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The molecular structure of the title compound, tris­[2,3,4,5-tetra­chloro-6-(4,8-di-tert-butyl-2,10-di­methyl-6-oxo-12H-5,7-dioxa-6λ5-phosphadibenzo­[a,d]­cyclo­octen-6-yl­oxy)­phenoxido]­aluminium benzene 0.25-solvate, [Al(C29H30Cl4O5P)3]·0.25C6H6, has been determined. The Al atom, with site symmetry 3, is hexacoordinate and is part of a new type of seven-membered chelate ring, with a catecholate O atom forming a covalent bond and a phospho­ryl O atom forming a coordinate covalent bond. As expected, the Al—O coordinate bond is longer than the Al—O covalent bond. The phospho­cine ring has a tub conformation, with an intramolecular C—H...O interaction between one of the ArCH2 H atoms and the phospho­ryl O atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804019592/hg6086sup1.cif
Contains datablocks global, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804019592/hg6086IIsup2.hkl
Contains datablock II

CCDC reference: 251617

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in solvent or counterion
  • R factor = 0.046
  • wR factor = 0.142
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.85 Ratio
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.632 0.831 Tmin' and Tmax expected: 0.774 0.797 RR' = 0.783 Please check that your absorption correction is appropriate. PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.78 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.04 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for C20 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5 PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 53.00 A   3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX6a (McArdle, 1995); software used to prepare material for publication: SHELXL97.

[tris(2,3,4,5-tetrachloro-6-(4,8-di-tert-butyl-2,10- dimethyl-6-oxo-12H-5,7-dioxa-6λ5-phosphadibenzo[a,d]cycloocten-6- yloxy)phenoxido]aluminium benzene 0.25-solvate top
Crystal data top
[Al(C29H30Cl4O5P)3]·0.25C6H6Dx = 1.313 Mg m3
Mr = 1940.41Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 8257 reflections
Hall symbol: -R 3θ = 2.7–20.4°
a = 22.4062 (7) ŵ = 0.46 mm1
c = 33.854 (2) ÅT = 298 K
V = 14718.8 (12) Å3Cube, colourless
Z = 60.55 × 0.50 × 0.50 mm
F(000) = 6027
Data collection top
Siemens SMART CCD area-detector
diffractometer
5770 independent reflections
Radiation source: fine-focus sealed tube4591 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2626
Tmin = 0.633, Tmax = 0.831k = 2626
28911 measured reflectionsl = 2640
