Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037427/bt2446sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037427/bt2446Isup2.hkl |
CCDC reference: 660064
All manipulations were carried out in an atmosphere of argon using standard Schlenk techniques. THF, diethyl ether and dioxane were dried (Na/benzophenone) and distilled prior to use. K and diphenylamine were purchased form Aldrich. 1H NMR and 13C NMR spectra were recorded at [D8]THF solution at ambient temperature on a Bruker AC 400 MHz s pectrometer and were referenced to deuterated THF as an internal standard.
Bis[tris(tetrahydrofuran-O)(µ2-diphenylamido)potassium] was prepared according to literature procedure (Gärtner et al., 2007) and recrystallized from hot 1,4-dioxane. Storage of this solution at ambient temperature led to the formation of single crystals within 12 h.
Physical data:
Mp: 90°C (decomposition).
1H NMR (400 MHz) δ 3.56 (dx), 6.14–6.18 (m, 2H), 6.85–6.90 (m, 8H).
13C NMR (100 MHz) δ 67.7 (dx), 112.3 (2 C, p–C), 118.0 (4 C, o–C), 129.7 (4 C, m–C), 158.3 (2 C, i–C).
MS (DEI, m/z [% '[%' %]]): 208 (M+, [1]).
IR (cm-1): 1592, 1570, 1551, 1313, 1255, 1212, 1165, 1118, 1080, 1047, 985, 888, 871, 798, 753, 710, 700, 613, 523, 503.
All hydrogen atoms were calculated at idealized positions with Caromatic—H = 0.95Å or C-methylene-H = 0.99Å and were refined with 1.5 times the isotropic displacement parameter of the corresponding carbon atoms.
In the past, potassium diphenylamide has been used for the synthesis of a lot of transition metal diphenylamides, for example those of Cr (Seidel & Reichardt, 1974), Pd (Villanueva et al., 1994), Th (Barnhart et al., 1995), Nb (Tayebani et al., 1998), Y and Sm (Gamer et al., 2001), Yb (Hitchcock et al., 2002), and Re (Hevia et al., 2002). Potassium diphenylamide also served as a catalyst in the polymerization of lactones and α,β-unsaturated cycloketones (Longi et al., 1965), octamethylcyclotetrasiloxane (Kucera & Jelinek, 1959), and isocyanates (Grogler & Windemuth, 1966). This compound is often mentioned in literature (Barnhart et al., 1995; Bergstrom et al., 1942; Cheshko & Goncharenko, 1971; Fröhlich, 1975), but neither a complete synthetic method nor structural or spectroscopic data have been published. The reaction of potassium with diphenylamine in boiling THF gives (thf)3K(µ2-NPh2)2K(thf)3. Recrystallization from hot dioxane yields single crystals of [(µ-O,O'-dx)(dx-O)K(µ-NPh2)]∞ ((I)) at ambient temperature. In the molecular structure of (I), potassium diphenylamide forms a dimeric molecule with a centosymmetric four-membered KNKiNi ring [symmetry code: (i) 2 - x, 1 - y, -z]. Additionally, each K atom is saturated with three molecules of dioxane, two of them are attached to neighbouring K atoms with the other oxygen atom. This leads to the formation of parallel layers parallel to (001). The coordination sphere of K is distorted square-pyramidal with O4 occupying the apical position and N1, N1i, O1, and O3 lying on the basal positions. The compound cocrystallizes with a molecule of dioxane in the asymmetric unit.
For the synthesis of transition metal diphenylamides, see: Seidel & Reichardt (1974); Villanueva et al. (1994); Barnhart et al. (1995); Tayebani et al. (1998); Gamer et al. (2001); Hitchcock et al. (2002); Hevia et al. (2002). For potassium diphenylamide as a catalyst in polymerization reactions, see: Longi et al. (1965); Kucera & Jelinek (1959); Grogler & Windemuth (1966). For the synthesis of the title compound, see: Barnhart et al. (1995); Bergstrom et al. (1942); Cheshko & Goncharenko (1971); Fröhlich (1975). For the synthesis and crystal structure of bis[tris(tetrahydrofuran-O)(µ2-diphenylamido)potassium], see: Gärtner et al. (2007).
