supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2287-m2288    [ doi:10.1107/S1600536807037427 ]

Poly[[[mu]-dioxane-[kappa]2O:O'-dioxane-[kappa]O-[mu]-diphenylamido-[kappa]2N:N-potassium] dioxane solvate]

M. Gärtner, H. Görls and M. Westerhausen

Abstract top

The title compound, {[K(C12H10N)(C4H8O2)2]·C4H8O2}n, contains a K atom surrounded by two bridging diphenylamido ligands and three molecules of dioxane. Two of these dioxane ligands are located on a centre of inversion and form bridges to neighbouring K atoms, yielding two-dimensional layers. The K atom is in a distorted square-pyramidal environment in which one bridging dioxane molecule occupies the apical position.

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 40% prabability displacement ellipsoides and the atom-numbering scheme. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The crystal structure of one layer. H atoms have been omitted for clarity.
Poly[[µ-dioxane-κ2O:O'-dioxane-κO-µ-diphenylamido-κ2N:N-\ potassium] dioxane solvate] top
Crystal data top
[K(C12H10N)(C4H8O2)2]·C4H8O2Z = 2
Mr = 471.62F000 = 504
Triclinic, P1Dx = 1.267 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 10.5417 (5) ÅCell parameters from 8425 reflections
b = 10.6758 (6) Åθ = 2.1–27.4º
c = 12.7711 (5) ŵ = 0.25 mm−1
α = 70.419 (3)ºT = 183 (2) K
β = 86.123 (3)ºPrism, colourless
γ = 66.278 (2)º0.06 × 0.06 × 0.05 mm
V = 1235.97 (10) Å3
Data collection top
Nonius KappaCCD
diffractometer		5472 independent reflections
Radiation source: fine-focus sealed tube3974 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 183(2) Kθmax = 27.4º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(Blessing, 1995)		h = −13→12
Tmin = 0.967, Tmax = 0.987k = −13→11
8425 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0488P)2 + 0.0755P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
5472 reflectionsΔρmax = 0.23 e Å−3
289 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[K(C12H10N)(C4H8O2)2]·C4H8O2γ = 66.278 (2)º
Mr = 471.62V = 1235.97 (10) Å3
Triclinic, P1Z = 2
a = 10.5417 (5) ÅMo Kα
b = 10.6758 (6) ŵ = 0.25 mm−1
c = 12.7711 (5) ÅT = 183 (2) K
α = 70.419 (3)º0.06 × 0.06 × 0.05 mm
β = 86.123 (3)º
Data collection top
Nonius KappaCCD
diffractometer		5472 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		3974 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.987Rint = 0.029
8425 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044289 parameters
wR(F2) = 0.107H-atom parameters constrained
S = 1.01Δρmax = 0.23 e Å−3
5472 reflectionsΔρmin = −0.25 e Å−3
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
xyzUiso*/Ueq
K10.80940 (3)0.58975 (4)0.06727 (3)0.02744 (12)
O10.73827 (13)0.51425 (15)0.28382 (9)0.0402 (3)
O20.68752 (13)0.35147 (15)0.49469 (10)0.0424 (3)
O30.58105 (12)0.54644 (14)0.04898 (10)0.0352 (3)
O40.61613 (12)0.86555 (13)0.04205 (10)0.0368 (3)
O50.88112 (13)0.75650 (14)0.39904 (10)0.0433 (3)
O60.71297 (15)1.04991 (15)0.27924 (11)0.0492 (4)
N11.08797 (13)0.42696 (15)0.14643 (10)0.0259 (3)
C11.12229 (16)0.53691 (18)0.15025 (13)0.0245 (4)
C21.07544 (16)0.66780 (18)0.05752 (13)0.0281 (4)
