Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010101664X/bm1474sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101664X/bm1474Isup2.hkl |
CCDC reference: 180154
Bis[2-(2-hydroxyphenoxy)ethyl]ether was synthesized according to a procedure previously reported (Kyba et al., 1977) and recrystallized from methanol.
The hydroxyl-H atoms of the methanol molecule and catechol units were found in the Fourier difference map and introduced as riding atoms with a displacement parameter equal to 1.2 times that of the parent atom. The O6—H6 bond length is slightly larger than usual, but was kept as found in the refinement. All other H atoms were introduced at calculated positions (CH 0.93, CH2 0.97, CH3 0.96 Å) as riding atoms with a displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom.
Data collection: KappaCCD Software (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997) and PARST97 (Nardelli, 1995).
C16H18O5·CH4O | F(000) = 688 |
Mr = 322.35 | Dx = 1.288 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8638 (7) Å | Cell parameters from 6010 reflections |
b = 9.6264 (5) Å | θ = 2.8–25.7° |
c = 15.9399 (9) Å | µ = 0.10 mm−1 |
β = 94.270 (3)° | T = 100 K |
V = 1662.4 (2) Å3 | Parallelepiped, colourless |
Z = 4 | 0.30 × 0.30 × 0.25 mm |
Nonius KappaCCD area detector diffractometer | 2190 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
Detector resolution: 18 pixels mm-1 | h = −13→13 |
ϕ scans | k = −11→11 |
6010 measured reflections | l = −19→19 |
3129 independent 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)] = 0.045 | Hydrogen site location: see text |
wR(F2) = 0.119 | See text |
S = 1.02 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.291P] where P = (Fo2 + 2Fc2)/3 |
3129 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C16H18O5·CH4O | V = 1662.4 (2) Å3 |
Mr = 322.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.8638 (7) Å | µ = 0.10 mm−1 |
b = 9.6264 (5) Å | T = 100 K |
c = 15.9399 (9) Å | 0.30 × 0.30 × 0.25 mm |
β = 94.270 (3)° |
Nonius KappaCCD area detector diffractometer | 2190 reflections with I > 2σ(I) |
6010 measured reflections | Rint = 0.047 |
3129 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.119 | See text |
S = 1.02 | Δρmax = 0.16 e Å−3 |
3129 reflections | Δρmin = −0.23 e Å−3 |
209 parameters |
Experimental. crystal-to-detector distance 28 mm |
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. A 180° range in ϕ was scanned during data collection, with 2° ϕ steps. Crystal-to-detector distance fixed at 28 mm. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms bound to O atoms have been found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.49490 (13) | 0.21467 (15) | −0.00582 (9) | 0.0362 (4) | |
H1 | 0.4672 | 0.2636 | 0.0372 | 0.043* | |
O2 | 0.62048 (11) | 0.35906 (13) | 0.11635 (8) | 0.0272 (3) | |