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Siemens, 1990); software used to prepare material for publication: SHELXL97.
[K(C12H10N)(C4H8O2)2]·C4H8O2 | Z = 2 |
Mr = 471.62 | F(000) = 504 |
Triclinic, P1 | Dx = 1.267 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.5417 (5) Å | Cell parameters from 8425 reflections |
b = 10.6758 (6) Å | θ = 2.1–27.4° |
c = 12.7711 (5) Å | µ = 0.25 mm−1 |
α = 70.419 (3)° | T = 183 K |
β = 86.123 (3)° | Prism, colourless |
γ = 66.278 (2)° | 0.06 × 0.06 × 0.05 mm |
V = 1235.97 (10) Å3 |
Nonius KappaCCD diffractometer | 5472 independent reflections |
Radiation source: fine-focus sealed tube | 3974 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 27.4°, θmin = 2.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −13→12 |
Tmin = 0.967, Tmax = 0.987 | k = −13→11 |
8425 measured reflections | l = −16→16 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0488P)2 + 0.0755P] where P = (Fo2 + 2Fc2)/3 |
5472 reflections | (Δ/σ)max < 0.001 |
289 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[K(C12H10N)(C4H8O2)2]·C4H8O2 | γ = 66.278 (2)° |
Mr = 471.62 | V = 1235.97 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.5417 (5) Å | Mo Kα radiation |
b = 10.6758 (6) Å | µ = 0.25 mm−1 |
c = 12.7711 (5) Å | T = 183 K |
α = 70.419 (3)° | 0.06 × 0.06 × 0.05 mm |
β = 86.123 (3)° |
Nonius KappaCCD diffractometer | 5472 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3974 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.987 | Rint = 0.029 |
8425 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.23 e Å−3 |
5472 reflections | Δρmin = −0.25 e Å−3 |
289 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 | ||
K1 | 0.80940 (3) | 0.58975 (4) | 0.06727 (3) | 0.02744 (12) | |
O1 | 0.73827 (13) | 0.51425 (15) | 0.28382 (9) | 0.0402 (3) | |
O2 | 0.68752 (13) | 0.35147 (15) | 0.49469 (10) | 0.0424 (3) | |
O3 | 0.58105 (12) | 0.54644 (14) | 0.04898 (10) | 0.0352 (3) | |
O4 | 0.61613 (12) | 0.86555 (13) | 0.04205 (10) | 0.0368 (3) | |
O5 | 0.88112 (13) | 0.75650 (14) | 0.39904 (10) | 0.0433 (3) | |
O6 | 0.71297 (15) | 1.04991 (15) | 0.27924 (11) | 0.0492 (4) | |
N1 | 1.08797 (13) | 0.42696 (15) | 0.14643 (10) | 0.0259 (3) | |
C1 | 1.12229 (16) | 0.53691 (18) | 0.15025 (13) | 0.0245 (4) | |
C2 | 1.07544 (16) | 0.66780 (18) | 0.05752 (13) | 0.0281 (4) | |
H2A | 1.0300 | 0.6720 | −0.0061 | 0.034* | |
C3 | 1.09369 (18) | 0.7895 (2) | 0.05649 (15) | 0.0347 (4) | |