H2A1.03000.6720−0.00610.034*
C31.09369 (18)0.7895 (2)0.05649 (15)0.0347 (4)
H3A1.05990.8752−0.00710.042*
C41.16059 (19)0.7883 (2)0.14690 (16)0.0388 (4)
H4A1.17360.87170.14600.047*
C51.20816 (18)0.6613 (2)0.23914 (16)0.0366 (4)
H5A1.25390.65860.30200.044*
C61.19035 (17)0.5389 (2)0.24136 (14)0.0308 (4)
H6A1.22460.45400.30560.037*
C71.16056 (16)0.28448 (18)0.21367 (12)0.0249 (4)
C81.09112 (18)0.18982 (19)0.24413 (13)0.0296 (4)
H8A0.99480.22780.22270.036*
C91.1595 (2)0.0436 (2)0.30425 (14)0.0357 (4)
H9A1.1093−0.01650.32350.043*
C101.2995 (2)−0.0164 (2)0.33671 (14)0.0377 (5)
H10A1.3461−0.11700.37780.045*
C111.37052 (18)0.0734 (2)0.30805 (14)0.0349 (4)
H11A1.46690.03370.33010.042*
C121.30370 (17)0.21958 (19)0.24804 (13)0.0295 (4)
H12A1.35550.27810.22940.035*
C130.8367 (2)0.4525 (2)0.37896 (15)0.0424 (5)
H13A0.81920.52510.41610.051*
H13B0.93210.42690.35410.051*
C140.82513 (19)0.3192 (2)0.46008 (16)0.0420 (5)
H14A0.85000.24370.42480.050*
H14B0.89130.28040.52600.050*
C150.5912 (2)0.4105 (2)0.40013 (15)0.0388 (5)
H15A0.49570.43430.42450.047*
H15B0.61110.33750.36290.047*
C160.60096 (19)0.5448 (2)0.31960 (14)0.0365 (4)
H16A0.53410.58380.25410.044*
H16B0.57600.61960.35560.044*
C170.5678 (2)0.4124 (2)0.10436 (16)0.0408 (5)
H17A0.48990.42840.15310.061*
H17B0.65400.34160.15190.061*
C180.45827 (19)0.6481 (2)−0.02155 (16)0.0374 (4)
H18A0.46890.7400−0.06150.056*
H18B0.37790.66970.02430.056*
C190.51208 (19)0.9214 (2)0.11231 (14)0.0392 (5)
H19A0.54080.97800.14600.059*
H19B0.50350.83950.17350.059*
C200.62656 (18)0.98288 (19)−0.04698 (14)0.0322 (4)
H20A0.69620.9445−0.09680.048*
H20B0.65811.0407−0.01690.048*
C210.7750 (2)0.8442 (2)0.44988 (15)0.0436 (5)
H21A0.80300.81280.53010.052*
H21B0.68840.83110.44350.052*
C220.7485 (2)1.0009 (2)0.39619 (16)0.0507 (6)
H22A0.67171.05960.43130.061*
H22B0.83261.01530.40860.061*
C230.8202 (2)0.9608 (2)0.22953 (16)0.0429 (5)
H23A0.90730.97220.23770.051*
H23B0.79410.99240.14890.051*
C240.8439 (2)0.8044 (2)0.28301 (14)0.0392 (5)
H24A0.75820.79200.27170.047*
H24B0.91900.74450.24750.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.02222 (18)0.0292 (2)0.0288 (2)−0.00831 (15)0.00330 (14)−0.01012 (15)
O10.0457 (8)0.0467 (8)0.0278 (6)−0.0231 (6)0.0062 (6)−0.0072 (6)
O20.0423 (7)0.0463 (8)0.0301 (7)−0.0195 (6)0.0013 (6)−0.0002 (6)
O30.0338 (6)0.0393 (8)0.0407 (7)−0.0212 (6)0.0021 (5)−0.0155 (6)
O40.0379 (7)0.0247 (7)0.0328 (6)−0.0029 (5)0.0073 (5)−0.0045 (5)
O50.0380 (7)0.0413 (8)0.0410 (7)−0.0046 (6)−0.0057 (6)−0.0148 (6)
O60.0516 (8)0.0381 (8)0.0445 (8)−0.0112 (7)0.0051 (7)−0.0067 (6)
N10.0259 (7)0.0243 (8)0.0247 (7)−0.0097 (6)−0.0015 (6)−0.0048 (6)
C10.0210 (8)0.0273 (9)0.0251 (8)−0.0088 (7)0.0051 (6)−0.0105 (7)
C20.0257 (8)0.0295 (10)0.0275 (8)−0.0103 (7)0.0059 (7)−0.0096 (7)
C30.0354 (10)0.0285 (10)0.0403 (10)−0.0138 (8)0.0148 (8)−0.0131 (8)
C40.0376 (10)0.0376 (11)0.0567 (12)−0.0226 (9)0.0221 (9)−0.0290 (10)
C50.0291 (9)0.0478 (12)0.0447 (11)−0.0168 (9)0.0091 (8)−0.0295 (9)
C60.0271 (8)0.0341 (10)0.0303 (9)−0.0093 (7)0.0027 (7)−0.0138 (8)
C70.0272 (8)0.0276 (9)0.0200 (8)−0.0101 (7)0.0044 (6)−0.0100 (7)
