Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109039833/uk3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109039833/uk3010Isup2.hkl |
CCDC reference: 760128
DEKTP was obtained in a simple and efficient one-step procedure using the acid-catalyzed oxidation reaction of diethylketone by hydrogen peroxide (Eyler et al., 1993). Over a period of 1 h, diethylketone (50 mmol, 5.6 ml) was added constantly [Dropwise?] to a mixture of hydrogen peroxide (4.6 ml) and sulfuric acid (7.3 ml, 70% v/v). The reaction is exothermic and was conducted at low temperature (263 K). After addition, the slurry was stirred for 2 h at low temperature. Subsequently, the organic and aqueous phases were allowed to separate. The organic layer was isolated, neutralized with a saturated ammonium sulfate aqueous solution, and re-extracted with petroleum ether (333 K). This phase was dried over anhydrous sodium sulfate for 12 h, filtered, and the solvent removed under reduced pressure. The crude product was crystallized from methanol, affording colourless crystals of DEKTP, (I) (m.p. 332–333 K; yield 80%).
Because of the intrinsic instability of DEKTP under X-ray irradiation, four crystals of quite similar sizes were used for data collection. In order to minimize damage, the beam shutter was left closed during dead times, ensuring non-continuous irradiation. Different parts of reciprocal space were measured for each crystal, with a common layer in each pair of crystals. Raw data were corrected for crystal decay, using the intensity of three standard reflections. The index range and decay for each crystal were as follows. Crystal 1: h − 12 → 3, decay 1 → 0.23; crystal 2: h − 12 → −6, decay 1 → 0.66; crystal 3: h − 1 → −3, decay 1 → 0.72; crystal 4: h − 3 → 5, decay 1 → 0.65. Finally, a dataset scaling by least-squares fitting of common reflections was used to produce a suitable intensities file (XPREP; Bruker, 1997). Scale factor and Rint indices for each contributing crystal in the final data set were as follows. Crystal 1: K = 1, Rint = 0.066; crystal 2: K = 0.09, Rint = 0.061; crystal 3: K = 0.60, Rint = 0.041; crystal 4: K = 0.34, Rint = 0.025.
Methylene H atoms were placed in idealized positions and refined as riding on their parent C atoms, with C—H = 0.97 Å. Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and the CH3 groups considered as rigid groups free to rotate about their C—C bonds. For all H atoms, Uiso(H) = 1.2Ueq(C) for methylene groups or 1.5Ueq(C) for methyl groups.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Version 2.0; Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C15H30O6 | F(000) = 1344 |
Mr = 306.39 | Dx = 1.115 Mg m−3 |
Monoclinic, P21/c | Melting point = 332–333 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4545 (12) Å | Cell parameters from 68 reflections |
b = 10.859 (3) Å | θ = 4.7–12.5° |
c = 32.168 (5) Å | µ = 0.09 mm−1 |
β = 91.796 (10)° | T = 296 K |
V = 3650.0 (12) Å3 | Needle, colourless |
Z = 8 | 0.6 × 0.4 × 0.3 mm |
Siemens P4 diffractometer | Rint = 0.045 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = −12→5 |
ω scans | k = −11→12 |
17260 measured reflections | l = −38→38 |
6424 independent reflections | 3 standard reflections every 97 reflections |