H3A | 1.0599 | 0.8752 | −0.0071 | 0.042* | |
C4 | 1.16059 (19) | 0.7883 (2) | 0.14690 (16) | 0.0388 (4) | |
H4A | 1.1736 | 0.8717 | 0.1460 | 0.047* | |
C5 | 1.20816 (18) | 0.6613 (2) | 0.23914 (16) | 0.0366 (4) | |
H5A | 1.2539 | 0.6586 | 0.3020 | 0.044* | |
C6 | 1.19035 (17) | 0.5389 (2) | 0.24136 (14) | 0.0308 (4) | |
H6A | 1.2246 | 0.4540 | 0.3056 | 0.037* | |
C7 | 1.16056 (16) | 0.28448 (18) | 0.21367 (12) | 0.0249 (4) | |
C8 | 1.09112 (18) | 0.18982 (19) | 0.24413 (13) | 0.0296 (4) | |
H8A | 0.9948 | 0.2278 | 0.2227 | 0.036* | |
C9 | 1.1595 (2) | 0.0436 (2) | 0.30425 (14) | 0.0357 (4) | |
H9A | 1.1093 | −0.0165 | 0.3235 | 0.043* | |
C10 | 1.2995 (2) | −0.0164 (2) | 0.33671 (14) | 0.0377 (5) | |
H10A | 1.3461 | −0.1170 | 0.3778 | 0.045* | |
C11 | 1.37052 (18) | 0.0734 (2) | 0.30805 (14) | 0.0349 (4) | |
H11A | 1.4669 | 0.0337 | 0.3301 | 0.042* | |
C12 | 1.30370 (17) | 0.21958 (19) | 0.24804 (13) | 0.0295 (4) | |
H12A | 1.3555 | 0.2781 | 0.2294 | 0.035* | |
C13 | 0.8367 (2) | 0.4525 (2) | 0.37896 (15) | 0.0424 (5) | |
H13A | 0.8192 | 0.5251 | 0.4161 | 0.051* | |
H13B | 0.9321 | 0.4269 | 0.3541 | 0.051* | |
C14 | 0.82513 (19) | 0.3192 (2) | 0.46008 (16) | 0.0420 (5) | |
H14A | 0.8500 | 0.2437 | 0.4248 | 0.050* | |
H14B | 0.8913 | 0.2804 | 0.5260 | 0.050* | |
C15 | 0.5912 (2) | 0.4105 (2) | 0.40013 (15) | 0.0388 (5) | |
H15A | 0.4957 | 0.4343 | 0.4245 | 0.047* | |
H15B | 0.6111 | 0.3375 | 0.3629 | 0.047* | |
C16 | 0.60096 (19) | 0.5448 (2) | 0.31960 (14) | 0.0365 (4) | |
H16A | 0.5341 | 0.5838 | 0.2541 | 0.044* | |
H16B | 0.5760 | 0.6196 | 0.3556 | 0.044* | |
C17 | 0.5678 (2) | 0.4124 (2) | 0.10436 (16) | 0.0408 (5) | |
H17A | 0.4899 | 0.4284 | 0.1531 | 0.061* | |
H17B | 0.6540 | 0.3416 | 0.1519 | 0.061* | |
C18 | 0.45827 (19) | 0.6481 (2) | −0.02155 (16) | 0.0374 (4) | |
H18A | 0.4689 | 0.7400 | −0.0615 | 0.056* | |
H18B | 0.3779 | 0.6697 | 0.0243 | 0.056* | |
C19 | 0.51208 (19) | 0.9214 (2) | 0.11231 (14) | 0.0392 (5) | |
H19A | 0.5408 | 0.9780 | 0.1460 | 0.059* | |
H19B | 0.5035 | 0.8395 | 0.1735 | 0.059* | |
C20 | 0.62656 (18) | 0.98288 (19) | −0.04698 (14) | 0.0322 (4) | |
H20A | 0.6962 | 0.9445 | −0.0968 | 0.048* | |
H20B | 0.6581 | 1.0407 | −0.0169 | 0.048* | |
C21 | 0.7750 (2) | 0.8442 (2) | 0.44988 (15) | 0.0436 (5) | |
H21A | 0.8030 | 0.8128 | 0.5301 | 0.052* | |
H21B | 0.6884 | 0.8311 | 0.4435 | 0.052* | |