C80.0309 (9)0.0327 (10)0.0272 (8)−0.0145 (8)0.0037 (7)−0.0107 (7)
C90.0496 (11)0.0315 (10)0.0297 (9)−0.0212 (9)0.0084 (8)−0.0097 (8)
C100.0498 (11)0.0252 (10)0.0290 (9)−0.0072 (9)0.0024 (8)−0.0080 (7)
C110.0309 (9)0.0336 (11)0.0311 (9)−0.0024 (8)−0.0005 (7)−0.0125 (8)
C120.0273 (8)0.0328 (10)0.0281 (8)−0.0113 (7)0.0051 (7)−0.0117 (7)
C130.0433 (11)0.0502 (13)0.0381 (10)−0.0249 (10)0.0028 (9)−0.0129 (9)
C140.0380 (10)0.0400 (12)0.0398 (10)−0.0109 (9)−0.0039 (8)−0.0084 (9)
C150.0379 (10)0.0422 (12)0.0332 (9)−0.0171 (9)0.0020 (8)−0.0077 (8)
C160.0403 (10)0.0331 (11)0.0294 (9)−0.0109 (8)0.0015 (8)−0.0072 (8)
C170.0466 (11)0.0386 (12)0.0405 (10)−0.0233 (9)−0.0045 (9)−0.0081 (9)
C180.0341 (9)0.0324 (11)0.0475 (11)−0.0127 (8)0.0035 (8)−0.0165 (9)
C190.0388 (10)0.0320 (11)0.0302 (9)−0.0044 (8)0.0078 (8)−0.0037 (8)
C200.0330 (9)0.0313 (10)0.0337 (9)−0.0132 (8)0.0081 (7)−0.0134 (8)
C210.0491 (12)0.0400 (12)0.0324 (10)−0.0091 (9)0.0039 (9)−0.0119 (9)
C220.0660 (14)0.0420 (13)0.0418 (11)−0.0167 (11)0.0051 (10)−0.0177 (10)
C230.0393 (11)0.0545 (13)0.0372 (10)−0.0230 (10)0.0071 (8)−0.0140 (9)
C240.0355 (10)0.0505 (13)0.0345 (10)−0.0160 (9)0.0029 (8)−0.0196 (9)
Geometric parameters (Å, °) top
K1—O32.6659 (12)C8—C91.383 (2)
K1—O42.7478 (12)C8—H8A0.9500
K1—O12.7518 (12)C9—C101.379 (3)
K1—N12.7899 (13)C9—H9A0.9500
K1—N1i2.9022 (14)C10—C111.386 (3)
K1—C23.2154 (17)C10—H10A0.9500
K1—C13.3009 (16)C11—C121.381 (2)
K1—C1i3.3953 (16)C11—H11A0.9500
K1—C2i3.4006 (18)C12—H12A0.9500
K1—C7i3.4257 (15)C13—C141.499 (3)
K1—K1i4.2249 (7)C13—H13A0.9900
O1—C161.429 (2)C13—H13B0.9900
O1—C131.439 (2)C14—H14A0.9900
O2—C141.425 (2)C14—H14B0.9900
O2—C151.424 (2)C15—C161.496 (3)
O3—C171.427 (2)C15—H15A0.9900
O3—C181.427 (2)C15—H15B0.9900
O4—C201.419 (2)C16—H16A0.9900
O4—C191.436 (2)C16—H16B0.9900
O5—C211.420 (2)C17—C18ii1.501 (3)
O5—C241.422 (2)C17—H17A0.9900
O6—C231.424 (2)C17—H17B0.9900
O6—C221.428 (2)C18—C17ii1.501 (3)
N1—C11.376 (2)C18—H18A0.9900
N1—C71.383 (2)C18—H18B0.9900
N1—K1i2.9022 (14)C19—C20iii1.506 (2)
C1—C61.418 (2)C19—H19A0.9900
C1—C21.419 (2)C19—H19B0.9900
C1—K1i3.3953 (16)C20—C19iii1.506 (2)
C2—C31.384 (3)C20—H20A0.9900
C2—K1i3.4005 (18)C20—H20B0.9900
C2—H2A0.9500C21—C221.493 (3)
C3—C41.387 (3)C21—H21A0.9900
C3—H3A0.9500C21—H21B0.9900
C4—C51.393 (3)C22—H22A0.9900
C4—H4A0.9500C22—H22B0.9900
C5—C61.384 (3)C23—C241.497 (3)
C5—H5A0.9500C23—H23A0.9900
C6—H6A0.9500C23—H23B0.9900
C7—C121.412 (2)C24—H24A0.9900
C7—C81.415 (2)C24—H24B0.9900
C7—K1i3.4257 (15)
O3—K1—O481.76 (4)C6—C5—C4121.50 (17)
O3—K1—O177.02 (4)C6—C5—H5A119.3
O4—K1—O186.30 (4)C4—C5—H5A119.3
O3—K1—N1138.80 (4)C5—C6—C1121.69 (16)
O4—K1—N1136.28 (4)C5—C6—H6A119.2
O1—K1—N188.65 (4)C1—C6—H6A119.2
O3—K1—N1i97.79 (4)N1—C7—C12125.56 (15)
O4—K1—N1i110.13 (4)N1—C7—C8118.58 (14)
O1—K1—N1i162.11 (4)C12—C7—C8115.63 (15)
N1—K1—N1i84.17 (4)N1—C7—K1i56.53 (8)
O3—K1—C2172.89 (4)C12—C7—K1i97.44 (10)
O4—K1—C295.44 (4)C8—C7—K1i113.50 (10)
O1—K1—C2109.43 (4)C9—C8—C7121.84 (16)
N1—K1—C246.22 (4)C9—C8—H8A119.1
N1i—K1—C276.96 (4)C7—C8—H8A119.1
O3—K1—C1161.37 (4)C10—C9—C8121.11 (18)
O4—K1—C1112.45 (4)C10—C9—H9A119.4
O1—K1—C191.47 (4)C8—C9—H9A119.4
