Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039219/fb2057sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039219/fb2057Isup2.hkl |
CCDC reference: 259387
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.074
- wR factor = 0.204
- Data-to-parameter ratio = 24.5
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.746 0.884 Tmin(prime) and Tmax expected: 0.966 0.983 RR(prime) = 0.858 Please check that your absorption correction is appropriate. PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 48 Perc. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.86 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.11 PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C3 .. 5.51 su PLAT230_ALERT_2_C Hirshfeld Test Diff for O2 - C12 .. 5.68 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.31 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.13 Ratio
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.112 Tmax scaled 0.983 Tmin scaled 0.829 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
In accordance with preparative methods of similar compounds (Wang & Wasielewski, 1997), 6 ml of the solution of HBr in acetic acid (100 ml of the latter solution contained 31 g of HBr) was added at once to a suspension of 1,4-bis(octyloxy)benzene (5.9 g, 15.1 mmol) and paraformaldehyde (0.93 g, 31.0 mmol) in acetic acid (50 ml). This mixture was then heated to 60–70 °C under stirring for 2 h.
After cooling down to room temperature, the suspension was poured into 300 ml of water. The precipitate was filtered and dissolved in 30 ml of hot chloroform (temperature: 50–55 °C), then 50 ml of methanol was added under stirring. After cooling to room temperature, the white solid was filtered off and dried under vacuum.
The white solid was dissolved in petroleum ether that boils in the interval 60–90°C. The crystals suitable for X-ray structure determination were obtained by slow evaporation at room temperature.
1HNMR and 13CNMR were determined with a Bruker Avance 400 MHz NMR spectrometer with tetramethylsilane as an internal standard.
1H NMR (CDCl3, 400 MHz) δ (p.p.m.) 6.91 (s, 2 H), 4.48 (s, 4 H), 3.93 (m, 4 H), 3.42 (s, 6 H), 1.76 (m, 4 H), 1.45 (m, 4 H), 1.32 (m, 18 H), 0.89 (t, 6 H); 13C NMR (CDCl3, 400 MHz) δ (p.p.m.) 150.0, 126.1, 111.9, 76.57, 68.73, 68.46, 57.86, 31.35, 28.98, 28.86, 28.78, 25.66, 13.60.
All the H atoms could be found in the difference Fourier maps. Nevertheless, they were placed into the idealized positions and refined in a riding atom approximation with following constraints: Cmethyl - Hmethyl = 0.96; Cmethylene - Hmethylene = 0.97; Caryl - Haryl = 0.93 Å. UisoH = 1.2UeqC except for methyls where UisoH = 1.5UeqC.
The title molecule (Fig. 1) is situated on a crystallographic inversion centre. The non-hydrogen atoms of the octyloxy chains and methoxylmethyl chains are almost coplanar with the benzene ring. The structure is interesting for its loose packing. The unit cell volume of the title structure is by 1.20 larger than it is expected if the 18 Å3 rule of the volume per non-hydrogen atom in the structure is taken into account (Kempster & Lipson, 1972). Despite the loose packing there are no large voids in the structure (Spek, 2003).
For related literature regarding the synthesis of the title compound, see: Wang & Wasielewski (1997). For related literature, see: Kempster & Lipson (1972); Spek (2003).