C22 | 0.7485 (2) | 1.0009 (2) | 0.39619 (16) | 0.0507 (6) | |
H22A | 0.6717 | 1.0596 | 0.4313 | 0.061* | |
H22B | 0.8326 | 1.0153 | 0.4086 | 0.061* | |
C23 | 0.8202 (2) | 0.9608 (2) | 0.22953 (16) | 0.0429 (5) | |
H23A | 0.9073 | 0.9722 | 0.2377 | 0.051* | |
H23B | 0.7941 | 0.9924 | 0.1489 | 0.051* | |
C24 | 0.8439 (2) | 0.8044 (2) | 0.28301 (14) | 0.0392 (5) | |
H24A | 0.7582 | 0.7920 | 0.2717 | 0.047* | |
H24B | 0.9190 | 0.7445 | 0.2475 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.02222 (18) | 0.0292 (2) | 0.0288 (2) | −0.00831 (15) | 0.00330 (14) | −0.01012 (15) |
O1 | 0.0457 (8) | 0.0467 (8) | 0.0278 (6) | −0.0231 (6) | 0.0062 (6) | −0.0072 (6) |
O2 | 0.0423 (7) | 0.0463 (8) | 0.0301 (7) | −0.0195 (6) | 0.0013 (6) | −0.0002 (6) |
O3 | 0.0338 (6) | 0.0393 (8) | 0.0407 (7) | −0.0212 (6) | 0.0021 (5) | −0.0155 (6) |
O4 | 0.0379 (7) | 0.0247 (7) | 0.0328 (6) | −0.0029 (5) | 0.0073 (5) | −0.0045 (5) |
O5 | 0.0380 (7) | 0.0413 (8) | 0.0410 (7) | −0.0046 (6) | −0.0057 (6) | −0.0148 (6) |
O6 | 0.0516 (8) | 0.0381 (8) | 0.0445 (8) | −0.0112 (7) | 0.0051 (7) | −0.0067 (6) |
N1 | 0.0259 (7) | 0.0243 (8) | 0.0247 (7) | −0.0097 (6) | −0.0015 (6) | −0.0048 (6) |
C1 | 0.0210 (8) | 0.0273 (9) | 0.0251 (8) | −0.0088 (7) | 0.0051 (6) | −0.0105 (7) |
C2 | 0.0257 (8) | 0.0295 (10) | 0.0275 (8) | −0.0103 (7) | 0.0059 (7) | −0.0096 (7) |
C3 | 0.0354 (10) | 0.0285 (10) | 0.0403 (10) | −0.0138 (8) | 0.0148 (8) | −0.0131 (8) |
C4 | 0.0376 (10) | 0.0376 (11) | 0.0567 (12) | −0.0226 (9) | 0.0221 (9) | −0.0290 (10) |
C5 | 0.0291 (9) | 0.0478 (12) | 0.0447 (11) | −0.0168 (9) | 0.0091 (8) | −0.0295 (9) |
C6 | 0.0271 (8) | 0.0341 (10) | 0.0303 (9) | −0.0093 (7) | 0.0027 (7) | −0.0138 (8) |
C7 | 0.0272 (8) | 0.0276 (9) | 0.0200 (8) | −0.0101 (7) | 0.0044 (6) | −0.0100 (7) |
C8 | 0.0309 (9) | 0.0327 (10) | 0.0272 (8) | −0.0145 (8) | 0.0037 (7) | −0.0107 (7) |
C9 | 0.0496 (11) | 0.0315 (10) | 0.0297 (9) | −0.0212 (9) | 0.0084 (8) | −0.0097 (8) |
C10 | 0.0498 (11) | 0.0252 (10) | 0.0290 (9) | −0.0072 (9) | 0.0024 (8) | −0.0080 (7) |
C11 | 0.0309 (9) | 0.0336 (11) | 0.0311 (9) | −0.0024 (8) | −0.0005 (7) | −0.0125 (8) |
C12 | 0.0273 (8) | 0.0328 (10) | 0.0281 (8) | −0.0113 (7) | 0.0051 (7) | −0.0117 (7) |
C13 | 0.0433 (11) | 0.0502 (13) | 0.0381 (10) | −0.0249 (10) | 0.0028 (9) | −0.0129 (9) |
C14 | 0.0380 (10) | 0.0400 (12) | 0.0398 (10) | −0.0109 (9) | −0.0039 (8) | −0.0084 (9) |
