The title compound, [Mo
2O
5(C
11H
10N
3O)
2]·2CH
3CN, is a dinuclear molybdenum complex. It has crystallographic
C2 symmetry with the central O atom located on a twofold rotation axis. The Mo atoms, octahedrally coordinated by four O and two N atoms, are bridged by a μ-O and two μ-pyrazolonyl groups. An intermolecular N—H
O hydrogen bond stabilizes the crystal packing.
Supporting information
CCDC reference: 175324
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.088
- Data-to-parameter ratio = 22.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C26 H26 Mo2 N8 O7
Atom count from _chemical_formula_moiety:C4 H6 N2
FcTpPhLi (0.31 g, 0.50 mmol) and Mo(CO)6 (0.20 g, 0.75 mmol) were dissolved
in acetonitrile (25 ml) and the mixture was refluxed for 6 h. After
filtration, the filtrate was driven off under reduced pressure. The residue
was dissolved in toluene (30 ml) and then 3-bromo-2-methylpropene (0.10 ml,
0.99 mmol) was added. The mixture was kept under reflux for 7 h, then cooled
to 293 K. The solvent was removed in vacuo and the solid residue washed
with hexane (15 ml). The crude product was recrystallized from CH3CN/toluene
(1:2). Upon standing in air for several days, the title complex was obtained
as yellow crystals as the diacetonitrile adduct. 1H NMR (250.1 MHz,
DMSO-d6): δ = 2.07 (s, 3H, CH3CN), 2.19 (s, 6H, CH3C=NH), 7.34 (mult,
6H, Ph—H3,4,5), 7.74 [d, 4H, J(HH) = 6.9 Hz, Ph—H2,6], 8.54 (s, 2H, pz-H).
All H atoms were located by difference Fourier synthesis and refined with fixed
individual displacement parameters [Uiso(H) = 1.2Ueq(N), 1.2
Ueq(C) or 1.5Ueq(Cmethyl)] using a riding model with N—H
= 0.88 Å, aromatic C—H = 0.95 Å or methyl C—H = 0.98 Å. The methyl
groups was allowed to rotate about their local threefold axes.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).
Crystal data top
[Mo2O5(C11H10N3O)2]·2CH3CN | Dx = 1.718 Mg m−3 |
Mr = 754.43 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 85437 reflections |
a = 14.2861 (4) Å | θ = 4.3–61.3° |
b = 11.8522 (4) Å | µ = 0.92 mm−1 |
c = 17.2215 (6) Å | T = 173 K |
V = 2915.97 (16) Å3 | Needle, yellow |
Z = 4 | 0.50 × 0.14 × 0.08 mm |
F(000) = 1512 | |
Data collection top
Stoe IPDSII two-circle diffractometer | 4464 independent reflections |
Radiation source: fine-focus sealed tube | 3841 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 30.6°, θmin = 2.2° |
Absorption correction: empirical (MULABS; Spek, 1990; Blessing, 1995) | h = −20→20 |
Tmin = 0.657, Tmax = 0.930 | k = −16→16 |
83661 measured reflections | l = −24→24 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.018P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4464 reflections | Δρmax = 0.74 e Å−3 |
198 parameters | Δρmin = −0.72 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0082 (5) |
