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(1RS,3RS,4RS,10SR)-2,2,3,10-Tetra­bromo-1,2,3,4-tetra­hydro-1,4-ethano­naphthalene, C12H10Br4, (I), is the first structure to be reported with four Br atoms bound to a 1,4-ethano­naphthalene framework and also the first which possesses three Br atoms in exo positions. Inter­actions between the Br atoms [three short intra­molecular Br...Br distances of 3.1094 (4), 3.2669 (4) and 3.4415 (5) Å] have little effect on the C—C bond lengths but lead to significant twisting of the cage structure compared with the parent hydro­carbon, which is expected to be fully eclipsed at the two saturated C2H4 bridge positions. Chemically related (1SR,4RS)-2,3-dibromo-1,4-etheno­naphthalene, C12H8Br2, (II), obtained by double dehydro­bromination of (I), represents the first structure of any halogen-substituted benzobarrelene. This cis-dibromide shows little evidence of steric congestion at the double bond [Br...Br = 3.5276 (8) Å] as a consequence of the large C—C—Br angles [average C=C—Br angle = 126.15 (10)°].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011300231X/gz3227sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011300231X/gz3227Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011300231X/gz3227IIsup3.hkl
Contains datablock II

CCDC references: 934559; 934560

Comment top

We recently reported the crystal and molecular structure of the useful intermediate 3,4-dibromo-6,7-benzobicyclo[3.2.1]octa-2,6-diene, (III) (Johnson et al., 2011) (Scheme 1). We report here on two related structures which provide access to a variety of substituted benzobarrelenes (Çakmak & Balcı, 1989; Bender et al., 2003). Compound (I) (Fig. 1) is formed by the addition of bromine to (III) and is the direct precursor, by double dehydrobromination, of the extremely useful compound (II) (Fig. 2). We have used (II), inter alia, in the preparation of specifically labelled deuterated species such as 2-bromo-3-deuteriobenzobarrelene (Bender et al., 2003).

The crystal structure of (I) is the first reported for any tetrabromo derivative of the 1,2,3,4-tetrahydro-1,4-ethanonaphthalene framework. Structures are known for two tribromides, (1RS,4SR,10SR)-2,2,10-tribromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (IV) [Cambridge Structural Database (CSD; Allen, 2002) refcode FOMREE (Ergin et al., 1987)] (Scheme 2) and (1RS,3SR,4SR)-2,2,3-tribromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (V) (refcode KAKVEZ; Eşsiz et al., 2011). Thus, (IV) lacks the Br at position 3, whilst (V) lacks that at position 10 compared with (I). Note that both of the variable Br-atom locations are in the exo position.

There are two reported structures for pentabromide isomers, (1SR,3RS,4RS,9SR,10RS)-2,2,3,9,10-pentabromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (VI) (refcode MOCWUW; Ülkü et al., 2002) and (1SR,3SR,4RS,9SR,10RS)-2,2,3,9,10-pentabromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (VII) (refcode TAFXIH; Hökelek et al., 1990). The latter two differ, respectively, in the endo versus exo orientation of the Br atom at position 3. The geometry of the parent hydrocarbon framework without substituents on the bicyclic cage is available in 5,8-diacetoxy-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (VIII) (refcode EDAGUM; Goh et al., 2007), and in the structure of a cocrystal of 5,6,7,8-tetramethyl-1,2,3,4-tetrahydro-1,4-ethanonaphthalene, (IX) (refcode PAWDIA; Rathore et al., 1998). In (IV)–(IX), the two single bonds attached to benzene [equivalent to C1—C2 and C7—C8 in (I)] average 1.505 (9) Å, a value not statistically different from the average value in (I) of 1.517 (6) Å. However, these bonds appear shorter than the remaining cage bonds at the 95% confidence level; the latter have a mean value in (IV)–(IX) of 1.544 (10) Å, once the lowest outliers in Fig. 3 are omitted. The mean value for these bonds in (I) of 1.545 (5) Å represents a very good match. Over all seven structures, there appears to be a slight trend towards longer C—C distances for those bonds substituted with two Br atoms at one end and one Br atom at the other, which average 1.558 (9) Å, but the difference from the distribution shown in Fig. 3 is not statistically significant for this sample.