C15 | 0.0379 (10) | 0.0422 (12) | 0.0332 (9) | −0.0171 (9) | 0.0020 (8) | −0.0077 (8) |
C16 | 0.0403 (10) | 0.0331 (11) | 0.0294 (9) | −0.0109 (8) | 0.0015 (8) | −0.0072 (8) |
C17 | 0.0466 (11) | 0.0386 (12) | 0.0405 (10) | −0.0233 (9) | −0.0045 (9) | −0.0081 (9) |
C18 | 0.0341 (9) | 0.0324 (11) | 0.0475 (11) | −0.0127 (8) | 0.0035 (8) | −0.0165 (9) |
C19 | 0.0388 (10) | 0.0320 (11) | 0.0302 (9) | −0.0044 (8) | 0.0078 (8) | −0.0037 (8) |
C20 | 0.0330 (9) | 0.0313 (10) | 0.0337 (9) | −0.0132 (8) | 0.0081 (7) | −0.0134 (8) |
C21 | 0.0491 (12) | 0.0400 (12) | 0.0324 (10) | −0.0091 (9) | 0.0039 (9) | −0.0119 (9) |
C22 | 0.0660 (14) | 0.0420 (13) | 0.0418 (11) | −0.0167 (11) | 0.0051 (10) | −0.0177 (10) |
C23 | 0.0393 (11) | 0.0545 (13) | 0.0372 (10) | −0.0230 (10) | 0.0071 (8) | −0.0140 (9) |
C24 | 0.0355 (10) | 0.0505 (13) | 0.0345 (10) | −0.0160 (9) | 0.0029 (8) | −0.0196 (9) |
K1—O3 | 2.6659 (12) | C8—C9 | 1.383 (2) |
K1—O4 | 2.7478 (12) | C8—H8A | 0.9500 |
K1—O1 | 2.7518 (12) | C9—C10 | 1.379 (3) |
K1—N1 | 2.7899 (13) | C9—H9A | 0.9500 |
K1—N1i | 2.9022 (14) | C10—C11 | 1.386 (3) |
K1—C2 | 3.2154 (17) | C10—H10A | 0.9500 |
K1—C1 | 3.3009 (16) | C11—C12 | 1.381 (2) |
K1—C1i | 3.3953 (16) | C11—H11A | 0.9500 |
K1—C2i | 3.4006 (18) | C12—H12A | 0.9500 |
K1—C7i | 3.4257 (15) | C13—C14 | 1.499 (3) |
K1—K1i | 4.2249 (7) | C13—H13A | 0.9900 |
O1—C16 | 1.429 (2) | C13—H13B | 0.9900 |
O1—C13 | 1.439 (2) | C14—H14A | 0.9900 |
O2—C14 | 1.425 (2) | C14—H14B | 0.9900 |
O2—C15 | 1.424 (2) | C15—C16 | 1.496 (3) |
O3—C17 | 1.427 (2) | C15—H15A | 0.9900 |
O3—C18 | 1.427 (2) | C15—H15B | 0.9900 |
O4—C20 | 1.419 (2) | C16—H16A | 0.9900 |
O4—C19 | 1.436 (2) | C16—H16B | 0.9900 |
O5—C21 | 1.420 (2) | C17—C18ii | 1.501 (3) |
O5—C24 | 1.422 (2) | C17—H17A | 0.9900 |
O6—C23 | 1.424 (2) | C17—H17B | 0.9900 |
O6—C22 | 1.428 (2) | C18—C17ii | 1.501 (3) |
N1—C1 | 1.376 (2) | C18—H18A | 0.9900 |
N1—C7 | 1.383 (2) | C18—H18B | 0.9900 |
N1—K1i | 2.9022 (14) | C19—C20iii | 1.506 (2) |
C1—C6 | 1.418 (2) | C19—H19A | 0.9900 |
C1—C2 | 1.419 (2) | C19—H19B | 0.9900 |
C1—K1i | 3.3953 (16) | C20—C19iii | 1.506 (2) |
C2—C3 | 1.384 (3) | C20—H20A | 0.9900 |
C2—K1i | 3.4005 (18) | C20—H20B | 0.9900 |
C2—H2A | 0.9500 | C21—C22 | 1.493 (3) |
C3—C4 | 1.387 (3) | C21—H21A | 0.9900 |
C3—H3A | 0.9500 | C21—H21B | 0.9900 |
C4—C5 | 1.393 (3) | C22—H22A | 0.9900 |
C4—H4A | 0.9500 | C22—H22B | 0.9900 |
C5—C6 | 1.384 (3) | C23—C24 | 1.497 (3) |
