The two new gem-dihalogenocyclopropanes (1'S,3R)-3-(2',2'-dichloro-1'-methylcyclopropyl)-6-oxoheptanoic acid, C11H16Cl2O3, (2), and (1'S,3R)-3-(2',2'-dibromo-1'-methylcyclopropyl)-6-oxoheptanoic acid, C11H16Br2O3, (3), are isostructural. Both present two stereogenic centers at C1' and C3. The absolute configuration was determined by X-ray methods. The cyclopropyl rings are unsymmetrical, the shortest bond being distal with respect to the alkyl-substituted C atom.
Supporting information
CCDC references: 182027; 182028
(R)-limonene oxide 1 was treated, in phase transfer catalysis conditions,
with dichloro (or dibromo) carbene (Tobey et al., 1964) generated in
situ from the reaction of chloroform (or bromoform) with sodium hydroxide
(Scheme 1). The resulting product was oxidized under Sharpless conditions
(Carlson et al., 1981) leading to a diastereoisomeric mixture of
3-(2',2'-dihalo-1'-methylcyclopropyl)-6-oxo-heptanoic acid. Crystals of 2 and
3 were obtained from the corresponding mixture by fractional crystallization
from chloroform.
The crystal of 3 was found to be twinned. However the two domains could be
indexed and the two orientation matrices were used in the integration process
(Stoe,1996) to produce a set of non-overlapped reflections for each domain.
Only the data from the domain with the strongest intensities were retained. As
the results were satisfactory, no search for untwinned crystal was undertaken.
In both compounds, all H atoms were introduced at calculated positions as
riding atoms (C—H= 0.97–0.98 Å, OH= 0.82 Å), using AFIX 37 for CH3
and AFIX 87 for hydroxyl groups, with a displacement parameter equal to 1.2
(CH, CH2) or 1.5(CH3,OH) times that of the parent atom. On the basis of
2006 and 1972 Friedel pairs for compounds 2 and 3 respectively, final
refinement allowed the fraction contribution of the inverted enantiomer to
vary (Bernardinelli & Flack, 1985; Flack, 1983), the absolute structure
parameter quoted being the refined value of this contribution.
For both compounds, data collection: IPDS Software (Stoe, 1996); cell refinement: IPDS Software (Stoe, 1996); data reduction: X-RED (Stoe, 1.08, 1996); program(s) used to solve structure: SIR97 (Altomare, et al.,1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1998); molecular graphics: ORTEPIII( Burnett and Johnson,1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
C11H16Cl2O3 | F(000) = 560 |
Mr = 267.14 | Dx = 1.414 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8000 reflections |
a = 7.2419 (5) Å | θ = 2.3–26.0° |
b = 9.7619 (8) Å | µ = 0.51 mm−1 |
c = 17.7469 (16) Å | T = 180 K |
V = 1254.61 (18) Å3 | Parallelepiped, colorless |
Z = 4 | 0.42 × 0.40 × 0.13 mm |
Data collection top
Stoe IPDS diffractometer | 2207 reflections with I > 2σ(I) |
ϕ scans | Rint = 0.034 |
Absorption correction: multi-scan SORTAV, Blessing (1995) | θmax = 26.0°, θmin = 2.3° |
Tmin = 0.788, Tmax = 0.913 | h = −8→8 |
9901 measured reflections | k = −12→12 |
2418 independent reflections | l = −21→21 |
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0375P)2 + 0.0454P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2418 reflections | Δρmax = 0.22 e Å−3 |
148 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (5) |
Crystal data top
C11H16Cl2O3 | V = 1254.61 (18) Å3 |
Mr = 267.14 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.2419 (5) Å | µ = 0.51 mm−1 |
b = 9.7619 (8) Å | T = 180 K |
c = 17.7469 (16) Å | 0.42 × 0.40 × 0.13 mm |
Data collection top
Stoe IPDS diffractometer | 2418 independent reflections |
