The acinitro group in the title compound, C6H16N+·C17H17N2O5-, is almost coplanar with the isoxazoline ring, which assumes a flattened envelope conformation. The cyclohexanone ring adopts a half-chair conformation and carries a perpendicular [83.54 (10)°] phenyl ring and a bent [64.30 (17)°] acetyl group. The triethylammonium residue forms a hydrogen bond with the nitronate moiety. Intermolecular interaction is exerted through a hydrogen bond between the acidic H atom of the cyclohexanone ring and the N atom of the isoxazoline ring.
Supporting information
CCDC reference: 198966
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.043
- wR factor = 0.125
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.00
From the CIF: _reflns_number_total 3539
Count of symmetry unique reflns 3546
Completeness (_total/calc) 99.80%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
A solution of 3-methyl-4-nitro-5-styrylisoxazole (1.15 g, 5.6 mmoles) and acetylacetone (1.5 g, 15 mmoles) in triethylamine (20 ml) and tetrahydrofuran (20 ml) was stirred at 353 K. After 3 h the reaction mixture was allowed to cool at room temperature and the solid obtained was filtered and washed with cold acetone (m.p. 428 K, from ethanol).
3488 Friedel pairs were merged before refinement. The absolute configuration was not determined.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 1990).
Triethylammonium 8-Acetyl-3-methyl-9-phenyl-7-oxo-2-azaspiro [4.5]dec-2-en-4-nitronate
top
Crystal data top
C17H17N2O5·C6H16N | F(000) = 928 |
Mr = 431.52 | Dx = 1.180 Mg m−3 |
Monoclinic, Cc | Melting point: 428 K |
Hall symbol: C -2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 21.815 (3) Å | Cell parameters from 44 reflections |
b = 10.464 (2) Å | θ = 3–25° |
c = 11.222 (2) Å | µ = 0.08 mm−1 |
β = 108.55 (1)° | T = 293 K |
V = 2428.6 (7) Å3 | Needles, colourless |
Z = 4 | 0.4 × 0.4 × 0.2 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.017 |
Radiation source: sealed tube | θmax = 30.0°, θmin = 2.7° |
Graphite monochromator | h = −30→30 |
ω scans | k = −14→14 |
7207 measured reflections | l = −15→15 |
3539 independent reflections | 3 standard reflections every 97 reflections |
2723 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0828P)2] where P = (Fo2 + 2Fc2)/3 |
3539 reflections | (Δ/σ)max = 0.014 |
345 parameters | Δρmax = 0.21 e Å−3 |
2 restraints | Δρmin = −0.13 e Å−3 |
Crystal data top
C17H17N2O5·C6H16N | V = 2428.6 (7) Å3 |
Mr = 431.52 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 21.815 (3) Å | µ = 0.08 mm−1 |
b = 10.464 (2) Å | T = 293 K |
c = 11.222 (2) Å | 0.4 × 0.4 × 0.2 mm |
β = 108.55 (1)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.017 |
7207 measured reflections | 3 standard reflections every 97 reflections |
3539 independent reflections | intensity decay: none |
2723 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 2 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.21 e Å−3 |