O3 | 0.49235 (12) | 0.44762 (13) | 0.24994 (8) | 0.0270 (3) | |
O4 | 0.24949 (11) | 0.36477 (13) | 0.27016 (8) | 0.0270 (3) | |
O5 | 0.14137 (12) | 0.20741 (14) | 0.14692 (8) | 0.0320 (3) | |
H5 | 0.2210 | 0.2565 | 0.1439 | 0.038* | |
C1 | 0.61996 (18) | 0.1992 (2) | 0.00656 (12) | 0.0279 (4) | |
C2 | 0.67928 (18) | 0.1102 (2) | −0.04486 (12) | 0.0332 (5) | |
H2 | 0.6336 | 0.0623 | −0.0872 | 0.040* | |
C3 | 0.80598 (19) | 0.0910 (2) | −0.03439 (13) | 0.0332 (5) | |
H3 | 0.8450 | 0.0308 | −0.0696 | 0.040* | |
C4 | 0.87403 (19) | 0.16201 (19) | 0.02877 (12) | 0.0309 (5) | |
H4 | 0.9590 | 0.1490 | 0.0362 | 0.037* | |
C5 | 0.81592 (18) | 0.2529 (2) | 0.08129 (12) | 0.0276 (4) | |
H5A | 0.8618 | 0.3004 | 0.1237 | 0.033* | |
C6 | 0.68984 (17) | 0.27176 (19) | 0.06988 (11) | 0.0249 (4) | |
C7 | 0.68325 (18) | 0.4313 (2) | 0.18555 (12) | 0.0287 (4) | |
H7A | 0.7524 | 0.4834 | 0.1666 | 0.034* | |
H7B | 0.7143 | 0.3659 | 0.2283 | 0.034* | |
C8 | 0.59168 (18) | 0.5277 (2) | 0.22049 (13) | 0.0299 (5) | |
H8A | 0.6313 | 0.5812 | 0.2665 | 0.036* | |
H8B | 0.5600 | 0.5919 | 0.1772 | 0.036* | |
C9 | 0.40896 (18) | 0.53039 (19) | 0.29455 (12) | 0.0293 (5) | |
H9A | 0.3629 | 0.5922 | 0.2558 | 0.035* | |
H9B | 0.4549 | 0.5865 | 0.3366 | 0.035* | |
C10 | 0.32203 (17) | 0.4364 (2) | 0.33606 (12) | 0.0276 (4) | |
H10A | 0.2689 | 0.4901 | 0.3701 | 0.033* | |
H10B | 0.3678 | 0.3703 | 0.3721 | 0.033* | |
C11 | 0.16499 (17) | 0.26858 (18) | 0.29434 (12) | 0.0253 (4) | |
C12 | 0.11061 (17) | 0.18857 (19) | 0.22800 (12) | 0.0261 (4) | |
C13 | 0.02417 (17) | 0.0889 (2) | 0.24427 (13) | 0.0315 (5) | |
H13 | −0.0126 | 0.0361 | 0.2004 | 0.038* | |
C14 | −0.00810 (18) | 0.0672 (2) | 0.32610 (14) | 0.0340 (5) | |
H14 | −0.0666 | 0.0003 | 0.3368 | 0.041* | |
C15 | 0.04669 (19) | 0.1451 (2) | 0.39130 (13) | 0.0336 (5) | |
H15 | 0.0255 | 0.1296 | 0.4460 | 0.040* | |
C16 | 0.13327 (18) | 0.2464 (2) | 0.37586 (13) | 0.0310 (5) | |
H16 | 0.1696 | 0.2990 | 0.4199 | 0.037* | |
O6 | 0.35039 (12) | 0.34310 (13) | 0.10620 (8) | 0.0294 (3) | |
H6 | 0.4092 | 0.3686 | 0.1574 | 0.035* | |
C17 | 0.3205 (2) | 0.4714 (2) | 0.06243 (14) | 0.0365 (5) | |
H17A | 0.2772 | 0.5317 | 0.0981 | 0.055* | |
H17B | 0.2692 | 0.4521 | 0.0121 | 0.055* | |
H17C | 0.3951 | 0.5158 | 0.0480 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0277 (7) | 0.0470 (9) | 0.0331 (8) | 0.0022 (7) | −0.0028 (6) | −0.0137 (7) |
O2 | 0.0268 (7) | 0.0281 (7) | 0.0265 (7) | −0.0008 (6) | 0.0000 (6) | −0.0054 (6) |
O3 | 0.0262 (7) | 0.0256 (7) | 0.0296 (7) | −0.0028 (6) | 0.0047 (5) | −0.0045 (6) |
O4 | 0.0278 (7) | 0.0266 (7) | 0.0262 (7) | −0.0057 (6) | 0.0001 (5) | −0.0017 (6) |
O5 | 0.0315 (7) | 0.0357 (8) | 0.0285 (8) | −0.0078 (6) | 0.0004 (6) | −0.0019 (6) |
C1 | 0.0266 (10) | 0.0298 (10) | 0.0270 (10) | −0.0009 (9) | −0.0006 (8) | 0.0004 (8) |