N1—K1—C124.31 (4)C9—C10—C11118.45 (17)
N1i—K1—C188.71 (4)C9—C10—H10A120.8
C2—K1—C125.11 (4)C11—C10—H10A120.8
O3—K1—C1i79.22 (4)C12—C11—C10121.14 (17)
O4—K1—C1i121.11 (4)C12—C11—H11A119.4
O1—K1—C1i140.27 (4)C10—C11—H11A119.4
N1—K1—C1i88.71 (4)C11—C12—C7121.84 (17)
N1i—K1—C1i23.62 (4)C11—C12—H12A119.1
C2—K1—C1i96.83 (4)C7—C12—H12A119.1
C1—K1—C1i101.77 (4)O1—C13—C14110.72 (16)
O3—K1—C2i78.16 (4)O1—C13—H13A109.5
O4—K1—C2i142.84 (4)C14—C13—H13A109.5
O1—K1—C2i118.58 (4)O1—C13—H13B109.5
N1—K1—C2i75.36 (4)C14—C13—H13B109.5
N1i—K1—C2i43.66 (4)H13A—C13—H13B108.1
C2—K1—C2i100.68 (4)O2—C14—C13110.90 (15)
C1—K1—C2i95.12 (4)O2—C14—H14A109.5
C1i—K1—C2i24.10 (4)C13—C14—H14A109.5
O3—K1—C7i95.50 (4)O2—C14—H14B109.5
O4—K1—C7i86.71 (4)C13—C14—H14B109.5
O1—K1—C7i170.42 (4)H14A—C14—H14B108.0
N1—K1—C7i100.93 (4)O2—C15—C16110.51 (16)
N1i—K1—C7i23.43 (4)O2—C15—H15A109.5
C2—K1—C7i77.77 (4)C16—C15—H15A109.5
C1—K1—C7i97.25 (4)O2—C15—H15B109.5
C1i—K1—C7i41.30 (4)C16—C15—H15B109.5
C2i—K1—C7i64.71 (4)H15A—C15—H15B108.1
O3—K1—K1i126.16 (3)O1—C16—C15110.88 (15)
O4—K1—K1i135.53 (3)O1—C16—H16A109.5
O1—K1—K1i129.65 (3)C15—C16—H16A109.5
N1—K1—K1i43.11 (3)O1—C16—H16B109.5
N1i—K1—K1i41.07 (3)C15—C16—H16B109.5
C2—K1—K1i52.27 (3)H16A—C16—H16B108.1
C1—K1—K1i51.88 (3)O3—C17—C18ii110.80 (15)
C1i—K1—K1i49.89 (3)O3—C17—H17A109.5
C2i—K1—K1i48.41 (3)C18ii—C17—H17A109.5
C7i—K1—K1i59.66 (3)O3—C17—H17B109.5
C16—O1—C13109.81 (13)C18ii—C17—H17B109.5
C16—O1—K1126.57 (9)H17A—C17—H17B108.1
C13—O1—K1123.22 (10)O3—C18—C17ii110.30 (15)
C14—O2—C15109.87 (13)O3—C18—H18A109.6
C17—O3—C18109.81 (13)C17ii—C18—H18A109.6
C17—O3—K1124.11 (10)O3—C18—H18B109.6
C18—O3—K1125.98 (10)C17ii—C18—H18B109.6
C20—O4—C19109.49 (13)H18A—C18—H18B108.1
C20—O4—K1118.01 (10)O4—C19—C20iii111.02 (14)
C19—O4—K1131.87 (10)O4—C19—H19A109.4
C21—O5—C24109.73 (13)C20iii—C19—H19A109.4
C23—O6—C22109.40 (15)O4—C19—H19B109.4
C1—N1—C7121.35 (13)C20iii—C19—H19B109.4
C1—N1—K199.13 (9)H19A—C19—H19B108.0
C7—N1—K1133.05 (10)O4—C20—C19iii110.36 (15)
C1—N1—K1i98.73 (9)O4—C20—H20A109.6
C7—N1—K1i100.04 (9)C19iii—C20—H20A109.6
K1—N1—K1i95.83 (4)O4—C20—H20B109.6
N1—C1—C6126.92 (15)C19iii—C20—H20B109.6
N1—C1—C2117.45 (14)H20A—C20—H20B108.1
C6—C1—C2115.41 (16)O5—C21—C22111.12 (16)
N1—C1—K156.56 (7)O5—C21—H21A109.4
C6—C1—K1139.36 (11)C22—C21—H21A109.4
C2—C1—K174.07 (9)O5—C21—H21B109.4
N1—C1—K1i57.66 (8)C22—C21—H21B109.4
C6—C1—K1i141.23 (11)H21A—C21—H21B108.0
C2—C1—K1i78.15 (9)O6—C22—C21111.51 (17)
K1—C1—K1i78.23 (4)O6—C22—H22A109.3
C3—C2—C1122.31 (16)C21—C22—H22A109.3
C3—C2—K1134.02 (11)O6—C22—H22B109.3
C1—C2—K180.82 (10)C21—C22—H22B109.3
C3—C2—K1i139.91 (11)H22A—C22—H22B108.0
C1—C2—K1i77.74 (10)O6—C23—C24110.94 (15)
K1—C2—K1i79.32 (4)O6—C23—H23A109.5
C3—C2—H2A118.8C24—C23—H23A109.5
C1—C2—H2A118.8O6—C23—H23B109.5
K1—C2—H2A56.3C24—C23—H23B109.5
K1i—C2—H2A55.1H23A—C23—H23B108.0
C2—C3—C4120.98 (17)O5—C24—C23110.51 (16)
C2—C3—H3A119.5O5—C24—H24A109.5
C4—C3—H3A119.5C23—C24—H24A109.5
C3—C4—C5118.11 (18)O5—C24—H24B109.5
C3—C4—H4A120.9C23—C24—H24B109.5
C5—C4—H4A120.9H24A—C24—H24B108.1
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+2, −z.
Acknowledgements top