C5—H5A | 0.9500 | C23—H23A | 0.9900 |
C6—H6A | 0.9500 | C23—H23B | 0.9900 |
C7—C12 | 1.412 (2) | C24—H24A | 0.9900 |
C7—C8 | 1.415 (2) | C24—H24B | 0.9900 |
C7—K1i | 3.4257 (15) | ||
O3—K1—O4 | 81.76 (4) | C6—C5—C4 | 121.50 (17) |
O3—K1—O1 | 77.02 (4) | C6—C5—H5A | 119.3 |
O4—K1—O1 | 86.30 (4) | C4—C5—H5A | 119.3 |
O3—K1—N1 | 138.80 (4) | C5—C6—C1 | 121.69 (16) |
O4—K1—N1 | 136.28 (4) | C5—C6—H6A | 119.2 |
O1—K1—N1 | 88.65 (4) | C1—C6—H6A | 119.2 |
O3—K1—N1i | 97.79 (4) | N1—C7—C12 | 125.56 (15) |
O4—K1—N1i | 110.13 (4) | N1—C7—C8 | 118.58 (14) |
O1—K1—N1i | 162.11 (4) | C12—C7—C8 | 115.63 (15) |
N1—K1—N1i | 84.17 (4) | N1—C7—K1i | 56.53 (8) |
O3—K1—C2 | 172.89 (4) | C12—C7—K1i | 97.44 (10) |
O4—K1—C2 | 95.44 (4) | C8—C7—K1i | 113.50 (10) |
O1—K1—C2 | 109.43 (4) | C9—C8—C7 | 121.84 (16) |
N1—K1—C2 | 46.22 (4) | C9—C8—H8A | 119.1 |
N1i—K1—C2 | 76.96 (4) | C7—C8—H8A | 119.1 |
O3—K1—C1 | 161.37 (4) | C10—C9—C8 | 121.11 (18) |
O4—K1—C1 | 112.45 (4) | C10—C9—H9A | 119.4 |
O1—K1—C1 | 91.47 (4) | C8—C9—H9A | 119.4 |
N1—K1—C1 | 24.31 (4) | C9—C10—C11 | 118.45 (17) |
N1i—K1—C1 | 88.71 (4) | C9—C10—H10A | 120.8 |
C2—K1—C1 | 25.11 (4) | C11—C10—H10A | 120.8 |
O3—K1—C1i | 79.22 (4) | C12—C11—C10 | 121.14 (17) |
O4—K1—C1i | 121.11 (4) | C12—C11—H11A | 119.4 |
O1—K1—C1i | 140.27 (4) | C10—C11—H11A | 119.4 |
N1—K1—C1i | 88.71 (4) | C11—C12—C7 | 121.84 (17) |
N1i—K1—C1i | 23.62 (4) | C11—C12—H12A | 119.1 |
C2—K1—C1i | 96.83 (4) | C7—C12—H12A | 119.1 |
C1—K1—C1i | 101.77 (4) | O1—C13—C14 | 110.72 (16) |
O3—K1—C2i | 78.16 (4) | O1—C13—H13A | 109.5 |
O4—K1—C2i | 142.84 (4) | C14—C13—H13A | 109.5 |
O1—K1—C2i | 118.58 (4) | O1—C13—H13B | 109.5 |
N1—K1—C2i | 75.36 (4) | C14—C13—H13B | 109.5 |
N1i—K1—C2i | 43.66 (4) | H13A—C13—H13B | 108.1 |
C2—K1—C2i | 100.68 (4) | O2—C14—C13 | 110.90 (15) |
C1—K1—C2i | 95.12 (4) | O2—C14—H14A | 109.5 |
C1i—K1—C2i | 24.10 (4) | C13—C14—H14A | 109.5 |
O3—K1—C7i | 95.50 (4) | O2—C14—H14B | 109.5 |
O4—K1—C7i | 86.71 (4) | C13—C14—H14B | 109.5 |
O1—K1—C7i | 170.42 (4) | H14A—C14—H14B | 108.0 |
N1—K1—C7i | 100.93 (4) | O2—C15—C16 | 110.51 (16) |
N1i—K1—C7i | 23.43 (4) | O2—C15—H15A | 109.5 |
C2—K1—C7i | 77.77 (4) | C16—C15—H15A | 109.5 |
C1—K1—C7i | 97.25 (4) | O2—C15—H15B | 109.5 |
C1i—K1—C7i | 41.30 (4) | C16—C15—H15B | 109.5 |
C2i—K1—C7i | 64.71 (4) | H15A—C15—H15B | 108.1 |
O3—K1—K1i | 126.16 (3) | O1—C16—C15 | 110.88 (15) |
O4—K1—K1i | 135.53 (3) | O1—C16—H16A | 109.5 |