3539 reflections | Δρmin = −0.13 e Å−3 |
345 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.17473 (10) | 0.60683 (19) | 0.0287 (2) | 0.0633 (7) | |
O2 | 0.06787 (8) | 0.61062 (16) | 0.22264 (15) | 0.0446 (5) | |
O3 | −0.14099 (9) | 0.6493 (2) | −0.02743 (19) | 0.0600 (6) | |
O4 | −0.08001 (10) | 0.5440 (2) | −0.11724 (17) | 0.0592 (6) | |
O5 | 0.23920 (11) | 0.3558 (3) | 0.1935 (2) | 0.0819 (9) | |
N1 | 0.02610 (11) | 0.67852 (18) | 0.27551 (18) | 0.0444 (6) | |
N2 | −0.08550 (9) | 0.6024 (2) | −0.01949 (18) | 0.0449 (6) | |
C1 | 0.13438 (10) | 0.39925 (19) | 0.05260 (19) | 0.0346 (5) | |
C2 | 0.10193 (10) | 0.35869 (19) | 0.15068 (18) | 0.0335 (5) | |
C3 | 0.03275 (10) | 0.4114 (2) | 0.1140 (2) | 0.0354 (5) | |
C4 | 0.03063 (10) | 0.55664 (19) | 0.10056 (18) | 0.0347 (5) | |
C5 | 0.06273 (12) | 0.5991 (2) | 0.0047 (2) | 0.0418 (6) | |
C6 | 0.12882 (11) | 0.5427 (2) | 0.02993 (19) | 0.0380 (6) | |
C7 | 0.10082 (11) | 0.2143 (2) | 0.1660 (2) | 0.0375 (6) | |
C8 | 0.12618 (15) | 0.1601 (3) | 0.2841 (3) | 0.0533 (9) | |
C9 | 0.1228 (2) | 0.0290 (3) | 0.2999 (3) | 0.0731 (13) | |
C10 | 0.0947 (2) | −0.0491 (3) | 0.1990 (4) | 0.0757 (15) | |
C11 | 0.0697 (2) | 0.0033 (3) | 0.0812 (4) | 0.0733 (10) | |
C12 | 0.07268 (16) | 0.1348 (2) | 0.0641 (3) | 0.0542 (8) | |
C13 | −0.03143 (12) | 0.6807 (2) | 0.1958 (2) | 0.0417 (6) | |
C14 | −0.03481 (10) | 0.6136 (2) | 0.0827 (2) | 0.0379 (6) | |
C15 | −0.08378 (17) | 0.7484 (4) | 0.2288 (3) | 0.0691 (11) | |
C16 | 0.20518 (12) | 0.3611 (3) | 0.0869 (3) | 0.0508 (8) | |
C17 | 0.22978 (19) | 0.3340 (5) | −0.0204 (4) | 0.0855 (14) | |
N3 | 0.32714 (12) | 0.1884 (3) | 0.6970 (2) | 0.0558 (7) | |
C18 | 0.3275 (3) | 0.3253 (4) | 0.7341 (4) | 0.0860 (16) | |
C19 | 0.35420 (18) | 0.1660 (4) | 0.5920 (4) | 0.0802 (15) | |
C20 | 0.26075 (15) | 0.1334 (3) | 0.6720 (3) | 0.0653 (10) | |
C21 | 0.2580 (2) | −0.0078 (4) | 0.6512 (4) | 0.0870 (14) | |
C22 | 0.3179 (3) | 0.2315 (9) | 0.4724 (4) | 0.136 (3) | |
C23 | 0.3939 (4) | 0.3808 (5) | 0.7842 (7) | 0.146 (3) | |
H1 | 0.1126 (14) | 0.364 (3) | −0.029 (3) | 0.0415* | |
H2 | 0.1279 (14) | 0.391 (3) | 0.235 (3) | 0.0402* | |
H3A | 0.0069 (15) | 0.372 (3) | 0.037 (3) | 0.047 (7)* | |
H3B | 0.0121 (16) | 0.390 (3) | 0.178 (3) | 0.059 (9)* | |
H5A | 0.0377 (14) | 0.565 (2) | −0.076 (3) | 0.039 (6)* | |
H5B | 0.0620 (14) | 0.686 (3) | −0.003 (3) | 0.049 (8)* | |
H8 | 0.1486 (16) | 0.212 (3) | 0.353 (3) | 0.056 (8)* | |
H9 | 0.1381 (18) | −0.009 (4) | 0.389 (4) | 0.071 (10)* | |
H10 | 0.095 (2) | −0.136 (4) | 0.209 (4) | 0.073 (10)* | |
H11 | 0.051 (2) | −0.043 (4) | 0.006 (4) | 0.087 (12)* | |
H12 | 0.0597 (15) | 0.170 (3) | −0.017 (3) | 0.048 (8)* | |
H15A | −0.06772 | 0.77705 | 0.31437 | 0.0828* | |
H15B | −0.11945 | 0.69121 | 0.21900 | 0.0828* | |
H15C | −0.09795 | 0.82065 | 0.17419 | 0.0828* | |
H17A | 0.27610 | 0.32822 | 0.01001 | 0.1026* | |
H17B | 0.21702 | 0.40174 | −0.08094 | 0.1026* | |
