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The title complex, [W(η5-C5H5CH3)I(CO)3], lies on a crystallographic mirror plane, with only one half-molecule per asymmetric unit. This four-legged piano-stool tungsten complex is strained at the W atom, with the trans-C—W—I angle [130.93 (18)°] larger than the cis-C—W—C angle [111.1 (3)°]. A possible trans influence due to a larger π back-bonding is marginal, with an insignificant difference between the W—C bond length trans to I [1.984 (6) Å] and the other W—CCO bond lengths [1.996 (5) Å].
Supporting information
CCDC reference: 238675
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.020
- wR factor = 0.047
- Data-to-parameter ratio = 19.8
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .... C6
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... W1
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: XPREP (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Tricarbonyliodo(
η5-methylcyclopentadienyl)tungsten
top
Crystal data top
[W(C6H8)I(CO)3] | F(000) = 848 |
Mr = 473.9 | Dx = 2.8 Mg m−3 |
Monoclinic, C2/m | Melting point: 456 K |
Hall symbol: -C 2y | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5020 (16) Å | Cell parameters from 939 reflections |
b = 8.4577 (10) Å | θ = 2.9–28.3° |
c = 10.1886 (12) Å | µ = 13.00 mm−1 |
β = 104.949 (2)° | T = 293 K |
V = 1124.1 (2) Å3 | Needle, orange |
Z = 4 | 0.35 × 0.12 × 0.1 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1485 independent reflections |
Radiation source: fine-focus sealed tube | 1363 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −12→17 |
Tmin = 0.165, Tmax = 0.273 | k = −11→11 |
3934 measured reflections | l = −13→11 |
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)] = 0.02 | H-atom parameters constrained |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.021P)2 + 2.5564P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1485 reflections | Δρmax = 0.80 e Å−3 |
75 parameters | Δρmin = −0.57 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: 0.00169 (9) |
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 | Occ. (<1) |
W1 | 0.725916 (15) | 0.5 | 0.70453 (2) | 0.03813 (9) | |
I2 | 0.58022 (3) | 0.5 | 0.86264 (4) | 0.05197 (12) | |
O2 | 0.5990 (3) | 0.8093 (5) | 0.6123 (4) | 0.0768 (10) | |
C2 | 0.6428 (3) | 0.6946 (6) | 0.6453 (4) | 0.0511 (10) | |
O1 | 0.6946 (4) | 0.5 | 0.3901 (5) | 0.0844 (18) | |