4356 reflections with I > 2σ(I) | intensity decay: >50% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.044P)2 + 0.5376P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
6424 reflections | Δρmax = 0.15 e Å−3 |
392 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0046 (4) |
C15H30O6 | V = 3650.0 (12) Å3 |
Mr = 306.39 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.4545 (12) Å | µ = 0.09 mm−1 |
b = 10.859 (3) Å | T = 296 K |
c = 32.168 (5) Å | 0.6 × 0.4 × 0.3 mm |
β = 91.796 (10)° |
Siemens P4 diffractometer | Rint = 0.045 |
17260 measured reflections | 3 standard reflections every 97 reflections |
6424 independent reflections | intensity decay: >50% |
4356 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.15 e Å−3 |
6424 reflections | Δρmin = −0.15 e Å−3 |
392 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.57682 (11) | 0.42338 (11) | 0.67141 (4) | 0.0569 (3) | |
O2 | 0.64392 (11) | 0.30702 (11) | 0.68168 (4) | 0.0580 (3) | |
O3 | 0.67111 (10) | 0.37723 (11) | 0.75086 (4) | 0.0575 (3) | |
O4 | 0.57335 (10) | 0.28663 (11) | 0.76263 (4) | 0.0566 (3) | |
O5 | 0.41644 (11) | 0.42489 (11) | 0.73694 (3) | 0.0560 (3) | |
O6 | 0.39324 (11) | 0.34037 (11) | 0.70158 (3) | 0.0572 (3) | |
C1 | 0.44428 (16) | 0.39613 (17) | 0.66591 (5) | 0.0536 (4) | |
C2 | 0.41999 (19) | 0.29785 (19) | 0.63246 (5) | 0.0679 (5) | |
H2A | 0.4582 | 0.2209 | 0.6419 | 0.081* | |
H2B | 0.3285 | 0.2847 | 0.6290 | 0.081* | |
C3 | 0.4734 (3) | 0.3313 (2) | 0.59054 (6) | 0.0929 (7) | |
H3A | 0.4630 | 0.2628 | 0.5718 | 0.139* | |
H3B | 0.5627 | 0.3507 | 0.5940 | 0.139* | |
H3C | 0.4283 | 0.4014 | 0.5793 | 0.139* | |
C4 | 0.38639 (17) | 0.52195 (18) | 0.65660 (6) | 0.0625 (5) | |
H4A | 0.4094 | 0.5774 | 0.6793 | 0.075* | |
H4B | 0.4233 | 0.5543 | 0.6316 | 0.075* | |
C5 | 0.24196 (19) | 0.5203 (2) | 0.65079 (7) | 0.0838 (7) | |
H5A | 0.2112 | 0.6030 | 0.6470 | 0.126* | |
H5B | 0.2046 | 0.4850 | 0.6749 | 0.126* | |
H5C | 0.2186 | 0.4720 | 0.6268 | 0.126* | |
C6 | 0.73208 (15) | 0.33097 (17) | 0.71521 (5) | 0.0549 (4) | |
C7 | 0.82448 (18) | 0.4350 (2) | 0.70541 (6) | 0.0697 (5) | |
H7A | 0.7769 | 0.5116 | 0.7033 | 0.084* | |
H7B | 0.8865 | 0.4432 | 0.7283 | 0.084* | |
C8 | 0.8955 (2) | 0.4155 (3) | 0.66541 (8) | 0.1025 (8) | |
H8A | 0.9405 | 0.4894 | 0.6585 | 0.154* | |
H8B | 0.8354 | 0.3954 | 0.6433 | 0.154* | |
H8C | 0.9556 | 0.3492 | 0.6692 | 0.154* | |
C9 | 0.79281 (18) | 0.20506 (19) | 0.72283 (6) | 0.0666 (5) | |
H9A | 0.7258 | 0.1463 | 0.7286 | 0.080* | |
H9B | 0.8334 | 0.1787 | 0.6976 | 0.080* | |
C10 | 0.8909 (2) | 0.2024 (3) | 0.75826 (8) | 0.1013 (8) | |
H10A | 0.9168 | 0.1189 | 0.7635 | 0.152* | |
H10B | 0.8542 | 0.2362 | 0.7828 | 0.152* | |
H10C | 0.9640 | 0.2504 | 0.7510 | 0.152* | |
C11 | 0.46000 (15) | 0.35313 (17) | 0.77143 (5) | 0.0527 (4) | |
C12 | 0.48267 (18) | 0.45023 (18) | 0.80509 (5) | 0.0621 (5) | |
H12A | 0.5406 | 0.5122 | 0.7948 | 0.075* | |
H12B | 0.4021 | 0.4904 | 0.8105 | 0.075* | |
C13 | 0.5383 (2) | 0.3983 (2) | 0.84564 (6) | 0.0881 (7) | |
H13A | 0.5527 | 0.4642 | 0.8652 | 0.132* | |
H13B | 0.6180 | 0.3579 | 0.8405 | 0.132* | |
H13C | 0.4794 | 0.3402 | 0.8568 | 0.132* | |
C14 | 0.36694 (16) | 0.25044 (18) | 0.78204 (6) | 0.0622 (5) | |
H14A | 0.3626 | 0.1919 | 0.7593 | 0.075* | |
