Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020986/lh6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020986/lh6016Isup2.hkl |
CCDC reference: 202292
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.050
- wR factor = 0.130
- Data-to-parameter ratio = 13.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
1,4-dibromo-2,3-dinitro-benzene was reacted with 2 equivalents of n-butyllithium (anhydrous THF, 173 K), followed by the addition of 2.5 equivalents of diphenylchlorophosphine (anhydrous THF, 193 K). The following workup (filtration, solvent removal, washings with diethyl ether) yielded a pale brown powder as a mixture of reaction products. Crystals of the title compound were obtained by allowing diethyl ether diffusion into a THF solution of the product mixture.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON (Spek, 1990); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
[Li(C18H18O3P)] | F(000) = 624 |
Mr = 296.21 | Dx = 1.306 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 5.790 (1) Å | θ = 10–15° |
b = 16.655 (3) Å | µ = 0.19 mm−1 |
c = 15.782 (3) Å | T = 293 K |
β = 98.07 (2)° | Prism, light yellow |
V = 1506.9 (6) Å3 | 0.35 × 0.15 × 0.10 mm |
Z = 4 |
Enraf-Nonius TurboCAD-4 diffractometer | Rint = 0.023 |
non–profiled ω/2θ scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: ψ-scan (North, Phillips & Mathews, 1968) | h = 0→6 |
Tmin = 0.941, Tmax = 0.981 | k = 0→19 |
2913 measured reflections | l = −18→18 |
2635 independent reflections | 3 standard reflections every 166 min |
1602 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.9374P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.130 | (Δ/σ)max = 0.006 |
S = 1.03 | Δρmax = 0.30 e Å−3 |
2635 reflections | Δρmin = −0.29 e Å−3 |
190 parameters |
[Li(C18H18O3P)] | V = 1506.9 (6) Å3 |
Mr = 296.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.790 (1) Å | µ = 0.19 mm−1 |
b = 16.655 (3) Å | T = 293 K |
c = 15.782 (3) Å | 0.35 × 0.15 × 0.10 mm |
β = 98.07 (2)° |
Enraf-Nonius TurboCAD-4 diffractometer | 1602 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North, Phillips & Mathews, 1968) | Rint = 0.023 |
Tmin = 0.941, Tmax = 0.981 | 3 standard reflections every 166 min |
2913 measured reflections | intensity decay: 2% |
2635 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.30 e Å−3 |
2635 reflections | Δρmin = −0.29 e Å−3 |
190 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. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.78088 (15) | 0.08508 (5) | 0.39213 (6) | 0.0283 (2) | |
O1 | 0.6158 (4) | 0.03503 (12) | 0.43570 (13) | 0.0315 (6) | |
O2 | 1.0371 (4) | 0.07388 (13) | 0.41791 (14) | 0.0360 (6) | |
Li1 | 0.7060 (9) | −0.0032 (3) | 0.5553 (3) | 0.0334 (13) | |
C1 | 0.7098 (6) | 0.18983 (19) | 0.4046 (2) | 0.0311 (8) | |
C2 | 0.8569 (7) | 0.2494 (2) | 0.3822 (2) | 0.0478 (10) | |
H2 | 0.9938 | 0.235 | 0.3615 | 0.057* | |
C3 | 0.8039 (8) | 0.3296 (2) | 0.3899 (3) | 0.0602 (12) | |
