organic papers
Acta Cryst.(2006). E62, o869–o870 doi:10.1107/S1600536806003035 Chenet al. C
22H20O4
o869
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
3-(Hydroxydiphenylmethyl)-2-(methoxy-methoxy)benzaldehyde
Wei-Zhu Chen, Qing-Le Zeng,* Hua Fang, Yu-Xing Gao and Yu-Fen Zhao
The Key Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, Xiamen University, Xiamen 361005, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 273 K
Mean(C–C) = 0.003 A˚
Rfactor = 0.050
wRfactor = 0.144
Data-to-parameter ratio = 15.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 23 December 2005 Accepted 25 January 2006
#2006 International Union of Crystallography
All rights reserved
The title compound, C22H20O4, was obtained from
methoxy-methyl phenyl ether by ortho-lithiation and electrophilic quenching. The molecular packing in the crystal structure is stabilized by an intramolecular hydrogen bond and van der Waals forces.
Comment
The title compound, (I), is an important intermediate in the synthesis of salicylaldehyde derivatives. We found a good method to synthesize 3-substituted salicylaldehyde derivatives by repeated ortho-lithiation followed by electrophilic quenching. Bond lengths and angles in (I) are in agreement with values reported in the literature (Tachiet al., 1999). The dihedral angle between the planes of the phenyl rings (C17– C22) and (C11–C16) is 106.76 (6). There is one
intra-molecular hydrogen bond (O4—H4B = 0.82 A˚ , O4 O3 = 2.89 A˚ and O4—H4B O3 = 178).
Experimental
An LiBu solution (12 ml, 1.6 M) was added to a solution of methoxymethyl phenyl ether (2.76 g, 20 mmol) in dry tetrahydro-furan (40 ml) in an ice-salt bath. After 3 h, a solution of diphenyl-methanone (3.64 g, 20 mmol) in dry tetrahydrofuran (10 ml) was added to the resulting slurry in the ice–salt bath. After another 3 h, the reaction was quenched by adding saturated NH4Cl. The
inter-mediate (2-methoxymethoxyphenyl)diphenylmethanol was obtained after work-up and purification by column chromatography. It was then redissolved in dry tetrahydrofuran (40 ml) and cooled in an ice– salt bath and LiBu solution in hexane (12 ml, 1.6M) was added. After 3 h, dimethylformamide (5 ml) was added to the cooled slurry. Saturated NH4Cl was again added to quench the reaction. The
purified by column chromatography to give (I) in 45% yield. Single crystals were grown by slow evaporation of a petroleum ether–ethyl acetate (5:1v/v) solution.
Crystal data
C22H20O4
Mr= 348.38
Orthorhombic,Pbca a= 8.6967 (16) A˚
b= 14.557 (3) A˚
c= 27.408 (5) A˚
V= 3469.7 (11) A˚3
Z= 8
Dx= 1.334 Mg m
3
MoKradiation Cell parameters from 7316
reflections = 2.2–28.2
= 0.09 mm1
T= 273 (2) K Chunk, colorless 0.140.050.03 mm
Data collection
Bruker APEX area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2001)
Tmin= 0.987,Tmax= 0.997 18443 measured reflections
3591 independent reflections 2916 reflections withI> 2(I)
Rint= 0.029
max= 26.5
h=10!10
k=18!16
l=27!34
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.050
wR(F2) = 0.144
S= 1.05 3591 reflections 236 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0793P)2 + 0.6714P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.22 e A˚
3
min=0.21 e A˚
3
The H atoms were positioned geometrically (C—H = 0.93, 0.93, 0.98, 0.97 and 0.96 A˚ for phenyl, formyl, tertiary, methylene and methyl H atoms, respectively, and O—H = 0.82 A˚ ) and were included in the refinement in the riding-model approximation. The displace-ment parameters of methyl H atoms were set at 1.5Ueq(parent atom),
while those of the other H atoms were set at 1.2Ueq.
Data collection:SMART(Bruker, 2001); cell refinement:SAINT
(Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEP-3(Farrugia, 1997) andViewerPro(Accelrys, 2001); software used to prepare material for publication:SHELXL97.
The authors thank the Ministry of Education of China (Key Project 104201) and the China Postdoctoral Science Found-ation for supporting this work, and MrZ.-B. Wei for technical assistance.
References
Accelrys (2001).ViewerPro. Version 4.2. Accelrys Inc., Burlington, Massa-chusetts, USA.
