The crystal structures of 2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl benzoate, C13H15NO5, (I), 2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl 4-chlorobenzoate, C13H14ClNO5, (II), and 5-nitroso-1,3-dioxan-5-yl 4-chlorobenzoate, C11H11NO5, (III), have been determined in order to gain insight into the conformational preference of α-benzoyloxynitroso. Unfavourable 1,3-diaxial interactions force (I) and (II) to crystallize in the 2,5 twist-boat conformation, whereas compound (III), lacking this destabilizing interaction, crystallizes in the chair conformation.
Supporting information
CCDC references: 652522; 652523; 652524
To a solution of 2,2-dimethyl-1,3-dioxan-5-one oxime (303 mg, 2.1 mmol) in
CH2Cl2 (21 ml) was added iodobenzene dibenzoate (933 mg, 2.1 mmol)
portionwise over a preiod of 45 min. The reaction mixture was stirred for 2 h
at room temperature before being quenched with an aqueous saturated NaHCO3
solution. The aqueous phase was extracted with CH2Cl2, dried over
Na2SO3, filtered and concentrated. Flash chromatography (heptane/ethyl
acetate, 9:1 to 7:3) afforded 396 mg (72%) of (I) as a bright-blue solid.
Recrystallization from pentane/diethyl ether led to blue crystals, suitable
for X-ray diffraction. Please specify details of syntheses of other two
compounds. NMR (1H and 13C) and IR spectra were collected for the
three compounds; the supplementary material contains these data.
H atoms were positioned geometrically and treated as riding. Refinement of the
Flack parameter (Flack & Schwarzenbach, 1988) for (III) was suppressed by the
MERG 4 command in SHELXL97 (Sheldrick, 1997).
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3.2 (Brueggemann & Schmid, 1990); software used to prepare material for publication: SHELXTL.
(I) 2,2-Dimethyl-5-nitroso-1,3-dioxan-5-yl benzoate
top
Crystal data top
C13H15NO5 | F(000) = 560 |
Mr = 265.26 | Dx = 1.348 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6252 reflections |
a = 6.2809 (5) Å | θ = 2.3–29.4° |
b = 21.9393 (19) Å | µ = 0.10 mm−1 |
c = 9.6452 (9) Å | T = 273 K |
β = 100.495 (2)° | Plate, blue |
V = 1306.9 (2) Å3 | 0.32 × 0.24 × 0.09 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 3401 independent reflections |
Radiation source: fine-focus sealed tube, X8 Apex II Bruker | 2914 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
phi and ω scans | θmax = 30.0°, θmin = 1.9° |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | h = −8→7 |
Tmin = 0.98, Tmax = 0.99 | k = −30→30 |
21059 measured reflections | l = −13→13 |
Refinement top
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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.150 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.3535P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.006 |
3401 reflections | Δρmax = 0.60 e Å−3 |
173 parameters | Δρmin = −0.41 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.069 (6) |
Crystal data top
C13H15NO5 | V = 1306.9 (2) Å3 |
Mr = 265.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.2809 (5) Å | µ = 0.10 mm−1 |
b = 21.9393 (19) Å | T = 273 K |
c = 9.6452 (9) Å | 0.32 × 0.24 × 0.09 mm |
β = 100.495 (2)° | |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 3401 independent reflections |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | 2914 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.022 |
21059 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.60 e Å−3 |
3401 reflections | Δρmin = −0.41 e Å−3 |
173 parameters | |
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. Treatment on H: H atoms of ligand were added geometrically and refined by
riding model. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2925 (2) | 1.07653 (6) | 0.20850 (13) | 0.0340 (3) | |
C5 | 0.1356 (3) | 1.12731 (7) | 0.22207 (17) | 0.0476 (4) | |
H5B | 0.0849 | 1.1451 | 0.1311 | 0.071* | |
H5C | 0.2072 | 1.1579 | 0.2850 | 0.071* | |
H5A | 0.0149 | 1.1113 | 0.2588 | 0.071* | |
C6 | 0.4895 (3) | 1.09770 (8) | 0.15200 (18) | 0.0516 (4) | |
H6A | 0.4441 | 1.1173 | 0.0624 | 0.077* | |
H6B | 0.5789 | 1.0632 | 0.1407 | 0.077* | |
H6C | 0.5703 | 1.1260 | 0.2170 | 0.077* | |
O2 | 0.17344 (16) | 1.03261 (4) | 0.11452 (9) | 0.0381 (3) | |
C2 | 0.2499 (2) | 0.97268 (6) | 0.14143 (13) | 0.0354 (3) | |
H2A | 0.4054 | 0.9713 | 0.1462 | 0.042* | |
H2B | 0.1824 | 0.9457 | 0.0665 | 0.042* | |
C3 | 0.1930 (2) | 0.95257 (6) | 0.28258 (13) | 0.0316 (3) | |