C1 | 0.7069 (5) | 0.5 | 0.5048 (6) | 0.0553 (15) | |
C4 | 0.8538 (4) | 0.5 | 0.9206 (6) | 0.0490 (14) | |
C5 | 0.8657 (3) | 0.6344 (6) | 0.8460 (5) | 0.0558 (11) | |
H5 | 0.859 | 0.7389 | 0.8708 | 0.067* | |
C6 | 0.8898 (3) | 0.5821 (7) | 0.7259 (5) | 0.0670 (14) | |
H6 | 0.9033 | 0.6465 | 0.6587 | 0.08* | |
C9 | 0.8400 (6) | 0.5 | 1.0624 (7) | 0.077 (2) | |
H9A | 0.822 | 0.3956 | 1.0851 | 0.116* | 0.5 |
H9B | 0.7865 | 0.5725 | 1.0675 | 0.116* | 0.5 |
H9C | 0.9029 | 0.5319 | 1.1252 | 0.116* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
W1 | 0.02792 (12) | 0.04960 (15) | 0.03782 (13) | 0 | 0.01023 (8) | 0 |
I2 | 0.0416 (2) | 0.0648 (3) | 0.0566 (2) | 0 | 0.02549 (17) | 0 |
O2 | 0.074 (2) | 0.074 (3) | 0.084 (2) | 0.027 (2) | 0.0247 (19) | 0.025 (2) |
C2 | 0.042 (2) | 0.066 (3) | 0.049 (2) | 0.005 (2) | 0.0159 (17) | 0.010 (2) |
O1 | 0.072 (3) | 0.139 (6) | 0.043 (3) | 0 | 0.016 (2) | 0 |
C1 | 0.040 (3) | 0.076 (5) | 0.051 (3) | 0 | 0.014 (3) | 0 |
C4 | 0.031 (3) | 0.067 (4) | 0.046 (3) | 0 | 0.005 (2) | 0 |
C5 | 0.041 (2) | 0.056 (3) | 0.063 (3) | −0.0109 (19) | 0.0012 (18) | −0.002 (2) |
C6 | 0.0315 (19) | 0.111 (4) | 0.057 (2) | −0.015 (2) | 0.0101 (17) | 0.015 (3) |
C9 | 0.057 (4) | 0.126 (7) | 0.043 (3) | 0 | 0.005 (3) | 0 |
Geometric parameters (Å, º) top
W1—C1 | 1.984 (6) | C4—C5i | 1.399 (6) |
W1—C2i | 1.996 (5) | C4—C5 | 1.399 (6) |
W1—C2 | 1.996 (5) | C4—C9 | 1.504 (9) |
W1—C6 | 2.275 (4) | C5—C6 | 1.416 (7) |
W1—C6i | 2.275 (4) | C5—H5 | 0.93 |
W1—C5 | 2.351 (4) | C6—C6i | 1.388 (12) |
W1—C5i | 2.351 (4) | C6—H6 | 0.93 |
W1—C4 | 2.422 (5) | C9—H9A | 0.96 |
W1—I2 | 2.8460 (5) | C9—H9B | 0.96 |
O2—C2 | 1.140 (5) | C9—H9C | 0.96 |
O1—C1 | 1.138 (7) | | |
| | | |
C1—W1—C2i | 77.05 (15) | C6—W1—I2 | 137.98 (12) |
C1—W1—C2 | 77.05 (15) | C6i—W1—I2 | 137.98 (12) |
C2i—W1—C2 | 111.1 (3) | C5—W1—I2 | 102.44 (12) |
C1—W1—C6 | 87.9 (2) | C5i—W1—I2 | 102.44 (12) |
C2i—W1—C6 | 137.5 (2) | C4—W1—I2 | 85.43 (14) |
C2—W1—C6 | 103.58 (19) | O2—C2—W1 | 177.1 (4) |
C1—W1—C6i | 87.9 (2) | O1—C1—W1 | 179.0 (6) |
C2i—W1—C6i | 103.58 (19) | C5i—C4—C5 | 108.7 (6) |
C2—W1—C6i | 137.5 (2) | C5i—C4—C9 | 125.6 (3) |
C6—W1—C6i | 35.5 (3) | C5—C4—C9 | 125.6 (3) |
C1—W1—C5 | 119.98 (19) | C5i—C4—W1 | 70.2 (3) |
C2i—W1—C5 | 152.14 (18) | C5—C4—W1 | 70.2 (3) |
C2—W1—C5 | 94.97 (18) | C9—C4—W1 | 129.6 (4) |
C6—W1—C5 | 35.60 (17) | C4—C5—C6 | 107.4 (5) |