Bruker (2001).SAINT(Version 6.22),SMART(Version 5.625) andSADABS
(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
[image:2.610.313.564.70.274.2]Tachi, Y. Nakayama, S. Tani, F., Ueno, G. & Naruta, Y. (1999).Acta Cryst.C55, 1351–1353.
Figure 1
supporting information
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Acta Cryst. (2006). E62, o869–o870
supporting information
Acta Cryst. (2006). E62, o869–o870 [https://doi.org/10.1107/S1600536806003035]
3-(Hydroxydiphenylmethyl)-2-(methoxymethoxy)benzaldehyde
Wei-Zhu Chen, Qing-Le Zeng, Hua Fang, Yu-Xing Gao and Yu-Fen Zhao
3-(Hydroxydiphenylmethyl)-2-(methoxymethoxy)benzaldehyde
Crystal data
C22H20O4 Mr = 348.38
Orthorhombic, Pbca
Hall symbol: -P 2ac 2ab
a = 8.6967 (16) Å
b = 14.557 (3) Å
c = 27.408 (5) Å
V = 3469.7 (11) Å3 Z = 8
F(000) = 1472
Dx = 1.334 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7316 reflections
θ = 2.2–28.2°
µ = 0.09 mm−1 T = 273 K Chunk, colorless 0.14 × 0.05 × 0.03 mm
Data collection
Bruker APEX area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001)
Tmin = 0.987, Tmax = 0.997
18443 measured reflections 3591 independent reflections 2916 reflections with I > 2σ(I)
Rint = 0.029
θmax = 26.5°, θmin = 1.5° h = −10→10
k = −18→16
l = −27→34
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.144 S = 1.05 3591 reflections 236 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0793P)2 + 0.6714P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.22 e Å−3
Δρmin = −0.21 e Å−3
Special details
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
C1 0.0626 (2) 0.79013 (13) 0.20113 (6) 0.0536 (4) O1 0.0892 (2) 0.93638 (12) 0.23690 (6) 0.0969 (6) O2 −0.11886 (13) 0.77828 (8) 0.13596 (4) 0.0509 (3) C2 −0.00426 (17) 0.73984 (11) 0.16359 (5) 0.0445 (4) O3 −0.08100 (16) 0.82420 (9) 0.05671 (4) 0.0626 (4) C3 0.04002 (17) 0.64910 (11) 0.15443 (5) 0.0435 (4) O4 0.04116 (14) 0.64123 (8) 0.06778 (4) 0.0511 (3)
H4B 0.0050 0.6930 0.0652 0.077*
C4 0.15251 (19) 0.61205 (13) 0.18406 (6) 0.0539 (4)
H4A 0.1832 0.5516 0.1789 0.065*
C5 0.2208 (2) 0.66176 (15) 0.22101 (6) 0.0638 (5)
H5A 0.2970 0.6351 0.2401 0.077*
C6 0.1763 (2) 0.74981 (15) 0.22942 (6) 0.0631 (5)
H6A 0.2225 0.7833 0.2543 0.076*
C7 0.0153 (3) 0.88514 (14) 0.21188 (7) 0.0684 (5)
H7A −0.0764 0.9065 0.1986 0.082*
C8 −0.0807 (2) 0.85286 (12) 0.10448 (6) 0.0554 (4)
H8A −0.1548 0.9021 0.1087 0.066*
H8B 0.0202 0.8764 0.1129 0.066*
C9 −0.2304 (3) 0.82358 (15) 0.03538 (8) 0.0772 (6)
H9A −0.2234 0.8030 0.0022 0.116*
H9B −0.2725 0.8845 0.0362 0.116*
H9C −0.2959 0.7828 0.0534 0.116*
C10 −0.02145 (18) 0.59768 (10) 0.10975 (5) 0.0417 (4) C11 −0.19650 (18) 0.59526 (10) 0.10694 (5) 0.0433 (4) C12 −0.2662 (2) 0.58410 (11) 0.06225 (6) 0.0558 (4)
