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Crystal structures are presented for two members of the homologous series of 1,2-dibromo-4,5-di­alk­oxy­benzenes, viz. those with decyl­oxy and hexa­decyl­oxy substituents, namely 1,2-dibromo-4,5-bis(decyl­oxy)­benzene, C26H44Br2O2, (II), and 1,2-dibromo-4,5-bis(hexa­decyl­oxy)­benzene, C38H68Br2O2, (III). The relative influences which halogen bonding, [pi]-[pi] stacking and van der Waals inter­actions have on these structures are analysed and the results compared with those already found for the lightest homologue, 1,2-dibromo-4,5-dimeth­oxy­benzene, (I) [Cukiernik, Zelcer, Garland & Baggio (2008). Acta Cryst. C64, o604-o608]. The results confirm that the prevalent inter­actions stabilizing the structures of (II) and (III) are van der Waals contacts between the aliphatic chains. In the case of (II), weak halogen C-Br...(Br-C)' inter­actions are also present and contribute to the stability of the structure. In the case of (III), van der Waals inter­actions between the aliphatic chains are almost exclusive, weaker C-Br...[pi] inter­actions being the only additional inter­actions detected. The results are in line with commonly accepted models concerning trends in crystal stability along a homologous series (as measured by their melting points), but the earlier report for n = 1, and the present report for n = 10 and 16, are among the few providing single-crystal information validating the hypothesis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113002485/uk3060sup1.cif
Contains datablocks II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002485/uk3060IIsup2.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002485/uk3060IIIsup3.hkl
Contains datablock III

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113002485/uk3060IIsup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113002485/uk3060IIIsup5.cml
Supplementary material

CCDC references: 925783; 925784

Comment top

The design of advanced materials exhibiting selected crystalline structures based on specific intermolecular interactions is nowadays one of the main conceptual tools in materials science. Knowledge of the strength and directionality of noncovalent interactions (hydrogen bonds, ππ stacking, halogen bonds etc.) allows for such design, and hundreds of successful examples can be found in growing research fields like crystal engineering (Desiraju, 2003) or supramolecular chemistry (Steed & Atwood, 2009; Bruce, 2012). In most cases, the structure is governed by one prevalent interaction (and was designed on this basis). The predictability of the crystalline structure a given compound will adopt, on the basis of the intermolecular interactions it can exhibit, is high in such cases, but diminishes when the number of competing interactions rises. One way to explore the relative influence of different interactions, keeping a few constant and allowing for a smooth variation of just one or two, is to work with different members of an homologous series.

In a study of the structure of dihalogenodimethoxybenzene compounds (Cukiernik et al., 2008), we found that the structure of 1,2-dibromo-4,5-dimethoxybenzene, (I) (Scheme 1), results from a combination of ππ, dipolar and halogen-bonding interactions. In this work, we report the crystal structures of two heavier homologues of this series, namely 1,2-dibromo-4,5-bis(decyloxy)benzene, (II), and 1,2-dibromo-4,5-bis(hexadecyloxy)benzene, (III) (Scheme 1), and analyse the relative influence halogen bonding, ππ stacking and van der Waals interactions have on the structures and, consequently, on some physical properties of these compounds.

Fig. 1 presents molecular views of both (II) and (III), where their striking `jellyfish-like' geometry (which defines their packing characteristics in some way) is apparent. The bond lengths and angles are featureless, and a distinguishing fact is the `straight' character of the terminal aliphatic chains, as disclosed by the extremely narrow span of the C—C—C—C torsion angles, viz. 171.0 (6)–179.9 (10)° in (II) and 174.13 (11)–179.9 (2)° in (III).

According to their geometric disposition, C—X···X—C interactions (X = halogen) have historically been divided into types I and II (see Scheme 2). [For further details on the subject, see Desiraju & Parthasarathy (1989, and references therein)]. In the case of (II), molecules interact weakly via C—Br···(Br—C) contacts of types I and II, some of them at the upper limit for stabilizing Br···Br distances {due to cumulative experimental evidence, there is an increasing tendency to accept small (though not negligible) stabilization effects arising from rather long Br···Br contacts [up to 10% longer than twice the Br van der Waals radius, ~3.7 Å; see, for example, Jones & Kuś (2007, 2011) and Al-Far & Ali (2007)]}, and details of these are presented in Table 1.

The first and second entries, corresponding respectively to type I and type II contacts (Fig. 2a, labelled A), define dimeric units arranged in a head-to-head fashion (Fig. 2a, labelled B). In turn, as a consequence of a third C—Br···(Br—C) type-I contact (Table 1, entry 3) in conjunction with van der Waals interactions between aliphatic chains, these dimeric units are held together as one-dimensional strands parallel to b. van der Waals interactions between parallel aliphatic chains also link the dimeric units along c, defining broad planar arrays parallel to (100), \sim a/2 wide along a (Is this Fig. 2a, the part labelled C?).

Fig. 2(b) gives a simplified view of the way in which both kinds of Br···Br' interactions build up.

The case of compound (III) is similar in general terms, viz. leading van der Waals interactions between aliphatic chains result in broad planar arrays parallel to (100), but the results are realised in quite different ways. To begin with, the head-to-head contacts joining antiparallel units in (II) are replaced by noticebly weaker C—Br···π contacts (Table 2) between parallel groups in (III), as shown in Fig. 3(a) (labelled A). These halogen···π interactions, presented in detail in Fig. 4, define columnar arrays along c (Fig. 3b, labelled B), which in turn interleave their long aliphatic chains, linking them into broad planar arrays parallel to (100), ~a/2 wide along a (Fig. 3, labelled C).

These results are of significance for interpreting some physical properties of these compounds, namely their melting point (m.p.). Indeed, the trend of the m.p. along the whole homologous series, according to literature data (Sauer & Wegner, 1988; Kalashnikova et al., 2003; Wohrle & Schmidt, 1988; Hanack et al., 1990), is shown in Fig. 5. In order to be able to discuss this trend in terms of the crystalline structures solved here, we measured the m.p. of the structurally characterized compounds directly by differential scanning calorimetry (DSC) on single crystals from the same crop used for structure elucidation. Single crystals of (II) melted at 316.5 K (ΔH = 66 kJ mol-1), and single crystals of (III) melted at 332.5 K (ΔH = 86 kJ mol-1), very close to the previously reported values for powder samples. This agreement validates the use of the present structural information for the interpretation of the m.p. trend along the whole series.

This kind of behaviour [an initial decrease in m.p. for increasing chain length (n), up to a certain n value, then a progressive increase in m.p. for further increase in n, up to a limiting value] is frequently found in homologous series with polar components (aliphatic alcohols, aliphatic carboxylic acids etc.; Lutton, 1967; Weast, 1986) and is often interpreted in terms of a diblock molecular architecture, in which both molecular blocks (here denoted 1 and 2) exhibit different packing requirements. For a homologous series, one of the molecular blocks (e.g. 2) is the aliphatic chain; in such a case, the usual argument takes the form that, for short aliphatic chains, the packing is governed by the 1 block; a progressive increase in chain length progressively disturbs this packing, facilitating the melting process. For long-chain homologues, the packing of the aliphatic chains is the main driving force for the crystalline structure; in those cases, the 1 block acts as a disturbing agent for the packing, this effect being stronger (lower m.p.) as chain length decreases. These kinds of arguments are found in the fields of physical organic chemistry, polymers and liquid crystals (Platé Shibaev, 1974; Weber et al., 1990; Ibn-Elhaj et al., 1992). However, even if accepted and often based on powder X-ray diffraction evidence, they are not always supported by single-crystal crystallographic evidence.