Absorption correction: multi-scan SORTAV, Blessing (1995) | 2207 reflections with I > 2σ(I) |
Tmin = 0.788, Tmax = 0.913 | Rint = 0.034 |
9901 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.059 | Δρmax = 0.22 e Å−3 |
S = 1.04 | Δρmin = −0.24 e Å−3 |
2418 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
148 parameters | Absolute structure parameter: 0.00 (5) |
0 restraints | |
Special details top
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS)
equipped with an Oxford Cryosystems cooler device. The crystal-to-detector
distance was 70 mm. 143 frames (3 min per frame) were obtained with 0 < ϕ <
200.2° and with the crystals rotated through 1.4° in ϕ. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.35355 (6) | 0.88785 (5) | 0.40672 (3) | 0.03284 (12) | |
Cl2 | 0.29567 (7) | 0.85649 (5) | 0.24692 (3) | 0.04162 (14) | |
O1 | 0.75687 (18) | 0.50736 (11) | 0.43588 (7) | 0.0284 (3) | |
O2 | 1.02114 (19) | 0.46852 (12) | 0.37546 (8) | 0.0309 (3) | |
H2 | 1.0003 | 0.3893 | 0.3883 | 0.046* | |
O3 | 0.9563 (2) | 1.20229 (11) | 0.39783 (7) | 0.0312 (3) | |
C1 | 0.7519 (2) | 0.78833 (14) | 0.38088 (9) | 0.0193 (3) | |
H1 | 0.6851 | 0.7735 | 0.4282 | 0.023* | |
C2 | 0.6208 (2) | 0.75365 (15) | 0.31616 (9) | 0.0209 (3) | |
C3 | 0.4663 (3) | 0.65102 (17) | 0.33088 (9) | 0.0253 (4) | |
H3A | 0.4289 | 0.5920 | 0.2896 | 0.030* | |
H3B | 0.4601 | 0.6092 | 0.3804 | 0.030* | |
C4 | 0.4233 (3) | 0.79866 (17) | 0.32490 (9) | 0.0244 (4) | |
C11 | 0.8099 (2) | 0.94040 (15) | 0.37805 (9) | 0.0205 (3) | |
H11A | 0.9147 | 0.9503 | 0.3444 | 0.025* | |
H11B | 0.7090 | 0.9943 | 0.3577 | 0.025* | |
C12 | 0.8612 (3) | 0.99546 (16) | 0.45525 (9) | 0.0230 (3) | |
H12A | 0.7561 | 0.9843 | 0.4886 | 0.028* | |
H12B | 0.9614 | 0.9405 | 0.4753 | 0.028* | |
C13 | 0.9190 (2) | 1.14322 (16) | 0.45630 (9) | 0.0215 (3) | |
C14 | 0.9290 (3) | 1.21279 (17) | 0.53099 (10) | 0.0289 (4) | |
H14A | 0.9508 | 1.3089 | 0.5237 | 0.043* | |
H14B | 1.0281 | 1.1741 | 0.5600 | 0.043* | |
H14C | 0.8146 | 1.2001 | 0.5574 | 0.043* | |
C16 | 0.9230 (3) | 0.69706 (15) | 0.38193 (10) | 0.0250 (4) | |
H16A | 0.9818 | 0.7018 | 0.3329 | 0.030* | |
H16B | 1.0094 | 0.7336 | 0.4185 | 0.030* | |
C17 | 0.8874 (2) | 0.54926 (15) | 0.40043 (9) | 0.0211 (3) | |
C21 | 0.7050 (3) | 0.7567 (2) | 0.23829 (10) | 0.0353 (4) | |
H21A | 0.8064 | 0.6934 | 0.2361 | 0.053* | |
H21B | 0.7488 | 0.8474 | 0.2275 | 0.053* | |
H21C | 0.6135 | 0.7312 | 0.2018 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0219 (2) | 0.0366 (2) | 0.0401 (2) | 0.00046 (18) | 0.00227 (18) | −0.01009 (19) |
Cl2 | 0.0409 (3) | 0.0428 (3) | 0.0411 (3) | −0.0065 (2) | −0.0194 (2) | 0.0139 (2) |
O1 | 0.0276 (8) | 0.0197 (5) | 0.0379 (7) | −0.0034 (5) | 0.0046 (5) | 0.0052 (5) |
O2 | 0.0324 (8) | 0.0154 (5) | 0.0450 (7) | 0.0020 (5) | 0.0078 (6) | 0.0020 (5) |
O3 | 0.0442 (8) | 0.0163 (5) | 0.0332 (7) | −0.0041 (5) | 0.0025 (6) | 0.0000 (5) |
C1 | 0.0196 (9) | 0.0158 (7) | 0.0224 (7) | −0.0032 (6) | 0.0010 (6) | 0.0018 (6) |
C2 | 0.0238 (10) | 0.0154 (7) | 0.0234 (8) | −0.0038 (6) | 0.0006 (7) | −0.0003 (6) |
C3 | 0.0281 (11) | 0.0215 (8) | 0.0262 (8) | −0.0074 (7) | −0.0027 (7) | 0.0003 (7) |
C4 | 0.0251 (10) | 0.0238 (8) | 0.0244 (8) | −0.0043 (7) | −0.0042 (7) | 0.0009 (6) |
C11 | 0.0211 (9) | 0.0143 (6) | 0.0259 (7) | −0.0018 (6) | −0.0008 (7) | 0.0009 (6) |
C12 | 0.0257 (10) | 0.0172 (7) | 0.0260 (8) | −0.0018 (7) | 0.0005 (7) | 0.0011 (6) |
C13 | 0.0167 (9) | 0.0188 (8) | 0.0292 (8) | 0.0034 (6) | −0.0009 (6) | −0.0007 (6) |
C14 | 0.0299 (10) | 0.0227 (8) | 0.0341 (9) | 0.0020 (7) | −0.0046 (8) | −0.0053 (7) |
