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In the title compound, [Li(C
14H
36N
2PSi
2)(C
5H
5N)
2], the bulky chelating monoanionic
P,
P-di-
tert-butyl-
N-trimethylsilyl-
P-(trimethylsilylamino)phosphine imidate ligand and two pyridine ligands bind to Li in a pseudo-tetrahedral arrangement with twofold symmetry. The Li-N
phosphine distance is 2.048 (5) Å, while the Li
P distance is 2.520 (6) Å.
Supporting information
CCDC reference: 184478
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
[
P,
P-Di-
tert-butyl-
N-trimethylsilyl-
P-(trimethylsilylamino)phosphine
imidato-
κ2N,
N']bis(pyridine-
κN)lithium(I)
top
Crystal data top
[Li(C14H36N2PSi2)(C5H5N)2] | F(000) = 1056 |
Mr = 484.74 | Dx = 1.062 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3164 reflections |
a = 8.8980 (2) Å | θ = 2.1–24.1° |
b = 19.3848 (5) Å | µ = 0.19 mm−1 |
c = 17.5894 (3) Å | T = 200 K |
β = 92.302 (1)° | Needle-like, colourless |
V = 3031.48 (12) Å3 | 0.83 × 0.29 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector Query diffractometer | 2410 independent reflections |
Radiation source: fine-focus sealed tube | 1674 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
φ and ω scans | θmax = 24.1°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | h = −10→10 |
Tmin = 0.56, Tmax = 0.97 | k = −22→22 |
11861 measured reflections | l = −20→20 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0764P)2 + 1.4419P] where P = (Fo2 + 2Fc2)/3 |
2410 reflections | (Δ/σ)max = 0.029 |
152 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Special details top
Experimental. Attempts to cut the long thin needle-like crystals resulted in shattering.
Therefore, a crystal was used which was longer than the beam-width. Correction
for this by SADABS may be the cause of the low Tmin. |
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 | |
Li1 | 0.5000 | 0.3058 (3) | 0.2500 | 0.0360 (16) | |
N1 | 0.4007 (2) | 0.38824 (11) | 0.19516 (12) | 0.0356 (6) | |
N2 | 0.6009 (3) | 0.23292 (12) | 0.17865 (14) | 0.0456 (7) | |
Si1 | 0.28204 (9) | 0.37396 (5) | 0.12070 (5) | 0.0429 (3) | |
P1 | 0.5000 | 0.43581 (5) | 0.2500 | 0.0326 (3) | |
C1 | 0.6270 (4) | 0.49019 (16) | 0.19230 (18) | 0.0486 (8) | |
C2 | 0.5443 (5) | 0.5240 (2) | 0.1241 (2) | 0.0811 (13) | |
H2A | 0.6170 | 0.5478 | 0.0929 | 0.122* | |
H2C | 0.4711 | 0.5574 | 0.1421 | 0.122* | |
H2B | 0.4918 | 0.4885 | 0.0935 | 0.122* | |
C3 | 0.7419 (4) | 0.4403 (2) | 0.1608 (2) | 0.0788 (13) | |
H3B | 0.8064 | 0.4650 | 0.1261 | 0.118* | |
H3C | 0.6892 | 0.4029 | 0.1333 | 0.118* | |
H3A | 0.8038 | 0.4209 | 0.2029 | 0.118* | |
C4 | 0.7120 (5) | 0.5450 (2) | 0.2390 (2) | 0.0941 (15) | |
H4C | 0.7636 | 0.5233 | 0.2831 | 0.141* | |
