Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023504/ci6185sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023504/ci6185Isup2.hkl |
CCDC reference: 204667
Key indicators
- Single-crystal X-ray study
- T = 213 K
- Mean (C-C) = 0.004 Å
- R factor = 0.065
- wR factor = 0.168
- Data-to-parameter ratio = 17.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.125
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared by the photo-induced reaction of 2-chloronaphtho-1,4-quinone with an excess of bicyclopropylidene in benzene solution, and was isolated by column chromatography on silica gel. Single crystals suitable for X-ray diffraction study were obtained from slow evaporation of a petroleum ether–ethyl acetate (20:1 v/v) solution.
The H atoms were fixed geometrically and treated as riding on their parent C atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C). The Cl atom was found to be disordered over two positions, Cl1 and Cl1A, bonded to C10 or C1 with occupancies of 0.864 (2) and 0.136 (2), respectively. During the refinement, similarity restraints were applied to the C10—Cl1 and C1—Cl1A distances and seven reflections showing a bad fit were suppressed. Owing to the poor diffraction quality of the crystal, the Rint value is high (0.126).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. For clarity, only the major component of the disordered Cl atom is shown. |
C16H13ClO2 | F(000) = 568 |
Mr = 272.71 | Dx = 1.400 Mg m−3 |
Monoclinic, P21/n | Melting point: 396(1) K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2794 (2) Å | Cell parameters from 4040 reflections |
b = 15.3344 (2) Å | θ = 2.7–28.4° |
c = 10.2590 (2) Å | µ = 0.29 mm−1 |
β = 96.639 (1)° | T = 213 K |
V = 1293.74 (4) Å3 | Slab, yellow |
Z = 4 | 0.34 × 0.34 × 0.06 mm |
Siemens SMART CCD area-detector diffractometer | 3140 independent reflections |
Radiation source: fine-focus sealed tube | 1736 reflections with > 2σ(I)' |
Graphite monochromator | Rint = 0.126 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −20→16 |
Tmin = 0.934, Tmax = 0.983 | l = −12→13 |
7752 measured reflections |
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)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0576P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max < 0.001 |
3133 reflections | Δρmax = 0.64 e Å−3 |
183 parameters | Δρmin = −0.55 e Å−3 |
1 restraint | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.066 (9) |
C16H13ClO2 | V = 1293.74 (4) Å3 |
Mr = 272.71 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2794 (2) Å | µ = 0.29 mm−1 |
b = 15.3344 (2) Å | T = 213 K |
c = 10.2590 (2) Å | 0.34 × 0.34 × 0.06 mm |
β = 96.639 (1)° |