C4 | 0.2268 (2) | 1.00621 (6) | 0.38470 (13) | 0.0343 (3) | |
H4A | 0.0895 | 1.0262 | 0.3862 | 0.041* | |
H4B | 0.2843 | 0.9918 | 0.4792 | 0.041* | |
O1 | 0.37409 (15) | 1.04821 (4) | 0.34089 (9) | 0.0345 (2) | |
N1 | −0.0348 (2) | 0.92740 (7) | 0.24786 (15) | 0.0481 (3) | |
O3 | −0.17159 (19) | 0.96490 (7) | 0.24833 (18) | 0.0678 (4) | |
O4 | 0.32776 (16) | 0.90072 (4) | 0.32507 (10) | 0.0369 (2) | |
C7 | 0.2854 (2) | 0.86946 (6) | 0.43828 (14) | 0.0369 (3) | |
O5 | 0.14166 (19) | 0.88311 (5) | 0.49898 (13) | 0.0514 (3) | |
C8 | 0.4347 (2) | 0.81704 (6) | 0.47515 (14) | 0.0370 (3) | |
C9 | 0.3865 (3) | 0.77541 (7) | 0.57403 (16) | 0.0454 (3) | |
H9 | 0.2622 | 0.7803 | 0.6126 | 0.054* | |
C10 | 0.5242 (3) | 0.72675 (7) | 0.61472 (18) | 0.0545 (4) | |
H10 | 0.4920 | 0.6988 | 0.6804 | 0.065* | |
C11 | 0.7080 (3) | 0.71970 (8) | 0.55824 (18) | 0.0555 (4) | |
H11 | 0.8006 | 0.6871 | 0.5866 | 0.067* | |
C12 | 0.7569 (3) | 0.76063 (8) | 0.45946 (19) | 0.0521 (4) | |
H12 | 0.8814 | 0.7555 | 0.4213 | 0.063* | |
C13 | 0.6197 (3) | 0.80945 (7) | 0.41742 (16) | 0.0442 (3) | |
H13 | 0.6516 | 0.8370 | 0.3508 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0361 (6) | 0.0354 (6) | 0.0289 (6) | −0.0012 (5) | 0.0021 (5) | 0.0015 (4) |
C5 | 0.0523 (9) | 0.0421 (8) | 0.0465 (8) | 0.0102 (6) | 0.0046 (6) | 0.0021 (6) |
C6 | 0.0541 (9) | 0.0571 (9) | 0.0467 (8) | −0.0117 (7) | 0.0173 (7) | 0.0032 (7) |
O2 | 0.0433 (5) | 0.0386 (5) | 0.0278 (4) | 0.0019 (4) | −0.0058 (4) | 0.0014 (3) |
C2 | 0.0409 (7) | 0.0370 (6) | 0.0266 (5) | 0.0028 (5) | 0.0022 (5) | −0.0023 (5) |
C3 | 0.0298 (6) | 0.0322 (6) | 0.0315 (6) | 0.0023 (5) | 0.0022 (4) | 0.0010 (4) |
C4 | 0.0382 (7) | 0.0370 (6) | 0.0277 (6) | −0.0009 (5) | 0.0063 (5) | −0.0010 (5) |
O1 | 0.0338 (5) | 0.0392 (5) | 0.0278 (4) | −0.0040 (4) | −0.0012 (3) | 0.0009 (3) |
N1 | 0.0347 (6) | 0.0539 (8) | 0.0530 (8) | −0.0038 (5) | 0.0009 (5) | 0.0006 (6) |
O3 | 0.0345 (6) | 0.0734 (9) | 0.0918 (11) | 0.0062 (6) | 0.0017 (6) | 0.0021 (7) |
O4 | 0.0380 (5) | 0.0362 (5) | 0.0372 (5) | 0.0073 (4) | 0.0090 (4) | 0.0061 (4) |
C7 | 0.0371 (7) | 0.0361 (6) | 0.0372 (6) | −0.0018 (5) | 0.0062 (5) | 0.0036 (5) |
O5 | 0.0490 (6) | 0.0537 (6) | 0.0566 (7) | 0.0071 (5) | 0.0233 (5) | 0.0114 (5) |
C8 | 0.0412 (7) | 0.0333 (6) | 0.0348 (6) | −0.0009 (5) | 0.0022 (5) | 0.0011 (5) |
C9 | 0.0553 (9) | 0.0382 (7) | 0.0420 (7) | −0.0041 (6) | 0.0072 (6) | 0.0039 (6) |
C10 | 0.0774 (12) | 0.0369 (7) | 0.0466 (8) | 0.0007 (8) | 0.0041 (8) | 0.0075 (6) |
C11 | 0.0704 (11) | 0.0383 (7) | 0.0523 (9) | 0.0130 (7) | −0.0036 (8) | −0.0008 (6) |
C12 | 0.0510 (9) | 0.0496 (9) | 0.0543 (9) | 0.0122 (7) | 0.0056 (7) | −0.0036 (7) |
C13 | 0.0452 (8) | 0.0429 (7) | 0.0445 (7) | 0.0043 (6) | 0.0081 (6) | 0.0045 (6) |
Geometric parameters (Å, º) top
C1—O1 | 1.4286 (15) | C4—H4A | 0.9700 |
C1—O2 | 1.4360 (15) | C4—H4B | 0.9700 |
C1—C5 | 1.509 (2) | N1—O3 | 1.1901 (19) |
C1—C6 | 1.513 (2) | O4—C7 | 1.3563 (16) |
O1—C4 | 1.4232 (16) | C7—O5 | 1.2001 (18) |
O2—C2 | 1.4076 (16) | C7—C8 | 1.4854 (19) |
C5—H5B | 0.9600 | C8—C13 | 1.387 (2) |
C5—H5C | 0.9600 | C8—C9 | 1.393 (2) |
C5—H5A | 0.9600 | C9—C10 | 1.385 (2) |
C6—H6A | 0.9600 | C9—H9 | 0.9300 |
C6—H6B | 0.9600 | C10—C11 | 1.372 (3) |
C6—H6C | 0.9600 | C10—H10 | 0.9300 |
C2—C3 | 1.5340 (18) | C11—C12 | 1.384 (3) |
C2—H2A | 0.9700 | C11—H11 | 0.9300 |
C2—H2B | 0.9700 | C12—C13 | 1.388 (2) |
C3—O4 | 1.4324 (15) | C12—H12 | 0.9300 |
C3—N1 | 1.5132 (18) | C13—H13 | 0.9300 |
C3—C4 | 1.5246 (18) | N1—O5 | 2.6573 (19) |
| | | |
O1—C1—O2 | 109.47 (10) | C4—C3—C2 | 108.89 (10) |
O1—C1—C5 | 112.17 (11) | O1—C4—C3 | 109.24 (10) |
O2—C1—C5 | 106.09 (11) | O1—C4—H4A | 109.8 |
O1—C1—C6 | 105.76 (11) | C3—C4—H4A | 109.8 |
O2—C1—C6 | 110.15 (12) | O1—C4—H4B | 109.8 |
C5—C1—C6 | 113.22 (13) | C3—C4—H4B | 109.8 |
C4—O1—C1 | 113.58 (9) | H4A—C4—H4B | 108.3 |
C2—O2—C1 | 112.92 (9) | O3—N1—C3 | 113.65 (13) |
C1—C5—H5B | 109.5 | C7—O4—C3 | 116.08 (10) |
C1—C5—H5C | 109.5 | O5—C7—O4 | 122.81 (13) |
H5B—C5—H5C | 109.5 | O5—C7—C8 | 125.07 (13) |
C1—C5—H5A | 109.5 | O4—C7—C8 | 112.12 (11) |
H5B—C5—H5A | 109.5 | C13—C8—C9 | 119.91 (14) |
H5C—C5—H5A | 109.5 | C13—C8—C7 | 122.35 (12) |
C1—C6—H6A | 109.5 | C9—C8—C7 | 117.72 (13) |
C1—C6—H6B | 109.5 | C10—C9—C8 | 119.79 (16) |
H6A—C6—H6B | 109.5 | C10—C9—H9 | 120.1 |
C1—C6—H6C | 109.5 | C8—C9—H9 | 120.1 |
H6A—C6—H6C | 109.5 | C11—C10—C9 | 120.10 (16) |
H6B—C6—H6C | 109.5 | C11—C10—H10 | 119.9 |
