Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042791/sj2349sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042791/sj2349Isup2.hkl |
CCDC reference: 663573
Mo(CO)6 and excess 1,10-phenanthroline were refluxed in toluene under an N2 atmosphere for seven hours. After cooling, air-stable greenish-black chunks of (I) were recovered by vacuum filtration and rinsing with light petroleum ether.
The hydrogen atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
The title compound, (I), Mo(CO)2(phen)2 (phen = 1,10-phenanthroline, C12H8N2), was first reported over forty years ago by Behrens & Harder (1964). Chisholm et al. (1984) described the crystal structure of its close analogue Mo(CO)2(bipy)2 (bipy = 2,2'-bipyridine, C10H8N2). Both compounds originate from Mo(CO)6 by the replacement of four carbonyl groups by two N,N-bidentate aromatic ligands.
The asymmetric unit of compound (I) is built up around a distorted cis-MoC2N4 octahedron (Table 1; Fig. 1). The N1—Mo1—N2 and N3—Mo1—N4 phen bite angles are 74.43 (17)° and 73.97 (18)°, respectively, The cis C1—Mo1—C2 angle of 88.0 (3)° in (I) indicates a near ideal (90°) geometry for this grouping. The equivalent angle in Mo(CO)2(bipy)2 is compressed to 82.6 (3)°. Theoretical calculations (Kubácek & Hoffmann, 1981) have suggested an electronic origin for this type of distortion: it is not clear why it occurs in Mo(CO)2(bipy)2 but not in (I).
Both phen ligands in (I) are close to planar and show normal geometrical parameters. The dihedral angle between N1/N2/C3—C13 and N3/N4/C14—C22 is 84.74 (9)°, i.e. the phen molecules are close to perpendicular, and Mo1 is displaced from the N1 and N3-containing molecules by 0.262 (4) Å and 0.068 (4) Å, respectively.
The short Mo1—C1 and Mo1—C2 distances in (I) imply a substantial electron transfer from the Mo 5 d orbitals to the CO antibonding π* orbitals (Chisholm et al., 1984). For comparison, the Mo—C separation in Mo(CO)6, in which the Mo d electrons are "shared out" between six Mo—C bonds, is 2.06 (2) Å (Cotton & Wing, 1965). The difference in Mo—N bond lengths in (I) was also seen in the analagous Mo(CO)2(bipy)2 (Chisholm et al., 1984), and related to models of possible Mo --> bipy(π*) back bonding.
An acute C—H···O bond (Table 2) and various π-π stacking interactions [centroid-centroid separation = 3.472 (3)–3.890 (4) Å] may help to establish the packing for (I), which appears to be quite different to that for Mo(CO)2(bipy)2.