H4A | 0.6408 | 0.5796 | 0.2565 | 0.141* | |
H4B | 0.7861 | 0.5674 | 0.2074 | 0.141* | |
C5 | 0.1425 (4) | 0.3061 (2) | 0.1454 (2) | 0.0752 (12) | |
H5A | 0.0808 | 0.3230 | 0.1863 | 0.113* | |
H5C | 0.1960 | 0.2643 | 0.1622 | 0.113* | |
H5B | 0.0778 | 0.2956 | 0.1005 | 0.113* | |
C6 | 0.1668 (4) | 0.44924 (19) | 0.0852 (2) | 0.0765 (12) | |
H6A | 0.2338 | 0.4859 | 0.0684 | 0.115* | |
H6B | 0.1059 | 0.4666 | 0.1262 | 0.115* | |
H6C | 0.1007 | 0.4345 | 0.0423 | 0.115* | |
C7 | 0.3810 (4) | 0.33967 (17) | 0.03652 (16) | 0.0553 (9) | |
H7A | 0.4395 | 0.2987 | 0.0517 | 0.083* | |
H7B | 0.4486 | 0.3751 | 0.0176 | 0.083* | |
H7C | 0.3066 | 0.3272 | −0.0038 | 0.083* | |
C8 | 0.5152 (4) | 0.18181 (15) | 0.15133 (19) | 0.0515 (9) | |
H8 | 0.4204 | 0.1744 | 0.1729 | 0.062* | |
C9 | 0.5570 (4) | 0.13899 (17) | 0.09324 (19) | 0.0578 (10) | |
H9 | 0.4924 | 0.1030 | 0.0752 | 0.069* | |
C10 | 0.6932 (5) | 0.14945 (19) | 0.06234 (19) | 0.0654 (11) | |
H10 | 0.7246 | 0.1212 | 0.0218 | 0.078* | |
C11 | 0.7832 (4) | 0.20072 (19) | 0.0902 (2) | 0.0653 (11) | |
H11 | 0.8791 | 0.2085 | 0.0699 | 0.078* | |
C12 | 0.7343 (4) | 0.24129 (17) | 0.14827 (19) | 0.0515 (9) | |
H12 | 0.7985 | 0.2769 | 0.1676 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.043 (4) | 0.032 (4) | 0.034 (4) | 0.000 | 0.014 (3) | 0.000 |
N1 | 0.0356 (14) | 0.0403 (14) | 0.0313 (13) | 0.0027 (11) | 0.0055 (11) | −0.0014 (11) |
N2 | 0.0507 (17) | 0.0414 (15) | 0.0458 (15) | −0.0030 (13) | 0.0149 (13) | −0.0055 (12) |
Si1 | 0.0403 (5) | 0.0575 (6) | 0.0307 (5) | 0.0015 (4) | 0.0009 (4) | −0.0082 (4) |
P1 | 0.0374 (6) | 0.0357 (6) | 0.0250 (6) | 0.000 | 0.0051 (4) | 0.000 |
C1 | 0.055 (2) | 0.0488 (19) | 0.0417 (18) | −0.0135 (16) | 0.0026 (16) | 0.0156 (15) |
C2 | 0.096 (3) | 0.088 (3) | 0.059 (3) | −0.014 (2) | 0.002 (2) | 0.037 (2) |
C3 | 0.068 (3) | 0.094 (3) | 0.077 (3) | −0.007 (2) | 0.044 (2) | 0.024 (2) |
C4 | 0.113 (4) | 0.092 (3) | 0.077 (3) | −0.061 (3) | −0.005 (3) | 0.018 (2) |
C5 | 0.058 (2) | 0.111 (3) | 0.056 (2) | −0.033 (2) | 0.0021 (19) | −0.019 (2) |
C6 | 0.071 (3) | 0.089 (3) | 0.068 (3) | 0.025 (2) | −0.023 (2) | −0.018 (2) |
C7 | 0.075 (2) | 0.065 (2) | 0.0253 (16) | 0.0051 (19) | 0.0037 (16) | −0.0056 (15) |
C8 | 0.054 (2) | 0.0434 (19) | 0.058 (2) | −0.0029 (16) | 0.0087 (17) | −0.0014 (17) |
C9 | 0.074 (3) | 0.050 (2) | 0.050 (2) | −0.0079 (18) | 0.0046 (19) | −0.0119 (17) |
C10 | 0.094 (3) | 0.061 (2) | 0.043 (2) | 0.009 (2) | 0.017 (2) | −0.0150 (18) |
C11 | 0.066 (3) | 0.070 (3) | 0.063 (2) | −0.001 (2) | 0.032 (2) | −0.012 (2) |
C12 | 0.053 (2) | 0.049 (2) | 0.053 (2) | −0.0090 (16) | 0.0161 (18) | −0.0043 (16) |
Geometric parameters (Å, º) top