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.09P)2 + 7.037P]
where P = (Fo2 + 2Fc2)/3
5770 reflections(Δ/σ)max < 0.001
365 parametersΔρmax = 0.61 e Å3
2 restraintsΔρmin = 0.30 e Å3
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*/UeqOcc. (<1)
Al10.66670.33330.02082 (3)0.0274 (2)
Cl10.58283 (4)0.19848 (5)0.08099 (2)0.0735 (3)
Cl20.47533 (6)0.19316 (7)0.14047 (3)0.1003 (4)
Cl30.38766 (5)0.26220 (5)0.11918 (3)0.0815 (3)
Cl40.40678 (4)0.33054 (4)0.03574 (2)0.0599 (2)
P10.52966 (3)0.30862 (3)0.053209 (17)0.03336 (17)
O10.48796 (8)0.22857 (8)0.05706 (5)0.0447 (4)
O20.49675 (8)0.33638 (9)0.08292 (5)0.0407 (4)
O30.50720 (8)0.32560 (8)0.01313 (5)0.0387 (4)
O40.58999 (7)0.26903 (8)0.00650 (4)0.0346 (4)
O50.60504 (7)0.34225 (8)0.05772 (4)0.0333 (4)
C10.44366 (14)0.18954 (13)0.08864 (9)0.0518 (7)
C20.37717 (15)0.13459 (14)0.07889 (11)0.0666 (9)
C30.34052 (18)0.09436 (18)0.11106 (14)0.0844 (12)
H30.29680.05700.10630.101*
C40.3639 (2)0.1055 (2)0.14921 (15)0.0879 (13)
C50.42776 (19)0.16154 (19)0.15693 (11)0.0761 (10)
H50.44360.17110.18280.091*
C60.46924 (15)0.20426 (15)0.12658 (10)0.0574 (8)
C70.53892 (15)0.26440 (16)0.13705 (9)0.0587 (8)
H7A0.55710.25140.15940.070*
H7B0.56990.27340.11500.070*
C80.53922 (14)0.32994 (16)0.14715 (8)0.0528 (7)
C90.52281 (12)0.36663 (14)0.12027 (7)0.0431 (6)
C100.52512 (14)0.42884 (14)0.12798 (8)0.0493 (6)
C110.54368 (17)0.45292 (18)0.16662 (9)0.0684 (9)
H110.54630.49440.17350.082*
C120.55829 (19)0.4181 (2)0.19509 (9)0.0755 (10)
C130.55689 (17)0.3578 (2)0.18522 (9)0.0703 (9)
H130.56800.33510.20430.084*
C140.3209 (3)0.0579 (3)0.18231 (16)0.130 (2)
H14A0.31040.08320.20120.195*
H14B0.34620.03910.19500.195*
H14C0.27880.02100.17170.195*
C150.5777 (3)0.4478 (3)0.23708 (11)0.1252 (19)
H15A0.54770.46470.24520.188*
H15B0.62450.48490.23730.188*
H15C0.57280.41230.25490.188*
C160.34609 (16)0.12223 (16)0.03721 (13)0.0734 (10)
C170.33743 (18)0.18299 (18)0.02580 (13)0.0888 (12)
H17A0.38130.22470.02720.133*
H17B0.30580.18600.04370.133*
H17C0.31980.17670.00060.133*
C180.38978 (19)0.11096 (17)0.00687 (12)0.0813 (11)
H18A0.37010.10630.01890.122*
H18B0.39090.06980.01330.122*
H18C0.43580.14970.00710.122*
C190.27360 (18)0.05800 (19)0.03606 (16)0.1098 (16)
H19A0.25570.05120.00970.165*
H19B0.24370.06440.05370.165*
H19C0.27630.01830.04410.165*
C200.50849 (15)0.46843 (14)0.09732 (8)0.0520 (7)
C210.43355 (17)0.42648 (18)0.08421 (12)0.0766 (10)
H21A0.42430.38210.07510.115*
H21B0.42530.45010.06320.115*
H21C0.40390.42080.10610.115*
C220.5188 (2)0.53596 (19)0.11392 (11)0.0874 (12)
