Di-μ-chloro-bis({[bis(trimethylsilyl)amino]dichlorophosphoraniminato}trichlorotantalum(V))
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007256/bt6258sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007256/bt6258Isup2.hkl |
CCDC reference: 214561
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (Si-C) = 0.007 Å
- R factor = 0.036
- wR factor = 0.088
- Data-to-parameter ratio = 26.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.703 Tmax scaled 0.368 Tmin scaled 0.289
Under an atmosphere of N2, one equivalent of (Me3Si)2NPCl2═NSiMe3 (1.09 g, 3.12 mmol; Niecke & Bitter, 1976) was reacted with TaCl5 (1.04 g, 2.90 mmol) at 298 K in 70 ml of dichloromethane. After 16 h, the volatiles were removed and the remaining white precipitate was washed with hexanes (2 × 50 ml) and recrystallized from dichloromethane (2 ml, 270 K) to give colourless blocks of (I). Yield: 0.11 g (6%). 31P{1H} NMR (CDCl3): 19.1 (s) p.p.m.; 1H NMR (CDCl3): 0.66 (s) p.p.m.
All H atoms were placed in calculated positions with C—H distances of 0.98 Å and included in the refinement in riding motion approximation with Uiso = 1.5Ueq of the carrier atom. The methyl groups were allowed to rotate but not to tip. The two largest electron-density peaks of 2.28 and 2.17 e Å−3 found in the final difference Fourier were within 1.0 Å of the Ta atom. The next largest peak was 0.81 e Å−3.
Data collection: COLLECT (Nonius, 1997-2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ta2Cl8(C6H18Cl2N2PSi2)2] | F(000) = 1144 |
Mr = 1198.05 | Dx = 2.042 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 12859 reflections |
a = 9.2497 (3) Å | θ = 2.6–27.5° |
b = 12.3549 (3) Å | µ = 6.66 mm−1 |
c = 17.4418 (6) Å | T = 150 K |
β = 102.209 (12)° | Plate, colourless |
V = 1948.15 (14) Å3 | 0.20 × 0.20 × 0.15 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 4422 independent reflections |
Radiation source: fine-focus sealed tube | 3734 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ scans and ω scans with κ offsets | h = −11→11 |
Absorption correction: multi-scan (SORTAV; Blessing 1995) | k = −15→16 |
Tmin = 0.411, Tmax = 0.524 | l = −18→22 |
11340 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.0565P] where P = (Fo2 + 2Fc2)/3 |
4422 reflections | (Δ/σ)max = 0.001 |
169 parameters | Δρmax = 2.28 e Å−3 |
0 restraints | Δρmin = −1.40 e Å−3 |
[Ta2Cl8(C6H18Cl2N2PSi2)2] | V = 1948.15 (14) Å3 |
Mr = 1198.05 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2497 (3) Å | µ = 6.66 mm−1 |
b = 12.3549 (3) Å | T = 150 K |
c = 17.4418 (6) Å | 0.20 × 0.20 × 0.15 mm |
β = 102.209 (12)° |
Nonius KappaCCD diffractometer | 4422 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing 1995) | 3734 reflections with I > 2σ(I) |
