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A topological analysis of the experimental electron density in racemic ethylenebis(1-indenyl)zirconium dichloride, C20H16Cl2Zr, measured at 100 (1) K, has been performed. The atomic charges calculated by the numerical integration of the electron density over the zero-flux atomic basins demonstrate the charge transfer of 2.25 e from the Zr atom to the two indenyl ligands (0.19 e to each) and two Cl atoms (0.93 e to each). All the atomic interactions were quantitatively characterized in terms of the electron density and the electronic energy-density features at the bond critical points. The Zr—C2 bond paths significantly curved towards the C1—C2 bond were found; no other bond paths connecting the Zr atom and indenyl ligand were located. At the same time, the π-electrons of the C1—C2 bond are significantly involved in the metal–ligand interaction. The electron density features indicate that the indenyl coordination can be approximately described as η1 with slippage towards η2. The `ligand-opposed' charge concentrations around the Zr atom were revealed using the Laplacian of the electron density and the one-particle potential; they were linked to the orbital representations. Bonds in the indenyl ligand were characterized using the Cioslowski–Mixon bond-order indices calculated directly from the experimental electron density.
Supporting information
CCDC reference: 280357
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Ethylenebis(1-indenyl)zirconium dichloride
top
Crystal data top
C20H16Cl2Zr | F(000) = 840 |
Mr = 418.45 | Dx = 1.696 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 40 reflections |
a = 15.3870 (5) Å | θ = 30.0–35.0° |
b = 10.5120 (5) Å | µ = 0.99 mm−1 |
c = 11.9270 (5) Å | T = 100 K |
β = 121.85 (1)° | Sphere, colourless |
V = 1638.7 (2) Å3 | 0.09 mm (radius) |
Z = 4 | |
Data collection top
MacScience four-circle diffractometer | 6151 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.020 |
Graphite monochromator | θmax = 50.0°, θmin = 2.5° |
ω/2θ? scans | h = −33→28 |
Absorption correction: for a sphere Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3
for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959)
p.302; Table 5.3.6 B for muR in the range 2.6-10.0.
The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975)
A31,146-148) is used with some modification. | k = −22→18 |
Tmin = 0.861, Tmax = 0.863 | l = −19→25 |
10224 measured reflections | 3 standard reflections every 30 reflections |
6602 independent reflections | intensity decay: 1.5% |
Refinement top
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)] = 0.030 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.072 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0356P)2 + 1.3284P] where P = (Fo2 + 2Fc2)/3 |
6602 reflections | (Δ/σ)max = 0.002 |
137 parameters | Δρmax = 1.37 e Å−3 |
0 restraints | Δρmin = −1.44 e Å−3 |
Crystal data top
C20H16Cl2Zr | V = 1638.7 (2) Å3 |
Mr = 418.45 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.3870 (5) Å | µ = 0.99 mm−1 |
b = 10.5120 (5) Å | T = 100 K |
c = 11.9270 (5) Å | 0.09 mm (radius) |
β = 121.85 (1)° | |
Data collection top
MacScience four-circle diffractometer | 6151 reflections with I > 2σ(I) |
Absorption correction: for a sphere Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3
for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959)