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. The molecular structure of title compound showing 50% probability displacement ellipsoids. | |
Fig. 2. The packing diagram of the title structure. |
C26H46O4 | Z = 1 |
Mr = 422.63 | F(000) = 234 |
Triclinic, P1 | Dx = 1.081 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6253 (9) Å | Cell parameters from 61 reflections |
b = 8.8218 (9) Å | θ = 4.9–15.1° |
c = 11.7625 (15) Å | µ = 0.07 mm−1 |
α = 106.662 (8)° | T = 293 K |
β = 95.398 (10)° | Prism, colourless |
γ = 96.066 (9)° | 0.48 × 0.38 × 0.25 mm |
V = 649.32 (14) Å3 |
Bruker P4 diffractometer | 1622 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 29.0°, θmin = 3.1° |
ω scans | h = −8→1 |
Absorption correction: ψ scan (XSCANS; Bruker, 1996) | k = −11→11 |
Tmin = 0.746, Tmax = 0.884 | l = −16→16 |
4198 measured reflections | 3 standard reflections every 97 reflections |
3375 independent reflections | intensity decay: 1.2% |
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)] = 0.074 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.204 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0902P)2] where P = (Fo2 + 2Fc2)/3 |
3375 reflections | (Δ/σ)max < 0.001 |
138 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
84 constraints |
C26H46O4 | γ = 96.066 (9)° |
Mr = 422.63 | V = 649.32 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.6253 (9) Å | Mo Kα radiation |
b = 8.8218 (9) Å | µ = 0.07 mm−1 |
c = 11.7625 (15) Å | T = 293 K |
α = 106.662 (8)° | 0.48 × 0.38 × 0.25 mm |
β = 95.398 (10)° |
Bruker P4 diffractometer | 1622 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Bruker, 1996) | Rint = 0.044 |
Tmin = 0.746, Tmax = 0.884 | 3 standard reflections every 97 reflections |
4198 measured reflections | intensity decay: 1.2% |
3375 independent reflections |
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.204 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.20 e Å−3 |
3375 reflections | Δρmin = −0.21 e Å−3 |
138 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 | ||
O1 | 0.3812 (2) | 0.14518 (16) | 0.61889 (13) | 0.0605 (5) | |
O2 | 0.0976 (3) | 0.33836 (18) | 0.38263 (15) | 0.0781 (6) | |
C1 | 0.0952 (3) | −0.0715 (2) | 0.57603 (17) | 0.0481 (6) | |
H1A | 0.1603 | −0.1192 | 0.6275 | 0.058* | |
C2 | 0.0963 (3) | 0.1405 (2) | 0.48497 (17) | 0.0457 (5) | |
C3 | 0.1910 (3) | 0.0668 (2) | 0.56160 (18) | 0.0468 (5) | |
C4 | 0.4938 (3) | 0.0743 (2) | 0.69460 (19) | 0.0504 (6) | |
H4A | 0.5184 | −0.0312 | 0.6493 | 0.061* | |
H4B | 0.4179 | 0.0642 | 0.7593 | 0.061* | |
C5 | 0.6946 (3) | 0.1825 (2) | 0.74413 (18) | 0.0519 (6) | |
H5A | 0.6666 | 0.2895 | 0.7830 | 0.062* | |
H5B | 0.7705 | 0.1874 | 0.6784 | 0.062* | |
C6 | 0.8262 (3) | 0.1272 (2) | 0.83323 (19) | 0.0515 (5) | |
H6A | 0.7490 | 0.1190 | 0.8978 | 0.062* | |
H6B | 0.8585 | 0.0217 | 0.7937 | 0.062* | |
C7 | 1.0233 (3) | 0.2394 (2) | 0.88503 (19) | 0.0543 (6) | |
H7A | 0.9905 | 0.3455 | 0.9223 | 0.065* | |
H7B | 1.1014 | 0.2455 | 0.8204 | 0.065* | |
C8 | 1.1552 (3) | 0.1891 (3) | 0.97676 (19) | 0.0573 (6) | |
H8A | 1.1896 | 0.0838 | 0.9389 | 0.069* | |
H8B | 1.0758 | 0.1810 | 1.0405 | 0.069* | |
