Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012807/fl6039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012807/fl6039Isup2.hkl |
CCDC reference: 217383
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.005 Å
- H-atom completeness 87%
- Disorder in solvent or counterion
- R factor = 0.043
- wR factor = 0.054
- Data-to-parameter ratio = 10.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.685 0.881 Tmin' and Tmax expected: 0.826 0.881 RR' = 0.829 Please check that your absorption correction is appropriate. REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.74 From the CIF: _reflns_number_total 3864 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4149 Completeness (_total/calc) 93.13% Alert C: < 95% complete THETM_01 Alert C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5889 PLAT_302 Alert C Anion/Solvent Disorder ......................... 29.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C47 H86 Cl2 Mn2 O2 Atom count from the _atom_site data: C47 H74 Cl2 Mn2 O2 CELLZ_01 From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C47 H86 Cl2 Mn2 O2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 47.00 47.00 0.00 H 86.00 74.00 12.00 Mn 2.00 2.00 0.00 O 2.00 2.00 0.00 Cl 2.00 2.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_weight 863.98 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 47.00 564.52 H 1.01 74.00 74.59 Mn 54.94 2.00 109.88 O 16.00 2.00 32.00 Cl 35.45 2.00 70.91 Calculated formula weight 851.89 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
Colorless crystalline [(η5-tBu3—C5H2)Mn(Cl)(thf)]2 was obtained in roughly 30% yield from the reaction of equimolar amounts of Na(tBu3—C5H2) and MnCl2 in tetrahydrofuran at room temperature, followed by extraction of the crude product with pentane and slow cooling to 243 K of a concentrated solution. The crystal was handled under a nitrogen atmosphere, mounted on a glass fiber with Paratone-N oil and cooled to 150 (1) K for data collection.
Data collection: SMART (Siemens, 1995-1999); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Fig. 1. View of the structure of (I), with displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. Packing diagram, viewed down the a axis of the unit cell. |
[Mn2Cl2(C17H29)2(C4H8O)2]·C5H12 | Z = 1 |
Mr = 863.98 | F(000) = 936 |
Triclinic, P1 | Dx = 1.189 Mg m−3 |
a = 10.6696 (8) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 10.6803 (8) Å | Cell parameters from 3267 reflections |
c = 12.414 (1) Å | θ = 2.7–24.7° |
α = 65.563 (1)° | µ = 0.67 mm−1 |
β = 70.336 (1)° | T = 150 K |
γ = 86.995 (1)° | Block, colorless |
V = 1206.5 (1) Å3 | 0.28 × 0.21 × 0.19 mm |
Bruker SMART 1K CCD diffractometer | 3864 independent reflections |
Radiation source: X-ray tube | 2734 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.063 |
ω scans | θmax = 24.7°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995) | h = 0→12 |