Siemens SMART CCD area-detector diffractometer | 3140 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1736 reflections with > 2σ(I)' |
Tmin = 0.934, Tmax = 0.983 | Rint = 0.126 |
7752 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 1 restraint |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.64 e Å−3 |
3133 reflections | Δρmin = −0.55 e Å−3 |
183 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.14177 (11) | 0.26306 (5) | 0.34459 (9) | 0.0447 (3) | 0.864 (2) |
Cl1A | 0.4403 (5) | 0.1333 (4) | 0.3746 (6) | 0.056 (2) | 0.136 (2) |
O1 | 0.3473 (3) | −0.04416 (14) | 0.3665 (3) | 0.0630 (7) | |
O2 | −0.1677 (2) | 0.17168 (14) | 0.3265 (2) | 0.0571 (7) | |
C1 | 0.2539 (3) | 0.09539 (17) | 0.2979 (3) | 0.0364 (7) | |
H1 | 0.3464 | 0.1222 | 0.3515 | 0.044* | 0.864 (2) |
C2 | 0.2302 (3) | 0.00383 (19) | 0.3380 (3) | 0.0379 (7) | |
C3 | 0.0615 (3) | −0.03029 (17) | 0.3317 (3) | 0.0326 (6) | |
C4 | 0.0365 (4) | −0.11971 (19) | 0.3377 (3) | 0.0449 (8) | |
H4 | 0.1251 | −0.1574 | 0.3449 | 0.054* | |
C5 | −0.1193 (4) | −0.1531 (2) | 0.3331 (3) | 0.0571 (9) | |
H5 | −0.1354 | −0.2131 | 0.3350 | 0.068* | |
C6 | −0.2518 (4) | −0.0970 (2) | 0.3255 (3) | 0.0577 (9) | |
H6 | −0.3564 | −0.1195 | 0.3225 | 0.069* | |
C7 | −0.2288 (3) | −0.0084 (2) | 0.3224 (3) | 0.0469 (8) | |
H7 | −0.3180 | 0.0287 | 0.3202 | 0.056* | |
C8 | −0.0733 (3) | 0.02653 (17) | 0.3227 (2) | 0.0317 (6) | |
C9 | −0.0551 (3) | 0.12260 (18) | 0.3147 (3) | 0.0351 (7) | |
C10 | 0.1059 (3) | 0.15830 (15) | 0.2792 (3) | 0.0317 (6) | |
H10 | 0.1309 | 0.2165 | 0.3155 | 0.038* | 0.136 (2) |
C11 | 0.1146 (3) | 0.15334 (17) | 0.1286 (3) | 0.0353 (7) | |
C12 | 0.2716 (3) | 0.10299 (18) | 0.1509 (3) | 0.0408 (7) | |
C13 | −0.0233 (4) | 0.1380 (2) | 0.0255 (3) | 0.0613 (10) | |
H13A | −0.1322 | 0.1381 | 0.0515 | 0.074* | |
H13B | −0.0067 | 0.0978 | −0.0448 | 0.074* | |
C14 | 0.0676 (4) | 0.2223 (2) | 0.0316 (3) | 0.0554 (9) | |
H14A | 0.1391 | 0.2333 | −0.0351 | 0.066* | |
H14B | 0.0135 | 0.2735 | 0.0612 | 0.066* | |
C15 | 0.3366 (5) | 0.0361 (2) | 0.0654 (4) | 0.0700 (12) | |
H15A | 0.2783 | 0.0266 | −0.0210 | 0.084* | |
H15B | 0.3858 | −0.0158 | 0.1073 | 0.084* | |
C16 | 0.4253 (4) | 0.1217 (2) | 0.0904 (4) | 0.0707 (12) | |
H16A | 0.5272 | 0.1212 | 0.1475 | 0.085* | |
H16B | 0.4197 | 0.1636 | 0.0192 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0574 (6) | 0.0287 (4) | 0.0512 (6) | −0.0048 (4) | 0.0195 (4) | −0.0142 (4) |
Cl1A | 0.033 (3) | 0.061 (4) | 0.072 (5) | −0.007 (2) | −0.005 (3) | −0.036 (3) |
C1 | 0.0254 (14) | 0.0375 (16) | 0.0473 (18) | −0.0009 (11) | 0.0089 (12) | −0.0040 (13) |
O1 | 0.0384 (13) | 0.0594 (15) | 0.0929 (19) | 0.0192 (11) | 0.0146 (12) | 0.0194 (13) |