C9 | 1.3533 (3) | 0.3028 (3) | 1.0317 (2) | 0.0592 (6) | |
H9A | 1.4318 | 0.3123 | 0.9679 | 0.071* | |
H9B | 1.3189 | 0.4078 | 1.0707 | 0.071* | |
C10 | 1.4858 (3) | 0.2508 (3) | 1.1217 (2) | 0.0662 (7) | |
H10A | 1.4068 | 0.2397 | 1.1849 | 0.079* | |
H10C | 1.5225 | 0.1467 | 1.0824 | 0.079* | |
C11 | 1.6788 (4) | 0.3651 (3) | 1.1768 (3) | 0.0897 (9) | |
H11A | 1.7535 | 0.3271 | 1.2346 | 0.135* | |
H11B | 1.6441 | 0.4687 | 1.2156 | 0.135* | |
H11C | 1.7618 | 0.3723 | 1.1154 | 0.135* | |
C12 | 0.2062 (3) | 0.2960 (2) | 0.47022 (18) | 0.0476 (5) | |
H12A | 0.2199 | 0.3812 | 0.5452 | 0.057* | |
H12B | 0.3424 | 0.2800 | 0.4497 | 0.057* | |
C13 | 0.1897 (4) | 0.4850 (3) | 0.3717 (2) | 0.0841 (9) | |
H13A | 0.1130 | 0.5101 | 0.3077 | 0.126* | |
H13B | 0.3276 | 0.4759 | 0.3548 | 0.126* | |
H13C | 0.1909 | 0.5683 | 0.4452 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0485 (9) | 0.0573 (9) | 0.0761 (10) | −0.0090 (7) | −0.0201 (8) | 0.0353 (8) |
O2 | 0.0733 (11) | 0.0697 (10) | 0.0955 (12) | −0.0189 (9) | −0.0216 (10) | 0.0518 (9) |
C1 | 0.0416 (12) | 0.0495 (11) | 0.0541 (12) | −0.0006 (9) | −0.0102 (10) | 0.0243 (10) |
C2 | 0.0409 (11) | 0.0458 (11) | 0.0502 (12) | −0.0006 (9) | −0.0039 (10) | 0.0195 (9) |
C3 | 0.0346 (11) | 0.0486 (11) | 0.0532 (12) | −0.0057 (9) | −0.0096 (9) | 0.0177 (9) |
C4 | 0.0410 (12) | 0.0537 (12) | 0.0577 (13) | −0.0012 (9) | −0.0099 (10) | 0.0263 (10) |
C5 | 0.0434 (12) | 0.0516 (12) | 0.0588 (13) | −0.0041 (10) | −0.0082 (10) | 0.0220 (10) |
C6 | 0.0423 (12) | 0.0560 (12) | 0.0553 (12) | −0.0022 (10) | −0.0083 (10) | 0.0233 (10) |
C7 | 0.0460 (13) | 0.0540 (12) | 0.0604 (13) | −0.0052 (10) | −0.0083 (11) | 0.0222 (10) |
C8 | 0.0444 (12) | 0.0618 (13) | 0.0635 (14) | −0.0050 (11) | −0.0105 (11) | 0.0251 (11) |
C9 | 0.0470 (13) | 0.0623 (14) | 0.0631 (14) | −0.0064 (11) | −0.0122 (11) | 0.0216 (11) |
C10 | 0.0531 (14) | 0.0697 (15) | 0.0700 (15) | −0.0027 (12) | −0.0175 (12) | 0.0237 (12) |
C11 | 0.0639 (17) | 0.101 (2) | 0.0935 (19) | −0.0119 (15) | −0.0290 (15) | 0.0328 (16) |
C12 | 0.0333 (11) | 0.0479 (11) | 0.0563 (12) | −0.0026 (9) | −0.0104 (9) | 0.0153 (9) |
C13 | 0.0745 (19) | 0.0752 (17) | 0.114 (2) | −0.0097 (14) | −0.0009 (17) | 0.0585 (16) |
O1—C3 | 1.382 (2) | C7—H7A | 0.9700 |
O1—C4 | 1.426 (2) | C7—H7B | 0.9700 |
O2—C12 | 1.363 (2) | C8—C9 | 1.528 (3) |
O2—C13 | 1.416 (2) | C8—H8A | 0.9700 |
C1—C3 | 1.377 (3) | C8—H8B | 0.9700 |
C1—C2i | 1.382 (2) | C9—C10 | 1.514 (3) |
C1—H1A | 0.9300 | C9—H9A | 0.9700 |
C2—C3 | 1.394 (3) | C9—H9B | 0.9700 |
C2—C12 | 1.547 (3) | C10—C11 | 1.506 (3) |
C3—C2 | 1.394 (3) | C10—H10A | 0.9700 |
C4—C5 | 1.512 (2) | C10—H10C | 0.9700 |
C4—H4A | 0.9700 | C11—H11A | 0.9600 |
C4—H4B | 0.9700 | C11—H11B | 0.9600 |
C5—C6 | 1.519 (3) | C11—H11C | 0.9600 |
C5—H5A | 0.9700 | C12—C2 | 1.547 (3) |
C5—H5B | 0.9700 | C12—H12A | 0.9700 |
C6—C7 | 1.513 (2) | C12—H12B | 0.9700 |
C6—H6A | 0.9700 | C13—H13A | 0.9600 |
C6—H6B | 0.9700 | C13—H13B | 0.9600 |
C7—C8 | 1.518 (3) | C13—H13C | 0.9600 |
C3—O1—C4 | 118.11 (15) | C7—C8—H8A | 108.7 |
C12—O2—C13 | 111.18 (17) | C9—C8—H8A | 108.7 |
C3—C1—C2i | 120.90 (18) | C7—C8—H8B | 108.7 |
C3—C1—H1A | 119.6 | C9—C8—H8B | 108.7 |