In the present case, the structures of (I), (II) and (III) provide direct experimental structural support for this interpretation. Indeed, the crystalline structure of (I) is essentially built up by ππ and halogen-bond interactions, while the prevalent interactions driving the structures of (II) and (III) are van der Waals interactions between the aliphatic chains. In the case of (II), halogen C—Br···(Br—C) contacts are still present and contribute to the global structure. In the case of (III), van der Waals interactions between the aliphatic chains are almost exclusive, weaker C—Br···(ring centroid) interactions being the only additional interactions detected.

Further possible steps for providing additional evidence for the homologous series under study could be to crystallize and solve the structure of the n = 2 homologue, as well as to find the `transition point', i.e. the n value for which the head-to-head arrangement found in (II) is replaced by the `tail-contact' arrangement found in (III). Further work on the subject is in progress.

Related literature top

For related literature, see: Al-Far & Ali (2007); Boden et al. (1993); Bruce (2012); Cukiernik et al. (2008); Desiraju (2003); Desiraju & Parthasarathy (1989); Hanack et al. (1990); Ibn-Elhaj, Guillon, Skoulios, Giroud-Godquin & Maldivi (1992); Jones & Kuś (2007, 2011); Kalashnikova et al. (2003); Lutton (1967); Platé & Shibaev (1974); Sauer & Wegner (1988); Steed & Atwood (2009); Weast (1986); Weber et al. (1990); Wohrle & Schmidt (1988).

Experimental top

All chemical precursors were purchased from Aldrich and used without further purification. Differential scanning calorimetry (DSC) was performed with a Shimadzu DSC-50 apparatus. Elemental analysis was carried out at Servicio a Terceros of INQUIMAE on a Carlo Erba CHNS-O EA1108 analyser. 1H NMR spectra were measured on a Bruker AM500 spectrometer, using CDCl3 as solvent and its residual peaks as internal references (7.26 p.p.m. for 1H).

Both (II) and (III) were synthesized in two steps from catechol (benzene-1,2-diol). The first step consisted of a Williamson's etherification of both hydroxy groups by reacting catechol with the appropriate bromoalkane, following published procedures (Boden et al., 1993). The second step was an aromatic electrophilic substitution in the activated para positions relative to the alkoxy chains.

For the preparation of 1,2-dibromo-4,5-bis(decyloxy)benzene, (II), 1,2-bis(decyloxy)benzene (1.282 g) was dissolved in cold CH2Cl2 (16 ml), placed in a two-necked flask equipped with an NaHSO3 bubbler with pressure compensation and immersed in an ice bath. Bromine (0.35 ml dissolved in 5 ml CH2Cl2) was added dropwise and the mixture was allowed to warm to room temperature. The progress of the reaction was monitored by thin-layer chromatography (TLC) (CH2Cl2–cyclohexane 1:3 v/v). When the reaction was complete, it was stopped by the addition of aqueous NaHSO3. The aqueous phase was discarded and the organic phase was washed successively with water, aqueous NaHSO3 and water, and then dried with anhydrous Na2SO4, filtered and evaporated to dryness in a rotary evaporator. The solid was recrystallized from ethanol (yield 1.56 g, 87%). Spectroscopic analysis: 1H NMR (Frequency?, CD3Cl, δ, p.p.m.): 7.058 (s, 2H), 3.94 (t, 4H), 1.78 (q, 4H), 1.44 (q, 4H), 1.34–1.27 (m, 24H), 0.88 (t, 6H). Single crystals were obtained by slow cooling (2 K per day) of a concentrated ethanol solution of (II).

For the preparation of 1,2-dibromo-4,5-bis(hexadecyloxy)benzene, (III), the synthetic procedure was identical to that followed for the preparation of (II), using 1,2-bis(hexadecyloxy)benzene (2.009 g dissolved in 25 ml CH2Cl2) instead of 1,2-bis(decyloxy)benzene and 0.40 ml Br2 instead of 0.35 ml (yield 1.88 g, 73%). Analysis, found (calculated for C38H68Br2O2) (%): C 63.6 (63.68), H 9.6 (9.56). Spectroscopic analysis: 1H NMR (Frequency?, CD3Cl, δ, p.p.m.): 7.06 (s, 2H), 3.94 (t, 4H), 1.78 (q, 4H), 1.44 (q, 4H), 1.34–1,27 (m, 48H) 0.88 (t, 6H). Single crystals were obtained by slow cooling of and solvent evaporation from a concentrated solution of (III) in chloroform.

Refinement top

Compound (III) posed no problems, either in the data collection or in the model refinement. In contrast, (II) showed disorder in the hydrophilic region, for which a low-temperature data set was needed to resolve the problem. In this way, a reasonable model could be refined, even when neglecting some (impossible to model) disorder effects. This was evident in some important reflection outliers, as well as some significant Δρ peaks, e.g. 1.67 e Å-3 at 2.04 Å from Br1.

All the H atoms in (III), and most of those in (II), were seen in difference maps, but they were subsequently placed in geometrically idealized positions and allowed to ride on their parent atoms, with aromatic C—H = 0.93 Å, methylene C—H = 0.97 Å and methyl C—H = 0.96 Å, and with Uiso(H) = 1.2, 1.2 and 1.5Ueq(C), respectively.