If the conformation around the boat cyclohexane ring (atoms C1, C10, C9, C8, C12 and C11) is considered, (I) is the most distorted of this comparison set from the essentially pure boat conformations observed in (VIII) and (XI) [even though (VI) and (VII) are pentabromides]. This may be a consequence of it being the only example with three exo Br atoms, arranged in an 1,2,4 all-axial substitution pattern around this saturated six-membered ring. Thus, the torsion angles at the ethane bridges of 18.8 (2) (Br1—C9—C10—Br2) and 35.3 (2)° (Br4—C11—C12—H12A) in (I) are considerably larger than in the comparison set. Visually, this ring is also distorted in (IV). A Cremer & Pople conformational analysis (Cremer & Pople, 1975) for (I), undertaken using PLATON (Spek, 2009), results in puckering parameters of Q = 0.829 (3) Å, θ = 92.8 (2)° and ϕ = 19.24 (19)° for the C1/C10/C9/C8/C12/C11 ring, whereas for (IV), Q = 0.823 (16) Å, θ = 94.3(s.u.?)° and ϕ = 7.4 (11)° for the C10/C12/C11/C7/C8/C9 ring. Thus, the conformation in (I) is intermediate but closer to the twist-boat limit (ϕ = 0° for boat and 30° for twisted), whereas that in (IV) is much closer to boat.

The molecules of (I) lack any symmetry and stack along the a axis of the unit cell, with short Br3···C4ii contacts of 3.430 (3) Å. However, the strongest interaction is probably between atom Br3 and the benzene ring centroid [3.332 (3) Å] (see Fig. 4 for symmetry code).

To date, no crystal structures have been reported for any derivatives of a mono-fused bicyclo[2.2.2]octa-1(7),4(8),5-triene (i.e. a benzobarrelene) bearing halogen substituents on the framework atoms. Indeed, a search of the CSD (WebCSD December 2012) returned only seven structures for this class of compound (excluding metal complexes). Of these, the examples with electron-withdrawing substituents that might be most comparable with (II) are methyl 2-benzoyl-1,4-dihydro-1,4-ethenonaphthalene-3-carboxylate, (X) (refcode LEKLAO; Pokkuluri, Scheffer, Trotter & Yap, 1994), dimethyl 7,8-benzobicyclo[2.2.2]octa-2,5,7-triene-2,3-dicarboxylate, (XI) (refcode SATPUY; Trotter, 1989), and dimethyl 9-phenyl-1,4-dihydro-1,4-ethenoanthracene-11,12-dicarboxylate, (XII) (refcode WEJBOC; Pokkuluri, Scheffer, & Trotter, 1994). In this sample of four structures, the single bonds of the barrelenes are indistinguishable, with an average length of 1.526 (9) Å. Interestingly, for the nonfused CC bonds, those in (II) fit best with the `unsubstituted' analogues, at an average distance of 1.315 (4) Å, whereas the CC bonds bearing the ester or ketone substituents in (X)–(XII) are longer at an average of 1.337 (6) Å, suggesting that in these cases there is steric congestion resulting from the 1,2-substitution of the carbonyl groups. And yet the Br atoms in (II) seem to cause little crowding; the intramolecular Br1···Br2 contact distance is 3.5276 (8) Å, only marginally less than the sums of their van der Waals radii [Standard reference?]. Whilst it is true that the C10—C9—Br1 [126.50 (14)°] and C9—C10—Br2 [125.79 (14)°] angles are wide, this is just as likely to be a consequence of the pinching of the interior angles at atoms C9 and C10 by the bicyclic cage geometry as to be due to steric pressure between the Br atoms.