Tmin = 0.685, Tmax = 0.881 | k = −12→12 |
6241 measured reflections | l = −12→14 |
Refinement on F | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.043 | Weighting scheme based on measured s.u.'s |
wR(F2) = 0.054 | (Δ/σ)max < 0.001 |
S = 1.66 | Δρmax = 0.39 e Å−3 |
2734 reflections | Δρmin = −0.50 e Å−3 |
250 parameters |
[Mn2Cl2(C17H29)2(C4H8O)2]·C5H12 | γ = 86.995 (1)° |
Mr = 863.98 | V = 1206.5 (1) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.6696 (8) Å | Mo Kα radiation |
b = 10.6803 (8) Å | µ = 0.67 mm−1 |
c = 12.414 (1) Å | T = 150 K |
α = 65.563 (1)° | 0.28 × 0.21 × 0.19 mm |
β = 70.336 (1)° |
Bruker SMART 1K CCD diffractometer | 3864 independent reflections |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995) | 2734 reflections with I > 3σ(I) |
Tmin = 0.685, Tmax = 0.881 | Rint = 0.063 |
6241 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.66 | Δρmax = 0.39 e Å−3 |
2734 reflections | Δρmin = −0.50 e Å−3 |
250 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.09070 (4) | 0.03376 (5) | 0.83963 (4) | 0.0207 (2) | |
Cl1 | 0.12031 (7) | 0.10717 (8) | 0.99383 (7) | 0.0260 (2) | |
O1 | −0.0243 (2) | 0.2079 (2) | 0.7705 (2) | 0.0280 (5) | |
C1 | 0.3232 (3) | −0.0047 (3) | 0.7446 (3) | 0.0218 (7) | |
C2 | 0.2878 (3) | 0.0991 (3) | 0.6427 (3) | 0.0214 (7) | |
C3 | 0.1823 (3) | 0.0336 (3) | 0.6314 (3) | 0.0205 (7) | |
H3A | 0.1427 | 0.0776 | 0.5635 | 0.025* | |
C4 | 0.1524 (3) | −0.1060 (3) | 0.7198 (3) | 0.0199 (6) | |
C5 | 0.2376 (3) | −0.1285 (3) | 0.7900 (3) | 0.0197 (6) | |
H5A | 0.2467 | −0.2208 | 0.8535 | 0.024* | |
C6 | 0.4390 (3) | −0.0108 (4) | 0.7944 (3) | 0.0274 (7) | |
C7 | 0.4009 (4) | −0.1228 (4) | 0.9318 (3) | 0.0340 (8) | |
H7A | 0.3736 | −0.2113 | 0.9357 | 0.051* | |
H7B | 0.3267 | −0.0955 | 0.9872 | 0.051* | |
H7C | 0.4783 | −0.1325 | 0.9592 | 0.051* | |
C8 | 0.4797 (3) | 0.1220 (4) | 0.7990 (3) | 0.0326 (8) | |
H8A | 0.5535 | 0.1069 | 0.8318 | 0.049* | |
H8B | 0.4031 | 0.1470 | 0.8542 | 0.049* | |
H8C | 0.5085 | 0.1971 | 0.7138 | 0.049* | |
C9 | 0.5617 (3) | −0.0546 (4) | 0.7131 (4) | 0.0376 (9) | |
H9A | 0.5356 | −0.1394 | 0.7102 | 0.056* | |
H9B | 0.6322 | −0.0711 | 0.7501 | 0.056* | |
H9C | 0.5950 | 0.0192 | 0.6274 | 0.056* | |
C10 | 0.3455 (3) | 0.2491 (3) | 0.5521 (3) | 0.0254 (7) | |
C11 | 0.3182 (4) | 0.3476 (4) | 0.6174 (3) | 0.0338 (8) | |
H11A | 0.3572 | 0.4413 | 0.5551 | 0.051* | |
H11B | 0.3586 | 0.3168 | 0.6832 | 0.051* | |
H11C | 0.2215 | 0.3474 | 0.6555 | 0.051* | |
C12 | 0.2793 (4) | 0.3058 (4) | 0.4503 (3) | 0.0317 (8) | |
H12A | 0.3165 | 0.4015 | 0.3927 | 0.048* | |
H12B | 0.1826 | 0.3028 | 0.4908 | 0.048* | |
H12C | 0.2969 | 0.2491 | 0.4027 | 0.048* | |
C13 | 0.4964 (3) | 0.2571 (4) | 0.4805 (3) | 0.0317 (8) | |
H13A | 0.5311 | 0.3536 | 0.4233 | 0.048* | |
H13B | 0.5106 | 0.2020 | 0.4316 | 0.048* | |
H13C | 0.5435 | 0.2207 | 0.5410 | 0.048* | |
C14 | 0.0595 (3) | −0.2140 (3) | 0.7255 (3) | 0.0235 (7) | |
C15 | −0.0713 (3) | −0.1575 (4) | 0.7103 (3) | 0.0312 (8) | |
H15A | −0.1283 | −0.2295 | 0.7144 | 0.047* | |
H15B | −0.0515 | −0.0776 | 0.6286 | 0.047* | |
H15C | −0.1177 | −0.1292 | 0.7781 | 0.047* | |
C16 | 0.1320 (4) | −0.2534 (4) | 0.6151 (3) | 0.0377 (9) | |
H16A | 0.0744 | −0.3229 | 0.6164 | 0.056* | |
H16B | 0.2155 | −0.2913 | 0.6237 | 0.056* | |
H16C | 0.1520 | −0.1710 | 0.5350 | 0.056* | |
C17 | 0.0274 (3) | −0.3444 (3) | 0.8489 (3) | 0.0295 (8) | |
H17A | −0.0324 | −0.4115 | 0.8495 | 0.044* | |
H17B | −0.0165 | −0.3206 | 0.9202 | 0.044* | |
H17C | 0.1105 | −0.3847 | 0.8562 | 0.044* | |
C18 | −0.0548 (4) | 0.3188 (3) | 0.8112 (3) | 0.0312 (8) | |
H18A | 0.0275 | 0.3641 | 0.8049 | 0.037* | |
H18B | −0.1178 | 0.2837 | 0.8992 | 0.037* | |
C19 | −0.1174 (5) | 0.4166 (5) | 0.7216 (5) | 0.0573 (12) | |
H19A | −0.1806 | 0.4691 | 0.7616 | 0.069* | |
H19B | −0.0482 | 0.4828 | 0.6446 | 0.069* | |
C20 | −0.1882 (5) | 0.3290 (4) | 0.6911 (5) | 0.0534 (12) | |
H20A | −0.1848 | 0.3768 | 0.6026 | 0.064* | |
H20B | −0.2830 | 0.3060 | 0.7473 | 0.064* | |
C21 | −0.1171 (4) | 0.2003 (4) | 0.7106 (4) | 0.0351 (8) | |
H21A | −0.1818 | 0.1168 | 0.7650 | 0.042* | |
H21B | −0.0685 | 0.1964 | 0.6287 | 0.042* | |
C22 | 0.3737 (9) | 0.4495 (9) | 0.9957 (8) | 0.049 (2) | 0.50 |
C23 | 0.5000 | 0.5000 | 1.0000 | 0.067 (2) | |
C24 | 0.5227 (9) | 0.5114 (9) | 1.0954 (8) | 0.049 (2) | 0.50 |
C25 | 0.6473 (6) | 0.5605 (6) | 1.1014 (7) | 0.086 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0246 (3) | 0.0224 (3) | 0.0178 (3) | 0.0060 (2) | −0.0086 (2) | −0.0104 (2) |
Cl1 | 0.0267 (4) | 0.0318 (5) | 0.0235 (4) | 0.0010 (3) | −0.0078 (3) | −0.0158 (3) |
O1 | 0.0345 (13) | 0.0262 (12) | 0.0320 (13) | 0.0097 (10) | −0.0178 (10) | −0.0163 (10) |
C1 | 0.024 (2) | 0.026 (2) | 0.022 (2) | 0.0068 (13) | −0.0094 (13) | −0.0151 (14) |
C2 | 0.021 (2) | 0.025 (2) | 0.022 (2) | 0.0059 (13) | −0.0069 (13) | −0.0144 (14) |
C3 | 0.025 (2) | 0.022 (2) | 0.019 (2) | 0.0049 (13) | −0.0110 (13) | −0.0100 (13) |
C4 | 0.024 (2) | 0.020 (2) | 0.020 (2) | 0.0045 (13) | −0.0084 (13) | −0.0117 (13) |
C5 | 0.023 (2) | 0.019 (2) | 0.022 (2) | 0.0064 (13) | −0.0105 (13) | −0.0108 (13) |
C6 | 0.026 (2) | 0.034 (2) | 0.030 (2) | 0.0079 (15) | −0.0157 (14) | −0.017 (2) |
C7 | 0.037 (2) | 0.042 (2) | 0.034 (2) | 0.012 (2) | −0.025 (2) | −0.017 (2) |
C8 | 0.030 (2) | 0.043 (2) | 0.034 (2) | 0.002 (2) | −0.017 (2) | −0.021 (2) |
C9 | 0.029 (2) | 0.059 (2) | 0.043 (2) | 0.019 (2) | −0.021 (2) | −0.033 (2) |
C10 | 0.025 (2) | 0.025 (2) | 0.025 (2) | 0.0017 (14) | −0.0073 (14) | −0.0098 (14) |
C11 | 0.039 (2) | 0.025 (2) | 0.036 (2) | −0.001 (2) | −0.009 (2) | −0.015 (2) |
C12 | 0.036 (2) | 0.027 (2) | 0.026 (2) | 0.0028 (15) | −0.012 (2) | −0.0047 (15) |
C13 | 0.028 (2) | 0.037 (2) | 0.027 (2) | −0.001 (2) | −0.0060 (15) | −0.013 (2) |
C14 | 0.024 (2) | 0.024 (2) | 0.026 (2) | 0.0024 (13) | −0.0096 (13) | −0.0124 (14) |
C15 | 0.030 (2) | 0.034 (2) | 0.037 (2) | 0.001 (2) | −0.018 (2) | −0.016 (2) |
C16 | 0.039 (2) | 0.044 (2) | 0.037 (2) | −0.005 (2) | −0.006 (2) | −0.029 (2) |
C17 | 0.033 (2) | 0.021 (2) | 0.035 (2) | 0.0005 (14) | −0.014 (2) | −0.0114 (15) |
C18 | 0.038 (2) | 0.027 (2) | 0.036 (2) | 0.011 (2) | −0.017 (2) | −0.019 (2) |
C19 | 0.085 (3) | 0.045 (2) | 0.077 (3) | 0.033 (2) | −0.060 (3) | −0.036 (2) |
C20 | 0.068 (3) | 0.034 (2) | 0.084 (3) | 0.022 (2) | −0.056 (3) | −0.028 (2) |
C21 | 0.041 (2) | 0.033 (2) | 0.045 (2) | 0.011 (2) | −0.027 (2) | −0.020 (2) |
C22 | 0.042 (5) | 0.039 (5) | 0.049 (5) | −0.004 (4) | −0.004 (4) | −0.010 (4) |
C23 | 0.062 (4) | 0.039 (4) | 0.118 (7) | 0.023 (3) | −0.047 (4) | −0.041 (4) |
C24 | 0.053 (5) | 0.041 (5) | 0.044 (5) | −0.002 (4) | −0.015 (4) | −0.009 (4) |
C25 | 0.081 (4) | 0.071 (4) | 0.138 (6) | 0.018 (3) | −0.060 (4) | −0.057 (4) |
Mn1—O1 | 2.202 (2) | C12—H12B | 0.98 |
Mn1—C5 | 2.406 (3) | C12—H12C | 0.98 |
Mn1—C3 | 2.437 (3) | C13—H13A | 0.98 |
Mn1—C4 | 2.439 (3) | C13—H13B | 0.98 |
Mn1—C1 | 2.457 (3) | C13—H13C | 0.98 |
Mn1—Cl1 | 2.4603 (8) | C14—C17 | 1.528 (4) |
Mn1—C2 | 2.484 (3) | C14—C15 | 1.530 (4) |
Mn1—Cl1i | 2.5013 (9) | C14—C16 | 1.544 (4) |
O1—C21 | 1.447 (4) | C15—H15A | 0.98 |
O1—C18 | 1.452 (4) | C15—H15B | 0.98 |
C1—C5 | 1.436 (4) | C15—H15C | 0.98 |
C1—C2 | 1.445 (4) | C16—H16A | 0.98 |
C1—C6 | 1.545 (4) | C16—H16B | 0.98 |
C2—C3 | 1.430 (4) | C16—H16C | 0.98 |
C2—C10 | 1.536 (4) | C17—H17A | 0.98 |
C3—C4 | 1.411 (4) | C17—H17B | 0.98 |
C3—H3A | 1.00 | C17—H17C | 0.98 |
C4—C5 | 1.408 (4) | C18—C19 | 1.497 (5) |
C4—C14 | 1.524 (4) | C18—H18A | 0.99 |
C5—H5A | 1.00 | C18—H18B | 0.99 |
C6—C8 | 1.534 (5) | C19—C20 | 1.466 (6) |
C6—C9 | 1.545 (5) | C19—H19A | 0.99 |
C6—C7 | 1.549 (5) | C19—H19B | 0.99 |
C7—H7A | 0.98 | C20—C21 | 1.505 (5) |
C7—H7B | 0.98 | C20—H20A | 0.99 |
C7—H7C | 0.98 | C20—H20B | 0.99 |
C8—H8A | 0.98 | C21—H21A | 0.99 |
C8—H8B | 0.98 | C21—H21B | 0.99 |
C8—H8C | 0.98 | C22—C24ii | 1.221 (11) |
C9—H9A | 0.98 | C22—C25ii | 1.343 (11) |
C9—H9B | 0.98 | C22—C23 | 1.503 (9) |
C9—H9C | 0.98 | C23—C24ii | 1.339 (9) |
C10—C11 | 1.537 (5) | C24—C25 | 1.490 (10) |
C10—C13 | 1.543 (4) | C23—C24 | 1.339 (9) |
C10—C12 | 1.544 (4) | C23—C22ii | 1.503 (9) |
C11—H11A | 0.98 | C24—C22ii | 1.221 (11) |
C11—H11B | 0.98 | C24—C25 | 1.490 (10) |
C11—H11C | 0.98 | C25—C22ii | 1.343 (11) |
C12—H12A | 0.98 | ||
O1—Mn1—C5 | 146.35 (9) | C2—C10—C11 | 113.2 (3) |
O1—Mn1—C3 | 90.97 (9) | C2—C10—C13 | 110.9 (3) |
C5—Mn1—C3 | 55.46 (10) | C11—C10—C13 | 110.8 (3) |
O1—Mn1—C4 | 115.79 (9) | C2—C10—C12 | 109.8 (3) |
C5—Mn1—C4 | 33.78 (10) | C11—C10—C12 | 105.8 (3) |
C3—Mn1—C4 | 33.63 (10) | C13—C10—C12 | 106.0 (3) |
O1—Mn1—C1 | 130.54 (10) | C10—C11—H11A | 109.5 |
C5—Mn1—C1 | 34.34 (10) | C10—C11—H11B | 109.5 |
C3—Mn1—C1 | 56.02 (10) | H11A—C11—H11B | 109.5 |
C4—Mn1—C1 | 56.93 (10) | C10—C11—H11C | 109.5 |
O1—Mn1—Cl1 | 92.95 (6) | H11A—C11—H11C | 109.5 |
C5—Mn1—Cl1 | 116.42 (7) | H11B—C11—H11C | 109.5 |
C3—Mn1—Cl1 | 148.01 (8) | C10—C12—H12A | 109.5 |
C4—Mn1—Cl1 | 150.18 (8) | C10—C12—H12B | 109.5 |
C1—Mn1—Cl1 | 98.92 (7) | H12A—C12—H12B | 109.5 |
O1—Mn1—C2 | 97.89 (9) | C10—C12—H12C | 109.5 |
C5—Mn1—C2 | 56.38 (10) | H12A—C12—H12C | 109.5 |
C3—Mn1—C2 | 33.78 (10) | H12B—C12—H12C | 109.5 |
C4—Mn1—C2 | 56.71 (10) | C10—C13—H13A | 109.5 |
C1—Mn1—C2 | 34.01 (10) | C10—C13—H13B | 109.5 |
Cl1—Mn1—C2 | 114.32 (7) | H13A—C13—H13B | 109.5 |
O1—Mn1—Cl1i | 90.13 (6) | C10—C13—H13C | 109.5 |
C5—Mn1—Cl1i | 105.96 (8) | H13A—C13—H13C | 109.5 |
C3—Mn1—Cl1i | 123.58 (7) | H13B—C13—H13C | 109.5 |
C4—Mn1—Cl1i | 98.97 (8) | C4—C14—C17 | 111.5 (3) |
C1—Mn1—Cl1i | 137.75 (8) | C4—C14—C15 | 111.7 (3) |
Cl1—Mn1—Cl1i | 88.17 (3) | C17—C14—C15 | 109.2 (3) |
C2—Mn1—Cl1i | 155.50 (8) | C4—C14—C16 | 107.7 (3) |
Mn1—Cl1—Mn1i | 91.83 (3) | C17—C14—C16 | 108.5 (3) |
C21—O1—C18 | 108.8 (2) | C15—C14—C16 | 108.1 (3) |
C21—O1—Mn1 | 121.4 (2) | C14—C15—H15A | 109.5 |
C18—O1—Mn1 | 126.8 (2) | C14—C15—H15B | 109.5 |
C5—C1—C2 | 106.6 (3) | H15A—C15—H15B | 109.5 |
C5—C1—C6 | 119.2 (3) | C14—C15—H15C | 109.5 |
C2—C1—C6 | 133.4 (3) | H15A—C15—H15C | 109.5 |
C5—C1—Mn1 | 70.9 (2) | H15B—C15—H15C | 109.5 |
C2—C1—Mn1 | 74.0 (2) | C14—C16—H16A | 109.5 |
C6—C1—Mn1 | 126.9 (2) | C14—C16—H16B | 109.5 |
C3—C2—C1 | 106.1 (3) | H16A—C16—H16B | 109.5 |
C3—C2—C10 | 121.4 (3) | C14—C16—H16C | 109.5 |
C1—C2—C10 | 132.4 (3) | H16A—C16—H16C | 109.5 |
C3—C2—Mn1 | 71.3 (2) | H16B—C16—H16C | 109.5 |
C1—C2—Mn1 | 72.0 (2) | C14—C17—H17A | 109.5 |
C10—C2—Mn1 | 123.7 (2) | C14—C17—H17B | 109.5 |
C4—C3—C2 | 110.8 (3) | H17A—C17—H17B | 109.5 |
C4—C3—Mn1 | 73.3 (2) | C14—C17—H17C | 109.5 |
C2—C3—Mn1 | 74.9 (2) | H17A—C17—H17C | 109.5 |
C4—C3—H3A | 124.4 | H17B—C17—H17C | 109.5 |
C2—C3—H3A | 124.4 | O1—C18—C19 | 103.7 (3) |
Mn1—C3—H3A | 124.42 | O1—C18—H18A | 111.0 |
C5—C4—C3 | 106.2 (3) | C19—C18—H18A | 111.0 |
C5—C4—C14 | 127.2 (3) | O1—C18—H18B | 111.0 |
C3—C4—C14 | 126.2 (3) | C19—C18—H18B | 111.0 |
C5—C4—Mn1 | 71.8 (2) | H18A—C18—H18B | 109.0 |
C3—C4—Mn1 | 73.1 (2) | C20—C19—C18 | 105.1 (3) |
C14—C4—Mn1 | 125.9 (2) | C20—C19—H19A | 110.7 |
C4—C5—C1 | 110.2 (3) | C18—C19—H19A | 110.7 |
C4—C5—Mn1 | 74.4 (2) | C20—C19—H19B | 110.7 |
C1—C5—Mn1 | 74.8 (2) | C18—C19—H19B | 110.7 |
C4—C5—H5A | 124.6 | H19A—C19—H19B | 108.8 |
C1—C5—H5A | 124.6 | C19—C20—C21 | 105.9 (3) |
Mn1—C5—H5A | 124.59 | C19—C20—H20A | 110.6 |
C8—C6—C1 | 116.2 (3) | C21—C20—H20A | 110.6 |
C8—C6—C9 | 109.5 (3) | C19—C20—H20B | 110.6 |
C1—C6—C9 | 108.3 (3) | C21—C20—H20B | 110.6 |
C8—C6—C7 | 105.1 (3) | H20A—C20—H20B | 108.7 |
C1—C6—C7 | 110.2 (3) | O1—C21—C20 | 106.2 (3) |
C9—C6—C7 | 107.2 (3) | O1—C21—H21A | 110.5 |
C6—C7—H7A | 109.5 | C20—C21—H21A | 110.5 |
C6—C7—H7B | 109.5 | O1—C21—H21B | 110.5 |
H7A—C7—H7B | 109.5 | C20—C21—H21B | 110.5 |
C6—C7—H7C | 109.5 | H21A—C21—H21B | 108.7 |
H7A—C7—H7C | 109.5 | C24ii—C22—C25ii | 70.9 (7) |