H14B | 0.3994 | 0.2073 | 0.8066 | 0.075* | |
C15 | 0.23330 (19) | 0.2970 (2) | 0.78999 (9) | 0.0988 (8) | |
H15A | 0.1775 | 0.2283 | 0.7944 | 0.148* | |
H15B | 0.2022 | 0.3436 | 0.7664 | 0.148* | |
H15C | 0.2355 | 0.3486 | 0.8142 | 0.148* | |
O21 | 0.81301 (11) | 0.12670 (12) | 0.41802 (3) | 0.0573 (3) | |
O22 | 0.89907 (11) | 0.02031 (11) | 0.42479 (3) | 0.0563 (3) | |
O23 | 1.06812 (12) | 0.14682 (12) | 0.40392 (4) | 0.0637 (3) | |
O24 | 1.11347 (11) | 0.15049 (11) | 0.44775 (4) | 0.0602 (3) | |
O25 | 0.95525 (11) | 0.29950 (11) | 0.46059 (4) | 0.0604 (3) | |
O26 | 0.88545 (11) | 0.20421 (11) | 0.48317 (3) | 0.0551 (3) | |
C21 | 0.77720 (15) | 0.16837 (17) | 0.45789 (5) | 0.0514 (4) | |
C22 | 0.71799 (17) | 0.06752 (17) | 0.48385 (5) | 0.0573 (5) | |
H22A | 0.7851 | 0.0122 | 0.4938 | 0.069* | |
H22B | 0.6800 | 0.1046 | 0.5079 | 0.069* | |
C23 | 0.6164 (2) | −0.0068 (2) | 0.46017 (6) | 0.0794 (6) | |
H23A | 0.5857 | −0.0712 | 0.4777 | 0.119* | |
H23B | 0.6527 | −0.0423 | 0.4359 | 0.119* | |
H23C | 0.5466 | 0.0462 | 0.4520 | 0.119* | |
C24 | 0.68985 (18) | 0.27793 (19) | 0.44725 (6) | 0.0661 (5) | |
H24A | 0.7358 | 0.3350 | 0.4300 | 0.079* | |
H24B | 0.6161 | 0.2485 | 0.4311 | 0.079* | |
C25 | 0.6436 (2) | 0.3463 (2) | 0.48475 (7) | 0.0888 (7) | |
H25A | 0.6009 | 0.4205 | 0.4759 | 0.133* | |
H25B | 0.7154 | 0.3666 | 0.5028 | 0.133* | |
H25C | 0.5852 | 0.2952 | 0.4994 | 0.133* | |
C26 | 1.00319 (17) | 0.03319 (18) | 0.39764 (5) | 0.0572 (5) | |
C27 | 0.9592 (2) | 0.0418 (2) | 0.35197 (5) | 0.0730 (6) | |
H27A | 0.9153 | 0.1197 | 0.3475 | 0.088* | |
H27B | 1.0339 | 0.0417 | 0.3349 | 0.088* | |
C28 | 0.8708 (2) | −0.0618 (2) | 0.33774 (7) | 0.0902 (7) | |
H28A | 0.8429 | −0.0478 | 0.3094 | 0.135* | |
H28B | 0.7979 | −0.0644 | 0.3551 | 0.135* | |
H28C | 0.9158 | −0.1387 | 0.3397 | 0.135* | |
C29 | 1.08606 (18) | −0.07766 (19) | 0.40901 (6) | 0.0659 (5) | |
H29A | 1.0897 | −0.0864 | 0.4390 | 0.079* | |
H29B | 1.0458 | −0.1511 | 0.3975 | 0.079* | |
C30 | 1.2219 (2) | −0.0698 (2) | 0.39369 (7) | 0.0892 (7) | |
H30A | 1.2651 | −0.1465 | 0.3990 | 0.134* | |
H30B | 1.2668 | −0.0047 | 0.4081 | 0.134* | |
H30C | 1.2195 | −0.0533 | 0.3644 | 0.134* | |
C31 | 1.08821 (17) | 0.26987 (17) | 0.46351 (6) | 0.0608 (5) | |
C32 | 1.1474 (2) | 0.3720 (2) | 0.43788 (8) | 0.0834 (6) | |
H32A | 1.0998 | 0.3791 | 0.4116 | 0.100* | |
H32B | 1.1389 | 0.4495 | 0.4526 | 0.100* | |
C33 | 1.2877 (2) | 0.3512 (3) | 0.42913 (11) | 0.1209 (10) | |
H33A | 1.3173 | 0.4155 | 0.4114 | 0.181* | |
H33B | 1.2976 | 0.2730 | 0.4157 | 0.181* | |
H33C | 1.3369 | 0.3518 | 0.4548 | 0.181* | |
C34 | 1.1376 (2) | 0.2585 (2) | 0.50854 (6) | 0.0724 (6) | |
H34A | 1.1070 | 0.1816 | 0.5199 | 0.087* | |
H34B | 1.2303 | 0.2550 | 0.5089 | 0.087* | |
C35 | 1.0968 (3) | 0.3636 (2) | 0.53648 (8) | 0.1039 (8) | |
H35A | 1.1301 | 0.3499 | 0.5643 | 0.156* | |
H35B | 1.0051 | 0.3674 | 0.5367 | 0.156* | |
H35C | 1.1296 | 0.4399 | 0.5262 | 0.156* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0466 (6) | 0.0605 (8) | 0.0632 (7) | −0.0059 (6) | −0.0027 (5) | 0.0021 (6) |
O2 | 0.0488 (7) | 0.0614 (8) | 0.0634 (7) | 0.0007 (6) | −0.0021 (5) | −0.0084 (6) |
O3 | 0.0437 (6) | 0.0659 (8) | 0.0630 (7) | −0.0043 (6) | 0.0026 (5) | −0.0111 (6) |
