn(1)i | 2.9031 (2) | O(5)—C(5) | 1.1420 (4) |
Mn(1)—C(1) | 1.8224 (4) | C(1)—C(2) | 2.6921 (4) |
Mn(1)—C(2) | 1.8593 (3) | C(1)—C(3) | 2.6685 (5) |
Mn(1)—C(3) | 1.8567 (3) | C(1)—C(4) | 2.7437 (4) |
Mn(1)—C(4) | 1.8589 (3) | C(1)—C(5) | 2.6591 (4) |
Mn(1)—C(5) | 1.8664 (3) | C(2)—C(3) | 2.6412 (4) |
O(1)—C(1) | 1.1472 (6) | C(2)—C(5) | 2.6652 (4) |
O(2)—C(2) | 1.1420 (4) | C(3)—C(4) | 2.5631 (4) |
O(3)—C(3) | 1.1437 (4) | C(4)—C(5) | 2.6318 (4) |
O(4)—C(4) | 1.1433 (4) | | |
| | | |
Mn(1)i—Mn(1)—C(1) | 175.570 (14) | O(2)—C(2)—C(3) | 135.20 (3) |
Mn(1)i—Mn(1)—C(2) | 83.241 (9) | O(2)—C(2)—C(5) | 135.78 (3) |
Mn(1)i—Mn(1)—C(3) | 90.492 (9) | C(1)—C(2)—C(3) | 60.037 (12) |
Mn(1)i—Mn(1)—C(4) | 86.540 (9) | C(1)—C(2)—C(5) | 59.516 (10) |
Mn(1)i—Mn(1)—C(5) | 84.397 (7) | C(3)—C(2)—C(5) | 88.973 (11) |
C(1)—Mn(1)—C(2) | 93.972 (15) | Mn(1)—C(3)—O(3) | 175.99 (3) |
C(1)—Mn(1)—C(3) | 92.985 (14) | Mn(1)—C(3)—C(1) | 43.000 (10) |
C(1)—Mn(1)—C(4) | 96.363 (15) | Mn(1)—C(3)—C(2) | 44.741 (8) |
C(1)—Mn(1)—C(5) | 92.245 (14) | Mn(1)—C(3)—C(4) | 46.420 (8) |
C(2)—Mn(1)—C(3) | 90.595 (12) | O(3)—C(3)—C(1) | 134.40 (3) |
C(2)—Mn(1)—C(4) | 169.534 (13) | O(3)—C(3)—C(2) | 138.50 (3) |
C(2)—Mn(1)—C(5) | 91.347 (12) | O(3)—C(3)—C(4) | 130.68 (3) |
C(3)—Mn(1)—C(4) | 87.230 (13) | C(1)—C(3)—C(2) | 60.927 (12) |
C(3)—Mn(1)—C(5) | 174.282 (15) | C(1)—C(3)—C(4) | 63.223 (11) |
C(4)—Mn(1)—C(5) | 89.896 (12) | C(2)—C(3)—C(4) | 90.696 (12) |
Mn(1)—C(1)—O(1) | 178.82 (8) | Mn(1)—C(4)—O(4) | 178.13 (5) |
Mn(1)—C(1)—C(2) | 43.550 (10) | Mn(1)—C(4)—C(1) | 41.310 (10) |
Mn(1)—C(1)—C(3) | 44.015 (10) | Mn(1)—C(4)—C(3) | 46.350 (9) |
Mn(1)—C(1)—C(4) | 42.327 (10) | Mn(1)—C(4)—C(5) | 45.167 (9) |
Mn(1)—C(1)—C(5) | 44.534 (10) | O(4)—C(4)—C(1) | 138.85 (3) |
O(1)—C(1)—C(2) | 135.52 (5) | O(4)—C(4)—C(3) | 131.78 (3) |
O(1)—C(1)—C(3) | 136.71 (5) | O(4)—C(4)—C(5) | 136.69 (3) |
O(1)—C(1)—C(4) | 138.62 (5) | C(1)—C(4)—C(3) | 60.264 (11) |
O(1)—C(1)—C(5) | 134.76 (5) | C(1)—C(4)—C(5) | 59.254 (11) |
C(2)—C(1)—C(3) | 59.035 (11) | C(3)—C(4)—C(5) | 91.407 (12) |
C(2)—C(1)—C(4) | 85.866 (13) | Mn(1)—C(5)—O(5) | 178.58 (4) |
C(2)—C(1)—C(5) | 59.740 (11) | Mn(1)—C(5)—C(1) | 43.220 (10) |
C(3)—C(1)—C(4) | 56.513 (11) | Mn(1)—C(5)—C(2) | 44.220 (8) |
C(3)—C(1)—C(5) | 88.527 (13) | Mn(1)—C(5)—C(4) | 44.937 (9) |
C(4)—C(1)—C(5) | 58.278 (10) | O(5)—C(5)—C(1) | 136.05 (2) |
Mn(1)—C(2)—O(2) | 178.96 (9) | O(5)—C(5)—C(2) | 137.04 (3) |
Mn(1)—C(2)—C(1) | 42.479 (10) | O(5)—C(5)—C(4) | 133.93 (3) |
Mn(1)—C(2)—C(3) | 44.664 (9) | C(1)—C(5)—C(2) | 60.745 (11) |
Mn(1)—C(2)—C(5) | 44.433 (8) | C(1)—C(5)—C(4) | 62.469 (12) |
O(2)—C(2)—C(1) | 136.49 (3) | C(2)—C(5)—C(4) | 88.694 (12) |
Symmetry code: (i) −x+1/2, y, −z. |
Experimental details
| (2) | (3) |
Crystal data |
Chemical formula | C10MnO10 | C10Mn2O10 |
Mr | 389.98 | 389.98 |
Crystal system, space group | Monoclinic, I2/a | Monoclinic, I2/a |
Temperature (K) | ? | ? |
a, b, c (Å) | 14.1257 (2), 6.8799 (1), 14.3121 (3) | 14.1257 (2), 6.8799 (1), 14.3121 (3) |
β (°) | 105.078 (1) | 105.078 (1) |
V (Å3) | 1343.01 (4) | 1343.01 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | ? | ? |
Crystal size (mm) | 0.45 × 0.45 × 0.4 | 0.45 × 0.45 × 0.40 |
|
Data collection |
Diffractometer | ? | ? |
Absorption correction | ? | ? |
No. of measured, independent and observed reflections | ?, 7052, 6664 [I > 2σ(I)] | ?, 7052, 6532 [I > 3u(I)] |
Rint | ? | ? |
Distance from source to specimen (mm) | – | 1.079 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.062, 1.11 | 0.014, 0.016, ? |
No. of reflections | 7052 | 6532 |
No. of parameters | 101 | 296 |
No. of restraints | 0 | ? |
Δρmax, Δρmin (e Å−3) | 0.62, −0.81 | 0.27, −0.20 |
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