H22A0.48740.52660.13540.131*
H22B0.51030.56060.09360.131*
H22C0.56530.56330.12320.131*
C230.55677 (18)0.48616 (16)0.06171 (9)0.0653 (8)
H23A0.60380.51180.07050.098*
H23B0.54800.51340.04330.098*
H23C0.54880.44440.04910.098*
C240.50208 (11)0.29390 (11)0.02323 (7)0.0360 (5)
C250.54506 (11)0.26732 (11)0.03194 (7)0.0338 (5)
C260.53388 (13)0.23530 (13)0.06877 (8)0.0448 (6)
C270.48599 (15)0.23320 (15)0.09556 (8)0.0547 (7)
C280.44644 (14)0.26289 (15)0.08604 (8)0.0518 (7)
C290.45466 (12)0.29305 (13)0.04938 (8)0.0430 (6)
C1S0.6218 (15)0.3535 (19)0.3346 (7)0.215 (8)*0.50
H1S0.58980.36780.33840.258*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0262 (3)0.0262 (3)0.0297 (6)0.01308 (17)0.0000.000
Cl10.0764 (5)0.1012 (7)0.0717 (5)0.0659 (5)0.0310 (4)0.0463 (5)
Cl20.1177 (8)0.1487 (10)0.0720 (6)0.0947 (8)0.0561 (6)0.0626 (6)
Cl30.0811 (6)0.1019 (7)0.0794 (6)0.0593 (5)0.0460 (5)0.0241 (5)
Cl40.0568 (4)0.0676 (5)0.0740 (5)0.0450 (4)0.0078 (3)0.0017 (4)
P10.0309 (3)0.0329 (3)0.0388 (3)0.0179 (3)0.0061 (2)0.0047 (2)
O10.0391 (9)0.0345 (9)0.0585 (11)0.0170 (8)0.0130 (8)0.0092 (8)
O20.0390 (9)0.0464 (10)0.0425 (9)0.0258 (8)0.0085 (7)0.0047 (7)
O30.0426 (9)0.0408 (9)0.0408 (9)0.0269 (8)0.0014 (7)0.0009 (7)
O40.0314 (8)0.0326 (8)0.0396 (9)0.0157 (7)0.0078 (7)0.0046 (6)
O50.0325 (8)0.0358 (8)0.0329 (8)0.0180 (7)0.0045 (6)0.0004 (6)
C10.0442 (15)0.0407 (14)0.077 (2)0.0258 (12)0.0236 (14)0.0244 (13)
C20.0419 (15)0.0378 (15)0.121 (3)0.0209 (13)0.0270 (17)0.0277 (16)
C30.0529 (19)0.057 (2)0.143 (4)0.0277 (16)0.038 (2)0.045 (2)
C40.072 (2)0.073 (2)0.129 (4)0.044 (2)0.056 (2)0.058 (2)
C50.081 (2)0.081 (2)0.084 (2)0.054 (2)0.0389 (19)0.0428 (19)
C60.0550 (17)0.0533 (17)0.074 (2)0.0344 (15)0.0248 (15)0.0276 (15)
C70.0621 (18)0.079 (2)0.0517 (16)0.0474 (17)0.0153 (13)0.0283 (15)
C80.0480 (15)0.0696 (19)0.0441 (15)0.0319 (14)0.0157 (12)0.0145 (13)
C90.0393 (13)0.0555 (16)0.0359 (13)0.0247 (12)0.0120 (10)0.0058 (11)
C100.0444 (15)0.0559 (16)0.0473 (15)0.0249 (13)0.0164 (12)0.0019 (12)
C110.068 (2)0.072 (2)0.0573 (19)0.0289 (17)0.0156 (15)0.0115 (16)
C120.073 (2)0.106 (3)0.0447 (18)0.043 (2)0.0043 (15)0.0080 (18)
C130.066 (2)0.102 (3)0.0433 (16)0.042 (2)0.0081 (14)0.0127 (17)
C140.114 (4)0.117 (4)0.164 (5)0.062 (3)0.089 (3)0.095 (4)
C150.150 (5)0.160 (5)0.054 (2)0.069 (4)0.011 (2)0.025 (3)
C160.0413 (16)0.0452 (17)0.124 (3)0.0147 (14)0.0069 (18)0.0115 (18)
C170.0540 (19)0.057 (2)0.148 (4)0.0222 (17)0.009 (2)0.021 (2)
C180.067 (2)0.0508 (19)0.108 (3)0.0157 (17)0.014 (2)0.0024 (19)