H3 | 0.9034 | 0.3687 | 0.3735 | 0.072* | |
C4 | 0.6049 (8) | 0.3517 (2) | 0.4217 (3) | 0.0632 (12) | |
H4 | 0.5706 | 0.4057 | 0.4283 | 0.076* | |
C5 | 0.4579 (7) | 0.2940 (3) | 0.4435 (3) | 0.0623 (12) | |
H5 | 0.3218 | 0.309 | 0.4645 | 0.075* | |
C6 | 0.5073 (6) | 0.2135 (2) | 0.4351 (2) | 0.0464 (10) | |
H6 | 0.4041 | 0.1749 | 0.45 | 0.056* | |
C7 | 0.7130 (6) | 0.07102 (18) | 0.2776 (2) | 0.0307 (8) | |
C8 | 0.8756 (7) | 0.0932 (2) | 0.2249 (2) | 0.0471 (10) | |
H8 | 1.0218 | 0.1113 | 0.2493 | 0.056* | |
C9 | 0.8236 (9) | 0.0886 (3) | 0.1371 (2) | 0.0597 (12) | |
H9 | 0.9345 | 0.1037 | 0.1029 | 0.072* | |
C10 | 0.6103 (10) | 0.0622 (3) | 0.1004 (3) | 0.0639 (13) | |
H10 | 0.5742 | 0.0604 | 0.0411 | 0.077* | |
C11 | 0.4492 (8) | 0.0382 (3) | 0.1508 (3) | 0.0630 (12) | |
H11 | 0.3053 | 0.0185 | 0.1258 | 0.076* | |
C12 | 0.5003 (7) | 0.0432 (2) | 0.2391 (2) | 0.0478 (10) | |
H12 | 0.3889 | 0.0274 | 0.2729 | 0.057* | |
O50 | 0.7923 (4) | 0.09484 (15) | 0.62916 (17) | 0.0531 (8) | |
C51 | 0.6510 (9) | 0.1517 (3) | 0.6643 (3) | 0.0808 (16) | |
H51A | 0.6071 | 0.1316 | 0.7175 | 0.097* | |
H51B | 0.5099 | 0.1617 | 0.6248 | 0.097* | |
C52 | 0.7878 (9) | 0.2271 (3) | 0.6802 (4) | 0.0879 (17) | |
H52A | 0.7046 | 0.2719 | 0.6509 | 0.105* | |
H52B | 0.8172 | 0.2389 | 0.7409 | 0.105* | |
C53 | 1.0093 (8) | 0.2122 (3) | 0.6460 (3) | 0.0755 (15) | |
H53A | 1.0057 | 0.2359 | 0.5896 | 0.091* | |
H53B | 1.1407 | 0.2342 | 0.6838 | 0.091* | |
C54 | 1.0246 (7) | 0.1237 (2) | 0.6417 (3) | 0.0638 (13) | |
H54A | 1.1053 | 0.1076 | 0.5946 | 0.077* | |
H54B | 1.1087 | 0.1026 | 0.6945 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0217 (4) | 0.0296 (4) | 0.0336 (5) | −0.0005 (4) | 0.0039 (3) | 0.0053 (4) |
O1 | 0.0242 (12) | 0.0340 (13) | 0.0369 (13) | −0.0020 (10) | 0.0067 (10) | 0.0082 (10) |
O2 | 0.0211 (12) | 0.0402 (14) | 0.0461 (14) | 0.0009 (10) | 0.0024 (10) | 0.0078 (11) |
Li1 | 0.029 (3) | 0.035 (3) | 0.037 (3) | −0.005 (2) | 0.009 (3) | 0.006 (2) |
C1 | 0.0289 (19) | 0.0303 (19) | 0.0324 (19) | −0.0019 (14) | −0.0021 (15) | 0.0015 (14) |
C2 | 0.044 (2) | 0.040 (2) | 0.062 (3) | −0.0037 (18) | 0.014 (2) | 0.0028 (19) |
C3 | 0.072 (3) | 0.035 (2) | 0.074 (3) | −0.012 (2) | 0.012 (3) | 0.006 (2) |
C4 | 0.068 (3) | 0.035 (2) | 0.081 (3) | 0.004 (2) | −0.008 (3) | −0.012 (2) |
C5 | 0.045 (3) | 0.051 (3) | 0.090 (3) | 0.009 (2) | 0.008 (2) | −0.021 (2) |
C6 | 0.037 (2) | 0.039 (2) | 0.064 (3) | −0.0022 (18) | 0.0096 (19) | −0.0081 (19) |
C7 | 0.0308 (19) | 0.0230 (18) | 0.0385 (19) | 0.0031 (15) | 0.0051 (15) | 0.0042 (14) |
C8 | 0.050 (2) | 0.051 (2) | 0.042 (2) | 0.001 (2) | 0.0133 (18) | 0.0075 (19) |
C9 | 0.080 (3) | 0.062 (3) | 0.041 (2) | 0.005 (3) | 0.022 (2) | 0.008 (2) |
C10 | 0.097 (4) | 0.056 (3) | 0.036 (2) | 0.013 (3) | 0.002 (3) | −0.003 (2) |
C11 | 0.064 (3) | 0.065 (3) | 0.055 (3) | 0.001 (2) | −0.012 (2) | −0.009 (2) |
C12 | 0.043 (2) | 0.052 (2) | 0.048 (2) | −0.0045 (19) | 0.0058 (19) | −0.0004 (19) |
