Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022532/lh2381sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022532/lh2381Isup2.hkl |
CCDC reference: 651439
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.007 Å
- R factor = 0.053
- wR factor = 0.156
- Data-to-parameter ratio = 17.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.80 mm PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 500 Ang. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT355_ALERT_3_C Long O-H Bond (0.82A) O1S - H1OB ... 1.01 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: All authors made significant contribution in this work. The idea of synthesis belongs to Kamalov and Kotlyar. The synthesis was performed by Grygorash and Pluzhnik-Gladyr. X-ray diffraction experiment was performed by Shishkina. The analysis of diffraction data was performed by Shishkin. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
N-Bromosuccinimide (1.9 g, 10.68 mmol) was added to a solution of [1.4]dibenzo-15-crown-5 (1.63 g, 5.15 mmol) in 15 ml CHCl3. The reaction mixture was refluxed for 1 h then cooled and filtered. The residue was washed with 15 ml of CHCl3 and the combined filtrates were evaporated at the lowered pressure until dry. The was residue was washed with water, filtered, dried at the open air to constant weight and crystallized from propanol-2. The yield of compound IV is 83% (2.03 g, white crystals), [m.p. 375–376 K]. Analysis, calculated for C18H18Br2O5: C 45.52, H 3.79, Br 33.68%; found: C 45.60, H 3.83, Br 33.70%. The crystals are soluble in benzene, acetone, dichloromethane, chloroform, dimethyl sulfoxide, dimethyl formamide and other organic solvents. 1H NMR spectrum (Varian VXR-300, in CDCl3, relative to the inner standard Me4Si): Har 7.22–7.20 (2H, dd), J=9.3, J=1.5; 7.06–7.03 (2H, d), J=9.3; 6.87–7.63 (2H, d), J=1.5; CH2CH2O - 4.18–4.15 (4H, m), 3.64–3.61 (4H, m), 3.52 (4H, s). TLC (Silufol UV 254, Kavalier, plates, the visualization was performed under UV light): Rf 0.54 (aceton-n-hexane = 1:1). Transparent colourless crystals of (IV).H2O, suitable for X-ray were obtained by spontaneous evaporation of 95% ethanol solution.
All hydrogen atoms were located in electron density difference maps but included in the refinement in the riding-model approximation with C—H = 0.95–0.99Å and Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were included in the refinement in their as found positions with Uiso(H) = 1.5Ueq(C). The three largest peaks on the final difference Fourier are 1.12, 0.79 and 1.87Å from C17, C11 and O1s, respectively.