Crystal data top
[Mo2O5(C11H10N3O)2]·2CH3CN | V = 2915.97 (16) Å3 |
Mr = 754.43 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 14.2861 (4) Å | µ = 0.92 mm−1 |
b = 11.8522 (4) Å | T = 173 K |
c = 17.2215 (6) Å | 0.50 × 0.14 × 0.08 mm |
Data collection top
Stoe IPDSII two-circle diffractometer | 4464 independent reflections |
Absorption correction: empirical (MULABS; Spek, 1990; Blessing, 1995) | 3841 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.930 | Rint = 0.056 |
83661 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.74 e Å−3 |
4464 reflections | Δρmin = −0.72 e Å−3 |
198 parameters | |
Special details top
Experimental. ; |
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 | |
Mo1 | 0.547352 (10) | −0.054912 (11) | 0.152042 (7) | 0.02119 (7) | |
O1 | 0.5000 | −0.10373 (13) | 0.2500 | 0.0240 (3) | |
O2 | 0.48649 (9) | −0.12357 (10) | 0.07992 (7) | 0.0274 (2) | |
O3 | 0.65325 (10) | −0.12211 (12) | 0.15252 (7) | 0.0325 (3) | |
N11 | 0.60061 (10) | 0.09185 (12) | 0.21902 (8) | 0.0233 (3) | |
N12 | 0.63504 (10) | 0.18120 (11) | 0.17592 (8) | 0.0252 (3) | |
C13 | 0.66131 (12) | 0.26856 (14) | 0.22357 (10) | 0.0269 (3) | |
H13 | 0.6867 | 0.3387 | 0.2072 | 0.032* | |
C14 | 0.64454 (12) | 0.23725 (14) | 0.29848 (9) | 0.0246 (3) | |
C15 | 0.60419 (11) | 0.12426 (13) | 0.29397 (9) | 0.0220 (3) | |
O15 | 0.57534 (11) | 0.06202 (10) | 0.34972 (6) | 0.0244 (2) | |
C16 | 0.62718 (11) | 0.17082 (14) | 0.09717 (9) | 0.0249 (3) | |
N16 | 0.59352 (10) | 0.07560 (12) | 0.07263 (8) | 0.0247 (3) | |
H16 | 0.5893 | 0.0637 | 0.0223 | 0.030* | |
C17 | 0.65401 (14) | 0.26909 (16) | 0.04797 (10) | 0.0316 (3) | |
H17A | 0.6557 | 0.2460 | −0.0066 | 0.047* | |
H17B | 0.7160 | 0.2963 | 0.0636 | 0.047* | |
H17C | 0.6080 | 0.3296 | 0.0546 | 0.047* | |
C21 | 0.66059 (12) | 0.30409 (14) | 0.36933 (9) | 0.0257 (3) | |
C22 | 0.72393 (13) | 0.39399 (15) | 0.36913 (10) | 0.0291 (3) | |
H22 | 0.7588 | 0.4104 | 0.3235 | 0.035* | |
C23 | 0.73628 (14) | 0.45969 (15) | 0.43561 (11) | 0.0316 (4) | |
H23 | 0.7794 | 0.5207 | 0.4350 | 0.038* | |
C24 | 0.68558 (15) | 0.43611 (14) | 0.50278 (11) | 0.0318 (4) | |
H24 | 0.6932 | 0.4818 | 0.5476 | 0.038* | |
C25 | 0.62409 (14) | 0.34591 (16) | 0.50396 (10) | 0.0330 (4) | |
H25 | 0.5904 | 0.3289 | 0.5501 | 0.040* | |
C26 | 0.61143 (13) | 0.28003 (15) | 0.43799 (10) | 0.0296 (3) | |
H26 | 0.5691 | 0.2182 | 0.4394 | 0.036* | |
N1L | 0.6401 (3) | 0.5477 (2) | 0.19500 (15) | 0.0729 (8) | |
C2L | 0.62611 (19) | 0.5964 (2) | 0.25022 (15) | 0.0489 (5) | |
C3L | 0.6073 (2) | 0.6587 (2) | 0.32048 (17) | 0.0555 (6) | |
H3L1 | 0.5868 | 0.7352 | 0.3072 | 0.083* | |
H3L2 | 0.6644 | 0.6626 | 0.3519 | 0.083* | |
H3L3 | 0.5580 | 0.6205 | 0.3500 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mo1 | 0.02475 (10) | 0.02034 (10) | 0.01850 (10) | 0.00079 (4) | −0.00086 (4) | −0.00117 (4) |