Tmin = 0.411, Tmax = 0.524 | Rint = 0.050 |
11340 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.03 | Δρmax = 2.28 e Å−3 |
4422 reflections | Δρmin = −1.40 e Å−3 |
169 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 | ||
Ta1 | 0.48534 (2) | 0.426937 (15) | 0.102779 (11) | 0.02198 (8) | |
Cl1 | 0.26316 (15) | 0.39217 (13) | 0.13975 (8) | 0.0400 (3) | |
Cl2 | 0.48291 (16) | 0.60424 (11) | 0.14879 (8) | 0.0341 (3) | |
Cl3 | 0.67549 (12) | 0.48546 (9) | 0.03136 (6) | 0.0254 (2) | |
Cl4 | 0.45694 (15) | 0.26855 (10) | 0.02711 (8) | 0.0359 (3) | |
Cl5 | 0.72306 (18) | 0.14912 (10) | 0.19600 (8) | 0.0432 (4) | |
Cl6 | 0.92536 (14) | 0.34350 (11) | 0.17422 (8) | 0.0381 (3) | |
P1 | 0.76000 (14) | 0.30355 (9) | 0.22602 (7) | 0.0226 (3) | |
Si1 | 0.71223 (17) | 0.41258 (10) | 0.36934 (8) | 0.0274 (3) | |
Si2 | 0.98303 (16) | 0.25322 (11) | 0.37260 (9) | 0.0312 (3) | |
N1 | 0.6218 (4) | 0.3729 (3) | 0.1852 (2) | 0.0235 (8) | |
N2 | 0.8105 (4) | 0.3147 (3) | 0.3193 (2) | 0.0236 (8) | |
C1 | 0.7673 (8) | 0.5502 (4) | 0.3457 (4) | 0.0440 (15) | |
H1A | 0.7334 | 0.5635 | 0.2893 | 0.066* | |
H1B | 0.8753 | 0.5567 | 0.3599 | 0.066* | |
H1C | 0.7226 | 0.6035 | 0.3752 | 0.066* | |
C2 | 0.7656 (7) | 0.3868 (5) | 0.4770 (3) | 0.0474 (15) | |
H2A | 0.7306 | 0.3149 | 0.4885 | 0.071* | |
H2B | 0.7208 | 0.4419 | 0.5050 | 0.071* | |
H2C | 0.8735 | 0.3899 | 0.4939 | 0.071* | |
C3 | 0.5095 (6) | 0.3965 (4) | 0.3422 (3) | 0.0351 (12) | |
H3A | 0.4713 | 0.4339 | 0.2925 | 0.053* | |
H3B | 0.4648 | 0.4276 | 0.3833 | 0.053* | |
H3C | 0.4849 | 0.3193 | 0.3363 | 0.053* | |
C4 | 0.9454 (7) | 0.1657 (5) | 0.4519 (4) | 0.0493 (16) | |
H4A | 0.9426 | 0.2099 | 0.4982 | 0.074* | |
H4B | 1.0238 | 0.1113 | 0.4652 | 0.074* | |
H4C | 0.8499 | 0.1295 | 0.4343 | 0.074* | |
C5 | 1.1096 (7) | 0.3666 (5) | 0.4075 (4) | 0.063 (2) | |
H5A | 1.0700 | 0.4096 | 0.4456 | 0.095* | |
H5B | 1.1189 | 0.4124 | 0.3629 | 0.095* | |
H5C | 1.2070 | 0.3381 | 0.4325 | 0.095* | |
C6 | 1.0717 (9) | 0.1662 (7) | 0.3098 (4) | 0.081 (3) | |
H6A | 1.0030 | 0.1089 | 0.2867 | 0.122* | |
H6B | 1.1614 | 0.1337 | 0.3415 | 0.122* | |
H6C | 1.0980 | 0.2099 | 0.2679 | 0.122* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ta1 | 0.02023 (13) | 0.02803 (14) | 0.01812 (12) | −0.00111 (7) | 0.00507 (8) | −0.00010 (7) |
Cl1 | 0.0225 (7) | 0.0626 (8) | 0.0368 (8) | −0.0033 (6) | 0.0102 (6) | 0.0099 (7) |
Cl2 | 0.0422 (8) | 0.0330 (6) | 0.0278 (7) | 0.0058 (6) | 0.0086 (6) | −0.0043 (5) |
Cl3 | 0.0200 (6) | 0.0358 (6) | 0.0205 (6) | −0.0002 (5) | 0.0047 (4) | 0.0021 (5) |
Cl4 | 0.0432 (8) | 0.0318 (6) | 0.0304 (7) | −0.0046 (6) | 0.0023 (6) | −0.0037 (5) |
Cl5 | 0.0663 (10) | 0.0256 (6) | 0.0388 (8) | −0.0011 (6) | 0.0136 (7) | −0.0061 (5) |