For background, see: Behrens & Harder (1964); Cotton & Wing (1965); Chisholm et al. (1984); Kubácek & Hoffmann (1981).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). |
[Mo(CO)2(C12H8N2)2] | F(000) = 1032 |
Mr = 512.37 | Dx = 1.669 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2524 reflections |
a = 9.7031 (6) Å | θ = 2.6–24.6° |
b = 14.5684 (10) Å | µ = 0.68 mm−1 |
c = 14.7006 (9) Å | T = 296 K |
β = 101.142 (2)° | Chunk, green–black |
V = 2038.9 (2) Å3 | 0.22 × 0.19 × 0.17 mm |
Z = 4 |
Bruker SMART 1000 CCD diffractometer | 3603 independent reflections |
Radiation source: fine-focus sealed tube | 2320 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −11→10 |
Tmin = 0.865, Tmax = 0.896 | k = −17→17 |
11958 measured reflections | l = −11→17 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0827P)2] where P = (Fo2 + 2Fc2)/3 |
3603 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 1.58 e Å−3 |
0 restraints | Δρmin = −1.12 e Å−3 |
[Mo(CO)2(C12H8N2)2] | V = 2038.9 (2) Å3 |
Mr = 512.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7031 (6) Å | µ = 0.68 mm−1 |
b = 14.5684 (10) Å | T = 296 K |
c = 14.7006 (9) Å | 0.22 × 0.19 × 0.17 mm |
β = 101.142 (2)° |
Bruker SMART 1000 CCD diffractometer | 3603 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2320 reflections with I > 2σ(I) |
Tmin = 0.865, Tmax = 0.896 | Rint = 0.069 |
11958 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 0.95 | Δρmax = 1.58 e Å−3 |
3603 reflections | Δρmin = −1.12 e Å−3 |
298 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. |
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 | ||
Mo1 | 0.75010 (5) | 0.22662 (4) | 0.54232 (3) | 0.03397 (19) | |
C1 | 0.6848 (6) | 0.1357 (5) | 0.6200 (5) | 0.0451 (16) | |
C2 | 0.5790 (7) | 0.2066 (4) | 0.4523 (4) | 0.0416 (16) | |
O1 | 0.6409 (5) | 0.0837 (4) | 0.6684 (4) | 0.0723 (16) | |
O2 | 0.4796 (5) | 0.1909 (4) | 0.3943 (3) | 0.0636 (14) | |
C3 | 1.0121 (7) | 0.2653 (4) | 0.7098 (4) | 0.0450 (15) | |
H3 | 0.9471 | 0.2952 | 0.7383 | 0.054* | |
C4 | 1.1505 (8) | 0.2633 (5) | 0.7554 (5) | 0.0572 (19) | |
H4 | 1.1766 | 0.2906 | 0.8133 | 0.069* | |
C5 | 1.2489 (7) | 0.2210 (5) | 0.7151 (4) | 0.0546 (18) | |
H5 | 1.3426 | 0.2206 | 0.7450 | 0.066* | |
C6 | 1.2089 (7) | 0.1778 (5) | 0.6280 (4) | 0.0456 (16) | |