C16 | 0.0204 (9) | 0.0157 (7) | 0.0389 (9) | −0.0027 (7) | 0.0021 (7) | 0.0030 (7) |
C17 | 0.0235 (10) | 0.0151 (7) | 0.0246 (8) | −0.0017 (6) | −0.0060 (7) | −0.0004 (6) |
C21 | 0.0426 (12) | 0.0364 (9) | 0.0270 (9) | −0.0079 (8) | 0.0089 (9) | −0.0041 (7) |
Geometric parameters (Å, º) top
Cl1—C4 | 1.7668 (17) | C11—C12 | 1.518 (2) |
Cl2—C4 | 1.7572 (17) | C11—H11A | 0.9700 |
O1—C17 | 1.207 (2) | C11—H11B | 0.9700 |
O2—C17 | 1.325 (2) | C12—C13 | 1.502 (2) |
O2—H2 | 0.8200 | C12—H12A | 0.9700 |
O3—C13 | 1.2175 (19) | C12—H12B | 0.9700 |
C1—C16 | 1.526 (2) | C13—C14 | 1.491 (2) |
C1—C2 | 1.528 (2) | C14—H14A | 0.9600 |
C1—C11 | 1.5436 (19) | C14—H14B | 0.9600 |
C1—H1 | 0.9800 | C14—H14C | 0.9600 |
C2—C4 | 1.505 (3) | C16—C17 | 1.502 (2) |
C2—C21 | 1.511 (2) | C16—H16A | 0.9700 |
C2—C3 | 1.524 (2) | C16—H16B | 0.9700 |
C3—C4 | 1.478 (2) | C21—H21A | 0.9600 |
C3—H3A | 0.9700 | C21—H21B | 0.9600 |
C3—H3B | 0.9700 | C21—H21C | 0.9600 |
| | | |
C17—O2—H2 | 109.5 | C13—C12—C11 | 114.80 (13) |
C16—C1—C2 | 112.60 (13) | C13—C12—H12A | 108.6 |
C16—C1—C11 | 109.92 (13) | C11—C12—H12A | 108.6 |
C2—C1—C11 | 110.96 (13) | C13—C12—H12B | 108.6 |
C16—C1—H1 | 107.7 | C11—C12—H12B | 108.6 |
C2—C1—H1 | 107.7 | H12A—C12—H12B | 107.5 |
C11—C1—H1 | 107.7 | O3—C13—C14 | 122.08 (14) |
C4—C2—C21 | 118.20 (15) | O3—C13—C12 | 120.41 (13) |
C4—C2—C3 | 58.42 (11) | C14—C13—C12 | 117.51 (14) |
C21—C2—C3 | 117.78 (14) | C13—C14—H14A | 109.5 |
C4—C2—C1 | 116.65 (14) | C13—C14—H14B | 109.5 |
C21—C2—C1 | 115.61 (16) | H14A—C14—H14B | 109.5 |
C3—C2—C1 | 118.21 (13) | C13—C14—H14C | 109.5 |
C4—C3—C2 | 60.11 (12) | H14A—C14—H14C | 109.5 |
C4—C3—H3A | 117.8 | H14B—C14—H14C | 109.5 |
C2—C3—H3A | 117.8 | C17—C16—C1 | 115.08 (15) |
C4—C3—H3B | 117.8 | C17—C16—H16A | 108.5 |
C2—C3—H3B | 117.8 | C1—C16—H16A | 108.5 |
H3A—C3—H3B | 114.9 | C17—C16—H16B | 108.5 |
C3—C4—C2 | 61.46 (11) | C1—C16—H16B | 108.5 |
C3—C4—Cl2 | 118.73 (12) | H16A—C16—H16B | 107.5 |
C2—C4—Cl2 | 120.84 (13) | O1—C17—O2 | 123.05 (14) |
C3—C4—Cl1 | 118.80 (12) | O1—C17—C16 | 125.03 (15) |
C2—C4—Cl1 | 120.02 (12) | O2—C17—C16 | 111.88 (15) |
Cl2—C4—Cl1 | 109.80 (10) | C2—C21—H21A | 109.5 |
C12—C11—C1 | 112.20 (13) | C2—C21—H21B | 109.5 |
C12—C11—H11A | 109.2 | H21A—C21—H21B | 109.5 |
C1—C11—H11A | 109.2 | C2—C21—H21C | 109.5 |
C12—C11—H11B | 109.2 | H21A—C21—H21C | 109.5 |
C1—C11—H11B | 109.2 | H21B—C21—H21C | 109.5 |
H11A—C11—H11B | 107.9 | | |
| | | |
C16—C1—C2—C4 | 158.71 (14) | C1—C2—C4—Cl2 | 143.58 (12) |
C11—C1—C2—C4 | −77.61 (17) | C21—C2—C4—Cl1 | −144.47 (14) |
C16—C1—C2—C21 | −55.52 (18) | C3—C2—C4—Cl1 | 108.60 (15) |
C11—C1—C2—C21 | 68.17 (19) | C1—C2—C4—Cl1 | 0.4 (2) |
C16—C1—C2—C3 | 92.01 (17) | C16—C1—C11—C12 | −81.29 (17) |
C11—C1—C2—C3 | −144.30 (14) | C2—C1—C11—C12 | 153.51 (15) |
C21—C2—C3—C4 | −107.65 (17) | C1—C11—C12—C13 | −179.97 (15) |
C1—C2—C3—C4 | 105.53 (16) | C11—C12—C13—O3 | −14.1 (2) |
C2—C3—C4—Cl2 | 111.55 (16) | C11—C12—C13—C14 | 166.17 (16) |
C2—C3—C4—Cl1 | −110.55 (15) | C2—C1—C16—C17 | −67.65 (18) |
C21—C2—C4—C3 | 106.93 (16) | C11—C1—C16—C17 | 168.09 (14) |
C1—C2—C4—C3 | −108.20 (15) | C1—C16—C17—O1 | −24.4 (2) |
C21—C2—C4—Cl2 | −1.3 (2) | C1—C16—C17—O2 | 157.88 (14) |
C3—C2—C4—Cl2 | −108.21 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.86 | 2.671 (2) | 169 |
C3—H3B···O1 | 0.98 | 2.56 | 3.141 (2) | 118 |
C1—H1···Cl1 | 0.98 | 2.67 | 3.078 (2) | 105 |
Symmetry code: (i) x, y−1, z. |
Crystal data top
C11H16Br2O3 | F(000) = 704 |
Mr = 356.06 | Dx = 1.819 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8000 reflections |