H17C | 0.21204 | 0.25465 | −0.05916 | 0.1026* | |
H18A | 0.30627 | 0.33303 | 0.79765 | 0.15 (2)* | |
H18B | 0.30275 | 0.37458 | 0.66150 | 0.084 (13)* | |
H19A | 0.39872 | 0.19511 | 0.61816 | 0.091 (13)* | |
H19B | 0.35434 | 0.07484 | 0.57646 | 0.093 (13)* | |
H20A | 0.24584 | 0.15241 | 0.74282 | 0.093 (13)* | |
H20B | 0.23145 | 0.17459 | 0.59841 | 0.083 (12)* | |
H21A | 0.21600 | −0.03895 | 0.64696 | 0.166 (9)* | |
H21B | 0.29024 | −0.04868 | 0.71955 | 0.166 (9)* | |
H21C | 0.26613 | −0.02650 | 0.57382 | 0.166 (9)* | |
H22A | 0.33908 | 0.21610 | 0.41064 | 0.166 (9)* | |
H22B | 0.31679 | 0.32176 | 0.48698 | 0.166 (9)* | |
H22C | 0.27458 | 0.19892 | 0.44238 | 0.166 (9)* | |
H23A | 0.39139 | 0.46531 | 0.81566 | 0.166 (9)* | |
H23B | 0.41304 | 0.38492 | 0.71813 | 0.166 (9)* | |
H23C | 0.42007 | 0.32793 | 0.85102 | 0.166 (9)* | |
H32 | 0.353 (2) | 0.146 (4) | 0.763 (4) | 0.082 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0482 (10) | 0.0493 (10) | 0.0930 (15) | −0.0093 (8) | 0.0232 (10) | 0.0147 (10) |
O2 | 0.0382 (8) | 0.0472 (9) | 0.0393 (8) | 0.0048 (7) | −0.0007 (6) | −0.0100 (7) |
O3 | 0.0366 (9) | 0.0781 (13) | 0.0583 (10) | 0.0178 (9) | 0.0052 (8) | 0.0044 (9) |
O4 | 0.0503 (10) | 0.0753 (13) | 0.0405 (8) | 0.0111 (9) | −0.0016 (7) | −0.0148 (8) |
O5 | 0.0411 (10) | 0.126 (2) | 0.0686 (14) | 0.0160 (12) | 0.0034 (10) | 0.0247 (14) |
N1 | 0.0536 (11) | 0.0428 (9) | 0.0348 (9) | 0.0023 (9) | 0.0113 (8) | −0.0063 (8) |
N2 | 0.0375 (10) | 0.0502 (11) | 0.0412 (10) | 0.0072 (8) | 0.0042 (8) | 0.0032 (8) |
C1 | 0.0325 (9) | 0.0350 (10) | 0.0346 (9) | 0.0014 (8) | 0.0083 (8) | 0.0012 (8) |
C2 | 0.0361 (9) | 0.0306 (9) | 0.0315 (9) | 0.0012 (7) | 0.0075 (7) | 0.0019 (7) |
C3 | 0.0337 (9) | 0.0338 (9) | 0.0377 (10) | −0.0008 (8) | 0.0101 (8) | 0.0014 (8) |
C4 | 0.0344 (9) | 0.0336 (9) | 0.0317 (9) | 0.0030 (8) | 0.0041 (7) | −0.0018 (8) |
C5 | 0.0453 (12) | 0.0357 (10) | 0.0432 (11) | 0.0055 (9) | 0.0125 (9) | 0.0091 (9) |
C6 | 0.0387 (10) | 0.0381 (10) | 0.0356 (10) | −0.0018 (8) | 0.0095 (8) | 0.0045 (8) |
C7 | 0.0394 (10) | 0.0316 (9) | 0.0423 (10) | 0.0011 (8) | 0.0140 (8) | 0.0046 (8) |
C8 | 0.0706 (18) | 0.0446 (13) | 0.0443 (13) | 0.0067 (12) | 0.0176 (12) | 0.0085 (11) |
C9 | 0.106 (3) | 0.0512 (16) | 0.0673 (19) | 0.0092 (16) | 0.0350 (18) | 0.0250 (14) |
C10 | 0.100 (3) | 0.0364 (14) | 0.095 (3) | −0.0044 (16) | 0.037 (2) | 0.0147 (16) |
C11 | 0.087 (2) | 0.0393 (13) | 0.085 (2) | −0.0135 (15) | 0.0153 (18) | −0.0085 (15) |
C12 | 0.0666 (16) | 0.0372 (11) | 0.0498 (13) | −0.0050 (12) | 0.0059 (12) | −0.0002 (11) |
C13 | 0.0481 (12) | 0.0379 (10) | 0.0400 (11) | 0.0036 (9) | 0.0152 (9) | 0.0012 (8) |
C14 | 0.0349 (10) | 0.0389 (10) | 0.0367 (10) | 0.0043 (8) | 0.0070 (8) | 0.0004 (8) |
C15 | 0.0641 (17) | 0.077 (2) | 0.0710 (18) | 0.0127 (15) | 0.0283 (15) | −0.0187 (16) |
C16 | 0.0388 (12) | 0.0519 (13) | 0.0625 (15) | 0.0084 (10) | 0.0173 (11) | 0.0116 (11) |