We thank the Deutsche Forschungsgemeinschaft (DFG, Bonn–Band Godesberg, Germany) for generous financial support. We also acknowledge funding from the Fonds der Chemischen Industrie (Frankfurt/Main, Germany). In addition, MG is very grateful to the Verband der Chemischen Industrie (VCI/FCI) for a scholarship.

references
References top

Barnhart, D. M., Clark, D. L., Grumbine, S. K. & Watkin, J. G. (1995). Inorg. Chem. 34, 1695–1699.

Bergstrom, F. W., Granara, I. M. & Erickson, V. (1942). J. Org. Chem. 7, 98–102.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Cheshko, F. F. & Goncharenko, I. A. (1971). US Patent 320 499.

Fröhlich, H. O. (1975). Z. Chem. 15, 316–317.

Gamer, M. T., Dehnen, S. & Roesky, P. W. (2001). Organometallics, 20, 4230–4236.

Gärtner, M., Görls, H. & Westerhausen, M. (2007). Acta Cryst. E63. Submitted.. Update?

Grogler, G. & Windemuth, E. (1966). Br. Patent 1 034 152.

Hevia, E., Perez, J. R. V. & Miguel, D. (2002). Organometallics, 21, 1966–1974.

Hitchcock, P. B., Khvostov, A. V., Lappert, M. F. & Protchenko, A. V. (2002). J. Organomet. Chem. 647, 198–204.

Kucera, M. & Jelinek, M. (1959). Czech. Patent 89809.

Longi, P., Greco, F. & Mapelli, F. (1965). Chim. Ind. (Milan), 47, 951–954.

Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Seidel, W. & Reichardt, W. (1974). Z. Anorg. Allg. Chem. 404, 225–229.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97, University of Göttingen, Germany.

Siemens (1990). SHELXTL/PC. Version ????. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Tayebani, M., Gambarotta, S. & Yap, G. (1998). Organometallics, 17, 3639–3641.

Villanueva, L. A., Abboud, K. A. & Boncella, J. M. (1994). Organometallics, 13, 3921–3931.