Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the title compound, C16H12Cl2O2, the tetra­hydro­benzene ring adopts a boat conformation, and both cyclo­propyl groups are orthogonal to the cyclo­butane ring. The cyclo­butane and tetra­hydro­benzene rings share one C-C bond, and are folded about this bond relative to each other.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021785/lh6019sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021785/lh6019Isup2.hkl
Contains datablock I

CCDC reference: 202366

Key indicators

  • Single-crystal X-ray study
  • T = 213 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.078
  • wR factor = 0.199
  • Data-to-parameter ratio = 15.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Photoinduced electron transfer (PET) reactions of electron donor bicyclopropylidene and its derivatives have not been widely investigated. With our continuing studies into the PET reactions of electron rich compounds, we have carried out PET reactions of bicyclopropylidene with several quinones (Wang et al., 2002). In this study, we have isolated the title compound, (I), and undertaken its X-ray crystal structure analyses in order to elucidate its steric configuration and conformation.

The bond lengths and angles in (I) (Fig. 1) are within normal ranges (Allen et al., 1987). Those within the dioxotetrahydrocyclobuta[b]napthalene moiety (O1/O2/C1—C12) agree with the corresponding values in a related structure (Taira et al., 1993), except for the C1—C10 bond length [1.587 (3) Å]. which isslightly longer than the corresponding values in the related structure, mainly due to the repulsions of the lone pair electrons of the two attached chlorine substituents.

In (I), the tetrahydronaphtalene moiety (C1–C10) is not coplanar with the attached tetrahydrobenzene ring, being distorted slightly towards a boat conformation. Atoms C2 and C9 are displaced from the C1/C3/C8/C10 plane by 0.339 (2) and 0.202 (2) Å, respectively, and the dihedral angle between the tetrahydrobenzene and benzene rings is 9.5 (1)°.

The cyclobutane moiety (C1/C10–C12) is slightly out of planarity, with the atoms deviating from its mean plane by ±0.042 (3); the dihedral angle of the C1/C10/C12 and C10/C11/C12 planes is 171.2 (2)°. The cyclobutane mean plane makes a dihedral angle of 78.7 (1)° with the tetrahydrobenzene ring, which is conditioned by the sp3 states of the shared C1 and C10 atoms.

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 [both are 9.2 (2)°], implying that atoms C11 and C12 are eclipsed. The Cl1—C1—C10—Cl2 torsion angle is 9.1 (2)°, also indicating an eclipsed configuration around atoms C1 and C10. The two cyclopropyl rings are orthogonal to the cyclobutane ring, with dihedral angles of 89.4 (2) and 89.5 (2)°. In the crystal, molecules are linked into extended chains by weak intermolecular C—H···O hydrogen bonds, via unit-cell translations in the a direction (see Fig. 2 and Table 2).

Experimental top

The title compound was prepared by photoinduced reactions of 2,3-dichloronaphto-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 (15:1 v/v) solution.

Refinement top

The H atoms were fixed geometrically and treated as riding on the parent C atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS; 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, 1990).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of compound (I), showing extended chains in the a direction. Dashed lines denote C—H···O intermolecular interactions.
2a',8a'-Dichloro-3,8-dioxo-1',2',2a',8a'-tetrahydrodispiro[cyclopropane- 1,1'- cyclobuta[b]napthalene-2',1"-cyclopropane] top
Crystal data top
C16H12Cl2O2Z = 2
Mr = 307.16F(000) = 316
Triclinic, P1Dx = 1.551 Mg m3
Hall symbol: -P 1Melting point: 432(1) K
a = 7.2430 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.0455 (2) ÅCell parameters from 3828 reflections
c = 10.0831 (2) Åθ = 3.1–28.3°
α = 85.47°µ = 0.49 mm1
β = 73.306 (1)°T = 213 K
γ = 69.401 (1)°Block, colorless
V = 657.59 (2) Å30.50 × 0.46 × 0.40 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
2753 independent reflections
Radiation source: fine-focus sealed tube2464 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: 8.33 pixels mm-1θmax = 27.0°, θmin = 3.1°
ω scansh = 89
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1211
Tmin = 0.792, Tmax = 0.828l = 1212
3750 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.199 w = 1/[σ2(Fo2) + (0.125P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2753 reflectionsΔρmax = 0.97 e Å3
182 parametersΔρmin = 1.22 e Å3
0 restraintsExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.68 (5)
Crystal data top
C16H12Cl2O2γ = 69.401 (1)°
Mr = 307.16V = 657.59 (2) Å3
Triclinic, P1Z = 2
a = 7.2430 (1) ÅMo Kα radiation
b = 10.0455 (2) ŵ = 0.49 mm1
c = 10.0831 (2) ÅT = 213 K
α = 85.47°0.50 × 0.46 × 0.40 mm
β = 73.306 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
2753 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2464 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.828Rint = 0.066
3750 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0780 restraints
wR(F2) = 0.199H-atom parameters constrained
S = 1.07Δρmax = 0.97 e Å3
2753 reflectionsΔρmin = 1.22 e Å3
182 parameters
Special details top