C17 | 0.069 (2) | 0.110 (3) | 0.090 (2) | 0.035 (2) | 0.043 (2) | 0.011 (2) |
N3 | 0.0531 (12) | 0.0605 (13) | 0.0446 (11) | 0.0079 (10) | 0.0024 (9) | 0.0052 (10) |
C18 | 0.124 (4) | 0.0615 (19) | 0.073 (2) | −0.004 (2) | 0.032 (2) | −0.0031 (17) |
C19 | 0.0588 (18) | 0.095 (3) | 0.093 (3) | 0.0086 (17) | 0.0328 (19) | −0.010 (2) |
C20 | 0.0542 (16) | 0.079 (2) | 0.0634 (18) | 0.0094 (15) | 0.0199 (14) | 0.0016 (15) |
C21 | 0.070 (2) | 0.078 (2) | 0.106 (3) | −0.0058 (19) | 0.018 (2) | −0.004 (2) |
C22 | 0.125 (4) | 0.231 (8) | 0.065 (2) | 0.002 (5) | 0.049 (3) | 0.014 (4) |
C23 | 0.171 (6) | 0.084 (3) | 0.142 (5) | −0.051 (4) | −0.009 (5) | 0.009 (3) |
Geometric parameters (Å, º) top
O1—C6 | 1.209 (3) | C3—H3B | 0.99 (3) |
O2—N1 | 1.425 (3) | C5—H5A | 0.96 (3) |
O2—C4 | 1.466 (3) | C5—H5B | 0.91 (3) |
O3—N2 | 1.283 (3) | C8—H8 | 0.94 (3) |
O4—N2 | 1.294 (3) | C9—H9 | 1.03 (4) |
O5—C16 | 1.192 (4) | C10—H10 | 0.92 (4) |
N1—C13 | 1.289 (3) | C11—H11 | 0.95 (4) |
N2—C14 | 1.321 (3) | C12—H12 | 0.94 (3) |
N3—C20 | 1.500 (4) | C15—H15A | 0.9595 |
N3—C18 | 1.491 (5) | C15—H15C | 0.9603 |
N3—C19 | 1.495 (5) | C15—H15B | 0.9598 |
N3—H32 | 0.89 (4) | C17—H17A | 0.9601 |
C1—C6 | 1.521 (3) | C17—H17B | 0.9598 |
C1—C16 | 1.521 (4) | C17—H17C | 0.9598 |
C1—C2 | 1.545 (3) | C18—C23 | 1.494 (10) |
C2—C3 | 1.535 (3) | C19—C22 | 1.491 (7) |
C2—C7 | 1.522 (3) | C20—C21 | 1.494 (5) |
C3—C4 | 1.527 (3) | C18—H18A | 0.9694 |
C4—C5 | 1.525 (3) | C18—H18B | 0.9702 |
C4—C14 | 1.500 (3) | C19—H19A | 0.9699 |
C5—C6 | 1.499 (4) | C19—H19B | 0.9699 |
C7—C8 | 1.385 (4) | C20—H20A | 0.9703 |
C7—C12 | 1.389 (4) | C20—H20B | 0.9698 |
C8—C9 | 1.388 (4) | C21—H21A | 0.9593 |
C9—C10 | 1.373 (5) | C21—H21B | 0.9606 |
C10—C11 | 1.374 (6) | C21—H21C | 0.9601 |
C11—C12 | 1.394 (4) | C22—H22A | 0.9610 |
C13—C15 | 1.487 (5) | C22—H22B | 0.9602 |
C13—C14 | 1.432 (3) | C22—H22C | 0.9593 |
C16—C17 | 1.493 (5) | C23—H23A | 0.9602 |
C1—H1 | 0.96 (3) | C23—H23B | 0.9607 |
C2—H2 | 0.99 (3) | C23—H23C | 0.9602 |
C3—H3A | 0.96 (3) | | |
| | | |
O1···C17 | 3.212 (5) | H1···O2i | 2.66 (3) |
O1···C20i | 3.402 (4) | H1···H17B | 2.5553 |
O3···C20ii | 3.376 (4) | H1···N1i | 2.44 (3) |
O3···C18ii | 3.139 (5) | H2···O2 | 2.63 (3) |
O3···N3ii | 2.974 (3) | H2···O5 | 2.64 (3) |
O3···C15 | 2.936 (4) | H2···H8 | 2.26 (4) |
O4···C19ii | 3.370 (5) | H3A···O4 | 2.78 (3) |
O4···C3 | 3.263 (3) | H3A···C12 | 2.83 (3) |
O4···C5 | 3.032 (3) | H3A···H5A | 2.58 (4) |
O4···N3ii | 2.836 (3) | H3A···H12 | 2.57 (5) |
O5···C22 | 3.319 (6) | H3B···H19Av | 2.5110 |
O5···C7 | 3.288 (4) | H5A···O4 | 2.47 (3) |
O1···H17B | 2.7736 | H5A···H3A | 2.58 (4) |
O1···H8i | 2.66 (3) | H8···H2 | 2.26 (4) |
O1···H18Bi | 2.7222 | H8···O1iv | 2.66 (3) |
O1···H20Bi | 2.5997 | H9···C11x | 2.99 (4) |
O2···H10iii | 2.73 (4) | H9···C12x | 3.07 (4) |
O2···H1iv | 2.66 (3) | H10···N1xi | 2.70 (4) |
O2···H2 | 2.63 (3) | H10···O2xi | 2.73 (4) |
O3···H23Cii | 2.8783 | H12···C3 | 3.07 (3) |