C2 | 0.0351 (11) | 0.0345 (11) | 0.0299 (11) | −0.0025 (10) | 0.0014 (9) | −0.0076 (9) |
C3 | 0.0358 (11) | 0.0341 (11) | 0.0304 (11) | 0.0027 (10) | 0.0074 (9) | −0.0025 (9) |
C4 | 0.0287 (10) | 0.0307 (10) | 0.0336 (11) | 0.0018 (9) | 0.0046 (8) | 0.0026 (9) |
C5 | 0.0279 (10) | 0.0267 (10) | 0.0280 (10) | −0.0024 (9) | 0.0012 (8) | 0.0014 (8) |
C6 | 0.0284 (10) | 0.0235 (9) | 0.0231 (10) | 0.0011 (9) | 0.0044 (8) | 0.0013 (8) |
C7 | 0.0293 (10) | 0.0295 (10) | 0.0271 (11) | −0.0053 (9) | 0.0003 (8) | −0.0049 (8) |
C8 | 0.0298 (10) | 0.0275 (10) | 0.0327 (11) | −0.0066 (9) | 0.0051 (9) | −0.0046 (8) |
C9 | 0.0293 (10) | 0.0245 (10) | 0.0342 (11) | 0.0000 (9) | 0.0041 (9) | −0.0066 (8) |
C10 | 0.0264 (10) | 0.0280 (10) | 0.0280 (11) | −0.0013 (9) | −0.0001 (8) | −0.0071 (8) |
C11 | 0.0221 (9) | 0.0208 (9) | 0.0332 (11) | 0.0028 (8) | 0.0034 (8) | 0.0013 (8) |
C12 | 0.0231 (9) | 0.0257 (9) | 0.0290 (10) | 0.0018 (8) | −0.0005 (8) | 0.0006 (8) |
C13 | 0.0244 (11) | 0.0286 (10) | 0.0408 (12) | −0.0021 (9) | −0.0016 (9) | −0.0030 (9) |
C14 | 0.0274 (10) | 0.0289 (11) | 0.0466 (13) | −0.0008 (9) | 0.0082 (9) | 0.0013 (10) |
C15 | 0.0332 (11) | 0.0311 (11) | 0.0377 (12) | 0.0002 (10) | 0.0100 (9) | 0.0006 (9) |
C16 | 0.0316 (11) | 0.0292 (10) | 0.0326 (11) | 0.0016 (9) | 0.0050 (9) | −0.0045 (9) |
O6 | 0.0311 (7) | 0.0317 (7) | 0.0250 (7) | −0.0014 (6) | −0.0008 (6) | 0.0027 (6) |
C17 | 0.0340 (11) | 0.0398 (12) | 0.0356 (12) | 0.0055 (10) | 0.0019 (9) | 0.0088 (10) |
O1—C1 | 1.366 (2) | C8—H8A | 0.9700 |
O1—H1 | 0.90 | C8—H8B | 0.9700 |
O2—C6 | 1.380 (2) | C9—C10 | 1.497 (3) |
O2—C7 | 1.433 (2) | C9—H9A | 0.9700 |
O3—C8 | 1.433 (2) | C9—H9B | 0.9700 |
O3—C9 | 1.434 (2) | C10—H10A | 0.9700 |
O4—C11 | 1.379 (2) | C10—H10B | 0.9700 |
O4—C10 | 1.441 (2) | C11—C16 | 1.385 (3) |
O5—C12 | 1.371 (2) | C11—C12 | 1.403 (3) |
O5—H5 | 0.99 | C12—C13 | 1.381 (3) |
C1—C2 | 1.378 (3) | C13—C14 | 1.391 (3) |
C1—C6 | 1.403 (3) | C13—H13 | 0.9300 |
C2—C3 | 1.386 (3) | C14—C15 | 1.380 (3) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.384 (3) | C15—C16 | 1.390 (3) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—C5 | 1.394 (3) | C16—H16 | 0.9300 |
C4—H4 | 0.9300 | O6—C17 | 1.444 (2) |
C5—C6 | 1.380 (3) | O6—H6 | 1.03 |
C5—H5A | 0.9300 | C17—H17A | 0.9600 |
C7—C8 | 1.498 (3) | C17—H17B | 0.9600 |
C7—H7A | 0.9700 | C17—H17C | 0.9600 |
C7—H7B | 0.9700 | ||
C1—O1—H1 | 109.4 | O3—C9—H9A | 109.9 |
C6—O2—C7 | 117.45 (14) | C10—C9—H9A | 109.9 |
C8—O3—C9 | 112.47 (13) | O3—C9—H9B | 109.9 |
C11—O4—C10 | 117.19 (14) | C10—C9—H9B | 109.9 |
C12—O5—H5 | 112.5 | H9A—C9—H9B | 108.3 |
O1—C1—C2 | 119.06 (17) | O4—C10—C9 | 107.20 (15) |
O1—C1—C6 | 121.91 (17) | O4—C10—H10A | 110.3 |
C2—C1—C6 | 119.03 (18) | C9—C10—H10A | 110.3 |
C1—C2—C3 | 121.01 (19) | O4—C10—H10B | 110.3 |
C1—C2—H2 | 119.5 | C9—C10—H10B | 110.3 |
C3—C2—H2 | 119.5 | H10A—C10—H10B | 108.5 |
C4—C3—C2 | 119.57 (19) | O4—C11—C16 | 125.65 (17) |
C4—C3—H3 | 120.2 | O4—C11—C12 | 114.19 (16) |
C2—C3—H3 | 120.2 | C16—C11—C12 | 120.16 (18) |
C3—C4—C5 | 120.35 (19) | O5—C12—C13 | 119.08 (17) |
C3—C4—H4 | 119.8 | O5—C12—C11 | 121.31 (17) |
C5—C4—H4 | 119.8 | C13—C12—C11 | 119.61 (18) |
C6—C5—C4 | 119.53 (18) | C12—C13—C14 | 120.19 (19) |
C6—C5—H5A | 120.2 | C12—C13—H13 | 119.9 |
C4—C5—H5A | 120.2 | C14—C13—H13 | 119.9 |
C5—C6—O2 | 125.84 (17) | C15—C14—C13 | 120.00 (19) |
C5—C6—C1 | 120.50 (17) | C15—C14—H14 | 120.0 |
O2—C6—C1 | 113.66 (16) | C13—C14—H14 | 120.0 |
O2—C7—C8 | 107.20 (15) | C14—C15—C16 | 120.50 (19) |
O2—C7—H7A | 110.3 | C14—C15—H15 | 119.8 |
C8—C7—H7A | 110.3 | C16—C15—H15 | 119.7 |
O2—C7—H7B | 110.3 | C11—C16—C15 | 119.53 (19) |
C8—C7—H7B | 110.3 | C11—C16—H16 | 120.2 |
H7A—C7—H7B | 108.5 | C15—C16—H16 | 120.2 |
O3—C8—C7 | 109.00 (15) | C17—O6—H6 | 106.5 |
O3—C8—H8A | 109.9 | O6—C17—H17A | 109.5 |
C7—C8—H8A | 109.9 | O6—C17—H17B | 109.5 |
O3—C8—H8B | 109.9 | H17A—C17—H17B | 109.5 |
C7—C8—H8B | 109.9 | O6—C17—H17C | 109.5 |
H8A—C8—H8B | 108.3 | H17A—C17—H17C | 109.5 |
O3—C9—C10 | 109.02 (14) | H17B—C17—H17C | 109.5 |
O1—C1—C2—C3 | −179.80 (19) | C8—O3—C9—C10 | −169.97 (15) |
C6—C1—C2—C3 | 0.5 (3) | C11—O4—C10—C9 | 178.05 (14) |
C1—C2—C3—C4 | 0.1 (3) | O3—C9—C10—O4 | −64.26 (19) |
C2—C3—C4—C5 | −0.4 (3) | C10—O4—C11—C16 | 8.1 (2) |
C3—C4—C5—C6 | −0.1 (3) | C10—O4—C11—C12 | −171.19 (16) |
C4—C5—C6—O2 | −179.29 (16) | O4—C11—C12—O5 | 0.1 (3) |
C4—C5—C6—C1 | 0.7 (3) | C16—C11—C12—O5 | −179.30 (17) |
C7—O2—C6—C5 | −3.5 (3) | O4—C11—C12—C13 | −179.81 (15) |
C7—O2—C6—C1 | 176.49 (16) | C16—C11—C12—C13 | 0.8 (3) |
O1—C1—C6—C5 | 179.39 (17) | O5—C12—C13—C14 | 179.62 (18) |
C2—C1—C6—C5 | −0.9 (3) | C11—C12—C13—C14 | −0.5 (3) |
O1—C1—C6—O2 | −0.6 (3) | C12—C13—C14—C15 | −0.3 (3) |
C2—C1—C6—O2 | 179.08 (16) | C13—C14—C15—C16 | 0.7 (3) |
C6—O2—C7—C8 | 175.01 (14) | O4—C11—C16—C15 | −179.68 (17) |
C9—O3—C8—C7 | 172.19 (15) | C12—C11—C16—C15 | −0.4 (3) |
O2—C7—C8—O3 | 61.43 (19) | C14—C15—C16—C11 | −0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.90 | 1.90 | 2.7566 (19) | 158 |
O5—H5···O6 | 0.99 | 1.78 | 2.7392 (18) | 163 |
O6—H6···O3 | 1.03 | 1.84 | 2.8485 (18) | 167 |
Experimental details
Crystal data | |
Chemical formula | C16H18O5·CH4O |
Mr | 322.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.8638 (7), 9.6264 (5), 15.9399 (9) |
β (°) | 94.270 (3) |
V (Å3) | 1662.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Nonius KappaCCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6010, 3129, 2190 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.119, 1.02 |
No. of reflections | 3129 |
No. of parameters | 209 |
H-atom treatment | See text |
Δρmax, Δρmin (e Å−3) | 0.16, −0.23 |