Molecules of (II) possess approximate point symmetry m. Short intermolecular Br2···C6i contacts [3.512 (2) Å] link them into a zigzag chain parallel to the crystallographic b axis (see Fig. 5 for symmetry codes). Here too, just as in (I), the strongest interaction is between Br and neighbouring benzene ring centroids, at 3.480 (3) Å.

Related literature top

For related literature, see: Allen (2002); Bender et al. (2003); Cremer & Pople (1975); Eşsiz et al. (2011); Ergin et al. (1987); Goh et al. (2007); Hökelek et al. (1990); Johnson et al. (2011); Kitahonoki et al. (1969); Pokkuluri, Scheffer & Trotter (1994); Pokkuluri, Scheffer, Trotter & Yap (1994); Rathore et al. (1998); Spek (2009); Trotter (1989); Ülkü et al. (2002); Çakmak & Balcı (1989).

Experimental top

Tetrabromide (I) was readily prepared by the addition of bromine to (III) at 253 K, accompanied by a rearrangement of the hydrocarbon cage, as shown in Scheme 1 (Kitahonoki et al., 1969; Johnson et al., 2011). Recrystallization of the reaction mixture from chloroform–hexane [Solvent ratio?] gave colourless rod-shaped [Block in CIF tables - please clarify] crystals of (I) (yield 54%, m.p. 418–419 K). Dibromide (II) was prepared by the double dehydrobromination of (I), according to the method of Çakmak & Balcı (1989) (yield > 80%, m.p. 344–345 K). [Recrystallization details?]

Refinement top

C-bound H atoms were treated as riding, with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene, C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C) for methine, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for vinyl and aromatic H atoms. No data were rejected for (I), but three intense reflections and one inconsistent equivalent in the data set of (II) were omitted from the refinement. The largest peak and hole in the final difference maps approach the equivalent electron density of an H atom but are located less than 1 Å from Br atoms.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The crystal is a racemate; the displayed molecule has the following stereochemical centres: C1 R, C8 R, C9 R and C11 S.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The crystal is a racemate; the displayed molecule has the following stereochemical centres: C1 S and C8 R.
[Figure 3] Fig. 3. The bond-length distribution for cage C—C bonds other than those attached to benzene rings in (IV)–(IX). The corresponding mean value in (I) is 1.545 (5) Å.
[Figure 4] Fig. 4. Short intermolecular Br3···C4 and Br3···benzene ring centroid contacts linking the molecules of (I) in a straight chain parallel to the crystallographic a axis. Ring centroids are indicated by large spheres and thin black lines denote the interactions. [Symmetry codes: (i) x - 1, y, z; (ii) x + 1, y, z.] [Should there also be lines actually to the centroids as well?]
[Figure 5] Fig. 5. Short intermolecular Br2···C6 and Br2···benzene ring centroid contacts linking the molecules of (II) in a zigzag chain parallel to the crystallographic a axis. Ring centroids are indicated by large spheres and dashed lines denote the interactions. [Symmetry codes: (i) -x + 3/2, y - 1/2, -z + 3/2; (ii) -x + 3/2, y + 1/2, -z + 3/2; (iii) x, y + 1, z.] [Should there also be lines actually to the centroids as well?]
(I) (1RS,3RS,4RS,10SR)-2,2,3,10-Tetrabromo-1,2,3,4-tetrahydro-1,4-ethanonaphthalene top
Crystal data top
C12H10Br4Z = 2
Mr = 473.84F(000) = 444
Triclinic, P1Dx = 2.412 Mg m3
Hall symbol: -P 1Melting point: 418 K
a = 6.9532 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.4323 (5) ÅCell parameters from 6183 reflections
c = 11.9669 (7) Åθ = 2.6–28.3°
α = 94.706 (1)°µ = 12.31 mm1
β = 91.257 (1)°T = 173 K
γ = 110.892 (1)°Block, colourless
V = 652.31 (7) Å30.45 × 0.27 × 0.27 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3074 independent reflections
Radiation source: fine-focus sealed tube, Bruker D82835 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 66.06 pixels mm-1θmax = 28.3°, θmin = 1.7°
ϕ and ω scansh = 99
Absorption correction: numerical
(SADABS; Bruker, 2008)
k = 1011
Tmin = 0.052, Tmax = 0.144l = 1515
7682 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)] = 0.022H-atom parameters constrained
wR(F2) = 0.055 w = 1/[σ2(Fo2) + (0.0202P)2 + 0.8639P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3074 reflectionsΔρmax = 0.78 e Å3
146 parametersΔρmin = 0.78 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0097 (6)
Crystal data top
C12H10Br4γ = 110.892 (1)°
Mr = 473.84V = 652.31 (7) Å3
Triclinic, P1Z = 2
a = 6.9532 (4) ÅMo Kα radiation
b = 8.4323 (5) ŵ = 12.31 mm1
c = 11.9669 (7) ÅT = 173 K
α = 94.706 (1)°0.45 × 0.27 × 0.27 mm
β = 91.257 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3074 independent reflections
Absorption correction: numerical
(SADABS; Bruker, 2008)
2835 reflections with I > 2σ(I)
Tmin = 0.052, Tmax = 0.144Rint = 0.024
7682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.05Δρmax = 0.78 e Å3
3074 reflectionsΔρmin = 0.78 e Å3
146 parameters
Special details top

Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass capillary and cooled in the gas stream of the diffractometer Kryoflex device. On consideration of the large absorption coefficient, a face-indexed numerical absorption correction was undertaken using SADABS software.

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
Br10.89779 (5)0.17616 (4)0.04487 (2)0.03611 (9)
Br21.08266 (4)0.55118 (3)0.18715 (2)0.02900 (8)
Br31.03300 (4)0.31408 (4)0.37875 (2)0.02923 (8)
Br40.70724 (4)0.72876 (3)0.18717 (2)0.03075 (9)
C10.7185 (3)0.4386 (3)0.3143 (2)0.0182 (4)
H10.78360.53210.37560.022*
C20.5540 (4)0.2863 (3)0.3576 (2)0.0199 (5)
C30.4997 (4)0.2671 (3)0.4675 (2)0.0249 (5)
H30.57040.35280.52600.030*
C40.3393 (4)0.1196 (4)0.4913 (2)0.0313 (6)
H40.30120.10470.56660.038*
C50.2358 (4)0.0045 (4)0.4063 (3)0.0327 (6)
H50.12650.10380.42350.039*
C60.2899 (4)0.0143 (3)0.2960 (3)0.0300 (6)
H60.21840.07160.23780.036*
C70.4492 (4)0.1597 (3)0.2715 (2)0.0220 (5)
C80.5393 (4)0.1937 (3)0.1582 (2)0.0223 (5)
H80.46600.09730.10010.027*
C90.7635 (4)0.2064 (3)0.1817 (2)0.0214 (5)
H90.75620.10920.22610.026*
C100.8784 (3)0.3726 (3)0.2598 (2)0.0188 (4)
C110.5907 (4)0.4919 (3)0.2267 (2)0.0202 (5)
H110.45720.48020.26120.024*
C120.5356 (4)0.3639 (3)0.1222 (2)0.0248 (5)
H12A0.63670.40550.06450.030*
H12B0.39690.34840.09020.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03552 (16)0.04056 (17)0.03069 (16)0.01369 (13)0.01088 (11)0.00776 (11)
Br20.02253 (13)0.02120 (13)0.04350 (17)0.00627 (10)0.01178 (11)0.00922 (10)
Br30.02532 (14)0.03823 (16)0.02935 (15)0.01712 (11)0.00090 (10)0.00695 (11)
Br40.03562 (16)0.02153 (13)0.03915 (16)0.01381 (11)0.00586 (11)0.00839 (10)
C10.0176 (10)0.0165 (10)0.0201 (11)0.0063 (9)0.0001 (8)0.0004 (8)
C20.0174 (11)0.0204 (11)0.0232 (12)0.0081 (9)0.0031 (9)0.0037 (9)
C30.0258 (12)0.0301 (13)0.0229 (12)0.0147 (11)0.0020 (10)0.0031 (10)
C40.0290 (13)0.0399 (15)0.0321 (14)0.0175 (12)0.0108 (11)0.0179 (12)
C50.0255 (13)0.0269 (13)0.0485 (17)0.0094 (11)0.0132 (12)0.0166 (12)
C60.0233 (12)0.0203 (12)0.0433 (16)0.0039 (10)0.0042 (11)0.0034 (11)
C70.0192 (11)0.0187 (11)0.0276 (13)0.0061 (9)0.0042 (9)0.0020 (9)