O4 | 0.0437 (6) | 0.0611 (8) | 0.0652 (7) | 0.0021 (6) | 0.0054 (5) | 0.0027 (6) |
O5 | 0.0572 (7) | 0.0604 (7) | 0.0501 (6) | 0.0046 (6) | −0.0022 (5) | 0.0003 (6) |
O6 | 0.0515 (7) | 0.0659 (8) | 0.0538 (6) | −0.0101 (6) | −0.0039 (5) | 0.0010 (6) |
C1 | 0.0449 (9) | 0.0652 (11) | 0.0502 (9) | −0.0105 (9) | −0.0038 (7) | 0.0030 (8) |
C2 | 0.0675 (12) | 0.0724 (13) | 0.0631 (11) | −0.0157 (11) | −0.0080 (9) | −0.0065 (10) |
C3 | 0.1160 (19) | 0.1025 (18) | 0.0605 (12) | −0.0188 (16) | 0.0064 (12) | −0.0127 (12) |
C4 | 0.0566 (11) | 0.0717 (13) | 0.0588 (10) | −0.0050 (10) | −0.0053 (9) | 0.0063 (9) |
C5 | 0.0595 (12) | 0.1072 (18) | 0.0838 (14) | 0.0070 (13) | −0.0094 (10) | 0.0049 (13) |
C6 | 0.0392 (9) | 0.0662 (12) | 0.0593 (10) | −0.0025 (9) | 0.0011 (8) | −0.0108 (9) |
C7 | 0.0464 (10) | 0.0764 (14) | 0.0864 (13) | −0.0105 (10) | 0.0015 (9) | −0.0042 (11) |
C8 | 0.0722 (15) | 0.124 (2) | 0.1131 (19) | −0.0179 (15) | 0.0302 (14) | 0.0068 (16) |
C9 | 0.0509 (10) | 0.0697 (13) | 0.0794 (12) | 0.0055 (10) | 0.0041 (9) | −0.0089 (10) |
C10 | 0.0781 (15) | 0.1055 (19) | 0.1185 (19) | 0.0120 (15) | −0.0265 (14) | 0.0067 (16) |
C11 | 0.0432 (9) | 0.0624 (11) | 0.0526 (9) | 0.0099 (9) | 0.0017 (7) | 0.0057 (8) |
C12 | 0.0601 (11) | 0.0719 (13) | 0.0544 (10) | 0.0084 (10) | 0.0037 (8) | −0.0024 (9) |
C13 | 0.0981 (17) | 0.1066 (18) | 0.0586 (11) | 0.0051 (15) | −0.0128 (11) | −0.0002 (12) |
C14 | 0.0489 (10) | 0.0698 (13) | 0.0682 (11) | 0.0047 (9) | 0.0067 (9) | 0.0101 (10) |
C15 | 0.0503 (12) | 0.0942 (18) | 0.153 (2) | 0.0072 (12) | 0.0198 (13) | 0.0153 (17) |
O21 | 0.0551 (7) | 0.0730 (8) | 0.0439 (6) | 0.0043 (6) | 0.0028 (5) | 0.0060 (6) |
O22 | 0.0588 (7) | 0.0610 (8) | 0.0497 (6) | 0.0004 (6) | 0.0121 (5) | 0.0028 (6) |
O23 | 0.0653 (8) | 0.0710 (9) | 0.0550 (7) | −0.0093 (7) | 0.0072 (6) | 0.0069 (6) |
O24 | 0.0581 (7) | 0.0587 (8) | 0.0632 (7) | 0.0003 (6) | −0.0053 (6) | −0.0006 (6) |
O25 | 0.0538 (7) | 0.0539 (7) | 0.0730 (8) | −0.0018 (6) | −0.0023 (6) | 0.0096 (6) |
O26 | 0.0531 (7) | 0.0609 (7) | 0.0512 (6) | −0.0030 (6) | −0.0023 (5) | 0.0064 (5) |
C21 | 0.0459 (9) | 0.0632 (11) | 0.0451 (8) | 0.0011 (8) | 0.0002 (7) | 0.0012 (8) |
C22 | 0.0574 (10) | 0.0682 (12) | 0.0465 (9) | 0.0005 (9) | 0.0072 (8) | 0.0017 (8) |
C23 | 0.0714 (13) | 0.0970 (16) | 0.0704 (12) | −0.0254 (13) | 0.0101 (10) | −0.0040 (12) |
C24 | 0.0551 (11) | 0.0772 (13) | 0.0656 (11) | 0.0078 (10) | −0.0028 (9) | 0.0112 (10) |
C25 | 0.0859 (16) | 0.0854 (16) | 0.0954 (16) | 0.0253 (13) | 0.0076 (13) | −0.0028 (13) |
C26 | 0.0574 (11) | 0.0660 (12) | 0.0488 (9) | −0.0059 (10) | 0.0118 (8) | 0.0000 (9) |
C27 | 0.0690 (12) | 0.1032 (17) | 0.0475 (10) | −0.0046 (12) | 0.0102 (9) | 0.0028 (11) |
C28 | 0.0816 (15) | 0.119 (2) | 0.0690 (13) | −0.0025 (15) | −0.0068 (11) | −0.0193 (13) |
C29 | 0.0688 (12) | 0.0685 (13) | 0.0607 (11) | 0.0018 (10) | 0.0070 (9) | −0.0068 (9) |
C30 | 0.0720 (14) | 0.1096 (19) | 0.0871 (15) | 0.0168 (14) | 0.0183 (12) | −0.0120 (14) |
C31 | 0.0486 (10) | 0.0554 (11) | 0.0779 (12) | −0.0039 (9) | −0.0049 (9) | 0.0003 (9) |
C32 | 0.0706 (14) | 0.0654 (14) | 0.1144 (17) | −0.0134 (11) | 0.0081 (12) | 0.0102 (12) |
C33 | 0.0766 (17) | 0.109 (2) | 0.178 (3) | −0.0214 (16) | 0.0296 (17) | 0.015 (2) |