a = 7.4006 (5) Å | θ = 2.3–26.0° |
b = 9.7511 (10) Å | µ = 6.23 mm−1 |
c = 18.0171 (13) Å | T = 180 K |
V = 1300.19 (19) Å3 | Parallelepiped, colorless |
Z = 4 | 0.3 × 0.28 × 0.18 mm |
Data collection top
Stoe IPDS diffractometer | 2070 reflections with I > 2σ(I) |
ϕ scans | Rint = 0.074 |
Absorption correction: multi-scan SORTAV, Blessing (1995) | θmax = 26.1°, θmin = 2.3° |
Tmin = 0.162, Tmax = 0.348 | h = −8→8 |
9311 measured reflections | k = −11→11 |
2376 independent reflections | l = −22→22 |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.1506P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.016 |
2376 reflections | Δρmax = 0.51 e Å−3 |
148 parameters | Δρmin = −0.56 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (2) |
Crystal data top
C11H16Br2O3 | V = 1300.19 (19) Å3 |
Mr = 356.06 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.4006 (5) Å | µ = 6.23 mm−1 |
b = 9.7511 (10) Å | T = 180 K |
c = 18.0171 (13) Å | 0.3 × 0.28 × 0.18 mm |
Data collection top
Stoe IPDS diffractometer | 2376 independent reflections |
Absorption correction: multi-scan SORTAV, Blessing (1995) | 2070 reflections with I > 2σ(I) |
Tmin = 0.162, Tmax = 0.348 | Rint = 0.074 |
9311 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 0.51 e Å−3 |
S = 1.09 | Δρmin = −0.56 e Å−3 |
2376 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
148 parameters | Absolute structure parameter: −0.03 (2) |
0 restraints | |
Special details top
Experimental. The data were collected on a Stoe Imaging Plate Diffraction System (IPDS)
equipped with an Oxford Cryosystems cooler device. The crystal-to-detector
distance was 70 mm. 143 frames (4 min per frame) were obtained with 0 < ϕ <
200.2° and with the crystals rotated through 1.4° in ϕ. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.35714 (9) | 0.88593 (6) | 0.41179 (3) | 0.03788 (17) | |
Br2 | 0.29276 (10) | 0.83970 (7) | 0.24107 (3) | 0.0465 (2) | |
O1 | 0.7668 (6) | 0.4995 (4) | 0.4370 (2) | 0.0347 (10) | |
O2 | 1.0233 (7) | 0.4611 (4) | 0.3769 (3) | 0.0399 (10) | |
H2 | 1.0029 | 0.3818 | 0.3896 | 0.060* | |
O3 | 0.9632 (7) | 1.1939 (4) | 0.4001 (2) | 0.0405 (11) | |
C1 | 0.7587 (8) | 0.7810 (5) | 0.3802 (3) | 0.0270 (12) | |
H1 | 0.6928 | 0.7664 | 0.4267 | 0.032* | |
C2 | 0.6291 (9) | 0.7452 (5) | 0.3164 (3) | 0.0263 (11) | |
C3 | 0.4830 (8) | 0.6403 (5) | 0.3326 (3) | 0.0304 (12) | |
H3A | 0.4473 | 0.5792 | 0.2927 | 0.036* | |
H3B | 0.4799 | 0.6000 | 0.3818 | 0.036* | |
C4 | 0.4359 (9) | 0.7880 (6) | 0.3254 (3) | 0.0339 (13) | |
C11 | 0.8158 (8) | 0.9331 (5) | 0.3781 (3) | 0.0282 (13) | |
H11A | 0.9206 | 0.9429 | 0.3463 | 0.034* | |
H11B | 0.7185 | 0.9871 | 0.3569 | 0.034* | |
C12 | 0.8607 (10) | 0.9880 (5) | 0.4550 (3) | 0.0336 (13) | |
H12A | 0.7547 | 0.9781 | 0.4862 | 0.040* | |
H12B | 0.9555 | 0.9315 | 0.4761 | 0.040* | |
C13 | 0.9207 (8) | 1.1353 (5) | 0.4574 (3) | 0.0316 (13) | |
C14 | 0.9257 (10) | 1.2040 (6) | 0.5312 (3) | 0.0388 (15) | |
H14A | 0.9340 | 1.3014 | 0.5245 | 0.058* | |
H14B | 1.0289 | 1.1722 | 0.5586 | 0.058* | |
H14C | 0.8175 | 1.1825 | 0.5582 | 0.058* | |
C16 | 0.9263 (9) | 0.6900 (5) | 0.3825 (3) | 0.0321 (13) | |
H16A | 0.9850 | 0.6942 | 0.3344 | 0.039* | |
H16B | 1.0096 | 0.7276 | 0.4187 | 0.039* | |
C17 | 0.8928 (8) | 0.5417 (5) | 0.4014 (3) | 0.0293 (13) | |
C21 | 0.7122 (10) | 0.7487 (6) | 0.2392 (3) | 0.0428 (15) | |
H21A | 0.8116 | 0.6856 | 0.2370 | 0.064* | |
H21B | 0.7547 | 0.8397 | 0.2288 | 0.064* | |
H21C | 0.6227 | 0.7231 | 0.2032 | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0343 (3) | 0.0354 (3) | 0.0439 (3) | 0.0003 (2) | 0.0014 (3) | −0.0071 (2) |
Br2 | 0.0482 (4) | 0.0462 (4) | 0.0450 (4) | −0.0071 (3) | −0.0144 (3) | 0.0133 (3) |
O1 | 0.038 (3) | 0.0238 (19) | 0.042 (2) | −0.0044 (17) | 0.0003 (18) | 0.0040 (15) |
O2 | 0.041 (3) | 0.0186 (19) | 0.061 (3) | 0.0012 (18) | 0.008 (2) | 0.0009 (17) |
O3 | 0.061 (3) | 0.021 (2) | 0.039 (2) | −0.0048 (18) | 0.004 (2) | 0.0004 (15) |
C1 | 0.031 (4) | 0.016 (2) | 0.034 (3) | −0.002 (2) | 0.000 (2) | 0.0023 (18) |
C2 | 0.033 (3) | 0.018 (2) | 0.028 (3) | 0.000 (2) | 0.001 (2) | 0.0009 (17) |
C3 | 0.035 (4) | 0.021 (3) | 0.035 (3) | −0.007 (2) | −0.002 (2) | 0.000 (2) |
C4 | 0.040 (4) | 0.025 (3) | 0.036 (3) | −0.008 (2) | −0.003 (2) | −0.002 (2) |
C11 | 0.032 (4) | 0.018 (2) | 0.035 (3) | −0.003 (2) | −0.002 (2) | 0.0010 (18) |
C12 | 0.041 (4) | 0.024 (3) | 0.035 (3) | 0.001 (3) | 0.000 (3) | 0.001 (2) |
C13 | 0.033 (4) | 0.024 (3) | 0.038 (3) | 0.002 (2) | 0.001 (2) | 0.000 (2) |
C14 | 0.040 (4) | 0.033 (3) | 0.043 (3) | 0.002 (3) | −0.005 (3) | −0.008 (2) |
C16 | 0.038 (4) | 0.019 (3) | 0.040 (3) | 0.000 (2) | 0.003 (2) | 0.001 (2) |
C17 | 0.033 (4) | 0.020 (3) | 0.035 (3) | −0.001 (2) | −0.005 (2) | 0.001 (2) |
C21 | 0.054 (4) | 0.041 (3) | 0.033 (3) | 0.001 (3) | 0.008 (3) | 0.002 (2) |
Geometric parameters (Å, º) top
Br1—C4 | 1.917 (6) | C11—C12 | 1.521 (7) |
Br2—C4 | 1.919 (6) | C11—H11A | 0.9700 |
O1—C17 | 1.204 (7) | C11—H11B | 0.9700 |
O2—C17 | 1.321 (7) | C12—C13 | 1.504 (8) |
O2—H2 | 0.8200 | C12—H12A | 0.9700 |
O3—C13 | 1.220 (7) | C12—H12B | 0.9700 |
C1—C16 | 1.525 (8) | C13—C14 | 1.490 (8) |
C1—C2 | 1.537 (8) | C14—H14A | 0.9600 |
C1—C11 | 1.543 (7) | C14—H14B | 0.9600 |
C1—H1 | 0.9800 | C14—H14C | 0.9600 |
C2—C4 | 1.499 (9) | C16—C17 | 1.506 (7) |
C2—C3 | 1.517 (8) | C16—H16A | 0.9700 |
C2—C21 | 1.520 (8) | C16—H16B | 0.9700 |
C3—C4 | 1.488 (8) | C21—H21A | 0.9600 |
C3—H3A | 0.9700 | C21—H21B | 0.9600 |
C3—H3B | 0.9700 | C21—H21C | 0.9600 |
| | | |
C17—O2—H2 | 109.5 | C13—C12—C11 | 115.3 (4) |
C16—C1—C2 | 113.3 (4) | C13—C12—H12A | 108.5 |
C16—C1—C11 | 109.7 (5) | C11—C12—H12A | 108.5 |
C2—C1—C11 | 111.8 (4) | C13—C12—H12B | 108.5 |
C16—C1—H1 | 107.3 | C11—C12—H12B | 108.5 |
C2—C1—H1 | 107.3 | H12A—C12—H12B | 107.5 |
C11—C1—H1 | 107.3 | O3—C13—C14 | 122.6 (5) |
C4—C2—C3 | 59.1 (4) | O3—C13—C12 | 119.9 (5) |
C4—C2—C21 | 118.6 (5) | C14—C13—C12 | 117.5 (5) |
C3—C2—C21 | 118.7 (5) | C13—C14—H14A | 109.5 |
C4—C2—C1 | 116.8 (5) | C13—C14—H14B | 109.5 |
C3—C2—C1 | 117.0 (4) | H14A—C14—H14B | 109.5 |
C21—C2—C1 | 115.3 (6) | C13—C14—H14C | 109.5 |
C4—C3—C2 | 59.9 (4) | H14A—C14—H14C | 109.5 |
C4—C3—H3A | 117.8 | H14B—C14—H14C | 109.5 |
C2—C3—H3A | 117.8 | C17—C16—C1 | 115.5 (5) |
C4—C3—H3B | 117.8 | C17—C16—H16A | 108.4 |
C2—C3—H3B | 117.8 | C1—C16—H16A | 108.4 |
H3A—C3—H3B | 114.9 | C17—C16—H16B | 108.4 |
C3—C4—C2 | 61.0 (4) | C1—C16—H16B | 108.4 |
C3—C4—Br1 | 118.9 (4) | H16A—C16—H16B | 107.5 |
C2—C4—Br1 | 121.1 (4) | O1—C17—O2 | 122.7 (5) |
C3—C4—Br2 | 116.9 (4) | O1—C17—C16 | 125.1 (5) |
C2—C4—Br2 | 121.0 (4) | O2—C17—C16 | 112.1 (5) |
Br1—C4—Br2 | 110.1 (3) | C2—C21—H21A | 109.5 |
C12—C11—C1 | 112.1 (4) | C2—C21—H21B | 109.5 |
C12—C11—H11A | 109.2 | H21A—C21—H21B | 109.5 |
C1—C11—H11A | 109.2 | C2—C21—H21C | 109.5 |
C12—C11—H11B | 109.2 | H21A—C21—H21C | 109.5 |
C1—C11—H11B | 109.2 | H21B—C21—H21C | 109.5 |
H11A—C11—H11B | 107.9 | | |
| | | |
C16—C1—C2—C4 | 157.4 (5) | C1—C2—C4—Br1 | 1.2 (6) |
C11—C1—C2—C4 | −78.1 (6) | C3—C2—C4—Br2 | −105.8 (5) |
C16—C1—C2—C3 | 90.2 (6) | C21—C2—C4—Br2 | 2.3 (7) |
C11—C1—C2—C3 | −145.2 (5) | C1—C2—C4—Br2 | 147.4 (4) |
C16—C1—C2—C21 | −56.4 (6) | C16—C1—C11—C12 | −81.8 (6) |
C11—C1—C2—C21 | 68.1 (6) | C2—C1—C11—C12 | 151.7 (5) |
C21—C2—C3—C4 | −108.0 (6) | C1—C11—C12—C13 | 179.0 (6) |
C1—C2—C3—C4 | 106.6 (5) | C11—C12—C13—O3 | −13.8 (9) |
C2—C3—C4—Br1 | −111.7 (5) | C11—C12—C13—C14 | 166.3 (6) |
C2—C3—C4—Br2 | 112.2 (5) | C2—C1—C16—C17 | −67.1 (6) |
C21—C2—C4—C3 | 108.1 (5) | C11—C1—C16—C17 | 167.2 (4) |
C1—C2—C4—C3 | −106.9 (5) | C1—C16—C17—O1 | −25.8 (8) |
C3—C2—C4—Br1 | 108.1 (5) | C1—C16—C17—O2 | 157.0 (5) |
C21—C2—C4—Br1 | −143.8 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.87 | 2.676 (5) | 170 |
C3—H3B···O1 | 0.97 | 2.54 | 3.136 (7) | 120 |
C1—H1···Br1 | 0.98 | 2.76 | 3.194 (6) | 108 |
Symmetry code: (i) x, y−1, z. |
Experimental details
| (2) | (3) |
Crystal data |
Chemical formula | C11H16Cl2O3 | C11H16Br2O3 |
Mr | 267.14 | 356.06 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 180 | 180 |
a, b, c (Å) | 7.2419 (5), 9.7619 (8), 17.7469 (16) | 7.4006 (5), 9.7511 (10), 18.0171 (13) |
V (Å3) | 1254.61 (18) | 1300.19 (19) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.51 | 6.23 |
Crystal size (mm) | 0.42 × 0.40 × 0.13 | 0.3 × 0.28 × 0.18 |
|
Data collection |
Diffractometer | Stoe IPDS diffractometer | Stoe IPDS diffractometer |
Absorption correction | Multi-scan SORTAV, Blessing (1995) | Multi-scan SORTAV, Blessing (1995) |
Tmin, Tmax | 0.788, 0.913 | 0.162, 0.348 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9901, 2418, 2207 | 9311, 2376, 2070 |
Rint | 0.034 | 0.074 |
(sin θ/λ)max (Å−1) | 0.617 | 0.618 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.059, 1.04 | 0.037, 0.096, 1.09 |
No. of reflections | 2418 | 2376 |
No. of parameters | 148 | 148 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 | 0.51, −0.56 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.00 (5) | −0.03 (2) |
Selected geometric parameters (Å, º) for (2) topCl1—C4 | 1.7668 (17) | C1—C2 | 1.528 (2) |
Cl2—C4 | 1.7572 (17) | C2—C4 | 1.505 (3) |
O1—C17 | 1.207 (2) | C2—C21 | 1.511 (2) |
O2—C17 | 1.325 (2) | C2—C3 | 1.524 (2) |
O3—C13 | 1.2175 (19) | C3—C4 | 1.478 (2) |
| | | |
C4—C2—C21 | 118.20 (15) | C3—C4—Cl2 | 118.73 (12) |
C4—C2—C3 | 58.42 (11) | C2—C4—Cl2 | 120.84 (13) |
C21—C2—C3 | 117.78 (14) | C3—C4—Cl1 | 118.80 (12) |
C4—C2—C1 | 116.65 (14) | C2—C4—Cl1 | 120.02 (12) |
C21—C2—C1 | 115.61 (16) | Cl2—C4—Cl1 | 109.80 (10) |
C3—C2—C1 | 118.21 (13) | O1—C17—O2 | 123.05 (14) |
C4—C3—C2 | 60.11 (12) | O1—C17—C16 | 125.03 (15) |
C3—C4—C2 | 61.46 (11) | O2—C17—C16 | 111.88 (15) |
| | | |
C16—C1—C11—C12 | −81.29 (17) | C2—C1—C16—C17 | −67.65 (18) |
C2—C1—C11—C12 | 153.51 (15) | C11—C1—C16—C17 | 168.09 (14) |
C1—C11—C12—C13 | −179.97 (15) | C1—C16—C17—O1 | −24.4 (2) |
C11—C12—C13—O3 | −14.1 (2) | C1—C16—C17—O2 | 157.88 (14) |
C11—C12—C13—C14 | 166.17 (16) | | |
Hydrogen-bond geometry (Å, º) for (2) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.86 | 2.671 (2) | 169 |
C3—H3B···O1 | 0.98 | 2.56 | 3.141 (2) | 118.0 |
C1—H1···Cl1 | 0.98 | 2.67 | 3.078 (2) | 105.0 |
Symmetry code: (i) x, y−1, z. |
Selected geometric parameters (Å, º) for (3) topBr1—C4 | 1.917 (6) | C1—C2 | 1.537 (8) |
Br2—C4 | 1.919 (6) | C2—C4 | 1.499 (9) |
O1—C17 | 1.204 (7) | C2—C3 | 1.517 (8) |
O2—C17 | 1.321 (7) | C2—C21 | 1.520 (8) |
O3—C13 | 1.220 (7) | C3—C4 | 1.488 (8) |
| | | |
C4—C2—C3 | 59.1 (4) | C3—C4—Br1 | 118.9 (4) |
C4—C2—C21 | 118.6 (5) | C2—C4—Br1 | 121.1 (4) |
C3—C2—C21 | 118.7 (5) | C3—C4—Br2 | 116.9 (4) |
C4—C2—C1 | 116.8 (5) | C2—C4—Br2 | 121.0 (4) |
C3—C2—C1 | 117.0 (4) | Br1—C4—Br2 | 110.1 (3) |
C21—C2—C1 | 115.3 (6) | O1—C17—O2 | 122.7 (5) |