C80.0206 (11)0.0212 (11)0.0215 (12)0.0041 (9)0.0006 (9)0.0030 (9)
C90.0242 (12)0.0189 (11)0.0211 (11)0.0077 (9)0.0054 (9)0.0003 (9)
C100.0157 (10)0.0196 (11)0.0210 (11)0.0061 (9)0.0018 (8)0.0032 (9)
C110.0176 (11)0.0187 (11)0.0243 (12)0.0062 (9)0.0001 (9)0.0034 (9)
C120.0227 (12)0.0280 (13)0.0224 (12)0.0080 (10)0.0030 (9)0.0010 (10)
Geometric parameters (Å, º) top
Br1—C91.946 (2)C5—C61.386 (4)
Br2—C101.945 (2)C5—H50.9500
Br3—C101.963 (2)C6—C71.386 (4)
Br4—C111.972 (2)C6—H60.9500
C1—C21.521 (3)C7—C81.512 (3)
C1—C101.544 (3)C8—C121.540 (4)
C1—C111.553 (3)C8—C91.542 (3)
C1—H11.0000C8—H81.0000
C2—C31.383 (3)C9—C101.558 (3)
C2—C71.401 (3)C9—H91.0000
C3—C41.398 (4)C11—C121.529 (3)
C3—H30.9500C11—H111.0000
C4—C51.380 (4)C12—H12A0.9900
C4—H40.9500C12—H12B0.9900
C2—C1—C10106.98 (18)C7—C8—H8111.1
C2—C1—C11101.56 (18)C12—C8—H8111.1
C10—C1—C11112.57 (19)C9—C8—H8111.1
C2—C1—H1111.7C8—C9—C10108.73 (19)
C10—C1—H1111.7C8—C9—Br1112.40 (16)
C11—C1—H1111.7C10—C9—Br1115.76 (16)
C3—C2—C7120.3 (2)C8—C9—H9106.4
C3—C2—C1127.0 (2)C10—C9—H9106.4
C7—C2—C1112.6 (2)Br1—C9—H9106.4
C2—C3—C4119.0 (2)C1—C10—C9109.21 (19)
C2—C3—H3120.5C1—C10—Br2110.96 (16)
C4—C3—H3120.5C9—C10—Br2114.66 (16)
C5—C4—C3120.5 (3)C1—C10—Br3108.67 (16)
C5—C4—H4119.8C9—C10—Br3107.65 (16)
C3—C4—H4119.8Br2—C10—Br3105.43 (11)
C4—C5—C6120.7 (3)C12—C11—C1109.83 (19)
C4—C5—H5119.7C12—C11—Br4111.59 (16)
C6—C5—H5119.7C1—C11—Br4116.66 (16)
C7—C6—C5119.4 (3)C12—C11—H11106.0
C7—C6—H6120.3C1—C11—H11106.0
C5—C6—H6120.3Br4—C11—H11106.0
C6—C7—C2120.1 (2)C11—C12—C8107.5 (2)
C6—C7—C8126.1 (2)C11—C12—H12A110.2
C2—C7—C8113.5 (2)C8—C12—H12A110.2
C7—C8—C12111.0 (2)C11—C12—H12B110.2
C7—C8—C9102.1 (2)C8—C12—H12B110.2
C12—C8—C9110.2 (2)H12A—C12—H12B108.5
C10—C1—C2—C3119.7 (3)C12—C8—C9—Br180.7 (2)
C11—C1—C2—C3122.1 (3)C2—C1—C10—C946.8 (2)
C10—C1—C2—C762.3 (3)C11—C1—C10—C964.0 (2)
C11—C1—C2—C755.9 (2)C2—C1—C10—Br2174.12 (15)
C7—C2—C3—C40.1 (4)C11—C1—C10—Br263.4 (2)
C1—C2—C3—C4178.0 (2)C2—C1—C10—Br370.40 (19)
C2—C3—C4—C50.4 (4)C11—C1—C10—Br3178.88 (15)
C3—C4—C5—C60.4 (4)C8—C9—C10—C116.4 (3)
C4—C5—C6—C70.2 (4)Br1—C9—C10—C1144.07 (17)
C5—C6—C7—C20.1 (4)C8—C9—C10—Br2108.78 (19)