Li1—N1 | 2.048 (5) | C4—H4A | 0.9800 |
Li1—N2 | 2.114 (5) | C4—H4B | 0.9800 |
Li1—P1 | 2.520 (6) | C5—H5A | 0.9800 |
N1—P1 | 1.579 (2) | C5—H5C | 0.9800 |
N1—Si1 | 1.672 (2) | C5—H5B | 0.9800 |
N2—C8 | 1.328 (4) | C6—H6A | 0.9800 |
N2—C12 | 1.332 (4) | C6—H6B | 0.9800 |
Si1—C5 | 1.871 (4) | C6—H6C | 0.9800 |
Si1—C7 | 1.875 (3) | C7—H7A | 0.9800 |
Si1—C6 | 1.876 (4) | C7—H7B | 0.9800 |
P1—C1 | 1.873 (3) | C7—H7C | 0.9800 |
C1—C4 | 1.525 (5) | C8—C9 | 1.379 (4) |
C1—C3 | 1.528 (5) | C8—H8 | 0.9500 |
C1—C2 | 1.530 (4) | C9—C10 | 1.363 (5) |
C2—H2A | 0.9800 | C9—H9 | 0.9500 |
C2—H2C | 0.9800 | C10—C11 | 1.356 (5) |
C2—H2B | 0.9800 | C10—H10 | 0.9500 |
C3—H3B | 0.9800 | C11—C12 | 1.373 (4) |
C3—H3C | 0.9800 | C11—H11 | 0.9500 |
C3—H3A | 0.9800 | C12—H12 | 0.9500 |
C4—H4C | 0.9800 | | |
| | | |
N1i—Li1—N1 | 77.5 (2) | H3C—C3—H3A | 109.5 |
N1i—Li1—N2 | 128.01 (10) | C1—C4—H4C | 109.5 |
N1—Li1—N2 | 115.30 (9) | C1—C4—H4A | 109.5 |
N2—Li1—N2i | 96.1 (3) | H4C—C4—H4A | 109.5 |
N2—Li1—P1 | 131.96 (14) | C1—C4—H4B | 109.5 |
P1—N1—Si1 | 153.57 (15) | H4C—C4—H4B | 109.5 |
P1—N1—Li1 | 87.00 (15) | H4A—C4—H4B | 109.5 |
Si1—N1—Li1 | 119.12 (16) | Si1—C5—H5A | 109.5 |
C8—N2—C12 | 117.0 (3) | Si1—C5—H5C | 109.5 |
C8—N2—Li1 | 117.5 (2) | H5A—C5—H5C | 109.5 |
C12—N2—Li1 | 124.3 (2) | Si1—C5—H5B | 109.5 |
N1—Si1—C5 | 109.80 (15) | H5A—C5—H5B | 109.5 |
N1—Si1—C7 | 112.05 (14) | H5C—C5—H5B | 109.5 |
C5—Si1—C7 | 105.71 (17) | Si1—C6—H6A | 109.5 |
N1—Si1—C6 | 116.85 (14) | Si1—C6—H6B | 109.5 |
C5—Si1—C6 | 105.38 (19) | H6A—C6—H6B | 109.5 |
C7—Si1—C6 | 106.28 (17) | Si1—C6—H6C | 109.5 |
N1—P1—N1i | 108.52 (17) | H6A—C6—H6C | 109.5 |
N1—P1—C1i | 108.96 (13) | H6B—C6—H6C | 109.5 |
N1—P1—C1 | 109.42 (13) | Si1—C7—H7A | 109.5 |
C1i—P1—C1 | 111.5 (2) | Si1—C7—H7B | 109.5 |
N1—P1—Li1 | 54.26 (8) | H7A—C7—H7B | 109.5 |
C1—P1—Li1 | 124.24 (11) | Si1—C7—H7C | 109.5 |
C4—C1—C3 | 108.2 (3) | H7A—C7—H7C | 109.5 |
C4—C1—C2 | 109.6 (3) | H7B—C7—H7C | 109.5 |
C3—C1—C2 | 107.2 (3) | N2—C8—C9 | 123.3 (3) |
C4—C1—P1 | 113.4 (2) | N2—C8—H8 | 118.3 |
C3—C1—P1 | 105.5 (2) | C9—C8—H8 | 118.3 |
C2—C1—P1 | 112.6 (2) | C10—C9—C8 | 118.4 (3) |
C1—C2—H2A | 109.5 | C10—C9—H9 | 120.8 |
C1—C2—H2C | 109.5 | C8—C9—H9 | 120.8 |
H2A—C2—H2C | 109.5 | C11—C10—C9 | 119.1 (3) |
C1—C2—H2B | 109.5 | C11—C10—H10 | 120.4 |
H2A—C2—H2B | 109.5 | C9—C10—H10 | 120.4 |
H2C—C2—H2B | 109.5 | C10—C11—C12 | 119.2 (3) |
C1—C3—H3B | 109.5 | C10—C11—H11 | 120.4 |
C1—C3—H3C | 109.5 | C12—C11—H11 | 120.4 |
H3B—C3—H3C | 109.5 | N2—C12—C11 | 122.9 (3) |
C1—C3—H3A | 109.5 | N2—C12—H12 | 118.6 |
H3B—C3—H3A | 109.5 | C11—C12—H12 | 118.6 |
Symmetry code: (i) −x+1, y, −z+1/2. |
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