O1—K1—K1i | 129.65 (3) | C15—C16—H16A | 109.5 |
N1—K1—K1i | 43.11 (3) | O1—C16—H16B | 109.5 |
N1i—K1—K1i | 41.07 (3) | C15—C16—H16B | 109.5 |
C2—K1—K1i | 52.27 (3) | H16A—C16—H16B | 108.1 |
C1—K1—K1i | 51.88 (3) | O3—C17—C18ii | 110.80 (15) |
C1i—K1—K1i | 49.89 (3) | O3—C17—H17A | 109.5 |
C2i—K1—K1i | 48.41 (3) | C18ii—C17—H17A | 109.5 |
C7i—K1—K1i | 59.66 (3) | O3—C17—H17B | 109.5 |
C16—O1—C13 | 109.81 (13) | C18ii—C17—H17B | 109.5 |
C16—O1—K1 | 126.57 (9) | H17A—C17—H17B | 108.1 |
C13—O1—K1 | 123.22 (10) | O3—C18—C17ii | 110.30 (15) |
C14—O2—C15 | 109.87 (13) | O3—C18—H18A | 109.6 |
C17—O3—C18 | 109.81 (13) | C17ii—C18—H18A | 109.6 |
C17—O3—K1 | 124.11 (10) | O3—C18—H18B | 109.6 |
C18—O3—K1 | 125.98 (10) | C17ii—C18—H18B | 109.6 |
C20—O4—C19 | 109.49 (13) | H18A—C18—H18B | 108.1 |
C20—O4—K1 | 118.01 (10) | O4—C19—C20iii | 111.02 (14) |
C19—O4—K1 | 131.87 (10) | O4—C19—H19A | 109.4 |
C21—O5—C24 | 109.73 (13) | C20iii—C19—H19A | 109.4 |
C23—O6—C22 | 109.40 (15) | O4—C19—H19B | 109.4 |
C1—N1—C7 | 121.35 (13) | C20iii—C19—H19B | 109.4 |
C1—N1—K1 | 99.13 (9) | H19A—C19—H19B | 108.0 |
C7—N1—K1 | 133.05 (10) | O4—C20—C19iii | 110.36 (15) |
C1—N1—K1i | 98.73 (9) | O4—C20—H20A | 109.6 |
C7—N1—K1i | 100.04 (9) | C19iii—C20—H20A | 109.6 |
K1—N1—K1i | 95.83 (4) | O4—C20—H20B | 109.6 |
N1—C1—C6 | 126.92 (15) | C19iii—C20—H20B | 109.6 |
N1—C1—C2 | 117.45 (14) | H20A—C20—H20B | 108.1 |
C6—C1—C2 | 115.41 (16) | O5—C21—C22 | 111.12 (16) |
N1—C1—K1 | 56.56 (7) | O5—C21—H21A | 109.4 |
C6—C1—K1 | 139.36 (11) | C22—C21—H21A | 109.4 |
C2—C1—K1 | 74.07 (9) | O5—C21—H21B | 109.4 |
N1—C1—K1i | 57.66 (8) | C22—C21—H21B | 109.4 |
C6—C1—K1i | 141.23 (11) | H21A—C21—H21B | 108.0 |
C2—C1—K1i | 78.15 (9) | O6—C22—C21 | 111.51 (17) |
K1—C1—K1i | 78.23 (4) | O6—C22—H22A | 109.3 |
C3—C2—C1 | 122.31 (16) | C21—C22—H22A | 109.3 |
C3—C2—K1 | 134.02 (11) | O6—C22—H22B | 109.3 |
C1—C2—K1 | 80.82 (10) | C21—C22—H22B | 109.3 |
C3—C2—K1i | 139.91 (11) | H22A—C22—H22B | 108.0 |
C1—C2—K1i | 77.74 (10) | O6—C23—C24 | 110.94 (15) |
K1—C2—K1i | 79.32 (4) | O6—C23—H23A | 109.5 |
C3—C2—H2A | 118.8 | C24—C23—H23A | 109.5 |
C1—C2—H2A | 118.8 | O6—C23—H23B | 109.5 |
K1—C2—H2A | 56.3 | C24—C23—H23B | 109.5 |
K1i—C2—H2A | 55.1 | H23A—C23—H23B | 108.0 |
C2—C3—C4 | 120.98 (17) | O5—C24—C23 | 110.51 (16) |
C2—C3—H3A | 119.5 | O5—C24—H24A | 109.5 |
C4—C3—H3A | 119.5 | C23—C24—H24A | 109.5 |
C3—C4—C5 | 118.11 (18) | O5—C24—H24B | 109.5 |