O2—C2—C3 | 107.79 (10) | C9—C10—H10 | 119.9 |
O2—C2—H2A | 110.1 | C10—C11—C12 | 120.56 (15) |
C3—C2—H2A | 110.1 | C10—C11—H11 | 119.7 |
O2—C2—H2B | 110.1 | C12—C11—H11 | 119.7 |
C3—C2—H2B | 110.1 | C11—C12—C13 | 119.86 (17) |
H2A—C2—H2B | 108.5 | C11—C12—H12 | 120.1 |
O4—C3—N1 | 105.02 (10) | C13—C12—H12 | 120.1 |
O4—C3—C4 | 115.01 (10) | C8—C13—C12 | 119.76 (15) |
N1—C3—C4 | 116.07 (11) | C8—C13—H13 | 120.1 |
O4—C3—C2 | 105.15 (10) | C12—C13—H13 | 120.1 |
N1—C3—C2 | 105.80 (11) | | |
| | | |
O2—C1—O1—C4 | −38.94 (14) | N1—C3—O4—C7 | −59.79 (14) |
C5—C1—O1—C4 | 78.54 (14) | C4—C3—O4—C7 | 69.06 (15) |
C6—C1—O1—C4 | −157.59 (12) | C2—C3—O4—C7 | −171.18 (11) |
O1—C1—O2—C2 | −29.53 (15) | C3—O4—C7—O5 | 1.3 (2) |
C5—C1—O2—C2 | −150.76 (12) | C3—O4—C7—C8 | −179.37 (10) |
C6—C1—O2—C2 | 86.36 (14) | O5—C7—C8—C13 | −168.74 (15) |
C1—O2—C2—C3 | 69.48 (14) | O4—C7—C8—C13 | 11.97 (19) |
O2—C2—C3—O4 | −162.94 (10) | O5—C7—C8—C9 | 9.7 (2) |
O2—C2—C3—N1 | 86.22 (13) | O4—C7—C8—C9 | −169.60 (12) |
O2—C2—C3—C4 | −39.20 (14) | C13—C8—C9—C10 | 0.3 (2) |
C1—O1—C4—C3 | 65.51 (13) | C7—C8—C9—C10 | −178.18 (14) |
O4—C3—C4—O1 | 95.20 (12) | C8—C9—C10—C11 | 0.3 (2) |
N1—C3—C4—O1 | −141.66 (11) | C9—C10—C11—C12 | −0.6 (3) |
C2—C3—C4—O1 | −22.46 (14) | C10—C11—C12—C13 | 0.3 (3) |
O4—C3—N1—O3 | 160.35 (14) | C9—C8—C13—C12 | −0.6 (2) |
C4—C3—N1—O3 | 32.14 (19) | C7—C8—C13—C12 | 177.85 (14) |
C2—C3—N1—O3 | −88.73 (16) | C11—C12—C13—C8 | 0.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3 | 0.97 | 2.34 | 2.7593 (19) | 105 |
C4—H4B···O5 | 0.97 | 2.57 | 3.0016 (17) | 107 |
C5—H5C···Cgi | 0.97 | 2.69 (1) | 3.6482 (18) | 173 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
(II) 2,2-Dimethyl-5-nitroso-1,3-dioxan-5-yl 4-chlorobenzoate
top
Crystal data top
C13H14ClNO5 | F(000) = 1248 |
Mr = 299.70 | Dx = 1.461 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7665 reflections |
a = 21.716 (3) Å | θ = 2.6–32.2° |
b = 6.1950 (8) Å | µ = 0.30 mm−1 |
c = 20.398 (2) Å | T = 100 K |
β = 96.927 (2)° | Plate, blue |
V = 2724.2 (6) Å3 | 0.21 × 0.17 × 0.15 mm |
Z = 8 | |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 3819 independent reflections |
Radiation source: fine-focus sealed tube, X8 APEX II Bruker | 3425 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
phi and ω scans | θmax = 32.2°, θmin = 2.0° |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | h = −32→32 |
Tmin = 0.93, Tmax = 0.96 | k = −9→9 |
26111 measured reflections | l = −30→30 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0586P)2 + 3.0066P] where P = (Fo2 + 2Fc2)/3 |
3819 reflections | (Δ/σ)max = 0.002 |
181 parameters | Δρmax = 1.09 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
C13H14ClNO5 | V = 2724.2 (6) Å3 |
Mr = 299.70 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.716 (3) Å | µ = 0.30 mm−1 |
b = 6.1950 (8) Å | T = 100 K |
c = 20.398 (2) Å | 0.21 × 0.17 × 0.15 mm |
β = 96.927 (2)° | |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 3819 independent reflections |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | 3425 reflections with I > 2σ(I) |
Tmin = 0.93, Tmax = 0.96 | Rint = 0.021 |
26111 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.09 e Å−3 |
3819 reflections | Δρmin = −0.54 e Å−3 |
181 parameters | |
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. Treatment on H: H atoms of ligand were added geometrically and refined by
riding model. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.84646 (5) | 0.13584 (18) | −0.02411 (6) | 0.0136 (2) | |
C5 | 0.82305 (6) | 0.2938 (2) | −0.07819 (6) | 0.0178 (2) | |
H5A | 0.7797 | 0.3210 | −0.0767 | 0.027* | |
H5B | 0.8289 | 0.2338 | −0.1204 | 0.027* | |
H5C | 0.8457 | 0.4267 | −0.0718 | 0.027* | |
C6 | 0.81331 (6) | −0.0798 (2) | −0.03048 (6) | 0.0189 (2) | |
H6A | 0.7695 | −0.0574 | −0.0311 | 0.028* | |
H6B | 0.8282 | −0.1698 | 0.0064 | 0.028* | |
H6C | 0.8212 | −0.1487 | −0.0708 | 0.028* | |
O2 | 0.83643 (4) | 0.23935 (14) | 0.03707 (4) | 0.01448 (17) | |
C2 | 0.87825 (5) | 0.16434 (19) | 0.09067 (6) | 0.0146 (2) | |
H2A | 0.8789 | 0.0078 | 0.0911 | 0.018* | |
H2B | 0.8655 | 0.2144 | 0.1320 | 0.018* | |
C3 | 0.94290 (5) | 0.25247 (18) | 0.08226 (6) | 0.0128 (2) | |
C4 | 0.95131 (5) | 0.24842 (18) | 0.00882 (6) | 0.0136 (2) | |
H4B | 0.9414 | 0.3888 | −0.0107 | 0.016* | |
H4A | 0.9941 | 0.2151 | 0.0036 | 0.016* | |
O1 | 0.91115 (4) | 0.08812 (13) | −0.02354 (4) | 0.01377 (17) | |
N1 | 0.94577 (5) | 0.47326 (17) | 0.11445 (5) | 0.0176 (2) | |
O3 | 0.92744 (5) | 0.61889 (15) | 0.07763 (5) | 0.0224 (2) | |
O4 | 0.98503 (4) | 0.12061 (14) | 0.12375 (4) | 0.01527 (18) | |
C7 | 1.04434 (6) | 0.19282 (19) | 0.13538 (6) | 0.0152 (2) | |
O5 | 1.06214 (4) | 0.35601 (15) | 0.11115 (5) | 0.0197 (2) | |
C8 | 1.08273 (6) | 0.05200 (19) | 0.18304 (6) | 0.0151 (2) | |
C9 | 1.14014 (6) | 0.1290 (2) | 0.21096 (6) | 0.0181 (2) | |
H9 | 1.1540 | 0.2633 | 0.1986 | 0.022* | |
C10 | 1.17673 (6) | 0.0052 (2) | 0.25731 (6) | 0.0204 (2) | |
H10 | 1.2150 | 0.0557 | 0.2765 | 0.024* | |
C11 | 1.15495 (6) | −0.1959 (2) | 0.27440 (6) | 0.0199 (3) | |
C12 | 1.09847 (6) | −0.2771 (2) | 0.24630 (7) | 0.0214 (3) | |
H12 | 1.0852 | −0.4131 | 0.2579 | 0.026* | |
C13 | 1.06186 (6) | −0.1515 (2) | 0.20035 (6) | 0.0186 (2) | |
H13 | 1.0236 | −0.2026 | 0.1812 | 0.022* | |
Cl | 1.199754 (16) | −0.34805 (7) | 0.333945 (17) | 0.02895 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0105 (5) | 0.0171 (5) | 0.0132 (5) | −0.0008 (4) | 0.0013 (4) | −0.0007 (4) |
C5 | 0.0156 (6) | 0.0221 (5) | 0.0155 (5) | 0.0007 (4) | 0.0009 (4) | 0.0034 (4) |
C6 | 0.0174 (6) | 0.0191 (5) | 0.0196 (6) | −0.0054 (4) | 0.0005 (5) | −0.0011 (4) |
O2 | 0.0118 (4) | 0.0186 (4) | 0.0130 (4) | 0.0014 (3) | 0.0014 (3) | −0.0007 (3) |
C2 | 0.0123 (5) | 0.0191 (5) | 0.0126 (5) | −0.0023 (4) | 0.0022 (4) | 0.0015 (4) |
C3 | 0.0118 (5) | 0.0140 (4) | 0.0123 (5) | −0.0004 (4) | 0.0007 (4) | 0.0008 (4) |
C4 | 0.0118 (5) | 0.0164 (5) | 0.0126 (5) | −0.0028 (4) | 0.0022 (4) | 0.0000 (4) |
O1 | 0.0104 (4) | 0.0160 (4) | 0.0148 (4) | −0.0008 (3) | 0.0011 (3) | −0.0033 (3) |
N1 | 0.0158 (5) | 0.0169 (4) | 0.0203 (5) | −0.0019 (4) | 0.0035 (4) | −0.0027 (4) |
O3 | 0.0231 (5) | 0.0155 (4) | 0.0289 (5) | 0.0015 (3) | 0.0044 (4) | 0.0010 (3) |
O4 | 0.0122 (4) | 0.0169 (4) | 0.0161 (4) | −0.0016 (3) | −0.0008 (3) | 0.0037 (3) |
C7 | 0.0128 (5) | 0.0186 (5) | 0.0139 (5) | −0.0013 (4) | 0.0004 (4) | −0.0007 (4) |
O5 | 0.0171 (4) | 0.0203 (4) | 0.0212 (4) | −0.0044 (3) | 0.0003 (4) | 0.0038 (3) |
C8 | 0.0137 (5) | 0.0195 (5) | 0.0121 (5) | 0.0006 (4) | 0.0014 (4) | 0.0001 (4) |
C9 | 0.0153 (6) | 0.0237 (5) | 0.0155 (5) | −0.0017 (4) | 0.0022 (5) | −0.0010 (4) |
C10 | 0.0131 (6) | 0.0330 (6) | 0.0149 (5) | 0.0000 (5) | 0.0009 (4) | −0.0018 (5) |
C11 | 0.0155 (6) | 0.0318 (6) | 0.0123 (5) | 0.0072 (5) | 0.0021 (4) | 0.0030 (4) |
C12 | 0.0195 (6) | 0.0247 (6) | 0.0201 (6) | 0.0023 (5) | 0.0022 (5) | 0.0053 (5) |
C13 | 0.0162 (6) | 0.0215 (5) | 0.0175 (6) | −0.0013 (4) | 0.0001 (5) | 0.0025 (4) |
Cl | 0.01825 (18) | 0.0473 (2) | 0.02100 (17) | 0.01040 (13) | 0.00116 (13) | 0.01219 (14) |
Geometric parameters (Å, º) top
C1—O1 | 1.4344 (14) | C4—O1 | 1.4296 (14) |
C1—O2 | 1.4428 (14) | C4—H4B | 0.9700 |
C1—C6 | 1.5154 (16) | C4—H4A | 0.9700 |
C1—C5 | 1.5160 (17) | O4—C7 | 1.3570 (14) |
C5—H5A | 0.9600 | C7—O5 | 1.2090 (14) |
C5—H5B | 0.9600 | C7—C8 | 1.4852 (17) |
C5—H5C | 0.9600 | C8—C9 | 1.3911 (18) |
C6—H6A | 0.9600 | C8—C13 | 1.3991 (17) |
C6—H6B | 0.9600 | C9—C10 | 1.3902 (19) |
C6—H6C | 0.9600 | C9—H9 | 0.9300 |
O2—C2 | 1.4131 (15) | C10—C11 | 1.392 (2) |
C2—C3 | 1.5351 (16) | C10—H10 | 0.9300 |
C2—H2A | 0.9700 | C11—C12 | 1.384 (2) |
C2—H2B | 0.9700 | C11—Cl | 1.7393 (13) |
C3—O4 | 1.4262 (14) | C12—C13 | 1.3916 (18) |
C3—N1 | 1.5153 (15) | C12—H12 | 0.9300 |
C3—C4 | 1.5310 (15) | C13—H13 | 0.9300 |
N1—O3 | 1.2101 (15) | N1—O5 | 2.6381 (14) |
| | | |
O1—C1—O2 | 109.54 (9) | O3—N1—C3 | 114.25 (10) |
O1—C1—C6 | 105.88 (9) | O1—C4—C3 | 108.97 (8) |
O2—C1—C6 | 110.27 (9) | O1—C4—H4B | 109.9 |
O1—C1—C5 | 112.40 (9) | C3—C4—H4B | 109.9 |
O2—C1—C5 | 105.68 (9) | O1—C4—H4A | 109.9 |
C6—C1—C5 | 113.10 (11) | C3—C4—H4A | 109.9 |
C1—C5—H5A | 109.5 | H4B—C4—H4A | 108.3 |
C1—C5—H5B | 109.5 | C4—O1—C1 | 113.76 (8) |
H5A—C5—H5B | 109.5 | C7—O4—C3 | 116.25 (9) |
C1—C5—H5C | 109.5 | O5—C7—O4 | 123.21 (11) |
H5A—C5—H5C | 109.5 | O5—C7—C8 | 125.23 (11) |
H5B—C5—H5C | 109.5 | O4—C7—C8 | 111.52 (10) |
C1—C6—H6A | 109.5 | C9—C8—C13 | 120.49 (12) |
C1—C6—H6B | 109.5 | C9—C8—C7 | 118.11 (11) |
H6A—C6—H6B | 109.5 | C13—C8—C7 | 121.40 (11) |
C1—C6—H6C | 109.5 | C10—C9—C8 | 119.97 (12) |
H6A—C6—H6C | 109.5 | C10—C9—H9 | 120.0 |
H6B—C6—H6C | 109.5 | C8—C9—H9 | 120.0 |
C2—O2—C1 | 111.91 (9) | C9—C10—C11 | 118.74 (12) |
O2—C2—C3 | 107.92 (9) | C9—C10—H10 | 120.6 |
O2—C2—H2A | 110.1 | C11—C10—H10 | 120.6 |
C3—C2—H2A | 110.1 | C12—C11—C10 | 122.16 (12) |
O2—C2—H2B | 110.1 | C12—C11—Cl | 119.04 (11) |
C3—C2—H2B | 110.1 | C10—C11—Cl | 118.79 (10) |
H2A—C2—H2B | 108.4 | C11—C12—C13 | 118.78 (12) |
O4—C3—N1 | 105.65 (9) | C11—C12—H12 | 120.6 |
O4—C3—C4 | 115.32 (9) | C13—C12—H12 | 120.6 |
N1—C3—C4 | 115.81 (9) | C12—C13—C8 | 119.84 (12) |
O4—C3—C2 | 105.05 (9) | C12—C13—H13 | 120.1 |
N1—C3—C2 | 105.25 (9) | C8—C13—H13 | 120.1 |
C4—C3—C2 | 108.80 (9) | | |
| | | |
O1—C1—O2—C2 | −32.63 (12) | C4—C3—O4—C7 | 73.11 (12) |
C6—C1—O2—C2 | 83.51 (12) | C2—C3—O4—C7 | −167.13 (9) |
C5—C1—O2—C2 | −153.94 (9) | C3—O4—C7—O5 | −1.96 (16) |
C1—O2—C2—C3 | 70.90 (11) | C3—O4—C7—C8 | 175.69 (9) |
O2—C2—C3—O4 | −162.05 (9) | O5—C7—C8—C9 | 11.46 (18) |
O2—C2—C3—N1 | 86.67 (11) | O4—C7—C8—C9 | −166.13 (10) |
O2—C2—C3—C4 | −38.04 (12) | O5—C7—C8—C13 | −169.35 (12) |
O4—C3—N1—O3 | 159.81 (10) | O4—C7—C8—C13 | 13.06 (15) |
C4—C3—N1—O3 | 30.85 (14) | C13—C8—C9—C10 | −1.16 (18) |
C2—C3—N1—O3 | −89.34 (11) | C7—C8—C9—C10 | 178.04 (11) |
O4—C3—C4—O1 | 93.29 (11) | C8—C9—C10—C11 | 0.53 (18) |
N1—C3—C4—O1 | −142.63 (10) | C9—C10—C11—C12 | 0.65 (18) |
C2—C3—C4—O1 | −24.39 (12) | C9—C10—C11—Cl | −178.36 (9) |
C3—C4—O1—C1 | 65.51 (12) | C10—C11—C12—C13 | −1.18 (19) |
O2—C1—O1—C4 | −36.24 (12) | Cl—C11—C12—C13 | 177.83 (10) |
C6—C1—O1—C4 | −155.13 (9) | C11—C12—C13—C8 | 0.53 (19) |
C5—C1—O1—C4 | 80.92 (11) | C9—C8—C13—C12 | 0.62 (18) |
N1—C3—O4—C7 | −56.14 (11) | C7—C8—C13—C12 | −178.55 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O3 | 0.97 | 2.35 | 2.7716 (15) | 106 |
C4—H4B···O5i | 0.97 | 2.58 | 3.4507 (16) | 149 |
C5—H5B···Cgii | 0.97 | 2.78 (1) | 3.7156 (14) | 164 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, y−1, −z+3/2. |
(III) 5-nitroso-1,3-dioxan-5-yl 4-chlorobenzoate
top
Crystal data top
C11H11NO5 | F(000) = 496 |
Mr = 237.21 | Dx = 1.455 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7119 reflections |
a = 9.3969 (5) Å | θ = 2.7–31.8° |
b = 9.4328 (5) Å | µ = 0.12 mm−1 |
c = 12.2133 (7) Å | T = 100 K |
V = 1082.58 (10) Å3 | Plate, blue |
Z = 4 | 0.21 × 0.16 × 0.14 mm |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 2327 independent reflections |
Radiation source: fine-focus sealed tube, X8 APEX II Bruker | 2041 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
phi and ω scans | θmax = 33.9°, θmin = 2.7° |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | h = −12→14 |
Tmin = 0.96, Tmax = 0.99 | k = −13→14 |
16965 measured reflections | l = −17→18 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0585P)2 + 0.0381P] where P = (Fo2 + 2Fc2)/3 |
2327 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C11H11NO5 | V = 1082.58 (10) Å3 |
Mr = 237.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.3969 (5) Å | µ = 0.12 mm−1 |
b = 9.4328 (5) Å | T = 100 K |
c = 12.2133 (7) Å | 0.21 × 0.16 × 0.14 mm |
Data collection top
Bruker SMART APEX II area-detector diffractometer | 2327 independent reflections |
Absorption correction: ψ scan (SADABS; Bruker, 2000) | 2041 reflections with I > 2σ(I) |
Tmin = 0.96, Tmax = 0.99 | Rint = 0.029 |
16965 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.36 e Å−3 |
2327 reflections | Δρmin = −0.17 e Å−3 |
154 parameters | |
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. Treatment on H: H atoms of ligand were added geometrically and refined by
riding model. Refinement of the Flack parameter (Flack & Schwarzenbach, 1988) was suppressed
by the MERG 4 command in SHELXL97 (Sheldrick, 1997) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.41257 (16) | 1.10525 (16) | 0.66731 (11) | 0.0214 (3) | |
H1A | 0.4096 | 1.2016 | 0.6396 | 0.026* | |
H1B | 0.4103 | 1.0413 | 0.6052 | 0.026* | |
O2 | 0.29252 (10) | 1.08076 (11) | 0.73385 (7) | 0.0194 (2) | |
C2 | 0.28660 (14) | 1.18248 (14) | 0.82006 (10) | 0.0175 (2) | |
H2A | 0.2041 | 1.1646 | 0.8658 | 0.021* | |
H2B | 0.2778 | 1.2770 | 0.7896 | 0.021* | |
C3 | 0.42241 (13) | 1.17229 (12) | 0.88889 (10) | 0.0145 (2) | |
C4 | 0.55148 (14) | 1.18430 (15) | 0.81322 (11) | 0.0192 (3) | |
H4A | 0.5569 | 1.2795 | 0.7835 | 0.023* | |
H4B | 0.6378 | 1.1664 | 0.8545 | 0.023* | |
O1 | 0.53999 (11) | 1.08459 (12) | 0.72621 (8) | 0.0217 (2) | |
N1 | 0.42062 (13) | 1.29968 (12) | 0.96344 (9) | 0.0200 (2) | |
O3 | 0.37322 (11) | 1.27543 (11) | 1.05311 (8) | 0.0229 (2) | |
O4 | 0.41342 (10) | 1.04097 (9) | 0.94535 (7) | 0.01517 (17) | |
C7 | 0.51737 (13) | 1.01089 (13) | 1.01934 (10) | 0.0140 (2) | |
O5 | 0.61208 (10) | 1.09256 (10) | 1.04222 (8) | 0.01918 (19) | |
C8 | 0.50125 (13) | 0.86631 (12) | 1.06546 (9) | 0.0134 (2) | |
C9 | 0.60143 (14) | 0.82179 (13) | 1.14258 (10) | 0.0165 (2) | |
H9 | 0.6737 | 0.8827 | 1.1649 | 0.020* | |
C10 | 0.59237 (16) | 0.68547 (14) | 1.18585 (10) | 0.0200 (3) | |
H10 | 0.6582 | 0.6553 | 1.2377 | 0.024* | |
C11 | 0.48514 (16) | 0.59493 (15) | 1.15159 (11) | 0.0206 (3) | |
H11 | 0.4798 | 0.5038 | 1.1803 | 0.025* | |
C12 | 0.38535 (15) | 0.63910 (14) | 1.07467 (11) | 0.0197 (3) | |
H12 | 0.3139 | 0.5776 | 1.0519 | 0.024* | |
C13 | 0.39276 (13) | 0.77570 (13) | 1.03195 (10) | 0.0162 (2) | |
H13 | 0.3256 | 0.8063 | 0.9813 | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0233 (6) | 0.0248 (6) | 0.0159 (5) | 0.0010 (6) | 0.0009 (5) | 0.0010 (5) |
O2 | 0.0208 (5) | 0.0207 (4) | 0.0168 (4) | −0.0025 (4) | −0.0018 (4) | 0.0017 (4) |
C2 | 0.0160 (5) | 0.0184 (5) | 0.0182 (5) | 0.0016 (5) | 0.0001 (4) | 0.0028 (5) |
C3 | 0.0147 (5) | 0.0130 (4) | 0.0158 (5) | −0.0008 (5) | 0.0008 (4) | 0.0013 (4) |
C4 | 0.0166 (5) | 0.0221 (6) | 0.0188 (5) | −0.0025 (5) | 0.0027 (5) | 0.0001 (5) |
O1 | 0.0201 (4) | 0.0254 (5) | 0.0197 (4) | 0.0035 (4) | 0.0019 (4) | −0.0016 (4) |
N1 | 0.0217 (5) | 0.0168 (5) | 0.0215 (5) | 0.0016 (4) | −0.0002 (5) | −0.0019 (4) |
O3 | 0.0254 (5) | 0.0236 (5) | 0.0196 (4) | 0.0062 (4) | 0.0013 (4) | −0.0014 (4) |
O4 | 0.0144 (4) | 0.0140 (4) | 0.0171 (4) | −0.0009 (3) | −0.0026 (3) | 0.0031 (3) |
C7 | 0.0130 (5) | 0.0142 (5) | 0.0147 (5) | 0.0024 (4) | −0.0006 (4) | −0.0008 (4) |
O5 | 0.0171 (4) | 0.0169 (4) | 0.0235 (4) | −0.0018 (4) | −0.0041 (4) | 0.0002 (4) |
C8 | 0.0141 (5) | 0.0130 (5) | 0.0130 (5) | 0.0020 (4) | 0.0011 (4) | −0.0010 (4) |
C9 | 0.0167 (5) | 0.0169 (5) | 0.0159 (5) | 0.0029 (5) | −0.0007 (4) | −0.0014 (4) |
C10 | 0.0235 (6) | 0.0199 (6) | 0.0167 (5) | 0.0061 (5) | −0.0014 (5) | 0.0018 (4) |
C11 | 0.0254 (6) | 0.0164 (5) | 0.0201 (5) | 0.0030 (5) | 0.0046 (5) | 0.0043 (5) |
C12 | 0.0200 (6) | 0.0164 (5) | 0.0228 (6) | −0.0023 (5) | 0.0022 (5) | 0.0005 (5) |
C13 | 0.0160 (5) | 0.0158 (5) | 0.0168 (5) | 0.0002 (4) | −0.0004 (4) | 0.0002 (4) |
Geometric parameters (Å, º) top
C1—O2 | 1.4094 (17) | O4—C7 | 1.3606 (15) |
C1—O1 | 1.4104 (17) | C7—O5 | 1.2098 (16) |
C1—H1A | 0.9700 | C7—C8 | 1.4833 (16) |
C1—H1B | 0.9700 | C8—C13 | 1.3918 (17) |
O2—C2 | 1.4256 (16) | C8—C9 | 1.3963 (17) |
C2—C3 | 1.5312 (18) | C9—C10 | 1.3928 (18) |
C2—H2A | 0.9700 | C9—H9 | 0.9300 |
C2—H2B | 0.9700 | C10—C11 | 1.386 (2) |
C3—O4 | 1.4202 (14) | C10—H10 | 0.9300 |
C3—N1 | 1.5078 (16) | C11—C12 | 1.391 (2) |
C3—C4 | 1.5290 (17) | C11—H11 | 0.9300 |
N1—O3 | 1.2042 (15) | C12—C13 | 1.3919 (18) |
C4—O1 | 1.4233 (17) | C12—H12 | 0.9300 |
C4—H4A | 0.9700 | C13—H13 | 0.9300 |
C4—H4B | 0.9700 | N1—O5 | 2.8248 (15) |
| | | |
O2—C1—O1 | 111.27 (10) | H4A—C4—H4B | 108.2 |
O2—C1—H1A | 109.4 | C1—O1—C4 | 110.73 (11) |
O1—C1—H1A | 109.4 | C7—O4—C3 | 117.49 (10) |
O2—C1—H1B | 109.4 | O5—C7—O4 | 123.28 (11) |
O1—C1—H1B | 109.4 | O5—C7—C8 | 124.95 (11) |
H1A—C1—H1B | 108.0 | O4—C7—C8 | 111.75 (10) |
C1—O2—C2 | 110.29 (10) | C13—C8—C9 | 120.49 (11) |
O2—C2—C3 | 109.31 (10) | C13—C8—C7 | 121.86 (11) |
O2—C2—H2A | 109.8 | C9—C8—C7 | 117.64 (11) |
C3—C2—H2A | 109.8 | C10—C9—C8 | 119.50 (12) |
O2—C2—H2B | 109.8 | C10—C9—H9 | 120.2 |
C3—C2—H2B | 109.8 | C8—C9—H9 | 120.2 |
H2A—C2—H2B | 108.3 | C11—C10—C9 | 119.93 (12) |
O4—C3—N1 | 113.65 (9) | C11—C10—H10 | 120.0 |
O4—C3—C4 | 113.91 (10) | C9—C10—H10 | 120.0 |
N1—C3—C4 | 108.35 (10) | C10—C11—C12 | 120.63 (12) |
O4—C3—C2 | 105.77 (10) | C10—C11—H11 | 119.7 |
N1—C3—C2 | 105.79 (10) | C12—C11—H11 | 119.7 |
C4—C3—C2 | 108.95 (10) | C11—C12—C13 | 119.78 (13) |
O3—N1—C3 | 113.70 (11) | C11—C12—H12 | 120.1 |
O1—C4—C3 | 110.01 (11) | C13—C12—H12 | 120.1 |
O1—C4—H4A | 109.7 | C8—C13—C12 | 119.67 (12) |
C3—C4—H4A | 109.7 | C8—C13—H13 | 120.2 |
O1—C4—H4B | 109.7 | C12—C13—H13 | 120.2 |
C3—C4—H4B | 109.7 | | |
| | | |
O1—C1—O2—C2 | 64.49 (14) | C2—C3—O4—C7 | −175.15 (10) |
C1—O2—C2—C3 | −59.07 (13) | C3—O4—C7—O5 | 3.32 (17) |
O2—C2—C3—O4 | −69.65 (12) | C3—O4—C7—C8 | −175.44 (9) |
O2—C2—C3—N1 | 169.48 (9) | O5—C7—C8—C13 | −177.27 (12) |
O2—C2—C3—C4 | 53.19 (13) | O4—C7—C8—C13 | 1.46 (16) |
O4—C3—N1—O3 | −19.51 (15) | O5—C7—C8—C9 | 1.19 (18) |
C4—C3—N1—O3 | −147.21 (12) | O4—C7—C8—C9 | 179.93 (10) |
C2—C3—N1—O3 | 96.09 (12) | C13—C8—C9—C10 | 0.13 (18) |
O4—C3—C4—O1 | 65.45 (13) | C7—C8—C9—C10 | −178.35 (11) |