Computing details top

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structutres of (a) (II) and (b) (III), with the atom-numbering schemes. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. Packing diagrams for (II), depicting (a) a general view along b and (b) a simplified diagram showing halogen interactions. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z + 1; (ii) x, y - 1, z; (iii) x, y + 1, z.]
[Figure 3] Fig. 3. Packing diagrams for (III), depicting (a) a general view along c, showing the chains in projection, and (b) a general view along b, showing the chains running horizontally. [Symmetry code: (i) x, -y + 1, z - 1/2.]
[Figure 4] Fig. 4. A packing view for (III), projected along c, showing a simplified version of the C—Br···π interactions. Terminal aliphatic tails have been shortened to a few C atoms, for clarity.
[Figure 5] Fig. 5. The melting point of 1,2-dibromo-4,5-dialkoxybenzene as a function of alkoxy chain length. Filled circles represent literature data and open squares represent data for (II) and (III).
(II) 1,2-Dibromo-4,5-bis(decyloxy)benzene top
Crystal data top
C26H44Br2O2F(000) = 2288
Mr = 548.43Dx = 1.358 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2ycCell parameters from 11243 reflections
a = 67.0788 (15) Åθ = 2.1–25.8°
b = 4.4717 (1) ŵ = 3.04 mm1
c = 18.2399 (4) ÅT = 150 K
β = 101.216 (2)°Plate, colourless
V = 5366.7 (2) Å30.56 × 0.27 × 0.07 mm
Z = 8
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
5387 independent reflections
Radiation source: fine-focus sealed tube4981 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
ω scans, thick slicesθmax = 26.2°, θmin = 1.9°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 8282
Tmin = 0.42, Tmax = 0.78k = 45
28792 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 1.21 w = 1/[σ2(Fo2) + (0.0236P)2 + 122.7172P]
where P = (Fo2 + 2Fc2)/3
5387 reflections(Δ/σ)max < 0.001
271 parametersΔρmax = 1.67 e Å3
0 restraintsΔρmin = 0.95 e Å3
Crystal data top
C26H44Br2O2V = 5366.7 (2) Å3
Mr = 548.43Z = 8
Monoclinic, C2/cMo Kα radiation
a = 67.0788 (15) ŵ = 3.04 mm1
b = 4.4717 (1) ÅT = 150 K
c = 18.2399 (4) Å0.56 × 0.27 × 0.07 mm
β = 101.216 (2)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
5387 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
4981 reflections with I > 2σ(I)
Tmin = 0.42, Tmax = 0.78Rint = 0.068
28792 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.184H-atom parameters constrained
S = 1.21 w = 1/[σ2(Fo2) + (0.0236P)2 + 122.7172P]
where P = (Fo2 + 2Fc2)/3
5387 reflectionsΔρmax = 1.67 e Å3
271 parametersΔρmin = 0.95 e Å3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.225869 (11)0.04646 (19)0.45773 (4)0.0389 (2)
Br20.249896 (11)0.45935 (19)0.34532 (4)0.0366 (2)
O10.17000 (7)0.1276 (11)0.2145 (3)0.0297 (10)
O20.18712 (7)0.2238 (10)0.1327 (2)0.0276 (10)
C10.21452 (10)0.1098 (16)0.3549 (3)0.0268 (14)
C20.22418 (8)0.2811 (14)0.3103 (3)0.0220 (12)
C30.21497 (10)0.3305 (15)0.2353 (4)0.0287 (14)
H30.22120.45680.20590.034*
C40.19705 (9)0.1950 (15)0.2051 (3)0.0244 (13)
C50.18738 (9)0.0024 (15)0.2497 (4)0.0268 (14)
C60.19618 (9)0.0303 (15)0.3267 (4)0.0265 (14)
H60.18970.14430.35780.032*
C70.15963 (10)0.3154 (15)0.2613 (4)0.0300 (14)
H7A0.15420.19310.29680.036*
H7B0.16910.45910.28880.036*
C80.14293 (10)0.4722 (15)0.2110 (4)0.0271 (13)
H8A0.13720.61890.24010.033*
H8B0.14860.58020.17380.033*
C90.12568 (10)0.2721 (15)0.1703 (4)0.0279 (14)
H9A0.12130.14120.20650.034*
H9B0.13090.14730.13480.034*
C100.10730 (10)0.4473 (17)0.1288 (4)0.0317 (15)
H10A0.11170.57680.09240.038*
H10B0.10220.57370.16440.038*
C110.09000 (10)0.2517 (16)0.0889 (4)0.0302 (14)
H11A0.09500.12390.05360.036*
H11B0.08540.12400.12530.036*
C120.07198 (11)0.4314 (17)0.0473 (5)0.0373 (17)
H12A0.07640.54760.00840.045*
H12B0.06770.57050.08190.045*
C130.05388 (11)0.2398 (17)0.0119 (4)0.0341 (15)
H13A0.04900.13210.05110.041*
H13B0.05840.09330.02060.041*
C140.03652 (11)0.4177 (19)0.0328 (5)0.0409 (18)
H14A0.03180.56050.00000.049*
H14B0.04150.52960.07110.049*
C150.01860 (12)0.223 (2)0.0699 (5)0.049 (2)
H15A0.01330.11630.03140.059*
H15B0.02340.07650.10160.059*
C160.00144 (13)0.403 (3)0.1167 (6)0.067 (3)
H16A0.00930.27050.13870.101*
H16B0.00360.54560.08550.101*
H16C0.00650.50670.15560.101*
C170.19550 (10)0.4289 (15)0.0888 (4)0.0280 (14)
H17A0.20900.36450.08360.034*
H17B0.19660.62470.11210.034*
C180.18131 (11)0.4434 (18)0.0114 (4)0.0367 (16)
H18A0.18750.56740.02170.044*
H18B0.17960.24400.00990.044*
C190.16053 (11)0.5708 (18)0.0163 (4)0.0341 (16)
H19A0.15360.43120.04350.041*
H19B0.16240.75620.04450.041*
C200.14738 (11)0.6299 (18)0.0591 (4)0.0343 (16)
H20A0.14560.44400.08700.041*
H20B0.15440.76820.08620.041*
C210.12653 (12)0.758 (2)0.0558 (4)0.0394 (18)
H21A0.12830.94270.02720.047*
H21B0.11930.61850.02970.047*
C220.11359 (12)0.822 (2)0.1328 (4)0.0416 (18)
H22A0.11200.63970.16200.050*
H22B0.12050.96720.15850.050*
C230.09249 (12)0.944 (2)0.1275 (4)0.045 (2)
H23A0.09411.12030.09600.055*
H23B0.08530.79440.10410.055*
C240.07956 (12)1.026 (2)0.2054 (4)0.047 (2)
H24A0.08641.18280.22780.057*
H24B0.07850.85210.23790.057*
C250.05857 (14)1.129 (3)0.2000 (5)0.075 (4)
H25A0.05961.30300.16770.090*
H25B0.05180.97230.17760.090*
C260.04596 (15)1.209 (3)0.2762 (6)0.076 (4)
H26A0.03271.27350.27050.114*
H26B0.04471.03580.30810.114*