C34 | 0.0637 (12) | 0.0676 (13) | 0.0848 (13) | 0.0020 (10) | −0.0151 (10) | −0.0094 (11) |
C35 | 0.124 (2) | 0.0822 (17) | 0.1031 (18) | 0.0079 (16) | −0.0277 (16) | −0.0281 (14) |
O1—C1 | 1.4224 (19) | O21—C21 | 1.4211 (19) |
O1—O2 | 1.4775 (17) | O21—O22 | 1.4762 (17) |
O2—C6 | 1.4207 (19) | O22—C26 | 1.424 (2) |
O3—C6 | 1.421 (2) | O23—C26 | 1.420 (2) |
O3—O4 | 1.4765 (16) | O23—O24 | 1.4739 (16) |
O4—C11 | 1.424 (2) | O24—C31 | 1.420 (2) |
O5—C11 | 1.4190 (19) | O25—C31 | 1.427 (2) |
O5—O6 | 1.4757 (16) | O25—O26 | 1.4711 (16) |
O6—C1 | 1.416 (2) | O26—C21 | 1.4269 (19) |
C1—C4 | 1.520 (3) | C21—C22 | 1.521 (2) |
C1—C2 | 1.531 (2) | C21—C24 | 1.532 (3) |
C2—C3 | 1.519 (3) | C22—C23 | 1.519 (3) |
C2—H2A | 0.9700 | C22—H22A | 0.9700 |
C2—H2B | 0.9700 | C22—H22B | 0.9700 |
C3—H3A | 0.9600 | C23—H23A | 0.9600 |
C3—H3B | 0.9600 | C23—H23B | 0.9600 |
C3—H3C | 0.9600 | C23—H23C | 0.9600 |
C4—C5 | 1.516 (3) | C24—C25 | 1.509 (3) |
C4—H4A | 0.9700 | C24—H24A | 0.9700 |
C4—H4B | 0.9700 | C24—H24B | 0.9700 |
C5—H5A | 0.9600 | C25—H25A | 0.9600 |
C5—H5B | 0.9600 | C25—H25B | 0.9600 |
C5—H5C | 0.9600 | C25—H25C | 0.9600 |
C6—C9 | 1.524 (3) | C26—C29 | 1.521 (3) |
C6—C7 | 1.526 (3) | C26—C27 | 1.529 (2) |
C7—C8 | 1.521 (3) | C27—C28 | 1.517 (3) |
C7—H7A | 0.9700 | C27—H27A | 0.9700 |
C7—H7B | 0.9700 | C27—H27B | 0.9700 |
C8—H8A | 0.9600 | C28—H28A | 0.9600 |
C8—H8B | 0.9600 | C28—H28B | 0.9600 |
C8—H8C | 0.9600 | C28—H28C | 0.9600 |
C9—C10 | 1.509 (3) | C29—C30 | 1.520 (3) |
C9—H9A | 0.9700 | C29—H29A | 0.9700 |
C9—H9B | 0.9700 | C29—H29B | 0.9700 |
C10—H10A | 0.9600 | C30—H30A | 0.9600 |
C10—H10B | 0.9600 | C30—H30B | 0.9600 |
C10—H10C | 0.9600 | C30—H30C | 0.9600 |
C11—C12 | 1.524 (2) | C31—C32 | 1.525 (3) |
C11—C14 | 1.525 (3) | C31—C34 | 1.527 (3) |
C12—C13 | 1.520 (3) | C32—C33 | 1.519 (3) |
C12—H12A | 0.9700 | C32—H32A | 0.9700 |
C12—H12B | 0.9700 | C32—H32B | 0.9700 |
C13—H13A | 0.9600 | C33—H33A | 0.9600 |
C13—H13B | 0.9600 | C33—H33B | 0.9600 |
C13—H13C | 0.9600 | C33—H33C | 0.9600 |
C14—C15 | 1.515 (3) | C34—C35 | 1.522 (3) |
C14—H14A | 0.9700 | C34—H34A | 0.9700 |
C14—H14B | 0.9700 | C34—H34B | 0.9700 |
C15—H15A | 0.9600 | C35—H35A | 0.9600 |
C15—H15B | 0.9600 | C35—H35B | 0.9600 |
C15—H15C | 0.9600 | C35—H35C | 0.9600 |
C1—O1—O2 | 107.68 (12) | C21—O21—O22 | 107.01 (10) |
C6—O2—O1 | 107.78 (11) | C26—O22—O21 | 107.87 (12) |
C6—O3—O4 | 107.64 (11) | C26—O23—O24 | 107.33 (11) |
C11—O4—O3 | 107.47 (12) | C31—O24—O23 | 107.96 (12) |
C11—O5—O6 | 107.58 (12) | C31—O25—O26 | 107.83 (11) |
C1—O6—O5 | 107.55 (11) | C21—O26—O25 | 107.89 (11) |
O6—C1—O1 | 112.24 (12) | O21—C21—O26 | 112.00 (13) |
O6—C1—C4 | 112.70 (15) | O21—C21—C22 | 112.93 (14) |
O1—C1—C4 | 102.58 (14) | O26—C21—C22 | 102.28 (12) |
O6—C1—C2 | 102.30 (14) | O21—C21—C24 | 102.57 (13) |
O1—C1—C2 | 111.83 (15) | O26—C21—C24 | 111.84 (15) |
C4—C1—C2 | 115.58 (15) | C22—C21—C24 | 115.59 (15) |
C3—C2—C1 | 113.57 (17) | C23—C22—C21 | 113.41 (15) |
C3—C2—H2A | 108.9 | C23—C22—H22A | 108.9 |
C1—C2—H2A | 108.9 | C21—C22—H22A | 108.9 |
C3—C2—H2B | 108.9 | C23—C22—H22B | 108.9 |
C1—C2—H2B | 108.9 | C21—C22—H22B | 108.9 |
H2A—C2—H2B | 107.7 | H22A—C22—H22B | 107.7 |
C2—C3—H3A | 109.5 | C22—C23—H23A | 109.5 |
C2—C3—H3B | 109.5 | C22—C23—H23B | 109.5 |
H3A—C3—H3B | 109.5 | H23A—C23—H23B | 109.5 |
C2—C3—H3C | 109.5 | C22—C23—H23C | 109.5 |
H3A—C3—H3C | 109.5 | H23A—C23—H23C | 109.5 |
H3B—C3—H3C | 109.5 | H23B—C23—H23C | 109.5 |
C5—C4—C1 | 113.75 (17) | C25—C24—C21 | 114.02 (16) |
C5—C4—H4A | 108.8 | C25—C24—H24A | 108.7 |
C1—C4—H4A | 108.8 | C21—C24—H24A | 108.7 |
C5—C4—H4B | 108.8 | C25—C24—H24B | 108.7 |
C1—C4—H4B | 108.8 | C21—C24—H24B | 108.7 |
H4A—C4—H4B | 107.7 | H24A—C24—H24B | 107.6 |
C4—C5—H5A | 109.5 | C24—C25—H25A | 109.5 |
C4—C5—H5B | 109.5 | C24—C25—H25B | 109.5 |
H5A—C5—H5B | 109.5 | H25A—C25—H25B | 109.5 |
C4—C5—H5C | 109.5 | C24—C25—H25C | 109.5 |
H5A—C5—H5C | 109.5 | H25A—C25—H25C | 109.5 |
H5B—C5—H5C | 109.5 | H25B—C25—H25C | 109.5 |
O2—C6—O3 | 112.38 (13) | O23—C26—O22 | 111.68 (14) |
O2—C6—C9 | 102.42 (14) | O23—C26—C29 | 112.79 (15) |
O3—C6—C9 | 112.48 (15) | O22—C26—C29 | 102.44 (14) |
O2—C6—C7 | 112.24 (15) | O23—C26—C27 | 102.23 (14) |
O3—C6—C7 | 102.00 (14) | O22—C26—C27 | 112.50 (15) |
C9—C6—C7 | 115.73 (15) | C29—C26—C27 | 115.59 (16) |
C8—C7—C6 | 113.62 (18) | C28—C27—C26 | 113.99 (17) |
C8—C7—H7A | 108.8 | C28—C27—H27A | 108.8 |
C6—C7—H7A | 108.8 | C26—C27—H27A | 108.8 |
C8—C7—H7B | 108.8 | C28—C27—H27B | 108.8 |
C6—C7—H7B | 108.8 | C26—C27—H27B | 108.8 |
H7A—C7—H7B | 107.7 | H27A—C27—H27B | 107.6 |
C7—C8—H8A | 109.5 | C27—C28—H28A | 109.5 |
C7—C8—H8B | 109.5 | C27—C28—H28B | 109.5 |
H8A—C8—H8B | 109.5 | H28A—C28—H28B | 109.5 |
C7—C8—H8C | 109.5 | C27—C28—H28C | 109.5 |
H8A—C8—H8C | 109.5 | H28A—C28—H28C | 109.5 |
H8B—C8—H8C | 109.5 | H28B—C28—H28C | 109.5 |
C10—C9—C6 | 114.12 (17) | C30—C29—C26 | 114.11 (18) |
C10—C9—H9A | 108.7 | C30—C29—H29A | 108.7 |
C6—C9—H9A | 108.7 | C26—C29—H29A | 108.7 |
C10—C9—H9B | 108.7 | C30—C29—H29B | 108.7 |
C6—C9—H9B | 108.7 | C26—C29—H29B | 108.7 |
H9A—C9—H9B | 107.6 | H29A—C29—H29B | 107.6 |
C9—C10—H10A | 109.5 | C29—C30—H30A | 109.5 |
C9—C10—H10B | 109.5 | C29—C30—H30B | 109.5 |
H10A—C10—H10B | 109.5 | H30A—C30—H30B | 109.5 |
C9—C10—H10C | 109.5 | C29—C30—H30C | 109.5 |
H10A—C10—H10C | 109.5 | H30A—C30—H30C | 109.5 |
H10B—C10—H10C | 109.5 | H30B—C30—H30C | 109.5 |
O5—C11—O4 | 111.83 (13) | O24—C31—O25 | 111.97 (14) |
O5—C11—C12 | 102.38 (14) | O24—C31—C32 | 112.83 (16) |
O4—C11—C12 | 112.34 (14) | O25—C31—C32 | 102.20 (15) |
O5—C11—C14 | 112.64 (14) | O24—C31—C34 | 101.76 (14) |
O4—C11—C14 | 102.38 (14) | O25—C31—C34 | 112.34 (16) |
C12—C11—C14 | 115.64 (15) | C32—C31—C34 | 116.14 (17) |
C13—C12—C11 | 113.58 (17) | C33—C32—C31 | 113.7 (2) |
C13—C12—H12A | 108.8 | C33—C32—H32A | 108.8 |
C11—C12—H12A | 108.8 | C31—C32—H32A | 108.8 |
C13—C12—H12B | 108.8 | C33—C32—H32B | 108.8 |
C11—C12—H12B | 108.8 | C31—C32—H32B | 108.8 |
H12A—C12—H12B | 107.7 | H32A—C32—H32B | 107.7 |
C12—C13—H13A | 109.5 | C32—C33—H33A | 109.5 |
C12—C13—H13B | 109.5 | C32—C33—H33B | 109.5 |
H13A—C13—H13B | 109.5 | H33A—C33—H33B | 109.5 |
C12—C13—H13C | 109.5 | C32—C33—H33C | 109.5 |
H13A—C13—H13C | 109.5 | H33A—C33—H33C | 109.5 |
H13B—C13—H13C | 109.5 | H33B—C33—H33C | 109.5 |
C15—C14—C11 | 113.07 (17) | C35—C34—C31 | 114.02 (17) |
C15—C14—H14A | 109.0 | C35—C34—H34A | 108.7 |
C11—C14—H14A | 109.0 | C31—C34—H34A | 108.7 |
C15—C14—H14B | 109.0 | C35—C34—H34B | 108.7 |
C11—C14—H14B | 109.0 | C31—C34—H34B | 108.7 |
H14A—C14—H14B | 107.8 | H34A—C34—H34B | 107.6 |
C14—C15—H15A | 109.5 | C34—C35—H35A | 109.5 |
C14—C15—H15B | 109.5 | C34—C35—H35B | 109.5 |
H15A—C15—H15B | 109.5 | H35A—C35—H35B | 109.5 |
C14—C15—H15C | 109.5 | C34—C35—H35C | 109.5 |
H15A—C15—H15C | 109.5 | H35A—C35—H35C | 109.5 |
H15B—C15—H15C | 109.5 | H35B—C35—H35C | 109.5 |
C1—O1—O2—C6 | −135.40 (13) | C21—O21—O22—C26 | −136.54 (13) |
C6—O3—O4—C11 | −135.28 (13) | C26—O23—O24—C31 | −136.54 (14) |
C11—O5—O6—C1 | −136.30 (13) | C31—O25—O26—C21 | −134.54 (14) |
O5—O6—C1—O1 | 57.42 (16) | O22—O21—C21—O26 | 59.57 (16) |
O5—O6—C1—C4 | −57.80 (15) | O22—O21—C21—C22 | −55.26 (16) |
O5—O6—C1—C2 | 177.44 (12) | O22—O21—C21—C24 | 179.66 (12) |
O2—O1—C1—O6 | 57.54 (16) | O25—O26—C21—O21 | 56.61 (16) |
O2—O1—C1—C4 | 178.77 (12) | O25—O26—C21—C22 | 177.80 (12) |
O2—O1—C1—C2 | −56.77 (16) | O25—O26—C21—C24 | −57.91 (16) |
O6—C1—C2—C3 | −176.63 (17) | O21—C21—C22—C23 | −47.0 (2) |
O1—C1—C2—C3 | −56.3 (2) | O26—C21—C22—C23 | −167.56 (16) |
C4—C1—C2—C3 | 60.5 (2) | C24—C21—C22—C23 | 70.7 (2) |
O6—C1—C4—C5 | −57.0 (2) | O21—C21—C24—C25 | −176.27 (17) |
O1—C1—C4—C5 | −177.93 (15) | O26—C21—C24—C25 | −56.1 (2) |
C2—C1—C4—C5 | 60.1 (2) | C22—C21—C24—C25 | 60.4 (2) |
O1—O2—C6—O3 | 58.51 (17) | O24—O23—C26—O22 | 58.39 (16) |
O1—O2—C6—C9 | 179.45 (12) | O24—O23—C26—C29 | −56.34 (16) |
O1—O2—C6—C7 | −55.78 (16) | O24—O23—C26—C27 | 178.88 (13) |
O4—O3—C6—O2 | 56.96 (17) | O21—O22—C26—O23 | 56.67 (16) |
O4—O3—C6—C9 | −58.01 (16) | O21—O22—C26—C29 | 177.63 (12) |
O4—O3—C6—C7 | 177.36 (12) | O21—O22—C26—C27 | −57.62 (18) |
O2—C6—C7—C8 | −54.1 (2) | O23—C26—C27—C28 | −172.48 (17) |
O3—C6—C7—C8 | −174.60 (18) | O22—C26—C27—C28 | −52.6 (2) |
C9—C6—C7—C8 | 63.0 (2) | C29—C26—C27—C28 | 64.6 (2) |
O2—C6—C9—C10 | −178.82 (17) | O23—C26—C29—C30 | −43.7 (2) |
O3—C6—C9—C10 | −57.9 (2) | O22—C26—C29—C30 | −163.93 (16) |
C7—C6—C9—C10 | 58.7 (2) | C27—C26—C29—C30 | 73.4 (2) |
O6—O5—C11—O4 | 58.43 (16) | O23—O24—C31—O25 | 58.89 (17) |
O6—O5—C11—C12 | 178.90 (12) | O23—O24—C31—C32 | −55.75 (18) |
O6—O5—C11—C14 | −56.24 (16) | O23—O24—C31—C34 | 179.07 (13) |
O3—O4—C11—O5 | 57.93 (16) | O26—O25—C31—O24 | 57.09 (17) |
O3—O4—C11—C12 | −56.54 (16) | O26—O25—C31—C32 | 178.11 (13) |
O3—O4—C11—C14 | 178.76 (11) | O26—O25—C31—C34 | −56.71 (18) |
O5—C11—C12—C13 | −176.61 (16) | O24—C31—C32—C33 | −49.3 (3) |
O4—C11—C12—C13 | −56.5 (2) | O25—C31—C32—C33 | −169.8 (2) |
C14—C11—C12—C13 | 60.5 (2) | C34—C31—C32—C33 | 67.6 (3) |
O5—C11—C14—C15 | −55.8 (2) | O24—C31—C34—C35 | −167.02 (18) |
O4—C11—C14—C15 | −176.08 (17) | O25—C31—C34—C35 | −47.1 (2) |
C12—C11—C14—C15 | 61.4 (2) | C32—C31—C34—C35 | 70.0 (3) |
Experimental details
Crystal data | |
Chemical formula | C15H30O6 |
Mr | 306.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 10.4545 (12), 10.859 (3), 32.168 (5) |
β (°) | 91.796 (10) |
V (Å3) | 3650.0 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.6 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17260, 6424, 4356 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.112, 1.03 |
No. of reflections | 6424 |
No. of parameters | 392 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.15 |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Version 2.0; Macrae et al., 2006).
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Cyclic gem-peroxides with three peroxidic functions are formed readily from the acid-catalyzed oxidation of carbonyl compounds with hydrogen peroxide to form a mixture of open-chain and cyclic peroxides, the latter arising from the former. The unusual reactivity of peroxides is generally attributed to the weakness of the O—O bond linkage (the reactive site) and hence the ease with which it is homolytically cleaved. Many studies have reported the thermal decomposition rate reaction constants (Cañizo, 2006; Eyler, 2006; Iglesias et al., 2009) for diethyl ketone triperoxide (DEKTP, C15H30O6) and triacetone triperoxide (TATP, C9H18O6). These reports showed that it is possible to compare the thermal solution behaviour for both compounds, and concluded that DEKTP has a higher thermal solution decomposition stability than TATP.
Cyclic peroxide derivatives have been studied mainly for two reasons. Firstly, they are potentially useful radical initiators, for example in the bulk polymerization of styrene (Cerna et al., 2002) or for controlled-rheology polypropylene (Pucci et al., 2004). In this application, their performance is similar to that presented by a multifunctional initiator, giving rise to high molecular weight polystyrene at a high reaction rate. Secondly, some members of this family are also interesting from a conformational point of view, since large rings including only sp3-hybridized atoms can be stabilized in different conformations, sometimes affording separable conformers. A classic example is TATP, a well known peroxide-based explosive material with a power close to that of TNT. A comprehensive study showed that the explosion of this product involves an entropic burst, which is the result of the formation of four gaseous compounds from one molecule of TATP in the solid state (Dubnikova et al., 2005). The X-ray structure of TATP has been established (Groth, 1969; Dubnikova et al., 2005; Jensen et al., 2009), showing that a single conformer is stabilized in the solid state, where the nine-membered cycle adopts a twisted boat–chair conformation with a local symmetry close to D3. However, some reports claim that two TATP conformers related by a flip-flop interconversion mechanism may exist at room temperature. Computational and experimental evidence supports this claim. For instance, it was found that the C2-TATP conformer is only 1.85 kcal mol−1 (1 kcal mol−1 = 4.184 kJ mol−1) less stable than the D3 conformer. On the other hand, the barrier for interconversion, at least in the gas phase, is sufficiently high to allow the two conformers to be separated (Denekamp et al., 2005).
A direct strategy for assessing the conformational flexibility of TATP is to synthesize and characterize closely related compounds. However, very few cyclic triperoxide derivatives bearing a cyclononane core have been X-ray characterized to date (Denekamp et al., 2005; Terent'ev et al., 2007), and all presented a D3 conformation. The present work deals with the room-temperature solid-state structure of the title compound, DEKTP, (I), where all methyl groups of TATP are formally substituted by ethyl groups. It should be emphasized that, although the compound is difficult to handle at room temperature, low-temperature data collection was not attempted, because the room-temperature structure is the one of interest regarding the relationship with the peculiar properties of the compound. On the other hand, these systems are known to be prone to polymorphism, as recently reported for TATP, for which an exceptional series of five new polymorphs were characterized at T = 180–200 K (Reany et al., 2009).
DEKTP crystallizes as well shaped colourless crystals with a rather low melting point (m.p. 332–333 K) and a strong unpleasant smell. Although the crystals are air-stable for several months, they slowly volatilize in the X-ray beam, as previously observed in the case of TATP (Dubnikova et al., 2005). Depending on the crystal size and power of irradiation, ca 75% diffraction decay is observed after 40 h of data collection. Four partial diffraction patterns with overlapping layers were thus measured, using four crystals, which afforded a complete scaled data set for structure refinement (see Experimental).
The crystal structure of DEKTP has no unexpected features. Molecules display a globular shape with a hydrophobic external surface, and are thus well separated in the crystal. The resulting packing index is rather low, 0.63 (PLATON; Spek, 2003), although no significant voids are detected in the crystal structure.
In contrast with TATP, the title peroxide has two molecules in the asymmetric unit, both located on general positions (Figs. 1 and 2). The two independent molecules have quite similar conformations: an overlay (Macrae et al., 2006) between both molecules computed with all non-H atoms affords an r.m.s. deviation of 0.115 Å. The largest differences arise from the peripheral ethyl groups, which are potentially free to rotate about their σ C—C bonds, providing that the C atoms in the cyclononane rings retain a tetrahedral geometry (Fig. 2, inset). The largest deviation of 0.348 Å corresponds to the pair of fitted atoms C10/C30. Each molecule displays the same twisted boat–chair conformation, similar to that found for TATP. Total puckering amplitudes (Cremer & Pople, 1975) are similar in both independent molecules, 1.3232 (13) and 1.3220 (13) Å for the O1- and O21-rings, respectively. Departures from ideal D3 symmetry for the cyclononane cores are small, as reflected in the range of the C—O—O—C torsion angles in the cycles, −134.54 (14)– −136.54 (14)°. The bond lengths for the O—O groups also span a very narrow range, 1.4711 (16)–1.4775 (17) Å, and compare well with those found in TATP [average 1.470 (2) Å at 180 K].
In conclusion, a comparison between the molecular structures of TATP and DEKTP clearly shows that substitution of methyl by ethyl groups does not introduce additional strain in the cyclononane ring system. Assuming a similar thermal decomposition pathway for both molecules, we can then suggest that DEKTP is not as sensitive to impact or temperature changes as TATP is, because some products of the decomposition process have higher molecular weights. For instance, acetone, the main product of TATP decomposition, should be diethylketone in the case of DEKTP decomposition. In the same way, methyl acetate as a product of decomposition of TATP is replaced by ethyl propanoate for DEKTP (see scheme 2 in Dubnikova et al., 2005).