p.302; Table 5.3.6 B for muR in the range 2.6-10.0.
The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975)
A31,146-148) is used with some modification. | Rint = 0.020 |
Tmin = 0.861, Tmax = 0.863 | 3 standard reflections every 30 reflections |
10224 measured reflections | intensity decay: 1.5% |
6602 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.072 | All H-atom parameters refined |
S = 1.02 | Δρmax = 1.37 e Å−3 |
6602 reflections | Δρmin = −1.44 e Å−3 |
137 parameters | |
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 | |
Zr | 0.0000 | 0.271052 (11) | 0.2500 | 0.01012 (2) | |
Cl | −0.136622 (17) | 0.42390 (2) | 0.18359 (2) | 0.01786 (4) | |
C1 | −0.00110 (7) | 0.07448 (8) | 0.13263 (9) | 0.01541 (12) | |
C2 | −0.09921 (7) | 0.13235 (10) | 0.05610 (9) | 0.01863 (14) | |
C3 | −0.09025 (8) | 0.24789 (10) | 0.00163 (9) | 0.01878 (15) | |
C3A | 0.01377 (7) | 0.26199 (9) | 0.04028 (8) | 0.01545 (12) | |
C4 | 0.06545 (10) | 0.35219 (10) | 0.00658 (10) | 0.02057 (16) | |
C5 | 0.16749 (10) | 0.33535 (11) | 0.05609 (12) | 0.02325 (18) | |
C6 | 0.22272 (9) | 0.23071 (12) | 0.13963 (12) | 0.02224 (16) | |
C7 | 0.17584 (8) | 0.14142 (10) | 0.17323 (10) | 0.01779 (13) | |
C7A | 0.06909 (7) | 0.15477 (8) | 0.12271 (8) | 0.01380 (11) | |
C8 | 0.02332 (10) | −0.04865 (9) | 0.20705 (11) | 0.02108 (16) | |
H2 | −0.1615 (16) | 0.102 (2) | 0.040 (2) | 0.029 (5)* | |
H3 | −0.1394 (15) | 0.301 (2) | −0.047 (2) | 0.025 (5)* | |
H4 | 0.0289 (15) | 0.4190 (19) | −0.0500 (19) | 0.020 (4)* | |
H5 | 0.2021 (18) | 0.390 (2) | 0.038 (2) | 0.039 (6)* | |
H6 | 0.2965 (17) | 0.222 (2) | 0.169 (2) | 0.027 (5)* | |
H7 | 0.2130 (16) | 0.070 (2) | 0.222 (2) | 0.028 (5)* | |
H81 | 0.1003 (15) | −0.0621 (19) | 0.2686 (19) | 0.022 (4)* | |
H82 | 0.0010 (15) | −0.118 (2) | 0.1477 (19) | 0.026 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zr | 0.00990 (4) | 0.01098 (4) | 0.00911 (4) | 0.000 | 0.00476 (3) | 0.000 |
Cl | 0.01714 (8) | 0.02022 (9) | 0.01815 (8) | 0.00735 (6) | 0.01064 (7) | 0.00518 (6) |
C1 | 0.0193 (3) | 0.0130 (3) | 0.0150 (3) | −0.0007 (2) | 0.0098 (3) | −0.0019 (2) |
C2 | 0.0166 (3) | 0.0210 (4) | 0.0153 (3) | −0.0029 (3) | 0.0063 (3) | −0.0051 (3) |
C3 | 0.0182 (3) | 0.0229 (4) | 0.0105 (2) | 0.0050 (3) | 0.0044 (2) | 0.0001 (2) |
C3A | 0.0210 (3) | 0.0149 (3) | 0.0115 (2) | 0.0032 (2) | 0.0093 (2) | 0.0012 (2) |
C4 | 0.0350 (5) | 0.0151 (3) | 0.0189 (3) | 0.0030 (3) | 0.0192 (4) | 0.0025 (3) |
C5 | 0.0342 (5) | 0.0204 (4) | 0.0270 (4) | −0.0036 (4) | 0.0243 (4) | −0.0019 (3) |
C6 | 0.0233 (4) | 0.0247 (4) | 0.0262 (4) | −0.0007 (3) | 0.0182 (3) | −0.0026 (4) |
C7 | 0.0192 (3) | 0.0184 (3) | 0.0185 (3) | 0.0044 (3) | 0.0118 (3) | 0.0008 (3) |
C7A | 0.0178 (3) | 0.0128 (3) | 0.0125 (2) | 0.0019 (2) | 0.0091 (2) | 0.0003 (2) |
C8 | 0.0338 (5) | 0.0120 (3) | 0.0253 (4) | 0.0018 (3) | 0.0209 (4) | 0.0003 (3) |
Geometric parameters (Å, º) top
Zr—Cli | 2.4230 (5) | C1—C2 | 1.4241 (15) |
Zr—Cl | 2.4230 (5) | C1—C7A | 1.4240 (13) |
Zr—C2 | 2.4655 (12) | C1—C8 | 1.5008 (14) |
Zr—C2i | 2.4655 (12) | C2—C3 | 1.4180 (16) |
Zr—C1 | 2.4910 (9) | C3—C3A | 1.4204 (15) |
Zr—C1i | 2.4910 (9) | C3A—C4 | 1.4250 (14) |
Zr—C3 | 2.5341 (12) | C3A—C7A | 1.4415 (12) |
Zr—C3i | 2.5341 (12) | C4—C5 | 1.3664 (18) |
Zr—C7Ai | 2.5754 (9) | C5—C6 | 1.4253 (18) |
Zr—C7A | 2.5754 (9) | C6—C7 | 1.3664 (15) |
Zr—C3A | 2.6210 (9) | C7—C7A | 1.4269 (13) |
Zr—C3Ai | 2.6210 (9) | C8—C8i | 1.530 (2) |
| | | |