H26C0.05251.36640.29820.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0387 (4)0.0495 (5)0.0265 (4)0.0037 (3)0.0012 (3)0.0035 (3)
Br20.0304 (4)0.0450 (4)0.0334 (4)0.0083 (3)0.0035 (3)0.0020 (3)
O10.029 (2)0.033 (3)0.026 (2)0.006 (2)0.0024 (18)0.001 (2)
O20.034 (2)0.023 (2)0.025 (2)0.0042 (19)0.0049 (18)0.0005 (19)
C10.035 (3)0.029 (3)0.014 (3)0.010 (3)0.001 (2)0.003 (3)
C20.014 (3)0.025 (3)0.027 (3)0.004 (2)0.004 (2)0.008 (3)
C30.035 (3)0.025 (3)0.028 (3)0.002 (3)0.014 (3)0.003 (3)
C40.028 (3)0.023 (3)0.021 (3)0.005 (3)0.004 (2)0.000 (3)
C50.017 (3)0.026 (3)0.040 (4)0.003 (2)0.011 (3)0.001 (3)
C60.022 (3)0.024 (3)0.035 (4)0.003 (3)0.009 (3)0.008 (3)
C70.036 (3)0.023 (3)0.033 (3)0.001 (3)0.013 (3)0.009 (3)
C80.036 (3)0.021 (3)0.026 (3)0.000 (3)0.009 (3)0.001 (3)
C90.031 (3)0.022 (3)0.035 (3)0.004 (3)0.015 (3)0.004 (3)
C100.034 (3)0.033 (4)0.031 (3)0.000 (3)0.011 (3)0.006 (3)
C110.035 (3)0.027 (3)0.029 (3)0.002 (3)0.008 (3)0.001 (3)
C120.034 (4)0.028 (4)0.049 (4)0.004 (3)0.006 (3)0.001 (3)
C130.039 (4)0.032 (4)0.030 (3)0.000 (3)0.004 (3)0.006 (3)
C140.039 (4)0.036 (4)0.047 (4)0.001 (3)0.007 (3)0.003 (4)
C150.037 (4)0.043 (5)0.065 (6)0.001 (4)0.005 (4)0.003 (4)
C160.038 (5)0.068 (7)0.085 (8)0.004 (5)0.013 (5)0.006 (6)
C170.037 (3)0.021 (3)0.029 (3)0.001 (3)0.016 (3)0.011 (3)
C180.039 (4)0.035 (4)0.035 (4)0.001 (3)0.006 (3)0.001 (3)
C190.045 (4)0.039 (4)0.017 (3)0.001 (3)0.005 (3)0.003 (3)
C200.041 (4)0.042 (4)0.020 (3)0.005 (3)0.005 (3)0.003 (3)
C210.049 (4)0.056 (5)0.016 (3)0.006 (4)0.011 (3)0.005 (3)
C220.045 (4)0.051 (5)0.028 (4)0.003 (4)0.005 (3)0.006 (4)
C230.044 (4)0.064 (6)0.030 (4)0.007 (4)0.012 (3)0.008 (4)
C240.041 (4)0.069 (6)0.031 (4)0.007 (4)0.005 (3)0.001 (4)
C250.048 (5)0.129 (11)0.046 (5)0.028 (6)0.006 (4)0.022 (7)
C260.050 (5)0.125 (11)0.051 (6)0.024 (7)0.002 (4)0.018 (7)
Geometric parameters (Å, º) top
Br1—C11.903 (6)C14—H14B0.9700
Br2—C21.895 (6)C15—C161.523 (12)
O1—C51.348 (8)C15—H15A0.9700
O1—C71.465 (8)C15—H15B0.9700
O2—C41.365 (7)C16—H16A0.9600
O2—C171.405 (7)C16—H16B0.9600
C1—C21.369 (9)C16—H16C0.9600
C1—C61.387 (9)C17—C181.543 (10)
C2—C31.406 (9)C17—H17A0.9700
C3—C41.363 (9)C17—H17B0.9700
C3—H30.9300C18—C191.525 (10)
C4—C51.425 (9)C18—H18A0.9700
C5—C61.421 (9)C18—H18B0.9700
C6—H60.9300C19—C201.506 (9)
C7—C81.479 (9)C19—H19A0.9700
C7—H7A0.9700C19—H19B0.9700
C7—H7B0.9700C20—C211.524 (10)
C8—C91.535 (9)C20—H20A0.9700
C8—H8A0.9700C20—H20B0.9700
C8—H8B0.9700C21—C221.528 (9)
C9—C101.531 (9)C21—H21A0.9700
C9—H9A0.9700C21—H21B0.9700
C9—H9B0.9700C22—C231.536 (11)
C10—C111.521 (9)C22—H22A0.9700
C10—H10A0.9700C22—H22B0.9700
C10—H10B0.9700C23—C241.558 (10)
C11—C121.525 (9)C23—H23A0.9700
C11—H11A0.9700C23—H23B0.9700
C11—H11B0.9700C24—C251.504 (12)
C12—C131.522 (10)C24—H24A0.9700
C12—H12A0.9700C24—H24B0.9700
C12—H12B0.9700C25—C261.522 (12)
C13—C141.511 (10)C25—H25A0.9700
C13—H13A0.9700C25—H25B0.9700
C13—H13B0.9700C26—H26A0.9600
C14—C151.530 (11)C26—H26B0.9600
C14—H14A0.9700C26—H26C0.9600
C5—O1—C7115.7 (5)C14—C15—H15A109.0
C4—O2—C17116.1 (5)C16—C15—H15B109.0
C2—C1—C6121.3 (6)C14—C15—H15B109.0
C2—C1—Br1121.6 (5)H15A—C15—H15B107.8
C6—C1—Br1117.0 (5)C15—C16—H16A109.5
C1—C2—C3119.8 (6)C15—C16—H16B109.5
C1—C2—Br2122.7 (5)H16A—C16—H16B109.5
C3—C2—Br2117.5 (5)C15—C16—H16C109.5
C4—C3—C2120.6 (6)H16A—C16—H16C109.5
C4—C3—H3119.7H16B—C16—H16C109.5
C2—C3—H3119.7O2—C17—C18107.8 (6)
C3—C4—O2125.1 (6)O2—C17—H17A110.2
C3—C4—C5120.1 (6)C18—C17—H17A110.2
O2—C4—C5114.8 (6)O2—C17—H17B110.2
O1—C5—C6125.5 (6)C18—C17—H17B110.2
O1—C5—C4115.9 (6)H17A—C17—H17B108.5
C6—C5—C4118.6 (6)C19—C18—C17111.7 (6)
C1—C6—C5119.2 (6)C19—C18—H18A109.3
C1—C6—H6120.4C17—C18—H18A109.3
C5—C6—H6120.4C19—C18—H18B109.3
O1—C7—C8107.4 (5)C17—C18—H18B109.3
O1—C7—H7A110.2H18A—C18—H18B107.9
C8—C7—H7A110.2C20—C19—C18113.0 (6)
O1—C7—H7B110.2C20—C19—H19A109.0
C8—C7—H7B110.2C18—C19—H19A109.0
H7A—C7—H7B108.5C20—C19—H19B109.0
C7—C8—C9115.6 (6)C18—C19—H19B109.0
C7—C8—H8A108.4H19A—C19—H19B107.8
C9—C8—H8A108.4C19—C20—C21114.1 (6)
C7—C8—H8B108.4C19—C20—H20A108.7
C9—C8—H8B108.4C21—C20—H20A108.7
H8A—C8—H8B107.4C19—C20—H20B108.7
C10—C9—C8113.5 (6)C21—C20—H20B108.7
C10—C9—H9A108.9H20A—C20—H20B107.6
C8—C9—H9A108.9C20—C21—C22113.3 (6)
C10—C9—H9B108.9C20—C21—H21A108.9
C8—C9—H9B108.9C22—C21—H21A108.9
H9A—C9—H9B107.7C20—C21—H21B108.9
C11—C10—C9114.1 (6)C22—C21—H21B108.9
C11—C10—H10A108.7H21A—C21—H21B107.7
C9—C10—H10A108.7C21—C22—C23112.0 (6)
C11—C10—H10B108.7C21—C22—H22A109.2
C9—C10—H10B108.7C23—C22—H22A109.2
H10A—C10—H10B107.6C21—C22—H22B109.2
C10—C11—C12113.1 (6)C23—C22—H22B109.2
C10—C11—H11A109.0H22A—C22—H22B107.9
C12—C11—H11A109.0C22—C23—C24112.5 (6)
C10—C11—H11B109.0C22—C23—H23A109.1
C12—C11—H11B109.0C24—C23—H23A109.1
H11A—C11—H11B107.8C22—C23—H23B109.1
C13—C12—C11113.8 (6)C24—C23—H23B109.1
C13—C12—H12A108.8H23A—C23—H23B107.8
C11—C12—H12A108.8C25—C24—C23112.0 (7)
C13—C12—H12B108.8C25—C24—H24A109.2
C11—C12—H12B108.8C23—C24—H24A109.2
H12A—C12—H12B107.7C25—C24—H24B109.2
C14—C13—C12113.6 (6)C23—C24—H24B109.2
C14—C13—H13A108.9H24A—C24—H24B107.9
C12—C13—H13A108.9C24—C25—C26111.9 (8)
C14—C13—H13B108.9C24—C25—H25A109.2
C12—C13—H13B108.9C26—C25—H25A109.2
H13A—C13—H13B107.7C24—C25—H25B109.2
C13—C14—C15113.4 (7)C26—C25—H25B109.2
C13—C14—H14A108.9H25A—C25—H25B107.9
C15—C14—H14A108.9C25—C26—H26A109.5
C13—C14—H14B108.9C25—C26—H26B109.5
C15—C14—H14B108.9H26A—C26—H26B109.5
H14A—C14—H14B107.7C25—C26—H26C109.5
C16—C15—C14113.0 (8)H26A—C26—H26C109.5
C16—C15—H15A109.0H26B—C26—H26C109.5