O1 | 0.0329 (8) | 0.0200 (7) | 0.0193 (6) | 0.000 | −0.0001 (6) | 0.000 |
O2 | 0.0353 (6) | 0.0248 (5) | 0.0221 (5) | −0.0017 (5) | −0.0015 (5) | −0.0023 (4) |
O3 | 0.0321 (7) | 0.0343 (7) | 0.0313 (6) | 0.0080 (5) | −0.0010 (5) | −0.0019 (5) |
N11 | 0.0261 (6) | 0.0236 (6) | 0.0202 (6) | −0.0046 (5) | −0.0005 (5) | 0.0010 (5) |
N12 | 0.0306 (7) | 0.0245 (6) | 0.0205 (6) | −0.0046 (5) | 0.0017 (5) | 0.0012 (5) |
C13 | 0.0296 (8) | 0.0255 (7) | 0.0255 (7) | −0.0058 (6) | 0.0007 (6) | −0.0015 (6) |
C14 | 0.0252 (7) | 0.0248 (7) | 0.0237 (7) | −0.0036 (6) | 0.0009 (6) | −0.0017 (5) |
C15 | 0.0213 (6) | 0.0240 (7) | 0.0209 (6) | −0.0008 (5) | −0.0020 (5) | −0.0014 (5) |
O15 | 0.0274 (6) | 0.0251 (6) | 0.0208 (6) | −0.0025 (4) | −0.0020 (4) | 0.0014 (4) |
C16 | 0.0254 (7) | 0.0273 (7) | 0.0220 (6) | −0.0001 (6) | 0.0016 (5) | 0.0011 (5) |
N16 | 0.0274 (7) | 0.0277 (6) | 0.0191 (6) | −0.0017 (5) | 0.0014 (5) | −0.0002 (5) |
C17 | 0.0380 (9) | 0.0303 (8) | 0.0267 (7) | −0.0045 (7) | 0.0015 (7) | 0.0041 (6) |
C21 | 0.0277 (8) | 0.0249 (7) | 0.0244 (7) | −0.0015 (6) | −0.0018 (6) | −0.0020 (6) |
C22 | 0.0331 (8) | 0.0270 (8) | 0.0274 (7) | −0.0050 (6) | −0.0009 (6) | −0.0005 (6) |
C23 | 0.0372 (9) | 0.0251 (7) | 0.0326 (8) | −0.0058 (7) | −0.0037 (7) | −0.0027 (6) |
C24 | 0.0397 (10) | 0.0269 (8) | 0.0288 (8) | 0.0013 (6) | −0.0050 (7) | −0.0061 (6) |
C25 | 0.0374 (9) | 0.0346 (9) | 0.0270 (7) | −0.0018 (7) | 0.0036 (7) | −0.0056 (6) |
C26 | 0.0314 (8) | 0.0295 (8) | 0.0279 (7) | −0.0062 (6) | 0.0018 (6) | −0.0032 (6) |
N1L | 0.114 (3) | 0.0609 (15) | 0.0436 (12) | 0.0231 (15) | 0.0080 (14) | 0.0042 (10) |
C2L | 0.0597 (15) | 0.0427 (11) | 0.0443 (11) | 0.0124 (10) | −0.0011 (11) | 0.0039 (9) |
C3L | 0.0561 (15) | 0.0525 (14) | 0.0580 (14) | 0.0154 (12) | −0.0064 (12) | −0.0124 (12) |
Geometric parameters (Å, º) top
Mo1—O3 | 1.7098 (14) | C17—H17A | 0.9800 |
Mo1—O2 | 1.7206 (12) | C17—H17B | 0.9800 |
Mo1—O1 | 1.9074 (5) | C17—H17C | 0.9800 |
Mo1—N16 | 2.1676 (14) | C21—C22 | 1.398 (2) |
Mo1—N11 | 2.2216 (13) | C21—C26 | 1.405 (2) |
Mo1—O15i | 2.2347 (14) | C22—C23 | 1.396 (2) |
O1—Mo1i | 1.9074 (5) | C22—H22 | 0.9500 |
N11—C15 | 1.3476 (19) | C23—C24 | 1.393 (3) |
N11—N12 | 1.3836 (18) | C23—H23 | 0.9500 |
N12—C16 | 1.3664 (19) | C24—C25 | 1.384 (3) |
N12—C13 | 1.373 (2) | C24—H24 | 0.9500 |
C13—C14 | 1.364 (2) | C25—C26 | 1.390 (2) |
C13—H13 | 0.9500 | C25—H25 | 0.9500 |
C14—C15 | 1.460 (2) | C26—H26 | 0.9500 |
C14—C21 | 1.473 (2) | N1L—C2L | 1.131 (4) |
C15—O15 | 1.2790 (19) | C2L—C3L | 1.442 (4) |
O15—Mo1i | 2.2347 (14) | C3L—H3L1 | 0.9800 |
C16—N16 | 1.297 (2) | C3L—H3L2 | 0.9800 |
C16—C17 | 1.490 (2) | C3L—H3L3 | 0.9800 |
N16—H16 | 0.8800 | | |
| | | |