O50 | 0.0354 (15) | 0.0499 (17) | 0.075 (2) | −0.0066 (13) | 0.0123 (13) | −0.0233 (14) |
C51 | 0.062 (3) | 0.070 (3) | 0.119 (4) | 0.003 (3) | 0.042 (3) | −0.023 (3) |
C52 | 0.080 (4) | 0.056 (3) | 0.127 (5) | 0.008 (3) | 0.012 (3) | −0.036 (3) |
C53 | 0.068 (3) | 0.055 (3) | 0.103 (4) | −0.016 (3) | 0.006 (3) | −0.014 (3) |
C54 | 0.036 (3) | 0.060 (3) | 0.097 (4) | −0.009 (2) | 0.011 (2) | −0.025 (3) |
P1—O2 | 1.494 (2) | C7—C8 | 1.391 (5) |
P1—O1 | 1.505 (2) | C8—C9 | 1.377 (5) |
P1—C1 | 1.810 (3) | C8—H8 | 0.93 |
P1—C7 | 1.811 (3) | C9—C10 | 1.362 (6) |
P1—Li1 | 3.049 (5) | C9—H9 | 0.93 |
O1—Li1i | 1.962 (6) | C10—C11 | 1.368 (6) |
O1—Li1 | 1.991 (6) | C10—H10 | 0.93 |
O2—Li1ii | 1.897 (6) | C11—C12 | 1.386 (5) |
Li1—O2ii | 1.897 (6) | C11—H11 | 0.93 |
Li1—O1i | 1.962 (6) | C12—H12 | 0.93 |
Li1—O50 | 2.028 (6) | O50—C51 | 1.414 (5) |
Li1—Li1i | 2.754 (11) | O50—C54 | 1.416 (4) |
C1—C6 | 1.386 (5) | C51—C52 | 1.487 (6) |
C1—C2 | 1.385 (5) | C51—H51A | 0.97 |
C2—C3 | 1.381 (5) | C51—H51B | 0.97 |
C2—H2 | 0.93 | C52—C53 | 1.481 (6) |
C3—C4 | 1.370 (6) | C52—H52A | 0.97 |
C3—H3 | 0.93 | C52—H52B | 0.97 |
C4—C5 | 1.360 (6) | C53—C54 | 1.478 (6) |
C4—H4 | 0.93 | C53—H53A | 0.97 |
C5—C6 | 1.381 (5) | C53—H53B | 0.97 |
C5—H5 | 0.93 | C54—H54A | 0.97 |
C6—H6 | 0.93 | C54—H54B | 0.97 |
C7—C12 | 1.375 (5) | ||
O2—P1—O1 | 118.46 (13) | C12—C7—C8 | 117.7 (3) |
O2—P1—C1 | 108.86 (14) | C12—C7—P1 | 122.6 (3) |
O1—P1—C1 | 108.38 (14) | C8—C7—P1 | 119.5 (3) |
O2—P1—C7 | 108.89 (14) | C9—C8—C7 | 121.1 (4) |
O1—P1—C7 | 108.76 (14) | C9—C8—H8 | 119.5 |
C1—P1—C7 | 102.28 (14) | C7—C8—H8 | 119.5 |
O2—P1—Li1 | 87.89 (14) | C10—C9—C8 | 120.2 (4) |
C1—P1—Li1 | 108.15 (15) | C10—C9—H9 | 119.9 |
C7—P1—Li1 | 138.09 (15) | C8—C9—H9 | 119.9 |
P1—O1—Li1i | 148.6 (2) | C9—C10—C11 | 119.9 (4) |
P1—O1—Li1 | 120.7 (2) | C9—C10—H10 | 120.1 |
Li1i—O1—Li1 | 88.3 (2) | C11—C10—H10 | 120.1 |
P1—O2—Li1ii | 148.8 (2) | C10—C11—C12 | 120.1 (4) |
O2ii—Li1—O1i | 122.6 (3) | C10—C11—H11 | 120 |
O2ii—Li1—O1 | 120.2 (3) | C12—C11—H11 | 120 |
O1i—Li1—O1 | 91.7 (2) | C7—C12—C11 | 121.0 (4) |
O2ii—Li1—O50 | 104.4 (3) | C7—C12—H12 | 119.5 |
O1i—Li1—O50 | 109.6 (3) | C11—C12—H12 | 119.5 |
O1—Li1—O50 | 107.3 (3) | C51—O50—C54 | 107.9 (3) |
O2ii—Li1—Li1i | 138.4 (4) | C51—O50—Li1 | 130.9 (3) |
O1i—Li1—Li1i | 46.29 (17) | C54—O50—Li1 | 120.4 (3) |
O1—Li1—Li1i | 45.40 (17) | O50—C51—C52 | 107.9 (4) |
O50—Li1—Li1i | 117.0 (3) | O50—C51—H51A | 110.1 |
O2ii—Li1—P1 | 106.7 (2) | C52—C51—H51A | 110.1 |
O1i—Li1—P1 | 116.1 (2) | O50—C51—H51B | 110.1 |
O1—Li1—P1 | 25.11 (10) | C52—C51—H51B | 110.1 |
O50—Li1—P1 | 92.5 (2) | H51A—C51—H51B | 108.4 |
Li1i—Li1—P1 | 70.1 (2) | C53—C52—C51 | 105.4 (4) |
C6—C1—C2 | 117.8 (3) | C53—C52—H52A | 110.7 |
C6—C1—P1 | 121.9 (3) | C51—C52—H52A | 110.7 |
C2—C1—P1 | 120.3 (3) | C53—C52—H52B | 110.7 |
C3—C2—C1 | 121.2 (4) | C51—C52—H52B | 110.7 |
C3—C2—H2 | 119.4 | H52A—C52—H52B | 108.8 |
C1—C2—H2 | 119.4 | C54—C53—C52 | 104.1 (4) |
C4—C3—C2 | 120.1 (4) | C54—C53—H53A | 110.9 |