C5—C6—C7—C8174.5 (3)Br1—C9—C10—Br218.8 (2)
C3—C2—C7—C60.1 (4)C8—C9—C10—Br3134.26 (17)
C1—C2—C7—C6178.0 (2)Br1—C9—C10—Br398.12 (16)
C3—C2—C7—C8175.1 (2)C2—C1—C11—C1273.6 (2)
C1—C2—C7—C86.7 (3)C10—C1—C11—C1240.5 (3)
C6—C7—C8—C12125.7 (3)C2—C1—C11—Br4158.19 (16)
C2—C7—C8—C1259.5 (3)C10—C1—C11—Br487.7 (2)
C6—C7—C8—C9116.9 (3)C1—C11—C12—C824.5 (3)
C2—C7—C8—C958.0 (3)Br4—C11—C12—C8155.47 (16)
C7—C8—C9—C1069.2 (2)C7—C8—C12—C1139.3 (3)
C12—C8—C9—C1048.8 (3)C9—C8—C12—C1173.1 (2)
C7—C8—C9—Br1161.26 (16)
(II) (1SR,4RS)-2,3-dibromo-1,4-ethenonaphthalene top
Crystal data top
C12H8Br2F(000) = 600
Mr = 312.00Dx = 1.990 Mg m3
Monoclinic, P21/nMelting point: 344 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.520 (3) ÅCell parameters from 8250 reflections
b = 6.5032 (18) Åθ = 2.3–28.7°
c = 17.124 (5) ŵ = 7.74 mm1
β = 100.826 (3)°T = 173 K
V = 1041.3 (5) Å3Block, colourless
Z = 40.21 × 0.16 × 0.15 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2378 independent reflections
Radiation source: fine-focus sealed tube, Bruker D82076 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Detector resolution: 66.06 pixels mm-1θmax = 27.5°, θmin = 2.3°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
k = 88
Tmin = 0.291, Tmax = 0.384l = 2222
14301 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)] = 0.020H-atom parameters constrained
wR(F2) = 0.049 w = 1/[σ2(Fo2) + (0.0201P)2 + 0.702P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
2378 reflectionsΔρmax = 0.51 e Å3
128 parametersΔρmin = 0.35 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0122 (5)
Crystal data top
C12H8Br2V = 1041.3 (5) Å3
Mr = 312.00Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.520 (3) ŵ = 7.74 mm1
b = 6.5032 (18) ÅT = 173 K
c = 17.124 (5) Å0.21 × 0.16 × 0.15 mm
β = 100.826 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2378 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2076 reflections with I > 2σ(I)
Tmin = 0.291, Tmax = 0.384Rint = 0.029
14301 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.049H-atom parameters constrained
S = 1.03Δρmax = 0.51 e Å3
2378 reflectionsΔρmin = 0.35 e Å3
128 parameters
Special details top

Experimental. A crystal coated in Paratone (TM) oil was mounted on the end of a thin glass capillary and cooled in the gas stream of the diffractometer Kryoflex device.

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
Br10.95694 (2)1.00116 (3)0.877281 (12)0.03051 (8)
Br20.91366 (2)0.51805 (3)0.782113 (12)0.02895 (8)
C10.7083 (2)0.4723 (3)0.89091 (11)0.0248 (4)
H10.69710.33470.86440.030*
C20.57169 (19)0.6026 (3)0.87439 (10)0.0228 (4)
C30.4419 (2)0.5494 (3)0.82843 (12)0.0299 (4)
H30.42910.41890.80320.036*
C40.3293 (2)0.6909 (4)0.81956 (12)0.0355 (5)
H40.23870.65500.78910.043*
C50.3489 (2)0.8822 (4)0.85474 (11)0.0329 (5)
H50.27210.97790.84730.039*
C60.4807 (2)0.9370 (3)0.90125 (11)0.0268 (4)
H60.49441.06890.92530.032*
C70.59055 (19)0.7949 (3)0.91135 (10)0.0216 (4)
C80.74157 (19)0.8223 (3)0.95989 (10)0.0222 (4)
H80.75660.95860.98720.027*
C90.83973 (18)0.7872 (3)0.89981 (11)0.0217 (4)
C100.82213 (18)0.6069 (3)0.86406 (11)0.0222 (4)
C110.7486 (2)0.4593 (3)0.98174 (12)0.0287 (4)
H110.76020.33261.00980.034*
C120.7658 (2)0.6398 (3)1.01740 (11)0.0279 (4)
H120.79080.65511.07350.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02660 (12)0.02868 (12)0.03774 (13)0.00821 (7)0.00988 (9)0.00147 (8)
Br20.03114 (12)0.03011 (12)0.02878 (12)0.00309 (7)0.01384 (8)0.00166 (7)
C10.0276 (9)0.0201 (8)0.0284 (10)0.0030 (7)0.0098 (8)0.0022 (7)
C20.0233 (9)0.0277 (9)0.0196 (8)0.0045 (7)0.0095 (7)0.0004 (7)
C30.0280 (10)0.0386 (10)0.0242 (9)0.0105 (8)0.0076 (8)0.0032 (8)
C40.0228 (10)0.0597 (14)0.0239 (10)0.0064 (9)0.0046 (8)0.0036 (9)
C50.0243 (9)0.0515 (13)0.0247 (10)0.0086 (9)0.0095 (8)0.0073 (9)
C60.0285 (9)0.0326 (10)0.0222 (9)0.0029 (8)0.0122 (8)0.0025 (8)
C70.0227 (9)0.0270 (9)0.0169 (8)0.0021 (7)0.0082 (7)0.0017 (7)
C80.0236 (9)0.0226 (9)0.0213 (9)0.0016 (7)0.0065 (7)0.0024 (7)
C90.0176 (8)0.0242 (9)0.0234 (9)0.0024 (7)0.0043 (7)0.0033 (7)
C100.0206 (8)0.0252 (9)0.0223 (9)0.0030 (7)0.0076 (7)0.0019 (7)
C110.0318 (10)0.0286 (10)0.0268 (10)0.0002 (8)0.0085 (8)0.0069 (8)
C120.0286 (10)0.0337 (10)0.0214 (9)0.0015 (8)0.0048 (8)0.0047 (8)
Geometric parameters (Å, º) top
Br1—C91.8687 (18)C5—C61.400 (3)
Br2—C101.8766 (18)C5—H50.9500
C1—C101.530 (2)C6—C71.382 (3)
C1—C111.533 (3)C6—H60.9500
C1—C21.533 (3)C7—C81.530 (2)
C1—H11.0000C8—C91.531 (2)
C2—C31.379 (3)C8—C121.532 (3)
C2—C71.398 (3)C8—H81.0000
C3—C41.399 (3)C9—C101.318 (3)
C3—H30.9500C11—C121.319 (3)
C4—C51.380 (3)C11—H110.9500
C4—H40.9500C12—H120.9500
C10—C1—C11106.24 (15)C6—C7—C2120.79 (17)
C10—C1—C2104.60 (14)C6—C7—C8126.99 (17)
C11—C1—C2105.06 (15)C2—C7—C8112.22 (15)
C10—C1—H1113.4C7—C8—C9104.32 (14)
C11—C1—H1113.4C7—C8—C12105.75 (14)
C2—C1—H1113.4C9—C8—C12106.20 (14)
C3—C2—C7120.53 (18)C7—C8—H8113.3
C3—C2—C1127.22 (17)C9—C8—H8113.3
C7—C2—C1112.25 (15)C12—C8—H8113.3
C2—C3—C4118.90 (19)C10—C9—C8113.85 (15)
C2—C3—H3120.5C10—C9—Br1126.50 (14)
C4—C3—H3120.5C8—C9—Br1119.41 (13)
C5—C4—C3120.51 (18)C9—C10—C1113.88 (16)
C5—C4—H4119.7C9—C10—Br2125.79 (14)
C3—C4—H4119.7C1—C10—Br2120.20 (13)
C4—C5—C6120.73 (19)C12—C11—C1114.00 (17)
C4—C5—H5119.6C12—C11—H11123.0
C6—C5—H5119.6C1—C11—H11123.0
C7—C6—C5118.50 (19)C11—C12—C8113.66 (17)
C7—C6—H6120.7C11—C12—H12123.2
C5—C6—H6120.7C8—C12—H12123.2
C10—C1—C2—C3123.85 (19)C2—C7—C8—C1254.79 (19)
C11—C1—C2—C3124.47 (19)C7—C8—C9—C1057.17 (19)
C10—C1—C2—C755.32 (19)C12—C8—C9—C1054.3 (2)
C11—C1—C2—C756.35 (18)C7—C8—C9—Br1117.51 (14)
C7—C2—C3—C40.1 (3)C12—C8—C9—Br1131.03 (13)
C1—C2—C3—C4179.24 (17)C8—C9—C10—C10.4 (2)
C2—C3—C4—C51.5 (3)Br1—C9—C10—C1174.62 (13)
C3—C4—C5—C61.3 (3)C8—C9—C10—Br2175.36 (12)
C4—C5—C6—C70.2 (3)Br1—C9—C10—Br21.1 (2)
C5—C6—C7—C21.6 (3)C11—C1—C10—C953.6 (2)
C5—C6—C7—C8179.54 (17)C2—C1—C10—C957.3 (2)
C3—C2—C7—C61.4 (3)C11—C1—C10—Br2130.43 (14)
C1—C2—C7—C6177.83 (16)C2—C1—C10—Br2118.75 (14)
C3—C2—C7—C8179.56 (16)C10—C1—C11—C1253.9 (2)
C1—C2—C7—C81.2 (2)C2—C1—C11—C1256.6 (2)
C6—C7—C8—C9121.96 (19)C1—C11—C12—C80.0 (2)
C2—C7—C8—C957.00 (18)C7—C8—C12—C1156.5 (2)
C6—C7—C8—C12126.26 (19)C9—C8—C12—C1154.0 (2)

Experimental details

(I)(II)
Crystal data
Chemical formulaC12H10Br4C12H8Br2
Mr473.84312.00
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)173173
a, b, c (Å)6.9532 (4), 8.4323 (5), 11.9669 (7)9.520 (3), 6.5032 (18), 17.124 (5)
α, β, γ (°)94.706 (1), 91.257 (1), 110.892 (1)90, 100.826 (3), 90
V3)652.31 (7)1041.3 (5)
Z24
Radiation typeMo KαMo Kα
µ (mm1)12.317.74
Crystal size (mm)0.45 × 0.27 × 0.270.21 × 0.16 × 0.15
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionNumerical
(SADABS; Bruker, 2008)
Multi-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.052, 0.1440.291, 0.384
No. of measured, independent and
observed [I > 2σ(I)] reflections
7682, 3074, 2835 14301, 2378, 2076
Rint0.0240.029
(sin θ/λ)max1)0.6660.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.055, 1.05 0.020, 0.049, 1.03
No. of reflections30742378
No. of parameters146128
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.78, 0.780.51, 0.35

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

 

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