O3···H21Cv | 2.9176 | H12···H1 | 2.36 (5) |
O3···H32ii | 2.31 (4) | H12···H3A | 2.57 (5) |
O3···H18Aii | 2.7269 | H12···N1i | 2.72 (3) |
O3···H15C | 2.8043 | H12···C1 | 2.87 (3) |
O3···H19Bv | 2.6355 | H15B···O3 | 2.6896 |
O3···H17Avi | 2.7270 | H15B···H22Avi | 2.5979 |
O3···H15B | 2.6896 | H15B···H21Bv | 2.4725 |
O4···H5A | 2.47 (3) | H15C···O3 | 2.8043 |
O4···H32ii | 1.96 (4) | H17A···O3xii | 2.7270 |
O4···H3A | 2.78 (3) | H17B···O1 | 2.7736 |
O5···H2 | 2.64 (3) | H17B···H1 | 2.5553 |
N1···C1iv | 3.352 (3) | H17B···C6 | 2.9915 |
N2···N3ii | 3.272 (3) | H17C···H1 | 2.5684 |
N3···O4vii | 2.836 (3) | H18A···C17xiii | 3.0202 |
N3···N2vii | 3.272 (3) | H18A···H20A | 2.2743 |
N3···O3vii | 2.974 (3) | H18A···O3vii | 2.7269 |
N1···H1iv | 2.44 (3) | H18B···C22 | 2.7019 |
N1···H12iv | 2.72 (3) | H18B···H20B | 2.5689 |
N1···H10iii | 2.70 (4) | H18B···H22B | 2.1486 |
N2···H23Cii | 2.7943 | H18B···O1iv | 2.7222 |
N2···H32ii | 2.43 (4) | H19A···C23 | 2.7172 |
N2···H19Bv | 2.6871 | H19A···H23B | 2.2535 |
C1···N1i | 3.352 (3) | H19A···H3Bxiv | 2.5110 |
C3···O4 | 3.263 (3) | H19B···C21 | 2.6438 |
C5···O4 | 3.032 (3) | H19B···H21C | 2.1891 |
C7···O5 | 3.288 (4) | H19B···O3xiv | 2.6355 |
C15···O3 | 2.936 (4) | H19B···N2xiv | 2.6871 |
C17···O1 | 3.212 (5) | H20A···H18A | 2.2743 |
C18···O3vii | 3.139 (5) | H20B···C22 | 2.7582 |
C19···O4vii | 3.370 (5) | H20B···H18B | 2.5689 |
C20···O1iv | 3.402 (4) | H20B···H22C | 2.2504 |
C20···O3vii | 3.376 (4) | H20B···O1iv | 2.5997 |
C22···O5 | 3.319 (6) | H21A···C9x | 3.0513 |
C1···H12 | 2.87 (3) | H21A···C10x | 3.0291 |
C3···H12 | 3.07 (3) | H21A···C11x | 3.0612 |
C6···H17B | 2.9915 | H21B···H32 | 2.4161 |
C9···H21Aviii | 3.0513 | H21B···H15Bxiv | 2.4725 |
C10···H21Aviii | 3.0291 | H21C···C19 | 2.7461 |
C11···H21Aviii | 3.0612 | H21C···H19B | 2.1891 |
C11···H9viii | 2.99 (4) | H21C···O3xiv | 2.9176 |
C12···H1 | 2.86 (3) | H22A···C15xii | 3.0488 |
C12···H9viii | 3.07 (4) | H22A···H15Bxii | 2.5979 |
C12···H3A | 2.83 (3) | H22B···C18 | 2.7082 |
C15···H22Avi | 3.0488 | H22B···H18B | 2.1486 |
C17···H18Aix | 3.0202 | H22C···C20 | 2.7741 |
C18···H22B | 2.7082 | H22C···H20B | 2.2504 |
C19···H23B | 2.7826 | H23B···C19 | 2.7826 |
C19···H21C | 2.7461 | H23B···H19A | 2.2535 |
C20···H22C | 2.7741 | H23C···H32 | 2.4127 |
C21···H19B | 2.6438 | H23C···O3vii | 2.8783 |
C22···H18B | 2.7019 | H23C···N2vii | 2.7943 |
C22···H20B | 2.7582 | H32···H21B | 2.4161 |
C23···H19A | 2.7172 | H32···H23C | 2.4127 |
H1···C12 | 2.86 (3) | H32···O3vii | 2.31 (4) |
H1···H12 | 2.36 (5) | H32···O4vii | 1.96 (4) |
H1···H17C | 2.5684 | H32···N2vii | 2.43 (4) |
| | | |
N1—O2—C4 | 110.10 (17) | C6—C5—H5B | 113 (2) |
O2—N1—C13 | 109.28 (18) | C7—C8—H8 | 119.6 (19) |
O3—N2—O4 | 117.5 (2) | C9—C8—H8 | 119.9 (19) |
O3—N2—C14 | 122.5 (2) | C10—C9—H9 | 120 (2) |
O4—N2—C14 | 120.0 (2) | C8—C9—H9 | 120 (2) |
C18—N3—C20 | 109.9 (3) | C9—C10—H10 | 120 (3) |
C19—N3—C20 | 113.1 (3) | C11—C10—H10 | 120 (3) |