C3—C4—H4A | 120.9 | C23—C24—H24B | 109.5 |
C5—C4—H4A | 120.9 | H24A—C24—H24B | 108.1 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [K(C12H10N)(C4H8O2)2]·C4H8O2 |
Mr | 471.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 10.5417 (5), 10.6758 (6), 12.7711 (5) |
α, β, γ (°) | 70.419 (3), 86.123 (3), 66.278 (2) |
V (Å3) | 1235.97 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.06 × 0.06 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.967, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8425, 5472, 3974 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.107, 1.01 |
No. of reflections | 5472 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.25 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Siemens, 1990), SHELXL97.
In the past, potassium diphenylamide has been used for the synthesis of a lot of transition metal diphenylamides, for example those of Cr (Seidel & Reichardt, 1974), Pd (Villanueva et al., 1994), Th (Barnhart et al., 1995), Nb (Tayebani et al., 1998), Y and Sm (Gamer et al., 2001), Yb (Hitchcock et al., 2002), and Re (Hevia et al., 2002). Potassium diphenylamide also served as a catalyst in the polymerization of lactones and α,β-unsaturated cycloketones (Longi et al., 1965), octamethylcyclotetrasiloxane (Kucera & Jelinek, 1959), and isocyanates (Grogler & Windemuth, 1966). This compound is often mentioned in literature (Barnhart et al., 1995; Bergstrom et al., 1942; Cheshko & Goncharenko, 1971; Fröhlich, 1975), but neither a complete synthetic method nor structural or spectroscopic data have been published. The reaction of potassium with diphenylamine in boiling THF gives (thf)3K(µ2-NPh2)2K(thf)3. Recrystallization from hot dioxane yields single crystals of [(µ-O,O'-dx)(dx-O)K(µ-NPh2)]∞ ((I)) at ambient temperature. In the molecular structure of (I), potassium diphenylamide forms a dimeric molecule with a centosymmetric four-membered KNKiNi ring [symmetry code: (i) 2 - x, 1 - y, -z]. Additionally, each K atom is saturated with three molecules of dioxane, two of them are attached to neighbouring K atoms with the other oxygen atom. This leads to the formation of parallel layers parallel to (001). The coordination sphere of K is distorted square-pyramidal with O4 occupying the apical position and N1, N1i, O1, and O3 lying on the basal positions. The compound cocrystallizes with a molecule of dioxane in the asymmetric unit.