Computer programs: KappaCCD Software (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997) and PARST97 (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O6 | 0.90 | 1.90 | 2.7566 (19) | 158 |
O5—H5···O6 | 0.99 | 1.78 | 2.7392 (18) | 163 |
O6—H6···O3 | 1.03 | 1.84 | 2.8485 (18) | 167 |
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In the course of our studies on complexes of catechol derivatives, we obtained the crystal structure of bis[2-(2-hydroxyphenoxy)ethyl]ether as a methanol solvate (I). The crystal structures of only two related compounds have been reported previously. One corresponds to the molecule with two methoxy groups in place of the OH ones in (I) (Chacko et al., 1984) and the other to the potassium picrate complex of the molecule with two carboxymethoxy substituents (Hughes et al., 1978). In the first of these, the catechol units are located trans to the central ether moiety, whereas in the second the arrangement is cis due to complexation to potassium ions.
The asymmetric unit of (I) comprises one bis[2-(2-hydroxyphenoxy)ethyl]ether and one methanol molecule (Fig. 1). The geometry of the former is cis due to the involvement of the methanol molecule in hydrogen bonding. The methanol hydroxyl proton is bound to the central ether-O atom whereas the methanol-O atom is hydrogen bonded to the two OH groups of the catechol units. The methanol O atom thus acts as a ring closure. The five atoms O1, O2, O3, O4 and O5 define a mean plane with a maximum deviation of 0.071 (1) Å, the methanol atom O6 lying 0.708 (1) Å from this plane. The situation is somewhat different in the hydrated form of the analogous compound with an ether chain longer by one O(CH2)2 unit (Suh et al., 1985), since in this case the array of O atoms is sufficiently large to encompass the water molecule close to its centre with, furthermore, one of the catechol hydroxyl proton involved in an intermolecular hydrogen bond.
The dihedral angle between the two aromatic rings in (I) is 117.76 (6)°, which gives the molecule a `butterfly' shape, the methanol molecule being located on the convex side. The O—C—C—O torsion angles in the ether part of the molecule are 61.4 (2) and -64.3 (2)° for O2—C7—C8—O3 and O3—C9—C10—O4, respectively, close to the ideal values for gauche angles, whereas the C—O—C—C torsion angles deviate from their ideal values of 0 or 180° by less than 10°.
The crystal packing contains an interesting feature. Molecules are related by the screw axis such that two protons of the ether chain (bound to C7 and C10) point towards the centroids of the aromatic rings of a neighbouring molecule. The H···centroid distances (2.56 and 2.58 Å) and the C—H···centroid angles (151 and 147°) indicate the possibility of weak CH···π interactions, at least on a geometrical basis (Jeffrey & Saenger, 1994).