C4—C3—C2 | 59.9 (4) | O1—C17—C16 | 125.1 (5) |
C3—C4—C2 | 61.0 (4) | O2—C17—C16 | 112.1 (5) |
| | | |
C16—C1—C11—C12 | −81.8 (6) | C2—C1—C16—C17 | −67.1 (6) |
C2—C1—C11—C12 | 151.7 (5) | C11—C1—C16—C17 | 167.2 (4) |
C1—C11—C12—C13 | 179.0 (6) | C1—C16—C17—O1 | −25.8 (8) |
C11—C12—C13—O3 | −13.8 (9) | C1—C16—C17—O2 | 157.0 (5) |
C11—C12—C13—C14 | 166.3 (6) | | |
Hydrogen-bond geometry (Å, º) for (3) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.87 | 2.676 (5) | 169.5 |
C3—H3B···O1 | 0.97 | 2.54 | 3.136 (7) | 119.6 |
C1—H1···Br1 | 0.98 | 2.76 | 3.194 (6) | 107.6 |
Symmetry code: (i) x, y−1, z. |
Comparison of C-C distances in some related dihalogenocyclopropanes topCompound | | X | R1 | R2 | C2-C3(Å) | C2-C4(Å) | C3-C4(Å) |
C11H16Cl2O3a | | Cl | Me | C7H11O3 | 1.524 (2) | 1.505 (3) | 1.478 (2) |
C11H16Br2O3a | | Br | Me | C7H11O3 | 1.517 (8) | 1.499 (9) | 1.488 (8) |
C12H14Cl4Ob | | Cl | Me | C8H9Cl2O | 1.514 | 1.488 | 1.464 |
C12H14Cl4Ob | | Cl | Me | C8H9Cl2O | 1.492 | 1.516 | 1.459 |
C15H10Cl4c | | Cl | C6H4Cl | C6H4Cl | 1.484 | 1.472 | 1.473 |
| | Cl | C6H4Cl | C6H4Cl | 1.517 | 1.543 | 1.546 |
C15H12Cl2d | | Cl | Ph | Ph | 1.529 | 1.520 | 1.490 |
C15H12Br2d | | Br | Ph | Ph | 1.508 | 1.509 | 1.477 |
C13H16Cl4e | | Cl | CO2 | C6H4OEt | 1.519 | 1.517 | 1.486 |
C5H6Cl2O2f | | Cl | Me | CO2 | 1.523 | 1.523 | 1.481 |
| | Cl | Me | CO2 | 1.520 | 1.520 | 1.483 |
C5H6Br2O2f | | Br | Me | CO2 | 1.518 | 1.519 | 1.497 |
C5H6Cl2O2f | | Cl | Me | CH2CO2 | 1.531 | 1.509 | 1.497 |
C18H14Cl4g | | Cl | Ph | C3H2PhCl2 | 1.520 | 1.505 | 1.472 |
| | Cl | Ph | C3H2PhCl2 | 1.525 | 1.508 | 1.472 |
| | Cl | Ph | C3H2PhCl2 | 1.527 | 1.535 | 1.469 |
| | Cl | Ph | C3H2PhCl2 | 1.516 | 1.533 | 1.477 |
C18H14Cl4g | | Cl | Ph | C3H2PhCl2 | 1.518 | 1.516 | 1.476 |
| | Cl | Ph | C3H2PhCl2 | 1.527 | 1.540 | 1.475 |
C18H14Br4g | | Br | Ph | C3H2PhBr2 | 1.544 | 1.514 | 1.488 |
| | Br | Ph | C3H2PhBr2 | 1.528 | 1.537 | 1.484 |
C11H10Cl2O2h | | Cl | Ph | CH2CO2 | 1.518 | 1.515 | 1.489 |
C11H10Br2O2h | | Br | Ph | CH2CO2 | 1.518 | 1.495 | 1.487 |
C10H9BrCl2h | | Cl | Ph | CH2Br | 1.508 | 1.507 | 1.493 |
C17H13Cl2NO4h | | Cl | Ph | CO2CPhNO2 | 1.520 | 1.512 | 1.483 |
C5H7Br2NOi | | Br | CH3 | CONH2 | 1.529 | 1.509 | 1.508 |
| | Br | CH3 | CONH2 | 1.532 | 1.493 | 1.490 |
C12H13Cl2Oj | | Cl | CH3 | CHOC6H4Me | 1.529 | 1.508 | 1.497 |
| | Cl | CH3 | CHOC6H4Me | 1.534 | 1.509 | 1.489 |
References:
a) This study;
b) Zukerman-Schpector et al. (1984);
c) DeLacy & Kennard (1972);
d) Lauher & Ibers (1975);
e) Poppleton (1986);
f) Romming & Sydnes (1987);
g) Lam et al. (1997);
h) Sydnes et al. (1991);
i) Baird et al. (1999);
j) Tanabe et al. (1999) |
Despite their high ring strain, cyclopropanes are commonly encountered among both naturally occurring and synthetic compounds. In addition, diastereoselectively substituted cyclopropanes have attracted attention as useful precursors of highly strained molecules (Boche et al., 1990; Tanabe et al., 1996) and biologically active pyrethroids (Hirota et al., 1996; Kunzer et al., 1996). Thus, promise of their usefulness as synthetic intermediates is growing rapidly. Here we describe the structure of two new polyfunctionalized dichloro and dibromo cyclopropanes 2 and 3, which could be valuable synthons for pyrethroid derivatives.