C7 | 1.0638 (6) | 0.1824 (4) | 0.5875 (4) | 0.0359 (14) | |
C8 | 1.0123 (6) | 0.1366 (4) | 0.5012 (4) | 0.0341 (13) | |
C9 | 1.1081 (6) | 0.0892 (4) | 0.4573 (4) | 0.0393 (15) | |
C10 | 1.2543 (7) | 0.0900 (5) | 0.4978 (5) | 0.0542 (19) | |
H10 | 1.3181 | 0.0611 | 0.4675 | 0.065* | |
C11 | 1.3007 (7) | 0.1321 (5) | 0.5797 (5) | 0.0536 (18) | |
H11 | 1.3963 | 0.1310 | 0.6050 | 0.064* | |
C12 | 1.0530 (8) | 0.0430 (5) | 0.3735 (4) | 0.0508 (18) | |
H12 | 1.1117 | 0.0122 | 0.3407 | 0.061* | |
C13 | 0.9112 (7) | 0.0450 (5) | 0.3422 (4) | 0.0484 (17) | |
H13 | 0.8725 | 0.0146 | 0.2876 | 0.058* | |
C14 | 0.8251 (7) | 0.0912 (4) | 0.3903 (4) | 0.0420 (16) | |
H14 | 0.7290 | 0.0900 | 0.3667 | 0.050* | |
C15 | 0.5923 (7) | 0.3434 (5) | 0.6732 (4) | 0.0455 (16) | |
H15 | 0.5796 | 0.2874 | 0.7008 | 0.055* | |
C16 | 0.5330 (7) | 0.4205 (5) | 0.7049 (5) | 0.0544 (19) | |
H16 | 0.4791 | 0.4151 | 0.7505 | 0.065* | |
C17 | 0.5542 (8) | 0.5049 (6) | 0.6686 (5) | 0.061 (2) | |
H17 | 0.5154 | 0.5574 | 0.6895 | 0.073* | |
C18 | 0.6350 (7) | 0.5108 (5) | 0.6000 (5) | 0.0477 (17) | |
C19 | 0.6890 (6) | 0.4298 (4) | 0.5716 (4) | 0.0392 (15) | |
C20 | 0.7682 (6) | 0.4315 (4) | 0.4978 (4) | 0.0392 (15) | |
C21 | 0.7944 (8) | 0.5157 (5) | 0.4583 (5) | 0.054 (2) | |
C22 | 0.7413 (8) | 0.5977 (5) | 0.4908 (6) | 0.067 (2) | |
H22 | 0.7598 | 0.6538 | 0.4655 | 0.080* | |
C23 | 0.6639 (9) | 0.5951 (5) | 0.5583 (6) | 0.066 (2) | |
H23 | 0.6289 | 0.6495 | 0.5778 | 0.079* | |
C24 | 0.8739 (8) | 0.5126 (6) | 0.3866 (5) | 0.062 (2) | |
H24 | 0.8949 | 0.5664 | 0.3582 | 0.075* | |
C25 | 0.9182 (9) | 0.4314 (6) | 0.3605 (5) | 0.068 (2) | |
H25 | 0.9707 | 0.4288 | 0.3139 | 0.081* | |
C26 | 0.8862 (7) | 0.3515 (5) | 0.4027 (4) | 0.0522 (18) | |
H26 | 0.9175 | 0.2960 | 0.3829 | 0.063* | |
N1 | 0.9670 (5) | 0.2270 (3) | 0.6277 (3) | 0.0366 (11) | |
N2 | 0.8708 (5) | 0.1393 (3) | 0.4707 (3) | 0.0347 (12) | |
N3 | 0.6669 (5) | 0.3443 (4) | 0.6053 (3) | 0.0367 (12) | |
N4 | 0.8127 (5) | 0.3502 (3) | 0.4701 (3) | 0.0373 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0355 (3) | 0.0410 (3) | 0.0249 (3) | 0.0045 (3) | 0.00437 (18) | 0.0041 (2) |
C1 | 0.032 (4) | 0.049 (4) | 0.052 (4) | 0.011 (3) | 0.004 (3) | 0.009 (3) |
C2 | 0.043 (4) | 0.045 (4) | 0.038 (4) | 0.011 (3) | 0.010 (3) | 0.005 (3) |
O1 | 0.060 (4) | 0.083 (4) | 0.079 (4) | 0.002 (3) | 0.026 (3) | 0.039 (3) |
O2 | 0.045 (3) | 0.094 (4) | 0.044 (3) | 0.007 (3) | −0.010 (2) | −0.006 (3) |
C3 | 0.054 (4) | 0.051 (4) | 0.030 (3) | −0.003 (3) | 0.010 (3) | 0.002 (3) |
C4 | 0.066 (5) | 0.067 (5) | 0.032 (4) | −0.004 (4) | −0.007 (3) | −0.003 (3) |
C5 | 0.047 (4) | 0.068 (5) | 0.042 (4) | −0.007 (4) | −0.010 (3) | 0.007 (3) |
C6 | 0.040 (4) | 0.056 (4) | 0.038 (4) | −0.002 (3) | −0.001 (3) | 0.009 (3) |
C7 | 0.037 (4) | 0.038 (3) | 0.032 (3) | −0.002 (3) | 0.007 (3) | 0.007 (3) |
C8 | 0.043 (4) | 0.033 (3) | 0.026 (3) | −0.001 (3) | 0.007 (3) | 0.006 (2) |
C9 | 0.039 (4) | 0.043 (4) | 0.037 (4) | 0.002 (3) | 0.011 (3) | 0.008 (3) |
C10 | 0.044 (4) | 0.061 (5) | 0.062 (5) | 0.006 (3) | 0.020 (3) | 0.002 (4) |
C11 | 0.032 (4) | 0.071 (5) | 0.057 (5) | 0.003 (3) | 0.005 (3) | 0.006 (4) |
C12 | 0.066 (5) | 0.055 (4) | 0.035 (4) | 0.014 (4) | 0.018 (3) | 0.008 (3) |
C13 | 0.057 (5) | 0.057 (4) | 0.027 (3) | 0.007 (4) | 0.000 (3) | −0.006 (3) |
C14 | 0.051 (4) | 0.043 (4) | 0.027 (3) | 0.003 (3) | −0.004 (3) | 0.001 (3) |
C15 | 0.046 (4) | 0.061 (5) | 0.030 (3) | 0.006 (3) | 0.009 (3) | 0.003 (3) |
C16 | 0.050 (4) | 0.079 (6) | 0.034 (4) | 0.011 (4) | 0.008 (3) | −0.014 (3) |
C17 | 0.057 (5) | 0.068 (5) | 0.051 (5) | 0.018 (4) | −0.004 (4) | −0.021 (4) |
C18 | 0.045 (4) | 0.046 (4) | 0.044 (4) | 0.004 (3) | −0.010 (3) | −0.007 (3) |
C19 | 0.039 (4) | 0.048 (4) | 0.025 (3) | 0.001 (3) | −0.008 (3) | −0.002 (3) |
C20 | 0.036 (4) | 0.044 (4) | 0.033 (3) | 0.001 (3) | −0.005 (3) | 0.008 (3) |
C21 | 0.064 (5) | 0.046 (4) | 0.041 (4) | −0.008 (3) | −0.012 (4) | 0.012 (3) |
C22 | 0.075 (6) | 0.037 (4) | 0.075 (6) | −0.004 (4) | −0.016 (5) | 0.013 (4) |
C23 | 0.078 (6) | 0.049 (5) | 0.059 (5) | 0.010 (4) | −0.013 (4) | −0.017 (4) |
C24 | 0.066 (5) | 0.058 (5) | 0.057 (5) | −0.013 (4) | −0.002 (4) | 0.031 (4) |
C25 | 0.078 (6) | 0.085 (7) | 0.043 (5) | 0.001 (5) | 0.017 (4) | 0.024 (4) |
C26 | 0.062 (5) | 0.059 (5) | 0.037 (4) | 0.002 (4) | 0.013 (3) | 0.009 (3) |
N1 | 0.044 (3) | 0.035 (3) | 0.029 (3) | −0.002 (3) | 0.001 (2) | 0.003 (2) |
N2 | 0.036 (3) | 0.042 (3) | 0.024 (3) | 0.000 (2) | 0.001 (2) | 0.004 (2) |
N3 | 0.030 (3) | 0.054 (3) | 0.024 (3) | 0.004 (2) | 0.001 (2) | 0.002 (2) |
N4 | 0.046 (3) | 0.039 (3) | 0.026 (3) | 0.001 (2) | 0.005 (2) | 0.005 (2) |
Mo1—C1 | 1.933 (7) | C13—C14 | 1.371 (9) |
Mo1—C2 | 1.935 (6) | C13—H13 | 0.9300 |
Mo1—N2 | 2.139 (5) | C14—N2 | 1.372 (7) |
Mo1—N3 | 2.177 (5) | C14—H14 | 0.9300 |
Mo1—N1 | 2.232 (5) | C15—N3 | 1.343 (7) |
Mo1—N4 | 2.233 (5) | C15—C16 | 1.382 (9) |
C1—O1 | 1.174 (8) | C15—H15 | 0.9300 |
C2—O2 | 1.180 (7) | C16—C17 | 1.371 (10) |
C3—N1 | 1.326 (7) | C16—H16 | 0.9300 |
C3—C4 | 1.380 (9) | C17—C18 | 1.396 (10) |
C3—H3 | 0.9300 | C17—H17 | 0.9300 |
C4—C5 | 1.364 (9) | C18—C19 | 1.388 (9) |
C4—H4 | 0.9300 | C18—C23 | 1.423 (10) |
C5—C6 | 1.412 (9) | C19—N3 | 1.372 (7) |
C5—H5 | 0.9300 | C19—C20 | 1.446 (9) |
C6—C11 | 1.410 (9) | C20—N4 | 1.350 (8) |
C6—C7 | 1.420 (8) | C20—C21 | 1.401 (9) |
C7—N1 | 1.367 (7) | C21—C22 | 1.419 (11) |
C7—C8 | 1.434 (8) | C21—C24 | 1.421 (11) |
C8—N2 | 1.360 (7) | C22—C23 | 1.355 (11) |
C8—C9 | 1.411 (8) | C22—H22 | 0.9300 |
C9—C12 | 1.415 (9) | C23—H23 | 0.9300 |
C9—C10 | 1.429 (8) | C24—C25 | 1.340 (10) |
C10—C11 | 1.348 (10) | C24—H24 | 0.9300 |
C10—H10 | 0.9300 | C25—C26 | 1.382 (9) |
C11—H11 | 0.9300 | C25—H25 | 0.9300 |
C12—C13 | 1.364 (9) | C26—N4 | 1.329 (8) |
C12—H12 | 0.9300 | C26—H26 | 0.9300 |
C1—Mo1—C2 | 88.0 (3) | C13—C14—H14 | 117.7 |
C1—Mo1—N2 | 99.0 (2) | N2—C14—H14 | 117.7 |
C2—Mo1—N2 | 93.0 (2) | N3—C15—C16 | 124.2 (7) |
C1—Mo1—N3 | 95.6 (2) | N3—C15—H15 | 117.9 |
C2—Mo1—N3 | 94.0 (2) | C16—C15—H15 | 117.9 |
N2—Mo1—N3 | 163.99 (19) | C17—C16—C15 | 119.6 (7) |
C1—Mo1—N1 | 92.9 (2) | C17—C16—H16 | 120.2 |
C2—Mo1—N1 | 167.4 (2) | C15—C16—H16 | 120.2 |
N2—Mo1—N1 | 74.43 (17) | C16—C17—C18 | 119.0 (7) |
N3—Mo1—N1 | 98.39 (17) | C16—C17—H17 | 120.5 |
C1—Mo1—N4 | 169.5 (2) | C18—C17—H17 | 120.5 |
C2—Mo1—N4 | 94.2 (2) | C19—C18—C17 | 117.5 (7) |
N2—Mo1—N4 | 91.20 (19) | C19—C18—C23 | 119.2 (7) |
N3—Mo1—N4 | 73.97 (18) | C17—C18—C23 | 123.3 (7) |
N1—Mo1—N4 | 87.24 (17) | N3—C19—C18 | 124.7 (7) |
O1—C1—Mo1 | 176.7 (6) | N3—C19—C20 | 115.4 (6) |
O2—C2—Mo1 | 175.7 (6) | C18—C19—C20 | 119.8 (6) |
N1—C3—C4 | 123.5 (6) | N4—C20—C21 | 123.3 (7) |
N1—C3—H3 | 118.3 | N4—C20—C19 | 117.2 (6) |
C4—C3—H3 | 118.3 | C21—C20—C19 | 119.4 (6) |
C5—C4—C3 | 119.8 (6) | C20—C21—C22 | 119.4 (8) |
C5—C4—H4 | 120.1 | C20—C21—C24 | 116.5 (7) |
C3—C4—H4 | 120.1 | C22—C21—C24 | 124.1 (7) |
C4—C5—C6 | 120.1 (6) | C23—C22—C21 | 120.8 (7) |
C4—C5—H5 | 119.9 | C23—C22—H22 | 119.6 |
C6—C5—H5 | 119.9 | C21—C22—H22 | 119.6 |
C11—C6—C5 | 125.2 (6) | C22—C23—C18 | 121.5 (7) |
C11—C6—C7 | 118.9 (6) | C22—C23—H23 | 119.3 |