C2i—C1—H1A | 119.6 | H8A—C8—H8B | 107.6 |
C1i—C2—C3 | 118.55 (17) | C10—C9—C8 | 114.05 (19) |
C1i—C2—C12 | 121.69 (17) | C10—C9—H9A | 108.7 |
C3—C2—C12 | 119.77 (17) | C8—C9—H9A | 108.7 |
C1—C3—O1 | 125.25 (18) | C10—C9—H9B | 108.7 |
C1—C3—C2 | 120.56 (17) | C8—C9—H9B | 108.7 |
O1—C3—C2 | 114.19 (17) | H9A—C9—H9B | 107.6 |
O1—C4—C5 | 107.17 (16) | C11—C10—C9 | 113.6 (2) |
O1—C4—H4A | 110.3 | C11—C10—H10A | 108.8 |
C5—C4—H4A | 110.3 | C9—C10—H10A | 108.8 |
O1—C4—H4B | 110.3 | C11—C10—H10C | 108.8 |
C5—C4—H4B | 110.3 | C9—C10—H10C | 108.8 |
H4A—C4—H4B | 108.5 | H10A—C10—H10C | 107.7 |
C4—C5—C6 | 113.12 (17) | C10—C11—H11A | 109.5 |
C4—C5—H5A | 109.0 | C10—C11—H11B | 109.5 |
C6—C5—H5A | 109.0 | H11A—C11—H11B | 109.5 |
C4—C5—H5B | 109.0 | C10—C11—H11C | 109.5 |
C6—C5—H5B | 109.0 | H11A—C11—H11C | 109.5 |
H5A—C5—H5B | 107.8 | H11B—C11—H11C | 109.5 |
C7—C6—C5 | 112.50 (17) | O2—C12—C2 | 110.14 (15) |
C7—C6—H6A | 109.1 | O2—C12—H12A | 109.6 |
C5—C6—H6A | 109.1 | C2—C12—H12A | 109.6 |
C7—C6—H6B | 109.1 | O2—C12—H12B | 109.6 |
C5—C6—H6B | 109.1 | C2—C12—H12B | 109.6 |
H6A—C6—H6B | 107.8 | H12A—C12—H12B | 108.1 |
C6—C7—C8 | 113.56 (17) | O2—C13—H13A | 109.5 |
C6—C7—H7A | 108.9 | O2—C13—H13B | 109.5 |
C8—C7—H7A | 108.9 | H13A—C13—H13B | 109.5 |
C6—C7—H7B | 108.9 | O2—C13—H13C | 109.5 |
C8—C7—H7B | 108.9 | H13A—C13—H13C | 109.5 |
H7A—C7—H7B | 107.7 | H13B—C13—H13C | 109.5 |
C7—C8—C9 | 114.26 (18) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O2i | 0.93 | 2.41 | 2.747 (3) | 101 |
C5—H5B···Cg1ii | 0.97 | 2.93 | 3.750 (2) | 143 |
C5—H5B···Cg1iii | 0.97 | 2.93 | 3.750 (2) | 143 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C26H46O4 |
Mr | 422.63 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6253 (9), 8.8218 (9), 11.7625 (15) |
α, β, γ (°) | 106.662 (8), 95.398 (10), 96.066 (9) |
V (Å3) | 649.32 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.48 × 0.38 × 0.25 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (XSCANS; Bruker, 1996) |
Tmin, Tmax | 0.746, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4198, 3375, 1622 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.204, 1.05 |
No. of reflections | 3375 |
No. of parameters | 138 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.21 |
Computer programs: XSCANS (Bruker, 1996), XSCANS, SHELXTL (Bruker, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SHELXTL, WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···O2i | 0.93 | 2.41 | 2.747 (3) | 101 |
C5—H5B···Cg1ii | 0.97 | 2.93 | 3.750 (2) | 143 |
C5—H5B···Cg1iii | 0.97 | 2.93 | 3.750 (2) | 143 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1. |
The title molecule (Fig. 1) is situated on a crystallographic inversion centre. The non-hydrogen atoms of the octyloxy chains and methoxylmethyl chains are almost coplanar with the benzene ring. The structure is interesting for its loose packing. The unit cell volume of the title structure is by 1.20 larger than it is expected if the 18 Å3 rule of the volume per non-hydrogen atom in the structure is taken into account (Kempster & Lipson, 1972). Despite the loose packing there are no large voids in the structure (Spek, 2003).