N1—C3—C4—O1 | −167.01 (10) | C8—C9—C10—C11 | 0.51 (19) |
C2—C3—C4—O1 | −52.36 (13) | C9—C10—C11—C12 | −0.5 (2) |
O2—C1—O1—C4 | −63.42 (14) | C10—C11—C12—C13 | −0.3 (2) |
C3—C4—O1—C1 | 57.20 (13) | C9—C8—C13—C12 | −0.84 (18) |
N1—C3—O4—C7 | −59.53 (13) | C7—C8—C13—C12 | 177.58 (11) |
C4—C3—O4—C7 | 65.23 (13) | C11—C12—C13—C8 | 0.90 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O5 | 0.97 | 2.41 | 2.9825 (17) | 117 |
C4—H4B···O3i | 0.97 | 2.54 | 3.4569 (17) | 157 |
C10—H10···O2ii | 0.93 | 2.58 | 3.2872 (17) | 133 |
C13—H13···O4 | 0.93 | 2.40 | 2.7235 (15) | 100 |
Symmetry codes: (i) x+1/2, −y+5/2, −z+2; (ii) x+1/2, −y+3/2, −z+2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C13H15NO5 | C13H14ClNO5 | C11H11NO5 |
Mr | 265.26 | 299.70 | 237.21 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, C2/c | Orthorhombic, P212121 |
Temperature (K) | 273 | 100 | 100 |
a, b, c (Å) | 6.2809 (5), 21.9393 (19), 9.6452 (9) | 21.716 (3), 6.1950 (8), 20.398 (2) | 9.3969 (5), 9.4328 (5), 12.2133 (7) |
α, β, γ (°) | 90, 100.495 (2), 90 | 90, 96.927 (2), 90 | 90, 90, 90 |
V (Å3) | 1306.9 (2) | 2724.2 (6) | 1082.58 (10) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.30 | 0.12 |
Crystal size (mm) | 0.32 × 0.24 × 0.09 | 0.21 × 0.17 × 0.15 | 0.21 × 0.16 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART APEX II area-detector diffractometer | Bruker SMART APEX II area-detector diffractometer | Bruker SMART APEX II area-detector diffractometer |
Absorption correction | ψ scan (SADABS; Bruker, 2000) | ψ scan (SADABS; Bruker, 2000) | ψ scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.98, 0.99 | 0.93, 0.96 | 0.96, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21059, 3401, 2914 | 26111, 3819, 3425 | 16965, 2327, 2041 |
Rint | 0.022 | 0.021 | 0.029 |
(sin θ/λ)max (Å−1) | 0.703 | 0.750 | 0.786 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.150, 1.12 | 0.037, 0.110, 1.09 | 0.034, 0.091, 1.03 |
No. of reflections | 3401 | 3819 | 2327 |
No. of parameters | 173 | 181 | 154 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.41 | 1.09, −0.54 | 0.36, −0.17 |
Selected geometric parameters (Å, º) for (I) topC1—O1 | 1.4286 (15) | O2—C2 | 1.4076 (16) |
C1—O2 | 1.4360 (15) | N1—O3 | 1.1901 (19) |
C1—C5 | 1.509 (2) | C7—O5 | 1.2001 (18) |
C1—C6 | 1.513 (2) | N1—O5 | 2.6573 (19) |
O1—C4 | 1.4232 (16) | | |
| | | |
O4—C3—N1—O3 | 160.35 (14) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3 | 0.9700 | 2.3400 | 2.7593 (19) | 105.00 |
C4—H4B···O5 | 0.9700 | 2.5700 | 3.0016 (17) | 107.00 |
C5—H5C···Cgi | 0.9700 | 2.6939 (18) | 3.6482 (18) | 172.64 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topC1—O1 | 1.4344 (14) | N1—O3 | 1.2101 (15) |
C1—O2 | 1.4428 (14) | C4—O1 | 1.4296 (14) |
C1—C6 | 1.5154 (16) | C7—O5 | 1.2090 (14) |
C1—C5 | 1.5160 (17) | N1—O5 | 2.6381 (14) |
O2—C2 | 1.4131 (15) | | |
| | | |
O4—C3—N1—O3 | 159.81 (10) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O3 | 0.9700 | 2.3500 | 2.7716 (15) | 106.00 |
C4—H4B···O5i | 0.9700 | 2.5800 | 3.4507 (16) | 149.00 |
C5—H5B···Cgii | 0.9700 | 2.7839 (13) | 3.7156 (14) | 163.81 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, y−1, −z+3/2. |
Selected geometric parameters (Å, º) for (III) topC1—O2 | 1.4094 (17) | N1—O3 | 1.2042 (15) |
C1—O1 | 1.4104 (17) | C4—O1 | 1.4233 (17) |
O2—C2 | 1.4256 (16) | C7—O5 | 1.2098 (16) |
C2—C3 | 1.5312 (18) | N1—O5 | 2.8248 (15) |
C3—C4 | 1.5290 (17) | | |
| | | |
O4—C3—N1—O3 | −19.51 (15) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O5 | 0.9700 | 2.4100 | 2.9825 (17) | 117.00 |
C4—H4B···O3i | 0.9700 | 2.5400 | 3.4569 (17) | 157.00 |
C10—H10···O2ii | 0.9300 | 2.5800 | 3.2872 (17) | 133.00 |
C13—H13···O4 | 0.9300 | 2.4000 | 2.7235 (15) | 100.00 |
Symmetry codes: (i) x+1/2, −y+5/2, −z+2; (ii) x+1/2, −y+3/2, −z+2. |
α-Acyloxynitroso derivatives have elicited recent interest as a new class of HNO donors (Sha et al., 2006). In 2004, we introduced α-acetoxy nitroso derivatives as reactive dienophiles in [4 + 2]-cycloaddition reactions and the synthetic relevance of this new class of nitroso dienophiles has been demonstrated (Calvet et al., 2004, 2005, 2007). The unprecedented behaviour of α-acetoxy nitroso in the presence of a 1,3-diene led us to investigate their conformational preference. This study was expected to trigger the development of more reactive/selective dienophiles. Moreover, the cycloaddition reaction of α-acetoxy nitroso complexed with a metallic salt bearing enantiopure ligands was a very exciting development. Such an investigation required the rational design of a reactive dienophile, which cannot be accomplished without a detailed crystallographic study.