Crown ethers (CE), containing diphenyl oxide fragment (I, n=1–3), are structural isomers of the corresponding distal ("symmertic", x=y if n=2) and proximal ("asymmetric", x≠y if n=1–3) dibenzoCE (II) (Fig. 3). Products of disubstitution in the aromatic fragment of compounds (I) were not obtained before. As known, dibenzoCE of type (II) in such reactions form only the mixture of cis- and trans-isomers (Hiraoka, 1982; Gokel & Korzeniowski, 1982), which can be very rarely separated. We found out (Kamalov et al., 2003) that bromination of [1.4]dibenzo-15-crown-5 (III) by N-bromosuccinimide leads only to 5,5I-dibromide (IV) (Fig. 4). In the case of other CE (I) under investigation the bromination also takes place selectively. In this paper we report the crystal structure of the compound (IV) monohydrate (Fig. 1), which is formed during treatment of the obtained CE with water. Analysis of the molecular structure of the title compound demonstrates that the O4, O5, O1 and O2 atoms are co-planar within 0.03 Å. The O3 atom is displaced from this plane by 0.76 Å. The O—C—C—O fragments have alternating +sc and -sc conformations (Table 1). The aromatic rings are rotated relative to each other (angle between their mean planes is 65.8 °) due to repulsion between them (there are shortened intramolecular contacts of H5···C7 = 2.62 Å [sum of van der Waals radii is 2.87 Å (Zefirov & Zorky, 1995)], H5···C8 = 2.76 Å, C5···C8 3.24 Å [sum of van der Waals radii is 3.42 Å]). The O1 and O2 atoms are displaced from the plane of aromatic ring (the O1—C7—C12—O2 torsion angle is 8.7 (7) °). In the crystal structure, molecules of compound (IV) form columns along the (0 0 1) crystallographic direction with parallel arrangement of aromatic rings (Fig.2). The distance between neighbouring phenyl rings in columns is ca 3.5 Å, and it allows us to assume the existence of π···π stacking interactions. The macrocycle cavity is capped from one side by water molecule, which is bonded with two oxygen atoms of macrocycle by intermolecular hydrogen bonds (see Table 1). The other side of cavity is capped by a phenyl ring of a symmetry related molecule. A weak intermolecular hydrogen bond C3—H3···O2(x,0.5 - y,1/2 + z) with H···O = 2.42 Å, C—H···O = 163 ° is also present. Some short intermolecular distances are also observed, e.g. Br1···H16b(x - 1,0.5 - y,1/2 + z) = 3.09 Å (3.23 Å), Br2···Br(2(-x,1 - y,2 - z) = 3.73 Å (3.94 Å), Br2···H15b(x - 1,y,1 + z) = 3.08 Å (3.23 Å).
For related literature, see: Gokel & Korzeniowski (1982); Hiraoka (1982); Kamalov et al. (2003); Zefirov & Zorky (1995).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C18H18Br2O5·H2O | F(000) = 984 |
Mr = 492.16 | Dx = 1.763 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 3187 reflections |
a = 10.012 (5) Å | θ = 4–35° |
b = 26.850 (5) Å | µ = 4.41 mm−1 |
c = 7.031 (5) Å | T = 100 K |
β = 101.245 (5)° | Needle, colourless |
V = 1853.8 (16) Å3 | 0.80 × 0.10 × 0.10 mm |
Z = 4 |
Oxford Diffraction Xcalibur 3 diffractometer | 4196 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2786 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 16.1827 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −13→12 |
Absorption correction: analytical (Alcock, 1970) | k = −34→20 |
Tmin = 0.267, Tmax = 0.674 | l = −9→7 |
8042 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0894P)2] where P = (Fo2 + 2Fc2)/3 |
4196 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 1.56 e Å−3 |
0 restraints | Δρmin = −1.40 e Å−3 |
C18H18Br2O5·H2O | V = 1853.8 (16) Å3 |
Mr = 492.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.012 (5) Å | µ = 4.41 mm−1 |
b = 26.850 (5) Å | T = 100 K |
c = 7.031 (5) Å | 0.80 × 0.10 × 0.10 mm |
β = 101.245 (5)° |
Oxford Diffraction Xcalibur 3 diffractometer | 4196 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 2786 reflections with I > 2σ(I) |
Tmin = 0.267, Tmax = 0.674 | Rint = 0.049 |
8042 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.56 e Å−3 |
4196 reflections | Δρmin = −1.40 e Å−3 |
235 parameters |
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 | ||
Br1 | 0.17500 (5) | 0.20334 (2) | 0.59174 (7) | 0.02721 (18) | |
Br2 | 0.09743 (5) | 0.45440 (2) | 0.88064 (7) | 0.02732 (18) | |
O1 | 0.4996 (3) | 0.36064 (14) | 0.6514 (5) | 0.0253 (8) | |
O2 | 0.4725 (4) | 0.41181 (13) | 0.3243 (5) | 0.0241 (8) | |
O3 | 0.7321 (3) | 0.42023 (14) | 0.2538 (5) | 0.0214 (7) | |
O4 | 0.8663 (3) | 0.33494 (13) | 0.4418 (5) | 0.0218 (8) | |
O5 | 0.7177 (3) | 0.30854 (14) | 0.7383 (5) | 0.0223 (8) | |
C1 | 0.5977 (5) | 0.28185 (19) | 0.7094 (6) | 0.0172 (10) | |
C2 | 0.5905 (5) | 0.2310 (2) | 0.7246 (7) | 0.0206 (10) | |
H2 | 0.6713 | 0.2118 | 0.7584 | 0.025* | |
C3 | 0.4628 (5) | 0.20763 (19) | 0.6897 (6) | 0.0196 (10) | |
H3 | 0.4565 | 0.1725 | 0.6998 | 0.024* | |
C4 | 0.3470 (5) | 0.2359 (2) | 0.6409 (6) | 0.0199 (10) | |
C5 | 0.3525 (5) | 0.28774 (19) | 0.6283 (6) | 0.0177 (10) | |
H5 | 0.2715 | 0.3069 | 0.5954 | 0.021* | |
C6 | 0.4782 (5) | 0.31043 (19) | 0.6646 (6) | 0.0190 (10) | |
C7 | 0.3927 (5) | 0.39384 (19) | 0.6106 (7) | 0.0194 (10) | |
C8 | 0.3062 (5) | 0.4028 (2) | 0.7389 (7) | 0.0193 (10) | |
H8 | 0.3116 | 0.3827 | 0.8514 | 0.023* | |
C9 | 0.2113 (5) | 0.4413 (2) | 0.7021 (7) | 0.0215 (11) | |
C10 | 0.2026 (5) | 0.4705 (2) | 0.5394 (7) | 0.0223 (11) | |
H10 | 0.1378 | 0.4967 | 0.5159 | 0.027* | |
C11 | 0.2878 (5) | 0.46175 (18) | 0.4100 (7) | 0.0204 (10) | |
H11 | 0.2805 | 0.4819 | 0.2974 | 0.024* | |
C12 | 0.3843 (5) | 0.42354 (19) | 0.4431 (7) | 0.0215 (10) | |
C13 | 0.5051 (5) | 0.44934 (19) | 0.1948 (7) | 0.0213 (11) | |
H13B | 0.5351 | 0.4803 | 0.2670 | 0.026* | |
H13A | 0.4244 | 0.4570 | 0.0933 | 0.026* | |
C14 | 0.6174 (5) | 0.4288 (2) | 0.1053 (7) | 0.0244 (11) | |
H14B | 0.5879 | 0.3972 | 0.0372 | 0.029* | |
H14A | 0.6408 | 0.4527 | 0.0097 | 0.029* | |
C15 | 0.8397 (5) | 0.3949 (2) | 0.1904 (7) | 0.0246 (11) | |
H15B | 0.8895 | 0.4180 | 0.1193 | 0.029* | |
H15A | 0.8032 | 0.3672 | 0.1026 | 0.029* | |
C16 | 0.9332 (5) | 0.3751 (2) | 0.3668 (7) | 0.0249 (11) | |
H16B | 1.0191 | 0.3634 | 0.3323 | 0.030* | |
H16A | 0.9552 | 0.4017 | 0.4655 | 0.030* | |
C17 | 0.9287 (5) | 0.3213 (2) | 0.6340 (7) | 0.0211 (10) | |
H17B | 0.9388 | 0.3509 | 0.7196 | 0.025* | |
H17A | 1.0201 | 0.3071 | 0.6358 | 0.025* | |
C18 | 0.8378 (5) | 0.2831 (2) | 0.7032 (7) | 0.0211 (10) | |
H18B | 0.8119 | 0.2569 | 0.6035 | 0.025* | |
H18A | 0.8864 | 0.2671 | 0.8239 | 0.025* | |
O1S | 0.7389 (4) | 0.42336 (15) | 0.6775 (5) | 0.0303 (9) | |
H1OA | 0.7401 | 0.4253 | 0.5621 | 0.046* | |
H1OB | 0.7213 | 0.3907 | 0.7409 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0280 (3) | 0.0202 (3) | 0.0331 (3) | −0.0049 (2) | 0.0050 (2) | −0.0027 (2) |
Br2 | 0.0275 (3) | 0.0268 (3) | 0.0303 (3) | 0.0004 (2) | 0.0121 (2) | −0.0046 (2) |
O1 | 0.0239 (18) | 0.0122 (18) | 0.041 (2) | 0.0017 (15) | 0.0104 (15) | 0.0093 (16) |
O2 | 0.0338 (19) | 0.0107 (18) | 0.0316 (19) | −0.0005 (16) | 0.0159 (15) | 0.0015 (15) |
O3 | 0.0257 (18) | 0.0184 (19) | 0.0205 (17) | 0.0036 (16) | 0.0059 (13) | 0.0013 (14) |
O4 | 0.0285 (18) | 0.0183 (19) | 0.0183 (16) | −0.0032 (16) | 0.0042 (13) | 0.0008 (14) |
O5 | 0.0242 (18) | 0.0177 (19) | 0.0265 (17) | 0.0012 (15) | 0.0084 (14) | −0.0010 (15) |
C1 | 0.021 (2) | 0.019 (3) | 0.014 (2) | −0.002 (2) | 0.0071 (17) | 0.0030 (19) |
C2 | 0.026 (2) | 0.016 (3) | 0.021 (2) | 0.004 (2) | 0.0082 (19) | 0.001 (2) |
C3 | 0.031 (3) | 0.011 (2) | 0.018 (2) | −0.001 (2) | 0.0091 (19) | 0.0009 (19) |
C4 | 0.024 (2) | 0.018 (3) | 0.018 (2) | −0.004 (2) | 0.0043 (18) | −0.002 (2) |
C5 | 0.021 (2) | 0.016 (3) | 0.017 (2) | 0.001 (2) | 0.0060 (17) | 0.0037 (19) |
C6 | 0.030 (3) | 0.012 (2) | 0.017 (2) | 0.004 (2) | 0.0094 (19) | −0.0003 (19) |
C7 | 0.018 (2) | 0.015 (3) | 0.025 (2) | 0.003 (2) | 0.0042 (18) | 0.002 (2) |
C8 | 0.018 (2) | 0.020 (3) | 0.020 (2) | −0.001 (2) | 0.0038 (17) | 0.002 (2) |
C9 | 0.024 (3) | 0.017 (3) | 0.024 (2) | −0.004 (2) | 0.0042 (19) | −0.005 (2) |
C10 | 0.024 (2) | 0.014 (3) | 0.026 (3) | 0.001 (2) | −0.002 (2) | −0.004 (2) |
C11 | 0.027 (3) | 0.008 (2) | 0.026 (2) | −0.001 (2) | 0.005 (2) | 0.000 (2) |
C12 | 0.028 (3) | 0.013 (3) | 0.024 (2) | −0.002 (2) | 0.0075 (19) | −0.001 (2) |
C13 | 0.030 (3) | 0.012 (3) | 0.021 (2) | 0.001 (2) | 0.005 (2) | 0.003 (2) |
C14 | 0.033 (3) | 0.020 (3) | 0.022 (2) | 0.003 (2) | 0.008 (2) | −0.002 (2) |
C15 | 0.030 (3) | 0.020 (3) | 0.026 (3) | −0.001 (2) | 0.013 (2) | −0.001 (2) |
C16 | 0.024 (2) | 0.024 (3) | 0.027 (3) | 0.000 (2) | 0.007 (2) | −0.002 (2) |
C17 | 0.023 (2) | 0.019 (3) | 0.022 (2) | 0.003 (2) | 0.0047 (19) | −0.002 (2) |
C18 | 0.021 (2) | 0.021 (3) | 0.024 (2) | 0.007 (2) | 0.0097 (18) | 0.002 (2) |
O1S | 0.047 (2) | 0.019 (2) | 0.0265 (19) | −0.0048 (18) | 0.0104 (16) | 0.0002 (16) |
Br1—C4 | 1.901 (5) | C8—H8 | 0.9500 |
Br2—C9 | 1.886 (5) | C9—C10 | 1.376 (7) |
O1—C6 | 1.371 (6) | C10—C11 | 1.383 (7) |
O1—C7 | 1.379 (6) | C10—H10 | 0.9500 |
O2—C12 | 1.365 (6) | C11—C12 | 1.398 (7) |
O2—C13 | 1.438 (6) | C11—H11 | 0.9500 |
O3—C14 | 1.412 (6) | C13—C14 | 1.498 (7) |
O3—C15 | 1.418 (6) | C13—H13B | 0.9900 |
O4—C17 | 1.421 (6) | C13—H13A | 0.9900 |
O4—C16 | 1.424 (6) | C14—H14B | 0.9900 |
O5—C1 | 1.380 (6) | C14—H14A | 0.9900 |
O5—C18 | 1.446 (6) | C15—C16 | 1.497 (7) |
C1—C2 | 1.373 (7) | C15—H15B | 0.9900 |
C1—C6 | 1.404 (7) | C15—H15A | 0.9900 |
C2—C3 | 1.402 (7) | C16—H16B | 0.9900 |
C2—H2 | 0.9500 | C16—H16A | 0.9900 |
C3—C4 | 1.371 (7) | C17—C18 | 1.514 (7) |
C3—H3 | 0.9500 | C17—H17B | 0.9900 |
C4—C5 | 1.398 (7) | C17—H17A | 0.9900 |
C5—C6 | 1.376 (7) | C18—H18B | 0.9900 |
C5—H5 | 0.9500 | C18—H18A | 0.9900 |
C7—C8 | 1.388 (6) | O1S—H1OA | 0.8159 |
C7—C12 | 1.411 (7) | O1S—H1OB | 1.0151 |
C8—C9 | 1.393 (7) | ||
C6—O1—C7 | 121.6 (4) | O2—C12—C7 | 116.1 (4) |
C12—O2—C13 | 118.7 (4) | C11—C12—C7 | 118.7 (5) |
C14—O3—C15 | 113.8 (4) | O2—C13—C14 | 106.8 (4) |
C17—O4—C16 | 113.3 (4) | O2—C13—H13B | 110.4 |
C1—O5—C18 | 117.3 (4) | C14—C13—H13B | 110.4 |
C2—C1—O5 | 124.2 (4) | O2—C13—H13A | 110.4 |
C2—C1—C6 | 120.4 (5) | C14—C13—H13A | 110.4 |
O5—C1—C6 | 115.4 (5) | H13B—C13—H13A | 108.6 |
C1—C2—C3 | 119.4 (5) | O3—C14—C13 | 108.5 (4) |
C1—C2—H2 | 120.3 | O3—C14—H14B | 110.0 |
C3—C2—H2 | 120.3 | C13—C14—H14B | 110.0 |
C4—C3—C2 | 119.6 (5) | O3—C14—H14A | 110.0 |
C4—C3—H3 | 120.2 | C13—C14—H14A | 110.0 |
C2—C3—H3 | 120.2 | H14B—C14—H14A | 108.4 |
C3—C4—C5 | 121.7 (5) | O3—C15—C16 | 107.5 (4) |
C3—C4—Br1 | 118.9 (4) | O3—C15—H15B | 110.2 |
C5—C4—Br1 | 119.4 (4) | C16—C15—H15B | 110.2 |
C6—C5—C4 | 118.4 (5) | O3—C15—H15A | 110.2 |
C6—C5—H5 | 120.8 | C16—C15—H15A | 110.2 |
C4—C5—H5 | 120.8 | H15B—C15—H15A | 108.5 |
O1—C6—C5 | 124.9 (5) | O4—C16—C15 | 108.2 (4) |
O1—C6—C1 | 114.5 (4) | O4—C16—H16B | 110.1 |
C5—C6—C1 | 120.5 (5) | C15—C16—H16B | 110.1 |
O1—C7—C8 | 122.3 (4) | O4—C16—H16A | 110.1 |
O1—C7—C12 | 117.1 (4) | C15—C16—H16A | 110.1 |
C8—C7—C12 | 120.1 (5) | H16B—C16—H16A | 108.4 |
C7—C8—C9 | 119.8 (4) | O4—C17—C18 | 107.4 (4) |
C7—C8—H8 | 120.1 | O4—C17—H17B | 110.2 |
C9—C8—H8 | 120.1 | C18—C17—H17B | 110.2 |
C10—C9—C8 | 120.5 (5) | O4—C17—H17A | 110.2 |
C10—C9—Br2 | 119.9 (4) | C18—C17—H17A | 110.2 |
C8—C9—Br2 | 119.6 (4) | H17B—C17—H17A | 108.5 |
C9—C10—C11 | 120.2 (5) | O5—C18—C17 | 107.8 (4) |
C9—C10—H10 | 119.9 | O5—C18—H18B | 110.1 |
C11—C10—H10 | 119.9 | C17—C18—H18B | 110.1 |
C10—C11—C12 | 120.7 (5) | O5—C18—H18A | 110.1 |
C10—C11—H11 | 119.7 | C17—C18—H18A | 110.1 |
C12—C11—H11 | 119.7 | H18B—C18—H18A | 108.5 |
O2—C12—C11 | 125.2 (4) | H1OA—O1S—H1OB | 121.9 |
C18—O5—C1—C2 | 26.5 (6) | C7—C8—C9—Br2 | −178.3 (4) |
C18—O5—C1—C6 | −154.4 (4) | C8—C9—C10—C11 | 0.3 (7) |
O5—C1—C2—C3 | −179.2 (4) | Br2—C9—C10—C11 | 178.6 (4) |
C6—C1—C2—C3 | 1.7 (7) | C9—C10—C11—C12 | −0.5 (7) |
C1—C2—C3—C4 | 0.0 (7) | C13—O2—C12—C11 | 22.8 (7) |
C2—C3—C4—C5 | −1.2 (7) | C13—O2—C12—C7 | −157.8 (4) |
C2—C3—C4—Br1 | 179.4 (3) | C10—C11—C12—O2 | 179.7 (5) |
C3—C4—C5—C6 | 0.6 (7) | C10—C11—C12—C7 | 0.4 (7) |
Br1—C4—C5—C6 | 180.0 (3) | O1—C7—C12—O2 | 8.4 (7) |
C7—O1—C6—C5 | 4.1 (7) | C8—C7—C12—O2 | −179.4 (4) |
C7—O1—C6—C1 | −179.2 (4) | O1—C7—C12—C11 | −172.2 (4) |
C4—C5—C6—O1 | 177.7 (4) | C8—C7—C12—C11 | 0.0 (7) |
C4—C5—C6—C1 | 1.3 (6) | C12—O2—C13—C14 | 172.0 (4) |
C2—C1—C6—O1 | −179.2 (4) | C15—O3—C14—C13 | 172.5 (4) |
O5—C1—C6—O1 | 1.7 (6) | O2—C13—C14—O3 | −62.3 (5) |
C2—C1—C6—C5 | −2.4 (7) | C14—O3—C15—C16 | −163.2 (4) |
O5—C1—C6—C5 | 178.5 (4) | C17—O4—C16—C15 | −165.0 (4) |
C6—O1—C7—C8 | 67.1 (6) | O3—C15—C16—O4 | 71.5 (5) |
C6—O1—C7—C12 | −120.8 (5) | C16—O4—C17—C18 | 173.1 (4) |
O1—C7—C8—C9 | 171.6 (5) | C1—O5—C18—C17 | 149.0 (4) |
C12—C7—C8—C9 | −0.2 (7) | O4—C17—C18—O5 | −72.2 (5) |
C7—C8—C9—C10 | 0.1 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1OA···O3 | 0.82 | 2.16 | 2.968 (5) | 172 |
O1S—H1OB···O5 | 1.02 | 2.21 | 3.125 (5) | 150 |
Experimental details
Crystal data | |
Chemical formula | C18H18Br2O5·H2O |
Mr | 492.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.012 (5), 26.850 (5), 7.031 (5) |
β (°) | 101.245 (5) |
V (Å3) | 1853.8 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.41 |
Crystal size (mm) | 0.80 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur 3 |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.267, 0.674 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8042, 4196, 2786 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.156, 1.03 |
No. of reflections | 4196 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.56, −1.40 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXTL (Sheldrick, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1OA···O3 | 0.82 | 2.16 | 2.968 (5) | 172.2 |
O1S—H1OB···O5 | 1.02 | 2.21 | 3.125 (5) | 149.9 |
Crown ethers (CE), containing diphenyl oxide fragment (I, n=1–3), are structural isomers of the corresponding distal ("symmertic", x=y if n=2) and proximal ("asymmetric", x≠y if n=1–3) dibenzoCE (II) (Fig. 3). Products of disubstitution in the aromatic fragment of compounds (I) were not obtained before. As known, dibenzoCE of type (II) in such reactions form only the mixture of cis- and trans-isomers (Hiraoka, 1982; Gokel & Korzeniowski, 1982), which can be very rarely separated. We found out (Kamalov et al., 2003) that bromination of [1.4]dibenzo-15-crown-5 (III) by N-bromosuccinimide leads only to 5,5I-dibromide (IV) (Fig. 4). In the case of other CE (I) under investigation the bromination also takes place selectively. In this paper we report the crystal structure of the compound (IV) monohydrate (Fig. 1), which is formed during treatment of the obtained CE with water. Analysis of the molecular structure of the title compound demonstrates that the O4, O5, O1 and O2 atoms are co-planar within 0.03 Å. The O3 atom is displaced from this plane by 0.76 Å. The O—C—C—O fragments have alternating +sc and -sc conformations (Table 1). The aromatic rings are rotated relative to each other (angle between their mean planes is 65.8 °) due to repulsion between them (there are shortened intramolecular contacts of H5···C7 = 2.62 Å [sum of van der Waals radii is 2.87 Å (Zefirov & Zorky, 1995)], H5···C8 = 2.76 Å, C5···C8 3.24 Å [sum of van der Waals radii is 3.42 Å]). The O1 and O2 atoms are displaced from the plane of aromatic ring (the O1—C7—C12—O2 torsion angle is 8.7 (7) °). In the crystal structure, molecules of compound (IV) form columns along the (0 0 1) crystallographic direction with parallel arrangement of aromatic rings (Fig.2). The distance between neighbouring phenyl rings in columns is ca 3.5 Å, and it allows us to assume the existence of π···π stacking interactions. The macrocycle cavity is capped from one side by water molecule, which is bonded with two oxygen atoms of macrocycle by intermolecular hydrogen bonds (see Table 1). The other side of cavity is capped by a phenyl ring of a symmetry related molecule. A weak intermolecular hydrogen bond C3—H3···O2(x,0.5 - y,1/2 + z) with H···O = 2.42 Å, C—H···O = 163 ° is also present. Some short intermolecular distances are also observed, e.g. Br1···H16b(x - 1,0.5 - y,1/2 + z) = 3.09 Å (3.23 Å), Br2···Br(2(-x,1 - y,2 - z) = 3.73 Å (3.94 Å), Br2···H15b(x - 1,y,1 + z) = 3.08 Å (3.23 Å).