C6—C1—C2—C33.4 (10)C4—C5—C6—C14.1 (9)
Br1—C1—C2—C3177.9 (5)C5—O1—C7—C8171.5 (5)
C6—C1—C2—Br2176.7 (5)O1—C7—C8—C966.3 (7)
Br1—C1—C2—Br22.0 (8)O2—C17—C18—C1965.0 (8)
C1—C2—C3—C43.9 (10)C7—C8—C9—C10171.0 (6)
Br2—C2—C3—C4176.1 (5)C8—C9—C10—C11179.4 (6)
C2—C3—C4—O2178.7 (6)C9—C10—C11—C12179.4 (6)
C2—C3—C4—C50.4 (10)C10—C11—C12—C13175.6 (6)
C17—O2—C4—C35.4 (9)C11—C12—C13—C14176.9 (7)
C17—O2—C4—C5175.5 (6)C12—C13—C14—C15178.5 (7)
C7—O1—C5—C60.4 (9)C13—C14—C15—C16178.2 (8)
C7—O1—C5—C4177.5 (6)C4—O2—C17—C18176.2 (5)
C3—C4—C5—O1178.3 (6)C17—C18—C19—C20171.6 (6)
O2—C4—C5—O10.8 (8)C18—C19—C20—C21179.8 (7)
C3—C4—C5—C63.6 (9)C19—C20—C21—C22178.9 (7)
O2—C4—C5—C6177.2 (6)C20—C21—C22—C23178.5 (7)
C2—C1—C6—C50.7 (10)C21—C22—C23—C24177.0 (8)
Br1—C1—C6—C5178.1 (5)C22—C23—C24—C25177.0 (9)
O1—C5—C6—C1178.0 (6)C23—C24—C25—C26179.9 (10)
(III) 1,2-Dibromo-4,5-bis(hexadecyloxy)benzene top
Crystal data top
C38H68Br2O2F(000) = 1528
Mr = 716.72Dx = 1.231 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71069 Å
Hall symbol: C -2ycCell parameters from 8379 reflections
a = 50.158 (5) Åθ = 3.6–29.0°
b = 8.360 (3) ŵ = 2.13 mm1
c = 9.248 (3) ÅT = 294 K
β = 94.136 (5)°Plate, colourless
V = 3868 (2) Å30.58 × 0.32 × 0.10 mm
Z = 4
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
6905 independent reflections
Radiation source: fine-focus sealed tube4926 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scans, thick slicesθmax = 27.0°, θmin = 3.6°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 5563
Tmin = 0.45, Tmax = 0.82k = 1010
16641 measured reflectionsl = 1111
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)] = 0.024H-atom parameters constrained
wR(F2) = 0.053 w = 1/[σ2(Fo2) + (0.0318P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.84(Δ/σ)max = 0.001
6905 reflectionsΔρmax = 0.26 e Å3
379 parametersΔρmin = 0.18 e Å3
2 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.087 (5)
Crystal data top
C38H68Br2O2V = 3868 (2) Å3
Mr = 716.72Z = 4
Monoclinic, CcMo Kα radiation
a = 50.158 (5) ŵ = 2.13 mm1
b = 8.360 (3) ÅT = 294 K
c = 9.248 (3) Å0.58 × 0.32 × 0.10 mm
β = 94.136 (5)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
6905 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
4926 reflections with I > 2σ(I)
Tmin = 0.45, Tmax = 0.82Rint = 0.024
16641 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.053Δρmax = 0.26 e Å3
S = 0.84Δρmin = 0.18 e Å3
6905 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
379 parametersAbsolute structure parameter: 0.087 (5)
2 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.265200 (6)0.10931 (4)0.61498 (3)0.08034 (10)
Br20.233107 (6)0.31448 (4)0.34048 (2)0.07120 (9)
O10.18247 (3)0.24640 (17)0.90673 (14)0.0424 (3)
O20.15942 (3)0.4158 (2)0.70339 (15)0.0475 (4)
C10.23212 (4)0.2101 (3)0.6346 (2)0.0460 (5)
C20.21907 (4)0.2945 (3)0.5242 (2)0.0437 (5)
C30.19459 (4)0.3661 (3)0.5428 (2)0.0423 (5)
H30.18590.42420.46780.051*
C40.18326 (4)0.3503 (2)0.6741 (2)0.0363 (5)
C50.19608 (4)0.2611 (2)0.7859 (2)0.0359 (5)
C60.22054 (4)0.1931 (3)0.7672 (2)0.0411 (5)
H60.22940.13590.84240.049*
C70.19065 (4)0.1218 (3)1.0097 (2)0.0447 (5)
H7A0.20630.15521.06970.054*
H7B0.19490.02450.95920.054*
C80.16749 (4)0.0940 (3)1.1017 (2)0.0439 (5)
H8A0.16330.19321.14940.053*
H8B0.17270.01621.17630.053*
C90.14270 (4)0.0343 (3)1.0145 (2)0.0449 (5)
H9A0.14750.05830.95890.054*
H9B0.13670.11690.94620.054*
C100.11952 (4)0.0115 (3)1.1042 (2)0.0458 (5)
H11A0.12510.09861.16870.055*
H11B0.11520.07911.16370.055*
C110.09473 (5)0.0619 (3)1.0130 (2)0.0494 (6)
H10A0.09920.15340.95490.059*
H10B0.08960.02460.94670.059*
C120.07085 (4)0.1052 (3)1.0966 (2)0.0489 (6)
H12A0.07580.19301.16160.059*
H12B0.06640.01431.15540.059*
C130.04641 (5)0.1527 (3)1.0012 (3)0.0513 (6)
H13A0.05100.24390.94300.062*
H13B0.04170.06510.93540.062*
C140.02199 (5)0.1954 (3)1.0813 (2)0.0507 (6)
H14A0.02650.28411.14620.061*
H14B0.01740.10481.14030.061*
C150.00213 (5)0.2403 (3)0.9834 (2)0.0542 (6)
H15A0.00260.33070.92450.065*
H15B0.00640.15160.91830.065*
C160.02704 (5)0.2835 (3)1.0589 (2)0.0541 (6)
H16A0.02300.37361.12280.065*
H16B0.03170.19381.11860.065*
C170.05075 (5)0.3254 (3)0.9581 (3)0.0568 (7)
H17A0.04600.41480.89830.068*
H17B0.05480.23520.89430.068*
C180.07597 (5)0.3694 (3)1.0318 (3)0.0567 (6)
H18A0.07210.46031.09490.068*
H18B0.08080.28041.09190.068*
C190.09948 (5)0.4099 (3)0.9274 (3)0.0599 (7)
H19A0.09460.49890.86750.072*
H19B0.10320.31900.86400.072*
C200.12493 (5)0.4535 (3)0.9980 (3)0.0606 (7)
H20A0.12130.54441.06150.073*
H20B0.12990.36451.05760.073*
C210.14827 (5)0.4942 (4)0.8926 (3)0.0752 (8)
H21A0.14330.58310.83290.090*
H21B0.15200.40320.82920.090*
C220.17372 (6)0.5381 (5)0.9634 (4)0.0953 (10)
H22A0.18760.56150.88970.143*
H22B0.17910.45001.02140.143*
H22C0.17050.63041.02390.143*
C230.14154 (4)0.4670 (3)0.5843 (2)0.0419 (5)
H23A0.13810.38030.51580.050*
H23B0.14910.55620.53410.050*
C240.11629 (4)0.5164 (3)0.6499 (2)0.0442 (5)
H24A0.12020.60580.71480.053*
H24B0.11020.42840.70740.053*
C250.09390 (4)0.5642 (3)0.5396 (2)0.0451 (5)
H25A0.09980.65360.48310.054*
H25B0.09000.47550.47380.054*
C260.06862 (4)0.6109 (3)0.6091 (2)0.0482 (6)
H26A0.07260.70090.67320.058*
H26B0.06330.52230.66830.058*
C270.04518 (5)0.6556 (3)0.5041 (2)0.0495 (6)
H27A0.05030.74540.44570.059*
H27B0.04110.56620.43940.059*
C280.02041 (4)0.6994 (3)0.5790 (2)0.0495 (6)
H28A0.02460.78880.64340.059*
H28B0.01560.60960.63840.059*
C290.00362 (5)0.7435 (3)0.4789 (2)0.0518 (6)
H29A0.00800.65460.41420.062*
H29B0.00090.83420.42010.062*
C300.02816 (4)0.7856 (3)0.5588 (2)0.0522 (6)
H30A0.03250.69510.61860.063*
H30B0.02370.87480.62310.063*
C310.05271 (5)0.8290 (3)0.4630 (3)0.0535 (6)
H31A0.05740.73970.39910.064*
H31B0.04860.91960.40310.064*
C320.07674 (4)0.8709 (3)0.5480 (2)0.0545 (6)
H32A0.08060.78070.60910.065*
H32B0.07200.96070.61100.065*
C330.10175 (5)0.9127 (3)0.4554 (2)0.0542 (6)
H33A0.10660.82310.39230.065*
H33B0.09801.00330.39460.065*
C340.12536 (5)0.9535 (3)0.5426 (3)0.0562 (6)
H34A0.12890.86290.60390.067*
H34B0.12051.04310.60570.067*
C350.15089 (5)0.9956 (3)0.4526 (3)0.0573 (7)
H35A0.15600.90550.39070.069*
H35B0.14741.08550.39040.069*
C360.17411 (5)1.0383 (4)0.5426 (3)0.0585 (7)
H36A0.17710.94980.60720.070*
H36B0.16911.13050.60210.070*
C370.19989 (5)1.0751 (4)0.4554 (3)0.0706 (9)
H37A0.20550.98130.39940.085*
H37B0.19681.16060.38780.085*
C380.22209 (6)1.1239 (4)0.5483 (3)0.0829 (9)
H38A0.23811.14410.48750.124*
H38B0.21701.21930.60110.124*
H38C0.22531.03950.61520.124*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03922 (15)0.1009 (2)0.1034 (2)0.02751 (17)0.02233 (13)0.0018 (2)
Br20.05548 (17)0.1022 (2)0.05902 (13)0.00078 (17)0.02555 (11)0.00573 (16)
O10.0394 (9)0.0432 (8)0.0460 (8)0.0086 (7)0.0122 (6)0.0078 (7)
O20.0338 (9)0.0651 (11)0.0443 (8)0.0207 (8)0.0067 (6)0.0098 (7)
C10.0251 (11)0.0487 (15)0.0649 (14)0.0019 (10)0.0069 (10)0.0076 (11)
C20.0369 (12)0.0472 (14)0.0488 (12)0.0037 (11)0.0144 (10)0.0078 (10)
C30.0329 (13)0.0474 (15)0.0468 (12)0.0016 (10)0.0046 (9)0.0010 (10)
C40.0234 (11)0.0374 (13)0.0480 (12)0.0027 (9)0.0029 (8)0.0030 (9)
C50.0263 (11)0.0344 (11)0.0470 (12)0.0037 (9)0.0038 (9)0.0028 (9)
C60.0225 (11)0.0460 (14)0.0543 (12)0.0021 (10)0.0007 (9)0.0010 (10)
C70.0286 (12)0.0523 (15)0.0523 (13)0.0059 (11)0.0037 (10)0.0133 (11)
C80.0394 (12)0.0516 (14)0.0397 (11)0.0025 (11)0.0042 (9)0.0122 (10)
C90.0354 (13)0.0558 (14)0.0432 (12)0.0045 (11)0.0016 (9)0.0021 (10)
C100.0399 (13)0.0567 (15)0.0409 (11)0.0069 (11)0.0032 (9)0.0032 (10)
C110.0399 (14)0.0607 (16)0.0483 (13)0.0076 (11)0.0071 (10)0.0016 (10)
C120.0372 (13)0.0618 (15)0.0481 (12)0.0042 (12)0.0051 (10)0.0010 (11)
C130.0393 (15)0.0642 (16)0.0512 (13)0.0077 (12)0.0079 (10)0.0020 (11)
C140.0363 (13)0.0621 (16)0.0538 (13)0.0066 (12)0.0037 (10)0.0015 (12)
C150.0424 (15)0.0686 (18)0.0522 (13)0.0082 (12)0.0084 (11)0.0003 (11)
C160.0382 (14)0.0708 (18)0.0534 (13)0.0072 (12)0.0045 (10)0.0008 (12)
C170.0389 (15)0.0754 (18)0.0573 (14)0.0093 (13)0.0110 (11)0.0054 (12)
C180.0370 (14)0.0742 (18)0.0594 (14)0.0102 (12)0.0074 (10)0.0035 (12)
C190.0399 (14)0.082 (2)0.0582 (15)0.0121 (14)0.0093 (11)0.0050 (13)
C200.0395 (14)0.0783 (18)0.0646 (15)0.0063 (13)0.0087 (11)0.0055 (13)
C210.0376 (15)0.105 (3)0.0832 (19)0.0136 (16)0.0081 (13)0.0021 (16)
C220.0400 (18)0.129 (3)0.118 (3)0.0182 (19)0.0089 (16)0.008 (2)
C230.0280 (12)0.0506 (14)0.0474 (12)0.0052 (10)0.0050 (9)0.0082 (10)
C240.0329 (12)0.0549 (15)0.0453 (12)0.0069 (11)0.0068 (9)0.0058 (10)
C250.0312 (12)0.0568 (15)0.0482 (12)0.0095 (11)0.0081 (9)0.0039 (10)
C260.0313 (12)0.0657 (16)0.0478 (12)0.0115 (12)0.0041 (9)0.0027 (11)
C270.0341 (13)0.0648 (16)0.0502 (13)0.0098 (12)0.0061 (10)0.0013 (11)
C280.0314 (12)0.0655 (17)0.0515 (12)0.0112 (11)0.0028 (9)0.0006 (11)
C290.0343 (13)0.0702 (17)0.0514 (13)0.0092 (12)0.0062 (10)0.0001 (11)
C300.0301 (12)0.0715 (18)0.0548 (13)0.0124 (11)0.0027 (9)0.0017 (12)
C310.0357 (14)0.0724 (18)0.0528 (13)0.0109 (12)0.0063 (11)0.0027 (12)
C320.0297 (12)0.0799 (18)0.0535 (13)0.0136 (12)0.0010 (10)0.0025 (11)
C330.0378 (13)0.0763 (19)0.0488 (13)0.0083 (12)0.0043 (10)0.0019 (12)
C340.0290 (13)0.0838 (18)0.0557 (14)0.0123 (13)0.0026 (10)0.0023 (12)
C350.0388 (14)0.083 (2)0.0503 (13)0.0137 (13)0.0056 (10)0.0026 (13)
C360.0384 (14)0.0829 (19)0.0542 (14)0.0110 (13)0.0026 (11)0.0015 (13)
C370.0430 (17)0.101 (3)0.0682 (18)0.0147 (16)0.0033 (13)0.0016 (16)
C380.0439 (17)0.112 (3)0.092 (2)0.0294 (17)0.0051 (14)0.0060 (19)
Geometric parameters (Å, º) top
Br1—C11.881 (2)C20—H20B0.9700
Br2—C21.893 (2)C21—C221.521 (4)
O1—C51.357 (2)C21—H21A0.9700
O1—C71.451 (3)C21—H21B0.9700
O2—C41.360 (2)C22—H22A0.9600
O2—C231.435 (3)C22—H22B0.9600
C1—C21.369 (3)C22—H22C0.9600
C1—C61.401 (3)C23—C241.501 (3)
C2—C31.388 (3)C23—H23A0.9700
C3—C41.383 (3)C23—H23B0.9700
C3—H30.9300C24—C251.515 (3)
C4—C51.393 (3)C24—H24A0.9700
C5—C61.374 (3)C24—H24B0.9700
C6—H60.9300C25—C261.514 (3)
C7—C81.506 (3)C25—H25A0.9700
C7—H7A0.9700C25—H25B0.9700
C7—H7B0.9700C26—C271.516 (3)
C8—C91.517 (3)C26—H26A0.9700
C8—H8A0.9700C26—H26B0.9700
C8—H8B0.9700C27—C281.510 (3)
C9—C101.525 (3)C27—H27A0.9700
C9—H9A0.9700C27—H27B0.9700
C9—H9B0.9700C28—C291.511 (3)
C10—C111.512 (3)C28—H28A0.9700
C10—H11A0.9700C28—H28B0.9700
C10—H11B0.9700C29—C301.522 (3)
C11—C121.515 (3)C29—H29A0.9700
C11—H10A0.9700C29—H29B0.9700
C11—H10B0.9700C30—C311.508 (3)
C12—C131.511 (3)C30—H30A0.9700
C12—H12A0.9700C30—H30B0.9700
C12—H12B0.9700C31—C321.526 (3)
C13—C141.519 (3)C31—H31A0.9700
C13—H13A0.9700C31—H31B0.9700
C13—H13B0.9700C32—C331.508 (3)
C14—C151.506 (3)C32—H32A0.9700
C14—H14A0.9700C32—H32B0.9700
C14—H14B0.9700C33—C341.519 (3)
C15—C161.518 (3)C33—H33A0.9700
C15—H15A0.9700C33—H33B0.9700
C15—H15B0.9700C34—C351.518 (3)
C16—C171.499 (3)C34—H34A0.9700
C16—H16A0.9700C34—H34B0.9700
C16—H16B0.9700C35—C361.522 (3)
C17—C181.524 (3)C35—H35A0.9700
C17—H17A0.9700C35—H35B0.9700
C17—H17B0.9700C36—C371.505 (3)
C18—C191.508 (3)C36—H36A0.9700
C18—H18A0.9700C36—H36B0.9700
C18—H18B0.9700C37—C381.511 (4)
C19—C201.519 (3)C37—H37A0.9700
C19—H19A0.9700C37—H37B0.9700
C19—H19B0.9700C38—H38A0.9600
C20—C211.507 (3)C38—H38B0.9600
C20—H20A0.9700C38—H38C0.9600
C5—O1—C7118.08 (16)C22—C21—H21A108.7
C4—O2—C23118.49 (15)C20—C21—H21B108.7
C2—C1—C6119.92 (19)C22—C21—H21B108.7
C2—C1—Br1122.46 (16)H21A—C21—H21B107.6
C6—C1—Br1117.60 (17)C21—C22—H22A109.5
C1—C2—C3120.64 (19)C21—C22—H22B109.5
C1—C2—Br2121.74 (16)H22A—C22—H22B109.5
C3—C2—Br2117.60 (17)C21—C22—H22C109.5
C4—C3—C2119.4 (2)H22A—C22—H22C109.5
C4—C3—H3120.3H22B—C22—H22C109.5
C2—C3—H3120.3O2—C23—C24105.69 (16)
O2—C4—C3123.98 (19)O2—C23—H23A110.6
O2—C4—C5115.67 (17)C24—C23—H23A110.6
C3—C4—C5120.34 (19)O2—C23—H23B110.6
O1—C5—C6124.96 (19)C24—C23—H23B110.6
O1—C5—C4115.26 (18)H23A—C23—H23B108.7
C6—C5—C4119.76 (19)C23—C24—C25113.97 (17)
C5—C6—C1119.89 (19)C23—C24—H24A108.8
C5—C6—H6120.1C25—C24—H24A108.8
C1—C6—H6120.1C23—C24—H24B108.8
O1—C7—C8106.76 (17)C25—C24—H24B108.8
O1—C7—H7A110.4H24A—C24—H24B107.7
C8—C7—H7A110.4C26—C25—C24112.64 (17)
O1—C7—H7B110.4C26—C25—H25A109.1
C8—C7—H7B110.4C24—C25—H25A109.1
H7A—C7—H7B108.6C26—C25—H25B109.1
C7—C8—C9112.76 (18)C24—C25—H25B109.1
C7—C8—H8A109.0H25A—C25—H25B107.8
C9—C8—H8A109.0C25—C26—C27115.21 (17)
C7—C8—H8B109.0C25—C26—H26A108.5
C9—C8—H8B109.0C27—C26—H26A108.5
H8A—C8—H8B107.8C25—C26—H26B108.5
C8—C9—C10114.92 (17)C27—C26—H26B108.5
C8—C9—H9A108.5H26A—C26—H26B107.5
C10—C9—H9A108.5C28—C27—C26113.06 (18)
C8—C9—H9B108.5C28—C27—H27A109.0
C10—C9—H9B108.5C26—C27—H27A109.0
H9A—C9—H9B107.5C28—C27—H27B109.0
C11—C10—C9113.27 (16)C26—C27—H27B109.0
C11—C10—H11A108.9H27A—C27—H27B107.8
C9—C10—H11A108.9C27—C28—C29115.14 (18)
C11—C10—H11B108.9C27—C28—H28A108.5
C9—C10—H11B108.9C29—C28—H28A108.5
H11A—C10—H11B107.7C27—C28—H28B108.5
C10—C11—C12115.50 (18)C29—C28—H28B108.5
C10—C11—H10A108.4H28A—C28—H28B107.5
C12—C11—H10A108.4C28—C29—C30113.36 (18)
C10—C11—H10B108.4C28—C29—H29A108.9
C12—C11—H10B108.4C30—C29—H29A108.9
H10A—C11—H10B107.5C28—C29—H29B108.9
C13—C12—C11113.76 (18)C30—C29—H29B108.9
C13—C12—H12A108.8H29A—C29—H29B107.7
C11—C12—H12A108.8C31—C30—C29115.16 (18)
C13—C12—H12B108.8C31—C30—H30A108.5
C11—C12—H12B108.8C29—C30—H30A108.5
H12A—C12—H12B107.7C31—C30—H30B108.5
C12—C13—C14115.21 (19)C29—C30—H30B108.5
C12—C13—H13A108.5H30A—C30—H30B107.5
C14—C13—H13A108.5C30—C31—C32113.24 (19)
C12—C13—H13B108.5C30—C31—H31A108.9
C14—C13—H13B108.5C32—C31—H31A108.9
H13A—C13—H13B107.5C30—C31—H31B108.9
C15—C14—C13113.97 (19)C32—C31—H31B108.9
C15—C14—H14A108.8H31A—C31—H31B107.7
C13—C14—H14A108.8C33—C32—C31114.63 (19)
C15—C14—H14B108.8C33—C32—H32A108.6
C13—C14—H14B108.8C31—C32—H32A108.6
H14A—C14—H14B107.7C33—C32—H32B108.6
C14—C15—C16115.77 (19)C31—C32—H32B108.6
C14—C15—H15A108.3H32A—C32—H32B107.6
C16—C15—H15A108.3C32—C33—C34113.54 (18)
C14—C15—H15B108.3C32—C33—H33A108.9
C16—C15—H15B108.3C34—C33—H33A108.9
H15A—C15—H15B107.4C32—C33—H33B108.9
C17—C16—C15114.32 (19)C34—C33—H33B108.9
C17—C16—H16A108.7H33A—C33—H33B107.7
C15—C16—H16A108.7C35—C34—C33114.82 (19)
C17—C16—H16B108.7C35—C34—H34A108.6
C15—C16—H16B108.7C33—C34—H34A108.6
H16A—C16—H16B107.6C35—C34—H34B108.6
C16—C17—C18115.2 (2)C33—C34—H34B108.6
C16—C17—H17A108.5H34A—C34—H34B107.5
C18—C17—H17A108.5C34—C35—C36113.76 (19)
C16—C17—H17B108.5C34—C35—H35A108.8
C18—C17—H17B108.5C36—C35—H35A108.8
H17A—C17—H17B107.5C34—C35—H35B108.8
C19—C18—C17113.8 (2)C36—C35—H35B108.8
C19—C18—H18A108.8H35A—C35—H35B107.7
C17—C18—H18A108.8C37—C36—C35114.6 (2)
C19—C18—H18B108.8C37—C36—H36A108.6
C17—C18—H18B108.8C35—C36—H36A108.6
H18A—C18—H18B107.7C37—C36—H36B108.6
C18—C19—C20114.9 (2)C35—C36—H36B108.6
C18—C19—H19A108.5H36A—C36—H36B107.6
C20—C19—H19A108.5C36—C37—C38113.0 (2)
C18—C19—H19B108.5C36—C37—H37A109.0
C20—C19—H19B108.5C38—C37—H37A109.0
H19A—C19—H19B107.5C36—C37—H37B109.0
C21—C20—C19114.5 (2)C38—C37—H37B109.0
C21—C20—H20A108.6H37A—C37—H37B107.8
C19—C20—H20A108.6C37—C38—H38A109.5
C21—C20—H20B108.6C37—C38—H38B109.5
C19—C20—H20B108.6H38A—C38—H38B109.5
H20A—C20—H20B107.6C37—C38—H38C109.5
C20—C21—C22114.4 (2)H38A—C38—H38C109.5
C20—C21—H21A108.7H38B—C38—H38C109.5
C6—C1—C2—C31.1 (3)C10—C11—C12—C13179.2 (2)
Br1—C1—C2—C3179.52 (16)C11—C12—C13—C14179.4 (2)
C6—C1—C2—Br2177.56 (16)C12—C13—C14—C15179.3 (2)
Br1—C1—C2—Br20.9 (3)C13—C14—C15—C16179.8 (2)
C1—C2—C3—C40.6 (3)C14—C15—C16—C17179.2 (2)
Br2—C2—C3—C4178.09 (16)C15—C16—C17—C18179.9 (2)
C23—O2—C4—C317.4 (3)C16—C17—C18—C19179.6 (2)
C23—O2—C4—C5161.66 (19)C17—C18—C19—C20179.8 (2)
C2—C3—C4—O2179.9 (2)C18—C19—C20—C21179.9 (2)
C2—C3—C4—C51.0 (3)C19—C20—C21—C22179.9 (3)
C7—O1—C5—C615.4 (3)C4—O2—C23—C24174.14 (18)
C7—O1—C5—C4163.21 (19)O2—C23—C24—C25175.97 (19)
O2—C4—C5—O12.6 (3)C23—C24—C25—C26179.1 (2)
C3—C4—C5—O1176.50 (18)C24—C25—C26—C27178.4 (2)
O2—C4—C5—C6178.69 (19)C25—C26—C27—C28179.4 (2)
C3—C4—C5—C62.2 (3)C26—C27—C28—C29179.5 (2)
O1—C5—C6—C1176.85 (19)C27—C28—C29—C30179.6 (2)
C4—C5—C6—C11.7 (3)C28—C29—C30—C31179.5 (2)
C2—C1—C6—C50.1 (3)C29—C30—C31—C32179.7 (2)
Br1—C1—C6—C5178.44 (16)C30—C31—C32—C33179.2 (2)
C5—O1—C7—C8160.79 (18)C31—C32—C33—C34179.9 (2)
O1—C7—C8—C962.6 (3)C32—C33—C34—C35179.8 (2)
C7—C8—C9—C10174.3 (2)C33—C34—C35—C36179.2 (2)
C8—C9—C10—C11176.9 (2)C34—C35—C36—C37178.0 (3)
C9—C10—C11—C12178.7 (2)C35—C36—C37—C38177.4 (3)