C4—C3—H3 | 120 | C52—C53—H53A | 110.9 |
C2—C3—H3 | 120 | C54—C53—H53B | 110.9 |
C5—C4—C3 | 119.4 (4) | C52—C53—H53B | 110.9 |
C5—C4—H4 | 120.3 | H53A—C53—H53B | 109 |
C3—C4—H4 | 120.3 | O50—C54—C53 | 106.5 (3) |
C4—C5—C6 | 121.1 (4) | O50—C54—H54A | 110.4 |
C4—C5—H5 | 119.5 | C53—C54—H54A | 110.4 |
C6—C5—H5 | 119.5 | O50—C54—H54B | 110.4 |
C5—C6—C1 | 120.4 (4) | C53—C54—H54B | 110.4 |
C5—C6—H6 | 119.8 | H54A—C54—H54B | 108.6 |
C1—C6—H6 | 119.8 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Li(C18H18O3P)] |
Mr | 296.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 5.790 (1), 16.655 (3), 15.782 (3) |
β (°) | 98.07 (2) |
V (Å3) | 1506.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.35 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius TurboCAD-4 diffractometer |
Absorption correction | ψ-scan (North, Phillips & Mathews, 1968) |
Tmin, Tmax | 0.941, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2913, 2635, 1602 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.130, 1.03 |
No. of reflections | 2635 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.29 |
Computer programs: CAD-4 EXPRESS (Enraf Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLUTON (Spek, 1990), WinGX publication routines (Farrugia, 1999).
P1—O2 | 1.494 (2) | O1—Li1i | 1.962 (6) |
P1—O1 | 1.505 (2) | O1—Li1 | 1.991 (6) |
P1—C1 | 1.810 (3) | Li1—O2ii | 1.897 (6) |
P1—C7 | 1.811 (3) | Li1—O50 | 2.028 (6) |
P1—O1—Li1i | 148.6 (2) | O1i—Li1—O1 | 91.7 (2) |
P1—O1—Li1 | 120.7 (2) | O2ii—Li1—O50 | 104.4 (3) |
Li1i—O1—Li1 | 88.3 (2) | O1i—Li1—O50 | 109.6 (3) |
O2ii—Li1—O1i | 122.6 (3) | O1—Li1—O50 | 107.3 (3) |
O2ii—Li1—O1 | 120.2 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1. |
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There has been only one previous reported structure of a lithium diorganophosphinate complex, namely Li[Mes2PO2] (Beswick et al., 1997). This complex consists of discrete dimeric molecules with two bridging Mes2PO2− (dimesitylphosphinate) ligands attached to two Li+ cations forming eight-membered rings. Two THF molecules, attached to each Li+ cation via lone pairs on the O atoms, complete the coordination geometry for these distinct dimers.
In contrast, the title compound, (I), has a linear polymeric arrangement with two types of rings alternate to one another. As seen in Fig. 1, there is an eight-membered ring, previously observed with bridging dimesitylphosphinate ligands, and also rectangular planar arrays consisting of two Li and two O atoms from adjacent phosphinate ligands (as seen in the packing diagram, Fig. 2). The rectangular part is a result of the eight-membered ring dimers binding with each other. An O atom from a THF molecule completes the tetrahedral geometry around each Li+ atom. This arrangement no doubt results as this Ph2PO2− ligand is less sterically hindered than the Mes2PO2− one. The linear arrangement appears to be very stable as the compound resists disolution in common organic solvents.