Cl6 | 0.0277 (7) | 0.0584 (8) | 0.0317 (7) | 0.0071 (6) | 0.0140 (5) | 0.0168 (6) |
P1 | 0.0259 (7) | 0.0238 (6) | 0.0197 (6) | 0.0006 (5) | 0.0083 (5) | 0.0013 (5) |
Si1 | 0.0347 (8) | 0.0264 (7) | 0.0232 (7) | −0.0002 (6) | 0.0105 (6) | −0.0008 (5) |
Si2 | 0.0304 (8) | 0.0368 (8) | 0.0257 (7) | 0.0060 (6) | 0.0043 (6) | 0.0075 (6) |
N1 | 0.020 (2) | 0.033 (2) | 0.018 (2) | −0.0025 (17) | 0.0067 (16) | −0.0026 (17) |
N2 | 0.024 (2) | 0.025 (2) | 0.022 (2) | 0.0062 (16) | 0.0049 (16) | 0.0037 (16) |
C1 | 0.059 (4) | 0.032 (3) | 0.044 (4) | −0.007 (3) | 0.017 (3) | −0.005 (3) |
C2 | 0.051 (4) | 0.069 (4) | 0.025 (3) | −0.002 (3) | 0.015 (3) | −0.007 (3) |
C3 | 0.035 (3) | 0.037 (3) | 0.035 (3) | 0.009 (2) | 0.012 (2) | 0.008 (2) |
C4 | 0.042 (4) | 0.053 (4) | 0.052 (4) | 0.001 (3) | 0.007 (3) | 0.024 (3) |
C5 | 0.029 (4) | 0.060 (4) | 0.094 (6) | −0.003 (3) | −0.003 (3) | 0.020 (4) |
C6 | 0.085 (6) | 0.109 (6) | 0.049 (4) | 0.073 (5) | 0.015 (4) | 0.015 (4) |
Ta1—N1 | 1.827 (4) | C1—H1A | 0.9800 |
Ta1—Cl1 | 2.3204 (13) | C1—H1B | 0.9800 |
Ta1—Cl2 | 2.3346 (13) | C1—H1C | 0.9800 |
Ta1—Cl4 | 2.3438 (12) | C2—H2A | 0.9800 |
Ta1—Cl3 | 2.4688 (11) | C2—H2B | 0.9800 |
Ta1—Cl3i | 2.7177 (12) | C2—H2C | 0.9800 |
Cl3—Ta1i | 2.7177 (12) | C3—H3A | 0.9800 |
Cl5—P1 | 1.9888 (17) | C3—H3B | 0.9800 |
Cl6—P1 | 1.9959 (16) | C3—H3C | 0.9800 |
P1—N1 | 1.578 (4) | C4—H4A | 0.9800 |
P1—N2 | 1.600 (4) | C4—H4B | 0.9800 |
Si1—N2 | 1.840 (4) | C4—H4C | 0.9800 |
Si1—C3 | 1.845 (6) | C5—H5A | 0.9800 |
Si1—C1 | 1.847 (5) | C5—H5B | 0.9800 |
Si1—C2 | 1.865 (6) | C5—H5C | 0.9800 |
Si2—N2 | 1.833 (4) | C6—H6A | 0.9800 |
Si2—C5 | 1.844 (7) | C6—H6B | 0.9800 |
Si2—C4 | 1.845 (5) | C6—H6C | 0.9800 |
Si2—C6 | 1.847 (6) | ||
N1—Ta1—Cl1 | 102.65 (12) | Si2—N2—Si1 | 119.7 (2) |
N1—Ta1—Cl2 | 97.35 (12) | Si1—C1—H1A | 109.5 |
Cl1—Ta1—Cl2 | 90.27 (5) | Si1—C1—H1B | 109.5 |
N1—Ta1—Cl4 | 96.55 (12) | H1A—C1—H1B | 109.5 |
Cl1—Ta1—Cl4 | 90.09 (5) | Si1—C1—H1C | 109.5 |
Cl2—Ta1—Cl4 | 165.66 (5) | H1A—C1—H1C | 109.5 |
N1—Ta1—Cl3 | 93.24 (12) | H1B—C1—H1C | 109.5 |
Cl1—Ta1—Cl3 | 164.11 (5) | Si1—C2—H2A | 109.5 |
Cl2—Ta1—Cl3 | 87.61 (4) | Si1—C2—H2B | 109.5 |
Cl4—Ta1—Cl3 | 88.13 (4) | H2A—C2—H2B | 109.5 |
N1—Ta1—Cl3i | 169.78 (11) | Si1—C2—H2C | 109.5 |
Cl1—Ta1—Cl3i | 87.55 (4) | H2A—C2—H2C | 109.5 |
Cl2—Ta1—Cl3i | 83.05 (4) | H2B—C2—H2C | 109.5 |
Cl4—Ta1—Cl3i | 82.65 (4) | Si1—C3—H3A | 109.5 |
Cl3—Ta1—Cl3i | 76.56 (4) | Si1—C3—H3B | 109.5 |
Ta1—Cl3—Ta1i | 103.44 (4) | H3A—C3—H3B | 109.5 |
N1—P1—N2 | 116.53 (19) | Si1—C3—H3C | 109.5 |
N1—P1—Cl5 | 108.91 (16) | H3A—C3—H3C | 109.5 |
N2—P1—Cl5 | 110.30 (15) | H3B—C3—H3C | 109.5 |
N1—P1—Cl6 | 106.65 (15) | Si2—C4—H4A | 109.5 |
N2—P1—Cl6 | 110.61 (16) | Si2—C4—H4B | 109.5 |
Cl5—P1—Cl6 | 102.92 (8) | H4A—C4—H4B | 109.5 |