Experimental details

(II)(III)
Crystal data
Chemical formulaC26H44Br2O2C38H68Br2O2
Mr548.43716.72
Crystal system, space groupMonoclinic, C2/cMonoclinic, Cc
Temperature (K)150294
a, b, c (Å)67.0788 (15), 4.4717 (1), 18.2399 (4)50.158 (5), 8.360 (3), 9.248 (3)
β (°) 101.216 (2) 94.136 (5)
V3)5366.7 (2)3868 (2)
Z84
Radiation typeMo KαMo Kα
µ (mm1)3.042.13
Crystal size (mm)0.56 × 0.27 × 0.070.58 × 0.32 × 0.10
Data collection
DiffractometerOxford Gemini S Ultra CCD area-detector
diffractometer
Oxford Gemini S Ultra CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.42, 0.780.45, 0.82
No. of measured, independent and
observed [I > 2σ(I)] reflections
28792, 5387, 4981 16641, 6905, 4926
Rint0.0680.024
(sin θ/λ)max1)0.6200.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.184, 1.21 0.024, 0.053, 0.84
No. of reflections53876905
No. of parameters271379
No. of restraints02
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0236P)2 + 122.7172P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0318P)2]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.67, 0.950.26, 0.18
Absolute structure?Flack (1983), with how many Friedel pairs?
Absolute structure parameter?0.087 (5)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

C—X···(X—C)' interactions (Å, °) in (II) (X = halogen) top
The mean interaliphatic distance is 3.80Å.
C—X···(X—C)'X···X'(C—X)···X'X···(X—C)'Interaction type
C1—Br1···(Br1-C1)i3.7722 (15)118.6 (2)118.6 (2)I
C1—Br1···(Br2-C2)i3.6437 (10)171.5 (2)122.1 (2)II
C1—Br1···(Br2-C2)ii3.8704 (11)73.0 (2)91.0 (2)I
Symmetry codes: (i) -x + 1/2, -y + 1/2, -z + 1; (ii) x, y - 1, z.
C—X···π interactions (Å, °) in (III) (X = halogen) top
Cg1 is the centre of the C1–C6 ring. The mean interaliphatic distance is 3.90 Å.
C—X···CgC···XX···CgC···CgC—X···Cg
C2—Br2···Cg1i1.8933.976 (3)4.941109.1
Symmetry code: (i) x, -y + 1, z - 1/2.
 

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