C5—C6—C7 | 115.9 (6) | C18—C23—H23 | 119.3 |
N1—C7—C6 | 123.3 (5) | C25—C24—C21 | 119.4 (7) |
N1—C7—C8 | 116.9 (5) | C25—C24—H24 | 120.3 |
C6—C7—C8 | 119.8 (6) | C21—C24—H24 | 120.3 |
N2—C8—C9 | 125.1 (5) | C24—C25—C26 | 120.1 (8) |
N2—C8—C7 | 115.8 (5) | C24—C25—H25 | 119.9 |
C9—C8—C7 | 119.0 (5) | C26—C25—H25 | 119.9 |
C8—C9—C12 | 117.4 (6) | N4—C26—C25 | 123.2 (7) |
C8—C9—C10 | 119.6 (6) | N4—C26—H26 | 118.4 |
C12—C9—C10 | 123.0 (6) | C25—C26—H26 | 118.4 |
C11—C10—C9 | 120.6 (7) | C3—N1—C7 | 117.4 (5) |
C11—C10—H10 | 119.7 | C3—N1—Mo1 | 128.5 (4) |
C9—C10—H10 | 119.7 | C7—N1—Mo1 | 114.1 (3) |
C10—C11—C6 | 122.0 (6) | C8—N2—C14 | 114.0 (5) |
C10—C11—H11 | 119.0 | C8—N2—Mo1 | 118.0 (4) |
C6—C11—H11 | 119.0 | C14—N2—Mo1 | 127.7 (4) |
C13—C12—C9 | 118.1 (6) | C15—N3—C19 | 114.9 (6) |
C13—C12—H12 | 121.0 | C15—N3—Mo1 | 127.3 (5) |
C9—C12—H12 | 121.0 | C19—N3—Mo1 | 117.7 (4) |
C12—C13—C14 | 120.8 (6) | C26—N4—C20 | 117.5 (6) |
C12—C13—H13 | 119.6 | C26—N4—Mo1 | 126.9 (4) |
C14—C13—H13 | 119.6 | C20—N4—Mo1 | 115.6 (4) |
C13—C14—N2 | 124.6 (6) | ||
N1—C3—C4—C5 | 0.8 (11) | C2—Mo1—N1—C3 | −169.4 (9) |
C3—C4—C5—C6 | −1.3 (11) | N2—Mo1—N1—C3 | −174.3 (5) |
C4—C5—C6—C11 | 180.0 (7) | N3—Mo1—N1—C3 | 20.4 (5) |
C4—C5—C6—C7 | 0.3 (10) | N4—Mo1—N1—C3 | 93.7 (5) |
C11—C6—C7—N1 | −178.3 (6) | C1—Mo1—N1—C7 | 105.3 (4) |
C5—C6—C7—N1 | 1.4 (9) | C2—Mo1—N1—C7 | 11.6 (12) |
C11—C6—C7—C8 | 3.3 (9) | N2—Mo1—N1—C7 | 6.8 (4) |
C5—C6—C7—C8 | −177.0 (6) | N3—Mo1—N1—C7 | −158.6 (4) |
N1—C7—C8—N2 | −2.8 (8) | N4—Mo1—N1—C7 | −85.3 (4) |
C6—C7—C8—N2 | 175.6 (5) | C9—C8—N2—C14 | −0.6 (8) |
N1—C7—C8—C9 | −179.6 (5) | C7—C8—N2—C14 | −177.2 (5) |
C6—C7—C8—C9 | −1.2 (8) | C9—C8—N2—Mo1 | −174.2 (4) |
N2—C8—C9—C12 | 2.0 (9) | C7—C8—N2—Mo1 | 9.2 (6) |
C7—C8—C9—C12 | 178.5 (5) | C13—C14—N2—C8 | −0.9 (9) |
N2—C8—C9—C10 | −178.4 (6) | C13—C14—N2—Mo1 | 172.0 (5) |
C7—C8—C9—C10 | −1.9 (9) | C1—Mo1—N2—C8 | −99.1 (4) |
C8—C9—C10—C11 | 3.0 (10) | C2—Mo1—N2—C8 | 172.5 (4) |
C12—C9—C10—C11 | −177.5 (7) | N3—Mo1—N2—C8 | 56.5 (8) |
C9—C10—C11—C6 | −0.8 (11) | N1—Mo1—N2—C8 | −8.6 (4) |
C5—C6—C11—C10 | 177.9 (7) | N4—Mo1—N2—C8 | 78.2 (4) |
C7—C6—C11—C10 | −2.3 (11) | C1—Mo1—N2—C14 | 88.3 (5) |
C8—C9—C12—C13 | −2.0 (9) | C2—Mo1—N2—C14 | −0.2 (5) |
C10—C9—C12—C13 | 178.5 (6) | N3—Mo1—N2—C14 | −116.2 (7) |
C9—C12—C13—C14 | 0.7 (10) | N1—Mo1—N2—C14 | 178.8 (5) |
C12—C13—C14—N2 | 0.8 (10) | N4—Mo1—N2—C14 | −94.4 (5) |
N3—C15—C16—C17 | −2.7 (10) | C16—C15—N3—C19 | 3.8 (8) |
C15—C16—C17—C18 | 0.3 (10) | C16—C15—N3—Mo1 | −174.6 (5) |
C16—C17—C18—C19 | 0.5 (9) | C18—C19—N3—C15 | −3.0 (8) |
C16—C17—C18—C23 | −179.6 (6) | C20—C19—N3—C15 | −179.5 (5) |
C17—C18—C19—N3 | 0.9 (9) | C18—C19—N3—Mo1 | 175.6 (4) |
C23—C18—C19—N3 | −179.0 (5) | C20—C19—N3—Mo1 | −0.9 (6) |
C17—C18—C19—C20 | 177.3 (6) | C1—Mo1—N3—C15 | −2.0 (5) |
C23—C18—C19—C20 | −2.6 (8) | C2—Mo1—N3—C15 | 86.4 (5) |
N3—C19—C20—N4 | −0.4 (8) | N2—Mo1—N3—C15 | −157.7 (6) |
C18—C19—C20—N4 | −177.1 (5) | N1—Mo1—N3—C15 | −95.8 (5) |
N3—C19—C20—C21 | 179.2 (5) | N4—Mo1—N3—C15 | 179.6 (5) |
C18—C19—C20—C21 | 2.5 (8) | C1—Mo1—N3—C19 | 179.7 (4) |
N4—C20—C21—C22 | 178.9 (6) | C2—Mo1—N3—C19 | −92.0 (4) |
C19—C20—C21—C22 | −0.7 (9) | N2—Mo1—N3—C19 | 23.9 (8) |
N4—C20—C21—C24 | −0.9 (9) | N1—Mo1—N3—C19 | 85.9 (4) |
C19—C20—C21—C24 | 179.5 (6) | N4—Mo1—N3—C19 | 1.2 (4) |
C20—C21—C22—C23 | −1.1 (10) | C25—C26—N4—C20 | 0.0 (10) |
C24—C21—C22—C23 | 178.7 (7) | C25—C26—N4—Mo1 | 178.8 (5) |
C21—C22—C23—C18 | 1.0 (11) | C21—C20—N4—C26 | 0.8 (9) |
C19—C18—C23—C22 | 0.9 (10) | C19—C20—N4—C26 | −179.7 (5) |
C17—C18—C23—C22 | −179.0 (7) | C21—C20—N4—Mo1 | −178.2 (4) |
C20—C21—C24—C25 | 0.4 (10) | C19—C20—N4—Mo1 | 1.4 (6) |
C22—C21—C24—C25 | −179.4 (7) | C1—Mo1—N4—C26 | 171.2 (11) |
C21—C24—C25—C26 | 0.3 (11) | C2—Mo1—N4—C26 | −87.2 (5) |
C24—C25—C26—N4 | −0.5 (11) | N2—Mo1—N4—C26 | 5.9 (5) |
C4—C3—N1—C7 | 0.8 (9) | N3—Mo1—N4—C26 | 179.8 (6) |
C4—C3—N1—Mo1 | −178.1 (5) | N1—Mo1—N4—C26 | 80.3 (5) |
C6—C7—N1—C3 | −1.9 (9) | C1—Mo1—N4—C20 | −10.0 (14) |
C8—C7—N1—C3 | 176.5 (5) | C2—Mo1—N4—C20 | 91.6 (4) |
C6—C7—N1—Mo1 | 177.2 (5) | N2—Mo1—N4—C20 | −175.3 (4) |
C8—C7—N1—Mo1 | −4.4 (6) | N3—Mo1—N4—C20 | −1.4 (4) |
C1—Mo1—N1—C3 | −75.8 (5) | N1—Mo1—N4—C20 | −100.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.47 | 3.381 (8) | 165 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mo(CO)2(C12H8N2)2] |
Mr | 512.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 9.7031 (6), 14.5684 (10), 14.7006 (9) |
β (°) | 101.142 (2) |
V (Å3) | 2038.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.22 × 0.19 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.865, 0.896 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11958, 3603, 2320 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.141, 0.95 |
No. of reflections | 3603 |
No. of parameters | 298 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.58, −1.12 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
Mo1—C1 | 1.933 (7) | Mo1—N3 | 2.177 (5) |
Mo1—C2 | 1.935 (6) | Mo1—N1 | 2.232 (5) |
Mo1—N2 | 2.139 (5) | Mo1—N4 | 2.233 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.93 | 2.47 | 3.381 (8) | 165 |
Symmetry code: (i) x+1, y, z. |
The title compound, (I), Mo(CO)2(phen)2 (phen = 1,10-phenanthroline, C12H8N2), was first reported over forty years ago by Behrens & Harder (1964). Chisholm et al. (1984) described the crystal structure of its close analogue Mo(CO)2(bipy)2 (bipy = 2,2'-bipyridine, C10H8N2). Both compounds originate from Mo(CO)6 by the replacement of four carbonyl groups by two N,N-bidentate aromatic ligands.
The asymmetric unit of compound (I) is built up around a distorted cis-MoC2N4 octahedron (Table 1; Fig. 1). The N1—Mo1—N2 and N3—Mo1—N4 phen bite angles are 74.43 (17)° and 73.97 (18)°, respectively, The cis C1—Mo1—C2 angle of 88.0 (3)° in (I) indicates a near ideal (90°) geometry for this grouping. The equivalent angle in Mo(CO)2(bipy)2 is compressed to 82.6 (3)°. Theoretical calculations (Kubácek & Hoffmann, 1981) have suggested an electronic origin for this type of distortion: it is not clear why it occurs in Mo(CO)2(bipy)2 but not in (I).
Both phen ligands in (I) are close to planar and show normal geometrical parameters. The dihedral angle between N1/N2/C3—C13 and N3/N4/C14—C22 is 84.74 (9)°, i.e. the phen molecules are close to perpendicular, and Mo1 is displaced from the N1 and N3-containing molecules by 0.262 (4) Å and 0.068 (4) Å, respectively.
The short Mo1—C1 and Mo1—C2 distances in (I) imply a substantial electron transfer from the Mo 5 d orbitals to the CO antibonding π* orbitals (Chisholm et al., 1984). For comparison, the Mo—C separation in Mo(CO)6, in which the Mo d electrons are "shared out" between six Mo—C bonds, is 2.06 (2) Å (Cotton & Wing, 1965). The difference in Mo—N bond lengths in (I) was also seen in the analagous Mo(CO)2(bipy)2 (Chisholm et al., 1984), and related to models of possible Mo --> bipy(π*) back bonding.
An acute C—H···O bond (Table 2) and various π-π stacking interactions [centroid-centroid separation = 3.472 (3)–3.890 (4) Å] may help to establish the packing for (I), which appears to be quite different to that for Mo(CO)2(bipy)2.