N2—Si1—C3 | 112.6 (2) | Si2—C4—H4C | 109.5 |
N2—Si1—C1 | 108.2 (2) | H4A—C4—H4C | 109.5 |
C3—Si1—C1 | 110.8 (3) | H4B—C4—H4C | 109.5 |
N2—Si1—C2 | 108.2 (2) | Si2—C5—H5A | 109.5 |
C3—Si1—C2 | 106.2 (3) | Si2—C5—H5B | 109.5 |
C1—Si1—C2 | 110.8 (3) | H5A—C5—H5B | 109.5 |
N2—Si2—C5 | 106.0 (2) | Si2—C5—H5C | 109.5 |
N2—Si2—C4 | 109.9 (2) | H5A—C5—H5C | 109.5 |
C5—Si2—C4 | 113.9 (3) | H5B—C5—H5C | 109.5 |
N2—Si2—C6 | 112.9 (3) | Si2—C6—H6A | 109.5 |
C5—Si2—C6 | 107.9 (4) | Si2—C6—H6B | 109.5 |
C4—Si2—C6 | 106.3 (3) | H6A—C6—H6B | 109.5 |
P1—N1—Ta1 | 155.9 (2) | Si2—C6—H6C | 109.5 |
P1—N2—Si2 | 121.0 (2) | H6A—C6—H6C | 109.5 |
P1—N2—Si1 | 118.1 (2) | H6B—C6—H6C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ta2Cl8(C6H18Cl2N2PSi2)2] |
Mr | 1198.05 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 9.2497 (3), 12.3549 (3), 17.4418 (6) |
β (°) | 102.209 (12) |
V (Å3) | 1948.15 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.66 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing 1995) |
Tmin, Tmax | 0.411, 0.524 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11340, 4422, 3734 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.088, 1.03 |
No. of reflections | 4422 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.28, −1.40 |
Computer programs: COLLECT (Nonius, 1997-2002), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick, 2001), SHELXTL.
Ta1—N1 | 1.827 (4) | Cl5—P1 | 1.9888 (17) |
Ta1—Cl1 | 2.3204 (13) | Cl6—P1 | 1.9959 (16) |
Ta1—Cl2 | 2.3346 (13) | P1—N1 | 1.578 (4) |
Ta1—Cl4 | 2.3438 (12) | P1—N2 | 1.600 (4) |
Ta1—Cl3 | 2.4688 (11) | Si1—N2 | 1.840 (4) |
Ta1—Cl3i | 2.7177 (12) | Si2—N2 | 1.833 (4) |
N1—Ta1—Cl1 | 102.65 (12) | Cl1—Ta1—Cl3i | 87.55 (4) |
N1—Ta1—Cl2 | 97.35 (12) | Cl2—Ta1—Cl3i | 83.05 (4) |
Cl1—Ta1—Cl2 | 90.27 (5) | Cl4—Ta1—Cl3i | 82.65 (4) |
N1—Ta1—Cl4 | 96.55 (12) | Cl3—Ta1—Cl3i | 76.56 (4) |
Cl1—Ta1—Cl4 | 90.09 (5) | Ta1—Cl3—Ta1i | 103.44 (4) |
Cl2—Ta1—Cl4 | 165.66 (5) | Cl5—P1—Cl6 | 102.92 (8) |
N1—Ta1—Cl3 | 93.24 (12) | P1—N1—Ta1 | 155.9 (2) |
Cl1—Ta1—Cl3 | 164.11 (5) | P1—N2—Si2 | 121.0 (2) |
Cl2—Ta1—Cl3 | 87.61 (4) | P1—N2—Si1 | 118.1 (2) |
Cl4—Ta1—Cl3 | 88.13 (4) | Si2—N2—Si1 | 119.7 (2) |
N1—Ta1—Cl3i | 169.78 (11) |
Symmetry code: (i) −x+1, −y+1, −z. |
As part our investigations into the use of novel inorganic heterocycles as monomers for ring-opening polymerization (ROP) reactions (Manners, 1996; Gates & Manners, 1997), we explored the reaction of the silylated aminoiminophosphoranimine (Me3Si)2NPCl2═NSiMe3 with various metal halides to give four-membered MNPN rings (M = group 4 or 5 metal) (Rivard et al., 2001, 2002). In the reaction of TaCl5 with (Me3Si)2NPCl2═NSiMe3, we occasionally also obtained the linear isomer [Cl4Ta—N═PCl2—N(SiMe3)2]2, (I).