These two compounds were prepared from (R)-limonene oxide 1 by dihalocyclopropanation of the C7=C8 double bond followed by oxidation of oxirane ring under Sharpless conditions (see Experimental). In order to confirm the structure assignments and establish the absolute stereochemistry, single X-ray studies were carried out on both compounds. The two derivatives crystallize isotypically; only the chloro compound 2 is illustrated in Fig. 1 (a view of molecule 3 is given in the supplementary material). Identical numbering schemes have been employed in both molecules. The absolute configuration (1'S,3R) has been unambiguously determined by refinement of the Flack (1983) parameter. Examination of the cyclopropyl moieties indicates that the rings are unsymmetrical, with unequal C—C bond lengths (Tables 1 & 3). The C(3)—C(4) bond length in the chloro derivative is 1.479 (2) Å while the bonds adjacent to the methyl and the polyfonctional substituents are longer, C(2)—C(4) 1.504 (3) Å and C(2)—C(3) 1.525 (3) Å. The same trend persists in the bromo derivative with identical C—C distances within experimental error. The bond angles within the three-membered ring reflect the difference observed between bond lengths with the smallest angle at C(2), C(3)—C(2)—C(4) 58.42 (12)° (59.1 (4)° for 3). The Cambridge Structural Database (CSD; Allen & Kennard, 1993) has been searched for related dihalogenocyclopropane structures having CH2 and CR2 groups(scheme 2). The search was limited to independent alkyl substuents R1 and R2 and excludes structures with interconnected R1 and R2 for which additional strain might influence the distances within the ring. The geometry of these cyclopropane rings (Table 5) shows the same tendancy observed for 2 and 3 with a shortening of the distal bond opposite the alkyl-substituted carbon and a lengthening of the vicinal bonds linking the alkyl and H substituted carbon atoms with respect to the mean C—C(ring) length of 1.509 (2)%A (Allen, 1980). These results are in agreement with a previous report (Allen, 1980). The C—Cl bond lengths average 1.762 (2) Å and the C—Br 1.918 (6) Å and are in good agreement with related gem-dihalogenocyclopropanes, as are the X—C—X angles of 109.8 (1)° for 2 and 110.1 (3)° for 3.
The 3-oxobutyl chain has an extended configuration with torsion angles C1—C11—C12—C13 - 180.0 (2)° [-179.0 (6) for 3] and C11—C12—C13—C14 166.2 (2)° [166.3 (6) for 3](Table 1 and 3). The substituents at C1, the carboxyl group and the cyclopropane ring are anti with respect to the oxobutyl chain. The orientations of the carboxyl group and the cyclopropane ring are influenced by intramolecular contacts C—H···O and C—H···Cl (or Br) that could be classified as hydrogen bonds. An interaction between an H atom of the cyclopropane carbon C3 and the O1 of the carboxyl (Table 2 and 4) results in a twisted conformation of the carboxyl group C17/O1/O2 with respect to the C1/C16/C17 plane [dihedral angle 23.1 (2)° for 2 and 24.2° for 3]. A further interaction occurs between Cl1 and the H at C1 (Table 2 and 4).
Fig. 2 illustrates the packing of 2 (the packing of 3 is shown in a supplementary file) in the cell, with extracellular molecules included to show the single-strand hydrogen-bonded catemers. The chain proceeds from the carboxyl of one molecule to the remote ketone (O2) of a neighbour (Table 4). Among hydrogen bonding catemers, the observed prevalence of subtypes, describing the relation of adjacent molecules, is screw > translation > glide, with the chains often following a cell axis(Brunskill et al., 2001). Here, the components of the chain are related by a translation along b. It is noteworthy that there are also short halogen···O1 contacts (3.056 (1) Å for the Cl and 3.020 (4) Å for the Br derivative) which connect the H bonded catemers.