O3—Mo1—O2 | 103.31 (6) | C16—N16—Mo1 | 121.87 (11) |
O3—Mo1—O1 | 99.69 (5) | C16—N16—H16 | 119.1 |
O2—Mo1—O1 | 108.40 (5) | Mo1—N16—H16 | 119.1 |
O3—Mo1—N16 | 93.80 (6) | C16—C17—H17A | 109.5 |
O2—Mo1—N16 | 92.05 (5) | C16—C17—H17B | 109.5 |
O1—Mo1—N16 | 151.94 (6) | H17A—C17—H17B | 109.5 |
O3—Mo1—N11 | 93.39 (6) | C16—C17—H17C | 109.5 |
O2—Mo1—N11 | 156.66 (5) | H17A—C17—H17C | 109.5 |
O1—Mo1—N11 | 84.25 (5) | H17B—C17—H17C | 109.5 |
N16—Mo1—N11 | 70.40 (5) | C22—C21—C26 | 118.72 (15) |
O3—Mo1—O15i | 169.42 (6) | C22—C21—C14 | 120.58 (15) |
O2—Mo1—O15i | 83.52 (5) | C26—C21—C14 | 120.69 (15) |
O1—Mo1—O15i | 85.52 (4) | C23—C22—C21 | 120.34 (17) |
N16—Mo1—O15i | 77.73 (5) | C23—C22—H22 | 119.8 |
N11—Mo1—O15i | 77.88 (5) | C21—C22—H22 | 119.8 |
Mo1i—O1—Mo1 | 144.69 (9) | C24—C23—C22 | 120.23 (17) |
C15—N11—N12 | 106.39 (12) | C24—C23—H23 | 119.9 |
C15—N11—Mo1 | 137.18 (11) | C22—C23—H23 | 119.9 |
N12—N11—Mo1 | 116.26 (9) | C25—C24—C23 | 119.82 (16) |
C16—N12—C13 | 133.11 (14) | C25—C24—H24 | 120.1 |
C16—N12—N11 | 115.75 (13) | C23—C24—H24 | 120.1 |
C13—N12—N11 | 110.71 (13) | C24—C25—C26 | 120.29 (17) |
C14—C13—N12 | 108.19 (14) | C24—C25—H25 | 119.9 |
C14—C13—H13 | 125.9 | C26—C25—H25 | 119.9 |
N12—C13—H13 | 125.9 | C25—C26—C21 | 120.58 (16) |
C13—C14—C15 | 105.58 (14) | C25—C26—H26 | 119.7 |
C13—C14—C21 | 127.59 (15) | C21—C26—H26 | 119.7 |
C15—C14—C21 | 126.80 (14) | N1L—C2L—C3L | 179.5 (3) |
O15—C15—N11 | 122.84 (14) | C2L—C3L—H3L1 | 109.5 |
O15—C15—C14 | 128.05 (14) | C2L—C3L—H3L2 | 109.5 |
N11—C15—C14 | 109.11 (13) | H3L1—C3L—H3L2 | 109.5 |
C15—O15—Mo1i | 126.89 (10) | C2L—C3L—H3L3 | 109.5 |
N16—C16—N12 | 115.60 (14) | H3L1—C3L—H3L3 | 109.5 |
N16—C16—C17 | 126.14 (15) | H3L2—C3L—H3L3 | 109.5 |
N12—C16—C17 | 118.21 (15) | | |
| | | |
O3—Mo1—O1—Mo1i | 123.39 (5) | C21—C14—C15—O15 | 0.0 (3) |
O2—Mo1—O1—Mo1i | −128.97 (5) | C13—C14—C15—N11 | 1.53 (19) |
N16—Mo1—O1—Mo1i | 5.81 (9) | C21—C14—C15—N11 | 179.73 (16) |
N11—Mo1—O1—Mo1i | 30.92 (4) | N11—C15—O15—Mo1i | −35.8 (2) |
O15i—Mo1—O1—Mo1i | −47.33 (3) | C14—C15—O15—Mo1i | 143.96 (14) |
O3—Mo1—N11—C15 | −94.33 (17) | C13—N12—C16—N16 | −175.46 (17) |
O2—Mo1—N11—C15 | 129.65 (17) | N11—N12—C16—N16 | −3.9 (2) |
O1—Mo1—N11—C15 | 5.08 (16) | C13—N12—C16—C17 | 2.3 (3) |
N16—Mo1—N11—C15 | 172.85 (17) | N11—N12—C16—C17 | 173.86 (15) |
O15i—Mo1—N11—C15 | 91.72 (17) | N12—C16—N16—Mo1 | 2.6 (2) |
O3—Mo1—N11—N12 | 91.18 (12) | C17—C16—N16—Mo1 | −175.03 (13) |
O2—Mo1—N11—N12 | −44.8 (2) | O3—Mo1—N16—C16 | −92.75 (14) |
O1—Mo1—N11—N12 | −169.42 (11) | O2—Mo1—N16—C16 | 163.76 (14) |
N16—Mo1—N11—N12 | −1.65 (11) | O1—Mo1—N16—C16 | 26.13 (19) |
O15i—Mo1—N11—N12 | −82.78 (11) | N11—Mo1—N16—C16 | −0.50 (13) |
C15—N11—N12—C16 | −172.55 (14) | O15i—Mo1—N16—C16 | 80.84 (13) |