C6i—W1—C5 | 58.80 (18) | C4—C5—W1 | 75.7 (3) |
C1—W1—C5i | 119.98 (19) | C6—C5—W1 | 69.3 (2) |
C2i—W1—C5i | 94.97 (17) | C4—C5—H5 | 126.3 |
C2—W1—C5i | 152.14 (18) | C6—C5—H5 | 126.3 |
C6—W1—C5i | 58.80 (18) | W1—C5—H5 | 120.5 |
C6i—W1—C5i | 35.60 (17) | C6i—C6—C5 | 108.2 (3) |
C5—W1—C5i | 57.8 (2) | C6i—C6—W1 | 72.24 (15) |
C1—W1—C4 | 143.6 (2) | C5—C6—W1 | 75.1 (2) |
C2i—W1—C4 | 119.24 (14) | C6i—C6—H6 | 125.9 |
C2—W1—C4 | 119.24 (14) | C5—C6—H6 | 125.9 |
C6—W1—C4 | 57.67 (17) | W1—C6—H6 | 118.6 |
C6i—W1—C4 | 57.67 (17) | C4—C9—H9A | 109.5 |
C5—W1—C4 | 34.06 (13) | C4—C9—H9B | 109.5 |
C5i—W1—C4 | 34.06 (13) | H9A—C9—H9B | 109.5 |
C1—W1—I2 | 130.93 (18) | C4—C9—H9C | 109.5 |
C2i—W1—I2 | 75.77 (12) | H9A—C9—H9C | 109.5 |
C2—W1—I2 | 75.77 (12) | H9B—C9—H9C | 109.5 |
| | | |
C1—W1—C4—C5i | −59.7 (3) | C2—W1—C5—C4 | 138.3 (3) |
C2i—W1—C4—C5i | 49.4 (4) | C6—W1—C5—C4 | −115.2 (4) |
C2—W1—C4—C5i | −168.8 (3) | C6i—W1—C5—C4 | −77.3 (3) |
C6—W1—C4—C5i | −80.9 (4) | C5i—W1—C5—C4 | −35.2 (3) |
C6i—W1—C4—C5i | −38.6 (3) | I2—W1—C5—C4 | 61.8 (3) |
C5—W1—C4—C5i | −119.4 (6) | C1—W1—C5—C6 | −28.5 (4) |
I2—W1—C4—C5i | 120.3 (3) | C2i—W1—C5—C6 | 94.0 (4) |
C1—W1—C4—C5 | 59.7 (3) | C2—W1—C5—C6 | −106.5 (3) |
C2i—W1—C4—C5 | 168.8 (3) | C6i—W1—C5—C6 | 38.0 (4) |
C2—W1—C4—C5 | −49.4 (4) | C5i—W1—C5—C6 | 80.0 (3) |
C6—W1—C4—C5 | 38.6 (3) | C4—W1—C5—C6 | 115.2 (4) |
C6i—W1—C4—C5 | 80.9 (4) | I2—W1—C5—C6 | 177.0 (3) |
C5i—W1—C4—C5 | 119.4 (6) | C4—C5—C6—C6i | 1.6 (4) |
I2—W1—C4—C5 | −120.3 (3) | W1—C5—C6—C6i | −65.2 (2) |
C1—W1—C4—C9 | 180.000 (2) | C4—C5—C6—W1 | 66.8 (3) |
C2i—W1—C4—C9 | −70.89 (15) | C1—W1—C6—C6i | −89.3 (2) |
C2—W1—C4—C9 | 70.89 (15) | C2i—W1—C6—C6i | −21.2 (2) |
C6—W1—C4—C9 | 158.84 (18) | C2—W1—C6—C6i | −165.5 (2) |
C6i—W1—C4—C9 | −158.84 (18) | C5—W1—C6—C6i | 115.1 (3) |
C5—W1—C4—C9 | 120.3 (3) | C5i—W1—C6—C6i | 38.03 (17) |
C5i—W1—C4—C9 | −120.3 (3) | C4—W1—C6—C6i | 78.3 (2) |
I2—W1—C4—C9 | 0.000 (2) | I2—W1—C6—C6i | 110.82 (17) |
C5i—C4—C5—C6 | −2.6 (6) | C1—W1—C6—C5 | 155.5 (3) |
C9—C4—C5—C6 | 172.4 (5) | C2i—W1—C6—C5 | −136.3 (3) |
W1—C4—C5—C6 | −62.5 (3) | C2—W1—C6—C5 | 79.4 (3) |
C5i—C4—C5—W1 | 59.9 (4) | C6i—W1—C6—C5 | −115.1 (3) |
C9—C4—C5—W1 | −125.1 (6) | C5i—W1—C6—C5 | −77.1 (4) |
C1—W1—C5—C4 | −143.8 (3) | C4—W1—C6—C5 | −36.8 (2) |
C2i—W1—C5—C4 | −21.2 (5) | I2—W1—C6—C5 | −4.3 (4) |
Symmetry code: (i) x, −y+1, z. |
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