H7B—C7—H7C | 109.5 | C24ii—C22—C23 | 57.8 (6) |
C6—C8—H8A | 109.5 | C25ii—C22—C23 | 128.6 (7) |
C6—C8—H8B | 109.5 | C24ii—C23—C24 | 179.998 (3) |
H8A—C8—H8B | 109.5 | C24ii—C23—C22 | 50.5 (5) |
C6—C8—H8C | 109.5 | C24—C23—C22 | 129.5 (5) |
H8A—C8—H8C | 109.5 | C24ii—C23—C22ii | 129.5 (5) |
H8B—C8—H8C | 109.5 | C24—C23—C22ii | 50.5 (5) |
C6—C9—H9A | 109.5 | C22—C23—C22ii | 179.999 (1) |
C6—C9—H9B | 109.5 | C22ii—C24—C23 | 71.8 (7) |
H9A—C9—H9B | 109.5 | C22ii—C24—C25 | 58.4 (6) |
C6—C9—H9C | 109.5 | C23—C24—C25 | 130.2 (7) |
H9A—C9—H9C | 109.5 | C22ii—C25—C24 | 50.7 (5) |
H9B—C9—H9C | 109.5 | ||
O1—Mn1—Cl1—Mn1i | 90.04 (6) | Cl1—Mn1—C3—C2 | 5.7 (3) |
C5—Mn1—Cl1—Mn1i | −106.93 (8) | Cl1i—Mn1—C3—C2 | −166.40 (15) |
C3—Mn1—Cl1—Mn1i | −173.39 (14) | C2—C3—C4—C5 | 1.4 (3) |
C4—Mn1—Cl1—Mn1i | −104.9 (2) | Mn1—C3—C4—C5 | −64.7 (2) |
C1—Mn1—Cl1—Mn1i | −138.13 (8) | C2—C3—C4—C14 | −171.4 (3) |
C2—Mn1—Cl1—Mn1i | −169.94 (8) | Mn1—C3—C4—C14 | 122.5 (3) |
Cl1i—Mn1—Cl1—Mn1i | 0.0 | C2—C3—C4—Mn1 | 66.1 (2) |
C5—Mn1—O1—C21 | 52.3 (3) | O1—Mn1—C4—C5 | 160.1 (2) |
C3—Mn1—O1—C21 | 55.9 (2) | C3—Mn1—C4—C5 | 114.0 (3) |
C4—Mn1—O1—C21 | 32.4 (3) | C1—Mn1—C4—C5 | 37.0 (2) |
C1—Mn1—O1—C21 | 99.8 (3) | Cl1—Mn1—C4—C5 | −3.2 (3) |
Cl1—Mn1—O1—C21 | −155.8 (2) | C2—Mn1—C4—C5 | 77.9 (2) |
C2—Mn1—O1—C21 | 89.1 (2) | Cl1i—Mn1—C4—C5 | −105.3 (2) |
Cl1i—Mn1—O1—C21 | −67.7 (2) | O1—Mn1—C4—C3 | 46.2 (2) |
C5—Mn1—O1—C18 | −149.5 (2) | C5—Mn1—C4—C3 | −114.0 (3) |
C3—Mn1—O1—C18 | −145.9 (3) | C1—Mn1—C4—C3 | −77.0 (2) |
C4—Mn1—O1—C18 | −169.5 (2) | Cl1—Mn1—C4—C3 | −117.2 (2) |
C1—Mn1—O1—C18 | −102.1 (3) | C2—Mn1—C4—C3 | −36.1 (2) |
Cl1—Mn1—O1—C18 | 2.3 (2) | Cl1i—Mn1—C4—C3 | 140.7 (2) |
C2—Mn1—O1—C18 | −112.7 (3) | O1—Mn1—C4—C14 | −76.6 (3) |
Cl1i—Mn1—O1—C18 | 90.5 (2) | C5—Mn1—C4—C14 | 123.2 (3) |
O1—Mn1—C1—C5 | −133.6 (2) | C3—Mn1—C4—C14 | −122.8 (3) |
C3—Mn1—C1—C5 | −77.0 (2) | C1—Mn1—C4—C14 | 160.2 (3) |
C4—Mn1—C1—C5 | −36.4 (2) | Cl1—Mn1—C4—C14 | 120.0 (2) |
Cl1—Mn1—C1—C5 | 124.7 (2) | C2—Mn1—C4—C14 | −158.9 (3) |
C2—Mn1—C1—C5 | −114.5 (2) | Cl1i—Mn1—C4—C14 | 17.9 (2) |
Cl1i—Mn1—C1—C5 | 27.5 (2) | C3—C4—C5—C1 | −1.3 (3) |
O1—Mn1—C1—C2 | −19.1 (2) | C14—C4—C5—C1 | 171.5 (3) |
C5—Mn1—C1—C2 | 114.5 (2) | Mn1—C4—C5—C1 | −66.8 (2) |
C3—Mn1—C1—C2 | 37.5 (2) | C3—C4—C5—Mn1 | 65.6 (2) |
C4—Mn1—C1—C2 | 78.1 (2) | C14—C4—C5—Mn1 | −121.7 (3) |
Cl1—Mn1—C1—C2 | −120.8 (2) | C2—C1—C5—C4 | 0.7 (3) |
Cl1i—Mn1—C1—C2 | 142.00 (15) | C6—C1—C5—C4 | −171.1 (3) |
O1—Mn1—C1—C6 | 113.7 (3) | Mn1—C1—C5—C4 | 66.6 (2) |
C5—Mn1—C1—C6 | −112.7 (3) | C2—C1—C5—Mn1 | −65.9 (2) |
C3—Mn1—C1—C6 | 170.3 (3) | C6—C1—C5—Mn1 | 122.3 (3) |
C4—Mn1—C1—C6 | −149.1 (3) | O1—Mn1—C5—C4 | −33.5 (3) |
Cl1—Mn1—C1—C6 | 11.9 (3) | C3—Mn1—C5—C4 | −37.9 (2) |
C2—Mn1—C1—C6 | 132.8 (4) | C1—Mn1—C5—C4 | −116.6 (3) |
Cl1i—Mn1—C1—C6 | −85.2 (3) | Cl1—Mn1—C5—C4 | 178.22 (15) |
C5—C1—C2—C3 | 0.2 (3) | C2—Mn1—C5—C4 | −79.0 (2) |
C6—C1—C2—C3 | 170.3 (3) | Cl1i—Mn1—C5—C4 | 82.2 (2) |