Mo1—N11—N12—C16 | 3.56 (18) | C13—C14—C21—C22 | −21.7 (3) |
C15—N11—N12—C13 | 0.84 (18) | C15—C14—C21—C22 | 160.49 (17) |
Mo1—N11—N12—C13 | 176.95 (11) | C13—C14—C21—C26 | 157.20 (19) |
C16—N12—C13—C14 | 171.97 (18) | C15—C14—C21—C26 | −20.6 (3) |
N11—N12—C13—C14 | 0.1 (2) | C26—C21—C22—C23 | −1.3 (3) |
N12—C13—C14—C15 | −0.98 (19) | C14—C21—C22—C23 | 177.60 (17) |
N12—C13—C14—C21 | −179.16 (16) | C21—C22—C23—C24 | 0.1 (3) |
N12—N11—C15—O15 | 178.35 (15) | C22—C23—C24—C25 | 1.2 (3) |
Mo1—N11—C15—O15 | 3.5 (3) | C23—C24—C25—C26 | −1.2 (3) |
N12—N11—C15—C14 | −1.44 (18) | C24—C25—C26—C21 | −0.1 (3) |
Mo1—N11—C15—C14 | −176.29 (12) | C22—C21—C26—C25 | 1.4 (3) |
C13—C14—C15—O15 | −178.24 (17) | C14—C21—C26—C25 | −177.57 (17) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16···O2ii | 0.88 | 2.19 | 2.9209 (18) | 141 |
C13—H13···N1L | 0.95 | 2.57 | 3.358 (3) | 140 |
C24—H24···N1Liii | 0.95 | 2.67 | 3.379 (3) | 132 |
C25—H25···N1Liii | 0.95 | 2.98 | 3.531 (3) | 118 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x, −y+1, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Mo2O5(C11H10N3O)2]·2CH3CN |
Mr | 754.43 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 173 |
a, b, c (Å) | 14.2861 (4), 11.8522 (4), 17.2215 (6) |
V (Å3) | 2915.97 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.50 × 0.14 × 0.08 |
|
Data collection |
Diffractometer | Stoe IPDSII two-circle diffractometer |
Absorption correction | Empirical (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.657, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 83661, 4464, 3841 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.716 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.05 |
No. of reflections | 4464 |
No. of parameters | 198 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.72 |
Selected geometric parameters (Å, º) topMo1—O3 | 1.7098 (14) | N11—C15 | 1.3476 (19) |
Mo1—O2 | 1.7206 (12) | N12—C13 | 1.373 (2) |
Mo1—O1 | 1.9074 (5) | C13—C14 | 1.364 (2) |
Mo1—N16 | 2.1676 (14) | C14—C15 | 1.460 (2) |
Mo1—N11 | 2.2216 (13) | C15—O15 | 1.2790 (19) |
Mo1—O15i | 2.2347 (14) | C16—N16 | 1.297 (2) |
| | | |
O3—Mo1—O2 | 103.31 (6) | O1—Mo1—N11 | 84.25 (5) |
O3—Mo1—O1 | 99.69 (5) | N16—Mo1—N11 | 70.40 (5) |
O2—Mo1—O1 | 108.40 (5) | O3—Mo1—O15i | 169.42 (6) |
O3—Mo1—N16 | 93.80 (6) | O2—Mo1—O15i | 83.52 (5) |
O2—Mo1—N16 | 92.05 (5) | O1—Mo1—O15i | 85.52 (4) |
O1—Mo1—N16 | 151.94 (6) | N16—Mo1—O15i | 77.73 (5) |
O3—Mo1—N11 | 93.39 (6) | N11—Mo1—O15i | 77.88 (5) |
O2—Mo1—N11 | 156.66 (5) | Mo1i—O1—Mo1 | 144.69 (9) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16···O2ii | 0.88 | 2.19 | 2.9209 (18) | 141 |
C13—H13···N1L | 0.95 | 2.57 | 3.358 (3) | 140.1 |
C24—H24···N1Liii | 0.95 | 2.67 | 3.379 (3) | 131.7 |