α-Benzoyloxynitroso derivatives (I) and (II) differ only by the nature of the aromatic para-substituent [for (I), R1 = H and R2 = Me; for (II), R1 = Cl and R2 = Me). The 1,3-dioxanyl ring system crystallizes in the 2,5 twist-boat conformation (Figs. 1 and 2), with the N═O and the benzoyloxy substituents occupying the isoclinal positions (Freeman & Do, 2002). The puckering parameters for compound (I) are Q = 0.750 (1) Å, θ = 91.7 (1)° and ϕ = 337.0 (1)°, and for (II) Q = 0.759 (1) Å, θ = 92.1 (1)° and ϕ = 334.4 (1)° for the atom sequence O1—C1—O2—C2—C3—C4 (Cremer & Pople, 1975). This twisted conformation occurs in the substituted 1,3-dioxanyl ring in order to relieve unfavourable 1,3-diaxial interaction (Rychnovsky et al., 1993), as in the case of a related 1,3-dioxanyl ring [Cambridge Structural Database (Allen, 2002) refcode OCECUU; Kanoh et al., 2000]. These diaxial interactions [e.g. H5A···H4A = 2.24 Å in (I)] are magnified by the shorter length of the C—O bonds [1.4076 (16)–1.4428 (14) Å] compared with the corresponding cyclohexyl ring (see Tables 1 and 3). The N═O bond distance in (II) is slightly longer [0.020 (2) Å] than that observed in (I). This difference could be attributed to the electron-withdrawing character of the p-chlorobenzoyl group (Figs. 1 and 2). The distance between carbonyl atom O5 and atom N1 of the nitroso group is also shorter in (II) by 0.019 (2) Å.
When the isopropylidene ketal unit of derivatives (I) and (II) is replaced by a methylene ketal, the conformation of the 1,3-dioxanyl ring changes dramatically (Fig. 3). α-Benzoyloxynitroso (III) (R1 = H and R2 = H) crystallizes in a chair conformation, with the nitroso unit in equatorial position and the benzoyloxy substituent in axial position. For compound (III), the corresponding puckering parameters are Q = 0.571 (1) Å, θ = 3.4 (1)° and ϕ = 82 (2)°. That the sterically smaller NO substituent adopts the equatorial position could be rationalized in terms of dipole interaction (Abraham et al., 1972) and/or repulsive gauche effect (Eliel & Juaristi, 1978) between the lone pairs of the intracyclic O1 and O2 atoms and the lone pairs of the nitroso group. The nitroso bond length is intermediate between values observed for derivatives (I) and (II). In contrast, the N1—O5 distance is longer than the average of that in (I) and (II) by 0.178 (3) Å. The dihedral angle O4—C3—N1—O3 is -19.51 (15)° for (III), similar to the reported value of -4.3 (1)° for the structure of 2,3,5,6-di-O-isopropylidene-1-C-nitroso-α-D-mannofuranosyl chloride (refcode FADSOS; Felber et al., 1986).
In each of the three molecules, there are weak intramolecular C–H···O hydrogen bonds (Tables 2, 4 and 6). These intramolecular hydrogen bonds affect the molecular conformation and stabilize the twist-boat conformation for (I) and (II). For compound (III), only one weak interaction appears, between C4/H4B and O5. We have also compared the three structures by superposition, maximizing the fit of atoms C3, O4 and C7 (Fig. 4). The figure shows clearly the exact superposition of (I) and (II). For (III), atom O3 is located `outside' the six-membered ring, whereas in (I) and (II), atom O3 adopts a more `inside' position. This allows the formation of an additional C—H···O hydrogen bond.
In (I), no intermolecular C—H···O hydrogen-bond interactions are found. In the other two compounds, the packing of the molecules involves C—H···O hydrogen bonds utilizing atoms O2 and O3. Thus molecules of (II) form dimers (Table 4). The molecules of (III) are linked into a two-dimensional framework by a combination of two C—H···O hydrogen bonds (Table 6). In the shorter of these, C10 acts as a hydrogen-bond donor to atom O2, thereby producing a chain running parallel to the [100] direction, generated by the 21 screw axis along (x, 1/4, 0). In the second C—H···O hydrogen bond, atom C4 acts as a hydrogen-bond donor to O3, so producing a chain running parallel to the [001] direction, as generated by the 21 screw axis along (-1/4, 0, z). In addition, weak C—H···π hydrogen bonds are presents in (I) and (II); for both compounds, atom C5 acts as a hydrogen-bond donor to the C8–C13 ring in an adjacent molecule (Tables 2 and 4).