Cli—Zr—Cl | 96.92 (2) | C2i—Zr—C3A | 123.49 (3) |
Cli—Zr—C2 | 134.40 (3) | C1—Zr—C3A | 54.09 (3) |
Cl—Zr—C2 | 94.85 (4) | C1i—Zr—C3A | 121.75 (3) |
Cli—Zr—C2i | 94.85 (4) | C3—Zr—C3A | 31.93 (3) |
Cl—Zr—C2i | 134.40 (3) | C3i—Zr—C3A | 147.32 (3) |
C2—Zr—C2i | 107.49 (6) | C7Ai—Zr—C3A | 144.26 (3) |
Cli—Zr—C1 | 118.76 (3) | C7A—Zr—C3A | 32.20 (3) |
Cl—Zr—C1 | 128.24 (3) | Cli—Zr—C3Ai | 101.84 (3) |
C2—Zr—C1 | 33.39 (3) | Cl—Zr—C3Ai | 80.97 (3) |
C2i—Zr—C1 | 81.59 (4) | C2—Zr—C3Ai | 123.49 (3) |
Cli—Zr—C1i | 128.24 (3) | C2i—Zr—C3Ai | 53.50 (3) |
Cl—Zr—C1i | 118.76 (3) | C1—Zr—C3Ai | 121.75 (3) |
C2—Zr—C1i | 81.59 (4) | C1i—Zr—C3Ai | 54.09 (3) |
C2i—Zr—C1i | 33.39 (3) | C3—Zr—C3Ai | 147.32 (3) |
C1—Zr—C1i | 67.90 (4) | C3i—Zr—C3Ai | 31.93 (3) |
Cli—Zr—C3 | 106.95 (4) | C7Ai—Zr—C3Ai | 32.20 (3) |
Cl—Zr—C3 | 80.55 (4) | C7A—Zr—C3Ai | 144.26 (3) |
C2—Zr—C3 | 32.92 (4) | C3A—Zr—C3Ai | 175.83 (4) |
C2i—Zr—C3 | 136.54 (4) | C2—C1—C7A | 106.71 (8) |
C1—Zr—C3 | 54.99 (3) | C2—C1—C8 | 126.68 (9) |
C1i—Zr—C3 | 114.47 (3) | C7A—C1—C8 | 126.60 (9) |
Cli—Zr—C3i | 80.55 (4) | C2—C1—Zr | 72.32 (6) |
Cl—Zr—C3i | 106.95 (4) | C7A—C1—Zr | 76.97 (5) |
C2—Zr—C3i | 136.54 (4) | C8—C1—Zr | 117.24 (6) |
C2i—Zr—C3i | 32.92 (4) | C3—C2—C1 | 109.46 (9) |
C1—Zr—C3i | 114.47 (3) | C3—C2—Zr | 76.20 (6) |
C1i—Zr—C3i | 54.99 (3) | C1—C2—Zr | 74.29 (6) |
C3—Zr—C3i | 168.97 (5) | C2—C3—C3A | 107.82 (8) |
Cli—Zr—C7Ai | 132.75 (3) | C2—C3—Zr | 70.88 (5) |
Cl—Zr—C7Ai | 87.17 (3) | C3A—C3—Zr | 77.41 (6) |
C2—Zr—C7Ai | 91.63 (3) | C3—C3A—C4 | 132.75 (9) |
C2i—Zr—C7Ai | 53.86 (3) | C3—C3A—C7A | 107.37 (8) |
C1—Zr—C7Ai | 93.16 (3) | C4—C3A—C7A | 119.74 (9) |
C1i—Zr—C7Ai | 32.59 (3) | C3—C3A—Zr | 70.66 (6) |
C3—Zr—C7Ai | 120.10 (4) | C4—C3A—Zr | 125.68 (6) |
C3i—Zr—C7Ai | 53.65 (3) | C7A—C3A—Zr | 72.16 (5) |
Cli—Zr—C7A | 87.17 (3) | C5—C4—C3A | 118.48 (9) |
Cl—Zr—C7A | 132.75 (3) | C4—C5—C6 | 121.83 (10) |
C2—Zr—C7A | 53.86 (3) | C7—C6—C5 | 121.52 (10) |
C2i—Zr—C7A | 91.63 (3) | C6—C7—C7A | 118.48 (9) |
C1—Zr—C7A | 32.59 (3) | C1—C7A—C7 | 131.38 (8) |
C1i—Zr—C7A | 93.16 (3) | C1—C7A—C3A | 108.62 (8) |
C3—Zr—C7A | 53.65 (3) | C7—C7A—C3A | 119.92 (8) |
C3i—Zr—C7A | 120.10 (4) | C1—C7A—Zr | 70.44 (5) |
C7Ai—Zr—C7A | 123.33 (4) | C7—C7A—Zr | 122.61 (6) |
Cli—Zr—C3A | 80.97 (3) | C3A—C7A—Zr | 75.64 (5) |
Cl—Zr—C3A | 101.84 (3) | C1—C8—C8i | 109.67 (7) |
C2—Zr—C3A | 53.50 (3) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C20H16Cl2Zr |
Mr | 418.45 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 15.3870 (5), 10.5120 (5), 11.9270 (5) |
β (°) | 121.85 (1) |
V (Å3) | 1638.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.09 (radius) |
|
Data collection |
Diffractometer | MacScience four-circle diffractometer |
Absorption correction | For a sphere Interpolation using Int.Tab. Vol. C (1992) p. 523,Tab. 6.3.3.3
for values of muR in the range 0-2.5, and Int.Tab. Vol.II (1959)
p.302; Table 5.3.6 B for muR in the range 2.6-10.0.
The interpolation procedure of C.W.Dwiggins Jr (Acta Cryst.(1975)
A31,146-148) is used with some modification. |
Tmin, Tmax | 0.861, 0.863 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10224, 6602, 6151 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 1.077 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.072, 1.02 |
No. of reflections | 6602 |
No. of parameters | 137 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.37, −1.44 |
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