C190.052 (2)0.058 (2)0.194 (5)0.0083 (18)0.000 (3)0.020 (3)
C200.0567 (16)0.0462 (15)0.0581 (17)0.0295 (13)0.0192 (13)0.0040 (12)
C210.062 (2)0.073 (2)0.106 (3)0.0417 (18)0.0079 (19)0.022 (2)
C220.131 (3)0.065 (2)0.082 (2)0.061 (2)0.028 (2)0.0007 (18)
C230.080 (2)0.0604 (18)0.0627 (18)0.0409 (17)0.0254 (16)0.0145 (15)
C240.0339 (12)0.0300 (11)0.0410 (13)0.0137 (10)0.0024 (10)0.0008 (10)
C250.0281 (11)0.0294 (11)0.0394 (13)0.0109 (9)0.0043 (9)0.0017 (9)
C260.0409 (13)0.0455 (14)0.0508 (15)0.0238 (12)0.0096 (11)0.0103 (11)
C270.0538 (16)0.0631 (18)0.0494 (16)0.0309 (14)0.0206 (13)0.0187 (13)
C280.0458 (15)0.0557 (16)0.0555 (16)0.0266 (13)0.0204 (12)0.0085 (13)
C290.0344 (13)0.0391 (13)0.0565 (15)0.0191 (11)0.0055 (11)0.0012 (11)
Geometric parameters (Å, º) top
Al1—O4i1.8461 (15)C13—H130.9300
Al1—O41.8461 (15)C14—H14A0.9600
Al1—O4ii1.8461 (15)C14—H14B0.9600
Al1—O5i1.9448 (15)C14—H14C0.9600
Al1—O5ii1.9448 (16)C15—H15A0.9600
Al1—O51.9448 (15)C15—H15B0.9600
Cl1—C261.720 (3)C15—H15C0.9600
Cl2—C271.720 (3)C16—C171.518 (5)
Cl3—C281.724 (3)C16—C181.524 (5)
Cl4—C291.724 (2)C16—C191.540 (4)
P1—O51.4736 (16)C17—H17A0.9600
P1—O21.5494 (16)C17—H17B0.9600
P1—O31.5588 (16)C17—H17C0.9600
P1—O11.5594 (17)C18—H18A0.9600
O1—C11.423 (3)C18—H18B0.9600
O2—C91.415 (3)C18—H18C0.9600
O3—C241.397 (3)C19—H19A0.9600
O4—C251.311 (3)C19—H19B0.9600
C1—C61.377 (4)C19—H19C0.9600
C1—C21.418 (4)C20—C221.519 (4)
C2—C31.390 (5)C20—C211.524 (4)
C2—C161.536 (5)C20—C231.533 (4)
C3—C41.369 (6)C21—H21A0.9600
C3—H30.9300C21—H21B0.9600
C4—C51.377 (6)C21—H21C0.9600
C4—C141.515 (5)C22—H22A0.9600
C5—C61.395 (4)C22—H22B0.9600
C5—H50.9300C22—H22C0.9600
C6—C71.509 (4)C23—H23A0.9600
C7—C81.504 (4)C23—H23B0.9600
C7—H7A0.9700C23—H23C0.9600
C7—H7B0.9700C24—C291.376 (3)
C8—C91.393 (4)C24—C251.394 (3)
C8—C131.400 (4)C25—C261.397 (3)
C9—C101.393 (4)C26—C271.388 (4)
C10—C111.397 (4)C27—C281.386 (4)
C10—C201.528 (4)C28—C291.381 (4)
C11—C121.378 (5)C1S—C1Siii1.294 (4)
C11—H110.9300C1S—C1Siv1.294 (4)
C12—C131.376 (5)C1S—H1S0.9300
C12—C151.537 (5)
O4i—Al1—O497.09 (7)C12—C15—H15B109.5
O4i—Al1—O4ii97.09 (7)H15A—C15—H15B109.5
O4—Al1—O4ii97.09 (7)C12—C15—H15C109.5
O4i—Al1—O5i88.31 (6)H15A—C15—H15C109.5
O4—Al1—O5i90.58 (6)H15B—C15—H15C109.5
O4ii—Al1—O5i169.98 (8)C17—C16—C18111.0 (3)
O4i—Al1—O5ii90.58 (6)C17—C16—C2108.8 (3)
O4—Al1—O5ii169.98 (8)C18—C16—C2112.2 (3)
O4ii—Al1—O5ii88.31 (6)C17—C16—C19106.5 (3)
O5i—Al1—O5ii83.18 (7)C18—C16—C19107.0 (3)
O4i—Al1—O5169.98 (8)C2—C16—C19111.3 (3)
O4—Al1—O588.31 (6)C16—C17—H17A109.5
O4ii—Al1—O590.58 (6)C16—C17—H17B109.5