Mn1—C1—C2—C3 | −63.6 (2) | O1—Mn1—C5—C1 | 83.1 (2) |
C5—C1—C2—C10 | −176.7 (3) | C3—Mn1—C5—C1 | 78.7 (2) |
C6—C1—C2—C10 | −6.6 (6) | C4—Mn1—C5—C1 | 116.6 (3) |
Mn1—C1—C2—C10 | 119.5 (3) | Cl1—Mn1—C5—C1 | −65.1 (2) |
C5—C1—C2—Mn1 | 63.8 (2) | C2—Mn1—C5—C1 | 37.7 (2) |
C6—C1—C2—Mn1 | −126.1 (3) | Cl1i—Mn1—C5—C1 | −161.16 (15) |
O1—Mn1—C2—C3 | −79.8 (2) | C5—C1—C6—C8 | −150.3 (3) |
C5—Mn1—C2—C3 | 76.7 (2) | C2—C1—C6—C8 | 40.5 (5) |
C4—Mn1—C2—C3 | 35.9 (2) | Mn1—C1—C6—C8 | −63.1 (4) |
C1—Mn1—C2—C3 | 114.7 (3) | C5—C1—C6—C9 | 86.1 (4) |
Cl1—Mn1—C2—C3 | −176.71 (15) | C2—C1—C6—C9 | −83.1 (4) |
Cl1i—Mn1—C2—C3 | 28.2 (3) | Mn1—C1—C6—C9 | 173.2 (2) |
O1—Mn1—C2—C1 | 165.4 (2) | C5—C1—C6—C7 | −30.9 (4) |
C5—Mn1—C2—C1 | −38.1 (2) | C2—C1—C6—C7 | 159.9 (3) |
C3—Mn1—C2—C1 | −114.7 (3) | Mn1—C1—C6—C7 | 56.3 (4) |
C4—Mn1—C2—C1 | −78.8 (2) | C3—C2—C10—C11 | 114.3 (3) |
Cl1—Mn1—C2—C1 | 68.6 (2) | C1—C2—C10—C11 | −69.2 (4) |
Cl1i—Mn1—C2—C1 | −86.5 (2) | Mn1—C2—C10—C11 | 26.9 (4) |
O1—Mn1—C2—C10 | 36.0 (2) | C3—C2—C10—C13 | −120.4 (3) |
C5—Mn1—C2—C10 | −167.5 (3) | C1—C2—C10—C13 | 56.1 (4) |
C3—Mn1—C2—C10 | 115.8 (3) | Mn1—C2—C10—C13 | 152.1 (2) |
C4—Mn1—C2—C10 | 151.7 (3) | C3—C2—C10—C12 | −3.6 (4) |
C1—Mn1—C2—C10 | −129.5 (3) | C1—C2—C10—C12 | 172.8 (3) |
Cl1—Mn1—C2—C10 | −60.9 (2) | Mn1—C2—C10—C12 | −91.1 (3) |
Cl1i—Mn1—C2—C10 | 144.0 (2) | C5—C4—C14—C17 | 20.9 (4) |
C1—C2—C3—C4 | −1.0 (3) | C3—C4—C14—C17 | −167.7 (3) |
C10—C2—C3—C4 | 176.3 (3) | Mn1—C4—C14—C17 | −72.8 (3) |
Mn1—C2—C3—C4 | −65.1 (2) | C5—C4—C14—C15 | 143.4 (3) |
C1—C2—C3—Mn1 | 64.1 (2) | C3—C4—C14—C15 | −45.2 (4) |
C10—C2—C3—Mn1 | −118.6 (3) | Mn1—C4—C14—C15 | 49.7 (3) |
O1—Mn1—C3—C4 | −139.5 (2) | C5—C4—C14—C16 | −98.0 (4) |
C5—Mn1—C3—C4 | 38.1 (2) | C3—C4—C14—C16 | 73.3 (4) |
C1—Mn1—C3—C4 | 79.9 (2) | Mn1—C4—C14—C16 | 168.2 (2) |
Cl1—Mn1—C3—C4 | 123.4 (2) | C21—O1—C18—C19 | −27.2 (4) |
C2—Mn1—C3—C4 | 117.7 (3) | Mn1—O1—C18—C19 | 172.4 (3) |
Cl1i—Mn1—C3—C4 | −48.7 (2) | O1—C18—C19—C20 | 32.4 (5) |
O1—Mn1—C3—C2 | 102.8 (2) | C18—C19—C20—C21 | −25.6 (5) |
C5—Mn1—C3—C2 | −79.6 (2) | C18—O1—C21—C20 | 11.5 (4) |
C4—Mn1—C3—C2 | −117.7 (3) | Mn1—O1—C21—C20 | 173.2 (3) |
C1—Mn1—C3—C2 | −37.8 (2) | C19—C20—C21—O1 | 9.2 (5) |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Mn2Cl2(C17H29)2(C4H8O)2]·C5H12 |
Mr | 863.98 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.6696 (8), 10.6803 (8), 12.414 (1) |
α, β, γ (°) | 65.563 (1), 70.336 (1), 86.995 (1) |
V (Å3) | 1206.5 (1) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.28 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (Blessing, 1995) |
Tmin, Tmax | 0.685, 0.881 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 6241, 3864, 2734 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.589 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.054, 1.66 |
No. of reflections | 2734 |
No. of parameters | 250 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.50 |