O2 | 0.0419 (13) | 0.0514 (14) | 0.0830 (17) | 0.0181 (10) | 0.0290 (12) | 0.0095 (12) |
C2 | 0.0326 (15) | 0.0427 (16) | 0.0397 (17) | 0.0094 (12) | 0.0100 (12) | 0.0037 (13) |
C3 | 0.0343 (15) | 0.0347 (15) | 0.0307 (15) | 0.0022 (12) | 0.0116 (12) | 0.0010 (12) |
C4 | 0.0552 (19) | 0.0357 (16) | 0.0463 (19) | 0.0013 (14) | 0.0164 (15) | 0.0032 (14) |
C5 | 0.077 (3) | 0.0435 (19) | 0.052 (2) | −0.0196 (18) | 0.0151 (18) | 0.0055 (15) |
C6 | 0.0441 (19) | 0.069 (2) | 0.059 (2) | −0.0204 (17) | 0.0022 (16) | 0.0164 (18) |
C7 | 0.0325 (16) | 0.057 (2) | 0.051 (2) | −0.0040 (14) | 0.0076 (14) | 0.0166 (16) |
C8 | 0.0328 (14) | 0.0372 (15) | 0.0263 (14) | −0.0006 (11) | 0.0080 (11) | 0.0035 (11) |
C9 | 0.0328 (15) | 0.0405 (16) | 0.0344 (16) | 0.0089 (12) | 0.0139 (12) | 0.0019 (12) |
C10 | 0.0341 (14) | 0.0291 (14) | 0.0336 (15) | 0.0015 (11) | 0.0117 (11) | −0.0081 (11) |
C11 | 0.0375 (15) | 0.0358 (15) | 0.0347 (16) | −0.0015 (12) | 0.0133 (12) | −0.0025 (12) |
C12 | 0.0406 (16) | 0.0353 (16) | 0.0511 (19) | 0.0023 (12) | 0.0255 (14) | −0.0023 (13) |
C13 | 0.057 (2) | 0.083 (3) | 0.043 (2) | −0.0107 (19) | 0.0042 (17) | 0.0018 (18) |
C14 | 0.063 (2) | 0.055 (2) | 0.050 (2) | 0.0087 (16) | 0.0186 (17) | 0.0102 (16) |
C15 | 0.091 (3) | 0.056 (2) | 0.074 (3) | 0.018 (2) | 0.054 (2) | −0.0036 (19) |
C16 | 0.055 (2) | 0.071 (3) | 0.096 (3) | 0.0084 (18) | 0.051 (2) | 0.021 (2) |
Cl1—C10 | 1.753 (2) | C7—C8 | 1.395 (4) |
C10—C9 | 1.523 (3) | C7—H7 | 0.93 |
C10—C1 | 1.554 (4) | C8—C9 | 1.484 (4) |
C10—C11 | 1.557 (4) | C11—C14 | 1.473 (4) |
C1—C2 | 1.483 (4) | C11—C13 | 1.482 (4) |
C1—C12 | 1.537 (4) | C11—C12 | 1.507 (4) |
C1—H1 | 0.98 | C12—C15 | 1.490 (4) |
O1—C2 | 1.225 (3) | C12—C16 | 1.506 (4) |
O2—C9 | 1.215 (3) | C13—C14 | 1.493 (5) |
C2—C3 | 1.486 (4) | C13—H13A | 0.97 |
C3—C4 | 1.389 (4) | C13—H13B | 0.97 |
C3—C8 | 1.410 (4) | C14—H14A | 0.97 |
C4—C5 | 1.383 (4) | C14—H14B | 0.97 |
C4—H4 | 0.93 | C15—C16 | 1.512 (5) |
C5—C6 | 1.389 (5) | C15—H15A | 0.97 |
C5—H5 | 0.93 | C15—H15B | 0.97 |
C6—C7 | 1.372 (4) | C16—H16A | 0.97 |
C6—H6 | 0.93 | C16—H16B | 0.97 |
C9—C10—C1 | 116.5 (2) | C14—C11—C13 | 60.7 (2) |
C9—C10—C11 | 111.2 (2) | C14—C11—C12 | 128.8 (2) |
C1—C10—C11 | 88.05 (18) | C13—C11—C12 | 127.4 (3) |
C9—C10—Cl1 | 110.62 (16) | C14—C11—C10 | 126.6 (2) |
C1—C10—Cl1 | 115.17 (17) | C13—C11—C10 | 126.6 (2) |
C11—C10—Cl1 | 113.53 (17) | C12—C11—C10 | 90.7 (2) |
C2—C1—C12 | 112.0 (2) | C15—C12—C16 | 60.6 (2) |
C2—C1—C10 | 119.6 (2) | C15—C12—C11 | 128.9 (3) |
C12—C1—C10 | 89.7 (2) | C16—C12—C11 | 126.5 (3) |
C2—C1—H1 | 111.2 | C15—C12—C1 | 127.4 (3) |
C12—C1—H1 | 111.2 | C16—C12—C1 | 126.8 (3) |
C10—C1—H1 | 111.2 | C11—C12—C1 | 90.54 (19) |