C18—N3—C19 | 113.7 (3) | C10—C11—H11 | 126 (3) |
C18—N3—H32 | 107 (3) | C12—C11—H11 | 114 (3) |
C19—N3—H32 | 106 (3) | C11—C12—H12 | 120.5 (19) |
C20—N3—H32 | 106 (3) | C7—C12—H12 | 118.8 (19) |
C2—C1—C6 | 111.10 (17) | C13—C15—H15B | 109.46 |
C6—C1—C16 | 108.8 (2) | C13—C15—H15C | 109.44 |
C2—C1—C16 | 113.95 (19) | C13—C15—H15A | 109.46 |
C3—C2—C7 | 109.72 (18) | H15A—C15—H15B | 109.52 |
C1—C2—C7 | 112.36 (17) | H15B—C15—H15C | 109.46 |
C1—C2—C3 | 110.14 (16) | H15A—C15—H15C | 109.49 |
C2—C3—C4 | 112.37 (18) | C16—C17—H17C | 109.46 |
C5—C4—C14 | 114.90 (18) | H17A—C17—H17B | 109.49 |
O2—C4—C3 | 107.52 (16) | C16—C17—H17B | 109.44 |
O2—C4—C5 | 107.75 (17) | H17B—C17—H17C | 109.50 |
C3—C4—C14 | 113.97 (18) | H17A—C17—H17C | 109.49 |
C3—C4—C5 | 110.71 (17) | C16—C17—H17A | 109.45 |
O2—C4—C14 | 101.11 (16) | N3—C18—C23 | 113.4 (5) |
C4—C5—C6 | 112.46 (18) | N3—C19—C22 | 114.1 (4) |
C1—C6—C5 | 116.16 (19) | N3—C20—C21 | 113.4 (3) |
O1—C6—C1 | 121.8 (2) | N3—C18—H18A | 108.92 |
O1—C6—C5 | 122.0 (2) | N3—C18—H18B | 108.91 |
C8—C7—C12 | 118.7 (2) | C23—C18—H18A | 108.88 |
C2—C7—C8 | 119.9 (2) | C23—C18—H18B | 108.86 |
C2—C7—C12 | 121.35 (19) | H18A—C18—H18B | 107.75 |
C7—C8—C9 | 120.4 (3) | N3—C19—H19A | 108.70 |
C8—C9—C10 | 120.7 (3) | N3—C19—H19B | 108.70 |
C9—C10—C11 | 119.5 (3) | C22—C19—H19A | 108.79 |
C10—C11—C12 | 120.3 (3) | C22—C19—H19B | 108.75 |
C7—C12—C11 | 120.4 (3) | H19A—C19—H19B | 107.65 |
N1—C13—C14 | 111.8 (2) | N3—C20—H20A | 108.88 |
C14—C13—C15 | 128.8 (2) | N3—C20—H20B | 108.93 |
N1—C13—C15 | 119.4 (2) | C21—C20—H20A | 108.87 |
C4—C14—C13 | 107.33 (19) | C21—C20—H20B | 108.88 |
N2—C14—C4 | 125.37 (19) | H20A—C20—H20B | 107.73 |
N2—C14—C13 | 127.3 (2) | C20—C21—H21A | 109.51 |
O5—C16—C1 | 121.6 (3) | C20—C21—H21B | 109.44 |
O5—C16—C17 | 122.1 (3) | C20—C21—H21C | 109.45 |
C1—C16—C17 | 116.2 (3) | H21A—C21—H21B | 109.48 |
C16—C1—H1 | 107.1 (19) | H21A—C21—H21C | 109.53 |
C6—C1—H1 | 103.3 (19) | H21B—C21—H21C | 109.42 |
C2—C1—H1 | 111.9 (19) | C19—C22—H22A | 109.43 |
C3—C2—H2 | 110.3 (18) | C19—C22—H22B | 109.50 |
C7—C2—H2 | 104.8 (18) | C19—C22—H22C | 109.55 |
C1—C2—H2 | 109.4 (18) | H22A—C22—H22B | 109.38 |
H3A—C3—H3B | 106 (3) | H22A—C22—H22C | 109.46 |
C2—C3—H3A | 109 (2) | H22B—C22—H22C | 109.51 |
C4—C3—H3B | 106.9 (19) | C18—C23—H23A | 109.54 |
C2—C3—H3B | 111 (2) | C18—C23—H23B | 109.53 |
C4—C3—H3A | 110.3 (19) | C18—C23—H23C | 109.53 |
C4—C5—H5B | 111 (2) | H23A—C23—H23B | 109.39 |
C4—C5—H5A | 107.7 (18) | H23A—C23—H23C | 109.44 |
C6—C5—H5A | 104.8 (18) | H23B—C23—H23C | 109.40 |
H5A—C5—H5B | 107 (2) | | |
| | | |
C4—O2—N1—C13 | −4.9 (2) | C3—C2—C7—C12 | 66.5 (3) |
N1—O2—C4—C3 | −113.36 (19) | C1—C2—C7—C8 | 125.9 (3) |
N1—O2—C4—C5 | 127.28 (18) | C1—C2—C3—C4 | −57.3 (2) |
N1—O2—C4—C14 | 6.4 (2) | C7—C2—C3—C4 | 178.46 (17) |
O2—N1—C13—C14 | 0.9 (3) | C2—C3—C4—O2 | −60.7 (2) |
O2—N1—C13—C15 | −179.0 (2) | C2—C3—C4—C5 | 56.8 (2) |
O3—N2—C14—C4 | 177.3 (2) | C2—C3—C4—C14 | −171.85 (17) |