Computer programs: SMART (Siemens, 1995-1999), SAINT (Bruker, 2002), SAINT, SIR92 (Altomare et al., 1993), TEXSAN.
Mn1—O1 | 2.202 (2) | Mn1—C1 | 2.457 (3) |
Mn1—C5 | 2.406 (3) | Mn1—Cl1 | 2.4603 (8) |
Mn1—C3 | 2.437 (3) | Mn1—C2 | 2.484 (3) |
Mn1—C4 | 2.439 (3) | Mn1—Cl1i | 2.5013 (9) |
O1—Mn1—Cl1 | 92.95 (6) | Cl1—Mn1—Cl1i | 88.17 (3) |
O1—Mn1—Cl1i | 90.13 (6) | Mn1—Cl1—Mn1i | 91.83 (3) |
Symmetry code: (i) −x, −y, −z+2. |
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Complexes of the type C5H5MnCl(L) are not well known in the literature. They have been proposed as reaction intermediates (Coffield, 1957; Fischer & Breitschaft, 1966). Patents claim the use of (RnC5H5-n)MnX in the synthesis of corresponding (RnC5H5-n)Mn(CO)3 molecules, useful to the fuel industry as anti-knock additives (Shapiro, 1959). Pioneering work was carried out by Köhler et al. (1984, 1987) using substituted cyclopentadienyl ligands. Sitzmannm & Wolmershauser (1995), Sitzmannm (2001) and Sitzmannm et al. (2003) were able to show that the introduction of steric bulk to the cyclopentadienyl ring significantly alters the reactivity of complexes containing main group elements, transition metals and lanthanides. This concept has been adopted by many other groups (Weber et al., 2002; Werkema & Andersen, 2001; Harvey & Hanusa, 2001; Schneider et al., 1999; Schneider & Krüger, 1992; Eichhorn et al., 2001). However, the synthetic potential of bulky cyclopentadienyl ligands in (RnC5H5-n)MnX has not been previously explored.
Di-µ-chloro-bis[(tetrahydrofuran-κO)(η5-1,2,4-tri-tert- butylcyclopentadienyl)manganese(II)] pentane solvate, (I), is a centrosymmetric dimer. The manganese centers are bridged by chlorides forming a nearly square four-membered Mn2Cl2 metallocycle. One tBu3—C5H2 ('''Cp) ligand, two chlorides and one O-coordinated tetrahydrofuran (thf) molecule establish a distorted-tetrahedral coordination sphere about each metal. The Mn—'''Cp (C1–C5) bond lengths are 2.449 (4), 2.490 (4), 2.431 (4), 2.444 (4) and 2.407 (4) Å, respectively. This deviation from ideal η5 coordination may be due to the relative trans influences of the chloride and thf. This trend agrees well with that observed in [(MeCp)Mn(PEt3)Cl]2, (II) (Köhler et al., 1984, 1987). Studies by Köhler et al. indicate that the Mn—'''Cp bond lengths are consistent with high-spin MnII. The intramolecular Mn···Mn distance (3.57 Å) in compound (I) is similar to that in (II) (3.52 Å). This separation is too large for any significant bonding interaction, therefore each manganese center should be considered formally a 17-electron species. The unit cell contains one molecule of pentane. The central C atom sits on the inversion center at (1/2, 1/2, 0). The C atoms at the two and four postions each have 50% occupancy, and the terminal C atoms have full occupancy. No H atoms for the disordered pentane were included in the refinement.