H12A −0.2060 0.5799 0.0343 0.067*
C13 −0.4238 (3) 0.57903 (13) 0.05847 (9) 0.0736 (6)
H13A −0.4696 0.5726 0.0280 0.088*
C14 −0.5132 (2) 0.58342 (13) 0.09949 (11) 0.0776 (7)
H14A −0.6197 0.5804 0.0970 0.093*
C15 −0.4457 (2) 0.59228 (13) 0.14377 (9) 0.0694 (6)
H15A −0.5061 0.5946 0.1717 0.083*
C16 −0.2877 (2) 0.59784 (12) 0.14761 (7) 0.0541 (4)
H16A −0.2427 0.6034 0.1782 0.065*
C17 0.03335 (18) 0.49810 (11) 0.10824 (5) 0.0434 (4) C18 0.12716 (19) 0.46686 (12) 0.07161 (6) 0.0500 (4)
H18A 0.1577 0.5067 0.0469 0.060*
C19 0.1766 (2) 0.37680 (13) 0.07118 (7) 0.0616 (5)
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Acta Cryst. (2006). E62, o869–o870
C20 0.1316 (2) 0.31668 (13) 0.10657 (8) 0.0649 (5)
H20A 0.1655 0.2561 0.1061 0.078*
C21 0.0360 (2) 0.34687 (13) 0.14284 (8) 0.0661 (5)
H21A 0.0039 0.3064 0.1670 0.079*
C22 −0.0127 (2) 0.43659 (13) 0.14374 (7) 0.0582 (5)
H22A −0.0775 0.4562 0.1686 0.070*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0523 (10) 0.0636 (11) 0.0449 (8) −0.0146 (8) 0.0059 (7) −0.0048 (7) O1 0.1349 (15) 0.0794 (10) 0.0765 (10) −0.0322 (10) −0.0054 (10) −0.0271 (8) O2 0.0469 (6) 0.0468 (6) 0.0592 (7) −0.0055 (5) −0.0039 (5) 0.0034 (5) C2 0.0396 (8) 0.0511 (9) 0.0427 (8) −0.0077 (6) 0.0035 (6) 0.0016 (7) O3 0.0717 (8) 0.0613 (8) 0.0548 (7) 0.0042 (6) 0.0015 (6) 0.0025 (6) C3 0.0381 (8) 0.0524 (9) 0.0398 (8) −0.0058 (6) 0.0044 (6) 0.0028 (6) O4 0.0614 (7) 0.0487 (6) 0.0433 (6) 0.0040 (5) 0.0136 (5) 0.0067 (5) C4 0.0471 (9) 0.0680 (11) 0.0467 (9) 0.0027 (8) 0.0001 (7) 0.0032 (8) C5 0.0521 (10) 0.0935 (15) 0.0458 (9) 0.0013 (9) −0.0064 (8) 0.0027 (9) C6 0.0572 (10) 0.0884 (14) 0.0437 (9) −0.0171 (10) −0.0024 (8) −0.0080 (9) C7 0.0859 (14) 0.0620 (11) 0.0573 (11) −0.0169 (10) 0.0072 (10) −0.0108 (9) C8 0.0615 (10) 0.0435 (9) 0.0611 (10) −0.0041 (7) −0.0026 (8) 0.0034 (7) C9 0.0944 (16) 0.0639 (12) 0.0733 (13) 0.0006 (11) −0.0246 (12) 0.0027 (10) C10 0.0436 (8) 0.0452 (8) 0.0363 (7) 0.0003 (6) 0.0031 (6) 0.0029 (6) C11 0.0456 (8) 0.0380 (7) 0.0463 (8) 0.0018 (6) −0.0025 (6) −0.0030 (6) C12 0.0666 (11) 0.0461 (9) 0.0546 (9) 0.0017 (8) −0.0135 (8) −0.0019 (7) C13 0.0739 (14) 0.0521 (10) 0.0947 (16) 0.0013 (9) −0.0406 (13) −0.0062 (10) C14 0.0449 (10) 0.0505 (11) 0.137 (2) −0.0020 (8) −0.0164 (13) −0.0121 (12) C15 0.0474 (10) 0.0569 (11) 0.1039 (16) −0.0058 (8) 0.0154 (11) −0.0168 (11) C16 0.0473 (9) 0.0575 (10) 0.0574 (10) −0.0045 (8) 0.0044 (7) −0.0099 (8) C17 0.0415 (8) 0.0462 (8) 0.0425 (8) −0.0006 (6) −0.0017 (6) 0.0007 (6) C18 0.0527 (9) 0.0511 (9) 0.0463 (9) −0.0007 (7) 0.0028 (7) −0.0012 (7) C19 0.0661 (11) 0.0567 (10) 0.0619 (11) 0.0086 (9) 0.0032 (9) −0.0097 (8) C20 0.0646 (11) 0.0465 (9) 0.0835 (13) 0.0069 (8) −0.0104 (10) 0.0008 (9) C21 0.0668 (12) 0.0559 (11) 0.0756 (13) 0.0020 (9) 0.0008 (10) 0.0212 (9) C22 0.0565 (10) 0.0583 (10) 0.0597 (10) 0.0065 (8) 0.0093 (8) 0.0139 (8)