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 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.31434 (9)0.53664 (6)0.65750 (6)0.0284 (3)
Cl20.16104 (9)0.62238 (6)0.71342 (6)0.0275 (3)
O10.4263 (3)0.7817 (2)0.55929 (18)0.0274 (5)
O20.3803 (3)0.9268 (2)0.7387 (2)0.0279 (5)
C10.1680 (3)0.7113 (2)0.7254 (2)0.0158 (5)
C20.2534 (3)0.8177 (2)0.6358 (2)0.0170 (5)
C30.1157 (3)0.9690 (2)0.6523 (2)0.0163 (5)
C40.2023 (4)1.0760 (3)0.6184 (2)0.0225 (5)
H40.34431.05190.59160.027*
C50.0775 (5)1.2176 (3)0.6247 (3)0.0275 (6)
H50.13581.28830.60390.033*
C60.1353 (4)1.2540 (3)0.6622 (3)0.0280 (6)
H60.21851.34890.66370.034*
C70.2237 (4)1.1492 (3)0.6975 (2)0.0222 (5)
H70.36581.17400.72310.027*
C80.0991 (3)1.0066 (2)0.6943 (2)0.0159 (5)
C90.1990 (3)0.8973 (2)0.7288 (2)0.0165 (5)
C100.0734 (3)0.7485 (2)0.7655 (2)0.0147 (5)
C110.0781 (3)0.7471 (2)0.9195 (2)0.0159 (5)
C120.1463 (3)0.7288 (2)0.8804 (2)0.0161 (5)
C130.2507 (4)0.8345 (3)1.0358 (2)0.0264 (6)
H13A0.37880.89041.01570.032*
H13B0.21570.87741.10360.032*
C140.1908 (4)0.6749 (3)1.0331 (2)0.0251 (6)
H14B0.11990.62201.09930.030*
H14A0.28300.63501.01140.030*
C150.2465 (4)0.8102 (3)0.9380 (3)0.0276 (6)
H15A0.16400.87201.01840.033*
H15B0.34740.84390.87300.033*
C160.3007 (4)0.6517 (3)0.9566 (3)0.0271 (6)
H16B0.43440.59040.90300.033*
H16A0.25110.61851.04840.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0235 (4)0.0179 (4)0.0309 (4)0.0011 (3)0.0030 (3)0.0049 (3)
Cl20.0297 (4)0.0260 (4)0.0334 (5)0.0161 (3)0.0094 (3)0.0035 (3)
O10.0144 (8)0.0348 (10)0.0265 (9)0.0061 (7)0.0000 (7)0.0049 (7)
O20.0138 (9)0.0327 (10)0.0380 (10)0.0075 (7)0.0110 (7)0.0079 (8)
C10.0112 (9)0.0132 (10)0.0181 (10)0.0001 (8)0.0017 (8)0.0012 (8)
C20.0131 (10)0.0233 (12)0.0152 (10)0.0056 (9)0.0064 (8)0.0036 (8)
C30.0166 (10)0.0201 (11)0.0134 (10)0.0070 (9)0.0062 (8)0.0043 (8)
C40.0248 (12)0.0277 (13)0.0203 (11)0.0143 (10)0.0092 (9)0.0061 (9)
C50.0411 (15)0.0241 (12)0.0262 (12)0.0193 (11)0.0148 (11)0.0076 (9)
C60.0391 (15)0.0151 (11)0.0309 (13)0.0056 (10)0.0170 (11)0.0036 (9)
C70.0222 (11)0.0190 (11)0.0237 (12)0.0023 (9)0.0099 (9)0.0014 (9)
C80.0166 (10)0.0187 (11)0.0127 (10)0.0051 (9)0.0065 (8)0.0029 (8)
C90.0142 (10)0.0203 (11)0.0145 (10)0.0046 (9)0.0052 (8)0.0018 (8)
C100.0137 (10)0.0157 (10)0.0158 (10)0.0060 (8)0.0046 (8)0.0004 (8)
C110.0152 (10)0.0162 (10)0.0152 (10)0.0045 (8)0.0042 (8)0.0026 (8)
C120.0124 (10)0.0179 (11)0.0167 (10)0.0035 (8)0.0048 (8)0.0033 (8)