O5i—Al1—O583.18 (7)H17A—C17—H17B109.5
O5ii—Al1—O583.18 (7)C16—C17—H17C109.5
O5—P1—O2112.42 (9)H17A—C17—H17C109.5
O5—P1—O3113.13 (9)H17B—C17—H17C109.5
O2—P1—O3100.98 (9)C16—C18—H18A109.5
O5—P1—O1116.99 (9)C16—C18—H18B109.5
O2—P1—O1106.01 (9)H18A—C18—H18B109.5
O3—P1—O1105.83 (9)C16—C18—H18C109.5
C1—O1—P1127.04 (17)H18A—C18—H18C109.5
C9—O2—P1127.37 (15)H18B—C18—H18C109.5
C24—O3—P1126.68 (14)C16—C19—H19A109.5
C25—O4—Al1138.90 (14)C16—C19—H19B109.5
P1—O5—Al1124.90 (9)H19A—C19—H19B109.5
C6—C1—C2123.8 (3)C16—C19—H19C109.5
C6—C1—O1118.3 (2)H19A—C19—H19C109.5
C2—C1—O1117.8 (3)H19B—C19—H19C109.5
C3—C2—C1113.9 (4)C22—C20—C21107.1 (3)
C3—C2—C16122.3 (3)C22—C20—C10111.5 (3)
C1—C2—C16123.7 (3)C21—C20—C10110.7 (2)
C4—C3—C2124.9 (4)C22—C20—C23107.2 (3)
C4—C3—H3117.5C21—C20—C23110.4 (3)
C2—C3—H3117.5C10—C20—C23109.8 (2)
C3—C4—C5118.3 (3)C20—C21—H21A109.5
C3—C4—C14121.3 (4)C20—C21—H21B109.5
C5—C4—C14120.4 (5)H21A—C21—H21B109.5
C4—C5—C6121.2 (4)C20—C21—H21C109.5
C4—C5—H5119.4H21A—C21—H21C109.5
C6—C5—H5119.4H21B—C21—H21C109.5
C1—C6—C5117.9 (3)C20—C22—H22A109.5
C1—C6—C7123.6 (2)C20—C22—H22B109.5
C5—C6—C7118.5 (3)H22A—C22—H22B109.5
C8—C7—C6115.0 (2)C20—C22—H22C109.5
C8—C7—H7A108.5H22A—C22—H22C109.5
C6—C7—H7A108.5H22B—C22—H22C109.5
C8—C7—H7B108.5C20—C23—H23A109.5
C6—C7—H7B108.5C20—C23—H23B109.5
H7A—C7—H7B107.5H23A—C23—H23B109.5
C9—C8—C13115.9 (3)C20—C23—H23C109.5
C9—C8—C7123.6 (3)H23A—C23—H23C109.5
C13—C8—C7120.5 (3)H23B—C23—H23C109.5
C10—C9—C8125.4 (3)C29—C24—C25123.5 (2)
C10—C9—O2116.5 (2)C29—C24—O3116.1 (2)
C8—C9—O2117.9 (2)C25—C24—O3120.33 (19)
C9—C10—C11114.6 (3)O4—C25—C24122.2 (2)
C9—C10—C20123.8 (2)O4—C25—C26122.6 (2)
C11—C10—C20121.6 (3)C24—C25—C26115.0 (2)
C12—C11—C10123.0 (3)C27—C26—C25122.5 (2)
C12—C11—H11118.5C27—C26—Cl1119.6 (2)
C10—C11—H11118.5C25—C26—Cl1117.87 (18)
C13—C12—C11119.4 (3)C28—C27—C26120.1 (2)
C13—C12—C15120.8 (4)C28—C27—Cl2120.0 (2)
C11—C12—C15119.8 (4)C26—C27—Cl2119.9 (2)
C12—C13—C8121.6 (3)C29—C28—C27118.9 (2)
C12—C13—H13119.2C29—C28—Cl3120.2 (2)
C8—C13—H13119.2C27—C28—Cl3120.9 (2)
C4—C14—H14A109.5C24—C29—C28119.9 (2)
C4—C14—H14B109.5C24—C29—Cl4119.0 (2)
H14A—C14—H14B109.5C28—C29—Cl4121.06 (19)
C4—C14—H14C109.5C1Siii—C1S—C1Siv119.5 (5)
H14A—C14—H14C109.5C1Siii—C1S—H1S120.2
H14B—C14—H14C109.5C1Siv—C1S—H1S120.2
C12—C15—H15A109.5
Symmetry codes: (i) y+1, xy, z; (ii) x+y+1, x+1, z; (iii) y+1/3, x+y+2/3, z+2/3; (iv) xy+1/3, x1/3, z+2/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7B···O50.972.353.141 (3)138
 

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