Geometric parameters (Å, º)
C1—C6 1.387 (3) C10—C11 1.525 (2)
C1—C2 1.390 (2) C10—C17 1.526 (2)
C1—C7 1.473 (3) C11—C16 1.369 (2)
O1—C7 1.200 (2) C11—C12 1.376 (2)
O2—C2 1.3710 (19) C12—C13 1.377 (3)
O2—C8 1.426 (2) C12—H12A 0.9300
C2—C3 1.399 (2) C13—C14 1.368 (3)
O3—C8 1.374 (2) C13—H13A 0.9300
C3—C4 1.381 (2) C14—H14A 0.9300
C3—C10 1.531 (2) C15—C16 1.380 (3)
O4—C10 1.4219 (17) C15—H15A 0.9300
O4—H4B 0.8200 C16—H16A 0.9300
C4—C5 1.379 (3) C17—C18 1.371 (2)
C4—H4A 0.9300 C17—C22 1.382 (2)
C5—C6 1.358 (3) C18—C19 1.380 (3)
C5—H5A 0.9300 C18—H18A 0.9300
C6—H6A 0.9300 C19—C20 1.364 (3)
C7—H7A 0.9300 C19—H19A 0.9300
C8—H8A 0.9700 C20—C21 1.368 (3)
C8—H8B 0.9700 C20—H20A 0.9300
C9—H9A 0.9600 C21—C22 1.373 (3)
C9—H9B 0.9600 C21—H21A 0.9300
C9—H9C 0.9600 C22—H22A 0.9300
C6—C1—C2 119.29 (17) O4—C10—C3 107.18 (12)
C6—C1—C7 119.00 (17) C11—C10—C3 113.59 (12) C2—C1—C7 121.71 (17) C17—C10—C3 112.14 (12) C2—O2—C8 118.41 (13) C16—C11—C12 118.22 (16) O2—C2—C1 119.86 (15) C16—C11—C10 122.48 (14) O2—C2—C3 119.11 (13) C12—C11—C10 119.16 (14) C1—C2—C3 120.99 (15) C11—C12—C13 120.77 (19)
C8—O3—C9 113.25 (16) C11—C12—H12A 119.6
C4—C3—C2 117.28 (15) C13—C12—H12A 119.6
C4—C3—C10 121.77 (15) C14—C13—C12 120.10 (19)
C2—C3—C10 120.60 (14) C14—C13—H13A 120.0
C10—O4—H4B 109.5 C12—C13—H13A 120.0
C3—C4—C5 122.14 (18) C15—C14—C13 119.62 (19)
C3—C4—H4A 118.9 C15—C14—H14A 120.2
C5—C4—H4A 118.9 C13—C14—H14A 120.2
C6—C5—C4 119.81 (18) C14—C15—C16 120.4 (2)
C6—C5—H5A 120.1 C14—C15—H15A 119.8
C4—C5—H5A 120.1 C16—C15—H15A 119.8
C5—C6—C1 120.49 (17) C11—C16—C15 120.89 (18)
C5—C6—H6A 119.8 C11—C16—H16A 119.6
C1—C6—H6A 119.8 C15—C16—H16A 119.6
O1—C7—C1 123.3 (2) C18—C17—C22 118.23 (16)
O1—C7—H7A 118.4 C18—C17—C10 121.38 (13)
C1—C7—H7A 118.4 C22—C17—C10 120.39 (14)
O3—C8—O2 110.18 (14) C17—C18—C19 120.45 (16)
O3—C8—H8A 109.6 C17—C18—H18A 119.8
O2—C8—H8A 109.6 C19—C18—H18A 119.8
O3—C8—H8B 109.6 C20—C19—C18 120.96 (17)
O2—C8—H8B 109.6 C20—C19—H19A 119.5
H8A—C8—H8B 108.1 C18—C19—H19A 119.5
O3—C9—H9A 109.5 C19—C20—C21 118.99 (18)
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Acta Cryst. (2006). E62, o869–o870
H9A—C9—H9B 109.5 C21—C20—H20A 120.5
O3—C9—H9C 109.5 C20—C21—C22 120.40 (18)
H9A—C9—H9C 109.5 C20—C21—H21A 119.8
H9B—C9—H9C 109.5 C22—C21—H21A 119.8
O4—C10—C11 110.59 (12) C21—C22—C17 120.95 (18) O4—C10—C17 106.36 (12) C21—C22—H22A 119.5 C11—C10—C17 106.76 (12) C17—C22—H22A 119.5