C130.0211 (12)0.0278 (13)0.0197 (11)0.0003 (10)0.0007 (9)0.0007 (9)
C140.0232 (12)0.0273 (13)0.0204 (11)0.0091 (10)0.0006 (9)0.0072 (9)
C150.0301 (13)0.0341 (14)0.0273 (12)0.0175 (11)0.0147 (10)0.0062 (10)
C160.0213 (12)0.0328 (14)0.0266 (12)0.0058 (10)0.0129 (10)0.0111 (10)
Geometric parameters (Å, º) top
Cl1—C11.770 (2)C8—C91.484 (3)
Cl2—C101.773 (2)C9—C101.532 (3)
O1—C21.210 (3)C10—C111.542 (3)
O2—C91.216 (3)C11—C141.501 (3)
C1—C21.528 (3)C11—C131.503 (3)
C1—C121.543 (3)C11—C121.505 (3)
C1—C101.587 (3)C12—C161.494 (3)
C2—C31.487 (3)C12—C151.505 (3)
C3—C41.399 (3)C13—C141.507 (4)
C3—C81.406 (3)C13—H13A0.9700
C4—C51.386 (4)C13—H13B0.9700
C4—H40.9300C14—H14B0.9700
C5—C61.394 (4)C14—H14A0.9700
C5—H50.9300C15—C161.510 (4)
C6—C71.389 (4)C15—H15A0.9700
C6—H60.9300C15—H15B0.9700
C7—C81.396 (3)C16—H16B0.9700
C7—H70.9300C16—H16A0.9700
C2—C1—C12112.53 (17)C14—C11—C1360.24 (16)
C2—C1—C10116.73 (17)C14—C11—C12127.45 (19)
C12—C1—C1087.88 (15)C13—C11—C12129.1 (2)
C2—C1—Cl1109.73 (15)C14—C11—C10126.07 (19)
C12—C1—Cl1113.80 (15)C13—C11—C10126.69 (19)
C10—C1—Cl1114.76 (15)C12—C11—C1090.93 (16)
O1—C2—C3121.7 (2)C16—C12—C11128.12 (19)
O1—C2—C1121.9 (2)C16—C12—C1560.48 (16)
C3—C2—C1116.33 (18)C11—C12—C15127.4 (2)
C4—C3—C8119.4 (2)C16—C12—C1126.87 (19)
C4—C3—C2119.0 (2)C11—C12—C191.77 (16)
C8—C3—C2121.48 (19)C15—C12—C1125.41 (18)
C5—C4—C3120.3 (2)C11—C13—C1459.83 (15)
C5—C4—H4119.8C11—C13—H13A117.8
C3—C4—H4119.8C14—C13—H13A117.8
C4—C5—C6120.1 (2)C11—C13—H13B117.8
C4—C5—H5119.9C14—C13—H13B117.8
C6—C5—H5119.9H13A—C13—H13B114.9
C7—C6—C5120.3 (2)C11—C14—C1359.94 (15)
C7—C6—H6119.9C11—C14—H14B117.8
C5—C6—H6119.9C13—C14—H14B117.8
C6—C7—C8119.9 (2)C11—C14—H14A117.8
C6—C7—H7120.0C13—C14—H14A117.8
C8—C7—H7120.0H14B—C14—H14A114.9
C7—C8—C3119.9 (2)C12—C15—C1659.38 (15)
C7—C8—C9118.4 (2)C12—C15—H15A117.8
C3—C8—C9121.6 (2)C16—C15—H15A117.8
O2—C9—C8121.3 (2)C12—C15—H15B117.8
O2—C9—C10120.0 (2)C16—C15—H15B117.8
C8—C9—C10118.42 (18)H15A—C15—H15B115.0
C9—C10—C11109.66 (16)C12—C16—C1560.14 (15)
C9—C10—C1116.29 (17)C12—C16—H16B117.8
C11—C10—C188.75 (15)C15—C16—H16B117.8
C9—C10—Cl2108.72 (14)C12—C16—H16A117.8
C11—C10—Cl2115.80 (14)C15—C16—H16A117.8
C1—C10—Cl2116.46 (14)H16B—C16—H16A114.9
C12—C1—C2—O1107.8 (2)C12—C1—C10—Cl2124.42 (15)
C10—C1—C2—O1152.7 (2)Cl1—C1—C10—Cl29.1 (2)
Cl1—C1—C2—O120.0 (3)C9—C10—C11—C14108.8 (2)
C12—C1—C2—C369.6 (2)C1—C10—C11—C14133.7 (2)
C10—C1—C2—C329.9 (3)Cl2—C10—C11—C1414.7 (3)
Cl1—C1—C2—C3162.62 (15)C9—C10—C11—C1331.7 (3)
O1—C2—C3—C421.8 (3)C1—C10—C11—C13149.2 (2)