O3—N2—C14—C13 | −2.6 (4) | C14—C4—C5—C6 | 178.02 (17) |
O4—N2—C14—C4 | −3.8 (3) | C3—C4—C14—N2 | −70.6 (3) |
O4—N2—C14—C13 | 176.3 (2) | O2—C4—C14—N2 | 174.3 (2) |
C20—N3—C19—C22 | 64.9 (5) | O2—C4—C14—C13 | −5.7 (2) |
C18—N3—C20—C21 | −172.2 (3) | O2—C4—C5—C6 | 66.2 (2) |
C19—N3—C20—C21 | 59.6 (4) | C3—C4—C5—C6 | −51.1 (2) |
C20—N3—C18—C23 | 169.0 (4) | C5—C4—C14—C13 | −121.4 (2) |
C18—N3—C19—C22 | −61.4 (5) | C3—C4—C14—C13 | 109.3 (2) |
C19—N3—C18—C23 | −63.1 (5) | C5—C4—C14—N2 | 58.6 (3) |
C6—C1—C16—C17 | −86.0 (3) | C4—C5—C6—O1 | −133.1 (2) |
C16—C1—C6—O1 | 6.7 (3) | C4—C5—C6—C1 | 49.0 (2) |
C16—C1—C6—C5 | −175.4 (2) | C2—C7—C8—C9 | 177.1 (3) |
C2—C1—C16—O5 | −32.0 (4) | C12—C7—C8—C9 | −0.7 (5) |
C2—C1—C16—C17 | 149.5 (3) | C2—C7—C12—C11 | −177.2 (3) |
C6—C1—C16—O5 | 92.6 (3) | C8—C7—C12—C11 | 0.5 (5) |
C6—C1—C2—C3 | 51.7 (2) | C7—C8—C9—C10 | 0.4 (6) |
C6—C1—C2—C7 | 174.36 (18) | C8—C9—C10—C11 | 0.0 (7) |
C16—C1—C2—C3 | 174.99 (19) | C9—C10—C11—C12 | −0.1 (7) |
C16—C1—C2—C7 | −62.4 (2) | C10—C11—C12—C7 | −0.1 (6) |
C2—C1—C6—O1 | 132.9 (2) | N1—C13—C14—C4 | 3.3 (3) |
C2—C1—C6—C5 | −49.2 (2) | C15—C13—C14—N2 | 3.1 (4) |
C1—C2—C7—C12 | −56.4 (3) | N1—C13—C14—N2 | −176.8 (2) |
C3—C2—C7—C8 | −111.2 (3) | C15—C13—C14—C4 | −176.8 (3) |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1/2, y+1/2, z−1; (iii) x, y+1, z; (iv) x, −y+1, z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) x−1/2, y+1/2, z; (vii) x+1/2, y−1/2, z+1; (viii) x, −y, z−1/2; (ix) x, y, z−1; (x) x, −y, z+1/2; (xi) x, y−1, z; (xii) x+1/2, y−1/2, z; (xiii) x, y, z+1; (xiv) x+1/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H32···O3vii | 0.89 (4) | 2.31 (4) | 2.974 (3) | 131 (4) |
N3—H32···O4vii | 0.89 (4) | 1.96 (4) | 2.836 (3) | 168 (4) |
N3—H32···N2vii | 0.89 (4) | 2.43 (4) | 3.272 (3) | 158 (4) |
C1—H1···N1i | 0.96 (3) | 2.44 (3) | 3.352 (3) | 159 (3) |
C5—H5A···O4 | 0.96 (3) | 2.47 (3) | 3.032 (3) | 117 (2) |
C20—H20B···O1iv | 0.9698 | 2.5997 | 3.402 (4) | 140.26 |
Symmetry codes: (i) x, −y+1, z−1/2; (iv) x, −y+1, z+1/2; (vii) x+1/2, y−1/2, z+1. |
Experimental details
Crystal data |
Chemical formula | C17H17N2O5·C6H16N |
Mr | 431.52 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 21.815 (3), 10.464 (2), 11.222 (2) |
β (°) | 108.55 (1) |
V (Å3) | 2428.6 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.4 × 0.4 × 0.2 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7207, 3539, 2723 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.125, 1.00 |
No. of reflections | 3539 |
No. of parameters | 345 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.13 |
Selected geometric parameters (Å, º) topO2—N1 | 1.425 (3) | C3—C4 | 1.527 (3) |
O2—C4 | 1.466 (3) | C4—C5 | 1.525 (3) |
O3—N2 | 1.283 (3) | C4—C14 | 1.500 (3) |
O4—N2 | 1.294 (3) | C13—C15 | 1.487 (5) |
N1—C13 | 1.289 (3) | C13—C14 | 1.432 (3) |
N2—C14 | 1.321 (3) | | |
| | | |
N1—O2—C4 | 110.10 (17) | N1—C13—C14 | 111.8 (2) |