O1—C2—C1 | 120.6 (3) | C11—C13—C14 | 59.3 (2) |
O1—C2—C3 | 120.9 (3) | C11—C13—H13A | 117.8 |
C1—C2—C3 | 118.4 (2) | C14—C13—H13A | 117.8 |
C4—C3—C8 | 119.4 (3) | C11—C13—H13B | 117.8 |
C4—C3—C2 | 119.3 (2) | C14—C13—H13B | 117.8 |
C8—C3—C2 | 121.2 (2) | H13A—C13—H13B | 115.0 |
C5—C4—C3 | 120.5 (3) | C11—C14—C13 | 60.0 (2) |
C5—C4—H4 | 119.8 | C11—C14—H14A | 117.8 |
C3—C4—H4 | 119.8 | C13—C14—H14A | 117.8 |
C4—C5—C6 | 120.0 (3) | C11—C14—H14B | 117.8 |
C4—C5—H5 | 120.0 | C13—C14—H14B | 117.8 |
C6—C5—H5 | 120.0 | H14A—C14—H14B | 114.9 |
C7—C6—C5 | 120.3 (3) | C12—C15—C16 | 60.2 (2) |
C7—C6—H6 | 119.9 | C12—C15—H15A | 117.8 |
C5—C6—H6 | 119.9 | C16—C15—H15A | 117.8 |
C6—C7—C8 | 120.7 (3) | C12—C15—H15B | 117.8 |
C6—C7—H7 | 119.7 | C16—C15—H15B | 117.8 |
C8—C7—H7 | 119.7 | H15A—C15—H15B | 114.9 |
C7—C8—C3 | 119.1 (3) | C12—C16—C15 | 59.2 (2) |
C7—C8—C9 | 118.7 (2) | C12—C16—H16A | 117.9 |
C3—C8—C9 | 122.2 (2) | C15—C16—H16A | 117.9 |
O2—C9—C8 | 121.7 (2) | C12—C16—H16B | 117.9 |
O2—C9—C10 | 120.3 (2) | C15—C16—H16B | 117.9 |
C8—C9—C10 | 117.8 (2) | H16A—C16—H16B | 115.0 |
C9—C10—C1—C2 | 4.8 (3) | Cl1—C10—C9—C8 | −153.1 (2) |
C11—C10—C1—C2 | −108.0 (3) | C9—C10—C11—C14 | 92.6 (3) |
Cl1—C10—C1—C2 | 136.8 (2) | C1—C10—C11—C14 | −149.6 (3) |
C9—C10—C1—C12 | 120.2 (2) | Cl1—C10—C11—C14 | −32.9 (4) |
C11—C10—C1—C12 | 7.35 (19) | C9—C10—C11—C13 | 14.6 (4) |
Cl1—C10—C1—C12 | −107.8 (2) | C1—C10—C11—C13 | 132.4 (3) |
C12—C1—C2—O1 | 84.7 (3) | Cl1—C10—C11—C13 | −110.9 (3) |
C10—C1—C2—O1 | −172.4 (3) | C9—C10—C11—C12 | −125.3 (2) |
C12—C1—C2—C3 | −90.1 (3) | C1—C10—C11—C12 | −7.50 (19) |
C10—C1—C2—C3 | 12.8 (4) | Cl1—C10—C11—C12 | 109.2 (2) |
O1—C2—C3—C4 | −10.2 (4) | C14—C11—C12—C15 | −69.7 (4) |
C1—C2—C3—C4 | 164.6 (3) | C13—C11—C12—C15 | 10.1 (5) |
O1—C2—C3—C8 | 168.4 (3) | C10—C11—C12—C15 | 149.5 (3) |
C1—C2—C3—C8 | −16.8 (4) | C14—C11—C12—C16 | 9.5 (5) |
C8—C3—C4—C5 | 0.9 (4) | C13—C11—C12—C16 | 89.4 (4) |
C2—C3—C4—C5 | 179.5 (3) | C10—C11—C12—C16 | −131.3 (3) |
C3—C4—C5—C6 | −1.5 (5) | C14—C11—C12—C1 | 148.4 (3) |
C4—C5—C6—C7 | 0.1 (5) | C13—C11—C12—C1 | −131.8 (3) |
C5—C6—C7—C8 | 2.0 (5) | C10—C11—C12—C1 | 7.58 (19) |
C6—C7—C8—C3 | −2.7 (4) | C2—C1—C12—C15 | −28.3 (4) |
C6—C7—C8—C9 | 178.0 (3) | C10—C1—C12—C15 | −150.4 (3) |
C4—C3—C8—C7 | 1.2 (4) | C2—C1—C12—C16 | −106.9 (3) |
C2—C3—C8—C7 | −177.4 (3) | C10—C1—C12—C16 | 131.0 (3) |
C4—C3—C8—C9 | −179.4 (2) | C2—C1—C12—C11 | 114.5 (2) |
C2—C3—C8—C9 | 2.0 (4) | C10—C1—C12—C11 | −7.60 (19) |
C7—C8—C9—O2 | 10.4 (4) | C12—C11—C13—C14 | −118.4 (3) |
C3—C8—C9—O2 | −168.9 (3) | C10—C11—C13—C14 | 115.8 (3) |
C7—C8—C9—C10 | −164.3 (3) | C12—C11—C14—C13 | 116.2 (4) |
C3—C8—C9—C10 | 16.4 (4) | C10—C11—C14—C13 | −115.7 (3) |