C25—H25···N1Liii | 0.95 | 2.98 | 3.531 (3) | 118.4 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x, −y+1, z+1/2. |
Ferrocene-based scorpionate ligands can serve as building blocks for the generation of redox-active, metal-containing polymers (Jäkle et al., 1996; Fabrizi de Biani et al., 1997; Herdtweck et al., 1998). Molybdenum is a multivalent element and can be coordinated in various ways. When this element is employed as a central metal of the polymer, some novel and peculiar physical properties may be expected. We tried to synthesize the monomer FcTpPhMo(CO)2(η3-C4H7) [Fc = ferrocenyl, TpPh = tris(4-phenylpyrazolyl)borate, C4H7 = 2-methylallyl; for the preparation of 4-phenyl pyrazole, see Tolf et al. (1979)], starting from FcTpPhLi and Mo(CO)6, followed by treatement with 3-bromo-2-methylpropene. Due to a leakage in the apparatus, the reaction mixture came into contact with air and moisture. As a result, the target compound was not obtained but, the title complex, (I), was isolated instead. Formation of (I) occurred via a complete breakdown of the scorpionate ligand, accompanied by molybdenum oxidation, as well as oxidative CH activation at the pyrazolyl moiety. Moreover, nucleophilic attack on acetonitrile by a pyrazolyl N atom led to the incorporation of solvent molecules into the complex.
Complex (I) (Fig. 1), characterized as its diacetonitrile adduct, has crystallographic C2 symmetry with the central O atom located on a twofold rotation axis. The Mo atoms are octahedrally coordinated by four O atoms and two N atoms. The two Mo═O double bonds, Mo1═O2 and Mo1═O3, are almost of equal length (Table 1), but the fact that O2 acts as an acceptor for an intermolecular hydrogen bond (Table 2) is reflected by its elongated distance to Mo. The O atom bridging the Mo atoms displays an angle of 144.69 (9)°. The longest bond to Mo is established by O15, which also forms a double bond to the pyrazolone ring. The length of this double bond is in agreement with 175 comparable structures retrieved from the Cambridge Structural Database (Version 5.21, April 2001; Allen & Kennard, 1993). For these structures, the following mean values were found: C═O 1.25 (4) Å, C—C 1.43 (3) Å and C═C 1.37 (3) Å. In contrast to parent pyrazole, which exhibits two C—C bonds of equal length [1.37 (2) Å], the C13—C14 and C14—C15 bond distances in (I) are significantly different from each other, i.e. 1.364 (2) and 1.460 (2) Å, respectively. These alternating bonds indicate the aromatic system of the pyrazole ring to be severely perturbed as is to be expected for a pyrazolone moiety. The pyrazolone and the phenyl ring are not coplanar, the dihedral angle between them is 21.41 (9)°. The gaps between the molecules of (I) are occupied by acetonitrile solvent molecules which form several weak hydrogen bonds (Table 2).