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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103000892/bs0019sup1.cif
Contains datablocks 1, 2, 3

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103000892/bs00193sup2.hkl
Contains datablock 3

CCDC references: 210871; 210872

Computing details top

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).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
(2) top
Crystal data top
C10MnO10V = 1343.01 (4) Å3
Mr = 389.98Z = 4
Monoclinic, I2/aF(000) = 760
Hall symbol: -I 2yaDx = 1.929 Mg m3
a = 14.1257 (2) ÅMo Kα radiation, λ = ? Å
b = 6.8799 (1) ÅApproximately spherical, orange-yellow
c = 14.3121 (3) Å0.45 × 0.45 × 0.4 mm
β = 105.078 (1)°
Data collection top
7052 independent reflectionsk = ??
6664 reflections with I > 2σ(I)l = ??
h = ??
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary 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 = 1.11Δρmax = 0.62 e Å3
7052 reflectionsΔρmin = 0.81 e Å3
101 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0107 (5)
Crystal data top
C10MnO10β = 105.078 (1)°
Mr = 389.98V = 1343.01 (4) Å3
Monoclinic, I2/aZ = 4
a = 14.1257 (2) ÅMo Kα radiation
b = 6.8799 (1) Å0.45 × 0.45 × 0.4 mm
c = 14.3121 (3) Å
Data collection top
7052 independent reflections6664 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.021101 parameters
wR(F2) = 0.0620 restraints
S = 1.11Δρmax = 0.62 e Å3
7052 reflectionsΔρmin = 0.81 e Å3
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
xyzUiso*/Ueq
Mn10.345608 (4)0.236587 (9)0.069064 (4)0.01293 (2)
O10.53285 (4)0.25081 (9)0.22218 (5)0.03935 (15)
O20.23744 (4)0.04643 (7)0.19924 (3)0.02622 (8)
O30.39561 (3)0.14901 (6)0.00299 (4)0.02605 (8)
O40.42231 (3)0.40678 (7)0.08994 (3)0.02391 (7)
O50.28892 (3)0.63559 (5)0.12092 (3)0.02114 (6)
C10.46124 (4)0.24531 (8)0.16240 (4)0.02395 (9)
C20.27780 (4)0.11905 (6)0.14908 (3)0.01763 (6)
C30.37340 (3)0.00467 (7)0.02464 (4)0.01809 (6)
C40.39292 (3)0.34525 (7)0.02889 (3)0.01701 (6)
C50.30926 (3)0.48348 (6)0.10165 (3)0.01570 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.01140 (2)0.01308 (3)0.01356 (3)0.000410 (10)0.00190 (2)0.002570 (10)
O10.0231 (2)0.0474 (3)0.0360 (3)0.00510 (18)0.01315 (19)0.0132 (2)
O20.0391 (2)0.02224 (15)0.02236 (15)0.00596 (15)0.01708 (15)0.00087 (12)
O30.02665 (17)0.01799 (14)0.0365 (2)0.00515 (12)0.01349 (16)0.00106 (13)
O40.02275 (15)0.02674 (17)0.02476 (15)0.00248 (12)0.01069 (12)0.00668 (13)
O50.02828 (16)0.01498 (11)0.01890 (12)0.00142 (11)0.00388 (11)0.00150 (9)
C10.01757 (17)0.0260 (2)0.0236 (2)0.00174 (13)0.00305 (15)0.00763 (15)
C20.02279 (16)0.01520 (13)0.01604 (13)0.00175 (11)0.00710 (12)0.00074 (10)
C30.01655 (13)0.01598 (14)0.02303 (16)0.00201 (11)0.00746 (12)0.00349 (12)
C40.01462 (12)0.01737 (14)0.01939 (14)0.00070 (10)0.00506 (11)0.00352 (11)
C50.01743 (13)0.01485 (12)0.01350 (12)0.00222 (10)0.00167 (10)0.00106 (9)
Geometric parameters (Å, º) top
Mn1—C11.8223 (5)O1—C11.1430 (7)
Mn1—C31.8556 (5)O2—C21.1416 (6)
Mn1—C21.8583 (4)O3—C31.1426 (6)
Mn1—C41.8597 (4)O4—C41.1417 (6)
Mn1—C51.8684 (4)O5—C51.1380 (6)
Mn1—Mn1i2.9027 (1)
C1—Mn1—C392.95 (3)C1—Mn1—Mn1i175.60 (2)
C1—Mn1—C294.01 (2)C3—Mn1—Mn1i90.512 (15)
C3—Mn1—C290.62 (2)C2—Mn1—Mn1i83.235 (15)
C1—Mn1—C496.32 (2)C4—Mn1—Mn1i86.548 (14)
C3—Mn1—C487.23 (2)C5—Mn1—Mn1i84.410 (12)
C2—Mn1—C4169.54 (2)O1—C1—Mn1178.77 (7)
C1—Mn1—C592.24 (2)O2—C2—Mn1178.98 (5)
C3—Mn1—C5174.324 (19)O3—C3—Mn1176.05 (4)
C2—Mn1—C591.296 (19)O4—C4—Mn1178.06 (5)
C4—Mn1—C589.924 (19)O5—C5—Mn1178.44 (4)
Symmetry code: (i) x+1/2, y, z.
(3) top
Crystal data top
C10Mn2O10V = 1343.01 (4) Å3
Mr = 389.98Z = 4
Monoclinic, I2/aDx = 1.929 Mg m3
a = 14.1257 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.8799 (1) ÅApproximately spherical, orange-yellow
c = 14.3121 (3) Å0.45 × 0.45 × 0.40 mm
β = 105.078 (1)°
Data collection top
7052 independent reflectionsh = ??
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)] = 0.014Δρmax = 0.27 e Å3
wR(F2) = 0.016Δρmin = 0.20 e Å3
6532 reflectionsExtinction correction: Becker-Coppens type 1 isotropic
296 parametersExtinction coefficient: 0.231 (7)
Weighting scheme based on measured s.u.'s
Crystal data top
C10Mn2O10β = 105.078 (1)°
Mr = 389.98V = 1343.01 (4) Å3
Monoclinic, I2/aZ = 4
a = 14.1257 (2) ÅMo Kα radiation
b = 6.8799 (1) Å0.45 × 0.45 × 0.40 mm
c = 14.3121 (3) Å
Data collection top
7052 independent reflections6532 reflections with I > 3u(I)
Refinement top
R[F2 > 2σ(F2)] = 0.014296 parameters
wR(F2) = 0.016Δρmax = 0.27 e Å3
6532 reflectionsΔρmin = 0.20 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/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
U11U22U33U12U13U23
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)i2.9031 (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 formulaC10MnO10C10Mn2O10
Mr389.98389.98
Crystal system, space groupMonoclinic, I2/aMonoclinic, 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)
V3)1343.01 (4)1343.01 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)??
Crystal size (mm)0.45 × 0.45 × 0.40.45 × 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 reflections70526532
No. of parameters101296
No. of restraints0?
Δρmax, Δρmin (e Å3)0.62, 0.810.27, 0.20

Computer programs: SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Koritsanszky et al., (1995), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

 

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