C1—C10—C9—O2 | 166.2 (3) | C11—C12—C15—C16 | 115.0 (4) |
C11—C10—C9—O2 | −95.0 (3) | C1—C12—C15—C16 | −115.8 (4) |
Cl1—C10—C9—O2 | 32.1 (3) | C11—C12—C16—C15 | −118.6 (4) |
C1—C10—C9—C8 | −19.0 (3) | C1—C12—C16—C15 | 116.7 (4) |
C11—C10—C9—C8 | 79.8 (3) |
Experimental details
Crystal data | |
Chemical formula | C16H13ClO2 |
Mr | 272.71 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 213 |
a, b, c (Å) | 8.2794 (2), 15.3344 (2), 10.2590 (2) |
β (°) | 96.639 (1) |
V (Å3) | 1293.74 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.34 × 0.34 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.934, 0.983 |
No. of measured, independent and observed [ > 2σ(I)'] reflections | 7752, 3140, 1736 |
Rint | 0.126 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.168, 0.93 |
No. of reflections | 3133 |
No. of parameters | 183 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.55 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
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Recently, we have carried out photo-induced electron transfer (PET) reactions of bicyclopropylidene with several quinones (Wang & Xu, 2002) giving dispiro[cyclopropane] derivatives. The crystal stucture of one these derivatives has been reported (Usman et al., 2002). With our continuing studies into these PET reactions, we have isolated the title compound, (I). An X-ray crystal structure analysis was undertaken to elucidate its configuration and conformation.
The bond lengths and angles in (I) (Fig. 1) agree with the corresponding values in related structures (Usman et al., 2002; Taira et al., 1993). The tetrahydrobenzene ring is out of planarity towards a boat conformation, as observed in the related structures. Atoms C2 and C9 are displaced from the C1/C3/C8/C10 plane by 0.167 (3) and 0.199 (3) Å, respectively, and the dihedral angle between the tetrahydrobenzene and benzene rings is 8.6 (1)°. The cyclobutane moiety (C1/C10—C12) is slightly out of planarity, with the atoms deviating from its mean plane by ±0.052 (3) Å; the dihedral angle between the C1/C10/C12 and C10/C11/C12 planes is 169.3 (2)°. The cyclobutane mean plane makes a dihedral angle of 74.1 (2)° with the tetrahydrobenzene ring.
The configurations of the two cyclopropyl rings (C11/C13/C14 and C12/C15/C16) with respect to the cyclobutane is determined by the C13—C11—C12—C15 and C14—C11—C12—C16 torsion angles [10.1 (5) and 9.5 (5)°, respectively], implying that atoms C11 and C12 are eclipsed. The two cyclopropyl rings are orthogonal to the cyclobutane ring, with dihedral angles of 89.2 (3) and 89.0 (3) Å.
The Cl atom shows positional disorder, bonded to C10 or C1 with populations of 86 and 14%, respectively.