O2—N1—C13 | 109.28 (18) | C14—C13—C15 | 128.8 (2) |
O3—N2—O4 | 117.5 (2) | N1—C13—C15 | 119.4 (2) |
O3—N2—C14 | 122.5 (2) | C4—C14—C13 | 107.33 (19) |
O4—N2—C14 | 120.0 (2) | N2—C14—C4 | 125.37 (19) |
O2—C4—C3 | 107.52 (16) | N2—C14—C13 | 127.3 (2) |
O2—C4—C5 | 107.75 (17) | N3—C18—C23 | 113.4 (5) |
O2—C4—C14 | 101.11 (16) | N3—C19—C22 | 114.1 (4) |
O1—C6—C1 | 121.8 (2) | N3—C20—C21 | 113.4 (3) |
O1—C6—C5 | 122.0 (2) | | |
| | | |
O4—N2—C14—C4 | −3.8 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H32···O4i | 0.89 (4) | 1.96 (4) | 2.836 (3) | 168 (4) |
C1—H1···N1ii | 0.96 (3) | 2.44 (3) | 3.352 (3) | 159 (3) |
C5—H5A···O4 | 0.96 (3) | 2.47 (3) | 3.032 (3) | 117 (2) |
C20—H20B···O1iii | 0.9698 | 2.5997 | 3.402 (4) | 140.26 |
Symmetry codes: (i) x+1/2, y−1/2, z+1; (ii) x, −y+1, z−1/2; (iii) x, −y+1, z+1/2. |
Spiroisoxazolines display a range of biological activity, including herbicidal, plant hormones and anticancer properties (Howe & Shelton, 1990; De Amici et al., 1990; Smietana et al., 1999). The title compound, (I), was obtained from a high stereoselective reaction in which three chiral centres are introduced in one step (Adamo et al., 2002). The interest in the relative configuration of the chiral centres and the structural details of this novel 3-acinitroisoxazoline prompted us to undertake a detailed analysis of the structure of compound (I).
The nitronate moiety is almost coplanar [4.62 (9)°] with the isoxazoline ring. The conjugation shows only a small effect both on the C=N bond length in the nitronate [N2—C14 = 1.321 (3) Å] and on the C=N and N—O bonds in the isoxazoline ring [N1—C13 = 1.289 (3) and N1—O2 = 1.425 (2) Å]. In comparison, the length of a C=N bond in a non-conjugated 2-nitropropanate has been reported as 1.311 (7) Å (Reetz et al., 1995) and the length of a C=N and an N—O bond in a non-conjugated nitroisaxazoline as 1.272 (4) and 1.419 (3) Å, respectively (Donati et al., 1994). These data exclude significative push-pull effects.
The isoxazoline ring assumes a very flattened envelope conformation, with puckering parameters (Cremer & Pople, 1975) ϕ = −173 (2)° and Q= 0.062 (2) Å and asymmetry parameter (Nardelli 1983) Δs (C4) 0.006 (1). The cyclohexanone ring lies perpendicular [85.84 (7)°] to the isoxazoline ring and assumes a chair conformation, with puckering parameters θ =172.6 (2)° and QT =-0.533 (2) Å. The phenyl group is approximatively perpendicular [83.54 (10)°] to the least-squares plane through the cyclohexanone, while the acetyl group forms an angle of 64.30 (17)° with this plane.
The nitrogen atom N3 of the triethylammonium residue is linked via a hydrogen bond with the oxygen atom O4 of the acinitro group and it is not coplanar with this group [dihedral angle C14—N2—O4—N3 = 148.1 (2)°]. There is also an intermolecular hydrogen bond between H1 in the cyclohexanone ring and N1 of the isoxazoline ring. Other short contact interactions are reported in Table 2.