C1—C2—C3—C4155.62 (19)Cl2—C10—C11—C1391.8 (2)
O1—C2—C3—C8155.0 (2)C9—C10—C11—C12111.39 (18)
C1—C2—C3—C827.6 (3)C1—C10—C11—C126.17 (16)
C8—C3—C4—C50.8 (3)Cl2—C10—C11—C12125.15 (15)
C2—C3—C4—C5176.1 (2)C14—C11—C12—C169.3 (4)
C3—C4—C5—C61.3 (4)C13—C11—C12—C1670.1 (3)
C4—C5—C6—C71.9 (4)C10—C11—C12—C16148.3 (2)
C5—C6—C7—C80.5 (4)C14—C11—C12—C1588.5 (3)
C6—C7—C8—C31.5 (3)C13—C11—C12—C159.0 (4)
C6—C7—C8—C9178.3 (2)C10—C11—C12—C15132.6 (2)
C4—C3—C8—C72.1 (3)C14—C11—C12—C1132.6 (2)
C2—C3—C8—C7174.62 (19)C13—C11—C12—C1147.9 (2)
C4—C3—C8—C9178.86 (19)C10—C11—C12—C16.35 (16)
C2—C3—C8—C92.1 (3)C2—C1—C12—C1693.0 (3)
C7—C8—C9—O211.3 (3)C10—C1—C12—C16148.9 (2)
C3—C8—C9—O2165.5 (2)Cl1—C1—C12—C1632.6 (3)
C7—C8—C9—C10163.04 (19)C2—C1—C12—C11124.34 (18)
C3—C8—C9—C1020.2 (3)C10—C1—C12—C116.17 (16)
O2—C9—C10—C1191.4 (2)Cl1—C1—C12—C11110.04 (16)
C8—C9—C10—C1183.0 (2)C2—C1—C12—C1515.8 (3)
O2—C9—C10—C1169.9 (2)C10—C1—C12—C15134.0 (2)
C8—C9—C10—C115.7 (3)Cl1—C1—C12—C15109.8 (2)
O2—C9—C10—Cl236.1 (2)C12—C11—C13—C14116.0 (3)
C8—C9—C10—Cl2149.46 (16)C10—C11—C13—C14114.8 (2)
C2—C1—C10—C98.9 (3)C12—C11—C14—C13118.5 (3)
C12—C1—C10—C9105.36 (18)C10—C11—C14—C13115.8 (2)
Cl1—C1—C10—C9139.33 (16)C11—C12—C15—C16117.4 (3)
C2—C1—C10—C11120.27 (19)C1—C12—C15—C16116.3 (2)
C12—C1—C10—C116.02 (15)C11—C12—C16—C15116.3 (3)
Cl1—C1—C10—C11109.29 (15)C1—C12—C16—C15114.1 (2)
C2—C1—C10—Cl2121.34 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O2i0.972.423.384 (4)172
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC16H12Cl2O2
Mr307.16
Crystal system, space groupTriclinic, P1
Temperature (K)213
a, b, c (Å)7.2430 (1), 10.0455 (2), 10.0831 (2)
α, β, γ (°)85.47, 73.306 (1), 69.401 (1)
V3)657.59 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.50 × 0.46 × 0.40
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.792, 0.828
No. of measured, independent and
observed [I > 2σ(I)] reflections
3750, 2753, 2464
Rint0.066
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.078, 0.199, 1.07
No. of reflections2753
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.97, 1.22

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT and SADABS, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected bond lengths (Å) top
C1—C121.543 (3)C11—C121.505 (3)
C10—C111.542 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C15—H15B···O2i0.972.423.384 (4)172
Symmetry code: (i) x+1, y, z.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds